TWI772095B - Release film for fabricating printed circuit board - Google Patents
Release film for fabricating printed circuit board Download PDFInfo
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- TWI772095B TWI772095B TW110124914A TW110124914A TWI772095B TW I772095 B TWI772095 B TW I772095B TW 110124914 A TW110124914 A TW 110124914A TW 110124914 A TW110124914 A TW 110124914A TW I772095 B TWI772095 B TW I772095B
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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
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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
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/02—Physical, chemical or physicochemical properties
- B32B7/022—Mechanical properties
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
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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
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- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
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- Non-Metallic Protective Coatings For Printed Circuits (AREA)
- Adhesive Tapes (AREA)
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Abstract
Description
本發明關於一種離型膜,該離型膜用於例如軟性印刷電路板(FPC)等印刷電路板的生產製程。 The present invention relates to a release film, which is used in the production process of printed circuit boards such as flexible printed circuit boards (FPC).
常用的離型膜含有一緩衝層,其位於高度方向的中段,用於吸收覆蓋膜和銅箔基板(CCL)於加熱沖壓時的凹凸不平。該緩衝層由柔軟的樹脂薄膜構成,例如:聚乙烯、高密度聚乙烯(HDPE)等熱塑性樹脂(請參照以下專利文獻1)。熱塑性樹脂薄膜理當有其熔點,當加熱到熔點以上時,該樹脂即具有流動性。 The commonly used release film contains a buffer layer, which is located in the middle section of the height direction to absorb the unevenness of the cover film and the copper foil substrate (CCL) during heating and stamping. The buffer layer is made of a flexible resin film, for example, a thermoplastic resin such as polyethylene and high-density polyethylene (HDPE) (refer to the following Patent Document 1). The thermoplastic resin film should have its melting point, and when heated above the melting point, the resin has fluidity.
然而用於印刷電路板的材料,特別是軟性印刷電路板所用的材料性能提高,因此近年來加工溫度趨於高溫化。例如,在覆蓋膜和CCL的熱壓合加工中所使用的樹脂,若是由環氧樹脂製成的通用品(FR4),其加工溫度為150℃;若是使用聚醯亞胺樹脂的耐熱品(FR5),加工溫度為170℃;而使用LCP(液晶高分子)者(FR6),加工溫度為250℃。再者,前述的「FR」係表示印刷電路板之材料銅箔基板的阻燃性指標(flame retardant grade),該指標目前共分為FR1~FR6。 However, the materials used for printed circuit boards, especially the materials used for flexible printed circuit boards, have improved performance, so the processing temperature tends to be higher in recent years. For example, if the resin used in the thermocompression processing of the cover film and CCL, if it is a general-purpose product (FR4) made of epoxy resin, the processing temperature is 150 °C; if it is a heat-resistant product using polyimide resin (FR4) FR5), the processing temperature is 170 °C; while the use of LCP (liquid crystal polymer) (FR6), the processing temperature is 250 °C. Furthermore, the aforementioned "FR" refers to the flame retardant grade of the copper foil substrate of the printed circuit board, which is currently divided into FR1~FR6.
此外,為了提升加工效率並縮短加工時間,即使材料為FR4或FR5也能在高溫下進行。 In addition, in order to improve processing efficiency and shorten processing time, it can be performed at high temperature even if the material is FR4 or FR5.
一般認為,今後的加工溫度將會更加趨於高溫化。 It is generally believed that the processing temperature will be higher in the future.
然而,若採用比重0.97的同質聚合物時,高密度聚乙烯的熔點係為136℃左右;因此,如果使用高密度聚乙烯作為緩衝層,離型膜溫度被加熱至熔點以上時,即會導致聚合物溶出而汙染模具或產品。 However, if a homogeneous polymer with a specific gravity of 0.97 is used, the melting point of HDPE is about 136°C; therefore, if HDPE is used as the buffer layer, when the temperature of the release film is heated above the melting point, it will cause The polymer dissolves and contaminates the mold or product.
專利文獻1:日本專利特開2007-98816號公報。 Patent Document 1: Japanese Patent Laid-Open No. 2007-98816.
目前為止,緩衝層以樹脂薄膜製作已是業界常識,但在防止模具等用品污染的層面上卻有其限制。 So far, it is common knowledge in the industry that the buffer layer is made of resin film, but there are limitations in preventing contamination of tools such as molds.
因此,由於本發明使用固化性黏合劑作為緩衝層,所以即使在高溫環境下也不會造成模具等用品受到污染。 Therefore, since the present invention uses a curable adhesive as a buffer layer, even in a high-temperature environment, there will be no contamination of articles such as molds.
為達上述目的,本發明的離型膜於兩層樹脂層之間設有一緩衝層,該兩層樹脂層中至少有一層是由熱塑性樹脂構成的離型樹脂層,其熔點為200℃以上;該緩衝層由具有交聯結構的固化性樹脂構成,其固化後彈性儲存率係在23℃時為10MPa以下。 In order to achieve the above purpose, the release film of the present invention is provided with a buffer layer between two resin layers, and at least one of the two resin layers is a release resin layer composed of thermoplastic resin, and its melting point is above 200 ℃; The buffer layer is made of a curable resin having a cross-linked structure, and the elastic storage rate after curing is 10 MPa or less at 23°C.
上述構造將緩衝層夾在樹脂層之間,而緩衝層所具有的交聯結構能防止固化性樹脂溶出。另外,彈性儲存率低的固化性樹脂非常柔軟,因此在進行熱沖壓時,可確保離型樹脂層的凹凸契合性。樹脂層中至少有一層的離型樹脂層具有高耐熱性,能發揮脫模的功能。 The above structure sandwiches the buffer layer between the resin layers, and the buffer layer has a cross-linked structure that prevents the elution of the curable resin. In addition, the curable resin with low elastic storage rate is very soft, so it is possible to ensure the conformability of the unevenness of the release resin layer during hot stamping. The release resin layer of at least one of the resin layers has high heat resistance and can exhibit the function of mold release.
本發明之離型膜因為緩衝層由具有交聯結構的固化性樹脂構成,所以即使在高溫環境下使用也不會汙染模具等用品,同時能獲得良好的凹凸契合性。 Because the buffer layer of the release film of the present invention is made of curable resin with a cross-linked structure, it will not contaminate articles such as molds even if it is used in a high temperature environment, and at the same time, good unevenness can be obtained.
11:離型膜 11: Release film
12:離型樹脂層 12: Release resin layer
13:緩衝層 13: Buffer layer
14:離型塗層 14: Release coating
15、16:樹脂層 15, 16: Resin layer
21a:單面銅箔基板 21a: Single-sided copper foil substrate
21b:雙面銅箔基板 21b: Double-sided copper foil substrate
22:覆蓋膜 22: cover film
23:加熱板 23: Heating plate
圖1係本發明離型膜的剖面圖。 FIG. 1 is a cross-sectional view of the release film of the present invention.
圖2係本發明離型膜一實施例之分離狀態剖面圖。 FIG. 2 is a sectional view of the separation state of an embodiment of the release film of the present invention.
圖3係本發明離型膜一實施例之沖壓成形時的剖面圖。 FIG. 3 is a cross-sectional view of an embodiment of the release film of the present invention during stamping.
圖4係本發明離型膜另一實施例之剖面圖。 4 is a cross-sectional view of another embodiment of the release film of the present invention.
圖5係本發明離型膜再一實施例之剖面圖。 FIG. 5 is a cross-sectional view of another embodiment of the release film of the present invention.
圖6係本發明離型膜又一實施例之剖面圖。 6 is a cross-sectional view of another embodiment of the release film of the present invention.
圖7係本發明離型膜其他實施例之剖面圖。 7 is a cross-sectional view of another embodiment of the release film of the present invention.
以下茲透過圖式說明本發明的實施形態。 Hereinafter, embodiments of the present invention will be described with reference to the drawings.
圖1係離型膜11的剖面圖。該離型膜11的結構係為兩樹脂層之間具有一緩衝層,該兩樹脂層中至少有一層是由熱塑性樹脂構成的離型樹脂層。
FIG. 1 is a cross-sectional view of the
圖1所示之離型膜11係於兩離型樹脂層12之間具有一緩衝層13,因此該離型膜至少有三層。該離型膜11具有優越的耐熱性,以適用於超過200℃或250℃的高溫環境。
The
離型樹脂層12分別位於上下兩最外層,其係由拉伸強度和延展伸度佳的熱塑性樹脂所構成,與模具或製品接觸並具有脫模功能。
The
如前所述,為了希望能在超過200℃之高溫環境下使用,因此需使用適當的材料製作,具體而言,例如:聚對苯二甲酸乙二酯(PET)、聚萘二甲酸乙二醇酯(PEN)、聚對苯二甲酸丁二醇酯(PBT)、聚芳酯(PAR)、聚醯亞胺(PI)、聚酰胺(PA)、聚醯胺醯亞胺(PAI)、聚醚醯亞胺(PEI)、聚醚醚酮(PEEK)、聚苯硫醚(PPS)等;該適當材料至少由前述材料之一形成,其熔點可為200℃或250℃以上。 As mentioned above, in order to be able to use in a high temperature environment exceeding 200 ° C, it is necessary to use appropriate materials, specifically, such as: polyethylene terephthalate (PET), polyethylene naphthalate Alcohol ester (PEN), polybutylene terephthalate (PBT), polyarylate (PAR), polyimide (PI), polyamide (PA), polyimide (PAI), Polyetherimide (PEI), polyetheretherketone (PEEK), polyphenylene sulfide (PPS), etc.; the suitable material is formed of at least one of the aforementioned materials, and its melting point may be 200°C or above 250°C.
離型樹脂層12的厚度可因應其材料或期望的功能而作適當設定,例如可設定在4μm以上、50μm以下;而從凹凸契合性的觀點來看,也可將其設定在6μm以上、25μm以下。
The thickness of the
離型樹脂層12中與緩衝層13接觸的那一面,可因應需求施以表面處理,例如透過電暈放電處理、等離子處理、底劑塗裝等進行表面改質,藉此提高與緩衝層13的接合性。
The side of the
離型樹脂層12中與緩衝層13接觸面的相對面,亦能層疊其他合適的膜,或是層疊數層相同的離型樹脂層12。
The surface opposite to the contact surface of the
緩衝層13係為吸收物件凹凸不平之層面,由具有交聯結構的固化性樹脂構成;換言之,固化性樹脂係藉由固化而具備有交聯結構。在本發明中,緩衝層13係使用黏合劑,特別是黏彈性體具有耐熱性的耐熱黏合劑。黏合劑係使用彈性儲存率低,也就是硬度值小的黏合劑;舉例來說,以23℃(室温)、頻率10Hz、升溫速度5℃/min的條件進行測量時,固化後彈性儲存率為0.1MPa以上、10MPa以下。較佳者,於23℃(室温)的前述上限內,彈性儲存率為0.6MPa以上、6MPa以下;或以300℃測量時,彈性儲存率為0.012MPa以上、0.6MPa以下。
The
前述黏合劑所使用的樹脂中,具有有助於固化反應的官能基,例如羥基、巰基、羧基、氧雜環丁烷基、胺基、乙烯基等。 The resins used in the aforementioned adhesives have functional groups that contribute to the curing reaction, such as hydroxyl groups, mercapto groups, carboxyl groups, oxetanyl groups, amine groups, vinyl groups, and the like.
再者,其固化方式有異氰酸鹽類固化、環氧樹脂固化、三聚氰胺固化、金屬固化、噁唑啉固化、由熱與起始劑產生的自由基固化、紫外線與光起始劑產生的自由基固化或陽離子固化、電子線固化等。 Furthermore, its curing methods include isocyanate curing, epoxy resin curing, melamine curing, metal curing, oxazoline curing, free radical curing generated by heat and initiator, ultraviolet and photoinitiator. Radical curing or cation curing, electron beam curing, etc.
該黏合劑亦能因應需求添加單體,以補充物性之不足;且藉由此一添加,黏合劑即可配合使用目的而特製化。例如為了提高緩衝層13的黏合力,可添加玻璃轉化溫度低的單體;若考量耐熱性不足問題,則可添加玻璃轉化溫度高或多功能的單體。
The adhesive can also be added with monomers according to requirements to supplement the lack of physical properties; and by adding this, the adhesive can be customized for the purpose of use. For example, in order to improve the adhesive force of the
從緩衝性的觀點來看,緩衝層13的厚度以5μm以上、100μm以下為佳,若是25μm以上、50μm以下更佳。
From the viewpoint of buffering properties, the thickness of the
離型膜11的整體厚度能配合期望來設定,例如可設定在13μm~200μm左右;而最常用的離型膜11厚度,則是設定在25μm~75μm左右。
The overall thickness of the
雖然該厚度根據需求緩衝性、最佳緩衝性、或離型樹脂層12的性質等而有異,不過若假設離型膜11的整體厚度為100,緩衝層13的厚度可設定在例如20~75%左右。
Although the thickness varies depending on the required cushioning properties, optimum cushioning properties, or the properties of the
具有上述之離型樹脂層12和緩衝層13的離型膜11,其製造方法敘述如下。
The manufacturing method of the
於其中一層離型樹脂層12的一側面塗佈黏合劑,黏合劑乾燥後,於溫度5℃以上、200℃以下,將其與另一層離型樹脂層12貼合。
An adhesive is coated on one side of one
於塗佈黏合劑時,黏合劑的反應性樹脂化合物會稀釋為有機溶劑或水性溶劑。有機溶劑或水性溶劑中除了水之外,也可單獨使用或併用乙醇、正丙醇、異丙醇、正丁醇等的乙醇類、乙二醇甲醚、乙二醇乙醚、乙二醇單丁醚、丙二醇甲醚、丙二醇單丁醚等之烷二醇單烷基醚類等的乙醇類溶劑、甲苯和二甲苯等芳香烴類、乙酸乙酯和乙酸丁酯等的酸酯類、丁酮和甲基異丁酮等酮類。 When the adhesive is applied, the reactive resin compound of the adhesive is diluted into an organic solvent or an aqueous solvent. In the organic solvent or aqueous solvent, in addition to water, ethanols such as ethanol, n-propanol, isopropanol, n-butanol, ethylene glycol methyl ether, ethylene glycol ethyl ether, and ethylene glycol monoethyl ether can be used alone or in combination. Ethanol-based solvents such as alkanediol monoalkyl ethers such as butyl ether, propylene glycol methyl ether, propylene glycol monobutyl ether, etc., aromatic hydrocarbons such as toluene and xylene, esters of ethyl acetate and butyl acetate, etc. Ketones such as ketone and methyl isobutyl ketone.
塗佈作業可適當的採用以下方法:凹版塗佈、滾軸塗佈、逗號式塗佈、氣動刮刀塗佈、接觸塗佈、簾狀塗佈、旋轉塗佈、線棒塗佈等。 The following methods can be appropriately used for the coating operation: gravure coating, roll coating, comma coating, pneumatic blade coating, contact coating, curtain coating, spin coating, wire bar coating, and the like.
乾燥作業中會將黏合劑含有的溶劑揮發,雖然乾燥溫度會因使用的溶劑種類不同,但通常會設定在23℃以上、200℃以下,大部分則可設定在80℃以上、120℃以下。 During the drying operation, the solvent contained in the adhesive will volatilize. Although the drying temperature varies depending on the type of solvent used, it is usually set at 23°C or higher and 200°C or lower, and most can be set at 80°C or higher and 120°C or lower.
貼合係利用乾燥後黏合劑層的黏著力進行乾式貼合。 The lamination system uses the adhesive force of the adhesive layer after drying for dry lamination.
於此種塗佈、溶劑乾燥、貼合之按順序進行的生產流程中,塗佈在其中一層離型樹脂層12的黏合劑將進行固化作業。 In this sequential production process of coating, solvent drying, and lamination, the adhesive coated on one of the release resin layers 12 will be cured.
固化的操作與時間點會因固化方式而有所不同。若是異氰酸鹽固化,則會於貼合後的固化處理(時效處理)時進行。固化處理可例如用以下方式進行:在23~60℃的加溫狀態下靜置預定時間(例如24~168小時)。 The operation and time of curing will vary depending on the curing method. In the case of isocyanate curing, it will be performed at the time of curing treatment (aging treatment) after bonding. The curing treatment can be performed, for example, by leaving it to stand for a predetermined time (for example, 24 to 168 hours) in a heated state of 23 to 60°C.
若是環氧樹脂固化、三聚氰胺固化、金屬固化、噁唑啉固化、經由熱與起始劑產生的自由基固化,固化會與溶劑乾燥同時進行。若是紫外線固化、電子線固化,固化會在貼合之前或之後照射紫外線或電子線來進行。紫外線係用例如50~2000mJ/cm2照射,電子線係用例如10~300kGry照射。 In the case of epoxy curing, melamine curing, metal curing, oxazoline curing, free radical curing via heat and initiators, curing occurs simultaneously with solvent drying. In the case of ultraviolet curing and electron beam curing, curing is performed by irradiating ultraviolet rays or electron beams before or after bonding. The ultraviolet ray is irradiated with, for example, 50 to 2000 mJ/cm 2 , and the electron beam is irradiated with, for example, 10 to 300 kGry.
以上構造的離型膜11,將用來生產後述之印刷電路板。
The
圖2係表示離型膜11使用於生產軟性印刷電路板時的實施例。圖2(a)係使用單面銅箔基板(CCL)21a生產軟性印刷電路板的實施例;圖2(b)係使用雙面銅箔基板(CCL)21b生產軟性印刷電路板的實施例。圖2中的標號22係一覆蓋膜(CL)。如圖3所示,銅箔基板係用離型膜11上下覆蓋後再用加熱板23夾合,接著進行加熱與加壓沖壓成形。
FIG. 2 shows an example in which the
此時,由於位在離型膜11上下層的離型樹脂層12其構造態樣相同,所以離型膜11無表裏面之分,使用時可無需在意離型膜11的表裏面。
At this time, since the release resin layers 12 located on the upper and lower layers of the
加熱與加壓以預定的溫度及預定的時間進行,例如在150℃以上、300℃以下的溫度,15分以上、120分以下的時間進行;待其冷卻至常溫後再生產軟性印刷電路板。 Heating and pressing are carried out at a predetermined temperature and a predetermined time, for example, at a temperature above 150°C and below 300°C, for a time of 15 minutes or more and 120 minutes or less; after cooling to room temperature, the flexible printed circuit board is produced.
因為離型膜11的緩衝層13由粘彈性體形成,具有交聯結構而不具有熔點,因此即使以高溫進行加熱壓縮也能防止溶出,避免模具或製品因樹脂溶出而遭受汙染,同時亦能抑制不良發生。
Because the
再者,因緩衝層13是由彈性儲存率低的黏合劑固化後所形成,所以對於製品等的凹凸面仍可保有其契合性。特別是如果將聚醚醚酮(PEEK)用於離型樹脂層12,熔點即能高達334℃,不僅具有拉伸強度等高機械特性,耐熱性更加,因此能製作出高性能的離型膜11。
Furthermore, since the
另外,在先前技術中,離型膜和加熱板的接觸面會用紙或緩衝膜作為中介,但本發明中可省略此中介無妨。 In addition, in the prior art, the contact surface between the release film and the heating plate is made of paper or buffer film as an intermediary, but this intermediary can be omitted in the present invention.
以下將說明離型膜的其他實施例。 Other examples of the release film will be described below.
圖4係離型膜11另一實施例之剖面圖,該實施例中的緩衝層13為複數層疊。如圖所示,緩衝層13不限定為只有一層,亦能視加工的實際狀況作成複數層。
FIG. 4 is a cross-sectional view of another embodiment of the
圖5係離型膜11再一實施例之剖面圖,該實施例中離型樹脂層12的表面另有一離型塗層14。離型塗層14係由例如矽或氟等物質塗佈而成,可提高或補足離型樹脂層12之功能。
FIG. 5 is a cross-sectional view of another embodiment of the
圖6係離型膜11又一實施例之剖面圖,該實施例中其中一層的離型樹脂層12與緩衝層13之間具有一樹脂層15。該樹脂層15可配合使用條件,由具有離型性質或不具有離型性質的樹脂構成。
FIG. 6 is a cross-sectional view of another embodiment of the
採用圖6結構的離型膜11有以下優點:若離型樹脂層12所用的合成樹脂價格較高,例如聚醚醚酮(PEEK),即能減少該樹脂的使用量。
The use of the
圖7係離型膜11其他實施例之剖面圖,該實施例中離型膜11於兩樹脂層之間具有緩衝層。兩樹脂層中的其中一層係由熱塑性樹脂構成的離型樹脂層12,另外一層則是由不具有離型性質的樹脂層16構成。
FIG. 7 is a cross-sectional view of another embodiment of the
11:離型膜 11: Release film
12:離型樹脂層 12: Release resin layer
13:緩衝層 13: Buffer layer
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JP2020117999A JP7038430B2 (en) | 2020-07-08 | 2020-07-08 | Release film |
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JPWO2015133630A1 (en) * | 2014-03-07 | 2017-04-06 | 旭硝子株式会社 | Release film, method for producing the same, and method for producing semiconductor package |
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