JP2001350277A - Remover for photoresist and/or etching resistant resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a remover which can remove a photoresist film or an etching resistant resin composition film remaining on the surface of a substrate after etching in a short time, does not cause the tarnish and corrosion of a metallic material used as the substrate and ensures easy washing work and easy waste water treatment because the remover does not use a chelating agent and is less liable to cause foaming in washing and in waste water treatment. SOLUTION: The remover consists of 1-10 wt.% one or more selected from polyols and their derivatives, 0.001-0.1 wt.% one or more selected from anionic surfactants, nonionic surfactants and fluorine-containing surfactants, 5-40 wt.% alkali hydroxide and the balance water.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a release agent for a photoresist and / or an etching resistant resin composition. In the production of a shadow mask, an aperture grill, a lead frame, and other etched parts, a photoresist film or an etching-resistant resin composition film remaining on the substrate surface after the substrate is etched is removed with a release agent and washed with water.
For example, when manufacturing a shadow mask by a two-step etching method, a photoresist film having a desired pattern is formed on both sides of a thin metal plate, and primary etching is performed on both sides to form a small-hole opening pattern on one side, and on the other side, After forming the large-hole opening pattern, an etching-resistant resin composition film is formed on one surface on the small-hole opening pattern side, and the other surface on the large-hole opening pattern side is secondarily etched to reduce the large-hole opening pattern. Penetrate through the hole opening pattern. After the metal sheet is thus etched in two stages, the photoresist film and the etching-resistant resin composition film remaining on the surface of the metal sheet are peeled off with a release agent and washed with water. The present invention relates to the improvement of the release agent as described above.

[0002]

2. Description of the Related Art Conventionally, aqueous solutions of caustic alkali, usually aqueous solutions of caustic soda, have been used as the above-mentioned photoresist and / or stripping agent for etching-resistant resin compositions. However, such a release agent has a problem that it takes time to remove the photoresist film or the etching-resistant resin composition film remaining on the substrate surface after etching, and causes discoloration and corrosion of the metal material used as the substrate. . In order to shorten the stripping time, as a similar stripping agent, an aqueous solution of caustic alkali mixed with a chelating agent, for example, an organic carboxylate or an amine compound is also used. However, such a stripping agent has a problem that a chromium compound mainly contained in a photoresist or an etching-resistant resin composition forms a chelate, which is carried into drainage water, so that the removal treatment is very troublesome.

[0003]

The problem to be solved by the present invention is that a photoresist film or an etching-resistant resin composition film remaining on the surface of a substrate after etching can be peeled off in a short time, so that it can be used as a substrate. It is an object of the present invention to provide a non-chelating type release agent which does not cause discoloration or corrosion of a metal material and is easily treated for drainage.

[0004]

The present invention for solving the above-mentioned problems comprises 1 to 10% by weight of the following component A, 0.001 to 10% by weight.
The present invention relates to a photoresist and / or a stripping agent for an etching resistant resin composition comprising 0.1% by weight of the following component B, 5 to 40% by weight of the following component C, and the balance being water. A component: One or more selected from polyhydric alcohols and derivatives thereof B component: One or more selected from anionic surfactants, nonionic surfactants, and fluorosurfactants C component: Caustic

The release agent according to the present invention comprises A component, B component,
It is a three-component system consisting of component C and water, excluding water. The component A used in the present invention is one or more selected from polyhydric alcohols and derivatives thereof. The polyhydric alcohol used as the component A includes 1) ethylene glycol, diethylene glycol, triethylene glycol,
Tetraethylene glycol, polyethylene glycol,
Dihydric alcohols such as propylene glycol, dipropylene glycol, trimethylene glycol, butanediol, pentanediol, hexanediol, cyclopentanediol, and cyclohexanediol; 2) trihydric alcohols such as glycerin; Alcohols having four or more valences, such as sorbitol, may be mentioned. Of these, dihydric or trihydric aliphatic alcohols are preferred.

Examples of the polyhydric alcohol derivative used as the component A include various known per se such as the above-mentioned polyhydric alcohol in which a part or all of the hydroxyl groups are etherified or esterified. . Among them, monoalkyl ethers of dihydric or trihydric aliphatic alcohols are preferable. Such preferred polyhydric alcohol derivatives include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether,
Examples include triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, glycerin monomethyl ether, glycerin monoethyl ether, and the like.

The component A is one or more selected from polyhydric alcohols and derivatives thereof as described above.
As the component A, it is preferable to use a mixture of a polyhydric alcohol and a derivative of the polyhydric alcohol. Among them, a mixture of a dihydric or trihydric aliphatic alcohol and a monoalkyl ether of a dihydric or trihydric aliphatic alcohol is more preferable.

The B component used in the present invention is one or more selected from anionic surfactants, nonionic surfactants and fluorine-containing surfactants. Among them, one or more selected from anionic surfactants and fluorine surfactants are preferred. Examples of such surfactants include various kinds of surfactants known per se. Examples of the anionic surfactant include an alkyl sulfonate or an alkyl ether sulfonate, and examples of the fluorosurfactant include perfluoroalkyl. More preferably, a sulfonate or perfluoroalkylcarboxylate is used. These surfactants improve the wet penetration of the release agent with respect to the photoresist film and the etch-resistant resin composition film remaining on the substrate surface after etching, and as a result, for removing these films in a short time. Auxiliary.

The C component used in the present invention is caustic. Examples of the caustic alkali include various kinds of known caustic alkalis, and among them, caustic soda or caustic potash is preferable.

The release agent according to the present invention comprises the components A, B, C and water as described above, but 1 to 10% by weight of the component A, 0.001 to 0.1% by weight. % Of component B, 5 to 40% by weight of component C and the balance being water, preferably 3 to 10% by weight of component A,
0.003 to 0.1% by weight of component B, 10 to 30% by weight
And the balance consists of water. Even if the content of any of the components is out of the above range, it is difficult to achieve the intended purpose. For example, when the content of the component B is more than 0.1% by weight, wastewater generated by the water washing at the time of water washing after peeling off the photoresist film or the etching resistant resin composition film remaining on the substrate surface is further removed. During the treatment, the foaming is severe, and the washing operation and drainage treatment become troublesome. On the other hand, if the content is less than 0.001% by weight, the photoresist film or the etching resistant resin remaining on the surface of the substrate after etching. It takes time to peel off the composition film, which causes discoloration and corrosion of the metal material used as the base material.

In the production of shadow masks, aperture grills, lead frames, and other etched parts, the release agent of the present invention removes a photoresist film or an etching resistant resin composition film remaining on the surface of a substrate after the substrate is etched. It is used when peeling. Above all, when applied in the case of manufacturing a shadow mask or an aperture grill by the two-stage etching method as described above, the effect is more manifested.

[0012]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the release agent according to the present invention include the following 1) to 10: 1) As a component A, 5 parts by weight of propylene glycol and 1 part by weight of ethylene glycol monobutyl ether, and as a B component, sodium linear alkylbenzene sulfonate (Neogen SC manufactured by Daiichi Kogyo Seiyaku Co., Ltd .; the same applies hereinafter).
A release agent for a photoresist and / or an etching-resistant resin composition comprising 1 part by weight, 20 parts by weight of caustic soda as a C component, and 73.9 parts by weight of water (100 parts by weight in total).

2) 5 parts by weight of glycerin and 1 part by weight of ethylene glycol monobutyl ether as the component A, 0.05 part by weight of sodium linear alkylbenzene sulfonate as the component B, 20 parts by weight of caustic soda as the component C,
And a release agent for a photoresist and / or an etching-resistant resin composition, comprising 73.95 parts by weight of water (100 parts by weight in total).

3) As the component A, glycerin 6 parts by weight, B
0.05 weight parts of sodium linear alkylbenzene sulfonate as a component, 20 weight parts of caustic soda as a C component,
And a release agent for a photoresist and / or an etching-resistant resin composition, comprising 73.95 parts by weight of water (100 parts by weight in total).

4) Propylene glycol 5 as the component A
Parts by weight and diethylene glycol monoethyl ether 1
Parts by weight, 0.05 parts by weight of sodium straight-chain alkylbenzene sulfonate as B component, caustic soda 2 as C component
A release agent for a photoresist and / or an etching-resistant resin composition comprising 0 parts by weight and 73.95 parts by weight of water (100 parts by weight in total).

5) As component A, 5 parts by weight of glycerin and 1 part by weight of triethylene glycol monomethyl ether;
Photoresist and / or etching-resistant resin composition comprising 0.01 parts by weight of sodium straight-chain alkylbenzene sulfonate as the B component, 20 parts by weight of caustic soda as the C component, and 73.99 parts by weight of water (100 parts by weight in total) Product release agent.

6) Propylene glycol 5 as the component A
Parts by weight, 1 part by weight of ethylene glycol monobutyl ether, and potassium perfluoroalkylsulfonate as a B component (trade name: FLORADE FC- manufactured by Sumitomo 3M Limited)
95, the same shall apply hereinafter) 0.1 parts by weight, 20 parts by weight of caustic soda as the C component, and 73.9 parts by weight of water (100 parts by weight in total) in a photoresist and / or a stripping agent for an etching resistant resin composition. .

7) As the component A, 5 parts by weight of glycerin and 1 part by weight of ethylene glycol monobutyl ether, and as the component B, 0.1 part of potassium perfluoroalkylsulfonate.
A stripping agent for a photoresist and / or an etching-resistant resin composition comprising 0.05 parts by weight, 20 parts by weight of caustic soda as a C component, and 73.95 parts by weight of water (100 parts by weight in total).

8) Propylene glycol 6 as the component A
Parts by weight, 0.05 parts by weight of potassium perfluoroalkylsulfonate as the B component, and caustic soda 20 as the C component
A photoresist and / or a stripping agent for an etching-resistant resin composition comprising parts by weight and 73.95 parts by weight of water (100 parts by weight in total).

9) Propylene glycol 5 as the component A
Parts by weight and diethylene glycol monoethyl ether 1
Parts by weight, 0.05 parts by weight of potassium perfluoroalkylsulfonate as the B component, and caustic soda 20 as the C component
A photoresist and / or a stripping agent for an etching-resistant resin composition comprising parts by weight and 73.95 parts by weight of water (100 parts by weight in total).

10) 5 parts by weight of glycerin and 1 part by weight of triethylene glycol monomethyl ether as the component A, 0.01 part by weight of potassium perfluoroalkylsulfonate as the B component, 20 parts by weight of caustic soda as the C component, and 73.99 water A photoresist and / or a stripping agent for an etching-resistant resin composition comprising 100 parts by weight (total).

[0022]

EXAMPLES Test Category 1 (Preparation of Release Agent) Example 1 5 parts by weight of propylene glycol and 1 part by weight of ethylene glycol monobutyl ether as the component A, and sodium linear alkylbenzene sulfonate (available from Daiichi Kogyo Seiyaku Co., Ltd.) as the component B 0.1 parts by weight of Neogen SC, the same applies hereinafter), 20 parts by weight of caustic soda as a C component, and water 7
3.9 parts by weight (total 100 parts by weight)
A release agent of Example 1 was prepared.

Examples 2 to 10 and Comparative Examples 1 to 5 In the same manner as in Example 1, release agents of Examples 2 to 10 and Comparative Examples 1 to 5 were prepared. Tables 1 and 2 show the compositions of the release agents prepared as described above.

[0024]

[Table 1]

[0025]

[Table 2]

In Tables 1 and 2, the numerical values in the tables are% by weight, and the remainder is water without description. * 1: Sodium linear alkylbenzene sulfonate (Neogen SC, trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) * 2: Potassium perfluoroalkyl sulfonate (trade name Florad FC-95, manufactured by Sumitomo 3M Limited)

Test Category 2 (Manufacture of Shadow Mask) A thin plate (0.1 mm thick) of amber material was degreased and washed with water according to a conventional method, and a photoresist composed of casein and ammonium bichromate was coated on both surfaces thereof. The composition was applied by a dipping method and dried to form a photosensitive film. After aligning the photomask with the small hole pattern corresponding to one side of the thin plate on which the photosensitive film is formed, and aligning the photomask with the large hole pattern corresponding to the other side, these are brought into close contact And exposed to ultraviolet light. After exposure, develop according to the usual method, remove unexposed areas, harden and form a photoresist film with a small hole pattern on one side and a photoresist film with a large hole pattern on the other side. did.

A ferric chloride solution is sprayed as an etching solution on both sides of the thin plate on which the photoresist film is formed, and the solution is subjected to primary etching to form a small hole pattern on one side and a large hole pattern on the other side. Formed. An etching-resistant resin composition solution is applied to one side of the primary-etched thin plate on the side of the small-hole opening pattern by a roller coating method, dried and cured to form an etching-resistant resin composition film. A ferric chloride solution was sprayed as an etchant on the other side of the side, and secondary etching was performed to penetrate the large hole opening pattern through the small hole opening pattern.

After the two-step etching, the thin plate is immersed in the release agent prepared in Test Category 1, the photoresist film and the etching-resistant resin composition film remaining on the surface are peeled off, and then washed with a spray method. Dry,
I got a shadow mask.

Test Category 3 (Evaluation of Release Agent) In the manufacture of the shadow mask of Test Category 2, the time required for peeling (seconds), the presence or absence of discoloration or corrosion on the thin plate surface of the amber material after peeling, and the state of bubbling at the time of washing were determined. The measurement or evaluation was performed as follows, and the results are summarized in Table 3. 1) Stripping time (second): The temperature of the stripping agent was kept at 90 ° C., and the immersion time (second) until the photoresist film and the etching-resistant resin composition film on the surface of the thin plate were completely stripped was determined. . 2) Discoloration or corrosion of the thin plate surface: The thin plate surface after peeling was visually observed and evaluated. 3) Foaming state at the time of rinsing: At the time of rinsing after peeling, the foaming state in the rinsing tank was visually observed and evaluated according to the following criteria. ○: small △; slightly large ×; severe

[0031]

[Table 3]

[0032]

As is apparent from the above description, the present invention described above allows the photoresist film or the etching-resistant resin composition film remaining on the surface of the substrate after etching to be peeled off in a short time, so that it can be used as a substrate. Since there is no discoloration or corrosion of the metal material, no chelating agent is used, and there is little foaming at the time of washing or drainage treatment, there is an effect that washing operation and drainage treatment are easy.

Claims (8)

[Claims] 1 to 10% by weight of the following component A, 0.00
A release agent for a photoresist and / or an etching-resistant resin composition comprising 1 to 0.1% by weight of the following component B, 5 to 40% by weight of the following component C, and the balance being water. A component: One or more selected from polyhydric alcohols and derivatives thereof B component: One or more selected from anionic surfactants, nonionic surfactants, and fluorosurfactants C component: Caustic 2. An amount of 3 to 10% by weight of component A, 0.003 to 3% by weight.
2. The photoresist according to claim 1, wherein 0.1% by weight of the B component, 10 to 30% by weight of the C component and the balance are water.
Alternatively, a release agent for an etching-resistant resin composition. 3. The stripping agent according to claim 1, wherein the component A is a mixture of a polyhydric alcohol and a derivative of the polyhydric alcohol. 4. The polyhydric alcohol is a dihydric or trihydric aliphatic alcohol, and the polyhydric alcohol derivative is a monoalkyl ether of a dihydric or trihydric aliphatic alcohol. A photoresist and / or a stripping agent for an etching-resistant resin composition as described above. 5. The photoresist and / or the etching resistant resin according to claim 1, wherein the component B is one or more selected from an anionic surfactant and a fluorine surfactant. Release agent for composition. 6. The anionic surfactant is an alkyl sulfonate or an alkyl ether sulfonate,
6. The stripper according to claim 5, wherein the fluorosurfactant is a perfluoroalkyl sulfonate or a perfluoroalkyl carboxylate. 7. The release agent for a photoresist and / or an etching-resistant resin composition according to claim 1, wherein the C component is caustic soda or caustic potash. 8. A photoresist and / or an etching resistant resin composition according to claim 1, which is for producing a shadow mask or an aperture grill by a two-step etching method. paint remover.