WO2018117607A1 - Adhesive composition and flexible flat cable using same - Google Patents

Adhesive composition and flexible flat cable using same Download PDF

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Publication number
WO2018117607A1
WO2018117607A1 PCT/KR2017/015037 KR2017015037W WO2018117607A1 WO 2018117607 A1 WO2018117607 A1 WO 2018117607A1 KR 2017015037 W KR2017015037 W KR 2017015037W WO 2018117607 A1 WO2018117607 A1 WO 2018117607A1
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WO
WIPO (PCT)
Prior art keywords
adhesive composition
polyester resin
flexible flat
urethane
flat cable
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PCT/KR2017/015037
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French (fr)
Korean (ko)
Inventor
김성문
박광석
유의덕
정인기
박수병
Original Assignee
주식회사 두산
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Publication of WO2018117607A1 publication Critical patent/WO2018117607A1/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
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • 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
    • C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such 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
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/06—Polyurethanes from polyesters
    • 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
    • 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
    • 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
    • C09J7/50—Adhesives in the form of films or foils characterised by a primer layer between the carrier and the adhesive
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H01B13/32—Filling or coating with impervious material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B7/00—Insulated conductors or cables characterised by their form
    • H01B7/08—Flat or ribbon cables
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B7/00—Insulated conductors or cables characterised by their form
    • H01B7/08—Flat or ribbon cables
    • H01B7/0861—Flat or ribbon cables comprising one or more screens

Definitions

  • a flexible flat cable is a flat multi-core cable used for a connection between a computer or a peripheral device or a digital device, and has a structure of insulating film / adhesive / plural conductors / adhesive / insulating film.
  • FFCs are used in a wider range of fields than flexible printed circuit boards (FPCBs) because of their excellent flexibility, low manufacturing cost and infinite size.
  • FFC is applied to harness wiring of a vehicle, signal connection wiring of various electronic devices, such as a flexible LED light source. Accordingly, the use environment temperature of the FFC is high, which increases the demand for high heat resistance FFC.
  • the LED when the LED is mounted on the FFC through soldering, the FFC must be able to withstand high heat of 260 ° C or higher because the soldering temperature is about 260 ° C or higher.
  • a hot melt type polyester adhesive is mainly used as a conventional FFC adhesive, and its use temperature is about 100 to 150 ° C. Accordingly, the conventional FFC polyester adhesives are pyrolyzed when soldering at a temperature of 260 ° C. or higher, resulting in a problem that the adhesive strength between the FFC conductor and the insulating film is lowered.
  • An object of the present invention is to provide an adhesive composition having excellent heat resistance properties.
  • Another object of the present invention is to provide a flexible flat cable having high mechanical properties, heat resistance and electrical properties even under severe conditions such as high temperature and high humidity using the adhesive composition described above.
  • the present invention (a) a urethane-modified polyester resin having a carboxyl group in the side chain; (b) epoxy resins; And (c) an isocyanate group-containing curing agent.
  • the adhesive composition may further include a polyester resin.
  • the present invention provides a flexible flat cable comprising an adhesive layer formed of the above-described adhesive composition.
  • the flexible flat cable is a conductor; And an insulating film positioned on at least one surface of the conductive wire and sequentially including an adhesive layer, a primer layer, and a resin layer, wherein the adhesive layer is formed of the adhesive composition described above.
  • the present invention provides a flexible flat cable module, a power supply device and a display device to which the above-described flexible flat cable is applied.
  • the adhesive composition according to the present invention uses a urethane-modified polyester resin having a carboxyl group in the side chain in combination with an epoxy resin and an isocyanate group-containing curing agent, whereby an adhesive layer made of a network polymer having excellent heat resistance upon curing is formed.
  • the operating temperature of the flat cable can be increased.
  • FIG. 1 is a view schematically showing a cross-sectional structure of a flexible flat cable according to an embodiment of the present invention.
  • Example 2 is a graph showing the change of the dimension of the adhesive composition of Example 4 and Comparative Examples 1 and 2 according to the temperature.
  • FIG. 3 is a photograph showing whether the flexible flat cable manufactured in Example 4 and Comparative Example 2 has been subjected to interlayer peeling after three reflows at 280 ° C.
  • FIG. 3 (a) is the flexible flat cable of Example 4, and
  • FIG. 3. (b) is the flexible flat cable of the comparative example 2.
  • FIG. 3 (a) is the flexible flat cable of Example 4, and
  • FIG. 3. (b) is the flexible flat cable of the comparative example 2.
  • the present inventors attempted to improve the heat resistance characteristics of the adhesive composition by using a urethane-modified polyester resin as the adhesive of the flexible flat cable instead of the conventional polyester adhesive.
  • a urethane-modified polyester resin as the adhesive of the flexible flat cable instead of the conventional polyester adhesive.
  • the urethane-modified polyester resin is used alone as an adhesive for a flexible flat cable, there is a problem that hardening does not occur well at a temperature of 100 ° C. or lower during the lamination process of the flexible flat cable, and the adhesive property is lowered.
  • a urethane-modified polyester resin (hereinafter referred to as "urethane-modified polyester resin") containing a carboxyl group in the side chain has a carboxyl group (-COOH) in the side chain and a hydroxyl group (-OH) at the terminal.
  • urethane-modified polyester resin can realize high heat resistance by reacting with an epoxy resin and an isocyanate group-containing curing agent in a short time even at low temperatures. That is, in the urethane-modified polyester resin, a polymer having a network structure may be formed by forming a crosslink by reacting a carboxyl group of a side chain with an epoxy group of an epoxy resin.
  • the urethane-modified polyester resin is a terminal hydroxyl group and / or side chain hydroxyl group may react with the isocyanate group of the isocyanate group-containing curing agent, the polymer of the interpenetrating polymer network (IPN) structure can be formed between the network structure.
  • the adhesive layer according to the present invention comprising a polymer of such a network structure and a polymer of an IPN structure has a glass transition temperature of 100 ° C. or less (preferably about 50-100 ° C.), and a softening point of about 200 ° C. or more (preferably, about 260 ⁇ ). 300 ° C.), even when soldering at a temperature of about 260 ° C.
  • the adhesive composition according to the present invention is a material for forming an adhesive layer that allows the insulating film to bond and bond to a conductive wire when the flexible flat cable is formed.
  • a urethane-modified polyester resin having a carboxyl group in a side chain and
  • Epoxy resins and
  • isocyanate group-containing curing agents are examples of the urethane-modified polyester resin having a carboxyl group in a side chain.
  • the adhesive composition comprises (a) a urethane-modified polyester resin having a carboxyl group in the side chain, (b) an epoxy resin, (c) an isocyanate group-containing curing agent, and (d) a polyester resin.
  • Urethane-modified polyester resin having a carboxyl group in the side chain (hereinafter referred to as "urethane-modified polyester resin") is a repeating unit containing a urethane group (-NHCOO-), repeating unit containing an ester group (-COO-) And it is a block or random copolymer which contains the repeating unit which has a carboxyl group (-COOH) in a side chain, and has a hydroxyl group (-OH) in at least one terminal of a main chain.
  • the urethane-modified polyester resin as the carboxyl group of the side chain reacts with the epoxy resin to form a network structure, since the terminal hydroxy group reacts with the isocyanate group-containing curing agent to form an IPN structure, the adhesive composition Can exhibit high heat resistance.
  • the urethane-modified polyester resin may be a urethane-modified polyester resin represented by the following formula (1).
  • X is an integer from 1 to 50
  • Y is an integer from 1 to 50
  • Z is an integer from 1 to 50.
  • the urethane-modified polyester resin may be a urethane-modified polyester resin having a carboxyl group (-COOH) and a hydroxyl group (-OH) in the side chain, and having a hydroxyl group (-OH) at the terminal, but is not limited thereto. Do not.
  • the urethane-modified polyester resin according to the present invention is not particularly limited in the equivalent of the carboxyl group, but in the range of about 500 to 3000 g / eq, preferably in the range of 1000 to 2000 g / eq, the heat resistance characteristics of the adhesive composition is further improved to a high temperature The adhesive properties at can be improved.
  • the urethane-modified polyester resin may contain a hydroxyl group in at least one of the terminal and the side chain.
  • the urethane-modified polyester resin contains a hydroxy group in the side chain, the urethane-modified polyester resin has heat resistance and high temperature adhesive properties of the adhesive composition when the equivalent of the total hydroxyl group is in the range of about 500 to 3000 g / eq. Can be improved.
  • the content of the carboxyl group in the urethane-modified polyester resin is higher than the content of the hydroxy group, a polymer having a network structure having a high degree of crosslinking may be formed, and thus the high heat resistance property of the adhesive composition may be further improved.
  • the urethane-modified polyester resin may contain a carboxyl group and a hydroxyl group in an equivalent ratio of 1: 1.5 to 2.5.
  • the urethane-modified polyester resin has a number average molecular weight in the range of about 10,000 to 20,000, and a glass transition temperature of about 5 to 25 °C.
  • the urethane-modified polyester resin used in the present invention can be synthesized by various methods known in the art.
  • the urethane modified polyester resin which has a carboxyl group in the said side chain can be obtained by making polyester which has a carboxyl group in a side chain, and organic diisocyanate react.
  • the polyester having a carboxyl group in the side chain is prepared according to a method known in the art, specifically prepared by the polymerization of polyols and polyhydric carboxylic acid or acid anhydride thereof.
  • the adhesive composition according to the present invention may further comprise a polyester resin.
  • a polyester resin usable in the present invention a number average molecular weight can be used in the range of about 13,000 to 25,000, preferably 13,000 to 22,000.
  • the content of the polyester resin is not particularly limited, but is based on 100 parts by weight of the urethane-modified polyester resin, about 0 to 100 parts by weight, preferably about 20 to 100 parts by weight, more preferably about 30 to 100 parts by weight. In the range, it is possible to improve the adhesive properties and heat resistance properties of the adhesive composition.
  • the adhesive composition according to the present invention is a flame retardant and an antiblocking agent in addition to the above-mentioned urethane-modified polyester resin, epoxy resin, and isocyanate group-containing curing agent, as long as the heat resistance and adhesive properties of the adhesive composition are not deteriorated.
  • a flame retardant and an antiblocking agent in addition to the above-mentioned urethane-modified polyester resin, epoxy resin, and isocyanate group-containing curing agent, as long as the heat resistance and adhesive properties of the adhesive composition are not deteriorated.
  • bromine-based flame retardant aluminum hydroxide, silica, titanium dioxide, antimony trioxide, and the like, but is not limited thereto.
  • the content thereof is not particularly limited, and may be in a range of about 1 to 20 parts by weight based on 100 parts by weight of the urethane-modified polyester resin.
  • the viscosity of the adhesive composition of the present invention described above is not particularly limited, the resin stability is excellent when it is in the range of about 500 to 4000 cPs.
  • the adhesive composition has a solid content of about 35 to 45% based on the total weight of the composition, the coating property of the composition can be improved to improve workability.
  • the present invention provides a flexible flat cable comprising an adhesive layer formed of the adhesive composition described above.
  • the flexible flat cable 100 as shown in Figure 1, the conductor (10); And an insulating film 20 positioned on at least one surface of the conductive wire and sequentially including an adhesive layer 21, a primer layer 22, and a resin layer 23, wherein the adhesive layer 21 is the adhesive composition described above. Is formed.
  • These flexible flat cables have excellent mechanical, thermal and electrical properties under high temperature / high humidity conditions.
  • the conductive wire 10 is a plurality of flat plate-like material having a predetermined width and thickness, it may be made of a conductive metal such as copper, tin-plated copper, nickel-plated copper. According to an example, the conductive wire 10 may be a thin material made of copper.
  • the thickness or shape of the conductive wire is not particularly limited, and conventional conductive wires known in the art may be used without limitation.
  • the thickness of the conductive wire may be in the range of about 20 to 50 ⁇ m in consideration of the sliding property of the flexible flat cable 100.
  • the insulating film 20 includes an adhesive layer 21, a primer layer 22 and a resin layer 22, which are sequentially stacked.
  • the insulating film 20 covers the conductive wires by being laminated by contacting the adhesive layer 21 on one or both surfaces of the conductive wires.
  • the adhesive layer 21 is to bond the insulating film 20 to the conductive wire 10 to be bonded, it is formed of the adhesive composition described above. Specifically, when the adhesive composition is cured at a temperature condition of about 100 to 180 ° C., the urethane-modified polyester resin reacts with an epoxy resin and an isocyanate group-containing curing agent to form a polymer having a network structure and / or an IPN structure. .
  • Such polymers are highly heat resistant resins having a glass transition temperature of about 100 ° C. or lower, preferably about 50 to 100 ° C., and a softening point of about 250 ° C. or higher, preferably about 250 to 300 ° C., even if soldered at a temperature of 260 ° C. or higher.
  • the adhesive strength between the adhesive layer and the conductive wire is about 1.5 to 2.0 kgf / cm.
  • the adhesive strength between the adhesive layer and the conductive layer is first applied to the copper foil of the adhesive composition of the present invention, and then compressed using a high temperature / high pressure press device (press conditions: 170 ° C., 5700 lb and 3 minutes) to prepare a sample. , The 90 degree adhesive force of the sample is measured.
  • urethane-modified polyester resin 100 parts by weight of urethane-modified polyester resin (number average molecular weight: 13,000, carboxyl equivalent: 1,600, hydroxy equivalent: 6,500), 10 parts by weight of epoxy resin (HY-30 from TOYOBO, epoxy equivalent: 190), 25 parts by weight of isocyanate ( Mitsui Chemicals, Takenate D-120N) and 100 parts by weight of polyester resin (Japanese synthetic, SP-181, number average molecular weight: 22,000) were mixed to obtain an adhesive composition.
  • the "parts by weight” is based on 100 parts by weight of the urethane-modified polyester resin.
  • One surface of the PET film was coated with an epoxy resin (Epoxy I in Table 1) to a thickness of 12 ⁇ m by a comma coat method, and cured at a temperature of 140 ° C. to form a primer layer.
  • an insulating film was prepared by coating the adhesive composition prepared in Example 1-1 on the primer layer and curing at a temperature of 130 ° C. to form an adhesive layer having a thickness of 20 ⁇ m.
  • a flexible flat cable was manufactured by sandwiching a conductor having a thickness of 35 ⁇ m between the adhesive layers of the two insulating films prepared in Example 1-2 and laminating at a speed of 0.8 m / min.
  • Examples 2 to 4 and Comparative Examples 1 and 2 having the compositions shown in Table 1 were prepared, respectively, and Examples 2 to 3 and Comparative Examples 1 to 1 were prepared using the resin layers and primer layers shown in Table 1 below. 2 insulating film was prepared. Thereafter, the flexible flat cables of Examples 2 to 3 and Comparative Examples 1 and 2 were prepared using the respective adhesive compositions and insulating films.
  • the glass transition temperature (Tg) and softening point (Ts) of the adhesive compositions of Example 4 and Comparative Examples 1 and 2 were measured according to the TMA Penetration method, and the measurement results are shown in Table 2 and FIG. 2.
  • the adhesive composition according to the present invention can be easily cured at a temperature of 100 ° C. or less because the glass transition temperature is 100 ° C. or less, and furthermore, even if soldering at a temperature of 200 ° C. or more, since the softening point is higher than 200 ° C. It was found that a decrease in the adhesive strength between the lead wire of the FFC and the insulating film was not caused.
  • Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 260 °C Reflow 3 times X X X X ⁇ 280 °C Reflow 3 times ⁇ ⁇ ⁇ X ⁇ ⁇
  • the adhesive composition which concerns on this invention is excellent in heat resistance characteristic, the use temperature of a flexible flat cable was able to be raised.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Insulated Conductors (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The present invention relates to an adhesive composition having excellent heat resistance and a flexible flat cable using the same, and the adhesive composition comprises: (a) a urethane modified polyester resin having a carboxyl group at a side chain thereof; (b) an epoxy resin; and (c) an isocyanate group-containing curing agent.

Description

접착제 조성물 및 이를 이용하는 플렉시블 플랫 케이블Adhesive composition and flexible flat cable using the same
본 발명은 내열성이 우수한 접착제 조성물 및 이를 이용하는 플렉시블 플랫 케이블에 대한 것이다.The present invention relates to an adhesive composition having excellent heat resistance and a flexible flat cable using the same.
일반적으로 플렉시블 플랫 케이블(Flexible Flat Cable, FFC)은 컴퓨터 혹은 그 주변장치나 디지털기기 간의 접속 등에 사용되는 평형 다심 케이블로, 절연필름/접착제/복수의 도선/접착제/절연필름의 구조를 갖는다. In general, a flexible flat cable (FFC) is a flat multi-core cable used for a connection between a computer or a peripheral device or a digital device, and has a structure of insulating film / adhesive / plural conductors / adhesive / insulating film.
이러한 FFC는 우수한 가요성, 낮은 제조비용 및 제조 크기의 무한대 때문에, 인쇄회로기판(Flexible Print Circuit Board, FPCB)에 비해 폭넓은 분야에 이용되고 있다. 또, FFC는 차량의 하네스 배선이나, 플렉시블 LED 광원 등의 각종 전자기기의 신호 연결 배선 등에 적용되고 있다. 이에 따라, FFC의 사용 환경 온도가 높아지고, 이로 인해 고내열성 FFC에 대한 요구가 증가하고 있다. 특히, FFC 상에 솔더링을 통해 LED를 탑재할 경우, 솔더링 온도가 약 260 ℃ 이상이기 때문에, FFC는 260 ℃ 이상의 고열을 견딜 수 있어야 한다. 그러나, 종래 FFC용 접착제로 핫멜트 타입의 폴리에스테르 접착제가 주로 사용되고 있는데, 이의 사용 온도는 100 내지 150 ℃ 정도이다. 따라서, 종래 FFC용 폴리에스테르 접착제는 260 ℃ 이상의 온도에서 솔더링시 열분해되어 FFC의 도선과 절연필름 간의 접착 강도가 저하되는 문제가 발생하였다.Such FFCs are used in a wider range of fields than flexible printed circuit boards (FPCBs) because of their excellent flexibility, low manufacturing cost and infinite size. Moreover, FFC is applied to harness wiring of a vehicle, signal connection wiring of various electronic devices, such as a flexible LED light source. Accordingly, the use environment temperature of the FFC is high, which increases the demand for high heat resistance FFC. In particular, when the LED is mounted on the FFC through soldering, the FFC must be able to withstand high heat of 260 ° C or higher because the soldering temperature is about 260 ° C or higher. However, a hot melt type polyester adhesive is mainly used as a conventional FFC adhesive, and its use temperature is about 100 to 150 ° C. Accordingly, the conventional FFC polyester adhesives are pyrolyzed when soldering at a temperature of 260 ° C. or higher, resulting in a problem that the adhesive strength between the FFC conductor and the insulating film is lowered.
* 선행기술문헌 1: 일본 공개특허공보 특개2003-327676호 * Prior art document 1: Japanese Patent Laid-Open No. 2003-327676
본 발명의 목적은 내열 특성이 우수한 접착제 조성물을 제공하고자 한다.An object of the present invention is to provide an adhesive composition having excellent heat resistance properties.
또, 본 발명의 다른 목적은 전술한 접착제 조성물을 이용하여 고온 및 고습 등의 가혹 조건하에서도 높은 기계적 특성, 내열 특성 및 전기적 특성을 갖는 플렉시블 플랫 케이블을 제공하고자 한다.In addition, another object of the present invention is to provide a flexible flat cable having high mechanical properties, heat resistance and electrical properties even under severe conditions such as high temperature and high humidity using the adhesive composition described above.
상기한 목적을 달성하기 위해, 본 발명은 (a) 측쇄에 카르복실기를 갖는 우레탄 변성 폴리에스테르 수지; (b) 에폭시 수지; 및 (c) 이소시아네이트기-함유 경화제를 포함하는 접착제 조성물을 제공한다. In order to achieve the above object, the present invention (a) a urethane-modified polyester resin having a carboxyl group in the side chain; (b) epoxy resins; And (c) an isocyanate group-containing curing agent.
또, 상기 접착제 조성물은 폴리에스테르 수지를 더 포함할 수 있다.In addition, the adhesive composition may further include a polyester resin.
한편, 본 발명은 전술한 접착제 조성물로 형성된 접착층을 포함하는 플렉시블 플랫 케이블을 제공한다.On the other hand, the present invention provides a flexible flat cable comprising an adhesive layer formed of the above-described adhesive composition.
일례에 따르면, 상기 플렉시블 플랫 케이블은 도선; 및 상기 도선의 적어도 일면에 위치하며, 접착층, 프라이머층 및 수지층을 순차적으로 포함하는 절연필름을 포함하고, 상기 접착층은 전술한 접착제 조성물로 형성된 것이 바람직하다.According to one example, the flexible flat cable is a conductor; And an insulating film positioned on at least one surface of the conductive wire and sequentially including an adhesive layer, a primer layer, and a resin layer, wherein the adhesive layer is formed of the adhesive composition described above.
또, 본 발명은 전술한 플렉시블 플랫 케이블을 적용한 플렉시블 플랫 케이블 모듈, 전원공급장치 및 디스플레이 장치를 제공한다.In addition, the present invention provides a flexible flat cable module, a power supply device and a display device to which the above-described flexible flat cable is applied.
본 발명에 따른 접착제 조성물은 측쇄에 카르복실기를 갖는 우레탄 변성 폴리에스테르 수지를 에폭시 수지 및 이소시아네이트기-함유 경화제와 병용(竝用)함으로써, 경화시 내열성이 우수한 네트워크 폴리머로 된 접착층이 형성되기 때문에, 플렉시블 플랫 케이블의 사용 온도를 높일 수 있다. The adhesive composition according to the present invention uses a urethane-modified polyester resin having a carboxyl group in the side chain in combination with an epoxy resin and an isocyanate group-containing curing agent, whereby an adhesive layer made of a network polymer having excellent heat resistance upon curing is formed. The operating temperature of the flat cable can be increased.
도 1은 본 발명의 일 실시예에 따른 플렉서블 플랫 케이블의 단면 구조를 개략적으로 도시한 도면이다. 1 is a view schematically showing a cross-sectional structure of a flexible flat cable according to an embodiment of the present invention.
도 2는 실시예 4 및 비교예 1~2의 접착제 조성물의 온도에 따른 dimension 변화를 나타낸 그래프이다.2 is a graph showing the change of the dimension of the adhesive composition of Example 4 and Comparative Examples 1 and 2 according to the temperature.
도 3은 실시예 4 및 비교예 2에서 제조된 플렉시블 플랫 케이블의 280 ℃에서의 3회 Reflow 후의 층간 박리 여부를 나타낸 사진으로, 도 3(a)는 실시예 4의 플렉시블 플랫 케이블이고, 도 3(b)는 비교예 2의 플렉시블 플랫 케이블이다.FIG. 3 is a photograph showing whether the flexible flat cable manufactured in Example 4 and Comparative Example 2 has been subjected to interlayer peeling after three reflows at 280 ° C. FIG. 3 (a) is the flexible flat cable of Example 4, and FIG. 3. (b) is the flexible flat cable of the comparative example 2. FIG.
** 부호의 설명 **** Explanation of Codes **
10: 도선 20: 절연필름10: wire 20: insulating film
21: 접착층 22: 중간층21: adhesive layer 22: intermediate layer
23: 수지층 100: 플렉시블 플랫 케이블23: resin layer 100: flexible flat cable
이하, 본 발명에 대하여 설명한다.EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated.
본 발명자들은 종래 폴리에스테르 접착제 대신 우레탄 변성 폴리에스테르 수지를 플렉시블 플랫 케이블의 접착제로 사용하여 접착제 조성물의 내열 특성을 향상시키고자 하였다. 그러나, 상기 우레탄 변성 폴리에스테르 수지를 플렉시블 플랫 케이블의 접착제로 단독 사용할 경우, 플렉시블 플랫 케이블의 적층 공정시 100 ℃ 이하의 온도에서 경화가 잘 이루어지지 않고, 접착 특성이 저하되는 문제가 있었다. 게다가, 상기 우레탄 변성 폴리에스테르 수지를 이소시아네이트기-함유 경화제와 함께 사용하더라도, 히드록시기와 이소시아네이트기의 반응성이 높아 접착 필름(접착층)의 수명 특성이 저하되어 플렉시블 플랫 케이블(FFC)의 수명 특성도 저하되었고, 또한 원하는 정도의 내열 특성이 구현되지 않았다. The present inventors attempted to improve the heat resistance characteristics of the adhesive composition by using a urethane-modified polyester resin as the adhesive of the flexible flat cable instead of the conventional polyester adhesive. However, when the urethane-modified polyester resin is used alone as an adhesive for a flexible flat cable, there is a problem that hardening does not occur well at a temperature of 100 ° C. or lower during the lamination process of the flexible flat cable, and the adhesive property is lowered. In addition, even when the urethane-modified polyester resin is used together with an isocyanate group-containing curing agent, the reactivity of the hydroxyl group and the isocyanate group is high, so that the life characteristics of the adhesive film (adhesive layer) are lowered, and the life characteristics of the flexible flat cable (FFC) are also lowered. In addition, the desired heat resistance characteristics have not been implemented.
이에, 본 발명자들은 측쇄에 카르복실기를 갖는 우레탄 변성 폴리에스테르 수지를 사용하되, 경화제 성분으로 이소시아네이트기-함유 경화제 이외 에폭시 수지를 함께 사용할 경우, 접착제 조성물의 고내열 특성 및 고접착 특성을 동시에 구현할 수 있다는 것을 알았다. Thus, the present inventors use a urethane-modified polyester resin having a carboxyl group in the side chain, but when using an epoxy resin other than the isocyanate group-containing curing agent as the curing agent component, it is possible to simultaneously realize the high heat resistance characteristics and high adhesion characteristics of the adhesive composition I knew that.
구체적으로, 측쇄에 카르복실기를 함유하는 우레탄 변성 폴리에스테르 수지(이하, '우레탄 변성 폴리에스테르 수지'라 함)는 측쇄에 카르복실기(-COOH)를 가지면서, 말단에 히드록시기(-OH)를 갖고 있는 고분자이다. 이러한 우레탄 변성 폴리에스테르 수지는 저온에서도 단시간에 에폭시 수지 및 이소시아네이트기-함유 경화제와 반응하여 고내열 특성을 구현할 수 있다. 즉, 상기 우레탄 변성 폴리에스테르 수지는 측쇄의 카르복실기가 에폭시 수지의 에폭시기와 반응하여 가교 결합을 형성함으로써, 네트워크 구조의 폴리머가 형성될 수 있다. 또한, 상기 우레탄 변성 폴리에스테르 수지는 말단의 히드록시기 및/또는 측쇄의 히드록시기가 이소시아네이트기-함유 경화제의 이소시아네이트기와 반응하여, 상기 네트워크 구조 사이에 IPN(interpenetrating polymer network) 구조의 폴리머가 형성될 수 있다. 이러한 네트워크 구조의 폴리머와 IPN 구조의 고분자를 포함하는 본 발명에 따른 접착층은 유리전이온도가 100 ℃ 이하(바람직하게 약 50~100 ℃)이고, 연화점이 약 200 ℃ 이상(바람직하게, 약 260 ~ 300 ℃)이기 때문에, 용이하게 경화되어 단시간에 접착층을 형성하면서, 약 260 ℃ 이상의 온도에서 솔더링하더라도 도선과 절연필름 간의 박리(탈착)를 최소화시킬 수 있다. 따라서, 본 발명의 접착제 조성물을 적용한 플렉시블 플랫 케이블은 종래 접착제 조성물을 적용한 플렉시블 플랫 케이블보다 더 높은 온도에서 사용될 수 있다.Specifically, a urethane-modified polyester resin (hereinafter referred to as "urethane-modified polyester resin") containing a carboxyl group in the side chain has a carboxyl group (-COOH) in the side chain and a hydroxyl group (-OH) at the terminal. to be. Such a urethane-modified polyester resin can realize high heat resistance by reacting with an epoxy resin and an isocyanate group-containing curing agent in a short time even at low temperatures. That is, in the urethane-modified polyester resin, a polymer having a network structure may be formed by forming a crosslink by reacting a carboxyl group of a side chain with an epoxy group of an epoxy resin. In addition, the urethane-modified polyester resin is a terminal hydroxyl group and / or side chain hydroxyl group may react with the isocyanate group of the isocyanate group-containing curing agent, the polymer of the interpenetrating polymer network (IPN) structure can be formed between the network structure. The adhesive layer according to the present invention comprising a polymer of such a network structure and a polymer of an IPN structure has a glass transition temperature of 100 ° C. or less (preferably about 50-100 ° C.), and a softening point of about 200 ° C. or more (preferably, about 260 ~). 300 ° C.), even when soldering at a temperature of about 260 ° C. or more while easily curing and forming an adhesive layer in a short time, peeling (desorption) between the conductive wire and the insulating film can be minimized. Therefore, the flexible flat cable to which the adhesive composition of the present invention is applied can be used at a higher temperature than the flexible flat cable to which the conventional adhesive composition is applied.
<접착제 조성물><Adhesive Composition>
본 발명에 따른 접착제 조성물은 플렉시블 플랫 케이블의 형성시 절연필름이 도선에 접착하여 결합하게 해주는 접착층을 형성하는 물질로, 일례에 따르면 (a) 측쇄에 카르복실기를 갖는 우레탄 변성 폴리에스테르 수지, (b) 에폭시 수지, 및 (c) 이소시아네이트기-함유 경화제를 포함한다.The adhesive composition according to the present invention is a material for forming an adhesive layer that allows the insulating film to bond and bond to a conductive wire when the flexible flat cable is formed. According to an example, (a) a urethane-modified polyester resin having a carboxyl group in a side chain, and (b) Epoxy resins, and (c) isocyanate group-containing curing agents.
본 발명의 다른 일례에 따르면, 접착제 조성물은 (a) 측쇄에 카르복실기를 갖는 우레탄 변성 폴리에스테르 수지, (b) 에폭시 수지, (c) 이소시아네이트기-함유 경화제, 및 (d) 폴리에스테르수지를 포함한다.According to another example of the present invention, the adhesive composition comprises (a) a urethane-modified polyester resin having a carboxyl group in the side chain, (b) an epoxy resin, (c) an isocyanate group-containing curing agent, and (d) a polyester resin. .
이하, 각 성분에 대하여 설명한다.Hereinafter, each component is demonstrated.
(a) (a) 측쇄에On the side chain 카르복실기를 갖는 우레탄 변성 폴리에스테르 수지 Urethane Modified Polyester Resin Having Carboxyl Group
상기 측쇄에 카르복실기를 갖는 우레탄 변성 폴리에스테르 수지(이하, '우레탄 변성 폴리에스테르 수지'라 함)는 우레탄기(-NHCOO-)를 함유하는 반복단위, 에스테르기(-COO-)를 함유하는 반복단위 및 측쇄에 카르복실기(-COOH)를 갖는 반복단위를 포함하면서, 주사슬의 적어도 일 말단에 히드록시기(-OH)를 갖고 있는 블록 또는 랜덤 공중합체이다. 따라서, 상기 우레탄 변성 폴리에스테르 수지는 전술한 바와 같이, 측쇄의 카르복실기가 에폭시 수지와 반응하여 네트워크 구조가 형성되면서, 말단의 히드록시기가 이소시아네이트기-함유 경화제와 반응하여 IPN 구조가 형성되기 때문에, 접착제 조성물의 고내열 특성을 발휘할 수 있다.Urethane-modified polyester resin having a carboxyl group in the side chain (hereinafter referred to as "urethane-modified polyester resin") is a repeating unit containing a urethane group (-NHCOO-), repeating unit containing an ester group (-COO-) And it is a block or random copolymer which contains the repeating unit which has a carboxyl group (-COOH) in a side chain, and has a hydroxyl group (-OH) in at least one terminal of a main chain. Therefore, as described above, the urethane-modified polyester resin, as the carboxyl group of the side chain reacts with the epoxy resin to form a network structure, since the terminal hydroxy group reacts with the isocyanate group-containing curing agent to form an IPN structure, the adhesive composition Can exhibit high heat resistance.
일례에 따르면, 상기 우레탄 변성 폴리에스테르 수지는 하기 화학식 1로 표시되는 우레탄 변성 폴리에스테르 수지일 수 있다. According to an example, the urethane-modified polyester resin may be a urethane-modified polyester resin represented by the following formula (1).
Figure PCTKR2017015037-appb-C000001
Figure PCTKR2017015037-appb-C000001
(상기 화학식 1에서,(In Formula 1,
X는 1 내지 50의 정수이고, X is an integer from 1 to 50,
Y는 1 내지 50의 정수이며,Y is an integer from 1 to 50,
Z는 1 내지 50의 정수임).Z is an integer from 1 to 50.
다른 일례에 따르면, 상기 우레탄 변성 폴리에스테르 수지는 측쇄에 카르복실기(-COOH) 및 히드록시기(-OH)를 가지면서, 말단에 히드록시기(-OH)를 갖는 우레탄 변성 폴리에스테르 수지일 수 있는데, 이에 한정되지 않는다. According to another example, the urethane-modified polyester resin may be a urethane-modified polyester resin having a carboxyl group (-COOH) and a hydroxyl group (-OH) in the side chain, and having a hydroxyl group (-OH) at the terminal, but is not limited thereto. Do not.
본 발명에 따른 우레탄 변성 폴리에스테르 수지는 카르복실기의 당량이 특별히 한정되지 않으나, 약 500 내지 3000 g/eq 범위, 바람직하게 1000 내지 2000 g/eq범위일 경우, 접착제 조성물의 내열 특성이 더 향상되어 고온에서의 접착 특성이 향상될 수 있다. 한편, 상기 우레탄 변성 폴리에스테르 수지는 말단 및 측쇄 중 적어도 어느 하나에 히드록시기를 함유할 수 있다. 만약, 상기 우레탄 변성 폴리에스테르 수지가 측쇄에 히드록시기를 함유하는 경우, 상기 우레탄 변성 폴리에스테르 수지는 전체 히드록시기의 당량이 약 500 내지 3000 g/eq 범위일 경우, 접착제 조성물의 내열 특성 및 고온 접착 특성이 향상될 수 있다. 여기서, 상기 우레탄 변성 폴리에스테르 수지 내 카르복실기의 함유량이 히드록시기의 함유량에 비해 더 많을 경우, 가교도가 큰 네트워크 구조의 고분자가 형성될 수 있고, 따라서 접착제 조성물의 고내열 특성이 더 향상될 수 있다. 일례에 따르면, 상기 우레탄 변성 폴리에스테르 수지는 카르복실기와 히드록시기를 1 : 1.5~2.5의 당량비로 함유할 수 있다.The urethane-modified polyester resin according to the present invention is not particularly limited in the equivalent of the carboxyl group, but in the range of about 500 to 3000 g / eq, preferably in the range of 1000 to 2000 g / eq, the heat resistance characteristics of the adhesive composition is further improved to a high temperature The adhesive properties at can be improved. On the other hand, the urethane-modified polyester resin may contain a hydroxyl group in at least one of the terminal and the side chain. If the urethane-modified polyester resin contains a hydroxy group in the side chain, the urethane-modified polyester resin has heat resistance and high temperature adhesive properties of the adhesive composition when the equivalent of the total hydroxyl group is in the range of about 500 to 3000 g / eq. Can be improved. Here, when the content of the carboxyl group in the urethane-modified polyester resin is higher than the content of the hydroxy group, a polymer having a network structure having a high degree of crosslinking may be formed, and thus the high heat resistance property of the adhesive composition may be further improved. According to an example, the urethane-modified polyester resin may contain a carboxyl group and a hydroxyl group in an equivalent ratio of 1: 1.5 to 2.5.
또, 상기 우레탄 변성 폴리에스테르 수지는 수평균분자량이 약 10,000 내지 20,000 범위이고, 유리전이온도가 약 5 내지 25 ℃ 정도이다. Further, the urethane-modified polyester resin has a number average molecular weight in the range of about 10,000 to 20,000, and a glass transition temperature of about 5 to 25 ℃.
본 발명에서 사용하는 우레탄 변성 폴레에스테르 수지는 당 업계에 알려진 다양한 방법에 의해 합성될 수 있다. 일례로, 상기 측쇄에 카르복실기를 갖는 우레탄 변성 폴레에스테르 수지는 측쇄에 카르복실기를 갖는 폴리에스테르와 유기 디이소시아네이트를 반응시킴으로써 얻을 수 있다. 이때, 상기 측쇄에 카르복실기를 갖는 폴리에스테르는 당 업계에 알려진 방법에 따라 제조되는데, 구체적으로 폴리올류 및 다가 카르복실산 또는 이의 산 무수물의 중합반응에 의해 제조된 것이다. The urethane-modified polyester resin used in the present invention can be synthesized by various methods known in the art. As an example, the urethane modified polyester resin which has a carboxyl group in the said side chain can be obtained by making polyester which has a carboxyl group in a side chain, and organic diisocyanate react. At this time, the polyester having a carboxyl group in the side chain is prepared according to a method known in the art, specifically prepared by the polymerization of polyols and polyhydric carboxylic acid or acid anhydride thereof.
상기 폴리올류의 예로는 에틸렌글리콜, 디에틸렌글리콜, 프로필렌글리콜, 디프로필렌글리콜, 네오펜틸글리콜, 트리메틸올글리콜, 1,4-부타디올, 펜타에리트리톨, 2-메틸-1,3-프로판디올 등이 있는데, 이에 한정되지 않는다.Examples of the polyols include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, neopentyl glycol, trimethylol glycol, 1,4-butadiol, pentaerythritol, 2-methyl-1,3-propanediol, and the like. There is, but is not limited to this.
상기 다가 카르복실산 및 이의 산 무수물의 예로는 디메틸테레프탈산, 테레프탈산, 이소프탈산, 나프탈렌디카르복실산, 사이클로헥산디카르복실산, 디페닐디카르복실산, 아디프산(Adipic Acid), 말레산, 푸마르산, 트리멜리트산, 피로멜리트산 등과 이들의 산 무수물이 있는데, 이에 한정되지 않는다.Examples of the polyhydric carboxylic acid and acid anhydride thereof include dimethyl terephthalic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, cyclohexanedicarboxylic acid, diphenyldicarboxylic acid, adipic acid and maleic acid. , Fumaric acid, trimellitic acid, pyromellitic acid and the like, but are not limited thereto.
상기 유기 디이소시아네이트의 예로는 2,4-톨릴렌디이소시아네이트, p-페닐렌디이소시아네이트, 디페닐메탄-4,4'-디이소시아네이트, 헥사메틸렌디이소시아네이트, 테트라메틸렌디이소시아네이트, 1,5-나프탈렌디이소시아네이트, 크실렌 디이소시아네이트 등이 있는데, 이에 한정되지 않는다. Examples of the organic diisocyanate include 2,4-tolylene diisocyanate, p-phenylene diisocyanate, diphenylmethane-4,4'-diisocyanate, hexamethylene diisocyanate, tetramethylene diisocyanate, 1,5-naphthalene diisocyanate And xylene diisocyanate, but are not limited thereto.
(b) 에폭시 수지(b) epoxy resin
본 발명에 따른 접착제 조성물은 에폭시 수지를 포함한다. 상기 에폭시 수지는 분자 내 1개 이상, 바람직하게 2개 이상, 더 바람직하게 2~3개의 에폭시기를 갖는 고분자로, 본 발명에서는 일종의 경화제 역할을 한다. 이러한 에폭시 수지가 접착제 조성물의 일 성분으로 사용됨으로써, 접착제 조성물의 고내열 특성이 구현될 수 있다. 구체적으로, 상기 에폭시 수지는 접착제 조성물의 경화시 상기 우레 변성 폴리에스테르 수지의 카르복실기와 가교 반응하여 네트워크(network) 구조를 형성하기 때문에, 플렉시블 플랫 케이블(FFC) 내 접착층의 고내열 특성이 구현될 수 있다. 다만, 상기 에폭시 수지는 반응성이 느리기 때문에, FFC의 적층 공정시 수지층 또는 프라이머층과 도선 간의 접착이 잘 이루어지지 않을 수 있고, 또한 에폭시 수지의 brittle 특성으로 인해 플렉시블 특성이 저하될 수 있다. 따라서, 본 발명에서는 플렉시블 특성의 저하 없이 고내열 특성 및 접착 특성을 함께 향상시키기 위해서 경화제 성분으로 에폭시 수지 이외, 하기 이소시아네이트기-함유 경화제를 더 포함한다. The adhesive composition according to the present invention comprises an epoxy resin. The epoxy resin is a polymer having one or more, preferably two or more, more preferably two to three epoxy groups in the molecule, and serves as a kind of curing agent in the present invention. By using such an epoxy resin as one component of the adhesive composition, high heat resistance characteristics of the adhesive composition may be realized. Specifically, since the epoxy resin crosslinks and reacts with the carboxyl group of the urethane-modified polyester resin when the adhesive composition is cured, a high heat resistance property of the adhesive layer in the flexible flat cable (FFC) may be realized. have. However, since the epoxy resin has a low reactivity, adhesion between the resin layer or the primer layer and the conductive wire may not be well performed during the lamination process of the FFC, and the flexible property may be reduced due to the brittle characteristics of the epoxy resin. Accordingly, the present invention further includes the following isocyanate group-containing curing agent in addition to the epoxy resin as a curing agent component in order to improve both high heat resistance and adhesive properties without deteriorating the flexible property.
본 발명에서 사용되는 에폭시 수지의 비제한적인 예로는 비스페놀 A형 에폭시 수지, 수소 첨가 비스페놀 A형 에폭시 수지, 비스페놀 F형 에폭시 수지, 비스페놀 S형 에폭시 수지, 노볼락형 에폭시 수지, 크레졸 노볼락형 에폭시 수지, 페놀 노볼락형 에폭시 수지, 디시클로펜타디엔형 에폭시 수지, 트리페닐메탄형 에폭시 수지, 나프탈렌형 에폭시 수지, 비페닐형 에폭시 수지, 수소 첨가 비페닐형 에폭시 수지, 인(P) 함유 에폭시 수지, 러버 변성 에폭시 수지 등이 있으며, 이들은 단독 또는 2종 이상이 혼합되어 사용될 수 있다. 또한, 상기 에폭시 수지는 러버와 혼합되어 사용될 수도 있다.Non-limiting examples of the epoxy resin used in the present invention include bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, novolac type epoxy resin, cresol novolac type epoxy Resin, phenol novolak type epoxy resin, dicyclopentadiene type epoxy resin, triphenylmethane type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, hydrogenated biphenyl type epoxy resin, phosphorus (P) containing epoxy resin And rubber-modified epoxy resins, and these may be used alone or in combination of two or more thereof. In addition, the epoxy resin may be used in combination with a rubber.
상기 에폭시 수지의 에폭시 당량은 특별히 한정되지 않으며, 일례에 따르면 약 100 내지 300 g/eq 범위일 수 있고, 다른 일례에 따르면, 약 150 내지 250 g/eq 범위일 수 있다.The epoxy equivalent of the epoxy resin is not particularly limited, and according to one example may range from about 100 to 300 g / eq, and according to another example, may range from about 150 to 250 g / eq.
또, 상기 에폭시 수지의 함량은 특별히 한정되지 않으며, 일례에 따르면, 상기 우레탄 변성 폴리에스테르 수지 100 중량부를 기준으로 약 5 내지 30 중량부, 바람직하게 약 10 내지 20 중량부 범위일 수 있다.In addition, the content of the epoxy resin is not particularly limited, and according to an example, based on 100 parts by weight of the urethane-modified polyester resin may be in the range of about 5 to 30 parts by weight, preferably about 10 to 20 parts by weight.
(c) 이소시아네이트기-함유 경화제(c) isocyanate group-containing curing agents
본 발명에 따른 접착제 조성물은 이소시아네이트기-함유 경화제를 포함한다. 상기 이소시아네이트기-함유 경화제를 접착제 조성물의 일 성분으로 포함할 경우, 종래에 비해 상대적으로 낮은 온도 및 압력하에서 적층 공정을 수행하여 플렉시블 플랫 케이블을 제조할 수 있을 뿐만 아니라, 플렉시블 플랫 케이블의 접착 특성 및 플렉시블 특성을 동시에 향상시킬 수 있다. 다만, 경화제 성분으로 전술한 에폭시 수지 없이 이소시아네이트기-함유 경화제를 단독으로 사용할 경우, 히드록시기와 이소시아네이트기의 반응성이 너무 높아 접착층의 수명 특성이 저하되어 플렉시블 플랫 케이블의 수명 특성이 저하될 수 있다. 따라서, 본 발명에서는 경화제 성분으로 이소시아네이트기-함유 경화제와 에폭시 수지를 포함한다.Adhesive compositions according to the invention comprise an isocyanate group-containing curing agent. When the isocyanate group-containing curing agent is included as one component of the adhesive composition, not only can the flexible flat cable be manufactured by performing the lamination process at a relatively low temperature and pressure, but also the adhesive properties and Flexible characteristics can be improved simultaneously. However, when the isocyanate group-containing curing agent is used alone without the above-described epoxy resin as the curing agent component, the reactivity of the hydroxy group and the isocyanate group is too high, thereby deteriorating the life characteristics of the adhesive layer, which may reduce the life characteristics of the flexible flat cable. Accordingly, the present invention includes an isocyanate group-containing curing agent and an epoxy resin as the curing agent component.
본 발명에서 사용되는 이소시아네이트기-함유 경화제는 이소시아네이트기를 함유하는 물질이라면 특별히 한정되지 않는다. 예를 들어, 말단에 이소시아네이트기를 함유하는 고분자(예, 말단에 이소시아네이트기를 갖는 폴리우레탄 등); 2개 이상의(바람직하게, 2~3개의) 이소시아네이트기를 함유하는 올리고머; 및 이소시아네이트기-함유 경화제의 비제한적인 예로는 2,4-톨릴렌디이소시아네이트, p-페닐렌디이소시아네이트, 디페닐메탄-4,4'-디이소시아네이트, 헥사메틸렌디이소시아네이트, 테트라메틸렌디이소시아네이트, 1,5-나프탈렌디이소시아네이트, 크실렌 디이소시아네이트 등과 같은 2개 이상의(바람직하게, 2~3개의) 이소시아네이트기-함유 경화제 등이 있는데, 이들은 단독으로 또는 2종 이상이 혼합되어 사용될 수 있다. The isocyanate group-containing curing agent used in the present invention is not particularly limited as long as it is a substance containing an isocyanate group. For example, the polymer containing an isocyanate group at the terminal (for example, polyurethane etc. which have an isocyanate group at the terminal); Oligomers containing two or more (preferably two to three) isocyanate groups; And non-limiting examples of isocyanate group-containing curing agents include 2,4-tolylene diisocyanate, p-phenylene diisocyanate, diphenylmethane-4,4'-diisocyanate, hexamethylene diisocyanate, tetramethylene diisocyanate, 1, There are two or more (preferably two to three) isocyanate group-containing curing agents such as 5-naphthalene diisocyanate, xylene diisocyanate and the like, which may be used alone or in combination of two or more thereof.
일례에 따르면, 이소시아네이트기-함유 경화제로 말단에 이소시아네이트기를 갖는 폴리우레탄을 사용할 경우, FFC의 플렉시블 특성 및 고내열 특성 향상에 효과적이다. 이때, 상기 고분자의 수평균분자량은 특별히 한정되지 않으나, 고내열 특성 측면에서 약 700 ~ 1,000 범위인 것이 바람직하다.According to an example, when using the polyurethane which has an isocyanate group at the terminal as an isocyanate group containing hardening | curing agent, it is effective in improving the flexible characteristic and high heat resistance characteristic of FFC. At this time, the number average molecular weight of the polymer is not particularly limited, but is preferably in the range of about 700 to 1,000 in terms of high heat resistance characteristics.
다른 일례에 따르면, 이소시아네이트기-함유 경화제로 3개의 이소시아네이트기를 함유하는 올리고머를 사용할 경우, 네트워크 구조를 용이하게 형성할 수 있기 때문에, 고내열 특성을 구현할 수 있다. 이때, 상기 올리고머의 수평균분자량은 특별히 한정되지 않으나, 고내열 특성 측면에서 약 500 ~ 800 범위인 것이 바람직하다. According to another example, when an oligomer containing three isocyanate groups is used as the isocyanate group-containing curing agent, since the network structure can be easily formed, high heat resistance characteristics can be realized. At this time, the number average molecular weight of the oligomer is not particularly limited, but is preferably in the range of about 500 ~ 800 in terms of high heat resistance characteristics.
상기 이소시아네이트기-함유 경화제의 함량은 특별히 한정되지 않으나, 상기 카르복실기 함유 우레탄 변성 폴리에스테르 수지 100 중량부를 기준으로 약 5 내지 30 중량부 범위, 바람직하게 약 10 내지 25 중량부 범위일 경우, 블로킹(blocking) 현상이 발생하지 않고, 건조 후 라미네이션 공정 진행시 접착층과 도선 간의 접착력이 높게 유지될 수 있다.The content of the isocyanate group-containing curing agent is not particularly limited, but blocking in the range of about 5 to 30 parts by weight, preferably about 10 to 25 parts by weight based on 100 parts by weight of the carboxyl group-containing urethane-modified polyester resin. ) Does not occur, and the adhesion between the adhesive layer and the conductive wire may be maintained during the lamination process after drying.
(d) 폴리에스테르 수지(d) polyester resin
본 발명에 따른 접착제 조성물은 폴리에스테르 수지를 더 포함할 수 있다. 본 발명에서 사용 가능한 폴리에스테르 수지는 수평균분자량이 약 13,000~25,000 범위, 바람직하게 13,000~22,000 범위인 것을 사용할 수 있다. 이러한 폴리에스테르 수지의 함량은 특별히 한정되지 않으나, 상기 우레탄 변성 폴리에스테르 수지 100 중량부를 기준으로 약 0~100 중량부 범위, 바람직하게 약 20~100 중량부 범위, 더 바람직하게 약 30~100 중량부 범위일 경우, 접착제 조성물의 접착 특성 및 내열 특성을 향상시킬 수 있다. The adhesive composition according to the present invention may further comprise a polyester resin. As the polyester resin usable in the present invention, a number average molecular weight can be used in the range of about 13,000 to 25,000, preferably 13,000 to 22,000. The content of the polyester resin is not particularly limited, but is based on 100 parts by weight of the urethane-modified polyester resin, about 0 to 100 parts by weight, preferably about 20 to 100 parts by weight, more preferably about 30 to 100 parts by weight. In the range, it is possible to improve the adhesive properties and heat resistance properties of the adhesive composition.
(e) 추가 성분(e) additional ingredients
본 발명에 따른 접착제 조성물은 전술한 우레탄 변성 폴리에스테르 수지, 에폭시 수지 및 이소시아네이트기-함유 경화제 이외, 필요에 따라 접착제 조성물의 내열 특성, 접착 특성을 저하시키지 않는 범위 내에서 난연제, 블로킹 방지제(antiblocking agent)를 사용할 수 있는데, 예컨대 브롬계 난연제, 수산화알루미늄, 실리카, 티타늄디옥사이드(titanium dioxide), 삼산화안티몬 등이 있는데, 이에 한정되지 않는다. 이들의 함량은 특별히 한정되지 않으며, 상기 우레탄 변성 폴리에스테르 수지 100 중량부를 기준으로 약 1 내지 20 중량부 범위일 수 있다.The adhesive composition according to the present invention is a flame retardant and an antiblocking agent in addition to the above-mentioned urethane-modified polyester resin, epoxy resin, and isocyanate group-containing curing agent, as long as the heat resistance and adhesive properties of the adhesive composition are not deteriorated. ), For example, bromine-based flame retardant, aluminum hydroxide, silica, titanium dioxide, antimony trioxide, and the like, but is not limited thereto. The content thereof is not particularly limited, and may be in a range of about 1 to 20 parts by weight based on 100 parts by weight of the urethane-modified polyester resin.
전술한 본 발명의 접착제 조성물의 점도는 특별히 한정되지 않으나, 약 500 내지 4000 cPs 범위일 경우, 레진 안정성이 우수하다. 또, 상기 접착제 조성물은 조성물 총 중량을 기준으로 고형분 함량이 약 35 내지 45 %일 경우, 조성물의 코팅성이 우수하여 작업성이 향상될 수 있다.Although the viscosity of the adhesive composition of the present invention described above is not particularly limited, the resin stability is excellent when it is in the range of about 500 to 4000 cPs. In addition, the adhesive composition has a solid content of about 35 to 45% based on the total weight of the composition, the coating property of the composition can be improved to improve workability.
<플렉시블 플랫 케이블><Flexible Flat Cable>
본 발명은 전술한 접착제 조성물로 형성된 접착층을 포함하는 플렉시블 플랫 케이블을 제공한다.The present invention provides a flexible flat cable comprising an adhesive layer formed of the adhesive composition described above.
일례에 따르면, 상기 플렉시블 플랫 케이블(100)은 도 1에 도시된 바와 같이, 도선(10); 및 상기 도선의 적어도 일면에 위치하며, 접착층(21), 프라이머층(22) 및 수지층(23)을 순차적으로 포함하는 절연필름(20)을 구비하되, 상기 접착층(21)은 전술한 접착제 조성물로 형성된다. 이러한 플렉시블 플랫 케이블은 고온/고습 조건하에서 기계적 특성, 열적 특성 및 전기적 특성이 우수하다.According to one example, the flexible flat cable 100, as shown in Figure 1, the conductor (10); And an insulating film 20 positioned on at least one surface of the conductive wire and sequentially including an adhesive layer 21, a primer layer 22, and a resin layer 23, wherein the adhesive layer 21 is the adhesive composition described above. Is formed. These flexible flat cables have excellent mechanical, thermal and electrical properties under high temperature / high humidity conditions.
상기 플렉시블 플랫 케이블(100)에서, 도선(10)는 소정의 폭 및 두께를 가지는 복수의 평판 형상의 물질로, 구리, 주석-도금 구리, 니켈-도금 구리 등의 도전성 금속으로 이루어질 수 있다. 일례에 따르면, 상기 도선(10)는 구리로 이루어진 박 형상의 물질일 수 있다.In the flexible flat cable 100, the conductive wire 10 is a plurality of flat plate-like material having a predetermined width and thickness, it may be made of a conductive metal such as copper, tin-plated copper, nickel-plated copper. According to an example, the conductive wire 10 may be a thin material made of copper.
이때 도선의 두께나 형상은 특별히 한정되지 않으며, 당 분야에 알려진 통상적인 도선을 제한없이 사용할 수 있다. 일례로, 플렉시블 플랫 케이블(100)의 슬라이딩성을 고려하여 도선의 두께는 약 20 내지 50 ㎛ 범위일 수 있다.In this case, the thickness or shape of the conductive wire is not particularly limited, and conventional conductive wires known in the art may be used without limitation. For example, the thickness of the conductive wire may be in the range of about 20 to 50 μm in consideration of the sliding property of the flexible flat cable 100.
본 발명의 플렉시블 플랫 케이블(100)에서, 절연필름(20)은 접착층(21), 프라이머층(22) 및 수지층(22)을 포함하며, 이들은 순차적으로 적층되어 있다. 이러한 절연필름(20)은 도선의 일면 또는 양면에 상기 접착층(21)이 접촉되어 적층됨으로써 도선을 피복한다. In the flexible flat cable 100 of the present invention, the insulating film 20 includes an adhesive layer 21, a primer layer 22 and a resin layer 22, which are sequentially stacked. The insulating film 20 covers the conductive wires by being laminated by contacting the adhesive layer 21 on one or both surfaces of the conductive wires.
상기 접착층(21)은 절연필름(20)이 도선(10)에 접착시켜 결합하는 것으로, 전술한 접착제 조성물로 형성된다. 구체적으로, 상기 접착제 조성물은 약 100 ~ 180 ℃의 온도 조건에서 경화를 실시하면 상기 우레탄 변성 폴리에스테르 수지가 에폭시 수지 및 이소시아네이트기-함유 경화제와 반응하여 네트워크 구조 및/또는 IPN 구조의 폴리머를 형성한다. 이러한 폴리머는 유리전이온도가 약 100 ℃ 이하, 바람직하게 약 50 내지 100 ℃ 범위이고, 연화점이 약 250 ℃ 이상, 바람직하게 약 250 내지 300 ℃로 고내열성 수지이기 때문에, 260 ℃ 이상의 온도에서 솔더링하더라도 도선과 절연필름 간의 박리(탈착)를 최소화시킬 수 있다. 이때, 상기 접착층과 도선 간의 접착 강도는 약 1.5 내지 2.0 kgf/cm이다. 이러한 접착층과 도선층 간의 접착강도는 먼저 본 발명의 접착제 조성물을 동박에 도포한 후, 고온/고압 프레스 장치를 이용하여 압축(프레스 조건: 170 ℃, 5700 lb 및 3분)하여 샘플을 제작한 다음, 상기 샘플의 90도 접착력을 측정한 것이다.The adhesive layer 21 is to bond the insulating film 20 to the conductive wire 10 to be bonded, it is formed of the adhesive composition described above. Specifically, when the adhesive composition is cured at a temperature condition of about 100 to 180 ° C., the urethane-modified polyester resin reacts with an epoxy resin and an isocyanate group-containing curing agent to form a polymer having a network structure and / or an IPN structure. . Such polymers are highly heat resistant resins having a glass transition temperature of about 100 ° C. or lower, preferably about 50 to 100 ° C., and a softening point of about 250 ° C. or higher, preferably about 250 to 300 ° C., even if soldered at a temperature of 260 ° C. or higher. Peeling (desorption) between the lead and the insulating film can be minimized. At this time, the adhesive strength between the adhesive layer and the conductive wire is about 1.5 to 2.0 kgf / cm. The adhesive strength between the adhesive layer and the conductive layer is first applied to the copper foil of the adhesive composition of the present invention, and then compressed using a high temperature / high pressure press device (press conditions: 170 ° C., 5700 lb and 3 minutes) to prepare a sample. , The 90 degree adhesive force of the sample is measured.
본 발명의 플렉시블 플랫 케이블(100)에서, 프라이머층(primer layer)(22)은 접착층(21)과 수지층(23) 사이에 위치하여 접착층과 수지층이 직접 결합했을 때의 부족한 결합력을 보완해주기 때문에, 플렉시블 플랫 케이블의 내열 특성 및 내습 특성이 더 향상될 수 있다. In the flexible flat cable 100 of the present invention, the primer layer 22 is positioned between the adhesive layer 21 and the resin layer 23 to compensate for the insufficient bonding strength when the adhesive layer and the resin layer are directly bonded. Because of this, the heat and moisture resistance characteristics of the flexible flat cable can be further improved.
이러한 프라이머층(22)을 형성하는 조성물(이하, '프라이머층 형성 조성물'이라 함)은 에폭시 수지, 설폰기-함유 고분자, 폴리에스테르 수지 및 폴리우레탄으로 이루어진 군에서 선택된 1종 이상의 프라이머 수지를 포함한다.The composition forming the primer layer 22 (hereinafter, referred to as a 'primer layer forming composition') includes at least one primer resin selected from the group consisting of an epoxy resin, a sulfone group-containing polymer, a polyester resin, and a polyurethane. do.
일례에 따르면, 에폭시 수지를 이용하여 프라이머층을 형성할 경우, 접착층과의 계면에서 상기 에폭시 수지가 접착층과 가교 반응할 수 있고, 따라서 접착층과 수지층 간의 접착 강도가 더 향상될 수 있다. 이러한 에폭시 수지의 예로는 상기 접착제 조성물의 에폭시 수지 부분에 기재된 바와 동일하다. According to an example, when the primer layer is formed using an epoxy resin, the epoxy resin may crosslink with the adhesive layer at the interface with the adhesive layer, and thus the adhesive strength between the adhesive layer and the resin layer may be further improved. Examples of such epoxy resins are the same as described in the epoxy resin portion of the adhesive composition.
상기 프라이머층 형성 조성물은 필요에 따라 프라이머층의 특성을 저하시키지 않는 범위 내에서 이소시아네이트기-함유 경화제, 실리카 및 질소계 촉매로 이루어진 군에서 선택된 1종 이상을 더 포함할 수 있다. 상기 이소시아네이트기-함유 경화제는 상기 접착제 조성물의 이소시아네이트기-함유 경화제 부분에 기재된 바와 동일하다. 이때, 이들의 함량은 각각 특별히 한정되지 않으며, 예를 들어 전술한 프라이머 수지 100 중량부를 기준으로 약 1 내지 20 중량부 범위일 수 있다.The primer layer forming composition may further include one or more selected from the group consisting of an isocyanate group-containing curing agent, silica, and a nitrogen-based catalyst within a range that does not deteriorate the properties of the primer layer, if necessary. The isocyanate group-containing curing agent is the same as described in the isocyanate group-containing curing agent portion of the adhesive composition. At this time, their content is not particularly limited, for example, may be in the range of about 1 to 20 parts by weight based on 100 parts by weight of the above-described primer resin.
본 발명의 플렉시블 플랫 케이블(100)에서, 수지층(23)은 절연필름의 최외각에 위치하며 도선(10)이 외부와 절연될 수 있도록 한다. 이러한 수지층(22)은 당 업계에서 알려진 절연성 수지라면 특별히 한정되지 않으며, 예컨대 폴리이미드 필름, 폴리아크릴로니트릴 필름, PET 필름(Poly ethylene therephtalate Film) 필름, PEEK 필름(Poly ether ether ketone Film), 폴리에스테르 수지 필름 등이 있다.In the flexible flat cable 100 of the present invention, the resin layer 23 is located at the outermost portion of the insulating film so that the conductive wire 10 can be insulated from the outside. The resin layer 22 is not particularly limited as long as it is an insulating resin known in the art, and for example, polyimide film, polyacrylonitrile film, PET film (Poly ethylene therephtalate Film) film, PEEK film (Poly ether ether ketone Film), Polyester resin films and the like.
또한, 본 발명은 전술한 절연필름을 포함하는 플렉시블 플랫 케이블(FFC)의 제조방법을 제공한다.In addition, the present invention provides a method of manufacturing a flexible flat cable (FFC) comprising the above-described insulation film.
구체적으로, 상기 FFC를 제조하는 일례를 들면, 절연필름을 2개 준비하는 단계; 및 2개의 절연필름의 접착층 사이에 도선을 개재시킨 후 합지하는 단계를 포함하여 구성될 수 있다.Specifically, as an example of manufacturing the FFC, preparing two insulating films; And laminating the conductive wires between the adhesive layers of the two insulating films.
본 발명에서는 상기 절연필름을 도선에 부착시키기 전에, 절연필름을 원하는 크기로 절단하는 단계를 추가로 수행할 수 있다.In the present invention, before attaching the insulating film to the conductive wire, the step of cutting the insulating film to a desired size may be further performed.
전술한 본 발명에 따른 플렉시블 플랫 케이블은 액정 표시 장치(LCD, liquid crystal display), 발광다이오드(LED: light emitting diode), 터치 패널, 전계방출 디스플레이(FED: field emission display), PDA, 플라즈마 표시패널(PDP: plasma display panel), BLU(backlight unit), 광원 부품 등에 사용될 수 있다. 또한, 본 발명의 플렉시블 플랫 케이블은 차량의 하네스 배선으로 사용될 수도 있다.The above-described flexible flat cable according to the present invention is a liquid crystal display (LCD), a light emitting diode (LED), a touch panel, a field emission display (FED), a PDA, a plasma display panel. (PDP: plasma display panel), BLU (backlight unit), light source components, etc. can be used. In addition, the flexible flat cable of the present invention can be used as a harness wiring of a vehicle.
이하, 구체적인 실시예를 통해 본 발명을 보다 구체적으로 설명한다. 하기 실시예는 본 발명의 이해를 돕기 위한 예시에 불과하며, 본 발명의 범위가 이에 한정되는 것은 아니다. Hereinafter, the present invention will be described in more detail with reference to specific examples. The following examples are merely examples to help understanding of the present invention, but the scope of the present invention is not limited thereto.
<< 실시예Example 1>  1>
1-1. 접착제 조성물의 제조1-1. Preparation of Adhesive Composition
100 중량부의 우레탄 변성 폴리에스테르 수지(수평균분자량: 13,000, 카르복실기 당량: 1,600, 히드록시기 당량: 6,500), 10 중량부의 에폭시 수지(TOYOBO社의 HY-30, 에폭시 당량: 190), 25 중량부의 이소시아네이트(미츠이 케미칼, Takenate D-120N) 및 100 중량부의 폴리에스테르수지(일본 합성, SP-181, 수평균 분자량: 22,000)를 혼합하여 접착제 조성물을 얻었다. 여기서, '중량부'는 우레탄 변성 폴리에스테르 수지 100 중량부를 기준으로 한 것이다.100 parts by weight of urethane-modified polyester resin (number average molecular weight: 13,000, carboxyl equivalent: 1,600, hydroxy equivalent: 6,500), 10 parts by weight of epoxy resin (HY-30 from TOYOBO, epoxy equivalent: 190), 25 parts by weight of isocyanate ( Mitsui Chemicals, Takenate D-120N) and 100 parts by weight of polyester resin (Japanese synthetic, SP-181, number average molecular weight: 22,000) were mixed to obtain an adhesive composition. Here, the "parts by weight" is based on 100 parts by weight of the urethane-modified polyester resin.
1-2. 절연 필름의 제조1-2. Manufacture of insulation film
PET 필름(두께: 25 ㎛)의 일면에 콤마 코트 방식으로 에폭시 수지(하기 표 1의 Epoxy Ⅰ)를 12 ㎛의 두께로 코팅하고, 140 ℃의 온도에서 경화하여 프라이머층을 형성하였다. 이후, 상기 프라이머층 상에 상기 실시예 1-1에서 제조된 접착제 조성물을 코팅하고 130 ℃의 온도에서 경화시켜 두께 20 ㎛의 접착층을 형성함으로써 절연 필름을 제조하였다.One surface of the PET film (thickness: 25 μm) was coated with an epoxy resin (Epoxy I in Table 1) to a thickness of 12 μm by a comma coat method, and cured at a temperature of 140 ° C. to form a primer layer. Thereafter, an insulating film was prepared by coating the adhesive composition prepared in Example 1-1 on the primer layer and curing at a temperature of 130 ° C. to form an adhesive layer having a thickness of 20 μm.
1-3. 1-3. 플렉시블flexible 플랫flat 케이블의 제조 Manufacture of cable
상기 실시예 1-2에서 제조된 2개의 절연필름의 접착층 사이에 두께 35 ㎛의 도체를 개재시킨 뒤, 0.8 m/min의 속도로 라미네이팅하여 플렉시블 플랫 케이블을 제조하였다.A flexible flat cable was manufactured by sandwiching a conductor having a thickness of 35 μm between the adhesive layers of the two insulating films prepared in Example 1-2 and laminating at a speed of 0.8 m / min.
<< 실시예Example 2~4> 및 < 2-4> and < 비교예Comparative example 1~2>  1 ~ 2>
하기 표 1에 나타낸 조성을 갖는 실시예 2~4 및 비교예 1~2의 접착제 조성물을 각각 제조하였고, 또 하기 표 1에 기재된 수지층 및 프라이머층을 이용하여 실시예 2~3 및 비교예 1~2의 절연필름을 제조하였다. 이후, 각 접착제 조성물 및 절연필름을 이용하여 실시예 2~3 및 비교예 1~2의 플렉시블 플랫 케이블을 각각 제조하였다. 하기 표 1에서 Epoxy Ⅰ은 비스페놀 A 에폭시 수지(a)와 아크릴 러버(b)의 혼합물(a:b=1:2 중량비율)이고, Epoxy Ⅱ는 비스페놀 A 에폭시 수지(a)와 NBR 러버(c)의 혼합물(a:c=2:1 중량비율)이다.The adhesive compositions of Examples 2 to 4 and Comparative Examples 1 and 2 having the compositions shown in Table 1 were prepared, respectively, and Examples 2 to 3 and Comparative Examples 1 to 1 were prepared using the resin layers and primer layers shown in Table 1 below. 2 insulating film was prepared. Thereafter, the flexible flat cables of Examples 2 to 3 and Comparative Examples 1 and 2 were prepared using the respective adhesive compositions and insulating films. In Table 1, Epoxy I is a mixture of bisphenol A epoxy resin (a) and acrylic rubber (b) (a: b = 1: 2 weight ratio), and Epoxy II is bisphenol A epoxy resin (a) and NBR rubber (c ) Is a mixture (a: c = 2: 1 weight ratio).
접착제 조성물의 조성(중량부)Composition of Adhesive Composition (parts by weight) 프라이머층의 성분Component of the primer layer
우레탄 변성 폴리에스테르 수지 Urethane Modified Polyester Resin 에폭시 수지Epoxy resin 이소시아네이트기-함유 경화제Isocyanate Group-Containing Curing Agent 폴리에스테르 수지Polyester resin 에폭시 수지Epoxy resin
실시예 1Example 1 100100 1010 2525 100100 Epoxy ⅠEpoxy Ⅰ
실시예 2Example 2 100100 2020 2525 100100 Epoxy ⅠEpoxy Ⅰ
실시예 3Example 3 100100 1010 1010 3030 Epoxy ⅠEpoxy Ⅰ
실시예 4Example 4 100100 1010 1010 100100 Epoxy ⅡEpoxy II
비교예 1Comparative Example 1 -- -- 6060 100100 Epoxy ⅡEpoxy II
비교예 2Comparative Example 2 100100 -- -- 100100 Epoxy ⅠEpoxy Ⅰ
<< 실험예Experimental Example 1>  1>
TMA Penetration method에 따라 실시예 4 및 비교예 1~2의 접착제 조성물의 유리전이온도(Tg) 및 연화점(Ts)를 측정하였고, 측정 결과를 표 2 및 도 2에 나타내었다. The glass transition temperature (Tg) and softening point (Ts) of the adhesive compositions of Example 4 and Comparative Examples 1 and 2 were measured according to the TMA Penetration method, and the measurement results are shown in Table 2 and FIG. 2.
측정 결과, 실시예 4의 접착제 조성물은 유리전이온도(Tg)가 약 71 ℃ 이었고, 연화점(Ts)가 250 ℃ 이상으로 측정되었다.As a result of the measurement, the adhesive composition of Example 4 had a glass transition temperature (Tg) of about 71 ° C. and a softening point (Ts) of 250 ° C. or more.
이와 같이, 본 발명에 따른 접착제 조성물은 유리전이온도가 100 ℃ 이하이기 때문에, 100 ℃ 이하의 온도에서 용이하게 경화될 수 있으며, 나아가 연화점이 200 ℃ 이상으로 높기 때문에, 200 ℃ 이상의 온도에서 솔더링하더라도 FFC의 도선과 절연필름 간의 접착 강도 저하가 초래되지 않는다는 것을 알 수 있었다.As described above, the adhesive composition according to the present invention can be easily cured at a temperature of 100 ° C. or less because the glass transition temperature is 100 ° C. or less, and furthermore, even if soldering at a temperature of 200 ° C. or more, since the softening point is higher than 200 ° C. It was found that a decrease in the adhesive strength between the lead wire of the FFC and the insulating film was not caused.
Tg (℃)Tg (℃) Ts (℃)Ts (℃)
실시예 4Example 4 7171 300 300
비교예 1Comparative Example 1 8989 217217
비교예 2Comparative Example 2 61 / 10361/103 145145
<< 실험예Experimental Example 2>  2>
소정의 회로 패턴이 형성되어 있는 FPCB 상부에 실시예 1~4 및 비교예 1~2의 플렉시블 플랫 케이블을 합지한 다음, 260℃의 온도에서 3회 Reflow 테스트를 진행하여 층간 박리(delamination)의 발생 여부를 확인하였고, 또한 280 ℃의 온도에서 3회 Reflow 테스트를 진행하여 층간 박리의 발생 여부를 확인하였다. 측정 결과를 하기 표 2 및 도 3에 나타내었다. 하기 표 3에서, 층간 박리가 발생한 경우는 "○"로 표시하였고, 층간 박리가 발생하지 않은 경우는 "X"로 표시하였다.Laminating the flexible flat cables of Examples 1 to 4 and Comparative Examples 1 and 2 on the FPCB having a predetermined circuit pattern, and then performing three reflow tests at a temperature of 260 ° C. to generate delamination. It was confirmed whether or not, and also in the reflow test three times at a temperature of 280 ℃ to determine whether the interlayer peeling occurred. The measurement results are shown in Table 2 and FIG. 3. In Table 3 below, when interlaminar peeling occurred, it was expressed as "○", and when interlaminar peeling did not occur, it was expressed as "X".
실시예 1Example 1 실시예 2Example 2 실시예 3Example 3 실시예 4Example 4 비교예 1Comparative Example 1 비교예 2Comparative Example 2
260 ℃ Reflow 3회260 ℃ Reflow 3 times XX XX XX XX XX ○○
280 ℃ Reflow 3회280 ℃ Reflow 3 times ○○ ○○ ○○ XX ○○ ○○
측정 결과, 260 ℃에서 3회 Reflow 진행한 후, 실시예 1~4의 플렉시블 플랫 케이블은 층간 박리가 발생하지 않았다. 반면, 비교예 1~2의 플렉시블 플랫 케이블은 층간 박리가 발생하였다. 특히, 실시예 4의 플렉시블 플랫 케이블은 280 ℃에서 3회 Reflow 진행한 후에도 층간 박리가 발생하지 않았다(도 3(a) 참조). 반면, 비교예 2의 플렉시블 플랫 케이블은 280 ℃에서 3회 Reflow 진행한 후 층간 박리가 발생하였다(도 3(b) 참조).As a result of measurement, after performing reflow three times at 260 degreeC, the interlayer peeling did not generate | occur | produce the flexible flat cable of Examples 1-4. On the other hand, in the flexible flat cables of Comparative Examples 1 and 2, delamination occurred. In particular, in the flexible flat cable of Example 4, the interlayer peeling did not occur even after reflowing three times at 280 ° C (see FIG. 3 (a)). On the other hand, in the flexible flat cable of Comparative Example 2 after the three reflow proceeds at 280 ℃ delamination occurred (see Figure 3 (b)).
이와 같이, 본 발명에 따른 접착제 조성물은 내열 특성이 우수하기 때문에, 플렉시블 플랫 케이블의 사용 온도를 높일 수 있었다.Thus, since the adhesive composition which concerns on this invention is excellent in heat resistance characteristic, the use temperature of a flexible flat cable was able to be raised.

Claims (17)

  1. (a) 측쇄에 카르복실기를 갖는 우레탄 변성 폴리에스테르 수지; (a) urethane modified polyester resin which has a carboxyl group in a side chain;
    (b) 에폭시 수지; 및 (b) epoxy resins; And
    (c) 이소시아네이트기-함유 경화제(c) isocyanate group-containing curing agents
    를 포함하는 접착제 조성물.Adhesive composition comprising a.
  2. 제1항에 있어서,The method of claim 1,
    폴리에스테르 수지를 더 포함하는 것이 특징인 접착제 조성물.Adhesive composition, characterized in that it further comprises a polyester resin.
  3. 제1항에 있어서,The method of claim 1,
    상기 측쇄에 카르복실기를 갖는 우레탄 변성 폴리에스테르 수지는 하기 화학식 1로 표시되는 우레탄 변성 폴리에스테르 수지인 것이 특징인 접착제 조성물:Adhesive composition characterized in that the urethane-modified polyester resin having a carboxyl group in the side chain is a urethane-modified polyester resin represented by the following formula (1):
    [화학식 1][Formula 1]
    Figure PCTKR2017015037-appb-I000001
    Figure PCTKR2017015037-appb-I000001
    (상기 화학식 1에서,(In Formula 1,
    X는 1 내지 50의 정수이고, X is an integer from 1 to 50,
    Y는 1 내지 50의 정수이며,Y is an integer from 1 to 50,
    Z는 1 내지 50의 정수임).Z is an integer from 1 to 50.
  4. 제1항에 있어서,The method of claim 1,
    상기 우레탄 변성 폴리에스테르 수지 내 카르복실기의 당량은 500 내지 3000 g/eq 범위인 것이 특징인 접착제 조성물.Adhesive composition, characterized in that the equivalent of the carboxyl group in the urethane-modified polyester resin is in the range of 500 to 3000 g / eq.
  5. 제1항에 있어서,The method of claim 1,
    상기 우레탄 변성 폴리에스테르 수지는 말단 및 측쇄 중 적어도 어느 하나에 히드록시기를 갖는 것이 특징인 접착제 조성물.Adhesive composition, characterized in that the urethane-modified polyester resin has a hydroxyl group in at least one of the terminal and side chain.
  6. 제5항에 있어서,The method of claim 5,
    상기 우레탄 변성 폴리에스테르 수지 내 히드록시기의 당량은 500 내지 3000 g/eq 범위인 것이 특징인 접착제 조성물.Adhesive composition, characterized in that the equivalent of the hydroxyl group in the urethane-modified polyester resin ranges from 500 to 3000 g / eq.
  7. 제1항에 있어서,The method of claim 1,
    상기 에폭시 수지는 에폭시 당량이 150 내지 250 g/eq 범위인 것이 특징인 접착제 조성물.The epoxy resin is an adhesive composition, characterized in that the epoxy equivalent range of 150 to 250 g / eq.
  8. 제1항에 있어서,The method of claim 1,
    상기 이소시아네이트기-함유 경화제는 말단에 이소시아네이트기를 함유하는 고분자; 2개 이상의 이소시아네이트기를 함유하는 올리고머; 및 2개 이상의 이소시아네이트기-함유 경화제로 이루어진 군에서 선택된 것이 특징인 접착제 조성물.The isocyanate group-containing curing agent is a polymer containing an isocyanate group at the terminal; Oligomers containing two or more isocyanate groups; And at least two isocyanate group-containing curing agents.
  9. 제1항에 있어서, The method of claim 1,
    상기 우레탄 변성 폴리에스테르 수지 100 중량부,100 parts by weight of the urethane-modified polyester resin,
    상기 에폭시 수지 5 내지 30 중량부, 및5 to 30 parts by weight of the epoxy resin, and
    상기 이소시아네이트기-함유 경화제 5 내지 30 중량부5 to 30 parts by weight of the isocyanate group-containing curing agent
    를 포함하는 접착제 조성물.Adhesive composition comprising a.
  10. 제1항 내지 제9항 중 어느 한 항에 기재된 접착제 조성물로 형성된 접착층을 포함하는 플렉시블 플랫 케이블.The flexible flat cable containing the adhesive layer formed from the adhesive composition in any one of Claims 1-9.
  11. 제10항에 있어서, The method of claim 10,
    도선; 및ferry; And
    상기 도선의 적어도 일면에 위치하며, 접착층, 프라이머층 및 수지층을 순차적으로 포함하는 절연필름Located on at least one surface of the conductive wire, the insulating film sequentially comprising an adhesive layer, a primer layer and a resin layer
    을 포함하는 플렉시블 플랫 케이블.Flexible flat cable including.
  12. 제10항에 있어서,The method of claim 10,
    상기 접착층은 연화점이 250 내지 300 ℃ 범위인 것이 특징인 플렉시블 플랫 케이블.Flexible adhesive cable is characterized in that the softening point is in the range of 250 to 300 ℃.
  13. 제11항에 있어서, The method of claim 11,
    상기 프라이머층은 폴리에스테르 수지, 폴리우레탄, 에폭시 수지 및 설폰기-함유 고분자로 이루어진 군에서 선택된 것으로 형성된 것이 특징인 플렉시블 플랫 케이블.The primer layer is a flexible flat cable, characterized in that formed from the group consisting of polyester resin, polyurethane, epoxy resin and sulfone group-containing polymer.
  14. 제11항에 있어서,The method of claim 11,
    상기 수지층은 폴리이미드 필름, 폴리아크릴로니트릴 필름, PET 필름(Poly ethylene therephtalate Film) 필름, PEEK 필름(Poly ether ether ketone Film), 폴리에스테르 수지 필름으로 이루어진 군에서 선택된 것으로 형성된 것이 특징인 플렉시블 플랫 케이블.The resin layer is a flexible flat, characterized in that formed of a polyimide film, polyacrylonitrile film, PET film (Poly ethylene therephtalate Film) film, PEEK film (Poly ether ether ketone Film), polyester resin film selected from the group consisting of cable.
  15. 제10항에 기재된 플렉시블 플랫 케이블을 구비하는 플렉시블 플랫 케이블 모듈.The flexible flat cable module provided with the flexible flat cable of Claim 10.
  16. 제15항에 기재된 플렉시블 플랫 케이블을 구비하는 전원공급장치.A power supply comprising the flexible flat cable of claim 15.
  17. 제16항에 기재된 전원공급장치를 구비하는 디스플레이 장치.A display device comprising the power supply device according to claim 16.
PCT/KR2017/015037 2016-12-23 2017-12-19 Adhesive composition and flexible flat cable using same WO2018117607A1 (en)

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