TWI393629B - Metal - resin laminate - Google Patents

Description

Metal-resin laminate

The present invention relates to a metal-resin laminate which is particularly useful as a material for a flexible printed wiring board.

In the mainstream of the metal-resin laminate used in the flexible printed wiring board, a metal foil is bonded to at least one side of the polyimide film via the adhesive layer. Such a laminate uses an adhesive layer between the polyimide film and the metal foil, and thus the properties of the laminate are controlled by the properties of the adhesive layer. Further, the characteristics of the subsequent layer also affect the flexible printed wiring board using such a laminate.

The adhesive layer is mainly an acrylic resin-based adhesive and an epoxy resin-based adhesive, and it is required to improve heat resistance, chemical resistance, moisture resistance, dimensional stability, mechanical properties, and the like.

Therefore, it has been studied to use a thermoplastic polyimide having a high heat resistance, chemical resistance, mechanical properties, and electrical properties as an adhesive layer. However, the thermoplastic polyimide contains a lack of adhesion to the metal, and therefore, in order to obtain practical adhesion, there is a method of using, for example, an arithmetic surface roughness Ra exceeding 0.2 μm, or a ten-point average roughness Rz exceeding 0.70 μm. The metal foil having a large surface roughness mainly improves the adhesion by the fixing effect.

On the other hand, with the increase in the density of the package of the electronic device, the ultra-fine pitch of the wiring of the flexible printed wiring board is progressing. If the surface roughness of the metal foil as the conductor layer is still large, it naturally restricts the ultrafine pitch. Furthermore, as the amount of information processed by the electronic device increases, the frequency of the transmitted signal becomes higher, so that the density of the current flowing in the conductor approaches the conductor. The phenomenon (skin effect) near the surface becomes remarkable, causing a problem that the surface roughness of the conductor adversely affects the transmission of the signal.

In view of the above, it is required to use a metal foil having a smaller surface roughness as a conductor layer used in a flexible printed wiring board. Therefore, it is expected to use a laminate having a metal foil having a small surface roughness and having a high adhesion between the metal and the resin.

Further, in order to improve the dimensional stability of the laminated body, it is desirable that the coefficient of hygroscopic expansion of the adhesive layer is low. However, in general, the thermoplastic polyimine has a coefficient of hygroscopic expansion higher than that of the polyimide film.

Heretofore, a laminate having a copper foil having a surface roughness of a predetermined value or less and a thermoplastic polyimide layer having a specific chemical structure of tetracarboxylic dianhydride as a raw material has been studied (Patent Documents 1 and 2). However, the thermoplastic polyimine disclosed in Patent Document 1 has a high symmetry in structure and a high degree of alignment of polymer molecules, so that there is a possibility that the adhesion to the copper foil is insufficient. Further, the thermoplastic polyimine disclosed in Patent Document 2 has a structure which is soft and has a high polarity, and further has an epoxy resin as an essential component for improving the adhesion, and therefore has a high coefficient of hygroscopic expansion.

Further, a laminate having a metal foil having a surface roughness of a certain value or less and a thermoplastic polyimide layer having a specific diamine as a raw material has been studied (for example, Patent Document 3). Patent Document 3 discloses a thermoplastic polyimide layer having a high adhesion to SUS (stainless steel). However, it is known that the adhesion between the copper foil and the polyimide is remarkably lower than that between the stainless steel and the polyimide (Non-Patent Document 1), and a laminate having a high adhesion to copper is desired. Further, the thermoplastic polyimine disclosed in Patent Document 3 has a more symmetrical structure. Low, and the degree of alignment of the polymer molecules is low, so there is a possibility that the coefficient of hygroscopic expansion is high. In view of such a situation, a thermoplastic polyimine having a high adhesion to a metal foil having a small surface roughness and having a low coefficient of hygroscopic expansion is desired.

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2004-82495

[Patent Document 2] International Publication No. 2003/006553

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2006-142834

[Non-Patent Document 1] Hiroyuki Hirota and others, "Adhesion of Coating and Film Making, Control of Adhesion and Evaluation", Japan Technical Information Association, May 2005, p27~29

The present invention has been made in view of the above, and it is an object of the invention to provide a (metal-resin) laminate (hereinafter, a laminate) which is particularly useful as a material for a flexible printed wiring board, which laminate contains a thermoplastic polyimide. The amine, the thermoplastic polyimide, has a higher adhesion to a metal foil having a smaller surface roughness and a lower coefficient of hygroscopic expansion.

The present inventors have made intensive studies to solve the above problems, and as a result, it has been found that a thermoplastic polyimine having a specific structure of tetracarboxylic dianhydride as a raw material and controlling the degree of alignment of molecules can have a low hygroscopic expansion coefficient. And good adhesion to a metal foil having a small surface roughness, thereby completing the present invention.

That is, the laminate of the present invention is characterized in that it comprises a laminate of a metal foil and a thermoplastic polyimide layer, the surface of the metal foil is low in roughness, and the hygroscopic expansion coefficient of the thermoplastic polyimide layer At 16 ppm/% RH under.

In the laminate of the present invention, it is preferred that the surface of the metal foil has an arithmetic mean roughness Ra of 0.20 μm or less and/or a ten-point average roughness Rz of 0.70 μm or less.

In the laminate of the present invention, it is preferred that the thermoplastic polyimide layer contains (i) a repeating unit A derived from (i) a tetracarboxylic dianhydride represented by the general formula (1), and (ii) derived from The repeating unit B and (iii) of the tetracarboxylic dianhydride represented by the formula (2) are derived from at least two or more of the repeating units C of the tetracarboxylic dianhydride represented by the formula (3). (In the formula (1), R ₁ represents hydrogen, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, and n is an integer of 2 or more) (In the formula (2), R ₂ represents an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms)

In the laminate of the present invention, it is preferred that the repeating unit A is derived from a repeating unit of a tetracarboxylic dianhydride represented by the following formula (4). (In the formula (4), R ₃ and R ₄ each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms).

In the laminate of the present invention, preferred is 4,4'-extended biphenyl (trimellitic acid monoester) dianhydride represented by the above formula (4).

In the laminate of the present invention, it is preferred that the repeating unit B is derived from a repeating unit of a tetracarboxylic dianhydride represented by the following formula (6). (In the formula (6), R ₅ represents an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms).

In the laminate of the present invention, preferred is 2,5-toluenebis(trimellitic acid monoester) dianhydride represented by the above formula (6).

In the laminate of the present invention, it is preferred that the repeating unit A is derived from a repeating unit of a tetracarboxylic dianhydride represented by the formula (4), and the repeating unit B is derived from the formula (6). A repeating unit of a tetracarboxylic dianhydride.

In the laminate of the present invention, it is preferred that the thermoplastic polyimide layer contains a repeating unit derived from a diamine represented by the formula (8), H ₂ NX-NH ₂ (8) (wherein X is a divalent group selected from the group (9) below)

In the laminate of the present invention, the diamine represented by the above formula (8) represented by the above formula (8) contained in the thermoplastic polyimide layer is preferably a diamine represented by the formula (10).

In the laminate of the present invention, it is preferred that the thermoplastic polyimide layer further contains a repeating unit derived from a diamine represented by the formula (11).

In the laminate of the present invention, the diamine represented by the above formula (11) is preferably a 1,3-bis(3-aminophenoxy)benzene represented by the formula (12).

In the laminate of the present invention, it is preferred that the thermoplastic polyimide layer further comprises a resin layer.

In the laminate of the present invention, it is preferred that the resin layer has a hygroscopic expansion coefficient of 16 ppm/% RH or less.

In the laminate of the present invention, it is preferred that the resin layer is a polyimide film.

In the laminate of the present invention, it is preferred that the polyimine film contains a repeating unit derived from pyromellitic dianhydride and/or 3,3',4,4'-biphenyltetracarboxylic dianhydride. As a constituent.

In the laminate of the present invention, the above metal foil-based copper foil is preferred.

The flexible printed wiring board of the present invention is characterized in that the laminated body is subjected to wiring processing.

The laminate of the present invention is characterized in that it comprises a laminate of a metal foil and a thermoplastic polyimide layer having an arithmetic mean roughness Ra of 0.20 μm or less and/or a ten-point average roughness Rz of 0.70. Below the μm, the thermoplastic polyimide layer contains at least the repeating unit B derived from the tetracarboxylic dianhydride represented by the formula (2), and has a hygroscopic expansion coefficient of 16 ppm/% RH or less.

In the laminate of the present invention, it is preferred that the repeating unit B is derived from a repeating unit of the tetracarboxylic dianhydride represented by the formula (6).

In the laminate of the present invention, the above-mentioned formula (6) is preferably a 2,5-toluenebis(trimellitic acid monoester) dianhydride represented by the formula (7).

According to the present invention, a flexible printed wiring board using a metal foil having a small surface roughness and having good adhesion and excellent dimensional stability can be manufactured.

Hereinafter, the present invention will be specifically described.

The laminate of the present invention contains a metal foil having a specific surface roughness and a thermoplastic polyimide layer having a specific chemical structure provided on the metal foil.

<metal foil>

The metal foil used in the laminate of the present invention is preferably a low-roughness copper foil from the viewpoint of ultrafine pitch wiring processing and skin effect, and the term "low roughness" means the above metal foil. The surface (one side) has an arithmetic mean roughness (Ra) of 0.20 μm or less and/or a ten-point average roughness (Rz) of 0.70 μm or less. Particularly preferably, Ra is 0.20 μm or less and Rz is Metal foil of 0.70 μm or less. A more preferable range of Ra is 0.15 μm or less, and from the viewpoint of adhesion to the thermoplastic polyimine, Ra is preferably 0.01 μm or more, and more preferably 0.03 μm or more. Further, a preferable range of Rz is 0.60 μm or less, and from the viewpoint of adhesion to the thermoplastic polyimine, Rz is preferably 0.20 μm or more, and more preferably 0.30 μm or more, and particularly preferably 0.40 μm or more. Here, Ra and Rz are values measured by the method specified in JIS B0601:1994.

The type of the metal foil used in the laminate of the present invention is not particularly limited as long as it has the above Ra and/or Rz, and a known metal foil or alloy foil can be used. Specifically, a copper foil, an aluminum foil, a stainless steel foil, or the like can be applied. Among these, from the viewpoints of cost, availability, and workability, copper foil such as an electrolytic copper foil, a rolled copper foil, or a copper foil with a carrier is preferable. Examples of the copper foil which can be preferably used include a product name U-WZ (manufactured by Furukawa Circuit Foil Co., Ltd., Ra = 0.11 μm, Rz = 0.60 μm), and a trade name of NA- DFF (manufactured by Mitsui Metals Mining Co., Ltd., Ra=0.11 μm, Rz=0.60 μm), trade name HLS (manufactured by Nippon Electrolysis Co., Ltd., Rz=0.60 μm), trade name HLP (Nikko Metal, Japan) )Manufactured by a company, Rz=0.70 μm).

The thickness of the metal foil is preferably 0.5 to 50 μm, more preferably 1 to 35 μm, from the viewpoints of ease of handling during production, flexural resistance or flexural resistance when the product is used. Good is 5~20 μm.

On the surface of the metal foil, it is possible to carry out plating treatment, chromate treatment, alkoxy aluminum treatment, aluminum chelate for the purpose of improving adhesion or rust resistance. Surface treatment such as compound treatment or decane coupling agent treatment.

In the present invention, since the metal foil having a low surface roughness is used, the transparency of the flexible wiring board produced by using the laminated body of the present invention can be improved, and the visibility can be improved. Therefore, positioning when loading a semiconductor wafer becomes easy, and it can be preferably used for high-density packaging materials.

<Thermoplastic polyimide layer>

The laminate of the present invention is characterized in that the surface of the metal foil is 0.20 μm or less and/or Rz is 0.70 μm or less, and is laminated to the thermoplastic polyimide layer.

The thermoplastic polyimine of the present invention is obtained by using at least one of tetracarboxylic dianhydride and at least one of diamines as a raw material. The term "thermoplastic" as used herein means a glass transition temperature in the range of 100 ° C to 400 ° C, and melt flow by heating at a temperature higher than the glass transition temperature, whereby the molding process can be performed.

According to a first embodiment of the present invention, the thermoplastic polyimine contains a repeating unit A derived from a tetracarboxylic dianhydride represented by the formula (1) in a molecule, and is represented by the formula (2). The repeating unit B of the tetracarboxylic dianhydride is at least two or more selected from the repeating units C of the tetracarboxylic dianhydride represented by the formula (3).

(In the formula (1), R ₁ represents hydrogen, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, and n is an integer of 2 or more) (In the formula (2), R ₂ is a C ₁ -C ₆ alkyl group, and a C ₁ -C ₆ alkoxy group)

In the above formula (1), the repeating unit A is preferably represented by n=2 to 4 in terms of the solubility of the acid dianhydride monomer or the thermoplastic polyimide precursor of the raw material. More preferably, it is represented by n = 2 to 3, and further preferably derived from a tetracarboxylic dianhydride represented by the following formula (4).

(In the formula (4), R ₃ and R ₄ are each independently and represent hydrogen, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms)

The general formula R (1) ₁ and in the (4) in the R _3, R _4, is preferably hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butoxy The base and the third butyl group are more preferably hydrogen or methyl groups from the viewpoint of heat resistance and hygroscopic expansion coefficient of the thermoplastic polyimide.

Particularly preferably, in the above formula (1), the repeating unit A is derived from the 4,4'-extended biphenyl (trimellitic acid monoester) dianhydride represented by the following formula (5).

As R ₂ in the above formula (2), preferred are methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, and t-butyl, in terms of thermoplastic polyimine. From the viewpoint of heat resistance, a methyl group is more preferable. Further, as the tetracarboxylic dianhydride represented by the formula (2), as the isomer of the substituted phenyl group in the center, there are three kinds of ortho, meta and para are present, and the coefficient of hygroscopic expansion is lowered. From the viewpoint, it is preferred to be a counterpart.

In the above formula (2), the repeating unit B is preferably one derived from the tetracarboxylic dianhydride represented by the following formula (6). Particularly preferably, the repeating unit B is derived from 2,5-toluenebis(trimellitic acid monoester) dianhydride represented by the following formula (7).

(In the formula (6), R ₅ represents an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms)

The tetracarboxylic dianhydride represented by the above formula (3), as an isomer of the phenyl group in the center, has three kinds of ortho, meta and para, and the viewpoint of lowering the coefficient of hygroscopic expansion In terms of comparison, it is preferred to be a counterpart.

In the present embodiment, it is more preferable that the thermoplastic polyimide contains the repeating unit B and the repeating unit C from the viewpoint of the adhesion of the metal foil or the coefficient of hygroscopic expansion. In this case, the content of the repeating unit C is preferably 10 mol% or more from the viewpoint of balance of physical properties such as adhesion of the metal foil or glass transition temperature based on 100 mol% of the repeating unit B. The mol% or less is more preferably 25 mol% or more and 500 mol% or less, and particularly preferably 50 mol% or more and 200 mol% or less.

Further, in the present embodiment, the thermoplastic polyimine contains repeating unit A and repeating unit B from the viewpoint of the adhesion of the metal foil or the coefficient of hygroscopic expansion. In this case, the content of the repeating unit B is not particularly limited, and from the viewpoint of the adhesion of the metal foil, based on the content of the repeating unit A of 100 mol%, it is preferably 25 mol% or more and 400 mol%. Hereinafter, it is more preferably 33 mol% or more and 300 mol% or less, and further preferably 50 mol% or more and 200 mol% or less, particularly preferably 65 mol% or more and 150 mol% or less.

In the present embodiment, the thermoplastic polyimine may contain repeating unit A, repeating unit B, and repeating unit C. In this case, the sum of the contents of the repeating units B and C is not particularly limited, and from the viewpoint of the adhesion of the metal foil, based on the content of the repeating unit A of 100 mol%, preferably 25 mol%. The above 400 mol% or less, more preferably 33 mol% or more and 300 mol% or less, and further preferably 50 mol% or more and 200 mol% or less, particularly preferably 65 mol% or more and 150 mol% or less.

In the present embodiment, the sum of the contents of the repeating unit A, the repeating unit B, and the repeating unit C is not particularly limited, and the thermoplastic polymer is obtained from the viewpoint of the adhesion of the metal foil, the glass transition temperature, and the hygroscopic expansion coefficient. 100 mol% of all repeating units derived from tetracarboxylic dianhydride contained in ruthenium imide, preferably 10 mol% or more, more preferably 20 mol% or more, and further preferably 50 mol% or more Especially good is 80 mol% or more.

In general, it is known that by using a tetracarboxylic dianhydride containing a rigid (poly)phenylene diester group, the alignment of the polyimine molecules is improved, and the coefficient of hygroscopic expansion is lowered. However, for example, the polyimine having the structure of the above repeating unit A or C alone has a structure which is rigid and highly complex, and has no thermoplasticity or even thermoplasticity, and has a low adhesion to other substances. problem. Therefore, in general, in order to improve the adhesion of polyimine, it is used by copolymerization with a tetracarboxylic dianhydride having a flexible structure. However, the introduction of such a highly flexible structure causes the alignment of the polyimine molecules to decrease and the coefficient of hygroscopic expansion to increase. Thus, it is difficult to provide a polyimine which has both a high adhesion and a low coefficient of hygroscopic expansion.

Previously, it was difficult to imagine that two or more types of just used were used to achieve the above problems. A (poly)phenylene diester-based tetracarboxylic dianhydride. In the present embodiment, the hygroscopic expansion coefficient is lowered by using a tetracarboxylic dianhydride containing a rigid (poly)phenylene diester group, and the poly(phenylene) benzoic acid in the tetracarboxylic dianhydride is used in combination. Two or more monomers having different structures, and moderately controlling the alignment of the thermoplastic polyimide molecules, thereby achieving higher adhesion to the metal foil, and having a lower coefficient of hygroscopic expansion and comparison High continuity.

In the present embodiment, the hygroscopic expansion coefficient of the thermoplastic polyimide may be 16 ppm/% RH or less, or preferably 14 ppm/% RH or less, more preferably 13 ppm/%. Below RH, further preferably 12 ppm/% RH or less, particularly preferably 10 ppm/% RH or less. The coefficient of hygroscopic expansion can be controlled by the content of each of the above repeating units or the choice of diamine.

According to a second embodiment of the present invention, the thermoplastic polyimine contains at least a repeating unit B derived from a tetracarboxylic dianhydride represented by the formula (2) in a molecule.

The content of the repeating unit B is not particularly limited, and the repeating unit derived from the tetracarboxylic dianhydride contained in the thermoplastic polyimine is considered from the viewpoint of the balance of the physical properties such as the adhesion of the metal foil or the glass transition temperature. 100 mol% as a standard, preferably 1 mol% or more and 99 mol% or less, more preferably 10 mol% or more and 95 mol% or less, and further preferably 30 mol% or more and 90 mol% or less, particularly preferably 50 More than 80 mol% of mol% or more.

As described above, the thermoplastic polyimine containing a rigid (poly)phenylene diester-based tetracarboxylic dianhydride alone has a problem of lower adhesion to other substances. In this embodiment, the lower hygroscopic expansion coefficient of the rigid (poly)phenylene diester group is maintained, and the phenyl group of the tetracarboxylic dianhydride is stretched. The introduction of the substituents moderately controls the alignment of the thermoplastic polyimide molecules, thereby achieving higher adhesion to the metal foil, and having both a lower coefficient of hygroscopic expansion and a higher adhesion.

In the present embodiment, the hygroscopic expansion coefficient of the thermoplastic polyimide may be 16 ppm/% RH or less, or preferably 14 ppm/% RH or less, more preferably 13 ppm/%. Below RH, further preferably 12 ppm/% RH or less, particularly preferably 10 ppm/% RH or less. The coefficient of hygroscopic expansion can be controlled by the content of the above repeating unit B or the choice of diamine.

The coefficient of hygroscopic expansion of the thermoplastic polyimide is preferably lower than the coefficient of hygroscopic expansion of the resin layer provided on the thermoplastic polyimide layer described later.

The thermoplastic polyimine of the present invention, wherein all of the repeating units derived from the tetracarboxylic dianhydride in the molecule may be composed of repeating units selected from the above repeating units A, B, and C, or may contain the above repeating units A, B, A repeating unit derived from tetracarboxylic dianhydride other than C.

As such a tetracarboxylic dianhydride, a well-known person can be used. Specific examples thereof include pyromellitic acid, pyromellitic acid, cyclobutane tetracarboxylic acid, 3,3',4,4'-biphenyltetracarboxylic acid, and 2,3,3',4'-linked. Pyromellitic acid, 2,3,2',3'-biphenyltetracarboxylic acid, 3,3',4,4'-benzophenone tetracarboxylic acid, 2,2',3,3'-di Benzophenone tetracarboxylic acid, 2,2',3,3'-oxydiphthalic acid, 3,3',4,4'-oxydiphthalic acid, 1,3-dihydro- 1,3-dioxo-5-isobenzofurancarboxylic acid-1,4-phenylene ester, 3,3',4,4'-diphenylphosphonium tetracarboxylic acid, 2,3,6, 7-naphthalenetetracarboxylic acid, 1,2,4,5-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 4,4' -(isopropylidene)diphthalic acid, 4,4'-(hexafluoroisopropylidene)diphthalic acid, 4,4'-(4,4'-isopropylidenediphenyloxide Di-phthalic acid, 4,4'-(4,4'-hexafluoroisopropylidenediphenoxy)diphthalic acid, bis(3,4-dicarboxyphenyl) sulfide, bis(3,4-dicarboxyl) Phenyl)methane, 1,3-bis(3,4-dicarboxyphenoxy)benzene, 1,4-bis(3,4-dicarboxyphenoxy)benzene, 4,4'-bis (3, 4-dicarboxyphenoxy)biphenyl, butane-1,2,3,4-tetracarboxylic acid, pentane-1,2,4,5-tetracarboxylic acid, cyclopentane-1,2,3 , 4-tetracarboxylic acid, cyclohexane-1,2,4,5-tetracarboxylic acid, cyclohex-1-ene-2,3,5,6-tetracarboxylic acid, 3-ethylcyclohexyl-1 -ene-3-(1,2),5,6-tetracarboxylic acid, 1-methyl-3-ethylcyclohexane-3-(1,2),5,6-tetracarboxylic acid, 1- Methyl-3-ethylcyclohex-1-en-3-(1,2),5,6-tetracarboxylic acid, 1-ethylcyclohexane-1-(1,2),3,4- Tetracarboxylic acid, 1-propylcyclohexane-1-(2,3), 3,4-tetracarboxylic acid, 1,3-dipropylcyclohexane-1-(2,3), 3-( 2,3)-tetracarboxylic acid, dicyclohexyl-3,4,3',4'-tetracarboxylic acid, bicyclo[2.2.1]heptane-2,3,5,6-tetracarboxylic acid, bicyclo[ 2.2.2] Octane-2,3,5,6-tetracarboxylic acid, bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic acid, 5-(2,5- Dioxotetrahydro-3-furanyl-3-methyl-3-cyclohexene-1,2-dicarboxylic acid, ethyl bis(trimellitic acid monoester), bisphenol A double Benzoic acid monoester), polyethylene glycol double (bias An acid dianhydride containing a dehydrated cyclization structure, such as a trimellitic acid monoester; and all or a part of the hydrogen atoms in the compounds are alkyl, halogenated alkyl, halogen, alkoxy, halogenated alkoxy, etc. Other substituents are substituted. Among them, in terms of thermal expansion coefficient, glass transition temperature, heat resistance, etc., 3,4,3',4'-biphenyltetracarboxylic dianhydride, pyromellitic dianhydride, 3,3' are preferred. , 4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-oxydiphthalic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride . These tetracarboxylic dianhydrides may be used singly or in combination.

The content of the repeating unit derived from the above tetracarboxylic dianhydride is not particularly limited, and the adhesion to the metal foil, the glass transition temperature, and the hygroscopic expansion coefficient are From the viewpoint of 100 mol% of all the repeating units derived from the tetracarboxylic dianhydride contained in the thermoplastic polyimine, it is preferably 90 mol% or less, more preferably 80 mol% or less. Further preferably, it is 50 mol% or less, and particularly preferably 20 mol% or less.

The thermoplastic polyimine of the present invention is obtained by using the above tetracarboxylic dianhydride and a diamine as a raw material, and the diamine is not particularly limited, and a known one can be used. For example, 1,4-phenylenediamine, 1,3-phenylenediamine, 2,4-diaminotoluene, xylylenediamine, diaminonaphthalene, diamino guanidine, 2,2- Bis(4-aminophenyl)propane, 2-(3-aminophenyl)-2-(4-aminophenyl)propane, 2,2-bis(3-aminophenyl)propane, 4 , 4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylanthracene , 3,4'-diaminodiphenylanthracene, 3,3'-diaminodiphenylanthracene, 4,4'-diaminobenzophenone, 3,4'-diaminodiphenyl Methyl ketone, 3,3'-diaminobenzophenone, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl Ether, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(3-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminobenzylidene)benzene, 1,3-bis(4-aminobenzimidyl)benzene, 1,4-bis(3-aminobenzimidyl)benzene, 1,4-bis(4-aminobenzimidyl)benzene, α,α'-bis(4-aminophenyl)-1 , 4-diisopropylbenzene, α,α'-bis(4-aminophenyl)-1,3-diisopropylbenzene, 4,4'-bis(4-aminophenoxy)di Benzophenone, 4,4'-double (3- Aminophenoxy)benzophenone, 4,4'-bis(4-aminophenoxy)diphenylphosphonium, 4,4'-bis(3-aminophenoxy)diphenylphosphonium , 4,4'-bis(4-aminophenoxy)biphenyl, 4,4'-bis(3-aminophenoxy)biphenyl, 2,2-bis(4-(4-amino) Phenoxy)phenyl)propane, 2,2-bis(4-(3-aminophenoxy)phenyl)propane, 2,2-bis(3-(3-aminophenoxy)phenyl ) propane, 4,4'-bis(4-aminophenoxy)diphenyl ether, 4,4'-bis(3-aminophenoxy)diphenyl ether, 1,3-double (4) -(3-Aminophenoxy)benzylidene)benzene, 4,4'-bis(4-(4-aminophenoxy)benzylidene)diphenyl ether, 9,9-double (4-Aminophenyl)purine, cis-1,4-diaminocyclohexane, cis-1,3-diaminocyclohexane, and cis-1,2-diamine Cyclohexane, 3-methyl-trans and cis-1,4-diaminocyclohexane, 3-methyl-3-aminomethyl-5,5'-dimethylcyclohexylamine, 1 , 3-diaminomethylcyclohexane, bis-(4,4'-aminocyclohexyl)methane, bis(3,3'-methyl-4,4'-aminocyclohexyl)methane, double -(Aminomethyl)norbornane, bis-(aminomethyl)-tricyclo[5,2,1,0 ^2,6 ]decane, 3,4-diaminobenzoic acid, 3,5 -diaminobenzoic acid, 3,4-diaminobenzene Methyl formate, methyl 3,5-diaminobenzoate, and the like. Further, a group of a hydrogen atom contained in the above diamine may be substituted with a group selected from the group consisting of a methyl group, an ethyl group, and a propyl group. These diamines may be used alone or in combination of two or more.

Among these, 4,4'-bis(4-aminophenoxy)biphenyl is preferred from the viewpoint of the adhesion of the metal foil and the low hygroscopic expansion coefficient of the thermoplastic polyimide. , 4,4'-bis(3-aminophenoxy)biphenyl, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene , 1,4-bis(3-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, α,α'-bis(4-aminophenyl)-1, 4-diisopropylbenzene, α,α'-bis(4-aminophenyl)-1,3-diisopropylbenzene, 2,2-bis(4-aminophenyl)propane, 2, 2-bis(4-(4-aminophenoxy)phenyl)propane, 4,4'-bis(4-aminophenoxy)diphenylanthracene, 9,9-bis(4-amino group A phenyl) hydrazine or the like which contains an ether bond and/or an aliphatic quaternary carbon atom is particularly preferably 2,2-bis(4-(4-aminophenoxy)phenyl)propane. Furthermore, the adhesion to the metal foil, From the viewpoint of the thermal expansion coefficient of the thermoplastic polyimine, it will be selected from the group consisting of 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1, At least one diamine of 4-bis(3-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene and 2,2-bis(4-(4-aminobenzene) The use of oxy)phenyl)propane is also effective.

The content of the repeating unit derived from the diamine is not particularly limited, and is contained in the thermoplastic polyimide from the viewpoint of the adhesion of the metal foil and the low hygroscopic expansion coefficient of the thermoplastic polyimide. The basis of 100 mol% of all the repeating units derived from the diamine is preferably 10 mol% or more, more preferably 20 mol% or more, further preferably 50 mol% or more, and particularly preferably 80 mol% or more.

Further, the terminal of the thermoplastic polyimide may be a structure blocked with a terminal blocking agent such as a dicarboxylic anhydride or a monoamine. The terminal blocking agent is not particularly limited, and a known one can be used.

Examples of the dicarboxylic acid anhydride used for terminal blocking include phthalic anhydride, maleic anhydride, benzophenone dicarboxylic anhydride, diphenyl ether dicarboxylic anhydride, biphenyl dicarboxylic anhydride, and diphenyl. Terpene dicarboxylic anhydride, naphthalene dicarboxylic anhydride, hydrazine dicarboxylic anhydride, 4-phenylethynyl phthalic anhydride, 3-phenylethynyl phthalic anhydride, phenyl ethynyl naphthalene dicarboxylic anhydride, phenyl Ethynylbiphenyltetracarboxylic anhydride, phenylethynyldiphenyl ether dicarboxylic anhydride, phenylethynylbenzophenone dicarboxylic anhydride, phenylethynyldiphenylphosphonium dicarboxylic anhydride, phenylethynylfluorene dicarboxylate An acid anhydride or a substituent having an aromatic ring. These dicarboxylic acid anhydrides may be used alone or in combination of two or more.

Examples of the monoamine used for terminal blocking include aniline, aminophenol, 2-aminobiphenyl, 3-aminobiphenyl, 4-aminobiphenyl, and o-toluene. Amine, m-toluidine, p-toluidine, 2,3-dimethylaniline, 2,6-dimethylaniline, 3,4-dimethylaniline, 3,5-dimethylaniline, 2-aminodiphenyl ether, 3-aminodiphenyl ether, 4-aminodiphenyl ether, 2-aminobenzophenone, 3-aminobenzophenone, 4-aminobenzophenone, 2-aminodiphenyl Anthraquinone, 3-aminodiphenyl hydrazine, 4-aminodiphenyl hydrazine, α-naphthylamine, β-naphthylamine, 1-aminoindole, 2-aminoindole. These monoamines may be used singly or in combination of two or more.

The thickness of the thermoplastic polyimide layer of the present invention is preferably from 0.1 to 30 μm, more preferably from 0.3 to 15 μm, from the viewpoint of adhesion and solvent drying in the production step. It is 0.5~8 μm, especially 1~5 μm.

In a flexible printed wiring board, soldering is usually used to connect the wiring to the device. Therefore, the glass transition temperature of the thermoplastic polyimide of the present invention is preferably 183 ° C or more of the melting point of the eutectic solder, and further, in order to use a lead-free solder having a high melting point, it is more preferable that the glass transition temperature is 200 ° C or more. Here, the glass transition temperature is a value measured by thermomechanical analysis (TMA).

Next, the synthesis method of the thermoplastic polyimine of the present invention and its precursor will be described.

The thermoplastic polyimine of the present invention is obtained by dissolving at least one of the above tetracarboxylic dianhydride and a diamine in an actual molar amount in an organic solvent, and reacting it to obtain a precursor as a precursor. The valine acid is further subjected to a hydrazine imidization reaction to obtain a thermoplastic polyimine.

The solvent used in the reaction is not particularly limited as long as it is inert to the reaction, and N,N-dimethylformamide or N,N-dimethyl group can be used. Acetamide, N-methyl-2-pyrrolidone, cresol, dimethyl hydrazine, γ-butyrolactone, and the like. Particularly preferred from the viewpoints of safety, handling difficulty, and the like are N,N-dimethylacetamide, N-methyl-2-pyrrolidone, and γ-butyrolactone. Further, a solvent such as benzene, xylene, mesitylene, hexane, chlorobenzene, tetrahydrofuran, 1,4-dioxane, acetonitrile or benzonitrile may be mixed in any solvent in an arbitrary ratio.

The reaction is usually carried out at a solute concentration of 5 to 80% at a temperature of -20 ° C to 150 ° C for 10 minutes to 24 hours. The above terminal blocking agent may be added to the reaction system as needed.

The degree of polymerization of the obtained polyamic acid is preferably from 2 to 600. Further, the degree of polymerization can be calculated based on the weight average molecular weight measured by GPC. The degree of polymerization is adjusted in the same manner as in the case of the usual polycondensation polymer, and can be controlled by adjusting the molar ratio of the monomer components. For example, 0.8 to 1.2 mol of a diamine component is used with respect to 1 mol of the acid component. It is preferred to use 0.9 to 1.1 mol of a diamine relative to 1 mol of the acid component.

It is known that it is generally effective to increase the mechanical strength of polyimine, and it is effective to increase the molecular weight ("The Japanese Polyimine Research Society, the latest poly-imine - foundation and application ~" (Japan Corporation NTS) p .106); and the main reason for the decrease in the adhesion of polyimine is the low molecular weight substance existing near the interface ("Development and high-functionality-imparting technology of new polyimine for electronics and electronic materials for the next generation" ( Technical Information Association) p.20). In the present invention, the weight average molecular weight (Mw) of the obtained polyamic acid is not particularly limited, and the thermoplastic polysiloxane is used in terms of ease of application and hygroscopic expansion coefficient of the thermoplastic polyimide. When the amine does not contain repeating unit A, The good is 1000~300,000, and the better is 50000~200000. Further, in the case of containing the repeating unit A, it is preferably from 10,000 to 200,000, and further preferably from 50,000 to 100,000.

The obtained polylysine has a viscosity of 0.2 to 200,000 mPa·s, more preferably 0.3 to 50,000 mPa·s, and more preferably 0.5 to 30000 mPa·s. The viscosity of the polyaminic acid solution was measured at 23 ° C using a cone-and-plate type rotational viscometer (E-type viscometer).

In the case where the thermoplastic polyimine is solvent-soluble, the above-mentioned polyaminic acid hydrazide reaction can be carried out in advance in a solution. Thereby, there is an advantage that the stability of the solution is improved or the heat treatment at the time of coating the film described later is simplified. Here, "solvent solubility" means that 1% by weight or more of the solvent is dissolved in the solvent to be used in a temperature range from room temperature to 100 °C.

The method of carrying out the oxime imidization reaction in the solution is not particularly limited, and a known method can be used. Specifically, the following method may be used: a method of performing a ruthenium reaction by heating; or by adding acetic anhydride, trifluoroacetic acid, polyphosphoric acid, phosphorus pentoxide, phosphorus pentachloride, sulfoxide A chemical conversion agent (dehydrating agent) represented by or the like, or a catalyst represented by isoquinoline, β-methylpyridine, pyridine, N-valerolactone or the like, which promotes dehydration and cyclization of polylysine to carry out hydrazine Method of imidization.

On the other hand, when the thermoplastic polyimide is not solvent-soluble, it is necessary to carry out the oxime imidization reaction after coating and drying the solution of the poly-proline. This aspect will be described in the manufacturing method of the laminate.

Further, in order to increase the stability of the solution of the polyimide precursor, the polyglycolic acid may be replaced by a polyphthalate or a polyisodecimide. The method is for example Revealed in "The Japanese Polyimine Research Society, the latest poly-imine ~ foundation and application ~" (Japan Corporation NTS).

Further, as a solution, a dehydrating agent, a filler such as cerium oxide, a surface modifying agent such as a decane coupling agent, or the like may be added to the solution of the thermoplastic polyimide or a precursor thereof. Further, in order to efficiently carry out the hydrazine imidization reaction described later, a ruthenium-imidation accelerator may be added to the solution of the thermoplastic polyimide precursor.

<Resin layer provided on the thermoplastic polyimide layer>

In the present invention, in terms of thermal expansion coefficient, heat resistance, modulus of elasticity, tear strength, tensile elongation at break, and the like of the laminate, it is preferred to use in addition to the above thermoplastic polyimide layer. The resin layer is provided in such a manner that the thermoplastic polyimide layer is in contact with each other. The resin layer is not particularly limited, and a known one can be used, and a polyimide film is preferable, and a non-thermoplastic polyimide film is more preferable. The term "non-thermoplastic" as used herein means that the glass transition temperature is not present at 400 ° C or lower, or the glass transition temperature does not cause the elastic modulus to be greatly lowered due to heating above the glass transition temperature, and the plasticity is not plasticized (not Melt flow).

The polyimide film is a film obtained by using tetracarboxylic dianhydride and a diamine as a raw material, and the composition thereof is not particularly limited, and a known one can be used. As an example of a commercially available polyimine film, Upilex (registered trademark) S, Upilex (registered trademark) SGA, Upilex (registered trademark) SN manufactured by Ube Industries, Ltd., Japan, Japan East Kapton (registered trademark) H, Kapton (registered trademark) V, Kapton (registered trademark) EN manufactured by Li Dubang Co., Ltd., Apical (registered by Kaneka, Japan) AH, Apical (registered trademark) NPI, Apical (registered trademark) NPP, Apical (registered trademark) HP, Apical (registered trademark) FP, and the like. These are all non-thermoplastic.

From the viewpoint of the adhesion between the thermoplastic polyimide layer and the polyimide film, it is more preferable that the above polyimide film contains a substance derived from pyromellitic dianhydride and/or 3, 3'. , a repeating unit of 4,4'-biphenyltetracarboxylic dianhydride.

The thickness of the resin layer of the present invention is preferably 2 μm or more and 125 μm or less. From the viewpoint of the rigidity of the laminate and the ease of film treatment, it is more preferably 5 μm or more. Moreover, it is more preferably 75 μm or less, more preferably 25 μm or less, and particularly preferably 17 μm or less from the viewpoint of film formation and bending difficulty of the printed wiring board.

The resin layer preferably has a coefficient of hygroscopic expansion of 16 ppm/% RH or less from the viewpoint of further improving the dimensional stability of the laminate.

The resin layer of the present invention may be surface-treated by sandblasting or wet blasting or polishing, or may be surface-treated by a corona discharge treatment or a plasma discharge treatment or a UV ozone treatment. By such treatment, the surface of the film is physically roughened, or a carboxyl group or the like is chemically formed to contribute to the subsequent functional group, whereby the adhesion can be further improved.

The corona discharge treatment can be carried out by a known method. As the electrode, a well-known electrode such as a stainless steel electrode, an aluminum electrode, a quartz electrode, a roller electrode, or a wire electrode can be applied. Further, the treatment roll can be applied to a known treatment roll such as a lining roll, an EPT lining roll, a chlorosulfonated polyethylene rubber (Hypalon) lining roll, a ceramic coating roll, and a nip roll. The ambient gas and the treatment density of the corona discharge treatment are not particularly limited. Regarding the corona discharge treatment conditions, any condition may be selected, and it is preferable to carry out electric treatment by dividing the discharge power by a discharge density of 40 W ‧ min/m ² or more, which is a value of the production speed and the treatment width. The electric treatment was carried out at a discharge density of 80 W ‧ min/m ² or more.

The plasma discharge treatment method may be a well-known method such as glow discharge, and the gas type, gas pressure, and treatment density of the plasma discharge treatment are not particularly limited. Further, the conditions of the plasma discharge treatment can be arbitrarily selected. When the plasma discharge treatment is performed by glow discharge, it is preferred that the discharge power is 20 to 2000 W ‧ min/m ² and the pressure is 1 Torr or less. The ambient gas for the plasma discharge treatment may be arbitrarily selected, and preferably a non-reactive gas such as tetrafluoromethane, oxygen, nitrogen, argon, helium, carbon dioxide, hydrogen or a mixture of two or more thereof or Reactive gas.

As the polishing and polishing treatment, a well-known apparatus can be used, and the kind of the polishing roller, the polishing pressure, and the number of rotations of the polishing roller are not particularly limited.

Before the corona discharge treatment or the plasma discharge treatment, sandblasting treatment or wet blasting treatment or polishing treatment may be performed.

These surface treatments may be carried out only on one side of the resin layer or on both sides.

<Manufacturing method of laminated body>

A method of producing a laminate of the present invention will be described.

The method for producing a laminate of the present invention is as follows: first, a solution of the thermoplastic polyimide or a precursor thereof is applied onto a metal foil or a resin layer, followed by drying, and if necessary, a ruthenium reaction is carried out. This forms a thermoplastic polyimide layer.

Hereinafter, the thermoplastic polyimide or a precursor thereof is coated on the resin layer. The method of the solution is described in detail.

The method of applying the solution of the thermoplastic polyimide or its precursor to the resin layer is not particularly limited, and various known coating methods can be used, and for example, a knife coater, a die coater, a knife coater, or a dipping can be used. Coater, Comma coater, reverse roll coater, gravure coater, lip coater, cap coater, bar coater The extrusion coater, the slope coater, and the curtain coater are used.

The solution of the thermoplastic polyimide or its precursor is coated and dried. The drying method or conditions are not limited. For example, hot air or infrared rays are used, and it is preferred to heat the solvent at a boiling point or higher (usually in the range of 100 ° C to 400 ° C) for 10 seconds to 10 hours.

In the case of coating a solution of a thermoplastic polyimide precursor, the oxime imidization reaction is carried out simultaneously with or after drying of the solvent to convert the thermoplastic polyimide precursor into a thermoplastic polyimide. This reaction is usually promoted by heating. The reaction conditions are not particularly limited, and well-known conditions can be applied, and it is generally practical to heat at 100 ° C to 400 ° C for 0.5 to 24 hours. Further, it may be carried out in an inert gas atmosphere such as nitrogen, argon or helium, as needed.

When a single-sided flexible printed wiring board is manufactured, a thermoplastic polyimide layer is formed on one surface of the resin layer. When a double-sided flexible printed wiring board is manufactured, a thermoplastic polyimide layer is formed on both sides of the resin layer. In this case, the composition and thickness of the thermoplastic polyimide layer formed on both sides may be the same or different.

The thermoplastic polyimide layer of the resin laminate obtained by the above method and the metal foil have Ra of 0.20 μm or less and/or Rz of 0.70 μm or less. The surface is brought into contact and pressed, whereby the laminated body of the present invention can be obtained by laminating integration.

As the pressing method, a pressing method is preferred. Examples of the pressing method include a flat plate vacuum pressing method, a flat plate non-vacuum pressing method, a roll pressing method, a double belt pressing method, and the like, and among them, a double belt pressing method and a roll pressing method are more preferable. The conditions for pressing are not particularly limited, and it is preferred to carry out continuous thermocompression bonding by a double belt pressing method or a rolling method at a temperature at which the thermoplastic polyimide is sufficiently flowed. In the double belt pressing method, the pressure between the belts is preferably from 1 to 10 MPa, more preferably from 2 to 6 MPa. In the rolling method, the pressure between the hot rolls is preferably from 1 to 500 N/mm, more preferably from 10 to 300 N/mm. In order to prevent thermal deterioration of the metal foil or the resin, the thermocompression bonding may be carried out in an inert gas atmosphere such as nitrogen or argon.

Furthermore, the order of lamination may be reversed, that is, a thermoplastic polyimide layer is formed on the metal foil, and then the thermoplastic polyimide layer is brought into contact with the resin layer and pressed, and the laminated layer is sequentially manufactured. The laminate of the present invention. In this case, when the thermoplastic polyimide layer is laminated so as to sandwich both sides of the resin layer, a laminate facing the double-sided flexible printed wiring board can be obtained.

In the laminate of the present invention, since the thermoplastic polyimine has a low coefficient of hygroscopic expansion, the dimensional stability of the laminate is good. Therefore, the accuracy in the steps of the wiring forming step or the packaging of the semiconductor wafer or the like can be improved, and it is suitable for use in high-density packaging materials.

In order to produce the flexible printed wiring board of the present invention, the metal foil of the laminate obtained above is subjected to wiring processing. Wiring processing can be performed by at least the following steps Proceed to happen.

A resist layer is formed on the metal foil of the laminate using a dry film resist, a resist ink or the like. Development is then carried out to pattern the resist layer into a desired shape. The copper foil portion exposed by development is dissolved with a chemical such as copper chloride or ferric chloride to remove the resist layer.

Moreover, in the case of producing a double-sided flexible printed wiring board, in addition to the above steps, the following double-sided conducting step is also performed: opening the hole for conducting the conduction between the metal foils on both sides, and further to the side of the hole Electroplating is performed to turn on both sides.

Generally, in a flexible printed wiring board, it is possible to reduce the occurrence of failure in the case where the substrate on which the packaged component is processed in an impact environment after the wiring is formed, and to reduce the processing of the substrate after the wiring is formed in a high-frequency bending environment. The higher the adhesion of the conductor layer-resin layer interface (the peel strength specified in A of JIS C6471 8.1), the better, preferably 0.6 N/mm or more, more preferably 0.8. N/mm or more, and further preferably 1.0 N/mm or more. According to the present invention, a flexible printed wiring board having good adhesion between the conductor layer and the resin layer interface can be obtained.

The surface of the metal foil, Ra and Rz, can be measured by removing the thermoplastic polyimide layer and the resin layer from the laminate or the flexible printed wiring board of the present invention. The method of removing the thermoplastic polyimide layer and the resin layer from the laminate may be carried out by peeling, dissolving, etching, oxidative decomposition, thermal decomposition, and the like. In particular, since the polyimide can be etched using an alkali solution, when the resin layer is a polyimide film, the surface of the metal foil can be exposed by caustic etching of the laminate. Depending on the type of resin layer, there is also no etching available. In the case where the peel strength is measured as described later, in most cases, (a) the interface between the thermoplastic polyimide layer and the metal foil is peeled off, or (b) the thermoplastic polyimide layer and the resin The interface of the layer is peeled off, or (c) produces a cohesive failure inside the thermoplastic polyimide layer. In the case of (a), the Ra and Rz of the metal foil can be directly tested. In the case of (b) or (c), the metal foil can be removed by etching to remove the thermoplastic polyimide layer remaining on the metal foil. The surface is exposed so that Ra and Rz can be measured. The values of Ra and Rz thus measured are usually almost the same as those of Ra and Rz of the metal foil as a raw material.

(Example)

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited by the examples. Further, the physical property evaluation in the following examples was carried out in the following manner.

(1) Peel strength

The copper foil-resin laminate was cut into a length of 140 mm and a width of 10 mm, and a polyvinyl chloride tape having a width of 1 mm was attached to the length direction of the copper foil surface to cover it. In the case where a copper foil layer is also present on the back surface, the entire back surface is covered with a polyvinyl chloride insulating tape. This was immersed in an aqueous solution of ferric chloride (manufactured by Nippon Tsurumi Co., Ltd.) to etch the copper foil layer, and the polyvinyl chloride insulating tape was removed, followed by washing with water to form a copper foil pattern having a width of 1 mm. The obtained sample was dried in a hot air dryer at 105 ° C for 1 hour, and then attached to a glass epoxy substrate of the same size as the laminate using a double-sided tape. The copper foil pattern having a width of 1 mm was peeled off from the polyimide layer, and the stress required for peeling was measured. The measurement is based on JIS C6471 8.1 A (90∘ peeling method) The method specified in the method was carried out at a peeling speed of 50 mm/min. Two test pieces were measured for the same composition, and the average value was made into the peeling strength.

(2) Heat aging

In the above (1), the sample obtained by etching the copper foil layer was heat-treated at 150 ° C for 7 days, and then a test piece was produced in the same manner as in (1), and the peel strength was measured.

(3) Hygroscopic expansion coefficient

A copper foil (trade name: USLP-SE, manufactured by Nippon Electrolysis Co., Ltd.) having a thickness of 12 μm was placed on a metal coating table having a temperature of 90 ° C so that the matte side surface became a surface. A solution (varnish) of a thermoplastic polyimine precursor having a concentration of 15% by weight was applied to a matte side of the copper foil using a doctor blade. Thereafter, it was allowed to stand on the coating table for 10 minutes, and further dried by heating in an air circulating type drying oven at 120 ° C for 10 minutes, thereby obtaining a non-tacky thermoplastic polyimide film (about 45 thick). Mm). Then, in a hot air drier, heating at 150 ° C for 30 minutes in a nitrogen atmosphere at a heating rate of 5 ° C / min, heating at 200 ° C for 60 minutes, and heating at 350 ° C for 60 minutes to carry out oxime imidization. A thermoplastic polyimide film with copper foil was obtained. The copper foil-coated film was immersed in an aqueous solution of ferric chloride (manufactured by Nippon Tsurumi Co., Ltd.) to remove the copper foil, thereby obtaining a thermoplastic polycondensation (constituting a thermoplastic polyimide layer) having a thickness of about 25 μm.醯 imine film.

Using a thermomechanical analyzer (TM-9400) and a humidity environment adjustment device (HC-1) manufactured by ULVAC-RIKO Co., Ltd., Japan, measured at 23 ° C and a load of 5 g from a low humidity environment (10 to 30% RH) When changing to a high humidity environment (70~80% RH), the width is 3 mm and the length is 30 mm (the length between the chucks is 15) The dimensional change of the thermoplastic polyimide film of mm) was calculated to calculate the coefficient of hygroscopic expansion.

(4) Thermal expansion coefficient, glass transition temperature

The size of the above thermoplastic polyimide film was measured using a thermomechanical analyzer (TMA-50) manufactured by Shimadzu Corporation of Japan Co., Ltd. at a load of 5 g and a length of 19 mm (length between chucks of 15 mm). The change was made to calculate the thermal expansion coefficient and the glass transition temperature in the range of 100 ° C to 200 ° C.

(5) Thermal decomposition temperature

The weight change of the above thermoplastic polyimide film at a temperature increase rate of 10 ° C /min to 30 ° C to 700 ° C under a nitrogen gas flow rate was measured using a thermogravimetric analyzer (TGA-50) manufactured by Shimadzu Corporation, Japan. .

(6) Tensile modulus of elasticity and tensile elongation at break

On a silicon wafer with an aluminum film formed by sputtering, a varnish having a concentration of 15% by weight was spin-coated, and then dried at 100 ° C for 20 minutes to form a thermoplastic polyimide film precursor layer having a thickness of 17 μm. Then, the mixture was heated at 150 ° C for 30 minutes, heated at 200 ° C for 60 minutes, and heated at 350 ° C for 60 minutes to carry out oxime imidization. The resulting polyimide wafer with thermoplastic polyimide was cut out to a width of 3 mm using a wafer dicing machine, immersed in 2 N hydrochloric acid to etch aluminum, and the thermoplastic polyimide was peeled off. Thereafter, it was washed with water and dried at 80 ° C for 1 hour to prepare a sample.

Further, in the case where the sample was a commercially available polyimide film, the polyimide film was cut out to 5 mm × 50 mm as a sample.

The sample was stretched with a test length of 50 mm and a test speed of 50 mm/min using a RTG-1210 tensile tester manufactured by OLIENTEC, Inc., Japan, and the elongation of the sample at the time of the break was measured (hereinafter, for example, 50 mm). When the sample is broken at a point of elongation of 100 mm, it is referred to as "tensile elongation at break" (100%). The tensile modulus of elasticity is calculated from the slope of the stress between 0.4 and 1.0% of the tensile elongation of the film.

(7) Pants tear strength

The polyimine film was cut out as a sample of 50 mm × 150 mm, and the RTG-1210 tensile tester (installed with the company's UR-50N-D type load cell) manufactured by OLIENTEC Co., Ltd., Japan, was used as the JIS. The method disclosed in K7128-1 was measured at a test speed of 50 mm/min.

(8) Weight average molecular weight (Mw)

The weight average molecular weight based on polystyrene was calculated by gel permeation chromatography using dimethylformamide as a developing solution.

(9) Infrared absorption spectrum

The measurement was carried out using a Fourier transform infrared spectroscopic analyzer Spec One, manufactured by Perkin Elmer Japan Co., Ltd., Japan.

(Example 1)

Add 2,2-bis(4-(4-aminophenoxy)phenyl)propane (hereinafter, BAPP) 1.22 g to a glass spiral tube with a capacity of 50 ml in a nitrogen-substituted hand-held work box. (3.0 mmol) and N-methyl-2-pyrrolidone (dehydrated) (manufactured by Nippon Wako Pure Chemical Industries, Ltd.) (hereinafter, NMP) 14.1 g, which were stirred at room temperature to dissolve. Further, 2.2 g (3.0 mmol) of 2,5-toluenebis(trimellitic acid monoester) dianhydride (hereinafter, TAMHQ) was added, and the lid was attached with a nitrogen introduction tube, and a magnetic stirrer was used under a nitrogen stream. The mixture was stirred at room temperature for 1 hour to obtain a solution (varnish) of a thermoplastic polyimine precursor having a concentration of 15% by weight. The varnish is further NMP Dilute to 150% to obtain a varnish having a concentration of 10% by weight.

The varnish having a concentration of 10% by weight was applied to a polyimide film maintained on a smooth plate maintained at 80 ° C using a #22 wire rod manufactured by RD Specialties, USA (trade name Apical (registered trademark) ) 17FP, manufactured by Kaneka Co., Ltd., Japan). After standing for 10 minutes, it was dried in an air circulating type drying oven at 120 ° C for 10 minutes, and further heat-treated at 150 ° C for 30 minutes under a nitrogen atmosphere, followed by heat treatment at 200 ° C for 60 minutes, followed by 350 ° C. The heat treatment was carried out for 60 minutes to carry out hydrazine imidization to form a thermoplastic polyimide layer.

The thermoplastic polyimide layer was bonded to a surface of a copper foil (trade name U-WZ, manufactured by Furukawa Copper Co., Ltd., Japan) having a surface roughness Ra of 0.11 μm, and vacuum-pressed under vacuum. It was pressed at 425 ° C for 30 minutes at 4.4 MPa, and then pressed at 5.9 MPa for 20 minutes, thereby obtaining a copper foil-resin laminate. The peel strength of the obtained copper foil-resin laminate was measured by the method described above.

Further, the hygroscopic expansion coefficient of 10% RH to 80% RH of the thermoplastic polyimide film prepared using a varnish having a concentration of 15% by weight was 15.5 ppm/% RH.

Further, the coefficient of thermal expansion was 64 ppm/°C.

(Example 2)

A mixture of TAMHQ 0.85 g (1.8 mmol) and p-phenylene bis(trimellitic acid monoester) dianhydride (hereinafter, TAHQ) 0.55 g (1.2 mmol) was used instead of TAMHQ 1.42 g as tetracarboxylic dianhydride. The same operation as in Example 1 was carried out to obtain a copper foil-resin laminate and a thermoplastic polyimide film. The peeling of the obtained copper foil-resin laminate was measured by the method described above. Deviation from strength. Further, 10% RH to 80% RH of a thermoplastic polyimide film made of a varnish having a concentration of 15% by weight had a hygroscopic expansion coefficient of 12.5 ppm/% RH and a coefficient of thermal expansion of 60 ppm/°C.

(Example 3)

A mixture of 0.44 g (1.5 mmol) of TAMHQ 0.71 g (1.5 mmol) and 3,3',4,4'-biphenyltetracarboxylic dianhydride (manufactured by Mitsubishi Chemical Corporation, Japan) (hereinafter, BPDA) was used instead. TAMHQ 1.42 g was subjected to the same operation as in Example 1 except for tetracarboxylic dianhydride to obtain a copper foil-resin laminate. The peel strength of the obtained copper foil-resin laminate was measured by the method described above.

(Comparative Example 1)

A nitrogen inlet tube was attached to a glass separable three-necked flask having a capacity of 1000 ml of a teflon-coated anchor type agitator, and the inside was replaced with nitrogen. BAPP 16.2 g (40 mmol) and NMP 199.0 g were added to the flask, and the mixture was stirred at room temperature to dissolve. Further, 18.3 g (40 mmol) of TAHQ was added, and the mixture was stirred at room temperature for 1 hour, and then heated to 80 ° C and further stirred for 3 hours to cause a reaction to obtain a varnish having a concentration of 15% by weight. The varnish was further diluted to 150% with NMP to obtain a varnish having a concentration of 10% by weight.

The varnish having a concentration of 10% by weight was applied to a polyimide film maintained on a smooth plate maintained at 80 ° C using a #22 wire rod manufactured by RD Specialties, USA (trade name Apical (registered trademark) 17FP, manufactured by Kaneka Co., Ltd., Japan, after being placed for 10 minutes, dried in an air circulating type drying oven at 120 ° C for 10 minutes, and further heat-treated at 150 ° C for 30 minutes under a nitrogen atmosphere, followed by 200 Heat treatment at °C 60 After a minute, heat treatment was carried out at 350 ° C for 60 minutes to carry out hydrazine imidization to form a thermoplastic polyimide layer. The thermoplastic polyimide layer produces white turbidity.

The thermoplastic polyimide layer was bonded to a surface of a copper foil (trade name U-WZ, manufactured by Furukawa Copper Co., Ltd., Japan) having a surface roughness Ra of 0.11 μm, and vacuum-pressed under vacuum. It was pressed at 425 ° C for 30 minutes at 4.4 MPa, and then pressed at 5.9 MPa for 20 minutes, thereby obtaining a copper foil-resin laminate. The peel strength of the obtained copper foil-resin laminate was measured by the method described above.

(Comparative Example 2)

A copper foil-resin laminate was obtained in the same manner as in Example 1 except that BPDA 0.88 g (3.0 mmol) was used instead of TAMHQ 1.42 g as the tetracarboxylic dianhydride. The peel strength of the obtained copper foil-resin laminate was measured by the method described above. Further, the hygroscopic expansion coefficient of 10% RH to 80% RH of the thermoplastic polyimide film produced using a varnish having a concentration of 15% by weight was 19.9 ppm/% RH.

(Comparative Example 3)

In addition to the use of 3,3',4,4'-benzophenonetetracarboxylic dianhydride (hereinafter, BTDA) 0.97 g (3.0 mmol) instead of TAMHQ 1.42 g, as Example 4 except for tetracarboxylic dianhydride In the same operation, a copper foil-resin laminate was obtained. The peel strength of the obtained copper foil-resin laminate was measured by the method described above.

The results of Examples 1 to 3 and Comparative Examples 1 to 3 are shown in Table 1. The peel strength of any of Examples 1 to 3 exceeded 0.6 N/mm before and after heat aging. On the other hand, the peel strength after heat aging in Comparative Example 1 was lowered to 0.56 N/mm. Moreover, in Comparative Examples 2 and 3, the peel strength was before and after heat aging. Below 0.6 N/mm.

(Example 4)

BAPP 1.23 g (3.00 mmol) and NMP 15.4 g were added to a 50 ml glass spiral tube in a nitrogen-substituted hand-held working box, and stirred at room temperature to dissolve. Slowly add 4,4'-extended biphenyl bis(trimellitic acid monoester) dianhydride (hereinafter, TABP) 0.64 g (1.2 mmol), and plug it tightly with a nitrogen inlet tube, using a magnetic stirrer. The mixture was stirred under a nitrogen stream at room temperature for 1 hour to cause a reaction. Further, TAMHQ 0.85 g (1.8 mmol) was added, and the mixture was stirred under a nitrogen stream at room temperature for 1 hour to obtain a solution (varnish) of a thermoplastic polyimine precursor having a concentration of 15% by weight. The varnish was further diluted to 150% with NMP to obtain a varnish having a concentration of 10% by weight.

The weight average molecular weight (Mw) of the thermoplastic polyimide precursor contained in the varnish was 8.2 × 10 ⁴ .

The varnish having a concentration of 10% by weight was applied to a polyimide film maintained on a smooth plate maintained at 80 ° C using a #22 wire rod manufactured by RD Specialties, USA (trade name Apical (registered trademark) ) 17FP, Japan Co., Ltd. manufactured by Kaneka). After standing for 10 minutes, it was dried in an air circulating type drying oven at 120 ° C for 10 minutes, and further heat-treated at 150 ° C for 30 minutes under a nitrogen atmosphere, followed by heat treatment at 200 ° C for 60 minutes, followed by 350 ° C. The heat treatment was carried out for 60 minutes to carry out hydrazine imidization to form a thermoplastic polyimide layer.

The thermoplastic polyimide layer was bonded to a surface of a copper foil (trade name: NA-DFF, manufactured by Mitsui Mining Co., Ltd., Japan) having a surface roughness Rz of 0.60 μm, and was vacuum-pressed. The copper foil-resin laminate was obtained by pressing at 4.4 MPa for 30 minutes under vacuum at 325 ° C, followed by pressing at 5.9 MPa for 20 minutes. The peel strength of the obtained copper foil-resin laminate was measured by the method described above and found to be 1.38 N/mm.

The hygroscopic expansion coefficient of 30% RH~70% RH of the thermoplastic polyimide film prepared using a varnish having a concentration of 15% by weight was 8.6 ppm/% RH.

(Example 5)

Add BAPP 1.23 g (3.00 mmol) and NMP 15.6 g to a 50 ml glass spiral tube in a nitrogen-substituted hand-held box. Stir at room temperature to dissolve, slowly add TABP 0.96 g (1.8 mmol). The plug was tightly packed with a nitrogen inlet tube, and the mixture was stirred under a nitrogen stream at room temperature for 1 hour using a magnetic stirrer. Further, TAMHQ 0.57 g (1.2 mmol) was added, and the mixture was stirred under a nitrogen stream at room temperature for 1 hour to obtain a solution (varnish) of a thermoplastic polyimine precursor having a concentration of 15% by weight. The varnish was further diluted to 150% with NMP to obtain a varnish having a concentration of 10% by weight.

Using the #22 wire rod made by R. D. Specialties of the United States, The varnish having a concentration of 10% by weight was applied to a polyimide film (trade name Apical (registered trademark) 17FP, manufactured by Kaneka Co., Ltd., Japan) which was kept on a smooth plate kept at 80 °C. After standing for 10 minutes, it was dried in an air circulating type drying oven at 120 ° C for 10 minutes, and further heat-treated at 150 ° C for 30 minutes under a nitrogen atmosphere, followed by heat treatment at 200 ° C for 60 minutes, followed by 350 ° C. The heat treatment was carried out for 60 minutes to carry out hydrazine imidization to form a thermoplastic polyimide layer.

The thermoplastic polyimide layer was bonded to a surface of a copper foil (trade name: NA-DFF, manufactured by Mitsui Mining Co., Ltd., Japan) having a surface roughness Rz of 0.60 μm, and was vacuum-pressed. The copper foil-resin laminate was obtained by pressing at 4.4 MPa for 30 minutes under vacuum at 325 ° C, followed by pressing at 5.9 MPa for 20 minutes. The peel strength of the obtained copper foil-resin laminate was measured by the method described above, and it was 1.00 N/mm.

(Comparative Example 4)

BAPP 1.23 g (3.00 mmol) and NMP 16.1 g were added to a 50 ml glass spiral tube in a nitrogen-substituted hand-held working box, and stirred at room temperature to dissolve. TABP 1.60 g (3.00 mmol) was slowly added, and the lid was placed with a nitrogen inlet tube, and the mixture was stirred for 1 hour at room temperature under a nitrogen atmosphere using a magnetic stirrer to obtain a thermoplastic polymer having a concentration of 15% by weight. A solution of a quinone imine precursor (varnish). The varnish was further diluted to 150% with NMP to obtain a varnish having a concentration of 10% by weight.

The resulting varnish having a concentration of 10% by weight was applied to a smoothing at 80 ° C using a #22 wire rod manufactured by R. D. Specialties, USA. A polyimide film (trade name Apical (registered trademark) 17FP, manufactured by Kaneka Co., Ltd., Japan) on the plate. After standing for 10 minutes, it was dried in an air circulating type drying oven at 120 ° C for 10 minutes, and further heat-treated at 150 ° C for 30 minutes under a nitrogen atmosphere, followed by heat treatment at 200 ° C for 60 minutes, followed by 350 ° C. The heat treatment was carried out for 60 minutes to carry out hydrazine imidization to form a thermoplastic polyimide layer.

The thermoplastic polyimide layer was bonded to a surface of a copper foil (trade name: NA-DFF, manufactured by Mitsui Mining Co., Ltd., Japan) having a surface roughness Rz of 0.60 μm, and was vacuum-pressed. The copper foil-resin laminate was obtained by pressing at 4.4 MPa for 30 minutes under vacuum at 325 ° C, followed by pressing at 5.9 MPa for 20 minutes. The peel strength of the obtained copper foil-resin laminate was measured by the method described above and found to be 0.27 N/mm.

(Example 6)

The same operation as in Example 1 was carried out except that the amount of use of BAPP was changed to 1.29 g (3.14 mmol).

The weight average molecular weight (Mw) of the thermoplastic polyimide precursor contained in the varnish was 5.6 × 10 ⁴ .

The peel strength of the copper foil-resin laminate produced using a varnish having a concentration of 10% by weight was 1.14 N/mm.

(Example 7)

The same operation as in Example 1 was carried out except that the amount of use of BAPP was changed to 1.26 g (3.07 mmol).

The weight average molecular weight (Mw) of the thermoplastic polyimide precursor contained in the varnish was 6.9 × 10 ⁴ .

The peel strength of the copper foil-resin laminate produced using a varnish having a concentration of 10% by weight was 1.18 N/mm.

(Example 8)

The same operation as in Example 1 was carried out except that the amount of use of BAPP was changed to 1.22 g (2.97 mmol).

The weight average molecular weight (Mw) of the thermoplastic polyimide precursor contained in the varnish was 8.1 × 10 ⁴ .

The peel strength of the copper foil-resin laminate produced using a varnish having a concentration of 10% by weight was 1.29 N/mm.

(Example 9)

Using a varnish having a concentration of 10% by weight obtained in Example 4, using Kapton (registered trademark) 80EN (manufactured by Toray DuPont Co., Ltd., 20 μm thick, containing 3,3',4,4'-biphenyl tetra Repeating unit of carboxylic acid dianhydride as a constituent component, tear strength of pants: 60 N/m, elastic modulus Number: 5.6 GPa (product catalogue value), maximum elongation: 81%, hygroscopic expansion coefficient: 16.0 ppm/% RH) As a polyimide film, a copper foil-resin laminate was produced in accordance with the above method. The peel strength of the copper foil-resin laminate was 1.36 N/mm.

(Embodiment 10)

BAPP 0.96 g (2.3 mmol) and NMP 14.8 g were added to a 50 ml glass spiral tube in a nitrogen-substituted hand-held working box, and stirred at room temperature to dissolve. TABP 0.64 g (1.2 mmol) was slowly added, and the lid was attached with a nitrogen introduction tube, and the mixture was stirred under a nitrogen flow at room temperature for 1 hour using a magnetic stirrer. Further, TAMHQ 0.85 g (1.8 mmol) and 1,3-bis(3-aminophenoxy)benzene (hereinafter, APB) 0.17 g (0.58 mmol) were added, and the mixture was stirred under a nitrogen stream at room temperature for 1 hour to cause a reaction. Thereby, a solution (varnish) of a thermoplastic polyimine precursor having a concentration of 15% by weight was obtained. The varnish was further diluted to 150% with NMP to obtain a varnish having a concentration of 10% by weight.

The weight average molecular weight (Mw) of the thermoplastic polyimide precursor contained in the varnish was 8.1 × 10 ⁴ .

The varnish having a concentration of 10% by weight was applied to a polyimide film maintained on a smooth plate maintained at 80 ° C using a #22 wire rod manufactured by RD Specialties, USA (trade name Apical (registered trademark) ) 9FP, manufactured by Kaneka Co., Ltd., Japan). After standing for 10 minutes, it was dried at 120 ° C for 10 minutes in an air circulating drying oven. The surface of the opposite side of the polyimide film was also coated and dried in the same order. Further heat treatment at 150 ° C for 30 minutes under nitrogen atmosphere, followed by addition at 200 ° C The heat treatment was carried out for 60 minutes, followed by heat treatment at 350 ° C for 60 minutes to carry out hydrazine imidization, and a thermoplastic polyimide layer was formed on both sides of the polyimide film.

The thermoplastic polyimide layer and the copper foil having a thickness of 9 μm (trade name: NA-DFF, manufactured by Mitsui Mining Co., Ltd., Japan) have a surface roughness Ra of 0.11 μm and an Rz of 0.60 μm. In the manner, the above polyimine film was sandwiched between two copper foils, pressed under vacuum at 200 ° C under no pressure for 30 minutes, and then pressed at 325 ° C for 5.9 MPa for 20 minutes. This obtained a copper foil-resin laminate having a double-sided copper foil. The peel strength of the obtained copper foil-resin laminate was measured by the method described above and found to be 1.19 N/mm.

Further, the hygroscopic expansion coefficient of 30% RH to 70% RH of the thermoplastic polyimide film produced using a varnish having a concentration of 15% by weight was 12.0 ppm/% RH.

(Example 11)

BAPP 0.72 g (1.7 mmol) and NMP 14.8 g were added to a 50 ml glass spiral tube in a nitrogen-substituted hand-held working box, and stirred at room temperature to dissolve. TABP 0.64 g (1.2 mmol) was slowly added, and the lid was attached with a nitrogen introduction tube, and the mixture was stirred under a nitrogen flow at room temperature for 1 hour using a magnetic stirrer. Further, TAMHQ 0.85 g (1.8 mmol) and APB 0.34 g (1.2 mmol) were added, and the mixture was stirred under a nitrogen stream at room temperature for 1 hour to obtain a solution of a thermoplastic polyimine precursor having a concentration of 15% by weight ( Varnish) The varnish was further diluted to 150% with NMP to obtain a varnish having a concentration of 10% by weight.

The weight average molecular weight (Mw) of the thermoplastic polyimide precursor contained in the varnish was 6.6 × 10 ⁴ .

A copper foil-resin laminate was produced in the same manner as in Example 10. The peel strength was 1.28 N/mm.

Further, the hygroscopic expansion coefficient of 30% RH to 70% RH of the thermoplastic polyimide film produced using a varnish having a concentration of 15% by weight was 12.0 ppm/% RH.

(Embodiment 12)

BAPP 0.81 g (2.0 mmol) and NMP 14.8 g were added to a glass-made spiral tube with a capacity of 50 ml in a nitrogen-substituted hand-held working box, and stirred at room temperature to dissolve. TABP 0.64 g (1.2 mmol) was slowly added, and the lid was attached with a nitrogen introduction tube, and the mixture was stirred under a nitrogen flow at room temperature for 1 hour using a magnetic stirrer. Further, TAMHQ 0.85 g (1.8 mmol) and 4,4'-bis(3-aminophenoxy)biphenyl (hereinafter, m-BAPB) 0.31 g (0.85 mmol) were added, and the mixture was stirred under a nitrogen stream at room temperature. The reaction was carried out in an hour, whereby a solution (varnish) of a thermoplastic polyimine precursor having a concentration of 15% by weight was obtained. The varnish was further diluted to 150% with NMP to obtain a varnish having a concentration of 10% by weight.

The weight average molecular weight (Mw) of the thermoplastic polyimide precursor contained in the varnish was 6.2 × 10 ⁴ .

A copper foil-resin laminate was produced in the same manner as in Example 10. The peel strength was 1.12 N/mm.

(Example 13)

BAPP 0.81 g (2.0 mmol) and NMP 14.8 g were added to a glass-made spiral tube with a capacity of 50 ml in a nitrogen-substituted hand-held working box, and stirred at room temperature to dissolve. TABP 0.64 g (1.2 mmol) was slowly added, and the lid was fitted with a nitrogen inlet tube, and a magnetic stirrer was used. The mixture was stirred and allowed to react at room temperature for 1 hour. Further, TAMHQ 0.85 g (1.8 mmol), m-BAPB 0.21 g (0.56 mmol), and APB 0.082 g (0.28 mmol) were added, and the mixture was stirred under a nitrogen stream at room temperature for 1 hour to obtain a concentration of 15% by weight. A solution of a thermoplastic polyimide precursor (varnish). The varnish was further diluted to 150% with NMP to obtain a varnish having a concentration of 10% by weight.

The weight average molecular weight (Mw) of the thermoplastic polyimide precursor contained in the varnish was 6.2 × 10 ⁴ .

A copper foil-resin laminate was produced in the same manner as in Example 10. The peel strength was 1.32 N/mm.

(Example 14)

A nitrogen inlet tube was attached to a glass separable three-necked flask having a capacity of 1000 ml of a teflon-coated anchor type agitator, and the inside was replaced with nitrogen. BAPP 20.9 g (50.8 mmol) and NMP 250 mL were added to the flask, and the mixture was stirred under a nitrogen stream at room temperature to dissolve. Further, TAHQ 14.2 g (30.9 mmol) and TAMHQ 9.72 g (20.6 mmol) were added, and the mixture was stirred under a nitrogen stream in a water bath for 1 hour, and further stirred at 80 ° C for 3 hours to obtain a thermoplastic polyazide having a concentration of 15% by weight. A solution of the amine precursor (varnish). The varnish was further diluted to 150% with NMP to obtain a varnish having a concentration of 10% by weight. The weight average molecular weight (Mw) of the thermoplastic polyimide precursor contained in the varnish was 18.5 × 10 ⁴ .

The varnish having a concentration of 10% by weight was applied to a polyimide film maintained on a smooth plate maintained at 80 ° C using a #22 wire rod manufactured by RD Specialties, USA (trade name Apical (registered trademark) ) 17FP, manufactured by Kaneka Co., Ltd., Japan). After standing for 10 minutes, it was dried in an air circulating type drying oven at 120 ° C for 10 minutes, and further heat-treated at 150 ° C for 30 minutes under a nitrogen atmosphere, followed by heat treatment at 200 ° C for 60 minutes, followed by 350 ° C. The heat treatment was carried out for 60 minutes to carry out hydrazine imidization to form a thermoplastic polyimide layer.

The thermoplastic polyimide layer was bonded to a surface of a copper foil having a thickness of 9 μm (trade name U-WZ, manufactured by Furukawa Copper Co., Ltd., Japan) having a surface roughness Ra of 0.11 μm and an Rz of 0.60 μm. The copper foil-resin laminate was obtained by pressing at 4.4 MPa for 30 minutes under vacuum at 325 ° C in a vacuum press, followed by pressing at 5.9 MPa for 20 minutes. The peel strength of the obtained copper foil-resin laminate was measured by the method described above and found to be 1.48 N/mm.

Further, the thermoplastic polyimide layer and a copper foil having a thickness of 9 μm (trade name: NA-DFF, manufactured by Mitsui Mining Co., Ltd., Japan) have a surface roughness Ra of 0.11 μm and an Rz of 0.60 μm. The mixture was pressed at 4.4 MPa for 30 minutes under vacuum at 325 ° C in a vacuum press, followed by pressing at 5.9 MPa for 20 minutes, thereby obtaining a copper foil-resin laminate. The peel strength of the obtained copper foil-resin laminate was measured by the method described above, and it was 1.49. N/mm.

The hygroscopic expansion coefficient of 30% RH to 70% RH of the thermoplastic polyimide film prepared using a varnish having a concentration of 15% by weight was 9.1 ppm/% RH. The glass transition temperature was 200 ° C, the coefficient of thermal expansion was 54 ppm / ° C, the 1% weight loss temperature (T _d1% ) was 421 ° C, and the 5% weight loss temperature (T _{d 5%} ) was 462 ° C. The tensile modulus of elasticity was 3.3 GPa, and the tensile elongation at break was 126%.

(Example 15)

A nitrogen inlet tube was attached to a glass separable three-necked flask having a capacity of 1000 ml of a teflon-coated anchor type agitator, and the inside was replaced with nitrogen. BAPP 20.7 g (50.3 mmol) and NMP 250 mL were added to the flask, and the mixture was stirred under a nitrogen stream at room temperature to dissolve. Further, TAMHQ 24.1 g (51.0 mmol) was added, and the mixture was stirred under a nitrogen stream in a water bath for 1 hour, and further stirred at 80 ° C for 3 hours to obtain a solution (varnish) of a thermoplastic polyimine precursor having a concentration of 15% by weight. . The varnish was further diluted to 150% with NMP to obtain a varnish having a concentration of 10% by weight. The weight average molecular weight (Mw) of the thermoplastic polyimide precursor contained in the varnish was 10.1 × 10 ⁴ .

A copper foil-resin laminate was produced in the same manner as in Example 14 and the peel strength was measured to be 1.01 N/mm in the case of using U-WZ as a copper foil and 0.98 N/mm in the case of using NA-DFF. .

The glass transition temperature of the thermoplastic polyimide film prepared using a varnish having a concentration of 15% by weight was 204 ° C, the 1% weight loss temperature (T _{d1 %} ) was 432 ° C, and the 5% weight loss temperature (T _{d 5%} ) was 468 ° C. . The tensile modulus of elasticity was 2.6 GPa, and the tensile elongation at break was 131%.

(Comparative Example 5)

A nitrogen inlet tube was attached to a glass separable three-necked flask having a capacity of 1000 ml of a teflon-coated anchor type agitator, and the inside was replaced with nitrogen. BAPP 25.9 g (63.1 mmol) and NMP 250 mL were added to the flask, and the mixture was stirred under a nitrogen stream at room temperature to dissolve. Further, 17.8 g (60.5 mmol) of BPDA was added, and the mixture was stirred under a nitrogen stream in a water bath for 1 hour, and further stirred at 80 ° C for 3 hours to obtain a solution (varnish) of a thermoplastic polyimine precursor having a concentration of 15% by weight. . The varnish was further diluted to 150% with NMP to obtain a varnish having a concentration of 10% by weight. The weight average molecular weight (Mw) of the thermoplastic polyimide precursor contained in the varnish was 8.4 × 10 ⁴ .

A copper foil-resin laminate was produced in the same manner as in Example 14 and the peel strength was measured to be 0.52 N/mm when U-WZ was used as the copper foil and 0.53 N/mm when using NA-DFF. .

(Embodiment 16)

A nitrogen inlet tube was attached to a glass separable three-necked flask having a capacity of 1000 ml of a teflon-coated anchor type agitator, and the inside was replaced with nitrogen. BAPP 12.7 g (31.0 mmol), APB 6.04 g (20.7 mmol) and NMP 250 mL were added to the flask, and the mixture was stirred under a nitrogen stream at room temperature to dissolve. Further, 11.2 g (20.9 mmol) of TABP was added, and the mixture was stirred at room temperature for 1 hour under a nitrogen stream, and further stirred at 80 ° C for 1 hour to cause a reaction. After cooling to room temperature, 14.8 g (31.4 mmol) of TAMHQ was added, and the mixture was stirred at room temperature for 1 hour, and stirred at 80 ° C for 2 hours to obtain a solution of a thermoplastic polyimine precursor having a concentration of 15% by weight. Varnish) The varnish was further diluted to 150% with NMP to obtain a varnish having a concentration of 10% by weight. The weight average molecular weight (Mw) of the thermoplastic polyimide precursor contained in the varnish was 5.3 × 10 ⁴ .

The varnish having a concentration of 10% by weight was applied to a polyimide film maintained on a smooth plate maintained at 80 ° C using a #22 wire rod manufactured by RD Specialties, USA (trade name Apical (registered trademark) ) 9FP, manufactured by Kaneka Co., Ltd., Japan). After standing for 10 minutes, it was dried at 120 ° C for 10 minutes in an air circulating drying oven. The surface of the opposite side of the polyimide film was also coated and dried in the same order. Further, the mixture was heat-treated at 150 ° C for 30 minutes in a nitrogen atmosphere, followed by heat treatment at 200 ° C for 60 minutes, followed by heat treatment at 350 ° C for 60 minutes to carry out hydrazide formation on both sides of the polyimide film. A thermoplastic polyimide layer.

The thermoplastic polyimide layer and the copper foil having a thickness of 9 μm (trade name: NA-DFF, manufactured by Mitsui Mining Co., Ltd., Japan) have a surface roughness Ra of 0.11 μm and an Rz of 0.60 μm. In the manner, the above polyimine film was sandwiched between two copper foils, pressed under vacuum at 200 ° C under no pressure for 30 minutes, and then pressed at 325 ° C for 5.9 MPa for 20 minutes. This obtained a copper foil-resin laminate having a double-sided copper foil. The peeling of the obtained copper foil-resin laminate was measured by the method described above. From the strength, the result was 1.23 N/mm.

The hygroscopic expansion coefficient of 30% RH~70% RH of the thermoplastic polyimide film prepared using a varnish having a concentration of 15% by weight was 11.8 ppm/% RH. The glass transition temperature was 192 ° C, the coefficient of thermal expansion was 61 ppm / ° C, the 1% weight loss temperature (T _d1% ) was 413 ° C, and the 5% weight loss temperature (T _{d 5%} ) was 455 ° C. The tensile modulus of elasticity was 3.1 GPa, and the tensile elongation at break was 108%.

(Example 17)

The same operation as in Example 16 was carried out except that the varnish having a concentration of 15% by weight was diluted to 150% to obtain a varnish having a concentration of 10% by weight, and γ-butyrolactone (γ-BL) was used instead of NMP as a solvent. The peel strength of the obtained copper foil-resin laminate was 1.31 N/mm.

(Comparative Example 6)

A nitrogen inlet tube was attached to a glass separable three-necked flask having a capacity of 1000 ml of a teflon-coated anchor type agitator, and the inside was replaced with nitrogen. 20.8 g (71.1 mmol) of APB and 240 mL of NMP were added to the flask, and the mixture was stirred under a nitrogen stream at room temperature to dissolve. Further, 33.0 g (71.9 mmol) of TAHQ was added, and the mixture was stirred under a nitrogen stream in a water bath for 1 hour, and further stirred at 80 ° C for 3 hours to obtain a solution (varnish) of a thermoplastic polyimine precursor having a concentration of 15% by weight. . The varnish was further diluted to 150% with NMP to obtain a varnish having a concentration of 10% by weight. The weight average molecular weight (Mw) of the thermoplastic polyimide precursor contained in the varnish was 21.7 × 10 ⁴ .

The resulting varnish having a concentration of 10% by weight was applied to a smoothing at 80 ° C using a #22 wire rod manufactured by R. D. Specialties, USA. A polyimide film (trade name Apical (registered trademark) 17FP, manufactured by Kaneka Co., Ltd., Japan) on the plate. After standing for 10 minutes, it was dried in an air circulating type drying oven at 120 ° C for 10 minutes, and further heat-treated at 150 ° C for 30 minutes under a nitrogen atmosphere, followed by heat treatment at 200 ° C for 60 minutes, followed by 350 ° C. The heat treatment was carried out for 60 minutes to carry out hydrazine imidization to form a thermoplastic polyimide layer.

The thermoplastic polyimide layer was bonded to a surface of a copper foil having a thickness of 9 μm (trade name U-WZ, manufactured by Furukawa Copper Co., Ltd., Japan) having a surface roughness Ra of 0.11 μm and an Rz of 0.60 μm. The copper foil-resin laminate was obtained by pressing at 4.4 MPa for 30 minutes under vacuum at 325 ° C in a vacuum press, followed by pressing at 5.9 MPa for 20 minutes. The copper foil/thermoplastic polyimide layer interface of the obtained copper foil-resin laminate had very low adhesion, and it was not possible to produce a sample for peel strength measurement.

[Industrial availability]

The present invention is applicable to a wiring substrate of an electronic device, and is particularly applicable to a flexible printed wiring board.

Figure 1 is an infrared absorption spectrum of the thermoplastic polyimine disclosed in Example 4.

(no component symbol description)

Claims (18)

A laminate comprising a metal foil and a thermoplastic polyimide layer, the thermoplastic polyimide layer containing at least a repeating unit B derived from a tetracarboxylic dianhydride represented by the formula (2), and The coefficient of hygroscopic expansion is 16 ppm/% RH or less: (In the formula (2), R ₂ represents an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms). The laminate according to claim 1, wherein the surface of the metal foil has an arithmetic mean roughness Ra of 0.20 μm or less and/or a ten-point average roughness Rz of 0.70 μm or less. The laminate according to claim 1 or 2, wherein the thermoplastic polyimide layer contains at least two or more selected from the group consisting of (i) to (iii): (i) derived from a tetracarboxylic acid represented by the general formula (1) a repeating unit A of acid dianhydride; (ii) a repeating unit B derived from a tetracarboxylic dianhydride represented by the formula (2); (iii) derived from a tetracarboxylic dianhydride represented by the formula (3) Repeat unit C; (In the formula (1), R ₁ represents hydrogen, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, and n represents an integer of 2 or more); (In the formula (2), R ₂ represents an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms; The laminate according to claim 3, wherein the repeating unit A is derived from a repeating unit of a tetracarboxylic dianhydride represented by the following formula (4): (In the formula (4), R ₃ and R ₄ each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms). The laminate according to claim 4, wherein the above formula (4) is a 4,4'-extended biphenyl (trimellitic acid monoester) dianhydride represented by the formula (5): [Chemical 5] The laminate according to claim 3, wherein the repeating unit B is derived from a repeating unit of a tetracarboxylic dianhydride represented by the following formula (6): (In the formula (6), R ₅ represents an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms). The laminate according to claim 6, wherein the above formula (6) is a 2,5-toluenebis(trimellitic acid monoester) dianhydride represented by the formula (7): The laminate according to claim 3, wherein the repeating unit A is derived from a repeating unit of a tetracarboxylic dianhydride represented by the following formula (4), and the repeating unit B is derived from the following formula (6) The repeating unit of the tetracarboxylic dianhydride represented: (in the formula (4), R ₃ and R ₄ each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms; (In the formula (6), R ₅ represents an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms). The laminate according to claim 3, wherein the thermoplastic polyimide layer contains a repeating unit derived from the diamine represented by the formula (8): [Chem. 8] H ₂ NX-NH ₂ (8) (wherein X Is a divalent group selected from the group (9) below; The laminate according to claim 9, wherein the diamine represented by the above formula (8) contained in the thermoplastic polyimine layer is a diamine represented by the formula (10): The laminate according to claim 10, wherein the thermoplastic polyimine layer further contains a repeating unit derived from the diamine represented by the formula (11): The laminate according to claim 11, wherein the diamine represented by the above formula (11) is 1,3-bis(3-aminophenoxy)benzene represented by the formula (12): The laminate according to claim 3, wherein the thermoplastic polyimide layer further comprises a resin layer. The laminate according to claim 13, wherein the resin layer has a hygroscopic expansion coefficient of 16 ppm/% RH or less. The laminate according to claim 14, wherein the resin layer is a polyimide film. The laminate according to claim 15, wherein the polyimine film comprises a repeating unit derived from pyromellitic dianhydride and/or 3,3',4,4'-biphenyltetracarboxylic dianhydride as a constituent component. . The laminate according to claim 3, wherein the metal foil is a copper foil. A flexible printed wiring board obtained by wiring a laminated body according to any one of claims 1 to 17.