KR20020078975A - Melt-flow controlling method for elastomer by UV irradiation - Google Patents
Melt-flow controlling method for elastomer by UV irradiation Download PDFInfo
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- KR20020078975A KR20020078975A KR1020010019489A KR20010019489A KR20020078975A KR 20020078975 A KR20020078975 A KR 20020078975A KR 1020010019489 A KR1020010019489 A KR 1020010019489A KR 20010019489 A KR20010019489 A KR 20010019489A KR 20020078975 A KR20020078975 A KR 20020078975A
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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
- C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
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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
- C09J109/00—Adhesives based on homopolymers or copolymers of conjugated diene hydrocarbons
- C09J109/02—Copolymers with acrylonitrile
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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
- C09J109/00—Adhesives based on homopolymers or copolymers of conjugated diene hydrocarbons
- C09J109/06—Copolymers with styrene
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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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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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
- C09J125/00—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 aromatic carbocyclic ring; Adhesives based on derivatives of such polymers
- C09J125/02—Homopolymers or copolymers of hydrocarbons
- C09J125/04—Homopolymers or copolymers of styrene
- C09J125/08—Copolymers of styrene
- C09J125/10—Copolymers of styrene with conjugated dienes
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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
- C09J125/00—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 aromatic carbocyclic ring; Adhesives based on derivatives of such polymers
- C09J125/02—Homopolymers or copolymers of hydrocarbons
- C09J125/04—Homopolymers or copolymers of styrene
- C09J125/08—Copolymers of styrene
- C09J125/12—Copolymers of styrene with unsaturated nitriles
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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
- C09J133/00—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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/18—Homopolymers or copolymers of nitriles
- C09J133/20—Homopolymers or copolymers of acrylonitrile
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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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
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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
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
- C09J2301/416—Additional features of adhesives in the form of films or foils characterized by the presence of essential components use of irradiation
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
본 발명은 반도체 패키지용 접착필름으로 사용되는 탄성접착제에 관한 것으로, 특히 탄성접착제의 제조시 코팅공정 후 유동성을 줄이기 위해 자외선을 조사하여 가교시키는 자외선 조사가교에 의한 반도체 패키지용 탄성접착제의 유동성 제어 방법에 관한 것이다.The present invention relates to an elastic adhesive used as an adhesive film for a semiconductor package, and in particular, a method of controlling fluidity of an elastic adhesive for a semiconductor package by ultraviolet irradiation crosslinking by irradiating with ultraviolet rays to reduce fluidity after coating in the manufacture of the elastic adhesive. It is about.
일반적으로 전자산업이 급속도로 발전하고 전자기기의 경박 단소화 및 고기능이 요구됨에 따라 전자기기의 메모리 및 구동회로를 담당하는 반도체의 고집적화와 더불어 얇고 작은 크기로 반도체를 효과적으로 패키징할 수 있는 패키지 방법에 대한 요구가 증가하고 있다. 이러한 요구에 부응하는 형태의 패키지가 CSP(Chip Size Package)이며, CSP중 반도체가 실장되는 보드와의 물리적 연결에 솔더볼을 사용하는 BGA(Ball Grid Array) 타입이 높은 신뢰도를 구현해 주는 현실적인 대안으로 받아들여지고 있다.BGA 패키지는 현재까지 개발된 CSP 중 가장 높은 수준의 신뢰성을 확보해 주는 패키지 타입으로 차세대 메모리 반도체로의 채택이 유력한 램버스 DRAM의 기본 패키지 방법으로 채택되어 있다.In general, as the electronic industry develops rapidly and the light weight and shortness of electronic devices are required and high functions are required, a package method that can effectively package semiconductors in a thin and small size as well as high integration of semiconductors in charge of memory and driving circuits of electronic devices The demand for it is increasing. The package that meets these requirements is the Chip Size Package (CSP), and the Ball Grid Array (BGA) type, which uses solder balls to physically connect to the boards on which semiconductors are mounted, is a realistic alternative that realizes high reliability. It is getting in. BGA package is the package type that ensures the highest level of reliability among the CSPs developed so far, and is adopted as a basic package method of Rambus DRAM, which is adopted as the next generation memory semiconductor.
BGA 패키지가 다른 패키지보다 높은 신뢰성을 갗출 수 있었던 것은 그 내부에 열응력 완충 접착층인 탄성접착제를 도입하였기 때문이다. 탄성접착제는 반도체 칩, 회로와 솔더 패드가 배선되어 있는 플렉스 서브스트레이트 및 PCB 사이의 열팽창 계수 차이에 의하여 발생할 수 있는 패키지의 열변형을 완화, 흡수함으로써 열반복 환경 하에서 솔더볼 조인트의 파괴를 지연하는 역할을 하여 차세대 패키지에도 널리 응용될 것이다. The BGA package was able to exhibit higher reliability than other packages because an elastic adhesive, a thermal stress buffer adhesive layer, was introduced therein. Elastomeric adhesives delay and destroy solder ball joints in thermally repetitive environments by mitigating and absorbing thermal deformation in the package, which can be caused by differences in thermal expansion coefficients between semiconductor substrates, flex substrates that are wired to circuits and solder pads, and PCBs. It will be widely applied to next generation packages.
독일의 베이어사에서 자외선용 불포화 폴리에스터에 관한 특허를 발표한 이후에 세계적으로 자외선 조사가교 방법에 대한 학문적 또는 실용적 연구가 주목을 받아왔으나 목재가구나 가정용품 및 일부 몇몇 분야에 그 응용분야가 국한되어 있는 실정이다.Since the German Bayer company issued a patent on UV unsaturated polyesters, academic and practical research on UV irradiation crosslinking methods has been attracting attention worldwide, but its applications are limited to wood furniture, household goods and some other fields. There is a situation.
종래의 패키지 공정 중에 탄성접착제는 고온(150℃~200℃)에서 작용하는 압력 (1Mpa~1.5Mpa) 하에 기판에 접착되게 된다. 이때 접착압력으로 인한 탄성접착제의 과다한 유동은 회로나 리드의 오염에 의한 전기적 불량이 발생되는 문제점이 있다. 따라서, 탄성접착제의 유동을 최소화하기 위해서 탄성접착제 제조시 가교 공정이 필요한 것이다.In the conventional packaging process, the elastic adhesive is adhered to the substrate under a pressure (1 Mpa to 1.5 Mpa) operating at high temperature (150 ° C to 200 ° C). At this time, the excessive flow of the elastic adhesive due to the adhesive pressure has a problem that the electrical failure caused by the contamination of the circuit or lead. Therefore, in order to minimize the flow of the elastic adhesive, a crosslinking process is required when preparing the elastic adhesive.
종래의 탄성접착제의 가교방식은 가열로를 이용한 열에 의한 경화 방식으로 탄성접착제를 제조하는데 사용되는 코팅용 레진은 접착력을 얻기 위한 에폭시 반응기를 가지고 있는 고분자 수지, 저탄성 특성을 얻기 위한 고무류 수지, 여러 가지 첨가제, 수지들을 용액화하기 위한 적절한 유기용매로 구성되어 있다.Conventional crosslinking method of the elastic adhesive is a coating resin used to prepare the elastic adhesive by heat curing method using a heating furnace is a polymer resin having an epoxy reactor for obtaining the adhesive force, a rubber resin for obtaining low elastic properties, various Eggplant additive, suitable organic solvents for the solution of the resin.
한편, 코팅용 레진으로부터 원하는 물성을 가지는 탄성접착제를 얻기 위해서종래에는 용매를 제거시킨 후 가교공정을 위해 다수의 가열로를 통과시켰다. 이렇게 열을 경화 반응의 에너지원으로 이용하여 에폭시 반응기의 중합반응을 일으키는 것이다.On the other hand, in order to obtain the elastic adhesive having the desired physical properties from the resin for coating, the solvent was conventionally removed and then passed through a plurality of heating furnaces for the crosslinking process. The heat is used as an energy source for the curing reaction to cause the polymerization of the epoxy reactor.
종래의 열경화 방식은 사용도가 다양하고 작업의 용이함 등 여러 가지 장점을 가지고 있으나 다음과 같은 문제점이 있다.Conventional thermosetting method has various advantages such as ease of use and ease of operation, but has the following problems.
열경화 방식은 다수의 열원을 이용함으로 에너지의 낭비와 비용이 많이 들며, 경화 장치인 가열로가 크기 때문에 설치면적이 크며 경화 시간이 수분에서 수시간 단위이기 때문에 생산성이 떨어지며 에폭시의 반응도가 크면 접착제의 특성을 얻기 어렵기 때문에 중합반응의 세세한 조절이 필요하며 에폭시 반응기가 부분적으로 가교반응에 참가하므로 저장 안정성이 떨어져 제품 수명이 짧은 문제점이 있다.The heat curing method wastes energy and costs a lot by using a large number of heat sources, and the installation area is large because the heating furnace, which is a curing device, is large, and the productivity decreases because the curing time is several minutes to several hours. Because it is difficult to obtain the characteristics of the polymerization reaction needs to be finely controlled, and because the epoxy reactor partially participates in the crosslinking reaction, there is a problem of short product life due to low storage stability.
본 발명은 상술한 바와 같은 문제점을 해결하기 위한 것으로, 반도체 패키지의 열응력 완화층으로 사용되는 탄성접착제 제조 공정에서 코팅된 고분자 조성물의 유동성과 가교도를 조절하기 위해 100~500nm의 파장을 가지는 자외선의 조사 공정을 실행하는 것이며, 자외선 가교 방식에 의한 탄성접착제 제조는 가열로를 사용하지 않아 에너지 낭비를 줄이며, 단시간 경화가 가능하므로 생산성을 향상시킬 수 있고, 자외선 광조사량에 의한 가교도 조절이 열가교법에 비해 용이하며, 자외선 조사기의 설치 면적이 가열로에 비해 작으며, 광중합시 에폭시 반응기가 가교반응에 거의 참가하지 않으므로 저장 안정성이 뛰어나서 제품 수명이 긴 자외선 조사가교에 의한 반도체 패키지용 탄성접착제의 유동성 제어 방법을 그 목적으로 한다.The present invention is to solve the problems described above, in order to control the fluidity and crosslinking degree of the polymer composition coated in the elastic adhesive manufacturing process used as a thermal stress relaxation layer of the semiconductor package of the ultraviolet ray having a wavelength of 100 ~ 500nm Irradiation process is carried out, and the production of elastic adhesive by UV crosslinking method does not use a heating furnace to reduce energy waste, and can shorten the curing time, thereby improving productivity, and controlling the degree of crosslinking by UV light irradiation. Compared to the heating furnace, the installation area of the UV irradiator is smaller than that of the heating furnace, and since the epoxy reactor hardly participates in the crosslinking reaction during the photopolymerization, the storage stability is excellent and the fluidity of the elastic adhesive for the semiconductor package by the ultraviolet irradiation crosslinking with a long product life is excellent. The control method is for that purpose.
도 1은 자외선 조사 전에 코팅 후 건조된 탄성접착제 필름.1 is an elastic adhesive film dried after coating before ultraviolet irradiation.
도 2는 도 1의 구조로 구성된 탄성접착제 필름에 자외선을 조사하는 개략도.Figure 2 is a schematic view of irradiating ultraviolet rays to the elastic adhesive film composed of the structure of Figure 1;
도 3은 본 발명의 탄성접착제 필름 위에 자외선을 조사하는 동작 순서도.Figure 3 is a flow chart of the operation of irradiating ultraviolet light on the elastic adhesive film of the present invention.
<도면의 주요 부분에 대한 설명>Description of the main parts of the drawing
10 : 코우팅 모재, 11 : 접착 필름,10: coating base material, 11: adhesive film,
12 : 라미네이션 필름, 20 : 회전롤,12 lamination film, 20 rotary roll,
21 : 탄성접착제, 22 : 자외선 램프.21: elastic adhesive, 22: ultraviolet lamp.
상술한 바와 같은 목적을 달성하기 위한 본 발명의 특징은, 코팅 모재에 원하는 두께로 코팅하는 과정과, 코팅 모재를 건조 후에 라미네이션하여 코팅모재, 접착필름, 라미네이션 필름의 3층 구조로 탄성접착제 필름을 만드는 과정과, 탄성접착제 필름 위에 자외선을 조사하는 과정과, 자외선 조사시에 자외선을 조사량을 조절하는 광중합 과정을 포함한다.A feature of the present invention for achieving the above object is a process of coating a coating base material to a desired thickness, and laminating the coating base material after drying to form an elastic adhesive film in a three-layer structure of a coating base material, an adhesive film, and a lamination film. And a process of irradiating ultraviolet rays onto the elastic adhesive film, and a photopolymerization process of controlling the amount of ultraviolet rays irradiated with ultraviolet rays.
본 발명의 다른 특징으로, 코팅 모재는 투명필름이며 박리 가능하며, 자외선조사량은 탄성접착제의 이동속도를 회전롤로 제어하고 자외선 램프의 광조사량을 제어하여 단위면적당, 단위시간당 탄성접착제에 가해지는 자외선 조사량을 제어하는 것이며, 자외선 램프는 발열에 의하여 자외선을 방출하는 아크타입 램프와 발생된 전자기파에 의하여 상기 자외선을 방출시키는 퓨전타입 램프를 단독 또는 혼합하여 사용하며, 접착필름은 광중합 개시제와 광중합 참여물질을 사용하며, 광중합 개시제는 1-하이드록시 헥실 페닐 키톤, 2-하이드록시-2-메칠-1-페닐 프로판-1-온, 4-(2-하이드록시에칠)페닐-(2-하이드록시-2-메칠프로필)키톤, 포스파이트 옥사이드, 사이클로펜타디에닐 페닐 아이언 엑사풀루오르 포스페이트, 디페닐키톤, 비스(2,6-이메톡시벤조일)-티부틸-2-메틸에틸포스핀옥사이드, 비스(2,4,6-트리메톡시벤조일) 페닐포스핀옥사이드를 단독 또는 혼합하여 사용하며, 광중합 참여물질은 디아크릴레이트계 단량체와 불포화 탄화수소를 함유하는 아크릴로니트릴-부타디엔 공중합체, 아크릴로니트릴 부타디엔 스티렌 공중합체, 아크릴로니트릴 부타디엔 메틸메타크릴레이트, n-부틸아크릴레이트 공중합체를 혼합하여 사용하며, 광중합 참여물질은 상기 불포화 탄화수소 농도가 작은 수소화 아크릴로니트릴-부타디엔 공중합체, 수소화 아크릴로니트릴 부타디엔 스티렌 공중합체, 수소화 아크릴로니트릴 부타디엔 메틸메타크릴레이트 실리콘 공중합체를 혼합하여 사용한다.In another aspect of the present invention, the coating base material is a transparent film and can be peeled off, the amount of ultraviolet radiation is applied to the elastic adhesive per unit area, per unit time by controlling the moving speed of the elastic adhesive with a rotary roll and controlling the light irradiation amount of the ultraviolet lamp. The UV lamp is used alone or in combination of the arc-type lamp that emits ultraviolet rays by heat and the fusion-type lamp that emits the ultraviolet rays by generated electromagnetic waves, and the adhesive film uses a photopolymerization initiator and a photopolymerization participating material. Photopolymerization initiator, 1-hydroxy hexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl propane-1-one, 4- (2-hydroxyethyl) phenyl- (2-hydroxy- 2-methylpropyl) ketone, phosphite oxide, cyclopentadienyl phenyl iron exapoulor phosphate, diphenylketone, bis (2,6-imoxybenzoyl) -tee Butyl-2-methylethylphosphine oxide, bis (2,4,6-trimethoxybenzoyl) phenylphosphine oxide may be used alone or in combination. The photopolymerization participant contains a diacrylate monomer and an unsaturated hydrocarbon. Acrylonitrile-butadiene copolymer, acrylonitrile butadiene styrene copolymer, acrylonitrile butadiene methyl methacrylate, n-butyl acrylate copolymer is used in combination, and the photopolymerization participant is hydrogenated acrylic having a low unsaturated hydrocarbon concentration. A ronitrile-butadiene copolymer, a hydrogenated acrylonitrile butadiene styrene copolymer, and a hydrogenated acrylonitrile butadiene methylmethacrylate silicone copolymer are used in mixture.
이하, 본 발명에 따른 실시 예를 첨부한 도면을 참조하여 상세히 설명하면 다음과 같다.Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings.
도 1은 코팅 후 건조되어 3층 구조를 가지는 필름의 단면을 도시한 것으로, 코우팅 모재(10), 접착필름(11), 라미네이션 필름(12)의 구조로 이루어진다. 코팅후에 건조되어 3층의 구조를 가지는 필름을 제조하는 것은 코우팅 머신에서 한 번의 공정으로 가능하다.1 is a cross-sectional view of a film having a three-layer structure dried after coating, consisting of a coating base material 10, an adhesive film 11, a lamination film 12. It is possible to produce a film having a three-layer structure after drying by coating in one process in a coating machine.
본 발명은 반도체 패키지용 접착필름으로 사용되는 탄성접착제의 제조시 코팅공정 후 유동성을 줄일 목적으로 자외선를 조사하는 것으로, 탄성접착제 제조를 위한 자외선 조사공정, 자외선에 의한 탄성접착제 조성물 개량에 관한 것이다.The present invention is to irradiate ultraviolet rays for the purpose of reducing the fluidity after the coating process in the production of the elastic adhesive used as the adhesive film for semiconductor packages, relates to an ultraviolet irradiation process for producing the elastic adhesive, to improve the elastic adhesive composition by the ultraviolet.
도 2는 도 1의 구조로 구성된 탄성접착제 필름에 자외선을 조사하는 개략도를 도시한 것으로 설명하면 다음과 같다.2 is a schematic diagram illustrating the irradiation of ultraviolet rays to the elastic adhesive film composed of the structure of Figure 1 as follows.
구성은 자외선램프(22)와 회전롤(20)과 탄성접착제 필름(21)으로 이루어지며, 자외선 조사에 의한 가교공정을 보다 구체적으로 설명하면 자외선 조사공정에 사용되는 자외선은 100nm에서 500nm사이의 파장을 사용하며, 주로 200nm에서 350nm 사이의 파장에서 최대값의 광조사량이 나오는 자외선 램프(22)를 사용하는 것이 효율적이다.The composition is composed of an ultraviolet lamp 22, a rotating roll 20, and an elastic adhesive film 21. When explaining the crosslinking process by ultraviolet irradiation in detail, the ultraviolet ray used in the ultraviolet irradiation process has a wavelength between 100 nm and 500 nm. It is efficient to use the ultraviolet lamp 22 which mainly produces the maximum light irradiation amount in the wavelength between 200 nm and 350 nm.
자외선 조사를 위하여 사용하는 자외선램프(22)는 발열에 의하여 바로 자외선를 방출하는 아크타입 램프와 마그네트론 등의 기기를 사용하여 전자기파를 발생하여 발생된 전자기파에 의하여 다시 자외선을 방출시키는 퓨전타입의 램프를 각각 또는 혼합하여 사용한다.The ultraviolet lamp 22 used for ultraviolet irradiation uses an arc type lamp that immediately emits ultraviolet rays by heat, and a fusion type lamp that emits ultraviolet rays again by generating electromagnetic waves using a device such as a magnetron. Or mixed.
3층의 구조를 가지는 탄성접착제 필름(21)을 조사하는데 자외선 램프(22)의 자외선 조사량과 회전롤(20)의 회전속도를 제어하여 단위면적과 단위시간당 탄성접착제 필름(21)이 받는 자외선 광조사량을 변화시킴으로써 광중합개시제의 반응 정도를 조절하여 세밀한 탄성접착제 필름(21)의 가교도의 유동성 조절이 가능하다.Irradiating the elastic adhesive film 21 having a three-layer structure to control the ultraviolet irradiation amount of the ultraviolet lamp 22 and the rotational speed of the rotary roll 20 by the ultraviolet light received by the elastic adhesive film 21 per unit area and unit time By varying the amount of irradiation, the degree of reaction of the photopolymerization initiator is controlled to control the fluidity of the degree of crosslinking of the fine elastic adhesive film 21.
도 3은 본 발명의 탄성접착제 필름 위에 자외선을 조사하는 동작 순서도로 설명하면 다음과 같다.3 is a flowchart illustrating an operation of irradiating ultraviolet rays onto the elastic adhesive film of the present invention.
먼저 탄성접착제 필름을 제조하기 위해 박리가 가능하고 자외선 투과도가 좋은 투명한 필름위에 원하는 두께로 블레이드 코우팅, 그라비아 코우팅, 압출식 코우팅 방법을 사용하여 코우팅한 후 건조하여 코우팅 모재(10), 접착필름(11), 라미네이션 필름(12)으로 3층의 구조를 가지는 탄성접착제 필름을 제조한다(스텝 S30, 스텝 S31).First, a coating is performed by coating a blade coating, a gravure coating, and an extrusion coating method to a desired thickness on a transparent film that can be peeled off and has good UV transmittance in order to manufacture an elastic adhesive film, and then coats the coating base material (10). The elastic adhesive film having a three-layer structure is produced from the adhesive film 11 and the lamination film 12 (step S30 and step S31).
제조된 탄성접착제 필름(21)에 행하는 자외선 조사는 코팅과정이 완료된 후 탄성접착제 필름(21) 위에 바로 행하게 되며 일정한 속도로 탄성접착제 필름(21)이 움직이는 연속적인 상태에서 이루어지게 된다. 이때 가교도는 탄성접착제 필름(21)이 이동하는 속도를 회전롤(20)로 조정하며, 자외선 램프(22)의 자외선 광조사량을 변화시킴으로써 탄성접착제 필름(21)이 단위면적과 단위시간당 받는 광조사량은 세밀하게 유동성의 조절이 가능하다(스텝 S31, 스텝 S32).UV irradiation on the prepared elastic adhesive film 21 is performed directly on the elastic adhesive film 21 after the coating process is completed and is made in a continuous state in which the elastic adhesive film 21 moves at a constant speed. At this time, the degree of crosslinking adjusts the speed at which the elastic adhesive film 21 moves with the rotary roll 20, and changes the amount of ultraviolet light irradiation of the ultraviolet lamp 22 so that the elastic adhesive film 21 receives the unit area and the amount of light received per unit time. Can adjust the fluidity finely (step S31, step S32).
한편, 탄성접착제 필름 가교에 사용된 강경화성 코팅 조성물은 불포화탄화수소를 포함하고 있어야 라디칼 반응에 의한 개시, 전파, 종결 반응으로 중합이 가능하다.On the other hand, the hardenable coating composition used for crosslinking the elastic adhesive film must contain unsaturated hydrocarbons so that polymerization can be initiated, propagated, or terminated by a radical reaction.
탄성접착제 조성물에 첨가되는 광중합 개시제로서는 일단 개시제의 흡수 피크와 자외선 램프의 파장이 일치해야 함을 전제 조건으로 한다. 탄성접착제의 경우 코팅 두께가 비교적 두꺼우므로(175㎛) 자외선 흡수 특성이 뛰어난 1-하이드록시 헥실 페닐 키톤, 2-하이드록시-2-메칠-1-페닐 프로판-1-온, 4-(2-하이드록시에칠)페닐-(2-하이드록시-2-메칠프로필)키톤, 포스파이트 옥사이드, 사이클로펜타디에닐 페닐 아이언 엑사풀루오르 포스페이트, 디페닐키톤, 비스(2, 6-이메톡시벤조일)-티부틸-2-메틸에틸포스핀옥사이드, 비스(2, 4, 6-트리메톡시벤조일) 페닐포스핀옥사이드 등을 단독 또는 혼합하여 사용하는 것이 바람직하다.As a photoinitiator added to an elastic adhesive composition, it is presupposed that the absorption peak of an initiator and the wavelength of an ultraviolet lamp must match once. In the case of the elastic adhesive, the coating thickness is relatively thick (175 μm), and thus, 1-hydroxy hexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl propane-1-one, 4- (2- Hydroxyethyl) phenyl- (2-hydroxy-2-methylpropyl) ketone, phosphite oxide, cyclopentadienyl phenyl iron exapoulor phosphate, diphenylketone, bis (2, 6-Imethoxybenzoyl)- It is preferable to use thibutyl-2-methylethylphosphine oxide, bis (2, 4, 6-trimethoxybenzoyl) phenylphosphine oxide, etc. alone or in combination.
광중합 개시제를 사용하여 광중합에 참여하는 물질로서는 광중합성 디아크릴레이트계 단량체를 기본으로 하여 불포화 탄화수소를 포함하고 있는 아크릴로니트릴-부타디엔 공중합체, 아크릴로니트릴 부타디엔 스티렌 공중합체, 아크로니트릴 부타디엔 메틸메타크릴레이트, n-부틸아크릴레이트 공중합체를 혼합하여 사용한다. 이때 코팅재의 불포화 탄화수소의 농도가 너무 크게 되면 중합 발열반응에 의한 코팅 모재의 손상이 우려되므로 불포화 탄화 수소농도가 보다 작은 수소화 아크릴로니트릴-부타디엔 공중합체, 수소화 아크릴로니트릴 부타디엔 스티렌 공중합체, 수소화 아크릴로니트릴 부타디엔 메틸메타크릴레이트 실리콘 공중합체 등을 사용하는 것이 보다 더 바람직하다.As a material which participates in photopolymerization using a photoinitiator, the acrylonitrile- butadiene copolymer which contains unsaturated hydrocarbon based on a photopolymerizable diacrylate-type monomer, the acrylonitrile butadiene styrene copolymer, and the acrylonitrile butadiene methylmethacryl Late and n-butyl acrylate copolymer are used in combination. At this time, if the concentration of unsaturated hydrocarbon in the coating material is too high, the coating base metal may be damaged due to the polymerization exothermic reaction. It is even more preferable to use ronitrile butadiene methylmethacrylate silicone copolymer or the like.
이러한 광중합과정에서 에폭시 반응기는 반응에 거의 참여하지 않는데 이는 열경화식의 탄성접착제와의 순차주사 열분석(DSC) 결과를 통하여 확인할 수 있었으며 이로부터 탄성접착제의 우수한 접착력, 저장안정성이 뛰어난 결과를 보였다.In the photopolymerization process, the epoxy reactor hardly participates in the reaction, which can be confirmed by the results of sequential scanning thermal analysis (DSC) with the thermosetting elastomeric adhesive, which shows excellent adhesion and storage stability of the elastic adhesive.
본 발명에 따른 탄성접착제의 특성을 실시 예를 통하여 상세히 설명하면 다음과 같다.When explaining the characteristics of the elastic adhesive agent according to the present invention in detail as follows.
먼저, 유동성시험으로 탄성접착제 접착머신(온도 160℃, 압력 2Mpa, 시간 18초)을 사용하여 탄성접착제의 유동량을 측정하는 것으로, 측정에 사용된 샘플크기는 10mm×20mm이며 이때 접착 후 20mm 모서리부에 수직으로 유동한 양을 평균한 것을 유동량으로 정하였을 때 유동량은 300㎛ 이하로 양호한 결과를 보였다.First, the flow rate test measures the flow rate of the elastic adhesive using the elastic adhesive adhesive machine (temperature 160 ℃, pressure 2Mpa, time 18 seconds), the sample size used for the measurement is 10mm × 20mm, 20mm edge after adhesion The flow rate was 300 µm or less when the average flow amount was calculated as the flow rate.
접착력시험은 탄성접착제 접착머신(온도 160℃, 압력 2Mpa, 시간 2초)을 이용하여 접착 모재인 폴리이미드 필름에 접착시킨 후 접착력을 T-peel 시험법으로 측정한 것으로, 접착력 값이 1500g/㎝ 이상으로 열경화 방식의 탄성접착제에 비해 300g 이상 향상되었다.Adhesion test was measured by T-peel test method after bonding to the polyimide film as an adhesive base material using an elastic adhesive adhesive machine (temperature 160 ℃, pressure 2Mpa, time 2 seconds), the adhesion value is 1500g / ㎝ As mentioned above, it improved more than 300g compared with the thermosetting elastic adhesive agent.
탄성접착제의 저장안전성 시험은 진공포장을 푼 후 방치시간에 따른 접착력을 값의 변화로 판단하는 것으로, 5℃ 이하에 방치하였을 경우는 6개월까지 접착력 값의 감소가 나타나지 않았으며 상온에 방치하였을 경우에도 열경화방식의 탄성접착제에 비해 접착력 감소가 원만하였다.The storage safety test of the elastic adhesive is to determine the adhesive force according to the leaving time after unpacking the vacuum packaging. When it is kept below 5 ℃, the adhesive force value does not decrease until 6 months. In addition, the adhesive force was reduced compared to the thermosetting elastic adhesive.
열분석시험은 제조직후 측정한 순차주사 열분석시험(DSC) 결과 에폭시 반응피크의 발열량이 100joule/g 이상으로 열경화방식의 60joule/g ~ 70joule/g 에 비해 크므로 광중합에 의해 에폭시 반응기가 거의 중합에 참여하지 않았음이 확인되었다.The thermal analysis test showed that the amount of calorific value of epoxy reaction peak was 100 joule / g or more, which was higher than that of 60 joule / g ~ 70joule / g of the thermosetting method. It was confirmed that it did not participate in the polymerization.
상술한 바와 같이, 본 발명은 패키지용 탄성접착제의 제조에 있어서 코팅과정이 완료된 후에 자외선 조사를 탄성접착제 필름 위에 바로 행하며 탄성접착제 필름이 일정한 속도로 움직이는 연속적인 상태에서 이루어지고, 탄성접착제 필름이 이동하는 속도를 회전롤로 조정함으로써 단위 면적과 단위 시간당 탄성접착제 필름이 받는 자외선 조사량을 변화시킬 수 있어서 세밀한 조절이 가능하다. 자외선을 조사하는 자외선 램프는 발열에 의하여 자외선을 방출하는 아크타입 램프와 마그네트론 등의 기기를 사용하여 전자기파를 발생하여 발생된 전자기파에 의하여 다시 자외선을 방출시키는 퓨전타입의 램프를 각각 또는 혼합하여 사용한다.As described above, the present invention is made in a continuous state in which the ultraviolet ray irradiation directly on the elastic adhesive film and the elastic adhesive film moves at a constant speed after the coating process is completed in the production of the elastic adhesive for the package, the elastic adhesive film is moved By adjusting the speed of rotation with a rotary roll, the amount of ultraviolet irradiation received by the elastic adhesive film per unit area and unit time can be changed, so that fine adjustment is possible. Ultraviolet lamps that irradiate ultraviolet rays use an arc type lamp that emits ultraviolet rays by heat and a fusion type lamp that emits ultraviolet rays again by electromagnetic waves generated by using electromagnetic devices such as magnetrons. .
한편, 탄성접착제 필름의 자외선 가교에 사용되는 광경화성 코팅 조성물은 불포화탄화수소를 함유하고 있어야하며, 조성물에 첨가되는 광중합 개시제는 자외선 흡수 특성이 뛰어난 1-하이드록시 헥실 페닐 키톤, 2-하이드록시-2-메칠-1-페닐프로판-1-온, 4-(2-하이드록시에칠)페닐-(2-하이드록시-2-메칠프로필)키톤, 포스파이트 옥사이드, 사이클로펜타디에닐 페닐 아이언 엑사풀루오르 포스페이트, 디페닐키톤, 비스(2, 6-이메톡시벤조일)-티부틸-2-메틸에틸포스핀옥사이드, 비스(2, 4, 6-트리메톡시벤조일) 페닐포스핀옥사이드 등을 단독 또는 혼합하여 사용한다.On the other hand, the photocurable coating composition used for ultraviolet crosslinking of the elastic adhesive film should contain unsaturated hydrocarbons, and the photopolymerization initiator added to the composition is 1-hydroxyhexyl phenyl ketone, 2-hydroxy-2 having excellent ultraviolet absorption properties. Methyl-1-phenylpropan-1-one, 4- (2-hydroxyethyl) phenyl- (2-hydroxy-2-methylpropyl) ketone, phosphite oxide, cyclopentadienyl phenyl iron exapoulor Phosphate, diphenylketone, bis (2, 6-imoxybenzoyl) -thibutyl-2-methylethylphosphine oxide, bis (2, 4, 6-trimethoxybenzoyl) phenylphosphine oxide or the like alone or in combination Use it.
또한, 광중합 개시제를 사용하여 광중합에 참여하는 물질은 코팅재의 불포화 탄화수소의 농도가 너무 크게 되면 중합 발열반응에 의한 코팅 모재의 손상이 우려되므로 불포화 탄화 수소농도가 보다 작은 수소화 아크릴로니트릴-부타디엔 공중합체, 수소화 아크릴로니트릴 부타디엔 스티렌 공중합체, 수소화 아크릴로니트릴 부타디엔 메틸메타크릴레이트 실리콘 공중합체 등을 사용하는 것이 더 좋은 결과를 얻는다.In addition, a material that participates in photopolymerization by using a photopolymerization initiator is a hydrogenated acrylonitrile-butadiene copolymer having a smaller unsaturated hydrocarbon concentration because the coating base material may be damaged by polymerization exothermic reaction if the concentration of the unsaturated hydrocarbon in the coating material is too large. It is better to use hydrogenated acrylonitrile butadiene styrene copolymer, hydrogenated acrylonitrile butadiene methylmethacrylate silicone copolymer, and the like.
이상과 같이, 본 발명은 반도체 패키지의 열응력 완화층으로 사용되는 탄성접착제 제조 공정에서 코팅된 고분자 조성물의 유동성과 가교도를 조절하기 위해 100~500nm의 파장을 가지는 자외선의 조사 공정을 실행하여 가열로를 사용하지 않아 에너지 낭비를 줄일 수 있으며 단시간 경화가 가능하여 생산성을 향상시킬 수 있고 자외선 광조사량에 의한 가교도 조절이 열가교법에 비해 용이하며 자외선 조사기의 설치면적이 가열로에 비해 작으며 광중합시 에폭시 반응기가 가교반응에 거의 참가하지 않으므로 저장 안정성이 뛰어나 제품 수명이 긴 효과가 있다.As described above, the present invention is a heating furnace by performing an irradiation process of ultraviolet rays having a wavelength of 100 ~ 500nm to control the fluidity and crosslinking degree of the coated polymer composition in the elastic adhesive manufacturing process used as a thermal stress relaxation layer of the semiconductor package It is possible to reduce energy waste by not using it, and to improve productivity by short curing time, and to control the degree of crosslinking by the amount of ultraviolet light irradiation is easier than the thermal crosslinking method. Since the epoxy reactor hardly participates in the crosslinking reaction, the storage stability is excellent and the product life is long.
또한, 본 발명에 따른 자외선 가교된 탄성접착제는 접착성, 저장안정성, 유동성이 열경화방식으로 제조된 종래의 탄성접착제 보다 탁월한 효과가 있다.In addition, the UV cross-linked elastic adhesive according to the present invention has an excellent effect than the conventional elastic adhesive prepared by the thermosetting method of adhesion, storage stability, fluidity.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100405951B1 (en) * | 2001-04-12 | 2003-11-14 | 엘지전선 주식회사 | Low poisson ratio elastomer by UV irradiation |
| WO2004035703A1 (en) * | 2002-10-18 | 2004-04-29 | Lg Cable Ltd. | Melt-flow controlling method for elastomer by uv irradiation |
| KR100718695B1 (en) * | 2006-12-07 | 2007-05-15 | (주)명성화학 | Double wall sewage pipe with improved rigidity and manufacturing method |
| KR100725024B1 (en) * | 2006-06-05 | 2007-06-07 | 주식회사 덕성 | Manufacturing method of super absorbent hydrocolloid |
| KR102256074B1 (en) * | 2020-05-21 | 2021-05-26 | (주)케이디엔에이 | Stretchable near infrared ray light emitting diode band for smart healthcare |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| KR101668745B1 (en) * | 2015-12-14 | 2016-10-24 | 주식회사 진양엠티에스 | Double-sided adhesive sheet having hybrid cross-linking acryl layer |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US23264A (en) * | 1859-03-15 | Fastening for folding doors | ||
| JPH05136248A (en) * | 1991-11-15 | 1993-06-01 | Hitachi Ltd | Adhesion control device for adhesive tape and device thereof |
| JPH07105368B2 (en) * | 1992-08-05 | 1995-11-13 | 日本加工製紙株式会社 | Adhesive sheet for semiconductor wafer dicing |
| JP3669196B2 (en) * | 1998-07-27 | 2005-07-06 | 日東電工株式会社 | UV curable adhesive sheet |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100405951B1 (en) * | 2001-04-12 | 2003-11-14 | 엘지전선 주식회사 | Low poisson ratio elastomer by UV irradiation |
| WO2004035703A1 (en) * | 2002-10-18 | 2004-04-29 | Lg Cable Ltd. | Melt-flow controlling method for elastomer by uv irradiation |
| KR100725024B1 (en) * | 2006-06-05 | 2007-06-07 | 주식회사 덕성 | Manufacturing method of super absorbent hydrocolloid |
| KR100718695B1 (en) * | 2006-12-07 | 2007-05-15 | (주)명성화학 | Double wall sewage pipe with improved rigidity and manufacturing method |
| KR102256074B1 (en) * | 2020-05-21 | 2021-05-26 | (주)케이디엔에이 | Stretchable near infrared ray light emitting diode band for smart healthcare |
| WO2021235865A1 (en) * | 2020-05-21 | 2021-11-25 | (주)케이디엔에이 | Stretchable near-infrared led band for smart healthcare |
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