JP5166233B2 - Laminate for wiring board having transparent insulating resin layer - Google Patents

Description

  The present invention relates to a laminate for a wiring board having excellent heat resistance and flexibility and having a highly transparent insulating resin layer.

  Polyimide resin is a heat-resistant resin obtained by ring-closing reaction of polyamic acid synthesized from aromatic tetracarboxylic acid anhydride and aromatic diamine, and these condensation reactions. Stiffness of molecular chain and resonance stabilization It has excellent resistance to thermal decomposition due to a strong chemical bond, has high durability against chemical changes such as oxidation or hydrolysis, and is excellent in flexibility, mechanical properties and electrical properties. In general, this polyimide resin is widely used for an insulating resin layer of a flexible printed circuit board (hereinafter referred to as FPC) used in an electronic device.

  The insulating resin layer of the commercially available copper clad laminate currently used for FPC is made of wholly aromatic polyimide resin, and shows a yellowish brown color due to the formation of intramolecular and intermolecular charge transfer complexes. Therefore, it is difficult to apply to applications that require the above.

  In order to make colorless and transparent polyimide resins, it has been proposed to suppress the formation of charge transfer complexes within and between molecules by using alicyclic diamines or alicyclic acid anhydrides as diamine components. . For example, Patent Document 1 discloses a colorless and transparent semi-alicyclic polyimide resin formed from an alicyclic diamine and an aromatic dianhydride, and Patent Document 2 discloses an alicyclic diamine and an alicyclic acid anhydride. A colorless and transparent all-cycloaliphatic polyimide resin comprising a product has been proposed. However, the glass transition temperature of the obtained polyimide resin is about 280 ° C. or less, and the heat resistance is insufficient, so that it is difficult to apply to the main constituent part of the FPC insulating layer. In addition, since the colorless and transparent polyimide resin suppresses charge transfer complex formation, there is a problem that it is difficult to satisfy the low thermal expansion required for FPC.

  Patent Document 3 and Patent Document 4 disclose a laminate of a metal and a polyimide resin using a fluorinated polyimide as an insulating resin layer. The laminate shown here focuses on the transparency of the insulating layer. For wiring boards suitable for FPC applications because of excellent transparency, but insufficient control of the thermal expansion coefficient of the insulating layer and other characteristics, and low adhesion to smooth metal layers The properties as a laminate were not fully satisfied.

  Wiring board laminates used in FPC are composed of thin metal foil and insulating resin layer including polyimide resin layer, and if the difference in coefficient of thermal expansion (CTE) between metal foil and insulating resin layer is greatly different, There are problems such as warping and curling, and changes in dimensions when mounting electronic parts, making accurate mounting impossible. On the other hand, a laminate for a wiring board having an insulating resin layer with excellent transparency has 1) excellent visibility from the insulating resin layer side when a semiconductor element is mounted on the wiring board, or 2) a semiconductor on the wiring board. This is advantageous for light irradiation from the insulating resin layer side when the element is bonded via a photocurable resin, and a wider application can be expected.

Japanese Patent Laid-Open No. 7-10993 JP 2008-163210 A Japanese Unexamined Patent Publication No. 4-47933 Japanese Patent Laid-Open No. 10-374611

  An object of this invention is to provide the laminated body for wiring boards which has the outstanding heat resistance, the dimensional stability represented by the thermal expansion coefficient, a softness | flexibility, and high transparency.

  As a result of repeated studies to solve the above problems, the present inventors used a specific polyimide resin for the polyimide resin constituting the laminate for a wiring board or the insulating resin layer of the FPC, and an appropriate layer structure, It has been found that the above problem can be solved by employing a copper foil having a specific surface roughness for the metal layer, and the present invention has been completed.

That is, the present invention provides a laminate having a metal layer on one or both sides of an insulating resin layer, the insulating resin layer having two or more different polyimide resin layers, and at least one of the polyimide resin layers is represented by the following general formula: A polyimide resin layer (i) containing 70 mol% or more of the structural unit represented by (1), and at least one of the polyimide resin layers has a glass transition temperature lower by 20 ° C. or more than the polyimide resin layer (i) The resin layer (ii) has a light transmittance of 75% or more at a wavelength of 500 nm of the insulating resin layer, a thermal expansion coefficient of 30 ppm / K or less, and a surface roughness Rz on the insulating resin layer contact surface side of the metal layer is 0. It is a laminate for a wiring board, characterized in that it is 5 μm or less. Here, the polyimide resin layer constituting the insulating resin layer is formed by laminating two or three polyimide resin layers selected from the polyimide resin layer (i) and the polyimide resin layer (ii).

A preferred embodiment of the present invention is shown below.
-The laminate for a wiring board, wherein the thickness of the insulating resin layer is in the range of 10 to 50 µm, and the thickness ratio of the polyimide resin layer (i) in the insulating resin layer is 70 to 95% of the thickness of the insulating resin layer.
The laminate for a wiring board, wherein the polyimide resin layer (ii) has a structural unit represented by the following general formula (2) as a main component, and the peel strength between the insulating resin layer and the metal layer is 0.6 kN / m or more. .
-The said laminated body for wiring boards whose YI value of an insulating resin layer is 30 or less.

  The laminate for a wiring board of the present invention or the FPC obtained therefrom has excellent heat resistance, dimensional stability represented by a thermal expansion coefficient, flexibility, and high transparency. Because of this, it can be used in a wide range of fields for electronic devices and the like, and thus contributes to the industry. Although the use is not particularly limited, it is suitably used for an application requiring colorless transparency such as mounting of a semiconductor element.

Below, the laminated body for wiring boards of this invention is demonstrated.
The laminate for a wiring board of the present invention has a metal layer on at least one surface of the insulating resin layer, that is, on one side or both sides. The insulating resin layer has two or more polyimide resin layers.

  In order to laminate the insulating resin layer and the metal layer, a polyimide precursor resin solution (also referred to as a polyamic acid solution) for forming the insulating resin layer is applied on a metal layer such as copper foil or stainless steel, and then dried and cured. A so-called casting method, a so-called laminating method in which a metal layer is thermally laminated after applying a thermoplastic polyimide to a polyimide film, a so-called conductive layer is formed by electroplating after forming a conductive layer on the surface of the polyimide film by sputtering. There are sputter plating methods. Any of these methods may be used, but the casting method in which the polyimide precursor resin solution is applied and then dried and cured is most suitable. However, the present invention is not limited to this.

  The insulating resin layer has two or more polyimide resin layers, and the main layer is a polyimide resin layer (i) containing 70 mol% or more of the structural unit represented by the general formula (1). The main layer refers to the thickest layer in the insulating resin layer composed of a plurality of polyimide resin layers, preferably 60% or more of the total thickness of the insulating resin layer, more preferably 70 to 95%. Say.

  Further, at least one of the polyimide resin layers is a polyimide resin layer (ii) having a glass transition temperature of 20 ° C. or more lower than that of the polyimide resin layer (i), preferably a structural unit represented by the general formula (2) Is the main component. Here, it is desirable that the glass transition temperature of the polyimide resin layer (i) and the polyimide resin layer (ii) has a difference of 30 ° C. or more, preferably 50 to 150 ° C.

The main chain of the polyimide resin layer is composed of structural units represented by the following general formula (3). Since such a polyimide resin is generally produced by a method in which a diamine and an aromatic dianhydride are reacted in a solvent, this method will be described as a representative example, but the polyimide resin used in the present invention will be described. The manufacturing method is not limited to this. In the structural unit represented by the following general formula (3), Ar ₁ is a tetravalent organic group having one or more aromatic rings, and can be said to be a residue generated from an aromatic dianhydride. ₂ is a divalent organic group having one or more aromatic rings, and can be said to be a residue derived from an aromatic diamine. Thus, Ar ₁ and Ar ₂ are understood by describing the aromatic dianhydrides and aromatic diamines used. In addition, the polyimide resin layer as used in this specification is understood to have the meaning of the polyimide resin which comprises a polyimide resin layer, when the chemical structure or manufacturing method of the resin is demonstrated.

（式中、Ar₁は芳香環を1個以上有する4価の有機基であり、Ar₂は芳香環を1個以上有する2価の有機基である。）

(In the formula, Ar ₁ is a tetravalent organic group having one or more aromatic rings, and Ar ₂ is a divalent organic group having one or more aromatic rings.)

The acid dianhydride used as an essential raw material component of the polyimide resin layer (i) is pyromellitic dianhydride (PMDA) represented by the following formula (4). PMDA can be used alone, but is preferably used in combination with 2,2-bis (3,4-dicarboxyphenyl) -hexafluoropropane dianhydride (6FDA).

The diamine used as an essential raw material component of the polyimide resin layer (i) is 2,2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl (TFMB) represented by the following formula (5). It is.

  The polyimide resin layer (ii) is not limited as long as it gives the glass transition temperature, but preferably includes a structural unit represented by the general formula (2). The polyimide resin layer (ii) whose main component is the structural unit represented by the general formula (2) has a low glass transition point, good adhesion to the metal layer, and excellent light transmittance.

Therefore, the acid dianhydride and diamine used as raw material components of the polyimide resin layer (ii) are 3,3 ′, 4,4′-biphenyltetra represented by the following formula (6) as the acid dianhydride. It is preferable to use carboxylic dianhydride (BPDA).

As the diamine, bis [4- (aminophenoxy) phenyl] sulfone (BAPS) represented by the following formula (7) is preferably used.

  As mentioned above, as the aromatic dianhydride used as the raw material component of the polyimide resin layer (i), other acid dianhydrides other than PMDA can be used in combination. Moreover, as an aromatic acid dianhydride used as a raw material component of a polyimide resin layer (ii), other acid dianhydrides other than BPDA can be used together as all or a part thereof.

  The aromatic dianhydride that can be used in combination with PMDA or BPDA is not particularly limited, but specific examples include BPDA and PMDA, and 3,3 ′, 4,4′-benzophenone tetracarboxylic acid. Dianhydride, 2,2 ', 3,3'-benzophenone tetracarboxylic dianhydride, 2,3,3', 4'-benzophenone tetracarboxylic dianhydride, naphthalene-1,2,5,6- Tetracarboxylic dianhydride, naphthalene-1,2,4,5-tetracarboxylic dianhydride, naphthalene-1,4,5,8-tetracarboxylic dianhydride, naphthalene-1,2,6,7 -Tetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5,6,7-hexahydronaphthalene-1,2,5,6-tetracarboxylic dianhydride, 4,8-dimethyl -1,2,3,5,6,7-hexahydronaphthalene-2,3,6,7-tetracarboxylic dianhydride, 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic acid Dianhydride, 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride 2,3,6,7-tetrachloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 1,4,5,8-tetrachloronaphthalene-2,3,6,7-tetra Carboxylic dianhydride, 2,2 ', 3,3'-biphenyltetracarboxylic dianhydride, 2,3,3', 4'-biphenyltetracarboxylic dianhydride, 3,3``, 4, 4 ''-p-terphenyltetracarboxylic dianhydride, h2,2 '', 3,3 ''-p-terphenyltetracarboxylic dianhydride, 2,3,3 '', 4 ''- p-Terphenyltetracarboxylic dianhydride, 2,2-bis (2,3-dicarboxyphenyl) -propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) -propane dianhydride Bis (2,3-dicarboxyphenyl) ether dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3.4-dicarboxyphenyl) methane dianhydride, bis (2,3- Dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) sulfone Dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, perylene-2,3,8, 9-tetracarboxylic dianhydride, perylene-3,4,9,10-tetracarboxylic dianhydride, perylene-4,5,10,11-tetracarboxylic dianhydride, perylene-5,6,11 , 12-tetracarboxylic dianhydride, phenanthrene-1,2,7,8-tetracarboxylic dianhydride, phenanthrene-1, 2,6,7-tetracarboxylic dianhydride, phenanthrene-1,2, 9,10-tetracarboxylic dianhydride, cyclopentane-1,2,3,4-tetracarboxylic dianhydride, pyrazine-2,3,5,6-tetracarboxylic dianhydride, pyrrolidine-2, 3,4,5-tetracarboxylic dianhydride, thiophene-2,3,4,5-tetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, (trifluoromethyl) pyromellitic acid Anhydride, Di (Trifluor Methyl) pyromellitic dianhydride, di (heptafluoropropyl) pyromellitic dianhydride, pentafluoroethyl pyromellitic dianhydride, bis {3,5-di (trifluoromethyl) phenoxy} pyromellitic acid Anhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 5,5'-bis (trifluoromethyl) -3,3 ', 4,4'-tetracarboxybiphenyl Anhydride, 2,2 ', 5,5'-tetrakis (trifluoromethyl) -3,3', 4,4'-tetracarboxybiphenyl dianhydride, 5,5'-bis (trifluoromethyl) -3 , 3 ', 4,4'-Tetracarboxydiphenyl ether dianhydride, 5,5'-bis (trifluoromethyl) -3,3', 4,4'-tetracarboxybenzophenone dianhydride, bis {(trifluoro Methyl) dicarboxyphenoxy} benzene dianhydride, bis {(trifluoromethyl) Til) dicarboxyphenoxy} trifluoromethylbenzene dianhydride, bis (dicarboxyphenoxy) trifluoromethylbenzene dianhydride, bis (dicarboxyphenoxy) bis (trifluoromethyl) benzene dianhydride, bis (dicarboxyphenoxy) ) Tetrakis (trifluoromethyl) benzene dianhydride, 2,2-bis {(4- (3,4-dicarboxyphenoxy) phenyl} hexafluoropropane dianhydride, bis {(trifluoromethyl) dicarboxyphenoxy} Biphenyl dianhydride, bis {(trifluoromethyl) dicarboxyphenoxy} bis (trifluoromethyl) biphenyl dianhydride, bis {(trifluoromethyl) dicarboxyphenoxy} diphenyl ether dianhydride, bis (dicarboxyphenoxy) bis (Trifluoro And methyl) biphenyl dianhydride. Moreover, these may be used independently or can also be used together 2 or more types.

  Similarly, as an aromatic diamine used as a raw material component of the polyimide resin layer (i), an aromatic diamine other than TFMB can be used in combination as a part thereof. Moreover, as aromatic diamine used as a raw material component of a polyimide resin layer (ii), other aromatic diamines other than BAPS can be used together as all or a part thereof.

  The diamine used together with the TFMB of the polyimide resin layer (i) and the BAPS of the polyimide resin layer (ii) is not particularly limited, but specific examples include BAPS and TFMB, and 4,6-dimethyl. -m-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, 2,4-diaminomesitylene, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,5,3 ', 5'-tetra Methyl-4,4'-diaminodiphenylmethane, 2,4-toluenediamine, m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenylpropane, 3,3'-diaminodiphenylpropane, 4,4'- Diaminodiphenylethane, 3,3'-diaminodiphenylethane, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 2,2-bis (4-aminophenoxyphenyl) propane, 2,2-bis [4 -(4-Aminophenoxy) phenyl] propane, 4,4 ' -Diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 1, 3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, benzidine, 3,3'-diaminobiphenyl, 3,3 '-Dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxybenzidine, 4,4 "-diamino-p-terphenyl, 3,3" -diamino-p-terphenyl, bis (p-aminocyclohexyl ) Methane, bis (p-β-amino-t-butylphenyl) ether, bis (p-β-methyl-δ-aminopentyl) benzene, p-bis (2-methyl-4-aminopentyl) benzene, p- Bis (1,1-dimethyl-5-aminopentyl) benzene, 1,5-diaminona Phthalene, 2,6-diaminonaphthalene, 2,4-bis (β-amino-t-butyl) toluene, 2,4-diaminotoluene, m-xylene-2,5-diamine, p-xylene-2,5- Diamine, m-xylylenediamine, p-xylylenediamine, 2,6-diaminopyridine, 2,5-diaminopyridine, 2,5-diamino-1,3,4-oxadiazole, piperazine, 4- (1H , 1H, 11H-eicosafluoroundecanoxy) -1,3-diaminobenzene, 4- (1H, 1H-perfluoro-1-butanoxy) -1,3-diaminobenzene, 4- (1H, 1H-per Fluoro-1-heptanoxy) -1,3-diaminobenzene, 4- (1H, 1H-perfluoro-1-octanoxy) -1,3-diaminobenzene, 4-pentafluorophenoxy-1,3-diaminobenzene, 4 -(2,3,5,6-tetrafluorophenoxy) -1,3-diaminobenzene, 4- (4-fluorophenoxy) -1,3-diaminobenzene, 4- (1H, 1H, 2H , 2H-perfluoro-1-hexanoxy) -1,3-diaminobenzene, 4- (1H, 1H, 2H, 2H-perfluoro-1-dodecanoxy) -1,3-diaminobenzene, (2,5)- Diaminobenzotrifluoride, diaminotetra (trifluoromethyl) benzene, diamino (pentafluoroethyl) benzene, 2,5-diamino (perfluorohexyl) benzene, 2,5-diamino (perfluorobutyl) benzene, 2,2 ' -Bis (trifluoromethyl) -4,4'-diaminobiphenyl, 3,3'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, octafluorobenzidine, 4,4'-diaminodiphenyl ether, 2, 2-bis (4-aminophenyl) hexafluoropropane, 1,3-bis (anilino) hexafluoropropane, 1,4-bis (anilino) octafluorobutane, 1,5-bis (anilino) decafluorope Tan, 1,7-bis (anilino) tetradecafluoroheptane, 2,2'-bis (trifluoromethyl) -4,4'-diaminodiphenyl ether, 3,3'-bis (trifluoromethyl) -4,4 '-Diaminodiphenyl ether, 3,3', 5,5'-tetrakis (trifluoromethyl) -4,4'-diaminodiphenyl ether, 3,3'-bis (trifluoromethyl) -4,4'-diaminobenzophenone, 4,4'-diamino-p-terphenyl, 1,4-bis (p-aminophenyl) benzene, p- (4-amino-2-trifluoromethylphenoxy) benzene, bis (aminophenoxy) bis (trifluoro Methyl) benzene, bis (aminophenoxy) tetrakis (trifluoromethyl) benzene, 2,2-bis {4- (4-aminophenoxy) phenyl} hexafluoropropane, 2,2-bis {4- (3-aminophenoxy) ) Phenyl} hexafluo Propane, 2,2-bis {4- (2-aminophenoxy) phenyl} hexafluoropropane, 2,2-bis {4- (4-aminophenoxy) -3,5-dimethylphenyl} hexafluoropropane, 2, 2-bis {4- (4-aminophenoxy) -3.5-ditrifluoromethylphenyl} hexafluoropropane, 4,4'-bis (4-amino-2-trifluoromethylphenoxy) biphenyl, 4,4'-bis (4-amino-3-trifluoromethylphenoxy) biphenyl, 4,4'-bis (4-amino-2-trifluoromethylphenoxy) diphenylsulfone, 4,4'-bis (3-amino-5-trifluoro Methylphenoxy) diphenylsulfone, 2,2-bis {4- (4-amino-3-trifluoromethylphenoxy) phenyl} hexafluoropropane, bis {(trifluoromethyl) aminophenoxy} biphenyl, bis [{(trifluoro Chill) aminophenoxy} phenyl] hexafluoropropane, bis {2 - [(aminophenoxy) phenyl] hexafluoroisopropyl} benzene, 4,4'-bis (4-aminophenoxy) octafluoro biphenyl. These can be used alone or in combination of two or more.

  In selecting aromatic diamine and aromatic dianhydride, the heat resistance of the polyimide resin layer, dimensional stability represented by the thermal expansion coefficient, flexibility, adhesion to metal foil, high transparency, etc. It will be chosen to develop the required properties. From the viewpoint of the above characteristics for the polyimide resin layer (i), TFMB is preferably selected as the diamine, and PMDA is preferably selected as the aromatic dianhydride, and BAPS is aromatic as the diamine of the polyimide resin layer (ii). BPDA is preferably selected as the acid dianhydride.

  The polyimide resin layer (i) constituting the polyimide resin layer contains 70 mol% or more of the structural unit represented by the general formula (1), and the polyimide resin layer (ii) is represented by the general formula (2). It is preferable that a structural unit is included and used as a main component. Here, the main component means that the structural unit is contained in an amount of 50 mol% or more, preferably 70 mol% or more, more preferably 90 mol% or more.

  Although the kind of metal layer is not particularly limited, it can be appropriately selected from copper foil, copper alloy foil, stainless steel foil, etc., but copper foil or copper alloy foil is preferable. In selecting these metal foils, the metal foil is selected so as to exhibit characteristics required for the purpose of use, such as light transmittance of the polyimide resin layer and adhesion between the metal layer and the polyimide resin layer. From the viewpoint of light transmittance of the polyimide resin layer, the surface roughness Rz of the metal layer needs to be 0.5 μm or less, and it is preferable to use one having a surface roughness of 0.1 to 0.4 μm. Such a metal foil can be selected from commercially available copper foils.

  The polyamic acid for forming the polyimide resin layer is a known method in which the aromatic diamine component and the aromatic tetracarboxylic dianhydride component shown above are used in substantially equimolar amounts and polymerized in an organic polar solvent. Can be manufactured by. That is, it is obtained by dissolving the diamine in an organic polar solvent such as N, N-dimethylacetamide under a nitrogen stream and then adding the aromatic tetracarboxylic dianhydride and reacting at room temperature for about 5 hours. Can do.

  The laminate for a wiring board of the present invention, for example, applies the polyamic acid solution obtained by the above reaction onto a metal foil serving as a support or a resin layer formed on the metal foil using an applicator or the like. It can be obtained by predrying at a temperature of 150 ° C. or lower for 2 to 20 minutes and then heat-treating at a temperature of usually about 130 to 360 ° C. for about 2 to 30 minutes to remove the solvent and imidize. Since the laminate for a wiring board of the present invention has a plurality of polyimide resin layers, after repeating the operation of applying a polyamic acid solution and drying, heat treatment is performed to remove the solvent, and this is further heat treated at a high temperature to obtain an imide. By forming, a polyimide resin layer can be formed. At this time, the total thickness of the formed polyimide resin layer is 3 to 75 μm, preferably 10 to 50 μm, more preferably 15 to 40 μm. If the total thickness of the polyimide resin layer becomes too thick, problems such as a decrease in light transmittance occur.

  In the present invention, the thickness range of the polyimide resin layer (i) relative to the total thickness of the polyimide resin layer may be 50% or more, preferably 70% or more and 95% or less. The thickness range of the polyimide resin layer (ii) is less than 50%, preferably 5 to 30%. The polyimide resin layer (i) preferably has a large thickness in the insulating layer in order to give the insulating layer transparency and high heat resistance. On the other hand, since the polyimide resin layer (ii) is excellent in adhesiveness, the polyimide resin layer (ii) is preferably provided in contact with the metal layer. When it has a metal layer on both surfaces, it is good for the both surface sides of an insulating layer to be polyimide resin layer (ii), and to make the thickness of each side into the said range.

  When the polyamic acid and the degree of polymerization of the polyimide used for forming the polyimide resin layer are expressed in the viscosity range of the polyamic acid solution, the solution viscosity is preferably in the range of 500 cP to 200,000 cP. The solution viscosity can be measured with a cone plate viscometer with a thermostatic water bath.

Moreover, when manufacturing the laminated body for wiring boards which has a metal layer on both surfaces, it adhere | attaches directly on the polyimide resin layer of the laminated body for single-sided wiring boards obtained by the said method, or the transparency of an insulating resin layer is not inhibited. After forming the layer, the metal layer can be obtained by laminating by means such as thermocompression bonding. In the present invention, the insulating layer is transparent, and from the viewpoint of exhibiting other characteristics of the polyimide resin such as heat resistance, it is preferable that the insulating resin layer is substantially composed only of the polyimide resin layer. The hot pressing temperature in the case of thermocompression bonding of the metal layer is not particularly limited, but is preferably equal to or higher than the glass transition temperature of the polyimide resin layer adjacent to the metal layer to be used. The hot press pressure is preferably in the range of 1 to 500 kg / m ² , although it depends on the type of press equipment used. Furthermore, the preferable metal foil used at this time can use the thing similar to the above-mentioned metal foil, The preferable thickness is also 50 micrometers or less, More preferably, it is the range of 5-40 micrometers.

  In the laminate for a wiring board of the present invention, the light transmittance at 500 nm of the insulating resin layer portion from which the metal layer is removed is 75% or more, and the thermal expansion coefficient of the insulating resin layer is 30 ppm / K or less, preferably 25 ppm / K or less. Thus, a laminate for a wiring board having a peel strength with a metal layer of 0.6 kN / m or more can be obtained. And, it is thought that the polyimide resin layer (i) contributes to the light transmittance and the thermal expansion coefficient, and the polyimide resin layer (ii) contributes to the peel strength. Absent. The light transmittance, the thermal expansion coefficient, and the peel strength are measured under the conditions described in the examples, and those not particularly described are measured values at room temperature (23 ° C.).

  EXAMPLES Hereinafter, although the content of this invention is demonstrated concretely based on an Example, this invention is not limited to the range of these Examples.

Abbreviations used in Examples and the like are shown below.
-TFMB: 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl-BAPS: bis [4- (aminophenoxy) phenyl] sulfone-PMDA: pyromellitic dianhydride-6FDA: 2, 2-Bis (3,4-dicarboxyphenyl) -hexafluoropropane dianhydride, BPDA: 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, DMAc: N, N-dimethylacetamide

  In addition, measurement methods and conditions for various physical properties in the examples are shown below.

[viscosity]
The viscosity was measured at 25 ° C. for the polyamic acid solution obtained in the synthesis example with a cone plate viscometer (manufactured by Tokimec Co., Ltd.) equipped with a constant temperature water bath.

[Coefficient of thermal expansion (CTE)]
A tensile test is performed in a temperature range from 30 ° C to 260 ° C at a constant rate of temperature increase (20 ° C / min) while applying a 5.0 g load with a thermomechanical analysis (TMA) device using a polyimide film of 3 mm × 15 mm size. The thermal expansion coefficient (ppm / K) was measured from the amount of elongation of the polyimide film with respect to temperature.

[Glass transition temperature (Tg)]
The dynamic viscoelasticity of a polyimide film (10 mm × 22.6 mm) was measured at a rate of 5 ° C./min from 20 ° C. to 500 ° C. with a dynamic thermomechanical analyzer, and the glass transition temperature (tan δ maximum value) : ° C.).

[Light transmittance]
The light transmittance at 500 nm was determined for a polyimide film (50 mm × 50 mm) with a U4000 self-recording spectrophotometer.
[Yellowness (YI)]
A polyimide film (50 mm × 50 mm) was measured for yellowness according to JISK7105 using a light source C with a U4000 type self-recording spectrophotometer.

[Peel strength]
Using a tension tester, the resin side of the test sample having a circuit with a width of 1 mm obtained from the laminate was fixed to the aluminum plate with double-sided tape, and the copper was peeled at a speed of 50 mm / min in the 180 ° direction to peel strength. Asked.

Synthesis Examples 1 to 4
In order to synthesize the polyamic acids A to D, the diamines shown in Table 1 were dissolved in the solvent DMAc while stirring in a 200 ml separable flask under a nitrogen stream. Subsequently, the tetracarboxylic dianhydride shown in Table 1 was added. Thereafter, the solution was stirred at room temperature for 5 hours to conduct a polymerization reaction, and kept for a whole day and night. A viscous polyamic acid solution was obtained, and it was confirmed that a polyamic acid having a high degree of polymerization was produced. Table 1 shows the solid content and solution viscosity of the obtained solutions of polyamic acids A to D (hereinafter referred to as polyamic acid solutions A to D). Here, the solid content is the polyamic acid concentration. The results are summarized in Table 1. The example which uses the polyamic acid A is made into the synthesis example 1, and the synthesis example number is attached | subjected in order below.

Reference Examples 1-4
Each of the polyamic acid solutions A to D obtained in Synthesis Examples 1 to 4 is approximately 25 μm after heat treatment using an applicator on an electrolytic copper foil having a thickness of 12 μm and a surface roughness Rz of 0.3 μm. After coating and drying at 125 ° C for 1 to 10 minutes, further heat treatment is performed at 130 ° C, 145 ° C, 160 ° C, 200 ° C, 280 ° C, 320 ° C, and 360 ° C for 1 to 15 minutes each, Four types of laminates having a single polyimide layer thereon were obtained. For each of the obtained laminates, a copper film was etched away using an aqueous ferric chloride solution to create a polyimide film, and the coefficient of thermal expansion (CTE), glass transition temperature (Tg), and light transmittance at 500 nm were determined. It was. Table 2 shows the measurement results. In addition, the example which uses the polyamic acid A is made into the reference example 1, and the reference example number is attached | subjected in order.

Reference Example 5
The light transmittance at 500 nm of CTE of a commercially available Kapton film (Kapton150EN) was determined. Various results are shown in Table 2.

Example 1
The polyamic acid solution D obtained in Synthesis Example 4 was applied onto an electrolytic copper foil having a thickness of 12 μm and a surface roughness Rz of 0.3 μm so that the cured thickness would be 1 μm, and the solvent was removed by heating at 125 ° C. did. Next, the polyamic acid solution A obtained in Synthesis Example 1 was applied thereon so that the thickness after curing was 20 μm, and dried by heating at 125 ° C. to remove the solvent. Furthermore, the polyamic acid solution D was applied thereon so that the thickness after curing was 1 μm, and the solvent was removed by heating and drying at 125 ° C. Thereafter, a stepwise heat treatment is performed at 130 ° C., 145 ° C., 160 ° C., 200 ° C., 280 ° C., 320 ° C., and 360 ° C. for 1 to 15 minutes each to form a wiring board comprising three polyimide layers on the copper foil. A laminate was prepared. The thickness of the polyimide layer on the copper foil is 1/22/1 μm in the order of D / A / D. For the evaluation of the polyimide resin layer, the thermal expansion coefficient (CTE), the light transmittance at 500 nm, and the peel strength were determined for the polyimide film from which the copper foil of the wiring board laminate was removed by etching. The evaluation results of the laminate are shown in Table 3.

Example 2
The polyamic acid solution A was applied onto an electrolytic copper foil having a thickness of 12 μm and a surface roughness Rz of 0.3 μm so that the thickness after curing was 24 μm, and dried by heating at 125 ° C. to remove the solvent. Furthermore, the polyamic acid solution D was coated thereon so that the thickness after curing was 2 μm, and the solvent was removed by heating and drying at 125 ° C. Thereafter, a stepwise heat treatment is performed at 130 ° C., 145 ° C., 160 ° C., 200 ° C., 280 ° C., 320 ° C., and 360 ° C. for 1 to 15 minutes each to form a wiring board composed of two polyimide layers on the copper foil. A laminate was prepared. The thickness of the polyimide layer on the copper foil is 24/2 μm in the order of A / D. The evaluation of the polyimide resin layer was performed on a polyimide film obtained by removing the copper foil of the wiring board laminate by etching. The evaluation results of the laminate are shown in Table 3. In addition, the laminated body for wiring boards obtained in Examples 1 and 2 had the same flexibility as a commercially available copper-clad laminate.

Comparative Example 1
A laminate for a wiring board was prepared in the same manner as in Example 1 except that the configuration of the polyimide resin layer was set to D / B / D and the thickness of each layer was set to 1/20/1 μm in order. The evaluation results of the laminate are shown in Table 3.

Comparative Example 2
A laminate for a wiring board was prepared in the same manner as in Example 1 except that the configuration of the polyimide resin layer was set to D / C / D and the thicknesses of the respective layers were set to 1/22/1 μm in order. The evaluation results of the laminate are shown in Table 3.

Comparative Example 3
A laminate for a wiring board was prepared in the same manner as in Example 1 except that a rolled copper foil having a thickness of 12 μm and a surface roughness Rz of 0.7 μm was used, and evaluated in the same manner as in Example 1. The evaluation results of the laminate are shown in Table 3.

Claims (4)

In a laminate having a metal layer on one or both sides of an insulating resin layer, the insulating resin layer has two or more different polyimide resin layers, and at least one of the polyimide resin layers is represented by the following general formula (1). A polyimide resin layer (i) containing 70 mol% or more of a structural unit, and at least one of the polyimide resin layers is a polyimide resin layer (ii) having a glass transition temperature of 20 ° C. or more lower than that of the polyimide resin layer (i). And the insulating resin layer comprises two or three polyimide resin layers selected from the polyimide resin layer (i) and the polyimide resin layer (ii), and the light transmittance at a wavelength of 500 nm of the insulating resin layer is 75% or more. A laminate for a wiring board having a thermal expansion coefficient of 30 ppm / K or less and a surface roughness Rz on the insulating resin layer contact surface side of the metal layer of 0.5 μm or less.

The laminate for a wiring board according to claim 1, wherein the thickness of the insulating resin layer is in the range of 10 to 50 µm, and the thickness ratio of the polyimide resin layer (i) in the insulating resin layer is 70 to 95% of the thickness of the insulating resin layer. body. The wiring board according to claim 1 or 2, wherein the polyimide resin layer (ii) includes a structural unit represented by the following general formula (2), and a peel strength between the insulating resin layer and the metal layer is 0.6 kN / m or more. Laminated body.

The laminated body for a wiring board according to claim 1, wherein the insulating resin layer has a YI value of 30 or less.