TWI540231B - Electrolyte composition for removing burr and method of removing burr - Google Patents

Description

除溢料用電解液組合物以及溢料的除去方法 Electrolyte composition for flashing and method for removing flash

本發明涉及一種除溢料用電解液組合物以及使用其的溢料之除去方法。 The present invention relates to an electrolyte composition for removing flash and a method for removing flash using the same.

更具體而言，本發明涉及一種在通電除去模塑成型品的導電部件的表面產生的溢料時，不會對除溢料以外的樹脂成型部造成損傷、並且能夠在例如1秒的非常短的通電時間內有效除去溢料的除溢料用電解液組合物以及使用了該除溢料用電解液組合物的溢料的除去方法。 More specifically, the present invention relates to a method of causing damage to a resin molded portion other than the flash material when the flash is generated by removing the surface of the conductive member of the molded article, and can be extremely short, for example, at 1 second. In the energization time, the electrolyte composition for removing the flash material and the method for removing the flash material using the electrolyte composition for the flash material are effectively removed.

以往，包括下部件的模塑成型品被廣泛使用：半導體積體電路或光半導體元件等電子元件；用於裝載電子元件、並將其與外部基板等電連接的、由金屬薄板形成的導電部件；以及用於確保導電部件中的規定位置的絕緣性、並維持電子元件與導電部件的一體性的樹脂成型部。 Conventionally, a molded article including a lower member has been widely used: an electronic component such as a semiconductor integrated circuit or an optical semiconductor element; a conductive member formed of a thin metal plate for mounting an electronic component and electrically connecting it to an external substrate or the like. And a resin molded portion for ensuring insulation at a predetermined position in the conductive member and maintaining integrity of the electronic component and the conductive member.

另外，這樣的模塑成型品可以通過至少將導電部件和絕緣性樹脂利用例如傳遞模塑成型而得到，關於電子元件，在將導電部件以及絕緣性樹脂模塑成型為一體時， 存在於將導電部件以及絕緣性樹脂模塑成型為一體而得到模塑成型品後，會附著在露出的導電部件上的情形。 Further, such a molded article can be obtained by, for example, at least a conductive member and an insulating resin by transfer molding, and when the conductive member and the insulating resin are integrally molded with respect to the electronic component, There is a case where a conductive member and an insulating resin are integrally molded to obtain a molded article, and then adhered to the exposed conductive member.

更具體地，單獨將導電部件或者將裝載有電子元件的狀態的導電部件載置在模具內後，將絕緣性樹脂壓入模具內，通過加熱等固化，從而形成樹脂成型部。 More specifically, after the conductive member or the conductive member in a state in which the electronic component is mounted is placed in the mold alone, the insulating resin is pressed into the mold and cured by heating or the like to form a resin molded portion.

但是，眾所周知，壓入絕緣性樹脂時，絕緣樹脂滲出至樹脂成型部周圍的導電部件，其結果，在導電部件表面產生由絕緣性樹脂形成的薄溢料。 However, it is known that when the insulating resin is pressed, the insulating resin oozes out to the conductive member around the resin molded portion, and as a result, a thin flash formed of an insulating resin is generated on the surface of the conductive member.

特別是在得到模塑成型品後，相對於露出的導電部件裝載電子元件時，在導電部件表面產生的溢料成為使電子元件與導電部件間的導電性降低的原因，因此需要預先可靠地除去。 In particular, when an electronic component is mounted on an exposed conductive member after the molded article is obtained, the flash generated on the surface of the conductive member causes a decrease in conductivity between the electronic component and the conductive member, and therefore it is necessary to reliably remove it in advance. .

因此，公開了除去上述溢料的技術(例如參照專利文獻1~5)。 Therefore, a technique of removing the above-mentioned flash material has been disclosed (for example, refer to Patent Documents 1 to 5).

即，如圖9(a)~(b)所示，專利文獻1中公開了一種形成於模塑成型品500的樹脂成型部h的溢料浮起裝置400，該裝置400用於將模塑成型品500浸漬於電解液中並輸送，通過將模塑成型品500與一個電極電連接而通電，從而使附著於模塑成型品500的溢料A的溢料浮起，其特徵在於，包括：具有水準移動路徑450的迴圈移動的迴圈輸送機構；預先以規定間隔安裝於迴圈輸送機構、能夠橫向卡緊模塑成型品500的卡緊單元470；以及在水準移動路徑450被卡緊於卡緊單元470的模塑成型品500被浸漬的電解液槽420。 That is, as shown in FIGS. 9(a) to 9(b), Patent Document 1 discloses a flash floating device 400 formed in a resin molded portion h of a molded product 500 for molding The molded article 500 is immersed in an electrolytic solution and transported, and is electrically connected by electrically connecting the molded product 500 to one electrode, thereby causing the flash of the flash A adhering to the molded product 500 to float, which is characterized by including a loop conveying mechanism having a loop movement of the level moving path 450; a chucking unit 470 attached to the loop conveying mechanism at a predetermined interval, capable of laterally clamping the molded product 500; and being jammed at the level moving path 450 The molded product 500 which is close to the clamping unit 470 is immersed in the electrolytic solution tank 420.

另外，作為所使用的電解液，記載有含有苛性鈉以及碳酸鹽作為有效成分的鹼性電解液、或者含有苛性鉀以及碳酸鹽作為有效成分的鹼性電解液。 In addition, as the electrolytic solution to be used, an alkaline electrolyte containing caustic soda and carbonate as an active ingredient or an alkaline electrolyte containing caustic potash and carbonate as an active ingredient is described.

另外，專利文獻2中公開了一種光半導體裝置的製造方法，具有：得到模塑成型品的步驟，利用使用了熱固性樹脂組合物的傳遞成型在配線部件上形成具有多個通孔的光反射層，用配線部件堵塞通孔的一個開口部而形成具有多個凹部的模塑成型品；使用藥液化學除去配線部件表面產生的由熱固性樹脂組合物形成的樹脂溢料的步驟；在配線部件的導體部件表面實施鍍敷的步驟；將光半導體元件分別設置在凹部內的步驟；在設置有光半導體元件的凹部內供給密封樹脂的步驟；使密封樹脂固化的步驟；以及分割模塑成型品，得到多個光半導體裝置的步驟。 Further, Patent Document 2 discloses a method of manufacturing an optical semiconductor device, comprising: a step of obtaining a molded article, and forming a light reflecting layer having a plurality of through holes on the wiring member by transfer molding using a thermosetting resin composition. Forming a molded article having a plurality of recesses by blocking one opening portion of the through hole with a wiring member; removing the resin flash formed by the thermosetting resin composition generated on the surface of the wiring member by using a chemical liquid; and wiring the member a step of plating the surface of the conductor member; a step of disposing the optical semiconductor element in the recess; a step of supplying a sealing resin in the recess in which the optical semiconductor element is provided; a step of curing the sealing resin; and dividing the molded article, A step of obtaining a plurality of optical semiconductor devices.

另外，作為用於除去樹脂溢料的藥液，記載有鹼性過錳酸水溶液、鉻酸-硫酸水溶液、濃硫酸、醯胺系溶液。 Further, as a chemical liquid for removing resin flash, an alkaline permanganic acid aqueous solution, a chromic acid-sulfuric acid aqueous solution, a concentrated sulfuric acid, and a guanamine-based solution are described.

另外，專利文獻3中公開了一種光半導體裝置用模塑成型品，在將用於至少裝載光半導體元件的、用於進行1至多個墊部與光半導體元件電連接的、具有有電連接區的金屬引線部的導電部件，與包圍墊部以及金屬引線部的、具有凹部的由樹脂成型形成的反射器部一體化而形成的用於光半導體元件的模塑成型品中，其特徵在於，導電部件與樹脂成型部的接合部的上表面被鍍敷被膜覆蓋，鍍敷被膜的總厚度為3μm以上，相對於該接合部從導電部 件的端部向鍍敷的水準方向的增長為1μm以上。 Further, Patent Document 3 discloses a molded article for an optical semiconductor device having an electrical connection region for electrically connecting at least one pad portion to an optical semiconductor device for loading at least an optical semiconductor device. The conductive member of the metal lead portion is molded into a molded article for an optical semiconductor element which is formed by integrating a reflector portion formed of a resin having a concave portion and a metal lead portion, and is characterized in that The upper surface of the joint portion between the conductive member and the resin molded portion is covered with a plating film, and the total thickness of the plating film is 3 μm or more, and the conductive portion is bonded to the conductive portion. The end portion of the member is increased by 1 μm or more in the direction of plating.

另外，專利文獻4中公開了一種光半導體裝置用模塑成型品，其特徵在於，包括：具有放置光半導體元件的一個面、和為一個面的背面的為平面的另一面的第1導電部件，在與一個面平行的方向與第1導電部件相對的第2導電部件，以及連接第1導電部件與第2導電部件彼此相對的連接端部之間的樹脂；至少第1導電部件的另一面的一部分從樹脂露出，在第1導電部件的另一面的連接端部側的端部、以及連接端部的至少一部分，通過對第1導電部件的鐳射加工形成金屬氧化物層。 Further, Patent Document 4 discloses a molded article for an optical semiconductor device, comprising: a first conductive member having one surface on which the optical semiconductor element is placed and the other surface on the back surface of one surface; a second conductive member facing the first conductive member in a direction parallel to one surface, and a resin connecting the connection ends of the first conductive member and the second conductive member to each other; at least the other surface of the first conductive member A part of the resin is exposed from the resin, and a metal oxide layer is formed by laser processing of the first conductive member at an end portion on the side of the connection end portion of the other surface of the first conductive member and at least a portion of the connection end portion.

另外，記載有通過電解等方法除去溢料的主旨。 Further, the purpose of removing the flash by means of electrolysis or the like is described.

另外，專利文獻5中公開了一種涉及在引線框熱固性樹脂被一體成型而形成的光半導體裝置用模塑成型品，以依次經過下述第1步驟~第3步驟為特徵的製造方法。 In addition, Patent Document 5 discloses a manufacturing method for a molded article for an optical semiconductor device in which a lead frame thermosetting resin is integrally molded, and which is characterized by sequentially passing through the following first to third steps.

第1步驟：將選自水、電解質水溶液、含有機化合物的水溶液、溶解於水的有機化合物的液體對導電部件以及樹脂成型部噴霧的步驟；第2步驟：使用了導電部件作為陰極的電解的步驟；第3步驟：對導電部件以及樹脂成型部進行超高壓的水噴霧的步驟。 First step: a step of spraying a liquid selected from the group consisting of water, an aqueous electrolyte solution, an aqueous solution containing an organic compound, and an organic compound dissolved in water on a conductive member and a resin molded portion; and a second step: electrolysis using a conductive member as a cathode Step; Step 3: a step of subjecting the conductive member and the resin molded portion to an ultrahigh pressure water spray.

另外記載了，作為電解中使用的電解液，使用 硫酸鈉或氫氧化鈉等電離度高的無機鹽或者氫氧化物。 Further, it is described as an electrolytic solution used for electrolysis. An inorganic salt or hydroxide having a high degree of ionization such as sodium sulfate or sodium hydroxide.

而且記載了，在實施例中，電解液的溫度為50℃，最大施加電流密度為8.0A/dm²，通電時間為180秒。 Further, in the examples, the temperature of the electrolytic solution was 50 ° C, the maximum applied current density was 8.0 A/dm ² , and the energization time was 180 seconds.

現有技術文獻 Prior art literature

專利文獻 Patent literature

專利文獻1：特開平9-17934號公報(申請專利範圍、說明書) Patent Document 1: Japanese Laid-Open Patent Publication No. Hei 9-17934 (Application No. Patent Specification, Specification)

專利文獻2：特開2011-91311號公報(申請專利範圍、說明書) Patent Document 2: JP-A-2011-91311 (Application Patent Range, Specification)

專利文獻3：特開2013-77727號公報(申請專利範圍、說明書) Patent Document 3: JP-A-2013-77727 (Application Patent Range, Specification)

專利文獻4：特開2014-96430號公報(申請專利範圍、說明書) Patent Document 4: JP-A-2014-96430 (Application Patent Range, Specification)

專利文獻5：特開2013-243294號公報(申請專利範圍、說明書) Patent Document 5: JP-A-2013-243294 (Application No. Patent Specification, Specification)

但是，在專利文獻1中公開的溢料浮起裝置中，由於所使用的電解液組合物不合適，因此，若想可靠除去溢料，可見對除溢料以外的樹脂成型部造成過度損傷的問題。 However, in the flash floating device disclosed in Patent Document 1, since the electrolyte composition to be used is not suitable, if the flash material is reliably removed, it is possible to cause excessive damage to the resin molded portion other than the flash material. problem.

特別是光半導體裝置用模塑成型品，在其構成上，由於僅從兩側導電部件的端面夾持而不穩定的樹脂成型部(以下也稱作“隔離部”)，因此，可見下述問題，該隔離部易從導電部件剝離，氣密性降低，使後續製造步驟 中填充的密封樹脂滲出，乃至光半導體裝置的品質顯著受損。 In particular, the molded article for an optical semiconductor device has a resin molded portion (hereinafter also referred to as a "separator portion" which is unstable from the end faces of the both side conductive members, and thus can be seen as follows. The problem is that the partition is easily peeled off from the conductive member, and the airtightness is lowered to make subsequent manufacturing steps. The encapsulating resin filled in is oozing out, and the quality of the optical semiconductor device is significantly impaired.

另外，在專利文獻2中公開的光半導體裝置的製造方法中，通過將鹼性過錳酸水溶液、鉻酸-硫酸水溶液、濃硫酸或者醯胺系溶液等用作藥液，能有效除去樹脂溢料，而不會對樹脂成型部造成損傷，能夠穩定確保氣密性。 Further, in the method for producing an optical semiconductor device disclosed in Patent Document 2, by using an alkaline permanganic acid aqueous solution, a chromic acid-sulfuric acid aqueous solution, a concentrated sulfuric acid or a guanamine-based solution or the like as a chemical liquid, the resin overflow can be effectively removed. The material is not damaged by the resin molded portion, and the airtightness can be stably ensured.

但是，實際上，使用這些藥液除去溢料時，可見對除溢料以外的樹脂成型部造成過度損傷、光半導體裝置用模塑成型品的氣密性易降低的問題。 However, in actuality, when the chemical liquid is used to remove the flash, it is seen that the resin molded portion other than the flash material is excessively damaged, and the airtightness of the molded article for an optical semiconductor device is liable to be lowered.

這一點在專利文獻2的說明書中記載有下述主旨，由於利用藥液進行處理，能夠適度破壞樹脂部分的壁面，因此能夠提高與後續製造步驟中填充的密封樹脂之間的密接性。 In the specification of Patent Document 2, the following description is described. Since the treatment with the chemical solution can appropriately break the wall surface of the resin portion, the adhesion to the sealing resin filled in the subsequent production step can be improved.

由此也可以看出，在專利文獻2中公開的光半導體裝置的製造方法中，對除溢料以外的樹脂成型部造成過度損傷。 In the method of manufacturing an optical semiconductor device disclosed in Patent Document 2, it is also possible to cause excessive damage to the resin molded portion other than the flash.

另外，專利文獻2中公開的溢料的除去方法是所謂的“化學浸漬”方式，必須根據作為溢料除去的物件的樹脂的種類，選擇專用的藥液，還可見更換製造線等煩雜的問題。 Further, the method of removing the flash disclosed in Patent Document 2 is a so-called "chemical immersion" method, and it is necessary to select a dedicated chemical solution depending on the type of the resin to be removed as a flash material, and it is also possible to find troublesome problems such as replacement of the manufacturing line. .

另外，在專利文獻3中公開的光半導體裝置用模塑成型品中，沒有記載具體的溢料的除去方法，但是，通過除去溢料，光半導體裝置用模塑成型品的氣密性降低成為問題。 Further, in the molded article for an optical semiconductor device disclosed in Patent Document 3, a specific method of removing the flash material is not described. However, by removing the flash material, the airtightness of the molded article for the optical semiconductor device is lowered. problem.

並且，在專利文獻3中，通過用鍍敷被膜來覆蓋導電部件與隔離部的接合部的上表面，以確保氣密性。 Further, in Patent Document 3, the upper surface of the joint portion between the conductive member and the partition portion is covered with a plating film to ensure airtightness.

但是，由於不僅在模塑成型後需要另外的鍍敷步驟，而且，不僅導電部件、就連直至與其接連的隔離部的一部分也必須形成鍍敷被膜，因此，製造步驟變複雜，品質穩定性和經濟性存在問題。 However, since an additional plating step is required not only after molding, but also a conductive coating is required not only for the conductive member but also for a part of the separator which is connected thereto, the manufacturing steps become complicated, quality stability and There is a problem with the economy.

另外，還可見通過鍍敷液使樹脂成型部受損的問題。 Further, the problem that the resin molded portion is damaged by the plating liquid can also be seen.

另外，在專利文獻4中公開的光半導體裝置用模塑成型品中，也僅記載有通過電解等方法除去溢料的主旨，但是，通過除去溢料，光半導體裝置用模塑成型品的氣密性降低成為問題。 In addition, in the molded article for an optical semiconductor device disclosed in Patent Document 4, only the method of removing the flash by means of electrolysis or the like is described. However, the gas of the molded article for the optical semiconductor device is removed by removing the flash. Reduced density becomes a problem.

並且，在專利文獻4中，為了將隔離部更穩定地固定於導電部件的端面，對導電部件的端面部分實施鐳射加工，形成具有微小凹凸的金屬氧化物層，對導電部件的端面部分進行表面改質。 Further, in Patent Document 4, in order to more stably fix the partition portion to the end surface of the conductive member, the end surface portion of the conductive member is subjected to laser processing to form a metal oxide layer having minute irregularities, and the end surface portion of the conductive member is subjected to surface treatment. Upgraded.

但是，由於需要另外的鐳射加工步驟，因此，製造步驟變複雜，品質穩定性和經濟性存在問題。 However, since an additional laser processing step is required, the manufacturing steps become complicated, and quality stability and economy are problematic.

另外，即使防止隔離部從導電部件的端面完全剝離，也不能抑制到產生微小間隙的程度，可見不能穩定確保充分的氣密性的問題。 Further, even if the separation portion is prevented from being completely peeled off from the end surface of the conductive member, the degree of occurrence of minute gaps cannot be suppressed, and the problem that sufficient airtightness cannot be stably ensured can be seen.

另外，在專利文獻5中公開的光半導體裝置用模塑成型品的製造方法中，僅有效除去溢料成為問題，還未認識到光半導體裝置用模塑成型品的氣密性降低成為問 題。 Further, in the method for producing a molded article for an optical semiconductor device disclosed in Patent Document 5, it is a problem to effectively remove only the flash, and it has not been recognized that the airtightness of the molded article for an optical semiconductor device is lowered. question.

因此，起因於所使用的電解液組合物不合適，可見對除溢料以外的樹脂成型部造成過度損傷、光半導體裝置用模塑成型品的氣密性容易降低的問題。 Therefore, the electrolyte composition to be used is not suitable, and it is seen that the resin molded portion other than the flash material is excessively damaged, and the airtightness of the molded article for an optical semiconductor device is liable to be lowered.

另外，起因於所使用的電解液組合物不合適，電解時的最大施加電流密度高至8.0A/dm²，並且通電時間必須為180秒，因此，實施溢料的除去自身，在經濟上時間上顯著不利，可見製造效率容易降低的問題。 In addition, since the electrolyte composition used is not suitable, the maximum applied current density at the time of electrolysis is as high as 8.0 A/dm ² , and the energization time must be 180 seconds, therefore, it is economically time to carry out the removal of the flash itself. Significantly disadvantageous, it can be seen that the manufacturing efficiency is easily reduced.

因此，本發明的發明人深入研究的結果發現，除去模塑成型品的導電部件表面產生的溢料時，通過將模塑成型品浸漬在以規定比例摻合四乙基氫氧化銨和水而成的電解液組合物中，並通電，不會對除溢料以外的樹脂成型部造成損傷，而且能夠在例如1秒的非常短的通電時間內有效除去溢料，從而完成本發明。 Therefore, as a result of intensive studies by the inventors of the present invention, it has been found that when the flash produced on the surface of the conductive member of the molded article is removed, the molded article is immersed in a predetermined ratio of tetraethylammonium hydroxide and water. The resulting electrolyte composition is energized to prevent damage to the resin molded portion other than the flash material, and the flash can be effectively removed in a very short energization time of, for example, 1 second, thereby completing the present invention.

即，本發明的目的在於提供一種能夠有效除去溢料，而不會對除溢料以外的樹脂成型部造成損傷的除溢料用電解液組合物以及使用了該除溢料用電解液組合物的溢料的除去方法，特別是即使以光半導體裝置用模塑成型品為物件物時，能夠防止隔離部從導電部件剝離、有效保持氣密性、且能夠在非常短的通電時間內有效除去溢料的除溢料用電解液組合物以及使用了該除溢料用電解液組合物的溢料的除去方法。 In other words, it is an object of the present invention to provide an electrolyte composition for removing impurities which can effectively remove flash material without causing damage to a resin molded portion other than the flash material, and an electrolyte composition for using the flash material. In the method of removing the flash material, in particular, when the molded article for an optical semiconductor device is used as an object, it is possible to prevent the separator from being peeled off from the conductive member, effectively maintaining airtightness, and being able to be effectively removed in a very short energization time. An electrolyte composition for flashing the flash material and a method for removing the flash material using the electrolyte solution for the flash material.

根據本發明，提供一種除溢料用電解液組合物，其用於對模塑成型品通電，並除去在將由金屬薄板形成的 導電部件與絕緣性樹脂模塑成型為一體時，產生在所得到的模塑成型品的所述導電部件的表面上的由所述絕緣性樹脂形成的溢料，其特徵在於：含有四乙基氫氧化銨和水；並且，相對於100重量%的所述除溢料用電解液組合物的總量，所述四乙基氫氧化銨的摻合比例為0.2~14重量%的範圍內的值，所述水的摻合比例為30~99.8重量%的範圍內的值，從而能夠解決上述問題。 According to the present invention, there is provided an electrolyte composition for removing impurities which is used for energizing a molded article and removed from a sheet to be formed of a metal sheet. When the conductive member is integrally molded with the insulating resin, a flash formed of the insulating resin on the surface of the conductive member of the obtained molded article is produced, which is characterized by containing tetraethyl And ammonium hydroxide and water; and the blending ratio of the tetraethylammonium hydroxide is in the range of 0.2 to 14% by weight based on 100% by weight of the total amount of the electrolyte composition for the flashover The value of the water blending ratio is a value in the range of 30 to 99.8% by weight, so that the above problem can be solved.

即，採用本發明的除溢料用電解液組合物時，由於以規定比例摻合四乙基氫氧化銨和水而成，因此，通電除去模塑成型品的導電部件的表面產生的溢料時，不會對除溢料以外的樹脂成型部造成損傷，並且能夠在例如1秒的非常短的通電時間內有效除去溢料。 In other words, in the case of using the electrolytic solution composition for the flashing of the present invention, since tetraethylammonium hydroxide and water are blended at a predetermined ratio, the flash generated by the surface of the conductive member of the molded article is removed by energization. At this time, damage to the resin molded portion other than the flash material is not caused, and the flash can be effectively removed in a very short energization time of, for example, 1 second.

因此，特別是以光半導體裝置用模塑成型品為物件物時，也能夠防止隔離部從導電部件剝離，能夠有效保持氣密性，並且，能夠在非常短的通電時間內有效除去溢料。 Therefore, in particular, when the molded article for an optical semiconductor device is used as an object, it is possible to prevent the separator from being peeled off from the conductive member, to effectively maintain the airtightness, and to effectively remove the flash in a very short energization time.

另外，能夠抑制用於反射光半導體元件發出的光的樹脂成型部(以下有時稱作“反射器部”)的表面的損傷，抑制反射率降低。 In addition, it is possible to suppress damage of the surface of the resin molded portion (hereinafter sometimes referred to as "reflector portion") for reflecting light emitted from the optical semiconductor element, and to suppress a decrease in reflectance.

此外，水的摻合比例為小於30~86重量%的範圍內的值時，通過進一步摻合除四乙基氫氧化銨和水以外的成分(以下有時稱作“其它成分”)，使除溢料用電解液組合物的總量為100重量%。 Further, when the blending ratio of water is a value in the range of less than 30 to 86% by weight, by further blending components other than tetraethylammonium hydroxide and water (hereinafter sometimes referred to as "other components"), The total amount of the electrolyte composition for flashing was 100% by weight.

另外，水的摻合比例為86重量%以上的值時， 可以不摻合其它成分，僅由四乙基氫氧化銨和水使除溢料用電解液組合物的總量為100重量%；也可以進一步摻合其它成分，使除溢料用電解液組合物的總量為100重量%。 In addition, when the blending ratio of water is 86% by weight or more, The total amount of the electrolyte composition for removing the flash may be 100% by weight without the addition of other components, and the other components may be further blended to dissolve the electrolyte for the flash. The total amount of the matter was 100% by weight.

另外，構成本發明的除溢料用電解液組合物時，相對於1離子當量的四乙基氫氧化銨，較佳以0.1~2離子當量的範圍內的值含有選自由羥基乙酸、甲酸以及乙酸組成的組中的至少一種。 Further, in the case of the electrolytic solution composition for flash cleaning according to the present invention, it is preferable to contain a value selected from the group consisting of glycolic acid and formic acid with respect to 1 ion equivalent of tetraethylammonium hydroxide in a range of 0.1 to 2 ion equivalents. At least one of the group consisting of acetic acid.

通過上述構成，能夠緩和由四乙基氫氧化銨帶來的向樹脂成型部的侵蝕性，因此，能夠擴大通電時間和電流密度(以下有時稱作“陰極電流密度”)等通電條件的幅度，乃至能夠更穩定地除去溢料。 According to the above configuration, the corrosion property to the resin molded portion by the tetraethylammonium hydroxide can be alleviated, so that the range of the energization conditions such as the energization time and the current density (hereinafter sometimes referred to as "cathode current density") can be increased. , or even more stable removal of flash.

另外，構成本發明的除溢料用電解液組合物時，相對於100重量%的除溢料用電解液組合物的總量，較佳以0.5~50重量%的範圍內的值含有選自由3-甲氧基-3-甲基-1-丁醇、3-甲氧基丁醇、乙二醇單丙基醚、乙二醇單異丙基醚、乙二醇單丁基醚、二乙二醇單甲基醚、二乙二醇單乙基醚、二丙二醇單甲基醚、二乙二醇二甲基醚以及二乙二醇二乙基醚組成的組中的至少一種。 In addition, when the electrolyte solution composition for the flashing of the present invention is used, it is preferable to contain a value selected from the range of 0.5 to 50% by weight based on 100% by weight of the total amount of the electrolyte composition for the cleaning liquid. 3-methoxy-3-methyl-1-butanol, 3-methoxybutanol, ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, two At least one selected from the group consisting of ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, diethylene glycol dimethyl ether, and diethylene glycol diethyl ether.

通過上述構成，能夠緩和由四乙基氫氧化銨帶來的向樹脂成型部的侵蝕性，因此，能夠擴大通電時間和陰極電流密度等通電時的條件的幅度，乃至能夠更穩定地除去溢料。 According to the above configuration, the corrosion property to the resin molded portion by the tetraethylammonium hydroxide can be alleviated, so that the range of the conditions at the time of energization such as the energization time and the cathode current density can be increased, and the flash can be removed more stably. .

另外，構成本發明的除溢料用電解液組合物時，較佳pH為3~14的範圍內的值。 Further, in the case of constituting the electrolyte solution for flashing of the present invention, the pH is preferably in the range of 3 to 14.

通過上述構成，能夠更穩定地抑制向除溢料以外的樹脂成型部的損傷，能夠有效地除去溢料。 According to the above configuration, damage to the resin molded portion other than the flash material can be more stably suppressed, and the flash can be effectively removed.

另外，構成本發明的除溢料用電解液組合物時，較佳構成模塑成型品的絕緣性樹脂為熱固性環氧系樹脂。 Further, in the case of constituting the electrolyte solution for flashing of the present invention, the insulating resin constituting the molded article is preferably a thermosetting epoxy resin.

通過上述構成，能夠更穩定地抑制向除溢料以外的樹脂成型部的損傷，能夠更有效地除去溢料。 According to the above configuration, damage to the resin molded portion other than the flash material can be more stably suppressed, and the flash can be removed more effectively.

另外，構成本發明的除溢料用電解液組合物時，模塑成型品較佳為光半導體裝置用模塑成型品。 Further, in the case of constituting the electrolytic solution composition for flash cleaning of the present invention, the molded article is preferably a molded article for an optical semiconductor device.

通過上述構成，能夠防止隔離部從導電部件剝離，有效保持氣密性，且能夠有效地除去溢料，並且，能夠抑制反射器部表面的損傷，抑制反射率降低。 According to the configuration described above, it is possible to prevent the separator from being separated from the conductive member, to effectively maintain the airtightness, and to effectively remove the flash, and to suppress damage on the surface of the reflector portion and to suppress a decrease in reflectance.

另外，本發明的另一種方式一種溢料的除去方法，其特徵在於，所述溢料是在將由金屬薄板形成的導電部件與絕緣性樹脂模塑成型為一體時，在所得到的模塑成型品的導電部件的表面產生的、由絕緣性樹脂形成的溢料；溢料的除去方法包括下述步驟(A)~(C)：(A)將模塑成型品浸漬在除溢料用電解液組合物中的步驟，其中所述除溢料用電解液組合物含有四乙基氫氧化銨和水，並且相對於100重量%的除溢料用電解液組合物的總量，四乙基氫氧化銨的摻合比例為0.2~14重量%的範圍內的值，水的摻合比例為30~99.8重量%的範圍內的值；(B)以模塑成型品中的導電部件為陰極、以 對電極為陽極進行通電的電解處理步驟；(C)通過對模塑成型品實施物理處理而除去溢料的步驟。 Further, another aspect of the present invention is a method for removing a flash, characterized in that the flash is obtained by molding a conductive member formed of a thin metal plate and an insulating resin into one body. a flash formed of an insulating resin produced on the surface of the conductive member of the product; the method for removing the flash includes the following steps (A) to (C): (A) immersing the molded article in the electrolytic solution for removing the flash a step in a liquid composition, wherein the electrolyte composition for flashing contains tetraethylammonium hydroxide and water, and tetraethylate relative to 100% by weight of the total amount of the electrolyte composition for flashing The blending ratio of ammonium hydroxide is in the range of 0.2 to 14% by weight, the blending ratio of water is in the range of 30 to 99.8% by weight; (B) the conductive member in the molded article is used as the cathode To An electrolytic treatment step of energizing the electrode for the anode; (C) a step of removing the flash by subjecting the molded article to physical treatment.

即，採用本發明的溢料的除去方法時，由於將模塑成型品浸漬在規定的除溢料用電解液組合物中，通電，使溢料浮起後，對其實施噴射等物理處理，以除去溢料，因此，能夠有效地除去溢料，而不會對除溢料以外的樹脂成型部造成損傷。 In other words, when the method of removing the flash material of the present invention is used, the molded article is immersed in a predetermined electrolyte solution for removing impurities, and is energized to float the flash material, and then subjected to physical treatment such as spraying. In order to remove the flash, it is possible to effectively remove the flash without causing damage to the resin molded portion other than the flash.

另外，實施本發明的溢料的除去方法時，在步驟(B)中，較佳陰極的電流密度為0.5~5A/dm²的範圍內的值，並且通電時間為0.5~5秒的範圍內的值。 Further, in the method of removing the flash of the present invention, in the step (B), the current density of the cathode is preferably in the range of 0.5 to 5 A/dm ² , and the energization time is in the range of 0.5 to 5 seconds. Value.

通過如上所述實施，能夠更有效地除去溢料，而不會對除溢料以外的樹脂成型部造成損傷。 By carrying out as described above, the flash can be removed more efficiently without causing damage to the resin molded portion other than the flash.

100‧‧‧光半導體裝置用模塑成型品 100‧‧‧Molded products for optical semiconductor devices

102a‧‧‧隔離部 102a‧‧‧Isolation Department

102b‧‧‧反射器部 102b‧‧‧Reflector

104a‧‧‧導電部件 104a‧‧‧Electrical parts

104b‧‧‧導電部件 104b‧‧‧Electrical parts

100′‧‧‧多個單位連結狀態下的光半導體裝置用模塑成型品 100'‧‧‧Molded products for optical semiconductor devices in a state in which a plurality of units are connected

106‧‧‧空腔 106‧‧‧ Cavity

110‧‧‧引線 110‧‧‧ lead

120‧‧‧光半導體元件 120‧‧‧Optical semiconductor components

130‧‧‧密封樹脂 130‧‧‧ sealing resin

132‧‧‧螢光塗料 132‧‧‧Fluorescent coating

150‧‧‧用密封樹脂密封了的狀態的光半導體裝置用模塑成型品 150‧‧‧Molded products for optical semiconductor devices in a state sealed with a sealing resin

200‧‧‧電解處理裝置 200‧‧‧Electrolysis treatment unit

202‧‧‧電解處理槽 202‧‧‧ Electrolytic treatment tank

204‧‧‧電解液組合物儲存槽 204‧‧‧ electrolyte composition storage tank

206‧‧‧調溫單元 206‧‧‧temperature control unit

208‧‧‧加熱器 208‧‧‧heater

210‧‧‧泵單元 210‧‧‧ pump unit

212‧‧‧配管 212‧‧‧Pipe

214‧‧‧工件支撐棒 214‧‧‧Workpiece support rod

216‧‧‧金屬電極棒 216‧‧‧Metal electrode rod

218‧‧‧對電極板 218‧‧‧electrode plate

220‧‧‧電源單元 220‧‧‧Power unit

250‧‧‧除溢料用電解液組合物 250‧‧‧Excluding electrolyte composition for flash

300‧‧‧高壓水噴射處理裝置 300‧‧‧High-pressure water jet treatment device

302‧‧‧箱體 302‧‧‧ cabinet

304‧‧‧工件固定夾具 304‧‧‧Working fixture

306‧‧‧高壓水噴射單元 306‧‧‧High pressure water jet unit

308‧‧‧高壓水噴射口 308‧‧‧High pressure water jet

圖1(a)~(b)是為了說明光半導體裝置用模塑成型品而提供的圖。 1(a) to 1(b) are views for explaining a molded article for an optical semiconductor device.

圖2是為了說明安裝光半導體元件、用密封樹脂密封了的狀態的光半導體裝置用模塑成型品而提供的圖。 FIG. 2 is a view for explaining a molded article for an optical semiconductor device in a state in which an optical semiconductor element is mounted and sealed with a sealing resin.

圖3是為了說明沿縱軸連結有多個光半導體裝置用模塑成型品的單位的形態的光半導體裝置用模塑成型品而提供的圖。 FIG. 3 is a view for explaining a molded article for an optical semiconductor device in a form in which a plurality of units of a molded article for an optical semiconductor device are connected to each other along a vertical axis.

圖4是為了說明四乙基氫氧化銨的摻合比例、與溢料除去性以及氣密保持性之間的關係而提供的圖。 Fig. 4 is a view for explaining the relationship between the blending ratio of tetraethylammonium hydroxide, the flash removal property, and the airtight retention.

圖5(a)~(b)是為了說明電解處理裝置而提供的圖。 5(a) to 5(b) are diagrams for explaining an electrolytic treatment apparatus.

圖6是為了說明電解處理裝置而另外提供的圖。 Fig. 6 is a view additionally provided for explaining an electrolytic treatment apparatus.

圖7(a)~(b)是為了說明高壓水噴射處理裝置而提供的圖。 7(a) to 7(b) are diagrams for explaining a high pressure water jet processing apparatus.

圖8(a)~(b)是為了說明高壓水噴射處理裝置而另外提供的圖。 8(a) to 8(b) are diagrams additionally provided to explain the high pressure water jet treatment device.

圖9(a)~(b)是為了說明以往的除去溢料的方法而提供的圖。 9(a) to 9(b) are diagrams for explaining a conventional method of removing flash.

〔第1實施方式〕 [First Embodiment]

第1實施方式涉及一種除溢料用電解液組合物，其用於對模塑成型品通電，並除去在將由金屬薄板形成的導電部件與絕緣性樹脂模塑成型為一體時，產生在所得到的模塑成型品的所述導電部件的表面上的由所述絕緣性樹脂形成的溢料，其特徵在於：含有四乙基氫氧化銨和水；並且，相對於100重量%的所述除溢料用電解液組合物的總量，所述四乙基氫氧化銨的摻合比例為0.2~14重量%的範圍內的值，所述水的摻合比例為30~99.8重量%的範圍內的值。 The first embodiment relates to an electrolytic solution composition for removing impurities, which is used for energizing a molded article, and is removed when a conductive member formed of a thin metal plate is molded integrally with an insulating resin. a flash formed of the insulating resin on the surface of the conductive member of the molded article, characterized by containing tetraethylammonium hydroxide and water; and, with respect to 100% by weight of the removal The total amount of the electrolyte composition for flashing, the blending ratio of the tetraethylammonium hydroxide is in the range of 0.2 to 14% by weight, and the blending ratio of the water is in the range of 30 to 99.8% by weight. The value inside.

以下適當參照附圖對本發明的第1實施方式進行具體說明。 Hereinafter, a first embodiment of the present invention will be specifically described with reference to the drawings.

1.四乙基氫氧化銨 Tetraethylammonium hydroxide

本發明的除溢料用電解液組合物的特徵為含有四乙基氫氧化銨。 The electrolyte composition for cleaning liquid of the present invention is characterized by containing tetraethylammonium hydroxide.

該理由如下，與後述的水的摻合相互作用，通電除去模塑成型品的導電部件表面產生的溢料時，不會對除溢料以外的樹脂成型部造成損傷，並且，能夠在例如1秒的非常短的通電時間內有效除去溢料。 This reason is as follows. When the powder is removed from the surface of the conductive member of the molded article by energization, the resin molded portion other than the flash material is not damaged, and can be, for example, 1 The flash is effectively removed in a very short power-on time of seconds.

更具體地，通過含有四乙基氫氧化銨，能夠局部提高溢料與導電部件的介面的除溢料用電解液組合物的作用，不會對除溢料以外的樹脂成型部造成損傷，並且能夠在非常短的通電時間內有效除去溢料。 More specifically, by containing tetraethylammonium hydroxide, it is possible to locally increase the effect of the electrolyte composition for the flashover and the interface of the conductive member, without causing damage to the resin molded portion other than the flash, and The flash can be effectively removed in a very short power-on time.

因此，特別是以圖1(a)~(b)所示的光半導體裝置用模塑成型品100為對象物時，能夠防止作為僅從兩側被導電部件(104a、104b)的端面夾持而不穩定的作為樹脂成型部的隔離部102a與導電部件(104a、104b)剝離，能夠有效保持氣密性，並且，能夠在非常短的通電時間內有效除去溢料。 Therefore, in particular, when the molded article 100 for an optical semiconductor device shown in FIGS. 1(a) to 1(b) is used as an object, it can be prevented from being sandwiched by the end faces of the conductive members (104a, 104b) only from both sides. On the other hand, the insulating portion 102a which is unstable as the resin molded portion is peeled off from the conductive members (104a, 104b), and the airtightness can be effectively maintained, and the flash can be effectively removed in a very short energization time.

另外，如圖2所示，能夠抑制作為用於發射光半導體元件120發出的光的樹脂成型部的反射器部102b的表面的損傷，能夠抑制反射率降低。 In addition, as shown in FIG. 2, it is possible to suppress damage of the surface of the reflector portion 102b which is a resin molded portion for emitting light emitted from the optical semiconductor element 120, and it is possible to suppress a decrease in reflectance.

另外，如圖3所示，作為溢料的除去物件的光半導體裝置用模塑成型品100′的形態，通常為沿縱軸連結有多個如圖1(a)~(b)所示的光半導體裝置用模塑成型品100的單位的形態。 In addition, as shown in FIG. 3, in the form of a molded article 100' for an optical semiconductor device as a material for removing a material, a plurality of molded products 100' are usually connected along the vertical axis as shown in FIGS. 1(a) to 1(b). The form of the unit of the molded article 100 for an optical semiconductor device.

該形態的光半導體裝置用模塑成型品100′在光半導體元件120的管芯焊接以及使用了引線110的引線接合、以及對空腔106的含有螢光塗料132的密封樹脂130 的填充和固化後，最終單位各自被隔斷。 In the die-molded article 100' for an optical semiconductor device of this form, die bonding of the optical semiconductor element 120 and wire bonding using the lead 110, and sealing resin 130 containing the fluorescent paint 132 to the cavity 106 are used. After filling and curing, the final units are each cut off.

此外，圖1(a)是光半導體裝置用模塑成型品100的立體圖，圖1(b)是沿圖1(a)所示的虛線A-A沿垂直方向切斷，向箭頭方向看時的光半導體裝置用模塑成型品100的截面圖。 1(a) is a perspective view of a molded article 100 for an optical semiconductor device, and FIG. 1(b) is a view taken along a broken line AA shown in FIG. 1(a) in a vertical direction and viewed in an arrow direction. A cross-sectional view of a molded article 100 for a semiconductor device.

另外，圖2是相對於圖1(b)所示的光半導體裝置用模塑成型品100安裝光半導體元件120、用密封樹脂130密封了的狀態的光半導體裝置用模塑成型品150的截面圖。 In addition, FIG. 2 is a cross section of the molded article 150 for an optical semiconductor device in a state in which the optical semiconductor element 120 is mounted on the molded article 100 for an optical semiconductor device shown in FIG. 1(b) and sealed with a sealing resin 130. Figure.

另外，圖3是沿縱軸連結有多個如圖1(a)~(b)所示的光半導體裝置用模塑成型品100的單位的狀態的光半導體裝置用模塑成型品100′的俯視圖。 In addition, FIG. 3 is a molded article 100' for an optical semiconductor device in a state in which a plurality of units of the molded article 100 for an optical semiconductor device shown in FIGS. 1(a) to 1(b) are connected to each other along the vertical axis. Top view.

另外，以相對於100重量%的除溢料用電解液組合物的總量，四乙基氫氧化銨的摻合比例為0.2~14重量%的範圍內的值為特徵。 In addition, the blending ratio of tetraethylammonium hydroxide is in the range of 0.2 to 14% by weight based on 100% by weight of the total amount of the electrolyte composition for cleaning.

該理由如下，四乙基氫氧化銨的摻合比例為小於0.2重量%的值時，存在難以在短的通電時間內有效除去溢料的情況。另外，無視效率，增大陰極電流密度、或者延長通電時間時，存在向除溢料以外的樹脂成型部的損傷變大的情況，特別是以光半導體裝置用模塑成型品為對象時，存在隔離部受損，氣密性容易降低的情況。另一方面，四乙基氫氧化銨的摻合比例為超過14重量%的值時，存在對於樹脂成型部的作用效果變得過高的情況，即使調節陰極電流密度或通電時間時，也存在難以抑制向除溢料以外 的樹脂成型部的損傷的情況。特別是以光半導體裝置用模塑成型品為對象時，存在隔離部受損，氣密性容易過度降低，並且反射器部受損，反射率容易過度降低的情況。 The reason is as follows. When the blending ratio of tetraethylammonium hydroxide is less than 0.2% by weight, it is difficult to effectively remove the flash in a short energization time. In addition, when the cathode current density is increased or the energization time is increased, the damage to the resin molded portion other than the flash material is increased, especially when the molded article for an optical semiconductor device is used. The isolation portion is damaged and the airtightness is easily lowered. On the other hand, when the blending ratio of tetraethylammonium hydroxide is more than 14% by weight, the effect on the resin molded portion becomes too high, and even when the cathode current density or the energization time is adjusted, there is It is difficult to suppress the addition of flash The case of damage of the resin molded portion. In particular, when a molded article for an optical semiconductor device is used, the separator may be damaged, the airtightness may be excessively lowered, and the reflector portion may be damaged, and the reflectance may be excessively lowered.

因此，四乙基氫氧化銨的摻合比例更佳為0.25重量%以上的值，進一步較佳為0.3重量%以上的值。 Therefore, the blending ratio of tetraethylammonium hydroxide is more preferably 0.25 wt% or more, and still more preferably 0.3 wt% or more.

另外，四乙基氫氧化銨的摻合比例更佳為8.8重量%以下的值，進一步較佳為7重量%以下的值。 Further, the blending ratio of tetraethylammonium hydroxide is more preferably 8.8 wt% or less, still more preferably 7% by weight or less.

此外，四乙基氫氧化銨通常以五水合物或者三水合物的形態存在，但是，本發明中的四乙基氫氧化銨的配當比例是以無水物為基準的值。 Further, tetraethylammonium hydroxide is usually present in the form of a pentahydrate or a trihydrate, but the ratio of the tetraethylammonium hydroxide in the present invention is a value based on an anhydride.

接著，使用圖4說明四乙基氫氧化銨的摻合比例、與溢料除去性以及氣密保持性之間的關係。 Next, the relationship between the blending ratio of tetraethylammonium hydroxide, the flash removal property, and the airtightness retainability will be described using FIG.

即，圖4中示出了橫軸為四乙基氫氧化銨的摻合比例(重量%)、左縱軸為溢料除去性(相對值)而得到的特性曲線A、和右縱軸為氣密保持性(相對值)而得到的特性曲線B。 That is, FIG. 4 shows a characteristic curve A in which the horizontal axis represents the blending ratio (% by weight) of tetraethylammonium hydroxide, the left vertical axis is the flash removal property (relative value), and the right vertical axis is Characteristic curve B obtained by hermetic retention (relative value).

另外，特性曲線A以及B的曲線是基於實施例1~5以及比較例1~2的資料而得到的。 Further, the curves of the characteristic curves A and B were obtained based on the data of Examples 1 to 5 and Comparative Examples 1 and 2.

在此，溢料除去性的相對值是以評價點1~3表示使用各種除溢料用電解液組合物，對光半導體裝置用模塑成型品一邊在液溫50℃、陰極電流密度2A/dm²、通電時間1秒的條件下通電一邊進行溢料除去的結果的值，其評價基準如下所述。 Here, the relative value of the flash removability is indicated by the evaluation points 1 to 3 using the various electrolyte compositions for the flash cleaning, and the molded product of the optical semiconductor device has a liquid temperature of 50 ° C and a cathode current density of 2 A/. dm ^2, the power energization time of 1 sec value overflow for removing material while the results, the evaluation criteria are as follows.

評價點3：在構成空腔的底面的導體部件的表 面沒有溢料 Evaluation point 3: Table of conductor parts constituting the bottom surface of the cavity No flash

評價點2：在構成空腔的底面的導體部件的表面僅有幾個殘留有溢料的單位 Evaluation point 2: There are only a few units remaining on the surface of the conductor member constituting the bottom surface of the cavity.

評價點1：在構成空腔的底面的導體部件的表面明確有溢料 Evaluation point 1: Clearly on the surface of the conductor member constituting the bottom surface of the cavity

此外，在實施例中記載有溢料除去性的評價方法等的詳細情況。 Further, in the examples, details of the evaluation method of the flash removal property and the like are described.

另外，氣密保持性的相對值是以評價點1~3表示使用各種除溢料用電解液組合物，對光半導體裝置用模塑成型品一邊通電一邊進行溢料除去後，對空腔填充光固性矽樹脂至包括反射器部的內側壁的上端，目視觀察光半導體裝置用模塑成型品的背面的結果的值，其評價基準如下所述。 In addition, the relative value of the airtightness retention is indicated by the evaluation points 1 to 3, and the cavity composition is filled with the electrolyte solution for the optical semiconductor device, and the cavity is filled with electricity while being energized. The value of the result of the back surface of the molded article of the optical semiconductor device was visually observed from the photocurable enamel resin to the upper end of the inner side wall of the reflector portion, and the evaluation criteria were as follows.

評價點3：在背面的隔離部的附近沒有光固性矽樹脂 Evaluation point 3: No photocurable resin in the vicinity of the separator on the back side

評價點2：在背面的隔離部的附近僅有由光固性矽樹脂引起的著色 Evaluation point 2: Only the coloring caused by the photocurable resin is in the vicinity of the partition on the back side

評價點1：在背面的隔離部的附近明確有光固性矽樹脂 Evaluation point 1: Clear photosetting resin in the vicinity of the separator on the back side

此外，在實施例中記載有氣密保持性的評價方法等的詳細情況。 Further, in the examples, the details of the evaluation method of the airtight retention property and the like are described.

首先，如由特性曲線A理解的那樣，伴隨著四乙基氫氧化銨的摻合比例從0重量%增加，溢料除去性最初急劇增加，之後維持高值。 First, as understood from the characteristic curve A, as the blending ratio of tetraethylammonium hydroxide increases from 0% by weight, the flash removability initially increases sharply and then maintains a high value.

即，可以看出，四乙基氫氧化銨的摻合比例為0.1重量%時，溢料除去性的相對值為1，難以得到充分的溢料除去性，但是，為0.2重量%以上的值時，能夠得到一定程度的溢料除去性，為0.5重量%時，溢料除去性的相對值增加至2，能夠以相當的程度除去溢料。 In other words, when the blending ratio of tetraethylammonium hydroxide is 0.1% by weight, the relative value of the flash removal property is 1, and it is difficult to obtain sufficient flash removability, but the value is 0.2% by weight or more. At this time, a certain degree of flash removability can be obtained, and when it is 0.5% by weight, the relative value of the flash removability is increased to 2, and the flash can be removed to a considerable extent.

並且，可以看出，四乙基氫氧化銨的摻合比例為2重量%時，能夠得到良好的溢料除去性，之後，能夠維持良好的溢料除去性，而不依賴摻合比例的增加。 Further, it can be seen that when the blending ratio of tetraethylammonium hydroxide is 2% by weight, good flash removability can be obtained, and thereafter, good flash removal property can be maintained without depending on the blending ratio. .

接著，如由特性曲線B理解的那樣，氣密保持性不依賴四乙基氫氧化銨的摻合比例的增加，從最初具有良好的氣密保持性，之後緩緩降低。 Next, as understood from the characteristic curve B, the airtight retention does not depend on the increase in the blending ratio of tetraethylammonium hydroxide, and has good airtightness retention from the beginning, and then gradually decreases.

即，可以看出，直至四乙基氫氧化銨的摻合比例為0~8重量%，氣密保持性的相對值為3，能夠維持良好的氣密保持性，另一方面，四乙基氫氧化銨的摻合比例超過8重量%時，氣密保持性緩緩開始降低，為超過14重量%的值時，不能得到充分的氣密保持性，為15重量%時，氣密保持性的相對值變成1，完全喪失氣密保持性。 That is, it can be seen that the blending ratio of tetraethylammonium hydroxide is 0 to 8 wt%, and the relative value of the airtight retention is 3, which can maintain good hermetic retention, and on the other hand, tetraethyl When the blending ratio of ammonium hydroxide is more than 8% by weight, the airtight retention gradually starts to decrease. When the value is more than 14% by weight, sufficient airtightness is not obtained, and when it is 15% by weight, the airtightness is maintained. The relative value becomes 1, and the airtight retention is completely lost.

因此，從特性曲線A以及B可以理解，特別是物件物為光半導體裝置用模塑成型品時，從同時具有溢料除去性和氣密保持性的觀點考慮，相對於100重量%的除溢料用電解液組合物的總量，四乙基氫氧化銨的摻合比例應該為0.2~14重量%的範圍內的值。 Therefore, it can be understood from the characteristic curves A and B that, in particular, when the article is a molded article for an optical semiconductor device, from the viewpoint of having both the flash removal property and the airtightness retention, it is relative to 100% by weight of the flash material. The blending ratio of tetraethylammonium hydroxide should be in the range of 0.2 to 14% by weight based on the total amount of the electrolyte composition.

2.水 2. Water

本發明的除溢料用電解液組合物以含有水為 特徵。 The electrolyte composition for removing impurities according to the present invention contains water as feature.

該理由如下，與上述的四乙基氫氧化銨的摻合相互作用，通電除去模塑成型品的導電部件的表面產生的溢料時，不會對除溢料以外的樹脂成型部造成損傷，並且，能夠在非常短的通電時間內有效地除去溢料。 This reason is as follows. When the above-mentioned tetraethylammonium hydroxide is blended and reacted to remove the flash generated on the surface of the conductive member of the molded article, the resin molded portion other than the flash material is not damaged. Moreover, the flash can be effectively removed in a very short energization time.

即，水由於是作為電解質的四乙基氫氧化銨的良好溶劑，因此能夠有效提高除溢料用電解液組合物的導電性。 That is, since water is a good solvent of tetraethylammonium hydroxide as an electrolyte, the conductivity of the electrolyte composition for flash cleaning can be effectively improved.

因此，通電時的電流密度能夠被均質化，乃至電解處理也能夠均質化。 Therefore, the current density at the time of energization can be homogenized, and even the electrolytic treatment can be homogenized.

此外，在非質子性的極性有機溶劑中電解質也溶解，但是，由於為低導電性，因此，引起物件物的邊緣部的電流密度變高，另一方面，平面部的電流密度變低的現象，難以實現電解處理的均質化。 Further, in the aprotic polar organic solvent, the electrolyte is also dissolved. However, since the conductivity is low, the current density at the edge portion of the object is increased, and the current density at the planar portion is lowered. It is difficult to achieve homogenization of the electrolytic treatment.

另外，以相對於100重量%的除溢料用電解液組合物的總量，水的摻合比例為30~99.8重量%的範圍內的值為特徵。 Further, the blending ratio of water is in a range of from 30 to 99.8% by weight based on 100% by weight of the total amount of the electrolyte composition for flashing.

該理由如下，水的摻合比例為小於30重量%的值時，存在對樹脂成型部的作用效果變得過高的情況，即使調節陰極電流密度或通電時間時，也存在難以抑制向除溢料以外的樹脂成型部的損傷的情況。另一方面，水的摻合比例為超過99.8重量%的值時，存在難以在短的通電時間內有效地除去溢料的情況。另外，無視效率，增大陰極電流密度、或者延長通電時間時，存在向除溢料以外的 樹脂成型部的損傷變大的情況。 The reason is that when the water blending ratio is less than 30% by weight, the effect on the resin molded portion may be excessively high. Even when the cathode current density or the energization time is adjusted, it is difficult to suppress the overflow. The case of damage of the resin molded portion other than the material. On the other hand, when the blending ratio of water is a value exceeding 99.8% by weight, there is a case where it is difficult to effectively remove the flash in a short energization time. In addition, when the efficiency is increased, the cathode current density is increased, or the energization time is extended, there is a The damage of the resin molded portion becomes large.

因此，水的摻合比例更佳為86重量%以上的值，進一步較佳為91.2重量%以上的值，更進一步較佳為93重量%以上的值。 Therefore, the blending ratio of water is more preferably 86% by weight or more, further preferably 91.2% by weight or more, and still more preferably 93% by weight or more.

另外，水的摻合比例更佳為99.75重量%以下的值，進一步較佳為99.7重量%以下的值。 Further, the blending ratio of water is more preferably 99.75 wt% or less, still more preferably 99.7% by weight or less.

此外，水的摻合比例為小於30~86重量%的範圍內的值時，通過進一步摻合除四乙基氫氧化銨與水以外的後述的其它成分，使除溢料用電解液組合物的總量為100重量%。 In addition, when the water blending ratio is a value in the range of less than 30 to 86% by weight, the electrolyte composition for removing the flash material is further blended by further blending other components described below other than tetraethylammonium hydroxide and water. The total amount is 100% by weight.

另外，水的摻合比例為86重量%以上的值時，可以不摻合其它成分，僅由四乙基氫氧化銨和水使除溢料用電解液組合物的總量為100重量%；也可以進一步摻合其它成分，使除溢料用電解液組合物的總量為100重量%。 Further, when the water blending ratio is 86% by weight or more, the other components may not be blended, and the total amount of the electrolyte composition for removing the flash is only 100% by weight from tetraethylammonium hydroxide and water; It is also possible to further blend other components so that the total amount of the electrolyte composition for the flashover is 100% by weight.

另外，所使用的水的電導率較佳為0.08~4μS/cm(測定溫度：25℃)的範圍內的值。 Further, the conductivity of the water to be used is preferably a value in the range of 0.08 to 4 μS/cm (measurement temperature: 25 ° C).

該理由如下，所使用的水的電導率為小於0.08μS/cm的值時，存在水的價格變得過高，經濟上變得不利的情況。 The reason is as follows. When the conductivity of water used is less than 0.08 μS/cm, the price of water may become too high, which may be economically disadvantageous.

另一方面，所使用的水的電導率為超過4μS/cm的值時，存在以下情況，水中所含的離子電沉積(鍍敷)在模塑成型品的導電部件上，殘留在表面上，變色或成為污點，對後面的引線接合密著性造成不良影響。 On the other hand, when the conductivity of the water used is a value exceeding 4 μS/cm, there is a case where ion electrodeposition (plating) contained in the water remains on the surface of the conductive member of the molded article, Discoloration or staining, which adversely affects the subsequent wire bonding adhesion.

因此，所使用的水的電導率更較佳為 0.09μS/cm以上的值，進一步較佳為0.1μS/cm以上的值。 Therefore, the conductivity of the water used is more preferably A value of 0.09 μS/cm or more is further preferably a value of 0.1 μS/cm or more.

另外，所使用的水的電導率更佳為2μS/cm以下的值，進一步較佳為1μS/cm以下的值。 Further, the conductivity of water to be used is more preferably 2 μS/cm or less, and still more preferably 1 μS/cm or less.

此外，作為具有這樣的電導率的水，例如較佳使用超純水、蒸餾水、離子交換水等。 Further, as the water having such conductivity, for example, ultrapure water, distilled water, ion-exchanged water or the like is preferably used.

3.其它成分 3. Other ingredients

另外，本發明的除溢料用電解液組合物，基本上較佳為僅由上述的四乙基氫氧化銨和水構成，但是也可以摻合其它成分。 Further, the electrolytic solution composition for cleaning the present invention is basically preferably composed only of the above-mentioned tetraethylammonium hydroxide and water, but other components may be blended.

例如，相對於1離子當量的四乙基氫氧化銨，較佳以0.1~2離子當量的範圍內的值含有選自由羥基乙酸、甲酸以及乙酸組成的組中的至少一種。 For example, at least one selected from the group consisting of glycolic acid, formic acid, and acetic acid is preferably contained in a range of 0.1 to 2 ion equivalents with respect to 1 ion equivalent of tetraethylammonium hydroxide.

該理由如下，通過含有這些酸，能夠緩和由四乙基氫氧化銨引起的向樹脂成型部的侵蝕性，因此，能夠擴大通電時間和陰極電流密度等通電條件的幅度，乃至能夠更穩定地除去溢料，能夠得到作為所謂“延遲劑”的效果。 The reason for this is that the corrosion of the resin molded portion due to tetraethylammonium hydroxide can be alleviated by the inclusion of these acids. Therefore, the range of energization conditions such as the energization time and the cathode current density can be increased, and the removal can be more stably performed. Over the flash, the effect as a so-called "retarding agent" can be obtained.

即，這些酸的摻合比例為小於0.1離子當量的值時，存在難以充分得到作為上述延遲劑的效果的情況。 另一方面，這些酸的摻合比例為超過2離子當量的值時，存在作為延遲劑的效果被過度發揮，難以有效除去溢料的情況。 That is, when the blending ratio of these acids is a value of less than 0.1 ion equivalent, there is a case where it is difficult to sufficiently obtain the effect as the retardation agent. On the other hand, when the blending ratio of these acids is a value exceeding 2 ion equivalents, the effect as a retarder is excessively exerted, and it is difficult to effectively remove the flash.

因此，這些酸的摻合比例更佳為0.3當量以上的值，進一步較佳為0.8當量以上的值。 Therefore, the blending ratio of these acids is more preferably 0.3 equivalent or more, and still more preferably 0.8 equivalent or more.

另外，這些酸的摻合比例更佳為1.5當量以下的值，進一步較佳為1.2當量以下的值。 Further, the blending ratio of these acids is more preferably 1.5 equivalents or less, and still more preferably 1.2 equivalents or less.

另外，相對於100重量%的除溢料用電解液組合物的總量，較佳以0.5~50重量%的範圍內的值含有選自由3-甲氧基-3-甲基-1-丁醇、3-甲氧基丁醇、乙二醇單丙基醚、乙二醇單異丙基醚、乙二醇單丁基醚、二乙二醇單甲基醚、二乙二醇單乙基醚、二丙二醇單甲基醚、二乙二醇二甲基醚以及二乙二醇二乙基醚組成的組中的至少一種。 Further, it is preferably contained in a range of from 0.5 to 50% by weight, based on 100% by weight of the total amount of the electrolyte composition for the flashover, selected from the group consisting of 3-methoxy-3-methyl-1-butene. Alcohol, 3-methoxybutanol, ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl At least one of the group consisting of a group ether, dipropylene glycol monomethyl ether, diethylene glycol dimethyl ether, and diethylene glycol diethyl ether.

該理由如下，通過含有這些極性溶劑，能夠與上述規定的酸同樣地，得到作為延遲劑的效果。 The reason for this is as follows. By containing these polar solvents, the effect as a retardation agent can be obtained similarly to the above-mentioned predetermined acid.

另外，能夠降低除溢料用電解液組合物的表面張力，能夠迅速除去附著於模塑成型品和對電極的表面的氫氣和氧氣的氣泡。 Further, the surface tension of the electrolyte solution for flashing can be reduced, and bubbles of hydrogen gas and oxygen gas adhering to the surfaces of the molded article and the counter electrode can be quickly removed.

即，這些極性溶劑的摻合比例為小於0.5重量%的值時，存在難以充分得到作為延遲劑的效果、或降低表面張力的效果的情況。另一方面，這些極性溶劑的摻合比例為超過50重量%的值時，存在作為延遲劑的效果被過度發揮，難以有效除去溢料的情況。 In other words, when the blending ratio of these polar solvents is a value of less than 0.5% by weight, there is a case where it is difficult to sufficiently obtain an effect as a retardation agent or an effect of lowering the surface tension. On the other hand, when the blending ratio of these polar solvents is more than 50% by weight, the effect as a retarder may be excessively exerted, and it may be difficult to effectively remove the flash.

因此，這些極性溶劑的摻合比例更佳為1重量%以上的值，進一步較佳為2重量%以上的值。 Therefore, the blending ratio of these polar solvents is more preferably 1% by weight or more, and still more preferably 2% by weight or more.

另外，這些極性溶劑的摻合比例更佳為20重量%以下的值，進一步較佳為10重量%以下的值。 Further, the blending ratio of these polar solvents is more preferably 20% by weight or less, and still more preferably 10% by weight or less.

另外，只要在不損害本發明的除溢料用電解液組合物的效果的範圍內，從潤濕性的改善和乾燥性的改善 等各個觀點考慮，還可以摻合除上述以外的其它成分。 In addition, improvement in wettability and improvement in drying property are possible within a range that does not impair the effect of the electrolytic solution composition for cleaning flash of the present invention. Other components other than the above may also be blended in consideration of various viewpoints.

但是，本發明的除溢料用電解液組合物，由於即使僅含四乙基氫氧化銨以及水，也能夠發揮充分的效果，因此，包含上述物質在內，其它成分的摻合比例，相對於100重量%的除溢料用電解液組合物的總量，較佳為0重量%，即使硬要摻合時，也較佳為50重量%以下的值，更佳為10重量%以下的值，進一步較佳為1重量%以下的值，更進一步較佳為0.1重量%以下的值。 However, the electrolytic solution composition for cleaning the present invention can exhibit a sufficient effect even if it contains only tetraethylammonium hydroxide and water. Therefore, the blending ratio of other components including the above-mentioned materials is relatively The total amount of the electrolyte composition for removing impurities in 100% by weight is preferably 0% by weight, and even if it is hard to be blended, it is preferably 50% by weight or less, more preferably 10% by weight or less. The value is more preferably 1% by weight or less, and still more preferably 0.1% by weight or less.

例如，作為除四乙基氫氧化銨以外的四烷基氫氧化銨，有四甲基氫氧化銨、四丙基氫氧化銨、四丁基氫氧化銨、單甲基三乙基氫氧化銨、二甲基二乙基氫氧化銨、三甲基單乙基氫氧化銨、單甲基三丙基氫氧化銨、二甲基二丙基氫氧化銨、三甲基單丙基氫氧化銨、單甲基三丁基氫氧化銨、二甲基二丁基氫氧化銨、三甲基單丁基氫氧化銨、單乙基三丙基氫氧化銨、二乙基二丙基氫氧化銨、三乙基單丙基氫氧化銨、單乙基三丁基氫氧化銨、二乙基二丁基氫氧化銨、三乙基單丁基氫氧化銨、單丙基三丁基氫氧化銨、二丙基二丁基氫氧化銨以及三丙基單丁基氫氧化銨等。 For example, as a tetraalkylammonium hydroxide other than tetraethylammonium hydroxide, there are tetramethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and monomethyltriethylammonium hydroxide. , dimethyldiethylammonium hydroxide, trimethylmonoethylammonium hydroxide, monomethyltripropylammonium hydroxide, dimethyldipropylammonium hydroxide, trimethylmonopropylammonium hydroxide , monomethyltributylammonium hydroxide, dimethyldibutylammonium hydroxide, trimethylmonobutylammonium hydroxide, monoethyltripropylammonium hydroxide, diethyldipropylammonium hydroxide , triethyl monopropyl ammonium hydroxide, monoethyltributy ammonium hydroxide, diethyl dibutyl ammonium hydroxide, triethyl monobutyl ammonium hydroxide, monopropyl tributyl ammonium hydroxide , dipropyl dibutyl ammonium hydroxide and tripropyl monobutyl ammonium hydroxide.

另外，作為(羥烷基)三烷基氫氧化銨，有膽鹼{(2-羥乙基)三甲基氫氧化銨}、(2-羥乙基)三乙基氫氧化銨、(2-羥乙基)二甲基乙基氫氧化銨、(2-羥乙基)甲基二乙基氫氧化銨、(2-羥乙基)三丙基氫氧化銨、(2-羥乙基)三丁基氫氧化銨、(2-羥丙基)三甲基氫氧化銨、(2-羥丙基)三乙基氫 氧化銨、(2-羥丙基)甲基二乙基氫氧化銨、(2-羥丙基)二甲基乙基氫氧化銨、(2-羥丙基)三丙基氫氧化銨、(2-羥丙基)三丁基氫氧化銨、(4-羥丁基)三甲基氫氧化銨、(4-羥丁基)三乙基氫氧化銨、(4-羥丁基)二甲基乙基氫氧化銨、(4-羥丁基)甲基二乙基氫氧化銨、(4-羥丁基)三丙基氫氧化銨、(4-羥丁基)三丁基氫氧化銨、(2-羥丁基)三甲基氫氧化銨、(2-羥丁基)三乙基氫氧化銨、(2-羥丁基)二甲基乙基氫氧化銨、(2-羥丁基)甲基二乙基氫氧化銨、(2-羥丁基)三丙基氫氧化銨以及(2-羥丁基)三丁基氫氧化銨等。 Further, as (hydroxyalkyl)trialkylammonium hydroxide, there are choline {(2-hydroxyethyl)trimethylammonium hydroxide}, (2-hydroxyethyl)triethylammonium hydroxide, (2) -hydroxyethyl)dimethylethylammonium hydroxide, (2-hydroxyethyl)methyldiethylammonium hydroxide, (2-hydroxyethyl)tripropylammonium hydroxide, (2-hydroxyethyl) Tributylammonium hydroxide, (2-hydroxypropyl)trimethylammonium hydroxide, (2-hydroxypropyl)triethylhydrogen Ammonium oxide, (2-hydroxypropyl)methyldiethylammonium hydroxide, (2-hydroxypropyl)dimethylethylammonium hydroxide, (2-hydroxypropyl)tripropylammonium hydroxide, ( 2-hydroxypropyl)tributylammonium hydroxide, (4-hydroxybutyl)trimethylammonium hydroxide, (4-hydroxybutyl)triethylammonium hydroxide, (4-hydroxybutyl)dimethyl Ethyl ammonium hydroxide, (4-hydroxybutyl) methyl diethyl ammonium hydroxide, (4-hydroxybutyl) tripropyl ammonium hydroxide, (4-hydroxybutyl) tributyl ammonium hydroxide , (2-hydroxybutyl)trimethylammonium hydroxide, (2-hydroxybutyl)triethylammonium hydroxide, (2-hydroxybutyl)dimethylethylammonium hydroxide, (2-hydroxybutyrate) Methyl diethyl ammonium hydroxide, (2-hydroxybutyl) tripropyl ammonium hydroxide, and (2-hydroxybutyl) tributyl ammonium hydroxide.

另外，作為雙(羥烷基)二烷基氫氧化銨，有雙(2-羥乙基)二甲基氫氧化銨、雙(2-羥乙基)二乙基氫氧化銨、雙(2-羥乙基)甲基乙基氫氧化銨、雙(2-羥丙基)二甲基氫氧化銨、雙(2-羥丙基)二乙基氫氧化銨、雙(2-羥丙基)甲基乙基氫氧化銨、雙(4-羥丁基)二甲基氫氧化銨、雙(4-羥丁基)二乙基氫氧化銨、雙(4-羥丁基)甲基乙基氫氧化銨、雙(2-羥丁基)二甲基氫氧化銨、雙(2-羥丁基)二乙基氫氧化銨以及雙(2-羥丁基)甲基乙基氫氧化銨等。 Further, as the bis(hydroxyalkyl)dialkylammonium hydroxide, there are bis(2-hydroxyethyl)dimethylammonium hydroxide, bis(2-hydroxyethyl)diethylammonium hydroxide, and bis (2). -hydroxyethyl)methylethylammonium hydroxide, bis(2-hydroxypropyl)dimethylammonium hydroxide, bis(2-hydroxypropyl)diethylammonium hydroxide, bis(2-hydroxypropyl) )methylethylammonium hydroxide, bis(4-hydroxybutyl)dimethylammonium hydroxide, bis(4-hydroxybutyl)diethylammonium hydroxide, bis(4-hydroxybutyl)methyl b Ammonium hydroxide, bis(2-hydroxybutyl)dimethylammonium hydroxide, bis(2-hydroxybutyl)diethylammonium hydroxide, and bis(2-hydroxybutyl)methylethylammonium hydroxide Wait.

另外，作為三(羥烷基)烷基氫氧化銨，有三(2-羥乙基)甲基氫氧化銨、三(2-羥乙基)乙基氫氧化銨、三(2-羥乙基)丙基氫氧化銨、三(2-羥乙基)丁基氫氧化銨、三(2-羥丙基)甲基氫氧化銨、三(2-羥丙基)乙基氫氧化銨、三(2-羥丙基)丙基氫氧化銨、三(2-羥丙基)丁基氫氧化銨、三(4-羥丁基)甲基氫氧化銨、三(4-羥丁基)乙基氫氧化銨、三(4-羥丁基)丙基氫氧化銨、三(4-羥丁基)丁基氫氧化銨、三(2- 羥丁基)甲基氫氧化銨、三(2-羥丁基)乙基氫氧化銨、三(2-羥丁基)丙基氫氧化銨以及三(2-羥丁基)丁基氫氧化銨等。 Further, as the tris(hydroxyalkyl)alkylammonium hydroxide, there are tris(2-hydroxyethyl)methylammonium hydroxide, tris(2-hydroxyethyl)ethylammonium hydroxide, and tris(2-hydroxyethyl). ) propyl ammonium hydroxide, tris(2-hydroxyethyl)butylammonium hydroxide, tris(2-hydroxypropyl)methylammonium hydroxide, tris(2-hydroxypropyl)ethylammonium hydroxide, three (2-hydroxypropyl)propylammonium hydroxide, tris(2-hydroxypropyl)butylammonium hydroxide, tris(4-hydroxybutyl)methylammonium hydroxide, tris(4-hydroxybutyl)B Ammonium hydroxide, tris(4-hydroxybutyl)propylammonium hydroxide, tris(4-hydroxybutyl)butylammonium hydroxide, tris(2- Hydroxybutyl)methylammonium hydroxide, tris(2-hydroxybutyl)ethylammonium hydroxide, tris(2-hydroxybutyl)propylammonium hydroxide, and tris(2-hydroxybutyl)butylhydroxide Ammonium, etc.

另外，作為苄基三烷基氫氧化銨，有苄基三甲基氫氧化銨、苄基三乙基氫氧化銨、苄基三丙基氫氧化銨等。 Further, examples of the benzyltrialkylammonium hydroxide include benzyltrimethylammonium hydroxide, benzyltriethylammonium hydroxide, and benzyltripropylammonium hydroxide.

另外，作為有機酸，有乙二酸、馬來酸、琥珀酸、戊二酸、己二酸、庚二酸、馬來酸、富馬酸以及苯二甲酸等二羧酸、偏苯三酸以及均苯三甲酸等三元羧酸、羥基酪酸、乳酸以及水楊酸等羥基單羧酸、蘋果酸以及酒石酸等羥基二羧酸、檸檬酸等羥基三元羧酸、天冬氨酸以及谷氨酸等氨基羧酸等。 In addition, as the organic acid, there are dicarboxylic acids such as oxalic acid, maleic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, maleic acid, fumaric acid, and phthalic acid, and trimellitic acid. And hydroxy monocarboxylic acids such as trimesic acid, hydroxybutyric acid, lactic acid and salicylic acid, hydroxydicarboxylic acid such as malic acid and tartaric acid, hydroxytricarboxylic acid such as citric acid, aspartic acid and valley Amino acid such as amino acid.

除此之外，有甲磺酸、苯磺酸、甲苯磺酸、二甲苯磺酸以及碳酸等。 In addition to this, there are methanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, xylenesulfonic acid, and carbonic acid.

另外，作為無機酸，有鹽酸、硫酸、硝酸、高氯酸以及磷酸等。 Further, examples of the inorganic acid include hydrochloric acid, sulfuric acid, nitric acid, perchloric acid, and phosphoric acid.

另外，作為極性溶劑，有甲醇、乙醇、丙醇、異丙醇、丁醇、異丁醇、叔丁醇、二丙酮醇、乙二醇單甲基醚、乙二醇單乙基醚、乙二醇單異丁基醚、乙二醇單叔丁基醚、二乙二醇單丙基醚、二乙二醇單異丙基醚、二乙二醇單丁基醚、二乙二醇單異丁基醚、丙二醇單甲基醚、丙二醇單乙基醚、丙二醇單丙基醚、丙二醇單異丙基醚、丙二醇單丁基醚、丙二醇單異丁基醚、丙二醇單叔丁基醚、二丙二醇單乙基醚、二丙二醇單丙基醚、二丙二醇單異丙基醚、乙二醇二甲基醚、乙二醇二乙基醚、乙二醇二丙基 醚、乙二醇二異丙基醚、乙二醇二丁基醚、二乙二醇二丙基醚、二乙二醇二丁基醚、丙二醇二甲基醚、丙二醇二乙基醚、丙二醇二丙基醚、二丙二醇二甲基醚、二丙二醇二乙基醚、二丙二醇二丙基醚、γ-丁內酯、N-甲基-2-吡咯烷酮、2-吡咯烷酮、二甲基亞碸、乙二醇、二乙二醇、丙二醇、二丙二醇、碳酸丙烯酯以及二甲基乙醯胺等。 Further, as the polar solvent, there are methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tert-butanol, diacetone alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and B. Glycol monoisobutyl ether, ethylene glycol mono-tert-butyl ether, diethylene glycol monopropyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, diethylene glycol single Isobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monoisopropyl ether, propylene glycol monobutyl ether, propylene glycol monoisobutyl ether, propylene glycol mono-tert-butyl ether, Dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoisopropyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl Ether, ethylene glycol diisopropyl ether, ethylene glycol dibutyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol Dipropyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dipropyl ether, γ-butyrolactone, N-methyl-2-pyrrolidone, 2-pyrrolidone, dimethyl alum , ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, propylene carbonate and dimethyl acetamide.

另外，作為無機導電劑，有氫氧化鋰、碳酸鋰、碳酸氫鋰、硫酸鋰、氫氧化鈉、碳酸鈉、碳酸氫鈉、硫酸鈉、氫氧化鉀、碳酸鉀、碳酸氫鉀以及硫酸鉀等。 Further, examples of the inorganic conductive agent include lithium hydroxide, lithium carbonate, lithium hydrogencarbonate, lithium sulfate, sodium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium sulfate, potassium hydroxide, potassium carbonate, potassium hydrogencarbonate, and potassium sulfate. .

另外，作為有機導電劑，有甲胺、乙胺、丙胺、異丙胺、丁胺、己胺、二甲胺、乙基甲胺、丙基甲胺、丁基甲胺、二乙胺、丙基乙胺、二異丙胺、三甲胺、乙基二甲胺、二乙基甲胺、三乙胺、三正丙胺、三正丁胺、單乙醇胺、二乙醇胺、三乙醇胺、二甲基氨基乙醇、二乙基氨基乙醇、N-甲基-二乙醇胺、單-正丙醇胺、單異丙醇胺、二-正丙醇胺、二異丙醇胺、三正丙醇胺、三異丙醇胺、2-氨基-2-甲基-1-丙醇、N-(氨乙基)乙醇胺、N,N-二甲基-2-氨基乙醇、2-(2-氨基乙氧基)乙醇胺、N-油烯基二乙醇胺、N-硬脂醯二乙醇胺、N,N-二丁基單乙醇胺、N,N-二辛基單乙醇胺、N,N-二癸基單乙醇胺、N-二油烯基單乙醇胺、N-二硬脂醯單乙醇胺、乙撐二胺、丙鄰二胺、丙撐二胺、丁撐二胺、己撐二胺、二乙撐三胺、三乙撐四胺、四乙撐五胺、己撐庚胺(hexamethylene heptamine)、亞氨基雙丙胺、雙(六甲撐)三胺、五乙撐六胺(Pentaethylenehexamine)、苯胺、苯二胺、 甲苯二胺、苯二甲基二胺、亞甲基二苯胺、二苯醚二胺、萘二胺、蒽二胺、異佛爾酮二胺、二氨基環己烷、呱嗪、N-氨乙基呱嗪、1,4-二氨乙基呱嗪等。 Further, as the organic conductive agent, there are methylamine, ethylamine, propylamine, isopropylamine, butylamine, hexylamine, dimethylamine, ethylmethylamine, propylmethylamine, butylmethylamine, diethylamine, propylethylamine. , diisopropylamine, trimethylamine, ethyl dimethylamine, diethylmethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, monoethanolamine, diethanolamine, triethanolamine, dimethylaminoethanol, diethyl Base aminoethanol, N-methyl-diethanolamine, mono-n-propanolamine, monoisopropanolamine, di-n-propanolamine, diisopropanolamine, tri-n-propanolamine, triisopropanolamine, 2-amino-2-methyl-1-propanol, N-(aminoethyl)ethanolamine, N,N-dimethyl-2-aminoethanol, 2-(2-aminoethoxy)ethanolamine, N- Olefinic diethanolamine, N-stearyl quinone diethanolamine, N,N-dibutylmonoethanolamine, N,N-dioctyl monoethanolamine, N,N-didecyl monoethanolamine, N-dioleyl Monoethanolamine, N-distearoin monoethanolamine, ethylenediamine, propylenediamine, propylenediamine, butadiene diamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetra Ethylene pentamine, hexamethylene heptamine, imino Propylamine, bis (hexamethylene) triamine, pentaethylene hexamine support (Pentaethylenehexamine), aniline, phenylenediamine, Toluene diamine, benzodimethyl diamine, methylene diphenylamine, diphenyl ether diamine, naphthalene diamine, decane diamine, isophorone diamine, diaminocyclohexane, pyridazine, N-ammonia Ethylpyridazine, 1,4-diaminoethylpyridazine, and the like.

另外，作為表面活性劑，有非離子性表面活性劑、陰離子性活性劑、陽離子性活性劑以及兩性活性劑。 Further, as the surfactant, there are a nonionic surfactant, an anionic active agent, a cationic active agent, and an amphoteric active agent.

在以上中列舉的其它成分可以作為剩餘成分進行摻合，使得四乙基氫氧化銨以及水分別成為規定的摻合比例。 The other components listed above may be blended as a residual component such that tetraethylammonium hydroxide and water each become a predetermined blending ratio.

4.pH 4.pH

另外，本發明的除溢料用電解液組合物在室溫下測定的pH較佳為3~14的範圍內的值。 Further, the pH of the electrolyte composition for flash cleaning according to the present invention measured at room temperature is preferably in the range of 3 to 14.

該理由如下，通過使pH為該範圍內的值，能夠更穩定地抑制向除溢料以外的樹脂成型部的損傷，並且能夠有效除去溢料。 For this reason, by setting the pH to a value within the range, damage to the resin molded portion other than the flash material can be more stably suppressed, and the flash can be effectively removed.

即，該pH為小於3的值時，存在以下情況，導電部件容易腐蝕，機械設備和地板為了應對耐酸性而成為高價，經濟上變得不利。 In other words, when the pH is less than 3, the conductive member is likely to be corroded, and the mechanical equipment and the floor are expensive in response to the acid resistance, which is economically disadvantageous.

因此，該pH更佳為4以上的值，進一步較佳為5以上的值。 Therefore, the pH is more preferably 4 or more, and still more preferably 5 or more.

另外，該pH更佳為13.95以下的值，進一步較佳為13.9以下的值。 Further, the pH is more preferably a value of 13.95 or less, and still more preferably a value of 13.9 or less.

5.對象物 5. Objects

使用本發明的除溢料用電解液組合物來在通電的同時除去溢料的物件物，是將由金屬薄板形成的導電 部件與絕緣性樹脂模塑成型為一體而成的模塑成型品。 The use of the electrolyte composition for cleaning liquid of the present invention to remove the object of the flash while energizing is a conductive material formed of a thin metal plate. A molded article in which a member is molded integrally with an insulating resin.

作為這樣的模塑成型品，没有特别的限制，例如有DIP(Dual Inline Package)、SIP(Single Inline Package)、ZIP(Zigzag Inline Package)、PGA(Pin Grid Array)、SOP(Small Outline Package)、SOJ(Small Outline J-leaded)、SOT(Small Outline Transistor)、QFP(Quad Flat Package)、PLCC(Plastic leaded chip carrier)、BGA(Ball grid array)、LGA(Land grid array)等各種半導體封裝件。 The molded article is not particularly limited, and examples thereof include DIP (Dual Inline Package), SIP (Single Inline Package), ZIP (Zigzag Inline Package), PGA (Pin Grid Array), and SOP (Small Outline Package). Various semiconductor packages such as SOJ (Small Outline J-leaded), SOT (Small Outline Transistor), QFP (Quad Flat Package), PLCC (Plastic Leaded Chip Carrier), BGA (Ball Grid Array), and LGA (Land Grid Array).

以這些半導體封裝件為物件物，使用本發明的除溢料用電解液組合物時，能夠有效除去溢料，而不會對除溢料以外的樹脂成型部造成損傷，因此，導電部件與樹脂成型部之間的接合面不會產生空隙，因此，能夠防止除溢料用電解液組合物浸透到半導體封裝件內。 When the semiconductor package is used as the object, the use of the electrolyte composition for cleaning powder of the present invention can effectively remove the flash without causing damage to the resin molded portion other than the flash, and therefore, the conductive member and the resin Since the joint surface between the molded portions does not generate voids, it is possible to prevent the electrolyte solution for flashing from permeating into the semiconductor package.

因此，能夠有效提高半導體封裝件的信賴性。 Therefore, the reliability of the semiconductor package can be effectively improved.

此外，模塑成型品只要是利用例如傳遞模塑成型、注射模塑成型以及壓縮模塑成型等以往公知的模塑成型而被成型後的模塑成型品，就沒有特別的限制。 In addition, the molded article is not particularly limited as long as it is molded by a conventionally known molding such as transfer molding, injection molding, and compression molding.

另外，使用本發明的除溢料用電解液組合物來在通電的同時除去溢料的物件物，較佳為如圖1(a)~(b)或者圖3所示的光半導體裝置用模塑成型品(100、100′)。 Further, it is preferable to use the electrolytic solution composition for removing the flash material of the present invention to remove the object of the flash material while being energized, and it is preferably a mold for an optical semiconductor device as shown in Figs. 1(a) to (b) or Fig. 3. Plastic molded articles (100, 100').

該理由如下，能夠防止光半導體裝置用模塑成型品(100、100′)中的隔離部102a從導電部件(104a、104b)剝離，能夠有效保持氣密性，並且能夠有效除去溢料。 The reason for this is that the separator 102a in the molded article (100, 100') for an optical semiconductor device can be prevented from being peeled off from the conductive members (104a, 104b), the airtightness can be effectively maintained, and the flash can be effectively removed.

其結果，如圖2所示，能夠有效抑制在後面的 步驟中填充於空腔106的密封樹脂130，通過在隔離部102a與導電部件(104a、104b)之間產生的空隙，滲出到光半導體裝置用模塑成型品(100、100′)的背面。 As a result, as shown in FIG. 2, it can be effectively suppressed in the latter The sealing resin 130 filled in the cavity 106 in the step is oozing out to the back surface of the molded article (100, 100') for an optical semiconductor device by a gap generated between the spacer portion 102a and the conductive members (104a, 104b).

另外，構成模塑成型品的絕緣性樹脂較佳為熱固性環氧系樹脂。 Further, the insulating resin constituting the molded article is preferably a thermosetting epoxy resin.

該理由如下，為熱固性環氧系樹脂時，使用本發明的除溢料用電解液組合物來除去溢料時，能夠進一步穩定地抑制向除溢料以外的樹脂成型部的損傷，並且能夠更有效地除去溢料。 In the case of the thermosetting epoxy resin, when the flash electrolyte composition of the present invention is used to remove the flash material, the damage to the resin molded portion other than the flash material can be further stably suppressed, and the damage can be further improved. Effectively remove flash.

另外，能夠有效地成型為尺寸穩定性以及強度良好的樹脂成型部。 Further, it is possible to efficiently form a resin molded portion having dimensional stability and strength.

另外，作為環氧樹脂，沒有特別的限定，但是，例如有以苯酚酚醛型環氧樹脂、鄰甲酚酚醛型環氧樹脂為代表的、將苯酚類和醛類的酚醛樹脂環氧化而成的環氧樹脂；雙酚A、雙酚F、雙酚S、烷基取代雙酚等的二縮水甘油醚；通過二氨基二苯甲烷、三聚異氰酸等多胺與環氧氯丙烷的反應而得到的縮水甘油胺型環氧樹脂；用過乙酸等過酸將烯鍵氧化而得到的線型脂肪族環氧樹脂；以及脂環族環氧樹脂等。 In addition, the epoxy resin is not particularly limited, and examples thereof include phenol phenolic epoxy resin and o-cresol novolac epoxy resin, and phenolic resins of phenols and aldehydes are epoxidized. Epoxy resin; diglycidyl ether of bisphenol A, bisphenol F, bisphenol S, alkyl substituted bisphenol, etc.; reaction of polyamines such as diaminodiphenylmethane and trimeric isocyanic acid with epichlorohydrin The obtained glycidylamine type epoxy resin; a linear aliphatic epoxy resin obtained by oxidizing an ethylenic bond with a peracid such as peracetic acid; and an alicyclic epoxy resin.

另外，這些環氧樹脂可以單獨使用，也可以兩種以上並用。 Further, these epoxy resins may be used singly or in combination of two or more.

另外，這些環氧樹脂中，較佳使用比較不著色的環氧樹脂，例如較佳雙酚A型環氧樹脂、雙酚F型環氧樹脂、雙酚S型環氧樹脂、三縮水甘油基三聚異氰酸酯。 Further, among these epoxy resins, a relatively uncolored epoxy resin is preferably used, for example, a preferred bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, and a triglycidyl group. Trimeric isocyanate.

另外，較佳相對於上述環氧樹脂適當摻合固化劑、固化促進劑、矽石等無機填充劑，氧化鈦等顏料，有機矽烷偶合劑等，構成熱固性環氧系樹脂。 In addition, it is preferable to mix a curing agent, a curing accelerator, an inorganic filler such as vermiculite, a pigment such as titanium oxide, an organic decane coupling agent, or the like with respect to the epoxy resin to form a thermosetting epoxy resin.

此外，除環氧系樹脂以外，較佳還使用矽系樹脂、聚酯系樹脂、聚鄰苯二醯胺樹脂等。 Further, in addition to the epoxy resin, a fluorene resin, a polyester resin, a polyphthalamide resin or the like is preferably used.

另外，作為導電部件，可以使用以往公知的導電部件，但是，可以較佳使用例如通過對由Cu-Fe合金等形成的金屬薄板實施光刻處理而形成規定回路的導電部件。 Further, as the conductive member, a conventionally known conductive member can be used. However, a conductive member in which a predetermined circuit is formed by performing a photolithography process on a thin metal plate formed of a Cu-Fe alloy or the like can be preferably used.

另外，導電部件也可以用銀等在表面設置鍍敷被膜。 Further, the conductive member may be provided with a plating film on the surface with silver or the like.

〔第2實施方式〕 [Second Embodiment]

第2實施方式涉及一種溢料的除去方法，其特徵在於，所述溢料是在將由金屬薄板形成的導電部件與絕緣性樹脂模塑成型為一體時，在所得到的模塑成型品的導電部件的表面產生的、由絕緣性樹脂形成的溢料；所述溢料的除去方法包括下述步驟(A)~(C)：(A)將模塑成型品浸漬在除溢料用電解液組合物中的步驟，其中所述除溢料用電解液組合物含有四乙基氫氧化銨和水，並且相對於100重量%的除溢料用電解液組合物的總量，四乙基氫氧化銨的摻合比例為0.2~14重量%的範圍內的值，水的摻合比例為30~99.8重量%的範圍內的值；(B)以模塑成型品中的導電部件為陰極、以對電極為陽極進行通電的電解處理步驟； (C)通過對模塑成型品實施物理處理而除去溢料的步驟。 The second embodiment relates to a method of removing flash material, characterized in that the flash material is electrically conductive in the obtained molded article when the conductive member formed of a thin metal plate is molded integrally with an insulating resin. a flash formed of an insulating resin produced on the surface of the member; the method for removing the flash includes the following steps (A) to (C): (A) immersing the molded article in an electrolyte for removing the flash a step in the composition, wherein the electrolyte composition for flashing contains tetraethylammonium hydroxide and water, and tetraethylhydrogen relative to 100% by weight of the total amount of the electrolyte composition for flashing The blending ratio of ammonium oxide is a value in the range of 0.2 to 14% by weight, the blending ratio of water is a value in the range of 30 to 99.8% by weight; (B) the conductive member in the molded article is used as a cathode, An electrolysis treatment step of energizing the counter electrode as an anode; (C) A step of removing flash by performing physical treatment on the molded article.

以下，適當參照附圖，省略與第1實施方式重複的內容，以一種實施方式為例具體說明本發明第2實施方式。 Hereinafter, the second embodiment of the present invention will be specifically described by taking an embodiment as an example, omitting the contents overlapping with the first embodiment as appropriate.

1.步驟(A)：浸漬步驟 1. Step (A): Impregnation step

步驟(A)為將模塑成型品浸漬在除溢料用電解液組合物中的步驟，其中所述除溢料用電解液組合物含有四乙基氫氧化銨和水，並且相對於100重量%的除溢料用電解液組合物的總量，四乙基氫氧化銨的摻合比例為0.2~14重量%的範圍內的值，水的摻合比例為30~99.8重量%的範圍內的值。 The step (A) is a step of immersing the molded article in the electrolyte solution for flashing, wherein the electrolyte composition for flashing contains tetraethylammonium hydroxide and water, and is relative to 100 weight % of the total amount of the electrolyte composition for flashing, the blending ratio of tetraethylammonium hydroxide is in the range of 0.2 to 14% by weight, and the blending ratio of water is in the range of 30 to 99.8% by weight. Value.

更具體地，如圖5(a)~(b)所示，準備電解處理裝置200，對電解處理槽202以及電解液組合物儲存槽204充分供給除溢料用電解液組合物250。 More specifically, as shown in FIGS. 5( a ) to 5 ( b ), the electrolytic treatment apparatus 200 is prepared, and the electrolytic solution composition 250 for the flash is sufficiently supplied to the electrolytic treatment tank 202 and the electrolytic solution composition storage tank 204 .

然後，利用設置於電解液組合物儲存槽204的調溫單元206、加熱器208以及泵單元210，將除溢料用電解液組合物250加熱，使之在電解處理槽202與電解液組合物儲存槽204之間迴圈，將除溢料用電解液組合物250的液溫維持為規定的溫度。 Then, the pyrolysis electrolyte composition 250 is heated by the temperature adjustment unit 206, the heater 208, and the pump unit 210 provided in the electrolyte composition storage tank 204 to be in the electrolytic treatment tank 202 and the electrolyte composition. The storage tanks 204 are looped between each other, and the liquid temperature of the electrolyte composition for flashing liquid is maintained at a predetermined temperature.

此時，從電解液組合物儲存槽204利用泵單元210被汲水、在電解處理槽202中成為過剩部分的除溢料用電解液組合物250，通過配管212被返回到電解液組合物儲存槽204。 At this time, the electrolyte solution composition 250 which is dehydrated by the pump unit 210 from the electrolytic solution composition storage tank 204 and which is excessive in the electrolytic treatment tank 202 is returned to the electrolyte composition storage through the pipe 212. Slot 204.

此外，圖5(a)是電解處理裝置200的俯視圖，圖5(b)是沿圖5(a)所示的虛線A-A沿垂直方向切斷、向箭頭方向看時的電解處理裝置200的截面圖。 5(a) is a plan view of the electrolytic treatment apparatus 200, and FIG. 5(b) is a cross section of the electrolytic treatment apparatus 200 when the vertical line is cut along the broken line AA shown in FIG. 5(a) and viewed in the direction of the arrow. Figure.

然後，利用4根工件支撐棒214支撐已準備的模塑成型品(在此，以圖3中所示的光半導體裝置用模塑成型品100′為例表示)，使之以垂直立起的狀態浸漬於充滿電解處理槽202的除溢料用電解液組合物250。 Then, the prepared molded article (here, as an example of the molded article 100' for an optical semiconductor device shown in FIG. 3) is supported by four workpiece support bars 214 so as to stand upright. The state is immersed in the electrolytic solution composition 250 for overflowing with the electrolytic treatment tank 202.

此時，如圖6所示，使模塑成型品100′的下端面(導電部件露出的端面)接觸作為陰極的金屬電極棒216的上表面。 At this time, as shown in FIG. 6, the lower end surface (the end surface on which the conductive member is exposed) of the molded product 100' is brought into contact with the upper surface of the metal electrode rod 216 as a cathode.

此外，圖6是從圖5(a)~(b)中所示的電解處理裝置200抽出由模塑成型品100′、金屬電極棒216以及工件支撐棒214組成的部分而表示的立體圖。 In addition, FIG. 6 is a perspective view showing a portion including the molded product 100', the metal electrode rod 216, and the workpiece support rod 214 from the electrolytic treatment apparatus 200 shown in FIGS. 5(a) to 5(b).

2.步驟(B)：電解處理步驟 2. Step (B): Electrolysis treatment step

步驟(B)是以模塑成型品中的導電部件為陰極、以對電極為陽極進行通電，進行電解處理的步驟。 The step (B) is a step of performing electrolysis treatment by using a conductive member in the molded article as a cathode and a counter electrode as an anode.

更具體地，以與模塑成型品100′的各個面相對的方式，將作為陽極的對電極板218設置於除溢料用電解液組合物250中後，通過電源單元220施加電壓，進行通電。 More specifically, the counter electrode plate 218 as an anode is placed in the electrolyte solution composition for cleaning E2, and the voltage is applied by the power source unit 220 to be energized, so as to face each surface of the molded product 100'. .

另外，通電時的陰極電流密度較佳為0.5~5A/dm²的範圍內的值。 Further, the cathode current density at the time of energization is preferably a value in the range of 0.5 to 5 A/dm ² .

該理由如下，陰極電流密度為小於0.5A/dm²的值時，存在難以穩定除去溢料的情況。另一方面，陰極電流密度為超過5A/dm²的值時，存在向除溢料以外的樹脂 成型部的損傷變大的情況。 The reason is as follows. When the cathode current density is less than 0.5 A/dm ² , it is difficult to stably remove the flash. On the other hand, when the cathode current density is more than 5 A/dm ² , the damage to the resin molded portion other than the flash material may increase.

因此，陽極電流密度更佳為1A/dm²以上的值，進一步較佳為1.5A/dm²以上的值。 Therefore, the anode current density is more preferably 1 A/dm ² or more, and still more preferably 1.5 A/dm ² or more.

另外，陽極電流密度更佳為4A/dm²以下的值，進一步較佳為3A/dm²以下的值。 Further, the anode current density is more preferably 4 A/dm ² or less, and still more preferably 3 A/dm ² or less.

此外，“陰極電流密度”是指流過模塑成型品的電流值(A)除以構成模塑成型品的導電部件中的未被樹脂成型部覆蓋的部分的表面積(其中，被溢料覆蓋的部分包含在未被樹脂成型部覆蓋的部分內)(dm²)得到的值。 Further, "cathode current density" means a current value (A) flowing through a molded article divided by a surface area of a portion of the conductive member constituting the molded article that is not covered by the resin molded portion (wherein covered by the flash material) The portion contains the value obtained in the portion not covered by the resin molding portion (dm ² ).

另外，通電時的通電時間較佳為0.5~5秒的範圍內的值。 Further, the energization time at the time of energization is preferably a value in the range of 0.5 to 5 seconds.

該理由如下，通電時間為小於0.5秒的值時，存在難以穩定除去溢料的情況。另一方面，通電時間為5秒以上的值時，不僅向除溢料以外的樹脂成型部的損傷變大，而且製造效率降低。 The reason is as follows. When the energization time is a value of less than 0.5 second, there is a case where it is difficult to stably remove the flash. On the other hand, when the energization time is a value of 5 seconds or more, not only the damage to the resin molded portion other than the flash material is increased, but also the manufacturing efficiency is lowered.

因此，通電時間更較佳為0.75秒以上的值，進一步較佳為1秒以上的值。 Therefore, the energization time is more preferably 0.75 seconds or more, and still more preferably 1 second or more.

另外，通電時間更較佳為4秒以下的值，進一步較佳為3秒以下的值。 Further, the energization time is more preferably 4 seconds or less, and still more preferably 3 seconds or less.

另外，通電時的除溢料用電解液組合物的溫度較佳為20~70℃的範圍內的值。 Further, the temperature of the electrolyte composition for flashing at the time of energization is preferably a value in the range of 20 to 70 °C.

該理由如下，除溢料用電解液組合物的溫度為小於20℃的值時，為了使除溢料用電解液組合物的液溫保持恒定，需要用於加熱和冷卻的兩個裝置，存在為維持液 溫而產生費用，經濟上變得不利的情況。 The reason is as follows. When the temperature of the electrolyte composition for flash is less than 20 ° C, in order to keep the liquid temperature of the electrolyte solution for flash cleaning constant, two devices for heating and cooling are required. To maintain liquid It costs a lot of money and becomes economically unfavorable.

另一方面，除溢料用電解液組合物的溫度為超過70℃的值時，存在向除溢料以外的樹脂成型部的損傷變大的情況。 On the other hand, when the temperature of the electrolyte composition for the flash is more than 70 ° C, the damage to the resin molded portion other than the flash material may increase.

因此，除溢料用電解液組合物的溫度更佳為25℃以上的值，進一步較佳為30℃以上的值。 Therefore, the temperature of the electrolyte composition for flashing is more preferably 25 ° C or higher, and still more preferably 30 ° C or higher.

另外，除溢料用電解液組合物的溫度更佳為60℃以下的值，進一步較佳為50℃以下的值。 Further, the temperature of the electrolyte composition for flashing is more preferably 60 ° C or lower, and still more preferably 50 ° C or lower.

3.步驟(C)：高壓水噴射步驟 3. Step (C): High pressure water jet step

步驟(C)是通過對模塑成型品實施物理處理而除去溢料的步驟。 The step (C) is a step of removing the flash by subjecting the molded article to physical treatment.

更具體地，準備圖7(a)~(b)中所示的高壓水噴射處理裝置300，以附著有溢料的面成為上側的方式，將通電後的模塑成型品100′固定在設置於箱體302的內部的工件固定夾具304的上表面。 More specifically, the high-pressure water jet treatment apparatus 300 shown in FIGS. 7(a) to 7(b) is prepared, and the molded product 100' after being energized is fixed in the setting so that the surface on which the flash adheres is the upper side. The upper surface of the workpiece fixing jig 304 inside the casing 302.

然後，利用一邊沿水準方向來回移動一邊向下方噴射10~20MPa的高壓水的高壓水噴射單元306，向模塑成型品100′的附著有溢料的面側噴射高壓水，物理性地除去通過電解處理而浮起的溢料。 Then, the high-pressure water jetting unit 306 that sprays high-pressure water of 10 to 20 MPa downward while moving back and forth in the horizontal direction sprays high-pressure water onto the surface side of the molded product 100' where the flash adheres, and physically removes it. A flash that floats by electrolysis.

另外，如圖8(a)~(b)所示，高壓水噴射單元306在下表面具有多個高壓水噴射口308。 Further, as shown in FIGS. 8(a) to 8(b), the high pressure water injection unit 306 has a plurality of high pressure water injection ports 308 on the lower surface.

因此，能夠一邊沿水準方向來回移動，一邊均勻地噴射高壓水，能夠有效除去溢料。 Therefore, it is possible to uniformly spray high-pressure water while moving back and forth in the horizontal direction, and it is possible to effectively remove the flash.

此外，圖7(a)是高壓水噴射處理裝置300的 俯視圖，圖7(b)是沿著圖7(a)中所示的虛線A-A沿垂直方向切斷，向箭頭方向看時的高壓水噴射處理裝置300截面圖。 In addition, FIG. 7( a ) is a high pressure water jet treatment device 300 In the plan view, FIG. 7(b) is a cross-sectional view of the high-pressure water jet treatment apparatus 300 taken along the broken line A-A shown in FIG. 7(a) in the vertical direction and viewed in the direction of the arrow.

另外，圖8(a)是從圖7(a)~(b)中所示的高壓水噴射處理裝置300抽出高壓水噴射單元306以及模塑成型品100′的部分而表示的立體圖，圖8(b)是高壓水噴射單元306的下表面圖。 In addition, FIG. 8(a) is a perspective view showing a portion of the high-pressure water jet processing unit 300 and the molded product 100' which are taken out from the high-pressure water jet processing apparatus 300 shown in FIGS. 7(a) to 7(b), and FIG. (b) is a lower surface view of the high pressure water jet unit 306.

另外，作為物理性的處理，以噴水器為例進行了說明，但是，也可以使用例如乾燥送風或加濕鼓風等。 Further, as the physical treatment, the water sprayer has been described as an example. However, for example, dry air blowing or humidifying air blowing may be used.

實施例 Example

以下，列舉實施例對本發明進行詳細說明。但是，當然，本發明並不受下述記載的任何限制。 Hereinafter, the present invention will be described in detail by way of examples. However, the present invention is of course not limited to the following description.

〔實施例1〕 [Example 1]

1.除溢料用電解液組合物的製備 1. Preparation of electrolyte composition for flashing

以相對於總量為四乙基氫氧化銨(TEAH)0.5重量%、離子交換水(電導率0.5μS/cm)99.5重量%的方式，將它們收納於容器內，使用作為攪拌裝置的混合器，充分攪拌，使之均勻，成為實施例1的除溢料用電解液組合物。 The mixture was placed in a container so that the total amount was 0.4% by weight of tetraethylammonium hydroxide (TEAH) and 99.5% by weight of ion-exchanged water (conductivity: 0.5 μS/cm), and a mixer as a stirring device was used. The mixture was thoroughly stirred and made uniform to become the electrolytic solution composition for the cleaning of Example 1.

此外，表1中示出了實施例1的除溢料用電解液組合物的摻合組成，省略組成成分的名稱時，用上述括弧內的縮寫標明(在其它實施例、比較例中也同樣)。 In addition, in Table 1, the blending composition of the electrolyte solution for flashing in the first embodiment is shown, and when the names of the constituents are omitted, they are indicated by the abbreviations in the above brackets (the same applies to the other examples and comparative examples). ).

2.光半導體裝置用模塑成型品的準備 2. Preparation of molded articles for optical semiconductor devices

準備利用傳遞模塑成型機將熱固性樹脂組合 物與導電部件模塑成型為一體而成的、光半導體裝置用模塑成型品，其中所述熱固性樹脂組合物通過相對於作為環氧系樹脂的三縮水甘油基三聚異氰酸酯摻合固化劑、固化促進劑、無機填充劑、白色顏料以及偶合劑而成，所述導電部件通過對厚度為0.15mm的、由Cu-Fe合金C194形成的板實施光刻處理而形成回路後，實施鍍銀而成。 Prepare to combine thermosetting resin with a transfer molding machine a molded article for an optical semiconductor device in which a material and a conductive member are integrally molded, wherein the thermosetting resin composition is blended with a triglycidyl trimer isocyanate as an epoxy resin, A curing accelerator, an inorganic filler, a white pigment, and a coupling agent are formed by performing a photolithography process on a plate formed of Cu-Fe alloy C194 having a thickness of 0.15 mm to form a circuit, and then performing silver plating. to make.

更具體地，得到如圖3所示的縱12個×橫15個的單位連結的狀態的、光半導體裝置用模塑成型品100′(縱75mm×橫124mm)。 More specifically, a molded article 100' for an optical semiconductor device (length 75 mm × width 124 mm) in a state in which 12 units in the vertical direction and 15 units in the horizontal direction are connected as shown in FIG. 3 is obtained.

3.評價 3. Evaluation

(1)溢料除去性的評價 (1) Evaluation of flash removal

評價所得到的除溢料用電解液組合物的溢料除去性。 The flash removal property of the obtained electrolyte composition for flashing was evaluated.

即，準備如圖5(a)~(b)中所示的電解處理裝置200，對電解處理槽202以及電解液組合物儲存槽204充分供給準備好的除溢料用電解液組合物250。 In other words, the electrolytic treatment apparatus 200 shown in FIGS. 5(a) to 5(b) is prepared, and the prepared electrolytic solution composition 250 for the cleaning is sufficiently supplied to the electrolytic treatment tank 202 and the electrolytic solution composition storage tank 204.

然後，利用設置於電解液組合物儲存槽204的調溫單元206、加熱器208以及泵單元210，對除溢料用電解液組合物250進行加熱，並使之在電解處理槽202與電解液組合物儲存槽204之間迴圈，將除溢料用電解液組合物250的液溫維持在50℃。 Then, the pyrolysis electrolyte composition 250 is heated by the temperature adjustment unit 206, the heater 208, and the pump unit 210 provided in the electrolyte composition storage tank 204, and is subjected to the electrolytic treatment tank 202 and the electrolyte. The composition storage tanks 204 were looped between each other, and the liquid temperature of the electrolyte composition for flash cleaning 250 was maintained at 50 °C.

然後，使準備好的光半導體裝置用模塑成型品100′利用4根工件支撐棒214支撐，使之以垂直立起的狀態浸漬於充滿於電解處理槽202的除溢料用電解液組合物 250。 Then, the prepared molded article 100' for an optical semiconductor device is supported by four workpiece support bars 214, and is immersed in a state of being vertically erected in the electrolyte solution for cleaning the electrode filled in the electrolytic treatment tank 202. 250.

此時，使光半導體裝置用模塑成型品100′的下端面(導體部件露出的端面)接觸作為陰極的金屬電極棒216的上表面。 At this time, the lower end surface (the end surface on which the conductor member is exposed) of the molded article 100' for the optical semiconductor device is brought into contact with the upper surface of the metal electrode rod 216 as the cathode.

然後，以與光半導體裝置用模塑成型品100′的各個面相對的方式，將作為陽極的對電極板218設置於除溢料用電解液組合物250中後，以對於光半導體裝置用模塑成型品100′的陰極電流密度為1A/dm²的方式，通過電源單元220施加電壓1秒，進行通電。 Then, the counter electrode plate 218 as an anode is placed in the electrolytic solution for removing the flash material 250 so as to face the respective surfaces of the molded article 100' for an optical semiconductor device, and the mold for the optical semiconductor device is used. The molded product 100' had a cathode current density of 1 A/dm ² , and a voltage was applied to the power source unit 220 for 1 second to conduct electricity.

然後，準備如圖7(a)~(b)中所示的高壓水噴射處理裝置300，以空腔側為上側的方式，將通電後的光半導體裝置用模塑成型品100′固定於設置於箱體302的內部的工件固定夾具304的上表面。 Then, the high-pressure water jet processing apparatus 300 shown in FIGS. 7(a) to 7(b) is prepared, and the molded product 100' for the optical semiconductor device after the energization is fixed to the upper side so that the cavity side is the upper side. The upper surface of the workpiece fixing jig 304 inside the casing 302.

然後，利用一邊沿水準方向來回移動一邊向下方噴射15MPa的高壓水的高壓水噴射單元306，向光半導體裝置用模塑成型品100′的空腔側噴射高壓水，物理性地除去通過電解處理而浮起的溢料。 Then, the high-pressure water ejecting unit 306 that ejects 15 MPa of high-pressure water downward in the horizontal direction is sprayed with high-pressure water onto the cavity side of the molded article 100' for optical semiconductor device, and physically removed by electrolytic treatment. And the floating overflow.

另外，對空腔側的背面也同樣地進行高壓水噴射處理。 Further, high pressure water jet treatment is also performed on the back surface on the cavity side in the same manner.

然後，利用純水清洗從高壓噴射處理裝置取出的光半導體裝置用模塑成型品，使之熱風乾燥後，利用恒溫槽進一步使環氧系樹脂固化。 Then, the molded article for an optical semiconductor device taken out from the high-pressure jet processing apparatus is washed with pure water, and dried by hot air, and then the epoxy resin is further cured by a constant temperature bath.

然後，目視觀察空腔側的外觀，沿下述基準評價溢料除去性。所得到的結果表示在表2中。 Then, the appearance of the cavity side was visually observed, and the flash removal property was evaluated along the following criteria. The results obtained are shown in Table 2.

○：在構成空腔的底面的導體部件的表面沒有溢料 ○: there is no flash on the surface of the conductor member constituting the bottom surface of the cavity

△：在構成空腔的底面的導體部件的表面僅有幾個殘留有溢料的單位 △: There are only a few units remaining on the surface of the conductor member constituting the bottom surface of the cavity.

×：在構成空腔的底面的導體部件的表面明確有溢料 ×: there is a clear flash on the surface of the conductor member constituting the bottom surface of the cavity

另外，在進行電解處理時，在對於光半導體裝置用模塑成型品的陰極電流密度保持為1A/dm²的同時，將電壓施加時間改變為2秒以及4秒，同樣地評價溢料除去性。 In the electrolytic treatment, the cathode current density of the molded article for an optical semiconductor device was maintained at 1 A/dm ² , and the voltage application time was changed to 2 seconds and 4 seconds, and the flash removal property was evaluated in the same manner. .

進一步，在將對於光半導體裝置用模塑成型品的陰極電流密度改變為2A/dm²、4A/dm²時，也分別將電壓施加時間改變為1秒、2秒、4秒，同樣地評價溢料除去性。所得到的結果表示在表2中。 Further, when the cathode current density of the molded article for an optical semiconductor device was changed to 2 A/dm ² or 4 A/dm ² , the voltage application time was also changed to 1 second, 2 seconds, and 4 seconds, respectively, and evaluated in the same manner. Flash removal. The results obtained are shown in Table 2.

(2)氣密保持性的評價 (2) Evaluation of airtight retention

評價所得到的除溢料用電解液組合物的氣密保持性。 The airtight retention of the obtained electrolyte composition for flashing was evaluated.

即，相對於上述的溢料除去性的評價後的光半導體裝置用模塑成型品的空腔一部分，填充光固性矽樹脂(信越化學工業(株)製造、LSP-7463)達到由反射器部形成的內側壁的上端，放置12小時以上。 In other words, a portion of the cavity of the molded article for an optical semiconductor device after the evaluation of the flash-removability is filled with a photo-curable enamel resin (manufactured by Shin-Etsu Chemical Co., Ltd., LSP-7463) to reach the reflector. The upper end of the inner side wall formed by the part is placed for 12 hours or more.

然後，目視觀察光半導體裝置用模塑成型品的背面，沿著下述基準評價氣密保持性。所得到的結果表示在表2中。 Then, the back surface of the molded article for an optical semiconductor device was visually observed, and the airtightness was evaluated along the following criteria. The results obtained are shown in Table 2.

○：在背面的隔離部的附近沒有光固性矽樹脂 ○: There is no photocurable resin in the vicinity of the separator on the back side.

△：在背面的隔離部的附近僅有由光固性矽樹脂引起的 著色 △: only in the vicinity of the partition on the back side, caused by photo-curable resin Coloring

×：在背面的隔離部的附近以形狀的形式明確有光固性矽樹脂 ×: The photocurable resin is clearly defined in the shape of the vicinity of the partition portion on the back surface.

(3)表面保持性的評價 (3) Evaluation of surface retention

評價所得到的除溢料用電解液組合物的表面保持性。 The surface retention of the obtained electrolyte composition for flashing was evaluated.

即，目視觀察上述的溢料除去性的評價後的光半導體裝置用模塑成型品的反射器部，沿著下述基準評價表面保持性。所得到的結果表示在表2中。 In other words, the reflector portion of the molded article for an optical semiconductor device after the evaluation of the above-described flash removal property was visually observed, and the surface retainability was evaluated along the following criteria. The results obtained are shown in Table 2.

○：與進行溢料除去前的反射器部比較，沒有差異 ○: There is no difference compared with the reflector section before the flash removal

△：與進行溢料除去前的反射器部比較，光澤略微降低 △: The gloss is slightly lowered as compared with the reflector portion before the flash is removed.

×：與進行溢料除去前的反射器部比較，明確光澤降低 ×: Clear gloss reduction as compared with the reflector portion before the flash removal

〔實施例2〕 [Example 2]

另外，在實施例2中，製備除溢料用電解液組合物時，除了將四乙基氫氧化銨(TEAH)的摻合比例改變為2重量%、將離子交換水的摻合比例改變為98重量%以外，與實施例1同樣地製備除溢料用電解液組合物，進行評價。所得到的結果表示在表1~2中。 Further, in Example 2, when the electrolyte composition for flashing was prepared, the blending ratio of tetraethylammonium hydroxide (TEAH) was changed to 2% by weight, and the blending ratio of ion-exchanged water was changed to The electrolyte solution for flashing was prepared and evaluated in the same manner as in Example 1 except for 98% by weight. The results obtained are shown in Tables 1-2.

〔實施例3〕 [Example 3]

另外，在實施例3中，製備除溢料用電解液組合物時，除了將四乙基氫氧化銨(TEAH)的摻合比例改變為5重量%、將離子交換水的摻合比例改變為95重量%以外，與實施例1同樣地製備除溢料用電解液組合物，進行評價。所得到的結果表示在表1~2中。 Further, in Example 3, when the electrolytic solution composition for flashing was prepared, the blending ratio of tetraethylammonium hydroxide (TEAH) was changed to 5% by weight, and the blending ratio of ion-exchanged water was changed to The electrolyte solution for flashing was prepared and evaluated in the same manner as in Example 1 except that the amount was 95% by weight. The results obtained are shown in Tables 1-2.

〔實施例4〕 [Example 4]

另外，在實施例4中，製備除溢料用電解液組合物時，除了將四乙基氫氧化銨(TEAH)的摻合比例改變為8重量%、將離子交換水的摻合比例改變為92重量%以外，與實施例1同樣地製備除溢料用電解液組合物，進行評價。所得到的結果表示在表1~2中。 Further, in Example 4, when the electrolyte composition for flashing was prepared, the blending ratio of tetraethylammonium hydroxide (TEAH) was changed to 8% by weight, and the blending ratio of ion-exchanged water was changed to The electrolyte solution for flashing was prepared and evaluated in the same manner as in Example 1 except that the amount was 92% by weight. The results obtained are shown in Tables 1-2.

〔實施例5〕 [Example 5]

另外，在實施例5中，製備除溢料用電解液組合物時，除了將四乙基氫氧化銨(TEAH)的摻合比例改變為12重量%、將離子交換水的摻合比例改變為88重量%以外，與實施例1同樣地製備除溢料用電解液組合物，進行評價。所得到的結果表示在表1~2中。 Further, in Example 5, in the preparation of the electrolyte composition for flashing, the blending ratio of tetraethylammonium hydroxide (TEAH) was changed to 12% by weight, and the blending ratio of ion-exchanged water was changed to The electrolyte solution for flashing was prepared and evaluated in the same manner as in Example 1 except for 88% by weight. The results obtained are shown in Tables 1-2.

〔實施例6〕 [Example 6]

另外，在實施例6中，製備除溢料用電解液組合物時，除了將四乙基氫氧化銨(TEAH)的摻合比例改變為5重量%、將離子交換水的摻合比例改變為92.5重量%，並且進一步摻合2.5重量%(相對於1離子當量的TEAH為0.97離子當量)的作為延遲劑的羥基乙酸以外，與實施例1同樣地製備除溢料用電解液組合物，進行評價。所得到的結果表示在表1~2中。 Further, in Example 6, when the electrolyte composition for flashing was prepared, the blending ratio of tetraethylammonium hydroxide (TEAH) was changed to 5% by weight, and the blending ratio of ion-exchanged water was changed to An electrolyte solution for flashing was prepared in the same manner as in Example 1 except that the glycolic acid as a retarding agent was further blended in an amount of 2.5% by weight and further 2.5% by weight (the amount of TEAH of the ion equivalent of 0.97). Evaluation. The results obtained are shown in Tables 1-2.

〔實施例7〕 [Example 7]

另外，在實施例7中，製備除溢料用電解液組合物時，除了將四乙基氫氧化銨(TEAH)的摻合比例改變為5重量%、將離子交換水的摻合比例改變為90重量%， 並且進一步摻合5重量%的作為延遲劑的3-甲氧基-3-甲基-1-丁醇(MMB)以外，與實施例1同樣地製備除溢料用電解液組合物，進行評價。所得到的結果表示在表1~2中。 Further, in Example 7, when the electrolytic solution composition for flashing was prepared, the blending ratio of tetraethylammonium hydroxide (TEAH) was changed to 5% by weight, and the blending ratio of ion-exchanged water was changed to 90% by weight, Further, in the same manner as in Example 1, except that 3-methoxy-3-methyl-1-butanol (MMB) as a retarding agent was further blended, the electrolytic solution composition for the flashing was prepared and evaluated. . The results obtained are shown in Tables 1-2.

〔實施例8〕 [Example 8]

另外，在實施例8中，製備除溢料用電解液組合物時，除了將四乙基氫氧化銨(TEAH)的摻合比例改變為4重量%、將離子交換水的摻合比例改變為95重量%，並且進一步摻合1重量%的作為其它有機鹼的四甲基氫氧化銨(TMAH)以外，與實施例1同樣地製備除溢料用電解液組合物，進行評價。所得到的結果表示在表1~2中。 Further, in Example 8, when the electrolyte composition for flashing was prepared, the blending ratio of tetraethylammonium hydroxide (TEAH) was changed to 4% by weight, and the blending ratio of ion-exchanged water was changed to An electrolyte solution composition for flashing was prepared and evaluated in the same manner as in Example 1 except that tetramethylammonium hydroxide (TMAH) as another organic base was further blended in an amount of 95% by weight. The results obtained are shown in Tables 1-2.

〔實施例9〕 [Example 9]

另外，在實施例9中，製備除溢料用電解液組合物時，除了將四乙基氫氧化銨(TEAH)的摻合比例改變為4重量%、將離子交換水的摻合比例改變為95重量%，並且進一步摻合1重量%的作為其它有機鹼的四丙基氫氧化銨(TPAH)以外，與實施例1同樣地製備除溢料用電解液組合物，進行評價。所得到的結果表示在表1~2中。 Further, in Example 9, when the electrolyte composition for flashing was prepared, the blending ratio of tetraethylammonium hydroxide (TEAH) was changed to 4% by weight, and the blending ratio of ion-exchanged water was changed to The electrolytic solution composition for the flashing was prepared and evaluated in the same manner as in Example 1 except that the amount of the tetrapropylammonium hydroxide (TPAH) which is another organic base was further blended in an amount of 95% by weight. The results obtained are shown in Tables 1-2.

〔實施例10〕 [Example 10]

另外，在實施例10中，製備除溢料用電解液組合物時，除了將四乙基氫氧化銨(TEAH)的摻合比例改變為4重量%、將離子交換水的摻合比例改變為95重量%，並且進一步摻合1重量%的作為無機鹼的氫氧化鈉(NaOH)以外，與實施例1同樣地製備除溢料用電解液組合物，進行評價。所得到的結果表示在表1~2中。 Further, in Example 10, when the electrolytic solution composition for flashing was prepared, the blending ratio of tetraethylammonium hydroxide (TEAH) was changed to 4% by weight, and the blending ratio of ion-exchanged water was changed to The electrolyte solution for flashing was prepared and evaluated in the same manner as in Example 1 except that the amount of sodium hydroxide (NaOH) as an inorganic base was further blended in an amount of 95% by weight. The results obtained are shown in Tables 1-2.

〔實施例11〕 [Example 11]

另外，在實施例11中，製備除溢料用電解液組合物時，除了將四乙基氫氧化銨(TEAH)的摻合比例改變為4重量%、將離子交換水的摻合比例改變為95重量%，並且進一步摻合1重量%的作為無機鹼的碳酸鉀(K₂CO₃)以外，與實施例1同樣地製備除溢料用電解液組合物，進行評價。所得到的結果表示在表1~2中。 Further, in Example 11, when the electrolyte composition for flashing was prepared, the blending ratio of tetraethylammonium hydroxide (TEAH) was changed to 4% by weight, and the blending ratio of ion-exchanged water was changed to The electrolyte solution for flashing was prepared and evaluated in the same manner as in Example 1 except that the amount of potassium carbonate (K ₂ CO ₃ ) as an inorganic base was further blended in an amount of 95% by weight. The results obtained are shown in Tables 1-2.

〔比較例1〕 [Comparative Example 1]

另外，在比較例1中，製備除溢料用電解液組合物時，除了將四乙基氫氧化銨(TEAH)的摻合比例改變為0.1重量%、將離子交換水的摻合比例改變為99.9重量%以外，與實施例1同樣地製備除溢料用電解液組合物，進行評價。所得到的結果表示在表1以及表3中。 Further, in Comparative Example 1, when the electrolytic solution composition for flashing was prepared, the blending ratio of tetraethylammonium hydroxide (TEAH) was changed to 0.1% by weight, and the blending ratio of ion-exchanged water was changed to The electrolyte solution for flashing was prepared and evaluated in the same manner as in Example 1 except for 99.9% by weight. The results obtained are shown in Table 1 and Table 3.

〔比較例2〕 [Comparative Example 2]

另外，在比較例2中，製備除溢料用電解液組合物時，除了將四乙基氫氧化銨(TEAH)的摻合比例改變為15重量%、將離子交換水的摻合比例改變為85重量%以外，與實施例1同樣地製備除溢料用電解液組合物，進行評價。所得到的結果表示在表1以及表3中。 Further, in Comparative Example 2, when the electrolytic solution composition for flashing was prepared, the blending ratio of tetraethylammonium hydroxide (TEAH) was changed to 15% by weight, and the blending ratio of ion-exchanged water was changed to The electrolytic solution composition for the flashing was prepared in the same manner as in Example 1 except for 85 wt%, and the evaluation was carried out. The results obtained are shown in Table 1 and Table 3.

〔比較例3〕 [Comparative Example 3]

另外，在比較例3中，製備除溢料用電解液組合物時，除了未摻合四乙基氫氧化銨(TEAH)，將離子交換水的摻合比例改變為95重量%，並且摻合5重量%的作為其它有機鹼的四甲基氫氧化銨(TMAH)以外，與實施例1 同樣地製備除溢料用電解液組合物，進行評價。所得到的結果表示在表1以及表3中。 Further, in Comparative Example 3, when the electrolyte composition for flashing was prepared, the blending ratio of ion-exchanged water was changed to 95% by weight, and blending was carried out except that tetraethylammonium hydroxide (TEAH) was not blended. 5 wt% of tetramethylammonium hydroxide (TMAH) as another organic base, and Example 1 The electrolytic solution composition for the flashing was prepared in the same manner and evaluated. The results obtained are shown in Table 1 and Table 3.

〔比較例4〕 [Comparative Example 4]

另外，在比較例4中，製備除溢料用電解液組合物時，除了未摻合四乙基氫氧化銨(TEAH)，將離子交換水的摻合比例改變為95重量%，並且摻合5重量%的作為其它有機鹼的四丙基氫氧化銨(TPAH)以外，與實施例1同樣地製備除溢料用電解液組合物，進行評價。所得到的結果表示在表1以及表3中。 Further, in Comparative Example 4, when the electrolyte composition for flashing was prepared, the blending ratio of ion-exchanged water was changed to 95% by weight, and blending was carried out except that tetraethylammonium hydroxide (TEAH) was not blended. An electrolyte solution composition for flashing was prepared and evaluated in the same manner as in Example 1 except that 5% by weight of tetrapropylammonium hydroxide (TPAH) as another organic base was used. The results obtained are shown in Table 1 and Table 3.

〔比較例5〕 [Comparative Example 5]

另外，在比較例5中，製備除溢料用電解液組合物時，除了未摻合四乙基氫氧化銨(TEAH)，將離子交換水的摻合比例改變為95重量%，並且摻合5重量%的作為其它無機鹼的氫氧化鈉(NaOH)以外，與實施例1同樣地製備除溢料用電解液組合物，進行評價。所得到的結果表示在表1以及表3中。 Further, in Comparative Example 5, when the electrolytic solution composition for flashing was prepared, the blending ratio of ion-exchanged water was changed to 95% by weight, and blended, except that tetraethylammonium hydroxide (TEAH) was not blended. The electrolyte solution for flashing was prepared and evaluated in the same manner as in Example 1 except that 5% by weight of sodium hydroxide (NaOH) as another inorganic base was used. The results obtained are shown in Table 1 and Table 3.

〔比較例6〕 [Comparative Example 6]

另外，在比較例6中，製備除溢料用電解液組合物時，除了未摻合四乙基氫氧化銨(TEAH)，將離子交換水的摻合比例改變為95重量%，並且摻合5重量%的作為其它無機鹼的碳酸鉀(K₂CO₃)以外，與實施例1同樣地製備除溢料用電解液組合物，進行評價。所得到的結果表示在表1以及表3中。 Further, in Comparative Example 6, when the electrolyte composition for flashing was prepared, the blending ratio of ion-exchanged water was changed to 95% by weight, and blending was carried out except that tetraethylammonium hydroxide (TEAH) was not blended. The electrolyte solution for flashing was prepared and evaluated in the same manner as in Example 1 except that 5% by weight of potassium carbonate (K ₂ CO ₃ ) as another inorganic base was used. The results obtained are shown in Table 1 and Table 3.

〔比較例7〕 [Comparative Example 7]

另外，在比較例7中，製備除溢料用電解液組合物時，除了未摻合四乙基氫氧化銨(TEAH)，將離子交換水的摻合比例改變為90重量%，並且摻合作為無機鹼的4重量%的過錳酸鉀(KMnO₄)、和6重量%的氫氧化鉀(KOH)以外，與實施例1同樣地製備除溢料用電解液組合物，進行評價。所得到的結果表示在表1以及表3中。 Further, in Comparative Example 7, when the electrolyte composition for flashing was prepared, the blending ratio of the ion-exchanged water was changed to 90% by weight, except for the undoped tetraethylammonium hydroxide (TEAH), and the blending was carried out. An electrolyte solution composition for flashing was prepared and evaluated in the same manner as in Example 1 except that 4% by weight of potassium permanganate (KMnO ₄ ) and 6% by weight of potassium hydroxide (KOH) were used as the inorganic base. The results obtained are shown in Table 1 and Table 3.

此外，在比較例7中，評價溢料除去性時，在電解處理後，導電部件的表面由於氧化而顯著變黑。 Further, in Comparative Example 7, when the flash removal property was evaluated, the surface of the conductive member was remarkably blackened by oxidation after the electrolytic treatment.

〔比較例8〕 [Comparative Example 8]

另外，在比較例8中，製備除溢料用電解液組合物時，除了未摻合四乙基氫氧化銨(TEAH)以及離子交換水，摻合作為季銨鹽的四甲基氯化銨(TMAC)1重量%、作為無機鹼的氫氧化鈉(NaOH)4重量%、作為有機溶劑的N-甲基-2-吡咯烷酮(NMP)79重量%、甲醇(MtOH)16重量%以外，與實施例1同樣地製備除溢料用電解液組合物，進行評價。所得到的結果表示在表1以及表3中。 Further, in Comparative Example 8, when the electrolyte composition for flashing was prepared, in addition to tetraethylammonium hydroxide (TEAH) and ion-exchanged water, tetramethylammonium chloride which was a quaternary ammonium salt was blended. (TMAC) 1% by weight, 4% by weight of sodium hydroxide (NaOH) as an inorganic base, 79% by weight of N-methyl-2-pyrrolidone (NMP) as an organic solvent, and 16% by weight of methanol (MtOH) In the same manner as in Example 1, an electrolyte solution for flashing was prepared and evaluated. The results obtained are shown in Table 1 and Table 3.

此外，在比較例8中，評價溢料除去性時，在電解處理後，即使提高施加電壓至10V，也未達到規定的陰極電流密度，因此，不能評價溢料除去性以及之後的氣密保持性以及表面保持性。 Further, in Comparative Example 8, when the flash removal property was evaluated, even after the electrolytic treatment was performed, even if the applied voltage was raised to 10 V, the predetermined cathode current density was not obtained. Therefore, the flash removal property and the subsequent airtight retention could not be evaluated. Sexuality and surface retention.

〔參考例1~5〕 [Reference Examples 1 to 5]

另外，在參考例1~5中，使光半導體裝置用模塑成型品浸漬於實施例1~5中製備的除溢料用電解液組合物(液溫75℃)，不通電放置3秒、30秒、600秒後，與 實施例1同樣地進行溢料除去性、氣密保持性以及表面保持性的評價。所得到的结果表示在表4中。 In addition, in the reference examples 1 to 5, the molded article for an optical semiconductor device was immersed in the electrolyte solution for flash cleaning prepared in Examples 1 to 5 (liquid temperature: 75 ° C), and was left unenergized for 3 seconds. After 30 seconds, 600 seconds, with In the same manner as in Example 1, the evaluation of the flash removal property, the airtightness retention property, and the surface retention property were performed. The results obtained are shown in Table 4.

工業實用性 Industrial applicability

根據本發明的除溢料用電解液組合物以及使用了該除溢料用電解液組合物的溢料的除去方法，除去模塑成型品的導電部件表面產生的溢料時，通過將模塑成型品浸漬在以規定比例摻合四乙基氫氧化銨和水而成的電解液組合物中，並通電，不會對除溢料以外的樹脂成型部造成損傷，而且能夠在例如1秒的非常短的通電時間內有效除去溢料。 According to the method for removing the flashing electrolyte composition of the present invention and the method for removing the flash using the electrolyte composition for the flashing material, when the flash generated on the surface of the conductive member of the molded article is removed, the molding is performed by molding The molded article is immersed in an electrolyte composition obtained by blending tetraethylammonium hydroxide and water at a predetermined ratio, and is energized, so as not to damage the resin molded portion other than the flash, and can be, for example, 1 second. The flash is effectively removed during a very short power-on time.

其結果，即使以光半導體裝置用模塑成型品為物件物時，也能夠防止隔離部從導電部件剝離，有效保持氣密性，且能夠在非常短的通電時間內有效除去溢料。 As a result, even when the molded article for an optical semiconductor device is used as an object, it is possible to prevent the separator from being peeled off from the conductive member, to effectively maintain airtightness, and to effectively remove the flash in a very short energization time.

因此，本發明的除溢料用電解液組合物以及使用了該除溢料用電解液組合物的溢料的除去方法，被期待對模塑成型品、特別是光半導體裝置用模塑成型品的高品質化以及製造效率的提高有顯著幫助。 Therefore, the electrolytic solution composition for removing the flash material of the present invention and the method for removing the flash material using the electrolytic solution composition for the cleaning liquid are expected to be molded articles for molded articles, particularly optical semiconductor devices. The high quality and the improvement of manufacturing efficiency have significantly helped.

100‧‧‧光半導體裝置用模塑成型品 100‧‧‧Molded products for optical semiconductor devices

102a‧‧‧隔離部 102a‧‧‧Isolation Department

102b‧‧‧反射器部 102b‧‧‧Reflector

104a‧‧‧導電部件 104a‧‧‧Electrical parts

104b‧‧‧導電部件 104b‧‧‧Electrical parts

106‧‧‧空腔 106‧‧‧ Cavity

Claims (8)

一種除溢料用電解液組合物，其用於對模塑成型品通電，並除去在將由金屬薄板形成的導電部件與絕緣性樹脂模塑成型為一體時，產生在所得到的模塑成型品的所述導電部件的表面上的由所述絕緣性樹脂形成的溢料，其特徵在於：含有四乙基氫氧化銨和水；以及相對於100重量%的所述除溢料用電解液組合物的總量，所述四乙基氫氧化銨的摻合比例為0.2~14重量%的範圍內的值，所述水的摻合比例為86~99.8重量%的範圍內的值。 An electrolyte composition for removing impurities, which is used for energizing a molded article and removing the molded article obtained by molding a conductive member formed of a thin metal plate and an insulating resin into one body. The flash formed of the insulating resin on the surface of the conductive member is characterized by containing tetraethylammonium hydroxide and water; and combining with 100% by weight of the electrolyte for the flashing material The blending ratio of the tetraethylammonium hydroxide is a value in the range of 0.2 to 14% by weight, and the blending ratio of the water is a value in the range of 86 to 99.8% by weight. 如申請專利範圍第1項所述之除溢料用電解液組合物，其特徵在於，相對於1離子當量的所述四乙基氫氧化銨，以0.1~2離子當量的範圍內的值含有選自由羥基乙酸、甲酸、以及乙酸所組成的群組中的至少一種。 The electrolyte composition for removing impurities according to the first aspect of the invention, characterized in that the tetraethylammonium hydroxide is contained in a range of 0.1 to 2 ion equivalents per 1 equivalent of the ion equivalent. At least one selected from the group consisting of glycolic acid, formic acid, and acetic acid is selected. 如申請專利範圍第1項所述之除溢料用電解液組合物，其特徵在於，相對於100重量%的所述除溢料用電解液組合物的總量，以0.5~10重量%的範圍內的值含有選自由3-甲氧基-3-甲基-1-丁醇、3-甲氧基丁醇、乙二醇單丙基醚、乙二醇單異丙基醚、乙二醇單丁基醚、二乙二醇單甲基醚、二乙二醇單乙基醚、二丙二醇單甲基醚、二乙二醇二甲基醚以及二乙二醇二乙基醚所組成的群組中的至少一種。 The electrolyte composition for removing impurities according to the first aspect of the invention, characterized in that the total amount of the electrolyte composition for the cleaning liquid is 0.5 to 10% by weight based on 100% by weight of the total amount of the electrolyte composition for the cleaning liquid. The range of values contains a selected from the group consisting of 3-methoxy-3-methyl-1-butanol, 3-methoxybutanol, ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, and ethylene Composition of alcohol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, diethylene glycol dimethyl ether and diethylene glycol diethyl ether At least one of the groups. 如申請專利範圍第1項所述之除溢料用電解液組合 物，其特徵在於，pH為3~14的範圍內的值。 The electrolyte solution for removing impurities according to item 1 of the patent application scope The substance is characterized by a pH in the range of 3 to 14. 如申請專利範圍第1項所述之除溢料用電解液組合物，其特徵在於，構成所述模塑成型品的所述絕緣性樹脂為熱固性環氧系樹脂。 The electrolyte solution for removing impurities according to the first aspect of the invention, wherein the insulating resin constituting the molded article is a thermosetting epoxy resin. 如申請專利範圍第1項所述之除溢料用電解液組合物，其特徵在於，所述模塑成型品為光半導體裝置用模塑成型品。 The electrolyte composition for a flashover according to the first aspect of the invention, wherein the molded article is a molded article for an optical semiconductor device. 一種溢料的除去方法，其用於除去在將由金屬薄板形成的導電部件與絕緣性樹脂模塑成型為一體時，產生在所得到的模塑成型品的所述導電部件的表面上的由所述絕緣性樹脂形成的溢料，其特徵在於，包括下述步驟(A)~(C)：(A)將所述模塑成型品浸漬在除溢料用電解液組合物中的步驟，其中所述除溢料用電解液組合物含有四乙基氫氧化銨和水，並且相對於100重量%的所述除溢料用電解液組合物的總量，所述四乙基氫氧化銨的摻合比例為0.2~14重量%的範圍內的值，所述水的摻合比例為86~99.8重量%的範圍內的值；(B)以所述模塑成型品中的所述導電部件為陰極，以對電極為陽極進行通電的電解處理步驟；(C)通過對所述模塑成型品實施物理處理而除去溢料的步驟。 A method for removing flash material for removing a surface on a surface of the conductive member of the obtained molded article when the conductive member formed of the thin metal plate is molded integrally with the insulating resin The flash formed of the insulating resin is characterized by comprising the following steps (A) to (C): (A) a step of immersing the molded article in an electrolyte solution for flashing, wherein The electrolyte composition for flashing contains tetraethylammonium hydroxide and water, and the tetraethylammonium hydroxide is relative to 100% by weight of the total amount of the electrolyte composition for the flashover. The blending ratio is a value in the range of 0.2 to 14% by weight, the blending ratio of the water is a value in the range of 86 to 99.8% by weight; and (B) the conductive member in the molded article An electrolysis treatment step of energizing the cathode with the counter electrode as the anode; (C) a step of removing the flash by subjecting the molded article to physical treatment. 如申請專利範圍第7項所述之溢料的除去方法，其特徵在於，在所述步驟(B)中，陰極的電流密度為0.5~ 5A/dm²的範圍內的值，並且通電時間為0.5~5秒的範圍內的值。 The method for removing flash as described in claim 7 is characterized in that, in the step (B), the current density of the cathode is a value in the range of 0.5 to 5 A/dm ² , and the energization time is A value in the range of 0.5 to 5 seconds.