JP3004595B2 - Photosensitive resin composition and dry film resist using the same - Google Patents

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 for a dry film resist used in the manufacture of a printed wiring board, and more particularly to a photosensitive resin composition having a high resolution and a high sensitivity, and also having a fine line adhesion. The present invention relates to a photosensitive resin composition.

[0002]

2. Description of the Related Art In the manufacture of printed wiring boards and the like, a photoresist method using a photosensitive resin composition is used. In this photoresist method, for example, a photosensitive material is first exposed on a support such as a transparent film. After applying the photosensitive resin composition to form a photosensitive resin composition layer, the photosensitive resin composition layer is laminated on the surface of a substrate on which a desired pattern is to be formed, and then the photosensitive resin composition layer is formed. After exposing the original image through a pattern mask, the unexposed portions are removed by a developing process using a solvent or an aqueous alkali solution to form a resist image, and the formed resist image is used as a protective mask,
After performing a well-known etching process or pattern plating process, the method of manufacturing a printed circuit board by stripping a resist is usually performed. In such a manufacturing process, it is required to have high sensitivity in order to improve productivity and shorten time. Further, in recent years, as electronic devices have become smaller and lighter, printed wiring boards have become finer and higher in density, and a dry film resist having a high resolution (DFR) has been demanded. I have.

As the photopolymerization initiator used in such a photosensitive resin composition, for example, conventional benzoins, ketones, quinones, diketones, alkyl oxime esters and the like, or a combination thereof, for example, JP 6
No. 1-173242 discloses benzophenone / Michler's ketone / N-phenylglycine;
In the publication, Michler's ketone or thioxanthone compound / N-phenylglycine is used. JP-A-2-48664 discloses a photopolymerization initiator comprising 4,
A resin composition having high sensitivity and high resolution using 4'-bis (dialkylamino) benzophenone / aromatic ketone / rofin dimer has been proposed. Further, JP-A-2-62
No. 545 discloses specific benzoins and 2,4,5-
A combination system of a triarylimidazole dimer is used, has a high curing rate, and has good storage stability,
The aim is to improve tenting and resolution.

[0004]

However, the photopolymerization initiator systems described in the above publications are not yet satisfactory in sensitivity in view of recent advances in technology and precision. When the concentration of the photopolymerization initiator is increased to increase the viscosity, the internal curability deteriorates, causing problems such as a reduction in resolution and developer resistance. Further, a combination system of 4,4'-bis (dialkylamino) benzophenone / aromatic ketone / rophin dimer described in JP-A-2-48664 and benzoins described in JP-A-2-62545 and 2,2 As a result of detailed studies by the present inventors, the use of a combination system of 4,5-triarylimidazole dimer alone is not satisfactory in terms of resolution, sensitivity and the like, and there is still room for improvement. Under such circumstances, the present invention has a high sensitivity and a high resolution under such a background, and further aims to provide a photosensitive resin composition having excellent fine line adhesion and a dry film resist using the same. I do.

[0005]

Means for Solving the Problems However, the present inventors have conducted intensive studies in order to solve such problems, and as a result, (a) a carboxyl group-containing polymer, (b) an ethylenically unsaturated compound, and (c) photopolymerization start (C-1) N-aryl-α-amino acid-based compound as a photopolymerization initiator, based on the total weight of (a) and (b). ~ 1.0% by weight, (c-2) N, N '
-Tetraalkyl-4,4'-diaminobenzophenone-based compound in an amount of 0.01 to 0.5% by weight, (c-3) lofin dimer in an amount of 0.5 to 6.0% by weight, (c-4) Chemical 1
It has been found that a photosensitive resin composition containing the compound represented by the formula (1) in an amount of 0.1 to 10% by weight satisfies the above object, thereby completing the present invention.

[0006]

Embedded image Here, R ₁ and R ₂ are hydrogen or an alkyl group, which may be the same or different from each other.

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described specifically. As the (a) carboxyl group-containing polymer used in the present invention, an acrylic copolymer containing (meth) acrylic acid ester as a main component and copolymerized with an ethylenically unsaturated carboxylic acid is preferably used. If necessary, an acrylic copolymer obtained by copolymerizing another copolymerizable monomer can be used. In this case, the content of each component is (meth) acrylate component 70 to 8
5% by weight, preferably 75 to 82% by weight, and 15 to 30% by weight, preferably 1 to 30% by weight of an ethylenically unsaturated carboxylic acid component.
8 to 25% by weight, other copolymerizable monomer components are 0 to
It is often 15% by weight.

Here, the (meth) acrylic acid ester includes methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate,
-Ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, and the like. You.

As the ethylenically unsaturated carboxylic acid, for example, monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid are preferably used.
Dicarboxylic acids such as fumaric acid and itaconic acid, or anhydrides and half esters thereof can also be used. Of these, acrylic acid and methacrylic acid are particularly preferred.

[0010] Other copolymerizable monomers include, for example, (meth) acrylic acid tetrahydrofurfuryl ester, (meth) acryldimethylaminoethyl ester,
(Meth) acrylic acid diethylaminoethyl ester, methacrylic acid glycidyl ester, 2,2,2-trifluoroethyl (meth) acrylate, (meth) acrylamide, 2,2,3,3-tetrafluoropropyl (meth) acrylate acrylamide, Examples include diacetone acrylamide, styrene, α-methylstyrene, vinyl toluene, vinyl acetate, alkyl vinyl ether, (meth) acrylonitrile and the like.

The carboxyl group-containing polymer (a) thus obtained may be used in combination with a polyester resin, a polyamide resin, a polyurethane resin, an epoxy resin, and the like. The carboxyl group-containing polymer has a weight average molecular weight of 10,000 to 300,000, preferably 10,000 to 150,000, more preferably 300 to 300,000.
When the molecular weight is small, cold flow is liable to occur. Conversely, when the molecular weight is large, development is difficult, and the resolution is lowered, and the peelability at the time of peeling the resist is poor.

(B) As the ethylenically unsaturated compound,
Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene Glycol di (meta)
Acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexane glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol Di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 2,2-bis (4-acryloxy) Diethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxypolyethoxyphenyl) propane, 2-hydroxy-3- (meth) acryloyloxypropyl acryle DOO, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate,
1,6-hexamethyldiglycidyl ether di (meth)
Acrylate, trimethylolpropane triglycidyl ether tri (meth) acrylate, bisphenol A
Examples include polyfunctional monomers such as diglycidyl ether di (meth) acrylate, diglycidyl phthalate di (meth) acrylate, and glycerin polyglycidyl ether poly (meth) acrylate.

An appropriate amount of a monofunctional monomer can be used together with these polyfunctional monomers. Examples of such a monofunctional monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2
-Phenoxy-2-hydroxypropyl (meth) acrylate, 2- (meth) acryloyloxy-2-hydroxypropylphthalate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, 2- (meth) ) Acryloyloxyethyl acid phosphate, phthalic acid derivative half (meth) acrylate, N-methylol (meth) acrylamide, and the like.

The compounding ratio of (b) the ethylenically unsaturated compound is as follows: (a) a carboxyl group-containing polymer and (b)
5-90% by weight, preferably 20-80% by weight, particularly preferably 40% by weight, based on the total weight of the ethylenically unsaturated compound.
It is desirable to select from the range of ６０60% by weight. (B) An insufficient amount of the ethylenically unsaturated compound causes poor curing, reduced plasticity, and a delay in the development speed. (B) An excessive amount of the ethylenically unsaturated compound causes an increase in tackiness, cold flow, and peeling of the cured resist. It is not preferable because the speed decreases.

(C) As the photopolymerization initiator, (c-1)
N-aryl-α-amino acid compounds, (c-2) N,
N'-tetraalkyl-4,4'-diaminobenzophenone-based compound, (c-3) lophin-based dimer, (c-
4) At least a compound represented by the above formula 1 is contained. (C-1) N-aryl-α-amino acid compounds include N-phenylglycine, N-methyl-N-phenylglycine, N-ethyl-N-phenylglycine,
-(N-propyl) -N-phenylglycine, N- (n
-Butyl) -N-phenylglycine, N- (2-methoxyethyl) -N-phenylglycine, N-methyl-N-
Phenylalanine, N-ethyl-N-phenylalanine, N- (n-propyl) -N-phenylalanine, N
-(N-butyl) -N-phenylalanine, N-methyl-N-phenylvaline, N-methyl-N-phenylleucine, N-ethyl-N- (p-tolyl) glycine, N-
(N-propyl) -N- (p-tolyl) glycine, N-
(N-butyl) -N- (p-tolyl) glycine, N-methyl-N- (p-chlorophenyl) glycine, N-ethyl-N- (p-chlorophenyl) glycine, N- (n-
Propyl) -N- (p-chlorophenyl) glycine, N
-Methyl-N- (p-bromophenyl) glycine, N-
Ethyl-N- (p-bromophenyl) glycine, N-
(N-butyl) -N- (p-bromophenyl) glycine, N, N'-diphenylglycine, N-methyl-N-
(P-iodophenyl) glycine, N- (p-bromophenyl) glycine, N- (p-chlorophenyl) glycine, N- (o-chlorophenyl) glycine, etc., and N-phenylglycine is preferably used. .

(C-2) N, N'-tetraalkyl-
As 4,4'-diaminobenzophenone-based compounds,
N, N'-tetramethyl-4,4'-diaminobenzophenone, N, N'-tetraethyl-4,4'-diaminobenzophenone, N, N'-tetrapropyl-4,4 '
-Diaminobenzophenone, N, N'-tetrabutyl-
4,4'-diaminobenzophenone and the like are preferable, and N, N'-tetraethyl-4,4'-diaminobenzophenone and N, N'-tetramethyl-4,4'-diaminobenzophenone are preferably used.

(C-3) Examples of the lophin dimer include triphenyl biimidals, particularly 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) 4,5-diphenylimidazole Dimer, 2,4- (p-methoxyphenyl) -5-phenylimidazole dimer, 2- (o-ethoxyphenyl) -4,5-diphenylimidazole dimer, 2,4-di (p- Ethoxyphenyl) -5-phenylimidazole dimer and the like.
(O-Chlorophenyl) -4,5-diphenylimidazole dimer is used. (C-4) Examples of the compound represented by the above formula 1 include benzyl dimethyl ketal, benzyl diethyl ketal and the like, preferably benzyl dimethyl ketal.

The amount of the photopolymerization initiator (c) is as follows:
It is 0.01 to 20% by weight, preferably 0.1 to 15% by weight, based on the total weight of (a) and (b). For each photopolymerization initiator, the amount of (c-1) Is
0.01 to 1.0% by weight, preferably 0.01 to 0.5% by weight, based on the total weight of (a) and (b);
The amount of (2) is 0.01 to 0.5% by weight, preferably 0.01 to 0.3% by weight, and the amount of (c-3) is 0.5 to 6.0% by weight. , Preferably 0.5 to 3.0
%, And the compounding amount of (c-4) needs to be 0.1 to 10% by weight, preferably 1.0 to 5.0% by weight.

When the amount of (c) is less than 0.01% by weight, poor curing results. When the amount is more than 20% by weight, the adhesion decreases. Also, (c-
If the amount of 1) is less than 0.01% by weight, the sensitivity is lowered,
If it exceeds 1.0% by weight, the adhesive strength is undesirably reduced. If the amount of (c-2) is less than 0.01% by weight, the resolving power will decrease, and if it exceeds 0.5% by weight, the adhesion will decrease, which is not preferable. The compounding amount of (c-3) is 0.5
If the content is less than 6.0% by weight, the effect of the present invention cannot be obtained.
Exceeding the adhesive strength and storage stability are undesirably reduced. If the amount of (c-4) is less than 0.1% by weight, the effects of the present invention cannot be obtained. If the amount exceeds 10% by weight, the adhesion and the resolving power decrease, which is not preferable.

In the present invention, it is also preferable to use other initiators in addition to (c-1) to (c-4) as the photopolymerization initiator (c). Other initiators include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether,
Benzoin n-butyl ether, benzoin phenyl ether, benzyl diphenyl disulfide, dibenzyl, diacetyl, anthraquinone, naphthoquinone, 3,
3'-dimethyl-4-methoxybenzophenone, benzophenone, p, p'-bis (dimethylamino) benzophenone, p, p'-bis (diethylamino) benzophenone, pivaloin ethyl ether, 1,1-dichloroacetophenone, p- t-butyldichloroacetophenone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-diethylthioxanthone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-dichloro-4- Phenoxyacetophenone, phenylglyoxylate, α-hydroxyisobutylphenone, dibezosparone, 1-
(4-Isopropylphenyl) -2-hydroxy-2-
Examples thereof include methyl-1-propanone, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone, tribromophenylsulfone, tribromomethylphenylsulfone, and the like. These may be used alone or in combination of two or more. Are used in combination.

Thus, the photosensitive resin composition of the present invention can be obtained from (a) a carboxyl group-containing polymer, (b) an ethylenically unsaturated compound, and (c) a photopolymerization initiator. As agents, thermal polymerization inhibitors, plasticizers, dyes (pigments, discoloring agents), adhesion promoters, antioxidants,
Solvents, surface tension modifiers, stabilizers, chain transfer agents, defoamers,
Additives such as a flame retardant can be appropriately added. For example, a thermal polymerization inhibitor is added to prevent thermal polymerization or polymerization with time of the photosensitive resin composition, and p-methoxyphenol, hydroquinone, t-butylcatechol, pyrogallol, 2-hydroxybenzophenone , 4
-Methoxy-2-hydroxybenzophenone, cuprous chloride, phenothiazine, chloranil, naphthylamine, β
-Naphthol, 2,6-di-t-butyl-p-cresol, nitrobenzene, picric acid, p-toluidine and the like.

The plasticizer is added to control the physical properties of the film. Examples of the plasticizer include phthalic esters such as dibutyl phthalate, diheptyl phthalate, dioctyl phthalate and diallyl phthalate; triethylene glycol diacetate, tetraethylene glycol diacetate and the like. Glycol esters; phosphate esters such as tricresyl phosphate and triphenyl phosphate;
Amides such as p-toluenesulfonamide, benzenesulfonamide, Nn-butylacetamide; aliphatic dibasic acid esters such as diisobutyl adipate, dioctyl adipate, dimethyl sebacate, dioctyl azelate, dibutyl malate; citric acid Triethyl, tributyl citrate, glycerin triacetyl ester,
Glycols such as butyl laurate, dioctyl 4,5-diepoxycyclohexane-1,2-dicarboxylate, polyethylene glycol and polypropylene glycol are exemplified.

Examples of the dye include tris (4-dimethylaminophenyl) methane [leucocrystal violet], tris (4-diethylamino-2-methylphenyl) methane, leucomalachite green, leucoaniline, leucomethyl violet, brilliant green, Eosin, ethyl violet, erythrosin B,
Methyl green, crystal violet, basic fuchsin, phenolphthalein, 1,3-diphenyltriazine, alizarin red S, thymolphthalein, methyl violet 2B, quinaldine red, rose bengal, methanil yellow, thymol sulfophthalein, xylenol blue , Methyl orange, orange
IV, diphenylthiocarbazone, 2,7-dichlorofluorescein, paramethyl red, congo red, benzopurpurine 4B, α-naphthyl red, nile blue A, phenacetaline, methyl violet, malachite green, parafuchsin, oil blue # 603 [ Orient Chemical Co., Ltd.], Victoria Pure Blue B
OH, Spiron Blue GN [Hodogaya Chemical Industry Co., Ltd.
And Rhodamine 6G. Among them, leuco dyes such as leuco crystal violet, malachite green, brilliant green are 0.01 to 0.5% by weight,
Preferably, the content is 0.01 to 0.2% by weight.

The discoloring agent is added to the photosensitive resin composition so that a visible image can be given by exposure, and specific examples thereof include diphenylamine, dibenzylaniline, triphenylamine, diethylaniline, Diphenyl-p-phenylenediamine, p-toluidine,
4,4'-biphenyldiamine, o-chloroaniline,
And the like.

Examples of the adhesion promoter include benzimidazole, benzthiazole, benzoxozole, benztriazole, 2-mercaptobenzthiazole,
-Mercaptobenzimidazole and the like. In addition, it is also preferable to use an organic halogen compound in combination with the above-mentioned dyes, such as amyl bromide, isoamyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzyl bromide, methylene bromide, and tribromomethylphenylsulfone. , Carbon tetrabromide, tris (2,3-dibromopropyl)
Phosphate, trischloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-trichloro-2,
2-bis (p-chlorophenyl) ethane hexachloroethane and the like.

The photosensitive resin composition of the present invention is generally used as a photoresist film having a laminated structure. The film is obtained by sequentially laminating a support film, a photosensitive resin composition layer, and a protective film.

The support film used in the present invention has heat resistance and solvent resistance when forming the photosensitive resin composition layer. Specific examples of the support film include, for example, a polyester film, a polyimide film, and an aluminum foil. However, the present invention is not limited to such examples. The thickness of the support film varies depending on the material of the film, and thus cannot be unconditionally determined. Usually, the thickness is appropriately adjusted according to the mechanical strength of the film.
It is about 0 μm.

When the thickness of the photosensitive resin composition layer is too small, the coating becomes non-uniform or pinholes are liable to be formed during coating and drying, and when the thickness is too large, Is usually 5 to 300 μm, especially 10 to 5 μm, because the exposure sensitivity is reduced and the developing speed is reduced.
It is preferably 0 μm.

When the photoresist film is used in the form of a roll, the photosensitive resin composition layer having adhesiveness may be transferred to a support film, or the protective film used in the present invention may be used as a protective film. It is used by being laminated on a photosensitive resin composition layer for the purpose of preventing a wall or the like from adhering to the layer. Examples of such a protective film include a polyester film, a polyethylene film, a polypropylene film, a Teflon film, and the like, but the present invention is not limited to only such examples. The thickness of the protective film is not particularly limited and is usually 10
５０50 μm, especially 10-30 μm.

Next, the production of a laminate for a dry film resist using the photosensitive resin composition of the present invention and the method of producing a printed wiring board using the same will be described. (Lamination method) The above photosensitive resin composition is coated on a support film surface such as a polyester film, a polypropylene film, and a polystyrene film, and then protected from above the coated surface with a polyethylene film, a polyvinyl alcohol-based film, and the like. The film is coated to form a laminate for a dry film resist. For applications other than dry film resist, the photosensitive resin composition of the present invention is
The photosensitive layer having a thickness of 1 to 150 μm can be easily formed by directly coating the (copper) substrate to be processed by a conventional method such as a dip coating method, a flow coating method, and a screen printing method. At the time of coating, methyl ethyl ketone, methyl cellosolve acetate, ethyl cellosolve acetate, cyclohexane, methyl cellosolve, methylene chloride, 1,1,
A solvent such as 1-trichloroethane can also be added.

(Exposure) In order to form an image using a dry film resist, the adhesive strength between the support film and the photosensitive resin composition layer and the adhesive strength between the protective film and the photosensitive resin composition layer are compared. After the lower film is peeled off, the photosensitive resin composition layer side is adhered to a metal surface such as a copper surface of a copper-clad substrate, and then the other film is exposed with a pattern mask adhered thereto. When the photosensitive resin composition does not have adhesiveness, the other film may be peeled off, and then the pattern mask may be brought into direct contact with the photosensitive resin composition layer for exposure. When directly applied to the metal surface,
A pattern mask is brought into contact with the coated surface directly or via a polyester film or the like, and exposed. Exposure is usually performed by ultraviolet irradiation, and as a light source at that time, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a carbon arc lamp, a xenon lamp, a metal halide lamp, a chemical lamp, or the like is used. After irradiation with ultraviolet rays, heating can be performed as necessary to complete the curing.

(Development) After exposure, development is performed after the film on the resist is removed. Since the photosensitive resin composition of the present invention is a rare alkali developing type, development after exposure is
This is performed using a dilute aqueous solution of about 0.3 to 2% by weight of alkali such as sodium carbonate and potassium carbonate. A surfactant, an antifoaming agent, a small amount of an organic solvent for accelerating development, and the like may be mixed in the alkaline aqueous solution.

(Etching, Plating) In the etching, etching is usually performed using an acidic etching solution such as an aqueous solution of cupric chloride-hydrochloric acid or an aqueous solution of ferric chloride-hydrochloric acid according to a conventional method. Rarely, an ammonia-based alkali etching solution is also used. In the plating method, after performing pretreatment using a plating pretreatment agent such as a degreasing agent and a soft etching agent, plating is performed using a plating solution. (Removal of Hardened Resist) After the etching step, the remaining hardened resist is stripped off. Removal of the hardened resist is performed by using 0.5% of sodium hydroxide, potassium hydroxide, etc.
This is performed using an alkaline stripping solution composed of an aqueous alkali solution having a concentration of about 5% by weight.

The photosensitive resin composition of the present invention and the laminate for a dry film resist of the composition are very useful as etching resists or plating resists used in the production of printed wiring boards, precision metal processing, lead frame production and the like. Useful, (a) a carboxyl group-containing polymer,
(B) an ethylenically unsaturated compound, (c) a photopolymerization initiator,
In particular, (c-1) an N-aryl-α-amino acid compound,
(C-2) N, N'-tetraalkyl-4,4'-diaminobenzophenone-based compound, (c-3) lophine dimer, (c-4) a specific compound represented by the above formula 1 in a specific amount Since it contains, it exhibits excellent effects in sensitivity, resolution, and fine line adhesion.

[0035]

The present invention will be described in more detail with reference to the following examples. Unless otherwise specified, “%” and “parts” are based on weight. Examples 1 to 4 and Comparative Examples 1 to 8 The following carboxyl group-containing polymers were used as (a), and (b), (c-1), (c-2), (c-3),
With respect to (c-4) and other additives, dopes of the photosensitive resin compositions having the compositions shown in Table 1 were prepared. (A) ・ Methyl methacrylate / butyl acrylate / 2-ethylhexyl acrylate / methacrylic acid (weight ratio: 4)
8/10/20/22) 40% methyl ethyl ketone / isopropyl alcohol (weight ratio 50/50) solution of copolymer having a weight average molecular weight of 70,000

[0036]

(Table 1) (a) (b) (c-1) (c-2) (c-3) (c-4) Other solids TMPT-TA HOA-MPE NPG EAB-F HABI BDK LCV MG TBMPS (% (%) (%) (%) (%) (%) (%) (%) (%) (%) Example 1 54.42 31.28 5.00 0.20 0.10 4.00 4.00 0.60 0.10 0.30 〃 2 55.26 18.42 18.42 0.10 0.10 4.00 3.00 0.60 0.10 --- ３3 55.20 18.40 18.40 0.10 0.20 4.00 3.00 0.60 0.10 --- ４4 55.26 18.42 18.42 0.10 0.10 3.00 4.00 0.60 0.10 --- Comparative example 1 54.54 31.36 5.00 --- 0.10 4.00 4.00 0.60 0.10 0.30 〃2 53.82 30.88 5.00 1.20 0.10 4.00 4.00 0.60 0.10 0.30 ３ 3 54.24 31.16 5.00 0.10 --- 4.00 4.00 0.60 0.10 0.80 ４ 4 53.76 30.84 5.00 0.10 0.80 4.00 4.00 0.60 0.10 0.80 ５ 5 55.92 18.64 18.64 0.20 0.10 --- 5.00 0.60 0.10 〃6 51.72 17.24 17.24 0.20 0.10 7.00 5.00 0.60 0.10 0.80 ７7 56.52 32.68 5.00 0.20 0.10 4.00 --- 0.60 0.10 0.80 ８8 49.32 27.88 5.00 0.20 0.10 4.00 12.00 0.60 0.10 0.80

Note) TMPT-TA: Trimethylolpropane triacrylate (manufactured by Nippon Kayaku Co., Ltd.) HOA-MPE: 2-acryloyloxyethyl-2-hydroxyethylphthalic acid (manufactured by Kyoeisha Yushi Co., Ltd.) NPG: N-phenylglycine ( EAB-F: N, N'-tetraethyl-4,4'-diaminobenzophenone (Hodogaya) HABI: 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer (Hodogaya) BDK: Benzyl dimethyl ketal (I-651: Ciba-Geigy) LCV: Leuco crystal violet (Hodogaya) MG: Malachite green (Hodogaya) TBMPS: Tribromomethylphenylsulfone (Tokyo Kasei)

Next, each of the dopes was coated on a polyester film having a thickness of 20 μm using an applicator having a gap of 10 mil and left at room temperature for 1 minute and 30 seconds.
The resultant was dried in an oven at 60 ° C., 90 ° C., and 110 ° C. for 3 minutes to obtain a dry film having a resist thickness of 50 μm (provided that no protective film was provided). This dry film was placed on a copper-clad substrate preheated to 60 ° C in an oven.
Laminate roll temperature 100 ° C, roll pressure 3kg / c
The lamination was performed at m ² and a lamination speed of 1.5 m / sec. The copper-clad board used here was 1.6 mm in thickness, and was a board with a width of 200 mm and a length of 250 mm in which a 35 μm copper foil was attached to both sides of a glass fiber epoxy base material.

Next, the obtained substrate was exposed with a 5 kW high-pressure mercury lamp (parallel light). At this time, a negative film (a 21-step stofer step tablet) made so that the light transmission amount was reduced stepwise so that the light sensitivity could be evaluated was used. 15 minutes after the exposure, the polyester film is peeled off, and a break point of a 1% aqueous sodium carbonate solution at 30 ° C. (time for completely dissolving unexposed portions)
The unexposed portion was dissolved and removed by spraying for twice the developing time to obtain a cured resin image. The substrate was etched with a cupric chloride etchant. At this time, the minimum required etching time was 60 seconds and the etching time was 90 seconds. Then, add 1% aqueous solution of 3% sodium hydroxide at 50 ° C.
After spraying for 20 seconds, the cured resin film used as the resist was peeled off to form a relief image.

In the above process, the following items were evaluated as follows. (Sensitivity) The sensitivity of the photosensitive resin composition was evaluated by measuring the exposure amount (mj / cm ² ) until the number of steps of the step tablet of the photocured film formed on the copper-clad substrate reached 8.

(Resolution) L / S (line / space) =
1/1 (10, 15, 20, 25, 30, 35, 40,
(45, 50 μm) and then developed for twice the break point, and evaluated by the minimum line width on which an image was formed.

(Fine wire adhesion) After laminating on a copper-clad substrate, the line width was 10, 15, 20, 25, 30, 35, 4
0, 45, 50 μm pattern mask (space width is 4
00 μm), and the minimum line width (μm) with good adhesion was examined in the same manner as described above.

Table 2 shows the evaluation results of the examples and comparative examples.

[Table 2]

[0044]

The photosensitive resin composition obtained according to the present invention and the laminate for a dry film resist using the same are excellent in sensitivity, resolution, and fine line adhesion, so that the fineness of printed wiring boards and the like can be reduced. This makes it possible to increase the density, and is useful as an etching resist or a plating resist used in the manufacture of printed wiring boards, the manufacture of lead frames, precision processing of metals, and the like.

Claims (5)

(57) [Claims] (1) a carboxyl group-containing polymer,
In the photosensitive resin composition comprising (b) an ethylenically unsaturated compound and (c) a photopolymerization initiator, (c) as a photopolymerization initiator, (c−) is based on the total weight of (a) and (b). 1) N
-Aryl-α-amino acid compound in an amount of 0.01 to 1.0
% By weight, (c-2) N, N'-tetraalkyl-4,
4′-diaminobenzophenone-based compound in an amount of 0.01 to
0.5% by weight, (c-3) 0.5 to 10%
6.0% by weight, (c-4) 0.1 to 10% by weight of a compound represented by the following formula (1): a photosensitive resin composition. Embedded image Here, R ₁ and R ₂ are hydrogen or an alkyl group, which may be the same or different from each other. 2. The photosensitive resin composition according to claim 1, comprising (c-1) N-phenylglycine as the N-aryl-α-amino acid compound. (C-2) N, N'-tetraalkyl-
As a 4,4'-diaminobenzophenone-based compound,
The photosensitive resin composition according to claim 1, comprising N, N'-tetraethyl-4,4-diaminobenzophenone. 4. The photosensitive resin composition according to claim 1, wherein (c-3) a triphenylbiimidazole is contained as a lophine dimer. 5. The photosensitive resin composition according to claim 1, wherein (c-4) the compound represented by the formula 1 contains benzyldimethyl ketal.