JP2002099080A - Photosensitive resin composition laminated body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition laminated body excellent in sensitivity, resolution, close adhesion or the like. SOLUTION: The photosensitive resin composition laminated body of the present invention comprising (a) a supporting film, (b) a photosensitive resin layer, and (C) a protective film, is characterized in that the supporting film (a) possesses a haze of 0.1-1.5% and a thickness of 10-30 μm, and in that the photosensitive resin layer (b) contains as an essential component a binder polymer, a photopolymerization initiator and a polymerizable vinyl compound, and in that an aromatic ketone is contained as a photopolymerization initiator.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a photosensitive resin composition laminate, and more particularly, to a photosensitive resin composition laminate capable of obtaining high resolution.

[0002]

2. Description of the Related Art Conventionally, in the fields of printed wiring board manufacture and metal precision processing, a photosensitive resin composition laminate (photosensitive film) has been used to form a fine circuit. That is, a method of laminating a photosensitive film on a base material, exposing and developing through a negative film (pattern mask), performing plating in some cases, and then performing etching, resist stripping, and the like.

[0003] The photosensitive film usually comprises a light-transmitting support film, a photosensitive resin layer, and a protective film.
As a method of use, first peel off the protective film,
The photosensitive resin layer is pressure-bonded (laminated) so as to directly touch the base material, the patterned negative film is adhered to the light-transmitting film, and irradiated (exposed) with actinic rays (often using ultraviolet rays), and then In general, a resist pattern is formed (developed) by spraying an organic solvent or an aqueous alkali solution to remove unnecessary portions, and then etching is performed using an aqueous solution of lead chloride. Particularly, from the viewpoint of environmental problems, a developing solution using an alkaline aqueous solution is required.

In recent years, the miniaturization and weight reduction of electronic equipment have been promoted, the circuit size of printed wiring boards has been required to be finer, the resist pattern has been finer, and the resolution of photosensitive films has been required to be higher. I have. However, a conventional photosensitive film having a three-layer structure cannot satisfy the requirements. That is, in order to increase the resolution, it is necessary to reduce the thickness of the film as much as possible in order to expose through a light-transmitting support film, but to serve as a support when applying a photosensitive resin, Is required, and generally needs a thickness of about 15 to 25 μm,
At present, the use of a conventional grade support film cannot meet the demand for higher resolution.

[0005] In response to these demands, various attempts have been made to achieve higher resolution. For example, there is a method in which the support film is peeled off before exposure, and a negative film is directly adhered to the photosensitive resin layer. Normally, the photosensitive resin layer has a certain degree of adhesiveness so that it adheres to the substrate, and if this method is directly applied, the negative film and the photosensitive resin layer will adhere to each other, making it difficult to remove the negative film and workability. Of the negative film, the photosensitive resin is contaminated with the negative film, and the sensitivity is reduced due to air inhibition.

Therefore, as an attempt to improve this method, JP-A-61-31855 and JP-A-1-221735 have been proposed.
JP-A-2-230149 and the like.
It has been practiced to use two or more photosensitive resin layers and a non-adhesive layer for a layer directly in contact with a negative film. However, this method requires a lot of time and labor for coating since the photosensitive resin layer is multi-layered, and has no effect on sensitivity reduction.

As another method, on a photosensitive resin layer,
Attempts to solve these disadvantages by providing an intermediate layer,
JP-B-56-40824, JP-A-55-5010
No. 72, Japanese Patent Publication No. 54-12215,
7-469, JP-A-59-97138, JP-A-59-216141, and JP-A-63-1979.
No. 42, and the like. However, in each of these cases, an intermediate layer must be provided between the support film and the photosensitive resin layer, so that the coating is troublesome twice, and it is difficult to handle a thin intermediate layer.

[0008]

SUMMARY OF THE INVENTION The present invention solves the above problems and provides a photosensitive resin composition laminate having improved sensitivity, resolution, adhesion and the like.

[0009]

According to the present invention, there is provided a photosensitive resin composition comprising a support film (a), a photosensitive resin layer (b) and a protective film (c).
Has a haze of 0.1 to 1.5% and a thickness of 10 to 30 μm.
m, the photosensitive resin composition laminate.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The support film (a) of the present invention comprises:
It goes without saying that it is transparent, and the haze representing its turbidity needs to be in the range of 0.1 to 1.5%. Haze is a value representing turbidity, and is calculated from the total transmittance T of light radiated by a lamp and transmitted through the sample and the transmittance D of light diffused and scattered in the sample. Is H =
D / T × 100. These are JIS K
7105, and can be easily measured by a commercially available turbidity meter, for example, NDH-1001DP manufactured by Nippon Denshoku Industries Co., Ltd. A support film having a haze of less than 0.1% is difficult to obtain, and a support film having a haze of more than 1.5% has no effect of improving sensitivity, resolution, adhesion, and the like. As a support film having a haze of 0.1 to 1.5%,
For example, polyethylene terephthalate films, such as Teijin's highly transparent film GS series, Diafoil Hoechst's M-310 series, and DuPont's Mylar D series, are mentioned.

The thickness of the support film (a) is from 10 to 30.
When the thickness exceeds 30 μm, the resolution is reduced and the cost is increased. Further, since the support film (a) is usually peeled off before development and discarded, the industrial waste is reduced. Not desirable from a viewpoint. Also 10
If it is less than μm, the film is too flexible and inconvenient to handle.

As the photosensitive resin layer (b) of the present invention, known ones can be used, and usually contain a binder polymer, a photopolymerization initiator and a polymerizable vinyl compound as essential components. As the binder polymer, an alkyl ester of (meth) acrylic acid [(meth) acrylic acid means methacrylic acid and acrylic acid. The same applies hereinafter) and copolymers with vinyl monomers copolymerizable therewith.

Examples of the alkyl ester of (meth) acrylic acid include methyl (meth) acrylate,
Examples include ethyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. Examples of the vinyl monomer copolymerizable with the alkyl (meth) acrylate include tetrahydrofurfuryl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, and the like. Glycidyl methacrylate, 2,2
2-trifluoroethyl (meth) acrylate, 2,
2,3,3-tetrafluoropropyl (meth) acrylate acrylamide, diacetone acrylamide, styrene, vinyltoluene (meth) acrylic acid, and the like. These copolymers can be used alone or in combination of two or more.

When the photosensitive resin composition layer (b) is of an alkali developing type, usually, a binder polymer obtained by copolymerizing (meth) acrylic acid with the above-mentioned alkyl ester and vinyl monomer may be used.

Examples of photopolymerization initiators include benzophenone, N-N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), N, N-tetramethyl-4,4'-diaminobenzophenone, 4-methoxy Aromatic ketones such as -4'-dimethylaminobenzophenone, 2-ethylanthraquinone and phenanthrenequinone; benzoin ethers such as benzoin methyl ether, benzoin ethyl ether and benzoin phenyl ether; benzoin such as methyl benzoin and ethyl benzoin; benzyl dimethyl Benzyl derivatives such as ketals,
2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5
Di (m-methoxyphenyl) imidazole dimer, 2
-(O-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,
5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer, 2,4-di (p-methoxyphenyl) -5-phenylimidazole dimer, 2- ( 2,4-dimethoxyphenyl) -4,5-diphenylimidazole dimer, 2-
2,4,5-triarylimidazole dimer such as (p-methylmercaptophenyl) -4,5-diphenylimidazole dimer, 9-phenylacridine, 1,7-
And acridine derivatives such as bis (9,9'-acridinyl) heptane. These can be used alone or in combination of two or more.

Examples of the photopolymerizable vinyl compound include urethane acrylate biscoat # 831 (trade name, manufactured by Osaka Organic Chemical Industry Co., Ltd.), polyether type urethane acrylate BTG-A (trade name, manufactured by Kyoeisha Yushi Kagaku Kogyo KK),
Urethane (meta) such as polyester-type urethane acrylate D-200A (trade name, manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd.), urethane acrylate photomer 6008 (trade name, manufactured by San Nopco), urethane diarylate chemlink 9503 (trade name, manufactured by Sartoma Co., Ltd.) Acrylate and trimethylolpropane ethoxy triacrylate (SR-454,
Sartomer Corp.), trimethylolpropanepropoxy triacrylate (R-924, Nippon Kayaku Co., Ltd.), polyethylene glycol di (meth) acrylate (with 2 to 14 ethylene groups), trimethylolpropane Di (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethylolmethane tri (meth) acrylate, tetramethylolmethanetetra (meth) acrylate, polypropylene glycol di (meth) acrylate (the number of propylene groups is 2 to 2)
14), dipentaerythritol penta (meta)
Acrylate, dipentaerythritol hexa (meth)
Bisphenol A, a compound obtained by reacting an α, β-unsaturated carboxylic acid with a polyhydric alcohol such as acrylate
Bisphenol A dioxyethylene di (meth) such as dioxyethylene di (meth) acrylate, bisphenol A trioxyethylene di (meth) acrylate, bisphenol A decaoxyethylene di (meth) acrylate
Compounds obtained by adding α, β-unsaturated carboxylic acid to glycidyl group-containing compounds such as acrylate, trimethylolpropane triglycidyl ether triacrylate, bisphenol A diglycidyl ether acrylate, and polycarboxylic acids such as phthalic anhydride Esterified with a substance having a hydroxyl group and an ethylenically unsaturated group such as β-hydroxyethyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, Examples thereof include (meth) acrylic acid alkyl esters such as 2-ethylhexyl ester.

In the photosensitive resin layer (b), a plasticizer, a dye, a pigment, an imaging agent, a filler, an adhesion-imparting agent, a stabilizer and the like can be used as necessary. The thickness varies depending on the application, but the thickness after drying is 10 to 10.
It is preferably about 100 μm.

As the protective film (c) of the present invention, a polyester film, a polyolefin film or the like is generally used, but a polyethylene film is preferred in view of price, flexibility, strength, hardness and the like. Also, its thickness is
It is preferably from 1.0 to 40 μm, and if it is less than 10 μm, the handleability tends to be inferior.
The cost tends to increase.

The photosensitive resin composition laminate (photosensitive film) of the present invention is usually prepared by (1) applying heat, pressure, etc., so that the photosensitive resin layer adheres to the substrate while peeling off the protective film. Laminating, (2) placing a negative film on the support film, exposing through the negative film,
(3) It is used in a method of forming an image (resist pattern) by developing after peeling off the support film.

The laminating step (1) is generally performed while heating and softening the photosensitive resin layer by using a heatable roll called a hot roll or a heating jacket called a heat shoe and a roll called a laminate roll.

The exposure step (2) is generally carried out by using a contact or non-contact type exposure apparatus having a dedicated exposure apparatus. As the lamp, a lamp that effectively emits ultraviolet rays, such as a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, and a xenon lamp, can be used.

The developing method (3) includes a dip method and a spray method, and a high-pressure spray method is most suitable for high resolution. The developer greatly differs between the solvent development type and the alkali development type, and it is general to use 1,1,1-trichloroethane for the solvent development type and 1% by weight of sodium carbonate for the alkali development type.

The processing after image formation includes steps such as etching and plating, and these may be performed by a known method as necessary.

[0024]

EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.

Examples 1-3 and Comparative Examples 1-2 Copolymers of methacrylic acid / methyl methacrylate / butyl methacrylate / 2-ethylhexyl acrylate (weight ratio 2
5/50/5/20, 40% by weight methylcellosolve / toluene (weight ratio 6/4) solution 1 with a weight average molecular weight of 80,000
00g (solid content 40g), 50 of methacrylic acid / methyl methacrylate / ethyl acrylate / styrene copolymer (weight ratio 30/30/30/10, weight average molecular weight 40,000)
40 g (solid content: 20 g) of a solution of a weight% methyl cellosolve / toluene (weight ratio: 8/2), 1.0 g of tribromomethylphenylsulfone, leuco crystal violet 1
g, malikaite green 0.05 g, methyl ethyl ketone 10 g, toluene 10 g, methanol 3 g, benzophenone 4.5 g and N, N′-tetraethyl-4,
0.2 g of 4'-diaminobenzophenone was blended to obtain a solution.

Next, the solution of the photosensitive resin composition is uniformly applied on various polyethylene terephthalate films (support film (a)) shown in Table 1, and dried with a hot air convection dryer at 100 ° C. for about 10 minutes. After forming a photosensitive resin layer (b), a 30 μm-thick polyethylene film was laminated as a protective film (c) to obtain a photosensitive film. The dried film thickness of the photosensitive resin layer was 50 μm.

On the other hand, the copper surface of a copper-clad laminate (manufactured by Hitachi Chemical Co., Ltd., trade name: MCL-E-61) which is a glass epoxy material having a copper foil (thickness: 35 μm) laminated on both sides is # 600.
Polishing using a polishing machine (manufactured by Sankeisha Co., Ltd.) having a considerable brush, washing with water, and drying in an air stream, heating the obtained copper-clad laminate to 80 ° C. The conductive resin composition layer was heated to 120 ° C. and laminated while peeling off the polyethylene film.

Next, a negative film (pattern mask) is placed on the polyethylene terephthalate film,
3kw high-pressure mercury lamp (manufactured by Oak Works, HMW-201
Exposure of 60 mJ / cm2 was performed in B). At this time, in order to evaluate the light sensitivity, a region where the amount of light transmission decreases stepwise in the negative film (the step of increasing the optical density by 0.15 for each step with the optical density of 0.05 as the first step) Tablet). In addition, the minimum line / space is 30 μm.
And a negative film for a resolution evaluation having a comb-shaped pattern in which both lines and spaces are increased every 10 μm and an adhesiveness having a comb-shaped pattern in which the line / space is at least 30 μm / 400 μm and only the line is increased every 10 μm A negative film for evaluation was also used for exposure.

Next, the polyethylene terephthalate film was removed, and an unexposed portion was removed by spraying a 1% by weight aqueous solution of sodium carbonate at 30 ° C. for 50 seconds. Furthermore, the photosensitivity of the photosensitive resin composition was evaluated by measuring the number of steps of the step tablet of the photocurable film formed on the copper-clad laminate, and the results are shown in Table 1. The light sensitivity is indicated by the number of steps of the step tablet. The higher the number of steps of the step tablet, the higher the light sensitivity.

The resolution is represented by the resolution (μm) of the comb pattern every 10 μm, and the smaller the numerical value of the resolution, the higher the resolution. Adhesion is expressed as the width (μm) of the line remaining without peeling after development. The smaller the value of this adhesion, the more tightly adhered the copper-clad laminate without peeling from the copper-clad laminate even with thin lines This indicates that the adhesiveness is high. The results are summarized in Table 1.
It was shown to.

[0031]

[Table 1]

[0032]

The photosensitive resin composition laminate of the present invention has excellent sensitivity, resolution, adhesion and the like.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Hitoko Kimura 4-3-1, Higashicho, Hitachi City, Ibaraki Prefecture F-term in Hitachi Chemical Co., Ltd. Yamazaki Plant (Reference) 2H025 AA01 AA02 AA14 AB11 AC01 AD01 BC13 BC42 CA01 CA03 CA11 DA05 EA08 FA17 5E339 AA02 AB02 CD01 CE16 CF16 CF17 DD02 5E343 AA16 AA33 BB24 BB67 CC63 DD32 ER16 ER18

Claims (4)

[Claims] 1. A photosensitive resin composition comprising a support film (a), a photosensitive resin layer (b) and a protective film (c), wherein the support film (a) has a haze of 0.1 to 0.1.
1.5%, the thickness is 10 to 30 μm, and
The photosensitive resin layer (b) is a photosensitive resin composition laminate containing a binder polymer, a photopolymerization initiator, and a polymerizable vinyl compound as essential components, and containing an aromatic ketone as a photopolymerization initiator. 2. The method according to claim 1, wherein the aromatic ketone is benzophenone,
The photosensitive resin according to claim 1, wherein the photosensitive resin is at least one selected from N, N'-tetramethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 2-ethylanthraquinone, and phenanthrenequinone. Composition laminate. 3. The photosensitive resin layer (b) has a thickness of 10 to 10
3. The photosensitive resin composition laminate according to claim 1, wherein the thickness is 0 μm. 4. 4. A printed wiring board obtained by laminating a photosensitive resin composition laminate according to any one of claims 1 to 3 on a substrate, exposing, and developing.