JP2769589B2 - Photosensitive resin composition - 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 in which the contrast difference between an exposed portion and an unexposed portion and the resistance to fluorinated acid are remarkably improved without impairing the storage stability after lamination on a copper surface. It relates to a composition.

[0002]

[Prior art]

<Lamination of the photosensitive resin composition on the metal surface, exposure> The photosensitive resin composition is applied in layers on a base film such as a polyester film, and a protective film such as a polyethylene film or a polyvinyl alcohol film is laminated thereon. The laminated film thus obtained is generally called a dry film, and is widely used for manufacturing printed wiring boards and precision processing of metal.

[0003] In use, first, the base film or the protective film having the smaller adhesive strength was peeled off from the dry film, and the photosensitive resin composition layer side was attached to the copper surface of the copper-clad substrate. Thereafter, exposure is performed in a state where the pattern mask is in contact with the other film (in some cases, exposure is performed after the other base film is peeled off), and then the other film is peeled off and subjected to development. . As a development method after exposure, there are a solvent development type and a dilute alkali development type.

In addition to a dry film, a method is also well known in which a photosensitive resin composition is applied directly onto a metal surface and formed into a layer, and a pattern mask is adhered to the layer through a film such as a polyester film laminated thereon. I have.

<Photosensitive resin composition containing benzotriazoles> Some of the above-mentioned photosensitive resin compositions contain a small amount of benzotriazoles in order to improve adhesion to copper surfaces and solder masks. There is.

For example, Japanese Patent Publication No. 50-9177 (containing a small amount of a heterocyclic nitrogen-containing compound such as benzotriazole and benzimidazole as an adhesion promoter) and Japanese Patent Publication No. 58-24035 (Japanese Patent Application Laid-Open No. 58-24035)
Publication) (benzotriazole, benzimidazole,
Benzothiazole, etc.), and JP-A-59-48752.
JP (Imidazole, thiazole, tetrazole, triazole or a derivative thereof is added)
JP-A-166541 (adding benzotriazole carboxylic acids), JP-A-61-223836 (adding a benzotriazole derivative), JP-A-61-56341
No. JP-A-61-5 (to which benzotriazole is added)
No. 6342 (addition of a salt of benzotriazole), JP-A-55-22481 (benzotriazole derivative), JP-A-55-65202 (with comparative examples to which benzotriazole is added), JP-A-55-65202 65203
(Comparative examples to which benzotriazole is added).

<Photosensitive resin composition containing triazine derivative> In the above-mentioned photosensitive resin composition, a small amount of a triazine derivative or the like is used in order to improve a contrast difference between an exposed portion and an unexposed portion by ultraviolet rays. There is a thing which mixes.

For example, JP-A-59-78339 discloses a photopolymerizable composition using 4,4'-bis (dialkylamino) benzophenone, benzophenone and the like, and an s-triazine compound as a photopolymerization initiator. Things are shown. The publication also mentions that an adhesion promoter such as benzotriazole may be used in combination, but no examples are given.

JP-A-2-48664 discloses a photopolymerizable composition in which a specific photopolymerization initiation system is used in combination with an organic halide such as an s-triazine compound. The publication states that known adhesion promoters may be used, and many publications are cited, and specific examples of adhesion promoters are also mentioned, but the specific examples include benzotriazole. Is not raised.

Japanese Unexamined Patent Publication (Kokai) No. 61-123602 discloses a highly sensitive photopolymerizable composition in which the photopolymerization initiation system comprises a benzanthrone derivative and a hexaarylbiimidazole or s-triazine compound. .

Japanese Patent Application Laid-Open No. 61-151644 discloses that
A photosensitive composition comprising a 4,6-bis (halomethyl) -s-triazine free radical generator and a compound that interacts with the free radical generator and a photolysis product is disclosed.
According to this photosensitive composition, a clear boundary is obtained between an exposed portion and an unexposed portion, and a visible image with high contrast is obtained. In the description of the prior art in this publication,
Vinyl-halomethyl-s-triazine compounds described in U.S. Pat. Nos. 3,954,475 and 39,870,37 and JP-A-48-36281, and JP-A-53-13342.
No. 8 and JP-A-55-32070 also disclose that s-triazine compounds such as halomethyl-s-triazine compounds have extremely high photodegradation sensitivity and excellent stability over time.

References which use a triazine derivative as a free radical generator for promoting the color development of a photochromic agent include, in addition, JP-A-54-74887, JP-A-62-61044, and JP-A-63-55539. No., JP-A-2-63
No. 054 and the like.

[0013]

The photosensitive resin composition containing the triazine derivative promotes the color development of leuco dyes and the like, and contributes to improving the contrast difference between an exposed portion and an unexposed portion. According to the studies by the inventors, there is a problem in that the storage stability after lamination on a copper surface is impaired, and abnormal increase or decrease in sensitivity occurs.

More specifically, a photosensitive resin composition containing a triazine derivative, after lamination (for example, one day) after lamination on a copper surface, has an excessively high sensitivity, resulting in a decrease in resolution and a short period of time. If it gets longer (for example, 3
Day), the sensitivity tends to decrease this time.

JP-A-59-78339 discloses that an adhesion promoter such as benzotriazole may be used in combination in a system using an s-triazine compound. There is a description that a known adhesion promoter may be used in a system using an s-triazine compound, but this only describes the possibility of use as an adhesion promoter, and no examples are given.

According to the present invention, in a system using a triazine derivative, the contrast difference between an exposed portion and an unexposed portion and the resistance to borofluoric acid are remarkably improved without impairing the storage stability after lamination on a copper surface. It is an object of the present invention to provide a photosensitive resin composition that can be used.

[0017]

The photosensitive resin composition of the present invention comprises a composition comprising a base polymer (A), an ethylenically unsaturated compound (B), a photopolymerization initiator (C) and a dye (D). Wherein the benzotriazoles (E) and the triazine derivative (F) are added to 100 parts by weight of the total amount of the base polymer (A), the ethylenically unsaturated compound (B), the photopolymerization initiator (C) and the dye (D). 0.0 each
3 to 1.0 part by weight, 0.05 to 1.0 part by weight , and benzotriazoles (E) at that time
And the molar ratio of the triazine derivative (F) to 1: 3 to 3: 1
It is characterized by being.

Hereinafter, the present invention will be described in detail.

Base Polymer (A) As the base polymer (A), an acrylic resin, a polyester resin, a polyamide resin, a polyurethane resin, an epoxy resin or the like is used. Among these, an acrylic copolymer containing (meth) acrylate as a main component and optionally copolymerizing an ethylenically unsaturated carboxylic acid or another copolymerizable monomer is important. An acetoacetyl group-containing acrylic copolymer can also be used.

Here, the acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and cyclohexyl. Examples thereof include (meth) acrylate, benzyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and glycidyl (meth) acrylate.

As the ethylenically unsaturated carboxylic acid, monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid are preferably used. In addition, dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid, and their anhydrides Products and half esters can also be used. Of these, acrylic acid and methacrylic acid are particularly preferred.

In the case of a dilute alkali developing type, about 15 to 30% by weight of an ethylenically unsaturated carboxylic acid (1
(About 200 to 200 mg KOH / g).

Examples of other copolymerizable monomers include acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, styrene, α-methylstyrene, vinyl acetate, and alkyl vinyl ether.

Ethylenically unsaturated compound (B) Examples of the ethylenically unsaturated compound (B) include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di ( (Meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexane glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, Glycerin di (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, 2,2-bi (4- (meth) acryloxydiethoxyphenyl) propane, 2,
2-bis (4- (meth) acryloxypolyethoxyphenyl) propane, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di Examples include polyfunctional monomers such as (meth) acrylate, 1,6-hexamethyldiglycidyl 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 monofunctional monomers include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 2-phenoxy-2-hydroxypropyl (meth) acrylate. 2- (meth) acryloyloxy-2-hydroxypropyl phthalate, 3-chloro-2-hydroxypropyl (meth) acrylate,
Examples include glycerin mono (meth) acrylate, 2- (meth) acryloyloxyethyl acid phosphate, phthalic acid derivative half (meth) acrylate, and N-methylol (meth) acrylamide.

The proportion of the ethylenically unsaturated compound (B) per 100 parts by weight of the base polymer (A) is preferably selected from the range of 10 to 200 parts by weight, particularly preferably 40 to 100 parts by weight. Too little ethylenically unsaturated compound (B) causes poor curing, reduced flexibility, and slows down development speed, while too much ethylenically unsaturated compound (B) increases tackiness, cold flow, and peeling of cured resist. It causes a reduction in speed.

Photopolymerization initiator (C) Examples of the photopolymerization initiator (C) include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin phenyl ether, benzyl diphenyl disulfide, and benzyl dimethyl ketal. , 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, hexaarylimidazole dimer, 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-methyl-1-propanone, 2-methyl- [4 (Methylthio) phenyl]
-2-morpholino-1-propanone, tribromophenylsulfone, tribromomethylphenylsulfone, N
-Phenylglycine and the like.

The mixing ratio of the photopolymerization initiator (C) is such that the total amount of the base polymer (A) and the ethylenically unsaturated compound (B) is 1
It is appropriate that the amount is about 1 to 20 parts by weight with respect to 00 parts by weight.

Dye (D) As the dye (D), leuco crystal violet, tris (4-diethylamino-o-tolyl) methane, bis (4-diethylamino-o-tolyl) phenylmethane,
Bis (4-diethylamino-o-tolyl) thienyl-2
-A coloring dye (D ₁ ) by light action such as methane, bis (2-chloro-4-diethylaminophenyl) phenylmethane, leucomalachite green, malachite green, victoria pure blue, fuchsin, methyl orange, nile blue 2B, night green B, Spiron blue,
Coloring dyes (D ₂ ) such as Acid Violet RRH and Auramine base.

Coloring dye (D ₁ ) and coloring dye as dye (D)
When the colored resin composition is produced in combination with (D ₂ ), the workability in the step of laminating the film on a copper substrate or the step of aligning a pattern mask in dry film applications is improved.

The mixing ratio of the dye (D) is based on the base polymer.
It is appropriate to use about 0.1 to 3 parts by weight based on 100 parts by weight of the total of (A) and the ethylenically unsaturated compound (B).

Benzotriazoles (E) Examples of the benzotriazoles (E) include: 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, and 4-carboxy-1 , 2,3-benzotriazole, -5-carboxy-1,2,3-benzotriazole, -bis (N-2-ethylhexyl) aminomethylene-
1,2,3-benzotriazole, bis (N-2-ethylhexyl) aminomethylene-
1,2,3-tolyltriazole, bis (N-2-hydroxyethyl) aminomethylene-
1,2,3-benzotriazole and the like are used.

Triazine derivative (F) Examples of the triazine derivative (F) include : 2,4,6- [tris ( trichloromethyl )]- s-
Triazine, 2-phenyl-4,6-bis (trichloromethyl)-
s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s
-Triazine, -2-n-propyl-4,6-bis (trichloromethyl) -s-triazine, -2- (p-chlorophenyl) -4,6-bis (trichloromethyl) -s-triazine, -2- (P-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-bis (trichloromethyl) -4'-methoxyphenyl-s-triazine, 2- (4-methoxy-naphtho) -1-yl) -4,6-
Bis-trichloromethyl-s-triazine, 2- (4-ethoxy-naphth-1-yl) -4,6-
Bis-trichloromethyl-s-triazine, 2- [4- (2-ethoxyethyl) -naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4,7- Dimethoxy-naphth-1-yl)-
4,6-bis-trichloromethyl-s-triazine, 2- (acenaphth-5-yl) -4,6-bis-trichloromethyl-s-tolidine, 2- (2 ', 4'-dichlorophenyl)- 4,6-bis (trichloromethyl) -s-triazine, • 2-n-nonyl-4,6-bis (trichloromethyl)
-S-triazine, 2- (α, α, β-trichloroethyl) -4,6-bis (trichloromethyl) -s-triazine, • 2-styryl-4,6-bis (trichloromethyl)-
s-triazine, 2-p-methylstyryl-4,6-bis (trichloromethyl) -s-triazine, 2-p-methoxystyryl-4,6-bis (trichloromethyl) -s-triazine, etc. can give.

The amounts of the benzotriazoles (E) and the triazine derivatives (F) added depend on the base polymer (A), the ethylenically unsaturated compound (B), the photopolymerization initiator (C) and the dye.
0.03 to 1.0 respectively for 100 parts by weight of the total amount of (D)
Parts by weight (preferably 0.05 to 0.5 parts by weight) and 0.05 to 1.0 parts by weight (preferably 0.1 to 0.5 parts by weight). An insufficient amount of the benzotriazoles (E) causes an insufficient effect of improving the storage stability after lamination on the copper surface, and an excessive amount impairs the soft etching property of the plating pretreatment. If the amount of the triazine derivative (F) is too small, a contrast difference between an exposed part and an unexposed part and insufficient fluoric acid resistance are caused, and the excessive amount impairs the soft etching property of the plating pretreatment.

[0035] In addition, the molar ratio of the benzotriazoles (E) and a triazine derivative (F) is 1: 3 to 3: 1, preferably 1: 2 to 2: set to 1, both the molar ratio of the range
If it is out of the range, the combined effect of the two cannot be sufficiently exhibited.

Other Additives The photosensitive resin composition of the present invention may further include an adhesion promoter, a plasticizer, an antioxidant, a thermal polymerization inhibitor, a solvent, a surface tension modifier, a stabilizer, and a chain transfer. Additives such as agents, defoamers and flame retardants can be added as appropriate.

Layering method The above-mentioned photosensitive resin composition is coated on a base film surface such as a polyester film, a polypropylene film or a polystyrene film, and then a polyethylene film, a polyvinyl alcohol film or the like is coated on the coated surface. A dry film is formed by coating the protective film.

In addition to a dry film, a photosensitive resin composition may be directly applied to a metal surface to form a layer.

In the case of an exposed dry film, the adhesive strength between the base film and the photosensitive resin composition layer and the adhesive strength between the protective film and the photosensitive resin composition layer are compared, and the film having the lower adhesive strength is peeled off. After that, the photosensitive resin composition layer side is attached 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 layer has no tackiness, 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.

In the case of directly coating a metal surface, a pattern mask is brought into contact with the coated surface directly or via a polyester film or the like, and exposed to light.

Exposure is usually performed by irradiation with ultraviolet light, 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 the ultraviolet irradiation, heating can be performed as necessary to complete the curing.

After development exposure, development is performed after the film on the resist is peeled off. When the photosensitive resin composition of the present invention is of a dilute alkali developing type, development after exposure is performed using a dilute aqueous solution of an alkali such as sodium carbonate or potassium carbonate. In the case of a solvent development type, development is performed using a solvent such as 1,1,1-trichloroethane.

When the etching or plating etching method is employed, the etching is performed according to a conventional method using an etching solution such as an aqueous ferric chloride solution or an aqueous cupric chloride solution. When the plating method is adopted, a pretreatment is performed using a plating pretreatment agent such as a degreasing agent or a soft etching agent, and then plating is performed using a plating solution.

Removal and Removal of the Cured Resist In the case of a solvent-developable photosensitive resin composition, the removal of the cured resist is carried out using a solvent such as methylene chloride. In the case of a rare alkali developing type photosensitive resin composition,
1-5% by weight of sodium hydroxide, potassium hydroxide, etc.
This is performed using an alkaline stripping solution composed of an alkaline aqueous solution having a moderate concentration.

Uses The photosensitive resin composition of the present invention can be used for various uses, such as for manufacturing printed wiring boards and for precision processing of metals.

[0046]

The photosensitive resin composition of the present invention has good storage stability after lamination on a copper surface, a large difference in contrast between exposed and unexposed areas, and has good resistance to acidity. Benzotriazoles (E) have a previously unknown effect of improving poor shelf stability after lamination when using only triazine derivatives (F) by using them in combination with triazine derivatives (F). Demonstrate.

[0047]

The present invention will be further described with reference to the following examples. Hereinafter, “parts” and “%” are expressed on a weight basis.

Examples 1 to 7, Comparative Examples 1 to 7 <Preparation of dope> 54 parts of the following base polymer (A), 36 parts of the following ethylenically unsaturated compound (B), and a photopolymerization initiator having the following formulation (C) 9.15 parts, and the following formula dye (D)
0.85 parts were mixed to prepare a resin composition. The weight ratio of (A) :( B) is 6/4, based on 100 parts of the total amount of (A) and (B).
The amounts of (C) and (D) are 10.2 parts and 0.94 parts, respectively.

Base polymer (A) methyl methacrylate / n-butyl methacrylate / 2
A copolymer having a copolymerization ratio of ethylhexyl acrylate / methacrylic acid of 55/8/15/22 by weight (acid value: 143.3, glass transition point: 66.3 ° C., weight average molecular weight: 8)
Ten thousand)

Mixture of ethylenically unsaturated compound (B) trimethylolpropane triacrylate / polyethylene glycol (600) dimethacrylate / ethylene oxide-modified phthalic acrylate (manufactured by Kyoeisha Yushi Kogyo Co., Ltd.) in a weight ratio of 20/10/6.

Formulation of photopolymerization initiator (C) 8.0 parts of benzophenone 0.15 parts of p, p'- bis ( diethylamino ) benzophenone 2,2'-bis (o-chlorophenyl) 4,5,4 ' , 5'-Tetraphenyl-1,2'-biimidazole 1.0 part Total 9.15 parts

Formulation of Dye (D) 0.8 parts of Leuco Crystal Violet (D ₁ ) 0.05 parts of Malachite Green (D ₂ ) 0.85 parts in total

The following benzotriazoles (E) and the following triazine derivatives (F) were further added to 100 parts of the composition comprising (A), (B), (C) and (D) described in Table 1 below.
And mixed well to prepare a dope.

Benzotriazoles (E) .E ₁ : 1,2,3-benzotriazole (molecular weight 11
9) · E _2: Bis (N-2-ethylhexyl) aminomethylene-1,2,3-benzotriazole (molecular weight 371) · E _3: 5- carboxy-1,2,3-benzotriazole (molecular weight 163)

[0055] triazine derivative _{(F) · F 1: 2,4,6-} [ tris (trichloromethyl)] -s-triazine (molecular weight _433.5) · F 2: 2,4- bis (trichloromethyl) - 4'-methoxyphenyl -s-preparative triazine (molecular weight _{422) · F 3: 2- (} 4- methoxy - naphth-1-yl) -4,6 [bis (trichloro Romechiru)] -s-triazine (molecular weight 472 )

<Preparation of Dry Film> Each of the dopes was coated on a 20 μm-thick polyester film using an applicator having a gap of 10 mils, and then dried at room temperature.
After leaving for 30 minutes, the samples were dried in ovens at 60 ° C., 90 ° C. and 110 ° C. for 3 minutes each to obtain a dry film having a resist thickness of 50 μm (provided that no protective film was provided).

<Lamination to Copper-Clad Laminate> This dry film was laminated on a copper-clad laminate preheated to 60 ° C. in an oven at a laminating roll temperature of 100 ° C., a roll pressure of 3 kg / cm ² , and a laminating speed of 1.5 m. / Min
Were laminated.

<Evaluation method> Sensitivity change Exposure amount X enough to give 22 steps of 8 steps or 41 steps of Stouffer without standing after lamination, and exposure required to give the same number of steps of Stouffer after standing 3 days after lamination ○ when the difference from the amount Y is less than 10 mj / cm ² , 10 mj / c
When it was m ² or more, it was judged as x.

The unexposed part of the contrast and the cured part exposed with the above X amount were subjected to ΔS (Lab) of the cured part by using “SZS-Σ80 COLOR MEASURING SYSTEM” manufactured by Nippon Denshoku Industries Co., Ltd.
(L ² + a ² + b ² ) ^1/2 ) was measured. A sample having a value of 14 or more was evaluated as ○, and a sample less than 14 was evaluated as ×.

Borofluoric Acid Resistance The substrate exposed on the whole surface with the above X amount is immersed in a solution of 42% aqueous fluoric acid 400 ml and water 600 ml at 20 ° C. for 15 hours, then washed with water and dried with an air knife. The condition was observed.ブ リ indicates that no blister was generated, and X indicates that it did.

Evaluation of soft etching After lamination, line / space = 100/15 in X amount
0 was drawn and developed. Thereafter, the developed substrate was immersed in a soft etching solution consisting of 120 g / l of sodium persulfate and 20 ml / l of 60% sulfuric acid at 30 ° C. for 1.5 minutes to confirm the soft etching. A sample that was normally soft-etched was evaluated as ○, and a sample that was not soft-etched partially or entirely was evaluated as ×. This soft etching evaluation is an evaluation method that is an alternative to the plating property evaluation.

Table 1 shows the formulation and results of the examples, and Table 2 shows the formulation and results of the comparative example.

[0063]

[Table 1]  Example 1 2 3 4 5 6 7 Formulation (A) Component 54 54 54 54 54 54 54 (B) Component 36 36 36 36 36 36 36 (C) Component 9.15 9.15 9.15 9.15 9.15 9.15 9.15 (D) Component 0.85 0.85 0.85 0.85 0.85 0.85 0.85 (E) Component 0.05 0.15 0.15 0.20 0.15 0.20 0.06 (E₁) (E₁) (E_Two) (E_Two) (E_Two) (E_Two) (E_Three) (F) component 0.10 0.5 0.15 0.30 0.20 0.20 0.15 (F_Two) (F_Two) (F_Two) (F_Two) (F₁) (F_Three) (F_Two) (E) / (F) molar ratio 1.77 1.07 1.14 0.60 0.88 1.00 1.04 Evaluation Sensitivity change ○ ○ ○ ○ ○ ○ Contrast 耐 ○ ○ ○ ○ ホ Etching evaluation ○ ○ ○ ○ ○ ○ ○ (Note) Numerical values in the column of formulation are parts by weight. (Note) In the evaluation column, “Etching evaluation” is soft
Etching evaluation.

[0064]

[Table 2]  Comparative example 1 2 3 4 5 6 7 Formulation (A) Component 54 54 54 54 54 54 54 (B) Component 36 36 36 36 36 36 36 (C) Component 9.15 9.15 9.15 9.15 9.15 9.15 9.15 (D) Component 0.85 0.85 0.85 0.85 0.85 0.85 0.85 (E) Component ---0.15 0.15 1.5 1.5 (E_Two) (E_Two) (E_Two) (E_Two) (F) component-0.02 0.15-1.5 0.15 1.5 (F_Two) (F_Two) (F_Two) (F_Two) (F_Two) (E) / (F) molar ratio 0.14 11.4 1.14 Evaluation Change in sensitivity ○ × × ○ × ○ ○ Contrast × ○ ○ × ○ ○ ○ Etching evaluation ○ × × ○ × × × (Note) Numerical values in the column of formulation are parts by weight. (Note) In the evaluation column, “Etching evaluation” is soft
Etching evaluation.

[0065]

The photosensitive resin composition of the present invention has good standing stability after lamination on a copper surface, has little change in sensitivity regardless of the elapsed time, and has a good effect on exposed and unexposed areas. Are excellent in that the effect of improving the contrast difference is large, and that the resistance to HF is good.

Continuation of the front page (56) References JP-A-4-122935 (JP, A) JP-A-2-84652 (JP, A) JP-A-64-35548 (JP, A) JP-A-1-164937 (JP) JP-A-2-311846 (JP, A) JP-A-64-55551 (JP, A) JP-A-3-231750 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB G03F 7/027 G03F 7/004

Claims (2)

(57) [Claims] 1. A composition comprising a base polymer (A), an ethylenically unsaturated compound (B), a photopolymerization initiator (C) and a dye (D), wherein a benzotriazole (E) and a triazine derivative (F) are used. In an amount of 0.03 to 1.0 part by weight, respectively, based on 100 parts by weight of the total amount of the base polymer (A), the ethylenically unsaturated compound (B), the photopolymerization initiator (C) and the dye (D). And benzotriazo at that time.
(E) and triazine derivative (F) have a molar ratio of
1: 3 to 3: 1, a photosensitive resin composition. 2. The photosensitive resin composition according to claim 1, which is a photosensitive resin composition for a dry film.