KR101420571B1 - Remover composition for dryfilm resist and removing method using the same - Google Patents

Abstract

The present invention relates to a dry film resist stripper composition containing a hydroxide compound, a chain amine compound, a triazole compound, and pure water at a predetermined mixing ratio, and a dry film resist removing method using the same, At the same time, corrosion of the metal layer is prevented, and the remover can be reused.

Description

Technical Field [0001] The present invention relates to a dry film resist stripping composition and a dry film resist removing method using the same.

The present invention relates to a dry film resist stripper composition and a method for removing a dry film resist using the same.

Flip Chip Chip Scale Package (FCCSP) has been developed as the demand for high performance, miniaturization and thinness of ball grid array (BGA) products has been developed. It is an increasing tendency. The FCCSP uses a bump to connect chips and printed circuit boards (PCBs) rather than wire bonding. In the past, bumps were manufactured using Metal Mask Printing (MMP) method. However, in recent years, in order to miniaturize bump pitch and ensure productivity, a blue stencil using a dry film resist (DFR) Printing (Blue Stencil Printing, BSP) method was developed.

The BSP method is advantageous for bump formation and productivity, but there is a problem in that defective organic material contamination is increased and metal damage is caused by the use of a dry film or a strong alkaline solution. Therefore, there is a desperate need to develop a new release agent suitable for such BSP method.

On the other hand, Patent Document 1 discloses a release agent composition for a printed circuit board. However, as a purpose of peeling a photoresist rather than a dry film resist, there is a problem that a remover is not completely removed and remnants remain on the substrate.

Patent Document 1: Korean Patent Publication No. 2000-0046480

Accordingly, the present invention provides a dry film resist stripper composition comprising a hydroxide compound, a chain amine compound, and a triazole compound, thereby preventing the residue of dry film resist on the substrate from remaining and minimizing the corrosion of the metal layer And the present invention has been completed on the basis thereof.

Accordingly, a first aspect of the present invention is to provide a dry film resist stripper composition comprising a hydroxide compound, a chain amine compound, and a triazole compound to completely remove the dry film resist residue on the substrate and minimize corrosion of the metal layer .

A second aspect of the present invention is to provide a method for removing a dry film resist using the dry film resist stripper composition.

A dry film resist stripper composition (hereinafter referred to as " first invention ") according to a representative embodiment of the present invention for achieving the first aspect comprises a hydroxide compound; Chain amine compounds; Triazole compounds; And pure water (H ₂ O).

In the first invention, it is preferable that the composition contains 0.5 to 15% by weight of a hydroxide compound, 1 to 40% by weight of a chain amine compound, 0.5 to 5% by weight of a triazole compound and the balance of pure water .

In the first invention, the composition is characterized in that it comprises 0.5 to 5% by weight of a hydroxide compound, 5 to 15% by weight of a chain amine compound, 0.5 to 5% by weight of a triazole compound and the balance of pure water .

In the first invention, the composition further comprises a glycol, an organic acid, a surfactant, an organic solvent, a defoaming agent, or a mixture thereof.

In the first invention, the hydroxide-based compound is characterized by being an inorganic alkali hydroxide or an alkylammonium hydroxide.

In the first invention, the alkylammonium hydroxide is characterized by being tetraethylammonium hydroxide, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, trimethylbenzylammonium hydroxide, or a mixture thereof .

In the first invention, the alkylammonium hydroxide is tetramethylammonium hydroxide.

In the first aspect of the present invention, the chain amine compound is selected from the group consisting of monoethanolamine, diethanolamine, triethanolamine, propanolamine, dipropanolamine, tripropanolamine, isopropanolamine, diisopropanolamine, triisopropanolamine, 2- Aminoethoxy) ethanol, 2- (2-aminoethylamino) ethanol, N, N-dimethylethanolamine, N, N-diethylethanolamine, N-methylethanolamine, N-ethylethanolamine, Amine and N-methylethanolamine.

In the first invention, the chain amine compound is monoethanolamine.

In the first invention, the triazole compound is characterized by being a tolythriazole.

In the first invention, the pure water (H ₂ O) has a resistivity of 18 (MΩ) or more.

A method of removing a dry film resist (hereinafter referred to as " second invention ") for achieving the second aspect of the present invention comprises: laminating a dry film on a substrate on which a predetermined circuit pattern is formed; Partially exposing the laminated dry film to form a dry film exposing part and a dry film unexposed part; Developing and removing the dry film non-visible portion to form an opening; Mounting a solder ball on the circuit pattern on which the opening is formed; And

And contacting the dry film resist stripper composition according to various embodiments of the present invention to the dry film exposure section.

According to a second aspect of the present invention, there is provided a method of removing a dry film resist, which comprises washing the dry film resist residue after the contacting.

The dry film resist stripper composition according to various embodiments of the present invention has an excellent effect of minimizing the corrosion of the metal layer in contact with the stripper and completely removing the dry film resist.

1 is a process diagram showing a method of removing a dry film resist using a dry film resist stripper composition according to an embodiment of the present invention.
2A is a photograph showing an ordinary gold pad.
FIG. 2B is a photograph showing the result of measuring the dry film resist peeling force on a gold pad using the dry film resist stripping solution according to Example 3 of the present invention. FIG.
2C is a photograph showing the result of measuring the dry film resist peeling force on a gold pad using the dry film resist stripping solution according to Comparative Example 2 of the present invention.
3A is a photograph showing general solder balls (Sn / Pb).
FIG. 3B is a photograph showing the result of measuring the corrosion of the surface of the solder ball using the dry film resist stripping solution according to the third embodiment of the present invention. FIG.
3C is a photograph showing the result of measuring the corrosion of the surface of the solder ball using the dry film resist stripping solution according to Comparative Example 2 of the present invention.
4A is a photograph showing a typical copper pad (Cu pad).
4B is a photograph showing a result of measuring the corrosion of the copper pad surface using the dry film resist stripping solution according to the third embodiment of the present invention.
4C is a photograph showing the result of measuring the corrosion of the copper pad surface using the dry film resist stripping solution according to Comparative Example 2 of the present invention.

Before describing the present invention in more detail, it is to be understood that the words or words used in the present specification and claims should not be construed in a conventional or dictionary sense, It should be interpreted in accordance with the meaning and concept consistent with the technical idea of the present invention based on the principle that it can be defined. Therefore, the constitution of the embodiments described in the present specification is merely a preferred example of the present invention, and does not represent all the technical ideas of the present invention, so that various equivalents and variations And the like.

Hereinafter, preferred embodiments of the present invention will be described in detail so that those skilled in the art can easily carry out the present invention.

In the following description, well-known functions or constructions are not described in detail since they would obscure the invention in unnecessary detail.

A dry film resist stripper composition according to exemplary embodiments of the present invention includes a hydroxide-based compound, a chain-like amine compound, a triazole compound, and pure water.

Hydroxide system  compound

The hydroxide-based compound in the dry film resist stripper composition according to exemplary embodiments of the present invention is an inorganic alkali hydroxide or an alkylammonium hydroxide. The alkylammonium hydroxide may be selected from the group consisting of tetraethyl ammonium hydroxide, tetramethyl ammonium hydroxide, tetrabutyl ammonium hydroxide, trimethylbenzyl ammonium hydroxide trimethylbenzyl ammonium hydroxide, or a mixture thereof may be used, and it is most appropriate to use tetramethylammonium hydroxide.

The hydroxide-based compound in the exfoliant composition is not particularly limited, but may have an amount of 0.5 to 15% by weight, particularly 0.5 to 5% by weight. If the amount of the hydroxide compound is less than 0.5% by weight, the ability to penetrate into the polymeric material constituting the dry film resist may decrease, so that it may be difficult to completely remove the dry film resist. If the amount exceeds 15% by weight, It may take a long time to remove the resist, which may adversely affect the corrosion of the metal film.

Chain type  Amine compound

In another exemplary embodiment of the present invention, the chain amine compound in the dry film resist stripper composition is selected from the group consisting of monoethanol amine, diethanol amine, triethanol amine, propanol amine, Propanol amine, tripropanol amine, isopropanol amine, diisopropanol amine, triisopropanol amine, 2- (2-aminoethoxy) ethanol (2 2-aminoethoxy ethanol, 2- (2-aminoethylamino) ethanol, N, N-dimethylethanol amine, N, N- N, N-diethylethanolamine, N-methylethanolamine, N-ethylethanolamine, N-butylethanolamine and N - N-methylethanol amine , And monoethanolamine is most suitably used.

The chain amine compound in the exfoliant composition is not particularly limited, but may have an amount of 1 to 40% by weight, particularly 5 to 15% by weight. If the amount of the chain amine compound used is less than 1% by weight, it may be difficult to completely remove the dry film resist. If the amount exceeds 40% by weight, the content of the other materials contained in the release agent composition may be lowered, The time is lengthened and the metal film may be corroded.

Triazole  compound

The triazole compound in the dry film resist stripper composition according to the exemplary embodiment of the present invention is a corrosion inhibitor, and the functional group contained in the triazole compound chemically or physically bonds to the metal film. The exchange of electrons between the metal film and the releasing agent serving as an electrolyte by the triazole compound is fundamentally prevented so that the metal film is not oxidized and corrosion does not occur. As the triazole compound, it is most appropriate to use tolyltriazole.

The triazole compound in the releasing agent composition is not particularly limited but may be suitably used in an amount of 0.5 to 5% by weight. If the amount is less than 0.5% by weight, the dry film resist stripping solution containing an amine compound If the amount exceeds 5% by weight, the content of the other materials contained in the release agent composition may be lowered, and the dry film resist may not be completely removed, resulting in an economical disadvantage.

pure ( H ₂ O )

The pure water in the dry film resist stripper composition according to the exemplary embodiment of the present invention uses pure water filtered through an ion exchange resin, and it may be appropriate that the resistivity is 18 (MΩ) or more.

The amount of pure water to be used in the exfoliant composition is not particularly limited, but an amount that is not affected by the composition ratio of the above-mentioned other composition can be used.

The dry film resist stripper composition may further comprise other components as long as the effect of the present invention is not impaired. Such components may include a glycol, an organic acid, a surfactant, an organic solvent, a defoamer, or a mixture thereof.

The glycol may be selected from the group consisting of ethyleneglycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, diethylene glycol monoethyl ether, At least one selected from the group consisting of ethylene glycol, hexylene glycol and glycerol can be used.

The organic acid may be at least one selected from the group consisting of acetic acid, citric acid, oxalic acid, and caprylic acid.

As the organic solvent, dimethylsulfoxide is most suitably used.

A method of removing a dry film resist using a release agent composition according to exemplary embodiments of the present invention can be found through a process diagram as shown in FIG. The dry film 20 is laminated on the substrate 100 on which the predetermined circuit pattern 10 is formed and the laminated dry film is partially exposed to expose the dry film exposing portion 22 and the dry film non- . The dry film exposing portion 21 is removed with a developing solution to form an opening portion, and a solder ball 30 is formed on the circuit pattern 10 of the opening portion. Then, the dry film unexposed portion 21 is removed using the dry film resist stripper composition of the present invention. The use of the release agent composition of the present invention minimizes the corrosion of the circuit pattern 10 present in the lower layer of the dry film unexposed portion 21 and the solder ball 30 placed on the circuit pattern 10, The non-visible light portion 21 can be completely removed. Also, in the removal agent composition of the present invention, since the residue of the dry film unexposed portion 21 is not dissolved in the release agent composition during the removal of the dry film unexposed portion 21, the release agent composition can be reused later .

In addition, the method of removing the dry film resist may further include washing the dry film resist residue after removing the dry film unexposed portion 21.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the scope of the present invention is not limited to the following examples.

Examples 1 to 15

Using the components and composition ratios described in Table 1 below, the mixture was stirred at room temperature (25 캜) for about 2 hours to prepare a dry film resist peeling solution.

Comparative Examples 1 to 5

Similarly, using the components and composition ratios described in Table 1 below, the mixture was stirred at room temperature (25 캜) for about 2 hours to prepare a dry film resist peeling solution.

division TMAH
(weight%) NMP
(weight%) MEA
(weight%) TT
(weight%) NaOH
(weight%) HMTA
(weight%) Pure (H ₂ O)
(weight%) Example 1 5.0 8.0 3.0 84.0 Example 2 4.0 8.0 3.0 85.0 Example 3 3.0 8.0 3.0 86.0 Example 4 2.0 8.0 3.0 87.0 Example 5 1.0 8.0 3.0 88.0 Example 6 3.0 14.0 3.0 80.0 Example 7 3.0 12.0 3.0 82.0 Example 8 3.0 10.0 3.0 84.0 Example 9 3.0 9.0 3.0 85.0 Example 10 3.0 6.0 3.0 88.0 Example 11 3.0 8.0 5.0 84.0 Example 12 3.0 8.0 4.5 84.5 Example 13 3.0 8.0 4.0 85.0 Example 14 3.0 8.0 3.5 85.5 Example 15 3.0 8.0 2.5 86.5 Comparative Example 1 8.0 2.5 89.5 Comparative Example 2 3.0 8.0 3.0 86.0 Comparative Example 3 50.0 15.0 35.0 Comparative Example 4 5.0 95.0 Comparative Example 5 25.0 3.0 72.0

TMAH: tetramethyl ammonium hydroxide < RTI ID = 0.0 >

NMP: 1-methyl-2-pyrrolidone

MEA: monoethanol amine

TT: tolyltriazole

NaOH: sodium hydroxide < RTI ID = 0.0 >

HMTA: hexamethylenetetra amine < RTI ID = 0.0 >

Peel force , Corrosion and / Peeling liquid  Aging test

A dry film resist was laminated on a substrate having a copper circuit pattern and a solder ball by a roll compression method at a temperature of about 95 캜 and a pressure of 3 kgf / cm 2 to prepare a test piece. As can be seen from the above Table 1, about 2 kg of the peeling liquid prepared in Examples and Comparative Examples and the prepared specimen were injected into the spraying apparatus for about 4 minutes under the conditions of about 50 캜 and 1 kgf / cm 2 , Then washed with pure water (H ₂ O) and dried with nitrogen. The specimens were observed with a naked eye and a microscope (SEM), and peel strength and corrosion were measured. Copper pad specimens were treated up to 100 sheets to observe discoloration of the copper pads with naked eyes due to detachment aging.

division Peel strength measurement Measurement of detachment aging degree Metal damage 100 sheets of copper pad peeling Solder balls (Sn / Pb) Copper pad Example 1 100% 0% 0% Example 2 100% 0% 0% Example 3 100% 0% 0% 0% Example 4 100% 0% 0% Example 5 80% 0% 0% Example 6 100% 10% 10% Example 7 100% 0% 0% Example 8 100% 0% 0% Example 9 100% 0% 0% Example 10 100% 0% 0% Example 11 90% 0% 0% Example 12 90% 0% 0% Example 13 100% 0% 0% Example 14 100% 0% 0% Example 15 100% 0% 0% Comparative Example 1 50% 0% 0% Comparative Example 2 70% 40% 50% 50% Comparative Example 3 50% 70% 70% Comparative Example 4 50% 100% 100% Comparative Example 5 50% 50% 50%

Peel force  Measure

As shown in Table 2, it can be seen that the peel strength results of Examples 1 to 15 are superior to the peel strength results of Comparative Examples 1 to 5.

2A is a photograph showing an ordinary gold pad.

2B and 2C. FIG. 2B is a photograph after removing the dry film resist using the peeling solution prepared in Example 3, and it can be seen that there is no residue on the surface. However, FIG. 2C is a photograph after removing the dry film resist using the peeling solution prepared in Comparative Example 2, showing that the residue remained on the surface of the pad, and remnants remained on the edge of the pad.

Measuring corrosion

As shown in Table 2, corrosion results of solder balls (Sn / Pb) and copper pads (Cu pad) were measured using the peeling solution prepared in Examples 1 to 15, Which is superior to the result obtained by using the exfoliation solution.

Figures 3a and 4a are photographs showing common solder balls and copper pads.

3B and 3C are photographs. FIG. 3B is a photograph of the surface of the solder ball after removing the dry film resist using the peeling solution prepared in Example 3, and it can be confirmed that the surface is not corroded. However, FIG. 3C is a photograph of the surface of the solder ball after removing the dry film resist using the exfoliation liquid prepared in Comparative Example 2, so that the surface is corroded and confirmed to be damaged.

4B and 4C. FIG. 4B is a photograph of the surface of the copper pad after removing the dry film resist using the exfoliation liquid prepared in Example 3, and it can be seen that the surface is not corroded have. However, FIG. 4C is a photograph of the surface of the copper pad after removing the dry film resist using the exfoliation liquid prepared in Comparative Example 2, so that the surface is corroded and confirmed to be damaged.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, the same is by way of illustration and example only and is not to be construed as limiting the present invention. It is obvious that it can be modified or improved.

It is intended that the present invention cover the modifications and variations of this invention provided they come within the scope of the appended claims and their equivalents.

10: circuit pattern 20: dry film
21: dry film non-exposure part 22: dry film exposure part
30: solder ball 100: substrate

Claims (13)

1 to 5% by weight of a hydroxide-based compound;
6 to 14% by weight of a chain-like amine compound;
2.5 to 5% by weight of a triazole compound; And
The remaining pure (H ₂ O);
Wherein the dry film resist stripper composition comprises:
delete delete The method according to claim 1,
Wherein the composition further comprises a glycol, an organic acid, a surfactant, an organic solvent, a defoaming agent, or a mixture thereof.
The method according to claim 1,
Wherein the hydroxide-based compound is an inorganic alkali hydroxide or an alkylammonium hydroxide.
The method of claim 5,
Wherein the alkylammonium hydroxide is tetraethylammonium hydroxide, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, trimethylbenzylammonium hydroxide, or a mixture thereof.
The method of claim 5,
Wherein the alkylammonium hydroxide is tetramethylammonium hydroxide. ≪ RTI ID = 0.0 > 11. < / RTI >
The method according to claim 1,
The chain amine compound may be selected from the group consisting of monoethanolamine, diethanolamine, triethanolamine, propanolamine, dipropanolamine, tripropanolamine, isopropanolamine, diisopropanolamine, triisopropanolamine, 2- (2-aminoethoxy) N-dimethylethanolamine, N, N-diethylethanolamine, N-methylethanolamine, N-ethylethanolamine, N-butylethanolamine and N-methylethanolamine Amines, and mixtures thereof. ≪ Desc / Clms Page number 24 >
The method according to claim 1,
Wherein the chain amine compound is monoethanol amine.
The method according to claim 1,
Wherein the triazole compound is a tolylthiazole.
The method according to claim 1,
Wherein the pure water (H ₂ O) has a resistivity of 18 (MΩ) or more.
Laminating a dry film on a substrate on which a predetermined circuit pattern is formed;
Partially exposing the laminated dry film to form a dry film exposing part and a dry film unexposed part;
Developing and removing the dry film non-visible portion to form an opening;
Mounting a solder ball on the circuit pattern on which the opening is formed; And
Contacting the dry film resist stripper composition according to any one of claims 1 and 4 to 11 with the dry film exposure section;
And removing the dry film resist.
The method of claim 12,
And washing the dry film resist residue after the contacting step.

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