CN1933954A - Method for producing synthetic resin film and synthetic resin film - Google Patents

Abstract

A method for continuous production of a synthetic resin film which comprises (A) a step of applying a composition containing a polymer and an organic solvent continuously on a support through allowing the composition to flow and extend thereon, to thereby form a gel film, (B) a step of ripping the gel film off the support and fixing both ends of the gel film, (C) a step of conveying the film in a heating furnace while fixing both ends of the film, wherein the film is fixed in such a manner that the tensile force in the direction of the width (TD direction) of the film is substantially zero in at least a part of the (C) step. The above film can be suitably used for the continuous production of a synthetic resin film exhibiting stable physical properties over the whole width thereof, in particular, a synthetic resin film having the molecular orientation controlled to MD direction, which is considered to be useful in the electronic field.

Description

The manufacture method of synthetic resin film and synthetic resin film

Technical field

The present invention relates to the manufacture method of synthetic resin film.In detail, the manufacture method that relates to the synthetic resin film of rerum natura stabilisation on whole width, the molecular orientation axis that for example relates to synthetic resin film is controlled so as to the novel manufacturing method of the synthetic resin film of direction of feed towards machinery (below, be called for short the MD direction).In more detail, relate on the whole width of the synthetic resin film of quantity-produced wide cut, molecular orientation axis is controlled so as to towards the novel manufacturing method of the synthetic resin film of MD direction.

Background technology

For example in the technical field of electronic equipment, the requirement of high-density installation is constantly surging day by day, with its together in the technical field of using flexible print circuit board (below, be called FPC), the requirement of high-density installation is also constantly surging.The manufacturing process of FPC roughly is distinguished into the operation of laminated metal on basement membrane, forms the operation of distribution in the metal surface, but the operation that change in size is big is the front and back of the operation of the folded metal of limit heating basement membrane boundary layer when laminated metal, the etching work procedure front and back when making metal form pattern, be the front and back of the operation that under the FPC state, heats in addition, require little in the change in size of the front and back of this operation FPC.In order to adapt to this requirement, the inventor etc. think: with molecularly oriented be controlled at machinery direction of feed (below, abbreviation MD direction) synthetic resin film, promptly, the molecularly oriented of film is orientated along the MD direction, it is useful making the film that has difference with the rerum natura of the vertical direction of direction of feed of machinery (below, be called for short the TD direction).More particularly, think molecularly oriented is controlled at the synthetic resin film of MD direction as basement membrane, when laminated metal, in the operation of the folded metal forming of limit heating basement membrane boundary layer, use, diminish useful to making change in size (formation pattern front and back, FPC heat front and back).

This is because if molecularly oriented is controlled at the MD direction, and the elastic modelling quantity that film flows to (MD direction) uprises, and the influence of tension force diminishes, thereby the change in size before and after the above-mentioned operation is diminished.

In addition, for example for the film that molecularly oriented is controlled at the MD direction, the elastic modelling quantity of MD direction uprises, and thinks thus to improve towards the slip bendability of the film of MD direction.

Like this, the film that molecularly oriented is controlled at the MD direction be considered to especially FPC, the TAB of electronic device field (Tape Automated Bonding) with film, COF (chip on film) with useful in the substrate etc., but also do not obtain the manufacture method of the molecularly oriented of controlling diaphragm at random now and molecularly oriented be controlled at the film of MD direction.Particularly when producing synthetic resin film continuously, the characteristic of controlling diaphragm is considered to very difficulty on whole width, obtain on whole width molecularly oriented being controlled at the method for the synthetic resin film of MD direction, does not also know up to now.

The polyimide film that will for example have proposed in patent documentation 1 after the limit will be burnt till is implemented the method that the annealing in process limit stretches along the MD direction.

In patent documentation 2, proposed in addition when film is made along the MD direction stretch 1.0～1.5 times, along stretch 0.5～0.99 times method of TD direction.

In patent documentation 3, proposed by will be with solvent expansion the stretch method of the polyimides that obtains simple tension of 3～100 times gel mould.

In patent documentation 4, proposed by giving 10kg/mm to polyimide film more than 250 ℃ ²Above tension force carries out the zone stretching and makes the method that orientation is controlled at the polyimide film of MD direction.

After in patent documentation 5, having proposed the aromatic polyimide precursor film of remaining solvent to be expanded, stretch unidirectional at least with swelling agent, after this remove swelling agent from this film after, carry out the manufacture method of heat drying.

In patent documentation 6, proposed by will be with solvent expansion the stretch method of the polyimides that obtains simple tension of 3～20 times gel mould.

In patent documentation 7, put down in writing with 3,3 ', 4,4 '-biphenyltetracarboxyacid acid composition and p-phenylenediamine (PPD) composition be as in the necessary polyimide film, control the both ends of self-supporting film and insert in the heating furnace, in 300 ℃ that roughly finish until the contraction of self-supporting film operation, make film control the method for narrowed width gradually.

In patent documentation 8, put down in writing the both ends of gel mould have been fixed, in heating furnace, make the film width set the stiff end distance successively with diminishing, after then making the film width become the earth setting stiff end distance successively, make the film width set the manufacture method of the polyimide film of stiff end distance successively again with diminishing.

Yet, in above-mentioned arbitrary document, become the two ends of no tension force ground immobilized gel film basically and the operation of in heating furnace, carrying for the tension force that makes the TD direction as characteristic of the present invention, all do not have open, different fully with the present invention.

[patent documentation 1] spy opens flat 8-174659 0017 paragraph

[patent documentation 2] spy opens flat 11-156936 0021 paragraph

[patent documentation 3] spy opens 2003-128811 0010 paragraph

[patent documentation 4] spy opens the 2nd page upper right section the 15th row of clear 63-197628

[patent documentation 5] spy opens 2002-1804 0007 paragraph

[patent documentation 6] spy opens 2003-145561 0014 paragraph

[patent documentation 7] spy opens 2002-179821 0020 paragraph

[patent documentation 8] spy opens 2004-331792 0008 paragraph

Summary of the invention

As mentioned above, up to the present the manufacture method that be considered to particularly useful in the technical field of electronic equipments such as FPC, molecularly oriented is controlled at the synthetic resin film of MD direction on the whole width of film does not also obtain.The inventor etc. are with in producing continuously, make the synthetic resin film that especially in electronic device field, is considered to useful, on the whole width of film, molecularly oriented is controlled at the MD direction, particularly polyimide film is a purpose, carries out intensive research repeatedly, and the result has finished the present invention.

The present invention can solve above-mentioned problem by the manufacture method of following novel synthetic resin film.

1) manufacture method of synthetic resin film is in the manufacture method of quantity-produced synthetic resin film, comprises the manufacture method of the synthetic resin film of following (A)～(C) at least:

(A) on supporter continuously curtain coating coating contain the composition of macromolecule and organic solvent, form the operation of gel mould,

(B) peel off gel mould from supporter, the operation at immobilized gel film two ends,

(C) the fixing limit, two ends of the film operation of in heating furnace, carrying in limit,

It is characterized in that: at least a portion of above-mentioned (C) operation, comprise the fixedly two ends operation of carrying of tension force that (C-1) make film width (TD direction) with becoming no tension force basically.

2) the above-mentioned 1) manufacture method of described synthetic resin film is characterized in that: the inlet of the heating furnace in above-mentioned (C) operation, the tension force that makes the TD direction is two ends fixedly with becoming no tension force basically.

3) the above-mentioned 2) manufacture method of described synthetic resin film is characterized in that: above-mentioned heating furnace is made up of a plurality of heating furnaces more than or equal to 2, and the temperature of the 1st heating furnace is below 300 ℃.

The manufacture method of each described synthetic resin film 4) above-mentioned 1)～3), it is characterized in that: in above-mentioned (C) operation, if the distance of both ends stiff end is the film width between X, both ends stiff end when being Y, make X and Y satisfy following formula, thereby the tension force that makes the TD direction fixedly between two ends with becoming no tension force basically.

20.0≥(Y-X)/Y×100＞0.00

5) above-mentioned 1)～4) manufacture method of described synthetic resin film is characterized in that: at least a portion of above-mentioned (C) operation, comprise (C-2) operation along TD direction stretched film.

6) the above-mentioned 5) manufacture method of described synthetic resin film, it is characterized in that: in above-mentioned (C-2) operation, the distance of the both ends stiff end of the TD direction before if stretch is Z, in the stove in-draw distance of the both ends stiff end during film when being W, make Z and W satisfy following formula, along TD direction stretched film.

40.0≥(W-Z)/Z×100＞0.00

The manufacture method of each described synthetic resin film 7) above-mentioned 1)～6) is characterized in that: above-mentioned synthetic resin film is a polyimide film.

The synthetic resin film that the manufacture method of each described synthetic resin film 8) use above-mentioned 1)～7) is made.

Manufacture method according to synthetic resin film of the present invention, can access the synthetic resin film that molecularly oriented is controlled at the MD direction, even particularly the synthetic resin film of quantity-produced wide cut also can access the synthetic resin film that molecularly oriented is controlled at the MD direction on whole width.

Description of drawings

Fig. 1 is the manufacturing installation schematic diagram of polyimide film.

Fig. 2 is used to illustrate that the film between the grasping device of polyimide film controls the schematic diagram of situation.

Fig. 3 is that expression is used for the figure at the sampling method of embodiment and the Comparative Examples mensuration degree of orientation and the angle of orientation.

Moreover, among Fig. 1 and/or Fig. 2, symbol 1 expression film conveying device, symbol 2,3,4,5 and 6 expression firing furnaces, symbol 7 expression films are controlled the beginning position, width X between the grasping device of symbol 8 expression films, symbol 9 expressions are the film width Y that is held in the TD direction of the gel mould between grasping device, symbol 10 expression film throughput directions, the width Z of the both ends stiff end of the TD direction before symbol 11 expressions stretch, symbol 12 is illustrated in the stove width W of the both ends stiff end when the TD direction has stretched film, the device (die head) of symbol 13 expression curtain coating coating organic solvent solutions, the supporter of symbol 14 expression organic solvent solutions, symbol 15 is illustrated in the device that applies tension force on the gel mould, and the position that gel mould is peeled off in symbol 16 expressions.

In addition, among Fig. 3, symbol 20 expression film width are more than or equal to 800mm, and symbol 21 is represented MD directions (film throughput direction), and symbol 22 expression film width are less than 800mm, and symbol 23 expression sample film width 40mm.

The specific embodiment

The present invention is the manufacture method of synthetic resin film, and it is in the manufacture method of quantity-produced synthetic resin film, comprises the manufacture method of the synthetic resin film of following (A)～(C) at least:

(A) on supporter continuously curtain coating coating contain the composition of macromolecule and organic solvent, form the operation of gel mould,

(B) peel off gel mould from supporter, the operation that the two ends of gel mould are fixing,

(C) the fixing limit, two ends of the film operation of in heating furnace, carrying in limit,

It is characterized in that: at least a portion of above-mentioned (C) operation, the tension force of film width (TD direction) is fixedly carried at two ends with becoming no tension force basically.Below, explain each operation.

(A) operation

(A) operation be on supporter continuously curtain coating coating contain the composition of macromolecule and organic solvent, obtain the operation of gel mould.In the manufacture method of the synthetic resin film of the present application, the so-called macromolecule that can be fit to use, generally be preferably the material that shows as " polymer ", as having used this high molecular synthetic resin film, for example can enumerate PI (polyimide film), PA (PA membrane), PEN (PEN), the polyamidoimide film, polypropylene screen, PC (polycarbonate membrane), PPS (polyphenylene sulfide film), LCP (liquid crystalline polymer film), PET (PETG film), PE (polyethylene film), PVA (polyvinyl alcohol film), PTFE (poly tetrafluoroethylene), PVDF (polyvinylidene fluoride film), PVF synthetic resin films such as (pvf films).As the preferred especially synthetic resin film that uses in electric purposes, preferably use polyimide film.

In the present application, what is called contains the composition of macromolecule and organic solvent, macromolecule dissolution in organic solvent and directly can be used, also can be to make the high molecular precursor of the synthetic resin film that formation finally obtains be dissolved in composition in the organic solvent.In addition, can also use the composition that has added other compositions such as reactant that can react with the polymer body that becomes precursor.

For example, when making polyimide film, can use the composition that in organic solvent, has dissolved as the polyamic acid of polyimide precursor as synthetic resin film.In said composition, can contain additives such as remover, imidization catalyst, dehydrating agent.In addition, equally also can use the composition of the polyimide resin that in organic solvent, is dissolved with imidizate.Have, when other resins, for example the PET film can be enumerated the composition that contains the PETG that is dissolved with PETG in organic solvent again.

Moreover, as the solid component concentration of the suitable organic solvent solution that uses of above-mentioned composition,, be the organic solvent solution of the ratio dissolving of 5～40 weight % with this macromolecule weight with respect to total solution weight, in manufacturing process, can reduce the organic solvent amount that will remove, therefore preferred.In addition, if in the manufacture method of the synthetic resin film under the solid component concentration more than above-mentioned scope, solution also has flowability, can be from the slit mouth ejection of die head, when when the die head curtain coating is on supporting body surface, if make the solution of the film that shows self-supporting, whatsoever the solution of sample concentration can both use.

The solvent that is fit to use as above-mentioned organic solvent, because the macromolecule difference of dissolving is also different, for example when making polyimide film, can enumerate tetramethylurea, N, the ureas that N-dimethyl ethyl urea is such, methyl-sulfoxide, diphenyl sulphone (DPS), sulfoxide that the tetramethyl sulfone is such or sulfone class, N, N-dimethylacetylamide (being called for short DMAc), N, dinethylformamide (being called for short DMF), N-N-methyl-2-2-pyrrolidone N-(being called for short NMP), gamma-butyrolacton, the amide-type that hexamethyl phosphoric triamide is such, the perhaps non-protonic solvent of phosphoramide types, chloroform, alkyl halide base class such as carrene, benzene, arenes such as toluene, phenol, phenols such as cresols, dimethyl ether, diethyl ether, ethers such as paracresol methyl ether.Usually use these solvents separately, but can make up aptly more than or equal to 2 kinds of uses as required.Among these, consider, preferably use amide-types such as DMF, DMAc, NMP as solvent from the high aspect of macromolecule dissolution.

As synthetic resin film,,, can use the polyamic acid of the precursor that becomes polyimide film as the macromolecule that in (A) operation, uses if exemplify the situation of making polyimide film.As polyamic acid, be not particularly limited, can be by in organic solvent, making the roughly polyamic acid solution that obtains of reaction with same mole of acid dianhydride and diamines.Moreover, polymerization as polyamic acid, which type of polymerization can use, and for example can use in organic solvent dissolving or disperse two amines more than or equal to a kind, adds the random copolymerization method of carrying out polymerization more than or equal to a kind acid dianhydride in this solution; Add the random copolymerization method of carrying out polymerization in dissolving or in being dispersed with more than or equal to the solution of a kind acid dianhydride more than or equal to a kind diamines; In making, add the methods such as polymerization that diamines or acid dianhydride finish polymerization again more than or equal to a kind diamines and solution more than or equal to a kind acid dianhydride polymerization.But the main idea of the present application is the manufacture method of synthetic resin film.Have no particular limits as the polymerization in the manufacture method of the above-mentioned polyamic acid solution of the precursor of polyimide film, which type of polymerization can use.

As the organic solvent that in the polymerization of polyamic acid, uses, can enumerate tetramethylurea, N, the ureas that N-dimethyl ethyl urea is such, methyl-sulfoxide, diphenyl sulphone (DPS), sulfoxide that the tetramethyl sulfone is such or sulfone class, N, N-dimethylacetylamide (being called for short DMAc), N, dinethylformamide (being called for short DMF), N-N-methyl-2-2-pyrrolidone N-(being called for short NMP), gamma-butyrolacton, the amide-type that hexamethyl phosphoric triamide is such, the perhaps non-protonic solvent of phosphoramide types, chloroform, alkyl halide base class such as carrene, benzene, arenes such as toluene, phenol, phenols such as cresols, dimethyl ether, diethyl ether, ethers such as paracresol methyl ether use these solvents usually separately, but can make up aptly more than or equal to 2 kinds of uses as required.Among these, consider, preferably use amide-types such as DMF, DMAc, NMP as solvent from the high aspect of macromolecule dissolution.

The weight % of the polyamic acid solid constituent in the polyamic acid solution considers from operating aspect, preferably dissolves 5～40 weight %, preferred 10～30 weight %, the more preferably polyamic acid of 13～25 weight % in organic solvent.Moreover the PEG (polyethylene glycol) that presses GPC converts, and the mean molecule quantity of polyamic acid is preferably more than from the film rerum natura and equals 10000.

In addition, the viscosity of above-mentioned polyamic acid solution, be incubated in 23 ℃ water-bath insulation 1 hour, using Brookfield viscometer, is the viscosity that 4rpm measures this moment with the revolution of rotor No.7, and this viscosity is preferably more than and equals 50Pas smaller or equal to 1000Pas, more preferably more than or equal to 100Pas smaller or equal to 500Pas, most preferably more than or equal to 200Pas smaller or equal to 350Pas, when making the film formed body, in operation most preferably.

In the manufacturing of relevant polyamic acid solution of the present invention, as the acid dianhydride that can be fit to use, can enumerate TOPOT 2,2 (trimellitic acid monoesters acid anhydrides), to methylphenylene two (trimellitic acid monoesters acid anhydrides), to (2,3-dimethyl phenylene) two (trimellitic acid monoesters acid anhydrides), 4,4 '-biphenylene two (trimellitic acid monoesters acid anhydrides), 1,4-naphthalene two (trimellitic acid monoesters acid anhydrides), 2,6-naphthalene two (trimellitic acid monoesters acid anhydrides), 2, two (4-hydroxy phenyl) the propane dibenzoates-3 of 2-, 3 ', 4,4 '-anhydrides such as ester such as tetracarboxylic dianhydride's grade, the ethylene-tetracarboxylic acid dianhydride, 1,2,3,4-ethylene-dimalonic acid dianhydride, cyclopentane tetracarboxylic acid dianhydride, pyromellitic acid anhydride, 1,2,3, the 4-PMDA, 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydride, 2,2 ', 3,3 '-bibenzene tetracarboxylic dianhydride, 3,3 ', 4,4 '-the benzophenone tetracarboxylic acid dianhydride, 2,2 ', 3,3 '-the benzophenone tetracarboxylic acid dianhydride, two (2, the anhydrous dicarboxyl phenyl of 3-) methane, two (3, the anhydrous dicarboxyl phenyl of 4-) methane, 1,1-two (2, the anhydrous dicarboxyl phenyl of 3-) ethane, 2, two (3, the anhydrous dicarboxyl phenyl of the 4-) propane of 2-, 2,2-two (2, the anhydrous dicarboxyl phenyl of 3-) propane, two (3, the anhydrous dicarboxyl phenyl of 4-) ether, two (2, the anhydrous dicarboxyl phenyl of 3-) ether, two (2, the anhydrous dicarboxyl phenyl of 3-) sulfone, 2,3,6,7-naphthalenetetracarbacidic acidic dianhydride, 1,4,5,8-naphthalenetetracarbacidic acidic dianhydride, 1,2,5,6-naphthalenetetracarbacidic acidic dianhydride, 2,3,6,7-anthracene tetracarboxylic acid dianhydride, 1,2,7, the luxuriant and rich with fragrance tetracarboxylic acid dianhydride of 8-, 3,4,9,10-perylene tetracarboxylic acid dianhydride, 4,4-(to the phenylene dioxy) two O-phthalic acid dianhydrides, 4,4-(metaphenylene dioxy) two O-phthalic acid dianhydrides, 2, acid dianhydrides such as two [(2, the anhydrous di carboxyl phenyloxy of the 3-) phenyl] propane of 2-, these can use separately or use more than or equal to 2 kinds.

In these acid dianhydrides, use to be selected from Pyromellitic Acid, 1,2,3,4-PMDA, 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydride, 2,2 ', 3,3 '-bibenzene tetracarboxylic dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic acid dianhydride, 2,2 ', 3,3 '-benzophenone tetracarboxylic acid dianhydride, TOPOT 2,2 (trimellitic acid monoesters acid anhydrides) more than or equal to a kind, give the polyimides film heat resistance, the elastic modelling quantity of film is improved, carry out the orientation of polyimide film easily, so preferred.

If the elastic modelling quantity of polyimide film improves, the volume contraction when bringing into play owing to the residual volatile ingredient in the film produces shrinkage stress in face, utilizes this shrinkage stress to promote the molecularly oriented that face is interior.Its result, the molecularly oriented development of polyimide film.

In addition, as the amines class, can enumerate p-phenylenediamine (PPD); m-phenylene diamine (MPD); o-phenylenediamine; 3; 3 '-diaminodiphenyl ether; 3,4 '-diaminodiphenyl ether; 4,4 '-diaminodiphenyl ether; 3; 3 '-diaminodiphenyl sulfide; 3,4 '-diaminodiphenyl sulfide; 4,4 '-diaminodiphenyl sulfide; 3; 3 '-DADPS; 3,4 '-DADPS; 4,4 '-DADPS; 3; 3 '-diaminobenzophenone; 3,4 '-diaminobenzophenone; 4,4 '-diaminobenzophenone; 3; 3 '-diaminodiphenyl-methane; 3,4 '-diaminodiphenyl-methane; 4,4 '-diaminodiphenyl-methane; 2; two (4-aminophenyl) propane of 2-; 2, two (3-aminophenyl) propane of 2-; 2-(3-aminophenyl)-2-(4-aminophenyl) propane; 2, two (the 4-aminophenyls)-1 of 2-; 1; 1,3,3; the 3-HFC-236fa; 2; two (the 3-aminophenyls)-1,1,1 of 2-; 3; 3, the 3-HFC-236fa; 2-(3-aminophenyl)-2-(4-aminophenyl)-1,1; 1; 3,3, the 3-HFC-236fa; 1; two (3-amino-benzene oxygen) benzene of 3-; 1; two (4-amino-benzene oxygen) benzene of 3-; 1, two (3-amino-benzene oxygen) benzene of 4-; 1, two (4-amino-benzene oxygen) benzene of 4-; 1; two (3-amino benzoyl) benzene of 3-; 1; two (3-amino benzoyl) benzene of 4-; 1, two (4-amino benzoyl) benzene of 3-; 1, two (4-amino benzoyl) benzene of 4-; 3; 3 '-diaminourea-4-phenoxy group benzophenone; 4; 4 '-diaminourea-5-phenoxy group benzophenone; 3,4 '-diaminourea-4-phenoxy group benzophenone; 3,4 '-diaminourea-5-phenoxy group benzophenone; 4; 4 '-two (4-amino-benzene oxygen) biphenyl; 3; 3 '-two (4-amino-benzene oxygen) biphenyl; 3,4 '-two (3-amino-benzene oxygen) biphenyl; two [4-(4-amino-benzene oxygen) phenyl] ketone; two [4-(3-amino-benzene oxygen) phenyl] ketone; two [3-(4-amino-benzene oxygen) phenyl] ketone; two [3-(3-amino-benzene oxygen) phenyl] ketone; 3,3 '-diaminourea-4; 4 '-two phenoxy group benzophenone; 4; 4 '-diaminourea-5,5 '-two phenoxy group benzophenone; 3,4 '-diaminourea-4; 5 '-two phenoxy group benzophenone; two [4-(4-amino-benzene oxygen) phenyl] thioether; two [3-(4-amino-benzene oxygen) phenyl] thioether; two [4-(3-amino-benzene oxygen) phenyl] thioether; two [3-(4-amino-benzene oxygen) phenyl] thioether; two [3-(3-amino-benzene oxygen) phenyl] thioether; two [3-(4-amino-benzene oxygen) phenyl] sulfone; two [4-(4-amino-benzene oxygen) phenyl] sulfone; two [3-(3-amino-benzene oxygen) phenyl] sulfone; two [4-(3-amino-benzene oxygen) phenyl] sulfone; two [4-(3-amino-benzene oxygen) phenyl] ether; two [4-(4-amino-benzene oxygen) phenyl] ether; two [3-(3-amino-benzene oxygen) phenyl] ether; two [4-(3-amino-benzene oxygen) phenyl] methane; two [4-(4-amino-benzene oxygen) phenyl] methane; two [3-(3-amino-benzene oxygen) phenyl] methane; two [3-(4-amino-benzene oxygen) phenyl] methane; 2; two [4-(3-amino-benzene oxygen) phenyl] propane of 2-; 2, two [4-(4-amino-benzene oxygen) phenyl] propane of 2-; 2, two [3-(3-amino-benzene oxygen) phenyl] propane of 2-; 2; two [4-(3-amino-benzene oxygen) phenyl]-1 of 2-; 1,1,3; 3; the 3-HFC-236fa; 2, two [4-(4-amino-benzene oxygen) phenyl]-1,1 of 2-; 1; 3,3, the 3-HFC-236fa; 2; two [3-(3-amino-benzene oxygen) phenyl]-1 of 2-; 1,1,3; 3; the 3-HFC-236fa; 2, two [3-(4-amino-benzene oxygen) phenyl]-1,1 of 2-; 1; 3,3, the 3-HFC-236fa; 1; two [4-(3-amino-benzene oxygen) benzoyl] benzene of 4-; 1; two [4-(3-amino-benzene oxygen) benzoyl] benzene of 3-; 1, two (3-amino-4-phenoxy group benzoyl) benzene of 3-; 1, two (3-amino-4-phenoxy group benzoyl) benzene of 4-; 1; two (4-amino-5-phenoxy group benzoyl) benzene of 3-; 1; two (4-amino-5-biphenylyloxy benzoyl) benzene of 3-; 1, two (4-amino-5-biphenylyloxy benzoyl) benzene of 4-; 1, two (3-amino-4-biphenylyloxy benzoyl) benzene of 3-; 1; two (3-amino-4-biphenylyloxy benzoyl) benzene of 4-; 1; two [4-(4-amino-benzene oxygen)-α, the α-Er Jiajibianji] benzene of 4-; 1, the two [4-(4-amino-benzene oxygen)-α of 3-; α-Er Jiajibianji] benzene; 1; two [4-(4-amino-6-4-trifluoromethylphenopendant)-α, the α-Er Jiajibianji] benzene of 3-; 1, the two [4-(4-amino-6-methyl fluoride phenoxy group)-α of 3-; α-Er Jiajibianji] benzene; 1; two [4-(4-amino-6-methylphenoxy)-α, the α-Er Jiajibianji] benzene of 3-; 1, the two [4-(4-amino-6-cyano-benzene oxygen)-α of 3-; α-Er Jiajibianji] benzene; the diaminourea polysiloxanes, these can use separately or can make up more than or equal to 2 kinds of uses.

Among these, from improving the hear resistance of polyimide film, can give the membrane rigidity aspect sets out, the preferred use is selected from p-phenylenediamine (PPD), m-phenylene diamine (MPD), 3,3 '-diaminodiphenyl ether, 3,4 '-diaminodiphenyl ether, 4,4 '-diaminodiphenyl ether, 2, two [4-(4-amino-benzene oxygen) phenyl] propane of 2-more than or equal to a kind.Have again, by with p-phenylenediamine (PPD) and/or 3,4 '-diaminodiphenyl ether is as must composition and usefulness, improves at the elastic modelling quantity that makes polyimide film, it is preferred carrying out on the orientation of polyimide film easily.

As particularly preferred polyimide film, 1. use p-phenylenediamine (PPD), 4,4 '-diaminodiphenyl ether, pyromellitic acid anhydride, the polyimide film that 4 monomers of TOPOT 2,2 (trimellitic acid monoesters acid anhydrides) are made, 2. use p-phenylenediamine (PPD), 4,4 '-diaminodiphenyl ether, pyromellitic acid anhydride, 3,3 ', 4,4 '-polyimide film that bibenzene tetracarboxylic dianhydride is made, 3. use p-phenylenediamine (PPD), 4,4 '-diaminodiphenyl ether, pyromellitic acid anhydride, 3,3 ', 4,4 '-polyimide film that the benzophenone tetracarboxylic acid dianhydride is made, 4. use p-phenylenediamine (PPD), 4,4 '-diaminodiphenyl ether, pyromellitic acid anhydride, TOPOT 2,2 (trimellitic acid monoesters acid anhydrides), 3,3 ', 4,4 '-polyimide film that bibenzene tetracarboxylic dianhydride is made, 5. use p-phenylenediamine (PPD), 4,4 '-diaminodiphenyl ether, 3,3 ', 4,4 '-polyimide film that bibenzene tetracarboxylic dianhydride is made, 6. use 4,4 '-diaminodiphenyl ether, 3,4 '-diaminodiphenyl ether, the polyimide film that pyromellitic acid anhydride is made, 7. use p-phenylenediamine (PPD), 4,4 '-diaminodiphenyl ether, 2, two [4-(4-amino-benzene oxygen) phenyl] propane of 2-, pyromellitic acid anhydride, 3,3 ', 4,4 '-polyimide film that bibenzene tetracarboxylic dianhydride is made, 8. use p-phenylenediamine (PPD), 3,3 ', 4,4 '-polyimide film that bibenzene tetracarboxylic dianhydride is made, have the advantage of easy control angle of molecular orientation, therefore be fit to use.

Contain in the method for compositions of macromolecule and organic solvent in this operation of curtain coating continuously on supporter described later, for example under the situation of polyimide film, adopt 1. direct curtain coating to contain the method for the solution of above-mentioned polyamic acid, 2. before containing the solution of above-mentioned polyamic acid, curtain coating mixes the imidization catalyst method of its solution of curtain coating again, 3. before containing the solution of above-mentioned polyamic acid, curtain coating mixes imidization catalyst and the dehydrating agent method of its solution of curtain coating again, 4. before the above-mentioned polyamic acid solution of curtain coating, mix the remover method etc. of its solution of curtain coating again.Therefore, imidization catalyst, dehydrating agent, remover at first are described.

As the imidization catalyst in this operation, for example use aliphatic tertiary amine classes such as trimethylamine, triethylamine, tri-n-butylamine, aromatic tertiary amines such as dimethylaniline, hetero ring type tertiary amines such as pyridine, isoquinolin, picoline etc.As dehydrating agent, can enumerate aliphatic anhydride, aromatic anhydrides etc. such as acetic anhydride.As remover, can use for example acetate etc.

With imidization catalyst, dehydrating agent, remover and before the polyamic acid organic solvent solution mixes, be provided with filter etc. and remove the operation of not dissolving raw material, sneaking into foreign matter, be preferred on the foreign matter in reducing film, the defective.The mesh of above-mentioned filter can be to obtain 1/2 of film thickness, preferably 1/5, be more preferably 1/10.

About in polyamic acid solution, only mixing the ratio of imidization catalyst, depend on the structural formula that constitutes polyamic acid, but amide groups molal quantity=10～0.01 in preferred imidization catalyst/polyamic acid.More preferably amide groups molal quantity=5～0.5 in imidization catalyst/polyamic acid.

With respect to polyamic acid, content when mixed dehydration agent and imidization catalyst, depend on the structural formula that constitutes polyamic acid, but amide groups molal quantity=10～0.01 in preferred dehydrating agent molal quantity/polyamic acid, amide groups molal quantity=10～0.01 in imidization catalyst/polyamic acid.More preferably amide groups molal quantity=5～0.5 in dehydrating agent molal quantity/polyamic acid, amide groups molal quantity=5～0.5 in imidization catalyst/polyamic acid.Moreover, in this occasion, also can and with response delay agent such as acetylacetone,2,4-pentanediones.In addition, dehydrating agent and catalyst can determine by mix back to the time (storage period) that viscosity begins to rise with dehydrating agent, catalyst mixture at 0 ℃ of polyamic acid with respect to the content of polyamic acid.Be 0.1 minute～120 minutes general storage period, is more preferably 0.5 minute～60 minutes.

In addition, in not hindering scope of the present invention, can add degree ground usually and add heat stabilizer, antioxidant, ultra-violet absorber, antistatic additive, fire retardant, pigment, dyestuff, fatty acid ester, organic lubricant (for example wax) etc.In addition, in order to give surperficial easy to be sliding property, wearability, marresistance etc., can add inorganic particulates such as clay, mica, titanium oxide, calcium carbonate, kaolin, talcum, wet method or dry method silica, colloidal state shape silica (colloidal silica), calcium phosphate, calcium monohydrogen phosphate, barium sulfate, aluminium oxide and zirconia, with acrylic compounds, styrene etc. as organic filler of constituent etc., maybe can contain the so-called internal particle of separating out, also can contain surfactant by the catalyst that when polyester reacts, adds etc.

Moreover the elastic modelling quantity of the polyimide film that uses in the present application is high more, is orientated control easily more, and elastic modelling quantity not only depends on the composition of polyimide film, also depends on manufacturing process etc. to a great extent.Therefore, measure the MD direction of the polyimide film after producing and the elastic modelling quantity of TD direction (vertical direction of MD direction), if the mean value that will be worth is defined as the elastic modelling quantity of film, then the elastic modelling quantity of film be more than or equal to 4.0GPa smaller or equal to 7.0GPa, preferred in the orientation control of carrying out polyimide film.Elastic modelling quantity is high more, and the orientation of polyimide film is easy more carries out.In the present application, preferably show the polyimide film of such elastic modelling quantity, such structure is by being selected in acid dianhydride or the diamines that uses in the polyimide film aptly, perhaps after selecting used monomer aptly, suitably change polymerization formula, have the selected aptly manufacture method (in the seasoning at conveyer belt position, the temperature in the Tenter oven etc.) that is used to improve elastic modelling quantity to realize again.

Curtain coating is coated with the composition that obtains so continuously on supporter.As supporter, if not by this solution resin dissolves, can also tolerate the needed heated support body of organic solvent solution that is used to remove this synthetic resin solution, which type of supporter can use.From making the coating fluid drying of solution shape, special preferred combination metallic plate and endless belt or the metal rotating cylinder made.Moreover the material of endless belt or rotating cylinder is preferably used metal, wherein preferably uses the SUS material.By using the material of implementing to electroplate on the surface with metals such as chromium, titanium, nickel, cobalts to improve the adaptation of lip-deep solvent, perhaps become and peel off easily, so preferably implement electroplating processes because of the dry resin molding of crossing.Have level and smooth surface on preferred endless belt, the metal rotating cylinder, but also can on endless belt or metal rotating cylinder, make countless concavo-convex and use.Preferably the concavo-convex diameter that is processed on endless belt or metal rotating cylinder is 0.1 μ m～100 μ m, and the degree of depth is 0.1 μ m～100 μ m.Concavo-convex by making in the metal surface, make and make fine projection possibility that become on the surface of synthetic resin film, utilize this projection, prevent the generation of the wound that the phase mutual friction by film causes or make the mutual sliding raising of film become possibility.

Gel mould in so-called the present application, be the organic solvent solution that heating, drying is contained macromolecule and organic solvent, the high molecula resin film of remaining a part of organic solvent or reaction product (these are called remaining composition) is called gel mould in polymeric membrane.In the manufacturing process of polyimide film, make organic solvent, imidization catalyst, dehydrating agent, the reaction product (the suction composition of dehydrating agent, water) of polyamic acid solution dissolving remaining as the remaining composition in the gel mould.Remain in the remaining component ratio in the gel mould, when calculating remaining remaining composition weight b (g) with respect to the bone dry synthetic resin weight a (g) that in this gel mould, exists, remaining component ratio c is the value that calculates with following calculating formula, preferred this remaining component ratio is smaller or equal to 500%, be more preferably more than or equal to 25% smaller or equal to 200%, especially preferably more than or equal to 30% smaller or equal to 150%.

C=b/a * 100 (formula 1)

Greater than 500% o'clock, operability is poor, and if the quantity of solvent during removal of solvents increase, it is big that the contraction of film becomes, the control of the orientation difficulty that becomes is therefore not preferred.In addition, remaining component ratio is more than or equal to 25%, and the orientation of polyimide film is easily towards the MD direction, and it is stable easily that the physics value of the film of width becomes, therefore preferred.

The computational methods of bone dry synthetic resin weight a and remaining composition weight b, behind the gel mould weight d that measures 100mm * 100mm, this gel mould after dry 20 minutes, is cooled to room temperature in 300 ℃ baking oven, gravimetry is as bone dry synthetic resin weight a then.Remaining composition weight b is calculated according to the calculating formula of b=d-a by gel mould weight d and bone dry synthetic resin weight a.

In making the operation of gel mould, heating on supporter, the temperature wind speed exhaust velocity when dry, preferred remaining component ratio become in the above-mentioned scope and determine.Especially, in the manufacturing process of polyimide film, preferably heating, drying contain the organic solvent solution of macromolecule and organic solvent under the temperature of 50～200 ℃ of scopes, particularly preferably in heat under 50～180 ℃, drying.Moreover carry out drying preferred drying time in 1～300 minute scope, with the temperature treatment drying of multisection type.

(B) operation

(B) operation is to peel off gel mould from supporter, continuously the operation at the two ends of immobilized gel film.The operation of the end of the immobilized gel film in so-called the present application, the operation that the grasping device that is to use needle plate, clip etc. generally to use in film manufacturing device is controlled the end of gel mould.Moreover, as the position at said fixedly two ends in the present application, for example can enumerate use Fig. 11 in record be installed in the position that end grasping device (needle plate or clip) on the film conveying device begins to control the film end (Fig. 1 7).

Basically become no tension force and the method for fixing as the tension force that makes the TD direction at least a portion in (C) described later operation, when the end of the immobilized gel film of this (B) operation, can make the tension force of TD direction become no tension force basically and fix.Be in fixing stage of film, make the tension force of TD direction become no tension force basically and carry out that former state is sent into the method for (C) operation.Specifically, when anchor portion, film is relaxed fix.

(C) operation

(C) operation is the fixedly limit, two ends of the film operation of carrying in heating furnace of limit.In the present invention, at least a portion of this (C) operation, making the tension force of film width (TD direction) become no tension force basically and fixedly carry, is important obtaining being orientated aspect the synthetic resin film that is controlled at the MD direction.

Wherein, the tension force of so-called TD direction is no tension force basically, means except the tension force that is produced by the deadweight of film, does not apply the tensile stress that the operation by machinery produces in the TD direction.Basically mean that film width between the stiff end of both ends (Fig. 2 9) is wideer than the distance of the both ends stiff end of film (Fig. 2 8), the film under this situation is called film under the essentially no tension force.If be illustrated with Fig. 2, film is fixed with grasping device, and 8 of Fig. 2 length is the distance of both ends fixture end at this moment.Usually, the two ends of film are the states that does not impose pin and tension force, and at this moment, the width 9 of the film between both ends stiff end distance 8 and both ends stiff end is identical.In the present invention, as shown in Figure 2, the width 9 of both ends stiff end distance 8 and therebetween film is different, and the distance of both ends stiff end diminishes.Specifically, make film lax and fix.Especially, the molecularly oriented aspect of calm MD direction easy to control considers,, preferably makes X and Y satisfy following formula and fixes for X, when establishing film width 9 between the stiff end of both ends for Y in the distance 8 of establishing the both ends stiff end.

20.0 〉=(Y-X)/Y * 100＞0.00 (formula 2)

If (Y-X)/Y * 100 (being referred to as the TD shrinkage factor for convenience sometimes) are increased to more than the above-mentioned scope, stably the lax difficulty that just becomes of controlling diaphragm changes sometimes with respect to the direct of travel slack.In addition, because the situation difference produces lax the coming off from the end grasping device of causing by film, can not make stable film sometimes.More preferably 15.0 〉=(Y-X)/Y * 100＞0.00.Preferred especially 10.0 〉=(Y-X)/Y * 100＞0.00.

In the present invention, the inlet of the heating furnace in (C) operation makes axis of orientation make towards the MD direction from the whole width at film and considers aspect the film, preferably makes the tension force of TD direction become no tension force basically and fixes.Inlet at heating furnace, make the tension force of TD direction become no tension force basically and fixedly carry, except above-mentioned (B) operation when the end of immobilized gel film, make the tension force of TD direction become no tension force basically and fix, the method (first method) that former state is sent into (C) operation in addition, can enumerate after (B) operation, once shorten the operation (mode of Fig. 1 record) of the distance of both ends stiff end, send into the method (second method) of (C) operation.First method preferably satisfies the method that formula is fixed (2) when the two ends of immobilized gel film, second method preferably satisfies the distance that formula shortens stiff end (2).

After carrying out first method or second method, enter the heating furnace of (C) operation after, can shorten the operation (third party's method) of distance of the distance of both ends stiff end again.In third party's method, shorten the both ends stiff end distance operation preferably smaller or equal to 300 ℃, more preferably smaller or equal to 250 ℃, carry out particularly preferably in temperature range smaller or equal to 200 ℃.Carried out for the 3rd when operation in the temperature province that is higher than 300 ℃, have the become tendency of difficulty of controlling diaphragm orientation, the orientation that particularly the exists in the film end unmanageable tendency that becomes.

In above the present application, before being about to apply temperature on the gel mould, the tension force of process TD direction is that tension-free state is important basically.

In (C) operation, because the film drying, and imidization reaction is carried out film generation contraction to a certain degree.Therefore, inlet at heating furnace, if make the tension force of TD direction fixedly carries with becoming no tension force basically, after this, because the film that heating causes shrinks, the film width diminishes, so both ends stiff end distance becomes identical with film width between the stiff end of both ends, can make the film that does not have wrinkle.

In the present invention, in (C) operation, can comprise (C-2) operation along TD direction stretched film.By further comprising this (C-2) operation, the degree of orientation that can controlling diaphragm.The so-called degree of orientation is the index of degree of orientation of the molecule of expression film.Below explanation is as the MOR and the MOR-c of degree of orientation use.When being configured as the test portion irradiating microwaves of membranaceous or sheet, the absorption intensity of microwave depends on the anisotropy of test portion.That is, measure microwave transmission intensity, can obtain the polar coordinates (orientation pattern) of intensity in transmission by omnirange at 360 °.The value that calculates from the ratio of polar major axis of this intensity in transmission and minor axis is MOR.In addition, among the present invention MOR is defined as the degree of orientation of expression molecularly oriented state.Moreover, can know the angle of orientation and anisotropic degree from above-mentioned orientation pattern.

The mensuration of MOR value can use prince's instrumentation machine system microwave molecularly oriented meter MOA2012A type to measure.

Moreover MOR-c is the value of MOR being carried out the thickness conversion.Because the degree of orientation is proportional to thickness, therefore will be converted into thickness 75 μ m with the MOR that this analyzer obtains with following formula (3), be defined as MOR-c.

MOR-c=(tc/t * (MOR-1))+1 formula (3)

Wherein, the thickness of t=test portion

The root thickness that tc=will revise (75 μ m)

The value that MOR=is obtained by said determination

The revised MOR of MOR-c=

In the above-mentioned formula, substitution 75 in tc, obtain revised MOR value.The value of the MOR-c that obtains, MOR-c is more near 1.000, and expression is the more little isotropic film of the degree of orientation.

The little film of approaching more isotropic degree of orientation can not have the difference of the physics value of MD direction and TD direction more, for example has the advantage that can produce the synthetic resin film that can not consider the service orientation of synthetic resin film and use.

Specifically, at the synthetic resin film of wanting to obtain the MD orientation, and when showing the synthetic resin film of the littler degree of orientation, can adopt the manufacture method that comprises (C-2) operation.

(C-2) among the present invention is through after (C-1) operation along the operation of TD direction stretched film, in heating furnace along the operation of TD direction stretched film.In (C-1) operation, the tension force of film width (TD direction) is fixedly carried with becoming no tension force basically, if but in heating furnace heating film, film will take place to shrink to a certain degree.Be make the lax forfeiture of film shrinking after, along TD direction stretched film.When amount of tension (being referred to as expansion rate for convenience) is Z (Fig. 1 11) at the width of the both ends stiff end of establishing the TD direction before stretching, the width of the both ends stiff end in stove during along TD direction stretched film is W (Fig. 1 12), preferably satisfy following formula.

40.0 〉=(W-Z)/Z * 100＞0.00 (formula 4)

If (W-Z)/Z * 100 (being referred to as the TD expansion rate for convenience sometimes) are increased to more than the above-mentioned scope, then the molecular orientation axis at the MD direction controling film becomes difficult sometimes.Be more preferably 30.0 〉=(W-Z)/Z * 100＞0.00.20.0 〉=(W-Z)/Z * 100＞0.00 especially preferably.

(C-2) operation can make the width of controlling of film little by little expand edge TD direction stretched film in the limit.As required, can also after (C-2) operation, shrink once more, also can make the expansion of film width again, about amount of contraction, extensive magnitude, preferably selected aptly.

Carry out the temperature of (C-2) operation, under the situation of the polyimide film of excellent heat resistance, because the elastic modelling quantity of polyimide film reduces, easy stretched film becomes, therefore be preferably greater than and equal 300 ℃ smaller or equal to 500 ℃, be preferably greater than especially and equal 350 ℃ smaller or equal to 480 ℃.Moreover under said temperature, film softens and extends sometimes.In the case, preferably set above-mentioned scope temperature in addition aptly.

Have again, in (C-2) operation,, can under the state of MD orientation, the degree of orientation of film be diminished by regulating the TD expansion rate.That is, by stretched film, the freely degree of orientation of controlling diaphragm in (C-2) operation.

In the present application, can regulate contraction and (C-2) film tension force, the remaining composition weight of gel mould, the heating-up temperature of the stretching in the operation and the MD direction when carrying in (C-1) operation aptly, make the film that orientation is controlled at the MD direction.In addition, when synthetic resin film is polyimide film, owing to carry out chemical imidizate or carry out hot-imide, the heating-up temperature of film, heat time heating time are different fully, even but during hot-imide,, also can access the required film of purpose if carry out control in the method for the present application.

The heating furnace that is adapted at using in the present application, use above film or below or from two towards the film integral spray more than or equal to 60 ℃ hot blast and the hot-blast stove of the mode that heats, perhaps shine far infrared and the far infrared line oven that possesses generating far infrared rays that film is burnt till.In heating process, the preferred stage temperature is risen and burn till, for this reason, preferably use hot-blast stove or far infrared line oven or make hot-blast stove and far infrared line oven mixing existence, the stage heating furnace that the linking number platform burns till.

In above-mentioned firing process in the present application, in the manufacturing process of polyimide film, controlling the heating-up temperature that at first give of gel mould when in stove, carrying, preferably smaller or equal to 300 ℃, more preferably greater than equaling 60 ℃ smaller or equal to 250 ℃, be preferably greater than especially and equal 100 ℃ smaller or equal to 200 ℃, the synthetic resin film aspect that orientation is controlled at the MD direction that is easy to get is calmly considered preferred.Specifically, preferably carry in more than or equal to a plurality of heating furnaces of 2, the temperature that makes first heating furnace (Fig. 1 2) is smaller or equal to 300 ℃.In addition, when being applied to other synthetic resin films, preferably considering the volatilization temperature of the kind of synthetic resin film and solvent and determine.The special boiling point of wishing to investigate the solvent that contains in the gel mould is managing than the temperature below the high 100 ℃ temperature of the boiling point of this solvent.

In the manufacturing of polyimide film, when the heating-up temperature that gives at first when carrying in stove is higher than 300 ℃, (because the influence of the contraction of film that bending phenomenon occurs, central portion is transported to inside heating furnace quickly than the end of film, therefore produce the phenomenon of strong molecularly oriented state in the end), exist along the tendency of the axis of orientation of the wayward film of MD direction end.When the burning till of polyimide film, the temperature of preferred No. 2 stove (Fig. 1 3) is set at the temperature more than 50 ℃ that is higher than No. 1 stove (Fig. 1 2), is higher than the temperature of No. 1 stove below 300 ℃.The temperature that be preferably set to the temperature more than 60 ℃ that is higher than No. 1 stove especially, is higher than No. 1 stove is below 250 ℃, along preferred aspect the molecular orientation axis of MD direction control polyimide film.Burn till under the temperature that the temperature of preferred stove is after this used in the manufacturing of common polyimide film.But, in the temperature of No. 1 stove (Fig. 1 2) during smaller or equal to 60 ℃, preferably the temperature of next stove (Fig. 1 3) is set at more than or equal to 100 ℃, smaller or equal to 250 ℃ temperature.During smaller or equal to 60 ℃, be set at said temperature by the temperature with No. 2 stoves in the temperature of No. 1 stove (Fig. 1 2), the manufacturing of the polyimide film of control molecular orientation axis just becomes possibility.In addition, the temperature of preferred initial stage temperature and next stove is set as described above, burns till under the firing temperature that preferred temperature is in addition used in the manufacturing of common polyimide film.For example,, in the burning till of polyimide film, can use and carry out the stage in the temperature that is up to 600 ℃ and burn till, be cooled to the method for room temperature etc. at leisure as the one example.Under the low situation of maximum sintering temperature, the imidizate rate is incomplete sometimes, just burns till fully to necessitate.

Bestow the tension force that gives on the MD direction of gel mould when carrying in stove, by calculating the tension force (load) that applies on every 1m film, preferably 1～20kg/m is more preferably 1～15kg/m, especially preferably 1～10kg/m., be difficult to film is stably carried during at tension force, exist and control film and make the become tendency of difficulty of stable film less than 1kg/m.In addition, the tension force on being applied to film especially is difficult to control molecularly oriented in the end of film along the MD direction during greater than 20kg/m, and the degree of orientation of film end becomes big than central part, exists to be controlled to be the become tendency of difficulty of the uniform degree of orientation of whole width.As the tension force generating means that on the gel mould of in stove, carrying, gives, use applies load roller, the dancer rools of load on gel mould rotary speed makes the roller of load variations, carries out the whole bag of tricks such as mode of the nip rolls of tension force control with 2 roller clamping gel moulds, can regulate the tension force to gel mould.

Moreover, give the tension force of film, preferably in above-mentioned scope, regulate aptly according to the thickness of polyimide film.As film thickness, 1～200 μ m preferably, 1～100 μ m especially preferably, form aspect the polyimide film preferred.At the thickness of film is 200 μ m when above, and it is big that the shrinkage stress that produces on the film becomes, even use the application's method, the degree of orientation of polyimide film can not be controlled at the MD direction sometimes, therefore not preferred.

If use method of the present invention, can access the synthetic resin film of molecule along MD direction orientation.Whether molecule can be confirmed with the molecularly oriented meter along MD direction orientation.The molecularly oriented of the film that is obtained by manufacture method of the present invention, when using the system molecularly oriented meter MOA2012A of prince's instrumentation machine Co., Ltd. to measure the orientation of film, angle of molecular orientation is preferably below 0 ± 25 °.So-called angle of molecular orientation is 0 °, means that molecular orientation axis is towards MD direction (the mechanical throughput direction of film).By molecular orientation axis being controlled in the above-mentioned scope, the elastic modelling quantity of MD direction improves, and the linear expansion coefficient value diminishes, and the dimensional stability of polyimide film improves.In addition, if surpass above-mentioned angular range, film becomes big at the linear expansion coefficient of incline direction, and unidirectional elastic modelling quantity also reduces, when therefore in the operation of the folded metal forming of limit heating film boundary layer, using, the change in size amount of incline direction (formation figure front and back, FPC heat front and back) becomes big, the dimensional stability reduction, so not preferred.

In addition, if use manufacture method of the present invention, can access the synthetic resin film that molecule is orientated along the MD direction on whole width.Molecule as shown in Figure 3, for the film of film width more than or equal to 800mm, comprises that two ends are uniformly-spaced to take 7 samples at least along the state of MD direction orientation on the whole width of so-called film in the present application.The film width comprises that less than the film of 800mm two ends are uniformly-spaced to take 5 samples at least.Though this method is not strictly measured on whole width, if but angle of molecular orientation satisfies below 0 ± 25 ° in whole samples of taking like this, when strictly on whole width, measuring sample, be also referred to as the satisfied film below 0 ± 25 ° of angle of molecular orientation.

Synthetic resin film among the present invention on the one side or two sides of the synthetic resin film that is obtained by manufacture method of the present invention, can be coated with more than or equal to other polymeric layers of 1 layer and uses.For example can directly or make layer such as adhesive between the stacked TPI in centre, polyester, polyolefin, polyamide, Vingon and acrylic polymer.In addition, when being polyimide film, for example can be to utilize simultaneously more than or equal to the coating simultaneously on supporting body surface of 1 slit mouth to be used to form the solution (contain thermoplastic polyimide resin or as the solution of the polyamic acid of its precursor) of thermoplastic polyimide layer and to be used to form the solution (containing solution) of heat resistant poly imide layer, the form that the making gel mould burns till as the polyamic acid of the precursor of heat resistant poly imide resin.

In addition, in the manufacture method of synthetic resin film of the present invention, also can be coated with the high-molecular resin solution of wanting the curtain coating coating successively overlappingly, can make the duplexer of synthetic resin film more than or equal to 1 layer of while or on supporter.Have again, when being polyimide film, after making the gel mould of polyimides, can with adopt in polyamic acid solution impregnated membranes or in imide solution dipping or use the method for coating machine at the surface of film coating polyamic acid solution or polyimide solution, the mode that the polyimides gel mould of making burns till is made film.

By the synthetic resin film that manufacture method of the present invention obtains, can heat-treat as required, processing arbitrarily such as shaping, surface treatment, stacked, coating, printing, embossing processing, etching.

The purposes of the synthetic resin film that obtains by manufacture method of the present invention, there is no particular restriction, but be particularly suitable for flexible printed circuit board purposes, TAB with belt base plate or high-density recording media with electric/electronic device substrate purposes, magnetic recording media purposes, electric insulation purposes etc. such as basement membranes.

Below, use embodiment to specifically describe the present invention, but the present invention is not limited only to these embodiment.The present application is put down in writing the embodiment in the manufacture method of polyimide film especially.

[embodiment]

(Determination of Modulus)

Use the method as benchmark with the 6.3.3 of JIS C2318, utilize the MD direction (throughput direction of film) of central part of the film that Shimadzu Corporation system AUTOGRAPH (model AGS-J) mensuration obtains and the elastic modelling quantity of TD direction (perpendicular to the direction of MD direction), use following calculating formula to obtain the elastic modelling quantity of film by the Determination of Modulus result of MD direction and TD direction.

The elastic modelling quantity of film=((elastic modelling quantity of MD direction)+(elastic modelling quantity of TD direction)) ÷ 2 (formula 5)

(mensuration of the degree of orientation, the angle of orientation)

As shown in Figure 3, for the film of film width, comprise that two ends are uniformly-spaced to take 7 samples at least more than or equal to 800mm.The film width comprises that less than the film of 800mm two ends are uniformly-spaced to take 5 samples at least.Use prince's instrumentation machine system microwave molecularly oriented meter MOA2012A type to measure this sample, obtain the degree of orientation and the angle of orientation of film.

(embodiment 1)

In the present embodiment, at N, in the dinethylformamide (DMF) with 50mol%4,4 '-diaminodiphenyl ether (ODA), 50mol% p-phenylenediamine (PPD) (p-PDA), 50mol% TOPOT 2,2 (trimellitic acid monoesters acid anhydrides) (TMHQ), the ratio of 50mol% pyromellitic acid anhydride (PMDA) adds in proper order by this and carries out polymerization, the synthesizing polyamides acid solution.In this polyamic acid solution, add the acetic anhydride of 2.0 times of equivalents and the isoquinolin of 1.0 times of equivalents with respect to the amic acid equivalent, with the thickness that becomes 20 μ m after burning till, with 1100mm width curtain coating on the endless belt, carry out heated-air drying under 100 ℃～150 ℃, the remaining component ratio that obtains having self-supporting is the gel mould of 54 weight %.After this, peel off from belt.As tension force, on the gel mould of peeling off, the MD direction applied to be transported in the Tenter oven under the state of tension force of 8kg/m and burn till.Moreover, in the present embodiment, burn till by 175 ℃ hot-air ovens (below be also referred to as 175 ℃ of stoves), 325 ℃ hot-air oven (below be also referred to as 325 ℃ of stoves), 450 ℃ hot-air oven (below be also referred to as 450 ℃ of stoves), 510 ℃ far infrared line oven (below be also referred to as 510 ℃ of far infrared line ovens).Gel mould, there are not loosely the fixedly both ends of TD direction with the wide 1000mm of pin, the limit is carried between the stiff end of gel mould limit with the stove inlet and is set at 956mm (gel mould width 1000mm), to be set at 956mm between the stiff end between 175 ℃ of stoves and the 325 ℃ of stoves, to be set at 956mm between the stiff end between 325 ℃ of stoves and the 450 ℃ of stoves, be set at 956mm between stiff end with the outlet of 510 ℃ of far infrared line ovens, be set at 956mm between the stiff end with outlet of still, polyimide film is made in the inside that polyimide film is transported to stove.Polyimide film carries out end cut unloading when fixedly batching, and obtains the wide film of 940mm.Measure the angle of orientation, the degree of orientation of the polyimide film of making like this.Experimental result is documented in table 1, the table 2.From the measurement result of molecular orientation axis as can be known, the angle that can be produced on molecular orientation axis on the whole width of film is controlled in 0 ± 25 ° MD orientation polyimide film.The elastic modelling quantity of the polyimide film that obtains is 6.0GPa.

(embodiment 2)

Mix the polyamic acid solution that uses in the present embodiment 1 and with the acetic anhydride and the isoquinolin of embodiment 1 equivalent, with the thickness that becomes 20 μ m after burning till, with 1100mm width curtain coating on the endless belt, carry out heated-air drying under 100 ℃～150 ℃, the remaining component ratio that obtains having self-supporting is the gel mould of 54 weight %.After this, peel off from belt.As tension force, on the gel mould of peeling off, the MD direction applied to be transported in the Tenter oven under the state of tension force of 8kg/m and burn till.Moreover, in the present embodiment, burn till by 190 ℃ hot-air ovens (below be also referred to as 190 ℃ of stoves), 400 ℃ hot-air oven (below be also referred to as 400 ℃ of stoves), 450 ℃ hot-air oven, 510 ℃ far infrared line oven.Gel mould, there are not loosely the fixedly both ends of TD direction with the wide 1000mm of pin, the limit is carried between the stiff end of gel mould limit with the stove inlet and is set at 956mm (gel mould width 1000mm), to be set at 956mm between the stiff end between 190 ℃ of stoves and the 400 ℃ of stoves, to be set at 956mm between the stiff end between 400 ℃ of stoves and the 450 ℃ of stoves, be set at 956mm between stiff end with the outlet of 510 ℃ of far infrared line ovens, be set at 956mm between the stiff end with outlet of still, polyimide film is made in the inside that polyimide film is transported to stove.Polyimide film carries out end cut unloading when fixedly batching, and obtains the wide film of 940mm.Measure the angle of orientation, the degree of orientation of the polyimide film of making like this.Experimental result is documented in table 1, the table 2.From the measurement result of molecular orientation axis as can be known, the angle that can be produced on molecular orientation axis on the whole width of film is controlled in 0 ± 25 ° MD orientation polyimide film.The elastic modelling quantity of the polyimide film that obtains is 6.0GPa.

(embodiment 3)

Mix the polyamic acid solution that uses in the present embodiment 1 and with the acetic anhydride and the isoquinolin of embodiment 1 equivalent, with the thickness that becomes 20 μ m after burning till, with 820mm width curtain coating on the endless belt, carry out heated-air drying under 100 ℃～120 ℃, the remaining component ratio that obtains having self-supporting is the gel mould of 60 weight %.After this, peel off from belt.As tension force, on the gel mould of peeling off, the MD direction applied to be transported in the Tenter oven under the state of tension force of 2kg/m and burn till.Moreover, in the present embodiment, burn till by 130 ℃ hot-air ovens (below be also referred to as 130 ℃ of stoves), 260 ℃ hot-air oven (below be also referred to as 260 ℃ of stoves), 360 ℃ hot-air oven (below be also referred to as 360 ℃ of stoves), 450 ℃ hot-air oven, 515 ℃ far infrared line oven (below be also referred to as 515 ℃ of far infrared line ovens).Gel mould, there are not loosely the fixedly both ends of TD direction with the wide 800mm of pin, the limit is carried between the stiff end of gel mould limit with the stove inlet and is set at 769mm (gel mould width 800mm), to be set at 769mm between the stiff end between 130 ℃ of stoves and the 260 ℃ of stoves, to be set at 769mm between the stiff end between 260 ℃ of stoves and the 360 ℃ of stoves, to be set at 769mm between the stiff end between 360 ℃ and 450 ℃ of stoves, be set at 769mm between stiff end with the outlet of 515 ℃ of far infrared line ovens, be set at 769mm between the stiff end with outlet of still, polyimide film is made in the inside that polyimide film is transported to stove.Polyimide film carries out end cut unloading when fixedly batching, and obtains the wide film of 740mm.Measure the angle of orientation, the degree of orientation of the polyimide film of making like this.Experimental result is documented in table 1, the table 2.From the measurement result of molecular orientation axis as can be known, the angle that can be produced on molecular orientation axis on the whole width of film is controlled in 0 ± 25 ° MD orientation polyimide film.The elastic modelling quantity of the polyimide film that obtains is 6.1GPa.

(embodiment 4)

Mix the polyamic acid solution that uses in the present embodiment 1 and with the acetic anhydride and the isoquinolin of embodiment 1 equivalent, with the thickness that becomes 20 μ m after burning till, with 850mm width curtain coating on the endless belt, carry out heated-air drying under 100 ℃～120 ℃, the remaining component ratio that obtains having self-supporting is the gel mould of 60 weight %.After this, peel off from belt.As tension force, on the gel mould of peeling off, the MD direction applied to be transported in the Tenter oven under the state of tension force of 2kg/m and burn till.Moreover, in the present embodiment, burn till by 130 ℃ hot-air ovens, 260 ℃ hot-air oven, 360 ℃ hot-air oven, 450 ℃ hot-air oven, 515 ℃ far infrared line oven.Gel mould, there are not loosely the fixedly both ends of TD direction with the wide 820mm of pin, the limit is carried between the stiff end of gel mould limit with the stove inlet and is set at 765mm (gel mould width 820mm), to be set at 765mm between the stiff end between 130 ℃ of stoves and the 260 ℃ of stoves, to be set at 765mm between the stiff end between 260 ℃ of stoves and 360 ℃ of stoves, to be set at 765mm between the stiff end between 360 ℃ and the 450 ℃ of stoves, be set at 765mm between stiff end with the outlet of 515 ℃ of far infrared line ovens, be set at 765mm between the stiff end with outlet of still, polyimide film is made in the inside that polyimide film is transported to stove.Polyimide film carries out end cut unloading when fixedly batching, and obtains the wide film of 740mm.Measure the angle of orientation, the degree of orientation of the polyimide film of making like this.Experimental result is documented in table 1, the table 2.From the measurement result of molecular orientation axis as can be known, the angle that can be produced on molecular orientation axis on the whole width of film is controlled in 0 ± 25 ° MD orientation polyimide film.The elastic modelling quantity of the polyimide film that obtains is 6.1GPa.

(embodiment 5)

Mix the polyamic acid solution that uses in the present embodiment 1 and with the acetic anhydride and the isoquinolin of embodiment 1 equivalent, with the thickness that becomes 20 μ m after burning till, with 1100mm width curtain coating on the endless belt, carry out heated-air drying under 100 ℃～150 ℃, the remaining component ratio that obtains having self-supporting is the gel mould of 54 weight %.After this, peel off from belt.As tension force, on the gel mould of peeling off, the MD direction applied to be transported in the Tenter oven under the state of tension force of 4kg/m and burn till.Moreover, in the present embodiment, burn till by 160 ℃ hot-air ovens, 300 ℃ hot-air oven, 400 ℃ hot-air oven, 510 ℃ far infrared line oven.Gel mould, there are not loosely the fixedly both ends of TD direction with the wide 1000mm of pin, the limit is carried between the stiff end of gel mould limit with the stove inlet and is set at 970mm (gel mould width 1000mm), to be set at 970mm between the stiff end between 160 ℃ of stoves and the 300 ℃ of stoves, to be set at 970mm between the stiff end between 300 ℃ of stoves and the 400 ℃ of stoves, be set at 970mm between stiff end with the outlet of 510 ℃ of far infrared line ovens, be set at 970mm between the stiff end with outlet of still, polyimide film is made in the inside that polyimide film is transported to stove.Polyimide film carries out end cut unloading when fixedly batching, and obtains the wide film of 940mm.Measure the angle of orientation, the degree of orientation of the polyimide film of making like this.Experimental result is documented in table 1, the table 2.From the measurement result of molecular orientation axis as can be known, the angle that can be produced on molecular orientation axis on the whole width of film is controlled in 0 ± 25 ° MD orientation polyimide film.The elastic modelling quantity of the polyimide film that obtains is 5.9GPa.

(embodiment 6)

Mix the polyamic acid solution that uses in the present embodiment 1 and with the acetic anhydride and the isoquinolin of embodiment 1 equivalent, with the thickness that becomes 20 μ m after burning till, with 1100mm width curtain coating on the endless belt, carry out heated-air drying under 100 ℃～150 ℃, the remaining component ratio that obtains having self-supporting is the gel mould of 54 weight %.After this, peel off from belt.As tension force, on the gel mould of peeling off, the MD direction applied to be transported in the Tenter oven under the state of tension force of 5kg/m and burn till.Moreover, in the present embodiment, burn till by 160 ℃ hot-air ovens (below be also referred to as 160 ℃ of stoves), 300 ℃ hot-air oven, 400 ℃ hot-air oven, 510 ℃ far infrared line oven.Gel mould, there are not loosely the fixedly both ends of TD direction with the wide 1000mm of pin, the limit is carried between the stiff end of gel mould limit with the stove inlet and is set at 960mm (gel mould width 1000mm), to be set at 960mm between the stiff end between 160 ℃ of stoves and the 300 ℃ of stoves, to be set at 960mm between the stiff end between 300 ℃ of stoves and the 400 ℃ of stoves, be set at 960mm between stiff end with the outlet of 510 ℃ of far infrared line ovens, be set at 960mm between the stiff end with outlet of still, polyimide film is made in the inside that polyimide film is transported to stove.Polyimide film carries out end cut unloading when fixedly batching, and obtains the wide film of 940mm.Measure the angle of orientation, the degree of orientation of the polyimide film of making like this.Experimental result is documented in table 1, the table 2.From the measurement result of molecular orientation axis as can be known, the angle that can be produced on molecular orientation axis on the whole width of film is controlled in 0 ± 25 ° MD orientation polyimide film.The elastic modelling quantity of the polyimide film that obtains is 5.9GPa.

(embodiment 7)

Mix the polyamic acid solution that uses in the present embodiment 1 and with the acetic anhydride and the isoquinolin of embodiment 1 equivalent, with the thickness that becomes 20 μ m after burning till, with 1100mm width curtain coating on the endless belt, carry out heated-air drying under 100 ℃～150 ℃, the remaining component ratio that obtains having self-supporting is the gel mould of 54 weight %.After this, peel off from belt.As tension force, on the gel mould of peeling off, the MD direction applied to be transported in the Tenter oven under the state of tension force of 6kg/m and burn till.Moreover, in the present embodiment, burn till by 160 ℃ hot-air ovens, 300 ℃ hot-air oven, 400 ℃ hot-air oven, 510 ℃ far infrared line oven.Gel mould, there are not loosely the fixedly both ends of TD direction with the wide 1000mm of pin, the limit is carried between the stiff end of gel mould limit with the stove inlet and is set at 960mm (gel mould width 1000mm), to be set at 960mm between the stiff end between 160 ℃ of stoves and the 300 ℃ of stoves, to be set at 960mm between the stiff end between 300 ℃ of stoves and the 400 ℃ of stoves, be set at 960mm between stiff end with the outlet of 510 ℃ of far infrared line ovens, be set at 960mm between the stiff end with outlet of still, polyimide film is made in the inside that polyimide film is transported to stove.Polyimide film carries out end cut unloading when fixedly batching, and obtains the wide film of 940mm.Measure the angle of orientation, the degree of orientation of the polyimide film of making like this.Experimental result is documented in table 1, the table 2.From the measurement result of molecular orientation axis as can be known, the angle that can be produced on molecular orientation axis on the whole width of film is controlled in 0 ± 25 ° MD orientation polyimide film.The elastic modelling quantity of the polyimide film that obtains is 5.9GPa.

(embodiment 8)

Mix the polyamic acid solution that uses in the present embodiment 1 and with the acetic anhydride and the isoquinolin of embodiment 1 equivalent, with the thickness that becomes 20 μ m after burning till, with 1100mm width curtain coating on the endless belt, carry out heated-air drying under 100 ℃～150 ℃, the remaining component ratio that obtains having self-supporting is the gel mould of 54 weight %.After this, peel off from belt.As tension force, on the gel mould of peeling off, the MD direction applied to be transported in the Tenter oven under the state of tension force of 8kg/m and burn till.Moreover, in the present embodiment, burn till by 160 ℃ hot-air ovens, 300 ℃ hot-air oven, 400 ℃ hot-air oven, 510 ℃ far infrared line oven.Gel mould, there are not loosely the fixedly both ends of TD direction with the wide 1000mm of pin, the limit is carried between the stiff end of gel mould limit with the stove inlet and is set at 960mm (gel mould width 1000mm), to be set at 960mm between the stiff end between 160 ℃ of stoves and the 300 ℃ of stoves, to be set at 960mm between the stiff end between 300 ℃ of stoves and the 400 ℃ of stoves, be set at 960mm between stiff end with the outlet of 510 ℃ of far infrared line ovens, be set at 960mm between the stiff end with outlet of still, polyimide film is made in the inside that polyimide film is transported to stove.Polyimide film carries out end cut unloading when fixedly batching, and obtains the wide film of 940mm.Measure the angle of orientation, the degree of orientation of the polyimide film of making like this.Experimental result is documented in table 1, the table 2.From the measurement result of molecular orientation axis as can be known, the angle that can be produced on molecular orientation axis on the whole width of film is controlled in 0 ± 25 ° MD orientation polyimide film.The elastic modelling quantity of the polyimide film that obtains is 6.0GPa.

(embodiment 9)

In the present embodiment, at N, in the dinethylformamide (DMF) with 75mol%4,4 '-ratio of diaminodiphenyl ether (ODA), 25mol% p-phenylenediamine (PPD) (p-PDA), 100mol% pyromellitic acid anhydride (PMDA) adds in proper order by this and carries out polymerization, the synthesizing polyamides acid solution.In this polyamic acid solution, add the acetic anhydride of 2.0 times of equivalents and the isoquinolin of 1.0 times of equivalents with respect to the amic acid equivalent, with the thickness that becomes 20 μ m after burning till, with 1100mm width curtain coating on the endless belt, carry out heated-air drying under 100 ℃～150 ℃, the remaining component ratio that obtains having self-supporting is the gel mould of 54 weight %.After this, peel off from belt.As tension force, on the gel mould of peeling off, the MD direction applied to be transported in the Tenter oven under the state of tension force of 8kg/m and burn till.Moreover, in the present embodiment, burn till by 175 ℃ hot-air ovens, 325 ℃ hot-air oven, 450 ℃ hot-air oven, 510 ℃ far infrared line oven.Gel mould, there are not loosely the fixedly both ends of TD direction with the wide 1000mm of pin, the limit is carried between the stiff end of gel mould limit with the stove inlet and is set at 956mm (gel mould width 1000mm), to be set at 956mm between the stiff end between 175 ℃ of stoves and the 325 ℃ of stoves, to be set at 956mm between the stiff end between 325 ℃ of stoves and the 450 ℃ of stoves, be set at 956mm between stiff end with the outlet of 510 ℃ of far infrared line ovens, be set at 956mm between the stiff end with outlet of still, polyimide film is made in the inside that polyimide film is transported to stove.Polyimide film carries out end cut unloading when fixedly batching, and obtains the wide film of 940mm.Measure the angle of orientation, the degree of orientation of the polyimide film of making like this.Experimental result is documented in table 1, the table 2.From the measurement result of molecular orientation axis as can be known, the angle that can be produced on molecular orientation axis on the whole width of film is controlled in 0 ± 25 ° MD orientation polyimide film.The elastic modelling quantity of the polyimide film that obtains is 4.2GPa.Even the kind of change polyimide film is if the elastic modelling quantity of polyimide film more than or equal to the polyimide film of 4.0GPa, also can be made along the polyimide film of MD direction orientation.

(embodiment 10)

In the present embodiment, at N, in the dinethylformamide (DMF) with 45mol%4,4 '-diaminodiphenyl ether (ODA), 55mol% p-phenylenediamine (PPD) (p-PDA), 80mol% pyromellitic acid anhydride (PMDA), 20mol%3,3 ', 4,4 '-ratio of biphenyl tetracarboxylic dianhydride adds in proper order by this and carries out polymerization, the synthesizing polyamides acid solution.In this polyamic acid solution, add the acetic anhydride of 2.0 times of equivalents and the isoquinolin of 1.0 times of equivalents with respect to the amic acid equivalent, with the thickness that becomes 20 μ m after burning till, with 1100mm width curtain coating on the endless belt, carry out heated-air drying under 100 ℃～150 ℃, the remaining component ratio that obtains having self-supporting is the gel mould of 54 weight %.After this, peel off from belt.As tension force, on the gel mould of peeling off, the MD direction applied to be transported in the Tenter oven under the state of tension force of 8kg/m and burn till.Moreover, in the present embodiment, burn till by 175 ℃ hot-air ovens, 325 ℃ hot-air oven, 450 ℃ hot-air oven, 510 ℃ far infrared line oven.Gel mould, there are not loosely the fixedly both ends of TD direction with the wide 1000mm of pin, the limit is carried between the stiff end of gel mould limit with the stove inlet and is set at 956mm (gel mould width 1000mm), to be set at 956mm between the stiff end between 175 ℃ of stoves and the 325 ℃ of stoves, to be set at 956mm between the stiff end between 325 ℃ of stoves and the 450 ℃ of stoves, be set at 956mm between stiff end with the outlet of 510 ℃ of far infrared line ovens, be set at 956mm between the stiff end with outlet of still, polyimide film is made in the inside that polyimide film is transported to stove.Polyimide film carries out end cut unloading when fixedly batching, and obtains the wide film of 940mm.Measure the angle of orientation, the degree of orientation of the polyimide film of making like this.Experimental result is documented in table 1, the table 2.From the measurement result of molecular orientation axis as can be known, the angle that can be produced on molecular orientation axis on the whole width of film is controlled in 0 ± 25 ° MD orientation polyimide film.The elastic modelling quantity of the polyimide film that obtains is 5.5GPa.Even the kind of change polyimide film is if the elastic modelling quantity of polyimide film more than or equal to the polyimide film of 4.0GPa, can be made along the polyimide film of MD direction orientation.

(embodiment 11)

Mix the polyamic acid solution that uses in the present embodiment 1 and with the acetic anhydride and the isoquinolin of embodiment 1 equivalent, with the thickness that becomes 20 μ m after burning till, with 1100mm width curtain coating on the endless belt, carry out heated-air drying under 100 ℃～140 ℃, the remaining component ratio that obtains having self-supporting is the gel mould of 28 weight %.After this, peel off from belt.As tension force, on the gel mould of peeling off, the MD direction applied to be transported in the Tenter oven under the state of tension force of 8kg/m and burn till.Moreover, firing condition, the firing time in each stove burns till by 175 ℃ hot-air ovens, 325 ℃ hot-air oven, 450 ℃ hot-air oven, 510 ℃ far infrared line oven.Gel mould, there are not loosely the fixedly both ends of TD direction with the wide 1000mm of pin, the limit is carried between the stiff end of gel mould limit with the stove inlet and is set at 956mm (gel mould width 1000mm), to be set at 956mm between the stiff end between 175 ℃ of stoves and the 325 ℃ of stoves, to be set at 956mm between the stiff end between 325 ℃ of stoves and the 450 ℃ of stoves, be set at 956mm between stiff end with the outlet of 510 ℃ of far infrared line ovens, be set at 956mm between the stiff end with outlet of still, polyimide film is made in the inside that polyimide film is transported to stove.Polyimide film carries out end cut unloading when fixedly batching, and obtains the wide film of 940mm.Measure the angle of orientation, the degree of orientation of the polyimide film of making like this.Experimental result is documented in table 1, the table 2.The elastic modelling quantity of the polyimide film that obtains is 6.2GPa.

(embodiment 12)

Mix the polyamic acid solution that uses in the present embodiment 1 and with the acetic anhydride and the isoquinolin of embodiment 1 equivalent, with the thickness that becomes 20 μ m after burning till, with 1100mm width curtain coating on the endless belt, carry out heated-air drying under 100 ℃～120 ℃, the remaining component ratio that obtains having self-supporting is the gel mould of 107 weight %.After this, peel off from belt.As tension force, on the gel mould of peeling off, the MD direction applied to be transported in the Tenter oven under the state of tension force of 3kg/m and burn till.Moreover, firing condition, the firing time in each stove burns till by 175 ℃ hot-air ovens, 325 ℃ hot-air oven, 450 ℃ hot-air oven, 510 ℃ far infrared line oven.Gel mould, there are not loosely the fixedly both ends of TD direction with the wide 1000mm of pin, the limit is carried between the stiff end of gel mould limit with the stove inlet and is set at 956mm (gel mould width 1000mm), to be set at 956mm between the stiff end between 175 ℃ of stoves and the 325 ℃ of stoves, to be set at 956mm between the stiff end between 325 ℃ of stoves and the 450 ℃ of stoves, be set at 956mm between stiff end with the outlet of 510 ℃ of far infrared line ovens, be set at 956mm between the stiff end with outlet of still, polyimide film is made in the inside that polyimide film is transported to stove.Polyimide film carries out end cut unloading when fixedly batching, and obtains the wide film of 940mm.Measure the angle of orientation, the degree of orientation of the polyimide film of making like this.Experimental result is documented in table 1, the table 2.The elastic modelling quantity of the polyimide film that obtains is 5.8GPa.

(embodiment 13)

Mix the polyamic acid solution that uses in the present embodiment 1 and with the acetic anhydride and the isoquinolin of embodiment 1 equivalent, with the thickness that becomes 20 μ m after burning till, with 900mm width curtain coating on the endless belt, carry out heated-air drying under 100 ℃～120 ℃, the remaining component ratio that obtains having self-supporting is the gel mould of 60 weight %.After this, peel off from belt.As tension force, on the gel mould of peeling off, the MD direction applied to be transported in the Tenter oven under the state of tension force of 2kg/m and burn till.Moreover, in the present embodiment, burn till by 130 ℃ hot-air ovens, 260 ℃ hot-air oven, 360 ℃ of hot-air ovens, 450 ℃ hot-air oven, 515 ℃ far infrared line oven.Gel mould, with the wide 820mm of pin, the width 860mm of gel mould, the fixing both ends of TD direction under relaxed state, the limit is carried between the stiff end of gel mould limit with the stove inlet and is set at 820mm, to be set at 820mm between the stiff end between 130 ℃ of stoves and the 260 ℃ of stoves, to be set at 820mm between the stiff end between 260 ℃ and the 360 ℃ of stoves, to be set at 820mm between the stiff end between 360 ℃ and the 450 ℃ of stoves, be set at 820mm between stiff end with the outlet of 515 ℃ of far infrared line ovens, be set at 820mm between the stiff end with outlet of still, polyimide film is made in the inside that polyimide film is transported to stove.Polyimide film carries out end cut unloading when fixedly batching, and obtains the wide film of 740mm.Measure the angle of orientation, the degree of orientation of the polyimide film of making like this.Experimental result is documented in table 1, the table 2.From the measurement result of molecular orientation axis as can be known, the angle that can be produced on molecular orientation axis on the whole width of film is controlled in 0 ± 25 ° MD orientation polyimide film.The elastic modelling quantity of the polyimide film that obtains is 6.0GPa.

(embodiment 14)

In the present embodiment, at N, dissolving 30mol%2 in the dinethylformamide (DMF), two [4-(4-amino-benzene oxygen) phenyl] propane (BAPP) and the 20mol%4 of 2-, 4 '-diaminodiphenyl ether (ODA).Add 20mol%3 therein, 3 ', 4,4 '-after biphenyl tetracarboxylic dianhydride makes its dissolving, make 35mol% pyromellitic acid anhydride (PMDA) dissolving.In this solution, add in proper order by this with the ratio of 50mol% p-phenylenediamine (PPD) (p-PDA), 45mol% pyromellitic acid anhydride (PMDA) and to carry out polymerization, the synthesizing polyamides acid solution.In this polyamic acid solution, add the acetic anhydride of 2.3 times of equivalents and the isoquinolin of 0.5 times of equivalent with respect to the amic acid equivalent, with the thickness that becomes 20 μ m after burning till, with 820mm width curtain coating on the endless belt, carry out heated-air drying under 100 ℃～130 ℃, the remaining component ratio that obtains having self-supporting is the gel mould of 75 weight %.After this, peel off from belt.As tension force, on the gel mould of peeling off, the MD direction applied to be transported in the Tenter oven under the state of tension force of 6kg/m and burn till.Gel mould does not have loosely the both ends of fixed width direction (gel mould width 800mm) with the wide 800mm of pin.This gel mould carries out stage the burning till of 130 ℃ (hot-air ovens), 260 ℃ (hot-air oven), 360 ℃ (hot-air oven), 450 ℃ (hot-air oven), 515 ℃ (far infrared line ovens), burns till to be polyimide film.The TD shrinkage factor becomes 3.9 in order to make, the TD expansion rate becomes 0.0, and edge TD direction makes the lax stretching limit of polyimide film carry out the conveying of film.Begin to shrink at the contraction of TD direction pin fixed position, make to shrink at the inlet of 130 ℃ of stoves and finish from gel mould.Polyimide film carries out end cut unloading when fixedly batching, and obtains the wide film of 740mm.The elastic modelling quantity of the polyimide film that obtains is 6.7GPa.The angle of orientation of the polyimide film that obtains like this, the mensuration of the degree of orientation.Experimental result is documented in table 1, the table 2.From the measurement result of molecular orientation axis as can be known, the angle that can be produced on molecular orientation axis on the whole width of film is controlled in 0 ± 25 ° MD orientation polyimide film.

(embodiment 15)

In the present embodiment, at N, in the dinethylformamide (DMF) with 50mol%4,4 '-diaminodiphenyl ether (ODA), 50mol% p-phenylenediamine (PPD) (p-PDA), 50mol% TOPOT 2,2 (trimellitic acid monoesters acid anhydrides) (TMHQ), the ratio of 50mol% pyromellitic acid anhydride (PMDA) adds in proper order by this and carries out polymerization, the synthesizing polyamides acid solution.In this polyamic acid solution, add the acetic anhydride of 2.0 times of equivalents and the isoquinolin of 1.0 times of equivalents with respect to the amic acid equivalent, with the thickness that becomes 20 μ m after burning till, with 820mm width curtain coating on the endless belt, carry out heated-air drying under 100 ℃～130 ℃, the remaining component ratio that obtains having self-supporting is the gel mould of 60 weight %.After this, peel off from belt.As tension force, on the gel mould of peeling off, the MD direction applied to be transported in the Tenter oven under the state of tension force of 2kg/m and burn till.Gel mould does not have loosely fixed width direction two ends (gel mould width 800mm) with the wide 800mm of pin.This gel mould carries out stage the burning till of 130 ℃ (hot-air ovens), 260 ℃ (hot-air oven), 360 ℃ (hot-air oven), 450 ℃ (hot-air oven), 515 ℃ (far infrared line ovens).Burn till and be polyimide film.The TD shrinkage factor becomes 3.9 in order to make, the TD expansion rate becomes 4.1, and edge TD direction makes the polyimide film stretching limit that relaxes carry out the conveying of film.In the contraction of TD direction, begin to shrink from the pin fixed position of gel mould, make to shrink at the inlet of 130 ℃ of stoves and finish.The stretching of TD direction stretches since the inlet of 450 ℃ of stoves, finishes stretching in the outlet of 450 ℃ of stoves.Polyimide film carries out end cut unloading when fixedly batching, and obtains the wide film of 740mm.The elastic modelling quantity of the polyimide film that obtains is 6.1GPa.

The angle of orientation of the polyimide film that obtains like this, the mensuration of the degree of orientation.Experimental result is documented in table 1, the table 2.From the measurement result of molecular orientation axis as can be known, the angle that can be produced on molecular orientation axis on the whole width of film is controlled in 0 ± 25 ° MD orientation polyimide film.

(embodiment 16)

The TD shrinkage factor is 2.0 except making, the TD expansion rate is 4.0, uses the manufacture method identical with embodiment 15 to make polyimide film.Polyimide film carries out end cut unloading when fixedly batching, and obtains the film of 740mm width.The elastic modelling quantity of the polyimide film that obtains is 6.0GPa.

The angle of orientation of the polyimide film that obtains like this, the mensuration of the degree of orientation.Experimental result is documented in table 1, the table 2.From the measurement result of molecular orientation axis as can be known, the angle that can be produced on molecular orientation axis on the whole width of film is controlled in 0 ± 25 ° MD orientation polyimide film.

(embodiment 17)

In the polyamic acid solution identical with present embodiment 15, with respect to the amic acid equivalent, add the acetic anhydride of 2.0 times of equivalents and the isoquinolin of 1.0 times of equivalents, with the thickness that becomes 20 μ m after burning till, with 1200mm width curtain coating on the endless belt, carry out heated-air drying under 100 ℃～140 ℃, the remaining component ratio that obtains having self-supporting is the gel mould of 54 weight %.After this, peel off from belt.As tension force, on the gel mould of peeling off, the MD direction applied to be transported in the Tenter oven under the state of tension force of 8kg/m and burn till.Gel mould does not have fixed width direction two ends loosely with the wide 1100mm of pin (gel mould width 1100mm).This gel mould is carried out stage the burning till of 175 ℃ (hot-air ovens), 300 ℃ (hot-air oven), 450 ℃ (hot-air oven), 515 ℃ (far infrared line ovens), burn till and be polyimide film.The TD shrinkage factor becomes 4.4 in order to make, the TD expansion rate becomes 2.3, and edge TD direction makes the polyimide film stretching limit that relaxes carry out the conveying of film.In the contraction of TD direction, begin to shrink from the pin fixed position of gel mould, make to shrink at the inlet of 175 ℃ of stoves and finish.The stretching of TD direction stretches since the inlet of 450 ℃ of stoves, in the outlet end stretching of 450 ℃ of stoves.Polyimide film carries out end cut unloading when fixedly batching, and obtains the wide film of 940mm.

The angle of orientation of the polyimide film that obtains like this, the mensuration of the degree of orientation.Experimental result is documented in table 1, the table 2.The elastic modelling quantity of the polyimide film that obtains is 6.0GPa.From the measurement result of molecular orientation axis as can be known, the angle that can be produced on molecular orientation axis on the whole width of film is controlled in 0 ± 25 ° MD orientation polyimide film.

(embodiment 18)

The TD shrinkage factor is 4.4 except making, the TD expansion rate is 4.6, uses the manufacture method identical with embodiment 17 to make polyimide film.Polyimide film carries out end cut unloading when fixedly batching, and obtains the wide film of 940mm.The elastic modelling quantity of the polyimide film that obtains is 5.9GPa.

The angle of orientation of the polyimide film that obtains like this, the mensuration of the degree of orientation.Experimental result is documented in table 1, the table 2.From the measurement result of molecular orientation axis as can be known, the angle that can be produced on molecular orientation axis on the whole width of film is controlled in 0 ± 25 ° MD orientation polyimide film.

(embodiment 19)

In the polyamic acid solution identical with present embodiment 14, with respect to the amic acid equivalent, add the acetic anhydride of 2.0 times of equivalents and the isoquinolin of 1.0 times of equivalents, with the thickness that becomes 20 μ m after burning till, with 1200mm width curtain coating on the endless belt, carry out heated-air drying under 100 ℃～140 ℃, the remaining component ratio that obtains having self-supporting is the gel mould of 62 weight %.After this, peel off from belt.As tension force, on the gel mould of peeling off, the MD direction applied to be transported in the Tenter oven under the state of tension force of 3.5kg/m and burn till.Gel mould does not have fixed width direction two ends loosely with the wide 1100mm of pin (gel mould width 1100mm).This gel mould is carried out stage the burning till of 165 ℃ (hot-air ovens), 300 ℃ (hot-air oven), 400 ℃ (hot-air oven), 515 ℃ (far infrared line ovens), burn till and be polyimide film.The TD shrinkage factor becomes 4.0 in order to make, the TD expansion rate becomes 2.1, and edge TD direction makes the polyimide film stretching limit that relaxes carry out the conveying of film.In the contraction of TD direction, begin to shrink from the pin fixed position of gel mould, make to shrink at the inlet of 165 ℃ of stoves and finish.The stretching of TD direction stretches since the inlet of 400 ℃ of stoves, in the outlet end stretching of 400 ℃ of stoves.Polyimide film carries out end cut unloading when fixedly batching, and obtains the wide film of 940mm.

The angle of orientation of the polyimide film that obtains like this, the mensuration of the degree of orientation.The elastic modelling quantity of the polyimide film that obtains is 6.0GPa.Experimental result is documented in table 1, the table 2.From the measurement result of molecular orientation axis as can be known, the angle that can be produced on molecular orientation axis on the whole width of film is controlled in 0 ± 25 ° MD orientation polyimide film.

(embodiment 20)

In the present embodiment, at N, in the dinethylformamide (DMF) with 75mol%4,4 '-ratio of diaminodiphenyl ether (ODA), 25mol% p-phenylenediamine (PPD) (p-PDA), 100mol% pyromellitic acid anhydride (PMDA) adds in proper order by this and carries out polymerization, the synthesizing polyamides acid solution.In this polyamic acid solution, add the acetic anhydride of 2.0 times of equivalents and the isoquinolin of 1.0 times of equivalents with respect to the amic acid equivalent, with the thickness that becomes 20 μ m after burning till, with 820mm width curtain coating on the endless belt, carry out heated-air drying under 100 ℃～150 ℃, the remaining component ratio that obtains having self-supporting is the gel mould of 60 weight %.As tension force, on the gel mould of peeling off, the MD direction applied to be transported in the Tenter oven under the state of tension force of 2kg/m and burn till.Gel mould does not have fixed width direction two ends loosely with the wide 800mm of pin (gel mould width 800mm).This gel mould is carried out stage the burning till of 130 ℃ (hot-air ovens), 260 ℃ (hot-air oven), 360 ℃ (hot-air oven), 450 ℃ (hot-air oven), 515 ℃ (far infrared line ovens), burn till and be polyimide film.The TD shrinkage factor becomes 3.9 in order to make, the TD expansion rate becomes 4.1, and edge TD direction makes the polyimide film stretching limit that relaxes carry out the conveying of film.In the contraction of TD direction, begin to shrink from the pin fixed position of gel mould, make to shrink at the inlet of 130 ℃ of stoves and finish.The stretching of TD direction stretches since the inlet of 450 ℃ of stoves, in the outlet end stretching of 450 ℃ of stoves.Polyimide film carries out end cut unloading when fixedly batching, and obtains the film of 740mm width.The elastic modelling quantity of the polyimide film that obtains is 4.2GPa.

The angle of orientation of the polyimide film that obtains like this, the mensuration of the degree of orientation.Experimental result is documented in table 1, the table 2.From the measurement result of molecular orientation axis as can be known, the angle that can be produced on molecular orientation axis on the whole width of film is controlled in 0 ± 25 ° MD orientation polyimide film.Even the kind of change polyimide film is if the elastic modelling quantity of polyimide film more than or equal to the polyimide film of 4.0GPa, can be made along the polyimide film of MD direction orientation.

(embodiment 21)

In the present embodiment, at N, in the dinethylformamide (DMF) with 45mol%4,4 '-diaminodiphenyl ether (ODA), 55mol% p-phenylenediamine (PPD) (p-PDA), 80mol% pyromellitic acid anhydride (PMDA), 20mol%3,3 ', 4,4 '-ratio of biphenyl tetracarboxylic dianhydride adds in proper order by this and carries out polymerization, the synthesizing polyamides acid solution.In this polyamic acid solution, add the acetic anhydride of 2.0 times of equivalents and the isoquinolin of 1.0 times of equivalents with respect to the amic acid equivalent, with the thickness that becomes 20 μ m after burning till, with 820mm width curtain coating on the endless belt, carry out heated-air drying under 100 ℃～150 ℃, the remaining component ratio that obtains having self-supporting is the gel mould of 60 weight %.After this, peel off from belt.As tension force, on the gel mould of peeling off, the MD direction applied to be transported in the Tenter oven under the state of tension force of 2kg/m and burn till.Gel mould does not have fixed width direction two ends loosely with the wide 800mm of pin (gel mould width 800mm).This gel mould is carried out stage the burning till of 130 ℃ (hot-air ovens), 260 ℃ (hot-air oven), 360 ℃ (hot-air oven), 450 ℃ (hot-air oven), 450 ℃ (far infrared line ovens), burn till and be polyimide film.The TD shrinkage factor becomes 3.9 in order to make, the TD expansion rate becomes 4.1, and edge TD direction makes the polyimide film stretching limit that relaxes carry out the conveying of film.In the contraction of TD direction, begin to shrink from the pin fixed position of gel mould, make to shrink at the inlet of 130 ℃ of stoves and finish.The stretching of TD direction stretches since the inlet of 450 ℃ of stoves (hot-air oven), in the outlet end stretching of 450 ℃ of stoves (hot-air oven).Polyimide film carries out end cut unloading when fixedly batching, and obtains the wide film of 740mm.The elastic modelling quantity of the polyimide film that obtains is 5.5GPa.

The angle of orientation of the polyimide film that obtains like this, the mensuration of the degree of orientation.Experimental result is documented in table 1, the table 2.From the measurement result of molecular orientation axis as can be known, the angle that can be produced on molecular orientation axis on the whole width of film is controlled in 0 ± 25 ° MD orientation polyimide film.Even the kind of change polyimide film is if the elastic modelling quantity of polyimide film more than or equal to the polyimide film of 4.0GPa, can be made along the polyimide film of MD direction orientation.

(embodiment 22)

In the present embodiment, at N, dissolving 30mol%2 in the dinethylformamide (DMF), two [4-(4-amino-benzene oxygen) phenyl] propane (BAPP) and the 20mol%4 of 2-, 4 '-diaminodiphenyl ether (ODA).To wherein adding 20mol%3,3 ', 4,4 '-after biphenyl tetracarboxylic dianhydride makes its dissolving, make 35mol% pyromellitic acid anhydride (PMDA) dissolving.In this solution, add in proper order by this and carry out polymerization, the synthesizing polyamides acid solution with the ratio of 50mol% p-phenylenediamine (PPD) (p-PDA), 45mol% pyromellitic acid anhydride (PMDA).In this polyamic acid solution, add the acetic anhydride of 2.3 times of equivalents and the isoquinolin of 0.5 times of equivalent with respect to the amic acid equivalent, with the thickness that becomes 20 μ m after burning till, with 820mm width curtain coating on the endless belt, carry out heated-air drying under 100 ℃～130 ℃, the remaining component ratio that obtains having self-supporting is the gel mould of 75 weight %.After this, peel off from belt.As tension force, on the gel mould of peeling off, the MD direction applied to be transported in the Tenter oven under the state of tension force of 6kg/m and burn till.Gel mould does not have loosely fixed width direction two ends (gel mould width 800mm) with the wide 800mm of pin.This gel mould is carried out stage the burning till of 130 ℃ (hot-air ovens), 260 ℃ (hot-air oven), 360 ℃ (hot-air oven), 450 ℃ (hot-air oven), 515 ℃ (far infrared line ovens), burn till and be polyimide film.The TD shrinkage factor becomes 3.9 in order to make, the TD expansion rate becomes 4.0, and edge TD direction makes the polyimide film stretching limit that relaxes carry out the conveying of film.In the contraction of TD direction, begin to shrink from the pin fixed position of gel mould, make to shrink at the inlet of 130 ℃ of stoves and finish.The stretching of TD direction stretches since the inlet of 450 ℃ of stoves, in the outlet end stretching of 450 ℃ of stoves.Polyimide film carries out end cut unloading when fixedly batching, and obtains the wide film of 740mm.The elastic modelling quantity of the polyimide film that obtains is 6.7GPa.

The angle of orientation of the polyimide film that obtains like this, the mensuration of the degree of orientation.Experimental result is documented in table 1, the table 2.From the measurement result of molecular orientation axis as can be known, the angle that can be produced on molecular orientation axis on the whole width of film is controlled in 0 ± 25 ° MD orientation polyimide film.

(comparative example 1)

Mix the polyamic acid solution that uses in the present embodiment 1 and with the acetic anhydride and the isoquinolin of embodiment 1 equivalent, with the thickness that becomes 20 μ m after burning till, with 1100mm width curtain coating on the endless belt, carry out heated-air drying under 100 ℃～140 ℃, the remaining component ratio that obtains having self-supporting is the gel mould of 54 weight %.After this, peel off from belt.As tension force, on the gel mould of peeling off, the MD direction applied to be transported in the Tenter oven under the state of tension force of 8kg/m and burn till.Moreover, in this comparative example, burn till by 350 ℃ hot-air ovens, 400 ℃ hot-air oven, 450 ℃ hot-air oven, 515 ℃ far infrared line oven.Gel mould, there are not loosely fixedly TD direction both ends with the wide 1000mm of pin, the limit is carried between the stiff end of gel mould limit with the stove inlet and is set at 1000mm (gel mould width 1000mm), to be set at 1000mm between the stiff end between 350 ℃ of stoves and 400 ℃ of stoves, to be set at 1000mm between the stiff end between 400 ℃ and the 450 ℃ of stoves, be set at 1000mm between stiff end with the outlet of 515 ℃ of far infrared line ovens, be set at 1000mm between stiff end with outlet of still, carry polyimide film to furnace interior, make polyimide film.Unload when fixedly batching at polyimide film and to carry out end cut, obtain the wide film of 940mm.The angle of orientation of the polyimide film that obtains like this, the mensuration of the degree of orientation.Experimental result is documented in table 1, the table 2.

(comparative example 2)

Mix the polyamic acid solution that uses in the present embodiment 1 and with the acetic anhydride and the isoquinolin of embodiment 1 equivalent, with the thickness that becomes 20 μ m after burning till, with 820mm width curtain coating on the endless belt, carry out heated-air drying under 100 ℃～130 ℃, the remaining component ratio that obtains having self-supporting is the gel mould of 60 weight %.After this, peel off from belt.As tension force, on the gel mould of peeling off, the MD direction applied to be transported in the Tenter oven under the state of tension force of 2kg/m and burn till.Moreover, in this comparative example, burn till by 130 ℃ hot-air ovens, 260 ℃ hot-air oven, 360 ℃ hot-air oven, 450 ℃ hot-air oven, 515 ℃ far infrared line oven.Gel mould, there are not loosely the fixedly both ends of TD direction with the wide 800mm of pin, the limit is carried between the stiff end of gel mould limit with the stove inlet and is set at 800mm (gel mould width 800mm), to be set at 800mm between the stiff end between 130 ℃ of stoves and the 260 ℃ of stoves, to be set at 800mm between the stiff end between 260 ℃ and the 360 ℃ of stoves, to be set at 800mm between the stiff end between 360 ℃ and the 450 ℃ of stoves, be set at 800mm between stiff end with the outlet of 515 ℃ of far infrared line ovens, be set at 800mm between stiff end with outlet of still, carry polyimide film to furnace interior, make polyimide film.Unload when fixedly batching at polyimide film and to carry out end cut, obtain the wide film of 740mm.The angle of orientation of the polyimide film that obtains like this, the mensuration of the degree of orientation.Experimental result is documented in table 1, the table 2.

(comparative example 3)

In this comparative example, at N, in the dinethylformamide (DMF) with 100mol%4,4 '-ratio of diaminodiphenyl ether (ODA) and 100mol% pyromellitic acid anhydride (PMDA) adds in proper order by this and carries out polymerization and the synthesizing polyamides acid solution.In this polyamic acid solution, add the acetic anhydride of 2.0 times of equivalents and the isoquinolin of 1.0 times of equivalents with respect to the amic acid equivalent, with the thickness that becomes 20 μ m after burning till, with 820mm width curtain coating on the endless belt, carry out heated-air drying under 100 ℃～150 ℃, the remaining component ratio that obtains having self-supporting is the gel mould of 40 weight %.As tension force, on the gel mould of peeling off, the MD direction applied to be transported in the Tenter oven under the state of tension force of 2kg/m and burn till.Gel mould does not have fixed width direction two ends loosely with the wide 800mm of pin (gel mould width 800mm).This gel mould is carried out stage the burning till of 130 ℃ (hot-air ovens), 260 ℃ (hot-air oven), 360 ℃ (hot-air oven), 450 ℃ (hot-air oven), 515 ℃ (far infrared line ovens), burn till and be polyimide film.The TD shrinkage factor becomes 4.0 in order to make, the TD expansion rate becomes 3.9, and edge TD direction makes the polyimide film stretching limit that relaxes carry out the conveying of film.In the contraction of TD direction, begin to shrink from the pin fixed position of gel mould, make to shrink at the inlet of 130 ℃ of stoves and finish.The stretching of TD direction stretches since the inlet of 450 ℃ of stoves, in the outlet end stretching of 450 ℃ of stoves.Unload when fixedly batching at polyimide film and to carry out end cut, obtain the film of 740mm width.The elastic modelling quantity of the polyimide film that obtains is 3.5GPa.

The angle of orientation of the polyimide film that obtains like this, the mensuration of the degree of orientation.Experimental result is documented in table 1, the table 2.

Creating conditions etc. of table 1 polyimide film

	Remaining component ratio %	Give the tension force kg/m of gel mould	TD shrinkage factor %	TD expansion rate (%)	The temperature of each stove/℃
										1	2	3	4	5
					Embodiment 1	54	8	4.4	0.0						175	325	450	510
Embodiment 2	54	8	4.4	0.0						190	400	450	510
					Embodiment 3	60	2	3.9	0.0						130	260	360	450	515
Embodiment 4	60	2	6.7	0.0						130	260	360	450	515
					Embodiment 5	54	4	3.0	0.0						160	300	400	515
Embodiment 6	54	5	4.0	0.0						160	300	400	515
					Embodiment 7	54	6	4.0	0.0						160	300	400	515
Embodiment 8	54	8	4.0	0.0						160	300	400	515
					Embodiment 9	54	8	4.4	0.0						175	325	450	510
Embodiment 10	54	8	4.4	0.0						175	325	450	450
					Embodiment 11	28	8	4.4	0.0						175	325	450	510
Embodiment 12	107	3	4.4	0.0						175	325	450	510
					Embodiment 13	60	2	6.7	0.0						130	260	360	450	515
Embodiment 14	75	6	3.9	0.0						130	260	360	450	515
					Embodiment 15	60	2	3.9	4.1						130	260	360	450	515
Embodiment 16	60	2	2.0	4.0						130	260	360	450	515
					Embodiment 17	54	8	4.4	2.3						175	300	450	515
Embodiment 18	54	8	4.4	4.6						175	300	450	515
					Embodiment 19	62	3.5	4.0	2.1						165	300	400	515
Embodiment 20	60	2	3.9	4.1						130	260	360	450	515
					Embodiment 21	60	2	3.9	4.1						130	260	360	450	450
Embodiment 22	75	6	3.9	4.0						130	260	360	450	515
					Comparative example 1	54	8	0.0	0.0						350	400	450	510
Comparative example 2	60	2	0.0	0.0						130	260	360	450	515
					Comparative example 3	40	2	4.0	3.9						130	260	360	450	515

The rerum natura table of table 2 polyimide film

	The Angle/ angle							MORc
															Measure the position							Measure position/mm
	A	B	C	D	E	F	G	A	B	C	D	E	F	G
															Embodiment 1	-3	-2	-7	-6	-6	-6	11	1.42	1.58	1.66	1.70	1.66	1.57	1.43
Embodiment 2	-16	-2	-1	-6	-7	-1	18	1.44	1.57	1.6	1.65	1.59	1.6	1.42
															Embodiment 3	-1	-2	0	3	5			1.55	1.50	1.48	1.53	1.66
Embodiment 4	-6	-2	1	2	5			2.13	1.97	1.90	1.90	1.94
															Embodiment 5	-17	-3	-2	-8	-9	-11	-2	1.44	1.44	1.45	1.32	1.58	1.67	1.46
Embodiment 6	-9	-1	1	-6	-10	-7	-2	1.55	1.62	1.57	1.50	1.75	1.74	1.60
															Embodiment 7	-9	-4	-7	-6	-9	-7	3	1.70	1.74	1.59	1.60	1.71	1.74	1.65
Embodiment 8	-17	-8	-8	-8	-6	-7	1	1.61	1.63	1.58	1.60	1.77	1.85	1.70
															Embodiment 9	-2	1	3	4	5	-1	-3	1.34	1.22	1.18	1.23	1.22	1.33	1.34
Embodiment 10	-8	-5	-7	-6	-4	-6	9	1.5	1.67	1.59	1.59	1.65	1.66	1.7
															Embodiment 11	-24	-17	-6	-1	4	15	20	1.8	1.58	1.52	1.55	1.7	1.65	1.85
Embodiment 12	-3	2	2	4	3	-5	-6	1.62	1.66	1.56	1.5	1.7	1.68	1.65
															Embodiment 13	-10	-5	5	3	10			2.13	1.97	1.9	1.9	1.94
Embodiment 14	-3	0	4	-13	13			1.32	1.27	1.32	1.18	1.35
															Embodiment 15	-4	0	-3	-2	-1			1.53	1.39	1.38	1.48	1.48
Embodiment 16	0	9	-8	7	19			1.30	1.12	1.13	1.24	1.32
															Embodiment 17	0	-4	-5	-3	-4	-1	6	1.54	1.43	1.55	1.49	1.56	1.45	1.43
Embodiment 18	-5	-8	10	-1	-1	2	10	1.55	1.29	1.31	1.25	1.37	1.35	1.36
															Embodiment 19	-15	0	-8	-13	-9	-8	2	1.61	1.44	1.38	1.63	1.66	1.62	1.5
Embodiment 20	5	8	-8	2	10			1.24	1.18	1.2	1.15	1.18
															Embodiment 21	5	4	-1	-3	6			1.44	1.35	1.42	1.48	1.39
Embodiment 22	-9	3	0	11	9			1.16	1.18	1.18	1.19	1.14
															Comparative example 1	-44	-35	-60	90	28	22	45	1.97	1.26	1.17	1.21	1.3	1.24	2.47
Comparative example 2	-19	64	58	39	37			1.35	1.05	1.17	1.26	1.47
															Comparative example 3	-40	-52	89	89	46			1.12	1.18	1.09	1.12	1.15

Claims (8)

1. the manufacture method of synthetic resin film is in the manufacture method of quantity-produced synthetic resin film, comprises the manufacture method of the synthetic resin film of following (A)～(C) at least:

(A) on supporter continuously curtain coating coating contain the composition of macromolecule and organic solvent, form the operation of gel mould,

(B) peel off gel mould from supporter, the operation at the two ends of immobilized gel film,

(C) the fixing limit, two ends of the film operation of in heating furnace, carrying in limit,

It is characterized in that: at least a portion of above-mentioned (C) operation, comprise the fixedly two ends operation of carrying of tension force that (C-1) make film width (TD direction) with becoming no tension force basically.

2. the manufacture method of the described synthetic resin film of claim 1 is characterized in that: the inlet of the heating furnace in above-mentioned (C) operation, the tension force that makes the TD direction is two ends fixedly with becoming no tension force basically.

3. the manufacture method of the described synthetic resin film of claim 2, it is characterized in that: above-mentioned heating furnace is made of many heating furnaces more than or equal to 2, and the temperature of first heating furnace is smaller or equal to 300 ℃.

4. the manufacture method of each described synthetic resin film in the claim 1～3, it is characterized in that: in above-mentioned (C) operation, if the distance of both ends stiff end is the film width between X, both ends stiff end when being Y, in order to make X and Y satisfy formula 20.0 〉=(Y-X)/Y * 100＞0.00, the tension force that makes the TD direction fixedly between two ends with becoming no tension force basically.

5. the manufacture method of each described synthetic resin film in the claim 1～4 is characterized in that: comprise (C-2) operation along TD direction stretched film at least a portion of above-mentioned (C) operation.

6. the manufacture method of the described synthetic resin film of claim 5, it is characterized in that: in above-mentioned (C-2) operation, the distance of the both ends stiff end of the TD direction before if stretch is that the distance of Z, the both ends stiff end when stove in-draw film is when being W, in order to make Z and W satisfy formula 40.0 〉=(W-Z)/Z * 100＞0.00, along TD direction stretched film.

7. the manufacture method of each described synthetic resin film in the claim 1～6, it is characterized in that: above-mentioned synthetic resin film is a polyimide film.

8. synthetic resin film, it uses the manufacture method manufacturing of each described synthetic resin film in claim 1～7.

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