JP2001290269A - Photosensitive resin composition and photosensitive film using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition having high resolution and excellent in adhesion and removability as a resist and a photosensitive film using the composition. SOLUTION: The photosensitive resin composition contains a binder component (A), a monomer component (B) and a photopolymerization initiator (C). The binder component (A) contains at least a vinyl polymer (A1) having a weight average molecular weight of 50,000-100,000 and 110-170 mgKOH/g acid value and a vinyl polymer (A2) having a weight average molecular weight of 5,000-45,000, 180-300 mgKOH/g acid value and 100-160 deg.C glass transition temperature. The photopolymerization initiator (C) contains at least a lophin dimer (C1).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a printed wiring board,
The present invention relates to a photosensitive resin composition used for forming a pattern such as a lead frame and a semiconductor package, and a photosensitive film using the same.

[0002]

2. Description of the Related Art Conventionally, in the production of printed wiring boards and lead frames, when a fine circuit pattern or a shape pattern is formed, a photosensitive film formed by forming a layer of a photosensitive resin composition has been used. ing.

As the photosensitive film, a light-transmitting support film is usually provided on one side of the photosensitive resin composition layer.
Further, a film having a multilayer structure in which a protective film is laminated on the other surface of the photosensitive resin composition layer is used. The formation of a circuit pattern using the photosensitive film is performed, for example, as follows. That is, a substrate for a circuit board in which a copper foil is laminated on a substrate is prepared, and a photosensitive resin composition layer is attached to the substrate surface while peeling off a protective film (cover film) layer. A pattern mask is placed thereon, and a circuit pattern is formed by passing through an exposure step, a development step, and an etching step.

[0004]

However, when the resist is stripped after the etching step, if the resist strip is in the form of a film, problems such as entanglement with the transport rolls of the automatic stripping machine occur, resulting in poor workability. Therefore, it is desirable to use a photosensitive film having a high resist peeling rate and a fine resist peeling strip as the photosensitive film.

The present invention has been made in view of such circumstances, and an object of the present invention is to provide a photosensitive resin composition having high resolution, excellent adhesion and excellent resist stripping properties, and a photosensitive film using the same. And

[0006]

In order to achieve the above object, the present invention provides a photosensitive resin composition containing a binder component (A), a monomer component (B) and a photopolymerization initiator (C). The binder component (A) contains at least both of the following (A1) and (A2), and the photopolymerization initiator (C) contains at least a rofin dimer (C1). The photosensitive resin composition is a first gist. (A1) A vinyl polymer having a weight average molecular weight of 50,000 to 100,000 and an acid value of 110 to 170 mgKOH / g. (A2) A vinyl polymer having a weight average molecular weight of 50,000 to 45,000, an acid value of 180 to 300 mg KOH / g, and a glass transition temperature of 100 to 160 ° C.

The present invention also provides a photosensitive film comprising a support resin film laminated on one surface of a photosensitive resin composition layer and a protective film laminated on the other surface of the photosensitive resin composition layer, A second gist of the present invention is a photosensitive film in which the photosensitive resin composition layer is formed using the photosensitive resin composition.

That is, the present inventors have conducted intensive studies on a photosensitive resin composition in order to obtain a photosensitive film having high resolution and excellent adhesion and resist stripping properties.
When the photopolymerization initiator (C) containing at least the lophine dimer (C1) is used, the high resolution and the adhesion are improved, but the resist strip is likely to be formed into a film, and the resist strippability is poor. I found it. Therefore, as a result of further research and development, good results may be obtained by using a blend of a high molecular weight / low acid value polymer and a low molecular weight / high acid value polymer as a binder component. Recall that experiments were repeated for both preferred molecular weight, acid number and glass transition temperature. As a result, a binder component (A) containing at least both the specific vinyl polymer (A1) and the specific vinyl polymer (A2) and a photopolymerization containing at least the rofin dimer (C1) The present inventors have found that a photosensitive resin composition containing an initiator (C) and a monomer component (B) can achieve an intended purpose, and have reached the present invention.

When the mixing ratio of the vinyl polymer (A1) and the vinyl polymer (A2) is within a specific range, the resist dispersibility and the tent film strength are improved.

When the monomer component (B) contains at least the compound (B1) represented by the general formula (1), the tent film strength is improved.

[0011]

Next, embodiments of the present invention will be described in detail.

The photosensitive resin composition of the present invention can be obtained by using a binder component (A), a monomer component (B), and a photopolymerization initiator (C). In the present invention, the binder component (A) contains at least both the specific vinyl polymer (A1) and the specific vinyl polymer (A2), and the photopolymerization initiator (C) The greatest feature is that it contains at least the rofin dimer (C1).

The binder component (A) comprises a specific vinyl polymer (A1) and a specific vinyl polymer (A
There is no particular limitation as long as both contain at least 2).

The above specific vinyl polymer (A1) has a weight average molecular weight of 50,000 to 100,000 and an acid value of 110 to 110.
It is necessary to use a compound having a weight average molecular weight of 65,000 to 80,000 and an acid value of 1 to 170 mgKOH / g.
20-150 mgKOH / g. That is, if the weight average molecular weight is less than 50,000, the strength of the tent film decreases, and if it exceeds 100,000, the resolution decreases. If the acid value is less than 110 mgKOH / g, the resolving power and the resist peeling rate decrease, and
This is because if it exceeds 0 mgKOH / g, the adhesion decreases.

The above-mentioned specific vinyl polymer (A1)
Has a glass transition temperature (Tg) of preferably from 30 to 80 ° C, particularly preferably from 40 to 65 ° C.

The monomer component of the specific vinyl polymer (A1) is not particularly limited, and includes, for example, (meth) acrylic acid, (meth) acrylate, n-butyl (meth) acrylate, 2-hydroxyethyl methacrylate and the like. Specific examples of the specific vinyl polymer (A1) include a polymer of methyl methacrylate, n-butyl acrylate, 2-hydroxyethyl methacrylate, and methacrylic acid, and a polymer of methyl methacrylate and n-acrylic acid. A polymer of -butyl and methacrylic acid is preferably used.

Further, the above specific vinyl polymer (A2)
It is necessary to use those having a weight average molecular weight of 50,000 to 45,000, an acid value of 180 to 300 mg KOH / g, and a glass transition temperature (Tg) of 100 to 160 ° C., preferably It has a weight average molecular weight of 15,000 to 40,000, an acid value of 200 to 250 mg KOH / g, and a glass transition temperature (Tg) of 110 to 150 ° C. That is, when the weight average molecular weight is less than 50,000, the strength of the tent film is reduced, and when it exceeds 45,000, the resist strip is formed into a film. Further, the acid value is 180 mgKOH /
If the amount is less than 100 g, the resist stripped piece becomes a film, and conversely 300
If the amount exceeds mgKOH / g, the adhesion will decrease and the resist shape will deteriorate. Further, when the glass transition temperature is lower than 100 ° C., when the photosensitive film is stored in a roll state, a phenomenon (hereinafter referred to as “cold flow”) in which the photosensitive resin composition layer protrudes from the end face of the roll occurs. On the other hand, if the temperature exceeds 160 ° C., the resist unevenness followability is reduced, and the film is embrittled to lower the tent film strength.

The monomer component of the specific vinyl polymer (A2) is not particularly limited. For example, (meth) acrylic acid, (meth) acrylic acid ester, acrylic acid n
-Butyl and the like. As the specific vinyl polymer (A2), specifically, a polymer of methyl methacrylate and methacrylic acid, a polymer of methyl methacrylate, n-butyl acrylate and methacrylic acid are preferably used. .

The mixing ratio (weight ratio) of the specific vinyl polymer (A1) and the specific vinyl polymer (A2) is A1
/ A2 = 90/10 to 30/70 is preferable, and A1 / A2 = 70/30 to 45/55 is particularly preferable. That is, the weight ratio of A1 exceeds 90 (A2
When the weight ratio of A1 is less than 10), the resist strippings turn into a film. On the contrary, when the weight ratio of A1 is less than 30 (the weight ratio of A2 exceeds 70), the strength of the tent film decreases and the cold flow decreases. Is generated.

The binder component (A) other than the vinyl polymer (A1) and the vinyl polymer (A2) includes, for example, (meth) acrylic acid as a main component, and an ethylenically unsaturated carboxylic acid and It is preferable to use an acrylic polymer obtained by copolymerizing other copolymerizable monomers.

Examples of the (meth) acrylic acid include 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. .

As the above-mentioned ethylenically unsaturated carboxylic acid, for example, monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid and the like are preferably used, and dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid, and the like. Anhydrides and half esters can also be used. Of these, acrylic acid and methacrylic acid are particularly preferred.

Examples of the other copolymerizable monomers include tetrahydrofurfuryl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, glycidyl methacrylate, and the like. 2,2,2
-Trifluoroethyl (meth) acrylate, (meth)
Acrylamide, 2,2,3,3-tetrafluoropropyl (meth) acrylate acrylamide, diacetone acrylamide, vinyltoluene, vinyl acetate, alkyl vinyl ether, (meth) acrylonitrile and the like can be mentioned.

The monomer component (B) used together with the binder component (A) preferably contains at least a compound (B1) represented by the following general formula (1).

[0025]

Embedded image

[0026] In the above general formula (1), R is preferably a methyl group, X is -CH ₂ CH ₂ O- are preferable, Y is -CH ₂ CH (CH ₃₎ O- are preferred.

In the above general formula (1), examples of the divalent hydrocarbon group having 2 to 20 carbon atoms represented by Z include:
In addition to-(CH ₂ ) _6- , those shown below can be mentioned.
Among them, - (CH _{2) 6} - is preferable.

[0028]

Embedded image

In the general formula (1), k is 10 to 2
An integer of 0 is preferable, m is preferably an integer of 3 to 6, and n
Is preferably an integer of 3 to 6.

The compound (B) represented by the above general formula (1)
The weight average molecular weight (Mw) of 1) is 1900 to 3500
Is preferred, and particularly preferably 2400 to 3000
It is.

The compound represented by the general formula (1)
Among the products (B1), R = —CH _Three, X = -CH_TwoC
H_TwoO-, Y = -CH_TwoCH (CH_Three) O-, Z =-
(CH _Two)₆−, K = 15, m = 6, n = 4
Compounds are particularly preferred.

The compound (B) represented by the above general formula (1)
As the monomer component (B) other than 1), an ethylenically unsaturated compound is preferable. For example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di ( Meta)
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, glycerin di (meth) acrylate, pentaerythritol di (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, diglycidyl phthalate Di (meth) acrylate,
Hydroxyhivalic acid-modified neopentyl glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane triethoxytriacrylate, trimethylolpropane tripropoxy triacrylate, 1,6-hexamethyldiglycidyl ether di (meth) A) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, glycerin polyglycidyl ether poly (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol Hexa (meth) acrylate, 2,2'-bis (4- (meth) acryloxydiethoxyphenyl) propane, 2,2'- Scan (4- (meth) acryloxy pentaethoxy phenyl) propane, 2,2'-bis (4
Polyfunctional monomers such as-(meth) acryloxypolyethoxyphenyl) propane, 2-hydroxy-3- (meth) acryloyloxypropyl acrylate, and trimethylolpropane triglycidyl ether tri (meth) acrylate. In addition, an appropriate amount of a monofunctional monomer can be used in combination with the polyfunctional monomer. Examples of such a monofunctional monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-hydroxyethyl (meth) acrylate. Hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2- (meth) acryloyloxy-2-hydroxypropyl phthalate, 3-chloro-2-hydroxypropyl (meth) acrylate,
Glycerin mono (meth) acrylate, 2- (meth) acryloyloxyethyl acid phosphate, half (meth) acrylate of phthalic acid derivative, N-methylol (meth) acrylamide, diethylaminoethyl methacrylate, polypropylene glycol (meth) acrylate, alkylphenol polyethoxy (Meth) acrylate and the like.

The compound (B) represented by the above general formula (1)
The content of 1) is preferably set in the range of 3 to 70% by weight of the entire monomer component (B), and particularly preferably 5 to 50% by weight. That is, the compound (B1)
If the content is less than 3% by weight, the effect of the tent film reliability is lost, and if it exceeds 70% by weight, the resist shape may be deteriorated and the resolution may be reduced.

The mixing ratio (weight ratio) of the binder component (A) and the monomer component (B) is A / B = 70 /
A range of 30 to 40/60 is preferred, and A is particularly preferred.
/ B = 60/40 to 45/55. That is, if the weight ratio of the monomer component (B) is less than 30, the curing rate may be reduced and the adhesion may be reduced. Conversely, if the weight ratio of the monomer component (B) exceeds 60, the peeling rate may be reduced. Is likely to be delayed.

The photopolymerization initiator (C) used together with the binder component (A) and the monomer component (B) is not particularly limited as long as it contains a lophine dimer (C1).

The rofin dimer (C1) is not particularly limited as long as it is a dimer of lophine (2,4,5-triphenylimidazole). For example, 2,2'-bis (o-chlorophenyl) ) -4,5,4 ', 5'-Tetraphenyl-1,2'-biimidazole, 2,2'-bis (o-chlorophenyl) -4,5,4', 5'-tetraphenyl-1, 1'-biimidazole, 2,2'-bis (o-fluorophenyl) -4,5,4 ', 5'-tetraphenyl-1,1'-biimidazole, 2,2'-bis (o-methoxy Phenyl) -4,5,4 ', 5'-tetraphenyl-1,1'-biimidazole, 2,2'-
Bis (p-methoxyphenyl) -4,5,4 ', 5'-
Tetraphenyl-1,1′-biimidazole, 2,4
2 ', 4'-bis [bi (p-methoxyphenyl)]-
5,5'-diphenyl-1,1'-biimidazole,
2,2'-bis (2,4-dimethoxyphenyl) -4,
5,4 ', 5'-diphenyl-1,1'-biimidazole, 2,2'-bis (p-methylthiophenyl) -4,
5,4 ', 5'-diphenyl-1,1'-biimidazole, bis (2,4,5-triphenyl) -1,1'-biimidazole and the like can be mentioned. These may be used alone or in combination of two or more. Of these,
2'-bis (o-chlorophenyl) -4,5,4 ',
5'-Tetraphenyl-1,2'-biimidazole is preferred.

The content of the above-mentioned rofin dimer (C1) is
With respect to 100 parts by weight (hereinafter abbreviated as “parts”) of the total amount of the binder component (A) and the monomer component (B), 1
A range of 0 parts is preferable, and a particularly preferable range is 2 to 6 parts. That is, if the amount is less than 1 part, the sensitivity is lowered, and if it is more than 10 parts, on the other hand, there is a possibility that it is deposited on the developing tank and causes contamination.

As the photopolymerization initiator (C) other than the above-mentioned lophine dimer (C1), ketones, thioxanthones,
Acridines, triazines, phenylglycine, triphenylphosphine, and the like;

The ketones include, for example, p-aminophenyl ketones, and specifically, N, N '
-Tetraalkyl-4,4'-diaminobenzophenone (Michler's ketone), benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, benzoin isophenyl ether, benzyl diphenyl disulfide, benzyl dimethyl ketal , Diacetyl, anthraquinone, naphthoquinone, 3,3'-dimethyl-4-methoxybenzophenone, benzophenone, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone and the like. Above all, 4,
4'-bis (diethylamino) benzophenone is preferred.

The content of the ketones is preferably in the range of 0.02 to 0.5 part, more preferably 0.1 to 100 parts, based on 100 parts of the total of the binder component (A) and the monomer component (B). 05 to 0.3 part. That is, 0.02
If the amount is less than 0.5 parts, the sensitivity and the resolving power decrease, and if it exceeds 0.5 part, the adhesion may decrease.

The photosensitive resin composition of the present invention contains, in addition to the binder component (A), the monomer component (B) and the photopolymerization initiator (C), a dye (dye, a discoloring agent) and a heat polymerization agent. Inhibitors, plasticizers, adhesion promoters, antioxidants, solvents,
A surface tension modifier, a stabilizer, a chain transfer agent, an antifoaming agent, a surfactant and the like may be blended. As the above dye,
For example, leuco crystal violet, malachite green and the like can be mentioned.

The photosensitive resin composition of the present invention comprises the above binder component (A), monomer component (B) and photopolymerization initiator (C) as essential components, and optionally other components such as a dye. Can be prepared by mixing and mixing.

That is, a support film (carrier film) is laminated on one side of a photosensitive resin composition layer using the photosensitive resin composition of the present invention.
On the other side of the photosensitive resin composition layer, a photosensitive film having a three-layer structure in which a protective film (cover film) is laminated is typically given.

The support film is not particularly limited, and includes, for example, a polyethylene terephthalate (PET) film and a polypropylene film (OPP), and is preferably a PET film.

The above protective film is used for the purpose of preventing transfer of the photosensitive resin composition layer having adhesiveness to the support film when the photosensitive film is used in the form of a roll. , For example, polyethylene (PE)
Film, PET film, polypropylene film (OPP, CPP), polyvinyl alcohol film,
Examples include a polytetrafluoroethylene (PTFE) film and a nylon film, and a PE film is preferable.

The photosensitive film of the present invention can be produced, for example, as follows. That is, the photosensitive resin composition of the present invention is uniformly applied on one surface of the support film, and dried in an oven at 90 ° C. for 5 minutes to form a photosensitive resin composition layer. Then, by pressing and laminating a protective film on the other surface of the photosensitive resin composition layer,
A photosensitive film having a three-layer structure in which a support film is laminated on one side of the photosensitive resin composition layer and a protective film is laminated on the other side of the photosensitive resin composition layer can be produced.

In the photosensitive film of the present invention, the thickness of the photosensitive resin composition layer is preferably 50 μm or less, particularly preferably 10 to 40 μm. That is, if the thickness of the photosensitive resin composition layer exceeds 50 μm, it becomes difficult to obtain a sufficient resolution. The thickness of the support film is usually from 5 to 25 μm, preferably from 12 to 20 μm. That is, if the thickness is less than 5 μm, the film is too flexible, which is inconvenient to handle. The thickness of the protective film is usually 10 to 50 μm, preferably 10 to 50 μm.
３０30 μm.

The photosensitive film of the present invention is used, for example, for manufacturing printed wiring boards and lead frames, and for precision processing of metals. The method for producing a printed wiring board using the photosensitive film of the present invention will be described below.

[Exposure] In order to form an image with a photosensitive film, the protective film is peeled off from the surface of the photosensitive resin composition layer, and then the surface of the photosensitive resin composition layer is removed.
Affixed to a metal surface such as a copper-clad substrate, 42 alloy, or SUS. Next, a pattern mask is brought into close contact with the support film on the opposite side of the photosensitive resin composition layer, and exposure is performed.
The above exposure is usually performed by ultraviolet irradiation, and as a light source at that time, a high-pressure mercury lamp, a carbon arc lamp, a xenon lamp, a metal halide lamp, a chemical lamp, or the like is used. In addition, if necessary, it is possible to complete the curing by heating after the irradiation of the ultraviolet rays.

[Development] After exposure, the support film on the photosensitive resin composition layer is peeled off and then developed.
When the photosensitive resin composition is a rare alkali developing type,
After the exposure, the development is performed using 0.3% of sodium carbonate, potassium carbonate, etc.
This is performed using an alkaline aqueous solution of about 2% by weight. In addition,
A surfactant, an antifoaming agent, a small amount of an organic solvent for accelerating the development, and the like may be mixed in the alkaline aqueous solution.

[Etching, Plating] Etching is usually performed using an acidic etching solution such as a cupric chloride-hydrochloric acid aqueous solution or a ferric chloride-hydrochloric acid aqueous solution in accordance with 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 or plating step, the remaining hardened resist (photosensitive resin composition) is stripped off. Removal and removal of the cured resist
This is carried out using an alkali stripping solution composed of an aqueous solution of an alkali such as sodium hydroxide or potassium hydroxide having a concentration of about 0.5 to 5% by weight or an aqueous solution containing amines.

Next, examples will be described together with comparative examples.

First, prior to Examples and Comparative Examples, the following materials were prepared.

[Vinyl-based polymer (A1)] Methyl methacrylate, n-butyl acrylate, 2-hydroxyethyl methacrylate and methacrylic acid are mixed at 50/15/15/2.
0 (weight ratio), a vinyl polymer (weight average molecular weight: 80,000, acid value: 130 mg KOH /
g, Tg = 45 ° C.)

[Vinyl polymer (A1)] Methyl methacrylate, n-butyl acrylate and methacrylic acid
/ 45/31 (weight ratio), a vinyl polymer (weight average molecular weight: 70,000, acid value: 140 m)
gKOH / g, Tg = 55 ° C)

[Vinyl polymer (A2)] A vinyl polymer obtained by polymerizing methyl methacrylate and methacrylic acid at a ratio of 65/35 (weight ratio) (weight average molecular weight: 30,000, acid value: 228 mg KOH / g, Tg = 141
℃)

[Vinyl polymer (A2)] Methyl methacrylate, n-butyl acrylate and methacrylic acid
/ 15/30 (weight ratio) obtained by polymerization at a ratio of vinyl polymer (weight average molecular weight: 30,000, acid value: 230 m
gKOH / g, Tg = 130 ° C)

[Binder component (A)] Methyl methacrylate, n-butyl acrylate and methacrylic acid are mixed in a ratio of 45/2.
A vinyl polymer obtained by polymerization at a ratio of 0/35 (weight ratio) (weight average molecular weight: 50,000, acid value: 228 mgK
OH / g, Tg = 84 ° C)

[Compound (B1)] In the above formula (1), R = —CH ₃ , X = —CH ₂ CH ₂ O—, Y = —
_{CH 2 CH (CH 3) O-} , Z = - (CH 2) 6 -, k
= 15, m = 6, monomer component represented by n = 4

[Monomer component (B)] 2,2'-bis (4-methacryloxypolyethoxyphenyl) propane

[Monomer component (B)] Polypropylene glycol monomethacrylate

[Monomer Component (B)] Nonylphenol tetraethoxyacrylate

[Monomer component (B)] β-hydroxyethyl-β'-acryloyloxyethyl-o-phthalate

[Photopolymerization initiator (C1)] Lophine dimer: 2,2'-bis (o-chlorophenyl) -4,5,4 ', 5'-tetraphenyl-1,2-
Biimidazole

[Photopolymerization initiator (C)] Ketones: 4,4'-bis (diethylamino) benzophenone

[Photopolymerization initiator (C)] Ketones: benzophenone

[0068]

Examples 1-5, Comparative Examples 1-6 The following Tables 1 and 2
Were dissolved in a solvent (methyl ethyl ketone: isopropanol = 9: 1 [weight ratio]) in the proportions shown in the same table to prepare a photosensitive resin composition. Then, the photosensitive resin composition was applied to a 19 μm thick P
Apply evenly on ET film (support film), 9
It was dried in an oven at 0 ° C. for 5 minutes to form a photosensitive resin composition layer having a thickness of 35 μm. Further, a PE film (protective film) having a thickness of 25 μm was laminated on the other surface of the photosensitive resin composition layer, and left for one day to obtain a photosensitive film. On the other hand, a copper-clad board (1.6 mm thick, 250 mm × 20 mm) formed by bonding a copper foil having a thickness of 35 μm.
0 mm) and prepare a copper foil surface with Scotch Bright SF
(Sumitomo 3M Co., Ltd.), polished with baffle, washed with water, dried with an air stream and leveled.
Preheated to 0 ° C. Then, a film composed of a PET film (support film) and a photosensitive resin composition layer is laminated on the copper foil surface using a hand-type roll laminator while peeling off the PE film (protective film) of the photosensitive film. (Lamination conditions: hot roll temperature: 100 ° C., roll pressure: about 0.3 MPa, lamination speed: 1.5 m / min).

[0069]

[Table 1]

[0070]

[Table 2]

Using the thus obtained examples and comparative examples, each characteristic was evaluated according to the following criteria. These results are shown in Tables 3 and 4 below.

[Resolution] Line / space = 1 on the surface of the photosensitive resin composition layer laminated on the copper-clad substrate.
/ 1 (10 μm, 15 μm, 20 μm, 25 μm, 30
(μm, 35 μm, 40 μm, 45 μm, 50 μm) pattern masks (made of glass chrome dry plate) were adhered in vacuum. Then, exposure is performed with a 2kW ultra-high pressure mercury short arc lamp (parallel light) with an exposure amount equivalent to 7 steps of a 21-step Stofa tablet, and the minimum development time is equivalent to twice the minimum development time so that a resist image is resolved after development. The line width was checked.

[Adhesion] The surface of the photosensitive resin composition layer laminated on the copper-clad substrate had a line width (10 μm,
15 μm, 20 μm, 25 μm, 30 μm, 35 μm,
The pattern masks (made of glass chrome dry plate) of the individual fine lines (40 μm, 45 μm, and 50 μm) were brought into close contact with each other and developed in the same manner as described above, and the minimum line width of the individual fine lines with good adhesion was examined.

[Tent film strength] TH having a diameter of 4.5 mm
A substrate having a thickness of 1.6 mm having through-holes is prepared, and a PET film (support film) and a photosensitive resin composition are peeled from the surface of the substrate while the PE film (protective film) of the photosensitive film is peeled off. A film consisting of layers was affixed. After exposure and development were performed under the same conditions as above, the tent film strength was measured using a tension gauge having a diameter of 2 mm.

[Resistant Property (Speed, Dispersibility)] A resist exposed to a resist (180 mm × 100 mm) at 50 ° C.
Spraying a weight percent aqueous sodium hydroxide solution with a spray,
The resist peeling speed (stripping end time) was measured. Also,
At that time, dispersibility of the resist (resist strip size) was visually evaluated. In addition, the evaluation was evaluated as ○ when the size of the peeled piece was less than 30 mm, and x when the size of the peeled piece exceeded 30 mm.

[Cold Flow Test] A photosensitive film roll (330 mm in width and 100 m in length) was prepared from the above photosensitive film, and stored at 40 ° C. in an atmosphere of 60% RH. Then, the occurrence of cold flow was visually evaluated. The evaluation was evaluated as が な い when no cold flow occurred for 5 days or more, and x when cold flow occurred within 4 days.

[0077]

[Table 3]

[0078]

[Table 4]

From the results shown in Tables 3 and 4, all of the examples have high resolution, excellent adhesion, and excellent resist peelability. In particular, it can be seen that Examples 3 to 5 using the specific compound (B1) have excellent tent film strength.

On the other hand, it can be seen that Comparative Example 1 is inferior in resolution and adhesion since it does not contain the rofin dimer (C1). Comparative Examples 2 to 6 do not use the high molecular weight / low acid value vinyl polymer (A1) and the low molecular weight / high acid value vinyl polymer (A2) in combination. It is understood that one of the properties is inferior.

[0081]

As described above, the photosensitive film of the present invention contains at least both the specific vinyl polymer (A1) and the specific vinyl polymer (A2), and the monomer component (B) ) And lophine dimer (C
Since a special photosensitive resin composition containing at least 1) is used, the composition has high resolution and excellent adhesion and resist peelability.

When the compounding ratio of the vinyl polymer (A1) and the vinyl polymer (A2) is in a specific range, the resolution and the adhesion are improved, and the resist stripping property is also improved.

When the monomer component (B) contains at least the compound (B1) represented by the general formula (1), the strength of the tent film is improved.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03F 7/004 512 G03F 7/004 512 7/027 502 7/027 502 513 513 513 7/031 7/031 7 / 033 7/033 H05K 3/06 H05K 3/06 HF term (reference) 2H025 AA00 AA02 AA14 AB11 AB15 AB16 AB17 AC01 AD01 BC14 BC45 CB14 CB51 CB55 CB60 FA03 FA17 FA40 FA43 FA48 4J011 AA05 PA69 PC02 PC08 QA03 QA13 QA23 QA23 QA38 QA42 QB16 SA25 SA28 SA29 SA32 SA34 SA54 SA63 SA78 SA83 UA01 VA01 WA01 4J027 AC02 AC03 AC06 AC09 AE04 BA07 BA08 BA19 BA20 BA21 BA23 BA26 BA28 CA03 CB10 CC05 CD10 4J100 AL08Q AL09Q AL62Q AL63Q BA66Q BA21 BA02 BB01Q BC43Q BC45Q CA04 CA05 CA06 JA38 5E339 BC02 BD11 BE13 CC01 CC02 CD01 CE11 CE16 CF15 CG04 DD04

Claims (4)

[Claims] 1. A photosensitive resin composition containing a binder component (A), a monomer component (B) and a photopolymerization initiator (C), wherein the binder component (A) comprises the following (A1) A photosensitive resin composition containing at least both (A2) and the photopolymerization initiator (C) containing at least a rofin dimer (C1). (A1) A vinyl polymer having a weight average molecular weight of 50,000 to 100,000 and an acid value of 110 to 170 mgKOH / g. (A2) A vinyl polymer having a weight average molecular weight of 50,000 to 45,000, an acid value of 180 to 300 mg KOH / g, and a glass transition temperature of 100 to 160 ° C. 2. The mixing ratio of the vinyl polymer (A1) and the vinyl polymer (A2) is A1 / A2 = 90 / by weight.
The photosensitive resin composition according to claim 1, wherein the ratio is from 10 to 30/70. 3. The photosensitive resin composition according to claim 1, wherein the monomer component (B) contains at least a compound (B1) represented by the following general formula (1). Embedded image 4. A photosensitive film comprising a support film laminated on one surface of a photosensitive resin composition layer and a protective film laminated on the other surface of the photosensitive resin composition layer, wherein the photosensitive resin A photosensitive film, wherein the composition layer is formed using the photosensitive resin composition according to claim 1.