JP2001005182A - Photosensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photosensitive resin composition having thermoplasticity, high adhesive power to a metallic conductor and high elongation and capable of exhibiting heat resistance, workability, etc., by blending a polyamic acid having specified repeating units and a specified logarithmic viscosity with a specified acrylamide compound, etc., in a specified ratio. SOLUTION: A polyamic acid having repeating units of the formula and 0.3 to 1.0 dl/g logarithmic viscosity is blended with 10 to 100 pts.wt. (meth) acrylate compound containing an alcoholic hydroxyl group and having >=3 photopolymerizable C-C unsaturated double bonds, 5 to 100 pts.wt. polyalkylene glycol di(meth)acrylate compound and 5 to 50 pts.wt. acrylamide compound of the formula (CH2=C(R1)-CONH)nR2 as essential components, based on 100 pts.wt. polyamic acid, and a photopolymerization initiator is further added as an essential component. In the formula, R1 is H or methyl, R2 is H, CH2 or the like and (n) is 1 or 2.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a photosensitive resin composition containing a polyamic acid as a main component. More specifically, the present invention comprises mixing a (meth) acrylate compound having a specific structure, an acrylamide compound having a specific structure, and a photopolymerization initiator in a specific ratio with a polyamic acid which is a precursor of a polyimide having a specific structure. It is a photosensitive resin composition that can be developed with an aqueous alkali solution and is suitable for a liquid resist ink composition, a cover coating agent, and an insulating film for a multilayer printed circuit board. The cured product has good heat resistance, adhesiveness, electrical properties, and good elongation properties, and is most suitable for manufacturing flexible circuit boards and the like.

[0002]

2. Description of the Related Art Conventionally, in a printed wiring board, after forming an etching resist or a plating resist pattern by a screen printing method, a metal foil is etched or plated to form a desired conductor circuit pattern. A thermosetting resin composition or a photocurable resin composition for the purpose of preventing oxidation of the conductor circuit pattern and maintaining insulation is formed in a desired shape by using a screen printing method in the same manner as when forming the conductor circuit. A film 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.

An etching or plating resist pattern formed by a photo method has a much higher positional accuracy and dimensional accuracy than a 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 this photosensitive film, and exposure and printing are performed with actinic rays such as ultraviolet rays. Active light transmitted through the transparent portion of the photomask cures the photosensitive film. Unexposed 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 alkaline 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 in which a reaction product obtained by adding an unsaturated monocarboxylic acid to an epoxy resin and further adding a polybasic acid anhydride is used as a base polymer. Is disclosed. JP-A-61-243869 discloses a photo solder resist using a reaction product obtained by adding a polybasic acid anhydride to a novolak type epoxy acrylate or the like as a base polymer and using an alkaline aqueous solution as a developer. A composition is disclosed. However, the solder-resist film obtained from the above composition is insufficient in heat resistance, solvent resistance and chemical resistance, and its properties relating to insulation and dielectric constant are not sufficient. In addition, because of its poor flexibility, it cannot be applied to flexible circuit boards.

Further, polyimide obtained by heat-treating a polyamic acid as a polyimide precursor is
Due to its excellent heat resistance and dielectric properties, a photosensitive polyimide precursor which has been used as a protective film and an interlayer insulating film for ICs and which can directly form a pattern by exposure and development has been proposed (Japanese Patent Application Laid-Open No. 60-1985). -22837, JP-A-59-52822).

However, these photosensitive polyimides use an organic solvent for development, and from the viewpoint of work safety, a photosensitive polyimide which can be developed with an alkaline aqueous solution is desired. Further, the photosensitive polyimide has an insufficient adhesive force to a conductor such as a copper foil, and in order to obtain a sufficient adhesive force, some treatment such as roughening the surface of the conductor is required. Further, the cured film lacks sufficient elongation that can be applied to a flexible circuit board.

[0009]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a film which can be developed with an aqueous alkali solution such as an aqueous sodium hydroxide solution or an aqueous sodium carbonate solution and which has been sufficiently cured during printing of an image by exposure. As a film property after imidization by heat treatment after development, it exhibits excellent heat resistance, adhesiveness to conductors, electrical properties, and even good elongation properties, and exhibits flexibility, photo solder resist, flexible It is an object of the present invention to provide a photosensitive resin composition suitable for a cover coating agent for a flexible circuit board. Another 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.

[0010]

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

Embedded image And a logarithmic viscosity (N,
N-dimethylacetamide solvent, concentration 0.5 g / 100
(B) at least 3 or more photopolymerizable C-Cs containing (B) an alcoholic hydroxyl group with respect to 100 parts by weight of a polyamic acid having a concentration of 0.3 to 1.0 dl / g). 10 to 100 parts by weight of a (meth) acrylate compound having an unsaturated double bond, 5 to 100 parts by weight of C) a polyalkylene glycol di (meth) acrylate compound, and (D) the following formula (2)

[0011]

Embedded image (Wherein R ¹ represents a hydrogen atom or a methyl group, R ² represents a hydrogen atom, CH ₂ or CH ₂ OH, and n is 1 or 2) 5 to 50 parts by weight of the acrylamide compound And (E) a photosensitive resin composition prepared by mixing a photopolymerization initiator as an essential component, and (2) the photosensitive resin composition according to (1) in an amount of 10 to 1 based on 100 parts of a nitrogen-containing organic solvent.
(1) or (1) wherein the photosensitive resin composition is diluted with a mixed solvent containing 000 parts of a glycol ether-based organic solvent, and (3) the film has an elongation of at least 20% after curing. It has a photosensitive resin composition according to 2) and a photosensitive film formed by applying and drying the photosensitive resin composition according to (4) (1) to (3) on metal, plastic or ceramic. Processed goods.

[0012]

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 formula (1), comprises 1,3-bis (3-aminophenoxy) benzene as an aromatic diamine. And 3,3′-4,4′-biphenyltetracarboxylic dianhydride as an aromatic dianhydride. These can be produced by condensing them in an organic solvent (JP-A-61-1434).
No. 77). 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 organic solvent used and the reaction temperature, but is usually a time sufficient for completing the generation of the polyamic acid, that is, 4 to 24 hours.

In the present invention, the logarithmic viscosity of the polyamic acid obtained as described above must be in the range of 0.3 to 1.0 dl / g. Here, the logarithmic viscosity is represented by the following equation (1).

(Equation 1) (In the formula, ln is a natural logarithm, η is a viscosity measured at 35 ° C. of a solution of 0.5 g of polyamic acid in 100 m of N, N-dimethylacetamide as a solvent, and η0 is 35 of the solvent.
Viscosity, measured in ° C., and C is the solution concentration of the polymer in grams of polyamic acid per 100 ml of the solvent. )
It is the value calculated in.

The logarithmic viscosity of this polyamic acid is 0.3 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 1.0 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 by changing the molar ratio between the aromatic diamine and the aromatic dianhydride.

The solvent used in the present invention is a nitrogen-containing organic solvent. Examples of the nitrogen-containing organic solvent include 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 the glycol ether-based organic solvent may be used as a mixture of two or more kinds. More preferably, the mixing ratio of the above-mentioned nitrogen-containing organic solvent and glycol ether-based organic solvent is such that the glycol ether-based organic solvent is 10 parts by weight to 1000 parts by weight with respect to 100 parts by weight of the nitrogen-containing organic solvent.
Parts by weight, more preferably in the range of 20 to 500 parts by weight. When the amount of the glycol ether organic solvent is 10
If the amount is less than 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 is difficult to dissolve the polyamic acid, which is not preferable.

The (meth) acrylate compounds having an alcoholic hydroxyl group and having at least three or more photopolymerizable CC unsaturated double bonds for use in the present invention include pentaerythritol triacrylate and pentaerythritol triacrylate. Erythritol trimethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, and the like, include compatibility with the polyamic acid, curability at the time of exposure, and further, unexposed to an aqueous alkali solution at the time of development. Due to the solubility of the pentaerythritol triacrylate, pentaerythritol triacrylate is most preferred.

The amount of the (meth) acrylate compound is 10 to 100 parts by weight based on 100 parts by weight of the polyamic acid.
Parts by weight. If the amount is less than 10 parts by weight, the film after exposure is not sufficiently cured, and the unexposed portion is not completely dissolved during alkali development, resulting in development residue. If it exceeds 100 parts by weight, the compatibility with the polyamic acid may be reduced, and the coating may be whitened after coating and drying. Further, the flexibility of the exposed portion is impaired, and the elongation of the film after exposure is significantly reduced. Examples of the polyalkylene glycol di (meth) acrylate compound used in the present invention include compounds represented by the following formulas, and formulas (3) to (8).

[0018]

Embedded image (In the formula, n is 2 to 12.)

[0019]

Embedded image (In the formula, n is 2 to 12.)

[0020]

Embedded image (In the formula, n is 2 to 12.)

[0021]

Embedded image (In the formula, n is 2 to 12.)

[0022]

Embedded image (In the formula, n is 2 to 12.)

[0023]

Embedded image (In the formula, n is 2 to 12.) The blending amount of the polyalkylene glycol di (meth) acrylate compound is 5 to 100 with respect to the polyamic acid.
Parts by weight. If the amount is less than 5 parts by weight, the flexibility of the exposed portion is not sufficient, and the elongation of the film after exposure is reduced. 100
If the amount is more than the weight part, heat resistance is remarkably impaired. The following equation (2) used in the present invention:

[0024]

Embedded image (Wherein R ¹ represents a hydrogen atom or a methyl group, R ² represents a hydrogen atom, CH ₂ or CH ₂ OH, and n is 1 or 2). Methacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, methylenebisacrylamide, methylenebismethacrylamide and the like can be used, and these can be used alone or as a mixture of two or more.

By blending the acrylamide compound in an amount of 5 to 50 parts by weight with respect to the polyamic acid, the compatibility between the polyamic acid and the acrylate compound is improved, and at the same time, the curability at the time of exposure is improved, and Curing is possible, and improvement in resolution can be expected. If it is less than 5 parts by weight, the curability is not sufficient, and if it exceeds 50 parts by weight, precipitation occurs, and a good film cannot be obtained.

The photopolymerization initiator used in the present invention is a known one. 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-hydroxycyclohexylphenylketone, benzoylbenzoic acid, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2,4,6 Trimethylbenzoyldiphenylphosphine oxide and the like.

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-hydroxycyclohexyl phenyl ketone and ethylene oxide, 2-fold molar adduct to 4-fold molar adduct, 1-hydroxycyclohexyl phenyl ketone Equimolar addition product of propylene oxide, 2-fold to 4-fold mole addition product, benzoylbenzoic acid and ethylene glycol equimolar reactant, benzoylbenzoic acid and propylene glycol equimolar reactant, hydroxybenzophenone and ethylene oxide equimolar Adduct, 2-fold to 4-fold molar addition, equimolar addition of hydroxybenzophenone and propylene oxide, 2-fold molar addition, 4-fold molar addition, 4- (2-hydroxyethoxy) phenyl- (2- Hydroxy-2-propyl) ketone, 4- (2-a) B 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. As these photopolymerization initiation aids, specifically, triethanolamine,
Examples thereof include diethanolamine, ethanolamine, tripropanolamine, dipropanolamine, propanolamine, ethyl 4-dimethylaminobenzoate, and isoamyl 4-dimethylaminobenzoate. The photopolymerization initiation aid is used alone or in combination of two or more. The blending amount of the photopolymerization initiator with respect to the total solid content of the photosensitive resin composition is 0.1 wt% to 20 wt%, more preferably 1.0 wt% to 10 wt%.

A method of forming a solder resist film or an insulating film on the surface of a metal, a metal laminate plate or a ceramic plate using the photosensitive resin composition includes a known roll coater, screen coating, bar coater and the like. It can be easily applied using. The applied photosensitive resin composition becomes a photosensitive film by volatilizing an 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. 10 to 6 at ~ 150 ° C
By drying for 0 minutes, a photosensitive film can be formed. 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. Further, the photosensitive resin composition of the present invention is not only a material for forming a solder resist film or an insulating film,
A photosensitive film can be obtained by coating and drying a colorless and transparent film such as polyethylene, polypropylene, and polyester. 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, the insulation reliability is poor, and if it exceeds 200 μm, the exposure sensitivity is lowered and development takes a long time, which is not preferable.

In order to obtain a solder resist film or an insulating film using the above-mentioned 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 at 98 to 490 kPa (1 kPa). ~ 5Kg
f / cm ² ) by thermocompression bonding to form a photosensitive film on a metal plate,
It can be formed on the surface of a metal laminate or ceramic plate. In this way, the photosensitive film is exposed using a normal 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. Heat treatment is 150 ~
It is performed continuously or stepwise at a temperature of 450 ° C. for 0.1 to 5 hours.

[0030]

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] (Polyamide 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
While dissolving 3.29 g (0.1825 mol), 53.214 g (0.1810 mol) of 3,3′-4,4′-biphenyltetracarboxylic dianhydride was dried while stirring as a dry solid. It was added in small portions. During this period, 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 Example 2] (Polyamic acid PA2) Pyromellitic dianhydride was used in place of 3,3'-4,4'-biphenyltetracarboxylic dianhydride in Synthesis Example 1, except that By operating exactly as in Synthesis Example 1, a polyamic acid was obtained. Table 1 shows the logarithmic viscosity of the polyamic acid.

[Synthesis Example 3] (Polyamide acid PA3) Except for using 4,4′-diaminodiphenyl ether in place of 1,3-bis (3-aminophenoxy) benzene in Synthesis Example 1, it was completely the same as in Synthesis Example 1. The same operation was performed to obtain a polyamic acid. Table 1 shows the logarithmic viscosity of the polyamic acid.

[Synthesis Examples 4 and 5] (Polyamic acid PA4
~ 5) The amount of 3,3'-4,4'-biphenyltetracarboxylic dianhydride in Synthesis Example 1 was 44.1 g (0.15 mol) (P
A4) or 53.655 g (0.1825 mol)
Except for changing to (PA5), the same operation as in Synthesis Example 1 was performed to obtain two kinds of polyamic acids. Table 1 shows the logarithmic viscosity of the polyamic acid.

[Synthesis Example 6] (Polyamide acid PA6) A polyamic acid was obtained in exactly the same manner as in Synthesis example 1 except that the total amount of the organic solvent in Synthesis example 1 was changed to 270 g of N, N-dimethylacetamide. Table 1 shows the logarithmic viscosity of the polyamic acid.

[0036]

[Table 1] Examples of the photosensitive resin composition of the present invention using the polyamic acid shown in the above synthesis examples are shown below.

Example 1 Compounding amount (parts by weight) Synthesis Example 1 Polyamic acid (PA1) 200 Pentaerythritol triacrylate (Aronix M-305 manufactured by Toagosei Co., Ltd.) 24 Tetraethylene glycol diacrylate (Aronix M manufactured by Toagosei Co. -240) 3 Methylene bisacrylamide (Tokyo Kasei Co., Ltd.) 3 IRUGACURE907 (Ciba Geigy Co., Ltd .; hereinafter abbreviated as IGC907)

Example 2 Compounding amount (parts by weight) Synthesis Example 1 Polyamic acid (PA1) 200 Pentaerythritol triacrylate 6 Tetraethylene glycol diacrylate 21 Methylenebisacrylamide 3 IGC907 4 DETX 1

[Comparative Example 1] Compounding amount (parts by weight) Synthesis Example 2 Polyamic acid (PA2) 200 Pentaerythritol triacrylate 24 Tetraethylene glycol diacrylate 3 Methylenebisacrylamide 3 IGC907 4 DETX 1

[Comparative Example 2] Compounding amount (parts by weight) Synthesis Example 3 Polyamic acid (PA3) 200 Pentaerythritol triacrylate 24 Tetraethylene glycol diacrylate 3 Methylenebisacrylamide 3 IGC907 4 DETX 1

[Comparative Example 3] Compounding amount (parts by weight) Synthesis Example 4 Polyamic acid (PA4) 200 Pentaerythritol triacrylate 24 Tetraethylene glycol diacrylate 3 Methylenebisacrylamide 3 IGC907 4 DETX 1

[Comparative Example 4] Compounding amount (parts by weight) Synthesis Example 5 Polyamic acid (PA5) 200 Pentaerythritol triacrylate 24 Tetraethylene glycol diacrylate 3 Methylenebisacrylamide 3 IGC907 4 DETX 1

Comparative Example 5 Compounding amount (parts by weight) Synthesis Example 6 Polyamic acid (PA6) 200 Pentaerythritol triacrylate 24 Tetraethylene glycol diacrylate 3 Methylenebisacrylamide 3 IGC907 4 DETX 1

Comparative Example 6 Compounding Amount (Parts by Weight) Synthesis Example 1 Polyamic Acid (PA1) 200 Pentaerythritol Triacrylate 27 Methylenebisacrylamide 3 IGC907 4 DETX 1

[Comparative Example 7] Compounding amount (parts by weight) Synthesis Example 1 Polyamic acid (PA1) 200 Tetraethylene glycol diacrylate 27 Methylenebisacrylamide 3 IGC907 4 DETX 1

Comparative Example 8 Compounding Amount (parts by weight) Synthesis Example 1 Polyamic acid (PA1) 200 Pentaerythritol triacrylate 15 Tetraethylene glycol diacrylate 15 IGC907 4 DETX 1 The above photosensitive resin composition was prepared. The printed circuit board on which the conductive circuit pattern was drawn was uniformly applied using a doctor blade. Then, it dried at 80 degreeC for 40 minutes, and produced the sample for a test. A test sample was obtained by coating and drying a 1 mm thick metal plate and a 1 oz. Copper foil glossy surface. The dried coating film thickness was adjusted so that a photosensitive film having a thickness of 20 to 25 μm was obtained on the conductive circuit, the metal plate, and the glossy surface of the copper foil.

Next, 3 kW using a desired photomask
500 mj / cm ^{2 on the} photosensitive film with an ultra-high pressure mercury lamp
Exposure was performed so that the amount of light could be irradiated. The exposed photosensitive film was immersed in a developer adjusted to 30 ° C. with a 1.0 wt% aqueous solution of sodium hydroxide for 50 seconds to perform development. In Examples 1 and 2 and Comparative Examples 1 and 2 and 6 and 7, the unexposed portions were easily peeled off with the developer to obtain desired images. In Comparative Example 3, the exposed portion was completely dissolved in the developing solution, and no image was obtained. In Comparative Example 4, the unexposed portion did not dissolve in the developer, and no image could be obtained. In Comparative Examples 5 and 8,
Although the desired image was obtained, the coating film cracked. Examples 1-2 and Comparative Examples 1-2, 6-7 were subjected to 250
The coating was converted to polyimide by heating at 10 ° C. for 10 minutes. 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, 12
After immersion for a time, the remaining amount of the 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% by weight hydrochloric acid aqueous solution at 60 ° C. for 12 hours, and the remaining amount of the 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 sodium hydroxide solution 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 confirm the presence or absence of cracks in the coating. Evaluation 8: 1 oz. In a test sample formed on a glossy surface of a rolled copper foil, the copper foil was etched to a width of 2 mm, and the film and the 2 mm-wide copper foil were peeled off at an angle of 90 °. Was shown by Peel strength (Kg / cm). Evaluation 9: 1 oz. On a test sample formed on a glossy surface of a rolled copper foil, the entire surface of the copper foil was etched to prepare a test sample having only a film. This is 15m wide
m, a test piece having a length of 150 mm was cut and subjected to a tensile elongation test to show the elongation (%) of the film.

Table 2 shows the evaluation results of Examples 1-2 and Comparative Examples 1-8. From the evaluation results, in Examples 1 and 2, it is possible to develop with an alkaline aqueous solution, and has excellent adhesiveness with a conductor, flexibility, chemical resistance, and film elongation. No swelling occurs. In Comparative Example 1, the elongation of the film was extremely low. In Comparative Example 2, the adhesion to the conductor was not sufficient. In Comparative Example 6, the elongation of the film was low. In Comparative Example 7, heat resistance was low, and peeling occurred after immersion in the solder.

[0049]

[Table 2]

[0050]

As can be seen from Table 2, the insulating film and the solder resist film comprising the photosensitive resin composition according to the present invention can be developed with an aqueous alkali solution.
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.
Further, the polyamic acid exhibits thermoplasticity by having a specific structure, has a strong adhesive force to a conductor such as a metal foil, and further contains a specific (meth) acrylate compound and a specific acrylamide compound. As a result, since the film has good elongation properties, excellent performance can be expected as an interlayer insulating material for a multilayer printed wiring board and a cover coat material for a flexible circuit board.

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Claims (4)

[Claims] (A) The following formula (1): Having a logarithmic viscosity (N, N
-Dimethylacetamide solvent, concentration 0.5 g / 100 m
(B, measured at 35 ° C.) of 100 to 100 parts by weight of a polyamic acid having a concentration of 0.3 to 1.0 dl / g, containing (B) an alcoholic hydroxyl group and at least three or more photopolymerizable Cs.
(C) 10 to 100 parts by weight of a (meth) acrylate compound having an unsaturated double bond, (C) 5 to 100 parts by weight of a polyalkylene glycol di (meth) acrylate compound, and (D) the following formula (2): 2] (Wherein R ¹ represents a hydrogen atom or a methyl group, R ² represents a hydrogen atom, CH ₂ or CH ₂ OH, and n is 1 or 2) 5 to 50 parts by weight of the acrylamide compound And (E) a photosensitive resin composition containing a photopolymerization initiator as an essential component. 2. The photosensitive resin composition according to claim 1,
A photosensitive resin composition obtained by diluting a mixed solvent containing 10 to 1000 parts of a glycol ether-based organic solvent with respect to 100 parts of a nitrogen-containing organic solvent. 3. The photosensitive resin composition according to claim 1, wherein the cured film has an elongation of 20% or more. 4. A processed product having a photosensitive film formed by applying and drying the photosensitive resin composition according to claim 1 on a metal, plastic or ceramic.