TW201434609A - Release film - Google Patents

Release film Download PDF

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Publication number
TW201434609A
TW201434609A TW102136740A TW102136740A TW201434609A TW 201434609 A TW201434609 A TW 201434609A TW 102136740 A TW102136740 A TW 102136740A TW 102136740 A TW102136740 A TW 102136740A TW 201434609 A TW201434609 A TW 201434609A
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Taiwan
Prior art keywords
film
release film
layer
release
polybutylene terephthalate
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TW102136740A
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Chinese (zh)
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TWI609755B (en
Inventor
Yusuke Mishiro
Kenji Shima
Masaru Shimizu
Eiichi Taguchi
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Mitsui Chemicals Tohcello Inc
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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
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • 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
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • 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
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
    • 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
    • B32B7/04—Interconnection of layers
    • B32B7/06—Interconnection of layers permitting easy separation
    • 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
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/51—Elastic
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/538—Roughness
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/54—Yield strength; Tensile strength
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/748—Releasability
    • 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
    • B32B2457/00—Electrical equipment
    • B32B2457/08—PCBs, i.e. printed circuit boards
    • 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
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/06—Lamination
    • H05K2203/063—Lamination of preperforated insulating layer

Landscapes

  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Laminated Bodies (AREA)
  • Non-Metallic Protective Coatings For Printed Circuits (AREA)

Abstract

The present invention addresses the problem of obtaining a release film having excellent release properties, particularly self-release properties from a cover lay in a roll-to-roll step, and that has heat resistance and does not require application of a silicone-based release agent or the like. The present invention is a release film including a layer comprising polyethylene terephthalate (A) as a surface layer, and is characterized in that the surface roughness (Ra) thereof after the film has been placed over a polyimide film having a thickness of 50 μ m and hot-pressed for 10 minutes at a temperature of 180 DEG C and a pressure of 3 MPa is in the range of 0.1-10 μm.

Description

離型薄膜 Release film

本發明係關於使用接著劑將薄膜或片狀積層物施行加壓成形等之時，所使用較佳的剝離性優異離型薄膜，更詳言之，當在已形成電子機器、電氣機器所使用電氣迴路的撓性印刷佈線基板本體上，利用接著劑將覆蓋層施行加壓接著時，所使用的剝離性優異離型薄膜。 In the present invention, when a film or a sheet-like laminate is subjected to press molding or the like using an adhesive, a preferred release film having excellent releasability is used, and more specifically, when it has been formed into an electronic device or an electric machine. When the coating layer is pressurized by an adhesive on the flexible printed wiring board main body of the electric circuit, the release film is excellent in release properties.

在印刷佈線基板、撓性印刷佈線基板、多層印刷佈線基板等的製造步驟中，當隔著預浸體或耐熱薄膜，將貼銅積層板或銅箔施行熱壓合時係有使用離型薄膜。又，在撓性印刷基板的製造步驟中，當在已形成有電氣迴路的撓性印刷基板本體上，利用熱硬化型接著劑或熱硬化性接著片，對覆蓋層薄膜或補強板施行熱壓合接著時，為防止覆蓋層薄膜與壓合熱板發生接著，而使用離型薄膜。 In the manufacturing steps of a printed wiring board, a flexible printed wiring board, and a multilayer printed wiring board, when a copper-clad laminate or a copper foil is thermocompression-bonded via a prepreg or a heat-resistant film, a release film is used. . Further, in the manufacturing process of the flexible printed circuit board, the cover film or the reinforcing plate is subjected to hot pressing on the flexible printed circuit board body on which the electrical circuit has been formed by using a thermosetting adhesive or a thermosetting adhesive sheet. In order to prevent the cover film and the pressed hot plate from coming on, a release film is used.

作為該用途所使用的離型薄膜，提案有例如：由結晶性芳香族聚酯所構成的片材(專利文獻1：日本專利特開2004-2593號公報)、或對表面施行粗糙化之含聚對苯二甲酸丁二酯的離型薄膜(專利文獻2：日本專利特開2010-149520號公報)。 For the release film to be used for this purpose, for example, a sheet made of a crystalline aromatic polyester (Patent Document 1: Japanese Patent Laid-Open Publication No. 2004-2593) or a roughened surface is proposed. A release film of polybutylene terephthalate (Patent Document 2: JP-A-2010-149520).

然而，該等提案的離型薄膜並未具有能輕易剝離程度的充分離型性。例如在撓性印刷佈線基板中對覆蓋層薄膜施行加熱壓合的方式中，壓合方式係利用片式的批次壓合實施，當將已接著覆蓋層 的撓性印刷佈線基板、與離型薄膜予以剝離的操作係由人工進行時，即便多少有離型性差的情形，但藉由操作員的技巧仍不會導致離型薄膜破裂，且能在不致使配線基板發生起皺的情況下進行離型。然而，最近為提升生產性，施行壓合的方式採行自動化捲繞式方式的壓合步驟正逐漸增加，而該壓合方式係離型薄膜必需具有在有限時間內可從配線基板上自然離型程度的離型性，但該等離型薄膜大多有直到離型為止耗較長時間、且因機械性剝離而導致配線基板發生起皺的問題。 However, the release films of such proposals do not have sufficient release properties to the extent that they are easily peeled off. For example, in the manner in which the cover film is heat-pressed in a flexible printed wiring board, the press-fit method is carried out by batch-type lamination, when the cover layer is subsequently covered. When the operation of peeling off the flexible printed wiring board and the release film is performed manually, even if the mold release property is poor, the mold of the release film is not broken by the skill of the operator, and The wiring substrate is caused to be detached in the case of wrinkling. However, recently, in order to improve productivity, the press-fitting method of adopting the automatic winding type is gradually increasing, and the pressing method is required to have a release film which can be naturally separated from the wiring substrate in a limited time. Although the release film has a large degree of release property, the release film has a problem that it takes a long time until the release film and wrinkles the wiring substrate due to mechanical peeling.

再者，專利文獻2中，雖有記載具有含特定黏彈性模數(viscoelastic modulus)聚對苯二甲酸丁二酯之離型層的離型薄膜，離型性、外觀起皺、形狀追蹤性均良好，但因為緩衝層的樹脂係由乙烯‧甲基丙烯酸甲酯共聚合體、低密度聚乙烯的單層所構成，因而有緩衝層與表皮層的層間接著強度較弱之缺點。因層間接著強度較弱，例如在壓花成形時當離型薄膜從經加熱壓花輥上離型時，因為表皮層與壓花輥的密接較強，反而導致與緩衝層間之層間接著強度較弱，因而有表皮層與緩衝層出現剝離的問題。又，在為了減弱與壓花輥間之密接而降低壓花輥溫度的情況，會有無法獲得所需表面粗糙度、損及離型性或耐起皺性的問題。 Further, in Patent Document 2, a release film having a release layer containing a specific viscoelastic modulus polybutylene terephthalate is described, and the release property, appearance wrinkles, and shape traceability are described. All of them are good. However, since the resin of the buffer layer is composed of a single layer of a vinyl ‧ methyl methacrylate copolymer and a low-density polyethylene, there is a disadvantage that the interlayer adhesion strength between the buffer layer and the skin layer is weak. Because the interlayer bonding strength is weak, for example, when the release film is released from the heated embossing roll during embossing, because the adhesion between the skin layer and the embossing roll is stronger, the interlayer bonding strength between the layer and the buffer layer is rather It is weak, and thus there is a problem that the skin layer and the buffer layer are peeled off. Further, in order to reduce the temperature of the embossing roll by weakening the adhesion to the embossing roll, there is a problem that the desired surface roughness, the release property, or the crease resistance cannot be obtained.

[先前技術文獻] [Previous Technical Literature] [專利文獻] [Patent Literature]

專利文獻1：日本專利特開2004-2593號公報 Patent Document 1: Japanese Patent Laid-Open No. 2004-2593

專利文獻2：日本專利特開2010-149520號公報 Patent Document 2: Japanese Patent Laid-Open Publication No. 2010-149520

本發明目的在於獲得：離型性，特別係在捲繞式步驟中，從覆蓋層上的自然剝離性優異、且具有耐熱性、不需要塗佈聚矽氧系離型劑等的離型薄膜。 An object of the present invention is to obtain a release film, in particular, a release film which is excellent in natural peelability from a cover layer and which has heat resistance and which does not need to be coated with a polysiloxane release agent or the like in a winding step. .

本發明所提供的離型薄膜，係含有由聚對苯二甲酸丁二酯(A)所構成層的薄膜，其特徵在於：將該薄膜與50μm厚的聚醯亞胺薄膜相重疊，經依180℃、3MPa施行10分鐘壓合後的表面粗糙度Ra達0.1μm以上。 The release film provided by the present invention is a film containing a layer composed of polybutylene terephthalate (A), which is characterized in that the film is overlapped with a 50 μm thick polyimide film. The surface roughness Ra after press-bonding at 180 ° C and 3 MPa for 10 minutes was 0.1 μm or more.

上述壓合較佳係在該薄膜與聚醯亞胺薄膜的二外側，利用鋁板(厚度0.1mm)、作為緩衝材的報紙10張、SUS板(厚度1mm)夾置而實施。 The above-mentioned pressure bonding is preferably carried out on the outer side of the film and the polyimide film, and is carried out by sandwiching an aluminum plate (thickness: 0.1 mm), ten sheets of a newspaper as a cushioning material, and a SUS plate (thickness: 1 mm).

又，本發明之該薄膜在施行熱壓合前的表面粗糙度Ra較佳係1μm~10μm的範圍。 Further, the surface roughness Ra of the film of the present invention before the thermocompression bonding is preferably in the range of 1 μm to 10 μm.

再者，本發明的印刷佈線基板之製造方法，係包括有：在印刷佈線基板上所設置的保護膜與加壓板之間，介設上述任一離型薄膜，並施行加熱‧加壓而施行印刷佈線基板與保護膜的熱接著，經加熱‧加壓後，再將該離型薄膜從保護膜上予以剝離的步驟。 Further, in the method of manufacturing a printed wiring board according to the present invention, the release film is placed between the protective film and the pressure plate provided on the printed wiring board, and the release film is placed and heated. The heat of the printed wiring board and the protective film is then applied, and after heating and pressing, the release film is peeled off from the protective film.

本發明印刷佈線基板所使用的保護膜，較佳係聚醯亞胺薄膜。由聚醯亞胺薄膜與環氧樹脂系接著劑所構成的薄膜，係當作覆蓋層(覆蓋層薄膜)並使用於印刷佈線基板。在覆蓋層薄膜預先打穿出窗口，並利用後續的鍍敷步驟在印刷佈線基材的導線部僅對打穿部施行鍍敷。 The protective film used for the printed wiring board of the present invention is preferably a polyimide film. A film composed of a polyimide film and an epoxy resin-based adhesive is used as a cover layer (cover film) and used for a printed wiring board. The cover film is pre-punched through the window, and only the puncture portion is plated on the lead portion of the printed wiring substrate by a subsequent plating step.

本發明的離型薄膜因為例如經壓合後從覆蓋層上的自然剝離時間係未滿30秒的較短時間，特別係利用捲繞式方式進行的撓 性印刷佈線基板之製造步驟時之離型性優異，當機械性施行離型時不會產生起皺，且具有耐熱性及耐污染性，因而頗適用於使用環氧樹脂系接著劑的印刷佈線基板、撓性印刷佈線基板、多層印刷佈線基板等之製造。 The release film of the present invention is, for example, a short time of less than 30 seconds from the natural peeling time after lamination, especially in a winding manner. The printed wiring board is excellent in release property in the production step, and does not cause wrinkles when mechanically released, and has heat resistance and stain resistance, so that it is suitable for printed wiring using an epoxy-based adhesive. Manufacturing of a substrate, a flexible printed wiring board, a multilayer printed wiring board, or the like.

1‧‧‧離型薄膜 1‧‧‧ release film

2‧‧‧覆蓋層薄膜(保護膜) 2‧‧‧Overlay film (protective film)

2-1‧‧‧聚醯亞胺薄膜 2-1‧‧‧ Polyimine film

2-2‧‧‧環氧樹脂系接著劑層 2-2‧‧‧Epoxy resin adhesive layer

3‧‧‧印刷佈線基板 3‧‧‧Printed wiring substrate

4‧‧‧窗口部 4‧‧‧ Window Department

圖1係表示使用本發明離型薄膜，在印刷佈線基材上，保護膜加熱壓接狀態的剖視圖。 Fig. 1 is a cross-sectional view showing a state in which a protective film is heated and crimped on a printed wiring substrate by using the release film of the present invention.

<聚對苯二甲酸丁二酯(A)> <polybutylene terephthalate (A)>

構成本發明離型薄膜的聚對苯二甲酸丁二酯(A)，係在骨架上具有1,4-丁二醇與對酞酸的聚合體之前提下，可為由1,4-丁二醇與對酞酸構成所謂通稱「PBT」的聚對苯二甲酸丁二酯，亦可為聚對苯二甲酸丁二酯、與聚醚、聚酯或聚己內醯胺等的嵌段共聚合體。 The polybutylene terephthalate (A) constituting the release film of the present invention is obtained by a polymer having 1,4-butanediol and p-citric acid on the skeleton, and may be 1,4-butyl The diol and the citric acid constitute a so-called "PBT" polybutylene terephthalate, and may also be a block of polybutylene terephthalate, polyether, polyester or polycaprolactam. Copolymer.

本發明的聚對苯二甲酸丁二酯(A)較佳係使用在減壓下或惰性氣體流通下，依200℃以上溫度進行固相聚合的原料。藉由固相聚合，便可調整為較容易薄膜成形的固有黏度，更可期待減少末端羧酸基量、及減少寡聚物。聚對苯二甲酸丁二酯(A)的固有黏度(IV)較佳係1.0~1.3。 The polybutylene terephthalate (A) of the present invention is preferably a raw material which is subjected to solid phase polymerization at a temperature of 200 ° C or higher under reduced pressure or under an inert gas flow. By solid phase polymerization, the intrinsic viscosity of the film formation can be adjusted, and the amount of the terminal carboxylic acid group can be reduced and the oligomer can be reduced. The intrinsic viscosity (IV) of polybutylene terephthalate (A) is preferably from 1.0 to 1.3.

本發明的聚對苯二甲酸丁二酯(A)係有例如由三菱工程塑膠公司依商品名NOVADURAN® 5010CS、NOVADURAN® 5020製造‧販售。 The polybutylene terephthalate (A) of the present invention is sold, for example, by Mitsubishi Engineering Plastics Co., Ltd. under the trade names of NOVADURAN® 5010CS and NOVADURAN® 5020.

本發明聚對苯二甲酸丁二酯(A)的熔點，係使用示差掃描型熱量計(DSC)依300℃施行5分鐘加熱熔融後，利用液態氮急冷而獲 得的樣品10mg，在氮氣流中，依10℃/分的升溫速度測定生熱‧吸熱曲線時，將因熔解而衍生的吸熱尖峰之頂點溫度設為熔點(Tm)(℃)。 The melting point of the polybutylene terephthalate (A) of the present invention is obtained by heating and melting at 300 ° C for 5 minutes using a differential scanning calorimeter (DSC), and then quenching with liquid nitrogen. 10 mg of the obtained sample was measured for the heat generation and the endothermic curve at a temperature elevation rate of 10 ° C /min in a nitrogen stream, and the peak temperature of the endothermic peak derived by the melting was set to a melting point (Tm) (° C.).

本發明的聚對苯二甲酸丁二酯(A)中，在不致損及本發明 目的之範圍內，亦可摻合慣用的添加劑等。該添加劑並無特別的限制，例如：抗氧化劑、耐熱安定劑等安定劑，此外尚可列舉：滑劑、紫外線吸收劑、觸媒去活化劑、結晶造核劑等。該等添加劑係可在聚合途中或聚合後添加。又，在本發明的聚對苯二甲酸丁二酯(A)中，為賦予所需性能，亦可摻合：難燃劑、染顏料等著色劑；抗靜電劑、發泡劑、可塑劑、耐衝擊性改良劑等。 In the polybutylene terephthalate (A) of the present invention, the present invention is not impaired Within the scope of the purpose, it is also possible to blend conventional additives and the like. The additive is not particularly limited, and examples thereof include stabilizers such as antioxidants and heat stabilizers, and examples thereof include slip agents, ultraviolet absorbers, catalyst deactivators, and crystal nucleating agents. These additives can be added during or after the polymerization. Further, in the polybutylene terephthalate (A) of the present invention, in order to impart desired properties, it is also possible to blend: a coloring agent such as a flame retardant or a dye; an antistatic agent, a foaming agent, and a plasticizer. , impact resistance improver, etc.

安定劑係可列舉：2,6-二-第三丁基-4-辛基酚、季戊四醇 -四[3-(3',5'-第三丁基-4'-羥苯基)丙酸酯]等酚化合物；3,3'-硫代二丙酸二月桂酯、季戊四醇-四(3-月桂基硫代二丙酸酯)等硫醚化合物；亞磷酸三苯酯、三(壬基苯基)亞磷酸酯、三(2,4-二第三丁基苯基)亞磷酸酯等磷化合物等抗氧化劑；滑劑係可列舉：石蠟、微晶蠟、聚乙烯蠟、褐煤酸、褐煤酸酯所代表的長鏈脂肪酸及其酯等。 The stabilizer can be exemplified by 2,6-di-tert-butyl-4-octylphenol and pentaerythritol. a phenolic compound such as tetrakis[3-(3',5'-t-butyl-4'-hydroxyphenyl)propionate]; 3,3'-dilaurate of dithiodipropionate, pentaerythritol-tetra ( a thioether compound such as 3-lauryl thiodipropionate; triphenyl phosphite, tris(nonylphenyl) phosphite, tris(2,4-di-t-butylphenyl) phosphite An antioxidant such as a phosphorus compound; and a slip agent may, for example, be a long-chain fatty acid represented by paraffin wax, microcrystalline wax, polyethylene wax, montanic acid or montanic acid ester, or an ester thereof.

結晶核劑係可列舉：脂肪族酯、脂肪族醯胺、脂肪酸金 屬鹽等。脂肪族酯係可列舉：硬脂酸單甘油酯、廿二酸單甘油酯等脂肪酸酯；12-羥基硬脂酸三酸甘油酯等羥基脂肪酸酯。脂肪族醯胺係可列舉：12-羥基硬脂酸單乙醇醯胺等羥基脂肪酸單醯胺；乙烯雙月桂酸醯胺、乙烯雙癸酸醯胺、乙烯雙辛酸醯胺等脂肪族雙醯胺；乙烯雙12-羥基硬脂酸醯胺、六亞甲基雙12-羥基硬脂酸醯胺等羥基脂肪酸雙醯胺。脂肪酸金屬鹽係可列舉：12-羥基硬脂酸鈣等羥基脂肪酸金屬鹽等。從結晶化速度、耐熱性、感溫性、以及透明性的觀點，較佳係12-羥基硬脂酸三酸甘油酯、廿二酸單甘油酯、乙烯雙12-羥基硬脂酸醯 胺、六亞甲基雙12-羥基硬脂酸醯胺、12-羥基硬脂酸單乙醇醯胺、乙烯雙辛酸醯胺、乙烯雙癸酸醯胺，更佳係12-羥基硬脂酸三酸甘油酯、乙烯雙12-羥基硬脂酸醯胺、六亞甲基雙12-羥基硬脂酸醯胺、12-羥基硬脂酸單乙醇醯胺，特佳係12-羥基硬脂酸三酸甘油酯、乙烯雙12-羥基硬脂酸醯胺、六亞甲基雙12-羥基硬脂酸醯胺，最佳係乙烯雙12-羥基硬脂酸醯胺、六亞甲基雙12-羥基硬脂酸醯胺。 The crystal nucleating agent system can be exemplified by aliphatic esters, aliphatic guanamines, and fatty acid gold. Is a salt and so on. Examples of the aliphatic esters include fatty acid esters such as stearic acid monoglyceride and sebacic acid monoglyceride; and hydroxy fatty acid esters such as 12-hydroxystearic acid triglyceride. Examples of the aliphatic amides include hydroxy fatty acid monodecylamines such as 12-hydroxystearic acid monoethanol decylamine; aliphatic bis-amines such as ethylene laurate decylamine, ethylene bismuth decyl amide, and ethylene bis decanoate; A hydroxy fatty acid bis-guanamine such as ethylenebis 12-hydroxystearic acid decylamine or hexamethylenebis 12-hydroxystearic acid decylamine. Examples of the fatty acid metal salt include a hydroxy fatty acid metal salt such as calcium 12-hydroxystearate. From the viewpoints of crystallization rate, heat resistance, temperature sensitivity, and transparency, 12-hydroxystearic acid triglyceride, sebacic acid monoglyceride, and ethylenebis 12-hydroxystearic acid strontium are preferred. Amine, hexamethylenebis 12-hydroxystearic acid decylamine, 12-hydroxystearic acid monoethanol decylamine, ethylene bis-caprylate decylamine, ethylene bismuth decanoate, more preferably 12-hydroxystearic acid Acid glyceride, ethylene bis- 12-hydroxystearic acid decylamine, hexamethylene bis 12-hydroxystearic acid decylamine, 12-hydroxystearic acid monoethanol decylamine, especially good 12-hydroxystearic acid three Acid glyceride, ethylene bis- 12-hydroxystearic acid decylamine, hexamethylene bis 12-hydroxystearic acid decylamine, optimal ethylene double 12-hydroxystearic acid decylamine, hexamethylene double 12- Guanylamine hydroxystearate.

難燃劑係可列舉例如：有機鹵化合物、銻化合物、磷化 合物、其他的有機難燃劑、無機難燃劑等。有機鹵化合物係可列舉例如：溴化聚碳酸酯、溴化環氧樹脂、溴化苯氧樹脂、溴化聚苯醚樹脂、溴化聚苯乙烯樹脂、溴化雙酚A、聚丙烯酸五溴苄酯等。銻化合物係可列舉例如：三氧化銻、五氧化銻、銻酸鈉等。磷化合物係可列舉例如：磷酸酯、聚磷酸、聚磷酸銨、紅磷等。其他的有機難燃劑係可列舉例如：三聚氰胺、三聚氰酸等氮化合物等。其他的無機難燃劑係可列舉例如：氫氧化鋁、氫氧化鎂、矽化合物、硼化合物等。 Examples of the flame retardant include an organic halogen compound, a ruthenium compound, and phosphating. Compound, other organic flame retardant, inorganic flame retardant, and the like. Examples of the organic halogen compound include brominated polycarbonate, brominated epoxy resin, brominated phenoxy resin, brominated polyphenylene ether resin, brominated polystyrene resin, brominated bisphenol A, and polybrominated pentabromine. Benzyl ester and the like. Examples of the ruthenium compound include antimony trioxide, antimony pentoxide, sodium citrate, and the like. Examples of the phosphorus compound include a phosphate ester, a polyphosphoric acid, ammonium polyphosphate, and red phosphorus. Examples of other organic flame retardants include nitrogen compounds such as melamine and cyanuric acid. Examples of other inorganic flame retardants include aluminum hydroxide, magnesium hydroxide, barium compounds, and boron compounds.

在本發明的聚對苯二甲酸丁二酯(A)中，於不致損及本發 明目的之範圍內，亦可摻合強化填充材。強化填充材並無特別的限制，可列舉例如：板狀無機填充材、陶瓷珠、石綿、矽灰石、滑石、黏土、雲母、沸石、高嶺土、鈦酸鉀、硫酸鋇、氧化鈦、氧化矽、氧化鋁、氫氧化鎂、或玻璃纖維、碳纖維、二氧化矽‧氧化鋁纖維、二氧化鋯纖維、硼纖維、氮化硼纖維、氮化矽鈦酸鉀纖維、金屬纖維等無機纖維；芳香族聚醯胺纖維、氟樹脂纖維等有機纖維等。該等強化填充材係可組合2種以上而使用。上述強化填充材中較佳係使用無機填充材，特別係玻璃纖維。 In the polybutylene terephthalate (A) of the present invention, it does not damage the hair In the range of the purpose of the purpose, the reinforcing filler material may also be blended. The reinforcing filler is not particularly limited, and examples thereof include a plate-shaped inorganic filler, ceramic beads, asbestos, ash, talc, clay, mica, zeolite, kaolin, potassium titanate, barium sulfate, titanium oxide, and cerium oxide. , alumina, magnesium hydroxide, or glass fiber, carbon fiber, cerium oxide ‧ alumina fiber, zirconia fiber, boron fiber, boron nitride fiber, barium strontium titanate potassium fiber, metal fiber and other inorganic fibers; An organic fiber such as a polyamide fiber or a fluororesin fiber. These reinforcing fillers can be used in combination of two or more kinds. It is preferable to use an inorganic filler, especially a glass fiber, in the above-mentioned reinforced filler.

強化填充材在為了提升與聚對苯二甲酸丁二酯(A)間之 界面密接性的前提下，較佳係利用上漿劑或表面處理劑施行表面處理後才使用。上漿劑或表面處理劑係可列舉例如：環氧系化合物、丙烯酸系化合物、異氰酸酯系化合物、矽烷系化合物、鈦酸酯系化合物等官能性化合物。強化填充材係可預先利用上漿劑或表面處理劑施行表面處理，或者亦可在調製聚對苯二甲酸丁二酯(A)的組成物時，添加上漿劑或表面處理劑施行表面處理。強化填充材的添加量係相對於聚對苯二甲酸丁二酯(A)100質量份，通常在150質量份以下、較佳係1~50質量份的範圍。 Reinforced filler material in order to improve between polybutylene terephthalate (A) On the premise of interface adhesion, it is preferably used after surface treatment with a sizing agent or a surface treatment agent. Examples of the sizing agent or the surface treatment agent include functional compounds such as an epoxy compound, an acrylic compound, an isocyanate compound, a decane compound, and a titanate compound. The reinforced filler material may be subjected to a surface treatment by using a sizing agent or a surface treatment agent in advance, or may be subjected to a surface treatment by adding a sizing agent or a surface treatment agent when preparing the composition of the polybutylene terephthalate (A). . The amount of the reinforcing filler added is usually 150 parts by mass or less, preferably 1 to 50 parts by mass, per 100 parts by mass of the polybutylene terephthalate (A).

在本發明的聚對苯二甲酸丁二酯(A)中，視需要亦可摻 合：聚乙烯、聚丙烯、聚甲基戊烯、聚苯乙烯、聚丙烯腈、聚甲基丙烯酸酯、ABS樹脂、聚碳酸酯、聚醯胺、聚苯硫醚、聚對苯二甲酸乙二酯、液晶聚酯、聚縮醛、聚苯醚等熱可塑性樹脂；酚樹脂、三聚氰胺樹脂、聚矽氧樹脂、環氧樹脂等熱硬化性樹脂。該等熱可塑性樹脂及熱硬化性樹脂係可組合2種以上而使用。 In the polybutylene terephthalate (A) of the present invention, it may be blended as needed Combination: polyethylene, polypropylene, polymethylpentene, polystyrene, polyacrylonitrile, polymethacrylate, ABS resin, polycarbonate, polyamine, polyphenylene sulfide, polyethylene terephthalate A thermoplastic resin such as a diester, a liquid crystal polyester, a polyacetal or a polyphenylene ether; a thermosetting resin such as a phenol resin, a melamine resin, a polyoxyxylene resin or an epoxy resin. These thermoplastic resins and thermosetting resins may be used in combination of two or more kinds.

本發明的聚對苯二甲酸丁二酯(A)中，若更進一步相對於 聚對苯二甲酸丁二酯(A)100質量份，含有核劑(B)較佳係3質量份以下、更佳係0.01~0.5質量份、特佳係0.05~0.3質量份，便可獲得剝離性更優異的剝離薄膜。 In the polybutylene terephthalate (A) of the present invention, if it is further 100 parts by mass of polybutylene terephthalate (A), preferably containing 3 parts by mass or less, more preferably 0.01 to 0.5 parts by mass, and particularly preferably 0.05 to 0.3 parts by mass of the nucleating agent (B). A release film which is more excellent in peelability.

在本發明的聚對苯二甲酸丁二酯(A)中摻合使用的核劑(B)，就該等核劑中較佳係：雙(4-甲基苯亞甲基)山梨糖醇、2,2'-亞甲基雙(4,6-二第三丁基苯基)磷酸鈉鹽、硬脂酸鎂、乙烯‧雙硬脂酸醯胺等。 In the polybutylene terephthalate (A) of the present invention, the nucleating agent (B) is blended, and among these nucleating agents, bis(4-methylbenzylidene) sorbitol is preferred. 2,2'-methylenebis(4,6-di-t-butylphenyl)phosphate sodium salt, magnesium stearate, ethylene bis bis-stearate, and the like.

<離型薄膜> <release film>

本發明的離型薄膜係由上述聚對苯二甲酸丁二酯(A)所構成的薄 膜。 The release film of the present invention is thinly composed of the above polybutylene terephthalate (A) membrane.

本發明的離型薄膜係在設有由上述聚對苯二甲酸丁二酯(A)所構成的層之前提下，亦可積層其他的層。 The release film of the present invention is provided before the layer composed of the above polybutylene terephthalate (A) is provided, and other layers may be laminated.

當本發明的離型薄膜係使用積層薄膜時，至少單面，即由聚對苯二甲酸丁二酯(A)所構成的層必需成為離型層，即與環氧樹脂系接著劑等接著劑的接合面。 When the release film of the present invention is a laminate film, at least one side, that is, a layer composed of polybutylene terephthalate (A) must be a release layer, that is, an epoxy resin-based adhesive or the like. The joint surface of the agent.

使用本發明的離型薄膜時，可均勻地施加加熱壓合的壓 力，亦可經與能追蹤印刷佈線之凹凸的其他層進行積層後才使用。此種緩衝性優異的其他層(雙層的情況便為背面層，3層以上的情況便為屬於內層的核心層)，具體而言，較佳係含有依50℃至150℃、較佳係70℃至120℃的範圍會軟化樹脂的薄膜，具體而言，低密度聚乙烯、聚丙烯、乙烯‧甲基丙烯酸甲酯共聚合體、乙烯‧醋酸乙烯酯共聚合體、乙烯‧丙烯共聚合體、乙烯‧丁烯共聚合體、丙烯‧丁烯共聚合體等聚烯烴樹脂，該等可單獨使用、亦可併用2種以上。 When the release film of the present invention is used, the pressure of the heat pressing can be uniformly applied The force can also be used after laminating with other layers that can track the unevenness of the printed wiring. Such a layer having excellent cushioning properties (the case of a double layer is a back layer, and the case of three or more layers is a core layer belonging to the inner layer), and specifically, it is preferably 50 ° C to 150 ° C, preferably. A range of 70 ° C to 120 ° C softens the film of the resin, specifically, low density polyethylene, polypropylene, ethylene ‧ methyl methacrylate copolymer, ethylene ‧ vinyl acetate copolymer, ethylene ‧ propylene copolymer, A polyolefin resin such as an ethylene/butene copolymer or a propylene/butene copolymer may be used singly or in combination of two or more kinds.

亦可利用將本發明離型薄膜與緩衝層共擠出成形而進 行多層化。於此情況下，例如使用由3台擠出機所構成的3層T模頭薄膜成形機，便可成形由本發明以聚對苯二甲酸丁二酯(A)所構成的離型層為外層、且以低密度聚乙烯層為內層的二種三層薄膜。又，上述低密度聚乙烯，改為使用經酸改質過的聚乙烯，例如乙烯‧甲基丙烯酸甲酯共聚合體，或者以提升與離型層間之層間接著強度為目的，亦可將乙烯‧甲基丙烯酸甲酯共聚合體與聚對苯二甲酸丁二酯(A)的組成物使用於內層。此情況的組成，較佳係以乙烯‧甲基丙烯酸甲酯共聚合體為主成分構成基質，乙烯‧甲基丙烯酸甲酯共聚合體為50至95質量%、聚對苯二甲酸丁二酯(A)為5至50質量%，較佳係乙烯‧甲基 丙烯酸甲酯共聚合體為50至80質量%、聚對苯二甲酸丁二酯(A)較佳係20至50質量%。又，為了更進一步提升層間接著強度，亦可在離型層與緩衝層之間設置接著層。若在此範圍內，即便施行高溫的壓花成形時，仍可在表皮層與緩衝層不發生層間剝離的情況下成形。又，在印刷佈線基板黏貼覆蓋層並壓合後進行離型時，表皮層與緩衝層亦可不發生層間剝離而良好地離型。 It is also possible to coextrud and form the release film of the present invention and the buffer layer. Multi-layered. In this case, for example, a three-layer T-die film forming machine composed of three extruders can be used to form the release layer composed of polybutylene terephthalate (A) of the present invention as an outer layer. And two low-density polyethylene layers as the inner layer of the two three-layer film. Further, the low-density polyethylene may be replaced by an acid-modified polyethylene such as ethylene/methyl methacrylate copolymer, or for the purpose of enhancing the interlayer adhesion between the release layer and the release layer. A composition of a methyl methacrylate copolymer and polybutylene terephthalate (A) is used for the inner layer. In this case, the composition is preferably composed of a vinyl ‧ methyl methacrylate copolymer as a main component, and the ethylene ‧ methyl methacrylate copolymer is 50 to 95% by mass of polybutylene terephthalate (A). ) is 5 to 50% by mass, preferably ethylene ‧ methyl The methyl acrylate copolymer is 50 to 80% by mass, and the polybutylene terephthalate (A) is preferably 20 to 50% by mass. Moreover, in order to further improve the interlayer adhesion strength, an adhesion layer may be provided between the release layer and the buffer layer. Within this range, even when high-temperature embossing is applied, the skin layer and the buffer layer can be formed without peeling between layers. Further, when the printed wiring board is adhered to the cover layer and pressed, and then released, the skin layer and the buffer layer can be favorably released without delamination.

<離型薄膜之製造方法> <Method for Producing Release Film>

本發明的離型薄膜係可利用各種公知的薄膜成形方法進行製造。例如當製造由上述聚對苯二甲酸丁二酯(A)所構成的單層薄膜時，利用T型模頭薄膜成形、充氣薄膜成形等成形方法便可製造。 The release film of the present invention can be produced by various known film forming methods. For example, when a single-layer film composed of the above-mentioned polybutylene terephthalate (A) is produced, it can be produced by a molding method such as T-die film formation or inflation film molding.

再者，當本發明的離型薄膜係製造積層薄膜時，使用多層T型模頭或多層環狀模頭，利用共擠出成形便可製造。其他尚可使用擠出層壓法、乾式層壓法等公知的層壓方法。 Further, when the release film of the present invention is used to produce a laminated film, it can be produced by co-extrusion molding using a multilayer T-die or a multilayer annular die. Other known lamination methods such as an extrusion lamination method and a dry lamination method can be used.

其中，使用多層T型模頭進行的共擠出成形法，就能使各層膜厚呈均勻、且可寬廣化的觀點係屬較優異。又，經製造寬廣的積層體後，由於配合多種多樣FPC的寬度而可輕易地窄寬化為所需寬度，因而頗適用為FPC製造用離型薄膜的製造方法。 Among them, the coextrusion molding method using a multilayer T-die is superior in that the film thickness of each layer is uniform and wide. Further, since a wide laminated body is produced and can be easily narrowed to a desired width by blending a wide variety of FPCs, it is suitable as a method for producing a release film for FPC production.

再者，本發明的離型薄膜較佳係由上述聚對苯二甲酸丁 二酯(A)所構成層的薄膜表面之至少其中一面，經施行壓花處理。而，經壓合後的薄膜表面層根據JIS B 0601的表面粗糙度Ra，係0.3~10μm、較佳係0.5~10μm、更佳係1~5μm、特佳係1.5μm~4μm的範圍。若該薄膜表面層的表面粗糙度在上述範圍內，便可獲得良好的離型性。為能獲得此種表面粗糙度，可利用加熱壓花輥的溫度進行控 制，加熱壓花輥溫度較理想係在150~200℃溫度範圍實施。若超過200℃，薄膜會過度軟化，導致對壓花輥的密接變得過強，較難從壓花輥上離型。又，若為了施行離型而提升薄膜的張力等，因薄膜的加熱尺寸變化率會導致MD出現大幅收縮，導致作為離型薄膜使用時的操作性變差。若壓花輥溫度未滿150℃，經壓合後的表面粗糙度會變小，造成FPC製造時的離型不足。壓花輥的花紋係可為圓形、方形等規則性花紋，亦可為噴砂等不規則花紋，並無特別的限制，就經加熱過薄膜的平滑性佳之觀點而言，較佳係通用的噴砂花紋。壓花輥的表面粗糙度Ra係1~20μm、較佳係2~15μm、更佳係3~10μm的範圍。針對壓花輥的表面粗糙度，藉由適當選擇加熱壓花輥溫度，便可控制從壓花輥對薄膜的壓花轉印率。又，利用壓花輥線壓亦可控制壓花轉印率，較佳的線壓係20~150kg/cm、更佳的線壓係50~100kg/cm。 Furthermore, the release film of the present invention is preferably composed of the above polybutylene terephthalate. At least one of the surfaces of the film of the layer composed of the diester (A) is subjected to embossing treatment. Further, the surface layer of the film after press-bonding is in the range of 0.3 to 10 μm, preferably 0.5 to 10 μm, more preferably 1 to 5 μm, and particularly preferably 1.5 to 4 μm, in accordance with the surface roughness Ra of JIS B 0601. If the surface roughness of the surface layer of the film is within the above range, good release property can be obtained. In order to obtain such surface roughness, the temperature of the heated embossing roll can be used for control. The temperature of the heated embossing roll is preferably in the range of 150 to 200 ° C. If it exceeds 200 ° C, the film will be excessively softened, resulting in an excessively strong adhesion to the embossing roll, which makes it difficult to release from the embossing roll. In addition, when the tension of the film is increased in order to perform the release, the rate of change in the heating dimensional change of the film causes a large shrinkage of the MD, and the workability when used as a release film is deteriorated. If the embossing roll temperature is less than 150 ° C, the surface roughness after pressing will become small, resulting in insufficient release of the FPC during manufacture. The pattern of the embossing roll may be a regular pattern such as a circular shape or a square shape, or may be an irregular pattern such as sand blasting, and is not particularly limited, and is preferably a general-purpose one in terms of the smoothness of the heated film. Sandblasted pattern. The surface roughness Ra of the embossing roll is in the range of 1 to 20 μm, preferably 2 to 15 μm, more preferably 3 to 10 μm. For the surface roughness of the embossing roll, the embossing transfer rate from the embossing roll to the film can be controlled by appropriately selecting the temperature of the heated embossing roll. Further, the embossing transfer rate can be controlled by the embossing roll line pressure, and a preferred line pressure system is 20 to 150 kg/cm, and a more preferable line pressure system is 50 to 100 kg/cm.

再者，本發明的離型薄膜，根據JIS K 7127在溫度23 ℃下的拉伸彈性模數較佳係600~2000MPa、更佳係600~1500MPa、特佳係600~1200MPa。若在此範圍的拉伸彈性模數，則能在不致使以捲繞式方式的輥搬送性或配線基板的精密配線出現斷線的情況下進行壓合。 Furthermore, the release film of the present invention is at a temperature of 23 according to JIS K 7127. The tensile modulus of elasticity at ° C is preferably 600 to 2000 MPa, more preferably 600 to 1500 MPa, and particularly preferably 600 to 1200 MPa. When the tensile modulus of elasticity is within this range, it is possible to perform press-bonding without causing the roll-type transfer property or the wire of the wiring board to be broken.

[離型薄膜之用途] [Use of release film]

本發明的離型薄膜係耐熱性與離型性均優異，頗適於使用為離型薄膜。具體而言，係可列舉：FPC製造用離型薄膜、飛機零件所使用的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、LED透鏡成形用離型薄膜、FRP成形用離型薄膜、橡膠片硬化用離型薄膜、特殊黏貼帶用離型薄膜。該等之中，本發明的 離型薄膜較佳係可使用為FPC製造用離型薄膜。 The release film of the present invention is excellent in heat resistance and release property, and is suitably used as a release film. Specifically, the release film for FPC production, the release film for ACM materials used for aircraft parts, the release film for producing a rigid printed circuit board, the release film for semiconductor sealing materials, and the release film for LED lens formation are mentioned. Film, release film for FRP molding, release film for rubber sheet curing, release film for special adhesive tape. Among these, the present invention The release film is preferably used as a release film for FPC production.

本發明的離型薄膜係若將依照上述所記載製造方法獲得的薄膜，更進一步施行加熱處理便可提升離型性，故屬較佳。 The release film of the present invention is preferred because the film obtained by the above-described production method is further subjected to heat treatment to improve the release property.

加熱條件較佳係大氣中、加熱溫度100~200℃，更佳係150℃~190℃。加熱時間係只要依照加熱方法再決定適當條件便可。 The heating condition is preferably in the atmosphere, the heating temperature is 100 to 200 ° C, and more preferably 150 ° C to 190 ° C. The heating time is determined by determining the appropriate conditions in accordance with the heating method.

對本發明離型薄膜施行加熱處理的方法係可為各種公知方法，具體而言，係可例示：使利用T型模頭施行成形而獲得的捲筒狀離型薄膜，利用捲繞式通過經加熱過熱風烤箱的方法；或者在利用捲繞式通過的線上，設置IR加熱器等加熱器而加熱離型薄膜的方法；或者將捲筒狀離型薄膜裁切為片狀後，再利用熱風烤箱施行加熱處理的方法；或者將利用T型模頭所成形的捲筒狀離型薄膜，利用捲繞式使接觸於經加熱過輥的方法等。 The method of heat-treating the release film of the present invention may be various known methods, and specifically, a roll-shaped release film obtained by molding using a T-die can be exemplified by heating by a winding type. a method of superheating an air oven; or a method of heating a release film by using a heater such as an IR heater on a wire passing through a winding type; or cutting a roll-shaped release film into a sheet shape, and then using a hot air oven A method of performing a heat treatment; or a method of bringing a roll-shaped release film formed by a T-die into contact with a heated roll by a winding type.

對離型薄膜施行加熱的熱源並無特別的限定，較佳係遠紅外線加熱器、短波長紅外線加熱器、中波長紅外線加熱器、碳製加熱器(carbon heater)等。 The heat source for heating the release film is not particularly limited, and is preferably a far-infrared heater, a short-wavelength infrared heater, a medium-wavelength infrared heater, a carbon heater or the like.

其中，使利用T型模頭所成形的捲筒狀離型薄膜，利用捲繞式接觸於經加熱過輥的方法，由於離型薄膜直接接觸到經加熱過輥，因而離型薄膜表面的熱傳導較快，所以加熱處理時間只要較短時間便可，故生產性較高。 Wherein, the roll-shaped release film formed by the T-die is brought into contact with the heated roll by the method of winding contact, since the release film directly contacts the heated roll, the heat conduction on the surface of the release film It is faster, so the heat treatment time can be as short as possible, so the productivity is high.

[實施例] [Examples] [實施例1~9及比較例1~8] [Examples 1 to 9 and Comparative Examples 1 to 8]

以下，針對本發明利用實施例進行更詳細說明，惟本發明在不逾越其主旨的前提下，並不僅侷限於以下的實施例。所使用的樹脂組成 物等係如下。 Hereinafter, the present invention will be described in more detail with reference to the embodiments, but the present invention is not limited to the following examples without departing from the spirit thereof. Resin composition used The items are as follows.

本發明實施例及比較例所使用的聚對苯二甲酸丁二酯係如下示。 The polybutylene terephthalate used in the examples and comparative examples of the present invention is as follows.

1.使用樹脂 Use resin

(1)聚對苯二甲酸丁二酯(單聚物) (1) Polybutylene terephthalate (monomer)

(A-1)Tm=224℃、IV=1.1、[三菱工程塑膠(股)製、商品名：NOVADURAN® 5010CS] (A-1) Tm = 224 ° C, IV = 1.1, [Mitsubishi Engineering Plastics Co., Ltd., trade name: NOVADURAN® 5010CS]

(A-2)Tm=224℃、IV=1.2、[三菱工程塑膠(股)製、商品名：NOVADURAN® 5020] (A-2) Tm = 224 ° C, IV = 1.2, [Mitsubishi Engineering Plastics Co., Ltd., trade name: NOVADURAN® 5020]

(2)聚對苯二甲酸丁二酯與聚四亞甲基二醇的共聚合體 (2) a copolymer of polybutylene terephthalate and polytetramethylene glycol

(A-3)Tm=222℃、IV=1.2、[三菱工程塑膠(股)製、商品名：NOVADURAN® 5505S] (A-3) Tm = 222 ° C, IV = 1.2, [Mitsubishi Engineering Plastics Co., Ltd., trade name: NOVADURAN® 5505S]

(3)乙烯‧甲基丙烯酸甲酯共聚合體(EMMA)Tm=100℃、MMA含量=10wt%、[住友化學(股)、商品名：ACRYFT® WD201-F] (3) Ethylene ‧ methyl methacrylate copolymer (EMMA) Tm = 100 ° C, MMA content = 10 wt%, [Sumitomo Chemical Co., Ltd., trade name: ACRYFT® WD201-F]

2.結晶核劑 2. Crystalline nucleating agent

(B-1)雙(4-甲基苯亞甲基)山梨糖醇、Tm=260℃[新日本理化(股)製、商品名：GEL ALL MD] (B-1) bis(4-methylbenzylidene) sorbitol, Tm = 260 ° C [Nippon Chemical and Chemical Co., Ltd., trade name: GEL ALL MD]

(B-2)雙(4-甲基苯亞甲基)山梨糖醇、Tm=200℃[新日本理化(股)製、商品名：GEL ALL E-200] (B-2) bis(4-methylbenzylidene) sorbitol, Tm = 200 ° C [Nippon Chemical and Chemical Co., Ltd., trade name: GEL ALL E-200]

<結晶核劑母料之製作方法、及離型薄膜製作方法> <Method for producing crystal core master batch and method for producing release film>

如表1所示，依照上述所記載聚對苯二甲酸丁二酯：100質量份、與上述所記載各結晶核劑5質量份的組成比進行摻合後，使用雙軸擠 出機，依250℃擠筒溫度施行熔融混練並顆粒化，便製得結晶核劑濃度5質量%的結晶核劑母料。 As shown in Table 1, after the blending ratio of 100 parts by mass of the polybutylene terephthalate described above and 5 parts by mass of each of the crystal nucleating agents described above, the biaxial extrusion was used. The machine was subjected to melt-kneading and granulation at a temperature of 250 ° C, and a crystal nucleate masterbatch having a crystal nucleating agent concentration of 5% by mass was obtained.

其次，將上述所記載聚對苯二甲酸丁二酯與結晶核劑母料進行摻合，並使用為離型層的原料。結晶核劑的添加量係相對於各聚對苯二甲酸丁二酯100質量份，依上述結晶核劑母料成為3質量份或5質量份，即結晶核劑添加量為1500ppm或2500ppm的方式進行摻合。 Next, the polybutylene terephthalate described above and the crystal nucleating agent masterbatch were blended, and a raw material which is a release layer was used. The amount of the crystal nucleating agent added is 3 parts by mass or 5 parts by mass based on 100 parts by mass of each of the polybutylene terephthalate, that is, the amount of the crystal nucleating agent added is 1500 ppm or 2500 ppm. Blending is carried out.

核心層(緩衝層)的原料係由乙烯‧甲基丙烯酸甲酯共聚合體、與聚對苯二甲酸丁二酯，依表1所示比率(二者合計100質量%)進行摻合。利用設有螺桿徑40mm之擠出機3台的3層T型模頭薄膜成形機，將各原料裝填於各擠出機中，在成形溫度250℃、冷硬軋輥溫度80℃、空氣室靜壓15mmH2O的條件下，獲得二外面為離型層、核心層為緩衝層的二種三層構造之積層薄膜。壓花處理係利用捲繞式使接觸於經加熱過的預熱輥溫度100℃後，再利用表面粗糙度Ra為4μm的壓花輥，依壓花輥溫度180℃、壓花線壓50kg/cm實施。 The raw material of the core layer (buffer layer) was blended with a polyethylene/methyl methacrylate copolymer and polybutylene terephthalate at a ratio shown in Table 1 (the total amount of both was 100% by mass). A three-layer T-die film forming machine equipped with three extruders having a screw diameter of 40 mm was used to load each raw material into each extruder at a forming temperature of 250 ° C, a chill roll temperature of 80 ° C, and an air chamber. Under the condition of pressure of 15 mmH 2 O, a laminated film of two three-layer structures in which the outer layer is a release layer and the core layer is a buffer layer is obtained. The embossing treatment is performed by using a winding type to contact the heated preheating roll at a temperature of 100 ° C, and then using an embossing roll having a surface roughness Ra of 4 μm, depending on the embossing roll temperature of 180 ° C and the embossing line pressure of 50 kg / Cm implementation.

<烤箱熱處理方法> <Oven heat treatment method>

使用熱風循環式烤箱，在大氣環境下，依180℃、5分鐘對上述積層薄膜施行熱處理，將經自然冷卻後的薄膜當作離型薄膜。 The laminated film was heat-treated at 180 ° C for 5 minutes in a hot air circulating oven, and the naturally cooled film was regarded as a release film.

針對上述離型薄膜依照以下方法施行評價。 The above release film was evaluated in accordance with the following method.

結果如表1所示。 The results are shown in Table 1.

(1)壓合後表面粗糙度之評價方法 (1) Evaluation method of surface roughness after pressing

使聚醯亞胺薄膜[商品名：UPILEX 50S(宇部興產(股)製)厚度：50μm]、與離型薄膜重疊，進而在其二外側利用鋁板(厚度0.1mm)、作為緩衝材的報紙10張、SUS板(厚度1mm)夾置，施行壓合成形。壓合係在3MPa壓力下，依180℃、10分鐘的條件實施。待壓合成形結束後，解除壓合壓，經自然冷卻後，將離型薄膜從聚醯亞胺薄膜上離型，測定與聚醯亞胺薄膜接觸過的離型薄膜之表面粗糙度。 Polyimide film [trade name: UPILEX 50S (manufactured by Ube Industries, Ltd.) thickness: 50 μm], which overlaps with the release film, and further uses an aluminum plate (thickness: 0.1 mm) and a newspaper as a cushioning material on the outer side of the film. Ten sheets of SUS plates (thickness 1 mm) were placed and pressed to form a composite shape. The press-fit system was carried out under the pressure of 3 MPa at 180 ° C for 10 minutes. After the completion of the compression molding, the pressing pressure was released, and after leaving the film, the release film was released from the polyimide film, and the surface roughness of the release film which was in contact with the polyimide film was measured.

<表面粗糙度測定方法> <Method for measuring surface roughness>

根據JIS B 0601，求取離型薄膜表面層的算術表面粗糙度Ra。 The arithmetic surface roughness Ra of the surface layer of the release film was determined in accordance with JIS B 0601.

接觸式粗糙度計：股份有限公司小坂研究所製三次元表面粗糙度測定器SE-3500K Contact Roughness Tester: Three-dimensional Surface Roughness Tester SE-3500K made by Otaru Research Institute Co., Ltd.

基準長度：2.5mm Base length: 2.5mm

速度：0.3mm/s Speed: 0.3mm/s

截止點：0.8mm Cut-off point: 0.8mm

(2)壓合前表面粗糙度之評價方法 (2) Evaluation method of surface roughness before pressing

依上述相同條件測定上述壓合前的離型薄膜之表面粗糙度。 The surface roughness of the release film before the press-bonding was measured under the same conditions as above.

(3)拉伸彈性模數之測定方法 (3) Method for measuring tensile modulus of elasticity

根據JIS K 7127，求取23℃下的拉伸彈性模數。 The tensile elastic modulus at 23 ° C was determined in accordance with JIS K 7127.

(4)自然剝離之評價 (4) Evaluation of natural stripping

依照實驗例所說明熱壓合步驟進行的自然剝離之評價，係依如下述實施。 The evaluation of the natural peeling performed by the thermocompression bonding step described in the experimental example was carried out as follows.

覆蓋層薄膜(聚醯亞胺層厚度：12μm、環氧樹脂系接著劑層厚度：15μm)、與銅箔(厚度：12μm)的尺寸係設為190mm×280mm，離型薄膜的尺寸係設為210mm×297mm。壓合係在4MPa壓力，依180℃、預熱10秒、加壓2分鐘的條件下施行貼合。壓合成形結束後，解除壓合壓，從壓合板中，將覆蓋層與離型薄膜依重疊積層體的狀態取出，靜置於常溫操作台上並使自然冷卻。隨自然冷卻，離型薄膜會從覆蓋層上自然剝離。 The cover film (thickness of polyimine layer: 12 μm, thickness of epoxy resin-based adhesive layer: 15 μm) and copper foil (thickness: 12 μm) were 190 mm × 280 mm, and the size of the release film was set to 210mm × 297mm. The press-fit was carried out at a pressure of 4 MPa, at 180 ° C, preheating for 10 seconds, and pressurization for 2 minutes. After the press-forming formation is completed, the press-fitting pressure is released, and the cover layer and the release film are taken out from the laminated plate in a state in which the laminate is stacked, and placed on a normal temperature stage to be naturally cooled. With natural cooling, the release film will naturally peel off from the cover.

將從壓合板中取出的時點起至覆蓋層大致全面自然剝離為止的時間，設為覆蓋層自然剝離時間，並施行評價。 The time from the time when the pressure-sensitive adhesive sheet was taken out until the coating layer was substantially completely and completely peeled off was taken as the natural peeling time of the coating layer, and evaluation was performed.

(5)耐起皺性評價 (5) Evaluation of crease resistance

依實驗例施行離型時，將印刷佈線基板彎曲只要有1處出現起皺的情況評為「×」，將沒有出現起皺的情況評為「○」。 When the release pattern is applied according to the experimental example, the printed wiring board is bent as long as one wrinkle is evaluated as "x", and the wrinkle is not evaluated as "○".

(實驗例)印刷佈線基板之製造過程中的熱壓合步驟 (Experimental Example) Thermal Compression Step in Manufacturing Process of Printed Wiring Substrate

針對製造印刷佈線基板時的一步驟，使用本發明離型薄膜施行的 熱壓合步驟進行說明。使用圖1中截面所示由聚醯亞胺層2-1與環氧樹脂系接著劑層2-2所構成的覆蓋層薄膜2[NIKKAN工業(股)製、商品名：CISV1215]。在該覆蓋層薄膜中，在相當於印刷佈線基板端子部分的部分處，施行複數打穿而形成窗口部4(圖1中僅圖示1個)。另一配線印刷佈線基板係於聚醯亞胺利用銅箔形成配線圖案。 A step for manufacturing a printed wiring substrate, using the release film of the present invention The thermal compression step is described. A cover film 2 (manufactured by NIKKAN Industrial Co., Ltd., trade name: CISV1215) composed of a polyimide layer 2-1 and an epoxy resin-based adhesive layer 2-2 shown in the cross section in Fig. 1 was used. In the cover film, a plurality of punctures are formed at a portion corresponding to the terminal portion of the printed wiring board to form the window portion 4 (only one is shown in Fig. 1). Another wiring printed wiring board is formed of a polyimide foil using a copper foil to form a wiring pattern.

如圖1的剖視圖所示，使該印刷佈線基材3與覆蓋層薄 膜2定位並重疊，在利用離型薄膜1夾置其二面側的狀態下，安裝於加熱壓合機中。對其施加一定時間加熱與壓力而施行加熱壓合，然後解開壓合板，待冷卻後，使離型薄膜1從已接著覆蓋層薄膜2的印刷佈線基材上進行離型。藉此，形成在印刷佈線基材的端子部分有開設窗口的覆蓋層，移往後續的鍍敷步驟。另外，亦可取代覆蓋層，而使用由與印刷佈線基板間具有接著機能的單層所構成的薄膜。各實施例及比較例的評價結果，整理於表2及表3。 As shown in the cross-sectional view of FIG. 1, the printed wiring substrate 3 and the cover layer are made thin. The film 2 is positioned and overlapped, and is attached to the heating press in a state in which the release film 1 is placed on both sides thereof. The heating and pressing are applied thereto for a certain period of time, and then the press-bonding plate is unwound, and after cooling, the release film 1 is released from the printed wiring substrate on which the cover film 2 has been attached. Thereby, a coating layer having a window to be opened at the terminal portion of the printed wiring substrate is formed, and is moved to a subsequent plating step. Further, instead of the cover layer, a film composed of a single layer having an adhesive function with the printed wiring board may be used. The evaluation results of the respective examples and comparative examples are summarized in Tables 2 and 3.

(產業上之可利用性) (industrial availability)

在印刷佈線基板、撓性印刷佈線基板、多層印刷佈線基板等的製造步驟中，當隔著預浸體或耐熱薄膜，將貼銅積層板或銅箔施行熱壓合時係有使用離型薄膜。又，在撓性印刷基板的製造步驟中，當於已形成有電氣迴路的撓性印刷基板本體上，利用熱硬化型接著劑或熱硬化性接著片，將覆蓋層薄膜或補強板施行熱壓合接著時，為防止覆蓋層薄膜與壓合熱板發生接著的情形，便可使用本發明的離型薄膜。 In the manufacturing steps of a printed wiring board, a flexible printed wiring board, and a multilayer printed wiring board, when a copper-clad laminate or a copper foil is thermocompression-bonded via a prepreg or a heat-resistant film, a release film is used. . Further, in the manufacturing process of the flexible printed circuit board, the cover film or the reinforcing plate is subjected to hot pressing on the flexible printed circuit board body on which the electrical circuit has been formed by using a thermosetting adhesive or a thermosetting adhesive sheet. In the case of the subsequent step, in order to prevent the cover film from coming into contact with the press-fit hot plate, the release film of the present invention can be used.

1‧‧‧離型薄膜 1‧‧‧ release film

2‧‧‧覆蓋層薄膜(保護膜) 2‧‧‧Overlay film (protective film)

2-1‧‧‧聚醯亞胺薄膜 2-1‧‧‧ Polyimine film

2-2‧‧‧環氧樹脂系接著劑層 2-2‧‧‧Epoxy resin adhesive layer

3‧‧‧印刷佈線基板 3‧‧‧Printed wiring substrate

4‧‧‧窗口部 4‧‧‧ Window Department

Claims (7)

一種離型薄膜，係含有由聚對苯二甲酸丁二酯(A)所構成層作為表層的離型薄膜，其特徵在於：將該薄膜與50μm厚的聚醯亞胺薄膜相重疊，經依180℃、3MPa施行10分鐘熱壓合後的表面粗糙度Ra係0.1~10μm的範圍。 A release film comprising a release film composed of a layer composed of polybutylene terephthalate (A) as a surface layer, characterized in that the film is overlapped with a 50 μm thick polyimide film, The surface roughness Ra after thermocompression bonding at 180 ° C and 3 MPa for 10 minutes was in the range of 0.1 to 10 μm. 如申請專利範圍第1項之離型薄膜，其中，在該薄膜施行熱壓合前的表面粗糙度Ra係1~10μm的範圍。 The release film of claim 1, wherein the surface roughness Ra before the film is subjected to thermocompression is in the range of 1 to 10 μm. 如申請專利範圍第1或2項之離型薄膜，其中，依23℃所測定的伸彈性模數係600MPa~2000MPa。 The release film according to claim 1 or 2, wherein the tensile modulus according to 23 ° C is 600 MPa to 2000 MPa. 如申請專利範圍第1項之離型薄膜，其中，聚對苯二甲酸丁二酯(A)的固有黏度(IV)係1.0~1.3。 The release film of claim 1, wherein the polybutylene terephthalate (A) has an intrinsic viscosity (IV) of 1.0 to 1.3. 如申請專利範圍第1項之離型薄膜，其中，背面層或內層係含有熔點50℃至150℃的樹脂45質量%以上。 The release film of claim 1, wherein the back layer or the inner layer contains 45 mass% or more of a resin having a melting point of 50 ° C to 150 ° C. 如申請專利範圍第1至5項中任一項之離型薄膜，係在大氣中，依100℃~200℃施行加熱處理。 The release film according to any one of claims 1 to 5 is subjected to heat treatment in the air at 100 ° C to 200 ° C. 一種印刷佈線基板之製造方法，係在印刷佈線基板上，將保護膜施行加熱‧加壓而熱接著的步驟，其包括有：保護膜與加壓板之間介設申請專利範圍第1至6項中任一項之離型薄膜，施行加熱‧加壓而熱接著，經熱接著後剝離該離型薄膜的步驟。 A method of manufacturing a printed wiring board is a step of heating, protecting, and thermally adhering a protective film on a printed wiring board, comprising: applying a patent range 1 to 6 between a protective film and a pressure plate The release film of any one of the items, which is subjected to heating, pressurization, and heat, followed by a step of peeling off the release film by heat.
TW102136740A 2013-03-14 2013-10-11 Release film and method of manufacturing printed wiring board using the same TWI609755B (en)

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