JP2005126559A - Film for laser via processing - Google Patents
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- JP2005126559A JP2005126559A JP2003363175A JP2003363175A JP2005126559A JP 2005126559 A JP2005126559 A JP 2005126559A JP 2003363175 A JP2003363175 A JP 2003363175A JP 2003363175 A JP2003363175 A JP 2003363175A JP 2005126559 A JP2005126559 A JP 2005126559A
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- 238000012545 processing Methods 0.000 title claims abstract description 22
- 230000009477 glass transition Effects 0.000 claims abstract description 10
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- 238000002834 transmittance Methods 0.000 claims abstract description 6
- 239000010410 layer Substances 0.000 claims description 29
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- 229910052751 metal Inorganic materials 0.000 claims description 10
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- 239000011112 polyethylene naphthalate Substances 0.000 claims description 4
- 239000011247 coating layer Substances 0.000 claims 1
- 239000000758 substrate Substances 0.000 abstract description 11
- 239000010408 film Substances 0.000 description 75
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- 239000003921 oil Substances 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- 229920001721 polyimide Polymers 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
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- 150000002009 diols Chemical class 0.000 description 3
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- 239000000377 silicon dioxide Substances 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229920001634 Copolyester Polymers 0.000 description 2
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 2
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- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
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- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
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- 230000003712 anti-aging effect Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
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- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
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- NEQFBGHQPUXOFH-UHFFFAOYSA-N 4-(4-carboxyphenyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-N 0.000 description 1
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- 239000004925 Acrylic resin Substances 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
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- 239000004952 Polyamide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
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- 125000002723 alicyclic group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- QHIWVLPBUQWDMQ-UHFFFAOYSA-N butyl prop-2-enoate;methyl 2-methylprop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.COC(=O)C(C)=C.CCCCOC(=O)C=C QHIWVLPBUQWDMQ-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
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- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
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- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
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- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 1
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- 238000012643 polycondensation polymerization Methods 0.000 description 1
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Abstract
Description
本発明は、電子機器などのフレキシブルプリント回路基板、ＩＣタグなどのフレキシブルアンテナ基板に有用な、レーザービア加工性に特に優れ、耐熱性が有り、なおかつ安価なフィルムに関する。 The present invention relates to a film that is particularly excellent in laser via processability, heat resistance, and inexpensive, useful for flexible printed circuit boards such as electronic devices and flexible antenna boards such as IC tags.
近年、電子機器の小型化に伴い、電子回路の高密度実装技術が発展してきている。このような実装技術には、スルーホールおよびブラインドビアホールを有する多層基板を用いたものが知られている。多層基板に対するスルーホールおよびブラインドビアホールの形成は、多層基板用の本体にスルーホール加工孔およびブラインドビアホール用加工孔を形成し、これら加工孔の内周面および層面に導電層を形成することにより行われる。 In recent years, with the miniaturization of electronic devices, high-density mounting technology for electronic circuits has been developed. As such a mounting technique, a technique using a multilayer substrate having a through hole and a blind via hole is known. Through holes and blind via holes are formed in a multilayer substrate by forming through hole processed holes and blind via hole processed holes in the multilayer substrate main body, and forming a conductive layer on the inner peripheral surface and layer surface of these processed holes. Is called.
従来、この種の多層基板におけるスルーホール用加工孔の形成方法には、多層基板用の本体にドリル加工を施すことによるものが採用されていた。一方、ブラインドビアホール用加工孔の形成には、例えば、銅層上であってブラインドビアホール用加工孔を形成するための部分を除く部位に接着層を塗布してから、この接着層上に銅層を印刷形成する方法（特開平３−２７２１９５号公報）や、予め絶縁層および導電層が接着層を介して積層してなる積層板にブラインドビアホール用加工孔の内面を形成する貫通孔を設け、次にこの貫通孔の絶縁層側開口部を閉塞するように絶縁層上に銅層を印刷形成する方法（特開平８−２７２１９５号公報）がある。 Conventionally, as a method for forming a through hole for a through hole in this type of multilayer substrate, a method by drilling a main body for the multilayer substrate has been adopted. On the other hand, for forming the blind via hole machining hole, for example, an adhesive layer is applied to a portion of the copper layer excluding a portion for forming the blind via hole machining hole, and then the copper layer is formed on the adhesive layer. A through hole for forming the inner surface of the blind via hole processing hole is provided in a laminated plate in which an insulating layer and a conductive layer are laminated in advance through an adhesive layer (Japanese Patent Laid-Open No. 3-272195). Next, there is a method (Japanese Patent Laid-Open No. 8-272195) for printing a copper layer on the insulating layer so as to close the opening on the insulating layer side of the through hole.
しかしながら、上記のごとき、ドリル加工、印刷加工による方法では、微細加工を施すことが困難なものとなり、近年における高密度実装化に応じることが出来ないという課題があった。こうような事から、紫外線レーザー（例えば，ＵＶ−ＹＡＧレーザー）、炭酸ガスレーザーなどを照射してビアホールなどを形成する方法（特開平１１−３４２４８５号公報）が微細加工可能な方法として提案されている。 However, as described above, the drilling and printing methods make it difficult to perform microfabrication, and there is a problem that it is impossible to meet the recent high-density mounting. For this reason, a method of forming a via hole by irradiating an ultraviolet laser (for example, UV-YAG laser), a carbon dioxide gas laser, or the like (Japanese Patent Laid-Open No. 11-342485) has been proposed as a method capable of fine processing. Yes.
しかしながら、レーザーによるビア加工でも、加工対象物が樹脂フィルムの場合には、素材などによる要因でレーザービア形状が、過度に孔が開きすぎたり、逆に孔が開かなかったり、孔周辺の盛り上がり（溶融高さが）が大きすぎたりする不適当な形状が発生したりする。このため、導電性ペーストを充填した際に、層間導通の不良、抵抗値のバラツキなどが発生することもある。上記ビアホールを形成する基板としてポリエチレンテレフタレート（特開２００２−２５６４１号公報）が提案されているが、ポリエチレンテレフタレートは、より微細なレーザービア加工性に乏しいと言う課題があった。また、一般にポリイミドフィルムが用いられているが、レーザービア非常に高価であると言う課題があった。 However, even in laser via processing, if the object to be processed is a resin film, the laser via shape may be excessively open due to factors such as the material, or conversely, the hole may not open, Inappropriate shapes may occur, such as the melt height is too large. For this reason, when the conductive paste is filled, defective interlayer conduction, variation in resistance value, and the like may occur. Polyethylene terephthalate (Japanese Patent Laid-Open No. 2002-25641) has been proposed as a substrate for forming the via hole. However, polyethylene terephthalate has a problem that it is poor in finer laser via workability. Further, a polyimide film is generally used, but there is a problem that laser vias are very expensive.
本発明はかかる課題を解決し、レーザービア加工性が良好なフィルムを生産性良く提供することを目的とする。 An object of the present invention is to solve such problems and to provide a film with good laser via processability with high productivity.
本発明のレーザービア加工用フィルムは、基材層が２軸延伸が施されたポリエステルフィルムである。なおかつ基材層は、ガラス転移温度が７０〜１６０℃、熱伝導率が０．１０Ｗ／（ｍ・Ｋ）以上であり、波長３５５ｎｍでの光線透過率が３０％以下、ヤング率が５〜２０ＧＰａである。 The film for laser via processing of the present invention is a polyester film in which a base material layer is biaxially stretched. The base material layer has a glass transition temperature of 70 to 160 ° C., a thermal conductivity of 0.10 W / (m · K) or more, a light transmittance at a wavelength of 355 nm of 30% or less, and a Young's modulus of 5 to 20 GPa. It is.
また、本発明のフィルムは、
（１）２００℃における熱収縮率の絶対値が３％以下であること。
（２）ポリエステルがポリエチレンナフタレートであること。
をそれぞれ好ましい態様として含んでいる。
The film of the present invention is
(1) The absolute value of heat shrinkage at 200 ° C. is 3% or less.
(2) The polyester is polyethylene naphthalate.
Are included as preferred embodiments.
本発明により、レーザービア加工性が良好なフィルムを生産性良く提供することができる。 According to the present invention, a film having good laser via processability can be provided with high productivity.
＜基材層組成＞
本発明フィルムの基材層を構成するポリエステル樹脂としては、ジオールとジカルボン酸とから縮重合によって得られるポリマーであり、ジカルボン酸としては、例えばテレフタル酸、イソフタル酸、２，６−ナフタリンジカルボン酸、４，４’−ジフェニルジカルボン酸、アジピン酸、セバシン酸等に代表されるものであり、またジオールとは、例えばエチレングリコール、１，４−ブタンジオール、１，４−シクロヘキサンジメタノール、１，６−ヘキサンジオール等で代表されるものである。特にポリエチレンテレフタレート、ポリエチレン−２，６−ナフタリンジカルボキシレートが好ましい。また、これらポリエステルはホモポリエステルであっても、共重合ポリエステルであっても良く、共重合成分としては、例えばジエチレングリコール、ネオペンチルグリコール、ポリアルキレングリコールなどのジオール成分、アジピン酸、セバシン酸、フタル酸、イソフタル酸、２，６−ナフタレンジカルボン酸、５−ナトリウムスルホイソフタル酸などのジカルボン酸成分があげられる。
<Base layer composition>
The polyester resin constituting the substrate layer of the film of the present invention is a polymer obtained by condensation polymerization from a diol and a dicarboxylic acid. Examples of the dicarboxylic acid include terephthalic acid, isophthalic acid, 2,6-naphthalene dicarboxylic acid, It is represented by 4,4′-diphenyldicarboxylic acid, adipic acid, sebacic acid and the like. Examples of the diol include ethylene glycol, 1,4-butanediol, 1,4-cyclohexanedimethanol, 1,6 -It is represented by hexanediol etc. Particularly preferred are polyethylene terephthalate and polyethylene-2,6-naphthalene dicarboxylate. These polyesters may be homopolyesters or copolyesters. Examples of copolymer components include diol components such as diethylene glycol, neopentyl glycol, and polyalkylene glycol, adipic acid, sebacic acid, and phthalic acid. And dicarboxylic acid components such as isophthalic acid, 2,6-naphthalenedicarboxylic acid, and 5-sodiumsulfoisophthalic acid.
本発明フィルムの基材層は、ガラス転移温度が７０〜１６０℃である。これは、好ましくは１００〜１６５℃、更に好ましくは１１５〜１５０℃である。７０℃未満であると、レーザービア加工時に微細な加工孔が形成されなかったり、溶融高さが発生したりする課題が起こる。一方、１６０℃を超えるものは過剰品質であり、該ガラス転移温度を超える樹脂の２軸延伸製膜は非常に作業性に劣り、安価なフィルムが得られない。これら、観点から基材層を構成する樹脂としては、ポリエチレンナフタレートが特に好ましい。 The substrate layer of the film of the present invention has a glass transition temperature of 70 to 160 ° C. This is preferably 100 to 165 ° C, more preferably 115 to 150 ° C. When the temperature is less than 70 ° C., there are problems in that fine processing holes are not formed during the laser via processing or the melt height is generated. On the other hand, if the temperature exceeds 160 ° C., the quality is excessive, and biaxial stretching of the resin exceeding the glass transition temperature is very inferior in workability, and an inexpensive film cannot be obtained. From these viewpoints, polyethylene naphthalate is particularly preferable as the resin constituting the base material layer.
また、このポリエステルの中には公知の各種添加剤、たとえば、酸化防止剤、帯電防止剤などが添加されていても良い。 Various known additives such as antioxidants and antistatic agents may be added to the polyester.
＜滑剤＞
本発明フィルムには、ハンドリング性を向上させるため、本目的を超えない範囲で不活性粒子を添加しても構わない。不活性粒子としては、たとえば、炭酸カルシウム、シリカ、タルク、クレー、などの無機粒子、シリコーンや熱可塑性樹脂や熱硬化性樹脂からなる有機粒子、硫酸バリウム、酸化チタン等の顔料を単独あるいは２種以上添加しても良い。
<Lubricant>
In order to improve the handleability, inert particles may be added to the film of the present invention within a range not exceeding this purpose. Examples of the inert particles include inorganic particles such as calcium carbonate, silica, talc, and clay, organic particles made of silicone, thermoplastic resin, and thermosetting resin, and pigments such as barium sulfate and titanium oxide, alone or in combination. You may add more.
これら不活性粒子をポリエステルへ添加含有させる前に、精製プロセスを用いて、粒径調整、粗大粒子除去を行うことが好ましい。生成プロセスの工業的手段としては、粉砕手段で例えばジェットミル、ボールミル等が挙げられ、また分級手段では例えば乾式もしくは湿式遠心分離機等が挙げられる。なお、これらの手段は２種以上を組み合わせ、段階的に精製しても良いのはもちろんである。 Before adding these inert particles to the polyester, it is preferable to adjust the particle size and remove coarse particles using a purification process. Examples of industrial means for the production process include a pulverizing means such as a jet mill and a ball mill, and classification means such as a dry or wet centrifuge. Of course, these means may be combined in two or more and purified in stages.
また、含有させる方法としては各種の方法を用いることができる。その代表的な方法として、下記のような方法を挙げることができる。
（ア）ポリエステル合成時のエステル交換反応もしくはエステル化反応終了前に添加、もしくは重縮合反応開始前に添加する方法。
（イ）ポリエステルに添加し、溶融混練する方法。
（ウ）上記（ア）、（イ）の方法において酸化チタンや他の滑剤を多量添加したマスターペレットを製造し、これら添加剤を含有しないポリエステルと混練して所定量の添加物を含有させる方法。
Moreover, various methods can be used as the method of inclusion. The following method can be mentioned as the typical method.
(A) A method of adding before transesterification or esterification reaction at the time of polyester synthesis or adding before the start of polycondensation reaction.
(A) A method of adding to polyester and melt-kneading.
(C) A method of producing master pellets in which a large amount of titanium oxide or other lubricant is added in the methods (a) and (b) above, and kneading with polyester not containing these additives to contain a predetermined amount of additives. .
なお、前記（ア）のポリエステル合成時に添加する方法を用いる場合には、酸化チタンや他の滑剤をグリコールに分散したスラリーとして、反応系に添加することが好ましい。 In addition, when using the method added at the time of the polyester synthesis | combination of said (a), it is preferable to add to a reaction system as a slurry which disperse | distributed titanium oxide and another lubricant to glycol.
＜塗膜＞
本発明においては、基材層の少なくとも片面に以下の成分からなる塗膜を積層することができる。その場合に、例えば延伸可能なポリエステルフィルムに塗膜を形成する成分を含む水溶液を塗布した後、乾燥、延伸し必要に応じて熱処理することにより積層することができる。
<Coating film>
In the present invention, a coating film comprising the following components can be laminated on at least one surface of the base material layer. In that case, after apply | coating the aqueous solution containing the component which forms a coating film, for example to the stretchable polyester film, it can laminate | stack by drying, extending | stretching, and heat-processing as needed.
コーティング塗剤のバインダー樹脂としては、熱可塑性樹脂または熱硬化性樹脂の各種樹脂が使用し得る。たとえば、ポリエステル、ポリイミド、ポリアミド、ポリエステルアミド、ポリ塩化ビニル、ポリ（メタ）アクリル酸エステル、ポリウレタン、ポリ塩化ビニル、ポリスチレン、ポリオレフィンや、これらの共重合体やブレンド物である。なかでもポリエステル、ポリイミド、ポリ（メタ）アクリル酸エステル、ポリウレタンが好ましい。更に架橋剤を加えて架橋したものでも良い。 As the binder resin of the coating agent, various resins such as a thermoplastic resin or a thermosetting resin can be used. For example, polyester, polyimide, polyamide, polyesteramide, polyvinyl chloride, poly (meth) acrylic acid ester, polyurethane, polyvinyl chloride, polystyrene, polyolefin, and copolymers and blends thereof. Of these, polyester, polyimide, poly (meth) acrylic acid ester, and polyurethane are preferable. Further, it may be crosslinked by adding a crosslinking agent.
コーティング塗剤の溶媒としては、トルエン、酢酸エチル、メチルエチルケトンなどの有機溶媒および混合物が使用でき、更に水を溶媒としてもよい。 As a solvent for the coating agent, organic solvents such as toluene, ethyl acetate, methyl ethyl ketone, and mixtures thereof can be used, and water may be used as a solvent.
また本発明においては少なくとも最外層には、コポリエステル、ポリアルキレンオキサイド及び微粒子を主成分とする塗膜を積層してもよい。 In the present invention, at least the outermost layer may be laminated with a coating film composed mainly of copolyester, polyalkylene oxide and fine particles.
本発明においては塗膜を形成する成分として、上記成分以外にメラミン樹脂等の他の樹脂、帯電防止剤、着色剤、界面活性剤等を使用することができる。また、所望に応じて、その他の成分を配合することができる。配合剤としては、軟質重合体、フィラー、熱安定剤、耐候安定剤、老化防止剤、レベリング剤、帯電防止剤、スリップ剤、アンチブロッキング剤、防曇剤、染料、顔料、天然油、合成油、ワックス、乳剤、充填剤、硬化剤、難燃剤などが挙げられ、その配合割合は、本発明の目的を損なわない範囲で適宜選択される。 In the present invention, as a component for forming a coating film, in addition to the above components, other resins such as melamine resin, antistatic agents, colorants, surfactants and the like can be used. Moreover, other components can be mix | blended as desired. Compounding agents include soft polymers, fillers, heat stabilizers, weathering stabilizers, anti-aging agents, leveling agents, antistatic agents, slip agents, antiblocking agents, antifogging agents, dyes, pigments, natural oils, and synthetic oils. , Waxes, emulsions, fillers, curing agents, flame retardants and the like, and the blending ratio thereof is appropriately selected within a range not impairing the object of the present invention.
ポリエステルフィルムへ水溶液を塗布する場合は、通常の塗工工程、すなわち二軸延伸熱固定したポリエステルフィルムに、該フィルムの製造工程と切り離した工程で塗布を行うと、埃やちり等を巻き込み易く好ましくない。かかる観点よりクリーンな雰囲気での塗布、すなわちフィルムの製造工程中での塗布が好ましい。そして、この塗布によれば、塗膜のポリエステルフィルムへの密着性が更に向上する。 When applying an aqueous solution to a polyester film, it is preferable to apply it to the normal coating process, that is, a biaxially stretched heat-fixed polyester film in a process separated from the film manufacturing process, so that dust and dust are easily involved. Absent. From such a viewpoint, application in a clean atmosphere, that is, application in the film production process is preferable. And according to this application | coating, the adhesiveness to the polyester film of a coating film further improves.
塗布方法としては、公知の任意の塗布方が適用できる。例えばロールコート法、グラビアコート法、ロールブラッシュ法、スプレーコート法、エアーナイフコート法、含浸法およびカーテンコート法などを単独または組み合わせて用いることができる。 As a coating method, any known coating method can be applied. For example, a roll coating method, a gravure coating method, a roll brush method, a spray coating method, an air knife coating method, an impregnation method, and a curtain coating method can be used alone or in combination.
＜金属箔＞
本発明では、フィルムを基材とし金属箔を積層することができる。そうした金属箔を積層しておくことで、本発明フィルムを適用した回路基板等を製造する際の工程の生産性を上げることができ好ましい。該金属箔としては、銅箔やアルミニウム箔などの金属箔が挙げられる。これら金属箔としては、圧延されて作成されたものや電解によって作成されたものなど一般的な方法で得られるものである。
<Metal foil>
In the present invention, a metal foil can be laminated using a film as a base material. By laminating such metal foils, it is preferable because the productivity of the process when manufacturing a circuit board or the like to which the film of the present invention is applied can be increased. Examples of the metal foil include metal foil such as copper foil and aluminum foil. These metal foils can be obtained by a general method such as one produced by rolling or one produced by electrolysis.
これら金属箔の積層方法としては、接着剤を介する方法やフィルム表層を溶融させ直接シールする方法などが挙げられる。接着剤については、特に言及するものではないが、耐熱性の観点から硬化性樹脂が好ましい。好適な硬化性樹脂としてはエポキシ樹脂、フェノール樹脂、アクリル樹脂、ポリイミド樹脂、ポリアミド樹脂、ポリイソシアネート樹脂、ポリエステル樹脂、ポリフェニルエーテル樹脂、脂環式オレフィン重合体などが挙げられる。 Examples of a method for laminating these metal foils include a method using an adhesive and a method for directly melting and sealing a film surface layer. The adhesive is not particularly mentioned, but a curable resin is preferable from the viewpoint of heat resistance. Suitable curable resins include epoxy resins, phenol resins, acrylic resins, polyimide resins, polyamide resins, polyisocyanate resins, polyester resins, polyphenyl ether resins, alicyclic olefin polymers, and the like.
また、所望に応じて、その他の成分を配合することができる。配合剤としては、紫外線吸収剤、軟質重合体、フィラー、熱安定剤、耐候安定剤、老化防止剤、レベリング剤、帯電防止剤、スリップ剤、アンチブロッキング剤、防曇剤、染料、顔料、天然油、合成油、ワックス、乳剤、充填剤、硬化剤、難燃剤などが挙げられ、その配合割合は、本発明の目的を損なわない範囲で適宜選択される。
また、メッキやスパッタリングなどによって直接基材フィルムに金属箔を形成させる方法であっても構わない。
Moreover, other components can be mix | blended as desired. Compounding agents include UV absorbers, soft polymers, fillers, heat stabilizers, weathering stabilizers, anti-aging agents, leveling agents, antistatic agents, slip agents, antiblocking agents, antifogging agents, dyes, pigments, natural Examples thereof include oils, synthetic oils, waxes, emulsions, fillers, curing agents, flame retardants, and the like, and the blending ratio thereof is appropriately selected within a range not impairing the object of the present invention.
Moreover, you may be the method of forming metal foil directly on a base film by plating, sputtering, etc.
＜製膜＞
本発明のフィルムは、テンター法、インフレーション法等の従来知られている製膜方法を用いて製造することができる。
<Film formation>
The film of the present invention can be produced using a conventionally known film production method such as a tenter method or an inflation method.
予め乾燥したポリエステル樹脂を２８０℃に加熱された押出機に供給し、Ｔダイよしシート状に成形する。このＴダイより押し出されたフィルムを表面温度１０〜６０℃の冷却ドラムで冷却固化し、この未延伸フィルムをロール加熱、赤外線加熱等で加熱し、縦方向（連続製膜方向）に延伸して縦延伸フィルムを得る。この延伸は２個以上のロールの周速差を利用して行うのが好ましい。延伸温度はポリエステルのガラス転移点（Ｔｇ）より高い温度、更にはＴｇより２０〜４０℃高い温度とするのが好ましい。延伸倍率は、この用途の要求特性にもよるが、２．５倍以上４．０倍以下とするのが好ましい。更に好ましくは、２．８倍以上３．９倍以下とするのが好ましい。２．５倍以下とするとフィルムの厚み斑が悪くなり良好なフィルムが得られず、４．０倍以上とすると製膜中に破断が発生し易くなり課題がある。 The polyester resin dried beforehand is supplied to the extruder heated at 280 degreeC, and it shape | molds in a sheet form by T die. The film extruded from the T-die is cooled and solidified with a cooling drum having a surface temperature of 10 to 60 ° C., and this unstretched film is heated by roll heating, infrared heating or the like, and stretched in the longitudinal direction (continuous film forming direction). A longitudinally stretched film is obtained. This stretching is preferably performed by utilizing the difference in peripheral speed between two or more rolls. The stretching temperature is preferably higher than the glass transition point (Tg) of the polyester, more preferably 20 to 40 ° C. higher than Tg. The draw ratio is preferably 2.5 times or more and 4.0 times or less, although it depends on the required characteristics of this application. More preferably, it is 2.8 times or more and 3.9 times or less. If it is 2.5 times or less, the thickness unevenness of the film is deteriorated, and a good film cannot be obtained.
縦延伸フィルムは、続いて、横延伸（連続製膜方向に垂直な方向への延伸）、熱固定、熱弛緩の処理を順次施して二軸配向フィルムとするが、これら処理はフィルムを走行させながら行う。横延伸の処理はポリエステルのガラス転移点（Ｔｇ）より２０℃高い温度から始める。そしてポリエステルの融点（Ｔｍ）より（１２０〜３０）℃低い温度まで昇温しながら行う。この延伸開始温度は（Ｔｇ＋４０）℃以下であることが好ましい。また延伸最高温度はＴｍより（１００〜４０）℃低い温度であることが好ましい。 The longitudinally stretched film is subsequently subjected to lateral stretching (stretching in the direction perpendicular to the continuous film-forming direction), heat setting, and thermal relaxation to form a biaxially oriented film. While doing. The transverse stretching process starts at a temperature 20 ° C. higher than the glass transition point (Tg) of the polyester. And it heats up to (120-30) degree C temperature lower than melting | fusing point (Tm) of polyester. The stretching start temperature is preferably (Tg + 40) ° C. or lower. Moreover, it is preferable that the extending | stretching maximum temperature is a temperature lower (100-40) degreeC than Tm.
横延伸過程での昇温は連続的でも段階的（逐次的）でもよい。通常逐次的に昇温する。例えばステンターの横延伸ゾーンをフィルム走行方向に沿って複数に分け、各ゾーンごとに所定温度の加熱媒体を流すことで昇温する。横延伸開始温度が低すぎるとフィルムの破れが起こり、好ましくない。また延伸最高温度が（Ｔｍ−１２０）℃より低いとフィルムの熱収が大きくなり、また幅方向の物性の均一性が低下し、好ましくない。一方延伸最高温度が（Ｔｍ−３０）℃より高いとフィルムが柔らかくなり外乱等によってフィルムの破れが起こり、好ましくない。 The temperature increase in the transverse stretching process may be continuous or stepwise (sequential). Usually the temperature is raised sequentially. For example, the transverse stretching zone of the stenter is divided into a plurality along the film running direction, and the temperature is raised by flowing a heating medium of a predetermined temperature for each zone. When the transverse stretching start temperature is too low, the film is torn, which is not preferable. On the other hand, if the maximum stretching temperature is lower than (Tm−120) ° C., the heat yield of the film increases, and the uniformity of physical properties in the width direction decreases, which is not preferable. On the other hand, if the maximum stretching temperature is higher than (Tm-30) ° C., the film becomes soft and the film is torn due to disturbance or the like.
横延伸の倍率は、この用途の要求特性にもよるが、２．５倍以上４．０倍以下とするのが好ましい。更に好ましくは、２．８倍以上３．９倍以下とするのが好ましい。２．５倍以下とするとフィルムの厚み斑が悪くなり良好なフィルムが得られず、４．０倍以上とすると製膜中に破断が発生し易くなり課題がある。 The transverse stretching ratio is preferably 2.5 times or more and 4.0 times or less, although it depends on the required characteristics of this application. More preferably, it is 2.8 times or more and 3.9 times or less. If it is 2.5 times or less, the thickness unevenness of the film is deteriorated and a good film cannot be obtained, and if it is 4.0 times or more, breakage tends to occur during film formation, which causes a problem.
なお、２軸延伸されたフィルムはその後、熱固定処理が施される。本熱固定を施すことにより、フィルムの熱寸法安定性が向上する。すなわち本発明で基材層は、２００℃における熱収縮率が−３〜３％が好ましい。これは、より好ましくは−２〜２％、更に好ましくは−１〜１％である。−３％未満や３％を超えると、例えば回路基板を形成する工程においてフィルムの熱収縮が大きくなり、良好な回路が形成できない場合があるため好ましくない。 The biaxially stretched film is then heat set. By performing the heat setting, the thermal dimensional stability of the film is improved. That is, in the present invention, the base material layer preferably has a thermal shrinkage at 200 ° C. of −3 to 3%. This is more preferably -2 to 2%, and still more preferably -1 to 1%. If it is less than -3% or more than 3%, for example, in the process of forming a circuit board, the film has a large thermal contraction, which is not preferable because a good circuit may not be formed.
こうした特性を満足するには、例えば本熱固定処理を（Ｔｍ−１００℃）以上の温度で施すことにより達成することができる。 Satisfying such characteristics can be achieved, for example, by applying the heat setting treatment at a temperature of (Tm-100 ° C.) or higher.
また本発明フィルムの基材層は、熱伝導率が０．１０Ｗ／（ｍ・Ｋ）以上である。これは、好ましくは０．１１Ｗ／（ｍ・Ｋ）以上、更に好ましくは０．１２Ｗ／（ｍ・Ｋ）以上である。０．１０Ｗ／（ｍ・Ｋ）未満であるとレーザービア、特に炭酸ガスレーザー加工時に十分に熱が伝わらず、良好な加工孔が形成されない。 The base material layer of the film of the present invention has a thermal conductivity of 0.10 W / (m · K) or more. This is preferably 0.11 W / (m · K) or more, more preferably 0.12 W / (m · K) or more. When it is less than 0.10 W / (m · K), heat is not sufficiently transmitted during laser via processing, particularly carbon dioxide laser processing, and good processing holes are not formed.
また本発明フィルムの基材層は、波長３５５ｎｍでの光線透過率が３０％以下である。これは、好ましくは２０％以下、更に好ましくは１５％以下である。３０％を超えるとレーザービア、特にＵＶレーザーでの加工性が良くなく、良好な加工孔が形成されない。また、本手段を達成するための方法として、例えば紫外線吸収剤を添加したりフィルム基材に塗布したりすることをしても構わない。 The base material layer of the film of the present invention has a light transmittance of 30% or less at a wavelength of 355 nm. This is preferably 20% or less, more preferably 15% or less. If it exceeds 30%, the processability with a laser via, particularly with a UV laser, is not good, and good processed holes are not formed. Moreover, as a method for achieving this means, for example, an ultraviolet absorber may be added or applied to a film substrate.
更に本発明フィルムの基材層は、ヤング率が５〜２０ＧＰａである。これは、好ましくは５〜１８ＧＰａ、更に好ましくは５〜１５ＧＰａである。ヤング率とレーザービア性の関係は明確にはわからないが、おそらくフィルムの剛性が関係しているものと思われる。５ＧＰａ未満であるとフィルムの剛性が不足しており、そのため加工孔経が必要以上に大きくなり好ましくない、一方２０ＧＰａを越えるものは、過剰品質であり、生産性を下げる。 Furthermore, the base material layer of the film of the present invention has a Young's modulus of 5 to 20 GPa. This is preferably 5 to 18 GPa, more preferably 5 to 15 GPa. The relationship between Young's modulus and laser via properties is not clearly understood, but it is probably related to the rigidity of the film. If it is less than 5 GPa, the rigidity of the film is insufficient, so that the processing hole diameter becomes unnecessarily large, which is not preferable. On the other hand, if it exceeds 20 GPa, the quality is excessive and the productivity is lowered.
ところで、本発明のフィルムは、その片面または両面に、他の機能を付与するために、他の層をさらに積層した積層体としてもよい。ここでいう、他の層とは透明なポリエステルフィルム、金属薄膜やハードコート層があげられる。 By the way, the film of this invention is good also as a laminated body which further laminated | stacked the other layer, in order to provide another function to the single side | surface or both surfaces. Here, the other layer includes a transparent polyester film, a metal thin film, and a hard coat layer.
＜評価方法＞
１．ガラス転移温度
サンプル約１０ｍｇを測定用のアルミニウム製パンに封入して示差熱量計（ＴＡｉｎｓｔｒｕｍｅｎｔｓ社製商品名「ＤＳＣ２９２０」）に装着し、２５℃から２０℃／分の速度で３００℃まで昇温させ、３００℃で５分間保持した後取出し、直ちに氷の上に移して急冷する。このパンを再度示差熱量計に装着し、−７０℃から１０℃／分の速度で昇温させてガラス転移温度（Ｔｇ：℃）を測定した。
<Evaluation method>
1. Glass transition temperature About 10 mg of sample is sealed in an aluminum pan for measurement and attached to a differential calorimeter (trade name “DSC2920” manufactured by TA instruments), and the temperature is raised from 25 ° C. to 300 ° C. at a rate of 20 ° C./min. Take out after holding at 300 ° C. for 5 minutes, immediately transfer to ice and quench. This pan was again attached to the differential calorimeter, and the glass transition temperature (Tg: ° C.) was measured by raising the temperature from −70 ° C. at a rate of 10 ° C./min.
２．熱伝導率
試料を直径１０ｍｍの円板状に切り、理学電機製ＬＦ／ＴＣＭ−ＦＡ８５１０Ｂを用い、試料前面にレーザー光を照射し、その瞬間に試料裏面の温度変化を熱電対で測定する。時間と温度の変化曲線を得る。この曲線から温度差△Ｔが飽和値の１／２になったときの時間（ｔ１／２）を測定する。そして下記式よりまず熱拡散率αを求め、続いて熱伝導率λを算出する。
α＝１．３７×（Ｌ／π）２／（ｔ１／２）
λ＝α・Ｃｐ・β
ここで、Ｌは試料の厚さ、Ｃｐは試料の比熱、βは密度を指す。
2. Thermal conductivity A sample is cut into a disk shape having a diameter of 10 mm, a laser beam is irradiated on the front surface of the sample using a LF / TCM-FA8510B manufactured by Rigaku Corporation, and the temperature change on the back surface of the sample is measured with a thermocouple at that moment. Obtain time and temperature change curves. From this curve, the time (t 1/2 ) when the temperature difference ΔT becomes 1/2 of the saturation value is measured. Then, the thermal diffusivity α is first obtained from the following formula, and then the thermal conductivity λ is calculated.
α = 1.37 × (L / π) 2 / (t 1/2 )
λ = α ・ Cp ・ β
Here, L is the thickness of the sample, Cp is the specific heat of the sample, and β is the density.
３．光線透過率
分光光度計（島津製作所製ＵＶ−３１０１ＰＣ）を用い、３５５ｎｍでの光線透過率を測定した。
3. Light transmittance The light transmittance at 355 nm was measured using a spectrophotometer (UV-3101PC manufactured by Shimadzu Corporation).
４．ヤング率
フィルムを試料幅１０ｍｍ、長さ１５ｃｍに切り、チャック間１００ｍｍにして引張速度１０ｍｍ／分、チャート速度５００ｍｍ／分でインストロンタイプの万能引張試験装置にて引張り、得られる過重−伸び曲線の立ち上がり部の接線より、フィルム連続製膜方向（ＭＤ方向）と、製膜方向に垂直な方向（ＴＤ方向）において、ヤング率を計算する。
4). Young's modulus The film was cut into a sample width of 10 mm and a length of 15 cm, and the tension between the chucks was set to 100 mm and pulled with an Instron type universal tensile tester at a tensile speed of 10 mm / min and a chart speed of 500 mm / min. From the tangent line of the rising portion, the Young's modulus is calculated in the film continuous film forming direction (MD direction) and the direction perpendicular to the film forming direction (TD direction).
５．熱収縮率
フィルムサンプルに３０ｃｍ間隔で標点をつけ、荷重をかけずに２００℃のオーブンで熱処理を実施し、熱処理後の標点間隔を測定して、フィルム連続製膜方向（ＭＤ方向）と、製膜方向に垂直な方向（ＴＤ方向）において、下記式にて熱収縮率Ｒ（％）を算出した。
Ｒ（％）＝｛（Ｌ１−Ｌ２）／Ｌ１｝×１００
ここで、Ｌ１は熱処理前標点間距離、Ｌ２は熱処理後標点間距離である。
5). Heat shrinkage rate Marks are attached to film samples at intervals of 30 cm, heat treatment is carried out in an oven at 200 ° C. without applying a load, the distance between the marks after heat treatment is measured, and the film is continuously formed (MD direction). In the direction perpendicular to the film forming direction (TD direction), the thermal contraction rate R (%) was calculated by the following formula.
R (%) = {(L1-L2) / L1} × 100
Here, L1 is the distance between the marks before heat treatment, and L2 is the distance between the marks after heat treatment.
６．レーザービア加工性
レーザー加工機（ＥＳＩ社製 Ｍｏｄｅｌ５３２０）を用い、加工エネルギー０．５Ｗ、周波数２０ＫＨｚ、孔径５０μのレーザー加工条件にてフィルムに照射後、キーエンス社製のレーザー顕微鏡（ＶＦ−７５１０）にて溶融高さをｎ＝５点観察測定し、その平均値をもとに下記基準で判定した。
○：溶融高さが８μｍ未満である。
×：溶融高さが８μｍ以上である。
6). Laser via processability Using a laser processing machine (Model 5320 manufactured by ESI), after irradiating the film under laser processing conditions of processing energy of 0.5 W, frequency of 20 KHz, and hole diameter of 50 μm, it was applied to a Keyence laser microscope (VF-7510). Then, the melt height was measured by observing n = 5 points, and judged based on the average value based on the following criteria.
○: The melt height is less than 8 μm.
X: The melt height is 8 μm or more.
［実施例１］
ポリエチレンナフタレート樹脂に平均粒径０．３μｍの球状シリカを０．１％添加し、２９０℃に加熱された押出機に供給し、２９０℃のダイスよりシート状に成形した。さらにこのシートを表面温度６０℃の冷却ドラムで冷却固化した未延伸フィルムを１４０℃に加熱したロール群に導き、長手方向（縦方向）に３．３倍で延伸し、６０℃のロール群で冷却した。続いて、縦延伸したフィルムの両端をクリップで保持しながらテンターに導き１５０℃に加熱された雰囲気中で長手に垂直な方向（横方向）に３．６倍で延伸した。その後テンタ−内で２３５℃の熱固定を行い、２４０℃で３％の弛緩後、均一に除冷して、室温まで冷やして７５μｍ二軸延伸フィルムを得た。得られたフィルムの特性は表１の通りである。本実施例のフィルムは、寸法安定性に優れていた。
[Example 1]
0.1% of spherical silica having an average particle size of 0.3 μm was added to polyethylene naphthalate resin, which was supplied to an extruder heated to 290 ° C. and molded into a sheet form from a 290 ° C. die. Furthermore, the unstretched film obtained by cooling and solidifying the sheet with a cooling drum having a surface temperature of 60 ° C. is led to a roll group heated to 140 ° C., stretched 3.3 times in the longitudinal direction (longitudinal direction), and the roll group at 60 ° C. Cooled down. Subsequently, the film was stretched at a magnification of 3.6 times in a direction perpendicular to the longitudinal direction (lateral direction) in an atmosphere heated to 150 ° C. while being guided to a tenter while holding both ends of the longitudinally stretched film with clips. Thereafter, the film was heat-set at 235 ° C. in a tenter, relaxed 3% at 240 ° C., uniformly cooled, and cooled to room temperature to obtain a 75 μm biaxially stretched film. The properties of the obtained film are as shown in Table 1. The film of this example was excellent in dimensional stability.
［比較例１］
ポリエチレンテレフタレート樹脂に平均粒径０．３μｍの球状シリカを０．１％添加し、２８０℃に加熱された押出機に供給し、２８０℃のダイスよりシート状に成形した。さらにこのシートを表面温度２０℃の冷却ドラムで冷却固化した未延伸フィルムを１１０℃に加熱したロール群に導き、長手方向（縦方向）に３．１倍で延伸し、２０℃のロール群で冷却した。続いて、縦延伸したフィルムの両端をクリップで保持しながらテンターに導き１２０℃に加熱された雰囲気中で長手に垂直な方向（横方向）に３．３倍で延伸した。その後テンタ−内で２３５℃の熱固定を行い、２４０℃で５％の弛緩後、均一に除冷して、室温まで冷やして７５μｍ二軸延伸フィルムを得た。得られたフィルムの特性は表１の通りである。ガラス転移温度が低いため、レーザービア加工性に劣るものであった。
[Comparative Example 1]
0.1% of spherical silica having an average particle size of 0.3 μm was added to the polyethylene terephthalate resin, and the resulting mixture was supplied to an extruder heated to 280 ° C. and molded into a sheet form from a die at 280 ° C. Further, the unstretched film obtained by cooling and solidifying the sheet with a cooling drum having a surface temperature of 20 ° C. is led to a roll group heated to 110 ° C., and stretched by 3.1 times in the longitudinal direction (longitudinal direction). Cooled down. Subsequently, the film was stretched by 3.3 times in a direction perpendicular to the longitudinal direction (lateral direction) in an atmosphere heated to 120 ° C. while being guided to a tenter while holding both ends of the longitudinally stretched film with clips. Thereafter, the film was heat-set at 235 ° C. in a tenter, relaxed by 5% at 240 ° C., uniformly cooled, and cooled to room temperature to obtain a 75 μm biaxially stretched film. The properties of the obtained film are as shown in Table 1. Since the glass transition temperature was low, the laser via processability was poor.
［比較例２］
東レ・デュポン製「カプトン；タイプＨ」の７５μｍフィルムを用いた。得られたフィルムの特性は表１の通りである。熱伝導率が低く、ヤング率も低くいためレーザービア加工性に劣るものであった。
[Comparative Example 2]
A 75 μm film of “Kapton; Type H” manufactured by Toray DuPont was used. The properties of the obtained film are as shown in Table 1. Since the thermal conductivity was low and the Young's modulus was low, the laser via processability was poor.
本発明のフィルムは、レーザービア加工性に優れ、電子機器などのフレキシブルプリント配線基板やＩＣタグなどのフレキシブルアンテナ基板などに有用である。 The film of the present invention is excellent in laser via processability, and is useful for flexible printed wiring boards such as electronic devices and flexible antenna boards such as IC tags.
Claims (6)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| JP2003363175A JP2005126559A (en) | 2003-10-23 | 2003-10-23 | Film for laser via processing |
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| JP2003363175A JP2005126559A (en) | 2003-10-23 | 2003-10-23 | Film for laser via processing |
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| JP2005126559A true JP2005126559A (en) | 2005-05-19 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016190435A (en) * | 2015-03-31 | 2016-11-10 | 積水化学工業株式会社 | Method for producing layered structure, and the structure |
| KR101761916B1 (en) * | 2009-12-18 | 2017-07-26 | 데이진 필름 솔루션스 가부시키가이샤 | Film for fpc board stiffener, fpc board stiffener therefrom and fpc board laminated body therefrom |
| JPWO2018194066A1 (en) * | 2017-04-19 | 2019-12-19 | 株式会社村田製作所 | Method for manufacturing carrier film and electronic component |
-
2003
- 2003-10-23 JP JP2003363175A patent/JP2005126559A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101761916B1 (en) * | 2009-12-18 | 2017-07-26 | 데이진 필름 솔루션스 가부시키가이샤 | Film for fpc board stiffener, fpc board stiffener therefrom and fpc board laminated body therefrom |
| JP2016190435A (en) * | 2015-03-31 | 2016-11-10 | 積水化学工業株式会社 | Method for producing layered structure, and the structure |
| JPWO2018194066A1 (en) * | 2017-04-19 | 2019-12-19 | 株式会社村田製作所 | Method for manufacturing carrier film and electronic component |
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