JP3193468B2 - Manufacturing method of printed circuit board - Google Patents
Manufacturing method of printed circuit boardInfo
- Publication number
- JP3193468B2 JP3193468B2 JP20610292A JP20610292A JP3193468B2 JP 3193468 B2 JP3193468 B2 JP 3193468B2 JP 20610292 A JP20610292 A JP 20610292A JP 20610292 A JP20610292 A JP 20610292A JP 3193468 B2 JP3193468 B2 JP 3193468B2
- Authority
- JP
- Japan
- Prior art keywords
- printed circuit
- circuit board
- added
- reaction
- solder
- 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 - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
- C04B28/04—Portland cements
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/52—Multiple coating or impregnating multiple coating or impregnating with the same composition or with compositions only differing in the concentration of the constituents, is classified as single coating or impregnation
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Non-Metallic Protective Coatings For Printed Circuits (AREA)
Description
【0001】[0001]
【産業上の利用分野】本発明は、プリント回路板の製造
方法の改良に関わり、さらに詳しくは耐熱性、耐薬品
性、絶縁性及び可撓性のよい光硬化性ポリイミド樹脂の
半田保護膜(ソルダーレジスト)の利用に係る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an improvement in a method of manufacturing a printed circuit board, and more particularly to a solder protective film of a photocurable polyimide resin having good heat resistance, chemical resistance, insulation and flexibility. Solder resist).
【0002】[0002]
【従来の技術】従来、産業用エレクトロニクスではリジ
ッドやフレキシブルのプリント回路板が使用されるが、
プリント回路板の組立てに際してソルダーレジストの形
成はほとんど必要工程の1 つである。従来、ソルダーレ
ジストとして、アルキッド/メラミン樹脂、エポキシ/
メラミン樹脂、二液性エポキシ樹脂等の熱硬化性ソルダ
ーレジスト組成物が用いられており、これらの熱硬化性
ソルダーレジストは、プリント回路板の表面に印刷その
他の方法で塗布され、その後加熱硬化させて保護膜を形
成していた。2. Description of the Related Art Conventionally, rigid and flexible printed circuit boards are used in industrial electronics.
The formation of solder resist is one of the most necessary steps when assembling a printed circuit board. Conventionally, alkyd / melamine resin, epoxy /
Melamine resin, a thermosetting solder resist composition such as a two-part epoxy resin is used, and these thermosetting solder resists are applied to the surface of a printed circuit board by printing or other methods, and then heat-cured. To form a protective film.
【0003】しかし、上記従来のソルダーレジストは、
塗布後の加熱硬化に相当の時間と温度を必要とするため
に生産性が悪く、また高い加熱硬化温度のために基板の
反り、収縮等が発生しやすいという問題があった。これ
らの問題点を解消すべく民生用プリント回路板に用いら
れている紫外線(UV)硬化のソルダーレジストが検討
されたが、産業用エレクトロニクスに使用されるプリン
ト回路板は、銀や銅の導体回路部の厚さは非常に厚く
(約50〜70μm )、ソルダーレジストの絶縁性を維持す
るために厚く塗布しなければならない。ところが、民生
用UV硬化レジストでは厚膜での硬化性に問題があり、
一方膜厚を薄くすると産業用プリント回路板に適用した
場合に、絶縁性および半田耐熱性が悪く、半田保護およ
び絶縁保護として信頼性を保つことはできないことがわ
かった。さらにフレキシブルプリント回路板の場合に
は、上記の信頼性に加えて極めて良好な造膜性と可撓性
が要求されるために、従来の加熱硬化およびUV硬化の
ソルダーレジストでは十分にその特性を満足させること
ができない。従って産業用プリント回路板やフレキシブ
ルプリント回路板に用いるUV硬化ソルダーレジストの
開発が要望されていた。However, the above-mentioned conventional solder resist is
There is a problem that productivity is poor because a considerable time and temperature are required for heat curing after application, and there is a problem that the substrate is easily warped or shrunk due to a high heat curing temperature. To solve these problems, ultraviolet (UV) -cured solder resists used in consumer printed circuit boards have been studied. However, printed circuit boards used in industrial electronics have been developed using silver or copper conductor circuits. The thickness of the part is very thick (about 50 to 70 μm) and must be applied thickly to maintain the insulating properties of the solder resist. However, there is a problem with the curability of thick UV-curable resist for consumer use.
On the other hand, it has been found that when the film thickness is reduced, when applied to an industrial printed circuit board, insulation and solder heat resistance are poor, so that reliability cannot be maintained as solder protection and insulation protection. Furthermore, in the case of flexible printed circuit boards, in addition to the above-mentioned reliability, extremely good film-forming properties and flexibility are required, so that conventional heat-cured and UV-cured solder resists have sufficient characteristics. I cannot be satisfied. Therefore, there has been a demand for the development of a UV-curable solder resist used for industrial printed circuit boards and flexible printed circuit boards.
【0004】[0004]
【発明が解決しようとする課題】本発明は、上記の事情
に鑑みてなされたもので、電気絶縁性、半田耐熱性、造
膜性、可撓性および耐薬品性に優れたソルダーレジスト
を利用する、プリント回路板の製造方法を提供しようと
するものである。SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and utilizes a solder resist excellent in electrical insulation, solder heat resistance, film forming property, flexibility and chemical resistance. And a method of manufacturing a printed circuit board.
【0005】[0005]
【課題を解決するための手段】本発明者は、上記の目的
を達成しようと鋭意研究を重ねた結果、ポリイミドのベ
ースポリマー側鎖にビニルエーテル基を有する新規な光
硬化性樹脂組成物を、ソルダーレジストに用いることに
よって、上記の目的を達成できることを見いだし、本発
明を完成したものである。Means for Solving the Problems As a result of intensive studies aimed at achieving the above object, the present inventors have developed a novel photocurable resin composition having a vinyl ether group in the side chain of a polyimide base polymer, and It has been found that the above object can be achieved by using the resist, and the present invention has been completed.
【0006】即ち、本発明は、 (A)次の一般式で示される構成単位を少なくとも1 個
含むポリイミド重合体That is, the present invention relates to (A) a polyimide polymer containing at least one structural unit represented by the following general formula:
【0007】[0007]
【化2】 (但し、式中、R1 は4 価の有機基を、R2 は3 価の芳
香族基を、R3 は2 価の有機基をそれぞれ表す) (B)希釈剤および (C)増感剤又は光重合開始剤を必須成分とする光硬化
性樹脂組成物を、回路基板上に塗布・露光硬化して保護
膜を形成し、次いで保護膜非形成部分に半田を析出させ
ることを特徴とするプリント回路板の製造方法である。Embedded image (Wherein, R 1 represents a tetravalent organic group, R 2 represents a trivalent aromatic group, and R 3 represents a divalent organic group.) (B) Diluent and (C) sensitization A photocurable resin composition containing an agent or a photopolymerization initiator as an essential component is coated and exposed and cured on a circuit board to form a protective film, and then a solder is deposited on a portion where no protective film is formed. This is a method for manufacturing a printed circuit board.
【0008】以下、本発明を詳細に説明する。Hereinafter, the present invention will be described in detail.
【0009】本発明に用いる(A)新規なポリイミド重
合体は、例えば、(a )化3の一般式で示される、テト
ラカルボン酸二無水物とジアミンからなるイミド分子鎖
とカルボキシル基側鎖をもつ構成単位を少なくとも1 個
有するポリイミド樹脂と、The (A) novel polyimide polymer used in the present invention comprises, for example, (a) an imide molecular chain composed of tetracarboxylic dianhydride and diamine and a carboxyl side chain represented by the general formula (3). A polyimide resin having at least one structural unit having
【0010】[0010]
【化3】 (但し、式中R1 は4 価の有機基を、R2 は3 価の芳香
族基をそれぞれ表す)(b )化4の一般式で示されるヒ
ドロキシアルキルビニルエーテルなどEmbedded image (Wherein R 1 represents a tetravalent organic group and R 2 represents a trivalent aromatic group) (b) hydroxyalkyl vinyl ether represented by the general formula
【0011】[0011]
【化4】HOR3 OCH=CH2 (但し、式中R3 は2 価の有機基を表す)とを反応させ
て得られる。[Image Omitted] The compound is obtained by reacting with HOR 3 OCHCHCH 2 (wherein R 3 represents a divalent organic group).
【0012】(a )一般式化3で示される構成単位の、
カルボキシル基を有するポリイミド樹脂は、有機溶剤可
溶なものであればよい。(A) a structural unit represented by the general formula 3
The polyimide resin having a carboxyl group only needs to be soluble in an organic solvent.
【0013】(b )一般式化4で示されるものとして、
ヒドロキシアルキルビニルエーテルでは、例えば2-ヒド
ロキシエチルビニルエーテル、1-ヒドロキシエチルビニ
ルエーテルなどが、そのほかでは4-ヒドロキシメチルフ
ェニルビニルエーテルなどが挙げられ、これらは単独又
は混合して使用することができる。(B) As shown in the general formula 4,
Examples of the hydroxyalkyl vinyl ether include 2-hydroxyethyl vinyl ether and 1-hydroxyethyl vinyl ether, and others include 4-hydroxymethylphenyl vinyl ether. These can be used alone or in combination.
【0014】(a )の一般式化3で示される構成単位を
含むポリイミド樹脂と、(b )のヒドロキシアルキルビ
ニルエーテル類との反応は、溶剤中で縮合剤の存在下、
塩基を共存させて両者を接触させることにより行うこと
ができる。The reaction between the (a) polyimide resin containing the structural unit represented by the general formula (3) and the (b) hydroxyalkyl vinyl ether is carried out in a solvent in the presence of a condensing agent.
It can be carried out by contacting both in the presence of a base.
【0015】ここで用いる溶剤としては、ジメチルスル
ホオキシド、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,N−ジメチルアセトアミ
ド、N,N−ジエチルアセトアミド、N−メチル−2-ピ
ロリドン、ヘキサメチレンホスホアミド等が挙げられ、
これらは単独又は 2種以上混合して使用することができ
る。縮合剤としては、ジシクロヘキシルカルボジイミ
ド、2,3-ジヒドロ-2−チオキソ−3-ベンゾオキサゾリル
ホスホン酸ジフェニル、1-メチル−3-(3-ジメチルアミ
ノプロピル)カルボジイミド等が挙げられ、これらは単
独又は 2種以上混合して使用することができる。また塩
基としては、ピリジン、ジメチルアミノピリジン、トリ
エチルアミン等が挙げられ、これらは単独又は 2種以上
混合して使用することができる。As the solvent used here, dimethyl sulfoxide, N, N-dimethylformamide, N, N-
Diethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N-methyl-2-pyrrolidone, hexamethylenephosphamide and the like;
These can be used alone or in combination of two or more. Examples of the condensing agent include dicyclohexylcarbodiimide, diphenyl 2,3-dihydro-2-thioxo-3-benzoxazolylphosphonate, 1-methyl-3- (3-dimethylaminopropyl) carbodiimide, and the like. Alternatively, two or more kinds can be used in combination. Examples of the base include pyridine, dimethylaminopyridine, triethylamine and the like, and these can be used alone or as a mixture of two or more.
【0016】ポリイミド樹脂とヒドロキシアルキルビニ
ルエーテル類との反応温度には、特に制限はないが、室
温から 100℃までの範囲が望ましい。またヒドロキシア
ルキルビニルエーテル類は、ポリイミド樹脂のカルボキ
シ当量に基づく化学的計算量で用いるのが好ましいが、
それよりも多くてもよい。通常は、ビニルオキシアルキ
ルオキシ基を含む構成単位:該基を含まない構成単位の
比が、 100:0 〜 5:95の範囲になるように用いる。The reaction temperature between the polyimide resin and the hydroxyalkyl vinyl ether is not particularly limited, but is preferably in the range from room temperature to 100 ° C. Also, hydroxyalkyl vinyl ethers are preferably used in a chemically calculated amount based on the carboxy equivalent of the polyimide resin,
May be more. Usually, it is used so that the ratio of the constitutional unit containing a vinyloxyalkyloxy group to the constitutional unit not containing the group is in the range of 100: 0 to 5:95.
【0017】こうして得られる新規なポリイミド重合体
は、白色の粉末で赤外吸収スペクトルにおいてイミド基
に基づく1785cm-1と1727cm-1の吸収、エステル基に基づ
く1720cm-1およびエーテル基に基づく1257cm-1の吸収が
見られる。このポリイミド重合体は、その側鎖にルイス
酸、プロトン酸、陽イオンに対して高い反応性を有する
ビニルオキシ基を持ち、非プロトン系の極性溶剤に可溶
なものである。The thus obtained novel polyimide polymers, absorption of 1785 cm -1 and 1727 cm -1 based on the imide group in an infrared absorption spectrum of a white powder, 1257Cm based on 1720 cm -1 and ether groups based on ester group - One absorption is seen. This polyimide polymer has a vinyloxy group having high reactivity with Lewis acids, proton acids and cations in its side chains, and is soluble in aprotic polar solvents.
【0018】本発明に用いる(B)希釈剤としては、ジ
メチルスルホキシド、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,N′−ジメ
チルアセトアミド、N,N′−ジエチルアセトアミド、
N−メチル−2-ピロリドン、ヘキサメチレンホスホアミ
ド、シクロヘキサノン、γ−ブチルラクトン等が挙げら
れ、これらは単独又は 2種以上混合して使用することが
できる。この希釈剤に(A)のポリイミド重合体を、造
膜上の理由から 5〜40重量%、好ましくは15〜30重量%
となるように溶解させることが望ましい。As the diluent (B) used in the present invention, dimethyl sulfoxide, N, N'-dimethylformamide, N, N'-diethylformamide, N, N'-dimethylacetamide, N, N'-diethylacetamide,
Examples thereof include N-methyl-2-pyrrolidone, hexamethylenephosphamide, cyclohexanone, and γ-butyl lactone, and these can be used alone or as a mixture of two or more. 5-40% by weight, preferably 15-30% by weight of the polyimide polymer (A) is added to this diluent for reasons of film formation.
It is desirable to dissolve so that
【0019】本発明に用いる(C)増感剤又は光重合開
始剤としては、各種オニウム塩類などが挙げられ、これ
らは単独又は 2種以上混合して使用することができる。
オニウム塩としては、例えばテトラフルオロホウ酸ジフ
ェニルヨードニウム、テトラフルオロホウ酸−4-メトキ
シジフェニルヨードニウム、テトラフルオロホウ酸-4,
4′−ジメチルジフェニルヨードニウム、テトラフルオ
ロホウ酸-4,4′ジイソプロピルジフェニルヨードニウム
などがある。増感剤又は光重合開始剤の配合割合は、ポ
リイミド重合体に対して 0.5〜20重量%、好ましくは
2.0〜10重量%配合することが望ましい。配合量が 0.5
重量%未満では硬化するのに長時間を要し、また20重量
%を超えると硬化性がそれ以上向上しないうえ不経済で
あり、好ましくない。Examples of the sensitizer or photopolymerization initiator (C) used in the present invention include various onium salts, and these can be used alone or as a mixture of two or more.
As onium salts, for example, diphenyliodonium tetrafluoroborate, 4-methoxydiphenyliodonium tetrafluoroborate, tetrafluoroborate-4,
4'-dimethyldiphenyliodonium, and 4,4'diisopropyldiphenyliodonium tetrafluoroborate. The compounding ratio of the sensitizer or the photopolymerization initiator is 0.5 to 20% by weight based on the polyimide polymer, preferably
It is desirable to mix 2.0 to 10% by weight. 0.5
If it is less than 20% by weight, it takes a long time to cure, and if it exceeds 20% by weight, the curability cannot be further improved and it is uneconomical.
【0020】本発明の光硬化性樹脂組成物は、(A)の
ポリイミド重合体と(B)の希釈剤および(C)増感剤
又は光重合開始剤を必須成分とするが、本発明の目的に
反しない範囲において、また必要に応じて、シリカ、炭
酸マグネシウム、炭酸カルシウム、硫酸ナトリウム、タ
ルク、ベントナイト等の無機充填剤、チキソトロピー
剤、フタロシアニングリーン等の着色剤、消泡剤、カッ
プリング剤、レベリング剤を添加配合させることができ
る。The photocurable resin composition of the present invention comprises the polyimide polymer (A), the diluent (B) and the sensitizer or photopolymerization initiator (C) as essential components. To the extent not contrary to the purpose, and if necessary, inorganic fillers such as silica, magnesium carbonate, calcium carbonate, sodium sulfate, talc, bentonite, coloring agents such as thixotropic agents, phthalocyanine green, defoaming agents, and coupling agents. And a leveling agent.
【0021】こうして得た光硬化性樹脂組成物を用いて
半田保護膜の形成をするには、フレキシブルプリント基
板やガラスエポキシプリント基板上にスクリーン印刷或
いは他の方法で塗布する。スクリーン印刷の場合には周
知の方法で基板上にパターン印刷し、印刷された基板を
80〜120 ℃で30〜60分間加熱して希釈剤を除去する。次
いで基板に光、例えば、紫外線を露光させて硬化させ
る。この一連の操作により得られた保護被膜は、10〜30
μm の膜厚を有するものである。ここで照射する紫外線
としては、 1000 〜 8000 オングストロームの間に主波
長を有するものが好ましく、その中でも特に 2000 〜 4
000 オングストロームの紫外線が適当であり、低圧水銀
灯、中圧水銀灯、高圧水銀灯、長高圧水銀灯、キセノン
ランプ等を用いることができる。露光時間は組成物の組
成、膜圧、ランプ強度、光源からの距離等に依存する
が、例えば30W/cmの入力をもつ高圧水銀灯での露光時
間は、5〜30秒である。In order to form a solder protective film using the photocurable resin composition thus obtained, it is applied on a flexible printed board or a glass epoxy printed board by screen printing or another method. In the case of screen printing, a pattern is printed on a board by a well-known method, and the printed board is printed.
Heat at 80-120 ° C for 30-60 minutes to remove diluent. Next, the substrate is exposed to light, for example, ultraviolet light, and cured. The protective coating obtained by this series of operations is 10 to 30
It has a thickness of μm. The ultraviolet rays to be irradiated here preferably have a dominant wavelength between 1000 and 8000 angstroms, and among them,
An ultraviolet ray of 000 angstroms is suitable, and a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, a long-high-pressure mercury lamp, a xenon lamp, or the like can be used. The exposure time depends on the composition of the composition, the film pressure, the lamp intensity, the distance from the light source, and the like. For example, the exposure time with a high-pressure mercury lamp having an input of 30 W / cm is 5 to 30 seconds.
【0022】[0022]
【作用】本発明のプリント回路板の製造方法によれば、
造膜性の優れた新規な光硬化性樹脂組成物を用いたこと
によって、電気絶縁性、半田耐熱性および可撓性に優れ
たプリント回路板を製造することができる。According to the method of manufacturing a printed circuit board of the present invention,
By using the novel photocurable resin composition having excellent film forming properties, a printed circuit board excellent in electrical insulation, solder heat resistance and flexibility can be manufactured.
【0023】[0023]
【実施例】次に本発明を実施例によって説明するが、本
発明はこれらの実施例によって限定されるものではな
い。Next, the present invention will be described with reference to examples, but the present invention is not limited to these examples.
【0024】実施例1 三口フラスコに乾燥窒素を通じてフラスコ内を置換した
後、3,5-ジアミノ安息香酸の76.1g を入れ、これにN−
メチル−2-ピロリドン(NMP) 1200ml を加えて溶解
した。溶解後 0℃に冷却し攪拌しながらヘキサフルオロ
イソプロピリデン−2,2-ジフタル酸無水物 222g を加え
た。反応による発熱を氷水中で抑えながら攪拌を続け、
そのまま 6時間反応させた。次いで反応溶液にキシレン
350g を加え、150 ℃で生成した水を共沸除去させなが
ら 1.5時間閉環反応を行った。その後、キシレンを減圧
下で留出除去させてイミド化を完結させた、反応後、反
応溶液をメタノールと水の混合溶液に投入してポリイミ
ド樹脂を析出させた。析出物を乾燥し、白色のポリイミ
ド樹脂粉末(対数粘度 0.5dl/g ) 280g を得た。Example 1 After replacing the inside of a three-necked flask with dry nitrogen through the flask, 76.1 g of 3,5-diaminobenzoic acid was added, and N-
1200 ml of methyl-2-pyrrolidone (NMP) was added and dissolved. After dissolution, the mixture was cooled to 0 ° C and 222 g of hexafluoroisopropylidene-2,2-diphthalic anhydride was added with stirring. Continue stirring while suppressing the heat generated by the reaction in ice water,
The reaction was allowed to proceed for 6 hours. Then, xylene was added to the reaction solution.
350 g was added, and a ring closure reaction was performed for 1.5 hours while azeotropically removing water generated at 150 ° C. Thereafter, xylene was distilled off under reduced pressure to complete the imidization. After the reaction, the reaction solution was poured into a mixed solution of methanol and water to precipitate a polyimide resin. The precipitate was dried to obtain 280 g of a white polyimide resin powder (logarithmic viscosity: 0.5 dl / g).
【0025】得られたポリイミド樹脂 201g をさらにN
MP 1100ml に溶解し、この溶液に2-ヒドロキシエチル
ビニルエーテル70.4g 、4-ジアミノピリジン15g 、ジシ
クロヘキシルカルボジイミド 124g を加え、室温で 4時
間反応させた。反応終了後、副生成物であるジシクロヘ
キシル尿素を吸引濾過により除去し炉液をメタノールと
水の混合溶液に投入して、ビニルエーテル化されたポリ
イミド重合体を析出させ、析出物を乾燥し、白色のビニ
ルエーテル化ポリイミド重合体粉末(対数粘度0.55dl
/g ) 220g を得た。このポリイミド重合体30g をジグ
ライム 70ml で溶解し、さらにテトラフルオロホウ酸ジ
フェニルヨードニウム3gとチクソトロピック剤として微
細シリカ粉末2gを加えて均一に混合して光硬化性樹脂組
成物を調製した。The obtained polyimide resin (201 g) was further added with N
The resulting solution was dissolved in 1100 ml of MP, and 70.4 g of 2-hydroxyethyl vinyl ether, 15 g of 4-diaminopyridine and 124 g of dicyclohexylcarbodiimide were added to the solution and reacted at room temperature for 4 hours. After the completion of the reaction, dicyclohexylurea, a by-product, was removed by suction filtration, and the reactor was poured into a mixed solution of methanol and water to precipitate a vinyl etherified polyimide polymer, and the precipitate was dried and dried. Vinyl etherified polyimide polymer powder (logarithmic viscosity 0.55dl
/ G) 220 g were obtained. 30 g of this polyimide polymer was dissolved in 70 ml of diglyme, and 3 g of diphenyliodonium tetrafluoroborate and 2 g of fine silica powder as a thixotropic agent were added and uniformly mixed to prepare a photocurable resin composition.
【0026】調製した光硬化性樹脂組成物をテトラクロ
ルエタンで脱脂したガラスエポキシ銅張積層板の銅箔側
に、280 メッシュのポリエステル繊維製ネット上に形成
されたパターンを当てて印刷し、次いで 120℃で30分間
乾燥後、 2KWの高圧水銀灯H−2000L/S(東芝
社製、商品名) 1個設置した紫外線照射炉で、 10cmの
距離からコンベアスピード 0.5m /min で 2回照射して
硬化させてプリント回路板を製造した。The prepared photocurable resin composition was degreased with tetrachloroethane and printed on the copper foil side of a glass epoxy copper-clad laminate by applying a pattern formed on a 280 mesh polyester fiber net, After drying at 120 ° C for 30 minutes, irradiation was performed twice at a conveyor speed of 0.5 m / min from a distance of 10 cm in an ultraviolet irradiation furnace equipped with one 2 kW high-pressure mercury lamp H-2000L / S (trade name, manufactured by Toshiba Corporation). Cured to produce a printed circuit board.
【0027】実施例2 三口フラスコに乾燥窒素を通じてフラスコ内を置換した
後、3,5-ジアミノ安香鉱酸の38g と 3,3′−ジメチル-
5,5′−ジエチル-4,4′−ジアミノジフェニルメタン
(MED)70.5g を入れ、これにN−メチル−2-ピロリ
ドン(NMP) 1200ml を加えて溶解した。溶解後 0℃
に冷却し攪拌しながら 3,3′-, 4,4′−ビフェニルエー
テルテトラカルボン酸二無水物(ODPA) 155.1g を
加えた。反応による発熱を氷水中で抑えながら攪拌を続
け、そのまま 6時間反応させた。次いで反応溶液にキシ
レン 350g を加え、150 ℃で生成した水を共沸除去させ
ながら1.5時間閉環反応を行った。その後、キシレンを
減圧下で留出除去させてイミド化を完結させた。反応
後、反応溶液をメタノールと水の混合溶液に投入してポ
リイミド樹脂を析出させた。析出物を乾燥し、白色のポ
リイミド樹脂粉末(対数粘度 0.5dl/g )256gを得た。Example 2 After the inside of the three-necked flask was purged with dry nitrogen, 38 g of 3,5-diaminobenzoic acid and 3,3'-dimethyl-
70.5 g of 5,5'-diethyl-4,4'-diaminodiphenylmethane (MED) was added, and 1200 ml of N-methyl-2-pyrrolidone (NMP) was added thereto and dissolved. 0 ℃ after melting
Then, 155.1 g of 3,3 '-, 4,4'-biphenylethertetracarboxylic dianhydride (ODPA) was added thereto while cooling and stirring. The stirring was continued while suppressing the heat generated by the reaction in ice water, and the reaction was allowed to proceed for 6 hours. Then, 350 g of xylene was added to the reaction solution, and a ring-closing reaction was performed at 150 ° C. for 1.5 hours while azeotropically removing generated water. Thereafter, xylene was distilled off under reduced pressure to complete the imidization. After the reaction, the reaction solution was poured into a mixed solution of methanol and water to precipitate a polyimide resin. The precipitate was dried to obtain 256 g of a white polyimide resin powder (logarithmic viscosity: 0.5 dl / g).
【0028】得られたポリイミド樹脂 211g をさらにN
MP985ml に溶解し、この溶液に2-ヒドロキシエチルビ
ニルエーテル35.2g 、4-ジメチルアミノピリジン 7.5g
、ジシクロヘキシルカルボジイミド61.9g を加え、室
温で 4時間反応させた。反応終了後、副生成物であるジ
シクロヘキシル尿素を吸引濾過により除去し炉液をメタ
ノールと水の混合溶液に投入して、ビニルエーテル化さ
れたポリイミド重合体を析出させ、析出物を乾燥し、白
色のビニルエーテル化ポリイミド重合体粉末(対数粘度
0.55dl /g ) 215g を得た。このポリイミド重合体30
g をジグライム 70ml で溶解し、さらにテトラフルオロ
ホウ酸ジフェニルヨードニウム3gとチクソトロピック剤
として微細シリカ粉末2gを加えて均一に溶解して光硬化
性樹脂組成物を調製した。[0028] 211 g of the obtained polyimide resin was further
MP985ml, and 35.2g of 2-hydroxyethyl vinyl ether and 7.5g of 4-dimethylaminopyridine were added to this solution.
Then, 61.9 g of dicyclohexylcarbodiimide was added and reacted at room temperature for 4 hours. After the completion of the reaction, dicyclohexylurea, a by-product, was removed by suction filtration, and the reactor was poured into a mixed solution of methanol and water to precipitate a vinyl etherified polyimide polymer, and the precipitate was dried and dried. Vinyl etherified polyimide polymer powder (logarithmic viscosity
0.55 dl / g) 215 g was obtained. This polyimide polymer 30
g was dissolved in 70 ml of diglyme, and 3 g of diphenyliodonium tetrafluoroborate and 2 g of fine silica powder as a thixotropic agent were added and uniformly dissolved to prepare a photocurable resin composition.
【0029】調製した光硬化性樹脂組成物を、実施例1
と同様に、印刷・乾燥・紫外線照射して硬化させ、プリ
ント回路板を製造した。The prepared photocurable resin composition was used in Example 1
In the same manner as in the above, printing, drying and curing were performed by irradiating ultraviolet rays to produce a printed circuit board.
【0030】実施例3 三口フラスコに乾燥窒素を通じてフラスコ内を置換した
後、3,5-ジアミノ安息香酸の38g と 3,3′−ジメチル-
5,5′−ジエチル-4,4′−ジアミノジフェニルメタン
(MED)70.5g を入れ、これにN−メチル-2−ピロリ
ドン(NMP) 1200 mlを加えて溶解した。溶解後 0℃
に冷却し攪拌しながら 3,3′−,4,4′−ビフェニルスル
ホンテトラカルボン酸二無水物(OSDA) 179g を加
えた。反応による発熱を氷水中で抑えながら攪拌を続
け、そのまま 6時間反応させた。次いで反応溶液にキシ
レン 350g を加え、150 ℃で生成した水を共沸除去させ
ながら 1.5時間閉環反応を行った。その後、キシレンを
減圧下で留出除去させてイミド化を完結させた。反応
後、反応溶液をメタノールと水の混合溶液に投入してポ
リイミド樹脂を析出させた。析出物を乾燥し、白色のポ
リイミド樹脂粉末(対数粘度0.5dl/g ) 246g を得
た。Example 3 After replacing the inside of a three-necked flask with dry nitrogen through a flask, 38 g of 3,5-diaminobenzoic acid and 3,3'-dimethyl-
70.5 g of 5,5'-diethyl-4,4'-diaminodiphenylmethane (MED) was added, and 1200 ml of N-methyl-2-pyrrolidone (NMP) was added thereto and dissolved. 0 ℃ after melting
179 g of 3,3 '-, 4,4'-biphenylsulfonetetracarboxylic dianhydride (OSDA) was added thereto while cooling and stirring. The stirring was continued while suppressing the heat generated by the reaction in ice water, and the reaction was allowed to proceed for 6 hours. Then, 350 g of xylene was added to the reaction solution, and a ring closure reaction was carried out at 150 ° C. for 1.5 hours while azeotropically removing generated water. Thereafter, xylene was distilled off under reduced pressure to complete the imidization. After the reaction, the reaction solution was poured into a mixed solution of methanol and water to precipitate a polyimide resin. The precipitate was dried to obtain 246 g of a white polyimide resin powder (logarithmic viscosity: 0.5 dl / g).
【0031】得られたポリイミド樹脂 230g をさらにN
MP 1060ml に溶解し、この溶液に2-ヒドロキシエチル
ビニルエーテル35.2g 、4-ジメチルアミノピリジン 7.5
g 、ジシクロヘキシルカルボジイミド61.9g を加え、室
温で 4時間反応させた。反応終了後、副生成物であるジ
シクロヘキシル尿素を吸引濾過により除去し炉液をメタ
ノールと水の混合溶液に投入して、ビニルエーテル化さ
れたポリイミド樹脂を析出させ、析出物を乾燥し、白色
のビニルエーテル化ポリイミド重合体粉末(対数粘度
0.55dl /g ) 238g を得た。このポリイミド重合体30g
をジグライム 70ml で溶解し、さらにテトラフルオロ
ホウ酸ジフェニルヨードニウム3gとチクソトロピック剤
として微細シリカ粉末2gを加えて均一に混合して光硬化
性樹脂組成物を調製した。[0031] 230 g of the obtained polyimide resin was further
MP was dissolved in 1060 ml, and 35.2 g of 2-hydroxyethyl vinyl ether and 7.5 ml of 4-dimethylaminopyridine were added to this solution.
g and 61.9 g of dicyclohexylcarbodiimide were added, and the mixture was reacted at room temperature for 4 hours. After completion of the reaction, dicyclohexylurea, a by-product, was removed by suction filtration, and the furnace solution was poured into a mixed solution of methanol and water to precipitate a vinyl etherified polyimide resin.The precipitate was dried, and white vinyl ether was dried. Polyimide polymer powder (logarithmic viscosity
0.55 dl / g) 238 g was obtained. 30 g of this polyimide polymer
Was dissolved in 70 ml of diglyme, and 3 g of diphenyliodonium tetrafluoroborate and 2 g of fine silica powder as a thixotropic agent were added and uniformly mixed to prepare a photocurable resin composition.
【0032】調製した光硬化性樹脂組成物を、実施例1
と同様に、印刷・乾燥・紫外線照射して硬化させ、プリ
ント回路板を製造した。The prepared photocurable resin composition was prepared in Example 1
In the same manner as in the above, printing, drying and curing were performed by irradiating ultraviolet rays to produce a printed circuit board.
【0033】比較例1 市販の汎用エポキシ系ソルダーレジスト処理されたガラ
スエポキシプリント回路板を入手した。Comparative Example 1 A commercially available glass epoxy printed circuit board treated with a general-purpose epoxy solder resist was obtained.
【0034】比較例2 市販の汎用エポキシ系ソルダーレジスト処理されたフレ
キシブルプリント回路板を入手した。Comparative Example 2 A commercially available flexible printed circuit board treated with a general-purpose epoxy solder resist was obtained.
【0035】実施例1〜3および比較例1〜2で製造ま
たは入手したプリント回路板の保護被膜にロジン系フラ
ックス液をハケ塗りして 260℃に溶融した半田浴に10秒
間浸漬した。また煮沸後の保護被膜のクロスカットテス
ト、電気絶縁性或いは屈曲性試験を行ったのでその結果
を表1および表2に示したが、本発明の顕著な効果を確
認することができた。A rosin flux was applied to the protective coating of the printed circuit board manufactured or obtained in Examples 1 to 3 and Comparative Examples 1 and 2 and immersed in a solder bath melted at 260 ° C. for 10 seconds. A cross-cut test, an electrical insulation property, and a flexibility test were performed on the protective coating after boiling. The results are shown in Tables 1 and 2, and the remarkable effects of the present invention could be confirmed.
【0036】[0036]
【表1】 *1 :JIS−C−2103により測定[Table 1] * 1: Measured according to JIS-C-2103
【0037】[0037]
【表2】 *1 :JIS−D−0202により測定 *2 :図1に示したような電極間距離 0.25 mm、導体間
0.25 mm、切断寸法 50mm、導体厚さ70μm の櫛形電極
1を用いて、JIS−Z−3197により測定 *3 :180 °折曲げ10回[Table 2] * 1: Measured according to JIS-D-0202 * 2: Distance between electrodes 0.25 mm as shown in Fig. 1, between conductors
Measured in accordance with JIS-Z-3197 using a comb-shaped electrode 1 with 0.25 mm, cut size of 50 mm, and conductor thickness of 70 μm * 3: 180 ° bending 10 times
【0038】[0038]
【発明の効果】以上の説明および表1,表2から明らか
なように、本発明のプリント回路板の製造方法によれ
ば、薄いソルダーレジスト膜であるにもかかわらず、半
田耐熱性、耐薬品性、電気絶縁性および可撓性に優れ、
産業用エレクトロニクスに好適なプリント回路板を製造
することができる。As is clear from the above description and Tables 1 and 2, according to the method for manufacturing a printed circuit board of the present invention, solder heat resistance and chemical resistance are obtained despite a thin solder resist film. Excellent in electrical properties, electrical insulation and flexibility,
A printed circuit board suitable for industrial electronics can be manufactured.
【図1】図1は、本発明のプリント回路板の電気絶縁性
試験に用いた櫛形電極の平面図である。FIG. 1 is a plan view of a comb-shaped electrode used for an electrical insulation test of a printed circuit board according to the present invention.
1 櫛形電極 1 Comb electrodes
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.7,DB名) G03F 7/038 G03F 7/027 H05K 3/28 ──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. 7 , DB name) G03F 7/038 G03F 7/027 H05K 3/28
Claims (1)
少なくとも1 個含むポリイミド重合体 【化1】 (但し、式中、R1 は4 価の有機基を、R2 は3 価の芳
香族基を、R3 は2 価の有機基をそれぞれ表す) (B)希釈剤および (C)増感剤又は光重合開始剤を必須成分とする光硬化
性樹脂組成物を、回路基板上に塗布・露光硬化して保護
膜を形成し、次いで保護膜非形成部分に半田を析出させ
ることを特徴とするプリント回路板の製造方法。(A) a polyimide polymer containing at least one structural unit represented by the following general formula: (Wherein, R 1 represents a tetravalent organic group, R 2 represents a trivalent aromatic group, and R 3 represents a divalent organic group.) (B) Diluent and (C) sensitization A photocurable resin composition containing an agent or a photopolymerization initiator as an essential component is coated and exposed and cured on a circuit board to form a protective film, and then a solder is deposited on a portion where no protective film is formed. Printed circuit board manufacturing method.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP20610292A JP3193468B2 (en) | 1992-07-09 | 1992-07-09 | Manufacturing method of printed circuit board |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP20610292A JP3193468B2 (en) | 1992-07-09 | 1992-07-09 | Manufacturing method of printed circuit board |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH0627667A JPH0627667A (en) | 1994-02-04 |
JP3193468B2 true JP3193468B2 (en) | 2001-07-30 |
Family
ID=16517840
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP20610292A Expired - Fee Related JP3193468B2 (en) | 1992-07-09 | 1992-07-09 | Manufacturing method of printed circuit board |
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US5718943A (en) * | 1995-07-20 | 1998-02-17 | Rohm And Haas Company | Method for producing efflorescence resistant coating on cementitious substrate |
JP2003131371A (en) * | 2001-10-24 | 2003-05-09 | Kanegafuchi Chem Ind Co Ltd | Flame-resistant photosensitive dry film resist |
JP4046563B2 (en) * | 2002-01-25 | 2008-02-13 | 旭化成エレクトロニクス株式会社 | High heat-resistant photosensitive resin composition |
US8063245B2 (en) | 2003-06-05 | 2011-11-22 | Kaneka Corporation | Phosphazene compound, photosensitive resin composition and use thereof |
-
1992
- 1992-07-09 JP JP20610292A patent/JP3193468B2/en not_active Expired - Fee Related
Also Published As
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