TWI658766B - Corrosion-resistant electronic substrate and coating composition used therefor - Google Patents
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Abstract
本發明提供一種遮擋硫化氫氣體等腐蝕性氣體而提高了耐蝕性的耐蝕性電子基板、以及用於形成該耐蝕性電子基板的塗敷層的腐蝕性氣體遮擋用塗敷組成物。一種耐蝕性電子基板,其是於構建電子零件後的基板本體的表面整體或一部分形成第一塗敷層之後,形成第二塗敷層,並藉由所述塗敷層將該電子零件的包含電極的導電性金屬部分被覆而成,所述第一塗敷層的硬化後的DMA的-20℃~0℃、10 Hz下的tanδ為0.10以上,且所述第二塗敷層於硬化後的藉由正電子壽命消滅法所得的自由體積半徑的測定值的分佈中,0.32 nm以下(不包含0)的分佈面積設為70%以上。The present invention provides a corrosion-resistant electronic substrate having improved corrosion resistance by shielding corrosive gases such as hydrogen sulfide gas, and a coating composition for corrosive gas shielding for forming a coating layer of the corrosion-resistant electronic substrate. A corrosion-resistant electronic substrate is formed by forming a first coating layer on the whole or a part of a surface of a substrate body after constructing an electronic component, and then forming a second coating layer, and including the electronic component by the coating layer. The conductive metal part of the electrode is coated. The DMA after curing of the first coating layer at -20 ° C to 0 ° C and tanδ at 10 Hz is 0.10 or more, and the second coating layer is cured after hardening. In the distribution of the measured value of the free volume radius obtained by the positron lifetime extinction method, the distribution area of 0.32 nm or less (excluding 0) is set to 70% or more.
Description
本發明是有關於一種將塗敷組成物塗敷於基板本體而提高了耐蝕性的電子基板、以及用於所述電子基板的塗敷組成物。The present invention relates to an electronic substrate in which a coating composition is applied to a substrate body to improve corrosion resistance, and a coating composition for the electronic substrate.
近年來,電源、溫度調節器、定時器及可程式邏輯控制器(Programmable Logic Controller,PLC)等中所使用的電子基板於要求防止結露或耐腐蝕性氣體性等耐環境性能的環境中使用的情形增加。因此,為了獲得此種耐環境性能,於電子基板中的基板本體的表面藉由可遮擋水蒸氣或腐蝕性氣體的塗敷組成物形成塗敷層,藉此可實現耐環境性能的提升。In recent years, electronic substrates used in power supplies, temperature regulators, timers, and programmable logic controllers (PLCs) have been used in environments that require environmental resistance such as condensation prevention and corrosion-resistant gas resistance. The situation has increased. Therefore, in order to obtain such environmental resistance, a coating layer is formed on the surface of the substrate body in the electronic substrate by a coating composition that can block water vapor or corrosive gas, thereby improving the environmental resistance.
以往,作為此種塗敷層,已知於撓性基板上進行交替包含有機層及阻擋(barrier)層的多層阻擋塗敷。該多層阻擋層可防止液體·氣體的浸入,並且柔軟,可防止龜裂(crack)等的產生。Conventionally, as such a coating layer, a multilayer barrier coating including an organic layer and a barrier layer alternately on a flexible substrate has been known. This multilayer barrier layer prevents the intrusion of liquids and gases, and is soft and prevents the occurrence of cracks and the like.
作為該多層阻擋塗敷的實現方法,藉由蒸鍍將無機材料形成為50 Å~500 Å的厚度,從而形成阻擋層。有機層為可聚合的交聯性單體,藉由蒸鍍將其形成為0.1 μm~1.0 μm。另外,為了提升有機層與阻擋層的層間的密著性,於藉由蒸鍍堆積有機層之前,對無基層的表面進行電漿處理。As a method for realizing the multilayer barrier coating, an inorganic material is formed to a thickness of 50 Å to 500 Å by evaporation to form a barrier layer. The organic layer is a polymerizable crosslinkable monomer, and is formed to a thickness of 0.1 μm to 1.0 μm by evaporation. In addition, in order to improve the adhesion between the organic layer and the barrier layer, the surface of the non-base layer is subjected to a plasma treatment before the organic layer is deposited by evaporation.
此種多層阻擋塗敷可實現結構性的應力緩和,且可改善耐龜裂性、撓性(flexibility)(例如,參照專利文獻1)。 [現有技術文獻] [專利文獻]Such a multilayer barrier coating can achieve structural stress relaxation, and can improve crack resistance and flexibility (for example, refer to Patent Document 1). [Prior Art Literature] [Patent Literature]
[專利文獻1]日本專利特表2005-528250號公報[Patent Document 1] Japanese Patent Publication No. 2005-528250
[發明所欲解決之課題] 但是,所述先前的多層阻擋塗敷由於對搭載有多個電子零件的電子基板蒸鍍有機層或阻擋層,因此擔心有可能對電子零件造成損傷。[Problems to be Solved by the Invention] However, since the above-mentioned multilayer barrier coating has an organic layer or a barrier layer deposited on an electronic substrate on which a plurality of electronic components are mounted, there is a concern that the electronic components may be damaged.
另外,藉由在焊接時使用焊劑(flux)而產生焊劑殘渣,因此,當有機層或阻擋層被塗敷於產生了該焊劑殘渣的電子基板上之類的情況下,若反覆對電子基板施加溫熱衝擊或冷熱衝擊,則產生以所述焊劑殘渣為起點的龜裂,由該龜裂引起的應力亦傳播於該些有機層或阻擋層,藉此多層阻擋層受到破裂等損傷。該情況下,氣體成分或液體成分沿著所述有機層或阻擋層的裂紋浸入裂紋內部,從而腐蝕電子基板,並誘發導通不良或短路等不良現象。該情況即使增加有機層與阻擋層的重疊亦不會改善。In addition, flux residues are generated by using a flux during soldering. Therefore, when an organic layer or a barrier layer is applied to an electronic substrate on which the flux residues are generated, the electronic substrates are repeatedly applied. Warm heat shock or cold heat shock generates cracks starting from the flux residue, and the stress caused by the cracks is also propagated to the organic layers or barrier layers, whereby the multilayer barrier layer is damaged by cracks and the like. In this case, a gas component or a liquid component immerses into the crack along the crack of the organic layer or the barrier layer, thereby corroding the electronic substrate, and causing defects such as poor conduction or short circuit. This situation does not improve even if the overlap of the organic layer and the barrier layer is increased.
本發明是鑒於所述實際狀況而成者,目的在於提供一種即使於腐蝕性氣體環境、或者反覆施加溫熱衝擊或冷熱衝擊的環境下,亦可遮擋腐蝕性氣體而提高耐蝕性的耐蝕性電子基板、以及用於形成該耐蝕性電子基板的塗敷層的塗敷組成物。The present invention has been made in view of the above-mentioned actual situation, and an object thereof is to provide a corrosion-resistant electron that can shield a corrosive gas and improve the corrosion resistance even in a corrosive gas environment or an environment where warm or cold shock is repeatedly applied A coating composition for a substrate and a coating layer for forming the corrosion-resistant electronic substrate.
[解決課題之手段] 用於解決所述課題的本發明的耐蝕性電子基板為如下電子基板,即,其是於構建電子零件後的基板本體的表面整體或一部分形成第一塗敷層之後,形成第二塗敷層,並藉由所述第一塗敷層以及所述第二塗敷層將該電子零件的包含電極的導電性金屬部分被覆而成,所述第一塗敷層的硬化後的動態機械分析儀(dynamic mechanical analyzer,DMA)的-20℃~0℃、10 Hz下的tanδ為0.10以上,且所述第二塗敷層於硬化後的藉由正電子壽命消滅法所得的自由體積半徑的測定值的分佈中,0.32 nm以下(不包含0)的分佈面積設為70%以上。[Means for Solving the Problem] The corrosion-resistant electronic substrate of the present invention for solving the above-mentioned problems is an electronic substrate that is formed after the first coating layer is formed on the whole or a part of the surface of the substrate body after the electronic components are constructed, A second coating layer is formed, and the conductive metal part including the electrode of the electronic component is covered with the first coating layer and the second coating layer, and the first coating layer is hardened. The dynamic mechanical analyzer (DMA) after the tan δ at -20 ° C to 0 ° C and 10 Hz is 0.10 or more, and the second coating layer is obtained by a positron lifetime extinction method after hardening. In the distribution of the measured value of the free volume radius, the distribution area of 0.32 nm or less (excluding 0) is set to 70% or more.
於所述耐蝕性電子基板中,亦可為,所述第一塗敷層與所述第二塗敷層經由其界面而為一體。In the corrosion-resistant electronic substrate, the first coating layer and the second coating layer may be integrated through an interface thereof.
於所述耐蝕性電子基板中,亦可為,所述第一塗敷層為選自苯乙烯系橡膠、胺基甲酸酯系橡膠、矽酮系橡膠、氟系橡膠、烯烴系彈性體、苯乙烯系彈性體、氟系彈性體中的任一種以上。In the corrosion-resistant electronic substrate, the first coating layer may be selected from the group consisting of styrene-based rubber, urethane-based rubber, silicone-based rubber, fluorine-based rubber, olefin-based elastomer, Any one or more of a styrene-based elastomer and a fluorine-based elastomer.
於所述耐蝕性電子基板中,亦可為,所述第二塗敷層為選自丙烯酸樹脂、聚酯樹脂、聚胺基甲酸酯樹脂、矽酮樹脂、氟樹脂及環氧樹脂中的一種以上。In the corrosion-resistant electronic substrate, the second coating layer may be selected from acrylic resin, polyester resin, polyurethane resin, silicone resin, fluororesin, and epoxy resin. More than one.
於所述耐蝕性電子基板中,亦可為,所述第一塗敷層的厚度為10 μm~500 μm,第二塗敷層的厚度為5 μm~200 μm。In the corrosion-resistant electronic substrate, the thickness of the first coating layer may be 10 μm to 500 μm, and the thickness of the second coating layer may be 5 μm to 200 μm.
用於解決所述課題的本發明的塗敷組成物為用於形成所述耐蝕性電子基板中的所述第一塗敷層的塗敷組成物,且所述塗敷組成物包含:所述第一塗敷層的硬化後的DMA的-20℃~0℃、10 Hz下的tanδ成為0.10以上的樹脂組成物,及其溶劑。The coating composition of the present invention for solving the problem is a coating composition for forming the first coating layer in the corrosion-resistant electronic substrate, and the coating composition includes: The resin composition containing tan δ at −20 ° C. to 0 ° C. and 10 Hz of the cured DMA of the first coating layer is 0.10 or more, and a solvent thereof.
用於解決所述課題的本發明的塗敷組成物為用於形成所述耐蝕性電子基板中的所述第二塗敷層的塗敷組成物,且所述塗敷組成物包含:所述第二塗敷層的硬化後的藉由正電子壽命消滅法所得的自由體積半徑的測定值的分佈中0.32 nm以下(不包含0)的分佈面積成為70%以上的樹脂組成物,及其溶劑。The coating composition of the present invention for solving the problem is a coating composition for forming the second coating layer in the corrosion-resistant electronic substrate, and the coating composition includes: Resin composition having a distribution area of 0.32 nm or less (excluding 0) in the distribution of the measured value of the free volume radius obtained by the positron lifetime extinction method after hardening of the second coating layer is 70% or more, and a solvent thereof .
[發明的效果] 如上所述,根據本發明,於構建電子零件後的基板本體的表面整體或一部分形成硬化後的DMA的-20℃~0℃、10 Hz下的tanδ為0.10以上的第一塗敷層之後,形成在硬化後的藉由正電子壽命消滅法所得的自由體積半徑的測定值的分佈中0.32 nm以下(不包含0)的分佈面積成為70%以上的第二塗敷層,並藉由所述第一塗敷層及第二塗敷層將該電子零件的包含電極的導電性金屬部分被覆,藉此,可遮擋腐蝕性氣體並防止電極及導電性金屬部分的腐蝕。另外,由於形成有硬化後的DMA的-20℃~0℃、10 Hz下的tanδ為0.10以上的第一塗敷層,因此,即使於施加反覆的溫熱衝擊或冷熱衝擊的環境下,亦可防止電子基板表面的焊劑殘渣的破裂、或者由該破裂引起的裂紋朝塗敷層的傳播,從而防止電子基板的腐蝕。[Effects of the Invention] As described above, according to the present invention, the entire or a part of the surface of the substrate body after the electronic component is constructed forms a hardened DMA with a tan δ at -20 ° C to 0 ° C and 10 Hz of 0.10 or more. After the coating layer, a second coating layer having a distribution area of 0.32 nm or less (excluding 0) in the distribution of the measured value of the free volume radius obtained by the positron lifetime extinction method after hardening becomes 70% or more, The conductive metal part including the electrode of the electronic component is covered with the first coating layer and the second coating layer, thereby shielding corrosive gas and preventing corrosion of the electrode and the conductive metal part. In addition, since the first coating layer having a tan δ at -20 ° C to 0 ° C and 10 Hz of 0.10 or more at a temperature of 0.10 or more is formed in the cured DMA, even in an environment where repeated warm and cold shocks are applied, It is possible to prevent cracking of the solder residue on the surface of the electronic substrate, or propagation of cracks caused by the cracking toward the coating layer, and prevent corrosion of the electronic substrate.
以下,參照圖式對本發明的實施形態進行說明。Hereinafter, embodiments of the present invention will be described with reference to the drawings.
圖1(a)~圖1(c)及圖2(a)、圖2(b)表示耐蝕性電子基板1的整體構成的概略,圖3表示所述耐蝕性電子基板1中的第二塗敷層5的物性,圖4表示所述耐蝕性電子基板1中的第二塗敷層5的主要部分。FIGS. 1 (a) to 1 (c) and FIGS. 2 (a) and 2 (b) show the outline of the overall configuration of the corrosion-resistant electronic substrate 1, and FIG. 3 shows a second coating in the corrosion-resistant electronic substrate 1. The physical properties of the cladding layer 5. FIG. 4 shows the main part of the second coating layer 5 in the corrosion-resistant electronic substrate 1.
耐蝕性電子基板1為於構建電子零件2後的基板本體3的表面整體或一部分形成第一塗敷層4之後,形成第二塗敷層5,並藉由所述第一塗敷層4以及所述第二塗敷層5將該電子零件2的包含電極21的導電性金屬部分20被覆而成者,所述第一塗敷層4的硬化後的DMA的-20℃~0℃、10 Hz下的tanδ為0.10以上,且所述第二塗敷層5於硬化後的藉由正電子壽命消滅法所得的自由體積半徑的測定值的分佈中,0.32 nm以下(不包含0)的分佈面積設為70%以上。The corrosion-resistant electronic substrate 1 is formed by forming a first coating layer 4 on the whole or a part of the surface of the substrate body 3 after the electronic component 2 is constructed, and then forming a second coating layer 5 through the first coating layer 4 and The second coating layer 5 covers the conductive metal part 20 including the electrode 21 of the electronic component 2. The hardened DMA of the first coating layer 4 is -20 ° C to 0 ° C, 10 ° C. The tanδ at Hz is 0.10 or more, and the distribution of the measured value of the free volume radius obtained by the positron lifetime extinction method after hardening of the second coating layer 5 is 0.32 nm or less (excluding 0). The area is set to 70% or more.
作為電子零件2,只要為構建於耐蝕性電子基板1的公知者,則並無特別限定,例如,可列舉:積體電路(Integrated Circuit,IC)、大型積體(Large-Scale Integration,LSI)等半導體元件、電阻、電容器(condenser)、電感器等。The electronic component 2 is not particularly limited as long as it is a known one constructed on the corrosion-resistant electronic substrate 1. For example, it may be an integrated circuit (IC) or a large-scale integration (LSI). Such as semiconductor components, resistors, capacitors, inductors, etc.
作為基板本體3,只要為用於耐蝕性電子基板1的公知者,則並無特別限定,例如,可列舉:矽酮基板、玻璃基板、陶瓷基板、樹脂基板、薄膜基板等。為了將電子零件2配置並構建於基板本體3,可藉由如下方式進行,即,藉由焊接等利用焊料22將各電子零件2的電極21的部分電性連接至形成於基板本體3的電路圖案的導電性金屬部分20。該連接方法並無特別限定,可使用該技術領域中公知的方法。The substrate body 3 is not particularly limited as long as it is a known one used for the corrosion-resistant electronic substrate 1, and examples thereof include a silicone substrate, a glass substrate, a ceramic substrate, a resin substrate, and a thin film substrate. In order to arrange and construct the electronic component 2 on the substrate body 3, it can be performed by electrically connecting a part of the electrode 21 of each electronic component 2 to a circuit formed on the substrate body 3 with solder 22 by soldering or the like. Patterned conductive metal portion 20. This connection method is not particularly limited, and a method known in the technical field can be used.
第一塗敷層4於將電子零件2構建於所述基板本體3之後,以被覆該電子零件2的包含電極21的基板本體3的導電性金屬部分20的方式設置於基板本體3的表面整體。或者,第一塗敷層4以被覆所述電子零件2的包含電極21的基板本體3的導電性金屬部分20的方式設置於基板本體3的一部分。因此,如圖2(a)所示,當導電性金屬部分20處於基板本體3的構建電子零件2的上表面側,並自該上表面側進行焊接之類的情況下,將第一塗敷層4設置於該上表面側。另外,如圖2(b)所示,當使電子零件2的電極21自構建該電子零件2的基板本體3的上表面側貫通至下表面側,並對該下表面側藉由流焊(Flow Soldering)進行焊接之類的情況下,將第一塗敷層4設置於該下表面側。雖然使電子零件2的電極21貫通,但電極21亦多少於基板本體3的上表面側露出,因此,該第一塗敷層4亦可設置於基板本體3的兩面側。The first coating layer 4 is provided on the entire surface of the substrate body 3 after the electronic component 2 is constructed on the substrate body 3 so as to cover the conductive metal portion 20 of the substrate body 3 including the electrodes 21 of the electronic component 2. . Alternatively, the first coating layer 4 is provided on a part of the substrate body 3 so as to cover the conductive metal portion 20 of the substrate body 3 including the electrodes 21 of the electronic component 2. Therefore, as shown in FIG. 2 (a), when the conductive metal portion 20 is located on the upper surface side of the electronic component 2 on which the substrate body 3 is constructed and soldered from the upper surface side or the like, the first coating is applied The layer 4 is provided on the upper surface side. In addition, as shown in FIG. 2 (b), when the electrode 21 of the electronic component 2 is passed from the upper surface side to the lower surface side of the substrate body 3 constituting the electronic component 2, the lower surface side is flow-welded ( In the case of welding or the like, the first coating layer 4 is provided on the lower surface side. Although the electrode 21 of the electronic component 2 is penetrated, the electrode 21 is exposed to some extent on the upper surface side of the substrate body 3. Therefore, the first coating layer 4 may be provided on both sides of the substrate body 3.
該第一塗敷層4可使用如下塗敷組成物,即,包含:硬化後的DMA的-20℃~0℃、10 Hz下的tanδ設為0.10以上的樹脂組成物,及其溶劑。The first coating layer 4 may be a coating composition containing a resin composition containing DMA at -20 ° C. to 0 ° C. and a tan δ at 10 Hz of 0.10 or more, and a solvent thereof.
作為硬化後的DMA的-20℃~0℃、10 Hz下的tanδ設為0.10以上的樹脂組成物,為苯乙烯·丙烯腈橡膠、苯乙烯·丁二烯橡膠、乙烯·丙烯橡膠、腈橡膠、丁基橡膠、丁二烯橡膠、氯丁二烯橡膠、丙烯酸橡膠、胺基甲酸酯系橡膠、矽酮系橡膠、氟系橡膠、烯烴系彈性體、苯乙烯系彈性體、聚酯系彈性體、胺基甲酸酯系彈性體、氯乙烯系彈性體、氟系彈性體、矽酮樹脂、矽酮改質環氧樹脂、矽酮改質丙烯酸樹脂,可列舉將該些溶解於甲基乙基酮(methyl ethyl ketone,MEK)或乙醇、異丙醇(isopropyl alcohol,IPA)等醇類等溶劑中而成者。只要滿足硬化後的藉由DMA測量的tanδ的要件,則該些樹脂組成物亦可使用一種或者組合使用多種。The resin composition with tan δ at -20 ° C to 0 ° C and 10 Hz of 0.10 or more as the cured DMA is styrene · acrylonitrile rubber, styrene · butadiene rubber, ethylene · propylene rubber, and nitrile rubber , Butyl rubber, butadiene rubber, chloroprene rubber, acrylic rubber, urethane rubber, silicone rubber, fluorine rubber, olefin elastomer, styrene elastomer, polyester Elastomers, urethane-based elastomers, vinyl chloride-based elastomers, fluorine-based elastomers, silicone resins, silicone-modified epoxy resins, and silicone-modified acrylic resins. It is made from solvents such as methyl ethyl ketone (MEK) or alcohols such as ethanol and isopropyl alcohol (IPA). As long as the requirements for tan δ measured by DMA after curing are satisfied, these resin compositions may be used alone or in combination.
於第一塗敷組成物中,除所述成分以外,亦可含有該技術領域中公知的顏料、染料、阻燃劑、黏度調整劑、抗氧化劑、填料等各種添加劑。關於所述添加劑的含量,只要為不阻礙本發明的效果的範圍內,則並無特別限定,可適當調整來使用。The first coating composition may contain various additives such as pigments, dyes, flame retardants, viscosity modifiers, antioxidants, and fillers, which are well known in the technical field, in addition to the components. The content of the additive is not particularly limited as long as it is within a range that does not inhibit the effects of the present invention, and can be appropriately adjusted for use.
藉由將如所述般構成的第一塗敷組成物塗佈於構建電子零件2後的基板本體3的表面整體或一部分,可將第一塗敷層4形成於該表面整體或一部分。By applying the first coating composition configured as described above to the entire or a part of the surface of the substrate body 3 after the electronic component 2 is constructed, the first coating layer 4 can be formed on the entire or a part of the surface.
於圖1(a)~圖1(c)所示的實施例中,示出了噴霧塗裝的例子,但此時,塗佈第一塗敷組成物的方法並無特別限定,可使用該技術領域中公知的方法。作為塗佈方法的具體例,可列舉:刷毛塗佈、刷塗、輥塗、噴霧塗佈、浸漬、滴注等。該些方法亦可單獨或者組合兩種以上的方法來進行。Although the example shown in FIG.1 (a)-FIG.1 (c) shows the example of spray coating, the method of apply | coating a 1st coating composition at this time is not specifically limited, You may use this Methods well known in the art. Specific examples of the coating method include bristle coating, brush coating, roll coating, spray coating, dipping, dripping, and the like. These methods may be performed alone or in combination of two or more methods.
第一塗敷層4可藉由將第一塗敷組成物塗佈後加以乾燥硬化而形成。此時,作為乾燥硬化方法,只要對應於所使用的第一塗敷組成物的種類適當決定即可。作為硬化方法的具體例,可列舉:室溫乾燥硬化、加熱硬化。The first coating layer 4 can be formed by applying a first coating composition and drying and hardening it. In this case, as the drying and curing method, it may be determined as appropriate in accordance with the type of the first coating composition to be used. Specific examples of the curing method include dry curing at room temperature and heat curing.
第一塗敷層4的厚度為10 μm~500 μm,較佳為20 μm~200 μm。若低於10 μm,則第一塗敷層4的應力緩和性缺乏,且難以吸收因焊劑殘渣23的龜裂而發生的應力傳播。另外,若超過500 μm,則由於塗敷層厚,溶劑因乾燥硬化而難以脫離,或者,因加熱效果而局部難以·容易硬化等,從而容易發生硬化不均。The thickness of the first coating layer 4 is 10 μm to 500 μm, and preferably 20 μm to 200 μm. If it is less than 10 μm, the stress relaxation property of the first coating layer 4 is insufficient, and it is difficult to absorb stress propagation caused by cracks in the flux residue 23. In addition, if it exceeds 500 μm, the thickness of the coating layer makes it difficult for the solvent to detach due to drying and hardening, or it is difficult or difficult to harden locally due to the heating effect, thereby causing uneven hardening.
關於如所述般於構建電子零件2後的基板本體3的表面整體或一部分形成有第一塗敷層4的電子基板1,藉由硬化後的狀態下的DMA的-20℃~0℃、10 Hz的tanδ成為0.10以上的第一塗敷層4,即使在施加有反覆的溫熱衝擊或冷熱衝擊的環境下焊料22的焊劑殘渣23產生龜裂,亦可吸收源於所述龜裂的應力傳播。其結果為,之後當於第一塗敷層4上形成具有對於腐蝕性氣體的阻擋性的第二塗敷層5時,可防止由焊劑殘渣23的龜裂應力傳播引起的第二塗敷層5的龜裂。As described above, the electronic substrate 1 on which the first coating layer 4 is formed on the entire or part of the surface of the substrate body 3 after the electronic component 2 is constructed is -20 ° C to 0 ° C, The tan δ at 10 Hz becomes the first coating layer 4 of 0.10 or more. Even if the flux residue 23 of the solder 22 is cracked in an environment where repeated warm or cold heat shocks are applied, it can absorb the crack originating from the crack. Stress propagation. As a result, when the second coating layer 5 having barrier properties against corrosive gases is formed on the first coating layer 4 later, the second coating layer caused by the crack stress propagation of the flux residue 23 can be prevented. 5 cracked.
但是,若DMA的-20℃~0℃、10 Hz的tanδ成為1.0以上,則第一塗敷層4容易變形,因此難以控制膜厚,其結果為,第二塗敷層5的形成變得不穩定。因此,第一塗敷層4較佳為使用硬化後的DMA的-20℃~0℃、10 Hz的tanδ未滿1.0的塗敷組成物。However, if the tan δ at -20 ° C to 0 ° C and 10 Hz of the DMA becomes 1.0 or more, the first coating layer 4 is easily deformed and it is difficult to control the film thickness. As a result, the formation of the second coating layer 5 becomes Unstable. Therefore, the first coating layer 4 is preferably a coating composition using a cured DMA at -20 ° C to 0 ° C and a tan δ of less than 1.0 at 10 Hz.
於形成第一塗敷層4之前,亦可對安裝有電子零件2的基板本體3進行電漿清洗。藉由進行電漿清洗而基板本體3的表面被改質,另外,異物被去除,藉此第一塗敷組成物的塗佈性能提升。另外,由於過剩的焊劑殘渣23減少,因此當反覆施加溫熱衝擊或冷熱衝擊時,亦可減少成為裂紋的應力傳播的原因的焊劑殘渣23。電漿清洗可使用空氣、氮氣、氬氣等公知的方法。就生產性的觀點而言,較佳為使用空氣的大氣壓電漿清洗。再者,存在安裝於基板本體3的電子零件2因電漿清洗而受到損傷的情況,因此,於進行電漿清洗的情況下,對可否應用進行判斷之後加以實施。Before the first coating layer 4 is formed, the substrate body 3 on which the electronic components 2 are mounted may be plasma-cleaned. By performing plasma cleaning, the surface of the substrate body 3 is modified, and foreign matter is removed, whereby the coating performance of the first coating composition is improved. In addition, since the excess flux residues 23 are reduced, the flux residues 23 that cause cracks to propagate can also be reduced when warm shock or cold shock is repeatedly applied. The plasma cleaning can be performed by a known method such as air, nitrogen, or argon. From the viewpoint of productivity, atmospheric piezoelectric slurry cleaning using air is preferred. In addition, the electronic component 2 mounted on the substrate body 3 may be damaged due to plasma cleaning. Therefore, when performing plasma cleaning, it is determined whether the application is possible or not.
如圖3所示,第二塗敷層5可使用腐蝕性氣體遮擋用塗敷組成物,所述腐蝕性氣體遮擋用塗敷組成物包含:在硬化後的藉由正電子壽命消滅法所得的自由體積半徑的測定值的分佈中0.32 nm以下(不包含0)的分佈面積設為70%以上的樹脂組成物,及其溶劑。As shown in FIG. 3, the second coating layer 5 can use a coating composition for corrosive gas shielding, the coating composition for corrosive gas shielding comprising: a hardened material obtained by a positron lifetime extinction method; The resin composition having a distribution area of 0.32 nm or less (excluding 0) in the distribution of the measured value of the free volume radius is 70% or more, and a solvent thereof.
作為在硬化後的藉由正電子壽命消滅法所得的自由體積半徑的測定值的分佈中0.32 nm以下(不包含0)的分佈面積設為70%以上的樹脂組成物,可列舉丙烯酸樹脂、聚酯樹脂、聚胺基甲酸酯樹脂、矽酮樹脂、氟樹脂及環氧樹脂中的任一種以上。只要滿足在硬化後的藉由正電子壽命消滅法所得的自由體積半徑的測定值的分佈中0.32 nm以下(不包含0)的分佈面積成為70%以上的要件,則該些樹脂組成物亦可使用一種或者組合使用多種。Examples of the resin composition in which the distribution area of 0.32 nm or less (excluding 0) in the distribution of the measured value of the free volume radius obtained by the positron lifetime extinction method after curing is 70% or more, include acrylic resins, polymers, and polymers. Any one or more of an ester resin, a polyurethane resin, a silicone resin, a fluororesin, and an epoxy resin. These resin compositions are also acceptable as long as the distribution area of 0.32 nm or less (excluding 0) in the distribution of the measured value of the free volume radius obtained by the positron lifetime extinction method after curing is 70% or more. Use one type or multiple types in combination.
作為丙烯酸樹脂,例如可列舉對多官能(甲基)丙烯酸酯單體進行紫外線(ultraviolet,UV)硬化、電子束硬化而成者。Examples of the acrylic resin include those obtained by subjecting a polyfunctional (meth) acrylate monomer to ultraviolet (UV) curing and electron beam curing.
作為聚酯樹脂,例如可列舉:利用硬化劑使於苯乙烯等反應性單體中稀釋溶解有藉由飽和二元酸或不飽和二元酸與甘醇的縮聚而生成的不飽和聚酯者、或者於藉由環氧樹脂與(甲基)丙烯酸的加成反應而生成的乙烯基酯中稀釋溶解有苯乙烯等反應性單體者、硬化而成者。Examples of the polyester resin include those in which a unsaturated polyester produced by polycondensation of a saturated dibasic acid or an unsaturated dibasic acid with a glycol is diluted and dissolved in a reactive monomer such as styrene with a hardener. Or, a vinyl monomer produced by the addition reaction of an epoxy resin and (meth) acrylic acid is diluted with a reactive monomer such as styrene and dissolved or hardened.
作為聚胺基甲酸酯樹脂,例如可列舉:對使聚異氰酸酯與平均分子量為6000以下的聚酯多元醇反應所得的胺基甲酸酯預聚物的末端(NCO)經(甲基)丙烯醯基改質而成者進行UV硬化所得者。Examples of the polyurethane resin include a (meth) propylene terminal (NCO) of a urethane prepolymer obtained by reacting a polyisocyanate with a polyester polyol having an average molecular weight of 6,000 or less. Those who have been modified by fluorene base are those who have undergone UV curing.
作為矽酮樹脂,例如可列舉有機聚矽氧烷等硬塗劑。Examples of the silicone resin include hard coating agents such as organic polysiloxane.
作為氟樹脂,例如可列舉:全氟己基乙基(甲基)丙烯酸酯、全氟丁基乙基(甲基)丙烯酸酯等全氟烷基(甲基)丙烯酸酯與(甲基)丙烯酸酯的共聚物(copolymer)。作為塗敷劑,可列舉將所述共聚物5重量%溶解於乙酸乙酯、甲苯等溶劑95%重量%中而成者。Examples of the fluororesin include perfluoroalkyl (meth) acrylates and (meth) acrylates such as perfluorohexylethyl (meth) acrylate and perfluorobutylethyl (meth) acrylate. Copolymer (copolymer). Examples of the coating agent include those obtained by dissolving 5% by weight of the copolymer in 95% by weight of a solvent such as ethyl acetate and toluene.
作為環氧樹脂,例如可列舉:於雙酚A型環氧樹脂、酚醛清漆型環氧樹脂、縮水甘油酯型環氧樹脂、縮水甘油胺型環氧樹脂中使用作為硬化劑的胺系、酸酐系、聚醯胺系並進行加熱硬化而成者。Examples of the epoxy resin include amine-based and acid anhydrides used as hardeners in bisphenol A epoxy resin, novolac epoxy resin, glycidyl ester epoxy resin, and glycidylamine epoxy resin. System, polyamine system and heat curing.
於第二塗敷組成物中,除所述成分以外,亦可含有該技術領域中公知的顏料、染料、阻燃劑、黏度調整劑、抗氧化劑、填料等各種添加劑。關於所述添加劑的含量,只要為不阻礙本發明的效果的範圍內,則並無特別限定,可適當調整來使用。The second coating composition may contain various additives such as pigments, dyes, flame retardants, viscosity modifiers, antioxidants, and fillers, which are well known in the technical field, in addition to the components. The content of the additive is not particularly limited as long as it is within a range that does not inhibit the effects of the present invention, and can be appropriately adjusted for use.
於將所述第一塗敷層4形成於構建電子零件2後的基板本體3的表面整體或一部分之後,以被覆該第一塗敷層4的方式自其上方將如所述般構成的第二塗敷組成物塗佈於所述基板本體3的表面整體或一部分,藉此可將第二塗敷層5形成於該表面整體或一部分。因此,當於基板本體3的上表面或下表面中的任一單面側設置有第一塗敷層4之類的情況下,以可被覆該第一塗敷層4的方式將第二塗敷層5設置於同一單面側,當於兩面設置有第一塗敷層4之類的情況下,同樣地將第二塗敷層5設置於兩面。After the first coating layer 4 is formed on the whole or a part of the surface of the substrate body 3 after the electronic component 2 is constructed, the first coating layer 4 covering the first coating layer 4 will cover the first structured layer as described above. The two coating compositions are applied to the whole or a part of the surface of the substrate body 3, whereby the second coating layer 5 can be formed on the whole or a part of the surface. Therefore, when the first coating layer 4 or the like is provided on any one side of the upper surface or the lower surface of the substrate body 3, the second coating layer is coated so as to cover the first coating layer 4. The cladding layer 5 is provided on the same single-sided side, and when the first coating layer 4 and the like are provided on both sides, the second coating layer 5 is similarly provided on both sides.
於圖1(a)~圖1(c)所示的實施例中,示出了噴霧塗裝的例子,但此時,塗佈第二塗敷組成物的方法並無特別限定,可使用該技術領域中公知的方法。作為塗佈方法的具體例,可列舉:刷毛塗佈、刷塗、輥塗、噴霧塗佈、浸漬、滴注等。該些方法亦可單獨或者組合兩種以上的方法來進行。Although the example shown in FIG.1 (a)-FIG.1 (c) shows the example of spray coating, the method of apply | coating a 2nd coating composition is not specifically limited at this time, You may use this Methods well known in the art. Specific examples of the coating method include bristle coating, brush coating, roll coating, spray coating, dipping, dripping, and the like. These methods may be performed alone or in combination of two or more methods.
第二塗敷層5可藉由將第二塗敷組成物塗佈後加以硬化而形成,但此時,作為硬化方法,只要對應於所使用的第二塗敷組成物的種類適當決定即可。作為硬化方法的具體例,可列舉:乾燥硬化、室溫硬化、加熱硬化、或者紅外線硬化、紫外線硬化、電子束硬化等。The second coating layer 5 can be formed by applying and curing the second coating composition, but in this case, as the curing method, it may be determined appropriately according to the type of the second coating composition used. . Specific examples of the curing method include dry curing, room temperature curing, heat curing, or infrared curing, ultraviolet curing, and electron beam curing.
第二塗敷層的厚度為5 μm~200 μm,較佳為10 μm~100 μm。若低於5 μm,則第二塗敷層的腐蝕性氣體的遮擋性缺乏,且難以防止電子基板1的腐蝕。另外,若超過200 μm,則硬化時第二塗敷層的硬化收縮應力變大,容易於與第一塗敷層的界面處發生剝離、或者發生第二塗敷層的破裂。The thickness of the second coating layer is 5 μm to 200 μm, and preferably 10 μm to 100 μm. If it is less than 5 μm, the barrier property of the corrosive gas of the second coating layer is insufficient, and it is difficult to prevent corrosion of the electronic substrate 1. In addition, if it exceeds 200 μm, the curing shrinkage stress of the second coating layer during hardening becomes large, and peeling at the interface with the first coating layer or cracking of the second coating layer easily occurs.
關於如所述般於構建電子零件2後的基板本體3的表面整體或一部分形成所述第一塗敷層4之後,進而以被覆該第一塗敷層4的方式形成有第二塗敷層5的電子基板1,利用在硬化後的藉由正電子壽命消滅法所得的自由體積半徑的測定分佈中0.32 nm以下(不包含0)的分佈面積成為70%以上的第二塗敷層5,將電子零件2的包含電極21的導電性金屬部分被覆,如圖4所示,硫化氫氣體等腐蝕性氣體的氣體分子6無法於與構成第二塗敷層5的分子鏈51的間隙相當的自由體積部分50通過。其結果為,第二塗敷層5可遮擋硫化氫氣體等腐蝕性氣體。藉此,電子基板1的對於腐蝕性氣體的耐蝕性提升,從而可獲得優異的耐環境性能。After forming the first coating layer 4 on the entire or part of the surface of the substrate body 3 after the electronic component 2 is constructed as described above, a second coating layer is formed so as to cover the first coating layer 4. The electronic substrate 1 of 5 uses the second coating layer 5 having a distribution area of 0.32 nm or less (excluding 0) in the measured distribution of the free volume radius obtained by the positron lifetime extinction method after curing, which is 70% or more. When the conductive metal part including the electrode 21 of the electronic component 2 is covered, as shown in FIG. The free volume portion 50 passes. As a result, the second coating layer 5 can shield corrosive gases such as hydrogen sulfide gas. Thereby, the corrosion resistance of the electronic substrate 1 to corrosive gas is improved, and excellent environmental resistance performance can be obtained.
另外,第二塗敷層5於硬化後的藉由正電子壽命消滅法所得的自由體積半徑的測定分佈中,0.32 nm以下(不包含0)的分佈面積設為70%以上,因此,雖然如所述般遮擋腐蝕性氣體的阻氣性優異,但分子結構緻密,剛性變高,因此,若僅為該第二塗敷層5,則缺乏應力緩和性。因此,於藉由施加反覆的溫熱衝擊或冷熱衝擊而變得容易破裂的(例如使用焊料22安裝有電子零件2之類)電子基板1的情況下,擔心硬化的焊劑殘渣23因溫熱衝擊或冷熱衝擊而破裂,且該裂紋傳播於第二塗敷層5並同樣地破裂,致使因溫熱衝擊或冷熱衝擊而失去阻氣性,但本發明中,於形成第一塗敷層4之後形成第二塗敷層5。而且,該第一塗敷層4的硬化後的狀態下的DMA的-20℃~0℃、10 Hz的tanδ設為0.10以上,並發揮防止由溫熱衝擊或冷熱衝擊引起的焊劑殘渣23的裂紋傳播於第二塗敷層5的功能,因此,即使於熱變化大的環境下,亦可維持優異的阻氣性。In addition, in the measured distribution of the free volume radius of the second coating layer 5 obtained by the positron lifetime extinction method after curing, the distribution area of 0.32 nm or less (excluding 0) is set to 70% or more. The above-mentioned barrier gas is excellent in gas barrier properties, but has a dense molecular structure and high rigidity. Therefore, if only the second coating layer 5 is used, stress relaxation properties are lacking. Therefore, in the case where the electronic substrate 1 is easily broken (for example, the electronic component 2 is mounted using the solder 22) by repeatedly applying a thermal shock or a thermal shock, there is a concern that the hardened flux residue 23 is subject to a thermal shock. Or cold and hot shock, and the crack propagates in the second coating layer 5 and breaks likewise, causing the gas barrier property to be lost due to warm or cold heat shock, but in the present invention, after the first coating layer 4 is formed A second coating layer 5 is formed. In addition, the tan δ of -20 ° C to 0 ° C and 10 Hz of the DMA in the cured state of the first coating layer 4 is set to 0.10 or more, and prevents the occurrence of flux residues 23 caused by warm shock or cold shock. Since cracks propagate through the function of the second coating layer 5, excellent gas barrier properties can be maintained even in an environment with large thermal changes.
因此,如圖2(b)所示,電子基板1於藉由產生大量焊劑殘渣23的流焊將電子零件2安裝於基板本體3的情況、或者於熱變化大的環境下使用的情況等下,可獲得特別顯著的阻氣性。Therefore, as shown in FIG. 2 (b), the electronic substrate 1 is used when the electronic component 2 is mounted on the substrate body 3 by flow soldering in which a large amount of flux residues 23 are generated, or when the electronic substrate 1 is used in an environment with large thermal changes. , Can obtain particularly significant gas barrier properties.
實施例 <樣品準備> 作為第一塗敷組成物,準備藉由稀釋劑(溶劑)將富士化學產業製造的希爾-格羅(Seal-glo)(橡膠系塗敷劑樹脂組成物)稀釋,並以藉由E型黏度計測量的黏度成為100 mPa·s~300 mPa·s左右的方式製備而成者。Example <Sample preparation> As a first coating composition, it is prepared to dilute Seal-glo (rubber-based coating agent resin composition) manufactured by Fuji Chemical Industries with a diluent (solvent). It is prepared so that the viscosity measured by an E-type viscometer becomes about 100 mPa · s to 300 mPa · s.
同樣地,作為第二塗敷組成物,準備藉由稀釋劑(溶劑)將艾爾·布朗(AR·Brown)製造的休米希(HumiSeal)(丙烯酸系塗敷劑樹脂組成物)稀釋,並以藉由E型黏度計測量的黏度成為100 mPa·s~300 mPa·s左右的方式製備而成者。 <物性評價用塗敷樣品的製作> 使用棒塗機(亞速旺(AS ONE)製造的No.75)將塗敷劑塗佈於脫模紙之上,並藉由減壓乾燥機(300托(torr))進行24小時的乾燥,藉此獲得硬化後的膜厚為100 μm~200 μm的第一塗敷層及第二塗敷層。 <藉由DMA的tanδ的測定> 對於第一塗敷層,使用UBM製造的動態黏彈性測定裝置(型式瑞奧格爾(Rheogel)-E4000),於-20℃~0℃的範圍內,以測量頻率10 Hz進行硬化後的tanδ的測量。 <自由體積半徑的測定> 對於第二塗敷層,使用富士·恩貝克(Fuji Imvac)公司製造的小型正電子束產生裝置帕爾斯(PALS)-200A(薄膜對應正電子消滅壽命測定裝置),使用22Na基質(base)的正電子束作為正電子束源,使用BaF 2製閃爍器+光電倍增管作為γ射線檢測器,於裝置常數:243 ps~246 ps、24.55 ps/ch,束強度:5 keV,測定深度:0 μm~2 μm(推測),測定溫度:室溫,測定環境:真空,總計數數目:約5000000計數,試樣前處理:室溫下真空除氣的條件下,進行硬化後的藉由正電子壽命消滅法的自由體積半徑的確認,測定0.32 nm以下(不包含0)的分佈面積。 <根據自由體積測定結果算出分佈面積> 作為根據所述自由體積半徑測定結果算出0.32 nm以下(不包含0)的分佈面積的方法,例如參照圖3,根據將分佈曲線與基線(baseline)的交點之間分割成100份所得的直方圖,算出0.32 nm以下的面積比例。 Similarly, as the second coating composition, HumiSeal (acrylic coating resin composition) manufactured by AR Brown was prepared to be diluted with a diluent (solvent), It is prepared so that the viscosity measured by an E-type viscometer may be about 100 mPa · s to 300 mPa · s. <Preparation of a coating sample for physical property evaluation> The coating agent was applied on a release paper using a bar coater (No. 75 manufactured by AS ONE), and a vacuum dryer (300 Torr) was dried for 24 hours to obtain a first coating layer and a second coating layer having a cured film thickness of 100 μm to 200 μm. <Measurement of tanδ by DMA> For the first coating layer, a dynamic viscoelasticity measuring device (type Rheogel-E4000) manufactured by UBM was used in the range of -20 ° C to 0 ° C. The measurement frequency was 10 Hz for tanδ measurement after hardening. <Measurement of Free Volume Radius> For the second coating layer, a small positron beam generating device Pals (PALS) -200A (thin film corresponding positron extinction life measuring device) manufactured by Fuji Imvac was used. Using a 22Na base positron as the positron source, using BaF 2 scintillator + photomultiplier tube as the γ-ray detector, device constants: 243 ps to 246 ps, 24.55 ps / ch, beam intensity : 5 keV, measurement depth: 0 μm to 2 μm (estimated), measurement temperature: room temperature, measurement environment: vacuum, total number of counts: about 5000000 counts, sample pretreatment: under vacuum degassing at room temperature, After confirming the free volume radius by the positron lifetime extinction method after hardening, a distribution area of 0.32 nm or less (excluding 0) was measured. <Calculate distribution area based on free volume measurement result> As a method of calculating a distribution area of 0.32 nm or less (excluding 0) based on the measurement result of free volume radius, for example, referring to FIG. 3, based on the intersection of the distribution curve and the baseline The histogram was divided into 100 parts, and the area ratio of 0.32 nm or less was calculated.
對於表1所示的第一塗敷組成物及第二塗敷組成物,分別藉由同樣的方法測定藉由DMA的tanδ及分佈面積。將結果示於表1。For the first coating composition and the second coating composition shown in Table 1, the tan δ and distribution area by DMA were measured by the same method, respectively. The results are shown in Table 1.
[表1]
實施例1-實施例12、比較例1-比較例9 <試片的製備> 作為電子基板,準備歐姆龍(Omron)製造的開關電源S8VK-S的基板。再者,電子零件朝電子基板的基板本體的安裝經過了焊劑塗佈、流焊塗佈步驟,並未特別進行焊劑清洗。Example 1 to Example 12, Comparative Example 1 to Comparative Example 9 <Preparation of test piece> As an electronic substrate, a substrate of a switching power supply S8VK-S manufactured by Omron was prepared. In addition, the mounting of the electronic component on the substrate body of the electronic substrate has undergone the steps of flux coating and flow solder coating, and the solder cleaning is not particularly performed.
使用武藏高科技(Musashi Engineering)製造的塗敷閥(coating valve)(CV-10)將第一塗敷組成物以成為膜厚30 μm的方式塗佈於該電子基板的基板本體。其後,藉由減壓乾燥機(300 torr)使其乾燥24小時而形成第一塗敷層。其後,再次使用上述閥,將第二塗敷組成物以成為30 μm的方式重疊塗佈於第一塗敷層之上,藉由減壓乾燥機(300 torr)進行24小時的乾燥,藉此形成第二塗敷層,從而獲得被覆有兩種塗敷層的電子基板。再者,塗敷層的膜厚是藉由使用測微計測定來調整。第一塗敷層的膜厚及第二塗敷層的膜厚均設為30 μm。A coating valve (CV-10) manufactured by Musashi Engineering was used to apply the first coating composition to the substrate body of the electronic substrate so as to have a film thickness of 30 μm. Thereafter, it was dried for 24 hours by a reduced pressure dryer (300 torr) to form a first coating layer. Thereafter, using the valve again, the second coating composition was superimposed on the first coating layer so as to have a thickness of 30 μm, and dried for 24 hours by a vacuum dryer (300 torr). This forms a second coating layer, thereby obtaining an electronic substrate covered with two kinds of coating layers. The film thickness of the coating layer was adjusted by measuring with a micrometer. The film thickness of the first coating layer and the film thickness of the second coating layer were both 30 μm.
第一塗敷層及第二塗敷層按照表2所示的組合來使用表1所示者。 <耐環境試驗的條件> 對形成有塗敷層的電子基板於低溫側-40℃×30 min、高溫側85℃×30 min反覆施加1000次循環的冷熱衝擊及溫熱衝擊。For the first coating layer and the second coating layer, the combinations shown in Table 2 were used as shown in Table 1. <Conditions of environmental resistance test> The electronic substrate on which the coating layer was formed was repeatedly subjected to cold and thermal shocks and warm and thermal shocks at a low temperature side of -40 ° C × 30 minutes and a high temperature side of 85 ° C × 30 minutes.
其後,於成為依據日本工業標準(Japanese Industrial Standards,JIS)C0048:1999的硫化系氣體(H 2S、SO 2的混合氣體)環境的試驗槽中靜置24小時。 Thereafter, it was left to stand in a test tank which became an environment of a sulfur-based gas (mixed gas of H 2 S, SO 2 ) in accordance with Japanese Industrial Standards (JIS) C0048: 1999.
靜置後,藉由目視來檢查塗敷層表面的外觀。作為觀察部位,主要觀察焊料、晶片端子、貫穿孔等包含銀及銅成分的材質的部位。 <評價> 將電子基板上的第一塗敷層、第二塗敷層無龜裂、電子基板上的金屬部外觀完全無變化者設為◎,將僅金屬部無變化者設為○。After standing, the appearance of the surface of the coating layer was checked visually. As the observation portion, a portion including a material including silver and copper components such as solder, a wafer terminal, and a through hole is mainly observed. <Evaluation> The case where the first coating layer and the second coating layer on the electronic substrate were free of cracks, and the appearance of the metal part on the electronic substrate was not changed at all was ◎, and the case where only the metal part was not changed was 设为.
另外,將電子基板表面的第一塗敷層、第二塗敷層發生龜裂者、或者於所述龜裂的附近電子基板上的金屬部外觀有變化者設為×。作為外觀檢查法,除目視以外,使用擴大鏡、放大鏡(loupe)、顯微鏡等放大至1倍~20倍來檢查。In addition, those in which the first coating layer and the second coating layer on the surface of the electronic substrate had cracks, or those in which the appearance of the metal portion on the electronic substrate in the vicinity of the cracks was changed, were set to ×. As the visual inspection method, in addition to visual inspection, magnification, magnification (loupe), microscope, etc. are used to magnify 1 to 20 times for inspection.
將結果示於表2。The results are shown in Table 2.
[表2]
根據以上結果,與本發明的實施例1-實施例12符合的電子基板既未產生龜裂,亦於其後的動作確認中確認到良好的結果。Based on the above results, the electronic substrates conforming to Examples 1 to 12 of the present invention neither cracked, and good results were confirmed in subsequent operation confirmation.
再者,本發明可不脫離其精神或主要特徵而以其他多種形態來實施。因此,所述實施例於所有方面僅為例示,不能進行限定性解釋。本發明的範圍藉由申請專利範圍來表示,完全不受說明書正文限制。進而,歸屬於申請專利範圍的變形或變更全部為本發明的範圍內者。In addition, the present invention can be implemented in various other forms without departing from the spirit or main characteristics thereof. Therefore, the embodiments are merely examples in all aspects and cannot be interpreted in a limited manner. The scope of the present invention is expressed by the scope of patent application, and is not limited at all by the text of the specification. Furthermore, all the deformation | transformation and change which belong to the scope of patent application are the scope of the present invention.
1:耐蝕性電子基板 2:電子零件 20:導電性金屬部分 21:電極 22:焊料 23:焊劑殘渣 3:基板本體 4:第一塗敷層 5:第二塗敷層 50:自由體積部分 51:分子鏈 6:腐蝕性氣體的氣體分子1: Corrosion-resistant electronic substrate 2: Electronic component 20: Conductive metal portion 21: Electrode 22: Solder 23: Flux residue 3: Substrate body 4: First coating layer 5: Second coating layer 50: Free volume portion 51 : Molecular chain 6: Gas molecules of corrosive gas
圖1(a)至圖1(c)是表示本發明的耐蝕性電子基板的製造步驟中的整體構成的概略的立體圖。 圖2(a)是圖1(c)中的I-I線剖面圖,圖2(b)是其他實施形態中的耐蝕性電子基板的剖面圖。 圖3是表示本發明的耐蝕性電子基板的第二塗敷層的物性的圖表。 圖4是表示本發明的耐蝕性電子基板的第二塗敷層的主要部分的概略圖。FIGS. 1 (a) to 1 (c) are schematic perspective views showing the overall configuration in the manufacturing steps of the corrosion-resistant electronic substrate of the present invention. Fig. 2 (a) is a sectional view taken along the line I-I in Fig. 1 (c), and Fig. 2 (b) is a sectional view of a corrosion-resistant electronic substrate in another embodiment. 3 is a graph showing physical properties of a second coating layer of a corrosion-resistant electronic substrate of the present invention. FIG. 4 is a schematic view showing a main part of a second coating layer of a corrosion-resistant electronic substrate of the present invention.
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