KR101567407B1 - Composition for Removing Thermosetting Solder Masks and Method for Forming Resist Patterns Using the Same - Google Patents

Abstract

Disclosed are an alkaline developer capable of effectively removing a solder mask in a thermosetting resin, and a method for forming a solder mask pattern of a printed circuit board using the same. The alkaline developer of the present invention comprises: 200-500 g/L of water soluble aliphatic amine; 200-500 g/L of an alkaline metal hydroxide; 50-200 g/L of a glycol ether solvent; 1-50 g/L of an azole-based corrosion inhibitor; 0.1~50 g/L of a surfactant; 50 g/L or less of an inorganic additive as an optional ingredient; and the remainder consisting of water. The alkaline developer and the method for forming the solder mask pattern of the printed circuit board of the present invention are suitable to manufacture an ultrathin high strength printed circuit board capable of realizing micropatterning.

Description

TECHNICAL FIELD The present invention relates to a composition for removing a thermosetting solder mask and a method for forming a resist pattern using the composition.

The present invention relates to the manufacture of printed circuit boards. More particularly, the present invention relates to a method for forming a solder resist pattern on a printed circuit board and an alkaline developer for the method.

In the rapid development of various electronic devices, including mobile phones, the direction of development is toward high functionality with thin device thickness. As a result, the demand for miniaturization of printed circuit boards, which are core components of electronic devices, is also critical. However, various automatic and passive components are mounted on a printed circuit board, so that it is difficult to simply transfer the signal to be transmitted, and the stiffness must be sufficient. For this, the strength of the solder resist must be accompanied. In manufacturing an ultra thin plate printed circuit board with a thickness of 0.15 t or less, a conventional acrylic resin-based photosensitive solder resist can not secure sufficient stiffness at a thin thickness, resulting in defective warpage during the substrate manufacturing process, There is a problem that the yield is low.

So far, epoxy-based thermoset solder mask resists have been reviewed to replace these problems, but there has been no effective means to remove thermoset solder masks by wet processes. For example, according to a conventional wet process (Korean Patent Laid-Open No. 10-2008-0016462), a method of selectively developing a photocurable resist using a 1% aqueous solution of sodium carbonate to selectively remove a solder mask has been disclosed, Such a photo-curing resist can not secure stiffness in an ultra-thin printed circuit board. Also, it is impossible to remove the thermosetting resist by using this 1% aqueous solution of sodium carbonate.

For this reason, selective removal of the thermosetting resin solder resist through the laser has been attempted on the other hand. However, in the method of removing a thermosetting solder resist through a laser, there are disadvantages such as remaining of a solder mask resist due to difficulty in setting processing conditions, defects such as copper wiring damage, and excessive process time.

In short, to date, the demand for an effective wet process to remove the solder mask of the thermosetting resin material which can support the ultra thin plate package substrate in this field is not satisfied.

The present invention provides a method of forming a solder mask pattern of a thermosetting resin material for manufacturing a highly rigid and highly reliable ultra thin plate package substrate, and a developer capable of effectively providing such a solder mask by a wet process.

According to one aspect of the present invention, there is provided a water-soluble organic solvent comprising 200 to 500 g / L of a water-soluble aliphatic amine, 200 to 500 g / L of an alkali metal hydroxide, 50 to 200 g / L of a glycol ether solvent, To 50 g / L and 0.1 to 50 g / L of a surfactant and the balance water. The alkali developer of the present invention may further contain at least one inorganic salt additive selected from silicates, phosphates or nitrates of sodium, potassium or ammonium cations in an amount of 50 g / L or less.

In another aspect of the present invention, a method of forming a solder mask pattern on a printed circuit board is disclosed. The solder mask pattern forming method of the present invention includes the following steps:

(A) a lay-up step of sequentially laminating a layer of a thermosetting resin and a copper foil layer on a substrate on which conductive wirings are formed on an inner layer substrate,

(B) a thermocompression step of heating the thermosetting resin laminated in (A) so that the curing of the thermosetting resin proceeds 50 to 90%

(C) a conformal mask forming step of etching the copper foil to form a pattern, and

(D) a solder mask etching step in which the unprotected portion of the thermosetting resin layer formed in (c) is exposed to a developing solution containing an aliphatic amine and an alkali metal hydroxide to remove the unprotected portion,

(E) a step of completing a solder mask for heating and curing the above-mentioned thermosetting resin layer,

(F) coating a resist of copper and another metal on the indentation where the thermosetting resin is removed from the thermosetting resin layer,

(G) removing the copper foil layer by etching; and

(A) removing the metal resist.

A solder mask pattern is formed of a thermosetting resin by using an alkali developing solution and a method of forming a solder mask pattern using the alkaline developer according to a preferred embodiment of the present invention, and the solder mask is patterned at a process temperature in the range of 40 to 80 ° C to a thickness of 2 to 8 μm / You can remove it at speed. As described above, the solder mask pattern forming method of the present invention assists replacing the conventional photosensitive acrylic solder mask resist with a thermosetting epoxy solder mask resist in the process of manufacturing an ultra thin plate package printed circuit board, and the alkaline developer of the present invention is mass- Support the removal of solder masks due to the excellent wet process.

1 is a schematic view showing a process of forming a solder mask pattern on a printed circuit board according to a solder mask pattern forming method of the present invention and developing the same.
2 is a schematic diagram showing the degree of stripping of a substrate during formation of a solder mask pattern using an alkaline developer of the prior art. FIG. 2A shows results obtained using the alkaline developer of Comparative Example 1 and FIG. 2B using the developer of Comparative Example 2. FIG.
3 is an electron micrograph of a printed circuit board manufactured using an alkali developer according to the present invention.

Hereinafter, the present invention will be described in detail. In interpreting the terms or words used in the present specification and claims, the inventors should interpret the present invention on the principle that the inventor can properly define the concept of the term in order to explain its own invention in the best way . That is, the terms used in describing the present invention are not necessarily interpreted by ordinary or dictionary meanings, but should be construed in accordance with the technical idea of the present invention.

Hereinafter, the present invention will be described in more detail with reference to the drawings.

In one aspect of the present invention, an aqueous alkaline developer composition is disclosed. The alkaline developer composition of the present invention is particularly useful for removing a solder mask or a solder resist based on an epoxy resin, for example, a thermosetting resin.

The alkali developer composition of the present invention may further comprise a water-soluble aliphatic amine, an alkali metal hydroxide, a glycol ether solvent, an azole-based corrosion inhibitor, a surfactant and water, and optionally, an inorganic salt additive.

In the alkaline developer composition of the present invention, the water-soluble aliphatic amine plays a leading role in dissolving the solder resist together with the alkali metal hydroxide.

In the present specification, a water-soluble aliphatic amine encompasses primary, secondary, and tertiary amines as amines derived from aliphatic hydrocarbons having at least one carbon atom. In this specification, the water-soluble aliphatic amine may further contain a hydrocarbon functional group and a hydroxyl group in addition to an amino group or imino group. As the water-soluble aliphatic amine, those known in the art may be used, for example, those having a solubility of 200 g or more per liter of aqueous solution at room temperature. Examples of specific water-soluble aliphatic amines that can be used in the present invention include monoethanolamine, diethanolamine, triethanolamine, aminomethylpropanol, triisopropanolamine, dibutylamine, tributylamine, diisopropanolamine, methylmonoethanolamine , Methyldiethanolamine, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dimethylethanolamine, isopropylamine, cyclopentylamine, cyclohexylamine, diamylamine and any ratio thereof Mixtures may be used.

In the alkali developer composition of the present invention, the water-soluble aliphatic amine is suitably contained at a ratio of 200 to 500 g / L.

In the alkaline developer composition of the present invention, the alkali metal hydroxide becomes a base for dissolving the solder resist together with the water-soluble aliphatic amine. As the alkali metal hydroxide in the composition of the present invention, a hydroxide of alkali metal and ammonium ion may be used. In a specific embodiment of the present invention, sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonium hydroxide, or a mixture thereof is used in terms of economy, performance, and ease of handling. In the alkali developer composition of the present invention, the alkali metal hydroxide is suitable when it occupies a content of 200 to 500 g / L.

In the alkaline developer of the present invention, the glycol ether solvent serves to swell the solder resist resin to accelerate the development speed. In the present specification, glycol ether-based solvents include not only ethylene glycol-based solvents but also glycol ethers of propylene glycol and butylene glycol skeleton. Herein, when it is referred to as a glycol ether solvent, not only ethylene glycol, propylene glycol, butylene glycol, etc. are ether-bonded, but also various units of these glycols (which may be the same or different) Ether is also included. In the glycol ether of the present invention, the functional group which is linked by an ether bond to such a glycol unit (s) is both an alkyl group and an aryl group. The glycol ether solvent of the present invention is not particularly limited as long as it has the above-mentioned content and solubility in water of 50 g / L or more. Examples of specific glycol ether solvents include ethylene glycol monomethyl ether, Diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, polyethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, polyethylene glycol monoethyl ether, ethylene glycol monobutyl Diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, polyethylene glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, ethylene glycol monoisopropyl ether, ethylene Glycol monoisobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monoethylhexyl ether, ethylene glycol monoaryl ether, ethylene glycol monophenyl ether, and mixtures of any of these.

In the alkaline developer composition of the present invention, the glycol ether solvent is suitable when it occupies a content of 50 to 200 g / L. When the content of the glycol ether solvent is within this range, the solder resist resin is swollen and the developing speed is increased, which is preferable from the viewpoint of productivity. On the other hand, when the content of the glycol ether solvent is less than 50 g / L, the swelling of the solder resist resin slows down and the effect on the developing speed is insignificant. When the content exceeds 200 g / L, the viscosity of the developer becomes high, It is not desirable.

In the alkaline developer composition of the present invention, the azole-based corrosion inhibitor serves to prevent the base component in the developer from causing undesired corrosion on the copper wiring layer of the substrate. In the present specification, the azole-based corrosion inhibitor is a 5-membered heterocycle containing a nitrogen as a constituent element in the ring as a 5-membered hydrocarbon ring, or a 5-membered heterocycle in which such a 5-membered heterocycle is fused with another hydrocarbon ring is a heterocyclic hydrocarbon Compounds ("azole-based compounds"). In the alkaline developer composition of the present invention, the azole-based corrosion inhibitor can be used in various types without particular limitation, but an azole-based compound having a solubility of 1 g / L or more can be used when an aqueous solution is prepared at room temperature. Specific examples of the azole-based corrosion inhibitor that can be used in the alkali developer composition of the present invention include benzotriazole, 5-aminotetrazole, tolyltriazole, 1,2-dimethylimidazole, 1-benzyl- Imidazole, 1-benzyl-2-phenylimidazole, 1-methylimidazole, 1-vinylimidazole, 2-bromo-4-nitroimidazole, N, N-diisopropylethylamine, N, N -diisopropylethylamine, N, N -diisopropylethylamine, N, Imidazoles and mixtures of any of these.

In the alkaline developer composition of the present invention, the azole-based corrosion inhibitor is suitable when it occupies a content of 1 to 50 g / L. When the content of the azole-based corrosion inhibitor is within this range, the corrosion inhibiting function against the copper wiring layer is exerted so that the solder resist is completely developed, and etching of the copper wiring layer does not occur even if the copper wiring layer is exposed to the developer composition. On the other hand, when the content of the azole corrosion inhibitor is less than 1 g / L, the corrosion inhibiting effect can not be expected, and even if the content exceeds 50 g / L, the corrosion inhibiting effect is not improved.

The surfactant in the alkaline developer composition of the present invention serves to prevent residues of the solder resist remaining on the substrate after dissolution. When a cationic surfactant is used as the surfactant in the composition of the present invention, an excellent effect can be obtained. The cationic surfactant that can be used in the alkali developer composition of the present invention is not particularly limited as long as it is used in this technical field. Some examples of cationic surfactants that may be used in the compositions of the present invention include, but are not limited to, oleylimidazolium methosulfate quaternary ammonium surfactants, oleylamidoamine methosulfate quaternary ammonium surfactants, dimethylalkylamine derivatives, Alkylamides, and mixtures thereof. The surfactant in the alkali developer composition of the present invention is suitable when it occupies a content of 0.1 to 50 g / L.

The alkaline developer composition of the present invention may further contain an inorganic salt additive as an optional component. These inorganic salt additives increase cleansing properties in alkaline environments and are used to prevent residues on the substrate after solder resist dissolution. In one embodiment of the invention, the inorganic salt additive is at least one inorganic salt selected from silicates, phosphates or nitrates of sodium, potassium or ammonium cations. Some examples of inorganic salt additives that can be used in the alkaline developer composition of the present invention include silicates such as sodium metasilicate, potassium monophosphate, potassium diphosphate, potassium triphosphate, sodium monophosphate, sodium diphosphate, sodium triphosphate, etc. Phosphoric acid, ammonium nitrate, sodium nitrate, potassium nitrate. The inorganic salt additive in the alkali developer composition of the present invention is suitable when it is used in an amount of 50 g / L or less.

The alkaline developer composition of the present invention further comprises water of the remainder in addition to the above-mentioned components. Water which can be used in the alkali developing solution composition of the present invention is suitable if it is used with an ultrapure water grade commonly used in a developer or etchant in the technical field, but it is not necessarily limited to this grade.

In the preferred embodiments of the present invention described above, it is possible to effectively and quickly remove the thermosetting resin layer in particular by using the alkaline developer composition having the above composition, and to provide an alkaline solution capable of minimizing occurrence of excessive etching of the substrate copper wiring layer, Thereby providing a developer composition. For example, in a more specific embodiment of the present invention, the thermosetting resin layer, for example solder resist, at a favorable process temperature in the range of 40 to 80 占 폚 can be removed at a high rate, for example, at a rate of 2 to 8 占 퐉 per minute .

Another aspect of the present invention provides a method of forming a solder mask pattern of a printed circuit board using a thermosetting resin. This method

(A) a lay-up step of sequentially laminating a layer of a thermosetting resin and a copper foil layer on a substrate on which conductive wirings are formed on an inner layer substrate;

(B) a thermocompression-bonding step of heating the thermosetting resin laminated in (A) so that curing proceeds 50 to 90%;

(C) forming a conformal mask for etching the copper foil to form a pattern;

(D) a solder mask etching step of exposing a portion of the thermosetting resin layer, which is not protected by the conformal mask formed in (c), to a developer containing an aliphatic amine and an alkali metal hydroxide;

(E) a step of completing a solder mask for heating and curing the above-mentioned thermosetting resin layer;

(F) coating a resist of a metal other than copper on the indentation where the thermosetting resin is removed from the thermosetting resin layer;

(G) removing the copper foil layer by etching; And

(A) removing the metal resist.

Hereinafter, a solder mask pattern forming method of the present invention will be described with reference to FIG.

Fig. 1 (a) shows the layup step of the pattern forming method of the present invention. In the lay-up step, the thermosetting resin 120 and the copper foil 200 are sequentially stacked on the inner layer substrate 100 on which the copper wiring 110 is formed.

In the method of forming a solder mask pattern according to the present invention, the inner layer substrate and the copper wiring layer to be disposed thereon may be those commonly used in the field of printed circuit boards, and a conventional method may be used.

In the solder mask pattern forming method of the present invention, an epoxy-based bismaleimide-triazine (BT) resin may be used as the thermosetting resin, and it may be used in the form of a roll or a sheet having a thickness of 10 to 50 탆

In the solder mast pattern forming method of the present invention, the copper foil layer serves as a conformal mask for pattern formation of the solder mask. The thickness of such a copper foil is sufficient if it is a commonly used one in this field. For example, if it is 1 to 18 탆, it is suitable, and the method of placing the copper foil on the resin layer is also a method commonly used in this industry, Since a press can be used, it is not described here.

The subsequent thermal compression step in the method of forming a solder mask pattern of the present invention is a step of thermosetting the thermosetting resin 120 previously laminated for a solder mask as shown in FIG. 1 (B) by partial curing, for example, a curing rate of 50 to 90% So that the copper foil is thermally bonded to the resin layer. Such partial curing can be realized in a manner known in the art, and an average technician in this field can determine the conditions of a process necessary for partial curing according to the thermosetting resin, so that the detailed process conditions Will not be described in detail herein. For example, if a 25 탆 thick BT resin is used as the thermosetting resin, the partial curing of the thermosetting step may be performed by heating at a temperature of 60 to 120 캜 for 30 to 60 minutes.

Subsequently, in the conformal mask forming step, the copper foil 200 is etched in a shape corresponding to the pattern of the solder mask in the future, as shown in FIG. The copper foil etching technique for forming such a conformal mask can be formed by a method known in the art. For example, in order to form a pattern, a dry film can be used as a masking material and a photolithography process can be used. As the copper etching solution, a hydrogen peroxide-sulfuric acid etching solution can be used. Those skilled in the art will not elaborate further herein because it is possible to select the etching method and process conditions appropriately according to the desired solder mask.

The solder mask etching step in the method of forming a solder mask pattern according to the present invention is a step of etching a portion of the partially cured thermosetting resin layer 120, which is not protected by the conformal mask of the copper foil 200, Is etched with a developing solution containing an aliphatic amine and an alkali metal hydroxide to remove it.

In one embodiment of the solder mask pattern forming method of the present invention, the above-described alkali developer composition of the present invention may be used as the developer containing the aliphatic amine and the alkali metal hydroxide. For example, in one specific embodiment, a partially cured thermosetting resin layer at a process temperature in the range of 40 to 80 占 폚 can be removed at a rate of 2 to 8 占 퐉, for example, using the alkali developing solution composition of the present invention.

In the subsequent step of completing the solder mask in the solder mask pattern forming method of the present invention, the partially cured thermosetting resin layer 120 is heated and completely cured as shown in FIG. 1 (e). As an average technician in the technical field capable of implementing the partial curing of the preceding step, the conditions of the process necessary for full curing can be determined in accordance with the thermosetting resin, so that detailed process conditions for implementing the complete curing step are described in detail in this specification . For example, if a BT resin having a thickness of 25 탆 is used as a thermosetting resin, complete curing of the solder mask can be accomplished by heating at 120 to 180 캜 for 1 to 2 hours.

The metal resist coating step, which is the next step in the method of forming a solder mask pattern of the present invention, is a method of forming a solder mask pattern by etching the solder mask, as shown in FIG. 1 (b) And covering the resist 300 of another metal. The portion of the solder resist coated with the metal resist and the copper wiring layer under the solder resist are prevented from being damaged in the subsequent copper foil etching step. As the metal resist, it is appropriate to use a metal that can not be dissolved as an etching solution used in the following copper foil etching step. In one embodiment of the present invention, tin (Sn) or a tin alloy (Sn alloy) material may be used as the metal resist.

The copper etching step, which is a subsequent step in the method of the present invention, is a step of etching the copper foil 200 used as a conformal mask as shown in FIG. The copper foil etching step of the present invention can be performed by using a copper etching solution commonly used in this technical field and conventional etching conditions. For example, a hydrogen peroxide-sulfuric acid-based etching solution can be used.

The metal resist removing step, which is the next step of the solder mask pattern forming method of the present invention, is a step of removing the metal resist 300 from the substrate as shown in (A) of FIG.

The solder mask pattern forming method according to the present invention can remove a thermosetting resin favorable for manufacturing a high-strength substrate by a wet process with excellent mass productivity. Therefore, in the manufacture of a printed circuit board of ultra thin plate package, And can be replaced with a thermosetting epoxy solder mask resist. Thus, there is an advantage that a highly rigid and highly reliable ultra thin plate package substrate can be mass-produced.

<Examples>

Hereinafter, the present invention will be described in more detail with reference to the following examples and experimental examples. However, it should be understood that the present invention is not limited thereto.

&Lt; Preparation Example > Preparation of alkaline developer

Four types of alkaline developer compositions (Examples 1 to 4) and four types of alkaline developer compositions of the prior art (Comparative Examples 1 to 4) according to the present invention were respectively prepared. The alkaline developers of these Examples and Comparative Examples contained the components per liter in the ratio listed in Table 1 below and the remainder in water.

* The cationic surfactant DQ-590ET

&Lt; Experimental Example > Comparative evaluation of solder mask removal performance

A test for evaluating the solder mask removal performance of the alkaline developer obtained in the above Production Example was carried out as follows. As a test circuit board, a substrate with a 200 μm diameter SMD ball pad was mounted on a double-sided CCL board of 18 μm thick copper through a conventional photolithography process. On this substrate, a 25 μm thick epoxy resin (LaZ 7752 made by Sumitomo Corporation) was laminated on the outer copper wiring layer of this substrate to form a solder mask. Then, a copper foil having a thickness of 12 μm was laminated and heated at 100 ° C. for 30 minutes so that the curing rate of the epoxy resin was 60%, thereby hot-pressing the copper foil. Then, a dry film (RY3315 manufactured by Hitachi, Ltd., Japan) was laminated, exposed and developed, and a copper mask was formed by etching the copper foil with a hydrogen peroxide-sulfuric acid type etching solution (HEP 50, manufactured by YMCT Co., Ltd.). The exposed epoxy resin was developed with the developer described in the present invention at 70 캜 for 200 seconds. The substrate on which the epoxy resin was developed was heated at 150 占 폚 for 2 hours to completely cure the epoxy resin as the solder resist. The exposed SMD ball pads were filled with a tin alloy paste by a screen method, and the copper foil used as a conformal mask was etched away with a hydrogen peroxide-sulfuric acid-based etching solution (HEP 50, manufactured by YMCT Co., Ltd.). Finally, the tin alloy metal masking material was removed using an inorganic acid-based etchant (WYMITE MS 90).

The etching of the solder mask was performed under the conditions summarized in Table 2 using the alkaline developer of the above-described Examples and Comparative Examples. Solder mask pattern formation was observed with an electron microscope to measure the appearance of the solder mask, the solder mask removal rate, the degree of undercut, and the etching rate for the copper wiring. The undercut was defined as the isotropic etch thickness on the basis of one side. The measurement results were combined to evaluate the performance. The evaluation criteria were as follows: No solder mask residue on the copper wiring layer, , And when the thickness is less than 10 μm and less than 20 μm, it is usually judged that the solder mask residue is left on the copper wiring layer or the undercut is not less than 20 μm.

From the results of comparative experiments in Table 2, it can be clearly seen that it is essential to have a combination of a water-soluble aliphatic amine, an alkali, a glycol ether, an azole-based corrosion inhibitor and a surfactant to solve the technical problem of the present invention. In the case of Comparative Examples 1 and 2, the removal rate of the solder mask is equal to or slightly faster than that of Examples 2 and 1, which have a similar process temperature, although the total content of amine and alkali is much larger. On the other hand, in Comparative Examples 1 and 2, occurrence of undercuts is much greater than in Examples 1 and 2. FIGS. 2A and 2B show the formation of the undercut caused by the developer of Comparative Examples 1 and 2 in which the excessive stripping 400 occurred. On the other hand, FIG. 3 shows a high strength ultra thin plate package substrate obtained by using the alkali developer of Example 4 of the present invention. The formation of regular and well-formed SMD ball pads confirms that this board has excellent solder mask resolution.

Further, it can be seen that the alkaline developer of the present invention is far superior to the comparative alkaline developer in the ability to suppress undesired etching on the copper wiring portion. In particular, when comparing Comparative Example 2 with Example 1, it can be seen that the etching rate of copper is 20 times or more different although it contains the same amount of benzotriazole. These results show that this difference is not simply due to the difference in the kind or content of the copper corrosion inhibitor. The above experimental results show that only alkaline developers with a combination of water-soluble aliphatic amines, alkalis, glycol ethers, azole-based copper corrosion inhibitors and surfactants can quickly remove solder masks without residue and prevent excessive undercuts and desired etching of the copper wiring layer .

While the present invention has been particularly shown and described with reference to certain exemplary embodiments thereof, it should be understood that the same is by way of illustration and example only and is not to be taken by way of limitation. It will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims. .

Accordingly, all equivalents of the claims and their equivalents, as well as the embodiments described hereinabove and the appended claims, are also within the scope of the present invention.

100: inner layer substrate 110: outer layer copper wiring
120: Thermosetting resin (solder mask resist)
200: metal foil 300: metal resist
400: area where the solder resist is excessively removed

Claims (14)

200 to 500 g / L of water-soluble aliphatic amine; 200 to 500 g / L of alkali metal hydroxide; 50-200 g / L glycol ether solvent; 1 to 50 g / L of an azole corrosion inhibitor; At least one cationic surfactant selected from oleylimidazolium methosulfate-based quaternary ammonium, oleylamidoamine methosulfate-based quaternary ammonium, dimethylalkylamine derivatives, and alkylamide-based surfactants 0.1 to 50 g / L ; At least one inorganic salt additive selected from sodium metasilicate, potassium monophosphate, potassium diphosphate, potassium triphosphate, sodium monophosphate, sodium diphosphate, sodium triphosphate, ammonium nitrate, sodium nitrate, and potassium nitrate at 50 g / L or less ; And water of the remainder. The alkaline developer composition for removing a resist of a thermosetting solder mask. The method of claim 1, wherein the water soluble aliphatic amine is selected from the group consisting of monoethanolamine, diethanolamine, triethanolamine, aminomethylpropanol, triisopropanolamine, dibutylamine, tributylamine, diisopropanolamine, methylmonoethanolamine, Is selected from amine, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dimethylethanolamine, isopropylamine, cyclopentylamine, cyclohexylamine, diamylamine and mixtures thereof An alkaline developer composition for removing a thermosetting solder mask resist. The alkaline developer composition of claim 1, wherein the alkali metal hydroxide is selected from the group consisting of sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonium hydroxide, and mixtures thereof. The method according to claim 1, wherein the glycol ether solvent is selected from the group consisting of ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, polyethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether , Triethylene glycol monoethyl ether, polyethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, polyethylene glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol mono Ethylene glycol monohexyl ether, ethylene glycol monohexyl ether, ethylene glycol monoaryl ether, ethylene glycol monophenyl ether, ethylene glycol monohexyl ether, ethylene glycol monohexyl ether, ethylene glycol monohexyl ether, ethylene glycol monoaryl ether, LE and these being selected from the mixture of the heat-curable solder mask resist composition for the alkali developing solution. The method of claim 1 wherein the azole corrosion inhibitor is selected from the group consisting of benzotriazole, 5-aminotetrazole, tolyltriazole, 1,2-dimethylimidazole, 1-benzyl- Methylimidazole, 2-bromo-4-nitroimidazole, 2-ethylimidazole, 2-isopropylimidazole, 2-methylimidazole, N, N -carbonyldiimidazole, N, N -carbonyldiimidazole, and mixtures thereof. The method according to claim 1, Wherein the thermosetting solder mask is a thermosetting solder mask. delete delete delete delete A method of forming a solder mask pattern of a printed circuit board,
A lay-up step of sequentially laminating a layer of a thermosetting resin and a copper foil layer on a substrate on which conductive wirings are formed on an inner layer substrate;
A thermocompression bonding step of heating the laminated thermosetting resin so that curing proceeds 50 to 90%;
Forming a conformal mask by etching the copper foil to form a pattern;
Etching the solder mask to expose and remove portions of the thermosetting resin layer, which are not protected by the conformal mask, with the alkaline developer composition for removing a thermosetting solder mask resist of claim 1 containing an aliphatic amine and an alkali metal hydroxide;
A solder mask completing step of heating and curing the thermosetting resin layer;
Coating a resist of a metal other than copper on the depression where the thermosetting resin is removed in the solder mask etching step;
Removing the copper foil layer by etching; And
And removing the metal resist. The pattern forming method according to claim 10, wherein the thermosetting resin is epoxy-based. The method of claim 11, wherein the step of etching the solder mask is performed at a temperature of 40 to 80 ° C. delete The pattern forming method according to claim 10, wherein the metal resist is a tin or tin alloy material.

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