JPH1124261A - Photosensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photosensitive resin compsn. showing high heat resistance and low moisture absorption which can be easily handled and processed, by using a hardened material of a resin compsn. having specified relative dielectric const., saturation moisture absorption rate and initiating temp. of thermal decomposition by irradiation of light. SOLUTION: As for a photosensitive resin compsn. which is changed into insoluble by irradiation of activating light, the hardened material of this photosensitive resin compsn. by irradiation of light has 2.5 to 3.8 relative dielectric const., 0.3 to 1.0% saturation moisture absorption rate and >=400 deg.C initiating temp. of thermal decomposition. The obtd. photosensitive film is an insulating film having high fluidity and excellent resin filling property between wirings compared to a conventional polyimide adhesive film. Since the obtd. film has photosensitivity, via holes can be easily formed and the film can be used for electronic parts having high density of wirings. Moreover, the film has excellent characteristics as an insulating layer such as high heat resistance, low moisture absorption and low dielectric const. Namely, the obtd. photosensitive film is easily handled and can be used to form a multilayered print board with fine wirings.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electric and electronic device which has high heat resistance and low moisture absorption, exhibits a low dielectric constant, is effective as an insulating material for electric and electronic parts, and can form a fine pattern. Provided is a photosensitive resin composition capable of miniaturizing parts.

[0002]

2. Description of the Related Art Polyimide has excellent heat resistance.
It has been widely used as an insulator for electronic and electrical components. A material obtained by imparting photosensitivity to this polyimide is mainly applied to a passivation film for a semiconductor or the like. But,
These photosensitive resins are usually supplied with a varnish and must undergo a process such as spin coating, and require a high-temperature treatment for complete curing. It has not been used in the field of parts.

A film obtained by blending a polyimide having a low softening point and a polyfunctional maleimide can be formed into a flexible film, which is easy to handle, and the reaction temperature is not as high as that of polyimide. A proposal has been made for application to an interlayer insulating film or the like (Japanese Patent Laid-Open No. 59-179558).
No., JP-A-2-124971). However, there is no example of imparting photosensitivity with such a material. That is, in order to produce a high-density multilayer wiring board, a via hole for conducting the upper and lower wirings must be formed by laser or dry etching with the above-mentioned material. Also, because it contains a large amount of high-molecular-weight, high-viscosity polyimide, if the fluidity of the film is poor and there are fine wiring etc. in the lower layer,
The space between the wirings cannot be filled, voids are generated, and electrical defects are formed.

On the other hand, insulating materials for electronic and electrical parts are required to have lower relative dielectric constant and lower moisture absorption in addition to heat resistance. Benzocyclobutene is a material that can impart photosensitivity with such a material, but it does not form a flexible film, and it is necessary to form a resin layer by printing or spin coating. Also, its heat resistance is inferior to the above-mentioned polyimides and the like.

[0005]

In the above prior art, not only high heat resistance, low dielectric constant, low moisture absorption and excellent characteristics as an electronic component insulating layer, but also easy handling and high density wiring board There is a problem that it is not compatible with the fact that it can be easily provided, and there is a problem to be improved here.

For example, a film obtained by blending a polyimide having a low softening point and a polyfunctional maleimide becomes a flexible film and has excellent heat resistance when cured.
Laser formation of via holes to conduct the upper and lower wiring,
Alternatively, there is a problem that the etching must be performed by dry etching or the like via a mask, and that the lower wiring pattern needs to be roughened in order to prevent defects from being formed in the insulating layer.

Benzocyclobutene, which has excellent electrical properties,
It is not necessary to form a flexible film, and it is necessary to form a resin layer by printing or spin coating.

Accordingly, an object of the present invention is to provide a photosensitive resin composition which is easy to handle and process and has high heat resistance, low moisture absorption, and low dielectric constant. An object of the present invention is to provide a method for easily producing a multilayer wiring board having excellent characteristics and high density.

[0009]

The feature of the photosensitive resin composition according to the present invention that achieves the above object is that (1) a photosensitive resin composition which is insolubilized by activating light is irradiated with light from the resin composition. Has a relative dielectric constant of 2.5 to 3.8,
Saturated moisture absorption of 0.3 to 1.0%, thermal decomposition onset temperature of 400
C. or higher.

Another characteristic is that (2) the photosensitive resin composition becomes a self-standing film, and when the film is heated, it flows and can be molded.

More specifically, (3) the photosensitive resin composition comprises (A) a polymer having a quinoline ring, (B) a polyfunctional maleimide, and (C) a reaction with a maleimide compound by light or polymerization of the maleimide compound. A photosensitive resin composition having the characteristics described above, comprising a compound.

Further, (4) a general formula [Chem. 11] in the structure (A) of the photosensitive resin composition.

[0013]

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A polymer containing a quinoline ring represented by the formula:
(B) a general formula [Formula 12],

[0015]

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(In the formula, Ar represents a divalent organic group containing at least two carbon atoms.) A photosensitive resin composition using a resin composition containing a bismaleimide compound represented by the following formula as an essential component: .

Alternatively, (5) (A) a polymer containing a quinoline ring is represented by the following general formula:

[0018]

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[0019]

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(Wherein R ¹ and R ² each independently represent an alkyl group, an aryl group, an alkoxy group, an allyloxy group,
Formyl group (-COR), ester group (-COR or -OCOR), amide group (-NRCOR or -CO
NRR), a heteroaryl group, a cyano group, or a divalent hydrocarbon group which may include an unsaturated bond formed by connecting two groups, wherein R is a hydrogen atom, an alkyl group, or a heteroaryl group ), M and n are each independently an integer of 0 to 5, X is a chemical bond, -O
-, - S -, - CO -, - SO -, - SO 2 -, - A
-, (OA) _q -O- or -Q- (where q is an integer of 1 to 3, and A is -Ar- (arylene group),-
Hr- (heteroarylene group), -Ar-O-Ar-,-
CO-Ar-, -Ar-S-Ar-, -Ar-SO-A
r-, -Ar- or -Ar-Q-Ar-, wherein Q is

[0021]

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(L ¹ and L ² represent a methyl group, a trifluoromethyl group or a divalent hydrocarbon group which may contain an unsaturated bond formed by linking two) and Z ¹
And Z ² each independently represent a chemical bond or an arylene group, and Y represents -O- or -O-A-O-. )
A photosensitive resin composition using a polymer containing a quinoline ring represented by the formula:

Alternatively, (6) the polyfunctional maleimide (B) in the photosensitive resin composition is represented by the general formula [Chem. 16] or [Chem. 17]

[0024]

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[0025]

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(Wherein R ₁ to R ₁₀ are H, CH ₃ , CH ₂
CH ₃ , F, and CF ₃ are shown and may be different from each other. n
May be 0 or an integer of 1 to 4 which may be different from each other. A photosensitive resin composition characterized by using a resin composition represented by a bismaleimide compound having in the structure thereof.

(7) In the photosensitive resin composition, (C) a compound capable of forming a polymer by reacting with a maleimide compound by light is represented by the following general formula:

[0028]

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(Wherein R ₁₁ and R ₁₂ are H, having 1 to 1 carbon atoms)
5 represents an alkyl group or an alkoxy group, which may be different from each other. A) a photosensitive resin composition which is a benzophenone compound represented by the formula:

Further, (8) in the photosensitive resin composition, (C) a compound capable of forming a polymer by reacting with a maleimide compound by light is represented by the following general formulas:

[0031]

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[0032]

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[0033] (wherein R _11, R ₁₂ and R ₁₃ are H, alkyl group having 1 to 15 carbon atoms, an alkoxy group, may be different from each other. Further, R ₁₄ is H, 1 to 3 carbon atoms A photosensitive resin composition which is a mixture of a benzophenone compound represented by the following formula:

(9) The polymerizable compound selected from (C) aromatic diamine, epoxy compound, polybutadiene compound and the like is added to the photosensitive resin composition shown in the above (3) to (4). A photosensitive resin composition.

Hereinafter, the present invention will be described in more detail.

(A) As a result of repeated studies on a polymer containing a quinoline ring represented by the above general formula [Formula 11],
(A) a polymer containing a quinoline ring having the structure of the above-mentioned general formula [Chemical formula 13] and (A) [Chemical formula 14], and (B)
It has been found that when a bismaleimide compound having the structure of the general formula [Chemical Formula 12] is combined, a self-standing film excellent in mechanical properties and excellent handling is obtained even though it is an uncured resin. This film can be flowed by heating and melt-pressed. Therefore, it is possible to fill the gap between the fine wirings in the lower layer without voids, and to adhere to the adherend to obtain excellent adhesiveness, and to provide a resin composition having excellent mechanical properties.

In particular, as a result of repeated studies on (B) the structure of the bismaleimide compound represented by the general formula [Chemical Formula 12], it was found that a polymer containing a quinoline ring and (B) a structure represented by the general formula [Chemical Formula 16] When the bismaleimide compound having the following formula (B) is combined, the compound having the above general formula (B) in the curing process can be obtained without impairing the characteristics of the polymer having the most quinoline ring.
The bismaleimide compound having the structure of 2] is uniformly dissolved and flows, and adheres to the adherend to obtain excellent adhesiveness.
It has been found that a resin composition having excellent mechanical properties can be provided.

The polymer (A) containing a quinoline ring used in the present invention includes, for example, 2- (2-fluorophenyl)
Polymer consisting of -5-fluoro-4-phenylquinoline, 2- (4-fluorophenyl) -5-fluoro-4
Polymer comprising 4-phenylquinoline, polymer comprising 4- (2-fluorophenyl) -5-fluoro-4-phenylquinoline, polymer comprising 2- (4-fluorophenyl) -7-fluoro-4-phenylquinoline Coalescing, 2, 4
Polymer consisting of -difluoroquinoline, polymer consisting of 2,5-difluoroquinoline, polymer consisting of 2,7-difluoroquinoline, polymer consisting of 2,7-difluoro-6-phenylquinoline, 4- (4- A polymer consisting of (fluorophenyl) -7-fluoroquinoline, 6,6 ′
-Bis [2- (2-fluorophenyl) -4-phenylquinoline], 6,6'-bis [2- (4
-Fluorophenyl) -4-phenylquinoline], a polymer consisting of 6,6'-bis [2- (4-fluorophenyl) -4-tert-butylquinoline],
6,6'-bis [4- (4-fluorophenyl) -2-
Phenylquinoline], 6,6'-bis-
Polymer consisting of 2-fluoroquinoline, polymer consisting of 6,6'-bis-4-fluoroquinoline, 6,6'-bis [4- (4-fluorophenyl) -2- (2-pyridyl) quinoline] 6,6'-bis [4-
(4-fluorophenyl) -2- (methyl) quinoline], a polymer consisting of 6,6′-bis [2-fluoro-4-phenylquinoline], oxy-6,6′-
A polymer composed of bis [2- (4-fluorophenyl) -4-phenylquinoline], 1,4-benzene-bis-2,
Polymer composed of 2- [2- (4-fluorophenyl) quinoline], polymer composed of 1,4-benzene-bis-2,2- [4-fluoroquinoline], 1,4-benzene-
Polymer composed of bis-2,2- [4- (4-fluorophenyl) quinoline], 1,1,1,3,3,3-hexafluoroisopropylidene-bis-[(4-phenoxy-4-phenyl ) -2- (4-fluoroquinoline)]. These polymers are used alone or in combination of two or more.

The bismaleimide compound (B) includes, for example, N, N'-ethylene dimaleimide,
N'-hexamethylenebismaleimide, N, N'-dodecamethylenebismaleimide, N, N'-m-xylylenebismaleimide, N, N'-p-xylylenebismaleimide, N, N'-1,3 -Bismethylenecyclohexanebismaleimide, N, N'-1,4-bismethylenecyclohexanebismaleimide, N, N'-2,4-tolylenebismaleimide, N, N'-2,6-tolylenebismaleimide, N, N'-3,3-diphenylmethane bismaleimide, N, N'-4,4-diphenylmethane bismaleimide, 3,3-diphenylsulfonebismaleimide, 4,4-diphenylsulfonebismaleimide, N,
N'-4,4-diphenyl sulfide bismaleimide,
N, N'-p-benzophenone bismaleimide, N,
N'-diphenylethanebismaleimide, N, N'-diphenyletherbismaleimide, N, N '-(methylene-ditetrahydrophenyl) bismaleimide,
N '-(3-ethyl) -4,4-diphenylmethanebismaleimide, N, N'-(3,3-dimethyl) -4,4
-Diphenylmethane bismaleimide, N, N '-(3,
3-diethyl) -4,4-diphenylmethanebismaleimide, N, N '-(3,3-dichloro) -4,4-diphenylmethanebismaleimide, N, N'-tolidinebismaleimide, N, N'-isophoronebis Maleimide,
N, N'-p, p'diphenyldimethylsilylbismaleimide, N, N'-benzophenonebismaleimide,
N, N'-diphenylpropanebismaleimide, N,
N'-naphthalenebismaleimide, N, N'-m-phenylenebismaleimide, N, N'-4,4- (1,1-
Diphenyl-cyclohexane) -bismaleimide, N,
N'-3,5- (1,2,4-triazole) -bismaleimide, N, N'-pyridine-2,6-diylbismaleimide, N, N'-5-methoxy-1,3- Phenylenebismaleimide, 1,2-bis (2-maleimidoethoxy) ethane, 1,3-bis (3-maleimidopropoxy) propane, N, N'-4,4-diphenylmethane-
Bis-dimethylmaleimide, N, N'-hexamethylene-bis-dimethylmaleimide, N, N'-4,4'-
(Diphenyl ether) -bis-dimethylmaleimide,
N, N'-4,4 '-(diphenylsulfone) -bis-
Bifunctional maleimide compounds represented by dimethylmaleimide, N, N'-bismaleimide of N, N'-4,4 '-(diamino) -triphenylphosphate, etc., reaction products of aniline and formalin (polyamine compounds) ,
Polyfunctional maleimide compounds obtained by the reaction of 3,4,4'-triaminodiphenylmethane, triaminophenol and the like with maleic anhydride, tris- (4-aminophenyl) -phosphate, tris (4-aminophenyl)-
Maleimide compounds obtained by reacting phosphate, tos (4-aminophenyl) -thiophosphate with maleic anhydride, 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane, 2,2-bis [3 -Chloro-4- (4-maleimidophenoxy) phenyl] propane, 2,2-bis [3-bromo-4- (4-maleimidophenoxy) phenyl] propane, 2,2-bis [3-
Ethyl-4- (4-maleimidophenoxy) phenyl]
Propane, 2,2-bis [3-propyl-4- (4-maleimidophenoxy) phenyl] propane, 2,2-bis [3-isopropyl-4- (4-maleimidophenoxy) phenyl] propane, 2,2- Bis [3-butyl-
4- (4-maleimidophenoxy) phenyl] propane, 2,2-bis [3-sec-butyl-4- (4-maleimidophenoxy) phenyl] propane, 2,2-bis [3-methoxy-4- (4 -Maleimidophenoxy) phenyl] propane, 1,1-bis [4- (4-maleimidophenoxy) phenyl] ethane, 1,1-bis [3-
Methyl-4- (4-maleimidophenoxy) phenyl]
Ethane, 1,1-bis [3-chloro-4- (4-maleimidophenoxy) phenyl] ethane, 1,1-bis [3
-Bromo-4- (4-maleimidophenoxy) phenyl)
Ethane, 1,1-bis [4- (4-maleimidophenoxy) phenyl] methane, 1,1-bis [3-methyl-4
-(4-maleimidophenoxy) phenyl] methane,
1,1-bis [3-chloro-4- (4-maleimidophenoxy) phenyl] methane, 1,1-bis [3-bromo-4- (4-maleimidophenoxy) phenyl] methane, 3,3-bis [ 4- (4-maleimidophenoxy)
Phenyl] pentane, 1,1-bis [4- (4-maleimidophenoxy) phenyl] propane, 1,1,1,
3,3,3-hexafluoro-2,2-bis [4- (4
-Maleimidophenoxy) phenyl] propane, 1,
1,1,3,3,3-hexafluoro-2,2-bis [3-5-dimethyl- (4-maleimidophenoxy) phenyl] propane, 1,1,1,3,3,3-hexafluoro- 2,2-bis [3-5-dibromo- (4-maleimidophenoxy) phenyl] propane and 1,1,
1,3,3,3-hexafluoro-2,2-bis [3-
5-methyl- (4-maleimidophenoxy) phenyl]
There are aromatic bismaleimide compounds such as propane,
It is not particularly limited to the above. These can be used alone or in combination of two or more.

Next, (A) a polyquinoline polymer represented by the above-mentioned general formula [Chemical formula 11] and (B) a polyquinoline polymer of the above-mentioned general formula [Chemical formula 12]
The photosensitivity can be imparted to the polyfunctional maleimide compound represented by the formula (C) by adding a compound capable of reacting with the polyfunctional maleimide compound by light (C) or polymerizing the maleimide compound. (C) in the present invention can be widely used as long as it is a compound that absorbs light and reacts with a polyfunctional maleimide compound or polymerizes the maleimide compound.
An ordinary photoradical generator and its sensitizer are one example. More preferably, the compounds represented by the general formulas [Chemical formula 21], [Chemical formula 2]
2] and [Formula 23]

[0041]

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[0042]

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[0043]

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[0044] (wherein R _11, R ₁₂ and R ₁₃ are H, alkyl group having 1 to 15 carbon atoms, an alkoxy group, may be different from each other. Further, R ₁₄ is H, 1 to 3 carbon atoms 2,5-dibenzoyl-p-xylene, 2,5-bis (4- (methoxy) benzoyl) -p-xylene, 2,5-bis (4
-(Ethoxy) benzoyl) -p-xylene, 2,5-
Bis (4- (isopropyloxy) benzoyl) -p-
There are benzophenone compounds such as xylene and 2,5-bis (4- (dodecyloxy) benzoyl) -p-xylene, and are not particularly limited to those described above. These can be used alone or in combination of two or more.

Next, (A) a polyquinoline polymer and (B)
Bismaleimide compound (C) In addition to a compound capable of reacting with or polymerizing a maleimide compound by light, (d) a polymerizable compound selected from (d) aromatic diamines, epoxy compounds, polybutadiene compounds, etc. depending on the intended use in an organic solvent in advance. After uniformly dissolving the resin, the organic solvent is removed to obtain a resin composition.

As the above-mentioned aromatic diamine, for example, m
-Phenylenediamine, p-phenylenediamine, 4,
4-diaminodiphenylmethane, 4,4-diaminodiphenylsulfide, 2,2-bis (4-aminophenyl) propane, 4,4-diaminodiphenylsulfone,
Bis- (4-aminophenyl) methylphosphine oxide, bis- (4-aminophenyl) phosphine oxide, bis- (4-aminophenyl) methylamine, 1,
5-diaminonaphthalene, m-xylylenediamine,
1,1-bis (p-aminophenyl) furan, p-xylylenediamine, 6,6-diamino-2,2-dipyridyl, -diaminodiphenylsulfone, bis- (4-aminophenyl) methylphosphine oxide, bis- (4-
Aminophenyl) phosphine oxide, bis- (4-aminophenyl) methylamine, 1,5-diaminonaphthalene, m-xylylenediamine, 1,1-bis (p-aminophenyl) furan, p-xylylenediamine, 6 ,
6-diamino-2,2-dipyridyl, 2,2-bis [3
-Propyl-4- (4-aminophenoxy) phenyl]
Propane, 2,2-bis [3-isopropyl-4- (4
-Aminophenoxy) phenyl] propane, 2,2-bis [3-butyl-4- (4-aminophenoxy) phenyl] propane, 2,2-bis [3-sec-butyl-4
-(4-aminophenoxy) phenyl] propane, 2,
2-bis [3-methoxy-4- (4-aminophenoxy) phenyl] propane, 1,1-bis [4- (4-aminophenoxy) phenyl] ethane, 1,1-bis [3
-Methyl-4- (4-aminophenoxy) phenyl] ethane, 1,1-bis [3-chloro-4- (4-aminophenoxy) phenyl] ethane, 1,1-bis [3-bromo-4- ( 4-aminophenoxy) phenyl] ethane,
1,1-bis [4- (4-aminophenoxy) phenyl] methane, 1,1-bis [3-methyl-4- (4-aminophenoxy) phenyl] methane, 1,1-bis [3
-Chloro-4- (4-aminophenoxy) phenyl] methane, 1,1-bis [3-bromo-4- (4-aminophenoxy) phenyl] methane, 3,3-bis [4- (4
-Aminophenoxy) phenyl] pentane, 1,1-bis [4- (4-aminophenoxy) phenyl] propane, 1,1,1,3,3,3-hexafluoro-2,2
-Bis [4- (4-aminophenoxy) phenyl] propane, 1,1,1,3,3,3-hexafluoro-2,
2-bis [3-5-dimethyl- (4-aminophenoxy) phenyl] propane, 1,1,1,3,3,3-hexafluoro-2,2-bis [3-5-dibromo- (4
-Aminophenoxy) phenyl] propane, and 1,
There is 1,1,3,3,3-hexafluoro-2,2-bis [3-5-methyl- (4-aminophenoxy) phenyl] propane and the like, and it is not particularly limited to the above. The aromatic compound is used because it is more advantageous in heat resistance than the aliphatic compound.

On the other hand, examples of epoxy compounds include diglycidyl ether of bisphenol A, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, and 4,4 '-(1,2-epoxyethyl) Biphenyl, 4,4 '-(1,2-epoxyethyl) biphenyl ether, resorcin diglycidyl ether, bis (2,3-epoxycyclopentyl) ether, N, N'-m-phenylenebis (4,5'-epoxy Bifunctional epoxy compounds such as -1,2-cyclohexanedicarbodiimide), triglycidyl compounds of p-aminophenol, 1,3,5-tri (1,2-epoxyethyl) benzene, tetraglycidoxytetraphenylethane, Phenol formaldehyde novolak resin trifunctional or more Epoxy compound, an epoxy compound having a hydantoin skeleton, at least one of an epoxy compound containing a halogen atom such as bromine epoxy compound
Seeds are used.

Further, as the polybutadiene compound, for example, 1,2-polybutadiene, cyclized 1,2-polybutadiene, epoxy-modified 1,2-polybutadiene, 1,2-polybutadiene with terminal epoxidation, 1,2-polybutadiene glycol, , 2-polybutadienecarboxylic acid,
Urethane-modified 1,2-polybutadiene, maleated 1,
At least one of 2-polybutadiene, terminal acrylic-modified 1,2-polybutadiene, terminal ester-modified 1,2-polybutadiene compound and the like are used.

These compositions can be obtained by dissolving the respective components in an organic solvent, applying the composition on a base film, and removing the organic solvent. As a method of use, it is possible to adopt a method in which this base film is overlaid on a wiring board, melt-pressed by heating and pressing, or in some cases directly applied or printed, and then dried to remove the organic solvent. I don't care. Further, the composition after the removal of the organic solvent can be pulverized and used as a fine powder. Examples of the organic solvent that can be used here include methylcellosolve, methylethylketone, N, N-dimethylformamide,
There are N, N-dimethylacetamide, N-methyl-2-pyrrolidone, quinoline, cyclopentanone, m-cresol, chloroform and the like, and at least one of them can be used in combination. As the developer, the same organic solvent and an aqueous solution thereof can be used.

In the present invention, the compounding ratio of the polymer containing a quinoline ring of the component (A) and the polyfunctional maleimide compound of the component (B) is based on 100 of the total solid content of both.
95 to 20% by weight of a polymer containing a quinoline ring as the component (A)
Is desirable. (A) a polymer containing a quinoline ring
If the content is 0% by weight or more, the fluidity becomes poor, and the adhesion to the substrate and the filling property deteriorate. When the content is 20% by weight or less, fluidity is excellent, but problems such as poor heat resistance and mechanical properties occur. The component (C) can be widely used in a molar ratio to the component (B) ranging from an equivalent amount to 1/5.

When the component (D) is added in the present invention, the content is preferably 40% by weight or less based on the whole resin component. If the component (D) is added in an amount of 40% by weight or more, the moldability and the adhesiveness are excellent, but the heat resistance is inferior.

[0052]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be specifically described with reference to embodiments.

Example 1 6,6'-bis (2- (4-
Polyquinoline comprising fluorophenyl) -4-phenylquinoline) and 4,4 '-(1,1,1,3,3,3-hexafluoro-2,2-propylidene) bisphenol; PQ1 (molecular weight (in terms of polystyrene) ; 47
000) and 280 g of cyclopentanone were placed in a 500 mL three-necked flask equipped with a stirrer, a condenser, and a thermometer and stirred at room temperature for 1 hour to dissolve. Further, 60 g of 2,2-bis ((4-maleimidophenoxy) phenyl) propane was added, and the mixture was stirred for 1 hour to obtain a desired varnish. This varnish was further treated with 2,5-dibenzoyl-
50 g of p-xylene was added and uniformly dissolved.

Next, a 200 mm × 200 mm × 2 mm Pyrex glass plate was covered with a 0.025 mm thick polyimide film (UPILEX-25s, Ube Industries) using a heat-resistant tape. The varnish was uniformly applied on the polyimide film using a bar coater, and the solvent was evaporated in a drying furnace with a profile of 100 ° C./20 minutes + 200 ° C./20 minutes. A free standing film was obtained by removing the polyimide film from this film. The resulting film had a thickness of 0.030 mm and was excellent in flexibility without breaking even when bent.

On a glass substrate, a height of 0.015 mm and a width of 0.15 mm were used.
An evaluation pattern is prepared in which ten copper wires each having a length of 03 mm and a length of 10 mm are formed at a line interval of 0.03 mm. On the evaluation pattern, the film prepared above was overlapped and pressed in a press.
Melt pressure bonding was performed at 70 ° C. for 30 minutes. The filling of the resin into the line was checked visually from the top of the film, and the cross section of the test piece was SE.
Observed at M and evaluated.

Further, a film is pressed on a copper plate by the same method, and 5 J / cm ² using a super-high pressure mercury lamp through a mask having a circular pattern every 0.01 mm from 0.15 mm to 0.05 mm in diameter. Exposure. The test piece was dipped in cyclopentanone at 40 ° C. in an ultrasonic cleaner, developed, and evaluated for resolution.

The sample prepared on the polyimide film prepared above was exposed to 5 J / cm ² using an extra-high pressure mercury lamp, and further heated in a dryer at 200 ° C. for 2 hours. The polyimide film was peeled from this film, and the mechanical properties, the dielectric constant at 1 KHZ, and the thermal decomposition onset temperature were measured. Using the same test piece, a 70% R
H, left at 150 ° C. to determine the saturated water absorption.

The above results are summarized in Table 1.

[0059]

[Table 1]

Example 2 6,6'-bis (2- (4-
Polyquinoline comprising fluorophenyl) -4-phenylquinoline) and 4,4 '-(1,1,1,3,3,3-hexafluoro-2,2-propylidene) bisphenol; PQ1 (molecular weight (in terms of polystyrene) ; 47
000) and 280 g of cyclopentanone were placed in a 500 mL three-necked flask equipped with a stirrer, a condenser, and a thermometer and stirred at room temperature for 1 hour to dissolve. Further, 60 g of 2,2-bis ((4-maleimidophenoxy) phenyl) propane was added, and the mixture was stirred for 1 hour to obtain a desired varnish. 50 g of 2,5-bis (4- (dodecyloxy) benzoyl) -p-xylene was further added to the varnish and uniformly dissolved.

Next, using the same method as that of the first embodiment, 0.2
A flexible film having a thickness of 030 mm was prepared, and the characteristics were evaluated in the same manner. Table 1 shows the results.

(Example 3) Varnish 1 obtained in Example 1
Of the epoxy-modified polybutadiene modified with diglycidyl ether bisphenol A and 0.44 of 4,4-diaminodiphenylmethane.
g and uniformly mixed to obtain a varnish.

Next, the same method as in the first embodiment was used to adjust
A flexible film having a thickness of 030 mm was prepared, and the characteristics were evaluated in the same manner. Table 1 shows the results.

Example 4 1,60 g of the polyquinoline shown in Example 1; PQ, was placed in a 200 mL three-necked flask equipped with a stirrer, a condenser, and a thermometer, and 280 g of cyclopentanone was added. Stir for hours to dissolve. 2,2-bis (4- (2-trifluoromethyl-4
-Maleimidophenoxy) phenyl) -1,1,1,
60 g of 3,3,3-hexafluoropropane was added, and the mixture was stirred for 1 hour. Subsequently, 50 g of 2,5-dibenzoyl-p-xylene was added to obtain a target varnish.

Thereafter, the same method as in Example 1 was used to set the value to 0.1.
A flexible film having a thickness of 030 mm was prepared, and the characteristics were evaluated in the same manner. Table 1 shows the results.

Example 5 6,6'-bis (2- (4-
Fluorophenyl) -4-phenylquinoline), 9,9
Polyquinoline comprising -bis (4-hydroxyphenyl) fluorene; PQ2 (molecular weight (in terms of polystyrene);
45800) 60 g, and cyclopentanone 280
g for 500 mL with stirring bar, cooling tube and thermometer set
The mixture was placed in a three-neck flask and stirred at room temperature for 1 hour to dissolve.
Further, 60 g of 2,2-bis ((4-maleimidophenoxy) phenyl) propane was added, and the mixture was stirred for 1 hour. Subsequently, 50 g of 2,5-dibenzoyl-p-xylene was added to obtain a target varnish.

Thereafter, the same method as in Example 1 was used to obtain 0.1%.
A flexible film having a thickness of 030 mm was prepared, and the characteristics were evaluated in the same manner. Table 1 shows the results.

(Example 6) 2,60 g of the polyquinoline shown in Example 5; PQ, was placed in a three-necked 500 mL flask equipped with a stirrer, a condenser, and a thermometer, and 280 g of cyclopentanone was added. Stir for hours to dissolve. 2,2-bis (4- (4-maleimidophenoxy)
60 g of phenyl) -propane was added, and the mixture was stirred for 1 hour. Subsequently, 50 g of 2,5-dibenzoyl-p-xylene was added to obtain a desired varnish.

Thereafter, the same method as in Example 1 was used to set the value to 0.1.
A flexible film having a thickness of 030 mm was prepared, and the characteristics were evaluated in the same manner. Table 1 shows the results.

Example 7 6,6'-bis (2- (4-
60 g of PQ3 (molecular weight (in terms of polystyrene; 49000)) of polyquinoline comprising fluorophenyl) -4-phenylquinoline), methyl-2,4-dihydroxybenzoate, and isopropylidenediphenol;
At room temperature, 280 g of cyclopentanone was placed in a three-necked 500 mL flask equipped with a stirring rod, a condenser, and a thermometer.
Stir for hours to dissolve. Further, 60 g of 2,2-bis ((4-maleimidophenoxy) phenyl) propane was added,
The mixture was stirred for 1 hour, and subsequently, 50 g of 2,5-dibenzoyl-p-xylene was added to obtain a desired varnish.

Hereinafter, by using the same method as that of the first embodiment, the following procedure is performed.
A flexible film having a thickness of 030 mm was prepared, and the characteristics were evaluated in the same manner. Table 1 shows the results.

(Example 8) 3,0 g of the polyquinoline shown in Example 7; PQ, was placed in a 200 mL three-necked flask equipped with a stirrer, a condenser, and a thermometer, and 70 g of cyclopentanone was further added. Stir for hours to dissolve.
2,2-bis (4- (2-trifluoromethyl-4-maleimidophenoxy) phenyl) -1,1,1,3,
15 g of 3,3-hexafluoropropane was added, and the mixture was stirred for 1 hour. Further, 15 g of 2,5-dibenzoyl-p-xylene was added to obtain a target varnish.

Thereafter, the same method as in Example 1 was used to reduce the
A flexible film having a thickness of 030 mm was prepared, and the characteristics were evaluated in the same manner. Table 1 shows the results.

(Example 9) 3,40 g of the polyquinoline shown in Example 7; PQ, was placed in a 200 mL three-necked flask equipped with a stirrer, a condenser, and a thermometer, and 70 g of cyclopentanone was further added. Stir for hours to dissolve.
2,2-bis (4- (2-trifluoromethyl-4-maleimidophenoxy) phenyl) -1,1,1,3,
10 g of 3,3-hexafluoropropane was added, the mixture was stirred for 1 hour, and 10 g of 2,5-dibenzoyl-p-xylene was added to obtain a target varnish.

Thereafter, the same method as in Example 1 was used to set the value to 0.1.
A flexible film having a thickness of 030 mm was prepared, and the characteristics were evaluated in the same manner. Table 1 shows the results.

Comparative Example 1 A 500-mL four-necked flask equipped with a stirrer, a thermometer, a nitrogen inlet tube, and a cooling tube was prepared as follows:
32.3 g of 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 63.2 g of 4,4'-bis [3- (4-amino-α, α'-dimethylbenzyl) phenoxy] diphenyl ketone , And 140 g of m-cresol and 30 g of toluene were stirred and dissolved. The mixture was heated and stirred at 150 ° C. for 16 hours under a nitrogen stream. 100 g of this polyimide varnish was taken, and 3.08 g of 2,2-bis ((4-maleimidophenoxy) phenyl) propane was added.

The varnish was applied on a glass substrate with a bar coater and dried in a drier at 160 ° C. for 30 minutes to obtain an uncured film having a thickness of 0.025 mm. This uncured film was applied to the same copper wiring pattern
The film was melt-thickened and hardened at 30 ° C. for 30 minutes to confirm the filling property. Further, the film obtained by coating and drying on a glass substrate is 230
After curing at 30 ° C. for 30 minutes, the mechanical properties, electrical properties, and moisture absorption were measured in the same manner as in the examples.

Comparative Example 2 Photosensitive benzocyclobutene (cycloten 5021, Dow Chemical) is spin-coated on an Si wafer at a rotation speed of 3000 rpm. Prebaking was performed at 70 ° C. for 20 minutes, and after removing the solvent in a drier, exposure was performed with an ultra-high pressure mercury lamp at 0.6 J / cm ² . At this time, two samples were prepared and one was performed through a mask having the same pattern as above. These were dipped in a developer for 2 minutes and developed to evaluate the resolution. These were further cured at 250 ° C./2 hours. The sample whose characteristics are to be measured was prepared by peeling off the Si wafer here.

[0079]

As is apparent from the above, the photosensitive film according to the present invention is an insulating film having higher fluidity and excellent resin filling property between wirings as compared with the conventional polyimide adhesive film. On the other hand, since it has photosensitivity, it is easy to form a via and can be applied to an electronic component having high-density wiring. Further, the properties of the insulating layer are very high, such as high heat resistance, low moisture absorption, and low dielectric constant. That is, the photosensitive film according to the present invention is easier to handle than conventional photosensitive resins, can form a multilayer wiring board with fine wiring, and has excellent properties as an insulating layer. The use of this film makes it possible to easily and inexpensively achieve high performance such as miniaturization of electronic and electric components.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI G03F 7/004 521 G03F 7/004 521 7/027 514 7/027 514 (72) Inventor Shin Nishimura Omikamachi, Hitachi-shi, Ibaraki Pref. Hitachi 1-1, Hitachi, Ltd. (72) Inventor Akio Takahashi 7-1-1, Omika-cho, Hitachi City, Ibaraki Pref., Hitachi Research Laboratory, Hitachi, Ltd.

Claims (9)

[Claims] In a photosensitive resin composition which is insolubilized by activating light, a cured product obtained by irradiating the resin composition with light has a relative dielectric constant of 2.5 to 3.8 and a saturated moisture absorption of 0.3. ~ 1.0%,
A photosensitive resin composition having a thermal decomposition onset temperature of 400 ° C. or higher. 2. The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition becomes a self-standing film, and when the film is heated, it flows and can be molded. 3. The method according to claim 1, wherein (A) a polymer having a quinoline ring, (B) a polyfunctional maleimide, and (C) a compound capable of reacting with or polymerizing the maleimide compound by light. Characteristic photosensitive resin composition. 4. The method according to claim 3, wherein the compound represented by the general formula [1] A polymer containing a quinoline ring represented by the formula: (B) a compound represented by the following general formula: (In the formula, Ar represents a divalent organic group containing at least two carbons.) A photosensitive resin composition using a resin composition containing a bismaleimide compound represented by the following formula as an essential component. 5. The polymer according to claim 3, wherein (A) the polymer containing a quinoline ring is represented by the general formula [3] or the general formula [4]: Embedded image (Wherein R ¹ and R ² each independently represent an alkyl group, an aryl group, an alkoxy group, an allyloxy group, a formyl group (—COR), an ester group (—COR or —OCO
R), amide group (-NRCOR or -CONR
R) represents a heteroaryl group, a cyano group, or a divalent hydrocarbon group which may contain an unsaturated bond formed by connecting two (R is a hydrogen atom, an alkyl group, or a heteroaryl group) ), M and n are each independently an integer of 0 to 5, X is a chemical bond, -O-, -S
-, - CO -, - SO -, - SO 2 -, - A -, (O-
A) _q- O- or -Q- (where q is an integer of 1 to 3, and A is -Ar- (arylene group), -Hr- (heteroarylene group), -Ar-O-Ar- , -CO-Ar
-, -Ar-S-Ar-, -Ar-SO-Ar-, -A
r- or -Ar-Q-Ar-, wherein Q is (L ¹ and L ² represent a methyl group, a trifluoromethyl group or a divalent hydrocarbon group which may contain an unsaturated bond formed by connecting two), and Z ¹ and Z ² are
Each independently represents a chemical bond or an arylene group;
Represents -O- or -OAO-. A photosensitive resin composition characterized by using a polymer containing a quinoline ring represented by the formula (1). 6. The method according to claim 3, wherein (B) the polyfunctional maleimide is represented by the general formula [6] or the general formula [7]. Embedded image (Where R ₁ to R ₁₀ are H, CH ₃ , CH ₂ CH ₃ , F, C
Shows the F _3, may be different from each other. n may be 0 or an integer of 1 to 4, which may be different from each other. A photosensitive resin composition characterized by using a resin composition represented by a bismaleimide compound having in the structure thereof. 7. The compound according to claim 3, wherein (C) the compound capable of reacting with the maleimide compound by light to form a polymer is:
General formula [Chemical formula 8] (Wherein R ₁₁ and R ₁₂ represent H, an alkyl group or an alkoxy group having 1 to 15 carbon atoms, which may be different from each other). 8. The compound according to claim 3, wherein (C) the compound capable of reacting with the maleimide compound by light to form a polymer is:
General formulas [Chemical formula 9] and [Chemical formula 10] Embedded image (Wherein R ₁₁ , R ₁₂ and R ₁₃ represent H, an alkyl group having 1 to 15 carbon atoms or an alkoxy group, which may be different from each other. R ₁₄ represents H, an alkyl group having 1 to 3 carbon atoms, A photosensitive resin composition which is a mixture of a benzophenone compound represented by the following formula: 9. A photosensitive resin composition according to claim 3, further comprising (C) a polymerizable compound selected from aromatic diamines, epoxy compounds, polybutadiene compounds and the like.