JP2002258475A - Photosensitive resin composition, photosensitive element using the same, resist pattern forming method and method for producing circuit board for semiconductor package - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a circuit board for a high density semiconductor package by using a photosensitive resin composition excellent in sensitivity, resolution, scumming resistance, plating resistance, work efficiency and productivity. SOLUTION: The photosensitive resin composition contains a binder polymer, a photopolymerizable compound having at least one ethylenically unsaturated bond, a photopolymerization initiator and a storage stabilizer which is vitamin E. The photosensitive element is obtained by disposing the photosensitive resin composition in a thin film shape on a base. The photosensitive resin composition is laminated on a substrate for forming a circuit and irradiated with active light corresponding to a developed image, the exposed part is photo-cured and the unexposed part is removed by development to form a resist pattern. A circuit corresponding to the resist pattern is formed on the substrate by etching or plating the substrate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a photosensitive resin composition, a photosensitive element using the same, a method for forming a resist pattern, and a method for manufacturing a circuit board for a semiconductor package.

[0002]

2. Description of the Related Art Conventionally, in the field of manufacturing printed wiring boards, a photosensitive resist composition processed into an emulsion or a photosensitive element processed into an emulsion is used as a resist material when performing etching or plating. Widely used. The photosensitive element is composed of a photosensitive resin composition film (dry film) and a support and a protective film that support the film, and is used for reasons such as ease of handling and reduction of pinholes. It is expanding rapidly. When manufacturing a printed wiring board using a photosensitive element, after laminating a dry film of the photosensitive element on a copper substrate, performing exposure corresponding to the wiring pattern and curing the exposed portion, and then curing the uncured portion. Removed with a developer to form a cured film development pattern and then etched from above (subtractive method)
Alternatively, after performing a plating (additive method) process to form a wiring pattern, the development pattern is peeled off from the substrate, thereby obtaining a substrate on which the wiring pattern is formed.

[0003] From the viewpoint of improving workability in a series of steps as described above, there is a demand for providing a photosensitive resin composition having high sensitivity and less contamination of a plating bath.

Regarding the improvement of the sensitivity of the photosensitive resin composition,
So far, photopolymerization initiators have been mainly studied, and German Patent No. 2,027,467, European Patent Publication No. 11,786, European Patent Publication No. 220, and European Patent Publication No. No. 589, JP-A-6-69631 and the like describe a highly sensitive photopolymerization initiator. However, these photosensitive resin compositions have a disadvantage that they contaminate the plating bath.

On the other hand, a photosensitive resin composition comprising a combination of a photopolymerization initiator 2,4,5-triarylimidazole dimer and a hydrogen-donating compound is disclosed in US Pat.
479,185. In the case of this photosensitive resin composition, the contamination of the plating bath is small, but when the amount of the photopolymerization initiator used is increased in accordance with the required sensitivity, the fineness decreases because the line width of the resist increases. And
When the amount of the hydrogen-donating compound used is increased, the adhesion to copper and the storage stability decrease. Therefore, there is a disadvantage that the improvement in sensitivity is hindered by practical problems.

In addition, the conventional photosensitive resin compositions include:
A small amount of a thermal polymerization inhibitor is contained as a storage stabilizer for stabilizing the photopolymerizable compound to increase the storage stability, but this also causes a decrease in sensitivity.

[0007]

As described above, it is difficult to change the composition while improving only specific properties of the photosensitive resin composition without affecting other properties. It is important to provide a photosensitive resin composition which is less likely to cause practical problems.

The present invention provides a photosensitive resin composition which can prevent a decrease in sensitivity due to a storage stabilizer of a photopolymerizable compound and is excellent in workability in manufacturing a circuit board for a semiconductor package. That is the task.

Further, the present invention can prevent a decrease in sensitivity due to a storage stabilizer of a photopolymerizable compound, and is excellent in resolution, scum generation resistance, plating resistance, workability and productivity, An object of the present invention is to provide a photosensitive resin composition that is effective for increasing the density of a circuit board for a semiconductor package and improving workability in circuit manufacture.

Further, the present invention can prevent a decrease in sensitivity due to a storage stabilizer of a photopolymerizable compound, and is excellent in resolution, scum generation resistance, plating resistance, workability and productivity, It is an object of the present invention to provide a photosensitive element which is effective for increasing the density of a semiconductor package substrate circuit and improving workability in circuit manufacture.

Further, the present invention can prevent a decrease in sensitivity due to a storage stabilizer of a photopolymerizable compound, and is excellent in resolution, scum generation resistance, plating resistance, workability and productivity, An object of the present invention is to provide a method for forming a resist pattern which is effective for increasing the density of a semiconductor package substrate circuit and improving workability in circuit manufacture.

Further, the present invention can prevent a decrease in sensitivity due to a storage stabilizer of a photopolymerizable compound, is excellent in resolution, workability, and productivity, and has a high density of semiconductor package substrate circuits. An object of the present invention is to provide a method of manufacturing a semiconductor package circuit board which is useful for improving workability in circuit manufacturing.

[0013]

In order to solve the above problems, the photosensitive resin composition of the present invention comprises a binder polymer, a photopolymerizable compound having at least one ethylenically unsaturated bond, a photopolymerization initiator, It is essential to contain vitamin E.

The photopolymerizable compound is 2,2-bis (4
-((Meth) acryloxypolyalkoxy) phenyl)
Allow to contain propane.

The photosensitive element of the present invention comprises the above-mentioned photosensitive resin composition disposed on a support in the form of a thin film.

The method of forming a resist pattern according to the present invention comprises:
Laminating the photosensitive resin composition on a circuit-forming substrate, irradiating the photosensitive resin composition with an actinic ray corresponding to a developed image to photo-harden an exposed portion, and removing an unexposed portion by development. Is the gist.

In the method of manufacturing a circuit board for a semiconductor package according to the present invention, the photosensitive resin composition is laminated on a circuit forming substrate, and the photosensitive resin composition is irradiated with actinic rays corresponding to a developed image. A resist pattern is formed on the substrate by photo-curing the exposed portion and the unexposed portion is removed by development, and a circuit corresponding to the resist pattern is provided on the substrate by etching or plating the substrate. It is characterized by the following.

The above photosensitive resin composition can be laminated on a circuit-forming substrate in a thickness of 1 to 100 μm in close contact.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION As a result of various searches for additives of a photopolymerizable compound, the present inventors have found that vitamin E not only contributes to the storage stability of a photosensitive resin composition but also prevents the sensitivity from lowering. Was found to be effective, and a photosensitive resin composition using the same as a storage stabilizer and a mode of use thereof were completed.

Hereinafter, the present invention will be described in detail. In the present invention, “(meth) acrylic acid” is
"Acrylic acid and methacrylic acid" means "(meth)
"Acrylate" is "acrylate and methacrylate"
And “(meth) acryloyl group” means “acryloyl group and methacryloyl group”. In the present invention, "EO" and "PO" represent "ethylene oxide" and "propylene oxide," respectively, and the "EO-modified" compound and the "PO-modified" compound have "a block structure of an ethylene oxide group." And a compound having a block structure of a propylene oxide group.

The photosensitive resin composition of the present invention contains a binder polymer, a photopolymerizable compound having at least one ethylenically unsaturated bond, a photopolymerization initiator, and vitamin E. Each component will be described in detail below.

The binder polymer is a component capable of molding a photopolymerizable compound, for example, an acrylic resin,
Styrene resin, epoxy resin, amide resin, amide epoxy resin, alkyd resin, phenol resin, and the like. From such a polymer, a development method,
They can be appropriately selected and used according to the peeling method and the required properties of the composition, and may be used alone or in combination of two or more. It is preferable to use an acrylic resin in the photosensitive resin composition for alkali development.

The binder polymer can be produced by radically polymerizing a polymerizable monomer. Examples of the polymerizable monomer include polymerizable styrene derivatives such as styrene, vinyltoluene, α-methylstyrene, p-methylstyrene, p-ethylstyrene, acrylamide, acrylonitrile, and vinyl-n-.
Ethers of vinyl alcohol such as butyl ether,
Alkyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate, 2,2,2 -Trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, (meth) acrylic acid, α-bromo (meth) acrylic acid, α-chloro (meth) acrylic acid, β -Furyl (meth) acrylic acid, β-
Styryl (meth) acrylic acid, maleic acid, maleic anhydride, monoester maleate such as monomethyl maleate, monoethyl maleate, monoisopropyl maleate, fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, Crotonic acid, propiolic acid and the like. With respect to the alkyl (meth) acrylate of the polymerizable monomer, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, (meth) Examples include pentyl acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and structural isomers thereof. These polymerizable monomers can be used alone or in combination of two or more.

The properties of the resulting photosensitive resin composition can be properly adjusted by selecting the polymerizable monomer used for preparing the binder polymer. For example, from the viewpoint of alkali developability, it is preferable to introduce a carboxyl group into the binder polymer, and this can be realized by radically polymerizing a polymerizable monomer having a carboxyl group and another polymerizable monomer. . As the polymerizable monomer having a carboxyl group in this case, methacrylic acid is particularly preferred. From the viewpoint of the flexibility of the photosensitive resin composition, it is preferable that styrene or a styrene derivative is contained as a polymerizable monomer of the binder polymer.

When styrene or a styrene derivative is used as a copolymer component, it is preferably 3 to 30% by weight, more preferably 3 to 30% by weight of the polymerizable monomer, in order to improve both the adhesion and the peeling properties of the photosensitive resin composition. Is copolymerized with styrene or a styrene derivative at a ratio of 4 to 28% by weight, particularly preferably 5 to 27% by weight. If this proportion is less than 3% by weight, the adhesion of the resin composition tends to decrease, and if it exceeds 30% by weight, the peeling pieces during the peeling treatment tend to be large and the peeling time tends to be long.

The binder polymer preferably has an acid value of 30 to 200 mg KOH / g, more preferably 50 to 200 mg KOH / g.
Adjust to 150 mgKOH / g. Acid value is 30
If it is less than mgKOH / g, the developing time tends to be long, and if it exceeds 200 mgKOH / g, the developing solution resistance of the photocured resist tends to decrease.

The weight average molecular weight of the binder polymer (gel permeation chromatography (GPC)
), And the polymerization reaction is adjusted so as to be preferably from 20,000 to 300,000, more preferably from 30,000 to 150,000. If the weight average molecular weight of the binder polymer is less than 20,000, the developer resistance tends to decrease, and if it exceeds 300,000, the development time tends to be long.

If necessary, a photosensitive group may be introduced into the binder polymer.

The binder polymer can be used alone or in combination of two or more. Examples of using two or more polymers in combination as a binder polymer include, for example, a combination of two or more polymers having different copolymerization components (monomers), a combination of two or more polymers having different weight average molecular weights, and a dispersion. 2 different degrees
Combinations of more than one type of polymer may be mentioned. Also,
A polymer having a multi-mode molecular weight distribution described in JP-A-11-327137 can also be used.

The photopolymerizable compound contained in the photosensitive resin composition of the present invention is a compound having at least one ethylenically unsaturated bond in a molecule. No restrictions. For example, a compound having one ethylenically unsaturated bond in a molecule includes a fumaric acid-based compound. Examples of those having two ethylenically unsaturated bonds in the molecule include polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, and polybutylene glycol di (meth) acrylate. Also,
Those having three ethylenically unsaturated bonds in the molecule include trimethylolpropane tri (meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate, PO-modified trimethylolpropane tri (meth) acrylate, EO, PO Modified trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, EO modified pentaerythritol tri (meth) acrylate, PO modified pentaerythritol tri (meth) acrylate, EO, PO modified pentaerythritol tri (meth) acrylate, Tetramethylol methane tri (meth) acrylate, EO-modified tetramethylol methane tri (meth) acrylate, P
O-modified tetramethylol methane tri (meth) acrylate, EO, PO modified tetramethylol methane tri (meth) acrylate, and the like. Available products include, for example, A-TMM-3 (trade name, tetramethylol methane triacrylate manufactured by Shin-Nakamura Chemical Co., Ltd.), TMPT21E, TMPT30E (sample name,
EO-modified trimethylolpropane trimethacrylate manufactured by Hitachi Chemical Co., Ltd.).

In the present invention, the above photopolymerizable compounds can be used alone or in combination of two or more.

As the photopolymerizable compound, 2,2-bis (4-((meth) acryloxypolyalkoxy) phenyl) propane having two ethylenically unsaturated bonds can also be used. When used in combination with the above-mentioned compounds as one of the photopolymerizable compounds, it is effective in terms of resolution and releasability.

The polyalkoxy groups of the 2,2-bis (4-((meth) acryloxypolyalkoxy) phenyl) propane may be the same or different. The plurality of alkoxy groups constituting the polyalkoxy group may be the same or different. When the polyalkoxy group is composed of two or more types of alkoxy groups, the various alkoxy groups may be present at random or may form a block.
Hereinafter, specific compounds will be exemplified.

As 2,2-bis (4-((meth) acryloxypolyalkoxy) phenyl) propane in which the polyalkoxy group is composed of one kind of alkoxy group, for example, 2,2-bis (4- ( (Meth) acryloxypolyethoxy) phenyl) propane, 2,2-bis (4-
((Meth) acryloxypolypropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypolybutoxy) phenyl) propane, 2,2-bis (4-
((Meth) acryloxypolyethoxypolypropoxy)
Phenyl) propane and the like.

The above-mentioned 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane in which the polyalkoxy group is a polyethoxy group includes compounds that differ depending on the number of ethoxy groups. 2-bis (4-
((Meth) acryloxydiethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytriethoxy) phenyl) propane, 2,2-bis (4-
((Meth) acryloxytetraethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypentaethoxy) phenyl) propane, 2,2-bis (4
-((Meth) acryloxyhexaethoxy) phenyl)
Propane, 2,2-bis (4-((meth) acryloxyheptaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyoctaethoxy) phenyl) propane, 2,2-bis ( 4-((meth) acryloxynonaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxydecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxy) Undecaethoxy) phenyl) propane, 2,2-
Bis (4-((meth) acryloxydodecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytridecaethoxy) phenyl) propane, 2,
2-bis (4-((meth) acryloxytetradecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypentadecaethoxy) phenyl) propane, 2,2-bis (4- ((Meth) acryloxyhexadecaethoxy) phenyl) propane.
Examples of commercially available 2,2-bis (4- (methacryloxypentaethoxy) phenyl) propane products include, for example, BPE-500 (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.). -Bis (4- (methacryloxypentadecaethoxy) phenyl) propane product has BPE
-1300 (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.) is commercially available.

Examples of the compound in which the polyalkoxy group is composed of a plurality of types of alkoxy groups include 2,2-bis (4-((meth) acryloxypolyethoxypolypropoxy) phenyl) propane.

The 2,2-bis (4-((meth) acryloxypolyethoxypolypropoxy) phenyl) propane includes compounds having different numbers of ethoxy groups and propoxy groups. (4-((meth) acryloxydiethoxyoctapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytetraethoxytetrapropoxy) phenyl) propane,
2,2-bis (4-((meth) acryloxyhexaethoxyhexapropoxy) phenyl) propane and the like.

The compounds exemplified above can be used alone or in combination of two or more as the photopolymerizable compound of the present invention.

The photosensitive resin composition of the present invention contains vitamin E
It contains. Vitamin E has antioxidant properties, suppresses thermal polymerization of the above-mentioned photopolymerizable compound, enables long-term storage of the photosensitive resin composition, and mainly functions as a storage stabilizer. From this role, in the preparation of the photosensitive resin composition, it is preferable to use the storage stabilizer in a state where the storage stabilizer is previously blended in the photopolymerizable compound, for example, the storage stabilizer during the preparation of the photopolymerizable compound By coexisting, thermal polymerization of the photopolymerizable compound is effectively suppressed. When vitamin E is used as a storage stabilizer, a decrease in the sensitivity of the photosensitive resin composition, which is a problem in addition of a conventional storage stabilizer, can be suppressed. It is preferable to use it as an antioxidant when synthesizing the photopolymerizable compound from the viewpoint of workability and productivity.

Vitamin E may have a substituent or a derivative as long as the effects of the present invention are not impaired.

As the photopolymerization initiator contained in the photosensitive resin composition of the present invention, for example, benzophenone, N,
N, N'-tetraalkyl- such as N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone)
4,4'-diaminobenzophenone, 2-benzyl-2
-Dimethylamino-1- (4-morpholinophenyl)-
Butanone-1,2-methyl-1- [4- (methylthio)
An aromatic ketone such as phenyl] -2-morpholino-propanone-1, a quinone such as alkylanthraquinone, a benzoin ether compound such as benzoin alkyl ether, a benzoin compound such as benzoin or alkylbenzoin, a benzyl derivative such as benzyldimethyl ketal;
2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5
-Di (methoxyphenyl) imidazole dimer, 2-
(O-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5
2,4,5-triarylimidazole dimer derivatives such as -diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer, 9-phenylacridine, 1,7- Screw (9, 9 '
Acridine derivatives such as -acridinyl) heptane;
Examples include phenylglycine, N-phenylglycine derivatives, coumarin compounds and the like.

The 2,4,5-triarylimidazole dimer derivative may be a target compound having the same substituent on two aryl groups or an asymmetric compound having different substituents. There may be. From the viewpoint of the sensitivity of the photosensitive resin composition and the adhesion to the substrate, 2,4,4
5-Triarylimidazole dimers are preferred. These can be used alone or in combination of two or more.

In the photosensitive resin composition of the present invention, the compounding amount of the binder polymer is preferably 40 to 80 parts by weight based on 100 parts by weight of the total amount of the binder polymer, the photopolymerizable compound and the storage stabilizer. . If the amount is less than 40 parts by weight, the photocured product tends to become brittle, and the film-forming ability when used as a photosensitive element tends to be poor. If the amount exceeds 80 parts by weight, the sensitivity of the photosensitive resin composition is reduced. It tends to be insufficient.

The compounding amount of the photopolymerizable compound is 100% of the total amount of the binder polymer, the photopolymerizable compound and the storage stabilizer.
It is preferable that the amount is 20 to 60 parts by weight with respect to parts by weight. If the amount is less than 20 parts by weight, the sensitivity tends to be insufficient, and if it exceeds 60 parts by weight, the photocured product tends to become brittle.

The amount of the photopolymerization initiator is preferably 0.1 to 10.0 parts by weight, more preferably 0.1 part by weight, based on 100 parts by weight of the total amount of the binder polymer, the photopolymerizable compound and the storage stabilizer. 5 to 6.0 parts by weight. If the amount is less than 0.1 part by weight, the sensitivity of the photosensitive resin composition tends to be insufficient. If the amount is more than 10.0 parts by weight, the curability of the bottom (deep portion) when forming the resist is reduced. And scum tends to occur.

The concentration of vitamin E in the photosensitive resin composition is as follows:
It is preferably 0.05 to 20 ppm (weight ratio),
More preferably, it is 0.1 to 10 ppm (weight ratio).

When vitamin E is used as an antioxidant when synthesizing a photopolymerizable compound, vitamin E is contained in the photopolymerizable compound preferably in an amount of 5 to 2000 ppm (weight ratio), more preferably 10 to 1000 ppm. In the proportion of If it is less than 5 ppm, the effect of preventing thermal polymerization becomes insufficient, and if it is more than 2000 ppm, it is not possible to suppress a decrease in sensitivity at the time of photopolymerization, which adversely affects the physical properties of the photosensitive element.

The photosensitive resin composition of the present invention may contain, if necessary, a cationic polymerization initiator, a dye such as malachite green, a photochromic agent such as tribromophenylsulfone or leucocrystal violet, a thermal coloring inhibitor, Plasticizers such as toluenesulfonamide, pigments, fillers, defoamers, flame retardants, stabilizers, adhesion promoters, leveling agents, release accelerators, antioxidants, fragrances, imaging agents, thermal crosslinking agents, etc. Each of the binder polymer, the photopolymerizable compound, and the storage stabilizer can be blended at a ratio of about 0.01 to 20 parts by weight with respect to 100 parts by weight in total. These can be used alone or in combination of two or more.

The form of use of the photosensitive resin composition is not particularly limited, but it can be used by preparing a solution using a solvent, if necessary. The prepared solution is copper,
A resist film of the photosensitive resin composition is formed by applying a liquid resist on a metal surface such as a copper-based alloy, iron, or an iron-based alloy and drying the resist. The dried photosensitive resin composition film may be coated with a protective film if necessary, and a resist pattern is generated by exposing the film to light. Alternatively, a film-form photosensitive resin composition supported on a support is obtained by applying and drying a solution of the photosensitive resin composition on a film serving as a support, and this is used as a photosensitive element in various applications. May be used. As a solvent for preparing the solution of the photosensitive resin composition, for example, methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N, N
-An organic solvent such as dimethylformamide and propylene glycol monomethyl ether or a mixed solvent thereof is used. When prepared as a solution having a solid content of about 30 to 60% by weight, the solution is suitable for coating.

The thickness of the film of the photosensitive resin composition may be changed as appropriate according to the intended use, but the thickness after drying is preferably about 1 to 100 μm, more preferably 3 to 80 μm, and particularly preferably 5 to 80 μm. ５０50 μm, very preferably 10-4
The thickness is 5 μm, and a thickness of 20 to 40 μm is most effective.
When the photosensitive resin composition film is used by coating with a protective film, a polymer film such as polyethylene or polypropylene can be used as the protective film.

When the above-mentioned photosensitive resin composition is used as a photosensitive element, it can be obtained by applying a solution of the photosensitive resin composition on a support and drying it as described above. As the support, for example, a polymer film such as polyethylene terephthalate, polypropylene, polyethylene, and polyester is used. The thickness of the support is preferably 1 to 100 μm. The application of the solution can be performed by a known method using equipment such as a roll coater, a comma coater, a gravure coater, an air knife coater, a die coater, and a bar coater. Also,
A good film is formed by performing drying at 70 to 150 ° C. for about 5 to 30 minutes. Further, the amount of residual solvent in the photosensitive resin composition film is desirably 2% by weight or less from the viewpoint of preventing solvent diffusion in a subsequent step.

The polymer films exemplified above are:
It may be used as a protective film for the photosensitive element,
One of the above polymer films can be laminated on both sides of the photosensitive resin composition layer as a support for the photosensitive resin composition layer and the other as a protective film of the photosensitive resin composition. In this case, the protective film is preferably a low fisheye polymer film, and the adhesive force between the photosensitive resin composition film and the protective film is better than the adhesive force between the photosensitive resin composition film and the support. It is preferable to select the polymer film so as to be small.

The photosensitive element has an intermediate layer and a protective layer such as a cushion layer, an adhesive layer, a light absorbing layer and a gas barrier layer in addition to the above-mentioned photosensitive resin composition film, support and protective film. May be.

As one form of storage of the photosensitive element, there is a method of storing it by winding it around a cylindrical core. The photosensitive element in this case may or may not have a protective film. For the core, at least the outer peripheral surface thereof may be made of plastic such as polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, and ABS resin (acrylonitrile-butadiene-styrene copolymer).
At the time of winding, it is preferable to wind the support so that the support is on the outside. From the viewpoint of protection of the end of the wound photosensitive element roll, it is preferable to provide an end face separator at the end of the photosensitive element, and it is preferable to use a moisture-proof end face separator from the viewpoint of edge fusion resistance. As a packing method, it is preferable to pack with a black sheet having low moisture permeability.

When a resist pattern is produced on a circuit-forming substrate using the above-mentioned photosensitive element, the photosensitive resin composition film is removed after removing the protective film, if any. It is pressed and laminated on a substrate for use. Preferably, the photosensitive resin composition film is 70 to 130
0.1-1MP on the circuit forming substrate while heating to about ℃
The layers are laminated by pressure bonding at a pressure of about a (about 1 to 10 kgf / cm ² ). It is also possible to laminate in a reduced pressure atmosphere. The surface to be laminated is usually a metal surface, but is not particularly limited.

The photosensitive resin composition film thus completed in lamination hardens into an image by irradiation with actinic rays through a negative mask pattern. The light source for the actinic ray may be any one that emits a light beam effective for photopolymerization, and includes known light sources, for example, ultraviolet rays such as carbon arc lamps, mercury vapor arc lamps, high-pressure mercury lamps, xenon lamps, and visible light. Can be used.

Next, if a support is present on the exposed photosensitive resin composition film, the support is removed, and the unexposed portion is removed using a developing solution and developed. Can be manufactured. The development includes wet development using an alkaline aqueous solution or another aqueous solution as a developer, dry development using an organic solvent as a developer, and the like. In the photosensitive resin composition of the present invention, development using an alkaline aqueous solution is preferable. . As the alkaline aqueous solution, for example, 0.1
Dilute solutions of sodium carbonate of 5 to 5% by weight, dilute solutions of 0.1 to 5% by weight of potassium carbonate, dilute solutions of 0.1 to 5% by weight of sodium hydroxide, and the like. The pH of the alkaline aqueous solution is preferably in the range of 9 to 11, and the temperature is adjusted according to the developability of the photosensitive resin composition. A surfactant, an antifoaming agent, an organic solvent and the like may be blended in the alkaline aqueous solution. As a method of the development,
For example, dip method, spray method, brushing,
Slapping and the like.

After the development, if necessary,
The resist pattern may be further cured by heating at about 250 ° C. or exposing at about 0.2 to 10 J / cm ² .

In order to effectively use the resist pattern of the photosensitive resin composition of the present invention, the thickness of the resist pattern is preferably 3 to 80 μm, more preferably 5 to 80 μm.
To 50 μm, particularly preferably 10 to 45 μm,
A film thickness of ４０40 μm is best.

When wiring is formed using the resist pattern of the present invention, the surface of the circuit forming substrate is treated by a known method such as etching or plating using the developed resist pattern as a mask. For etching the metal surface, for example, a cupric chloride solution, a ferric chloride solution, an alkali etching solution, or the like can be used. Examples of the plating include copper plating, nickel plating, alloy plating such as gold plating and solder plating.

Thereafter, the resist pattern is peeled off to form a metal wiring corresponding to the pattern on the substrate. For stripping the resist pattern, for example, an aqueous solution that is more strongly alkaline than the alkaline aqueous solution used for development is used. Examples of the alkaline aqueous solution for stripping include a 1 to 10% by weight aqueous sodium hydroxide solution,
% Aqueous potassium hydroxide solution. Examples of the peeling method include an immersion method and a spray method. The resist pattern of the present invention can cope with high-density wiring and is suitable for use in manufacturing a substrate for a semiconductor package, but can also be used for manufacturing a printed wiring board, and can be used for a multilayer printed wiring board or a small-diameter through hole. Can be suitably manufactured.

[0062]

The present invention will be described below with reference to examples and comparative examples.

[Preparation of EO-modified trimethylolpropane trimethacrylate containing vitamin E (TMPT21E (VE))]
EO-modified trimethylolpropane (trade name: TAA-0880) was placed in a 4-liter separable flask equipped with a stirrer, thermometer, air introduction tube, and rectification tower (15 stages).
4, Nippon Emulsifier) 720 g (0.68 mol), methyl methacrylate 3000 g (30 mol), vitamin E0.
172 g was charged and heated and refluxed while blowing dry air at a rate of 200 ml / min to remove water in the system. Next, 2.5 g of isopropyl orthotitanate (titanium tetraisopropoxide) was added as a catalyst, and the mixture was heated to reflux to allow a transesterification reaction to proceed. In the heating and refluxing of the reaction mixture, the top temperature of the rectification column was initially around 100 ° C., which is the boiling point of methyl methacrylate, but approached the boiling point of the azeotropic mixture of methanol and methyl methacrylate with the progress of the reaction. Therefore, the reaction was carried out while adjusting the reflux ratio such that the tower top temperature was in the range of 64 to 66 ° C. and distilling off methanol as an azeotrope with methyl methacrylate.

About 3 hours after the catalyst was added, the temperature at the top of the column began to rise and rose to about 90 ° C., and accordingly the reflux ratio was gradually increased, and finally the reflux ratio was set to 15. The reaction continued. During this time, the reaction solution 3 hours after the start of the reaction was subjected to high performance liquid chromatography (HLC).
As a result, no EO-modified trimethylolpropane as a raw material alcohol was detected, and an intermediate product E
O-modified trimethylolpropane monomethacrylate 2.0% (HLC area ratio), EO-modified trimethylolpropane dimethacrylate 2.2% (HLC area ratio),
The reaction was completed when the trimethacrylic acid ester of the alcohol, which was the target compound, was 95.8% (HLC area ratio).

When the reaction solution was cooled to 70 ° C.,
% Catalyst was added to hydrolyze the catalyst to make it insoluble. After allowing to stand for 30 minutes, the oil layer was placed in a 1-liter eggplant-shaped flask by decantation, and excess methyl methacrylate was distilled off under reduced pressure using a rotary evaporator. Then, the liquid in the eggplant flask was suction-filtered under reduced pressure. After filtration, the target substance, EO-modified trimethylolpropane trimethacrylate containing vitamin E was obtained. Yield 830.1 g
(Total yield: 96.7%).

Examples 1 to 4 and Comparative Examples 1 to 4 Solutions were prepared by mixing the following components and solvents.

Binder polymer solution 120 g (solid content 58 g) Solid component (weight ratio): methacrylic acid / methyl methacrylate / styrene / butyl methacrylate / ethyl acrylate (30/22/30/8/10) Solvent (weight) Ratio): methyl cellosolve / toluene (3 /
2) Polymer weight average molecular weight: 50,000 Solid content acid value: 194 mg KOH / g Photopolymerization initiator 2,2'-bis (2-chlorophenyl) -4,4 ',
5,5'-tetraphenylbisimidazole 3.2 g 4,4'-bis (diethylamino) benzophenone
0.06 g-Color former Leuco Crystal Violet 0.4 g-Thermal polymerization inhibitor 4-tert-butylcatechol (TBC) 0.04 g-Dye malachite green 0.04 g-Solvent Acetone 10 g Toluene 7 g N, N-dimethylformamide 3 g Methanol 3 g Next, the photopolymerizable compound PPC1 shown below was added to the above solution.
A solution of the photosensitive resin composition was prepared by adding a mixture of -PPC6 and a storage stabilizer in the proportions shown in Tables 1 and 2. The storage stabilizer incorporated in the photopolymerizable compound was vitamin E (VE), p-methoxyphenol (MEH
Q) or 4-tert-butylcatechol (TBC)
In the case where the photopolymerizable compound PPC3 was mixed with vitamin E as a storage stabilizer, the EO-modified trimethylolpropane trimethacrylate (TMPT21E (VE)) containing vitamin E prepared above was used.

Photopolymerizable compound PPC1 represented by the following formula (1), wherein p + q ≒ 10,
2-bis (4- (methacryloxypentaethoxy) phenyl) propane (trade name: BPE500, manufactured by Shin-Nakamura Chemical Co., Ltd.) Photopolymerizable compound PPC2 is represented by the following formula (1), and p + q ≒ 14 Certain 2,2-bis (4- (methacryloxyheptaethoxy) phenyl)
Propane (trade name: BPEO14MA, manufactured by Shin-Nakamura Chemical Co., Ltd.)

Embedded image -Photopolymerizable compound PPC3 EO-modified trimethylolpropane trimethacrylate represented by the following formula (2) (sample name: TMPT21E, manufactured by Hitachi Chemical Co., Ltd.)

Embedded image -Photopolymerizable compound PPC4 EO-modified trimethylolpropane triacrylate represented by the following formula (3) (sample name: SR454, manufactured by Sartomer Co., Ltd.)

Embedded image -Photopolymerizable compound PPC5 Nonylphenoxytetraethyleneoxyacrylate (trade name: NP-4EA, manufactured by Kyoeisha Chemical Co., Ltd.) represented by the following formula (4)

Embedded image ・ Photopolymerizable compound PPC6 Nonaethylene glycol dimethacrylate (trade name: 9
G, manufactured by Shin-Nakamura Chemical Co., Ltd.)-Storage stabilizer 4-tert-butylcatechol (TBC): Wako Pure Chemical Industries, Ltd.
Reagent p-methoxyphenol (MEHQ): Reagent manufactured by Wako Pure Chemical Industries, Ltd.

Table 1 Photo-polymerizable compound Example 1 Example 2 Example 3 Example 4 (Storage) (Stabilizer) --------------------------------------------------------------------------------------------------------- PPC1 (VE) 28-28-PPC2 (VE)-28-28 PPC3 ( VE) 4 4--PPC4 (MEHQ)--44 PPC5 (VE) 4444 PPC6 (MEHQ) 66 6 6------------------------------------------------------------------------------------------------------------------- −−−−−−−− Total VE concentration in the photopolymerizable compound (ppm) 70 70 70 70 Total MEHQ concentration (ppm) in the photopolymerizable compound 15 15 15 15 −−−−−−−−−−−−−−−− −−−−−−−−−−−−−−−−−−−−

Table 2 Photopolymerizable compound Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 PPC1 (MEHQ) 28---PPC1 (TBC)-28--PPC2 (Stabilizer)---------------------------PPC1 (MEHQ) 28---PPC1 (TBC)-28--PPC2 ( --28-PPC2 (TBC)---28 PPC3 (MEHQ) 4-4-PPC3 (TBC)-4-4 PPC5 (MEHQ) 4-4-PPC5 (TBC)-4-4 PPC6 (MEHQ) 6 6 6 6-6------------------------------------------------------------------------------ Total MEHQ concentration (ppm) in the compound 80 15 80 15---------------------------------------------------Prepared Examples 1-4 and Comparative Examples 1 to The solution of the photosensitive resin composition was uniformly coated on a polyethylene terephthalate film having a thickness of 16μm and dried 10 minutes at 100 ° C. hot air convection dryer, to obtain a photosensitive element. The thickness of the photosensitive resin composition film was 30 μm.

On the other hand, a copper-clad laminate (trade name: MCL) in which copper foil (thickness: 35 μm) is laminated on both sides of a glass epoxy plate
-E-67, manufactured by Hitachi Chemical Co., Ltd.)
Polishing was carried out using a polishing machine (manufactured by Sankei Co., Ltd.) having a brush equivalent to # 600, washed with water, and then dried with an air stream.
The obtained copper-clad laminate was heated to 80 ° C., and the photosensitive resin composition film of the photosensitive element was brought into contact with the copper surface and heated to 110 ° C. to laminate.

Using the copper-clad laminate on which the photosensitive resin composition film was laminated as described above, the following operation was performed to evaluate the photosensitive resin composition film.

[Sensitivity] On a photosensitive resin composition film of the laminate, a 41-step stofer step tablet was placed as a negative, and a parallel light exposure machine having a high pressure mercury lamp (model name: EXM1201, manufactured by Oak Manufacturing Co., Ltd.) ) Co., Ltd.) ^{using, 60mJ / cm 2, 120mJ /} cm 2 and 240 mJ /
Three irradiations of cm ² were performed.

Thereafter, the polyethylene terephthalate film was peeled off, and an unexposed portion was removed by spraying a 1% by weight aqueous solution of sodium carbonate at 30 ° C. for 40 seconds to develop a pattern.

The number of steps of the step tablet of the photocured film formed on the laminate by the above-described three kinds of exposure and development was measured, and the 41 step tablet (ΔOD = 0.05) was obtained from the measured value. The sensitivity of the photosensitive resin composition was evaluated by calculating the exposure amount (mJ / cm ² ) required to cure the 15 steps. The lower the exposure value, the higher the sensitivity of the photosensitive resin composition.

[Resolution] A glass negative mask (manufactured by Hitachi Chemical Co., Ltd.) was placed on the photosensitive resin composition film of the laminate, and an exposure dose (corresponding to the sensitivity obtained in the above sensitivity evaluation) was obtained. 15 steps / 41 steps). Thereafter, the same operation as the developing operation in the sensitivity evaluation was repeated.

The pattern of the cured film obtained after the development was observed, the minimum value of the line width (μm) remaining as a line and space was obtained, and the resolution was evaluated. The smaller the value, the higher the resolution. [Storage stability] The copper-clad laminate having the photosensitive resin composition film laminated thereon was placed in a thermo-hygrostat at a temperature of 30 ° C. and a humidity of 90% for 24 hours.
Hold for hours. Thereafter, the sample was taken out of the thermo-hygrostat and subjected to the same operations as the above-described sensitivity evaluation and resolution evaluation. By comparison with the value when the treatment in the constant temperature and humidity chamber is not performed,
The storage stability can be evaluated, and the closer to the value where no thermostatic bath treatment is performed, the higher the storage stability.

[Releasability] The copper-clad laminate on which the photosensitive resin composition film was laminated was irradiated with an exposure amount (15 steps / 41 steps) corresponding to the sensitivity obtained in the above-mentioned sensitivity evaluation, and was carried out at 30 ° C. ,
Development was carried out using a 1% by weight aqueous solution of sodium carbonate. 1
After standing for 24 hours, the mixture was poured into a 3% by weight aqueous solution of sodium hydroxide at 50 ° C., observed with stirring with a stirrer, and the time (second) until peeling of the photocured product was measured to evaluate peelability. The shorter the time until peeling, the lower the peelability.

[Generation of scum] 0.5 m ² of the photosensitive resin composition film of the photosensitive element was dissolved in 1 liter of a 1% by weight aqueous sodium carbonate solution without exposure, and the solution was kept at 30 ° C. While circulating in a spray developing machine for 90 minutes. After standing for 2 minutes, the presence or absence of oily products (scum) adhering to the wall of the developing machine was observed.

A: No scum B: With scum [Plating resistance] A negative mask was placed on a copper-clad laminate on which a photosensitive resin composition film was laminated, and an exposure corresponding to the sensitivity obtained in the sensitivity evaluation described above. (15 steps / 41 steps). Thereafter, the same operation as the developing operation in the sensitivity evaluation was repeated. This is degreased and washed with water, and 3.0 A / dm ²
For 30 minutes, washed with water, immersed in borofluoric acid, soldered at 1.5 A / dm ² for 10 minutes, and washed with water. Remove water with an airbrush, and use a 24 mm wide adhesive tape (trade name: Cellotape, manufactured by Sekisui Chemical Co., Ltd.)
Were adhered to each other and peeled off at a stretch, and the presence or absence of peeling of the cured product was examined.

A: No peeling B: With peeling The results of the above evaluation performed on the photosensitive resin composition films of Examples 1 to 4 and Comparative Examples 1 to 4 are shown in Tables 3 and 4.

[0080]

Table 3---------------------------------------------------------------------------------------------------------------- −−−−−−−−−−−−−−−−−−−−−−−− Film thickness (μm) 30 30 30 30 −−−−−−−−−−−−−−−−−−−−−−− −−−−−−−−−− Sensitivity (mJ / cm ² ) 150 150 150 150 Resolution (μm) 7777 77 Storage stability test (30 ° C., 90% RH, 24 hr value) Sensitivity (mJ / cm ² ) 150 150 150 150 Resolution (μm) 77 77 77 Peeling time (sec) 50 50 50 50 Scum generation A A A A Plating resistance A A A A --------------- −−−−−−−−−−−−−−−

[Table 4] ------------------------------------------------------------------- Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 ------ −−−−−−−−−−−−−−−−−−−−−−−− Film thickness (μm) 30 30 30 30 −−−−−−−−−−−−−−−−−−−−−−− −−−−−−−−−− Sensitivity (mJ / cm ² ) 200 220 200 220 Resolution (μm) 7777 Storage stability test (30 ° C., 90% RH, 24 hr value) Sensitivity (mJ / cm ² ) 200 220 200 220 Resolution (μm) 77 77 77 Peeling time (sec) 50 50 50 50 Scum generation A A A A Plating resistance A A A A ------------------------------- −−−−−−−−−−−−−−−

[0081]

Industrial Applicability The photosensitive resin composition of the present invention can prevent a decrease in sensitivity due to a storage stabilizer of a photopolymerizable compound, and can improve workability in circuit formation of a substrate for a semiconductor package. can do. Further, it has excellent resolution, scum generation resistance and plating resistance.

Further, the photosensitive element of the present invention is excellent in sensitivity, resolution, scum generation resistance, plating resistance, workability and productivity, and is useful for increasing the density of circuits of a substrate for a semiconductor package.

Further, the method for forming a resist pattern according to the present invention is excellent in sensitivity, resolution, scum generation, plating resistance, workability and productivity of a resist film, and is suitable for manufacturing a circuit board for a high-density semiconductor package. Suitable for.

The method of manufacturing a semiconductor package substrate of the present invention is to manufacture a high-density semiconductor package circuit board by using a resist film excellent in sensitivity, resolution, scum resistance, plating resistance, workability and productivity. Can be.

Continuation of the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) C08F 291/00 C08F 291/00 G03F 7/004 502 G03F 7/004 502 512 512 7/028 7/028 7/032 7 03/2 H05K 3/00 H05K 3/00 F Address Hitachi Chemical Co., Ltd. Goi Works F-term (reference) 2H025 AA00 AA01 AA02 AB11 AB16 AB17 AC01 AD01 BC14 BC42 CA01 CA20 CA28 CB13 CB14 CB16 CB23 CB28 CB30 CB43 CC01 FA03 FA17 FA39 FA40 FA43 4J011 PA35 PA65 PA69 QA23 QA24 QB16 RA03 RA06 RA07 RA10 SA21 SA25 SA31 SA36 SA51 SA63 SA78 4J026 AA17 AA45 AB01 AB04 AB11 AB28 BA28 DB36 FA05 GA07 4J027 AC02 AC06 BA26 BA28 CA02 CA03 CA06 CA07 CA10 CA29 CB10 CC03 CD10

Claims (5)

[Claims] 1. A photosensitive resin composition comprising a binder polymer, a photopolymerizable compound having at least one ethylenically unsaturated bond, a photopolymerization initiator, and vitamin E. 2. The photosensitive resin composition according to claim 1, wherein the photopolymerizable compound contains 2,2-bis (4-((meth) acryloxypolyalkoxy) phenyl) propane. 3. A photosensitive element comprising the photosensitive resin composition according to claim 1 disposed on a support in the form of a thin film. 4. The photosensitive resin composition according to claim 1 or 2 is laminated on a substrate for forming a circuit, and an actinic ray corresponding to a developed image is irradiated on the photosensitive resin composition to cure the exposed portion. And removing the unexposed portions by development. 5. The photosensitive resin composition according to claim 1 or 2 is laminated on a substrate for forming a circuit, and the photosensitive resin composition is irradiated with an actinic ray corresponding to a developed image to photo-cur the exposed portion. Forming a resist pattern on the substrate by removing unexposed portions by development, and providing a circuit corresponding to the resist pattern on the substrate by applying etching or plating to the substrate. A method for manufacturing a circuit board for a semiconductor package.