WO2022009591A1 - Mold release film - Google Patents

Mold release film Download PDF

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Publication number
WO2022009591A1
WO2022009591A1 PCT/JP2021/021751 JP2021021751W WO2022009591A1 WO 2022009591 A1 WO2022009591 A1 WO 2022009591A1 JP 2021021751 W JP2021021751 W JP 2021021751W WO 2022009591 A1 WO2022009591 A1 WO 2022009591A1
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WIPO (PCT)
Prior art keywords
resin
release film
release
curing
cushion layer
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PCT/JP2021/021751
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French (fr)
Japanese (ja)
Inventor
拓樹 古橋
昌史 福井
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株式会社東京セロレーベル
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Publication of WO2022009591A1 publication Critical patent/WO2022009591A1/en

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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
    • 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
    • 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]
    • 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
    • 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

Definitions

  • the present invention relates to a release film such as that used in the manufacturing process of a printed circuit board such as a flexible printed circuit board (FPC).
  • a printed circuit board such as a flexible printed circuit board (FPC).
  • a commonly used release film has a cushion layer in the middle of the thickness direction for absorbing unevenness during heat pressing of a coverlay film and a copper-clad laminated plate (CCL), and the cushion layer is formed.
  • the cushion layer is formed.
  • it is composed of a flexible resin film such as polyethylene which is a thermoplastic resin and high density polyethylene (HDPE) (see Patent Document 1 below).
  • the thermoplastic resin film has a melting point, and when heated above the melting point, the resin becomes fluid.
  • the processing temperature has risen in recent years due to the higher performance of materials used for printed circuit boards, especially flexible printed circuit boards.
  • the processing temperature was 150 ° C. for a general-purpose resin (FR4) in which the resin used was an epoxy resin, but a heat-resistant resin using a polyimide resin ( In the case of FR5), it is 170 ° C., and in the case of using LCP (liquid crystal polymer) (FR6), it is 250 ° C.
  • FR is an index (flame retardant grade) indicating the flame retardancy of the copper-clad laminate, which is a member of the printed circuit board, and is currently from FR1 to FR6.
  • the melting point of the high-density polyethylene is about 136 ° C. for a homopolymer having a specific gravity of 0.97
  • the release film using the high-density polyethylene as the cushion layer is heated above the melting point.
  • the polymer may melt out and contaminate the mold or product.
  • the main object of the present invention is to use a curable adhesive for the cushion layer so as not to cause contamination of the mold or the like even when used in a high temperature range.
  • the means for that is a release film having a cushion layer between the two resin layers, and at least one of the resin layers is a release resin layer made of a thermoplastic resin, the melting point of which is 200 ° C.
  • a release film in which the cushion layer is made of a curable resin having a crosslinked structure, and the storage elasticity before curing is 10 MPa or less at 23 ° C.
  • the crosslinked structure of the cushion layer sandwiched between the resin layers prevents the curable resin from leaching out.
  • the curable resin having a low storage elastic modulus is very soft, and secures the unevenness-following property of the release resin layer at the time of hot pressing.
  • At least one of the resin layers, the mold release resin layer has high heat resistance and exhibits a mold release function.
  • a cushion layer made of a curable resin having a crosslinked structure can prevent contamination of a mold or the like even when used in a high temperature range, and also has good unevenness followability. Can also be obtained.
  • Sectional drawing of the release film Sectional drawing of the separated state which shows the use example of a release film. Sectional drawing at the time of press molding which shows the use example of a release film. Sectional drawing of the release film which concerns on another example. Sectional drawing of the release film which concerns on another example. Sectional drawing of the release film which concerns on another example. Sectional drawing of the release film which concerns on another example. Sectional drawing of the release film which concerns on another example.
  • FIG. 1 shows a cross-sectional view of the release film 11.
  • the release film has a structure in which a cushion layer is provided between two resin layers, and at least one of the resin layers is a release resin layer made of a thermoplastic resin.
  • the release film 11 shown in FIG. 1 is provided with a cushion layer 13 between two release resin layers 12, and has at least three layers.
  • the release film 11 is provided with high heat resistance so that it can be used even in a high temperature range exceeding 200 ° C. or 250 ° C.
  • the mold release resin layer 12 located on the outermost layers of the front and back is a layer having a mold release function in contact with a mold or a product, and is composed of a thermoplastic resin having good tensile strength and elongation and elongation.
  • An appropriate material is used so that it can be used even in a desired high temperature range exceeding 200 ° C. as described above.
  • it is formed of at least one material such as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyarylate, polyimide, polyamide, polyamideimide, polyetherimide, polyetheretherketone, and poniphenylen sulphide. You can use things.
  • a material having a melting point of 250 ° C. or higher may be selected instead of 200 ° C.
  • the thickness of the release resin layer 12 is appropriately set according to the material and the desired function, but is preferably set to, for example, 4 ⁇ m or more and 50 ⁇ m or less, and is preferably set to 6 ⁇ m or more and 25 ⁇ m or less from the viewpoint of unevenness followability.
  • the surface of the release resin layer 12 including the cushion layer 13 may be surface-treated as necessary.
  • surface modification can be performed by corona discharge treatment, plasma treatment, primer coating, or the like to improve the bondability with the cushion layer 13.
  • the surface of the release resin layer 12 opposite to the surface provided with the cushion layer 13 may be provided with another appropriate layer, or the release resin layer 12 itself may be composed of a plurality of layers.
  • the cushion layer 13 is a layer for absorbing unevenness, and is made of a curable resin having a crosslinked structure. That is, the curable resin has a crosslinked structure by being cured, and in the present invention, a pressure-sensitive adhesive is used, and the curable resin is composed of a viscoelastic body, particularly a heat-resistant pressure-sensitive adhesive.
  • the pressure-sensitive adhesive has a small storage elastic modulus, that is, a value indicating hardness, and has a storage elastic modulus of 0.1 MPa after curing when measured at 10 Hz at 23 ° C (room temperature) and a heating rate of 5 ° C / min. Use one with a pressure of 10 MPa or less.
  • the storage at the above-mentioned upper limit at 23 ° C. (room temperature) is 0.6 MPa or more and 6 MPa or less, and the storage at 300 ° C. is 0.012 MPa or more and 0.6 MPa or less.
  • Examples of the resin used as such a pressure-sensitive adhesive include those having a hydroxy group, a thiol group, a carboxy group, an epoxy group, an oxetane group, an amino group, a vinyl group and the like as functional groups contributing to the curing reaction.
  • the curing methods include isocyanate curing, epoxy curing, melamine curing, metal curing, oxazoline curing, radical curing with heat and an initiator, radical curing or cation curing with ultraviolet rays and a light initiator, electron beam curing, and the like.
  • Monomers may be added to the adhesive as needed for the purpose of supplementing the lacking physical characteristics. This enables customization according to the application. For example, in order to increase the adhesive strength of the cushion layer 13, a monomer having a low glass transition temperature may be added, and if it is considered that the heat resistance is insufficient, a monomer having a high glass transition temperature or a polyfunctional monomer may be added.
  • the thickness of the cushion layer 13 is preferably 5 ⁇ m or more and 100 ⁇ m or less, preferably 25 ⁇ m or more and 50 ⁇ m or less, from the viewpoint of cushioning properties.
  • the thickness of the entire release film 11 can be set as desired, and can be, for example, about 13 ⁇ m to 200 ⁇ m.
  • the thickness of the release film 11 that can be used most widely is about 25 ⁇ m to 75 ⁇ m.
  • the thickness of the cushion layer 13 is, for example, 20 to 75%. Set to degree.
  • the release film 11 having the release resin layer 12 and the cushion layer 13 as described above is manufactured as follows.
  • An adhesive is applied to one side of one release resin layer 12, dried, and then laminated with the other release resin layer 12 at 5 ° C or higher and 200 ° C or lower.
  • the pressure-sensitive adhesive When applying the pressure-sensitive adhesive, the pressure-sensitive adhesive dilutes the reactive resin compound with an organic solvent or an aqueous solvent.
  • organic solvent or water-based solvent include water, alcohols such as ethyl alcohol, n-propyl alcohol, isopropyl alcohol, and n-butyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, and propylene glycol.
  • Monomethyl ether, propylene glycol Alcohol-based solvents such as monobutyl ethers such as alkylene glycol monoalkyl ethers, aromatic hydrocarbons such as toluene and xylene, acetates such as ethyl acetate and butyl acetate, methyl ethyl ketone, methyl isobutyl ketone and the like. Ketones and the like can be used alone or in combination.
  • the coating should be done by an appropriate method such as gravure coat, roll coat, comma coat, air knife coat, kiss (lip) coat, curtain coat, spin coat, wire bar coat, etc.
  • the drying temperature varies depending on the type of solvent used, but is generally 23 ° C. or higher and 200 ° C. or lower, and in most cases 80 ° C. or higher and 120 ° C. or lower.
  • Laminating can be done by dry laminating using the adhesive strength of the dried adhesive layer.
  • the adhesive applied to one of the release resin layers 12 is cured.
  • the operation and timing of curing differ depending on the curing method.
  • isocyanate curing it is performed at the time of curing (aging) after laminating.
  • Curing is performed, for example, at 23 to 60 ° C. under a heated state for a predetermined time (for example, 24 to 168 hours).
  • curing is performed at the same time as solvent drying.
  • curing is performed by irradiating ultraviolet rays or electron beams before or after laminating. Ultraviolet rays are irradiated at, for example, 50 to 2000 mJ / cm 2 , and electron beams are irradiated at, for example, 10 to 300 kGry.
  • the release film 11 configured as described above is used as follows to manufacture a printed circuit board.
  • FIG. 2 shows an example of using the release film 11 when manufacturing a flexible printed circuit board.
  • FIG. 2A shows a single-sided copper-clad plate (CCL) 21a
  • FIG. 2B shows a single-sided copper-clad plate (CCL) 21a.
  • An example of manufacturing a flexible printed circuit board using a double-sided copper-clad plate (CCL) 21b is shown.
  • 22 is a coverlay (CL).
  • both sides thereof are covered with the release film 11 and then sandwiched between the hot plates 23 to perform heating / pressure press molding.
  • the release resin layers 12 located on both sides of the release film 11 have the same configuration mode, there is no distinction between the front and back sides of the release film 11. Therefore, the release film 11 can be used without being aware of the front and back sides.
  • Heating and pressurization are performed at a predetermined temperature for a predetermined time, for example, 150 ° C. or higher, 300 ° C. or lower for 15 minutes or longer, 120 minutes or shorter, and then cooled to room temperature to manufacture a flexible printed substrate.
  • the cushion layer 13 made of a viscoelastic body of the release film 11 has a crosslinked structure, so that it does not have a melting point and can be prevented from leaching out. Therefore, it is possible to prevent the mold and the product from being contaminated with the melted resin, and it is possible to suppress the occurrence of defects.
  • the cushion layer 13 is formed by curing a pressure-sensitive adhesive having a low storage elastic modulus, it is possible to secure the ability to follow the unevenness of the surface of the product or the like.
  • PEEK polyetheretherketone
  • the melting point is extremely high at 334 ° C. and it also has high mechanical properties such as tensile strength, so that the release film has better heat resistance and higher performance. 11 can be obtained.
  • paper or cushion film is interposed on the surface in contact with the hot plate, but these can be omitted.
  • FIG. 4 is a cross-sectional view of the release film 11 according to another example, and shows an example in which a plurality of cushion layers 13 are stacked.
  • the cushion layer 13 is not limited to one layer, and may be a plurality of layers according to the actual situation of processing.
  • FIG. 5 is a cross-sectional view of the release film 11 according to another example, and shows an example in which the release coating layer 14 is provided on the surface of the release resin layer 12.
  • the release coating layer 14 enhances or supplements the function of the release resin layer 12, and is formed by coating, for example, silicon or fluorine.
  • FIG. 6 is a cross-sectional view of the release film 11 according to another example, and is an example in which the resin layer 15 is provided between the release resin layer 12 and the cushion layer 13.
  • the resin layer 15 may be made of a resin having releasability under the conditions of use, or may be made of a resin having no releasability.
  • the release film 11 having such a configuration is advantageous in that the amount of the synthetic resin used as the release resin layer 12 can be reduced when it is expensive, for example, polyetheretherketone.
  • FIG. 7 is a cross-sectional view of the release film 11 according to another example.
  • one of the resin layers is made of a thermoplastic resin.
  • An example is shown in which the release resin layer 12 is formed and the other is composed of the resin layer 16 having no releasability.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Laminated Bodies (AREA)
  • Non-Metallic Protective Coatings For Printed Circuits (AREA)
  • Adhesive Tapes (AREA)
  • Moulds For Moulding Plastics Or The Like (AREA)

Abstract

[Problem] The present invention addresses the problem of preventing contamination of a mold and the like even if the production of a flexible printed board is carried out in a high temperature range. [Solution] A mold release film 11 which is provided with a cushion layer 13 between two mold release resin layers 12, wherein the mold release resin layers 12 are configured from a thermoplastic resin that has a melting point of 250°C or higher. In addition, the cushion layer 13 is configured from a curable resin that has a crosslinked structure. The present invention uses a curable resin which has a storage elastic modulus after curing of 6 MPa or less at 23°C, and a storage elastic modulus after curing of 0.6 MPa or less at 300°C.

Description

離型フィルムRelease film
　この発明は、例えばフレキシブルプリント基板（ＦＰＣ）のようなプリント基板の製造工程で使用されるような離型フィルムに関する。 The present invention relates to a release film such as that used in the manufacturing process of a printed circuit board such as a flexible printed circuit board (FPC).
　一般的に使用されている離型フィルムは、カバーレイフィルムと銅張積層板（ＣＣＬ）の加熱プレス時における凹凸吸収のためのクッション層を厚み方向の中間に有しており、そのクッション層は、例えば熱可塑性樹脂であるポリエチレン、高密度ポリエチレン（ＨＤＰＥ）等の柔軟な樹脂フィルムで構成されている（下記特許文献１参照）。当然のことながら、熱可塑性樹脂フィルムには融点があり、融点以上に加熱すると樹脂は流動性を持つようになる。 A commonly used release film has a cushion layer in the middle of the thickness direction for absorbing unevenness during heat pressing of a coverlay film and a copper-clad laminated plate (CCL), and the cushion layer is formed. , For example, it is composed of a flexible resin film such as polyethylene which is a thermoplastic resin and high density polyethylene (HDPE) (see Patent Document 1 below). As a matter of course, the thermoplastic resin film has a melting point, and when heated above the melting point, the resin becomes fluid.
　ところが、プリント基板、特にフレキシブルプリント基板に使用される材料の高性能化によって、近年，加工温度が高温化している。例えば、カバーレイフィルムとＣＣＬの熱圧着加工において、使用される樹脂がエポキシ樹脂からなる一般用のもの（ＦＲ４）では加工温度は１５０℃であったが、ポリイミド樹脂を用いた耐熱性のもの（ＦＲ５）の場合には１７０℃であり、ＬＣＰ（液晶ポリマー）を用いたもの（ＦＲ６）では２５０℃である。なお、前記「ＦＲ」は、プリント基板の部材である銅張り積層板の難燃性を示す指標（ｆｌａｍｅ　ｒｅｔａｒｄａｎｔ　ｇｒａｄｅ）であり、現在、ＦＲ１～ＦＲ６まである。 However, the processing temperature has risen in recent years due to the higher performance of materials used for printed circuit boards, especially flexible printed circuit boards. For example, in the thermocompression bonding of a coverlay film and CCL, the processing temperature was 150 ° C. for a general-purpose resin (FR4) in which the resin used was an epoxy resin, but a heat-resistant resin using a polyimide resin ( In the case of FR5), it is 170 ° C., and in the case of using LCP (liquid crystal polymer) (FR6), it is 250 ° C. The "FR" is an index (flame retardant grade) indicating the flame retardancy of the copper-clad laminate, which is a member of the printed circuit board, and is currently from FR1 to FR6.
　また、材料がＦＲ４やＦＲ５の場合であっても、加工の効率化をはかり加工時間を短縮するために高温化が行われている。 Even when the material is FR4 or FR5, the temperature is raised in order to improve the processing efficiency and shorten the processing time.
　今後、加工温度の更なる高温化が進むと考えられる。 It is expected that the processing temperature will continue to rise in the future.
　しかしながら、高密度ポリエチレンの融点は、比重０．９７のホモポリマーで１３６℃前後であるので、高密度ポリエチレンをクッション層に用いた離型フィルムは、融点以上に加熱されることになる。このため、ポリマーが溶け出して、金型や製品を汚染することがあった。 However, since the melting point of the high-density polyethylene is about 136 ° C. for a homopolymer having a specific gravity of 0.97, the release film using the high-density polyethylene as the cushion layer is heated above the melting point. As a result, the polymer may melt out and contaminate the mold or product.
特開２００７－９８８１６号公報Japanese Unexamined Patent Publication No. 2007-98816
　これまでクッション層には樹脂フィルムを用いるのが常識であって、金型等の汚染を防止するのには限度があった。 Until now, it was common sense to use a resin film for the cushion layer, and there was a limit to prevent contamination of molds and the like.
　そこで、この発明は、クッション層に硬化性粘着剤を用いることによって、高温域で使用しても金型等の汚染を引き起こすことがないようにすることを主な目的とする。 Therefore, the main object of the present invention is to use a curable adhesive for the cushion layer so as not to cause contamination of the mold or the like even when used in a high temperature range.
　そのための手段は、２つの樹脂層の間にクッション層を備えた離型フィルムであって、前記樹脂層のうち少なくとも一方が、熱可塑性樹脂からなる離型樹脂層であり、その融点が２００℃以上であるとともに、前記クッション層が架橋構造を有する硬化性樹脂で構成され、その硬化前の貯蔵弾性率が２３℃において１０ＭＰａ以下である、離型フィルムである。 The means for that is a release film having a cushion layer between the two resin layers, and at least one of the resin layers is a release resin layer made of a thermoplastic resin, the melting point of which is 200 ° C. In addition to the above, it is a release film in which the cushion layer is made of a curable resin having a crosslinked structure, and the storage elasticity before curing is 10 MPa or less at 23 ° C.
　この構成では、樹脂層に挟まれたクッション層は、その架橋構造が硬化性樹脂の溶け出しを防止する。また貯蔵弾性率が低い硬化性樹脂はとても柔らかく、熱プレス時における離型樹脂層の凹凸追従性を確保する。樹脂層のうち少なくとも一方の離型樹脂層は、高い耐熱性を有し離型機能を発揮する。 In this configuration, the crosslinked structure of the cushion layer sandwiched between the resin layers prevents the curable resin from leaching out. Further, the curable resin having a low storage elastic modulus is very soft, and secures the unevenness-following property of the release resin layer at the time of hot pressing. At least one of the resin layers, the mold release resin layer, has high heat resistance and exhibits a mold release function.
　この発明によれば、架橋構造を有する硬化性樹脂からなるクッション層によって、高温域で使用しても金型等の汚染を引き起こすことがないようにすることができる上に、良好な凹凸追従性も得られる。 According to the present invention, a cushion layer made of a curable resin having a crosslinked structure can prevent contamination of a mold or the like even when used in a high temperature range, and also has good unevenness followability. Can also be obtained.
離型フィルムの断面図。Cross-sectional view of the release film. 離型フィルムの使用例を示す分離状態の断面図。Sectional drawing of the separated state which shows the use example of a release film. 離型フィルムの使用例を示すプレス成形時の断面図。Sectional drawing at the time of press molding which shows the use example of a release film. 他の例に係る離型フィルムの断面図。Sectional drawing of the release film which concerns on another example. 他の例に係る離型フィルムの断面図。Sectional drawing of the release film which concerns on another example. 他の例に係る離型フィルムの断面図。Sectional drawing of the release film which concerns on another example. 他の例に係る離型フィルムの断面図。Sectional drawing of the release film which concerns on another example.
　この発明を実施するための一形態を、以下図面を用いて説明する。 A mode for carrying out the present invention will be described below with reference to the drawings.
　図１に離型フィルム１１の断面図を示す。離型フィルムは、２つの樹脂層の間にクッション層を備えた構成であって、樹脂層のうち少なくとも一方が、熱可塑性樹脂からなる離型樹脂層である。 FIG. 1 shows a cross-sectional view of the release film 11. The release film has a structure in which a cushion layer is provided between two resin layers, and at least one of the resin layers is a release resin layer made of a thermoplastic resin.
　図１に示した離型フィルム１１は２つの離型樹脂層１２の間にクッション層１３を備えており、少なくとも３層を有している。この離型フィルム１１は、２００℃又は２５０℃を超える高温域でも使用できるように、高い耐熱性が備えられている。 The release film 11 shown in FIG. 1 is provided with a cushion layer 13 between two release resin layers 12, and has at least three layers. The release film 11 is provided with high heat resistance so that it can be used even in a high temperature range exceeding 200 ° C. or 250 ° C.
　表裏の最外層に位置する離型樹脂層１２は、金型や製品に接し、離型機能を有する層であり、引張強度や伸長伸度の良好な熱可塑性樹脂で構成されている。 The mold release resin layer 12 located on the outermost layers of the front and back is a layer having a mold release function in contact with a mold or a product, and is composed of a thermoplastic resin having good tensile strength and elongation and elongation.
　前述のような２００℃を超える所望の高温域でも使用できるように、適宜の材料が用いられる。具体的には例えば、ポリエチレンテレフタレート、ポリエチレンナフタレート、ポリブチレンテレフタレート、ポリアリレート、ポリイミド、ポリアミド、ポリアミドイミド、ポリエーテルイミド、ポリエーテルエーテルケトン、ポニフェニレンスルファイドなど、少なくとも一つの材料で形成されたものを使用できる。融点は２００℃ではなく、２５０℃以上の材料を選択してもよい。 An appropriate material is used so that it can be used even in a desired high temperature range exceeding 200 ° C. as described above. Specifically, it is formed of at least one material such as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyarylate, polyimide, polyamide, polyamideimide, polyetherimide, polyetheretherketone, and poniphenylen sulphide. You can use things. A material having a melting point of 250 ° C. or higher may be selected instead of 200 ° C.
　離型樹脂層１２の厚みは、材料や所望の機能に応じて適宜設定されるが、例えば４μｍ以上５０μｍ以下であるとよく、凹凸追従性の観点から例えば６μｍ以上２５μｍ以下に設定するとよい。 The thickness of the release resin layer 12 is appropriately set according to the material and the desired function, but is preferably set to, for example, 4 μm or more and 50 μm or less, and is preferably set to 6 μm or more and 25 μm or less from the viewpoint of unevenness followability.
　離型樹脂層１２におけるクッション層１３を備える面には、必要に応じて表面処理を施すとよい。例えばコロナ放電処理、プラズマ処理、プライマーコーティングなどによって表面改質を行って、クッション層１３との接合性を高めることができる。 The surface of the release resin layer 12 including the cushion layer 13 may be surface-treated as necessary. For example, surface modification can be performed by corona discharge treatment, plasma treatment, primer coating, or the like to improve the bondability with the cushion layer 13.
　離型樹脂層１２におけるクッション層１３を備える面とは反対側の面には、その他の適宜の層を備えてもよく、離型樹脂層１２自体を複数層で構成してもよい。 The surface of the release resin layer 12 opposite to the surface provided with the cushion layer 13 may be provided with another appropriate layer, or the release resin layer 12 itself may be composed of a plurality of layers.
　クッション層１３は、凹凸を吸収するための層であり、架橋構造を有する硬化性樹脂で構成されている。つまり、硬化性樹脂は硬化することにより架橋構造を備えるものであり、この発明では粘着剤が用いられ、粘弾性体、特に耐熱性を有する耐熱性粘着剤で構成されている。粘着剤は、貯蔵弾性率、つまり硬さを示す値が小さいものであり、２３℃（室温）における１０Ｈｚ、昇温速度５℃／分で測定した際の硬化後の貯蔵弾性率が０．１ＭＰａ以上１０ＭＰａ以下のものを用いる。より好ましくは２３℃（室温）における前述の上限における貯蔵が０．６ＭＰａ以上６ＭＰａ以下で、且つ３００℃における貯蔵が０．０１２ＭＰａ以上０．６ＭＰａ以下のものを用いる。 The cushion layer 13 is a layer for absorbing unevenness, and is made of a curable resin having a crosslinked structure. That is, the curable resin has a crosslinked structure by being cured, and in the present invention, a pressure-sensitive adhesive is used, and the curable resin is composed of a viscoelastic body, particularly a heat-resistant pressure-sensitive adhesive. The pressure-sensitive adhesive has a small storage elastic modulus, that is, a value indicating hardness, and has a storage elastic modulus of 0.1 MPa after curing when measured at 10 Hz at 23 ° C (room temperature) and a heating rate of 5 ° C / min. Use one with a pressure of 10 MPa or less. More preferably, the storage at the above-mentioned upper limit at 23 ° C. (room temperature) is 0.6 MPa or more and 6 MPa or less, and the storage at 300 ° C. is 0.012 MPa or more and 0.6 MPa or less.
　このような粘着剤として使用される樹脂としては、硬化反応に寄与する官能基として、ヒドロキシ基、チオール基、カルボキシ基、エポキシ基、オキセタン基、アミノ基、ビニル基などを有するものがあげられる。 Examples of the resin used as such a pressure-sensitive adhesive include those having a hydroxy group, a thiol group, a carboxy group, an epoxy group, an oxetane group, an amino group, a vinyl group and the like as functional groups contributing to the curing reaction.
　また、硬化方式には、イソシアネート硬化、エポキシ硬化、メラミン硬化、金属硬化、オキサゾリン硬化、熱と開始剤によるラジカル硬化、紫外線と光開始剤によるラジカル硬化又はカチオン硬化、電子線硬化などがある。 Further, the curing methods include isocyanate curing, epoxy curing, melamine curing, metal curing, oxazoline curing, radical curing with heat and an initiator, radical curing or cation curing with ultraviolet rays and a light initiator, electron beam curing, and the like.
　粘着剤には、不足している物性を補完する目的で、必要に応じてモノマーを添加してもよい。これによって、用途に応じたカスタマイズが可能になる。例えばクッション層１３の粘着力を高めるためには、ガラス転移温度の低いモノマーを添加し、耐熱性が不足すると考えられる場合には、ガラス転移温度の高い、又は多官能のモノマーを添加するとよい。 Monomers may be added to the adhesive as needed for the purpose of supplementing the lacking physical characteristics. This enables customization according to the application. For example, in order to increase the adhesive strength of the cushion layer 13, a monomer having a low glass transition temperature may be added, and if it is considered that the heat resistance is insufficient, a monomer having a high glass transition temperature or a polyfunctional monomer may be added.
　クッション層１３の厚みは、クッション性の観点から、５μｍ以上１００μｍ以下であるとよく、好ましくは、２５μｍ以上５０μｍ以下であるとよい。 The thickness of the cushion layer 13 is preferably 5 μm or more and 100 μm or less, preferably 25 μm or more and 50 μm or less, from the viewpoint of cushioning properties.
　離型フィルム１１全体の厚みは、所望に応じて設定でき、例えば１３μｍから２００μｍ程度とすることができる。最も広く使用され得る離型フィルム１１の厚みは、２５μｍ～７５μｍ程度である。 The thickness of the entire release film 11 can be set as desired, and can be, for example, about 13 μm to 200 μm. The thickness of the release film 11 that can be used most widely is about 25 μm to 75 μm.
　要求されるクッション性や最適なクッション性、離型樹脂層１２の性状などによっても異なるが、離型フィルム１１の全体の厚みを１００とした場合、クッション層１３の厚みは、例えば２０～７５％程度に設定される。 Although it depends on the required cushioning property, the optimum cushioning property, the properties of the release resin layer 12, etc., when the total thickness of the release film 11 is 100, the thickness of the cushion layer 13 is, for example, 20 to 75%. Set to degree.
　前述のような離型樹脂層１２とクッション層１３を有する離型フィルム１１は、次のようにして製造される。 The release film 11 having the release resin layer 12 and the cushion layer 13 as described above is manufactured as follows.
　一方の離型樹脂層１２の片面に粘着剤を塗工し、乾燥させたのち、５℃以上、２００℃以下において他方の離型樹脂層１２とラミネートする。 An adhesive is applied to one side of one release resin layer 12, dried, and then laminated with the other release resin layer 12 at 5 ° C or higher and 200 ° C or lower.
　粘着剤の塗工に際して、粘着剤は反応性樹脂化合物を有機溶剤又は水系溶剤に希釈する。有機溶剤又は水系溶剤としては、水のほか、エチルアルコール、ｎ－プロピルアルコール、イソプロピルアルコール、ｎ－ブチルアルコール等のアルコール類、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノブチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノブチルエーテル等のアルキレングリコールモノアルキルエーテル類等のアルコール系溶剤、トルエン、キシレン等の芳香族炭化水素類、酢酸エチル、酢酸ブチル等の酢酸エステル類、メチルエチルケトン、メチルイソブチルケトン等のケトン類等を単独または併用して用いることができる。 When applying the pressure-sensitive adhesive, the pressure-sensitive adhesive dilutes the reactive resin compound with an organic solvent or an aqueous solvent. Examples of the organic solvent or water-based solvent include water, alcohols such as ethyl alcohol, n-propyl alcohol, isopropyl alcohol, and n-butyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, and propylene glycol. Monomethyl ether, propylene glycol Alcohol-based solvents such as monobutyl ethers such as alkylene glycol monoalkyl ethers, aromatic hydrocarbons such as toluene and xylene, acetates such as ethyl acetate and butyl acetate, methyl ethyl ketone, methyl isobutyl ketone and the like. Ketones and the like can be used alone or in combination.
　塗工は、グラビアコート、ロールコート、コンマコート、エアナイフコート、キス（リップ）コート、カーテンコート、スピンコート、ワイヤーバーコートなど適宜の方法で行うとよい。 The coating should be done by an appropriate method such as gravure coat, roll coat, comma coat, air knife coat, kiss (lip) coat, curtain coat, spin coat, wire bar coat, etc.
　乾燥工程では、粘着剤に含まれている溶剤を飛ばす。乾燥温度は使用する溶剤種等によって異なるが、一般には２３℃以上２００℃以下であり、多くの場合８０℃以上１２０℃以下でよい。 In the drying process, the solvent contained in the adhesive is removed. The drying temperature varies depending on the type of solvent used, but is generally 23 ° C. or higher and 200 ° C. or lower, and in most cases 80 ° C. or higher and 120 ° C. or lower.
　ラミネートは、乾燥させた粘着剤層の粘着力を利用して、ドライラミネートで行える。 Laminating can be done by dry laminating using the adhesive strength of the dried adhesive layer.
　このような塗工、溶剤乾燥、ラミネートと順次行われる工程のなかで、一方の離型樹脂層１２に塗工された粘着剤の硬化を行う。 In the process of coating, solvent drying, and laminating in sequence, the adhesive applied to one of the release resin layers 12 is cured.
　硬化の操作と時期は、硬化方式によって異なる。イソシアネート硬化の場合には、ラミネート後の養生（エージング）時に行う。養生は例えば２３～６０℃で加温状態下に所定時間（例えば２４～１６８時間）置いて行う。 The operation and timing of curing differ depending on the curing method. In the case of isocyanate curing, it is performed at the time of curing (aging) after laminating. Curing is performed, for example, at 23 to 60 ° C. under a heated state for a predetermined time (for example, 24 to 168 hours).
　エポキシ硬化、メラミン硬化、金属硬化、オキサゾリン硬化、熱と開始剤によるラジカル硬化の場合には、硬化は、溶剤乾燥と同時に行われる。紫外線硬化、電子線硬化の場合には、硬化は、ラミネートの前又は後において紫外線又は電子線を照射して行う。紫外線は例えば５０～２０００ｍＪ／ｃｍ２で照射し、電子線は例えば１０～３００ｋＧｒｙで照射する。 In the case of epoxy curing, melamine curing, metal curing, oxazoline curing, and radical curing with heat and initiator, curing is performed at the same time as 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 laminating. Ultraviolet rays are irradiated at, for example, 50 to 2000 mJ / cm 2 , and electron beams are irradiated at, for example, 10 to 300 kGry.
　以上のように構成された離型フィルム１１は、次のように使用されてプリント基板が製造される。 The release film 11 configured as described above is used as follows to manufacture a printed circuit board.
　図２はフレキシブルプリント基板を製造するときの離型フィルム１１の一使用例を示しており、図２の（ａ）には片面銅張板（ＣＣＬ）２１ａを、図２の（ｂ）には両面銅張板（ＣＣＬ）２１ｂを用いたフレキシブルプリント基板を製造する場合の例を示している。図２中、２２はカバーレイ（ＣＬ）である。これらの両面を、図３に示したように離型フィルム１１で覆ったうえで熱板２３で挟んで加熱・加圧プレス成形を行う。 FIG. 2 shows an example of using the release film 11 when manufacturing a flexible printed circuit board. FIG. 2A shows a single-sided copper-clad plate (CCL) 21a, and FIG. 2B shows a single-sided copper-clad plate (CCL) 21a. An example of manufacturing a flexible printed circuit board using a double-sided copper-clad plate (CCL) 21b is shown. In FIG. 2, 22 is a coverlay (CL). As shown in FIG. 3, both sides thereof are covered with the release film 11 and then sandwiched between the hot plates 23 to perform heating / pressure press molding.
　このとき、離型フィルム１１の両面に位置する離型樹脂層１２は構成態様が同じであるので、離型フィルム１１に表裏の区別はない。このため、離型フィルム１１は表裏を意識することなく使用できる。 At this time, since the release resin layers 12 located on both sides of the release film 11 have the same configuration mode, there is no distinction between the front and back sides of the release film 11. Therefore, the release film 11 can be used without being aware of the front and back sides.
　加熱・加圧は、所定の温度で所定時間、例えば１５０℃以上、３００℃以下で１５分以上、１２０分以下で行い、その後常温まで冷却して、フレキシブルプリント基板を製造する。 Heating and pressurization are performed at a predetermined temperature for a predetermined time, for example, 150 ° C. or higher, 300 ° C. or lower for 15 minutes or longer, 120 minutes or shorter, and then cooled to room temperature to manufacture a flexible printed substrate.
　高温で加熱圧縮をしても、離型フィルム１１の粘弾性体からなるクッション層１３は、架橋構造を有するので、融点を有さず、溶け出しを防止できる。このため、金型や製品が溶け出した樹脂で汚染されることを回避でき、不良の発生を抑制できる。 Even when heated and compressed at a high temperature, the cushion layer 13 made of a viscoelastic body of the release film 11 has a crosslinked structure, so that it does not have a melting point and can be prevented from leaching out. Therefore, it is possible to prevent the mold and the product from being contaminated with the melted resin, and it is possible to suppress the occurrence of defects.
　しかも、クッション層１３は、貯蔵弾性率の低い粘着剤を硬化して構成しているので、製品等の表面の凹凸に対する追従性を確保できる。特に、離型樹脂層１２にポリエーテルエーテルケトン（ＰＥＥＫ）を使用すると、融点が３３４℃と極めて高く、引張強度など高い機械的特性も有するので、耐熱性がより良好で高性能の離型フィルム１１を得ることができる。 Moreover, since the cushion layer 13 is formed by curing a pressure-sensitive adhesive having a low storage elastic modulus, it is possible to secure the ability to follow the unevenness of the surface of the product or the like. In particular, when polyetheretherketone (PEEK) is used for the release resin layer 12, the melting point is extremely high at 334 ° C. and it also has high mechanical properties such as tensile strength, so that the release film has better heat resistance and higher performance. 11 can be obtained.
　また、従来、熱板に接する面に紙やクッションフィルムを介在させたが、これらを省略することができる。 Also, conventionally, paper or cushion film is interposed on the surface in contact with the hot plate, but these can be omitted.
　以下、他の例に係る離型フィルムを説明する。 Hereinafter, the release film according to another example will be described.
　図４は、他の例に係る離型フィルム１１の断面図であり、クッション層１３を複数重ねた例を示している。このようにクッション層１３は一層に限定されるものではなく、加工の実情に合わせて複数層にすることができる。 FIG. 4 is a cross-sectional view of the release film 11 according to another example, and shows an example in which a plurality of cushion layers 13 are stacked. As described above, the cushion layer 13 is not limited to one layer, and may be a plurality of layers according to the actual situation of processing.
　図５は、他の例に係る離型フィルム１１の断面図であり、離型樹脂層１２の表面に離型コーティング層１４を備えた例を示している。離型コーティング層１４は、離型樹脂層１２の機能を高めたり補ったりするもので、例えばシリコンやフッ素などをコーティングして形成される。 FIG. 5 is a cross-sectional view of the release film 11 according to another example, and shows an example in which the release coating layer 14 is provided on the surface of the release resin layer 12. The release coating layer 14 enhances or supplements the function of the release resin layer 12, and is formed by coating, for example, silicon or fluorine.
　図６は、他の例に係る離型フィルム１１の断面図であり、一方の離型樹脂層１２とクッション層１３との間に、樹脂層１５を備えた例である。この樹脂層１５は使用条件において離型性を有する樹脂で構成しても、離型性を有しない樹脂で構成してもよい。 FIG. 6 is a cross-sectional view of the release film 11 according to another example, and is an example in which the resin layer 15 is provided between the release resin layer 12 and the cushion layer 13. The resin layer 15 may be made of a resin having releasability under the conditions of use, or may be made of a resin having no releasability.
　このような構成の離型フィルム１１は、離型樹脂層１２として使用する合成樹脂が、例えばポリエーテルエーテルケトンのように高価である場合に、その使用量を低減できる点で有利である。 The release film 11 having such a configuration is advantageous in that the amount of the synthetic resin used as the release resin layer 12 can be reduced when it is expensive, for example, polyetheretherketone.
　図７は、他の例に係る離型フィルム１１の断面図であり、２つの樹脂層の間にクッション層を備えた離型フィルム１１において、樹脂層のうちの一方を、熱可塑性樹脂からなる離型樹脂層１２で構成し、他方を、離型性を有しない樹脂層１６で構成した例を示している。 FIG. 7 is a cross-sectional view of the release film 11 according to another example. In the release film 11 having a cushion layer between two resin layers, one of the resin layers is made of a thermoplastic resin. An example is shown in which the release resin layer 12 is formed and the other is composed of the resin layer 16 having no releasability.
　１１…離型フィルム
　１２…離型樹脂層
　１３…クッション層
　１４…離型コーティング層
　１５，１６…樹脂層 11 ... Release film 12 ... Release resin layer 13 ... Cushion layer 14 ... Release coating layer 15, 16 ... Resin layer

Claims (5)

  1. ２つの樹脂層の間にクッション層を備えた離型フィルムであって、
    前記樹脂層のうち少なくとも一方が、熱可塑性樹脂からなる離型樹脂層であり、その融点が２００℃以上であるとともに、
    前記クッション層が架橋構造を有する硬化性樹脂で構成され、その硬化後の貯蔵弾性率が２３℃において１０ＭＰａ以下である
    離型フィルム。     A release film having a cushion layer between two resin layers.
    At least one of the resin layers is a release resin layer made of a thermoplastic resin, which has a melting point of 200 ° C. or higher and has a melting point of 200 ° C. or higher.
    A release film in which the cushion layer is made of a curable resin having a crosslinked structure, and the storage elastic modulus after curing is 10 MPa or less at 23 ° C.
  2. ２つの樹脂層の間にクッション層を備えた離型フィルムであって、
    前記樹脂層のうち少なくとも一方が、熱可塑性樹脂からなる離型樹脂層であり、その融点が２００℃以上であるとともに、
    前記クッション層が架橋構造を有する硬化された粘弾性体で構成された
    離型フィルム。     A release film having a cushion layer between two resin layers.
    At least one of the resin layers is a release resin layer made of a thermoplastic resin, which has a melting point of 200 ° C. or higher and has a melting point of 200 ° C. or higher.
    A release film in which the cushion layer is made of a cured viscoelastic body having a crosslinked structure.
  3. ２つの樹脂層の間にクッション層を備えた離型フィルムであって、
    前記樹脂層のうち少なくとも一方が、熱可塑性樹脂からなる離型樹脂層であり、その融点が２００℃以上であるとともに、
    前記クッション層が架橋構造を有する硬化された耐熱性粘着剤で構成された
    離型フィルム。     A release film having a cushion layer between two resin layers.
    At least one of the resin layers is a release resin layer made of a thermoplastic resin, which has a melting point of 200 ° C. or higher and has a melting point of 200 ° C. or higher.
    A release film composed of a cured heat-resistant adhesive whose cushion layer has a crosslinked structure.
  4. 前記硬化性樹脂の硬化後の貯蔵弾性率が２３℃において６ＭＰａ以下である
    請求項１に記載の離型フィルム。     The release film according to claim 1, wherein the cured elastic modulus of the curable resin after curing is 6 MPa or less at 23 ° C.
  5. 前記硬化性樹脂の硬化後の貯蔵弾性率が３００℃において０．６ＭＰａ以下である
    請求項１または請求項４に記載の離型フィルム。     The release film according to claim 1 or 4, wherein the cured elastic modulus of the curable resin after curing is 0.6 MPa or less at 300 ° C.
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