JPWO2007083538A1 - Epoxy bleed-out prevention agent - Google Patents

Epoxy bleed-out prevention agent Download PDF

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JPWO2007083538A1
JPWO2007083538A1 JP2007528901A JP2007528901A JPWO2007083538A1 JP WO2007083538 A1 JPWO2007083538 A1 JP WO2007083538A1 JP 2007528901 A JP2007528901 A JP 2007528901A JP 2007528901 A JP2007528901 A JP 2007528901A JP WO2007083538 A1 JPWO2007083538 A1 JP WO2007083538A1
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epoxy bleed
epoxy
bleed
wiring substrate
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JP4082625B2 (en
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相場　玲宏
玲宏 相場
久 中村
久 中村
智晴 三村
智晴 三村
土田　克之
克之 土田
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Nippon Mining Holdings Inc
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Nippon Mining and Metals Co Ltd
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Abstract

低応力タイプのダイボンディング樹脂を用いた場合においても、ダイボンディング強度や、アセンブリ特性に悪影響を与えず、変色防止処理や封孔処理効果を損なうことのないエポキシブリードアウト防止剤を提供する。炭素原子が３個以上２４個以下であるフルオロ炭化水素基ＣｘＨｙＦｚ−（ｘ＝３〜２４、ｙ＝０〜４８、ｚ＝１〜４９、ｙ＋ｚ≦２ｘ＋１）と極性基Ｒ−を有する含フッ素有機化合物を含有することを特徴とするダイボンディング工程におけるエポキシブリードアウト防止剤。Provided is an epoxy bleedout preventing agent that does not adversely affect die bonding strength and assembly characteristics even when a low stress type die bonding resin is used, and does not impair the discoloration prevention treatment and sealing treatment effects. Fluorine-containing organic compound having a fluorohydrocarbon group CxHyFz- (x = 3 to 24, y = 0 to 48, z = 1 to 49, y + z ≦ 2x + 1) having 3 to 24 carbon atoms and a polar group R- An epoxy bleed-out preventing agent in a die bonding process, comprising a compound.

Description

本発明は、リードフレームやプリント配線板等の半導体配線基材とＩＣチップとをエポキシ樹脂によって接着固定するダイボンディング工程におけるエポキシブリードアウト防止剤及び防止方法に関する。   The present invention relates to an epoxy bleed-out preventing agent and a preventing method in a die bonding process in which a semiconductor wiring substrate such as a lead frame or a printed wiring board and an IC chip are bonded and fixed with an epoxy resin.

リードフレームやプリント配線板等の半導体配線基材とＩＣチップとをエポキシ樹脂によって接着固定するダイボンディング工程においては、接着面（通常、金、銀、銅、パラジウム等のめっきが施されている）の表面粗さが大きすぎたり、表面が変色防止剤、封孔処理剤等の有機物で汚染されていると、エポキシ樹脂塗布時に、樹脂または添加剤の滲み出し（エポキシブリードアウト）が発生する。このエポキシブリードアウトは、ダイボンディング強度を低下させたり、その後のワイヤーボンディング工程での不良原因となったりする。従来、このようなエポキシブリードアウトを防止するために、接着面の表面粗さを小さくし、毛細管現象を抑制したり、表面を洗浄し汚染物を取り除いたりしていた。しかし、接着面の表面粗さは、ダイボンディング強度や、アセンブリマシンの画像認識能力に影響を与えるため、一概に小さくすることはできない。また、表面を洗浄することは、変色防止処理や封孔処理効果まで損なってしまうため問題であった。   Adhesive surface (usually plated with gold, silver, copper, palladium, etc.) in the die-bonding process that bonds and fixes semiconductor wiring substrates such as lead frames and printed wiring boards and IC chips with epoxy resin If the surface roughness is too large, or the surface is contaminated with organic substances such as anti-discoloring agents and sealing agents, bleeding of the resin or additive (epoxy bleed out) occurs when the epoxy resin is applied. This epoxy bleed-out may reduce the die bonding strength or cause a defect in the subsequent wire bonding process. Conventionally, in order to prevent such epoxy bleed-out, the surface roughness of the bonding surface is reduced to suppress capillary action, and the surface is washed to remove contaminants. However, since the surface roughness of the bonding surface affects the die bonding strength and the image recognition capability of the assembly machine, it cannot be generally reduced. In addition, cleaning the surface has been a problem because the effect of preventing discoloration and sealing effect are lost.

これらの問題を解決するために、カルボン酸、チオール等を主成分とする溶液に基材を浸漬し、１〜数分子程度の有機被膜を吸着させることで、基材面の表面粗さを変えたり、変色防止被膜や封孔処理被膜を洗浄剥離することなく、また、吸着する有機被膜が非常に薄いため、ワイヤーボンディング性、モールディング性等のアセンブリ特性に悪影響を与えず、エポキシブリードアウトを防止できることが特許文献１に示されている。   In order to solve these problems, the surface roughness of the substrate surface is changed by immersing the substrate in a solution containing carboxylic acid, thiol or the like as a main component and adsorbing an organic film of about 1 to several molecules. In addition, the organic coating to be adsorbed is extremely thin without adversely affecting assembly properties such as wire bonding and molding properties, and prevents epoxy bleeding out. Patent Document 1 shows that this can be done.

しかし、最近の半導体チップの大型化や半導体パッケージの薄型化に伴い、反りの問題等を改善するため、低応力、低弾性、低粘度のダイボンディング樹脂（以下、低応力タイプのダイボンディング樹脂と称す）の使用が多くなっており、これらの樹脂は滲み出し易い成分を含有している場合が多く、その結果、エポキシブリードアウトが発生しやすくなってきている。上記特許文献１の技術では、低応力タイプのダイボンディング樹脂を用いた場合には、対応しきれずエポキシブリードアウトが発生してしまう。従って、低応力タイプのダイボンディング樹脂にも対応したエポキシブリードアウト防止剤の開発が望まれている。
特開平１１−１９５６６２号公報 However, with the recent increase in size of semiconductor chips and thinning of semiconductor packages, low-stress, low-elasticity, low-viscosity die bonding resins (hereinafter referred to as low-stress type die bonding resins) In many cases, these resins contain components that tend to exude, and as a result, epoxy bleed-out is likely to occur. In the technique of the above-mentioned Patent Document 1, when a low stress type die bonding resin is used, it cannot cope with it and an epoxy bleed out occurs. Therefore, development of an epoxy bleed-out preventing agent corresponding to a low stress type die bonding resin is desired.
Japanese Patent Laid-Open No. 11-195562

本発明は、リードフレームやプリント配線板等の半導体配線基材とＩＣチップとをエポキシ樹脂によって接着固定するダイボンディング工程において、上述の低応力タイプのダイボンディング樹脂を用いた場合においても、ダイボンディング強度や、アセンブリ特性に悪影響を与えず、変色防止処理や封孔処理効果を損なうことがなく、エポキシブリードアウトの発生を防止することができるエポキシブリードアウト防止剤を提供することを目的とする。   In the die bonding process of bonding and fixing a semiconductor wiring substrate such as a lead frame or a printed wiring board and an IC chip with an epoxy resin, the present invention can perform die bonding even when the low-stress type die bonding resin is used. An object of the present invention is to provide an epoxy bleed-out preventing agent capable of preventing the occurrence of epoxy bleed-out without adversely affecting the strength and assembly characteristics, without impairing the effect of discoloration prevention and sealing treatment.

本発明者らは、鋭意研究を行った結果、エポキシブリードアウト防止剤を含有する溶液に基材を浸漬し、めっき面の表面に有機被膜を吸着させることによってエポキシブリードアウトを防止する工程で、従来より更に低応力タイプのダイボンディング樹脂に対してもブリードアウトを防止する効果をもつ一群の有機化合物を見出した。即ち、上記文献に記載のカルボン酸、チオール化合物等よりエポキシブリードアウト防止効果が高い化合物を見出し本発明を成すに至った。
本発明は以下のとおりである。As a result of diligent research, the present inventors have immersed the base material in a solution containing an epoxy bleed-out inhibitor, and in the step of preventing epoxy bleed-out by adsorbing an organic coating on the surface of the plating surface, We have discovered a group of organic compounds that have the effect of preventing bleed-out even for low-stress type die bonding resins. That is, the present inventors have found a compound having a higher epoxy bleed-out preventing effect than the carboxylic acid, thiol compound and the like described in the above documents.
The present invention is as follows.

（１）炭素原子が３個以上２４個以下であるフルオロ炭化水素基ＣｘＨｙＦｚ−（ｘ＝３〜２４、ｙ＝０〜４８、ｚ＝１〜４９、ｙ＋ｚ≦２ｘ＋１）と極性基Ｒ−を有する含フッ素有機化合物を含有することを特徴とするダイボンディング工程におけるエポキシブリードアウト防止剤。 (1) having a fluorohydrocarbon group CxHyFz- (x = 3-24, y = 0-48, z = 1-49, y + z ≦ 2x + 1) having 3 to 24 carbon atoms and a polar group R- An epoxy bleed-out preventing agent in a die bonding process characterized by containing a fluorine-containing organic compound.

（２）極性基Ｒ−が、イオウ（Ｓ）、窒素（Ｎ）、リン（Ｐ）、酸素（Ｏ）のいずれかを含む極性基であることを特徴とする前記（１）に記載のエポキシブリードアウト防止剤。 (2) The epoxy according to (1), wherein the polar group R- is a polar group containing any of sulfur (S), nitrogen (N), phosphorus (P), and oxygen (O). Bleed-out prevention agent.

（３）極性基Ｒ−が、メルカプト基、アミノ基、含窒素複素環基、リン酸エステル基、カルボキシル基のいずれかであることを特徴とする前記（２）に記載のエポキシブリードアウト防止剤。 (3) The epoxy bleedout inhibitor as described in (2) above, wherein the polar group R- is any one of a mercapto group, an amino group, a nitrogen-containing heterocyclic group, a phosphate ester group, and a carboxyl group. .

（４）含窒素複素環基が、イミダゾリル基、トリアゾリル基、テトラゾリル基、およびそれらの誘導体のいずれかであることを特徴とする前記（３）に記載のエポキシブリードアウト防止剤。 (4) The epoxy bleedout inhibitor as described in (3) above, wherein the nitrogen-containing heterocyclic group is any one of an imidazolyl group, a triazolyl group, a tetrazolyl group, and derivatives thereof.

（５）変色防止剤又は封孔処理剤を含有することを特徴とする前記（１）〜（４）のいずれかに記載のエポキシブリードアウト防止剤。 (5) The epoxy bleed-out inhibitor according to any one of (1) to (4) above, which contains a discoloration inhibitor or a sealing agent.

（６）変色防止剤が、含窒素複素環状化合物を含有することを特徴とする前記（５）に記載のエポキシブリードアウト防止剤。 (6) The epoxy bleed-out inhibitor as described in (5) above, wherein the discoloration inhibitor contains a nitrogen-containing heterocyclic compound.

（７）含窒素複素環状化合物が、イミダゾール誘導体、トリアゾール誘導体、テトラゾール誘導体、チアゾール誘導体のいずれかであることを特徴とする前記（６）に記載のエポキシブリードアウト防止剤。 (7) The epoxy bleedout inhibitor as described in (6) above, wherein the nitrogen-containing heterocyclic compound is any one of an imidazole derivative, a triazole derivative, a tetrazole derivative, and a thiazole derivative.

（８）前記（１）〜（７）のいずれかに記載のエポキシブリードアウト防止剤を含有する溶液に配線基材を浸漬するか、または該エポキシブリードアウト防止剤を含有する溶液を配線基材に散布・塗布することを特徴とするエポキシブリードアウト防止方法。 (8) The wiring substrate is immersed in a solution containing the epoxy bleed-out preventing agent according to any one of (1) to (7), or the solution containing the epoxy bleed-out preventing agent is used as the wiring substrate. Epoxy bleed-out prevention method characterized by spraying and applying to the surface.

（９）前記（１）〜（７）のいずれかに記載のエポキシブリードアウト防止剤を含有する溶液に配線基材を浸漬するか、または該エポキシブリードアウト防止剤を含有する溶液を配線基材に散布・塗布することことによりエポキシブリードアウト防止処理を施したことを特徴とする配線基材。 (9) A wiring substrate is immersed in a solution containing the epoxy bleed-out preventing agent according to any one of (1) to (7), or a solution containing the epoxy bleed-out preventing agent is used as a wiring substrate. A wiring base material that has been subjected to an epoxy bleed-out prevention treatment by spraying and coating on the substrate.

（１０） 前記（１）〜（７）のいずれかに記載のエポキシブリードアウト防止剤が表面に吸着していることを特徴とする配線基材。 (10) A wiring substrate, wherein the epoxy bleed-out preventing agent according to any one of (1) to (7) is adsorbed on the surface.

（１１） 前記（９）又は（１０）に記載の配線基材を用いたことを特徴とする半導体パッケージ。 (11) A semiconductor package using the wiring substrate according to (9) or (10).

本発明のエポキシブリードアウト防止剤を用いてリードフレーム、プリント配線板等の半導体配線基材表面にエポキシブリードアウト防止機能を有する有機化合物を吸着させるエポキシブリードアウト防止処理を行うことによって、低応力タイプのダイボンディング樹脂に対しても、変色防止効果や封孔処理効果を損なうことなくダイボンディング工程におけるエポキシブリードアウトを防止することが可能である。また、ワイヤーボンディング特性やモールディング性等のアセンブリ特性にも悪影響を与えることがない。   By using the epoxy bleed-out preventing agent of the present invention, an epoxy bleed-out preventing treatment is performed by adsorbing an organic compound having an epoxy bleed-out preventing function on the surface of a semiconductor wiring substrate such as a lead frame or a printed wiring board. It is possible to prevent epoxy bleeding out in the die bonding process without impairing the discoloration preventing effect and the sealing effect. Further, the assembly characteristics such as wire bonding characteristics and molding properties are not adversely affected.

実施例の耐エポキシブリードアウト性評価におけるエポキシブリードアウト量の測定方法を示す図である。It is a figure which shows the measuring method of the epoxy bleed-out amount in the epoxy bleed-out resistance evaluation of an Example.

本発明のエポキシブリードアウト防止剤は、炭素原子が３個以上２４個以下であるフルオロ炭化水素基ＣｘＨｙＦｚ−（ｘ＝３〜２４、ｙ＝０〜４８、ｚ＝１〜４９、ｙ＋ｚ≦２ｘ＋１）と極性基Ｒ−を有する含フッ素有機化合物を含有する。   The epoxy bleed-out inhibitor of the present invention is a fluorohydrocarbon group CxHyFz- (x = 3-24, y = 0-48, z = 1-49, y + z ≦ 2x + 1) having 3 to 24 carbon atoms. And a fluorine-containing organic compound having a polar group R-.

前記フルオロ炭化水素基としては、フルオロアルキル基、２重結合を含むフルオロアルケニル基、３重結合を含むフルオロアルキニル基等が挙げられ、フルオロアルキル基が好ましい。また、これらのフルオロ炭化水素基は、フルオロ炭化水素基全体の炭素原子が３個から２４個であれば、直鎖状のものであっても良いし、側鎖を有していても良い。フルオロ炭化水素基の炭素数ｘは、３〜２４であり、５〜１２のものが特に好ましい。炭素数が少なすぎるとエポキシブリードアウト防止効果が低く、多すぎるとモールディング性（モールディング樹脂の密着性）を低下させる。また、フッ素数ｚは、多いほどエポキシブリードアウト防止効果が高いが、炭素数が多く分子が長い場合には、フッ素数が多すぎるとモールディング性の低下を招く場合もあるので、フッ素数ｚは１１〜２５が好ましい。   Examples of the fluorohydrocarbon group include a fluoroalkyl group, a fluoroalkenyl group containing a double bond, a fluoroalkynyl group containing a triple bond, and the like, and a fluoroalkyl group is preferred. Further, these fluorohydrocarbon groups may be linear or have a side chain as long as the total number of carbon atoms in the fluorohydrocarbon group is 3 to 24. Carbon number x of a fluoro hydrocarbon group is 3-24, and the thing of 5-12 is especially preferable. If the carbon number is too small, the effect of preventing epoxy bleed out is low, and if it is too large, the molding property (adhesiveness of the molding resin) is lowered. In addition, the larger the number of fluorine z, the higher the effect of preventing epoxy bleed out. However, when the number of carbon atoms is long and the molecule is long, if the number of fluorine is too large, the molding property may be deteriorated. 11-25 are preferable.

前記フルオロ炭化水素基としては、Ｆ（ＣＦ2）6−、Ｆ（ＣＦ2）8−、Ｆ（ＣＦ2）10−、Ｆ（ＣＦ2）6（ＣＨ2）2−、Ｆ（ＣＦ2）8（ＣＨ2）2−、Ｆ（ＣＦ2）10（ＣＨ2）2−、等を好ましく用いることができる。As the fluorohydrocarbon group, F (CF 2) 6 - , F (CF 2) 8 -, F (CF 2) 10 -, F (CF 2) 6 (CH 2) 2 -, F (CF 2) 8 (CH 2 ) 2 —, F (CF 2 ) 10 (CH 2 ) 2 —, and the like can be preferably used.

また、前記極性基Ｒ−としては、イオウ（Ｓ）、窒素（Ｎ）、リン（Ｐ）、酸素（Ｏ）のいずれかを含む極性基、例えば、メルカプト基、アミノ基、含窒素複素環基、リン酸エステル基、カルボキシル基のいずれかを好ましく用いることができ、含窒素複素環基としては、例えば、イミダゾリル基、トリアゾリル基、テトラゾリル基、およびそれらの誘導体を好ましく用いることができる。
前記極性基がリン酸エステル基の場合は、モノエステル（−ＯＰ(Ｏ)(ＯＨ)2）、ジエステル（(−Ｏ)2Ｐ(Ｏ)(ＯＨ)）、トリエステル（(−Ｏ)3Ｐ(Ｏ)）を用いることができる。The polar group R- includes polar groups containing any of sulfur (S), nitrogen (N), phosphorus (P), and oxygen (O), such as mercapto groups, amino groups, and nitrogen-containing heterocyclic groups. Any one of a phosphoric acid ester group and a carboxyl group can be preferably used. As the nitrogen-containing heterocyclic group, for example, an imidazolyl group, a triazolyl group, a tetrazolyl group, and derivatives thereof can be preferably used.
When the polar group is a phosphate group, a monoester (—OP (O) (OH) 2 ), a diester ((—O) 2 P (O) (OH)), a triester ((—O) 3 P (O)) can be used.

含窒素複素環基であるイミダゾリル基、トリアゾリル基、テトラゾリル基については、異性体が存在するが、本発明においては、異性体のどれをも用いることができ、また、混合物でも構わない。合成の都合上、含窒素環状化合物の窒素が直接フルオロ炭化水素基と結合しているものが得られやすく、好ましく用いることができる。また、イミダゾリル基、トリアゾリル基、テトラゾリル基の誘導体としては、置換基としてアルキル基やフェニル基を有するもの等が挙げられる。   As for the imidazolyl group, triazolyl group, and tetrazolyl group that are nitrogen-containing heterocyclic groups, isomers exist, but in the present invention, any of the isomers can be used, and a mixture may be used. For the convenience of synthesis, it is easy to obtain a nitrogen-containing cyclic compound in which nitrogen of the nitrogen-containing cyclic compound is directly bonded to a fluorohydrocarbon group, and it can be preferably used. Examples of the imidazolyl group, triazolyl group, and tetrazolyl group derivative include those having an alkyl group or a phenyl group as a substituent.

したがって、本発明のエポキシブリードアウト防止剤として、好ましい含フッ素有機化合物としては、前記フルオロ炭化水素基ＣｘＨｙＦｚ−をＡ−として示すと、例えば、Ａ−ＳＨ、Ａ−ＮＨ2、Ａ−ＯＰ(Ｏ)(ＯＨ)2、(Ａ−Ｏ)2Ｐ(Ｏ)(ＯＨ)、(Ａ−Ｏ)3Ｐ(Ｏ)、Ａ−ＣＯＯＨ、Ａ−Ｎ2Ｃ3Ｈ3（１−イミダゾリル）、Ａ−Ｎ3Ｃ2Ｈ2（１，２，３−トリアゾル−１−イル）、Ａ−Ｎ4ＣＨ（１−テトラゾリル）等を挙げることができる。Therefore, as a preferable fluorine-containing organic compound as the epoxy bleed-out inhibitor of the present invention, when the fluorohydrocarbon group CxHyFz- is represented as A-, for example, A-SH, A-NH 2 , A-OP (O ) (OH) 2, (A -O) 2 P (O) (OH), (A-O) 3 P (O), A-COOH, A-N 2 C 3 H 3 (1- imidazolyl), A -N 3 C 2 H 2 (1,2,3-triazol-1-yl), A-N 4 CH (1-tetrazolyl) and the like can be mentioned.

本発明のエポキシブリードアウト防止剤は、水、有機溶媒等の溶媒に溶解させ、エポキシブリードアウト防止剤溶液として用いる。前記防止剤溶液中の上記有機化合物の濃度は０．１ｍｇ／Ｌ〜１００ｇ／Ｌ、好ましくは１０ｍｇ／Ｌ〜１０ｇ／Ｌである。
上記有機化合物の濃度が低すぎる場合には、エポキシブリードアウト防止効果がなく、また濃度が高すぎても、効果が飽和し、それ以上の効果を期待できないため好ましくない。The epoxy bleed out inhibitor of the present invention is dissolved in a solvent such as water or an organic solvent and used as an epoxy bleed out inhibitor solution. The concentration of the organic compound in the inhibitor solution is 0.1 mg / L to 100 g / L, preferably 10 mg / L to 10 g / L.
If the concentration of the organic compound is too low, there is no effect of preventing epoxy bleed-out, and if the concentration is too high, the effect is saturated and no further effect can be expected.

溶媒として水を用いる場合、上記有機化合物が水に溶けにくい場合には、必要に応じてアルコール、ケトンなどの有機溶剤を添加する。添加する量は、上記有機化合物が水に溶けるのに必要な濃度でよいが、通常０．１ｇ／Ｌ〜２００ｇ／Ｌであり、好ましくは１ｇ／Ｌ〜５０ｇ／Ｌである。添加する量が少なすぎると溶解性が低く、また多すぎても上記有機化合物を溶解する効果は変わらないばかりか、上記有機化合物の濃度が薄くなりすぎて好ましくない。   When water is used as a solvent, an organic solvent such as an alcohol or a ketone is added as necessary if the organic compound is difficult to dissolve in water. The amount to be added may be a concentration necessary for the organic compound to dissolve in water, but is usually 0.1 g / L to 200 g / L, and preferably 1 g / L to 50 g / L. If the amount added is too small, the solubility is low, and if it is too large, the effect of dissolving the organic compound does not change, and the concentration of the organic compound becomes too thin, which is not preferable.

さらに、上記有機化合物が水に溶けにくい場合には、必要に応じて、アニオン系、カチオン系、ノニオン系の界面活性剤のいずれかまたはこれらの混合物を１μｇ／Ｌ〜１０ｇ／Ｌ、好ましくは１０μｇ／Ｌ〜１ｇ／Ｌ添加する。   Further, when the organic compound is hardly soluble in water, an anionic, cationic or nonionic surfactant or a mixture thereof is added at 1 μg / L to 10 g / L, preferably 10 μg, if necessary. / L to 1 g / L is added.

また、防止剤溶液中には、必要に応じて、リン酸系、ホウ酸系、有機酸系のｐＨ緩衝剤を０．１ｇ／Ｌ〜２００ｇ／Ｌ、好ましくは１〜５０ｇ／Ｌ添加する。少なすぎるとｐＨ緩衝効果が低く、多すぎると効果が飽和し、多く加えるメリットがない。   Further, in the inhibitor solution, 0.1 g / L to 200 g / L, preferably 1 to 50 g / L of a phosphoric acid-based, boric acid-based, or organic acid-based pH buffering agent is added as necessary. If the amount is too small, the pH buffering effect is low. If the amount is too large, the effect is saturated and there is no merit to add more.

また、防止剤溶液中に金属の溶出がある場合は必要に応じて、金属隠蔽剤として、アミン系、アミノカルボン酸系、カルボン酸系の錯化剤を０．１ｇ／Ｌ〜２００ｇ／Ｌ、好ましくは１ｇ／Ｌ〜５０ｇ／Ｌ添加する。少なすぎると金属を錯化して隠蔽する効果が少なく、多すぎると効果が飽和し、多く加えるメリットがない。   Further, when there is metal elution in the inhibitor solution, if necessary, 0.1 g / L to 200 g / L of an amine-based, aminocarboxylic acid-based, or carboxylic acid-based complexing agent as a metal masking agent, Preferably, 1 g / L to 50 g / L is added. If the amount is too small, the effect of concealing the metal by complexing is small, and if it is too large, the effect is saturated and there is no merit to add more.

エポキシブリードアウト防止剤溶液のｐＨは特に限定する必要はないが、通常はｐＨ１〜１４の間であり、ｐＨ２〜１２で処理することが好ましい。この範囲を逸脱すると、素材のダメージが大きく、エポキシブリードアウト防止効果が低い。
また、エポキシブリードアウト防止剤溶液の温度は、水溶液で行いうる温度範囲で可能であるが、通常５〜９０℃、好ましくは１０〜６０℃とする。温度が低すぎるとエポキシブリードアウト効果が低く、高すぎても効果が飽和し、作業性が悪くなるだけで、温度を高くするメリットがない。The pH of the epoxy bleed out inhibitor solution need not be particularly limited, but is usually between pH 1 and 14, and is preferably treated at pH 2-12. If it deviates from this range, the damage of the material is large and the effect of preventing epoxy bleed out is low.
Moreover, the temperature of the epoxy bleedout inhibitor solution can be within a temperature range that can be carried out with an aqueous solution, but is usually 5 to 90 ° C, preferably 10 to 60 ° C. If the temperature is too low, the epoxy bleed-out effect is low, and if it is too high, the effect is saturated, the workability is deteriorated, and there is no merit of raising the temperature.

溶媒として有機溶媒を用いる場合、有機溶媒としては、メタノール、エタノール、イソプロパノール等のアルコール、アセトン、メチルエチルケトン等のケトンが挙げられる。有機溶媒を用いる際のエポキシブリードアウト防止剤溶液の温度は室温が好ましい。   When an organic solvent is used as the solvent, examples of the organic solvent include alcohols such as methanol, ethanol and isopropanol, and ketones such as acetone and methyl ethyl ketone. The temperature of the epoxy bleedout inhibitor solution when using an organic solvent is preferably room temperature.

さらに、エポキシブリードアウト防止剤溶液での処理時間は、０．１秒以上３００秒以下で効果を見て適宜調整すればよく、作業の再現性と効率を考慮すると１秒以上１２０秒以下が好ましい。短すぎると、エポキシブリードアウト防止の効果が低く、また作業の再現性が難しくなるし、長すぎても効果が飽和し、かつ作業効率が低くなる。   Furthermore, the treatment time with the epoxy bleed-out inhibitor solution may be appropriately adjusted in view of the effect in the range of 0.1 seconds to 300 seconds, and is preferably 1 second to 120 seconds in consideration of work reproducibility and efficiency. . If it is too short, the effect of preventing epoxy bleed-out will be low, the reproducibility of the work will be difficult, and if it is too long, the effect will be saturated and the work efficiency will be low.

また、エポキシブリードアウト防止方法は、エポキシブリードアウト防止剤溶液に配線基材を浸漬するか、またはエポキシブリードアウト防止剤溶液を基材にシャワー、スプレーなどにより散布するか、スピンコーターなどにより塗布するなどして接触させた後、水洗、乾燥すればよい。   Moreover, the epoxy bleed-out prevention method immerses the wiring substrate in the epoxy bleed-out inhibitor solution, or sprays the epoxy bleed-out inhibitor solution on the substrate by shower, spray, etc., or applies it by a spin coater or the like. After contacting them with water, they may be washed with water and dried.

また、エポキシブリードアウト防止剤に主成分である上記含フッ素有機化合物とともに、めっき皮膜や金属素材等の金属表面の変色防止剤や封孔処理剤を含有させることにより、変色防止効果、封孔処理効果とブリードアウト効果を同時に付与することができる。
このような変色防止剤または封孔処理剤としては、それぞれ公知のものを用いることができる。例えば変色防止剤としては、イミダゾール誘導体、トリアゾール誘導体、テトラゾール誘導体、チアゾール誘導体等の含窒素複素環状化合物を用いることが好ましい。In addition to the above-mentioned fluorine-containing organic compound as the main component in the epoxy bleed-out preventing agent, a discoloration preventing effect and a sealing treatment can be achieved by including a discoloration preventing agent and a sealing agent for metal surfaces such as plating films and metal materials. An effect and a bleed-out effect can be imparted simultaneously.
As such a discoloration preventing agent or sealing agent, known ones can be used. For example, it is preferable to use a nitrogen-containing heterocyclic compound such as an imidazole derivative, a triazole derivative, a tetrazole derivative, or a thiazole derivative as the discoloration preventing agent.

上記のようなエポキシブリードアウト防止処理を行うことによって、配線基材表面のめっき面には上記含フッ素有機化合物が吸着し、１〜数分子程度の厚さの含フッ素有機化合物からなる被膜が形成される。そのため、めっき面とエポキシ樹脂との接触角を増加させ、エポキシ樹脂の滲み出しを抑制することが可能となる。なお、吸着する含フッ素有機化合物の被膜は非常に薄いため、ワイヤーボンディング性、モールディング性等のアセンブリ特性には悪影響を与えない。また、変色防止効果や封孔処理効果を損なうこともない。上記の方法によってエポキシブリードアウト防止処理を施した配線基材、およびそれを用いた半導体パッケージも本発明に包含される。   By performing the epoxy bleed-out prevention treatment as described above, the above-mentioned fluorine-containing organic compound is adsorbed on the plating surface of the wiring substrate surface, and a film made of a fluorine-containing organic compound having a thickness of about 1 to several molecules is formed. Is done. Therefore, it is possible to increase the contact angle between the plated surface and the epoxy resin, and to suppress the seepage of the epoxy resin. In addition, since the film | membrane of the fluorine-containing organic compound to adsorb | suck is very thin, it does not have a bad influence on assembly characteristics, such as wire bonding property and molding property. Further, the discoloration preventing effect and the sealing treatment effect are not impaired. The present invention also includes a wiring substrate subjected to epoxy bleed-out prevention treatment by the above method and a semiconductor package using the wiring substrate.

以下、実施例に基づいて本発明を説明するが、本発明はこれらの実施例に限定されるものではない。   EXAMPLES Hereinafter, although this invention is demonstrated based on an Example, this invention is not limited to these Examples.

実施例１〜１０
銅合金（Ｃｕ：９７．７％−Ｓｎ：２．０％−Ｎｉ：０．２％−Ｐ：０．０３％）製リードフレーム基材に密着性向上のために下地として銅ストライクめっきを行った後、リードフレーム全面に金めっき、銀めっき、銅めっきのいずれかを施した。その後表１に記載したエポキシブリードアウト防止剤処理を浸漬により行った。
尚、実施例８、９、１０で用いたエポキシブリードアウト防止剤の極性基−Ｎ2Ｃ3Ｈ3、−Ｎ3Ｃ2Ｈ2、−Ｎ4ＣＨは、それぞれ１−イミダゾリル基、１，２，３−トリアゾル−１−イル基、１−テトラゾリル基である。
これらの基材について、ダイボンディングを行い、耐エポキシブリードアウト性（耐ＥＢＯ性）、ワイヤーボンディング性（Ｗ／Ｂ性）、モールディング性、耐変色性の評価を行った。結果を表１に示す。表１中、浴組成における「−」は添加しないことを示し、評価における「−」は評価対象外であることを示す。Examples 1-10
Copper strike plating is performed as a base for improving adhesion to a lead frame substrate made of copper alloy (Cu: 97.7% -Sn: 2.0% -Ni: 0.2% -P: 0.03%) After that, either the gold plating, the silver plating, or the copper plating was applied to the entire lead frame. Thereafter, the epoxy bleed-out inhibitor treatment described in Table 1 was performed by immersion.
The polar groups —N 2 C 3 H 3 , —N 3 C 2 H 2 , and —N 4 CH of the epoxy bleed-out inhibitor used in Examples 8, 9, and 10 are a 1-imidazolyl group, 1, 2,3-triazol-1-yl group and 1-tetrazolyl group.
About these base materials, die bonding was performed and epoxy bleed-out resistance (EBO resistance), wire bonding (W / B resistance), molding property, and discoloration resistance were evaluated. The results are shown in Table 1. In Table 1, “-” in the bath composition indicates that it is not added, and “-” in the evaluation indicates that it is not subject to evaluation.

耐エポキシブリードアウト性の評価は以下の方法で行った。
市販の低応力ダイボンディング用エポキシ樹脂（エイブルボンド８３４０、エイブルスティック社製）をエポキシブリードアウト防止剤処理を行っためっき面にシリンジを用いて塗布後、大気中ホットプレートで、１７５℃、３０分加熱硬化した後、エポキシ塗布部を金属顕微鏡（１００倍）で観察した。図１に示すようにダイボンディング用エポキシ樹脂の周りに見られるエポキシブリードアウト（図１中、ダイボンディング用エポキシ樹脂は黒い円で示され、その黒い円の周囲にややうすく見える幅の狭い部分がエポキシブリードアウト部を示している）において、最もエポキシブリードアウトが激しい部分の滲み量（ＥＢＯ量）を測定し、以下のように評価した。
○： １０μｍ未満
△： １０μｍ以上１００μｍ未満
×： １００μｍ以上Epoxy bleed-out resistance was evaluated by the following method.
A commercially available epoxy resin for low-stress die bonding (Able Bond 8340, manufactured by Able Stick Co., Ltd.) is applied to the plated surface treated with the epoxy bleed-out inhibitor using a syringe, and then heated at 175 ° C. for 30 minutes in an atmospheric hot plate. After heat curing, the epoxy coated part was observed with a metal microscope (100 times). As shown in FIG. 1, the epoxy bleed-out seen around the epoxy resin for die bonding (in FIG. 1, the epoxy resin for die bonding is shown by a black circle, and a narrow portion that is slightly faint around the black circle is shown. In the epoxy bleed-out portion, the amount of bleeding (EBO amount) at the portion where the epoxy bleed-out was most severe was measured and evaluated as follows.
○: Less than 10 μm Δ: 10 μm or more and less than 100 μm ×: 100 μm or more

ワイヤーボンディング性の評価は以下の方法で行った。
２５μｍの金ワイヤーを用いて、超音波併用熱圧着方式（温度：２００℃、荷重：５０ｇ、時間：１０ｍｓ）でワイヤーボンディングを行い、プルテスターでプル強度を測定し、以下のように評価した。
○： １０ｇｆ以上
×： １０ｇｆ未満The wire bonding property was evaluated by the following method.
Using a gold wire of 25 μm, wire bonding was performed by an ultrasonic combined thermocompression bonding method (temperature: 200 ° C., load: 50 g, time: 10 ms), and the pull strength was measured with a pull tester and evaluated as follows.
○: 10 gf or more ×: Less than 10 gf

モールディング特性の評価は以下の方法で行った。
市販のモールディング用エポキシ樹脂（住友ベークライト製 ＥＭＥ−６３００）をエポキシブリードアウト防止剤処理を行っためっき面に塗布した後、１７５℃、５時間加熱硬化し、その後、せん断強度を測定し、以下のように評価した。
○： １０ｋｇｆ／ｃｍ2以上
×： １０ｋｇｆ／ｃｍ2未満The molding characteristics were evaluated by the following method.
A commercially available epoxy resin for molding (EME-6300 manufactured by Sumitomo Bakelite) was applied to the plated surface subjected to the epoxy bleed-out inhibitor treatment, and then cured by heating at 175 ° C. for 5 hours, and then the shear strength was measured. It was evaluated as follows.
○: 10 kgf / cm 2 or more ×: Less than 10 kgf / cm 2

変色防止効果の評価は、以下の方法で行った。
４０℃、湿度９０％で９６時間加湿後、外観観察を行い、以下のように評価した。
○： 変色がない
×： 変色があるEvaluation of the discoloration preventing effect was performed by the following method.
After humidifying at 40 ° C. and a humidity of 90% for 96 hours, the appearance was observed and evaluated as follows.
○: No discoloration ×: Discoloration

比較例１
主成分としてカルボン酸を用いて、表１に記載のエポキシブリードアウト防止剤処理を施した以外は実施例１と同様にエポキシブリードアウト防止剤処理を行い、実施例１と同様に評価した。結果を表１に示す。Comparative Example 1
An epoxy bleed out inhibitor treatment was performed in the same manner as in Example 1 except that the epoxy bleed out inhibitor treatment described in Table 1 was performed using carboxylic acid as a main component, and evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.

比較例２
表１に記載の基板を用い、エポキシブリードアウト防止剤処理を行わなかった以外は実施例１と同様に行い、実施例１と同様に評価した。結果を表１に示す。Comparative Example 2
The same procedure as in Example 1 was performed, except that the epoxy bleed-out inhibitor treatment was not performed, and evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.

Figure 2007083538
Figure 2007083538

Figure 2007083538
Figure 2007083538

Figure 2007083538
Figure 2007083538

（１）炭素原子が３個以上２４個以下であるフルオロ炭化水素基ＣｘＨｙＦｚ−（ｘ＝３〜２４、ｙ＝０〜４８、ｚ＝１〜４９、ｙ＋ｚ≦２ｘ＋１）と、メルカプト基、アミノ基、リン酸エステル基、カルボキシル基、イミダゾリル基、トリアゾリル基及びテトラゾリル基からなる群から選ばれた極性基Ｒ−を有する含フッ素有機化合物を含有することを特徴とするダイボンディング工程におけるエポキシブリードアウト防止剤。

（２）変色防止剤又は封孔処理剤を含有することを特徴とする前記（１）に記載のエポキシブリードアウト防止剤。
（３）変色防止剤が、含窒素複素環状化合物を含有することを特徴とする前記（２）項に記載のエポキシブリードアウト防止剤。
（４）含窒素複素環状化合物が、イミダゾール誘導体、トリアゾール誘導体、テトラゾール誘導体、チアゾール誘導体のいずれかであることを特徴とする前記（３）に記載のエポキシブリードアウト防止剤。
（５）（１）〜（４）のいずれかに記載のエポキシブリードアウト防止剤を含有する溶液に配線基材を浸漬するか、または該エポキシブリードアウト防止剤を含有する溶液を配線基材に散布・塗布することを特徴とするエポキシブリードアウト防止方法。
（６）（１）〜（４）のいずれかに記載のエポキシブリードアウト防止剤を含有する溶液に配線基材を浸漬するか、または該エポキシブリードアウト防止剤を含有する溶液を配線基材に散布・塗布することによりエポキシブリードアウト防止処理を施したことを特徴とする配線基材。
（７）（１）〜（４）のいずれかに記載のエポキシブリードアウト防止剤が表面に吸着していることを特徴とする配線基材。
（８）（６）又は（７）に記載の配線基材を用いたことを特徴とする半導体パッケージ。 (1) a fluorohydrocarbon group CxHyFz- (x = 3 to 24, y = 0 to 48, z = 1 to 49, y + z ≦ 2x + 1) having 3 to 24 carbon atoms , a mercapto group, and an amino group An epoxy bleed-out prevention in a die bonding process, characterized by containing a fluorine-containing organic compound having a polar group R- selected from the group consisting of a phosphate group, a carboxyl group, an imidazolyl group, a triazolyl group and a tetrazolyl group Agent.

( 2 ) The epoxy bleed-out inhibitor as described in (1) above, which contains a discoloration inhibitor or a sealing agent.
( 3 ) The epoxy bleedout inhibitor as described in the above item ( 2 ), wherein the discoloration inhibitor contains a nitrogen-containing heterocyclic compound.
( 4 ) The epoxy bleedout inhibitor as described in ( 3 ) above, wherein the nitrogen-containing heterocyclic compound is any one of an imidazole derivative, a triazole derivative, a tetrazole derivative, and a thiazole derivative.
( 5 ) The wiring substrate is immersed in a solution containing the epoxy bleed-out preventing agent according to any one of (1) to ( 4 ), or a solution containing the epoxy bleed-out preventing agent is used as the wiring substrate. Epoxy bleed-out prevention method characterized by spraying and applying.
( 6 ) The wiring substrate is immersed in a solution containing the epoxy bleed-out preventing agent according to any one of (1) to ( 4 ), or a solution containing the epoxy bleed-out preventing agent is used as the wiring substrate. A wiring substrate characterized in that an epoxy bleed-out prevention treatment is applied by spraying and applying.
( 7 ) A wiring substrate, wherein the epoxy bleed-out preventing agent according to any one of (1) to ( 4 ) is adsorbed on the surface.
( 8 ) A semiconductor package using the wiring substrate according to ( 6 ) or ( 7 ).

Claims (11)

炭素原子が３個以上２４個以下であるフルオロ炭化水素基ＣｘＨｙＦｚ−（ｘ＝３〜２４、ｙ＝０〜４８、ｚ＝１〜４９、ｙ＋ｚ≦２ｘ＋１）と極性基Ｒ−を有する含フッ素有機化合物を含有することを特徴とするダイボンディング工程におけるエポキシブリードアウト防止剤。   Fluorine-containing organic compound having a fluorohydrocarbon group CxHyFz- (x = 3 to 24, y = 0 to 48, z = 1 to 49, y + z ≦ 2x + 1) having 3 to 24 carbon atoms and a polar group R- An epoxy bleed-out preventing agent in a die bonding process, comprising a compound. 極性基Ｒ−が、イオウ（Ｓ）、窒素（Ｎ）、リン（Ｐ）、酸素（Ｏ）のいずれかを含む極性基であることを特徴とする請求の範囲第１項に記載のエポキシブリードアウト防止剤。   The epoxy bleed according to claim 1, wherein the polar group R- is a polar group containing any of sulfur (S), nitrogen (N), phosphorus (P), and oxygen (O). Anti-out agent. 極性基Ｒ−が、メルカプト基、アミノ基、含窒素複素環基、リン酸エステル基、カルボキシル基のいずれかであることを特徴とする請求の範囲第２項に記載のエポキシブリードアウト防止剤。   The epoxy bleed-out inhibitor according to claim 2, wherein the polar group R- is any one of a mercapto group, an amino group, a nitrogen-containing heterocyclic group, a phosphate group, and a carboxyl group. 含窒素複素環基が、イミダゾリル基、トリアゾリル基、テトラゾリル基、およびそれらの誘導体のいずれかであることを特徴とする請求の範囲第３項に記載のエポキシブリードアウト防止剤。   The epoxy bleed-out inhibitor according to claim 3, wherein the nitrogen-containing heterocyclic group is any one of an imidazolyl group, a triazolyl group, a tetrazolyl group, and derivatives thereof. 変色防止剤又は封孔処理剤を含有することを特徴とする請求の範囲第１項〜第４項のいずれかに記載のエポキシブリードアウト防止剤。   The epoxy bleed-out inhibitor according to any one of claims 1 to 4, further comprising a discoloration inhibitor or a sealing agent. 変色防止剤が、含窒素複素環状化合物を含有することを特徴とする請求の範囲第５項に記載のエポキシブリードアウト防止剤。   6. The epoxy bleed-out inhibitor according to claim 5, wherein the discoloration inhibitor contains a nitrogen-containing heterocyclic compound. 含窒素複素環状化合物が、イミダゾール誘導体、トリアゾール誘導体、テトラゾール誘導体、チアゾール誘導体のいずれかであることを特徴とする請求の範囲第６項に記載のエポキシブリードアウト防止剤。   The epoxy bleed-out inhibitor according to claim 6, wherein the nitrogen-containing heterocyclic compound is any one of an imidazole derivative, a triazole derivative, a tetrazole derivative, and a thiazole derivative. 請求の範囲第１項〜第７項のいずれかに記載のエポキシブリードアウト防止剤を含有する溶液に配線基材を浸漬するか、または該エポキシブリードアウト防止剤を含有する溶液を配線基材に散布・塗布することを特徴とするエポキシブリードアウト防止方法。   A wiring substrate is immersed in a solution containing the epoxy bleed-out preventing agent according to any one of claims 1 to 7, or a solution containing the epoxy bleed-out preventing agent is used as a wiring substrate. Epoxy bleed-out prevention method characterized by spraying and applying. 請求の範囲第１項〜第７項のいずれかに記載のエポキシブリードアウト防止剤を含有する溶液に配線基材を浸漬するか、または該エポキシブリードアウト防止剤を含有する溶液を配線基材に散布・塗布することことによりエポキシブリードアウト防止処理を施したことを特徴とする配線基材。   A wiring substrate is immersed in a solution containing the epoxy bleed-out preventing agent according to any one of claims 1 to 7, or a solution containing the epoxy bleed-out preventing agent is used as a wiring substrate. A wiring substrate characterized in that an epoxy bleed-out prevention treatment is applied by spraying and applying. 請求の範囲第１項〜第７項のいずれかに記載のエポキシブリードアウト防止剤が表面に吸着していることを特徴とする配線基材。   A wiring base material, wherein the epoxy bleed-out preventing agent according to any one of claims 1 to 7 is adsorbed on the surface. 請求の範囲第９項又は第１０項に記載の配線基材を用いたことを特徴とする半導体パッケージ。   A semiconductor package using the wiring substrate according to claim 9 or 10.
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