JP2006110999A - Metal clad white laminated body - Google Patents
Metal clad white laminated body Download PDFInfo
- Publication number
- JP2006110999A JP2006110999A JP2005239621A JP2005239621A JP2006110999A JP 2006110999 A JP2006110999 A JP 2006110999A JP 2005239621 A JP2005239621 A JP 2005239621A JP 2005239621 A JP2005239621 A JP 2005239621A JP 2006110999 A JP2006110999 A JP 2006110999A
- Authority
- JP
- Japan
- Prior art keywords
- white
- metal
- clad
- resin composition
- layer
- 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.)
- Granted
Links
Landscapes
- Laminated Bodies (AREA)
Abstract
Description
本発明はポリイミドと白色顔料を含む白色樹脂組成物を用いた金属張り白色積層体に関する。この金属張り白色積層体は、ＬＥＤ（発光ダイオード）を実装するフレキシブルなプリント配線基板に好適に利用される。 The present invention relates to a metal-clad white laminate using a white resin composition containing polyimide and a white pigment. This metal-clad white laminate is suitably used for a flexible printed wiring board on which an LED (light emitting diode) is mounted.
従来、ＬＥＤ実装用として使用されているプリント配線板は、白色顔料を含有する熱硬化性樹脂をシート状ガラス基材に含浸させたプリプレグと金属箔とを加熱プレス成型して得たリジッド金属張積層板が主に用いられていた。 Conventionally, printed wiring boards used for LED mounting are rigid metal-clad obtained by hot press molding a prepreg impregnated with a thermosetting resin containing a white pigment into a sheet glass substrate and a metal foil. Laminates were mainly used.
現在の電子機器は、携帯性および外観を向上させるために、薄型化・軽量化が進んでいる。それに応じて、使用される発光素子としてチップＬＥＤが主流となっているが、このチップＬＥＤもさらに軽量化、薄型化が求められている。また、ＬＣＤ（液晶ディスプレイ）のバックライト等で使用される白色チップＬＥＤ用の基板では、反射率が大きく白色度の高いものが求められている。 Current electronic devices are becoming thinner and lighter in order to improve portability and appearance. Accordingly, chip LEDs are mainly used as light-emitting elements to be used, and the chip LEDs are also required to be lighter and thinner. Further, a substrate for white chip LED used in a backlight of an LCD (liquid crystal display) or the like is required to have a high reflectance and a high whiteness.
ところが、従来のリジッド金属張積層板では、軽量化・薄型化に限界があった（特許文献１〜３参照。）。
このため、耐熱性に優れる接着剤あるいは接着性フィルムが求められている。これらとしては、ポリイミドあるいはポリアミド酸の分散液を接着剤として絶縁性基材に塗布し、その後溶剤除去と場合によってはイミド化処理を行い、熱圧着性の接着層を形成する方法が開示されている（特許文献４、５参照。）。また、ポリイミドあるいはポリアミド酸の分散液をガラス板などに塗布し、その後溶剤除去、場合によってはイミド化処理を行い、熱圧着性の接着性フィルムを形成する方法が開示されている。このようにして形成された接着層、接着性フィルムに、金属層などの被接着物が熱圧着される（特許文献４〜６参照。）。
However, conventional rigid metal-clad laminates have limitations in reducing weight and thickness (see Patent Documents 1 to 3).
For this reason, the adhesive agent or adhesive film excellent in heat resistance is calculated | required. These include a method in which a dispersion of polyimide or polyamic acid is applied to an insulating substrate as an adhesive, followed by solvent removal and optionally imidization to form a thermocompression-bonding adhesive layer. (See Patent Documents 4 and 5). In addition, a method is disclosed in which a dispersion of polyimide or polyamic acid is applied to a glass plate or the like, and thereafter a solvent is removed and imidization treatment is performed in some cases to form a thermocompression-bonding adhesive film. An object to be bonded such as a metal layer is thermocompression bonded to the adhesive layer and the adhesive film thus formed (see Patent Documents 4 to 6).
これらの耐熱性に優れる接着剤あるいは接着性フィルムは、芳香族テトラカルボン酸二無水物と芳香族ジアミン類との重縮合反応により得られる芳香族ポリイミドあるいは芳香族ポリアミド酸からなる分散液またはフィルムが広く用いられている。しかし、この様な芳香族ポリイミド樹脂は、優れた耐熱性および機械特性を有するものの、可視光の吸収が大きく淡黄色から赤褐色に着色している為に、白色顔料と混合した樹脂組成物は反射率が低く、さらに白色度も低くなる。そのため、かかる樹脂組成物を接着層に用いたフレキシブル金属張積層体はＬＥＤ実装用途において輝度が低下し実用的ではないという問題があった。 These adhesives or adhesive films having excellent heat resistance include dispersions or films made of aromatic polyimide or aromatic polyamic acid obtained by polycondensation reaction of aromatic tetracarboxylic dianhydride and aromatic diamines. Widely used. However, although such aromatic polyimide resin has excellent heat resistance and mechanical properties, it absorbs visible light and is colored from pale yellow to reddish brown, so the resin composition mixed with the white pigment is reflective. The rate is low and the whiteness is also low. Therefore, the flexible metal-clad laminate using such a resin composition for the adhesive layer has a problem in that the luminance decreases in LED mounting applications and is not practical.
ポリイミドを構成するモノマーに脂肪族系のものを用いることにより、テトラカルボン酸二無水物部分とジアミン部分との間の電荷移動が抑制されるために着色が抑制される事が知られている（非特許文献１参照。）。脂肪族系モノマーを用いたポリイミドは透明性に加えて、耐熱性も兼ね備えるという特徴を生かして、液晶配向膜に多く利用されている（特許文献７参照。）。しかしながら、ＬＥＤ実装用途を目的として、脂肪族系モノマーを用いたポリイミドおよび白色顔料を混合した樹脂組成物を接着層に用いたフレキシブル金属張積層体に関する報告例は無い。 It is known that the use of an aliphatic monomer constituting the polyimide suppresses the color transfer because the charge transfer between the tetracarboxylic dianhydride moiety and the diamine moiety is suppressed ( (Refer nonpatent literature 1.). Polyimides using aliphatic monomers are often used for liquid crystal alignment films by taking advantage of heat resistance in addition to transparency (see Patent Document 7). However, there is no report on a flexible metal-clad laminate using a resin composition in which a polyimide using an aliphatic monomer and a white pigment are mixed for the purpose of LED mounting.
本発明の課題は、従来、ＬＥＤを実装するプリント配線板の絶縁層に用いられてきた材料の問題点を解決し、反射率および白色度が高く耐光性に優れた白色樹脂組成物を用いた、薄型化かつ軽量化が容易なフレキシブル金属張り積層体を提供することにある。 An object of the present invention is to solve the problems of materials conventionally used for an insulating layer of a printed wiring board on which an LED is mounted, and to use a white resin composition having high reflectance and whiteness and excellent light resistance. Another object of the present invention is to provide a flexible metal-clad laminate that is thin and lightweight.
本発明者らは上記の課題を解決するため鋭意検討した結果、脂肪族テトラカルボン酸構造を有する繰り返し単位を有するポリイミドと白色顔料を混合した樹脂組成物が反射率および白色度が高く耐光性に優れている上に、該樹脂組成物を用いると薄型化かつ軽量化が容易なフレキシブル金属張り白色積層体が得られることを見出し、本発明に到達した。 As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a resin composition in which a polyimide having a repeating unit having an aliphatic tetracarboxylic acid structure and a white pigment are mixed has high reflectance and whiteness, and has high light resistance. The present inventors have found that a flexible metal-clad white laminate that is excellent in thickness and weight can be easily obtained by using the resin composition.
すなわち、本発明は、一般式Ｉで示される繰り返し単位を有するポリイミドに白色顔料を混合した樹脂組成物からなる白色樹脂層が、少なくとも１の金属層の接着層である金属張り白色積層体である。 That is, the present invention is a metal-clad white laminate in which a white resin layer made of a resin composition in which a white pigment is mixed with a polyimide having a repeating unit represented by the general formula I is an adhesive layer of at least one metal layer. .
本発明においては、前記一般式Ｉ中のＲがシクロヘキサン構造を有する４価の基であること、前記白色顔料が酸化チタン、酸化ジルコニウム、酸化カルシウム、酸化ケイ素、酸化亜鉛、酸化アルミニウム、硫化亜鉛、硫酸カルシウム、硫酸バリウム、炭酸鉛、水酸化鉛、塩基性モリブデン酸亜鉛、塩基性モリブデン酸カルシウム亜鉛、鉛白、モリブデンホワイト、およびリトポンからなる群より選ばれる１種以上であること、特に前記白色顔料が、表面に被覆層を形成したルチル型酸化チタンであることであり、さらに、前記酸化チタンの被覆層が、ＳｉＯ２またはＡｌ２Ｏ３処理であること、前記酸化チタンの被覆層が、ＳｉＯ２またはＡｌ２Ｏ３処理した後、ポリオール処理、シロキサン処理してなるものである金属張り白色積層体である。
前記樹脂組成物中の白色顔料の含有率が１０〜７０重量％、より好ましくは２０〜５０重量％であり、前記樹脂組成物層の白色度が７０以上である。また、金属層を除去することにより露出させた前記白色樹脂層に、波長幅が４００ｎｍ〜４８０ｎｍであり４２０ｎｍに波長のピークを持つ青色光を空気中において白色樹脂層の単位面積あたりに対して９０Ｗ／ｍ２の強さで１０００時間連続して照射した後の白色度が６０以上である。
In the present invention, R in the general formula I is a tetravalent group having a cyclohexane structure, and the white pigment is titanium oxide, zirconium oxide, calcium oxide, silicon oxide, zinc oxide, aluminum oxide, zinc sulfide, It is at least one selected from the group consisting of calcium sulfate, barium sulfate, lead carbonate, lead hydroxide, basic zinc molybdate, basic calcium zinc molybdate, lead white, molybdenum white, and lithopone, especially the white color The pigment is rutile-type titanium oxide having a coating layer formed on the surface, and further, the titanium oxide coating layer is treated with SiO 2 or Al 2 O 3 , and the titanium oxide coating layer is after processing SiO 2 or Al 2 O 3, polyol process, the metal-clad white laminate is made by siloxane treatment It is.
The white pigment content in the resin composition is 10 to 70% by weight, more preferably 20 to 50% by weight, and the whiteness of the resin composition layer is 70 or more. Further, the white resin layer exposed by removing the metal layer is subjected to 90 W of blue light having a wavelength width of 400 nm to 480 nm and having a wavelength peak at 420 nm in the air per unit area of the white resin layer. The whiteness after continuous irradiation for 1000 hours at an intensity of / m 2 is 60 or more.
そして、本発明の白色樹脂層が、前記樹脂組成物の有機溶剤（溶媒）分散液を予め製造された金属箔に塗布した後、溶剤（溶媒）を蒸発させて形成したものである前記白色樹脂層が、予め製造した前記樹脂組成物フィルムに予め製造された金属箔を重ね、加熱圧着して形成したものであるフレキシブル金属張り白色積層体である。 The white resin layer according to the present invention is formed by applying an organic solvent (solvent) dispersion of the resin composition to a metal foil prepared in advance and then evaporating the solvent (solvent). The layer is a flexible metal-clad white laminate formed by stacking a pre-manufactured metal foil on the pre-manufactured resin composition film and thermocompression bonding.
本発明は、白色顔料、特に表面被覆処理したルチル型酸化チタンを配合してなる特定のポリイミド樹脂組成物を用いたフレキシブル金属張り白色積層体であり、白色度とその耐光性に優れ、特に、ＬＥＤ（発光ダイオード）を実装するプリント配線基板に好適に利用することができる。 The present invention is a flexible metal-clad white laminate using a specific polyimide resin composition formed by blending a white pigment, particularly a rutile-type titanium oxide that has been surface-coated, and is excellent in whiteness and its light resistance, It can utilize suitably for the printed wiring board which mounts LED (light emitting diode).
本発明で用いるポリイミドは、上記の一般式Ｉで示される繰り返し単位を有する。
一般式Ｉで示される繰り返し単位の含有量は、全繰り返し単位の１０〜１００モル％、好ましくは５０〜１００モル％であり、実質的に１００モル％であることが特に好ましい。また、ポリイミド１分子中の一般式Ｉで示される繰り返し単位の個数は、１０〜２０００であるのが好ましく、２０〜２００であるのがより好ましい。
The polyimide used in the present invention has a repeating unit represented by the above general formula I.
The content of the repeating unit represented by the general formula I is from 10 to 100 mol%, preferably from 50 to 100 mol%, particularly preferably substantially 100 mol%, based on all repeating units. In addition, the number of repeating units represented by the general formula I in one molecule of polyimide is preferably 10 to 2000, and more preferably 20 to 200.
一般式ＩのＲは、４価の脂肪族基である。好ましいＲとしてはシクロヘキサン、シクロペンタン、シクロブタン、ビシクロ［２．２．２］オクタ−７−エン構造を有する４価の置換基およびその立体異性体が挙げられる。より具体的には、下記構造式で表される４価の脂肪族基が挙げられ、中でもシクロヘキサンから誘導される４価の置換基およびその立体異性体がより好ましい。 R in the general formula I is a tetravalent aliphatic group. Preferred examples of R include a tetravalent substituent having a cyclohexane, cyclopentane, cyclobutane, bicyclo [2.2.2] oct-7-ene structure, and stereoisomers thereof. More specifically, a tetravalent aliphatic group represented by the following structural formula is exemplified, and among them, a tetravalent substituent derived from cyclohexane and a stereoisomer thereof are more preferable.
一般式ＩのΦは、炭素数２〜３９の構成単位であり、脂肪族構成単位、脂環族構成単位、芳香族構成単位、オルガノシロキサン構成単位、またはこれらの組み合わせあるいは繰り返しからなる構成単位であり、Φの主鎖には−Ｏ−、−ＳＯ２−、−ＣＯ−、−ＣＨ２−、−Ｃ（ＣＨ３）２−、−Ｃ２Ｈ４Ｏ−、および−Ｓ−からなる群から選ばれた少なくとも１の部分構造が介在していてもよいものである。
好ましいΦとしては、ポリアルキレン、末端がアルキルまたはアロマチックである（ポリ）オキシアルキレン、キシリレン、およびそれらのアルキル置換体、ハロゲン置換体などの脂肪族構成単位；シクロヘキサン、ジシクロヘキシルメタン、ジメチルシクロヘキサン、イソホロン、ノルボルナン、およびそれらのアルキル置換体、ハロゲン置換体などから誘導される脂環族構成単位；および、ベンゼン、ナフタレン、ビフェニル、ジフェニルメタン、ジフェニルエーテル、ジフェニルスルフォン、ベンゾフェノン、およびそれらのアルキル置換体,ハロゲン置換体などから誘導される芳香族構成単位、オルガノシロキサン構成単位が挙げられる。より具体的には、下記構造式で表される構成単位が挙げられる。
なお、下記の構造式中のＲは、二価のアルキルまたはアロマチック基を示し、ｎは上記したΦの炭素数２〜３９を満たす整数である。
Φ in the general formula I is a structural unit having 2 to 39 carbon atoms, and is a structural unit composed of an aliphatic structural unit, an alicyclic structural unit, an aromatic structural unit, an organosiloxane structural unit, or a combination or repetition thereof. And the main chain of Φ is a group consisting of —O—, —SO 2 —, —CO—, —CH 2 —, —C (CH 3 ) 2 —, —C 2 H 4 O—, and —S—. At least one partial structure selected from may be interposed.
Preferable Φ includes polyalkylene, (poly) oxyalkylene having a terminal alkyl or aromatic, xylylene, and aliphatic structural units such as alkyl-substituted and halogen-substituted products thereof; cyclohexane, dicyclohexylmethane, dimethylcyclohexane, isophorone , Norbornane, and alicyclic structural units derived from their alkyl-substituted, halogen-substituted, etc .; and benzene, naphthalene, biphenyl, diphenylmethane, diphenyl ether, diphenylsulfone, benzophenone, and their alkyl-substituted, halogen-substituted Aromatic structural units and organosiloxane structural units derived from the body and the like. More specifically, structural units represented by the following structural formulas can be given.
In the following structural formula, R represents a divalent alkyl or aromatic group, and n is an integer satisfying the above-described Φ carbon number of 2 to 39.
本発明で用いるポリイミドは、通常、テトラカルボン酸成分とジアミン系成分（ジアミン及びその誘導体）とを溶液中で反応させることにより得られる。
反応に用いるテトラカルボン酸成分は、脂肪族テトラカルボン酸、脂肪族テトラカルボン酸アルキルエステル、脂肪族テトラカルボン酸二無水物が挙げられる。
具体的には、１，２，４，５−シクロヘキサンテトラカルボン酸、１，２，４，５−シクロヘキサンテトラカルボン酸二無水物、１，２，４，５−シクロヘキサンテトラカルボン酸メチルエステル、１，２，３，４−ブタンテトラカルボン酸、１，２，３，４−ブタンテトラカルボン酸二無水物、１，２，３，４−ブタンテトラカルボン酸メチルエステル、１，２，３，４−シクロブタンテトラカルボン酸、１，２，３，４−シクロブタンテトラカルボン酸二無水物、１，２，３，４−シクロブタンテトラカルボン酸メチルエステル、１，２，４，５−シクロペンタンテトラカルボン酸、１，２，４，５−シクロペンタンテトラカルボン酸二無水物、１，２，４，５−シクロペンタンテトラカルボン酸メチルエステル、３−カルボキシメチル−１，２，４−シクロペンタントリカルボン酸、ビシクロ[２．２．２]オクタ−７−エン−２，３，５，６−テトラカルボン酸、ビシクロ[２．２．２]オクタ−７−エン−２，３，５，６−テトラカルボン酸二無水物、ビシクロ[２．２．２]オクタ−７−エン−２，３，５，６−テトラカルボン酸メチルエステル、ジシクロヘキシルテトラカルボン酸、ジシクロヘキシルテトラカルボン酸二無水物、ジシクロヘキシルテトラカルボン酸メチルエステルなどが挙げられる。これらテトラカルボン酸成分は位置異性体を含む。
The polyimide used in the present invention is usually obtained by reacting a tetracarboxylic acid component and a diamine component (diamine and derivatives thereof) in a solution.
Examples of the tetracarboxylic acid component used in the reaction include aliphatic tetracarboxylic acid, aliphatic tetracarboxylic acid alkyl ester, and aliphatic tetracarboxylic dianhydride.
Specifically, 1,2,4,5-cyclohexanetetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic acid methyl ester, 1 , 2,3,4-butanetetracarboxylic acid, 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-butanetetracarboxylic acid methyl ester, 1,2,3,4 -Cyclobutanetetracarboxylic acid, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic acid methyl ester, 1,2,4,5-cyclopentanetetracarboxylic acid 1,2,4,5-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclopentanetetracarboxylic acid methyl ester, 3-carboxymethyl 1,2,4-cyclopentanetricarboxylic acid, bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic acid, bicyclo [2.2.2] oct-7-ene -2,3,5,6-tetracarboxylic dianhydride, bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic acid methyl ester, dicyclohexyltetracarboxylic acid, dicyclohexyl Examples thereof include tetracarboxylic dianhydride and dicyclohexyl tetracarboxylic acid methyl ester. These tetracarboxylic acid components include regioisomers.
上記テトラカルボン酸成分のうちシクロへキサンテトラカルボン酸骨格を有するポリイミドは高分子量化が容易で、フレキシブルなフィルムが得られ易い上に、溶剤に対する溶解度も充分に大きいので、フィルムの成形加工の面で有利である。この点から特に、これらの中でシクロヘキサンテトラカルボン酸二無水物が好ましい。 Among the above tetracarboxylic acid components, polyimide having a cyclohexanetetracarboxylic acid skeleton is easy to obtain a high molecular weight, and a flexible film can be easily obtained, and the solubility in a solvent is sufficiently high. Is advantageous. Among these, cyclohexanetetracarboxylic dianhydride is particularly preferable among these.
前記のテトラカルボン酸成分には、ポリイミドの溶剤可溶性、フィルムのフレキシビリティ、熱圧着性、透明性を損なわない範囲で、他のテトラカルボン酸またはその誘導体、例えば、ピロメリット酸、３，３’，４，４’−ビフェニルテトラカルボン酸、２，３，３’，４’−ビフェニルテトラカルボン酸、２，２−ビス（３，４−ジカルボキシフェニル）プロパン、２，２−ビス（２，３−ジカルボキシフェニル）プロパン、２，２−ビス（３，４−ジカルボキシフェニル）−１，１，１，３，３，３−ヘキサフルオロプロパン、２，２−ビス（２，３−ジカルボキシフェニル）−１，１，１，３，３，３−ヘキサフルオロプロパン、ビス（３，４−ジカルボキシフェニル）スルホン、ビス（３，４−ジカルボキシフェニル）エーテル、ビス（２，３−ジカルボキシフェニル）エーテル、３，３’，４、４’−ベンゾフェノンテトラカルボン酸、２，２’，３，３’−ベンゾフェノンテトラカルボン酸、４，４−（ｐ−フェニレンジオキシ）ジフタル酸、４，４−（ｍ−フェニレンジオキシ）ジフタル酸、エチレンテトラカルボン酸、１，１−ビス（２，３−ジカルボキシフェニル）エタン、ビス（２，３−ジカルボキシフェニル）メタン、ビス（３，４−ジカルボキシフェニル）メタン、およびそれらの誘導体から選ばれる少なくとも１種の化合物を含んでいてもよい。 The tetracarboxylic acid component includes other tetracarboxylic acids or derivatives thereof such as pyromellitic acid, 3, 3 ′ within the range that does not impair the solvent solubility of polyimide, film flexibility, thermocompression bonding, and transparency. , 4,4′-biphenyltetracarboxylic acid, 2,3,3 ′, 4′-biphenyltetracarboxylic acid, 2,2-bis (3,4-dicarboxyphenyl) propane, 2,2-bis (2, 3-dicarboxyphenyl) propane, 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (2,3-di Carboxyphenyl) -1,1,1,3,3,3-hexafluoropropane, bis (3,4-dicarboxyphenyl) sulfone, bis (3,4-dicarboxyphenyl) ether, (2,3-dicarboxyphenyl) ether, 3,3 ′, 4,4′-benzophenone tetracarboxylic acid, 2,2 ′, 3,3′-benzophenone tetracarboxylic acid, 4,4- (p-pheny Rangeoxy) diphthalic acid, 4,4- (m-phenylenedioxy) diphthalic acid, ethylenetetracarboxylic acid, 1,1-bis (2,3-dicarboxyphenyl) ethane, bis (2,3-dicarboxyphenyl) ) At least one compound selected from methane, bis (3,4-dicarboxyphenyl) methane, and derivatives thereof may be included.
反応に用いるジアミン系成分としては、ジアミン、ジイソシアネート、ジアミノジシラン類などが上げられるが、好ましいのはジアミンである。ジアミン系成分中のジアミン含量は、好ましくは５０モル％以上（１００モル％を含む）である。 Examples of the diamine component used in the reaction include diamines, diisocyanates, diaminodisilanes, and the like. Preferred is a diamine. The diamine content in the diamine-based component is preferably 50 mol% or more (including 100 mol%).
前記ジアミンは、脂肪族ジアミンであっても芳香族ジアミンであってもよく、それらの混合物でもよい。なお、本発明において“芳香族ジアミン”とは、アミノ基が芳香族環に直接結合しているジアミンを表し、その構造の一部に脂肪族基、脂環基、その他の置換基を含んでいてもよい。“脂肪族ジアミン”とは、アミノ基が脂肪族基または脂環基に直接結合しているジアミンを表し、その構造の一部に芳香族基、その他の置換基を含んでいてもよい。 The diamine may be an aliphatic diamine, an aromatic diamine, or a mixture thereof. In the present invention, “aromatic diamine” means a diamine in which an amino group is directly bonded to an aromatic ring, and an aliphatic group, an alicyclic group, and other substituents are included in a part of the structure. May be. The “aliphatic diamine” represents a diamine in which an amino group is directly bonded to an aliphatic group or an alicyclic group, and an aromatic group and other substituents may be included in a part of the structure.
前記の脂肪族ジアミンとしては、例えば、４，４’−ジアミノジシクロヘキシルメタン、エチレンジアミン、ヘキサメチレンジアミン、ポリエチレングリコールビス（３−アミノプロピル）エーテル、ポリプロピレングリコールビス（３−アミノプロピル）エーテル、１,３−ビス（アミノメチル）シクロヘキサン、１，４−ビス（アミノメチル）シクロヘキサン、ｍ−キシリレンジアミン、ｐ−キシリレンジアミン、イソホロンジアミン、ノルボルナンジアミン、シロキサンジアミン類などが挙げられる。
前記の芳香族ジアミンとしては、例えば、４,４’−ジアミノジフェニルエーテル、４,４’−ジアミノジフェニルメタン、４,４’−ジアミノジフェニルスルホン、ｍ−フェニレンジアミン、ｐ−フェニレンジアミン、ジアミノベンゾフェノン、２,６−ジアミノナフタレン、１,５−ジアミノナフタレンなどが挙げられる。
Examples of the aliphatic diamine include 4,4′-diaminodicyclohexylmethane, ethylenediamine, hexamethylenediamine, polyethylene glycol bis (3-aminopropyl) ether, polypropylene glycol bis (3-aminopropyl) ether, and 1,3. -Bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, m-xylylenediamine, p-xylylenediamine, isophorone diamine, norbornane diamine, siloxane diamines and the like.
Examples of the aromatic diamine include 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, m-phenylenediamine, p-phenylenediamine, diaminobenzophenone, 2, Examples include 6-diaminonaphthalene and 1,5-diaminonaphthalene.
樹脂組成物を構成するポリイミドのガラス転移温度は、主に選択するジアミンにより決定されるが、概ね３５０℃以下である。ガラス転移温度以上の温度で接着性が発現する。ガラス転移温度が高すぎると熱圧着温度が高くなりすぎるので不適当であり、ガラス転移温度が低すぎるとポリイミド層の耐熱性が不足し、好ましくない。ガラス転移温度の範囲は２００〜３５０℃、好ましくは、２５０〜３２０℃である。 Although the glass transition temperature of the polyimide which comprises a resin composition is mainly determined by the diamine selected, it is 350 degrees C or less in general. Adhesiveness develops at temperatures above the glass transition temperature. If the glass transition temperature is too high, the thermocompression bonding temperature becomes too high, which is inappropriate. If the glass transition temperature is too low, the heat resistance of the polyimide layer is insufficient, which is not preferable. The range of the glass transition temperature is 200 to 350 ° C, preferably 250 to 320 ° C.
本発明のポリイミドは、通常、有機溶媒溶液として製造する。
有機溶媒としては特に限定されないが、例えば、Ｎ−メチル−２−ピロリドン、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ，Ｎ−ジエチルアセトアミド、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジエチルホルムアミド、Ｎ−メチルカプロラクタム、ヘキサメチルホスホルアミド、テトラメチレンスルホン、ジメチルスルホキシド、ｍ−クレゾ−ル、フェノ−ル、ｐ−クロルフェノール、２−クロル−４−ヒドロキシトルエン、ジグライム、トリグライム、テトラグライム、ジオキサン、γ−ブチロラクトン、ジオキソラン、シクロヘキサノン、シクロペンタノンなどが使用可能であり、２種以上を併用しても良い。しかし、ポリイミドと溶媒からなるポリイミド溶液として用いる場合、Ｎ−メチル−２−ピロリドン（ＮＭＰ）、Ｎ，Ｎ−ジメチルアセトアミド（ＤＭＡＣ）、γ−ブチロラクトン（ＧＢＬ）を単独、又は併用するのが好ましい。また、溶液重合による製造の場合、これら溶媒と併せてヘキサン、ヘプタン、ベンゼン、トルエン、キシレン、クロルベンゼン、ｏ−ジクロロベンゼン等の貧溶媒を、重合体が析出しない程度に使用することができる。
The polyimide of the present invention is usually produced as an organic solvent solution.
The organic solvent is not particularly limited. For example, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylformamide, N, N-diethylformamide, N-methyl Caprolactam, hexamethylphosphoramide, tetramethylene sulfone, dimethyl sulfoxide, m-cresol, phenol, p-chlorophenol, 2-chloro-4-hydroxytoluene, diglyme, triglyme, tetraglyme, dioxane, γ- Butyrolactone, dioxolane, cyclohexanone, cyclopentanone and the like can be used, and two or more kinds may be used in combination. However, when used as a polyimide solution comprising polyimide and a solvent, it is preferable to use N-methyl-2-pyrrolidone (NMP), N, N-dimethylacetamide (DMAC), or γ-butyrolactone (GBL) alone or in combination. In the case of production by solution polymerization, a poor solvent such as hexane, heptane, benzene, toluene, xylene, chlorobenzene, o-dichlorobenzene and the like can be used together with these solvents to such an extent that the polymer does not precipitate.
ポリイミドは、上記したテトラカルボン酸二無水物成分と、ジアミン成分とを用いて、いずれの製造法でも製造可能である。これらとしては、（１）溶液重合法、（２）ポリアミック酸溶液を得て製膜などした後、イミド化する方法、（３）塩又はオリゴマーを得、固相重合を行なう方法、（４）テトラカルボン酸二無水物とジイソシアネートを原料とする方法、その他、従来公知の方法で可能であり、それぞれの方法を併用することもできる。更に、反応にあたって、酸、三級アミン類、無水物といった従来公知の触媒などを用いる事ができる。 Polyimide can be produced by any production method using the above-described tetracarboxylic dianhydride component and diamine component. These include (1) a solution polymerization method, (2) a method of forming a film after obtaining a polyamic acid solution, and (3) a method of obtaining a salt or oligomer and performing solid phase polymerization, (4) It is possible by a method using tetracarboxylic dianhydride and diisocyanate as raw materials, or other conventionally known methods, and these methods can be used in combination. Furthermore, in the reaction, conventionally known catalysts such as acids, tertiary amines, and anhydrides can be used.
ポリイミドの有機溶媒溶液は下記の（１）〜（３）の方法で製造する。
（１）．ジアミン系成分の有機溶媒溶液にテトラカルボン酸成分を添加し、または、テトラカルボン酸成分の有機溶媒溶液にジアミン系成分を添加し、好ましくは８０℃以下、特に室温付近ないしそれ以下の温度で０．５〜３時間保つ。得られた反応中間体のポリアミド酸溶液にトルエンあるいはキシレンなどの共沸脱水溶媒を添加して、生成水を共沸により系外へ除きつつ脱水反応を行い、ポリイミドの有機溶媒溶液を得る。
（２）．上記１と同様にして得た反応中間体のポリアミド酸溶液に無水酢酸などの脱水剤を加えてイミド化した後、メタノールなどのポリイミドに対する溶解能が乏しい溶媒を添加して、ポリイミドを沈殿させる。ろ過・洗浄・乾燥により固体として分離した後、有機溶媒に溶解してポリイミドの有機溶媒溶液を得る。
（３）．上記１において、クレゾールなどの高沸点溶媒を用いてポリアミド酸溶液を調製し、そのまま１５０〜２２０℃に３〜１２時間保ってポリイミド化させた後、メタノールなどのポリイミドに対する溶解能が乏しい溶媒を添加して、ポリイミドを沈殿させる。ろ過・洗浄・乾燥により固体として分離した後、Ｎ，Ｎ−ジメチルアセトアミドなどの有機溶媒に溶解してポリイミドの有機溶媒溶液を得る。
The organic solvent solution of polyimide is produced by the following methods (1) to (3).
(1). The tetracarboxylic acid component is added to the organic solvent solution of the diamine-based component, or the diamine-based component is added to the organic solvent solution of the tetracarboxylic acid component, and is preferably 0 ° C. or less, particularly at about room temperature or lower. Hold for 5 to 3 hours. An azeotropic dehydration solvent such as toluene or xylene is added to the resulting polyamic acid solution of the reaction intermediate, and a dehydration reaction is performed while removing the generated water out of the system by azeotropy to obtain an organic solvent solution of polyimide.
(2). After adding a dehydrating agent such as acetic anhydride to the polyamic acid solution of the reaction intermediate obtained in the same manner as in 1 above to imidize, a solvent having poor solubility in polyimide such as methanol is added to precipitate the polyimide. After being separated as a solid by filtration, washing and drying, it is dissolved in an organic solvent to obtain an organic solvent solution of polyimide.
(3). In 1 above, a polyamic acid solution is prepared using a high-boiling solvent such as cresol, and is maintained as it is at 150 to 220 ° C. for 3 to 12 hours to form a polyimide, and then a solvent having poor solubility in polyimide such as methanol is added. Then, the polyimide is precipitated. After being separated as a solid by filtration, washing and drying, it is dissolved in an organic solvent such as N, N-dimethylacetamide to obtain an organic solvent solution of polyimide.
本発明のポリイミドを溶液重合で製造する場合、触媒として３級アミン化合物を用いる事が好ましい。これらとしては、トリメチルアミン、トリエチルアミン（ＴＥＡ）、トリプロピルアミン、トリブチルアミン、トリエタノールアミン、Ｎ，Ｎ−ジメチルエタノールアミン、Ｎ，Ｎ−ジエチルエタノールアミン、トリエチレンジアミン、Ｎ−メチルピロリジン、Ｎ−エチルピロリジン、Ｎ−メチルピペリジン、Ｎ−エチルピペリジン、イミダゾール、ピリジン、キノリン、イソキノリンなどが挙げられる。 When manufacturing the polyimide of this invention by solution polymerization, it is preferable to use a tertiary amine compound as a catalyst. These include trimethylamine, triethylamine (TEA), tripropylamine, tributylamine, triethanolamine, N, N-dimethylethanolamine, N, N-diethylethanolamine, triethylenediamine, N-methylpyrrolidine, N-ethylpyrrolidine. N-methylpiperidine, N-ethylpiperidine, imidazole, pyridine, quinoline, isoquinoline and the like.
また、ポリイミドの溶液の濃度は、５〜７０重量％、好ましくは１０〜５０重量％であり、特に１０〜４０重量％がより好ましい。５重量％未満であると樹脂組成物層の厚さが不均一になり易く好ましく、７０重量％を超えると粘度が著しく大きくなり、取り扱いが困難となり好ましくない。
ポリイミドの有機溶媒溶液には、下記するように白色顔料を配合するが、フッ素系、ポリシロキサン系などの界面活性剤を添加しても良い。これによって、表面平滑性の良好なポリイミド層、ポリイミドフィルムを得やすくなる。
The concentration of the polyimide solution is 5 to 70% by weight, preferably 10 to 50% by weight, and more preferably 10 to 40% by weight. If it is less than 5% by weight, the thickness of the resin composition layer tends to be nonuniform, and if it exceeds 70% by weight, the viscosity becomes remarkably large and handling becomes difficult.
In the organic solvent solution of polyimide, a white pigment is blended as described below, but a fluorine-based or polysiloxane-based surfactant may be added. This makes it easy to obtain a polyimide layer and a polyimide film with good surface smoothness.
本発明で用いる白色顔料は、酸化チタン、酸化ジルコニウム、酸化カルシウム、酸化ケイ素、酸化亜鉛、酸化アルミニウム、硫化亜鉛、硫酸カルシウム、硫酸バリウム、炭酸鉛、水酸化鉛、塩基性モリブデン酸亜鉛、塩基性モリブデン酸カルシウム亜鉛、鉛白、モリブデンホワイト、およびリトポンからなる群より選ばれる１種以上のものである。
これらの中で、、表面に被覆層を形成したルチル型酸化チタンが好ましく、被覆層としては、ＳｉＯ２またはＡｌ２Ｏ３処理であり、さらに、被覆層が、ＳｉＯ２またはＡｌ２Ｏ３処理した後、ポリオール処理、シロキサン処理してなるものであるルチル型酸化チタンが好ましい。
The white pigment used in the present invention is titanium oxide, zirconium oxide, calcium oxide, silicon oxide, zinc oxide, aluminum oxide, zinc sulfide, calcium sulfate, barium sulfate, lead carbonate, lead hydroxide, basic zinc molybdate, basic One or more selected from the group consisting of calcium zinc molybdate, white lead, white molybdenum, and lithopone.
Among these, rutile type titanium oxide having a coating layer formed on the surface is preferable. The coating layer is treated with SiO 2 or Al 2 O 3 , and the coating layer is treated with SiO 2 or Al 2 O 3. Then, rutile type titanium oxide which is obtained by polyol treatment or siloxane treatment is preferred.
なお、白色顔料は通常、ポリイミド溶液に配合した白色顔料分散液として用いる。配合は、ポリイミドの合成、溶解操作の前、合成中、あるいは合成終了後、さらには合成終了後希釈溶媒にて希釈した後のいずれかで行っても良いが、通常、合成終了後に行う。
白色顔料の攪拌分散は適切な攪拌能力を有する攪拌機を付設した攪拌槽にて実施してもよく、ボールミルなどの混合を目的とした装置、または、公転・自転型の混合装置を用いても行うことができる。
The white pigment is usually used as a white pigment dispersion mixed in a polyimide solution. The blending may be performed either before or after the synthesis or dissolution of the polyimide, during the synthesis, after the synthesis, or after being diluted with a diluting solvent after the synthesis is completed.
Stirring and dispersion of the white pigment may be performed in a stirring tank equipped with a stirrer having an appropriate stirring ability, or may be performed using a device for mixing such as a ball mill or a revolving / spinning type mixing device. be able to.
本発明で用いる白色顔料の粒径は０．０５〜５μｍ、好ましくは０．１〜１μｍである。粒径が０．０５μｍより小さい場合には、光線反射率が低下し、一方、５μｍを超える場合には樹脂組成物層表面の凹凸が目立ち外観不良を起こしたり、機械的性質、特に破断伸びの低下が大きくなるので好ましくない。
また、ポリイミドに対する白色顔料の含有率は、固形分基準で１０〜７０重量％、より好ましくは２０〜５０重量％である。含有率が７０重量％を超える場合は、機械的性質、特に破断強度が低下したり、十分な接着強度が得られなくなり好ましくない。また、含有率が１０重量％より小さい場合は、十分な反射率と白色度が得られなくなり好ましくない。
The particle size of the white pigment used in the present invention is 0.05 to 5 μm, preferably 0.1 to 1 μm. When the particle size is smaller than 0.05 μm, the light reflectivity is lowered. On the other hand, when it exceeds 5 μm, the unevenness on the surface of the resin composition layer is conspicuous, resulting in poor appearance or mechanical properties, particularly elongation at break. This is not preferable because the reduction is increased.
Moreover, the content rate of the white pigment with respect to a polyimide is 10 to 70 weight% on a solid content basis, More preferably, it is 20 to 50 weight%. When the content exceeds 70% by weight, the mechanical properties, particularly the breaking strength, is lowered, and sufficient adhesive strength cannot be obtained, which is not preferable. Further, when the content is less than 10% by weight, it is not preferable because sufficient reflectance and whiteness cannot be obtained.
本発明の白色樹脂層の反射率は、４１０ｎｍ〜７８０ｎｍにおいて５０％以上であることが好ましい。５０％未満では、光の裏抜けが生じるため好ましくない。
また、白色樹脂層の白色度は７０以上であることが好ましい。白色度７０未満では、光の吸収が生じ黄色味を帯びてしまうので好ましくない。
さらに、本発明においては、金属層を除去することにより露出させた前記白色樹脂層に、波長幅が４００ｎｍ〜４８０ｎｍであり４２０ｎｍに波長のピークを持つ青色光を空気中において白色樹脂層の単位面積あたりに対して９０Ｗ／ｍ２の強さで１０００時間連続して照射した後の白色度が６０以上、好ましくは７０以上であることが実用上からは好ましい。白色度６０未満では、光の吸収が大きく黄色に着色してしまうので好ましくない。
The reflectance of the white resin layer of the present invention is preferably 50% or more at 410 nm to 780 nm. If it is less than 50%, it is not preferable because light breakthrough occurs.
Moreover, it is preferable that the whiteness degree of a white resin layer is 70 or more. If the whiteness is less than 70, light is absorbed and yellowish.
Furthermore, in the present invention, the white resin layer exposed by removing the metal layer is subjected to blue light having a wavelength width of 400 nm to 480 nm and a wavelength peak at 420 nm in the air in the unit area of the white resin layer. It is practically preferable that the whiteness after continuous irradiation for 1000 hours at an intensity of 90 W / m 2 is about 60 or more, preferably 70 or more. If the degree of whiteness is less than 60, light absorption is large and the color is yellow.
金属層に用いられる金属箔としては、銅、アルミニウム、ステンレス、金、銀、ニッケルなどがあげられるが、好ましくは、銅、アルミニウム、ステンレスである。金属箔の厚さは、特に制限がないが、通常使用される５〜１００μｍの範囲であれば良好な加工性が得られる。
また、金属層はスパッタリング、蒸着および無電解めっきなどによっても製造でき、金属としては、銅、ニッケル、クロム、すず、コバルト、金などがあげられるが、好ましくは、銅、ニッケル、金であり、適宜、多層化される。金属層の厚さは、特に制限がないが、薄膜形成方法の特徴を活かすには他の方法では得ることが難しい１０μｍ以下が好ましく、２〜１０μｍがより好ましい。
Examples of the metal foil used for the metal layer include copper, aluminum, stainless steel, gold, silver, and nickel. Copper, aluminum, and stainless steel are preferable. Although there is no restriction | limiting in particular in the thickness of metal foil, if it is the range of 5-100 micrometers normally used, favorable workability will be obtained.
Further, the metal layer can also be produced by sputtering, vapor deposition, electroless plating, etc., and examples of the metal include copper, nickel, chromium, tin, cobalt, gold, etc., preferably copper, nickel, gold, It is multilayered as appropriate. The thickness of the metal layer is not particularly limited, but is preferably 10 μm or less, more preferably 2 to 10 μm, which is difficult to obtain by other methods in order to make use of the characteristics of the thin film forming method.
本発明においては、適宜、絶縁性基材を使用できる。
これらとしてはフレキシブルタイプのものが好ましい。フレキシブルタイプの絶縁性基材としては、ポリイミド、ポリベンズイミダゾール、ポリベンズオキサゾール、ポリアミド（アラミドを含む）、ポリエーテルイミド、ポリアミドイミド、ポリエステル（液晶性ポリエステルを含む）、ポリスルホン、ポリエーテルスルホン、ポリエーテルケトン、ポリエーテルエーテルケトンが挙げられ、好ましくは、ポリイミド、ポリベンズイミダゾール、ポリアミド（アラミドを含む）、ポリエーテルイミド、ポリアミドイミド、ポリエーテルスルホンである。また、絶縁性基材として本発明の樹脂組成物からなるものも当然に用いることができる。フレキシブルタイプの絶縁性基材の厚さは特に限定されないが、３〜１５０μｍであるのが好ましい。
また、これらを用いて得た片面金属箔張シートやフィルムから製造したプリント配線シートやフィルムも上記絶縁性基材と同様に用いて金属箔張とし、多層プリント配線シートやフィルムとできる。
In the present invention, an insulating base material can be used as appropriate.
These are preferably flexible types. Flexible insulating base materials include polyimide, polybenzimidazole, polybenzoxazole, polyamide (including aramid), polyetherimide, polyamideimide, polyester (including liquid crystalline polyester), polysulfone, polyethersulfone, poly Examples include ether ketone and polyether ether ketone, and preferred are polyimide, polybenzimidazole, polyamide (including aramid), polyetherimide, polyamideimide, and polyethersulfone. Moreover, what consists of the resin composition of this invention as an insulating base material can also be used naturally. The thickness of the flexible type insulating substrate is not particularly limited, but is preferably 3 to 150 μm.
Moreover, the printed wiring sheet and film manufactured from the single-sided metal foil tension sheet | seat and film obtained using these can also be used as a metal foil tension | tensile_strength similarly to the said insulating base material, and can be used as a multilayer printed wiring sheet and film.
本発明のフレキシブル金属張り白色積層体は、上記に説明した構成成分を用い、一般に、下記（１）〜（４）で製造する。
（１）．金属箔に、白色樹脂の溶液を塗布し、溶媒を除去する方法。
（２）．金属箔を、予め製造した白色樹脂のフィルムと重ね、加熱圧着する方法。
（３）．金属箔を、予め白色樹脂層を形成した絶縁基材と重ね、加熱圧着する方法。
（４）．予め製造した白色樹脂のフィルムまたは白色樹脂層を形成した絶縁基材上に、金属層をスパッタリング、蒸着、その他の気相法や無電解メッキなどし、適宜、電解メッキして形成する方法。
本発明の一般式Ｉのポリイミドは、溶液として使用できること、および加熱圧着できることから、これらを利用した（１）〜（３）が好ましく、特に、（１）および（２）が好ましい。
The flexible metal-clad white laminate of the present invention is generally produced by the following (1) to (4) using the components described above.
(1). A method of applying a white resin solution to a metal foil to remove the solvent.
(2). A method in which a metal foil is overlapped with a previously produced white resin film and thermocompression bonded.
(3). A method in which a metal foil is overlapped with an insulating base material on which a white resin layer is previously formed and thermocompression bonded.
(4). A method in which a metal layer is formed by sputtering, vapor deposition, other vapor phase methods, electroless plating, or the like, and electrolytic plating as appropriate on an insulating base material on which a white resin film or a white resin layer is formed in advance.
Since the polyimide of the general formula I of the present invention can be used as a solution and can be thermocompression bonded, (1) to (3) utilizing these are preferable, and (1) and (2) are particularly preferable.
上記において、予め白色樹脂のフィルムを製造する方法は、通常、剥離性を付与した基材上に白色樹脂溶液を塗布し、溶剤を除去し、剥離し、適宜、後乾燥することによる。
金属箔上または絶縁性基材上に白色樹脂層を形成する方法、または予め白色樹脂のフィルムを製造する方法において、溶剤の蒸発除去は、通常、温度１００〜３５０℃にて、適宜、不活性雰囲気或いは減圧の条件下に溶剤を蒸発させることにより製造する。
フィルムまたは白色樹脂層の厚さは３〜１００μｍであり、白色樹脂のフィルムや金属箔上に形成する白色樹脂層としては１５〜１００μｍを通常選択し、絶縁性基材上に形成する白色樹脂層としては３〜５０μｍを通常選択する。
なお、上記（４）において、蒸着法を用いる場合の蒸着法は、通常の蒸着に加えて、ＣＶＤ法、イオンプレーティング法等も適用できる。蒸着法にて金属層を形成する場合、この時に金属層を形成する前に、白色樹脂層面をアルカリ性薬液による処理、プラズマ処理、サンドブラスト処理等の公知の前処理を施してもよい。このような前処理により、樹脂組成物フィルムと金属層との接着強度が一層向上する。
In the above, the method for producing a white resin film in advance is usually by applying a white resin solution on a substrate to which peelability has been imparted, removing the solvent, peeling off, and appropriately post-drying.
In a method of forming a white resin layer on a metal foil or an insulating substrate or a method of producing a white resin film in advance, the solvent is usually removed by evaporation at a temperature of 100 to 350 ° C. It is produced by evaporating the solvent under atmospheric or reduced pressure conditions.
The thickness of the film or white resin layer is 3 to 100 μm, and the white resin layer formed on the insulating substrate is usually selected from 15 to 100 μm as the white resin layer formed on the white resin film or metal foil. Usually, 3 to 50 μm is selected.
In the above (4), as a vapor deposition method when using the vapor deposition method, a CVD method, an ion plating method, or the like can be applied in addition to the normal vapor deposition. When forming a metal layer by a vapor deposition method, before forming a metal layer at this time, you may perform well-known pretreatments, such as a process by an alkaline chemical | medical solution, a plasma process, and a sandblast process, on the white resin layer surface. By such pretreatment, the adhesive strength between the resin composition film and the metal layer is further improved.
また、白色樹脂層は、加熱圧着を用いることにより、金属箔、絶縁基材、プリント配線網などの面と積層して一体化できる。
さらに、白色樹脂層に、金属箔、白色樹脂層を形成した金属箔の白色樹脂層面、絶縁フィルムおよび白色樹脂層を形成した金属箔並びに絶縁フィルムおよび白色樹脂フィルムおよび金属箔などを重ね熱圧着して両面張りとすること、さらに、プリント配線板の配線上に、上記の各方法により得られた白色樹脂層を重ね熱圧着して多層化することなど適宜実施できる。なお、プリント配線板は、本フレキシブル金属張り白色積層体から製造したものも当然に含まれるものである。
Further, the white resin layer can be laminated and integrated with a surface such as a metal foil, an insulating base, and a printed wiring network by using thermocompression bonding.
Furthermore, the white resin layer, the white resin layer surface of the metal foil on which the white resin layer is formed, the metal foil on which the insulating film and the white resin layer are formed, the insulating film, the white resin film, and the metal foil are overlapped and thermocompression bonded. Further, it is possible to appropriately carry out double-sided stretching, and further, multilayering by overlapping the white resin layer obtained by each of the above methods on the wiring of the printed wiring board by thermocompression bonding. The printed wiring board naturally includes those produced from the flexible metal-clad white laminate.
熱圧着は、熱プレスにより行ってもよいし、加圧ロールなどを使用して連続的に行ってもよい。熱圧着温度は、好ましくは２００〜４００℃、より好ましくは２５０〜３５０℃である。加圧力は、好ましくは０．１〜２００ｋｇｆ／ｃｍ２、より好ましくは１〜１００ｋｇｆ／ｃｍ２である。また、溶剤及び気泡を除くために減圧雰囲気で熱圧着しても良い。以上の条件で製造されたフレキシブル金属張り白色積層体における金属層と樹脂組成物層との接着強度は極めて良好であり、例えば電解銅箔と樹脂組成物層では、１ｋｇｆ／ｃｍ２以上の接着強度が達成される。 Thermocompression bonding may be performed by hot pressing, or may be performed continuously using a pressure roll or the like. The thermocompression bonding temperature is preferably 200 to 400 ° C, more preferably 250 to 350 ° C. The applied pressure is preferably 0.1 to 200 kgf / cm 2 , more preferably 1 to 100 kgf / cm 2 . Further, thermocompression bonding may be performed in a reduced pressure atmosphere to remove the solvent and bubbles. The adhesive strength between the metal layer and the resin composition layer in the flexible metal-clad white laminate produced under the above conditions is extremely good. For example, in the electrolytic copper foil and the resin composition layer, the adhesive strength is 1 kgf / cm 2 or more. Is achieved.
本発明に用いられる樹脂組成物を構成するポリイミドは、上記に例示した有機溶媒に可溶性である。そのため、上記の各方法により得られた金属張り白色積層体や回路パターンを形成した後のプリント配線板の樹脂組成物層を、非プロトン性極性有機溶媒をエッチャントとしてウェットエッチングすることによりパターニングすることが可能であり、例えば、ビアホールやフライングリードの形成、端子部分のカバーコートの除去に適用できる。 The polyimide constituting the resin composition used in the present invention is soluble in the organic solvents exemplified above. Therefore, patterning the resin composition layer of the printed wiring board after forming the metal-clad white laminate and circuit pattern obtained by the above methods by wet etching using an aprotic polar organic solvent as an etchant For example, it can be applied to the formation of via holes and flying leads, and the removal of the cover coat of the terminal portion.
以下、実施例により本発明を具体的に説明する。なお、本発明はこれらの実施例により何ら制限されるものではない。 Hereinafter, the present invention will be described specifically by way of examples. In addition, this invention is not restrict | limited at all by these Examples.
実施例および比較例で得られたポリイミドフィルム、樹脂組成物フィルム、片面フレキシブル銅張り積層板、および両面フレキシブル銅張り積層板の評価は以下のように行った。また使用した白色顔料の粒径測定は以下のように行った。
（１）ガラス転移温度
島津製作所（Shimadzu Corporation）製の示差走査熱量計装置（ＤＳＣ−５０）を用い、昇温速度１０℃／ｍｉｎの条件でＤＳＣ測定を行い、ガラス転移温度を求めた。
（２）接着強度
ＪＩＳ Ｃ ６４７１に準拠して回転式冶具を用いて９０°剥離強度を測定した。
（３）反射率
東京電色製の分光白色度光度計ＥＲＰ−８０ＷＸを用い、４５０ｎｍと５５０ｎｍを樹脂組成物層に照射して分光反射率を測定した。
Evaluation of the polyimide films, resin composition films, single-sided flexible copper-clad laminates, and double-sided flexible copper-clad laminates obtained in Examples and Comparative Examples was performed as follows. The particle size of the white pigment used was measured as follows.
(1) Glass transition temperature Using a differential scanning calorimeter (DSC-50) manufactured by Shimadzu Corporation, DSC measurement was performed under the condition of a heating rate of 10 ° C./min to obtain a glass transition temperature.
(2) Adhesive strength 90 ° peel strength was measured using a rotary jig in accordance with JIS C 6471.
(3) Reflectance Using a spectral whiteness photometer ERP-80WX manufactured by Tokyo Denshoku, the spectral reflectance was measured by irradiating the resin composition layer with 450 nm and 550 nm.
（４）白色度
東京電色製の分光白色度光度計ＥＲＰ−８０ＷＸを用い、標準板（酸化マグネシウム板）に波長４５７ｎｍの光を照射したときの光の反射率を１００％として、樹脂組成物層の反射率を標準板の反射率に対する百分率として表した。
（５）耐光性
波長幅４００ｎｍ〜４８０ｎｍであり、４２０ｎｍに波長のピークを持つ青色光を空気中において、樹脂組成物層の単位面積あたりに対して９０Ｗ／ｍ２の強さで１０００時間連続して照射した後の白色度で表した。
（６）粒径
株式会社堀場製作所製レーザ回折／散乱式粒度分布測定装置ＬＡ−９１０を使用して、水を分散媒とし、透過率が定常になるまで超音波照射して測定を実施した。体積基準で累積５０％に相当する粒子系をメジアン径とした。
(4) Whiteness Resin composition using a spectral whiteness photometer ERP-80WX manufactured by Tokyo Denshoku, and a light reflectance of 100% when a standard plate (magnesium oxide plate) is irradiated with light having a wavelength of 457 nm. The reflectivity of the layer was expressed as a percentage of the reflectivity of the standard plate.
(5) Light resistance Blue light having a wavelength width of 400 nm to 480 nm and having a wavelength peak at 420 nm is continuously in air for 1000 hours at an intensity of 90 W / m 2 with respect to the unit area of the resin composition layer. The whiteness after irradiation was expressed.
(6) Particle size Using a laser diffraction / scattering particle size distribution measuring apparatus LA-910 manufactured by Horiba, Ltd., water was used as a dispersion medium and measurement was performed by irradiating with ultrasonic waves until the transmittance became steady. The particle system corresponding to 50% cumulative on a volume basis was defined as the median diameter.
参考例１
１，２，４，５-シクロヘキサンテトラカルボン酸二無水物の合成。
内容積５リットルのハステロイ製(ＨＣ２２)オートクレーブにピロメリット酸５５２ｇ、活性炭にロジウムを担持させた触媒（エヌ・イーケムキャット株式会社（N.E. Chemcat Corporation）製）２００ｇ、水１６５６ｇを仕込み、攪拌をしながら反応器内を窒素ガスで置換した。次に水素ガスで反応器内を置換し、反応器の水素圧を５．０ＭＰａとして６０℃まで昇温した。水素圧を５．０ＭＰａに保ちながら２時間反応させた。反応器内の水素ガスを窒素ガスで置換し、反応液をオートクレーブより抜き出し、この反応液を熱時濾過して触媒を分離した。濾過液をロータリーエバポレーターで減圧下に水を蒸発させて濃縮し、結晶を析出させた。析出した結晶を室温で固液分離し、乾燥して１，２，４，５-シクロヘキサンテトラカルボン酸４８１ｇ（収率８５．０％）を得た。
Reference example 1
Synthesis of 1,2,4,5-cyclohexanetetracarboxylic dianhydride.
A 5 liter Hastelloy (HC22) autoclave was charged with 552 g of pyromellitic acid, 200 g of a catalyst with rhodium supported on activated carbon (manufactured by NE Chemcat Corporation), and 1656 g of water while stirring. The inside of the reactor was replaced with nitrogen gas. Next, the inside of the reactor was replaced with hydrogen gas, and the temperature of the reactor was increased to 60 ° C. with a hydrogen pressure of 5.0 MPa. The reaction was carried out for 2 hours while maintaining the hydrogen pressure at 5.0 MPa. The hydrogen gas in the reactor was replaced with nitrogen gas, the reaction solution was extracted from the autoclave, and the reaction solution was filtered while hot to separate the catalyst. The filtrate was concentrated by evaporating water under reduced pressure using a rotary evaporator to precipitate crystals. The precipitated crystals were separated into solid and liquid at room temperature and dried to obtain 481, g (yield: 85.0%) of 1,2,4,5-cyclohexanetetracarboxylic acid.
続いて、得られた１，２，４，５−シクロヘキサンテトラカルボン酸４５０gと無水酢酸４０００gとを、５リットルのガラス製セパラブルフラスコ（ジムロート冷却管付）に仕込み、攪拌しながら反応器内を窒素ガスで置換した。窒素ガス雰囲気下で溶媒の還流温度まで昇温し、１０分間溶媒を還流させた。攪拌しながら室温まで冷却し、結晶を析出させた。析出した結晶を固液分離し、乾燥して一次結晶を得た。更に分離母液をロータリーエバポレーターで減圧下に濃縮し、結晶を析出させた。この結晶を固液分離し、乾燥して二次結晶を得た。一次結晶、二次結晶を合わせて１，２，４，５−シクロヘキサンテトラカルボン酸二無水物３７５gが得られた（無水化の収率９６．６％）。 Subsequently, 450 g of the obtained 1,2,4,5-cyclohexanetetracarboxylic acid and 4000 g of acetic anhydride were charged into a 5-liter glass separable flask (with Dimroth condenser), and the inside of the reactor was stirred. Replaced with nitrogen gas. The temperature was raised to the reflux temperature of the solvent under a nitrogen gas atmosphere, and the solvent was refluxed for 10 minutes. While stirring, the mixture was cooled to room temperature to precipitate crystals. The precipitated crystals were separated into solid and liquid and dried to obtain primary crystals. Further, the separated mother liquor was concentrated under reduced pressure using a rotary evaporator to precipitate crystals. The crystals were separated into solid and liquid and dried to obtain secondary crystals. The primary crystal and the secondary crystal were combined to obtain 375 g of 1,2,4,5-cyclohexanetetracarboxylic dianhydride (anhydrous yield of 96.6%).
参考例２
温度計、撹拌器、窒素導入管、側管付き滴下ロート、ディーンスターク、冷却管を備えた５００ｍＬ５つ口フラスコに、窒素気流下、４，４’−ジアミノジフェニルエーテル１０．０ｇ（０．０５モル）と、溶剤としてＮ−メチル−２−ピロリドン８５ｇを仕込んで溶解させた後、参考例１で合成した１，２，４，５−シクロヘキサンテトラカルボン酸二無水物１１．２ｇ（０．０５モル）を室温にて固体のまま１時間かけて分割投入し、室温下２時間撹拌した。次に共沸脱水溶剤としてキシレン３０．０ｇを添加して１８０℃に昇温して３時間反応を行い、ディーンスタークでキシレンを還流させて、共沸してくる生成水を分離した。
Reference example 2
In a 500 mL five-necked flask equipped with a thermometer, stirrer, nitrogen inlet tube, dropping funnel with side tube, Dean Stark, and condenser tube, 10.0 g (0.05 mol) of 4,4′-diaminodiphenyl ether under nitrogen flow And 85 g of N-methyl-2-pyrrolidone as a solvent were dissolved and then 11.2 g (0.05 mol) of 1,2,4,5-cyclohexanetetracarboxylic dianhydride synthesized in Reference Example 1. Was kept in a solid state at room temperature over 1 hour and stirred at room temperature for 2 hours. Next, 30.0 g of xylene was added as an azeotropic dehydration solvent, the temperature was raised to 180 ° C., the reaction was carried out for 3 hours, and xylene was refluxed with a Dean Stark to separate azeotropically produced water.
３時間後、水の留出が終わったことを確認し、１時間かけて１９０℃に昇温しながらキシレンを留去し２９．０ｇを回収した後、内温が６０℃になるまで空冷してポリイミドの有機溶剤溶液を取り出した。得られたポリイミドの有機溶剤溶液をガラス板に塗布し、９０℃のホットプレート上で１時間加熱して溶剤を蒸発させた後、ガラス板から剥がして自立膜を得た。この自立膜をステンレス製の固定治具に固定して熱風乾燥器中２２０℃で２時間加熱して溶剤をさらに蒸発させ、薄茶色のフレキシブルな膜厚１００μｍのフィルムを得た。このフィルムのＩＲスペクトルを測定したところ、ν（Ｃ＝Ｏ）１７７２、１７００（ｃｍ−１）にイミド環の特性吸収が認められ、下記式ＩＩの繰り返し単位を有するポリイミドであると同定された。 After 3 hours, it was confirmed that the distillation of water had ended, xylene was distilled off while raising the temperature to 190 ° C. over 1 hour, 29.0 g was recovered, and then air-cooled until the internal temperature reached 60 ° C. Then, the organic solvent solution of polyimide was taken out. The obtained organic solvent solution of polyimide was applied to a glass plate, heated on a hot plate at 90 ° C. for 1 hour to evaporate the solvent, and then peeled off from the glass plate to obtain a self-supporting film. This self-supporting film was fixed to a stainless steel fixing jig and heated in a hot air dryer at 220 ° C. for 2 hours to further evaporate the solvent, thereby obtaining a light brown flexible film having a thickness of 100 μm. When the IR spectrum of this film was measured, characteristic absorption of an imide ring was observed at ν (C═O) 1772 and 1700 (cm −1 ), and it was identified as a polyimide having a repeating unit of the following formula II.
得られたフィルムのガラス転移温度は３１５℃であった。また、このフィルムを、ＪＩＳ Ｋ７１０５に準拠して、ヘイズメーター（日本電色（株）製 Ｚ−Σ８０）により全光線透過率を測定したところ、９０％と高い値を示した。
このポリイミドフィルムを空気中２２０℃で４時間熱処理し、熱処理前後の全光線透過率を測定したが、９０％で変化は無く、目視観察でも着色は見られなかった。
The glass transition temperature of the obtained film was 315 ° C. Moreover, when the total light transmittance of this film was measured with a haze meter (Nippon Denshoku Co., Ltd. Z-Σ80) in accordance with JIS K7105, it showed a high value of 90%.
This polyimide film was heat treated in air at 220 ° C. for 4 hours, and the total light transmittance before and after the heat treatment was measured. However, there was no change at 90%, and no coloration was observed even by visual observation.
参考例３
温度計、撹拌器、窒素導入管、側管付き滴下ロート、ディーンスターク、冷却管を備えた５００ｍＬ５つ口フラスコに、窒素気流下、４，４’−ジアミノジフェニルエーテル１０．０ｇ（０．０５モル）と、溶剤としてＮ−メチル−２−ピロリドン８５ｇを仕込んで溶解させた後、シクロペンタン−１，２，３，４−テトラカルボン酸（アルドリッチ社製）１２．３ｇ（０．０５モル）を室温にて固体のまま1時間かけて分割投入し、室温下２時間撹拌した。次に共沸脱水溶剤としてキシレン３０．０ｇを添加して１８０℃に昇温して７時間反応を行い、ディーンスタークでキシレンを還流させて、共沸してくる生成水を分離した。
Reference example 3
In a 500 mL five-necked flask equipped with a thermometer, stirrer, nitrogen inlet tube, dropping funnel with side tube, Dean Stark, and condenser tube, 10.0 g (0.05 mol) of 4,4′-diaminodiphenyl ether under nitrogen flow Then, 85 g of N-methyl-2-pyrrolidone as a solvent was added and dissolved, and then 12.3 g (0.05 mol) of cyclopentane-1,2,3,4-tetracarboxylic acid (manufactured by Aldrich) was added at room temperature. The solution was added in portions over 1 hour with stirring at room temperature and stirred at room temperature for 2 hours. Next, 30.0 g of xylene was added as an azeotropic dehydration solvent, the temperature was raised to 180 ° C., the reaction was carried out for 7 hours, and xylene was refluxed with a Dean Stark to separate the azeotropic product water.
３時間後、水の留出が終わったことを確認し、１時間かけて１９０℃に昇温しながらキシレンを留去し２９．０ｇを回収した後、内温が６０℃になるまで空冷してポリイミドの有機溶剤溶液を取り出した。得られたポリイミドの有機溶剤溶液をガラス板に塗布し、９０℃のホットプレート上で１時間加熱して溶剤を蒸発させた後、ガラス板から剥がして自立膜を得た。この自立膜をステンレス製の固定治具に固定して熱風乾燥器中２２０℃で２時間加熱して溶剤をさらに蒸発させ、薄茶色のフレキシブルな膜厚１００μｍのフィルムを得た。このフィルムのＩＲスペクトルを測定したところ、ν（Ｃ＝Ｏ）１７７２、１７００（ｃｍ−１）にイミド環の特性吸収が認められ、下記式ＩＩＩの繰り返し単位を有するポリイミドであると同定された。 After 3 hours, it was confirmed that the distillation of water had ended, xylene was distilled off while raising the temperature to 190 ° C. over 1 hour, 29.0 g was recovered, and then air-cooled until the internal temperature reached 60 ° C. Then, the organic solvent solution of polyimide was taken out. The obtained organic solvent solution of polyimide was applied to a glass plate, heated on a hot plate at 90 ° C. for 1 hour to evaporate the solvent, and then peeled off from the glass plate to obtain a self-supporting film. This self-supporting film was fixed to a stainless steel fixing jig and heated in a hot air dryer at 220 ° C. for 2 hours to further evaporate the solvent, thereby obtaining a light brown flexible film having a thickness of 100 μm. When the IR spectrum of this film was measured, characteristic absorption of an imide ring was observed at ν (C═O) 1772 and 1700 (cm −1 ), and it was identified as a polyimide having a repeating unit of the following formula III.
得られたフィルムをＪＩＳ Ｋ７１０５に準拠して、ヘイズメーター（日本電色（株）製 Ｚ−Σ８０）により全光線透過率を測定したところ、８９％と高い値を示した。
このポリイミドフィルムを空気中２２０℃で４時間熱処理し、熱処理前後の全光線透過率を測定したが、８９％で変化は無く、目視観察でも着色は見られなかった。
When the total light transmittance of the obtained film was measured with a haze meter (Nippon Denshoku Co., Ltd. Z-Σ80) in accordance with JIS K7105, a high value of 89% was shown.
This polyimide film was heat-treated in air at 220 ° C. for 4 hours, and the total light transmittance before and after the heat treatment was measured. However, there was no change at 89%, and no coloration was observed even by visual observation.
参考例４
温度計、撹拌器、窒素導入管、側管付き滴下ロート、ディーンスターク、冷却管を備えた５００ｍＬ５つ口フラスコに、窒素気流下、４，４’−ジアミノジフェニルエーテル１０．０ｇ（０．０５モル）と、溶剤としてＮ−メチル−２−ピロリドン８５ｇを仕込んで溶解させた後、ピロメリット酸二無水物１０．９ｇ（０．０５モル）を室温にて固体のまま１時間かけて分割投入し、室温下２時間撹拌した。得られたポリアミド酸の有機溶剤溶液をガラス板に塗布し、９０℃のホットプレート上で１時間加熱して溶剤を蒸発させた後、ガラス板から剥がして自立膜を得た。この自立膜をステンレス製の固定治具に固定して熱風乾燥器中２２０℃で２時間加熱して溶剤をさらに蒸発させ、さらに３００℃で１時間加熱して熱イミド化し、茶褐色のフレキシブルな膜厚１００μｍのフィルムを得た。このフィルムのＩＲスペクトルを測定したところ、ν（Ｃ＝Ｏ）１７７２、１７００（ｃｍ−１）にイミド環の特性吸収が認められ、下記式ＩＶの繰り返し単位を有するポリイミドであると同定された。
Reference example 4
In a 500 mL five-necked flask equipped with a thermometer, stirrer, nitrogen inlet tube, dropping funnel with side tube, Dean Stark, and condenser tube, 10.0 g (0.05 mol) of 4,4′-diaminodiphenyl ether under nitrogen flow Then, 85 g of N-methyl-2-pyrrolidone as a solvent was charged and dissolved, and then 10.9 g (0.05 mol) of pyromellitic dianhydride was dividedly charged over 1 hour as a solid at room temperature. Stir at room temperature for 2 hours. The obtained organic solvent solution of polyamic acid was applied to a glass plate, heated on a hot plate at 90 ° C. for 1 hour to evaporate the solvent, and then peeled off from the glass plate to obtain a self-supporting film. This self-supporting film is fixed to a stainless steel fixing jig and heated in a hot air dryer at 220 ° C. for 2 hours to further evaporate the solvent, and further heated at 300 ° C. for 1 hour to thermally imidize, thereby forming a brown-colored flexible film A film having a thickness of 100 μm was obtained. When the IR spectrum of this film was measured, characteristic absorption of an imide ring was observed at ν (C═O) 1772 and 1700 (cm −1 ), and it was identified as a polyimide having a repeating unit of the following formula IV.
得られたフィルムをＪＩＳ Ｋ７１０５に準拠して、ヘイズメーター（日本電色（株）製 Ｚ−Σ８０）により全光線透過率を測定したところ４８％であった。 When the total light transmittance of the obtained film was measured with a haze meter (Nippon Denshoku Co., Ltd. Z-Σ80) in accordance with JIS K7105, it was 48%.
実施例１
３００ｍｌのマヨネーズ瓶に参考例２で合成したポリイミドの有機溶剤溶液５５ｇ（固形分１０ｇ）とメジアン径０．４３μｍのルチル型酸化チタン５ｇ（石原産業製ＰＦ−６９１）（酸化チタンに近い方からＳｉＯ２処理、ポリオール処理、シロキサン処理の順で表面処理を施したもの。）とＮ−メチルピロリドン３０ｇを加え、さらに直径２ｍｍのアルミナビーズ１０ｇを入れてしっかりと蓋をし、マヨネーズ瓶が破損しないように外側に保護テープを貼り付けた。８０℃に加熱した熱風乾燥機中に３０分間入れて加熱した後、ＵＮＩＯＮ，Ｎ．Ｊ．社製ＰＡＩＮＴ ＣＯＮＤＩＴＩＯＮＥＲ ＲＥＤ ＤＥＶＩＬ ＴＯＯＬにマヨネーズ瓶を固定し３０分間混合分散した。アルミナビーズを濾別して樹脂組成物を得た。
Example 1
55 g of polyimide organic solvent solution synthesized in Reference Example 2 in a 300 ml mayonnaise bottle (solid content 10 g) and 5 g of rutile titanium oxide with a median diameter of 0.43 μm (PF-691 made by Ishihara Sangyo) (from the side closer to titanium oxide SiO 2 2 treatment, polyol treatment, and siloxane treatment in order)) and 30 g of N-methylpyrrolidone, and 10 g of alumina beads with a diameter of 2 mm are added and tightly covered to prevent the mayonnaise bottle from being damaged. A protective tape was attached to the outside. After heating for 30 minutes in a hot air dryer heated to 80 ° C., UNION, N. J. et al. A mayonnaise bottle was fixed to PAINT CONDITIONER RED DEVI TOOL made by the company and mixed and dispersed for 30 minutes. The alumina beads were separated by filtration to obtain a resin composition.
続いて厚さ１８μｍの電解銅箔(三井金属鉱業株式会社（Mitsui Mining & Smelting Co. Ltd.）製３ＥＣ−ＶＬＰ)上に、得られた樹脂組成物を塗布し、１００℃のホットプレート上で１時間加熱して溶剤を蒸発させた後、ステンレス製の固定治具に固定して熱風乾燥器中２２０℃で２時間加熱して溶剤をさらに蒸発させ、片面フレキシブル銅張り白色積層体を得た（樹脂組成物層２５μｍ）。
また得られた片面フレキシブル銅張り白色積層体の樹脂組成物層面に、別にもう１枚用意した同仕様の厚さ１８μｍの電解銅箔を重ね、二枚の金型に挟み３３０℃に設定した熱プレスで最高圧力５０ｋｇｆ／ｃｍ２で３０分熱圧着した後、金型ごと取り出して冷却プレスにて５分間冷却した後取り出し、両面フレキシブル銅張り白色積層体を得た。両面フレキシブル銅張り白色積層体の接着強度１．１Ｎ／ｍｍであった。両面フレキシブル銅張り白色積層体の銅箔をエッチングして除去した後の白色面について反射率、白色度および耐光性を評価した。結果を表１に示す。
Subsequently, the obtained resin composition was applied onto an electrolytic copper foil having a thickness of 18 μm (3EC-VLP manufactured by Mitsui Mining & Smelting Co. Ltd.), and then on a hot plate at 100 ° C. After heating for 1 hour to evaporate the solvent, it was fixed to a stainless steel fixture and heated in a hot air dryer at 220 ° C. for 2 hours to further evaporate the solvent to obtain a single-sided flexible copper-clad white laminate. (Resin composition layer 25 μm).
In addition, another 18-μm thick electrolytic copper foil of the same specification prepared on the surface of the resin composition layer of the obtained single-sided flexible copper-clad white laminate was stacked, and the heat set at 330 ° C. was sandwiched between two molds. After thermocompression bonding with a press at a maximum pressure of 50 kgf / cm 2 for 30 minutes, the whole mold was taken out, cooled with a cooling press for 5 minutes and then taken out to obtain a double-sided flexible copper-clad white laminate. The adhesive strength of the double-sided flexible copper-clad white laminate was 1.1 N / mm. The reflectance, whiteness, and light resistance of the white surface after etching and removing the copper foil of the double-sided flexible copper-clad white laminate were evaluated. The results are shown in Table 1.
実施例２
実施例１で得た樹脂組成物を、予めエタノール洗浄した厚さ５２．８μｍのカプトン２００Ｈ（東レ・デュポン（株）製）上に、得られた樹脂組成物の有機溶剤分散液を塗布し、１００℃のホットプレート上で１時間加熱して溶剤を蒸発させた後、ステンレス製の固定治具に固定して熱風乾燥器中２２０℃で２時間加熱して溶剤をさらに蒸発させた（樹脂組成物層４μｍ）。さらに厚さ１８μｍの電解銅箔(三井金属鉱業株式会社（Mitsui Mining & Smelting Co. Ltd.）製３ＥＣ−ＶＬＰ)の粗面を樹脂組成物層上に重ね、実施例１と同様にしてフレキシブル銅張白色積層体を得た。フレキシブル銅張白色積層体の接着強度は１．１Ｎ／ｍｍであった。
フレキシブル銅張白色積層体の銅箔をエッチングし除去した樹脂組成物層について反射率と白色度を評価した。結果を表１に示す。
Example 2
The resin composition obtained in Example 1 was applied with an organic solvent dispersion of the resin composition obtained on Kapton 200H (manufactured by Toray DuPont Co., Ltd.) having a thickness of 52.8 μm that had been washed with ethanol in advance. After heating on a hot plate at 100 ° C. for 1 hour to evaporate the solvent, it was fixed on a stainless steel fixture and heated in a hot air dryer at 220 ° C. for 2 hours to further evaporate the solvent (resin composition Material layer 4 μm). Further, a rough surface of 18 μm thick electrolytic copper foil (3EC-VLP manufactured by Mitsui Mining & Smelting Co. Ltd.) was overlaid on the resin composition layer, and flexible copper was formed in the same manner as in Example 1. A tight white laminate was obtained. The adhesive strength of the flexible copper-clad white laminate was 1.1 N / mm.
The reflectance and whiteness of the resin composition layer obtained by etching away the copper foil of the flexible copper-clad white laminate were evaluated. The results are shown in Table 1.
実施例３
メジアン径０．４３μｍのルチル型酸化チタン５ｇ（石原産業製ＰＦ−６９１）の代わりにメジアン径０．４３μｍのルチル型酸化チタン７．５ｇ（石原産業製ＰＦ−６９１）を用いて得た樹脂組成物を使用したこと以外は実施例１と同様に行い、樹脂組成物層２５μｍを有する片面フレキシブル銅張り白色積層体を得た。片面フレキシブル銅張り白色積層体の銅箔をエッチングして除去した後の白色面について反射率、白色度および耐光性を評価した。結果を表１に示す。
Example 3
Resin composition obtained by using 7.5 g of rutile titanium oxide with a median diameter of 0.43 μm (PF-691 made by Ishihara Sangyo) instead of 5 g of rutile titanium oxide with a median diameter of 0.43 μm (PF-691 made by Ishihara Sangyo) Except having used the thing, it carried out similarly to Example 1 and obtained the single-sided flexible copper-clad white laminated body which has a resin composition layer 25micrometer. The reflectance, whiteness, and light resistance of the white surface after the copper foil of the single-sided flexible copper-clad white laminate was removed by etching were evaluated. The results are shown in Table 1.
実施例４
実施例３で得た樹脂組成物を用いた以外は実施例２と同様に行い、樹脂組成物層４μｍを有するフレキシブル銅張白色積層体を得た。フレキシブル銅張白色積層体の接着強度は１．１Ｎ／ｍｍであった。フレキシブル銅張白色積層体の銅箔をエッチングし除去した樹脂組成物層について反射率と白色度を評価した。結果を表１に示す。
Example 4
Except having used the resin composition obtained in Example 3, it carried out similarly to Example 2 and obtained the flexible copper clad white laminated body which has a resin composition layer 4 micrometers. The adhesive strength of the flexible copper-clad white laminate was 1.1 N / mm. The reflectance and whiteness of the resin composition layer obtained by etching away the copper foil of the flexible copper-clad white laminate were evaluated. The results are shown in Table 1.
実施例５
実施例１において酸化チタンの種類をメジアン径０．４３μｍのルチル型酸化チタン５ｇ（石原産業製ＰＦ−６９１、シロキサン処理を施したもの）の代わりに、メジアン径０．５５μｍのルチル型酸化チタン５ｇ（石原産業製ＰＣ−３）（酸化チタンに近い方からＳｉＯ２処理、ポリオール処理、シロキサン処理の順で表面処理を施したもの。）を使用した以外は実施例１と同様に行い、樹脂組成物層２５μｍを有する片面フレキシブル銅張り白色積層体を得た。片面フレキシブル銅張り白色積層体の銅箔をエッチングして除去した後の白色面について反射率、白色度および耐光性を評価した。結果を表１に示す。
Example 5
In Example 1, instead of 5 g of rutile type titanium oxide having a median diameter of 0.43 μm (PF-691 manufactured by Ishihara Sangyo Co., Ltd. subjected to siloxane treatment), 5 g of rutile type titanium oxide having a median diameter of 0.55 μm was used. (Ishihara Sangyo PC-3) (Surface treatment was performed in the order of SiO 2 treatment, polyol treatment, and siloxane treatment from the side closer to titanium oxide.) A single-sided flexible copper-clad white laminate having a physical layer of 25 μm was obtained. The reflectance, whiteness and light resistance of the white surface after the copper foil of the single-sided flexible copper-clad white laminate was removed by etching were evaluated. The results are shown in Table 1.
実施例６
実施例１において酸化チタンの種類をメジアン径０．４３μｍのルチル型酸化チタン５ｇ（石原産業製ＰＦ−６９１、シロキサン処理を施したもの）の代わりに、メジアン径０．６４μｍのルチル型酸化チタン５ｇ（石原産業製ＰＦ−７１１）（酸化チタンに近い方からＳｉＯ２処理、ポリオール処理の順で表面処理を施したもの。）を使用した以外は実施例１と同様に行い、樹脂組成物層２５μｍを有する片面フレキシブル銅張り白色積層体を得た。片面フレキシブル銅張り白色積層体の銅箔をエッチングして除去した後の白色面について反射率、白色度および耐光性を評価した。結果を表１に示す。
Example 6
In Example 1, instead of 5 g of rutile type titanium oxide having a median diameter of 0.43 μm (PF-691 manufactured by Ishihara Sangyo Co., Ltd. subjected to siloxane treatment), 5 g of rutile type titanium oxide having a median diameter of 0.64 μm was used. (Ishihara Sangyo PF-711) (Surface treatment was performed in the order of SiO2 treatment and polyol treatment from the side closer to titanium oxide.) The same procedure as in Example 1 was carried out to obtain a resin composition layer of 25 μm. The obtained single-sided flexible copper-clad white laminate was obtained. The reflectance, whiteness, and light resistance of the white surface after the copper foil of the single-sided flexible copper-clad white laminate was removed by etching were evaluated. The results are shown in Table 1.
実施例７
実施例１において酸化チタンの種類をメジアン径０．４３μｍのルチル型酸化チタン５ｇ（石原産業製ＰＦ−６９１、シロキサン処理を施したもの）の代わりに、メジアン径０．６７μｍのルチル型酸化チタン５ｇ（石原産業製ＣＲ−９０−２）（酸化チタンに近い方からＳｉＯ２処理、ポリオール処理の順で表面処理を施したもの。）を使用した以外は実施例１と同様に行い、樹脂組成物層２５μｍを有する片面フレキシブル銅張り白色積層体を得た。片面フレキシブル銅張り白色積層体の銅箔をエッチングして除去した後の白色面について反射率、白色度および耐光性を評価した。結果を表１に示す。
Example 7
In Example 1, instead of 5 g of rutile type titanium oxide having a median diameter of 0.43 μm (PF-691 manufactured by Ishihara Sangyo Co., Ltd. subjected to siloxane treatment), 5 g of rutile type titanium oxide having a median diameter of 0.67 μm was used. (Ishihara Sangyo CR-90-2) (Surface treatment was performed in the order of SiO 2 treatment and polyol treatment from the side closer to titanium oxide.) Resin composition was carried out in the same manner as in Example 1. A single-sided flexible copper-clad white laminate having a layer of 25 μm was obtained. The reflectance, whiteness, and light resistance of the white surface after the copper foil of the single-sided flexible copper-clad white laminate was removed by etching were evaluated. The results are shown in Table 1.
実施例８
実施例１において酸化チタンの種類をメジアン径０．４３μｍのルチル型酸化チタン５ｇ（石原産業製ＰＦ−６９１、シロキサン処理を施したもの）の代わりに、メジアン径０．７５μｍのルチル型酸化チタン５ｇ（石原産業製ＣＲ−８０、ＳｉＯ２処理を施したもの）を使用した以外は実施例１と同様に行い、樹脂組成物層２５μｍを有する片面フレキシブル銅張り白色積層体を得た。片面フレキシブル銅張り白色積層体の銅箔をエッチングして除去した後の白色面について反射率、白色度および耐光性を評価した。結果を表１に示す。
Example 8
In Example 1, instead of 5 g of rutile type titanium oxide having a median diameter of 0.43 μm (PF-691 manufactured by Ishihara Sangyo Co., Ltd., subjected to siloxane treatment), 5 g of rutile type titanium oxide having a median diameter of 0.75 μm was used. Except for using (Ishihara Sangyo CR-80, SiO 2 treated), the same procedure as in Example 1 was performed to obtain a single-sided flexible copper-clad white laminate having a resin composition layer of 25 μm. The reflectance, whiteness, and light resistance of the white surface after the copper foil of the single-sided flexible copper-clad white laminate was removed by etching were evaluated. The results are shown in Table 1.
実施例９
実施例１において酸化チタンの種類をメジアン径０．４３μｍのルチル型酸化チタン５ｇ（石原産業製ＰＦ−６９１、シロキサン処理を施したもの）の代わりに、メジアン径０．７７μｍのルチル型酸化チタン５ｇ（堺化学工業製ＳＲ−１、Ａｌ２Ｏ３処理を施したもの）を使用した以外は実施例１と同様に行い、樹脂組成物層２５μｍを有する片面フレキシブル銅張り白色積層体を得た。片面フレキシブル銅張り白色積層体の銅箔をエッチングして除去した後の白色面について反射率、白色度および耐光性を評価した。結果を表１に示す。
Example 9
In Example 1, instead of 5 g of rutile type titanium oxide having a median diameter of 0.43 μm (PF-691 manufactured by Ishihara Sangyo Co., Ltd. subjected to siloxane treatment), 5 g of rutile type titanium oxide having a median diameter of 0.77 μm was used. A single-sided flexible copper-clad white laminate having a resin composition layer of 25 μm was obtained in the same manner as in Example 1 except that SR-1 manufactured by Sakai Chemical Industry Co., Ltd. (treated with Al 2 O 3 treatment) was used. The reflectance, whiteness, and light resistance of the white surface after the copper foil of the single-sided flexible copper-clad white laminate was removed by etching were evaluated. The results are shown in Table 1.
実施例１０
３００ｍｌのマヨネーズ瓶に参考例３で合成したポリイミドの有機溶剤溶液５３ｇ（固形分１０ｇ）とメジアン径０．４３μｍのルチル型酸化チタン５ｇ（石原産業製ＰＦ−６９１）（酸化チタンに近い方からＳｉＯ２処理、ポリオール処理、シロキサン処理の順で表面処理を施したもの。）とＮ−メチルピロリドン３０ｇを加え、さらに直径２ｍｍのアルミナビーズ１０ｇを入れてしっかりと蓋をし、マヨネーズ瓶が破損しないように外側に保護テープを貼り付けた。８０℃に加熱した熱風乾燥機中に３０分間入れて加熱した後、ＵＮＩＯＮ，Ｎ．Ｊ．社製ＰＡＩＮＴ ＣＯＮＤＩＴＩＯＮＥＲ ＲＥＤ ＤＥＶＩＬ ＴＯＯＬにマヨネーズ瓶を固定し３０分間混合分散した後、アルミナビーズを濾別して樹脂組成物を得た。
Example 10
53 g of organic solvent solution of polyimide synthesized in Reference Example 3 in a 300 ml mayonnaise bottle (solid content 10 g) and 5 g of rutile titanium oxide with a median diameter of 0.43 μm (PF-691 manufactured by Ishihara Sangyo) (from the side closer to titanium oxide SiO 2 2 treatment, polyol treatment, and siloxane treatment in order)) and 30 g of N-methylpyrrolidone, and 10 g of alumina beads with a diameter of 2 mm are added and tightly covered to prevent the mayonnaise bottle from being damaged. A protective tape was attached to the outside. After heating for 30 minutes in a hot air dryer heated to 80 ° C., UNION, N. J. et al. A mayonnaise bottle was fixed to PAINT CONDITIONER RED DEVIL TOOL manufactured by the company and mixed and dispersed for 30 minutes, and then the alumina beads were separated by filtration to obtain a resin composition.
続いて厚さ１８μｍの電解銅箔(三井金属鉱業株式会社（Mitsui Mining & Smelting Co. Ltd.）製３ＥＣ−ＶＬＰ)上に、得られた樹脂組成物を塗布し、１００℃のホットプレート上で１時間加熱して溶剤を蒸発させた後、ステンレス製の固定治具に固定して熱風乾燥器中２２０℃で２時間加熱して溶剤をさらに蒸発させ、片面フレキシブル銅張り白色積層体を得た（樹脂組成物層２５μｍ）。片面フレキシブル銅張り白色積層体の銅箔をエッチングして除去した後の白色面について反射率、白色度および耐光性を評価した。結果を表１に示す。 Subsequently, the obtained resin composition was applied onto an electrolytic copper foil having a thickness of 18 μm (3EC-VLP manufactured by Mitsui Mining & Smelting Co. Ltd.), and then on a hot plate at 100 ° C. After heating for 1 hour to evaporate the solvent, it was fixed to a stainless steel fixture and heated in a hot air dryer at 220 ° C. for 2 hours to further evaporate the solvent to obtain a single-sided flexible copper-clad white laminate. (Resin composition layer 25 μm). The reflectance, whiteness, and light resistance of the white surface after the copper foil of the single-sided flexible copper-clad white laminate was removed by etching were evaluated. The results are shown in Table 1.
比較例１
３００ｍｌのマヨネーズ瓶に参考例４で合成したポリアミド酸の有機溶剤溶液５５ｇ（固形分１０ｇ）とメジアン径０．４３μｍのルチル型酸化チタン５ｇ（石原産業製ＰＦ−６９１）（酸化チタンに近い方からＳｉＯ２処理、ポリオール処理、シロキサン処理の順で表面処理を施したもの。）とＮ−メチルピロリドン３０ｇを加え、さらに直径２ｍｍのアルミナビーズ１０ｇを入れてしっかりと蓋をし、マヨネーズ瓶が破損しないように外側に保護テープを貼り付けた。８０℃に加熱した熱風乾燥機中に３０分間入れて加熱した後、ＵＮＩＯＮ，Ｎ．Ｊ．社製ＰＡＩＮＴ ＣＯＮＤＩＴＩＯＮＥＲ ＲＥＤ ＤＥＶＩＬ ＴＯＯＬにマヨネーズ瓶を固定し３０分間混合分散した後、アルミナビーズを濾別して樹脂組成物を得た。
Comparative Example 1
55 g of organic solvent solution of polyamic acid synthesized in Reference Example 4 in a 300 ml mayonnaise bottle (solid content 10 g) and 5 g of rutile titanium oxide with a median diameter of 0.43 μm (PF-691 manufactured by Ishihara Sangyo) (from the side closer to titanium oxide) SiO 2 treatment, polyol treatment, siloxane treatment in order)) and 30 g of N-methylpyrrolidone are added, and 10 g of alumina beads with a diameter of 2 mm are added and the lid is tightly closed so that the mayonnaise bottle does not break. A protective tape was affixed to the outside. After heating for 30 minutes in a hot air dryer heated to 80 ° C., UNION, N. J. et al. A mayonnaise bottle was fixed to PAINT CONDITIONER RED DEVIL TOOL manufactured by the company and mixed and dispersed for 30 minutes, and then the alumina beads were separated by filtration to obtain a resin composition.
続いて厚さ１８μｍの電解銅箔(三井金属鉱業株式会社（Mitsui Mining & Smelting Co. Ltd.）製３ＥＣ−ＶＬＰ)上に、得られた樹脂組成物を塗布し、１００℃のホットプレート上で１時間加熱して溶剤を蒸発させた後、ステンレス製の固定治具に固定して熱風乾燥器中２２０℃で２時間加熱して溶剤をさらに蒸発させ、さらに３００℃で１時間加熱して熱イミド化し、片面フレキシブル銅張り白色積層体を得た（樹脂組成物層２５μｍ）。片面フレキシブル銅張り白色積層体の銅箔をエッチングして除去した後の白色面について反射率、白色度および耐光性を評価した。結果を表１に示す。 Subsequently, the obtained resin composition was applied onto an electrolytic copper foil having a thickness of 18 μm (3EC-VLP manufactured by Mitsui Mining & Smelting Co. Ltd.), and then on a hot plate at 100 ° C. After heating for 1 hour to evaporate the solvent, it was fixed to a stainless steel fixture and heated in a hot air dryer at 220 ° C for 2 hours to further evaporate the solvent, and further heated at 300 ° C for 1 hour to heat. Imidized to obtain a single-sided flexible copper-clad white laminate (resin composition layer 25 μm). The reflectance, whiteness, and light resistance of the white surface after the copper foil of the single-sided flexible copper-clad white laminate was removed by etching were evaluated. The results are shown in Table 1.
比較例２
メジアン径０．４３μｍのルチル型酸化チタン５ｇ（石原産業製ＰＦ−６９１）の代わりにメジアン径０．４３μｍのルチル型酸化チタン１ｇ（石原産業製ＰＦ−６９１）を用いて得た樹脂組成物を使用したこと以外は実施例１と同様に行い、樹脂組成物層２５μｍを有する片面フレキシブル銅張り白色積層体を得た。片面フレキシブル銅張り白色積層体の銅箔をエッチングして除去した後の白色面について反射率、白色度および耐光性を評価した。結果を表１に示す。
Comparative Example 2
A resin composition obtained by using 1 g of rutile titanium oxide with a median diameter of 0.43 μm (PF-691 made by Ishihara Sangyo) instead of 5 g of rutile titanium oxide with a median diameter of 0.43 μm (PF-691 made by Ishihara Sangyo) Except having used, it carried out similarly to Example 1, and obtained the single-sided flexible copper clad white laminated body which has a resin composition layer 25micrometer. The reflectance, whiteness, and light resistance of the white surface after the copper foil of the single-sided flexible copper-clad white laminate was removed by etching were evaluated. The results are shown in Table 1.
実施例１１
実施例１で得た樹脂組成物の有機溶剤分散液をガラス板に塗布し、９０℃のホットプレート上で１時間加熱して溶剤を蒸発させた後、ガラス板から剥がして自立膜を得た。この自立膜をステンレス製の固定治具に固定して熱風乾燥器中２２０℃で２時間加熱して溶剤をさらに蒸発させ、フレキシブルな膜厚４μｍのフィルムを得た。
続いて予めエタノール洗浄した厚さ５２．８μｍのカプトン２００Ｈ（東レ・デュポン（株）製）と得られた樹脂組成物フィルムを重ね、さらに厚さ１８μｍの電解銅箔(三井金属鉱業株式会社（Mitsui Mining & Smelting Co. Ltd.）製３ＥＣ−ＶＬＰ)の粗面を樹脂組成物フィルム上に重ね、二枚の金型に挟み３３０℃、５０ｋｇｆ／ｃｍ２に設定した熱プレスで３０分熱圧着した後、金型ごと取り出して冷却プレスにて５分間冷却した後取り出し、フレキシブル銅張白色積層体を得た。フレキシブル銅張白色積層体の接着強度は１．１Ｎ／ｍｍであった。
フレキシブル銅張り白色積層体の銅箔をエッチングし除去した樹脂組成物層について反射率と白色度を評価した。結果を表１に示す。
Example 11
The organic solvent dispersion of the resin composition obtained in Example 1 was applied to a glass plate, heated on a hot plate at 90 ° C. for 1 hour to evaporate the solvent, and then peeled off from the glass plate to obtain a self-supporting film. . This self-supporting film was fixed to a stainless steel fixing jig and heated in a hot air dryer at 220 ° C. for 2 hours to further evaporate the solvent, thereby obtaining a flexible film having a thickness of 4 μm.
Subsequently, 52.8 μm thick Kapton 200H (manufactured by Toray DuPont Co., Ltd.) that had been washed with ethanol in advance and the obtained resin composition film were layered, and further an 18 μm thick electrolytic copper foil (Mitsui Metal Mining Co., Ltd.) Mining & Smelting Co. Ltd. (3EC-VLP) rough surface was layered on the resin composition film, sandwiched between two molds, and thermocompression bonded for 30 minutes with a hot press set at 330 ° C. and 50 kgf / cm 2 . Thereafter, the entire mold was taken out, cooled for 5 minutes with a cooling press, and then taken out to obtain a flexible copper-clad white laminate. The adhesive strength of the flexible copper-clad white laminate was 1.1 N / mm.
The reflectance and whiteness of the resin composition layer obtained by etching and removing the copper foil of the flexible copper-clad white laminate were evaluated. The results are shown in Table 1.
実施例１２
実施例１０で得た樹脂組成物を、予めエタノール洗浄した厚さ５２．８μｍのカプトン２００Ｈ（東レ・デュポン（株）製）上に、得られた樹脂組成物の有機溶剤分散液を塗布し、１００℃のホットプレート上で１時間加熱して溶剤を蒸発させた後、ステンレス製の固定治具に固定して熱風乾燥器中２２０℃で２時間加熱して溶剤をさらに蒸発させた（樹脂組成物層４μｍ）。さらに厚さ１８μｍの電解銅箔(三井金属鉱業株式会社（Mitsui Mining & Smelting Co. Ltd.）製３ＥＣ−ＶＬＰ)の粗面を樹脂組成物層上に重ね、二枚の金型に挟み３３０℃、５０ｋｇｆ／ｃｍ２に設定した熱プレスで３０分熱圧着した後、金型ごと取り出して冷却プレスにて５分間冷却した後取り出し、フレキシブル銅張白色積層体を得た。フレキシブル銅張白色積層体の接着強度は１．１Ｎ／ｍｍであった。
フレキシブル銅張り白色積層体の銅箔をエッチングし除去した樹脂組成物層について反射率と白色度を評価した。結果を表１に示す。
Example 12
The resin composition obtained in Example 10 was applied to an organic solvent dispersion of the obtained resin composition on Kapton 200H (manufactured by Toray DuPont Co., Ltd.) having a thickness of 52.8 μm, which had been washed with ethanol in advance. After heating on a hot plate at 100 ° C. for 1 hour to evaporate the solvent, it was fixed on a stainless steel fixture and heated in a hot air dryer at 220 ° C. for 2 hours to further evaporate the solvent (resin composition Material layer 4 μm). Further, a rough surface of 18 μm thick electrolytic copper foil (3EC-VLP manufactured by Mitsui Mining & Smelting Co. Ltd.) is overlaid on the resin composition layer and sandwiched between two molds at 330 ° C. Then, after thermocompression bonding with a hot press set to 50 kgf / cm 2 for 30 minutes, the whole mold was taken out, cooled with a cooling press for 5 minutes and then taken out to obtain a flexible copper-clad white laminate. The adhesive strength of the flexible copper-clad white laminate was 1.1 N / mm.
The reflectance and whiteness of the resin composition layer obtained by etching and removing the copper foil of the flexible copper-clad white laminate were evaluated. The results are shown in Table 1.
比較例３
比較例１で得た樹脂組成物を、予めエタノール洗浄した厚さ５２．８μｍのカプトン２００Ｈ（東レ・デュポン（株）製）上に、得られた樹脂組成物の有機溶剤分散液を塗布し、１００℃のホットプレート上で１時間加熱して溶剤を蒸発させた後、ステンレス製の固定治具に固定して熱風乾燥器中２２０℃で２時間加熱して溶剤をさらに蒸発させた（樹脂組成物層４μｍ）。さらに厚さ１８μｍの電解銅箔(三井金属鉱業株式会社（Mitsui Mining & Smelting Co. Ltd.）製３ＥＣ−ＶＬＰ)の粗面を樹脂組成物層上に重ね、二枚の金型に挟み３３０℃、５０ｋｇｆ／ｃｍ２に設定した熱プレスで３０分熱圧着した後、金型ごと取り出して冷却プレスにて５分間冷却した後取り出し、フレキシブル銅張り白色積層体を得た。フレキシブル銅張白色積層体の接着強度は１．１Ｎ／ｍｍであった。
フレキシブル銅張白色積層体の銅箔をエッチングし除去した樹脂組成物層について反射率と白色度を評価した。結果を表１に示す。
Comparative Example 3
The resin composition obtained in Comparative Example 1 was applied with an organic solvent dispersion of the obtained resin composition on Kapton 200H (manufactured by Toray DuPont Co., Ltd.) having a thickness of 52.8 μm, which had been washed with ethanol in advance. After heating on a hot plate at 100 ° C. for 1 hour to evaporate the solvent, it was fixed on a stainless steel fixture and heated in a hot air dryer at 220 ° C. for 2 hours to further evaporate the solvent (resin composition Material layer 4 μm). Further, a rough surface of 18 μm thick electrolytic copper foil (3EC-VLP manufactured by Mitsui Mining & Smelting Co. Ltd.) is overlaid on the resin composition layer and sandwiched between two molds at 330 ° C. After thermocompression bonding with a hot press set to 50 kgf / cm 2 for 30 minutes, the whole mold was taken out, cooled with a cooling press for 5 minutes and then taken out to obtain a flexible copper-clad white laminate. The adhesive strength of the flexible copper-clad white laminate was 1.1 N / mm.
The reflectance and whiteness of the resin composition layer obtained by etching away the copper foil of the flexible copper-clad white laminate were evaluated. The results are shown in Table 1.
［表１］
酸化チタン 反射率（％） 白色度 耐光性
品名 （％） ４５７nm ５５０nm
実施例１ PF691 ３３ ９５ ８６ ８６ ７７
実施例２ PF691 ３３ ９４ ８６ ８４ ７６
実施例３ PF691 ４３ ９６ ８８ ８６ ７６
実施例４ PF691 ４３ ９５ ８７ ８６ ７５
実施例５ PC3 ３３ ８０ ７７ ７２ ６５
実施例６ PF711 ３３ ８４ ８０ ７６ ６３
実施例７ CR-90-2 ３３ ８７ ８２ ７８ ６５
実施例８ CR-80 ３３ ７９ ７８ ７１ ６２
実施例９ SR1 ３３ ７２ ８０ ７５ ６２
実施例１０ PF691 ３３ ８８ ７９ ７９ ６８
実施例１１ PF691 ３３ ９２ ８４ ８３ ７５
実施例１２ PF691 ３３ ８７ ７７ ７８ ６６
比較例１ PF691 ３３ ３０ ５２ ２５ １３
比較例２ PF691 ３３ ６８ ７４ ６１ ４３
比較例３ PF691 ３３ ２８ ４９ ２５ １１
[Table 1]
Titanium oxide reflectance (%) Whiteness light resistance
Product name (%) 457nm 550nm
Example 1 PF691 33 95 86 86 77
Example 2 PF691 33 94 86 84 76
Example 3 PF691 43 96 88 86 76
Example 4 PF691 43 95 87 86 75
Example 5 PC3 33 80 77 72 65
Example 6 PF711 33 84 80 76 63
Example 7 CR-90-2 33 87 82 78 65
Example 8 CR-80 33 79 78 71 62
Example 9 SR1 33 72 80 75 62
Example 10 PF691 33 88 79 79 68
Example 11 PF691 33 92 84 83 75
Example 12 PF691 33 87 77 78 66
Comparative Example 1 PF691 33 30 52 25 13
Comparative Example 2 PF691 33 68 74 61 43
Comparative Example 3 PF691 33 28 49 25 11
Claims (11)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005239621A JP5124921B2 (en) | 2004-08-23 | 2005-08-22 | Metal-clad white laminate |
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004241904 | 2004-08-23 | ||
| JP2004241904 | 2004-08-23 | ||
| JP2004270945 | 2004-09-17 | ||
| JP2004270945 | 2004-09-17 | ||
| JP2005239621A JP5124921B2 (en) | 2004-08-23 | 2005-08-22 | Metal-clad white laminate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2006110999A true JP2006110999A (en) | 2006-04-27 |
| JP5124921B2 JP5124921B2 (en) | 2013-01-23 |
Family
ID=36379895
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2005239621A Active JP5124921B2 (en) | 2004-08-23 | 2005-08-22 | Metal-clad white laminate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5124921B2 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009020169A1 (en) * | 2007-08-08 | 2009-02-12 | Ishida, Sachio | Method for producing wiring board and wiring board |
| JP2009164540A (en) * | 2008-01-10 | 2009-07-23 | Denki Kagaku Kogyo Kk | Metal-base circuit board and method for manufacturing thereof |
| JP2010201625A (en) * | 2009-02-27 | 2010-09-16 | Nippon Steel Chem Co Ltd | Laminate for flexible substrate and thermally conductive polyimide film |
| JP2010212278A (en) * | 2009-03-06 | 2010-09-24 | Teijin Dupont Films Japan Ltd | Biaxially oriented polyester film for light emitting diode mounting flexible printed circuit board, and laminate for light emitting diode mounting flexible printed circuit board |
| JP2011074029A (en) * | 2009-09-30 | 2011-04-14 | Mitsubishi Chemicals Corp | Bisimide alcohol compound, process for producing the same and polymer compound obtained by polymerizing the same |
| JP2011216515A (en) * | 2010-03-31 | 2011-10-27 | Casio Computer Co Ltd | Flexible printed board, light source device and display device |
| JP2013067718A (en) * | 2011-09-22 | 2013-04-18 | Mitsubishi Gas Chemical Co Inc | Optical laminated film |
| JP2017079320A (en) * | 2015-10-19 | 2017-04-27 | サムソン エレクトロ−メカニックス カンパニーリミテッド． | Circuit board and method of producing the same |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6147932A (en) * | 1984-08-15 | 1986-03-08 | Nissan Chem Ind Ltd | Liquid crystal display element |
| JPH01247461A (en) * | 1988-03-30 | 1989-10-03 | Japan Synthetic Rubber Co Ltd | Colored resin composition |
| JPH0299978A (en) * | 1988-10-06 | 1990-04-11 | Stanley Electric Co Ltd | Eraser for copying machine |
| JPH02208324A (en) * | 1989-02-08 | 1990-08-17 | Nitto Denko Corp | Low-permittivity sheet, and laminate and multilayer circuit board prepared by using same sheet |
| JPH0532778A (en) * | 1991-07-30 | 1993-02-09 | Toray Dow Corning Silicone Co Ltd | Silicone-modified polyimide resin and its production |
| JPH09234956A (en) * | 1996-02-29 | 1997-09-09 | Fuji Photo Film Co Ltd | Multi-color heat-sensitive recording material |
| JPH10202789A (en) * | 1997-01-22 | 1998-08-04 | Shin Kobe Electric Mach Co Ltd | Laminated plate |
| JP2003060321A (en) * | 2001-08-10 | 2003-02-28 | Risho Kogyo Co Ltd | White laminated board used as printed wiring board |
| JP2003141936A (en) * | 2001-11-02 | 2003-05-16 | Mitsubishi Gas Chem Co Inc | Transparent conductive film |
-
2005
- 2005-08-22 JP JP2005239621A patent/JP5124921B2/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6147932A (en) * | 1984-08-15 | 1986-03-08 | Nissan Chem Ind Ltd | Liquid crystal display element |
| JPH01247461A (en) * | 1988-03-30 | 1989-10-03 | Japan Synthetic Rubber Co Ltd | Colored resin composition |
| JPH0299978A (en) * | 1988-10-06 | 1990-04-11 | Stanley Electric Co Ltd | Eraser for copying machine |
| JPH02208324A (en) * | 1989-02-08 | 1990-08-17 | Nitto Denko Corp | Low-permittivity sheet, and laminate and multilayer circuit board prepared by using same sheet |
| JPH0532778A (en) * | 1991-07-30 | 1993-02-09 | Toray Dow Corning Silicone Co Ltd | Silicone-modified polyimide resin and its production |
| JPH09234956A (en) * | 1996-02-29 | 1997-09-09 | Fuji Photo Film Co Ltd | Multi-color heat-sensitive recording material |
| JPH10202789A (en) * | 1997-01-22 | 1998-08-04 | Shin Kobe Electric Mach Co Ltd | Laminated plate |
| JP2003060321A (en) * | 2001-08-10 | 2003-02-28 | Risho Kogyo Co Ltd | White laminated board used as printed wiring board |
| JP2003141936A (en) * | 2001-11-02 | 2003-05-16 | Mitsubishi Gas Chem Co Inc | Transparent conductive film |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009020169A1 (en) * | 2007-08-08 | 2009-02-12 | Ishida, Sachio | Method for producing wiring board and wiring board |
| JP2009043914A (en) * | 2007-08-08 | 2009-02-26 | Ishida Yukio | Method for producing wiring board and wiring board |
| US8512856B2 (en) | 2007-08-08 | 2013-08-20 | Ain Co., Ltd. | Method for producing wiring board and wiring board |
| JP2009164540A (en) * | 2008-01-10 | 2009-07-23 | Denki Kagaku Kogyo Kk | Metal-base circuit board and method for manufacturing thereof |
| JP2010201625A (en) * | 2009-02-27 | 2010-09-16 | Nippon Steel Chem Co Ltd | Laminate for flexible substrate and thermally conductive polyimide film |
| JP2010212278A (en) * | 2009-03-06 | 2010-09-24 | Teijin Dupont Films Japan Ltd | Biaxially oriented polyester film for light emitting diode mounting flexible printed circuit board, and laminate for light emitting diode mounting flexible printed circuit board |
| JP2011074029A (en) * | 2009-09-30 | 2011-04-14 | Mitsubishi Chemicals Corp | Bisimide alcohol compound, process for producing the same and polymer compound obtained by polymerizing the same |
| JP2011216515A (en) * | 2010-03-31 | 2011-10-27 | Casio Computer Co Ltd | Flexible printed board, light source device and display device |
| JP2013067718A (en) * | 2011-09-22 | 2013-04-18 | Mitsubishi Gas Chemical Co Inc | Optical laminated film |
| JP2017079320A (en) * | 2015-10-19 | 2017-04-27 | サムソン エレクトロ−メカニックス カンパニーリミテッド． | Circuit board and method of producing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5124921B2 (en) | 2013-01-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US8642181B2 (en) | Metal-clad white laminate | |
| JP7382447B2 (en) | Double-sided metal-clad laminates and circuit boards | |
| JP5124921B2 (en) | Metal-clad white laminate | |
| CN113874420B (en) | Resin film and metal-clad laminate | |
| US10844175B2 (en) | Polyamide acid, thermoplastic polyimide, resin film, metal-clad laminate and circuit board | |
| TWI461119B (en) | Multilayer fluorine resin film and printed wiring board | |
| JP4883432B2 (en) | Flexible metal-clad laminate | |
| TWI715700B (en) | Polyimide adhesive | |
| JP5824818B2 (en) | Colored light shielding polyimide film | |
| EP2535367A1 (en) | Polyimide film, polyimide laminate comprising same, and polyimide/metal laminate comprising same | |
| JP2017165909A (en) | Polyimide, resin film, and metal clad laminate | |
| JP2008168439A (en) | White polyimide-metal laminate and its manufacturing method | |
| JP5532069B2 (en) | Method for producing flexible metal laminate | |
| JP2004111152A (en) | Transparent conductive film | |
| JP7248394B2 (en) | Polyimide film and metal-clad laminate | |
| TW200930563A (en) | Metal laminate | |
| JP2004358961A (en) | Metal plated laminate | |
| JP7195848B2 (en) | Polyamic acid, polyimide, resin film, metal-clad laminate and manufacturing method thereof | |
| JP2022099997A (en) | Conductor-polyimide laminate | |
| JP5152028B2 (en) | Polymer blend composition, film, and metal laminate | |
| JP7492702B2 (en) | Polyimide, polyimide film, polyamic acid, multilayer polyimide film and method for producing the same, polyimide laminate | |
| JP7252728B2 (en) | Resin film and metal-clad laminate | |
| JP2000022290A (en) | Flexible printed board | |
| JP2004359941A (en) | Adhesive and adhesive film | |
| WO2023190687A1 (en) | Polyimide precursor composition for flexible wiring boards, polyimide film, and polyimide metal multilayer body |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20080804 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20110628 |
|
| RD04 | Notification of resignation of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7424 Effective date: 20120117 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20120529 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20120730 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20121002 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20121015 |
|
| R151 | Written notification of patent or utility model registration |
Ref document number: 5124921 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R151 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20151109 Year of fee payment: 3 |