JP2001166471A - Photosensitive resin composition and photosensitive film using same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition excellent in flexibility and resistance to the heat of soldering, developable with a dilute alkali solution and suitable for an etching resist and a cover lay and a photosensitive film using the composition. SOLUTION: The photosensitive resin composition developable with an aqueous alkali solution contains a carboxyl-containing polyamide oligomer (A) obtained by reacting a diamine compound (a) with a polybasic acid anhydride (b) having two acid anhydride groups in one molecule and a (meth)acrylate (c) having one epoxy group in one molecule and a photopolymerization initiator (B).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition, in particular, a photosensitive resin composition suitable for forming an etching resist or a protective film (coverlay) which can be used for manufacturing a flexible printed wiring board and the like, and a photosensitive composition using the same. Sex film.

[0002]

2. Description of the Related Art Conventionally, in the production of printed wiring boards, liquid or film-shaped photosensitive resin compositions have been used. For example, as a resist for etching a copper foil of a copper-clad laminate, a printed wiring board on which wiring is formed is used for limiting a soldering position, protecting wiring, and the like.
2. Description of the Related Art Some printed wiring boards have a film shape that can be folded and incorporated into a small device such as a camera, and this is called an FPC. This FPC also requires a resist for limiting the soldering position and protecting the wiring, which is called a coverlay or a covercoat. The coverlay is formed by punching polyimide or polyester having an adhesive layer into a predetermined mold, and then by thermocompression bonding on an FPC.The cover coat is formed by printing and curing a thermosetting or photocurable ink. Formed.

In these resists used for the purpose of limiting the soldering position of the FPC and protecting the wiring, flexibility is a particularly important characteristic, and therefore, a polyimide coverlay excellent in flexibility is often used. . However, this coverlay requires an expensive mold for die cutting,
In addition, due to the manual bonding of the die-cut film and the sticking-out of the adhesive, the yield is low and the manufacturing cost is high, which is an obstacle to the expansion of the FPC market. It is difficult to respond.

Accordingly, a photosensitive resin composition for forming a highly accurate and highly reliable coverlay excellent in dimensional accuracy and resolution by a photographic development method (a method of forming an image by a phenomenon following image exposure), In particular, the appearance of a photosensitive film has been desired. For this purpose, attempts have been made to use a photosensitive resin composition for forming a solder mask. For example, photosensitive resin compositions containing an acrylic polymer and a photopolymerizable monomer as main components (JP-A-53-56018 and JP-A-54-56018).
As a photosensitive resin composition having good heat resistance, a composition mainly composed of a photosensitive epoxy resin having a chalcone group in a main chain and an epoxy resin curing agent (JP-A-54-82073) JP-A-58-62636), a composition mainly composed of a novolak-type epoxy acrylate containing an epoxy group and a photopolymerization initiator (JP-A-61-272, etc.), safety and economy As a photosensitive resin composition for forming a solder mask that can be developed with an alkaline aqueous solution, a carboxyl group-containing polymer,
Compositions comprising a monomer, a photopolymerization initiator and a thermosetting resin as main components (JP-A-48-73148, JP-A-57-73148)
178237, JP-A-58-42040,
JP-A-59-151152, etc.), but all have insufficient flexibility.

[0005]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned drawbacks of the prior art, and provides a photosensitive resin composition which is excellent in workability, excellent in flexibility, solder heat resistance and the like. To provide a photosensitive film.

[0006]

The present invention relates to (1) a diamine compound (a), a polybasic anhydride (b) having at least two acid anhydride groups in the molecule, and one polyamine anhydride in the molecule. A resin composition containing a carboxyl group-containing polyamide oligomer (A) obtained by reacting an epoxy group-containing (meth) acrylate (c), (2) a carboxyl group-containing polyamide oligomer (A) described in (1) and light A photosensitive resin composition containing a polymerization initiator (B), (3) the photosensitive resin composition according to (2), wherein the carboxyl group-containing polyamide oligomer (A) has an acid value of 10 to 200 mgKOH / g, (4) A photosensitive film obtained by laminating a layer of the photosensitive resin composition according to (2) to (3) on a support film, and (5) a photosensitive resin composition according to (2) to (4). And film hardness And (6) an article having the cured product according to claim 5.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The carboxyl group-containing polyamide oligomer (A) used in the present invention comprises a diamine compound (a) and a polybasic acid anhydride (b) having at least two acid anhydride groups in a molecule. It can be obtained by reacting (meth) acrylate (c) having one epoxy group in the molecule.

The diamine compound (a) is not particularly restricted but includes, for example, aromatic diamines and aliphatic diamines.

As the aromatic diamine, for example, 2,2-
Bis [4- (4-aminophenoxy) phenyl] propane, bis [4- (4-aminophenoxy) phenyl] sulfone, 2,2-bis- [4- (3-aminophenoxy) phenyl] hexafluoropropane, bis [4-
(4-aminophenoxy) phenyl] biphenyl, bis [4- (4-aminophenoxy) phenyl] methane, bis [4- (3-aminophenoxy) phenyl] methane,
Bis [4- (4-aminophenoxy) phenyl] ether, bis [4- (3-aminophenoxy) phenyl] ether, bis [4- (3-aminophenoxy) phenyl] benzophenone, bis [4- (4-amino) Phenoxy) phenyl] benzanilide, bis [4- (3-aminophenoxy) phenyl] benzanilide, 9,9-bis [4- (3-aminophenoxy) phenyl] fluorene, p-phenylenediamine, m-phenylenediamine, p- Xylylenediamine, m-xylylenediamine, 1,5-diaminonaphthalene, 4,4′-benzophenonediamine, and the like.

Examples of the aliphatic diamine include ethylenediamine, tetramethylenediamine, hexamethylenediamine, 1,2-diaminocyclohexane, diaminopolysiloxane, Jeffamine D-230 (hereinafter, manufactured by San Techno Chemical Co., Ltd.), and D-400. , D-200
0, D-4000, ED-600, ED-900, ED
-2001, EDR-148 and the like. These can be used alone or in combination of two or more.

The polybasic acid anhydride (b) having at least two acid anhydride groups in the molecule is preferably a carboxylic acid anhydride, for example, pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, biphenyltetraacid anhydride. Carboxylic acid dianhydride, biphenyl ether tetracarboxylic dianhydride, diphenylsulfone tetracarboxylic dianhydride, butanetetracarboxylic dianhydride, ethylene glycol bis (anhydrotrimellitate) and the like,
They can be used alone or in combination of two or more.

The (meth) acrylate (c) having one epoxy group in the molecule includes, for example, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate and the like. A mixture of more than one species can be used.

The carboxyl group-containing polyamide oligomer (A) used in the present invention can be synthesized, for example, as follows. First, a diamine compound (a) is reacted with a polybasic acid anhydride (b) having at least two acid anhydride groups in a molecule to prepare a polyamide prepolymer having a terminal amine carboxyl group. 1
(Meth) acrylate (c) having two epoxy groups is reacted.

The terminal amine carboxyl group-containing polyamide prepolymer has a polybasic acid anhydride (b) having at least two acid anhydride groups in the molecule per one equivalent of the amine group of the diamine compound (a). Preferably, the reaction is carried out in an amount of from 0.5 to 0.98 equivalents (as acid anhydride equivalents). The reaction temperature of this amidation reaction is 0 to 80 ° C, and the reaction time is 1 to 10
Time is preferred.

Next, the polyamide prepolymer having a terminal amine carboxyl group is preferably reacted with a (meth) acrylate (c) having one epoxy group in the molecule to obtain a carboxyl group-containing polyamide oligomer (A). The epoxy group of (meth) acrylate (d) having one epoxy group in the molecule per one equivalent of the total number of carboxyl groups and amino groups of the terminal amine carboxyl group-containing polyamide prepolymer is 0.05. ~
It is preferable to react 0.95 equivalent, particularly preferably 0.1 to 0.8 equivalent. The reaction temperature is usually from room temperature to 100 ° C, preferably from 50 to 90 ° C. To prevent gelation due to radical polymerization during this reaction, usually 5
It is preferable to add 0 to 2000 ppm of a polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, p-methoxyphenol, and p-benzoquinone. Although the reaction between the carboxyl group and the epoxy group proceeds without a catalyst, a basic compound such as triethylamine or triphenylphosphine may be added as a catalyst.

Although an organic solvent may be added during this reaction, a nitrogen-free polar solvent is preferred. Specific examples of organic solvents include, for example, aromatic hydrocarbons such as toluene and xylene; lactones such as γ-butyrolactone, γ-valerolactone, γ-caprolactone, α-acetyl-γ-butyrolactone; ethyl acetate, acetic acid Esters such as butyl; ethers such as 1,4-dioxane, diethylene glycol diethyl ether and triethylene glycol dimethyl ether; ketones such as methyl ethyl ketone and methyl isobutyl ketone; glycols such as butyl cellosolve acetate, carbitol acetate, propylene glycol monomethyl ether acetate Derivatives include alicyclic hydrocarbons such as cyclohexanone and cyclohexane, and petroleum solvents such as petroleum ether and petroleum naphtha. One or more of these organic solvents may be added.

The resin composition of the present invention (photosensitive resin composition)
Is preferably 10 to 99% by weight, particularly preferably 20 to 95% by weight in the composition.

In the present invention, a diluent can be contained. Examples of the diluent include the above-mentioned organic solvents and photopolymerizable monomers. Examples of the photopolymerizable monomers include 2-hydroxyethyl (meth) acrylate, 2
-Hydroxypropyl (meth) acrylate, cyclohexane-1,2-dimethylol mono (meth) acrylate, glycerin di (meth) acrylate, trimethylo-
Lepropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate carbitol (meth) acrylate, fanoxyethyl (meth) acrylate,
Acryloyl morpholine, bisphanol A polyethoxydi (meth) acrylate, polyethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol ditrimethylolpropane tetra (meth) acrylate, tris (2-hydroxyethyl) isocyanatetra (meth) A) acrylate, dipentaerythritol hexa (meth) acrylate and the like. These reactive monomers may be used alone or in combination of two or more.

In the present invention, a photopolymerization initiator (B) is used. Examples of the photopolymerization initiator include benzoys such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether and benzoin isobutyl ether; acetophenone, 2,2-diethoxy-2-phenylacetophenone, 2,2-diethoxy. 2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxycyclohexylphenylketone, 2- Methyl-
Acetophenones such as 1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one; anthraquinones such as 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-chloroanthraquinone and 2-amylanthraquinone And 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 2-
Thioxanthones such as chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenone, 4-benzoyl-
Benzophenones such as 4'-methyldiphenyl sulfide and 4,4'-bismethylaminobenzophenone;
Examples thereof include phosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide.

These can be used alone or as a mixture of two or more. Further, tertiary amines such as triethanolamine and methyldiethanolamine, N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoate It can be used in combination with an accelerator such as a benzoic acid derivative such as acid isoamyl ester.

The amount of the photopolymerization initiator (B) used is 1 to 30 parts by weight, preferably 5 to 20 parts by weight, based on 100 parts by weight of the total amount of (A).

The photosensitive resin composition of the present invention is a mixture containing the carboxyl group-containing polyamide oligomer (A) and the photopolymerization initiator (B). The acid value (mgKOH / g) of the carboxyl group-containing polyamide oligomer (A) used here is preferably from 10 to 200,
Particularly preferably, it is 30 to 150.

The photosensitive resin composition of the present invention may contain a thermoplastic polymer (C). For example, acrylic resin, polyester resin, vinyl acetate resin, vinyl chloride-vinyl acetate copolymer and the like can be mentioned. The thermoplastic polymer (C) includes a polymer having a carboxyl group and a polymer having no carboxyl group, and a polymer having a carboxyl group can be preferably used. More specifically, for example, acrylic acid, methacrylic acid, methyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, ethyl acrylate, methyl acrylate, styrene, α-methylstyrene, vinyl toluene, N-vinylpyrrolidone, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, acrylamide, 2-hydroxypropyl methacrylate, 2-hydroxypropyl acrylate, acrylonitrile, methacrylonitrile, dimethylaminoethyl methacrylate, dimethylaminoethyl acrylate, styrene / mailen A half ester of an acid copolymer is exemplified. These are used alone or in combination of two or more.

The weight average molecular weight of the component (C) is 5,000
It is preferably from 0 to 300,000. If the weight average molecular weight is less than 5,000, the film properties tend to decrease, and if it exceeds 300,000, the developability tends to decrease. Further, the carboxyl group content of the component (C) is preferably 0 to 50 mol%, more preferably 15 to 50 mol%. If it exceeds 50 mol%, pattern formation tends to be difficult. The component (C) is preferably soluble or swellable in an aqueous alkaline solution.

The amount of the component (C) contained in the photosensitive resin composition of the present invention is preferably 5 to 75% by weight, more preferably 10 to 70% by weight in the composition.

In the present invention, a thermosetting component (D) can be used. By using this, solder heat resistance and electrical characteristics can be further improved. Examples of the thermosetting component (D) include an epoxy resin, a melamine compound, an oxazoline compound, and a phenol compound. Specific examples of the epoxy resin include bisphenol A epoxy resin, bisphenol F epoxy resin, phenol novolak epoxy resin, cresol novolak epoxy resin, trisphenolmethane epoxy resin, brominated epoxy resin, and biphenol epoxy resin. Glycidyl ethers such as epoxy resins; 3,4-
Epoxy-6-methylcyclohexylmethyl-3,4-
Epoxy-6-methylcyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl-3,4-
Alicyclic epoxy resins such as epoxycyclohexanecarboxylate and 1-epoxyethyl-3,4-epoxycyclohexane; glycidyl esters such as diglycidyl phthalate, diglycidyl tetrahydrophthalate and glycidyl dimer; tetraglycidyl diamino Glycidylamines such as diphenylmethane; and heterocyclic epoxy resins such as triglycidyl isocyanurate. Among them, an epoxy resin having a melting point of 50 ° C. or more is preferable because a tack-free photopolymerizable film can be formed after drying.

Examples of the melamine compound include melamine and a melamine resin which is a polycondensate of melamine and formalin. Examples of the urea compound include urea and urea resins which are polycondensates of urea and formalin.

Examples of the oxazoline compound include 2-oxazoline, 2-methyl-2-oxazoline, 2-phenyl-2-oxazoline, 2,5-dimethyl-2-oxazoline, 5-methyl-2-phenyl-2-oxazoline,
2,4-diphenyloxazoline and the like.

Examples of the phenol compound include phenol, cresol, chilenol, catechol, resorcin, hydroquinone, pyrogallol, resol and the like.

When an epoxy resin is used as the thermosetting component (D), it is preferable to use a curing accelerator. Specific examples of the curing accelerator for the epoxy resin include 2-methylimidazole and 2-methylimidazole. Imidazole compounds such as ethyl-3-methylimidazole, 2-undecylimidazole, 2-phenylimidazole, 1-cyanoethyl-2-ethylimidazole, 1-cyanoethyl-2-undecylimidazole, etc .; melamine, guanamine, acetoguanamine, benzoguanamine , Ethyldiaminotriazine, 2,4-diaminotriazine, 2,4
Triazine derivatives such as -diamino-6-tolyltriazine and 2,4-diamino-6-xylyltriazine; tertiary amines such as trimethylamine, triethanolamine, N, N-dimethyloctylamine, pyridine and m-aminophenol Polyphenols and the like.
These curing accelerators can be used alone or in combination.

In the present invention, various additives and the like can be further added as needed. As various additives,
For example, fillers such as talc, barium sulfate, calcium carbonate, magnesium carbonate, barium titanate, aluminum hydroxide, aluminum oxide, silica, clay,
Thixotropic agents such as Aerosil, phthalocyanine blue, phthalocyanine green, coloring agents such as titanium oxide, silicone, fluorine-based leveling agents and defoamers, dyes, hydroquinone, P-methoxyphenol,
And polymerization inhibitors such as hydroquinone monotyl ether.

The photosensitive film of the present invention can be produced by laminating a layer of the photosensitive resin composition of the present invention on a support film. Examples of the support include a polymer film, for example, a film made of polyethylene terephthalate, polypropylene, polyethylene and the like. Among them, a polyethylene terephthalate film is preferable. Since these polymer films must be removed from the photosensitive layer later, they must not be surface-treated or made of a material that cannot be removed. The thickness of these polymer films is 5 to 10
The thickness is preferably 0 μm, more preferably 10 to 30 μm. These polymer films can be laminated on both sides of the photosensitive layer as a support film for one photosensitive layer and another as a protective film for the photosensitive layer.

The photosensitive resin composition and the photosensitive film of the present invention are obtained by dissolving the components (A), (B) and (C) and the above-mentioned diluent, thermosetting component (D) or various additives. It can be prepared and manufactured by mixing and kneading.

Next, the prepared resin composition is uniformly coated on the polymer film of the support film,
The solvent can be removed by heating and / or blowing with hot air to form a dry film. The thickness of the dried film is not particularly limited, and is preferably 10 to 100 μm.
It is more preferable that the thickness be 60 μm.

The photosensitive film of the present invention comprising two layers, a photosensitive layer and a polymer film, obtained as described above, may be used as it is or by further laminating a protective film on the other surface of the photosensitive layer to form a roll. It can be wound up and stored.

The photosensitive resin composition and the photosensitive film of the present invention are particularly useful as resists such as etching resists and solder resists for flexible printed wiring boards, and can also be used as paints, coating agents, adhesives and the like. .

As a method for producing a photoresist image using the photosensitive film of the present invention, if the protective film is present, the protective film is removed, and then the photosensitive layer is press-bonded to the substrate while heating. By doing so, they can be laminated. At this time, it is preferable that the layers are stacked under reduced pressure. The surface to be laminated is not particularly limited, and is preferably an FPC on which wiring is formed by etching or the like. The heating temperature of the photosensitive layer is not particularly limited,
The temperature is preferably set to 90 to 130 ° C. The pressure for pressing is not particularly limited, and it is preferable that the pressing be performed under reduced pressure.

The photosensitive layer thus completed in lamination is
It is imagewise exposed to active light using a negative film or a positive film.At this time, if the polymer film present on the photosensitive layer is transparent, it can be exposed as it is, but if it is opaque, Need to be removed. From the viewpoint of protecting the photosensitive layer, the polymer film is transparent, and it is preferable to expose the polymer film while leaving the polymer film remaining. As the active light, a known active light source can be used, and examples thereof include light generated from a carbon arc, a mercury vapor arc, a xenon arc, and the like.
Since the sensitivity of the photopolymerization initiator contained in the photosensitive layer is usually maximum in the ultraviolet region, the active antigen in that case preferably emits ultraviolet light effectively.

Next, after exposure, if a polymer film is present on the photosensitive layer, the polymer film is removed and then removed by a known method such as spraying, rocking immersion, and brushing using an aqueous alkali solution. The unexposed portion can be removed and developed. Examples of the base of the alkaline aqueous solution include alkali hydroxides such as lithium, sodium or potassium hydroxide, alkali carbonates such as lithium or sodium or potassium carbonate or bicarbonate, potassium phosphate, and sodium phosphate. And alkali metal pyrophosphates such as sodium pyrophosphate and potassium pyrophosphate. Among them, an aqueous solution of sodium carbonate is preferable. The pH of the aqueous alkali solution used for development is preferably 9 to 11. The developing temperature can be adjusted according to the developability of the photosensitive layer. In the alkaline aqueous solution,
A surfactant, an antifoaming agent, and a small amount of an organic solvent for promoting development can be mixed.

Further, after the development, ultraviolet irradiation or heating by a high-pressure mercury lamp can be performed for the purpose of improving the solder heat resistance and chemical resistance as a coverlay of the FPC. The irradiation amount of ultraviolet rays is 0.2 to 10 J / cm ^2.
It is preferable that at the time of this irradiation, 60 to 150
It is preferably accompanied by heat of ° C. The heating temperature during heating is preferably 100 to 170 ° C. Either the irradiation of the ultraviolet rays or the heating may be performed first. After the characteristics of the coverlay are given in this way,
Mounting (soldering) of components such as LSIs, and mounting to devices such as cameras.

[0041]

The present invention will be described below with reference to examples. It goes without saying that the present invention is not limited to the following examples. In the following, “parts” means “parts by weight” unless otherwise specified.

Synthesis Example 1 (Synthesis example of carboxyl group-containing polyamide oligomer (A)) 601 g of 3,4′-diaminophenyl ether, 436 of pyromellitic anhydride (acid value: 1011 mg KOH / g)
g, 1030 g of γ-butyrolactone and reacted at 40 ° C. for about 5 hours to obtain a polyamide prepolymer having a terminal amine carboxyl group (acid value of solid: 212.5 mg KO).
H / g). Then, glycidyl methacrylate 5
08 g and 1.75 g of p-methoxyphenol, and reacted at 95 ° C. for 10 hours.
A carboxyl group-containing polyamide oligomer (A-1) having gKOH / g, a weight average molecular weight of about 5000 (by GPC method) and a solid content of 60% was obtained.

Synthesis Example 2 (Synthesis Example of Thermoplastic Polymer (C) Having Carboxyl Group) 121.5 g of γ-butyrolactone was placed in a flask, heated to 85 ° C., and left for 1 hour. Next, 13.5 g of methacrylic acid, 46.8 g of methyl methacrylate, 38.2 g of ethyl acrylate, 3.2 g of 2-hydroxyethyl methacrylate, and 1.5 g of 2-ethylhexyl acrylate
g, azobisisobutyronitrile 0.17 g, and a solution of γ-butyrolactone 31.2 g were reacted dropwise over 4 hours. Thereafter, 7.1 g of γ-butyrolactone was added, and the mixture was kept warm for 2 hours. A solution of 0.6 g of methacrylic acid, 0.54 g of azobisisobutyronitrile, and 4.8 g of γ-butyrolactone was added, and the mixture was further kept warm for 2 hours. Thereafter, 0.024 g of azobisisobutyronitrile was added to γ-butyrolactone 1.2
g, and after keeping the solution warm for 5 hours, 0.01 g of hydroquinone was added and cooled, and the average molecular weight was 84,000.
Solids acid value of 38.5% by weight of non-volatile content (mgKOH /
g) a thermoplastic polymer having 85 carboxyl groups (C
-1) was obtained.

EXAMPLES AND COMPARATIVE EXAMPLES A photosensitive resin composition containing the materials shown in Table 1 was 25 μm
The film was uniformly coated on a polyethylene terephthalate film having a thickness of 5 mm and dried to remove the solvent. The thickness of the photosensitive layer after drying was 50 μm. Next, a polyethylene film was laminated as a protective film on the photosensitive layer to obtain a photosensitive laminate.

Table 1 Compounding amount (parts by weight) Material Example 1 Example 2 Example 3 Comparative Example A-1 75.0 90.0 158.3 C-1 105.3 85.3 250.3 DPCA-60 * 1 20.0 20.0 20.0 20.0 EAB * 2 0.1 0.1 0.1 0.1 Benzophenone 5.0 5.0 5.0 5.0 Melamine 10.0 10.0 10 0.0 10.0 γ-butyrolactone 115.0 120.0 137.0 45.0

Note) * 1: DPCA-60; KAYA, manufactured by Nippon Kayaku Co., Ltd.
RAD DPCA-60 (ε of dipentaerythritol
* 2: EAB; 4,4'-dimethylaminobenzophenone manufactured by Hodogaya Chemical Co., Ltd.

Separately, the copper surface of an FPC substrate (trade name, F30VC125RC11, manufactured by Nikkan Kogyo Co., Ltd.) having a 35 μm thick copper foil laminated on a polyimide substrate was polished with an abrasive brush, washed with water, and dried. The photosensitive film was laminated on this substrate (23 ° C.) using a vacuum laminator.

Next, the sample thus obtained was added with a stofer 2
Exposure was performed at 200 mJ / cm ² using a single-step tablet and a negative film having a linear line of 150 μm / 150 μm line / space, and then left at room temperature for 30 minutes. Next, spray development was performed at 30 ° C. for 100 seconds using a 1% aqueous solution of sodium carbonate. Here, the number of remaining step tablets is measured, and the results are shown in Table 2.
It was shown to. Next, a heat treatment was performed at 150 ° C. for 45 minutes, and further, ultraviolet irradiation at ³ J / cm ² was performed to obtain a coverlay.

This sample was heated at 180 ° C. for evaluation of flexibility.
After bending, coverlay was observed for cracks and other abnormalities. Then, rosin crack MH-820V
(Trade name, manufactured by Tamura Kaken Co., Ltd.), soldered at 260 ° C. for 10 seconds, observed for abnormalities such as blistering as solder heat resistance, and then evaluated for flexibility. Therefore, the coverlay was bent at 180 ° C., and the coverlay was observed for cracks and other abnormalities. Table 2 shows the above evaluation results.

Table 2 Number of remaining steps Solder heat resistance Bendability (180 ° C.) (260 ° C., 10 seconds) Before soldering After soldering Example 1 9 Good Good Good Example 2 9 Good Good Good Example 3 9 Good Good Good Comparative Example 2 8 Good Cracking Cracking

As is clear from Table 2, when the photosensitive resin composition of the present invention is used, a coverlay having both good solder heat resistance and bending property (flexibility) can be obtained.

[0052]

The photosensitive resin composition of the present invention has good workability, excellent flexibility and excellent solder heat resistance, and is suitable for an etching resist for FPC and a photosensitive film for coverlay.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) H05K 3/28 H05K 3/28 D // C08J 5/18 CFG C08J 5/18 CFG F-term (reference) 2H025 AA10 AA13 AB11 AB15 AB20 AC01 AD01 BC13 BC31 BC68 BC83 BC85 FA17 FA43 4F071 AA31 AA42 AA60 AA78 AH13 BA03 BB02 BC02 BC12 4J002 CM041 EE036 EE056 EV016 EV306 EW146 FD010 FD090 GP03 5E314 AA27 FF01 CC12 CC12 CCA CC CF16 CF17 DD02

Claims (6)

[Claims] 1. A diamine compound (a), a polybasic acid anhydride (b) having at least two acid anhydride groups in a molecule, and a (meth) acrylate (c) having one epoxy group in a molecule. A resin composition containing a carboxyl group-containing polyamide oligomer (A) obtained by reacting 2. A photosensitive resin composition comprising the carboxyl group-containing polyamide oligomer (A) according to claim 1 and a photopolymerization initiator (B). 3. The photosensitive resin composition according to claim 2, wherein the carboxyl group-containing polyamide oligomer (A) has an acid value of 10 to 200 mgKOH / g. 4. A photosensitive film obtained by laminating a layer of the photosensitive resin composition according to claim 2 on a support film. 5. A cured product of the photosensitive resin composition and the film according to claim 2. 6. An article having the cured product according to claim 5.