TWI414554B - A film and a release film - Google Patents
A film and a release film Download PDFInfo
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- TWI414554B TWI414554B TW96123220A TW96123220A TWI414554B TW I414554 B TWI414554 B TW I414554B TW 96123220 A TW96123220 A TW 96123220A TW 96123220 A TW96123220 A TW 96123220A TW I414554 B TWI414554 B TW I414554B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/14—Monomers containing five or more carbon atoms
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
- H05K3/28—Applying non-metallic protective coatings
- H05K3/281—Applying non-metallic protective coatings by means of a preformed insulating foil
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Abstract
Description
本發明係關於含有由4-甲基-1-戊烯系共聚合體所形成之層的耐熱性與離型性均優越之薄膜,以及在藉由加壓成形製造薄膜或片材狀之層合物時所適合使用之離型薄膜。更詳言之,係關於在將保護層之覆蓋層(cover layer)藉由黏著劑予以加熱及加壓而黏著於可撓性印刷基板(以下亦稱為「FPC」)中之形成有電路(銅箔)之面上時,所適合使用之離型薄膜。The present invention relates to a film which is excellent in heat resistance and release property of a layer formed of a 4-methyl-1-pentene-based copolymer, and a laminate which is formed into a film or a sheet by press molding. A release film suitable for use in the case of a material. More specifically, a circuit is formed by adhering a cover layer of a protective layer to a flexible printed circuit board (hereinafter also referred to as "FPC") by heating and pressurizing with an adhesive (hereinafter also referred to as "FPC"). A release film suitable for use on the surface of copper foil).
在於金屬板等挾持複數之原料薄膜或片材,並藉由加壓成形製造層合物時,為了防止金屬板等與所得之層合物之間的黏著,一般係使用離型薄膜。又,於加壓成形時大多伴隨有加熱,故對於離型薄膜要求高耐熱性與優越之離型性。When a plurality of raw material films or sheets are held by a metal plate or the like, and a laminate is formed by press molding, in order to prevent adhesion between a metal plate or the like and the obtained laminate, a release film is generally used. Moreover, since heating is often accompanied by press molding, high heat resistance and excellent release property are required for the release film.
離型薄膜係使用作為可撓性印刷電路基板(以下亦稱為「FPC」)製造用離型薄膜、航空機零件所使用之ACM材料用離型薄膜、剛性印刷基板製造用離型薄膜、半導體密封材用離型薄膜、FRP成形用離型薄膜、橡膠片材硬化用離型薄膜、特殊黏著膠帶用離型薄膜等。The release film is a release film for manufacturing a flexible printed circuit board (hereinafter also referred to as "FPC"), a release film for ACM materials used for aircraft parts, a release film for producing a rigid printed circuit board, and a semiconductor seal. A release film for a material, a release film for FRP molding, a release film for curing a rubber sheet, and a release film for a special adhesive tape.
FPC中,通常將形成了電路之基板與覆蓋層藉由熱硬化型黏著劑進行黏著。在僅於基板單面上形成了電路的情況下,此覆蓋層僅黏著於形成了電路之基板單面上;在於基板兩面或多層互相設有電路的情況下,此覆蓋層則黏著於基板兩面上。而且,於該黏著時,通常將基板與塗佈了熱硬化型黏著劑之覆蓋層挾持於金屬板中,進行加熱及加壓。然後,為了防止此覆蓋層與金屬板之間的黏著,而將FPC製造用離型薄膜挾持於金屬板與覆蓋層之間而使用。In FPC, the substrate on which the circuit is formed and the cover layer are usually adhered by a thermosetting adhesive. In the case where only a circuit is formed on one side of the substrate, the cover layer adheres only to one side of the substrate on which the circuit is formed; in the case where two or more layers of the substrate are provided with circuits, the cover layer is adhered to both sides of the substrate. on. Further, at the time of the adhesion, the substrate and the coating layer coated with the thermosetting adhesive are usually held in a metal plate to be heated and pressurized. Then, in order to prevent adhesion between the cover layer and the metal plate, the FPC manufacturing release film is held between the metal plate and the cover layer.
習知以來,作為FPC製造用離型薄膜,係使用聚四氟乙烯、四氟乙烯-六氟丙烯共聚合體、及聚氟化乙烯等之氟系聚合體的薄膜;聚甲基戊烯之薄膜等。Conventionally, as a release film for FPC production, a film of a polytetrafluoroethylene, a tetrafluoroethylene-hexafluoropropylene copolymer, and a fluorine-based polymer such as polyvinyl fluoride; a film of polymethylpentene; Wait.
於形成了FPC之電路的面,形成有電路之印刷部、與未形成電路之非印刷部的高度相異。因此,以薄膜狀之覆蓋層進行被覆時,於非印刷部將形成空隙,被封入於該空隙之殘存空氣將使電路氧化,而有使電路壽命顯著降低的問題。On the surface on which the circuit of the FPC is formed, the printed portion on which the circuit is formed differs from the height of the non-printed portion in which the circuit is not formed. Therefore, when coating with a film-like cover layer, voids are formed in the non-printing portion, and the residual air enclosed in the gap oxidizes the circuit, which causes a problem that the life of the circuit is remarkably lowered.
於FPC中,為了與其他零件之電性連接,係形成電路之端子部分,該端子部分未被覆蓋層所被覆而呈現露出。而且,為了將端子部分以外部分進行被覆而塗佈於覆蓋層之黏著劑,將於藉由加熱及加壓進行黏著時發生熔融,常常有流出至該電路端子部分,形成黏著劑之覆蓋層,而成為電性連接不良之原因的問題。另外,相對於基板、覆蓋層及金屬板,由於習知之覆蓋層的熱膨脹率較大,故於加熱及加壓壓製以進行覆蓋層之黏著時,於離型薄膜之表面將發生皺紋。因此,該發生皺紋之部分,將有因離型薄膜之追隨不良而於電路與離型薄膜之間發生空隙的問題,再者,將有由於皺紋轉印至FPC,而無法得到具有能夠充分滿足之外觀的FPC的問題。In the FPC, in order to electrically connect with other parts, a terminal portion of the circuit is formed, and the terminal portion is exposed without being covered by the cover layer. Further, in order to coat the portion other than the terminal portion and apply the adhesive to the coating layer, it is melted when it is adhered by heating and pressurization, and often flows out to the terminal portion of the circuit to form a coating layer of the adhesive. However, it becomes a cause of poor electrical connection. Further, since the conventional cover layer has a large coefficient of thermal expansion with respect to the substrate, the cover layer, and the metal plate, wrinkles are formed on the surface of the release film when it is heated and pressed to adhere the cover layer. Therefore, in the wrinkle-forming portion, there is a problem that a gap occurs between the circuit and the release film due to the tracking failure of the release film, and further, the wrinkle is transferred to the FPC, and the wrinkle cannot be obtained. The appearance of the FPC problem.
於專利文獻1及專利文獻2中,揭示有以解決上述問題為目的之離型薄膜。然而,此等離型薄膜於用於將覆蓋層黏著於基板表面之電路上之進行加熱及加壓的步驟中,防止於薄膜產生皺紋的效果未必充分,而有無法得到具有可滿足之外觀之FPC的問題。Patent Document 1 and Patent Document 2 disclose a release film for the purpose of solving the above problems. However, in the step of heating and pressurizing the release film on the circuit for adhering the cover layer to the surface of the substrate, the effect of preventing wrinkles on the film is not necessarily sufficient, and there is no possibility of obtaining a satisfactory appearance. FPC problem.
專利文獻1:日本專利特開平2-175247號公報專利文獻2:日本專利特開2003-211602號公報Patent Document 1: Japanese Patent Laid-Open No. Hei 2-175247. Patent Document 2: Japanese Patent Laid-Open No. 2003-211602
本發明係提供一種適合於離型薄膜之薄膜,尤其是一種適合於製造FPC之加熱及加壓步驟中,可防止覆蓋層與金屬板之黏著、及黏著劑流出而黏著至其他零件,於非印刷部不形成空隙,於電路之端子部分等之露出的部分不因黏著劑之熔融流出而被污染,而且不產生皺紋之離型薄膜的薄膜。The invention provides a film suitable for a release film, in particular, a heating and pressing step suitable for manufacturing an FPC, which prevents the adhesion of the cover layer and the metal plate, and the adhesive flows out and adheres to other parts. The printed portion does not form a void, and the exposed portion of the terminal portion of the circuit is not contaminated by the melt flow of the adhesive, and the film of the release film which does not cause wrinkles is formed.
本發明者等人為了解決上述問題而潛心研究,結果發現,含有由特定之4-甲基-1-戊烯系共聚合體所形成之層,且具有特定厚度構成與熱收縮率的薄膜,能夠解決上述問題,遂完成本發明。The inventors of the present invention have intensively studied to solve the above problems, and as a result, have found that a film comprising a layer formed of a specific 4-methyl-1-pentene-based copolymer and having a specific thickness and a heat shrinkage ratio can To solve the above problems, the present invention has been completed.
亦即,本發明係提供下述者:[1]一種薄膜,其特徵為,具有至少一層由4-甲基-1-戊烯系共聚合體所形成之層(A),該4-甲基-1-戊烯系共聚合體係具有95.5質量%~99.5質量%之來自4-甲基-1-戊烯的構成單位及0.5質量%~4.5質量%之來自4-甲基-1-戊烯以外之碳原子數3~20之烯烴的構成單位;層(A)整體厚度為40 μm~90 μm;且薄膜整體之熱收縮率為1%~5%。That is, the present invention provides the following: [1] A film having at least one layer (A) formed of a 4-methyl-1-pentene copolymer, the 4-methyl group The 1-pentene-based copolymerization system has a constituent unit derived from 4-methyl-1-pentene of from 95.5 mass% to 99.5% by mass and from 0.5% by mass to 4.5% by mass of 4-methyl-1-pentene. The constituent unit of the olefin having 3 to 20 carbon atoms; the overall thickness of the layer (A) is 40 μm to 90 μm; and the thermal contraction rate of the entire film is 1% to 5%.
[2]如上述[1]之薄膜,係上述層(A)之單層薄膜。[2] The film according to the above [1], which is a single layer film of the above layer (A).
[3]如上述[1]之薄膜,其含有多層,係除了上述層(A)之外,進一步具有由根據ASTM D1525之域克軟化溫度為50℃~150℃之軟質聚烯烴所形成之層(B),且至少1層之上述層(A)為最外層。[3] The film according to the above [1], which comprises a plurality of layers, in addition to the above layer (A), further having a layer formed of a soft polyolefin having a domain softening temperature of 50 ° C to 150 ° C according to ASTM D1525. (B), and at least one of the above layers (A) is the outermost layer.
[4]如上述[1]之薄膜,其含有多層,係具有由根據ASTM D1525之域克軟化溫度為50℃~150℃之軟質聚烯烴所形成之層(B)、與至少2層之上述層(A);且上述層(A)之2層為薄膜兩側之最外層。[4] The film according to the above [1], comprising a plurality of layers having a layer (B) formed of a soft polyolefin having a domain softening temperature of 50 ° C to 150 ° C according to ASTM D1525, and at least two layers of the above Layer (A); and the two layers of the above layer (A) are the outermost layers on both sides of the film.
[5]如上述[1]~[3]中任一項之薄膜,其中,4-甲基-1-戊烯以外之碳原子數3~20之烯烴,係選自1-辛烯、1-癸烯、1-十四烯及1-十八烯之至少1種。[5] The film according to any one of the above [1] to [3] wherein the olefin having 3 to 20 carbon atoms other than 4-methyl-1-pentene is selected from the group consisting of 1-octene, 1 At least one of terpene, 1-tetradecene and 1-octadecene.
[6]如上述[3]或[4]之薄膜,其中,軟質聚烯烴係將選自乙烯、丙烯、丁烯、戊烯、己烯及甲基戊烯之1種以上的烯烴進行(共)聚合而成之聚合體。[6] The film of the above [3] or [4] wherein the soft polyolefin is one or more olefins selected from the group consisting of ethylene, propylene, butene, pentene, hexene, and methylpentene (total a polymer obtained by polymerization.
[7]如上述[3]或[4]之薄膜,其中,軟質聚烯烴係選自乙烯與丙烯酸酯之共聚合體、乙烯與甲基丙烯酸酯之共聚合體、乙烯與丙烯酸之共聚合體、乙烯與甲基丙烯酸之共聚合體及其等之部分離子交聯物的共聚合體。[7] The film according to the above [3] or [4] wherein the soft polyolefin is selected from the group consisting of a copolymer of ethylene and acrylate, a copolymer of ethylene and methacrylate, a copolymer of ethylene and acrylic acid, and ethylene. a copolymer of a copolymer of methacrylic acid and a portion of its ionic crosslinks.
[8]如上述[3]~[7]中任一項之薄膜,其中,上述層(A)整體厚度為薄膜整體厚度之25%~80%。[8] The film according to any one of [3] to [7] wherein the thickness of the layer (A) is 25% to 80% of the entire thickness of the film.
[9]如上述[2]~[8]中任一項之薄膜,其中,由上述層(A)所形成之薄膜表面的至少一者係進行壓紋處理。[9] The film according to any one of [2] to [8] wherein at least one of the surfaces of the film formed by the layer (A) is embossed.
[10]如上述[1]~[9]中任一項之薄膜,係藉由擠出成形法或共擠出成形法所獲得。[10] The film according to any one of the above [1] to [9], which is obtained by an extrusion molding method or a coextrusion molding method.
[11]一種離型薄膜,係由上述[1]~[10]中任一項之薄膜所獲得。[11] A release film obtained by the film according to any one of the above [1] to [10].
本發明之含有由特定之4-甲基-1-戊烯系共聚合體所形成之層、且具有特定厚度構成及熱收縮率之薄膜,由於耐熱性及離型性優越,故適合使用作為離型薄膜。特別是藉由於FPC製造時使用作為離型薄膜,而可防止將基板與覆蓋層進行加熱及加壓而予以黏著時之金屬板與覆蓋層之黏著、及黏著劑流出而黏著至其他零件,同時,於成形時在非印刷部不形成空隙,電路之端子部分等之露出部分不因黏著劑之熔融流出而被污染。The film containing a layer formed of a specific 4-methyl-1-pentene copolymer, having a specific thickness and a heat shrinkage ratio, is excellent in heat resistance and release property, and is therefore suitable for use as a separation. Type film. In particular, since the FPC is used as a release film, it is possible to prevent the adhesion between the metal plate and the cover layer when the substrate and the cover layer are heated and pressurized, and the adhesive flows out and adheres to other parts. At the time of molding, no void is formed in the non-printing portion, and the exposed portion of the terminal portion of the circuit is not contaminated by the melted and discharged of the adhesive.
另外,由於藉加熱及加壓使覆蓋層黏著時,於離型薄膜不產生皺紋,故不因追隨不良而生成空隙,可有效率地使經改善了因皺紋轉印所導致之外觀不良的FPC成形,而於工業上極有價值。Further, when the coating layer is adhered by heat and pressure, no wrinkles are formed in the release film, so that voids are not formed due to the tracking failure, and the FPC having improved appearance defects due to wrinkle transfer can be efficiently obtained. Formed, and extremely valuable in industry.
再者,含有特定軟質聚烯烴之層,將賦予用於使離型薄膜追隨形成了電路之基板面之凹凸的良好緩衝性,且加熱及加壓時之溢出較少,不致發生因其附著於形成了電路之基板面和使用於加熱及加壓之金屬板上所造成之FPC製品產率降低和作業性降低等問題。Further, the layer containing the specific soft polyolefin imparts a good cushioning property for causing the release film to follow the unevenness of the surface of the substrate on which the circuit is formed, and the overflow during heating and pressurization is less, so that it does not adhere to it. The substrate surface of the circuit and the metal plate used for heating and pressurization have problems such as a decrease in the yield of the FPC product and a decrease in workability.
本發明之薄膜係具有至少1層由4-甲基-1-戊烯系共聚合體所形成之層(A),層(A)整體厚度為40 μm~90 μm,且薄膜整體之熱收縮率為1%~5%。The film of the present invention has at least one layer (A) composed of a 4-methyl-1-pentene copolymer, and the layer (A) has an overall thickness of 40 μm to 90 μm, and the overall heat shrinkage rate of the film. It is 1% to 5%.
本發明所使用之4-甲基-1-戊烯系共聚合體,係指具有95.5質量%~99.5質量%之來自4-甲基-1-戊烯的構成單位及0.5質量%~4.5質量%之來自4-甲基-1-戊烯以外之碳原子數3~20之烯烴的構成單位的結晶性共聚合體。較佳係來自4-甲基-1-戊烯的構成單位為96質量%~99質量%及來自4-甲基-1-戊烯以外之碳原子數3~20之烯烴的構成單位為1質量%~4質量%;更佳係來自4-甲基-1-戊烯的構成單位為97質量%~98質量%及來自4-甲基-1-戊烯以外之碳原子數3~20之烯烴的構成單位為2質量%~3質量%。The 4-methyl-1-pentene copolymer used in the present invention means a constituent unit derived from 4-methyl-1-pentene and having a mass ratio of from 0.55% by mass to 4.55% by mass, and from 0.5% by mass to 4.5% by mass. A crystalline copolymer of a constituent unit derived from an olefin having 3 to 20 carbon atoms other than 4-methyl-1-pentene. Preferably, the constituent unit derived from 4-methyl-1-pentene is 96% by mass to 99% by mass, and the constituent unit of the olefin having 3 to 20 carbon atoms other than 4-methyl-1-pentene is 1 % by mass to 4% by mass; more preferably, the constituent unit derived from 4-methyl-1-pentene is 97% by mass to 98% by mass, and the number of carbon atoms other than 4-methyl-1-pentene is 3 to 20%. The constituent unit of the olefin is 2% by mass to 3% by mass.
於將本發明之薄膜作為離型薄膜使用於FPC之製造時,若來自4-甲基-1-戊烯以外之碳原子數3~20之烯烴的構成單位為上述上限值以下,則可防止離型薄膜之皺紋發生,又,若為上述下限值以上,則離型薄膜之緩衝性良好,故離型薄膜可追隨電路面印刷部與非印刷部所造成之凹凸而變形。When the film of the present invention is used as a release film in the production of FPC, if the constituent unit of the olefin having 3 to 20 carbon atoms other than 4-methyl-1-pentene is at most the above upper limit value, When the wrinkle of the release film is prevented, the cushioning property of the release film is good, and the release film can be deformed following the irregularities caused by the printed portion and the non-printed portion of the circuit surface.
本發明所使用之4-甲基-1-戊烯以外之碳原子數3~20之烯烴,可舉例如選自丙烯、1-丁烯、1-己烯、1-辛烯、1-癸烯、1-十四烯及1-十八烯之至少1種烯烴。此等之中,由與4-甲基-1-戊烯之共聚合性良好、可得到良好韌性方面而言,較佳為1-癸烯、1-十四烯及1-十八烯。The olefin having 3 to 20 carbon atoms other than 4-methyl-1-pentene used in the present invention may, for example, be selected from the group consisting of propylene, 1-butene, 1-hexene, 1-octene, and 1-oxime. At least one olefin of an alkene, 1-tetradecene and 1-octadecene. Among these, from the viewpoint of good copolymerizability with 4-methyl-1-pentene and good toughness, 1-decene, 1-tetradecene and 1-octadecene are preferred.
本發明所使用之4-甲基-1-戊烯系共聚合體中,根據ASTM D1238(溫度260℃,負重5.0kg)之熔融流動速度為0.5g/10分~200g/10分,較佳為5g/10分~100g/10分,更佳為10g/10分~50g/l0分。若該熔融流動速度為200g/10分以下,則可得到充分之機械強度,另一方面,若該熔融流動速度為0.5g/10分以上,則可得到良好之成形性,故較佳。In the 4-methyl-1-pentene copolymer used in the present invention, the melt flow rate according to ASTM D1238 (temperature: 260 ° C, weight: 5.0 kg) is from 0.5 g/10 min to 200 g/10 min, preferably 5g/10 points ~ 100g/10 points, more preferably 10g/10 points ~ 50g / l0 points. When the melt flow rate is 200 g/10 minutes or less, sufficient mechanical strength can be obtained. On the other hand, when the melt flow rate is 0.5 g/10 minutes or more, good moldability can be obtained, which is preferable.
本發明所使用之4-甲基-1-戊烯系共聚合體之以DSC所測定之熔點(Tm),較佳為220℃~240℃之範圍,更佳為225℃~240℃之範圍。又,根據ASTM D1525進行測定所得之域克軟化溫度,較佳為160℃~200℃之範圍,更佳為170℃~200℃之範圍。The melting point (Tm) of the 4-methyl-1-pentene copolymer used in the present invention measured by DSC is preferably in the range of from 220 ° C to 240 ° C, more preferably in the range of from 225 ° C to 240 ° C. Further, the domain softening temperature measured according to ASTM D1525 is preferably in the range of 160 ° C to 200 ° C, more preferably in the range of 170 ° C to 200 ° C.
本發明所使用之4-甲基-1-戊烯系共聚合體,可依習知方法進行製造,對於聚合觸媒和聚合方法亦無特別限制。The 4-methyl-1-pentene copolymer used in the present invention can be produced by a known method, and the polymerization catalyst and the polymerization method are also not particularly limited.
作為觸媒,可舉例如齊格勒型觸媒(根據載持或非載持含鹵素之鈦化合物與鋁化合物之組合者)、菲利浦型觸媒(根據載持氧化鉻者)、卡敏斯基型觸媒(根據載持或非載持二茂金屬型化合物與有機鋁化合物、尤其是與鋁氧烷(alumoxane)之組合者)。Examples of the catalyst include a Ziegler type catalyst (according to a combination of a halogen-containing titanium compound and an aluminum compound), a Phillips type catalyst (based on a chromium oxide-supporting person), and a card. Minsky type catalyst (according to the combination of a supported or unsupported metallocene type compound with an organoaluminum compound, especially with alumoxane).
作為聚合方法,可舉例如於上述觸媒存在下之漿料聚合法、氣相流動床聚合法、溶液聚合法,或於壓力20MPa以上、聚合溫度100℃以上之高壓整體聚合法。The polymerization method may, for example, be a slurry polymerization method, a vapor phase fluidized bed polymerization method, a solution polymerization method in the presence of the above catalyst, or a high pressure bulk polymerization method having a pressure of 20 MPa or more and a polymerization temperature of 100 ° C or higher.
更具體而言,可如日本專利特開昭59-206418號公報、特開昭61-113604號公報、及特開2003-105022號公報所記載般,於觸媒存在下,使4-甲基-1-戊烯與其以外之碳原子數3~20之烯烴進行共聚合,藉由得到本發明所使用之4-甲基-1-戊烯系共聚合體。More specifically, in the presence of a catalyst, 4-methyl group can be used as described in JP-A-59-206418, JP-A-61-113604, and JP-A-2003-105022. 1-pentene is copolymerized with an olefin having 3 to 20 carbon atoms other than the above, and a 4-methyl-1-pentene copolymer which is used in the present invention is obtained.
本發明之薄膜,亦可為上述層(A)之單層薄膜。The film of the present invention may also be a single layer film of the above layer (A).
另外,本發明之薄膜,亦可為多層薄膜,係除了上述層(A)之外,進一步具有由根據ASTM D1525之域克軟化溫度為50℃~150℃之軟質聚烯烴所形成之層(B),且至少1層之上述層(A)為最外層。Further, the film of the present invention may be a multilayer film which, in addition to the above layer (A), further has a layer formed of a soft polyolefin having a domain softening temperature of 50 ° C to 150 ° C according to ASTM D1525 (B). And at least one of the above layers (A) is the outermost layer.
軟質聚烯烴係指,於將本發明之薄膜使用作為離型薄膜時之加熱及加壓時,對離型薄膜賦予變得柔軟之特性者。The soft polyolefin refers to a property of imparting flexibility to a release film when the film of the present invention is used as a release film for heating and pressurization.
軟質聚烯烴之根據ASTM D1525之域克軟化溫度為50℃~150℃,較佳為60℃~150℃,更佳為70℃~150℃;根據ASTM D1238(溫度260℃,負重5.0kg)之熔融流動速度之值為0.5g/10分~200g/10分,較佳為5g/10分~100g/10分;以DSC所測定之熔點(Tm)為80℃~240℃、更佳100℃~240℃。The soft polyolefin has a softening temperature according to ASTM D1525 of 50 ° C to 150 ° C, preferably 60 ° C to 150 ° C, more preferably 70 ° C to 150 ° C; according to ASTM D1238 (temperature 260 ° C, weight 5.0 kg) The melt flow rate is from 0.5 g/10 min to 200 g/10 min, preferably from 5 g/10 min to 100 g/10 min; the melting point (Tm) measured by DSC is from 80 ° C to 240 ° C, more preferably 100 ° C. ~240 °C.
於使用本發明之多層薄膜作為FPC製造用之離型薄膜時,上述軟質聚烯烴係用於對離型薄膜賦予所謂的緩衝性。When the multilayer film of the present invention is used as a release film for FPC production, the soft polyolefin is used to impart so-called cushioning properties to the release film.
從而,於製造FPC時,上述軟質聚烯烴將使於表面形成有電路之基板面的凹凸追隨性提升,並防止黏著劑自覆蓋層端面流出至電路上。Therefore, in the production of the FPC, the soft polyolefin improves the unevenness of the surface of the substrate on which the circuit is formed on the surface, and prevents the adhesive from flowing out from the end surface of the cover layer to the circuit.
滿足上述條件之軟質聚烯烴,具體可例示如:選自乙烯、丙烯、丁烯、戊烯、己烯、及甲基戊烯之1種以上之烯烴的單聚物或共聚合體;乙烯與丙烯酸酯之共聚合體、乙烯與甲基丙烯酸酯之共聚合體、乙烯與丙烯酸之共聚合體、乙烯與甲基丙烯酸之共聚合體、及其等之部分離子交聯物、複數之乙烯與丙烯酸或丙烯酸酯共聚合體的摻合物等;其他亦可舉例如日本專利特開平2-175247號公報所揭示之軟質聚烯烴等。此等可單獨使用,亦可並用2種以上。Specific examples of the soft polyolefin satisfying the above conditions include a monomer or a copolymer of one or more olefins selected from the group consisting of ethylene, propylene, butene, pentene, hexene, and methylpentene; ethylene and acrylic acid; a copolymer of an ester, a copolymer of ethylene and methacrylate, a copolymer of ethylene and acrylic acid, a copolymer of ethylene and methacrylic acid, and a partial ionomer thereof, and a copolymer of a plurality of ethylene and acrylic acid or acrylate A blend of a compound or the like, which is disclosed in Japanese Laid-Open Patent Publication No. 2-175247, and the like. These may be used alone or in combination of two or more.
此等之中,由具有適度柔軟性與緩衝性之觀點而言,例如丙烯.丁烯-1共聚合體、乙烯.丙烯酸乙酯共聚合體為特別適合使用。又,此等軟質聚烯烴可依1層進行使用,亦可作為2層以上之多層而使用。Among these, from the viewpoint of moderate flexibility and cushioning, such as propylene. Butene-1 copolymer, ethylene. The ethyl acrylate copolymer is particularly suitable for use. Further, these soft polyolefins may be used in one layer or in a plurality of layers of two or more layers.
此等軟質聚烯烴亦可由市場輕易取得,可舉例如三井化學(股)製之商品名:TAFMER XR、三井DU PONT POLYCHEMICAL(股)製之商品名:EVEFLEX等。These soft polyolefins are also easily available from the market, and are commercially available under the trade names of TAFMER XR and Mitsui DU PONT POLYCHEMICAL (trade name): EVEFLEX.
本發明之薄膜係具有至少一層由4-甲基-1-戊烯系共聚合體所形成之層(A),該4-甲基-1-戊烯系共聚合體係具有95.5質量%~99.5質量%之來自4-甲基-1-戊烯的構成單位及0.5質量%~4.5質量%之來自4-甲基-1-戊烯以外之碳原子數3~20之烯烴的構成單位;層(A)整體厚度為40 μm~90 μm;且薄膜整體之熱收縮率為1%~5%。The film of the present invention has at least one layer (A) formed of a 4-methyl-1-pentene copolymer having a mass ratio of 95.5 mass% to 99.5. % of a constituent unit derived from 4-methyl-1-pentene and 0.5% by mass to 4.5% by mass of a constituent unit of an olefin having 3 to 20 carbon atoms other than 4-methyl-1-pentene; A) The overall thickness is 40 μm~90 μm; and the overall thermal shrinkage of the film is 1% to 5%.
本發明之薄膜之特徵在於具有上述層(A)。從而,本發明之薄膜為僅由上述層(A)所形成之單層薄膜、至少具有1層上述層(A)之多層薄膜。The film of the present invention is characterized by having the above layer (A). Therefore, the film of the present invention is a single layer film formed only of the above layer (A), and a multilayer film having at least one layer (A).
於使用上述多層薄膜作為離型薄膜時,由於上述層(A)之離型性優越,故較佳至少1層之上述層(A)為最外層。When the above-mentioned multilayer film is used as the release film, since the release property of the layer (A) is excellent, it is preferable that at least one of the layers (A) is the outermost layer.
在不損及本發明目的之下,上述層(A)亦可含有例如聚四氟乙烯等之氟系樹脂、聚苯硫、聚酯等作為4-甲基-1-戊烯系共聚合體以外之聚合體,但上述層(A)較佳係含有90質量%~100質量%之4-甲基-1-戊烯系共聚合體、更佳95質量%~100質量%、特佳100質量%。The layer (A) may contain, for example, a fluorine-based resin such as polytetrafluoroethylene, polyphenylene sulfide, polyester or the like as a 4-methyl-1-pentene-based copolymer, without impairing the object of the present invention. The polymer (B) preferably contains 90% by mass to 100% by mass of a 4-methyl-1-pentene copolymer, more preferably 95% by mass to 100% by mass, particularly preferably 100% by mass. .
於使用本發明之多層薄膜作為FPC製造用之離型薄膜時,尤其是在表面形成了電路之基板面的起伏差較大、需要更良好之緩衝性的情況下,較佳係進一步具有由軟質聚烯烴所形成之層(B)的多層薄膜,而上述層(B)亦可為2層以上之多層。When the multilayer film of the present invention is used as a release film for FPC production, in particular, when the surface of the substrate on which the circuit is formed has a large undulation difference and a better cushioning property is required, it is preferable to further have a soft film. The multilayer film of the layer (B) formed of the polyolefin, and the layer (B) may be a multilayer of two or more layers.
在不損及本發明目的之範圍內,上述層(B)亦可含有例如聚甲基丙烯、聚對苯二甲酸乙二酯(PET)、聚對苯二甲酸丁二酯(PBT)等之聚酯,聚醯胺-6、聚醯胺-6,6、聚醯胺11、聚醯胺12等之聚醯胺,但層(B)較佳係含有90質量%~100質量%之軟質聚烯烴、更佳95質量%~100質量%、特佳100質量%。The layer (B) may contain, for example, polymethacrylic acid, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), etc., within the range not impairing the object of the present invention. Polyamide, polyamido-6, polyamide-6,6, polyamide 11, polyamine 12, etc., but layer (B) preferably contains 90% to 100% by mass of soft The polyolefin is more preferably 95% by mass to 100% by mass, particularly preferably 100% by mass.
作為本發明之多層薄膜,在不損及本發明目的之下,亦可具有層(A)及層(B)以外之層(C)。The multilayer film of the present invention may have a layer (C) other than the layer (A) and the layer (B) without impairing the object of the present invention.
作為可使用於層(C)之樹脂,較佳為耐熱性高之熱可塑性樹脂。可舉例如:聚丙烯等之聚烯烴;聚對苯二甲酸乙二酯(PET)、聚對苯二甲酸丁二酯(PBT)等之聚酯;以及聚醯胺-6、聚醯胺-6,6、聚醯胺11、聚醯胺12等之聚醯胺。此等樹脂可由市場輕易取得。可舉例如:PRIME POLYMER公司製之PRIMEPOLYPRO、三菱工程塑膠(股)製之商品名NOVAPET、東麗(股)製之商品名AMILANE等。又,此等樹脂可單獨使用,亦可組合2種以上使用。As the resin which can be used for the layer (C), a thermoplastic resin having high heat resistance is preferable. For example, polyolefins such as polypropylene; polyesters such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT); and polyamine-6, polyamine- 6,6, polyamine, polyamine, and the like. These resins are readily available from the market. For example, PRIMEPOLYPRO manufactured by PRIME POLYMER Co., Ltd., NOVAPET manufactured by Mitsubishi Engineering Plastics Co., Ltd., and AMILANE manufactured by Toray Industries Co., Ltd., etc., may be mentioned. Further, these resins may be used singly or in combination of two or more.
作為本發明之多層薄膜,具體可舉例如:層(A)/層(B)及層(A)/層(C)之2層構造的層合體;層(A)/層(B)/層(C)、層(A)/層(C)/層(A)及層(A)/層(B)/層(A)之3層構造。Specific examples of the multilayer film of the present invention include a layered structure of a layer (A)/layer (B) and a layer (A)/layer (C); a layer (A)/layer (B)/layer (C), Layer (A) / Layer (C) / Layer (A) and Layer (A) / Layer (B) / Layer (A) three-layer structure.
為了於使用作為離型薄膜時省略辨別表背而使用之步驟,較佳係具有至少2層以上之上述層(A),且上述層(A)之2層為薄膜兩側之最外層,為了得到良好緩衝性,以含有上述層(B)為佳。特佳為層(A)/層(B)/層(A)之3層薄膜。In order to use the step of omitting the identification of the front and back when using the release film, it is preferred to have at least two or more layers (A), and the two layers of the layer (A) are the outermost layers on both sides of the film, in order to A good cushioning property is obtained, and it is preferable to contain the above layer (B). A three-layer film of layer (A) / layer (B) / layer (A) is particularly preferred.
本發明之多層薄膜中,上述層(A)係作用為離型層,上述層(B)係作用為緩衝層。而且,上述層(B)由於具有適度之緩衝性,故於FPC製造之製程步驟中,將確實進行覆蓋層對非印刷部的押入,而可達成完全無空隙、一體化之FPC的成形。In the multilayer film of the present invention, the layer (A) functions as a release layer, and the layer (B) functions as a buffer layer. Further, since the layer (B) has a moderate cushioning property, in the process of manufacturing the FPC, the coating of the cover layer to the non-printing portion is surely performed, and the formation of the FPC which is completely void-free and integrated can be achieved.
本發明之薄膜中,在上述層(A)為1層時,上述層(A)之厚度較佳為40 μm~90 μm,更佳為40 μm~80 μm。In the film of the present invention, when the layer (A) is one layer, the thickness of the layer (A) is preferably from 40 μm to 90 μm, more preferably from 40 μm to 80 μm.
另外,本發明之多層薄膜中,在上述層(A)為2層以上時,上述層(A)整體厚度,較佳為40 μm~90 μm,更佳為40 μm~80 μm。Further, in the multilayer film of the present invention, when the layer (A) is two or more layers, the thickness of the layer (A) as a whole is preferably 40 μm to 90 μm, more preferably 40 μm to 80 μm.
在將上述層(A)設為兩側之最外層時,若此等層(A)之厚度相同,則多層薄膜不致發生曲翹、亦即無彎曲成弓形的情況,故較佳。When the layer (A) is the outermost layer on both sides, if the thickness of the layers (A) is the same, the multilayer film is preferably not warped, that is, it is not bent into a bow shape, which is preferable.
若上述層(A)之厚度為上述下限值以上,則可防止皺紋發生,若為上述上限值以下,則可維持緩衝性,故較佳。When the thickness of the layer (A) is at least the above lower limit value, wrinkles can be prevented from occurring, and if it is at most the above upper limit value, cushioning properties can be maintained, which is preferable.
上述層(B)之厚度為30~100 μm,較佳40~90 μm。The layer (B) has a thickness of 30 to 100 μm, preferably 40 to 90 μm.
若上述層(B)之厚度為上述下限值以上,則可維持緩衝性,故較佳,若為上述上限值以下,則於進行加熱及加壓處理時之層(B)的溢出量可減低,故較佳。When the thickness of the layer (B) is at least the above lower limit value, the cushioning property can be maintained. Therefore, when the thickness is equal to or less than the above upper limit value, the amount of the layer (B) at the time of heating and pressure treatment is excessive. It can be reduced, so it is better.
本發明之多層薄膜中,相對於薄膜整體厚度之上述層(A)整體厚度的比例為25%~80%,較佳30%~60%,更佳30%~50%。In the multilayer film of the present invention, the ratio of the overall thickness of the layer (A) to the entire thickness of the film is 25% to 80%, preferably 30% to 60%, more preferably 30% to 50%.
在為含有上述層(B)之多層薄膜的情況下,若相對於薄膜整體厚度之上述層(A)整體厚度的比例為上述下限值以上,則可防止皺紋發生,若為上述上限值以下,則可維持緩衝性,故較佳。In the case of the multilayer film containing the layer (B), if the ratio of the thickness of the entire layer (A) to the entire thickness of the film is at least the above lower limit, wrinkles can be prevented, and the upper limit is Hereinafter, the cushioning property can be maintained, which is preferable.
本發明之薄膜整體之熱收縮率為1%~5%,較佳1%~3%,更佳1.5%~2.5%。若熱收縮率為1%以上,尤其是於使用本發明之薄膜作為在將覆蓋層黏著於FPC時之離型薄膜的情況下,於薄膜表面將不致發生皺紋,故較佳。另外,若熱收縮率在5%以下,則在黏著覆蓋層時,電路面與離型薄膜之間不發生空隙,故較佳。The heat shrinkage of the film of the present invention as a whole is 1% to 5%, preferably 1% to 3%, more preferably 1.5% to 2.5%. If the heat shrinkage rate is 1% or more, in particular, when the film of the present invention is used as a release film when the cover layer is adhered to the FPC, wrinkles are not caused on the surface of the film, which is preferable. Further, when the heat shrinkage ratio is 5% or less, it is preferable that no gap is formed between the circuit surface and the release film when the cover layer is adhered.
本發明之薄膜之熱收縮率,係指將本發明薄膜進行加熱使其收縮時,相對於加熱前之薄膜長度,薄膜所收縮的比例。亦即,作成於加熱前在室溫下所測定之薄膜長度L1,與在溫度170℃氣體環境下放置30分鐘後取出、並於室溫進行冷卻30分鐘後所測定之相對於上述L1之部分的長度L2,再將依下式(1)所求得之值作為熱收縮率。The heat shrinkage ratio of the film of the present invention means the ratio at which the film shrinks with respect to the length of the film before heating when the film of the present invention is heated to shrink. That is, the film length L1 measured at room temperature before heating is taken out after being left in a gas atmosphere at 170 ° C for 30 minutes, and after cooling at room temperature for 30 minutes, the portion relative to the above L1 is determined. The length L2 is determined by the value obtained by the following formula (1) as the heat shrinkage rate.
熱收縮率(%)=(L1-L2)/L1×100 (1)(式中,L1:加熱前之薄膜長度,cm;L2:加熱後之相當於L1之部分的長度,cm)Heat shrinkage ratio (%) = (L1 - L2) / L1 × 100 (1) (wherein L1: film length before heating, cm; L2: length of the portion corresponding to L1 after heating, cm)
本發明之薄膜的熱收縮率,係薄膜延伸方向上的值。亦即,測定熱收縮率時之薄膜長度,係平行於薄膜延伸方向之方向上的長度。The heat shrinkage rate of the film of the present invention is a value in the direction in which the film is stretched. That is, the film length at the time of measuring the heat shrinkage rate is a length parallel to the direction in which the film extends.
例如,在將本發明之薄膜進行擠出成形或共擠出成形後,立即直接連續地使用延伸輥進行延伸時之MD方向,亦即,擠出方向之長度。另外,本發明之薄膜亦可進行雙軸延伸,雙軸延伸可為逐次或同時雙軸延伸。經雙軸延伸時之熱收縮率,為各個延伸方向之值。又,擠出方向係平行於薄膜表面所發生之模頭線的方向,可自該模頭線輕易地判定。For example, immediately after the film of the present invention is subjected to extrusion molding or co-extrusion molding, the MD direction in the stretching direction, that is, the length in the extrusion direction, is directly and continuously used. Alternatively, the film of the present invention may be biaxially stretched, and the biaxial extension may be a sequential or simultaneous biaxial extension. The heat shrinkage rate when biaxially stretched is the value of each extending direction. Further, the direction of extrusion is parallel to the direction of the die line which occurs on the surface of the film, and can be easily determined from the die line.
另外,本發明之薄膜,較佳係對由上述層(A)所形成之薄膜表面的至少一者進行壓紋處理。該壓紋處理後之薄膜表面層之根據JIS B0601的面粗度Ry為0.01~20 μm,較佳0.1~10 μm,更佳0.1~5 μm,特佳0.1~2 μm。該薄膜表面層之面粗度若為上述範圍內,則可得到良好之離型性。Further, the film of the present invention is preferably embossed by at least one of the surfaces of the film formed by the layer (A). The surface roughness of the surface layer of the embossed film according to JIS B0601 is 0.01 to 20 μm, preferably 0.1 to 10 μm, more preferably 0.1 to 5 μm, and particularly preferably 0.1 to 2 μm. When the surface roughness of the surface layer of the film is within the above range, good release property can be obtained.
另外,本發明之薄膜中,溫度150℃下之彈性模數(E’)較佳為1.5×107 ~8.5×107 MPa之範圍。於此,溫度150℃下之彈性模數(E’)係表示延伸方向之溫度150℃下之動態貯藏彈性模數。具體而言,可自本發明之薄膜切出於延伸方向之長度為0.13mm、於垂直延伸方向之方向為5mm之樣本,使用動態貯藏彈性模數測定裝置、例如TA公司製(RSA-II),依測定溫度-150~200℃、升溫速度3℃/分、測定模式:拉伸、測定頻率數1Hz之條件進行測定,則可求得溫度150℃下之彈性模數(E’)。Further, in the film of the present invention, the modulus of elasticity (E') at a temperature of 150 ° C is preferably in the range of 1.5 × 10 7 to 8.5 × 10 7 MPa. Here, the elastic modulus (E') at a temperature of 150 ° C indicates the dynamic storage elastic modulus at a temperature of 150 ° C in the extending direction. Specifically, a sample having a length of 0.13 mm in the extending direction and a direction of 5 mm in the direction of the vertical extending direction can be used for the film of the present invention, and a dynamic storage elastic modulus measuring device, for example, a TA company (RSA-II) is used. According to the measurement temperature -150 to 200 ° C, the temperature increase rate of 3 ° C / min, and the measurement mode: tensile and measurement frequency 1 Hz, the elastic modulus (E') at a temperature of 150 ° C can be obtained.
於使用本發明之薄膜作為FPC製造用之離型薄膜時,用於將覆蓋層黏著於FPC而進行加熱時之離型薄膜的溫度為接近150℃。從而,若溫度150℃下之彈性模數為上述下限值以上,則可防止離型薄膜發生皺紋,又,若為上述上限值以下,則離型薄膜可得到良好之緩衝性。When the film of the present invention is used as a release film for FPC production, the temperature of the release film used for heating the cover layer to the FPC is close to 150 °C. Therefore, when the modulus of elasticity at a temperature of 150 ° C is at least the above lower limit value, wrinkles can be prevented from occurring in the release film, and if it is at most the above upper limit value, the release film can have good cushioning properties.
本發明之薄膜係具有至少一層由4-甲基-1-戊烯系共聚合體所形成之層(A),該4-甲基-1-戊烯系共聚合體係具有95.5質量%~99.5質量%之來自4-甲基-1-戊烯的構成單位及0.5質量%~4.5質量%之來自4-甲基-1-戊烯以外之碳原子數3~20之烯烴的構成單位;層(A)整體厚度為40 μm~90 μm;且薄膜整體之熱收縮率為1%~5%。The film of the present invention has at least one layer (A) formed of a 4-methyl-1-pentene copolymer having a mass ratio of 95.5 mass% to 99.5. % of a constituent unit derived from 4-methyl-1-pentene and 0.5% by mass to 4.5% by mass of a constituent unit of an olefin having 3 to 20 carbon atoms other than 4-methyl-1-pentene; A) The overall thickness is 40 μm~90 μm; and the overall thermal shrinkage of the film is 1% to 5%.
本發明之薄膜可將藉由使用了T字模裝置之擠出成形法、共擠出成形法、加熱壓製法和溶媒澆鑄法依單層進行製膜者予以層合並加熱壓著等公知方法進行製造。尤其是使用了T字模裝置之擠出成形法或共擠出成形法係藉由調節模具狹縫部之模具孔口的間隔,而可輕易且均勻地控制薄膜之各層厚度,且可予以寬廣化,故較佳。再者,於製造了寬廣的薄膜後,由於可輕易地進行狹縫為配合各種FPC寬度之寬度,使用了T字模裝置之擠出成形法或共擠出成形法適合作為FPC製造用之離型薄膜的製造方法。另外,若為共擠出成形法,則由於在各樹脂間之黏著界面處可良好地進行熔融狀態下的混合,故可得到黏著強度亦優越之層合薄膜。The film of the present invention can be produced by a known method such as extrusion molding, coextrusion molding, hot pressing, and solvent casting using a T-die device, and forming a film by a single layer. . In particular, the extrusion molding method or the coextrusion molding method using the T-die device can easily and uniformly control the thickness of each layer of the film by adjusting the interval of the die orifices of the slit portion of the mold, and can be broadened. Therefore, it is better. Further, after a wide film is manufactured, since the slit can be easily used to match the width of various FPC widths, the extrusion molding method or the coextrusion molding method using the T-die device is suitable as a release for FPC production. A method of manufacturing a film. Further, in the case of the coextrusion molding method, since the mixing in the molten state can be favorably performed at the adhesion interface between the respective resins, a laminated film excellent in adhesion strength can be obtained.
具體而言,於製造僅由層(A)所形成之單層薄膜時,例如可使用附有單層T字模之擠出成形機,將擠出機及T字模的溫度設定為260~330℃而進行擠出成形。Specifically, in the case of producing a single-layer film formed only of the layer (A), for example, an extruder having a single-layer T-die can be used, and the temperature of the extruder and the T-die is set to 260 to 330 ° C. And extrusion molding is carried out.
具體而言,於製造由層(A)/層(B)/層(A)所形成之上述3層薄膜時,例如可使用2種附有3層T字模之擠出成形機,將擠出機及T字模的溫度設定為230~330℃而進行擠出成形。Specifically, in the production of the above-described three-layer film formed of the layer (A) / layer (B) / layer (A), for example, two types of extrusion molding machines with three layers of T-shaped molds can be used for extrusion. The temperature of the machine and the T-die was set to 230 to 330 ° C to carry out extrusion molding.
另外,此多層薄膜可藉由黏著劑將各層一體化而作為多層薄膜,並於各層間將胺基甲酸乙酯系、異氰酸酯系、環氧系般之黏著劑塗佈成薄膜狀,視需要將此等進行壓黏而予以成形。Further, the multilayer film can be integrated into a multilayer film by an adhesive, and an urethane-based, isocyanate-based or epoxy-based adhesive can be applied to the film between the layers, and if necessary, These are formed by pressure bonding.
另外,作為其他方法,亦可於各樹脂層之間,使順丁烯二酸酐接枝聚乙烯、順丁烯二酸酐接枝聚丙烯般之黏著性樹脂依薄膜狀與各樹脂層同時進行擠出、層合。另外,亦可採用使預先成形成薄膜或片材依上述順序進行熱壓黏或熱軋壓之方法。Further, as another method, a maleic anhydride-grafted polyethylene or a maleic anhydride-grafted polypropylene-like adhesive resin may be simultaneously extruded between the respective resin layers in a film form and each resin layer. Out, lamination. Further, a method of forming a film or a sheet in advance by thermal compression bonding or hot rolling in the above-described order may be employed.
另外,本發明之熱收縮率為1%~5%之薄膜,在屬於單層薄膜的情況下,可藉由於製造上述層(A)之單層薄膜後,將該薄膜進行延伸而獲得;又,於多層薄膜的情況下,可藉由於製造了具有由上述軟質聚烯烴所形成之層(B)、且至少1層之上述層(A)為最外層的多層薄膜後,將該薄膜進行延伸而獲得。Further, in the case of a single-layer film, the film having a heat shrinkage ratio of 1% to 5% of the present invention can be obtained by stretching the film after the single layer film of the layer (A) is produced; In the case of a multilayer film, the film can be stretched by manufacturing a multilayer film having the layer (B) formed of the above soft polyolefin and at least one layer of the layer (A) as the outermost layer. And get.
另外,作為延伸方法可適當採用習知方法,可藉由拉幅法、輥延伸法等之方法進行延伸。例如,於將由上述層(A)/層(B)/層(A)所形成之多層薄膜進行延伸的情況下,為了使延伸方向之熱收縮率成為1%~5%,則延伸時之加熱溫度為50℃~200℃、較佳100℃~150℃之範圍。另外,必須依微量之延伸倍率進行延伸,延伸倍率通常為1%~5%、較佳2%~4%。又,延伸可依單軸延伸或雙軸延伸進行,雙軸延伸可為逐次或同時進行。Further, as the stretching method, a conventional method can be suitably employed, and the stretching can be carried out by a method such as a tenter method or a roll stretching method. For example, when the multilayer film formed of the layer (A) / layer (B) / layer (A) is stretched, heating in the extension is performed so that the heat shrinkage ratio in the extending direction is 1% to 5%. The temperature is in the range of 50 ° C to 200 ° C, preferably 100 ° C to 150 ° C. In addition, it is necessary to extend at a slight extension ratio, and the stretching ratio is usually from 1% to 5%, preferably from 2% to 4%. Further, the extension may be performed by uniaxial stretching or biaxial stretching, and the biaxial stretching may be performed sequentially or simultaneously.
具體而言,本發明之薄膜可將依擠出成形法或共擠出成形法所得之原料薄膜,使用輥進行延伸。於將依擠出成形法或共擠出成形法所得之原料薄膜,接觸並通過於至少2根以上獨立旋轉之圓周速度相異的輥表面時,使原料薄膜於後來所接觸之輥的圓周速度(m/分)較原料薄膜所先接觸之輥的圓周速度(m/分)更快。亦即,本發明之薄膜之延伸方法,係依原料薄膜通過後來所接觸之輥表面的速度快於通過先接觸之輥表面的速度的方式,控制輥之圓周速度,藉此於使薄膜通過該2根以上之輥之間時進行延伸。Specifically, the film of the present invention can be stretched by a roll using a raw material film obtained by an extrusion molding method or a co-extrusion molding method. When the raw material film obtained by the extrusion molding method or the co-extrusion molding method is contacted and passed through the surface of the roller having different circumferential speeds of at least two independent rotations, the peripheral speed of the raw material film is contacted at the subsequent contact roller (m/min) is faster than the peripheral speed (m/min) of the roller which is first contacted with the raw material film. That is, the film stretching method of the present invention controls the peripheral speed of the roll according to the speed of the raw material film passing through the surface of the roll which is subsequently contacted, which is faster than the speed of the surface of the roll which is first contacted, thereby allowing the film to pass through the film. The extension is carried out between two or more rolls.
延伸所使用之輥係表面為鏡面之輥,或亦可使用壓紋輥。於壓紋輥之情況下,壓紋深度較佳係使用加工成平均粗度(Ra)為1 μm~200 μm,較佳2 μm~100 μm之輥。The roller surface used for the extension is a mirrored roller, or an embossing roller may be used. In the case of an embossing roll, the embossing depth is preferably a roll processed to have an average thickness (Ra) of from 1 μm to 200 μm, preferably from 2 μm to 100 μm.
其次,針對製造上述由層(A)/層(B)/層(A)所形成之薄膜的情況進行例示。表示本發明之薄膜之製造裝置之一例的圖4中,以3台擠出機20分別所熔融之4-甲基-1-戊烯系共聚合體及軟質聚烯烴,係通過多歧管型之3層共擠出T型模21而被擠出,並以冷卻輥22暫時冷卻至50℃~150℃,形成薄膜。其次,將薄膜以溫度50℃~200℃之加熱輥23進行加熱,接著,以溫度50℃~200℃之第1壓紋輥24、其次是第2壓紋輥25進行壓紋處理,同時使第2壓紋輥之圓周速度快於第1壓紋輥之圓周速度,亦即,使薄膜通過第2壓製輥27與第2壓紋輥25之間的速度快於通過第1壓製輥26與第1壓紋輥24之間的速度,藉此將薄膜於第1壓紋輥與第2壓紋輥之間進行延伸,則可得到本發明之薄膜8,為了得到熱收縮率為1%~5%之薄膜,於延伸薄膜時,較佳係相對於該薄膜所先接觸之輥表面的圓周速度,將該薄膜後來所接觸之輥的圓周速度設為1.01~1.05倍、更佳1.02~1.04倍。另外,此時之輥溫度為50℃~200℃、較佳100℃~150℃之範圍。又,該薄膜後來所接觸之輥表面的圓周速度,亦即加工速度為5m/分~100m/分、較佳10m/分~70m/分。又,若為熱收縮率未小於1%之範圍,則為了防止離型薄膜保管時之自然收縮,亦可於延伸處理後以未滿樹脂熔點之溫度進行回火處理。Next, a case where the above-described film formed of the layer (A) / layer (B) / layer (A) is produced will be exemplified. In Fig. 4 showing an example of the apparatus for producing a film of the present invention, a 4-methyl-1-pentene copolymer and a soft polyolefin which are respectively melted by three extruders 20 are passed through a multi-manifold type. The three layers were coextruded from the T-die 21 and extruded, and temporarily cooled to 50 ° C to 150 ° C by a cooling roll 22 to form a film. Next, the film is heated by a heating roller 23 having a temperature of 50 ° C to 200 ° C, and then embossed by a first embossing roll 24 having a temperature of 50 ° C to 200 ° C and a second embossing roll 25, and simultaneously The circumferential speed of the second embossing roller is faster than the peripheral speed of the first embossing roller, that is, the speed between the second pressing roller 27 and the second embossing roller 25 is faster than that passing through the first pressing roller 26 The speed between the first embossing rolls 24 is such that the film is stretched between the first embossing roll and the second embossing roll, whereby the film 8 of the present invention can be obtained, in order to obtain a heat shrinkage rate of 1%. The film of 5% is preferably about 1.01 to 1.05 times, more preferably 1.02 to 1.04, of the circumferential speed of the roller which the film is contacted with when the film is stretched. Times. Further, the roll temperature at this time is in the range of 50 ° C to 200 ° C, preferably 100 ° C to 150 ° C. Further, the peripheral speed of the surface of the roll which the film is later contacted, that is, the processing speed is 5 m/min to 100 m/min, preferably 10 m/min to 70 m/min. Further, in the case where the heat shrinkage ratio is not less than 1%, in order to prevent natural shrinkage during storage of the release film, tempering may be performed at a temperature less than the melting point of the resin after the stretching treatment.
尚且,薄膜之成形步驟、與該薄膜之延伸步驟,可分別二步驟而進行。Further, the step of forming the film and the step of extending the film can be carried out in two steps.
於分開進行薄膜成形步驟與延伸步驟時,為了防止成形所得之薄膜的自然收縮,亦可於依未滿樹脂熔點之溫度進行回火處理後,再進行延伸。另外,當然亦可連續實施薄膜之成形步驟與延伸步驟。用於實施此種步驟之裝置係一般市售者。When the film forming step and the stretching step are separately performed, in order to prevent natural shrinkage of the formed film, it may be further tempered after being subjected to tempering at a temperature not exceeding the melting point of the resin. In addition, it is of course also possible to continuously carry out the forming step and the stretching step of the film. The apparatus used to carry out such steps is generally marketed.
本發明之薄膜係耐熱性與離型性優越,可適合使用作為離型薄膜。具體而言,可舉例如FPC製造用離型薄膜、航空機零件所使用之ACM材料用離型薄膜、剛性印刷基板製造用離型薄膜、半導體密封材用離型薄膜、FRP成形用離型薄膜、橡膠片材硬化用離型薄膜、特殊黏著膠帶用離型薄膜等。The film of the present invention is excellent in heat resistance and release property, and can be suitably used as a release film. Specifically, for example, a release film for FPC production, a release film for ACM materials used for aircraft parts, a release film for producing a rigid printed circuit board, a release film for a semiconductor sealing material, and a release film for FRP molding, Release film for rubber sheet hardening, release film for special adhesive tape, etc.
此等之中,本發明之薄膜可適合使用於FPC製造用之離型薄膜。Among these, the film of the present invention can be suitably used for a release film for FPC production.
於FPC製造時,包括使用熱硬化型之黏著劑,將形成了電路之基板與覆蓋層挾持於金屬板並予以加熱及加壓而使其黏著的步驟。該步驟中,為了避免覆蓋層與金屬板在進行加熱及加壓時發生黏著的事態,而於其中間挾持使用本發明之離型薄膜。In the production of FPC, a step of holding a substrate and a cover layer of a circuit on a metal plate and heating and pressurizing it is carried out by using a thermosetting type adhesive. In this step, in order to avoid the occurrence of adhesion between the cover layer and the metal sheet during heating and pressurization, the release film of the present invention is used in the middle.
圖1為本發明之多層薄膜的剖面圖。又,圖2為使用本發明之離型薄膜、於成形FPC時之壓製時的狀態的剖面圖。藉由使用本發明之離型薄膜,非印刷部之空隙將由覆蓋層所完全押入密接,並一體化。圖2中,8為本發明之薄膜,9為FPC。Figure 1 is a cross-sectional view showing a multilayer film of the present invention. Moreover, Fig. 2 is a cross-sectional view showing a state in which the release film of the present invention is used for pressing at the time of forming an FPC. By using the release film of the present invention, the voids of the non-printing portion are completely adhered by the cover layer and integrated. In Fig. 2, 8 is a film of the present invention, and 9 is an FPC.
本發明之離型薄膜係於壓製成形時藉由覆蓋層而在所塗佈之熱硬化型的黏著劑因加熱而開始流動前發生變形,而且由於中間層(B)之緩衝性與最外層(A)之離型性優越,故如圖3所示般,離型薄膜之本發明之薄膜8將密接於覆蓋層6之端面與電路之銅箔面10,不致發生黏著劑之流出,而可依露出部與覆蓋層被覆部之境界區分分明的狀態進行FPC成形。The release film of the present invention is deformed by a coating layer before press-forming of the applied thermosetting adhesive by heating, and due to the cushioning property and the outermost layer of the intermediate layer (B). A) is excellent in release property, so as shown in FIG. 3, the film 8 of the present invention of the release film is adhered to the end face of the cover layer 6 and the copper foil face 10 of the circuit, so that the adhesive does not flow out, but FPC molding is performed in a state in which the boundary between the exposed portion and the cover layer portion is clearly defined.
再者,本發明之離型薄膜係於將覆蓋層進行黏著之加熱及加壓成形時,於離型薄膜不易發生皺紋,故不致發生因離型薄膜對於發生皺紋之部分之電路面凹凸的追隨不良所造成之空隙生成,且皺紋不轉印至FPC,故可得到外觀極良好之FPC。Further, in the release film of the present invention, when the cover layer is subjected to heating and pressure molding, the release film is less likely to wrinkle, so that the release film does not follow the unevenness of the circuit surface of the wrinkled portion. The voids caused by the defects are generated, and the wrinkles are not transferred to the FPC, so that an FPC having an excellent appearance can be obtained.
再者,將覆蓋層進行黏著之加熱及加壓成形時,由於上述層(B)之溢出較少,故不致發生因上述層(B)附著於形成了電路之基板面、和加熱及加壓成形所使用之金屬板上所造成之FPC製品產率降低和作業性降低等問題。Further, when the cover layer is subjected to adhesion heating and press molding, since the layer (B) is less likely to overflow, the layer (B) does not adhere to the surface of the substrate on which the circuit is formed, and is heated and pressurized. The yield of the FPC product caused by the metal sheet used for forming is lowered and the workability is lowered.
以下藉由實施例更詳細說明本發明,但本發明並不限定於此等實施例。Hereinafter, the present invention will be described in more detail by way of examples, but the invention is not limited thereto.
(1)測定對象樹脂(4-甲基-1-戊烯系共聚合體、軟質聚烯烴)(1) Resin for measurement (4-methyl-1-pentene copolymer, soft polyolefin)
(2)熔融流動速率(MFR)樹脂之MFR係根據ASTM D1238,依負重5.0kg、溫度260℃進行測定。(2) The MFR of the melt flow rate (MFR) resin was measured in accordance with ASTM D1238, with a load of 5.0 kg and a temperature of 260 °C.
(3)密度樹脂密度係根據ASTM D1505,依密度梯度管法進行測定。(3) Density The density of the resin was measured by a density gradient tube method in accordance with ASTM D1505.
(4)熔點樹脂之熔點係以DSC裝置(Seiko Instruments公司製)所測定。(4) The melting point of the melting point resin was measured by a DSC apparatus (manufactured by Seiko Instruments Co., Ltd.).
使用DSC裝置(Seiko Instruments公司製),於空氣中以10℃/分升溫至較各樹脂之熔點高30℃之溫度,將此時根據熔解之吸熱波峰溫度設為樹脂之熔點。其後,於較各樹脂熔點高30℃之溫度下保持3分間,其次依10℃/分降溫至室溫。Using a DSC apparatus (manufactured by Seiko Instruments Co., Ltd.), the temperature was raised to 10 ° C higher than the melting point of each resin in air at 10 ° C / min. At this time, the endothermic peak temperature of the melting was taken as the melting point of the resin. Thereafter, it was kept at a temperature 30 ° C higher than the melting point of each resin for 3 minutes, and then cooled to room temperature at 10 ° C / minute.
(5)域克軟化溫度樹脂之域克軟化溫度係使用射出成形所得之各樹脂厚度1/6英吋之平板,根據ASTM D1525予以測定。(5) Domain softening temperature The softening temperature of the resin is measured by using a flat plate of 1/6 inch thickness of each resin obtained by injection molding according to ASTM D1525.
(1)熱收縮率於製造薄膜時,使用附T字模之擠出成形機或共擠出成形機。將擠出機之設定溫度及T字模之設定溫度設為290℃。擠出成形所得之薄膜的寬為600mm。自此薄膜之任意位置切出於擠出方向(以下稱為MD方向)之長度為30cm、垂直於MD方向之方向(以下稱為TD方向)之長度為30cm的薄膜,將此作為試驗薄膜。將後述之加熱前的試驗薄膜之室溫下的MD方向長度設為L1(cm)。將試驗薄膜於溫度170℃之空氣烘爐中加熱30分鐘後取出,於室溫下冷卻30分鐘。將冷卻後之試驗薄膜之室溫下的MD方向長度設為L2(cm)。將以下式(1)所得之值作為薄膜之熱收縮率。(1) Heat Shrinkage Rate When manufacturing a film, an extrusion molding machine or a co-extrusion molding machine with a T-die is used. The set temperature of the extruder and the set temperature of the T-die were set to 290 °C. The film obtained by extrusion molding has a width of 600 mm. From the arbitrary position of the film, a film having a length of 30 cm in the extrusion direction (hereinafter referred to as MD direction) and a length of 30 cm perpendicular to the MD direction (hereinafter referred to as TD direction) was cut out as a test film. The length in the MD direction at room temperature of the test film before heating described later was set to L1 (cm). The test film was heated in an air oven at 170 ° C for 30 minutes, taken out, and cooled at room temperature for 30 minutes. The length of the test film at the time of cooling in the MD direction at room temperature was set to L2 (cm). The value obtained by the following formula (1) was taken as the heat shrinkage ratio of the film.
熱收縮率(%)=(L1-L2)/L1×100 (1)Heat shrinkage rate (%) = (L1-L2) / L1 × 100 (1)
(2)外觀皺紋於製造薄膜時使用附T字模之擠出成形機或共擠出成形機。將擠出機之設定溫度及T字模之設定溫度設為290℃。擠出成形所得之薄膜的寬為600mm。以每5m切出MD方向之長度為30cm、TD方向之長度為21cm的薄膜共10片,將此作為試驗薄膜。將此試驗薄膜設置於圖2所示之8的位置以進行加熱及加壓步驟。該步驟之條件為溫度160℃、壓力2MPa、加熱及加壓時間30分鐘。將流動開始溫度80℃之環氧系黏著劑以30 μm之厚度塗佈於覆蓋層上。將由聚醯亞胺薄膜所形成之覆蓋層(厚度25 μm)黏著於形成在基板上之電路面上。其後,取出試驗薄膜,以目視依下述評價薄膜之皺紋發生狀況。(2) Appearance wrinkles In the production of a film, an extrusion molding machine or a co-extrusion molding machine with a T-shaped mold is used. The set temperature of the extruder and the set temperature of the T-die were set to 290 °C. The film obtained by extrusion molding has a width of 600 mm. A total of 10 films each having a length of 30 cm in the MD direction and a length of 21 cm in the TD direction were cut out every 5 m, and this was used as a test film. This test film was placed at the position of 8 shown in Fig. 2 to perform a heating and pressurizing step. The conditions of this step were a temperature of 160 ° C, a pressure of 2 MPa, and a heating and pressurization time of 30 minutes. An epoxy-based adhesive having a flow start temperature of 80 ° C was applied to the cover layer at a thickness of 30 μm. A cover layer (thickness 25 μm) formed of a polyimide film was adhered to the circuit surface formed on the substrate. Thereafter, the test film was taken out, and the occurrence of wrinkles of the film was evaluated by visual observation as follows.
以目視於全部10片試驗薄膜上未確認到皺紋的情況:○以目視於全部10片試驗薄膜中1~4片上確認到皺紋的情況:△以目視於全部10片試驗薄膜之5~10片確認到皺紋的情況:×The case where wrinkles were not observed on all of the 10 test films was visually observed: ○When the wrinkles were observed on 1 to 4 of all the 10 test films, Δ was confirmed by visually observing 5 to 10 of all 10 test films. To the case of wrinkles: ×
(3)溢出量於製造薄膜時使用附T字模之擠出成形機或共擠出成形機。將擠出機之設定溫度及T字模之設定溫度設為290℃。擠出成形所得之薄膜的寬為600mm。自該薄膜之任意位置,切出MD方向之長度為10cm、TD方向之長度為10cm之薄膜共4片,將此設為試驗薄[S1]。(3) Overflow amount An extrusion molding machine or a co-extrusion molding machine with a T-shaped mold was used in the production of a film. The set temperature of the extruder and the set temperature of the T-die were set to 290 °C. The film obtained by extrusion molding has a width of 600 mm. From the arbitrary position of the film, a total of four films having a length of 10 cm in the MD direction and a length of 10 cm in the TD direction were cut out, and this was made into a test thin [S1].
將不銹鋼板(32cm×32cm×厚5mm)作為[A],將緩衝材之報紙10張(30cm×30cm)作為[B],將鋁板(30cm×30cm×厚0.1mm)作為[C]。A stainless steel plate (32 cm × 32 cm × thickness 5 mm) was designated as [A], 10 sheets (30 cm × 30 cm) of the buffer material were designated as [B], and an aluminum plate (30 cm × 30 cm × thickness 0.1 mm) was designated as [C].
作為測定溢出量之檢體,係使用由下開始依序重疊[A]/[B]/[C]/[S1]/[C]/[B]/[A]者。於此,重疊於[C]上之試驗薄膜[S1]4片係並排為各自不重疊。As the sample for measuring the overflow amount, the ones [A]/[B]/[C]/[S1]/[C]/[B]/[A] are sequentially superimposed from the bottom. Here, the test film [S1] superimposed on [C] was arranged side by side so as not to overlap each other.
其次,將上述檢體以溫度180℃、壓力8MPa進行加熱及加壓處理10分鐘後,以壓力5MPa進行保壓,以3分鐘冷卻至室溫再取出4片之試驗薄膜[S1]。分別測定自取出之4片試驗薄膜[S1]之層(A)之端部溢出之層(B)的長度,將其最大值作為溢出量。Next, the sample was heated and pressurized at a temperature of 180 ° C and a pressure of 8 MPa for 10 minutes, and then held at a pressure of 5 MPa, and cooled to room temperature for 3 minutes, and then four test films [S1] were taken out. The length of the layer (B) overflowing from the end of the layer (A) of the four test films [S1] taken out was measured, and the maximum value thereof was taken as the overflow amount.
(4)表面粗度(Ry)於製造薄膜時使用附T字模之擠出成形機或共擠出成形機。將擠出機之設定溫度及T字模之設定溫度設為290℃。擠出成形所得之薄膜的寬為600mm。自該薄膜之任意位置,切出MD方向之長度為10cm、TD方向之長度為10cm之薄膜,將此作為試驗薄膜。自此試驗薄膜之中心,於任意方向上以5cm作為基準長度,根據JIS B0601,求得薄膜之表面層的表面粗度。(4) Surface roughness (Ry) An extrusion molding machine or a co-extrusion molding machine with a T-shaped mold was used in the production of a film. The set temperature of the extruder and the set temperature of the T-die were set to 290 °C. The film obtained by extrusion molding has a width of 600 mm. From the arbitrary position of the film, a film having a length of 10 cm in the MD direction and a length of 10 cm in the TD direction was cut out, and this was used as a test film. From the center of the test film, the surface roughness of the surface layer of the film was determined in accordance with JIS B0601 by using 5 cm as the reference length in any direction.
(5)彈性模數(E’)薄膜之彈性模數(E’),係藉由測定薄膜之MD方向之溫度150℃下的動態貯藏彈性模數而予以評價。(5) The elastic modulus (E') of the elastic modulus (E') film was evaluated by measuring the dynamic storage elastic modulus at a temperature of 150 ° C in the MD direction of the film.
於製造薄膜時使用附T字模之擠出成形機或共擠出成形機。將擠出機之設定溫度及T字模之設定溫度設為290℃。擠出成形所得之薄膜的寬為600mm。自該薄膜之任意位置,切出MD方向之長度為0.13mm、TD方向之長度為5mm之薄膜,將此設為試驗薄膜。藉由動態貯藏彈性模數測定裝置(TA公司製,RSA-II)測定該試驗薄膜之MD方向之溫度150℃下的動態貯藏彈性模數。測定條件為測定溫度-150~200℃、升溫速度3℃/分、測定模式:拉伸、測定頻率數1Hz。藉由上述測定結果求得溫度150℃下之薄膜的彈性模數(E’)。An extrusion molding machine or a co-extrusion molding machine with a T-shaped mold is used in the production of the film. The set temperature of the extruder and the set temperature of the T-die were set to 290 °C. The film obtained by extrusion molding has a width of 600 mm. From the arbitrary position of the film, a film having a length of 0.13 mm in the MD direction and a length of 5 mm in the TD direction was cut out, and this was designated as a test film. The dynamic storage elastic modulus at a temperature of 150 ° C in the MD direction of the test film was measured by a dynamic storage elastic modulus measuring device (RSA-II, manufactured by TA Corporation). The measurement conditions were a measurement temperature of -150 to 200 ° C, a temperature increase rate of 3 ° C / min, and a measurement mode: stretching, and a measurement frequency of 1 Hz. From the above measurement results, the elastic modulus (E') of the film at a temperature of 150 ° C was obtained.
於製造薄膜時使用多歧管型之3層共擠出附T字模之擠出機。以第1擠出機及第3擠出機將(A1)4-甲基-1-戊烯系共聚合體(1-癸烯含量2.4質量%,MFR:25g/10分,熔點233℃)以溫度300℃進行可塑化。另外,以第2擠出機將(B1)丙烯.1-丁烯共聚合體(密度0.89g/cm3 ,MFR:30g/10分,熔點110℃,域克軟化溫度78℃,1-丁烯含量20莫耳%)以溫度300℃進行可塑化。A multi-manifold type 3-layer co-extruded extruder with a T-shaped mold was used in the production of the film. (A1) 4-methyl-1-pentene-based copolymer (1-decene content: 2.4% by mass, MFR: 25 g/10 min, melting point: 233 ° C) in a first extruder and a third extruder Plasticization was carried out at a temperature of 300 °C. In addition, the second extruder will be (B1) propylene. The 1-butene copolymer (density 0.89 g/cm 3 , MFR: 30 g/10 min, melting point 110 ° C, domain softening temperature 78 ° C, 1-butene content 20 mol %) was plasticized at a temperature of 300 ° C.
將A1當作層(A)、將B1當作層(B),進行共擠出,在T字模中進行層(A)/層(B)/層(A)之複合化。進而,用輥拉取該複合化物(20m/分),製造包含3層之多層薄膜。A1 was used as the layer (A) and B1 was used as the layer (B), and co-extrusion was carried out, and the layer (A) / layer (B) / layer (A) was combined in a T-type mold. Further, the composite (20 m/min) was taken up by a roll to produce a multilayer film comprising three layers.
其次,將所得之多層薄膜的表面,以平均粗度(Ra)為25 μm之2根壓紋輥進行壓紋處理。設為輥溫度130℃、壓紋加工速度20m/分。相對於多層薄膜所先接觸之第1壓紋輥的圓周速度,將多層薄膜後來所接觸之第2壓紋輥的圓周速度設為1.03倍。藉由將兩圓周速度之比設為1.03倍,而得到A1/B1/A1=25/70/25 μm之構成、總厚度120 μm、MD方向(延伸方向)之彈性模數(E’)為5×107 MPa、熱收縮率為2.1%之多層薄膜。Next, the surface of the obtained multilayer film was embossed by two embossing rolls having an average thickness (Ra) of 25 μm. The roll temperature was 130 ° C and the embossing speed was 20 m/min. The peripheral speed of the second embossing roll to which the multilayer film was subsequently contacted was set to 1.03 times with respect to the peripheral speed of the first embossing roll which was first contacted by the multilayer film. By setting the ratio of the two circumferential speeds to 1.03 times, the configuration of A1/B1/A1=25/70/25 μm, the total thickness of 120 μm, and the elastic modulus (E') in the MD direction (extension direction) are obtained. A multilayer film of 5 × 10 7 MPa and a heat shrinkage ratio of 2.1%.
其次,將所得之多層薄膜設置於圖2所示之加熱及加壓步驟中,將覆蓋層黏著於形成在基板上之電路面,作成FPC。設定溫度160℃、壓力2MPa、加熱及加壓時間30分之條件。該覆蓋層係由聚醯亞胺薄膜所形成,厚度為25 μm。又,將流動開始溫度80℃之環氧系黏著劑以30 μm之厚度塗佈於覆蓋層。Next, the obtained multilayer film was placed in the heating and pressurizing step shown in Fig. 2, and the cover layer was adhered to the circuit surface formed on the substrate to form an FPC. The conditions were set at a temperature of 160 ° C, a pressure of 2 MPa, and a heating and pressurization time of 30 minutes. The cover layer is formed of a polyimide film having a thickness of 25 μm. Further, an epoxy-based adhesive having a flow start temperature of 80 ° C was applied to the cover layer at a thickness of 30 μm.
所作成之FPC,係覆蓋層與基板本體完全地密接,未見到空氣殘存部分。In the FPC made, the cover layer is completely in close contact with the substrate body, and no air remains.
另外,以目視評價,並未在覆蓋層之黏著時所使用之多層薄膜(3層薄膜)上發生皺紋,又,所得之可撓性印刷基板之外觀亦良好。將評價結果整合示於表1。Further, by visual evaluation, wrinkles did not occur on the multilayer film (three-layer film) used when the cover layer was adhered, and the obtained flexible printed circuit board also had a good appearance. The evaluation results are shown in Table 1.
除了取代B1使用(B2)乙烯.丙烯酸乙酯共聚合體(MFR:27g/10分,熔點90℃,域克軟化溫度70℃,丙烯酸乙酯含量15莫耳%)以外,其餘依表1所示條件以與實施例1相同順序製造多層薄膜。Except for the use of (B2) ethylene. acrylate ethyl ester copolymer (MFR: 27 g/10 min, melting point 90 ° C, domain softening temperature 70 ° C, ethyl acrylate content 15 mol%) in place of B1, the others are shown in Table 1. Conditions A multilayer film was produced in the same order as in Example 1.
其次,藉由將此多層薄膜依與實施例1相同之條件進行加熱及加壓,而將覆蓋層黏著於形成在基板上之電路面上。Next, the cover film was adhered to the circuit surface formed on the substrate by heating and pressurizing the multilayer film under the same conditions as in Example 1.
如同實施例1進行評價,結果示於表1。Evaluation was carried out as in Example 1, and the results are shown in Table 1.
除了取代B1,使用(B3)丙烯.1-丁烯.4-甲基-1-戊烯共聚合體(丙烯含量36莫耳%、1-丁烯含量14莫耳%、4-甲基-1-戊烯含量50莫耳%,密度0.880g/cm3 ,MFR:27g/10分,域克軟化溫度80℃)50質量%與直鏈狀低密度聚乙烯(密度0.92g/cm3 ,MFR:15g/10分,域克軟化溫度100℃)50質量%之摻合物(MFR:20g/10分,域克軟化溫度85℃)以外,其餘依表1所示條件以與實施例1相同順序製造多層薄膜。In addition to replacing B1, use (B3) propylene. 1-butene. 4-methyl-1-pentene copolymer (propylene content 36 mol%, 1-butene content 14 mol%, 4-methyl-1-pentene content 50 mol%, density 0.880 g/cm 3 , MFR: 27g/10 minutes, domain softening temperature 80 ° C) 50% by mass and linear low density polyethylene (density 0.92g / cm 3 , MFR: 15g / 10 minutes, domain softening temperature 100 ° C) 50 mass A multilayer film was produced in the same manner as in Example 1 except for the blend of % (MFR: 20 g/10 minutes, domain softening temperature: 85 ° C).
其次,藉由將此多層薄膜依與實施例1相同之條件進行加熱及加壓,而將覆蓋層黏著於形成在基板上之電路面上。Next, the cover film was adhered to the circuit surface formed on the substrate by heating and pressurizing the multilayer film under the same conditions as in Example 1.
如同實施例1進行評價,結果示於表1。Evaluation was carried out as in Example 1, and the results are shown in Table 1.
除了藉由改變第1擠出機及第3擠出機之擠出量,使層(A)之厚度成為20 μm以外,其餘依表1所示條件以與實施例1相同順序製造多層薄膜。A multilayer film was produced in the same manner as in Example 1 except that the thickness of the layer (A) was changed to 20 μm by changing the extrusion amount of the first extruder and the third extruder.
其次,藉由將此多層薄膜依與實施例1相同之條件進行加熱及加壓,而將覆蓋層黏著於形成在基板上之電路面上。Next, the cover film was adhered to the circuit surface formed on the substrate by heating and pressurizing the multilayer film under the same conditions as in Example 1.
如同實施例1進行評價,結果示於表1。Evaluation was carried out as in Example 1, and the results are shown in Table 1.
除了藉由改變第1擠出機及第3擠出機之擠出量,使層(A)之厚度成為35 μm以外,其餘依表1所示條件以與實施例1相同順序製造多層薄膜。A multilayer film was produced in the same manner as in Example 1 except that the thickness of the layer (A) was changed to 35 μm by changing the extrusion amount of the first extruder and the third extruder.
其次,藉由將此多層薄膜依與實施例1相同之條件進行加熱及加壓,而將覆蓋層黏著於形成在基板上之電路面上。Next, the cover film was adhered to the circuit surface formed on the substrate by heating and pressurizing the multilayer film under the same conditions as in Example 1.
如同實施例1進行評價,結果示於表1。Evaluation was carried out as in Example 1, and the results are shown in Table 1.
除了僅使用第1擠出機,將層(A)之厚度設為50 μm之單層薄膜以外,其餘依表1所示條件以與實施例1相同順序製造多層薄膜。A multilayer film was produced in the same manner as in Example 1 except that the first extruder was used, and the thickness of the layer (A) was 50 μm.
其次,藉由將此多層薄膜依與實施例1相同之條件進行加熱及加壓,而將覆蓋層黏著於形成在基板上之電路面上。Next, the cover film was adhered to the circuit surface formed on the substrate by heating and pressurizing the multilayer film under the same conditions as in Example 1.
如同實施例1進行評價,結果示於表1。Evaluation was carried out as in Example 1, and the results are shown in Table 1.
除了取代A1使用(A2)4-甲基-1-戊烯系共聚合體(1-癸烯含量1.0質量%,MFR:25g/10分,熔點238℃)以外,其餘依表1所示條件以與實施例1相同順序製造多層薄膜。Except for the substitution of A1, the (A2) 4-methyl-1-pentene copolymer (1-decene content 1.0% by mass, MFR: 25 g/10 minutes, melting point 238 ° C) was used, except for the conditions shown in Table 1. A multilayer film was produced in the same order as in Example 1.
其次,藉由將此多層薄膜依與實施例1相同之條件進行加熱及加壓,而將覆蓋層黏著於形成在基板上之電路面上。Next, the cover film was adhered to the circuit surface formed on the substrate by heating and pressurizing the multilayer film under the same conditions as in Example 1.
如同實施例1進行評價,結果示於表1。Evaluation was carried out as in Example 1, and the results are shown in Table 1.
除了取代A1使用(A3)4-甲基-1-戊烯系共聚合體(1-癸烯含量4.0質量%,MFR:27g/10分,熔點229℃)以外,其餘依表1所示條件以與實施例1相同順序製造多層薄膜。Except for the substitution of A1, the (A3) 4-methyl-1-pentene copolymer (1-decene content 4.0% by mass, MFR: 27 g/10 minutes, melting point 229 ° C) was used, except for the conditions shown in Table 1. A multilayer film was produced in the same order as in Example 1.
其次,藉由將此多層薄膜依與實施例1相同之條件進行加熱及加壓,而將覆蓋層黏著於形成在基板上之電路面上。Next, the cover film was adhered to the circuit surface formed on the substrate by heating and pressurizing the multilayer film under the same conditions as in Example 1.
如同實施例1進行評價,結果示於表1。Evaluation was carried out as in Example 1, and the results are shown in Table 1.
除了取代Al使用(A4)A4:4-甲基-1-戊烯系共聚合體(1-十四烯含量2質量%,MFR:22g/10分,熔點232℃)以外,其餘依表1所示條件以與實施例1相同順序製造多層薄膜。Except for the substitution of Al, (A4) A4: 4-methyl-1-pentene-based copolymer (1-tetradecene content 2% by mass, MFR: 22 g/10 minutes, melting point 232 ° C), A multilayer film was produced in the same order as in Example 1 under the conditions shown.
其次,藉由將此多層薄膜依與實施例1相同之條件進行加熱及加壓,而將覆蓋層黏著於形成在基板上之電路面上。Next, the cover film was adhered to the circuit surface formed on the substrate by heating and pressurizing the multilayer film under the same conditions as in Example 1.
如同實施例1進行評價,結果示於表1。Evaluation was carried out as in Example 1, and the results are shown in Table 1.
除了藉由改變第1擠出機及第3擠出機之擠出量,使層(A)之厚度成為5 μm以外,其餘依表2所示條件以與實施例1相同順序製造多層薄膜。A multilayer film was produced in the same manner as in Example 1 except that the thickness of the layer (A) was changed to 5 μm by changing the extrusion amount of the first extruder and the third extruder.
其次,藉由將此多層薄膜依與實施例1相同之條件進行加熱及加壓,而將覆蓋層黏著於形成在基板上之電路面上。Next, the cover film was adhered to the circuit surface formed on the substrate by heating and pressurizing the multilayer film under the same conditions as in Example 1.
如同實施例1進行評價,結果示於表2。Evaluation was carried out as in Example 1, and the results are shown in Table 2.
除了藉由改變第1擠出機及第3擠出機之擠出量,使層(A)之厚度成為50 μm以外,其餘依表2所示條件以與實施例1相同順序製造多層薄膜。A multilayer film was produced in the same manner as in Example 1 except that the thickness of the layer (A) was changed to 50 μm by changing the extrusion amount of the first extruder and the third extruder.
其次,藉由將此多層薄膜依與實施例1相同之條件進行加熱及加壓,而將覆蓋層黏著於形成在基板上之電路面上。Next, the cover film was adhered to the circuit surface formed on the substrate by heating and pressurizing the multilayer film under the same conditions as in Example 1.
如同實施例1進行評價,結果示於表2。Evaluation was carried out as in Example 1, and the results are shown in Table 2.
除了取代A1使用(A5)4-甲基-1-戊烯系共聚合體(1-癸烯含量5.0質量%,MFR:24g/10分,熔點226℃)以外,其餘依表2所示條件以與實施例1相同順序製造多層薄膜。Except for the substitution of A1 using (A5) 4-methyl-1-pentene copolymer (1-nonene content 5.0% by mass, MFR: 24 g/10 minutes, melting point 226 ° C), the conditions shown in Table 2 were A multilayer film was produced in the same order as in Example 1.
其次,藉由將此多層薄膜依與實施例1相同之條件進行加熱及加壓,而將覆蓋層黏著於形成在基板上之電路面上。Next, the cover film was adhered to the circuit surface formed on the substrate by heating and pressurizing the multilayer film under the same conditions as in Example 1.
如同實施例1進行評價,結果示於表2。Evaluation was carried out as in Example 1, and the results are shown in Table 2.
除了取代A1使用(A5)4-甲基-1-戊烯系共聚合體(1-癸烯含量5.0質量%,MFR:24g/10分,熔點226℃),並取代B1使用B2以外,其餘依表2所示條件以與實施例1相同順序製造多層薄膜。In addition to the substitution A1, the (A5) 4-methyl-1-pentene copolymer (1-nonene content 5.0% by mass, MFR: 24 g/10 minutes, melting point 226 ° C) was used, and B1 was used instead of B1. The conditions shown in Table 2 were carried out in the same order as in Example 1 to produce a multilayer film.
其次,藉由將此多層薄膜依與實施例1相同之條件進行加熱及加壓,而將覆蓋層黏著於形成在基板上之電路面上。Next, the cover film was adhered to the circuit surface formed on the substrate by heating and pressurizing the multilayer film under the same conditions as in Example 1.
如同實施例1進行評價,結果示於表2。Evaluation was carried out as in Example 1, and the results are shown in Table 2.
除了取代A1使用(A5)4-甲基-1-戊烯系共聚合體(1-癸烯含量5.0質量%,MFR:24g/10分,熔點226℃),並取代B1使用B3以外,其餘依表2所示條件以與實施例1相同順序製造多層薄膜。In addition to the substitution A1, the (A5) 4-methyl-1-pentene copolymer (1-nonene content 5.0% by mass, MFR: 24 g/10 minutes, melting point 226 ° C) was used, and B1 was used instead of B1. The conditions shown in Table 2 were carried out in the same order as in Example 1 to produce a multilayer film.
其次,藉由將此多層薄膜依與實施例1相同之條件進行加熱及加壓,而將覆蓋層黏著於形成在基板上之電路面上。Next, the cover film was adhered to the circuit surface formed on the substrate by heating and pressurizing the multilayer film under the same conditions as in Example 1.
如同實施例1進行評價,結果示於表2。Evaluation was carried out as in Example 1, and the results are shown in Table 2.
除了取代A1使用(A6)4-甲基-1-戊烯系共聚合體(1-癸烯含量0.2質量%,MFR:25g/10分,熔點241℃)以外,其餘依表2所示條件以與實施例1相同順序製造多層薄膜。In addition to the substitution of A1, the (A6) 4-methyl-1-pentene copolymer (1-decene content 0.2% by mass, MFR: 25 g/10 minutes, melting point 241 ° C) was used, except for the conditions shown in Table 2 A multilayer film was produced in the same order as in Example 1.
其次,藉由將此多層薄膜依與實施例1相同之條件進行加熱及加壓,而將覆蓋層黏著於形成在基板上之電路面上。Next, the cover film was adhered to the circuit surface formed on the substrate by heating and pressurizing the multilayer film under the same conditions as in Example 1.
如同實施例1進行評價,結果示於表2。Evaluation was carried out as in Example 1, and the results are shown in Table 2.
除了取代A1使用(A7)4-甲基-1-戊烯系共聚合體(1-癸烯含量10質量%,MFR:22g/10分,熔點221℃)以外,其餘依表2所示條件以與實施例1相同順序製造多層薄膜。Except for the substitution of A1, (A7) 4-methyl-1-pentene-based copolymer (1-decene content: 10% by mass, MFR: 22 g/10 minutes, melting point: 221 ° C), the conditions shown in Table 2 were A multilayer film was produced in the same order as in Example 1.
其次,藉由將此多層薄膜依與實施例1相同之條件進行加熱及加壓,而將覆蓋層黏著於形成在基板上之電路面上。Next, the cover film was adhered to the circuit surface formed on the substrate by heating and pressurizing the multilayer film under the same conditions as in Example 1.
如同實施例1進行評價,結果示於表2。Evaluation was carried out as in Example 1, and the results are shown in Table 2.
除了取代A1使用(A8)4-甲基-1-戊烯系共聚合體(乙烯含量2質量%,MFR:26g/10分,熔點241℃)以外,其餘依表2所示條件以與實施例1相同順序製造多層薄膜。The conditions shown in Table 2 were compared with the examples except that the (A8) 4-methyl-1-pentene copolymer (A8 content: ethylene content: 2% by mass, MFR: 26 g/10 minutes, melting point: 241 ° C) was used instead of A1. 1 A multilayer film was produced in the same order.
其次,藉由將此多層薄膜依與實施例1相同之條件進行加熱及加壓,而將覆蓋層黏著於形成在基板上之電路面上。Next, the cover film was adhered to the circuit surface formed on the substrate by heating and pressurizing the multilayer film under the same conditions as in Example 1.
如同實施例1進行評價,結果示於表2。Evaluation was carried out as in Example 1, and the results are shown in Table 2.
除了將第1壓紋輥與第2壓紋輥之圓周速度設為相同以外,其餘與實施例1相同地進行而製造未延伸之多層薄膜。An unstretched multilayer film was produced in the same manner as in Example 1 except that the peripheral speeds of the first embossing roll and the second embossing roll were the same.
其次,藉由將此薄膜依與實施例1相同之條件進行加熱及加壓,而將覆蓋層黏著於形成在基板上之電路面上。Next, the film was adhered to the circuit surface formed on the substrate by heating and pressurizing the film under the same conditions as in Example 1.
以目視進行評價,覆蓋層之黏著所使用之離型薄膜上發生有皺紋,該皺紋轉印至可撓性印刷基板上而形成外觀有問題的可撓性印刷基板。評價結果示於表2。The evaluation was carried out by visual observation, and wrinkles were formed on the release film used for the adhesion of the cover layer, and the wrinkles were transferred onto the flexible printed circuit board to form a flexible printed circuit board having a problem in appearance. The evaluation results are shown in Table 2.
除了相對於第1壓紋輥之圓周速度,將第2壓紋輥之圓周速度設為1.15倍,並於MD方向上延伸15%以外,其餘與實施例1相同地進行而製造多層薄膜。A multilayer film was produced in the same manner as in Example 1 except that the peripheral speed of the second embossing roll was 1.15 times the circumferential speed of the first embossing roll and 15% in the MD direction.
其次,藉由將此多層薄膜依與實施例1相同之條件進行加熱及加壓,而將覆蓋層黏著於形成在基板上之電路面上。Next, the cover film was adhered to the circuit surface formed on the substrate by heating and pressurizing the multilayer film under the same conditions as in Example 1.
所完成之可撓性印刷基板係覆蓋層與基板本體之密接性差劣,發生了空氣存在部分。又,起因於延伸不均之模樣轉印至可撓性印刷基板上,而可撓性印刷基板之外觀不良。評價結果示於表2。The adhesive layer of the completed flexible printed circuit board is inferior in adhesion to the substrate body, and an air is present. Further, the pattern which is unevenly extended is transferred onto the flexible printed circuit board, and the appearance of the flexible printed circuit board is poor. The evaluation results are shown in Table 2.
除了僅使用第1擠出機,作成層(A)之厚度設為20 μm之單層薄膜以外,其餘依表2所示條件以與實施例1相同順序製造多層薄膜。A multilayer film was produced in the same manner as in Example 1 except that the first extruder was used and a single layer film having a layer (A) thickness of 20 μm was formed.
其次,藉由將此多層薄膜依與實施例1相同之條件進行加熱及加壓,而將覆蓋層黏著於形成在基板上之電路面上。Next, the cover film was adhered to the circuit surface formed on the substrate by heating and pressurizing the multilayer film under the same conditions as in Example 1.
如同實施例1進行評價,結果示於表2。Evaluation was carried out as in Example 1, and the results are shown in Table 2.
除了僅使用第1擠出機,作成層(A)之厚度設為150 μm之單層薄膜以外,其餘依表2所示條件以與實施例1相同順序製造多層薄膜。A multilayer film was produced in the same manner as in Example 1 except that the first extruder was used, and the single layer film having the thickness of the layer (A) of 150 μm was formed.
其次,藉由將此多層薄膜依與實施例1相同之條件進行加熱及加壓,而將覆蓋層黏著於形成在基板上之電路面上。Next, the cover film was adhered to the circuit surface formed on the substrate by heating and pressurizing the multilayer film under the same conditions as in Example 1.
如同實施例1進行評價,結果示於表2。Evaluation was carried out as in Example 1, and the results are shown in Table 2.
本發明之含有由特定之4-甲基-1-戊烯系共聚合體所形成之層、且具有特定厚度構成及熱收縮率的薄膜,由於耐熱性及離型性優越,故適合使用作為離型薄膜。尤其是製造FPC時,藉由使用作為離型薄膜,則可防止金屬板與覆蓋層之間的黏著、及黏著劑流出而黏著至其他零件的情形,而且於成形時,在非印刷部不形成空隙,電路端子部份等之露出的部份不因黏著劑之熔融流出而被污染。The film of the present invention containing a layer formed of a specific 4-methyl-1-pentene copolymer, having a specific thickness and a heat shrinkage ratio, is excellent in heat resistance and release property, and is therefore suitable for use as a separation. Type film. In particular, when FPC is produced, by using as a release film, adhesion between the metal plate and the cover layer, and adhesion of the adhesive to the other parts can be prevented, and the non-printed portion is not formed during molding. The exposed portion of the gap, the circuit terminal portion, and the like is not contaminated by the melted out of the adhesive.
由於藉加熱及加壓使覆蓋層黏著時,在離型薄膜並未發生皺紋,故不致有於發生皺紋之部分處離型薄膜對於形成電路之基板表面凹凸的追隨不良所導致之空隙生成,可有效率地使經改善了因皺紋轉印所導致之外觀不良的FPC成形,故可適合使用作為FPC製造用之離型薄膜。When the cover layer is adhered by heat and pressure, wrinkles are not formed on the release film, so that the gap formed by the release film on the surface of the substrate on which the circuit is formed is not generated at the portion where wrinkles occur. Since FPC molding which is improved in appearance due to wrinkle transfer is efficiently formed, a release film which is used for FPC production can be suitably used.
另外,於使用離型薄膜作為FPC製造時之具有含特定軟質聚烯烴之層的薄膜的情況下,該離型薄膜係具有良好之緩衝性,並可追隨FPC表面的凹凸,且加熱及加壓時之黏著劑的溢出較少,並未發生黏著劑附著於FPC、以及加熱及加壓時所使用之金屬板而造成之FPC製品產率降低、作業性降低等問題。Further, in the case where a release film is used as a film having a layer containing a specific soft polyolefin at the time of FPC production, the release film has good cushioning properties and can follow the unevenness of the surface of the FPC, and is heated and pressurized. In the case where the adhesive is less likely to overflow, there is no problem that the FPC product yield is lowered and the workability is lowered due to adhesion of the adhesive to the FPC and the metal plate used for heating and pressurization.
1...由4-甲基-1-戊烯系共聚合體所形成之層(A)1. . . Layer formed by 4-methyl-1-pentene copolymer (A)
2...由軟質聚烯烴所形成之層(B)2. . . Layer formed of soft polyolefin (B)
3...加熱、加壓用金屬板3. . . Metal plate for heating and pressurization
4...不銹鋼板4. . . Stainless steel plate
5...離型薄膜(單層)5. . . Release film (single layer)
6...覆蓋層6. . . Cover layer
7...塗佈於覆蓋層之熱硬化型黏著劑7. . . Thermosetting adhesive applied to the cover layer
8...本發明之薄膜8. . . Film of the invention
9...可撓性印刷電路基板9. . . Flexible printed circuit board
10...電路之銅箔10. . . Circuit copper foil
11...可撓性印刷電路基板之電路部11. . . Circuit part of flexible printed circuit board
20...擠出機20. . . Extruder
21...多歧管型之3層共擠出T型模twenty one. . . Multi-manifold type 3-layer co-extruded T-die
22...冷卻輥twenty two. . . Cooling roller
23...加熱輥twenty three. . . Heating roller
24...第1壓紋輥twenty four. . . First embossing roller
25...第2壓紋輥25. . . Second embossing roller
26...第1壓製輥26. . . First pressing roll
27...第2壓製輥27. . . Second pressing roll
圖1為本發明之薄膜的剖面圖。Figure 1 is a cross-sectional view of a film of the present invention.
圖2為表示使用本發明之薄膜而使可撓性印刷電路基板成形之狀態之一例的剖面圖。2 is a cross-sectional view showing an example of a state in which a flexible printed circuit board is molded by using the film of the present invention.
圖3為表示使用本發明之薄膜而成形之可撓性印刷電路基板之端子露出部之一例的剖面圖。3 is a cross-sectional view showing an example of a terminal exposed portion of a flexible printed circuit board formed by using the film of the present invention.
圖4為表示本發明之薄膜之製造裝置之一例的圖。Fig. 4 is a view showing an example of a manufacturing apparatus of a film of the present invention.
1...由4-甲基-1-戊烯系共聚合體所形成之層(A)1. . . Layer formed by 4-methyl-1-pentene copolymer (A)
2...由軟質聚烯烴所形成之層(B)2. . . Layer formed of soft polyolefin (B)
Claims (11)
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JPWO2008001682A1 (en) | 2009-11-26 |
WO2008001682A1 (en) | 2008-01-03 |
JP5180826B2 (en) | 2013-04-10 |
TW200806731A (en) | 2008-02-01 |
CN101479327B (en) | 2012-05-30 |
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