KR100871609B1 - Laminating film of plastic-silicon and method for preparing the same - Google Patents

Laminating film of plastic-silicon and method for preparing the same Download PDF

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KR100871609B1
KR100871609B1 KR1020060100035A KR20060100035A KR100871609B1 KR 100871609 B1 KR100871609 B1 KR 100871609B1 KR 1020060100035 A KR1020060100035 A KR 1020060100035A KR 20060100035 A KR20060100035 A KR 20060100035A KR 100871609 B1 KR100871609 B1 KR 100871609B1
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plastic
film
silicone rubber
reactive functional
plastic substrate
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KR1020060100035A
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KR20080033821A (en
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송승호
원유덕
이학민
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선우에이엠씨주식회사
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Priority to PCT/KR2007/004975 priority patent/WO2008044884A1/en
Priority to EP07833286A priority patent/EP2074188A1/en
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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
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/14—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of germanium, tin or lead
    • 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
    • C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
    • C09J183/04—Polysiloxanes
    • 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
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/24—Plastics; Metallised plastics based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/241—Polyolefin, e.g.rubber
    • C09J7/243—Ethylene or propylene polymers
    • 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
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/255—Polyesters

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
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Abstract

본 발명은 플라스틱-실리콘 접착필름 및 그 제조방법에 관한 것으로서, 플라스틱 기재의 표면에 플라즈마 처리를 통해 반응성 작용기를 활성시키고, 또한 상기 반응성 작용기와 화학적 결합이 가능한 실란 커플링제를 함유시킨 액상 실리콘 고무를 상기 플라스틱 기재에 도포하여 경화시킴으로써, 상기 플라스틱 기재와 실리콘 고무간의 결합강도를 향상시킬 수 있는 플라스틱-실리콘 접착필름 및 그 제조방법에 관한 것이다.The present invention relates to a plastic-silicon adhesive film and a method for manufacturing the same, wherein a liquid silicone rubber containing a silane coupling agent capable of activating a reactive functional group through plasma treatment on the surface of the plastic substrate and chemically bonding the reactive functional group to The present invention relates to a plastic-silicon adhesive film and a method of manufacturing the same, by applying and curing the plastic substrate to improve the bonding strength between the plastic substrate and the silicone rubber.

플라스틱-실리콘 접착필름, 플라즈마 처리, 실리콘 고무 Plastic-Silicone Adhesive Film, Plasma Treatment, Silicone Rubber

Description

플라스틱-실리콘 접착필름 및 그 제조방법{LAMINATING FILM OF PLASTIC-SILICON AND METHOD FOR PREPARING THE SAME}Plastic-silicon adhesive film and its manufacturing method {LAMINATING FILM OF PLASTIC-SILICON AND METHOD FOR PREPARING THE SAME}

도 1은 플라즈마 처리를 거치기 이전의 플라스틱 표면의 접촉각을 나타나는 도면.1 shows the contact angle of a plastic surface before undergoing plasma treatment.

도 2는 본 발명에 따른 플라즈마 처리를 거친 직후의 플라스틱 표면의 접촉각을 나타내는 도면.Figure 2 shows the contact angle of the plastic surface immediately after the plasma treatment according to the present invention.

도 3은 본 발명에 따른 플라즈마 처리를 거치고 24시간을 방치한 후의 플라스틱 표면의 접촉각을 나타내는 도면.3 is a view showing the contact angle of the plastic surface after leaving the plasma treatment in accordance with the present invention for 24 hours.

본 발명은 플라스틱-실리콘 접착필름 및 그 제조방법에 관한 것으로서, 보다 상세하게는 플라스틱 기재의 표면을 플라즈마 처리를 통해 반응성 작용기를 활성시키고, 실리콘 고무에 상기 반응성 작용기와 화학적 결합이 가능한 실란 커플링제를 함유시킴으로써 상기 플라스틱 기재와 실리콘 고무간의 결합강도를 향상시킨 플라스틱-실리콘 접착필름 및 그 제조방법에 관한 것이다.The present invention relates to a plastic-silicon adhesive film and a method of manufacturing the same, and more particularly, to a surface of a plastic substrate to activate a reactive functional group through plasma treatment, and to provide a silicone rubber with a silane coupling agent capable of chemically bonding to the reactive functional group. The present invention relates to a plastic-silicon adhesive film and a method for producing the same, wherein the bonding strength between the plastic substrate and the silicone rubber is improved.

실리콘 고무는 내열성, 전기절연성 등이 우수하며 고무 특유의 탄성을 갖고 있어 각종 전자제품의 가스킷 등으로 사용되고 있다.Silicone rubber is excellent in heat resistance, electrical insulation, etc. and has elasticity peculiar to rubber, which is used as a gasket of various electronic products.

그러나, 이러한 실리콘 고무는 실리콘 특유의 이형성에 의하여 점착제 내지 접착제를 도포할 시 상호 결합하지 못하여 실리콘 고무를 다른 물질에 접합시키지 못할 뿐만 아니라 탄성이력(elastic hysteresis)에 의하여 재작업 시 치수가 안정하지 못한 문제점이 있다.However, these silicone rubbers are not bonded to each other when applying the adhesive or adhesive due to the silicone-specific release property, and thus the silicone rubber is not bonded to other materials, and the dimensions of the silicone rubber are not stable when reworked due to elastic hysteresis. There is a problem.

상기와 같은 실리콘 고무의 문제점을 해결하기 위하여 종래에는 폴리에스테르 필름과 같은 플라스틱 기재(substrate)와 상기 실리콘 고무를 접착제 내지 점착제를 도포한 테이프로 접합시킴으로써 상기의 문제점을 극복하고자 하였으나 실리콘 고무와 테이프가 물리적으로 결합하고 있어 열과 같은 외부 충격에 의하여 쉽게 박리되는 문제점을 여전히 가지고 있다.In order to solve the above problems of the silicone rubber, conventionally, a plastic substrate, such as a polyester film, and the silicone rubber are bonded by a tape coated with an adhesive or an adhesive. Due to the physical bonding, there is still a problem of being easily peeled off by external impact such as heat.

본 발명자들은 종래 기술의 문제점을 해결하기 위하여 연구를 거듭한 결과, 플라스틱 기재의 표면에 플라즈마 처리를 통해 반응성 작용기를 생성시키고, 상기 반응성 작용기와 화학적 결합이 가능한 실란 커플링제를 함유하는 액상 실리콘 고무(LSR, Liquid Silicone Rubber)를 상기 플라스틱 기재에 도포하여 경화시킬 경우 상기 플라스틱 기재와 실리콘 고무간의 결합강도를 비약적으로 향상시킬 수 있음을 확인함으로써 본 발명에 이르게 되었다. The present inventors have conducted research to solve the problems of the prior art, and as a result, a liquid silicone rubber containing a silane coupling agent capable of chemically bonding with the reactive functional groups by generating a reactive functional group through plasma treatment on the surface of the plastic substrate ( LSR (Liquid Silicone Rubber) was applied to the plastic substrate to harden the present invention by confirming that can significantly improve the bonding strength between the plastic substrate and the silicone rubber.

따라서, 본 발명의 목적은 플라스틱 기재와 실리콘 고무 간의 결합강도를 비약적으로 향상시킬 수 있는 플라스틱-실리콘 접착필름을 제공하는 데 있다.Accordingly, it is an object of the present invention to provide a plastic-silicon adhesive film that can dramatically improve the bonding strength between a plastic substrate and silicone rubber.

본 발명의 또 다른 목적은 상기 플라스틱-실리콘 접착필름의 제조방법을 제 공하는 데 있다.Another object of the present invention to provide a method for producing the plastic-silicon adhesive film.

상기 목적을 달성하기 위하여, 본 발명은 In order to achieve the above object, the present invention

플라즈마 처리를 통해 표면에 반응성 작용기를 생성시킨 플라스틱 기재; 상기 반응성 작용기와 화학적 결합이 가능한 실란 커플링제; 및 상기 실란 커플링제를 함유하고 상기 플라스틱 기재에 도포되는 실리콘 고무;를 포함하는 것을 특징으로 하는 플라스틱-실리콘 접착필름을 제공한다.Plastic substrates that generate reactive functional groups on the surface through plasma treatment; Silane coupling agents capable of chemically bonding to the reactive functional groups; And a silicone rubber containing the silane coupling agent and applied to the plastic substrate.

또한, 본 발명은In addition, the present invention

ⅰ) 플라즈마 처리를 통해 플라스틱 기재의 표면에 반응성 작용기를 생성시키는 단계; 및Iii) generating reactive functional groups on the surface of the plastic substrate via plasma treatment; And

ⅱ) 상기 반응성 작용기와 화학적 결합이 가능한 실란 커플링제를 함유한 액상실리콘 고무를 상기 플라스틱 기재 표면에 도포한 후 경화시키는 단계;Ii) applying liquid silicone rubber containing a silane coupling agent capable of chemically bonding with the reactive functional group to the surface of the plastic substrate and then curing;

를 포함하는 것을 특징으로 하는 플라스틱-실리콘 접착필름의 제조방법을 제공한다.It provides a method for producing a plastic-silicon adhesive film comprising a.

이하, 본 발명을 보다 각 단계에 따라 상세하게 설명한다.Hereinafter, the present invention will be described in detail with each step.

ⅰ) 플라즈마 처리를 통해 플라스틱 기재의 표면에 반응성 작용기를 생성시키는 단계Iii) generating reactive functional groups on the surface of the plastic substrate via plasma treatment

본 단계는 플라스틱 기재와 상기 플라스틱 기재에 도포되어 경화되는 액상 실리콘 고무 간의 결합강도를 향상시키기 위하여, 상기 플라스틱 기재의 표면에 플라즈마 처리를 실시한다. 상기 플라즈마 처리를 통해 상기 플라스틱 기재의 표면에 반응성 작용기가 생성되는데, 상기 반응성 작용기는 -OH, -OOH, -COOH, -C-O-, -C=O, -O-C-O- 등의 산소 함유 반응성 작용기로 추정된다.In this step, a plasma treatment is performed on the surface of the plastic substrate to improve the bonding strength between the plastic substrate and the liquid silicone rubber which is applied to the plastic substrate and cured. The plasma treatment generates a reactive functional group on the surface of the plastic substrate, and the reactive functional group is assumed to be an oxygen-containing reactive functional group such as -OH, -OOH, -COOH, -CO-, -C = O, or -OCO-. do.

상기 플라즈마 처리에 있어서, 통상의 방법에 따라 플라즈마 처리를 실시할 수 있으나, 플라스틱 기재의 표면에 효과적인 반응성 작용기를 생성하기 위해 1× 10-3 torr 이하의 압력 하에서 수행하는 것이 바람직하다. 상기 압력보다 높은 압력에서 플라즈마 처리를 하게 되면 불순물에 의한 아크방전이 일어나거나 산란에 의한 반응성 작용기의 발생밀도가 떨어지는 문제점이 발생할 수 있기 때문이다. In the plasma treatment, the plasma treatment may be performed according to a conventional method, but it is preferably performed under a pressure of 1 × 10 −3 torr or less in order to generate an effective reactive functional group on the surface of the plastic substrate. This is because if the plasma treatment is performed at a pressure higher than the pressure, arc discharge may occur due to impurities or the density of generation of reactive functional groups due to scattering may occur.

상기 플라즈마 처리시 이온 건(ion gun)에 주입되는 산소와 아르곤 가스의 함량 역시 특별히 한정할 필요는 없으나, 산소 대 아르곤 중량비가 1:1 내지 4:1 인 것이 바람직하다.The content of oxygen and argon gas injected into the ion gun during the plasma treatment need not be particularly limited, but the oxygen to argon weight ratio is preferably 1: 1 to 4: 1.

또한, 플라즈마 발생시의 인가 전압이 증가할수록 플라즈마 방전 밀도가 높아져 플라스틱 기재의 표면에 상기 반응성 작용기의 생성이 증가하게 되는바, 인가 전압은 10 내지 4000 W이 바람직하며, 더욱 바람직하게는 100 내지 3000 W일 수 있다.In addition, as the voltage applied during plasma generation increases, the plasma discharge density increases to increase the generation of the reactive functional groups on the surface of the plastic substrate. The applied voltage is preferably 10 to 4000 W, more preferably 100 to 3000 W. Can be.

통상적으로 플라즈마 처리를 하면 단순히 표면 식각이 발생할 것으로 예상되나, 상기 도 1 내지 도 3을 살펴보면, 플라즈마 처리 전(도 1), 플라즈마 처리한 직후(도 2) 및 플라즈마 처리 후 24시간 방치된 경우(도 3)에 대한 각각의 접촉각이 67.27°, 3.27°, 39.86°인 것으로 표시되는데, 이는 본 발명에 따른 플라즈마 처리로 인해 플라스틱 기재의 표면에 반응성 작용기가 생성되었다가 시간이 경과하 면서 상기 반응성 작용기가 대기 중의 물질과 반응되어 감소되었음을 의미하는 것으로서, 이를 통해 본 발명에 따른 플라스틱의 플라즈마 처리를 거치면 그 표면에 반응성 작용기가 발생함을 명확히 확인할 수 있다.In general, it is expected that the surface etching will simply occur when the plasma treatment is performed. However, referring to FIGS. 1 to 3, when the plasma treatment is left before the plasma treatment (FIG. 1), immediately after the plasma treatment (FIG. 2) and after the plasma treatment (24 hours) Each contact angle for FIG. 3) is shown to be 67.27 °, 3.27 °, 39.86 °, which results in the generation of reactive functional groups on the surface of the plastic substrate due to the plasma treatment according to the present invention and over time. Means that the reaction with the material in the atmosphere has been reduced, through which the plasma treatment of the plastic according to the present invention can clearly confirm that the reactive functional group is generated on the surface.

상기 플라스틱 기재로는 표면에 극성기를 갖는 필름 뿐만 아니라 비극성기를 갖는 올레핀계 필름에도 적용할 수 있으며 특히 전자재료로 많이 사용되는 폴리에틸렌 필름, 폴리프로필렌 필름, 폴리스티렌 필름, 폴리에스터 필름, 폴리아미드 필름, 폴리이미드 필름, 폴리카보네이트 필름, 테트라아세틸셀룰로스 필름 등이 있다.The plastic substrate may be applied not only to a film having a polar group on its surface but also to an olefin-based film having a non-polar group, and in particular, a polyethylene film, a polypropylene film, a polystyrene film, a polyester film, a polyamide film, and a poly A mid film, a polycarbonate film, a tetraacetylcellulose film, and the like.

ⅱ) Ii) 실란Silane 거플링제를Guffling Agent 함유한 액상 실리콘 고무를 상기 플라스틱 기재 표면에 도포한 후 경화시키는 단계 Applying a liquid silicone rubber containing to the surface of the plastic substrate and then curing

본 단계에서는 상기 플라스틱 기재의 표면에 형성된 반응성 작용기와 화학적 결합이 가능한 실란 커플링제를 함유하는 액상 실리콘 고무를 상기 플라스틱 기재에 도포하여 경화시킨다. 상기 실란 커플링제는 플라스틱 기재와 실리콘 고무 간에 고분자 화합결합을 유도함으로써 접착강도를 증가시킨다. In this step, a liquid silicone rubber containing a silane coupling agent capable of chemically bonding with a reactive functional group formed on the surface of the plastic substrate is applied to the plastic substrate and cured. The silane coupling agent increases the adhesive strength by inducing a polymer compound bond between the plastic substrate and the silicone rubber.

상기 실란 커플링제는 하기 화학식 1로 표시되는 화합물 중 1종 이상 선택하여 사용될 수 있다. The silane coupling agent may be used by selecting one or more of the compounds represented by the following formula (1).

Figure 112007085884341-pat00008
Figure 112007085884341-pat00008

(상기 식에서, R1은 수소 혹은 비닐기이며, R2 내지 R4는 탄소수가 1내지 18인 알킬기 혹은 말단에 에폭시기를 갖는 탄소수가 3내지 18인 알킬기이다.)(Wherein, R1 is hydrogen or vinyl group, R2 to R4 is an alkyl group having 1 to 18 carbon atoms or an alkyl group having 3 to 18 carbon atoms having an epoxy group at the terminal.)

상기 실란 커플링제의 함량은 실리콘 고무 100 중량부에 대하여 0.1 내지 30 중량부일 수 있으며, 바람직하게는 0.5 내지 15중량부일 수 있다.The content of the silane coupling agent may be 0.1 to 30 parts by weight, and preferably 0.5 to 15 parts by weight, based on 100 parts by weight of the silicone rubber.

상기 커플링제의 함량이 0.1 중량부 미만일 경우에는 접착력이 미약할 수 있고, 30 중량부 초과할 경우에는 부산물에 의한 기포발생으로 인해 접착력이 저하되는 문제점이 발생할 수 있다.When the content of the coupling agent is less than 0.1 parts by weight, the adhesive strength may be weak. When the content of the coupling agent is more than 30 parts by weight, the adhesive force may be deteriorated due to the bubble generation by the byproduct.

본 발명에서 상기 실란 커플링제가 상기 플라스틱 필름의 표면에 형성된 반응성 작용기와 용이하게 반응시키기 위하여 촉매인 주석 화합물을 사용할 수 있으며, 상기 주석 화합물은 하기 화학식 2로 표시되는 화합물일 수 있다..In the present invention, the silane coupling agent may use a tin compound which is a catalyst in order to easily react with the reactive functional groups formed on the surface of the plastic film, and the tin compound may be a compound represented by the following Chemical Formula 2.

Figure 112006074201633-pat00002
Figure 112006074201633-pat00002

(상기 식에서, R5 내지 R8은 탄소수 1 내지 18인 알킬기이다.)(Wherein, R5 to R8 is an alkyl group having 1 to 18 carbon atoms.)

상기 촉매의 함량은 실리콘 고무 100 중량부 기준으로 0.05 내지 5 중량부일 수 있으며, 바람직하게는 0.1 내지 2 중량부일 수 있다.The content of the catalyst may be 0.05 to 5 parts by weight, based on 100 parts by weight of the silicone rubber, preferably 0.1 to 2 parts by weight.

상기 실리콘 고무는 상기 실리콘계 고무는 디메틸 실록산, 비닐기를 가지는 실록산 및 실록산계 가교제로 이루어진 원료로부터 제조될 수 있으나, 반드시 이에 한정되는 것은 아니다.The silicone rubber may be prepared from a raw material consisting of dimethyl siloxane, a siloxane having a vinyl group, and a siloxane-based crosslinking agent, but is not limited thereto.

상기 액상 실리콘 고무에는 경화제 및 필요에 따라 무기제 필러, 액상실리콘 경화촉매, 물성개량제 등이 추가로 더 함유될 수 있다.The liquid silicone rubber may further contain a curing agent and, if necessary, an inorganic filler, a liquid silicone curing catalyst, and a physical property improving agent.

이하, 하기의 실시예를 통하여 본 발명을 더욱 상세하게 설명하지만, 본 발명의 범위가 실시예에 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to the following examples, but the scope of the present invention is not limited to the examples.

[실시예]EXAMPLE

실시예 1Example 1

산소와 아르곤의 중량비가 4:1이고, 1,000V / 0.2~1.0A (200~1000W)의 전압이 인가되는 플라즈마 처리장치를 이용하여 폴리에틸렌 테레프탈레이트(PET) 필름의 표면에 반응성 작용기를 생성하였다.Reactive functional groups were generated on the surface of the polyethylene terephthalate (PET) film by using a plasma treatment apparatus in which a weight ratio of oxygen to argon was 4: 1 and a voltage of 1,000 V / 0.2 to 1.0 A (200 to 1000 W) was applied.

비닐기로 마감된 액상실리콘[Poly(dimethyl siloxane) fluid] 55중량부, 경화제[Poly(methylhydro siloxane-co-dimethyl siloxane) fluid) 3중량부, 무기제 필러(alumina) 40중량부, 실란 커플링제 0.5중량부, 주석 화합물 촉매 0.1중량부, 백금계 액상실리콘 경화촉매 0.5중량부, 물성개량제인 실리카 나노입자 0.9중량부로 이루어진 액상 실리콘 고무 조성물을 상기 플라스마로 표면을 처리한 플라스틱 필름의 표면에 도포한 후 100℃에서 5분간 경화시켜 플라스틱-실리콘 접착필름을 제조하였다.55 parts by weight of poly (dimethyl siloxane) fluid finished with vinyl group, 3 parts by weight of poly (methylhydro siloxane-co-dimethyl siloxane) fluid as curing agent, 40 parts by weight of inorganic alumina, silane coupling agent 0.5 After applying the liquid silicone rubber composition consisting of 0.1 parts by weight of the tin compound catalyst, 0.1 parts by weight of the platinum-based liquid silicone curing catalyst, 0.9 parts by weight of silica nanoparticles as a physical modifier to the surface of the plastic film treated with the plasma 5 minutes at 100 ℃ to prepare a plastic-silicon adhesive film.

실시예 2Example 2

비닐기로 마감된 액상실리콘 25.5중량부, 실란 커플링제 30중량부를 사용한 것 외에는 상기 실시예 1과 동일하게 실시하였다.The same procedure as in Example 1 was carried out except that 25.5 parts by weight of the liquid silicone finished with a vinyl group and 30 parts by weight of the silane coupling agent were used.

실시예 3Example 3

비닐기로 마감된 액상실리콘 40.5중량부, 실란 커플링제 15중량부를 사용한 것 외에는 상기 실시예 1과 동일하게 실시하였다.The same procedure as in Example 1 was carried out except that 40.5 parts by weight of the liquid silicone finished with a vinyl group and 15 parts by weight of the silane coupling agent were used.

실시예 4Example 4

비닐기로 마감된 액상실리콘 48.6중량부, 실란 커플링제 5중량부 및 주석 화합물 촉매 2 중량부를 사용한 것 외에는 상기 실시예 1과 동일하게 실시하였다.The same procedure as in Example 1 was carried out except that 48.6 parts by weight of the liquid silicone finished with a vinyl group, 5 parts by weight of the silane coupling agent, and 2 parts by weight of the tin compound catalyst were used.

[비교예][Comparative Example]

비교예 1Comparative Example 1

비닐기로 마감된 액상실리콘 40.5중량부, 경화제 3중량부, 무기제 필러 40중량부, 실란 커플링제 15중량부, 주석 화합물 촉매 0.1중량부, 액상실리콘 경화촉매 0.5중량부, 물성개량제 0.9중량부로 이루어진 액상 실리콘 고무 조성물을 플라스마로 처리하지 않은 플라스틱 필름의 표면에 도포한 후 100℃에서 5분간 경화시켜 플라스틱-실리콘 접착필름을 제조하였다.40.5 parts by weight of liquid silicone finished with vinyl, 3 parts by weight of hardener, 40 parts by weight of inorganic filler, 15 parts by weight of silane coupling agent, 0.1 parts by weight of tin compound catalyst, 0.5 parts by weight of liquid silicone curing catalyst, and 0.9 parts by weight of physical modifier. The liquid silicone rubber composition was applied to the surface of the plastic film not treated with plasma, and then cured at 100 ° C. for 5 minutes to prepare a plastic-silicon adhesive film.

비교예Comparative example 2 2

비닐기로 마감된 액상실리콘 55.6중량부를 사용하고, 실란 커플링제는 사용하지 않은 것을 제외하고는 상기 실시예 1과 동일하게 실시하였다.55.6 parts by weight of liquid silicone finished with a vinyl group was used, and the same procedure as in Example 1 was conducted except that no silane coupling agent was used.

[실험예] Experimental Example

상기 실시예 1 내지 4 및 비교예 1 내 2에 따라 제조된 플라스틱-실리콘을 하기 표 1에 기재된 바와 같이 박리 여부를 실험하였다.The plastic-silicon prepared according to Examples 1 to 4 and Comparative Examples 1 and 2 was tested for peeling as described in Table 1 below.

구분division 제조시At the time of manufacture 제조 후 24시간 경과시24 hours after manufacture 내환경 시험 후 (120℃)After environmental test (120 ℃) 100시간100 hours 500시간500 hours 1,000시간1,000 hours 실시예 1Example 1 박리안됨No peeling off 박리안됨No peeling off 박리안됨No peeling off 박리안됨No peeling off 박리안됨No peeling off 실시예 2Example 2 박리안됨No peeling off 박리안됨No peeling off 박리안됨No peeling off 기포발생Bubble 박리됨Peeled 실시예 3Example 3 박리안됨No peeling off 박리안됨No peeling off 박리안됨No peeling off 박리안됨No peeling off 박리안됨No peeling off 실시예 4Example 4 박리안됨No peeling off 박리안됨No peeling off 박리안됨No peeling off 박리안됨No peeling off 박리안됨No peeling off 비교예 1Comparative Example 1 박리안됨No peeling off 박리됨Peeled 비교예 2Comparative Example 2 박리안됨No peeling off 박리됨Peeled

플라즈마 처리를 하지 않은 플라스틱 필름을 사용한 비교예 1 및 플라즈마 처리는 하되 실란 커플링제가 함유되지 않은 비교예 2는 제조 후 24시간이 경과된 시점에서 박리되는 반면, 플라즈마 표면처리를 한 플라스틱 필름에 실란 커플링제를 함유하는 액상 실리콘 고무를 도포하였던 실시예 1 내지 4는 제조 후 24시간 경과된 시점에서도 박리가 이루어지 않았으며, 120℃에서 500시간이 경과한 시점에서도 여전히 박리가 이루어지지 않았음을 확인할 수 있었다.Comparative Example 1 using a plastic film not subjected to plasma treatment and Comparative Example 2 subjected to plasma treatment but containing no silane coupling agent were peeled off when 24 hours had elapsed, whereas silane was applied to the plastic film subjected to plasma surface treatment. Examples 1 to 4 to which the liquid silicone rubber containing the coupling agent were applied were not peeled off even after 24 hours of manufacture, and were still not peeled off even when 500 hours had elapsed at 120 ° C. I could confirm it.

본 발명에 따라 제조된 플라스틱-실리콘 접착필름은 플라즈마 처리를 통해 플라스틱 기재의 표면에 발생한 반응성 작용기와 실리콘 고무에 함유된 실란 커플링제와의 화학적 결합으로 인해 상기 플라스틱 기재와 실리콘 고무간의 결합강도를 비약적으로 향상시킬 수 있는 효과가 있다.The plastic-silicon adhesive film prepared according to the present invention has dramatically reduced the bond strength between the plastic substrate and the silicone rubber due to chemical bonding between the reactive functional groups generated on the surface of the plastic substrate and the silane coupling agent contained in the silicone rubber through plasma treatment. There is an effect that can be improved.

Claims (6)

1× 10-3torr 이하의 압력 및 산소 대 아르곤 중량비가 1:1 내지 4:1인 산소 분위기 하에서의 플라즈마 처리를 통해 표면에 반응성 작용기가 생성된 플라스틱 기재; 상기 반응성 작용기와 화학적으로 결합되는 하기 화학식 1 구조의 실란 커플링제; 및 상기 플라스틱 기재에 도포되고 상기 실란 커플링제와 화학적으로 결합하는 실리콘 고무;를 포함하고, 상기 실리콘 고무는 하기 화학식 2의 구조를 가지는 촉매를 더 함유하는 것을 특징으로 하는 플라스틱-실리콘 접착필름.Plastic substrates having reactive functional groups formed on surfaces through plasma treatment under an oxygen atmosphere having a pressure of 1 × 10 −3 torr or less and an oxygen to argon weight ratio of 1: 1 to 4: 1; Silane coupling agents chemically bonded to the reactive functional groups; And a silicone rubber applied to the plastic substrate and chemically bonded to the silane coupling agent, wherein the silicone rubber further contains a catalyst having a structure of Formula 2 below. [화학식 1][Formula 1]
Figure 112008057203100-pat00009
Figure 112008057203100-pat00009
 (상기 식에서, R1은 수소 혹은 비닐기이며, R2 내지 R4는 탄소수가 1내지 18인 알킬기 혹은 말단에 에폭시기를 갖는 탄소수가 3내지 18인 알킬기이다.)(Wherein, R1 is hydrogen or vinyl group, R2 to R4 is an alkyl group having 1 to 18 carbon atoms or an alkyl group having 3 to 18 carbon atoms having an epoxy group at the terminal.) [화학식 2][Formula 2]
Figure 112008057203100-pat00011
Figure 112008057203100-pat00011
 (상기 식에서, R5 내지 R8은 탄소수 1 내지 18인 알킬기이다.)(Wherein, R5 to R8 is an alkyl group having 1 to 18 carbon atoms.) 삭제delete 제1항에 있어서,The method of claim 1, 상기 실란 커플링제의 함량은 전체 실리콘 고무 100 중량부를 기준으로 0.1 내지 30 중량부인 것을 특징으로 하는 플라스틱-실리콘 접착필름.The content of the silane coupling agent is a plastic-silicon adhesive film, characterized in that 0.1 to 30 parts by weight based on 100 parts by weight of the total silicone rubber. 삭제delete 제1항에 있어서,The method of claim 1, 상기 플라스틱 기재는 폴리에틸렌, 폴리프로필렌 필름, 폴리스티렌 필름, 폴리에스터 필름, 폴리아미드 필름, 폴리이미드 필름, 폴리카보네이트 필름 또는 테트라아세틸셀룰로스 필름인 것을 특징으로 하는 플라스틱-실리콘 접착필름.The plastic substrate is a plastic-silicon adhesive film, characterized in that the polyethylene, polypropylene film, polystyrene film, polyester film, polyamide film, polyimide film, polycarbonate film or tetraacetylcellulose film. ⅰ) 1× 10-3torr 이하의 압력 및 산소 대 아르곤 중량비가 1:1 내지 4:1인 산소 분위기 하에서의 플라즈마 처리를 통해 플라스틱 기재의 표면에 반응성 작용기를 생성시키는 단계; 및Iii) generating reactive functional groups on the surface of the plastic substrate through plasma treatment under an oxygen atmosphere having a pressure of 1 × 10 −3 torr or less and an oxygen to argon weight ratio of 1: 1 to 4: 1; And ⅱ) 상기 반응성 작용기와 화학적 결합이 가능한 하기 화학식 1 구조의 실란 거플링제 및 하기 화학식 2의 구조를 가지는 촉매를 함유한 액상실리콘 고무를 상기 플라스틱 기재 표면에 도포한 후 경화시키는 단계;Ii) applying a cured liquid silicone rubber containing a silane coupling agent having a structure of Chemical Formula 1 and a catalyst having a structure of Chemical Formula 2 to chemically bond with the reactive functional group to the surface of the plastic substrate, and then curing it; 를 포함하는 것을 특징으로 하는 플라스틱-실리콘 접착필름의 제조방법.Method for producing a plastic-silicon adhesive film comprising a. [화학식 1][Formula 1]
Figure 112008057203100-pat00010
Figure 112008057203100-pat00010
 (상기 식에서, R1은 수소 혹은 비닐기이며, R2 내지 R4는 탄소수가 1내지 18인 알킬기 혹은 말단에 에폭시기를 갖는 탄소수가 3내지 18인 알킬기이다.)(Wherein, R1 is hydrogen or vinyl group, R2 to R4 is an alkyl group having 1 to 18 carbon atoms or an alkyl group having 3 to 18 carbon atoms having an epoxy group at the terminal.) [화학식 2][Formula 2]
Figure 112008057203100-pat00012
Figure 112008057203100-pat00012
 (상기 식에서, R5 내지 R8은 탄소수 1 내지 18인 알킬기이다.)(Wherein, R5 to R8 is an alkyl group having 1 to 18 carbon atoms.)
KR1020060100035A 2006-10-13 2006-10-13 Laminating film of plastic-silicon and method for preparing the same KR100871609B1 (en)

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KR101049927B1 (en) * 2009-09-04 2011-07-15 선우에이엠씨주식회사 Silicone coated plastic bonding sheet and method of making same

Citations (4)

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Publication number Priority date Publication date Assignee Title
JPH05194930A (en) * 1992-01-21 1993-08-03 Shin Etsu Chem Co Ltd Adhesive silicone rubber composition
JP2003225972A (en) * 2002-02-04 2003-08-12 Dow Corning Toray Silicone Co Ltd Silicone rubber composite and its manufacturing method
KR20050100904A (en) * 2004-04-16 2005-10-20 한국화학연구원 Method for modifying surface of silicon rubber sheet
KR20060104737A (en) * 2005-03-31 2006-10-09 삼성전기주식회사 Mold-release treating method of imprint mold for printed circuit board

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05194930A (en) * 1992-01-21 1993-08-03 Shin Etsu Chem Co Ltd Adhesive silicone rubber composition
JP2003225972A (en) * 2002-02-04 2003-08-12 Dow Corning Toray Silicone Co Ltd Silicone rubber composite and its manufacturing method
KR20050100904A (en) * 2004-04-16 2005-10-20 한국화학연구원 Method for modifying surface of silicon rubber sheet
KR20060104737A (en) * 2005-03-31 2006-10-09 삼성전기주식회사 Mold-release treating method of imprint mold for printed circuit board

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