CN110105757A

CN110105757A - Porous polyimide film base film, its manufacturing method and composition

Info

Publication number: CN110105757A
Application number: CN201910087385.2A
Authority: CN
Inventors: 石川薰; 西端巳季夫; 川村芳次; 中尾浩章
Original assignee: Tokyo Ohka Kogyo Co Ltd; JFE Chemical Corp
Current assignee: Tokyo Ohka Kogyo Co Ltd; JFE Chemical Corp
Priority date: 2018-02-01
Filing date: 2019-01-29
Publication date: 2019-08-09
Anticipated expiration: 2039-01-29
Also published as: JP7397570B2; KR20190093502A; TWI797220B; JP2019131747A; TW201936715A; CN110105757B

Abstract

The issue of the present invention is to provide the excellent Porous polyimide film base film of tensile strength and bending strength, its manufacturing method and the compositions that can be suitably used for its manufacture.Solution of the invention is the Porous polyimide film base film that the tensile strength as defined in ASTM standard D638 is 45MPa or more.The Porous polyimide film base film includes: the polyimides containing the structural unit that following formula (1-1) structural unit indicated and following formula (1-2) indicate.In above-mentioned formula, A¹¹And A¹²Each independently represent the aromatic group of 4 valences as derived from the acid anhydrides comprising aromatic tetracarboxylic acid's acid anhydride, B¹¹And B¹²The diamines residue of the divalent as derived from aromatic diamine is each independently represented, selected from by A¹²And B¹²At least one in the group of composition includes the spacer group of divalent in its structure.

Description

Porous polyimide film base film, its manufacturing method and composition

Technical field

The present invention relates to the excellent Porous polyimide film base film of tensile strength and bending strength, its manufacturing method and It can be suitably used for the composition of its manufacture.

Background technique

Polyimide resin has mechanical strength, chemical stability, the characteristic of excellent heat resistance.By having these excellent spies Property the polyimide film of Porous that is formed of polyimide resin attract attention in a variety of applications where.

For example, describing a kind of Porous polyimide film in patent document 1, the Porous polyimide film passes through Containing the non-crosslinked resin other than polyimide resin and polyimide resin, thus with only including the porous of polyimide resin Matter polyimide film is compared, and the generation of cracking is suppressed.

However, for the Porous polyimide film recorded in citation 1, for force when manufacture Fragility can only be manufactured by single chip mode, and manufacture adaptability is poor.

Existing technical literature

Patent document

Patent document 1: Japanese Unexamined Patent Publication 2016-183273 bulletin

Summary of the invention

Problems to be solved by the invention

The present invention be the project in view of the above-mentioned prior art and make, and it is an object of the present invention to provide a kind of tensile strength and bending Porous polyimide film base film, its manufacturing method and the composition that its manufacture can be suitably used for of excellent strength.

Means for solving the problems

The inventors of the present application found that for the polyimides of the polyimides comprising the structural unit containing specific structure For film, even if tensile strength and bending strength are also excellent in the case where being formed as Porous, when can inhibit to manufacture because of base film The force such as stretching, winding caused by the generation that ruptures of film, the windability of long size shape (for example, at least 1m or more) can be made Excellent base film, so as to complete the present invention.That is, the present invention is as described below.

1st mode of the invention is a kind of Porous polyimide film base film (Japanese: former anti-), and the Porous polyamides is sub- The tensile strength as defined in ASTM standard D638 of amine film base film is 45MPa or more.

2nd mode of the invention is a kind of Porous polyimide film base film, it includes: it is indicated containing following formula (1-1) Structural unit and following formula (1-2) indicate structural unit polyimides.

(in above-mentioned formula, A¹¹And A¹²Each independently represent 4 valences as derived from the acid anhydrides comprising aromatic tetracarboxylic acid's acid anhydride Aromatic group, B¹¹And B¹²The diamines residue of the divalent as derived from aromatic diamine is each independently represented, selected from by A¹²And B¹² At least one in the group of composition includes the spacer group (spacer group) of divalent in its structure.)

3rd mode of the invention is a kind of Porous polyimide film base film, it includes: it is indicated containing following formula (2-1) Structural unit and following formula (2-2) indicate structural unit polyimides.

(in above-mentioned formula, A²¹And A²²Each independently represent 4 valences as derived from the acid anhydrides comprising aromatic tetracarboxylic acid's acid anhydride Aromatic group, B²¹And B²²Each independently represent the diamines residue of the divalent as derived from aromatic diamine, A²²And B²²Meet choosing Freely at least one condition in the group of following (I) and (II) composition.

(I) derivative A²²Aromatic tetracarboxylic acid's acid anhydride electron affinity energy (Ea) be 2.6eV or less.

(II) derivative B²²Aromatic diamine be and derivative B²¹The different aromatic diamine of aromatic diamine, and 40 DEG C water in solubility be 0.1g/L or more.)

4th mode of the invention is the manufacturing method of Porous polyimide film base film comprising following processes:

Envelope formation process will be applied to substrate comprising the composition of polyamic acid and particle as polyimide precursor Film above is formed, then by above-mentioned dried coating film, forms the envelope comprising above-mentioned polyimide precursor and particle；And

Above-mentioned envelope is burnt by firing process,

Above-mentioned firing process doubles as the particle removal step for removing above-mentioned particle, alternatively, further comprising above-mentioned particle Removal step,

Before the above-mentioned firing process after above-mentioned envelope formation process, after above-mentioned firing process or above-mentioned particle remove work After sequence, including the stripping process for removing above-mentioned envelope or manufactured Porous polyimide film base film from above-mentioned substrate,

The tensile strength as defined in ASTM standard D638 of above-mentioned Porous polyimide film base film is 45MPa or more.

5th mode of the invention is a kind of composition, and it includes particles, and include: being indicated containing following formula (3-1) The polyamic acid for the structural unit that structural unit and following formula (3-2) indicate or the structural unit indicated containing following formula (4-1) And the polyamic acid of the structural unit of following formula (4-2) expression.

(in above-mentioned formula, A¹¹、A¹²、B¹¹And B¹²It is identical as these abbreviation meanings in above-mentioned formula (1-1) and (1-2), it is selected from By A¹²And B¹²At least one in the group of composition includes the spacer group of divalent in its structure.)

(in above-mentioned formula, A²¹、A²²、B²¹And B²²It is identical as these abbreviation meanings in above-mentioned formula (2-1) and (2-2), A²²And B²²Meet at least one condition in the group being made of above-mentioned (I) and (II).)

The effect of invention

For Porous polyimide film base film of the invention, since tensile strength and bending strength are excellent, thus The generation that adaptability is excellent, and film ruptures caused by stretching, the winding etc. when can inhibit because of the manufacture of base film exert a force is manufactured, can be made The windability excellent base film of long size shape (for example, at least 1m or more).

The manufacturing method of the present invention can suitably manufacture above-mentioned Porous polyimide film base film.

Composition of the invention can be suitably used for the manufacture of above-mentioned Porous polyimide film base film, be based especially on volume Manufacture to volume (roll-to-roll) manufacturing method.

Specific embodiment

Hereinafter, detailed description of embodiments of the present invention, but the present invention is not by any of the following embodiments and the accompanying drawings Limitation, can be suitably changed in the range of the purpose of the present invention to implement.

" Porous polyimide film base film "

The tensile strength as defined in ASTM standard D638 for the Porous polyimide film base film that 1st mode is related to is 45MPa or more.

By making above-mentioned tensile strength 45MPa or more, can inhibit caused by exerting a force because of the stretching etc. when base film manufactures The generation of film rupture, can be made the windability excellent base film of long size shape.

As above-mentioned tensile strength, preferably 70MPa or more, more preferably 80MPa or more, further preferably 90MPa More than, particularly preferably 100MPa or more.

It as the upper limit value of above-mentioned tensile strength, is not particularly limited, as long as not damaging effect of the invention.Tension Intensity can be 300MPa hereinafter, can be 200MPa or less typically.

The bending strength as defined in ASTM standard D790 of above-mentioned Porous polyimide film base film be preferably 60MPa with On.

By making above-mentioned bending strength 60MPa or more, can inhibit caused by exerting a force because of the stretching etc. when base film manufactures The generation of film rupture, can be made the windability excellent base film of long size shape.

As above-mentioned bending strength, preferably 70MPa or more, more preferably 80MPa or more, further preferably 90MPa More than, particularly preferably 100MPa or more, most preferably 110MPa or more.

It as the upper limit value of above-mentioned bending strength, is not particularly limited, as long as not damaging effect of the invention.Bending Intensity can be 400MPa hereinafter, can be 300MPa or less typically.

From the viewpoint of tensile strength and bending strength, the Porous polyimide film base film that the 1st mode is related to is preferred Include: the polyimides containing the structural unit that aftermentioned formula (1-1) and (1-2) indicate.

From the viewpoint of tensile strength and bending strength, the Porous polyimide film base film that the 1st mode is related to is also excellent Choosing includes: the polyimides containing aftermentioned formula (2-1) structural unit indicated and (2-2) structural unit indicated.

The Porous polyimide film base film that 2nd mode is related to includes: containing formula (1-1) structural unit indicated and formula The polyimides for the structural unit that (1-2) is indicated.

(in above-mentioned formula, A¹¹And A¹²Each independently represent 4 valences as derived from the acid anhydrides comprising aromatic tetracarboxylic acid's acid anhydride Aromatic group, B¹¹And B¹²The diamines residue of the divalent as derived from aromatic diamine is each independently represented, selected from by A¹²And B¹² At least one in the group of composition includes the spacer group of divalent in its structure.)

By making selected from by A¹²And B¹²At least one in the group of composition includes the spacer group of divalent in its structure, from And the tensile strength (for example, 45MPa or more) and bending strength (such as 60MPa or more) suitable for the manufacture of base film can be reached.

From the viewpoint of it can more reliably reach tensile strength and bending strength, preferably A¹²It in its structure include divalent Spacer group.

Derivative A¹¹And A¹²The aromatic tetracarboxylic dianhydride of the aromatic group for 4 valences being related to can be from the past as polyamide It is suitably selected in the aromatic tetracarboxylic dianhydride that the synthesis material of acid uses, as long as selected from by A¹²And B¹²In the group of composition extremely Few 1 in its structure comprising the spacer group of divalent.

As the preferred concrete example of aromatic tetracarboxylic dianhydride, bis- (2, the 3- dicarboxyphenyi) ethane two of 1,1- can be enumerated Acid anhydride, bis- (2,3- dicarboxyphenyi) methane dianhydrides, bis- (3,4- dicarboxyphenyi) methane dianhydrides, the bis- phthalic acid anhydride groups of 9,9- Fluorenes (9,9-bis (phthalicanhydride) fluorene), 3,3 ', 4,4 '-diphenyl sulfone tetracarboxylic acid dianhydrides, 2,2- it is bis- (3, 4- dicarboxyphenyi) propane dianhydride, bis- (2,3- dicarboxyphenyi) propane dianhydrides of 2,2-, 2,2- bis- (3,4- dicarboxyphenyis)- 1,1,1,3,3,3- hexafluoropropane dianhydride, 2,2- bis- (2,3- dicarboxyphenyi) -1,1,1,3,3,3- hexafluoropropane dianhydrides, 3, 3 ', 4,4 '-benzophenone tetracarboxylic dianhydrides, bis- (3,4- dicarboxyphenyi) ether dianhydrides, bis- (2,3- dicarboxyphenyi) ether dianhydrides, 2,2 ', 3,3 '-benzophenone tetracarboxylic dianhydrides, 4,4- (to two oxygroup of benzene (p-phenylenedioxy)) two phthalic acids two Acid anhydride, 4,4- (two oxygroup of isophthalic (m-phenylenedioxy)) two O-phthalic acid dianhydrides, pyromellitic acid anhydride (PMDA), 3, 3 ', 4,4 '-bibenzene tetracarboxylic dianhydrides (BPDA), 2,3,3 ', 4 '-bibenzene tetracarboxylic dianhydrides, 2,2,6,6- bibenzene tetracarboxylic dianhydride, 1,2,5,6- naphthalenetetracarbacidic acidic dianhydride, 1,4,5,8 naphthalenetetracarboxylic acid dianhydride, 2,3,6,7- naphthalenetetracarbacidic acidic dianhydride, 1,2,3,4- benzene tetramethyl Acid dianhydride, 3,4,9,10- tetracarboxylic acid dianhydride, 2,3,6,7- anthracene tetracarboxylic acid dianhydride, 1,2,7,8- phenanthrene tetracarboxylic acid dianhydride etc..These Tetracarboxylic dianhydride can be used alone or mix two or more and uses.

In addition, derivative B¹¹And B¹²The aromatic diamine of the diamines residue for the divalent being related to can be from previous as polyamic acid It is suitably selected in the aromatic diamine that synthesis material uses, as long as selected from by A¹²And B¹²At least one in the group of composition is in its knot It include the spacer group of divalent in structure.

As aromatic diamine, can enumerate phenyl ring or 2 or more and 10 phenyl ring bondings below and/or it is condensed and At it is polycyclic on be bonded with the diamino compounds of 2 amino.Phenyl ring in aromatic diamine polycyclic can have substituent group. Specifically, for phenylenediamine and its derivative, benzidine compound and its derivative, diamino-diphenyl compound and its Derivative, diamino triphenyl compound and its derivative, diamino naphthalene and its derivative, aminophenyiamino indane and its spread out Biology, diamino tetraphenyl compound and its derivative, diamino hexaphenyl compound and its derivative, Cardo type fluorenediamine Derivative.

Phenylenediamine is m-phenylene diamine (MPD) (MDA), p-phenylenediamine (PDA) etc..As phenylenediamine derivative, for be bonded with methyl, The diamines of the alkyl such as ethyl.Phenylenediamine derivative is, for example, 2,4 di amino toluene, 2,4- triphenylene diamines (2,4- Triphenylenediamine) etc..

Benzidine compound is compound made of 2 aminophenyls bond together.Benzidine compound example For example 4,4 '-benzidines, 4,4 '-diamino -2,2 '-bis- (trifluoromethyl) biphenyl etc..

Diamino-diphenyl compound is compound made of linking group bonding of 2 aminophenyls via divalent.Divalent Linking group be oxygroup (- O-), sulfonyl, sulfenyl (- S-), alkylidene or its deriveding group, imino group, azo group (- N= N-), phosphinyl (- P (=O) R-, R: being bonded to the hydrogen atom or 1 valence organic group of phosphorus atoms), amide groups (- CONH-), ureylene Base (- NH-CO-NH-) etc..Alkylidene is that carbon atom number is 1 or more and 6 groups below, and deriveding group is 1 of alkylidene Group obtained from the above hydrogen atom is replaced by halogen atom etc..

As the example of diamino-diphenyl compound, 3,3 '-diamino-diphenyl ethers, 3,4 '-diamino two can be enumerated Phenyl ether, 4,4 '-diamino-diphenyl ethers, 3,3 '-diamino diphenyl sulfones, 3,4 '-diamino diphenyl sulfones, 4,4 '-diaminos Base diphenyl sulfone, 3,3 '-diaminodiphenyl-methanes, 3,4 '-diaminodiphenyl-methanes, 4,4 '-diaminodiphenyl-methanes, 4,4 '-diamino diphenyl sulfides, 3,3 '-diamino-diphenyl ketone, 3,4 '-diamino-diphenyl ketone, the bis- (p-aminophenyls of 2,2- Base) propane, 2,2 '-bis- (p-aminophenyl) hexafluoropropane, bis- (the p-aminophenyl) -1- amylenes of 4- methyl -2,4-, 4- methyl - It is bis- (p-aminophenyl) pentanes of bis- (the p-aminophenyl) -2- amylenes of 2,4-, imino-diacetic aniline, 4- methyl -2,4-, bis- (to ammonia Base phenyl) phosphine oxide, 4,4 '-chrysoidines, 4,4 '-diamino-diphenyl ureas, 4,4 '-diamino-diphenyl amides, 1, Bis- (4- amino-benzene oxygen) benzene of 4-, bis- (4- amino-benzene oxygen) benzene of 1,3-, bis- (3- amino-benzene oxygen) benzene of 1,3-, 4,4 '-bis- (4- Amino-benzene oxygen) biphenyl, bis- [4- (4- amino-benzene oxygen) phenyl] sulfones, bis- [4- (3- amino-benzene oxygen) phenyl] sulfones, 2,2- be bis- Bis- [4- (4- amino-benzene oxygen) phenyl] hexafluoropropane of [4- (4- amino-benzene oxygen) phenyl] propane, 2,2- etc..

Diamino triphenyl compound is made of the linking group bonding of 2 aminophenyls and 1 phenylene via divalent Compound.Linking group is same as diamino-diphenyl compound.As the example of diamino triphenyl compound, 1 can be enumerated, Bis- (m-aminophenyl oxygroup) benzene of 3-, bis- (p-aminophenyl oxygroup) benzene of 1,3-, bis- (p-aminophenyl oxygroup) benzene of 1,4- etc..

As the example of diaminonaphthalene, 1,5-diaminonaphthalene and 2,6- diaminonaphthalene can be enumerated.

As the example of aminophenyiamino indane, 5- amino -1- (p-aminophenyl) -1,3,3- trimethyl indenes can be enumerated Full and 6- amino -1- (p-aminophenyl) -1,3,3- trimethyl indane.

As the example of diamino tetraphenyl compound, 4,4 '-bis- (p-aminophenyl oxygroup) biphenyl, 2 can be enumerated, 2 '-is bis- It is [p- (p '-amino-benzene oxygen) phenyl] propane, 2,2 '-bis- [p- (p '-amino-benzene oxygen) xenyl] propane, 2,2 '-bis- [right (m-aminophenyl oxygroup) phenyl] benzophenone etc..

As the example of Cardo type fluorenediamine derivative, bis- (4- aminophenyl) fluorenes of 9,9- etc. can be enumerated.

Aromatic diamine is also possible to the hydrogen atom of these diamines by selected from halogen atom, methyl, methoxyl group, cyano, benzene Compound obtained from least one kind of substituent group in the group of base etc. replaces.

As the spacer group of above-mentioned divalent, ehter bond, thioether bond, carbonyl, alkylidene, fluorianted alkylene, sulphonyl can be enumerated Base, fluorenylidene (divalent group obtained from 2 hydrogen atoms removal of 9 carbon atoms of fluorenes will be bonded to) etc..

As above-mentioned alkylidene, preferably carbon atom number is 1 or more and 5 straight-chain or branched alkylidenes below.Make It is the concrete example of 1 or more and 5 straight-chain or branched alkylidenes below for carbon atom number, methylene, ethylidene, Asia can be enumerated Propyl, dimethylmethylene etc..

As above-mentioned fluorianted alkylene, preferably carbon atom number is that 1 or more and 5 straight-chain or branched fluoro below are sub- Alkyl.It is the concrete example of 1 or more and 5 straight-chain or branched fluorianted alkylenes below as carbon atom number, difluoro can be enumerated Methylene, tetrafluoro ethylidene, bis- (trifluoromethyl) methylene etc..

A¹²When in its structure including the spacer group of divalent, A¹²It can be indicated by following formula (1-2-1).

In addition, B¹²When in its structure including the spacer group of divalent, B¹²It can be indicated by following formula (1-2-2).

(in above-mentioned formula, A¹²¹And A¹²²Each independently represent the aromatic group of trivalent, B¹²¹And B¹²²Table each independently Show the aromatic group of divalent, X¹And X²The spacer group of divalent is each independently represented, * indicates chemical bond.)

As the aromatic group of trivalent, three base of benzene, three base of naphthalene etc. can be enumerated.Wherein, preferred three base of benzene.As three base of benzene, It is preferred that three base of benzene -1,2,4-.

As the aromatic group of divalent, phenylene, naphthylene etc. can be enumerated.Wherein, preferred phenylene.As phenylene, It is preferred that phenylene or metaphenylene, more preferably to phenylene.

A¹²When in its structure including the spacer group of divalent, as derivative A¹²The virtue of the aromatic group for 4 valences being related to The concrete example of fragrant race's tetracarboxylic anhydride can enumerate bis- (2,3- dicarboxyphenyi) the ethane dianhydrides of 1,1-, bis- (2,3- dicarboxyphenyis) Methane dianhydride, bis- (3,4- dicarboxyphenyi) methane dianhydrides, the bis- phthalic acid anhydride group fluorenes (BPAF) of 9,9-, 3,3 ', 4,4 '-two Bis- (3,4- dicarboxyphenyi) propane dianhydrides of phenylsulfone tetracarboxylic acid dianhydride (DSDA), 2,2-, 2,2- bis- (2,3- dicarboxyphenyis) Bis- (3,4- the dicarboxyphenyi) -1,1,1,3,3,3- hexafluoropropane dianhydrides (6FDA) of propane dianhydride, 2,2-, the bis- (2,3- bis- of 2,2- Carboxyl phenyl) -1,1,1,3,3,3- hexafluoropropane dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydrides (BTDA), bis- (3,4- Dicarboxyphenyi) ether dianhydride (ODPA), bis- (2,3- dicarboxyphenyi) ether dianhydrides, 2,2 ', 3,3 '-benzophenone tetracarboxylics two Acid anhydride, 4,4- (to two oxygroup of benzene) two O-phthalic acid dianhydrides, 4,4- (two oxygroup of isophthalic) two O-phthalic acid dianhydrides etc..

B¹²When in its structure including the spacer group of divalent, as derivative B¹²The fragrance of the diamines residue for the divalent being related to The concrete example of race's diamines can enumerate 3,3 '-diamino-diphenyl ethers, 3,4 '-diamino-diphenyl ethers, 4,4 '-diamino hexichol Base ether (ODA), 3,3 '-diamino diphenyl sulfones, 3,4 '-diamino diphenyl sulfones, 4,4 '-diamino diphenyl sulfones (DDS), 3, 3 '-diaminodiphenyl-methanes, 3,4 '-diaminodiphenyl-methanes, 4,4 '-diaminodiphenyl-methanes (DDM), 4,4 '-two Aminodiphenyl base thioether, 3,3 '-diamino-diphenyl ketone, 3,4 '-diamino-diphenyl ketone, bis- (p-aminophenyls) third of 2,2- Alkane, 2,2 '-bis- (p-aminophenyl) hexafluoropropane, bis- (the p-aminophenyl) -1- amylenes of 4- methyl -2,4-, 4- methyl -2,4- are double Bis- (p-aminophenyl) pentanes of (p-aminophenyl) -2- amylene, imino-diacetic aniline, 4- methyl -2,4-, bis- (p-aminophenyls) Phosphine oxide, 4,4 '-chrysoidines, 4,4 '-diamino-diphenyl ureas, 4,4 '-diamino-diphenyl amides, the bis- (4- of 1,4- Amino-benzene oxygen) benzene, bis- (4- amino-benzene oxygen) benzene of 1,3-, bis- (3- amino-benzene oxygen) benzene of 1,3-, 4,4 '-bis- (4- aminobenzenes Oxygroup) biphenyl, bis- [4- (4- amino-benzene oxygen) phenyl] sulfones, bis- [4- (3- amino-benzene oxygen) phenyl] sulfones, the bis- [4- (4- of 2,2- Amino-benzene oxygen) phenyl] propane, bis- [4- (4- amino-benzene oxygen) phenyl] hexafluoropropane of 2,2- etc..

As the content for the structural unit that the above-mentioned formula (1-1) in above-mentioned polyimides indicates, from tensile strength and bending From the viewpoint of intensity, preferably 40 moles of % or more, more preferably 50 moles of % or more, further preferably 60 moles of % with On.

The upper limit value of content as above-mentioned formula (1-1) structural unit indicated, is not particularly limited, as long as not damaging this The effect of invention.The content for the structural unit that formula (1-1) indicates can be 99 moles of % hereinafter, can be 95 moles of % with Under, it can be 90 moles of % or less typically.

As the content for the structural unit that the above-mentioned formula (1-2) in above-mentioned polyimides indicates, from tensile strength and bending From the viewpoint of intensity, preferably 60 moles of % hereinafter, more preferably 50 moles of % hereinafter, further preferably 40 moles of % with Under.

The lower limit value of content as above-mentioned formula (1-2) structural unit indicated, is not particularly limited, as long as not damaging this The effect of invention.The content for the structural unit that formula (1-2) indicates can be 1 mole of % or more, can for 5 moles of % with On, it can be 10 moles of % or more typically.

The Porous polyimide film base film that 3rd mode is related to includes: the knot indicated containing following formula (2-1) and (2-2) The polyimides of structure unit.

By making A²²And B²²Meet at least one condition in the group being made of above-mentioned (I) and (II), so as to reach At the tensile strength (for example, 45MPa or more) and bending strength (such as 60MPa or more) for being suitable for the manufacture of base film.

From the viewpoint of more reliably reaching tensile strength and bending strength, preferably A²²Meet the condition of above-mentioned (I).

For derivative A²¹And A²²For the aromatic tetracarboxylic dianhydride of the aromatic group for 4 valences being related to, as long as A²²And B²² Meet at least one condition in the group being made of above-mentioned (I) and (II), it can be from the previous synthesis as polyamic acid It is suitably selected in the aromatic tetracarboxylic dianhydride that raw material uses.

As derivative A²¹And A²²The concrete example of the aromatic tetracarboxylic dianhydride of the aromatic group for 4 valences being related to can be enumerated With as derivative A¹¹And A¹²The concrete example of the aromatic tetracarboxylic dianhydride of the aromatic group for 4 valences being related to and hereinbefore say The same compound of bright compound.

Derivative B¹¹And B¹²The aromatic diamine of the diamines residue for the divalent being related to can be from the previous synthesis as polyamic acid It is suitably selected in the aromatic diamine that raw material uses, as long as A²²And B²²Meet in the group being made of above-mentioned (I) and (II) At least one condition.

As derivative B¹¹And B¹²The concrete example of the aromatic diamine of the diamines residue for the divalent being related to, can enumerate with as spreading out Raw B¹¹And B¹²The concrete example of the aromatic diamine of the diamines residue for the divalent being related to and the compound that is illustrated above is same Compound.

About above-mentioned (I), derivative A²²Aromatic tetracarboxylic acid's acid anhydride Ea in document CONSULTANTS BUREAU company POLYIMIDES Thermally Stable Polymers(M.I.Bessonov,M.M.Koton,V.V.Kudryavtsev, L.A.Laius write), V.M.Svetlichnyi, K.K.Kalnin ' sh, V.V.Kudryavtsev, and M.M.Kotton, Dokl.Akad.Nauk., on the books in 237,612-615 (1977) etc..

Derivative A²²The electron affinity energy (Ea) of aromatic tetracarboxylic acid's acid anhydride be preferably 2.3eV or less.

As the lower limit value of Ea, it is not particularly limited.Ea can be able to be typically 1.3eV or more for 1.0eV or more.

Derivative A illustrated below²²Aromatic tetracarboxylic acid's acid anhydride structure and its electron affinity energy.Derivative A²²Aromatic series four Carboxylic acid anhydrides compound not limited to the following.

It should be noted that the numerical value in bracket is electron affinity energy in following examples.

About above-mentioned (II), " solubility in 40 DEG C of water is 0.1g/L or more " refers to: derivative B²²Aromatic series two Amine is dissolved in the limiting quantity (g) in 40 DEG C of water 1L (liter).The value can be by as the retrieval based on databases such as chemical abstracts Service and known SciFinder (registered trademark) is easily retrieved.It herein, can in the solubility under the conditions of various Using by Advanced Chemistry Development (ACD/Labs) software V11.02 (all rights reserved 1994- Value when 2011ACD/Labs) pH calculated is 7.

Derivative B²²The solubility of aromatic diamine be preferably 0.5g/L or more, more preferably 1.0g/L or more.

As the upper limit value of solubility, it is not particularly limited.Solubility can be 500g/L hereinafter, typically, Ke Yiwei 400g/L or less.

Derivative B illustrated below²²Aromatic diamine structure and its solubility in 40 DEG C of water, but the present invention not by Their limitation.

It should be noted that the numerical value in bracket is the solubility in 40 DEG C of water in following examples.

As the content for the structural unit that the above-mentioned formula (2-1) in above-mentioned polyimides indicates, from tensile strength and bending From the viewpoint of intensity, preferably 40 moles of % or more, more preferably 50 moles of % or more, further preferably 60 moles of % with On.

The upper limit value of content as above-mentioned formula (2-1) structural unit indicated, is not particularly limited, as long as not damaging this The effect of invention.The content for the structural unit that formula (2-1) indicates can be 99 moles of % hereinafter, can be 95 moles of % with Under, it can be 90 moles of % or less typically.

As the content for the structural unit that the above-mentioned formula (2-2) in above-mentioned polyimides indicates, from tensile strength and bending From the viewpoint of intensity, preferably 60 moles of % hereinafter, more preferably 50 moles of % hereinafter, further preferably 40 moles of % with Under.

The lower limit value of content as above-mentioned formula (2-2) structural unit indicated, is not particularly limited, as long as not damaging this The effect of invention.The content for the structural unit that formula (2-2) indicates can be 1 mole of % or more, can for 5 moles of % with On, it can be 10 moles of % or more typically.

The weight average molecular weight for the polyimides for including in the Porous polyimide film base film being related to as the 1st~3 mode (Mw), it is not particularly limited, as long as not damaging effect of the invention.From the viewpoint of tensile strength and bending strength, The weight average molecular weight (Mw) for the polyimides for including in the Porous polyimide film base film that 1st~3 mode is related to is preferably 5000 or more, more preferably 8000 or more, further preferably 10,000 or more, particularly preferably 10,000 5 thousand or more.

In addition, the Mw of polyimides is not particularly limited when aftermentioned polyimide precursor solution includes organic solvent, only Otherwise damage effect of the invention.From the viewpoint of tensile strength and bending strength, the Mw of polyimides can be 30,000 More than, preferably 50,000 or more.

The upper limit value of Mw as polyimides, is not particularly limited, as long as not damaging effect of the invention.Polyamides The Mw of imines is preferably 100,000 hereinafter, more preferably 80,000 or less.

In this specification, weight average molecular weight (Mw) is using gel permeation chromatography (GPC) and by weight of polystyrene Obtained from measured value.

The Porous polyimide film base film that 1st~3 mode is related to preferably has to be irregularly formed in base film surface Multiple opening portions and Porous in multiple opening portions that base back of the membrane is irregularly formed.

The Porous polyimide film base film that 1st~3 mode is related to, which preferably has, connects base film surface and base back of the membrane The Porous of logical intercommunicating pore.Specifically, it is preferable that above-mentioned base film surface formed multiple opening portions at least part, with At least part in multiple opening portions that above-mentioned base back of the membrane is formed is connected to inside polyimide film.

Porous polyimide film for example can be used as make liquid and/or ionic molecule pass through or keep the diaphragm of electrolyte, The filter of trapping or separation predetermined substance uses.From the viewpoint of the connectivity for being suitable for these purposes, the 1st~3 mode is related to And the porosity of Porous polyimide film base film be preferably 50% or more, more preferably 55% or more, further preferably 60% or more, particularly preferably 65% or more.

As the upper limit value of porosity, it is not particularly limited.However, from the viewpoint of intensity, porosity is preferably 90% hereinafter, more preferably 80% or less.

Porosity for example indicates the ratio of the hole of per unit volume base film.Porosity can for example pass through formula below (A) It calculates.

Porosity (%)={ volume (cm of test film³)-[test film weight (g)/polyimides specific gravity (g/ cm³)] volume (cm of/test film³)×100···(A)

The partial size of the particle used when by suitably adjusting manufacture base film as described later, content, can form desired Porosity.

The tensile strength and bending strength for the Porous polyimide film base film that 1st~3 mode is related to are excellent.Therefore, energy The generation that film ruptures caused by the forces such as stretching, winding when inhibiting because of the manufacture of base film.As a result, the base of long size shape can be manufactured Film.As the film length for the Porous polyimide film base film that the 1st~3 mode is related to, it is not particularly limited.Film length is preferably 1m or more, more preferably 5m or more, further preferably 10m or more, particularly preferably 30m or more, most preferably 40m or more.

As the upper limit value of film length, it is not particularly limited.Film length can be 2000m hereinafter, typically, Ke Yiwei 1000m or less.

It as the film width of base film, is not particularly limited, can be suitable for setting.

As the thickness of base film, it is not particularly limited.Thickness is preferably 1 μm or more and 500 μm hereinafter, more preferably 3 μm Above and 200 μm hereinafter, further preferably 5 μm or more and 100 μm hereinafter, particularly preferably 7 μm or more and 80 μm or less.

For the Porous polyimide film base film that the 1st~3 mode is related to, since tensile strength and bending strength are excellent It is different excellent thus windability excellent, therefore, can be wound in diameter be 2.5cm (1 inch) more than and 25cm (10 inches) it is below Core and formed.It is 5cm (2 inches) or more that the Porous polyimide film base film that 1st~3 mode is related to, which is preferably wound in diameter, And 10cm (4 inches) core below and formed.The spooling length of every base film of volume 1 is elongated as a result, can reduce transport save at This.

As the material of core, it is not particularly limited.The concrete example of material as core, can enumerate stainless steel (for example, SUS), polyethylene terephthalate (PET) etc..

" purposes of Porous polyimide film base film "

Porous polyimide film base film described above can provide various diaphragms (for example, nickel-cadmium cell, ni-mh are electric The secondary cells diaphragm such as pond and lithium ion battery), various filters, electrolyte film in fuel cell, advanced low-k materials.

For Porous polyimide film base film described above, since tensile strength and bending strength are excellent, Therefore, the generation that film ruptures caused by exerting a force because of stretching, the winding etc. when base film manufactures can be inhibited, long size shape can be made The windability excellent base film of (for example, at least 1m or more), therefore, the manufacture suitable for battery, filter for installation.

" manufacturing method of Porous polyimide film base film "

The manufacturing method for the Porous polyimide film base film that 4th mode is related to includes following processes:

Envelope formation process, by the composition comprising polyamic acid and particle as polyimide precursor (hereinafter, also simple Referred to as " polyimide precursor solution ".) be applied to form film on substrate, then by above-mentioned dried coating film, formed comprising upper State the envelope of polyimide precursor and particle；And

Above-mentioned envelope is burnt by firing process,

As the preferred scope of above-mentioned tensile strength, with the Porous polyimide film base film that is related to for the 1st mode and The range being illustrated above is same.

The preferred scope of the bending strength as defined in ASTM standard D790 about above-mentioned Porous polyimide film base film, Also with the Porous polyimide film base film that is related to for the 1st mode and the range that is illustrated above is same.

From the viewpoint of productivity, the manufacture of Porous polyimide film base film carries out preferably in a manner of roll-to-roll.

< envelope formation process >

(polyamic acid)

Above-mentioned polyimide precursor is preferably the structural unit for containing formula (3-1) expression and the structure list that formula (3-2) indicates The polyamic acid of the polyamic acid of member or the structural unit indicated containing formula (4-1) structural unit indicated and formula (4-2).

(in above-mentioned formula, A¹¹、A¹²、B¹¹And B¹²With in formula (1-1) and formula (1-2) these abbreviation meanings it is identical, selected from by A¹²And B¹²At least one in the group of composition includes the spacer group of divalent in its structure.)

(in above-mentioned formula, A²¹、A²²、B²¹And B²²It is identical as these abbreviation meanings in formula (2-1) and formula (2-2), A²²And B²² Meet at least one condition in the group being made of above-mentioned (I) and (II).)

The composition that 5th mode is related to includes aftermentioned particle, and includes: the structural unit indicated containing formula (3-1) And formula (3-2) indicate structural unit polyamic acid or containing formula (4-1) indicate structural unit and formula (4-2) indicate knot The polyamic acid of structure unit.

The composition that 5th mode is related to can be used as the polyimide precursor solution in the manufacturing method that the 4th mode is related to and Suitably use.Gather as a result, the Porous that the tensile strength as defined in ASTM standard D638 is 45MPa or more can be manufactured suitably Acid imide film base film.

The structural unit that the structural unit or formula (4-1) indicated as the formula (3-1) in above-mentioned polyamic acid indicates contains Amount, preferably 40 moles of % or more, more preferably 50 moles of % or more, further preferably 60 moles of % or more.

The upper limit value of content as formula (3-1) structural unit indicated or the structural unit of formula (4-1) expression, without spy It does not limit, as long as not damaging effect of the invention.The structure list that the structural unit or formula (4-1) that formula (3-1) indicates indicate The content of member can be 99 moles of % hereinafter, can be 95 moles of % hereinafter, can be 90 moles of % or less typically.

The content of structural unit as above-mentioned formula (3-2) or (4-2) expression in above-mentioned polyamic acid, preferably 60 rub Your % hereinafter, more preferably 50 moles of % hereinafter, further preferably 40 moles of % or less.

As the lower limit value of above-mentioned formula (3-2) or the content of the structural unit of (4-2) expression, it is not particularly limited, as long as Effect of the invention is not damaged.The content for the structural unit that the structural unit or formula (4-2) that formula (3-2) indicates indicate can be with It can be able to be typically 10 moles of % or more for 5 moles of % or more for 1 mole of % or more.

Aromatic tetracarboxylic dianhydride can be and polymerizeing by the polyamic acid as polyimide precursor with aromatic diamine It obtains.Aromatic tetracarboxylic dianhydride and the usage amount of aromatic diamine are not particularly limited.About relative to aromatic tetracarboxylic acid The usage amount of aromatic diamine for 1 mole of dianhydride, it is preferable to use 0.50 mole or more and 1.50 moles hereinafter, more preferably 0.60 mole or more and 1.30 moles hereinafter, particularly preferably 0.70 mole or more and 1.20 moles or less.

The aromatic tetracarboxylic dianhydride that aromatic tetracarboxylic dianhydride can be used from the previous synthesis material as polyamic acid In suitably select.Aromatic tetracarboxylic dianhydride also can be used in combination two or more.

As the concrete example of aromatic tetracarboxylic dianhydride, can enumerate and as derivative A¹¹And A¹²The aromatic series for 4 valences being related to The concrete example of the aromatic tetracarboxylic dianhydride of group and the same compound of compound being illustrated above.

Aromatic diamine can suitably be selected from the aromatic diamine that the previous synthesis material as polyamic acid uses.Virtue Fragrant race's diamines also can be used in combination two or more.

As the concrete example of aromatic diamine, can enumerate and as derivative B¹¹And B¹²The virtue of the diamines residue for the divalent being related to The concrete example of fragrant race's diamines and the same compound of compound being illustrated above.

The means of manufacture polyamic acid are not particularly limited.Such as can be used make aromatic tetracarboxylic acid in organic solvent Method known to method that dianhydride and aromatic diamine are reacted etc..

Aromatic tetracarboxylic dianhydride usually carries out in organic solvent with reacting for aromatic diamine.Aromatic tetracarboxylic acid two Workable organic solvent is not particularly limited in the reacting of acid anhydride and aromatic diamine, as long as can be by aromatic tetracarboxylic dianhydride And the organic solvent that aromatic diamine is dissolved and do not reacted with aromatic tetracarboxylic dianhydride and aromatic diamine.It is organic molten Agent can be used alone or mix two or more and use.

As the example of organic solvent used in the reacting of aromatic tetracarboxylic dianhydride and aromatic diamine, N- can be enumerated N-methyl-2-2-pyrrolidone N, DMAC N,N' dimethyl acetamide, N, N- diethyl acetamide, N,N-dimethylformamide, N, N- diethyl Formamide, N- methyl caprolactam, N, N, N ', the nitrogenous polar solvent such as N '-tetramethylurea；Beta-propiolactone, gamma-butyrolacton, γ- The lactones such as valerolactone, δ-valerolactone, γ-hexalactone, 6-caprolactone system polar solvent；Dimethyl sulfoxide；Acetonitrile；Ethyl lactate, The fatty acid esters such as butyl lactate；Diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dioxane, tetrahydrofuran, The ethers such as methylcellosolve acetate, ethyl cellosolve acetate；The phenol systems solvent such as cresols class.These organic solvents can be independent Using or mix two or more and use.Wherein, the combination of preferably above-mentioned nitrogenous polar solvent and lactone system polar solvent.To having The usage amount of solvent is not particularly limited.The usage amount of organic solvent is preferably to make 5 matter of content of the polyamic acid generated Measure % or more and 50 mass % amounts below.

In these organic solvents, consider from the dissolubility of the polyamic acid of generation, preferably n-methyl-2-pyrrolidone, N, N- dimethyl acetamide, N, N- diethyl acetamide, N,N-dimethylformamide, N, N- diethylformamide, N- methyl are in oneself Amide, N, N, N ', the nitrogenous polar solvent such as N '-tetramethylurea.In addition, considering from viewpoints such as film formings, it can be and be added to γ- The mixed solvent of the lactones such as butyrolactone system polar solvent.Generally speaking lactone system polar solvent preferably to be relative to organic solvent 1 mass % or more and 20 mass % amount addition below, more preferably 5 mass % or more and 15 mass % or less.

Polymerization temperature is usually -10 DEG C or more and 120 DEG C hereinafter, preferably 5 DEG C or more and 30 DEG C or less.Polymerization time root It is different according to the difference of the raw material composition used, usually 3 hours or more and 24 hours or less.In addition, in such a situa-tion The intrinsic viscosity of obtained polyamic acid solution is preferably 1000cP (centipoise) or more and 100000cP hereinafter, still more preferably For 5000cP or more and 70000cP range below.

It as the Mw of above-mentioned polyamic acid, is not particularly limited, as long as not damaging effect of the invention.From manufacture From the viewpoint of the tensile strength and bending strength of base film, the Mw of above-mentioned polyamic acid is preferably 5000 or more, more preferably 8000 or more, further preferably 10,000 or more, particularly preferably 10,000 5 thousand or more.

In addition, the Mw of above-mentioned polyamic acid is not particularly limited when polyimide precursor solution includes organic solvent, as long as Effect of the invention is not damaged.From the viewpoint of the tensile strength and bending strength of the base film of manufacture, above-mentioned polyamide The Mw of acid can be 30,000 or more, preferably 50,000 or more.

The upper limit value of Mw as above-mentioned polyamic acid, is not particularly limited, as long as not damaging effect of the invention. The Mw of above-mentioned polyamic acid is preferably 100,000 hereinafter, more preferably 80,000 or less.

(particle)

It as the material for the particle for including in polyimide precursor solution, is not particularly limited, as long as insoluble in being wrapped The solvent contained and the material that can be removed from Porous polyimide film base film in subsequent particle removal step, can Using known material.

The material of particle be inorganic material when, the material of inorganic particles is not particularly limited, as long as can using be chemically treated, The methods of heating removes inorganic particles.As the material of inorganic particles, silica (silica), carbonic acid can be enumerated Calcium, titanium oxide, aluminium oxide (Al₂O₃) etc. metal oxides.As preferred inorganic particles, calcium carbonate, colloidal silica can be enumerated The silicon dioxide microparticles such as silicon.

When the material of particle is organic material, as the material of organic fine particles, high molecular weight olefin based polymer can be enumerated The polymerization of the aromatic ethenyls such as (polypropylene, polyethylene, polybutadiene, polyisoprene, polytetrafluoroethylene (PTFE) etc.), polystyrene Object, acrylic resin (acrylic acid, methyl acrylate, methyl methacrylate, Isobutyl methacrylate, polymethyl Sour methyl esters (PMMA) etc.), epoxy resin, cellulose, polyvinyl alcohol, polyvinyl butyral, polyester, organic high score such as polyethers Son.These organic polymers can be copolymer (for example, the copolymer of methyl methacrylate and styrene, acrylic acid and benzene The copolymer of ethylene).In addition, the organic fine particles of different materials can be applied in combination.

For the gross mass of polyamic acid and particle in polyimide precursor solution, the ratio of the quality of particle Preferably 35 mass % or more, more preferably 40 mass % or more.

The upper limit value of the ratio of quality as particle, is not particularly limited.From the viewpoint of intensity, the quality of particle Ratio be preferably 90 mass % hereinafter, more preferably 85 mass % or less.

The shape of particle is not particularly limited, and can be spherical particle, is also possible to platy particles.As particle, preferably Spherical particle, the high spherical particle of more preferable rate of small round spheres.

The partial size (average diameter or median particle diameter) of particle is not particularly limited.For example, average diameter or median particle diameter are excellent Be selected as 10nm or more and 2000nm hereinafter, more preferably 50nm or more and 1500nm hereinafter, more preferably 100nm or more and 1000nm or less.

The particle diameter distribution index (d25/d75) of above-mentioned particle be preferably 1 or more and 6 hereinafter, more preferably 1 or more and 5 with Under, further preferably 1 or more and 3 or less.

Herein, d25 and d75 indicates that the cumulative frequency of size distribution is respectively 25% and 75% partial size, and d25 is that partial size is big A side.

As the solvent that may include in polyimide precursor solution, water, the aqueous solution of organic solvent, You Jirong can be enumerated Agent.

As the concrete example of organic solvent, can enumerate as making in the reacting of aromatic tetracarboxylic dianhydride and aromatic diamine Solvent and the organic solvent enumerated.Organic solvent can be used separately or in combination two or more.

As the organic solvent in the case where the aqueous solution for forming organic solvent, polar solvent, water-soluble solvent can be enumerated. As polar solvent, the concrete example of water-soluble solvent, can enumerate methanol, ethyl alcohol, 1- propyl alcohol, 2- propyl alcohol, n-butyl alcohol, 2- butanol, 2- methyl-1-propyl alcohol, 1- amylalcohol, 2- amylalcohol, 4- methyl-2- amylalcohol, 1,1- dimethyl ethanol, 2,2- dimethyl-1- propyl alcohol, four The alcohols such as tetrahydrofurfuryl alcohol；Glycols such as ethylene glycol, ethylene glycol single methyl ether, ethylene glycol monomethyl ether, diethylene glycol etc..It is organic molten The preferred alcohols of agent.

In addition, B²²When meeting above-mentioned (II), as the solvent that may include in polyimide precursor solution, preferably water or above-mentioned The aqueous solution of organic solvent.

When using organic fine particles as particle, solvent is preferably the aqueous solution of water or above-mentioned organic solvent.

When using inorganic particles as particle, as the organic solvent that may include in polyimide precursor solution, preferably It can dissolve the organic solvent of polyamic acid, polyimides etc. but insoluble inorganic particles.

The solid component concentration of polyimide precursor solution is preferably 5 mass % or more and 50 mass % hereinafter, more preferably For 10 mass % or more and 40 mass % or less.

(other compositions)

Polyimide precursor solution may include dispersing agent.In addition, for polyimide precursor solution, in addition to above-mentioned Except ingredient, for antistatic, the purpose of anti-flammability, low-temperature firing, imparting release property, raising coating is assigned, according to need May include antistatic agent, fire retardant, chemical imidization agent, condensing agent, release agent, surface conditioner etc. it is appropriate it is known at Point.

As above-mentioned base material, such as PET (polyethylene terephthalate) or PEN (poly- naphthalenedicarboxylic acid second two can be enumerated Alcohol ester) etc. film, SUS substrate, preferably PET film.

As will be upper after it will form film on polyimide precursor solution application (such as coating) Yu Shangshu substrate Dried coating film (prebake conditions) are stated to the method that forms envelope, the following methods can be given: under normal pressure or vacuum in 0 DEG C or more and 120 DEG C or less (preferably 0 DEG C or more and 90 DEG C or less), it is more preferably (further excellent in 10 DEG C or more and 100 DEG C or less under normal pressure Select 10 DEG C or more and 90 DEG C or less) by dried coating film to forming envelope.

As the thickness of film, it is not particularly limited.The thickness of film is preferably 1 μm or more and 800 μm hereinafter, more preferably For 3 μm or more and 200 μm hereinafter, further preferably 5 μm or more and 100 μm hereinafter, particularly preferably 7 μm or more and 80 μm with Under.

< firing process >

Using the firing process being burnt into the above-mentioned envelope comprising the polyamic acid as polyimide precursor, can make Polyamic acid closed loop and form polyimides, so as to which polyimide film is made.

For example, the structure list indicated containing formula (3-1) structural unit indicated and formula (3-2) can be made using firing process The polyamic acid closed loop of member and to form the polyamides containing formula (1-1) structural unit indicated and (1-2) structural unit indicated sub- Amine can make the polyamic acid closed loop of the structural unit indicated containing formula (4-1) structural unit indicated and formula (4-2) and be formed and be contained The polyimides for the structural unit that the structural unit and formula (2-2) for having formula (2-1) to indicate indicate.

Firing temperature is preferably 120 DEG C or more and 500 DEG C hereinafter, more preferably 150 DEG C or more and 450 DEG C of temperature below Degree.

About firing condition, for example, can also be used: with 3 hours from room temperature to 420 DEG C, then keeping 20 in 420 DEG C The method of minute；420 DEG C (being kept for 20 minutes at each temperature) are periodically warming up to from room temperature with 20 DEG C of interval, most finally 420 DEG C keep the interim drying-hot-imide method such as 20 minutes.

(particle removal step)

Above-mentioned manufacturing method may further include particle removal step.

Inorganic particles are dissolved and the inorganic particles contacts such as aqueous solution for making hydrofluoric acid (HF) etc. and silica, energy Inorganic particles are removed.When inorganic particles are calcium carbonate, it is possible to use aqueous hydrochloric acid solution replaces the aqueous solution of hydrofluoric acid.

When particle is organic fine particles and is non-crosslinked resin particle, using insoluble polyimide film but can will be non-crosslinked The organic solvent of resin particle dissolution, non-crosslinked resin particle is dissolved and is removed.As such organic solvent, can enumerate for example The ethers such as tetrahydrofuran；The aromatics such as toluene；The ketones such as acetone；The esters such as ethyl acetate.In these, preferred tetrahydrofuran etc. Ethers further preferably uses tetrahydrofuran.

When above-mentioned firing process doubles as above-mentioned particle removal step, above-mentioned particle is preferably organic fine particles.

It, can be not to poly- if the organic material of organic fine particles is the material decomposed at temperature more lower than polyimides Acid imide only makes organic fine particles disappear in the case where assigning thermal damage.

For example, the resin particle formed by linear polymer, known depolymerization polymer can be enumerated.It is common linear poly- It closes object strand of polymer in thermal decomposition randomly to be cut off, depolymerization polymer is that polymer is decomposed in thermal decomposition At the polymer of monomer.It is by decomposing to low-molecular weight or CO₂And it disappears from polyimide film.The resin used is micro- The decomposition temperature of grain is for example preferably 200 DEG C or more and 400 DEG C or less.

< stripping process >

In above-mentioned manufacturing method, before the above-mentioned firing process after above-mentioned envelope formation process, after above-mentioned firing process or After above-mentioned particle removal step, including above-mentioned envelope or manufactured Porous polyimide film base film are removed from above-mentioned substrate Stripping process.

In addition, when Porous polyimide film base film is long size (such as 1m or more), from the viewpoint of productivity, on Stating manufacturing method, it is also preferable to include be wound in the process that diameter is 2.5cm or more and 25cm core below.

Embodiment

Hereinafter, showing embodiment further specifically describes the present invention, but the scope of the present invention is not by these embodiments Limitation.

(synthesis example)

It reacts aromatic tetracarboxylic acid's acid anhydride shown in following table 1 with aromatic diamine, obtains with forming in following table 1 Include the polyamic acid 1~3 of anhydride residue and diamines residue than (mole %) and compares polyamic acid 1 and 2.

In following table 1, " solubility " indicates the solubility (g/L) in 40 DEG C of water.

[table 1]

(embodiment 1)

Using homogenizer, by spherical silicon dioxide, (intermediate value average grain diameter is 280nm, and particle diameter distribution index (d25/d75) is 1.5 or less) 42g is dispersed in dimethyl acetamide (DMAC) 42g, obtains silica dispersions 84g.

The DMAC solution (concentration of polyamic acid 1 is 20 mass %) for preparing polyamic acid 1 obtained above, by the solution 52.5g, above-mentioned silica dispersions 84g and DMAC13.5g, which are mixed and used, practices Taro (trade name, Thinky corporation) Mix it uniformly, the polyimide precursor solution (composition) for obtaining embodiment 1 (about mass ratio, spherical silicon dioxide: is gathered Amic acid=80:20, volume ratio are spherical silicon dioxide: polyamic acid=73:27.).

(comparative example 1 and 2)

Instead of the DMAC solution of polyamic acid 1, (compare polyamic acid 1 using the DMAC solution for comparing polyamic acid 1 respectively Concentration be 20 mass %), compare the DMAC solution (concentration for comparing polyamic acid 2 is 20 mass %) of polyamic acid 2, remove this Except, it operates similarly with example 1, obtains the polyimide precursor solution of comparative example 1 and 2.

(embodiment 2)

By the spherical particle comprising polystyrene (PS), (intermediate value average grain diameter is 260nm, particle diameter distribution index (d25/ D75) for 1.5 hereinafter, hereinafter referred to as " polystyrene particle ".) polystyrene particle aqueous dispersions (40 mass %) and on Aqueous solution (concentration of polyamic acid 1 the is 15 mass %) mixing for the polyamic acid 1 stated, adds pure water, further with solid State constituent concentration is uniformly mixed as the mode of 23 mass %, obtains the polyimide precursor solution of embodiment 2 (about quality Than polystyrene particle: polyamic acid=60:40, about volume ratio, polystyrene particle: polyamic acid=68:32.).

(embodiment 3)

Instead of the aqueous solution (concentration of polyamic acid 1 is 15 mass %) of polyamic acid 1 obtained above, obtained using above-mentioned (concentration of polyamic acid 1 is 15 mass %, water/IPA=9/1 (matter to water/IPA (isopropanol) aqueous solution of the polyamic acid 1 arrived Measure ratio)), it in addition to this, operates similarly to Example 2, obtains the polyimide precursor solution of embodiment 3.

(embodiment 4)

Instead of the aqueous solution (concentration of polyamic acid 1 is 15 mass %) of polyamic acid 1 obtained above, obtained using above-mentioned (concentration of polyamic acid 1 is 15 mass %, water/NMP to water/NMP (N-Methyl pyrrolidone) aqueous solution of the polyamic acid 1 arrived =9/1 (mass ratio)), it in addition to this, operates similarly to Example 2, obtains the polyimide precursor solution of embodiment 4.

(embodiment 5 and 6 and comparative example 3)

Instead of the aqueous solution of above-mentioned polyamic acid 1, respectively using above-mentioned polyamic acid 2 aqueous solution (polyamic acid 2 it is dense Degree is 15 mass %), the aqueous solution (concentration of polyamic acid 3 is 15 mass %) of above-mentioned polyamic acid 3, compare polyamic acid 2 Aqueous solution (compare polyamic acid 2 concentration be 15 mass %), in addition to this, operate, implemented similarly to Example 2 The polyimide precursor solution of example 5 and 6 and the polyimide precursor solution of comparative example 3.

(embodiment 7)

By the non-crosslink styrene acrylic acid series copolymer (hreinafter referred to as " A/ for being 0.1 μm comprising average grain diameter St".) aqueous dispersions (21 mass %) and polyamic acid obtained above 1 aqueous solution (concentration of polyamic acid 1 be 21 matter Measure %) uniformly mixing, obtain embodiment 7 polyimide precursor solution (about mass ratio, A/St: polyamic acid=50:50, About volume ratio, A/St: polyamic acid=57:43.).

(embodiment 8)

The aqueous dispersions (40 comprising calcium carbonate microparticle (average grain diameter 700nm) that will be obtained with aftermentioned manufacturing method Quality %) and polyamic acid obtained above 1 aqueous solution (concentration of polyamic acid 1 be 30 mass %) uniformly mixing, obtain Embodiment 8 polyimide precursor solution (about mass ratio, about calcium carbonate particle: polyamic acid=73:27, about body Product ratio, calcium carbonate particle: polyamic acid=40:60.).

[dispersion liquid of calcium carbonate microparticle]

The unmodified calcium carbonate microparticle in surface is added into isopropanol 50g, and (vaterite (vaterite) type, average grain diameter are 700nm) 10g, it is cooling with ice water on one side, stir within 1 hour with blender on one side, the isopropanol for preparing calcium carbonate microparticle suspends Liquid.On the other hand, adipic acid 0.2g is added in isopropanol 23g, stir within 10 minutes, made it completely dissolved, prepare different Propanol solution.At normal temperature above-mentioned isopropanol suspension and above-mentioned aqueous isopropanol stir within 2 hours, be obtained comprising surface The slurry of calcium carbonate microparticle and isopropanol through adipic acid modification.It is using paulownia mountain funnel (paulownia mountain makes made) and trapping partial size 1 μm of cellulose filter paper, is filtered above-mentioned slurry, then carries out drying in 1 hour to filter cake in 120 DEG C, obtains surface The calcium carbonate microparticle modified through adipic acid.Calcium carbonate microparticle 7.2g is added in pure water 10.8g, using homogenizer, with 20% crushing power homogenize within 40 seconds, next homogenize within 40 seconds with 30% crushing power, obtains calcium carbonate Particle dispersion liquid.

(envelope formation process and stripping process)

Using apparatus for coating, by Examples 1 to 8 obtained above and the polyimide precursor solution (group of comparative example 1~3 Close object) it is coated on PET film in such a way that final film thickness (film thickness of Porous polyimide film base film) becomes 25 μm, it is formed and is applied Film puts into the PET film for foring film into oven, in 80 DEG C of progress drying in 5 minutes, forms envelope.

Obtained envelope is removed from PET film.

The film of < envelope ruptures resistance test >

According to following benchmark, by visual observation, as " film rupture patience (envelope) " to envelope caused by due to above-mentioned removing Film rupture situation evaluated.Show the result in following table 2.

Zero: no film rupture.

×: by film strength fragility, film rupture has occurred.

××: it is very fragile by film strength, a large amount of film ruptures have occurred.

About the envelope that the polyimide precursor solution by comparative example 1~3 is formed, film rupture occurs and not can be carried out subsequent Firing process and particle removal step.

(firing process of the envelope after removing)

Using firing furnace, with 420 DEG C of in-furnace temperature, carrying out 5 minutes to above-mentioned envelope, (wherein, embodiment 7 is 380 DEG C, 5 minutes) firing, formed polyimide film.

About the envelope that the polyimide precursor solution by embodiment 2~6 is formed, above-mentioned firing process is removed as particle Process can obtain as a result, the Porous for the embodiment 2~6 that film thickness is 25 μm by above-mentioned firing by polystyrene particle burn off Polyimide film base film.

(particle removal step)

About the polyimide film that the polyimide precursor solution by embodiment 1 is formed, in the hydrofluoric acid of 10 mass % (HF) it is impregnated 10 minutes in aqueous solution, silica is dissolved, the Porous polyamides for obtaining the embodiment 1 that film thickness is 25 μm is sub- Amine film base film.

About the polyimide film that the polyimide precursor solution by embodiment 7 is formed, instead of the hydrofluoric acid of 10 mass % Aqueous solution and be in addition to this carried out similarly dipping using tetrahydrofuran (THF), A/St is dissolved, embodiment 7 is obtained Porous polyimide film base film.

About the polyimide film that the polyimide precursor solution by embodiment 8 is formed, instead of the hydrofluoric acid of 10 mass % Aqueous solution and use 10 mass % hydrochloric acid be in addition to this carried out similarly dipping, by dissolution of calcium carbonate, obtain embodiment 8 Porous polyimide film base film.

The porosity of the Porous polyimide film base film of Examples 1 to 6 obtained above is measured, as a result, institute There is base film in 60% or more and 70% or less range.Embodiment 7 and embodiment 8 are in 50% or more and 60% model below In enclosing.

< tensile strength and bending strength test >

For the test film of the Porous polyimide film base film of Examples 1 to 8 obtained above and comparative example 1~3, press (measurement device: EZ-TEST/CE (Shimadzu Seisakusho Ltd. is measured to tensile strength and bending strength according to standard method below System)).

Tensile strength: ASTM D638

Bending modulus: ASTM D790

Show the result in following table 2.

[table 2]

*: envelope occurs film rupture and not can be carried out firing, as a result, does not also carry out to particle removal step.

The result shows that, be unsatisfactory for for having used as shown in above-mentioned table 2 " containing formula (3-1) structural unit indicated and The important document of the structural unit that formula (3-2) indicates " and " the structure list indicated containing formula (4-1) structural unit indicated and formula (4-2) For the comparative example 1~3 of the comparison polyamic acid 1,2 of any important document in the important document of member ", after being coated drying and removing The equal intensity of envelope is fragile, and film rupture has occurred.

The Porous polyimide film base film of comparative example 1~3 do not meet tensile strength and the 60MPa of 45MPa or more with On bending strength.Using the Porous polyimide film base film of comparative example 1~3, fail to manufacture long size shape (such as 1m with On) base film.

On the other hand, meet " the structure indicated containing formula (3-1) structural unit indicated and formula (3-2) for having used In the important document of unit " and the important document of " structural unit indicated containing formula (4-1) structural unit indicated and formula (4-2) " at least In the polyamic acid 1~3 of one side for any Examples 1 to 8, the envelope after being coated drying and removing does not occur The envelope for the long size that film rupture, energy formation length are 40m.

The Porous polyimide film base film of Examples 1 to 8 is all satisfied the tensile strength and 60MPa or more of 45MPa or more Bending strength (60MPa or more), have excellent tensile strength and bending strength.The Porous polyamides of Examples 1 to 8 is sub- Amine film base film roll is around in the core that diameter is 3 inches, is able to manufacture the web-like base film that length is 40m.

By having used (the structural unit that the structural unit or formula (4-2) that wherein, formula (3-2) indicates indicate of polyamic acid 1 Content be 60 moles of % or less) embodiment 1, with used polyamic acid 3 (wherein, formula (3-2) indicate structural unit or formula The comparison of embodiment 6 of the content of the structural unit of (4-2) expression greater than 60 moles of %) is it is found that the structure list that formula (3-2) indicates When the content for the structural unit that member or formula (4-2) indicate is 60 moles of % or less, tensile strength and bending strength are excellent.

Claims

1. Porous polyimide film base film, the tension as defined in ASTM standard D638 of the Porous polyimide film base film Intensity is 45MPa or more.

2. Porous polyimide film base film as described in claim 1, the Porous polyimide film base film by ASTM Bending strength as defined in standard D790 is 60MPa or more.

3. Porous polyimide film base film as claimed in claim 1 or 2, it includes: the knot indicated containing following formula (1-1) The polyimides for the structural unit that structure unit and following formula (1-2) indicate,

In the formula, A¹¹And A¹²Each independently represent the aromatic series of 4 valences as derived from the acid anhydrides comprising aromatic tetracarboxylic acid's acid anhydride Group, B¹¹And B¹²The diamines residue of the divalent as derived from aromatic diamine is each independently represented, selected from by A¹²And B¹²Composition At least one in group includes the spacer group of divalent in its structure.

4. Porous polyimide film base film as claimed in claim 1 or 2, it includes: the knot indicated containing following formula (2-1) The polyimides for the structural unit that structure unit and following formula (2-2) indicate,

In the formula, A²¹And A²²Each independently represent the aromatic series of 4 valences as derived from the acid anhydrides comprising aromatic tetracarboxylic acid's acid anhydride Group, B²¹And B²²Each independently represent the diamines residue of the divalent as derived from aromatic diamine, A²²And B²²Meet selected under At least one condition in the group of (I) and (II) composition is stated,

(I) derivative A²²Aromatic tetracarboxylic acid's acid anhydride electron affinity energy be 2.6eV hereinafter,

(II) derivative B²²Aromatic diamine be and derivative B²¹The different aromatic diamine of aromatic diamine, and in 40 DEG C of water In solubility be 0.1g/L or more.

5. Porous polyimide film base film, it includes: contain following formula (1-1) structural unit indicated and following formula (1-2) The polyimides of the structural unit of expression,

6. Porous polyimide film base film, it includes: contain following formula (2-1) structural unit indicated and following formula (2-2) The polyimides of the structural unit of expression,

7. such as Porous polyimide film base film described in claim 5 or 6, wherein the formula (1- in the polyimides 2) or the content of the structural unit of (2-2) expression is 60 moles of % or less.

8. the film of Porous polyimide film base film as claimed in claim 1 or 2, the Porous polyimide film base film is long Degree is 1m or more.

9. Porous polyimide film base film as claimed in claim 1 or 2, be wound in diameter be 2.5cm or more and 25cm core below and formed.

10. Porous polyimide film base film as claimed in claim 1 or 2, the hole of the Porous polyimide film base film Gap rate is 60 mass % or more.

11. the manufacturing method of Porous polyimide film base film comprising following processes:

Envelope formation process, will comprising the composition of polyamic acid and particle as polyimide precursor be applied to substrate on and Film is formed, then by the dried coating film, forms the envelope comprising the polyimide precursor and particle；And

The envelope is burnt by firing process,

The firing process doubles as the particle removal step for removing the particle, alternatively, further comprising that the particle removes Process,

Before the firing process after the envelope formation process, after the firing process or after the particle removal step, Including the stripping process for removing the envelope or manufactured Porous polyimide film base film from the substrate,

The tensile strength as defined in ASTM standard D638 of the Porous polyimide film base film is 45MPa or more.

12. manufacturing method as claimed in claim 11, wherein in the Porous polyimide film, by ASTM standard D790 Defined bending strength is 70MPa or more.

13. the manufacturing method as described in claim 11 or 12, wherein the film length of the Porous polyimide film base film is 1m or more, the manufacturing method further include the Porous polyimide film base film roll is around in diameter be 2.5cm or more and The process of 25cm core below.

14. the manufacturing method as described in claim 11 or 12, wherein the particle diameter distribution index (d25/d75) of the particle is 1 Above and 6 hereinafter, d25 and d75 indicates that the cumulative frequency of size distribution is respectively 25% and 75% partial size, and d25 is that partial size is big A side.

15. the manufacturing method as described in claim 11 or 12, wherein the firing process doubles as the particle removal step When, the particle is organic fine particles.

16. composition, it includes particles, and include: containing following formula (3-1) structural unit indicated and following formula (3-2) The polyamic acid of the structural unit of expression or the knot indicated containing following formula (4-1) structural unit indicated and following formula (4-2) The polyamic acid of structure unit,

In the formula, A¹¹And A¹²Each independently represent the aromatic series of 4 valences as derived from the acid anhydrides comprising aromatic tetracarboxylic acid's acid anhydride Group, B¹¹And B¹²The diamines residue of the divalent as derived from aromatic diamine is each independently represented, selected from by A¹²And B¹²Composition At least one in group includes the spacer group of divalent in its structure,