KR102158580B1 - Developing Solution Composition to come true precision circuit - Google Patents
Developing Solution Composition to come true precision circuit Download PDFInfo
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- KR102158580B1 KR102158580B1 KR1020190013321A KR20190013321A KR102158580B1 KR 102158580 B1 KR102158580 B1 KR 102158580B1 KR 1020190013321 A KR1020190013321 A KR 1020190013321A KR 20190013321 A KR20190013321 A KR 20190013321A KR 102158580 B1 KR102158580 B1 KR 102158580B1
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- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
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- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
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- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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Abstract
본 발명은 인쇄회로기판(Printed Circuit Board, PCB)의 제조 공정에 있어 현상공정에 사용되는 현상용액에 관한 것으로 상세하게는 반응성 계면활성제를 함유하여 PCB의 현상 공정 중에서 회로의 정밀도를 향상시킬 수 있는 정밀 회로구현이 가능한 현상 조성물에 관한 것이다.The present invention relates to a developing solution used in a developing process in a manufacturing process of a printed circuit board (PCB), and in detail, it contains a reactive surfactant to improve the precision of a circuit in the developing process of a PCB. It relates to a developing composition capable of implementing a precision circuit.
Description
본 발명은 인쇄회로기판(Printed Circuit Board, PCB)의 제조 공정에 있어 현상공정에 사용되는 현상용액에 관한 것으로 상세하게는 반응성 계면활성제를 함유하여 PCB의 현상 공정 중에서 회로의 정밀도를 향상시킬 수 있는 정밀 회로구현이 가능한 현상 조성물에 관한 것이다.The present invention relates to a developing solution used in a developing process in a manufacturing process of a printed circuit board (PCB), and in detail, it contains a reactive surfactant to improve the precision of a circuit in the developing process of a PCB. It relates to a developing composition capable of implementing a precision circuit.
PCB는 Photo-lithography 공정을 이용하여 제조하게 된다. 기판에 드라이필름 레지스트 (Dry Film Resist, DFR)를 이용하여 기판에 DFR을 라미네이션을 한다. DFR이 라미네이션 된 기판을 DFR이 기판에 접착력과 안정화를 위해 열처리 또는 상온에서 15 ~ 30분 방치한다. 회로가 형성된 마스크를 이용하여 노광을 수행한다. 마스크에는 빛이 통과하는 영역과 비 통과하는 영역으로 구분되어 있어, 노광 중에 빛이 통과하여 DFR에 도달하면 광 개시반응을 통해 중합과 가교반응이 발생한다. 중합과 가교반응이 발생한 영역과 미 노광부인 중합과 가교반응이 발생하지 않은 영역으로 나누어진다.The PCB is manufactured using a photo-lithography process. Laminate DFR on the substrate using Dry Film Resist (DFR) on the substrate. The DFR-laminated substrate is heat treated or left at room temperature for 15 to 30 minutes for adhesion and stabilization to the DFR substrate. Exposure is performed using a mask on which a circuit is formed. The mask is divided into an area through which light passes and an area through which light passes. When the light passes and reaches DFR during exposure, polymerization and crosslinking reaction occur through a photo-initiated reaction. It is divided into a region where polymerization and crosslinking reaction occurred and a region where polymerization and crosslinking reaction, which is an unexposed portion, did not occur.
반응이 발생한 영역과 발생하지 않은 영역은 알카리에서 용해도의 차이가 발생하고 발생된 용해도 차이를 이용하여 선택적으로 DFR 용해하는 과정을 현상공정이라고 하며, 일반적으로 0.6 ~ 1.5 wt%의 탄산나트륨 또는 탄산가리 수용액이 사용된다. 이때, 미 반응된 DFR의 카르복실산과 탄산나트륨과의 비누화 반응을 통해 용해되고, 가교반응이 된 DFR의 경우에는 용해되지 않고 기판에 잔존하게 된다. In the area where the reaction occurred and the area where the reaction did not occur, the difference in solubility occurs in alkali and the process of selectively dissolving DFR using the difference in solubility generated is called a developing process. In general, 0.6 ~ 1.5 wt% sodium carbonate or garnish aqueous solution Is used. At this time, the unreacted DFR is dissolved through a saponification reaction between the carboxylic acid and sodium carbonate, and in the case of the crosslinked DFR, it does not dissolve and remains on the substrate.
다음 공정은 회로의 구리가 노출된 영역을 에칭으로 부식하여 회로를 형성하고 남아있는 DFR은 박리 용액에서 제거되어 회로를 형성하게 된다. In the next step, the copper-exposed area of the circuit is etched to form a circuit, and the remaining DFR is removed from the stripping solution to form a circuit.
위와 같은 공정을 DES (Developing Etching Stripping) 공정이라고 한다. 이때 회로를 형성하는 공정에서 초기에 시작되는 현상공정에서 현상의 특성이 회로의 정밀도 및 미세패턴을 가능하게 하지만 DFR이 슬러리 및 스컴이 발생되고 발생된 스컴 등은 회로에 재 흡착되어 불량을 유발시키는 문제가 대두되고 있다. 또한 비누화 반응으로 인한 기포의 발생이 급격하게 발생하면서 공정에 불량을 유발하는 인자로 작용되고 있다.The above process is called DES (Developing Etching Stripping) process. At this time, in the development process that starts at the beginning of the circuit forming process, the characteristics of the phenomenon enable the precision and fine pattern of the circuit, but the DFR generates slurry and scum, and the generated scum is re-adsorbed to the circuit, causing defects. Problems are emerging. In addition, bubbles are rapidly generated due to the saponification reaction, which acts as a factor causing defects in the process.
또한 종래에는 발생된 기포를 억제하기 위해 소포제를 사용하여 문제를 해결하고 있으나 소포제를 과량 투입할 경우 현상액의 오염원과 스컴 발생을 촉진하는 문제를 내포하고 있다. 그리고 현상액의 오염 및 스컴으로 인한 현상 탱크의 청소주기가 빨라 원가 상승의 문제도 가지고 있다.In addition, conventionally, the problem is solved by using an antifoaming agent to suppress generated air bubbles, but when an excessive amount of the antifoaming agent is added, the problem of accelerating the generation of contaminants and scum of the developer is implicated. In addition, there is a problem of cost increase because the cleaning cycle of the developing tank is fast due to contamination of the developer and scum.
최근 전자제품의 소형화 그리고 처리속도도 급격하게 빠르게 향상 되고 데이터 용량이 커지고 있어 PCB 기판의 회로의 정밀도가 매우 중요한 문제가 대두되어 지고 있다. 따라서 기판의 회로의 정밀도 향상을 위해 현상 용액에 반응성 계면활성제를 첨가하여 회로의 정밀도을 향상시키기 위한 조성물이 요구되고 있는 실정이다.Recently, the miniaturization and processing speed of electronic products are rapidly improved, and the data capacity is increasing, and thus, the precision of the circuit of the PCB board is a very important problem. Accordingly, there is a demand for a composition for improving the accuracy of the circuit by adding a reactive surfactant to the developing solution in order to improve the accuracy of the circuit of the substrate.
따라서 본 발명의 목적은 반응성 계면활성제를 부여함으로서 용액 내에서 DFR의 뭉침 현상을 줄여주면서 계면활성제 부가로 인한 스컴 및 기포 억제하고 계면장력을 최소화를 통해 회로의 정밀도를 향상시킬 수 있는 정밀 회로구현이 가능한 현상 조성물을 제공하는 것이다.Therefore, it is an object of the present invention to implement a precision circuit that can improve the precision of the circuit by reducing the aggregation of DFR in the solution by providing a reactive surfactant, suppressing scum and air bubbles due to the addition of the surfactant, and minimizing the interfacial tension. It is to provide a possible developing composition.
상기 목적을 달성하기 위한 본 발명의 정밀 회로구현이 가능한 현상 조성물은, PCB의 현상 정밀도를 향상을 목적으로 하고, PCB 현상용액에 스컴의 생성을 억제하거나 방지하기 위해 반응성 계면활성제를 함유하는 것이 특징이다.The developing composition capable of implementing a precision circuit of the present invention to achieve the above object is characterized in that it contains a reactive surfactant for the purpose of improving the development precision of the PCB and to suppress or prevent the generation of scum in the PCB developing solution. to be.
하나의 예로써, 상기 반응성 계면활성제의 농도를 0.1wt% 내지 5wt% 첨가하는 것이 특징이다.As an example, it is characterized in that the concentration of the reactive surfactant is added in an amount of 0.1 wt% to 5 wt%.
하나의 예로써, 상기 반응성 계면활성제는 Polyethyleneimine 및 이민계열 및 아민계열을 포함하는 것이 특징이다.As an example, the reactive surfactant is characterized by including polyethyleneimine and imine series and amine series.
이와 같이 본 발명의 정밀 회로구현이 가능한 현상 조성물은, PEI (Polyethyleneimine) 및 아민을 포함하는 현상용액 조성물로서 회로의 형성 시, 회로의 정밀도를 향상시키고 또한 분산성과 소포성을 부여하여 용액내의 스컴을 억제할 수 있는 효과가 있다. As described above, the developing composition capable of implementing a precision circuit of the present invention is a developing solution composition containing PEI (Polyethyleneimine) and an amine. When forming a circuit, it improves the precision of the circuit and imparts dispersibility and defoaming properties to reduce scum in the solution. It has a suppressive effect.
뿐만 아니라 본 발명에 의하면, 계면활성제가 함유되어 있어 현상의 형상이 잘 되고 칫수 구현을 정밀하게 할 수 있는 효과가 있다.In addition, according to the present invention, since the surfactant is contained, the shape of the development is good and there is an effect that the dimension can be accurately implemented.
도 1은 현상용액에서 PEI 유무에 따른 스컴의 발생 비교 사진.
도 2는 PEI 1Wt% 함유한 현상 용액의 낙차 실험에 의한 기포발생 실험.
도 3은 PEI가 함유된 현상용액으로 형성된 회로 구현.
도 4는 Resist Foot 측정 사진.1 is a comparative picture of the occurrence of scum according to the presence or absence of PEI in a developing solution.
2 is a bubble generation experiment by a drop test of a developing solution containing 1Wt% PEI.
3 is a circuit implementation formed with a developer solution containing PEI.
Figure 4 is a photograph of a resist foot measurement.
이하, 본 발명의 구성 및 작용을 첨부된 도면에 의거하여 좀 더 구체적으로 설명한다. 본 발명을 설명함에 있어서, 본 명세서 및 청구범위에 사용된 용어나 단어는 발명자가 그 자신의 발명을 가장 최선의 방법으로 설명하기 위해 용어의 개념을 적절하게 정의할 수 있다는 원칙에 입각하여 본 발명의 기술적 사상에 부합하는 의미와 개념으로 해석되어야만 한다.Hereinafter, the configuration and operation of the present invention will be described in more detail based on the accompanying drawings. In describing the present invention, terms or words used in the present specification and claims are the present invention based on the principle that the inventor can appropriately define the concept of terms in order to explain his or her invention in the best way. It must be interpreted as a meaning and concept consistent with the technical idea of
본 발명의 정밀 회로구현이 가능한 현상 조성물은 PEI(Polyethyleneimine) 및 아민을 포함하는 현상 조성물을 제공한다. The developing composition capable of implementing a precision circuit of the present invention provides a developing composition including polyethyleneimine (PEI) and an amine.
또한, 본 발명은 소포성이 함유한 현상용액으로서 현상 공정 중에서 DFR의 카르복실산과 이민과의 산염기 반응을 통해 현상 용액의 소포성이 향상되는 현상 조성물을 제공한다. In addition, the present invention provides a developing solution containing antifoaming properties, in which the antifoaming property of the developing solution is improved through an acid-based reaction between a carboxylic acid of DFR and an imine during a development process.
또한, PEI 계면활성제의 분산성과 양이온 수소와의 반응성을 확보하여 카르복실산이 양이온 수소와의 반응을 억제하여 스컴의 발생을 억제하는 현상 조성물을 제공한다. In addition, there is provided a developing composition in which the dispersibility of the PEI surfactant is secured and the reactivity with cationic hydrogen is secured to suppress the reaction of the carboxylic acid with cationic hydrogen to suppress the generation of scum.
아울러, 본 발명은 계면활성제를 포함하여 계면간의 계면장력을 최소화하며 회로의 정밀도를 향상시킬 수 있도고 한다.In addition, the present invention also includes a surfactant to minimize the interfacial tension between interfaces and improve the precision of the circuit.
본 발명의 정밀 회로구현이 가능한 현상 조성물은 PEI를 함유하는 현상 조성물로, 탄산가리, 탄산나트륨 또는 탄산암모늄 용액에 0.01 ~ 5%의 PEI를 포함한다.The developing composition capable of implementing a precision circuit of the present invention is a developing composition containing PEI, and contains 0.01 to 5% of PEI in a solution of gari carbonate, sodium carbonate or ammonium carbonate.
상기 현상 조성물에 탄산가리 또는 탄산나트륨 또는 탄산암모늄을 혼합하여 사용할 수 있다.Gari carbonate, sodium carbonate, or ammonium carbonate may be mixed with the developing composition.
상기 탄산염 등의 농도는 0.05 ~ 1.5Wt%가 바람직하다. 0.05 Wt%보다 낮을 경우에는 현상 속도가 급격하게 저하되는 문제점을 함유하고, 1.5Wt%보다 높을 경우 가교된 DFR이 용해되는 문제가 있다.The concentration of the carbonate or the like is preferably 0.05 to 1.5 Wt%. If it is lower than 0.05 Wt%, there is a problem in that the development rate is rapidly lowered, and if it is higher than 1.5 Wt%, there is a problem that the crosslinked DFR is dissolved.
이때 첨가하는 PEI의 종류는 다양한 종류를 사용할 수 있으며, 예를 들면 Polyethylenimine, linear, Polyethylenimine hydrochloride, Hexamethyleneimine, N-Methylethylenediamine, 1,3-Diamino-2-propanol 인 것이 바람직하다. At this time, various types of PEI can be used, and for example, polyethylenimine, linear, polyethylenimine hydrochloride, hexamethyleneimine, N-Methylethylenediamine, and 1,3-Diamino-2-propanol are preferable.
상기 반응성 계면활성제는 0.1 ~ 5 wt%인 것이 바람직하고, 0.05 ~ 3 Wt% 인 것이 더욱 바람직하다. 여기서 0.01wt% 보다 낮을 경우 소포성과 반응성이 떨어져 효과가 반감이 되고, 5Wt% 보다 높을 경우 소포성과 반응성 특성효과의 차이가 없으며, 점성이 올라가는 문제가 발생한다.The reactive surfactant is preferably 0.1 to 5 wt%, and more preferably 0.05 to 3 Wt%. Here, if it is lower than 0.01wt%, the antifoaming property and reactivity are lowered, and the effect is halved. If it is higher than 5Wt%, there is no difference in the antifoaming property and reactivity effect, and a problem of increasing viscosity occurs.
상기 현상의 온도는 20 내지 50℃ 범위인 것이 바람직하고, 여기서, 현상용액의 온도는 20 내지 50℃ 범위에서 온도가 낮은 때에는, 현상속도가 급격하게 저하되는 문제가 발생할 수 있으며, 온도가 높을 때에는 가교된 DFR의 용해가 발생할 수 있다. It is preferable that the temperature of the development is in the range of 20 to 50°C. Here, when the temperature of the developing solution is in the range of 20 to 50°C, when the temperature is low, a problem that the development speed is rapidly decreased may occur, and when the temperature is high Dissolution of the crosslinked DFR can occur.
이하, 본 발명을 구체적으로 설명하기 위해 실시예를 들어 상세히 설명하기로 한다. 본 발명은 하기의 실시예에 의하여 보다 더 잘 이해 될 수 있으며, 하기의 실시예는 본 발명의 예시 목적을 위한 것이며, 첨부된 특허청구범위에 의하여 한정되는 보호범위를 제한하고자 하는 것은 아니다.Hereinafter, examples will be described in detail in order to describe the present invention in detail. The present invention may be better understood by the following examples, and the following examples are for illustrative purposes of the present invention, and are not intended to limit the scope of protection defined by the appended claims.
실시예Example
본 발명의 일 실시예로서 탄산나트륨 또는 탄산가리를 물에 0.5 wt%, 1 Wt%, 1.5 Wt%의 농도로 용액을 각각 제조한다. As an embodiment of the present invention, a solution of sodium carbonate or garridium carbonate in water at a concentration of 0.5 wt%, 1 Wt%, and 1.5 Wt% is prepared, respectively.
이때 상온에서 200RPM으로 교반하여 분말을 완전히 용해한다. 여기에 다양한 PEI를 0.1 W%, 0.5W%, 1Wt%, 3Wt%, 5Wt%를 첨가하여 시료를 제조하였다. At this time, the powder is completely dissolved by stirring at 200RPM at room temperature. Samples were prepared by adding 0.1 W%, 0.5W%, 1Wt%, 3Wt%, and 5Wt% of various PEIs.
제조된 시료에 DFR 1.0M2/L 양으로 용해하였다. The prepared sample was dissolved in an amount of DFR of 1.0M2/L.
교반기를 이용하여 5시간 이상 충분하게 DFR을 용해하였으며, 용해된 시료는 불투명한 푸른색을 나타내었다. 제조된 시료는 pH를 2가 될 때까지 염산을 투입하여 용액의 변화를 관찰 한다. DFR was sufficiently dissolved for 5 hours or more using a stirrer, and the dissolved sample showed an opaque blue color. In the prepared sample, hydrochloric acid is added until the pH becomes 2, and the change of the solution is observed.
스컴의 발생유무를 관찰하고 여과하여 무게로 스컴의 발생을 평가하였다. 하기 [표 1]은 탄산 종류 및 PEI에 따른 슬러지 발생 유무를 나타내는 비교표로, [표 1]을 본 실시 예에 따른 스컴 발생 여부를 확인할 수 있다.The occurrence of scum was observed and filtered to evaluate the occurrence of scum by weight. The following [Table 1] is a comparison table showing the occurrence of sludge according to the type of carbonic acid and PEI, and it is possible to check whether scum occurs according to the present embodiment from [Table 1].
한편 도 1은 스컴 발생 유/무 사진이며, 사진에서 도시된 바와 같이 PEI를 첨가하지 않은 시료의 경우에는 DFR 뭉쳐 스컴이 발생된 것을 확인 할 수 있다. Meanwhile, FIG. 1 is a picture of the presence/absence of scum generation, and as shown in the photo, in the case of a sample without adding PEI, it can be confirmed that scum is generated due to DFR aggregation.
이후 제조된 현상 조성물은 기포 발생실험을 수행하였다. 결과는 도 2에 도시된 바와 같이 기포가 발생하지 않은 것을 알 수 있었다. Then, the prepared developing composition was subjected to a bubble generation test. As a result, it was found that no air bubbles were generated as shown in FIG. 2.
또한 제조된 현상용액을 이용하여 회로의 정밀도 측정하였다.다양한 Line/Space 이용하여 현상을 하였고, 도 3에 보여지고 있는 것처럼 현상이 잘 형성되어 있는 것을 확인되었다. 또한 칫수 구현도 잘되어 있는 것을 확인 하였다. 또한 도 4에 Resist Foot도 500nm 이하로 발생하는 것을 확인하였다. In addition, the precision of the circuit was measured using the prepared developing solution. Development was performed using various lines/spaces, and it was confirmed that the phenomenon was well formed as shown in FIG. 3. It was also confirmed that the dimensions were well implemented. In addition, it was confirmed that the Resist Foot also occurs below 500 nm in FIG. 4.
이상 설명한 내용을 통해 당업자라면 본 발명의 기술사상을 일탈하지 아니하는 범위에서 다양한 변경 및 수정 가능함을 알 수 있을 것이다. 따라서, 본 발명의 기술적 범위는 명세서의 상세한 설명에 기재된 내용으로 한정되는 것이 아니라 특허청구범위에 의해 정해져야만 할 것이다.It will be appreciated by those skilled in the art through the above description that various changes and modifications can be made without departing from the technical idea of the present invention. Therefore, the technical scope of the present invention is not limited to the contents described in the detailed description of the specification, but should be determined by the claims.
Claims (3)
상기 반응성 계면활성제는 Polyethyleneimine 및 이민계열 및 아민계열을 포함하는 것을 특징으로 하는 정밀 회로구현이 가능한 현상 조성물.
For the purpose of improving the development precision of the PCB, it contains a reactive surfactant to suppress or prevent the formation of scum in the PCB developing solution,
The reactive surfactant is a developing composition capable of implementing a precision circuit, characterized in that it contains polyethyleneimine and imine series and amine series.
상기 반응성 계면활성제의 농도를 0.1wt% 내지 5wt% 첨가하는 것을 특징으로 정밀 회로구현이 가능한 현상 조성물.
The method of claim 1,
A developing composition capable of implementing a precision circuit, characterized in that 0.1wt% to 5wt% of the concentration of the reactive surfactant is added.
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