JP2012175053A - Novel white cover lay film - Google Patents

Novel white cover lay film Download PDF

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JP2012175053A
JP2012175053A JP2011038454A JP2011038454A JP2012175053A JP 2012175053 A JP2012175053 A JP 2012175053A JP 2011038454 A JP2011038454 A JP 2011038454A JP 2011038454 A JP2011038454 A JP 2011038454A JP 2012175053 A JP2012175053 A JP 2012175053A
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white
thermosetting resin
film
resin composition
coverlay film
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Masayoshi Shimizu
雅義 清水
Akio Matsutani
晃男 松谷
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Kaneka Corp
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Kaneka Corp
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Abstract

PROBLEM TO BE SOLVED: To provide a cover lay film with a white resin layer, which has at least one kind or more of advantages, such as no process contamination, high flexibility, high whiteness, high reflectance, excellent flame retardancy, no bleeding-out during hot pressing, and reduced reflectance-hue change after irradiation with light, and to provide a printed wiring board.SOLUTION: There is provided a white cover lay film comprising at least a white thermosetting resin composition layer and a polyimide film, the white thermosetting resin composition layer containing (A) a thermosetting resin substantially containing no silicon in a molecule, (B) a white coloring agent and (C) a filler-type flame retardant.

Description

この発明は、白色カバーレイフィルム、プリント配線板およびそれらを用いた発光装置等に関するものである。   The present invention relates to a white coverlay film, a printed wiring board, a light emitting device using them, and the like.

近年、電子機器の高性能化、高機能化、小型化が急速に進んでおり、これに伴って電子機器に用いられる電子部品に対しても小型化、軽量化の要請が高まっている。上記要請を受け、フレキシブルプリント配線板は、可撓性を有し、繰り返しの屈曲に耐えるため、狭い空間に立体的高密度の実装が可能であり、電子機器への配線、ケーブル、あるいはコネクター機能を付与した複合部品としてのその用途が拡大している。   2. Description of the Related Art In recent years, electronic devices have been rapidly improved in performance, function, and size, and accordingly, there is an increasing demand for downsizing and weight reduction of electronic components used in electronic devices. In response to the above requirements, the flexible printed wiring board is flexible and can withstand repeated bending, so it can be mounted in three-dimensional high density in a narrow space, and functions as a wiring, cable, or connector for electronic devices. Its use as a composite part with the

このような状況の中、ポリイミド樹脂は、耐熱性、電気絶縁信頼性や耐薬品性、機械特性に優れることから電子機器に用いられる電子部品に広く使用されている。例えば、半導体デバイス上への絶縁フィルム、フレキシブル回路基板や集積回路等の基材材料や表面保護材料に用いられている。   Under such circumstances, polyimide resins are widely used in electronic parts used in electronic devices because of their excellent heat resistance, electrical insulation reliability, chemical resistance, and mechanical properties. For example, it is used for base materials and surface protection materials such as insulating films on semiconductor devices, flexible circuit boards and integrated circuits.

特に、フレキシブル回路基板用の表面保護材料として用いる場合には、その使用上の簡便さや、丈夫さからポリイミドフィルム等の成形体に接着剤を塗布して得られるカバーレイフィルムが広く用いられている。   In particular, when used as a surface protection material for flexible circuit boards, coverlay films obtained by applying an adhesive to a molded body such as a polyimide film are widely used because of its ease of use and durability. .

一方、回路基板用の表面保護材料としては、ソルダーレジストなどが用いられる場合もある。この表面保護用ソルダーレジストとしては、エポキシ樹脂等を主体とした樹脂組成物が用いられるが、このソルダーレジストは、絶縁材料としては電気絶縁信頼性に優れるが、屈曲性等の機械特性が悪く、硬化収縮が大きいためフレキシブル回路基板などの薄くて柔軟性に富む回路基板に積層した場合、基板の反りが大きくなり、フレキシブル回路基板用に用いるのは難しいという問題がある。また、難燃性にも乏しく、難燃性を付与する目的で難燃剤を添加した場合に、物性低下や硬化膜から難燃剤がしみ出すブリードアウトによる接点障害や工程汚染も問題になっている。   On the other hand, a solder resist or the like may be used as a surface protective material for a circuit board. As this surface protective solder resist, a resin composition mainly composed of an epoxy resin or the like is used, but this solder resist is excellent in electrical insulation reliability as an insulating material, but has poor mechanical properties such as flexibility, Since the curing shrinkage is large, when it is laminated on a thin and flexible circuit board such as a flexible circuit board, there is a problem that the warpage of the board becomes large and it is difficult to use for a flexible circuit board. In addition, it has poor flame retardancy, and when a flame retardant is added for the purpose of imparting flame retardancy, contact failure and process contamination due to bleed out that the flame retardant exudes from the cured film is a problem .

ところで、近年、発光ダイオード(LED)は低消費電力、長寿命、小型化・薄膜化・軽量化が可能な点で携帯機器、パソコン、テレビ等の液晶ディスプレイのバックライト、照明装置への応用が実用化されており、LEDチップを実装するプリント配線板は、LEDチップからの光を効率的に活用するために、プリント配線板の絶縁保護膜であるカバーレイフィルムにも白色性、高反射性が求められている。   By the way, in recent years, light emitting diodes (LEDs) can be applied to backlights and lighting devices of liquid crystal displays such as portable devices, personal computers, and televisions in that they can have low power consumption, long life, miniaturization, thinning, and weight reduction. The printed wiring board on which the LED chip is mounted has whiteness and high reflectivity in the coverlay film, which is an insulating protective film of the printed wiring board, in order to efficiently use the light from the LED chip. Is required.

このような白色性、高反射性の回路基板用表面保護材料として、コーティング性、はんだ耐熱性、密着性、電気絶縁性などの特性を有し、経時による反射率の低下および劣化による着色を抑えた高反射率のソルダーレジスト組成物が提案されている(例えば、特許文献1参照。)。   As such a white and highly reflective surface protection material for circuit boards, it has coating properties, solder heat resistance, adhesion, electrical insulation, etc., and suppresses coloration due to deterioration and deterioration of reflectance over time. In addition, a solder resist composition having a high reflectance has been proposed (see, for example, Patent Document 1).

また、半田リフロー時の高温に晒されたり、または光が照射されたりしたときに、白色から変色し難く、かつ反射率が低下し難い、シロキサンポリマー、白色フィラー、酸無水物基又はカルボキシル基と、不飽和二重結合を有する樹脂を含有するレジスト材料が提案されている(例えば、特許文献2参照。)。   In addition, when exposed to high temperatures during solder reflow or when irradiated with light, it is difficult to change color from white, and the reflectance is not easily lowered, and siloxane polymer, white filler, acid anhydride group or carboxyl group A resist material containing a resin having an unsaturated double bond has been proposed (see, for example, Patent Document 2).

特開2009−149879号公報JP 2009-149879 A 国際公開第2009/090867号International Publication No. 2009/090867

上記特許文献では、ソルダーレジストの課題を解決する種々の方法が提案されている。しかし、特許文献1に記載されているソルダーレジスト組成物は、ルチル型酸化チタンを含有するため高反射率であり経時による反射率の低下および劣化による着色が抑えられているものの、難燃性、柔軟性に乏しく硬化時の収縮が大きいため、フレキシブルプリント配線板の絶縁保護膜として利用した場合、難燃性、耐折れ性に乏しく反りが大きい問題があった。特許文献2に記載されているレジスト材料は、シロキサンポリマー、白色フィラー、酸無水物基又はカルボキシル基と、不飽和二重結合とを有する樹脂とを含有するため、半田リフロー時の高温に晒されたり、または光が照射されたりしたときに、白色から変色し難く、かつ反射率が低下し難いものの、フレキシブルプリント配線板の絶縁保護膜として利用した場合、シロキサンポリマーによる接着不良、工程汚染、不純物のブリードアウトによる接点障害が問題となり、また難燃性、耐折れ性に乏しく反りが大きい問題があった。   In the said patent document, the various method which solves the subject of a soldering resist is proposed. However, although the solder resist composition described in Patent Document 1 contains rutile-type titanium oxide, it has a high reflectivity, and the coloration due to deterioration and deterioration of reflectivity over time is suppressed. Due to poor flexibility and large shrinkage during curing, when used as an insulating protective film for flexible printed wiring boards, there is a problem of poor flame resistance and breakage resistance and large warpage. Since the resist material described in Patent Document 2 contains a siloxane polymer, a white filler, an acid anhydride group or a carboxyl group, and a resin having an unsaturated double bond, it is exposed to high temperatures during solder reflow. When it is used as an insulating protective film for flexible printed wiring boards, it is difficult to change its color from white when exposed to light or when irradiated with light. There are problems of contact failure due to bleed-out, as well as problems of poor flame resistance and breakage resistance and large warpage.

本発明者らは上記課題を解決すべく鋭意研究した結果、少なくとも、(A)分子内にケイ素を実質的に含有しない熱硬化性樹脂、(B)白色着色剤、及び(C)フィラー型難燃剤を含有する白色熱硬化性樹脂組成物層及びポリイミドフィルムを含む白色カバーレイフィルムから、工程汚染がない、柔軟性に富む、白色度および反射率が高い、難燃性に優れる、加熱プレス時に染み出しが起こらない、光照射後の反射率・色相変化が少ないなどの少なくとも1以上の効果を奏する白色カバーレイフィルム及プびリント配線板が得られる知見を得、これらの知見に基づいて、本発明に達したものである。本発明は以下の新規な構成の白色熱硬化性樹脂組成物からなる層がポリイミドフィルムの少なくとも片面に設けられていることを特徴とする白色カバーレイフィルムにより上記課題を解決しうる。   As a result of diligent research to solve the above problems, the present inventors have at least (A) a thermosetting resin substantially free of silicon in the molecule, (B) a white colorant, and (C) a filler type difficulty. From white thermosetting resin composition layer containing flame retardant and white coverlay film including polyimide film, no process contamination, high flexibility, high whiteness and reflectivity, excellent flame retardancy, during hot press Obtained the knowledge that white coverlay film and printed wiring board with at least one effect such as no bleeding, low reflectance and hue change after light irradiation, etc. are obtained, based on these findings, The present invention has been achieved. The present invention can solve the above problems with a white coverlay film in which a layer made of a white thermosetting resin composition having the following novel structure is provided on at least one surface of a polyimide film.

すなわち本願発明は、少なくとも、(A)分子内にケイ素を実質的に含有しない熱硬化性樹脂、(B)白色着色剤、及び(C)フィラー型難燃剤を含有する白色熱硬化性樹脂組成物層及びポリイミドフィルムを含む白色カバーレイフィルムである。   That is, the present invention provides a white thermosetting resin composition containing at least (A) a thermosetting resin substantially free of silicon in the molecule, (B) a white colorant, and (C) a filler-type flame retardant. A white coverlay film comprising a layer and a polyimide film.

また、本願発明にかかる白色熱硬化性樹脂組成物では、前記(C)フィラー型難燃剤がホスフィン酸塩を含有することが好ましい。   Moreover, in the white thermosetting resin composition concerning this invention, it is preferable that the said (C) filler type flame retardant contains a phosphinic acid salt.

また、本願発明にかかる白色熱硬化性樹脂組成物では、前記(A)熱硬化性樹脂が、少なくとも硬化後においてウレタン結合を含有することが好ましい。   Moreover, in the white thermosetting resin composition concerning this invention, it is preferable that the said (A) thermosetting resin contains a urethane bond at least after hardening.

また、本願発明にかかる白色熱硬化性樹脂組成物では、前記(B)白色着色剤が酸化チタンを含有することが好ましい。   Moreover, in the white thermosetting resin composition concerning this invention, it is preferable that the said (B) white colorant contains a titanium oxide.

また、本願発明にかかるフレキシブルプリント配線板は上記白色カバーレイフィルムのポリイミドフィルム面に接着剤層を設けた接着剤層付き白色カバーレイフィルムを、回路に被覆することによって得られるものである。   Moreover, the flexible printed wiring board concerning this invention is obtained by coat | covering the circuit with the white coverlay film with an adhesive layer which provided the adhesive bond layer in the polyimide film surface of the said white coverlay film.

また、本願発明にかかるLEDを実装した発光装置は上記フレキシブルプリント配線板にLEDを実装することによって得られるものである。   Moreover, the light-emitting device which mounted LED concerning this invention is obtained by mounting LED in the said flexible printed wiring board.

本願発明の白色カバーレイフィルムは、少なくとも、(A)分子内にケイ素を実質的に含有しない熱硬化性樹脂、(B)白色着色剤、及び(C)フィラー型難燃剤を含有する白色熱硬化性樹脂組成物層及びポリイミドフィルムであるため、工程汚染がない、柔軟性に富む、白色度および反射率が高い、難燃性に優れる、加熱プレス時に染み出しが起こらない、光照射後の反射率・色相変化が少ないなどの少なくとも1以上の効果を奏する。従って、本願発明の多層フィルムは種々の回路基板の保護膜等に使用でき、優れた効果を奏するものである。   The white coverlay film of the present invention has at least (A) a thermosetting resin containing substantially no silicon in the molecule, (B) a white colorant, and (C) a filler-type flame retardant. Since it is a conductive resin composition layer and polyimide film, there is no process contamination, high flexibility, high whiteness and reflectivity, excellent flame retardancy, no oozing during heating press, reflection after light irradiation There are at least one effect such as a small rate and hue change. Therefore, the multilayer film of the present invention can be used as a protective film for various circuit boards and exhibits excellent effects.

以下本願発明について、(I)白色熱硬化性樹脂組成物、(II)ポリイミドフィルム、(III)白色カバーレイフィルム、(IV)白色カバーレイフィルムの利用方法の順に詳細に説明する。   Hereinafter, the present invention will be described in detail in the order of (I) white thermosetting resin composition, (II) polyimide film, (III) white coverlay film, and (IV) white coverlay film.

(I)白色熱硬化性樹脂組成物
本願発明の白色熱硬化性樹脂組成物とは、少なくとも、(A)分子内にケイ素を実質的に含有しない熱硬化性樹脂、(B)白色着色剤、及び(C)フィラー型難燃剤を含有するものである。ここで、本願発明の熱硬化性樹脂とは加熱によって不可逆的に反応する反応点を持ち、硬化後に絶縁性を示す樹脂であればよい。この不可逆的な反応点は多数の繰り返し単位を持つポリマー鎖の中に組み込まれてもよいし、1種の構成単位からなるモノマーに含まれていてもよい。また、本発明における熱硬化性樹脂は1種類だけであっても複数種を組み合わせたものであっても良い。
(I) White thermosetting resin composition The white thermosetting resin composition of the present invention is at least (A) a thermosetting resin substantially free of silicon in the molecule, (B) a white colorant, And (C) a filler-type flame retardant. Here, the thermosetting resin of the present invention may be any resin that has a reaction point that reacts irreversibly by heating and exhibits insulating properties after curing. This irreversible reaction point may be incorporated into a polymer chain having a large number of repeating units or may be contained in a monomer composed of one kind of structural unit. Further, the thermosetting resin in the present invention may be one kind or a combination of plural kinds.

本願発明の(A)が分子内にケイ素を実質的に含有しないとは、基本的には分子内にケイ素を全く含有しないことを意味するが、熱硬化時に脱離し、樹脂組成物中より消失してしまう保護基等については含有していてもよい。かかる(A)分子内にケイ素を実質的に含有しない熱硬化性樹脂としては、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、ポリグリコール型エポキシ樹脂、脂肪族エポキシ樹脂、脂環式エポキシ樹脂、シクロペンタジエン型エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂、トリアジン骨格含有エポキシ樹脂、脂肪族ジイソシアネート化合物、脂肪族ポリイソシアネート化合物、脂環式ジイソシアネート化合物、脂環式ポリイソシアネート化合物及びこれらイソシアネート化合物のブロック体、メラミン樹脂、メラミンホルムアルデヒド樹脂等が好ましいが、これらに限定されない。特に本発明においてはエポキシ化合物、イソシアネート化合物が好ましく用いられ、更に好ましくはイソシアネート化合物を用いることが柔軟性の付与の観点から好ましい。さらに、イソシアネート化合物を用いる場合にはこれらと反応点を持つカルボキシル基、アミノ基、チオール基、水酸基を含み実質的にケイ素を含有しない樹脂と組み合わせて用いることができる。中でも反応性や取り扱いの容易さの観点から水酸基を含有する樹脂を用いることが好ましく、これらを用いた場合、熱硬化後にウレタン結合を有することで白色熱硬化性樹脂層に柔軟性を持たせることができるためより好ましい。また、あらかじめウレタン結合を有し、上記エポキシ樹脂やイソシアネート樹脂と反応する反応点を持った樹脂を用いることもできる。さらに、触媒として金属類を用いたり、3級アミン類を用いることもできる。このように、本件発明においては、(A)熱硬化性樹脂が、少なくとも硬化後においてウレタン結合を含むことが好ましい。   The fact that (A) of the present invention contains substantially no silicon in the molecule basically means that no silicon is contained in the molecule, but it is desorbed during thermosetting and disappears from the resin composition. It may contain about the protecting group etc. which do. Examples of the thermosetting resin that substantially does not contain silicon in the molecule (A) include, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, polyglycol type epoxy resin, aliphatic epoxy resin, and alicyclic epoxy. Resin, cyclopentadiene type epoxy resin, dicyclopentadiene type epoxy resin, triazine skeleton-containing epoxy resin, aliphatic diisocyanate compound, aliphatic polyisocyanate compound, alicyclic diisocyanate compound, alicyclic polyisocyanate compound, and block of these isocyanate compounds Body, melamine resin, melamine formaldehyde resin and the like are preferred, but not limited thereto. Particularly in the present invention, an epoxy compound and an isocyanate compound are preferably used, and more preferably an isocyanate compound is used from the viewpoint of imparting flexibility. Further, when an isocyanate compound is used, it can be used in combination with a resin containing a carboxyl group, an amino group, a thiol group, or a hydroxyl group having a reactive site with these compounds and containing substantially no silicon. Among these, it is preferable to use a hydroxyl group-containing resin from the viewpoint of reactivity and ease of handling, and when these are used, the white thermosetting resin layer should have flexibility by having a urethane bond after thermosetting. Is more preferable because In addition, a resin having a urethane bond in advance and having a reaction point that reacts with the epoxy resin or isocyanate resin can be used. Furthermore, metals can be used as the catalyst, and tertiary amines can also be used. Thus, in this invention, it is preferable that (A) thermosetting resin contains a urethane bond at least after hardening.

次に(B)白色着色剤について説明する。本願発明の白色着色剤とは樹脂を白色に着色する機能を持つものであり、熱硬化後の白色熱硬化性樹脂組成物層を白色に着色していれば良い。本願発明においては金属酸化物、金属窒化物といった無機顔料および/またはそれらを有機物、ガラス等で表面処理したものを単一、または組み合わせて用いることが好ましい。さらに本発明では(B)が酸化チタンを含有することがより好ましい。酸化チタンを含むことによって紫外線を効率よく吸収し紫外線による樹脂劣化および着色を防ぐことができる。また、本発明における白色着色剤の添加量は、上記熱硬化性樹脂成分に対して1〜200wt%が好ましく、50〜150wt%添加することがより好ましい。   Next, (B) white colorant will be described. The white colorant of the present invention has a function of coloring the resin white, and the white thermosetting resin composition layer after thermosetting only needs to be colored white. In the present invention, it is preferable to use a single or a combination of inorganic pigments such as metal oxides and metal nitrides and / or surface treatments thereof with organic matter, glass or the like. In the present invention, it is more preferable that (B) contains titanium oxide. By containing titanium oxide, it is possible to efficiently absorb ultraviolet rays and prevent resin deterioration and coloring due to ultraviolet rays. Moreover, 1-200 wt% is preferable with respect to the said thermosetting resin component, and, as for the addition amount of the white colorant in this invention, it is more preferable to add 50-150 wt%.

次に(C)フィラー型難燃剤について説明する。本願発明のフィラー型難燃剤とは白色熱硬化性樹脂組成物層中において難燃効果を持つ成分が溶解せず、粒子状の難燃成分が白色熱硬化樹脂組成物中において分散された状態で存在していることを意味する。特に本発明においてフィラー型難燃剤は難燃性効果と高耐熱性の観点からホスフィン酸塩を含むことが好ましい。上記のホスフィン酸塩は、1種を単独で又は2種以上を組み合わせて使用することができる。また、上記ホスフィン酸塩は市販品として購入することもでき、例えば、EXOLIT OP 930、EXOLIT OP 935、EXOLIT OP 940(いずれもクラリアント社製、商品名)を用いることもできる。特に耐折曲げ性の観点から、上記市販品のホスフィン酸塩を、ビーズミル等を用いて粉砕したものを用いることが好ましい。また、本発明におけるフィラー型難燃剤の添加量は、上記熱硬化性樹脂成分に対して1〜50wt%が好ましく、5〜30wt%添加することがより好ましい。   Next, (C) filler type flame retardant will be described. The filler-type flame retardant of the present invention is a component in which the flame retardant effect is not dissolved in the white thermosetting resin composition layer, and the particulate flame retardant component is dispersed in the white thermosetting resin composition. It means that it exists. In particular, in the present invention, the filler-type flame retardant preferably contains a phosphinate from the viewpoints of flame retardancy and high heat resistance. Said phosphinic acid salt can be used individually by 1 type or in combination of 2 or more types. Moreover, the said phosphinic acid salt can also be purchased as a commercial item, for example, EXOLIT OP 930, EXOLIT OP 935, EXOLIT OP 940 (all are the brand names made by Clariant) can also be used. In particular, from the viewpoint of bending resistance, it is preferable to use a product obtained by pulverizing the commercially available phosphinate using a bead mill or the like. Moreover, 1-50 wt% is preferable with respect to the said thermosetting resin component, and, as for the addition amount of the filler type flame retardant in this invention, it is more preferable to add 5-30 wt%.

また、本発明に記載の白色熱硬化性樹脂組成物は必要に応じて各種添加剤を用いても良い。添加剤の例としては、酸化防止剤、紫外線吸収剤、光安定剤等をあげることができる。これらの添加剤は市販されているあらゆるものを単独、または組み合わせて使用することができる。酸化防止剤としては、アデカスタブAO−60(株式会社ADEKA製)やIRGANOX1010(BASF製)といったフェノール系の酸化防止剤や、アデカスタブHP−10といったリン系酸化防止剤、アデカスタブAO−503といったチオール系酸化防止剤などが例示できる。また、紫外線吸収剤としてはアデカスタブLA−31といったベンゾトリアゾール型、アデカスタブ1413といったベンゾフェノン型、アデカスタブLA−46といったトリアジン型のものが例示できる。光安定剤としてはアデカスタブLA−81といったヒンダードアミン系のものが例示できる。これらの添加剤は白色樹脂組成物の特性を損なわない範囲で用いれば良いが、樹脂組成物に対して0.01wt%以上10wt%以下の範囲で用いることが一般的である。   Moreover, you may use various additives for the white thermosetting resin composition as described in this invention as needed. Examples of additives include antioxidants, ultraviolet absorbers, light stabilizers, and the like. Any of these commercially available additives can be used alone or in combination. Antioxidants include phenolic antioxidants such as ADK STAB AO-60 (manufactured by ADEKA) and IRGANOX 1010 (manufactured by BASF), phosphorus antioxidants such as ADK STAB HP-10, and thiol oxidations such as ADK STAB AO-503. An inhibitor etc. can be illustrated. Examples of ultraviolet absorbers include benzotriazole types such as ADK STAB LA-31, benzophenone types such as ADK STAB 1413, and triazine types such as ADK STAB LA-46. Examples of the light stabilizer include hindered amines such as ADK STAB LA-81. These additives may be used in a range that does not impair the properties of the white resin composition, but are generally used in a range of 0.01 wt% to 10 wt% with respect to the resin composition.

(II)ポリイミドフィルム
次に本発明におけるポリイミドフィルムについて説明する。本発明に係るポリイミドフィルムは、通常、ポリアミド酸をその前駆体として用いて製造することができる。ポリアミド酸の製造方法としては公知のあらゆる方法を用いることができる。通常、芳香族酸二無水物と芳香族ジアミンを、実質的に等モル量となるように有機溶媒中に溶解、反応させてポリアミド酸有機溶媒溶液として得ることができる。
(II) Polyimide film Next, the polyimide film in this invention is demonstrated. The polyimide film according to the present invention can be usually produced using polyamic acid as a precursor thereof. Any known method can be used for producing the polyamic acid. Usually, an aromatic acid dianhydride and an aromatic diamine can be dissolved and reacted in an organic solvent so as to have a substantially equimolar amount to obtain a polyamic acid organic solvent solution.

また、本発明に係るポリイミドフィルムの製造方法としては公知のあらゆる方法を用いることができる。特に、上記ポリアミド酸溶液に無水酢酸等のイミド化促進剤を加え加熱焼成によってイミド化する方法が生産性の観点から好ましい。   Moreover, as a manufacturing method of the polyimide film which concerns on this invention, all well-known methods can be used. In particular, from the viewpoint of productivity, a method of adding an imidization accelerator such as acetic anhydride to the polyamic acid solution and imidizing by heating and baking is preferable.

本発明に係るポリイミドフィルムは市販品として購入することもできアピカルNPI(株式会社カネカ社製、商品名)等のこれまで単独でカバーレイフィルムとして用いられてきたものを用いることができる。   The polyimide film concerning this invention can also be purchased as a commercial item, and what has been used as a coverlay film by itself, such as Apical NPI (a Kaneka company make, brand name), can be used.

本発明で用いられるポリイミドフィルムは白色熱硬化性樹脂層との密着性や、カバーレイフィルムとして用いる場合の接着剤との密着性を上げる目的で表面処理をされていても良い。表面処理の方法は、コロナ処理やプラズマ処理等が挙げられるが、これらに限定されるものではない。   The polyimide film used in the present invention may be subjected to a surface treatment for the purpose of improving the adhesiveness with the white thermosetting resin layer or the adhesive when used as a coverlay film. Examples of surface treatment methods include, but are not limited to, corona treatment and plasma treatment.

本発明で用いられるポリイミドフィルムの厚みは特に限定されるものではないが柔軟性、折り曲げ性の観点から5〜50μmが好ましく、5〜30μmがより好ましい。   Although the thickness of the polyimide film used by this invention is not specifically limited, 5-50 micrometers is preferable from a softness | flexibility and a bendable viewpoint, and 5-30 micrometers is more preferable.

(III)白色カバーレイフィルム
本発明に係る白色カバーレイフィルムは上記白色熱硬化性樹脂層がポリイミドフィルムの片方の面に設けられていることを特徴とする。白色熱硬化性樹脂層をポリイミドフィルム上へ設ける方法は特に限定されないが、未硬化の白色熱硬化性樹脂溶液をポリイミド上へ塗布し加熱によって乾燥・硬化させる方法が生産性の観点からは好ましい。塗布する方法は従来公知のあらゆる方法を用いることができるが粉体を多く含むためリバースコーターやダイコーターを用いることが好ましい。
(III) White coverlay film The white coverlay film according to the present invention is characterized in that the white thermosetting resin layer is provided on one surface of a polyimide film. The method of providing the white thermosetting resin layer on the polyimide film is not particularly limited, but a method of applying an uncured white thermosetting resin solution onto the polyimide and drying and curing by heating is preferable from the viewpoint of productivity. Any conventionally known method can be used as the coating method, but a reverse coater or a die coater is preferably used because it contains a large amount of powder.

(IV)白色カバーレイフィルムの利用方法
本発明に係る白色カバーレイフィルムの利用方法について説明する。上記のようにしてポリイミドフィルムの片面に白色熱硬化性樹脂層を設けたフィルムの、もう一方の面、すなわち白色熱硬化性樹脂層とは反対側のポリイミドフィルム面に接着剤層を設けこの接着剤層を介して回路を形成したフレキシブル配線板を被覆することで白色かつ難燃性をもったフレキシブルプリント配線板を得ることができる。
(IV) Utilization Method of White Coverlay Film A utilization method of the white coverlay film according to the present invention will be described. As described above, an adhesive layer is provided on the other side of the film provided with the white thermosetting resin layer on one side of the polyimide film, that is, on the side opposite to the white thermosetting resin layer. A flexible printed wiring board having a white color and flame retardancy can be obtained by covering a flexible wiring board having a circuit formed through an agent layer.

以下本発明を実施例により具体的に説明するが本発明はこれらの実施例により限定されるものではない。   EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.

<白色熱硬化性樹脂組成物の調合>
(A)分子内にケイ素を実質的に含有しない熱硬化性樹脂として、水酸基を有する東亞合成株式会社製アクリルポリオールUH−2041を40.0gとイソシアネート基を有する旭化成ケミカルズ株式会社製デュラネートTPA-B80Eを26.1g量りとり溶媒として60gの2‐ブタノン中へ溶解した。TPA−B80Eはブロック型イソシアネートであり加熱時にブロック型保護基が外れ、水酸基とウレタン結合を形成することができる。次に(B)白色着色剤成分として石原産業製ルチル型酸化チタンCR−60を60g、(C)フィラー型難燃剤としてホスフィン酸塩であるクラリアント社製Exolit OP−935を10g、酸化防止剤としてBASF社製Irganox1010を0.15gをAIMEX社製ビーズミルに入れ、760rpmで混合攪拌した。次いで、粒径1mmのジルコニアビーズを充填率70%になるよう添加し、1000rpmで攪拌して分散した後にジルコニアビーズを濾別し、本願発明の白色熱硬化性樹脂組成物溶液を取得した。混合溶液を脱泡装置で溶液中の泡を完全に脱泡して下記評価を実施した。評価結果は表1に記載した。
<Preparation of white thermosetting resin composition>
(A) As thermosetting resin substantially free of silicon in the molecule, 40.0 g of acrylic polyol UH-2041 manufactured by Toagosei Co., Ltd. having a hydroxyl group and Duranate TPA-B80E manufactured by Asahi Kasei Chemicals Co., Ltd. having an isocyanate group 26.1 g was dissolved in 60 g of 2-butanone as a solvent. TPA-B80E is a block-type isocyanate, and when heated, the block-type protective group is removed, and a hydroxyl group and a urethane bond can be formed. Next, (B) 60 g of rutile titanium oxide CR-60 manufactured by Ishihara Sangyo Co., Ltd. as a white colorant component, 10 g of Exolit OP-935 manufactured by Clariant, which is a phosphinic acid salt as a filler type flame retardant, as an antioxidant 0.15 g of Irganox 1010 manufactured by BASF was put in a bead mill manufactured by AIMEX, and mixed and stirred at 760 rpm. Next, zirconia beads having a particle diameter of 1 mm were added so as to have a filling rate of 70%, and after stirring and dispersing at 1000 rpm, the zirconia beads were separated by filtration to obtain a white thermosetting resin composition solution of the present invention. The following evaluation was carried out by completely defoaming the foam in the solution with a defoaming device. The evaluation results are shown in Table 1.

<ポリイミドフィルム上への塗膜の作製>
上記白色熱硬化性樹脂組成物を、ベーカー式アプリケーターを用いて、25μmのポリイミドフィルム(株式会社カネカ製:商品名25NPI)に最終乾燥厚みが16μmになるように300mm×200mmの面積に流延・塗布し、80℃で2分乾燥した後、180℃のオーブン中で30分加熱硬化させてポリイミドフィルム上に白色熱硬化性樹脂組成物の硬化膜を作製した。
<Preparation of coating film on polyimide film>
The white thermosetting resin composition was cast on an area of 300 mm × 200 mm on a 25 μm polyimide film (manufactured by Kaneka Corporation: product name 25 NPI) using a Baker type applicator so that the final dry thickness was 16 μm. After applying and drying at 80 ° C. for 2 minutes, a cured film of a white thermosetting resin composition was prepared on a polyimide film by heating and curing in an oven at 180 ° C. for 30 minutes.

<硬化膜の評価>
(i)柔軟性の評価
白色熱硬化性樹脂組成物の硬化膜積層フィルムを50mm×10mmの短冊に切り出して、白色熱硬化性樹脂組成物の硬化膜を外側にして25mmのところで180°に折り曲げ、折り曲げ部に5kgの荷重を3秒間乗せた後、荷重を取り除き、折り曲げ部の頂点を顕微鏡で観察した。顕微鏡観察後、折り曲げ部を開いて、再度5kgの荷重を3秒間乗せた後、荷重を取り除き完全に硬化膜積層フィルムを開いた。上記操作を繰り返し、折り曲げ部にクラックが発生する回数を折り曲げ回数とした。
○:折り曲げ回数5回で硬化膜にクラックが無いもの。
△:折り曲げ回数3回で硬化膜にクラックが無いもの。
×:折り曲げ1回目に硬化膜にクラックが発生するもの。
<Evaluation of cured film>
(I) Evaluation of flexibility A cured film laminated film of a white thermosetting resin composition is cut into a 50 mm × 10 mm strip and bent at 180 ° at 25 mm with the cured film of the white thermosetting resin composition facing outward. Then, after applying a load of 5 kg to the bent portion for 3 seconds, the load was removed, and the vertex of the bent portion was observed with a microscope. After microscopic observation, the bent portion was opened, and a 5 kg load was again applied for 3 seconds, and then the load was removed to completely open the cured film laminated film. The above operation was repeated, and the number of occurrences of cracks in the bent portion was defined as the number of bending times.
A: The cured film has no cracks after being bent five times.
Δ: The cured film has no cracks after being bent three times.
X: A crack occurs in the cured film at the first folding.

(ii)反り
硬化膜積層フィルムを50mm×50mmの面積に切り出して平滑な台の上に塗布膜が上面になるように置き、フィルム端部の反りの最大高さを測定してそり量とした。ポリイミドフィルム表面での反り量が少ない程、プリント配線板表面での応力が小さくなり、プリント配線板の反り量も低下することになる。反り量は5mm以下であることが好ましい。尚、筒状に丸まる場合は×とした。
(Ii) Warpage Cut the cured film laminated film into an area of 50 mm x 50 mm and place it on a smooth base so that the coating film is on the upper surface, and measure the maximum height of the warp at the end of the film as the amount of warpage . The smaller the amount of warpage on the polyimide film surface, the smaller the stress on the surface of the printed wiring board and the lower the amount of warping of the printed wiring board. The warp amount is preferably 5 mm or less. In addition, when rounding cylindrically, it was set as x.

(iii)燃焼性
硬化膜積層フィルムを寸法:50mm幅×200mm長さ×41μm 厚み(ポリイミドフィルムの厚みを含む)に切り出し、125mmの部分に標線を入れ、直径約13mmの筒状に丸め、標線よりも上の重ね合わせ部分(75mmの箇所)、及び、上部に隙間がないようにPIテープを貼り、燃焼性試験用の筒を20本用意した。 そのうち10本は(1)23℃/50%相対湿度/48時間で処理し、残りの10本は(2)70℃で168時間処理後無水塩化カルシウム入りデシケーターで4時間以上冷却した。これらのサンプルの上部をクランプで止めて垂直に固定し、サンプル下部にバーナーの炎を3秒間近づけて着火する。3秒間経過したらバーナーの炎を遠ざけて、サンプルの炎や燃焼が何秒後に消えるか測定する。
○:各条件((1)、(2))につき、サンプルからバーナーの炎を遠ざけてから平均(10本の平均)で10秒以内、最高で10秒以内に炎や燃焼が停止し自己消火し、かつ、評線まで燃焼が達していないもの。
×:1本でも10秒以内に消火しないサンプルがあったり、炎が評線以上のところまで上昇して燃焼するもの。
(Iii) Combustibility The cured film laminated film is cut into a dimension: 50 mm width × 200 mm length × 41 μm thickness (including the thickness of the polyimide film), a marked line is put in a 125 mm portion, and it is rolled into a cylindrical shape having a diameter of about 13 mm, PI tape was affixed so that there was no gap at the overlapping part (75 mm) above the marked line and at the top, and 20 flammability test tubes were prepared. Of these, 10 were treated at (1) 23 ° C./50% relative humidity / 48 hours, and the remaining 10 were treated at (2) 70 ° C. for 168 hours and then cooled in a desiccator containing anhydrous calcium chloride for 4 hours or more. The upper part of these samples is clamped and fixed vertically, and a burner flame is brought close to the lower part of the sample for 3 seconds to ignite. After 3 seconds, move the burner flame away and measure how many seconds after the sample flame or burning disappears.
○: For each condition ((1), (2)), the flame and combustion stopped within 10 seconds on average (average of 10) after the flame of the burner was moved away from the sample, and self-extinguishment within 10 seconds at maximum However, it has not burned to the rating line.
×: Even one sample does not extinguish within 10 seconds, or the flame rises above the rating line and burns.

(iv)加熱プレス時の染み出し
硬化膜積層フィルムを50mm×50mmに切り出しポリイミドフィルム2枚に挟み更に厚さ2mmの2枚のSUS板の間に挟んで180℃で30分、3MPaの圧力をかけて処理した試験片を観察し、試験片表面の微小な膨れ、油状物質の染み出しなどを観察した。
○:試験片表面に膨れ、染み出しなどの異常が見られないもの
×:試験片表面に膨れ、染み出しなどの異常が見られるもの
(Iv) Bleeding during heating press The cured film laminated film is cut out into 50 mm x 50 mm, sandwiched between two polyimide films, sandwiched between two SUS plates with a thickness of 2 mm, and a pressure of 3 MPa is applied at 180 ° C for 30 minutes. The treated test piece was observed, and minute swelling on the surface of the test piece, exudation of oily substances, and the like were observed.
○: No abnormalities such as swelling and exudation on the surface of the specimen ×: No abnormalities such as swelling and exudation on the surface of the specimen

(v)初期反射率
硬化膜積層フィルムを用いて、白色熱硬化性樹脂組成物硬化膜層の初期反射率を下記方法で測定し、450nmにおける測定値を初期反射率とした。
使用装置:日本分光株式会社製 紫外可視分光光度計 V−650
測定波長領域:300〜800nm
標準白板:ラブスフェア社製 スペクトラロンTM。
(V) Initial reflectance Using the cured film laminated film, the initial reflectance of the white thermosetting resin composition cured film layer was measured by the following method, and the measured value at 450 nm was defined as the initial reflectance.
Equipment used: UV-visible spectrophotometer V-650 manufactured by JASCO Corporation
Measurement wavelength region: 300 to 800 nm
Standard white board: Spectralon TM manufactured by Labsphere.

(vi)初期色相
硬化膜積層フィルムを用いて、白色熱硬化性樹脂組成物硬化膜層のL、a、b値を下記装置で測定した。尚、Lは明度を、aは赤味を、bは黄味を示す。
使用装置:日本電色工業株式会社製 ハンディー色差計 NR−3000。
(Vi) L, a, and b values of the white thermosetting resin composition cured film layer were measured with the following apparatus using the initial hue cured film laminated film. L represents lightness, a represents reddishness, and b represents yellowishness.
Device used: Nippon Denshoku Industries Co., Ltd. Handy color difference meter NR-3000.

(vii)光照射後の反射率変化
上記(v)初期反射率の測定に用いた硬化膜積層フィルムを下記条件で100J/cmのUVを照射し、(v)初期反射率測定方法と同様の方法で反射率を測定した。
使用装置:岩崎電気株式会社製 コンベア型UV照射器
出力:120W/cm
ランプ:メタルハライドランプ、6kW、2灯
照射器:コールドミラー集光型
光照射前の初期反射率から光照射後の反射率への変化率を算出した。
○:反射率の変化率が5%未満のもの。
△:反射率の変化率が5%以上、10%未満のもの。
×:反射率の変化率が10%以上のもの。
(Vii) Reflectance change after light irradiation The cured film laminated film used in the above (v) measurement of the initial reflectance was irradiated with 100 J / cm 2 of UV under the following conditions, and (v) the same as the initial reflectance measurement method. The reflectance was measured by the method.
Equipment used: Conveyor type UV irradiator manufactured by Iwasaki Electric Co., Ltd. Output: 120 W / cm
Lamp: Metal halide lamp, 6 kW, 2 lamp irradiator: Cold mirror Condensation type The change rate from the initial reflectance before the light irradiation to the reflectance after the light irradiation was calculated.
A: The rate of change in reflectance is less than 5%.
Δ: The reflectance change rate is 5% or more and less than 10%.
X: The rate of change in reflectance is 10% or more.

(viii)光照射後の色相変化
上記(vi)初期色相の測定に用いた硬化膜積層フィルムを(vii)光照射後の反射率変化と同様の条件で100J/cmのUVを照射し、(vi)初期色相測定方法と同様の方法でL、a、b値を測定した。
○:L値が80以上、a値が1未満、b値が1未満のもの。
△:L値が80以上、a値が2未満、b値が2未満のもの。
×:L値が80以下、a値が2以上、b値が2以上のもの。
(Viii) Hue change after light irradiation (vi) The cured film laminated film used for the measurement of initial hue is irradiated with 100 J / cm 2 of UV under the same conditions as (vii) reflectance change after light irradiation, (Vi) L, a, and b values were measured by the same method as the initial hue measurement method.
○: L value is 80 or more, a value is less than 1, and b value is less than 1.
Δ: L value is 80 or more, a value is less than 2, and b value is less than 2.
X: L value is 80 or less, a value is 2 or more, b value is 2 or more.

Figure 2012175053
Figure 2012175053

上記評価結果から、本発明における白色カバーレイはケイ素を実質的に含有しないため工程汚染がない、柔軟性に富む、白色度および反射率が高い、難燃性に優れる、加熱プレス時に染み出しが起こらない、光照射後の反射率・色相変化が少ないなどの少なくとも1以上の効果を奏する白色樹脂層付きカバーレイフィルムであることがわかる。   From the above evaluation results, the white coverlay in the present invention does not substantially contain silicon, so there is no process contamination, high flexibility, high whiteness and reflectance, excellent flame retardancy, and exudation during hot press. It can be seen that this is a coverlay film with a white resin layer that does not occur and has at least one effect such as little change in reflectance and hue after light irradiation.

Claims (6)

少なくとも、(A)分子内にケイ素を実質的に含有しない熱硬化性樹脂、(B)白色着色剤、及び(C)フィラー型難燃剤を含有する白色熱硬化性樹脂組成物層及びポリイミドフィルムを含む白色カバーレイフィルム。   At least (A) a thermosetting resin substantially free of silicon in the molecule, (B) a white colorant, and (C) a white thermosetting resin composition layer and a polyimide film containing a filler-type flame retardant. Including white coverlay film. 前記(C)フィラー型難燃剤がホスフィン酸塩を含むことを特徴とする請求項1に記載の白色カバーレイフィルム。   The white coverlay film according to claim 1, wherein the (C) filler-type flame retardant contains a phosphinate. 前記(A)熱硬化性樹脂が、少なくとも硬化後においてウレタン結合を含むことを特徴とする請求項1または2に記載の白色カバーレイフィルム。   The white coverlay film according to claim 1 or 2, wherein the (A) thermosetting resin contains a urethane bond at least after curing. 前記(B)白色着色剤が酸化チタンを含むことを特徴とする請求項1〜3のいずれか1項に記載の白色カバーレイフィルム。   The white coverlay film according to any one of claims 1 to 3, wherein the (B) white colorant contains titanium oxide. 請求項1〜4のいずれか1項に記載の白色カバーレイフィルムのポリイミドフィルム面に接着剤層を設けた接着剤層付き白色カバーレイフィルムを、回路に被覆したことを特徴とするフレキシブルプリント配線板。   A flexible printed wiring, wherein a circuit is coated with a white coverlay film with an adhesive layer in which an adhesive layer is provided on a polyimide film surface of the white coverlay film according to any one of claims 1 to 4. Board. 請求項5記載のフレキシブルプリント配線板にLEDを実装した発光装置。   A light emitting device in which an LED is mounted on the flexible printed wiring board according to claim 5.
JP2011038454A 2011-02-24 2011-02-24 Novel white cover lay film Pending JP2012175053A (en)

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JP2015090954A (en) * 2013-11-07 2015-05-11 ナミックス株式会社 Flexible printed wiring board and method for manufacturing the same
KR20150078585A (en) * 2013-12-31 2015-07-08 도레이첨단소재 주식회사 White coverlay film
JP2016086737A (en) * 2014-11-05 2016-05-23 シーアイ化成株式会社 Olefin system agricultural film
CN118360017A (en) * 2024-05-14 2024-07-19 皇冠新材料科技股份有限公司 White halogen-free flame-retardant epoxy resin composition and cover film prepared by using same

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JP2015090954A (en) * 2013-11-07 2015-05-11 ナミックス株式会社 Flexible printed wiring board and method for manufacturing the same
KR20150078585A (en) * 2013-12-31 2015-07-08 도레이첨단소재 주식회사 White coverlay film
JP2016086737A (en) * 2014-11-05 2016-05-23 シーアイ化成株式会社 Olefin system agricultural film
CN118360017A (en) * 2024-05-14 2024-07-19 皇冠新材料科技股份有限公司 White halogen-free flame-retardant epoxy resin composition and cover film prepared by using same

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