JP3415928B2 - Photosensitive resin composition and photosensitive film using the same - Google Patents
Photosensitive resin composition and photosensitive film using the sameInfo
- Publication number
- JP3415928B2 JP3415928B2 JP12718594A JP12718594A JP3415928B2 JP 3415928 B2 JP3415928 B2 JP 3415928B2 JP 12718594 A JP12718594 A JP 12718594A JP 12718594 A JP12718594 A JP 12718594A JP 3415928 B2 JP3415928 B2 JP 3415928B2
- Authority
- JP
- Japan
- Prior art keywords
- component
- photosensitive resin
- resin composition
- meth
- molecular weight
- 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.)
- Expired - Lifetime
Links
Landscapes
- Manufacturing Of Printed Circuit Boards (AREA)
- Manufacturing Of Printed Wiring (AREA)
Description
【0001】[0001]
【産業上の利用分野】本発明はプリント配線板等の製造
に用いられる感光性樹脂組成物及びこれを用いた感光性
フィルムに関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive resin composition used for manufacturing printed wiring boards and the like and a photosensitive film using the same.
【0002】[0002]
【従来の技術】印刷配線板の製造に用いられるレジスト
として感光性樹脂組成物が用いられており、特に支持体
上に感光性樹脂組成物をあらかじめ塗布しフィルム状に
した感光性フィルムを用いることは広く知られている。
この感光性樹脂組成物又は感光性フィルムをレジストと
して印刷配線板を作成する工法として、近年、省資源、
工程短縮等の面から部分めっき法が注目されている。こ
の工法は、適当な方法を用いて銅パターンを作成した印
刷配線板上に、更に感光性フィルムをラミネートし露
光、現像工程を経た後めっきすることにより所望の銅パ
ターン上のみにめっきを施す方法である。この工法によ
り、銅パターン上に部分的に半田、金等の金属を析出
し、部品搭載性、耐摩耗性等の品質を向上させることが
できる。2. Description of the Related Art A photosensitive resin composition is used as a resist used in the production of printed wiring boards, and in particular, a photosensitive film formed by previously coating the support with the photosensitive resin composition is used. Is widely known.
As a method for producing a printed wiring board using the photosensitive resin composition or the photosensitive film as a resist, recently, resource saving,
Partial plating has been drawing attention from the viewpoint of process shortening. This method is a method of plating only on a desired copper pattern by laminating a photosensitive film on a printed wiring board on which a copper pattern is formed by using an appropriate method, exposing and developing, and then plating. Is. By this method, it is possible to partially deposit a metal such as solder or gold on the copper pattern and improve the quality such as component mountability and wear resistance.
【0003】初期には粘着テープをレジストとして用い
てこの様な印刷配線板を作成していたが、テープを配線
板に付着する作業は人手を用いて行っているため、精度
向上、能率向上などの面から感光性フィルムを用いる工
法が考えられている。しかし、従来の感光性フィルムを
用いると、銅パターンに感光性フィルムを追従させるた
め感光性樹脂層を厚くする必要があったり、また、薄膜
の感光性樹脂層を何らかの方法で埋め込ませた場合で
も、銅パターン間の感光性樹脂層が厚くなり、現像時間
が長くなり生産性が低下してしまう問題があった。Initially, such a printed wiring board was prepared by using an adhesive tape as a resist, but since the work of adhering the tape to the wiring board is performed manually, the accuracy and efficiency are improved. From the aspect, a method using a photosensitive film is considered. However, when a conventional photosensitive film is used, it is necessary to thicken the photosensitive resin layer in order to make the photosensitive film follow the copper pattern, or even when the thin photosensitive resin layer is embedded by some method. However, there is a problem that the photosensitive resin layer between the copper patterns becomes thick, the developing time becomes long, and the productivity is lowered.
【0004】[0004]
【発明が解決しようとする課題】本発明は前記した従来
の技術の問題を解決し、パターンへの埋め込み性が向上
した、現像性の良好な感光性樹脂組成物及びこれを用い
た感光性フィルムを提供するものである。DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems of the prior art, improves the embedding property in a pattern and has a good developability, and a photosensitive film using the same. Is provided.
【0005】[0005]
【課題を解決するための手段】本発明は、(A)カルボ
キシル基含有ポリマー、(B)重合可能な二重結合を分
子内に少なくとも2個以上持つ化合物及び(C)光重合
開始剤を含有し、前記(A)成分に数平均分子量5,0
00〜20,000、重量平均分子量20,000〜5
0,000、分散度1.5〜3.0の成分(A−1)及
び数平均分子量20,000〜80,000、重量平均
分子量70,000〜160,000、分散度1.5〜
3.0の成分(A−2)を含み、かつ成分(A−1)の
配合量が成分(A−2)の配合量より多く、前記(B)
成分にポリプロピレングリコールジアクリレートを含む
感光性樹脂組成物並びに支持体上にこの感光性樹脂組成
物を塗布乾燥してなる感光性フィルムに関する。The present invention comprises (A) a carboxyl group-containing polymer, (B) a compound having at least two polymerizable double bonds in the molecule, and (C) a photopolymerization initiator. And the component (A) has a number average molecular weight of 5,0.
00-20,000, weight average molecular weight 20,000-5
Component (A-1) having a polydispersity of 1.5 to 3.0 and a number average molecular weight of 20,000 to 80,000, a weight average molecular weight of 70,000 to 160,000, and a dispersity of 1.5 to
The component (A-2) of 3.0 is contained, and the compounding amount of the component (A-1) is larger than the compounding amount of the component (A-2).
The present invention relates to a photosensitive resin composition containing polypropylene glycol diacrylate as a component, and a photosensitive film obtained by coating and drying the photosensitive resin composition on a support.
【0006】次に、本発明の感光性樹脂組成物に含まれ
る成分について詳述する。本発明に(A)成分(成分
(A−1)及び成分(A−2)を含む)として用いられ
るカルボキシル基含有ポリマーとしては、例えば、(メ
タ)アクリル酸アルキルエステル〔(メタ)アクリル酸
とはメタクリル酸及びアクリル酸を意味する。以下同
じ〕と(メタ)アクリル酸とこれらと共重合しうるビニ
ルモノマーとの共重合体等が挙げられる。これらの共重
合体は、単独で又は2種以上を組み合わせて用いられ
る。Next, the components contained in the photosensitive resin composition of the present invention will be described in detail. Examples of the carboxyl group-containing polymer used as the component (A) (including the component (A-1) and the component (A-2)) in the present invention include (meth) acrylic acid alkyl ester [(meth) acrylic acid and Means methacrylic acid and acrylic acid. The same shall apply hereinafter] and a copolymer of (meth) acrylic acid and a vinyl monomer copolymerizable therewith, and the like. These copolymers may be used alone or in combination of two or more.
【0007】(メタ)アクリル酸アルキルエステルとし
ては、例えば、(メタ)アクリル酸メチルエステル、
(メタ)アクリル酸エチルエステル、(メタ)アクリル
酸ブチルエステル、(メタ)アクリル酸2−エチルヘキ
シルエステル等が挙げられる。また、(メタ)アクリル
酸アルキルエステルや(メタ)アクリル酸と共重合しう
るビニルモノマーとしては、例えば、(メタ)アクリル
酸テトラヒドロフルフリルエステル、(メタ)アクリル
酸ジメチルアミノエチルエステル、(メタ)アクリル酸
ジエチルアミノエチルエステル、メタクリル酸グリシジ
ルエステル、2,2,2−トリフルオロエチル(メタ)
アクリレート、2,2,3,3−テトラフルオロプロピ
ル(メタ)アクリレートアクリルアミド、ジアセトンア
クリルアミド、スチレン、ビニルトルエン等が挙げられ
る。As the (meth) acrylic acid alkyl ester, for example, (meth) acrylic acid methyl ester,
(Meth) acrylic acid ethyl ester, (meth) acrylic acid butyl ester, (meth) acrylic acid 2-ethylhexyl ester and the like can be mentioned. Examples of vinyl monomers copolymerizable with (meth) acrylic acid alkyl ester and (meth) acrylic acid include (meth) acrylic acid tetrahydrofurfuryl ester, (meth) acrylic acid dimethylaminoethyl ester, (meth) Acrylic acid diethylaminoethyl ester, methacrylic acid glycidyl ester, 2,2,2-trifluoroethyl (meth)
Acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate acrylamide, diacetone acrylamide, styrene, vinyltoluene and the like can be mentioned.
【0008】共重合体の製造は、公知の溶液重合法、懸
濁重合法、乳化重合法等を用いて行うことができ、分子
量の調整は、重合開始剤量、連鎖移動剤量等の量を調整
することにより行われる。現像性は、酸価、共重合モノ
マの吸水率により調整でき、最終的には、感光性樹脂組
成物を作成し実際に現像して比較可能である。現像性、
レジスト形状、追従性、耐めっき性、密着性等の観点か
ら、成分(A−1)の数平均分子量は5,000〜2
0,000、重量平均分子量は2,000〜50,00
0、分散度は1.5〜3.0とされ、成分(A−2)の
数平均分子量は20,000〜80,000、重量平均
分子量は70,000〜160,000、分散度は1.
5〜3.0とされる。また、レジスト形状などの観点か
ら、成分(A−1)及び成分(A−2)が、分子量を等
しくし、(A)カルボキシル基含有ポリマーとして各々
単独に用い別々の感光性樹脂組成物を作成した場合、希
アルカリ現像液に対する現像性が(A−2)を用いた感
光性樹脂組成物の方が(A−1)を用いた感光性樹脂組
成物よりも大であることが好ましい。現像性は、最少現
象時間の測定によって求められる。The copolymer can be produced by a known solution polymerization method, suspension polymerization method, emulsion polymerization method or the like. The molecular weight can be adjusted by controlling the amount of the polymerization initiator, the amount of the chain transfer agent and the like. It is done by adjusting. The developability can be adjusted by adjusting the acid value and the water absorption of the copolymerization monomer, and finally, the photosensitive resin composition can be prepared and actually developed for comparison. Developability,
The number average molecular weight of the component (A-1) is 5,000 to 2 from the viewpoint of resist shape, conformability, plating resistance, adhesion, etc.
50,000, the weight average molecular weight is 2,000 to 50,000.
0, the polydispersity is 1.5 to 3.0, the number average molecular weight of the component (A-2) is 20,000 to 80,000, the weight average molecular weight is 70,000 to 160,000, and the polydispersity is 1. .
It is set to 5 to 3.0. In addition, from the viewpoint of the resist shape and the like, the component (A-1) and the component (A-2) have the same molecular weight and are used individually as the (A) carboxyl group-containing polymer to prepare different photosensitive resin compositions. In this case, it is preferable that the developability of the photosensitive resin composition using (A-2) with respect to the diluted alkaline developer is higher than that of the photosensitive resin composition using (A-1). Developability is determined by measuring the minimum phenomenon time.
【0009】本発明において、(A)成分の配合量は、
(A)成分及び(B)成分の総量100重量部に対して
40〜80重量部の範囲とすることが好ましい。40重
量部未満では光硬化物が脆くなり易く、また感光性フィ
ルムとして用いた場合、塗膜性に劣る傾向があり、80
重量部を超えると感度が不充分となる傾向がある。In the present invention, the compounding amount of the component (A) is
The total amount of the components (A) and (B) is preferably 40 to 80 parts by weight based on 100 parts by weight. If it is less than 40 parts by weight, the photocured product tends to become brittle, and when used as a photosensitive film, the coating property tends to be poor.
If the amount is more than parts by weight, the sensitivity tends to be insufficient.
【0010】本発明に(B)成分として用いられる重合
可能な二重結合を分子内に少なくとも2個以上持つ化合
物(光重合性モノマ)としては、例えば、ウレタンアク
リレートビスコート#831(大阪有機化学工業社製商
品名)、ポリエーテル型ウレタンアクリレートBTG−
A(共栄社油脂化学工業社製商品名)、ポリエステル型
ウレタンアクリレートD−200A(共栄社油脂化学工
業社製商品名)、ウレタンアクリレートフォトマー60
08(サンノプコ社製商品名)、ウレタンジアクリレー
トケムリンク9503(サートマ社製商品名)、これら
のウレタンメタクリレート等が用いられる。また、トリ
メチルヘキサンメチレンジイソシアネート等のイソシア
ネート化合物と必要に応じて用いられるシクロヘキサン
ジメタノール等のジアルコール化合物と2−ヒドロキシ
エチルアクリレート等のヒドロキシル基含有(メタ)ア
クリレートとを反応させ得られる化合物、トリメチロー
ルプロパンエトキシトリアクリレート(SR−454、
サートマ社製商品名)、トリメチロールプロパンプロポ
キシトリアクリレート(R−924、日本化薬社製商品
名)、ポリエチレングリコールジ(メタ)アクリレート
(エチレン基の数が2〜14のもの)、トリメチロール
プロパンジ(メタ)アクリレート、トリメチロールプロ
パントリ(メタ)アクリレート、テトラメチロールメタ
ントリ(メタ)アクリレート、テトラメチロールメタン
テトラ(メタ)アクリレート、ポリプロピレングリコー
ルジ(メタ)アクリレート、ジペンタエリスリトールペ
ンタ(メタ)アクリレート、ジペンタエリスリトールヘ
キサ(メタ)アクリレート等の多価アルコールにα,β
−不飽和カルボン酸を反応させて得られる化合物、ビス
フェノールAジオキシエチレンジ(メタ)アクリレー
ト、ビスフェノールAトリオキシエチレンジ(メタ)ア
クリレート、ビスフェノールAデカオキシエチレンジ
(メタ)アクリレート、トリメチロールプロパントリグ
リシジルエーテルトリアクリレート、ビスフェノールA
ジグリシジルエーテルアクリレート等のグリシジル基含
有化合物にα,β−不飽和カルボン酸を付加して得られ
る化合物、無水フタル酸等の多価カルボン酸とβ−ヒド
ロキシエチル(メタ)アクリレート等の水酸基及びエチ
レン性不飽和基を有する物質とのエステル化物、(メ
タ)アクリル酸メチルエステル、(メタ)アクリル酸エ
チルエステル、(メタ)アクリル酸ブチルエステル、
(メタ)アクリル酸2−エチルヘキシルエステル等の
(メタ)アクリル酸のアルキルエステルなどが挙げられ
る。これらのうちで、レジスト形状の観点からポリプロ
ピレングリコールジアクリレートを必ず用い、他の化合
物については任意に用いることが可能である。Examples of the compound (photopolymerizable monomer) having at least two polymerizable double bonds in the molecule used as the component (B) in the present invention include urethane acrylate biscoat # 831 (Osaka Organic Chemistry). Trade name, manufactured by Kogyo Co., Ltd., polyether type urethane acrylate BTG-
A (trade name of Kyoeisha Oil and Fat Chemical Co., Ltd.), polyester type urethane acrylate D-200A (trade name of Kyoeisha Oil and Fat Chemical Co., Ltd.), urethane acrylate Photomer 60
08 (trade name, manufactured by San Nopco), urethane diacrylate Chemlink 9503 (trade name, manufactured by Sartoma), and urethane methacrylates thereof are used. Also, a compound obtained by reacting an isocyanate compound such as trimethylhexanemethylene diisocyanate with a dialcohol compound such as cyclohexanedimethanol optionally used and a hydroxyl group-containing (meth) acrylate such as 2-hydroxyethyl acrylate, trimethylol Propane ethoxy triacrylate (SR-454,
Satoma brand name), trimethylolpropane propoxytriacrylate (R-924, Nippon Kayaku brand name), polyethylene glycol di (meth) acrylate (having 2 to 14 ethylene groups), trimethylolpropane Di (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethylolmethane tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, polypropylene glycol di (meth) acrylate, dipentaerythritol penta (meth) acrylate, Α, β in polyhydric alcohols such as dipentaerythritol hexa (meth) acrylate
-Compounds obtained by reacting unsaturated carboxylic acids, bisphenol A dioxyethylene di (meth) acrylate, bisphenol A trioxyethylene di (meth) acrylate, bisphenol A decaoxyethylene di (meth) acrylate, trimethylolpropane tri Glycidyl ether triacrylate, bisphenol A
Compounds obtained by adding α, β-unsaturated carboxylic acids to glycidyl group-containing compounds such as diglycidyl ether acrylate, polyvalent carboxylic acids such as phthalic anhydride, and hydroxyl groups and ethylene such as β-hydroxyethyl (meth) acrylate With a substance having an unsaturated group, (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid butyl ester,
Examples thereof include alkyl esters of (meth) acrylic acid such as (meth) acrylic acid 2-ethylhexyl ester. Of these, polypropylene glycol diacrylate is always used from the viewpoint of resist shape, and other compounds can be arbitrarily used.
【0011】また、(B)成分の配合量は、(A)成分
及び(B)成分の総量100重量部に対し、20〜60
重量部の範囲とすることが好ましい。この配合量が20
重量部未満では感度が不充分となる傾向があり、60重
量部を超えると光硬化物が脆くなる傾向がある。なお、
(B)成分中の必須成分であるポリプロピレングリコー
ルジアクリレート配合量は5〜30重量部の範囲
((A)成分及び(B)成分の総量100重量部に対し
て)とすることが好ましい。The blending amount of the component (B) is 20 to 60 based on 100 parts by weight of the total amount of the components (A) and (B).
It is preferably in the range of parts by weight. This blend amount is 20
If it is less than 60 parts by weight, the sensitivity tends to be insufficient, and if it exceeds 60 parts by weight, the photocured product tends to become brittle. In addition,
The amount of polypropylene glycol diacrylate, which is an essential component in the component (B), is preferably in the range of 5 to 30 parts by weight (based on 100 parts by weight of the total amount of the components (A) and (B)).
【0012】本発明に(C)成分として用いられる光重
合開始剤としては、例えば、ベンゾフェノン、N,N′
−テトラメチル−4,4′−ジアミノベンゾフェノン
(ミヒラーケトン)、N,N−テトラメチル−4,4′
ジアミノベンゾフェノン、4−メトキシ−4′−ジメチ
ルアミノベンゾフェノン、2−エチルアントラキノン、
フェナントレンキノン等の芳香族ケトン、ベンゾインメ
チルエーテル、ベンゾインエチルエーテル、ベンゾイン
フェニルエーテル等のベンゾインエーテル、メチルベン
ゾイン、エチルベンゾイン等のベンゾイン、ベンジルジ
メチルケタール等のベンジル誘導体、2−(o−クロロ
フェニル)−4,5−ジフェニルイミダゾール二量体、
2−(o−クロロフェニル)−4,5−ジ(m−メトキ
シフェニル)イミダゾール二量体、2−(o−フルオロ
フェニル)−4,5−ジフェニルイミダゾール二量体、
2−(o−メトキシフェニル)−4,5−ジフェニルイ
ミダゾール二量体、2−(p−メトキシフェニル)−
4,5−ジフェニルイミダゾール二量体、2,4−ジ
(p−メトキシフェニル)−5−ジフェニルイミダゾー
ル二量体、2−(2,4−ジメトキシフェニル)−4,
5−ジフェニルイミダゾール二量体、2−(p−メチル
メルカプトフェニル)−4,5−ジフェニルイミダゾー
ル二量体等の2,4,5−トリアリールイミダゾール二
量体、9−フェニルアクリジン、1,7−ビス(9,
9′−アクリジニル)ヘプタン等のアクリジン誘導体な
どが挙げられる。これらは、単独で又は2種以上を組み
合わせて用いられる。Examples of the photopolymerization initiator used as the component (C) in the present invention include benzophenone, N, N '.
-Tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), N, N-tetramethyl-4,4 '
Diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 2-ethylanthraquinone,
Aromatic ketones such as phenanthrenequinone, benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether and other benzoin ethers, methylbenzoin, ethylbenzoin and other benzoins, benzyl dimethyl ketal and other benzyl derivatives, 2- (o-chlorophenyl) -4 , 5-diphenylimidazole dimer,
2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer,
2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl)-
4,5-diphenylimidazole dimer, 2,4-di (p-methoxyphenyl) -5-diphenylimidazole dimer, 2- (2,4-dimethoxyphenyl) -4,
2,4,5-triarylimidazole dimer such as 5-diphenylimidazole dimer and 2- (p-methylmercaptophenyl) -4,5-diphenylimidazole dimer, 9-phenylacridine, 1,7 -Bis (9,
Examples include acridine derivatives such as 9'-acridinyl) heptane. These are used alone or in combination of two or more.
【0013】光重合開始剤である(C)成分の配合量
は、(A)成分及び(B)成分の総量100重量部に対
して0.05〜10重量部の範囲とすることが好まし
い。0.05重量部未満では感度が不充分となる傾向が
あり、10重量部を超えると露光の際に組成物の表面で
の吸収が増大して内部の光硬化が不充分となる傾向があ
る。The amount of the component (C) which is a photopolymerization initiator is preferably in the range of 0.05 to 10 parts by weight based on 100 parts by weight of the total amount of the components (A) and (B). If it is less than 0.05 parts by weight, the sensitivity tends to be insufficient, and if it exceeds 10 parts by weight, the absorption on the surface of the composition is increased during exposure and the internal photocuring tends to be insufficient. .
【0014】本発明の感光性樹脂組成物は、必要に応じ
て可塑剤、染料、顔料レベリング剤、充填剤、イメージ
ング剤、密着性向上剤等を添加して用いても良い。The photosensitive resin composition of the present invention may be added with a plasticizer, a dye, a pigment leveling agent, a filler, an imaging agent, an adhesion improver, etc., if necessary.
【0015】本発明の感光性樹脂組成物は、金属面、例
えば、銅、ニッケル、クロム等の表面、好ましくは銅表
面上に、液状レジストとして塗布して乾燥後、保護フィ
ルムを被覆して用いるか、あるいは感光性フィルムとし
て用いられる。感光性フィルム中の感光性樹脂組成物の
厚みは用途により異なるが、乾燥後の厚みで10〜10
0μm程度であることが好ましい。液状レジストの場合
は、保護フィルムとしてポリエチレン、ポリプロピレン
等の不活性なポリオレフィンフィルム、ポリエステルフ
ィルム等が用いられる。The photosensitive resin composition of the present invention is applied as a liquid resist on a metal surface, for example, a surface of copper, nickel, chromium or the like, preferably a copper surface, dried and then coated with a protective film. Or used as a photosensitive film. The thickness of the photosensitive resin composition in the photosensitive film varies depending on the use, but the thickness after drying is 10 to 10
It is preferably about 0 μm. In the case of a liquid resist, an inert polyolefin film such as polyethylene or polypropylene, a polyester film or the like is used as the protective film.
【0016】感光性フィルムは、ポリエステル等の支持
体フィルム上に感光性樹脂組成物を塗布、乾燥すること
により積層し、必要に応じてポリオレフィン等の保護フ
ィルムを積層して得られる。感光性樹脂組成物は、必要
に応じてアセトン、メチルエチルケトン、塩化メチレ
ン、トルエン、メタノール、エタノール、プロパノー
ル、ブタノール、メチルグリコール、エチルグリコー
ル、プロピレングリコール、エチレングリコールモノメ
チルエーテル等の溶剤又はこれらの混合溶剤と混合して
溶液として塗布してもよい。The photosensitive film can be obtained by coating a support film such as polyester with a photosensitive resin composition and drying it to form a laminate, and if necessary, laminating a protective film such as polyolefin. The photosensitive resin composition, if necessary, with a solvent such as acetone, methyl ethyl ketone, methylene chloride, toluene, methanol, ethanol, propanol, butanol, methyl glycol, ethyl glycol, propylene glycol, ethylene glycol monomethyl ether or a mixed solvent thereof. You may mix and apply as a solution.
【0017】前記の感光性樹脂組成物層は、アートワー
クと呼ばれるネガ又はポジマスクパターンを通して活性
光線が照射された後、現像液で現像され、レジストパタ
ーンとされる。この際用いられる活性光線としては、例
えば、カーボンアーク灯、超高圧水銀灯、高圧水銀灯、
キセノンランプ等の紫外線を有効に放射するものが用い
られる。The photosensitive resin composition layer is irradiated with an actinic ray through a negative or positive mask pattern called an artwork, and then developed with a developing solution to form a resist pattern. Examples of the actinic ray used at this time include a carbon arc lamp, an ultra-high pressure mercury lamp, a high pressure mercury lamp,
What effectively emits ultraviolet rays, such as a xenon lamp, is used.
【0018】現像液としては、安全かつ安定であり、操
作性が良好なものが用いられ、アルカリ現像型のフォト
レジストでは炭酸ナトリウムの希薄溶液等が用いられ
る。現像の方法には、ディップ方式、スプレー方式等が
あり、高圧スプレー方式が解像度向上のためには最も適
している。As the developing solution, a developing solution which is safe and stable and has good operability is used, and a dilute solution of sodium carbonate or the like is used for an alkali developing type photoresist. Development methods include a dip method and a spray method, and the high pressure spray method is most suitable for improving the resolution.
【0019】現像後に行われる電気めっきには、硫酸銅
めっき、ピロリン酸銅めっき等の銅めっき、ハイスロー
はんだめっき等のはんだめっき、ワット浴(硫酸ニッケ
ル−塩化ニッケル)めっき、スルファミン酸ニッケルめ
っき等のニッケルめっき、ハード金めっき、ソフト金め
っき等の金めっきなどがある。The electroplating performed after development includes copper sulfate plating, copper plating such as copper pyrophosphate plating, solder plating such as high-throw solder plating, Watts bath (nickel sulfate-nickel chloride) plating, nickel sulfamate plating and the like. Gold plating such as nickel plating, hard gold plating, and soft gold plating is available.
【0020】[0020]
【実施例】次に本発明を実施例により詳しく説明する
が、本発明はこれらにより制限されるものではない。実
施例1〜7及び比較例1〜2マラカイトグリーン0.0
5g、メチルエチルケトン10g、トルエン10g、メ
タノール3g及び1,7−ビス(9,9′−アクリジニ
ル)ヘプタン〔(C)成分〕0.2g、4,4′−ビス
〔(N,N−ジエチルアミノ)メチル〕ベンゾフェノン
0.05g、トリブロモメチルフェニルスルホン0.5
g、3−ジエチルアミノ−6−メチル−7−アルキル
(C8〜C16)アミノフルオラン0.5gを配合し溶液
を得た。EXAMPLES The present invention will now be described in more detail by way of examples, which should not be construed as limiting the invention. Examples 1-7 and Comparative Examples 1-2 Malachite Green 0.0
5 g, methyl ethyl ketone 10 g, toluene 10 g, methanol 3 g and 1,7-bis (9,9'-acridinyl) heptane [(C) component] 0.2 g, 4,4'-bis [(N, N-diethylamino) methyl ] Benzophenone 0.05 g, Tribromomethylphenyl sulfone 0.5
g, to give 3-diethylamino-6-methyl-7-alkyl (C 8 ~C 16) blended aminofluoran 0.5g solution.
【0021】この溶液に、表1に示す組成のA成分及び
B成分を、表2に記載の量を溶解させて感光性樹脂組成
物の溶液を得た。The components A and B having the compositions shown in Table 1 were dissolved in the solution in the amounts shown in Table 2 to obtain a solution of a photosensitive resin composition.
【0022】[0022]
【表1】 [Table 1]
【0023】[0023]
【表2】 [Table 2]
【0024】次いで、この感光性樹脂組成物の溶液を2
5μm厚のポリエチレンテレフタレートフィルム上に均
一に塗布し、100℃の熱風対流式乾燥機で約10分間
乾燥して感光性フィルムを得た。感光性樹脂組成物層の
乾燥後の膜厚は、50μmであった。Then, a solution of this photosensitive resin composition was added to
It was evenly coated on a polyethylene terephthalate film having a thickness of 5 μm and dried by a hot air convection dryer at 100 ° C. for about 10 minutes to obtain a photosensitive film. The film thickness of the photosensitive resin composition layer after drying was 50 μm.
【0025】一方、銅箔(厚さ35μm)を両面に積層
したガラスエポキシ材である銅張り積層板(日立化成工
業社製商品名、MCL−E−61)及び0.5mm間隔で
銅ラインを形成した銅張積層板(銅厚35、50、70
μmの3種類)の銅表面を#600相当のブラシを持つ
研磨機(三啓社製)を用いて研磨し、水洗後、空気流で
乾燥し、得られた銅張り積層板を80℃に加温し、その
銅表面上に前記感光性樹脂組成物層を120℃に加熱し
ながらラミネートした。On the other hand, a copper-clad laminate (MCL-E-61 manufactured by Hitachi Chemical Co., Ltd.), which is a glass epoxy material in which copper foil (thickness 35 μm) is laminated on both sides, and copper lines are provided at 0.5 mm intervals. Formed copper clad laminate (copper thickness 35, 50, 70
(3 types of μm) are polished with a polishing machine (manufactured by Sankei Co., Ltd.) having a brush equivalent to # 600, washed with water, and then dried with an air stream, and the obtained copper-clad laminate is heated to 80 ° C. It heated and laminated the said photosensitive resin composition layer on the copper surface, heating at 120 degreeC.
【0026】次いで、ポリエチレンテレフタレートフィ
ルム上に、ネガフィルムを載置し、3kW高圧水銀灯(オ
ーク製作所社製、HMW−201B)で60mJ/cm2の露
光を行った。この際、光感度を評価できるように、ネガ
フィルムに光透過量が段階的に少なくなる領域(光学密
度0.05を1段目とし、1段ごとに光学密度が0.1
5ずつ増加するステップタブレット(ST))を設け
た。Then, a negative film was placed on the polyethylene terephthalate film, and exposed at 60 mJ / cm 2 with a 3 kW high pressure mercury lamp (HMW-201B manufactured by Oak Manufacturing Co., Ltd.). At this time, in order to evaluate the photosensitivity, a region where the amount of light transmission gradually decreases in the negative film (the optical density of 0.05 is set as the first step and the optical density is set to 0.1% for each step).
A step tablet (ST) increasing by 5 was provided.
【0027】次いで、ポリエチレンテレフタレートフィ
ルムを除去し、30℃で1重量%炭酸ナトリウム水溶液
を50秒間スプレーすることにより、未露光部分を除去
した。さらに、銅張り積層板上に形成された光硬化膜の
ステップタブレットの段数を測定することにより、感光
性樹脂組成物の光感度を評価した。その結果を表3に示
した。光感度は、ステップタブレットの段数で示され、
このステップタブレットの段数が高いほど、光感度が高
いことを示す。ステップタブレットの1段部分(光学密
度0.05)を走査形電子顕微鏡で観察し、レジスト形
状の評価をした。その結果を表3に示す。Then, the polyethylene terephthalate film was removed, and an unexposed portion was removed by spraying a 1 wt% sodium carbonate aqueous solution at 30 ° C. for 50 seconds. Furthermore, the photosensitivity of the photosensitive resin composition was evaluated by measuring the number of steps of the step tablet of the photocured film formed on the copper-clad laminate. The results are shown in Table 3. Light sensitivity is indicated by the number of steps of the step tablet,
The higher the number of steps of this step tablet, the higher the photosensitivity. The one-step portion (optical density 0.05) of the step tablet was observed with a scanning electron microscope to evaluate the resist shape. The results are shown in Table 3.
【0028】また一方、感光性フィルムをラミネートし
た基板の最少現像時間を測定し、その結果を表3に合わ
せて記載した。最少現像時間は、125mm×200mmの
銅張積層板に前記感光性フィルムをラミネートし、未露
光の状態でポリエチレンテレフタレートフィルムをはが
し、圧力1.8kgf/cm2を有するスプレー式現像機で現
像(1重量%の炭酸ナトリウム水溶液、30℃)し、次
いで水洗、乾燥した後観察し、表面に感光性樹脂層の存
在が認められなくなる最少の時間を示す。この最少現像
時間が短い程、現像性が大きい。また、0.5mm間隔の
銅パターンを形成した銅張積層板(銅厚35μm、50
μm、70μm)に感光性フィルムをラミネートした基
板は、その断面形状を観察し、感光性樹脂層の凹凸への
追従性(銅厚70μmでの埋め込み性)及びその最少現
像時間を測定し表3に合わせて記載した。On the other hand, the minimum development time of the substrate laminated with the photosensitive film was measured, and the results are shown in Table 3 together. The minimum development time is such that the photosensitive film is laminated on a copper-clad laminate of 125 mm × 200 mm, the polyethylene terephthalate film is peeled off in an unexposed state, and the development is carried out by a spray type developing machine having a pressure of 1.8 kgf / cm 2. A weight% sodium carbonate aqueous solution (30 ° C.), followed by washing with water and drying, and then observing shows the minimum time when the presence of the photosensitive resin layer is not recognized on the surface. The shorter the minimum development time, the higher the developability. In addition, a copper clad laminate (copper thickness 35 μm, 50
For a substrate having a photosensitive film laminated to a thickness of 70 .mu.m), the cross-sectional shape was observed, and the followability to irregularities of the photosensitive resin layer (embedding property at a copper thickness of 70 .mu.m) and its minimum development time were measured. It is described in accordance with.
【0029】[0029]
【表3】 [Table 3]
【0030】表3より、カルボキシル基含有ポリマーと
して低分子量と高分子量を程良くブレンドすることで埋
込み性と凹凸部の最少現像時間が短縮できることが分か
る。更に、重合可能な二重結合を分子内に少なくとも2
個以上持つ化合物(光重合性モノマー)としてポリプロ
ピレングリコールジアクリレートを用いることで、レジ
スト形状が良好になることが分かる。It can be seen from Table 3 that the embedding property and the minimum development time of the uneven portion can be shortened by appropriately blending the low molecular weight and the high molecular weight as the carboxyl group-containing polymer. Furthermore, at least two polymerizable double bonds are included in the molecule.
It can be seen that the use of polypropylene glycol diacrylate as a compound having more than one (photopolymerizable monomer) improves the resist shape.
【0031】[0031]
【発明の効果】本発明により、追従性が良好で埋込部の
現像性良好な感光性樹脂組成物及びこれを用いた感光性
フィルムが提供できる。According to the present invention, it is possible to provide a photosensitive resin composition having good followability and good developability of the embedded portion, and a photosensitive film using the same.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 FI H05K 3/06 H05K 3/06 J 3/18 3/18 D 3/24 3/24 A ─────────────────────────────────────────────────── ─── Continued Front Page (51) Int.Cl. 7 Identification Code FI H05K 3/06 H05K 3/06 J 3/18 3/18 D 3/24 3/24 A
Claims (5)
(B)重合可能な二重結合を分子内に少なくとも2個以
上持つ化合物及び(C)光重合開始剤を含む感光性樹脂
組成物であって、 前記(A)成分が、数平均分子量5,000〜20,0
00、重量平均分子量20,000〜50,000、分
散度1.5〜3.0の成分(A−1)及び数平均分子量
20,000〜80,000、重量平均分子量70,0
00〜160,000、分散度1.5〜3.0の成分
(A−2)を含み、かつ成分(A−1)の配合量が成分
(A−2)の配合量より多く、 前記(B)成分がポリプロピレングリコールジアクリレ
ート、ことを特徴とする感光性樹脂組成物。1. A polymer containing a carboxyl group (A),
A photosensitive resin composition comprising (B) a compound having at least two polymerizable double bonds in a molecule and (C) a photopolymerization initiator, wherein the component (A) has a number average molecular weight of 5, 000 to 20,0
00, weight average molecular weight 20,000 to 50,000, component (A-1) having a dispersity of 1.5 to 3.0, and number average molecular weight 20,000 to 80,000, weight average molecular weight 70,0.
Including the component (A-2) having a dispersity of 1.5 to 3.0 and an amount of the component (A-1) greater than the amount of the component (A-2), Component B) is a polypropylene glycol diacrylate, which is a photosensitive resin composition.
シエチレンジ(メタ)アクリレート、ビスフェノールA
トリオキシエチレンジ(メタ)アクリレート又はビスフ
ェノールAデカオキシエチレンジ(メタ)アクリレート
を更に含む、請求項1記載の感光性樹脂組成物。2. The component (B) is bisphenol A dioxyethylene di (meth) acrylate, bisphenol A.
The photosensitive resin composition according to claim 1, further comprising trioxyethylene di (meth) acrylate or bisphenol A decaoxyethylene di (meth) acrylate.
(メタ)アクリル酸アルキルエステルと(メタ)アクリ
ル酸とこれらと共重合しうるビニルモノマーとの共重合
体である、請求項1又は2記載の感光性樹脂組成物。3. The component (A-1) and the component (A-2) are
The photosensitive resin composition according to claim 1 or 2, which is a copolymer of (meth) acrylic acid alkyl ester, (meth) acrylic acid, and a vinyl monomer copolymerizable therewith.
分子量を等しくし、(A)カルボキシル基含有ポリマー
として各々単独に用い別々の感光性樹脂組成物を作成し
た場合、希アルカリ現像液に対する現像性が(A−2)
を用いた感光性樹脂組成物の方が(A−1)を用いた感
光性樹脂組成物よりも大である、請求項1〜3のいずれ
か1項記載の感光性樹脂組成物。4. The component (A-1) and the component (A-2) are
When different photosensitive resin compositions having the same molecular weight and each of (A) a carboxyl group-containing polymer are separately used, the developability with respect to a dilute alkaline developer is (A-2).
The photosensitive resin composition according to any one of claims 1 to 3, wherein the photosensitive resin composition containing (A) is larger than the photosensitive resin composition containing (A-1).
記載の感光性樹脂組成物を塗布、乾燥してなる感光性フ
ィルム。5. A photosensitive film obtained by coating the support with the photosensitive resin composition according to claim 1 and drying the composition.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP12718594A JP3415928B2 (en) | 1994-06-09 | 1994-06-09 | Photosensitive resin composition and photosensitive film using the same |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP12718594A JP3415928B2 (en) | 1994-06-09 | 1994-06-09 | Photosensitive resin composition and photosensitive film using the same |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH07333846A JPH07333846A (en) | 1995-12-22 |
JP3415928B2 true JP3415928B2 (en) | 2003-06-09 |
Family
ID=14953790
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP12718594A Expired - Lifetime JP3415928B2 (en) | 1994-06-09 | 1994-06-09 | Photosensitive resin composition and photosensitive film using the same |
Country Status (1)
Country | Link |
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JP (1) | JP3415928B2 (en) |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH10161308A (en) * | 1996-11-26 | 1998-06-19 | Asahi Chem Ind Co Ltd | Photopolymerizable resin composition and its use |
JPH10198027A (en) * | 1997-01-14 | 1998-07-31 | Asahi Chem Ind Co Ltd | Photopolymerizable resin and its use |
JP3100040B2 (en) * | 1997-07-04 | 2000-10-16 | 日本合成化学工業株式会社 | Photoresist film |
US5962190A (en) * | 1997-08-27 | 1999-10-05 | E. I. Du Pont De Nemours And Company | Photopolymerizable compositions having improved sidewall geometry and development latitude |
JP4517257B2 (en) * | 2000-04-25 | 2010-08-04 | 日立化成工業株式会社 | Photosensitive resin composition, photosensitive element using the same, resist pattern manufacturing method, and printed wiring board manufacturing method |
WO2001098832A1 (en) * | 2000-06-22 | 2001-12-27 | Hitachi Chemical Co., Ltd. | Photosensitive resin composition, photosensitive element comprising the same, process for producing resist pattern, and process for producing printed circuit board |
JP4529289B2 (en) * | 2001-01-09 | 2010-08-25 | 日立化成工業株式会社 | Photosensitive resin composition, photosensitive element using the same, resist pattern manufacturing method, and printed wiring board manufacturing method |
JP6064480B2 (en) * | 2011-10-26 | 2017-01-25 | 日立化成株式会社 | Photosensitive resin composition, photosensitive element, resist pattern forming method and printed wiring board manufacturing method |
CN103076719B (en) * | 2011-10-26 | 2019-08-09 | 日立化成株式会社 | The manufacturing method of photosensitive polymer combination, photosensitive element, the forming method of corrosion-resisting pattern and printing distributing board |
CN104730863B (en) * | 2014-11-03 | 2018-08-14 | 杭州福斯特应用材料股份有限公司 | A kind of dry film photoresist |
-
1994
- 1994-06-09 JP JP12718594A patent/JP3415928B2/en not_active Expired - Lifetime
Also Published As
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---|---|
JPH07333846A (en) | 1995-12-22 |
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