JP6559027B2 - Polyamide acid, polyimide, resin film and metal-clad laminate - Google Patents

Description

  The present invention relates to polyamic acid, polyimide, and a resin film and a metal-clad laminate using the polyimide.

  In recent years, with the progress of downsizing, weight reduction, and space saving of electronic devices, flexible printed wiring boards (FPCs) that are thin, light, flexible, and have excellent durability even after repeated bending are used. The demand for Circuits) is increasing. FPC can be mounted three-dimensionally and densely in a limited space. For example, it can be used for wiring of movable parts of electronic devices such as HDDs, DVDs, mobile phones, and parts such as cables and connectors. It is expanding.

  In addition to the above-described higher density, higher performance of equipment has been advanced, so that it is necessary to cope with higher frequency transmission signals. When transmitting a high-frequency signal, if the transmission loss of the signal transmission path is large, inconveniences such as loss of the electric signal and long signal delay time occur. For this reason, it is important to reduce the transmission loss of the FPC. In order to cope with higher frequencies, FPC using a liquid crystal polymer characterized by a low dielectric constant and a low dielectric loss tangent as a dielectric layer is used. However, although the liquid crystal polymer is excellent in dielectric properties, there is room for improvement in heat resistance and adhesion to metal foil.

  In order to improve heat resistance and adhesiveness, a metal-clad laminate using polyimide as an insulating layer has been proposed (Patent Document 1). According to Patent Document 1, it is generally known that the dielectric constant is lowered by using an aliphatic polymer as a monomer, and an aliphatic (chain) tetracarboxylic dianhydride is used. Since the heat resistance of the polyimide obtained in this way is extremely low, it cannot be used for processing such as soldering, and there is a problem in practical use. It is said that polyimide with improved heat resistance can be obtained. However, although such a polyimide film has a dielectric constant at 10 GHz of 3.2 or less, the dielectric loss tangent exceeds 0.01, and the dielectric properties have not been sufficient. In addition, many polyimides using aliphatic monomers described above have a large coefficient of thermal expansion, and warpage occurs in metal-clad laminates using these as insulating layers, making it difficult to form an insulating layer for circuit boards. It was.

JP 2004-358916 A

  An object of the present invention is to provide an insulating layer material for a circuit board that can suppress the occurrence of warping while enabling the high frequency accompanying the downsizing and high performance of electronic equipment.

  In order to solve the above-mentioned problems, the present inventors have a low thermal expansion coefficient (CTE) when a resin film is formed while a polyimide obtained from a polyamic acid having a specific diamine structure has low dielectric properties. It has been found that a circuit board such as an FPC having good transmission characteristics can be obtained while suppressing the occurrence of warpage, and the present invention has been completed.

The polyamic acid of the present invention is obtained by reacting a diamine component with an acid anhydride component containing a tetracarboxylic acid anhydride. In the polyamic acid of the present invention, the diamine component contains a diamine compound represented by the following general formula (i) within a range of 10 to 60 mol% with respect to the total diamine component,
And,
The acid anhydride component is one or more tetracarboxylic anhydrides selected from the group consisting of pyromellitic anhydride (PMDA) and 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (BPDA) In the range of 50 to 100 mol% with respect to the total acid anhydride component.

［式中、Ｒは炭素数４〜８の分岐鎖のアルキル基を意味し、ｐは１〜２の数を意味する。ここで、ｐが２の場合、Ｒは独立して異なる炭素数をとり得る。］

[Wherein, R represents a branched alkyl group having 4 to 8 carbon atoms, and p represents a number of 1 to 2. Here, when p is 2, R can independently have different carbon numbers. ]

In the polyamic acid of the present invention, 2,2′-dimethyl-4,4′-diaminobiphenyl (m-TB), 2,2′-diethyl-4,4′-diaminobiphenyl (m-EB) is added to the diamine component. ) And 2,2′- di- n-propyl-4,4′-diaminobiphenyl (m-NPB) in an amount of 40 to 90 mol% based on the total diamine component. It may be included within the range.

In the polyamic acid of the present invention, the diamine component contains the 2,2′-dimethyl-4,4′-diaminobiphenyl (m-TB), and the diamine compound represented by the general formula (i) is 1, Even 4-bis (4-aminophenoxy) -2,5-di-tert-butylbenzene (DTBAB) and / or 1,4-bis (4-aminophenoxy) -2,3-di-tert-butylbenzene Good. In this case, the acid anhydride component and the 1,4bis (4-aminophenoxy) -2,5-di-tert-butylbenzene (DTBAB) and / or the 1,4bis (4-aminophenoxy) -2 , 3-di-tert-butylbenzene may satisfy the relationship represented by the following formula A.
y = 0.2996x−8.4193 (Equation A)
[Wherein, x represents the 1,4-bis (4-aminophenoxy) -2,5-di-tert-butylbenzene (DTBAB) and / or the 1,4-bis (4-aminophenoxy) -2,3 -The value obtained by multiplying the total amount (mol%) of di-tert-butylbenzene by a factor of 2.1 and 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride in the acid anhydride component It means the sum with the blending amount (mol%) of (BPDA), and y means a number in the range of 10 to 30]

In the polyamic acid of the present invention, the diamine component contains the 2,2′-diethyl-4,4′-diaminobiphenyl (m-EB), and the diamine compound represented by the general formula (i) is 1, Even 4-bis (4-aminophenoxy) -2,5-di-tert-butylbenzene (DTBAB) and / or 1,4-bis (4-aminophenoxy) -2,3-di-tert-butylbenzene Good. In this case, the acid anhydride component and the 1,4bis (4-aminophenoxy) -2,5-di-tert-butylbenzene (DTBAB) and / or the 1,4bis (4-aminophenoxy) -2 , 3-Di-tert-butylbenzene may satisfy the relationship represented by the following formula B.
y = 0.0.313x-3.3320 (Formula B)
[Wherein x is the 1,4-bis (4-aminophenoxy) -2,5-di-tert-butylbenzene (DTBAB) and / or the 1,4-bis (4-aminophenoxy) -2,3- A value obtained by multiplying the total amount (mol%) of di-tert-butylbenzene by a factor of 1.9, and 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride ( BPDA) is the sum of the amount (mol%) and y is a number in the range of 10 to 30]

In the polyamic acid of the present invention, the diamine component contains 2,2′- di- n-propyl-4,4′-diaminobiphenyl (m-NPB) and the diamine compound represented by the general formula (i) Is 1,4-bis (4-aminophenoxy) -2,5-di-tert-butylbenzene (DTBAB) and / or 1,4-bis (4-aminophenoxy) -2,3-di-tert-butylbenzene There may be. In this case, the acid anhydride component and the 1,4bis (4-aminophenoxy) -2,5-di-tert-butylbenzene (DTBAB) and / or the 1,4bis (4-aminophenoxy) -2 , 3-di-tert-butylbenzene may satisfy the relationship represented by the following formula C.
y = 0.3005x + 15.0500 (Equation C)
[Wherein x is the 1,4-bis (4-aminophenoxy) -2,5-di-tert-butylbenzene (DTBAB) and / or the 1,4-bis (4-aminophenoxy) -2,3- A value obtained by multiplying the total amount (mol%) of di-tert-butylbenzene by a coefficient of 1.3, and 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride in the acid anhydride component ( BPDA) is the sum of the amount (mol%) and y is a number in the range of 10 to 30]

In the polyamic acid of the present invention, the diamine component contains the 2,2′-dimethyl-4,4′-diaminobiphenyl (m-TB), and the diamine compound represented by the general formula (i) is 1, It may be 4-bis (4-aminophenoxy) -2,5-di (1-methylpropyl) benzene. In this case, the blending amount of the acid anhydride component and 1,4bis (4-aminophenoxy) -2,5-di (1-methylpropyl) benzene satisfies the relationship represented by the following formula D. Also good.
y = 0.2986x-8.3997 (Formula D)
[Wherein x is a value obtained by multiplying the blending amount (mol%) of 1,4-bis (4-aminophenoxy) -2,5-di (1-methylpropyl) benzene by a coefficient of 4.3, and the acid Means the sum of the 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (BPDA) content in the anhydride component (mol%), and y is a number in the range of 10 to 30 Means]

In the polyamic acid of the present invention, the diamine component contains the 2,2′-diethyl-4,4′-diaminobiphenyl (m-EB), and the diamine compound represented by the general formula (i) is 1, It may be 4-bis (4-aminophenoxy) -2,5-di (1-methylpropyl) benzene. In this case, the blending amount of the acid anhydride component and the 1,4-bis (4-aminophenoxy) -2,5-di (1-methylpropyl) benzene satisfies the relationship represented by the following formula E. May be.
y = 0.003x−3.4028 (Equation E)
[Wherein x is a value obtained by multiplying the blending amount (mol%) of 1,4-bis (4-aminophenoxy) -2,5-di (1-methylpropyl) benzene with a coefficient of 4.1 It means the sum of the amount of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (BPDA) in the anhydride component (mol%), and y is in the range from 10 to 30 Means number]

In the polyamic acid of the present invention, the diamine component contains the 2,2′-dimethyl-4,4′-diaminobiphenyl (m-TB), and the diamine compound represented by the general formula (i) is 1, It may be 4-bis (4-aminophenoxy) -2,6-di-tert-butylbenzene. In this case, even if the blending amount of the acid anhydride component and the 1,4-bis (4-aminophenoxy) -2,6-di-tert-butylbenzene satisfies the relationship represented by the following formula F Good.
y = 0.2971x−8.3862 ... (Formula F)
[Wherein x is a value obtained by multiplying the blending amount (mol%) of 1,4-bis (4-aminophenoxy) -2,6-di-tert-butylbenzene by a factor of 4.5, and the acid anhydride It means the sum with the amount (mol%) of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (BPDA) in the component, and y means a number in the range of 10 to 30 To do]

In the polyamic acid of the present invention, the diamine component contains the 2,2′-diethyl-4,4′-diaminobiphenyl (m-EB), and the diamine compound represented by the general formula (i) is 1, It may be 4-bis (4-aminophenoxy) -2,6-di-tert-butylbenzene. In this case, even if the blending amount of the acid anhydride component and the 1,4-bis (4-aminophenoxy) -2,6-di-tert-butylbenzene satisfies the relationship represented by the following formula G: Good.
y = 0.2986x-3.397 ... (Formula G)
[Wherein x is a value obtained by multiplying the blending amount (mol%) of 1,4-bis (4-aminophenoxy) -2,6-di-tert-butylbenzene by a coefficient of 4.3, and the acid anhydride This means the sum of the amount of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (BPDA) in the component and the sum (mol%), and y is a number in the range from 10 to 30 means]

In the polyamic acid of the present invention, the diamine component contains the 2,2′-dimethyl-4,4′-diaminobiphenyl (m-TB), and the diamine compound represented by the general formula (i) is 1, It may be 4-bis (4-aminophenoxy) -2,5-di (2-methylpropyl) benzene. In this case, the blending amount of the acid anhydride component and the 1,4-bis (4-aminophenoxy) -2,5-di (2-methylpropyl) benzene satisfies the relationship represented by the following formula H. May be.
y = 0.3011x−8.6596 (Equation H)
[Wherein x is a value obtained by multiplying the blending amount (mol%) of 1,4-bis (4-aminophenoxy) -2,5-di (2-methylpropyl) benzene by a factor of 6.1, and the acid Means the sum of the 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (BPDA) content in the anhydride component (mol%), and y is a number in the range of 10 to 30 Means]

In the polyamic acid of the present invention, the diamine component contains the 2,2′-diethyl-4,4′-diaminobiphenyl (m-EB), and the diamine compound represented by the general formula (i) is 1, It may be 4-bis (4-aminophenoxy) -2,5-di (2-methylpropyl) benzene. In this case, the blending amount of the acid anhydride component and the 1,4 bis (4-aminophenoxy) -2,5-di (2-methylpropyl) benzene satisfies the relationship represented by the following formula I. May be.
y = 0.2984x-3.6137 ... (Formula I)
[Wherein x is a value obtained by multiplying the blending amount (mol%) of 1,4-bis (4-aminophenoxy) -2,5-di (2-methylpropyl) benzene by a factor of 6.0 and the acid It means the sum of the amount of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (BPDA) in the anhydride component (mol%), and y is in the range from 10 to 30 Means number]

  The polyimide of the present invention is obtained by imidizing the above polyamic acid.

  The resin film of this invention contains the polyimide obtained by imidating the said polyamic acid.

The resin film of the present invention may have a thermal expansion coefficient in the range of 10 × 10 ⁻⁶ to 30 × 10 ⁻⁶ (1 / K).

  The metal-clad laminate of the present invention has a resin layer containing the polyimide.

  The polyamic acid and polyimide of the present invention form a resin film while having low dielectric properties by using a diamine compound of the general formula (i) in which a branched alkyl group having 4 to 8 carbon atoms is introduced into the side chain. In this case, the coefficient of thermal expansion (CTE) can be kept low. Therefore, the resin film using the polyamic acid and the polyimide of the present invention can be suitably used, for example, as a base film layer of a metal-clad laminate. Further, by using the polyamic acid and polyimide of the present invention as an insulating layer material, it is possible to provide a circuit board such as an FPC having good transmission characteristics while suppressing the occurrence of warping.

  Embodiments of the present invention will be described below.

[Polyamide acid and polyimide]
<Polyamide acid>
The polyamic acid of the present embodiment is a precursor of the polyimide of the present embodiment, and is obtained by reacting a diamine component and an acid anhydride component containing a tetracarboxylic acid anhydride. Here, the diamine component is a diamine compound represented by the general formula (i) (hereinafter sometimes referred to as “diamine compound (i)”) in the range of 10 to 60 mol% with respect to the total diamine component. Including.

［式中、Ｒは炭素数４〜８の分岐鎖のアルキル基を意味し、ｐは１〜２の数を意味する。ここで、ｐが２の場合、Ｒは独立して異なる炭素数をとり得る。］

[Wherein, R represents a branched alkyl group having 4 to 8 carbon atoms, and p represents a number of 1 to 2. Here, when p is 2, R can independently have different carbon numbers. ]

  The diamine compound (i) is characterized by a branched alkyl group having 4 to 8 carbon atoms in the side chain (that is, a branched butyl group, a pentyl group, a hexyl group, as a group R in the general formula (i), A ptyl group or an octyl group). By using the diamine compound (i) having a branched alkyl group having 4 to 8 carbon atoms in the side chain as a diamine component, the imide group concentration is lowered, the dielectric constant is reduced, and the resin film is greatly improved. Increase in CTE can be suppressed.

  In the polyamic acid of the present embodiment, the acid anhydride component is pyromellitic anhydride (PMDA) and / or 3,3 ′, 4, within a range of 50 to 100 mol% with respect to the total acid anhydride component. Contains 4'-biphenyltetracarboxylic dianhydride (BPDA). By using PMDA and / or BPDA at a blending amount of 50 mol% or more, the molecular orientation in the polyimide is controlled and the CTE increase is suppressed, so the polyamic acid of this embodiment is used. It is possible to reduce the CTE of the formed resin film.

Moreover, in the polyamic acid of this Embodiment, a diamine component is a compounding quantity within the range of 40-90 mol% with respect to all the diamine components, and 2,2'- dimethyl- 4,4'- diaminobiphenyl (m -TB) The group consisting of 2,2'-diethyl-4,4'-diaminobiphenyl (m-EB) and 2,2'- di- n-propyl-4,4'-diaminobiphenyl (m-NPB) It preferably contains one or more diamine compounds selected from the above (hereinafter sometimes referred to as “biphenyl-based diamine compounds”). Use of these biphenyl-based diamine compounds as raw materials contributes to both low dielectric constant and low CTE of the resin film formed using the polyamic acid of the present embodiment.

<Polyimide>
The polyimide of the present embodiment is formed by imidizing the polyamic acid. The polyimide of the present embodiment preferably has structural units represented by the following general formulas (1) and (2).

［式中、ＡｒはＰＭＤＡ及び／又はＢＰＤＡを含む芳香族テトラカルボン酸無水物から誘導される４価の芳香族基、Ｒ_１はジアミン化合物(i)から誘導される２価の芳香族ジアミン残基、Ｒ_２はジアミン化合物(i)以外の芳香族ジアミンから誘導される２価の芳香族ジアミン残基をそれぞれ表し、ｍ、ｎは各構成単位の存在モル比を示し、ｍは０．１〜０．６の範囲内、ｎは０．４〜０．９の範囲内である］

[Wherein Ar is a tetravalent aromatic group derived from an aromatic tetracarboxylic anhydride containing PMDA and / or BPDA, and R ₁ is a divalent aromatic diamine residue derived from a diamine compound (i). Group R ₂ represents a divalent aromatic diamine residue derived from an aromatic diamine other than the diamine compound (i), m and n represent the molar ratio of each constituent unit, and m is 0.1 In the range of ~ 0.6, n is in the range of 0.4 to 0.9]

  Examples of the group Ar include those represented by the following formula (3) or formula (4).

［式中、Ｗは単結合、炭素数１〜１５の２価の炭化水素基、−Ｏ−、−Ｓ−、−ＣＯ−、−ＳＯ−、−ＳＯ_２−、−ＮＨ−若しくは−ＣＯＮＨ−から選ばれる２価の基を示す］

[Wherein, W is a single bond, a divalent hydrocarbon group having 1 to 15 carbon atoms, —O—, —S—, —CO—, —SO—, —SO ₂ —, —NH— or —CONH— Represents a divalent group selected from

  In particular, from the viewpoint of reducing the polar group of polyimide and improving the dielectric properties, the group Ar is represented by the formula (3) or W in the formula (4) is a single bond and a divalent carbon atom having 1 to 15 carbon atoms. What is represented by a hydrogen group, -O-, and -S- is preferable, and W in Formula (3) or Formula (4) is more preferably a single bond or a divalent hydrocarbon group having 1 to 15 carbon atoms. .

  In addition, the structural unit represented by the general formulas (1) and (2) may be present in the homopolymer or may be present as a structural unit of the copolymer. In the case of a copolymer having a plurality of structural units, it may exist as a block copolymer or a random copolymer.

Since polyimide is generally produced by reacting an acid anhydride and a diamine, a specific example of the polyimide of the present embodiment can be understood by explaining the acid anhydride and the diamine. In the above general formulas (1) and (2), the group Ar can be referred to as an acid anhydride residue, and the groups R ₁ and R ₂ can be referred to as diamine residues. And diamine.

  As the acid anhydride having the group Ar as a residue, at least one of PMDA and BPDA in which the group Ar is represented by the above formula (3) is used. By using PMDA and / or BPDA, the orientation of the molecules in the polyimide is controlled, thereby suppressing an increase in CTE, and the CTE of the resin film using the polyimide of this embodiment can be reduced. In addition to PMDA and BPDA, examples of the acid anhydride having a group Ar as a residue include 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride and 4,4′-oxydiphthalic anhydride. A thing is illustrated preferably. Further, 2,2 ′, 3,3′-, 2,3,3 ′, 4′- or 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 2,3 ', 3,4'-biphenyltetracarboxylic dianhydride, 2,2', 3,3'-biphenyltetracarboxylic dianhydride, 2,3 ', 3,4'-diphenyl ether tetracarboxylic dianhydride Bis (2,3-dicarboxyphenyl) ether dianhydride, 3,3 ″, 4,4 ″-, 2,3,3 ″, 4 ″-or 2,2 ″, 3, 3 ″ -p-terphenyltetracarboxylic dianhydride, 2,2-bis (2,3- or 3,4-dicarboxyphenyl) -propane dianhydride, bis (2,3- or 3.4 -Dicarboxyphenyl) methane dianhydride, bis (2,3- or 3,4-dicarboxyphenyl) sulfone dianhydride, 1,1-bis (2,3- or 3,4-dicarboxyphenyl) ethane Dianhydride, 1,2,7,8-, 1,2,6,7- or 1,2,9, 0-phenanthrene-tetracarboxylic dianhydride, 2,3,6,7-anthracenetetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) tetrafluoropropane dianhydride, 2, 3,5,6-cyclohexane dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1,4,5,8 -Naphthalenetetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5,6,7-hexahydronaphthalene-1,2,5,6-tetracarboxylic dianhydride, 2,6- Or 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,3,6,7- (or 1,4,5,8-) tetrachloronaphthalene-1,4, 5,8- (or 2,3,6,7-) tetracarboxylic dianhydride, 2,3,8,9-, 3,4,9,10-, 4,5,10,11- or 5 , 6,11,12- Rylene-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′-bis (2,3-dicarboxyphenoxy) diphenylmethane dianhydride, etc. It is done.

The group R ₁ is a divalent aromatic diamine residue derived from the diamine compound (i). By using the diamine compound (i) having a branched alkyl group having 4 to 8 carbon atoms in the side chain as a diamine component, the imide group concentration is lowered and the low dielectric properties are obtained. CTE increase can be suppressed.

  The charging amount of the diamine compound (i) is in the range of 10 to 60 mol%, preferably in the range of 19 to 44 mol% with respect to the total diamine component. If the diamine compound (i) is less than 10 mol%, the thermal expansion coefficient of the polyimide tends to decrease and the dielectric constant tends to increase. If it exceeds 60 mol%, the thermal expansion coefficient of the polyimide increases excessively. Since it becomes a tendency, the subject that the obtained metal-clad laminated board warps generate | occur | produces.

Examples of the group R ₂ include those represented by the following formulas (5) to (7).

［式（５）〜式（７）において、Ｒ_３は独立に炭素数１〜６の１価の炭化水素基又はアルコキシ基を示し、Ｚは単結合、炭素数１〜１５の２価の炭化水素基、−Ｏ−、−Ｓ−、−ＣＯ−、−ＳＯ−、−ＳＯ_２−、−ＮＨ−若しくは−ＣＯＮＨ−から選ばれる２価の基を示し、ｎ_１は独立に０〜４の整数を示す］

[In Formula (5)-Formula (7), R < ₃ > shows a C1-C6 monovalent hydrocarbon group or an alkoxy group independently, Z is a single bond and C1-C15 bivalent carbonization. A divalent group selected from a hydrogen group, —O—, —S—, —CO—, —SO—, —SO ₂ —, —NH— or —CONH—, wherein n ₁ is independently 0-4; Indicates an integer]

In particular, from the viewpoint of reducing the polar groups of polyimide and improving the dielectric properties, the group R ₂ includes Z in the formulas (5) to (7) as a single bond and a divalent carbon atom having 1 to 15 carbon atoms. It is preferable that the hydrogen group, R ₃ is a monovalent hydrocarbon group having 1 to 6 carbon atoms, and n ₁ is an integer of 0 to 4.

Examples of the diamine having the group R ₂ as a residue include 4,4′-diaminodiphenyl ether, 2′-methoxy-4,4′-diaminobenzanilide, 1,4-bis (4-aminophenoxy) benzene, 1, 3-bis (4-aminophenoxy) benzene, 2,2′-bis [4- (4-aminophenoxy) phenyl] propane, 2,2′-dimethyl-4,4′-diaminobiphenyl (m-TB), 2,2′-diethyl-4,4′-diaminobiphenyl (m-EB), 2,2′- di- n-propyl-4,4′-diaminobiphenyl (m-NPB), 3,3′-dihydroxy -4,4'-diaminobiphenyl, 4,4'-diaminobenzanilide, 2,2-bis- [4- (3-aminophenoxy) phenyl] propane, bis [4- (4-aminophenoxy) phenyl] sulfone Bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy)] bif Nyl, bis [4- (3-aminophenoxy) biphenyl, bis [1- (4-aminophenoxy)] biphenyl, bis [1- (3-aminophenoxy)] biphenyl, bis [4- (4-aminophenoxy) Phenyl] methane, bis [4- (3-aminophenoxy) phenyl] methane, bis [4- (4-aminophenoxy) phenyl] ether, bis [4- (3-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy)] benzophenone, bis [4- (3-aminophenoxy)] benzophenone, bis [4,4 '-(4-aminophenoxy)] benzanilide, bis [4,4'-(3-aminophenoxy )] Benzanilide, 9,9-bis [4- (4-aminophenoxy) phenyl] fluorene, 9,9-bis [4- (3-aminophenoxy) phenyl] fluorene, 2,2-bis- [4- ( 4-Aminophenoxy) phenyl] he Safluoropropane, 2,2-bis- [4- (3-aminophenoxy) phenyl] hexafluoropropane, 4,4'-methylenedi-o-toluidine, 4,4'-methylenedi-2,6-xylidine, 4 , 4'-methylene-2,6-diethylaniline, 4,4'-diaminodiphenylpropane, 3,3'-diaminodiphenylpropane, 4,4'-diaminodiphenylethane, 3,3'-diaminodiphenylethane, 4 , 4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone 4,4'-diaminodiphenyl ether, 3,3-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, benzidine, 3,3'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3 , 3'-Dimethoxyben Dizine, 4,4 ''-diamino-p-terphenyl, 3,3 ''-diamino-p-terphenyl, m-phenylenediamine, p-phenylenediamine, 2,6-diaminopyridine, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 4,4 '-[1,4-phenylenebis (1-methylethylidene)] bisaniline, 4,4'-[1, 3-phenylenebis (1-methylethylidene)] bisaniline, bis (p-aminocyclohexyl) methane, bis (p-β-amino-tert-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-diaminonaphthalene, 2,6-diaminonaphthalene, 2, 4-bis (β-amino-tert-butyl) toluene, 2,4-diaminotoluene, m-xylene-2,5-diamine, p-xyle 2,5-diamine, m-xylylenediamine, p-xylylenediamine, 2,6-diaminopyridine, 2,5-diaminopyridine, 2,5-diamino-1,3,4-oxadiazole, And piperazine.

  Based on the dielectric properties of polyimide, it is essential to use 50 mol% or more of PMDA and / or BPDA as the aromatic tetracarboxylic acid anhydride used for preparing the polyimide precursor of this embodiment. By using 50 mol% or more of PMDA and / or BPDA, it is possible to reduce the CTE of the resin film using the polyimide of the present embodiment. Examples of aromatic tetracarboxylic anhydrides other than PMDA and BPDA include 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride (BTDA), 3,3 ′, 4,4′- A diphenyl sulfone tetracarboxylic dianhydride (DSDA) etc. can be mentioned. Among them, particularly preferred acid anhydrides include 4,4′-oxydiphthalic dianhydride (ODPA). These aromatic tetracarboxylic acid anhydrides can be blended in combination of two or more.

In addition, based on the dielectric properties of polyimide, the aromatic diamine that is suitably used for the preparation of the polyimide precursor of the present embodiment includes the diamine compound (i) as an essential component. Bis (4-aminophenoxyphenyl) propane (BAPP), 2,2′-divinyl-4,4′-diaminobiphenyl (VAB), 2,2′-dimethyl-4,4′-diaminobiphenyl (m-TB) 2,2′-diethyl-4,4′-diaminobiphenyl (m-EB), 2,2′- di- n-propyl-4,4′-diaminobiphenyl (m-NPB), 2,2 ′, Examples include 6,6′-tetramethyl-4,4′-diaminobiphenyl, 2,2′-diphenyl-4,4′-diaminobiphenyl, 9,9-bis (4-aminophenyl) fluorene, and the like. These aromatic diamines can be blended in combination of two or more. Among them, as a diamine component contributing to low CTE of the resin film using the polyimide of the present embodiment, 1,4 bis (4-aminophenoxy) -2,5-di-tert-butylbenzene (DTBAB), 2,2-bis (4-aminophenoxyphenyl) propane (BAPP), 2,2′-divinyl-4,4′-diaminobiphenyl (VAB), 2,2′-dimethyl-4,4′-diaminobiphenyl ( m-TB), 2,2′-diethyl-4,4′-diaminobiphenyl (m-EB), 2,2′- di- n-propyl-4,4′-diaminobiphenyl (m-NPB) and the like. Particularly preferred.

  In addition, preferred specific examples of the diamine compound (i) used in the present embodiment include those represented by the following formulas (ia) to (if).

  Formula (ia) is 1,4 bis (4-aminophenoxy) -2,5-di-tert-butylbenzene (DTBAB). The formula (ib) is 1,4 bis (4-aminophenoxy) -2,3-di-tert-butylbenzene. Here, when the diamine compound represented by the general formula (i) is a compound represented by the formula (ia) and / or the formula (ib) and m-TB is used as another diamine component, It is preferable that the compounding amount of the acid anhydride component and the compound represented by the formula (ia) and / or the formula (ib) satisfies the relationship represented by the following formula A. In this case, it is assumed that PMDA and / or BPDA is used in an amount of 50 mol% or more as the acid anhydride component, and preferably only PMDA and / or BPDA is used as the acid anhydride component.

y = 0.2996x−8.4193 (Equation A)
[Wherein x is a value obtained by multiplying the total blending amount (mol%) of the compound represented by the formula (ia) and / or the formula (ib) by a factor of 2.1 and the BPDA in the acid anhydride component It means the sum of the amount (mol%), and y means a number in the range of 10 to 30]

In the above formula A, y corresponds to a thermal expansion coefficient [× 10 ⁻⁶ (1 / K)] when the polyamic acid obtained using each of the above monomers is imidized and processed into a film shape. Therefore, a polyimide film having a thermal expansion coefficient in the range of 10 × 10 ⁻⁶ to 30 × 10 ⁻⁶ (1 / K) can be formed by blending each monomer so as to satisfy the above formula A.

  Moreover, the diamine compound represented by the general formula (i) is a compound represented by the formula (ia) and / or the formula (ib), and 2,2′-diethyl-4 as another diamine component , 4'-diaminobiphenyl (m-EB), the relationship shown in the following formula B is the blending amount of the acid anhydride component and the compound represented by formula (ia) and / or formula (ib) It is preferable to satisfy. In this case, it is assumed that PMDA and / or BPDA is used in an amount of 50 mol% or more as the acid anhydride component, and preferably only MDA and / or BPDA is used as the acid anhydride component.

y = 0.0.313x-3.3320 (Formula B)
[Wherein x is a value obtained by multiplying the total blending amount (mol%) of the compound represented by formula (ia) and / or formula (ib) by a factor of 1.9, and blending of BPDA in the acid anhydride component Means the sum of the amount (mol%) and y means a number in the range of 10 to 30]

In the above formula B, y corresponds to a thermal expansion coefficient [× 10 ⁻⁶ (1 / K)] when the polyamic acid obtained using each of the above monomers is imidized and processed into a film shape. Therefore, a polyimide film having a thermal expansion coefficient in the range of 10 × 10 ⁻⁶ to 30 × 10 ⁻⁶ (1 / K) can be formed by blending each monomer so as to satisfy the above mathematical formula B.

Moreover, the diamine compound represented by the general formula (i) is a compound represented by the formula (ia) and / or the formula (ib), and 2,2′- di- n as another diamine component. When -propyl-4,4′-diaminobiphenyl (m-NPB) is used, the compounding amount of the acid anhydride component and the compound represented by the formula (ia) and / or the formula (ib) is as follows: It is preferable to satisfy the relationship indicated by C. In this case, it is assumed that PMDA and / or BPDA is used in an amount of 50 mol% or more as the acid anhydride component, and preferably only PMDA and / or BPDA is used as the acid anhydride component.

y = 0.3005x + 15.0500 (Equation C)
[Wherein x is a value obtained by multiplying the total blending amount (mol%) of the compound represented by formula (ia) and / or formula (ib) by a factor of 1.3 and blending of BPDA in the acid anhydride component It means the sum with the amount (mol%), and y means a number in the range of 10 to 30]

In the above formula C, y corresponds to the thermal expansion coefficient [× 10 ⁻⁶ (1 / K)] when the polyamic acid obtained using each of the above monomers is imidized and processed into a film. Therefore, a polyimide film having a thermal expansion coefficient in the range of 10 × 10 ⁻⁶ to 30 × 10 ⁻⁶ (1 / K) can be formed by blending each monomer so as to satisfy the above formula C.

  Formula (ic) is 1,4 bis (4-aminophenoxy) -2,5-di (1-methylpropyl) benzene. Here, when the diamine compound represented by the general formula (i) is a compound represented by the formula (ic) and m-TB is used as another diamine component, an acid anhydride component, a formula The compounding amount of the compound represented by (ic) preferably satisfies the relationship represented by the following formula D. In this case, it is assumed that PMDA and / or BPDA is used in an amount of 50 mol% or more as the acid anhydride component, and preferably only PMDA and / or BPDA is used as the acid anhydride component.

y = 0.2986x-8.3997 (Formula D)
[Wherein x is the sum of the compounding amount (mol%) of the compound represented by the formula (ic) multiplied by a coefficient 4.3 and the compounding amount (mol%) of BPDA in the acid anhydride component. Y represents a number in the range of 10 to 30]

In the above formula D, y corresponds to a thermal expansion coefficient [× 10 ⁻⁶ (1 / K)] when the polyamic acid obtained using each of the above monomers is imidized and processed into a film shape. Therefore, a polyimide film having a thermal expansion coefficient in the range of 10 × 10 ⁻⁶ to 30 × 10 ⁻⁶ (1 / K) can be formed by blending each monomer so as to satisfy the above formula D.

  The diamine compound represented by the general formula (i) is a compound represented by the formula (ic), and 2,2′-diethyl-4,4′-diaminobiphenyl (as another diamine component) When m-EB) is used, it is preferable that the blending amount of the acid anhydride component and the compound represented by the formula (ic) satisfies the relationship represented by the following formula E. In this case, it is assumed that PMDA and / or BPDA is used in an amount of 50 mol% or more as the acid anhydride component, and preferably only PMDA and / or BPDA is used as the acid anhydride component.

y = 0.003x−3.4028 (Equation E)
[Wherein x is a value obtained by multiplying the compounding amount (mol%) of the compound represented by the formula (ic) by a coefficient of 4.1 and the compounding amount (mol%) of BPDA in the acid anhydride component. And y means a number in the range of 10 to 30]

In the above formula E, y corresponds to a thermal expansion coefficient [× 10 ⁻⁶ (1 / K)] when the polyamic acid obtained using each of the above monomers is imidized and processed into a film shape. Therefore, a polyimide film having a thermal expansion coefficient in the range of 10 × 10 ⁻⁶ to 30 × 10 ⁻⁶ (1 / K) can be formed by blending each monomer so as to satisfy the above formula E.

  Formula (id) is 1,4 bis (4-aminophenoxy) -2,6-di-tert-butylbenzene. Here, when the diamine compound represented by the general formula (i) is a compound represented by the formula (id) and m-TB is used as another diamine component, an acid anhydride component, a formula The compounding amount of the compound represented by (id) preferably satisfies the relationship represented by the following formula F. In this case, it is assumed that PMDA and / or BPDA is used in an amount of 50 mol% or more as the acid anhydride component, and preferably only PMDA and / or BPDA is used as the acid anhydride component.

y = 0.2971x−8.3862 ... (Formula F)
[Wherein x is the sum of the compounding amount (mol%) of the compound represented by formula (id) multiplied by a factor of 4.5 and the compounding amount (mol%) of BPDA in the acid anhydride component. Y represents a number in the range of 10 to 30]

In the above formula F, y corresponds to a thermal expansion coefficient [× 10 ⁻⁶ (1 / K)] when the polyamic acid obtained by using each of the above monomers is imidized and processed into a film shape. Therefore, a polyimide film having a thermal expansion coefficient in the range of 10 × 10 ⁻⁶ to 30 × 10 ⁻⁶ (1 / K) can be formed by blending each monomer so as to satisfy the above formula F.

  In addition, the diamine compound represented by the general formula (i) is a compound represented by the formula (id), and 2,2′-diethyl-4,4′-diaminobiphenyl (as another diamine component) When m-EB) is used, it is preferable that the blending amount of the acid anhydride component and the compound represented by the formula (id) satisfies the relationship represented by the following formula G. In this case, it is assumed that PMDA and / or BPDA is used in an amount of 50 mol% or more as the acid anhydride component, and preferably only PMDA and / or BPDA is used as the acid anhydride component.

y = 0.2986x-3.397 ... (Formula G)
[Wherein x is a value obtained by multiplying the compounding amount (mol%) of the compound represented by the formula (id) by a coefficient 4.3, and the compounding amount (mol%) of BPDA in the acid anhydride component, And y is a number in the range of 10 to 30]

In the above formula G, y corresponds to a thermal expansion coefficient [× 10 ⁻⁶ (1 / K)] when the polyamic acid obtained using each of the above monomers is imidized and processed into a film shape. Therefore, a polyimide film having a thermal expansion coefficient in the range of 10 × 10 ⁻⁶ to 30 × 10 ⁻⁶ (1 / K) can be formed by blending each monomer so as to satisfy the above formula G.

  Formula (ie) is 1,4 bis (4-aminophenoxy) -2,5-di (2-methylpropyl) benzene. Here, when the diamine compound represented by the general formula (i) is a compound represented by the formula (ie) and m-TB is used as another diamine component, an acid anhydride component, a formula The compounding amount of the compound represented by (ie) preferably satisfies the relationship represented by the following formula H. In this case, it is assumed that PMDA and / or BPDA is used in an amount of 50 mol% or more as the acid anhydride component, and preferably only PMDA and / or BPDA is used as the acid anhydride component.

y = 0.3011x−8.6596 (Equation H)
[Wherein x is the sum of the compounding amount (mol%) of the compound represented by formula (ie) multiplied by a factor of 6.1 and the compounding amount (mol%) of BPDA in the acid anhydride component. Y represents a number in the range of 10 to 30]

In the above formula H, y corresponds to a thermal expansion coefficient [× 10 ⁻⁶ (1 / K)] when the polyamic acid obtained using each of the above monomers is imidized and processed into a film shape. Therefore, a polyimide film having a thermal expansion coefficient in the range of 10 × 10 ⁻⁶ to 30 × 10 ⁻⁶ (1 / K) can be formed by blending each monomer so as to satisfy the above formula H.

  The diamine compound represented by the general formula (i) is a compound represented by the formula (ie), and 2,2′-diethyl-4,4′-diaminobiphenyl (as another diamine component) When m-EB) is used, it is preferable that the compounding amount of the acid anhydride component and the compound represented by the formula (ie) satisfies the relationship represented by the following formula I. In this case, it is assumed that PMDA and / or BPDA is used in an amount of 50 mol% or more as the acid anhydride component, and preferably only PMDA and / or BPDA is used as the acid anhydride component.

y = 0.2984x-3.6137 ... (Formula I)
[Wherein x is a value obtained by multiplying the compounding amount (mol%) of the compound represented by the formula (id) by a factor of 6.0, and the compounding amount (mol%) of BPDA in the acid anhydride component, And y is a number in the range of 10 to 30]

In the above formula I, y corresponds to the thermal expansion coefficient [× 10 ⁻⁶ (1 / K)] when the polyamic acid obtained using each of the above monomers is imidized and processed into a film shape. Therefore, a polyimide film having a thermal expansion coefficient in the range of 10 × 10 ⁻⁶ to 30 × 10 ⁻⁶ (1 / K) can be formed by blending each monomer so as to satisfy the above formula I.

  Formula (if) is 1,4 bis (4-aminophenoxy) -2,5-di (1-methylheptyl) benzene.

  Each of the acid anhydrides and diamines may be used alone or in combination of two or more. In addition, other diamines and acid anhydrides not included in the above general formulas (1) and (2) can be used together with the above acid anhydrides or diamines. In this case, use of other acid anhydrides or diamines is also possible. The ratio is preferably 10 mol% or less, more preferably 5 mol% or less. By selecting the types of acid anhydrides and diamines, and the respective molar ratios when using two or more acid anhydrides or diamines, the thermal expansibility, adhesiveness, glass transition temperature, etc. can be controlled. .

  The polyimide having the structural units represented by the general formulas (1) and (2) contains the aromatic tetracarboxylic acid anhydride containing the PMDA and / or BPDA, the diamine compound (i) and another aromatic diamine in a solvent. It can be produced by reacting to produce a precursor resin and then ring closure by heating. For example, it is a polyimide precursor by dissolving an acid anhydride component and a diamine component in an approximately equimolar amount in an organic solvent and stirring and polymerizing at a temperature in the range of 0 to 100 ° C. for 30 minutes to 24 hours. A polyamic acid is obtained. In the reaction, the reaction components are dissolved so that the precursor to be produced is in the range of 5 to 30% by weight, preferably in the range of 10 to 20% by weight in the organic solvent. Examples of the organic solvent used for the polymerization reaction include N, N-dimethylformamide, N, N-dimethylacetamide (DMAC), N-methyl-2-pyrrolidone, 2-butanone, dimethyl sulfoxide, dimethyl sulfate, cyclohexanone, and dioxane. , Tetrahydrofuran, diglyme, triglyme and the like. Two or more of these solvents can be used in combination, and further, aromatic hydrocarbons such as xylene and toluene can be used in combination. The amount of such organic solvent used is not particularly limited, but the amount used is such that the concentration of the polyamic acid solution (polyimide precursor solution) obtained by the polymerization reaction is about 5 to 30% by weight. It is preferable to adjust and use.

  The synthesized precursor is usually advantageously used as a reaction solvent solution, but can be concentrated, diluted, or replaced with another organic solvent if necessary. Moreover, since a precursor is generally excellent in solvent solubility, it is advantageously used. The method for imidizing the precursor is not particularly limited, and for example, heat treatment such as heating in the solvent at a temperature within the range of 80 to 400 ° C. for 1 to 24 hours is suitably employed.

[Resin film]
The resin film of the present embodiment is not particularly limited as long as it is an insulating resin film including a polyimide layer formed from the polyimide of the present embodiment, and may be a film (sheet) made of an insulating resin. Alternatively, it may be a film of an insulating resin laminated on a substrate such as a resin sheet such as a copper foil, a glass plate, a polyimide film, a polyamide film, or a polyester film. Moreover, the thickness of the resin film of this Embodiment becomes like this. Preferably it exists in the range of 3-100 micrometers, More preferably, it exists in the range of 3-75 micrometers.

The polyimide of this embodiment is suitable for application as a base film layer (main layer of an insulating resin layer). Specifically, the thermal expansion coefficient is in the range of 10 × 10 ⁻⁶ to 30 × 10 ⁻⁶ (1 / K), preferably in the range of 10 × 10 ^{−6 to} 25 × 10 ⁻⁶ (1 / K). More preferably, when a low thermal expansion polyimide layer in the range of 15 × 10 ^{−6 to} 25 × 10 ⁻⁶ (1 / K) is applied to the base film layer, a great effect can be obtained. Among the low thermal expansion polyimides, a polyimide that can be suitably used is a non-thermoplastic polyimide. The thickness when the low thermal expansion base film layer is formed using the polyimide of the present embodiment is preferably in the range of 5 to 50 μm, more preferably in the range of 10 to 35 μm.

  On the other hand, the polyimide layer exceeding the thermal expansion coefficient is also preferably applied as an adhesive layer with a base material such as a metal layer or another resin layer. As the polyimide that can be suitably used as such an adhesive polyimide layer, the glass transition temperature is preferably, for example, 360 ° C. or less, and more preferably in the range of 200 to 320 ° C.

  Among the adhesive polyimides, a polyimide that can be suitably used is a thermoplastic polyimide. Examples of the acid anhydride suitably used for forming the thermoplastic polyimide include pyromellitic anhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4. Examples include '-diphenylsulfonetetracarboxylic dianhydride, 4,4'-oxydiphthalic anhydride. In addition, the acid anhydride mentioned in description of the said polyimide can be mentioned. Among these, particularly preferred acid anhydrides include pyromellitic anhydride (PMDA), 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (BPDA), 3,3 ′, 4,4′— Examples thereof include one or more acid anhydrides selected from benzophenone tetracarboxylic dianhydride (BTDA), 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride (DSDA).

  As an aromatic diamine preferably used for forming a thermoplastic polyimide, from the viewpoint of heat resistance and adhesiveness, those having a phenylene group or a biphenylene group in the molecule, or containing an oxygen element or a sulfur element in the molecule Those having a divalent linking group are preferred, for example, 1,4 bis (4-aminophenoxy) -2,5-di-tert-butylbenzene (DTBAB), 4,4′-diaminodiphenyl ether, 2′-methoxy. -4,4'-diaminobenzanilide, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 2,2-bis [4- (4-aminophenoxy) Phenyl] propane, 2,2′-dimethyl-4,4′-diaminobiphenyl, 3,3′-dihydroxy-4,4′-diaminobiphenyl, 4,4′-diaminobenzanilide and the like. In addition, the diamine mentioned by description of said polyimide can be mentioned. Among these, particularly preferred diamine components include 1,3-bis (4-aminophenoxy) -2,2-dimethylpropane (DANPG), 2,2-bis [4- (4-aminophenoxy) phenyl] propane ( From BAPP), 1,3-bis (3-aminophenoxy) benzene (APB), paraphenylenediamine (p-PDA), 3,4'-diaminodiphenyl ether (DAPE34), 4,4'-diaminodiphenyl ether (DAPE44) One or more selected diamines may be mentioned.

  The method for forming the polyimide film as the resin film of the present embodiment is not particularly limited. For example, after applying a polyimide solution (or polyamic acid solution) on an arbitrary substrate, heat treatment (drying and curing) is performed. An example is a method of forming a polyimide film (or polyamic acid layer) on a substrate and then peeling it to form a polyimide film. The method for applying the polyimide solution (or polyamic acid solution) on the substrate is not particularly limited, and for example, it can be applied by a coater such as a comma, die, knife, lip or the like. In forming a multi-layer polyimide layer, a method of repeatedly applying and drying a polyimide solution (or polyamic acid solution) on a substrate is preferable.

  The resin film of the present embodiment can include a single layer or a plurality of polyimide layers. In this case, at least one polyimide layer (preferably a base film layer) may be formed using the non-thermoplastic polyimide of the present embodiment. For example, if the non-thermoplastic polyimide layer is P1 and the thermoplastic polyimide layer is P2, when the resin film is two layers, it is preferable to laminate with a combination of P2 / P1, and when the resin film is three layers Are preferably laminated in the order of P2 / P1 / P2, or in the order of P2 / P1 / P1. Here, P1 is a base film layer formed using the non-thermoplastic polyimide of the present embodiment. P2 may be made of a polyimide other than the polyimide of the present embodiment.

  The resin film of this Embodiment may contain an inorganic filler in a polyimide layer as needed. Specific examples include silicon dioxide, aluminum oxide, magnesium oxide, beryllium oxide, boron nitride, aluminum nitride, silicon nitride, aluminum fluoride, and calcium fluoride. These may be used alone or in combination of two or more.

  What applied the resin film of this Embodiment as a low-thermal-expansion polyimide film can be applied, for example as a film material for coverlays in a coverlay film. A cover lay film can be formed by laminating an arbitrary adhesive layer on the resin film of the present embodiment. The thickness of the coverlay film material layer is not particularly limited, but is preferably 5 μm or more and 100 μm or less, for example. The thickness of the adhesive layer is not particularly limited, but is preferably 25 μm or more and 50 μm or less, for example.

  What applied the resin film of this Embodiment as an adhesive polyimide film can be utilized also as a bonding sheet of multilayer FPC, for example. When used as a bonding sheet, the resin film of the present embodiment may be used as it is as a bonding sheet on an arbitrary base film, or the resin film is used in a state laminated with an arbitrary base film. Also good.

[Metal-clad laminate]
The metal-clad laminate of the present embodiment has an insulating resin layer and a metal layer laminated on at least one surface of the insulating resin layer. Preferable specific examples of the metal-clad laminate include, for example, a copper-clad laminate (CCL).

<Insulating resin layer>
In the metal-clad laminate of the present embodiment, the insulating resin layer has a single layer or a plurality of polyimide layers. In this case, in order to impart excellent high frequency characteristics to the metal-clad laminate, at least one of the polyimide layers (preferably the base film layer) must be formed using the non-thermoplastic polyimide of the present embodiment. That's fine. Moreover, in order to improve the adhesiveness of an insulating resin layer and a metal layer, it is preferable that the layer which touches the metal layer in an insulating resin layer is a thermoplastic polyimide layer. For example, when two insulating resin layers are used, P1 is a non-thermoplastic polyimide layer, P2 is a thermoplastic polyimide layer, and M1 is a metal layer. Here, P1 is a base film layer formed using the non-thermoplastic polyimide of the present embodiment. P2 may be made of a polyimide other than the polyimide of the present embodiment.

<Metal layer>
The material of the metal layer in the metal-clad laminate of the present embodiment is not particularly limited. For example, copper, stainless steel, iron, nickel, beryllium, aluminum, zinc, indium, silver, gold, tin, zirconium, tantalum , Titanium, lead, magnesium, manganese, and alloys thereof. Among these, copper or a copper alloy is particularly preferable. Note that the material of the wiring layer in the circuit board of the present embodiment described later is the same as that of the metal layer.

  When a high-frequency signal is supplied to the signal wiring, current flows only on the surface of the signal wiring, the effective cross-sectional area through which the current flows decreases, the DC resistance increases, and the signal attenuates (skin effect) is there. By reducing the surface roughness of the surface of the metal layer in contact with the insulating resin layer, an increase in the resistance of the signal wiring due to the skin effect can be suppressed. However, if the surface roughness is lowered to satisfy the electrical performance requirement standard, the adhesive strength (peeling strength) between the copper foil and the dielectric substrate becomes weak. Therefore, from the viewpoint of satisfying the electrical performance requirements and improving the visibility of the metal-clad laminate while ensuring adhesion with the insulating resin layer, the surface roughness of the surface of the metal layer in contact with the insulating resin layer is The ten-point average roughness Rz is preferably 1.5 μm or less, and the arithmetic average roughness Ra is preferably 0.2 μm or less.

  The metal-clad laminate is prepared, for example, by preparing a resin film including the polyimide according to the present embodiment, forming a seed layer by sputtering a metal on the resin film, and then forming a metal layer by plating, for example. May be.

  The metal-clad laminate may be prepared by preparing a resin film including the polyimide of the present embodiment and laminating a metal foil on the resin film by a method such as thermocompression bonding.

  Further, the metal-clad laminate is cast on a metal foil containing a polyamic acid which is a polyimide precursor of the present embodiment, dried to form a coating film, and then heat treated to imidize, You may prepare by forming a polyimide layer.

[Circuit board]
The circuit board of the present embodiment includes an insulating resin layer and a wiring layer formed on the insulating resin layer. In the circuit board of this embodiment, the insulating resin layer can include a single layer or a plurality of polyimide layers. In this case, in order to impart excellent high frequency characteristics to the circuit board, at least one of the polyimide layers (preferably the base film layer) may be formed using the non-thermoplastic polyimide of the present embodiment. . Moreover, in order to improve the adhesiveness of an insulating resin layer and a wiring layer, it is preferable that the layer which touches the wiring layer in an insulating resin layer is the thermoplastic polyimide layer formed using the polyimide of this Embodiment. For example, when two insulating resin layers are used, P1 is a non-thermoplastic polyimide layer, P2 is a thermoplastic polyimide layer, and M2 is a wiring layer. P1 / P2 / M2 are preferably laminated in this order. Here, P1 is a base film layer formed using the non-thermoplastic polyimide of the present embodiment. P2 may be made of a polyimide other than the polyimide of the present embodiment.

  There is no limitation on the method for producing the circuit board except that the polyimide according to the present embodiment is used. For example, a subtractive method in which a metal-clad laminate composed of an insulating resin layer containing polyimide and a metal layer according to the present embodiment is prepared and wiring is formed by etching the metal layer may be used. Alternatively, a semi-additive method may be used in which a seed layer is formed on the polyimide layer of this embodiment, a resist is patterned, and a metal is pattern-plated to form a wiring.

  Hereinafter, a method for manufacturing a circuit board according to the present embodiment will be specifically described by taking as an example a combination of a casting method and a subtractive method.

First, the method for producing a metal-clad laminate of the present embodiment can include the following steps (1) to (3).
Step (1):
Step (1) is a step of obtaining a polyamic acid resin solution that is a polyimide precursor of the present embodiment. As described above, this step can be performed by reacting a raw material diamine compound (i) and a diamine component containing another aromatic diamine and an acid anhydride component in an appropriate solvent.

Step (2):
Step (2) is a step of applying a polyamic acid resin solution onto a metal foil to be a metal layer to form a coating film. The metal foil can be used in the form of a cut sheet, a roll, or an endless belt. In order to obtain productivity, it is efficient to use a roll-like or endless belt-like form so that continuous production is possible. Furthermore, the copper foil is preferably in the form of a roll that is formed in a long shape from the viewpoint of expressing the effect of improving the accuracy of the wiring pattern on the circuit board.

  The coating film can be formed by directly applying the polyamic acid resin solution on the metal foil or by applying the solution on the polyimide layer supported by the metal foil and then drying. The method of applying is not particularly limited, and it is possible to apply with a coater such as a comma, die, knife, lip or the like.

  The polyimide layer may be a single layer or a plurality of layers. In the case where a plurality of polyimide layers are used, other precursors can be sequentially applied on the precursor layers made of different components. When the precursor layer is composed of three or more layers, the precursor having the same configuration may be used twice or more. A two-layer or a single layer having a simple layer structure is preferable because it can be advantageously obtained industrially. The thickness of the precursor layer (after drying) is, for example, in the range of 3 to 100 μm, preferably in the range of 3 to 75 μm.

  When multiple polyimide layers are used, the precursor film is formed so that the base film layer is a non-thermoplastic polyimide layer made of the polyimide of the present embodiment, and the polyimide layer in contact with the metal layer is a thermoplastic polyimide layer. It is preferable to do. By using thermoplastic polyimide, adhesion with the metal layer can be improved. Such a thermoplastic polyimide preferably has a glass transition temperature (Tg) of 360 ° C. or lower, more preferably 200 to 320 ° C.

  It is also possible to once imidize a single layer or a plurality of precursor layers into a single layer or a plurality of polyimide layers, and further form a precursor layer thereon.

Step (3):
Step (3) is a step of forming an insulating resin layer by heat-treating the coating film to imidize it. The imidization method is not particularly limited, and for example, heat treatment such as heating for 1 to 60 minutes under a temperature condition in the range of 80 to 400 ° C. is suitably employed. In order to suppress the oxidation of the metal layer, heat treatment in a low oxygen atmosphere is preferable. Specifically, it is performed in an inert gas atmosphere such as nitrogen or a rare gas, in a reducing gas atmosphere such as hydrogen, or in a vacuum. Is preferred. By the heat treatment, the polyamic acid in the coating film is imidized to form polyimide.

  As described above, a metal-clad laminate having a polyimide layer (single layer or multiple layers) and a metal layer can be produced.

  In addition to the steps (1) to (3), the circuit board manufacturing method of the present embodiment can further include the following step (4).

Step (4):
Step (4) is a step of forming a wiring layer by patterning the metal foil of the metal-clad laminate. In this step, the circuit layer is obtained by forming a pattern by etching the metal layer into a predetermined shape and processing it into a wiring layer. Etching can be performed by any method using, for example, photolithography.

  In the above description, only the characteristic steps of the circuit board manufacturing method have been described. That is, when manufacturing a circuit board, processes other than the above normally performed, for example, processes such as through-hole processing in a previous process, terminal plating in a subsequent process, and external processing can be performed according to a conventional method.

  As described above, by using the polyimide of the present embodiment, a metal-clad laminate with reduced transmission loss can be formed.

  The features of the present invention will be described more specifically with reference to examples. However, the scope of the present invention is not limited to the examples. In the following examples, various measurements and evaluations are as follows unless otherwise specified.

[Measurement of coefficient of thermal expansion (CTE)]
The coefficient of thermal expansion was from 30 ° C. to 265 ° C. at a constant temperature increase rate while applying a load of 5.0 g using a thermomechanical analyzer (trade name: 4000SA) made of a polyimide film having a size of 3 mm × 20 mm. Then, the temperature was further maintained at that temperature for 10 minutes, followed by cooling at a rate of 5 ° C./minute, and an average thermal expansion coefficient (linear thermal expansion coefficient) from 250 ° C. to 100 ° C. was determined.

[Measurement of dielectric constant and dissipation factor]
The dielectric constant and dielectric loss tangent were determined by the following methods.
Using a cavity resonator perturbation method dielectric constant evaluation apparatus (manufactured by Agilent, trade name: Vector Network Analyzer E8363B), the dielectric constant and dielectric loss tangent of the resin sheet (cured resin sheet) at a frequency of 3 GHz were measured. In addition, the resin sheet used for the measurement was left for 24 hours under the conditions of temperature; 24-26 ° C., humidity: 45-55%.

Abbreviations used in Examples and Comparative Examples indicate the following compounds.
Diamine A (DTBAB): 1,4 bis (4-aminophenoxy) -2,5-di-tert-butylbenzene (CAS number 189344-59-0)
Diamine B: 1,4bis (4-aminophenoxy) -2,3-di-tert-butylbenzenediamine C: 1,4bis (4-aminophenoxy) -2,5-di (1-methylpropyl) benzene Diamine D: 1,4-bis (4-aminophenoxy) -2,6-di-tert-butylbenzenediamine E: 1,4-bis (4-aminophenoxy) -2,5-di (2-methylpropyl) benzene Diamine F: 1,4-bis (4-aminophenoxy) -2,5-di (1-methylheptyl) benzene m-TB: 2,2′-dimethyl-4,4′-diaminobiphenyl m-EB: 2, 2'-diethyl-4,4'-diamino biphenyl m-NPB: 2,2 '- di -n- propyl-4,4'-diaminobiphenyl BAPP: 2,2-bis (4-aminophenoxy) propane PM A: pyromellitic dianhydride BPDA: 3,3 ', 4,4' - biphenyltetracarboxylic acid dianhydride DMAc: N, N-dimethylacetamide DMF: N, N-dimethylformamide

[Synthesis Example 1]
Under a nitrogen stream, 1.050 g of DTBAB (0.0026 mol), 4.957 g of m-TB (0.0234 mol) and 68.0 g of DMAc were charged into a 300 ml separable flask and stirred at room temperature. And dissolved. Next, 1.511 g of BPDA (0.0051 mol) and 4.482 g of PMDA (0.0206 mol) were added, and then the polymerization reaction was continued for 3 hours at room temperature to obtain a polyamic acid solution A-a. Got. The solution viscosity of the polyamic acid solution Aa was 7,025 cps.

[Synthesis Examples 2 to 8]
Polyamic acid solutions Ab to Ah were prepared in the same manner as in Synthesis Example 1 except that the raw material compositions shown in Table 1 and Table 2 were used.

[Example 1]
After uniformly applying the polyamic acid solution Aa prepared in Synthesis Example 1 to one side (surface roughness Rz; 2.1 μm) of an electrolytic copper foil having a thickness of 18 μm so that the thickness after curing is about 25 μm. Then, the solvent was removed by heating and drying at 120 ° C. Furthermore, stepwise heat treatment was performed from 120 ° C. to 360 ° C. to complete imidization. About the obtained metal clad laminated board, the copper foil was etched away using the ferric chloride aqueous solution, and the resin film was obtained. In addition, the polyimide which comprises the obtained resin film was non-thermoplastic.
The thermal expansion coefficient, glass transition temperature, dielectric constant and dielectric loss tangent of the obtained resin film were determined. Table 3 shows the measurement results.

[Examples 2 to 4, Reference Examples 1 to 3]
Resin films of Examples 2 to 4 and Reference Examples 1 to 3 were obtained in the same manner as in Example 1 except that the polyamic acid solution shown in Table 3 was used. The thermal expansion coefficient, glass transition temperature, dielectric constant and dielectric loss tangent of the obtained resin film were determined. Table 3 shows the measurement results.

[Example 5]
After applying the polyamic acid solution Ah uniformly on one surface (surface roughness Rz; 1.39 μm) of an electrolytic copper foil having a thickness of 12 μm so that the thickness after curing is about 2 to 3 μm, at 120 ° C. The solvent was removed by heating to dryness. Next, the polyamic acid solution Aa was uniformly applied thereon so that the thickness after curing was about 25 μm, and the solvent was removed by heating and drying at 120 ° C. Further, the polyamic acid solution Ah was uniformly applied thereon so that the thickness after curing was about 2 to 3 μm, and then dried by heating at 120 ° C. to remove the solvent. Thus, after forming the polyamic acid layer of 3 layers, stepwise heat processing was performed from 120 degreeC to 360 degreeC, imidation was completed, and the metal-clad laminated board was obtained.

[Example 6]
A metal-clad laminate was obtained in the same manner as in Example 5 except that the polyamic acid solution Ab was used instead of the polyamic acid solution Aa in Example 5.

[Example 7]
A metal-clad laminate was obtained in the same manner as in Example 5, except that the polyamic acid solution Ac was used instead of the polyamic acid solution Aa in Example 5.

[Example 8]
A metal-clad laminate was obtained in the same manner as in Example 5, except that the polyamic acid solution A-d was used instead of the polyamic acid solution A-a in Example 5.

  From the above results, it was confirmed that CTE can be kept low by forming a resin film using a polyamic acid and a polyimide containing a predetermined ratio of DTBAB in the diamine component. Therefore, it was shown that by using the polyamic acid and polyimide of the present invention as the insulating layer material, it is possible to provide a circuit board such as an FPC having good transmission characteristics while suppressing the occurrence of warping.

[Synthesis Example A-1]
In a nitrogen atmosphere, 15 g of 2,5-bis (1,1-dimethylethyl) hydroquinone (67.5 mmol) was added to a three-necked flask containing a stir bar and dissolved in 202.5 ml of DMF. 20.5 g of potassium carbonate (148.4 mmol) and 23.4 g of 4-fluoronitrobenzene (148.4 mmol) were added to the solution, and the reaction was performed at 100 ° C. for 6 hours. The reaction was stopped after a predetermined time, cooled, poured into purified water, extracted with chloroform, and then the solvent was removed from the organic layer. Purification by recrystallization with chloroform / hexane gave compound A.

[Synthesis Example A-2]
Under a nitrogen atmosphere, 9.01 g of iron powder (161.5 mmol) was weighed into a three-necked flask containing a stirring bar, and 53.8 ml of a saturated aqueous ammonium chloride solution was added. After heating the three-necked flask to 110 ° C., 25 g of Compound A (53.8 mmol) dissolved in 140 ml of DMF was dropped into the three-necked flask with a dropping funnel, and then reacted at 120 ° C. for 3 hours. Immediately after completion of the reaction, iron powder was removed by Celite filtration, and the filtration residue was sufficiently washed with boiling DMF. The filtrate was cooled to 0 ° C., and the precipitate was washed with a large amount of purified water and dried to obtain diamine A.

[Synthesis Examples B-1 and B-2]
Similar to Synthesis Examples A-1 and A-2, except that 2,3-bis ((1,1-dimethylethyl) hydroquinone was used instead of 2,5-bis (1,1-dimethylethyl) hydroquinone Thus, diamine B was obtained.

[Synthesis Examples C-1 and C-2]
In the same manner as in Synthesis Examples A-1 and A-2, except that 2,5-bis (1-methylpropyl) hydroquinone was used instead of 2,5-bis (1,1-dimethylethyl) hydroquinone, Diamine C was obtained.

[Synthesis Examples D-1 and D-2]
Similar to Synthesis Examples A-1 and A-2, except that 2,6-bis ((1,1-dimethylethyl) hydroquinone was used instead of 2,5-bis (1,1-dimethylethyl) hydroquinone Thus, diamine D was obtained.

[Synthesis Examples E-1 and E-2]
In the same manner as in Synthesis Examples A-1 and A-2, except that 2,2-bis (2,2-dimethylethyl) hydroquinone was used instead of 2,5-bis (1,1-dimethylethyl) hydroquinone. Diamine E was obtained.

[Synthesis Examples F-1 and F-2]
In the same manner as in Synthesis Examples A-1 and A-2, except that 2,5-bis (1-methylheptyl) hydroquinone was used instead of 2,5-bis (1,1-dimethylethyl) hydroquinone. Diamine F was obtained.

[Synthesis Example 9]
Under a nitrogen stream, a 300 ml separable flask was charged with 3.567 g of diamine A (0.0043 mol), 8.045 g of m-TB (0.0387 mol) and 127.5 g of DMAc, and at room temperature. Stir to dissolve. Next, after 2.746 g of BPDA (0.0426 mol) was added, stirring was continued at room temperature for 3 hours to carry out a polymerization reaction to obtain a polyamic acid solution Ba. The weight average molecular weight of the polyamic acid solution Ba was 141,000.

[Synthesis Examples 10 to 48]
The polyamic acid solutions BB to Bi, Ca to Ci, Da to DF, E were used in the same manner as in Synthesis Example 9 except that the raw material compositions shown in Tables 4 to 11 were used. -A to Ef, Fa to Ff, Ga to Gc, and Ha were prepared.

[Example 9]
After uniformly applying the polyamic acid solution Ba prepared in Synthesis Example 9 to one surface (surface roughness Rz; 1.06 μm) of an electrolytic copper foil having a thickness of 12 μm so that the thickness after curing is about 25 μm. Then, the solvent was removed by heating and drying at 120 ° C. Furthermore, heat treatment was performed from 120 ° C. to 360 ° C. to complete imidization. About the obtained metal clad laminated board, the copper foil was etched away using the ferric chloride aqueous solution, and the resin film was obtained.
The thermal expansion coefficient (CTE) and dielectric constant of the obtained resin film were determined. Table 12 shows the measurement results.

[Examples 10 to 47]
Resin films of Examples 10 to 47 were obtained in the same manner as Example 9 except that the polyamic acid solutions shown in Tables 12 to 18 were used. The thermal expansion coefficient (CTE) and dielectric constant of the obtained resin film were determined. Each measurement result is shown in Tables 12-18.

[Example 48]
After applying the polyamic acid solution Ha uniformly on one surface (surface roughness Rz; 1.39 μm) of an electrolytic copper foil having a thickness of 12 μm so that the thickness after curing is about 2 to 3 μm, at 120 ° C. The solvent was removed by heating to dryness. Next, the polyamic acid solution Ba was uniformly coated thereon so that the thickness after curing was about 25 μm, and dried by heating at 120 ° C. to remove the solvent. Further, the polyamic acid solution Ha was uniformly applied thereon so that the thickness after curing was about 2 to 3 μm, and then dried by heating at 120 ° C. to remove the solvent. Thus, after forming the polyamic acid layer of 3 layers, stepwise heat processing was performed from 120 degreeC to 360 degreeC, imidation was completed, and the metal-clad laminated board was obtained.

[Example 49]
A metal-clad laminate was obtained in the same manner as in Example 48 except that the polyamic acid solution B-b was used instead of the polyamic acid solution Ba in Example 48.

[Example 50]
A metal-clad laminate was obtained in the same manner as in Example 48 except that the polyamic acid solution Bc was used instead of the polyamic acid solution Ba in Example 48.

[Example 51]
A metal-clad laminate was obtained in the same manner as in Example 48 except that the polyamic acid solution B-d was used instead of the polyamic acid solution Ba in Example 48.

[Example 52]
A metal-clad laminate was obtained in the same manner as in Example 48 except that the polyamic acid solution Be was used instead of the polyamic acid solution Ba in Example 48.

[Example 53]
A metal-clad laminate was obtained in the same manner as in Example 48 except that the polyamic acid solution Bf was used instead of the polyamic acid solution Ba in Example 48.

[Example 54]
A metal-clad laminate was obtained in the same manner as in Example 48 except that the polyamic acid solution B-g was used instead of the polyamic acid solution Ba in Example 48.

[Example 55]
A metal-clad laminate was obtained in the same manner as in Example 48 except that the polyamic acid solution Bh was used instead of the polyamic acid solution Ba in Example 48.

[Example 56]
A metal-clad laminate was obtained in the same manner as in Example 48 except that the polyamic acid solution Bi was used instead of the polyamic acid solution Ba in Example 48.

[Example 57]
A metal-clad laminate was obtained in the same manner as in Example 48 except that the polyamic acid solution Ca was used instead of the polyamic acid solution Ba in Example 48.

[Example 58]
A metal-clad laminate was obtained in the same manner as in Example 48 except that the polyamic acid solution Cb was used instead of the polyamic acid solution Ba in Example 48.

[Example 59]
A metal-clad laminate was obtained in the same manner as in Example 48 except that the polyamic acid solution Cc was used instead of the polyamic acid solution Ba in Example 48.

[Example 60]
A metal-clad laminate was obtained in the same manner as in Example 48 except that the polyamic acid solution Cd was used instead of the polyamic acid solution Ba in Example 48.

[Example 61]
A metal-clad laminate was obtained in the same manner as in Example 48 except that the polyamic acid solution Ce was used instead of the polyamic acid solution Ba in Example 48.

[Example 62]
A metal-clad laminate was obtained in the same manner as in Example 48 except that the polyamic acid solution Cf was used instead of the polyamic acid solution Ba in Example 48.

[Example 63]
A metal-clad laminate was obtained in the same manner as in Example 48 except that the polyamic acid solution C-g was used instead of the polyamic acid solution Ba in Example 48.

[Example 64]
A metal-clad laminate was obtained in the same manner as in Example 48 except that the polyamic acid solution Ch was used instead of the polyamic acid solution Ba in Example 48.

[Example 65]
A metal-clad laminate was obtained in the same manner as in Example 48 except that the polyamic acid solution Ci was used instead of the polyamic acid solution Ba in Example 48.

[Example 66]
A metal-clad laminate was obtained in the same manner as in Example 48 except that the polyamic acid solution Da was used instead of the polyamic acid solution Ba in Example 48.

[Example 67]
A metal-clad laminate was obtained in the same manner as in Example 48 except that the polyamic acid solution Db was used instead of the polyamic acid solution Ba in Example 48.

[Example 68]
A metal-clad laminate was obtained in the same manner as in Example 48 except that the polyamic acid solution Dc was used instead of the polyamic acid solution Ba in Example 48.

[Example 69]
A metal-clad laminate was obtained in the same manner as in Example 48 except that the polyamic acid solution D-d was used instead of the polyamic acid solution Ba in Example 48.

[Example 70]
A metal-clad laminate was obtained in the same manner as in Example 48 except that the polyamic acid solution De was used instead of the polyamic acid solution Ba in Example 48 .

[Example 71]
Instead of the polyamic acid solution B-a in Example 48, except for using a polyamic acid solution D-f, in the same manner as in Example 48, to obtain a metal-clad laminate.

[Example 72]
A metal-clad laminate was obtained in the same manner as in Example 48 except that the polyamic acid solution Ea was used instead of the polyamic acid solution Ba in Example 48 .

[Example 73]
Instead of the polyamic acid solution B-a in Example 48, except for using a polyamic acid solution E-b, in the same manner as in Example 48, to obtain a metal-clad laminate.

[Example 74]
A metal-clad laminate was obtained in the same manner as in Example 48 except that the polyamic acid solution Ec was used instead of the polyamic acid solution Ba in Example 48 .

[Example 75]
Instead of the polyamic acid solution B-a in Example 48, except for using a polyamic acid solution E-d, in the same manner as in Example 48, to obtain a metal-clad laminate.

[Example 76]
A metal-clad laminate was obtained in the same manner as in Example 48 except that the polyamic acid solution Ee was used instead of the polyamic acid solution Ba in Example 48.

[Example 77]
A metal-clad laminate was obtained in the same manner as in Example 48 except that the polyamic acid solution Ef was used instead of the polyamic acid solution Ba in Example 48.

[Example 78]
A metal-clad laminate was obtained in the same manner as in Example 48 except that the polyamic acid solution Fa was used instead of the polyamic acid solution Ba in Example 48.

[Example 79]
A metal-clad laminate was obtained in the same manner as in Example 48 except that the polyamic acid solution Fb was used instead of the polyamic acid solution Ba in Example 48.

[Example 80]
A metal-clad laminate was obtained in the same manner as in Example 48 except that the polyamic acid solution Fc was used instead of the polyamic acid solution Ba in Example 48.

[Example 81]
A metal-clad laminate was obtained in the same manner as in Example 48 except that the polyamic acid solution F-d was used instead of the polyamic acid solution Ba in Example 48.

[Example 82]
A metal-clad laminate was obtained in the same manner as in Example 48 except that the polyamic acid solution Fe was used instead of the polyamic acid solution Ba in Example 48.

[Example 83]
A metal-clad laminate was obtained in the same manner as in Example 48 except that the polyamic acid solution Ff was used instead of the polyamic acid solution Ba in Example 48.

[Example 84]
A metal-clad laminate was obtained in the same manner as in Example 48 except that the polyamic acid solution Ga was used instead of the polyamic acid solution Ba in Example 48.

[Example 85]
A metal-clad laminate was obtained in the same manner as in Example 48 except that the polyamic acid solution Gb was used instead of the polyamic acid solution Ba in Example 48.

[Example 86]
A metal-clad laminate was obtained in the same manner as in Example 48 except that the polyamic acid solution Gc was used instead of the polyamic acid solution Ba in Example 48.

  As mentioned above, although embodiment of this invention was described in detail for the purpose of illustration, this invention is not restrict | limited to the said embodiment, A various deformation | transformation is possible.

Claims (14)

A polyamic acid obtained by reacting a diamine component with an acid anhydride component containing a tetracarboxylic acid anhydride,
The diamine component is represented by the following general formula (i):

[Wherein, R represents a branched alkyl group having 4 to 8 carbon atoms, and p represents a number of 1 to 2. Here, when p is 2, R can independently have different carbon numbers. ]
The diamine compound represented by the formula is contained in the range of 10 to 60 mol% with respect to the total diamine component , and 2,2′-dimethyl-4,4′-diaminobiphenyl (m-TB), 2,2 ′. -One or more diamines selected from the group consisting of diethyl-4,4'-diaminobiphenyl (m-EB) and 2,2'-di-n-propyl-4,4'-diaminobiphenyl (m-NPB) Containing the compound in the range of 40 to 90 mol% with respect to the total diamine component,
And,
The acid anhydride component is one or more tetracarboxylic anhydrides selected from the group consisting of pyromellitic anhydride (PMDA) and 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (BPDA) In the range of 50 to 100 mol% with respect to the total acid anhydride component. The diamine component contains the 2,2′-dimethyl-4,4′-diaminobiphenyl (m-TB), and the diamine compound represented by the general formula (i) is 1,4-bis (4-aminophenoxy). ) -2,5-di-tert-butylbenzene (DTBAB) and / or 1,4bis (4-aminophenoxy) -2,3-di-tert-butylbenzene, and
The acid anhydride component and the 1,4bis (4-aminophenoxy) -2,5-di-tert-butylbenzene (DTBAB) and / or the 1,4bis (4-aminophenoxy) -2,3- The blending amount of di-tert-butylbenzene is the following formula A;
y = 0.2996x−8.4193 (Equation A)
[Wherein, x represents the 1,4-bis (4-aminophenoxy) -2,5-di-tert-butylbenzene (DTBAB) and / or the 1,4-bis (4-aminophenoxy) -2,3 -The value obtained by multiplying the total amount (mol%) of di-tert-butylbenzene by a factor of 2.1 and 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride in the acid anhydride component It means the sum with the blending amount (mol%) of (BPDA), and y means a number in the range of 10 to 30]
The polyamic acid according to claim 1 , which satisfies the relationship represented by: The diamine component contains the 2,2′-diethyl-4,4′-diaminobiphenyl (m-EB), and the diamine compound represented by the general formula (i) is 1,4-bis (4-aminophenoxy). ) -2,5-di-tert-butylbenzene (DTBAB) and / or 1,4 bis (4-aminophenoxy) -2,3-di-tert-butylbenzene, and the acid anhydride component Said 1,4 bis (4-aminophenoxy) -2,5-di-tert-butylbenzene (DTBAB) and / or said 1,4 bis (4-aminophenoxy) -2,3-di-tert-butylbenzene Of the following formula B;
y = 0.0.313x-3.3320 (Formula B)
[Wherein x is the 1,4-bis (4-aminophenoxy) -2,5-di-tert-butylbenzene (DTBAB) and / or the 1,4-bis (4-aminophenoxy) -2,3- A value obtained by multiplying the total amount (mol%) of di-tert-butylbenzene by a factor of 1.9, and 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride ( BPDA) is the sum of the amount (mol%) and y is a number in the range of 10 to 30]
The polyamic acid according to claim 1 , which satisfies the relationship represented by: The diamine component contains 2,2′- di- n-propyl-4,4′-diaminobiphenyl (m-NPB) and the diamine compound represented by the general formula (i) is 1,4 bis (4 -Aminophenoxy) -2,5-di-tert-butylbenzene (DTBAB) and / or 1,4 bis (4-aminophenoxy) -2,3-di-tert-butylbenzene, and the acid anhydride And 1,4 bis (4-aminophenoxy) -2,5-di-tert-butylbenzene (DTBAB) and / or 1,4 bis (4-aminophenoxy) -2,3-di-tert -The amount of butylbenzene blended is the following formula C;
y = 0.3005x + 15.0500 (Equation C)
[Wherein x is the 1,4-bis (4-aminophenoxy) -2,5-di-tert-butylbenzene (DTBAB) and / or the 1,4-bis (4-aminophenoxy) -2,3- A value obtained by multiplying the total amount (mol%) of di-tert-butylbenzene by a coefficient of 1.3, and 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride in the acid anhydride component ( BPDA) is the sum of the amount (mol%) and y is a number in the range of 10 to 30]
The polyamic acid according to claim 1 , which satisfies the relationship represented by: The diamine component contains the 2,2′-dimethyl-4,4′-diaminobiphenyl (m-TB), and the diamine compound represented by the general formula (i) is 1,4-bis (4-aminophenoxy). ) -2,5-di (1-methylpropyl) benzene, and the acid anhydride component and 1,4-bis (4-aminophenoxy) -2,5-di (1-methylpropyl) benzene The quantity is the following formula D;
y = 0.2986x-8.3997 (Formula D)
[Wherein x is a value obtained by multiplying the blending amount (mol%) of 1,4-bis (4-aminophenoxy) -2,5-di (1-methylpropyl) benzene by a coefficient of 4.3, and the acid Means the sum of the 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (BPDA) content in the anhydride component (mol%), and y is a number in the range of 10 to 30 Means]
The polyamic acid according to claim 1 , which satisfies the relationship represented by: The diamine component contains the 2,2′-diethyl-4,4′-diaminobiphenyl (m-EB), and the diamine compound represented by the general formula (i) is 1,4-bis (4-aminophenoxy). ) -2,5-di (1-methylpropyl) benzene, and the anhydride component and the 1,4-bis (4-aminophenoxy) -2,5-di (1-methylpropyl) benzene The blending amount is the following formula E;
y = 0.003x−3.4028 (Equation E)
[Wherein x is a value obtained by multiplying the blending amount (mol%) of 1,4-bis (4-aminophenoxy) -2,5-di (1-methylpropyl) benzene with a coefficient of 4.1 It means the sum of the amount of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (BPDA) in the anhydride component (mol%), and y is in the range from 10 to 30 Means number]
The polyamic acid according to claim 1 , which satisfies the relationship represented by: The diamine component contains the 2,2′-dimethyl-4,4′-diaminobiphenyl (m-TB), and the diamine compound represented by the general formula (i) is 1,4-bis (4-aminophenoxy). ) -2,6-di-tert-butylbenzene, and the amount of the acid anhydride component and the 1,4 bis (4-aminophenoxy) -2,6-di-tert-butylbenzene is Formula F below;
y = 0.2971x−8.3862 ... (Formula F)
[Wherein x is a value obtained by multiplying the blending amount (mol%) of 1,4-bis (4-aminophenoxy) -2,6-di-tert-butylbenzene by a factor of 4.5, and the acid anhydride It means the sum with the amount (mol%) of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (BPDA) in the component, and y means a number in the range of 10 to 30 To do]
The polyamic acid according to claim 1 , which satisfies the relationship represented by: The diamine component contains the 2,2′-diethyl-4,4′-diaminobiphenyl (m-EB), and the diamine compound represented by the general formula (i) is 1,4-bis (4-aminophenoxy). ) -2,6-di-tert-butylbenzene, and the amount of the acid anhydride component and the 1,4 bis (4-aminophenoxy) -2,6-di-tert-butylbenzene is Formula G below;
y = 0.2986x-3.397 ... (Formula G)
[Wherein x is a value obtained by multiplying the blending amount (mol%) of 1,4-bis (4-aminophenoxy) -2,6-di-tert-butylbenzene by a coefficient of 4.3, and the acid anhydride This means the sum of the amount of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (BPDA) in the component and the sum (mol%), and y is a number in the range from 10 to 30 means]
The polyamic acid according to claim 1 , which satisfies the relationship represented by: The diamine component contains the 2,2′-dimethyl-4,4′-diaminobiphenyl (m-TB), and the diamine compound represented by the general formula (i) is 1,4-bis (4-aminophenoxy). ) -2,5-di (2-methylpropyl) benzene, and the acid anhydride component and the 1,4-bis (4-aminophenoxy) -2,5-di (2-methylpropyl) benzene The blending amount is the following formula H;
y = 0.3011x−8.6596 (Equation H)
[Wherein x is a value obtained by multiplying the blending amount (mol%) of 1,4-bis (4-aminophenoxy) -2,5-di (2-methylpropyl) benzene by a factor of 6.1, and the acid Means the sum of the 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (BPDA) content in the anhydride component (mol%), and y is a number in the range of 10 to 30 Means]
The polyamic acid according to claim 1 , which satisfies the relationship represented by: The diamine component contains the 2,2′-diethyl-4,4′-diaminobiphenyl (m-EB), and the diamine compound represented by the general formula (i) is 1,4-bis (4-aminophenoxy). ) -2,5-di (2-methylpropyl) benzene, and the acid anhydride component and the 1,4-bis (4-aminophenoxy) -2,5-di (2-methylpropyl) benzene The blending amount is the following formula I;
y = 0.2984x-3.6137 ... (Formula I)
[Wherein x is a value obtained by multiplying the blending amount (mol%) of 1,4-bis (4-aminophenoxy) -2,5-di (2-methylpropyl) benzene by a factor of 6.0 and the acid It means the sum of the amount of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (BPDA) in the anhydride component (mol%), and y is in the range from 10 to 30 Means number]
The polyamic acid according to claim 1 , which satisfies the relationship represented by: The polyimide obtained by imidating the polyamic acid of any one of Claim 1 to 10 . The resin film containing the polyimide obtained by imidating the polyamic acid of any one of Claim 1 to 10 . The resin film according to claim 12 , wherein the thermal expansion coefficient is in the range of 10 × 10 ⁻⁶ to 30 × 10 ⁻⁶ (1 / K). A metal-clad laminate having a resin layer containing the polyimide according to claim 11 .