TW201807189A - Remover liquid for resist - Google Patents

Abstract

Provided is a remover liquid for resists which is characterized by containing a quaternary ammonium salt, an alkanolamine, and an aliphatic amine. Even when the remover liquid is used over days and carbonic acid dissolves therein with a lapse of the days, the remover liquid is less apt to deteriorate in performance.

Description

Resist stripping solution

The present invention relates to a stripping solution of a resist that can be peeled off from a resist-applied substrate.

In the manufacture of printed circuit boards, the stripping solution of the resist (dry film) used in the semi-additive method is mainly an amine-based stripping solution with fine wiring.

However, it is known that carbonates accumulate in the conventional amine-based barrier agent stripping solution as carbon dioxide in the air dissolves, and the peeling performance decreases.

Therefore, in order to solve the problem of lowering the peeling performance, there have been reports in the literature on technologies such as electrolytically regenerating the peeling liquid and sending carbon dioxide-removed air into the peeling processing chamber to suppress the degradation of the peeling liquid performance (Patent Documents 1 and 2) .

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2012-79830

[Patent Document 2] Japanese Patent Laid-Open No. 2013-183080

However, in these techniques, it is impossible to prevent carbonic acid from being dissolved in the stripping solution of the resist. Therefore, an object of the present invention is to provide a stripping solution that is not easily reduced even if the carbonic acid dissolving performance is not easily reduced.

As a result of research conducted by the present inventors in order to solve the above-mentioned problems, they have discovered that by using two amines having different structures as the stripping solution of the current resist, even if carbonic acid is dissolved, the performance is not as good as that of the conventional stripping solution Generally reduced, the present invention has been completed.

That is, the present invention is a stripping solution for a resist, which is characterized in that it contains a level 4 ammonium salt, an alkanolamine, and an aliphatic amine.

In addition, the present invention is a peeling liquid kit of a resist, which is characterized by comprising a first liquid containing an alkanolamine and an aliphatic amine and a second liquid containing a fourth-grade ammonium salt.

In addition, the present invention is a method for removing a plating resist, which is characterized in that the substrate to which the resist is applied is treated with the peeling solution of the resist.

Furthermore, the present invention is a method for manufacturing a printed circuit board, a semiconductor substrate, a flat display or a lead frame, which is a printed circuit board, semiconductor substrate, flat display or The method for manufacturing a lead frame is characterized in that the resist is removed using the peeling solution of the resist.

Even if the stripping liquid of the resist of the present invention is dissolved in the liquid with the passage of the use days, the performance is not easily reduced as in the conventional stripping liquid.

In addition, the stripping solution of the resist of the present invention can recover its performance only by replenishing the consumable components (such as grade 4 ammonium salt) after the use days have passed.

The quaternary ammonium salt used in the stripping solution of the resist of the present invention (hereinafter referred to simply as "the stripping solution of the present invention") is not particularly limited, and examples thereof include tetraethylammonium hydroxide and tetramethylammonium hydroxide. These quaternary ammonium salts can be used alone or in combination of two or more. The content of the quaternary ammonium salt in the stripping solution of the present invention is not particularly limited, and is, for example, 1 to 25 g / L, and preferably 5 to 20 g / L.

The alkanolamine used in the peeling liquid of the present invention is not particularly limited, and examples thereof include monoethanolamine, triethanolamine, and 2- (dimethylamino) ethanol. These alkanolamines can be used alone or in combination of two or more. The content of the alkanolamine in the peeling liquid of the present invention is not particularly limited, and is, for example, 10 to 150 g / L, and preferably 40 to 100 g / L.

The aliphatic amine used in the peeling liquid of the present invention is not particularly limited, and examples thereof include ethylenediamine, triethylamine, and hexamethylenediamine. These aliphatic amines can be used alone or in combination of two or more. The content of the aliphatic amine in the stripping solution of the present invention is not particularly limited, and is preferably 0.5 to 40 g / L, for example. It is 8 ~ 25g / L.

In the stripping solution of the present invention, the combination of the alkanolamine and the aliphatic amine is not particularly limited. For example, the alkanolamine is preferably monoethanolamine, and the aliphatic amine is preferably triethylamine or ethylenediamine. Ethylenediamine is preferred.

The peeling liquid of the present invention may further contain an organic solvent. The organic solvent used in the peeling liquid of the present invention is not particularly limited, and examples thereof include fluorenes, glycols, and lactams.

Examples of the above arsenic include dimethylarsin and the like. The content of the arsenic in the peeling liquid of the present invention is not particularly limited, and is, for example, 1 to 40 g / L, and preferably 3.5 to 10 g / L.

Examples of the above glycols include propylene glycol, diethylene glycol monoethyl ether, and the like. The content of the glycols in the stripping solution of the present invention is not particularly limited, and is, for example, 10 to 100 g / L, and preferably 20 to 60 g / L. .

Examples of the aforementioned lactams include N-methyl-2-pyrrolidone and the like. The content of lactamamines in the stripping solution of the present invention is not particularly limited, and is, for example, 10 to 800 g / L, and preferably 10 to 50 g / L.

The above organic solvents can be used singly or in combination of two or more kinds. It is preferable to use at least stilbene, stilbene and glycols, and dimethylmethylene and propylene glycol.

In addition, the peeling liquid of the present invention is preferably composed of only the above-mentioned components, and as long as the effect of the present invention is not impaired, it may contain, for example, an antifoaming agent. In addition, since a foaming surfactant and the like may impair the effect of the present invention, it is preferable that the surfactant is not contained in the peeling liquid of the present invention.

The peeling liquid of the present invention described above can be prepared by dissolving the above components in water.

The peeling liquid of the present invention may be a liquid prepared by dissolving all components in water in advance, or a liquid containing a first liquid containing an alkanolamine and an aliphatic amine (using an organic solvent as necessary) and a fourth-grade ammonium salt may be used. The peeling liquid kit of the second liquid resist is prepared during use.

By using the peeling liquid of the present invention to treat a substrate to which a resist is applied, the resist is pulverized to be fine and the resist can be removed.

The conditions under which the resist-applied substrate is treated with the peeling liquid of the present invention are not particularly limited, and examples include conditions in which the substrate is immersed in the peeling liquid of the present invention adjusted at 10 to 80 ° C. for about 1 to 60 minutes, or adjusted. The stripping solution of the present invention at 10 to 80 ° C. is sprayed on the substrate for about 1 to 60 minutes. In addition, the substrate may be shaken during immersion or an ultrasonic wave may be emitted to the peeling liquid of the present invention.

The type of the resist is not particularly limited, and for example, it is preferably an alkali-soluble type. Examples of the alkali-soluble resist include UFG-258 (25 μm thick for SAP) (manufactured by Asahi Kasei Corporation).

The base material to which the resist is applied is not particularly limited, and examples thereof include films, substrates, and parts made of various metals or alloys used in printed circuit boards, semiconductor substrates, flat-panel displays, and lead frames.

As described above, the peeling liquid of the present invention can remove the resist from the base material to which the resist is applied, so that it can be used for a method for manufacturing a printed circuit board, a semiconductor substrate, a flat display, a lead frame, and the like including the step of removing the resist. .

Among the above-mentioned manufacturing methods, a method for manufacturing a printed circuit board including a step of removing the resist from a substrate to which the resist is applied is preferred, and a method for manufacturing a printed circuit board using a semi-additive method is particularly preferred.

[Example]

The following examples illustrate the present invention in detail, but the present invention is not limited at all by these examples.

Example 1 Preparation of stripping solution:

The components described in Table 1 below were dissolved in water to prepare a peeling solution.

The value of () is g / L.

TMAH: Tetramethylammonium hydroxide

MEA: Monoethanolamine

TEA: Triethanolamine

DMAE: 2- (dimethylamino) ethanol

EDA: Ethylenediamine

TEN: Triethylamine

PG: propylene glycol

DGME: Diethylene glycol monoethyl ether

DMSO: Dimethoate

Example 2 Performance of peeling liquid: (1) Peel test

A substrate obtained by laminating a dry film (manufactured by Asahi Kasei: UFG-258 (for SAP); 25 μm thick) on a copper-clad laminate (manufactured by Furukawa Electric Co., Ltd .: CCL secondary electrolytic copper foil GTS 35 μm foil), A 50 × 50 mm ² portion was cut out as a test piece.

The test piece was immersed in each peeling liquid having a liquid temperature of 50 ° C., the substrate was shaken at 1 reciprocation / 1 second, and the time until the dry film was completely peeled off and the size (long side) of the peeling sheet after peeling were measured.

(2) Carbon dioxide resistance

The peeling liquid (1 L) was maintained at 50 ° C. while air bubbling was performed at an air flow rate of 1 L / min for 192 hours (8 days). After foaming, the same peel test as in (1) was performed.

(3) Recovery

After foaming in (2), the analysis of the consumption components by titration analysis revealed that the fourth-order ammonium salt was consumed. So, to restore the amount of the composition of Table 1 To supply level 4 ammonium. After replenishment, the same peel test as in (1) was performed.

(4) Results

The results of the above tests are shown in Table 2.

From the above results, it was found that by using two substances, alkanolamines and aliphatic amines, as amines, even after foaming for 8 days, performance (especially peeling size) did not decrease as in conventional peeling liquids. In addition, by replenishing the consumable components, the peeling liquid is in a state close to the original performance. It can be seen that among the above-mentioned peeling liquids, if the use in an actual production line is considered, from the standpoint of peeling time and size, the compositions 2 and 5 are preferable, and from the viewpoint of performance after 8 days of foaming, the composition 2 is preferable.

[Industrial availability]

The present invention can be used in a method for manufacturing a printed circuit board, a semiconductor substrate, a flat display, or a lead frame including a step of removing the resist from a resist-applied substrate.

Claims (10)

A stripping solution for a resist, characterized in that it contains a level 4 ammonium salt, an alkanolamine and an aliphatic amine. For example, the stripping solution of the barrier agent in the scope of application for the patent, wherein the alkanolamine is monoethanolamine and the aliphatic amine is ethylenediamine. For example, the stripping solution for the resist in the scope of patent application No. 1 or 2 further contains an organic solvent. For example, the stripping solution of the resist in the third item of the patent application, wherein at least a solvent of the subfluorene type is used as the organic solvent. A peeling liquid kit for a resist, comprising: a first liquid containing an alkanolamine and an aliphatic amine; and a second liquid containing a grade 4 ammonium salt. A method for removing a resist, characterized in that the base material to which the resist is applied is treated with a stripping solution of the resist according to any one of claims 1 to 4 of the patent application scope. A method for manufacturing a printed circuit board, which is a method for manufacturing a printed circuit board including a step of removing a resist from a base material to which the resist is applied, which is characterized by using any one of items 1 to 4 of the scope of patent application Stripping Liquid to remove the resist. A method for manufacturing a semiconductor substrate, which is a method for manufacturing a semiconductor substrate including a step of removing the resist from a base material to which the resist is applied, which is characterized by using a resist as described in any one of claims 1 to 4 of the scope of patent application. Remover of the agent to remove the resist. A method of manufacturing a flat display, which is a method of manufacturing a flat display including a step of removing the resist from a base material to which the resist is applied, which is characterized by using a resist such as any one of claims 1 to 4 in the scope of patent application. Remover of the agent to remove the resist. A method for manufacturing a lead frame, which is a method for manufacturing a lead frame including a step of removing the resist from a base material to which the resist is applied, which is characterized by using a resist such as any one of claims 1 to 4 in the scope of patent application. Remover of the agent to remove the resist.