Resin composition and electronic device

文档序号：555116 发布日期：2021-05-14 浏览：6次中文

阅读说明：本技术 树脂组合物和电子设备 (Resin composition and electronic device ) 是由菅井智美大津信也西村浩谷邦夫于 2019-10-02 设计创作，主要内容包括：本发明的树脂组合物是含有树脂或树脂前体与含氮芳香族杂环化合物的树脂组合物,上述含氮芳香族杂环化合物具有下述通式(1)、通式(6)或通式(7)所示的结构,并且相对于上述树脂或树脂前体,在0.10～30质量％的范围内含有该含氮芳香族杂环化合物。[通式(1)中,A1和A2与氮原子一起表示6元的含氮芳香族杂环,该6元的含氮芳香族杂环可以形成缩环。L表示单键、来自芳香族烃环、芳香族杂环或烷基的连接基团]。(The resin composition of the present invention is a resin composition containing a resin or a resin precursor and a nitrogen-containing aromatic heterocyclic compound, wherein the nitrogen-containing aromatic heterocyclic compound has a structure represented by the following general formula (1), general formula (6) or general formula (7), and is contained in an amount of 0.10 to 30% by mass relative to the resin or the resin precursor. [ in the general formula (1), A1 and A2 represent a 6-membered nitrogen-containing aromatic heterocycle together with the nitrogen atom, and the 6-membered nitrogen-containing aromatic heterocycle may form a condensed ring. L represents a single bond, a linking group derived from an aromatic hydrocarbon ring, an aromatic heterocyclic ring or an alkyl group]。)

1. A resin composition comprising a resin or a resin precursor and a nitrogen-containing aromatic heterocyclic compound,

the nitrogen-containing aromatic heterocyclic compound has a structure represented by the following general formula (1), the following general formula (6) or the following general formula (7),

the nitrogen-containing aromatic heterocyclic compound is contained in an amount of 0.10 to 30% by mass based on the resin or the resin precursor,

general formula (1)

General formula (6)

General formula (7)

In the general formula (1), A1 and A2 represent a 6-membered nitrogen-containing aromatic heterocycle together with a nitrogen atom, the 6-membered nitrogen-containing aromatic heterocycle may form a condensed ring, L represents a single bond, a linking group derived from an aromatic hydrocarbon ring, an aromatic heterocycle or an alkyl group,

in the general formula (6), X₁～X₆represents-N ═ NH-or-CR₁-，R₁Represents a hydrogen atom, an aryl group, a heteroaryl group, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an amino group, a cyano group, a silyl group, a thiol group, a carbonyl group, a halogen atom, a trifluoromethyl group or a hydroxyl group, may further have a substituent, A1 and A2 form a heteroaromatic ring,

in the general formula (7), X₇～X₉represents-N ═,-NH-or-CR₁-，X₁₀～X₁₃denotes-N ═ CR₁-，R₁Represents a hydrogen atom, an aryl group, a heteroaryl group, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an amino group, a cyano group, a silyl group, a thiol group, a carbonyl group, a halogen atom, a trifluoromethyl group or a hydroxyl group, and may further have a substituent, X₁₀～X₁₃At least one of which represents-N-A3 and a4 form a heteroaromatic ring.

2. The resin composition according to claim 1, wherein the resin contains any one of a polyimide resin, an acrylic resin, a cellulose ester resin, a polycarbonate resin, a cycloolefin resin, a phenol resin, an epoxy resin, a polyphenylene ether resin, a polyester resin, or a melamine resin.

3. The resin composition according to claim 1 or 2, wherein the resin contains any one of a polyimide resin, an acrylic resin, or a melamine resin.

4. The resin composition according to any one of claims 1 to 3, wherein the compound having a structure represented by the general formula (1), the general formula (6) or the general formula (7) is contained in an amount of 1 to 10% by mass relative to the resin or the resin precursor.

5. The resin composition according to any one of claims 1 to 4, wherein, in the general formula (1), at least one of A1 and A2 represents a pyridine ring, a pyrimidine ring, a pyrazine ring, a quinazoline ring, a quinoxaline ring, an azacarbazolyl ring, an azadibenzofuran ring, an azadibenzothiophene ring, an imidazole ring, a benzimidazole ring, a pyrazole ring or a benzopyrazole ring.

6. The resin composition according to any one of claims 1 to 5, wherein in the general formula (1), at least one of A1 and A2 represents a pyridine ring, a pyrimidine ring, a quinazoline ring, an azacarbazole ring, an azadibenzofuran ring, an azadibenzothiophene ring, or a benzimidazole ring.

7. The resin composition according to any one of claims 1 to 6, wherein at least one of A1 and A2 of the general formula (1) has a structure represented by the following general formula (2),

general formula (2)

In the general formula (2), Ra, Rb and Rc each independently represent a hydrogen atom or a substituent, n1 represents an integer of 1 to 4, and the position of the linkage to the linking group L in the general formula (1) is a substitutable position among the substituents represented by Ra, Rb and Rc or a substitutable position other than the position where Ra, Rb and Rc exist as substituents in the quinazoline ring.

8. The resin composition according to any one of claims 1 to 6, wherein at least one of A1 and A2 of the general formula (1) has a structure represented by the following general formula (3),

general formula (3)

In the general formula (3), Re, Rd and Rf each independently represents a hydrogen atom or a substituent,

n2 represents an integer of 1 to 4, and the position of the linkage to the linking group L in the general formula (1) is a substitutable position among the substituents represented by Re, Rd and Rf or a substitutable position other than the position where Re, Rd and Rf exist as substituents in the quinoxaline ring.

9. The resin composition according to any one of claims 1 to 6, wherein the compound having a structure represented by the general formula (1) is a compound having a structure represented by the following general formula (4),

general formula (4)

In the general formula (4), Rg, Rh, Ri, and Rj each independently represents a hydrogen atom or a substituent, at least one of Rg, Rh, Ri, and Rj represents a 6-membered aromatic heterocyclic ring, the 6-membered aromatic heterocyclic ring may form a condensed ring, and L2 represents a single bond, a linking group derived from an aromatic hydrocarbon ring, an aromatic heterocyclic ring, or an alkyl group.

10. The resin composition according to any one of claims 1 to 6, wherein the compound having a structure represented by the general formula (1) is a compound having a structure represented by the following general formula (5),

general formula (5)

Ar-(Rk)_n3

In the general formula (5), Ar represents a carbazole ring, a dibenzofuran ring, an azadibenzofuran ring, a dibenzothiophene ring, an azadibenzothiophene ring, an azacarbazole ring, a naphthalene ring, an anthracene ring, a phenanthrene ring or a fluorene ring, Rk represents a hydrogen atom or a substituent, at least two of Rk represent a 6-membered aromatic heterocyclic ring, the 6-membered aromatic heterocyclic ring may form a condensed ring, and n3 represents 2 or more.

11. An electronic device having a resin layer and a metal conductive layer,

the resin layer contains the resin composition according to any one of claims 1 to 10,

the resin layer is adjacent to the metal conductive layer.

12. The electronic device according to claim 11, wherein the metal conductive layer contains any one of Ag, Cu, Al, Mo, W, or Ti, or an alloy containing any one of Ag, Cu, Al, Mo, W, or Ti.

13. The electronic device according to claim 11 or 12, wherein the resin composition contains 2 or more kinds of resin precursors.

14. The electronic device according to any one of claims 11 to 13, wherein the resin layer contains inorganic particles.

15. The electronic device according to any one of claims 11 to 14, wherein the resin layer is a resin layer composed of a cured product cured by light or a thermal polymerization initiator.

16. An electronic device having a resin layer and a metal conductive layer,

an intermediate layer containing a compound having a structure represented by the following general formula (1), the following general formula (6), or the following general formula (7) is provided between the resin layer and the metal conductive layer,

general formula (1)

General formula (6)

General formula (7)

in the general formula (6), X₁～X₆represents-N ═ NH-or-CR₁-，R₁Represents a hydrogen atom, an aryl group, a heteroaryl group, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an amino group, a cyano group, a silyl group, a thiol group, or a carbonyl groupA halogen atom, a trifluoromethyl group or a hydroxyl group, may further have a substituent, A1 and A2 form a heteroaromatic ring,

in the general formula (7), X₇～X₉represents-N ═ NH-or-CR₁-，X₁₀～X₁₃denotes-N ═ CR₁-，R₁Represents a hydrogen atom, an aryl group, a heteroaryl group, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an amino group, a cyano group, a silyl group, a thiol group, a carbonyl group, a halogen atom, a trifluoromethyl group or a hydroxyl group, and may further have a substituent, X₁₀～X₁₃At least one of which represents-N-A3 and a4 form a heteroaromatic ring.

17. The resin composition according to claim 16, wherein the resin contains any one of a polyimide resin, an acrylic resin, a cellulose ester resin, a polycarbonate resin, a cycloolefin resin, a phenol resin, an epoxy resin, a polyphenylene ether resin, a polyester resin, or a melamine resin.

18. The resin composition according to claim 16 or 17, wherein, in the general formula (1), at least one of a1 and a2 represents a pyridine ring, a pyrimidine ring, a pyrazine ring, a quinazoline ring, a quinoxaline ring, an azacarbazole ring, an azadibenzofuran ring, an azadibenzothiophene ring, an imidazole ring, a benzimidazole ring, a pyrazole ring, or a benzopyrazole ring.

19. The resin composition according to any one of claims 16 to 18, wherein at least one of A1 and A2 in the general formula (1) has a structure represented by the following general formula (2),

general formula (2)

20. The resin composition according to any one of claims 16 to 18, wherein at least one of A1 and A2 in the general formula (1) has a structure represented by the following general formula (3),

general formula (3)

In the general formula (3), Re, Rd and Rf each independently represents a hydrogen atom or a substituent,

21. The resin composition according to any one of claims 16 to 18, wherein the compound having a structure represented by the general formula (1) is a compound having a structure represented by the following general formula (4),

general formula (4)

22. The resin composition according to any one of claims 16 to 18, wherein the compound having a structure represented by the general formula (1) is a compound having a structure represented by the following general formula (5),

general formula (5)

Ar-(Rk)_n3

23. The electronic device of any one of claims 16-22, wherein the metal conductive layer comprises any one of Ag, Cu, Al, Mo, W, or Ti, or an alloy comprising any one of Ag, Cu, Al, Mo, W, or Ti.

Technical Field

The present invention relates to a resin composition and an electronic device, and more particularly to a resin composition and an electronic device having excellent adhesion to a metal conductive layer, stability during high-temperature storage, and light transmittance.

Background

In recent years, lightweight conductive elements have been used in various fields such as touch panels represented by various displays such as liquid crystal displays, plasma displays, organic electroluminescence displays, and field emission displays, substrates of optoelectronic devices such as mobile phones, electronic paper, various solar cells, and various electro-luminescence devices, electrodes of various sensors, electromagnetic wave shielding layers, antifogging films, and heating elements for snow melting baths. As a conductive layer used for these conductive elements, a metal conductive layer is widely used.

However, when a layer made of a resin exists below the metal conductive layer, the interface between the metal conductive layer and the resin layer has a problem in adhesion and stability during high-temperature storage.

As the material of the metal conductive layer constituting the conductive element, for example, metals such as Au, Ag, Pt, Cu, Rh, Pd, Al, Cr, Mo, W, Ti, alloys of Ag, Cu, Al, Mo, W, Ti, In, etc., can be used₂O₃、CdO、CdIn₂O₄、Cd₂SnO₄、TiO₂、SnO₂And metal materials such as ZnO and Indium Tin Oxide (ITO). Among these metal materials, silver is most commonly used, but silver is very easily aggregated with each other. Therefore, a uniform film cannot be formed at the interface between the metal conductive layer and the resin layer, and it is generally a sea-island structure, and it is difficult to form a silver layer thinly, so that the light transmittance is poor, and the separation of the silver layer and the resin layer further progresses during high-temperature storage, which causes a problem in stability during high-temperature storage. Metals other than silver also have the same problem.

As the resin layer, for example, the techniques of patent documents 1 and 2 are disclosed, but adhesion at the interface between the metal conductive layer and the resin layer and stability during high-temperature storage are not regarded as problems.

Documents of the prior art

Patent document

Patent document 1: international publication No. 2013/024849

Patent document 2: japanese laid-open patent publication No. 2015-178628

Disclosure of Invention

The present invention has been made in view of the above problems and circumstances, and an object of the present invention is to provide a resin composition having excellent adhesion to a metal conductive layer, stability during high-temperature storage, and light transmittance, and an electronic device using the resin composition.

The present inventors have studied the causes of the above problems in order to solve the above problems, and have found that in this process, by containing a specific amount of a nitrogen-containing aromatic heterocyclic compound having a specific structure in a resin or a resin precursor, the nitrogen-containing aromatic heterocyclic compound can interact with a metal in a metal conductive layer to suppress diffusion of the metal, and as a result, a mixture or the like having good adhesion to the metal conductive layer and excellent stability and light transmittance during high-temperature storage can be provided, and have completed the present invention.

That is, the above problem of the present invention can be solved by the following means.

1. A resin composition comprising a resin or a resin precursor and a nitrogen-containing aromatic heterocyclic compound,

the nitrogen-containing aromatic heterocyclic compound has a structure represented by the following general formula (1), the following general formula (6) or the following general formula (7),

the nitrogen-containing aromatic heterocyclic compound is contained in an amount of 0.10 to 30% by mass relative to the resin or the resin precursor.

General formula (1)

General formula (6)

General formula (7)

[ in the general formula (1), A1 and A2 represent a 6-membered nitrogen-containing aromatic heterocycle together with the nitrogen atom, and the 6-membered nitrogen-containing aromatic heterocycle may form a condensed ring. L represents a single bond, a linking group derived from an aromatic hydrocarbon ring, an aromatic heterocyclic ring or an alkyl group.

In the general formula (6), X₁～X₆represents-N ═ NH-or-CR₁-。R₁Represents a hydrogen atom, an aryl group, a heteroaryl group, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an amino group, a cyano group, a silyl group, a thiol group, a carbonyl group, a halogen atom, a trifluoromethyl group or a hydroxyl group, and may further have a substituent. A1 and a2 form a heteroaromatic ring.

In the general formula (7), X₇～X₉represents-N ═ NH-or-CR₁-。X₁₀～X₁₃To represent-N＝、-CR₁-。R₁Represents a hydrogen atom, an aryl group, a heteroaryl group, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an amino group, a cyano group, a silyl group, a thiol group, a carbonyl group, a halogen atom, a trifluoromethyl group or a hydroxyl group, and may further have a substituent, X₁₀～X₁₃At least one of represents-N ═ N. A3 and A4 form a heteroaromatic ring]

3. The resin composition according to claim 1 or 2, wherein the resin contains any one of a polyimide resin, an acrylic resin, and a melamine resin.

4. The resin composition according to any one of items 1 to 3, wherein the compound having a structure represented by the general formula (1), the general formula (6) or the general formula (7) is contained in an amount of 1 to 10% by mass based on the resin or the resin precursor.

5. The resin composition according to any one of items 1 to 4, wherein, in the general formula (1), at least one of A1 and A2 represents a pyridine ring, a pyrimidine ring, a pyrazine ring, a quinazoline ring, a quinoxaline ring, an azacarbazolyl ring, an azadibenzofuran ring, an azadibenzothiophene ring, an imidazole ring, a benzimidazole ring, a pyrazole ring or a benzopyrazole ring.

6. The resin composition according to any one of items 1 to 5, wherein, in the general formula (1), at least one of A1 and A2 represents a pyridine ring, a pyrimidine ring, a quinazoline ring, an azacarbazole ring, an azadibenzofuran ring, an azadibenzothiophene ring, or a benzimidazole ring.

7. The resin composition according to any one of items 1 to 6, wherein at least one of A1 and A2 of the general formula (1) has a structure represented by the following general formula (2).

General formula (2)

[ in the general formula (2), Ra, Rb and Rc each independently represent a hydrogen atom or a substituent. n1 represents an integer of 1 to 4. The position of the linkage to the linking group L in the above general formula (1) is a position that can be substituted in the substituents represented by Ra, Rb and Rc or a position that can be substituted other than the position in the quinazoline ring where Ra, Rb and Rc exist as substituents ]

8. The resin composition according to any one of items 1 to 6, wherein at least one of A1 and A2 of the general formula (1) has a structure represented by the following general formula (3).

General formula (3)

In the general formula (3), Re, Rd and Rf each independently represent a hydrogen atom or a substituent. n2 represents an integer of 1 to 4. The linking position with the linking group L in the above general formula (1) is a position that can be substituted in the substituents represented by Re, Rd and Rf or a position that can be substituted other than the position in which Re, Rd and Rf exist as substituents in the quinoxaline ring ]

9. The resin composition according to any one of items 1 to 6, wherein the compound having a structure represented by the general formula (1) is a compound having a structure represented by the following general formula (4).

General formula (4)

In the general formula (4), Rg, Rh, Ri and Rj each independently represent a hydrogen atom or a substituent. At least one of Rg, Rh, Ri, and Rj represents a 6-membered aromatic heterocycle, and the 6-membered aromatic heterocycle may form a condensed ring. L2 represents a single bond, a linking group derived from an aromatic hydrocarbon ring, an aromatic heterocyclic ring or an alkyl group ]

10. The resin composition according to any one of items 1 to 6, wherein the compound having a structure represented by the general formula (1) is a compound having a structure represented by the following general formula (5).

General formula (5)

Ar-(Rk)_n3

In the general formula (5), Ar represents a carbazole ring, a dibenzofuran ring, an azabicyclofuran ring, a dibenzothiophene ring, an azabicyclo thiophene ring, an azacarbazole ring, a naphthalene ring, an anthracene ring, a phenanthrene ring or a fluorene ring. Rk represents a hydrogen atom or a substituent. At least two of Rk represent a 6-membered aromatic heterocycle, and the 6-membered aromatic heterocycle may form a condensed ring. n3 represents 2 or more

11. An electronic device having a resin layer and a metal conductive layer,

the resin layer contains the resin composition according to any one of items 1 to 10,

the resin layer is adjacent to the metal conductive layer.

12. The electronic device according to claim 11, wherein the metal conductive layer contains any one of Ag, Cu, Al, Mo, W, and Ti, or an alloy containing any one of Ag, Cu, Al, Mo, W, and Ti.

13. The electronic device according to claim 11 or 12, wherein the resin composition contains 2 or more kinds of resin precursors.

14. The electronic device according to any one of claims 11 to 13, wherein the resin layer contains inorganic particles.

15. The electronic device according to any one of claims 11 to 14, wherein the resin layer is a resin layer formed of a cured product cured by light or a thermal polymerization initiator.

16. An electronic device having a resin layer and a metal conductive layer,

an intermediate layer is provided between the resin layer and the metal conductive layer, and the intermediate layer contains a compound having a structure represented by the following general formula (1), the following general formula (6), or the following general formula (7).

General formula (1)

General formula (6)

General formula (7)

In the general formula (7), X₇～X₉represents-N ═ NH-or-CR₁-。X₁₀～X₁₃denotes-N ═ CR₁-。R₁Represents a hydrogen atom, an aryl group, a heteroaryl group, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an amino group, a cyano group, a silyl group, a thiol group, a carbonyl group, a halogen atom, a trifluoromethyl group or a hydroxyl group, and may further have a substituent, X₁₀～X₁₃At least one of represents-N ═ N. A3 and A4 form a heteroaromatic ring]

18. The resin composition according to item 16 or 17, wherein, in the general formula (1), at least one of a1 and a2 represents a pyridine ring, a pyrimidine ring, a pyrazine ring, a quinazoline ring, a quinoxaline ring, an azacarbazole ring, an azadibenzofuran ring, an azadibenzothiophene ring, an imidazole ring, a benzimidazole ring, a pyrazole ring, or a benzopyrazole ring.

19. The resin composition according to any one of items 16 to 18, wherein at least one of A1 and A2 of the general formula (1) has a structure represented by the following general formula (2).

General formula (2)

20. The resin composition according to any one of items 16 to 18, wherein at least one of A1 and A2 of the general formula (1) has a structure represented by the following general formula (3).

General formula (3)

In the general formula (3), Re, Rd and Rf each independently represent a hydrogen atom or a substituent.

n2 represents an integer of 1 to 4. The linking position with the linking group L in the above general formula (1) is a position that can be substituted in the substituents represented by Re, Rd and Rf or a position that can be substituted other than the position in which Re, Rd and Rf exist as substituents in the quinoxaline ring ]

21. The resin composition according to any one of items 16 to 18, wherein the compound having a structure represented by the general formula (1) is a compound having a structure represented by the following general formula (4).

General formula (4)

22. The resin composition according to any one of items 16 to 18, wherein the compound having a structure represented by the general formula (1) is a compound having a structure represented by the following general formula (5).

General formula (5)

Ar-(Rk)_n3

23. The electronic device according to any one of claims 16 to 22, wherein the metal conductive layer contains any one of Ag, Cu, Al, Mo, W, and Ti, or an alloy containing any one of Ag, Cu, Al, Mo, W, and Ti.

The above means of the present invention can provide a resin composition excellent in adhesion to a metal conductive layer, stability during high-temperature storage, and light transmittance, and an electronic device using the resin composition.

The mechanism of expression or the mechanism of action of the effect of the present invention is not clear, but is presumed as follows.

The compound having the structure represented by the general formula (1), the general formula (6), or the general formula (7) has an aromatic heterocycle containing a nitrogen atom in the molecule, and therefore interacts with a metal to fix the metal. That is, diffusion of the metal can be suppressed.

Here, the general aromatic heterocyclic compound containing a nitrogen atom has a weak interaction with a metal and has a weak effect of suppressing metal diffusion. Therefore, we have conducted intensive studies and as a result, strong effects can be obtained when the following two interacting compounds (compounds having the following structures a and B) are mainly formed. In the compounds having the following structures a and B, M represents a metal.

A: in the presence of nitrogen (N) atoms in ortho-position to the condensed ring structure

B: in the case of a large number of freely rotating nitrogen (N) atoms within a molecule, 2 intermolecular interactions occur.

Therefore, when the compound having the structure represented by the general formulae (2) and (3) is used as the compound having the structure a, and the compound having the structure represented by the general formulae (4) and (5) is used as the compound having the structure B, the diffusion of the metal can be reliably suppressed, and as a result, the adhesion to the metal conductive layer is good, and the stability during high-temperature storage is excellent. Further, since the metal conductive layer can be formed as a thin film, it is presumed that the light transmittance is excellent.

Detailed Description

The resin composition of the present invention is a resin composition containing a resin or a resin precursor and a nitrogen-containing aromatic heterocyclic compound, wherein the nitrogen-containing aromatic heterocyclic compound has a structure represented by the following general formula (1), general formula (6) or general formula (7), and is contained in an amount of 0.10 to 30% by mass relative to the resin or the resin precursor.

This feature is a feature common to or corresponding to each of the embodiments described below.

In the embodiment of the present invention, the resin preferably contains any one of a polyimide resin, an acrylic resin, a cellulose ester resin, a polycarbonate resin, a cycloolefin resin, a phenol resin, an epoxy resin, a polyphenylene ether resin, a polyester resin, and a melamine resin, and particularly preferably contains any one of a polyimide resin, an acrylic resin, and a melamine resin, from the viewpoint of mechanical properties and electrical properties.

From the viewpoint of stability during storage at high temperature and good production of the resin layer, it is preferable that the compound having a structure represented by the general formula (1), the general formula (6) or the general formula (7) is contained in an amount of 1 to 10% by mass relative to the resin or the resin precursor.

In the general formula (1), at least one of a1 and a2 preferably represents a pyridine ring, a pyrimidine ring, a pyrazine ring, a quinazoline ring, a quinoxaline ring, an azacarbazolyl ring, an azadibenzofuran ring, an azadibenzothiophene ring, an imidazole ring, a benzimidazole ring, a pyrazole ring, or a benzopyrazole ring, and particularly preferably represents a pyridine ring, a pyrimidine ring, a quinazoline ring, an azacarbazolyl ring, an azadibenzofuran ring, an azadibenzothiophene ring, or a benzimidazole ring, from the viewpoints of affinity for a metal conductive layer and stability.

From the viewpoints of suppression of metal diffusion, adhesion to a metal conductive layer, and stability during high-temperature storage, the compound having the structure represented by the general formula (1) is preferably any of the compounds having the structures represented by the general formulae (2) to (5).

The electronic device of the present invention is an electronic device having a resin layer and a metal conductive layer, wherein the resin layer contains the resin composition, and the resin layer is adjacent to the metal conductive layer.

Thus, an electronic device having excellent adhesion at the interface between the metal conductive layer and the resin layer, stability during high-temperature storage, and light transmittance can be obtained.

In view of interaction with the organic compound containing a nitrogen atom having an unshared electron pair of the present invention, the metal conductive layer preferably contains any one of Ag, Cu, Al, Mo, W, and Ti, or an alloy containing any one of Ag, Cu, Al, Mo, W, and Ti.

In view of the ability to combine the properties of each resin, the resin composition preferably contains 2 or more resin precursors.

In addition, the resin layer preferably contains inorganic particles in order to improve physical strength and the like.

Further, from the viewpoint of surface curability, pencil hardness, heat resistance, and the like, it is preferable that the resin layer is a resin layer composed of a cured product cured by light or a thermal polymerization initiator.

Another electronic device of the present invention is an electronic device including a resin layer and a metal conductive layer, wherein an intermediate layer including a compound having a structure represented by the general formula (1), the general formula (6), or the general formula (7) is provided between the resin layer and the metal conductive layer. This also enables to produce an electronic device having excellent adhesion at the interface between the metal conductive layer and the resin layer, stability during high-temperature storage, and light transmittance.

The present invention and its constituent elements, and modes and embodiments for carrying out the present invention will be described below. In the present application, "to" is used to include numerical values recited before and after the "to" as the lower limit value and the upper limit value.

[ resin composition ]

The resin composition of the present invention is a resin composition containing a resin or a resin precursor, and a nitrogen-containing aromatic heterocyclic compound having a structure represented by the following general formula (1), general formula (6) or general formula (7), and containing the nitrogen-containing aromatic heterocyclic compound in an amount of 0.10 to 30% by mass relative to the resin or the resin precursor.

General formula (1)

General formula (6)

General formula (7)

From the viewpoint of stability during storage at high temperatures and good production of a resin layer, the resin composition of the present invention preferably contains a compound having a structure represented by the general formula (1), the general formula (6), or the general formula (7) in an amount of 1 to 10% by mass relative to the resin or the resin precursor.

< Compound having the structure represented by the general formula (1) >

In the general formula (1), examples of the 6-membered aromatic heterocyclic ring formed together with the nitrogen atom and represented by a1 and a2 include pyridine, pyrimidine, pyrazine, and triazine. Examples of the 6-membered nitrogen-containing aromatic heterocycle having a condensed ring include quinazoline, quinoline, isoquinoline, azabiphofuran, azacarbazole, azabiphthaline, benzimidazole ring, benzoquinoline ring, and benzoisoquinoline ring.

Examples of the aromatic hydrocarbon ring used as the linking group represented by L include a benzene ring (phenyl ring), a biphenyl ring, a terphenyl ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, or a fluorene ring, examples of the aromatic heterocyclic ring include a carbazole ring, a dibenzofuran ring, an azabenzofuran ring, a dibenzothiophene ring, an azabenzothiophene ring, and an azacarbazole ring, and examples of the alkyl group include a methyl group, an ethyl group, an isopropyl group, a propyl group, a butyl group, a tert-butyl group, and a hexyl group.

Further, at least one of a1 and a2 in the general formula (1) preferably has a structure represented by the following general formula (2) or (3). The compound having the structure represented by the above general formula (1) is preferably a compound having a structure represented by the following general formula (4) or (5).

< Structure of the general formula (2) >

General formula (2)

In the general formula (2), examples of the substituent represented by Ra, Rb and Rc include an aromatic hydrocarbon ring, an aromatic heterocyclic ring, an alkyl group, a cyano group, a halogen atom and the like. The 6-membered aromatic heterocyclic ring represented by at least one of Ra, Rb and Rc is the same as the 6-membered aromatic heterocyclic ring exemplified in a1 and a2 of the general formula (1).

< Structure of the general formula (3) >

General formula (3)

In the general formula (3), the substituents represented by Re, Rd and Rf are the same as those represented by Ra, Rb and Rc in the general formula (2). The 6-membered aromatic heterocyclic ring represented by at least one of Re, Rd and Rf is the same as the 6-membered aromatic heterocyclic ring exemplified in a1 and a2 of the general formula (1).

< Compound having the structure represented by the general formula (4) >

General formula (4)

In the general formula (4), Rg, Rh, Ri and Rj each independently represent a hydrogen atom or a substituent. At least one of Rg, Rh, Ri, and Rj represents a 6-membered aromatic heterocycle, and the 6-membered aromatic heterocycle may form a condensed ring. L is₂Represents a single bond, a linking group derived from an aromatic hydrocarbon ring, an aromatic heterocyclic ring or an alkyl group]

In the general formula (4), the substituents represented by Rg, Rh, Ri, and Rj are the same as those represented by Ra, Rb, and Rc in the general formula (2). The 6-membered aromatic heterocyclic ring represented by at least one of Rg, Rh, Ri, and Rj is the same as the 6-membered aromatic heterocyclic ring exemplified in a1 and a2 of the general formula (1).

In addition, as L₂The aromatic hydrocarbon ring, aromatic heterocyclic ring and alkyl group represented are the same as those exemplified for the aromatic hydrocarbon ring, aromatic heterocyclic ring and alkyl group in L of the general formula (1).

< Compound having the structure represented by the general formula (5) >

General formula (5)

Ar-(Rk)_n3

In the general formula (5), the substituents represented by Rk are the same as those represented by Ra, Rb and Rc in the general formula (2). The 6-membered aromatic heterocyclic ring represented by Rk is the same as the 6-membered aromatic heterocyclic rings exemplified in a1 and a2 of the general formula (1).

Hereinafter, exemplary compounds of the compound having the structure represented by the above general formula (1) are exemplified, but the present invention is not limited to these compounds.

< Compound having the structure represented by the general formula (6) >

In the general formula (6), X₁～X₆represents-N ═ NH-or-CR₁-。

R₁Represents a hydrogen atom, an aryl group, a heteroaryl group, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an amino group, a cyano group, a silyl group, a thiol group, a carbonyl group, a halogen atom, a trifluoromethyl group or a hydroxyl group, and may further have a substituent.

A1 and a2 form a heteroaromatic ring.

-CR₁Preferably, an aryl or heteroaryl group. Further preferably, the aryl group or the heteroaryl group is substituted with an alkyl group, an alkoxy group or a carbonyl group.

Hereinafter, exemplary compounds of the compound having the structure represented by the above general formula (6) are exemplified, but the present invention is not limited to these compounds.

< Compound having the structure represented by the general formula (7) >

-CR₁Preferably having aromatic groupsA group or a heteroaryl group. Further preferably, the aryl group or the heteroaryl group is substituted with an alkyl group, an alkoxy group or a carbonyl group.

Hereinafter, exemplary compounds of the compound having the structure represented by the above general formula (7) are exemplified, but the present invention is not limited to these compounds.

< resin or resin precursor >

The resin preferably contains any one of a polyimide resin, an acrylic resin, a cellulose ester resin, a polycarbonate resin, a cycloolefin resin, a phenol resin, an epoxy resin, a polyphenylene ether resin, a polyester resin, and a melamine resin, from the viewpoints of mechanical properties such as heat resistance and dimensional stability, and electrical properties such as insulation.

Examples of the cellulose ester resin include triacetyl cellulose (TAC), diacetyl cellulose, and acetyl propionyl cellulose.

Examples of the polycarbonate resin include Panlite and Multilon (made by imperial corporation).

Examples of the cycloolefin resin include ZEONOR (manufactured by japan rison corporation), ARTON (manufactured by JSR corporation), and APEL (manufactured by mitsui chemical corporation).

Examples of the acrylic resin include polymethyl methacrylate, ACRYLITE (manufactured by mitsubishi yang corporation), sumiex (manufactured by sumitomo chemical corporation), and the like.

Examples of the polyester resin include polyethylene terephthalate (abbreviated as PET) and polyethylene naphthalate (abbreviated as PEN).

Among the above resins, one of a polyimide resin, an acrylic resin, an epoxy resin, and a melamine resin is more preferably contained, and particularly, when the resin layer is a resin film, a polyimide resin is preferably contained, and when the resin layer is a Resist (Resist), an acrylic resin or an epoxy resin is preferably contained.

As the polyimide resin, a resin having a structure represented by the following general formula can be used.

[ in the general formula, R represents an aromatic hydrocarbon ring, an aromatic heterocyclic ring, or a 4-valent aliphatic or alicyclic hydrocarbon group having 4 to 39 carbon atoms. Phi is a 2-valent aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group having 2 to 39 carbon atoms, or a combination thereof, and may contain one or more elements selected from the group consisting of-O-, -SO₂-、-CO-、-CH₂-、-C(CH₃)₂-、-OSi(CH₃)₂-、-C₂H₄At least one of O-and-S-as a linking group]

Examples of the aromatic hydrocarbon ring represented by R include a fluorene ring, a benzene ring, a biphenyl ring, a naphthalene ring, an azulene ring, an anthracene ring, a phenanthrene ring, a pyrene ring, a perylene ring, a,Cyclo, tetracene ring, triphenylene ring, ortho-triphenyl ring, meta-triphenyl ring, para-triphenyl ring, acenaphthene ring, coronene ring, fluoranthene ring, tetracene ring, pentacene ring, perylene ring, pentaphene ring, picene ring, pyrene ring, pyranthrene ring, anthanthrene (anthrene) ring, and the like.

Examples of the aromatic heterocycle represented by R include silacyclopentadiene ring, furan ring, thiophene ring, and,An azole ring, a pyrrole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a triazine,A triazole ring, an imidazole ring, a pyrazole ring, a thiazole ring, an indole ring, a benzimidazole ring, a benzothiazole ringAn azole ring, a quinoxaline ring, a quinazoline ring, a phthalazine ring, a thienothiophene ring, a carbazole ring, an azacarbazole ring (which means that at least one of carbon atoms constituting the carbazole ring is substituted by a nitrogen atom), a dibenzosilacyclopentadiene ring, a dibenzofuran ring, a dibenzothiophene ring, a benzothiophene ring, a ring in which at least one of carbon atoms constituting the dibenzofuran ring is substituted by a nitrogen atom, a benzodifuran ring, a benzodithiophene ring, an acridine ring, a benzoquinoline ring, a phenanthridine ring, a phenanthroline ring, a oxazine ring, a quiclloline ring, a tidin ring, a quinuclidine ring, a triphenzodiazine ring, a triphenodithiazine ring, a triphenodioxazine ring, a thienothiophene ring, a benzothiophene ringOxazine rings, phenazine rings, anthracenzazine rings, perimidine rings, naphthofuran rings, naphthothiophene rings, naphthodifuran rings, naphthodithiophene rings, anthrafuran rings, anthradifuran rings, anthradithiophene rings, thianthrene rings, oxathianthrene rings, dibenzocarbazole rings, indolocarbazole rings, dithienobenzene rings, and the like.

Examples of the C4-39 aliphatic hydrocarbon group having a valence of 4 represented by R include butane-1, 1,4, 4-triyl, octane-1, 1,8, 8-triyl, decane-1, 1,10, 10-triyl and the like.

Examples of the 4-valent alicyclic hydrocarbon group having 4 to 39 carbon atoms represented by R include cyclobutane-1, 2,3, 4-tetrayl, cyclopentane-1, 2,4, 5-tetrayl, cyclohexane-1, 2,4, 5-tetrayl, bicyclo [2.2.2] oct-7-ene-2, 3,5, 6-tetrayl, bicyclo [2.2.2] octane-2, 3,5, 6-tetrayl, 3',4,4' -dicyclohexyltetrayl, 3, 6-dimethylcyclohexane-1, 2,4, 5-tetrayl, 3, 6-diphenylcyclohexane-1, 2,4, 5-tetrayl, and the like.

Examples of the aliphatic hydrocarbon group having 2 to 39 carbon atoms and a valence of 2 represented by Φ, which may or may not have the linking group, include groups represented by the following structural formulae.

Examples of the C2-39 alicyclic hydrocarbon group represented by Φ, which may or may not have the linking group, include groups represented by the following structural formulae.

Examples of the 2-valent aromatic hydrocarbon group of 2 to 39 carbon atoms, which may or may not have the linking group, represented by Φ include groups represented by the following structural formulae.

Examples of the group represented by Φ and composed of a combination of an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group include groups represented by the following structural formulae.

The resin is preferably used in a resin film or a resist, which will be described later, and the resin film may be a film produced by melt casting film formation or a film produced by solution casting film formation.

In this case, a compound having a structure represented by the above general formula (1) is mixed with the resin precursor (varnish or the like), and then cured by heat, light or the like, and then the mixture can be used. The resin precursor of the present invention is a component (monomer, oligomer, etc.) constituting the resin.

When the resin is used in the form of a resist, the resin preferably has a photoreactive functional group and a thermosetting functional group in the molecule.

Examples of the photoreactive functional group include a (meth) acryloyl group, and examples of the thermosetting functional group include a hydroxyl group, a carboxyl group, an isocyanate group, an imino group, an epoxy group, an oxetanyl group, a mercapto group, a methoxymethyl group, a methoxyethyl group, an ethoxymethyl group, an ethoxyethyl group, a carboxyl group, an isocyanato group,oxazoline groups, and the like.

Specific examples of the monomer having 1 (meth) acryloyl group in the molecule include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isoamyl acrylate, isobutyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, octyl acrylate, decyl acrylate, isomyristyl acrylate, isostearyl acrylate, 2-ethylhexyl diglycol acrylate, 2-hydroxybutyl acrylate, 2-acryloyloxyethyl hexahydrophthalic acid, butoxyethyl acrylate, ethoxydiglycol acrylate, methoxydiglycol acrylate, methoxypolyethylene glycol acrylate, methoxypropylene glycol acrylate, phenoxyethyl acrylate, tetrahydrofurfuryl acrylate, isobornyl acrylate, and mixtures thereof, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-acryloyloxyethyl succinic acid, 2-acryloyloxyethyl phthalic acid, 2-acryloyloxyethyl-2-hydroxyethyl-phthalic acid, glycidyl methacrylate, lactone-modified flexible acrylate, t-butylcyclohexyl acrylate, acryloylmorpholine and the like.

Specific examples of the polyfunctional monomer having 2 (meth) acryloyl groups in the molecule include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, tripropylene glycol diacrylate, polypropylene glycol diacrylate, 1, 4-butanediol diacrylate, 1, 6-hexanediol diacrylate, 1, 9-nonanediol diacrylate, neopentyl glycol diacrylate, dimethylol tricyclodecane diacrylate, urethane diacrylates, PO adduct diacrylate of bisphenol A, hydroxypivalic acid neopentyl glycol diacrylate, polytetramethylene glycol diacrylate, and the like.

Examples of the polyfunctional group include pentaerythritol triacrylate, trimethylolpropane triacrylate, ethylene oxide-modified pentaerythritol tetraacrylate, propylene oxide-modified trimethylolpropane triacrylate, epichlorohydrin-modified trimethylolpropane triacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, pentaerythritol ethoxytetraacrylate, tetramethylolmethane tetraacrylate, ethylene oxide-modified phosphoric triacrylate, epichlorohydrin-modified glycerol triacrylate, dipentaerythritol hexaacrylate, dipentaerythritol monohydroxypentaacrylate, ditrimethylolpropane tetraacrylate, glyceropropoxyacrylate, caprolactone-modified trimethylolpropane triacrylate, caprolactam-modified dipentaerythritol hexaacrylate, trimethylolpropane triacrylate, and the like, And multifunctional acrylates such as bisphenol fluorene dihydroxy acrylate, bisphenol fluorene dimethacrylate, silsesquioxane modified products thereof, and methacrylate monomers corresponding thereto.

Specific examples of the hydroxyl group as the thermosetting functional group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol monohydroxypenta (meth) acrylate, and 2-hydroxypropyl (meth) acrylate, and commercially available products include LIGHT ESTER HO, LIGHTESTER HOP, and LIGHT ESTER HOA (trade names of Kyoeisha chemical Co., Ltd.).

Specific examples of the carboxyl group as the thermosetting functional group include acrylic acid, methacrylic acid, acrylic acid dimer, 2-methacryloyloxyethylsuccinic acid, 2-methacryloyloxyethylhexahydrophthalic acid, and phthalic acid monohydroxyethyl acrylate, and commercially available products include LI GHT ESTER HO-MS, LIGHT ESTER HO-HH (trade name of Kyoeisha chemical Co., Ltd.), ARONIX M-5400 (trade name of Toyo chemical Co., Ltd.).

Specific examples of the isocyanate group as the thermosetting functional group include 2-methacryloyloxyethyl isocyanate (for example, MOI, a trade name of Showa Denko K.K.).

Specific examples of the epoxy group as the thermosetting functional group include glycidyl methacrylate and (meth) acryloyl group-containing alicyclic epoxy resins, and commercially available products include Cyclomer M100, Cyclomer a200 and Cyclomer 2000 (trade name of celluloid chemical corporation).

Specific examples of the oxetanyl group as the thermosetting functional group include oxetane (meth) acrylate and the like, and examples of commercially available products include OXE-10 and OXE-30 (trade name manufactured by Osaka organic chemical Co., Ltd.).

Specific examples of the thermosetting functional group which is a mercapto group include ethyl thioacrylate, ethyl thiomethacrylate, biphenyl thioacrylate, biphenyl thiomethacrylate, nitrophenylthioacrylate, nitrophenylthiomethacrylate, triphenylmethylthioacrylate, triphenylmethylthiomethacrylate, triacrylate of 1, 2-bis [ (2-mercaptoethyl) thio ] -3-mercaptopropane, 2- (mercaptomethyl) -methyl-2-acrylate, and 2- [ (2-mercaptoethyl) thio ] ethyl-methacrylate.

Specific examples of the methoxymethyl group as the thermosetting functional group include methoxymethyl acrylate, methoxymethyl methacrylate, dimethoxymethyl acrylate, dimethoxymethyl methacrylate and the like, and examples of commercially available products include NIKALAC MX-302 (acrylic acid-modified alkylated melamine, trade name of Sanyo chemical Co., Ltd.).

Specific examples of the methoxyethyl group as the thermosetting functional group include 1-methoxyethyl acrylate, 1-methoxyethyl methacrylate, 2-methoxyethyl acrylate, 2-methoxyethyl methacrylate, 1-methoxyethyl acrylate, 1-methoxyethyl methacrylate and the like.

Specific examples of the ethoxyethyl group as the thermosetting functional group include 1-ethoxyethyl acrylate, 1-ethoxyethyl methacrylate, 2-ethoxyethyl acrylate, and 2-ethoxyethyl methacrylate.

Specific examples of the ethoxymethyl group as the thermosetting functional group include N-ethoxymethacrylamide, N-ethoxymethylmethacrylamide, ethoxymethyl acrylate, ethoxymethyl methacrylate, and the like.

As the thermosetting functional group isSpecific examples of the oxazoline group include 2-methyl-2- { [3- (4, 5-dihydro-2-Azolyl) benzoyl]Amino } ethyl ester, 2-methyl-2- (4, 5-dihydro-2-propanoic acidAzolyl) ethyl esters, 3- (4, 5-dihydro-4, 4-dimethyl-2-propenoic acidOxazolyl) propyl esters, and the like.

[ electronic apparatus ]

(1) Embodiment 1

An electronic device according to embodiment 1 of the present invention is an electronic device including a resin layer and a metal conductive layer, wherein the resin layer contains the resin composition, and the resin layer is adjacent to the metal conductive layer.

< Metal conductive layer >

As the metal used for the metal conductive layer, for example, a metal such as gold, silver, platinum, zinc, palladium, rhodium, osmium, ruthenium, iridium, copper, nickel, cobalt, iron, tin, chromium, titanium, tantalum, tungsten, indium, or an alloy thereof can be used.

In addition, as the metal compound, a metal oxide can be preferably used, and for example, TiO can be mentioned₂ITO (indium tin oxide), ZnO, Nb₂O₅、ZnO/Sb₂O₅(Zinc antimonate), ZrO₂、CeO₂、Ta₂O₅、Ti₃O₅、Ti₄O₇、Ti₂O₃、TiO、SnO₂、La₂Ti₂O₇IZO (indium zinc oxide), AZO (aluminum zinc oxide), GZO (gallium zinc oxide), ATO (antimony tin oxide), ICO (indium cerium oxide), Bi₂O₃、a-GIO、Ga₂O₃、GeO₂、SiO₂、Al₂O₃、HfO₂、SiO、MgO、Y₂O₃、WO₃a-GIO (gallium indium oxide), and the like.

< resin layer >

The resin layer of the present invention contains the above-mentioned resin composition of the present invention.

The resin composition contains a resin or a resin precursor and a compound having a structure represented by the general formula (1), the general formula (6) or the general formula (7).

The resin is not particularly limited, and preferably contains any of the polyimide resin, acrylic resin, cellulose ester resin, polycarbonate resin, cycloolefin resin, phenol resin, epoxy resin, polyphenylene ether resin, polyester resin, or melamine resin described above in view of mechanical properties and electrical properties. Further, it is more preferable to contain any of a polyimide resin, an acrylic resin, an epoxy resin, and a melamine resin. In particular, when the resin layer is a resin film, the resin preferably contains a polyimide resin, and when the resin layer is a resist, the resin preferably contains an acrylic resin or an epoxy resin. When the resin layer is a resist, it is preferable that 2 or more resin precursors are contained or the resin layer is a resin layer containing a photo-or thermal polymerization initiator and formed of a cured product thereof and contains inorganic particles. The 2 or more resin precursors are preferably precursors of acrylic resins or epoxy resins.

The compound having a structure represented by the general formula (1), the general formula (6) or the general formula (7) (nitrogen-containing aromatic heterocyclic compound) is characterized by being contained in an amount of 0.10 to 30% by mass relative to the resin or the resin precursor, and preferably contained in an amount of 1 to 10% by mass in view of good stability during high-temperature storage and good film production.

The resin layer preferably contains the following additives in addition to the resin composition.

Since the additive contained in the case where the resin layer is a resin film is different from that contained in the case where the resin layer is a resist, the following description will be separately made.

(A) Resin film

When a resin film is used as the resin layer, the resin layer preferably contains a matting agent, an ultraviolet absorber, an antioxidant, a peeling accelerator, and the like as needed in addition to the resin composition.

(matting agent)

The resin film of the present invention may contain inorganic fine particles such as silica, titania, alumina, zirconia, calcium carbonate, kaolin, talc, calcined calcium silicate, hydrated calcium silicate, aluminum silicate, magnesium silicate, and calcium phosphate, and a matting agent such as a crosslinked polymer, for example, in order to improve the handling properties. Among these, silica is preferable because it can reduce the haze of the film.

(ultraviolet absorber)

The resin film of the present invention preferably contains an ultraviolet absorber from the viewpoint of improving light resistance. The ultraviolet absorber preferably has a transmittance at a wavelength of 370nm in the range of 0.1 to 30%, more preferably 1 to 20%, and still more preferably 2 to 10%, for the purpose of improving light resistance by absorbing ultraviolet rays of 400nm or less.

(antioxidant)

Antioxidants are also known as anti-deterioration agents. When an electronic device or the like is left in a high-humidity high-temperature state, degradation of the resin film may occur.

The antioxidant has a function of, for example, retarding or preventing decomposition of the resin film due to a residual solvent amount of halogen in the resin film, phosphoric acid of a phosphoric acid-based plasticizer, or the like, and therefore the resin film of the present invention can contain the antioxidant.

As such an antioxidant, a hindered phenol-based compound is preferably used, and examples thereof include 2, 6-di-t-butyl-p-cresol, pentaerythritol-tetrakis [3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ], triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate ], 1, 6-hexanediol-bis [3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ], 2, 4-bis- (n-octylthio) -6- (4-hydroxy-3, 5-di-t-butylanilino) -1,3, 5-triazine, 2-thiodiethylene bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], octadecyl-3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, N' -hexamethylenebis (3, 5-di-tert-butyl-4-hydroxy-hydrocinnamamide), 1,3, 5-trimethyl-2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene, tris- (3, 5-di-tert-butyl-4-hydroxybenzyl) -isocyanurate, and the like.

Particularly preferred are 2, 6-di-t-butyl-p-cresol, pentaerythritol-tetrakis [3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ], triethylene glycol bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate ]. Further, for example, a hydrazine-based metal deactivator such as N, N' -bis [3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionyl ] hydrazine, or a phosphorus-based processing stabilizer such as tris (2, 4-di-t-butylphenyl) phosphite may be used in combination.

(peeling promoters)

As an additive for reducing the peeling resistance of the resin film, many additives having a remarkable effect are available among surfactants, and as a preferable peeling agent, a phosphate ester surfactant, a carboxylic acid or carboxylate salt surfactant, a sulfonic acid or sulfonate salt surfactant, and a sulfate ester surfactant are effective. Further, a fluorine-based surfactant in which a part of hydrogen atoms of a hydrocarbon chain bonded to the surfactant is substituted with fluorine atoms is also effective. Hereinafter, a release agent is exemplified.

RZ-1 C₈H₁₇O-P(＝O)-(OH)₂

RZ-2 C₁₂H₂₅O-P(＝O)-(OK)₂

RZ-3 C₁₂H₂₅OCH₂CH₂O-P(＝O)-(OK)₂

RZ-4 C₁₅H₃₁(OCH₂CH₂)₅O-P(＝O)-(OK)₂

RZ-5 {C₁₂H₂₅O(CH₂CH₂O)₅}₂-P(＝O)-OH

RZ-6 {C₁₈H₃₅(OCH₂CH₂)₈O}₂-P(＝O)-ONH₄

RZ-7 (t-C₄H₉)₃-C₆H₂-OCH₂CH₂O-P(＝O)-(OK)₂

RZ-8 iso-C₉H₁₉-C₆H₄-O-(CH₂CH₂O)₅-P(＝O)-(OK)(OH)

RZ-9 C₁₂H₂₅SO₃Na

RZ-10 C₁₂H₂₅OSO₃Na

RZ-11 C₁₇H₃₃COOH

RZ-12 C₁₇H₃₃COOH·N(CH₂CH₂OH)₃

RZ-13 iso-C₈H₁₇-C₆H₄-O-(CH₂CH₂O)₃-(CH₂)₂SO₃Na

RZ-14 (iso-C₉H₁₉)₂-C₆H₃-O-(CH₂CH₂O)₃-(CH₂)₄SO₃Na

RZ-15 Triisopropyl Naphthalenesulfonic acid sodium salt

RZ-16 Tri-tert-butylnaphthalenesulfonic acid sodium salt

RZ-17 C₁₇H₃₃CON(CH₃)CH₂CH₂SO₃Na

RZ-18 C₁₂H₂₅-C₆H₄SO₃·NH₄

(B) Resist and method for producing the same

When a resist is used as the resin layer, the resin layer preferably contains a photopolymerization initiator, a thermal curing agent, a colorant, inorganic particles (filler), a gelling agent, and the like as necessary in addition to the resin composition.

(photopolymerization initiator)

Examples of the photopolymerization initiator include a photo radical initiator and a photo cation polymerization initiator. In the present invention, as the photopolymerization initiator, a photo radical polymerization initiator can be used. Any compound that generates a radical by light, laser, electron beam, or the like and initiates a radical polymerization reaction can be used as the photo radical polymerization initiator.

Examples of the photo-radical polymerization initiator include benzoin and benzoin alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether, acetophenones such as acetophenone, 2-dimethoxy-2-phenylacetophenone, 2-diethoxy-2-phenylacetophenone and 1, 1-dichloroacetophenone; 2-methyl-1- [4- (methylthio) phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2- (dimethylamino) -2- [ (4-methylphenyl) methyl]-1- [4- (4-morpholinyl) phenyl]Aminoacetophenones such as-1-butanone and N, N-dimethylaminoacetophenone; anthraquinones such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone and 1-chloroanthraquinone; thioxanthones such as 2, 4-dimethylthioxanthone, 2, 4-diethylthioxanthone, 2-chlorothioxanthone and 2, 4-diisopropylthioxanthone; ketals such as acetophenone dimethyl ketal and benzil dimethyl ketal; 2,4, 5-triarylimidazole dimer; riboflavin tetrabutyrate; 2-mercaptobenzimidazole, 2-mercaptobenzeThiol compounds such as oxazole and 2-mercaptobenzothiazole; organic halogen compounds such as 2,4, 6-tris-s-triazine, 2,2, 2-tribromoethanol, tribromomethylphenyl sulfone and the like; benzophenones or xanthenes such as benzophenone, 4' -bisdiethylaminobenzophenone and the likeXanthones; phosphine oxides such as 2,4, 6-trimethylbenzoyldiphenylphosphine oxide.

One kind of photopolymerization initiator may be used, or two or more kinds may be used in combination.

(Heat curing agent)

Examples of the heat-curing agent include organic acids, amine compounds, amide compounds, hydrazide compounds, imidazole compounds, imidazoline compounds, phenol compounds, urea compounds, polysulfide compounds, and acid anhydrides. As the heat curing agent, a modified polyamine compound such as an amine-epoxy adduct may be used, and a heat curing agent other than these may be used.

(coloring agent)

Examples of the colorant include known and conventional pigments and dyes such as phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, crystal violet, titanium oxide, carbon black, and naphthalene black.

Such colorants may be used alone or in combination of two or more.

(inorganic particles)

Examples of the inorganic particles (filler) include silica, talc, clay, mica, hydrotalcite, alumina, magnesia, aluminum hydroxide, aluminum nitride, and boron nitride.

In addition, from the viewpoint of further improving the thickness accuracy of the resin composition and further making the resin composition more resistant to the generation of voids, it is preferable that the content of the filler in the composition is smaller.

(gelling agent)

Examples of the gelling agent include, but are not limited to, fatty acid alcohols such as stearone (18-tridecanone), 16-trioctadone, 12-tricosanone, and UNILIN425, fatty acid esters, inulin stearate fatty acid dextrin (available from millettia as Rheopearl series), L-glutamic acid derivatives (available from daidzein fine technologies), fatty acid amides (FATTY AMID series, available from kawakawa), glyceryl behenate (Nomcort HK-G, rihiio), and jojoba esters (florester 70 available from pool field products) having a molecular weight of less than 1000.

Specific examples of the gelling agent of the fatty acid amide include FATTY AMID E: erucamide, FATTY AMID T: oleamide, FATTY AMID O-N: hydrogenated tallow Amide (available from queen corporation, supra), Nikka Amide AP 1: stearic acid amide (available from chemical company of japan), GP-1: N-lauroyl-L-glutamic acid dibutylamide (available from Aomoto Fine technologies, Inc.), and the like.

From the viewpoint of gelling ability, particularly preferably used gelling agents include compounds having structures represented by the following general formulae (I) and (II).

General formula (I): r₁-CO-R₂

General formula (II): r₃-COO-R₄

[ in the formula, R₁～R₄Each independently represents an alkyl chain which has a straight chain part having 12 or more carbon atoms and may have a branch]

The compound having the structure represented by the above general formula (I) is referred to as a ketone wax, and the compound having the structure represented by the above general formula (II) is referred to as a fatty acid ester.

Examples of the ketone wax include distearyl ketone, dipalmityl ketone, and dilauryl ketone, and examples of the fatty acid ester include stearyl stearate, cetyl palmitate, and behenyl behenate, but are not limited thereto.

By incorporating the above-mentioned gelling agent into the resist, the pinning property of the resin composition can be improved by phase transition of the sol-gel layer by the gelling agent.

(other Components)

The resist may further contain other components. The other components are not particularly limited, and examples thereof include a pigment dispersant, a bonding assistant such as a coupling agent, a leveling agent, an antifoaming agent, and a polymerization inhibitor.

< method for producing resin film >

The resin film used as the resin layer of the present invention may be a film produced by melt casting film formation or a film produced by solution casting film formation.

Hereinafter, a method for producing a polyimide film will be described as an example of a solution casting film-forming method as a method for producing a resin film of the present invention, and other resin films such as an acrylic film can be produced by the same method.

The method for producing the polyimide film preferably includes the steps of: a step of dissolving the polyimide in a solvent to prepare a dope (dope preparation step); a step (casting step) of casting the dope on a support to form a casting film; a step of evaporating the solvent from the casting film on the support (solvent evaporation step); a step (peeling step) of peeling the casting film from the support; a step of drying the obtained film (1 st drying step); a step of stretching the film (stretching step); a step of further drying the stretched film (2 nd drying step); and a step of winding the obtained polyimide film (winding step).

< method for producing resist >

The method for producing a resist used as a resin layer of the present invention preferably includes the steps of: forming a coating film of a resist composition on a substrate; a step of forming a pattern by exposing the coating film; a step of developing the exposed coating film with an alkaline aqueous solution; replacing a basic ionic group bonded to an acid group contained in the developed coating film with a hydrogen ionic group by a cleaning liquid; a step of thermally curing the coating film.

Alternatively, it is preferable to have the following steps: a step of patterning the resist composition by using an ink jet device; and a step of forming a resist pattern by irradiating the resist composition drawn in a pattern with light and applying heat to cure the resist composition.

The metal conductive layer is formed on the resin film or the resist manufactured as described above.

The metal conductive layer can be formed by a vacuum film formation method such as a chemical vapor deposition method (CVD) or a physical vapor deposition method (PVD), and among them, a physical vapor deposition method such as a vacuum deposition method, a sputtering method, an ion plating method, or an electron beam deposition method is preferable.

The metal conductive layer can be formed by applying a composition for forming a metal conductive layer, or when the metal conductive layer is a metal mesh, a fine metal wire can be patterned in a lattice form on a resin film or a resist. Further, the metal conductive layer may be pressure-bonded via an adhesive.

(2) Embodiment 2

An electronic device according to embodiment 2 of the present invention is an electronic device including a resin layer and a metal conductive layer, and an intermediate layer including a compound having a structure represented by the general formula (1), the general formula (6), or the general formula (7) is provided between the resin layer and the metal conductive layer. That is, the electronic device according to embodiment 1 is configured as a layer in which a resin layer and a metal conductive layer are adjacent to each other, and the resin layer contains a resin or a resin precursor and a compound having a structure represented by general formula (1), general formula (6), or general formula (7), and the electronic device according to embodiment 2 is configured as a layer in which an intermediate layer containing a compound having a structure represented by general formula (1), general formula (6), or general formula (7) is provided between the resin layer containing a resin or a resin precursor and the metal conductive layer.

< Metal conductive layer >

The metal conductive layer of the electronic device according to embodiment 2 is the same layer as the metal conductive layer of the electronic device according to embodiment 1.

< resin layer >

The resin layer of the electronic device according to embodiment 2 contains a resin or a resin precursor, and does not contain a compound (nitrogen-containing aromatic heterocyclic compound) having a structure represented by the general formula (1), the general formula (6), or the general formula (7).

The resin layer may contain an additive used in the resin layer of the electronic device according to embodiment 1, in addition to the nitrogen-containing aromatic heterocyclic compound.

< intermediate layer >

The intermediate layer is a layer containing a compound (nitrogen-containing aromatic heterocyclic compound) having a structure represented by the general formula (1), the general formula (6), or the general formula (7), and does not contain the resin or the resin precursor contained in the resin layer.

The intermediate layer may contain other organic low-molecular compounds (UV absorber, antioxidant, etc.) in addition to the nitrogen-containing aromatic heterocyclic compound. The nitrogen-containing aromatic heterocyclic compound is preferably contained as a main component in the intermediate layer, and is preferably contained in a range of 60 to 100 mass% with respect to the entire intermediate layer.

The structures represented by the general formula (1), the general formula (6), or the general formula (7) are the same as the structures described above, and the same applies to the compounds described above.

[ use ]

Examples of the electronic device of the present invention include an organic EL device, a liquid crystal display device (LCD), an organic photoelectric conversion device, a printed circuit board, a thin film transistor, a touch panel, a polarizing plate, and a retardation film. From the viewpoint of more effectively obtaining the effects of the present invention, the present invention can be preferably used for a flexible printed circuit board, an LED lighting device, and a front member for a flexible display.

< Flexible printed substrate >

The flexible printed board can be obtained by pressure-bonding a metal conductive layer to a resin film containing the resin composition of the present invention through an adhesive. Examples of the adhesive used here include acrylic, polyimide, and epoxy adhesives.

In addition, the metal conductive layer thermocompression bonded to the resin film through the adhesive is preferably a copper foil from the viewpoint of cost reduction, but may be another metal foil such as aluminum, gold, silver, nickel, or tin.

< LED lighting device >

The LED lighting device is not particularly limited as long as an LED substrate using a resin film containing the resin composition of the present invention is used, and examples thereof include a double-sided substrate and a composite substrate of an aluminum plate. When heat dissipation is further required along with the increase in luminance of LEDs, the heat dissipation can be improved by combining with an aluminum plate. And also to an organic electroluminescent lighting device using an organic material.

Front panel for flexible display

The front member for a flexible display is not particularly limited as long as it is formed using a resin film containing the resin composition of the present invention. The flexible display on which the front member for a flexible display is mounted is configured by, for example, an organic EL device in which organic functional layers such as a light-emitting layer are laminated on a substrate, a gas barrier film, a film color filter, a polarizing plate having a polarizing plate protective film on one or both surfaces, a film-type touch sensor, and the like, which are laminated in this order. The front surface member for a flexible display is laminated on the film-type touch sensor of the flexible display configured as described above, for example.

The resin film containing the resin composition of the present invention can be used for a substrate of an organic EL device constituting the flexible display, and can also be used for a polarizer protective film of a polarizer constituting the flexible display.

Examples

The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In the examples, "part" or "%" is used, and unless otherwise specified, "part by mass" or "% by mass" is used.

[ example 1]

The polyimide used in the examples was prepared according to the following procedure.

< Synthesis of polyimide A >

A500 mL separable 4-necked flask equipped with a stainless steel anchor stirrer, a nitrogen inlet, and a dean-Stark apparatus was charged with 56.11g (0.18 mol) of 4,4' -oxydiphthalic anhydride (ODPA), 32.09g (0.18 mol) of diethyltoluenediamine (DETDA), 326.87g of gamma-butyrolactone (GBL), 2.85g of pyridine, and 33g of toluene, and the inside of the reaction system was purged with nitrogen. ODPA was dissolved by stirring at 80 ℃ for 30 minutes under a nitrogen stream, and then heated to 180 ℃ for 6 hours with stirring.

The water produced in the reaction was removed as an azeotropic mixture with toluene and pyridine. After the reaction was completed, the reaction mixture was cooled to room temperature to obtain a polyimide solution having a concentration of 20% by mass. The structure of the obtained polyimide is shown in the following formula.

Isopropyl alcohol was added to the polyimide solution, and after stirring, the mixture was cooled to obtain a solid of polyimide a.

[ in the formula, R¹～R³One of them represents a methyl group and two represent an ethyl group]

< Synthesis of polyimide B >

In an apparatus similar to the apparatus used for the synthesis of the polyimide A, 46.80g (0.15 mol) of ODPA46, 38.16g (0.15 mol) of 4,4' -diamino-3, 3',5,5' -tetramethyldiphenylmethane, 2.39g of pyridine, 50g of toluene were charged, and the inside of the reaction system was replaced with nitrogen. ODPA was dissolved by stirring at 80 ℃ for 30 minutes under a nitrogen stream, and then heated to 180 ℃ for 7 hours with stirring.

The water produced in the reaction was removed as an azeotropic mixture with toluene and pyridine. After the reaction, GBL100g was added thereto after cooling to 120 ℃ to obtain a 25 mass% polyimide solution. The structure of the obtained polyimide is shown in the following formula. Isopropyl alcohol was added to the polyimide solution, and after stirring, the mixture was cooled to obtain a solid of polyimide B.

[ wherein n represents the number of repeating units ]

< Synthesis of polyimide C >

Tetracarboxylic dianhydride was produced by the method described on page 1117 of Macromolecules (volume 27) published in 1994 using 5-norbornene-2-spiro-2 '-cyclopentanone-5' -spiro-2 "-5" -norbornene. As a result of producing tetracarboxylic dianhydride in this manner, norbornane-2-spiro- α -cyclopentanone- α' -spiro-2 ″ -norbornane-5, 5 ″,6,6 ″ -tetracarboxylic dianhydride was obtained in a total yield of 88%.

Next, the 30ml three-necked flask was dried by heating with a heat gun. Then, in the three-necked flask which was sufficiently dried, 0.200g (1.00mmol) of 4,4' -diaminodiphenyl ether (solid) was put in, and then 2.7g of dimethylacetamide was added thereto and stirred to dissolve the solid, thereby obtaining a solution.

Then, 0.384g (1.00mmol) of norbornane-2-spiro- α -cyclopentanone- α' -spiro-2 ″ -norbornane-5, 5 ″,6,6 ″ -tetracarboxylic dianhydride thus obtained was added to the solution, and the three-necked flask was placed in an atmosphere of nitrogen, followed by stirring at room temperature (25 ℃) for 12 hours in an atmosphere of nitrogen to obtain a reaction solution containing a polyimide having the following structure. Isopropyl alcohol was added to the polyimide solution, and after stirring, the mixture was cooled to obtain a solid of polyimide C.

< Synthesis of polyimide D >

Tetracarboxylic dianhydride was produced using 5-norbornene-2-spiro-2 '-cyclohexanone-6' -spiro-2 '-5' -norbornene according to the method described on page 1117 of Macromolecules (volume 27), released in 1994. Thus, a tetracarboxylic dianhydride was produced, and as a result, norbornane-2-spiro- α -cyclohexanone- α' -spiro-2 ″ -norbornane-5, 5 ″,6,6 ″ -tetracarboxylic dianhydride was obtained in a total yield of 87%.

Then, 0.398g (1.00mmol) of the norbornane-2-spiro- α -cyclopentanone- α' -spiro-2 ″ -norbornane-5, 5 ″,6,6 ″ -tetracarboxylic dianhydride described above was added to the solution, and the three-necked flask was placed in an atmosphere of nitrogen, and then stirred at room temperature (25 ℃) for 12 hours in an atmosphere of nitrogen to obtain a reaction solution containing a polyimide having the following structure. Isopropyl alcohol was added to the polyimide solution, and after stirring, the mixture was cooled to obtain a solid of polyimide D.

< Synthesis of polyimide E >

In a 4-neck flask equipped with a dry nitrogen introduction tube, a cooler, a toluene-charged dean Stark trap and a stirrer, 25.59g (57.6mmol) of 2, 2-bis (3, 4-dicarboxyphenyl) -1,1,1,3,3, 3-hexafluoropropane dianhydride (the following acid anhydride 1) (manufactured by Dajin industries, Ltd.) was added to N, N-dimethylacetamide (134g), and the mixture was stirred at room temperature under a nitrogen stream.

To this was added 19.2g (60mmol) of 4,4 '-diamino-2, 2' -bis (trifluoromethyl) biphenyl (diamine 1 described below) (manufactured by Dajin industries, Ltd.), and the mixture was stirred at 80 ℃ for 6 hours.

Thereafter, the mixture was heated to 190 ℃ and water produced by imidization was azeotropically distilled off together with toluene. Heating, refluxing and stirring were continued for 6 hours, and as a result, generation of water was not observed. Subsequently, the mixture was heated for 7 hours while distilling off toluene, and after further distilling off toluene, methanol was added thereto for reprecipitation, and the solid was dried to obtain a solid of polyimide E.

< Synthesis of polyimide F >

(polymerization of polyimide precursor)

Polyamic acid was produced using a reaction apparatus equipped with a separable flask made of stainless steel as a reaction vessel, 2 paddles as a stirring apparatus in the separable flask, and a cooling apparatus. In the polymerization reaction, in order to prevent the mixing of water, the nitrogen gas dehydrated through the calcium chloride tube was passed through the tube at a rate of 0.05L/min to conduct the polymerization reaction.

The separable flask was charged with 223.5g of N, N-Dimethylacetamide (DMAC) as a polymerization solvent, and 40.0g (0.125 mol) of diamine 2 as an exemplary diamine was dissolved therein. To this solution, 55.5g (0.125 mol) of acid anhydride 2, which is an exemplary compound of an acid anhydride, was added and completely dissolved by stirring. The charged concentration of the diamine 2 and the acid anhydride 2 in the reaction solution was 30 mass% based on the total reaction solution.

(chemical imidization to polyimide)

DMAC was added to the solution so that the solid content concentration became 15 mass%, and pyridine (pkBH +, 5.17)60g (molar ratio of imidization accelerator/amide group in polyamic acid: 3) was added as an imidization accelerator, and completely dispersed. To the solution after dispersion, 30.6g of acetic anhydride (molar ratio of the dehydrating agent to the amide group in the polyamic acid: 1.2) was added at a rate of 1 minute and 1g, and the mixture was stirred for 30 minutes. After stirring, the internal temperature was raised to 50 ℃ and 5 hours of hot stirring was carried out.

(extraction of polyimide)

The resulting solution was added to methanol to precipitate the objective polyimide powder. The obtained white precipitate was sufficiently washed with methanol, dried by heating to 50 ℃ using a drying apparatus, and taken out as polyimide F. The weight-average molecular weight of the polyimide F was 203000, and the imidization rate was 100%.

< Synthesis of polyimide G >

Polyimide G was synthesized in the same manner as polyimide F except that the following diamine 3 and acid anhydride 3 were used for the synthesis of polyimide F.

< Synthesis of polyimide H >

Polyimide H was synthesized in the same manner as polyimide F except that the following diamine 4 and acid anhydride 4 were used.

< production of polyimide film 101 >

(preparation of mucilage)

A master cement of the following composition was prepared. First, methylene chloride (boiling point: 40 ℃) was added to a pressure dissolution tank. The polyimide a prepared as described above was put into a pressurized dissolving tank containing a solvent while stirring. The resulting mixture was heated and dissolved completely with stirring, and the mixture was filtered using an andex filter paper No.244 manufactured by andex filter co.

(composition of the Main mucilage)

350 parts by mass of methylene chloride

100 parts by mass of polyimide A

0.5 part by mass of a matting agent (AEROSILR812, manufactured by AEROSIL CORPORATION, Japan)

(casting Process)

Next, the dope was uniformly cast on a stainless steel belt support at a temperature of 30 ℃ in a width of 1500mm using an endless belt casting apparatus. The temperature of the stainless steel belt was controlled to 30 ℃.

(peeling step)

On the stainless steel belt support, the solvent was evaporated until the amount of the residual solvent in the cast (cast) film became 75%, and then, peeled off from the stainless steel belt support at a peeling tension of 180N/m.

(stretching Process)

The peeled polyimide film was stretched 1.50 times in the width direction using a clip tenter while applying heat at 200 ℃. The residual solvent amount at the start of stretching was 20% by mass.

(drying Process)

The stretched film was dried at a drying temperature at which the residual solvent content was less than 0.1 mass% with a transport tension of 100N/m and a drying time of 15 minutes, to obtain a polyimide film 101 having a dry film thickness of 50 μm.

(electrode production Process)

A50 mm X50 mm dry polyimide film 101 was cut out and fixed to a substrate holder of a commercially available vacuum deposition apparatus.

The crucible for vapor deposition in the vacuum vapor deposition apparatus was filled with silver in an amount most suitable for production. The crucible for vapor deposition was made of a tantalum resistance heating material.

The vacuum degree is reduced to 1X 10^-4After Pa, the crucible for vapor deposition containing silver was heated by energization at a vapor deposition rateThe polyimide electrode 101 was formed by vapor deposition at 0.1 nm/sec to form an electrode having a thickness of 8 nm.

< production of polyimide film 103 >

A polyimide film 103 and an electrode 103 thereof were produced in the same manner as in the production of the polyimide electrode 101, except that CDBP, which is a comparative compound, was further used to prepare the following main paste.

(composition of the Main mucilage)

< production of polyimide film 107 >

A polyimide film 107 was produced in the same manner as in the production of the polyimide film 101, except that the compound (2) of the present invention was further used to prepare the following master batch. In addition, the electrode 107 was fabricated in the same manner as for the fabrication of the electrode 101, except that the film thickness was set to 10 nm.

(composition of the Main mucilage)

< production of polyimide films 102, 104 to 106, and 108 to 211 >

In the preparation of the polyimide film 107, the polyimide films 102, and 7-47 were prepared in the same manner as shown in tables I and II except that the kinds of polyimides, the amounts of the added compounds (compound (2), compound (12), compound (18), compound (30), compound (32), compound (47), compound (6-5), compound (6-6), compound (6-9), compound (6-18), compound (6-21) to compound (6-32), compound (7-1), compound (7-5), compound (7-12), compound (7-13), compound (7-32), and compound (7-34) to compound (7-47)) and the amounts of the added compounds and the thicknesses of the electrodes were changed as shown in tables I and II below 104 to 106, 108 to 211 and electrodes thereof. The total amount of the additive compound and the polyimide used was 100 parts by mass, and the additive amount in the table indicates the parts by mass.

The polyimide films 102, 146, 147, 158, 169, 180, 197, 202, and 207 in the comparative examples were polyimide films obtained by using the polyimides B to H alone in the same manner as in the production of the polyimide film 101.

[ evaluation ]

< light transmittance (%) >)

The light transmittance at a wavelength of 550nm was measured for each of the polyimide electrodes thus produced.

The light transmittance was measured using a spectrophotometer (U-3300, Hitachi high tech science) with the state without the substrate as a baseline.

< sheet resistance value >

The sheet resistance value [ Ω/sq ] was measured for each of the polyimide electrodes thus produced.

The sheet resistance was measured by a 4-terminal 4-probe method with low current application using a resistivity meter (MCP-T610 manufactured by Mitsubishi chemical analysis).

< change in sheet resistance under high temperature storage >

The obtained sheet resistance values after high-temperature storage were compared with the sheet resistance values measured above, and the rate of change in the resistance values was evaluated based on the following evaluation criteria. The following evaluations 3,4 and 5 were set to levels that were not problematic in practical use.

5: the change rate of the sheet resistance value after high-temperature storage showed a value of less than 5.0%.

4: the change rate of the sheet resistance value after high-temperature storage was 5.0% or more and less than 7.5%.

3: the change rate of the sheet resistance value after high-temperature storage was 7.5% or more and less than 10.0%.

2: the change rate of the sheet resistance value after high-temperature storage was 10.0% or more.

1: the sheet resistance value after high-temperature storage could not be measured.

[ Table 1]

TABLE 1-1

[ Table 2]

Tables 1 to 2

[ Table 3]

TABLE II

From the above results, it is understood that the polyimide film using the compound of the present invention is superior to the polyimide film of the comparative example in light transmittance, sheet resistance value, and change in sheet resistance value under high-temperature storage.

[ example 2]

An acrylic film and an electrode thereof were produced and evaluated in the same manner as in example 1, except that the acrylic resin used in example was prepared and an acrylic film was formed by the following method.

< production of acrylic film 201 >

(composition of the Main mucilage)

Acrylic resin (Hitaroid7927, Hitachi chemical Co., Ltd.) 90 parts by mass

After preparing the main paste having the above composition, the coating liquid was applied to a glass substrate to form a coating film, dried at 70 ℃, and then purged with nitrogen gas to an atmosphere having an oxygen concentration of 1.0 vol% or less while using an ultraviolet lamp with the illuminance of the irradiated portion set at 300mW/cm²The irradiation dose was set to 0.3J/cm²The coated film is cured to obtain the acrylic film 201.

(electrode production Process)

A50 mm X50 mm dried acrylic film 201 was cut out and fixed to a substrate holder of a commercially available vacuum deposition apparatus.

The vacuum degree is reduced to 1X 10^-4After Pa, the crucible for vapor deposition containing silver was heated by energization, and vapor deposition was performed at a vapor deposition rate of 0.1 nm/sec to form an electrode having a film thickness of 8nm, thereby preparing an electrode 201.

< production of acrylic film 202 >

An acrylic film 202 and an electrode thereof were produced in the same manner as described above except that the following main paste was prepared in the production of the acrylic film 201.

(composition of the Main mucilage)

Acrylic resin (Hitaroid7927, Hitachi chemical Co., Ltd.) 90 parts by mass of Compound (2) 10 parts by mass

< production of acrylic films 203-207, 222 and 223 >

Acrylic films 203 to 207, 222 and 223 and electrodes thereof were produced in the same manner as described above except that the compound (2) was replaced with the following compound in the production of the acrylic film 202.

Acrylic film 203 … Compound (12)

Acrylic film 204 … Compound (18)

Acrylic film 205 … Compound (30)

Acrylic film 206 … Compound (32)

Acrylic film 207 … Compound (47)

Acrylic film 222 … Compound (6-9)

Acrylic film 223 … Compound (7-13)

< production of acrylic film 208 >

The acrylic film 208 and the electrode thereof are produced in the same manner as described above, except that the acrylic film is formed by the following method in the production of the acrylic electrode 201.

(composition of the Main mucilage)

Diethylene glycol monoethyl ether acetate 80 parts by mass

Styrene acrylic resin (YL-1098, available from Astro-Co., Ltd.) 90 parts by mass

After preparing the main syrup having the above composition, the coating liquid is coated on a glass substrate to form a coating film, which is dried to obtain the acrylic film 208.

< production of acrylic film 209 >

An acrylic film 209 and an electrode thereof were produced in the same manner as in the production of the acrylic electrode 208 except that the following main paste was prepared.

(composition of the Main mucilage)

Diethylene glycol monoethyl ether acetate 80 parts by mass

Styrene acrylic resin (YL-1098, available from Astro PMC Co., Ltd.) 90 parts by mass of Compound (2) 10 parts by mass

< production of acrylic films 210 to 214, 224, 225 >

The acrylic films 210 to 214, 224, and 225 and the electrodes thereof were produced in the same manner except that the compound (2) was replaced with the following compound in the production of the acrylic film 209.

Acrylic film 210 … Compound (12)

Acrylic film 211 … Compound (18)

Acrylic film 212 … Compound (30)

Acrylic film 213 … Compound (32)

Acrylic film 214 … Compound (47)

Acrylic film 224 … Compound (6-9)

Acrylic film 225 … Compound (7-13)

< production of acrylic film 215 >

An acrylic film 215 and an electrode thereof were produced in the same manner as described above, except that an acrylic film was formed by the following method in the production of the acrylic electrode 201.

(composition of the Main mucilage)

150 parts by mass of methyl ethyl ketone

Acrylic resin (Hitaroid 7975, Hitachi chemical Co., Ltd.) 90 parts by mass

After preparing the main paste of the above composition, the coating liquid is coated on the glass substrateA coating film was formed, dried at 70 ℃, and then subjected to nitrogen purging to an atmosphere having an oxygen concentration of 1.0 vol% or less while using an ultraviolet lamp to set the illuminance of an irradiation part at 300mW/cm²The irradiation dose was set to 0.3J/cm²The coated film was cured to obtain an acrylic film 215.

< production of acrylic acid film 216 >

An acrylic film 216 and an electrode thereof were produced in the same manner as in the production of the acrylic electrode 215, except that the following main paste was prepared.

(composition of the Main mucilage)

150 parts by mass of methyl ethyl ketone

Acrylic resin (Hitaroid 7975, Hitachi chemical Co., Ltd.) 90 parts by mass of Compound (2) 10 parts by mass

< production of acrylic films 217 to 221, 226 and 227 >

The acrylic films 217 to 221, 226 and 227 and the electrodes thereof were produced in the same manner except that the compound (2) was replaced with the following compound in the production of the acrylic film 216.

Acrylic film 217 … Compound (12)

Acrylic film 218 … Compound (18)

Acrylic film 219 … Compound (30)

Acrylic film 220 … Compound (32)

Acrylic film 221 … Compound (47)

Acrylic film 226 … Compound (6-9)

Acrylic film 227 … Compound (7-13)

The sheet resistance at the initial stage of the production and the sheet resistance at 80 ℃ for 10 hours were measured for the acrylic film electrode produced above. The resistance value change rates were evaluated by comparing the sheet resistance values before and after the high-temperature storage, and the change rates of the electrodes using the acrylic films 202 to 207, 209 to 214, 216 to 221, and 222 to 227 of the present invention were within 7%, and the storage stability was excellent, and the change rates of the resistance values were found to vary by 10% or more in comparative examples 201, 208, and 215.

[ example 3]

Using the polyimide film produced in example 1, a polyimide electrode was obtained according to the following configuration.

< production of polyimide electrode 301 >

(electrode production Process)

A50 mm X50 mm dry polyimide film 101 was cut out and fixed to a substrate holder of a commercially available vacuum deposition apparatus.

< production of polyimide electrodes 302 to 324 >

Polyimide electrodes 302 to 324 were produced in the same manner as in the production of the polyimide electrode 301, except that the polyimide film as the substrate was changed as shown in table III below.

< production of polyimide electrodes 325 to 378 >

In the production of the polyimide electrodes 301, polyimide electrodes 325 to 378 were produced in the same manner as in table IV below, except that the electrodes were changed to copper or titanium and the polyimide film as the substrate was changed.

[ evaluation ]

< change in sheet resistance under high temperature storage >

The polyimide electrodes 301 to 378 prepared above were measured for sheet resistance at the initial stage of film formation and sheet resistance at 80 ℃ for 10 hours.

The sheet resistance after the high-temperature storage and at the initial stage of film formation were compared, and the rate of change in the resistance value was evaluated based on the following evaluation criteria. The following evaluations 3,4 and 5 were set to levels that were practically free from problems.

5: the change rate of the sheet resistance value after high-temperature storage showed a value of less than 5.0%

4: the change rate of the sheet resistance value after high-temperature storage is 5.0% or more and less than 7.5%

3: the change rate of the sheet resistance value after high-temperature storage is 7.5% or more and less than 10.0%

2: the change rate of the sheet resistance value after high-temperature storage shows a value of 10.0% or more

1: the sheet resistance after high temperature storage could not be measured

< adhesion >

The obtained polyimide electrodes 301 to 378 were used to perform a tape peeling test. The tape peeling test was carried out according to JIS K5600.

6 strips were cut at a depth of a base material which reached the base material but was not cut, in the longitudinal direction, and 6 cuts were cut in the transverse direction at intervals of 1mm in width using a cutter, thereby forming 25 lattices in total of 5 lattices × 5 lattices. A commercially available cellophane tape (24mm wide, manufactured by Nichiban corporation) was strongly pressed against the lattice portion with a finger pad, and one end of the tape was peeled off at an angle of 60 ° at one stroke, and the state of the remaining lattice was evaluated based on the following evaluation criteria.

Very good: no change (good)

O: the entire lattice was not peeled off, but a part of the lattice was peeled off. (practically no problem)

And (delta): peeling 1-5 lattices. (not practical)

X: peeling more than 6 lattices. (not practical)

[ Table 4]

TABLE III

[ Table 5]

TABLE IV

From the above results, it was found that the polyimide electrode using the compound of the present invention is superior to the polyimide electrode of the comparative example in the change in sheet resistance value under high-temperature storage.

[ example 4]

A polyimide electrode was obtained according to the following configuration using a paste having the same composition as that of the polyimide film used in example 1.

< production of Metal film >

A glass substrate of 150mm X150 mm and 0.7mm in thickness was fixed to a substrate holder of a commercially available vacuum deposition apparatus.

The vacuum degree is reduced to 1X 10^-4After Pa, the crucible for vapor deposition containing silver was heated by energization, and vapor deposition was carried out at a vapor deposition rate of 0.1 nm/sec to form an electrode having a thickness of 50 nm.

< production of polyimide electrode 401 >

On the glass substrate with silver film prepared as described above, a polyimide electrode 401 was prepared using a paste having the same composition as that of the polyimide film 101 used in example 1.

The assembly base was assembled such that the height of the glass substrate was the same as the surrounding height, and then, a polyimide electrode 401 was fabricated on the silver film-coated glass substrate by using the main paste composition of the polyimide film 101 and a commercially available film dispenser, followed by drying and curing steps.

< production of polyimide electrodes 402 to 415 >

In the production of the polyimide electrodes 401, polyimide electrodes 402 to 415 were produced in the same manner except that the polyimide film as the substrate was changed as shown in table V below.

[ evaluation ]

< change in sheet resistance under high temperature storage >

The polyimide electrodes 401 to 415 produced as described above were measured for sheet resistance at the initial stage of film formation and sheet resistance at 80 ℃ for 10 hours.

The sheet resistance value was measured by an eddy current method using a resistance measuring instrument (EC-80, NAPSON Co., Ltd.).

5: the change rate of the sheet resistance value after high-temperature storage showed a value of less than 5.0%.

4: the change rate of the sheet resistance value after high-temperature storage was 5.0% or more and less than 7.5%.

3: the change rate of the sheet resistance value after high-temperature storage was 7.5% or more and less than 10.0%.

2: the change rate of the sheet resistance value after high-temperature storage was 10.0% or more.

1: the sheet resistance value after high-temperature storage could not be measured.

[ Table 6]

TABLE V

[ example 5]

Organic EL devices were fabricated using the polyimide films 101 to 211 produced in example 1, according to the following configurations.

< manufacture of organic EL element >

The polyimide films 101 to 107 and 109 to 211 prepared in example 1 were fixed to a substrate holder of a commercially available vacuum vapor deposition apparatus and used as substrates.

The evaporation crucibles in the respective vacuum evaporation apparatuses are each filled with the constituent material of each layer in an amount optimal for the production of the elements. The crucible for vapor deposition was made of a resistance heating material made of molybdenum or tungsten.

Reducing the vacuum degree to 1 × 10-⁴After Pa, the crucible for vapor deposition containing Ag was heated by energization, and vapor deposition was carried out on the polyimide film substrate at a vapor deposition rate of 0.1 nm/sec to form an anode having a layer thickness of 100 nm.

HAT-CN (1,4,5,8,9, 12-hexaazatriphenylhexacyano-nitrile) was deposited on the Ag electrode at a deposition rate of 0.1 nm/sec to form a hole injection layer having a layer thickness of 10 nm.

Next, α -NPD (4,4' -bis [ N- (1-naphthyl) -N-phenylamino ] biphenyl) was deposited on the hole injection layer at a deposition rate of 0.1 nm/sec to form a hole transport layer having a layer thickness of 40 nm.

The following CBP as a host compound and the following Ir (ppy) as a light emitting dopant₃The co-deposition was carried out at a deposition rate of 0.1 nm/sec so as to obtain 90% and 10% by volume, respectively, to form a light-emitting layer having a layer thickness of 30 nm.

Next, Alq is added₃(tris (8-hydroxyquinoline) aluminum) and LiF were deposited on the light-emitting layer at a deposition rate of 0.1 nm/sec to form an electron-transporting layer having a thickness of 40nm, respectively.

Further, LiQ (8-hydroxyquinoline lithium) was formed in a film thickness of 2nm, and then aluminum was deposited at 100nm to form a cathode. Then, 200nm of silicon nitride was deposited on the cathode by CVD to form an insulating film, thereby producing an organic EL element unit.

Next, a glass barrier film was formed using a polyethylene terephthalate film having a thickness of 20 μm and a gas barrier layer, and a sealing unit was prepared in which a thermosetting liquid adhesive (epoxy resin) was applied as a sealing layer on one surface of the gas barrier film to a thickness of 25 μm.

Next, the organic EL element unit and the sealing unit formed to the transparent substrate to the insulating layer were pressed and held for 5 minutes under reduced pressure conditions of 90 ℃ and 0.1 MPa. Next, the laminate was returned to the atmospheric pressure environment, and the adhesive was further cured by heating at 90 ℃ for 30 minutes to produce an organic EL device.

The front luminance of the organic EL element manufactured as described above when a DC voltage of 6V was applied was 1200cd/m². The front brightness was determined as follows: a spectral radiance meter CS-1000 manufactured by Konika Mingta is used, for the front brightness of a 2-degree visual angle, the optical axis of the spectral radiance meter is consistent with the normal line of a self-luminous surface, the brightness of visible light with the wavelength of 430-480 nm is measured, and the integral intensity is taken.

Further, the organic EL element thus fabricated was heated at 80 ℃ and 2.5mA/cm²The voltage measured under the constant current condition of (1) was measured as the driving voltage immediately after the start of light emission and as the driving voltage 100 hours after the start of light emission.

As a result of comparing the obtained driving voltages before and after high-temperature storage and evaluating the rate of change in the driving voltage, the rate of change in the driving voltage of the devices using the polyimide films 105 to 107, 109 to 145, 148 to 157, 159 to 168, 170 to 179, 181 to 186, 188 to 191, 193 to 196, 198 to 201, 203 to 206, and 208 to 211 of the present invention was within 5%, and the storage stability was excellent, and the variation of the rate of change in the driving voltage was found to be 10% or more in comparative examples 101 to 104, 146, 147, 158, 169, 180, 197, 202, and 207.

[ example 6]

Resin films and electrodes thereof described in table VI were prepared and evaluated in the same manner as in example 1, except that the resin films used in the examples were prepared and the resin films were formed by the following methods.

< production of TAC film 601 >

TAC film 601 and electrode 601 thereof are produced in the same manner as in example 1, except that the following main dope is prepared in producing TAC film 601.

(composition of the Main mucilage)

350 parts by mass of methylene chloride

100 parts by mass of triacetyl cellulose (TAC)

< production of polyimide electrode 601 >

(electrode production Process)

A dried TAC film 601 of 50mm X50 mm was cut out and fixed on a substrate holder of a commercially available vacuum deposition apparatus.

< production of TAC film 602 >

TAC film 602 and electrodes thereof were produced in the same manner as described above except that the following main dope was prepared in the production of the acrylic film 601.

(composition of the Main mucilage)

350 parts by mass of methylene chloride

90 parts by mass of triacetyl cellulose (TAC)

10 parts by mass of Compound (30)

< production of resin films 603 to 632 >

Resin films 603 to 632 and electrodes thereof were produced in the same manner as described above with the exception that the main pastes shown in table VI were prepared in the production of TAC film 602.

(resin)

Polycarbonate resin (PC)

Cycloolefin resin (ZEONOR)

Polyester resin (polyethylene terephthalate (PET)

Melamine resin

[ evaluation ]

< change in sheet resistance under high temperature storage >

The resin electrodes 601 to 632 produced as described above were measured for the sheet resistance value at the initial stage of film formation and the sheet resistance value at 80 ℃ for 10 hours.

5: the change rate of the sheet resistance value after high-temperature storage showed a value of less than 5.0%

4: the change rate of the sheet resistance value after high-temperature storage is 5.0% or more and less than 7.5%

3: the change rate of the sheet resistance value after high-temperature storage is 7.5% or more and less than 10.0%

2: the change rate of the sheet resistance value after high-temperature storage shows a value of 10.0% or more

1: the sheet resistance value after high-temperature storage could not be measured.

[ Table 7]

TABLE VI

From the above results, it is understood that the electrode using the compound of the present invention is superior to the electrode of the comparative example in the change in sheet resistance value under high-temperature storage.

[ example 7]

A copper-clad laminate (manufactured by Sunhayato) (hereinafter also referred to as a copper substrate) was subjected to a surface treatment using a stripping solution, and then a laminate was obtained according to the following procedure.

< production of laminate 701 >

(composition of the Main mucilage)

350 parts by mass of methylene chloride

100 parts by mass of the polyimide A

0.5 part by mass of a matting agent (AEROSILR812, manufactured by AEROSIL CORPORATION, Japan)

After preparing the main paste having the above composition, a coating liquid was applied to the surface-treated copper substrate to form a coating film, and the coating film was dried at a drying temperature at which the residual solvent was less than 0.1 mass%, to obtain a laminate 701 having a dry film thickness of 20 μm.

< preparation of laminate 727 >

(composition of the Main mucilage)

Acrylic resin (Hitaroid 7927) 90 parts by mass

After preparing the main slurry having the above composition, the coating liquid was applied to a surface-treated copper substrate to form a coating film, and after drying at 70 ℃, the coating film was subjected to nitrogen purging until the oxygen concentration was 1.0 vol% or less, while using an ultraviolet lamp, the illuminance of the irradiated portion was set to 300mW/cm²The irradiation dose was set to 0.3J/cm²The coating film was cured to obtain a laminate 727 having a dry film thickness of 20 μm.

< production of laminate 754 >

(composition of the Main mucilage)

After preparing the main paste having the above composition, the coating liquid is applied to the surface-treated copper substrate to form a coating film, and the coating film is dried at 150 ℃ to obtain a laminate 754 having a dry film thickness of 20 μm.

< production of laminates 702 to 706, 728 to 753, and 755 to 780 >

Laminates 702 to 706, 728 to 753, and 755 to 780 were produced in the same manner except that the amounts of the resin and the additive compound were changed as shown in table VII below. In the compound to be added, the amount of solid components in the main cement used was 100 parts by mass, and the amount added in the table indicates the parts by mass.

The resins shown in the table are as follows.

Polyimide (I): polyimide A

Acrylic acid: hitaroid7927

And (3) epoxy: epoxy resin (25) HP-5000: methoxynaphthalenedimethylene type epoxy resin, available from DI C Ltd, epoxy equivalent of 250

[ evaluation ]

< peel strength at high temperature storage >

The respective laminates thus prepared were measured for peel strength at the initial stage of film formation and peel strength at a temperature of 80 ℃ for 168 hours.

The peel strength was measured by using SAICAS (manufactured by Daipla Wintes, NN-04T) in a constant load mode.

The laminates 701, 727 and 754 as comparative examples were each set to 100%, and the measured values of the examples and comparative examples were compared and evaluated.

[ Table 8]

TABLE VII-1

[ Table 9]

TABLE VII-2

From the above results, it is understood that the laminate using the compound of the present invention is superior to the laminate of the comparative example in adhesion after storage at high temperature.

[ example 8]

A solder resist solution (hereinafter, also referred to as SR) as a commercial product was prepared from a combination of a resin and an additive compound (SR composition) shown in Table VIII below, and the solution was applied in a comb pattern (line width/space width: 75/75 μm) to obtain cured products 801 to 860 having a thickness of 30 μm through a curing step. The curing process is based on the technical data of each SR.

SR1 … SR-4000 HT-1/CA-40 HT-1 (manufactured by SUN INK MAKING CO., LTD.)

The SR1 contains acrylic resin, epoxy resin, and the like.

SR2 … PSR-4000 LEW3/CA-40 LEW3 (manufactured by Suzuki ink Co., Ltd.)

The SR2 contains acrylic resin, epoxy resin, and the like.

SR3 … PLAS FINE PSR-310 (product of Strobiluros chemical Co., Ltd.) (ultraviolet-curing solder resist)

[ evaluation ]

< surface curability > (UV curability)

The surface of the cured product obtained above was touched with a finger to evaluate the tackiness (stickiness).

Good: without stickiness

And (delta): slightly sticky with residual fingerprints

X: stickiness

Hardness of pencil

The cured product obtained above was left to stand at 25 ℃ and 60% RH for 24 hours, and then the pencil hardness of the surface was measured according to JIS-K-5400 to evaluate the pencil hardness on the following scale.

Good: pencil hardness of 2H or more

And (delta): pencil hardness B, F, H

X: pencil hardness of 2B or less

< storage stability >

After each SR before curing was adjusted, the viscosity at room temperature was measured every 1 hour by using a dynamic viscoelasticity measuring apparatus. The time at which the viscosity reached 2 times the initial value was measured as the usable time. The usable time exceeding 2 hours was judged to be "good," and the usable time within 2 hours was judged to be "poor.

< confirmation of insulating Property of solder resist >

After measuring the initial insulation resistance of the cured products 801 to 860, a humidification test was performed for 1500 hours under conditions of 85 ℃ and 85% relative temperature and 75V DC application. After the humidification test, the insulation resistance was measured again, and the insulation properties of the solder resist were evaluated in the following scale.

Good: insulation resistance change is less than 1 × 10 from initial stage²Ω

X: insulation resistance change was 1X 10 from the initial stage²Omega or more

[ Table 10]

TABLE VIII-1

[ Table 11]

TABLE VIII-2

From the above results, it is understood that a cured product using the compound of the present invention is superior to the cured product of the comparative example in the insulating property of the solder resist and does not impair the resist characteristics.

[ example 9]

A copper-clad laminate (manufactured by Sunhayato) (hereinafter also referred to as a copper substrate) was subjected to a surface treatment with a stripping solution, and then a laminate was obtained according to the following procedure.

< production of laminate 901 >

(formation of resin layer)

350 parts by mass of methylene chloride

100 parts by mass of the polyimide A

0.5 part by mass of a matting agent (AEROSILR812, manufactured by AEROSIL CORPORATION, Japan)

After preparing the main paste having the above composition, the coating liquid was applied to the surface-treated copper substrate to form a coating film, and the coating film was dried at a drying temperature at which the residual solvent was less than 0.1 mass%, to obtain a laminate 901 having a resin layer with a dry film thickness of 20 μm.

< preparation of laminate 902 >

(formation of intermediate layer)

After dissolving 5mg of compound (12) in 1mL of toluene, the resulting solution was applied to a surface-treated copper substrate by spin coating (3000rpm, 30 seconds) to form an intermediate layer having a dry film thickness of 30 nm.

(formation of resin layer)

After preparing a main slurry having the same composition as that of the formation of the resin layer in the production of the laminate 901, a coating solution was applied to the intermediate layer to form a coating film, and the coating film was dried at a drying temperature at which the residual solvent was less than 0.1 mass% to form a resin layer, thereby obtaining a laminate 902 having a dry film thickness of 20 μm of the intermediate layer and the resin layer.

< production of laminate 910 >

(formation of resin layer)

Acrylic resin (Hitaroid 7927) 90 parts by mass

< production of laminate 911 >

(formation of intermediate layer)

After 5mg of the compound (2) was dissolved in 1mL of toluene, the resulting solution was applied to a surface-treated copper substrate by a spin coating method (3000rpm, 30 seconds) to form an intermediate layer having a dry film thickness of 30 nm.

(formation of resin layer)

After preparing a main slurry having the same composition as that of the formation of the resin layer in the production of the laminate 910, a coating solution was applied to the intermediate layer to form a coating film, and the coating film was dried at a drying temperature at which the residual solvent was less than 0.1 mass% to form a resin layer, thereby obtaining a laminate 911 having a dry film thickness of 20 μm of the intermediate layer and the resin layer.

< production of laminate 917 >

(formation of resin layer)

After preparing the master slurry having the above composition, the coating liquid was applied to the surface-treated copper substrate to form a coating film, and the coating film was dried at 150 ℃ to obtain a laminate 917 having a dry film thickness of 20 μm.

< production of laminate 918 >

(formation of intermediate layer)

After dissolving 5mg of compound (51) in 1mL of toluene, the resulting solution was applied to a surface-treated copper substrate by spin coating (3000rpm, 30 seconds) to form an intermediate layer having a dry film thickness of 30 nm.

(formation of resin layer)

After preparing a main slurry having the same composition as that of the formation of the resin layer in the production of the laminate 917, a coating solution was applied to the intermediate layer to form a coating film, and the coating film was dried at a drying temperature at which the residual solvent was less than 0.1 mass% to form a resin layer, thereby obtaining a laminate 918 having a dry film thickness of 20 μm of the intermediate layer and the resin layer.

< production of laminates 903 to 909, 912 to 916, and 919 to 923 >

Laminates 903 to 909, 912 to 916, and 919 to 923 were produced in the same manner except that the resin and the additive compound were changed as shown in table IX below.

The resins shown in the table are as follows.

Polyimide (I): polyimide A

Acrylic acid: hitaroid7927

And (3) epoxy: epoxy resin (25) HP-5000: methoxynaphthalenedimethylene type epoxy resin having an epoxy equivalent of 250, available from DIC Ltd

[ evaluation ]

< peel strength at high temperature storage >

The respective laminates thus prepared were measured for peel strength at the initial stage of film formation and peel strength at a temperature of 80 ℃ for 168 hours.

The peel strength was measured by using SAICAS (manufactured by Daipra Wintes, NN-04T) in a constant load mode.

The laminates 901, 910, and 917 as comparative examples were each set to 100%, and the measured values of the examples and comparative examples were compared and evaluated.

[ Table 12]

TABLE IX

Industrial applicability

The present invention can be used for a resin composition and an electronic device that have excellent adhesion to a metal conductive layer, stability during high-temperature storage, and light transmittance.

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