WO2019045336A1 - Film adhésif de silicone de type sans substrat - Google Patents

Film adhésif de silicone de type sans substrat Download PDF

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Publication number
WO2019045336A1
WO2019045336A1 PCT/KR2018/009496 KR2018009496W WO2019045336A1 WO 2019045336 A1 WO2019045336 A1 WO 2019045336A1 KR 2018009496 W KR2018009496 W KR 2018009496W WO 2019045336 A1 WO2019045336 A1 WO 2019045336A1
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WO
WIPO (PCT)
Prior art keywords
adhesive layer
silicone
release film
silicone adhesive
film
Prior art date
Application number
PCT/KR2018/009496
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English (en)
Korean (ko)
Inventor
이주형
이재훈
황용재
Original Assignee
주식회사 두산
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Publication of WO2019045336A1 publication Critical patent/WO2019045336A1/fr

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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02Non-macromolecular additives
    • C09J11/06Non-macromolecular additives organic
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J183/00Adhesives 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
    • C09J183/04Polysiloxanes
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00Adhesives in the form of films or foils
    • C09J7/20Adhesives in the form of films or foils characterised by their carriers
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00Adhesives in the form of films or foils
    • C09J7/40Adhesives in the form of films or foils characterised by release liners
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00Additional features of adhesives in the form of films or foils
    • C09J2301/20Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive itself
    • C09J2301/208Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive itself the adhesive layer being constituted by at least two or more adjacent or superposed adhesive layers, e.g. multilayer adhesive
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00Additional features of adhesives in the form of films or foils
    • C09J2301/30Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature

Definitions

  • a semiconductor packaging process is generally performed by placing a chip on a circuit pattern of a printed circuit board (PCB) substrate and then performing a post-process such as an EMC molding and a baking process.
  • PCB printed circuit board
  • the reflow process at 220 ° C or more can not be performed because of low thermal stability.
  • the present invention has been conceived in order to solve the above-mentioned problems, and it is an object of the present invention to provide an adhesive film which can form an adhesive film without using a base film, exhibits high heat resistance, high adhesive property and transcription property, Substrate-type silicone adhesive film which does not cause contamination due to heat and moisture.
  • the present invention provides a light emitting device comprising: a first release film; A second release film; And a silicone adhesive layer formed between the first release film and the second release film, wherein the adhesive strength of the silicone adhesive layer to the first release film or the second release film measured by ASTM D3330 is 10 to 900 gf / inch And a non-substrate-type silicone adhesive film.
  • the present invention also relates to a film forming method comprising: a first release film; A second release film; A first silicone adhesive layer and a second silicone adhesive layer respectively formed between the first release film and the second release film; And a silicone non-adhesive layer formed between the first silicone adhesive layer and the second silicone adhesive layer, wherein the first silicone adhesive layer or the second silicone adhesive layer for the first release film or the second release film measured by ASTM D3330 And the adhesive strength of the adhesive layer is 10 to 900 gf / inch, respectively.
  • the inorganic silicone-type adhesive film of the present invention is capable of producing an adhesive film without using a base film, has good coating appearance characteristics, and has excellent transfer characteristics of the silicone adhesive layer after removing the release film.
  • a silicon adhesive layer having a high heat resistance of 260 ⁇ ⁇ or more it can be applied to a packaging process such as a reflow process without lowering the adhesive force.
  • FIG. 1 is a structural view of a non-substrate type silicone adhesive film according to an embodiment of the present invention.
  • FIG. 2 is a structural view of an inorganic silicone-type adhesive film according to another embodiment of the present invention.
  • FIG. 3 is an FE-SEM photograph and an EDS analysis graph using the inorganic silicone-type adhesive film of Example 1.
  • FIG. 5 is an FT-IR analysis graph using the inorganic silicone-type adhesive film of Example 1.
  • FIG. 7 is an FT-IR analysis graph of the inorganic material-type silicone adhesive film of the present invention having the release film subjected to the aging treatment.
  • FIG. 9 is a photograph showing the transfer characteristics of the inorganic type silicone adhesive film of the present invention having a release film subjected to aging (untreated).
  • thermogravimetric analysis (TGA) graph using a commercialized silicone adhesive film control.
  • the base material to which the silicone adhesive layer 120 is transferred may be attached to a printed circuit board (e.g., a PCB thin film) and may be subjected to a high temperature process such as reflow if necessary. Alternatively, after the reflow process, , And then re-peeling off. At this time, since the residue of the silicone adhesive layer is not present on the surface of the re-peeled printed circuit board substrate, contamination due to use of silicon is not caused. In addition, it is possible to suppress the occurrence of a step of thickness in a post-process such as molding. In addition, since the thin film substrate can be faithfully performed as a thickness reinforcing material during the packaging process, it is possible to prevent the warpage problem during the manufacturing process and easily peel off after the packaging process.
  • a printed circuit board e.g., a PCB thin film
  • the residual presence of the silicone adhesive layer can be measured by various analytical methods. For example, FT-IR, EDS, and GC / MS.
  • the silicon adhesive layer 120 is transferred onto one side of a substrate and attached to a printed circuit board (PCB thin film), reflowed at 220 to 260 ° C,
  • PCB thin film printed circuit board
  • the surface of the removed printed circuit board is analyzed by FT-IR spectrum, there is no Si-C peak observed in the region of 1265 ⁇ 15 cm -1 .
  • the content of the silicon (Si) element is not detected.
  • the first release film 110 and the second release film 130 may be used as a coating base for forming the silicone adhesive layer 120 to support the silicone adhesive layer It plays a protective role.
  • the components of the first release film 110 and the second release film 130 may be the same as or different from each other, and may be independently used conventional materials known in the art.
  • it may be a conventional fluorine release film.
  • the platinum catalyst is composed of a fluorine releasing agent mixed with a fluorine silicone release agent itself, a flame retardant, and a tackiness additive.
  • one of the first release film 110 and the second release film 130 may have been subjected to an aging treatment before the silicone adhesive layer 120 is formed.
  • the release film thus subjected to the aging treatment is used, the chemical bonding with the silicone adhesive layer formed thereon is significantly reduced, and the transfer characteristics can be further increased.
  • the aging treatment conditions are not particularly limited, and aging may be performed at 40 to 80 ° C for 72 to 200 hours, for example.
  • FIG. 2 is a cross-sectional structural view of a triple-type inorganic material type silicone adhesive film according to another embodiment of the present invention.
  • the constitution and physical properties of the first silicone adhesive layer 220 and the second silicone adhesive layer 230 can be modified according to the needs of the user, respectively.
  • the composition, adhesion, thickness, or both of the first silicone adhesive layer 220 and the second silicone adhesive layer 230 can be adjusted to be different from each other.
  • silicone non-adhesive layer 240 a component that maintains excellent heat resistance and is not physically miscible with the siliconeic adhesive layer 1-2 can be used.
  • a silicone polymer or silicone rubber commonly known in the art can be used.
  • the thickness of the silicon non-adhesive layer 240 is not particularly limited, and may be in the range of 1 to 50 mu m, preferably 3 to 30 mu m.
  • the triple inorganic silicone type adhesive film 200 may be formed of a first release film 210, a first silicon adhesive layer 220, a silicon non-adhesive layer 240, a second silicon adhesive layer 230, 2 release film 250 are laminated in this order.
  • the triple inorganic silicone type adhesive film 200 is obtained by laminating three layers of a silicone (non) adhesive layer on a substrate (for example, a Cu foil, a CCL) after peeling off one of the 1-2 first release films, The silicone adhesive layer 22, the silicon non-adhesive layer 240, and the second silicon adhesive layer 230 are transferred. At this time, the transfer characteristics after the removal of the release film are excellent.
  • the residue of the silicone adhesive layer does not exist on the surface of the re-peeled printed circuit board substrate, contamination due to use of silicon is not caused.
  • the thin film type substrate serves as a thickness reinforcing material during the packaging process, it is possible to prevent the warpage problem during the manufacturing process and can be easily removed after the packaging process.
  • the inorganic silicone adhesive film of the present invention can be produced by a conventional method known in the art, except that a silicone adhesive layer is used.
  • the inorganic silicone-type adhesive film can be largely manufactured in two ways according to the first embodiment (single type) and the second embodiment (triple type) described above.
  • the first release film used as a coating base of the silicone adhesive composition is preferably one subjected to aging treatment.
  • the silicone adhesive layer is formed by coating and curing the surface of one of the first release film and the second release film, for example, on the first release film.
  • the silicone adhesive composition may be applied to the first release film by a conventional coating method such as a dip coating method, an air knife coating method, a curtain coating method, a wire bar coating method, a gravure coating method, A comma coating method, a slot coat method, an extrusion coating method, a spin coating method, a slit scanning method, and an ink jet method.
  • the curing process can be appropriately carried out under ordinary conditions known in the art.
  • the curing may be carried out at 100 to 250 ° C for 1 to 10 minutes.
  • the silicone adhesive layer thus formed means a fully cured state with a degree of curing of 90-100%.
  • the lamination step may be carried out suitably within the conventional range known in the art, and may be carried out under a temperature condition of 20 to 150 ° C.
  • a temperature condition of 20 to 150 ° C.
  • it can be produced through a lamination process including a heating roll of the above-mentioned temperature condition.
  • the triple-type inorganic material type silicone adhesive film according to the second embodiment of the present invention can be produced by the following two methods, but is not particularly limited thereto.
  • One embodiment of making the triple inorganic silicone type adhesive film comprises the steps of (i) coating and curing a first silicone adhesive composition on a first side of a first release film to form a first silicone adhesive layer ; (ii) coating and curing a silicone non-sticking composition on the silicone sticking layer to form a silicone non-sticking layer; (iii) coating and curing a second silicone adhesive composition on the first side of the second release film to form a second silicone adhesive layer; And (iv) arranging the silicon non-adhesive layer of the first release film and the second silicone adhesive layer of the second release film so as to be in contact with each other, and then performing lamination.
  • a first silicone adhesive composition is coated and cured on the first side of the first release film to form a first silicone adhesive layer ; (ii) coating and curing a silicone non-sticking composition on the silicone sticking layer to form a silicone non-sticking layer; (iii) coating and curing the second silicone adhesive composition on the silicon non-adhesive layer to form a second silicone adhesive layer; And (iv) arranging the second silicone adhesive layer of the first release film and the first surface of the second release film so as to be in contact with each other, and then performing lamination.
  • the first release film used as a coating base of the silicone adhesive composition is preferably one subjected to aging treatment.
  • the lamination step may be carried out suitably within the ordinary range known in the art, and may be carried out under a temperature condition of 20 to 150 ° C.
  • a temperature condition of 20 to 150 ° C.
  • it can be produced through a lamination process including a heating roll of the above-mentioned temperature condition.
  • the inorganic silicone-type adhesive film produced as described above is applicable to various fields requiring high heat resistance and excellent transfer characteristics.
  • the present invention can be applied to a heat-resistant adhesive film for manufacturing a semiconductor packaging used for reinforcing a thin film-like substrate in semiconductor packaging and a semiconductor packaging manufacturing method using the silicon adhesive film.
  • Silicon adhesive layer Solution A (wt%) Liquor B (wt%) Remarks Silicone adhesive composition 1 80 20 Tank A: 7657 (Dow Corning), Tank B: 7654 (Dow Corning) Silicone adhesive composition 2 100 - Tank A: 7657 (Dow Corning) Silicone adhesive composition 3 100 - Tank A: 7652 (Dow Corning) Silicone adhesive composition 4 100 - Solution A: SG6500A (KCC) Silicone adhesive composition 5 80 20 Liquid A: 7652 (Dow Corning), liquid B: 7651 (Dow Corning) Silicone adhesive composition 6 60 40 Tank A: 4580 (Dow Corning), Tank B: 7646 (Dow Corning, less than 100,000 Mn of silicon polymer) Silicone non-stick composition 7 100 - Solution A: SC3300L (KCC)
  • Silicone (non) adhesive layer thickness ( ⁇ ⁇ )
  • the adhesive strength (gf / inch) of the silicone (non) One 2 3 4 5 6 7 5 30 200 50 250 10 20 0 10 40 300 80 340 20 30 0 20 75 650 120 700 40 50 0 30 90 730 160 800 55 60 0 40 120 820 200 900 75 90 0
  • the silicone adhesive composition 1 was coated on one surface of a first release film (Fluorine release film) having a thickness of 50 ⁇ and cured, and then cured using a second release film (Fluorine release film) 50 ⁇ thick and a laminator at 100 ⁇ To prepare an inorganic material transfer film of Example 1.
  • the inorganic pressure-sensitive transfer film (1) of each of Examples 2 to 5 was prepared by varying the composition of the silicone pressure-sensitive adhesive composition as shown in Table 3 below.
  • the silicone adhesive composition 1 was coated on one surface of a first release film (Fluorine release film) having a thickness of 50 ⁇ and cured, and the silicone non-adhesive composition 7 was coated thereon and then cured.
  • a first release film Fluorine release film
  • the inorganic pressure-sensitive transfer film (2) of each of Examples 7 to 9 was prepared by varying the composition of the silicone pressure-sensitive adhesive composition as shown in Table 4 below.
  • the second silicon adhesive layer adhered to the reinforcing plate is stronger than the first silicon adhesive layer adhered to the printed circuit board (PCB thin film).
  • composition of the first silicone adhesive layer Silicon non-adhesive layer
  • composition of the second silicone adhesive layer Example 6 Silicone adhesive composition 1 Silicone non-stick composition 7 Silicone adhesive composition 4 Example 7 Silicone adhesive composition 2 Example 8 Silicone adhesive composition 3 Example 9 Silicone adhesive composition 5
  • Example 1 After the inorganic silicone-type adhesive film of Example 1 was exposed at 260 ⁇ ⁇ for 5 minutes, outgassing occurring in the adhesive layer was confirmed.
  • the intensity of the Si-H functional group at 950-980 cm -1 was high in the control group in which the aging treatment was not performed (see FIG. 8), whereas in the aging treatment, the intensity was 950-980 cm -1 The strength of the unreacted Si-H functional group was remarkably lowered (see FIG. 7).
  • the bonding force between the fluorine releasing film and the silicone adhesive layer is lowered, and the transfer characteristics of the silicone adhesive layer can be improved.
  • Example 1 As the sample, the inorganic type silicone adhesive film of Example 1 was used and a silicone adhesive film commercialized as a control group was used.
  • the sample of Example 1 was expected to greatly improve the crosslinking density compared to the commercially available silicone adhesive film in the manufacturing process, and to have higher heat resistance stability than the conventional silicone adhesive film.
  • the above products were used to measure a 5 wt% loss temperature while raising the temperature at a rate of 10 DEG C / minute, and the weight of pyrolyzed at 400 DEG C was measured.
  • the silicone adhesive layer according to the present invention secures the adhesive strength even when the heat treatment process is performed about 8 times.
  • the change in adhesive force according to the heat treatment process was about 5 gf / inch (see FIG. 12).
  • the delamination characteristics were confirmed by using the inorganic pressure-sensitive silicone adhesive film according to the present invention.
  • the printed circuit board (PCB thin film) was attached and the reflow process was repeated about 8 times. Thereafter, (Scanning Acoustic Tomography).
  • the inorganic silicone-type adhesive film of the present invention had stable adhesion properties without occurrence of delamination even if other processes such as Reflow were applied (see Table 6 and Figs. 13 to 14).
  • the inorganic silicone type adhesive film of the present invention was applied as a stiffener of a printed circuit board (thin film type PCB), and the deflection characteristics during the PCB package manufacturing process were evaluated.
  • a silicon adhesive layer of an inorganic silicone adhesive film is transferred onto a Cu substrate and applied as a reinforcing material for strengthening the rigidity of the printed circuit board (PCB).
  • a silicon adhesive layer of the reinforcing material and one side of a strip printed circuit board (strip PCB, thickness: 85 ⁇ ⁇ ) were arranged to be in contact with each other, and then bonded. Subsequently, the bonded body was subjected to a reflow process (one or more times), a chip was placed on the other surface of the printed circuit board, heat treatment was performed through an EMC molding process, and the reinforcing material was detached. At this time, a strip printed circuit board on which the above-described reinforcing material was not used was used as a control group.
  • a silicon adhesive layer 120, 220, 230: a silicon adhesive layer, a first silicon adhesive layer, a second silicon adhesive layer

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Laminated Bodies (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

La présente invention concerne un film adhésif de silicone de type sans substrat qui ne nécessite pas de film de base pour la formation d'un film adhésif, présente une résistance élevée à la chaleur et d'excellentes propriétés adhésives et de transfert, et ne provoque pas de contamination par le silicone après son détachement.
PCT/KR2018/009496 2017-08-31 2018-08-20 Film adhésif de silicone de type sans substrat WO2019045336A1 (fr)

Applications Claiming Priority (2)

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KR10-2017-0111337 2017-08-31
KR1020170111337A KR102041675B1 (ko) 2017-08-31 2017-08-31 무기재형 실리콘 점착필름

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021116908A1 (fr) * 2019-12-09 2021-06-17 3M Innovative Properties Company Film adhésif
US20220025236A1 (en) * 2018-11-28 2022-01-27 Nissan Chemical Corporation Adhesive agent composition, layered product and production method for layered product, and method for reducing thickness of semiconductor forming substrate

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102282519B1 (ko) * 2019-09-27 2021-07-29 주식회사 모두테크 반도체 패키지 제조공정을 위한 접착 테이프 및 그 제조방법

Citations (5)

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JPH0734041A (ja) * 1993-07-22 1995-02-03 Sekisui Chem Co Ltd 粘着シート
JP3018715U (ja) * 1995-05-29 1995-11-28 株式会社コスモテック 基材無しシリコーン粘着シート
JPH08337763A (ja) * 1995-06-13 1996-12-24 Yakumo Tsuzuki 基材なし粘着剤転写シート及びテープ類
KR20100077476A (ko) * 2008-12-29 2010-07-08 도레이첨단소재 주식회사 필름 형 점착제 및 이를 이용하는 외장재
KR20140075685A (ko) * 2011-10-08 2014-06-19 미쓰비시 쥬시 가부시끼가이샤 기재가 없는 양면 점착 시트

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JPH0734041A (ja) * 1993-07-22 1995-02-03 Sekisui Chem Co Ltd 粘着シート
JP3018715U (ja) * 1995-05-29 1995-11-28 株式会社コスモテック 基材無しシリコーン粘着シート
JPH08337763A (ja) * 1995-06-13 1996-12-24 Yakumo Tsuzuki 基材なし粘着剤転写シート及びテープ類
KR20100077476A (ko) * 2008-12-29 2010-07-08 도레이첨단소재 주식회사 필름 형 점착제 및 이를 이용하는 외장재
KR20140075685A (ko) * 2011-10-08 2014-06-19 미쓰비시 쥬시 가부시끼가이샤 기재가 없는 양면 점착 시트

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20220025236A1 (en) * 2018-11-28 2022-01-27 Nissan Chemical Corporation Adhesive agent composition, layered product and production method for layered product, and method for reducing thickness of semiconductor forming substrate
US11776837B2 (en) * 2018-11-28 2023-10-03 Nissan Chemical Corporation Adhesive agent composition, layered product and production method for layered product, and method for reducing thickness of semiconductor forming substrate
WO2021116908A1 (fr) * 2019-12-09 2021-06-17 3M Innovative Properties Company Film adhésif
CN114846101A (zh) * 2019-12-09 2022-08-02 3M创新有限公司 粘合剂膜
US11667815B2 (en) 2019-12-09 2023-06-06 3M Innovative Properties Company Adhesive film
CN114846101B (zh) * 2019-12-09 2023-07-14 3M创新有限公司 粘合剂膜

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KR20190024386A (ko) 2019-03-08

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