JP2002278065A - Photosensitive resin composition and photosensitive dry film resist using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition excellent in processability and adhesiveness, having sufficient mechanical strength after curing, and excellent heat resistance, and a photosensitive dry film resist using the same. And to provide a photosensitive coverlay film laminated substrate in which the dry film resist is laminated on a printed circuit board and has good physical properties. SOLUTION: (A) COOH equivalent is 200 to 3000.
A photosensitive resin composition comprising: a soluble polyimide, (B) a polyfunctional (meth) acrylic compound and / or a polyfunctional (meth) acrylic compound composed of an analog thereof, and (C) a photoreaction initiator. .

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a photosensitive resin composition,
And a photosensitive dry film resist using the same. Further, the present invention relates to a photosensitive coverlay film using the dry film resist, which is used for a printed circuit board used in the field of electronic materials, or used for a suspension for a hard disk; and Having the cover film,
The present invention relates to a photosensitive coverlay film laminated printed board.

[0002]

2. Description of the Related Art In recent years, electronic equipment has become more sophisticated and more sophisticated.
In addition, miniaturization is rapidly progressing, and accordingly, miniaturization and weight reduction of electronic components are required. For this reason, a flexible printed wiring board (hereinafter, referred to as FPC), which is more flexible than a conventional rigid printed wiring board, has been attracting more attention than ever before, and the demand for the wiring board has rapidly increased.

Incidentally, a polymer film called a coverlay film is bonded to the surface of the FPC for the purpose of protecting the conductor surface. As a method of bonding this cover lay film to the surface of the conductor surface, a method of laminating a cover lay film with an adhesive on the conductor surface processed into a predetermined shape, positioning, and then thermocompression bonding with a press or the like is used. General. Usually, an adhesive is applied to a long cover lay film, dried, and continuously laminated with the conductor surface of the FPC. However, the adhesives used here are mainly epoxy-based, acrylic-based adhesives, and have low heat resistance such as solder heat resistance and adhesive strength at high temperatures, or lack flexibility, so coverlay films The heat resistance performance of the polyimide film used for the above could not be fully utilized.

Further, when a cover lay film is bonded to an FPC using a conventional epoxy or acrylic adhesive, a bonding portion between a terminal portion and a component of a circuit is attached to the cover lay film before bonding. The holes and windows must be made in accordance with the requirements. However, not only is it difficult to drill holes and the like in thin coverlay films, but the alignment of the holes and the like in the coverlay films with the joints with the terminals and components of the FPC is almost a manual operation. Was. For this reason, there are disadvantages in that the positional accuracy is poor, the workability of bonding is poor, and the cost is high.

In order to improve the workability and positional accuracy, a method has been developed in which a photosensitive composition is applied to a conductor surface to form a protective layer. Furthermore, a photosensitive coverlay film was developed, and after laminating the coverlay film on an FPC, it was possible to form a pattern by exposure and development, and to form holes and the like at required positions. Therefore, workability and position accuracy have been improved.

However, since the above-mentioned photosensitive coverlay film uses an acrylic resin, the heat resistance temperature and the brittleness of the film are not sufficient. Therefore, photosensitive polyimide has been studied as a material for the photosensitive coverlay film. As such a photosensitive polyimide, a photosensitive polyamide having a methacryloyl group introduced through an ester bond is obtained, and the resulting polyimide is obtained by imidization (JP-B-55-030207, JP-B-55-0414).
22); Further, using an amine compound or a diisocyanate compound having a methacryloyl group, a polyamic acid having a methacryloyl group introduced at a carboxyl group is obtained, and a polyimide obtained by imidating the polyamic acid (Japanese Patent Laid-Open No. 54-1979). 145794, JP-A-59-1
60140, JP-A-03-170547, JP-A-03-17047
186847, and JP-A-61-118424).

However, since these photosensitive polyimides are obtained only after imidization after exposure and development in the state of polyamic acid, a temperature of 250 ° C. or higher must be applied to the FPC for the imidization. Therefore, components other than the copper foil or the polyimide on the substrate may be deteriorated. Further, depending on the photosensitive polyimide, it is necessary to remove the acryloyl group contained in the polyimide by heat, and at that time, there is a problem that the film thickness is largely reduced.

In order to solve the above-mentioned drawbacks, there is a demand for a photosensitive polyimide which can be dissolved in a solvent. A photosensitive polyimide soluble in a solvent is disclosed in, for example, JP-A-6-276.
No. 67 is described. The publication discloses a composition containing a polyimide, a diluent, and a sensitizer or a photopolymerization initiator. This polyimide has a structure having a vinyl ether group in a polymer side chain, and has solubility in a solvent. However, this composition is designed as a solder resist for a substrate, and the polyimide has poor developing performance due to poor solubility in an alkaline solution.

[0009]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned conventional problems, and has as its object to be easy to handle because it is soluble in an organic solvent, to be excellent in heat resistance, and to be further processed. An object of the present invention is to provide a photosensitive resin composition having excellent mechanical properties and adhesiveness, and a coating film obtained having sufficient mechanical strength, and a photosensitive dry film resist using the same. Another object of the present invention is to provide a photosensitive coverlay film comprising the dry film resist and exhibiting good physical properties,
It is another object of the present invention to provide a photosensitive coverlay film laminated printed board obtained by laminating the coverlay film on a printed board.

[0010]

Means for Solving the Problems The present inventors have succeeded in developing a photosensitive resin composition which does not require an imidation step by using a predetermined soluble polyimide, and have completed the present invention. Was.

The photosensitive resin composition of the present invention comprises (A) CO
A soluble polyimide having an OH equivalent of 200 to 3000,
(B) polyfunctional (meth) acrylic compounds comprising a polyfunctional (meth) acrylic compound and / or an analog thereof,
And (C) a photoreaction initiator.

In a preferred embodiment, the soluble polyimide is derived from a diamine having two or more COOH groups in a molecule.

[0013] In a preferred embodiment, the soluble polyimide is dissolved in a solvent having a boiling point of 120 ° C or lower.

In a preferred embodiment, the polyfunctional (meth) acrylic compound is bifunctional and (-
_{O-CH 2 CH} 2 - has the repeating units of).

[0015] In a preferred embodiment, the photoreaction initiator has a radical generating ability by at least one of g-line and i-line.

In a preferred embodiment, the soluble polyimide is derived from a siloxane diamine represented by the following general formula (I):

[0017]

Embedded image

(Wherein R ¹ is each independently C ₁ to C
₁₂ are an alkyl group or a phenyl group, x is each independently an integer of 1 to 20, and y is an integer of 1 to 40).

In a preferred embodiment, the soluble polyimide contains 5 to 70 mol% of the siloxane diamine.
Is obtained as a raw material.

The photosensitive dry film resist of the present invention is obtained from the above composition.

In a preferred embodiment, the photosensitive dry film resist is insoluble in an aqueous alkali solution by a polymerization reaction upon exposure, and is soluble when not exposed.

In a preferred embodiment, the starting temperature of thermal decomposition of the photosensitive dry film resist after curing is 30.
0 ° C. or higher.

In a preferred embodiment, the curing temperature of the photosensitive dry film resist is 200 ° C. or lower.

In a preferred embodiment, the photosensitive dry film resist can be laminated at a temperature of 150 ° C. or less.

The photosensitive coverlay film for a printed circuit board of the present invention comprises the above photosensitive dry film resist.

In the photosensitive cover lay film-laminated printed board of the present invention, the above-described photosensitive cover lay film is directly laminated on the printed board.

[0027]

BEST MODE FOR CARRYING OUT THE INVENTION The soluble polyimide used in the present invention (hereinafter sometimes referred to as soluble polyimide (A)) has a COOH equivalent of 200 to 3000. Such a soluble polyimide (A) can be obtained by a usual polyimide production method. For example, it is obtained by a method of reacting an acid dianhydride with a diamine in an organic solvent to form a polyamic acid, followed by imidization by a dehydration reaction; or a method of reacting an acid dianhydride with a diisocyanate in a solvent. . Of these, the former method of reacting an acid dianhydride with a diamine to obtain a polyamic acid and then imidizing by a dehydration reaction is preferably used.

The acid dianhydride used as a raw material for the soluble polyimide (A) is not particularly limited, and for example, the following compounds are used: 2,2′-hexafluoropropylidene diphthalic dianhydride, 2,2 -Bis (4-hydroxyphenyl) propanedibenzoate-3,3 ', 4,
4'-tetracarboxylic dianhydride, butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4
-Cyclobutanetetracarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-
Tricarboxycyclopentylacetic acid dianhydride, 3,5
6-tricarboxynorbornane-2-acetic acid dianhydride,
2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, bicyclo [2 , 2,2] -Octo-
Aliphatic or alicyclic tetracarboxylic dianhydride such as 7-ene-2,3,5,6-tetracarboxylic dianhydride; pyromellitic dianhydride, 3,3 ′, 4,4′- Benzophenonetetracarboxylic dianhydride, 3,3 ', 4,4'
-Biphenylsulfonetetracarboxylic dianhydride, 1,
4,5,8-naphthalenetetracarboxylic dianhydride,
2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenylethertetracarboxylic dianhydride, 3,3 ′, 4,4′-dimethyldiphenylsilanetetracarboxylic Acid dianhydride, 3,3 ',
4,4'-tetraphenylsilanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride , 4,4′-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3 ′,
4,4'-perfluoroisopropylidene diphthalic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, bis (phthalic acid) phenylphosphine oxide dianhydride, p-phenylene- Bis (triphenylphthalic acid) dianhydride, m-phenylene-bis (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4'-diphenyl ether dianhydride, bis (triphenylphthalic acid) ) Aromatic tetracarboxylic dianhydrides such as -4,4'-diphenylmethane dianhydride; and 1,3,3a, 4,5,9b-hexahydro-2,5
-Dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b-
Hexahydro-5-methyl-5- (tetrahydro-2,
5-dioxo-3-furanyl) -naphtho [1,2-c]
Furan-1,3-dione, 1,3,3a, 4,5,9b
-Hexahydro-8-methyl-5- (tetrahydro-
2,5-dioxo-3-furanyl) -naphtho [1,2-
c] Furan-1,3-dione, a compound represented by the following general formula (II):

[0029]

Embedded image

(Wherein R ² represents a divalent organic group having an aromatic ring, and R ³ and R ⁴ each independently represent a hydrogen atom or an alkyl group), and a compound represented by the following general formula (III) :

[0031]

Embedded image

(Wherein R ⁵ represents a divalent organic group having an aromatic ring, and R ⁶ and R ⁷ each independently represent a hydrogen atom or an alkyl group). Dianhydride. These tetracarboxylic dianhydrides can be used alone or in combination of two or more.

In addition, compounds of the following formula (IV) or (V) are also preferably used:

[0034]

Embedded image

(R ⁸ represents a divalent organic group).

[0036]

Embedded image

(R ⁹ is a single bond, —O—, —CH ₂ —,
— (C ＝ O) —, —C (CH ₃ ) ₂ —, or —C (C
F ₃ ) _2- ).

In particular, it is desirable to use the acid dianhydride represented by the formula (IV) or (V) in order to express heat resistance and mechanical properties at a high level.

In order to obtain a polyimide having high solubility in an organic solvent, a compound represented by the above formula (IV),
It is desirable to use 2'-hexafluoropropylidene diphthalic dianhydride and 2,3,3 ', 4'-biphenyltetracarboxylic dianhydride as a part of the acid dianhydride. In that case, the R of the compound represented by the above formula (IV)
^The following groups are preferred as ⁸ . —CH ₂ C (CH ₃ )
₂ CH ₂ —, —C _q H _2q — (q is an integer of 1 to 20) and a divalent group selected from the following:

[0040]

Embedded image

[0041]

Embedded image

(Where R¹⁰Is each independently hydrogen,
Halogen, methoxy, or C₁~ C ₁₆Alkyl group
Is shown).

The diamine used as a raw material of the soluble polyimide (A) includes a carboxyl group (COOH
A diamine having two or more groups in the molecule;
A combination of a diamine having two or more (OHH groups) in a molecule and another diamine is preferable. Thereby, a soluble polyimide having a carboxyl group can be obtained.

The diamine having two or more carboxyl groups in the molecule is not particularly limited. For example, the following compounds may be mentioned: diaminophthalic acids such as 2,5-diaminoterephthalic acid; 3,3′-diamino-4,4′-dicarboxybiphenyl, 4,4′-diamino-3,3 ′
-Dicarboxybiphenyl, 4,4'-diamino-2,
2'-dicarboxybiphenyl, 4,4'-diamino-
Carboxybiphenyl compounds such as 2,2 ', 5,5'-tetracarboxybiphenyl;3,3'-diamino-
4,4′-dicarboxydiphenylmethane, 2,2-bis [3-amino-4-carboxyphenyl] propane,
2,2-bis [4-amino-3-carboxyphenyl] propane, 2,2-bis [3-amino-4-carboxyphenyl] hexafluoropropane, 4,4′-diamino-2,2 ′, 5 Carboxydiphenylalkanes such as 5'-tetracarboxydiphenylmethane;3,3'-
Diamino-4,4'-dicarboxydiphenyl ether, 4,4'-diamino-3,3'-dicarboxydiphenyl ether, 4,4'-diamino-2,2'-dicarboxydiphenyl ether, 4,4'-diamino-
Carboxydiphenyl ether compounds such as 2,2 ′, 5,5′-tetracarboxydiphenyl ether;
3'-diamino-4,4'-dicarboxydiphenylsulfone, 4,4'-diamino-3,3'-dicarboxydiphenylsulfone, 4,4'-diamino-2,
2'-dicarboxydiphenylsulfone, 4,4'-
Diphenylsulfone compounds such as diamino-2,2 ', 5,5'-tetracarboxydiphenylsulfone;
Bis [(carboxyphenyl) phenyl] alkane compounds such as 2,2-bis [4- (4-amino-3-carboxyphenoxy) phenyl] propane;
Bis [4- (4-amino-3-carboxyphenoxy)
Bis [(carboxyphenoxy) phenyl] sulfone compounds such as phenyl] sulfone.

Examples of the other diamines (diamines having no or one carboxyl group in the molecule) include diamines having one hydroxyl group or carboxyl group in the molecule, siloxane diamines, and other diamines. Can be

The diamine having one hydroxyl group or carboxyl group in the molecule includes the following compounds: diaminophenols such as 2,4-diaminophenol; 3,3′-diamino-4,4′- Dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, 4,4'-diamino-2,2'-dihydroxybiphenyl, 4,4'-diamino-2,2 ',
Hydroxybiphenyl compounds such as 5,5'-tetrahydroxybiphenyl;3,3'-diamino-4,4'-
Dihydroxydiphenylmethane, 4,4'-diamino-
3,3'-dihydroxydiphenylmethane, 4,4'-
Diamino-2,2'-dihydroxydiphenylmethane,
2,2-bis [3-amino-4-hydroxyphenyl] propane, 2,2-bis [4-amino-3-hydroxyphenyl] propane, 2,2-bis [3-amino-4-hydroxyphenyl] hexa Fluoropropane, 4,4'-
Hydroxydiphenylalkanes such as hydroxydiphenylmethane such as diamino-2,2 ', 5,5'-tetrahydroxydiphenylmethane;3,3'-diamino-
4,4′-dihydroxydiphenyl ether, 4,4 ′
-Diamino-3,3'-dihydroxydiphenyl ether, 4,4'-diamino-2,2'-dihydroxydiphenyl ether, 4,4'-diamino-2,2 ', 5
Hydroxy diphenyl ether compounds such as 5'-tetrahydroxy diphenyl ether; 3,3'-diamino-
4,4′-dihydroxydiphenylsulfone, 4,
4'-diamino-3,3'-dihydroxydiphenylsulfone, 4,4'-diamino-2,2'-dihydroxydiphenylsulfone, 4,4'-diamino-2,
Diphenylsulfone compounds such as 2 ', 5,5'-tetrahydroxydiphenylsulfone; 2,2-bis [4
Bis [(hydroxyphenyl) phenyl] alkane compounds such as-(4-amino-3-hydroxyphenoxy) phenyl] propane; 4,4′-bis (4-amino-
Bis (hydroxyphenoxy) biphenyl compounds such as 3-hydroxyphenoxy) biphenyl; 2,2-bis [4
Bis [(hydroxyphenoxy) phenyl] sulfone compounds such as-(4-amino-3-hydroxyphenoxy) phenyl] sulfone; diaminobenzoic acids such as 3,5-diaminobenzoic acid; and 4,4'-diamino-
3,3'-dihydroxydiphenylmethane, 4,4'-
Diamino-2,2'-dihydroxydiphenylmethane,
Bis (hydroxyphenoxy) biphenyl compounds such as 2,2-bis [3-amino-4-carboxyphenyl] propane and 4,4′-bis (4-amino-3-hydroxyphenoxy) biphenyl.

As the siloxane diamine, a compound represented by the following formula (I) is suitable:

[0048]

Embedded image

(Wherein R ¹ is each independently C ₁ to C
₁₂ are an alkyl group or a phenyl group, x is each independently an integer of 1 to 20, and y is an integer of 1 to 40).

Use of such a siloxane diamine is preferable because a soluble imide having high flexibility and high solubility can be obtained. Preferred examples of R ^{1 in} the compound of the above formula (I) include a methyl group, an ethyl group and a phenyl group, and more preferred is a methyl group. x is 2
It is preferably from 10 to 10, particularly preferably from 2 to 5. y is preferably 4 to 30, more preferably 5 to 20, and particularly preferably 8 to 15.
Among them, the range of the value of y greatly affects the physical properties,
If the value of y is small, the flexibility of the obtained polyimide is poor, and if it is too large, the polyimide heat resistance tends to be impaired.

The siloxane diamine is preferably contained at a ratio of 5 to 70 mol% based on the total diamine used as a raw material. More preferably, 10 to 50 mol%
It is contained in the ratio of.

Other diamines include the following compounds: p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenylmethane,
4,4′-diaminophenylethane, 4,4′-diaminophenyl ether, 4,4′-diaminodiphenyl sulfide, 4,4′-diaminodiphenyl sulfone,
1,5-diaminonaphthalene, 3,3-dimethyl-4,
4'-diaminobiphenyl, 5-amino-1- (4'-
Aminophenyl) -1,3,3-trimethylindane,
6-amino-1- (4'-aminophenyl) -1,3,3
3-trimethylindane, 4,4'-diaminobenzanilide, 3,5-diamino-3'-trifluoromethylbenzanilide, 3,5-diamino-4'-trifluoromethylbenzanilide, 3,4'-diamino Diphenyl ether, 2,7-diaminofluorene, 2,2-bis (4-aminophenyl) hexafluoropropane,
4,4′-methylene-bis (2-chloroaniline),
2,2 ', 5,5'-tetrachloro-4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 3,3'-dimethoxy- 4,4′-diaminobiphenyl, 4,4′-diamino-2,2′-bis (trifluoromethyl) biphenyl, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2- Bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 1,4
-Bis (4-aminophenoxy) benzene, 4,4'-
Bis (4-aminophenoxy) -biphenyl, 1,3 ′
-Bis (4-aminophenoxy) benzene, 9,9'-
Bis (4-aminophenyl) fluorene, 4,4'-
(P-phenyleneisopropylidene) bisaniline,
4,4 '-(m-phenyleneisopropylidene) bisaniline, 2,2'-bis [4- (4-amino-2-trifluoromethylphenoxy) phenyl] hexafluoropropane, 4,4'-bis [4- Aromatic diamines such as (4-amino-2-trifluoromethyl) phenoxy] -octafluorobiphenyl (aromatic diamines having no heterocycle); aromatic diamines having a heterocycle such as diaminotetraphenylthiophene; and 1,1-metaxylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, octamethylenediamine, nonamethylenediamine, 4,4-
Diaminoheptamethylenediamine, 1,4-diaminocyclohexane, isophoronediamine, tetrahydrodicyclopentadienylenediamine, hexahydro-4,
Aliphatic diamines or alicyclic diamines such as ^7- methanoindanylene dimethylene diamine, tricyclo [6,2,1,0 ^2,7 ] -undecylene dimethyl diamine, and 4,4′-methylene bis (cyclohexylamine). In addition to the above-mentioned compounds, phenylenediamines having a steroid group of the following formula (VI) are also used as aromatic diamines:

[0053]

Embedded image

(Wherein R ¹¹ represents —O—, —COO—,
2 selected from OCO-, -CONH- and -CO-
R ¹² represents a valent organic group;
These diamines (which represent a valence organic group) can be used alone or in combination of two or more.

In the case where an aromatic diamine is used, if the two amino groups are located at the m-position (the 3-position) on the aromatic ring, the light of the soluble imide itself in the g-line and i-line regions is obtained. Absorption tends to be small, which is advantageous when designing a photosensitive resin.

As described above, the soluble polyimide contained in the photosensitive resin composition of the present invention can be obtained, for example, by reacting an acid dianhydride with a diamine in an organic solvent to obtain a polyamic acid, and then subjecting the soluble polyimide to a dehydration reaction. It is obtained by imidization. This polyamic acid can be obtained, for example, by dissolving a diamine in an organic solvent or diffusing it in a slurry state in an inert atmosphere such as argon or nitrogen, and adding an acid dianhydride thereto to cause a reaction. Acid anhydrides are
It is added in a state of being dissolved in an organic solvent and dispersed in a slurry state or in a solid state.

The organic solvent used in the above reaction is not particularly limited as long as it can dissolve the obtained polyamic acid. Usually, an organic polar solvent is used. For example, the following solvents are used: sulphoxide solvents such as dimethylsulfoxide and diethylsulfoxide; formamide solvents such as N, N-dimethylformamide and N, N-diethylformamide; N, N-dimethylacetamide, N, N- Acetamide solvents such as diethylacetamide; N-methyl-2-pyrrolidone;
A pyrrolidone-based solvent such as N-vinyl-2-pyrrolidone;
Phenol solvents such as phenol, o-, m- or p-cresol, xylenol, halogenated phenol, catechol; ether solvents such as tetrahydrofuran and dioxane; alcohol solvents such as methanol, ethanol and butanol; cellosolve such as butyl cellosolve System solvent; hexamethylphosphoramide; γ-butyrolactone and the like. These are preferably used alone or as a mixture, but it is also possible to use an aromatic hydrocarbon such as xylene or toluene. As will be described later, after the polyamic acid synthesis reaction, the solvent is removed and imidation is carried out simultaneously by heating and reducing the pressure. Is advantageous in terms of the process.

The reaction temperature during the synthesis of the above polyamic acid is as follows:
-20 ° C to 90 ° C is desirable. Reaction time is 30 minutes to 2
It is about 4 hours. The average molecular weight (weight average molecular weight) of the obtained polyamic acid is desirably 5,000 to 1,000,000. When the average molecular weight is less than 5000,
The molecular weight of the soluble polyimide obtained from the polyimide acid decreases. When a photosensitive resin composition containing such a soluble polyimide is used, for example, the obtained dry film resist tends to be brittle. On the other hand, if the molecular weight exceeds 1,000,000, the viscosity of the solution (varnish) containing the polyamic acid tends to be too high and handling tends to be difficult.

The polyamic acid obtained above is converted into a polyimide by a dehydration reaction. The method of imidization is not particularly limited, but a method in which the reaction mixture obtained by synthesizing the polyamic acid is heated under reduced pressure is suitably employed. According to this method, since water generated by imidization can be positively removed from the system, hydrolysis of the polyimide by the water can be suppressed, and a decrease in molecular weight can be avoided. . In general, in the used acid dianhydride, a tetracarboxylic acid that has been hydrolyzed and ring-opened or one in which one of the acid dianhydrides has been hydrolyzed may be mixed. However, the polymerization reaction of polyamic acid is stopped, and a high molecular weight polyimide cannot be obtained. However, when the above-described method of heating under reduced pressure is adopted, the acid dianhydride opened by heating is closed again to form an acid dianhydride, and reacts with the amine remaining in the system.
At this time, water is effectively removed from the system because of the reduced pressure, and hydrolysis by the water is avoided. Therefore, a higher molecular weight polyimide can be obtained.

In addition to the above, any of the general imidization methods can be employed. For example, a method in which an azeotropic solvent such as toluene or xylene is added to a reaction mixture in which the above-mentioned polyamic acid has been synthesized and heated to perform imidization and simultaneously remove water by azeotropic distillation; There is a method in which an aliphatic acid dianhydride such as acetic anhydride and a tertiary amine such as triethylamine, pyridine, picoline, isoquinoline and the like are added to the resulting reaction mixture, and imidation is performed and dehydration is performed at the same time.

However, in the former azeotropic removal of water, since water is present in the reaction system, hydrolysis by water may occur. The latter chemical imidization method is more advantageous than the former system in terms of hydrolysis because the generated water is chemically removed by the conversion of the aliphatic acid dianhydride to the aliphatic acid. However, since aliphatic dianhydride and tertiary amine remain in the system, a step of removing them is required. As described above, these methods also have the above-mentioned problems, so that an imidation method is selected according to the purpose. The method of heating under reduced pressure is particularly preferably employed.

When the imidization method of heating under reduced pressure is employed, the heating temperature is preferably from 80 to 400 ° C. At such a temperature, imidization is performed efficiently. Preferably 100 ° C. or higher where water is efficiently removed,
In particular, it is preferable to employ a temperature of 120 ° C. or higher. The maximum temperature is desirably set to a temperature not higher than the thermal decomposition temperature of the polyimide used. Usually, the imidization is almost completed at about 200 to 350 ° C., so that the maximum temperature can be set at this level.

The pressure of the reaction system is preferably low as described above, but may be any pressure under which the water generated during imidization can be efficiently removed under the above heating conditions. Specifically, the pressure in the system is 0.9 to 0.001 atm, desirably 0.8 to 0.001 atm, and more desirably,
0.7-0.01 atm.

Specifically, the soluble polyimide used in the present invention is advantageously prepared, for example, by heating and drying a polyamic acid solution under reduced pressure to directly imidize the solution. For example, the polyimideation reaction is accomplished using a vacuum oven as a batch-type method or using a twin-screw or 3-screw extruder with a decompression device as a continuous method. These methods are appropriately selected depending on the production amount. The twin-screw or triple-screw extruder with a decompression device referred to here is a general melt extruder that heat-melts and extrudes a thermoplastic resin, and is accompanied by a device that removes a solvent by decompressing a general melt extruder. . The polyamic acid solution is heated and kneaded by such an extruder to remove a solvent and water generated during imidization. In this way, a soluble polyimide is formed.

The “soluble” of the soluble polyimide contained in the photosensitive resin composition of the present invention means that it is soluble in an organic solvent having a boiling point of 120 ° C. or lower in a temperature range of room temperature to 100 ° C. Examples of such an organic solvent include ether solvents such as dioxane, dioxolan, and tetrahydrofuran; and halogen solvents such as chloroform and methylene chloride. Such a polyimide that is easily dissolved in an organic solvent is suitably produced, for example, by using an acid dianhydride having an ester bond as shown in the above formula (IV) as a raw material.

The COOH equivalent of the soluble polyimide is
200-3000. The COOH equivalent of the polyimide corresponds to a value (average value) obtained by dividing the molecular weight of the polyimide by the number of carboxyl groups present in the polyimide molecule. Such a polyimide having a COOH equivalent of 200 to 3000 is realized, for example, by using the above-described diamine having a carboxyl group as at least a part of a raw material of a soluble polyimide. Preferred COOH equivalents of the soluble polyimide are 250 to 2500,
More preferably, it is 300 to 2000. COOH
When the equivalent is more than 3000, the resin composition containing the polyimide hardly dissolves in an aqueous alkaline developer,
The development time tends to be long. Considering the structure and molecular weight of the acid dianhydride as the raw material used to prepare the soluble polyimide, the COOH equivalent of the soluble polyimide is usually 200 or more as described above. For example,
The COOH equivalent of a polyimide synthesized from a compound represented by the above formula (V) (R ⁹ is a single bond), which is one of relatively simplified models, and diaminophthalic acid is 227. When the compound of the above formula (V) in which R ⁹ is —C (CF ₃ ) ₂ —, the COOH equivalent becomes 299.

In order to realize the above-mentioned COOH equivalent, it is desirable to use a diamine having two or more in the molecule.
By using this diamine and other diamines in combination,
A polyimide having a predetermined carboxylic acid equivalent and having desired physical properties can be easily designed.

The “polyfunctional (meth) acrylic compound” contained in the photosensitive resin composition of the present invention refers to at least one of a polyfunctional acrylic compound and a polyfunctional methacrylic compound. This polyfunctional acrylic compound refers to at least two acryloyl groups (CH ₂ =
CHCO-), and a polyfunctional methacrylic compound is defined as at least two methacryloyl groups (C
H ₂ ＣC (CH ₃ ) CO—).
The “analog of the polyfunctional (meth) acrylic compound” is a compound having a group having a reactive double bond, which is similar to the acryloyl group or the methacryloyl group. Examples of such a compound include a compound having an allyl group. In the present specification, such polyfunctional (meth) acrylic compounds and their analogs may be collectively referred to as polyfunctional (meth) acrylic compounds (B). Such a compound is polymerized by exposure to light and forms a stitch-like resin matrix to insolubilize the entire composition.

The polyfunctional (meth) acrylic compounds (B) include, but are not limited to, the following compounds: bisphenol F EO modified diacrylate (n = 2 to 50) (EO is Ethylene oxide, n is the number of moles of ethylene oxide added; the same applies hereinafter), bisphenol A EO-modified diacrylate (n
= 2-50), bisphenol S EO modified diacrylate (n = 2-50), bisphenol F EO modified dimethacrylate (n = 2-50), bisphenol S
EO-modified dimethacrylate (n = 2 to 50), bisphenol A EO-modified dimethacrylate (n = 2 to 50)
50), 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, ethylene glycol diacrylate, pentaerythritol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol hexaacrylate, tetramethylolpropane tetraacrylate , Tetraethylene glycol diacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, ethylene glycol dimethacrylate, pentaerythritol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate,
Dipentaerythritol hexamethacrylate, tetramethylolpropane tetramethacrylate, tetraethylene glycol dimethacrylate, methoxydiethylene glycol methacrylate, methoxypolyethylene glycol methacrylate, β-methacryloyloxyethyl hydrogen phthalate, β-methacryloyloxyethyl hydrogen succinate, 3-chloro- 2
-Hydroxypropyl methacrylate, stearyl methacrylate, phenoxyethyl acrylate, phenoxydiethylene glycol acrylate, phenoxy polyethylene glycol acrylate, β-acryloyloxyethyl hydrogen succinate, lauryl acrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene Glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate,
Neopentyl glycol dimethacrylate, polypropylene glycol dimethacrylate, 2-hydroxy 1,
3-dimethacryloyloxypropane, polyethylene glycol diacrylate, tripropylene glycol diacrylate, polypropylene glycol diacrylate, 2-hydroxy 1-acryloyloxy 3-methacryloyloxypropane, trimethylolpropane trimethacrylate, tetramethylolmethane triacrylate, tetramethylol Methanetetraacrylate, methoxydipropylene glycol methacrylate, methoxytriethylene glycol acrylate, nonylphenoxy polyethylene glycol acrylate, nonylphenoxy polypropylene glycol acrylate, 1-acryloyloxypropyl-2-phthalate, isostearyl acrylate, polyoxyethylene alkyl ether acrylate Nonylphenoxy ethylene glycol acrylate, polypropylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 3
-Methyl-1,5-pentanediol dimethacrylate, 1,6-hexanediol dimethacrylate, 1,
9-nonanediol dimethacrylate, 2,4-diethyl-1,5-pentanediol dimethacrylate, 1,
4-cyclohexane dimethanol dimethacrylate, dipropylene glycol diacrylate, tricyclodecane dimethanol diacrylate, 2,2-hydrogenated bisphenol AEO-modified diacrylate (n = 2 to 50), bisphenol A PO-modified diacrylate (n = 2-5
0) (PO is propylene oxide, n is the number of moles of propylene oxide added), 2,4-diethyl-1,5-
Pentanediol diacrylate, ethoxylated tomethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, isocyanuric acid E
O-modified triacrylate, pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate, propoxylated pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol polyacrylate, triallyl isocyanurate, glycidyl methacrylate, glycidyl allyl ether, 1, 3,5-triacryloylhexahydro-s-triazine, triallyl 1,3
5-benzenecarboxylate, triallylamine, triallyl citrate, triallyl phosphate, allobarbital, diallylamine, diallyldimethylsilane, diallyl disulfide, diallyl ether, diallyl cyanurate, diallyl isophthalate, diallyl terephthalate, 1,3-diaryloxy -2-propanol, diallyl sulfide, diallyl maleate, 4,
4′-isopropylidene diphenol dimethacrylate, 4,4′-isopropylidene diphenoxy diacrylate and the like. These polyfunctional (meth) acrylic compounds (B) may be a single compound or a mixture of several compounds.

From the viewpoint that the flexibility of the dry resist obtained from the photosensitive resin composition of the present invention can be exhibited, the above polyfunctional (meth) acrylic compounds (B)
Examples include bisphenol F EO modified diacrylate, bisphenol A EO modified diacrylate, bisphenol S EO modified diacrylate, bisphenol F EO modified dimethacrylate, and bisphenol A
EO-modified dimethacrylate, bisphenol SE
It is preferable to use O-modified dimethacrylate or the like.
Particularly, a compound in which the repeating unit of EO contained in one molecule of diacrylate or dimethacrylate is in the range of 2 to 50, particularly 4 to 40 is preferable. The solubility of the EO repeating unit in an aqueous alkaline solution is improved, so that the development time after exposure of the obtained resin composition is shortened and the resolution is increased. If it exceeds 50, the heat resistance of the obtained resin composition tends to deteriorate.

The polyfunctional (meth) acrylic compound (B) is the same as the soluble polyimide (A) 100 of the present invention.
It is preferably contained in an amount of 1 to 200 parts by weight, more preferably 3 to 150 parts by weight, based on parts by weight. 1 to
If the amount is out of the range of 200 parts by weight, the intended effect may not be obtained or the developability may be adversely affected.

The photoreaction initiator (C) contained in the photosensitive resin composition of the present invention is not particularly limited. A compound that generates a radical by light having a long wavelength of about g-line by light is preferably used. Such compounds include 3,
Examples include 3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, and acylphosphine oxide compounds represented by the following general formulas (VII) and (VIII). Further, a commonly used sensitizer or a combination of the sensitizer and a photopolymerization auxiliary can also be used as the photoreaction initiator (C). The radical generated by the photoreaction initiator (C) is
Reactive groups having a double bond (vinyl group, acryloyl group,
(Methacryloyl group, allyl group, etc.). Therefore, the polymerization reaction of the polyfunctional (meth) acrylic compound (B) proceeds, and the crosslinking is promoted.

[0073]

Embedded image

(Wherein R ¹² is C ₆ H ₅ —, C ₆ H _{4
(CH 3) -, C 6} H 2 (CH 3) 3 -, (CH 3) 3
C-, or _C 6 _H 3 Cl ₂ - ^{indicates, R 13} and R
¹⁴ are each independently C ₆ H ₅ —, methoxy, ethoxy, C ₆ H ₄ (CH ₃ ) —, or C ₆ H ₂ (CH ₃ )
_3- is shown. )

[0075]

Embedded image

(Wherein R ¹⁵ and R ¹⁷ are each independently C ₆ H ₅ —, C ₆ H ₄ (CH ₃ ) —, C ₆ H ₂ (C
_{H 3) 3 -, (CH} 3) 3 C-, or _C 6 _H 3 Cl ₂
And R ¹⁶ represents C ₆ H ₅ —, methoxy, ethoxy, C ₆ H ₄ (CH ₃ ) —, or C ₆ H ₂ (CH ₃ ).
_3- is shown. )

The acylphosphine oxide represented by the general formula (VII) generates two radicals, and the acylphosphine oxide represented by the general formula (VIII) generates four radicals by α-cleavage. appear. Acylphosphine oxides represented by the general formula (VIII) are particularly preferred.

The sensitizers include, but are not limited to, the following compounds: Michler's ketone, bis-4,4'-diethylaminobenzophenone, benzophenone, camphorquinone, benzyl, 4,4'-dimethylaminobenzyl , 3,5-bis (diethylaminobenzylidene) -N-methyl-4-piperidone, 3,5-
Bis (dimethylaminobenzylidene) -N-methyl-4
-Piperidone, 3,5-bis (diethylaminobenzylidene) -N-ethyl-4-piperidone, 3,3'-carbonylbis (7-diethylamino) coumarin, riboflavin tetrabutyrate, 2-methyl-1- [4- ( Methylthio) phenyl] -2-morpholinopropane-1-
ON, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 3,5-dimethylthioxanthone, 3,5-diisopropylthioxanthone, 1-phenyl-2- (ethoxycarbonyl) oxyiminopropane -1-on,
Benzoin ether, benzoin isopropyl ether, benzanthrone, 5-nitroacenaphthene, 2-
Nitrofluorene, anthrone, 1,2-benzanthraquinone, 1-phenyl-5-mercapto-1H-tetrazole, thioxanthen-9-one, 10-thioxanthenone, 3-acetylindole, 2,6-di (p-
Dimethylaminobenzal) -4-carboxycyclohexanone, 2,6-di (p-dimethylaminobenzal)-
4-hydroxycyclohexanone, 2,6-di (p-diethylaminobenzal) -4-carboxycyclohexanone, 2,6-di (p-diethylaminobenzal) -4
-Hydroxycyclohexanone, 4,6-dimethyl-7
-Ethylaminocoumarin, 7-diethylamino-4-methylcoumarin, 7-diethylamino-3- (1-methylbenzimidazolyl) coumarin, 3- (2-benzimidazolyl) -7-diethylaminocoumarin, 3- (2-
Benzothiazolyl) -7-diethylaminocoumarin, 2
-(P-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) quinoline,
-(P-dimethylaminostyryl) quinoline, 2- (p
-Dimethylaminostyryl) zenzothiazole, 2-
(P-dimethylaminostyryl) -3,3-dimethyl-3H-indole and the like.

The sensitizer is a soluble polyimide resin (A) 1
The composition is preferably contained in the composition at a ratio of 0.1 to 50 parts by weight with respect to 00 parts by weight, more preferably 0.3 to 2 parts by weight.
It is contained in a proportion of 0 parts by weight. If the amount is outside the range of 0.1 to 50 parts by weight, the sensitizing effect may not be obtained or the developing property may be unfavorably affected. As the sensitizer, one kind of compound may be used, or a mixture of several kinds may be used.

The photopolymerization aid is used to enhance the photosensitivity of the photosensitive resin composition of the present invention. Photopolymerization aids include, but are not limited to, the following compounds: 4-diethylaminoethylbenzoate, 4-
Dimethylaminoethylbenzoate, 4-diethylaminopropylbenzoate, 4-dimethylaminopropylbenzoate, 4-dimethylaminoisoamylbenzoate, N-phenylglycine, N-methyl-N-phenylglycine, N- (4-cyanophenyl) glycine, 4
-Dimethylaminobenzonitrile, ethylene glycol dithioglycolate, ethylene glycol di (3-mercaptopropionate), trimethylolpropanethioglycolate, trimethylolpropanetri (3-mercaptopropionate), pentaerythritol tetrathioglycolate , Pentaerythritol tetra (3-
Mercaptopropionate), trimethylolethanetrithioglycolate, trimethylolpropanetrithioglycolate, trimethylolethanetri (3-mercaptopropionate), dipentaerythritol hexa (3-mercaptopropionate), thioglycol Acid, α-mercaptopropionic acid, t-butylperoxybenzoate, t-butylperoxymethoxybenzoate, t-butylperoxynitrobenzoate, t
-Butyl peroxyethyl benzoate, phenyl isopropyl peroxy benzoate, di-t-butyl diperoxy isophthalate, tri-t-butyl triperoxy trimellitate, tri-t-butyl triperoxy trimellitate, tetra-t-butyl tetraperoxy pyromellitate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, 3,3 ′, 4,4′-tetra (t
-Butylperoxycarbonyl) benzophenone, 3,
3,4,4′-tetra (t-amylperoxycarbonyl) benzophenone, 3,3 ′, 4,4′-tetra (t
-Hexylperoxycarbonyl) benzophenone,
2,6-di (p-azidobenzal) -4-hydroxycyclohexanone, 2,6-di (p-azidobenzal)-
4-carboxycyclohexanone, 2,6-di (p-azidobenzal) -4-methoxycyclohexanone,
6-di (p-azidobenzal) -4-hydroxymethylcyclohexanone, 3,5-di (p-azidobenzal)
-1-methyl-4-piperidone, 3,5-di (p-azidobenzal) -4-piperidone, 3,5-di (p-azidobenzal) -N-acetyl-4-piperidone, 3,5
-Di (p-azidobenzal) -N-methoxycarbonyl-4-piperidone, 2,6-di (p-azidobenzal)
-4-hydroxycyclohexanone, 2,6-di (m-
Azidobenzal) -4-carboxycyclohexanone,
2,6-di (m-azidobenzal) -4-methoxycyclohexanone, 2,6-di (m-azidobenzal) -4
-Hydroxymethylcyclohexanone, 3,5-di (m
-Azidobenzar) -N-methyl-4-piperidone;
3,5-di (m-azidobenzal) -4-piperidone,
3,5-di (m-azidobenzal) -N-acetyl-4
-Piperidone, 3,5-di (m-azidobenzal) -N
-Methoxycarbonyl-4-piperidone, 2,6-di (p-azidocinnamylidene) -4-hydroxycyclohexanone, 2,6-di (p-azidocinnamylidene)
-4-carboxycyclohexanone, 2,6-di (p-
Azidocinnamylidene) -4-cyclohexanone, 3,
5-di (p-azidocinnamylidene) -N-methyl-4
-Piperidone, 4,4'-diazidochalcone, 3,3 '
-Diazidochalcone, 3,4'-diazidochalcone,
4,3'-diazidochalcone, 1,3-diphenyl-
1,2,3-propanetrione-2- (o-acetyl)
Oxime, 1,3-diphenyl-1,2,3-propanetrione-2- (on-propylcarbonyl) oxime, 1,3-diphenyl-1,2,3-propanetrione-2- (o-methoxy Carbonyl) oxime, 1,3
-Diphenyl-1,2,3-propanetrione-2-
(O-ethoxycarbonyl) oxime, 1,3-diphenyl-1,2,3-propanetrione-2- (o-benzoyl) oxime, 1,3-diphenyl-1,2,3-
Propanetrione-2- (o-phenyloxycarbonyl) oxime, 1,3-bis (p-methylphenyl)-
1,2,3-propanetrione-2- (o-benzoyl) oxime, 1,3-bis (p-methoxyphenyl)
-1,2,3-propanetrione-2- (o-ethoxycarbonyl) oxime, 1- (p-methoxyphenyl)
-3- (p-nitrophenyl) -1,2,3-propanetrione-2- (o-phenyloxycarbonyl) oxime and the like. As an auxiliary agent of a type other than the above, it is possible to include trialkylamines such as triethylamine, tributylamine, and triethanolamine. As these photopolymerization assistants, one kind of compound may be used, or several kinds may be mixed.

The photopolymerization assistant is soluble polyimide (A) 1
The composition is preferably contained in the composition at a ratio of 0.1 to 50 parts by weight with respect to 00 parts by weight, more preferably 0.3 to 2 parts by weight.
It is contained in a proportion of 0 parts by weight. If the amount is outside the range of 0.1 to 50 parts by weight, the intended sensitizing effect may not be obtained, or may adversely affect the developability.

The photosensitive resin composition of the present invention contains the above-mentioned soluble polyimide (A), polyfunctional (meth) acrylic compounds (B), and (C) a photoreaction initiator, and optionally contains the above-mentioned photoreaction initiator. It contains a sensitizer, a photopolymerization auxiliary, and various other components.

The other components include resins other than the soluble polyimide (A) and the polyfunctional (meth) acrylic compound (B), organic or inorganic fillers,
Examples include a reinforcing material, a coupling agent, various additives, and an organic solvent.

Examples of the resin other than the soluble polyimide (A) and the polyfunctional (meth) acrylic compound (B) include a thermosetting resin and a thermoplastic resin. Examples of the thermosetting resin include an epoxy resin and a thermosetting acrylic resin, and examples of the thermoplastic resin include polyester, polyamide, polyurethane, and polycarbonate.

The epoxy resin is contained in order to improve the adhesiveness of the photosensitive resin composition. The type of epoxy resin is not particularly limited, but includes the following compounds:
Bisphenol resins such as Epicoat 828 (manufactured by Yuka Shell); orthocresol novolak resins such as 180S65 (manufactured by Yuka Shell); bisphenol A novolak resins such as 157S70 (manufactured by Yuka Shell); 1032H
Trishydroxyphenylmethane novolak resin such as 60 (manufactured by Yuka Shell); naphthalene aralkyl novolak resin such as ESN375; tetraphenylolethane 1
031S (manufactured by Yuka Shell), YGD414S (Toto Kasei), Trishydroxyphenylmethane EPPN502
H (Nippon Kayaku), special bisphenol VG3101L
(Mitsui Chemicals), special naphthol NC7000 (Nippon Kayaku), TETRAD-X, TETRAD-C (manufactured by Mitsubishi Gas Chemical Company), and other glycidylamine-type resins.

The epoxy resin is preferably used in a mixture with a compound having an epoxy group and a double bond or a triple bond in a molecule, or with another thermosetting resin. Such compounds include allyl glycidyl ether,
Glycidyl acrylate, glycidyl methacrylate,
Glycidyl vinyl ether, propargyl glycidyl ether, glycidyl propiolate, ethynyl glycidyl ether and the like can be exemplified. Examples of the other thermosetting resins include bismaleimide, bisallylnadiimide, phenol resin, and cyanate resin.

When the photosensitive resin composition of the present invention contains an epoxy resin, if a curing agent for the epoxy resin is further contained, a cured product having good physical properties can be obtained. Such a curing agent is not particularly limited, for example, amine-based,
Examples include imidazole-based, acid anhydride-based, and acid-based curing agents.

As described above, the photosensitive composition of the present invention comprises
An organic solvent may be contained. If it is dissolved in an appropriate organic solvent, it can be used in a solution (varnish) state, which is convenient for coating and drying. The solvent used is preferably an aprotic polar solvent from the viewpoint of solubility. Specifically, the following compounds are mentioned: N
-Methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N-benzyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, hexamethylphosphortriamide,
N-acetyl-ε-caprolactam, dimethylimidazolidinone, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, γ-butyrolactone, dioxane, dioxolan, tetrahydrofuran, chloroform, methylene chloride and the like. These may be used alone or as a mixed system.

The organic solvent is a soluble polyimide (A)
The solvent used in the synthesis reaction may be left as it is, or may be newly added to the isolated soluble polyimide. In order to improve the coatability of the resin composition solution,
Solvents other than the above, such as toluene, xylene, diethyl ketone, methoxybenzene, and cyclopentanone, may be mixed in a range that does not adversely affect the solubility of the polymer.

The soluble polyimide contained in the composition of the present invention has good solubility in an organic solvent. Can be dissolved in a solvent having a boiling point of 120 ° C. or lower. In particular, as the main components of the acid dianhydride, 2,2′-hexafluoropropylidene diphthalic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, the above-mentioned formula (IV Using an ester-based acid dianhydride represented by the formula (1), in addition to a diamine having two or more carboxyl groups in the molecule, an aromatic diamine having an amino group at the m-position, a diamine having a sulfone group, The solubility of the soluble polyimide (A) obtained by using the siloxane diamine represented by the above formula (I) is extremely high. Since the above-mentioned boiling point can be dissolved in a solvent having a boiling point of 120 ° C. or less, when the photosensitive resin composition is applied and dried as a solution in which such a solvent is dissolved, a high temperature is required during the drying. The thermal polymerization of the contained (meth) acrylic compound (B) can be prevented.

The photosensitive resin composition of the present invention containing the above components is used for various uses. Preferably, the solvent in the solution composition is removed to obtain a film-shaped photosensitive dry film resist. This dry film resist can be obtained as a single film by applying a solution of the composition of the present invention on a support made of metal or PET, drying and drying, and then peeling off the support. Alternatively, it is also possible to form a dry film resist on a required film base material such as PET by the above-described means, and use the dry film resist in a state of being laminated. The drying temperature of the photosensitive resin composition solution is determined by the double bond of the polyfunctional (meth) acrylic compound (B) due to heat, or the double bond, triple bond, epoxy bond of another compound contained in the composition. It is desirable to use a temperature at which the groups do not react and become inactive. Specifically, the temperature is 180 ° C or lower, preferably 150 ° C or lower.

The photosensitive dry film resist of the present invention is suitably used as a coverlay film for protecting the surface of an electronic circuit board or the like. For example, the above-mentioned photosensitive dry film resist is bonded to a conductor surface of a substrate such as an FPC on which a circuit is formed in advance by a conductor such as a copper foil. Specifically, combining FPC and photosensitive dry film film resist,
Lamination is performed by hot lamination, hot press or hot vacuum lamination.

The bonding temperature at this time is determined by the double bond of the polyfunctional (meth) acrylic compound (B) due to heat, or the double bond, triple bond or epoxy group of another compound contained in the composition. It is desirable to use a temperature that does not cause reaction and inactivation. Specifically, the temperature is 180 ° C. or lower, preferably 150 ° C. or lower, more preferably 130 ° C. or lower, and particularly preferably 110 ° C. or lower. The photosensitive dry film resist of the present invention comprises 1
It can be laminated at a temperature of 50 ° C. or less, and can be directly laminated on a printed circuit board without using an adhesive. Thus, the photosensitive coverlay film laminated printed board of the present invention is obtained.

The use of this photosensitive coverlay film-laminated printed circuit board eliminates the conventional disadvantages.
That is, conventionally, a hole or a window corresponding to a terminal portion of a circuit or a joint portion with a component is previously formed in a coverlay film, and a hole or the like of the coverlay film is
Positioning was performed to match the terminals of C and the joints with the parts. However, this was almost manual work, and the work size was small. There was a disadvantage that this was the case. According to the present invention, as described later, a hole or the like can be easily formed at a desired position, and such a disadvantage is solved.

Next, the photosensitive dry film resist (photosensitive coverlay film) on the substrate is irradiated with light through a photomask of a predetermined pattern, and then exposed to light using a basic solution as a developing solution. The part is dissolved and removed to obtain a desired pattern. This developing step may be performed using a normal positive-type photoresist developing device.

The base contained in the basic solution used as the developer is soluble in water or alcohol,
The solution is not particularly limited as long as it is a compound exhibiting basicity (basic compound). Such compounds include, for example, hydroxides, carbonates, amine salts of alkali metals, alkaline earth metals, or ammonium ions. Specifically, the compounds include the following: 2-dimethylaminoethanol, 3-dimethylamino-1-propanol, 4-dimethylamino-1-butanol, 5-dimethylamino-1-pentanol, 6-dimethylaminoethanol Dimethylamino-1-hexanol, 2-dimethylamino-2-methyl-1-propanol, 3-dimethylamino-2,21-dimethyl-1-propanol, 2-diethylaminoethanol, 3-diethylamino-1-propanol, 2- Diisopropylaminoethanol, 2-di-n-butylaminoethanol, N, N-dibenzyl-2-aminoethanol, 2- (2-dimethylaminoethoxy) ethanol, 2- (2-diethylaminoethoxy) ethanol,
1-dimethylamino-2-propanol, 1-diethylamino-2-propanol, N-methyldiethanolamine, N-ethyldiethanolamine, Nn-butyldiethanolamine, Nt-butyldiethanolamine, N-lauryldiethanolamine, 3-diethylamino- 1,2-propanediol, triethanolamine, triisopropanolamine, N-methylethanolamine, N-ethylethanolamine, Nn-butylethanolamine, Nt-butylethanolamine, diethanolamine, diisopropanolamine ,
2-aminoethanol, 3-amino-1-propanol, 4-amino-1-butanol, 6-amino-1-hexanol, 1-amino-2-propanol, 2-amino-2,2-dimethyl-1-propanol , 1-aminobutanol, 2-amino-1-butanol, N- (2-
Aminoethyl) ethanolamine, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-ethyl-1,3-propanediol, 3-amino-1,2
-Propanediol, 2-amino-2-hydroxymethyl-1,3-propanediol, sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate,
Potassium carbonate, ammonium carbonate, sodium bicarbonate, potassium bicarbonate, ammonium bicarbonate, tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropyl ammonium hydroxide, tetraisopropyl ammonium hydroxide, amino methanol, 2-amino ethanol, -Aminopropanol, 2-aminopropanol, methylamine, ethylamine, propylamine, isopropylamine, dimethylamine, diethylamine, dipropylamine, diisopropylamine, trimethylamine, triethylamine, tripropylamine, triisopropylamine and the like.

These compounds may be used alone or in combination of two or more. The developer is usually an aqueous solution of these compounds, but in order to improve the solubility of polyimide, methanol, ethanol, propanol, isopropanol, N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N- A water-soluble organic solvent such as dimethylacetamide may be partially contained. The concentration of the basic compound is generally 0.1 to 5
Although it is 0% by weight, it is preferably 0.1 to 30% by weight in consideration of the influence on the supporting substrate and the like.

The pattern formed by the development is then washed with a rinsing liquid to remove the developing liquid. Preferable examples of the rinsing liquid include methanol, ethanol, isopropyl alcohol, and water having good miscibility with the developing liquid.

By subjecting the substrate having the resist film on which the pattern obtained by the above-described process is formed to a heat treatment at an appropriate temperature from 20 ° C. to 200 ° C.,
Unreacted groups (such as double bonds) react and the resist is sufficiently cured. If the heating temperature at this time exceeds 200 ° C., care must be taken because the crystal structure of copper mainly used for the conductor layer of the substrate changes and the strength decreases. In this way, a substrate having a polyimide film on which a desired pattern of high resolution is formed as a coverlay film is obtained. This film has high heat resistance and excellent mechanical properties.

As described above, it is possible to easily prepare a substrate having a coverlay film having a desired pattern using the photosensitive dry film resist of the present invention.

As described above, since the soluble polyimide (A) contained in the photosensitive resin composition of the present invention is soluble in an organic solvent, the composition is easily formed into a film by casting or the like. Thus, a photosensitive dry film resist can be obtained. This photosensitive dry film resist can be easily bonded to the conductor surface of the printed circuit board by thermal fusion. By exposing and developing this, a hole or the like for joining to the substrate terminal portion can be formed at a required location. The composition of the present invention is easily insoluble in a developer by exposure, and the unexposed portion has high solubility in the developer. Therefore, a pattern is formed with high accuracy. As described above, a coverlay film laminated substrate excellent in positional accuracy with good work efficiency can be obtained.

When such a substrate is joined to another component by soldering, the substrate is usually exposed to a high temperature of 200 ° C. or higher for several seconds. The heat-resistant temperature of the composition of the present invention after heat curing is high, usually 300 ° C. or higher, preferably 320 ° C.
° C or higher, more preferably 340 ° C or higher. Therefore,
The coverlay film-laminated printed circuit board can be joined to desired components without deteriorating the cured coverlay film.

[0103]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to only these examples.

In this example, each evaluation was performed as follows. (1) Thermal decomposition starting temperature: The rate of temperature rise in air was 1 using a thermal analysis measurement device (TG / DTA220) manufactured by Seiko Denshi Kogyo.
Measure the temperature range from room temperature to 500 ° C at 0 ° C / min,
The temperature at which the weight loss was 5% was defined as the pyrolysis onset temperature. (2) Elastic modulus: Measured according to JIS C 2318. (3) Peel adhesive strength: The peel adhesive strength was measured in accordance with JIS C 6481 peeling strength (90 degrees). However, the width of the sample film was measured with a width of 3 mm and converted to a width of 1 cm. (4) Weight average molecular weight: Measured using Waters GPC under the following conditions. (Column: K manufactured by Shodex
D-806M 2 tubes, temperature 60 ° C., detector: RI, flow rate: 1 ml / min, developing solution: DMF (lithium bromide 0.0
3M, phosphoric acid 0.03M), sample concentration: 0.2 wt%,
Injection volume: 20 μl, reference substance: polyethylene oxide) (5) Measurement of imidation ratio: (i) Polyamic acid solution (D
MF solution) on a PET film,
For 10 minutes and at 130 ° C. for 10 minutes, and then peeled off from the PET film. Fix this to the pin frame,
60 minutes at 200 ° C. for 60 minutes and 250 ° C.
For 60 minutes to obtain a polyimide film having a thickness of 5 μm. (Ii) The polyimide prepared in Examples or Comparative Examples was dissolved in DMF, cast on a PET film, heated at 100 ° C. for 30 minutes, peeled off the PET film, and fixed to a pin frame. In a vacuum oven,
Heat and dry under the conditions of 80 ° C and 5 mmHg for 12 hours,
A polyimide film having a thickness was obtained. (I) and (ii)
The IR of each film obtained in the above was measured, and the ratio of imide absorption / benzene ring absorption was determined. When the ratio of imide absorption / benzene ring obtained by measuring the film obtained in (i) is 100% and the ratio of imide absorption / benzene ring of film (ii) is what percentage, I asked for the equivalent. This value was taken as the imidation ratio.

In this example, the following abbreviations indicate the compounds shown on the right, respectively: ESDA: 2,2-bis (4-hydroxyphenyl) propanedibenzoate-3,3 ', 4,4'-tetracarboxylic acid Dianhydride BAPS-M: bis [4- (3-aminophenoxy) phenyl] sulfone DMAc: N, N-dimethylacetamide DMF: N, N-dimethylformamide

Here, the COOH equivalent corresponds to a value (average value) obtained by dividing the molecular weight of a compound having a COOH group by the number of COOH groups present in the molecule of the compound.

Example 1 2000 m with a stirrer
8.60 g of BAPS-M in a 1 l separable flask
(0.02 mol), siloxane diamine (K
F8010; in the siloxane diamine represented by the formula (I), x = 3, y = 10, R ¹ = CH ₃ ) 16.6 g
(0.02 mol) and 200 g of DMF were added thereto, and 57.65 g (0.10 mol) of ESDA was added thereto at once with vigorous stirring, and stirring was continued for 30 minutes.
Then, 17.2 g (0.06 mol) of bis (4-amino-3-carboxy-phenyl) methane was added to 75 g of DMF.
And added to the above solution, followed by stirring for 30 minutes to obtain a polyamic acid solution. The weight average molecular weight (hereinafter referred to as Mw) of this polyamic acid was 60,000.

The polyamic acid solution was placed on a Teflon (registered trademark) -coated vat and placed in a vacuum oven for 15 minutes.
0 ° C. for 10 minutes, 160 ° C. for 10 minutes, 170 ° C. for 10 minutes, 180 ° C. for 10 minutes, 190 ° C. for 10 minutes
And heated at 210 ° C. for 30 minutes at a pressure of 5 mmHg under reduced pressure. It was taken out from the vacuum oven to obtain 96 g of a soluble polyimide having a carboxyl group. The Mw of this polyimide was 62,000, and the imidation ratio was 100% (COOH equivalent: 804).

The soluble polyimide was dissolved in dioxolan to obtain a 30% by weight solution. As a photoreaction initiator, 0.5 g (1.2 mmol) of bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide and bisphenol A EO-modified (n) were added to 100 g of the obtained 30% by weight soluble imide solution. # 30) 25 g of diacrylate (ABE-30 manufactured by Shin-Nakamura Chemical) and 10 mg of methoxyphenol as a polymerization inhibitor were added. The obtained solution was applied on a PET film having a thickness of 25 μm,
C. for 5 minutes and then at 65.degree. C. for 5 minutes to obtain a photosensitive polyimide film (38 .mu.m thickness) / PET film (25 .mu.m thickness) two-layer film.

A copper foil was added to this two-layer film, and the copper foil / photosensitive polyimide film (38 μm) / PET film (2
5 μm), 100 ° C., 100 N / c
and laminating under the conditions of m. After lamination, exposure was performed for 3 minutes from the PET film side surface (exposure condition: 400 nm).
10 mJ / cm ² ). After peeling off the PET film, the film was post-baked at 100 ° C. for 3 minutes and cured at 180 ° C. for 2 hours.

[0111] The peel adhesion strength of the obtained polyimide film / copper foil (flexible copper-clad board) was 11.8 N / c.
m (1.2 kgf / cm), and no defects such as swelling were observed even when immersed in a 260 ° C. solder bath for 1 minute.

After the copper foil of the flexible copper-clad plate was removed by etching, the elasticity of the remaining cured coverlay film was 1000 N / mm ² , the elongation was 25%, and the thermal decomposition onset temperature was 370 ° C. there were.

Separately, a copper foil is laminated on the two-layer film of the photosensitive polyimide film (38 μm) / PET film (25 μm) so as to be copper foil / photosensitive polyimide film / PET film. ° C, 10
Lamination was performed under the condition of 0 N / cm. After lamination, a mask having a line / space of 100/100 μm was covered and exposed for 3 minutes from the PET film side (exposure conditions:
400 nm light is 10 mJ / cm ² ). After peeling off the PET film, post-bake at 100 ° C for 3 minutes.
% KOH aqueous solution (liquid temperature 40 ° C), then 180 ° C
For 2 hours. When the pattern of this coverlay film was observed with a microscope, a pattern of line / space = 100/100 μm could be drawn.

Example 2 100 g of the 30% by weight soluble polyimide solution obtained in Example 1 was added with bis (2,4,6).
-Trimethylbenzoyl) -phenylphosphine oxide 0.5 g (1.2 mmol), bisphenol F
5 g of EO-modified (n @ 2) diacrylate (Aronix M-208 manufactured by Toagosei), bisphenol A EO-modified (n @ 30) diacrylate (ABE-3 manufactured by Shin-Nakamura Chemical)
0) 20 g and methoxyphenol 10 mg as a polymerization inhibitor were added. The obtained solution was applied on a PET film having a thickness of 25 μm and dried at 45 ° C. for 5 minutes and then at 65 ° C. for 5 minutes to obtain a photosensitive polyimide film (38 μm thickness) / PET film (25 μm thickness). A layer film was obtained.

A copper foil was bonded to this two-layer film in the same manner as in Example 1 to obtain a flexible copper bonded plate. The peel adhesive strength of this flexible copper-clad board is 10.8 N / cm
(1.1 kg weight / cm), and no defects such as swelling were observed even when immersed in a 260 ° C. solder bath for 1 minute. The elastic modulus of the coverlay film after the copper foil of the flexible copper-clad board is removed by etching and cured is 1500 N /
mm ² , elongation is 20%, and thermal decomposition onset temperature is 37
5 ° C.

Separately from this, a copper foil is superimposed on the two-layer film of the photosensitive polyimide film (38 μm) / PET film (25 μm) so as to become copper foil / photosensitive polyimide film / PET film. ° C, 10
Lamination was performed under the condition of 0 N / cm. After lamination, a mask having a line / space of 100/100 μm was covered and exposed from the surface of the PET film for 3 minutes (exposure condition: 400 nm light at 10 mJ / cm ² ). After peeling off the PET film, post-baking at 100 ° C. for 3 minutes, developing with an aqueous solution of 1% KOH (liquid temperature 40 ° C.),
The composition was cured at 80 ° C. for 2 hours. When the pattern of this coverlay film was observed with a microscope, a pattern of line / space = 100/100 μm could be drawn.

Example 3 2000 m with a stirrer
8.61 g of BAPS-M in a 1-separable flask
(0.02 mol) and 260 g of DMF were added thereto, and 57.65 g (0.1 mol) of ESDA was added thereto at once with vigorous stirring, and stirring was continued for 30 minutes. Silicon diamine (KF8010 manufactured by Shin-Etsu Chemical) 24.
9 g (0.03 mol) was added and stirred for 30 minutes, and then 9.81 g (0.05%) of 2,5-diaminoterephthalic acid was added.
Mol) and stirred while cooling with ice water to obtain a polyamic acid solution. The Mw of this polyamic acid was 53,000. This polyamic acid solution is placed on a Teflon-coated vat and placed in a vacuum oven at 150 ° C. for 10 minutes, 160 ° C. for 10 minutes, 170 ° C. for 10 minutes,
10 minutes at 80 ° C., 10 minutes at 190 ° C., and 2
The mixture was heated under reduced pressure at a pressure of 5 mmHg at 10 ° C. for 30 minutes. It was taken out of the vacuum oven to obtain a soluble polyimide having a carboxyl group. The Mw of this polyimide was 60,000, and the imidation ratio was 100% (COOH equivalent: 974).

This soluble polyimide was dissolved in dioxolan to obtain a 30% by weight solution. To 100 g of the obtained 30% by weight soluble imide solution, 0.3 g of 4,4'-bis (diethylamino) benzophenone and BTTB (2
1.0 g of 5% toluene solution), bisphenol A EO
Modified (n ≒ 30) diacrylate (ABE manufactured by Shin-Nakamura Chemical Co., Ltd.)
-30) 20 g, bisphenol A EO modified (n ≒ 1)
0) Diacrylate (Shin Nakamura Chemical ABE-10) 5
g, and methoxyphenol 10 m as a polymerization inhibitor
g was added to obtain a photosensitive resin composition solution. This solution is
Apply on a 5μm thick PET film,
After drying at 65 ° C. for 5 minutes, the photosensitive polyimide film (38 μm thickness) / PET film (25
(thickness μm).

A copper foil was bonded to the two-layer film in the same manner as in Example 1 to obtain a flexible copper bonded plate. The peel adhesive strength of this flexible copper-clad board is 10 N / cm
(1.02 kgf / cm), and no defects such as swelling were observed even when immersed in a 260 ° C. solder bath for 1 minute.
The elastic modulus of the cured coverlay film after removing the copper foil of the flexible copper laminated board by etching is 1250N.
/ Mm ² , the elongation is 25%, and the thermal decomposition onset temperature is 3
80 ° C.

Separately from this, a copper foil is laminated on the two-layered film of the photosensitive polyimide film (38 μm) / PET film (25 μm) so as to be copper foil / photosensitive polyimide film / PET film. ° C, 10
Lamination was performed under the condition of 0 N / cm. After lamination, a mask having a line / space of 100 // 100 μm was put thereon and exposed for 1 minute from the PET film side (exposure conditions:
400 nm light is 10 mJ / cm ² ). After peeling off the PET film, post-bake at 100 ° C for 3 minutes.
% KOH aqueous solution (liquid temperature 40 ° C), then 180 ° C
For 2 hours. When the pattern of the coverlay film obtained by curing was observed with a microscope,
A pattern of line / space = 100/100 μm could be drawn.

Example 4 The same operation as in Example 1 was carried out except that the raw material composition ratio of the soluble polyimide was changed as follows. 17.20 g (0.04 mol) of BAPS-M, siloxane diamine (KF8010 manufactured by Shin-Etsu Chemical; siloxane diamine represented by formula (I); x = 3, y = 10, R ¹
= CH ₃ ) 24.9 g (0.03 mol), ESDA5
7.65 g (0.10 mol) and 8.6 g (0.0%) of bis (4-amino-3-carboxy-phenyl) methane
3 mol). The molecular weight of the obtained amic acid was 59,000. Imidation was carried out in the same manner as in Example 1 to obtain 104 g of a soluble polyimide (COOH equivalent: 1746).

In the same manner as in Example 1, the photosensitive polyimide /
A two-layer film of a PET film was prepared, and then a copper foil was stuck to the two-layer film in the same manner as in Example 1.
A flexible copper-clad board was obtained. The peel adhesive strength of this flexible copper-clad board is 11.8 N / cm (1.2 kgf /
cm) and no defects such as swelling were observed even when immersed in a 260 ° C. solder bath for 1 minute. The copper foil of the flexible copper-clad plate was etched away, and the elasticity of the remaining cured coverlay film was 1000 N / mm ² , the elongation was 25%, and the thermal decomposition onset temperature was 370 ° C.

Separately from this, a copper foil is laminated on the two-layer film of the photosensitive polyimide film (38 μm) / PET film (25 μm) so as to become copper foil / photosensitive polyimide film / PET film. ° C, 10
Lamination was performed under the condition of 0 N / cm. After lamination, a mask having a line / space of 100/100 μm was covered and exposed from the surface of the PET film for 3 minutes (exposure condition: 400 nm light at 10 mJ / cm ² ). After the PET film was peeled off, it was post-baked at 100 ° C. for 3 minutes, and a 0.5% solution of tetramethyl hydroxide in isopropyl alcohol / water = 50/50 weight ratio (liquid temperature 40
C), and cured at 180 ° C. for 2 hours.
When the pattern of this coverlay film was observed with a microscope, a pattern of line / space = 100/100 μm could be drawn.

Comparative Example 1 The same operation was carried out except that the raw material composition ratio of the soluble polyimide in Example 1 was changed as follows: 17.22 g (0.04 mol) of BAPS-M, siloxane diamine (manufactured by Shin-Etsu Chemical Co., Ltd.) KF8010; a siloxane diamine represented by the formula (I); x = 3, y = 10, R ¹
= CH ₃ ) 24.9 g (0.03 mol), ESDA5
7.65 g (0.10 mol), 4.56 g (0.03 mol) of 3,5-diaminobenzoic acid. The molecular weight of the obtained amic acid was 59,000. Imidization was carried out in the same manner as in Example 1 to obtain 99 g of a soluble polyimide (COOH equivalent: 3358).

In the same manner as in Example 1, the photosensitive polyimide /
A two-layer film of a PET film was prepared, and then a copper foil was stuck to the two-layer film in the same manner as in Example 1.
A flexible copper-clad board was obtained. The peel adhesive strength of this flexible copper-clad board is 11.8 N / cm (1.2 kgf /
cm) and no defects such as swelling were observed even when immersed in a 260 ° C. solder bath for 1 minute. The copper foil of the flexible copper-clad plate was etched away, and the elasticity of the remaining cured coverlay film was 1000 N / mm ² , the elongation was 25%, and the thermal decomposition onset temperature was 370 ° C.

Separately from this, a copper foil is laminated on the above-mentioned two-layer film of photosensitive polyimide film (38 μm) / PET film (25 μm) so as to become copper foil / photosensitive polyimide film / PET film. ° C, 10
Lamination was performed under the condition of 0 N / cm. After lamination, a mask having a line / space of 100/100 μm was covered and exposed for 3 minutes from the PET film side (exposure conditions:
400 nm light is 10 mJ / cm ² ). After peeling off the PET film, post-bake at 100 ° C for 3 minutes.
% KOH aqueous solution (liquid temperature 40 ° C)
The unexposed portion did not dissolve and a pattern could not be drawn.

[0127]

According to the present invention, a photosensitive resin composition comprising a soluble polyimide (A) having a predetermined COOH equivalent, a polyfunctional (meth) acrylic compound (B), and a photoreaction initiator (C) Things are provided. A photosensitive dry film resist using this composition can be easily laminated on a conductor surface of a printed circuit board by thermal fusion,
It can be used as a photosensitive coverlay film. The composition of the present invention can be easily developed using an alkali solution after exposure, for example, to obtain a coverlay film laminated substrate having a desired pattern with high accuracy by a simple operation. Can be. When the composition of the present invention is used as a photosensitive cover lay film, operations such as positioning on a substrate, which are conventionally required, become unnecessary. The cured composition of the present invention has sufficient mechanical strength and excellent heat resistance. Therefore, the composition and the dry film resist of the present invention are effectively used for protection of a printed circuit board used particularly in the field of electronic materials or for a suspension for a hard disk.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03F 7/004 512 G03F 7/004 512 7/075 521 7/075 521 H05K 3/28 H05K 3/28 D F-term (reference) 2H025 AA10 AA13 AA14 AB11 AB15 AC01 AD01 BC13 BC42 CB25 CB33 CB43 CB51 CB52 DA19 FA17 4J011 AC04 PA97 PC02 QA03 QA07 QA08 QA12 QA13 QA18 QA20 QA23 QA24 QA25 QA27 QA27 QA27 QA27 QA27 QA27 QA27 QA27 QA25 SA23 SA25 SA26 SA28 SA32. SA06 SA42 SA43 SA44 SA47 SA52 SA54 SA62 SA71 SA72 SA85 SB01 SB02 SB03 SB04 TA22 TA66 TA67 TA71 TA78 TB01 TB02 UA022 UA032 UA041 UA042 UA051 UA052 UA061 UA082 UA121 UA122 UA131 UA132 UA141 UA142 UA151 UA152 UA231 UA241 UA261 UA262 UA622 UA672 UA711 UB011 UB012 UB021 UB022 UB061 UB062 UB071 UB121 UB122 UB131 UB132 UB152 UB172 UB221 UB222 UB281 UB282 UB301 UB302 UB382 UB401 UB402 VA021 VA022 VA031 VA032 VA041 VA061 VA062 XA13 YA06 ZA12 ZA31 ZA33 ZA46 ZB11 ZB22 ZB50 5E314 AA27 AA36 CC15 FF19 GG08

Claims (14)

[Claims] (A) COOH equivalent is 200 to 3000
A photosensitive resin composition comprising: a soluble polyimide, (B) a polyfunctional (meth) acrylic compound and / or a polyfunctional (meth) acrylic compound composed of an analog thereof, and (C) a photoreaction initiator. . 2. The soluble polyimide is derived from a diamine having two or more COOH groups in a molecule.
3. The photosensitive resin composition according to item 1. 3. The photosensitive resin composition according to claim 1, wherein the soluble polyimide is dissolved in a solvent having a boiling point of 120 ° C. or lower. 4. The polyfunctional (meth) acrylic compound according to claim 1, which is bifunctional and has a (—O—CH ₂ CH ₂ —) repeating unit. Photosensitive resin composition. 5. The photosensitive resin composition according to claim 1, wherein the photoreaction initiator has a radical generating ability by at least one of g-line and i-line. 6. The photosensitive resin composition according to claim 1, wherein the soluble polyimide is derived from a siloxane diamine represented by the following general formula (I). (Wherein, R ¹ is each independently a C ₁ to C ₁₂ alkyl group or a phenyl group, and x is each independently 1 to 2
An integer of 0, and y represents an integer of 1 to 40). 7. The photosensitive resin composition according to claim 6, wherein the soluble polyimide is obtained from a diamine containing the siloxane diamine at a ratio of 5 to 70 mol%. 8. A photosensitive dry film resist obtained from the composition according to claim 1. 9. The photosensitive dry film resist according to claim 8, wherein the photosensitive dry film resist is insoluble in an aqueous alkali solution by a polymerization reaction upon exposure, and is soluble when not exposed. 10. The photosensitive dry film resist according to claim 8, wherein a thermal decomposition initiation temperature after curing is 300 ° C. or higher. 11. The photosensitive dry film resist according to claim 8, wherein the curing temperature is 200 ° C. or lower. 12. The photosensitive dry film resist according to claim 8, which can be laminated at a temperature of 150 ° C. or lower. 13. A photosensitive coverlay film for a printed circuit board, comprising the photosensitive dry film resist according to claim 8. 14. A photosensitive coverlay film-laminated printed circuit board, wherein the photosensitive coverlay film according to claim 13 is directly laminated on a printed circuit board.