CN107312329A

CN107312329A - Polyimide film and copper-clad laminated board

Info

Publication number: CN107312329A
Application number: CN201710279853.7A
Authority: CN
Inventors: 松下祐之; 金子和明; 须藤芳树
Original assignee: Nippon Steel Chemical Co Ltd
Current assignee: Nippon Steel Chemical and Materials Co Ltd
Priority date: 2016-04-27
Filing date: 2017-04-25
Publication date: 2017-11-03
Anticipated expiration: 2037-04-25
Also published as: CN113527882A; TW201806746A; JP6839594B2; JP7029006B2; KR102386047B1; TWI763311B; KR20170122661A; TW202126477A; JP2021088191A; CN107312329B; TWI721162B; JP2017200759A; KR20210086588A; KR102272630B1

Abstract

The present invention provides a kind of polyimide film of change in size when reducing high temperature process and uses the copper-clad laminated board of the polyimide film.The polyimide film of the present invention has thermoplastic polyimide layer at least side of non-thermal plasticity polyimide layer, and meets：(i) thermal coefficient of expansion is in the range of 10ppm/K~30ppm/K；(ii) glass transition temperature of TPI is in more than 200 DEG C and less than 350 DEG C of scope；(iii) value of (RO) is postponed in face in more than 5nm and below 50nm scope；(iv) RO of width (TD directions) inhomogeneity (Δ RO) is below 10nm.

Description

Polyimide film and copper-clad laminated board

Technical field

The present invention relates to a kind of polyimide film and copper-clad laminated board.

Background technology

In recent years, with electronic equipment miniaturization, lightweight, space saving development, thin and light amount, with flexible Even if property, alternating bending also with excellent durability flexible printing wiring board (Flexible Printed Circuits, FPC constantly increase the need for).Even if FPC can also realize three-dimensional and highdensity installation in the confined space, therefore its purposes is not Such as hard disk drive (Hard Disk Drive, HDD), digital versatile disc (Digital Versatile are expanded to disconnectedly Disc, DVD), the wiring of the moving part of electronic equipment such as mobile phone or cable (cable), connector (connector) etc. zero Part.

FPC be by etch copper-clad laminated board (Copper-Clad Laminate, CCL) layers of copper carry out wiring processing and Manufacture.For continuous bend in mobile phone or smart mobile phone or the FPC of 180 ° of bending, rolled copper foil is used as the material of layers of copper mostly Material.For example in patent document 1 propose：Bending resistance of the regulation using the copper-clad laminated board made by rolled copper foil is come with the number of times of resistance to jackknifing Qu Xing.In addition, proposing a kind of use in patent document 2 with the copper-clad laminated of rolled copper foil as defined in glossiness and bending number of times Plate.

During to the photoetching of copper-clad laminated board (photolithography) process or installation FPC, to be arranged on Engaged, cut off, being exposed, being etched on the basis of alignment mark (alignment mark) in copper-clad laminated board etc. it is various plus Work.Machining accuracy in these processes becomes important in terms of the reliability for the electronic equipment for maintaining to be equipped with FPC.However, covering Layers of copper lamination has the structure for being laminated the different layers of copper of thermal coefficient of expansion and resin bed, therefore due to layers of copper and resin bed Thermal coefficient of expansion difference and interlayer produce stress.Part or all of the stress carries out wiring processing in etched copper In the case of be released from, thus produce flexible, cause the change in size of wiring pattern.Therefore, finally occurs chi in FPC stage Very little change, as causing between wiring or the reason for wiring is with the loose contact of terminal, make the reliability or yield drop of circuit substrate It is low.Therefore, for the copper-clad laminated board as circuit base material, dimensional stability is very important characteristic.But, In the patent document 1, patent document 2, the dimensional stability on copper-clad laminated board does not make any consideration.

It is used as the method for manufacture polyimide film, it is known that following methods：For the self-supporting gel mould of polyamic acid, together When or continuously carry out uniaxial extension and hot-imide, polyimide molecule chain orientation and showing is appeared interior two-fold Penetrate.Now, in order to control to postpone (retardation), liter when uniaxial extension operation and hot-imide is accurately controlled The conditions such as warm speed, final solidification temperature, heavy burden.For example in patent document 3 propose following technology：By polyimide film one side A face uniaxial extension is heated, thus control delay.

[prior art literature]

[patent document]

[patent document 1] Japanese Patent Laid-Open 2014-15674 publications (claims etc.)

[patent document 2] Japanese Patent Laid-Open 2014-11451 publications (claims etc.)

[patent document 3] Japanese Patent Laid-Open 2000-356713 publications (claims etc.)

The content of the invention

[invention problem to be solved]

The first aspect of the present invention provides a kind of polyimide film of change in size when reducing high temperature process and used The copper-clad laminated board of the polyimide film.Even if in addition, the second aspect of the present invention, which provides one kind, is placed in TPI Glass transition temperature more than heating environment under also realize high dimensionally stable precision, and the polyimides that can stably produce Film and the copper-clad laminated board using the polyimide film.

[technological means for solving problem]

The present inventor etc. has been carried out making great efforts research, as a result finds, delay can be solved in the face by controlling polyimide film The problem, so that complete the present invention.

That is, polyimide film of the invention in the non-thermal plasticity polyimide layer comprising non-thermal plasticity polyimides at least Side has the thermoplastic polyimide layer comprising TPI.The polyimide film of the present invention is characterised by meeting Following conditions (i)~condition (iv)；

(i) thermal coefficient of expansion is in the range of 10ppm/K~30ppm/K；

(ii) glass transition temperature of the TPI is in more than 200 DEG C and less than 350 DEG C of scope；

(iii) value of (RO) is postponed in face in more than 5nm and below 50nm scope；

(iv) inhomogeneity (Δ of (RO) is postponed in the face of width (Transverse Direction, TD directions) RO) it is below 10nm.

The polyimide film of the present invention is alternatively in the environment of 360 DEG C of temperature with pressure 340MPa/m², the retention time 15 The variable quantity of delay (RO) is below 20nm in face before and after minute pressurization.

The polyimide film of the present invention can also make the non-thermal plasticity polyimides contain tetrabasic carboxylic acid residue and diamines residue, The tetrabasic carboxylic acid residue and diamines residue are aromatic series base, and the aromatic series base includes the base of biphenyl four or biphenylene, and Relative to total 100 molar parts of the tetrabasic carboxylic acid residue and diamines residue, the base of biphenyl four or biphenylene are 40 moles More than part.

The polyimide film of the present invention can also make the TPI contain tetrabasic carboxylic acid residue and diamines residue, institute It is aromatic series base to state tetrabasic carboxylic acid residue and diamines residue, and the aromatic series base includes the base of biphenyl four or biphenylene, and phase For total 100 molar parts of the tetrabasic carboxylic acid residue and diamines residue, the base of biphenyl four or biphenylene are 30 molar parts Above and in the scope below 80 molar parts.

The polyimide film of the present invention is alternatively residual relative to all tetrabasic carboxylic acids contained by the non-thermal plasticity polyimides The molar part of base 100, by 3,3 ', 4, tetrabasic carboxylic acid residue derived from 4 '-biphenyl tetracarboxylic dianhydride is more than 20 molar parts and 70 rub In scope below your part.

The polyimide film of the present invention is alternatively relative to all tetrabasic carboxylic acid residues contained by the TPI 100 molar parts, by 3,3 ', 4, tetrabasic carboxylic acid residue derived from 4 '-biphenyl tetracarboxylic dianhydride is more than 40 molar parts.

The polyimide film of the present invention is alternatively relative to all diamines residues contained by the non-thermal plasticity polyimides 100 molar parts, the diamines residue represented by following formulas (1) is more than 20 molar part.

[changing 1]

[in formula, R₁、R₂Independently represent the alkyl or carbon number 1~3 of carbon number 1~3 that can replace through halogen atom or phenyl Alkoxy or carbon number 2~3 alkenyl]

The polyimide film of the present invention is alternatively relative to all diamines residues 100 contained by the TPI Molar part, the diamines residue represented by following formulas (2) is in the scope more than 3 molar parts and below 60 molar parts.

[changing 2]

[in formula, R₃、R₄Independently represent the alkyl or carbon number 1~3 of carbon number 1~3 that can replace through halogen atom or phenyl Alkoxy or alkenyl]

The copper-clad laminated board of the present invention possesses insulating barrier and the layers of copper at least one face of the insulating barrier.Moreover, The copper-clad laminated board of the present invention is characterised by：The insulating barrier has the thermoplasticity polyamides contacted with the surface of the layers of copper sub- Amine layer and the non-thermal plasticity polyimide layer being laminated indirectly,

The insulating barrier includes any polyimide film.

The copper-clad laminated board of the present invention is alternatively the length direction (Machine before and after the etching of the layers of copper Direction, MD direction) size changing amount and the size changing amount of width (TD directions) be less than 2%.

[The effect of invention]

Even if the variable quantity that the polyimide film of the present invention postpones in the environment of high temperature, high pressure is also inhibited, therefore Even if being for example situation about being thermally compressed at high temperature with copper foil, dimensional stability is also excellent.Therefore, by using the poly- of the present invention Acid imide film, can shorten the time of the manufacturing process of copper-clad laminated board, and production stability is excellent.Especially with volume to volume (roll- To-roll) mode is handled the polyimide film of wide cut, laminated copper foil and in the case of manufacturing copper-clad laminated board, film Also size changing rate is low for overall with, dimensionally stable, therefore can be by as the FPC high-density installations obtained by the copper-clad laminated board.Therefore, lead to Cross the polyimide film of the present invention and be used as FPC materials using the copper-clad laminated board of the polyimide film, can be to circuit substrate Realize the raising of reliability and yield.

Brief description of the drawings

The evaluation side that Fig. 1 is evaluated the dimensional stability of the copper-clad laminated board of one embodiment of the present invention for expression Copper-clad laminated board used and the stereogram of the schematic configuration of test piece in method.

Fig. 2 is the figure illustrated to the mark position in test piece.

Fig. 3 is the partial enlarged drawing of the central area of test piece.

Fig. 4 is the partial enlarged drawing of the corner regions of test piece.

The figure that Fig. 5 illustrates for the size changing amount of device to hole and the interval in hole.

Fig. 6 is the figure of the evaluation sample for explanation embodiment.

Fig. 7 is the figure of the preparation of the evaluation sample for explanation embodiment.

[explanation of symbol]

10：Test piece

20：Imaginary square

20a：Center

20b：Corner

21：Central area

23a、23b：Corner regions

30：Hole

30a：The center in hole 30

100：Copper-clad laminated board

L0、L1：Distance

MD、TD：Direction

Δ₁、Δ₁+Δ₂：Size changing amount

Embodiment

Secondly, it is simultaneously appropriate one to be illustrated referring to the drawings in face of embodiments of the present invention.

The polyimide film of present embodiment has thermoplasticity polyamides sub- at least side of non-thermal plasticity polyimide layer Amine layer.That is, thermoplastic polyimide layer is provided in the one or two sides of non-thermal plasticity polyimide layer.For example be made by In the case of the copper-clad laminated board that the polyimide film of present embodiment is constituted with layers of copper, layers of copper is to be layered in thermoplasticity polyamides On the face of imine layer.

Here so-called non-thermal plasticity polyimides, produces softening and does not also show cementability even if usually carrying out heating Polyimides, and refer in the present invention use Measurement of Dynamic Viscoelasticity device (dynamic mechanical analysis (Dynamic Mechanical Analysis, DMA)) the storage modulus at determined 30 DEG C is 1.0 × 10⁹At more than Pa, and 360 DEG C It is 1.0 × 10 to store modulus⁸More than Pa polyimides.In addition, so-called TPI, is usually clearly to confirm To glass transition temperature (Tg) polyimides, and refer to that the storage modulus at 30 DEG C that use DMA to be determined is in the present invention 1.0×10⁹Storage modulus at more than Pa, and 360 DEG C is less than 1.0 × 10⁸Pa polyimides.

The polyimide film of present embodiment can be film (piece), or be layered in copper foil, glass plate, polyimides system The film of state on the base materials such as the resin sheets such as film, polyamide mesentery, polyester mesentery.

The polyimide film of present embodiment is for example in the case where the insulating barrier of circuit substrate is made in application, in order to prevent sticking up Bent generation or the reduction of dimensional stability, it is important that thermal coefficient of expansion (Coefficients of Thermal Expansion, CTE) in more than 10ppm/K and below 30ppm/K scope, preferably with more than 10ppm/K and 25ppm/K with Under scope in be advisable.If CTE is less than 10ppm/K or more than 30ppm/K, warpage, or dimensional stability reduction are produced.Separately Outside, in the polyimide film of present embodiment, relative to the CTE of the layers of copper comprising copper foil etc., the CTE of polyimide film is more preferably In ± below 5ppm/K scope, most preferably in ± below 2ppm/K scope.

In the polyimide film of present embodiment, the thickness of polyimide film can be set as set model according to application target Enclose interior thickness.The thickness of polyimide film is for example preferably in the range of 8 μm~50 μm, more preferably in 11 μm~26 μm of model In enclosing.If the thickness of polyimide film is less than the lower limit, electrical insulating property can not be ensured sometimes, or produce because of operability drop It is low and the problems such as processing becomes difficult in manufacturing process.On the other hand, if the thickness of polyimide film exceedes the higher limit, In order to postpone (RO) in chain of command, it is necessary to accurately control manufacturing condition, the undesirable conditions such as productivity reduction are produced.

In the polyimide film of present embodiment, non-thermal plasticity polyimide layer constitutes the polyimides of low heat expansion Layer, thermoplastic polyimide layer constitutes the expansile polyimide layer of hyperpyrexia.Here, the polyimide layer of low heat expansion refers to In thermal coefficient of expansion (CTE) preferably more than 1ppm/K and below 25ppm/K scope, more preferably more than 3ppm/K and 25ppm/K Polyimide layer in following scope.In addition, the expansile polyimide layer of hyperpyrexia refers to preferred more than 35ppm/K of CTE, more It is preferred that in more than 35ppm/K and below 80ppm/K scope and then in preferably more than 35ppm/K and below 70ppm/K scope Polyimide layer.Polyimide layer can be by combination, thickness, drying and the curing condition of raw material used in suitably changing The polyimide layer with required CTE is made.

In addition, in the polyimide film of present embodiment, with non-thermal plasticity polyimide layer and thermoplastic polyimide layer Thickness ratio (non-thermal plasticity polyimide layer/thermoplastic polyimide layer) be 1.5~6.0 in the range of be advisable.This than value If less than 1.5, the non-thermal plasticity polyimide layer overall relative to polyimide film is thinning, therefore postpones (RO) no in face Homogeneity easily becomes big, and thermoplastic polyimide layer is thinning if more than 6.0, therefore polyimide film is bonding with layers of copper reliable Property is easily reduced.The resin for postponing each polyimide layer of the control of (RO) with constituting polyimide film in the face is constituted and its thick Degree is relevant.For as the thermoplastic polyimide layer that cementability is high thermal expansivity or the resin composition of softening is assigned, Its thickness is bigger, then the influence that the value to the RO of polyimide film is caused is bigger.Therefore, non-thermal plasticity polyimide layer is increased The ratio of thickness, reduces the ratio of the thickness of thermoplastic polyimide layer, reduces the RO of polyimide film value and its heterogeneity Property.

In the polyimide film of present embodiment, constituting the polyimides of thermoplastic polyimide layer can improve and layers of copper Adhesion.The glass transition temperature of this TPI is in more than 200 DEG C and less than 350 DEG C of scope preferably 200 More than DEG C and in less than 320 DEG C of scope.

From the viewpoint of the improvement for the dimensional accuracy for just larger showing the polyimide film of present embodiment, this The polyimide film of embodiment is preferably in a width of more than the 490mm of film and below 1100mm scope, and the length of strip Spend for more than 20m.In the case where being continuously manufactured by the polyimide film of present embodiment, width (hereinafter also referred to TD Direction) wider film, The effect of invention more especially becomes apparent.In addition, the polyamides for also including being continuously manufactured by present embodiment is sub- After amine film, cut on the length direction (hereinafter also referred to MD directions) of the polyimide film of strip and TD directions with certain certain value Cut the film obtained by (slit).

Postpone the value of (RO) in the face of the polyimide film of present embodiment in more than 5nm and below 50nm scope, It is preferred that in more than 5nm and below 20nm scope, in more preferably more than 5nm and below 15nm scope.In addition, the RO in TD directions Inhomogeneity (Δ RO) be below 10nm, more preferably preferably below 5nm, below 3nm, due to being controlled in this scope System, therefore especially even thickness is more than 25 μm of film, dimensional accuracy is also improved.

The polyimide film of present embodiment is preferably with pressure 340MPa/m in the environment of 360 DEG C of temperature², keep Postpone the variable quantity of (RO) in face before and after the pressurization of 15 minutes time for below 20nm, more preferably below 10nm, and then preferably 5nm Below.Even if the polyimide film of present embodiment is in the glass transfer more than the polyimides for constituting thermoplastic polyimide layer At a temperature of temperature, also RO variable quantity is controlled in below the higher limit.Thus, for example this is implemented by heat lamination Before and after the process that the polyimide film of mode is fitted with copper foil, RO is not easy to change, therefore poly- as excellent in dimensional stability Acid imide film.

In addition, in the range of the preferred 3.0GPa~10.0GPa of the modulus in tension of the polyimide film of present embodiment, it is more excellent In the range of selecting 4.5GPa~8.0GPa.If the modulus in tension of polyimide film be less than 3.0GPa, polyimides itself it is strong Degree reduction, produces the operational problem such as the cracking of film sometimes when copper-clad laminated board thus being processed into circuit substrate.On the contrary, If the modulus in tension of polyimide film rises, as a result will covered more than 10.0GPa, the rigidity for bending of copper-clad laminated board When layers of copper lamination is bent, the bending stress that thin copper film applies is risen, bending resistance reduction.By by the stretching of polyimide film Modulus is set in the scope, it can be ensured that polyimides film strength and flexibility.

The embodiment example of the manufacture method of the polyimide film of present embodiment if any：[1] it is coated with supporting base material The solution of polyamic acid and after being dried, the method for being subject to imidizate and manufacturing polyimide film；And [2] are in branch support group After the solution of polyamic acid is coated with material and is dried, the gel mould of polyamic acid is peeled off from supporting base material, is subject to acyl sub- Amination and the method for manufacturing polyimide film.In addition, the polyimide film of present embodiment is comprising multilayer polyimide layer Polyimide film, therefore the embodiment of its manufacture method can for example enumerate：[3] polyamic acid is repeated in supporting base material Being coated with of solution, dry after, carry out the method (hereinafter referred to as casting) of imidizate；And [4] are same by multilayer extrusion When the state of folding polyamic acid with multilayer formation be coated, dry after, carry out method (the hereinafter referred to as multilayer of imidizate Extrusion molding) etc..

[1] method for example may include following process 1a~process 1c；

(1a) is coated with the solution of polyamic acid in supporting base material, and is subject to dry process；

(1b) is heat-treated and imidizate in supporting base material to polyamic acid, is consequently formed the work of polyimide layer Sequence；And

(1c) separates supporting base material with polyimide layer, the process for being derived from polyimide film.

[2] method for example may include following process 2a~process 2c；

(2a) is coated with the solution of polyamic acid in supporting base material, and is subject to dry process；

(2b) is by supporting base material and the process of the gel UF membrane of polyamic acid；And

(2c) is heat-treated and imidizate to the gel mould of polyamic acid, the process for being derived from polyimide film.

[3] method is to repeat multiple process 1a or process 2a in [1] method or [2] method, in branch The laminate structure of polyamic acid is formed on support group material, in addition, can be implemented in the same manner as [1] method or [2] method.

[4] method be in the process 1a of [1] method or the process 2a of [2] method, it is same by multilayer extrusion When coating polyamic acid laminate structure and be dried, in addition, can be in the same manner as [1] method or [2] method Implement.

The polyimide film manufactured in the present invention is preferably the imidizate that polyamic acid is completed in supporting base material.By In carrying out imidizate in the state of the resin bed of polyamic acid is fixed in supporting base material, therefore imidizate can be suppressed During polyimide layer telescopic variation, maintain polyimide film thickness or dimensional accuracy.

However, in supporting base material complete polyamic acid imidizate polyimide film for, due to from Supporting base material separate applied during polyimide film to the tension force of polyimide film or for example using the knife edge (knife It is produced to stress of polyimide film etc. during stripping edge) etc., and polyimide film is extended.Therefore, easily produce Postpone the inhomogeneity of (RO), especially a width of more than the 490mm of film polyimide film in the face of polyimide film, RO is not Homogeneity more becomes apparent.For the polyimide film of present embodiment, to constitute non-thermal plasticity polyimide layer and thermoplastic Property polyimide layer polyimides easily formed order structure mode set, thus make stress necessary to stripping It is dispersed in each layer of polyimide film, thus can control RO.

In addition, can also carry out delay (RO) in chain of command by the following method：By the gel of the polyamic acid in supporting base material UF membrane, the gel mould uniaxial extension or twin shaft of polyamic acid are extended, imidizate is simultaneously or successively carried out.Now, it is RO is more closely highly controlled, programming rate, acid imide when preferably appropriate adjustment extension operation and imidizate The conditions such as completion temperature, the heavy burden of change.

(non-thermal plasticity polyimides)

In the polyimide film of present embodiment, preferably non-thermal plasticity polyimides contains tetrabasic carboxylic acid residue and diamines Residue, these residues are aromatic series base, and include the base of biphenyl four or biphenylene.Here, the base of biphenyl four or biphenylene with Diphenyl skeleton is synonymous, and the substituent such as also can make halogen atom, alkyl, alkoxy, alkenyl is bonded to biphenyl four Base or biphenylene, but especially out of face that reduce under hot environment from the viewpoint of the variable quantity of delay (RO), such as it is more excellent Choosing is that the carbon number of the substituents such as alkyl, alkoxy, alkenyl is set in the range of 1~3.

In addition, in the present invention, so-called tetrabasic carboxylic acid residue represents quaternary groups, so-called two as derived from tetracarboxylic dianhydride Amine residue, represents the divalent group as derived from diamine compound.In addition, diamine compound is the chemical combination with two amino Hydrogen atom in thing, but each amino can also be replaced through arbitrary substituent.

Tetrabasic carboxylic acid residue and diamines residue contained by non-thermal plasticity polyimides are aromatic series base, by being set to aromatic series Base, can reduce the variable quantity for postponing (RO) in the face under the hot environment of polyimide film.And then, relative to tetrabasic carboxylic acid residue and The base of biphenyl four or biphenylene, are preferably set to more than 40 molar parts, more preferably by total 100 molar parts of diamines residue It is set to more than 50 molar parts, is thus easily formed as the order structure obtained by the base of biphenyl four or biphenylene, polyamides can be reduced The variable quantity of RO under the hot environment of imines film, and suppress RO inhomogeneity.

In addition, the tetrabasic carboxylic acid residue contained by non-thermal plasticity polyimides is for example preferably enumerated by 3,3 ', 4,4 '-biphenyl Tetracarboxylic dianhydride (Biphenyltetracarboxylic dianhydride, BPDA), 2,2 ', 3,3 '-biphenyl tetracarboxylic dianhydride Deng derivative tetrabasic carboxylic acid residue.In these tetrabasic carboxylic acid residues, tetrabasic carboxylic acid residue is (hereinafter also referred to especially as derived from BPDA BPDA residues) order structure is easily formed, the variable quantity for postponing (RO) in the face under hot environment can be reduced, therefore it is especially excellent Choosing.In addition, though BPDA residues can assign the self-supporting of the gel mould of the polyamic acid as polyimides predecessor, having makes The tendency of CTE increases after imidizate.From the point of view of this viewpoint, relative to all tetracarboxylic acids contained by non-thermal plasticity polyimides The sour molar part of residue 100, BPDA residues with the range of the molar part of preferably 20 molar parts~70, more preferably 20 molar part~60 rub It is advisable in the range of your part.

The tetrabasic carboxylic acid residue beyond the BPDA residues contained by non-thermal plasticity polyimides is preferably enumerated by equal benzene (hereinafter also referred to PMDA is residual for tetrabasic carboxylic acid residue derived from tetracarboxylic acid dianhydride (Pyromellitic dianhydride, PMDA) Base).Relative to all molar parts of tetrabasic carboxylic acid residue 100 contained by non-thermal plasticity polyimides, PMDA residues are with preferably 0 molar part It is advisable in the range of~60 molar parts, in the range of the molar part of more preferably 0 molar part~50.PMDA residues are any, but are hair Wave control thermal coefficient of expansion and control the residue of the effect of glass transition temperature.

Other tetrabasic carboxylic acid residues can for example enumerate the tetrabasic carboxylic acid residue as derived from following aromatic tetracarboxylic acid's dianhydride：3, 3 ', 4,4 '-diphenyl sulfone tetracarboxylic dianhydride, 4,4 '-epoxide double phthalic anhydride, 2,3 ', 3,4 '-biphenyl tetracarboxylic dianhydride, 2,2 ', 3,3 '-benzophenone tetracarboxylic dianhydride, 2,3,3 ', 4 '-benzophenone tetracarboxylic dianhydride or 3,3 ', 4,4 '-benzophenone Tetracarboxylic dianhydride, 2,3 ', 3,4 '-diphenyl ether tetracarboxylic dianhydride, double (2,3- dicarboxyphenyi) ether dianhydrides, 3,3 ", 4,4 "-right Terphenyl tetracarboxylic dianhydride, 2,3,3 ", 4 "-para-terpheny tetracarboxylic dianhydride or 2,2 ", 3,3 "-para-terpheny tetracarboxylic dianhydride, 2,2- double (2,3- dicarboxyphenyi)-propane dianhydride or 2,2- double (3,4- dicarboxyphenyi)-propane dianhydride, double (2,3- dicarboxyls Base phenyl) methane dianhydride or double (3,4- dicarboxyphenyi) methane dianhydrides, double (2,3- dicarboxyphenyi) sulfone dianhydrides or double (3,4- Dicarboxyphenyi) sulfone dianhydride, double (2,3- dicarboxyphenyi) the ethane dianhydrides of 1,1- or double (3, the 4- dicarboxyphenyi) ethane of 1,1- Dianhydride, 1,2,7,8- phenanthrene-tetracarboxylic dianhydride, 1,2,6,7- phenanthrene-tetracarboxylic dianhydride or 1,2,9,10- phenanthrene-tetracarboxylic dianhydride, 2,3, 6,7- anthracene tetracarboxylic dianhydrides, 2,2- double (3,4- dicarboxyphenyi) tetrafluoropropane dianhydride, 2,3,5,6- hexamethylene dianhydrides, 1,2,5, 6- naphthalene tetracarboxylic acids dianhydride, Isosorbide-5-Nitrae, 5,8- naphthalene tetracarboxylic acid dianhydrides, 2,3,6,7- naphthalene tetracarboxylic acid dianhydrides, 4,8- dimethyl -1,2,3,5, 6,7- hexahydro naphthalenes -1,2,5,6- tetracarboxylic dianhydrides, 2,6- or 2,7- dichloronaphtalene-Isosorbide-5-Nitrae, 5,8- tetracarboxylic dianhydrides, 2,3,6,7- tetra- Chloronaphthalene-Isosorbide-5-Nitrae, 5,8- tetracarboxylic dianhydrides or Isosorbide-5-Nitrae, 5,8- Tetrachloronaphthalenes -2,3,6,7- tetracarboxylic dianhydrides, 2,3,8,9- perylenes-tetrabasic carboxylic acid Dianhydride, 3,4,9,10- perylenes-tetracarboxylic dianhydride, 4,5,10,11- perylenes-tetracarboxylic dianhydride or 5,6,11,12- perylenes-tetracarboxylic dianhydride, Pentamethylene -1,2,3,4- tetracarboxylic dianhydrides, pyrazine -2,3,5,6- tetracarboxylic dianhydrides, pyrrolidines -2,3,4,5- tetracarboxylic dianhydrides, Thiophene -2,3,4,5- tetracarboxylic dianhydrides, 4,4 '-bis- (2,3- di carboxyl phenyloxy) diphenyl methane dianhydrides etc..

In tetrabasic carboxylic acid residue contained by non-thermal plasticity polyimides, relative to all four contained by non-thermal plasticity polyimides The molar part of carboxylic acid residues 100, by 2,3 ', 3,4 '-diphenyl ether tetracarboxylic dianhydride, 3,3 ', 4,4 '-diphenyl sulfone tetrabasic carboxylic acid two Acid anhydride, 4, the double phthalic anhydrides and 2 of 4 '-epoxide, 3 ', 3, four derived from the tetracarboxylic dianhydride of 4 '-biphenyltetracaboxylic dianhydride Carboxylic acid residues below preferably 20 molar parts, below more preferably 15 molar parts to be advisable.If relative to non-thermal plasticity polyimides institute All tetrabasic carboxylic acid residues for containing and these tetrabasic carboxylic acid residues are more than the orientation reduction of 20 molar parts, then molecule, delay in face (RO) control becomes difficult.

In the polyimide film of present embodiment, the diamines residue contained by non-thermal plasticity polyimides is for example preferably lifted Go out the diamines residue represented by following formulas (1).

[changing 3]

In the formula (1), R₁、R₂Independently represent the alkyl or carbon of carbon number 1~3 that can replace through halogen atom or phenyl The alkoxy of number 1~3 or the alkenyl of carbon number 2~3.

Diamines residue represented by formula (1) easily forms order structure, is particularly advantageous under suppression hot environment Postpone the variable quantity of (RO) in face.From the point of view of this viewpoint, relative to all diamines residues contained by non-thermal plasticity polyimides 100 molar parts, diamines residue represented by formula (1) with more than preferably 20 molar parts, more than more preferably 50 molar parts, Jin Eryou Select and be advisable in the range of the molar part of 60 molar parts~90.

The preferred concrete example of diamines residue represented by formula (1) can be enumerated two as derived from following diamine compound Amine residue：2,2 '-dimethyl -4,4 '-benzidine (m-TB), 2,2 '-diethyl -4,4 '-benzidine (m-EB), 2, 2 '-diethoxy -4,4 '-benzidine (m-EOB), 2,2 '-dipropoxy -4,4 '-benzidine (m-POB), 2,2 ' - N-propyl -4,4 '-benzidine (m-NPB), 2,2 '-divinyl -4,4 '-benzidine (VAB), 4,4 '-diaminourea Biphenyl, 4,4 '-diaminourea -2,2 '-bis- (trifluoromethyl) biphenyl (TFMB) etc..In these diamine compounds, especially 2,2 '-diformazan Base -4,4 '-benzidine (m-TB) easily forms order structure, can reduce the change for postponing (RO) in the face under hot environment Amount, therefore particularly preferably.

The diamines residue beyond diamines residue represented by formula (1) preferably enumerate by p-phenylenediamine (p-PDA), Diamines residue derived from phenylenediamine (m-PDA) etc., more preferably with diamines residue (the hereinafter also referred to PDA as derived from p-PDA Residue) it is advisable.Relative to all molar parts of tetrabasic carboxylic acid residue 100 contained by non-thermal plasticity polyimides, PDA residues are with preferably 0 It is advisable in the range of the molar part of molar part~80, in the range of the molar part of more preferably 0 molar part~50.PDA residues are any, but For the residue for the effect for playing control thermal coefficient of expansion and control glass transition temperature.

In addition, elongation and bending resistance in the case of polyimide film etc. is made in order to improve, it is preferably non-thermal Plastic polyimide contain selected from by the group that the diamines residue represented by following formulas (3)~formula (5) is constituted extremely A kind of few diamines residue.

[changing 4]

In the formula (3), R₅And R₆Separately represent hydrogen atom or halogen atom or carbon number 1~4 can be through halogen The alkyl or alkoxy or alkenyl of plain atom substitution, X independently represent to be selected from-O- ,-S- ,-CH₂-、-CH(CH₃)-、-C (CH₃)₂-、-CO-、-COO-、-SO₂-, the divalent group in-NH- or-NHCO-, m and n independently represent 1~4 integer.

[changing 5]

In the formula (4), R₅、R₆And R₇Separately represent hydrogen atom or halogen atom or carbon number 1~4 can The alkyl or alkoxy or alkenyl replaced through halogen atom, X independently represents to be selected from-O- ,-S- ,-CH₂-、-CH(CH₃)-、-C (CH₃)₂-、-CO-、-COO-、-SO₂-, the divalent group in-NH- or-NHCO-, m, n and o independently represent 1~4 integer.

[changing 6]

In the formula (5), R₅、R₆、R₇And R₈Separately represent hydrogen atom or halogen atom or carbon number 1~4 The alkyl or alkoxy or alkenyl that can replace through halogen atom, X₁And X₂Separately represent singly-bound or selected from-O- ,-S- ,- CH₂-、-CH(CH₃)-、-C(CH₃)₂-、-CO-、-COO-、-SO₂-, the divalent group in-NH- or-NHCO-, by X₁And X₂Both Except the situation of singly-bound, m, n, o and p independently represent 1~4 integer.

Diamines residue represented by formula (3)~formula (5) has the position of bendability, therefore polyimide film can be assigned Give flexibility.Herein, formula (4) and diamines residue represented by formula (5) due to phenyl ring be 3 or 4, therefore in order to suppress The terminal groups for being bonded to phenyl ring are preferably set to contraposition by the increase of thermal coefficient of expansion (CTE).In addition, to polyimides From the viewpoint of film assigns flexibility and suppresses thermal coefficient of expansion (CTE) increase, relative to non-thermal plasticity polyimides institute All molar parts of diamines residue 100 contained, the diamines residue represented by formula (3)~formula (5) is with preferably 10 molar part~40 It is advisable in the range of molar part, in the range of the molar part of more preferably 10 molar parts~30.If formula (3)~formula (5) is represented Diamines residue be less than 10 molar parts, then produce the elongation reduction being made in the case of film, the reduction such as bending resistance.The opposing party Face, if more than 40 molar parts, the orientation of molecule is reduced, and low CTEization becomes difficult.

In formula (3), group R₅And group R₆Preference can enumerate：Hydrogen atom or carbon number 1~4 can be through halogen atom Substituted alkyl or the alkoxy or alkenyl of carbon number 1~3.In addition, in formula (3), concatenating group X preference can enumerate- O-、-s-、-CH₂-、-CH(CH₃)-、-SO₂- or-CO-.The preferred concrete example of diamines residue represented by formula (3) can enumerate by Diamines residue derived from following diamine compound：4,4 '-diamino-diphenyl ether (4,4 '-DAPE), 3,3 '-diaminourea two Phenyl ether, 3,4 '-diamino-diphenyl ether, 4,4 '-diaminodiphenyl-methane, 3,3 '-diaminodiphenyl-methane, 3,4 '- Diaminodiphenyl-methane, 4,4 '-diamino-diphenyl propane, 3,3 '-diamino-diphenyl propane, 3,4 '-diaminourea hexichol Base propane, 4,4 '-diamino diphenyl sulfide, 3,3 '-diamino diphenyl sulfide, 3,4 '-diamino diphenyl sulfide, 4, 4 '-diamino diphenyl sulfone, 3,3 '-diamino diphenyl sulfone, 4,4 '-diaminobenzophenone, 3,4 '-diaminourea hexichol first Ketone, 3,3 '-diaminobenzophenone etc..

In formula (4), group R₅, group R₆And group R7 preference can be enumerated：Hydrogen atom or carbon number 1~4 can be through halogen The alkyl of plain atom substitution or the alkoxy or alkenyl of carbon number 1~3.In addition, in formula (4), concatenating group X preference can Enumerate-O- ,-S- ,-CH₂-、-CH(CH₃)-、-SO₂- or-CO-.The preferred concrete example of diamines residue represented by formula (4) can Enumerate the diamines residue as derived from following diamine compound：1,3- double (4- amino-benzene oxygens) benzene (TPE-R), Isosorbide-5-Nitraes-bis- (4- amino-benzene oxygens) benzene (TPE-Q), double (4- amino-benzene oxygens) -2,5- di-t-butyls benzene (DTBAB), double (the 4- amino of 4,4- Phenoxy group) benzophenone (BAPK), double [2- (4- the aminophenyls) -2- propyl group] benzene of 1,3-, Isosorbide-5-Nitrae-bis- [2- (4- aminophenyls) - 2- propyl group] benzene etc..

In formula (5), group R₅, group R₆, group R₇And group R₈Preference can enumerate：Hydrogen atom or carbon number 1~4 The alkyl that can replace through halogen atom or carbon number 1~3 alkoxy or alkenyl.In addition, in formula (5), concatenating group X₁And Concatenating group X₂Preference can enumerate singly-bound ,-O- ,-S- ,-CH₂-、-CH(CH₃)-、-SO₂- or-CO-.Wherein, from imparting bending From the viewpoint of position, by concatenating group X₁And concatenating group X₂Except both is the situations of singly-bound.Diamines represented by formula (5) is residual The preferred concrete example of base can enumerate the diamines residue as derived from following diamine compound：4,4 '-bis- (4- amino-benzene oxygens) Biphenyl (BAPB), 2,2 '-bis- [4- (4- amino-benzene oxygens) phenyl] propane (BAPP), 2,2 '-bis- [4- (4- amino-benzene oxygens) benzene Base] ether (BAPE), double [4- (4- amino-benzene oxygens) phenyl] sulfones etc..

Other diamines residues can for example enumerate the diamines residue as derived from following aromatic diamine compound：2,2- Double-[4- (3- amino-benzene oxygens) phenyl] propane, double [4- (3- amino-benzene oxygens) phenyl] sulfones, double [4- (3- amino-benzene oxygens) Biphenyl, double [1- (3- amino-benzene oxygens)] biphenyl, double [4- (3- amino-benzene oxygens) phenyl] methane, double [4- (3- aminobenzene oxygen Base) phenyl] ether, double [4- (3- amino-benzene oxygens)] benzophenone, 9,9- double [4- (3- amino-benzene oxygens) phenyl] fluorenes, 2,2- Double-[4- (4- amino-benzene oxygens) phenyl] HFC-236fa, 2,2- be double-[4- (3- amino-benzene oxygens) phenyl] HFC-236fa, 3,3 '- Dimethyl -4,4 '-benzidine, 4, the ortho-aminotoluene of 4 '-methylene two, 4,4 '-methylene two -2,6- dimethylanilines, 4,4 ' - Methylene -2,6- diethylaniline, 3,3 '-diamino-diphenyl ethane, 3,3 '-benzidine, 3,3 '-dimethoxy-biphenyl Amine, 3,3 "-diaminourea para-terpheny, 4,4 '-[Isosorbide-5-Nitrae-phenylene is double (1- methyl ethylidene)] dianils, 4,4 '-[1,3- sub- benzene Base is double (1- methyl ethylidene)] it is dianil, bis(p-aminocyclohexyl)methane, double (p- beta-amino tert-butyl-phenyl) ethers, double (p- Beta-methyl-δ-Aminopentyl) benzene, to double (2- methyl -4- Aminopentyls) benzene, to double (1,1- dimethyl -5- amino penta Base) benzene, 1,5-diaminonaphthalene, 2,6- diaminonaphthalenes, double (the beta-amino tert-butyl group) toluene of 2,4-, 2,4- diaminotoluenes, two Toluene-2,4-diisocyanate, 5- diamines, paraxylene -2,5- diamines, m-xylene diamine, paraxylene diamines, DAP, 2,5- Diamino-pyridine, 2,5- diaminostilbenes, 3,4- oxadiazoles, piperazine etc..

In non-thermal plasticity polyimides, by selecting the species of the tetrabasic carboxylic acid residue and diamines residue or applying two Respective mol ratio in the case of the tetrabasic carboxylic acid residue or diamines residue of kind of the above, can control thermal coefficient of expansion, storage modulus, Modulus in tension etc..In addition, in non-thermal plasticity polyimides in the case of the construction unit with a variety of polyimides, can be with embedding Section form exist, also can randomly exist, from suppression face in delay (RO) inhomogeneity from the viewpoint of, preferably without Rule ground is present.

(TPI)

In the polyimide film of present embodiment, preferably TPI contains tetrabasic carboxylic acid residue and diamines is residual Base, these residues are aromatic series base, and include the base of biphenyl four or biphenylene.Here, on the base of biphenyl four or biphenylene, The substituent such as also can make halogen atom, alkyl, alkoxy, alkenyl is bonded to the base of biphenyl four or biphenylene, especially from suppression From the viewpoint of the variable quantity for postponing (RO) in face under preparing high-temp environment, the carbon of substituent such as alkyl, alkoxy, alkenyl Number is preferably set as in the range of 1~3.

Tetrabasic carboxylic acid residue and diamines residue contained by TPI are aromatic series base, by being set to aromatic series Base, can suppress to postpone the variable quantity of (RO) in the face under the hot environment of polyimide film.And then, relative to tetrabasic carboxylic acid residue and Total 100 molar parts of diamines residue, the base of biphenyl four or biphenylene are set to more than 30 molar parts and below 80 molar parts In the range of.If the base of biphenyl four or biphenylene are less than 30 molar parts, it is difficult to be formed as obtained by the base of biphenyl four or biphenylene The variable quantity increase of RO under order structure, the hot environment of polyimide film.On the other hand, if the base of biphenyl four or biphenylene More than 80 molar parts, then thermoplasticity is impaired.

In addition, the tetrabasic carboxylic acid residue contained by TPI is for example preferably enumerated by BPDA, 2,3 ', 3,4 '- Biphenyl tetracarboxylic dianhydride, 2,2 ', 3, tetrabasic carboxylic acid residue derived from 3 '-biphenyl tetracarboxylic dianhydride etc..In these tetrabasic carboxylic acid residues, Especially BPDA residues easily form order structure, can suppress to postpone the variable quantity of (RO) in the face under hot environment, therefore especially It is preferred that.Accordingly, with respect to all molar parts of tetrabasic carboxylic acid residue 100 contained by TPI, BPDA residues are with preferably 40 It is advisable more than molar part, more than more preferably 50 molar parts.

The tetrabasic carboxylic acid residue beyond the BPDA residues contained by TPI preferably enumerates PMDA residues. Relative to all molar parts of tetrabasic carboxylic acid residue 100 contained by TPI, PMDA residues are rubbed with preferably 0 molar part~60 It is advisable in the range of your part, in the range of the molar part of more preferably 0 molar part~50.PMDA residues are any, but to play control The residue of the effect of thermal coefficient of expansion and control glass transition temperature.

Other tetrabasic carboxylic acid residues can for example enumerate the tetrabasic carboxylic acid residue as derived from following aromatic tetracarboxylic acid's dianhydride：3, 3 ', 4,4 '-diphenyl sulfone tetracarboxylic dianhydride, 4,4 '-epoxide double phthalic anhydride, 2,2 ', 3,3 '-benzophenone tetrabasic carboxylic acid two Acid anhydride, 2,3,3 ', 4 '-benzophenone tetracarboxylic dianhydride or 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 2,3 ', 3,41- hexichol Base ether tetracarboxylic dianhydride, double (2,3- dicarboxyphenyi) ether dianhydrides, 3,3 ", 4,4 "-para-terpheny tetracarboxylic dianhydride, 2,3,3 ", 4 "-para-terpheny tetracarboxylic dianhydride or 2,2 ", 3,3 "-para-terpheny tetracarboxylic dianhydride, double (2, the 3- dicarboxyphenyis)-the third of 2,2- Alkane dianhydride or 2,2- double (3,4- dicarboxyphenyi)-propane dianhydride, double (2,3- dicarboxyphenyi) methane dianhydrides or double (3,4- bis- Carboxyl phenyl) methane dianhydride, double (2,3- dicarboxyphenyi) sulfone dianhydrides or double (3,4- dicarboxyphenyi) sulfone dianhydrides, 1,1- be double (2,3- dicarboxyphenyi) ethane dianhydride or 1,1- double (3,4- dicarboxyphenyi) ethane dianhydride, 1,2,7,8- phenanthrene-tetrabasic carboxylic acid two Acid anhydride, 1,2,6,7- phenanthrene-tetracarboxylic dianhydride or 1,2,9,10- phenanthrene-tetracarboxylic dianhydride, 2,3,6,7- anthracene tetracarboxylic dianhydrides, 2,2- are double (3,4- dicarboxyphenyi) tetrafluoropropane dianhydride, 2,3,5,6- hexamethylene dianhydrides, 1,2,5,6- naphthalene tetracarboxylic acid dianhydrides, Isosorbide-5-Nitrae, 5,8- Naphthalene tetracarboxylic acid dianhydride, 2,3,6,7- naphthalene tetracarboxylic acid dianhydrides, 4,8- dimethyl -1,2,3,5,6,7- hexahydro naphthalenes -1,2,5,6- tetracarboxylic acids Acid dianhydride, 2,6- or 2,7- dichloronaphtalene-Isosorbide-5-Nitrae, 5,8- tetracarboxylic dianhydrides, 2,3,6,7- Tetrachloronaphthalenes-Isosorbide-5-Nitrae, 5,8- tetracarboxylic dianhydrides Or Isosorbide-5-Nitrae, 5,8- Tetrachloronaphthalenes -2,3,6,7- tetracarboxylic dianhydrides, 2,3,8,9- perylenes-tetracarboxylic dianhydride, 3,4,9,10- perylenes-tetrabasic carboxylic acid Dianhydride, 4,5,10,11- perylenes-tetracarboxylic dianhydride or 5,6,11,12- perylenes-tetracarboxylic dianhydride, pentamethylene -1,2,3,4- tetrabasic carboxylic acids two Acid anhydride, pyrazine -2,3,5,6- tetracarboxylic dianhydrides, pyrrolidines -2,3,4,5- tetracarboxylic dianhydrides, thiophene -2,3,4,5- tetracarboxylic dianhydrides, Double [4- (3, the 4- di carboxyl phenyloxy) phenyl] propane of 4,4 '-bis- (2,3- di carboxyl phenyloxy) diphenyl methane dianhydrides, 2,2- Dianhydride etc..

In the polyimide film of present embodiment, the diamines residue contained by TPI is for example preferably enumerated Diamines residue represented by following formulas (2).

[changing 7]

In the formula (2), R₃、R₄Independently represent the alkyl or carbon of carbon number 1~3 that can replace through halogen atom or phenyl The alkoxy or alkenyl of number 1~3.

Diamines residue represented by formula (2) easily forms order structure, is particularly advantageous under suppression hot environment Postpone the variable quantity of (RO) in face.From the point of view of this viewpoint, relative to all diamines residues 100 contained by TPI Molar part, diamines residue represented by formula (2) with the range of the molar part of preferably 3 molar parts~60, more preferably 5 molar parts~ It is advisable in the range of 40 molar parts.If the diamines residue represented by formula (2) is less than 3 molar parts, it is difficult to form order structure, Postpone the variable quantity increase of (RO) in face under the hot environment of polyimide film, if more than 60 molar parts, thermoplasticity is damaged.

The preferred concrete example of diamines residue represented by formula (2) can be enumerated two as derived from following diamine compound Amine residue：2,2 '-dimethyl -4,4 '-benzidine (m-TB), 2,2 '-diethyl -4,4 '-benzidine (m-EB), 2, 2 '-diethoxy -4,4 '-benzidine (m-EOB), 2,2 '-dipropoxy -4,4 '-benzidine (m-POB), 2,2 ' - N-propyl -4,4 '-benzidine (m-NPB), 2,2 '-divinyl -4,4 '-benzidine (VAB), 4,4 '-diaminourea Biphenyl, 4,4 '-diaminourea -2,2 '-bis- (trifluoromethyl) biphenyl (TFMB) etc..In these compounds, especially 2,2 '-dimethyl- 4,4 '-benzidine (m-TB) easily forms order structure, can reduce the variable quantity for postponing (RO) in the face under hot environment, Therefore particularly preferably.

The diamines residue beyond diamines residue represented by formula (2) preferably enumerate by p-phenylenediamine (p-PDA), Diamines residue derived from phenylenediamine (m-PDA) etc., it is more preferably (following to be also referred to as with the diamines residue as derived from p-PDA For PDA residues) it is advisable.Relative to all molar parts of diamines residue 100 contained by TPI, PDA residues are with preferably 3 It is advisable in the range of the molar part of molar part~60, in the range of the molar part of more preferably 5 molar parts~40.PDA residues are any, but Due to upright and outspoken structure, therefore with the effect that order structure is totally assigned to polymer.

In addition, the flexibility in order to improve polyimide molecule chain, assigns thermoplasticity, TPI is preferably It is residual containing at least one of the group constituted selected from the diamines residue represented by following formulas (6)~formula (12) diamines Base.

[changing 8]

In the formula (6)~formula (12), R₉The monovalent hydrocarbon or alkoxy of carbon number 1~6 are independently represented, concatenating group A is only On the spot represent to be selected from-O- ,-S- ,-CO- ,-SO- ,-SO₂-、-COO、-CH₂-、-C(CH₃)₂-, the divalence in-NH- or-CONH- Group, n₁Independently represent 0~4 integer.Wherein, from formula (8) will with except formula (7) repetition person, will be with from formula (10) Except formula (9) repetition person.In addition, so-called " independently ", refers in one in the formula (6)~formula (12) or two or more In, multiple concatenating group A, multiple R₉Or multiple n₁It may be the same or different.

Diamines residue represented by formula (6)~formula (12) is advisable with following situation：Relative to TPI In the range of contained all molar parts of diamines residue 100, the molar part of at least one total amount preferably 40 molar parts~97.If The total amount of diamines residue represented by formula (6)~formula (12) is less than 40 molar parts, then the flexibility of polyimides is not enough And thermoplasticity can not be obtained, if more than 97 molar parts, there is the change for postponing (RO) in the face under the hot environment of polyimide film The tendency of change amount increase.

Diamines residue represented by formula (6) is the aromatic diamine residue with two phenyl ring.For as formula (6) institute table For the diamine compound in the source of the diamines residue shown, it is believed that the amino and two of phenyl ring is bonded directly to by least one Valency concatenating group A is located at meta, and the free degree that polyimide molecule chain has increases and with high bendability, is favorably improved The flexibility of polyimide molecule chain.Therefore, by using the diamines residue represented by formula (6), the thermoplasticity of polyimides is carried It is high.Here, concatenating group A preferably-O- ,-CH₂-、-C(CH₃)₂-、-CO-、-SO₂-、-S-。

Diamines residue represented by formula (6) can for example enumerate the diamines residue as derived from following diamine compound：3, 3 '-diaminodiphenyl-methane, 3,3 '-diamino-diphenyl propane, 3,3 '-diamino diphenyl sulfide, 3,3 '-diaminourea two Phenylsulfone, 3,3- diamino-diphenyls ether, 3,4 '-diamino-diphenyl ether, 3,4 '-diaminodiphenyl-methane, 3,4 '-diamino Base diphenyl propane, 3,4 '-diamino diphenyl sulfide, 3,3 '-diaminobenzophenone, (3,3 '-bis- amino) diphenylamine Deng.

Diamines residue represented by formula (7) is the aromatic diamine residue with three phenyl ring.For as formula (7) institute table For the diamine compound in the source of the diamines residue shown, it is believed that the amino and two of phenyl ring is bonded directly to by least one The concatenating group A of valency is located at meta, and the free degree that polyimide molecule chain has increases and with high bendability, helps to carry The flexibility of high polyimide molecule chain.Therefore, if using the diamines residue represented by formula (7), the thermoplasticity of polyimides Improve.Here, concatenating group A preferably-O-.

Diamines residue represented by formula (7) can for example enumerate the diamines residue as derived from following diamine compound：1, 4- double (3- amino-benzene oxygens) benzene, 3- [4- (4- amino-benzene oxygens) phenoxy group] aniline, 3- [3- (4- amino-benzene oxygens) benzene oxygen Base] aniline etc..

Diamines represented by formula (8) is the aromatic diamine residue with three phenyl ring.For the diamines represented by formula (8) For residue, it is believed that be located at meta, polyimides each other by the concatenating group A for two divalence for being bonded directly to a phenyl ring The free degree that strand has increases and with high bendability, is favorably improved the flexibility of polyimide molecule chain.Cause This, by using the diamines residue represented by formula (8), the thermoplasticity of polyimides is improved.Here, concatenating group A preferably-O-.

Diamines residue represented by formula (8) can for example enumerate the diamines residue as derived from following diamine compound：1, Double (4- amino-benzene oxygens) benzene (TPE-R) of 3-, double (3- amino-benzene oxygens) benzene (APB) of 1,3-, 4,4 '-[2- methyl-(1,3- Asia Phenyl) dioxygen base] dianil, 4,4 '-[4- methyl-(1,3- phenylene) dioxygen base] dianils, 4,4 '-[5- methyl-(1,3- Phenylene) dioxygen base] dianil etc..

Diamines residue represented by formula (9) is the aromatic diamine residue with four phenyl ring.For as formula (9) institute table For the diamine compound in the source of the diamines residue shown, it is believed that the amino and two of phenyl ring is bonded directly to by least one The concatenating group A of valency is located at meta, and with high bendability, is favorably improved the flexibility of polyimide molecule chain.Therefore, lead to Cross using the diamines residue represented by formula (9), the thermoplasticity of polyimides is improved.Here, concatenating group A preferably-O- ,-CH₂-、-C (CH₃)₂-、-SO₂-、-CO-、-CONH-。

Diamines residue represented by formula (9) can enumerate the diamines residue as derived from following diamine compound：Double [4- (3- amino-benzene oxygens) phenyl] methane, double [4- (3- amino-benzene oxygens) phenyl] propane, double [4- (3- amino-benzene oxygens) phenyl] Ether, double [4- (3- amino-benzene oxygens) phenyl] sulfones, double [4- (3- amino-benzene oxygens)] benzophenone, double [4,4 '-(3- aminobenzenes Epoxide)] benzanilide etc..

Diamines residue represented by formula (10) is the aromatic diamine residue with four phenyl ring.It is represented for formula (10) Diamines residue for, it is believed that between being located at each other by the concatenating group A for two divalence for being bonded directly at least one phenyl ring Position, the free degree that polyimide molecule chain has increases and with high bendability, is favorably improved polyimide molecule chain Flexibility.Therefore, by using the diamines residue represented by formula (10), the thermoplasticity of polyimides is improved.Here, concatenating group A preferably-O-.

Diamines residue represented by formula (10) can be enumerated by 4- [3- [4- (4- amino-benzene oxygens) phenoxy group] phenoxy group] benzene Amine, 4, the diamines residue derived from diamine compound such as 4 '-[epoxide is double (3,1- sub- phenoxy group)] dianils.

Diamines residue represented by formula (11) is the aromatic diamine residue with four phenyl ring.It is represented on formula (11) Diamines residue, it is believed that by with least two ehter bonds have high bendability, be favorably improved polyimide molecule The flexibility of chain.Therefore, by using the diamines residue represented by formula (11), the thermoplasticity of polyimides is improved.Here, link Base A preferably-C (CH₃)₂-、-O-、-SO₂-、-CO-。

Diamines residue represented by formula (11) can for example enumerate the diamines residue as derived from following diamine compound：2, 2- double [4- (4- amino-benzene oxygens) phenyl] propane (BAPP), double [4- (4- amino-benzene oxygens) phenyl] ethers (BAPE), double [4- (4- amino-benzene oxygens) phenyl] sulfone (BAPS), double [4- (4- amino-benzene oxygens) phenyl] ketone (BAPK) etc..

Diamines residue represented by formula (12) is the aromatic diamine residue with four phenyl ring.It is represented for formula (12) Diamines residue for, it is believed that due to having the concatenating group A of the high divalence of bendability respectively in the both sides of diphenyl skeleton, because This is favorably improved the flexibility of polyimide molecule chain.Therefore, by using the diamines residue represented by formula (12), polyamides is sub- The thermoplasticity of amine is improved.Here, concatenating group A preferably-O-.

Diamines residue represented by formula (12) can be for example enumerated by double [4- (3- amino-benzene oxygens)] biphenyl, double [4- (4- ammonia Phenoxyl)] the diamines residue derived from diamine compound such as biphenyl.

In TPI, by selecting the species of the tetrabasic carboxylic acid residue and diamines residue or using two kinds Respective mol ratio in the case of tetrabasic carboxylic acid residue above or diamines residue, can control thermal coefficient of expansion, modulus in tension, glass Glass transition temperature etc..In addition, in TPI in the case of the construction unit with a variety of polyimides, can be with embedding The form of section is present, and also can randomly exist, and preferably randomly exists.

In the range of the weight average molecular weight of TPI such as preferably 10,000~400,000, more preferably In the range of 50,000~350,000.If weight average molecular weight is less than 10,000, then there is film strength to reduce and easily embrittlement Tendency.On the other hand, if weight average molecular weight is more than 400,000, then increase with having excess stickiness and in coat operations Easily produce the bad tendencies such as non-uniform film thickness one, striped.

(synthesis of non-thermal plasticity polyimides and TPI)

Usual polyimides can be manufactured in the following manner：Tetracarboxylic dianhydride is set to be reacted in a solvent with diamine compound, Generate and heating closed loop is carried out after polyamic acid.Tetracarboxylic dianhydride is for example set to be dissolved in diamine compound with substantially equimolar In machine solvent, in the range of 0 DEG C~100 DEG C at a temperature of stirring 30 minutes~24 hours and carry out polymerisation, thus obtain Must as the predecessor of polyimides polyamic acid.During reaction, 5 weights are turned into the predecessor generated in organic solvent Mode in the range of amount %~30 weight %, in the range of the weight % of preferably 10 weight %~20 dissolves reacted constituent.It is poly- Closing organic solvent used in reaction can for example enumerate：DMF (DMF), DMA (DMAc), N, N- diethyl acetamide, N- methyl -2- Pyrrolizidines ketone (NMP), 2- butanone, dimethyl sulfoxide (DMSO) (DMSO), hexamethyl Phosphamide, N- methyl caprolactams, dimethyl suflfate, cyclohexanone, dioxanes, tetrahydrofuran, diethylene glycol dimethyl ether, three second two Diethylene glycol dimethyl ether, cresols etc..Also can by these solvents and with two or more, and then also can and with fragrant as dimethylbenzene, toluene Race's hydrocarbon.In addition, there is no particular restriction for the usage amount of this organic solvent, preferably it is adjusted to poly- as obtained by polymerisation Usage amount as the concentration of acid amides acid solution turns into weight % of 5 weight %~30 or so and use.

Synthesized polyamic acid is frequently advantageous that in the form of reaction dissolvent solution and uses, and can optionally concentrate, dilute Release or be substituted for other organic solvents.In addition, polyamic acid usual solvents solubility is excellent, therefore it is advantageously used.Polyamides In the range of the preferred 500cps~100,000cps of viscosity of the solution of amino acid.If deviateing the scope, entered using coating machine etc. Uneven thickness one, striped etc. are easily produced during row coat operations bad.The method for making polyamic acid be subject to imidizate has no spy Do not limit, for example, be adapted to using the heating 1 hour~24 under the temperature conditionss in the range of 80 DEG C~400 DEG C in the solvent The heat treatment of hour.

<Copper-clad laminated board>

The copper-clad laminated board of present embodiment possesses insulating barrier and the copper foil at least one face of the insulating barrier etc. Layers of copper, as long as insulating barrier is formed using the polyimide film of present embodiment.In addition, in order to improve insulating barrier and layers of copper Cementability, the layer contacted with layers of copper of insulating barrier is thermoplastic polyimide layer.Layers of copper be provided in insulating barrier one side or On two sides.That is, the copper-clad laminated board of present embodiment can be one side copper-clad laminated board (one side CCL), or double-sided copper-clad layer Lamination (two sides CCL).In the case of one side CCL, the layers of copper being layered on the one side of insulating barrier is considered as to " the first bronze medal of the present invention Layer ".In the case of the CCL of two sides, the layers of copper being layered on the one side of insulating barrier is considered as to " the first layers of copper " of the present invention, will be laminated It is considered as in a insulating layer with being laminated with the face of the first layers of copper for the layers of copper on the face of opposite side " the second layers of copper " of the present invention.This reality The copper-clad laminated board for applying mode is layers of copper to be etched etc. and carry out wired circuit processing, thin copper film is formed, as FPC.

Copper-clad laminated board for example can also be prepared in the following manner：Prepare the polyimide film containing present embodiment and structure Into resin film, its jet-plating metallization is formed after Seed Layer, for example, layers of copper is formed by copper facing.

In addition, copper-clad laminated board can also be prepared in the following manner：Prepare the polyimide film containing present embodiment and The resin film of composition, copper foil is laminated using methods such as thermo-compression bonding to it.

And then, copper-clad laminated board can also be prepared in the following manner：Before copper foil upper contains as polyimides The coating fluid of the polyamic acid of thing is driven, is dried and is made after coated film, be heat-treated and imidizate, polyamides is formed sub- Amine layer.

(the first layers of copper)

In the copper-clad laminated board of present embodiment, copper foil used in the first layers of copper (hereinafter sometimes referred to as " the first copper foil ") It is not particularly limited, for example, can be alternatively electrolytic copper foil for rolled copper foil.

The thickness of first copper foil in the range of preferably less than 13 μm, more preferably 6 μm~12 μm to be advisable.If the first copper foil Thickness increases the bending stress that layers of copper (or thin copper film) applies more than 13 μm when then copper-clad laminated board (or FPC) is bent, by This bending resistance is reduced.In addition, from the viewpoint of production stability and operability, the lower limit of the thickness of the first copper foil is preferred Be set to 6 μm.

In addition, in the range of for example preferred 10GPa~35GPa of the modulus in tension of the first copper foil, more preferably 15GPa~ In the range of 25GPa.In the case of rolled copper foil is used in the present embodiment as the first copper foil, if being entered by heat treatment Row annealing, then flexibility is easily improved.Therefore, if the modulus in tension of copper foil is less than the lower limit, in the first bronze medal of strip Formed on paper tinsel in the process of insulating barrier, the rigidity reduction of the first copper foil itself is caused because of heating.On the other hand, if modulus in tension More than the higher limit, then apply bigger bending stress when FPC is bent to thin copper film, thus its bending resistance is reduced.This Outside, rolled copper foil has its modulus in tension according to heat treatment condition when insulating barrier is formed on copper foil or formed after insulating barrier Annealing of copper foil etc. and change tendency.Therefore, in present embodiment, as long as in the copper-clad laminated board finally obtained, the The modulus in tension of one copper foil is in the scope.

First copper foil is not particularly limited, and commercially available rolled copper foil can be used.

(the second layers of copper)

Second layers of copper be layered in insulating barrier with the first layers of copper on the face of opposite side.Copper foil used in second layers of copper (the second copper foil) is not particularly limited, for example, can be alternatively electrolytic copper foil for rolled copper foil.In addition, city can also be used in the second copper foil The copper foil sold.In addition, it is possible to use be used as the second copper foil with the first copper foil identical copper foil.

The copper-clad laminated board of present embodiment preferably by the 10mm obtained by following evaluation methods circuit substrate chi The accumulative conversion size changing amount of the wiring pattern of very little (FPC sizes) is being tried relative to the ratio of cloth line width and routing space sum Inhomogeneity is less than ± 2% in face in piece.The value of the so-called inhomogeneity is less than ± 2%, refers to the length before and after etching It is less than 2% to spend the size changing amount in direction (MD directions) and the size changing amount of width (TD directions).In the inequality The value of one property exceed ± 2% in the case of, in the FPC processed by copper-clad laminated board, as cause wiring between or connect up The reason for loose contact with terminal, cause reliability or the yield reduction of circuit substrate.Here, simultaneously 1~Fig. 7 of reference picture, One evaluation method of the dimensional stability of copper-clad laminated board for facing to use in present embodiment is illustrated.The evaluation method bag Include following process (1)~process (6).

(1) process of test piece is prepared：

In the process, as illustrated in Fig. 1, the copper-clad laminated board 100 of strip is cut off with set length, it is thus accurate Standby test piece 10.In addition, in the following description, the length direction of the copper-clad laminated board 100 of strip is defined as into MD directions, by width Degree direction is defined as TD directions (also identical for test piece 10).Test piece 10 is preferably with as close to square shape Mode and make copper-clad laminated board 100 width (length in TD directions) and cut-out interval (length in MD directions) it is roughly equal. Though omitting diagram, copper-clad laminated board 100 has insulating resin layer and the one side for being layered in the insulating resin layer or the copper of both sides Layer.

The copper-clad laminated board 100 of object as this evaluation method, which can be used, utilizes the copper clad layers prepared by arbitrary method Lamination.For example copper-clad laminated board 100 can be prepared in the following manner：Prepare resin film, Seed Layer is formed to its jet-plating metallization Afterwards, layers of copper is formed by plating.In addition, copper-clad laminated board 100 also can be by using methods such as thermo-compression bonding by resin film and copper Layers of foil is pressed and prepared.And then, copper-clad laminated board 100 can also be made by the coating resin solution formation insulating resin layer on copper foil It is standby.

(2) process that multiple marks are formed in test piece：

In the process, as shown in FIG. 2, contemplating first in test piece 10 has the side parallel with MD directions and TD directions Imaginary square 20 (be simply denoted as sometimes below " square 20 ").The length on one side of the imaginary square 20 It may be set to the length corresponding with the width (length in TD directions) of copper-clad laminated board 100.In addition, on imaginary square 20 area, in the case where taking more several test pieces, the limit for being processed into FPC scope is included in evaluation object, therefore Preferably it is set as that the area for the scope for being processed into FPC can be covered.Therefore, the length on one side of square 20 is preferably In the range of be set as the length in the TD directions of test piece 10 (width of copper-clad laminated board 100) 60%~90%, more preferably It is set in the range of 70%~80%.The feelings for being for example 250mm in the width (length in TD directions) of copper-clad laminated board 100 Under condition, the length on one side of imaginary square 20, which is preferably, to be set as in the range of 150mm~225mm, more preferably It is set as in the range of 175mm~200mm.

Then, as Fig. 2~as shown in Figure 4, the central area 21 comprising center 20a of imaginary square 20, with Two corner regions 23a, the corner regions 23b of the sidewise two corner 20b in TD side one by one comprising shared square 20 In, the multiple marks for including linear arrangement are formed respectively.Mark is, for example, the circular hole 30 through test piece 10.Multiple holes 30 are excellent Choosing is equally spaced to be formed.In addition, as mark hole 30 such as can be triangle, rectangle it is polygon-shaped.In addition, mark As long as note can recognize that its position, then through hole is not limited to, such as also can form groove, otch in test piece 10, or utilized The decorative pattern of the printings such as ink.

The center 20a of imaginary square 20 turns into the benchmark for the flexible coordinate for determining test piece 10, therefore this is commented In valency method, the central area 21 comprising center 20a is regard as measure object.In central area 21, as long as comprising linear Arrangement, then the position for forming multiple holes 30 is any, such as also can be arranged in T-shaped, L-shaped, preferably can be from vacation Think that the center 20a of square 20 is equably arranged on MD directions and TD directions cross.That is, as shown in Fig. 3, preferably It is that multiple holes 30 are upwardly formed in MD directions and TD side along the cross of the center 20a by imaginary square 20, more Preferably configured in the cross cross section mode overlapping with the center 20a of imaginary square 20.In this case, with Hole 30 overlapping center 20a be as constitute this two direction of MD directions and TD directions arrangement hole 30 and repeat count.

In addition, in central area 21, in order to evaluate the chi for including the change in size inhomogeneity in the face of test piece 10 exactly Very little stability, is advisable with following situation：From the center 20a of square 20, it is respectively relative on MD directions and TD directions One edge lengths of square 20 and in the range of at least more than 12.5%, preferably 12.5%~32.5%, more preferably Hole 30 is formed in the range of 12.5%~25%.

In the copper-clad laminated board 100 of strip as shown in Figure 1, sidewise two of the TD side of square 20 is had Most easily to stretch around the 20b of corner, change in size easily becomes big region.Therefore, will be one by one comprising altogether in the evaluation method There are both the sidewise two corner 20b in TD side two corner regions 23a, corner regions 23b of square 20 as survey Determine object.

In corner regions 23a, corner regions 23b, as long as comprising linear arrangement, then forming the position in hole 30 to appoint Meaning, such as preferably as shown in FIG. 4, along the clamping corner 20b of imaginary square 20 two sides, in MD directions And multiple holes 30 are formed as into L-shaped on TD directions.In this case, being as composition MD directions in the overlapping holes 30 of corner 20b And the arrangement in this two direction of TD directions hole 30 and repeat count.In addition, Fig. 4 illustrate only a corner regions 23b, but for It is also identical for another corner regions 23a.

In two corner regions 23a, corner regions 23b, become to evaluate exactly comprising the size in the face of test piece 10 Change the dimensional stability of inhomogeneity, be advisable with following situation：From the sidewise two ends in the TD side of square 20 (i.e. positive four side The corner 20b of shape 20) towards the center side in MD directions, be respectively relative to MD directions an edge lengths and at least 12.5% with It is upper, in the range of preferably 12.5%~32.5%, in the range of more preferably 12.5%~25% form hole 30.

In addition, in two corner regions 23a, corner regions 23b, in order to evaluate exactly comprising the chi in the face of test piece 10 The dimensional stability of very little change inhomogeneity, is advisable with following situation：From the sidewise two ends in the TD side of square 20 (i.e. just The corner 20b of quadrangle 20) towards the center side in TD directions, it is respectively relative to an edge lengths in TD directions and at least 12.5% More than, in the range of preferably 12.5%~32.5%, in the range of more preferably 12.5%~25% form hole 30.

In addition, holding in face in order to cover test piece 10 and exactly the change in size at each position, it can also make center Be arranged in a straight line in domain 21 shape two ends hole 30 between arrangement scope, with corner regions 23a, corner regions 23b identical Be arranged in a straight line on direction shape two ends hole 30 between arrangement overlapping ranges.

Specifically, it can also configure as follows：When being moved in parallel on TD directions, at least arranged in central area 21 The position at the two ends in the multiple holes 30 of row in the MD direction, with being arranged respectively in two corner regions 23a, corner regions 23b The location overlap (overlap) in the hole 30 of innermost side (side away from corner 20b) in multiple holes 30 in the MD direction.

Similarly, it can also configure as follows：When moving in parallel in the MD direction, at least arranged in central area 21 Closest to corner regions 23a, the position in corner regions 23b hole 30 in multiple holes 30 on TD directions, and in two corners Innermost side (one away from corner 20b in multiple holes 30 on TD directions is arranged separately in region 23a, corner regions 23b Side) hole 30 location overlap.

If it is most reasonable that multiple holes 30 are arranged into across in view of being configured as above, in central area 21, in addition, two In corner regions 23a, corner regions 23b, multiple holes 30 are arranged in L-shaped most reasonable.

In the imaginary square 20 of test piece 10, formed hole 30 scope can by the size in hole 30, the number in hole 30, The length at hole 30 and the interval in hole 30 and adjust.

In order to improve the accuracy of detection of change in size, the size in hole 30 is preferably the interval that is set as hole 30 and hole 30 In less than 20% scope of length.

For forming multiple holes 30 in the central area 21 and two corner regions 23a, corner regions 23b Say, in order to which the dimensional stability for including the change in size inhomogeneity in the face of test piece 10 can be evaluated exactly, preferably in MD On direction and TD directions respectively include at least linear arrangement of more than 11, more preferably comprising more than 20 linearly Arrangement.Here, if the number in hole 30 is set into n, the adjacent hole of measurement object is turned into subsequent handling (3), process (5) 30 turn at n-1 with the space-number in hole 30.On adjacent hole 30 and the interval in hole 30, such as number in hole 30 is 10 In the case of turn into 9 at, hole 30 number be 21 in the case of turn into 20 at.In this case, preferably in MD directions and On TD directions, the number in hole 30 is identical.

In order to improve the accuracy of detection of change in size, the distance between hole 30 and hole 30 are preferably set as more than 2mm.

(3) first measurement processes：

In the process, the position in multiple holes 30 is determined.Moreover, calculating adjoining according to the measurement result of the position in each hole 30 The distance between hole 30 and hole 30 L0.If for example the number in hole 30 is 21, to 20 between adjacent hole 30 and hole 30 Obtain apart from L0 at the interval at place.Here, as shown in FIG. 5, the distance between adjacent hole 30 and hole 30 L0 refer to from some Distances of the center 30a in hole 30 to the center 30a in adjacent hole 30.

The measurement of the position in hole 30 is not particularly limited, for example can be by the image according to test piece 10 come the position of detection hole 30 The method put and implement.

The measurement of the position in the hole 30 of the process can be implemented after the process (2), but it is preferred that before measuring The process that the state (condition) of adjustment test piece 10 is set.One of the state adjustment of test piece 10 can enumerate conditioning.Adjust Wet process can by the way that test piece 10 to be stood to certain time (such as 23 DEG C, 50RH% in the environment of 24 hours) under certain environment and Carry out.

(4) etching work procedure：

In the process, by part or all of etching of the layers of copper of test piece 10.In order to evaluate the dimensionally stable geared to actual circumstances Property, the content of etching is preferably carried out according to the FPC formed by copper-clad laminated board 100 wiring pattern.In test piece 10 Be as prepared by double-sided copper-clad laminated board in the case of, the layers of copper of both sides can be also etched.In addition, adding in actual FPC In work with heat treatment in the case of, the processing for heating test piece 10 with arbitrary temp can be also carried out after the etching.

(5) second measurement processes：

The process is the process for the position for determining multiple holes 30 again after the etching of (4).Moreover, as shown in Fig. 5 Like that, the distance between adjacent hole 30 and hole 30 L1 is calculated according to the measurement result of the position in each hole 30.In the process The measurement of the position in hole 30 is carried out using with the process (3) identical method.

The measurement of the position in the hole 30 of the process can be implemented after the process (4), but it is preferred that with the work The process that sequence (3) similarly sets the state of adjustment test piece 10.The situation of state adjustment has especially been carried out in the process (3) Under, it is also preferred that implementing state adjustment before measuring with identical condition in the process.

(6) process for calculating size changing amount：

In the process, as shown in FIG. 5, the first measurement work is calculated to the interval in two holes 30 of identical afterwards before the etch The difference L1-L0 apart from L1 of gained in the measurement processes of L0 and second of gained in sequence.Moreover, to being arranged in same straight line The hole 30 of shape with the 2 of the interval in hole 30 more than, at preferably 10 more than, more preferably all in the same manner as calculate poor L1-L0.By the difference L1-L0 is used as " size changing amount Δ ".

(7) it is converted into the process of Specification Of Wiring：

In the process, the size changing amount Δ of gained in process (6) is converted into what is formed by copper-clad laminated board 100 The specification of wiring pattern in FPC, gained is represented with the cloth line width and the ratio of routing space sum relative to wiring pattern Scaled value.By the process, in the case where the actual processing of copper-clad laminated board 100 tested will be supplied into FPC, can easily it obtain Know and show the influence that the change in size of copper-clad laminated board 100 is caused to FPC wiring pattern.

In the process, size changing amount Δ is converted into first in the predetermined FPC formed by copper-clad laminated board 100 The specification of cloth line width/routing space of L/S wiring patterns, the size changing amount obtained by conversion is added up and accumulative conversion ruler is obtained Very little variable quantity.For example between two holes 30 before relative to etching apart from L0, make a reservation for wiring pattern in the FPC that is formed Cloth line width and routing space are respectively that in the case of the L0 1/Y, size changing amount Δ is converted into reduction according to following formula (downsizing) value during specification for being 2 × (1/Y), obtains the accumulative conversion size changing amount of 2 × (1/Y) specification.

Accumulative conversion size changing amount=[∑_I=1 ¹(2×Δ_i/Y)]

In the formula, mark ∑_I=1 ¹The summation of expression 1 to i.In addition, size changing amount Δ represents n-th of hole after etching 30 and (n-1)th hole 30 apart from L1 subtract n-th of hole 30 before etching and (n-1)th hole 30 apart from value (this obtained by L0 In, n is more than 2 integer).For example, Δ₁Size for the length (distance between two adjacent holes 30) at the 1st interval becomes Change amount, Δ_iThe size changing amount for the length being spaced for i-th (i refers to positive integer).

Then, the displacement ratio of wiring is obtained according to following formula by accumulative conversion size changing amount.The displacement ratio of the wiring It is to represent tired with the ratio of routing space (Smm) sum with the cloth line width (Lmm) of the L/S wiring patterns relative to predetermined formation Meter conversion size changing amount.

The displacement ratio (%) of wiring=

{[∑_I=1 ¹(2×Δ_i/Y)]/[L+S]}×100

The displacement ratio of the wiring of MD and TD in the FPC that will be calculated as above is plotted on chart, is thus obtained Obtain the near linear (in addition, omit diagram of chart) corresponding with FPC sizes.Here, so-called " FPC sizes ", refers in FPC Distance in a plurality of wiring formed between the wiring at the farthest two ends of distance.The size of the slope of chart refers to the big of cloth displacement of the lines Small, the size of the inhomogeneity of the slope of chart refers to the size of inhomogeneity in the face of cloth displacement of the lines.

By the process, in the case where the actual processing of copper-clad laminated board 100 tested will be supplied into circuit, can easily it obtain Know and show the influence that the change in size of copper-clad laminated board 100 is caused to FPC wiring pattern.In addition, approximate by making The chart of straight line, can it is corresponding with FPC sizes and see and show as try body copper-clad laminated board 100 made by Inhomogeneity in the size of the displacement of wiring or face.

In addition, after also the size changing amount Δ of gained in the process (6) can be added up, accumulative size changing amount is converted Into the specification of cloth line width/routing space of the L/S wiring patterns in the predetermined FPC formed by copper-clad laminated board 100, obtain Accumulative conversion size changing amount.For example the size changing amount Δ at each interval is added up, accumulative size changing amount ∑ is obtained.This adds up Size changing amount ∑ can be calculated by following formula.

∑=Δ₁+Δ₂+Δ₃+···+Δ_i=∑_I=1 ¹Δ_i

Accumulative size changing amount ∑ can be to the MD directions of copper-clad laminated board 100, the either direction in TD directions, preferably two sides To obtaining.According to the size of accumulative size changing amount ∑, the MD directions of evaluable copper-clad laminated board 100, the size in TD directions are steady It is qualitative.In addition, obtaining the near linear of specification increase (scale up) according to the measured value of accumulative size changing amount ∑.

As more than, according to the evaluation method, can accurately it be evaluated comprising face by process (1)~process (7) The change in size of the copper-clad laminated board 100 of interior inhomogeneity.Even if in addition, taking more several test pieces from copper-clad laminated board 100 In the case of, also dimensional stability can be evaluated respectively to each region for being processed into FPC.

<FPC>

The copper-clad laminated board of present embodiment is useful mainly as FPC materials.That is, using well-established law by present embodiment The layers of copper of copper-clad laminated board is processed into pattern-like and forms wiring layer, thus can manufacture as one embodiment of the present invention FPC。

[embodiment]

Embodiment described below is more particularly described to the feature of the present invention.However, the scope of the present invention is not limited to Embodiment.In addition, in following embodiment, as long as no special instructions, then various measure, evaluation is to utilize following methods.

[measure of viscosity]

On the measure of viscosity, using E types viscosimeter, (rich strangle flies the manufacture of (Brookfield) company, trade name：DV-II+ Pro the viscosity at 25 DEG C) is determined.The setting speed in the way of moment of torsion (torque) turns into 10%~90%, starts to have determined warp Cross after 2 minutes, read value during viscosity stabilization.

[measure of weight average molecular weight]

Weight average molecular weight is to utilize gel permeation chromatograph (eastern Cao (Tosoh) limited company manufacture, commodity Name：HLC-8220GPC) it is measured.Using polystyrene as standard substance, developing solvent uses N, N- dimethylacetamides Amine.

[measure of glass transition temperature (Tg)]

On glass transition temperature, Measurement of Dynamic Viscoelasticity device (DMA is used：UBM companies manufacture, trade name： E4000F), from 30 DEG C to 400 DEG C using 4 DEG C/min of programming rate, frequency 11Hz to size as 5mm × 20mm polyimide film It is measured, modulus of elasticity is changed to (tan δ) and reaches that the temperature of maximum is used as glass transition temperature.In addition, DMA institutes will be used The storage modulus at 30 DEG C determined is 1.0 × 10⁹More than Pa, the storage modulus at 360 DEG C are less than 1.0 × 10⁸Pa person is considered as " thermoplasticity ", is 1.0 × 10 by the storage modulus at 30 DEG C⁹More than Pa, the storage modulus at 360 DEG C show 1.0 × 10⁸Pa Above person is considered as " non-thermal plasticity ".

[measure of thermal coefficient of expansion (CTE)]

Using thermomechanical analyzer, (Brooker (Bruker) company manufactures, trade name：4000SA), to size be 3mm × 20mm polyimide film one side applies 5.0g heavy burden, simultaneously it is warming up to 265 DEG C from 30 DEG C with certain programming rate, And then after being kept for 10 minutes at such a temperature, cooled down with 5 DEG C/min of speed, obtain 250 DEG C to 100 DEG C of average thermal expansion Coefficient (thermal coefficient of expansion).

[measure of the surface roughness of copper foil]

On the surface roughness of copper foil, AFM (Atomic Force Microscope, AFM) (Bu Lu is used The manufacture of gram AXS (Bruker AXS) company, trade name：Dimension icon (Dimension Icon) type SPM), probe (Brooker AXS (Bruker AXS) company manufactures, trade name：TESPA (NCHV), front end radius of curvature 10nm, spring constant 42N/m), with Tapping-mode (tapping mode) is measured to the scope of 80 μm of 80 μ m of copper foil surface, obtains 10 mean roughness (Rz)。

[measure of peel strength]

1) the cast side (resin coated side) of one side copper-clad laminated board

The copper foil of one side copper-clad laminated board (copper foil/resin bed) is carried out after circuit fabrication with width 1.0mm, with width： 8cm × length：4cm is cut off, formation determination sample 1.On the peel strength for the cast side for determining sample 1, extension test is used (Toyo Seiki makes manufactured to machine (Tensilon tester), trade name：Universal testing machine (Strograph) VE-1D), profit The resin bed side for determining sample 1 is fixed on aluminium sheet with two-sided tape, by copper foil towards 90 ° of directions with the speed of 50mm/ minutes Peel off, obtain by copper foil from resin bed peel off 10mm when central intensity.It regard the value as peel strength 1A.

2) the cast side (resin coated side) of double-sided copper-clad laminated board

By the thermo-compression bonding side of double-sided copper-clad laminated board (copper foil/resin bed/copper foil) with pouring into a mould the copper foil on side two sides with width 0.8mm is carried out after circuit fabrication (carrying out wiring processing in the way of the copper foil on two sides turns into same position), with width：8cm× Length：4em is cut off, formation determination sample 2.On the peel strength for the cast side for determining sample 2, stretching testing machine is used (Tensilon tester) (Toyo Seiki makes manufactured, trade name：Universal testing machine (Strograph) VE-1D), utilize The copper-clad surface that two-sided tape will determine the thermo-compression bonding side of sample 2 is fixed on aluminium sheet, by copper foil towards 90 ° of directions with 50mm/ minutes Speed peel off, obtain by the copper foil of resin coated side from resin bed peel off 10mm when median intensity.It regard the value as stripping From intensity 2A.

[measure for postponing (RO) in face]

On postponing (RO) in face, using birefringence meter, (photonic crystal lattice (Photonic-Lattice) company manufactures, business The name of an article：Wide scope (wide range) birefringence evaluation system WPA-100, mensuration region：MD：140mm×TD：100mm), ask Go out the delay in direction in the face of set sample.In addition, incidence angle is 0 °, measure wavelength is 543nm.

[measure of modulus in tension]

It is equal with the treatment process of copper-clad laminated board using having been carried out using vacuum drying oven on the modulus in tension of copper foil The copper foil of heat treatment, universal testing machine (Strograph) R-1 that limited company of institute manufactures is made using Toyo Seiki, The value of modulus in tension is determined in the environment of 23 DEG C of temperature, relative humidity 50%.

Abbreviation used represents following compound in embodiment and comparative example.

NTCDA：2,3,6,7- naphthalene tetracarboxylic acid dianhydrides

BPDA：3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride

PMDA：Pyromellitic acid anhydride

m-TB：2,2 '-dimethyl -4,4 '-benzidine

m-EOB：2,2 '-diethoxy -4,4 '-benzidine

TPE-R：1,3- double (4- amino-benzene oxygens) benzene

DAPE：4,4 '-diamino-diphenyl ether

BAPP：2,2- double [4- (4- amino-benzene oxygens) phenyl] propane

DMAc：DMA

(synthesis example 1)

Under nitrogen flowing, the m-TB (5.4 molar part) and 175.4 parts by weight of 1146.4 parts by weight are put into reactive tank TPE-R (0.6 molar part) and polymerization after solid component concentration turn into 15 weight % amount DMAc, be stirred at room temperature and Dissolved.Then, the BPDA (2.4 molar part) of 706.1 parts by weight of the addition and NTCDA (3.6 molar part) of 965.4 parts by weight Afterwards, continue to stir 3 hours and carry out polymerisation at room temperature, obtain polyamic acid solution 1.The solution of polyamic acid solution 1 Viscosity is 41,100cps.

Then, polyamic acid solution 1 is uniformly coated on stainless steel in the way of the thickness after hardening turns into about 25 μm After in supporting base material, the heat drying at 120 DEG C and remove solvent.And then, carried out from 120 DEG C to 360 DEG C within 30 minutes Interim heat treatment, completes imidizate, prepares polyimide film 1 (base of biphenyl four and biphenylene：65 moles of %, it is non-thermal Plasticity, Tg：More than 400 DEG C, CTE：7.7ppm/K).

(synthesis example 2)

Under nitrogen flowing, the m-TB (3.5 molar part) and 672.4 parts by weight of 743.0 parts by weight are put into reactive tank TPE-R (2.3 molar part) and polymerization after solid component concentration turn into 15 weight % amount DMAc, be stirred at room temperature and Dissolved.Then, the BPDA (1.2 molar part) of 353.1 parts by weight of addition and (4.6 moles of the NTCDA of 1233.6 parts by weight Part) after, continue to stir 3 hours and carry out polymerisation at room temperature, obtain polyamic acid solution 2.Polyamic acid solution 2 it is molten Fluid viscosity is 41,900cps.

Then, polyamic acid solution 2 is uniformly coated on stainless steel in the way of the thickness after hardening turns into about 25 μm After in supporting base material, the heat drying at 120 DEG C and remove solvent.And then, carried out from 120 DEG C to 360 DEG C within 30 minutes Interim heat treatment, completes imidizate, prepares polyimide film 2 (base of biphenyl four and biphenylene：41 moles of %, it is non-thermal Plasticity, Tg：391 DEG C, CTE：19.1ppm/K).

(synthesis example 3)

Under nitrogen flowing, the m-TB (4.9 molar part) and 350.8 parts by weight of 1040.2 parts by weight are put into reactive tank TPE-R (1.2 molar part) and polymerization after solid component concentration turn into 15 weight % amount DMAc, be stirred at room temperature and Dissolved.Then, BPDA (1.8 molar part), the NTCDA (2.4 molar part) of 643.6 parts by weight of 529.6 parts by weight are added And 392.6 parts by weight PMDA (1.8 molar part) after, at room temperature continue stir 3 hours and carry out polymerisation, obtain polyamides Amino acid solution 3.The solution viscosity of polyamic acid solution 3 is 32,500cps.

Then, polyamic acid solution 3 is uniformly coated on stainless steel in the way of the thickness after hardening turns into about 25 μm After in supporting base material, the heat drying at 120 DEG C and remove solvent.And then, carried out from 120 DEG C to 360 DEG C within 30 minutes Interim heat treatment, completes imidizate, prepares polyimide film 3 (base of biphenyl four and biphenylene：55 moles of %, it is non-thermal Plasticity, Tg：377 DEG C, CTE：14.8ppm/K).

(synthesis example 4)

Under nitrogen flowing, the m-TB (2.6 molar part) and 760.9 parts by weight of 552.0 parts by weight are put into reactive tank DAPE (3.8 molar part) and polymerization after solid component concentration turn into 15 weight % amount DMAc, be stirred at room temperature and Dissolved.Then, after the NTCDA (6.4 molar part) of 1716.3 parts by weight of addition, continue to stir 3 hours and enter at room temperature Row polymerisation, obtains polyamic acid solution 4.The solution viscosity of polyamic acid solution 4 is 42,300cps.

Then, polyamic acid solution 4 is uniformly coated on stainless steel in the way of the thickness after hardening turns into about 25 μm After in supporting base material, the heat drying at 120 DEG C and remove solvent.And then, carried out from 120 DEG C to 360 DEG C within 30 minutes Interim heat treatment, completes imidizate, prepares (the biphenylene of polyimide film 4：20 moles of %, non-thermal plasticity, Tg：400 More than DEG C, CTE：32.1ppm/K).

(synthesis example 5)

Under nitrogen flowing, the m-EOB (3.3 molar part) and 660.8 parts by weight of 898.7 parts by weight are put into reactive tank DAPE (3.3 molar part) and polymerization after solid component concentration turn into 15 weight % amount DMAc, be stirred at room temperature and Dissolved.Then, after the PMDA (6.6 molar part) of 1439.6 parts by weight of addition, continue to stir 3 hours and carry out at room temperature Polymerisation, obtains polyamic acid solution 5.The solution viscosity of polyamic acid solution 5 is 31,700cps.

Then, polyamic acid solution 5 is uniformly coated on stainless steel in the way of the thickness after hardening turns into about 25 μm After in supporting base material, the heat drying at 120 DEG C and remove solvent.And then, carried out from 120 DEG C to 360 DEG C within 30 minutes Interim heat treatment, completes imidizate, prepares (the biphenylene of polyimide film 5：25 moles of %, non-thermal plasticity, Tg：376 DEG C, CTE：33.5ppm/K).

(synthesis example 6)

Under nitrogen flowing, the m-TB (0.3 molar part) and 1490.9 parts by weight of 63.7 parts by weight are put into reactive tank TPE-R (5.1 molar part) and polymerization after solid component concentration turn into 15 weight % amount DMAc, be stirred at room temperature and Dissolved.Then, the BPDA (3.8 molar part) of 1118.0 parts by weight of the addition and PMDA (1.6 molar part) of 349.0 parts by weight Afterwards, continue to stir 3 hours and carry out polymerisation at room temperature, obtain polyamic acid solution 6.The solution of polyamic acid solution 6 Viscosity is 6,700cps, and weight average molecular weight is 163,400.

Then, polyamic acid solution 6 is uniformly coated on stainless steel in the way of the thickness after hardening turns into about 25 μm Supporting base material on after, the heat drying at 120 DEG C and remove solvent.And then, entered from 120 DEG C to 360 DEG C within 30 minutes The interim heat treatment of row, completes imidizate, prepares polyimide film 6 (base of biphenyl four and biphenylene：38 moles of %, heat Plasticity, Tg：242 DEG C, 30 DEG C of storage modulus：4.3×10⁹Pa, 360 DEG C of storage modulus：1.4×10⁷Pa)。

(synthesis example 7)

Under nitrogen flowing, the m-TB (3.5 molar part) and 672.4 parts by weight of 743.0 parts by weight are put into reactive tank TPE-R (2.3 molar part) and polymerization after solid component concentration turn into 15 weight % amount DMAc, be stirred at room temperature and Dissolved.Then, the BPDA (4.1 molar part) of 1206.3 parts by weight of the addition and PMDA (1.7 molar part) of 370.8 parts by weight Afterwards, continue to stir 3 hours and carry out polymerisation at room temperature, obtain polyamic acid solution 7.The solution of polyamic acid solution 7 Viscosity is 7,200cps, and weight average molecular weight is 112,000.

Then, polyamic acid solution 7 is uniformly coated on stainless steel in the way of the thickness after hardening turns into about 25 μm After in supporting base material, the heat drying at 120 DEG C and remove solvent.And then, carried out from 120 DEG C to 360 DEG C within 30 minutes Interim heat treatment, completes imidizate, prepares polyimide film 7 (base of biphenyl four and biphenylene：66 moles of %, thermoplastic Property, Tg：266 DEG C, 30 DEG C of storage modulus：4.3×10⁹Pa, 360 DEG C of storage modulus：7.1×10⁷Pa)。

(synthesis example 8)

Under nitrogen flowing, the m-TB (1.1 molar part) and 1344.7 parts by weight of 233.5 parts by weight are put into reactive tank TPE-R (4.6 molar part) and polymerization after solid component concentration turn into 15 weight % amount DMAc, be stirred at room temperature and Dissolved.Then, the BPDA (2.3 molar part) of 676.7 parts by weight of the addition and PMDA (3.4 molar part) of 741.6 parts by weight Afterwards, continue to stir 3 hours and carry out polymerisation at room temperature, obtain polyamic acid solution 8.The solution of polyamic acid solution 8 Viscosity is 7,400eps, and weight average molecular weight is 163,400.

Then, polyamic acid solution 8 is uniformly coated on stainless steel in the way of the thickness after hardening turns into about 25 μm After in supporting base material, the heat drying at 120 DEG C and remove solvent.And then, carried out from 120 DEG C to 360 DEG C within 30 minutes Interim heat treatment, completes imidizate, and preparing polyimide film 8, (base of biphenyl four and biphenylene are 30 moles of %, thermoplastic Property, Tg：279 DEG C, 30 DEG C of storage modulus：4.1×10⁹Pa, 360 DEG C of storage modulus：7.9×10⁷Pa)。

[embodiment 1-1]

In endless belt-shaped stainless steel supporting base material, the three-layer co-extruded of branch manifold (multimanifold) formula is used Go out multilayer die head, with the three-decker of the order of the polyamic acid solution 7 of 7/ polyamic acid solution of polyamic acid solution 1/ continuously It is extrusion coated, the heat drying 3 minutes at 130 DEG C and remove solvent.Then, carried out from 130 DEG C to 360 DEG C at interim heat Reason, completes imidizate, prepares the thickness of thermoplastic polyimide layer/non-thermal plasticity polyimide layer/thermoplastic polyimide layer Degree is respectively 2.5 μm/20 μm/2.5 μm of polyimide film 1a '.Using knife edge method by the polyimide film 1a ' in supporting base material Peel off, the length for preparing width is 1100mm strip polyimide film 1a.

By the end of left and right two (left side (Left) and right side (Right)) in strip polyimide film 1a TD directions with And central portion (Center) is respectively with A4 sizes (TD：210mm×MD：297mm) cut off, prepare sample L1 (Left), sample R1 And sample C1 (Center) (Right).

Sample L1, sample R1 and sample C1 are each distinguished in aspect of measure and postpone (RO).By the measured value of each sample most Big value regard the difference of the maxima and minima in the measured value for postponing (RO) in face as " width as " postponing (RO) in face " Postpone the inhomogeneity (Δ RO) of (RO) in the face in direction (TD directions) ".In addition, " with pressure in the environment of 360 DEG C of temperature 340MPa/m², 15 minutes retention times pressurization before and after face in delay (RO) variable quantity " be set to before sample C1 pressurization And the difference of the maximum in each face after pressurization in the measured value of delay (RO).

In addition, the mensuration region in each sample is as follows.

Sample L1：The left end region in TD directions and the middle section in MD directions

Sample R1：The right side end area in TD directions and the middle section in MD directions

Sample C1：TD directions and the middle section in MD directions

Strip polyimide film 1a evaluation result is as follows.

CTE：17ppm/K

Postpone (RO) in face：11nm

Postpone the inhomogeneity (Δ RO) of (RO) in the face of width (TD directions)：1nm

With pressure 340MPa/m in the environment of 360 DEG C of temperature², 15 minutes retention times pressurization before and after face in delay (RO) variable quantity：3nm

[embodiment 1-2]

In addition to the length of width (TD directions) is set into 540mm, strip is prepared as with embodiment 1-1 Polyimide film 1b.

Strip polyimide film 1b evaluation result is as follows.

CTE：17ppm/K

Postpone (RO) in face：11nm

[embodiment 1-3]

In copper foil 1 (rolled copper foil, the manufacture of JX Metallgesellschaft AG, trade name of strip：GHY5-93F-HA-V2 Paper tinsel, thickness：12 μm, the modulus in tension after heat treatment：18GPa, the length of width：On surface 540mm), after hardening Thickness turn into after 2.5 μm of mode even spread polyamic acid solution 7, the heat drying 1 minute at 120 DEG C and remove molten Agent.Thereon in the way of the thickness after hardening turns into 20 μm after even spread polyamic acid solution 1, heated at 120 DEG C dry Dry 3 minutes and remove solvent.And then, in the even spread polyamic acid 7 in the way of the thickness after hardening turns into 2.5 μm thereon Afterwards, at 120 DEG C heat drying 1 minute and remove solvent.Then, interim heat treatment is carried out from 130 DEG C to 360 DEG C, it is complete Into after imidizate, one side copper-clad laminated board 1a is prepared.

The evaluation knot for the strip polyimide film for removing and preparing is etched to one side copper-clad laminated board 1a copper foil Fruit is as follows.

CTE：17ppm/K

Postpone (RO) in face：11nm

In the polyimide layer side superimposed copper foil 1 of the one side copper-clad laminated board 1a, in 360 DEG C of temperature, pressure 340MPa/ m²Under conditions of be thermally compressed 15 minutes, prepare double-sided copper-clad laminated board 1a.Double-sided copper-clad laminated board 1a copper foil is etched Delay (RO) is 8nm in the face for the strip polyimide film for removing and preparing.

Cutting processing is carried out to prepared double-sided copper-clad laminated board 1a central portion, prepares the copper-clad laminated board of strip (end is wide by 1a '：250mm) as dimensional stability evaluation sample material.

The copper-clad laminated board 1a ' is cut off with length 250mm in the MD direction, MD is made：250mm×TD：250mm. As shown in FIG. 6, the MD of copper-clad laminated board after severance：200mm×TD：Positive four side of imagination is contemplated in the range of 200mm Shape.In the corner regions (Left of left and right two for including shared sidewise two corners in TD side one by one of the imaginary square And Right) and the middle section (Center) at center comprising imaginary square in, respectively on MD and TD directions with 2.5mm interval continuously carries out 21 perforate processing, prepares evaluation sample.In addition, perforate processing uses diameter 0.105mm Drill bit (drill).

Using noncontact computer numerical control (Computer Numerical Control, CNC), (three is rich for determining image machine (Mitutoyo) company manufactures, trade name：Quick video (Quick Vision) QV-X404PIL-C), to by evaluation sample Two sides copper foil layer all etching and the position in each hole before and after removing is measured.Calculated according to measured value before and after etching The size changing amount and accumulative size changing amount of adjacent two distance between borehole.

Prepare the copper-clad laminated board 1a ' of strip, evaluation sample 1, evaluation sample 2 are prepared as shown in FIG. 7.It is right Evaluate the position for determining each hole before and after Center, Left and Right etching respectively with sample 1, evaluation sample 2.According to Measured value calculates the size changing amount of the distance between the adjacent holes before and after etching and these total accumulative size (at 20) Variable quantity.

According to copper-clad laminated board 1a ' evaluation result, MD accumulative size changing amount and inhomogeneity are shown in Table 1. In addition, in table 1, imagination is converted into Left, Center, Right accumulative size changing rate and by accumulative size changing amount FPC sizes 10mm accumulative conversion size changing amount is represented, also shows that the inequality of Left, Center, Right gamut One property.In addition, " accumulative size changing rate " refers to aggregate value of the accumulative size changing amount relative to two distance between borehole before etching Ratio (%).In addition, the numerical value of " scope " in table refer to the median of Left, Center, Right gamut ± on Lower scope (identical in table 2, table 3).

[table 1]

According to the result, confirming can be to using wiring substrate (L/S formed by copper-clad laminated board 1a ' as material =0.025mm/0.0025mm) the displacement ratio of wiring and the inhomogeneity of the size changing rate in test piece face are evaluated, and can The inhomogeneity of the displacement ratio of wiring during confirmation embodiment 1-3 double-sided copper-clad laminated board 1a each FPC sizes is small.In addition Can confirm, in order to realize the only CTE of control polyimide film in the case of the high size of copper-clad laminated board that can not reach it is steady Determine precision, it is important that postpone in chain of command.

[embodiment 1-4]

Copper foil 1 is overlapped on the strip polyimide film 1b prepared in embodiment 1-2 two sides, with 360 DEG C of temperature, pressure Power 340MPa/m²Condition be thermally compressed 15 minutes, prepare double-sided copper-clad laminated board 1b, prepare strip in the same manner as embodiment 1-3 (end is wide by the copper-clad laminated board 1b ' of shape：250mm), the evaluation of dimensional stability is carried out.It the results are shown in table 2.

[table 2]

[comparative example 1-1]

Prepare strip polyimide film 1c (thickness：25 μm, the manufacture of Zhong Yuan (Kaneka) company, trade name：This Austria of pik (Pixeo))。

Strip polyimide film 1c evaluation result is as follows.

CTE：17ppm/K

Postpone (RO) in face：200nm

Postpone the inhomogeneity (Δ RO) of (RO) in the face of width (TD directions)：80nm

With pressure 340MPa/m in the environment of 360 DEG C of temperature², 15 minutes retention times pressurization before and after face in delay (RO) variable quantity：30nm

[comparative example 1-2]

Copper foil 1 is overlapped on strip polyimide film 1c two sides, with 360 DEG C of temperature, pressure 340MPa/m²Condition Thermo-compression bonding 15 minutes, prepares double-sided copper-clad laminated board 1c, the copper-clad laminated board 1c ' of strip is prepared as with embodiment 1-3 (end is wide：250mm), the evaluation of dimensional stability is carried out.It the results are shown in table 3.

[table 3]

[embodiment 2-1]

In addition to the three-decker of the order of the polyamic acid solution 8 of 8/ polyamic acid solution of polyamic acid solution 1/, with The strip polyimide film 2 that the length that embodiment 1-1 is prepared as width is 1100mm.

The evaluation result of strip polyimide film 2 is as follows.

CTE：17ppm/K

Postpone (RO) in face：11nm

With pressure 340MPa/m in the environment of 360 DEG C of temperature², 15 minutes retention times pressurization before and after face in delay (RO) variable quantity：5nm

[embodiment 3-1]

In addition to the three-decker of the order of the polyamic acid solution 6 of 6/ polyamic acid solution of polyamic acid solution 2/, with The strip polyimide film 3 that the length that embodiment 1-1 is prepared as width is 1100mm.

The evaluation result of strip polyimide film 3 is as follows.

CTE：17ppm/K

Postpone (RO) in face：17nm

Postpone the inhomogeneity (Δ RO) of (RO) in the face of width (TD directions)：3nm

With pressure 340MPa/m in the environment of 360 DEG C of temperature², 15 minutes retention times pressurization before and after face in delay (RO) variable quantity：7nm

[embodiment 4-1]

In addition to the three-decker of the order of the polyamic acid solution 8 of 8/ polyamic acid solution of polyamic acid solution 3/, with The strip polyimide film 4 that the length that embodiment 1-1 is prepared as width is 1100mm.

The evaluation result of strip polyimide film 4 is as follows.

CTE：17ppm/K

Postpone (RO) in face：15nm

Postpone the inhomogeneity (Δ RO) of (RO) in the face of width (TD directions)：2nm

With pressure 340MPa/m in the environment of 360 DEG C of temperature², 15 minutes retention times pressurization before and after face in delay (RO) variable quantity：10nm

More than, embodiments of the present invention are described in detail for the purpose of illustration, but the present invention is not by the reality The limitation of mode is applied, various modifications can be carried out.

Present application advocates the excellent of the Japanese patent application case 2016-89514 filed an application based on April 27th, 2016 First weigh, all the elements of this application case are referenced to herein.

Claims

1. a kind of polyimide film, has at least side of the non-thermal plasticity polyimide layer comprising non-thermal plasticity polyimides Thermoplastic polyimide layer comprising TPI, and

The polyimide film is characterised by meeting following condition i~condition iv：

I thermal coefficient of expansions is in the range of 10ppm/K~30ppm/K；

The glass transition temperature of TPI described in ii is in more than 200 DEG C and less than 350 DEG C of scope；

The value postponed in iii faces is in more than 5nm and below 50nm scope；

The inhomogeneity postponed in the face of iv widths is below 10nm.

2. polyimide film according to claim 1, it is characterised in that：

In addition to the condition of the i~iv, further meet：

V is in the environment of 360 DEG C of temperature with pressure 340MPa/m², 15 minutes retention times pressurization before and after face in delay change Measure as below 20nm.

3. polyimide film according to claim 1 or 2, it is characterised in that：

In addition to the condition of the i~iv, further meet：

Non-thermal plasticity polyimides described in vi contains tetrabasic carboxylic acid residue and diamines residue, and the tetrabasic carboxylic acid residue and diamines residue are equal For aromatic series base, the aromatic series base includes the base of biphenyl four or biphenylene, and relative to the tetrabasic carboxylic acid residue and diamines Total 100 molar parts of residue, the base of biphenyl four or biphenylene are more than 40 molar parts.

4. polyimide film according to claim 1 or 2, it is characterised in that：

In addition to the condition of the i~iv, further meet：

TPI described in vii contains tetrabasic carboxylic acid residue and diamines residue, and the tetrabasic carboxylic acid residue and diamines residue are equal For aromatic series base, the aromatic series base includes the base of biphenyl four or biphenylene, and relative to the tetrabasic carboxylic acid residue and diamines Total 100 molar parts of residue, the base of biphenyl four or biphenylene are the scope more than 30 molar parts and below 80 molar parts It is interior.

5. polyimide film according to claim 1 or 2, it is characterised in that：

Relative to all molar parts of tetrabasic carboxylic acid residue 100 contained by the non-thermal plasticity polyimides, by 3,3 ', 4,4 '-biphenyl Tetrabasic carboxylic acid residue derived from tetracarboxylic dianhydride is in the scope more than 20 molar parts and below 70 molar parts.

6. polyimide film according to claim 1 or 2, it is characterised in that：

Relative to all molar parts of tetrabasic carboxylic acid residue 100 contained by the TPI, by 3,3 ', 4,4 '-biphenyl four Tetrabasic carboxylic acid residue derived from carboxylic acid dianhydride is more than 40 molar parts.

7. polyimide film according to claim 1 or 2, it is characterised in that：

Relative to all molar parts of diamines residue 100 contained by the non-thermal plasticity polyimides, represented by following formulas (1) Diamines residue be 20 molar parts more than,

In formula, R₁、R₂Independently represent the alkyl or the alcoxyl of carbon number 1~3 of carbon number 1~3 that can replace through halogen atom or phenyl The alkenyl of base or carbon number 2~3.

8. polyimide film according to claim 1 or 2, it is characterised in that：

Relative to all molar parts of diamines residue 100 contained by the TPI, two represented by following formulas (2) Amine residue be 3 molar parts more than and 60 molar parts below scope in,

In formula, R₃、R₄Independently represent the alkyl or the alcoxyl of carbon number 1~3 of carbon number 1~3 that can replace through halogen atom or phenyl Base or alkenyl.

9. a kind of copper-clad laminated board, the layers of copper with insulating barrier and at least one face of the insulating barrier, and it is described Copper-clad laminated board is characterised by：

The insulating barrier has the thermoplastic polyimide layer contacted with the surface of the layers of copper and the non-thermoplastic being laminated indirectly Property polyimide layer,

The insulating barrier includes the polyimide film as any one of claim 1 to 8.

10. copper-clad laminated board according to claim 9, it is characterised in that：Length direction before and after the etching of the layers of copper Size changing amount and the size changing amount of width be less than 2%.