KR970008724B1 - Adhesive composition - Google Patents
Adhesive composition Download PDFInfo
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- KR970008724B1 KR970008724B1 KR1019940000116A KR19940000116A KR970008724B1 KR 970008724 B1 KR970008724 B1 KR 970008724B1 KR 1019940000116 A KR1019940000116 A KR 1019940000116A KR 19940000116 A KR19940000116 A KR 19940000116A KR 970008724 B1 KR970008724 B1 KR 970008724B1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J129/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Adhesives based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Adhesives based on derivatives of such polymers
- C09J129/14—Homopolymers or copolymers of acetals or ketals obtained by polymerisation of unsaturated acetals or ketals or by after-treatment of polymers of unsaturated alcohols
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
- C09J161/04—Condensation polymers of aldehydes or ketones with phenols only
- C09J161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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- Organic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
본 발명은 인쇄회로 기판용 동박적층판의 제조시 동박을 배선기판에 결합시키기 위하여 사용되는 접착제 조성물에 관한 것으로, 특허 납조 내열성과 동박접착력이 우수한 동박접착용 접착제 조성물에 관한 것이다.BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an adhesive composition used to bond copper foil to a wiring substrate in the manufacture of a copper foil laminated plate for a printed circuit board, and relates to a copper foil adhesive adhesive composition excellent in patent solder bath heat resistance and copper foil adhesive strength.
최근들어 일반 소비자용 전자부품이 소형 고성능화되면서 인쇄배선판이 점점 고밀도화되고 있다. 이에 따라 인쇄배선판의 기재로 이용되는 인쇄회로 기판용 동박 적층판(CCL, Cooper Clad Laminate)이 갖추어야 할 여러가지 특성들의 향상이 필요하게 되었다. 전자회로가 점점 세선화됨에 따라 절연기재와 동박을 접착시키는 동박접착제의 동박접착력 및 전자부품 실장시 필요한 납조내열성의 향상이 크게 대두되고 있는 실정이다.In recent years, printed circuit boards are becoming more dense as consumer electronic components become smaller and higher performance. Accordingly, there is a need for improvement of various characteristics that a copper clad laminate (CCL, Cooper Clad Laminate) for a printed circuit board, which is used as a substrate of a printed wiring board, is required. As electronic circuits become thinner and thinner, the improvement of the copper foil adhesion strength of the copper foil adhesive that bonds the insulating material and the copper foil, and the heat resistance of the lead bath required when mounting the electronic components, is increasing.
종래에 페놀수지 함침기재에 사용되었던 동박 적층판용 접착제는 폴리비닐부티랄(PVB, POLYⅥNYL-BUTYRAL)수지에 레졸(RESOLE)형 페놀(PHENOL)수지를 가해 사용하다가 동박접착력 및 납조내열성의 향상을 위해 멜라민 수지, 에폭시 수지등 다수의 수지를 첨가시킨 것들이 주로 이용되어 왔다. 그러나 종래의 이러한 접착제들은 내열성과 동박접착력의 특성향상 효과도 충분하지 못하며 그 특성을 동시에 향상시키는데는 한계가 있었다.The copper foil laminate adhesive used in the phenolic resin impregnation base is applied to polyvinyl butyral (PVB, POLYVINYL-BUTYRAL) resin by adding RESOLE type phenol (PHENOL) resin to improve copper adhesive strength and heat resistance of the bath. Melamine resins, epoxy resins, etc., to which many resins have been added have been mainly used. However, these conventional adhesives are not enough to improve the properties of heat resistance and copper foil adhesion force, and there was a limit to improve the properties at the same time.
따라서 본 발명의 목적은 상술한 문제점들을 해결할 수 있는 인쇄회로 기판용 접착제 조성물을 제공하는데 있다.Accordingly, an object of the present invention to provide an adhesive composition for a printed circuit board that can solve the above problems.
상기 목적을 달성하기 위하여 본 발명의 조성물은 폴리비닐 부티랄수지 40-60중량%, 레졸형 페놀 수지 15-40중량%, 에폭시수지 5-30중량% 및 노블락 에폭시 변성 페놀수지 5-30중량%로 이루어진다.In order to achieve the above object, the composition of the present invention is 40-60% by weight of polyvinyl butyral resin, 15-40% by weight of resol type phenolic resin, 5-30% by weight of epoxy resin and 5-30% by weight of noblock epoxy-modified phenolic resin. Is made of.
이하 본 발명을 좀 더 구체적으로 살펴보면 다음과 같다.Looking at the present invention in more detail as follows.
본 발명에 사용된 폴리비닐부랄 수지는 그 종류에 특별한 제한은 없지만, 부티랄화도 60-75mol%, 중합도 1500-2500정도의 것이 최종제품에 요구된 효과를 얻는데 바람직하다. 상기 조건에 상응하는 시판품으로는 일본 적수화학의 S-LEC BX-1. BX-2, BX-5 또는 KS-5, 또는 일본 전기화학의 전하부티랄 5000-A 또는 6000-C 등이 있으며, 본 발명에서는 이들 수지를 단독 또는 혼합하여 사용할 수 있다. 상기 수지의 사용량은 전체 수지에 대하여 40-60중량%가 바람직하며, 40중량% 이하이면 동박접착력이 충분하지 못하고, 60중량% 이상이면 납조내열성이 충분하지 못하다.The polyvinylbural resin used in the present invention is not particularly limited in its kind, but preferably a butyralization degree of 60-75 mol% and a polymerization degree of 1500-2500 are preferred for obtaining the desired effect for the final product. Commercially available products corresponding to the above conditions include S-LEC BX-1. BX-2, BX-5 or KS-5, or the charge butyral 5000-A or 6000-C of the Japanese electrochemical, etc., These resin can be used individually or in mixture in this invention. The amount of the resin is preferably 40-60% by weight relative to the total resin, 40% by weight or less is not enough copper foil adhesive force, 60% by weight or more is not enough lead bath heat resistance.
상기 레졸형 페놀수지는 페놀(P)과 포름알데히드(F)의 몰비를 F/P=1.3-1.8로 하여 알카리성 촉매하에 반응시켜 얻은 액상수지로서, 수지의 중량 평균 분자량이 1000-3000이고, 150℃에서 겔화시간이 50-150초 정도가 본 발명에 바람직하며, 상기 수지의 사용량은 전체 수지에 대하여 15-40중량%가 바람직하며, 15중량% 이하이면 납조내열성이 충분하지 못하고. 40중량% 이상이면 동방접착력이 충분하지 못하다.The resol type phenol resin is a liquid resin obtained by reacting an phenol (P) and a formaldehyde (F) with an alkaline catalyst with a molar ratio of F / P = 1.3-1.8, wherein the weight average molecular weight of the resin is 1000-3000, and 150 It is preferable that the gelation time at about 50-150 seconds in the present invention, the amount of the resin used is 15-40% by weight relative to the total resin, if the 15% by weight or less, the lead bath heat resistance is not enough. If it is 40 weight% or more, the isotropic adhesive force is not enough.
본 발명에 사용되는 에폭시 수지는 비스페놀 A형 에폭시 수지, 비스체놀 F형 에폭시 수지, 페놀 노블락형 에폭시수지, 크레졸 노블락형 에폭시수지 또는 고무변성 에폭시수지 모두 사용가능하며, 좀 더 구체적으로는 EPO THOTO YD-028, YD-011, YD-012 또는 YD-014(국도화학, 비스페놀 A형), EPO THOTO YDF-162 또는 YDF-180(국도화학, 비스페놀 F형). EPO THOTO YDPN-638(국도화학, 페놀노블락형), EPO THOTO YDCN-701, YDCN-702, YDCN-703 또는 YDCN-704(국도화학, 크레졸 노블락형), 또는 EPO THOTO YR-170, YR-207(국도화학, 고무 변성에폭시수지) 등이 있다. 본 발명에서는 상기 에폭시 수지를 단독 또는 그 이상 혼합하여 사용할 수 있으며, 사용량은 전체 수지에 대하여 5-30 중량%가 바람직하며, 5중량% 이하이면 납조내열성이 충분하지 못하고, 30중량% 이상이면 동박접착력이 충분하지 못하다.Epoxy resins used in the present invention can be used both bisphenol A epoxy resin, bisphenolol F epoxy resin, phenol noblock type epoxy resin, cresol noblock type epoxy resin or rubber modified epoxy resin, more specifically EPO THOTO YD -028, YD-011, YD-012 or YD-014 (Kukdo Chemical, Bisphenol A), EPO THOTO YDF-162 or YDF-180 (Kukdo Chemical, Bisphenol F). EPO THOTO YDPN-638 (Kukdo Chemical, Phenolic Block), EPO THOTO YDCN-701, YDCN-702, YDCN-703 or YDCN-704 (Kukdo Chemical, Cresol Noble Type), or EPO THOTO YR-170, YR-207 (Kukdo Chemical, rubber modified epoxy resin). In the present invention, the epoxy resin may be used alone or in admixture, and the amount of the epoxy resin may be used in an amount of 5-30% by weight based on the total amount of the resin. Adhesion is not sufficient
본 발명에 있어서, 노불락 에폭시 변성 페놀수지는 페놀(P), 파라포름알데히드(F) 및 노블락 에폭시 수지로 구성되며, 상기 P와 F의 몰비가 P/F=0.7-1.5이 바람직하고, 상기 노블락 에폭시 수지는 페놀 100중량부에 대하여 20-5중량부가 바람직하다. 이때 상기 P와 F의 몰비가 상기 범위를 벗어나면 수지내 미반응물의 증가로 납조내열성이 저하되는 문제점이 있고, 상기 노블락 에폭시 수지가 상기 범위를 벗어나면 반응을 제어하기 힘든 문제점이 있다.In the present invention, the nobulac epoxy-modified phenol resin is composed of phenol (P), paraformaldehyde (F) and a noblock epoxy resin, and the molar ratio of P and F is preferably P / F = 0.7-1.5. 20-5 weight part of a noblock epoxy resin is preferable with respect to 100 weight part of phenols. At this time, when the molar ratio of P and F is out of the range, there is a problem in that lead bath heat resistance is lowered due to an increase in unreacted substances in the resin, and when the noblock epoxy resin is out of the range, it is difficult to control the reaction.
본 발명에 있어서, 상기 노블락 에포기 수지는 페놀 노블락 에폭시수지 및/또는 크레졸 노블락 에폭시 수지 모두 사용가능하고, 이들의 구체적인 예로는 국도화학의 EPO THOTO YDPN-638, 또는 YDCN -701, 702, 703또는 704등이 있다.In the present invention, the noble block epoxy resin can be used both phenolic noble block epoxy resin and / or cresol noble block epoxy resin, specific examples thereof are EPO THOTO YDPN-638, or YDCN -701, 702, 703 or 704, etc.
상기 조성물들에 트리 에탄올 아민과 같은 아민계 촉매를 사용하여 반응온도 80-90℃에서 약 2-3시간 반응시켜 중량 평균 분자량이 1000-3000이고. 겔화 시간이 150℃에서 100-150초인 수지를 제조할 수 있다The compositions were reacted with an amine catalyst such as triethanolamine at a reaction temperature of 80-90 ° C. for about 2-3 hours to obtain a weight average molecular weight of 1000-3000. A resin having a gelation time of 100-150 seconds at 150 ° C. can be prepared.
이렇게 제조된 노블락 에폭시 변성 페놀수지는 최종 조성물에 대하여 5-30중량%로 혼합되어 접착제 조성물에서 레졸형 페놀수지와 에폭시 수지와의 상용성을 증가시켜 이들 수지간의 반응성을 우수하게 하나, 상기 범위를 벗어나면 그 효과를 충분히 볼 수가 없다. 따라서 접착제 경화후의 각 수지간의 가교밀도의 증가로 인하여 내열성 및 동박접착력이 향상되는 것이다.The noblock epoxy modified phenolic resin thus prepared was mixed at 5-30% by weight with respect to the final composition to increase the compatibility between the resol type phenolic resin and the epoxy resin in the adhesive composition, thereby improving the reactivity between these resins, If you get off, you won't see the effect. Therefore, heat resistance and copper foil adhesive force are improved by increasing the crosslinking density between resins after curing of the adhesive.
상기와 같이 구성된 접착제 조성물에 용제로서 메탄올, 메틸에틸케톤. 톨루엔등을 가하여 25℃에서 점도가 2000-5000cps 정도되는 수지용액으로 제조한 다음, 이 수지액을 20-45㎛ 정도의 두께로 동박에 도포시킨 후 상온에서 30분 정도 방치한 다음, 140-160℃에서 3-7분 건조시켜 접착제 도포동박을 제조하여 적층판에 동박을 접착시킨다.Methanol and methyl ethyl ketone as a solvent in the adhesive composition comprised as mentioned above. Toluene was added to prepare a resin solution having a viscosity of about 2000-5000 cps at 25 ° C. Then, the resin solution was applied to copper foil with a thickness of about 20-45 μm, and left at room temperature for about 30 minutes, and then 140-160 It dried at 3 degreeC for 3-7 minutes, the adhesive coated copper foil was produced, and the copper foil was adhere | attached on a laminated board.
동박에 상기 수지의 도포량은 25-35g/㎡으로 하여 이것을 통상의 방법으로 유리 부직포, 종이등의 기재위에 페놀수지. 에폭시수지등의 수지를 함침한 수지 함침 기재 적층판을 놓고서 가온, 가압시켜 접착한다.The coating amount of the said resin on copper foil is 25-35 g / m <2>, and this is a phenol resin on base materials, such as a glass nonwoven fabric and paper by a normal method. The resin-impregnated base material laminated board which impregnated resin, such as an epoxy resin, was put, and it heated and pressed and bonded.
이하 제조예, 실시예 및 비교예를 통하여 본 발명의 구성 및 효과를 좀 더 구체적으로 살펴보지만, 하기 예에 본 발명의 범주가 한정되는 것은 아니다.Although the configuration and effects of the present invention will be described in more detail with reference to Preparation Examples, Examples, and Comparative Examples, the scope of the present invention is not limited to the following Examples.
제조예 1(레졸형 페놀수지의 제조)Preparation Example 1 (Preparation of Resol Type Phenol Resin)
레졸형 페놀수지는 페놀(P)과 87%, 파라포름알데히드(F)를 몰비 F/P=1.8로 하고 여기에 반응촉매로 트리 에탄을 아민을 페놀에 대해 0.3중량% 넣고 80℃에서 2시간 반응시킨 후 메탄올을 첨가시켜 고형분 50중량%의 수지를 제조하였다. 이 수지의 평균분자량은 1600이었고 150℃에서의 겔화시간은 150초 이었다.Resol type phenol resin was 87% of phenol (P) and paraformaldehyde (F) in molar ratio F / P = 1.8, and triethane was added 0.3% by weight of amine to phenol as a reaction catalyst. After the reaction, methanol was added to prepare a resin having a solid content of 50% by weight. The average molecular weight of this resin was 1600 and the gelation time at 150 ° C. was 150 seconds.
제조예 2(노블락 에폭시 변성 페놀수지의 제조)Production Example 2 (Preparation of Noble Epoxy Modified Phenol Resin)
노블락 에폭시 변성 페놀수지는 페놀 100중량부에 87% 파라포름 알데히드 33중량부와 국도화학의 EPO THOTO YDCN-703 30중량부를 반응촉매로서 트리 에탄올 아민을 0.5중량부 사용하여 온도 90℃에서 2시간 반응시킨 후 탈수 공정없이 메탄올을 가하여 고형분 50%의 수지를 제조하였다. 이 수지의 중량평균 분자량은 2000이었으며 150℃에서 겔화시간은 150초이었다.Noble Epoxy Modified Phenolic Resin was reacted for 2 hours at 90 ° C using 100 parts by weight of phenol and 33 parts by weight of 87% paraformaldehyde and 30 parts by weight of Kukdo Chemical's EPO THOTO YDCN-703 as a reaction catalyst. After the addition, methanol was added without dehydration to prepare a resin having a solid content of 50%. The weight average molecular weight of this resin was 2000 and the gelation time was 150 seconds at 150 ° C.
실시예 1-6 및 비교예 1-3Example 1-6 and Comparative Example 1-3
하기 <표 1>에 기재된 수지배합을 메탄올, 메틸에틸케톤, 톨루엔의 혼합용제에 수지분이 20%되게 균일하게 용해시킨 후 이 접착제를 둥근 유리봉으로 두께 35㎛의 동박에 도포한 후 상온에서 30분, 150에서 5분 건조경화후 접착제층의 두께가 30㎛되는 접착제 부터 동박을 얻었다. 상기 동박의 접착제층에 페놀수지 함침기재 8매를 적충체로서 놓고 150℃, 110kgf/㎠으로 35분간 가열·가압으로 성형시켜 동박적층판을 제조하였다. 하기 <표 1>에 상기 동박적층판의 납조내열성 및 동박접착력을 JIS C6481의 방법으로 그 특성을 측정하여 하기 <표 1>에 기재하였다.After dissolving the resin mixture shown in Table 1 below in a mixed solvent of methanol, methyl ethyl ketone, and toluene so that the resin content was 20%, the adhesive was applied to a copper foil having a thickness of 35 μm with a round glass rod, and then 30 at room temperature. The copper foil was obtained from the adhesive whose thickness of an adhesive bond layer is 30 micrometers after dry hardening for 150 minutes and 150 minutes. Eight phenolic resin impregnated base materials were placed as an antagonist on the adhesive layer of the said copper foil, and it shape | molded by 150 degreeC and 110 kgf / cm <2> by heating and pressure for 35 minutes, and manufactured the copper foil laminated board. In Table 1, the lead bath heat resistance and copper foil adhesion of the copper-clad laminate were measured by the method of JIS C6481 and described in Table 1 below.
[표 1]TABLE 1
전술한 바와 같이, 본 발명의 접착제 조성물은 노블락 에폭시 수지변성 페놀수지를 공지의 접착제 조성물에 첨가시킴으로써 납조내열성 및 동박접착강도를 동시에 향상시켰다. 또한, 고온시의 동박접착강도의 향상이 가능하여 부품 실장시 불량율이 거의 발생되지 않는 인쇄회로 기판의 제조가 가능하다.As described above, the adhesive composition of the present invention simultaneously improved the lead bath heat resistance and the copper foil adhesive strength by adding a noblock epoxy resin-modified phenol resin to a known adhesive composition. In addition, it is possible to improve the copper foil adhesive strength at high temperature, and to manufacture a printed circuit board in which a defect rate is hardly generated when mounting parts.
Claims (9)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019940000116A KR970008724B1 (en) | 1994-01-05 | 1994-01-05 | Adhesive composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019940000116A KR970008724B1 (en) | 1994-01-05 | 1994-01-05 | Adhesive composition |
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| Publication Number | Publication Date |
|---|---|
| KR950023691A KR950023691A (en) | 1995-08-18 |
| KR970008724B1 true KR970008724B1 (en) | 1997-05-28 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1019940000116A KR970008724B1 (en) | 1994-01-05 | 1994-01-05 | Adhesive composition |
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| Country | Link |
|---|---|
| KR (1) | KR970008724B1 (en) |
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1994
- 1994-01-05 KR KR1019940000116A patent/KR970008724B1/en not_active IP Right Cessation
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| Publication number | Publication date |
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| KR950023691A (en) | 1995-08-18 |
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