TW200930563A - Metal laminate - Google Patents

Abstract

The subject of the present invention is to provide a flexural metal laminate and a flexural printed substrate having excellent flexural property, bending resistance, resistance to heat confidence, hygroscopic property, and size accuracy, which can be produced inexpensively. The present invention provides a flexural metal laminate, which is characterized in that the flexural metal laminate is formed by laminating a metal foil on at least one side of a resin film resistant to heat, and the said resin film resistant to heat consists of two layers of polyamideimide resin soluble to organic solvents, wherein one layer is formed by a resin layer having 4800MPa and less of elastic module, having (a) 80 mole% and more of monomer having phenalene group, while the amount of acid component being 100 mole%, the amount of amine component being 100%, and the total amount of acid component and amine component being 200 mole%; (b) the mole ratio of imide bonds and amide bonds being 99/1 to 60/40; and (c) the imidized ratio of imide bonds being 50% and more; and the remaining another layer is formed by a low humidity expansion resin layer having 20ppm and less of the humidity expansion coefficient.

Description

[Technical Field] The present invention relates to a flexible metal laminate and a flexible printed circuit board in which a metal foil is laminated on at least one surface of a heat resistant resin film, and more specifically, A flexible metal excellent in flexibility, such as peeling strength after soldering, heat resistance after soldering treatment, and heat resistance reliability and humidity dimensional change rate, which are excellent in flexibility, folding resistance, and insulation properties. Laminated body, flexible printed circuit board. The "flexible metal-clad laminate" as used in the specification and the patent application refers to a laminate formed of a metal foil and a resin layer, for example, a useful laminate such as a flexible printed substrate. In addition, the "flexible printed circuit board" is, for example, a part which can be manufactured by a conventionally known method such as a subtractive process using a metal-clad laminate, and a cover film or screen printing ink is used as necessary. Or a fully printed circuit board (FPC), a flexible printed circuit board (FPC), a flat cable, a tape for Tape Automated Bonging (TAB), or a TCP (tape-wrap package); Tape Carrier Package) A general term for boards for packaging (Chip On Flexible substrates, etc.). [Prior Art] A flexible metal-clad laminate system for a flexible printed circuit board is formed by laminating a polyimide film and an adhesive such as an epoxy resin or an acrylic resin modified with a rubber foil. . The flexible printed circuit board formed by the flexible metal-clad laminate which is bonded by using the adhesive has a heat resistance of 200930563, because the heat resistance of the adhesive is significantly inferior to that of the polyimide film. Poor thermal stability, insulation reliability, etc. In order to solve such problems, there is a proposal (for example, 1, 2) to disclose a technique in which a non-adhesive layer is formed by directly applying a resin solution to a metal foil. Layer structure (two-layer CCL) technology. However, these two-layer CCL points: • Since the coated polyimine-based resin is not dissolved in the precursor, i.e., the poly-proline solution, it must be imidized by gold treatment. Therefore, the workability of the resin film layer formed on the metal foil is improved in the above-described workability and bending resistance in order to improve the above-described workability and bending resistance of the flexible printed circuit board. The proposal discloses a technique in which an organic solvent is used and a resin composition having a low modulus of elasticity of a film is a foil and dried to form a two-layer CCL. However, in this case, although the workability and the bending resistance are excellent, the dimensional accuracy such as the chemical conversion rate and the peeling strength after the soldering treatment are inferior, and there is a so-called COF substrate (clip-chip) which is not suitable for packaging a semiconductor element. A soft-flexible substrate; a use of a Chip-on-line, or a high-density circuit board, and a high-density circuit board is required. [Patent Document 1] JP-A-57-66690 [Patent Document 2] JP-A-57-66690 [Patent Document 3] JP-A-2001-105530, SUMMARY OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION The coated polyimine metal-clad laminate has the following unsuitable solvent, and is coated with a high temperature heat on a foil. The purpose of the folding resistance is to overcome the disadvantages such as a heat-resistant letter (TCP package) or a flexible substrate which is soluble in a resin group which is directly applied to gold and which is used for humidity dimensional change. 200930563 The object of the present invention is to solve the above problems, and in particular to provide a flexible metal laminate and flexibility for manufacturing a flexible printed circuit board for use in a high-density circuit board requiring fine pitch. Printed substrate. That is, the object of the present invention is to provide excellent heat resistance and reliability such as excellent flexibility and folding resistance, small dimensional change rate, high Tg, peel strength after soldering treatment, and solder heat resistance after humidification treatment. A flexible metal laminate or a flexible printed circuit board made of an excellent substrate material. [Means for Solving the Problem] The inventors of the present invention have focused on the layer structure and processing method of a resin composition containing a soluble agent and having excellent heat resistance and a flexible printed circuit board containing the same. As a result of the discussion, the present invention has been achieved. That is, the present invention is the following flexible metal-clad laminate or flexible printed circuit board. (1) A flexible metal laminate which is characterized in that a flexible metal laminate is formed by laminating a metal foil on at least one surface of a heat resistant resin film, and the heat resistant resin film is made of a polysiloxane which is soluble in an organic solvent. A two-layer structure composed of an amine imine resin, wherein one layer is a) the total amount of the acid component is 100 mol%, the total amount of the amine component is 1 mol%, and the total of the acid component and the amine component. When it is 200 mol%, the monomer component having a naphthyl group is 80 mol% or more, and b) the ratio of the quinone imine bond to the guanamine bond is 99/1 to 60/4 0 molar ratio, Ο醯亚The amine bond having an oxime imidization ratio of 50% or more is formed of a resin layer having an elastic modulus of 4,800 MPa or less, and the remaining other layer is formed of a low-humidity expandable resin having a humidity expansion coefficient of 2 Oppm or less. 200930563 (2) The flexible metal laminate according to (1), which is formed by laminating a metal foil on one side, wherein the heat-resistant resin layer on the side in contact with the metal foil is a) the total amount of the acid component is 100. When the total amount of the molar % and the amine component is 200% by mole of the total of the acid component and the amine component, the monomer component having a naphthyl group is 80 mol% or more, and b) The ratio of the amine bond to the guanamine bond is 99/1 to 60/40 molar ratio, c) the yttrium imine bond has a yttrium imidation ratio of 50% or more and a resin layer having an elastic modulus of 4,800 MPa or less, and The resin layer on the side not in contact with the metal foil is a low-humidity expandable resin layer having a humidity expansion coefficient of 20 ppm or less. (3) A flexible metal laminate which is characterized in that a flexible metal laminate such as (1) or (2) is formed by forming a metal foil on one side, wherein a low humidity expansion property having a humidity expansion coefficient of 2 Oppm or less The resin is a) a monomer having a biphenyl group when the total amount of the acid component is 100 mol%, the total amount of the amine component is 100 mol%, and the total of the acid component and the amine component is 200 mol%. It is 100 mol% or more, and b) the ratio of the quinone imine bond to the brewing amine bond is 99/1 to 65/35 molar ratio, and c) the sulfhydryl imidation ratio of the quinone imine bond is 50% or more. (4) The flexible metal laminate according to any one of (1) to (3), wherein a) the total amount of the acid component is taken as 100 mol%, and the total amount of the amine component is 1 mol% When the total of the acid component and the amine component is 200 mol%, the monomer component having a naphthyl group is 80 mol% or more, and b) the ratio of the quinone bond to the guanamine bond is from 99/1 to 60/40. Mohr ratio, c) The yttrium imidization ratio of the yttrium imine bond is 50% or more, and the thickness (T1) of the resin layer having an elastic modulus of 4800 MPa or less and the humidity expansion of 200930563 are low humidity expansion resins of 20 ppm or less. The ratio of the thickness (T2) of the layer (Τ1)/(Τ2) is from 0.05 to 5. (5) A double-sided flexible metal laminate obtained by laminating a flexible metal laminate according to any one of (1) to (4) in such a manner that a metal foil is formed on both sides. A flexible printed circuit board obtained by the flexible metal-clad laminate according to any one of (1) to (5).

[Effects of the Invention] The flexible metal laminate system of the present invention is composed of a plurality of resin compositions which are excellent in flexibility, folding resistance, and adhesion, and have a small change in humidity size and a high Tg, and are formed and processed by the layer. The conditions, the folding resistance, the peel strength after the soldering treatment, and the solder heat resistance after the humidification treatment are excellent in heat resistance and dimensional accuracy. Further, since the resin composition to be used is soluble in an organic solvent, it is not required to be heat-treated at a high temperature and can be produced inexpensively. Therefore, it is industrially advantageous because it can inexpensively manufacture a flexible substrate which can be used for high-density packaging applications such as COF substrates. [Embodiment] The flexible metal laminate system of the present invention is composed of two layers of a resin film layer, and a metal ruthenium foil is laminated on at least one surface of the resin film layer. The resin used in the two-layer resin film layer is composed of a polyamidoximine resin which is soluble in an organic solvent. Among the two-layered resin films, one layer is formed of a resin film having an elastic modulus of 4,800 MPa or less, preferably 4,500 MPa or less, more preferably 4,300 MPa or less (hereinafter referred to as a low-elastic modulus resin layer), and The first layer is formed of a resin film layer (hereinafter referred to as a low-humidity expandable resin layer) having a humidity expansion coefficient of 20 ppm or less, preferably 15 ppm - 10 200930563 or less, more preferably 13 ppm or less. When the elastic modulus of the low elastic modulus resin layer is more than 480 OMPa, the flexibility and the folding resistance of the flexible metal laminate are deteriorated, and the heat resistance and the like such as the adhesion strength and the peel strength after the solder treatment are deteriorated. Further, in particular, when the elastic modulus of the low-elastic modulus resin layer is increased, the solder heat resistance of the humidifying treatment is remarkably lowered, and particularly, the humidity expansion coefficient of the low-humidity expandable resin layer is remarkable. tendency. Although it is not known for a clear reason, it is presumed that the soldering process at the time of the humidification treatment is a task of buffering the desorption moisture or thermal expansion generated during the soldering process. Further, when the humidity expansion coefficient is more than 20 ppm, the humidity dimensional change rate is high, the dimensional accuracy is deteriorated, and the heat resistance reliability such as the solder heat resistance of the humidification treatment is also deteriorated. Although the elastic modulus of the low elastic modulus resin layer is preferably as low as possible, it is preferably 100 MPa or more. When it is less than 1000 MPa, handling properties and handling properties may be lowered. Further, although it is determined that the required performance is determined, it is not limited to 2000 MPa or more, and further preferably 2500 MPa or more. Although the humidity V expansion coefficient is preferably as low as possible, it is preferably 1 ppm or more. Although it is determined by the required performance, it is not inconsistent, more than 5 ppm, and more preferably more than 7 ppm. Since the humidity expansion coefficient of the metal foil is theoretically 0 ppm, the lower the humidity expansion coefficient of the low-humidity expandable resin layer is. In addition, in the resin film layer of the two layers, the heat-resistant resin layer on the side in contact with the metal foil is a low-humidity-expandable resin layer, and the heat-resistant reliability such as peeling after the soldering treatment can be obtained. A flexible metal laminate having excellent bendability and folding resistance is preferred. Although it is not known for a clear reason, it is predicted that the low elastic modulus -11-200930563 resin layer is disposed on the side in contact with the metal foil, and since the layer exhibits cushioning properties, it is excellent in properties such as bendability and folding resistance. Further, although the low elastic modulus resin layer has a tendency to have a hygroscopic expansion coefficient higher than usual, it is expected that the heat resistant resin layer on the side in contact with the metal foil is a low elastic modulus resin layer, and is not bonded to the metal foil. The heat-resistant resin layer on the contact side is a low-humidity expandable resin layer, and the metal foil layer and the low-humidity expandable resin layer sandwich the low-elastic modulus resin layer, and the structure of the metal laminate is a low-elastic modulus resin layer. Since it is not easily affected by the humidity, the heat resistance and the reliability of the solder heat resistance after the humidification treatment are also excellent, but the reason is not clear. The heat resistant resin film used in the present invention may be, for example, a polyimine, a polyamidimide resin, a polyether quinone, a polyester quinone, a poly-panic acid, a polyallyl ester, or an aromatic poly Aramid (Aramid) and the like are classified into resins in the category of so-called engineering plastics having excellent heat resistance. In terms of heat resistance, dimensional accuracy, etc., it is preferred to use polyimine and polyamidimide, and from the viewpoint of processability, it is soluble in organic solvent-based polyimine and polyamidimide. More preferably, a polyamidoximine which is soluble in an organic solvent is preferred. [Low modulus of elasticity resin layer] In the low elastic modulus resin layer, a necessary condition for satisfying the implementation of the present invention is that the total amount of the acid component is 100% by mole and the total amount of the amine component is 100 moles. When the total of the acid component and the amine component is 200 mol%, the monomer component having a naphthyl group is 80 mol% or more of a polyamidoximine resin. The monomer component having a naphthyl group is preferably 90 mol% or more, more preferably 100 mol% or more, and the naphthyl group is less than 80 mol%, because the moisture absorption property is deteriorated, and the humidity dimensional change rate is dimensionally accurate. Since the requirements of the present invention are not satisfied and the heat resistance is also lowered, the peeling strength after the soldering treatment and the heat resistance such as the solder heat resistance after the humidification treatment of -12-200930563 are also lowered. Further, the monomer component having a naphthyl group is preferably 170 mol% or less, more preferably 160 mol% or less, and still more preferably 150 mol% or less. When it is more than 170 mol%, there is a tendency that the modulus of elasticity rises and the solubility decreases. The molar ratio of the quinone bond to the guanamine bond is from 99/1 to 60/40 mol ratio. The molar ratio of the quinone bond to the guanamine bond is preferably from 99/1 to 75/25, more preferably from 90/10 to 80/20. When the molar ratio of the quinone bond to the guanamine bond is less than 60/40, the heat resistance and the heat resistance are deteriorated, and in particular, the peel strength after the solder treatment is lowered. Further, when the ratio is more than 99/1, the "modulus of elasticity becomes high", and the folding resistance and the bending property are lowered. Further, since the solubility is also deteriorated, the workability of the flexible metal laminate is deteriorated. When a preferred embodiment of the low elastic modulus resin layer having an elastic modulus of 4,800 MPa or less used for achieving the object of the present invention is used, it is preferable to use the unit represented by the general formula (1) as an essential component. The polyaminoamine quinone imine resin having a repeating unit containing at least one unit selected from the group consisting of the general formula (2), the general formula (3) and the general formula (4) in the molecular chain is more preferable. In the 'general formula (2), in particular, in terms of low elastic modulus, Tg, heat resistance, adhesion to copper foil, 'X is S02 or direct bonding (biphenyl), or n = 0 Preferably, direct bonding (biphenyl) or n = 0 is preferred. Further, in the general formula (3), in the same manner as described above, in terms of low elastic modulus, Tg, heat resistance reliability and adhesion to copper foil, γ is a diphenylketone type (co) or a direct bond. Type (biphenyl) is preferred. Further, the units represented by the following general formula (2) and the general formula (3) may be used alone or in combination. Further, a substituent may be bonded to the naphthalene skeleton or the benzene skeleton. The lower the elastic modulus is, the better it is 'so' to take the ratio of the general formula (1) relative to {the general formula (2) + the general formula (3) + the general formula (4)} 'and relative to the 醯- 13- 200930563 Amine bond is preferred as a means to reduce the proportion of quinone bond. The content ratio of the general formula (1), the general formula (2), the general formula (3), and the general formula (4), and the content ratio is {general (1)} / {formula (2) + formula (3) + General formula (4)} = 1/99~40/60 (mole ratio) is preferable, and the molar ratio of the quinone bond to the guanamine bond is 99/1 to 60/40 molar ratio. With {Formula(1)}/{Formula (2) + Formula (3) + Formula (4)} = 1 0/9 0~3 0/70 (Mohr ratio) and the quinone bond The molar ratio of the guanamine bond is preferably from 99/1 to 75/25, and is represented by the formula (1)}/{Formula (2) + Formula (3) + Formula (4)} = 10/ 90 to 2 0/8 0 (mole ratio) and the molar ratio of the quinone bond to the guanamine bond is preferably 90/10 to 80/20. Heat resistance (Tg when the content ratio of the general formula (1)} / { general formula (2) + general formula (3) + general formula (4)} is more than 4 〇 / 6 〇 or less than 1 / 99 ), each of the low elastic modulus and the adhesion to the copper foil tends to be difficult to be combined. In particular, when the content ratio of the general formula (2) + the general formula (3) + the general formula (4)} is more than 40/60, the heat resistance is deteriorated, and when it is less than 1/99, the solubility to the solvent is deteriorated and resistant. There is a tendency for the folding to decrease. Further, when the molar ratio of the quinone bond to the guanamine bond is less than 60/40, the heat resistance and the heat resistance are deteriorated, and in particular, the peel strength after the solder treatment is lowered. When the molar ratio of the quinone bond to the guanamine bond is more than 9 9/1, the elastic modulus becomes high, and the folding resistance and the bending property are deteriorated. Further, since the solubility is also deteriorated, the workability of the flexible metal laminate is also deteriorated. Further, from the viewpoint of heat resistance and moisture absorption characteristics, a preferred embodiment is a component comprising a guanidine-forming component of the formula (2) and a quinone imine component of the formula (3) and/or the formula (4). The ratio is adjusted to a molar ratio of {general formula (2)}/{formula (3) + general formula (4)} = 5/95 to 95/5. When the content of the formula (2) in the formula (2), the formula (3) and/or the formula (4) is less than 5 mol%, the hygroscopic property may be deteriorated. Moreover, when it is more than 95% by mole, heat resistance tends to be deteriorated. Illustrative-14 - 200930563 In a preferred embodiment, the formula (1) is a repeating unit derived from benzenetricarboxylic anhydride and 1,5-naphthalene-isocyanate, and the general formula (2) is derived from citric acid and 1 , a repeating unit of 5-naphtho-isocyanate, the general formula (3) is derived from a repeating unit of biphenyltetracarboxylic dianhydride, and/or diphenyl ketone tetracarboxylic dianhydride and hydrazine, 5-naphthyl diisocyanate The ratio of the formula is {general formula (2) + formula (3) + formula (4)} = 1/99 to 40/60 molar ratio, and {general formula (2)} / {general formula (3)}=10/90~90/10 Mo ratio is better. In the above formula (1), formula (2), formula (3) and formula (4), the content of the formula (1) is more than 40 mol%, and the heat resistance and hygroscopic property are lowered, When it is less than 1 mol%, there is a tendency that the solvent solubility is deteriorated or the film elastic modulus is also high. Further, in the general formula (2), the general formula (3), and the general formula (4), when the content of the general formula (2) is less than 10 mol%, the hygroscopic property may be lowered, and it may be more than 90 m. When % is used, the solvent solubility of the resin tends to be deteriorated. A preferred aspect of the above-described embodiments will be described. It is particularly preferable that the ratio of the formula (2) 'the indole bond is in the para position to each other and the ratio of the mutual ratio to the meta position to satisfy the alignment/meta position = 5/95 to 100/0 mol%. It is better to satisfy the align/meta position when the ratio of the guanamine bond to the alignment of each other and the ratio of the ratio of the meta-positions to each other to satisfy the align/meta position = 20/80 to 100/0 mol%. = 50/50~100/0% when it is the best. When the alignment is 5 mol% or less, the effect of improving the heat resistance tends to be deteriorated. Further, from the viewpoint of environmental considerations, the polyamidimide resin is preferably a halogen-free one which does not contain a halogen such as fluorine, chlorine, bromine or iodine. The ruthenium imine bond of the polyamidoximine resin must have a ruthenium imidation ratio of 50% or more. More preferably 90% or more, and more preferably 95% or more. The higher the yield of hydrazine, the better, and the upper limit is 1 〇 0%. When the ruthenium imidization ratio of the quinone imine bond is less than 50% -15 to 200930563, the adhesion between the low elastic modulus resin film and the low moisture absorbing resin film is deteriorated, and there is a tendency for peeling between the resin layers, and soldering After the treatment, etc., the peel strength is lowered. As a result, reliability such as folding resistance, flexibility, and heat resistance (peeling strength) tends to be deteriorated. The reason for this is presumed to be that when the second layer is laminated before the completion of the hydrazine imidization reaction of the first layer, the hydrazine imidization reaction proceeds with heating in the subsequent processing, and the condensation water generated therewith Characteristics such as folding resistance between the resin layers or the interface between the resin and the metal foil cause adverse effects. Therefore, the resin composition used in the present invention is preferably obtained by a method such as an isocyanate method described later, in which the quinone imidization of the resin varnish obtained after the polymerization is completed, and of course, it can be dissolved in a polymerization solvent. The composition is preferably soluble in an organic solvent. Further, even if it is produced by the isocyanate method, the imidization reaction is not completed after polymerization, and the production conditions must be paid attention to due to the influence of the purity of the monomer or the type of the solvent. In order to make the ruthenium iodide ratio 50% or more, it is preferred to synthesize the precursor by the usual method in the amine method and slowly raise the temperature to above Tg after the film formation, and in the vicinity of Tg (± l 〇 ° C ) The mixture was heated for about 1 hour to carry out sufficient hydrazide treatment. Further, in the isocyanate method, it is preferred to increase the water content to 50 mol% or less of the monomer mole number during the polymerization, or to increase the purity of the monomer. For example, when the ring closure ratio of the 1,2,4-benzenetricarboxylic anhydride is high, the purity of the monomer such as the amount of the diamine component of the impurity in the diisocyanate component is preferably high. Further, the oxime imidization ratio can be measured, and the method described in the examples below can be used. Further, in terms of workability in forming a laminated film of a flexible metal-clad laminate or a pressure-sensitive adhesive layer to be described later, the polyamidoximine resin must be soluble in an organic solvent at -16 to 200930563. Further, the organic solvent referred to herein is selected from, for example, N-methyl-2-pyrrolidone, hydrazine, hydrazine dimethylformamide, hydrazine, hydrazine dimethyl acetamide, 1,3-two. At least one of a group consisting of methyl-2-imidazolidinone, tetramethylurea, cyclobutyl hydrazine, dimethyl hydrazine, r-butyrolactone, cyclohexanone, cyclopentanone, etc., or such Part of the use is selected from at least one selected from the group consisting of toluene, xylene, diglyme, triglyme, tetrahydrofuran, methyl ethyl ketone, and methyl isobutyl ketone. Adult. Further, in the present invention, the organic solvent is soluble in any one of the above-mentioned individual solvents or at least one of the mixed organic solvents containing at least one of hydrazine and 20% or more. It is preferably 15% by weight or more, more preferably 20% by weight or more. Further, the dissolution was judged by adding a predetermined weight of the resin powder passing through 80 mesh in a 200 ml beaker, and the solution after being smoothly stirred at 25 ° C for 24 hours was allowed to stand at 25 ° C for 24 hours to gel. Any one of the undistributed, non-uniform, white turbid, and precipitated was judged to be dissolved. In order to be soluble in a solvent, it can be achieved by the following method, etc. (1) The preferable resin composition mentioned above is employ|adopted. (2) Lowering the ratio of quinone imine/melamine groups. (3) A polycarboxylic acid component having a alicyclic group to be described later and a polyamine component are copolymerized. (4) A polycarboxylic acid component having a fatty group to be described later and a polyamine component are copolymerized. (5) Introducing a bendable group into the aromatic ring. (6) Introducing bulky compounds into the polymer chain. (7) Polymer modification is carried out using an epoxy compound or the like described later. As described above, by using a naphthalene skeleton as a main skeleton and a key ratio of -17 to 200930563, the rigidity/bending property of the polymer chain itself, the intermolecular force between the polymer chains, and the surface alignment property are relatively good. The ground balance can achieve the object of the present invention such as solvent solubility, low modulus of elasticity, and heat resistance. Ο Λ

(1) •• General formula (1)

(Υ indicates that the oxygen atom, CO or OOC-R-COO' η represents 0 or 1, and R represents a divalent organic group) -18- 200930563 ο ο

• General formula (4) [Low humidity expandable resin layer] The low humidity expandable resin layer must be formed of a polyamidoximine resin having a humidity expansion coefficient of 20 ρηη or less. The humidity expansion coefficient is preferably from i5PPm ® or less, and more preferably a polyamidoximine resin film layer (low-humidity expandable resin layer) of 13 PP or less. When the total amount of the acid component is 100 mol%, the total amount of the amine component is 100 mol%, and the total of the acid component and the amine component is 200 mol%, the low-humidity expandable resin layer has a biphenyl group. The monomer component is preferably 100 mol or more, more preferably 1 20 mol% or more, and most preferably 1 40 mol% or more. When the biphenyl group is less than 100% by mole, the dimensional reliability of the moisture absorption characteristics, the dimensional change rate of the moisture absorption, and the solder heat resistance of the humidification treatment tend to deteriorate. Further, the monomer having a biphenyl group is preferably 180 mol% or less, more preferably 170 mol% or less, and most preferably 160 mol% or less. When it is more than 180 mol%, the solubility tends to decrease. Here, the molar ratio of the quinone bond to the guanamine bond is preferably from 99/1 to 65/3 5 molar ratio, more preferably from 90/10 to 70/30 molar ratio. When the molar ratio of the quinone bond to the guanamine bond is less than 6 5/3 5 , the dimensional accuracy such as the peel strength or the moisture absorbing dimensional change rate after the solder treatment is deteriorated' and the peel strength after the humidification treatment The heat resistance and the moisture resistance of the solder heat resistance after the humidification treatment tend to be deteriorated. When the molar ratio of the amine bond is more than 9 9/1, the solubility is deteriorated, and the elastic modulus is increased, the folding resistance, and the bending property tend to be deteriorated. When a preferred embodiment of the low-humidity expandable resin layer having a humidity expansion coefficient of 20 ppm or less, which is used for the purpose of the present invention, is given, the general formula (5), the general formula (6), and the The repeating unit constituted by the formula (7) is an essential component, and the copolymerization ratio thereof is {general (5)} / {formula (6)} / general formula (7)) = 30 to 75/10 to 50 / Polyamine amide resin of 10 to 50 (mole ratio). It is more preferable to {general (5)} / { general formula (6)} / general formula (7)) = 35~65/10~3 0/20~5〇 (mole ratio), {general formula ( 5)}/{Formula (6)}/Formula (7)) = 40~5 0/10~25/2 5~40 (Morbi) is the best. Here, the molar ratio of the quinone bond to the guanamine bond is preferably from 99/1 to 65/35, and the molar ratio is preferably from 90/10 to 70/30. When the general formula (5) is more than 75 mol% and the general formula (6) or the general formula (7 is less than the lower limit thereof, the dimensional accuracy such as the moisture absorption dimensional change ratio is increased, or the peeling after the humidification treatment is performed. The heat resistance and the moisture resistance of the solder heat resistance after the humidification treatment tend to be deteriorated. Further, the general formula (5) is less than 30%, and the general formula (6) and the general formula (7) are each When it is larger than the upper limit, the solubility is poor, and the elastic modulus of the resin film becomes high, and it is difficult to secure the object of the present invention, that is, the flexibility and the folding resistance. Further, the oxime bond and the guanamine bond When the molar ratio is 65/3 5, the dimensional accuracy such as the peel strength after the soldering treatment or the moisture absorbing dimensional change rate is deteriorated, and the peeling strength after the humidification treatment and the solder heat resistance after the humidification treatment The heat resistance and moisture resistance tend to be deteriorated. When the molar ratio of the quinone bond to the guanamine bond is more than 99/1, the solubility is deteriorated, and the elastic modulus is increased, and the folding resistance is high. The tendency of the characteristics and the bending property is deteriorated. Especially among the acid component and the amine component, the optimum combination is used with two-20-2 00930563 When a monomer having a 2-substituted biphenyl group such as methyldiaminobiphenyl, the acid component is 1,2,4-benzenetricarboxylic anhydride, 3,3',4,4'-diphenylketone IV a combination of carboxylic acid dianhydride and 3,3',4,4'-biphenyltetracarboxylic dianhydride, and the amine component is 3,3'-dimethyl-4,4'-diaminobiphenyl The layer is formed of a resin film layer (low-humidity expandable resin layer) having a humidity expansion coefficient of 20 ppm or less, and the humidity expansion coefficient is preferably as low as possible. Therefore, the amount of the stretched phenyl group is increased or The ratio of the guanidine bond to the guanamine bond is increased or the yttrium imidation ratio is preferably increased. Here, in the formula (7), Y is preferably a direct bond (biphenyl bond) or an ether bond, particularly In terms of dimensional accuracy such as low moisture absorption dimensionality, direct bonding (biphenyl bond) is more preferable. Further, each unit type represented by the following formula (7) is one or two species. Further, from the viewpoint of environmental considerations, it is preferred that the polyamidoximine resin does not contain a halogen-free one such as fluorine, chlorine, bromine or iodine. The bond imidization ratio is preferably 5 More than 0%, more preferably 90% or more, more preferably 95% or more. The higher the ruthenium imidation rate, the higher the ratio is 1 〇〇%. The ruthenium imidization ratio of the quinone imine bond is less than 50. When the % is low, the adhesion between the low-elasticity modulus resin film and the low-humidity-expandable resin film is deteriorated, and there is a tendency for peeling between the resin layers. After the soldering treatment, the peel strength is lowered. As a result, the folding resistance and the flexibility are improved. The reliability of heat resistance (peeling strength) and the like tends to be deteriorated. The reason for this is that the heat treatment such as heat treatment is performed before the completion of the sulfimine reaction of the second layer. In the present invention, the hydrazine imidization proceeds with heat treatment, and the condensed water generated therewith adversely affects characteristics such as folding resistance between the resin layers or the interface between the resin and the metal foil. The resin composition to be used, the second layer of the resin composition of the second layer of the invention is also preferably produced by a method such as the isocyanate method described later, and the quinone imidization of the resin varnish obtained after the polymerization is preferably completed. Be able to dissolve In the polymerization solvent, the composition may be dissolved in an organic solvent is preferred. Further, even if it is produced by the isocyanate method, the imidization reaction is completed after the polymerization is not required due to the purity of the monomer or the influence of the type of the solvent, and therefore, the production conditions must be noted. In order to make the ruthenium iodide ratio 50% or more, in the amine method, it is preferred to synthesize the precursor by a usual method and slowly raise the temperature to Tg or more after the film formation, and

D

The vicinity of Tg (±10 °c) was heated for about 1 hour to carry out sufficient hydrazine imidization treatment. Further, in the isocyanate method, it is preferred to increase the water content to 50 mol% or less of the monomer mole number or to increase the purity of the monomer during the polymerization. For example, when the ring closure ratio of 1,2,4·benzenetricarboxylic anhydride is high, the purity of the monomer such as the amount of the diamine component of the impurity in the diisocyanate component is preferably high. Further, the method of the examples described later can be used by measuring the ruthenium iodide ratio. Further, in order to obtain workability in forming a laminated film of a flexible metal-clad laminate or a pressure-sensitive adhesive layer to be described later, the polyimide quinone imine resin must be soluble in an organic solvent. Further, the organic solvent referred to herein is selected from, for example, N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, 1,3-two. At least one of a group consisting of methyl-2-imidazolidone, tetramethylurea, cyclobutyl hydrazine, dimethyl hydrazine, r-butyrolactone, cyclohexanone, cyclopentanone, etc., or such Part of the use is selected from at least one selected from the group consisting of toluene, xylene, diglyme, triglyme, tetrahydrofuran, methyl ethyl ketone, and methyl isobutyl ketone. Adult. Further, in the present invention, the organic solvent is soluble in any one of the above-mentioned individual solvents or at least one of the mixed organic solvents containing 20% or more of the above, and is dissolved in an amount of 10 -22 to 200930 563 % by weight or more. More preferably, it is 15% by weight or more, and more preferably 20% by weight or more. Further, in the case where the resin is solid, a resin powder having a predetermined weight of 80 mesh is added to a 200 ml beaker, and the solution after being smoothly stirred at 25 ° C for 24 hours is placed at 25 ° C. For 24 hours, any one of gelation, unevenness, white turbidity, and precipitation was judged to be dissolved. In order to be soluble in a solvent, it can be achieved by the following methods.

Ο (1) The above preferred resin composition is employed. (2) Lowering the ratio of quinone imine/melamine groups. (3) A polycarboxylic acid component having a alicyclic group to be described later and a polyamine component are copolymerized. (4) A polycarboxylic acid component having a fatty group described later is copolymerized with a polyamine component. (5) Introducing a bendable group into the aromatic ring. (6) Introducing bulky compounds into the polymer chain. (7) Polymer modification is carried out using an epoxy compound or the like described later.

—N Η υ ·. Formula (5) (wherein R5 and R6 may be the same or different, each represents hydrogen or an alkyl or alkoxy group having 1 to 4 carbon atoms) -23- 200930563

•• General formula (6) (wherein R3 and R4 may be the same or different, each represents hydrogen or an alkyl or alkoxy group having a carbon number of i to 4)

•• General formula (7) (wherein R1 and R2 may be the same or different, each represents hydrogen or an alkyl or alkoxy group having a carbon number of 1 to 4; further, γ represents a direct bond (biphenyl) Key) or ether bond (-〇-)). An example of means for achieving the desired low-humidity expandable resin layer of the present invention is as described above, but the means for achieving the invention is not limited thereto. That is, when a hydrophobic substituent such as a methyl group, an ethyl group, or a fluorine-based substituent is introduced to lower the polarity of the bond and an appropriate molecular design is performed to lower the original water absorption rate of the resin, a low-humidity expandable resin layer can be obtained. In order to lower the polarity of the bond, for example, there is a means of increasing the ratio of the quinone bond to the guanamine bond. [Production of Polyamidimide Resin] The production of the above polyamidoximine resin can be carried out by a usual method. For example, there are an isocyanate method, an amine method (an oxime method, a low-temperature solution polymerization method, a room temperature solution polymerization method, etc.), etc., and the polyamidoximine resin used in the present invention must be soluble in an organic solvent, and further, in order to secure The above-mentioned folding resistance property, heat resistance reliability, etc., or because it can be directly applied industrially, it is preferable to use the iso-24-200930563 cyanate ester method. In the isocyanate method, the aromatic tricarboxylic anhydride of the raw material, the aromatic dicarboxylic acid, the aromatic tetracarboxylic dianhydride, and the like, and the aromatic diisocyanate can be roughly stoichiometrically reacted in an organic solvent to obtain the present invention. Resin composition. Here, as the aromatic tricarboxylic anhydride, 1,2,4-benzenetricarboxylic anhydride or the like can be used, and for the aromatic tetracarboxylic anhydride, pyromellitic dianhydride, diphenyl ketone tetracarboxylic dianhydride, and biphenyl tetra can be used. A carboxylic acid dianhydride, a diphenyl ether-3,3'-4,4'-tetracarboxylic acid, etc., and an aromatic dicarboxylic acid can use a phthalic acid, an isophthalic acid, a biphenyl dicarboxylic acid, a diphenyl group. Ether dicarboxylic acid, diphenyl sulfonium dicarboxylic acid, etc., and aromatic diisocyanate can be used as 1,4-naphthalene diisocyanate, 1,5-naphthalene diisocyanate, 2,6-naphthalene diisocyanate, 2,7-naphthalene Isocyanate, ortho-toluidine diisocyanate, and the like. The reaction is carried out in an organic solvent, usually at 10 ° C to 200 ° C for 1 hour to 24 hours, and the reaction may also be in the reaction of an isocyanate with an active hydrogen compound such as a tertiary amine or an alkali metal. It is carried out in the presence of a compound, an alkaline earth metal compound or the like. In order to produce the polymerization solvent of the polyamidoximine resin of the present invention, an organic solvent capable of dissolving the above polyamidoximine resin can be used. Typical examples of such an organic solvent are, for example, N-methyl-2-pyrrolidone, hydrazine, hydrazine-dimethylformamide, hydrazine, hydrazine dimethylacetamide, 1,3-dimethyl- 2-imidazolidinone, tetramethyl sulfonium, cyclobutyl hydrazine |, monomethyl arsenic, 7-butane vinegar, cyclohexyl copper, cyclopentanone, etc., preferably Ν-methyl-2-pyrrolidone . Further, a hydrocarbon-based organic solvent such as toluene or xylene; an ether solvent such as diglyme, triethylene glycol dimethyl ether or tetrahydrofuran; methyl ethyl ketone or methyl isobutyl ketone or the like may be used. The ketone solvent replaces a portion of these. -25- 200930563 The molecular weight of the polyamidoximine resin of the present invention is equivalent to N-methyl-2-pyrrolidone (polymer concentration: 0.5 g/d) at a logarithmic viscosity of 30 ° C It is preferably a molecular weight of from 0.3 to 2.5 dl/g, more preferably a molecular weight of from 0.5 to 2.0 dl/g. When the logarithmic viscosity is less than 〇3 dl/g, it is a molded article such as a film, and the mechanical properties may be insufficient. When the viscosity is more than 2.0 dl/g, the viscosity of the solution may become high, which may cause difficulty in forming. . The polyamidoquinone imide resin of the present invention does not impair the present invention in order to obtain a balance of various properties such as heat resistance, adhesion, dimensional stability, flexibility, insulation (migration resistance), and moisture absorption characteristics. In the range of the target characteristics, the acid component and the amine component shown below may be copolymerized in addition to the acid component, the isocyanate component or the amine component described above. Further, a resin obtained by separately polymerizing a combination of the acid component and the amine component may be used. In particular, it is also possible to use a mixture of the above-mentioned acid component and a combination of an amine component and a polymer which is polymerized, and it is also possible to use the above-mentioned acid component and also add the acid component described below and the above-mentioned amine component. It is also possible to mix the resin obtained by further adding a combination of the amine components described below. The acid component may, for example, be the following. a) Tricarboxylic acid: diphenyl ether-3,3,,4'-tricarboxylic acid, diphenylphosphonium-3,3,-4'-tricarboxylic acid, diphenylketone-3,3'- Separate or two or more of monoanhydrides and esterified products such as tricarboxylic acid such as tricarboxylic acid, naphthalene-1,2,4-tricarboxylic acid and butane-1,2,4-tricarboxylic acid mixture. b) tetracarboxylic acid: diphenyl sulfonium-3,3,,4,4,-tetracarboxylic acid, naphthalene-2,3,6,7-tetracarboxylic acid, naphthalene-1,2,4,5-four Carboxylic acid, naphthalene-1,4,5,8-tetracarboxylic acid, butane-1,2,3,4--26- 200930563 tetracarboxylic acid, cyclopentane-1,2,3,4-tetracarboxylate A single or a mixture of two or more kinds of acid anhydride, dianhydride, esterified product or the like. c) Dicarboxylic acids: dicarboxylic acids of adipic acid, sebacic acid, sebacic acid, cyclohexane-4,4'-dicarboxylic acid and such mono-anhydrides or esters. The amine component may, for example, be the following. d) Amine component 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-diethyl-4,4'-diaminobiphenyl, 2,2'-di Methyl-4,4'-diaminobiphenyl, 2,2'-diethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-di Aminobiphenyl, 3,3'-diethoxy-4,4'-diaminobiphenyl, p-phenylenediamine, meta-phenylenediamine, 3,4'-diaminodiphenyl 'Ether, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl base, 3,3'-diaminodiphenylanthracene, 3,4'-diamine Biphenyl, 3,3'-diaminobiphenyl, 3,3'-diaminobenzoxanil, 4,4'-diaminobenzoxanil, 4,4'-diamine Diphenyl ketone, 3,3'-diaminodiphenyl ketone, 3,4'-diaminodiphenyl ketone, 2,6-methyl-tolyldiamine, 2,4-tolylylene Amine, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenylpropane, 3,3'-diamine Diphenylpropane, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, p-xylylenediamine, m-xylylenediamine, 2,2'-double (4-aminophenyl)propane 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 2, 2-bis[4-(4-aminophenoxy)phenyl]propane, bis[4-(4-aminophenoxy)phenyl]anthracene, bis[4-(3-aminophenoxy) Phenyl] anthracene, bis[4-(3-aminophenoxy)phenyl]propane, 4,4'-bis(4-aminophenoxy)biphenyl, 4,4'-bis (3) -aminophenoxy)biphenyl, tetramethylenediamine,hexamethylenediamine,isophoronediamine, 4,4'-dicyclohexylmethanediamine, cyclohexane-1,4 - Diamine, diaminopyridoxane-27- 200930563 or a diisocyanate or the like, alone or in a mixture of two or more. Of course, the monomer component used in the first layer can also be used in a portion of the second layer, and vice versa. [Polyurethane ylide resin solution] If necessary, in order to improve various properties of the flexible metal-clad laminate or the flexible printed circuit board, such as mechanical properties, electrical properties, slip properties, flame retardancy, etc. The above polyamidoximine resin solution of the invention may be mixed with other resins or organic compounds and inorganic compounds, or may be used in combination. In the range which does not impair the object of the present invention, for example, a slip agent (cerium oxide, talc, polyfluorene oxide, etc.), an adhesion promoter, a flame retardant (pity or three tillage, aluminum hydroxide, etc.) can be used in combination. Stabilizer (antioxidant, UV absorber, polymerization inhibitor, etc.), plating activator, organic or inorganic tantalum (talc, titanium oxide, cerium oxide, fluorine polymer microparticles, pigments, dyes, calcium carbide, etc.) Other resins such as hydrazine compounds, fluorine compounds, isocyanate compounds, blocked isocyanate compounds, acrylic resins, urethane resins, polyester resins, polyamide resins, epoxy resins, phenol resins, or organic compounds, or An inorganic compound such as a hardener, cerium oxide, titanium oxide, calcium carbonate or iron oxide. Further, a polyfluorinated catalyst such as an aliphatic third-order amine, an aromatic third-order amine, a heterocyclic third-order amine, an aliphatic acid anhydride, an aromatic acid anhydride or a hydroxy compound may be added as necessary. For example, triethylamine, triethylenediamine, dimethylaniline, pyridine, methylpyridine, isoquinoline, imidazole, undecene, hydroxyethylbenzene, etc., preferably a pyridine compound, an imidazole compound, and eleven A carbene compound is particularly preferred, wherein benzimidazole, triazole, 4-pyridinemethanol, 2-hydroxypyridine, dioxabicyclo[5·4·0]undecene-7, and 2-hydroxyl group are preferred. Pyridine, dioxabicyclo[5.4.0]undecene-7 is more preferred. -28- 200930563 The concentration of the quinone imine resin in the polyamidoximine resin solution thus obtained can be selected from a wide range, and is usually about 5%, preferably about 8 to 20% by weight. In the concentration range, the coating property tends to decrease. From the coating property, etc., the solvent of the amine quinone imide resin solution is N,N-dimethylformamide, acetamide, 1,3-dimethyl-2-imidazole s ketone, tetramethylurea, two Methyl sub-milling, T-butyrolactone, cyclohexanone, cyclopentanone, etc. are particularly preferred as methyl-2-pyrrolidone. Further, toluene, a dihydrocarbon organic solvent, an ether solvent such as diglyme or triglyme, or a substitution such as methyl ethyl ketone or methyl isobutyl ketone may be used. a part of. Further, since these solvents can also be used as a solvent, the polymerization solution can be directly applied, and a resin solution having excellent workability can be easily obtained. A suitable solution viscosity is preferably in the range of B-type viscosity at 25 °C. If the viscosity is outside the above range, there is a coating condition. [Metal foil] The polyamidoximine resin or the resin composition of the present invention is laminated with a foil, and can be used as a flexible metal-clad laminate. In the metal foil of the present invention, a metal foil obtained by treating the composite metal foil or zinc or chromium metal compound obtained by using the copper foil, the aluminum foil, the steel foil, the nickel foil or the like can be used. The thickness of the metal foil is not particularly suitable as a metal foil of 3 to 50 μm. In particular, in order to finely pitch, it is preferable to use a thickness of 3 to 12 μm and a coated grain of 0.5 to 2.0 μm. The characteristics of the respective copper foils are as follows: polyamine N, N-dimethylcyclobutyl sulphate, and tetrahydrofuranone solvent such as N toluene are combined to form a polydose to add ~1 0 0 0 low-pollution material and used by Jinming, can also be other restrictions, such as the precision Rz of the circuit is the lower limit 値 -29-200930563, the peel strength is reduced, and when the upper limit is above, there will be fine The pitching becomes a tendency to be difficult. Usually, the metal foil is in the form of a belt, and the length thereof is not particularly limited. Further, the thickness of the strip-shaped metal foil is not particularly limited, and is usually preferably about 25 to 300 cm, and particularly preferably about 50 to 150 cm. As the metal foil, a commercially available electrolytic foil or a rolled foil can be used as it is. For example, "HLS" manufactured by Sakamoto Electrolysis Co., Ltd., "F0-WS" manufactured by Furukawa CIRCUIT FOIL Co., Ltd., "U-WZ" or "NA-VLP" and "DFF" manufactured by Mitsui Mining & Mining Co., Ltd. Wait. "Method for Producing Flexible Metal-clad Laminates In the present invention, only a polyimide film having a metal laminate of a metal foil on one side can be directly or through an adhesive layer, for example, on the aforementioned metal foil. A solution of the above two types of polyamidoximine resin (low elastic modulus resin, low humidity expansion resin) is applied in this order, and the coating film is dried (hereinafter referred to as initial drying), and heat treatment is performed as the case may be. The solvent is formed by desolvation (hereinafter referred to as secondary drying). The method of laminating two kinds of resins in a metal foil can be carried out by applying the first layer and drying the initial layer, then applying the second layer and drying it initially. It may be produced by heat treatment, or may be produced by applying the first layer, initially drying and secondary drying, then applying the second layer, and drying it in the initial stage and secondary drying, or applying the second layer and applying the second layer. The layer is produced by initial drying and secondary drying. In this case, the first layer and the second layer may be simultaneously applied. (Coating) The present invention is applied to the metal foil directly or through the adhesive layer. - 200930563 Polyamide amide imine resin solution is dried and dried. The coating method is not particularly limited, and a previously known method can be applied. For example, it can be coated by a roll coater, a knife coater, a blade coater, or a squeegee. The viscosity of the coating liquid, that is, the polyamidoximine resin solution, is adjusted by a coating, a gravure coater, a die coater, a reverse roll coater, etc., and then coated on the metal foil directly or through the adhesive layer. The composition of the adhesive at the time of application of the coating layer is not particularly limited. The composition of the adhesive when applied through the adhesive layer is not particularly limited, and an acrylonitrile butadiene rubber (NBR)-based adhesive, an epoxy resin, or an acrylic resin can be used. Adhesives such as polyimine resin, polyamidimide resin, polyester phthalimide resin, etc., because of heat resistance, adhesion, bending resistance, etc., polyimine resin, polyamine Preferably, the bismuth imine resin or the resin composition obtained by disposing the epoxy resin in the resin is preferably a thickness of the adhesive layer of about 5 to 30 μm. Further, the coating liquid of the present invention is applied to the metal foil. That is, the polyamidoximine resin can be applied or coated and dried directly or through an adhesive layer, and the above-mentioned adhesive can be further coated for the purpose of improving various characteristics of the flexible printed circuit board. From heat resistance and adhesion. From the viewpoints of the bending resistance and the curling property of the flexible printed wiring board, the adhesive composition and thickness are the same as described above, and the conditions of application and drying can also be applied to the same conditions as the polyamidoximine resin solution of the present invention. (Drying) The drying condition after the coating of the present invention is not particularly limited, and is usually 70 ° C to 130 ° lower than the boiling point (Tb (° C )) of the solvent used in the polyamidoximine resin solution. After the initial temperature of C is dried, it is preferably dried (secondary drying) at a temperature near the boiling point of the solvent or above the boiling point. -31- 200930563 When the initial drying temperature is higher than (Tb-70) °C, there will be Foaming occurs on the coated surface, or the unevenness of the residual solvent in the thickness direction of the resin layer becomes large, and warpage (curling) occurs in the metal laminated body, and the flexible printed circuit board is processed. Qu Yi Become bigger. Further, when the drying temperature is lower than (Tb - 130) °C, the drying time becomes long and the productivity is lowered. The initial drying temperature varies depending on the type of the solvent, and is usually about 60 to 150 ° C, preferably about 80 to 120 ° C. The time required for the initial drying is preferably an effective time of a solvent residual ratio of about 5 to 40% in the coating film under the above temperature conditions, and is usually about 1 to 30 minutes, preferably 2 to 15 minutes. The left and right are especially good. Further, the secondary drying conditions are not particularly limited, and may be carried out at a temperature near the boiling point of the solvent or at a temperature equal to or higher than the boiling point, and is usually about 120 to 400 ° C, preferably about 200 to 300 ° C. When the temperature is less than 120 °C, the drying time becomes long and the productivity is lowered. When the temperature is more than 300 °C, the resin composition may undergo a deterioration reaction to cause the resin film to become brittle. The time required for the secondary drying is usually at the above temperature conditions, and the solvent residual ratio in the coating film is preferably not effective, and usually the coefficient is from about minutes to several tens of hours. In the present invention, drying can also be carried out under an inert gas atmosphere or under reduced pressure. The inert gas may, for example, be nitrogen, carbon dioxide, helium, argon or the like, but it is preferred to use nitrogen which is easily available. In addition, it is preferably 1 (Γ5 to 1〇3 Pa), and it is preferably carried out at a pressure of about 10·1 to 200 Pa. In the present invention, the initial drying and the secondary drying are not particularly limited. It can be carried out by a previously known method such as a roll supporting method or a floating method. Further, it is also possible to carry out continuous heat treatment in a heating furnace such as a tenter type, or to wind up in a roll state and heat-treat in a batch type oven. In the batch mode, it is preferable to take up the uncoated surface of the coated surface and the non-coated surface. Further, the heating method can apply a previously known electric furnace, an IR heater, a far-infrared heater or the like. The thickness (T1) ratio of the resin layer (low-elasticity modulus resin layer) having a modulus of elasticity of 48 00 MPa or less (T1) and the resin layer (low-humidity-expandable resin layer) having a coefficient of humidity expansion of 2 Oppm or less (T1) / (T2) is preferably 0.05 to 5, preferably 0.1 to 5, more preferably 0.15 to 5. (Τ1) / (Τ2) is less than 0.05, flexibility, folding resistance, heat resistance Deterioration, the dimensional stability is worse when it is greater than 5. From the viewpoint of the combination of heat resistance, flexibility, folding resistance, and dimensional stability, a more preferable lamination method is that the heat-resistant resin layer on the side in contact with the metal foil has a modulus of elasticity of 4 8 . a low-elasticity modulus resin layer of OOMPa or less and a low-humidity expandable resin layer having a layer-based humidity expansion coefficient of not more than 20 ppm on the side in contact with the metal foil. The flexible metal-clad laminate of the present invention obtained as described above At least one side of the polyimide film layer of the polyimide film is provided with a metal foil, which is excellent in heat resistance, dimensional stability, and adhesion. Further, since the isocyanate method does not require a ruthenium imidization process, it can be carried out only. The solvent is dried and molded, or does not need to be heat-treated at a high temperature, and is characterized in that it can be manufactured inexpensively, and is excellent in flexibility, folding resistance, and heat resistance. The film thickness of the low elastic modulus resin layer is 3 to 5 It is preferably 0 μm, more preferably 5 to 30 μm, and most preferably 7 to 20 μm. When the thickness is less than 3 μm, the peel strength, bendability, and folding endurance after soldering tend to be lowered. The hygroscopic dimensional change rate tends to decrease at 50 μm. The film thickness of the low-humidity expansive resin layer is preferably from 10 to 60 μm in stomach-33 to 200930563, more preferably from 20 to 50 μm, and from 25 to 40 μm. Optimum. The change rate of moisture absorption size tends to be larger when it is less than 10 μm. When bent more than 60 μm, the bentonite compound has a tendency to reduce the folding resistance, and the film layer is formed from a polyimide film. The thickness of the entire polyimide film of the flexible metal-clad laminate of the present invention, which is composed of a metal foil, can be selected from a wide range, and usually the thickness after drying is preferably 5 to 100 μm. It is more preferably about 10 to 50 μm. When the thickness is less than 5 μm, mechanical properties or handleability such as film strength are deteriorated, and on the other hand, flexibility or workability (dryness) when the thickness is more than 100 μm There is a tendency to decrease in coating properties. Further, the flexible metal-clad laminate □ of the present invention may be subjected to surface treatment as necessary. For example, surface treatment such as water treatment, low temperature plasma, physical roughening, and easy adhesion coating treatment can be performed. The double-sided flexible metal laminate system of the present invention has a metal laminate having a metal foil on both sides, and can be, for example, between resin faces of a metal laminate which is formed by laminating only a metal foil on the surface formed as described above. It is manufactured by a method such as lamination using a previously known method. The lamination method is not particularly limited, and a conventionally known method such as roll lamination, pressure lamination, and belt press laminator can be employed, and the lamination temperature is usually not less than the Tg of the resin, for example, a low-humidity expandable resin layer The Tg or more of the resin layer of the joint surface is preferably 300 ° C to 500 ° C, more preferably 350 ° C to 450 ° C, and more preferably 3 80 ° C to 43 ° ° C. When the temperature is less than 300 °C, the adhesion is insufficient, and when it is more than 500 °C, the resin tends to deteriorate and the mechanical properties tend to be lowered. Further, the lamination time is not particularly limited, and is usually 10 seconds to 1 hour, preferably 1 minute to 1 hour, more preferably 3 minutes to 30 minutes. When the thickness is less than 1 sec., the adhesion is insufficient. When the temperature is more than 1 〇, there is a tendency that the resin layer is deteriorated and the mechanical properties are lowered. The adhesive composition at the time of application through the adhesive layer is not particularly limited, and an acrylonitrile butadiene rubber (NBR)-based adhesive, a polyamide-based adhesive, a polyester-based adhesive, or a polyester urethane can be used. Adhesives such as adhesives, epoxy resins, acrylic resins, polyimine resin resins, polyamidoximine resin resins, polyester phthalimide resins, etc., heat resistance, adhesion, and bending resistance The properties of the adhesive layer are preferably 5 to 3 in terms of properties such as a polyimide resin, a polyamide resin, or a resin composition in which the resin is blended with the resin. 0 micron is preferred. Further, from the viewpoint of insulating properties and the like, a resin composition obtained by blending an epoxy resin with a polyester or a polyamide amide resin or a resin thereof is preferable, and the thickness of the adhesive layer is 5 to 30. It is better to be around micrometers. The thickness of the adhesive is not particularly limited as long as it does not impede the performance of the flexible printed circuit board. When the thickness is too thin, it is difficult to obtain sufficient adhesion. On the other hand, when the thickness is too thick, there is a case where the thickness is too thick. The case where the workability (dryness, coatability) and the like are lowered. In addition, the heat-resistant film formed of the heat-resistant resin of the present invention to be described later and the metal foil can be laminated by using the above-mentioned adhesive, etc., by means of a layered structure of the adhesive layer. fit. [Flexible Printed Substrate] A flexible printed substrate can be produced by using the above-described flexible metal-clad laminate of the present invention in accordance with, for example, a subtractive process. When the surface of the circuit is covered for the purpose of protecting the solder resist of the conductor circuit or from contamination or injury, it is suitable to apply a well-known method and to apply a heat-resistant film such as polyimide to the wiring board through an adhesive ( A method of forming a base substrate formed of a conductor circuit, or a method of applying a liquid coating agent to a wiring board by using a screen printing-35-200930563 brush method. The liquid coating agent can be a previously known epoxy-based or polyimide-based ink, preferably a polyimide. Further, it is also possible to directly bond an adhesive sheet such as an epoxy resin or a polyimide film to a wiring board. The flexible printed circuit board thus obtained is excellent in heat resistance, dimensional stability, and adhesion, and is excellent in bendability, folding resistance, moisture absorption property, and insulation property, and is also used in high-density circuit boards requiring fine pitch. It can be used and has great advantages in industry. 〇 (Manufacturing Method of Flexible Printed Substrate) The flexible printed circuit board of the present invention can be produced by a conventionally known process, in addition to the above-described respective layers of materials. A preferred embodiment is a cover film which is formed by laminating an adhesive layer of a polyimide film to form an adhesive. On the other hand, a semi-finished product in which a desired circuit pattern is formed on a base film layer (hereinafter referred to as a "substrate film-side semi-product" is produced. The adhesive film-attached film and base obtained as described above are obtained. The film side half product is bonded to each other to obtain a flexible printed wiring base.

(Method for Producing Base Film Side Semi-Product) The base film side semi-product can be produced by using the above-described flexible metal-clad laminate and forming a circuit on the metal foil layer. The formation of the circuit can be by a previously known method. It is also possible to use an additive process or a subtractive process. It is better to use the subtraction method. The wiring pattern of the circuit can form an arbitrary pattern. The flexible printed circuit board of the present invention can exhibit high level of performance even in a circuit in which a particularly fine wiring pattern is applied, and the flexible printed circuit board of the invention is particularly useful in the implementation of a fine wiring pattern. of. Specifically, the circuit wiring thickness may be 100 micrometers or less, and the wiring thickness may be 50 micrometers or less. The wiring thickness may be 30 micrometers or less, and the wiring thickness may be 10 micrometers or less. The wiring interval may be 10 Below 0 micrometers, it may be 30 micrometers or less, or may be 10 micrometers or less. The sum of the wiring thickness and the wiring interval (circuit pitch) may be 100 μm or less, 60 μm or less, or 20 μm or less. (Method for Producing Cover Film with Adhesive) The cover film with an adhesive can be produced, for example, by applying an adhesive to a polyimide film and drying it. The adhesive is not particularly limited, and an acrylonitrile butadiene rubber (NBR)-based adhesive, a polyamide-based adhesive, a polyester-based adhesive, a polyester urethane-based adhesive, or an epoxy resin can be used. Adhesives such as an acrylic resin, a polyimide resin, a polyamidimide resin, or a polyester phthalimide resin, in terms of heat resistance, adhesion, and bending resistance, etc. It is preferred that the polyimide composition is a polyimine resin, a polyamide amine imide resin, or a resin composition in which an epoxy resin is blended in the resin. The method of laminating the adhesive can be applied to a usual method, and is not particularly limited, and for example, a roll coater, a knife coater, a blade coater, a blade coater, a gravure coater, a die coater, a reverse roll coater can be used. A coating method such as an equalizer is applied to the insulating film and dried to be laminated. The above coating method may be used to form an adhesive layer on the release film as the case may be, and the adhesive layer is laminated to the insulating film by a transfer method. The drying conditions are appropriately set in accordance with the adhesive to be used. Usually it is about 30 °C ~ 150 °C. Further, a crosslinking reaction may be carried out on the applied adhesive as necessary. Preferably, the embodiment of -37-200930563 is semi-hardened using an adhesive layer. The obtained adhesive film with an adhesive can be used for bonding to a substrate-side semi-finished product, or can be attached to a release-molded film and then stored for bonding to a base film-side semi-finished product. (Adhesion of the base film side semi-product and the adhesive-attached cover film) Any method of bonding the base film side semi-product and the adhesive-attached cover film can be used. For example, it can be bonded using a press machine or a roller or the like. Further, it is also possible to bond both while heating by a method such as a heating press or a heating roll press. For example, 'when the adhesive layer of the semi-finished product is in an unhardened ρ state or a semi-hardened state', it is also possible to harden the adhesive layer by heating at the time of bonding, and the adhesive layer can be easily obtained. The final product of hardening. When the crosslinking reaction is insufficient, or when the crosslinking reaction must be precisely controlled, it can be laminated by any of the above methods, and then post-cured as necessary. [Method of Using Flexible Printed Substrate] The flexible printed circuit board of the present invention can be formed by any laminated structure. As described above, for example, it may be a flexible printed circuit board comprising four layers of a base film layer, a metal foil layer, an adhesive layer, and a cover film. Further, if necessary, it may be a laminate of two or more sheets of the above-described flexible printed circuit board. For example, the above-described four-layer type flexible printed circuit board is laminated on a plurality of sheets, and if necessary, an adhesive can be used for adhesion between the flexible printed circuit board and the flexible printed circuit board. More specifically, the base film layer of the first flexible printed circuit board, the metal foil layer of the first flexible printed circuit board, the adhesive layer of the first flexible printed circuit board, and the first -38- may be laminated in the following order. 200930563 Protective layer of flexible printed circuit board, adhesive layer of metal foil layer of first flexible printed circuit board and second flexible printed circuit board, base film layer of second flexible printed circuit board, and second flexible printing The total thickness of the metal foil layer of the substrate, the adhesive layer of the second flexible printed circuit board, and the cover film layer of the second flexible printed circuit board is nine layers. Further, it is also possible to form a film of the base material 9 of the two-layer type flexible printed circuit board, which is adhered to each other with an adhesive layer and a back surface. In this case, for example, when the above-described four-layer type flexible printed circuit board is used, it is possible to laminate the film of the first flexible printed circuit board, the adhesive layer of the first flexible printed circuit board, and the adhesive layer of the first flexible printed circuit board. The metal foil layer of the first flexible printed circuit board, the base film layer of the first flexible printed circuit board, and the adhesive which adheres between the first flexible printed circuit board and the base film of the second flexible printed circuit board, and the second The base film layer of the flexible printed circuit board, the metal foil layer of the second flexible printed circuit board, the adhesive layer of the second flexible printed circuit board, and the cover film layer of the second flexible printed circuit board. [Use of Flexible Printed Substrate] The flexible printed circuit board of the present invention can use various products used in the prior flexible printed circuit board. Further, the flexible printed circuit board of the present invention is excellent in heat resistance, dimensional stability, flexibility, folding resistance, and insulating properties, and can be suitably used for applications of fine wiring and narrowing of wiring intervals. For example, it is suitable for a product having a thickness of 30 μm or less. Further, it is preferable that the wiring is -39-200930563 at intervals of 60 μm or less, the wiring interval is preferably 3 μm or less, and the wiring interval is preferably 10 μm or less. Therefore, it is possible to suitably use the narrowness of the wiring and the wiring interval (circuit pitch). For products having a circuit pitch of 100 μm or less, it is preferable to use a product having a circuit pitch of 60 μm or less, and a product having a circuit pitch of 30 μm or less is more preferable, and a product having a circuit pitch of 20 μm or less is particularly preferable. Further, examples of the specific final product that can be used for the flexible printed circuit board of the present invention include a flat panel display, a drive module for liquid crystal monitoring such as a mobile phone, and the like. [Examples] Hereinafter, the present invention will be described in more detail by way of examples. Further, the present invention is not limited to the embodiments. The evaluation method of the characteristics of each embodiment is as follows. Further, the powdery polyamidoximine resin sample used for the evaluation was produced by reprecipitating and purifying the polymerized cement obtained in each of the synthesis examples using a large amount of acetone. In addition, the resin film (base film) used for various measurement and evaluation was not notified in advance, and 35% of ferric chloride was used for the metal foil of the flexible metal-clad laminate obtained in each of the examples and the comparative examples. The uranium was removed at 40 ° C to obtain a resin film. <Logarithmic viscosity> A powdery polymer sample was dissolved in N-methyl-2-pyrrolidone at a polymer concentration of 〇.5 g/dl, and a Uberd-type viscometer was used at 3 〇. C The solution viscosity and solvent viscosity of the solution were measured and calculated according to the following formula. Logarithmic viscosity (dl/g) = [ln(Vl/V2)]/V3 -40- 200930563 In the above formula, VI represents the viscosity of the solution measured by a Uberund-type viscometer, and V2 is represented by Uberlau The solvent viscosity measured by the German viscometer, VI and V2, was determined from the time when the polymer solution and the solvent (N-methyl-2-pyrrolidone) passed through the capillary of the viscosity tube. Also, the V3 polymer concentration (g/dl). <Tg> The sample of the polyamidoximine resin described in Table 1 was applied to a metal foil and dried, and then the gold foil was removed by etching with 35% ferric chloride (40 ° C) to obtain a single layer. Resin film. The resin film (sample size: 4 mm wide x 15 mm long) was subjected to a dynamic viscoelasticity measuring apparatus (RHEOVIBRON, manufactured by ORIENTEC Co., Ltd.) at a frequency of 1 Η z and a temperature rising rate of 10 ° C /min from tan 5 Find the Tg at the top of the peak. <Coefficient of Thermal Expansion (CTE)> After the sample of the polyamidoximine resin described in Table 1 was applied to a metal foil and dried, the metal foil was removed by etching with 35% ferric chloride (40 ° C). A single layer of a resin film was obtained. The tensile load was tensile using TMA (manufactured by Thermomechanical Analysis Co., Ltd.) and the thermal expansion coefficient of the resin film was measured using the following conditions. Further, the film was brought to a temperature increase rate of 10 in nitrogen. (: / min, a film that is heated to the inflection point and then cooled to room temperature for measurement. Load: 5 g sample size: 4 (width) X 20 (length) mm Heating rate: 10 ° C / min Environment: Nitrogen measurement temperature range: 100 ° c to 200 ° c -41 - 200930563 <Dimensional change rate > According to IPC-FC241 (IPC-TM-650, 2.2.4 (c)) and 150 ° C x 30 minutes, the measurement MD direction and TD direction and obtain the average 値. <Adhesive strength> Use according to 1卩〇邛€241(1?(:-丁]^-650, 2.4.9(〇) and by subtraction method A sample made of a circuit pattern is produced, and the adhesion strength between the circuit pattern and the heat-resistant resin layer is measured. <Peel strength after soldering treatment> According to 1?(:邛邛241(1?(:-丁1^-650) , 2.4.9 (〇) and the circuit pattern was fabricated by subtraction, and the sample was floated in a solder bath for 30 seconds at 350 ° C to determine the adhesion strength. Further, the sample floated in the solder bath. The film was exposed to the surface of the resin substrate. <Temperature expansion coefficient (CHE)> First, a sample of the polyamidoximine resin described in Table 1 was applied to the metal. A metal-clad laminate made of foil and dried, and then measured as follows: (1) According to IPC-FC241 (IPC-TM-650, 2.2.4(c)), perforated at a specified position of the metal-clad laminate and at 25 °C 6 5 % humidity adjustment for 4 hours to measure the distance between the holes. (2) The metal-clad laminate was removed (etched) using the entire surface of the ferric chloride, and the obtained resin film was at a relative humidity of 20%, 40%. In 65% and 90% of each environment, the humidity was conditioned at 25 ° C for 24 hours. (3) According to IPC-FC241 (IPC-TM-6 50, 2.2.4 (c)), the pores of the resin film were measured. The dimensional change rate is obtained by using the distance between the holes of the metal foil laminate of (1) as a reference. -42- 200930563 (4) The dimensional change rate of each relative humidity is plotted (3), and The inclination of the humidity is used as the humidity expansion coefficient (CHE). <Folding resistance characteristics> The resin film obtained by removing the metal foil from the uranium (sample size: 25.4 mm χ 8 8.9 mm), using the GURLEY type manufactured by Toyo Seiki Co., Ltd. The softness tester measures softness (standard of repulsive force) in accordance with JIS 1 096. The judgment of the measurement result is softness. 120 mg or more was judged to be X, and when it was less than 1 20 mg, it was judged as 〇. <Strength, elongation, and elastic modulus of resin film> A sample of the polyamidoximine resin described in Table 1 was applied to a metal foil. After drying, the metal and foil were removed by using 35% of ferric chloride (401) uranium to obtain a single-layer resin film. A sample having a width of 10 mm and a length of 100 mm was produced from the resin film, and a tensile tester (trade name "TENSILON tensile tester", manufactured by Toyo BALDWIN Co., Ltd.) was used at a tensile speed of 20 mm/min. The distance between the heads is 40 mm to measure. <Rhodium imidization ratio> Absorption of ruthenium (I 3 80 cm-1) and benzene by a KBr method using an infrared spectrophotometer (manufactured by Shimadzu Corporation) using a powdery polymer sample The absorption of the nucleus (1510 cm-l) is used to determine its absorbance ratio. The calculation of the imidization ratio of the ruthenium is carried out on a copper-clad laminate film made of the same resin, and a powdery sample prepared by peeling off the surface of the resin is obtained, and the yttrium imine is obtained by the same method (1380<^ -1) and the absorbance ratio of the benzene nucleus (151 〇: 111-1), and the absorbance is calculated as 100%. <Manufacturing method of copper-clad laminate film> Electrolytic copper foil having a thickness of 12 μm (trade name "HLS", manufactured by Nippon Electric Co., Ltd. - 43-200930563), using a doctor blade and desolventizing The thickness was applied in a manner of 20 μm and dried at a temperature of 100 ° C for 5 minutes. Then, under reduced pressure drying conditions: 200 ° C X 24 hours (decompression degree is volatilized by a solvent, varying between 10 and 100 Pa) and heating under nitrogen (flow rate: 20 L / min); 260 ° C X 10 hours Heat treatment. <Solder heat resistance after humidification treatment> According to 1卩(:邛241(1?(:-丁丁1^-650, 2.4.9(<〇)), a circuit pattern is manufactured by subtraction method And humidification treatment was carried out for 24 hours in an environment of 40 ° C and 90% RH. Then, using a sample which was floated at 280 ° C for 30 seconds and allowed to float in a solder bath, the presence or absence of swelling or peeling was visually observed. Or the peeler was evaluated as 〇, and the swelled or peeled was X. Synthesis Example 1 (Resin 1) 192 g of 1,2,4-benzenetricarboxylic acid (Mitsubishi Gas Chemical Co., Ltd.), 209 was added to the reaction vessel. 1,5-naphthalene diisocyanate (100 mol%, manufactured by Sumitomo BAYER URETHANE Co., Ltd.), 1 g of dioxabicycloundecene (made by SAN-APRO), and 1 836 g of N-methyl 2-pyrrolidone (hereinafter abbreviated as NMP) (manufactured by Mitsubishi Chemical Corporation) (polymer concentration: 15%), and the temperature was raised to 10 ° C for 2 hours, and the reaction was carried out in this state. Then, 5 34 g of NMP (polymer concentration: 12% by weight) was added and cooled to room temperature. The obtained reconstituted cement was yellow-brown and the polymer was dissolved in NMP. Logarithmic viscosity, yttrium The chemical conversion rate is shown in Table 1. Further, the metal foil of the metal laminate obtained by molding the resin solution according to the method described in Example 1 was etched using 35% ferric chloride (40 ° C). The Tg, strength, elongation, elastic modulus, and CHE of the resin film (film characteristics of a single layer) were removed, as shown in Table 1. -44- 200930563 Moreover, the purity of each monomer was 99% or more. Synthesis Example 2 to 1 3 A resin varnish was produced using the same polymerization conditions as in Synthesis Example 1 except that the monomer composition was changed to the content shown in Table 1. Logarithmic viscosity, oxime imidization ratio, Tg, strength, and elongation The degree and the modulus of elasticity are shown in Table 1. Examples 1 to 5, 8 to 9 and Comparative Examples 1 to 6 The polymer solution obtained as described above was used, and the following molding processing conditions were used to produce a flexible coating. The metal laminate was evaluated for various characteristics as shown in Tables 1 and 2. (A) Initial drying The resin solution obtained above was laminated using the laminate shown in Table 2 to obtain a base resin layer having two layers. A flexible metal-clad laminate that is initially dried. In other words, an electrolytic copper foil having a thickness of 12 μm (trade name “NA-VLP”, manufactured by Mitsui Mining Co., Ltd.) was coated with a knife coater and the thickness after solvent removal was as described in Table 2. The first layer was dried at a temperature of 100 ° C for 5 minutes. Then, the same method was applied, and the thickness after desolvation was applied as described in Table 2, and the coating was again applied at a temperature of 1 ° C. After drying for 10 minutes, a flexible metal-clad laminate which was initially dried was obtained. (B) Secondary drying The above-mentioned initially dried flexible metal-clad laminate was wound around the outer surface of the coated flexible metal laminate to have an outer diameter of 16 inches. The aluminum can was crucible and heat treated using a vacuum dryer or an inert oven using the conditions shown below. The solvent in the coating film of the obtained laminate was completely removed. -45- 200930563 * Drying under reduced pressure: 2 〇 0 ° C x 24 hours (decompression is caused by evaporation of solvent, varying between 10 and 100 Pa) and heating under nitrogen (flow: 20 L / min); 260 Heat treatment was carried out at °C x10 hours. Examples 3 and 4 In addition to changing the copper foil to an electrolytic copper foil "U-WZ" manufactured by Furukawa Circuit F〇il (thickness) having a thickness of 12 μm and an electrolytic copper foil manufactured by Japanese Electrolysis Co., Ltd. having a thickness of 12 μm. In addition to the "HLS", each of the flexible metal-clad laminates was produced by the same 0 method as in Example 1, and various characteristics shown in Tables 1 and 2 were evaluated. ❿ -46 - 200930563 [Table i] Synthesis of monomer composition () Inner molar ratio Logarithmic viscosity dl/g Strength MPa Elongation (%) Elastic 雠 MPa CHE ppm CTE ppm Tg roization rate w 1 (Resin 1) TMA /NDI (100/100) 1,18 240 31 5000 40 17 365 99 2 (Resin 2) TMA/BTDA/BPDA/PMA/NDI (30/40/20/10/100) 1.44 280 38 4500 30 18 > 400 100 3 (Resin 3) TMA/BTDA/BPDA/PMA/TPA/NDI (10/40/20/10/20/100) 1.46 290 42 4800 28 17 >400 100 4 (Resin 4) TMa/btda /bpda/todi (85/10/5/100) 1.43 260 33 6800 17 25 310 100 5 (Resin 5) TMA/BTDA/BPDA/TODI (55/15/30/ΐω) 1.62 300 43 6500 12 17 330 99 6 (Resin 6) TMA/TDI/TODI (100/20/80) 1.40 290 40 6000 30 22 300 99 7 (Resin 7) TMA/BPDA/NDI (90/10/100) 1.33 240 20 4300 45 21 370 99 8 (Resin 8) TMA/BTDA/BPDA/TODI (75/20/5/100) 1.44 290 35 7200 16 23 330 100 9 (Resin 9) TMA/BTDA/BPDA/NDI (40/35/25/100) 1.31 210 20 4000 35 19 380 100 10 (Resin 10) TMA/BTDA/BPDA/PMA/NDI (20/45/25/10/100) 1.15 290 21 4500 26 16 395 99 11 (Resin 11) TMA/TPA/ BTDA/NDI (40/20/40/100) 1.20 180 33 4600 32 24 3 75 100 12 (Resin 12) TMA/BTDA/BPDAyTODI (70/10/20/100) 1.54 310 39 6800 19 19 340 100 13 mm η) TMA/DSDA/BPDA/NDI (10/65/25/100) 1.74 220 16 4800 42 32 350 100 The meaning of the symbol TMA: 1,2,4-benzenetricarboxylic anhydride BTDA : 3,3,' 4,4' - IT·Phenylketone tetracarboxylic dianhydride BPDA : 3,3, '4,4'-biphenyl ketone tetracarboxylic dianhydride PMA : pyrogallite anhydride TPA : phthalic acid NDI : 1,5-naphthalene diisocyanate TODI : o-toluidine diisocyanate DSDA : 3,3,' 4,4'-diphenyltricarboxylic acid dianhydride CHE: humidity expansion coefficient, CTE: thermal expansion coefficient -47- 200930563 [Table 2] Example Comparative Example 1st layer 2nd layer thickness (micrometer) Adhesive strength (N /cm) Peel strength after soldering treatment (N/cm) Dimensional change rate (%) Folding resistance Solder heat resistance after humidification treatment 1st layer 2nd layer Example 1 Resin 2 Resin 5 10 30 7 7 -0.028 〇〇 Example 2 Resin 3 Resin 5 10 30 7 7 • 0.033 〇〇Comparative Example 1 Resin 4 Resin 4 10 30 9 3 -0.060 X 〇Comparative Example 2 Resin 1 Resin 1 10 30 7 2 -0.100 XX Comparative Example 3 Resin 1 Resin 4 10 30 7 3 -0.120 XX Example 3 Resin 3 Resin 5 10 30 8 6 -0.011 〇〇 Example 4 Resin 3 Resin 5 10 30 6 6 -0.020 〇〇Comparative Example 4 Resin 1 Resin 6 10 30 7 2 -0.060 〇X Comparative Example 5 Resin 4 Resin 1 10 30 5 2 -0.090 XX Comparative Example 树脂 Resin 7 Resin 8 25 10 5 3 -0.030 〇X Example 5 Resin 9 Resin 5 10 25 8 7 0.035 〇〇 Example 6 Resin 2 Resin 12 10 25 8 6 - 0.032 〇〇 Example 7 Resin 10 Resin 5 10 25 8 6 -0.011 〇〇 Example 8 Resin 11 Resin 5 10 25 8 7 -0.021 〇〇 Example 9 Resin 13 Resin 5 10 25 9 8 -0.045 〇〇

[Industrial Applicability] As described above, the flexible metal-clad laminate system of the present invention is composed of a plurality of resin compositions which are excellent in flexibility and folding resistance, and have a small change in humidity size and a high Tg. It is excellent in composition, heating conditions, folding resistance, bendability, dimensional accuracy, and heat resistance. Further, since the resin composition to be used is soluble in an organic solvent, it can be produced inexpensively without requiring heat treatment at a high temperature. Therefore, it is industrially advantageous because it can inexpensively manufacture a flexible substrate that can be used even in high-density package substrates. [Simple description of the diagram] ίΕΒΕ. [Main component symbol description] ίΕΕ 〇 -48-

Claims (1)

200930563 X. Patent application scope: 1. A flexible metal laminate characterized by a flexible metal laminate formed by laminating a metal foil on at least one side of a heat resistant resin film, the heat resistant resin film being soluble in A two-layer structure composed of a polyamidoximine resin of an organic solvent, wherein one layer is a) the total amount of the acid component is 10% by mole, and the total amount of the amine component is 100 mole%, and the acid component When the total amount of the amine component is 2% by mole, the monomer component having a naphthyl group is 80 mol% or more, and the ratio of the b) imine bond to the chiral amine bond is 99/1 to 60/40. Ear ratio, c) The yttrium imine bond has a bismuth imidization ratio of 50% or more and a resin modulus of 4800 MPa or less, and the remaining layer is swelled by a low humidity of 20 ppm or less. Formed by a resin. 2. The flexible metal laminate according to the first aspect of the patent application, which is formed by laminating a metal foil on one side, wherein the heat-resistant resin layer on the side in contact with the metal foil is a) When the total amount of the methanol component and the amine component is 100 mol%, and the total of the acid component and the amine component is 200 mol%, the monomer component having a naphthyl group is 80 mol% or more, and b) a ratio of an amine bond to a guanamine bond of 99/1 to 60/40 molar ratio, a yttrium imide bond having a oxime imidization ratio of 50% or more and a resin modulus of 4 800 MPa or less, and The resin layer on the side not in contact with the metal foil is a low-humidity expandable resin layer having a humidity expansion coefficient of 2 〇 ppm or less. • 49- 200930563 3. A flexible metal laminate characterized by a metal foil formed on one side as in the flexible metal laminate of claim 1 or 2, wherein the humidity expansion coefficient is lower than 20 ppm. The humidity-expandable resin is a) when the total amount of the acid component is 1% by mole, the total amount of the amine component is 100% by mole, and the total of the acid component and the amine component is 200% by mole. The monomer component of the base is 1 〇〇 mol% or more, and b) the ratio of the yttrium bond to the guanamine bond is 99/1 to 65/35 molar ratio, φ c) quinone imine bond quinone The rate of conversion is 50% or more. 4. The flexible metal laminate according to any one of claims 1 to 3, wherein a) the total amount of the acid component is taken as 100 mol% of the total amount of 1 mol% of the amine component, When the total of the acid component and the amine component is 200 mol%, the monomer component having a naphthyl group is 80 mol% or more, and the ratio of the b) imine bond to the tanning amine bond is 99/1 to 60/40. Ear ratio, c) the yttrium imidization ratio of the quinone imine bond is 50% or more, the thickness of the resin layer having a modulus of elasticity of 4800 MPa or less (T1), and the low humidity expansion resin layer having a humidity expansion coefficient of 20 ppm or less. The ratio (Τ1) / (Τ2) of the thickness (T2) is 0.05 to 5. A double-sided flexible metal laminate is obtained by laminating a metal laminated body according to any one of claims 1 to 4 in a manner of forming a metal foil on both sides. A flexible printed circuit board is obtained by a flexible metal-clad laminate according to any one of claims 1 to 3. -50- 200930563 VII. Designation of representatives: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: ίΕΕ y y\\\ 8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: