JP6175827B2 - Method for flattening coating film of liquid photocurable resin composition on substrate, method for producing printed wiring board, and printed wiring board - Google Patents
Method for flattening coating film of liquid photocurable resin composition on substrate, method for producing printed wiring board, and printed wiring board Download PDFInfo
- Publication number
- JP6175827B2 JP6175827B2 JP2013059051A JP2013059051A JP6175827B2 JP 6175827 B2 JP6175827 B2 JP 6175827B2 JP 2013059051 A JP2013059051 A JP 2013059051A JP 2013059051 A JP2013059051 A JP 2013059051A JP 6175827 B2 JP6175827 B2 JP 6175827B2
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- JP
- Japan
- Prior art keywords
- coating film
- resin composition
- liquid photocurable
- photocurable resin
- substrate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 238000000576 coating method Methods 0.000 title claims description 60
- 239000011248 coating agent Substances 0.000 title claims description 58
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- 238000000034 method Methods 0.000 title claims description 32
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- 239000005060 rubber Substances 0.000 claims description 21
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- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 16
- 239000007795 chemical reaction product Substances 0.000 claims description 14
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
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- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 description 5
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- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 4
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- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
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- 229920000459 Nitrile rubber Polymers 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 4
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- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 4
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Landscapes
- Photosensitive Polymer And Photoresist Processing (AREA)
- Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
- Materials For Photolithography (AREA)
- Non-Metallic Protective Coatings For Printed Circuits (AREA)
Description
本発明は、液状光硬化性樹脂組成物の塗膜を基板上で平坦化する方法に関し、更に詳しくは、電子材料分野において用いられる液状光硬化性樹脂組成物の塗膜を基板上で平坦化する方法、プリント配線板の製造方法、及びプリント配線板に関する。 The present invention relates to a method for flattening a coating film of a liquid photocurable resin composition on a substrate, and more particularly, to planarize a coating film of a liquid photocurable resin composition used in the field of electronic materials on a substrate. The present invention relates to a method for manufacturing a printed wiring board and a printed wiring board.
従来、プリント配線板製造における永久マスクレジストは、熱硬化型レジストインキ又は紫外線硬化型レジストインキをスクリーン印刷する方法で作製されていた。近年、電子デバイスの高集積化に伴い、プリント配線板において配線パターン、絶縁パターンの高精細化が必要とされるようになってきたが、従来のスクリーン印刷によるレジスト形成法では、印刷時に滲み、ダレ等が発生するため、高精細なレジストパターンを形成するのが困難である。
そこで、フォトリソグラフィーによるレジスト像形成法が開発されるに至った。具体的な方法としては、まず、ドライフィルム型光硬化性レジストを基材上に熱圧着する、又は液状光硬化性レジストを基材上にカーテン、スプレー塗布する。次に、基材上に設けられた光硬化性レジストに、ネガマスクを介して、紫外線などの活性光線を照射する。そして、活性光線を照射した光硬化性レジストを現像することにより、レジスト像形成を行う。
ドライフィルム型光硬化性レジストでは、基材への熱圧着時に空気を巻き込んでしまい、気泡を生じる場合がある。ドライフィルム型光硬化性レジストに気泡が生じた場合、光硬化性レジストと基材との密着性の低下及びレジスト像の乱れを引き起こし、レジスト性能の低下が懸念される。
Conventionally, a permanent mask resist in the production of printed wiring boards has been produced by a screen printing method using a thermosetting resist ink or an ultraviolet curable resist ink. In recent years, along with the high integration of electronic devices, it has become necessary to increase the definition of wiring patterns and insulating patterns in printed wiring boards, but in conventional resist forming methods by screen printing, bleeding occurs during printing, Since sagging or the like occurs, it is difficult to form a high-definition resist pattern.
Therefore, a resist image forming method by photolithography has been developed. As a specific method, first, a dry film type photocurable resist is thermocompression-bonded on a base material, or a liquid photocurable resist is curtain-sprayed on a base material. Next, the photocurable resist provided on the substrate is irradiated with actinic rays such as ultraviolet rays through a negative mask. Then, a resist image is formed by developing the photocurable resist irradiated with actinic rays.
In a dry film type photocurable resist, air may be entrained at the time of thermocompression bonding to a base material, and bubbles may be generated. When bubbles are generated in the dry film type photocurable resist, the adhesion between the photocurable resist and the base material is deteriorated and the resist image is disturbed.
上述のドライフィルム型光硬化性レジストのレジスト性能の低下を懸念して、液状光硬化性レジストを採用することがある。液状光硬化性レジストは、溶剤現像型とアルカリ現像型があり、作業環境保全、地球環境保全の観点からアルカリ現像型が主流になっている。液状光硬化性レジストを用いる場合では、塗膜の耐熱性、耐薬品性、電気特性を向上させる目的で、更に紫外線露光や加熱を行い、架橋反応を促進させている（例えば、特許文献１及び２参照。）。 A liquid photo-curing resist may be employed in consideration of a decrease in resist performance of the dry film type photo-curing resist. Liquid photocurable resists are classified into a solvent development type and an alkali development type, and the alkali development type is mainly used from the viewpoints of work environment preservation and global environment preservation. In the case of using a liquid photo-curable resist, for the purpose of improving the heat resistance, chemical resistance and electrical properties of the coating film, UV exposure and heating are further performed to promote the crosslinking reaction (for example, Patent Document 1 and 2).
しかしながら、従来の液状光硬化性レジストは、実用特性上の耐湿熱性、耐熱性の点でまだ問題がある。すなわち、アルカリ現像型の液状光硬化性レジストは、アルカリ現像を可能にするために親水性基を有するものが主成分となっているため、薬液、水等が浸透しやすく、レジスト皮膜の実用特性を低下させていると推察される。 However, conventional liquid photocurable resists still have problems in terms of wet heat resistance and heat resistance in practical characteristics. In other words, the alkali-developable liquid photocurable resist is mainly composed of a hydrophilic group in order to enable alkali development. It is guessed that
ところで、近頃は、電子機器の小型化、軽量化、高性能化に伴い、半導体パッケージの小型化、多ピン化が実用化され、量産化が進められている。例えば、ボールグリッドアレイ（ＢＧＡ）、チップサイズパッケージ（ＣＳＰ）等の半導体パッケージにおいて、高信頼性の点から特に耐湿熱性ともいうべき耐プレッシャークッカーテスト性（耐ＰＣＴ性）が必要である。しかし、このような厳しい条件下において、従来の液状光硬化性レジストは、数時間〜十数時間程度しかもたないのが現状である。
更に、実装方法が、挿入実装から表面実装に変わることにより実装時にパッケージにかかる温度が高くなる傾向がある。具体的には、表面実装の場合、予めクリームはんだを必要部分に印刷し、全体を赤外線で加熱し、はんだをリフローして固定する。よって、パッケージ内外部の到達温度は２２０〜２８０℃と著しく高くなり、従来の液状光硬化性レジストでは、熱衝撃で塗膜にクラックが発生したり、基板や封止材から剥離したりと、いわゆる耐リフロー性低下の問題があり、その改良が求められている。
Recently, along with the downsizing, lightening, and high performance of electronic devices, downsizing of semiconductor packages and increasing the number of pins have been put into practical use and mass production is being promoted. For example, in a semiconductor package such as a ball grid array (BGA) and a chip size package (CSP), a pressure cooker test resistance (PCT resistance) that should be particularly referred to as moisture and heat resistance is required from the viewpoint of high reliability. However, under such severe conditions, the conventional liquid photo-curable resist is currently only a few hours to a few dozen hours.
Furthermore, when the mounting method is changed from insertion mounting to surface mounting, the temperature applied to the package at the time of mounting tends to increase. Specifically, in the case of surface mounting, cream solder is printed in advance on a necessary portion, the whole is heated with infrared rays, and the solder is reflowed and fixed. Therefore, the reached temperature inside and outside of the package is remarkably high at 220 to 280 ° C., and in the conventional liquid photocurable resist, cracks occur in the coating film due to thermal shock, or peeling from the substrate or the sealing material, There is a problem of so-called reduction in reflow resistance, and an improvement is demanded.
また、液状光硬化性レジストにおいて、レジスト膜厚の均一性が求められている。即ち、配線を形成した半導体パッケージ基板に液状光硬化性レジストを塗布した場合、レジスト膜厚のばらつきが大きくなると、その後に形成するはんだバンプの高さのばらつきが大きくなり、半導体素子との接続信頼性に問題を生じることがある。そこで、レジスト膜厚のばらつき低減が求められている。 Further, in a liquid photocurable resist, uniformity of the resist film thickness is required. That is, when a liquid photocurable resist is applied to a semiconductor package substrate on which wiring is formed, if the variation in the resist film thickness increases, then the variation in the height of solder bumps to be formed increases, resulting in reliable connection to the semiconductor element. May cause problems with sex. Therefore, there is a demand for reducing variations in resist film thickness.
本発明の目的は、耐熱性、耐湿熱性、密着性、機械特性、電気特性に優れた高性能なレジストマスクを得ることができ、電子材料分野での製造に好適に用いられる液状光硬化性樹脂組成物の塗膜を基板上で平坦化する方法、プリント配線板の製造方法、及びプリント配線板を提供することである。 An object of the present invention is to provide a high-performance resist mask excellent in heat resistance, heat and humidity resistance, adhesion, mechanical properties, and electrical properties, and is a liquid photocurable resin that can be suitably used for manufacturing in the field of electronic materials. It is providing the method of planarizing the coating film of a composition on a board | substrate, the manufacturing method of a printed wiring board, and a printed wiring board.
本発明は以下に記載の各事項に関する。
（１）軟化点３０℃〜１００℃の樹脂（Ａ）と、光重合開始剤（Ｂ）と、希釈剤（Ｃ）と、硬化剤（Ｄ）とを含有する液状光硬化性樹脂組成物の塗膜を基板上で平坦化する方法において、前記液状光硬化性樹脂組成物をプリント配線が形成された前記基板上に塗布して乾燥し、塗膜を形成する工程と、前記塗膜上に透明フィルムを配置し、前記液状光硬化性樹脂組成物のガラス転移温度より５℃〜５０℃高い温度にて、ゴムロール機を用いて０．００５〜１．０ＭＰａで、前記透明フィルムと前記塗膜とを加熱圧着する工程とを含み、前記透明フィルムを剥がして現像した後の前記塗膜の表面粗さ（凹凸度）を４μｍ以下とする液状光硬化性樹脂組成物の塗膜を基板上で平坦化する方法。
（２）液状光硬化性樹脂組成物の塗膜を基板上で平坦化する方法で得られた平坦化された前記塗膜に対して、前記透明フィルムを介して所望のパターンに露光する工程と、露光された前記塗膜から前記透明フィルムを剥がす工程と、露光された前記塗膜を現像してマスクレジストを形成する工程とを含むプリント配線板の製造方法。
（３）軟化点３０℃〜１００℃の樹脂（Ａ）と、光重合開始剤（Ｂ）と、希釈剤（Ｃ）と、硬化剤（Ｄ）とを含有する液状光硬化性樹脂組成物で構成されるマスクレジストを備え、前記マスクレジストの表面粗さ（凹凸度）が４μｍ以下であるプリント配線板。
The present invention relates to each item described below.
(1) A liquid photocurable resin composition containing a resin (A) having a softening point of 30 ° C to 100 ° C, a photopolymerization initiator (B), a diluent (C), and a curing agent (D). In the method of flattening a coating film on a substrate, the liquid photocurable resin composition is applied onto the substrate on which printed wiring is formed and dried to form a coating film; A transparent film is disposed, and the transparent film and the coating film are 0.005 to 1.0 MPa using a rubber roll machine at a temperature 5 to 50 ° C. higher than the glass transition temperature of the liquid photocurable resin composition. A film of a liquid photocurable resin composition having a surface roughness (degree of unevenness) of 4 μm or less on the substrate after peeling and developing the transparent film. How to flatten.
(2) A step of exposing the flattened coating film obtained by the method of flattening a coating film of the liquid photocurable resin composition on a substrate to a desired pattern through the transparent film; A method for producing a printed wiring board, comprising: a step of peeling the transparent film from the exposed coating film; and a step of developing the exposed coating film to form a mask resist.
(3) A liquid photocurable resin composition containing a resin (A) having a softening point of 30 ° C to 100 ° C, a photopolymerization initiator (B), a diluent (C), and a curing agent (D). A printed wiring board comprising a mask resist, wherein the mask resist has a surface roughness (roughness) of 4 μm or less.
本発明によれば、耐熱性、耐湿熱性、密着性、機械特性、電気特性に優れた高性能なレジストマスクを得ることができ、電子材料分野での製造に好適に用いられる液状光硬化性樹脂組成物の塗膜を基板上で平坦化する方法、プリント配線板の製造方法、及びプリント配線板を提供することができる。 According to the present invention, a high-performance resist mask excellent in heat resistance, heat-and-moisture resistance, adhesion, mechanical properties, and electrical properties can be obtained, and a liquid photocurable resin that can be suitably used for manufacturing in the field of electronic materials. The method of planarizing the coating film of a composition on a board | substrate, the manufacturing method of a printed wiring board, and a printed wiring board can be provided.
以下、本発明の一実施形態について詳述するが、本発明は以下の実施形態に限定されるものではない。 Hereinafter, one embodiment of the present invention will be described in detail, but the present invention is not limited to the following embodiment.
本発明の実施形態に係る液状光硬化性樹脂組成物の塗膜を基板上で平坦化する方法で用いる液状光硬化性樹脂組成物は、軟化点３０℃〜１００℃の樹脂（Ａ）と、光重合開始剤（Ｂ）と、希釈剤（Ｃ）と、硬化剤（Ｄ）とを含有する。
液状光硬化性樹脂組成物の塗膜を基板上で平坦化する方法としては、液状光硬化性樹脂組成物をプリント配線が形成された基板上に塗布して乾燥し、塗膜を形成する工程と、塗膜上に透明フィルムを配置し、液状光硬化性樹脂組成物のガラス転移温度より２０℃〜５０℃高い温度にて、ゴムロール機を用いて０．００５〜１．０ＭＰａで、透明フィルムと塗膜とを加熱圧着する工程とを含む。尚、透明フィルムを剥がして現像した後の塗膜の表面の凹凸度は４μｍ以下である。表面の凹凸度が４μｍより大きいと、レジスト膜厚のばらつきが大きくなり、その後に形成するはんだバンプの高さのばらつきが大きくなり、半導体素子との接続信頼性に問題を生じてしまう。
A liquid photocurable resin composition used in a method for flattening a coating film of a liquid photocurable resin composition according to an embodiment of the present invention on a substrate includes a resin (A) having a softening point of 30 ° C to 100 ° C, A photoinitiator (B), a diluent (C), and a hardening | curing agent (D) are contained.
As a method of flattening the coating film of the liquid photocurable resin composition on the substrate, the liquid photocurable resin composition is applied on the substrate on which the printed wiring is formed and dried to form a coating film. And a transparent film on the coating film, and at a temperature 20 ° C. to 50 ° C. higher than the glass transition temperature of the liquid photocurable resin composition, using a rubber roll machine, 0.005 to 1.0 MPa, And a step of thermocompression bonding the coating film. In addition, the unevenness | corrugation degree of the surface of the coating film after peeling and developing a transparent film is 4 micrometers or less. If the surface irregularity is larger than 4 μm, the variation in the resist film thickness becomes large, and the variation in the height of solder bumps to be formed thereafter becomes large, resulting in a problem in connection reliability with the semiconductor element.
基板としては、例えば、ガラスエポキシ樹脂基板、セラミック基板、ガラス基板、シリコン基板、プラスチック基板、金属基板、樹脂層付き基板、金属層付き基板、プラスチックフィルム、樹脂層付きプラスチックフィルム、金属層付きプラスチックフィルムなどが挙げられる。プリント配線が形成された基板としては、表面実装型半導体パッケージ基板などが挙げられる。 Examples of the substrate include a glass epoxy resin substrate, a ceramic substrate, a glass substrate, a silicon substrate, a plastic substrate, a metal substrate, a substrate with a resin layer, a substrate with a metal layer, a plastic film, a plastic film with a resin layer, and a plastic film with a metal layer. Etc. Examples of the substrate on which the printed wiring is formed include a surface mount semiconductor package substrate.
ゴムロール機としては、常圧ラミネータ又は減圧ラミネータなどが挙げられる。 Examples of the rubber roll machine include a normal pressure laminator and a reduced pressure laminator.
具体的な、液状光硬化性樹脂組成物の塗膜を基板上で平坦化する方法としては、プリント配線が形成された基板に、スクリーン印刷法、スプレー法、ロールコート法、カーテンコート法、静電塗装法等の方法で１０〜２００μｍの膜厚で塗布し、次に塗膜を６０〜１１０℃で乾燥させた後、ゴムロール機として常圧ラミネータ（大成ラミネータ株式会社製、ＶＡ−７０００）を用いて、ポリエチレンテレフタレートフィルムを乾燥させた組成物に貼り付ける際に所定条件で加圧作業を行う。 As a specific method for flattening a coating film of a liquid photocurable resin composition on a substrate, a screen printing method, a spray method, a roll coating method, a curtain coating method, a static coating method is applied to a substrate on which a printed wiring is formed. After coating with a film thickness of 10 to 200 μm by a method such as electrocoating, and then drying the coating film at 60 to 110 ° C., a normal pressure laminator (VA-7000, manufactured by Taisei Laminator Co., Ltd.) is used as a rubber roll machine. The pressure is applied under a predetermined condition when the polyethylene terephthalate film is attached to the dried composition.
液状光硬化性樹脂組成物の塗膜をマスクレジストとして用いるプリント配線板の製造方法は、上述の平坦化する方法で平坦化された塗膜に対して、透明フィルムを介して所望のパターンに露光する工程と、露光された塗膜から透明フィルムを剥がす工程と、露光された塗膜を現像してマスクレジストを形成する工程とを含む。 The method of manufacturing a printed wiring board using a coating film of a liquid photocurable resin composition as a mask resist is to expose a coating pattern flattened by the above-described planarization method to a desired pattern through a transparent film. A step of peeling off the transparent film from the exposed coating film, and a step of developing the exposed coating film to form a mask resist.
液状光硬化性樹脂組成物の塗膜を平坦化してマスクレジストとして用いるプリント配線板は、平坦性が優れているので、高密度多層板及び半導体パッケージ等の電子材料分野の製造に好適に用いられる。 A printed wiring board used as a mask resist by flattening a coating film of a liquid photocurable resin composition is excellent in flatness, and is therefore suitably used for manufacturing electronic materials such as high-density multilayer boards and semiconductor packages. .
具体的な、プリント配線板の製造方法は、液状光硬化性樹脂組成物の塗膜をプリント配線が形成された基板上で平坦化した後、所望のパターンを有するネガフィルムを透明フィルムと直接接触（又は透明なフィルムを介して）させて、活性光（例、紫外線）を好ましくは１０〜１，０００ｍＪ／ｃｍ２照射して露光する。そして、透明フィルム及びネガフィルムを塗膜から剥がす。その後、未露光部を希アルカリ水溶液で溶解除去（現像）する。次に、露光部分を後露光（紫外線露光）及び／又は後加熱によってマスクレジストを十分硬化させて硬化膜とすることが好ましい。後露光は例えば１〜５Ｊ／ｃｍ２が好ましく、後加熱は、１００〜２００℃で３０分〜１２時間が好ましい。 A specific method for producing a printed wiring board is to directly apply a negative film having a desired pattern to a transparent film after flattening a coating film of a liquid photocurable resin composition on a substrate on which printed wiring is formed. (Or through a transparent film) and exposure is performed by irradiation with active light (eg, ultraviolet rays), preferably 10 to 1,000 mJ / cm 2 . Then, the transparent film and the negative film are peeled off from the coating film. Thereafter, the unexposed portion is dissolved and removed (developed) with a dilute alkaline aqueous solution. Next, it is preferable that the exposed portion of the mask resist is sufficiently cured by post-exposure (ultraviolet exposure) and / or post-heating to form a cured film. The post-exposure is preferably, for example, 1 to 5 J / cm 2 , and the post-heating is preferably 100 to 200 ° C. for 30 minutes to 12 hours.
樹脂（Ａ）は、軟化点３０℃〜１００℃の樹脂であればよい。樹脂（Ａ）は、酸変性ビニル基含有エポキシ樹脂であることが好ましい。酸変性ビニル基含有エポキシ樹脂としては、エポキシ樹脂を有機酸、好ましくはビニル基含有モノカルボン酸で変性した樹脂が用いられるが、好ましくは一般式（I）で示されるノボラック型エポキシ樹脂、一般式（II）で示されるビスフェノールＡ型エポキシ樹脂又はビスフェノールＦ型エポキシ樹脂、及び一般式（III）で示されるサリチルアルデヒド型エポキシ樹脂からなる群から選択される少なくとも１種類のエポキシ樹脂（ａ）とビニル基含有モノカルボン酸（ｂ）とを反応させて得られる第１反応生成物（Ａ１）が用いられる。 The resin (A) may be a resin having a softening point of 30 ° C to 100 ° C. The resin (A) is preferably an acid-modified vinyl group-containing epoxy resin. As the acid-modified vinyl group-containing epoxy resin, a resin obtained by modifying an epoxy resin with an organic acid, preferably a vinyl group-containing monocarboxylic acid, is used, but preferably a novolak-type epoxy resin represented by the general formula (I), At least one epoxy resin (a) selected from the group consisting of bisphenol A type epoxy resin or bisphenol F type epoxy resin represented by (II) and salicylaldehyde type epoxy resin represented by general formula (III) and vinyl The first reaction product (A1) obtained by reacting the group-containing monocarboxylic acid (b) is used.
液状光硬化性樹脂組成物において、酸変性ビニル基含有エポキシ樹脂（Ａ）は、紫外線や熱により橋架け反応（硬化反応）が進行することで、硬化収縮して樹脂内部に歪み（内部応力）が加わり、可とう性や接着性が低下する場合がある。そこで、柔軟性を持つエラストマーを適宜添加することで、硬化膜の応力を緩和し、硬化塗膜の改質をすることができる。例えば、酸変性ビニル基含有エポキシ樹脂（Ａ）にエラストマーを併用し、ポリマーアロイ化することで、硬化膜の硬化収縮、可とう性を改質することができる。 In the liquid photocurable resin composition, the acid-modified vinyl group-containing epoxy resin (A) is cured and contracted by the crosslinking reaction (curing reaction) caused by ultraviolet rays or heat, and is distorted inside the resin (internal stress). May be added and flexibility and adhesiveness may decrease. Therefore, by appropriately adding a flexible elastomer, the stress of the cured film can be relaxed and the cured coating film can be modified. For example, the curing shrinkage and flexibility of the cured film can be improved by using an elastomer together with the acid-modified vinyl group-containing epoxy resin (A) and polymerizing it.
酸変性ビニル基含有エポキシ樹脂（Ａ）は、エポキシ樹脂（ａ）とビニル基含有モノカルボン酸（ｂ）とを反応させることにより得られる第１反応生成物（Ａ１）を用いることができる。また、酸変性ビニル基含有エポキシ樹脂（Ａ）は、第１反応生成物（Ａ１）に飽和若しくは不飽和基含有多塩基酸無水物（ｃ）を反応させることにより得られる第２反応生成物（Ａ２）を用いることができる。
第１反応生成物（Ａ１）は、具体的には、エポキシ樹脂（ａ）のエポキシ基とビニル基含有モノカルボン酸（ｂ）のカルボキシル基との付加反応により水酸基が形成されると推察される。第２反応生成物（Ａ２）は、最初の反応として、エポキシ樹脂（ａ）のエポキシ基とビニル基含有モノカルボン酸（ｂ）のカルボキシル基との付加反応により水酸基が形成され、次の反応で生成した水酸基（エポキシ樹脂（ａ）中にある元来ある水酸基も含む）と飽和若しくは不飽和基含有多塩基酸無水物（ｃ）の酸無水物基とが半エステル反応しているものと推察される。
As the acid-modified vinyl group-containing epoxy resin (A), the first reaction product (A1) obtained by reacting the epoxy resin (a) with the vinyl group-containing monocarboxylic acid (b) can be used. The acid-modified vinyl group-containing epoxy resin (A) is a second reaction product (A) obtained by reacting the first reaction product (A1) with a saturated or unsaturated group-containing polybasic acid anhydride (c). A2) can be used.
Specifically, the first reaction product (A1) is speculated that a hydroxyl group is formed by an addition reaction between the epoxy group of the epoxy resin (a) and the carboxyl group of the vinyl group-containing monocarboxylic acid (b). . In the second reaction product (A2), as the first reaction, a hydroxyl group is formed by an addition reaction between the epoxy group of the epoxy resin (a) and the carboxyl group of the vinyl group-containing monocarboxylic acid (b). It is inferred that the generated hydroxyl group (including the original hydroxyl group in the epoxy resin (a)) and the acid anhydride group of the saturated or unsaturated group-containing polybasic acid anhydride (c) undergo a half-ester reaction. Is done.
一般式（I）で示されるノボラック型エポキシ樹脂は、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂があり、公知の方法でフェノールノボラック樹脂、クレゾールノボラック樹脂にエピクロルヒドリンを反応させることで得られる。 The novolak-type epoxy resin represented by the general formula (I) includes a phenol novolak-type epoxy resin and a cresol novolak-type epoxy resin, and can be obtained by reacting a phenol novolak resin or a cresol novolak resin with epichlorohydrin by a known method.
一般式（II）で示される、Ｘがグリシジル基であるビスフェノールＡ型エポキシ樹脂及びビスフェノールＦ型エポキシ樹脂は、例えば、一般式（IV）で示されるビスフェノールＡ型エポキシ樹脂及びビスフェノールＦ型エポキシ樹脂の水酸基とエピクロルヒドリンを反応させることにより得ることができる。水酸基とエピクロルヒドリンとの反応を促進するためには、反応温度５０〜１２０℃でアルカリ金属水酸化物存在下、ジメチルホルムアミド、ジメチルアセトアミド、ジメチルスルホキシド等の極性有機溶剤中で反応を行うのが好ましい。反応温度が５０℃〜１２０℃では反応が好適に進行し、副反応が生じないので好ましい。 The bisphenol A type epoxy resin and bisphenol F type epoxy resin represented by the general formula (II) where X is a glycidyl group are, for example, bisphenol A type epoxy resin and bisphenol F type epoxy resin represented by the general formula (IV). It can be obtained by reacting a hydroxyl group with epichlorohydrin. In order to promote the reaction between the hydroxyl group and epichlorohydrin, the reaction is preferably carried out in a polar organic solvent such as dimethylformamide, dimethylacetamide or dimethylsulfoxide in the presence of an alkali metal hydroxide at a reaction temperature of 50 to 120 ° C. A reaction temperature of 50 ° C. to 120 ° C. is preferable because the reaction proceeds suitably and no side reaction occurs.
一般式（III）で示されるサリチルアルデヒド型エポキシ樹脂としては、具体的にはＦＡＥ−２５００、ＥＰＰＮ−５０１Ｈ、ＥＰＰＮ−５０２Ｈ（以上、日本化薬株式会社製、商品名）等が挙げられる。 Specific examples of the salicylaldehyde type epoxy resin represented by the general formula (III) include FAE-2500, EPPN-501H, EPPN-502H (above, Nippon Kayaku Co., Ltd., trade name) and the like.
ビニル基含有モノカルボン酸（ｂ）としては、例えば、アクリル酸、アクリル酸の二量体、メタクリル酸、β−フルフリルアクリル酸、β−スチリルアクリル酸、桂皮酸、クロトン酸、α−シアノ桂皮酸等が挙げられる。また、ビニル基含有モノカルボン酸（ｂ）としては、水酸基含有アクリレートと飽和あるいは不飽和二塩基酸無水物との反応生成物である半エステル化合物、ビニル基含有モノグリシジルエーテル若しくはビニル基含有モノグリシジルエステルと飽和あるいは不飽和二塩基酸無水物との反応生成物である半エステル化合物が挙げられる。これら半エステル化合物は、水酸基含有アクリレート、ビニル基含有モノグリシジルエーテル若しくはビニル基含有モノグリシジルエステルと飽和あるいは不飽和二塩基酸無水物とを等モル比で反応させることで得られる。これらビニル基含有モノカルボン酸（ｂ）は、単独、又は二種類以上併用して用いることができる。 Examples of the vinyl group-containing monocarboxylic acid (b) include acrylic acid, dimer of acrylic acid, methacrylic acid, β-furfurylacrylic acid, β-styrylacrylic acid, cinnamic acid, crotonic acid, α-cyanocinnamic acid. An acid etc. are mentioned. The vinyl group-containing monocarboxylic acid (b) includes a half ester compound, a vinyl group-containing monoglycidyl ether or a vinyl group-containing monoglycidyl which is a reaction product of a hydroxyl group-containing acrylate and a saturated or unsaturated dibasic acid anhydride. A half ester compound which is a reaction product of an ester and a saturated or unsaturated dibasic acid anhydride can be used. These half ester compounds are obtained by reacting a hydroxyl group-containing acrylate, a vinyl group-containing monoglycidyl ether or a vinyl group-containing monoglycidyl ester with a saturated or unsaturated dibasic acid anhydride in an equimolar ratio. These vinyl group-containing monocarboxylic acids (b) can be used alone or in combination of two or more.
ビニル基含有モノカルボン酸（ｂ）の一例である上記半エステル化合物の合成に用いられる水酸基含有アクリレート、ビニル基含有モノグリシジルエーテル、ビニル基含有モノグリシジルエステルとしては、例えば、ヒドロキシエチルアクリレート、ヒドロキシエチルメタクリレート、ヒドロキシプロピルアクリレート、ヒドロキシプロピルメタクリレート、ヒドロキシブチルアクリレート、ヒドロキシブチルメタクリレート、ポリエチレングリコールモノアクリレート、ポリエチレングリコールモノメタクリレート、トリメチロールプロパンジアクリレート、トリメチロールプロパンジメタクリレート、ペンタエリスルトールトリアクリレート、ペンタエリスリトールトリメタクリレート、ジペンタエリスリトールペンタアクリレート、ペンタエリスリトールペンタメタクリレート、グリシジルアクリレート、グリシジルメタクリレート等が挙げられる。
また、ビニル基含有モノカルボン酸（ｂ）の一例である上記半エステル化合物の合成に用いられるビニル基含有モノグリシジルエーテルとしては、アリルグリシジルエーテル、３−メタクリロイルオキシメチルシクロヘキセンオキサイド、３−アクリロイルオキシメチルシクロヘキセンオキサイド、３−ビニルシクロヘキセンオキサイド、ビニルグリシジルエーテル等が挙げられる。
Examples of the hydroxyl group-containing acrylate, vinyl group-containing monoglycidyl ether, and vinyl group-containing monoglycidyl ester used in the synthesis of the half ester compound as an example of the vinyl group-containing monocarboxylic acid (b) include hydroxyethyl acrylate, hydroxyethyl Methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, polyethylene glycol monoacrylate, polyethylene glycol monomethacrylate, trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol tris Methacrylate, dipentaerythritol pentaacrylate, Data dipentaerythritol methacrylate, glycidyl acrylate, glycidyl methacrylate and the like.
Examples of the vinyl group-containing monoglycidyl ether used for the synthesis of the half ester compound as an example of the vinyl group-containing monocarboxylic acid (b) include allyl glycidyl ether, 3-methacryloyloxymethylcyclohexene oxide, and 3-acryloyloxymethyl. Examples include cyclohexene oxide, 3-vinylcyclohexene oxide, and vinyl glycidyl ether.
上記半エステル化合物の合成に用いられる飽和あるいは不飽和二塩基酸無水物としては、例えば、無水コハク酸、無水マレイン酸、テトラヒドロ無水フタル酸、無水フタル酸、メチルテトラヒドロ無水フタル酸、エチルテトラヒドロ無水フタル酸、ヘキサヒドロ無水フタル酸、メチルヘキサヒドロ無水フタル酸、エチルヘキサヒドロ無水フタル酸、無水イタコン酸等が挙げられる。 Examples of the saturated or unsaturated dibasic acid anhydride used in the synthesis of the half ester compound include succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, methyltetrahydrophthalic anhydride, and ethyltetrahydrophthalic anhydride. Examples thereof include acid, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, ethylhexahydrophthalic anhydride, itaconic anhydride and the like.
エポキシ樹脂（ａ）とビニル基含有モノカルボン酸（ｂ）との反応において、光重合性が高くなり、光感度が大きくなるという観点から、エポキシ樹脂（ａ）のエポキシ基１当量に対して、ビニル基含有モノカルボン酸（ｂ）が０．８〜１．０５当量となる比率で反応させることが好ましく、更に好ましくは０．９〜１．０当量である。 In the reaction between the epoxy resin (a) and the vinyl group-containing monocarboxylic acid (b), from the viewpoint of increasing photopolymerization and increasing photosensitivity, with respect to 1 equivalent of the epoxy group of the epoxy resin (a), The vinyl group-containing monocarboxylic acid (b) is preferably reacted at a ratio of 0.8 to 1.05 equivalent, more preferably 0.9 to 1.0 equivalent.
エポキシ樹脂（ａ）とビニル基含有モノカルボン酸（ｂ）は有機溶剤に溶かして反応させられ、有機溶剤としては、例えば、エチルメチルケトン、シクロヘキサノン等のケトン類、トルエン、キシレン、テトラメチルベンゼン等の芳香族炭化水素類、メチルセロソルブ、ブチルセロソルブ、メチルカルビトール、ブチルカルビトール、プロピレングリコールモノメチルエーテル、ジプロピレングリコールモノエチルエーテル、ジプロピレングリコールジエチルエーテル、トリエチレングリコールモノエチルエーテル等のグリコールエーテル類、酢酸エチル、酢酸ブチル、ブチルセロソルブアセテート、カルビトールアセテート等のエステル類、オクタン、デカンなどの脂肪族炭化水素類、石油エーテル、石油ナフサ、水添石油ナフサ、ソルベントナフサ等の石油系溶剤等が挙げられる。 The epoxy resin (a) and the vinyl group-containing monocarboxylic acid (b) are dissolved and reacted in an organic solvent. Examples of the organic solvent include ketones such as ethyl methyl ketone and cyclohexanone, toluene, xylene, tetramethylbenzene and the like. Aromatic hydrocarbons, methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, glycol ethers such as propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether, Esters such as ethyl acetate, butyl acetate, butyl cellosolve acetate, carbitol acetate, aliphatic hydrocarbons such as octane, decane, petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, sorbet Petroleum solvents such as Tonafusa like.
更に、エポキシ樹脂（ａ）とビニル基含有モノカルボン酸（ｂ）の反応を促進させるために触媒を用いるのが好ましい。用いられる触媒としては、例えば、トリエチルアミン、ベンジルメチルアミン、メチルトリエチルアンモニウムクロライド、ベンジルトリメチルアンモニウムクロライド、ベンジルトリメチルアンモニウムブロマイド、ベンジルトリメチルメチルアンモニウムアイオダイド、トリフェニルホスフィン等が挙げられる。触媒の使用量は、エポキシ樹脂とビニル基含有モノカルボン酸との反応が促進されるという観点から、エポキシ樹脂（ａ）とビニル基含有モノカルボン酸（ｂ）の合計１００質量部に対して、好ましくは０．１〜１０質量部である。 Furthermore, it is preferable to use a catalyst for promoting the reaction between the epoxy resin (a) and the vinyl group-containing monocarboxylic acid (b). Examples of the catalyst used include triethylamine, benzylmethylamine, methyltriethylammonium chloride, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylmethylammonium iodide, and triphenylphosphine. From the viewpoint that the reaction between the epoxy resin and the vinyl group-containing monocarboxylic acid is promoted, the amount of the catalyst used is based on a total of 100 parts by mass of the epoxy resin (a) and the vinyl group-containing monocarboxylic acid (b). Preferably it is 0.1-10 mass parts.
また、エポキシ樹脂（ａ）とビニル基含有モノカルボン酸（ｂ）の反応中の重合を防止する目的で、重合防止剤を使用するのが好ましい。重合禁止剤としては、例えば、ハイドロキノン、メチルハイドロキノン、ハイドロキノンモノメチルエーテル、カテコール、ピロガロール等が挙げられる。重合防止剤の使用量は、反応中の重合防止と組成物の貯蔵安定性（シェルフライフ）が改良されるという観点から、エポキシ樹脂（ａ）とビニル基含有モノカルボン酸（ｂ）の合計１００質量部に対して、好ましくは０．０１〜１質量部である。反応温度は、同様の観点から、好ましくは６０〜１５０℃、更に好ましくは８０〜１２０℃である。 Moreover, it is preferable to use a polymerization inhibitor for the purpose of preventing polymerization during the reaction of the epoxy resin (a) and the vinyl group-containing monocarboxylic acid (b). Examples of the polymerization inhibitor include hydroquinone, methyl hydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol and the like. The amount of the polymerization inhibitor used is a total of 100 of the epoxy resin (a) and the vinyl group-containing monocarboxylic acid (b) from the viewpoint of preventing polymerization during the reaction and improving the storage stability (shelf life) of the composition. Preferably it is 0.01-1 mass part with respect to a mass part. From the same viewpoint, the reaction temperature is preferably 60 to 150 ° C, more preferably 80 to 120 ° C.
ビニル基含有モノカルボン酸（ｂ）は、必要に応じて、無水トリメリット酸、無水ピロメリット酸、ベンゾフェノンテトラカルボン酸無水物、ビフェニルテトラカルボン酸無水物等の多塩基酸無水物と併用することができる。 The vinyl group-containing monocarboxylic acid (b) should be used in combination with polybasic acid anhydrides such as trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, biphenyltetracarboxylic anhydride as necessary. Can do.
飽和若しくは不飽和基含有多塩基酸無水物（ｃ）としては、例えば、無水コハク酸、無水マレイン酸、テトラヒドロ無水フタル酸、無水フタル酸、メチルテトラヒドロ無水フタル酸、エチルテトラヒドロ無水フタル酸、ヘキサヒドロ無水フタル酸、メチルヘキサヒドロ無水フタル酸、エチルヘキサヒドロ無水フタル酸、無水イタコン酸等が挙げられる。 Examples of the saturated or unsaturated group-containing polybasic acid anhydride (c) include succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, methyltetrahydrophthalic anhydride, ethyltetrahydrophthalic anhydride, hexahydro anhydride Examples include phthalic acid, methylhexahydrophthalic anhydride, ethylhexahydrophthalic anhydride, itaconic anhydride and the like.
第１反応生成物（Ａ１）と飽和若しくは不飽和基含有多塩基酸無水物（ｃ）との反応において、第１反応生成物（Ａ１）中の水酸基１当量に対して、飽和若しくは不飽和基含有多塩基酸無水物（ｃ）を０．１〜１．０当量反応させることで、酸変性ビニル基含有エポキシ樹脂（Ａ）の酸価を調整できる。酸変性ビニル基含有エポキシ樹脂（Ａ）の酸価は３０〜１５０ｍｇＫＯＨ／ｇであることが好ましく、５０〜１２０ｍｇＫＯＨ／ｇであることが更に好ましい。酸価が３０ｍｇＫＯＨ／ｇ未満では液状光硬化性樹脂組成物の希アルカリ溶液への溶解性が低下し、１５０ｍｇＫＯＨ／ｇを超えると硬化膜の電気特性が低下する傾向がある。第１反応生成物（Ａ１）と飽和若しくは不飽和基含有多塩基酸無水物（ｃ）との反応温度は、６０〜１２０℃が好ましい。 In the reaction of the first reaction product (A1) with the saturated or unsaturated group-containing polybasic acid anhydride (c), the saturated or unsaturated group is equivalent to 1 equivalent of the hydroxyl group in the first reaction product (A1). The acid value of the acid-modified vinyl group-containing epoxy resin (A) can be adjusted by reacting the contained polybasic acid anhydride (c) in an amount of 0.1 to 1.0 equivalent. The acid value of the acid-modified vinyl group-containing epoxy resin (A) is preferably 30 to 150 mgKOH / g, and more preferably 50 to 120 mgKOH / g. When the acid value is less than 30 mgKOH / g, the solubility of the liquid photocurable resin composition in a dilute alkali solution is lowered, and when it exceeds 150 mgKOH / g, the electric characteristics of the cured film tend to be lowered. The reaction temperature between the first reaction product (A1) and the saturated or unsaturated group-containing polybasic acid anhydride (c) is preferably 60 to 120 ° C.
エポキシ樹脂（ａ）は、必要に応じて、例えば、水添ビスフェノールＡ型エポキシ樹脂を一部併用することもできる。更に、酸変性ビニル基含有エポキシ樹脂（Ａ）は、スチレン−無水マレイン酸共重合体のヒドロキシエチルアクリレート変性物あるいはスチレン−無水マレイン酸共重合体のヒドロキシエチルアクリレート変性物等のスチレン−マレイン酸系樹脂を一部併用することができる。 As for an epoxy resin (a), a hydrogenated bisphenol A type epoxy resin can also be used together partially as needed. Further, the acid-modified vinyl group-containing epoxy resin (A) is a styrene-maleic acid-based styrene-maleic anhydride copolymer modified with hydroxyethyl acrylate or a styrene-maleic anhydride copolymer modified with hydroxyethyl acrylate. A part of the resin can be used in combination.
光重合開始剤（Ｂ）としては、例えば、（２，６−ジメトキシベンゾイル）−２，４，６−トリメチルベンゾイル−ペンチルホスフィンオキサイド、ビス（２，４，６−トリメチルベンゾイル）−フェニルホスフィンオキサイド、２，４，６−トリメチルベンゾイルジフェニルホスフィンオキサイド、エチル−２，４，６−トリメチルベンゾイルフェニルホスフィネイト等のホスフィン類、ベンゾイン、ベンゾインメチルエーテル、ベンゾインイソプロピルエーテル等のベンゾイン類、アセトフェノン、２，２−ジメトキシ−２−フェニルアセトフェノン、２，２−ジエトキシ−２−フェニルアセトフェノン、１，１−ジクロロアセトフェノン、１−ヒドロキシシクロヘキシルフェニルケトン、２−メチル−１−［４−（メチルチオ）フェニル］−２−モルフォリノ−１−プロパノン、Ｎ，Ｎ−ジメチルアミノアセトフェノン等のアセトフェノン類、２−メチルアントラキノン、２−エチルアントラキノン、２−tert−ブチルアントラキノン、１−クロロアントラキノン、２−アミルアントラキノン、２−アミノアントラキノン等のアントラキノン類、２，４−ジメチルチオキサントン、２，４−ジエチルチオキサントン、２−クロロチオキサントン、２，４−ジイソプロピルチオキサントン等のチオキサントン類、アセトフェノンジメチルケタール、ベンジルジメチルケタール等のケタール類、ベンゾフェノン、メチルベンゾフェノン、４，４′−ジクロロベンゾフェノン、４，４′−ビス（ジエチルアミノ）ベンゾフェノン、ミヒラーズケトン、４−ベンゾイル−４′−メチルジフェニルサルファイド等のベンゾフェノン類、１，２−オクタンジオン−１−［４−（フェニルチオ）フェニル］−２−（ｏ−ベンゾイルオキシム）等のオキシム類があり、これらは単独あるいは２種以上を組合せて用いることができる。 Examples of the photopolymerization initiator (B) include (2,6-dimethoxybenzoyl) -2,4,6-trimethylbenzoyl-pentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, Phosphines such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide, ethyl-2,4,6-trimethylbenzoylphenylphosphinate, benzoins such as benzoin, benzoin methyl ether, benzoin isopropyl ether, acetophenone, 2,2 -Dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) pheny ] -2-morpholino-1-propanone, acetophenones such as N, N-dimethylaminoacetophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone, 2 Anthraquinones such as aminoanthraquinone, thioxanthones such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone, ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal, Benzophenone, methylbenzophenone, 4,4'-dichlorobenzophenone, 4,4'-bis (diethylamino) benzophenone, Michler's ketone, 4-benzoyl-4'-methyldi There are benzophenones such as phenyl sulfide, and oximes such as 1,2-octanedione-1- [4- (phenylthio) phenyl] -2- (o-benzoyloxime). These may be used alone or in combination of two or more. Can be used.
更に、光重合開始剤（Ｂ）としては、Ｎ，Ｎ−ジメチルアミノ安息香酸エチルエステル、Ｎ，Ｎ−ジメチルアミノ安息香酸イソアミルエステル、ペンチル−４−ジメチルアミノベンゾエート、トリエチルアミン、トリエタノールアミン等の三級アミン類のような光重合開始助剤を単独あるいは２種以上を組合せて用いることができる。 Further, the photopolymerization initiator (B) includes N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-dimethylaminobenzoate, triethylamine, triethanolamine and the like. Photopolymerization initiation assistants such as secondary amines can be used alone or in combination of two or more.
液状光硬化性樹脂組成物中に含まれる光重合開始剤（Ｂ）の量は、液状光硬化性樹脂組成物中、好ましくは０．５〜２０質量％、更に好ましくは２〜１５質量％用いられる。０．５〜２０質量％では、露光部が現像中に溶出することがなく、耐熱性が低下することもないので好ましい。 The amount of the photopolymerization initiator (B) contained in the liquid photocurable resin composition is preferably 0.5 to 20% by mass, more preferably 2 to 15% by mass in the liquid photocurable resin composition. It is done. An amount of 0.5 to 20% by mass is preferable because the exposed portion does not elute during development and the heat resistance does not decrease.
希釈剤（Ｃ）としては、例えば、有機溶剤及び／又は光重合性モノマーが使用できる。有機溶剤としては、例えば、エチルメチルケトン、シクロヘキサノン等のケトン類、トルエン、キシレン、テトラメチルベンゼン等の芳香族炭化水素類、メチルセロソルブ、ブチルセロソルブ、メチルカルビトール、ブチルカルビトール、プロピレングリコールモノメチルエーテル、ジプロピレングリコールモノエチルエーテル、ジプロピレングリコールジエチルエーテル、トリエチレングリコールモノエチルエーテル等のグリコールエーテル類、酢酸エチル、酢酸ブチル、ブチルセロソルブアセテート、カルビトールアセテート等のエステル類、オクタン、デカンなどの脂肪族炭化水素類、石油エーテル、石油ナフサ、水添石油ナフサ、ソルベントナフサ等の石油系溶剤等が挙げられる。 As the diluent (C), for example, an organic solvent and / or a photopolymerizable monomer can be used. Examples of the organic solvent include ketones such as ethyl methyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene, methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, Glycol ethers such as dipropylene glycol monoethyl ether, dipropylene glycol diethyl ether and triethylene glycol monoethyl ether, esters such as ethyl acetate, butyl acetate, butyl cellosolve acetate and carbitol acetate, aliphatic carbonization such as octane and decane Examples thereof include petroleum solvents such as hydrogen, petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha.
また、光重合性モノマーとしては、例えば、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート等のヒドロキシアルキル（メタ）アクリレート類、エチレングリコール、メトキシテトラエチレングリコール、ポリエチレングリコール等のグリコールのモノ又はジ（メタ）アクリレート類、Ｎ，Ｎ−ジメチル（メタ）アクリルアミド、Ｎ−メチロール（メタ）アクリルアミド等の（メタ）アクリルアミド類、Ｎ，Ｎ−ジメチルアミノエチル（メタ）アクリレート等のアミノアルキル（メタ）アクリレート類、ヘキサンジオール、トリメチロールプロパン、ペンタエリスリトール、ジトリメチロールプロパン、ジペンタエリスリトール、トリス−ヒドロキシエチルイソシアヌレート等の多価アルコール又はこれらのエチレンオキサイドあるいはプロピレンオキサイド付加物の多価（メタ）アクリレート類、フェノキシエチル（メタ）アクリレート、ビスフェノールＡのポリエトキシジ（メタ）アクリレート等のフェノール類のエチレンオキサイドあるいはプロピレンオキサイド付加物の（メタ）アクリレート類、グリセリンジグリシジルエーテル、トリメチロールプロパントリグリシジルエーテル、トリグリシジルイソシアヌレートなどのグリシジルエーテルの（メタ）アクリレート類、及びメラミン（メタ）アクリレート等を挙げることができる。 Examples of the photopolymerizable monomer include hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate, ethylene glycol, methoxytetraethylene glycol, and polyethylene glycol. Glycol mono- or di (meth) acrylates, N, N-dimethyl (meth) acrylamide, (meth) acrylamides such as N-methylol (meth) acrylamide, amino such as N, N-dimethylaminoethyl (meth) acrylate Polyhydric alcohols such as alkyl (meth) acrylates, hexanediol, trimethylolpropane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, tris-hydroxyethyl isocyanurate, etc. Polyethylene (meth) acrylates of these ethylene oxide or propylene oxide adducts, phenoxyethyl (meth) acrylate, (meth) acrylates of phenolic ethylene oxide or propylene oxide adducts such as polyethoxydi (meth) acrylate of bisphenol A And (meth) acrylates of glycidyl ethers such as glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, triglycidyl isocyanurate, and melamine (meth) acrylate.
希釈剤（Ｃ）は、単独あるいは２種以上を組み合わせて用いられ、液状光硬化性樹脂組成物中に含まれる希釈剤（Ｃ）の量は、液状光硬化性樹脂組成物中、好ましくは５〜８０質量％、更に好ましくは１０〜７０質量％用いられる。５〜８０質量％では、光感度が高く露光部が現像中に溶出することがなく、耐熱性が低下することもないので好ましい。 The diluent (C) is used alone or in combination of two or more, and the amount of the diluent (C) contained in the liquid photocurable resin composition is preferably 5 in the liquid photocurable resin composition. -80 mass%, More preferably, 10-70 mass% is used. 5 to 80% by mass is preferable because the photosensitivity is high and the exposed portion is not eluted during development, and the heat resistance is not lowered.
硬化剤（Ｄ）としては、それ自体が熱、紫外線等で硬化する化合物、あるいは本発明の組成物中の光硬化性樹脂成分である酸変性ビニル基含有エポキシ樹脂（Ａ）のカルボキシ基、水酸基と熱、紫外線等で硬化する化合物が好ましい。硬化剤を用いることで、最終硬化膜の耐熱性、密着性、耐薬品性等を向上させることができる。 Examples of the curing agent (D) include a compound that cures itself by heat, ultraviolet rays, or the like, or a carboxyl group or a hydroxyl group of an acid-modified vinyl group-containing epoxy resin (A) that is a photocurable resin component in the composition of the present invention. And a compound that is cured by heat, ultraviolet rays or the like. By using a curing agent, the heat resistance, adhesion, chemical resistance, etc. of the final cured film can be improved.
硬化剤（Ｄ）としては、例えば、熱硬化性化合物として、エポキシ化合物、メラミン化合物、尿素化合物、オキサゾリン化合物等を挙げることができる。エポキシ化合物としては、例えば、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、水添ビスフェノールＡ型エポキシ樹脂、臭素化ビスフェノールＡ型エポキシ樹脂、ノボラック型エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂、ビフェニル型エポキシ樹脂あるいは、トリグリシジルイソシアヌレート等の複素環式エポキシ樹脂、ビキシレノール型エポキシ樹脂等が挙げられる。メラミン化合物としては、例えば、トリアミノトリアジン、ヘキサメトキシメラミン、ヘキサブトキシ化メラミン等が挙げられる。尿素化合物としては、ジメチロール尿素等が挙げられる。 As a hardening | curing agent (D), an epoxy compound, a melamine compound, a urea compound, an oxazoline compound etc. can be mentioned as a thermosetting compound, for example. Examples of the epoxy compound include bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, brominated bisphenol A type epoxy resin, novolac type epoxy resin, bisphenol S type epoxy resin, and biphenyl type epoxy resin. Alternatively, heterocyclic epoxy resins such as triglycidyl isocyanurate, bixylenol type epoxy resins and the like can be mentioned. Examples of the melamine compound include triaminotriazine, hexamethoxymelamine, hexabutoxylated melamine and the like. Examples of the urea compound include dimethylol urea.
硬化剤（Ｄ）は、単独あるいは２種以上を組み合わせて用いられ、液状光硬化性樹脂組成物中に含まれる硬化剤（Ｄ）の量は、液状光硬化性樹脂組成物中、好ましくは２〜５０質量％、更に好ましくは１０〜４０質量％用いられる。２〜５０質量％では、最終硬化塗膜の耐熱性が高くなり、現像性が低下することがないので好ましい。 The curing agent (D) is used alone or in combination of two or more. The amount of the curing agent (D) contained in the liquid photocurable resin composition is preferably 2 in the liquid photocurable resin composition. -50 mass%, More preferably, 10-40 mass% is used. A content of 2 to 50% by mass is preferable because the heat resistance of the final cured coating film increases and the developability does not deteriorate.
液状光硬化性樹脂組成物には、最終硬化膜の耐熱性、密着性、耐薬品性等の諸特性を更に向上させる目的でエポキシ樹脂硬化剤を併用することができる。 An epoxy resin curing agent can be used in combination with the liquid photocurable resin composition for the purpose of further improving various properties such as heat resistance, adhesion, and chemical resistance of the final cured film.
このようなエポキシ樹脂硬化剤の具体例としては、例えば、２−メチルイミダゾール、２−エチル−４−メチルイミダゾール、１−ベンジル−２−メチルイミダゾール、２−フェニルイミダゾール、２−フェニル−４−メチル−５−ヒドロキシメチルイミダゾール等のイミダゾール誘導体：アセトグアナミン、ベンゾグアナミン等のグアナミン類：ジアミノジフェニルメタン、ｍ−フェニレンジアミン、ｍ−キシレンジアミン、ジアミノジフェニルスルフォン、ジシアンジアミド、尿素、尿素誘導体、メラミン、多塩基ヒドラジド等のポリアミン類：これらの有機酸塩及び／又はエポキシアダクト：三フッ化ホウ素のアミン錯体：エチルジアミノ−Ｓ−トリアジン、２，４−ジアミノ−Ｓ−トリアジン、２，４−ジアミノ−６−キシリル−Ｓ−トリアジン等のトリアジン誘導体類：トリメチルアミン、トリエタノールアミン、Ｎ，Ｎ−ジメチルオクチルアミン、Ｎ−ベンジルジメチルアミン、ピリジン、Ｎ−メチルモルホリン、ヘキサ（Ｎ−メチル）メラミン、２，４，６−トリス（ジメチルアミノフェノール）、テトラメチルグアニジン、ｍ−アミノフェノール等の三級アミン類：ポリビニルフェノール、ポリビニルフェノール臭素化物、フェノールノボラック、アルキルフェノールノボラック等のポリフェノール類：トリブチルホスフィン、トリフェニルホスフィン、トリス−２−シアノエチルホスフィン等の有機ホスフィン類：トリ−ｎ−ブチル（２，５−ジヒドロキシフェニル）ホスホニウムブロマイド、ヘキサデシルトリブチルホスニウムクロライド等のホスホニウム塩類：ベンジルトリメチルアンモニウムクロライド、フェニルトリブチルアンモニウムクロライド等の４級アンモニウム塩類：前記の多塩基酸無水物：ジフェニルヨードニウムテトラフルオロボレート、トリフェニルスルホニウムヘキサフルオロアンチモネート、２，４，６−トリフェニルチオピリリウムヘキサフルオロホスフェート等が挙げられる。 Specific examples of such an epoxy resin curing agent include, for example, 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methyl. Imidazole derivatives such as -5-hydroxymethylimidazole: guanamines such as acetoguanamine and benzoguanamine: diaminodiphenylmethane, m-phenylenediamine, m-xylenediamine, diaminodiphenylsulfone, dicyandiamide, urea, urea derivatives, melamine, polybasic hydrazide, etc. Polyamines: These organic acid salts and / or epoxy adducts: Amine complexes of boron trifluoride: ethyldiamino-S-triazine, 2,4-diamino-S-triazine, 2,4-diamino-6-xylyl- S Triazine derivatives such as triazine: trimethylamine, triethanolamine, N, N-dimethyloctylamine, N-benzyldimethylamine, pyridine, N-methylmorpholine, hexa (N-methyl) melamine, 2,4,6-tris ( Tertiary amines such as dimethylaminophenol), tetramethylguanidine and m-aminophenol: polyphenols such as polyvinylphenol, polyvinylphenol bromide, phenol novolak, alkylphenol novolak: tributylphosphine, triphenylphosphine, tris-2-cyanoethyl Organic phosphines such as phosphine: phosphonium salts such as tri-n-butyl (2,5-dihydroxyphenyl) phosphonium bromide, hexadecyltributylphosnium chloride : Quaternary ammonium salts such as benzyltrimethylammonium chloride and phenyltributylammonium chloride: The above polybasic acid anhydrides: diphenyliodonium tetrafluoroborate, triphenylsulfonium hexafluoroantimonate, 2,4,6-triphenylthiopyrylium Examples include hexafluorophosphate.
エポキシ樹脂硬化剤は、単独あるいは２種類以上を組み合わせて用いられ、液状光硬化性樹脂組成物中に含まれるエポキシ樹脂硬化剤の量は、耐薬品性、耐熱性、電気絶縁性の効果が得られるという観点から、液状光硬化性樹脂組成物中、好ましくは０．０１〜２０質量％、更に好ましくは０．１〜１０質量％用いられる。 The epoxy resin curing agent is used alone or in combination of two or more, and the amount of the epoxy resin curing agent contained in the liquid photocurable resin composition is effective for chemical resistance, heat resistance and electrical insulation. In the liquid photocurable resin composition, preferably 0.01 to 20% by mass, more preferably 0.1 to 10% by mass.
本発明の液状光硬化性樹脂組成物には、密着性、塗膜硬度等の諸特性を更に向上させる目的で、必要に応じて、硫酸バリウム、チタン酸バリウム、シリカ、タルク、焼成カオリン、炭酸マグネシウム、酸化アルミニウム、水酸化アルミニウム、雲母等の公知の無機フィラーを、単独あるいは２種類以上を組み合わせて用いることができる。無機フィラーの使用量は、密着性、耐熱性、耐熱衝撃性の効果が得られるという観点から、液状光硬化性樹脂組成物中、好ましくは２〜８０質量％、更に好ましくは５〜５０質量％用いられる。 In the liquid photocurable resin composition of the present invention, barium sulfate, barium titanate, silica, talc, calcined kaolin, carbonic acid are optionally added for the purpose of further improving various properties such as adhesion and coating film hardness. Known inorganic fillers such as magnesium, aluminum oxide, aluminum hydroxide, and mica can be used alone or in combination of two or more. The amount of the inorganic filler used is preferably 2 to 80% by mass, more preferably 5 to 50% by mass in the liquid photocurable resin composition from the viewpoint that the effects of adhesion, heat resistance and thermal shock resistance can be obtained. Used.
本発明の液状光硬化性樹脂組成物には、必要に応じて、フタロシアニン・ブルー、フタロシアニン・グリーン、アイオディン・グリーン、ジアゾイエロー、クリスタルバイオレット、酸化チタン、カーボンブラック、ナフタレンブラック等の公知の着色剤、ハイドロキノン、メチルハイドロキノン、ハイドロキノンモノメチルエーテル、カテコール、ピロガロール等の重合禁止剤、ベントン、モンモリロナイト等の増粘剤、シリコーン系、フッ素系、ビニル樹脂系の消泡剤、シランカップリング剤等の公知慣用の各種添加剤を用いることができる。更に、臭素化エポキシ化合物、酸変性臭素化エポキシ化合物、アンチモン化合物、及びリン系化合物のホスフェート化合物、芳香族縮合リン酸エステル、含ハロゲン縮合リン酸エステル等の難燃剤を用いることができる。 In the liquid photocurable resin composition of the present invention, as required, known colorants such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, carbon black, naphthalene black Polymerization inhibitors such as hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, catechol and pyrogallol, thickeners such as benton and montmorillonite, silicone, fluorine and vinyl resin antifoaming agents, silane coupling agents, etc. These various additives can be used. Further, flame retardants such as brominated epoxy compounds, acid-modified brominated epoxy compounds, antimony compounds, phosphate compounds of phosphorus compounds, aromatic condensed phosphate esters, and halogen-containing condensed phosphate esters can be used.
本発明の液状光硬化性樹脂組成物には、必要に応じて、エラストマーとして、スチレン系エラストマー、オレフィン系エラストマー、ウレタン系エラストマー、ポリエステル系エラストマー、ポリアミド系エラストマー、アクリル系エラストマー、及びシリコーン系エラストマーを用いることができる。これらのエラストマーは、ハードセグメント成分とソフトセグメント成分から成り立っている。一般にハードセグメント成分が耐熱性、強度に寄与しており、ソフトセグメント成分が柔軟性、強靭性に寄与している。 If necessary, the liquid photocurable resin composition of the present invention includes, as an elastomer, a styrene elastomer, an olefin elastomer, a urethane elastomer, a polyester elastomer, a polyamide elastomer, an acrylic elastomer, and a silicone elastomer. Can be used. These elastomers are composed of a hard segment component and a soft segment component. In general, the hard segment component contributes to heat resistance and strength, and the soft segment component contributes to flexibility and toughness.
スチレン系エラストマーとしては、スチレン−ブタジエン−スチレンブロックコポリマー、スチレン−イソプレン−スチレンブロックコポリマー、スチレン−エチレン−ブチレン−スチレンブロックコポリマー、スチレン−エチレン−プロピレン−スチレンブロックコポリマーが挙げられる。スチレン系エラストマーを構成する成分であるスチレンのほかに、α−メチルスチレン、３−メチルスチレン、４−プロピルスチレン、４−シクロヘキシルスチレン等のスチレン誘導体を用いることができる。スチレン系エラストマーとして、具体的には、タフプレン、ソルプレンＴ、アサプレンＴ、タフテック（以上、旭化成工業株式会社製）、エラストマーＡＲ（アロン化成製）、クレイトンＧ、過リフレックス（以上、シェルジャパン製）、ＪＳＲ−ＴＲ、ＴＳＲ−ＳＩＳ、ダイナロン（以上、日本合成ゴム株式会社製）、デンカＳＴＲ（電気化学工業株式会社製）、クインタック（日本ゼオン製）、ＴＰＥ−ＳＢシリーズ（住友化学工業株式会社製）、ラバロン（三菱化学株式会社製）、セプトン、ハイブラー（以上、クラレ製）、スミフレックス（住友ベークライト株式会社製）、レオストマー、アクティマー（以上、理研ビニル工業製）等が挙げられる。 Examples of the styrenic elastomer include styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, styrene-ethylene-butylene-styrene block copolymer, and styrene-ethylene-propylene-styrene block copolymer. In addition to styrene, which is a component constituting the styrene-based elastomer, styrene derivatives such as α-methylstyrene, 3-methylstyrene, 4-propylstyrene, and 4-cyclohexylstyrene can be used. Specific examples of styrene-based elastomers include Tufrene, Solprene T, Asaprene T, Tuftec (above, manufactured by Asahi Kasei Kogyo Co., Ltd.), Elastomer AR (manufactured by Aron Kasei Co., Ltd.), Kraton G, and Super Reflex (above, made by Shell Japan). , JSR-TR, TSR-SIS, Dynalon (manufactured by Nippon Synthetic Rubber Co., Ltd.), Denka STR (manufactured by Denki Kagaku Kogyo Co., Ltd.), Quintac (manufactured by Nippon Zeon), TPE-SB series (Sumitomo Chemical Industries, Ltd.) Product), Lavalon (manufactured by Mitsubishi Chemical Corporation), Septon, Hibler (manufactured by Kuraray Co., Ltd.), Sumiflex (manufactured by Sumitomo Bakelite Co., Ltd.), Rheostomer, Actimer (manufactured by Riken Vinyl Industry), and the like.
オレフィン系エラストマーは、エチレン、プロピレン、１−ブテン、１−ヘキセン、４−メチル−ペンテン等の炭素数２〜２０のα−オレフィンの共重合体であり、例えば、エチレン−プロピレン共重合体（ＥＰＲ）、エチレン−プロピレン−ジエン共重合体（ＥＰＤＭ）等が挙げられ、また、ジシクロペンタジエン、１，４−ヘキサジエン、シクロオクタジエン、メチレンノルボルネン、エチリデンノルボルネン、ブタジエン、イソプレン等の炭素数２〜２０の非共役ジエンとα−オレフィン共重合体が挙げられる。また、オレフィン系エラストマーとして、ブタジエン−アクリロニトリル共重合体にメタクリル酸を共重合したカルボキシ変性ＮＢＲが挙げられる。オレフィン系エラストマーとして、具体的には、エチレン・α−オレフィン共重合体ゴム、エチレン・α−オレフィン・非共役ジエン共重合体ゴム、プロピレン・α−オレフィン共重合体ゴム、ブテン・α−オレフィン共重合体ゴム等が挙げられる。更に、オレフィン系エラストマーとして、具体的には、ミラストマ（三井石油化学製）、ＥＸＡＣＴ（エクソン化学製）、ＥＮＧＡＧＥ（ダウケミカル製）、水添スチレン−ブタジエンラバー“ＤＹＮＡＢＯＮ ＨＳＢＲ”（日本合成ゴム株式会社製）、ブタジエン−アクリロニトリル共重合体“ＮＢＲシリーズ”（日本合成ゴム株式会社製）、及び架橋点を有する両末端カルボキシル基変性ブタジエン−アクリロニトリル共重合体の“ＸＥＲシリーズ”（日本合成ゴム株式会社製）等が挙げられる。 The olefin elastomer is a copolymer of an α-olefin having 2 to 20 carbon atoms such as ethylene, propylene, 1-butene, 1-hexene, 4-methyl-pentene, for example, an ethylene-propylene copolymer (EPR). ), Ethylene-propylene-diene copolymer (EPDM), etc., and also having 2 to 20 carbon atoms such as dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methylene norbornene, ethylidene norbornene, butadiene, isoprene and the like. Non-conjugated dienes and α-olefin copolymers. Examples of the olefin elastomer include carboxy-modified NBR obtained by copolymerizing butadiene-acrylonitrile copolymer with methacrylic acid. Specific examples of olefin elastomers include ethylene / α-olefin copolymer rubber, ethylene / α-olefin / non-conjugated diene copolymer rubber, propylene / α-olefin copolymer rubber, butene / α-olefin copolymer rubber. Examples thereof include polymer rubber. Furthermore, as olefin elastomers, specifically, Miralastoma (manufactured by Mitsui Petrochemical), EXACT (manufactured by Exxon Chemical), ENGAGE (manufactured by Dow Chemical), hydrogenated styrene-butadiene rubber “DYNABON HSBR” (Nippon Synthetic Rubber Co., Ltd.) ), Butadiene-acrylonitrile copolymer “NBR series” (manufactured by Nippon Synthetic Rubber Co., Ltd.), and “XER series” of both terminal carboxyl group-modified butadiene-acrylonitrile copolymers having a crosslinking point (manufactured by Nippon Synthetic Rubber Co., Ltd.) ) And the like.
ウレタンエラストマーは、低分子のグリコールとジイソシアネートからなるハードセグメント成分と高分子（長鎖）ジオールとジイソシアネートからなるソフトセグメント成分との構造単位からなり、高分子（長鎖）ジオールとしてポリプロピレングリコール、ポリテトラメチレンオキサイド、ポリ（１，４−ブチレンアジペート）、ポリ（エチレン・１，４−ブチレンアジペート）、ポリカプロラクトン、ポリ（１，６−ヘキシレンカーボネート）、ポリ（１，６−ヘキシレン・ネオペンチレンアジペート）等が挙げられる。高分子（長鎖）ジオールの数平均分子量は、５００〜１０，０００が好ましい。エチレングリコールの他に、プロピレングリコール、１，４−ブタンジオール、ビスフェノールＡ等の短鎖ジオールを用いることができ、短鎖ジオールの数平均分子量は、４８〜５００が好ましい。ウレタンエラストマーの具体例として、ＰＡＮＤＥＸ Ｔ−２１８５、Ｔ−２９８３Ｎ（大日本インキ製）、シラクトランＥ７９０等が挙げられる。 Urethane elastomers consist of structural units of a hard segment component consisting of low-molecular glycol and diisocyanate, and a soft segment component consisting of a polymer (long-chain) diol and diisocyanate. Methylene oxide, poly (1,4-butylene adipate), poly (ethylene / 1,4-butylene adipate), polycaprolactone, poly (1,6-hexylene carbonate), poly (1,6-hexylene neopentylene) Adipate) and the like. The number average molecular weight of the polymer (long chain) diol is preferably 500 to 10,000. In addition to ethylene glycol, short chain diols such as propylene glycol, 1,4-butanediol, and bisphenol A can be used, and the number average molecular weight of the short chain diol is preferably 48 to 500. Specific examples of the urethane elastomer include PANDEX T-2185, T-2983N (manufactured by Dainippon Ink), sylactolan E790, and the like.
ポリエステル系エラストマーとしては、ジカルボン酸又はその誘導体及びジオール化合物又はその誘導体を重縮合して得られるものが挙げられる。ジカルボン酸の具体例として、テレフタル酸、イソフタル酸、ナフタレンジカルボン酸等の芳香族ジカルボン酸及びこれらの芳香核の水素原子がメチル基、エチル基、フェニル基等で置換された芳香族ジカルボン酸、アジピン酸、セバシン酸、ドデカンジカルボン酸等の炭素数２〜２０の脂肪族ジカルボン酸、及びシクロヘキサンジカルボン酸などの脂環式ジカルボン酸などが挙げられる。ポリエステル系エラストマーとして、これらの化合物を単独で又は２種以上で用いることができる。ジオール化合物の具体例としては、エチレングリコール、１，３−プロパンジオール、１，４−ブタンジオール、１，６−ヘキサンジオール、１，１０−デカンジオール、１，４−シクロヘキサンジオール等の脂肪族ジオール及び脂環式ジオール、又は、下記一般式（Ｖ）で示される二価フェノールが挙げられる。 Examples of the polyester elastomer include those obtained by polycondensation of a dicarboxylic acid or a derivative thereof and a diol compound or a derivative thereof. Specific examples of dicarboxylic acids include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid, and aromatic dicarboxylic acids in which hydrogen atoms of these aromatic nuclei are substituted with methyl groups, ethyl groups, phenyl groups, and the like. Examples thereof include aliphatic dicarboxylic acids having 2 to 20 carbon atoms such as acid, sebacic acid and dodecanedicarboxylic acid, and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid. These compounds can be used alone or in combination of two or more as the polyester elastomer. Specific examples of the diol compound include aliphatic diols such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,10-decanediol, and 1,4-cyclohexanediol. And a dihydric phenol represented by the following general formula (V).
二価フェノールの具体例として、ビスフェノールＡ、ビス−（４−ヒドロキシフェニル）メタン、ビス−（４−ヒドロキシ−３−メチルフェニル）プロパン、レゾルシン等が挙げられる。これらの化合物は単独で又は２種以上用いることができる。また、芳香族ポリエステル（例えば、ポリブチレンテレフタレート）部分をハードセグメント成分に、脂肪族ポリエステル（例えば、ポリテトラメチレングリコール）部分をソフトセグメント成分にしたマルチブロック共重合体を用いることができる。ハードセグメント成分とソフトセグメント成分の種類、比率、分子量の違いによりさまざまなグレードのものがある。具体例として、ハイトレル（デュポン−東レ株式会社製）、ペルプレン（東洋紡績株式会社製）、エスペル（日立化成工業株式会社製）等が挙げられる。 Specific examples of the dihydric phenol include bisphenol A, bis- (4-hydroxyphenyl) methane, bis- (4-hydroxy-3-methylphenyl) propane, resorcin and the like. These compounds can be used alone or in combination of two or more. In addition, a multiblock copolymer having an aromatic polyester (for example, polybutylene terephthalate) portion as a hard segment component and an aliphatic polyester (for example, polytetramethylene glycol) portion as a soft segment component can be used. There are various grades depending on the type, ratio, and molecular weight of the hard segment component and soft segment component. Specific examples include Hytrel (manufactured by DuPont-Toray Industries, Inc.), Perprene (manufactured by Toyobo Co., Ltd.), Espel (manufactured by Hitachi Chemical Co., Ltd.), and the like.
ポリアミド系エラストマーは、ハードセグメント成分にポリアミドを、ソフトセグメント成分にポリエーテルやポリエステルを用いたポリエーテルブロックアミド型とポリエーテルエステルブロックアミド型の２種類に大別される。ポリアミドとしては、ポリアミド−６、１１、１２等が用いられ、ポリエーテルとしては、ポリオキシエチレン、ポリオキシプロピレン、ポリテトラメチレングリコール等が用いられる。具体的には、ＵＢＥポリアミドエラストマ（宇部興産株式会社製）、ダイアミド（ダイセルヒュルス株式会社製）、ＰＥＢＡＸ（東レ株式会社製）、グリロンＥＬＹ（エムスジャパン株式会社製）、ノパミッド（三菱化学株式会社製）、グリラックス（大日本インキ株式会社製）等が挙げられる。 Polyamide elastomers are broadly classified into two types: polyether block amide type and polyether ester block amide type using polyamide as a hard segment component and polyether or polyester as a soft segment component. As the polyamide, polyamide-6, 11, 12 or the like is used, and as the polyether, polyoxyethylene, polyoxypropylene, polytetramethylene glycol or the like is used. Specifically, UBE polyamide elastomer (manufactured by Ube Industries Co., Ltd.), Daiamide (manufactured by Daicel Huls Co., Ltd.), PEBAX (manufactured by Toray Industries, Inc.), Grilon ELY (manufactured by MMS Japan Co., Ltd.), Nopamid (Mitsubishi Chemical Corporation) Manufactured), Glase (Dainippon Ink Co., Ltd.) and the like.
アクリル系エラストマーは、アクリル酸エステルを主成分とし、エチルアクリレート、ブチルアクリレート、メトキシエチルアクリレート、エトキシエチルアクリレート等が用いられ、また、架橋点モノマーとして、グリシジルメタクリレート、アリルグリシジルエーテル等が用いられる。更に、アクリロニトリルやエチレンを共重合することもできる。具体的には、アクリロニトリル−ブチルアクリレート共重合体、アクリロニトリル−ブチルアクリレート−エチルアクリレート共重合体、アクリロニトリル−ブチルアクリレート−グリシジルメタクリレート共重合体等が挙げられる。 The acrylic elastomer is mainly composed of an acrylic ester, and ethyl acrylate, butyl acrylate, methoxyethyl acrylate, ethoxyethyl acrylate, or the like is used, and glycidyl methacrylate, allyl glycidyl ether, or the like is used as a crosslinking point monomer. Furthermore, acrylonitrile and ethylene can be copolymerized. Specific examples include acrylonitrile-butyl acrylate copolymer, acrylonitrile-butyl acrylate-ethyl acrylate copolymer, acrylonitrile-butyl acrylate-glycidyl methacrylate copolymer, and the like.
シリコーン系エラストマーとしては、オルガノポリシロキサンを主成分としたもので、ポリジメチルシロキサン系、ポリメチルフェニルシロキサン系、ポリジフェニルシロキサン系に分けられる。一部をビニル基、アルコキシ基等で変性したものもある。具体例として、ＫＥシリーズ（信越化学工業株式会社製）、ＳＥシリーズ、ＣＹシリーズ、ＳＨシリーズ（以上、東レダウコーニングシリコーン株式会社製）等が挙げられる。 Silicone elastomers are mainly composed of organopolysiloxane, and can be classified into polydimethylsiloxane, polymethylphenylsiloxane, and polydiphenylsiloxane. Some are modified with vinyl groups, alkoxy groups, and the like. Specific examples include the KE series (manufactured by Shin-Etsu Chemical Co., Ltd.), SE series, CY series, SH series (above, manufactured by Toray Dow Corning Silicone Co., Ltd.) and the like.
また、上記の熱可塑性エラストマー以外に、ゴム変性したエポキシ樹脂を用いることができる。ゴム変性したエポキシ樹脂は、例えば、上述のビスフェノールＦ型エポキシ樹脂、ビスフェノールＡ型エポキシ樹脂、サリチルアルデヒド型エポキシ樹脂、フェノールノボラック型エポキシ樹脂あるいはクレゾールノボラック型エポキシ樹脂の一部又は全部のエポキシ基を両末端カルボン酸変性型ブタジエン−アクリロニトリルゴム、末端アミノ変性シリコーンゴム等で変性することによって得られる。これらのエラストマーの中で、せん断接着性の点で、両末端カルボキシル基変性ブタジエン−アクリロニトリル共重合体、水酸基を有するポリエステル系エラストマーであるエスペル（日立化成工業株式会社製、エスペル１６１２、１６２０）が好ましい。 In addition to the above thermoplastic elastomer, a rubber-modified epoxy resin can be used. The rubber-modified epoxy resin includes, for example, a part or all of the epoxy groups of the bisphenol F type epoxy resin, bisphenol A type epoxy resin, salicylaldehyde type epoxy resin, phenol novolac type epoxy resin or cresol novolac type epoxy resin. It is obtained by modifying with a terminal carboxylic acid-modified butadiene-acrylonitrile rubber, a terminal amino-modified silicone rubber or the like. Among these elastomers, both ends carboxyl group-modified butadiene-acrylonitrile copolymer and Espel (Espel 1612, 1620, manufactured by Hitachi Chemical Co., Ltd.) which is a polyester-based elastomer having a hydroxyl group are preferable in terms of shear adhesiveness. .
エラストマーの配合量は、酸変性ビニル基含有エポキシ樹脂（Ａ）１００質量部に対して、好ましくは２〜３０質量部、更に好ましくは４〜２０質量部用いられる。２〜３０質量部では、硬化膜の高温領域での弾性率が低くなる傾向があり、未露光部が現像液で溶出する傾向があるので好ましい。 The compounding amount of the elastomer is preferably 2 to 30 parts by mass, more preferably 4 to 20 parts by mass with respect to 100 parts by mass of the acid-modified vinyl group-containing epoxy resin (A). The amount of 2 to 30 parts by mass is preferable because the elastic modulus in the high temperature region of the cured film tends to be low and the unexposed part tends to be eluted with the developer.
液状光硬化性樹脂組成物は、配合成分をロールミル、ビーズミル等で均一に混練、混合することにより得ることができる。 The liquid photocurable resin composition can be obtained by uniformly kneading and mixing the blending components with a roll mill, a bead mill or the like.
以下、本発明の合成例及び実施例により更に具体的に説明するが、本発明はこれに限定されるものではない。なお、合成例中、実施例中の部、及び表中の配合量は質量部を示す。 Hereinafter, although the synthesis example and Example of this invention demonstrate further more concretely, this invention is not limited to this. In addition, the part in an Example and the compounding quantity in a table | surface in a synthesis example show a mass part.
［合成例１］
ＹＤＣＮ７０４（東都化成株式会社製、クレゾールノボラック型エポキシ樹脂、一般式（I）において、Ｘ＝グリシジル基、Ｒ＝メチル基）２２０質量部、アクリル酸７２質量部、ハイドロキノン１．０質量部、カルビトールアセテート１８０質量部を仕込み、９０℃に加熱、撹拌して反応混合物を溶解した。次に、６０℃に冷却し、塩化ベンジルトリメチルアンモニウム１質量部を仕込み、１００℃に加熱して、固形分酸価が１ｍｇＫＯＨ／ｇになるまで反応させた。次に、テトラヒドロ無水フタル酸１５２質量部とカルビトールアセテート１００質量部を仕込み、８０℃に加熱し、約６時間反応し冷却し、固形分濃度が６０質量％になるようにカルビトールアセテートで希釈して酸変性ビニル基含有エポキシ樹脂（I）を得た。軟化点は６０℃である。なお、樹脂の軟化点は、ＪＩＳ−Ｋ７２３４（１９８６年制定）に定める環球法に準拠して測定した。昇温速度は、５℃／分で行った。
[Synthesis Example 1]
YDCN704 (manufactured by Toto Kasei Co., Ltd., cresol novolac type epoxy resin, in general formula (I), X = glycidyl group, R = methyl group) 220 parts by mass, acrylic acid 72 parts by mass, hydroquinone 1.0 part by mass, carbitol 180 parts by mass of acetate was charged and heated to 90 ° C. and stirred to dissolve the reaction mixture. Next, the mixture was cooled to 60 ° C., charged with 1 part by mass of benzyltrimethylammonium chloride, heated to 100 ° C., and reacted until the solid content acid value reached 1 mgKOH / g. Next, 152 parts by mass of tetrahydrophthalic anhydride and 100 parts by mass of carbitol acetate were added, heated to 80 ° C., reacted for about 6 hours, cooled, and diluted with carbitol acetate to a solid content concentration of 60% by mass. Thus, an acid-modified vinyl group-containing epoxy resin (I) was obtained. The softening point is 60 ° C. The softening point of the resin was measured according to the ring and ball method defined in JIS-K7234 (established in 1986). The heating rate was 5 ° C./min.
［合成例２］
ＥＰＰＮ５０２Ｈ（日本化薬株式会社製、サリチルアルデヒド型エポキシ樹脂、一般式（III）において、Ｘ＝グリシジル基）３３０質量部に、アクリル酸１４４質量部、ハイドロキノン１．５質量部、カルビトールアセテート２５０質量部を仕込み、９０℃に加熱、撹拌して反応混合物を溶解した。次に、６０℃に冷却し、塩化ベンジルトリメチルアンモニウム２質量部を仕込み、１００℃に加熱して、酸価が１ｍｇＫＯＨ／ｇになるまで反応させた。次に、テトラヒドロ無水フタル酸２３０質量部とカルビトールアセテート１８０質量部を仕込み、８０℃に加熱し、約６時間反応し冷却し、固形分濃度が６０質量％になるようにカルビトールアセテートで希釈して酸変性ビニル基含有エポキシ樹脂（II）を得た。軟化点は６８℃である。なお、樹脂の軟化点は、ＪＩＳ−Ｋ７２３４（１９８６年制定）に定める環球法に準拠して測定した。昇温速度は、５℃／分で行った。
[Synthesis Example 2]
EPPN502H (manufactured by Nippon Kayaku Co., Ltd., salicylaldehyde type epoxy resin, in general formula (III), X = glycidyl group) 330 parts by mass, 144 parts by mass of acrylic acid, 1.5 parts by mass of hydroquinone, 250 parts by mass of carbitol acetate The reaction mixture was dissolved by heating and stirring to 90 ° C. Next, the mixture was cooled to 60 ° C., charged with 2 parts by mass of benzyltrimethylammonium chloride, heated to 100 ° C., and reacted until the acid value reached 1 mgKOH / g. Next, 230 parts by mass of tetrahydrophthalic anhydride and 180 parts by mass of carbitol acetate were added, heated to 80 ° C., reacted for about 6 hours, cooled, and diluted with carbitol acetate to a solid content concentration of 60% by mass. Thus, an acid-modified vinyl group-containing epoxy resin (II) was obtained. The softening point is 68 ° C. The softening point of the resin was measured according to the ring and ball method defined in JIS-K7234 (established in 1986). The heating rate was 5 ° C./min.
［合成例３］
ＹＤＦ２００１（東都化成株式会社製、ビスフェノールＦ型エポキシ樹脂、一般式（II）において、Ｘ＝グリシジル基、Ｒ＝Ｈ）４７５質量部、アクリル酸７２質量部、ハイドロキノン０．５質量部、カルビトールアセテート１２０質量部を仕込み、９０℃に加熱、撹拌して反応混合物を溶解した。次に、６０℃に冷却し、塩化ベンジルトリメチルアンモニウム２質量部を仕込み、１００℃に加熱して、酸価が１ｍｇＫＯＨ／ｇになるまで反応させた。次に、テトラヒドロ無水フタル酸２３０質量部とカルビトールアセテート８５質量部を仕込み、８０℃に加熱し、約６時間反応し冷却し、固形分濃度が６０質量％になるようにカルビトールアセテートで希釈して酸変性ビニル基含有エポキシ樹脂（III）を得た。軟化点は５４℃である。なお、樹脂の軟化点は、ＪＩＳ−Ｋ７２３４（１９８６年制定）に定める環球法に準拠して測定した。昇温速度は、５℃／分で行った。
[Synthesis Example 3]
YDF2001 (manufactured by Toto Kasei Co., Ltd., bisphenol F type epoxy resin, in general formula (II), X = glycidyl group, R = H) 475 parts by mass, acrylic acid 72 parts by mass, hydroquinone 0.5 parts by mass, carbitol acetate 120 parts by mass were charged and heated to 90 ° C. and stirred to dissolve the reaction mixture. Next, the mixture was cooled to 60 ° C., charged with 2 parts by mass of benzyltrimethylammonium chloride, heated to 100 ° C., and reacted until the acid value reached 1 mgKOH / g. Next, 230 parts by mass of tetrahydrophthalic anhydride and 85 parts by mass of carbitol acetate are added, heated to 80 ° C., reacted for about 6 hours, cooled, and diluted with carbitol acetate to a solid content concentration of 60% by mass. Thus, an acid-modified vinyl group-containing epoxy resin (III) was obtained. The softening point is 54 ° C. The softening point of the resin was measured according to the ring and ball method defined in JIS-K7234 (established in 1986). The heating rate was 5 ° C./min.
［評価方法］
評価方法は以下のとおりである。
[Evaluation method]
The evaluation method is as follows.
＜平坦性＞
表面粗さ計（小坂研究所製、サーフコーダＳＥ−３４００）を用いて、プリント配線板の配線パターンを横切るように走査して塗布後の液状光硬化性樹脂組成物の表面粗さ（厚みの凹凸度）を計測した。
測定は、以下の測定条件で行った。
走査速度：０．５ｍｍ／ｓ
圧子の材質：ダイヤモンド
圧子の先端部の形状：円錐 頂角９０度
圧子の先端半径：Ｒ２μｍ
測定力：０．７ｍＮ
カットオフ値：０．８ｍｍ
測定長さ：１０ｍｍ
<Flatness>
Using a surface roughness meter (Surfcoder SE-3400, manufactured by Kosaka Laboratories), the surface roughness (thickness of the liquid photocurable resin composition after application by scanning across the wiring pattern of the printed wiring board was scanned. The degree of unevenness was measured.
The measurement was performed under the following measurement conditions.
Scanning speed: 0.5mm / s
Indenter material: Diamond Shape of tip of indenter: cone 90 ° apex radius Radius of indenter: R2μm
Measuring force: 0.7mN
Cut-off value: 0.8mm
Measurement length: 10mm
＜光感度＞
８０℃で乾燥後、塗膜にステップタブレット２１段（ストファー社製）を密着させ積算露光量５００ｍＪ／ｃｍ２の紫外線を照射し、１質量％の炭酸ナトリウム水溶液で６０秒間現像、その後、現像されずに残った塗膜の段数を確認した。
○：８段以上
△：５〜７段
×：４段以下
<Light sensitivity>
After drying at 80 ° C., 21 steps of Step Tablet (made by Stoffer) were adhered to the coating film, irradiated with ultraviolet rays with an integrated exposure amount of 500 mJ / cm 2 , developed with a 1% by weight aqueous sodium carbonate solution for 60 seconds, and then developed. The number of remaining coating films was confirmed.
○: 8 steps or more △: 5 to 7 steps ×: 4 steps or less
＜密着性＞
ＪＩＳ Ｋ５６００−５−６（１９９９年制定）に準じて、試験片に１ｍｍの格子を２５個作製してセロハンテープにより剥離試験を行った。
格子の剥離状態を観察し、以下の基準で評価した。
○：２２／２５以上で剥離なし
△：１２／２５以上〜２２／２５未満で剥離なし
×：０／２５〜１２／２５未満で剥離なし
<Adhesion>
In accordance with JIS K5600-5-6 (established in 1999), 25 1 mm grids were prepared on the test piece, and a peel test was performed using a cellophane tape.
The state of peeling of the lattice was observed and evaluated according to the following criteria.
○: No peeling at 22/25 or more Δ: No peeling at 12/25 or more to less than 22/25 ×: No peeling at less than 0/25 to 12/25
＜耐溶剤性＞
試験片をイソプロピルアルコールに室温で３０分間浸漬し、外観に異常がないかを目視で確認後、セロハンテープにより剥離試験を行った。
○：塗膜外観に異常がなく、剥離のないもの
×：塗膜外観に異常がある、又は剥離があるもの
<Solvent resistance>
The test piece was immersed in isopropyl alcohol at room temperature for 30 minutes, and after visually confirming that there was no abnormality in the appearance, a peel test was performed using a cellophane tape.
○: No abnormality in the appearance of the coating film and no peeling ×: No abnormality in the appearance of the coating film or peeling
＜耐酸性＞
試験片を１０質量％塩酸水溶液に室温で３０分間浸漬し、外観に異常がないかを目視で確認後、セロハンテープにより剥離試験を行った。
○：塗膜外観に異常がなく、剥離のないもの
×：塗膜外観に異常がある、又は剥離があるもの
<Acid resistance>
The test piece was immersed in a 10% by mass aqueous hydrochloric acid solution at room temperature for 30 minutes, and after visually confirming that there was no abnormality in the appearance, a peel test was performed using a cellophane tape.
○: No abnormality in the appearance of the coating film and no peeling ×: No abnormality in the appearance of the coating film or peeling
＜耐アルカリ性＞
試験片を５質量％水酸化ナトリウム水溶液に室温で３０分間浸漬し、外観に異常がないかを目視で確認後、セロハンテープにより剥離試験を行った。
○：塗膜外観に異常がなく、剥離のないもの
×：塗膜外観に異常がある、又は剥離があるもの
<Alkali resistance>
The test piece was immersed in a 5% by mass aqueous sodium hydroxide solution at room temperature for 30 minutes, and after visually confirming that there was no abnormality in appearance, a peel test was performed using a cellophane tape.
○: No abnormality in the appearance of the coating film and no peeling ×: No abnormality in the appearance of the coating film or peeling
＜はんだ耐熱性＞
試験片にロジン系フラックス及び水溶性フラックスを塗布し、２６０℃のはんだ槽に１０秒間浸漬した。これを１サイクルとして、６サイクル繰り返した後、塗膜外観を目視観察した。
○：塗膜外観に異常（剥離、フクレ）がなく、はんだのもぐりがないもの
×：塗膜外観に異常（剥離、フクレ）がある、又ははんだのもぐりがあるもの
<Solder heat resistance>
A rosin-based flux and a water-soluble flux were applied to the test piece and immersed in a solder bath at 260 ° C. for 10 seconds. This was defined as one cycle, and after repeating 6 cycles, the appearance of the coating film was visually observed.
○: No abnormal appearance (peeling or blistering) in the coating film appearance and no solder peeling ×: Abnormality (peeling or blistering) in the coating film appearance or solder peeling
＜せん断接着性＞
試験片に直径３．６ｍｍ、高さ４ｍｍの円錐形状に封止材（ＣＥＬ９２００日立化成工業株式会社製）をモールドして、吸湿後の接着性を評価した。使用機器は、ボンドテスタ（ＤＡＧＥ社製）、圧子の形状が円錐、頂角９０度、測定温度２４５℃である。
<Shear adhesiveness>
A sealing material (CEL9200 manufactured by Hitachi Chemical Co., Ltd.) was molded into a conical shape having a diameter of 3.6 mm and a height of 4 mm on the test piece, and the adhesiveness after moisture absorption was evaluated. The equipment used is a bond tester (manufactured by DAGE), the shape of the indenter is a cone, the apex angle is 90 degrees, and the measurement temperature is 245 ° C.
＜耐熱衝撃性＞
試験片を、−５５℃／３０分、１２５℃／３０分を１サイクルとして熱履歴を加え、１，０００サイクル経過後、試験片を目視観察、顕微鏡観察（倍率５０倍）した。
○：クラック発生なし
×：クラック発生あり
<Heat shock resistance>
The test piece was subjected to thermal history with -55 ° C / 30 minutes and 125 ° C / 30 minutes as one cycle, and after 1,000 cycles, the test piece was visually observed and observed with a microscope (50 times magnification).
○: No crack occurred ×: Crack occurred
＜ガラス転移点温度＞
組成物をガラス板に塗布し、８０℃に設定した熱風循環式乾燥機で３０分間乾燥させた。乾燥させた試験片を約１０ｍｇ削り取って、示差走査熱量測定（セイコーII製）を用いて−３０℃から１５０℃まで昇温速度１０℃／分で昇温させてガラス転移点温度を測定した。
<Glass transition temperature>
The composition was applied to a glass plate and dried for 30 minutes with a hot air circulation dryer set at 80 ° C. About 10 mg of the dried test piece was scraped off, and the glass transition temperature was measured by increasing the temperature from -30 ° C. to 150 ° C. at a rate of temperature increase of 10 ° C./min using differential scanning calorimetry (manufactured by Seiko II).
［実施例１〜６、比較例１〜３］
表１に示す配合組成に従って組成物を配合し、３本ロールミルで混練し液状光硬化性樹脂組成物を調製した。比較例１は実施例１の液状光硬化性樹脂組成物を使用し、比較例２は実施例２の液状光硬化性樹脂組成物を使用し、比較例３は実施例３の液状光硬化性樹脂組成物を使用した。これをスクリーン印刷法により、１２０メッシュのテトロンスクリーンを用いて、約３０μｍの厚さ（乾燥後）になるように所定の配線パターンが形成されたプリント配線が形成された基板に塗布し、８０℃に設定した熱風循環式乾燥機で３０分間乾燥させた。次に、ゴムロール機、すなわち具体的には常圧ラミネータ（大成ラミネータ株式会社製、ＶＡ−７０００）を用いて、ポリエチレンテレフタレートフィルムを乾燥させた組成物に貼り付ける際に所定条件で加圧作業を行った。次に、所定のパターンを有するネガマスクを塗膜に密着させ紫外線露光装置を用いて、５００ｍＪ／ｃｍ２露光した。露光後、ポリエチレンテレフタレートフィルムを剥がして、１質量％の炭酸ナトリウム水溶液で６０秒間、０．１８ＭＰａの圧力でスプレー現像し、未露光部を溶解現像した。得られた像を用いて現像性、光感度を評価し、次に１５０℃で１時間加熱し試験板を作製した。
試験板について、平坦性、光感度、耐酸性、耐アルカリ性、耐溶剤性、密着性、耐溶剤性、はんだ耐熱性、せん断接着性、耐熱衝撃性、ガラス転移点温度の評価を行った。表１に光感度、耐酸性、耐アルカリ性、耐溶剤性、密着性、耐溶剤性、はんだ耐熱性、せん断接着性、耐熱衝撃性、ガラス転移点温度の評価結果を示す。平坦性については、実施例１〜６のそれぞれでゴムロール温度及び圧力の条件を変えて評価を行ったので、実施例１〜６のそれぞれの評価結果を表２〜７に示す。
また、平坦性については、比較例１〜３のそれぞれでゴムロール温度及び圧力の条件を変えて評価を行ったので、比較例１〜３のそれぞれの評価結果を表２〜４に示す。
[Examples 1-6, Comparative Examples 1-3]
A composition was blended according to the blending composition shown in Table 1, and kneaded with a three-roll mill to prepare a liquid photocurable resin composition. Comparative Example 1 uses the liquid photocurable resin composition of Example 1, Comparative Example 2 uses the liquid photocurable resin composition of Example 2, and Comparative Example 3 uses the liquid photocurable resin of Example 3. A resin composition was used. This is applied by screen printing to a substrate on which printed wiring on which a predetermined wiring pattern is formed so as to have a thickness of about 30 μm (after drying) using a 120 mesh Tetron screen, It was made to dry for 30 minutes with the hot-air circulation type dryer set to (1). Next, using a rubber roll machine, that is, an atmospheric laminator (VA-7000, manufactured by Taisei Laminator Co., Ltd.), when a polyethylene terephthalate film is attached to a dried composition, a pressure operation is performed under predetermined conditions. went. Next, a negative mask having a predetermined pattern was brought into close contact with the coating film and exposed to 500 mJ / cm 2 using an ultraviolet exposure device. After the exposure, the polyethylene terephthalate film was peeled off, spray-developed with a 1% by mass aqueous sodium carbonate solution for 60 seconds at a pressure of 0.18 MPa, and the unexposed area was dissolved and developed. The developability and photosensitivity were evaluated using the obtained image, and then heated at 150 ° C. for 1 hour to prepare a test plate.
The test plate was evaluated for flatness, photosensitivity, acid resistance, alkali resistance, solvent resistance, adhesion, solvent resistance, solder heat resistance, shear adhesion, thermal shock resistance, and glass transition temperature. Table 1 shows the evaluation results of photosensitivity, acid resistance, alkali resistance, solvent resistance, adhesion, solvent resistance, solder heat resistance, shear adhesion, thermal shock resistance, and glass transition temperature. Since the flatness was evaluated by changing the conditions of the rubber roll temperature and pressure in each of Examples 1 to 6, Tables 2 to 7 show the evaluation results of Examples 1 to 6, respectively.
Moreover, since it evaluated by changing the conditions of rubber-roll temperature and pressure in each of Comparative Examples 1-3 about flatness, each evaluation result of Comparative Examples 1-3 is shown to Tables 2-4.
＊２ ＳＰ１６２０：飽和ポリエステル樹脂（日立化成製）
＊３ ＸＥＲ−９１：両末端カルボキシ基変性ブタジエンーアクニロニトリル共重合体(日本合成ゴム製)
＊４ エピコート８２８：ビスフェノールＡ型エポキシ樹脂（油化シェルエポキシ製）
＊５ カヤラッドＤＰＨＡ：ジペンタエリスリトールペンタアクリレート（日本化薬製）
＊６ イルガキュア９０７：２‐メチル‐〔４‐（メチルチオ）フェニル〕モルホリノ‐１‐プロパン（チバ・ガイギー製）
＊７ カヤキュアＤＥＴＸ‐Ｓ：２，４−ジエチルチオキサントン（日本化薬製）
* 2 SP1620: Saturated polyester resin (manufactured by Hitachi Chemical)
* 3 XER-91: Carboxyl group-modified butadiene-acrylonitrile copolymer (made by Nippon Synthetic Rubber)
* 4 Epicoat 828: Bisphenol A type epoxy resin (Oilized shell epoxy)
* 5 Kayalad DPHA: Dipentaerythritol pentaacrylate (Nippon Kayaku)
* 6 Irgacure 907: 2-methyl- [4- (methylthio) phenyl] morpholino-1-propane (Ciba Geigy)
* 7 Kayacure DETX-S: 2,4-diethylthioxanthone (manufactured by Nippon Kayaku)
［比較例４〜６］
表８に示す配合組成に従って組成物を配合し、３本ロールミルで混練し液状光硬化性樹脂組成物を調製した。これをスクリーン印刷法により、１２０メッシュのテトロンスクリーンを用いて、約３０μｍの厚さ（乾燥後）になるように所定の配線パターンが形成された銅張り積層板に塗布し、８０℃に設定した熱風循環式乾燥機で３０分間乾燥させた。次に、所定のパターンを有するネガマスクを塗膜に密着させ紫外線露光装置を用いて、５００ｍＪ／ｃｍ２露光した。露光後、ポリエチレンテレフタレートフィルムを剥がして、１質量％の炭酸ナトリウム水溶液で６０秒間、１．８ｋｇｆ／ｃｍ２の圧力でスプレー現像し、未露光部を溶解現像した。得られた像を用いて現像性、光感度を評価し、次に１５０℃で１時間加熱し試験板を作製した。
試験板について、平坦性、光感度、耐酸性、耐アルカリ性、耐溶剤性、密着性、耐溶剤性、はんだ耐熱性、せん断接着性、耐熱衝撃性、ガラス転移温度の評価を行った。表８に光感度、耐酸性、耐アルカリ性、耐溶剤性、密着性、耐溶剤性、はんだ耐熱性、せん断接着性、耐熱衝撃性、ガラス転移温度の評価結果を示す。平坦性については、比較例４〜６のそれぞれの評価結果を表９に示す。
[Comparative Examples 4 to 6]
A composition was blended according to the blending composition shown in Table 8, and kneaded with a three-roll mill to prepare a liquid photocurable resin composition. This was applied by screen printing to a copper-clad laminate on which a predetermined wiring pattern was formed to a thickness of about 30 μm (after drying) using a 120 mesh Tetron screen and set to 80 ° C. It dried for 30 minutes with the hot air circulation type dryer. Next, a negative mask having a predetermined pattern was brought into close contact with the coating film and exposed to 500 mJ / cm 2 using an ultraviolet exposure device. After exposure, the polyethylene terephthalate film was peeled off and spray-developed with a 1% by mass aqueous sodium carbonate solution for 60 seconds at a pressure of 1.8 kgf / cm 2 to dissolve and develop the unexposed area. The developability and photosensitivity were evaluated using the obtained image, and then heated at 150 ° C. for 1 hour to prepare a test plate.
The test plate was evaluated for flatness, photosensitivity, acid resistance, alkali resistance, solvent resistance, adhesion, solvent resistance, solder heat resistance, shear adhesion, thermal shock resistance, and glass transition temperature. Table 8 shows the evaluation results of photosensitivity, acid resistance, alkali resistance, solvent resistance, adhesion, solvent resistance, solder heat resistance, shear adhesion, thermal shock resistance, and glass transition temperature. About flatness, each evaluation result of Comparative Examples 4-6 is shown in Table 9.
［評価結果］
表１及び表８から、実施例１〜６、比較例４〜６のいずれも光感度、耐酸性、耐アルカリ性、耐溶剤性、密着性、耐溶剤性、はんだ耐熱性、せん断接着性、耐熱衝撃性、ガラス転移点温度が好適であることが判った。
表２〜７から、実施例１〜６の平坦性については、ゴムロール温度及び圧力の条件を変えても凹凸度が最大でも３．９μｍであり、所望の値である４μｍ以下であった。
表２〜４から、比較例１〜３の平坦性については、ゴムロールの温度が２０度である場合では凹凸度が最大で４．４μｍであり、所望の値である４μｍを超えてしまった。また、ゴムロールの温度が２０度である場合（比較例１−１、２−１、３−１）では空気の巻き込みが発生し、ゴムロールの温度が９０度である場合（比較例１−２、２−２、３−２）では一部に現像残りが発生した。
表９から、比較例４〜６の平坦性については、ゴムロール機（ラミネータ）を使用しなかったので、実施例１〜６で行ったゴムロール温度及び圧力の条件を変えて評価することはできなかった。比較例４〜６の平坦性は、凹凸度が最小でも７．４μｍであり、所望の値である４μｍを超えてしまった。
[Evaluation results]
From Tables 1 and 8, Examples 1-6 and Comparative Examples 4-6 all have photosensitivity, acid resistance, alkali resistance, solvent resistance, adhesion, solvent resistance, solder heat resistance, shear adhesion, heat resistance. It was found that impact properties and glass transition temperature were suitable.
From Tables 2-7, about the flatness of Examples 1-6, even if it changed the conditions of rubber roll temperature and pressure, the unevenness | corrugation degree was 3.9 micrometers at maximum, and it was 4 micrometers or less which is a desired value.
From Tables 2-4, about the flatness of Comparative Examples 1-3, when the temperature of a rubber roll is 20 degree | times, the unevenness | corrugation degree was 4.4 micrometers at maximum, and exceeded 4 micrometers which is a desired value. When the temperature of the rubber roll is 20 degrees (Comparative Examples 1-1, 2-1, 3-1), air entrainment occurs, and when the temperature of the rubber roll is 90 degrees (Comparative Examples 1-2, In 2-2 and 3-2), a development residue occurred in part.
From Table 9, about the flatness of Comparative Examples 4-6, since the rubber roll machine (laminator) was not used, it was not possible to evaluate by changing the rubber roll temperature and pressure conditions performed in Examples 1-6. It was. The flatness of Comparative Examples 4 to 6 was 7.4 μm even when the degree of unevenness was a minimum, and exceeded the desired value of 4 μm.
Claims (7)
前記液状光硬化性樹脂組成物をプリント配線が形成された前記基板上に塗布して乾燥し、塗膜を形成する工程と、
前記塗膜上に透明フィルムを配置し、前記液状光硬化性樹脂組成物のガラス転移温度より２０℃〜５０℃高い温度にて、ゴムロール機を用いて０．００５〜１．０ＭＰａで、前記透明フィルムと前記塗膜とを加熱圧着する工程
とを含み、前記透明フィルムを剥がして現像した後の前記塗膜の表面粗さ（凹凸度）を４μｍ以下とする液状光硬化性樹脂組成物の塗膜を基板上で平坦化する方法。 A coating film of a liquid photocurable resin composition containing a resin (A) having a softening point of 30 ° C to 100 ° C, a photopolymerization initiator (B), a diluent (C), and a curing agent (D). In a method of planarizing on a substrate,
Applying the liquid photocurable resin composition onto the substrate on which the printed wiring is formed and drying to form a coating film; and
A transparent film is disposed on the coating film, and is 0.005-1.0 MPa using a rubber roll machine at a temperature 20 ° C. to 50 ° C. higher than the glass transition temperature of the liquid photocurable resin composition. Applying a liquid photocurable resin composition having a surface roughness (degree of unevenness) of 4 μm or less after the transparent film is peeled off and developed. A method of planarizing a film on a substrate.
〔式（I）中、Ｒ１１は水素原子又はメチル基を示し、Ｙ１は水素原子又はグリシジル基を示し、ｎ１は１以上の整数を示す。少なくとも一つのＹ１はグリシジル基を示し、複数存在するＲ１１及びＹ１はそれぞれ同一でも異なっていてもよい。〕
〔式（II）中、Ｒ１２は水素原子又はメチル基を示し、Ｙ２は水素原子又はグリシジル基を示し、ｎ２は１以上の整数を示す。複数存在するＲ１２は同一でも異なっていてもよい。〕
〔式（III）中、Ｙ３は水素原子又はグリシジル基を示し、ｎ３は１以上の整数を示す。複数存在するＹ３は同一でも異なっていてもよい。〕 The resin (A) is a novolak type epoxy resin represented by the general formula (I), a bisphenol A type epoxy resin or a bisphenol F type epoxy resin represented by the general formula (II), and a salicyl represented by the general formula (III). The first reaction product (A1) obtained by reacting at least one epoxy resin (a) selected from the group consisting of aldehyde type epoxy resins and a vinyl group-containing monocarboxylic acid (b). A method for flattening a coating film of the liquid photocurable resin composition according to 1 or 2 on a substrate.
[In Formula (I), R 11 represents a hydrogen atom or a methyl group, Y 1 represents a hydrogen atom or a glycidyl group, and n 1 represents an integer of 1 or more. At least one Y 1 represents a glycidyl group, and a plurality of R 11 and Y 1 may be the same or different. ]
Wherein (II), R 12 represents a hydrogen atom or a methyl group, Y 2 is a hydrogen atom or a glycidyl group, n2 represents an integer of 1 or greater. A plurality of R 12 may be the same or different. ]
Wherein (III), Y 3 represents a hydrogen atom or a glycidyl group, n3 is an integer of 1 or more. A plurality of Y 3 may be the same or different. ]
露光された前記塗膜から前記透明フィルムを剥がす工程と、
露光された前記塗膜を現像してマスクレジストを形成する工程
とを含むプリント配線板の製造方法。 With respect to the flattened coating film obtained by the method of flattening the coating film of the liquid photocurable resin composition according to any one of claims 1 to 6 through the transparent film Exposing to a desired pattern;
Removing the transparent film from the exposed coating film;
And developing the exposed coating film to form a mask resist.
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