JPH1152570A - Photosensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photosensitive resin compsn. developable with an aq. alkali soln. and ensuring superior heat resistance, adhesiveness to a conductor, electrical characteristics and flexibility by containing a soln. prepd. by dissolving a polyamic acid having specified repeating units and a specified logarithmic viscosity in a nitrogen-contg. org. solvent. SOLUTION: The photosensitive resin compsn. consists of a soln. prepd. by dissolving a polyamic acid having repeating units represented by formula I and 0.1-2.0 dl/g logarithmic viscosity in a nitrogen-contg. org. solvent, a compd. having a photopolymerizable C-C unsatd. double bond and a photopolymn. initiator. In the formula I, R is one of tetravalent groups represented by formulae II. The polyamic acid is produced by using 1,3-bis(3-aminophenoxy)benzene as an arom. diamine and condensing it with an arom. tetracarboxylic acid dianhydride in an org. solvent. The nitrogen-contg. org. solvent is, e.g. N,N- dimethylformamide or N,N-dimethylacetamide.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive resin composition containing a polyamic acid as a main component, and more particularly, to a photopolymerizable C-C-C with a polyamic acid which is a precursor of a polyimide having a specific structure. By incorporating a compound having an unsaturated bond and a photopolymerization initiator, good heat resistance,
Has adhesive properties, electrical properties, etc., especially printed wiring boards,
The present invention relates to a liquid resist ink composition, a cover coating agent, and an insulating film for a multilayer printed board which can be developed with an alkaline aqueous solution suitable for manufacturing a flexible circuit board and the like.

[0002]

2. Description of the Related Art Conventionally, a printed wiring board is formed by etching or plating a metal foil after forming an etching resist or a plating resist pattern by a screen printing method to form a desired conductor circuit pattern. Was. For the purpose of preventing oxidation of the conductive circuit pattern and maintaining insulation, a thermosetting resin composition or a photocurable resin composition is formed in a desired shape using a screen printing method in the same manner as when forming the conductive circuit. Was formed. Recently, miniaturization of conductor circuits has been advanced in order to increase the pattern density. For this reason, it is widely used to form an etching or plating resist at the time of forming a conductor circuit by using a photo method.

[0003] Etching formed by a photo method or
The positional accuracy and dimensional accuracy of the plating resist pattern are further enhanced as compared with the screen printing method. Due to miniaturization of conductor circuit patterns and improvement of position accuracy, and further miniaturization of mounted components and fine pitch of IC package leads, formation of insulation films such as solder resist films also requires improvement of image accuracy and position accuracy. And it was. Therefore, in recent years, a method of forming a solder resist film or an insulating film by using the photo method has been widely used as a method for forming a film with high accuracy.

[0004] In the photo method, a photosensitive resin composition is applied to a desired size, and then dried if necessary to form a photosensitive film. A negative photomask is placed on the photosensitive film and exposed and baked with actinic rays such as ultraviolet rays. Active light transmitted through the transparent portion of the photomask cures the photosensitive film. Uncured parts are peeled off by development,
Remove the photosensitive film. The photosensitive film formed by the above photo method is further cured by heat curing or actinic rays to form a solder resist film or an insulating film, but the formed image can be formed with extremely close precision to a photomask. Image and position accuracy can be easily obtained.

[0005] However, this method requires a development step later. In the development, the uncured portions of the unexposed portions were removed by dissolution and peeling with an organic solvent. The solvent is 1,
A highly toxic or flammable solvent such as 1,1-trichloroethane is generally used, and a photo solder resist using an aqueous alkali solution as a developing solution has been desired from the viewpoint of work safety. Therefore, research on an aqueous alkali solution-developing type photo solder resist has been actively conducted in recent years, and some compositions have been disclosed. For example, JP-B-56-40329 discloses a photosensitive resin composition having a reaction product obtained by adding an unsaturated monocarboxylic acid to an epoxy resin and further adding a polybasic acid anhydride as a base polymer. I have. Alternatively, JP-A-61-243
869 discloses a photo solder resist composition in which a reaction product obtained by adding a polybasic anhydride to a novolak type epoxy acrylate or the like is used as a base polymer and an alkaline aqueous solution is used as a developer. However, the solder resist film obtained from the above composition is insufficient in heat resistance, solvent resistance and chemical resistance, and has insufficient insulation and dielectric properties. Also,
Because of its poor flexibility, it cannot be applied to flexible circuit boards.

A polyimide obtained by heat-treating a polyamic acid as a polyimide precursor is
Due to their excellent heat resistance and dielectric properties, photosensitive polyimide precursors that have been used as protective films and interlayer insulating films for ICs and that can directly form patterns by exposure and development have been proposed. However, these photosensitive polyimides use an organic solvent for development, and are photosensitive polyimides which can be developed with an aqueous alkali solution from the viewpoint of work safety. Is desired. In addition, the photosensitive polyimide has an insufficient adhesive force with a conductor such as a copper foil,
In order to obtain a sufficient adhesive strength, some treatment such as roughening the conductor surface was required.

[0007]

SUMMARY OF THE INVENTION In addition to being able to be developed with an aqueous alkali solution such as an aqueous sodium hydroxide solution or an aqueous sodium carbonate solution, a sufficiently hardened film can be obtained at the time of printing an image by exposure. Excellent heat resistance as film properties after imidization by
An object of the present invention is to provide a photosensitive resin composition and a photo solder resist exhibiting adhesiveness to a conductor, electrical characteristics, and flexibility, and a photosensitive resin composition suitable for a cover coat agent for a flexible circuit board. An object of the present invention is to provide a metal processed product excellent in heat resistance, oxidation resistance, and electrical insulation properties by using these photosensitive films.

[0008]

That is, the present invention provides: (Claim 1) (A) The following structural formula (1)

[0009]

Embedded image (Wherein R is a structural formula (2)

[0010]

Embedded image And a tetravalent group selected from the group consisting of ) Having a logarithmic viscosity (N, N-dimethylacetamide solvent, concentration 0.5 g / 100 ml-solvent, measured at 35 °) of 0.1 to 2.0 dl / g. A solution in which polyamic acid is dissolved in a nitrogen-containing organic solvent,
A photosensitive resin composition comprising (B) a compound having a photopolymerizable CC unsaturated double bond and (C) a photopolymerization initiator. (Claim 2) The photosensitive resin composition according to claim 1, wherein the nitrogen-containing organic solvent further contains 10 to 1,000 parts of a glycol ether-based organic solvent based on 100 parts of the nitrogen-containing organic solvent. (Claim 3) The photosensitive resin composition according to claim 1 or 2, further comprising an organic filler, an inorganic filler or a pigment. (Claim 4) A processed product having a photosensitive film formed by applying and drying the photosensitive resin composition according to claim 1, 2 or 3 on a metal, plastic or ceramic. Is provided.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The polyamic acid used in the present invention, that is, the polymer having a repeating unit represented by the above structural formula (1) is 1,3-bis (3-aminophenoxy) as an aromatic diamine. It can be produced by using benzene and condensing it with an aromatic tetracarboxylic dianhydride in an organic solvent (JP-A-61-143377).
Described). As the above aromatic tetracarboxylic dianhydride, the structural formula (3)

[0012]

Embedded image (Wherein, R is a tetravalent group selected from the group consisting of the structural formulas (2)).

[0013] Specifically, 3,3 ^{', 4,4'} - benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4
^' -Biphenyltetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride and 2,3,6 , 7-Naphthalenetetracarboxylic dianhydride. These may be used alone or in combination of two or more.

In the above condensation reaction, the reaction temperature is usually from 10 to 60 ° C., preferably from 20 to 50 ° C., and the pressure is not particularly limited, and the reaction can be carried out at normal pressure. The reaction time varies depending on the type of the aromatic tetracarboxylic dianhydride and the organic solvent to be used, and the reaction temperature, but usually, a time sufficient for completing the generation of the polyamic acid, that is, from 4 to
24 hours.

In the present invention, the logarithmic viscosity of the polyamic acid obtained as described above needs to be in the range of 0.1 to 2.0 dl / g. Here, the logarithmic viscosity is represented by the following equation (1).

[0016]

Logarithmic viscosity = ln (η / η ₀ ) / C (1) (where, ln is a natural logarithm, and η is a solution obtained by dissolving 0.5 g of polyamic acid in 100 ml of N, N-dimethylacetamide as a solvent. the viscosity measured at 35 ° C. of, eta ₀ 3 of the solvent
The viscosity, measured at 5 ° C., and C is the solution concentration of the polymer in g of polyamic acid per 100 ml of the solvent. ).

The logarithmic viscosity of this polyamic acid is 0.1 dl.
If it is less than / g, the degree of polymerization of the polyamic acid is small, and during development, the coating film on the exposed portion cannot obtain sufficient strength. On the other hand, if the logarithmic viscosity exceeds 2.0 dl / g, the degree of polymerization of the polyamic acid becomes too large, and undeveloped portions become poorly dissolved during development. The logarithmic viscosity can be arbitrarily adjusted, for example, by changing the molar ratio of tetracarboxylic dianhydride to aromatic diamine. The solvent used in the present invention is a nitrogen-containing organic solvent. As a nitrogen-containing organic solvent,
N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone and the like.

In the present invention, it is preferable to use a nitrogen-containing organic solvent and a glycol ether-based organic solvent in combination. Examples of the glycol ether-based organic solvent include ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, and the like.

The nitrogen-containing organic solvent or glycol ether-based organic solvent may be used as a mixture of two or more kinds. More preferably, the mixing ratio of the nitrogen-containing organic solvent and the glycol ether-based organic solvent is such that the glycol ether-based organic solvent is 10 parts by weight to 1000 parts by weight, more preferably 20 parts by weight, per 100 parts by weight of the nitrogen-containing organic solvent.
It is in the range of parts by weight to 500 parts by weight. If the amount of the glycol ether-based organic solvent is less than 10 parts by weight, cracks occur in the coating film during alkali development. On the other hand, if the amount of the glycol ether-based organic solvent exceeds 1000 parts by weight, it becomes difficult to dissolve the polyamic acid, which is not preferable.

The compound having a photopolymerizable C--C unsaturated double bond used in the present invention is a known acrylate compound, methacrylate compound or allylate compound. The acrylate compounds can be classified as follows. (A) Structural classification (classified from raw materials, products, etc.) Alkyl acrylates, alkylamino acrylates, hydroxylalkyl acrylates, oligoester acrylates, polyester acrylates, oligoether acrylates, polyether acrylates, epoxy acrylates (B) Classification of the number of functional groups (classified from the number of acryloyl groups) Monofunctional acrylates, difunctional acrylates, trifunctional acrylates to polyfunctional acrylates, (c) amino group classification (depending on the presence or absence of amino groups) Classification) Amino acrylates, non-amino acrylates.

Specifically, alkyl acrylates such as ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate and the like. As alkylaminoacrylates, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, dimethylaminomethyl acrylate, diethylaminomethyl acrylate, an adduct of diacrylate and diethylamine, an adduct of trimethylolpropane triacrylate and diethylamine,
Hydroxyethyl acrylates, hydroxypropyl acrylates as hydroxyalkyl acrylates,
Hydroxybutyl acrylate and the like. KAYARAD MANDA, KAY as oligoester acrylates
ARAD R526, etc. Polyester acrylates such as polyethylene glycol adipate / 2 mol acrylic acid condensate, polydiethylene glycol adipate / 2 mol acrylic acid condensate, poly 1,4 butanediol adipate / 2 mol acrylic acid condensate, polyneopentyl glycol adipate Condensates of 2 molar acrylic acid, etc. Examples of oligoether acrylates include diethylene glycol diacrylate, triethylene glycol diacrylate, dipropylene glycol diacrylate, and tripropylene glycol diacrylate. Polyether acrylates include polyethylene glycol diacrylate, polypropylene glycol diacrylate, polytetramethylene ether glycol diacrylate, and the like. Bisphenol F diglycidyl ether / 2 mol acrylic acid adduct as epoxy acrylates,
Bisphenol A diglycidyl ether 2 mol acrylic acid adduct, bisphenol S diglycidyl ether
2 mol acrylic acid adduct, novolak epoxy and acrylic acid adduct, cresol novolak epoxy and acrylic acid adduct, etc.

Monofunctional acrylates such as phenoxyethyl acrylate, nonylphenoxyethyl acrylate, phenoxypropyl acrylate, nonylphenoxypropyl acrylate and the like. Examples of bifunctional acrylates include diethylene glycol diacrylate, neopentyl glycol diacrylate, butylene glycol diacrylate, and hexamethylene glycol diacrylate. Trifunctional acrylates such as trimethylolpropane triacrylate, pentaerythritol triacrylate, and glycerin triacrylate. Examples of polyfunctional acrylates include dipentaerythritol hexaacrylate, KAYARAD DCP30, an adduct of novolak epoxy and acrylic acid, and an adduct of cresol novolak epoxy and acrylic acid.

As amino acrylates, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, dimethylaminomethyl acrylate, diethylaminomethyl acrylate, trimethylolpropane triacrylate / monoethanolamine from 1 mol to 2 mol
Molar adduct, bifunctional acrylate and alkylamine (C
Equimolar adduct from ₁ carbon number of C _6), 3 2-fold molar adduct equimolar functional acrylates and alkyl amine (carbon number of from C ₁ C _6), from 4-functional acrylates and alkyl amine (C ₁ Equimolar to 3 times molar adduct of (C ₆ carbon number), Aronix M215, Aronix M315
etc.

Non-amino acrylates include nonylphenoxypropyl acrylate, ethylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, and adducts of cresol novolak epoxy with acrylic acid.
These may be used alone or in combination of two or more. The methacrylate compound is a compound obtained by substituting the acrylate compound with methacrylate.

Very typical arylate compounds include, for example, phenylarylate, nonylphenoxyarylate, diethylene glycol diallylate, trimethylolpropane triarylate, pentaerythritol tetraarylate, dipentaerythritol hexaarylate, trimethylolpropane diallyl ether and allyl alcohol. A reactant of isophorone diisocyanate,
Compounds such as a reaction product of pentaerythritol triallyl ether, allyl alcohol, and isophorone diisocyanate are exemplified.

Further, a polyene / thiol compound may be used. The ratio of the compound to the total solid content of the photosensitive resin composition depends on the properties of the compound, but is 4.5 w.
t% to 99 wt%, more preferably 5 wt% to 90 wt%
%.

The photopolymerization initiator used in the present invention is a known one, and specifically, benzophenone, Michler's ketone,
Benzoin, benzoin ethyl ether, benzoin butyl ether, benzoin isobutyl ether, 2,2
-Dimethoxy-2-phenylacetophenone, 2-hydroxy-2-phenylacetophenone, 2-hydroxy-
2-methylpropiophenone, 2-hydroxy-4-isopropyl-2-methylpropiophenone, 2-ethylanthraquinone, 2-t-butylanthraquinone, diethylthioxanthone, chlorothioxanthone, benzyl, benzyldimethylketal, 1-hydroxycyclohexyl Examples include phenyl ketone, benzoylbenzoic acid, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, and 2,4,6 trimethylbenzoyldiphenylphosphine oxide.

Further, an equimolar addition product of benzoin and ethylene oxide, a 2-fold to 4-fold molar addition product,
Equimolar addition of benzoin and propylene oxide or 2
4-fold molar adduct to 4-fold molar adduct, α-allylbenzoin, equimolar adduct of 1-hydroxycyclohexylphenyl ketone and ethylene oxide, 2-fold molar adduct to 4-fold molar adduct, 1-hydroxycyclohexylphenyl ketone and propylene Equimolar adduct of oxide, 2-fold to 4-fold molar adduct, benzoylbenzoic acid and ethylene glycol equimolar reactant, benzoylbenzoic acid and propylene glycol equimolar reactant, hydroxybenzophenone and ethylene oxide equimolar addition , A 2-fold to 4-fold molar addition product, an equimolar addition product of hydroxybenzophenone and propylene oxide, a 2-fold molar addition product, a 4-fold molar addition product, and 4- (2-hydroxyethoxy) phenyl- (2- Hydroxy-2-propyl) ketone, 4- (2-act Oxy ethoxy) - phenyl -
(2-hydroxy-2-propyl) ketone, 4- (2-
(Hydroxyethoxy) phenyl- (2-hydroxy-2
-Propyl) ketone and ethylene oxide equimolar adduct, 2-fold to 4-fold molar adduct, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-
Propyl) ketone and propylene oxide equimolar adduct, 2-fold to 4-fold molar adduct, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4 -Decylphenyl) -2-
And hydroxy-2-methylpropan-1-one. These may be used alone or in combination of two or more.

A known photopolymerization initiation aid may be used in combination. Specific examples of these photopolymerization initiation aids include triethanolamine, diethanolamine, ethanolamine, tripropanolamine, dipropanolamine,
Examples thereof include propanolamine, ethyl 4-dimethylaminobenzoate, and isoamyl 4-dimethylaminobenzoate. The photopolymerization initiation aid is used alone or in combination of two or more. The ratio of the photopolymerization initiator to the total solid content of the photosensitive resin composition is 0.1 wt% to 20 wt%, and more preferably 0.15 wt% to 15 wt%.

The filler used in the present invention is an organic filler or an inorganic filler. As the organic filler, epoxy resin, melamine resin, urea resin, acrylic resin,
It is a filler of a type in which a solvent such as a phenol resin, a polyimide resin, a Teflon resin, a polyethylene resin, a polyester resin, and a polyamide resin is polymerized into fine particles until it is no longer required, or is a cross-linked fine particle type. As the inorganic filler, metal oxide fine particles such as alumina, silica, magnesia, and ferrite, or silicates such as talc, mica, kaolin, and zeolite, and fine particles such as barium sulfate and calcium carbonate are used. The filler is used alone or in combination of two or more.

The filler is preferably fine particles having an average particle size of 10 μm or less, more preferably 5 μm or less. The specific surface area of the fine particles is 100
m ² / g or less, preferably 60 m ² / g or less. If the specific surface area of the fine particles exceeds 100 m ² / g, uniform mixing and dispersion becomes difficult, which is not preferable. The amount of the filler added is 80% by weight based on the total solid content of the photosensitive resin composition.
Or less, preferably 50% by weight or less. If it exceeds 80% by weight, it is difficult to form a photosensitive film or an insulating film, which is not preferable.

The pigment used in the present invention is a known coloring pigment such as phthalocyanine blue, phthalocyanine green, and titanium oxide. When mixing the filler, the pigment, the photosensitive resin, the organic solvent, and the like, it is preferable that the filler and the pigment are uniformly dispersed in the resin composition. Dispersion can be performed by a known method, for example, ball mill, roll mill,
A photosensitive resin composition having good dispersion and mixing can be obtained by using a dispersing device having a strong shearing force such as a medium mill. Further, in order to perform good dispersion mixing, a wetting agent, a dispersant, a silane coupling agent, a titanium coupling agent, an antifoaming agent and the like can be added.

In this way, a photosensitive resin composition can be obtained. A method for forming a solder resist film or an insulating film on the surface of a metal or a metal laminate using these photosensitive resin compositions. Can be easily applied using a known roll coater, screen coating, bar coater or the like. The applied photosensitive resin composition becomes a photosensitive film by volatilizing the organic solvent, and drying may be performed by a known method, for example, using a hot air dryer, a far infrared ray, a near infrared ray dryer, or the like. A photosensitive film can be formed by drying at ~ 150 ° C for 10-60 minutes. The thickness of the photosensitive film is suitably from 5 to 200 μm, preferably from 15 to 100 μm. If the film thickness is less than 5 μm, the insulation reliability is poor, and if it exceeds 200 μm, the exposure sensitivity is lowered and the development time is undesirably long.

The photosensitive resin composition of the present invention can be used not only as a material for forming a solder resist film or an insulating film, but also by applying it to a colorless and transparent film such as polyethylene, polypropylene and polyester and drying it. A film can be obtained. The photosensitive film can be applied to the above-mentioned film having a thickness of 10 to 100 μm by a known method such as a reverse roll coater, a gravure roll coater, a comma coater, and a curtain coater. Drying can be performed at a temperature of 50 to 120 ° C. using a dryer using hot air drying or far-infrared rays or near-infrared rays, and more preferably by drying at 60 to 100 ° C. for 10 to 60 minutes to obtain a photosensitive film. it can. At this time, the thickness of the photosensitive resin composition is from 5 to 200 μm, and more preferably from 15 to 100 μm. If the film thickness is less than 5 μm, insulation reliability is poor, and if it exceeds 200 μm, exposure sensitivity is lowered and development takes time, which is not preferable.

In order to obtain a solder resist film or an insulating film using the photosensitive film, a known method such as a flat plate press or a roll press may be used while heating the film to 40 to 150 ° C. while heating to 1 to 5 kgf / cm. ^By performing thermocompression bonding in step ² , a photosensitive film can be formed on the surface of a metal plate or a metal laminate.

In this manner, the photosensitive film is exposed using a usual photomask. The actinic rays used at this time include, for example, ultraviolet rays, electron beams, X-rays and the like, and among these, ultraviolet rays are more preferable, and as the light source, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, An ultra-high pressure mercury lamp, a halogen lamp and the like can be mentioned. After the exposure, when performing development using a developer, an immersion method or a spray method can be used. As the developing solution, an aqueous alkaline solution such as an aqueous sodium hydroxide solution and an aqueous sodium carbonate solution is used. After development, it is desirable to rinse with an acidic aqueous solution such as dilute hydrochloric acid or dilute sulfuric acid. The pattern obtained by the development is then converted into a polyimide pattern by heat treatment. The heat treatment is
It is performed continuously or stepwise at a temperature of 150 to 450 ° C. for 0.1 to 5 hours.

[0037]

EXAMPLES The present invention will be described below in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. [Synthesis Example 1] (Polyamic acid PA1) Reactor (with stirrer, reflux condenser and nitrogen inlet tube)
Medium, under nitrogen atmosphere, N, N-dimethylacetamide 13
5 g, 135 g of diethylene glycol dimethyl ether
1,3-bis (3-aminophenoxy) benzene 5
Was dissolved 3.29 g (0.1825 mol) while stirring it, 3,3 ^{', 4,4'} - benzophenone tetracarboxylic dianhydride 58.282g of (0.1810 mol) remains dry solids It was added in small portions. During this time, the temperature of the reactor was maintained at 25 to 30 ° C., and stirring was continued under a nitrogen atmosphere for 20 hours after the addition to obtain a polyamic acid having a solid content of 30%. Table 1 shows the logarithmic viscosity of the polyamic acid.

[Synthesis Examples 2 to 5] (Polyamic acid PA2
5) 3,3 Synthesis Example 1 ^{', 4,4'} - instead of benzophenone tetracarboxylic dianhydride, except for using the compound described in Table 1, exactly the same procedure as in Synthesis Example 1, Four types of polyamic acids were obtained. Table 1 shows the logarithmic viscosities of these polyamic acids.

[Synthesis Examples 6 and 7] (Polyamic acid PA6
To 7) 3,3 Synthesis Example 1 ^{', 4,4'} - the amount of benzophenonetetracarboxylic dianhydride 32.2 g (0.10 mol)
The same operation was carried out except that (PA6) or 58.765 g (0.1825 mol) (PA7) was used, to obtain two kinds of polyamic acids. Table 1 shows the logarithmic viscosities of these polyamic acids.

[Synthesis Example 8] (Polyamide acid PA8) A polyamic acid was obtained in exactly the same manner as in Synthesis Example 1, except that the total amount of the organic solvent was changed to 270 g of N, N-dimethylacetamide. Table 1 shows the logarithmic viscosity of the polyamic acid.

[0041] [Synthesis Example 9] (polyamic acid PA9) of 1,3-bis Synthesis Example 1 (3-aminophenoxy) 4,4 benzene ^'- except for changing the diaminodiphenyl ether is operated exactly like, polyamide The acid was obtained. Table 1 shows the logarithmic viscosity of the polyamic acid.

[0042]

[Table 1] * 1) 1,3-bis (3-aminophenoxy) benzene * 2) 3,3 ^'4,4' - benzophenonetetracarboxylic acid dianhydride * 3) 3,3 ^'4,4' - biphenyltetracarboxylic Carboxylic acid dianhydride * 4) 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride * 5) bis (3,4-dicarboxyphenyl) sulfone dianhydride * 6) 2,3 6,7-naphthalene tetracarboxylic dianhydride * 7) 4,4 ^'- diaminodiphenyl ether

Using the polyamic acid shown in the above synthesis example,
Examples of the photosensitive resin composition of the present invention are shown below. [Example 1] Compounding amount (parts by weight) Synthesis Example 1 Polyamic acid (PA1) 220 Pentaerythritol triacrylate 25 IRUGACURE907 (manufactured by Ciba-Geigy Corp., hereinafter abbreviated as IGC907) 6 Kayacure DETX (manufactured by Nippon Kayaku, abbreviated as DETX) 2 N , N-dimethylacetamide 4

Example 2 Amount (parts by weight) Synthesis Example 2 Polyamic acid (PA2) 220 Pentaerythritol triacrylate 25 IGC907 6 DETX 2 N, N-dimethylacetamide 4

Example 3 Amount (parts by weight) Synthesis Example 3 Polyamic acid (PA3) 220 Pentaerythritol triacrylate 25 IGC907 6 DETX 2 N, N-dimethylacetamide 4

Example 4 Amount (parts by weight) Synthesis Example 4 Polyamic acid (PA4) 220 Pentaerythritol triacrylate 25 IGC907 6 DETX 2 N, N-dimethylacetamide 4

Example 5 Compounding Amount (Parts by Weight) Synthesis Example 5 Polyamic Acid (PA5) 220 Pentaerythritol Triacrylate 25 IGC907 6 DETX 2 N, N-Dimethylacetamide 4

Example 6 Amount (parts by weight) Synthesis Example 1 Polyamic acid (PA1) 220 Pentaerythritol triacrylate 25 IGC907 6 DETX 2 Barium sulfate (B-34 manufactured by Sakai Chemical) 30 Aerosil # 300 (produced by Nippon Aerosil) ) 3 Phthalocyanine green 0.6 N, N-dimethylacetamide 8

[Comparative Example 1] Compounding amount (parts by weight) Synthesis Example 6 Polyamic acid (PA6) 220 Pentaerythritol triacrylate 25 IGC907 6 DETX 2 N, N-dimethylacetamide 4

[Comparative Example 2] Compounding amount (parts by weight) Synthesis Example 7 Polyamic acid (PA7) 220 Pentaerythritol triacrylate 25 IGC907 6 DETX 2 N, N-dimethylacetamide 4

[Comparative Example 3] Compounding amount (parts by weight) Synthesis Example 8 Polyamic acid (PA8) 220 Pentaerythritol triacrylate 25 IGC907 6 DETX 2 N, N-dimethylacetamide 4

[Comparative Example 4] Compounding amount (parts by weight) Synthesis Example 9 Polyamic acid (PA9) 220 Pentaerythritol triacrylate 25 IGC907 6 DETX 2 N, N-dimethylacetamide 4

The above photosensitive resin composition was prepared and uniformly applied to a printed wiring board on which a conductor circuit pattern was drawn, using a doctor blade. Then, it dried at 80 degreeC for 40 minutes, and produced the sample for a test. In addition, thickness 1
The test sample was applied to a 1 mm-thick metal plate and a 1-oz copper foil glossy surface and dried. The dried coating film thickness is 20 to 25 on a conductive circuit, a metal plate and a copper foil glossy surface.
It was adjusted to obtain a photosensitive film of μm. Next, the photosensitive film was exposed to light with a light intensity of 500 mj / cm ² by using a desired photomask with an ultrahigh-pressure mercury lamp of 3 kW.

The exposed photosensitive film was immersed in a developing solution adjusted to 30 ° C. with a 1.0 wt% aqueous sodium hydroxide solution for 50 seconds to perform development. Examples 1 to 6 and Comparative Example 9
In, the unexposed portion was easily peeled off with a developer to obtain a desired image. In Comparative Example 1, the exposed portion was completely dissolved in the developer and no image was obtained. In Comparative Example 2, the unexposed portion did not dissolve in the developer, and no image could be obtained. In Comparative Example 3, although a desired image was obtained, cracks occurred in the coating film. In Comparative Example 4, although the desired image was obtained, the adhesion to the glossy copper foil surface after imidization by heat treatment was extremely poor, and the practicality was poor. Examples 1 to 6 and Comparative Example 3 were heated at 250 ° C. for 10 minutes to convert the coating film to polyimide.

Each of the test samples converted into the above polyimide was evaluated by the following methods. Evaluation 1: The pencil hardness test was performed by the method described in (JIS K-5405). Evaluation 2: Adhesion after cross cut was determined according to (JIS K-5)
405). Evaluation 3: In the solvent resistance test, after a cross cut described in JIS K-5405 was inserted, the sample was immersed in acetone at room temperature for 12 hours, and the remaining amount in a grid was measured. Evaluation 4: In the chemical resistance test, after a cross cut described in JIS K-5405 was inserted, the sample was immersed in a 10 wt% hydrochloric acid aqueous solution at 60 ° C. for 12 hours, and the remaining amount in a grid was measured. Evaluation 5: In the chemical resistance test, after a cross cut described in JIS K-5405 was inserted, the sample was immersed in a 10% by weight aqueous solution of sodium hydroxide at 60 ° C. for 12 hours, and the remaining amount of the grid was measured. Evaluation 6: A copper foil laminated plate having a solder resist pattern formed of a photosensitive film was subjected to a test under an environment of 60 ° C. and 95% RH for 10 days.
Left for 0 hours. This sample was immersed in a solder melted at 280 ° C. for 20 seconds, and the presence or absence of peeling or blistering of the copper foil and the solder resist film was confirmed. Evaluation 7: A test sample formed on a 0.2 mm copper plate was subjected to a bending test at an angle of 90 ° to check for cracks in the coating. Evaluation 8: 1 oz. In a test sample formed on a rolled copper foil glossy surface, the copper foil was then etched to a width of 2 mm, and the strength when the coating and the 2 mm width copper foil were peeled off at an angle of 90 ° was evaluated. It was shown in Peel strength (Kg / cm).

Table 2 shows the evaluation results of Examples 1 to 6 and Comparative Examples 1 to 4. From this evaluation result, in Examples 1 to 6, it is possible to develop with an alkaline aqueous solution and has excellent adhesiveness with a conductor, flexibility, and chemical resistance, and furthermore, it is difficult to cause peeling or swelling due to solder heat resistance. The feature is the point.

[0057]

[Table 2]

[0058]

As described in Examples and Comparative Examples, the insulating film and the solder resist film made of the photosensitive resin composition according to the present invention can be developed with an alkaline aqueous solution, as can be seen from Table 2. it can. In addition, by using a polyamic acid as a main component, the polyimide itself corresponding to the polyamic acid can exhibit excellent heat resistance, workability, electrical characteristics, and flexibility, and form an insulating film on a printed wiring board. Ideal for materials and cover coat materials for flexible circuit boards. Further, the polyamic acid exhibits thermoplasticity by having a specific structure, and has a strong adhesive force to a conductor such as a metal foil, so that excellent performance can be expected as an interlayer insulating material of a multilayer printed wiring board. .

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI G03F 7/004 505 G03F 7/004 505 7/027 502 7/027 502 7/038 504 7/038 504 H05K 3/06 H05K 3 / 06 H 3/18 3/18 D 3/28 3/28 D 3/46 3/46 T

Claims (4)

[Claims] (A) The following structural formula (1) (Wherein R is a structural formula (2) And a tetravalent group selected from the group consisting of ) Having a logarithmic viscosity (N, N-dimethylacetamide solvent, concentration 0.5 g / 100 ml-solvent, measured at 35 °) of 0.1 to 2.0 dl / g. A solution in which polyamic acid is dissolved in a nitrogen-containing organic solvent,
A photosensitive resin composition comprising (B) a compound having a photopolymerizable CC unsaturated double bond and (C) a photopolymerization initiator. 2. The photosensitive resin composition according to claim 1, wherein the nitrogen-containing organic solvent further contains 10 to 1000 parts of a glycol ether-based organic solvent based on 100 parts of the nitrogen-containing organic solvent. 3. The photosensitive resin composition according to claim 1, further comprising an organic filler, an inorganic filler or a pigment. 4. A processed product having a photosensitive film formed by applying and drying the photosensitive resin composition according to claim 1, 2 or 3 on a metal, plastic or ceramic.