JP2001318461A - 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, excellent particularly in the adhesion of thin lines and free of edge fusion. 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 an acrylic resin having a weight average molecular weight of 5,000-45,000 and the monomer component (B) contains at least a compound of formula (1) (where X1-X6 are each -CO-CR1= CH2 or -(CO-C5H10-O)m-CO-CR2=CH2 (R1 and R2 are each H or methyl and may be the same or different and (m) is an integer of 1-5) and at least two of X1-X6 are -(CO-C5H10-O)m-CO-CR2=CH2).

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. Next, a circuit pattern is formed by placing a pattern mask thereon and passing it through an exposure step, a development step, and an etching step.

[0004]

However, in recent years,
With the finer pitch of circuit patterns, it has been required to improve the resolution. As a countermeasure for such high resolution, the molecular weight of the polymer component, which is a material for forming the photosensitive resin composition layer of the photosensitive film, has been increased. Has been adopted. However, by reducing the molecular weight of the polymer as a binder component, when the photosensitive film is stored in a roll state, a phenomenon in which the photosensitive resin composition layer protrudes from the end face of the roll (hereinafter, referred to as “edge fusion”) occurs. When a photosensitive film is used, there are problems that the apparatus is contaminated, and that the adhesion of fine lines in pattern formation is poor.

As a countermeasure against such a problem, for example, with respect to edge fusion, it has been proposed to increase the content ratio of a binder component in a photosensitive resin composition, but the adhesion and sensitivity are reduced. There was a disadvantage that it would. Furthermore, as another method, a photosensitive resin composition contains a citric acid derivative (Japanese Patent Laid-Open No. 7-3191).
No. 54), containing a polypropylene glycol (JP-A-7-319153), containing a crystalline vinyl polymerizable polymer binder (JP-A-9-244230), and containing a cellulose derivative (JP-A-9-244230). 11-1
No. 74667) has been proposed.

However, in the proposal of containing the above-mentioned various compounds, none of the above-mentioned compounds has an ethylenically unsaturated group. However, this method is not suitable for applications in which the adhesion of fine wires is emphasized.

SUMMARY OF THE INVENTION The present invention has been made in view of such circumstances, and a photosensitive resin composition having high resolution, particularly excellent adhesion of fine wires, and which does not cause edge fusion, and a photosensitive film using the same. Its purpose is to provide.

[0008]

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 an acrylic resin having a weight average molecular weight of 5,000 to 45,000, and the monomer component (B) is a structural unit represented by the following general formula (1). The first gist is a photosensitive resin composition containing at least a compound having the formula:

[0009]

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The present invention also provides a photosensitive film comprising a support film laminated on one side of a photosensitive resin composition layer and a protective film laminated on the other side 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 mainly on a photosensitive resin composition in order to obtain a photosensitive film having high resolution and excellent adhesion, and free from edge fusion. As a result, when the monomer component (B) containing at least the compound represented by the general formula (1) is used as the monomer component (B) together with the low molecular weight acrylic resin as the binder component (A), It has been found that the object of the invention can be achieved, and the present invention has been achieved.

When the content of the compound represented by the above general formula (1) is within the above-mentioned specific range, generation of edge fusion occurs even when stored in a roll while maintaining a balance between high resolution and adhesion. It was found that it was possible to prevent. When the ratio is outside the above range, edge fusion occurs, or a photo-cured photosensitive film becomes brittle, and as a result, a problem such as a decrease in adhesion tends to occur. .

Furthermore, it has been found that, when the photopolymerization initiator (C) contains at least a rofin dimer, the resistance to chemicals such as a developing solution is improved, so that even a finer line can be adhered.

[0014]

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). The most characteristic feature of the present invention is that the binder component (A) contains at least an acrylic resin having a specific molecular weight, and the monomer component (B) contains at least the specific compound.

The binder component (A) is not particularly limited as long as it contains at least a specific acrylic resin.

It is necessary to use a specific acrylic resin having a weight average molecular weight of 5,000 to 45,000. Further, the acid value is 90 to 250 mgKOH / g,
Those having a glass transition temperature of 40 to 130 ° C are preferred. More preferably, the weight average molecular weight is 10,000 to 35,000.
0, acid value 100-190 mgKOH / g, glass transition temperature 60-125 ° C. And what contains a styrene component in a molecule | numerator 2 to 70 weight% is preferable, and especially preferable is 5 to 50 weight%.

That is, the weight average molecular weight is 5,000
If it is less than 0, it will be difficult to act as a binder, and the flexibility when the resin composition is formed into a film will be low.
Conversely, if it exceeds 45,000, it is difficult to obtain high resolution. Further, the acid value is 90 mgK
If the OH / g is less than OH / g, the alkali developability and the peelability after photo-curing are inferior when using the photosensitive resin composition, and the workability tends to be reduced. This is because there is a tendency to be inferior in sex. Further, when the glass transition temperature is out of the above range, wrinkles may be formed at the time of sticking to the substrate, edge fusion may easily occur, or the glass may be hard and brittle, so that handling tends to be difficult.

As the specific acrylic resin, for example, a (meth) acrylic acid ester compound as a main component,
An acrylic polymer obtained by copolymerizing an ethylenically unsaturated carboxylic acid and another copolymerizable monomer is used for this.

Examples of the (meth) acrylic ester compound include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, and 2-ethylhexyl ( (Meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, dimethylaminoethyl (meth)
Acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate Glycidyl methacrylate, 2,2,2-trifluoroethyl (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, 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 styrene, (meth) acrylamide,
2,3,3-tetrafluoropropyl (meth) acrylate acrylamide, diacetone acrylamide, vinyl toluene, vinyl acetate, alkyl vinyl ether,
(Meth) acrylonitrile and the like. In particular, it is preferable to use styrene. The amount of the styrene component is 2 to 7 in the molecule of the acrylic resin.
It is preferable to contain it in the range of 0% by weight. That is, if it is out of this range, there is a tendency that poor chemical resistance results in poor adhesion, or brittleness results in poor adhesion.

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

[0024]

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In the general formula (1), both R ₁ and R ₂ are preferably hydrogen. Then, X in the above general formula (1)
Of ₁ to X _6, at least two - (CO-C ₅ H ₁₀
—O) m—CO—CR ₂ ＣＨCH ₂ , particularly preferably at least 3 are — (CO—C ₅ H ₁₀ —
O) is a _{m-CO-CR 2 = CH} 2. The number m of repetitions is particularly preferably an integer of 1 to 2.

Further, as the monomer component (B), it is preferable to use a urethane di (meth) acrylate compound in combination with the compound represented by the general formula (1). By using this urethane di (meth) acrylate compound, it is possible to impart flexibility to the resist after photo-curing, and an effect of preventing a decrease in adhesion due to cracks can be achieved.

The urethane di (meth) acrylate compound includes a CH ₂ CHCH ₃ O chain, —C ₄ H ₈ O—
And at least one of a chain and -CO-C ₅ H ₁₀ O- linkage, and C ₂ H ₄ chain contains four urethane bonds, is preferably used with more terminal ethylenic groups.

As the urethane di (meth) acrylate compound, those having a weight average molecular weight (Mw) of 1,000 to 10,000 are preferably used from the viewpoint of compatibility, resolution and flexibility.

As the monomer component (B) other than the compound represented by the general formula (1) and the urethane di (meth) acrylate compound, 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 (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, 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, 1,6-hexamethyldiglycidyl ether di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate
Acrylate, pentaerythritol tetrapropoxy 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 ′
-Bis [4- (meth) acryloxypentaethoxyphenyl] propane, 2,2'-bis [4- (meth) acryloxypolyethoxyphenyl] propane, 2-hydroxy-3- (meth) acryloyloxypropyl acrylate, Examples include polyfunctional monomers such as trimethylolpropane triglycidyl ether tri (meth) acrylate. In addition, an appropriate amount of a monofunctional monomer may be used in combination with the polyfunctional monomer. 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-hydroxypropyl phthalate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, 2- ( Examples thereof include (meth) acryloyloxyethyl acid phosphate, phthalic acid derivative half (meth) acrylate, and N-methylol (meth) acrylamide.

The content of the compound represented by the above general formula (1) is preferably set in the range of 1 to 20% by weight, particularly preferably 2 to 15% by weight, based on the whole photosensitive resin composition. . That is, when the content of the compound represented by the general formula (1) is less than 1% by weight, the effect of preventing the occurrence of edge fusion is hardly obtained, and when it exceeds 20% by weight, the photosensitive resin composition This is because there is a tendency that the adhesion between the film and the support film or the protective film becomes too low and the handling becomes difficult.

The content of the urethane di (meth) acrylate compound is from 1 to 20 of the entire photosensitive resin composition.
It is preferably set in the range of weight%, particularly preferably 2 to 15 weight%. That is, when the content of the urethane di (meth) acrylate compound is less than 1% by weight, the effect of imparting flexibility to the resist after photocuring is small, and when the content exceeds 20% by weight, the resolution tends to deteriorate. Is seen.

The mixing ratio (weight ratio) of the binder component (A) and the monomer component (B) is A / B = 35 /
It is preferably in the range of 65 to 70/30, particularly preferably A
/ B = 42/58 to 65/35. That is, when the weight ratio of the monomer component (B) is less than 30, not only the resolution is deteriorated, but also the curing speed is slowed. Conversely, when the weight ratio of the monomer component (B) exceeds 65, edge fusion occurs. This is because there is a possibility that the peeling speed may be reduced.

The photopolymerization initiator (C) used together with the binder component (A) and the monomer component (B) is not particularly limited, but is preferably a lophine dimer.

The rofin dimer 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
-Methoxyphenyl) -4,5,4 ', 5'-tetraphenyl-1,1'-biimidazole, 2,2'-bis (p-methoxyphenyl) -4,5,4', 5'-tetra Phenyl-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.

[0035] The content of the above-mentioned lophine dimer is 100% in total of the above-mentioned binder component (A) and monomer component (B).
The amount is preferably from 1 to 8 parts by weight, particularly preferably from 2 to 5 parts by weight (hereinafter abbreviated as "part"). That is, when the amount is less than 1 part, the sensitivity is lowered, and when the amount exceeds 8 parts, on the other hand, there is a possibility that the toner is deposited on the developing tank and causes contamination.

Examples of the photopolymerization initiator (C) other than the above-mentioned lophine dimer include ketones and organic peroxides.

The ketones include, for example, p-aminophenyl ketones. 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, chlorothioxanthone and the like. . Among them, 4,4'-bis (diethylamino) benzophenone is preferred.

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 color changing 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 flame retardant and the like may be blended. Examples of the dye include leuco crystal violet, malachite green, and the like.

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.

Next, representative examples of the photosensitive film using the photosensitive resin composition of the present invention will be described. 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, and a protective film ( A typical example is a photosensitive film having a three-layer structure in which a cover film is laminated.

The support film is not particularly limited, but is preferably a film which is resistant to solvents and drying and has good transparency. For example, a polyethylene terephthalate (PET) film is generally used.

The protective film is used for the purpose of preventing the 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)
Examples include a film, a polypropylene film, a polyvinyl alcohol film, a polytetrafluoroethylene (PTFE) film, and a polystyrene 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 40 μm or less, particularly preferably 10 to 30 μm. That is, if the thickness of the photosensitive resin composition layer exceeds 40 μm, it is difficult to obtain a sufficient resolution. The thickness of the support film is usually from 10 to 30 μm, preferably from 14 to 22 μm. That is, when the thickness is less than 10 μm, the film is too flexible, which is inconvenient to handle. On the other hand, when the thickness exceeds 30 μm, the resolution is lowered and the cost is increased, which is not preferable. The thickness of the protective film is usually 10 to 35 μm, preferably 1 to 35 μm.
5 to 30 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 the 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.
By this development, unexposed portions are eluted and removed. When the photosensitive resin composition is a dilute alkali developing type, development after exposure is performed using an aqueous solution of about 0.3 to 2% by weight of an alkali such as sodium carbonate or potassium carbonate. In addition, a surfactant, an antifoaming agent, a small amount of an organic solvent for promoting development, and the like may be mixed in the alkaline aqueous solution. After development, washing and drying steps are usually followed.

[Etching, Plating] 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 or plating step, the remaining hardened resist (photosensitive resin composition) is peeled off. Removal and removal of the cured resist
An alkali stripper consisting of an aqueous alkali solution such as sodium hydroxide or potassium hydroxide having a concentration of about 0.5 to 5% by weight or an aqueous solution containing ethanolamines or the like, or an aqueous solution containing an alkaline organic stripper is used. .

Next, examples will be described together with comparative examples.

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

[Acrylic resin (A)] Methyl methacrylate, styrene and methacrylic acid are mixed in a ratio of 40/40/20.
(Weight ratio): A vinyl polymer obtained by polymerization at a ratio of (weight average molecular weight: 19,000, acid value: 130 mg KOH)
/ G, Tg = 122 ° C)

[Acrylic resin (A)] Methyl methacrylate, n-butyl acrylate and methacrylic acid
Vinyl polymer obtained by polymerization at a ratio of 20/20 (weight ratio) (weight average molecular weight: 80,000, acid value: 130 mg)
KOH / g, Tg = 72 ° C)

[Compound (B) represented by formula (1)
1)] Nippon Kayaku Co., Ltd., DPCA-60 [in formula (1),
X₁~ X₆All are-(CO-C _FiveH_Ten-O) m-CO-
CR_Two= CH_Two(M = 1, R_TwoIs H). ]

[Compound (B) represented by formula (1)
1)] Nippon Kayaku Co., Ltd., DPCA-120 [Formula (1)
Where X _{1 to} X ₆ are all-(CO-C ₅ H ₁₀ -O) m-C
_{O-CR 2 = CH 2 (} m = 2, R 2 is H) is. ]

[Compound (B) represented by formula (1)
1)] Nippon Kayaku Co., Ltd., DPCA-30 [in formula (1),
Three will of X ₁ to X ₆ is _{- (CO-C 5 H 10} -O) m
_{-CO-CR 2 = CH 2 (} m = 1, R 2 is H), the remaining three are _{-CO-CR 1 = CH 2 (} R 1 is H) is. ]

[Urethane di (meth) acrylate compound (B2)] A compound represented by the following structural formula (a).

Embedded image

[Urethane di (meth) acrylate compound (B2)] A compound represented by the following structural formula (b).

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[Ethylenically unsaturated compound] BPE: 2,2'-bis [4- (methacryloxypolyethoxy) phenyl] propane (EO = 10)

[Ethylenically unsaturated compound] TMP-3PA: trimethylolpropane tripropoxy acrylate

[Ethylenically unsaturated compound] P-4PA: pentaerythritol tetrapropoxy acrylate

[Ethylenically unsaturated compound] HOA-MPE: 2-acryloyloxyethyl-2-
Hydroxyethyl phthalate

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

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

[Other Additives] LCV: Leuco Crystal Violet

[Other additives] MG: malachite grate

[0067]

Examples 1 to 6 and Comparative Examples 1 to 3 Tables 1 and 2 below
The components shown in Table 1 were blended and mixed in the proportions shown in the same table to prepare a dope having a resin content of 58% in the photosensitive resin composition (the values in Tables 1 and 2 are based on the case where the whole is 100% by weight). It is the composition ratio of each compound, and indicates the weight ratio of each compound). In addition,
The acrylic resin is a reflux condenser, thermometer, stirrer,
The solution was synthesized in a flask equipped with a heater and used as a solution of methyl ethyl ketone / isopropylene alcohol (weight ratio: 80/20) having a resin content of 45%. In addition, methyl ethyl ketone was used for dilution at the time of dope preparation.
Then, the photosensitive resin composition is coated with a 19 μm-thick PET film (support film) using an applicator.
The composition was uniformly coated on the top, dried with a hot air dryer at 60 ° C. for 2 minutes, and further dried with a hot air dryer at 90 ° C. for 5 minutes to form a 25 μm-thick photosensitive resin composition layer. further,
On the other side of the photosensitive resin composition layer, a 25 μm thick PE
A film (protective film) was laminated and left for one day to obtain a photosensitive film. On the other hand, a copper-clad substrate (1.6 mm thick, 250 mm × 200 mm) prepared by bonding a copper foil having a thickness of 35 μm is prepared, and the surface of the copper foil is polished with a scotch bright SF (manufactured by Sumitomo 3M Limited). After being washed with water, it was dried in a stream of air, leveled, and preheated to 60 ° C. in an oven. Then, while peeling off the PE film (protective film) of the photosensitive film on the surface of the copper foil, a film composed of the PET film (support film) and the photosensitive resin composition layer is auto-cut laminator (manufactured by Hakutosha Co., Ltd .; The laminate was laminated using MACH610i) (lamination conditions: hot roll temperature: 100 ° C., roll pressure: about 0.3 MPa, lamination speed: 1.5 m / min).

[0068]

[Table 1]

[0069]

[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.

[Sensitivity] On a surface of the photosensitive resin composition layer laminated on the copper-clad substrate, a 21-step stofer step tablet (a negative film made so that the amount of light transmission decreases stepwise) was prepared. Exposure was performed using a 2kW ultra-high pressure mercury short arc lamp (parallel light) using an exposure machine (EXM-1171-A00) manufactured by Oak Manufacturing Co., Ltd. Then
A 1% by weight aqueous solution of sodium carbonate at 30 ° C. was spray-developed for twice the minimum development time. Based on each exposure amount and the number of steps remaining after the development, an exposure amount sufficient to give 5 steps with a 21-step Stofa tablet was examined.

[Resolution] Line / space = 1 on the surface of the photosensitive resin composition layer laminated on the copper-clad substrate.
/ 1 (6 μm, 8 μm, 10 μm, 12 μm, 14 μm
m, 16 μm, 18 μm, 20 μm, 25 μm, 30 μ
, 35 μm, and 40 μm) of each pattern mask (made of a glass cloth dry plate) were adhered in vacuum. Then 2kW
Exposure was performed with an ultra-high pressure mercury short arc lamp (parallel light) at an exposure amount equivalent to 5 steps of a 21-step Stofa tablet, and the minimum line width at which a resist image was resolved after development was examined.

[Adhesion] Line / space = 1 on the surface of the photosensitive resin composition layer laminated on the copper-clad substrate.
/ 1 (6 μm, 8 μm, 10 μm, 12 μm, 14 μm
m, 16 μm, 18 μm, 20 μm, 25 μm, 30 μ
Each of the pattern masks (made of glass chrome dry plate) of the independent fine lines (m, 35 μm, 40 μm) is adhered in vacuum, and development is performed in the same manner as in the evaluation of the resolution described above. Examined.

[Developer resistance] The minimum line width was examined in the same manner as described above, except that the development time was set to 4.0 times the minimum development time.

[Edge Fusion] A photosensitive film roll (width: 330 mm, length: 100 m) was prepared from the above photosensitive film, and stored at 50 ° C. in an atmosphere of 60% RH. Then, the presence or absence of occurrence of edge fusion was visually evaluated. The evaluation was evaluated as ○ when no occurrence of edge fusion was observed even after one week, and evaluated as × when occurrence of edge fusion was confirmed within 2 days.

[0076]

[Table 3]

[0077]

[Table 4]

From the results shown in Tables 3 and 4, all of the examples exhibited high resolution, excellent adhesion, and good sensitivity. Further, the developer resistance was excellent, and no edge fusion occurred.

On the other hand, in Comparative Example 1, an acrylic resin having a low molecular weight was used, but the compound represented by the general formula (1) (dipentaerythritol derivative) was not used. Occurrence was confirmed.
In Comparative Example 2, although the compound represented by the general formula (1) (dipentaerythritol derivative) was used, edge fusion did not occur because a low molecular weight acrylic resin was not used. The results were inferior in resolution, adhesion and developer resistance. Further, Comparative Example 3
A conventional photosensitive resin composition not using both the low molecular weight acrylic resin and the compound represented by the general formula (1) (dipentaerythritol derivative) was used, and no edge fusion occurred. The results were inferior in resolution, adhesion and developer resistance.

[0080]

As described above, the photosensitive film of the present invention contains at least a specific acrylic resin as the binder component (A) and is represented by the general formula (1) as the monomer component (B). Because a special photosensitive resin composition containing at least a compound is used,
A photosensitive film having high resolution, particularly excellent adhesion of fine wires, and free from edge fusion when stored in a roll is obtained.

When the content of the compound represented by the general formula (1) is within the above-mentioned specific range, generation of edge fusion occurs even when stored in a roll while maintaining a balance between high resolution and adhesion. Can be prevented. When the ratio is outside the above range, edge fusion occurs, or a photo-cured photosensitive film becomes brittle, and as a result, a problem such as a decrease in adhesion tends to occur. .

Further, when at least the above-mentioned lophine dimer is contained as the photopolymerization initiator (C), the chemical resistance of the developer and the like is improved, so that even finer lines can be adhered.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03F 7/004 512 G03F 7/004 512 7/031 7/031 7/033 7/033 (72) Inventor Naotoshi Yamamoto 1-88, Oyodonaka, Kita-ku, Osaka City, Osaka Prefecture F-term in Nichigo Morton Co., Ltd. PA69 PB40 PC02 PC08 QA13 QA14 QA17 QA22 QA23 QA24 RA03 SA21 SA31 SA41 SA51 SA78 SA83 UA01 UA06 VA01 WA01 4J026 AA17 AA43 AA45 AA47 AA48 BA28 BA29 BA30 DB06 DB11 DB36 GA06 GA07 4J100 AL66P AL67P BA02

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) has a weight average molecular weight of 5,000 to A photosensitive resin composition containing at least 45,000 acrylic resins, and wherein the monomer component (B) contains at least a compound represented by the following general formula (1). Embedded image 2. The photosensitive resin composition according to claim 1, wherein the content of the compound represented by the general formula (1) is set to 1 to 20% by weight of the whole photosensitive resin composition. 3. The photosensitive resin composition according to claim 1, wherein the photopolymerization initiator (C) contains at least a lophine dimer. 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.