JP2001215736A - Photoresist removing solution composition, removing method and circuit board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an excellent photoresist removing solution composition which brings no residue on removal and does not cause corrosion to a metallic thin film part, and to provide a removing method using the composition and a circuit board produced by the method. SOLUTION: The photoresist removing solution composition contains 60-95 wt.% water-soluble organic solvent, 0.05-10 wt.% at least one alkaline compound selected from the group comprising a tetraalkylammonium hydroxide and an organic amine, 0. 05-15 wt.% at least one compound selected from glycols each having a molecular weight of <=300 and 0.05-15 wt.% water.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resist stripping composition, and more particularly, to a photoresist suitable for photofabrication such as fine wiring and bump formation performed when a semiconductor or electronic component is mounted on a circuit board. The present invention relates to a stripping solution composition for use, a stripping method using the stripping solution composition, and a circuit board manufactured by the method.

[0002]

2. Description of the Related Art Photofabrication is a technique in which a radiation-sensitive photoresist is applied to the surface of a workpiece such as a silicon wafer or a copper-clad laminate, and the resulting coating is patterned by photolithography to obtain a pattern. A general term for technologies that manufacture various precision parts by using an electroforming technology such as chemical etching, physical etching, electrolytic etching, or electroplating alone or in combination with a workpiece as a mask. It is the mainstream of current precision processing technology.

In recent years, with the miniaturization of electronic equipment, high integration and multi-layering of semiconductor devices have been rapidly advanced, and it is necessary to mount semiconductor devices on a substrate at a high density (high-density mounting). Has become. In high-density mounting, it is necessary to miniaturize wiring and to increase the precision of minute electrodes called bumps, which are connection terminals for conducting, and such demands are expected to increase further in the future.

In high-density mounting, for example, a circuit board having bumps and fine wiring is manufactured. For the manufacture of bumps and fine wiring, a liquid resist for photolithography or a dry film resist is used. After forming the fine wiring, it is removed by chemical or physical peeling. If the resist film is left unremoved or the metal thin film on the substrate surface is corroded in this peeling step, conduction through wirings or bumps cannot be sufficiently obtained, causing a problem. The stripping of the resist is more difficult as the height of the remaining pattern or bump is higher with respect to the width of the portion to be removed by the development, and the stripping of the photoresist is more likely to occur. If photoresist residue remains,
Although the peeling residue can be removed by ashing treatment using oxygen plasma, it is not practical as an industrial manufacturing process because a special device is required, and the process is lengthened and the manufacturing cost is increased. Until now, various stripping compositions have been developed, but no industrially satisfactory stripping compositions having no peeling residue and no metal corrosion have been found.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a photoresist which is necessary for manufacturing circuit boards such as fine wiring and bump formation, particularly a negative type liquid photoresist and a negative type dry film resist which can be developed with alkali. To provide an extremely excellent resist stripping composition having excellent stripping ability and not corrosive to a metal substrate such as aluminum or a wiring under a photoresist to be stripped, and to use a new stripping solution for resist. And a circuit board manufactured by peeling (in the present invention, the circuit board is used in the sense of an electronic component substrate having one or both of bumps and fine wiring). It is.

[0006]

In order to achieve the above object, the present invention relates to a water-soluble organic solvent of 60 to 95% by weight, at least one kind of an alkaline compound selected from the group consisting of tetraalkylammonium hydroxide and organic amine. 0.
A stripper composition for a photoresist, comprising 0.05 to 15% by weight of at least one compound selected from glycols having a molecular weight of 300 or less and 0.05 to 15% by weight of water and 0.05 to 15% by weight of water. Offer things. Furthermore, the present invention provides a stripping method using the stripping solution composition, and a circuit board manufactured by the stripping method, particularly a circuit board having bumps or fine wiring.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
Water-soluble organic solvent used in the stripping composition of the present invention,
Dimethylsulfoxide (abbreviated as DMSO), dimethylformamide, dimethylacetamide, 1-methyl-2-pyrrolidinone, 2,4-dimethylsulfolane, dimethylsulfone, 1,3-dimethyl-2-imidazolidinone (DM
I), γ-butyrolactone, acetone, 1,4-dioxane, tetrahydrofuran, methanol, ethanol, isopropyl alcohol, and the like. Of these, dimethyl sulfoxide is particularly preferred. These water-soluble organic solvents may be used alone or in combination of two or more.

The amount of the water-soluble organic solvent used is 60 to 95% by weight, preferably 65 to 93% by weight, more preferably 68 to 90% by weight in the stripping composition of the present invention. If the amount of the preferred water-soluble organic solvent is less than 60% by weight, the compatibility of the stripping solution composition with the photoresist may be reduced, and a stripping residue may be generated. The amount of the water-soluble organic solvent used is 9
If it exceeds 5% by weight, the peeling ability may be reduced, and peeling residue may be generated.

The tetraalkylammonium hydroxide used in the stripping composition of the present invention includes a compound represented by the general formula (2). ^{R 3 R 4 R 5 R 6} N + OH - (2) R 3 shown in formula ^{(2), R 4, R} 5 and R ⁶ represents an alkyl group having an alkyl group or a substituted group, or different may be the same May be. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, and a benzyl group. Examples of the substituent of the alkyl group having a substituent include a hydroxyl group and an alkoxy group. For example, a 2-hydroxyethyl group, a 3-hydroxypropyl group, a 4-hydroxybutyl group, a 2-methoxyethyl group, a 2- (2- (Hydroxyethoxy) ethyl group and the like. A specific example of such a tetraalkylammonium hydroxide is tetramethylammonium hydroxide (TMA
H), tetraethylammonium hydroxide,
Tetra (n-propyl) ammonium hydroxide, tetra (n-butyl) ammonium hydroxide, benzyltrimethylammonium hydroxide, tetra (2-
Hydroxyethyl) ammonium hydroxide, trimethyl (2-hydroxyethyl) ammonium hydroxide, trimethyl {2- (2-hydroxyethoxy) ethyl} ammonium hydroxide, dimethyldiethylammonium hydroxide and the like, among which tetramethylammonium Hydroxide, trimethyl (2
It is preferred to use (-hydroxyethyl) ammonium hydroxide.

The organic amine used in the present invention includes monoethanolamine (abbreviated as EA), piperazine,
(2-hydroxyethyl) piperazine, morpholine,
Examples thereof include 1,2,3-benzotriazole, 4- (2-hydroxyethyl) pyridine, 2- (2-hydroxyethyl) pyridine, lutidine, and collidine, among which monoethanolamine is preferable. These tetraalkylammonium hydroxides and organic amines may be used alone or as a mixture of two or more. The amount of at least one alkaline compound selected from the group consisting of tetraalkylammonium hydroxide and organic amine is 0.05 to 10% by weight, preferably 0.08 to 9% by weight, more preferably 0.1 to 10% by weight. 8% by weight. When the content is less than 0.05% by weight, the peeling ability is low, and a peeling residue may occur. When the content exceeds 10% by weight, corrosion of the metal substrate may be observed.

The glycols having a molecular weight of 300 or less used in the present invention are preferably compounds represented by the general formula (3). HO (CHR ¹ —CHR ² O) _n H (3) (where R ¹ and R ² each independently represent hydrogen or a methyl group (except when both groups are simultaneously a methyl group), and n Represents an integer selected from 1 to 4.) Examples of the glycols include ethylene glycol (abbreviated as EG), diethylene glycol (abbreviated as DEG), triethylene glycol (abbreviated as TOEG), tetraethylene glycol (abbreviated as TEEG), Examples thereof include propylene glycol (abbreviated as PG), dipropylene glycol (abbreviated as DPG), tripropylene glycol (abbreviated as TOPG), tetrapropylene glycol (abbreviated as TEPG), and isomers thereof. Of these, ethylene glycol, diethylene glycol, triethylene glycol and tetraethylene glycol are preferred, and ethylene glycol is particularly preferred.

The amount of the glycol compound having a molecular weight of 300 or less used in the present invention is 0.05 to 15% by weight, preferably 0.1 to 13% by weight, more preferably 0.5 to 1% by weight.
2% by weight. If the content is less than 0.05% by weight, corrosion of the metal on the substrate such as aluminum may be observed, and if the content exceeds 15% by weight, the peeling ability may be reduced and the peeling residue may be generated. The content of water used in the stripping composition of the present invention is 0.1.
From 0.5 to 15% by weight, preferably from 0.1 to 13% by weight,
More preferably, it is 0.2 to 12% by weight. When the water content is less than 0.05%, the peeling ability is low and peeling residue may be observed. When the water content exceeds 15% by weight, corrosion of a metal on a substrate such as aluminum may be observed.

The stripping composition of the present invention may be used by adding other known components, if necessary. Other components include, for example, a surfactant for the purpose of lowering the surface tension and increasing the affinity for the photoresist.

Specific examples of the surfactant include cationic surfactants such as stearylamine acetate, dimethyllaurylbenzylammonium chloride, trimethylbenzylammonium chloride, lauryldimethylamine oxide, laurylbetaine, stearylbetaine, laurylcarboxydimethylhydroxyethyl. Amphoteric surfactants such as imidazolinium betaine, sodium alkylnaphthalenesulfonate, sodium dialkylsulfosuccinate, sodium alkyldiphenyletherdisulfonate, sodium polyoxyethylene alkylether sulfate, sodium polyoxyethylenealkylphenylether sulfate, sodium alkane sulfonate, Anion such as sodium salt of β-naphthalenesulfonic acid formalin condensate Surfactant, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyethylene glycol monostearate, higher fatty acid ester of pentaerythritol, higher fatty acid ester of trimethylolpropane, sorbitan oleate, polyoxyethylene stearylamine ether Polyoxyethylene alkyl ether (for example, manufactured by Daiichi Kogyo Seiyaku Co., Ltd .; Neugen ET-10)
7, non-ionics such as ET-140E and ET-149), glycerol tristearate, and polyoxyethylene polyoxypropylene glycol alkyl ether (for example, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd .; Evan 450, 680, and 785). -Based surfactants, furthermore, fluorine-based surfactants, for example, manufactured by BM Chemie; BM-1000, BM-110
0, manufactured by Dainippon Ink and Chemicals, Inc .; Megafac F1
42D, F172, F173, F183, manufactured by Sumitomo 3M Limited; Florard FC-135, FC-1
70C, FC-430, FC-431, Asahi Glass Co., Ltd.
Made; Surflon S-112, S-113, S-13
1, S-141, S-145, manufactured by Toray Dow Corning Silicone Co., Ltd .; SH-28PA, SH-190, SH
-193, SZ-6032, SF-8428 and the like.

When these surfactants are added, the amount of addition is preferably 5% by weight or less in the stripping solution composition.
If it exceeds 5% by weight, bubbles may be generated at the time of peeling and peeling may be difficult.

The stripping composition of the present invention may be used, if necessary,
A known antifoaming agent may be added for use. Examples of the antifoaming agent include polyalkylene glycols, silicon compounds, inorganic particles mixed silicon compounds, sorbitan fatty acid esters, aluminum carboxylate,
Examples thereof include higher alcohols having 6 or more carbon atoms, higher fatty acids, paraffin wax, liquid paraffin, mineral acids, light oils, and vinyl acetate / ethylene emulsions. Specifically, antifoaming agents that are commercially available, for example, Anticross manufactured by Daiichi Kogyo Seiyaku Co., Ltd., and AQUALEN SB-551, 800, and 80 manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd.
5, 1488, 7447, SB-551, 30
62, SB-905, Carolin 102, 104, 202, 302, DC-53, manufactured by Sanyo Chemical Industries, Ltd.
5 and the same DF.

The resist using the resist stripping solution of the present invention is not particularly limited, but an alkali-soluble polymer such as an alkali-soluble poly (meth) acrylate is used as a resin component, and a radical-generating light Dry film resist using a radical-generating type photopolymerization initiator using a alkali-soluble negative type liquid photoresist using a polymerization initiator or an alkali-soluble poly (meth) acrylate ester as a resin component, a novolak resin and a naphthoquinonediazide And a positive or negative chemically amplified photoresist, and both negative and positive dry film resists. The photoresist to which the present invention can be preferably applied is an alkali-soluble negative-type liquid resist and an alkali-soluble negative-type dry film resist,
Particularly preferred is an alkali-soluble negative liquid resist.

Although the thickness of the photoresist to be applied is not particularly limited, it is usually used at a thickness of 20 to 150 μm for forming fine wirings and bumps which are the object of the present invention. The method for applying the liquid photoresist is not particularly limited, but any method such as spin coating, dipping, die coating, curtain coating, and printing may be used.

When a dry film resist is used, a thin film is formed by a lamination method. The lamination method may be either thermocompression lamination under normal pressure or vacuum lamination under vacuum. The temperature of the laminating roll during lamination is preferably 50 to 150
° C, more preferably 70 to 120 ° C. When the laminating temperature is lower than 50 ° C., sufficient adhesion to the substrate may not be obtained, and the resist pattern may be peeled off during development. When the laminating temperature is higher than 150 ° C., the resist is deteriorated by heat during lamination and a desired resist pattern is obtained. There may not be. The stripping solution composition of the present invention is also suitable for stripping dry film resists.

An exposure method for forming a photoresist pattern can be arbitrarily selected according to the purpose, using a commercially available exposure apparatus such as an aligner, a projection, and a stepper. Can be used. After the formation of the photoresist pattern, plating is applied to the portions removed by development. Either electrolytic plating or electroless plating may be used as a plating method, and a metal type of plating is selected and used as necessary, such as gold, copper, nickel, and solder. After the plating is completed, the photoresist is stripped using the stripping solution composition of the present invention.

Next, a stripping method using the stripping solution composition of the present invention and a circuit board manufactured by the stripping method will be described. The stripping method of the present invention is to strip and remove a resist pattern remaining after forming fine wiring and / or bumps on a substrate having a metal thin film on the entire surface or part using the stripping solution composition of the present invention. This is a feature of the resist stripping method.

The circuit board of the present invention includes: a. A step of forming a metal thin film over the entire surface or a part of a silicon wafer or glass substrate; b. A step of forming a photoresist film on the metal thin film; c. Exposing and developing the photoresist film through a predetermined mask; d. Plating the exposed substrate; and e. Removing the remaining resist film using the remover composition of the present invention. And a circuit board having fine wirings and / or bumps manufactured by a method including:

The details will be described below. A photoresist, for example, an alkali-developable negative liquid resist is spin-coated on a substrate, which is entirely or partially covered with a metal such as copper, gold, vanadium, or aluminum, to form a photoresist coating film After that, or after laminating a dry film resist that can be developed with an alkali on a substrate to form a photoresist coating film, exposure is performed through a predetermined mask and development is performed to obtain a predetermined resist pattern.

The temperature of the stripping solution at the time of stripping is from 20 to 9
0 ° C., preferably 25-80 ° C., more preferably 30 ° C.
７０70 ° C. When the temperature of the stripping solution is lower than 20 ° C., the stripping speed is slow and impractical, and the stripping residue may be observed. On the other hand, if the stripping temperature exceeds 90 ° C., corrosion on the metal may be observed, or a specific component in the stripping solution composition, for example, water may evaporate and become unusable. As a peeling method, there is a dipping method in which a substrate to be peeled is immersed in a peeling tank containing a peeling liquid, and the peeling liquid is stirred to peel. When peeling by the dipping method, ultrasonic waves may be used together. In addition, it is also possible to perform stripping by a shower method in which a stripping solution is sprayed through a spray nozzle.

The stripping time can be appropriately selected depending on the shape and thickness of the photoresist pattern, the temperature of the stripping solution, the stripping method and the like, but is usually about 1 to 20 minutes. After removing the photoresist, the substrate is washed with water and dried by spraying with air or baking. If the metal pattern formed by plating in the above process is a line pattern, it is used as a wiring, and if it is a dot pattern, it is used as a bump. Wiring and bumps manufactured using the stripping solution composition of the present invention and the same,
It is possible to manufacture a circuit board having fine wirings and bumps, which has never existed before. The stripping solution composition of the present invention has no peeling residue after the photoresist stripping treatment, and further has extremely low or no corrosiveness with respect to metals such as aluminum. This is useful for manufacturing a circuit board used for high-density wiring.

[0026]

EXAMPLES The present invention will be described below in more detail with reference to examples, but the present invention is not limited to these examples. In addition,
In the following, “%” and “parts” are “% by weight” and “parts by weight” unless otherwise specified. <Preparation of Photoresist for Stripping> Liquid Photoresist Example 1 (abbreviated as L1) Methacrylic acid / dicyclopentanyl methacrylate / styrene / 1,3-butadiene = 25/45/15/15
To 100 parts by weight of an alkali-soluble polymer (Polymer 1) obtained by copolymerizing the following components in a weight ratio, a uniform solution containing the following components is prepared, filtered, and alkali-developed negative-type liquid photoresist (L1 ) Was prepared. Glycerin triacrylate 50 parts by weight 2,2-Dimethoxy-2-phenylacetophenone 25 parts by weight Florard FC430 (manufactured by Sumitomo 3M Ltd.) 0.5 parts by weight 120 parts by weight methyl 3-methoxypropionate

Liquid photoresist examples 2 to 8 (L2 to L8
In the same manner as in L1, except that the following (Polymer 2) to (Polymer 8) were used instead of the alkali-soluble polymer in the preparation of L1, an alkali-developing negative liquid photoresist (L2 to L8) was prepared. Prepared.

(Polymer 2) methacrylic acid / dicyclopentanyl methacrylate / styrene / 2-hexahydrophthaloyloxyethyl methacrylate / isoprene =
19/46/15/15/5 (Polymer 3) methacrylic acid / dicyclopentanyl methacrylate / n-butyl acrylate / methoxydipropylene glycol acrylate / isoprene = 19/4
6 / 22.5 / 7.5 / 5 (Polymer 4) methacrylic acid / dicyclopentanyl methacrylate / n-butyl acrylate / isoprene = 1
9/46/30/5 (Polymer 5) methacrylic acid / dicyclopentanyl methacrylate / 2-hexahydrophthaloyloxyethyl methacrylate / styrene / isoprene = 14/46 /
15/20/5 (Polymer 6) methacrylic acid / n-butyl acrylate / p-hydroxy-α-methylstyrene = 5/60/35 (Polymer 7) methacrylic acid / n-butyl acrylate / dicyclopentanyl methacrylate / p -Hydroxy-
α-methylstyrene = 20/20/40/20 (Polymer 8) methacrylic acid / n-butyl acrylate / p-hydroxy-α-methylstyrene = 5/60/35

In the liquid photoresist examples 9 and 10, commercially available photoresists were used as they were. Liquid photoresist example 9 (abbreviated as L9) JSR Corporation negative type photoresist THB-1 for thick film
20N liquid photoresist example 10 (abbreviated as L10) Photoresist THB-6 for positive type thick film manufactured by JSR Corporation
11P

Dry Film Resist Example 1 (abbreviated as F1) The photosensitive resin composition of Liquid Photoresist Example 3 (L3) was coated on a polyethylene terephthalate (PET) film having a thickness of 25 μm and a width of 400 mm using a die coater. , Applied so that the film thickness after drying is 25 ± 1μm,
It was dried by passing through an oven at a temperature of 60 ° C. to produce a dry film resist (F1). 25 μm thick polyethylene (PE) on the surface of this dry film resist
The film was laminated and protected.

In Dry Film Resist Example 2, a commercially available negative type dry film resist was used as it was. Dry film resist example 2 (abbreviated as F2) FDR-4000 manufactured by JSR Corporation (resist film thickness 40 μm)
m)

<Preparation of Circuit Board> Fabrication method of circuit board using liquid photoresist (A
A negative type liquid photoresist is spin-coated on a 1500-Å-thick silicon wafer with a sputter-deposited aluminum film having a thickness of 1500 angstroms, and the coated film is pre-baked on a hot plate at 90 ° C. for 10 minutes. A 50 μm photoresist film is formed. Then, 500 mJ / c through a photomask having a square pattern with a punch pattern size of 60 μm on each side.
Exposure is performed with a light irradiation amount of m ² (converted using a sensor having a wavelength of 365 nm). Next, the exposed photoresist film is developed with a 2.38% by weight aqueous solution of tetramethylammonium hydroxide to prepare a substrate having a predetermined pattern of the photoresist. After the substrate is post-baked at 100 ° C. for 10 minutes, plating is performed. The plating is
Using a cyan gold plating solution N44 manufactured by Echem Cat Co., Ltd., a plating bath temperature of 60 ° C., and a plating current density of 0.67.
A / dm ² is performed while stirring the plating solution to a film thickness of 20 μm.
m gold-plated bumps (cubes with a side of 60 μm and a height of 20 μm) are formed. After washing the plated substrate with water, the substrate is blown with air and dried to produce a circuit board from which the resist has not been stripped.

2. Method of fabricating circuit board using dry film resist (abbreviated as method B) A dry film resist is roll-laminated at a temperature of 90 ° C. on a 1500-Å thick silicon wafer with a sputtered aluminum film having a thickness of 1500 angstroms. Thickness (25 μm for F1, 4 μm for F2
(0 μm). Next, exposure is performed with a light irradiation amount of 350 mJ / cm ² through a photomask having a wiring pattern of line / space = 40 μm / 40 μm. Next, the exposed photoresist is developed using a 1% by weight aqueous solution of sodium carbonate at a temperature of 30 ° C. and a spray pressure of 1.5 kgf / cm ^{2 for} 2 minutes to produce a wiring substrate having a predetermined pattern of the photoresist. . After the substrate is post-baked at 100 ° C. for 5 minutes, plating is performed. The plating was carried out using a cyan gold plating solution (N44, manufactured by N.C.
The plating is performed at a current density of 0.67 A / dm ² while stirring the plating solution to form a gold-plated wiring having a thickness of 20 μm and a wiring width of 40 μm. After washing the plated substrate with water,
Air is blown and dried to produce a circuit board from which the resist has not been stripped.

<Method of Stripping Photoresist> (abbreviated as Method C) A circuit board before resist stripping is immersed in a stripping solution composition maintained at a predetermined temperature for 5 minutes, washed with running water, then blown with air and dried. Thus, a circuit board from which the resist has been stripped is obtained. <Evaluation method of circuit board after resist stripping> (abbreviated as method D) The degree of residue removal and the corrosion state of the aluminum film on the substrate surface are observed using a scanning electron microscope (SEM) and an optical microscope.

<Preparation of stripping solution composition> Preparation of stripping solution composition (H1): 2610 g of dimethyl sulfoxide (DMS) was placed in a 3 L separable flask.
O), 60 g of tetramethylammonium hydroxide (TMAH), 150 g of ethylene glycol (EG)
And 180 g of water were weighed and stirred at room temperature for 30 minutes to prepare a stripping composition. The weight ratio of the composition is shown in the stripping solution composition column of stripping solution No. H1 in Table 1. (H1: D
MSO / TMAH / EG / water = 87/2/5/6)

Preparation of stripper compositions (H2 to H13): Stripper compositions (H2 to H13) of the present invention were prepared in the same manner as in the preparation of stripper composition (H1). The contents of the composition are described in the stripping solution composition column of Tables 1 and 2.

Stripping composition for Comparative Example (CH1 to CH8)
Preparation: Stripper compositions (CH1 to CH8) outside the scope of the present invention were prepared in the same manner as in the preparation of stripper composition (H1). The contents of the composition are shown in the stripping solution composition column of Table 3.

<Examples> Example 1-1 A circuit board before the resist was peeled off was prepared by using the above-mentioned (L1) as a liquid photoresist and by the circuit board manufacturing method (Method A). The circuit board from which the resist has not been stripped is stripped using the stripping solution composition (H1) of the present invention in accordance with the above-described photoresist stripping method (Method C, but with a stripping temperature of 70 ° C.). It was created. Next, the circuit board was evaluated according to the evaluation method (Method D) to evaluate the stripping solution composition. The experimental conditions and evaluation results are shown in Table 1. No peeling residue was observed on the bump portion of the obtained circuit board, and the board after peeling was good without corrosion.

Examples 1-2 to 1-11 The type of the stripping solution composition was kept constant at H1, the type of the photoresist was changed to L2 to L10 and L1, and the stripping temperature was set at the same level as in Example 1-11. The experiment and evaluation were performed as in Example 1-1 except that the temperature was changed to 50 ° C. The experimental conditions and results are shown in Table 1.

Examples 1-12 and 1-13 Two types of circuit boards before the resist was peeled off were prepared by using a dry film resist (F1 and F2) by a circuit board manufacturing method (Method B). Using the stripping solution composition (H1), the resist was stripped according to the photoresist stripping method (stripping temperature: 60 ° C.) to prepare a circuit board. Then, according to the evaluation method, by observing the circuit board,
The stripper composition was evaluated. The experimental conditions and evaluation results are shown in Table 1.

Example 2 and Example 3 A method of manufacturing a circuit board (A) using a photoresist (L1)
Method), two circuit boards before peeling the resist were prepared. By using the stripper composition (H2 and H3) of the present invention to prepare a circuit board according to the photoresist stripping method (stripping temperature 70 ° C.) and observing the circuit board according to the evaluation method, The stripper composition was evaluated. The experimental conditions and evaluation results are shown in Table 1.

Example 4-1 to Example 4-3 Using the liquid photoresist (L1) and the dry film resist (F1, F2), the method for manufacturing the circuit board (L1 is A method, F1, F2 was used according to the B method) to prepare three types of circuit boards before the resist was stripped. Using the stripper composition (H4) of the present invention for these,
A circuit board was prepared according to the photoresist stripping method (stripping temperature of 50 ° C.), and the circuit board was observed according to the evaluation method to evaluate the stripping liquid composition. Table 2 shows the experimental conditions and evaluation results.

Examples 5 to 10 Six circuit boards before the resist was stripped were prepared by using the liquid photoresist (L1) and following the circuit board manufacturing method (Method A). A circuit board was prepared according to a photoresist stripping method (stripping temperature of 50 ° C.) using the stripping solution composition (H4 to H10) of the present invention in which the type of glycol was changed, and the circuit board was stripped according to the evaluation method. By observing, the release liquid composition was evaluated. Table 2 shows the experimental conditions and evaluation results.

Example 11 Using a liquid photoresist (L1), a circuit board before the resist was stripped was manufactured in accordance with the circuit board manufacturing method (Method A). Using the stripping solution composition (H11), a circuit board was prepared according to the photoresist stripping method (stripping temperature: 70 ° C.), and the circuit board was observed according to the evaluation method to evaluate the stripping solution composition. Was done. Table 2 shows the experimental conditions and evaluation results.

Example 12-1 to Example 12-3 The photoresist (L1, F1, F2) was used as a photoresist, and a resist was prepared in accordance with the circuit board manufacturing method (L1 was used for the A method, F1, F2 was used for the B method). Three types of circuit boards without peeling were prepared. About these, as a stripping solution composition (H1
2: using a water-soluble organic solvent of DMSO / DMI) and removing the photoresist (stripping temperature of 6).
0 ° C.), and a circuit board is manufactured according to the evaluation method.
The stripper composition was evaluated by observing the circuit board. Table 2 shows the experimental conditions and evaluation results.

Example 13 Using a liquid photoresist (L1), a circuit board from which the resist was not stripped was manufactured according to the circuit board manufacturing method (Method A). Using (H13: using monoethanolamine as the organic amine) as the stripping solution composition,
A circuit board was prepared according to a photoresist stripping method (stripping temperature: 70 ° C.), and the circuit board was observed according to an evaluation method to evaluate the stripping liquid composition. Table 2 shows the experimental conditions and evaluation results.

Comparative Example 1-1 Using a liquid photoresist (L1), a circuit board from which the resist was not peeled was manufactured according to the circuit board manufacturing method (Method A). A circuit board was prepared according to a photoresist stripping method (stripping temperature of 60 ° C.) using (CH1: one containing no glycols essential in the present invention) as a stripping solution composition, and evaluated according to an evaluation method. Table 3 shows the experimental conditions and the evaluation results. In the case of this stripping solution composition, a slight stripping residue was observed on the circuit board, which was unacceptable.

Comparative Example 1-2 A stripping solution composition (CH1) was prepared in the same manner as in Comparative Example 1-1 except that the dry film resist (F1) was used and the method for producing a circuit board (Method B) was followed. evaluated. Table 3 shows the experimental conditions and the evaluation results. In the case of this stripping solution composition, a stripping residue was observed on the circuit board, and the board was rejected.

Comparative Example 2-1 and Comparative Example 2-2 Using the above (L1, F2) as a photoresist, according to the circuit board manufacturing method (L1 is A method, F2 is B method)
Two types of circuit boards from which the resist was not stripped were produced. A photoresist stripping method (stripping temperature of 60) using (CH2: one containing an excess of glycols) as a stripping solution composition.
C), and a circuit board was prepared according to the evaluation method. Table 3 shows the experimental conditions and the evaluation results.
In this stripping solution composition, no corrosion was observed on the two types of circuit boards, but peeling residue was observed, and both were rejected.

Comparative Examples 3-1 to 2-2 Comparative Examples 2-1 to 2-2 were conducted except that (CH3: one containing an excessive amount of an alkali compound) was used as the stripping solution composition.
The experiment and evaluation were performed in the same manner as in Example 2. Table 3 shows the experimental conditions and the evaluation results. In the case of this stripping composition, the two types of circuit boards had no peeling residue and were good, but corrosion was observed, and both were rejected.

Comparative Examples 4 to 8 Using the above (L9) as a photoresist, five circuit boards from which the resist had not been stripped were manufactured according to the method for manufacturing a circuit board (Method A). CH4 ~
8), a circuit board was prepared according to a photoresist stripping method (stripping temperature 60 ° C.), and evaluated according to an evaluation method. Table 3 shows the experimental conditions and the evaluation results. The characteristics of this stripping composition are (CH4: too small amount of alkali compound), (CH5: too much glycols), (CH
6: glycols too small), (CH7: water too much),
(CH8: water was too small), but as a result of the evaluation, peeling residue or corrosion was observed, and all five types failed.

<< Description of Tables 1 to 3 >>》, Δ,
And × indicate the following:

The abbreviations in the table have the following meanings. (Water-soluble organic solvent) DMSO = dimethylsulfoxide DMI = 1,3-dimethyl-2-imidazolidinone (tetraalkylammonium hydroxide) TMAH = tetramethylammonium hydroxide (organic amine) EA = monoethanolamine (glycols) EG = ethylene glycol DEG = diethylene glycol TOEG = triethylene glycol TEEG = tetraethylene glycol PG = propylene glycol DPG = dipropylene glycol TOPG = tripropylene glycol TEPG = tetrapropylene glycol

[0054]

[Table 1]

[0055]

[Table 2]

[0056]

[Table 3]

[0057]

As can be seen from the results shown in Tables 1 and 2, the resist stripping solution composition according to the present invention does not show any photoresist residue at the time of stripping, and is susceptible to corrosion. It is an excellent stripper composition which does not corrode, and can be used for any of negative type liquid photoresist, positive type liquid photoresist and dry film resist. Using the resist stripping solution composition according to the present invention, the resist can be stripped in the final step of manufacturing a circuit board having bumps and fine wiring, and a circuit board having bumps and fine wiring can be manufactured. Was.

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[Procedure amendment]

[Submission date] February 7, 2000 (2000.2.7)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0055

[Correction method] Change

[Correction contents]

[0055]

[Table 2]

 ────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Katsutoshi Igarashi 2-11-24 Tsukiji, Chuo-ku, Tokyo FSR term in JSR Co., Ltd. (reference) 2H096 AA00 AA25 AA26 BA01 LA02 LA03 5E339 CE12 CG01 CG04 EE10 GG02

Claims (6)

[Claims] (1) 60 to 95% by weight of a water-soluble organic solvent, at least one alkaline compound selected from the group consisting of tetraalkylammonium hydroxide and organic amine 0.0
5 to 10% by weight, at least one compound selected from glycols having a molecular weight of 300 or less 0.05 to 15% by weight
A stripper composition for a photoresist, comprising 0.05 to 15% by weight of water. 2. The stripper composition according to claim 1, wherein the glycol is a compound represented by the general formula (1). HO (CHR ¹ -CHR ² O) _n H (1) (wherein R ¹ and R ² each independently represent hydrogen or a methyl group (except when both groups simultaneously become a methyl group), and n Represents an integer selected from 1 to 4) 3. The organic amine is monoethanolamine, piperazine, 1- (2-hydroxyethyl) piperazine, morpholine, 1,2,3-benzotriazole,
The stripper according to claim 1 or 2, wherein the stripper is at least one compound selected from the group consisting of (2-hydroxyethyl) pyridine, 2- (2-hydroxyethyl) pyridine, lutidine and collidine. Composition. 4. The stripping composition according to claim 1, which is used for stripping a negative liquid resist. 5. A stripping method using the stripping solution composition according to claim 1. 6. A circuit board peeled by the method according to claim 5.