JP3372903B2 - Photoresist stripper - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photoresist stripping agent used particularly in the production of printed wiring boards, lead frames, and semiconductor packages. The present invention relates to a photoresist remover having excellent properties.

[0002]

2. Description of the Related Art A photoresist method using a photosensitive resin composition is used for manufacturing printed wiring boards, lead frames, semiconductor packages, etc. In this photoresist method, for example, a transparent film is first used. After forming a photosensitive resin composition layer by coating the photosensitive resin composition on a support such as, the photosensitive resin composition layer is laminated on the substrate surface to form a desired pattern, then the After exposing the photosensitive resin composition layer through a pattern mask, the unexposed portion is removed by a developing treatment with a solvent or an alkaline aqueous solution to form a resist image, and the formed resist image is used as a protective mask. After the etching treatment or the pattern plating treatment, a method of manufacturing a printed circuit board by removing the cured resist with a resist release agent is usually performed. .

In these methods, an alkaline aqueous solution such as sodium hydroxide is usually used as a stripping agent for photoresist. However, in recent years, with the advancement of technology, the density of printed wiring boards and the fine patterning have remarkably advanced, and the penetrability to the cured resist is insufficient with the above-mentioned release agent, and sufficient resist release property is obtained. It is a difficult situation to obtain.

Further, in the case of forming a fine pattern, the pattern plating method is advantageous in order to reduce the etching of the metal conductor as much as possible. In this plating method, if the resist stripping time becomes long, solder plating or the like may occur. Attack on metal resist plating is also a problem.

As a countermeasure against this, an organic release agent has been proposed. For example, Japanese Patent Publication No. 82382/1995 discloses a photoresist removing agent comprising 10 to 100% by weight of a specific water-soluble amine and 0 to 90% by weight of a water-soluble propylene glycol derivative. , Alkanolamines, alkoxyalkylamines or alkoxyalkanolamines 5 to 50% by weight, acid amides 1 to 30% by weight, sugars or sugar alcohols 0.5 to 15% by weight, the balance being water. A photoresist stripping agent is disclosed in JP-A-9-152721, in which alkanolamine is 5 to 40% by weight, N, N-diethylhydroxylamine is 5 to 30% by weight, diethylene glycol monoalkyl ether is 5 to 40% by weight, and saccharide 2 is used. The resist stripping agent comprising 30 to 30% by weight and 35 to 70% by weight of water is disclosed in JP-A-7-28254. In the publication, at least one substance selected from the group consisting of sugar alcohol, isopropyl alcohol, dimethyl sulfoxide, and 1,3-dimethyl-2-imidazolidinone, alcohol amine, water, and optionally a quaternary compound. A resist stripping solution composed of ammonium hydroxide has been proposed.

[0006]

However, in the technique disclosed in the above publication, although some improvement can be recognized in the photoresist stripping time and the strip shape, it is still satisfactory in view of the recent sophistication and high definition of the technique. However, further improvement in resist releasability is desired, and in the plating method, improvement in attackability on metal resist plating is also desired. Under the circumstances, it is an object of the present invention to provide a photoresist stripping agent having excellent resist strippability.

[0007]

However, as a result of intensive studies conducted by the present inventors to solve such problems, the water-soluble amine (a) represented by the general formula (1) and the general formula (2) are represented. It was found that a photoresist stripping agent comprising an ammonium hydroxide (b), an ammonium hydroxide (c) represented by the general formula (3) and a benzotriazole (d) meets the above-mentioned object. It came to completion.

[0008]

[Chemical 5] (In the formula, R ₁ , R ₂ , R ₃ and R ₄ are hydrogen atoms or carbon atoms 1
To 3 alkyl groups, which may be the same or different. n and m are integers of 0 to 2 (however, the sum of n and m is at least 2), and x is an integer of 1 to 3.

[0009]

[Chemical 6] (In the formula, R ₅ , R ₆ and R ₇ are alkyl groups having 1 to 3 carbon atoms and may be the same or different. N is 0 to
It is an integer of 2. )

[0010]

[Chemical 7] (In the formula, R ₈ , R ₉ , R ₁₀ and R ₁₁ are hydrogen or a carbon number 1 to
4 alkyl groups, which may be the same or different. )

Further, in the present invention, the water-soluble propylene glycols (e) represented by the general formula (4) are added to 100 parts by weight of the water-soluble amine (a) represented by the general formula (1).
When the content is 1 to 10 parts by weight, the effect of the present invention is remarkably exhibited.

[0012]

[Chemical 8] (In formula, R <_12> , R < ₁₃ > is a hydrogen atom or a C1-C4 alkyl group, and may be the same or different. Y is 1-
It is an integer of 3. )

The photoresist stripper of the present invention comprises a binder polymer (f), an ethylenically unsaturated compound (g) and a photopolymerization initiator (h). The photopolymerization initiator (h) is used as a binder polymer. 2.5 to 5 parts by weight of the lophine dimer (h1) and 0.05 parts by weight of the p-aminophenyl ketone (h2) are added to 100 parts by weight of the total amount of (f) and the ethylenically unsaturated compound (g). When a photosensitive resin composition containing 0.2 to 0.2 parts by weight is used, a particularly remarkable effect is exhibited.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be specifically described below. The water-soluble amine used in the present invention (a), without being particularly limited as long as it is a compound having a structure represented by the general formula (1), for example, monoethanolamine A <br/> Mi emissions, 1, Examples include 1,2,2-tetramethylmonoethanolamine. Among them, monoethanolamine is preferably used.

The ammonium hydroxide (b) represented by the general formula (2) is not particularly limited, and examples thereof include trimethyl (2-hydroxyethyl) ammonium hydroxide and triethyl (2-hydroxyethyl) ammonium hydroxide. Examples thereof include oxide and dimethylethyl (2-hydroxyethyl) ammonium hydroxide. Among them, trimethyl (2-hydroxyethyl) ammonium hydroxide is preferably used.

The content of the ammonium hydroxide (b) is 10% by weight of the water-soluble amine (a) represented by the general formula (1).
The amount is preferably 5 to 15 parts by weight, more preferably 5.5 to 12.5 parts by weight, and particularly preferably 7 to 11 parts by weight, based on 0 parts by weight. If the content is less than 5 parts by weight, the effect of shortening the peeling time cannot be obtained, and if it exceeds 15 parts by weight, the peeling dispersibility tends to be poor, such being undesirable.

The ammonium hydroxide (c) represented by the general formula (3) is not particularly limited, and examples thereof include ammonium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide and tetrabutylammonium hydroxide. Etc. Among them, tetramethylammonium hydroxide is preferably used.

The content of the ammonium hydroxide (c) is 10% by weight of the water-soluble amine (a) represented by the general formula (1).
The amount is preferably 15 to 25 parts by weight, more preferably 16.5 to 23.5 parts by weight, and particularly preferably 18 to 22 parts by weight with respect to 0 parts by weight. Such content is 1
If it is less than 5 parts by weight, the effect of reducing the peeling time cannot be obtained, and
If it exceeds the weight part, the peeling dispersibility tends to be poor, which is not preferable.

Further, examples of the benzotriazoles (d) include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, 4-carboxy-1,2,3-benzotriazole. , 5-carboxy-1,2,3-benzotriazole, bis (N-2-ethylhexyl) aminomethylene-1,2,3-benzotriazole, bis (N-2-ethylhexyl) aminomethylene-1,2,3 -Tolyltriazole, bis (N-
2-hydroxyethyl) aminomethylene-1,2,3-
Benzotriazole, bis (N-2-ethylhexyl)
Aminomethylene-4-carboxy-1,2,3-benzotriazole and the like can be mentioned. Of these, 1,2,3-benzotriazole is preferably used.

The content of the benzotriazoles (d) is 10% by weight of the water-soluble amine (a) represented by the general formula (1).
It is preferably 0.5 to 5 parts by weight, more preferably 0.5 to 4 parts by weight, and particularly preferably 0.8 to 2 parts by weight, relative to 0 parts by weight. If the content is less than 0.5 parts by weight, the attack on the metal resist plating such as solder plating becomes large, and if it exceeds 5 parts by weight, the washability of the release substrate tends to deteriorate, which is not preferable.

Thus, the photoresist release agent comprising the above (a) to (d) can be obtained, but in the present invention, it is preferable to further contain a water-soluble propylene glycol (e) represented by the general formula (4). , Such content is
It is preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the water-soluble amine (a) represented by the general formula (1),
More preferably 0.5 to 7 parts by weight, particularly preferably 1 to
3 parts by weight. If the content is less than 0.1 parts by weight, it is difficult to obtain the effect of improving the peeling property, and if it exceeds 10 parts by weight, the attack on the metal resist plating becomes large, which is not preferable.

The water-soluble propylene glycol (e) represented by the general formula (4) is not particularly limited, and examples thereof include dipropylene glycol methyl ether,
Examples include tripropylene glycol methyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol dimethyl ether, propylene glycol monopropyl ether and the like. Among them, propylene glycol monomethyl ether is preferably used.

Thus, in the present invention, the above (a)-
A photoresist release agent containing (d), preferably (e), is obtained.
Is 11 to 13 and the alkalinity is 11.8 to 12.
It is preferably 8 meq / g. Particularly preferred pH
Is 11.5 to 13, more preferably 11.5 to 12.
It is 5. The particularly preferred alkalinity is 11.9 to 1.
2.6 meq / g, more preferably 12.1-12.
It is 5 meq / g. If the pH is less than 11, it is difficult to obtain the effect of reducing the peeling speed, and if it exceeds 13, the peeling dispersibility tends to be poor, which is not preferable. Also, the alkalinity is 1
If it is less than 1.8 meq / g, it is difficult to obtain the effect of reducing the peeling speed, and if it exceeds 12.8 meq / g, the peeling dispersibility tends to be poor, which is not preferable.

In the present invention, the photoresist release agent obtained above can be used as it is as a release agent for the cured resist of the photosensitive resin composition, but preferably (a) to (d) or (a). It is desired to use the photoresist stripping agent consisting of (e) to 5 to 30% by weight, preferably 5 to 20% by weight, particularly preferably 6 to 10% by weight. If the concentration of the aqueous solution is less than 5% by weight, it is difficult to obtain the effect of improving the peelability, and if it exceeds 30% by weight, the amine odor becomes strong and it is not economical and not preferable.

Thus, the photoresist stripping agent of the present invention is used for stripping a cured resist obtained by providing a photosensitive resin composition on a substrate and irradiating it with an actinic ray to cure, and particularly for manufacturing a printed wiring board or Used for lead frame processing and semiconductor package manufacturing.

The photosensitive resin composition is not particularly limited as long as it is a photosensitive resin composition comprising a binder polymer (f), an ethylenically unsaturated compound (g) and a photopolymerization initiator (h). By using the above-mentioned release agent, an excellent effect of resist releasability is exhibited. Above all, as the photopolymerization initiator (h), a lophine dimer (h1) and p
The effect of the present invention is remarkably exhibited when the photosensitive resin composition contains -aminophenyl ketone (h2).

The binder polymer (f) is not particularly limited, but is preferably a carboxyl group-containing binder polymer. Specifically, it contains (meth) acrylate as a main component and is copolymerized with an ethylenically unsaturated carboxylic acid. The acrylic copolymer described above is preferably used,
If necessary, an acrylic copolymer obtained by copolymerizing another copolymerizable monomer can be used. In this case, the content of each component is 55 to 8 (meth) acrylate component.
5% by weight, preferably 60 to 72% by weight, the ethylenically unsaturated carboxylic acid component is 15 to 30% by weight, preferably 1
8 to 25% by weight, 0 to other copolymerizable monomer components
It is 15% by weight.

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

As the ethylenically unsaturated carboxylic acid, for example, monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid are preferably used, and in addition, dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid, or their Anhydrides and half esters can also be used. Among these, acrylic acid and methacrylic acid are particularly preferable.

Other copolymerizable monomers include, for example, tetrahydrofurfuryl (meth) acrylate, (meth) acryldimethylaminoethyl ester, diethylaminoethyl (meth) acrylate, glycidyl methacrylate, 2,2,2-trifluoroethyl. (Meth) acrylate, (meth) acrylamide, 2,2,3,3
-Tetrafluoropropyl (meth) acrylate acrylamide, diacetone acrylamide, styrene, α-
Methylstyrene, vinyltoluene, vinyl acetate, alkyl vinyl ether, (meth) acrylonitrile and the like can be mentioned.

In addition to the above, the binder polymer (f) thus obtained may be used in combination with a polyester resin, a polyamide resin, a polyurethane resin, an epoxy resin or the like. The weight average molecular weight of the binder polymer (f) is 10,000 to 300,000, preferably 10,000 to 150,000, more preferably 3
Those in the range of 10,000 to 100,000 are preferable,
If the molecular weight is small, cold flow is likely to occur, while if it is large, it is difficult to develop, resulting in a decrease in resolution and poor releasability at the time of resist stripping.

As the ethylenically unsaturated compound (g),
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 (meta)
Acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexane glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol Di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 2,2′-bis (4-acryiate) Roxydiethoxyphenyl) propane, 2,2′-bis (4- (meth) acryloxypolyethoxyphenyl)
Propane, 2-hydroxy-3- (meth) acryloyloxypropyl acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, 1,6-hexamethyldiglycidyl ether di (meth) Acrylate, trimethylolpropane triglycidyl ether tri (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, phthalic acid diglycidyl ester di (meth) acrylate,
Polyfunctional monomers such as glycerin polyglycidyl ether poly (meth) acrylate are used.

An appropriate amount of monofunctional monomer may be used in combination with these polyfunctional monomers. Examples of such monofunctional monomer include nonylphenoxy polyethylene glycol (meth) acrylate, 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-
Examples thereof include 2-hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, 2- (meth) acryloyloxyethyl acid phosphate, a phthalic acid derivative half (meth) acrylate, and N-methylol (meth) acrylamide.

The mixing ratio of the ethylenically unsaturated compound (g) is 5 to 90% by weight, preferably 20 to 80% by weight based on the total weight of the binder polymer (f) and the ethylenically unsaturated compound (g). %, Particularly preferably 40 to 60% by weight. The insufficient amount of the ethylenically unsaturated compound (g) is
Inadequate curing, deterioration of plasticity, delay of development rate, and an excessive amount of the ethylenically unsaturated compound (g) are not preferable because increase in tackiness, cold flow, and decrease in peeling rate of the cured resist are caused.

The photopolymerization initiator (h) is not particularly limited, and examples thereof include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether,
Benzoin phenyl ether, dibenzyl, diacetyl, anthraquinone, 2-ethylanthraquinone, 2-
tert-butylanthraquinone, methylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-
Diphenylanthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, 2-methylanthraquinone, 1,4-dimethylanthraquinone, 2,3-dimethylanthraquinone, 3-chloro-2-methylanthraquinone, 9,10-phenanthraquinone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-diethylthioxanthone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-dichloro-4-phenoxyacetophenone, phenylglyoxy Rate, α-hydroxyisobutylphenone, dibezosparone, 1- (4-isopropylphenyl) -2-hydroxy-2-methyl-1-propanone, 2-methyl- [4- (methylthio) phenyl]
2-morpholino-1-propanone, tribromophenyl sulfone, tribromomethylphenyl sulfone, benzyl dimethyl ketal and the like can be mentioned.

Further, N-phenylglycine, N-methyl-
N-phenylglycine, N-ethyl-N-phenylglycine, N- (n-propyl) -N-phenylglycine,
N- (n-butyl) -N-phenylglycine, N- (2
-Methoxyethyl) -N-phenylglycine, N-methyl-N-phenylalanine, N-ethyl-N-phenylalanine, N- (n-propyl) -N-phenylalanine, N- (n-butyl) -N-phenylalanine, N-
Methyl-N-phenylvaline, N-methyl-N-phenylleucine, N-methyl-N- (p-tolyl) glycine, N-ethyl-N- (p-tolyl) glycine, N-
(N-Propyl) -N- (p-tolyl) glycine, N-
(N-Butyl) -N- (p-tolyl) glycine, N-methyl-N- (p-chlorophenyl) glycine, N-ethyl-N- (p-chlorophenyl) glycine, N- (n-
Propyl) -N- (p-chlorophenyl) glycine, N
-Methyl-N- (p-bromophenyl) glycine, N-
Ethyl-N- (p-bromophenyl) glycine, N-
(N-Butyl) -N- (p-bromophenyl) glycine, N, N'-diphenylglycine, N-methyl-N-
N-aryl-α-amino acid compounds such as (p-iodophenyl) glycine, N- (p-bromophenyl) glycine, N- (p-chlorophenyl) glycine, and N- (o-chlorophenyl) glycine are also included. These may be used alone or in combination of two or more, but in the present invention, it is particularly preferable to use the lophine dimer (h1) and p-aminophenyl ketone (h2) as the photopolymerization initiator (h). preferable.

The lophine dimer (h1) is not particularly limited, but hexaarylbiimidazoles are preferable. 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′-tetraphenyl-1,1′-biimidazole, 2,4,2 ′, 4 '-Bis [bi (p-methoxyphenyl)]-5,5'-diphenyl-1,1'-biimidazole, 2,2'-bis (2,4-dimethoxyphenyl) -4,5,4', 5 '
-Diphenyl-1,1'-biimidazole, 2,2'-
Bis (p-methylthiophenyl) -4,5,4 ', 5'
-Diphenyl-1,1'-biimidazole, bis (2,2
4,5-triphenyl) -1,1'-biimidazole and the like can be mentioned. Furthermore, 1,2'-, 1,4'-, 2,
It is also possible to use tautomers which are covalently linked at the 4'-. Among them, 2,2'-bis (o-chlorophenyl)-
4,5,4 ', 5'-Tetraphenyl-1,2'-biimidazole is preferably used.

Examples of p-aminophenyl ketone (h2) include p-aminobenzophenone, p-butylaminophenone, p-dimethylaminoacetophenone and p-aminoaminophenone.
-Dimethylaminobenzophenone, p, p'-bis (ethylamino) benzophenone, p, p'-bis (dimethylamino) benzophenone [Michler's ketone], p,
p'-bis (diethylamino) benzophenone, p,
Examples thereof include p'-bis (dibutylamino) benzophenone, and among them, p, p'-bis (diethylamino) benzophenone is particularly preferable.

The content of the photopolymerization initiator (h) is 0.5 to 15 parts by weight based on 100 parts by weight of the total amount of the binder polymer (f) and the ethylenically unsaturated compound (g). Is preferable, and particularly preferably 2.5 to 6
Parts by weight.

The content of the lophine dimer (h1) is 1 to 10 parts by weight based on 100 parts by weight of the total amount of the binder polymer (f) and the ethylenically unsaturated compound (g). The content of the p-aminophenyl ketone (h2) is preferably 2.5 to 5 parts by weight, more preferably 3 to 4 parts by weight, and the binder polymer (f) and the ethylenically unsaturated compound ( g) total amount 1
The amount is preferably 0.02 to 0.5 part by weight, particularly preferably 0.05 to 0.2 part by weight, and further preferably 0.05 to 0.15 part by weight, relative to 00 parts by weight.

The photosensitive resin composition preferably further contains a leuco compound (i). Examples of the leuco compound (i) include tris (4-dimethylaminophenyl) methane [leuco crystal violet],
Examples include tris (4-diethylamino-2-methylphenyl) methane, leucomalachite green, leucoaniline, leucomethyl violet and the like. Among them, tris (4-dimethylaminophenyl) methane [leuco crystal violet] is preferably used.

The content of the leuco compound (i) is preferably 0.05 to 3 parts by weight based on 100 parts by weight of the total amount of the binder polymer (f) and the ethylenically unsaturated compound (g). , And 0.1 to 2 parts by weight,
It is particularly preferably 0.2 to 1 part by weight.

Thus, the binder polymer (f), the ethylenically unsaturated compound (g), and the photopolymerization initiator (h), preferably the lophine dimer (h1) and p.
-A photosensitive resin composition comprising a photopolymerization initiator (h) containing an aminophenyl ketone (h2) can be obtained. If necessary, other additives such as a thermal polymerization inhibitor, a plasticizer,
Dyes (colorants (excluding leuco compound (i)), discolorants),
Additives such as an antioxidant, a solvent, a surface tension modifier, a stabilizer, a chain transfer agent, a defoaming agent, and a flame retardant can be appropriately added.

The photoresist stripping agent of the present invention is used for stripping the cured resist of the photosensitive resin composition as described above, and the production of such a cured resist will be described below. The photosensitive resin composition obtained above can be used as a photoresist even in a liquid state, but usually,
It is used as a photoresist film having a laminated structure.
The film is formed by sequentially laminating a support film, a photosensitive resin composition layer and a protective film.

The support film used in the present invention is one having heat resistance and solvent resistance when forming the photosensitive resin composition layer, and specific examples of the support film include, for example, usually , Polyester film, polyimide film, aluminum foil, etc., but the present invention is not limited to these examples.

The thickness of the support film cannot be unconditionally determined because it depends on the material of the film and is usually adjusted appropriately according to the mechanical strength of the film, but usually 3 It is about 50 μm.

The thickness of the photosensitive resin composition layer is 5 to 3
The thickness is preferably 00 μm, preferably 10 to 50 μm, and if it is less than 5 μm, the coating becomes non-uniform and pinholes are easily generated during coating and drying.
If it is larger than 0 μm, the exposure sensitivity is lowered and the developing speed is slowed down, which is not preferable.

The protective film used in the present invention is such that when a photoresist film is used in the form of a roll, the photosensitive resin composition layer having adhesiveness is transferred to the support film or the photosensitive resin composition layer is used. It is used by being laminated on the photosensitive resin composition layer for the purpose of preventing dust and the like from adhering to it. Examples of such a protective film include a polyester film, a polyvinyl alcohol film, a polyethylene film, a polypropylene film, a Teflon (registered trademark) film, and the like, but the present invention is not limited to these examples. The thickness of the protective film is not particularly limited and is usually 10 to 50 μm.
m, especially 10 to 30 μm.

When the photosensitive resin composition is used in a liquid state other than the photoresist film, the photosensitive resin composition is processed by a conventional method such as a dip coating method, a flow coating method or a screen printing method. The photosensitive layer having a thickness of 1 to 150 μm can be easily formed by directly coating on the (copper) substrate to be formed. At the time of coating, a solvent such as methyl ethyl ketone, methyl cellosolve acetate, ethyl cellosolve acetate, cyclohexane, methyl cellosolve, methylene chloride, or 1,1,1-trichloroethane can be added.

In order to form an image with a photoresist film, the adhesive force between the support film and the photosensitive resin composition layer and the adhesive force between the protective film and the photosensitive resin composition layer are compared, and the one having lower adhesive force is compared. After peeling off the film, the photosensitive resin composition layer side is attached to a metal surface such as a copper surface of a copper clad substrate, and then a pattern mask is brought into close contact with the other film for exposure. When the photosensitive resin composition does not have tackiness, the other film may be peeled off and then the pattern mask may be brought into direct contact with the photosensitive resin composition layer for exposure. When the metal surface is directly coated, a pattern mask is brought into contact with the coated surface directly or through a polyester film or the like, and the metal surface is exposed.

The exposure is usually carried out by irradiation with ultraviolet rays, and as a light source at that time, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a short arc lamp, a carbon arc lamp, a xenon lamp, a metal halide lamp, a chemical lamp or the like is used. After irradiation with ultraviolet rays, heating can be performed as necessary to achieve complete curing.

After the exposure, the film on the resist is peeled off and then developed. Since the above-mentioned photosensitive resin composition is a dilute alkali developing type, development after exposure is carried out using a dilute aqueous solution of about 0.3 to 2 wt% alkali such as sodium carbonate and potassium carbonate. A surface active agent, a defoaming agent, and a small amount of an organic solvent for accelerating the development may be mixed in the alkaline aqueous solution.

After the development, etching treatment or plating treatment is performed. The etching treatment is usually performed using an acidic etching solution such as a cupric chloride-hydrochloric acid aqueous solution or a ferric chloride-hydrochloric acid aqueous solution according to a conventional method. In rare cases, an ammonia-based alkaline etching solution is also used. The plating treatment is performed by using a plating solution after performing a pretreatment using a plating pretreatment agent such as a degreasing agent or a soft etching agent. Copper plating solution, nickel plating solution,
Iron plating solution, silver plating solution, gold plating solution, tin plating solution,
Examples thereof include a cobalt plating solution, a zinc plating solution, a nickel-cobalt plating solution, and a solder plating solution.

Thus, the cured resist which is removed by stripping is formed, and the resist is stripped after the cured resist is formed. Hereinafter, a method for removing a cured resist using the photoresist remover of the present invention will be described. After the etching process or the plating process, the remaining cured resist is removed. Regarding the removal and removal of the cured resist, by using the above-mentioned photoresist release agent of the present invention, excellent effects such as improvement of the release time, release dispersibility, and low attack on metal resist plating are exhibited. In using the photoresist remover of the present invention,
As described above, it is preferably used as an aqueous solution of 5 to 30% by weight, preferably 5 to 20% by weight, more preferably 6 to 10% by weight. The temperature of the aqueous solution is preferably about 45 to 60 ° C.

The stripping device is the same as in the case of a normal aqueous solution of sodium hydroxide, and the spray pressure is 1.2 to 3 kg / cm ² , and the cured resist is stripped. Thus, the cured resist is stripped and removed by the photoresist stripping agent of the present invention, and high-density and high-definition pattern formation can be obtained.

The photoresist stripping agent of the present invention comprises a specific water-soluble amine (a), a specific ammonium hydroxide (b), a specific ammonium hydroxide (c) and benzotriazoles (d), preferably Further, since it is composed of water-soluble propylene glycol (e), it exhibits excellent effects in stripping time, stripping dispersibility, and low attack on plating, and is a photoresist stripping agent suitable for obtaining a high-density and high-definition pattern. Therefore, it is effectively used for manufacturing printed wiring boards, precision machining of metals, manufacturing lead frames, manufacturing semiconductor packages, and the like.

[0057]

The present invention will be described in more detail below with reference to examples. Unless otherwise specified, “%” and “part” are based on weight.

Examples 1 to 4 and Comparative Examples 1 to 5 The following were used as the binder polymer (f), the ethylenically unsaturated compound (g), the photopolymerization initiator (h) and other additives. A dope of the resin composition was prepared.

[0059] [Binder polymer (f)]   Methyl methacrylate / styrene / n-butyl acrylate   / Methacrylic acid = 57/15/5/23 (weight ratio) copolymerization   Body (resin content 40%, solvent: methyl ethyl ketone / isopropyl ester   Alcohol = 9/1 (weight ratio)) and the weight average molecular weight is 6   50,000, acid value 150mgKOH / g, glass transition temperature 59 parts   Is 104 ° C. (Solid content)

[0060] [Ethylenically unsaturated compound (g)]   ・ Trimethylolpropane triacrylate (TMPTA) 7.53 parts   -2,2'-bis (4-methacryloxypolyethoxyphene     Nyl) propane (EO≈10) (BPE) 30 parts

[0061] [Photopolymerization initiator (h)]   .2,2'-bis (o-chlorophenyl) -4,5,4 '     , 5'-Tetraphenyl-1,2'-biimidazole     (H1) (HABI) 3 copies   .P, p'-bis (diethylamino) benzophenone     (H2) (EAB) 0.12 part

[0062] [Other additives]   ・ Leuco crystal violet (i) (LCV) 0.3 parts   ・ Malachite Green (MG) 0.05 part

Next, each dope was coated on a polyester film having a thickness of 20 μm using an applicator having a gap of 8 mil, and left at room temperature for 1 minute 30 seconds, and then 6
The film was dried in an oven at 0 ° C., 90 ° C. and 110 ° C. for 2 minutes, respectively, and further coated with a polyethylene film having a thickness of 25 μm to form a photoresist film having a resist thickness of 40 μm, and left for one day.

After peeling off the polyethylene film of this photoresist film, the photosensitive resin composition layer was placed on a copper clad substrate preheated to 60 ° C. in an oven at a laminate roll temperature of 100 ° C. and a roll pressure of 3 kg / cm ² , It was laminated at a laminating speed of 1.5 m / min and left for 3 days. The copper clad substrate used here has a thickness of 1.6 mm, and is a substrate having a width of 200 mm and a length of 250 mm in which 35 μm copper foil is laminated on both surfaces of a glass fiber epoxy base material.

Then, on the obtained substrate, with a 2 kW mercury short arc lamp (parallel light source), the numerical value of the Stouffer 21-step step tablet (a negative film made so that the amount of light transmission gradually decreases) was 8. The exposure was performed with the following exposure amount. Fifteen minutes after the exposure, peel the polyester film, and use a 1% sodium carbonate aqueous solution at 30 ° C. as a break point (time for completely dissolving the unexposed portion) of 2
The unexposed portion was dissolved and removed by spraying at a spray pressure of 1.5 kg / cm ² for a double development time to obtain a cured resist image. This base material was plated with a copper sulfate plating solution to a copper plating thickness of 30 μm, and then with a borofluoride solder plating solution, 5 μm solder plating was performed.

After plating, the cured resist was peeled off using a photoresist peeling agent having the composition shown in Table 1 to form a high-density, high-definition pattern. As for the method of removing the cured resist, 8% of the removing solution is 50 ° C. and the spray pressure is 2 kg /
Spraying was performed for 90 seconds under the condition of cm ² .

[0067]

[Table 1] Water-soluble Ammonium Ammonium Benzotri Water-soluble Fluorine Concentration Amine Hydroxide Hydroxide Azole Phenol glycol (%) (a) (b) (c) (d) (e) (part) (part) (part) ) (Part) (Part) Example 1 MEA TMHEAH TMAH BT --- 8 (100) (9) (20) (0.8) 〃 2 MEA TMHEAH TMAH BT --- 8 (100) (13) (23) ( 1.4) 〃 3 MEA TMHEAH TMAH BT PGM 8 (100) (9) (20) (0.8) (2) 〃 4 MEA TMHEAH TMAH BT PGM 8 (100) (7) (17) (0.8) (2) Comparative example 1 --- TMHEAH TMAH BT --- 8 (9) (20) (0.8) 〃 2 MEA --- TMAH BT --- 8 (100) (20) (0.8) 〃 3 MEA TMHEAH --- BT- --8 (100) (9) (0.8) 〃 4 MEA TMHEAH TMAH --- --- 8 (100) (9) (20) 〃 5 3% sodium hydroxide aqueous solution is used

Note) The concentration (%) is the concentration as an aqueous solution. MEA: monoethanolamine TMHEAH: trimethyl (2-hydroxyethyl) ammonium hydroxide TMAH: tetramethylammonium hydroxide BT: 1,2,3-benzotriazole PGM: propylene glycol monomethyl ether

In the above steps, the resist peeling property and the plating attack property were evaluated as follows. After forming a pattern of line / space = 50 μm / 50 μm,
The space is plated with 30 μm of copper and further with 5 μm of solder, and then the stripping solution shown in Table 1 is used.
The resist was stripped by spraying at 90 ° C. and a spray pressure of 2 kg / cm ² for 90 seconds, and the resist stripping time (seconds), the presence or absence of a resist residue, and the attack on solder plating were observed. The evaluation criteria are as follows.

(Presence or absence of resist residue) ○: No residue was found △: Some residue was observed ×: Residue was observed

(Attack to solder plating) ○: No discoloration of solder plating was observed △: Some discoloration was observed ×: Discoloration was observed

Further, a 180 mm × 230 mm substrate was subjected to solid exposure (exposure amount was 8 on a 21-step Stouffer step tablet), and then the stripping solution shown in Table 1 was applied at 50 ° C. and a spray pressure of 2 kg / peel off at cm ² ,
The shape of the resist strip was observed. The evaluation criteria are as follows.

(Shape of resist strip) ○ ... Peeling piece size is less than 5mm square △: peeling piece size is less than 5 to 20 mm square ×: peeling piece size is 20 mm square or more Table 2 shows the evaluation results of Examples and Comparative Examples.

[0074]

[Table 2] Stripping time for resist stripping (seconds) Stripping residue Stripping profile Attackability Example 1 37 ○ ○ ○ 〃 2 33 ○ ○ ○ 〃 3 35 ○ ○ ○ 〃 4 42 ○ ○ ○ Comparative Example 1 60 △ ○ △ 〃 2 54 ○ △ ○ 〃 3 56 ○ ○ △ △ 〃 4 37 ○ ○ × 〃 5 42 △ × ×

[0075]

The photoresist stripper of the present invention comprises a specific water-soluble amine (a), a specific ammonium hydroxide (b), a specific ammonium hydroxide (c) and benzotriazoles (d), Since it is more preferably composed of water-soluble propylene glycol (e), it exhibits excellent effects in stripping time, stripping dispersibility, and low attack on plating, and is suitable for obtaining a pattern of high density and high definition. It is a photoresist stripping agent and is effectively used for manufacturing printed wiring boards, precision metal processing, lead frame manufacturing, semiconductor package manufacturing, and the like.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification code FI C11D 7/60 C11D 7/60 17/00 17/00 H01L 21/027 H01L 21/30 572B (56) Reference JP-A-9 -319098 (JP, A) JP 7-28254 (JP, A) JP 7-271057 (JP, A) JP 7-120937 (JP, A) JP 11-52588 (JP, A) ) (58) Fields surveyed (Int.Cl. ⁷ , DB name) G03F 7/42 C09D 9/00 C09D 201/00 C11D 7/32 C11D 7/50 C11D 7/60 C11D 17/00 H01L 21/027

Claims (8)

(57) [Claims] 1. A water-soluble amine (a) represented by the general formula (1), an ammonium hydroxide (b) represented by the general formula (2), and an ammonium hydroxide (c represented by the general formula (3). ) And a benzotriazole (d), a photoresist stripping agent. [Chemical 1] (In the formula, R ₁ , R ₂ , R ₃ and R ₄ are hydrogen atoms or carbon atoms 1
To 3 alkyl groups, which may be the same or different. n and m are integers of 0 to 2 (however, the sum of n and m is at least 2), and x is an integer of 1 to 3. [Chemical 2] (In the formula, R ₅ , R ₆ and R ₇ are alkyl groups having 1 to 3 carbon atoms and may be the same or different. N is 0 to
It is an integer of 2. ) [Chemical 3] (In the formula, R ₈ , R ₉ , R ₁₀ and R ₁₁ are hydrogen or a carbon number 1 to
4 alkyl groups, which may be the same or different. ) 2. 5 to 15 parts by weight of the ammonium hydroxide (b) represented by the general formula (2) is added to 100 parts by weight of the water-soluble amine (a) represented by the general formula (1). If the amount of ammonium hydroxide (c) represented by (3) is 15 to
25 parts by weight and 0.5 to 5 parts of benzotriazoles (d)
The photoresist stripping agent according to claim 1, wherein the photoresist stripping agent is contained in an amount of 5 parts by weight. 3. A water-soluble propylene glycol (e) represented by the general formula (4) is added in an amount of 0.1 to 10 relative to 100 parts by weight of the water-soluble amine (a) represented by the general formula (1).
The photoresist stripping agent according to claim 1 or 2, wherein the photoresist stripping agent is contained in an amount of 1 part by weight. [Chemical 4] (In formula, R <_12> , R < ₁₃ > is a hydrogen atom or a C1-C4 alkyl group, and may be the same or different. Y is 1-
It is an integer of 3. ) 4. The photoresist stripper according to claim 1, wherein the water-soluble amine (a) represented by the general formula (1) is monoethanolamine. 5. The photoresist stripping method according to claim 1, wherein the ammonium hydroxide (b) represented by the general formula (2) is trimethyl (2-hydroxyethyl) ammonium hydroxide. Agent. 6. The photoresist stripping agent according to claim 1, wherein the ammonium hydroxide (c) represented by the general formula (3) is tetramethylammonium hydroxide. 7. The photoresist stripping agent according to claim 1, further comprising water so as to be an aqueous solution of 5 to 30% by weight. 8. A binder polymer (f), an ethylenically unsaturated compound (g) and a photopolymerization initiator (h),
Binder polymer (f) as photopolymerization initiator (h)
2.5 to 5 parts by weight of the lophine dimer (h1) and 0.05 to 0.05 parts by weight of the p-aminophenyl ketone (h2), based on 100 parts by weight of the total amount of the ethylenically unsaturated compound (g).
The photosensitive resin composition containing 0.2 part by weight is provided on a substrate, and is used for peeling off a cured resist obtained by irradiating with actinic rays and curing. Photoresist remover.