CN1946823A - Adhesive film, flexible metal-clad laminate, and process for producing the same - Google Patents

Abstract

An adhesive film with which a flexible metal-clad laminate inhibited from suffering a dimensional change is obtained through laminating; and a flexible metal-clad laminate comprising the adhesive film and a metal foil bonded thereto. The adhesive film comprises a polyimide film and, formed on at least one side thereof, an adhesive layer comprising a thermoplastic polyimide and has coefficients of linear expansion satisfying the relationship 1.0>(coefficient of MD linear expansion)/(coefficient of TD linear expansion)>0.1. This adhesive film may be one produced continuously and further satisfying the relationship 1.70>(MD modulus)/(TD modulus)>1.05 when the adhesive film has an MD modulus of 5 GPa or higher throughout the whole width thereof. That adhesive film may be one produced continuously and further satisfying the relationship 2.00>(MD modulus)/(TD modulus)>1.10 when the adhesive film has an MD modulus less than 5 GPa throughout the whole width thereof.

Description

Adhering film, flexible metal-clad laminate and preparation method thereof

Technical field

The present invention relates to a kind of at least one surface of Kapton, be provided with the adhering film of the adhesive linkage that contains thermoplastic polyimide and on this adhering film applying tinsel and the flexible metal-clad laminate that obtains, and preparation method thereof.

Background technology

In recent years, be accompanied by lightweight, miniaturization, the densification of electronic product, the needs of various printed base plates are increased, wherein particularly the needs of flexible overlapping plate (being also referred to as flexible printing patch panel (FPC) etc.) increase.

The flexible overlapping plate has the structure that forms the circuit of being made by tinsel on the insulativity film.The flexible overlapping plate normally will also adopt heating, crimping that the lip-deep method that tinsel is fitted in this substrate is prepared by various adhesivess by various insulating material insulativity film that form, that have flexibility as substrate.

As above-mentioned insulativity film, preferably use Kapton etc.

As above-mentioned adhesives, use heat-curable adhesives such as epoxy system, acrylic acid series (below, also will use the FPC of these heat-curable adhesives to be called three layers of FPC) usually.

Heat-curable adhesive have can be bonding under lower temperature advantage.But,, think that the reply when using three layers of FPC of heat-curable adhesive becomes difficult along with the characteristic requirement to thermotolerance, bendability, electric reliability from now on becomes strict.

To this, proposed on insulativity film (Kapton), metal level to be set directly, the FPC of use thermoplastic polyimide on adhesive linkage (below, be also referred to as two layers of FPC).These two layers of FPC have than three layers of FPC excellent characteristic, the expansion that expectation will need from now on.

Making method as the flexible metal-clad laminate that in two layers of FPC, uses, can enumerate, after curtain coating on the tinsel, coating are as the polyamic acid of polyimide precursor, carry out again imidization teeming practice, adopt sputter, be plated on metalikon that metal level directly is set on the Kapton, by the fit laminating of Kapton and tinsel of thermoplastic polyimide.

This wherein, laminating has following advantage, the thickness range of the tinsel that can connect is wideer than teeming practice, installation cost is lower than metalikon.As carrying out laminated device, extract roller shape material out Yi Bian can use, Yi Bian carry out laminated hot-roll lamination device or biobelt pressure (Double belt press) device etc. continuously.Among above-mentioned, from productivity, more preferably use cast coating.

When preparing existing three layers of FPC, owing in adhesive linkage, used thermosetting resin, therefore can carry out (with reference to patent documentation 1) under less than 200 ℃ at laminating temperature with laminating.To this, two layers of FPC will show heat fusion and be necessary to be heated to more than 200 ℃ owing to use thermoplastic polyimide as adhesive linkage, according to circumstances will be heated to the high temperature near 400 ℃.Therefore, on the flexible metal-clad laminate that lamination obtains, produce residual strain, when etching forms distribution, and dimensional change can occur during levelling (solder reflow) again for installation parts carries out scolding tin.

Particularly, if enumerate an example of laminating, have and on Kapton, be provided with when containing the adhesive linkage of thermoplastic polyimide, imidization is carried out in heating continuously after curtain coating, coating are as the polyamic acid of thermoplastic polyimide precursor, the method of the tinsel of fitting, but owing to will carry out heating and pressurizing continuously, material is to place under the heating environment being under the tensile state mostly not only in the imidization step, and when the applying metal level.Its result from the flexible overlapping plate during the etching metal paper tinsel, by scolding tin levelling again, discharges this strain when heating, occur the situation of dimensional change before and after these steps mostly.

In recent years, for the miniaturization, the lightweight that realize electronic machine, the distribution that is arranged on the substrate develops to miniaturization, and mounted component is also installed with the product of miniaturization, densification.Therefore, the dimensional change that forms behind the fine distribution becomes big, can be created in the design phase to depart from from the parts installation site problem that parts and substrate can not well be connected.

Therefore, carried out suppressing the trial (with reference to patent documentation 2 or 3) of dimensional change by the tension force of key-course pressure pressure, control adhering film.

But, though can improve dimensional change by these methods, still abundant inadequately, require further to improve dimensional change.

Patent documentation 1: the spy opens flat 9-199830 communique

Patent documentation 2: the spy opens the 2002-326308 communique

Patent documentation 3: the spy opens the 2002-326280 communique

Summary of the invention

The problem that invention will solve

The present invention makes in view of above-mentioned problem, provides a kind of adhering film that has suppressed dimensional change and superimposed tinsel and the flexible metal-clad laminate that obtains.

Solve the means of problem

1. the inventor waits in view of found that above-mentioned problem is furtherd investigate, on at least one surface of polyimide, be provided with in the adhering film of the adhesive linkage that contains thermoplastic polyimide, linear expansivity under 100～200 ℃ of each leisures of the MD direction of adhering film and TD direction satisfies under the situation of particular kind of relationship, can be suppressed at the dimensional change that the manufacturing step (be the Copper Foil of the etching FCCL step that form pattern specifically,, added thermosetting the step of FPC of pattern) of FCCL (flexible metallizing multilayer body) and FPC produces down.

And, also find alone, particularly for the quantity-produced adhering film, MD direction and TD direction linear expansivity separately at adhering film under the whole width satisfy under the situation of particular kind of relationship, for example when the imidization of thermoplastic polyimide or when metal foil laminated, can relax the generation of thermal stresses, suppress the generation of dimensional change effectively, thereby finish the present invention.

That is, adopt following novel adhering film and flexible metal-clad laminate and manufacture method thereof can solve above-mentioned problem.

1) a kind of adhering film, this adhering film are provided with the adhesive linkage that contains thermoplastic polyimide at least one surface of Kapton, wherein, the linear expansivity of this adhering film satisfies:

1.0＞(linear expansivity of MD direction)/(linear expansivity of TD direction)＞0.1

(linear expansivity is the mean value in 100～200 ℃).

2) a kind of adhering film, this adhering film are provided with the adhesive linkage that contains thermoplastic polyimide at least one surface of Kapton, wherein, this adhering film is a quantity-produced, and the linear expansivity of the whole width of this adhering film satisfies simultaneously:

1.0＞(linear expansivity of MD direction)/(linear expansivity of TD direction)＞0.1

(linear expansivity is the mean value in 100～200 ℃).

3) as 1) or 2) described adhering film, wherein, above-mentioned adhering film is the wide above long size film of 250mm that is.

4) as 1)～3) described adhering film, wherein,, superimposed with tinsel continuously by a pair of above metallic roll heating and pressurization.

5) a kind of flexible metal-clad laminate, it is by 1)～4) on any one described adhering film the applying tinsel obtain.

6) a kind of manufacture method of flexible metal-clad laminate, wherein, limit heating and add flanging continuously superimposed 1)～3) described adhering film and tinsel.

2. the inventor waits in view of found that above-mentioned problem is furtherd investigate, for the adhering film that the adhesive linkage that contains thermoplastic polyimide is set at least one surface of polyimide, when the modulus of elasticity of adhering film satisfies particular kind of relationship, can be suppressed at the dimensional change that produces in the manufacturing step of FPC.Specifically, the Copper Foil that can suppress etching FCCL forms the dimensional change that produces in the step of pattern, the step of FPC of pattern that added thermosetting.

In addition, also find alone, particularly for the quantity-produced adhering film, modulus of elasticity at adhering film under the whole width satisfies under the situation of particular kind of relationship, for example when the imidization of thermoplastic polyimide and when metal foil laminated, can relax the generation of thermal stresses, suppress the generation of dimensional change effectively, thereby finish the present invention.

That is, adopt following novel adhering film and flexible metal-clad laminate and manufacture method thereof can solve above-mentioned problem.

7) a kind of adhering film, this adhering film is provided with the adhesive linkage that contains thermoplastic polyimide at least one surface of Kapton, the modulus of elasticity of the MD direction of this adhering film is more than the 5GPa, and satisfies 1.70＞(modulus of elasticity of MD direction)/(modulus of elasticity of TD direction)＞1.05.

8) a kind of adhering film, this adhering film is provided with the adhesive linkage that contains thermoplastic polyimide at least one surface of Kapton, wherein, this adhering film is a quantity-produced, and the modulus of elasticity on the MD direction of the whole width of this adhering film satisfies 1.70＞(modulus of elasticity of MD direction)/(modulus of elasticity of TD direction)＞1.05 when 5GPa is above.

9) as 8) described adhering film, wherein, above-mentioned adhering film is the wide above long size film of 250mm that is.

10) as 7)～9) described adhering film, wherein,, superimposed with tinsel continuously by a pair of above metallic roll heating and pressurization.

11) a kind of flexible metal-clad laminate, it is by 7)～10) on any one described adhering film the applying tinsel obtain.

12) a kind of manufacture method of flexible metal-clad laminate, wherein, limit heating and add flanging continuously superimposed 7)～9) described adhering film and tinsel.

3. the inventor waits in view of found that above-mentioned problem is furtherd investigate, for the adhering film that the adhesive linkage that contains thermoplastic polyimide is set at least one surface of polyimide, when the modulus of elasticity of adhering film satisfies under the situation of particular kind of relationship, can suppress the dimensional change that produces in the manufacturing step of FPC.Particularly, the Copper Foil that can be suppressed at etching FCCL forms the dimensional change that produces in the step of pattern, the step of FPC of pattern that added thermosetting.

In addition, also find alone, particularly for the quantity-produced adhering film, modulus of elasticity at adhering film under the whole width satisfies under the situation of particular kind of relationship, for example when the imidization of thermoplastic polyimide and when metal foil laminated, can relax the generation of thermal stresses, suppress the generation of dimensional change effectively, thereby finish the present invention.

That is, adopt following novel adhering film and flexible metal-clad laminate and manufacture method thereof can solve above-mentioned problem.

13) a kind of adhering film, this adhering film is provided with the adhesive linkage that contains thermoplastic polyimide at least one surface of Kapton, modulus of elasticity on the MD direction of this adhering film is lower than 5GPa, and satisfies 2.00＞(modulus of elasticity of MD direction)/(modulus of elasticity of TD direction)＞1.10.

14) a kind of adhering film, this adhering film is provided with the adhesive linkage that contains thermoplastic polyimide at least one surface of Kapton, this adhering film is a quantity-produced, and when the modulus of elasticity on the MD direction of the whole width of this adhering film is lower than 5GPa, satisfy 2.00＞(modulus of elasticity of MD direction)/(modulus of elasticity of TD direction)＞1.10.

15) as 14) described adhering film, wherein, above-mentioned adhering film is the wide above long size film of 250mm that is.

16) as 13)～15) described adhering film, wherein,, superimposed with tinsel continuously by a pair of above metallic roll heating and pressurization.

17) a kind of flexible metal-clad laminate, it is by 13)～16) on any one described adhering film the applying tinsel obtain.

18) a kind of manufacture method of flexible metal-clad laminate, wherein, limit heating and add flanging superimposed continuously 13)～15) described adhering film and tinsel.

The effect of invention

Adhering film of the present invention and flexible metallizing multilayer body can suppress the generation of dimensional change, particularly can effectively suppress the generation of dimensional change in the laminating.

Particularly, (1) can reduce the size changing rate of MD direction and TD direction respectively to removing the size changing rate of tinsel front and back, reduces the difference of the dimensional change of MD direction and TD direction simultaneously, for example can be the scope below 0.30%.

And, (2) for the accumulated value that under 250 ℃, carries out the size changing rate before and after 30 minutes the heating after removing the size changing rate before and after the tinsel and removing tinsel, can reduce MD direction and TD direction accumulated value separately respectively, reduce the difference of the accumulated value of MD direction and TD direction simultaneously, the difference that for example can make MD direction and TD direction is the scope below 0.60%.

Thereby the present invention is adapted at forming middle uses the such as FPC of fine distribution, can improve problems such as position deviation.Particularly during the adhering film more than continuous production width 250mm, not only above-mentioned size changing rate is little, and can play the effect of the whole width dimensions velocity of variation of stabilizing films.

Description of drawings

[Fig. 1] Fig. 1 is the sectional view of film relaxed state.

[Fig. 2] Fig. 2 is the figure of Tenter oven and expansion shrinking percentage.

[Fig. 3] Fig. 3 illustrates the figure of the sampling method that is used for the size up variation.

[Fig. 4] Fig. 4 illustrates the figure of the sampling method that is used for the size up variation.

[Fig. 5] Fig. 5 illustrates the figure of the sampling method that is used for the size up variation.

Embodiment

The following describes embodiments of the present invention.

The feature of adhering film of the present invention is that the adhesive linkage that contains thermoplastic polyimide is set at least one surface of Kapton.

(1) among the present invention, by the linear expansivity of regulation adhering film at MD direction and TD direction both direction, in the flexible metal-clad laminate that can obtain in superimposed tinsel, reduce to remove the difference of the size changing rate of MD direction before and after the tinsel and TD direction, and the accumulated value of the size changing rate before and after heating after can reducing to remove the size changing rate before and after the tinsel and removing tinsel.

That is, the linear expansivity of adhering film of the present invention satisfies:

1.0＞(linear expansivity of MD direction)/(linear expansivity of TD direction)＞0.1

(linear expansivity is the mean value in 100～200 ℃).

The linear expansivity of MD direction is than the linear expansivity of TD direction hour, superimposed with tinsel and in the flexible metal-clad laminate that obtains, can reduce to remove the MD direction of tinsel front and back and the difference of TD direction size changing rate, in addition, can reduce to remove the size changing rate before and after the tinsel and remove tinsel after the accumulated value of size changing rate before and after heating.

The value of the usefulness of adhering film of the present invention (linear expansivity of MD direction)/(linear expansivity of TD direction) regulation must be than 1.0 little, and is bigger than 0.1.

By reducing (linear expansivity of MD direction)/(linear expansivity of TD direction), can reduce the dimensional change that produces in the manufacturing step of FPC to than 1.0 little.

The words that (linear expansivity of MD direction)/(linear expansivity of TD direction) is littler than 1.0, think and to improve dimensional change, but the value of being somebody's turn to do is too little, because the equilibrated situation of the dimensional change that can not guarantee MD direction and TD direction is arranged, so lower limit is preferably 0.1.Particularly, the dimensional change of TD direction has the situation of variation.

In addition, linear expansivity is to cut out rectangular working sample along film length direction and perpendicular direction (width), measures in all directions respectively.Mensuration is thermomechanical analytical equipment, the trade(brand)name that adopts Seiko Instruments company to make: TMA (thermomechanical analyzer) 120C, under nitrogen gas stream, with 10 ℃/minute of heat-up rates, in 10 ℃ to 400 ℃ temperature range, measuring postcooling to room temperature, under nitrogen gas stream, with 10 ℃/minute of heat-up rates, after in 10 ℃ to 400 ℃ temperature range, measuring, obtain 100～200 ℃ the interior mean value of scope.

The method that acquisition has the adhering film of such linear expansivity is not particularly limited, for example, can enumerate: the film of linear expansivity that (a) uses the linear expansivity controlled the MD direction, TD direction is as the Kapton at center, by selecting the thickness of Kapton and adhesive linkage respectively, control the method for the linear expansivity of adhering film simultaneously; (b) under Kapton comprises the state of volatile component, adhesive linkage is set, by extending in TD direction and/or MD direction under the state that contains volatile component at Kapton, controls the method for the linear expansivity of adhering film simultaneously; (c) method that forms by coextrusion polyimide film layer and adhesive linkage etc.

Particularly, in the quantity-produced adhering film, linear expansivity in adhering film MD direction under the whole width and TD direction satisfies under the situation of above-mentioned relation formula, for example, can suppress the generation of the dimensional change of and the tinsel superimposed FPC that obtain continuous by cast coating effectively.

This wherein uses the Kapton of the linear expansivity of having controlled MD direction and TD direction, suitably selects the method for the thickness of Kapton and adhesive linkage can easily obtain the adhering film of target simultaneously, thereby is preferred.

(2) in the present invention, by the modulus of elasticity of regulation adhering film in MD direction and TD direction, in the flexible metal-clad laminate that obtains in superimposed tinsel, can reduce to remove the difference of the size changing rate of MD direction before and after the tinsel and TD direction, and the accumulated value of the size changing rate before and after heating after can reducing to remove the size changing rate before and after the tinsel and removing tinsel.

That is, adhering film of the present invention is more than the 5GPa at the modulus of elasticity of MD direction, and satisfies 1.70＞(modulus of elasticity of MD direction)/(modulus of elasticity of TD direction)＞1.05.

When the modulus of elasticity of MD direction is bigger than the modulus of elasticity of TD direction, superimposed with tinsel and in the flexible metal-clad laminate that obtains, can reduce to remove the difference of the size changing rate of MD direction before and after the tinsel and TD direction, and, the accumulated value of the size changing rate before and after heating after can reducing to remove the size changing rate of tinsel front and back and removing tinsel.

The value of the usefulness of adhering film of the present invention (modulus of elasticity of MD direction)/(modulus of elasticity of TD direction) regulation must be than 1.70 little, and is bigger than 1.05.

The words that (modulus of elasticity of MD direction)/(modulus of elasticity of TD direction) is bigger than 1.05, think and to improve dimensional change, but the value of being somebody's turn to do is too big, because the equilibrated situation of the dimensional change that can not guarantee MD direction and TD direction is arranged, so the upper limit is preferably 1.70.Particularly, the dimensional change of TD direction has the situation of variation.

In addition, modulus of elasticity is to cut out rectangular working sample along film length direction and perpendicular direction (width), measures according to ASTM D882 in all directions respectively.

The method that acquisition has the adhering film of such modulus of elasticity is not particularly limited, for example, can enumerate: the film of modulus of elasticity that (a) uses the modulus of elasticity controlled the MD direction, TD direction is as the Kapton at center, by selecting the thickness of Kapton and adhesive linkage respectively, control the method for the modulus of elasticity of adhering film simultaneously; (b) under Kapton comprises the state of volatile component, adhesive linkage is set, simultaneously by on TD direction and/or MD direction, extending the method for the modulus of elasticity of control adhering film under the state that contains volatile component at Kapton; (c) method that forms by coextrusion polyimide film layer and adhesive linkage etc.

Particularly, in the quantity-produced adhering film, modulus of elasticity at adhering film under the whole width satisfies under the situation of above-mentioned relation formula, for example, can suppress the generation of the dimensional change of and the tinsel superimposed FPC that obtain continuous by cast coating effectively.

This wherein uses the Kapton of the modulus of elasticity of control MD direction and TD direction, suitably selects the method for the thickness of Kapton and adhesive linkage can easily obtain the adhering film of target simultaneously, thereby is preferred.

And, when adhering film of the present invention is lower than 5GPa at the modulus of elasticity of MD direction, satisfy 2.00＞(modulus of elasticity of MD direction)/(modulus of elasticity of TD direction)＞1.10.

When the modulus of elasticity of MD direction is bigger than the modulus of elasticity of TD direction, superimposed with tinsel and in the flexible metal-clad laminate that obtains, can reduce to remove the difference of the size changing rate of MD direction before and after the tinsel and TD direction, and, the accumulated value of the size changing rate before and after heating after can reducing to remove the size changing rate of tinsel front and back and removing tinsel.

The value of the usefulness of adhering film of the present invention (modulus of elasticity of MD direction)/(modulus of elasticity of TD direction) regulation must be than 2.00 little, and is bigger than 1.10.

When (modulus of elasticity of MD direction)/(modulus of elasticity of TD direction) is bigger than 1.10, think and can improve dimensional change, but the value of being somebody's turn to do is too big, because the equilibrated situation of the dimensional change that can not guarantee MD direction and TD direction is arranged, so the upper limit is preferably 2.00.Specifically, the dimensional change of TD direction has the situation of variation.

In addition, modulus of elasticity is to cut out rectangular working sample along film length direction and perpendicular direction (width), measures according to ASTM D882 in all directions respectively.

The method that acquisition has the adhering film of such modulus of elasticity is not particularly limited, for example, can enumerate: the film of modulus of elasticity that (a) uses the modulus of elasticity controlled the MD direction, TD direction is as the Kapton at center, simultaneously by selecting the thickness of Kapton and adhesive linkage respectively, the method for the modulus of elasticity of control adhering film; (b) under Kapton comprises the state of volatile component, adhesive linkage is set, simultaneously by on TD direction and/or MD direction, extending the method for the modulus of elasticity of control adhering film under the state that contains volatile component at Kapton; (c) method that forms by coextrusion polyimide film layer and adhesive linkage etc.Particularly, in the quantity-produced adhering film, the modulus of elasticity of adhering film satisfies under the situation of above-mentioned relation formula in whole width, for example, can suppress the generation of the dimensional change of and FPC that metal foil laminates obtain continuous by cast coating effectively.

This wherein uses the Kapton of having controlled MD direction and TD direction modulus of elasticity, suitably selects the method for the thickness of Kapton and adhesive linkage can easily obtain the adhering film of target simultaneously, thereby is preferred.

The manufacturing of the manufacturing of the Kapton of the adhering film of the present invention of explanation formation successively, the adhesive linkage that contains thermoplastic polyimide, adhered thin film, flexible metal-clad laminate, flexible metal-clad laminate below.

(I) Kapton of formation adhering film of the present invention

The Kapton that constitutes adhering film of the present invention can adopt following preparation method, it comprise for example polymerization as the step of the polyamic acid of the precursor of polyimide, on supporter continuously curtain coating, coating comprise the polyamic acid that obtains and organic solvent composition, form the step of gel film, gel film peeled from the supporter and the step at immobilized gel film two ends, the step that transport in process furnace on limit, fixed film two ends, limit, give an example below.

(first method)

First method is the preparation method who comprises the Kapton of following step:

(A) step of polymeric polyamide acid

(B) after curtain coating, coating comprise the composition of polyamic acid and organic solvent on the supporter, form the step of gel film

(C) peel off this gel film, and with two ends fixed step

(D) limit, two ends of the limit fixed film step of in process furnace, transporting

(E) film two ends fixed state heats, the tensile step to remove in step (D) back.

(A) step

(A) step is the step of polymerization as the polyamic acid of polyimide precursor.

Manufacture method as polyamic acid, can use known method, usually can make by the following method: in organic solvent, dissolve at least a aromatic tetracarboxylic acid's dianhydride and at least a aromatic diamine with equimolar in fact amount, under the condition of controlled temperature, stir the organic solvent solution that obtains, up to the polymerization of finishing above-mentioned aromatic tetracarboxylic acid's dianhydride and aromatic diamine.These organic solvent solutions are usually with 5～35wt%, and the concentration of preferred 10～30wt% obtains.Occasion for the concentration of this scope can obtain suitable molecular weight and soltion viscosity.

All known method can be used as polymerization process, but, following method can be enumerated as particularly preferred polymerization process.

That is, 1) aromatic diamine is dissolved in the organic polar solvent, itself and equimolar in fact aromatic tetracarboxylic acid's two anhydride reactants are come the polymeric method.

2) in organic polar solvent, make aromatic tetracarboxylic acid's dianhydride and the aromatic diamine reaction of comparing less molar weight with it, obtain the prepolymer that two ends have anhydride group.Then use aromatic diamine to carry out polymerization and make aromatic tetracarboxylic acid's dianhydride and aromatic diamine equimolar in fact method in whole steps.

3) in organic polar solvent, make aromatic tetracarboxylic acid's dianhydride and excessive aromatic diamine reaction, obtain two ends and have amino prepolymer.Then after wherein appending the interpolation aromatic diamine, use aromatic tetracarboxylic acid's dianhydride to carry out polymerization and make aromatic tetracarboxylic acid's dianhydride and aromatic diamine equimolar in fact method in whole steps.

4) in organic polar solvent, make aromatic tetracarboxylic acid's dianhydride dissolving and/or disperse after, use actual equimolar aromatic diamine to come the polymeric method.

5) in organic polar solvent, make the mixture reaction of equimolar in fact aromatic tetracarboxylic acid's dianhydride and aromatic diamine come the polymeric method.

These methods can be used separately, also can partly be used in combination.

Here, the material that uses in the polyamic acid organic solvent composition that the present invention relates to is described.

Operable in the present invention suitable aromatic tetracarboxylic acid's dianhydride comprises: pyromellitic acid dianhydride, 2,3,6,7-naphthalene tetracarboxylic acid dianhydride, 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, 1,2,5,6-naphthalene tetracarboxylic acid dianhydride, 2,2 ', 3,3 '-biphenyl tetracarboxylic dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 4,4 '-oxo O-phthalic acid dianhydride (4,4 '-oxyphthalic dianhydride), 2, two (3,4-dicarboxyl phenyl) the propane dianhydrides of 2-, 3,4,9, the 10-perylenetetracarboxylic dianhydride, two (3,4-dicarboxyl phenyl) propane dianhydride, 1,1-two (2,3-dicarboxyl phenyl) ethane dianhydride, 1, two (3,4-dicarboxyl phenyl) the ethane dianhydrides of 1-, two (2,3-dicarboxyl phenyl) methane dianhydride, two (3,4-dicarboxyl phenyl) ethane dianhydride, the oxydiphthalic acid dianhydride, two (3,4-dicarboxyl phenyl) sulfone dianhydride, TOPOT 2,2 (trimellitic acid monoesters acid anhydrides), ethylenebis (trimellitic acid monoesters acid anhydrides), dihydroxyphenyl propane two (trimellitic acid monoesters acid anhydrides) and analogues thereof can preferably use or use the mixture of arbitrary proportion separately.

As the suitable aromatic diamine that can in the polyamic acid that the present invention relates to, use, can enumerate, 4,4 '-diamino-diphenyl propane, 4,4 '-diaminodiphenylmethane, p-diaminodiphenyl, 3,3 '-dichlorobenzidine, 3,3 '-tolidine, 2,2 '-tolidine, 3,3 '-dimethoxy benzidine, 2,2 '-dimethoxy benzidine, 4,4 '-diaminodiphenyl sulfide, 3,3 '-diaminodiphenylsulfone(DDS), 4,4 '-diaminodiphenylsulfone(DDS), 4,4 '-oxo pentanoic, 3,3 '-oxo pentanoic, 3,4 '-oxo pentanoic, 1, the 5-diaminonaphthalene, 4,4 '-diamino-diphenyl diethylsilane, 4,4 '-diamino-diphenyl silane, 4,4 '-diamino-diphenyl ethyl phosphine oxide, 4,4 '-diamino-diphenyl N-methylamine, 2, two (the 4-amino-benzene oxygen phenyl) propane of 2-, 4,4 '-diamino-diphenyl N-phenyl amine, 1,4-diaminobenzene (Ursol D), 1, the 3-diaminobenzene, 1, the 2-diaminobenzene, two { 4-(4-amino-benzene oxygen) phenyl } sulfone, two { 4-(3-amino-benzene oxygen) phenyl } sulfone, 4,4 '-two (4-amino-benzene oxygen) biphenyl, 4,4 '-two (3-amino-benzene oxygen) biphenyl, 1, two (3-amino-benzene oxygen) benzene of 3-, 1, two (4-amino-benzene oxygen) benzene of 3-, 1, two (4-amino-benzene oxygen) benzene of 3-, 1, two (3-amino-benzene oxygen) benzene of 3-, 3,3 '-diaminobenzophenone, 4,4 '-diaminobenzophenone, Ursol D and their analogue etc.

As the aromatic diamine composition, also can use aromatic diamine with rigid structure and aromatic diamine simultaneously with flexible structure.During the value of the linear expansivity that the film that obtains in control has, the usage rate of the aromatic diamine of rigid structure becomes big words, can reduce linear expansivity, the usage ratio with aromatic diamine of flexible structure becomes big, can reduce linear expansivity.

In the present invention, said aromatic diamine with rigid structure is meant the compound that usefulness [Chemical formula 1] is represented.

[Chemical formula 1]

H ₂N-R ₂-NH ₂ (1)

(R2 in the formula is

[Chemical formula 2]

The group that is selected from the divalent aromatic group of expression, the R3 in the formula can be identical or different, is to be selected from H-, CH ₃-,-OH ,-CF ₃,-SO ₄,-COOH ,-CO-NH ₂, Cl-, Br-, F-and CH ₃Any one group among the O-).

In addition, said diamines with flexible structure is the diamines with flexible structures such as ether, sulfuryl, ketone group, sulfide groups, preferably uses the compound of following general formula (2) expression.

[chemical formula 3]

(R4 in the formula is selected from:

[chemical formula 4]

The group of the divalent organic group of expression, the R5 in the formula can be identical or different, is to be selected from H-, CH ₃-,-OH ,-CF ₃,-SO ₄, COOH ,-CO-NH ₂, Cl-, Br-, F-and CH ₃Any one group among the O-).

The Kapton that uses among the present invention can recently obtain by kind, the mixing that suitably determines to use aromatic tetracarboxylic acid's dianhydride and aromatic diamine, so that it becomes the film that has desired characteristic in above-mentioned scope.

As sour composition, the necessary film characteristics of FPC, resistance to chemical reagents, water-intake rate, wet swelling coefficient aspect beyond can the control line coefficient of expansion, in aromatic tetracarboxylic acid's dianhydride, preferred especially the use is selected from pyromellitic acid dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 4,4 '-oxo O-phthalic acid dianhydride, 3,3 ', 4, at least a in 4 '-biphenyl tetracarboxylic dianhydride, the TOPOT 2,2 (trimellitic acid monoesters acid anhydrides).

In addition, in these aromatic tetracarboxylic acid's dianhydrides, use and be selected from 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 4,4 '-oxo O-phthalic acid dianhydride, 3,3 ', 4, preferred usage quantity during at least a in 4 '-biphenyl tetracarboxylic dianhydride, the TOPOT 2,2 (trimellitic acid monoesters acid anhydrides) is below the 60mol% with respect to all acid dianhydride, is preferably below the 55mol%, more preferably below the 50mol%.Use 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 4,4 '-oxo O-phthalic acid dianhydride, 3,3 ', 4, during at least a in 4 '-biphenyl tetracarboxylic dianhydride, the TOPOT 2,2 (trimellitic acid monoesters acid anhydrides), its usage quantity exceeds the words of this scope, because the second-order transition temperature of Kapton is low excessively sometimes, the storage modulus when perhaps hot is crossed low and is made the system film become difficult, thereby is not preferred.

In addition, when using pyromellitic acid dianhydride, preferred usage quantity is 40～100mol%, and more preferably 45～100mol% is preferably 50～100mol% especially.By in this scope, using pyromellitic acid dianhydride, using or the storage modulus of second-order transition temperature and Re Shi is being remained on suitable scope during the system film easily.

In addition, preferred 4 from can controlling the necessary film characteristics of FPC, resistance to chemical reagents, water-intake rate, the wet swelling coefficient aspect except linear expansivity as the aromatic diamine composition, 4 '-oxo pentanoic, Ursol D.

Particularly, as preferred aromatic diamine composition, the viewpoint of calm linear expansivity easy to control and modulus of elasticity is seen, preferably as 4 of the aromatic diamine with flexible structure, the Ursol D that 4 '-diaminodiphenyl oxide, conduct have the aromatic diamine composition of rigid structure more preferably uses simultaneously.

In addition, consider that from environment resistant (down hot and humid expose) viewpoint of film the usage ratio of the diamines of rigid structure is preferably 80 moles below the % with respect to whole diamines, more preferably 75 moles below the %.

In the polyimide of above-mentioned acquisition, consider, be more preferably at the Kapton of the repeating unit that comprises following general formula (3)～(6) expression in the molecule from the viewpoint of the characteristic (modulus of elasticity, linear expansivity, wet swelling coefficient) of film.

[chemical formula 5]

General formula (3)～(6)

In addition, the number of repeating units of the general formula in the above-mentioned molecule (3)～(6) expressions is respectively a, b, c, d, and during a+b+c+d=s, any one of preferred (a+b)/s, (a+c)/s, (b+d)/s, (c+d)/s all satisfies 0.20～0.80.

And,, preferably use pyromellitic acid dianhydride, 4 at least simultaneously, 4 '-diaminodiphenyl oxide, Ursol D in order to show the modulus of elasticity of appropriateness.Viewpoint consideration from environment resistant (hot and humid expose down after deterioration), processing film and the film characteristics (modulus of elasticity control) of film, preferred 4, the usage quantity of 4 '-diaminodiphenyl oxide is 35 moles more than the % with respect to whole aromatic diamine compositions, and the usage quantity of Ursol D is 65 moles below the % with respect to whole aromatic diamine compositions.

The preferred solvent that is used for synthesizing polyamides acid, so long as the solvent of dissolving polyamic acid, then can use solvent arbitrarily, as the acid amides series solvent is N, dinethylformamide (below abbreviate DMF as), N,N-dimethylacetamide (below abbreviate DMAc as), N-N-methyl-2-2-pyrrolidone N-(below abbreviate NMP as) etc. especially preferably use N, dinethylformamide, N,N-dimethylacetamide.

(B) step

(B) be after curtain coating, coating contain the composition (being also referred to as polyamic acid solution) of polyamic acid and organic solvent on the supporter, form the step of gel film.

(B) composition that uses in the step also can use added can with the composition of other compositions such as reagent of polyamic acid reaction.

For the method that these polyamic acid solutions is converted into polyimide, can use present known method.Hot-imide method and chemical imidization method can have been enumerated in these methods.The hot-imide method is that above-mentioned dewatering agent and imidization catalyst are not had an effect, and only promotes the method for imidization by heating.

The kind that heating condition can be by polyamic acid, the thickness of film wait and change.

Chemistry imidization method is the method that makes dewatering agent and imidization catalyst effect in the polyamic acid organic solvent solution.

As dewatering agent, can enumerate, for example aromatic anhydrides such as aliphatic anhydride, benzoyl oxide such as acetic anhydride etc.

As imidization catalyst, can enumerate, for example hetero ring type tertiary amines such as aromatic tertiary amines such as aliphatic tertiary amine class, xylidine, pyridine, picoline, isoquinoline 99.9 such as triethylamine etc.

In the middle of these, especially preferably use acetic anhydride, especially preferably use isoquinoline 99.9 as imidization catalyst as dewatering agent.Amido acid with respect to 1 mole of polyamic acid organic solvent solution, acetic anhydride adds 1.0～4.0 with molar ratio computing, preferred interpolation 1.2～3.5, more preferably add 1.5～2.5, with respect to the amido acid of 1 mole of polyamic acid organic solvent solution, isoquinoline 99.9 adds 0.1～2.0 with molar ratio computing, preferred interpolation 0.2～1.5, more preferably add 0.3～1.2, when especially preferably adding 0.3～1.1 ratio, can obtain good Kapton.

In addition, in order to improve every characteristic of sliding, thermal conductivity, electroconductibility, corona resistance (corona resistance), loop rigidity films such as (loop stiffness), can also add filler.As filler, can use any goods,, can enumerate silicon-dioxide, titanium oxide, aluminum oxide, silicon nitride, boron nitride, secondary calcium phosphate, calcium phosphate, mica etc. as preferred example.

The particle diameter of filler is determined according to the kind of the filler of wanting the film characteristics of modification and interpolation because be, therefore be not particularly limited, but median size is 0.05～100 μ m usually, is preferably 0.1～75 μ m, more preferably 0.1～50 μ m is preferably 0.1～25 μ m especially.When particle diameter is lower than above-mentioned scope, be difficult to show modified effect, when surpassing this scope, damage superficiality sometimes greatly, perhaps mechanical characteristics reduces greatly.And therefore the interpolation umber of filler is not particularly limited because also be to wait to determine according to the film characteristics of wanting modification and packing material size.Usually the addition of filler is 0.01～100 weight part with respect to the polyimide of 100 weight parts, is preferably 0.01～90 weight part, more preferably 0.02～80 weight part.When the addition of filler is lower than this scope, be difficult to show the modified effect that brings by filler, when surpassing this scope, the impaired greatly possibility of mechanical characteristics of film arranged.Any one method during the interpolation of filler can make with the following method: 1. before polymerization or add the method for polymerization liquid midway, after 2. polymerization finishes, use the method for 3 mixing fillers such as roller, 3. prepare to contain the dispersion liquid of filler, and it is mixed into method in the polyamic acid organic solvent solution.In addition, for filler being disperseed well or making the dispersion state stabilization, can in the scope that does not influence the film rerum natura, use dispersion agent, tackifier etc.

With the composition that obtains like this continuously curtain coating, be applied on the supporter.As supporter, so long as be insoluble to this solution resin, and can tolerate for the needed heated support body of the organic solvent solution of removing this synthetic resin solution, then can use supporter arbitrarily.From the dry aspect of the coating fluid that can make the solution shape, the endless belt or the metal roller of preferred especially bonding metal plates preparation.

And the material of endless belt or cylinder is preferably used metal, wherein, preferably uses the SUS material.Owing to can improve lip-deep solvent bonding or peel off exsiccant organic insulation film easily by the goods that use the surface to go up metals such as chromium plating, titanium, nickel, cobalt, the therefore preferred electroplating processes of implementing.Preferably have level and smooth surface on endless belt, the metal roller, but also can on endless belt or metal roller, make numerous concavo-convex.Preferably the concavo-convex diameter of processing on endless belt or metal roller is 0.1 μ m～100 μ m, and the degree of depth is 0.1～100 μ m.By concavo-convexly can on the surface of organic insulation film, making fine projection making on the metallic surface, can improve the damage that film rubs each other and causes by this projection, perhaps can improve film sliding each other.

So-called gel film in the present application is with heating, dry polyamic acid solution, and the macromolecule resin film of remaining a part of organic solvent or resultant of reaction (they are called remaining composition) is called gel film in macromolecule membrane.In the manufacturing step of Kapton, organic solvent, imidization catalyst, dewatering agent, the resultant of reaction (the suction composition of dewatering agent, water) of dissolving polyamic acid solution are residual as the remaining composition in the gel film.Remaining residual component ratio is with respect to weight (the being solids component weight) a (g) of the dried film that exists in this gel film in the gel film, when calculating remaining remaining composition weight b (g), remaining component proportions c is the value of being calculated by following calculating formula, this remaining component proportions is preferably below 500%, more preferably more than 10% below 300%, be preferably especially more than 20% below 100%.

C=b/a * 100 ... (formula 1)

500% when above, the uneven of remaining component proportions becomes big relatively in the surface, has the situation that is difficult to the film characteristics that evenly control obtains.In the film surface inequality of remaining component proportions be will regulation remaining component proportions during as X, be easy to get calmly and controlled the film of molecular orientation on the MD direction, be preferably the scope of following (formula 2) expression.

0.8X≤X≤1.2X ... (formula 2)

In the scope that X is controlled at (formula 2), can enumerate the methods such as drying on supporter, for example, with the nozzle mode when dry, as far as possible vertically to the film blowing hot-air, than the film on the supporter more broadly blowing hot-air or on the thin-film width direction as far as possible controlled temperature be method such as certain.

The method of calculation of the weight a of dried gel film and remaining composition weight b are, after measuring the gel film weight d of 100mm * 100mm, drying is after 20 minutes in 450 ℃ baking oven with this gel film, and behind the cool to room temperature, gravimetry is as complete drying synthetic resins weight a.Remaining composition weight b calculates by the formula of b=d-a by gel film weight d and complete drying synthetic resins weight a.

In the step of making gel film, temperature, wind speed, exhaust velocity when heating on supporter, drying preferably make remaining component proportions decide in above-mentioned scope.Particularly, in the manufacturing processed of Kapton, preferably contain the organic solvent solution of polymer and organic solvent, particularly preferably in 50～180 ℃ of following heating, drying 50～200 ℃ temperature range internal heating, drying.And be the scope inner drying at 20 seconds～30 minutes time of drying, preferably dry under the control of multi-stage type temperature.

(C) step

(C) step is to peel off gel film from supporter, continuously the step at the two ends of immobilized gel film.The step of the end of the so-called immobilized gel film in the present application is meant the step of using the common grasping device that uses such as needle plate, anchor clamps to control the end of gel film in the manufacturing installation of film.

(D) step

(D) step is the two ends of limit fixed film, the step that transport in process furnace on the limit.From the viewpoint of the film of the linear expansivity that obtains to have controlled MD/TD direction in the whole width range or modulus of elasticity, (D) the preferably the highest atmosphere temperature degree of the Heating temperature in the step is below 450 ℃.More preferably below 400 ℃.

So-called atmosphere temperature degree is meant in the far infrared heater tenter machine near the temperature the film of advancing in stove.In the tenter machine of hot air circulation type, be meant the round-robin hot blast temperature.

(D) heating steps of step is from going up the viewpoint of even heating film at width (TD direction), and preferred hot blast is handled or far infrared rays is handled.In addition, from width (TD direction), heating the viewpoint of film equably, the combination that preferred hot blast is handled and far infrared rays is handled.When (D) heat treated of step was the hot blast processing, preferred hot blast below 450 ℃ was handled, and more preferably the hot blast below 400 ℃ is handled, and when far infrared rays was handled, preferred far infrared rays below 430 ℃ was handled, and more preferably the far infrared rays below 400 ℃ is handled.

In addition,, can use hotblast stove or FAR INFRARED HEATING stove separately, perhaps be used in combination a plurality of stoves, also can use the stove of calcination process film under hot blast and far infrared rays simultaneously in addition as method with hot blast and far infrared rays calcination process film.

(E) step

(E) step is the stripping films such as the needle plate from fixing two ends, anchor clamps etc. after (D) step, and is removing the step that heats under the fixed state of film two ends.

(E) tension force in the step preferably is 0.10kg/mm on film ²～1.50kg/mm ²Be 0.10kg/mm ²During following tension force, the linear expansivity or the linear expansivity of modulus of elasticity and TD direction or the situation of modulus of elasticity that are difficult to control the MD direction are arranged, be 1.5kg/mm ²When above, have the situation of film flatness forfeiture.Be preferably 0.20kg/mm ²～1.0kg/mm ², 0.20kg/mm more preferably ²～0.80kg/mm ²

From can obtain to have controlled this point of film of molecular orientation whole width, (E) the preferably the highest atmosphere temperature degree of the Heating temperature of step is more than 430 ℃.More preferably more than 450 ℃, more preferably more than 500 ℃.

From going up this point of even heating film at width (TD direction), (E) heat treated of step preferably adopts hot blast to handle or the far infrared rays processing.And, from going up this point of even heating film at width (TD direction), the combination that preferred hot blast is handled and far infrared rays is handled.

When (E) heat treated of step was the hot blast processing, preferred hot blast more than 430 ℃ was handled, and further preferably heat-treated under 450 ℃～570 ℃, carried out the hot blast processing under 470 ℃～560 ℃.When far infrared rays was handled, preferred far infrared rays more than 400 ℃ was handled, and more preferably 430 ℃～570 ℃, preferred especially 450 ℃～560 ℃.

In addition, in (E) step, this puts from going up the even heating film at width (TD direction), preferably carries out hot blast processing and far infrared rays simultaneously and handles, and more preferably at 430 ℃～570 ℃ down handle preferably more than 400 ℃ this moment.

(E) the FAR INFRARED HEATING stove during the hotblast stove during the hot blast of step is handled, far infrared rays are handled can use the device of enumerating in (B) step.

In addition, after removing film end fixing, can be after temporary transient film with low-temperature bake batches, be provided in (E) step (for example in process furnace such as hotblast stove that can have the film transporter and FAR INFRARED HEATING stove with spool (roll to roll) control tensile, the low-temperature bake film that batches is passed through, carry out (E) step etc.), also can be after (D) step, under the state of not using latching anchor portion such as (pin), then, carry out (E) step by medium methods of process furnace such as hotblast stove or FAR INFRARED HEATING stoves.

And from the viewpoint of the size changing rate of caking agent coating processibility and FPC procedure of processing, the thickness in all surfaces of the organic insulation film that uses in FCCL and FPC is preferably in following scope.

(about the thickness regulation)

In the time of will expecting thickness (central value) as the T micron, preferably satisfy following (A)～(C) condition simultaneously:

(A) go up to more than T-T * 0.10 micron on the full surface of film, and below T+T * 0.10 micron

(B) for film flow direction (MD) direction, below maximum value-minimum value=T * 0.15 micron

(C) for the film vertical direction (TD direction) that flows, below maximum value-minimum value=T * 0.15 micron.

(second method)

Second method is a kind of manufacture method of producing the organic insulation film continuously, and this method comprises at least:

(A) step of polymeric polyamide acid,

(B) after curtain coating, coating comprise the composition of polyamic acid and organic solvent on the supporter, the step of formation gel film,

(C) peel off this gel film and with two ends fixed step,

(D) two ends of limit fixed film, the step that transport in process furnace on the limit, wherein,

Above-mentioned (D) step comprises: (D-1) at least a portion step is not have the step that the such fixed mode of tension force is transported in fact with thin-film width direction (TD direction).

(A) step

(A) step can adopt and above-mentioned (first method) the middle the same method of (A) step that describes in detail.

(B) step

(B) step can adopt and above-mentioned (first method) the middle the same method of (B) step that describes in detail.The residual component ratio of the gel film in this step is preferably below 500%, and more preferably 25～250%, be preferably 30～200% especially.

(C) step

(C) step can adopt and above-mentioned (first method) the middle the same method of (C) step that describes in detail.In addition, not having the method that tension force fixes as at least a portion in (D) described later step in fact with the TD direction, can be when the immobilized gel film end of this (C) step, does not have tension force in fact with the TD direction and fixes.In the fixed film stage, do not have tension force ground in fact with the TD direction and carry out, and former state deliver to method in (D) step.Particularly, during anchor portion, film is relaxed fix.

(D) step

(D) step that transport in process furnace on the limit, two ends of limit fixed film during step.Among the present invention, from can obtain the MD direction controlled orientation the organic insulation film this put, preferably should comprise the step that (D-1) do not fix and transport along thin-film width direction (TD direction) with having tension force in fact at least a portion of (D) step.

Here, so-called TD direction does not have tension force in fact be meant except the tension force that film deadweight brings the tensile stress that is not caused by power operation on the TD direction.In fact, being meant that thin-film width between the inboardend of both ends (Fig. 1 8) is wideer than the distance of film both ends inboardend (Fig. 1 7), is the film that does not have in fact under the tension force at film under such state.

Use Fig. 1 to illustrate that film is fixed with grasping device, 7 of Fig. 1 length is the distance of both ends stationary installation end at this moment.Usually the film two ends are in the tension recovery state with latching, this both ends inboardend apart from 7 with the both ends inboardend between the width 8 of film identical.Among the present invention, as shown in Figure 1, both ends inboardend distance 7 and 8 differences of the thin-film width between them, the distance of both ends inboardend diminishes.Particularly, film is the fixed that relaxing on TD direction (width).This puts molecular orientation on the particularly calm MD direction easy to control, with the distance 7 of both ends inboardend as X, the thin-film width 8 between the inboardend of both ends is during as Y, the relation that preferred X and Y satisfy following formula fixes.

20.0 〉=(Y-X)/Y * 100＞0.00 ... (formula 3-1)

When (Y-X)/Y * 100 (for convenience, being referred to as the TD shrinking percentage sometimes) surpassing above-mentioned scope, be difficult to stably control the lax of film, slack changes sometimes with respect to carrying out method.And according to circumstances take place sometimes to come off from the end grasping device, thereby can not stably make the situation of film because film is lax.More preferably 15.0 〉=(Y-X)/Y * 100＞0.00.Preferred especially 10.0 〉=(Y-X)/Y * 100＞0.00.

Among the present invention, the MD direction is made film towards axis of orientation this is put from the whole width of film, and preferably the inlet of the process furnace in (D) step is not fixed with the TD direction with having tension force in fact.

Method 1 is not in order to fix with the TD direction at the inlet of process furnace with having tension force in fact and to transport, and when the two ends of the immobilized gel film of above-mentioned (C) step, the TD direction is not fixed with having tension force in fact, and directly delivers to the method for (D) step.

After method 2 (C) step, temporarily shorten the operation (method of Fig. 2 record) of the distance of both ends inboardend, deliver to the method for (D) step again.

Method 1 preferably satisfies the method that (formula 3-1) fixes when immobilized gel film two ends.

The method 2 preferred distances of inboardend that shorten are to satisfy following formula (formula 3-2).

0.00＞(B-X)/X×100＞-20.0

X: the both ends inboardend width among Fig. 2 (place of the fixing beginning of gel film)

B: the both ends inboardend width among Fig. 2 (in process furnace inlet or the process furnace)

Method 3 also can be in the operation of shortening both ends inboardend distance after the process furnace again that enters into of (D) step.

These methods also can make up carries out.The operation of shortening the distance of both ends inboardend in method 3 is preferably being carried out below 300 ℃, is more preferably carrying out below 250 ℃, particularly preferably in carrying out in the temperature range below 200 ℃.When the temperature range more than 300 ℃ is carried out, under the situation of method 3, have the tendency that is difficult to control thin film alignment, particularly, there is the tendency of the orientation be difficult to be controlled at the film end.

(D) in the step, because heat film sharp, film has contraction to a certain degree.Thereby, when the process furnace inlet does not fixedly transport with the TD direction with having tension force in fact, because the film that heating causes shrinks the width that can reduce film, makes that the thin-film width between both ends inboardend distance and the both ends inboardend is identical, can make film wrinkle resistantly.

The process furnace that the present application be fit to be used be adopt on film or below or all sprays the hotblast stove of the mode that the hot blast more than 100 ℃ heats from two towards film, perhaps use has and shines the far infrared line oven that far infrared rays comes the generating far infrared rays of roasting film.In heating steps, the preferred temperature that promotes is come roasting stagely, and therefore preferred hotblast stove or the far infrared line oven of using perhaps mixes hotblast stove and several the stage process furnace that are connected roasting with the far infrared line oven.For the heat that makes forehearth does not pass to following stove, the device that is used to separate each stove is installed between each stove preferably.

In the above-mentioned roasting process, from easy acquisition the MD direction controlled orientation the organic insulation film this put, the present application is controlled gel film in the manufacturing step of Kapton, and the Heating temperature of giving at first when being transported in the stove is preferably more than 100 ℃ below 250 ℃, is preferably especially more than 120 ℃ below 200 ℃.Particularly, above-mentioned process furnace preferably sets a plurality of process furnace more than 2, and the temperature of first process furnace is set at more than 100 ℃ below 250 ℃.In addition, when being adapted to other organic insulation film, consider that preferably the kind of organic insulation film and the volatilization temperature of solvent decide.The boiling point of the primary solvent that comprises in the special survey of anticipation gel film, and in high 100 ℃ temperature range, carry out temperature control from temperature than low 100 ℃ of this solvent boiling point.

In the manufacturing of Kapton, the Heating temperature of giving at first when transporting in the stove is more than 250 ℃ the time, on Kapton, can produce buckling phenomenon (because the influence that film shrinks, middle body is than the early inside heating furnace that enters in the end of film, produce the phenomenon of strong molecular orientation state in the end), have the tendency of the axis of orientation that is difficult to control the film end.In addition, below 100 ℃ the time, be set in temperature more than 100 ℃, below 250 ℃ by temperature with following stove, can production control the Kapton of molecular orientation axis.And the temperature of initial stage temperature and following stove is preferably as above set, roasting under the maturing temperature that temperature is in addition preferably used in the manufacturing of Kapton usually.

The tension force that is subjected on the gel film MD direction when transporting in stove is to calculate with the tension force that every 1m film bears, and is preferably 1～20kg/m, is preferably 1～15kg/m especially.Tension force is difficult to stably transport film when 1kg/m is following, the tendency that is difficult to controlling the stable film of preparation under the film is arranged.And the tension force of film particularly exists the MD direction to be difficult to control the tendency of molecular orientation in the end of film when 20kg/m is above.

As the tension force generation device that the gel film that transports in the stove is applied, can use gel film is applied roller that the heavy burden roller of heavy burden, the speed of rotation of adjusting roller change heavy burden, clamps the whole bag of tricks such as mode that gel film carries out the nip roll of tension control with 2 rollers and adjust tension force to gel film.

In addition, the tension force that film is given is preferably suitably adjusted in above-mentioned scope by the thickness of Kapton.It is thick that the thickness of film is preferably 1～200 μ m, is preferably 1～100 μ m especially.

Above-mentioned (D) step also can comprise (D-2) step of oriented film on the TD direction.

Among the present invention, be through after (D-1) step (D-2) in the step of oriented film on the TD direction, in process furnace along the step of TD direction oriented film.(D-1) in the step, the tension force of thin-film width direction (TD direction) is fixed in tension-free in fact mode and is transported, but when process furnace internal heating film, film can carry out contraction to a certain degree., after making the lax disappearance of film film is stretched along the TD direction in contraction.As B (Fig. 2), when the width of both ends inboardend is as C (Fig. 2) when the TD direction stretches in stove with film, preferably it satisfies following formula to tensile amount (for convenience, being referred to as rate of expansion) with the width of the both ends inboardend of the TD direction before stretching.

40.0 〉=(C-B)/B * 100＞0.00 (formula 4)

When (C-B)/B * 100 (for convenience, being referred to as the TD rate of expansion sometimes) above above above-mentioned scope, the molecular orientation axis of control film becomes difficult sometimes on the MD direction.30.0 〉=(C-B)/B * 100＞0.00 more preferably.Preferred especially 20.0 〉=(C-B)/B * 100＞0.00.

(D-2) in the step, Yi Bian can slowly enlarge the width one edge TD direction oriented film of film grip portion.In addition, also can after (D-2) step, shrink once more as required, in addition, can also enlarge thin-film width, preferably suitably select according to shrinkage, extensive magnitude.

Synthetic resin film be the conservation rate of modulus of elasticity at high temperature reduce film the time, the temperature of carrying out (D-2) step preferably stretches under the temperature of temperature ± 100 that its modulus of elasticity changes ℃.Particularly for the Kapton of excellent heat resistance, because more than 300 ℃ below 500 ℃, particularly reduce at the modulus of elasticity of Kapton below 480 ℃ more than 350 ℃, oriented film easily, thereby be preferred.And, when under draft temperature, synthetic resin film being transported, the situation of the softening elongation of film is arranged in stove.At this moment, the preferred above-mentioned scope temperature in addition of suitably setting.

Above-mentioned, reduction for the modulus of elasticity of determining film, use normally used storage modulus determinator, measure the mensuration temperature of this storage modulus, preferably storage modulus is begun to reduce and dissolving fully, perhaps storage modulus begins to reduce and shows the reduction temperature of the temperature of certain storage modulus as modulus of elasticity.

Among the present invention, can suitably regulate in (D-1) step contraction and (D-2) stretching in the step and when transporting memberane stress, the remaining composition weight of gel film, the Heating temperature of MD direction, be manufactured on the film that the MD direction has been controlled orientation.In addition, when synthetic resin film is Kapton, though the Heating temperature of film, heat-up time are different fully, but by carrying out chemical imidization or hot-imide, even under the situation of hot-imide, if carry out the control in the present application method, also can obtain the film of target.

(II) contain the adhesive linkage of thermoplastic polyimide

The thermoplastic polyimide that comprises in the adhesive linkage as adhering film among the present invention can preferably be used thermoplastic polyimide, polyamide thermoplastic imide, thermoplastic polyether imide, thermoplastic polyester imide etc.Wherein, from low moisture-absorption characteristics, especially preferably use the thermoplastic polyester imide.

In addition, from can consider with existing device lamination and the thermotolerance of not damaging the shop metal laminate that obtains the time, the thermoplastic polyimide preferred glass transition temperature (Tg) among the present invention is 150～300 ℃ a scope.In addition, Tg can obtain according to the value of the flex point of the storage modulus of being measured by Measurement of Dynamic Viscoelasticity device (DMA).

Thermoplastic polyimide can be by obtaining as the polyamic acid imidization of precursor.

For the thermoplastic polyimide precursor, be not particularly limited, can use known all polyamic acids.

In addition, about this manufacture method, can use known raw material and reaction conditions etc.

In addition, can also add inorganic or organic filler as required.

(III) manufacturing of adhering film

Adhering film of the present invention can obtain by the adhesive linkage that contains thermoplastic polyimide is set at least one surface of the specific Kapton of above-mentioned quantity-produced.As its concrete manufacture method, can preferably enumerate, form the method for adhesive linkage on as the Kapton of body material film or adhesive linkage is shaped to sheet, it is fitted to method on the above-mentioned Kapton etc.This wherein, when adopting the former method, because during the thermoplastic polyimide precursor that in adhesive linkage, contains to be polyamic acid complete imidization, the solvability of organic solvent there is the situation of reduction, therefore be difficult on Kapton, be provided with above-mentioned adhesive linkage sometimes.Thereby from above-mentioned viewpoint, preferably adopt with such an order: preparation contains the solution that the thermoplastic polyimide precursor is a polyamic acid, and it is applied on the body material film, then carries out imidization.

Method for curtain coating on Kapton, coating polyamic acid solution is not particularly limited, and can use existent method such as mould coating, counter-rotating coating, scraper coating.Under the situation that adhesive linkage forms continuously, effect of the present invention is remarkable.That is, the Kapton that as above obtains is batched, it is extracted out, will contain method as the continuous coating of solution of thermoplastic polyimide precursor polyamic acid.And, in above-mentioned polyamic acid solution, also can contain for example such other materials of filler as required.

In addition, for the thickness formation of each layer of heat resistant adhesive film, can suitably adjust to reach total thickness corresponding to purposes.In addition, can also before being set, adhesive linkage implement various surface treatments such as corona treatment, Cement Composite Treated by Plasma, coupling processing to the center film surface as required.

As the imidization method of thermoplastic polyimide, can use any of thermal curing method or chemosetting method.When adopting arbitrarily the imidization order, heat in order to carry out imidization expeditiously, the temperature of this moment preferably sets in the scope of (second-order transition temperature of thermoplastic polyimide-100 ℃)～(second-order transition temperature+200 ℃), more preferably be set in (second-order transition temperature of thermoplastic polyimide-50 ℃)～scope of (second-order transition temperature+150 ℃) in.

Can quicken curing speed by imidization because heat curing temperature causes when high easily, consider it is preferred from productivity.But too high words thermoplastic polyimide can produce thermolysis.

About the imidization time, can get and make imidization and drying finish adequate time in fact, limit without exception, but suitably set in the scope about 1～600 second usually.In addition, in order to improve the melt fluidity of adhesive linkage, can reduce imidization rate and/or residual solvent wittingly.

The tension force that applies during as imidization, is preferably set in the scope of 1kg/m～15kg/m when film thickness is 25 μ m with respect to the MD direction, preferably sets in the scope of 3kg/m～10kg/m especially.The above-mentioned scope of warp tension ratio hour can produce laxly when transporting film, produce problem such as can not evenly batch sometimes.In addition, when changing film thickness, tension force is appropriate change thereupon.On the contrary, when bigger,,, on adhering film, also can produce thermal stresses sometimes, thereby dimensional change is brought influence even central film is orientated on MD because be under the state that adhering film is applied high tension, to be heated to high temperature than above-mentioned scope.

Consider from the viewpoint of thermotolerance, resistance to bend(ing) and the cementability of FPC, the thickness of adhesive linkage be preferably 0.5 μ m above, below the 10 μ m.

In addition, during as T, the uneven thickness of preferred adhesive linkage preferably satisfies 0.7T＞T＞1.3T with the thickness of expectation.When above-mentioned scope was above, thickness of adhibited layer linear expansivity uneven and adhering film changed, and can bring influence to the dimensional change inequality of FCCL, because be not preferred.

(IV) flexible metal-clad laminate and manufacture method thereof

Flexible metal-clad laminate of the present invention applying tinsel on above-mentioned adhering film obtains.Be not particularly limited as the tinsel of using, but when in electronic machine, electric apparatus purposes, using flexible metal-clad laminate of the present invention, can enumerate, for example the paper tinsel that makes of copper or copper alloy, stainless steel or its alloy, nickel or nickelalloy (comprising 42 alloys), aluminum or aluminum alloy.

General flexible metal-clad laminate uses the Copper Foil that is called rolled copper foil, electrolytic copper foil mostly, also can preferably use in the present invention.In addition, in order to improve rustproof layer and refractory layer cementability with it, can implement coupler processing etc. to the surface of these tinsels.In the present invention, the thickness of above-mentioned tinsel is not particularly limited,, gets final product so long as can give full play to the thickness of function according to its purposes.

When adhering film of the present invention makes it fit with tinsel by pressing (DBP) to handle continuously with hot-roll lamination device that for example has a pair of above metallic roll or biobelt, can show effect especially significantly.

In addition, after adhering film cuts into suitable thin-film width, superimposed with tinsel continuously, but thin-film width is when 250mm is above, because size changing rate is little, and whole width range inside dimension velocity of variation is stable, thereby can be described as the form that shows effect of the present invention especially easily.

Consider it is that favourable this put from simple, the with low cost aspect of apparatus structure, preferably use hot-roll lamination device with a pair of above metallic roll with the superimposed opening and closing of metal.

When using such hot-roll lamination device, be not easy to occur dimensional change.Therefore, adhering film of the present invention is undertaken showing significant effect when superimposed by the hot-roll lamination device with a pair of above metallic roll.Here said " the hot-roll lamination device with a pair of above metallic roll " gets final product so long as have the device that is used for the metallic roll of material heating and pressurizing, and its concrete apparatus structure is not particularly limited.

The concrete structure of implementing the device of above-mentioned heat lamination is not particularly limited, but good for the outward appearance of the laminated plate that makes acquisition, is preferably adding configuration protection material between pressure surface and the tinsel.As protecting materials, the Heating temperature of lamination step as long as ability is heated then is not particularly limited, and can suitably use tinsels such as heat-resistant plastic, Copper Foil, aluminium foil, SUS paper tinsel such as non-thermal plasticity Kapton etc.This wherein from thermotolerance, the good aspect of usability isoequilibrium again, more preferably uses the non-thermal plasticity Kapton.

In addition, during thin thickness, the buffering in the time of can not giving full play to lamination and the effect of protection, so the thickness of non-thermal plasticity Kapton is preferably more than the 75 μ m.

And this protecting materials may not be 1 layer, also can be the multilayered structure more than 2 layers with different qualities.

The type of heating by laminated material in the above-mentioned heat lamination device is not particularly limited, and for example can use thermal cycling mode, hot blast type of heating, induce type of heating etc., the heating means of the known method that heats under the temperature of regulation.Similarly, the pressuring method by laminated material in the above-mentioned heat lamination device also is not particularly limited, and for example can use the pressurizing device that has adopted oil pressure mode, air pressure mode, clearance pressure mode etc. can apply the existing known manner of specified pressure.

Heating temperature in the above-mentioned heat lamination step, be laminating temperature be preferably adhering film second-order transition temperature (Tg)+50 ℃ more than temperature, more preferably more than the Tg+100 of adhering film ℃.If in the temperature more than Tg+50 ℃, can well adhering film and tinsel be carried out heat lamination.

In addition, if be more than Tg+100 ℃, laminate speed improved, thereby further improve productivity.

In addition, Heating temperature is more than 200 ℃ and then is can show the invention effect especially significantly more than 300 ℃ the time.Usually, when in adhesive linkage, using thermoplastic polyimide,, be necessary to apply more than 200 ℃, according to circumstances will apply near the high temperature 400 ℃ in order to show heat fusion.Therefore, produce residual stress in the flexible metal-clad laminate that lamination obtains, can produce dimensional change during levelling again when etching forms distribution and for installation parts carries out scolding tin.Adhering film of the present invention is because use film that whole width has specific rerum natura as Kapton, even therefore lamination at high temperature, it is little also to obtain size changing rate, and at the stable flexible metal-clad laminate of whole width dimensions velocity of variation.

Laminate speed in above-mentioned heat lamination step is preferably more than the 0.5m/ branch, more than more preferably 1.0m/ divides.If for more than 0.5m/ divides, heat lamination fully is if for more than the 1.0m/ branch, can improve productivity more.

Pressure in the above-mentioned heat lamination step is that lamination pressure is high more, and laminating temperature is low more, and can accelerate laminate speed, is favourable, but lamination pressure is too high usually, and the dimensional change of the laminated plate that obtains has the situation of deterioration.In addition, on the contrary, lamination pressure is too low, and the tinsel of the laminated plate that obtains and the bonding strength of thermoplastic polyimide can reduce.

Therefore, lamination pressure is preferably 49～490N/cm (in 5～50kgf/cm) the scope, more preferably 98～294N/cm is (in 10～30kgf/cm) the scope.In this scope, laminating temperature, laminate speed and three conditions of lamination pressure are reached well, thereby can improve productivity more.

The tension force of the adhering film in the above-mentioned lamination step is preferably 0.01～4N/cm, and more preferably 0.02～2.5N/cm is preferably 0.05～1.5N/cm especially.When tension force is lower than above-mentioned scope, when lamination transports, can produce laxly or snakelike, can not deliver in the warming mill uniformly, thereby be difficult to obtain the good flexible metal-clad laminate of outward appearance.

On the contrary, when surpassing above-mentioned scope, tensile influence grow can not relax poor dimensional stability down to the Tg of adhesive linkage and the control of storage modulus.

In order to obtain the flexible metal-clad laminate among the present invention, heat continuously by the heat lamination device of laminated material limit pressing on the preferred limit of using, but this heat lamination device also can be provided with at the leading portion of heat lamination device extraction by laminated material by the laminated material withdrawing device, can also the back segment setting of heat lamination device batch by laminated material by the laminated material take-up mechanism.By this device is set, can further improve the productivity of above-mentioned heat lamination device.Above-mentionedly be not particularly limited, for example, can enumerate known roller shape reeling machine of the laminated plate that can batch adhering film and tinsel or obtain etc. by the laminated material withdrawing device with by the concrete structure of the take-up mechanism of laminated material.

In addition, if protecting materials take-up mechanism or the protecting materials withdrawing device that batches or extract out protecting materials is set, then more preferred.If possess the take-up mechanism of these protecting materialss, the withdrawing device of protecting materials, in the heat lamination step,, can reuse protecting materials by being provided with once more and having used protecting materials once batching, extract out side.And, when batching protecting materials,, end position detection apparatus can be set and batch position correcting apparatus for the both ends that make protecting materials are neat.

Thus, because the end of protecting materials is fitly batched, can improve the efficient that re-uses.In addition, the take-up mechanism of these protecting materialss, the withdrawing device of protecting materials, end position detection apparatus and the concrete structure that batches position correcting apparatus are not particularly limited, and can use known various devices at present.

In the flexible metal-clad laminate that obtains by manufacture method of the present invention, under 250 ℃, heat the size changing rate aggregate value of 30 minutes front and back in MD direction, TD direction are-0.4～+ 0.4 scope after preferably removing the size changing rate of tinsel front and back and removing tinsel.Remove of specified dimension and the difference of specified dimension etching step after and recently the representing of specified dimension above-mentioned etching step before of the size changing rate of tinsel front and back with the flexible metal-clad laminate before the etching step.Size changing rate before and after the heating is specified dimension and the difference of the specified dimension behind the heating steps and recently the representing of the specified dimension before the above-mentioned heating steps with the flexible metal-clad laminate behind the etching step.

When size changing rate breaks away from this scope, in flexible metal-clad laminate, form fine distribution after, and the dimensional change during installation parts becomes big, has from the situation of the position deviation of the installation parts of design phase.Its result, mounted component might be able to not well contact with substrate.In other words, size changing rate is in the above-mentioned scope, can regard as and not hinder the parts installation.

The measuring method of above-mentioned size changing rate is not particularly limited, and in flexible metal-clad laminate, gets final product so long as can measure the method for the size increase and decrease that produces before and after etching or the heating steps, can use known any method at present.

Here, the mensuration of size changing rate must be measured on MD direction, TD direction both direction.Continuously when imidization and lamination, because the MD direction is different with the tension force of TD direction, thereby the table of degree of thermal expansion, contraction reveals difference, and size changing rate is also different.Therefore, the material requirements that size changing rate is little is all little at MD direction and TD direction both sides' velocity of variation.In the present invention, very preferably flexible metal-clad laminate remove size changing rate before and after the tinsel and tinsel remove the back 250 ℃ down the size changing rate aggregate value before and after the heating 30 minutes in MD direction, TD direction all in-0.4～+ 0.4 scope.

In addition, the actual conditions of the etching step during the size up velocity of variation is not particularly limited.That is, according to the shape of the pattern distribution of the kind of tinsel or formation etc., the etching condition difference, thereby the condition of the etching step during the size up velocity of variation can be known any condition at present among the present invention.Similarly, also can not heat 30 minutes down at 250 ℃ in the heating steps, actual conditions is not particularly limited.

As mentioned above, make the flexible metal-clad laminate that Preparation Method obtains according to of the present invention, if the etching metal paper tinsel forms the pattern distribution of expectation, then can be as the flexible wiring sheet of the parts that various miniaturizations, densification have been installed.Certainly, purposes of the present invention is not limited thereto, so long as contain the multilayer body of tinsel, then can be used for various uses.

Embodiment

Specify the present invention according to embodiment below, but the present invention is not only limited to these embodiment.

1. evaluation method

The evaluation method of the size changing rate of the second-order transition temperature of the thermoplastic polyimide in synthesis example, embodiment and the comparative example, the modulus of elasticity of Kapton and linear expansivity, flexible metal-clad laminate is as described below.

(1) thermoplastic polyimide

(second-order transition temperature)

Second-order transition temperature is the DMS200 that makes by Seiko Instruments company, under 3 ℃/minute of heat-up rates, in the temperature range of room temperature to 400 ℃ (measure frequency: 5Hz) measure down, with the flex point of storage modulus as second-order transition temperature.

(2) Kapton

(modulus of elasticity) modulus of elasticity is along the length direction of film and perpendicular direction (width), and (working sample of 15mm * 200mm) is measured the modulus of elasticity of all directions according to ASTM D882 to cut out 5 rectangles.

(linear expansivity)

The linear expansivity of adhering film is by Seiko Instruments company thermo-mechanical analysis device, trade(brand)name: TMA (Thermomechanical Analyzer) 120C, under nitrogen gas stream, under 10 ℃/minute of the heat-up rates, after in 10 ℃ to 400 ℃ temperature range, measuring, cool to room temperature, under the nitrogen gas stream, with 10 ℃/minute of heat-up rates, after in 10 ℃ to 400 ℃ temperature range, measuring, obtain the mean value in 100～200 ℃ of scopes.In addition, mensuration is that the MD direction and the TD direction of adhering film are carried out.

(3) flexible metal-clad laminate

(size changing rate)

Based on JIS C6481 5.16, on flexible metal-clad laminate, form 4 holes, measure the distance of each hole between separately.

Then, implement etching step, remove tinsel from flexible metal-clad laminate after, in 20 ℃, the thermostatic chamber of 60%RH, placed 24 hours.

Then, with the same before the etching step, measure the distance of above-mentioned 4 holes between separately.

As D1, the Determination of distance value of removing each hole after the tinsel is as D2 with the Determination of distance value of removing each hole before the tinsel, obtains size changing rate before and after the etching according to following formula.

Size changing rate (%)=(D2-D1)/D1} * 100

Then, the working sample after adding thermal etching under 250 ℃ is after 30 minutes, places 24 hours in 20 ℃, the thermostatic chamber of 60%RH.Then, measure the distance of 4 holes between separately.Determination of distance value between each hole after the heating as D3, is obtained the size changing rate of heating front and back according to following formula.

Size changing rate (%)=(D3-D2)/D2} * 100

In addition, above-mentioned size changing rate is that MD direction and TD direction both sides are measured.

(synthesis example 1: the making of Kapton)

With pyromellitic acid dianhydride/4,4 '-oxo pentanoic/Ursol D is with the ratio of mol ratio 1/0.75/0.25, at N, and polymerization under N '-dimethylacetamide solvent, obtaining solids component is 18%.

Particularly, will be 4 of 75 moles of % with respect to whole two amine components, 4 '-oxo pentanoic is dissolved in N, in N '-dimethylacetamide solvent, then full dose drops into pyromellitic acid dianhydride (that is, with respect to the acid anhydrides of the two amine components input 133% that has dropped into), obtains sour terminal prepolymer.

Then, in the pre-polymer solution of this acid end, make the first-class mole of two amine components (being Ursol D) and all acid composition essence ground add the remaining not enough diamines that divides and make it reaction, obtain polymeric solution.

This polymeric solution is cooled to about 0 ℃, with respect to 1 mole of amido acid that is cooled to about 0 ℃ polyamic acid organic solvent solution, add the acetic anhydride of 2.0 moles of % and the isoquinoline 99.9 of 0.5 mole of %, after fully stirring, extrude by die head, after dry, the roasting on the endless belt curtain coating, coating reach 25 μ m.On the endless belt, heat, obtain the gel film that remaining component proportions is 30 weight %.

Peel this gel film, then, the state that is fixed on the needle plate that transports sheet continuously with the two ends of sheet transports in hotblast stove, 250 ℃ down heating then in 350 ℃, 400 ℃ hotblast stove, transport after 20 seconds, respectively carry out heating in 20 seconds.Then, use FAR INFRARED HEATING stove (below be called far-infrared oven), carry out heating in 20 seconds under 350 ℃, when take out of the annealing region, peel film from pin, reeling obtains 25 wide μ m end fixed films of about 1m (growing the size goods).

As aftertreatment, with the film that obtains on one side with spool control tension force limit in hotblast stove, far-infrared oven, heat, tension force handles.The condition of this moment is that the interior residence time of stove is 50 seconds, and temperature is 500 ℃ in the stove, tension force 0.51kg/mm ²

(synthesis example 2: the making of Kapton)

Except changing to condition shown in the table 1, implement similarly to Example 1 on one side to control the tension force of film in roller-suspension column-roller, Yi Bian in hotblast stove, far-infrared oven, heat, the tension force processing.

(synthesis example 3: the making of Kapton)

With pyromellitic acid dianhydride/TOPOT 2,2 (trimellitic acid monoesters acid anhydrides)/4,4 '-diaminodiphenyl oxide/Ursol D is with the ratio of mol ratio 1/1/1/1, at N, and polymerization under N '-dimethylacetamide solvent, obtaining solids component is 18%.

This polymeric solution is cooled to about 0 ℃, with respect to 1 mole of amido acid that is cooled to about 0 ℃ polyamic acid organic solvent solution, add the acetic anhydride of 2.1 moles of % and the isoquinoline 99.9 of 1.1 moles of %, after fully stirring, extrude by the die head that is maintained at about 5 ℃, curtain coating is applied on the endless belt, and heating, drying obtain the residual component ratio and be 60% gel film.

Peel this raw cook (green sheet) (gel film) with self-supporting, then the two ends with sheet are fixed on the needle plate that transports sheet continuously, in hot-blast heater, far-infrared oven, annealing furnace, transport, when from annealing furnace, taking out of, peel film from latching, reeling obtains the Kapton of 18 wide μ m of about 1.0m.

The atmosphere temperature degree of process furnace (for hotblast stove) (1～4 stove), far-infrared oven, annealing furnace and residence time, shrinking percentage and rate of expansion (being expressed as the expansion shrinking percentage) are as shown in table 3.Shorten two ends inboardend distance so that the TD direction do not have in fact tension force ground fixed step be in stove, insert film before terminated, expand the step of two ends inboardend distance and carry out at 4 stoves.IR stove in the table is represented far-infrared oven.

(synthesis example 4: the making of Kapton)

With pyromellitic acid dianhydride/TOPOT 2,2 (trimellitic acid monoesters acid anhydrides)/4,4 '-diaminodiphenyl oxide/Ursol D is with the ratio of mol ratio 1/1/1/1, at N, and polymerization under N '-dimethylacetamide solvent, obtaining solids component is 18%.

This polymeric solution is cooled to about 0 ℃, with respect to 1 mole of amido acid that is cooled to about 0 ℃ polyamic acid organic solvent solution, add the acetic anhydride of 2.1 moles of % and the isoquinoline 99.9 of 1.1 moles of %, after fully stirring, extrude with the die head that is maintained at about 5 ℃, curtain coating is applied on the endless belt, and heating, drying obtain the residual component ratio and be 60% gel film.

Peel this raw cook with self-supporting (gel film), then the two ends with sheet are fixed on the needle plate that transports sheet continuously, in hot-blast heater, far-infrared oven, annealing furnace, transport, when from annealing furnace, taking out of, peel film from latching, reeling obtains the Kapton of 18 wide μ m of about 1.0m.

The atmosphere temperature degree of process furnace (being hotblast stove) (1～3 stove), far-infrared oven, annealing furnace and residence time, expansion shrinking percentage are as shown in table 4.Shorten two ends inboardend distance so that the TD direction do not have in fact tension force ground fixed step be in stove, insert film before terminated, expand the step of two ends inboardend distance and carry out at 3 stoves.IR stove in the table is represented far-infrared oven.

(synthesis example 5: the making of Kapton)

With pyromellitic acid dianhydride/4,4 '-oxo pentanoic/Ursol D is with the ratio of mol ratio 1/0.75/0.25, at N, and polymerization under N '-dimethylacetamide solvent, obtaining solids component is 18%.

Particularly, at N, dissolving is 4 of 75 moles of % with respect to whole two amine components in N '-dimethylacetamide solvent, 4 '-oxo pentanoic, then full dose drops into pyromellitic acid dianhydride (that is, with respect to the acid anhydrides of the two amine components input 133% that has dropped into), obtains sour terminal prepolymer.Then, in the terminal pre-polymer solution of this acid, make the first-class mole of two amine components (being Ursol D) and all acid composition essence ground add remaining not enough two amine components that divide and make it reaction, obtain polymeric solution.

This polymeric solution is cooled to about 0 ℃, with respect to 1 mole of amido acid that is cooled to about 0 ℃ polyamic acid organic solvent solution, add the acetic anhydride of 2.0 moles of % and the isoquinoline 99.9 of 0.5 mole of %, after fully stirring, extrude by die head, after dry, the roasting on the endless belt curtain coating, coating reach 25 μ m.On the endless belt, heat, obtain the gel film that remaining component proportions is 30 weight %.

Peel this gel film, then, the state that is fixed on the needle plate that transports sheet continuously with the two ends of sheet transports in hotblast stove, 250 ℃ down heating then in 350 ℃, 400 ℃ hotblast stove, transport after 20 seconds, respectively carry out heating in 20 seconds.Then, use the FAR INFRARED HEATING stove, carry out heating in 20 seconds under 530 ℃, when take out of the annealing region, peel film from pin, reeling obtains 25 wide μ m end fixed films of about 1m (growing the size goods).

(synthesis example 6: the making of Kapton)

Except will expand shrinking percentage, heating condition change to as shown in table 4 and synthesis example 4 similarly obtain film.

(synthesis example 7: thermoplastic polyimide precursor synthetic)

Capacity be add in the glass flask of 2000ml 780g DMF, 115.6g 2, two [4-(4-amino-benzene oxygen) phenyl] propane of 2-(below be called BAPP), stir under nitrogen atmosphere gas on the limit, the BPDA of 78.7g is slowly added on the limit.Then, add 3.8g ethylene glycol bis trimelitic dianhydride (below be called TMEG), under ice bath, stirred 30 minutes.The TMEG for preparing 2.0g in addition is dissolved in the solution among the DMF of 20g, while note regulating viscosity it is slowly added in the above-mentioned reaction soln, and stirs.Viscosity stops when reaching 3000 pools adding, stirring, and obtains polyamic acid solution (thermoplastic polyimide precursor).

And, in order to investigate the second-order transition temperature of the polyimide polymer that from obtain polyamic acid solution, obtains, at thick PET film (the Cerapeel HP of 25 μ m, the manufacturing of Toyo Metallizing company) goes up the polyamic acid solution that curtain coating obtains, and to make final thickness be 20 μ m, carries out 5 minutes dryings under 120 ℃.After peeling off dried self-supporting film from PET, be fixed on the latching frame that metal makes, in the drying of carrying out carrying out under 5 minutes, 200 ℃ carrying out under 5 minutes, 250 ℃ carrying out under 5 minutes, 350 ℃ 5 minutes under 150 ℃.The second-order transition temperature of the single-layer sheet that mensuration obtains is 240 ℃.

(synthesis example 8: the making of Kapton)

With pyromellitic acid dianhydride/TOPOT 2,2 (trimellitic acid monoesters acid anhydrides)/4,4 '-diaminodiphenyl oxide/Ursol D is with the ratio of mol ratio 1/1/1/1, at N, and polymerization under N '-solvent dimethylformamide, obtaining solids component is 18%.

This polymeric solution is cooled to about 0 ℃, with respect to 1 mole of amido acid that is cooled to about 0 ℃ polyamic acid organic solvent solution, add the acetic anhydride of 1.6 moles of % and the isoquinoline 99.9 of 0.8 mole of %, after fully stirring, extrude with the die head that is maintained at about-5 ℃, curtain coating is applied on the endless belt.By on the endless belt to heat below 140 ℃, obtain the residual component ratio and be 60% gel film.

Peel this raw cook with self-supporting (gel film), then the two ends with sheet are fixed on the needle plate that transports sheet continuously, in hot-blast heater, far-infrared oven, annealing furnace, transport, when from annealing furnace, taking out of, peel film from latching, reeling obtains the Kapton of 18 wide μ m of about 1.5m.

Atmosphere temperature degree, residence time, shrinking percentage and the expansion chlorine of process furnace (1～3 stove), far-infrared oven, annealing furnace (being collectively referred to as the expansion shrinking percentage) is as shown in table 8.

The expansion shrinking percentage be-when (bear), being illustrated in this stove inlet film and being in relaxed state in the TD direction, and expand shrinking percentage and be+when (just), represent that film is in stretched state.

(synthesis example 9: the making of Kapton)

Except the expansion shrinking percentage, heating condition is as shown in table 8 change and synthesis example 8 similarly make Kapton.

(synthesis example 10: the making of Kapton)

Except the expansion shrinking percentage, heating condition is as shown in table 9 change and synthesis example 8 similarly make Kapton.

(synthesis example 11: the making of Kapton)

Except the expansion shrinking percentage, heating condition is as shown in table 8 change and synthesis example 8 similarly make Kapton.

(synthesis example 12: the making of Kapton)

With pyromellitic acid dianhydride/TOPOT 2,2 (trimellitic acid monoesters acid anhydrides)/4,4 '-diaminodiphenyl oxide/Ursol D is with the ratio of mol ratio 1/1/1/1, at N, and polymerization under N '-dimethylacetamide solvent, obtaining solids component is 18%.

This polymeric solution is cooled to about 0 ℃, with respect to 1 mole of amido acid that is cooled to about 0 ℃ polyamic acid organic solvent solution, add the acetic anhydride of 1.6 moles of % and the isoquinoline 99.9 of 0.8 mole of %, after fully stirring, extrude with the die head that is maintained at about-5 ℃, curtain coating is applied on the endless belt.On the endless belt to heat below 140 ℃, obtain the residual component ratio and be 28% gel film.Peel this raw cook with self-supporting (gel film), then the two ends with sheet are fixed on the needle plate that transports sheet continuously, in hot-blast heater, far-infrared oven, annealing furnace, transport, when from annealing furnace, taking out of, peel film from latching, reeling obtains the Kapton of 18.5 wide μ m of about 1.5m.As the aftertreatment of the film that obtains, used the heating stretch processing (stretching) of IR stove with spool (roll to roll) to the MD direction, obtain film.

The atmosphere temperature degree and the residence time of process furnace (1～3 stove), far-infrared oven, annealing furnace are shown in Table 3.The condition that stretch processing is promptly heated in aftertreatment is shown in Table 10.

(synthesis example 13: the making of Kapton)

Except the expansion shrinking percentage, heating condition is as shown in table 9 change and synthesis example 8 similarly make film.

(synthesis example 14: the making of Kapton)

Except change as shown in table 10 is controlled at tension force in the spool as one side of the aftertreatment of film, in hotblast stove, far-infrared oven heat, condition that tension force handle beyond, with synthesis example 12 similarly implement on one side.

(synthesis example 15: thermoplastic polyimide precursor synthetic)

Capacity be add in the glass flask of 2000ml 780g DMF, 115.6g 2, two [4-(4-amino-benzene oxygen) phenyl] propane of 2-(below be called BAPP), stir under nitrogen atmosphere gas on the limit, 78.7g BPDA is slowly added on the limit.Then, add 3.8g TMEG, under ice bath, stirred 30 minutes.Prepare 2.0g TMEG in addition and be dissolved in solution among the 20g DMF, while note regulating viscosity it is slowly added in the above-mentioned reaction soln, and stir.Viscosity stops when reaching 3000 pools adding, stirring, and obtains polyamic acid solution (thermoplastic polyimide precursor).

And, in order to investigate the second-order transition temperature of the polyimide polymer that from obtain polyamic acid solution, obtains, at thick PET film (the Cerapeel HP of 25 μ m, the manufacturing of Toyo Metallizing company) goes up the polyamic acid solution that curtain coating obtains, and to make final thickness be 20 μ m, carries out 5 minutes dryings under 120 ℃.After peeling off dried self-supporting film from PET, be fixed on the latching frame that metal makes, in the drying of carrying out carrying out under 5 minutes, 200 ℃ carrying out under 5 minutes, 250 ℃ carrying out under 5 minutes, 350 ℃ 5 minutes under 150 ℃.

The second-order transition temperature of the single thin film that mensuration obtains is 240 ℃.

(synthesis example 16: the making of Kapton)

With pyromellitic acid dianhydride/4,4 '-oxo pentanoic/Ursol D is with the ratio of mol ratio 1/0.75/0.25, at N, and polymerization under N '-dimethylacetamide solvent, obtaining solids component is 18%.

Particularly, at N, dissolving is 4 of 75 moles of % with respect to whole two amine components in N '-dimethylacetamide solvent, 4 '-oxo pentanoic, then full dose drops into pyromellitic acid dianhydride (that is, with respect to the acid anhydrides of the two amine components input 133% that has dropped into), obtains sour terminal prepolymer.Then, in the terminal pre-polymer solution of this acid, make the first-class mole of two amine components (being Ursol D) and all acid composition essence ground add the diamines that residual deficiency is divided, and make it reaction, obtain polymeric solution.

This polymeric solution is cooled to about 0 ℃, with respect to 1 mole of amido acid that is cooled to about 0 ℃ polyamic acid organic solvent solution, add the acetic anhydride of 2.0 moles of % and the isoquinoline 99.9 of 0.5 mole of %, after fully stirring, extrude by die head, after dry, the roasting on the endless belt curtain coating, coating reach 25 μ m.On the endless belt, heat, obtain the gel film that remaining component proportions is 50 weight %.Peel this gel film, then, the state that is fixed on the needle plate that transports sheet continuously with the two ends of sheet transports in hotblast stove, 250 ℃ down heating then in 350 ℃, 400 ℃ hotblast stove, transport after 30 seconds, respectively carry out heating in 30 seconds.Then, use the FAR INFRARED HEATING stove, carry out heating in 30 seconds under 350 ℃, when take out of the annealed zone, peel film from pin, reeling obtains 25 wide μ m end fixed films of about 1m (growing the size goods).

As aftertreatment, the film that obtains is controlled tension force with spool on one side, on one side in hotblast stove, far-infrared oven, heat, tension force handles.The condition of this moment is that the interior residence time of stove is 30 seconds, and temperature is 460 ℃ in the stove, tension force 0.32kg/mm ²

(synthesis example 17: the making of Kapton)

Except change as shown in table 13 is controlled at tension force on the spool as one side of the aftertreatment of film, in hotblast stove, far-infrared oven heat, condition that tension force handle beyond, with synthesis example 16 similarly implement on one side.

(synthesis example 18: the making of Kapton)

Except change as shown in table 13 is controlled at tension force on the spool as one side of the aftertreatment of film, in hotblast stove, far-infrared oven heat, condition that tension force handle beyond, with synthesis example 16 similarly implement on one side.

(synthesis example 20: the preparation of Kapton)

Except change as shown in table 13 is controlled at tension force on the spool as one side of the aftertreatment of film, in hotblast stove, far-infrared oven heat, condition that tension force handle beyond, with synthesis example 16 similarly implement on one side.

(synthesis example 19: the preparation of Kapton)

With pyromellitic acid dianhydride/4,4 '-oxo pentanoic/Ursol D is with the ratio of mol ratio 1/0.75/0.25, at N, and polymerization under N '-dimethylacetamide solvent, obtaining solids component is 18%.

Particularly, at N, dissolving is 4 of 75 moles of % with respect to whole two amine components in N '-dimethylacetamide solvent, 4 '-oxo pentanoic, then full dose drops into pyromellitic acid dianhydride (that is, with respect to the acid anhydrides of the two amine components input 133% that has dropped into), obtains sour terminal prepolymer.Then, in the terminal pre-polymer solution of this acid, make the first-class mole of two amine components (being Ursol D) and all acid composition essence ground add the diamines that residual deficiency is divided, and make it reaction, obtain polymeric solution.

This polymeric solution is cooled to about 0 ℃, with respect to 1 mole of amido acid that is cooled to about 0 ℃ polyamic acid organic solvent solution, add the acetic anhydride of 2.0 moles of % and the isoquinoline 99.9 of 0.5 mole of %, after fully stirring, extrude by die head, after dry, the roasting on the endless belt curtain coating, coating reach 25 μ m.On the endless belt, heat, obtain the gel film that remaining component proportions is 50 weight %.

Peel this gel film, then, the state that is fixed on the needle plate that transports sheet continuously with the two ends of sheet transports in hotblast stove, 250 ℃ down heating then in 350 ℃, 400 ℃ hotblast stove, transport after 30 seconds, respectively carry out heating in 30 seconds.Then, use the FAR INFRARED HEATING stove, carry out heating in 30 seconds under 520 ℃, when take out of the annealed zone, peel film from pin, reeling obtains 25 wide μ m end fixed films of about 1m (growing the size goods).

(synthesis example 21: thermoplastic polyimide precursor synthetic)

Capacity be add in the glass flask of 2000ml 780g DMF, 115.6g 2, two [4-(4-amino-benzene oxygen) phenyl] propane of 2-(below be called BAPP), stir under nitrogen atmosphere gas on the limit, 78.7g BPDA is slowly added on the limit.Then, add the ethylene glycol bis trimelitic dianhydride (below be called TMEG) of 3.8g, under ice bath, stirred 30 minutes.The TMEG for preparing 2.0g in addition is dissolved in the solution among the 20g DMF, while note regulating viscosity it is slowly added in the above-mentioned reaction soln, and stirs.Viscosity stops when reaching 3000 pools adding, stirring, and obtains polyamic acid solution (thermoplastic polyimide precursor).

And, in order to investigate the second-order transition temperature of the polyimide polymer that from obtain polyamic acid solution, obtains, at thick PET film (the Cerapeel HP of 25 μ m, the manufacturing of Toyo Metallizing company) goes up the polyamic acid solution that curtain coating obtains, and to make final thickness be 20 μ m, carries out 5 minutes dryings under 120 ℃.After peeling off dried self-supporting film from PET, be fixed on the latching frame that metal makes, in the drying of carrying out carrying out under 5 minutes, 200 ℃ carrying out under 5 minutes, 250 ℃ carrying out under 5 minutes, 350 ℃ 5 minutes under 150 ℃.The second-order transition temperature of the single thin film that mensuration obtains is 240 ℃.

(embodiment 1)

With the polyamic acid solution that obtains in the DMF dilution synthesis example 7 after solid component concentration is 10 weight %, the two sided coatings polyamic acid of the Kapton (the wide 1000mm of film) that in synthesis example 1, obtains, make that the final single face thickness of thermoplastic polyimide layer (adhesive linkage) is 4 μ m, under 140 ℃, carry out heating in 1 minute then.Then, under tension force 5kg/m, with the FAR INFRARED HEATING stove of 20 second time, add hot-imide, obtain adhering film by 390 ℃ of atmosphere temperature degree.

Use the rolled copper foil (BHY-22B-T, JapanEnergy company makes) of 18 μ m in the both sides of the adhering film that obtains, on the Copper Foil both sides, use protecting materials (Apical 125NPI again; Kaneka company makes), tension force at Kapton is 0.4N/cm, and laminating temperature is 360 ℃, and lamination pressure is 196N/cm (20kgf/cm), laminate speed is to carry out heat lamination continuously under 1.5m/ minute the condition, makes flexible metal-clad laminate of the present invention.

(embodiment 2)

The Kapton that the Kapton that obtains replaces obtaining in the synthesis example 1, carry out operation similarly to Example 1 in using synthesis example 2, make adhering film and flexible metal-clad laminate.

(embodiment 3)

With the polyamic acid solution that obtains in the DMF dilution synthesis example 7 after solid component concentration is 10 weight %, the two sided coatings polyamic acid of the Kapton (the wide 1000mm of film) that in synthesis example 3, obtains, make that the final single face thickness of thermoplastic polyimide layer (adhesive linkage) is 4 μ m, under 140 ℃, carry out heating in 1 minute then.Then, under tension force 5kg/m,, add hot-imide, obtain adhering film with the FAR INFRARED HEATING stove of 20 second time by 390 ℃ of atmosphere temperature degree.

Use the rolled copper foil (BHY-22B-T, JapanEnergy company makes) of 18 μ m in the both sides of the adhering film that obtains, on the Copper Foil both sides, use protecting materials (Apical 125NPI again; Kaneka company makes), tension force at Kapton is 0.4N/cm, and laminating temperature is 360 ℃, and lamination pressure is 196N/cm (20kgf/cm), laminate speed is to carry out heat lamination continuously under 1.5m/ minute the condition, makes flexible metal-clad laminate of the present invention.

(embodiment 4)

The Kapton that the Kapton that obtains replaces obtaining in the synthesis example 3, carry out operation similarly to Example 3 in using synthesis example 4, make adhering film and flexible metal-clad laminate.

(comparative example 1)

The Kapton that the Kapton that obtains replaces obtaining in the synthesis example 1, carry out operation similarly to Example 1 in using synthesis example 5, make adhering film and flexible metal-clad laminate.

(comparative example 2)

The Kapton that the Kapton that obtains replaces obtaining in the synthesis example 1, carry out operation similarly to Example 3 in using synthesis example 6, make adhering film and flexible metal-clad laminate.

The sampling method of the dimensional change working sample of the flexible metal-clad laminate of embodiment 1～4, comparative example 1,2 as shown in Figure 3.

Table 1 illustrates the manufacturing conditions of film synthesis example 1,2,5.

[table 1]

Table 1

	Atmosphere temperature degree (epimere: temperature ℃ hypomere: second residence time)				Heating, tension force are handled
									1 stove	2 stoves	3 stoves	The IR stove	Temperature (℃)	Residence time (second)	Tension force (kg2/mm2)	Tension force (kg/m)
	Synthesis example 1	250	350	400	350	500	50	0.51									12.7
20									20	20	20
		Synthesis example 2	250	350	400							350	510	50	0.54	13.5
20	20					20	20
			Synthesis example 5	250	350			400	530	-	-	-					-
20	20	20				20

Table 2 illustrates the linear expansion coefficient determining result of embodiment 1,2, comparative example 1.

Table 2

	Linear expansivity		Linear expansivity MD/TD ratio
				MD	TD
	ppm/℃
				Embodiment 1	16.7	37.8	0.44
Embodiment 2	13.2	43.5	0.30
				Comparative example 1	26.3	23.7	1.11

Table 3 shows the manufacturing conditions of film synthesis example 3.

[table 3]

Table 3

	Atmosphere temperature degree (epimere: temperature ℃ hypomere: second residence time)						Expansion shrinking percentage (%)
													1 stove	2 stoves	3 stoves	4 stoves	The IR stove	Annealing furnace	1 stove	2 stoves	3 stoves	4 stoves	The IR stove	Annealing furnace
	Synthesis example 3	130	250	350	450	510	490 450 350	-1.9	0	0	4	0													0
60													60	60	60	70	200

Table 4 shows the manufacturing conditions of film synthesis example 4,6.

[table 4]

Table 4

	Atmosphere temperature degree (epimere: temperature ℃ hypomere: second residence time)					Expansion shrinking percentage (%)
											1 stove	2 stoves	3 stoves	The IR stove	Annealing furnace	1 stove	2 stoves	3 stoves	The IR stove	Annealing furnace
	Synthesis example 4	150	300	450	570	520 460 410 350 290 240	-4.3	0	4.3	0											0
25											25	20	20	60
		Synthesis example 6	300	400	450	570									520 460 410 350 290 240	0	0	0	0	0
25	25						20	20	60

Table 5 shows the dimensional change measurement result of embodiment 1,2, comparative example 1.

[table 5]

Table 5

	Locate	After the etching (%)			Heating back (%)		Accumulation (after the etching+the heating back)
										MD	TD	The MD/TD difference	MD	TD	MD	TD	The MD/TD difference
		Embodiment 1	A	-0.13	0.00	0.13	-0.12	0.15	-0.25									0.15	0.40
B	-0.15									0.01	0.16	-0.12	0.19	-0.27	0.20	0.47
			C	-0.11	0.04	0.15	-0.09	0.20	-0.20								0.24	0.44
Embodiment 2	A									-0.08	-0.08	0.02	-0.07	0.15	-0.15	0.09			0.24
		B	-0.08	-0.03	0.03	-0.09	0.17	-0.15	0.14								0.29
	C									-0.03	-0.05	0.02	-0.07	0.19	-0.10	0.14		0.24
		Comparative example 1	A	-0.27	0.26	0.53	-0.18	0.19	-0.45								0.45		0.90
B	-0.27									0.27	0.54	-0.19	0.18	-0.45	0.43	0.89
			C	-0.25	0.26	0.51	-0.20	0.18	-0.45								0.44	0.89

Table 6 shows the linear expansion coefficient determining result of embodiment 3,4, comparative example 2.

[table 6]

Table 6

	Linear expansivity		Linear expansivity MD/TD ratio
				MD	TD
	ppm/℃
				Embodiment 3	20.1	22.4	0.90
Embodiment 4	19.4	24.1	0.80
				Comparative example 2	22.0	20.1	1.09

Table 7 shows the dimensional change measurement result of embodiment 3,4, comparative example 2.

[table 7]

Table 7

	Locate	After the etching (%)			Heating back (%)		Accumulation (after the etching+the heating back)
										MD	TD	The MD/TD difference	MD	TD	MD	TD	The MD/TD difference
		Embodiment 3	A	-0.01	0.03	0.04	-0.09	0.07	-0.10									0.10	0.20
B	-0.02									0.01	0.03	-0.11	0.06	-0.13	0.07	0.20
			C	-0.02	0.03	0.05	-0.11	0.06	-0.13								0.09	0.22
Embodiment 4	A									-0.03	-0.04	0.01	-0.10	0.06	-0.13	0.02			0.15
		B	-0.03	-0.03	0.00	-0.09	0.05	-0.12	0.02								0.14
	C									-0.03	-0.04	0.01	-0.09	0.07	-0.12	0.03		0.15
		Comparative example 2	A	-0.05	0.05	0.10	-0.12	0.11	-0.17								0.16		0.33
B	-0.05									0.05	0.12	-0.13	0.09	-0.18	0.15	0.34
			C	-0.05	0.05	0.11	-0.12	0.11	-0.18								0.16	0.34

Like this, shown in comparative example 1, when the characteristic of adhering film surpassed specific scope, the result was that the dimensional change of flexible metallizing multilayer body becomes big.To this, be among the embodiment 1～4 of certain limit in the characteristic of adhering film, suppressed the generation of the dimensional change of flexible metallizing multilayer body.

(embodiment 5)

With the polyamic acid solution that obtains in the DMF dilution synthesis example 15 after solid component concentration is 10 weight %, the two sided coatings polyamic acid of the Kapton that in synthesis example 8, obtains, make that the final single face thickness of thermoplastic polyimide layer (adhesive linkage) is 4 μ m, under 140 ℃, carry out heating in 1 minute then.Then,, add hot-imide, obtain adhering film with the FAR INFRARED HEATING stove of 20 second time by 390 ℃ of atmosphere temperature degree.Use the rolled copper foil (BHY-22B-T, Japan Energy company makes) of 18 μ m in the both sides of the adhering film that obtains, use protecting materials (Apical 125NPI again in the Copper Foil both sides; Kaneka company makes), tension force at Kapton is 0.4N/cm, and laminating temperature is 360 ℃, and lamination pressure is 196N/cm (20kgf/cm), laminate speed is to carry out heat lamination continuously under 1.5m/ minute the condition, makes flexible metal-clad laminate of the present invention.

(embodiment 6)

The Kapton that the Kapton that obtains replaces obtaining in the synthesis example 8, carry out operation similarly to Example 5 in using synthesis example 9, make adhering film and flexible metal-clad laminate.

(embodiment 7)

The Kapton that the Kapton that obtains replaces obtaining in the synthesis example 8, carry out operation similarly to Example 5 in using synthesis example 10, make adhering film and flexible metal-clad laminate.

(embodiment 8)

The Kapton that the Kapton that obtains replaces obtaining in the synthesis example 8, carry out operation similarly to Example 5 in using synthesis example 12, make adhering film and flexible metal-clad laminate.

(embodiment 9)

The Kapton that the Kapton that obtains replaces obtaining in the synthesis example 8, carry out operation similarly to Example 5 in using synthesis example 14, make adhering film and flexible metal-clad laminate.

(comparative example 3)

The Kapton that the Kapton that obtains replaces obtaining in the synthesis example 8, carry out operation similarly to Example 5 in using synthesis example 11, make adhering film and flexible metal-clad laminate.

(reference example)

The Kapton that the Kapton that obtains replaces obtaining in the synthesis example 8, carry out operation similarly to Example 5 in using synthesis example 13, make adhering film and flexible metal-clad laminate.

The modulus of elasticity of the adhering film that obtains in each embodiment, the comparative example is shown in Table 11.

The evaluation result of the characteristic of flexible metal-clad laminate is shown in Table 12.The adhering film that obtains, the sampling method of flexible metal-clad laminate are as shown in Figure 4.

Table 8 shows the manufacturing conditions of synthesis example 8,9,10.

[table 8]

Table 8

	Expansion shrinking percentage (%)				Mist enclose the temperature degree (℃)
										Hotblast stove			The IR stove
	1 stove	2 stoves	3 stoves	1 stove										2 stoves	3 stoves	The IR stove	Annealing furnace
					Synthesis example 8	-4.4	0.0	4.4	0.0	150	300	450						570	520 460 410 350 290 240
Synthesis example 9	-4.4	0.0	2.2	0.0									180	300	450	570	520 460 410 350 290 240
					Synthesis example 11	0.0	0.0	0.0	0.0	350	400	450						570	520 460 410 350 290 240
Residence time (second)													25	25	20	20	60

Table 9 illustrates the manufacturing conditions of synthesis example 10,13.

[table 9]

Table 9

	Expansion shrinking percentage (%)				Mist enclose the temperature degree (℃)
										Hotblast stove			The IR stove
	1 stove	2 stoves	3 stoves	1 stove										2 stoves	3 stoves	The IR stove	Annealing furnace
					Synthesis example 10	-5.0	0.0	0.0	0.0	200	330	450						570	520 460 410 350 290 240
Synthesis example 13	-15.0	0.0	0.0	0.0									200	330	450	570	520 460 410 350 290 240
					Residence time (second)					60	60	30						40	80

Table 10 illustrates the manufacturing conditions of synthesis example 12,14.

[table 10]

Table 10

	Mist enclose the temperature degree (℃)					Post-processing temperature (℃)	Aftertreatment tension force (kg/m)	Aftertreatment tension force (kg/mm 2)
									1 stove	2 stoves	3 stoves	The IR stove	Annealing furnace
	Synthesis example 12	350	400	450	410									410 350 290 240	500	8	0.43
Synthesis example 14						350	400	450	410	410 350 290 240	500	13.5	0.73
	Residence time (second)	25	25	20	20									60	30

Table 11 illustrates the modulus of elasticity measurement result of the adhering film of embodiment 5～9, comparative example 3, reference example.

[table 11]

Table 11

	The Kapton synthesis example	The caking agent synthesis example	Modulus of elasticity (G Pa)		Modulus of elasticity compares MD/TD
						MD	TD
			Embodiment 5	8				15	5.57	5.31	1.05
Embodiment 6	9	15			5.60	5.07	1.10
			Embodiment 7	10				15	5.84	4.86	1.20
Embodiment 8	12	15			5.90	4.79	1.23
			Embodiment 9	14				15	5.27	3.12	1.69
Comparative example 3	11	15			5.40	5.43	0.99
			Reference example	13				15	7.52	3.51	2.14

Table 12 illustrates the dimensional change measurement result of embodiment 5～9, comparative example 3, reference example.

[table 12]

Table 12

	The Kapton synthesis example	The caking agent synthesis example	The sample position	Dimensional change (%)
											After the etching		After the heating		Accumulation		The difference of MD and TD
				MD	TD	MD	TD	MD	TD
										Embodiment 5	8	15	A	-0.03	-0.03	-0.09		0.05	-0.12	0.02	0.14
B	-0.03	-0.04	-0.07	0.05	-0.10	0.01	0.11
								C	-0.04				-0.04	-0.08	0.05	-0.12	0.01	0.13
D	-0.03	-0.02	-0.07	0.04	-0.10	0.02	0.12
								E	-0.02				-0.04	-0.07	0.05	-0.09	0.01	0.10
F	-0.03	-0.03	-0.08	0.03	-0.11	0.02	0.13
								G	-0.03				-0.03	-0.07	0.04	-0.10	0.01	0.11
H	-0.04	-0.03	-0.09	0.05	-0.13	0.03	0.16
								I	-0.03				-0.02	-0.07	0.05	-0.10	0.03	0.13
Embodiment 6	9	15	A	-0.02	-0.06	-0.08	0.04												-0.10	-0.02	0.08
								B	-0.02	-0.05	-0.08	0.05	-0.10	0.00	0.10
			C	-0.03	-0.05	-0.09	0.04									-0.12	-0.01	0.11
								D	-0.02	-0.05	-0.09	0.03	-0.11	-0.02	0.09
			E	-0.02	-0.05	-0.08	0.05									-0.10	0.00	0.10
								F	-0.02	-0.06	-0.07	0.03	-0.09	-0.03	0.06
			G	-0.03	-0.06	-0.08	0.08									-0.11	0.00	0.11
								H	-0.02	-0.05	-0.08	0.04	-0.10	-0.01	0.09
			I	-0.03	-0.07	-0.07	0.04									-0.10	-0.03	0.07
								Embodiment 7	10	15	A	0.03	-0.06	-0.07	0.04				-0.04	-0.02	0.02
B	0.02	-0.05	-0.06	0.03	-0.04	-0.02	0.02
											C	0.02	-0.05	-0.06	0.04	-0.04	-0.01	0.03
D	0.02	-0.05	-0.06	0.04	-0.04	-0.01	0.03
											E	0.02	-0.05	-0.07	0.04	-0.05	-0.01	0.04
F	0.02	-0.06	-0.05	0.03	-0.03	-0.03	0.00
											G	0.03	-0.06	-0.07	0.00	-0.04	-0.03	0.01
H	0.03	-0.04	-0.06	0.03	-0.03	-0.01	0.02
											I	0.02	-0.08	-0.06	0.05	-0.04	-0.01	0.03
Embodiment 8	12	15	A	-0.04	-0.02	-0.09	0.04												-0.13	0.02	0.15
								B	-0.03	-0.02	-0.10	0.02	-0.13	0.00	0.13
			C	-0.05	-0.01	-0.08	0.04									-0.13	0.03	0.16
								D	-0.03	-0.01	-0.09	0.03	-0.12	0.02	0.14
			E	-0.03	0.00	-0.08	0.03									-0.12	0.03	0.15
								F	-0.04	-0.02	-0.08	0.03	-0.12	0.01	0.13
			G	-0.03	0.00	-0.07	0.04									-0.10	0.04	0.14
								H	-0.05	-0.02	-0.10	0.02	-0.15	0.00	0.15
			I	-0.04	-0.02	-0.08	0.03									-0.12	0.01	0.13
								Embodiment 9	14	15	A	-0.02	-0.05	-0.08	0.14				-0.10	0.09	0.19
B	0.00	-0.04	-0.07	0.15	-0.07	0.11	0.18
											C	-0.02	-0.05	-0.07	0.15	-0.09	0.10	0.18
D	-0.01	-0.03	-0.07	0.12	-0.08	0.09	0.17
											E	0.00	-0.04	-0.08	0.14	-0.08	0.10	0.18
F	-0.03	-0.05	-0.09	0.13	-0.12	0.07	0.19
											G	0.00	-0.04	-0.08	0.14	-0.08	0.10	0.18
H	-0.02	-0.04	-0.06	0.14	-0.08	0.10	0.18
											I	-0.03	-0.04	-0.04	0.13	-0.09	0.03	0.18
Comparative example 3	11	15	A	-0.07	-0.01	-0.10	0.05												-0.17	0.04	0.21
								B	-0.07	-0.02	-0.11	0.06	-0.18	0.04	0.22
			C	-0.05	-0.02	-0.11	0.05									-0.19	0.03	0.22
								D	-0.09	0.00	0.10	0.06	-0.19	0.06	0.25
			E	-0.08	-0.01	0.10	0.07									-0.18	0.06	0.24
								F	-0.08	-0.02	-0.10	0.05	-0.18	0.03	0.21
			G	-0.09	-0.02	-0.12	0.05									-0.21	0.03	0.24
								H	-0.07	0.00	-0.11	0.06	0.18	0.06	0.24
			I	-0.09	-0.02	-0.11	0.05									-0.20	0.03	0.23
								Reference example	13	15	A	0.01	-0.30	-0.05	0.00				-0.04	-0.30	0.26
B	0.02	-0.30	-0.04	0.01	-0.02	-0.29	0.27
											C	0.02	-0.31	-0.05	0.00	-0.03	-0.31	0.28
D	0.01	-0.29	-0.04	-0.01	-0.03	-0.30	0.27
											E	0.01	-0.29	-0.05	-0.02	-0.04	-0.31	0.27
F	0.00	-0.29	-0.04	0.00	-0.04	-0.28	0.24
											G	0.02	-0.30	-0.05	0.02	-0.03	-0.28	0.25
H	0.01	-0.30	-0.05	0.00	-0.04	-0.30	0.26
											I	0.01	-0.31	-0.06	0.01	-0.05	-0.30	0.25

Like this, when the characteristic of the adhering film shown in the comparative example 3 exceeded specified range, the result was that the dimensional change of flexible metallizing multilayer body becomes big.To this, in the characteristic of adhering film is embodiment 5～9 in the certain limit, suppressed the generation of the dimensional change of flexible metallizing multilayer body.

(embodiment 10)

With the polyamic acid solution that obtains in the DMF dilution synthesis example 21 after solid component concentration is 10 weight %, the two sided coatings polyamic acid of the Kapton (the wide 1000mm of film) that in synthesis example 16, obtains, make that the final single face thickness of thermoplastic polyimide layer (adhesive linkage) is 4 μ m, under 140 ℃, carry out heating in 1 minute then.Then, be under the 5kg/m at tension force, with 20 second time be 390 ℃ FAR INFRARED HEATING stove by atmosphere temperature degree, add hot-imide, obtain adhering film.

Use the rolled copper foil (BHY-22B-T, JapanEnergy company makes) of 18 μ m in the both sides of the adhering film that obtains, on the Copper Foil both sides, use protecting materials (Apical 125NPI again; Kaneka company makes), tension force at Kapton is 0.4N/cm, and laminating temperature is 360 ℃, and lamination pressure is 196N/cm (20kgf/cm), laminate speed is to carry out heat lamination continuously under 1.5m/ minute the condition, makes flexible metal-clad laminate of the present invention.

(embodiment 11)

The Kapton that the Kapton that obtains replaces obtaining in the synthesis example 16, carry out operation similarly to Example 10 in using synthesis example 17, make adhering film and flexible metal-clad laminate.

(embodiment 12)

The Kapton that the Kapton that obtains replaces obtaining in the synthesis example 16, carry out operation similarly to Example 10 in using synthesis example 18, make adhering film and flexible metal-clad laminate.

(comparative example 4)

The Kapton that the Kapton that obtains replaces obtaining in the synthesis example 16, carry out operation similarly to Example 10 in using synthesis example 19, make adhering film and flexible metal-clad laminate.

(reference example)

The Kapton that the Kapton that obtains replaces obtaining in the synthesis example 16, carry out operation similarly to Example 10 in using synthesis example 20, make adhering film and flexible metal-clad laminate.

Use the adhering film that obtains in each embodiment, the comparative example and the evaluation result of the characteristic of the flexible metal-clad laminate that obtains is shown in the table 13,14.And, as shown in Figure 5 for the evaluation (sampling method) of adhering film and flexible metal-clad laminate.

Table 12 illustrates heating, the stretching condition of synthesis example 16～20.

[table 13]

Table 13

	Heating, elongation condition
					Temperature	Residence time	Tension force
	℃	Second	kg/m	kg/mm 2
					Synthesis example 16	460	45	8.0	0.32
Synthesis example 17	510	45	8.0	0.32
					Synthesis example 18	510	45	12.7	0.51
Synthesis example 20	-	-	-	-
					Synthesis example 19	510	45	20.1	0.80

Table 14 illustrates the modulus of elasticity measurement result of the adhering film of embodiment 10～12, comparative example 4, reference example.

Table 14

	Modulus of elasticity		Modulus of elasticity MD/TD ratio
				MD	TD
	G Pa	G Pa
				Embodiment 10	4.10	3.50	1.17
Embodiment 11	4.35	3.39	1.28
				Embodiment 12	4.71	3.18	1.48
Comparative example 4	3.80	3.95	0.96
				Reference example	5.81	2.88	2.02

Table 15 illustrates the dimensional change measurement result of embodiment 10～12, comparative example 4, reference example.

[table 15]

Table 15

	Dimensional change locates	Dimensional change
										After the etching (%)			Heating back (%)		Accumulation (after the etching+the heating back) (%)
		MD	TD	The difference of MD and TD	MD	TD	MD	TD	The difference of MD and TD
										Embodiment 10	A	-0.19	0.09	0.28	-0.12	0.13	-0.31	0.22	0.53
B	-0.20	0.08	0.28	-0.12	0.12	-0.32	0.20	0.52
									C		-0.18	0.09	0.27	-0.12	0.15	-0.30	0.24	0.54
D	-0.18	0.08	0.26	-0.11	0.14	-0.29	0.22	0.51
									E		-0.19	0.08	0.27	-0.12	0.13	-0.31	0.21	0.52
F	-0.19	0.09	0.28	-0.12	0.14	-0.31	0.23	0.54
									Embodiment 11		A	-0.18	0.07	0.25	-0.13	0.16	-0.31	0.23	0.54
B	-0.17	0.06	0.23	-0.11	0.16	-0.28	0.22	0.50
										C	-0.18	0.08	0.26	-0.13	0.15	-0.31	0.23	0.54
D	-0.17	0.06	0.23	-0.13	0.15	-0.30	0.21	0.51
										E	-0.16	0.08	0.24	-0.11	0.16	-0.27	0.24	0.51
F	-0.18	0.06	0.24	-0.11	0.15	-0.29	0.21	0.50
										Embodiment 12	A	-0.12	0.02	0.14	-0.11	0.18	-0.23	0.20	0.43
B	-0.10	0.04	0.14	-0.10	0.15	-0.20	0.19	0.39
									C		-0.15	0.00	0.15	-0.09	0.18	-0.24	0.18	0.42
D	-0.13	0.00	0.13	-0.10	0.15	-0.23	0.15	0.38
									E		-0.12	0.03	0.15	-0.11	0.16	-0.23	0.19	0.42
F	-0.12	0.02	0.14	-0.08	0.17	-0.20	0.19	0.39
									Comparative example 4		A	-0.27	0.26	0.53	-0.18	0.19	-0.45	0.45	0.90
B	-0.27	0.27	0.54	-0.19	0.16	-0.46	0.43	0.89
										C	-0.25	0.26	0.51	-0.20	0.18	-0.45	0.44	0.89
D	-0.25	0.27	0.52	-0.19	0.17	-0.44	0.44	0.88
										E	-0.26	0.26	0.52	-0.18	0.18	-0.44	0.44	0.88
F	-0.27	0.26	0.53	-0.19	0.17	-0.46	0.43	0.89
										Reference example	A	0.59	-0.48	1.07	0.11	0.15	0.70	-0.33	1.03
B	0.60	-0.47	1.07	0.11	0.16	0.71	-0.31	1.02
									C		0.60	-0.47	1.07	0.10	0.14	0.70	-0.33	1.03
D	0.58	-0.48	1.06	0.12	0.17	0.70	-0.31	1.01
									E		0.61	-0.49	1.10	0.13	0.15	0.74	-0.34	1.08
F	0.59	-0.48	1.07	0.10	0.15	0.69	-0.33	1.02

Like this, when the characteristic of the adhering film shown in the comparative example 4 exceeded specified range, the result was that the dimensional change of flexible metallizing multilayer body becomes big.To this, in the characteristic of adhering film is embodiment 10～12 in the certain limit, suppressed the generation of the dimensional change of flexible metallizing multilayer body.

Claims (18)

1. adhering film, it is provided with the adhesive linkage that contains thermoplastic polyimide at least one surface of Kapton, and wherein, the linear expansivity of this adhering film satisfies:

1.0＞(linear expansivity of MD direction)/(linear expansivity of TD direction)＞0.1

(linear expansivity is the mean value in 100～200 ℃).

2. adhering film, it is provided with the adhesive linkage that contains thermoplastic polyimide at least one surface of Kapton, and wherein, this adhering film is a quantity-produced, and this adhering film satisfies at the linear expansivity of whole width simultaneously:

1.0＞(linear expansivity of MD direction)/(linear expansivity of TD direction)＞0.1

(linear expansivity is the mean value in 100～200 ℃).

3. the described adhering film of claim 2, wherein, above-mentioned adhering film is the wide above long size film of 250mm that is.

4. claim 2 or 3 described adhering films are wherein, by a pair of above metallic roll heating and pressurization, superimposed with tinsel continuously.

5. flexible metal-clad laminate, it obtains by applying tinsel on any one described adhering film in claim 1～4.

6. the manufacture method of a flexible metal-clad laminate, wherein, limit heating and add described adhering film of the continuously superimposed claim 1～3 of flanging and tinsel.

7. adhering film, it is provided with the adhesive linkage that contains thermoplastic polyimide at least one surface of Kapton, wherein, the modulus of elasticity of the MD direction of this adhering film is more than the 5GPa, and satisfies 1.70＞(modulus of elasticity of MD direction)/(modulus of elasticity of TD direction)＞1.05.

8. adhering film, it is provided with the adhesive linkage that comprises thermoplastic polyimide at least one surface of Kapton, wherein, this adhering film is a quantity-produced, and, satisfy 1.70＞(modulus of elasticity of MD direction)/(modulus of elasticity of TD direction)＞1.05 when the modulus of elasticity on the MD direction in the whole width of this adhering film is 5GPa when above.

9. the described adhering film of claim 8, wherein, above-mentioned adhering film is the wide above long size film of 250mm that is.

10. claim 8 or 9 described adhering films are wherein, by a pair of above metallic roll heating and pressurization, superimposed with tinsel continuously.

11. a flexible metal-clad laminate, it obtains by applying tinsel on any one described adhering film in claim 7～10.

12. the manufacture method of a flexible metal-clad laminate, wherein, limit heating and add described adhering film of the continuously superimposed claim 7～9 of flanging and tinsel.

13. adhering film, it is provided with the adhesive linkage that contains thermoplastic polyimide at least one surface of Kapton, wherein, modulus of elasticity on the MD direction of this adhering film is lower than 5GPa, and satisfies 2.00＞(modulus of elasticity of MD direction)/(modulus of elasticity of TD direction)＞1.10.

14. adhering film, it is provided with the adhesive linkage that contains thermoplastic polyimide at least one surface of Kapton, wherein, this adhering film is a quantity-produced, and when the modulus of elasticity on the MD direction in the whole width of this adhering film is lower than 5GPa, satisfy 2.00＞(modulus of elasticity of MD direction)/(modulus of elasticity of TD direction)＞1.10.

15. the described adhering film of claim 14, wherein, above-mentioned adhering film is the wide above long size film of 250mm that is.

16. claim 14 or 15 described adhering films are wherein, by a pair of above metallic roll heating and pressurization, superimposed with tinsel continuously.

17. a flexible metal-clad laminate, it is to obtain by applying tinsel on any one the described adhering film in claim 13～16.

18. the manufacture method of a flexible metal-clad laminate, wherein, limit heating and add described adhering film of the continuously superimposed claim 13～15 of flanging and tinsel.

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