KR20010009433A - A method for conversion coating of printed circuit board by using acidic based conversion coating composition - Google Patents
A method for conversion coating of printed circuit board by using acidic based conversion coating composition Download PDFInfo
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- KR20010009433A KR20010009433A KR1019990027790A KR19990027790A KR20010009433A KR 20010009433 A KR20010009433 A KR 20010009433A KR 1019990027790 A KR1019990027790 A KR 1019990027790A KR 19990027790 A KR19990027790 A KR 19990027790A KR 20010009433 A KR20010009433 A KR 20010009433A
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F24—HEATING; RANGES; VENTILATING
- F24H—FLUID HEATERS, e.g. WATER OR AIR HEATERS, HAVING HEAT-GENERATING MEANS, e.g. HEAT PUMPS, IN GENERAL
- F24H9/00—Details
- F24H9/18—Arrangement or mounting of grates or heating means
- F24H9/1809—Arrangement or mounting of grates or heating means for water heaters
- F24H9/1832—Arrangement or mounting of combustion heating means, e.g. grates or burners
- F24H9/1845—Arrangement or mounting of combustion heating means, e.g. grates or burners using solid fuel
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F24—HEATING; RANGES; VENTILATING
- F24H—FLUID HEATERS, e.g. WATER OR AIR HEATERS, HAVING HEAT-GENERATING MEANS, e.g. HEAT PUMPS, IN GENERAL
- F24H1/00—Water heaters, e.g. boilers, continuous-flow heaters or water-storage heaters
- F24H1/22—Water heaters other than continuous-flow or water-storage heaters, e.g. water heaters for central heating
- F24H1/34—Water heaters other than continuous-flow or water-storage heaters, e.g. water heaters for central heating with water chamber arranged adjacent to the combustion chamber or chambers, e.g. above or at side
- F24H1/36—Water heaters other than continuous-flow or water-storage heaters, e.g. water heaters for central heating with water chamber arranged adjacent to the combustion chamber or chambers, e.g. above or at side the water chamber including one or more fire tubes
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F24—HEATING; RANGES; VENTILATING
- F24H—FLUID HEATERS, e.g. WATER OR AIR HEATERS, HAVING HEAT-GENERATING MEANS, e.g. HEAT PUMPS, IN GENERAL
- F24H1/00—Water heaters, e.g. boilers, continuous-flow heaters or water-storage heaters
- F24H1/48—Water heaters for central heating incorporating heaters for domestic water
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- A—HUMAN NECESSITIES
- A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
- A47J—KITCHEN EQUIPMENT; COFFEE MILLS; SPICE MILLS; APPARATUS FOR MAKING BEVERAGES
- A47J37/00—Baking; Roasting; Grilling; Frying
- A47J37/06—Roasters; Grills; Sandwich grills
- A47J37/07—Roasting devices for outdoor use; Barbecues
- A47J37/0786—Accessories
- A47J37/079—Charcoal igniting devices
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F24—HEATING; RANGES; VENTILATING
- F24B—DOMESTIC STOVES OR RANGES FOR SOLID FUELS; IMPLEMENTS FOR USE IN CONNECTION WITH STOVES OR RANGES
- F24B15/00—Implements for use in connection with stoves or ranges
- F24B15/005—Igniting devices; Fire-igniting fans
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F24—HEATING; RANGES; VENTILATING
- F24H—FLUID HEATERS, e.g. WATER OR AIR HEATERS, HAVING HEAT-GENERATING MEANS, e.g. HEAT PUMPS, IN GENERAL
- F24H2230/00—Solid fuel fired boiler
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- Combustion & Propulsion (AREA)
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- Manufacturing Of Printed Wiring (AREA)
Abstract
Description
본 발명은 산성(acidic)기초 화성피막 조성물을 이용한 인쇄회로기판의 화성피막 처리방법에 관한 것이며, 보다 상세하게는 우수한 밀착성 및 내산성을 나타내는 인쇄회로기판의 화성피막 처리방법에 관한 것이다.The present invention relates to a method for processing a chemical film of a printed circuit board using an acidic based chemical film composition, and more particularly, to a method for processing a chemical film of a printed circuit board showing excellent adhesion and acid resistance.
다층인쇄회로기판(MLB) 제조과정에서 내층회로의 흑화처리공정을 채택하고 있는데 흑화처리공정은 다층기판 제조시 내층회로를 주위환경으로부터 보호하고 각 내층과 외층(결합시이트, 프리프레그)을 결합하는 적층공정시 점착력을 극대화할 목적으로 행하여지는 필수불가결한 공정이다.In the manufacturing process of multilayer printed circuit board (MLB), the blackening process of inner layer circuit is adopted. The blackening process protects the inner layer circuit from the surrounding environment and combines each inner layer and outer layer (bonding sheet, prepreg). It is an indispensable process performed for the purpose of maximizing the adhesive force during the lamination process.
지금까지 PCB산업에서 다층인쇄회로기판(MLB) 내층을 흑화처리(Black Oxide)하기 위해서는 흑화처리하기 전에 전처리과정으로서 알카리용액을 이용한 탈지, 수세, 소프트-에칭(Soft-Etching), 산처리, 예비-침지(Pre-Dip)의 공정을 거친후 가성소다 또는 가성알카리(NaOH, KOH)의 알카리 분위기하에서 아염소산 소다(NaClO2)와 같은 산화제를 사용하여 높은 온도(70∼80℃)에서 구리로 이루어진 내층회로를 흑색으로 산화시키는 방법이 사용되어 왔다.Until now, in the PCB industry, in order to black oxide the multilayer printed circuit board (MLB) inner layer, degreasing, washing, soft-etching, acid treatment, preliminary processing using alkaline solution as a pretreatment process before blackening is performed. -After immersion (Pre-Dip) process, using a oxidizing agent such as sodium chlorite (NaClO 2 ) in an alkaline atmosphere of caustic soda or caustic alkali (NaOH, KOH) to copper at high temperature (70 ~ 80 ℃) A method of oxidizing the formed inner layer circuit to black has been used.
상기 종래의 흑화처리공정에 의해 생성된 흑화막은 구리가 산화된 제 2산화구리(CuO)층으로 내산성이 극히 취약하여 흑화처리 후 계속되는 산성욕, 즉 무전해동도금 공정의 소프트-에칭(Soft-Etching, H2SO4/H2O2), 산성구리도금액(CuSO4/H2SO4) 및 그 전처리를 거치면서 드릴링된 홀(hole) 주위의 흑화막이 산에 침식되어 발생하는 핑크링(Pinkring)이라는 심각한 문제가 야기되어 왔다. 이러한 문제점을 해결하기 위하여 종래에는 CuO(Cupric Oxide)층을 내산성이 비교적 우수한 Cu2O(Cuprous Oxide)층으로 환원시키는 공정을 채택하고 있는데 이 환원층은 CuO 층에 비하여 내산성은 우수하지만 근본적으로 소프트 에칭공정 및 황산, 염산, 질산등의 무기산에 용해되는 문제는 해결하지 못한 것이다.The blackening film produced by the conventional blackening process is a copper oxidized cupric oxide (CuO) layer, which is extremely weak in acid resistance, and thus is soft-etched in an acidic bath, that is, an electroless copper plating process, after blackening. , H 2 SO 4 / H 2 O 2 ), acidic copper plating solution (CuSO 4 / H 2 SO 4 ) and the pink ring formed by erosion of blackening around holes drilled through the pretreatment Pinkring has caused a serious problem. In order to solve this problem, conventionally, a process of reducing a CuO (Cupric Oxide) layer to a Cu 2 O (Cuprous Oxide) layer having excellent acid resistance is adopted. The problem of dissolving in the etching process and inorganic acids such as sulfuric acid, hydrochloric acid and nitric acid has not been solved.
또한, 환원공정에 사용되는 환원제는 DMAB(Dimethyl Amine Borane), MPB(Morpholine Borane), HCHO(Formalin), NaBH4(Sodium Borohydride), KBH4(Potassium Borohydride)등이 있으나 주로 사용되고 있는 DMAB와 MPB는 매우 고가의 약품으로 흑화처리 공정비용의 대부분을 차지하고 있는 실정이다.Reducing agents used in the reduction process include DMAB (Dimethyl Amine Borane), MPB (Morpholine Borane), HCHO (Formalin), NaBH 4 (Sodium Borohydride), and KBH 4 (Potassium Borohydride). It is a very expensive drug and accounts for most of the cost of the blackening process.
그 외에도 현재 산성부위기에서 진행하는 흑화처리공정이 몇가지 소개되어 있으나 욕조(bath)의 염소이온농도에 극히 민감하여 관리에 어려운 점이 있으며 접착강도(Peel 혹은 Bonding Strength)가 1kg/㎠ 미만으로 신뢰성면에서 취약한 면을 보이고 있다.In addition, there are some blackening processes that are carried out at acidic sites. However, they are extremely sensitive to chlorine ion concentration in the bath, which makes them difficult to manage. Its reliability is less than 1kg / ㎠. Is vulnerable.
이에 본 발명의 목적은 종래의 알카리 흑화처리공정의 문제점을 해결한 것으로 인쇄회로기판에 내산성 및 접착강도가 우수한 갈색 산화피막을 형성하는 인쇄회로기판의 화성피막형성 방법을 제공하는 것이다.Accordingly, an object of the present invention is to solve the problems of the conventional alkali blackening process to provide a method for forming a chemical conversion film of a printed circuit board to form a brown oxide film having excellent acid resistance and adhesive strength on the printed circuit board.
본 발명의 다른 목적은 종래의 흑화처리공정에 필수적으로 요구되는 전처리 및 후처리공정을 필요로하지 않음으로써 공정라인 및 공정단가가 현저하게 절감되는 인쇄회로기판의 화성피막 형성방법을 제공하는 것이다.Another object of the present invention is to provide a method for forming a chemical conversion film of a printed circuit board, which does not require the pretreatment and posttreatment processes required for the conventional blackening treatment process, thereby significantly reducing process lines and process costs.
도 1에서 (가)는 종래의 흑화처리방법을 (나)는 본 발명에 의한 화성피막처리공정을 나타내는 도면,In Figure 1 (a) is a conventional blackening method (b) is a view showing the chemical conversion coating process according to the present invention,
도 2는 본 발명에 의한 방법으로 형성된 코팅피막의 내약품성에 대한 결과는 나타내는 기판사진이며,Figure 2 is a substrate photograph showing the results on the chemical resistance of the coating film formed by the method according to the present invention,
도 3a 내지 도 3j은 실시예 6에서 본 발명의 화성피막처리방법에 따라 처리된 인쇄기판의 표면상태를 나타내는 사진이다.3A to 3J are photographs showing the surface state of a printed board processed according to the chemical conversion film treatment method of the present invention in Example 6. FIG.
본 발명에 의하면,According to the invention,
Ⅰ. 인쇄회로기판을 세척하는 단계;I. Washing the printed circuit board;
Ⅱ. 수세하는 단계;II. Washing with water;
Ⅲ. 예비침적 조성물의 총 부피를 기준으로 (1)황산 0.1∼5.0v% (2)과산화수소 0.1∼10.0v% 및 (3)황화합물과 반응촉진제 및 안정화중 최소 일성분의 혼합물 10wt%이하로 구성된 예비침적 조성물에 인쇄회로기판을 10∼60℃에서 1∼10분간 예비-침적(Pre-Dip)하는 단계;III. Based on the total volume of the preliminary composition, (1) 0.1 to 5.0 v% sulfuric acid; (2) 0.1 to 10.0 v% hydrogen peroxide; and (3) 10 wt% or less of a mixture of sulfur compounds, reaction accelerators, and at least one component during stabilization. Pre-dipping the printed circuit board into the composition at 10 to 60 ° C. for 1 to 10 minutes;
Ⅳ. 화성피막 조성물의 총 부피를 기준으로 (1)황산 0.1∼30v% (2)과산화수소 0.1∼15v% 및 (3)황화합물과 피막형성보조제, 에칭속도조절제, 반응촉진제 및 안정화제중 최소 일성분의 혼합물 50wt%이하로 구성된 화성피막조성물에 인쇄회로기판을 10∼60℃에서 1∼10분간 적용하여 화성피막 처리하는 단계;Ⅳ. (1) 0.1-30 v% sulfuric acid (2) 0.1-15 v% hydrogen peroxide, and (3) a mixture of sulfur compounds and at least one component of the film-forming aid, etching rate regulator, reaction accelerator and stabilizer based on the total volume of the chemical composition. Applying a printed circuit board to the chemical film composition composed of 50 wt% or less at 10 to 60 ° C. for 1 to 10 minutes to process the chemical film;
Ⅴ. 수세하는 단계; 및Ⅴ. Washing with water; And
Ⅵ. 건조하는 단계;Ⅵ. Drying;
로 구성되는 인쇄회로 기판의 화성피막 형성방법이 제공된다.Provided is a method for forming a chemical film of a printed circuit board.
이하, 본 발명에 대하여 상세히 설명한다.EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.
본 발명에 의한 화성피막 형성방법에서는 산성 기초 화성피막 조성물을 사용하여 인쇄회로기판에 화성피막을 형성함으로써 공정이 단축되며, 또한 인쇄회로기판에 우수한 우수한 내산성 및 내밀착성을 갖는 흑갈색산화피막이형성된다.In the method for forming a chemical film according to the present invention, a process is shortened by forming a chemical film on a printed circuit board using an acidic basic chemical film composition, and a black-brown oxide film having excellent acid resistance and adhesion resistance on the printed circuit board is formed.
본 발명의 화성피막 형성방법에서 먼저 화성피막을 형성하고자하는 하는 인쇄회로기판을 탈지(세척)한다. 화성피막형성시 탈지는 통상 행하여지는 단계로서, 기판에서 전공정(D/F)의 잔사, 이물질 및 지문등이 제거된다. 그 후 수세한다. 수세후, 예비-침적 조성물에 인쇄회로기판을 예비-침적(Pre-Dip)한다.In the method for forming a chemical film of the present invention, first, a printed circuit board to be formed on the chemical film is degreased (washed). Degreasing is usually performed when forming a chemical film, and the residue, foreign matter, fingerprints, etc. of the previous process (D / F) are removed from the substrate. Wash with water after that. After washing with water, the printed circuit board is pre-dipped in the pre-deposited composition.
예비-침적은 화성피막처리전에 화성피막 조성물과 유사한 성분으로 조성되며, 농도는 화성피막조성물보다 농도가 묽은 예비-침적 조성물에 인쇄회로기판을 예비-침적함으로써 화성피막 형성공정에 적합하도록 구리표면을 활성화시켜 코팅초기반응을 앞당기며 균일한 피막이 형성될 수 있는 조건이 갖추어진다. 예비-침적공정은 세척, 컨디셔닝, 촉매 및 활성화등의 기능을 한다.The pre-deposition is composed of a composition similar to that of the chemical film composition before the chemical film treatment, and the concentration is a copper surface suitable for the chemical film forming process by pre-immersing the printed circuit board in a pre-deposit composition having a lower concentration than the chemical film composition. By activating, the initial reaction of the coating is accelerated and the conditions for forming a uniform film are prepared. The pre-deposition process functions as washing, conditioning, catalyst and activation.
예비-침적공정시 사용되는 예비-침적 조성물은 황산, 과산화수소, 유기산, 질소화합물 및 규소화합물 그리고 반응촉진제 및 안정화제중 최소 일성분으로 구성된다.The pre-deposition composition used in the pre-deposition process is composed of at least one component of sulfuric acid, hydrogen peroxide, organic acids, nitrogen compounds and silicon compounds, and reaction accelerators and stabilizers.
예비침적 조성물에 황산은 예비-침적 조성물의 부피를 기준으로 0.1∼5.0v%, 바람직하게는 0.1∼1.0v%로 과산화수소는 예비-침적 조성물의 부피를 기준으로 0.1∼10.0v%, 바람직하게는 0.1∼5.0v%로 사용된다. 황산 및 과산화수소가 0.1v%이하로 사용되면 의도하는 효과를 나타내지 못하며, 황산이 5.0v% 혹은 과산화수소가 10.0v%이상으로 사용되는 경우에는 예비-침적시 구리가 에칭됨으로 바람직하지 않은 것이다.Sulfuric acid in the pre-deposited composition is 0.1 to 5.0 v%, preferably 0.1 to 1.0 v% based on the volume of the pre-deposited composition and hydrogen peroxide is 0.1 to 10.0 v%, preferably based on the volume of the pre-deposited composition It is used at 0.1 to 5.0 v%. If sulfuric acid and hydrogen peroxide are used at less than 0.1v%, the intended effect is not exhibited. If sulfuric acid is used at 5.0v% or hydrogen peroxide of 10.0v% or more, copper is etched during pre-deposition, which is undesirable.
황화합물은 반응촉진제 및 안정화제중 최소 일성분과 후술한 각 조성비내의 조성범위로 혼합하여 혼합물로서 총 예비-침적조성물의 부피를 기준으로 10wt%이하의 양으로 사용된다. 즉, 상기 혼합물은 화성피막조성물 농도의 5/1정도의 농도수준으로 사용하는 것이 예비-침적에서 의도하는 효과를 가장 적절히 달성할 수 있는 것으로 바람직한 것이다.The sulfur compound is used in an amount of 10 wt% or less based on the total volume of the pre-deposited composition as a mixture by mixing at least one component of the reaction accelerator and stabilizer with the composition range within each composition ratio described below. That is, it is preferable that the mixture is used at a concentration level of about 5/1 of the chemical conversion composition concentration so as to most appropriately achieve the intended effect of pre-deposition.
예비-침적은 상기한 바와 같은 조성으로된 예비-침적 조성물에 약 10∼60℃의 온도에서 10초∼10분간 행한다. 예비-침적은 구리표면을 활성화시켜 코팅초기반응을 앞당길 수 있도록 하는 공정으로써 예비-침적하지 않는 경우에는 단지 화성피막형성시 그 반응속도가 지연된다.Pre-deposition is carried out for 10 seconds to 10 minutes at a temperature of about 10-60 ° C. to the pre-deposition composition having the composition as described above. Pre-deposition is a process that activates the copper surface to speed up the initial coating reaction. If it is not pre-deposited, the reaction rate is delayed only when forming the chemical film.
상기한 바와 같이 예비-침적후, 임의로 수세할 수 있으며, 수세하는 것이 바람직하다. 상기 예비-침적 혹은 수세하는 경우에는 수세후, 화성피막조성물읠 인쇄회로기판에 적용함으로써 화성피막을 형성한다.After pre-deposition as described above, washing with water can be optionally performed, and washing with water is preferred. In the case of the pre-deposition or washing with water, after washing with water, a chemical film composition is applied to a printed circuit board to form a chemical film.
화성피막조성물은 (1)황산, (2)과산화수소, (3)황화합물과 (4)피막형성보조제, 에칭속도조절제, 반응촉진제 및 안정화제중 최소 일성분으로 구성되며, 화성피막조성물이 구리 회로에 적용되어 조성물 중 황산 및 과산화수소는 조성물의 산성도를 유지하면서 구리를 에칭하는 작용을 하게 되며 이러한 에칭작용을 구동력으로 하여 황화합물이 금속 구리 표면에 착색되면서 흑갈색 산화피막을 형성하게 된다.The chemical composition is composed of (1) sulfuric acid, (2) hydrogen peroxide, (3) sulfur compounds and (4) film forming aids, etching rate regulators, reaction promoters, and stabilizers. The sulfuric acid and hydrogen peroxide in the composition are used to etch copper while maintaining the acidity of the composition, and the etching action is used as a driving force to form a black-brown oxide film as the sulfur compound is colored on the metal copper surface.
이 때, 황산등을 포함하는 무기 및 유기산 및 과산화수소는 생성된 코팅막의 응집력을 크게하고 접착력을 증대시키며 코팅막의 색상을 보조하는 이차적인 작용을 하게 된다.At this time, the inorganic and organic acids including sulfuric acid and hydrogen peroxide have a secondary function of increasing the cohesion of the resulting coating film, increasing the adhesion and assisting the color of the coating film.
상기 화성피막조성물에 황산은 화성피막조성물의 부피를 기준으로 0.1∼30v%, 바람직하게는 1.0-15 v%로 사용한다. 황산의 양이 0.1 v% 미만인 경우에는 피막을 형성하기 어렵고 30 v% 이상이면 피막의 조직이 치밀하게 형성되지 않는다.Sulfuric acid is used in the chemical composition as 0.1-30v%, preferably 1.0-15v% based on the volume of the chemical composition. If the amount of sulfuric acid is less than 0.1 v%, it is difficult to form a film. If the amount of sulfuric acid is 30 v% or more, the structure of the film is not formed densely.
과산화수소는 화성피막조성물의 부피를 기준으로 0.1∼15v%, 바람직하게는 1.0-10v%를 사용한다. 과산화수소의 양이 0.1 v% 미만인 경우 피막을 형성하기 어렵고, 15v% 이상인 경우 구리의 에칭능력이 지나치게 활성화되어 생성된 피막이 균일하지 못할 뿐만 아니라 재용해의 위험도 따르게 된다.Hydrogen peroxide is used in an amount of 0.1 to 15 v%, preferably 1.0 to 10 v%, based on the volume of the chemical composition. If the amount of hydrogen peroxide is less than 0.1 v%, it is difficult to form a film. If the amount of hydrogen peroxide is more than 15 v%, the etching ability of copper is excessively activated, resulting in an uneven film and a risk of re-dissolution.
황화합물은 피막형성 보조제, 에칭속도 조절제, 반응촉진제 및 안정화제중 최소 일성분은 하기 각 조성비의 범위내의 조성으로 혼합하여 혼합물로서 화성피막조성물의 부피를 기준으로 50wt%이하의 양으로 사용된다.The sulfur compound is used in an amount of 50wt% or less based on the volume of the chemical conversion composition as a mixture by mixing at least one component of the film forming aid, the etching rate control agent, the reaction accelerator and the stabilizer in a composition within the following composition ratio.
즉, 상기 예비-침적 조성물 및 화성피막 조성물에 사용하기 위해 황화합물과 기타 첨가제를 혼합하는 경우, 각 성분을 다음과 같은 비율로 혼합된다.That is, in the case of mixing the sulfur compound and other additives for use in the pre-deposited composition and the chemical conversion composition, each component is mixed in the following ratio.
예비-침적 조성물 및 화성피막조성물에 사용되는 황화합물은 피막조성물의 총부피를 기준으로 0.1∼30wt%, 바람직하게는 0.1∼20wt%, 보다 바람직하게는 0.5∼15wt%의 양으로 사용된다. 0.1wt%이하인 경우에는 코팅층이 지나치게 얇게 형성되며 30 wt%이상일 경우에는 코팅층의 두께워지고 코팅증의 경화도가 지나치게 증대되어 밀착력을 저하시킨다.The sulfur compound used in the pre-deposition composition and the chemical conversion composition is used in an amount of 0.1 to 30 wt%, preferably 0.1 to 20 wt%, more preferably 0.5 to 15 wt%, based on the total volume of the coating composition. If it is less than 0.1wt%, the coating layer is formed too thin. If it is more than 30wt%, the coating layer becomes thick and the degree of curing of the coating is excessively increased, thereby decreasing adhesion.
황화합물로는 무기 황화합물, 유기 황화합물이 모두 사용될 수 있으며, 사용되는 무기 황화합물로는 암모늄염((NH4)2S등) 또는 알칼리금속염(Na2S, K2S)이 그리고 유기 황화합물로는 유기 황화합물로는 술포 술포네이트, 티오시아네이트, 티오술페이트, 티오우레아 및 그 유도체, 티오 인산 및 그 염, 티오 글리콜산 및 그 염, 티오 술페이트 및 술포네이트화합물과 같은 티오화합물 및 메르캅토화합물등 황을 함유하는 어떠한 종류의 유기화합물이 사용된다.Inorganic sulfur compounds and organic sulfur compounds may be used as sulfur compounds, and the inorganic sulfur compounds used may be ammonium salts ((NH 4 ) 2 S, etc.) or alkali metal salts (Na 2 S, K 2 S), and organic sulfur compounds as organic sulfur compounds. Examples thereof include sulfur such as sulfo sulfonate, thiocyanate, thiosulfate, thiourea and derivatives thereof, thiophosphoric acid and its salts, thioglycolic acid and its salts, thio compounds and mercapto compounds Any kind of organic compound containing is used.
한편, -S- 또는 -S-S-, -S-S-S-, R-S-, R-SH, R=S, R-S-(단 화학식 중 R은 탄소, 탄화수소, 또는 질소 및 이들을 포함하는 라디칼 혹은 화합물이다.) 등과 같은 활성황을 포함하는 황화합물이 보다 바람직하며 또한 황화합물 중 질소를 함유하는 것이 더욱 바람직한 것이다.On the other hand, -S- or -SS-, -SSS-, RS-, R-SH, R = S, RS- (wherein R is carbon, hydrocarbon, or nitrogen and radicals or compounds containing them) and the like. Sulfur compounds containing the same active sulfur are more preferred, and it is more preferable to contain nitrogen in the sulfur compounds.
본 발명에 의한 코팅 조성물은 상기 화합물들 외에 그 반응성 및 신뢰성을 증대시키기 위해 다음의 첨가제들을 최소 일종 이상 포함한다.The coating composition according to the present invention contains at least one of the following additives in order to increase the reactivity and reliability in addition to the above compounds.
첨가제로서 피막형성 보조제는 균일한 착색피막이 형성되도록 첨가되는 것으로 하이드로 퀴논(Hydro Quinone), 레조르시놀(Resorcinol), 피로카테올(Pyrocatehol), 피로가롤(Pyrogalol) 및 그 유도체, 1H 벤조트리아졸, 톨리트리아졸, 벤조티아졸, 이미다졸 및 그 유도체가 사용될 수 있다.As an additive, the film forming auxiliary agent is added to form a uniform colored film, such as hydroquinone, resorcinol, pyrocatehol, pyrogalol and its derivatives, 1H benzotriazole , Tolytriazole, benzothiazole, imidazole and derivatives thereof may be used.
상기 피막형성 보조제는 코팅조성물의 부피를 기준으로 0.1-20 wt%, 바람직하게는 0.1-15 wt%, 보다 바람직하게는 0.5-10wt%의 양으로 사용한다. 0.1wt% 이하로 사용할 경우 그 효력이 미비하며 20wt% 이상일 경우 피막형성 반응을 방해하거나 피막의 결합력을 저하시킨다.The film forming aid is used in an amount of 0.1-20 wt%, preferably 0.1-15 wt%, more preferably 0.5-10 wt%, based on the volume of the coating composition. If the amount is less than 0.1wt%, the effect is insignificant, and if it is more than 20wt%, the film forming reaction is disturbed or the bond strength of the film is lowered.
에칭속도 조절제는 코팅반응의 구동력이 되는 구리의 에칭속도를 조절하기 위해 첨가되는 보조제로서 N-메틸-2-피롤리돈, N-시클로헥실-2-피롤리돈, 2-피롤리돈, 디메틸포름아미드, 디메틸 아세트아미드, 테트라하이드로 퓨란, 아세토 니트릴, 디옥산, 알킬 락테이트, 알킬 글리콜레이트, 알킬 포스페이트, 케톤 및 알콜등으로 구성되는 그룹으로부터 선택된 극성용매를 단독 또는 혼합하여 사용한다.Etch rate modifiers are additives to control the etching rate of copper, which is the driving force for the coating reaction. N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, 2-pyrrolidone, dimethyl Polar solvents selected from the group consisting of formamide, dimethyl acetamide, tetrahydrofuran, acetonitrile, dioxane, alkyl lactate, alkyl glycolate, alkyl phosphate, ketones and alcohols are used alone or in combination.
상기 에칭속도 조절제는 코팅조성물의 부피를 기준으로 0.1-30 wt%, 바람직하게는 0.1-20 wt%, 보다 바람직하게는 0.5-10 wt%의 범위로 사용한다. 0.1 wt% 이하로 사용할 경우 에칭속도에 영향을 주지 못하며 30wt% 이상으로 사용할 경우 에칭되는 동의 용해도를 현저하게 감소시킨다.The etch rate modifier is used in the range of 0.1-30 wt%, preferably 0.1-20 wt%, more preferably 0.5-10 wt%, based on the volume of the coating composition. If it is used below 0.1 wt%, it does not affect the etching rate. If it is used above 30wt%, the solubility of copper etched is significantly reduced.
반응 촉진제는 반응촉진 및 피막 생성을 보조하기 위해 예비침적 조성물 및/또는 화성피막 조성물에 첨가되는 것으로 암모늄, 소디움, 포타슘 퍼옥시설페이트와 같은 퍼설페이트류, 소디움, 포타슘 퍼옥시 모노설페이트와 같은 모노설페이트류; NaClO3, KClO3, NH4Cl, FeCl3, CuCl2와 같은 염소산염 및 염산을 포함하는 염화물류; 질산 또는 질산나트륨, 질산칼륨, 질산암모늄과 같은 질산염; 인산 또는 인산염; 질산철, 황산철, 시트르산철과 같은 3 가 철염; 으로 구성되는 그룹으로부터 선택된다.Reaction accelerators are added to pre-deposition compositions and / or chemical conversion compositions to aid in the promotion of reactions and the formation of coatings. Ryu; Chlorides including chlorate and hydrochloric acid such as NaClO 3 , KClO 3 , NH 4 Cl, FeCl 3 , CuCl 2 ; Nitrates or nitrates such as sodium nitrate, potassium nitrate, ammonium nitrate; Phosphoric acid or phosphate salts; Trivalent iron salts such as iron nitrate, iron sulfate and iron citrate; It is selected from the group consisting of.
상기 반응촉진제는 코팅조성물의 부피를 기준으로 0.1-20 wt%, 바람직하게는 0.1-15 wt%, 보다 바람직하게는 0.5-10 wt%의 범위로 사용된다. 0.1 wt% 이하로 사용할 경우 반응촉진 효력이 미비하며 20 wt% 이상으로 사용할 경우 피막색상을 전체적으로 흐리게 만들며 균일한 색상을 얻기 힘들다.The reaction accelerator is used in the range of 0.1-20 wt%, preferably 0.1-15 wt%, more preferably 0.5-10 wt%, based on the volume of the coating composition. If it is used at less than 0.1 wt%, reaction promoting effect is insignificant. If it is used at more than 20 wt%, the film color is blurred overall and it is difficult to obtain uniform color.
안정화제로는 예비-침적 조성물 및/또는 화성피막 조성물에 사용되는 것으로 NTA(Nitrilo Triacetic Acid) 및 그 금속염, EDTA 및 그 금속염, DPTA 및 그 금속염 등과 같은 킬레이트제를 사용된다.Stabilizers are used in pre-deposition compositions and / or chemical conversion compositions, and chelating agents such as Nitrilo Triacetic Acid (NTA) and its metal salts, EDTA and its metal salts, DPTA and its metal salts, and the like.
상기 안정화제는 코팅조성물에 그 총 부피를 기준으로 0.1-20 g/l, 바람직하게는 1-5 g/l의 양으로 사용한다. 0.1 g/l 이하로 사용할 경우 과산화수소를 보호하는 작용이 미미하며 20 g/l 이상으로 사용할 경우 동의 에칭속도를 현저하게 감소시킨다.The stabilizer is used in the coating composition in an amount of 0.1-20 g / l, preferably 1-5 g / l, based on its total volume. If it is used below 0.1 g / l, the protection of hydrogen peroxide is insignificant. If it is used above 20 g / l, the copper etching rate is significantly reduced.
상기 화성피막형성단계는 약 10∼60℃, 바람직하게는 30∼50℃의 온도에서 1∼6분간, 바람직하게는 2∼5분간 행하며, 이 때 화성피막은 화성피막조성물을 인쇄회로기판에 분무하거나 혹은 조성물에 인쇄회로기판을 침지함으로써 형성한다. 10℃이하에서는 화성피막의 밀착력이 저조하며, 60℃이상에서는 필강도가 저하된다.The chemical film forming step is performed for about 1 to 6 minutes, preferably 2 to 5 minutes at a temperature of about 10 to 60 ℃, preferably 30 to 50 ℃, where the chemical film is sprayed on the printed circuit board composition Or by dipping the printed circuit board into the composition. Below 10 ° C, the adhesion of the chemical film is poor, and above 60 ° C, the peel strength decreases.
상기 본 발명의 코팅 조성물은 종래 다층인쇄회로기판(MLB)의 흑화처리공정에서 행하여지던 소프트-에칭(Soft-etching), 산처리, 환원처리공정을 거칠 필요없이 내층기판을 세정 및 수세한 후 기판에 적용함으로써 동(Cu)회로에 흑갈색막을 형성하여 내산성 및 적층시 부여하게 된다.The coating composition of the present invention is a substrate after washing and washing the inner layer substrate without the need to go through the soft-etching, acid treatment, reduction process conventionally performed in the blackening process of the multilayer printed circuit board (MLB) substrate When applied to, a black-brown film is formed in the copper (Cu) circuit to give acid resistance and lamination.
상기한 바와 같은 컨버젼 코팅조성물로 인쇄회로기판을 컨버젼 코팅한 후, 수세하고 건조함으로써 인쇄회로기판의 컨버젼 코팅공정이 완료된다.After conversion coating the printed circuit board with the conversion coating composition as described above, the conversion coating process of the printed circuit board is completed by washing with water and drying.
수세는 3단 수세로 행하고, 그 중 1단은 핫-린스(hot-rinse)로 행한다.Water washing is performed by three steps of water washing, and one step is performed by hot-rinse.
건조는 기판에 수분 혹은 공기가 남아서 기판형성후 라미네이트 공극등 기판을 팽창시키는 결함으로 작용하지 않도록 약 110℃의 온도에서 약 30분간 충분히 건조시킨다.Drying is sufficiently dried at a temperature of about 110 ° C. for about 30 minutes so that moisture or air remains on the substrate so that the substrate does not act as a defect of inflating the substrate such as laminate voids.
이와 같은 화성피막 처리방법은 기판의 표면처리, 레이져드릴, 롤코터, 드라이 필름의 밀착, 인쇄회로 잉크나 열경화성 잉크의 접착력 증대에 적용된다.Such a chemical coating treatment method is applied to the surface treatment of a substrate, the adhesion of a laser drill, a roll coater, a dry film, and the increase of the adhesive force of a printed circuit ink or a thermosetting ink.
이하, 본 발명의 실시예에 대하여 상세히 설명한다.Hereinafter, embodiments of the present invention will be described in detail.
실시예Example
다음 각 실시예에서는 50℃에서 3분간 HD 250™를 사용하여 탈지하고 수세한 후 예비-침적조성물에 25℃에서 1분간 예비-침적 처리한 구리호일과 라미네이트 코어시편(20 x 30cm)을 다음 하기 표 1-1 내지 표 3-1의 각 조성물에 적용하여 인쇄회로기판의 화성피막처리를 행하였으며 그 결과를 하기 표 1-2 내지 3-2에 나타내었다.In each of the following examples, degreased and washed with HD 250 ™ at 50 ° C. for 3 minutes, and then pre-deposited copper foil and laminated core specimens (20 × 30 cm) were subjected to pre-deposition at 25 ° C. for 1 minute. Applying to each composition of Table 1-1 to Table 3-1 was subjected to the chemical conversion coating of the printed circuit board and the results are shown in Table 1-2 to 3-2.
본 실시예 전반에서 사용한 예비침적 조성물은 과산화수소 30ml/l, 황산 5ml/l, 인산 1g/l, 초산 0.1g/l, 2-메르캅토 피리딘 25g/l를 혼합하여 제조하였다.Preliminary immersion compositions used throughout this Example were prepared by mixing 30 ml / l of hydrogen peroxide, 5 ml / l of sulfuric acid, 1 g / l of phosphoric acid, 0.1 g / l of acetic acid, and 25 g / l of 2-mercapto pyridine.
컨버젼 코팅후 수세하고 구리호일 및 라미네이트 코일을 100℃에서 30분간 건조시킨 다음 다음과 같은 조건으로 적층하였다.After the conversion coating, it was washed with water, and the copper foil and the laminate coil were dried at 100 ° C. for 30 minutes, and then laminated under the following conditions.
〈적층 조건〉<Lamination condition>
프리프레그 1080 2장 (다작용성 에폭시 수지 140℃ Tg)2 pieces of prepreg 1080 (140 ℃ Tg of multifunctional epoxy resin)
압력 30 kg/㎠Pressure 30 kg / ㎠
온도 185℃Temperature 185 ℃
시간 170분170 minutes
한편, 구리호일 및 라미네이트 코어 시편에 코팅조성물을 화성피막코팅한 후, 인쇄회로기판의 외관, 접착강도 및 열충격에 대하여 측정하였다.On the other hand, after coating coating the coating composition on the copper foil and laminate core specimens, the appearance, adhesive strength and thermal shock of the printed circuit board were measured.
인쇄회로기판의 외관은 육안관찰하였다.The appearance of the printed circuit board was visually observed.
접착강도는 JIS 규격 C 6481에 의거하여 코팅된 동박을 내층(CCL 원판) 1매와 프리프레그(1080) 상하 2매와 적층성형하고 성형물에 폭 1㎝인 테이프를 붙인다음 동박을 제거하고 테이프를 기준으로 좌,우 1㎝폭을 두고 동박을 에칭한 시편을 잘라서 3cm길이의 시편을 제작하고 테이프를 제거한 후 동박을 90。(직각이 되도록) 4cm 정도 벗긴후 인장강도 측정기로 측정하였다.The adhesive strength is formed by laminating a copper foil coated according to JIS standard C 6481 with one inner layer (CCL disc) and two upper and lower sheets of prepreg 1080, attaching a tape 1cm wide to the molding, and then removing the copper foil. As a reference, the specimens having the width of 1 cm left and right were cut out to prepare a 3 cm long specimen, and after removing the tape, the copper foil was peeled off about 90 cm (to a right angle) about 4 cm and measured by a tensile strength meter.
열충격(Solder Shock)시험은 MIL, JIS 규격에 의해 납(Pb)을 용해시킨 260℃ 및 288℃조에 적층성형된 시편 및 최종 완성된 회로기판을 각각 20초(1사이클, 260℃; JIS C6481 5.5항), 10초(1사이클, 288℃; MIL-S-13949H)동안 침지한 후 마이크로섹션(Micro-Section)하여 딜라미네이션 들뜸 및 라이네이트 손상(liminate void)의 유·무를 관찰하였다.The thermal shock test was performed for 20 seconds (1 cycle, 260 ° C; JIS C6481 5.5) for the laminated specimen and the finished circuit board in 260 ° C and 288 ° C baths in which lead (Pb) was dissolved according to MIL and JIS standards. And immersion for 10 seconds (1 cycle, 288 ° C; MIL-S-13949H), followed by microsection to observe the presence or absence of delamination lifting and laminate voids.
실시예 1Example 1
본 실시예에서는 컨버젼코팅 온도변화에 따른 갈색 산화피막의 형성에 대하여 측정하였다.In this example, the formation of the brown oxide film according to the conversion coating temperature was measured.
하기 표 1의 컨버젼 코팅 조성물을 준비한 후, 상기한 바와 같이 탈지 및 예비-침지 처리한 구리호일 및 라미네이트 코어시편를 코팅조성물의 온도를 25℃, 30℃, 35℃ 및 40℃로 변화시키면서 코팅조성물에 3분간 침지하여 컨버젼 코팅처리하였다. 이때 조성물은 약 0.1m/sec의 속도로 교반하였다.After preparing the conversion coating composition of Table 1, degreased and pre-soaked copper foil and laminate core specimen as described above to the coating composition while changing the temperature of the coating composition to 25 ℃, 30 ℃, 35 ℃ and 40 ℃ It was immersed for 3 minutes to convert coating. At this time, the composition was stirred at a speed of about 0.1 m / sec.
상기 표 1b에서 알 수 있는 바와 같이, 30∼50℃의 온도범위내에서 컨버젼 코팅함으로써 충분한 접착강도를 갖는 갈색 산화피막이 형성되었으며 또한 디라미네션 들뜸 및 라미네이트 손상이 없었다.As can be seen in Table 1b, by converting coating within a temperature range of 30 to 50 ℃ brown oxide film having a sufficient adhesive strength was formed and there was no delamination lift and laminate damage.
실시예 2Example 2
본 실시예에서는 컨버젼 코팅 시간의 변화에 따른 갈색 산화피막의 형성에 대하여 측정하였다.In this example, the formation of the brown oxide film according to the change of the conversion coating time was measured.
하기 표 2a의 코팅 조성물을 준비한 후 상기 실시예에 기술한 바와 같이 전처리하고 코팅시간을 1분, 2분, 3분 4분간으로 변화시켜가면서 시편에 화성피막을 형성하였으며 그 결과를 하기 표 2b에 나타내었다. 이 때 화성피막 처리온도는 35℃로 하였으며, 코팅조성물은 약 0.1m/sec의 속도로 교반하였다.To prepare a coating composition of the following Table 2a and then pre-treatment as described in the above Examples and the coating time was changed to 1 minute, 2 minutes, 3 minutes 4 minutes to form a chemical coating on the specimen and the results are shown in Table 2b Indicated. At this time, the chemical conversion coating temperature was 35 ° C., and the coating composition was stirred at a speed of about 0.1 m / sec.
상기 표 2b의 결과에서 알 수 있는 바와 같이, 2∼5분동안 화성피막처리함으로써 충분한 접착강도를 갖는 갈색의 산화피막이 형성되었으며 또한 라미네션 들뜸 및 라미네이트 공극이 없었다.As can be seen from the results of Table 2b, a brown oxide film having sufficient adhesive strength was formed by chemical conversion coating for 2 to 5 minutes, and there was no lamination lift and laminate voids.
실시예 3Example 3
본 실시예에서는 화성피막 조성물의 교반속도에 따른 갈색 산화피막의 형성에 대하여 측정하였다.In this embodiment, the formation of the brown oxide film according to the stirring speed of the chemical conversion composition was measured.
하기 표 3의 코팅 조성물을 준비한 후 상기 실시예에서 기술한 바와 같이 전처리하고 교반조건을 정체, 0.1 m/s 및 0.2 m/s 로 변화시키면서 화성피막처리하였으며 그 결과를 하기 표 3-2에 나타내었다. 이때, 화성피막처리는 35℃온도에서 3분간 침지하여 행하였다.To prepare a coating composition of the following Table 3 and then pre-treatment as described in the above Example and the chemical conversion coating while changing the stirring conditions to stagnation, 0.1 m / s and 0.2 m / s and the results are shown in Table 3-2 It was. At this time, the chemical conversion treatment was performed by immersion at 35 ° C for 3 minutes.
상기 표 3b의 결과에서 알 수 있듯이, 본원발명에 의한 컨버젼 코팅방법으로 코팅함으로써 충분한 강도의 갈색 산화피막이 형성되며 또한 라미네이션 들뜸 및 라이네이트 손상이 형성되지 않았다.As can be seen from the results of Table 3b, by coating with a conversion coating method according to the present invention, a brown oxide film having sufficient strength was formed, and lamination lifting and lining damage were not formed.
실시예 4Example 4
본 실시예에서는 본 발명에 의한 방법으로 화성피막을 형성하여 제조한 적층 인쇄회로기판의 접착강도를 16회 반복 측정하였다.In this embodiment, the adhesive strength of the multilayer printed circuit board manufactured by forming the chemical film by the method according to the present invention was measured 16 times.
전처리 및 접착강도는 상기 실시예에 기재한 방법으로 측정하였으며,Pretreatment and adhesive strength were measured by the method described in the above examples.
예비침적조성물은 실시예에 기재한 그리고 화성피막조성물은 실시에 3의 조성물 사용하였다. 예비침적은 20∼30℃의 온도에서 1분간 그리고 화성피막처리는 40℃에서 3분간 행하였다.The preliminary deposition composition is described in the examples and the chemical composition was used in the composition of Example 3. Preliminary deposition was performed for 1 minute at the temperature of 20-30 degreeC, and chemical conversion treatment was performed for 40 minutes at 40 degreeC.
종래 사용되된 DMAB 및 MB를 사용하여 흑화처리하는 경우에는 종래의 흑화처리 공정에 따라 기판을 처리하였으며, 시험결과는 하기 표 4에 나타내었다.In the case of blackening treatment using conventionally used DMAB and MB, the substrate was treated according to the conventional blackening treatment process, and the test results are shown in Table 4 below.
상기 표 4-2에서 알수 있는 바와 같이 본원발명에 의한 방법으로 화성피막을 형성하는 경우 그 접착강도가 개선되었다.As can be seen in Table 4-2, when forming a chemical film by the method of the present invention, the adhesive strength was improved.
실시예 5Example 5
본 실시예에서는 본 발명에 의한 방법으로 컨버젼 코팅한 후 형성된 산화막의 내열성(내약품성)에 대하여 측정하였으며 그 결과를 도 2에 나타내었다.In the present embodiment was measured for the heat resistance (chemical resistance) of the oxide film formed after the conversion coating by the method according to the present invention and the results are shown in FIG.
예비-침적은 상기 실시예에 기재한 조성물을 사용하여 20∼30℃의 온도에서 1분간 그리고 화성피막처리는 실시예 3의 화성피막조성물을 사용하였으며, 처리시간은 3분, 3분 30초, 4분 및 5분으로 그리고 처리온도는 24℃, 28℃ 및 32℃로 변화시켜가면서 화성피막코팅하였다.Pre-deposition was carried out for 1 minute at a temperature of 20 ~ 30 ℃ using the composition described in the above Example, and the chemical film treatment was used for the chemical film composition of Example 3, the treatment time is 3 minutes, 3 minutes 30 seconds, The coating film was coated at 4 and 5 minutes and the treatment temperature was changed to 24 ° C, 28 ° C and 32 ° C.
이와 같이 화성피막이 형성된 인쇄회로기판을 전기동, 중화조, 98%황산 및 35% 염산에 각각 1시간동안 침적하였다.Thus, the printed circuit board on which the chemical conversion film was formed was immersed in the copper copper, the neutralization tank, 98% sulfuric acid, and 35% hydrochloric acid for 1 hour.
도 2에서 알 수 있듯이 본 발명에 의한 방법으로 형성된 갈색 산화피막은 98% 황산이나 35%염산에 침적하여도 산화피막이 손상되지 않는 우수한 내약품성을 나타내었다.As can be seen in Figure 2 the brown oxide film formed by the method according to the present invention exhibited excellent chemical resistance that does not damage the oxide film even when deposited in 98% sulfuric acid or 35% hydrochloric acid.
실시예 6Example 6
본 실시예에서 예비-침적은 상기 실시예에 기재한 조성물을 사용하여 20∼30℃의 온도에서 1분간 그리고 화성피막처리는 실시예 3의 화성피막조성물을 사용하였으며, 처리시간을 1회에는 2분, 2분 30초, 3분 및 4분으로 2회에는 2분, 2분 30초, 3분, 3분 30초, 4분 및 5분을 변화시키면서 40℃에서 화성피막처리하였다. 1회 시험시에는 조성물을 교반하지 않았으며 2회 시험시에는 조성물을 1m/s로 교반하였다.In this embodiment, pre-deposition was performed for 1 minute at a temperature of 20 to 30 ° C. using the composition described in the above example, and the chemical conversion treatment was performed using the chemical conversion composition of Example 3, and the treatment time was 2 at a time. In 2 minutes, 2 minutes 30 seconds, 3 minutes and 4 minutes, 2 times, 2 minutes 30 seconds, 3 minutes, 3 minutes 30 seconds, 4 minutes and 5 minutes were subjected to chemical coating at 40 ° C. The composition was not stirred in one test and the composition was stirred at 1 m / s in two tests.
시험결과는 도 3a 내지 도 3j에 나타내었으며, 본 발명에 의한 방법으로 화성피막을 형성한 경우 인쇄회로기판은 우수한 조도를 나타내었다.The test results are shown in FIGS. 3A to 3J, and when the chemical conversion film was formed by the method of the present invention, the printed circuit board showed excellent roughness.
실시예 7Example 7
다음 각 항목에 대하여 본 발명에 의한 화성피막형성방법으로 제작된 인쇄회로기판의 환경시험을 행하였다.For each of the following items, an environmental test of a printed circuit board manufactured by the chemical conversion film forming method according to the present invention was conducted.
본 실시예에서는 5% 250™을 사용하여 50℃에서 3∼5분간 세척하고 40∼50℃에서 1분간 예비침지 하였으며, 40℃에서 3분간 화성피막처리하였다. 그외에 공정은 상기 실시예에 기재한 바와 같이 행하였으며, 예비침적조성물은 실시예에 화성피막 조성물은 실시예 3에 기재된 조성물을 각각 사용하였다.In this example, 5% 250 ™ was used to wash for 3 to 5 minutes at 50 ° C, preliminary immersion at 40 to 50 ° C for 1 minute, and chemical conversion treatment at 40 ° C for 3 minutes. In addition, the process was performed as described in the said Example, and the prepositioned composition used the composition of Example 3 for the chemical conversion film composition for the Example, respectively.
JIS 시험기준에 의거하여 열충격성시험(Thermal Stress-Solder), 기상시험(Air to Air Thermal Cycle), 액상시험(Liquid to Liquid Thermal Shock) 및 항온·항습시험(High Temp. Humidity Test)를 행하였으며, 각각 JIS시험기준에서 요구하는 물성을 통과하는 양호한 특성을 나타내었다.In accordance with the JIS test standards, thermal stress-solder, air to air thermal cycle, liquid to liquid thermal shock, and high temp. And humidity test were performed. , And exhibited good characteristics of passing the physical properties required by the JIS test standard.
본 발명에 의한 화성피막 형성방법으로 조성물을 인쇄회로기판에 코팅함으로써 내산성 및 접착강도가 우수한 흑갈색 산화피막이 형성되며, 나아가, 환원처리공정이 단축되고 종래 사용되된 고가의 환원처리약품의 사용이 배재됨으로 공정 단가가 절감되는 것이다.By coating the composition on the printed circuit board by the method of forming a chemical film according to the present invention, a black-brown oxide film having excellent acid resistance and adhesive strength is formed, and furthermore, the reduction treatment process is shortened and the use of expensive reducing treatment chemicals conventionally used is excluded. The process cost is reduced.
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CN106029795A (en) * | 2014-03-06 | 2016-10-12 | 株式会社Lg化学 | Offset printing composition, printing method using same, and pattern comprising offset printing composition |
US9868868B2 (en) | 2014-03-06 | 2018-01-16 | Lg Chem, Ltd. | Offset printing composition, printing method using same, and pattern comprising offset printing composition |
CN106029795B (en) * | 2014-03-06 | 2019-04-19 | 株式会社Lg化学 | Hectographic printing composition uses the printing process of the hectographic printing composition and the pattern including the hectographic printing composition |
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