CN1714119A - Polyimide film and process for producing the same - Google Patents

Abstract

An oriented polyimide film with a high Young's modulus, satisfactory moist heat resistance and low moisture absorptivity, and a process for its production. The polyimide film is composed mainly of a pyromellitic acid component, with a p-phenylenediamine component at between 30 mole percent and 99 mole percent and a diamine component represented by the structural unit of the following formula (II) at between 1 mole percent and 70 mole percent: (wherein Ar<IIa> and Ar<IIb> are each independently a C6-20 aromatic group optionally having an non-reactive substituent, and X in structural unit (II) consists of at least one group selected from among -O-, -O-Ar<IIc>-O-, -SO2- and -O-Ar<IId>-O-Ar<IIe>-O-), and the polyimide film is characterized by having two perpendicular directions in which the in-plane Young's modulus is 3 GPa or greater, and having a moisture absorptivity of no greater than 3.3 wt% at 72% RH, 25 DEG C.

Description

Kapton and manufacture method thereof

Technical field

The present invention relates to that humidity resistance is good, agent of low hygroscopicity and mechanical characteristics obtain Kapton and the method for making thereof highly improved.

Prior art

Full aromatic polyimide is used widely industrial because of its good thermotolerance, mechanical properties, and particularly its film occupies critical positions as the base material that is used for the thin layer electronic component in the purposes headed by mounting with electronics.To the strong request of electronic component miniaturization, need the thinner Kapton of used thickness along with in recent years, but be accompanied by reducing of thickness, high rigidity becomes indispensable prerequisite in film application or the operation.

The method that makes full aromatic polyimide film have high Young's modulus has following two kinds: (1) adopts the method for upright and outspoken and linear high chemical structure as the molecular skeleton of formation polyimide; (2) make polyimide carry out the method for molecular orientation by physical method.About the chemical structure of method (1), with pyromellitic acid or 3,3 ', 4,4 '-bibenzene tetracarboxylic is as sour composition, as amine component, perhaps adopts their nuclear substituted various combinations with Ursol D or p-diaminodiphenyl, carries out various raw materials researchs.The theoretical Young's modulus of the equal diimides of polyparaphenylene the highest (referring to fiber association will 43 volume, the field is for waiting (1987)) wherein, and raw material is cheap, thereby be the material that is hopeful most as the high Young's modulus film raw material.No matter but its potential how, knownly can only obtain the equal diimides film of extremely crisp polyparaphenylene by existing Kapton manufacture method commonly used.

For addressing this problem, people have proposed various schemes, for example the polyamic acid solution that Ursol D and pyromellitic acid anhydride reactant the are obtained method (referring to Japanese kokai publication hei 1-282219 communique) of carrying out chemical cyclisation; Make and have substituent Ursol D and the pyromellitic acid anhydride reactant obtains polyamic acid solution, in this polyamic acid, add a large amount of diacetyl oxides and obtain dope, with this dope curtain coating, dry under low temperature, decompression, the method for heat-treating afterwards (Japanese kokai publication hei 6-172529 communique).Yet, though these methods still can only obtain the high obviously fragile film of Young's modulus.In addition, as method with the polymeric amide stretch orientation, following proposal has been proposed: after being used as the polyamic acid solution system film of the equal diimides precursor of polyparaphenylene, dried polyamic acid film is carried out uniaxial drawing in solvent, the method of carrying out imidization afterwards is (referring to polymer collection of thesis the 56th volume, the 5th phase, the 282-290 page or leaf); The precursor polyesteramide that has imported long-chain (carbonatoms 10-18) ester group in the polymer chain is carried out the wet type spinning, the gained silk is carried out stretch orientation, then by overheated method of carrying out imidization (referring to the 3752nd page of the Polymer Preprint Japan of the 141st volume the 9th phase (1992)).But all do not have the record about the biaxial stretching that can average out in face in the aforesaid method, acquisition had not obtained in-plane equilibrium, having high Young's modulus and flexible simultaneously can the practical equal diimides film of polyparaphenylene.

As the method for improving this problem of in-plane equilibrium, someone has proposed following method: make the reaction of polyamic acid solution and dewatering agent, to carry out biaxial stretching by the gel-film that the dehydration imidization reaction obtains, preparation has obtained the biax orientation Kapton (referring to TOHKEMY 2001-302821 communique, TOHKEMY 2002-030519 communique, TOHKEMY WO-01/81456 communique, Japanese kokai publication hei 05-237928 communique) of in-plane equilibrium.

But, though the equal diimides film of polyparaphenylene mechanical characteristics is good, but water absorbability height, during the processing for example under the environment of moisture is arranged, carrying out sharply rising with temperature, will be because of moisture vaporization etc. and to make with the Kapton be that the parts of base material break, perhaps produce bad because of dilatational strain.Therefore, wish that the high Young's modulus Kapton has low rate of moisture absorption.Simultaneously, also there is the rerum natura that is caused by moisture this problem that descends in the equal diimides of polyparaphenylene.For example, in 121 ℃ saturated steam, its mechanics rerum natura will significantly reduce.And, consider the trafficability characteristic in various complete processings and require adaptability in the purposes of resistance to deflection that the equal diimides of polyparaphenylene still exists extension at break low, need further give its toughness this problem at flexible print circuit board etc.Therefore, wish to develop the Kapton that humidity resistance is good, have characteristics such as more practical toughness and high Young's modulus concurrently.

On the other hand, someone has proposed a kind of like this scheme: with the part of the equal diimides of polyparaphenylene as constituent, make itself and aromatic diamine composition 3, the copolymerization of 4 '-diaminodiphenyl oxide, formed copolyimide film are the materials (referring to Japanese kokai publication sho 62-117815) with superior mechanical rerum natura.But these materials are that prerequisite proposes with the fiber, for it by not knowing in twin shaft height-oriented situation that obtains the snappiness rate and obtain the plates of in-plane equilibrium on direction.The somebody has proposed following method: by the pyromellitic acid of (being 100% among the embodiment) more than 80% mole and more than 80% mole (being 100% among the embodiment) 3,4 '-diaminodiphenyl oxide forms Kapton, at 250 ℃-450 ℃, is to carry out twin shaft to xeothermic stretching (referring to No. 2626827 special permission communique) under 350 ℃ hot conditions with this film among the embodiment.This method can make the film of high Young's modulus really, can carry out so xeothermic stretching composition but exist, and its thermotolerance is still not enough, particularly the problem that at high temperature dimensional stability is not enough and Young's modulus descends along with contraction.And the temperature condition more than 350 ℃, for xeothermic drawing process condition, be very high temperature, when considering industrial production, the cost height, unrealistic.Therefore, still need to have between environmental stabilities such as low rate of moisture absorption, humidity resistance and the mechanical characteristics and obtain the high Young's modulus of excellent balance, high heat-pesistant thin film.

Summary of the invention

The object of the invention is to provide humidity resistance, agent of low hygroscopicity and the mechanical characteristics that can't obtain with prior art, particularly good Kapton aspect high Young's modulus.

Other purpose of the present invention is to provide the manufacture method of the Kapton with highly good humidity resistance, agent of low hygroscopicity and mechanical characteristics.

Purpose of the present invention and benefit can be learnt by following explanation.

The first, above-mentioned purpose of the present invention and benefit can realize that this film is to form by constituting the unit shown in the following formula (II) that constitutes unit and 1% mole-70% molar ratio shown in 30% mole-99% mole the following formula (I) by a kind of Kapton,

[Ar ^IaNon-reacted substituent 1 for containing, the 4-phenylene.]

(Ar ^IIaAnd Ar ^IIbIndependent of separately containing the aryl of non-reacted substituent carbonatoms 6-20, the X in the above-mentioned formation unit (II) is made of at least a structural formula that is selected from following (II-i), (II-ii), (II-iii), (II-iv):

-O-????????????……(II-i)

-O-Ar ^IIc-O-????……(II-ii)

[Ar ^IIcFor containing the aryl of non-reacted substituent carbonatoms 6-20.]

With

[Ar ^IIdAnd Ar ^IIeIndependent of separately containing the aryl of non-reacted substituent carbonatoms 6-20.])，

Described film is characterised in that: having Young's modulus in the face is the above vertical both direction of 3GPa, is below the 3.3wt% at 72%RH, 25 ℃ rate of moisture absorption.

The aromatic polyimide that the present invention has studied having upright and outspoken structure carries out high elongation, make the technology of molecular orientation, found that: by formation unit (II) and above-mentioned formation unit (I) copolymerization that makes specified quantitative, it is good to obtain Young's modulus, obtained mechanical characteristics balance in the face, and humidity resistance, the improved Kapton of rate of moisture absorption.

The second, above-mentioned purpose of the present invention and benefit can realize that this manufacture method comprises the steps: by a kind of manufacture method of Kapton

Step 1: make (A) pyromellitic acid acid anhydride, (B) following formula (III)

H ₂N-Ar ^Ia-NH ₂????……(III)

[Ar ^IaNon-reacted substituent 1 for containing, the 4-phenylene.]

Shown in aromatic diamine compound and (C) following formula (IV)

H ₂N-Ar ^IIa-X-Ar ^IIb-NH ₂????……(IV)

(Ar ^IIaAnd Ar ^IIbIndependent of separately containing the aryl of non-reacted substituent carbonatoms 6-20, X is made of at least a structural formula that is selected from following (IV-i), (IV-ii), (IV-iii), (IV-iv):

-O-????????????……(IV-i)

-O-Ar ^IIc-O-????……(IV-ii)

[Ar ^IIcFor containing the aryl of non-reacted substituent carbonatoms 6-20.]

With

[Ar ^IIdAnd Ar ^IIeIndependent of separately containing the aryl of non-reacted substituent carbonatoms 6-20.])

Shown in aromatic diamine compound, react in solvent with the ratio that satisfies following formula (1) and (2) simultaneously, obtain polyamic acid solution,

0.95≤a/(b+c)≤1.05????……(1)

0.01≤c/(b+c)≤0.70????……(2)

[wherein a represents the mole number of pyromellitic acid acid anhydride, and b represents the mole number of aromatic diamine compound shown in the following formula (III), and c represents the mole number of aromatic diamine compound shown in the following formula (IV).]；

Step 2: make the reaction of gained polyamic acid solution and dewatering agent, make at least a portion of polyamic acid convert poly-different imide to, form gel film;

Step 3: the gained gel film is carried out biaxial stretching;

Step 4: the gained biaxially drawn films is heat-treated.

The preferred embodiment of invention

At first Kapton of the present invention is described.

Kapton of the present invention is to form by constituting the unit shown in the following formula (II) that constitutes unit and 1% mole-70% molar ratio shown in 30% mole of-99% mole of following formula (I),

[Ar ^IaNon-reacted substituent 1 for containing, the 4-phenylene.]

(Ar ^IIaAnd Ar ^IIbIndependent of separately containing the aryl of non-reacted substituent carbonatoms 6-20, the X in the above-mentioned formation unit (II) is made of at least a structural formula that is selected from following (II-i), (II-ii), (II-iii), (II-iv):

-O-????????????……(II-i)

-O-Ar ^IIc-O-????……(II-ii)

[Ar ^IIcFor containing the aryl of non-reacted substituent carbonatoms 6-20.]

With

[Ar ^IIdAnd Ar ^IIeIndependent of separately containing the aryl of non-reacted substituent carbonatoms 6-20.])，

This film is characterised in that: having Young's modulus in the face is the above vertical both direction of 3GPa, is below the 3.3wt% at 72%RH, 25 ℃ rate of moisture absorption.

Wherein, the Ar in the following formula (I) ^IaNon-reacted substituent 1 for containing, 4-phenylene, non-reacted substituting group for example can be that carbonatomss such as methyl are that carbonatomss such as the alkyl, methoxyl group of 1-6 are halogeno-groups such as alkoxyl group, chlorine or fluorine of 1-6 etc.Following formula Ar ^IaPreferred example have 1,4-phenylene, 1,3-phenylene, 2-chloro-1,4-phenylene, 2-methyl isophthalic acid, 4-phenylene, 2,5-two chloro-1,4-phenylene, 2,5-dimethyl-1,4-phenylene, 2-chloro-5-methyl isophthalic acid, 4-phenylene, 2-methoxyl group-1,4-phenylene etc.Preferred example is 1, the 4-phenylene.That is, particularly preferred formation unit (I) can exemplify following formula (I-a) in fact.

In addition, also two or more formations unit (I) can be used in combination.

Ar in the above-mentioned formation unit (II) ^IIaAnd Ar ^IIbIndependent of separately containing the aryl of non-reacted substituent carbonatoms 6-20.The example of aryl has phenylene, naphthylidene, biphenylene etc.The part or all of hydrogen of aryl can be replaced by non-reacted substituting group.Described non-reacted substituting group for example can be that carbonatomss such as methyl are that carbonatomss such as the alkyl, methoxyl group of 1-6 are halogeno-groups such as alkoxyl group, chlorine or fluorine of 1-6 etc.Ar in the above-mentioned formation unit (II) ^IIaAnd Ar ^IIbPreferred example have 1,4-phenylene and/or 1,3-phenylene.

X in the above-mentioned formation unit (II) is made of at least a above-mentioned (II-i), (II-ii), (II-iii) and the structural formula (II-iv) of being selected from.

When X was above-mentioned formula (II-i), more preferred example was the Ar in the above-mentioned formation unit (II) ^IIaAnd Ar ^IIbBe 1,4-phenylene and 1, the structure of the combination of 3-phenylene.That is, the more preferred example of above-mentioned formation unit (II) is following formula (II-i-a).

At this moment, two amine components in the following formula (II-i-a) are unsymmetric structure, can be in fact stereospecifics, also can be atactic, preferred atactic.

When X is following formula (II-ii), the Ar in the formula (II-ii) ^IIcBe independent of the Ar in the above-mentioned formation unit (II) ^IIaAnd Ar ^IIb, for containing the aryl of non-reacted substituent carbonatoms 6-20.The example of aryl has phenylene, naphthylidene, biphenylene etc.The part or all of hydrogen of aryl can be replaced by non-reacted substituting group.This non-reacted substituting group for example can be that carbonatomss such as methyl are that carbonatomss such as the alkyl, methoxyl group of 1-6 are halogeno-groups such as alkoxyl group, chlorine or fluorine of 1-6 etc.Above-mentioned Ar ^IIcPreferred example have 1,4-phenylene and/or 1,3-phenylene.More preferred example is 1, the 3-phenylene.And, the Ar in above-mentioned formation unit this moment (II) ^IIaAnd Ar ^IIbBe preferably 1,4-phenylene and/or 1, the 3-phenylene is preferably 1 especially, the 3-phenylene.Therefore, the example of particularly preferred formation unit (II) is following formula (II-ii-a).

When X was following formula (II-iii), more preferred example was the Ar in the above-mentioned formation unit (II) ^IIaAnd Ar ^IIbBe 1, the structure of 3-phenylene.That is, the particularly preferred example of above-mentioned formation unit (II) is following formula (II-iii-a).

When X is following formula (II-iv), the Ar in the formula (II-iv) ^IIdAnd Ar ^IIeIndependently separately be aryl that can to contain non-reacted substituent carbonatoms be 6-20.The example of aryl has phenylene, naphthylidene, biphenylene etc.The part or all of hydrogen of aryl can be replaced by non-reacted substituting group.This non-reacted substituting group for example can be that carbonatomss such as methyl are that carbonatomss such as the alkyl, methoxyl group of 1-6 are halogeno-groups such as alkoxyl group, chlorine or fluorine of 1-6 etc.Above-mentioned Ar ^IIdAnd Ar ^IIePreferred example have 1,4-phenylene and/or 1,3-phenylene.More preferred example is 1, the 4-phenylene.And, the Ar in above-mentioned formation unit this moment (II) ^IIaAnd Ar ^IIbBe preferably 1,4-phenylene and/or 1, the 3-phenylene is preferably 1 especially, the 3-phenylene.Therefore, the example of particularly preferred formation unit (II) is a following formula (II-iv-a) and/or (II-iv-b).

Wherein more preferred example is following formula (II-iv-a).

The preferred X that constitutes in the unit (II) is a structure shown in the following formula (II-i), and constituting unit (I) is the 40-70% mole, and constituting unit (II) is the 30-60% mole.Such formation can obtain having abundant Young's modulus and the good Kapton of humidity resistance.

The Young's modulus of preferred gained Kapton all is being more than the 3GPa, more preferably more than the 6GPa on the both direction.

The preferred X that constitutes in the unit (II) is at least a being selected from (II-ii), (II-iii) and structure (II-iv), and constituting unit (I) is the 60-90% mole, and constituting unit (II) is the 10-40% mole.

And then by research of the present invention as can be known: the imino-concentration [imide] in the polyimide is the important factor in order that acquisition has the Kapton of abundant Young's modulus and good humidity resistance concurrently.More particularly, as the preferred composition of the Kapton that has abundant Young's modulus and good humidity resistance concurrently, preferred wherein imino-concentration satisfies the composition of 5.7-6.2eq/kg.More preferably 5.8-6.1eq/kg, preferred especially 5.85-6.05eq/kg.Here said imino-concentration is the equivalent value of existing imino-in the 1kg polyimide.

By such formation, can obtain to have abundant Young's modulus, and the good Kapton of humidity resistance.

Kapton of the present invention, its Young's modulus value has reached the height that does not have so far, and has obtained good balance, has good practicality.That is, having Young's modulus in the face is the above vertical both direction of 3GPa.If Young's modulus less than 3GPa, particularly making under the situation of film, the rigidity deficiency will occur, the situation of transporting property of operation difference.The Young's modulus of preferred gained Kapton all is being more than the 3GPa, more preferably more than the 6GPa on the both direction.

The rate of moisture absorption of Kapton of the present invention under 72%RH, 25 ℃ is below the 3.3wt%.When being 3.3wt% when above, high-temperature heating treatment will make Kapton decompose, and foamed phenomenon appears in the rapid expansion because of moisture sometimes, so not preferred.More preferably below the 3.1wt%, more preferably below the 2.9wt%.

Preferred Kapton of the present invention tensile strength in one direction is more than the 150MPa.More preferably more than the 180MPa, be preferably more than the 200MPa especially.

The tension fracture elongation in one direction of preferred Kapton of the present invention is more than 3%.More preferably more than 5%, more preferably more than 10%.

The imino-ratio is more than 95% in the polyimide of preferred Kapton of the present invention.If the imino-ratio is less than 95%, then the hydrolytic resistance of Kapton reduces, thereby not preferred.

The imino-ratio is meant that the nitrogen-atoms that comes from imino-contained in the Kapton is with respect to nitrogen-atoms that comes from the acid amides acidic group and the ratio (% mole) that comes from the nitrogen-atoms sum of imino-.

The inventor has studied having the aromatic polyimide high elongation of upright and outspoken structure, make the technology of molecular orientation, found that: the formation unit (II) and above-mentioned formation unit (I) copolymerization that make specified quantitative, gained precursor amido acid is carried out chemical treatment with ad hoc approach, make gelinite, because this gelinite has high stretch under near the low temperature the room temperature, thereby by postheat treatment that this gelinite is stretched under solvent swelling state, it is good to obtain Young's modulus, obtained mechanical characteristics balance in the face, and the improved Kapton of rate of moisture absorption.

The imino-ratio is more than 95% in the polyimide of preferred Kapton of the present invention.If the imino-ratio is less than 95%, then the hydrolytic resistance of Kapton descends.In an embodiment the imino-ratio is defined.

Kapton of the present invention, its Young's modulus value reached the height that does not have so far, and obtained Young's modulus well balanced in pellicular front, has good practicality.That is, exist Young's modulus all to surpass the vertical both direction of 3GPa in the pellicular front.Exist Young's modulus all to surpass the vertical both direction of 6GPa in the preferred film face.

Preferred Kapton of the present invention tensile strength in one direction is more than the 150MPa.More preferably tensile strength in one direction is more than the 300MPa, to be preferably more than the 400MPa especially.

Next, the method for making Kapton of the present invention is described in detail.

Manufacture method of the present invention comprises the steps (1)-(4).

Step 1: make (A) pyromellitic acid acid anhydride, (B) following formula (III)

H ₂N-Ar ^Ia-NH ₂????……(III)

[Ar ^IaNon-reacted substituent 1 for containing, the 4-phenylene.]

Shown in aromatic diamine compound and (C) following formula (IV)

H ₂N-Ar ^IIa-X-Ar ^IIb-NH ₂????……(IV)

(Ar ^IIaAnd Ar ^IIbIndependent of separately containing the aryl of non-reacted substituent carbonatoms 6-20, X is made of at least a structural formula that is selected from following (IV-i), (IV-ii), (IV-iii), (IV-iv):

-O-????????????……(IV-i)

-O-Ar ^IIc-O-????……(IV-ii)

[Ar ^IIcFor containing the aryl of non-reacted substituent carbonatoms 6-20.]

With

[Ar ^IIdAnd Ar ^IIeIndependent of separately containing the aryl of non-reacted substituent carbonatoms 6-20.])

Shown in aromatic diamine compound, react in solvent with the ratio that satisfies following formula (1) and (2) simultaneously, obtain polyamic acid solution,

0.95≤a/(b+c)≤1.05????……(1)

0.01≤c/(b+c)≤0.70????……(2)

[wherein a represents the mole number of pyromellitic acid acid anhydride, and b represents the mole number of aromatic diamine compound shown in the following formula (III), and c represents the mole number of aromatic diamine compound shown in the following formula (IV).]；

Step 2: make the reaction of gained polyamic acid solution and dewatering agent, make at least a portion of polyamic acid convert poly-different imide to, form gel film;

Step 3: the gained gel film is carried out biaxial stretching;

Step 4: the gained biaxially drawn films is heat-treated.

In the step 1, the solution polymerization by polyamic acid makes polyamic acid solution.The polymerization process of polyamic acid can adopt known method always.

Wherein, the Ar in the following formula (III) ^IaNon-reacted substituent 1 for containing, the 4-phenylene.That is, identical with group in the above-mentioned formation unit (I).Therefore, aromatic diamine compound shown in the particularly preferred following formula (III) for example is a compound shown in the following formula (III-a).

Aromatic diamine compound can two or more be used in combination shown in the following formula (III).

Ar in the following formula (IV) ^IIaAnd Ar ^IIbIndependent separately is the aryl that can contain the carbonatoms 6-20 of non-reacted substituting group or ehter bond.That is, identical with group in the above-mentioned formation unit (II).In addition, the X in the following formula (IV) is made of at least a following formula (IV-i), (IV-ii), (IV-iii) and the structure (IV-iv) of being selected from.Therefore, in fact respectively with above-mentioned formation unit (II) in formula (II-i), (II-ii), (II-iii) and (II-iv) the same.So the more preferred example of aromatic diamine compound shown in the following formula (IV) has following formula (IV-i-a), (IV-ii-a), (IV-iii-a), (IV-iv-a) and (IV-iv-b).

Hereinafter respectively with following formula (IV-i-a), (IV-ii-a), (IV-iv-a) and aromatic diamine compound (IV-iv-b) abbreviate 3 as, 4 '-DAPE, APB, BAPS-M and BAPS.Aromatic diamine compound can two or more be used in combination shown in the following formula (IV).Particularly preferred formation unit for example be (IV-i-a) 3,4 '-DAPE.

A in following formula (1) and (2) represents the mole number of pyromellitic acid acid anhydride, and b represents the mole number of aromatic diamine shown in the following formula (III), and c represents the mole number of aromatic diamine compound shown in the following formula (IV).When the value of a/ (b+c) less than 0.95 or greater than 1.05 the time, the polymerization degree of gained polyamic acid is low, the system film difficulty that becomes.Be preferably more than 0.97 but less than 1.03.

The value of c/ (b+c) is 0.01-0.7.When aromatic diamine compound was following formula (IV-i-a) shown in the following formula (IV), the value of preferred c/ (b+c) was 0.3-0.6.

When aromatic diamine compound is (IV-ii-a), (IV-iii-a), (IV-iv-a) and (IV-iv-b) time, the value of preferred c/ (b+c) is 0.1-0.4.

And then, as the front described in the composition of polyimide, as can be known by research of the present invention: the imino-concentration in the polyimide is an important factor in order that obtains to have concurrently abundant Young's modulus and good humidity resistance Kapton.More particularly, the additional proportion of preferred aromatic tetracarboxylic acid dianhydride and aromatic diamine compound is the ratio that satisfies following condition: promptly the polyimide Central Asia amino group concentration of gained Kapton is 5.7-6.2eq/kg.More preferably satisfy the ratio of 5.8-6.1eq/kg, be preferably the ratio that satisfies 5.85-6.05eq/kg especially.Here said imino-concentration is the normal value of existing imino-in the expression 1kg polyimide.

Adding method to each raw material (A), (B), (C) is not particularly limited, and interpolation order and addition means can be existing any methods.Preferably at first be dissolved in the solvent, under required temperature of reaction, add (A) then, make its polymerization with two amine components (B) with (C).(A) interpolation can be disposable interpolation predetermined amount, also can be to be divided into several times adding.Particularly be difficult to because of reaction heat under the situation of control reaction temperature, preferably be divided into several times and add.

Temperature of reaction during preferred this polyamic acid polymerization is-20 ℃ to 80 ℃.When being lower than-20 ℃, not preferred because of not obtaining sufficient speed of response.If be higher than 80 ℃, then imidization will partly take place, side reaction perhaps takes place, thereby occurs stablizing the situation that obtains polyamic acid.Be preferably-10 ℃ straight 70 ℃, more preferably 0 ℃ to 50 ℃.

The example of reaction solvent has and contains at least a N-of being selected from N-methyl-2-2-pyrrolidone N-(being designated hereinafter simply as NMP), N, dinethylformamide, N,N-dimethylacetamide, 1, the solvent of 3-dimethyl-imidazolinone.Be preferably NMP and/or N,N-dimethylacetamide, more preferably NMP.

The concentration of preferred this polyamic acid solution is 0.1wt%-30wt%.During less than 0.1wt%, polymerization is difficult to fully carry out, when making film, and the solution that can't obtain having abundant viscosity sometimes.And concentration is during greater than 30wt%, otherwise high viscosity then occurs, becomes the solution that is unsuitable for making film.Be preferably 1wt%-25wt%, more preferably 1.5wt%-20wt%.Can the polymerization of polyamic acid midway and/or polymerization use solvent cut when finishing, the concentration of final gained polyamic acid solution is adjusted.

Preferably under the low humidity condition, implement step 1 of the present invention.For example, preferably under low humidity inert gas atmosphere such as nitrogen, argon gas, perhaps under dry air atmosphere, carry out.Raw material, solvent used in the preferred steps 1 also use exsiccant material as far as possible.

Preferably the polyamic acid in this polyamic acid solution is carried out end-blocking.When using end-capping reagent to carry out end-blocking, as the preferred example of end-capping reagent, the acid anhydrides composition has Tetra hydro Phthalic anhydride and replaces body, hexahydrophthalic anhydride and replacement body, succinyl oxide and replacement body thereof, and amine component has aniline and replaces body.Wherein, Tetra hydro Phthalic anhydride and replacement body thereof and/or aniline and replacement body thereof are more preferred examples.The selection of time of adding end-capping reagent is not particularly limited, and can be when dress adds the polymer raw of polyamic acid, also can be in polymerization midway or any time of polymerization when finishing.Addition is so long as termination reaction and the viscosity of polyamic acid solution is reached stablize required amount and get final product in fact can be judged suitable addition by simple experiment.

In the step 2, make the reaction of gained polyamic acid solution and dewatering agent, convert at least a portion of polyamic acid to poly-different imide, obtain gel film.In more detail, step 2 is diacetyl oxide and the organic amines that add again in the polyamic acid solution that makes in step 1 as dewatering agent, form polyamic acid composition, with said composition curtain coating on carrier, by it is heated up, heat treated, make it carry out dehydration reaction, convert at least a portion of polyamic acid to polyimide or poly-different imide, form gel film (method 1).Perhaps with the polyamic acid solution curtain coating on carrier that makes in the above-mentioned steps (1), obtain film, gained film and described carrier be impregnated in together in the different imidization solution that contains the solvent the same, dewatering agent diacetyl oxide and organic amine then with step 1, make at least a portion of polyamic acid convert poly-different imide to, form gelatinous membrane (method 2).Specify two kinds of methods now.

Reacting the method 1 that obtains gel film with dewatering agent, more particularly, is to add organic amine and mixing in the polyamic acid solution that at first makes in above-mentioned steps (1).Operable organic amine compound is the compound that the catalysts as diacetyl oxide and polyamic acid works, and for example can use aliphatic tertiary amines such as Trimethylamine 99, triethylamine, Tributylamine, diisopropylethylamine, triethylenediamine; N, accelerine, 1, aromatic amines such as 8-two (N, N-dimethylamino) naphthalene; Pyridine and derivative thereof, picoline and derivative thereof, lutidine, quinoline, isoquinoline 99.9,1,8-diazabicyclo [5.4.0] undecylene, N, heterogeneous ring compounds such as N-dimethyl aminopyridine.Wherein from economic considerations, preferred pyridine and picoline.In addition, triethylenediamine and N, N-dimethyl aminopyridine and diacetyl oxide combination owing to can obtain high imino-ratio, make the high gel film of water tolerance, so preferred the use.The addition of organic amine compound is the 0.1-20 mole with respect to 1 mole of polyamic acid repeating unit.When being less than 0.1 mole, can not get sufficient additive effect.And during more than 20 moles, the viscosity of resulting composition will descend, thereby not preferred.Preferred scope is the 0.5-10 mole.The mixing temperature of polyamic acid solution and organic amine is preferably-30 ℃ to 30 ℃.When mixing temperature was higher than 30 ℃, polyamic acid lacked viscosity stability, thereby not preferred.And when being lower than-30 ℃, the viscosity that polymeric amide holds liquid obviously increases, and is difficult to mix.More preferably-25 ℃ to 10 ℃.And can further add acetate this moment as required, to suppress the volatilization of organic amine compound.Under the situation of adding acetate, all unqualified to the addition means and the order of organic amine compound and acetate, but preferably make organic amine compound and acetate form salt in advance, and then the method for adding.Amount to acetate is not particularly limited, but with respect to 1 mole of organic amine compound, acetate is below 4 moles.Be preferably below 2 moles.In gained solution, mix diacetyl oxide then.Preferred diacetyl oxide consumption is the 0.1-20 mole with respect to 1 mole of polyamic acid repeating unit.Be less than 0.1 mole, then react insufficient, the gained gel film is crisp.And, viscosity degradation, decreased solubility then will occur, thereby gel film devitrification more than 20 moles.Be preferably the 0.5-10 mole.The mixing temperature of diacetyl oxide is preferably-30 ℃ to 30 ℃ scope.When mixing temperature was higher than 30 ℃, polyamic acid lacked viscosity stability, thereby not preferred.When being lower than-30 ℃, the viscosity of polyamide solution significantly increases, and the blended situation can occur being difficult to.Preferred temperature range is-25 ℃ to 10 ℃.The mixing of these organic amine compounds and diacetyl oxide can be adopted always known any method.For example, under the situation of continuous mixing, methods such as the kneader of use, extruding machine, static mixer, Banbury are arranged.Under the situation of batch melting, can adopt the container of equipping stirrer to carry out mixing.Add to as mentioned above and carry out mixing organic amine compound and diacetyl oxide in the polyamic acid solution, can directly add like this, add again after also can being diluted in the N,N-dimethylacetamide.

Method 2 in the step (2) is that the polyamic acid solution that will make in the above-mentioned steps (1) carries out curtain coating on carrier, obtain film, gained film and described carrier be impregnated in together in the different imidization solution that contains the solvent the same, dewatering agent diacetyl oxide and organic amine then with step 1, make at least a portion of polyamic acid convert poly-different imide to, form gelatinous membrane.

Polyamic acid solution curtain coating on carrier can be adopted any film-forming methods such as common known wet type and dry-and wet-type forming method.Described film-forming method can be the method for for example die head expressing technique, the curtain coating of using coating roll, use coating machine etc.During the curtain coating polyamic acid, carrier can use metal strip, curtain coating drum etc.Also can be on organic high molecular layers such as polyester or polypropylene curtain coating, and directly import in the condensing agent solution.These optimal processes carry out under low humidity atmosphere.

Used organic amine compound is the compound that the catalysts as diacetyl oxide and polyamic acid works, and for example can use aliphatic tertiary amines such as Trimethylamine 99, triethylamine, Tributylamine, diisopropylethylamine, triethylenediamine; N, accelerine, 1, aromatic amines such as 8-two (N, N-dimethylamino) naphthalene; Pyridine and derivative thereof, picoline and derivative thereof, lutidine, quinoline, isoquinoline 99.9,1,8-diazabicyclo [5.4.0] undecylene, N, heterogeneous ring compounds such as N-dimethyl aminopyridine.Wherein from economic considerations, preferred pyridine and picoline.In addition, triethylenediamine and N, N-dimethyl aminopyridine and diacetyl oxide combination owing to can obtain high imino-ratio, make the high gel film of water tolerance, so preferred the use.At this moment, the amount of organic amine compound with respect to diacetyl oxide is not particularly limited, but is preferably more than 0.5% mole, more preferably more than 10% mole.

Diacetyl oxide concentration in the mixing solutions is not particularly limited, carries out, be preferably 0.5% weight-99% weight for reacting fully.30% weight-99% weight more preferably.Temperature of reaction is not had special stipulation, can adopt the temperature range more than the zero pour of mixing solutions, below the boiling point.

Characteristics we can say the maximum of second method for making just are in this step (2), by making diacetyl oxide and polyamic acid in the solvent that can dissolve polyamic acid, there is reaction down in the organic amine compound catalyzer, obtains evenly and the height swollen is imbued with the not stretching gel film of stretchiness.

In this step (2), at least a portion of polyamic acid has converted poly-different imide to, forms gelatinous membrane.The different imino-ratio of preferred gelatinous membrane is more than 90%, can obtain high stretching ratio like this.

Used organic amine is the compound that the catalysts as diacetyl oxide and polyamic acid works in the method 2, for example can use aliphatic tertiary amines such as Trimethylamine 99, triethylamine, Tributylamine, diisopropylethylamine, triethylenediamine; N, accelerine, 1, aromatic amines such as 8-two (N, N-dimethylamino) naphthalene; Pyridine and derivative thereof, picoline and derivative thereof, lutidine, quinoline, isoquinoline 99.9,1,8-diazabicyclo [5.4.0] undecylene, N, heterogeneous ring compounds such as N-dimethyl aminopyridine.Wherein from economic considerations, preferred pyridine and picoline.In addition, triethylenediamine and N, N-dimethyl aminopyridine and diacetyl oxide combination owing to can obtain high imino-ratio, make the high gel film of water tolerance, so preferred the use.At this moment, the amount of organic amine with respect to diacetyl oxide is not particularly limited, but is preferably more than 0.5% mole, more preferably more than 10% mole, more preferably 50% mole.Diacetyl oxide concentration in the mixing solutions is not particularly limited, carries out, be preferably 0.5% weight-99% weight for reacting fully.30% weight-99% weight more preferably.Temperature of reaction is not had special stipulation, can adopt the temperature range more than the zero pour of mixing solutions, below the boiling point.

The film-forming method of this polyamic acid solution for example has the die head expressing technique, uses the curtain coating of coating roll, uses the method for coating machine etc.During the curtain coating polyamic acid, carrier can use metal strip, curtain coating drum etc.Also can be on organic high molecular layers such as polyester or polypropylene curtain coating, and directly import in the dewatering agent solution.

Described step (2) is preferably carried out under low humidity atmosphere.In this step (2),, can obtain the not stretching gel film that homogeneous and height swollen are imbued with stretchiness by making the reaction of polyamic acid and dewatering agent.

In this step (2), at least a portion of polyamic acid has converted poly-different imide to, forms gelatinous membrane.The different imino-ratio of preferred gelatinous membrane is more than 2%, can obtain high stretching ratio like this.More preferably different imino-ratio is more than 3%, more preferably more than 10%.Thus, characteristics we can say the maximum of step (2) just are to obtain the non-stretched film that homogeneous and height swollen are imbued with the stability that stretches.The different imino-ratio of this gel film and the detailed calculated method of imino-ratio can easily be calculated by infrared absorption spectrum as described later.

Curtain coating forms film and can adopt any film-forming methods such as common known wet type and dry pressing method on carrier.Described film-forming method can be the method for for example die head expressing technique, the curtain coating of using coating roll, use coating machine etc.During the curtain coating polyamic acid, carrier can use metal strip, curtain coating drum etc.Also can use organic high molecular layers such as polyester or polypropylene as carrier.

Organic amine uses for example aliphatic tertiary amines such as Trimethylamine 99, triethylamine pyridine, Tributylamine, diisopropylethylamine, triethylenediamine; N, accelerine, 1, aromatic amines such as 8-two (N, N-dimethylamino) naphthalene; Pyridine derivate, picoline and derivatives thereof such as pyridine and 4-(N, N-dimethyl) aminopyridine.Wherein preferably use pyridine, triethylenediamine, picoline, 4-(N, N-dimethyl) aminopyridine, especially preferably use pyridine, triethylenediamine.

Consumption and strength of solution thereof to imide/different imidization agent are not particularly limited.As long as all be to make the abundant chemical reaction of target amido acid become imide/required amount of different imide in two kinds of methods, the top condition of this tittle is different and different with various conditions such as reaction times, temperature, polyamic acid concentration, curtain coating thickness.

Imide in the gained gel film/different imido ratio is not particularly limited.This ratio has a great difference with the kind difference of imidization agent.

The gel film that obtains by step 2 is evenly and the film of height swollen with good stretchiness as mentioned above.The gel film that obtains to have so good stretchiness is the feature that the present invention is worth a book, be step by the back obtain height-oriented Kapton indispensable condition.

And then for the gel film of step 2, preferably the different imino-ratio of its component of polymer and imino-ratio sum are below 60%.This aggregate value is 60% when above, and the orientation effect that obtains by stretching in the subsequent step 3 is not enough, in the subsequent step 4 deterioration etc. will take place, and the situation that mechanical properties descends occurs.More preferably this aggregate value is more than 80%.The different imino-ratio of this gel film and the detailed calculated method of imino-ratio sum can easily be calculated by infrared absorption spectrum as described later.

Above-mentioned steps 2 among the present invention is preferably carried out under low humidity atmosphere.Preferably in inert gas atmospheres such as nitrogen, argon gas or dry air, carry out,, most preferably in dry air, carry out from industrial production cost equal angles.

This gel film comprises the material after other organic solvent except that imidization catalyst, cleaning solvent etc. has been removed in washing.Washing methods, temperature, time are not particularly limited, for example in steps in 1 as the aromatic hydrocarbons such as material, toluene or other alkyl benzene of solvent, with the aliphatic alcohol class headed by the Virahol or higher alcohols, benzylalcohol or other ester class organic solvent, organic solvent of ketone etc., this gel film can flood washing in these organic solvents.Particularly making with dicyclohexylcarbodiimide under the situation of gel film,, be in subsequent step, to obtain effective stretch orientation effect, preferably in toluene etc., carrying out thorough washing owing in the gel film a lot of different imino-s are arranged.On the other hand, making with aliphatic anhydrides and organic amine under the situation of gel film, owing in the gel film more imino-is arranged, thereby preferably use the organic solvent identical to wash with the polyamic acid polymer solvent.The washing of gel film can be period gel film on carrier in, it also can not the stage that rests on step 2, but for example after the step 3 from the carrier after separating wash, perhaps and then stretch processing after wash, can divide several to carry out in each period.

In the step 3, step 2 gained gel film is separated from carrier, carry out biaxial stretching then.Can stretch with 1.03-10.0 multiplying power doubly on all directions in length and breadth.Preferred 1.05-8.00 times, more preferably 1.10-6.00 doubly.Draft temperature is not particularly limited for example preferred-10 ℃ to 100 ℃.More preferably-5 ℃ to 90 ℃, further preferred 0 ℃ to 80 ℃.Stretching can be adopted one by one drawing process, any method such as biaxial stretching method simultaneously, and can be in solvent, in the air, carry out in the medium any atmosphere of inert atmosphere.Particularly preferably in carrying out in the air.

The gel film of the biaxial stretching of preferred supplying step 3 has the swelling capacity of 200-10000%.If be lower than 200%, the situation of abundant stretchiness then can appear can not get.And if be higher than 10000%, sufficient self-supporting then can appear obtaining, be difficult to supply with the situation of stretching step.More preferably swelling capacity is 250-9000%, more preferably 300-8000%.

At last, in step 4, will heat-treat, form the Kapton of biax orientation by the biaxially drawn films that step 3 makes.Heat treating method has hot blast heating, heating under vacuum, infrared heating, microwave heating, and also useful hot plate, hot-rolling carry out methods such as Contact Heating.At this moment, preferably by elevated temperature progressively, remove desolvate and drying, imidization and/or different imide to imido conversion reaction.

This thermal treatment can or exist under the tensile situation in fixed length to be carried out.Beginning temperature to thermal treatment temp is not particularly limited, and preferably heat-treats as top temperature with 250-650 ℃.Can multistep heat up gradually and/or the cooling situation under carry out.In a word, by this thermal treatment, can suppress to be orientated the lax imidization rate that obtains simultaneously and surpass 95% Kapton.The thermal treatment that is lower than 250 ℃ is difficult to realize surpassing 95% imidization rate, if will obtain to surpass 95% imidization rate, then needs the long time, thereby not preferred.Be higher than under 650 ℃ the pyroprocessing situation, the situation of polyimide generation thermal degradation when can occur, thus not preferred.Preferably 300-600 ℃, more preferably 350-550 ℃.

As mentioned above, the biax orientation Kapton that makes is the Kapton of the high Young's modulus that molecular chain is orientated in pellicular front strongly, in-plane equilibrium is good, be that the Young's modulus value that records on two vertical direction in face surpasses 3GPa, more preferably surpass 6GPa, and formed special microtexture, and the film that therefore intensity is improved by stretch orientation.Such high Young's modulus Kapton even thickness is the following films of 10 μ m, also can be used for electronic applications because of the rigidity height, for example lamination the circuit board carrier etc. of Copper Foil.Also can be used as the winding of metallic circuit, flexible circuit board, TAB (flexible band is from being dynamically connected), the supporter that LOC (Lead-on-Chip encapsulation) uses band.Can also be as the basilar membrane of tape.

Embodiment

By the following examples the inventive method is carried out detailed specific description.But these embodiment do not constitute any limitation of the invention.

The reducing viscosity of polyamic acid is as lysate, in polymer concentration 0.05wt%, 0 ℃ of value of measuring down of temperature with 1wt% lithium chloride/nmp solution.

Swelling capacity (wt/wt%) is calculated by following formula (3) by weight under the solvent swelling state (Ww) and the weight (Wd) under the drying regime.

Swelling capacity (wt/wt%)=(Ww/Wd-1) * 100 ... (3)

Tensile strength, extension at break and Young's modulus are the samples with 50mm * 10mm, with 5mm/ minute draw speed, measure with Orientech UCT-1T.

Different imino-ratio and imino-ratio are with Fourier transform infrared spectrophotometer (Nicolet Magna 750), by the result who records through transmission method, calculate with following formula (4), (5).

Different imino-ratio (%)=(A ₉₂₀/ A ₁₀₂₄)/11.3 * 100 ... (4)

A ₉₂₀: the peak (920cm that is derived from different imido key of sample ^-1) absorption intensity

A ₁₀₂₄: the peak (1024cm that is derived from phenyl ring of sample ^-1) absorption intensity

Imino-ratio (%)=(A ₇₂₀/ A ₁₀₂₄)/5.1 * 100 ... (5)

A ₇₂₀: the peak (720cm that is derived from the imido key of sample ^-1) absorption intensity

A ₁₀₂₄: the peak (1024cm that is derived from phenyl ring of sample ^-1) absorption intensity

Pressure cooker is handled (PCT): with film in the HAST chamber (EHS-221M) that Tabai Espec makes under 121 ℃, 100%RH condition wet heat treatment 24 hours.

Rate of moisture absorption is that sample was placed 72 hours under the atmosphere of 25 ℃ of temperature, relative humidity 72%RH, measures its weight (W1), and with this sample on 270 ℃ hot air dryer dry 30 minutes, gravimetry (W2) calculated with following formula (6) then then.

Rate of moisture absorption (wt/wt%)=(W1/W2-1) * 100 ... (6)

The imino-concentration [imide] of polyimide is the normal value of existing imino-in the expression 1kg polyimide, can calculate by following formula (7).

[imide] be (average repeating unit molecular weight) (eq/kg)=2000/ ... (7)

Comparative example 1

In the reaction vessel that thermometer, whipping appts and raw materials mouth are housed, under nitrogen atmosphere, add 1920g dehydration N-N-methyl-2-2-pyrrolidone N-(hereinafter referred to as NMP), add the 26.52g Ursol D again, it is dissolved fully.With the ice bath cooling, make the temperature of two amine aqueous solutions reach 3 ℃ afterwards.In these cooled two amine aqueous solutions, add 53.46g pyromellitic acid acid anhydride, make its reaction 1 hour.This moment, the temperature of reaction soln was 5-20 ℃.This reaction solution was reacted 3 hours down in room temperature (23 ℃), add the 0.091g Tetra hydro Phthalic anhydride then, make its reaction carry out the amine end-blocking in 1 hour, obtain polyamic acid nmp solution into viscous solution.The reducing viscosity of gained polyamic acid is 13.8.

Gained polyamic acid solution scraper plate with thick 1.0mm on sheet glass is carried out curtain coating, dipping is 30 minutes in 30 ℃ of dehydrating condensations that contain 250ml diacetyl oxide, 74g triethylenediamine and 2000ml NMP are bathed, make its imide/different imidization, separate from the carrier sheet glass, obtain gel film.The imino-ratio of this gel film is 83%, and different imino-ratio is 3%.

With the gained gel film in NMP under room temperature dipping washed in 20 minutes, then the two ends of this gel film are fixed with chuck, at room temperature, carry out biaxial stretching simultaneously with the speed of 10mm/sec on axially, make the stretching ratio on all directions all reach 1.05 times at vertical two.The swelling capacity of the gel film when stretching beginning is 1510%.

With the gel film frame fixation after stretching, on the hot air dryer that uses dry air from 160 ℃ of temperature-gradient methods to 300 ℃, enforcement drying and thermal treatment.Use heated air circulation type baking oven temperature-gradient method to 300 ℃-450 ℃ then, obtain Kapton.

Young's modulus, tensile strength, extension at break and the imino-ratio measured on the thickness of gained Kapton, two vertical direction in face are as shown in table 1.This film is carried out after PCT handles, and the remarkable embrittlement of film is so that can not carry out the mechanical properties evaluation.

[imide] of this Kapton is 6.89eq/kg.

Embodiment 1

In the reaction vessel that thermometer, whipping appts and raw materials mouth are housed, under nitrogen atmosphere, add 2010g NMP, add 40.95g Ursol D and 91.77g 3 again, 4 '-DAPE (aromatic diamine compound shown in the following formula (IV-i-a)) dissolves it fully.With the ice bath cooling, make the temperature of two amine aqueous solutions reach 3 ℃ afterwards.In these cooled two amine aqueous solutions, add 181.8g pyromellitic acid acid anhydride, make its reaction 1 hour.This moment, the temperature of reaction soln was 5-20 ℃.This reaction solution was reacted 8 hours down in room temperature (23 ℃), add the 0.247g Tetra hydro Phthalic anhydride then, make its reaction carry out the amine end-blocking in 1 hour, obtain polyamic acid nmp solution into viscous solution.The NMP concentration of gained polyamic acid is 13wt%, and reducing viscosity is 6.39.

Polyamic acid nmp solution scraper plate with thick 1.0mm on sheet glass of gained 13wt% is carried out curtain coating, dipping is 30 minutes in 30 ℃ of dehydrating condensations that contain 1050ml diacetyl oxide, 450ml pyridine and 1500ml NMP are bathed, make its imide/different imidization, separate from the carrier sheet glass, obtain gel film.The imino-ratio of this gel film is 82%, and different imino-ratio is 18%.

With the gained gel film in NMP under room temperature dipping washed in 20 minutes, then the two ends of this gel film are fixed with chuck, at room temperature, carry out biaxial stretching simultaneously with the speed of 10mm/sec on axially, make the stretching ratio on all directions all reach 3.10 times at vertical two.The swelling capacity of the gel film when stretching beginning is 394%.

With the gel film frame fixation after stretching, on the hot air dryer that uses dry air from 160 ℃ of temperature-gradient methods to 300 ℃, enforcement drying and thermal treatment.Use heated air circulation type baking oven temperature-gradient method to 300 ℃-450 ℃ then, obtain Kapton.

Young's modulus, tensile strength, extension at break and the imino-ratio measured on the thickness of gained Kapton, two vertical direction in face are as shown in table 1.This film is carried out not seeing obvious deterioration after PCT handles.Young's modulus, tensile strength, extension at break after PCT handles are as shown in table 1.

[imide] of this Kapton is 5.87eq/kg.

Embodiment 2

In the reaction vessel that thermometer, whipping appts and raw materials mouth are housed, under nitrogen atmosphere, add 1800g dehydration NMP, add 58.03g Ursol D and 11.93g 3 again, 4 '-DAPE (aromatic diamine compound shown in the following formula (IV-i-a)) dissolves it fully.With the ice bath cooling, make the temperature of two amine aqueous solutions reach 3 ℃ afterwards.In these cooled two amine aqueous solutions, add 130.0g pyromellitic acid acid anhydride, make its reaction 1 hour.This moment, the temperature of reaction soln was 5-20 ℃.This reaction solution was reacted 8 hours down in room temperature (23 ℃).Add the 0.221g Tetra hydro Phthalic anhydride then, make its reaction carry out the amine end-blocking in 1 hour, obtain polyamic acid nmp solution into viscous solution.The gained polyamic acid is diluted to 4wt% with dehydration NMP, is used to make film.The reducing viscosity of gained polyamic acid is 7.94.

Polyamic acid nmp solution scraper plate with thick 1.5mm on sheet glass of gained 4wt% is carried out curtain coating, dipping is 30 minutes in 30 ℃ of dehydrating condensations that contain 1050ml diacetyl oxide, 450ml pyridine and 1500ml NMP are bathed, make its imide/different imidization, separate from the carrier sheet glass, obtain gel film.The imino-ratio of this gel film is 49%, and different imino-ratio is 41%.

With the gained gel film in NMP under room temperature dipping washed in 20 minutes, then the two ends of this gel film are fixed with chuck, at room temperature, carry out biaxial stretching simultaneously with the speed of 10mm/sec on axially, make the stretching ratio on all directions all reach 1.80 times at vertical two.The swelling capacity of the gel film when stretching beginning is 1820%.

With the gel film frame fixation after stretching, on the hot air dryer that uses dry air from 160 ℃ of temperature-gradient methods to 300 ℃, enforcement drying and thermal treatment.Use heated air circulation type baking oven temperature-gradient method to 300 ℃-450 ℃ then, obtain Kapton.Young's modulus, tensile strength, extension at break, elongation and rate of moisture absorption and the imino-ratio measured on the thickness of gained Kapton, two vertical direction in face are as shown in table 1.

[imide] of this Kapton is 6.68eq/kg.

Embodiment 3

The 4wt% polyamic acid nmp solution of gained among the embodiment 2 is used to make film.With embodiment 2 the same operations, this polyamic acid nmp solution is carried out curtain coating and makes it carry out gelation reaction, obtain gel film.This moment, the imino-ratio of gel film was 45%, and different imino-ratio is 43%.

Then, all make vertical two all directions stretching ratios on axially into 1.90 times, in addition, carry out the stretching of gel film with embodiment 2 the same operations.And then the thermal treatment outlet temperature become 450 ℃, in addition, carry out the drying and the thermal treatment of film with embodiment 2 the same operations.Young's modulus, tensile strength, elongation and rate of moisture absorption and the imino-ratio measured on the thickness of gained Kapton, two vertical direction in face are as shown in table 1.

[imide] of this Kapton is 6.68eq/kg.

Embodiment 4

Use 50.20g Ursol D and 23.22g 3, in addition 4 '-DAPE, 126.5g pyromellitic acid acid anhydride, 0.215g Tetra hydro Phthalic anhydride with embodiment 2 the same operations, carry out the polyamic acid polymerization.This polyamic acid is diluted to 5wt% with dehydration NMP, is used to make film.The reducing viscosity of gained polyamic acid is 10.8.

Polyamic acid nmp solution and the embodiment 2 the same films made from gained 5wt% obtain gel film.The imino-ratio of this gel film is 39%, and different imino-ratio is 38%.Carry out for 2.10 times with all directions at vertical two stretching ratios on axially, in addition, obtain Kapton with embodiment 2 the same operations.The swelling capacity of the gel film when stretching beginning is 1910%.Young's modulus, tensile strength, elongation and rate of moisture absorption and the imino-ratio measured on the thickness of gained Kapton, two vertical direction in face are as shown in table 1.

[imide] of this Kapton is 6.48eq/kg.

Embodiment 5

Use 42.79g Ursol D and 33.93g 3, in addition 4 '-DAPE, 123.2g pyromellitic acid acid anhydride, 0.209g Tetra hydro Phthalic anhydride with embodiment 2 the same operations, carry out the polyamic acid polymerization.This polyamic acid is diluted to 6wt% with dehydration NMP, is used to make film.The reducing viscosity of gained polyamic acid is 7.91.

Polyamic acid nmp solution and the embodiment 2 the same films made from gained 6wt% obtain gel film.The imino-ratio of this gel film is 46%, and different imino-ratio is 31%.Carry out for 2.40 times with all directions at vertical two stretching ratios on axially, in addition, obtain Kapton with embodiment 2 the same operations.The swelling capacity of the gel film when stretching beginning is 1990%.Young's modulus, tensile strength, elongation and rate of moisture absorption and the imino-ratio measured on the thickness of gained Kapton, two vertical direction in face are as shown in table 1.

[imide] of this Kapton is 6.29eq/kg.

Table 1

	I (% mole)	II (% mole)	Thickness (μ m)	??PCT	Measure direction	Young's modulus (GPa)	Intensity (MPa)	Elongation (%)	Rate of moisture absorption (%)	Imino-ratio (%)
											Comparative example 1	??100	??0	??21	Be untreated	??MD ??TD	??15 ??14	??370 ??360	??4 ??3	??4.8	??99
After the processing	??MD ??TD	Can't measure	Can't measure	Can't measure	Can't measure	??-
							Embodiment 1	??45	??55	??12					Be untreated	??MD ??TD	??9 ??9	??320 ??330	??30 ??31	??-	??-
After the processing	??MD ??TD	??10 ??9	??280 ??270	??20 ??24	??-	??-
											Embodiment 2	??90	??10	??15	Be untreated	??MD ??TD	??10 ??11	??429 ??433	??9 ??6	??3.2	??99
Embodiment 3	??90	??10	??12	Be untreated	??MD ??TD	??12 ??13	??260 ??330	??9 ??15	??3.1	??99
											Embodiment 4	??90	??20	??11	Be untreated	??MD ??TD	??12 ??11	??280 ??300	??8 ??24	??2.7	??99
Embodiment 5	??70	??30	??9	Be untreated	??MD ??TD	??10 ??10	??330 ??270	??34 ??27	??1.9	??99

Embodiment 6

In the reaction vessel that thermometer, whipping appts and raw materials mouth are housed, under nitrogen atmosphere, add 1800g dehydration NMP, add 56.47g Ursol D and 16.96g APB (aromatic diamine compound shown in the following formula (IV-ii-a)) again, it is dissolved fully.With the ice bath cooling, make the temperature of two amine aqueous solutions reach 3 ℃ afterwards.In these cooled two amine aqueous solutions, add 126.5g pyromellitic acid acid anhydride, make its reaction 1 hour.This moment, the temperature of reaction soln was 5-20 ℃.This reaction solution was reacted 8 hours down in room temperature (23 ℃).Add the 0.215g Tetra hydro Phthalic anhydride then, make its reaction carry out the amine end-blocking in 1 hour, obtain polyamic acid nmp solution into viscous solution.The gained polyamic acid is diluted to 4wt% with dehydration NMP, is used to make film.The reducing viscosity of gained polyamic acid is 13.5.

Polyamic acid nmp solution scraper plate with thick 1.5mm on sheet glass of gained 4wt% is carried out curtain coating, dipping is 30 minutes in 30 ℃ of dehydrating condensations that contain 1050ml diacetyl oxide, 450ml pyridine and 1500ml NMP are bathed, make its imide/different imidization, separate from the carrier sheet glass, obtain gel film.The imino-ratio of this gel film is 44%, and different imino-ratio is 38%.

With the gained gel film in NMP under room temperature dipping washed in 20 minutes, then the two ends of this gel film are fixed with chuck, at room temperature, carry out biaxial stretching simultaneously with the speed of 10mm/sec on axially, make the stretching ratio on all directions all reach 1.84 times at vertical two.The swelling capacity of the gel film when stretching beginning is 1900%.

With the gel film frame fixation after stretching, on the hot air dryer that uses dry air from 160 ℃ of temperature-gradient methods to 300 ℃, enforcement drying and thermal treatment.Use heated air circulation type baking oven temperature-gradient method to 300 ℃-450 ℃ then, obtain Kapton.Young's modulus, tensile strength, extension at break, elongation and rate of moisture absorption and the imino-ratio measured on the thickness of gained Kapton, two vertical direction in face are as shown in table 2.

[imide] of this Kapton is 6.48eq/kg.

Embodiment 7

Vertical two stretching ratios on are axially changed into all directions carry out for 1.80 times, in addition, obtain Kapton with embodiment 6 the same operations.Young's modulus, tensile strength, extension at break and rate of moisture absorption and the imino-ratio measured on the thickness of gained Kapton, two vertical direction in face are as shown in table 2.

[imide] of this Kapton is 6.48eq/kg.

Embodiment 8

Vertical two stretching ratios on are axially changed into all directions carry out for 1.65 times, in addition, obtain Kapton with embodiment 6 the same operations.Young's modulus, tensile strength, extension at break and rate of moisture absorption and the imino-ratio measured on the thickness of gained Kapton, two vertical direction in face are as shown in table 2.

[imide] of this Kapton is 6.48eq/kg.

Embodiment 9

Make the final thermal treatment temp in the system film step into 350 ℃, in addition, obtain Kapton with embodiment 6 the same operations.Young's modulus, tensile strength, extension at break and rate of moisture absorption and the imino-ratio measured on the thickness of gained Kapton, two vertical direction in face are as shown in table 2.

[imide] of this Kapton is 6.48eq/kg.

Embodiment 10

Use 47.65g Ursol D and 32.20g APB (aromatic diamine compound shown in the following formula (IV-ii-a)), 120.1g pyromellitic acid acid anhydride, 0.20g Tetra hydro Phthalic anhydride, in addition, carry out the polyamic acid polymerization with embodiment 6 the same operations.This polyamic acid is diluted to 5wt% with dehydration NMP, is used to make film.The reducing viscosity of gained polyamic acid is 10.8.

Polyamic acid nmp solution and the embodiment 6 the same films made from gained 5wt% obtain gel film.The imino-ratio of this gel film is 44%, and different imino-ratio is 38%.Carry out for 1.86 times with all directions at vertical two stretching ratios on axially, in addition with embodiment 6 the same stretchings.The swelling capacity of the gel film when stretching beginning is 2180%.With this gel film and embodiment 6 the same heat-treating, obtain Kapton.Young's modulus, tensile strength, extension at break and rate of moisture absorption and the imino-ratio measured on the thickness of gained Kapton, two vertical direction in face are as shown in table 2.

[imide] of this Kapton is 6.11eq/kg.

Embodiment 11

Use 39.68g Ursol D and 45.97g APB (aromatic diamine compound shown in the following formula (IV-ii-a)), 114.3g pyromellitic acid acid anhydride, 0.19g Tetra hydro Phthalic anhydride, in addition, carry out the polyamic acid polymerization with embodiment 6 the same operations.This polyamic acid is diluted to 6wt% with dehydration NMP, is used to make film.The reducing viscosity of gained polyamic acid is 11.9.

Polyamic acid nmp solution and the embodiment 6 the same films made from gained 6wt% obtain gel film.The imino-ratio of this gel film is 44%, and different imino-ratio is 39%.Carry out for 2.00 times with all directions at vertical two stretching ratios on axially, in addition with embodiment 6 the same stretchings.The swelling capacity of the gel film when stretching beginning is 2320%.With this gel film and embodiment 6 the same heat-treating, obtain Kapton.Young's modulus, tensile strength, extension at break and rate of moisture absorption and the imino-ratio measured on the thickness of gained Kapton, two vertical direction in face are as shown in table 2.

This film is carried out not seeing significant deterioration after PCT handles.Young's modulus, tensile strength, extension at break after PCT handles are as shown in table 2.

[imide] of this Kapton is 5.79eq/kg.

Embodiment 12

Use the polyamic acid nmp solution of the 5wt% of gained among the embodiment 10, dehydrating condensation is bathed consists of 250ml diacetyl oxide, 74g triethylenediamine and 2000ml NMP, in addition with embodiment 2 the same operations, obtains gel film.The imino-ratio of this gel film is 96%, and different imino-ratio is 1%.All make vertical two all directions stretching ratios on axially into 1.46 times, in addition with embodiment 6 the same stretchings.The swelling capacity of the gel film when stretching beginning is 1620%.With this gel film and embodiment 6 the same heat-treating, obtain Kapton.Young's modulus, tensile strength, elongation and rate of moisture absorption and the imino-ratio measured on the thickness of gained Kapton, two vertical direction in face are as shown in table 2.

[imide] of this Kapton is 6.11eq/kg.

Table 2

	I (% mole)	II (% mole)	Thickness (μ m)	??PCT	Measure direction	Young's modulus (GPa)	Intensity (MPa)	Elongation (%)	Rate of moisture absorption (%)	Imino-ratio (%)
											Embodiment 6	??90	??10	??14	Be untreated	??MD ??TD	??14 ??15	??429 ??433	??10 ??10	??2.9	??98
Embodiment 7	??90	??10	??15	Be untreated	??MD ??TD	??16 ??13	??444 ??464	??14 ??15	??2.8	??99
											Embodiment 8	??90	??10	??19	Be untreated	??MD ??TD	??14 ??15	??391 ??428	??10 ??12	??3.0	??99
Embodiment 9	??90	??10	??16	Be untreated	??MD ??TD	??13 ??14	??341 ??352	??17 ??12	??2.8	??99
											Embodiment 10	??80	??20	??23	Be untreated	??MD ??TD	??13 ??14	??385 ??405	??12 ??16	??2.5	??99
Embodiment 11	? ??70	? ??30	? ??18	Be untreated	??MD ??TD	??13 ??13	??397 ??382	??21 ??16	??1.8	??99
											After the processing	??MD ??TD	??14 ??14	??338 ??351	??17 ??14	??-	??-
				Embodiment 12	??80	??20	??27	Be untreated	??MD ??TD	??13 ??13								??395 ??403	??22 ??19	??2.4	??98

Embodiment 13

In the reaction vessel that thermometer, whipping appts and raw materials mouth are housed, under nitrogen atmosphere, add 1800g dehydration NMP, add 54.27g Ursol D and 24.10gBAPS-M (aromatic diamine compound shown in the following formula (IV-iv-a)) again, it is dissolved fully.With the ice bath cooling, make the temperature of two amine aqueous solutions reach 3 ℃ afterwards.In these cooled two amine aqueous solutions, add 121.4g pyromellitic acid acid anhydride, make its reaction 1 hour.This moment, the temperature of reaction soln was 5-20 ℃.This reaction solution was reacted 4 hours down in room temperature (23 ℃).Add the 0.206g Tetra hydro Phthalic anhydride then, make its reaction carry out the amine end-blocking in 1 hour, obtain polyamic acid nmp solution into viscous solution.This polyamic acid is diluted to 5wt% with dehydration NMP, is used to make film.The reducing viscosity of gained polyamic acid is 6.1.

Polyamic acid nmp solution scraper plate with thick 1.5mm on sheet glass of gained 5wt% is carried out curtain coating, dipping is 30 minutes in 30 ℃ of dehydrating condensations that contain 1050ml diacetyl oxide, 450ml pyridine and 1500ml NMP are bathed, make its imide/different imidization, separate from the carrier sheet glass, obtain gel film.The imino-ratio of this gel film is 41%, and different imino-ratio is 39%.

With the gained gel film in NMP under room temperature dipping washed in 20 minutes, then the two ends of this gel film are fixed with chuck, at room temperature, carry out biaxial stretching simultaneously with the speed of 10mm/sec on axially, make the stretching ratio on all directions all reach 1.8 times at vertical two.The swelling capacity of the gel film when stretching beginning is 1860%.

With the gel film frame fixation after stretching, on the hot air dryer that uses dry air from 160 ℃ of temperature-gradient methods to 300 ℃, enforcement drying and thermal treatment.Use heated air circulation type baking oven temperature-gradient method to 300 ℃-450 ℃ then, obtain Kapton.Young's modulus, tensile strength, extension at break, elongation and rate of moisture absorption and the imino-ratio measured on the thickness of gained Kapton, two vertical direction in face are as shown in table 3.

[imide] of this Kapton is 6.20eq/kg.

Embodiment 14

Vertical two stretching ratios on are axially changed into all directions carry out for 1.58 times, in addition, obtain Kapton with embodiment 13 the same operations.Young's modulus, tensile strength, elongation and rate of moisture absorption and the imino-ratio measured on the thickness of gained Kapton, two vertical direction in face are as shown in table 3.

[imide] of this Kapton is 6.20eq/kg.

Embodiment 15

Change vertical two stretching ratios on axially into all directions 1.58 times, and change the thermal treatment outlet temperature into 350 ℃, in addition, obtain Kapton with embodiment 13 the same operations.Young's modulus, tensile strength, elongation and rate of moisture absorption and the imino-ratio measured on the thickness of gained Kapton, two vertical direction in face are as shown in table 3.

[imide] of this Kapton is 6.20eq/kg.

Embodiment 16

To carry out curtain coating with polyamic acid nmp solution scraper plate with thick 1.0mm on sheet glass of the embodiment 13 the same 5wt% that make, dipping is 30 minutes in 30 ℃ of dehydrating condensations that contain 250ml diacetyl oxide, 74g triethylenediamine and 2000ml NMP are bathed, make its imide/different imidization, separate from the carrier sheet glass, obtain gel film.The imino-ratio of this gel film is 96%, and different imino-ratio is 2%.

With the gained gel film in NMP under room temperature dipping washed in 20 minutes, then the two ends of this gel film are fixed with chuck, at room temperature, carry out biaxial stretching simultaneously with the speed of 10mm/sec on axially, make the stretching ratio on all directions all reach 1.4 times at vertical two.The swelling capacity of the gel film when stretching beginning is 1860%.

With the gel film frame fixation after stretching, on the hot air dryer that uses dry air from 160 ℃ of temperature-gradient methods to 300 ℃, enforcement drying and thermal treatment.Use heated air circulation type baking oven temperature-gradient method to 300 ℃-450 ℃ then, obtain Kapton.Young's modulus, tensile strength, elongation and rate of moisture absorption and the imino-ratio measured on the thickness of gained Kapton, two vertical direction in face are as shown in table 3.

[imide] of this Kapton is 6.20eq/kg.

Embodiment 17

Use 35.75g Ursol D and 61.23g BAPS-M (aromatic diamine compound shown in the following formula (IV-iv-a)), 103.0g pyromellitic acid acid anhydride, 0.176g Tetra hydro Phthalic anhydride, and polymerization time is set at 6 hours, in addition equally carry out polymerization with embodiment 13.This polyamic acid is diluted to 6wt% with dehydration NMP, is used to make film.The reducing viscosity of gained polyamic acid is 7.2.

Polyamic acid nmp solution and the embodiment 13 the same films made from gained 6wt% obtain gel film.The imino-ratio of this gel film is 43%, and different imino-ratio is 35%.Carry out for 2.1 times with all directions at vertical two stretching ratios on axially, in addition with embodiment 14 the same stretchings.The swelling capacity of the gel film when stretching beginning is 2120%.With this gel film and embodiment 13 the same heat-treating, obtain Kapton.Young's modulus, tensile strength, elongation and rate of moisture absorption and the imino-ratio measured on the thickness of gained Kapton, two vertical direction in face are as shown in table 3.

[imide] of this Kapton is 5.16eq/kg.

Embodiment 18

Use 54.27g Ursol D, 24.10g BAPS (aromatic diamine compound shown in the following formula (IV-iv-b)) and 121.4g pyromellitic acid acid anhydride as raw material monomer, in addition equally carry out polymerization with embodiment 13.Obtain the polyamic acid nmp solution of 5wt%.The reducing viscosity of gained polyamic acid is 7.6.

Make film, stretching, thermal treatment with the polyamic acid nmp solution of gained 5wt% and embodiment 13 are the same.This moment, the imino-ratio of gained gel film was 44%, and different imino-ratio is 32%, and the swelling capacity of the gel film when stretching beginning is 1790%.Young's modulus, tensile strength, elongation and rate of moisture absorption and the imino-ratio measured on the thickness of gained Kapton, two vertical direction in face are as shown in table 3.

[imide] of this Kapton is 6.20eq/kg.

Embodiment 19

Use 57.20g Ursol D, 14.59g two (3-aminophenyl) sulfone and 128.1g pyromellitic acid acid anhydride as raw material monomer, in addition equally carry out polymerization, obtain the polyamic acid nmp solution of 5wt% with embodiment 13.The reducing viscosity of gained polyamic acid is 8.3.

Make film, stretching, thermal treatment with the polyamic acid nmp solution of gained 5wt% and embodiment 13 are the same.This moment, the imino-ratio of gained gel film was 38%, and different imino-ratio is 39%, and the swelling capacity of the gel film when stretching beginning is 1840%.Young's modulus, tensile strength, elongation and rate of moisture absorption and the imino-ratio measured on the thickness of gained Kapton, two vertical direction in face are as shown in table 3.

[imide] of this Kapton is 6.57eq/kg.

Table 3

	I (% mole)	II (% mole)	Thickness (μ m)	??PCT	Measure direction	Young's modulus (GPa)	Intensity (MPa)	Elongation (%)	Rate of moisture absorption (%)	Imino-ratio (%)
											Embodiment 13	??90	??10	??17	Be untreated	??MD ??TD	??16 ??15	??428 ??407	??12 ??11	??3.1	??99
Embodiment 14	??90	??10	??26	Be untreated	??MD ??TD	??13 ??13	??392 ??372	??8 ??7	??3.2	??99
											Embodiment 15	??90	??10	??25	Be untreated	??MD ??TD	??12 ??11	??314 ??284	??5 ??7	??3.2	??99
Embodiment 16	??90	??10	??29	Be untreated	??MD ??TD	??13 ??11	??368 ??381	??10 ??10	??3.3	??99
											Embodiment 17	??70	??30	??10	Be untreated	??MD ??TD	??11 ??10	??373 ??354	??21 ??18	??1.8	??99
Embodiment 18	??90	??10	??16	Be untreated	??MD ??TD	??16 ??16	??380 ??392	??9 ??10	??3.0	??99
											Embodiment 19	??90	??10	??17	Be untreated	??MD ??TD	??15 ??14	??378 ??381	??11 ??10	??3.1	??99

Embodiment 20

In the reaction vessel that thermometer, whipping appts and raw materials mouth are housed, adding the 20L water ratio under nitrogen atmosphere is the dehydration NMP of 10ppm, add 225.29g Ursol D and 417.41g 3 again, 4 '-DAPE (aromatic diamine compound shown in the following formula (IV-i-a)) dissolves it fully.With the ice bath cooling, the temperature of two amine aqueous solutions is reached-5 ℃ afterwards.In these cooled two amine aqueous solutions, add 909.08g pyromellitic acid acid anhydride, make its reaction 1 hour.This moment, the temperature of reaction soln was 0-5 ℃.Make this reaction solution 10-15 ℃ of reaction 4 hours again.Add the 1.23g Tetra hydro Phthalic anhydride then, make its reaction carry out the amine end-blocking in 2 hours, obtain polyamic acid nmp solution into viscous solution.The concentration of this polyamic acid nmp solution is 7wt%, and the reducing viscosity of gained polyamic acid is 9.1.

The polyamic acid nmp solution of gained 7wt% is cooled to-10 ℃ under nitrogen atmosphere, add pyridine with the ratio that is 4 moles of pyridines with respect to 1 mole of polyamic acid repeating unit then, mix with static mixer, add diacetyl oxide with the ratio that is 6 mole of acetic anhydride with respect to 1 mole of polyamic acid repeating unit subsequently, mix with static mixer.Dehydration reaction does not take place in gained polyamic acid nmp solution composition, keeps the state of viscous solution.Polyamic acid nmp solution composition extruded by die head on the PET film carry out curtain coating, making its thickness is 0.5mm.Directly be warming up to 40 ℃ with carrier PET film.At this moment,, heat up after 1 hour, at room temperature impregnated among the NMP and wash together with carrier by the beginning dehydration reaction that heats up.Carrier of separating obtains evenly and is imbued with the gel film of stretchiness.The imino-ratio of this gel film is 74%, and different imino-ratio is 21%.

The two ends of this gel film are fixed with chuck, at room temperature, carried out biaxial stretching simultaneously with the speed of 10mm/sec on axially, make the stretching ratio of MD direction/TD direction be respectively 2.4 times/2.8 times at vertical two.The swelling capacity of the gel film when stretching beginning is 1181%.

With the gel film frame fixation after stretching, on the hot air dryer that uses dry air from 160 ℃ of temperature-gradient methods to 300 ℃, enforcement drying and thermal treatment.Use heated air circulation type baking oven temperature-gradient method to 300 ℃-450 ℃ then, obtain Kapton.Young's modulus, tensile strength, extension at break, elongation and rate of moisture absorption and the imino-ratio measured on the thickness of gained Kapton, two vertical direction in face are as shown in table 4.

[imide] of this Kapton is 5.95eq/kg.

Embodiment 21

Use the polyamic acid nmp solution composition that makes among the embodiment 20, and be 1.0mm, in addition, obtain gel film with embodiment 20 the same operations with thickness setting.The imino-ratio of this gel film is 71%, and different imino-ratio is 28%.

The two ends of this gel film are fixed with chuck, at room temperature, carried out biaxial stretching simultaneously with the speed of 10mm/sec on axially, make the stretching ratio of MD direction/TD direction be respectively 2.1 times/2.7 times at vertical two.The swelling capacity of the gel film when stretching beginning is 1283%.

Carry out drying and thermal treatment with the gel film after stretching and embodiment 20 are the same, obtain Kapton.Young's modulus, tensile strength, elongation and rate of moisture absorption and the imino-ratio measured on the thickness of gained Kapton, two vertical direction in face are as shown in table 4.

This film is carried out not seeing tangible deterioration after PCT handles.Young's modulus, tensile strength, extension at break after PCT handles are as shown in table 4.

[imide] of this Kapton is 5.95eq/kg.

Table 4

	I (% mole)	II (% mole)	Thickness (μ m)	??PCT	Measure direction	Young's modulus (GPa)	Intensity (MPa)	Elongation (%)	Rate of moisture absorption (%)	Imino-ratio (%)
											Embodiment 20	??50	??50	??5	Be untreated	??MD ??TD	??9 ??9	??313 ??318	??34 ??31	??1.8	??98
Embodiment 21	??50	??50	??12	Be untreated	??MD ??TD	??9 ??9	??368 ??337	??48 ??51	??1.7	??99
											After the processing	??MD ??TD	??10 ??9	??325 ??312	??35 ??36	??-	???-

Claims (15)

1. Kapton, this film is to form by constituting the unit shown in the following formula (II) that constitutes unit and 1% mole-70% molar ratio shown in 30% mole-99% mole the following formula (I), it is characterized in that: having Young's modulus in the face is the above vertical both direction of 3GPa, at 72%RH, 25 ℃ rate of moisture absorption is below the 3.3wt%

Ar ^IaNon-reacted substituent 1 for containing, the 4-phenylene;

Ar ^IIaAnd Ar ^IIbIndependent of separately containing the aryl of non-reacted substituent carbonatoms 6-20, the X in the above-mentioned formation unit (II) is made of at least a structure that is selected from following (II-i), (II-ii), (II-iii), (II-iv):

-O-????????????……(II-i)

-O-Ar ^IIc-O-????……(II-ii)

Ar ^IIcFor can containing the aryl of non-reacted substituent carbonatoms 6-20,

With

Ar ^IIdAnd Ar ^IIeIndependent of separately containing the aryl of non-reacted substituent carbonatoms 6-20.

2. the Kapton of claim 1 is characterized in that: constitute X in the unit (II) by following formula (II-i) expression, constituting unit (I) be the 40-70% mole, and formation unit (II) is the 30-60% mole.

3. the Kapton of claim 1, it is characterized in that: the X that constitutes in the unit (II) is represented by at least a being selected from (II-ii), (II-iii) and structure (II-iv), constituting unit (I) is the 70-95% mole, and constituting unit (II) is the 10-40% mole.

4. the Kapton of claim 1 is characterized in that: the imino-concentration [imide] of used polyimide is 5.7-6.2eq/kg.

5. the Kapton of claim 2 is characterized in that: constitute unit (II) and be following formula (II-a)

Shown in structure.

6. the Kapton of claim 1, it is characterized in that: the tensile strength on the direction of this film is more than the 150MPa.

7. the Kapton of claim 1, wherein the imino-ratio of polyimide is more than 95%.

8. the manufacture method of a Kapton, this method comprises the steps:

Step 1: make aromatic diamine compound shown in (A) pyromellitic acid acid anhydride, (B) following formula (III) and (C) aromatic diamine compound shown in the following formula (IV), in solvent, react, obtain polyamic acid solution with the ratio that satisfies following formula (1) and (2) simultaneously,

0.95≤a/(b+c)≤1.05……(1)

0.01≤c/(b+c)≤0.70……(2)

Wherein a represents the mole number of pyromellitic acid acid anhydride, and b represents the mole number of aromatic diamine compound shown in the following formula (III), and c represents the mole number of aromatic diamine compound shown in the following formula (IV),

H ₂N-Ar ^Ia-NH ₂??????????……(III)

Ar ^IaNon-reacted substituent 1 for containing, the 4-phenylene,

H ₂N-Ar ^IIa-X-Ar ^IIb-NH ₂??……(IV)

Ar ^IIaAnd Ar ^IIbIndependent of separately containing the aryl of non-reacted substituent carbonatoms 6-20, X is made of at least a structure that is selected from following (IV-i), (IV-ii), (IV-iii), (IV-iv):

-O-?????????????????????……(IV-i)

-O-Ar ^IIc-O-?????????????……(IV-ii)

Ar ^IIcFor can containing the aryl of non-reacted substituent carbonatoms 6-20,

With

Ar ^IIdAnd Ar ^IIeIndependent of separately containing the aryl of non-reacted substituent carbonatoms 6-20;

Step 2: make the reaction of gained polyamic acid solution and dewatering agent, make at least a portion of polyamic acid convert poly-different imide to, form gel film;

Step 3: the gained gel film is carried out biaxial stretching;

Step 4: the gained biaxially drawn films is heat-treated.

9. the manufacture method of the Kapton of claim 8, it is characterized in that: in step 2, in the polyamic acid solution that makes by step 1, add diacetyl oxide and organic amine again as dewatering agent, form polyamic acid composition, with said composition curtain coating on carrier, by it is heated up, heat treated, make it carry out dehydration reaction, convert at least a portion of polyamic acid to polyimide or poly-different imide, form gel film.

10. the manufacture method of the Kapton of claim 8, it is characterized in that: in step 2, polyamic acid solution curtain coating on carrier that will make by above-mentioned steps (1), obtain film, gained film and described carrier be impregnated in the different imidization solution that contains the solvent the same with step 1, dewatering agent diacetyl oxide and organic amine together, make at least a portion of polyamic acid convert poly-different imide to, form gelatinous membrane.

11. the manufacture method of the Kapton of claim 8, wherein the different imino-ratio of gained gelatinous membrane is more than 90% in the step (2).

12. the manufacture method of the Kapton of claim 8, the gelatinous membrane that wherein is used for carrying out in step (3) biaxial stretching has 200-10,000% swelling capacity.

13. the manufacture method of the Kapton of claim 8, wherein the thermal treatment of step (4) is in fixed length or exist under the tensile condition and implement under 250-650 ℃ temperature.

14. the metal line circuit card that forms by the Kapton of claim 1.

15. the band that is used for LOC that forms by the Kapton of claim 1.