JP5435699B2 - Wiring board manufacturing method, wiring board, and semiconductor device - Google Patents

Wiring board manufacturing method, wiring board, and semiconductor device Download PDF

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JP5435699B2
JP5435699B2 JP2009053819A JP2009053819A JP5435699B2 JP 5435699 B2 JP5435699 B2 JP 5435699B2 JP 2009053819 A JP2009053819 A JP 2009053819A JP 2009053819 A JP2009053819 A JP 2009053819A JP 5435699 B2 JP5435699 B2 JP 5435699B2
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film
wiring board
manufacturing
wiring
carbon atoms
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JP2010212291A (en
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慎 寺木
真樹 吉田
聡子 高橋
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Namics Corp
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    • H—ELECTRICITY
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    • H01L24/02—Bonding areas ; Manufacturing methods related thereto
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    • H01L2224/10—Bump connectors; Manufacturing methods related thereto
    • H01L2224/1012—Auxiliary members for bump connectors, e.g. spacers
    • H01L2224/10122—Auxiliary members for bump connectors, e.g. spacers being formed on the semiconductor or solid-state body to be connected
    • H01L2224/10125—Reinforcing structures
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    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/44—Structure, shape, material or disposition of the wire connectors prior to the connecting process
    • H01L2224/45—Structure, shape, material or disposition of the wire connectors prior to the connecting process of an individual wire connector
    • H01L2224/45001—Core members of the connector
    • H01L2224/45099—Material
    • H01L2224/451—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te) and polonium (Po), and alloys thereof
    • H01L2224/45138—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te) and polonium (Po), and alloys thereof the principal constituent melting at a temperature of greater than or equal to 950°C and less than 1550°C
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    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
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    • H01L2224/481—Disposition
    • H01L2224/48151—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
    • H01L2224/48221—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
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    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/481—Disposition
    • H01L2224/48151—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
    • H01L2224/48221—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
    • H01L2224/48225—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation
    • H01L2224/48227—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation connecting the wire to a bond pad of the item
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    • H01L2924/1025—Semiconducting materials
    • H01L2924/10251—Elemental semiconductors, i.e. Group IV
    • H01L2924/10253—Silicon [Si]

Description

本発明は配線パターンをレーザー加工により作製して得た配線基板の製造方法、得られた配線基板およびそれを用いた半導体装置に関する。   The present invention relates to a method for manufacturing a wiring board obtained by producing a wiring pattern by laser processing, the obtained wiring board, and a semiconductor device using the same.

半導体装置用配線基板は、通常、絶縁基板表面を熱酸化したり、ＣＶＤ法やスパッタ法によって酸化膜、窒化膜などの薄膜を形成し、スピンコーターなどを用いて感光材（レジスト材）を塗布し、ステッパ装置で露光し、現像し、エッチング後、感光材をプラズマアッシャー、オゾンアッシャー、ウエットステーションなどを用いて剥離して製造されている。従来の製造方法は工程数が多く、そのため配線基板の歩留まりが低く、かつ装置費（設備費）が大規模になるという課題があった。
これに対し、レーザー光照射により絶縁基板表面に配線パターンを作製する方法は、工程数が減るため配線基板の歩留まりが上がり、装置費の大幅軽減が期待できる。 For wiring boards for semiconductor devices, the insulating substrate surface is usually thermally oxidized, or a thin film such as an oxide film or nitride film is formed by CVD or sputtering, and a photosensitive material (resist material) is applied using a spin coater or the like. The photosensitive material is exposed to light with a stepper device, developed, and etched, and then the photosensitive material is peeled off using a plasma asher, ozone asher, wet station or the like. The conventional manufacturing method has a number of processes, so that there is a problem that the yield of the wiring board is low and the apparatus cost (equipment cost) becomes large.
On the other hand, in the method for producing a wiring pattern on the surface of an insulating substrate by laser light irradiation, the number of steps is reduced, so that the yield of the wiring substrate is increased, and the device cost can be expected to be greatly reduced.

しかし、レーザー加工法は、絶縁基板表面にレーザー光を照射し熱で絶縁基板の表面を溶融飛散させる工程を必須とするため、照射面に絶縁基板の一部が飛散し付着し、付着物の除去が非常に困難であり、配線基板の歩留まりが著しく低い。該飛散、付着を防止するために、絶縁基板表面に水溶性樹脂を塗布しマスクフィルムを製膜する方法や、水溶性樹脂のマスクフィルムを接着する方法が提案されている。   However, the laser processing method requires a process in which the surface of the insulating substrate is irradiated with laser light and the surface of the insulating substrate is melted and scattered by heat, so that a part of the insulating substrate is scattered and adhered to the irradiated surface. Removal is very difficult and the yield of the wiring board is extremely low. In order to prevent the scattering and adhesion, a method of applying a water-soluble resin to the surface of an insulating substrate and forming a mask film, and a method of adhering a mask film of a water-soluble resin have been proposed.

例えば、シリコンウエハ表面に水溶性樹脂であるポリメチルメタクリレートの溶液をスピンコート法で塗布し、焼成（硬化）を行い被膜を製膜し、これをＹＡＧレーザー加工した後、得られた配線パターン付き基板に溶媒中で超音波を付与して被膜を溶解除去し、水洗し乾燥して配線基板を製造する方法が提案されている（特許文献１）。   For example, a solution of polymethylmethacrylate, which is a water-soluble resin, is applied to the surface of a silicon wafer by spin coating, fired (cured) to form a film, and this is YAG laser processed, and then obtained with a wiring pattern There has been proposed a method of manufacturing a wiring substrate by applying ultrasonic waves to a substrate in a solvent to dissolve and remove the coating, washing with water and drying (Patent Document 1).

また、シリコンウエハ表面に水溶性接着剤を介してアルミ箔などの保護シートを装着し、これをＹＡＧレーザー加工した後、得られた配線パターン付き基板に水を供給して保護シートを接着剤とともに溶解除去して配線基板を製造する方法が提案されている（特許文献２）。   In addition, a protective sheet such as an aluminum foil is attached to the surface of the silicon wafer via a water-soluble adhesive, and after this is YAG laser processed, water is supplied to the obtained substrate with a wiring pattern to attach the protective sheet together with the adhesive. A method of manufacturing a wiring board by dissolving and removing has been proposed (Patent Document 2).

また、シリコンウエハ表面に水溶性レーザー光吸収剤を含有する水溶性樹脂を塗布し乾燥して保護膜を製膜し、これをＹＡＧレーザー加工した後、保護膜を水洗除去して配線基板を製造する方法が提案されている（特許文献３）。   In addition, a water-soluble resin containing a water-soluble laser light absorber is applied to the silicon wafer surface and dried to form a protective film. After this is YAG laser processed, the protective film is washed and removed to produce a wiring board. A method has been proposed (Patent Document 3).

前記に加えて、水溶性樹脂、水溶性接着剤のマスクフィルムの代わりに、非水溶性の剥離可能なシートを用い、これを剥離除去する方法も提案されている。例えば、シリコンウエハ表面に、薄い剥離可能シートを貼り付け、レーザー光照射して配線パターンを作製した後、配線パターンに金属微粉を含有するエポキシ樹脂などのペースト状導電体を埋め込み、エポキシ樹脂を硬化後、剥離可能シートを剥離して配線基板を製造する方法が提案されている（特許文献４）。   In addition to the above, a method of peeling and removing a water-insoluble peelable sheet using a water-soluble resin or water-soluble adhesive mask film instead of a water-soluble resin or water-soluble adhesive mask film has also been proposed. For example, a thin peelable sheet is attached to the surface of a silicon wafer, and a wiring pattern is produced by laser light irradiation. Then, a paste-like conductor such as an epoxy resin containing fine metal powder is embedded in the wiring pattern, and the epoxy resin is cured. Thereafter, a method of manufacturing a wiring board by peeling a peelable sheet has been proposed (Patent Document 4).

しかし、水溶性樹脂、水溶性接着剤のマスクフィルムを溶媒により溶解除去する方法は、樹脂または接着剤やそれらの分解物等（スミア）による配線基板の汚染、溶媒の浄化または廃水処理の負担が大きいという問題がある。
一方、剥離可能シートを剥離する方法に適用できる剥離可能シートの内容および剥離手段・方法が、前記公報には具体的に記載されていない。
なお、本発明に使用される樹脂組成物を用いたフィルムが、配線基板上に実装される電子部品を封止するための封止用フィルムに使用されることが知られている。しかし、封止用フィルムであり配線基板から除去されることはなく、剥離性には言及されていない（特許文献５）。
要するに、絶縁基板表面に対する接着性、レーザー照射時の耐熱性、レーザー照射後の剥離性等の諸特性を同時に満足できるフィルム材料はこれまでに知られていない。無論、該フィルム材料を配線基板の製造に使用することも知られていない。 However, the method of dissolving and removing the water-soluble resin and water-soluble adhesive mask film with a solvent has the burden of contamination of the wiring board by the resin or adhesive or their decomposition products (smear), solvent purification or wastewater treatment. There is a problem of being big.
On the other hand, the content of the peelable sheet and the peeling means / method applicable to the method of peeling the peelable sheet are not specifically described in the publication.
In addition, it is known that the film using the resin composition used for this invention is used for the film for sealing for sealing the electronic component mounted on a wiring board. However, it is a sealing film and is not removed from the wiring board, and no mention is made of peelability (Patent Document 5).
In short, a film material that can simultaneously satisfy various properties such as adhesion to the surface of an insulating substrate, heat resistance during laser irradiation, and peelability after laser irradiation has not been known. Of course, it is not known to use the film material for manufacturing a wiring board.

特開平５−３３００４６号公報JP-A-5-330046 特開２００５−３１３１８８号公報JP-A-2005-313188 特開２００６−１４０３１１号公報JP 2006-140311 A 特開２００６−６０１５０号公報JP 2006-60150 A 特開２００８−２１８４９６号公報JP 2008-218496 A

本発明は、絶縁基板表面に対する接着性、レーザー照射時の耐熱性、レーザー照射後の絶縁基板表面からの加熱剥離性などの諸特性を同時に満足できるフィルム形成可能な樹脂組成物を見出し、この樹脂組成物を剥離可能なマスクフィルムの材料として用いて、スミアの飛散、付着を防止するレーザー加工法による配線基板の製造方法の具体的方法を提供することが目的である。また、本発明は、その方法により得られた配線基板およびそれを用いた半導体装置を提供することも目的である。   The present invention has found a resin composition capable of forming a film that can simultaneously satisfy various properties such as adhesion to an insulating substrate surface, heat resistance during laser irradiation, and heat release from the insulating substrate surface after laser irradiation. An object of the present invention is to provide a specific method of manufacturing a wiring board by a laser processing method that prevents the smear from scattering and adhering by using the composition as a peelable mask film material. Another object of the present invention is to provide a wiring board obtained by the method and a semiconductor device using the wiring board.

本発明は、下記の［１］〜［１２］に記載したとおりである。
［１］絶縁基板表面にマスクフィルムを設置し、レーザー光を照射して配線パターンを作製し、前記絶縁基板表面に配線層を形成した後、加熱により前記マスクフィルムを前記絶縁基板表面から剥離除去し、前記配線パターンに配線を形成することを特徴とする配線基板の製造方法。 The present invention is as described in the following [1] to [12].
[1] A mask film is placed on the surface of the insulating substrate, and a wiring pattern is produced by irradiating a laser beam. After forming a wiring layer on the surface of the insulating substrate, the mask film is peeled off from the surface of the insulating substrate by heating. And forming a wiring on the wiring pattern.

［２］前記マスクフィルムが、下記式（１）で示されるビニル化合物（Ａ）ならびにゴムおよび／または熱可塑性エラストマーを含有する樹脂組成物のフィルムおよびポリイミドフィルムからなる積層フィルムであり、前記樹脂組成物のフィルムが基板表面に接する前記〔１〕に記載の配線基板の製造方法。
[2] The mask film is a laminated film comprising a film of a resin composition containing a vinyl compound (A) represented by the following formula (1) and rubber and / or a thermoplastic elastomer, and a polyimide film, and the resin composition The method for manufacturing a wiring board according to [1], wherein the film of the object contacts the substrate surface.

［式（１）中、Ｒ1、Ｒ2、Ｒ3、Ｒ4、Ｒ5、Ｒ6およびＲ7はそれぞれ独立に水素原子、ハロゲン原子、炭素原子数１〜６のアルキル基、炭素原子数１〜６のハロゲン化アルキル基またはフェニル基を表し、複数のＲ1、Ｒ2、Ｒ3、Ｒ4、Ｒ5、Ｒ6およびＲ7は同一であっても異なっていてもよい。
−（Ｏ−Ｘ−Ｏ）−は下記式（２）で表される構造であり、−（Ｙ−Ｏ）−は下記式（３）で表される繰返し単位であり、Ｚは酸素原子、窒素原子、イオウ原子、ハロゲン原子を含んでいてもよい炭素原子数１〜３の有機基を表す。
ａおよびｂは少なくとも一方が０でない０〜３００の整数を表し、ｃおよびｄはそれぞれ独立に０または１の整数を表す。］
[In the formula (1), R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, or the number of carbon atoms. 1 to 6 halogenated alkyl groups or phenyl groups, and a plurality of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 may be the same or different.
-(O-X-O)-is a structure represented by the following formula (2),-(YO)-is a repeating unit represented by the following formula (3), Z is an oxygen atom, An organic group having 1 to 3 carbon atoms which may contain a nitrogen atom, a sulfur atom or a halogen atom.
a and b each represents an integer of 0 to 300 in which at least one is not 0, and c and d each independently represents an integer of 0 or 1. ]

［式（２）中、Ｒ8、Ｒ9、Ｒ10、Ｒ14およびＲ15はそれぞれ独立にハロゲン原子、炭素原子数６以下のアルキル基またはフェニル基を表し、Ｒ11、Ｒ12およびＲ13はそれぞれ独立に水素原子、ハロゲン原子、炭素原子数６以下のアルキル基またはフェニル基を表す。
式（３）中、Ｒ16およびＲ17はそれぞれ独立にハロゲン原子、炭素原子数６以下のアルキル基またはフェニル基を表し、Ｒ18およびＲ19はそれぞれ独立に水素原子、ハロゲン原子、炭素原子数６以下のアルキル基またはフェニル基を表す。］ [In the formula (2), R 8 , R 9 , R 10 , R 14 and R 15 each independently represents a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group, R 11 , R 12 and R 13 Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group.
In the formula (3), R 16 and R 17 each independently represent a halogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group, and R 18 and R 19 each independently represent a hydrogen atom, a halogen atom, or a carbon atom number. The alkyl group or phenyl group of 6 or less is represented. ]

［３］前記（Ａ）成分の−（Ｏ−Ｘ−Ｏ）−が下記式（４）で表される構造であり、前記−（Ｙ−Ｏ）−が下記式（５）または（６）で表される繰返し単位である前記［２］に記載の配線基板の製造方法。
[3]-(O-X-O)-of the component (A) is a structure represented by the following formula (4), and the-(YO)-is represented by the following formula (5) or (6). The method for producing a wiring board according to the above [2], which is a repeating unit represented by:

［４］前記（Ａ）成分の−（Ｙ−Ｏ）−が前記式（６）で表される繰返し単位である前記［３］に記載の配線基板の製造方法。
［５］前記（Ｂ）成分が熱可塑性エラストマーである前記［２］〜［４］のいずれかに記載の配線基板の製造方法。
［６］前記（Ａ）成分と前記（Ｂ）成分との質量割合が４０：６０〜６０：４０である前記［２］〜［５］のいずれかに記載の配線基板の製造方法。 [4] The method for manufacturing a wiring board according to [3], wherein — (YO) — of the component (A) is a repeating unit represented by the formula (6).
[5] The method for manufacturing a wiring board according to any one of [2] to [4], wherein the component (B) is a thermoplastic elastomer.
[6] The method for manufacturing a wiring board according to any one of [2] to [5], wherein a mass ratio of the component (A) and the component (B) is 40:60 to 60:40.

［７］前記加熱が温度２００〜３００℃である前記［１］〜［６］のいずれかに記載の配線基板の製造方法。
［８］前記配線パターンの作製がＹＡＧレーザー光の照射による前記［１］〜［７］のいずれかに記載の配線基板の製造方法。
［９］前記配線層の形成が金属のスパッタ法、真空蒸着法またはメッキによる前記［１］〜［８］のいずれかに記載の配線基板の製造方法。
［１０］前記［１］〜［９］のいずれかに記載の配線基板の製造方法により製造したことを特徴とする配線基板。
［１１］前記［１０］に記載の配線基板を用いたことを特徴とする半導体装置。
［１２］前記式（１）で示されるビニル化合物（Ａ）ならびにゴムおよび／または熱可塑性エラストマーを含有する樹脂組成物のフィルムおよびポリイミドフィルムからなるマスクフィルム用積層フィルム。 [7] The method for manufacturing a wiring board according to any one of [1] to [6], wherein the heating is performed at a temperature of 200 to 300 ° C.
[8] The method for manufacturing a wiring board according to any one of [1] to [7], wherein the wiring pattern is produced by irradiation with YAG laser light.
[9] The method for manufacturing a wiring board according to any one of [1] to [8], wherein the wiring layer is formed by a metal sputtering method, a vacuum evaporation method, or plating.
[10] A wiring board manufactured by the method for manufacturing a wiring board according to any one of [1] to [9].
[11] A semiconductor device using the wiring board according to [10].
[12] A laminated film for a mask film comprising a film of a resin composition containing a vinyl compound (A) represented by the formula (1) and rubber and / or a thermoplastic elastomer, and a polyimide film.

本発明により、レーザー光照射により配線パターンを絶縁基板表面に作製する際に、積層マスクフィルムの一層を構成する樹脂組成物が適度に硬化し、耐熱性があり、炭化しないため、マスクフィルムが、レーザー加工の際に生じる絶縁基板のスミアの飛散、付着および汚染を防止し、加工精度を低下させることなく、設計とおりの配線パターンを作製することができる。また、何らの外力を加えることなく、加熱により樹脂組成物のフィルムが絶縁基板表面から極めて容易に界面剥離し、絶縁基板にスミアを残さないので、効率よく配線基板を製造することができる。
また、マスクフィルムを溶解除去するための有機溶剤や水を使用する必要がないので、溶剤処理、廃水処理が不要になる。
また、本発明により、加工精度が良い配線基板および小型、高性能の半導体装置を製造することができる。 According to the present invention, when the wiring pattern is produced on the surface of the insulating substrate by laser light irradiation, the resin composition constituting one layer of the laminated mask film is appropriately cured, heat resistant, and not carbonized. It is possible to prevent the smear of the insulating substrate from being scattered, adhered and contaminated during laser processing, and to produce a wiring pattern as designed without reducing the processing accuracy. Further, since the film of the resin composition is peeled off from the surface of the insulating substrate very easily by heating without applying any external force, and no smear is left on the insulating substrate, the wiring substrate can be manufactured efficiently.
Moreover, since it is not necessary to use an organic solvent or water for dissolving and removing the mask film, solvent treatment and waste water treatment are not required.
In addition, according to the present invention, it is possible to manufacture a wiring board and a small, high-performance semiconductor device with high processing accuracy.

本発明の配線基板の製造方法の工程の一例を示す模式断面図である。It is a schematic cross section which shows an example of the process of the manufacturing method of the wiring board of this invention. 本発明の配線基板の実施例１の断面写真（倍率１５００倍）である。It is a cross-sectional photograph (1500 times magnification) of Example 1 of the wiring board of the present invention.

本発明は、シリコンウエハ等の絶縁基板表面に、特定成分を含有する樹脂組成物のフィルム（以後、組成物フィルムとも記す）とポリイミドフィルムとの積層フィルムからなるマスクフィルムを設置し、ステッパ装置を用いてレーザー光照射により配線パターンを作製し、さらに、スパッタリングなどにより配線層（金属膜）を形成し、マスクフィルムを加熱により剥離除去する配線基板の製造方法である。なお、前記積層フィルムは、組成物フィルムとポリイミドフィルムとを絶縁基板上で加熱接着して得られる積層フィルムも包含する。
本発明において、絶縁基板表面にマスクフィルムを設置する工程から配線層を形成するまでの工程は、絶縁基板に公知のレーザー加工を施して配線基板を製造する方法の工程を適用することができる。
本発明の配線基板の製造方法は、マスクフィルムが従来法の水溶性樹脂、接着剤のフィルムではなく、特定成分を含有する非水溶性樹脂組成物のフィルムとポリイミドフィルムとの積層フィルムからなり、加熱により剥離可能な積層フィルムをマスクフィルムとして用いる点に特徴がある。 In the present invention, a mask film made of a laminated film of a resin composition film containing a specific component (hereinafter also referred to as a composition film) and a polyimide film is installed on the surface of an insulating substrate such as a silicon wafer. This is a method for manufacturing a wiring board in which a wiring pattern is produced by laser beam irradiation, a wiring layer (metal film) is formed by sputtering, and the mask film is peeled off by heating. In addition, the said laminated | multilayer film also includes the laminated | multilayer film obtained by heat-bonding a composition film and a polyimide film on an insulated substrate.
In the present invention, the steps from the step of placing the mask film on the surface of the insulating substrate to the step of forming the wiring layer can be applied to the method of manufacturing the wiring substrate by subjecting the insulating substrate to known laser processing.
The method for producing a wiring board of the present invention is a mask film made of a laminated film of a polyimide film and a water-insoluble resin composition film containing a specific component, rather than a conventional water-soluble resin and adhesive film, It is characterized in that a laminated film that can be peeled off by heating is used as a mask film.

樹脂組成物を構成するビニル化合物（Ａ）と、ゴムおよび／または熱可塑性エラストマー（Ｂ）について説明する。なお、ビニル化合物（Ａ）は特開２００４−５９６４４号公報に記載されたビニル化合物（Ａ）と同じである。   The vinyl compound (A) and rubber and / or thermoplastic elastomer (B) constituting the resin composition will be described. The vinyl compound (A) is the same as the vinyl compound (A) described in JP-A-2004-59644.

（ビニル化合物）
ビニル化合物（Ａ）は下記式（１）で示されるエーテル結合とベンゼン核を有するビニル化合物である。
(Vinyl compound)
The vinyl compound (A) is a vinyl compound having an ether bond and a benzene nucleus represented by the following formula (1).

［式（１）中、Ｒ1、Ｒ2、Ｒ3、Ｒ4、Ｒ5、Ｒ6およびＲ7はそれぞれ独立に水素原子、ハロゲン原子、炭素原子数１〜６のアルキル基、炭素原子数１〜６のハロゲン化アルキル基またはフェニル基を表し、複数のＲ1、Ｒ2、Ｒ3、Ｒ4、Ｒ5、Ｒ6およびＲ7は同一であっても異なっていてもよい。
−（Ｏ−Ｘ−Ｏ）−は下記式（２）で表される構造であり、−（Ｙ−Ｏ）−は下記式（３）で表される繰返し単位であり、Ｚは酸素原子、窒素原子、イオウ原子、ハロゲン原子を含んでいてもよい炭素原子数１〜３の有機基を表す。
ａおよびｂは少なくとも一方が０でない０〜３００の整数を表し、ｃおよびｄはそれぞれ独立に０または１の整数を表す。］
[In the formula (1), R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, or the number of carbon atoms. 1 to 6 halogenated alkyl groups or phenyl groups, and a plurality of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 may be the same or different.
-(O-X-O)-is a structure represented by the following formula (2),-(YO)-is a repeating unit represented by the following formula (3), Z is an oxygen atom, An organic group having 1 to 3 carbon atoms which may contain a nitrogen atom, a sulfur atom or a halogen atom.
a and b each represents an integer of 0 to 300 in which at least one is not 0, and c and d each independently represents an integer of 0 or 1. ]

［式（２）中、Ｒ8、Ｒ9、Ｒ10、Ｒ14およびＲ15はそれぞれ独立にハロゲン原子、炭素原子数６以下のアルキル基またはフェニル基を表し、Ｒ11、Ｒ12およびＲ13はそれぞれ独立に水素原子、ハロゲン原子、炭素原子数６以下のアルキル基またはフェニル基を表す。
式（３）中、Ｒ16およびＲ17はそれぞれ独立にハロゲン原子、炭素原子数６以下のアルキル基またはフェニル基を表し、Ｒ18およびＲ19はそれぞれ独立に水素原子、ハロゲン原子、炭素原子数６以下のアルキル基またはフェニル基を表す。］ [In the formula (2), R 8 , R 9 , R 10 , R 14 and R 15 each independently represents a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group, R 11 , R 12 and R 13 Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group.
In the formula (3), R 16 and R 17 each independently represent a halogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group, and R 18 and R 19 each independently represent a hydrogen atom, a halogen atom, or a carbon atom number. The alkyl group or phenyl group of 6 or less is represented. ]

前記（Ａ）成分の−（Ｏ−Ｘ−Ｏ）−は下記式（４）で表される構造であり、前記−（Ｙ−Ｏ）−は下記式（５）または（６）で表される繰返し単位である。
-(O-X-O)-in the component (A) is a structure represented by the following formula (4), and-(YO)-is represented by the following formula (5) or (6). It is a repeating unit.

前記（Ａ）成分の−（Ｙ−Ｏ）−は前記式（６）で表される繰返し単位である。   -(YO)-in the component (A) is a repeating unit represented by the formula (6).

本発明に使用されるビニル化合物（Ａ）は数平均分子量が５００〜５０００であることが好ましく、１０００〜３０００であることがより好ましい。その理由は、ビニル化合物（Ａ）と成分（Ｂ）を含有する樹脂組成物の溶融粘度を低くすることができ、ビニル化合物（Ａ）同士の反応性が良好にできるからである。なお、数平均分子量はＧＰＣにより、標準ポリスチレンによる検量線を用いて求めた値である。   The vinyl compound (A) used in the present invention preferably has a number average molecular weight of 500 to 5000, more preferably 1000 to 3000. The reason is that the melt viscosity of the resin composition containing the vinyl compound (A) and the component (B) can be lowered, and the reactivity between the vinyl compounds (A) can be improved. The number average molecular weight is a value determined by GPC using a standard polystyrene calibration curve.

ビニル化合物（Ａ）は好ましくは、前記式（１）において、Ｒ1〜Ｒ7が水素であり、−（Ｏ−Ｘ−Ｏ）−が前記式（４）であり、−（Ｙ−Ｏ）−が前記式（６）であり、Ｚがメチレン基であり、ｃおよびｄが１である化合物で数平均分子量が１０００〜３０００のものである。 The vinyl compound (A) is preferably, in the formula (1), R 1 to R 7 are hydrogen, — (O—X—O) — is the formula (4), and — (Y—O) -Is the formula (6), Z is a methylene group, c and d are 1, and the number average molecular weight is 1000 to 3000.

（ゴム、熱可塑性エラストマー）
本発明に使用される成分（Ｂ）のゴムおよび／または熱可塑性エラストマーは以下に示すとおりである。
ゴムとしてはスチレン−ブタジエンゴム（ＳＢＲ）、ブチルゴム（ＩＩＲ）、ブタジエンゴム（ＢＲ）、アクリルゴム（ＡＣＭ）、ニトリルゴム（ＮＢＲ）等が挙げられる。スチレン−ブタジエンゴムは（Ａ）成分との相溶性が良好で、得られる樹脂組成物からなるフィルムが絶縁基板との接着性が良好で、加熱剥離性に優れるので好ましい。 (Rubber, thermoplastic elastomer)
The rubber and / or thermoplastic elastomer of component (B) used in the present invention is as shown below.
Examples of the rubber include styrene-butadiene rubber (SBR), butyl rubber (IIR), butadiene rubber (BR), acrylic rubber (ACM), and nitrile rubber (NBR). Styrene-butadiene rubber is preferred because it has good compatibility with the component (A), and a film made of the resulting resin composition has good adhesion to an insulating substrate and is excellent in heat peelability.

一方、熱可塑性エラストマーとして、具体的にはスチレン‐ジエン共重合体、スチレン‐ブタジエン‐スチレンブロック共重合体（ＳＢＳ）、水添スチレン‐ブタジエン‐スチレン共重合体（ＳＥＢＳ）、スチレン‐イソプレン‐スチレン共重合体（ＳＩＳ）、水添スチレン‐イソプレン‐スチレン共重合体（ＳＥＰＳ）、水添スチレン（ブタジエン／イソプレン）共重合体等のスチレン系熱可塑性エラストマー、オレフィン系熱可塑性エラストマー、ポリエステル系熱可塑性エラストマー等が挙げられる。   On the other hand, specific examples of thermoplastic elastomers include styrene-diene copolymers, styrene-butadiene-styrene block copolymers (SBS), hydrogenated styrene-butadiene-styrene copolymers (SEBS), and styrene-isoprene-styrene. Styrenic thermoplastic elastomers such as copolymers (SIS), hydrogenated styrene-isoprene-styrene copolymers (SEPS), hydrogenated styrene (butadiene / isoprene) copolymers, olefin thermoplastic elastomers, polyester thermoplastics An elastomer etc. are mentioned.

（Ｂ）成分としては、マスクフィルムの特性の点から熱可塑性エラストマーが好ましい。特に、マスクフィルムのシリコンウエハ等の絶縁基板に対する流動性、接着性の観点から、重量平均分子量は２０，０００〜２５０，０００のスチレン系熱可塑性エラストマーが好ましい。なお、重量平均分子量はＧＰＣにより、標準ポリスチレンによる検量線を用いて求めた値である。   (B) As a component, a thermoplastic elastomer is preferable from the point of the characteristic of a mask film. In particular, a styrene-based thermoplastic elastomer having a weight average molecular weight of 20,000 to 250,000 is preferable from the viewpoint of fluidity and adhesiveness of the mask film to an insulating substrate such as a silicon wafer. The weight average molecular weight is a value determined by GPC using a standard polystyrene calibration curve.

また、本発明においては、このようなゴムおよび／または熱可塑性エラストマーは、１種単独で用いてもよく、２種以上を併用してもよい。   In the present invention, such rubber and / or thermoplastic elastomer may be used singly or in combination of two or more.

（樹脂組成物）
本発明においては、（Ａ）成分と（Ｂ）成分の質量割合は１０：９０〜９０：１０であるのが好ましく、得られるマスクフィルムの硬化物の特性の点から４０：６０〜６０：４０であるのがより好ましく、４５：５５〜５５：４５であるのがさらに好ましい。 (Resin composition)
In this invention, it is preferable that the mass ratio of (A) component and (B) component is 10: 90-90: 10, and 40: 60-60: 40 from the point of the characteristic of the hardened | cured material of the mask film obtained. It is more preferable that it is 45: 55-55: 45.

本発明においては、（Ａ）成分および（Ｂ）成分を含有する樹脂組成物は、本発明の効果を損なわない範囲で、無機フィラー、粘着性付与剤、消泡剤、流動調整剤、製膜補助剤、分散助剤、難燃化剤等の公知の添加剤を含有していてもよい。特に、樹脂組成物からなるマスクフィルムの加熱による溶融剥離温度を低温化するために、樹脂組成物に溶融温度を低下させる成分を添加したり、ビニル化合物（Ａ）や成分（Ｂ）の溶融温度を低下させるための変性をすることが好ましい。   In the present invention, the resin composition containing the component (A) and the component (B) is an inorganic filler, a tackifier, an antifoaming agent, a flow regulator, and a film-forming, as long as the effects of the present invention are not impaired. You may contain well-known additives, such as an adjuvant, a dispersion | distribution adjuvant, and a flame retardant. In particular, in order to lower the melt peeling temperature by heating the mask film made of the resin composition, a component for decreasing the melting temperature is added to the resin composition, or the melting temperature of the vinyl compound (A) or the component (B). It is preferable to carry out modification to reduce the amount.

本発明において、樹脂組成物は加熱により硬化するので、硬化触媒、硬化促進剤を必ずしも含有させなくてよい。   In the present invention, since the resin composition is cured by heating, it is not always necessary to contain a curing catalyst and a curing accelerator.

本発明に使用される樹脂組成物は、公知の方法により製造することができる。例えば、溶媒の存在下または非存在下で、（Ａ）成分および（Ｂ）ならびに所望により含有してもよい各種添加剤の各々を混合する方法により製造することができる。   The resin composition used in the present invention can be produced by a known method. For example, it can be produced by a method of mixing each of component (A) and component (B) and various additives that may be optionally contained in the presence or absence of a solvent.

（樹脂組成物のフィルム）
本発明のマスクフィルムを製造するには、まず樹脂組成物のフィルム化を行う。例えば、樹脂組成物を有機溶剤に溶解または分散させてワニスとした後に、ポリエチレンテレフタレート（ＰＥＴ）フィルムなどの基材フィルムに塗布し、乾燥させて製膜し、基材フィルムから剥離する方法等が挙げられる。本発明が適用される基材フィルムは特に限定されない。基材フィルムの厚さは１〜５０μｍであるのが好ましく、５〜４０μｍであるのがより好ましく、１０〜３０μｍであるのがさらに好ましい。 (Resin composition film)
In order to produce the mask film of the present invention, first, the resin composition is formed into a film. For example, a method in which a resin composition is dissolved or dispersed in an organic solvent to form a varnish, which is then applied to a base film such as a polyethylene terephthalate (PET) film, dried to form a film, and then peeled off from the base film. Can be mentioned. The base film to which the present invention is applied is not particularly limited. The thickness of the base film is preferably 1 to 50 μm, more preferably 5 to 40 μm, and even more preferably 10 to 30 μm.

ワニスを基材フィルムに塗布する方法は特に限定されないが、薄膜化、膜厚制御の観点からグラビア法、スロットダイ法、ドクターコ一タ一方式等が挙げられ、所望のフィルムの厚み等に応じて適宜選択されるが、特にグラビア法がフィルムの厚みを薄く設計しうることから好ましい。   The method of applying the varnish to the base film is not particularly limited, but from the viewpoint of thinning and film thickness control, there are a gravure method, a slot die method, a doctor coater method, etc., depending on the desired film thickness, etc. The gravure method is particularly preferable because the thickness of the film can be designed thin.

ワニス用有機溶剤としては、例えば、トルエン、キシレンなどの芳香族炭化水素系溶剤；メチルエチルケトン、メチルイソブチルケトンなどのケトン系溶剤；ジオクチルフタレート、ジブチルフタレートなどの高沸点溶媒等が挙げられ、これらを１種単独で用いてもよく、２種以上を併用してもよい。
有機溶剤の使用量は特に限定されないが、固形分濃度が２０〜９０質量％となるように使用するのが好ましく、２０〜５０質量％となるように使用するのがより好ましい。
作業性の観点から、ワニスは１００〜６００ｍＰａ・ｓの粘度であるのが好ましい。
ここで、粘度はＥ型粘度計を用いて、回転数６０ｒｐｍ、２５℃で測定した値とする。 Examples of the organic solvent for varnish include aromatic hydrocarbon solvents such as toluene and xylene; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; and high boiling solvents such as dioctyl phthalate and dibutyl phthalate. One species may be used alone, or two or more species may be used in combination.
Although the usage-amount of an organic solvent is not specifically limited, It is preferable to use it so that solid content concentration may be 20-90 mass%, and it is more preferable to use it so that it may become 20-50 mass%.
From the viewpoint of workability, the varnish preferably has a viscosity of 100 to 600 mPa · s.
Here, the viscosity is a value measured using an E-type viscometer at a rotation speed of 60 rpm and 25 ° C.

ワニスを塗布した後の乾燥条件は、ワニスに使用される有機溶剤の種類や量、塗布の厚み等に応じて適宜設定することができ、一般に、大気圧下、６０〜１２０℃で、１〜３０ｍｉｎ程度行うことが好ましく、防爆機能を有する乾燥機を使用することが安全上の観点から好ましい。また、乾燥は大気中または窒素雰囲気中にて行うことができる。   The drying conditions after applying the varnish can be appropriately set according to the type and amount of the organic solvent used in the varnish, the thickness of the application, etc., and generally 1 to 60 to 120 ° C. under atmospheric pressure. It is preferable to carry out for about 30 minutes, and it is preferable from the viewpoint of safety to use a dryer having an explosion-proof function. Moreover, drying can be performed in air | atmosphere or nitrogen atmosphere.

基材フィルム上の組成物フィルムの厚さは０．５〜３０μｍであるのが好ましく、１〜２０μｍであるのがより好ましく、２〜１５μｍであるのがさらに好ましい。組成物フィルムの厚さが前記範囲にあれば、マスクフィルムとして十分なフィルム強度を維持し、加熱真空プレス、レーザー光照射および加熱剥離に際しても、炭化せず、溶融するまで変形せず、亀裂、皺等の発生もない。   The thickness of the composition film on the base film is preferably 0.5 to 30 μm, more preferably 1 to 20 μm, and further preferably 2 to 15 μm. If the thickness of the composition film is within the above range, it maintains a sufficient film strength as a mask film, and is not carbonized or deformed until it melts even during heating vacuum press, laser light irradiation and heat peeling, cracks, There is no occurrence of wrinkles.

（配線パターンの作製）
絶縁基板表面上にマスクフィルムを接着する方法は従来公知の方法による。例えば、シリコンウエハ表面に、組成物フィルムとポリイミドフィルムからなる積層フィルムの組成物フィルムが接するように置くか、または、シリコンウエハ表面に、組成物フィルムを置き、その上に、ポリイミドフィルムを載せ、真空下、１５０〜２５０℃、好ましくは１８０〜２００℃に加熱し、圧力０．５〜１０Ｍｐａで１０〜１２０ｍｉｎ、好ましくは３０〜６０ｍｉｎプレスする方法が挙げられる。この際、マスクフィルムの一層を構成するビニル化合物（Ａ）、ゴムおよび／または熱可塑性エラストマーを含有する樹脂組成物が硬化する。樹脂組成物の硬化度が高いほど、耐熱性が上がり、炭化することもなく、かつ、後工程の加熱剥離の際にスミアを残さず、剥離が円滑に進行するので、硬化度は高いほど好ましい。 (Production of wiring pattern)
A method of adhering the mask film on the surface of the insulating substrate is a conventionally known method. For example, a laminated film composed of a composition film and a polyimide film is placed on the silicon wafer surface so that the composition film is in contact with the silicon wafer surface, or a composition film is placed on the silicon wafer surface, and a polyimide film is placed thereon. The method includes heating to 150 to 250 ° C., preferably 180 to 200 ° C. under vacuum, and pressing at a pressure of 0.5 to 10 MPa for 10 to 120 minutes, preferably 30 to 60 minutes. At this time, the resin composition containing the vinyl compound (A), rubber and / or thermoplastic elastomer constituting one layer of the mask film is cured. The higher the degree of cure of the resin composition, the higher the heat resistance, the less carbonization occurs, and no smear is left in the subsequent heat peeling, and the peeling proceeds smoothly. .

組成物フィルムおよび基材フィルムからなる積層フィルムの組成物フィルムを接着した絶縁基板表面への配線パターンの作製は、従来公知のレーザー加工方法、条件により実施される。ＹＡＧレーザーが好ましいが、エキシマレーザーも使用できる。   The production of the wiring pattern on the surface of the insulating substrate to which the composition film of the laminated film composed of the composition film and the base film is bonded is performed by a conventionally known laser processing method and conditions. A YAG laser is preferred, but an excimer laser can also be used.

（配線層の形成）
配線パターンが形成された絶縁基板表面に、従来公知のスパッタ法、真空蒸着法、メッキ等の方法により公知の条件で金属の薄膜を製膜し、被覆し、配線層を形成する。好ましい方法はスパッタ法である。配線層の厚さは５μｍ未満であり、１〜３μｍであるのが好ましい。 (Formation of wiring layer)
On the surface of the insulating substrate on which the wiring pattern is formed, a metal thin film is formed under a known condition by a conventionally known sputtering method, vacuum vapor deposition method, plating method or the like, and coated to form a wiring layer. A preferred method is sputtering. The thickness of the wiring layer is less than 5 μm, and preferably 1 to 3 μm.

（マスクフィルムの剥離）
配線層が形成された絶縁基板表面を加熱するとマスクフィルムが絶縁基板表面から外力を加えずとも自然に界面剥離を開始し、一挙に剥離が完了する。マスクフィルムとともにマスクフィルムを被覆している金属膜も勿論一挙に剥離除去される。加熱条件はマスクフィルムを構成する樹脂組成物の成分（Ａ）および（Ｂ）の種類や組成比、樹脂組成物の硬化度、マスクフィルムの厚さ等により変わるので一様ではないが、加熱温度は１５０〜４００℃、好ましくは２００〜３００℃であり、加熱時間は１００〜５００ｈｒ、好ましくは２００〜３００ｈｒである。マスクフィルムの一層を構成する材料である樹脂組成物に、溶融温度を低下させる成分を含有したり、ビニル化合物（Ａ）や成分（Ｂ）の溶融温度を低下させる変性をした場合には、剥離のための加熱温度、時間を低減できることは言うまでもない。
加熱は大気中で実施することができる。
加熱手段は特に限定されないが、加熱オーブンが好ましい。
加熱により剥離する理由は不明であるが、組成物フィルムの加熱による凝集と推定される。 (Removal of mask film)
When the surface of the insulating substrate on which the wiring layer is formed is heated, the mask film starts to peel off the interface naturally without applying external force from the surface of the insulating substrate, and the peeling is completed at once. Of course, the metal film covering the mask film as well as the mask film is peeled and removed all at once. The heating conditions are not uniform because they vary depending on the types and composition ratios of the components (A) and (B) of the resin composition constituting the mask film, the degree of cure of the resin composition, the thickness of the mask film, etc. Is 150 to 400 ° C., preferably 200 to 300 ° C., and the heating time is 100 to 500 hr, preferably 200 to 300 hr. When the resin composition, which is a material constituting one layer of the mask film, contains a component that lowers the melting temperature or is modified to lower the melting temperature of the vinyl compound (A) or the component (B), it is peeled off. Needless to say, the heating temperature and time for the heat treatment can be reduced.
Heating can be carried out in the atmosphere.
The heating means is not particularly limited, but a heating oven is preferable.
Although the reason for peeling by heating is unknown, it is estimated that the composition film is agglomerated by heating.

マスクフィルムを剥離除去して得た配線基板は、必要ならば洗浄して、製品としての配線基板になる。配線基板にはスミアが存在しないので、配線基板の性能は実用化可能な水準にある。   The wiring substrate obtained by peeling and removing the mask film is washed if necessary to become a wiring substrate as a product. Since there is no smear in the wiring board, the performance of the wiring board is at a level where it can be put into practical use.

（半導体装置）
本発明の配線基板を用いた半導体装置は従来公知の方法により製造することができる。例えば、本発明の配線基板を、有機配線板または無機配線板にＳｎ/Ｐｂ、Ａｕ/Ｓｉなどでダイボンティングし、配線基板の金属配線と配線板上のパターンをＡｕまたはＡｌのワイヤで接合する。その後、封止剤により絶縁し本発明の半導体装置を製造する。もちろん、この方法に限定される訳ではなく、フリップチップにより接合する半導体装置も製造可能である。本発明の半導体装置は従来法による半導体装置と何ら変わるところがない性能を有しており、各種製品に使用することができる。 (Semiconductor device)
A semiconductor device using the wiring board of the present invention can be manufactured by a conventionally known method. For example, the wiring board of the present invention is die bonded to an organic wiring board or an inorganic wiring board with Sn / Pb, Au / Si, etc., and the metal wiring of the wiring board and the pattern on the wiring board are joined with Au or Al wires. . Thereafter, the semiconductor device of the present invention is manufactured by insulating with a sealant. Of course, the present invention is not limited to this method, and a semiconductor device bonded by flip chip can be manufactured. The semiconductor device of the present invention has the same performance as a conventional semiconductor device and can be used for various products.

（実施例１）
（樹脂組成物）
2,2’,3,3’,5,5’−ヘキサメチルビフェニル−4,4’−ジオール−2,6−ジメチルフェノールとクロロメチルスチレンとの反応で得られる、前記式（１）において、Ｒ1〜Ｒ7が水素であり、−（Ｏ−Ｘ−Ｏ）−が構造式（４）であり、−（Ｙ−Ｏ）−が構造式（６）であり、Ｚがメチレン基であり、ｃおよびｄが１である化合物（Ａ１）（数平均分子量２２００；「 ＯＰＥ‐２Ｓｔ−２２００」；三菱ガス化学株式会社製）１５質量部と、スチレン−ブタジエン−スチレンブロック共重合体ＳＢＳ（重量平均分子量１００，０００；「ＴＲ２００３」；ＪＳＲ株式会社製）１５質量部を溶剤ＭＥＫ７０質量部に入れ、７０℃で８ｈｒ攪拌混合してワニス（固形分濃度３０質量％、粘度２５０ｍＰａ・s）を調製した。 Example 1
(Resin composition)
In the above formula (1) obtained by reaction of 2,2 ′, 3,3 ′, 5,5′-hexamethylbiphenyl-4,4′-diol-2,6-dimethylphenol and chloromethylstyrene, R 1 to R 7 are hydrogen, — (O—X—O) — is the structural formula (4), — (Y—O) — is the structural formula (6), and Z is a methylene group. Compound (A1) in which c and d are 1 (number average molecular weight 2200; “OPE-2St-2200”; manufactured by Mitsubishi Gas Chemical Co., Ltd.) and 15 parts by weight of styrene-butadiene-styrene block copolymer SBS (weight) Average molecular weight 100,000; “TR2003” (manufactured by JSR Corporation) 15 parts by mass in 70 parts by mass of solvent MEK and stirred and mixed at 70 ° C. for 8 hours to prepare a varnish (solid content concentration 30 mass%, viscosity 250 mPa · s) did.

（樹脂組成物のフィルム）
前記ワニスを、膜厚７５μｍのＰＥＴフィルム（「ＰＥＴ７５ＧＳ」；リンテック株式会社製）に、グラビアロール機（ナミックス株式会社製）を用いて、塗布膜厚３０μｍになるように均一に塗布した。グラビアロール機と一体化している熱風乾燥機で、ワニスを蒸発させ残留ＭＥＫが０．１％以下、膜厚９μｍの組成物フィルム２を得た。 (Resin composition film)
The varnish was uniformly applied to a PET film having a film thickness of 75 μm (“PET75GS”; manufactured by Lintec Corporation) using a gravure roll machine (manufactured by NAMICS Co., Ltd.) so as to have a coating film thickness of 30 μm. The varnish was evaporated by a hot air dryer integrated with a gravure roll machine to obtain a composition film 2 having a residual MEK of 0.1% or less and a film thickness of 9 μm.

図１に基いて、配線基板を製造する方法を説明する。
（積層体）
シリコンウエハ１（板厚６００μｍ）表面全体を覆うように、ＰＥＴフィルムから剥離した前記組成物フィルム２を載せ、その上にポリイミドフィルム３（膜厚２５μｍ；「カプトン１００Ｈ」；東レ株式会社製）を載せ、２００℃、６０ｍｉｎ、圧力１Ｍｐａ、真空度１０ｋＰａ未満の条件で真空加熱プレスし、２５０℃で２４ｈｒ加熱（硬化）を行い、組成物フィルム２およびポリイミドフィルム３との積層フィルムを作製するとともに、積層フィルムがシリコンウエハ１に接着した積層体４を製造した。（図１−Ａ） A method for manufacturing a wiring board will be described with reference to FIG.
(Laminate)
The composition film 2 peeled from the PET film is placed so as to cover the entire surface of the silicon wafer 1 (plate thickness 600 μm), and a polyimide film 3 (film thickness 25 μm; “Kapton 100H”; manufactured by Toray Industries, Inc.) is placed thereon. Placed, 200 ° C., 60 min, pressure 1 Mpa, vacuum heating press under conditions of less than 10 kPa, and heated (cured) at 250 ° C. for 24 hours to produce a laminated film with the composition film 2 and the polyimide film 3, A laminated body 4 in which the laminated film was bonded to the silicon wafer 1 was manufactured. (Fig. 1-A)

（配線パターン）
ＹＡＧレーザー加工機（「ＭＬ６０５ＧＴＸ」；三菱電機株式会社製）を用いて、レーザー光の周波数１００Ｈｚ、パルス幅１０μｍ、パルスエネルギー０．３ｍＪの条件で、アルゴンガスを積層体４に吹き付け、ステッパ装置を用いて、１ブロック配線数１００本の設計通りの配線パターン５（パターン厚１〜３μｍ、パターン幅６０μｍ、パターン長さ２０ｍｍ）をパターン間隔４０μｍで得た。（図１−Ｂ） (Wiring pattern)
Using a YAG laser processing machine (“ML605GTX”; manufactured by Mitsubishi Electric Corporation), argon gas was sprayed onto the laminate 4 under the conditions of a laser beam frequency of 100 Hz, a pulse width of 10 μm, and a pulse energy of 0.3 mJ, and the stepper device was As a result, a wiring pattern 5 (pattern thickness 1 to 3 μm, pattern width 60 μm, pattern length 20 mm) as designed with 100 block wirings was obtained at a pattern interval of 40 μm. (Figure 1-B)

（配線基板）
配線パターン５が形成された積層体４にスパッタ装置を用いて、金板をターゲットとして真空雰囲気下でスパッタリングし、金膜６（膜厚３μｍ）を製膜し、積層体４表面を被覆した。（図１−Ｃ） (Wiring board)
Using a sputtering apparatus, the laminate 4 on which the wiring pattern 5 was formed was sputtered in a vacuum atmosphere using a gold plate as a target to form a gold film 6 (film thickness: 3 μm), thereby covering the surface of the laminate 4. (Figure 1-C)

金膜６で被覆された積層体４を加熱オーブンに入れ、大気雰囲気下、２５０℃に加熱した。２５０℃で２００ｈｒ経過しても変化が見られなかったが、３００ｈｒ経過すると、積層体４の形状が維持されたまま組成物フィルム２がシリコンウエハ１表面からポリイミドフィルム３および金膜６とともに、一挙に剥離した。（図１−Ｄ）   The laminate 4 covered with the gold film 6 was placed in a heating oven and heated to 250 ° C. in an air atmosphere. Although no change was observed after 200 hours at 250 ° C., when 300 hours passed, the composition film 2 together with the polyimide film 3 and the gold film 6 was formed from the surface of the silicon wafer 1 while maintaining the shape of the laminate 4. Peeled off. (Fig. 1-D)

冷却後の配線基板は、配線１００本のうち、スミアがある配線は０本であった。
配線基板８の断面を顕微鏡で１５００倍に拡大した写真に見られるように、配線パターン５に金配線７が奇麗に形成された配線基板８が得られた。（図２） As for the wiring board after cooling, out of 100 wirings, there were 0 wirings with smears.
As can be seen in a photograph in which the cross section of the wiring board 8 was magnified 1500 times with a microscope, the wiring board 8 in which the gold wiring 7 was formed beautifully on the wiring pattern 5 was obtained. (Figure 2)

（実施例２）
実施例１において、樹脂組成物を構成するビニル化合物を数平均分子量が２２００のもの（Ａ−1）から、数平均分子量が１２００のもの（Ａ−２）に変更する以外は、実施例１と同様な方法と条件で、配線基板を製造した。
配線基板８を顕微鏡で１５００倍に拡大しても、シリコンウエハによるスミアも、組成物フィルムおよびポリイミドフィルムのスミアも認められなかった。 (Example 2)
In Example 1, except that the vinyl compound constituting the resin composition is changed from one having a number average molecular weight of 2200 (A-1) to one having a number average molecular weight of 1200 (A-2), and A wiring board was manufactured by the same method and conditions.
Even when the wiring board 8 was magnified 1500 times with a microscope, neither a smear due to a silicon wafer nor a smear of a composition film or a polyimide film was observed.

（実施例３）
実施例１において、組成物フィルム２の膜厚９μｍを１８μｍに変更して製膜し、マスクフィルムの膜厚を４３μｍにする以外は実施例１と同様な方法で配線基板を製造した。 配線基板を顕微鏡で１５００倍に拡大しても、シリコンウエハによるスミアも、組成物フィルムおよびポリイミドフィルムのスミアも認められなかった。 (Example 3)
In Example 1, a wiring board was produced in the same manner as in Example 1 except that the film thickness of the composition film 2 was changed to 18 μm and the film thickness of the mask film was changed to 43 μm. Even when the wiring board was magnified 1500 times with a microscope, neither a smear due to the silicon wafer nor a smear of the composition film or the polyimide film was observed.

１ シリコンウエハ
２ 樹脂組成物フィルム
３ ポリイミドフィルム
４ 積層体
５ 配線パターン
６ 金膜
７ 金線
８ 配線基板 DESCRIPTION OF SYMBOLS 1 Silicon wafer 2 Resin composition film 3 Polyimide film 4 Laminated body 5 Wiring pattern 6 Gold film 7 Gold wire 8 Wiring board

Claims (8)

絶縁基板表面にマスクフィルムを設置し、レーザー光を照射して配線パターンを作製し、前記絶縁基板表面に配線層を形成した後、加熱により前記マスクフィルムを前記絶縁基板表面から剥離除去し、前記配線パターンに配線を形成する配線基板の製造方法であって、前記マスクフィルムが、下記式（１）で示されるビニル化合物（Ａ）ならびにゴムおよび／または熱可塑性エラストマーを含有する樹脂組成物のフィルムおよびポリイミドフィルムからなる積層フィルムであり、前記樹脂組成物のフィルムが基板表面に接する、ことを特徴とする配線基板の製造方法。

［式（１）中、Ｒ 1 、Ｒ 2 、Ｒ 3 、Ｒ 4 、Ｒ 5 、Ｒ 6 およびＲ 7 はそれぞれ独立に水素原子、ハロゲン原子、炭素原子数１〜６のアルキル基、炭素原子数１〜６のハロゲン化アルキル基またはフェニル基を表し、複数のＲ 1 、Ｒ 2 、Ｒ 3 、Ｒ 4 、Ｒ 5 、Ｒ 6 およびＲ 7 は同一であっても異なっていてもよい。
−（Ｏ−Ｘ−Ｏ）−は下記式（２）で表される構造であり、−（Ｙ−Ｏ）−は下記式（３）で表される繰返し単位であり、Ｚは酸素原子、窒素原子、イオウ原子、ハロゲン原子を含んでいてもよい炭素原子数１〜３の有機基を表す。
ａおよびｂは少なくとも一方が０でない０〜３００の整数を表し、ｃおよびｄはそれぞれ独立に０または１の整数を表す。］

［式（２）中、Ｒ 8 、Ｒ 9 、Ｒ 10 、Ｒ 14 およびＲ 15 はそれぞれ独立にハロゲン原子、炭素原子数６以下のアルキル基またはフェニル基を表し、Ｒ 11 、Ｒ 12 およびＲ 13 はそれぞれ独立に水素原子、ハロゲン原子、炭素原子数６以下のアルキル基またはフェニル基を表す。
式（３）中、Ｒ 16 およびＲ 17 はそれぞれ独立にハロゲン原子、炭素原子数６以下のアルキル基またはフェニル基を表し、Ｒ 18 およびＲ 19 はそれぞれ独立に水素原子、ハロゲン原子、炭素原子数６以下のアルキル基またはフェニル基を表す。］ A mask film is set on the surface of the insulating substrate, and a wiring pattern is produced by irradiating a laser beam. After forming a wiring layer on the surface of the insulating substrate, the mask film is peeled off from the surface of the insulating substrate by heating, A method of manufacturing a wiring board for forming wiring on a wiring pattern , wherein the mask film is a resin composition film containing a vinyl compound (A) represented by the following formula (1) and rubber and / or a thermoplastic elastomer: A method for producing a wiring board , comprising: a laminated film comprising a polyimide film, wherein the film of the resin composition contacts a substrate surface .

[In the formula (1), R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, or the number of carbon atoms. 1 to 6 halogenated alkyl groups or phenyl groups, and a plurality of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 may be the same or different.
-(O-X-O)-is a structure represented by the following formula (2),-(YO)-is a repeating unit represented by the following formula (3), Z is an oxygen atom, An organic group having 1 to 3 carbon atoms which may contain a nitrogen atom, a sulfur atom or a halogen atom.
a and b each represents an integer of 0 to 300 in which at least one is not 0, and c and d each independently represents an integer of 0 or 1. ]

[In the formula (2), R 8 , R 9 , R 10 , R 14 and R 15 each independently represents a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group, R 11 , R 12 and R 13 Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group.
In the formula (3), R 16 and R 17 each independently represent a halogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group, and R 18 and R 19 each independently represent a hydrogen atom, a halogen atom, or a carbon atom number. The alkyl group or phenyl group of 6 or less is represented. ] 前記（Ａ）成分の−（Ｏ−Ｘ−Ｏ）−が下記式（４）で表される構造であり、前記−（Ｙ−Ｏ）−が下記式（５）または（６）で表される繰返し単位である請求項１に記載の配線基板の製造方法。
 -(O-X-O)-in the component (A) is a structure represented by the following formula (4), and-(YO)-is represented by the following formula (5) or (6). The method for manufacturing a wiring board according to claim 1, wherein the method is a repeating unit .
前記（Ａ）成分の−（Ｙ−Ｏ）−が前記式（６）で表される繰返し単位である請求項２に記載の配線基板の製造方法。 The method for manufacturing a wiring board according to claim 2, wherein — (YO) — of the component (A) is a repeating unit represented by the formula (6) . 前記（Ｂ）成分が熱可塑性エラストマーである請求項１〜３のいずれかに記載の配線基板の製造方法。 The method for manufacturing a wiring board according to claim 1, wherein the component (B) is a thermoplastic elastomer . 前記（Ａ）成分と前記（Ｂ）成分との質量割合が４０：６０〜６０：４０である請求項１〜４のいずれかに記載の配線基板の製造方法。 The method for manufacturing a wiring board according to claim 1, wherein a mass ratio of the component (A) and the component (B) is 40:60 to 60:40 . 前記加熱が温度２００〜３００℃である請求項１〜５のいずれかに記載の配線基板の製造方法。 The method for manufacturing a wiring board according to claim 1, wherein the heating is performed at a temperature of 200 to 300 ° C. 6 . 前記配線パターンの作製がＹＡＧレーザー光の照射による請求項１〜６のいずれかに記載の配線基板の製造方法。 The method for manufacturing a wiring board according to claim 1, wherein the wiring pattern is produced by irradiation with YAG laser light . 前記配線層の形成がスパッタ法、真空蒸着法またはメッキによる請求項１〜７のいずれかに記載の配線基板の製造方法。 The method for manufacturing a wiring board according to claim 1, wherein the wiring layer is formed by sputtering, vacuum deposition, or plating .
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