JP2017080901A - Metal-clad laminate, printed wiring board using the same, and electronic apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a metal-clad laminate excellent in adhesion between a metal foil and a polyimide layer.SOLUTION: In a metal-clad laminate including a metal foil and a polyimide layer laminated on the metal foil, the polyimide layer is a layer comprising polyimide containing a repeating unit (A) having a carboxyl group and a repeating unit (B) not having a carboxyl group, and preferably, the metal foil includes, on the surface, a surface treatment layer comprising a silane coupling agent containing a nitrogen atom.SELECTED DRAWING: None

Description

  The present invention relates to a metal-clad laminate including a polyimide layer, a printed wiring board using the same, and an electronic device.

  Polyimide films are excellent in mechanical strength and electrical insulation, and are used in various applications such as electrical insulation materials and substrate films for wiring boards. Moreover, since a polyimide film is excellent in heat resistance, it is utilized as a resin film for a base material of a copper clad laminate that requires heat treatment at a high temperature when bonded to a copper foil. However, the conventional copper clad laminate provided with a polyimide layer does not necessarily have sufficient adhesion between the copper foil and the polyimide layer. For this reason, in order to improve the adhesiveness of copper foil and a polyimide layer, various methods are examined.

  For example, in JP-A-2005-48269 (Patent Document 1), the adhesion between the copper foil and the polyimide layer is improved by treating the surface of the copper foil with a silane coupling agent containing nitrogen. Is described. In addition, in Japanese Patent Application Laid-Open No. 2012-76278 (Patent Document 2) and Japanese Patent Application Laid-Open No. 2012-76363 (Patent Document 3), a Ni layer and a Cr layer are sequentially formed on the surface of a copper foil, and a specific layer is formed thereon. It is described that the adhesion between the copper foil and the polyimide layer is improved by forming a polyimide layer having a structure. Furthermore, JP, 2014-141736, A (patent documents 4) describes that the adhesiveness of copper foil and a polyimide layer improves by performing roughening processing to the copper foil surface.

  On the other hand, International Publication No. 2011/099518 (Patent Document 5) describes an alicyclic polyimide having a specific structure. This alicyclic polyimide had sufficient light transmittance and high heat resistance.

JP 2005-48269 A JP 2012-76278 A JP 2012-76363 A JP, 2014-141736, A International Publication No. 2011/099518

  However, the methods described in Patent Documents 1 to 4 are mainly methods for improving the adhesion between the copper foil and the polyimide layer by treating the surface of the copper foil, and the polyimide layer is almost studied. There was still room for improvement. As for polyimide, there is a demand for a new polyimide that can be more easily produced than the polyimide described in Patent Document 5.

  The present invention has been made in view of the above-described problems of the prior art. A metal-clad laminate having excellent adhesion between a metal foil (in particular, a copper foil) and a polyimide layer, a printed wiring board using the same, and An object is to provide electronic equipment.

  As a result of intensive studies to achieve the above object, the inventors of the present invention, in a metal-clad laminate including a metal foil and a polyimide layer, have carboxyl groups in some repeating units of polyimide constituting the polyimide layer. It has been found that by introducing a group derived from an aromatic diamine, the adhesion between the metal foil (especially copper foil) and the polyimide layer is improved, and the present invention has been completed.

That is, the metal-clad laminate of the present invention comprises a metal foil and a polyimide layer laminated on the metal foil, and
The polyimide layer has the following general formula (1):

[In the formula (1), A represents a single bond, a divalent aliphatic group having 1 to 12 carbon atoms forming a chain structure, or 3 to 12 carbon atoms forming a cyclic structure. 1 type selected from the group which consists of a certain bivalent alicyclic group and the bivalent aromatic group whose number of carbon atoms which form an aromatic ring is 6-30, shows the said alicyclic group and the said The aromatic group may have a substituent, and each of the plurality of R ¹ is independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a hydroxyl group, and a nitro group. Or two R ¹ bonded to the same carbon atom may be combined to form a methylidene group, and R ² and R ³ each independently represent a hydrogen atom and a carbon number of 1 to 10 represents one selected from the group consisting of alkyl group, an aromatic R ¹⁰ is a carboxyl group di- It shows the Min-derived group. ]
A repeating unit (A) having a carboxyl group represented by the following general formula (2):

[In the formula (2), A represents a single bond, a divalent aliphatic group having 1 to 12 carbon atoms forming a chain structure, or 3 to 12 carbon atoms forming a cyclic structure. 1 type selected from the group which consists of a certain bivalent alicyclic group and the bivalent aromatic group whose number of carbon atoms which form an aromatic ring is 6-30, shows the said alicyclic group and the said The aromatic group may have a substituent, and each of the plurality of R ¹ is independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a hydroxyl group, and a nitro group. Or two R ¹ bonded to the same carbon atom may be combined to form a methylidene group, and R ² and R ³ each independently represent a hydrogen atom and a carbon number of 1 to 10 represents one selected from the group consisting of alkyl groups, aromatic R ¹¹ is without a carboxyl group Indicating the amine-derived groups. ]
It is a layer which consists of a polyimide containing the repeating unit (B) which does not have a carboxyl group represented by these.

In such a metal-clad laminate, A in the general formulas (1) and (2) may have a substituent, and the number of carbon atoms forming an aromatic ring is 6 to 30. Certain divalent aromatic groups are preferred. Further, as the ^{R 10,} the following general formula (101) to (104):

[In the formula (101), R ¹² represents one selected from the group consisting of a hydrogen atom, a methoxy group, and an ethoxy group. ]
One group selected from the group represented by formula (II) is preferred, and the R ¹¹ is represented by the following general formula (201):

The group represented by these is preferable. Moreover, as said metal foil, what equips the surface with the surface treatment layer which consists of a silane coupling agent containing a nitrogen atom is preferable. Moreover, copper foil is preferable.

  Moreover, the printed wiring board of the present invention includes the metal-clad laminate of the present invention, and the electronic device of the present invention includes the printed wiring board of the present invention. Is.

The polyimide of the present invention comprises a repeating unit (A) having a carboxyl group represented by the general formula (1) and a repeating unit (B) having no carboxyl group represented by the general formula (2). It contains. In such a polyimide, as A in the general formulas (1) and (2), a divalent which may have a substituent and has 6 to 30 carbon atoms forming an aromatic ring. The aromatic group is preferred. Further, as the ^{R 10,} 1 kind of group selected from groups represented by the general formula (101) to (104) are preferred, and as the ^{R 11,} the above general formula (201) The group represented by these is preferable.

  In the metal-clad laminate of the present invention, the reason why the adhesion between the metal foil (particularly copper foil) and the polyamide layer is not necessarily clear, but the present inventors speculate as follows. That is, the polyimide layer according to the present invention comprises a repeating unit (A) having a carboxyl group represented by the general formula (1) and a repeating unit (B) having no carboxyl group represented by the general formula (2). ) And a polyimide layer. When such a polyimide layer is laminated on a metal foil, an interaction works between the carboxyl group in the repeating unit (A) and the surface of the metal foil, so that the metal foil (especially copper foil) and the polyimide layer It is presumed that the adhesion is improved. In particular, when a surface treatment layer made of a silane coupling agent containing a nitrogen atom (for example, a silane coupling agent having an amino group) is formed on the surface of the metal foil, a group containing a nitrogen atom (for example, Since a stronger interaction acts between the amino group and the carboxyl group, it is presumed that the adhesion between the metal foil (particularly, copper foil) and the polyimide layer is further improved.

  ADVANTAGE OF THE INVENTION According to this invention, it becomes possible to provide the metal-clad laminated board excellent in the adhesiveness of metal foil (especially copper foil) and a polyimide layer, a printed wiring board using the same, and an electronic device.

2 is a graph showing an infrared absorption spectrum (IR spectrum) of the polyimide film obtained in Example 1. FIG.

  Hereinafter, the present invention will be described in detail with reference to preferred embodiments thereof.

[Metal-clad laminate]
The metal-clad laminate of the present invention comprises a metal foil and a polyimide layer laminated on the metal foil, and
The polyimide layer has the following general formula (1):

[In the formula (1), A represents a single bond, a divalent aliphatic group having 1 to 12 carbon atoms forming a chain structure, or 3 to 12 carbon atoms forming a cyclic structure. 1 type selected from the group which consists of a certain bivalent alicyclic group and the bivalent aromatic group whose number of carbon atoms which form an aromatic ring is 6-30, shows the said alicyclic group and the said The aromatic group may have a substituent, and each of the plurality of R ¹ is independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a hydroxyl group, and a nitro group. Or two R ¹ bonded to the same carbon atom may be combined to form a methylidene group, and R ² and R ³ each independently represent a hydrogen atom and a carbon number of 1 to 10 represents one selected from the group consisting of alkyl group, an aromatic R ¹⁰ is a carboxyl group di- It shows the Min-derived group. ]
A repeating unit (A) having a carboxyl group represented by the following general formula (2):

[In the formula (2), A represents a single bond, a divalent aliphatic group having 1 to 12 carbon atoms forming a chain structure, or 3 to 12 carbon atoms forming a cyclic structure. 1 type selected from the group which consists of a certain bivalent alicyclic group and the bivalent aromatic group whose number of carbon atoms which form an aromatic ring is 6-30, shows the said alicyclic group and the said The aromatic group may have a substituent, and each of the plurality of R ¹ is independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a hydroxyl group, and a nitro group. Or two R ¹ bonded to the same carbon atom may be combined to form a methylidene group, and R ² and R ³ each independently represent a hydrogen atom and a carbon number of 1 to 10 represents one selected from the group consisting of alkyl groups, aromatic R ¹¹ is without a carboxyl group Indicating the amine-derived groups. ]
It is a layer which consists of a polyimide containing the repeating unit (B) which does not have a carboxyl group represented by these.

(Metal foil)
The metal foil used in the present invention is not particularly limited, and a known metal foil capable of laminating a polyimide layer can be appropriately used. As such metal foil, for example, copper foil, phosphor bronze, red copper, brass, western white, titanium copper, Corson alloy, etc., copper alloy foil, stainless steel foil, aluminum foil, iron foil, iron alloy foil, nickel There are foil, nickel alloy foil and the like. In the present invention, copper foil is particularly preferable.

  Hereinafter, the metal foil used in the present invention will be described in detail using a copper foil as an example.

  The copper foil used in the present invention may be a rolled copper foil or an electrolytic copper foil, but a rolled copper foil is preferred. In such a copper foil, the surface on which the polyimide layer is laminated may be roughened. The roughening treatment can be performed by copper-cobalt-nickel alloy plating treatment, copper-nickel-phosphorus alloy plating treatment, or the like, as described in Japanese Patent Application Laid-Open No. 2014-141736.

  Moreover, a heat resistant layer or a rust preventive layer may be formed on the surface of the copper foil on which the polyimide layer is laminated (the roughened surface when the roughened treatment is performed). On the copper foil surface that has not been subjected to the roughening treatment, a heat-resistant layer or a rust-preventing layer can be formed by applying a nickel plating treatment or the like, as described in Japanese Patent Application Laid-Open No. 2014-141736. it can. In addition, as described in Japanese Patent Application Laid-Open No. 2014-141736, the surface of the copper foil subjected to the roughening treatment is subjected to a cobalt-nickel alloy plating treatment or the like, followed by a zinc plating treatment or a zinc alloy plating. By performing treatment or the like, a heat-resistant layer or a rust-proof layer can be formed.

  Furthermore, the surface of the copper foil on which the polyimide layer is laminated (the surface of the roughened surface when roughened or the surface of the layer when a heat-resistant layer or a rust-proof layer is formed) contains nitrogen atoms. It is preferable that the surface treatment layer which consists of a silane coupling agent containing is formed. Thereby, the adhesiveness of copper foil and a polyimide layer improves further. Examples of such a silane coupling agent containing a nitrogen atom include N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N -(2-aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propyl Silane coupling agents containing amino groups such as amine, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane; N- [3- (Triethoxysilyl) propyl] -4,5-dihydroimidazole, etc. Silane coupling agent containing a dazole group; Silane coupling agent containing an isocyanurate group such as tris- (trimethoxysilylpropyl) isocyanurate; Silane coupling containing a ureido group such as 3-ureidopropyltrialkoxysilane Agents; silane coupling agents containing isocyanate groups such as 3-isocyanatopropyltriethoxysilane.

  In the present invention, as such a copper foil, JX Nippon Mining & Metals Co., Ltd. manufactures and sells, for example, a base foil excellent in bending characteristics such as HA foil, HA-V2 foil, tough pitch foil, and fine roughening It is possible to use rolled copper foil in which particles are formed or electrolytic copper foil such as JXEFL.

  The thickness of the copper foil used in the present invention is not particularly limited as long as it can be applied to a copper clad laminate.

(Polyimide layer)
The polyimide layer concerning this invention is laminated | stacked on the said metal foil, and is represented by the repeating unit (A) which has a carboxyl group represented by the said General formula (1), and the said General formula (2). It is the layer which consists of a polyimide containing the repeating unit (B) which does not have a carboxyl group.

  A in the general formula (1) is one selected from the group consisting of a single bond, a divalent aliphatic group, a divalent alicyclic group and a divalent aromatic group, and the alicyclic ring The aromatic group and the aromatic group may have a substituent. Among such linking groups, a single bond or a divalent aromatic group is preferred from the viewpoint of ease of synthesis and purification of tetracarboxylic dianhydride.

  The number of carbons forming a chain structure contained in the aliphatic group is 1 to 12, and the number of carbons forming a cyclic structure contained in the alicyclic group (herein, “cyclic structure” "The number of carbons forming" means that when the alicyclic group has a substituent containing carbon (such as a hydrocarbon group), the number of carbons in the substituent is not included, and the alicyclic group This refers only to the number of carbons in the cyclic structure, for example, in the case of 2-ethyl-1,4-cyclohexylene group, the number of carbons forming the chain structure is 6). Yes, the number of carbons forming an aromatic ring contained in the aromatic group (herein, “the number of carbons forming an aromatic ring” means that the aromatic group contains a carbon-containing substituent (hydrocarbon) Group), the number of carbons in the substituent is not included, only the number of carbons in the aromatic ring in the aromatic group Say. For example, in the case of 2-ethyl-1,4-phenylene group, the number of carbon forming an aromatic ring is 6.) Is 6-30. When the number of carbons forming such a chain structure, cyclic structure or aromatic ring exceeds the upper limit, the polyimide tends to be colored. Moreover, from the viewpoint of transparency of the obtained polyimide and ease of synthesis and purification of tetracarboxylic dianhydride, the number of carbons forming the chain structure of the divalent aliphatic group is 1-10. More preferably, it is more preferably 1-6, particularly preferably 1-3, and the number of carbons forming the cyclic structure of the divalent alicyclic group is 3-10. Is more preferably 4-10, particularly preferably 5-8, and the number of carbons forming the aromatic ring of the divalent aromatic group is more preferably 6-18. Preferably, it is 6-12.

  Such a divalent aliphatic group is not particularly limited as long as it satisfies the above condition of the number of carbons. For example, methane, ethane, propane, butane, pentane, hexane, heptane, octane, nonane , Decane, undecane, dodecane and other aliphatic compounds from which two hydrogen atoms are eliminated (in addition, as such a residue, the position of the hydrogen atom to be eliminated is not particularly limited, for example, Methylene group, ethylene group, ethylidene group, 1,2-propylene group (1-methylethylene group), 1,3-propylene group (trimethylene group), 1,2-butylene group (1-ethylethylene group), 1, A 3-butylene group (1-methyl-1,3-propylene group), a 1,4-butylene group (tetramethylene group) and the like can be used as appropriate.

  Such a divalent alicyclic group is not particularly limited as long as it satisfies the above condition of the number of carbons. For example, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, Residues in which two hydrogen atoms are eliminated from an alicyclic compound such as cyclononane, cyclodecane, cycloundecane, cyclododecane, etc. (Note that the position of the leaving hydrogen atom is not particularly limited as such a residue. For example, 1,2-cyclopropylene group, 1,3-cyclobutylene group, 1,4-cyclohexylene group, etc.); and at least one hydrogen atom in the residue is substituted with a substituent Group (for example, 3-methyl-1,2-cyclopropylene group, 2-methyl-1,3-cyclobutylene group, 2-methyl-1,4-cyclyl) Hexylene, 2,5-1,4- cyclohexylene group) can be appropriately used.

  Such a divalent aromatic group is not particularly limited as long as it satisfies the above condition of the number of carbons. For example, benzene, naphthalene, terphenyl, anthracene, phenanthrene, triphenylene, pyrene, chrysene, Residues from which two hydrogen atoms have been eliminated from an aromatic compound such as biphenyl, terphenyl, quaterphenyl, or kinkphenyl (Note that the position of the hydrogen atom to be eliminated is particularly limited as such a residue. And, for example, 1,4-phenylene group, 2,6-naphthylene group, 4,4'-biphenylene group, 9,10-anthracenylene group, etc.); and at least one hydrogen in the residue A group in which an atom is substituted with a substituent (for example, 2,5-dimethyl-1,4-phenylene group, 2,3,5,6-tetramethyl-1,4-phenyl); Ylene group) and the like can be used as appropriate.

  In addition, among these divalent aromatic groups, when a polyimide is produced, the solubility of the polyimide in the solvent becomes better, and from the viewpoint of obtaining a higher degree of workability, each substituent is changed. A phenylene group, a biphenylene group, a naphthylene group, an anthracenylene group or a terphenylene group, which may or may not be present, is preferably a phenylene which may or may not have a substituent. Group, biphenylene group, and naphthylene group are more preferable, and a phenylene group and a biphenylene group, which may or may not have a substituent, are further preferable.

  Further, in A in the general formula (1), the substituent that the divalent alicyclic group and the divalent aromatic group may have is not particularly limited, and examples thereof include an alkyl group and an alkoxy group. And halogen atoms. Among the substituents that the divalent alicyclic group and the divalent aromatic group may have, the solubility of the polyimide in the solvent becomes better, and higher processability is obtained. From the viewpoint, an alkyl group having 1 to 10 carbon atoms and an alkoxy group having 1 to 10 carbon atoms are more preferable. When the number of carbon atoms of the alkyl group and alkoxy group suitable as such a substituent exceeds 10, the heat resistance of the polyimide tends to decrease. In addition, the number of carbon atoms of the alkyl group and alkoxy group suitable as such a substituent is preferably 1 to 6 and more preferably 1 to 5 from the viewpoint that higher heat resistance can be obtained. 1 to 4 is more preferable, and 1 to 3 is particularly preferable. In addition, each of the alkyl group and alkoxy group that can be selected as such a substituent may be linear or branched.

The alkyl group that can be selected as R ¹ in the general formula (1) is an alkyl group having 1 to 10 carbon atoms. When the number of carbon atoms exceeds 10, the glass transition temperature is lowered and a sufficiently high heat resistance cannot be achieved. As the number of carbon atoms in the alkyl group such can be selected as R ^1, from the viewpoint of purification becomes easier, is preferably 1-6, more preferably 1-5, 1 4 is more preferable, and 1 to 3 is particularly preferable. Such an alkyl group that can be selected as R ¹ may be linear or branched. Further, such an alkyl group is more preferably a methyl group or an ethyl group from the viewpoint of ease of purification.

Further, among the plurality of R ¹ in the general formula (1), the same two R ¹ attached to a carbon atom, they form a methylidene group together (= CH ₂₎ Also good. That is, two R ¹ bonded to the same carbon atom in the general formula (1) are combined to form the carbon atom (of the carbon atoms forming the norbornane ring structure, two R ¹ are bonded). May be bonded as a methylidene group (methylene group) by a double bond.

As R ¹ in the general formula (1), when a polyimide is produced, higher heat resistance is obtained, raw materials are easily obtained, purification is easier, and the like. Therefore, each independently is preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group or an isopropyl group, and particularly preferably a hydrogen atom or a methyl group. In addition, a plurality of R ¹ in such a formula may be the same or different from each other, but may be the same from the viewpoint of ease of purification and the like. preferable.

R ² and R ³ in the general formula (1) are each independently one selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 10 carbon atoms. When the carbon number of such an alkyl group selected as R ² and R ³ exceeds 10, the heat resistance of the polyimide is lowered. Moreover, as carbon number of the alkyl group which can be selected as such R < ² > and R < ³ >, it is preferable that it is 1-6 from a viewpoint that higher heat resistance is obtained, and it is 1-5. More preferably, it is still more preferably 1-4, and particularly preferably 1-3. Further, such an alkyl group that can be selected as R ² and R ³ may be linear or branched.

In addition, R ² and R ³ in the general formula (1) have higher heat resistance when the polyimide is produced, are easily available, and are more easily purified. From the viewpoints of, etc., it is more preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, or an isopropyl group, and particularly preferably a hydrogen atom or a methyl group. In addition, R ² and R ³ in the general formula (1) may be the same or different from each other, but are the same from the viewpoint of ease of purification and the like. Preferably there is.

Moreover, it is particularly preferable that all of R ¹ , R ² and R ³ in the general formula (1) are hydrogen atoms. Thus, in the repeating unit represented by the general formula (1), when all of the substituents represented by R ¹ , R ² and R ³ are hydrogen atoms, higher heat resistance is obtained. Tend to be.

R ¹⁰ in the general formula (1) is a group derived from an aromatic diamine having a carboxyl group. The metal-clad laminate of the present invention has a repeating unit (A) containing a group derived from an aromatic diamine having such a carboxyl group as the polyimide constituting the polyimide layer. The adhesion between the foil) and the polyimide layer is improved. The base which can be selected as R ¹⁰ in the general formula (1) is a metal foil (particularly, copper) from the viewpoint of adhesion between the polyimide layer is further improved by the following general formula (101) - ( 104):

[In the formula (101), R ¹² represents one selected from the group consisting of a hydrogen atom, a methoxy group, and an ethoxy group. ]
Is preferably selected from the group represented by the general formula (101) or (102), more preferably a group represented by the general formula (101). Particularly preferred is a group.

Furthermore, ^A in the general formula ^{(2), R 1, R} 2, R 3 have the same meaning as ^{A, R 1, R 2,} R 3 in the general formula (1). Ie, ^A in the general formula ^{(2), R 1, R} 2, R 3 are, ^A in the general formula ^{(1), R 1, R} 2, R 3 and is similar (their preferred Are the same as the preferable ones of A, R ¹ , R ² and R ^{3 in} the general formula (1).

In addition, R ¹¹ in the general formula (2) is a group derived from an aromatic diamine having no carboxyl group. Although there is no restriction | limiting in particular as a group derived from aromatic diamine which does not have such a carboxyl group, From a heat resistant viewpoint, following General formula (21)-(24):

[In the formula (23), R ¹³ represents one selected from the group consisting of a hydrogen atom, a fluorine atom, a methyl group, an ethyl group, and a trifluoromethyl group. In the formula (24), Q represents a formula: _{-O -, - O-C 6} H 4 -O -, - O-C 6 H 4 -C 6 H 4 -O -, - S -, - CO -, - O-C 6 H 4 -CO-C _{6 H 4 -O -, - CONH} -, - COO -, - C 6 H 4 -, - C 10 H 6 -, - NHCO-C 6 H 4 -CONH -, - CONH-C 6 H 4 -NHCO- _{, -OCO-C 6 H 4 -COO} -, - COO-C 6 H 4 -OCO -, - O-C 10 H 6 -O -, - OCO-C 10 H 6 -COO -, - COO-C 10 _{H 6 -OCO -, - CONH-} C 10 H 6 -NHCO -, - NHCO-C 10 H 6 -CONH -, - SO 2 - _{, -C (CF 3) 2 -} , - C (CH 3) 2 -, - CH 2 -, - O-C 6 H 4 -C (CH 3) 2 -C 6 H 4 -O -, - O- _{C 6 H 4 -C (CF 3} ) 2 -C 6 H 4 -O -, - O-C 6 H 4 -SO 2 -C 6 H 4 -O-, and, -C _{(CH 3)} 2 -C _{6 H 4 -C (CH 3)} 2 - shows the one selected from the group consisting of groups represented by. ]
The group represented by general formula (23) or (24) is more preferable, and the group represented by general formula (24) is still more preferable.

From the viewpoint of heat resistance, R ¹³ in the general formula (23) is more preferably a hydrogen atom, a fluorine atom, a methyl group or an ethyl group, particularly preferably a hydrogen atom, and the general formula (24). the Q in the _{formula: -CONH -, - O-C} 6 H 4 -C 6 H 4 -O -, - COO -, - C 6 H 4 -, - O-C 6 H 4 -C (CH ₃₎ is more preferably ₂ -C ₆ H group represented by ₄ -O-, _{formula: -CONH -, - O-C} 6 H 4 -C 6 H 4 -O -, - C 6 H 4 -, - A group represented by O—C ₆ H ₄ —C (CH ₃ ) ₂ —C ₆ H ₄ —O— is more preferred, and the formula: —CONH—, —O—C ₆ H ₄ —C ₆ H ₄ —O —, —O—C ₆ H ₄ —C (CH ₃ ) ₂ —C ₆ H ₄ —O— is particularly preferred, and the formula: —O—C ₆ H ₄ —C _{(CH 3)} is most preferred groups represented by 2 _-C 6 _H 4 -O-.

Among the groups derived from aromatic diamines having no carboxyl group, R ¹¹ in the general formula (2) has heat resistance and adhesion between the metal foil (especially copper foil) and the polyimide layer. From the viewpoint, the following general formula (201):

Is particularly preferred.

  In the polyimide layer according to the present invention, the content ratio of the repeating unit (A) having a carboxyl group represented by the general formula (1) is 1 to 50 mol with respect to 100 mol% of all repeating units constituting the polyimide. %, More preferably 2 to 30 mol%, further preferably 3 to 20 mol%, particularly preferably 3 to 10 mol%. When the content ratio of the repeating unit (A) is less than the lower limit, the adhesion between the metal foil (especially copper foil) and the polyimide layer tends not to be improved. On the other hand, when the upper limit is exceeded, a polyimide layer is formed. Tend to be difficult to do. Moreover, as a content rate of the repeating unit (B) which does not have a carboxyl group represented by the said General formula (2), 50-99 mol% is preferable with respect to 100 mol% of all the repeating units which comprise a polyimide. 70-98 mol% is more preferable, 80-97 mol% is still more preferable, and 90-97 mol% is especially preferable.

  Moreover, in the polyimide layer concerning this invention, in the range which does not impair the effect of this invention, you may contain other repeating units other than the said repeating unit (A) and (B). Such other repeating unit is not particularly limited, and a known repeating unit capable of constituting polyimide can be appropriately used. For example, tetracarboxylic dianhydride represented by the following general formula (3) Repeating units formed from the reaction of the product with other diamines other than aromatic diamines, other tetracarboxylic dianhydrides other than the tetracarboxylic dianhydrides represented by the general formula (3) described later A repeating unit formed from the reaction of a diamine with an aromatic diamine, other than the tetracarboxylic dianhydride and the aromatic diamine other than the tetracarboxylic dianhydride represented by the general formula (3) described later Examples thereof include a repeating unit formed by reaction with other diamine. As the content ratio of such other repeating units, from the viewpoints of heat resistance of the polyimide layer, adhesion to metal foil (especially copper foil) and transparency, 100 mol% of all repeating units constituting the polyimide. 50 mol% or less is preferable, 25 mol% or less is more preferable, 10 mol% or less is more preferable, 5 mol% or less is particularly preferable, and 0 mol% is most preferable.

  Although the thickness in particular of the polyimide layer concerning this invention is not restrict | limited, It is preferable that it is 1-500 micrometers, and it is more preferable that it is 5-100 micrometers. If the thickness is less than the lower limit, the strength tends to decrease and the glass tends to break. On the other hand, if the upper limit is exceeded, multiple coatings are required, or it is difficult to dry the solvent during production. Therefore, bubbles, voids, whitening and spots are generated, and it is difficult to maintain the uniformity of the layer.

  Further, such a polyimide layer preferably has a linear expansion coefficient of 0 to 100 ppm / K, more preferably 5 to 50 ppm / K, and still more preferably 10 to 25 ppm / K. When such a linear expansion coefficient exceeds the upper limit, the difference from the linear expansion coefficient of the metal foil (for example, the linear expansion coefficient of copper: 16 ppm / K) becomes too large, and the metal foil is easily peeled off due to thermal history. Tend to be. Further, when the linear expansion coefficient is less than the lower limit, peeling or curling tends to occur. In addition, the following values are employ | adopted as a value of the linear expansion coefficient of such a polyimide layer. That is, first, regarding a polyimide layer as a measurement target, a film having a length of 76 mm, a width of 52 mm, and a thickness of 13 μm made of the same material as the material (polyimide) for forming the polyimide layer is formed. Thereafter, the film is vacuum-dried (120 ° C. for 1 hour) and heat-treated at 200 ° C. for 1 hour in a nitrogen atmosphere to obtain a dry film. The dry film thus obtained was used as a sample, and a thermomechanical analyzer (trade name “TMA8310” manufactured by Rigaku) was used as a measuring device, under a nitrogen atmosphere, in a tensile mode (49 mN), ascending. Adopting a temperature rate of 5 ° C./min, measuring the change in the length of the sample in the vertical direction from 50 ° C. to 200 ° C., and measuring per 1 ° C. (1K) in the temperature range of 50 ° C. to 200 ° Find the average length change. Then, the average value thus obtained is adopted as the value of the linear expansion coefficient of the polyimide layer according to the present invention (the value of the linear expansion coefficient of the polyimide layer when the thickness is 13 μm is used in the present invention). Adopted as the value of the linear expansion coefficient of such a polyimide layer).

  Furthermore, as a polyimide which comprises such a polyimide layer, that whose glass transition temperature (Tg) is 250 degreeC or more is preferable, and the thing of 300-500 degreeC is more preferable. If the glass transition temperature (Tg) is less than the lower limit, sufficient heat resistance tends to be difficult to achieve, and if it exceeds the upper limit, it tends to be difficult to produce a polyimide having such characteristics. It is in. In addition, such a glass transition temperature (Tg) consists of the material similar to the material (polyimide) which forms the polyimide layer regarding the polyimide layer as a measuring object, 5 mm long, 5 mm wide, 0.013 mm (13 micrometers in thickness). ) Is prepared as a measurement sample, and a thermomechanical analyzer (trade name “TMA8311” manufactured by Rigaku) is used as a measuring device and can be measured simultaneously by the same method as the softening temperature measurement. . In the measurement of such a glass transition temperature, it is preferable to perform the measurement by scanning a range of 30 ° C. to 550 ° C. in a nitrogen atmosphere under a temperature increase rate of 5 ° C./min.

  Moreover, as a polyimide which comprises such a polyimide layer, a softening temperature of 250-550 degreeC is preferable, a 350-550 degreeC thing is more preferable, and a 360-510 degreeC thing is still more preferable. When the softening temperature is lower than the lower limit, the heat resistance is lowered, and it becomes difficult to sufficiently suppress deterioration of the quality of the polyimide layer (such as occurrence of cracks) in the heating step in the production process of the metal-clad laminate. On the other hand, when the above upper limit is exceeded, when the polyimide layer is formed, a sufficient solid phase polymerization reaction does not proceed simultaneously with the thermal ring-closing condensation reaction of the polyamic acid, and when the polyimide layer is formed, a brittle polyimide layer and Tend to be.

  In addition, the softening temperature of such a polyimide can be measured as follows. That is, regarding a polyimide layer as a measurement target, a film having a length of 5 mm, a width of 5 mm, and a thickness of 0.013 mm (13 μm) made of the same material as that for forming the polyimide layer (polyimide) is used as a measurement sample. A temperature of 30 ° C. to 550 ° C. was prepared using a thermomechanical analyzer (trade name “TMA8311” manufactured by Rigaku) as a measuring device and employing a temperature rising rate of 5 ° C./min in a nitrogen atmosphere. It can be measured simultaneously with the glass transition temperature (Tg) by inserting a transparent quartz pin (tip diameter: 0.5 mm) into the film under a range of conditions at a pressure of 500 mN (so-called penetration method). Can be measured). In such measurement, the softening temperature is calculated based on the measurement data in accordance with the method described in JIS K 7196 (1991).

  Moreover, as a polyimide which comprises such a polyimide layer, a 5% weight loss temperature (Td5%) has a preferable thing of 400 degreeC or more, and a 450-550 degreeC thing is more preferable. If such a 5% weight loss temperature is less than the lower limit, sufficient heat resistance tends to be difficult to achieve, and if it exceeds the upper limit, it tends to be difficult to produce a polyimide having such characteristics. It is in. In addition, regarding such a 5% weight reduction temperature, a film made of the same material as the material for forming the polyimide layer (polyimide) is prepared as a measurement sample with respect to the polyimide layer as a measurement target, and under a nitrogen gas atmosphere, While flowing nitrogen gas, the scanning temperature was set to 30 ° C. to 550 ° C., and the rate of temperature increase was 10 ° C./min. It can be determined by measuring the temperature at which the weight of the used sample is reduced by 5% under the conditions of In addition, for such measurement, for example, a thermogravimetric analyzer (“TG / DTA220” manufactured by SII Nano Technology Co., Ltd.) can be used as a measuring device.

  Furthermore, as a polyimide which comprises such a polyimide layer, a thermal decomposition temperature (Td) is preferably 450 ° C. or higher, and more preferably 480 to 600 ° C. If such a thermal decomposition temperature (Td) is less than the lower limit, sufficient heat resistance tends to be difficult to achieve, and if it exceeds the upper limit, it is difficult to produce a polyimide having such characteristics. There is a tendency. In addition, regarding such a thermal decomposition temperature (Td), a film made of the same material as the material (polyimide) forming the polyimide layer is prepared as a measurement sample for the polyimide layer as a measurement target, and TG / DTA 220 heat Using a gravimetric analyzer (made by SII Nano Technology Co., Ltd.), a temperature increase rate of 10 ° C./min. It can be determined by measuring the temperature at the intersection of the tangent lines drawn on the decomposition curve before and after thermal decomposition under the conditions of

  Moreover, as a number average molecular weight (Mn) of the polyimide which comprises such a polyimide layer, it is preferable that it is 1000-1 million in polystyrene conversion, and it is more preferable that it is 10000-500000. When the number average molecular weight is less than the lower limit, it is difficult to achieve sufficient heat resistance, and polyimide is not sufficiently precipitated from the polymerization solvent when forming the polyimide layer, making it difficult to efficiently form the polyimide layer. On the other hand, when the above upper limit is exceeded, the viscosity increases, so that it takes a long time to dissolve or a large amount of solvent is required, so that processing tends to be difficult.

  Moreover, as a weight average molecular weight (Mw) of the polyimide which comprises such a polyimide layer, it is preferable that it is 1000-5 million in polystyrene conversion. Moreover, as a lower limit of the numerical range of such a weight average molecular weight (Mw), it is more preferable that it is 5000, It is further more preferable that it is 10,000, It is especially preferable that it is 20000. Moreover, as an upper limit of the numerical range of a weight average molecular weight (Mw), it is more preferable that it is 5000000, It is further more preferable that it is 500,000, It is especially preferable that it is 100,000. When the weight average molecular weight is less than the lower limit, it is difficult to achieve sufficient heat resistance, and polyimide is not sufficiently precipitated from the polymerization solvent when forming the polyimide layer, making it difficult to efficiently form the polyimide layer. On the other hand, when the upper limit is exceeded, the viscosity increases, so that it takes a long time to dissolve or a large amount of solvent is required, so that processing tends to be difficult.

  Furthermore, the molecular weight distribution (Mw / Mn) of the polyimide constituting such a polyimide layer is preferably 1.1 to 5.0, and more preferably 1.5 to 3.0. If such a molecular weight distribution is less than the lower limit, it tends to be difficult to produce, whereas if it exceeds the upper limit, it tends to be difficult to obtain a uniform polyimide layer. In addition, the molecular weight (Mw or Mn) and molecular weight distribution (Mw / Mn) of such a polyimide are the same as the material for forming the polyimide layer (polyimide) with respect to the polyimide layer as a measurement sample. As a measuring device, a gel permeation chromatography (GPC) measuring device (Degasser: DG-2080-54 manufactured by JASCO, liquid pump: PU-2080 manufactured by JASCO, interface: LC-NetII / ADC manufactured by JASCO Column: Shodex GPC column KF-806M (× 2), column oven: JASCO 860-CO, RI detector: JASCO RI-2031, column temperature 40 ° C., chloroform solvent (flow rate 1 mL / min) .) Is used to replace the data measured with polystyrene. It is possible to determined.

  Moreover, as such a polyimide layer, it is preferable that transparency is high enough. As a result, the visibility of the metal-clad laminate can be improved, misalignment when joining a plurality of printed wiring boards with solder, anisotropic conductive film ACF, or the like can be suppressed, and a decrease in yield can be suppressed. Is possible. Specifically, it is preferable that the total light transmittance is 80% or more (more preferably 85% or more, particularly preferably 87% or more). Further, such a polyimide layer is more preferably one having a haze (turbidity) of 5 or less (more preferably 4 or less, particularly preferably 3 or less) from the viewpoint of obtaining higher transparency. Further, such a polyimide layer is more preferably one having a yellowness (YI) of 10 or less (more preferably 8 or less, particularly preferably 6 or less) from the viewpoint of obtaining higher transparency. Such total light transmittance, haze (turbidity), and yellowness (YI) can be easily achieved by appropriately selecting the type of polyimide. In addition, as such total light transmittance, haze (turbidity), and yellowness (YI), the longitudinal direction which consists of the material similar to the material (polyimide) which forms the polyimide layer regarding the polyimide layer as a measuring object is used. : A film having a size of 76 mm, width 52 mm, and thickness 13 μm is formed as a measurement sample, and a value measured using a product name “Haze Meter NDH-5000” manufactured by Nippon Denshoku Industries Co., Ltd. is employed as a measuring device. .

(Metal-clad laminate)
The metal-clad laminate of the present invention contains the metal foil, the repeating unit (A) having the carboxyl group and the repeating unit (B) having no carboxyl group, which are laminated on the metal foil. A layer made of polyimide is provided. Such a metal-clad laminate has excellent adhesion between the metal foil (especially copper foil) and the polyimide layer. For example, the peel strength between the metal foil and the polyimide layer is 0. It is preferably 60 kg / cm or more, more preferably 0.65 kg / cm or more, further preferably 0.70 kg / cm or more, particularly preferably 0.80 kg / cm or more. Most preferably, it is 0.0 kg / cm or more. As such peel strength, a measurement sample obtained by cutting a metal-clad laminate into a size of about 100 mm in length: about 25 mm in width: Tensilon type universal testing machine (A A value measured under the condition of a tensile speed of 50 mm / min by a 90-degree peel test method in accordance with JIS C 6481 is employed using “UCT-10T” manufactured by Andy.

  Moreover, since the metal-clad laminated board of this invention is equipped with the said polyimide layer excellent in transparency, it is excellent in visibility. In manufacturing multi-layer printed wiring boards, by using such a metal-clad laminate with excellent visibility, misalignment when bonding multiple printed wiring boards with solder or anisotropic conductive film ACF is suppressed. This makes it possible to suppress a decrease in yield.

  Furthermore, since the metal-clad laminate of the present invention includes the polyimide layer having high heat resistance, heat treatment at a high temperature is possible when the metal foil and the polyimide layer are bonded. For this reason, in the metal-clad laminate of this invention, it becomes possible to adhere | attach a metal foil and a polyimide layer, without using an adhesive agent.

  Such a metal-clad laminate of the present invention is a component of various electronic devices, such as a two-layer flexible copper-clad laminate (two-layer FCCL), a three-layer flexible copper-clad laminate (three-layer FCCL), and a single-sided flexible print. Materials for printed wiring boards such as wiring boards (single-sided FPC), double-sided flexible printed wiring boards (double-sided FPC), multilayer flexible printed wiring boards (multi-layer FPC), touch panel members by printed electronics technology, electronic paper members, digital signage Members, flexible display members, optical compensation film members, linearly polarized / circularly polarized film members for reflective panels, 1 / 4λ film members for preventing reflected light incidence, internal antireflective film members for organic EL panels, base materials for organic EL, etc. (Optical isotropic film, retardation film) materials, environmental sensor Chromatography, battery member, lighting, etc. member, can be used as a gas separation membrane member.

  In particular, the metal-clad laminate of the present invention has excellent adhesion between a metal foil (especially copper foil) and a polyimide layer, and can form a fine wiring pattern, and thus has high-density wiring. It can be suitably used as a material for a printed wiring board. In addition, the metal-clad laminate of the present invention is excellent in visibility, and it is possible to suppress misalignment when laminated, so from the viewpoint of suppressing yield reduction, a plurality of printed wiring boards are provided. It can be suitably used for manufacturing by bonding with solder, anisotropic conductive film ACF or the like. Furthermore, since the metal-clad laminate of the present invention has high heat resistance and can be bonded to a metal foil and a polyimide layer without using an adhesive by heat treatment at high temperature, two layers It can be suitably used as a non-adhesive copper clad laminate such as a flexible copper clad laminate (two-layer FCCL).

(Method for producing metal-clad laminate)
The method for producing the metal-clad laminate of the present invention is not particularly limited as long as it can laminate the polyimide layer on the metal foil. For example, in the presence of a polymerization solvent, the following general formula (3) :

Wherein ^{(3), A, R 1} , R 2, R 3 have the same meanings as ^{A, R 1, R 2,} R 3 in the general formula (1). ]
Are reacted with an aromatic diamine having a carboxyl group and an aromatic diamine having no carboxyl group, to thereby give the following general formula (4):

Wherein ^{(4), A, R 1} , R 2, R 3, R 10 has the same meaning as ^{A, R 1, R 2,} R 3, R 10 in the general formula (1). ]
A repeating unit (A ′) having a carboxyl group represented by the following general formula (5):

Wherein ^{(5), A, R 1} , R 2, R 3, R 11 has the same meaning as ^{A, R 1, R 2,} R 3, R 11 in the general formula (2). ]
After forming a polyamic acid containing a repeating unit (B ′) having no carboxyl group represented by the following formula, a polyamic acid solution containing this polyamic acid is applied onto the metal foil and imidized. A layer made of polyimide containing the repeating unit (A) having a carboxyl group represented by the general formula (1) and the repeating unit (B) having no carboxyl group represented by the general formula (2) The method of forming the polyimide layer on the metal foil can be employed. The repeating unit formed from the reaction between the tetracarboxylic dianhydride represented by the general formula (3) and the aromatic diamine having the carboxyl group is the repeating unit (A) having the carboxyl group. And the repeating unit formed from the reaction between the tetracarboxylic dianhydride represented by the general formula (3) and the aromatic diamine having no carboxyl group is a repeating unit having no carboxyl group. Unit (B).

Regarding the tetracarboxylic dianhydride represented by the general formula (3), A, R ¹ , R ² and R ³ in the general formula (3) are A in the general formula (1). , R ¹ , R ² , and R ^3, and preferable examples thereof are the same as the preferable examples of A, R ¹ , R ² , and R ^{3 in} the general formula (1).

Regarding the repeating unit (A ′) having a carboxyl group in the polyamic acid formed by the reaction of the tetracarboxylic dianhydride represented by the general formula (3) and the aromatic diamine having the carboxyl group, ^a in the formula (4) ^{in, R 1, R 2, R} 3, R 10 has the same meaning as ^{a, R 1, R 2, R} 3, R 10 in the general formula (1), the suitable what is also the same as those preferred for ^{a, R 1, R 2,} R 3, R 10 in the general formula (1). Moreover, the repeating unit which does not have a carboxyl group in the said polyamic acid formed by reaction with the tetracarboxylic dianhydride represented by the said General formula (3) and the aromatic diamine which does not have the said carboxyl group ( relates B '), ^a in the general formula ^{(5), R 1, R} 2, R 3, R 11 is ^a in the general formula ^{(2), R 1, R} 2, R 3, R 11 as defined The preferred ones are also the same as the preferred ones of A, R ¹ , R ² , R ³ and R ^{11 in} the general formula (2).

  Of the tetracarboxylic dianhydrides represented by the general formula (3) used in the method for producing such a metal-clad laminate, A in the general formula (3) forms a chain structure. A divalent aliphatic group having 1 to 12 carbon atoms, a divalent alicyclic group having 3 to 12 carbon atoms forming a cyclic structure, and a carbon atom forming an aromatic ring The tetracarboxylic dianhydride, which is one selected from the group consisting of divalent aromatic groups in which is 6 to 30, can be produced, for example, by the following method. That is, at least one reducing agent selected from the group consisting of formic acid, 2-propanol and hydrogen, a base, a palladium catalyst, and the following general formula (6):

Wherein ^(6), R ^1, R 2, ^{R 3} have the same meanings as ^{R 1,} R 2, ^{R 3} in the general formula (3). ]
An acid anhydride represented by the following general formula (7):
R ⁴ -A-R ⁵ (7)
[In Formula (7), A is a divalent aliphatic group having 1 to 12 carbon atoms forming a chain structure, and a divalent having 3 to 12 carbon atoms forming a cyclic structure. And the alicyclic group and the aromatic group are selected from the group consisting of divalent aromatic groups having 6 to 30 carbon atoms to form an aromatic ring. ^May have a substituent, and R ⁴ and R ⁵ each independently represent a leaving group. ]
In the mixed solution containing the aromatic compound represented by the above formula, the acid anhydride and the aromatic compound are reacted to give a tetracarboxylic dianhydride represented by the general formula (3) (however, In the general formula (3), A is a single bond is excluded).

Relates acid anhydrides represented by the above general formula (6), ^{R 1,} R 2, ^{R 3} as defined in ^{R 1,} R 2, ^{R 3} in the general formula (6) is the general formula (3) The preferred ones are also the same as the preferred ones of R ¹ , R ² and R ^{3 in} the general formula (3). Therefore, examples of the acid anhydride represented by the general formula (6) include nadic anhydride, 5-methyl nadic anhydride, 5,6-dimethyl nadic anhydride, and 5-ethyl-6-methyl nadic anhydride. 5,6-diethyl nadic anhydride, 5-methyl-6-isopropyl nadic anhydride, 5-n-butyl nadic anhydride and the like. In addition, the method for manufacturing the acid anhydride represented by the general formula (6) is not particularly limited, and a known method can be appropriately employed. Moreover, as an acid anhydride represented by the general formula (6), a commercially available product may be appropriately used.

Regarding the aromatic compound represented by the general formula (7), A in the general formula (7) has the same meaning as A in the general formula (3) (however, a single bond is excluded). Is the same as the preferable one of A in the general formula (3) (except for a single bond). In the general formula (7), R ⁴ and R ⁵ each independently represent a leaving group. The leaving group represented by R ⁴ or R ⁵ is not particularly limited as long as it enables a so-called reductive Heck reaction. For example, a fluorine atom, a chlorine atom, a bromine atom, Examples include halogen atoms such as iodine atom, trifluoromethanesulfonyl group, p-toluenesulfonyl group, methanesulfonyl group, and nonafluorobutanesulfonyl group. Among such leaving groups represented by R ⁴ and R ⁵ , a halogen atom is more preferable, a chlorine atom, a bromine atom, and an iodine atom are more preferable, and a bromine atom and an iodine atom are particularly preferable. Examples of such aromatic compounds include diiodobenzene, diiodobiphenyl, dibromobenzene, 2,5-dibromo-p-xylene, diethyldibromobenzene, dichlorobenzene and the like. In addition, the method for manufacturing such an aromatic compound is not particularly limited, and a known method can be appropriately employed. Moreover, as such an aromatic compound, you may utilize a commercially available thing suitably.

  Further, when producing the tetracarboxylic dianhydride represented by the general formula (3) (except that A in the general formula (3) is a single bond), the general formula (6 The mixed solution containing the reducing agent, the base, and the palladium catalyst is used together with the acid anhydride represented by (II) and the aromatic compound represented by the general formula (7). Thus, by including a palladium catalyst in the mixed solution, the reaction can proceed in the presence of the palladium catalyst.

  Such a palladium catalyst is not particularly limited, and a known palladium catalyst can be appropriately used. For example, a palladium complex or a catalyst having palladium supported on a carrier can be preferably used. Examples of such a palladium catalyst include palladium acetate, palladium chloride, palladium nitrate, palladium sulfate, palladium propionate, palladium carbon, palladium alumina, and palladium black. As such a palladium catalyst, from the viewpoint of the reaction yield, palladium acetate, palladium chloride or other ligands (other complex ions and other molecules: for example, in the case of palladium acetate, other than acetate ions) It is more preferable to use a complex in which a complex ion or molecule is further bonded, and it is particularly preferable to use palladium acetate or a complex in which a ligand (another complex ion or another molecule) is further bonded thereto. In addition, such a palladium catalyst can be used individually by 1 type or in combination of 2 or more types. Moreover, as a complex suitable for such a palladium catalyst, other ligands or other complex ions or other molecules are further bonded to palladium acetate, for example, trans-di- (μ-acetate) bis [o- And a complex such as (di-o-tolylphosphino) benzyl] dipalladium (Herrmann's catalyst).

  Moreover, it is preferable that the liquid mixture further contains a compound that binds to palladium as a ligand. Examples of the compound that binds to palladium as a ligand include, for example, phosphine compounds (organic phosphorus compounds: for example, 2- (dicyclohexylphosphino) -2′-dimethylaminobiphenyl, 2- (dicyclohexylphosphino) -2. '-Methylbiphenyl, ortho-bis (dimethylaminophosphino) toluene, tris (2-methylphenyl) phosphine, triphenylphosphine, tricyclohexylphosphine, and the like). By using such a compound, it is possible to react by forming a new palladium complex in which a palladium complex and a ligand are bonded in the mixed solution, thereby improving the reaction efficiency. It becomes. Moreover, as a compound couple | bonded with such palladium as a ligand, it is preferable to use a phosphine compound from a viewpoint of reaction efficiency, Especially, 2- (dicyclohexylphosphino) -2'-dimethylamino biphenyl, 2- More preferably, (dicyclohexylphosphino) -2′-methylbiphenyl, ortho-bis (dimethylaminophosphino) toluene, tris (2-methylphenyl) phosphine is used.

In addition, in such a palladium catalyst, the palladium in the catalyst is more preferably divalent, and the formula: PdX ₂ [wherein X is a monovalent ion capable of forming a divalent palladium complex (for example, acetic acid). Ion, halogen ion, sulfate ion, etc.). A compound containing a compound (or structure) represented by

The base is not particularly limited, and a known base that can be used for the so-called reductive Heck reaction can be appropriately used. Such a base is not particularly limited, and examples thereof include triethylamine, N, N-diisopropylethylamine, pyridine, piperidine, pyrrolidine, sodium acetate, potassium acetate, calcium acetate, magnesium acetate, sodium carbonate, potassium carbonate, calcium carbonate, Examples thereof include magnesium carbonate. Examples of such a base include, for example, the formula: NR ₃ [wherein R is a monovalent organic group capable of forming an amine independently (for example, a linear or branched chain having 1 to 20 carbon atoms) In the amine represented by the formula: NR ₃ , each R independently represents 1 to 20 carbon atoms (more preferably 1 to 5) is preferably a linear or branched saturated hydrocarbon group, and when such a carbon number exceeds the upper limit, purification tends to be difficult. From the viewpoint of improving the reaction yield, it is more preferable to use triethylamine, N, N-diisopropylethylamine, sodium acetate or potassium acetate, and it is more preferable to use triethylamine or N, N-diisopropylethylamine. Preferred. Such a base can be used alone or in combination of two or more thereof.

  In the mixed solution, in addition to the acid anhydride represented by the general formula (6), the aromatic compound represented by the general formula (7), the reducing agent, the base, and the palladium catalyst, Furthermore, it is preferable to contain a solvent. By using the solvent in this way, it becomes possible to advance the reaction more efficiently in the solvent. As such a solvent, a known solvent can be used and is not particularly limited, and examples thereof include N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, toluene, N-methylpyrrolidone and the like. Among these solvents, N, N-dimethylformamide, N, N-dimethylacetamide, and dimethyl sulfoxide are preferably used because the reaction yield is improved and the solubility of each component used is high. N, N-dimethylformamide and N, N-dimethylacetamide are more preferable.

  In addition, the method for containing the reducing agent and the base in the mixed solution is not particularly limited, and a known method can be appropriately employed. For example, the reducing agent (for example, formic acid) and the base ( For example, triethylamine or the like) may be added to the mixture to contain the reducing agent and the base, and a salt composed of the reducing agent (for example, formic acid) and the base may be added to the mixture. By adding, the reducing agent and the base may be contained in the mixed solution. Examples of the salt composed of the reducing agent (for example, formic acid) and the base include ammonium formate, triethylamine formate, and the like.

  Moreover, content of the acid anhydride represented by the said General formula (6) in such a liquid mixture is 0.5-10 with respect to 1 mol of aromatic compounds represented by the said General formula (7). It is preferable to set it as a mol, and it is more preferable to set it as 1.5-5 mol. When the content of the acid anhydride represented by the general formula (6) is less than the lower limit, the reaction efficiency tends to decrease. On the other hand, when the content exceeds the upper limit, the by-product tends to increase.

  Moreover, it is preferable to set it as 1-80 mass%, and, as for the total amount of the compound represented by the said General formula (6) and (7) in such a liquid mixture, it is more preferable to set it as 5-50 mass%. . When the total amount is less than the lower limit, the reaction efficiency tends to decrease. On the other hand, when the total amount exceeds the upper limit, the by-products tend to increase.

  Moreover, as content of the palladium catalyst in such a liquid mixture, the molar amount of palladium in the said palladium catalyst is 0.00001-0.1 of the molar amount of the compound represented by the said General formula (6). It is preferable to set the amount to be a double mole (more preferably 0.0001 to 0.05 mole). When the content of the palladium catalyst is less than the lower limit, the reaction efficiency tends to decrease. On the other hand, when the content exceeds the upper limit, the reaction proceeds excessively and tends to be difficult to control.

  When the mixed solution further contains a compound (preferably a phosphine compound) that binds to palladium as a ligand, the content of the compound is 0.5 to the molar amount of palladium in the palladium catalyst. It is preferable to make it the quantity used as 10 times mole (more preferably 1-5 times mole). If the content of such a compound is less than the lower limit, the yield tends to decrease. On the other hand, if the content exceeds the upper limit, the reaction proceeds excessively and tends to be difficult to control.

  Moreover, as content of the base in such a liquid mixture, it is 0.5-10.0 times mole with respect to the molar amount of the compound represented by the said General formula (6) (more preferably, 1.0- The amount is preferably 5.0 times mole). When the content of such a base is less than the lower limit, the reaction rate tends to decrease. On the other hand, when the content exceeds the upper limit, a by-product tends to increase.

  Further, the content of the reducing agent in the mixed solution is not particularly limited, but the molar amount of the reducing agent is 0.5 to 10 times the molar amount of the compound represented by the general formula (6). It is preferable that the amount is (more preferably 1.0 to 5.0 times mol). When the content of such a reducing agent is less than the lower limit, the reaction rate tends to decrease. On the other hand, when the content exceeds the upper limit, the by-products tend to increase.

  As content of the solvent in such a liquid mixture, it is preferable to set it as 20-99 mass% with respect to the whole quantity of a liquid mixture, and it is more preferable to set it as 50-95 mass%. When the amount of such a solvent used is less than the lower limit, by-products tend to increase. On the other hand, when the amount exceeds the upper limit, the reaction efficiency tends to decrease.

  In producing the tetracarboxylic dianhydride represented by the general formula (3) (excluding those in which A in the general formula (3) is a single bond), in the mixed solution, An acid anhydride is reacted with the aromatic compound. An outline of such a reaction is shown by the following reaction formula (I):

[In Reaction formula ^{(I), R 1, R} 2, R 3, R 4, R 5, A , respectively the general formula (3), ^R 1 in (6) and ^{(7), R} 2, R ³ , R ⁴ , R ⁵ and A are the same as defined above (except that A in the above general formulas (3) and (7) is a single bond). ]
It will be something like that. As the base in the above reaction formula (I), the above-mentioned bases may be appropriately used. For example, the formula: NR ₃ [wherein R is a monovalent organic group capable of independently forming an amine ( For example, an amine represented by a linear saturated hydrocarbon group having 1 to 20 carbon atoms, etc.] Further, as the palladium catalyst in the above reaction formula (I), the above-mentioned palladium catalyst may be used. For example, it is represented by the formula: PdX ₂ [wherein X represents a monovalent ion (for example, acetate ion, halogen ion, sulfate ion, etc.) capable of forming a divalent palladium complex]. You may use the catalyst containing a compound etc. The said Reaction formula (I) is the outline of the process with which the said acid dianhydride and the said aromatic compound are made to react by what is called reductive Heck reaction in presence of a palladium catalyst. As you can see, The tetracarboxylic acid anhydride represented by the general formula (3) (excluding those in which A in the general formula (3) is a single bond) is represented by the palladium catalyst and the general formula (6). Acid dianhydride, an aromatic compound represented by the general formula (7), at least one reducing agent selected from the group consisting of formic acid, 2-propanol and hydrogen, and a base. In the mixed liquid, it can be produced by a reaction of the acid dianhydride and the aromatic compound in the presence of a palladium catalyst by a reductive Heck reaction.

  As the conditions of the atmospheric gas in such a reaction, an inert gas atmosphere is preferable from the viewpoint of the stability of the raw material and the product. Such an inert gas is not particularly limited, and examples thereof include nitrogen, helium, and argon. In addition, the reaction temperature during such a reaction varies depending on the type of raw material compound and palladium catalyst used, and is not particularly limited. For example, the reaction temperature may be 20 to 180 ° C., and higher reaction efficiency is obtained. From such a viewpoint, it is more preferable to heat to 40 to 150 ° C, and it is more preferable to heat to 50 to 120 ° C. When the temperature condition of such reaction temperature is less than the lower limit, the reaction efficiency tends to decrease, and when it exceeds the upper limit, the by-product tends to increase. In addition, the reaction time of such a reaction is preferably 0.5 to 20 hours (more preferably 2 to 15 hours). If the reaction time is less than the lower limit, the yield tends to decrease. On the other hand, if the upper limit is exceeded, by-products tend to increase.

  In this way, the tetracarboxylic dianhydride represented by the above general formula (3) is sufficiently efficiently obtained by allowing the reductive Heck reaction to proceed, for example, by appropriately heating using the mixed solution. , Except that A in the general formula (3) is a single bond).

  On the other hand, the tetracarboxylic dianhydride in which A in the general formula (3) is a single bond can be produced, for example, by the following method. That is, the following general formula (8):

Wherein ^(8), R ^1, R 2, ^{R 3} has the same meaning as ^{R 1,} R 2, ^{R 3} in the general formula (3), a plurality of ^{R 6} is independently a hydrogen atom, the number of carbon atoms Selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms. One type is shown. ]
Is heated in a carboxylic acid having 1 to 5 carbon atoms using an acid catalyst, and the following general formula (9):

Wherein ^(9), R ^1, R 2, ^{R 3} have the same meanings as ^{R 1,} R 2, ^{R 3} in the general formula (8). ]
The tetracarboxylic dianhydride represented by the formula (tetracarboxylic dianhydride in which A in the general formula (3) is a single bond) can be obtained.

Relates carbonyl compound represented by the above general formula (8), ^{R 1,} R 2, ^{R 3} in the general formula (8) is ^{R 1,} R 2, ^{R 3} as defined in the general formula (3) And preferred ones thereof are the same as the preferred ones of R ¹ , R ² and R ^{3 in} the general formula (3). Also relates to the tetracarboxylic dianhydride represented by the above general formula (9), ^R 1, ^{R 2} of ^{R 1,} R 2, ^{R 3} in the general formula (9) is the general formula (8) in , R ^3, and preferable examples thereof are the same as the preferable examples of R ¹ , R ² , and R ^{3 in} the general formula (8). The plurality of R ¹ in the general formulas (8) and (9) may be the same or different from each other, but are the same from the viewpoint of ease of purification and the like. It is preferable that. Furthermore, R ² and R ^{3 in the} general formulas (8) and (9) may be the same or different, respectively, but from the viewpoint of ease of purification, It is preferable that they are the same.

Moreover, it is especially preferable that all of the plurality of R ¹ , R ² and R ³ in the general formulas (8) and (9) are hydrogen atoms. Thus, in the carbonyl compound represented by the general formula (8) and the tetracarboxylic dianhydride represented by the general formula (9), the substituents represented by R ¹ , R ² and R ³ are When both are hydrogen atoms, higher heat resistance tends to be obtained.

Moreover, the alkyl group which can be selected as R < ⁶ > in the said General formula (8) is a C1-C10 alkyl group. When the carbon number of such an alkyl group exceeds 10, purification becomes difficult. Moreover, as carbon number of the alkyl group which can be selected as such some R < ⁶ >, it is more preferable that it is 1-5 from a viewpoint that refinement | purification becomes easier, and it is still more preferable that it is 1-3. . In addition, the alkyl group that can be selected as the plurality of R ⁶ may be linear or branched.

Moreover, the cycloalkyl group which can be selected as R < ⁶ > in the said General formula (8) is a C3-C10 cycloalkyl group. If the number of carbon atoms in such a cycloalkyl group exceeds 10, purification becomes difficult. As the number of carbon atoms of the cycloalkyl group which may be selected as a plurality of R ⁶ such as this, from the viewpoint of purification becomes easier, more preferably 3-8, to be 5-6 further preferable.

Furthermore, the alkenyl group that can be selected as R ⁶ in the general formula (8) is an alkenyl group having 2 to 10 carbon atoms. When the carbon number of such an alkenyl group exceeds 10, purification becomes difficult. Further, the number of carbon atoms of the alkenyl group that can be selected as the plurality of R ⁶ is more preferably 2 to 5 and even more preferably 2 to 3 from the viewpoint of easier purification. .

The aryl group that can be selected as R ⁶ in the general formula (8) is an aryl group having 6 to 20 carbon atoms. If the number of carbon atoms in such an aryl group exceeds 20, purification becomes difficult. As the carbon number of a plurality of such aryl group which may be selected as R ^6, from the viewpoint of purification becomes easier, more preferably 6-10, more preferably 6-8 .

The aralkyl group that can be selected as R ⁶ in the general formula (8) is an aralkyl group having 7 to 20 carbon atoms. If the number of carbon atoms in such an aralkyl group exceeds 20, purification becomes difficult. In addition, the number of carbon atoms of the aralkyl group that can be selected as the plurality of R ⁶ is more preferably 7 to 10 and even more preferably 7 to 9 from the viewpoint of easier purification. .

Further, as the plurality of R ⁶ in the general formula (8), from the viewpoint that purification becomes easier, each of them is independently a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, It is preferably an isobutyl group, sec-butyl, t-butyl, cyclohexyl group, allyl group, phenyl group or benzyl group, more preferably a methyl group, an ethyl group or an n-propyl group, a methyl group, an ethyl group. Is more preferable, and a methyl group is particularly preferable. In addition, although several R < ⁶ > in the said General formula (8) may be respectively the same or different, it is more preferable that it is the same from a synthetic viewpoint.

  The carbonyl compound represented by the general formula (8) can be produced, for example, by the following method. That is, in the presence of a palladium catalyst and an oxidizing agent, the following general formula (10):

Wherein ^(10), R ^1, R 2, ^{R 3} have the same meanings as ^{R 1,} R 2, ^{R 3} in the general formula (8). ]
The carbonyl compound represented by the above general formula (8) can be obtained by reacting the norbornene-based compound represented by general formula (8) with alcohol and carbon monoxide.

In the production of the carbonyl compound, a norbornene compound represented by the general formula (10) is used as a raw material compound. In the norbornene compound represented by the general formula (10), ^R 1, ^{R 2} and ^{R 3} in the general formula (10) ^R 1, ^{R 2} and ^{R 3} as defined in the general formula (8) The preferred ones are also the same as the preferred ones of R ¹ , R ² and R ^{3 in} the general formula (8). The plurality of R ¹ in the general formula (10) may be the same or different from each other, but are the same from the viewpoint of ease of purification and the like. It is preferable. Further, R ² and R ³ in the general formula (10) may be the same or different, but from the viewpoint of ease of purification and the like, they are the same. Preferably there is.

Moreover, it is particularly preferable that all of R ¹ , R ² and R ³ in the general formula (10) are hydrogen atoms. Thus, when the substituents represented by R ¹ , R ² and R ³ are all hydrogen atoms in the norbornene compound represented by the general formula (10), higher heat resistance can be obtained. Tend to be.

  The norbornene compound represented by the general formula (10) is, for example, 5,5′-bibicyclo [2.2.1] hept-2-ene (also known as 5,5′-bi-2-). Also referred to as norbornene (CAS number: 36806-67-4), 3-methyl-3′-methylene-2,2′-bis (bicyclo [2.2.1] heptene-5,5′-diene) (CAS No .: 5212-61-3), 5,5′-bisbicyclo [2.2.1] hept-5-ene-2,2′-diol (CAS number: 15971-85-4) and the like. The method for producing the norbornene-based compound represented by the general formula (10) is not particularly limited, and a known method can be appropriately employed.

Further, when the carbonyl compound represented by the general formula (8) is produced, the norbornene compound represented by the general formula (10) is reacted with an alcohol. Such alcohol is not particularly limited, but from the viewpoint of ease of purification, the following general formula (11):
R ^a OH (11)
[In the formula (11), R ^a is an atom other than a hydrogen atom among the atoms and groups that can be selected as R ⁶ in the general formula (8). ]
It is preferable that it is alcohol represented by these. That is, as such an alcohol, an alkyl alcohol having 1 to 10 carbon atoms, a cycloalkyl alcohol having 3 to 10 carbon atoms, an alkenyl alcohol having 2 to 10 carbon atoms, an aryl alcohol having 6 to 20 carbon atoms, It is preferable to use aralkyl alcohol having 7 to 20 carbon atoms.

  Specific examples of such alcohols include methanol, ethanol, butanol, allyl alcohol, cyclohexanol, benzyl alcohol, and the like. Among these, methanol, methanol, Ethanol is more preferred and methanol is particularly preferred. Such alcohols may be used alone or in combination of two or more.

In the production of the carbonyl compound represented by the general formula (8), in the presence of a palladium catalyst and an oxidizing agent, the alcohol (preferably R ^a OH) and carbon monoxide (CO) are mixed with the general formula. By reacting with the norbornene-based compound represented by (10), carbon in the olefin moiety in the norbornene-based compound represented by the general formula (10) is respectively represented by the following general formula (12):
-COOR ^a (12)
Wherein (12), the ^{R a} is synonymous with ^{R a} in the general formula (11). ]
It is possible to introduce an ester group represented by the formula (wherein R ⁶ may be the same or different at each introduced position), whereby the general formula (8) The carbonyl compound represented can be obtained. Thus, in the presence of a palladium catalyst and an oxidant, an alcohol (preferably R ^a OH) and carbon monoxide (CO) are used to introduce an ester group into the carbon of the olefin moiety in the carbonyl compound (hereinafter, Such a reaction is sometimes simply referred to as “esterification reaction”) to obtain a carbonyl compound represented by the general formula (8).

The palladium catalyst used in such esterification reaction is not particularly limited, and a known catalyst containing palladium can be appropriately used. For example, palladium inorganic acid salt, palladium organic acid salt, palladium is supported on a carrier. And the like. Examples of such a palladium catalyst include palladium chloride, palladium nitrate, palladium sulfate, palladium acetate, palladium propionate, palladium carbon, palladium alumina, palladium black, and palladium acetate having a nitrite ligand (formula: Pd ₃ ( CH ₃ COO) ₅ (NO ₂ ) and the like are preferable.

Further, as such a palladium catalyst, it is possible to sufficiently suppress the formation of by-products, and to produce the carbonyl compound represented by the general formula (8) with higher selectivity. From the viewpoint of becoming, a palladium catalyst containing a nitrite ligand-containing palladium acetate (a catalyst represented by the formula: Pd ₃ (CH ₃ COO) ₅ (NO ₂ )) (hereinafter sometimes referred to simply as “Pd ₃ (OAc)”. ) ₅ (NO ₂ ) ”).

Further, palladium acetate having such a nitrite ligands _{(Pd 3 (OAc) 5 (} NO 2)) in a palladium catalyst containing palladium acetate _{(Pd 3} with nitrous acid ligand _(OAc) 5 _(NO 2) ) Is preferably 10 mol% or more in terms of metal (relative to the total amount of palladium in the palladium catalyst). When the content ratio of palladium acetate having such a nitrous acid ligand is less than the lower limit, it is difficult to sufficiently suppress the formation of by-products, and is represented by the general formula (8) with a sufficiently high selectivity. It tends to be difficult to produce a carbonyl compound. In addition, as the palladium catalyst, acetic acid having a nitrite ligand can be used from the viewpoint that the production of by-products can be suppressed at a higher level and an ester compound can be produced with higher selectivity. The content ratio of palladium (Pd ₃ (OAc) ₅ (NO ₂ )) is more preferably 30 mol% or more in terms of metal (relative to the total amount of palladium in the palladium catalyst), and 40 mol% or more. More preferably, it is more preferably 50 mol% or more, and most preferably 70 mol% to 100 mol%.

Further, as the palladium catalyst used for the esterification reaction, palladium acetate having a nitrite ligands _{(Pd 3 (OAc) 5 (} NO 2)) in the case of using those _{containing, Pd 3 (OAc) 5 (} NO 2) The other catalyst (other palladium catalyst component) that can be contained in addition to the above is not particularly limited, and is a known catalyst that can be used when reacting carbon monoxide and an alcohol with an olefin site (during esterification). Palladium-based catalyst components (for example, palladium chloride, palladium nitrate, palladium sulfate, palladium acetate, palladium propionate, palladium carbon, palladium alumina, palladium black, etc.) can be used as appropriate.

Moreover, as a component other than palladium acetate having a nitrite ligand that can be contained in such a palladium catalyst (palladium-based catalyst component), from the viewpoint of suppressing the generation of by-products such as a polymer and improving selectivity. It is preferable to use palladium acetate. In addition, as the palladium catalyst, palladium acetate having a nitrite ligand (Pd ₃ (OAc) ₅ (NO ₂ )) and palladium acetate are used from the viewpoint of suppressing generation of by-products such as a polymer and improving selectivity. And a catalyst comprising only palladium acetate having a nitrite ligand (Pd ₃ (OAc) ₅ (NO ₂ )) can be used more suitably.

Incidentally, no particular restriction on a method for the production of palladium acetate _{(Pd 3 (OAc) 5 (} NO 2)) having such a nitrite ligands, can be appropriately used a known method, for example, A method described in pages 1989 to 1992 of Dalton Trans (vol. 11) issued on June 7, 2005 (author: Vladimir I, Bakhmutov, et al.) May be used as appropriate. .

As the oxidizing agent used in the esterification reaction, when the Pd ²⁺ of the palladium catalyst in the esterification reaction has been reduced to Pd ^0, long as it can oxidize the Pd ⁰ to Pd ²⁺ That's fine. Such an oxidizing agent is not particularly limited, and examples thereof include a copper compound and an iron compound. Moreover, as such an oxidizing agent, specifically, cupric chloride, cupric nitrate, cupric sulfate, cupric acetate, ferric chloride, ferric nitrate, ferric sulfate, And ferric acetate.

  Furthermore, the amount of alcohol used in such an esterification reaction is not particularly limited as long as it is an amount capable of obtaining the carbonyl compound represented by the general formula (8). For example, the general formula ( The alcohol may be added to the amount theoretically required to obtain the carbonyl compound represented by 8) (theoretical amount), and the excess alcohol may be used as a solvent as it is.

  In the esterification reaction, the carbon monoxide may be supplied in a required amount to the reaction system. Therefore, it is not necessary to use a high purity gas of carbon monoxide as the carbon monoxide, and a mixed gas in which a gas inert to the esterification reaction (for example, nitrogen) and carbon monoxide may be used. . Further, the pressure of such carbon monoxide is not particularly limited, but is preferably normal pressure (about 0.1 MPa [1 atm]) or more and 10 MPa or less.

  Furthermore, a method for supplying the carbon monoxide to the reaction system is not particularly limited, and a known method can be appropriately employed. For example, the alcohol, the norbornene compound represented by the general formula (10), the palladium catalyst, A method of supplying carbon monoxide by bubbling into a mixed solution containing, or a method of supplying carbon monoxide to the reaction system by introducing carbon monoxide into the atmospheric gas in the vessel when using a reaction vessel, etc. Can be adopted as appropriate.

  In addition, when carbon monoxide is supplied into a mixed solution containing the alcohol, the norbornene compound represented by the general formula (10), and the palladium catalyst, the carbon monoxide is represented by the general formula (10). 0.002 to 0.2 molar equivalent / minute (more preferably 0.005 to 0.1 molar equivalent / minute, still more preferably 0.005 to 0.05 molar equivalent / minute) with respect to the norbornene-based compound represented. ) Is preferably supplied at a rate (supply speed). When the supply ratio of carbon monoxide is less than the lower limit, the reaction rate tends to be slow, and by-products such as polymers tend to be generated. On the other hand, when the upper limit is exceeded, the reaction rate is improved and the reaction is performed at once. Tends to become difficult to control the reaction. In addition, since 4 mol equivalent of carbon monoxide theoretically reacts with respect to 1 mol of the norbornene-based compound represented by the general formula (10) as a raw material, for example, the ratio (feed rate) is 0.00. If it is 1 molar equivalent / minute, in order to introduce a theoretical molar equivalent with respect to 1 mole of the tetracarboxylic dianhydride compound represented by the general formula (9), 40 minutes (4 [mol Equivalent] /0.1 [molar equivalent / minute] = 40 minutes). Further, as a method for supplying carbon monoxide at such a supply rate, bubbling is performed in a mixed solution containing the alcohol, the norbornene compound represented by the general formula (10), and the palladium catalyst. It is preferable to employ a method of supplying carbon oxide.

  Further, when supplying the carbon monoxide by bubbling, a specific method of the bubbling is not particularly limited, and a known bubbling method can be appropriately employed. For example, a so-called bubbling nozzle and a large number of holes are provided. Carbon monoxide may be bubbled and supplied into the mixed solution using a tube or the like as appropriate.

  Furthermore, the method for controlling the supply rate of the carbon monoxide is not particularly limited, and a known control method may be adopted as appropriate. For example, in the case of supplying carbon monoxide by bubbling, the bubbling nozzle or many A method of controlling the supply rate of carbon monoxide at the above-mentioned ratio using a known apparatus capable of supplying a gas at a specific ratio to a pipe or the like provided with the holes may be adopted. In addition, when supplying carbon monoxide by bubbling, when a reaction vessel is used, it is preferable to adjust a bubbling nozzle, a pipe, and the like near the bottom of the vessel. This is to promote contact between the norbornene compound represented by the general formula (10) present at the bottom and carbon monoxide supplied from a bubbling nozzle or the like.

  In the esterification reaction, the amount of the palladium catalyst used is such that the molar amount of palladium in the palladium catalyst is 0.001 to 0.1 relative to the norbornene compound represented by the general formula (10). It is preferable that the amount be double mole (more preferably 0.001 to 0.01 mole). If the amount of the palladium catalyst used is less than the lower limit, the yield tends to decrease due to a decrease in the reaction rate. On the other hand, if the upper limit is exceeded, it is difficult to remove palladium from the product, and the purity of the product Tend to decrease.

  The amount of the oxidizing agent used is 2 to 16 times mol (more preferably 2 to 8 times mol, further preferably 2 to 6 times mol) based on the norbornene compound represented by the general formula (10). It is preferable that If the amount of the oxidizing agent used is less than the lower limit, the oxidation reaction of palladium cannot be promoted sufficiently, and as a result, a large amount of by-products tend to be formed. The purity of the product tends to decrease.

  In addition, a solvent may be used for the reaction (esterification reaction) of the norbornene compound represented by the general formula (10) with alcohol and carbon monoxide. Such a solvent is not particularly limited, and a known solvent that can be used for the esterification reaction can be appropriately used, and examples thereof include hydrocarbon solvents such as n-hexane, cyclohexane, benzene, and toluene.

  Furthermore, in the esterification reaction, an acid is by-produced from the oxidizing agent or the like, and therefore a base may be added to remove the acid. As such a base, fatty acid salts such as sodium acetate, sodium propionate, and sodium butyrate are preferable. Further, the amount of such base used may be appropriately adjusted according to the amount of acid generated.

  In addition, the reaction temperature condition in the esterification reaction is not particularly limited, but is 0 ° C to 200 ° C {more preferably 0 ° C to 100 ° C, more preferably about 10 to 60 ° C, particularly preferably 20 to 50 ° C. It is preferable that the temperature is about the same. When such a reaction temperature exceeds the upper limit, the yield tends to decrease. On the other hand, when the reaction temperature is less than the lower limit, the reaction rate tends to decrease. The reaction time for the esterification reaction is not particularly limited, but is preferably about 30 minutes to 24 hours.

  Further, the atmospheric gas in the esterification reaction is not particularly limited, and a gas that can be used for the esterification reaction can be appropriately used. For example, an inert gas (nitrogen, argon, etc.) for the esterification reaction , Carbon monoxide, mixed gas of carbon monoxide and other gas (nitrogen, air, oxygen, hydrogen, carbon dioxide, argon, etc.), from the viewpoint of not affecting the catalyst and oxidant, Carbon monoxide, a gas inert to the esterification reaction, and a mixed gas of carbon monoxide and a gas inert to the esterification reaction are preferable. In addition, when adopting a method of introducing carbon monoxide by bubbling as a method of supplying carbon monoxide into the mixed solution, for example, the atmosphere gas is made of a gas inert to the esterification reaction before the reaction. Alternatively, the reaction may be started by bubbling as described above, and as a result, the reaction may proceed so that the atmospheric gas becomes a mixed gas of carbon monoxide and a gas inert to the esterification reaction.

  Further, the pressure condition in the esterification reaction (atmospheric gas pressure condition: when the reaction is allowed to proceed in the reaction vessel) is not particularly limited, but is 0.05 MPa to 15 MPa. The pressure is preferably normal pressure (0.1 MPa [1 atm]) to 15 MPa, more preferably 0.1 MPa to 10 MPa, and particularly preferably 0.11 MPa to 5 MPa. When the pressure condition is less than the lower limit, the reaction rate tends to decrease and the yield of the target product tends to decrease. On the other hand, when the upper limit is exceeded, the reaction rate improves and the reaction proceeds at a stretch, making it difficult to control the reaction There is a tendency that facilities that can carry out the reaction are limited.

By allowing the esterification reaction to proceed in this manner, the carbonyl compound (tetraester compound) represented by the general formula (8) in which R ⁶ in the general formula (8) is a group other than a hydrogen atom. Can be obtained. In the case where the carbonyl compound represented by the general formula (8) in which R ⁶ in the formula (8) is a hydrogen atom is produced, the above formula: —COOR ^a represents the esterification reaction. Then, in order to convert the group into a group represented by the formula: —COOH where R ^a is a hydrogen atom, a hydrolysis treatment or a transesterification reaction with a carboxylic acid may be performed. The method of such a reaction is not particularly limited, and a known method capable of converting the group (ester group) represented by the formula: —COOR ^a into the formula: —COOH (carboxy group) may be appropriately adopted. it can.

  In producing the tetracarboxylic dianhydride represented by the general formula (9), the carbonyl compound represented by the general formula (8) is converted to a carboxylic acid having 1 to 5 carbon atoms using an acid catalyst. Heat in. The acid catalyst used in producing the tetracarboxylic dianhydride is not particularly limited, and may be a homogeneous acid catalyst or a heterogeneous acid catalyst (solid catalyst). Among such acid catalysts, a homogeneous acid catalyst is preferable from the viewpoint of ease of purification.

  Such a homogeneous acid catalyst is not particularly limited, and a known homogeneous acid catalyst that can be used for a reaction in which a carboxylic acid is an anhydride or a reaction in which an ester compound is an acid anhydride can be appropriately used. it can. Examples of such a homogeneous acid catalyst include trifluoromethanesulfonic acid, tetrafluoroethanesulfonic acid, pentafluoroethanesulfonic acid, heptafluoropropanesulfonic acid, heptafluoroisopropanesulfonic acid, nonafluorobutanesulfonic acid, heptafluoro Examples thereof include decanesulfonic acid, bis (nonafluorobutanesulfonyl) imide, N, N-bis (trifluoromethanesulfonyl) imide, and chlorodifluoroacetic acid.

  As such a homogeneous acid catalyst, from the viewpoint of improving the reaction yield, trifluoromethanesulfonic acid, tetrafluoroethanesulfonic acid, nonafluorobutanesulfonic acid, and chlorodifluoroacetic acid are more preferable. More preferred is fluoroethanesulfonic acid. In addition, as such a homogeneous acid catalyst, you may use 1 type individually or in combination of 2 or more types.

  The amount of the acid catalyst (more preferably a homogeneous acid catalyst) used is not particularly limited, but the carbonyl compound (tetracarboxylic dianhydride raw material compound) represented by the general formula (8) is used. It is preferable to set the amount so that the molar amount of the acid in the acid catalyst is 0.001 to 2.00 molar equivalent (more preferably 0.01 to 1.00 molar equivalent) with respect to the amount (molar amount). . When the amount of the acid catalyst used is less than the lower limit, the reaction rate tends to decrease. On the other hand, when the upper limit is exceeded, purification becomes somewhat difficult and the purity of the product tends to decrease. The molar amount of the acid in the acid catalyst referred to here is a molar amount in terms of a functional group (for example, a sulfonic acid group (sulfo group) or a carboxylic acid group (carboxy group)) in the acid catalyst.

  Further, the amount of the acid catalyst (more preferably a homogeneous acid catalyst) used is preferably 0.1 to 100 parts by mass with respect to 100 parts by mass of the carbonyl compound represented by the general formula (8). It is more preferable that it is 1-20 mass parts. When the amount of the acid catalyst used is less than the lower limit, the reaction rate tends to decrease. On the other hand, when the amount exceeds the upper limit, a side reaction product tends to be generated.

  Furthermore, in producing the tetracarboxylic dianhydride, a carboxylic acid having 1 to 5 carbon atoms (hereinafter sometimes simply referred to as “lower carboxylic acid”) is used. When the carbon number of such a lower carboxylic acid exceeds the upper limit, production and purification become difficult. Examples of such lower carboxylic acids include formic acid, acetic acid, propionic acid, butyric acid, etc. Among them, formic acid, acetic acid, propionic acid are preferable from the viewpoint of ease of production and purification, and formic acid, acetic acid Is more preferable. Such lower carboxylic acids may be used singly or in combination of two or more.

  The amount of such lower carboxylic acid (for example, formic acid, acetic acid, propionic acid) is not particularly limited, but is 4 to 100 times mol with respect to the carbonyl compound represented by the general formula (8). It is preferable. If the amount of such a lower carboxylic acid (formic acid, acetic acid, propionic acid, etc.) used is less than the lower limit, the yield tends to decrease, whereas if it exceeds the upper limit, the reaction rate tends to decrease.

  Moreover, when manufacturing the said tetracarboxylic dianhydride, since the said carbonyl compound is heated in the said lower carboxylic acid, it is preferable to contain the said carbonyl compound in the said lower carboxylic acid. As content of the carbonyl compound represented by the said General formula (8) in such a lower carboxylic acid, it is preferable that it is 1-40 mass%, and it is more preferable that it is 2-30 mass%. When the content of such a carbonyl compound is less than the lower limit, the yield tends to decrease. On the other hand, when the content exceeds the upper limit, the reaction rate tends to decrease.

  As mentioned above, although the carbonyl compound represented by the said General formula (8) used when manufacturing the said tetracarboxylic dianhydride, an acid catalyst, and a C1-C5 carboxylic acid were demonstrated, these were then used. A heating step (a step of heating the carbonyl compound in a carboxylic acid having 1 to 5 carbon atoms using an acid catalyst) will be described.

When the carbonyl compound is a compound represented by the general formula (8) and R ⁶ in the formula is a hydrogen atom (tetracarboxylic acid), the carbonyl compound is obtained by the heating step. A reaction (positive reaction) in which tetracarboxylic dianhydride and water are generated from (tetracarboxylic acid) proceeds. Such a normal reaction and a reverse reaction in which the carbonyl compound (tetracarboxylic acid) is generated from tetracarboxylic dianhydride and water are equilibrium reactions. In the present invention, when the carbonyl compound is a compound represented by the general formula (8) and R ⁶ in the formula is a group other than a hydrogen atom, the carbonyl compound is obtained by the heating step. And a reaction (positive reaction) in which tetracarboxylic dianhydride, a lower carboxylic acid ester compound and water are produced from the lower carboxylic acid. Such a forward reaction and a reverse reaction in which the carbonyl compound and the lower carboxylic acid are generated from the carboxylic acid anhydride, the ester compound of the lower carboxylic acid, and water are equilibrium reactions. Therefore, in such a heating step, it is possible to efficiently advance the reaction (positive reaction) by appropriately changing the concentration of the component in the system.

  The conditions that can be employed in such a heating step (including heating temperature and atmospheric conditions) are not particularly limited, and the carbonyl compound is heated in the lower carboxylic acid using the acid catalyst. As long as the method (conditions) enables the ester group and / or carboxy group (carboxylic acid group) in the carbonyl compound to be an acid anhydride group, the conditions can be appropriately employed. Conditions such as those employed in known reactions capable of forming acid anhydride groups can be used as appropriate.

  In such a heating step, it is preferable to first prepare a mixture of the lower carboxylic acid, the carbonyl compound and the acid catalyst so that heating in the lower carboxylic acid is possible. The method for preparing such a mixture is not particularly limited, and may be appropriately prepared according to the apparatus used for the heating step. For example, the mixture may be prepared by adding (introducing) them in the same container. .

  Further, in such a heating step, another solvent may be added to the lower carboxylic acid for use. Examples of such solvents (other solvents) include aromatic solvents such as benzene, toluene, xylene and chlorobenzene; ether solvents such as ether, THF and dioxane; ester solvents such as ethyl acetate; hexane and cyclohexane , Hydrocarbon solvents such as heptane and pentane; nitrile solvents such as acetonitrile and benzonitrile; halogen solvents such as methylene chloride and chloroform; ketone solvents such as acetone and MEK; amides such as DMF, NMP, DMI and DMAc And system solvents.

  The temperature condition for heating the carbonyl compound represented by the general formula (8) in the lower carboxylic acid is not particularly limited, but the upper limit of the heating temperature is 180 ° C. (more preferably 150 ° C., still more preferably). Is preferably 140 ° C., particularly preferably 130 ° C., while the lower limit of the heating temperature is preferably 80 ° C. (more preferably 100 ° C., still more preferably 110 ° C.). As a temperature range (temperature condition) at the time of such heating, it is preferable to set it as 80-180 degreeC, It is more preferable to set it as 80-150 degreeC, It is further more preferable to set it as 100-140 degreeC, 110-110 A temperature of 130 ° C. is particularly preferable. If the temperature condition is less than the lower limit, the reaction does not proceed sufficiently, and the target tetracarboxylic dianhydride tends to be unable to be produced sufficiently efficiently. The activity tends to decrease. Further, such a heating temperature is preferably set to a temperature lower than the boiling point of the homogeneous acid catalyst within the range of the temperature condition. By setting the heating temperature in this way, the product can be obtained more efficiently.

  In addition, the heating step includes a step of refluxing the mixture (mixture of the lower carboxylic acid, the carbonyl compound, and the acid catalyst) by heating from the viewpoint of more efficiently generating a carboxylic acid anhydride. Also good. Thus, it becomes possible to manufacture a carboxylic anhydride more efficiently by including a refluxing step in the heating step. That is, in the heating step, in the initial stage of heating, since the reaction does not proceed sufficiently, by-products such as water are hardly generated. Therefore, until the reaction proceeds to some extent (initial stage of heating), the carboxylic acid dianhydride is not significantly affected by by-products (water, etc.) without removing the distillate component (steam). It is possible to efficiently proceed the positive reaction for producing. Therefore, in particular, in the initial stage of heating, it becomes possible to efficiently use the lower carboxylic acid by refluxing to allow the forward reaction to proceed efficiently, thereby producing the carboxylic acid anhydride more efficiently. Is possible.

Here, the degree of progress of the positive reaction can be determined by confirming the amount of by-products (for example, water or an ester compound of lower carboxylic acid) contained in the steam. Therefore, when the reflux step is performed, the reflux time is appropriately set so that the reaction proceeds efficiently while confirming the amount of by-products in the steam (for example, an ester compound of a lower carboxylic acid), You may perform the removal process of a distilling component, heating. By performing the distilling component removal step in this manner, by-products (eg, ester compounds of lower carboxylic acid and water) can be removed from the reaction system, and the positive reaction can proceed more efficiently. It becomes possible. Further, in the step of removing the distillate component, when the distillate component (vapor) is appropriately distilled off, the lower carboxylic acid is reduced (for example, a lower carboxylic acid ester compound and water are formed as by-products). When the carboxylic acid is consumed and the vapor is distilled off, resulting in a decrease in the carboxylic acid, etc.), the reduced amount of the lower carboxylic acid is appropriately added (in some cases, continuously). It is preferable to carry out heating. In this way, by adding a lower carboxylic acid (in some cases, continuously added), for example, the carbonyl compound is represented by the general formula (8), and R ⁶ in the formula is other than a hydrogen atom. In the case of a compound that is a group, the positive reaction can proceed more efficiently.

  In addition, when such a heating step includes a step of refluxing the mixture, the reflux conditions are not particularly limited, and known conditions can be appropriately employed, and are suitable according to the type of the carbonyl compound (raw material compound) to be used. Can be appropriately changed to various conditions.

  In addition, the pressure condition (pressure condition at the time of reaction) when heating the carbonyl compound (raw material compound) represented by the general formula (8) in the lower carboxylic acid is not particularly limited, In addition, it may be under pressurized conditions or under reduced pressure conditions, and the reaction can proceed under any conditions. Therefore, during the heating step, for example, without particularly controlling the pressure, for example, in the case of adopting the above-described refluxing step, the reaction is performed under a pressurized condition with a vapor of a lower carboxylic acid serving as a solvent. Also good. Moreover, as such a pressure condition, it is preferable to set it as 0.001-10 Mpa, and it is still more preferable to set it as 0.1-1.0 Mpa. If the pressure condition is less than the lower limit, the lower carboxylic acid tends to vaporize. On the other hand, if the pressure condition exceeds the upper limit, the ester compound of the lower carboxylic acid produced by the reaction by heating does not volatilize, and the positive The reaction tends to be difficult to proceed.

  Further, the atmospheric gas for heating the carbonyl compound represented by the general formula (8) in the lower carboxylic acid is not particularly limited. For example, even an air is an inert gas (nitrogen, argon, etc.). It may be. In addition, in order to volatilize by-products (lower carboxylic acid ester compounds and water) generated in the reaction efficiently and to advance the reaction more efficiently (to make the equilibrium reaction of transesterification more prone to the generation system), The above gas (preferably an inert gas such as nitrogen or argon) may be bubbled, or may be agitated while venting the gas phase portion of the reactor (reaction vessel).

  The heating time for heating the carbonyl compound represented by the general formula (8) in the lower carboxylic acid is not particularly limited, but is preferably 0.5 to 100 hours, preferably 1 to 50 More preferably, it is time. If the heating time is less than the lower limit, the reaction does not proceed sufficiently, and a sufficient amount of carboxylic anhydride tends to be unable to be produced. On the other hand, if the upper limit is exceeded, the reaction proceeds further. However, there is a tendency that the production efficiency is lowered and the economy is lowered.

  In addition, when the carbonyl compound represented by the general formula (8) is heated in the lower carboxylic acid, the lower carboxylic acid (more than The reaction may be allowed to proceed while stirring the mixture of the lower carboxylic acid, the carbonyl compound and the acid catalyst.

  Further, in the step of heating the carbonyl compound represented by the general formula (8) in the lower carboxylic acid (heating step), it is preferable to use acetic anhydride together with the lower carboxylic acid. That is, in the present invention, it is preferable to use acetic anhydride during the heating. By using acetic anhydride in this way, it is possible to react the water produced during the reaction with acetic anhydride to form acetic acid, and to efficiently remove the water produced during the reaction. The positive reaction can be advanced more efficiently. Moreover, when utilizing such acetic anhydride, the usage-amount of this acetic anhydride is although it does not restrict | limit, It is preferable to set it as 4-100 times mole with respect to the carbonyl compound represented by the said General formula (8). When the amount of acetic anhydride used is less than the lower limit, the reaction rate tends to decrease, and when it exceeds the upper limit, the yield tends to decrease.

  Even when acetic anhydride is used in this way, it is preferable to adopt the conditions described in the above heating step for the temperature conditions, pressure conditions, atmospheric gas conditions, heating time conditions, etc. during heating. . In addition, when acetic anhydride is used in this way, it is possible to form acetic acid by reacting water produced during the reaction with acetic anhydride, and it can be produced during the reaction without vapor distillation. Water can be efficiently removed, and the reaction (positive reaction) in which acetic acid is formed from acetic anhydride and water to produce tetracarboxylic dianhydride proceeds more efficiently. Will be. Therefore, in the case of using acetic anhydride in this way, it is possible to efficiently advance the reaction by employing the refluxing step in the heating step. From such a viewpoint, when acetic anhydride is used, the heating step is preferably a step of refluxing the mixture. In this way, when refluxing is performed using acetic anhydride, the reaction can be performed only by performing the refluxing step without performing steps such as distillation of vapor or addition of lower carboxylic acid depending on the amount of use. Can be made to proceed sufficiently, and tetracarboxylic dianhydride can be more efficiently produced.

  Moreover, as aromatic diamine which has the said carboxyl group, from a viewpoint that the adhesiveness of metal foil (especially copper foil) and a polyimide layer improves further, following general formula (301)-(304):

[In the formula (301), R ¹² represents one selected from the group consisting of a hydrogen atom, a methoxy group, and an ethoxy group. ]
It is preferable that it is 1 type selected from the aromatic diamine represented by the above-mentioned, it is more preferable that it is group represented by the said general formula (301) or (302), and the said general formula (301) It is particularly preferable that the group is represented. As the aromatic diamine having such a carboxyl group, commercially available products may be used as appropriate.

  Moreover, there is no restriction | limiting in particular as aromatic diamine which does not have the said carboxyl group, Although the well-known aromatic diamine which does not have a carboxyl group can be used, from a heat resistant viewpoint, following General formula (41)- (44):

[In formula (43), R ¹³ has the same meaning as R ¹³ in general formula (23), and in formula (44), Q has the same meaning as Q in general formula (24). ]
The aromatic diamine represented by the general formula (43) or (44) is more preferable, and the aromatic diamine represented by the general formula (44) is more preferable. Such R ¹³ in the general formula (43) has the same meaning as R ¹³ in the general formula (23), and its preferable one is the same as the preferable one of R ^{13 in} the general formula (23). It is. Further, Q in the general formula (44) has the same meaning as Q in the general formula (24), and the preferable one thereof is the same as the preferable one of Q in the general formula (24). Among such aromatic diamines having no carboxyl group, from the viewpoint of further improving the heat resistance and the adhesion between the metal foil (especially copper foil) and the polyimide layer, the following general formula (401):

The aromatic diamine represented by these is especially preferable. Moreover, you may utilize suitably a commercially available thing as such aromatic diamine which does not have a carboxyl group.

  In such a method for producing a metal-clad laminate, a tetracarboxylic dianhydride represented by the general formula (3), an aromatic diamine having the carboxyl group, and an aromatic diamine having no carboxyl group, The ratio of use of tetracarboxylic dianhydride represented by the above general formula (3) with respect to 1 equivalent of all amino groups in the aromatic diamine having a carboxyl group and the aromatic diamine having no carboxyl group The acid anhydride group of the product is preferably 0.2 to 2 equivalents, more preferably 0.3 to 1.2 equivalents. When such a use ratio is less than the lower limit, the polymerization reaction does not proceed efficiently, and a high molecular weight polyamic acid tends not to be obtained. On the other hand, when the upper limit is exceeded, a high molecular weight polyamic acid is obtained as described above. It tends to be impossible.

  Moreover, in the manufacturing method of such a metal-clad laminated board, it is preferable that the mixing ratio of the aromatic diamine which has the said carboxyl group is 1-50 mol% with respect to the total amount of diamine 100 mol%, It is more preferably 30 mol%, further preferably 3 to 20 mol%, particularly preferably 3 to 10 mol%. Thereby, the polyimide layer which contains the repeating unit (A) which has a carboxyl group represented by the said General formula (1) with the said ratio can be formed. The mixing ratio of the aromatic diamine having no carboxyl group is preferably 50 to 99 mol%, more preferably 70 to 98 mol%, and more preferably 80 to 97 mol% with respect to 100 mol% of the total amount of diamine. More preferably, 90 to 97 mol% is particularly preferable. Thereby, the polyimide layer which contains the repeating unit (B) which does not have a carboxyl group represented by the said General formula (2) by the said ratio can be formed.

  Furthermore, in the method for producing such a metal-clad laminate, other tetracarboxylic dianhydrides other than the tetracarboxylic dianhydride represented by the general formula (3) are within the range not impairing the effects of the present invention. You may mix things. Such other tetracarboxylic dianhydrides are not particularly limited, and other known tetracarboxylic dianhydrides capable of constituting polyimide can be appropriately used. The mixing ratio of such other tetracarboxylic dianhydrides is preferably 50 mol% or less with respect to 100 mol% of the total amount of tetracarboxylic dianhydrides, from the viewpoint of heat resistance and transparency of the polyimide layer. 25 mol% or less is more preferable, 10 mol% or less is more preferable, 5 mol% or less is particularly preferable, and 0 mol% is most preferable.

  Moreover, in the manufacturing method of such a metal-clad laminated board, you may mix other diamines other than aromatic diamine in the range which does not impair the effect of this invention. Such other diamines are not particularly limited, and other known diamines that can constitute polyimide can be appropriately used. As a mixing ratio of such other diamines, from the viewpoint of heat resistance of the polyimide layer, adhesion to metal foil (especially copper foil) and transparency, 50 mol% with respect to 100 mol% of the total amount of diamine. Or less, more preferably 25 mol% or less, still more preferably 10 mol% or less, particularly preferably 5 mol% or less, and most preferably 0 mol%.

  As said polymerization solvent used for reaction with the tetracarboxylic dianhydride represented by the said General formula (3), the aromatic diamine which has the said carboxyl group, and the aromatic diamine which does not have the said carboxyl group, said general It is preferably an organic solvent capable of dissolving all of the tetracarboxylic dianhydride represented by the formula (3), the aromatic diamine having a carboxyl group, and the aromatic diamine having no carboxyl group. . Examples of such an organic solvent include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide, γ-butyrolactone, propylene carbonate, tetramethylurea, 1,3- Aprotic polar solvents such as dimethyl-2-imidazolidinone, hexamethylphosphoric triamide, pyridine; phenolic solvents such as m-cresol, xylenol, phenol, halogenated phenol; tetrahydrofuran, dioxane, cellosolve, glyme And ether solvents such as diglyme; aromatic solvents such as benzene, toluene and xylene; ketone solvents such as cyclopentanone and cyclohexanone; and nitrile solvents such as acetonitrile and benzonitrile. Such polymerization solvents (organic solvents) may be used alone or in combination of two or more.

  Furthermore, as the usage-amount of the said polymerization solvent (organic solvent) in such a polymerization reaction, the tetracarboxylic dianhydride represented by the said General formula (3), the aromatic diamine which has the said carboxyl group, and the said carboxyl group It is preferable that the total amount of the aromatic diamine not having the amount is 1 to 80% by mass (more preferably 5 to 50% by mass) with respect to the total amount of the reaction solution. If the amount of such an organic solvent used is less than the lower limit, it tends to be impossible to obtain polyamic acid efficiently. On the other hand, if it exceeds the upper limit, stirring tends to be difficult due to the increase in viscosity.

  In the method for producing the metal-clad laminate of the present invention, the tetracarboxylic dianhydride represented by the general formula (3), the aromatic diamine having the carboxyl group, and the aromatic not having the carboxyl group The method for reacting with diamine is not particularly limited, and a known method capable of reacting tetracarboxylic dianhydride with aromatic diamine can be appropriately employed. For example, nitrogen, After dissolving the aromatic diamine having a carboxyl group and the aromatic diamine having no carboxyl group in a solvent under an inert atmosphere such as helium or argon, the tetracarboxylic acid represented by the general formula (3) is used. You may employ | adopt the method of adding an acid dianhydride and making it react for 10 to 48 hours after that. In such a reaction, the temperature condition is preferably about 15 to 100 ° C. If the reaction time or reaction temperature is less than the lower limit, it tends to be difficult to cause sufficient reaction. On the other hand, if the upper limit is exceeded, the probability of mixing a substance (such as oxygen) that degrades the polymer increases and the molecular weight increases. It tends to decrease.

  In addition, when the tetracarboxylic dianhydride represented by the general formula (3) is reacted with the aromatic diamine having the carboxyl group and the aromatic diamine not having the carboxyl group, the reaction rate is improved. From the viewpoint of obtaining a polyamic acid having a high degree of polymerization, a basic compound may be further added to the polymerization solvent. Examples of such basic compounds include, but are not limited to, triethylamine, tetrabutylamine, tetrahexylamine, 1,8-diazabicyclo [5.4.0] -undecene-7, pyridine, isoquinoline, α-picoline, and the like. Can be mentioned. Moreover, it is preferable that the usage-amount of such a basic compound shall be 0.001-10 equivalent with respect to 1 equivalent of tetracarboxylic dianhydrides represented by the said General formula (3), 0.01 It is more preferable to set it to -0.1 equivalent. If the amount of such a basic compound used is less than the above lower limit, the effect of addition tends not to be exhibited. On the other hand, if it exceeds the upper limit, it tends to cause coloring or the like.

  The polyimide acid thus formed preferably has an intrinsic viscosity [η] of 0.05 to 3.0 dL / g, and more preferably 0.1 to 2.0 dL / g. When the intrinsic viscosity [η] is smaller than the lower limit, a polyimide layer formed using the same tends to be brittle. On the other hand, when the upper limit is exceeded, the viscosity is too high and the workability is lowered, and the uniform It tends to be difficult to form a simple polyimide layer.

  The intrinsic viscosity [η] of such polyamic acid can be measured as follows. That is, first, N, N-dimethylacetamide is used as a solvent, and the polyamic acid is dissolved in the N, N-dimethylacetamide so as to have a concentration of 0.5 g / dL, and a measurement sample (solution) is obtained. obtain. Next, using the measurement sample, the viscosity of the measurement sample is measured using a kinematic viscometer under a temperature condition of 30 ° C., and the obtained value is adopted as the intrinsic viscosity [η]. In addition, as such a kinematic viscometer, an automatic viscosity measuring apparatus (trade name “VMC-252”) manufactured by Koiso Co., Ltd. is used.

  In such a method for producing a metal-clad laminate, the method for applying the polyamic acid solution on the metal foil is not particularly limited. For example, spin coating, spray coating, dip coating, dropping, Known methods such as a gravure printing method, a screen printing method, a relief printing method, a die coating method, a curtain coating method, and an ink jet method can be appropriately employed.

  Further, in such a method for producing a metal-clad laminate, the method for imidizing the polyamic acid is not particularly limited, and may be any method that can imidize polyamic acid, and is not particularly limited. Can be adopted. As a method for imidizing such a polyamic acid, for example, a method of imidizing the polyamic acid by subjecting the polyamic acid to a heat treatment at a temperature of 60 to 400 ° C. (more preferably 150 to 350 ° C.) or so-called “ It is preferable to employ a method of imidization using an “imidating agent”.

  In the case of adopting a method for imidizing by performing such a heat treatment, if the heating temperature is less than the lower limit, the progress of the reaction tends to be delayed, and on the other hand, if the upper limit is exceeded, coloring or thermal decomposition occurs. There is a tendency for molecular weight to decrease. Moreover, it is preferable that reaction time (heating time) in the case of employ | adopting the method to imidize by heat-processing shall be 0.5 to 5 hours. If such a reaction time is less than the lower limit, it tends to be difficult to sufficiently imidize. On the other hand, if it exceeds the upper limit, it tends to be colored or decrease in molecular weight due to thermal decomposition.

  Moreover, when employ | adopting the method of imidating using what is called an "imidating agent", it is preferable to imidize the said polyamic acid in a solvent in presence of an imidizing agent. As such a solvent, the thing similar to the polymerization solvent (organic solvent) used for the said polymerization reaction can be used conveniently.

  As such an imidizing agent, a known imidizing agent can be appropriately used. For example, acid anhydrides such as acetic anhydride, propionic anhydride, trifluoroacetic anhydride, pyridine, collidine, lutidine, triethylamine, N -Tertiary amines such as methylpiperidine can be mentioned. Moreover, it is preferable that the reaction temperature in the case of imidation in the case of imidating by adding an imidizing agent is 0-180 degreeC, and it is more preferable that it is 30-150 degreeC. The reaction time is preferably 0.1 to 48 hours. If the reaction temperature or time is less than the lower limit, it tends to be difficult to sufficiently imidize. On the other hand, if the upper limit is exceeded, the mixing probability of a substance (such as oxygen) that degrades the polymer increases, and the molecular weight increases. It tends to decrease. The amount of the imidizing agent used is not particularly limited, and is the total of the repeating unit represented by the general formula (4) and the repeating unit represented by the general formula (5) in the polyamic acid. What is necessary is just to make it several millimoles-several mol (preferably about 0.05-4.0 mol) with respect to 1 mol.

  In the case of chemical imidization using such an imidizing agent, as the imidizing agent, a condensing agent (carboxylic anhydride, carbodiimide, acid azide, active esterifying agent, etc.) and a reaction accelerator (tertiary amine) are used. Etc.) is preferably used (a combination thereof). In this way, a combination of a condensing agent (a so-called dehydrating condensing agent such as carboxylic acid anhydride, carbodiimide, acid azide, and active esterifying agent) and a reaction accelerator (tertiary amine, etc.) can be used under low temperature conditions. (More preferably, under a temperature condition of about 100 ° C. or less), the polyamic acid can be more efficiently dehydrated and closed and imidized.

  Such a condensing agent is not particularly limited, and examples thereof include carboxylic anhydrides such as acetic anhydride, propionic anhydride and trifluoroacetic anhydride, carbodiimides such as N, N′-dicyclohexylcarbodiimide (DCC), and diphenyl phosphoric acid. Examples thereof include acid azides such as azide (DPPA), active esterifying agents such as Castro reagent, and dehydrating condensation agents such as 2-chloro-4,6-dimethoxytriazine (CDMT). Among such condensing agents, acetic anhydride, propionic anhydride, and trifluoroacetic anhydride are preferable, acetic anhydride and propionic anhydride are more preferable, and acetic anhydride is still more preferable from the viewpoint of reactivity, availability, and practicality. Such condensing agents may be used alone or in combination of two or more.

  The reaction accelerator is not particularly limited as long as it can be used when the polyamic acid is condensed to form a polyimide, and a known compound can be appropriately used. Such a reaction accelerator can also function as an acid scavenger that supplements the acid by-produced during the reaction. Therefore, by using such a reaction accelerator, acceleration of the reaction and a reverse reaction due to by-product acid are suppressed, and the reaction can proceed more efficiently. Such a reaction accelerator is not particularly limited, but more preferably also serves as an acid scavenger, such as triethylamine, diisopropylethylamine, N-methylpiperidine, pyridine, collidine, lutidine, 2-hydroxypyridine, Tertiary amines such as 4-dimethylaminopyridine (DMAP), 1,4-diazabicyclo [2.2.2] octane (DABCO), diazabicyclononene (DBN), diazabicycloundecene (DBU), etc. be able to. Among such reaction accelerators, triethylamine, diisopropylethylamine, N-methylpiperidine, and pyridine are preferable from the viewpoint of reactivity, availability, and practicality, triethylamine, pyridine, and N-methylpiperidine are more preferable, and triethylamine, N -More preferred is methylpiperidine. Such reaction accelerators may be used alone or in combination of two or more.

  In the case of chemical imidization using such an imidizing agent, for example, a catalytic amount of a reaction accelerator (DMAP, etc.) and an azeotropic dehydrating agent (benzene, toluene, xylene, etc.) are added to form a polyamic acid. The water generated when the imide is formed may be removed by azeotropic dehydration to perform chemical imidization. Thus, in chemical imidization (imidation using an imidizing agent), an azeotropic dehydrating agent may be appropriately used together with the reaction accelerator. Such an azeotropic dehydrating agent is not particularly limited, and may be appropriately selected from known azeotropic dehydrating agents according to the type of material used in the reaction.

  Moreover, in the manufacturing method of such a metal clad laminated board, when employ | adopting the method of imidating by performing heat processing, it represents with the said General formula (3) in a polymerization solvent (organic solvent). It can be obtained without reacting tetracarboxylic dianhydrides with the aromatic diamine having a carboxyl group and the aromatic diamine having no carboxyl group and isolating the resulting polyamic acid before imidization. The reaction solution (the reaction solution containing the polyamic acid) is used as it is, and after the reaction solution is applied onto a metal foil, the solvent is removed by drying treatment and imidization is performed by performing the heat treatment. It may be adopted. The temperature condition for the drying treatment in such a method is preferably 0 to 180 ° C, more preferably 30 to 150 ° C. If the temperature condition in such a drying process is less than the lower limit, it tends to be difficult to sufficiently evaporate and remove the solvent. On the other hand, if the temperature exceeds the upper limit, the solvent boils and becomes a film containing bubbles and voids. There is a tendency. In addition, it does not restrict | limit especially as a coating method of the said reaction liquid, A well-known method (cast method etc.) can be employ | adopted suitably. In addition, the polyamic acid may be isolated from the reaction solution and used. In that case, the polyamic acid isolation method is not particularly limited, and a known method capable of isolating the polyamic acid is appropriately used. For example, a method of isolating as a reprecipitate may be employed.

  On the other hand, when a method of imidizing using an “imidating agent” is adopted, the method of imidizing using an “imidizing agent” is originally imidized in a solvent (more preferably, the polymerization solvent). Therefore, for example, in an organic solvent (polymerization solvent), the tetracarboxylic dianhydride represented by the general formula (3), the aromatic diamine having the carboxyl group, and the carboxyl The reaction solution (the reaction solution containing the polyamic acid) is used as it is without reacting with an aromatic diamine not having a group and isolating the produced polyamic acid before imidization. A method of applying an imidizing agent to the metal foil and then imidizing it by coating on a metal foil can be suitably employed.

  Moreover, as a solvent used when adopting a method for imidizing using an “imidating agent (preferably a combination of a condensing agent and a reaction accelerator)”, the above-mentioned viewpoint (the reaction solution as it is) is used. From the viewpoint of use, the polymerization solvent is preferable, and among them, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N, N-dimethylformamide, 1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide And N, N-dimethylacetamide is more preferable. Such polymerization solvents may be used alone or in combination of two or more.

  In the case where the reaction solution (the reaction solution containing the polyamic acid) is used as it is and imidized by adding an imidizing agent to the reaction solution, the organic solvent (polymerization solvent) has a boiling point of 20 ° C. or higher. It is preferable that it is a thing of 50-250 degreeC. If the boiling point is less than the above lower limit, polymerization at atmospheric pressure and room temperature becomes difficult, and there is a tendency to be carried out under special conditions such as under pressure and low temperature. When a body-like polyimide is obtained, it is difficult to remove the organic solvent (solvent) in the step of drying after washing, and the solvent tends to remain in the resulting polyimide.

  Moreover, when using what combined the condensing agent and the reaction accelerator as an imidating agent, it is preferable that the temperature conditions in the case of chemical imidation shall be -40 degreeC-200 degreeC, and -20 degreeC- It is more preferable to set it as 150 degreeC, It is more preferable to set it as 0-150 degreeC, It is especially preferable to set it as 50-100 degreeC. If such a temperature exceeds the upper limit, an undesirable side reaction tends to proceed and polyimide cannot be obtained. On the other hand, if the temperature is lower than the lower limit, the reaction rate of chemical imidation decreases or the reaction itself does not proceed. Tend not to be obtained. As described above, when a condensing agent and a reaction accelerator are used in combination, imidization can be performed in a relatively low temperature range such as −40 ° C. to 200 ° C., so that the environmental load is less. It is possible to make it an advantageous method in the manufacturing process.

  Further, when using a combination of a condensing agent and a reaction accelerator as an imidizing agent, the amount of the condensing agent is not particularly limited, but is 0.05 to 1 mol per 1 mol of the repeating unit in the polyamic acid. It is preferable to set it as 10.0 mol, and it is still more preferable to set it as 1-5 mol. If the amount of such a condensing agent (imidizing agent) is less than the lower limit, the reaction rate of chemical imidization tends to decrease, or the reaction itself does not proceed sufficiently and polyimide cannot be obtained sufficiently, When the upper limit is exceeded, an undesirable side reaction proceeds, and thus polyimide cannot be obtained efficiently.

  Moreover, when using what combined the condensing agent and the reaction accelerator as an imidation agent, the usage-amount of the said reaction accelerator is although it does not restrict | limit in particular, It is 0.00 with respect to 1 mol of repeating units in a polyamic acid. It is preferable to set it as 05-4.0 mol, and it is still more preferable to set it as 0.5-2 mol. If the amount of the reaction accelerator used is less than the lower limit, the reaction rate of chemical imidization decreases, or the reaction itself does not proceed sufficiently and polyimide cannot be obtained sufficiently. On the other hand, it exceeds the upper limit. As a result, an undesirable side reaction proceeds, and thus polyimide cannot be obtained efficiently.

  In addition, as atmospheric conditions for performing such chemical imidization, from the viewpoint of preventing coloring due to oxygen in the air and molecular weight reduction due to water vapor in the air, an inert gas atmosphere such as nitrogen gas or under vacuum It is preferable that Moreover, it does not restrict | limit especially as pressure conditions at the time of performing such chemical imidation, However, It is preferable that it is 0.01 hPa-1 MPa, and it is more preferable that it is 0.1 hPa-0.3 MPa. If such pressure is less than the lower limit, the solvent, the condensing agent, and the reaction accelerator are gasified, the stoichiometry is lost, the reaction is adversely affected, and the reaction tends to be difficult to proceed sufficiently. On the other hand, when the above upper limit is exceeded, undesirable side reactions proceed or the solubility of the polyamic acid is lowered and tends to precipitate before imidization.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example.

  First, chemical formulas of aromatic diamines used in each Example and each Comparative Example and abbreviations of the compounds are shown below.

  In addition, as said aromatic diamine, all are commercial items (3,5-DABA: Nippon Pure Chemicals Co., Ltd., NJM05: Nippon Pure Chemicals Co., Ltd., NJM06: Nihon Pure Chemicals Co., Ltd., NJM1410: Nippon Pure Chemicals Co., Ltd. NJM10 manufactured by Nippon Pure Chemicals Co., Ltd., MBAA manufactured by Wakayama Seika Kogyo Co., Ltd., BAPP manufactured by Wakayama Seika Kogyo Co., Ltd.) were used.

  Next, a method for evaluating the characteristics of the copper clad laminates obtained in each example and each comparative example will be described.

<Identification of molecular structure>
Identification of the molecular structure of the polyimide obtained in each example and each comparative example uses the polyimide film prepared in each example and each comparative example, and as a measuring device an IR measuring machine (trade name: manufactured by JASCO Corporation). (FT / IR-4100) was used for IR measurement.

<Measurement of intrinsic viscosity [η]>
The value (unit: dL / g) of the intrinsic viscosity [η] of the polyamic acid obtained as an intermediate in each example and each comparative example is an automatic viscosity measuring device (trade name “VMC-252”) manufactured by Koiso Co., Ltd. Was measured at a temperature of 30 ° C. using a measurement sample having a concentration of 0.5 g / dL using N, N-dimethylacetamide as a solvent.

<Measurement of linear expansion coefficient>
The value of the linear expansion coefficient (unit: ppm / ° C.) of the polyimide layer obtained in each example and each comparative example was vacuum-dried (1 at 120 ° C.) with respect to the polyimide film prepared in each example and each comparative example Time), a dry film obtained by heat treatment at 200 ° C. for 1 hour in a nitrogen atmosphere was used as a measurement sample, and a thermomechanical analyzer (trade name “TMA8310” manufactured by Rigaku) was used as the measurement device. Utilizing a tension mode (49 mN) under a nitrogen atmosphere and a temperature rising rate of 5 ° C./min, the change in length of the sample at 50 ° C. to 200 ° C. is measured, and 50 ° C. to 200 ° C. It measured by calculating | requiring the average value of the change of the length per 1 degreeC in the temperature range of degreeC.

<Measurement of softening point>
The value (unit: ° C) of the softening temperature (softening point) of the polyimide obtained in each example and each comparative example is the same as that of the polyimide film prepared in each example and each comparative example at 150 ° C in a nitrogen atmosphere. After drying, the film was cut into a size of 5 mm in length, 5 mm in width and 13 μm in thickness as a measurement sample, and a thermomechanical analyzer (trade name “TMA8311” manufactured by Rigaku) was used as the measurement device, and nitrogen was used. A transparent quartz pin (tip diameter: 0.5 mm) is needled into the measurement sample at a pressure of 500 mN under conditions of a temperature rise rate of 5 ° C./min and a temperature range of 30 ° C. to 550 ° C. (scanning temperature). (Measurement by a so-called penetration method). In such measurement, the softening temperature was calculated based on the measurement data in accordance with the method described in JIS K7196 (1991) except that the measurement sample was used.

<Measurement of 5% weight loss temperature (Td 5%)>
The value (unit: ° C.) of 5% weight loss temperature (Td 5%) of the polyimide obtained in each example and each comparative example is 150 ° C. under the nitrogen atmosphere of the polyimide film prepared in each example and each comparative example. After drying under the above conditions, a film cut into a size of 5 mm in length, 5 mm in width and 13 μm in thickness is used as a measurement sample, and a thermogravimetric analyzer (“TG / DTA220” manufactured by SII NanoTechnology Co., Ltd.) is used as the measurement device. )), The scanning temperature was set to 30 ° C. to 550 ° C., and nitrogen gas was allowed to flow at 10 ° C./min. The temperature was determined by measuring the temperature at which the weight of the sample used was reduced by 5%.

<Measurement of total light transmittance, haze (turbidity) and yellowness (YI)>
The values of the total light transmittance (unit:%), haze (turbidity: HAZE) and yellowness (YI) of the polyimide layers obtained in each example and each comparative example were prepared in each example and each comparative example. The obtained polyimide film was used, and the product name “Haze Meter NDH-5000” manufactured by Nippon Denshoku Industries Co., Ltd. was used as a measuring device to perform measurement in accordance with JIS K7361-1 (issued in 1997).

<Measurement of peel strength>
The value (unit: kg / cm) of the peel strength between the copper foil and the polyimide layer in the copper clad laminate obtained in each example and each comparative example is the copper clad laminate produced in each example and each comparative example. Using a measurement sample cut into a size of about 100 mm in length: about 25 mm in width, using a Tensilon type universal testing machine (“UCT-10T” manufactured by A & D Co., Ltd.) as a measuring device. In accordance with JIS C 6481, measurement was performed by a 90-degree peel test method at a tensile speed of 50 mm / min.

(Synthesis Example 1)
<Synthesis process of tetracarboxylic dianhydride>
First, 5-norbornene-2,3-dicarboxylic acid anhydride (12.3 g, 75.0 mmol), 1,4-diiodobenzene (12.4 g, 37.5 mmol), palladium acetate (168 mg, 0.750 mmol) And 2- (dicyclohexylphosphino) -2′-dimethylaminobiphenyl (590 mg, 1.50 mmol) were introduced into a 500 mL three-necked flask, and the atmosphere gas inside the flask was replaced with nitrogen. Next, N, N-dimethylformamide (180 mL), triethylamine (14.6 mL, 105 mmol) and formic acid (3.96 mL, 105 mmol) were further added to the inside of the three-necked flask to obtain a mixed solution. Subsequently, the mixed solution was stirred for 6 hours under a temperature condition of 80 ° C. to obtain a reaction solution. In the resulting reaction solution, black palladium (Pd (0)) powder (palladium black) derived from the palladium acetate (palladium catalyst) was deposited.

  Next, palladium black powder was removed from the reaction solution by filtration to obtain a filtrate. Next, while heating the filtrate at 60 ° C., the filtrate was concentrated under reduced pressure until a solid (solid content) was precipitated, thereby obtaining a concentrated liquid in which a solid (solid content) was precipitated. Thereafter, methanol (250 mL) was added to the concentrated solution, and the solid content was dispersed in methanol, followed by stirring at 25 ° C. for 3 hours to obtain a dispersion. Next, the solid dispersed in the dispersion is separated by filtration, and the obtained solid is allowed to stand at 80 ° C. for 3 hours under vacuum conditions, and the solvent (N, N-dimethylformamide, methanol, etc.) were removed to obtain the product (3.08 g, yield: 20.2%).

  In order to confirm the structure of the product (compound) thus obtained, IR measurement, NMR measurement and FD-MS measurement were performed. As a result, the obtained compound has the following general formula (13):

It was confirmed that it is tetracarboxylic dianhydride represented by. The outline of the reaction for obtaining such a compound is shown in the reaction formula (A).

Example 1
<Preparation process of polyamic acid>
First, a 50 ml screw tube was heated with a heat gun and sufficiently dried. Next, the atmosphere gas in the screw tube sufficiently dried was replaced with nitrogen, and the inside of the screw tube was set to a nitrogen atmosphere. Subsequently, 0.35-mmol (0.0456 g: 3,5-DABA) of 3,5-diaminobenzoic acid as an aromatic diamine having a carboxyl group and 2,2 as an aromatic diamine having no carboxyl group are added to the screw tube. -Bis [4- (4-aminophenoxy) phenyl] propane 5.70 mmol (2.34 g: BAPP) and tetracarboxylic dianhydride 6.00 mmol (2.44 g) represented by the above general formula (13) After the introduction, 19.30 g of N, N-dimethylacetamide was further added, and the two kinds of aromatic diamines (a mixture of 3,5-DABA and BAPP (3,5 -The molar ratio of DABA to BAPP ([3,5-DABA]: [BAPP]) is 5:95)) and the above general formula (13) To obtain a mixture containing the tetracarboxylic acid dianhydride.

  Next, the mixed solution was stirred at 80 ° C. for 3 hours under a nitrogen atmosphere to obtain a reaction solution. In this way, polyamic acid was formed in the reaction solution.

  A part of the reaction solution (polyamide acid N, N-dimethylacetamide solution: polyamic acid solution) was used to prepare an N, N-dimethylacetamide solution with a polyamic acid concentration of 0.5 g / dL. Then, as described above, the intrinsic viscosity [η] of the polyamic acid as the reaction intermediate was measured. The results are shown in Table 1.

<Manufacturing process of copper clad laminate>
Rolled copper foil manufactured by JX Nippon Mining & Metals Co., Ltd. as a copper foil (HA-V2 foil (manufactured by JX Nippon Mining & Metals Co., Ltd.) excellent in bending properties) is surface treated with a silane coupling agent containing nitrogen atoms. Copper foil, 100 mm in length, 100 mm in width, 12 μm in thickness), and the reaction solution (polyamic acid solution) obtained as described above is coated on the surface of the copper foil with the thickness of the coating film after heat curing. Was spin-coated to a thickness of 25 μm to form a coating film on the copper foil. Thereafter, the copper foil on which the coating film was formed was placed on a hot plate at 60 ° C. and allowed to stand for 2 hours, and the solvent was evaporated and removed from the coating film (solvent removal treatment).

  After performing such a solvent removal treatment, the copper foil on which the coating film has been formed is put into an inert oven in which nitrogen is flowing at a flow rate of 3 L / min. After standing at temperature conditions for 0.5 hours, heated at 135 ° C. for 0.5 hours, further heated at 300 ° C. for 1 hour (final heating temperature) to cure the coating film, A copper-clad laminate having a polyimide layer formed on the copper foil was obtained.

<Polyimide film production process>
Using a glass substrate (large slide glass “S9213” manufactured by Matsunami Glass Industrial Co., Ltd., length 76 mm, width 52 mm, thickness 1.3 mm) instead of copper foil, polyimide is applied onto the glass substrate in the same manner as described above. A polyimide-coated glass coated with a thin film (polyimide film) was obtained. The polyimide-coated glass was produced at the same time as the copper-clad laminate in order to match the production conditions of the polyimide film with the production conditions of the copper-clad laminate.

  Next, the polyimide-coated glass thus obtained is immersed in hot water at 90 ° C., and the polyimide film is peeled off from the glass substrate to obtain a polyimide film (length 76 mm, width 52 mm, thickness 13 μm). Size film).

The IR spectrum of the polyimide film thus obtained was measured. The result is shown in FIG. As is clear from the results shown in FIG. 1, since the peak of wave number 1706 cm ⁻¹ indicating C═O stretching vibration of imide carbonyl was observed in the obtained IR spectrum, the obtained film was made of polyimide. It was confirmed to be a thing.

  Moreover, the obtained polyimide is a repeating unit corresponding to the repeating unit represented by the general formula (1) (repeating unit corresponding to the repeating unit (A) having a carboxyl group) based on the type of monomer used and the amount ratio thereof. Unit) and a repeating unit corresponding to the repeating unit represented by the general formula (2) (repeating unit corresponding to the repeating unit (B) having no carboxyl group) is a molar ratio ([repeating unit The repeating unit corresponding to (A)]: [the repeating unit corresponding to the repeating unit (B)]) was 5:95. Furthermore, regarding the obtained copper-clad laminate and polyimide film, the evaluation results of properties (peel strength and the like determined by the above-described property evaluation method) are shown in Table 1.

(Examples 2 to 6)
In each Example, a copper-clad laminate and a polyimide film were produced in the same manner as in Example 1 except that the type of aromatic diamine having a carboxyl group was changed to that shown in Table 1. In addition, when the IR spectrum of the obtained film was measured, it was confirmed that the film obtained in each Example was made of polyimide. With respect to the copper-clad laminate and polyimide film obtained in each example, the evaluation results of properties (peel strength and the like determined by the above-described property evaluation method) are shown in Table 1.

  Moreover, about the polyimide obtained in each Example, from the kind of monomer used, and its quantity ratio, the repeating unit (repeating unit (A) which has a carboxyl group) corresponded to the repeating unit represented by the said General formula (1). Content ratio of the repeating unit corresponding to the repeating unit represented by the general formula (2) (repeating unit corresponding to the repeating unit (B) having no carboxyl group) [molar ratio ( [Repeating unit corresponding to repeating unit (A)]: [Repeating unit corresponding to repeating unit (B)])]. The results are shown in Table 1.

(Comparative Example 1)
A copper-clad laminate and a polyimide film were produced in the same manner as in Example 1 except that 3,5-DABA was not used and the amount of BAPP was changed to 6.00 mmol. In addition, when the IR spectrum of the obtained film was measured, it was confirmed that the obtained film was made of polyimide. With respect to the obtained copper-clad laminate and polyimide film, the evaluation results of properties (peel strength and the like determined by the above-described property evaluation method) are shown in Table 1.

  In addition, the obtained polyimide is a repeating unit corresponding to the repeating unit represented by the general formula (2) (corresponding to the repeating unit (B) having no carboxyl group) from the kind of monomer used and the amount ratio thereof. The content ratio of the repeating unit is 100 mol%.

  As is clear from the results shown in Table 1, the copper-clad laminates (Examples 1 to 6) of the present invention each have a peel strength of 0.60 kg / cm or more, and the copper foil and the polyimide layer. It was confirmed that the adhesive was excellent. Moreover, as for the copper clad laminated board (Examples 1-6) of this invention, the softening point of a polyimide is 280 degreeC or more, 5% weight reduction temperature is 450 degreeC or more, and has high heat resistance. It was confirmed that there was. From these results, the copper-clad laminate (copper-clad laminate of the present invention) obtained in each example is excellent in adhesion between the copper foil and the polyimide layer and has high heat resistance. I understood.

  On the other hand, the copper clad laminate obtained in Comparative Example 1 has a peel strength of 0.53 kg / cm, and compared with the copper clad laminate (Examples 1 to 6) of the present invention, a copper foil and a polyimide layer. Adhesion with was not sufficient.

  From such a result, in a copper clad laminate comprising a copper foil and a polyimide layer laminated on the copper foil, an aromatic diamine having a carboxyl group in some repeating units of the polyimide constituting the polyimide layer It was found that a copper clad laminate having excellent adhesion between the copper foil and the polyimide layer can be obtained by introducing a group derived from the origin.

  As described above, according to the present invention, it is possible to suppress misalignment when joining a plurality of printed wiring boards with solder, anisotropic conductive film ACF, or the like, and metal foil (particularly copper foil) and It is possible to obtain a metal-clad laminate having excellent adhesion to the polyimide layer. Such a metal-clad laminate of the present invention is useful as a flexible printed circuit board (FPC) material (flexible copper-clad laminate (FCCL)). In addition, in the metal-clad laminate excellent in adhesion between the metal foil (particularly copper foil) and the polyimide layer, it is possible to form a fine wiring pattern, so the metal-clad laminate of the present invention is It is also useful as a material for printed wiring boards having high density wiring.

  In addition, the metal-clad laminate of the present invention is excellent in visibility and can suppress misalignment when bonding a plurality of printed wiring boards, so that the metal-clad laminate is bonded with solder, anisotropic conductive film ACF, or the like. It is also useful as a material for printed wiring boards.

  Furthermore, since the metal-clad laminate of the present invention has high heat resistance and can be bonded to a metal foil and a polyimide layer without using an adhesive by heat treatment at high temperature, two layers It is useful as a non-adhesive type copper clad laminate such as a flexible copper clad laminate (two-layer FCCL). The metal-clad laminate is also effective in the touch panel and printed electronics fields.

Claims (12)

Comprising a metal foil and a polyimide layer laminated on the metal foil, and
The polyimide layer has the following general formula (1):
[In the formula (1), A represents a single bond, a divalent aliphatic group having 1 to 12 carbon atoms forming a chain structure, or 3 to 12 carbon atoms forming a cyclic structure. 1 type selected from the group which consists of a certain bivalent alicyclic group and the bivalent aromatic group whose number of carbon atoms which form an aromatic ring is 6-30, shows the said alicyclic group and the said The aromatic group may have a substituent, and each of the plurality of R ¹ is independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a hydroxyl group, and a nitro group. Or two R ¹ bonded to the same carbon atom may be combined to form a methylidene group, and R ² and R ³ each independently represent a hydrogen atom and a carbon number of 1 to 10 represents one selected from the group consisting of alkyl group, an aromatic R ¹⁰ is a carboxyl group di- It shows the Min-derived group. ]
A repeating unit (A) having a carboxyl group represented by the following general formula (2):
[In the formula (2), A represents a single bond, a divalent aliphatic group having 1 to 12 carbon atoms forming a chain structure, or 3 to 12 carbon atoms forming a cyclic structure. 1 type selected from the group which consists of a certain bivalent alicyclic group and the bivalent aromatic group whose number of carbon atoms which form an aromatic ring is 6-30, shows the said alicyclic group and the said The aromatic group may have a substituent, and each of the plurality of R ¹ is independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a hydroxyl group, and a nitro group. Or two R ¹ bonded to the same carbon atom may be combined to form a methylidene group, and R ² and R ³ each independently represent a hydrogen atom and a carbon number of 1 to 10 represents one selected from the group consisting of alkyl groups, aromatic R ¹¹ is without a carboxyl group Indicating the amine-derived groups. ]
The metal-clad laminate which is a layer which consists of a polyimide containing the repeating unit (B) which does not have a carboxyl group represented by these.   A in the general formulas (1) and (2) is a divalent aromatic group which may have a substituent and has 6 to 30 carbon atoms to form an aromatic ring. Item 2. The metal-clad laminate according to Item 1. R ¹⁰ represents the following general formulas (101) to (104):
[In the formula (101), R ¹² represents one selected from the group consisting of a hydrogen atom, a methoxy group, and an ethoxy group. ]
The metal-clad laminate according to claim 1, wherein the metal-clad laminate is a group selected from the group represented by: R ¹¹ is represented by the following general formula (201):
The metal-clad laminate according to claim 1, wherein the metal-clad laminate is a group represented by:   The metal-clad laminate according to any one of claims 1 to 4, wherein the metal foil has a surface treatment layer made of a silane coupling agent containing a nitrogen atom on the surface.   The metal-clad laminate according to any one of claims 1 to 5, wherein the metal foil is a copper foil.   A printed wiring board comprising the metal-clad laminate according to any one of claims 1 to 6.   An electronic device comprising the printed wiring board according to claim 7. The following general formula (1):
[In the formula (1), A represents a single bond, a divalent aliphatic group having 1 to 12 carbon atoms forming a chain structure, or 3 to 12 carbon atoms forming a cyclic structure. 1 type selected from the group which consists of a certain bivalent alicyclic group and the bivalent aromatic group whose number of carbon atoms which form an aromatic ring is 6-30, shows the said alicyclic group and the said The aromatic group may have a substituent, and each of the plurality of R ¹ is independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a hydroxyl group, and a nitro group. Or two R ¹ bonded to the same carbon atom may be combined to form a methylidene group, and R ² and R ³ each independently represent a hydrogen atom and a carbon number of 1 to 10 represents one selected from the group consisting of alkyl group, an aromatic R ¹⁰ is a carboxyl group di- It shows the Min-derived group. ]
A repeating unit (A) having a carboxyl group represented by the following general formula (2):
[In the formula (2), A represents a single bond, a divalent aliphatic group having 1 to 12 carbon atoms forming a chain structure, or 3 to 12 carbon atoms forming a cyclic structure. 1 type selected from the group which consists of a certain bivalent alicyclic group and the bivalent aromatic group whose number of carbon atoms which form an aromatic ring is 6-30, shows the said alicyclic group and the said The aromatic group may have a substituent, and each of the plurality of R ¹ is independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a hydroxyl group, and a nitro group. Or two R ¹ bonded to the same carbon atom may be combined to form a methylidene group, and R ² and R ³ each independently represent a hydrogen atom and a carbon number of 1 to 10 represents one selected from the group consisting of alkyl groups, aromatic R ¹¹ is without a carboxyl group Indicating the amine-derived groups. ]
The polyimide containing the repeating unit (B) which does not have a carboxyl group represented by these.   A in the general formulas (1) and (2) is a divalent aromatic group which may have a substituent and has 6 to 30 carbon atoms to form an aromatic ring. Item 10. The polyimide according to Item 9. R ¹⁰ represents the following general formulas (101) to (104):
[In the formula (101), R ¹² represents one selected from the group consisting of a hydrogen atom, a methoxy group, and an ethoxy group. ]
The polyimide according to claim 9 or 10, which is one kind of group selected from the group represented by: R ¹¹ is represented by the following general formula (201):
The polyimide as described in any one of Claims 8-11 which is group represented by these.