TW202239867A - Resin composition and electrical/electronic part encapsulation body - Google Patents
Resin composition and electrical/electronic part encapsulation body Download PDFInfo
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
- C08L67/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the carboxyl- and the hydroxy groups directly linked to aromatic rings
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- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
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- C08L77/08—Polyamides derived from polyamines and polycarboxylic acids from polyamines and polymerised unsaturated fatty acids
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- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
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Abstract
Description
本發明關於樹脂組成物。更詳細而言,係關於能封裝電氣電子零件之封裝用樹脂組成物及電氣電子零件封裝體。The present invention relates to resin compositions. More specifically, it relates to a resin composition for encapsulation capable of encapsulating electric and electronic parts, and an electric and electronic part package.
就使用於汽車、電器等的電氣電子零件之封裝所使用的絕緣性樹脂而言,一般會使用二液硬化型環氧樹脂、矽樹脂,但考量需要長時間之步驟、或也有可能因硬化時之收縮應力而破壞電氣電子零件,故近年已知有利用使用熱塑性樹脂之低壓成形所為之電氣電子零件的封裝。For the insulating resin used in the packaging of electrical and electronic parts such as automobiles and electrical appliances, two-component curing epoxy resins and silicone resins are generally used, but it is considered that it takes a long time to process, or it may be due to curing time. Therefore, in recent years, it has been known to package electrical and electronic components by low-pressure molding using thermoplastic resins.
考慮電氣絕緣性、耐水性、耐久性、熔融黏度之觀點,聚酯樹脂係作為理想的材料而被使用作為電氣電子零件之封裝樹脂,但在為了減少對電氣電子零件之損壞的低溫、低壓成形中,電氣電子零件和封裝樹脂的黏接性會變得不足,常有作為目的之電氣絕緣性、防水性無法充分發揮的情況。因此,已有人積極地探討考慮從根本提高黏接性之觀點而摻合具有官能基之賦黏劑等的嘗試(例如專利文獻1)。 [先前技術文獻] [專利文獻] Considering electrical insulation, water resistance, durability, and melt viscosity, polyester resin is used as an ideal material as an encapsulation resin for electrical and electronic parts, but it is molded at low temperature and low pressure to reduce damage to electrical and electronic parts In this case, the adhesiveness between electrical and electronic parts and encapsulating resin will become insufficient, and the intended electrical insulation and waterproof properties may not be fully exhibited. Therefore, an attempt to blend a tackifier having a functional group or the like from the viewpoint of fundamentally improving the adhesiveness has been actively studied (for example, Patent Document 1). [Prior Art Literature] [Patent Document]
[專利文獻1]日本特開2004-210893號公報[Patent Document 1] Japanese Patent Laid-Open No. 2004-210893
[發明所欲解決之課題][Problem to be Solved by the Invention]
另一方面,除了如上述要求的物性之外,在電氣電子零件中,有時會要求耐油性,但使用摻合了如專利文獻1之賦黏劑的熱塑性樹脂時,雖然黏接性會改善,但會有無法保證耐油性、絕緣性之問題。在習知技術中,尚未有人提出尤其可在維持低壓成形優良的樹脂之流動性的狀態下兼顧耐油性及絕緣性之封裝用樹脂組成物。On the other hand, in addition to the physical properties required above, oil resistance is sometimes required for electrical and electronic parts, but when using a thermoplastic resin blended with a tackifier such as Patent Document 1, although the adhesiveness can be improved , but there will be problems that oil resistance and insulation cannot be guaranteed. In the prior art, no one has proposed a resin composition for encapsulation that can achieve both oil resistance and insulation while maintaining the fluidity of the resin excellent in low pressure molding.
本發明係以該習知技術之課題為背景而成。亦即,本發明的目的在於提供一種樹脂組成物,在維持低壓成形優良的樹脂之流動性的狀態下不會使耐油性降低,尤其不會使在切削油浸漬時的物性降低,且絕緣性優良。本發明之樹脂組成物特別適於電氣電子零件之封裝用途。 [解決課題之手段] The present invention is made on the background of the subject of this prior art. That is, the object of the present invention is to provide a resin composition that does not degrade oil resistance, especially does not degrade physical properties during cutting oil immersion while maintaining the fluidity of the resin excellent in low-pressure molding, and has insulation properties. excellent. The resin composition of the present invention is particularly suitable for encapsulation of electric and electronic parts. [Means to solve the problem]
本發明人們經過深入探討後之結果發現,利用如下所示之手段可解決上述課題,乃至完成本發明。亦即本發明係由如下構成而成。As a result of intensive studies, the present inventors have found that the above-mentioned problems can be solved by the following means, and the present invention has been completed. That is, the present invention is constituted as follows.
[1] 一種樹脂組成物,含有: 溶解度參數(SP)值為10.0(cal/cm 3) 1/2以上之聚酯樹脂(A), 二聚酸聚醯胺(B),及 環氧樹脂(C)。 [1] A resin composition comprising: polyester resin (A) with a solubility parameter (SP) value of 10.0 (cal/cm 3 ) 1/2 or more, dimer acid polyamide (B), and epoxy resin (C).
[2] 如前述[1]所記載之樹脂組成物,其中,聚酯樹脂(A)具有對苯二甲酸、間苯二甲酸、丁烷二醇及聚四亞甲基二醇作為構成單元。[2] The resin composition according to the above [1], wherein the polyester resin (A) has terephthalic acid, isophthalic acid, butanediol, and polytetramethylene glycol as constituent units.
[3] 如前述[1]或[2]所記載之樹脂組成物,其中,聚酯樹脂(A)及二聚酸聚醯胺(B)的玻璃轉移溫度均為-20℃以下。[3] The resin composition according to [1] or [2] above, wherein both the polyester resin (A) and the dimer acid polyamide (B) have a glass transition temperature of -20°C or lower.
[4] 如前述[1]~[3]中任一項所記載之樹脂組成物,更含有賦黏劑(D)。[4] The resin composition described in any one of [1] to [3] above, further comprising a tackifier (D).
[5] 如前述[4]所記載之樹脂組成物,其中,賦黏劑(D)的SP值為9.0(cal/cm 3) 1/2以上。 [5] The resin composition as described in [4] above, wherein the SP value of the tackifier (D) is 9.0 (cal/cm 3 ) 1/2 or more.
[6] 如前述[1]~[5]中任一項所記載之樹脂組成物,更含有抗氧化劑(E)。[6] The resin composition described in any one of [1] to [5] above, further containing an antioxidant (E).
[7] 一種封裝用樹脂組成物,含有如前述[1]~[6]中任一項所記載之樹脂組成物。[7] A resin composition for encapsulation, comprising the resin composition described in any one of [1] to [6] above.
[8] 一種電氣電子零件封裝體,係以如前述[7]所記載之封裝用樹脂組成物進行封裝。 [發明之效果] [8] A package for electrical and electronic components, which is packaged with the resin composition for packaging described in [7] above. [Effect of Invention]
本發明之樹脂組成物展現優良的流動性,且耐油性及絕緣性優良。因此,尤其藉由在電氣電子零件封裝體中使用作為封裝材,可製造耐油性及絕緣性令人滿意的電氣電子零件封裝體。The resin composition of the present invention exhibits excellent fluidity, and is excellent in oil resistance and insulation. Therefore, especially by using it as a packaging material in an electrical and electronic component package, an electrical and electronic component package with satisfactory oil resistance and insulation properties can be manufactured.
以下,詳述本發明。Hereinafter, the present invention will be described in detail.
<聚酯樹脂(A)> 本發明所使用的聚酯樹脂(A)宜由如下之化學結構構成;該化學結構係主要由聚酯鏈段構成的硬鏈段及主要由聚伸烷基二醇成分構成的軟鏈段利用酯鍵鍵結而成的。前述聚酯鏈段主要由聚酯構成較理想;該聚酯係利用芳香族二羧酸與脂肪族二醇及/或脂環族二醇之聚縮合所能形成的結構。 <Polyester resin (A)> The polyester resin (A) used in the present invention is preferably composed of the following chemical structure; the chemical structure is a hard segment mainly composed of a polyester segment and a soft segment mainly composed of a polyalkylene glycol component. formed by ester bonds. The aforementioned polyester segment is preferably mainly composed of polyester; the polyester is a structure that can be formed by polycondensation of aromatic dicarboxylic acid and aliphatic diol and/or alicyclic diol.
本發明所使用的聚酯樹脂(A)之SP值必須為10.0(cal/cm 3) 1/2以上。宜為10.5(cal/cm 3) 1/2以上。切削油的SP值一般而言約為7~8(cal/cm 3) 1/2,SP值低,且和切削油的SP值愈接近,則親和性愈良好,有時會有浸漬於切削油時,樹脂會吸收切削油,並因為樹脂的膨潤而使耐油性惡化的情況。另一方面,SP值過高時,和二聚酸聚醯胺(B)的相容性會降低,有時反而會有樹脂組成物之絕緣性、耐油性、機械特性差的情況。因此,SP值宜為12.5(cal/cm 3) 1/2以下,為12.0(cal/cm 3) 1/2以下更佳,為11.5(cal/cm 3) 1/2以下再更佳。SP值可藉由單體的選擇、調整酯鍵濃度來進行調整,藉由將極性高的單體予以共聚合或提高酯鍵濃度,可獲得高SP值。在此,本發明所使用的SP值係利用從分子結構進行推算之Fedors的計算方法求得的值。計算方法記載於如下文獻;Polym. Eng. Sci., 14[2], 147-154(1974)。 The polyester resin (A) used in the present invention must have an SP value of 10.0 (cal/cm 3 ) 1/2 or more. It is preferably 10.5 (cal/cm 3 ) 1/2 or more. Generally speaking, the SP value of cutting oil is about 7~8(cal/cm 3 ) 1/2 . The lower the SP value, and the closer it is to the SP value of cutting oil, the better the affinity, and sometimes there will be impregnation in cutting oil. When oil is used, the resin absorbs cutting oil, and the oil resistance deteriorates due to the swelling of the resin. On the other hand, if the SP value is too high, the compatibility with the dimer acid polyamide (B) will decrease, and the insulation, oil resistance, and mechanical properties of the resin composition may be poor on the contrary. Therefore, the SP value is preferably 12.5 (cal/cm 3 ) 1/2 or less, more preferably 12.0 (cal/cm 3 ) 1/2 or less, and even more preferably 11.5 (cal/cm 3 ) 1/2 or less. The SP value can be adjusted by selecting monomers and adjusting the concentration of ester bonds. By copolymerizing highly polar monomers or increasing the concentration of ester bonds, a high SP value can be obtained. Here, the SP value used in the present invention is a value obtained by the calculation method of Fedors estimated from the molecular structure. The calculation method is described in the following literature; Polym. Eng. Sci., 14[2], 147-154 (1974).
本發明所使用的聚酯樹脂(A)之玻璃轉移溫度宜為-20℃以下,為-30℃以下更佳。The glass transition temperature of the polyester resin (A) used in the present invention is preferably below -20°C, more preferably below -30°C.
本發明所使用的聚酯樹脂(A)之酯基濃度的上限宜為8000當量/10 6g。理想的上限為7500當量/10 6g,為7000當量/10 6g更佳。又,要求對切削油、燈油、汽油、機油、其它烴系溶劑等之耐油性時,下限宜為1000當量/10 6g。更理想的下限為1500當量/10 6g,為2000當量/10 6g再更佳。在此,酯基濃度的單位係表示每10 6g樹脂的酯基之當量數,可由聚酯樹脂的組成及其共聚合比進行計算而得。 The upper limit of the ester group concentration of the polyester resin (A) used in the present invention is preferably 8000 equivalents/10 6 g. The ideal upper limit is 7500 equivalents/10 6 g, more preferably 7000 equivalents/10 6 g. Also, when oil resistance to cutting oil, kerosene, gasoline, engine oil, and other hydrocarbon solvents is required, the lower limit is preferably 1000 equivalents/10 6 g. A more desirable lower limit is 1500 equivalents/10 6 g, more preferably 2000 equivalents/10 6 g. Here, the unit of ester group concentration represents the equivalent number of ester groups per 10 6 g of resin, which can be calculated from the composition of polyester resin and its copolymerization ratio.
本發明所使用的聚酯樹脂(A)之酸價宜為100當量/10 6g以下,為70當量/10 6g以下更佳,為50當量/10 6g以下再更佳。酸價過高的話,有時會有因產生自羧酸的酸而促進聚酯樹脂(A)的水解,並造成樹脂強度降低的情況。酸價的下限並無特別限制,宜為10當量/10 6g以上,為20當量/10 6g以上更佳。酸價過低的話,有時會有黏接性降低的情況。 The acid value of the polyester resin (A) used in the present invention is preferably 100 equivalents/10 6 g or less, more preferably 70 equivalents/10 6 g or less, even more preferably 50 equivalents/10 6 g or less. When the acid value is too high, the hydrolysis of the polyester resin (A) may be accelerated by the acid derived from the carboxylic acid, and the strength of the resin may decrease. The lower limit of the acid value is not particularly limited, but it is preferably at least 10 equivalents/10 6 g, more preferably at least 20 equivalents/10 6 g. When the acid value is too low, the adhesiveness may decrease.
本發明所使用的聚酯樹脂(A)之數目平均分子量的下限並無特別限制,宜為3,000以上,為5,000以上更佳,為7,000以上再更佳。又,數目平均分子量的上限並無特別限制,宜為80,000以下,為70,000以下更佳,為60,000以下再更佳。數目平均分子量過低的話,有時會有樹脂組成物之耐水解性不足、保持在高溫高濕下的強延伸性不足的情況,數目平均分子量過高的話,有時會有樹脂組成物的熔融黏度變高,並使成形壓力變得過高或成形困難的情況。The lower limit of the number average molecular weight of the polyester resin (A) used in the present invention is not particularly limited, but it is preferably 3,000 or more, more preferably 5,000 or more, and even more preferably 7,000 or more. Also, the upper limit of the number average molecular weight is not particularly limited, but it is preferably 80,000 or less, more preferably 70,000 or less, and even more preferably 60,000 or less. If the number average molecular weight is too low, the hydrolysis resistance of the resin composition may be insufficient, and the strong extensibility under high temperature and high humidity may be insufficient. If the number average molecular weight is too high, the resin composition may melt Viscosity becomes high, making molding pressure too high or molding difficult.
本發明所使用的聚酯樹脂(A)之熔融黏度的上限,在成形溫度下(例如230℃)宜未達5000dPa・s,未達4000dPa・s更佳,未達3000dPa・s再更佳。又,熔融黏度的下限並無特別限制,宜為50dPa・s以上,為300dP・s更佳,為500dPa・s再更佳,為1000dPa・s最佳。熔融黏度過高的話,有時會有成形時的流動性變差,或造成成形困難的情況,熔融黏度過低的話,有時會有耐油性、機械特性降低、或無法排解毛邊等成形之外觀不良的情況。The upper limit of the melt viscosity of the polyester resin (A) used in the present invention is preferably less than 5000dPa・s, more preferably less than 4000dPa・s, more preferably less than 3000dPa・s at the molding temperature (eg 230°C). Also, the lower limit of the melt viscosity is not particularly limited, but it is preferably 50 dPa・s or more, more preferably 300 dPa・s, more preferably 500 dPa・s, most preferably 1000 dPa・s. If the melt viscosity is too high, the fluidity during molding may be deteriorated or molding may be difficult. If the melt viscosity is too low, the appearance of molding such as oil resistance and mechanical properties may be reduced, or burrs cannot be removed. bad situation.
本發明所使用的聚酯樹脂(A)宜為飽和聚酯樹脂,也可為具有50當量/10 6g以下之微量的乙烯基之不飽和聚酯樹脂。為具有高濃度的乙烯基之不飽和聚酯的話,有時會有熔融時引發交聯等的可能性,熔融安定性差的情況。 The polyester resin (A) used in the present invention is preferably a saturated polyester resin, and may also be an unsaturated polyester resin having a trace amount of vinyl groups of 50 equivalents/10 6 g or less. If it is an unsaturated polyester having a high concentration of vinyl groups, crosslinking or the like may occur during melting, resulting in poor melt stability.
本發明所使用的聚酯樹脂(A)因應需要將偏苯三甲酸酐、三羥甲基丙烷等三官能以上之多元羧酸、多元醇予以共聚合,並製成具有分支的聚酯亦無妨。The polyester resin (A) used in the present invention may be prepared by copolymerizing trifunctional or higher polycarboxylic acids and polyhydric alcohols, such as trimellitic anhydride and trimethylolpropane, to produce branched polyesters.
本發明所使用的聚酯樹脂(A)為了使熱劣化盡可能不發生而予以成型,要求在210~240℃之快速的熔融。因此,聚酯樹脂(A)之熔點的上限宜為210℃。理想為200℃,為190℃更佳。考慮在常溫下的操作性及通常的耐熱性的話,聚酯樹脂(A)的熔點宜為90℃以上,為100℃以上更佳,為110℃以上再更佳,為120℃以上特佳,為130℃以上最佳。The polyester resin (A) used in the present invention requires rapid melting at 210 to 240° C. in order to mold it so that thermal deterioration does not occur as much as possible. Therefore, the upper limit of the melting point of the polyester resin (A) is preferably 210°C. The ideal temperature is 200°C, more preferably 190°C. Considering the workability at room temperature and the usual heat resistance, the melting point of the polyester resin (A) is preferably 90°C or higher, more preferably 100°C or higher, more preferably 110°C or higher, and most preferably 120°C or higher. The best temperature is above 130°C.
本發明所使用的聚酯樹脂(A)之製造方法可採用公知的方法。例如,藉由使後述多元羧酸成分及多元醇成分在150~250℃進行酯化反應後,再使其邊減壓邊於230~300℃進行聚縮合反應,可獲得聚酯。或,藉由使用後述多元羧酸之二甲基酯等衍生物及多元醇成分並使其在150℃~250℃進行酯交換反應後,再使其邊減壓邊於230℃~300℃進行聚縮合反應,可獲得聚酯。A known method can be used for the production method of the polyester resin (A) used in the present invention. For example, polyester can be obtained by carrying out the polycondensation reaction at 230-300°C while reducing the pressure after carrying out the esterification reaction of the polycarboxylic acid component and the polyol component described below at 150-250°C. Or, by using derivatives such as dimethyl esters of polycarboxylic acids described later and polyhydric alcohol components to carry out transesterification at 150°C to 250°C, and then carrying out the reaction at 230°C to 300°C while reducing pressure. Polycondensation reaction, polyester can be obtained.
<聚酯樹脂(A)之硬鏈段> 構成本發明所使用的聚酯樹脂(A)之硬鏈段主要由聚酯鏈段構成較理想。聚酯鏈段主要以多元羧酸成分及多元醇成分作為構成單元。 <Hard segment of polyester resin (A)> It is preferable that the hard segment constituting the polyester resin (A) used in the present invention is mainly composed of a polyester segment. Polyester chain segments mainly use polycarboxylic acid components and polyol components as constituent units.
構成前述聚酯鏈段之多元羧酸成分並無特別限制,含有芳香族二羧酸的話,就可使聚酯樹脂(A)之耐熱性改善的觀點較為理想。芳香族二羧酸之具體例可列舉:對苯二甲酸、萘二甲酸、二苯基二甲酸、間苯二甲酸、5-磺基間苯二甲酸鈉等。尤其,芳香族二羧酸為對苯二甲酸及/或萘二甲酸的話,除了改善耐熱性之外,還和二醇具有高反應性,就聚合性及生產性的觀點較為理想。令構成聚酯鏈段之全部多元羧酸成分為100莫耳%時,對苯二甲酸及萘二甲酸的合計宜為50莫耳%以上,為60莫耳%以上更佳,為80莫耳%以上再更佳,為95莫耳%以上特佳,全部多元羧酸成分係由對苯二甲酸及/或萘二甲酸構成亦無妨。The polyvalent carboxylic acid component constituting the polyester segment is not particularly limited, but it is preferable from the viewpoint of improving the heat resistance of the polyester resin (A) if it contains an aromatic dicarboxylic acid. Specific examples of aromatic dicarboxylic acids include terephthalic acid, naphthalene dicarboxylic acid, diphenyl dicarboxylic acid, isophthalic acid, and sodium 5-sulfoisophthalate. In particular, when the aromatic dicarboxylic acid is terephthalic acid and/or naphthalene dicarboxylic acid, in addition to improving heat resistance, it has high reactivity with diols, and is preferable from the viewpoint of polymerizability and productivity. When the total polycarboxylic acid component constituting the polyester segment is 100 mole%, the total of terephthalic acid and naphthalene dicarboxylic acid is preferably 50 mole% or more, more preferably 60 mole% or more, and is 80 mole% More preferably more than 95% by mole, especially preferably more than 95% by mole, and it does not matter if all the polycarboxylic acid components are composed of terephthalic acid and/or naphthalene dicarboxylic acid.
構成聚酯鏈段之其它多元羧酸成分可列舉:環己烷二甲酸、四氫苯二甲酸酐等脂環族二羧酸;琥珀酸、戊二酸、己二酸、壬二酸、癸二酸、十二烷二酸、二聚酸、氫化二聚酸等脂肪族二羧酸等二羧酸。這些二羧酸成分可在不使聚酯樹脂(A)之熔點大幅降低的範圍內使用,其共聚合比率為全部多元羧酸成分的50莫耳%以下,宜為40莫耳%以下。又,構成聚酯鏈段之其它多元羧酸成分也可使用偏苯三甲酸、均苯四甲酸等3官能以上之多元羧酸。3官能以上之多元羧酸的共聚合比率,考慮防止樹脂組成物的凝膠化之觀點,宜設定為全部多元羧酸成分的10莫耳%以下,設定為5莫耳%以下更佳。Other polycarboxylic acid components constituting the polyester segment include: cyclohexanedicarboxylic acid, tetrahydrophthalic anhydride and other alicyclic dicarboxylic acids; succinic acid, glutaric acid, adipic acid, azelaic acid, decane Dicarboxylic acids such as aliphatic dicarboxylic acids such as diacids, dodecanedioic acids, dimer acids, and hydrogenated dimer acids. These dicarboxylic acid components can be used within the range that does not significantly lower the melting point of the polyester resin (A), and the copolymerization ratio thereof is 50 mol% or less, preferably 40 mol% or less, of the total polyvalent carboxylic acid components. In addition, as other polyvalent carboxylic acid components constituting the polyester segment, trifunctional or higher polycarboxylic acids such as trimellitic acid and pyromellitic acid may be used. The copolymerization ratio of polyhydric carboxylic acids with more than 3 functions is preferably set to 10 mol% or less, more preferably 5 mol% or less, based on the viewpoint of preventing gelation of the resin composition.
又,構成聚酯鏈段之多元醇成分並無特別限制,就可使聚酯樹脂(A)之耐熱性改善的觀點,宜為脂肪族二醇及/或脂環族二醇。其中,就脂肪族二醇及/或脂環族二醇而言,宜為碳數2~10之伸烷基二醇類,為碳數2~8之伸烷基二醇類更佳。特佳的脂肪族二醇及脂環族二醇成分具體可列舉:乙二醇、1,3-丙二醇、1,4-丁烷二醇、1,6-己烷二醇、1,4-環己烷二甲醇等,為1,4-丁烷二醇及1,4-環己烷二甲醇最佳。脂肪族二醇及/或脂環族二醇宜為全部多元醇成分的50莫耳%以上,為70莫耳%以上更佳。又,多元醇成分的一部分也可使用甘油、三羥甲基丙烷、新戊四醇等3官能以上之多元醇,考慮防止樹脂組成物之凝膠化的觀點,宜設定為全部多元醇成分的10莫耳%以下,設定為5莫耳%以下更佳。Also, the polyol component constituting the polyester segment is not particularly limited, but is preferably an aliphatic diol and/or alicyclic diol from the viewpoint of improving the heat resistance of the polyester resin (A). Among them, the aliphatic diol and/or the alicyclic diol are preferably alkylene glycols having 2 to 10 carbon atoms, more preferably alkylene glycols having 2 to 8 carbon atoms. Particularly preferred aliphatic diol and alicyclic diol components specifically include: ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,4- Cyclohexanedimethanol and the like are most suitable for 1,4-butanediol and 1,4-cyclohexanedimethanol. The aliphatic diol and/or alicyclic diol is preferably at least 50 mol%, more preferably at least 70 mol%, of the total polyol components. In addition, trifunctional or higher polyols such as glycerin, trimethylolpropane, and neopentyl glycol may be used as a part of the polyol component, and it is preferable to set it as the entire polyol component in view of preventing gelation of the resin composition. 10 mol% or less, preferably 5 mol% or less.
就構成聚酯鏈段之成分而言,由對苯二甲酸丁二酯單元或萘二甲酸丁二酯單元構成者,可使聚酯樹脂(A)成為高熔點並使耐熱性改善,又,考量成形性、性價比之觀點為特佳。As for the components constituting the polyester segment, those composed of a butylene terephthalate unit or a butylene naphthalate unit can make the polyester resin (A) have a high melting point and improve heat resistance, and, Considering formability and cost performance are especially good.
構成聚酯鏈段之多元羧酸成分及多元醇成分也可含有來自生質之原料。The polycarboxylic acid component and polyol component constituting the polyester segment may contain biomass-derived raw materials.
<聚酯樹脂(A)之軟鏈段> 本發明所使用的聚酯樹脂(A)之軟鏈段主要由聚伸烷基二醇成分構成較理想。軟鏈段的共聚合比率在令構成前述聚酯樹脂(A)之多元醇成分整體為100莫耳%時,宜為0.5莫耳%以上,為2.5莫耳%以上更佳,為5莫耳%以上再更佳。又,宜為50莫耳%以下,為45莫耳%以下更佳,為40莫耳%以下再更佳。軟鏈段的共聚合比率過低的話,會有發生本發明之樹脂組成物的熔融黏度變高而無法在低壓成形、或結晶化速度快而發生短射等之問題的傾向。又,軟鏈段的共聚合比率過高的話,會有發生製成封裝體時的耐熱性不足等之問題的傾向。 <Soft segment of polyester resin (A)> The soft segment of the polyester resin (A) used in the present invention is preferably composed mainly of polyalkylene glycol components. The copolymerization ratio of the soft segment is preferably 0.5 mol % or more, more preferably 2.5 mol % or more, and 5 mol % when the total polyol component constituting the polyester resin (A) is 100 mol % More than % is better. Also, it is preferably not more than 50 mol%, more preferably not more than 45 mol%, and more preferably not more than 40 mol%. If the copolymerization ratio of the soft segment is too low, problems such as high melt viscosity of the resin composition of the present invention that cannot be molded at low pressure, or high crystallization speed and short shot tend to occur. Also, if the copolymerization ratio of the soft segment is too high, problems such as insufficient heat resistance when forming a package tend to occur.
軟鏈段的數目平均分子量並無特別限制,宜為400以上,為800以上更佳。軟鏈段的數目平均分子量過低的話,會有發生無法賦予柔軟性而對封裝後的電子基板之應力負荷變大之問題的傾向。又,軟鏈段的數目平均分子量宜為5000以下,為3000以下更佳。數目平均分子量過高的話,會有發生和其它共聚合成分之相容性差而無法共聚合之問題的傾向。The number-average molecular weight of the soft segment is not particularly limited, and is preferably at least 400, more preferably at least 800. When the number-average molecular weight of the soft segment is too low, the problem that flexibility cannot be imparted and the stress load on the packaged electronic substrate tends to increase. Also, the number average molecular weight of the soft segment is preferably 5,000 or less, more preferably 3,000 or less. When the number average molecular weight is too high, the compatibility with other copolymerization components tends to be poor, and the problem of being unable to copolymerize tends to arise.
軟鏈段所使用的聚伸烷基二醇成分之具體例可列舉:聚乙二醇、聚三亞甲基二醇、聚四亞甲基二醇等。就賦予柔軟性、低熔融黏度化方面,為聚四亞甲基二醇最佳。Specific examples of the polyalkylene glycol component used for the soft segment include polyethylene glycol, polytrimethylene glycol, polytetramethylene glycol, and the like. Polytetramethylene glycol is the best in terms of imparting flexibility and lowering melt viscosity.
本發明所使用的聚酯樹脂(A)為非晶性或結晶性均無妨,但宜為結晶性。本發明中結晶性係指使用差示掃描型熱量計(DSC),以20℃/min之昇溫速度加熱熔融至230℃,然後,使用液態氮以20℃/min冷卻至-130℃,保持5分鐘後,從-130℃至230℃以20℃/min之昇溫速度進行昇溫時,該二次的昇溫步驟之任一次中有展現明確的熔解峰部者。另一方面,非晶性係指任一昇溫步驟均未展現熔解峰部者。The polyester resin (A) used in the present invention may be amorphous or crystalline, but is preferably crystalline. Crystallinity in the present invention refers to using a differential scanning calorimeter (DSC), heating and melting at a heating rate of 20°C/min to 230°C, and then cooling to -130°C with liquid nitrogen at a rate of 20°C/min, and keeping for 5 Minutes later, when the temperature was raised from -130° C. to 230° C. at a heating rate of 20° C./min, any one of the second heating steps showed a clear melting peak. On the other hand, the term "amorphous" means that no melting peak is exhibited in any temperature raising step.
<二聚酸聚醯胺(B)> 本發明之樹脂組成物含有二聚酸聚醯胺(B)。二聚酸聚醯胺(B)係含有二聚酸作為構成單元之聚醯胺。藉由將二聚酸予以共聚合作為聚醯胺的酸成分,可維持聚醯胺的耐油性同時降低熔融黏度。因此,和聚酯樹脂(A)在樹脂組成物中可維持優良的耐油性同時賦予成形時的流動性。又,玻璃轉移溫度亦降低,耐低溫性亦優良。 <Dimer acid polyamide (B)> The resin composition of the present invention contains dimer acid polyamide (B). Dimer acid polyamide (B) is a polyamide containing dimer acid as a constituent unit. By copolymerizing the dimer acid as the acid component of the polyamide, the oil resistance of the polyamide can be maintained while the melt viscosity can be reduced. Therefore, fluidity during molding can be imparted while maintaining excellent oil resistance in the resin composition together with the polyester resin (A). In addition, the glass transition temperature is also lowered, and the low temperature resistance is also excellent.
本發明所使用的二聚酸聚醯胺(B)之玻璃轉移溫度宜為-20℃以下,為-30℃以下更佳。The glass transition temperature of the dimer acid polyamide (B) used in the present invention is preferably below -20°C, more preferably below -30°C.
本發明所使用的二聚酸聚醯胺(B)為了使熱劣化盡可能不發生而予以成形,要求在210~240℃之快速的熔融。因此,二聚酸聚醯胺(B)的軟化點宜為210℃以下,為200℃以下更佳。考慮在常溫下的操作性及通常的耐熱性的話,二聚酸聚醯胺(B)的軟化點宜為90℃以上,為100℃以上更佳,為110℃以上再更佳,為120℃以上特佳,為130℃以上最佳。The dimer acid polyamide (B) used in the present invention requires rapid melting at 210 to 240°C in order to prevent thermal deterioration as much as possible and to mold it. Therefore, the softening point of the dimer acid polyamide (B) is preferably below 210°C, more preferably below 200°C. Considering the operability at room temperature and normal heat resistance, the softening point of the dimer acid polyamide (B) is preferably 90°C or higher, more preferably 100°C or higher, more preferably 110°C or higher, and 120°C The above is especially good, and the best is above 130°C.
本發明之樹脂組成物中,令聚酯樹脂(A)與二聚酸聚醯胺(B)的合計量為100質量份時,二聚酸聚醯胺(B)的含量宜為10質量份以上且50質量份以下,為20質量份以上且40質量份以下再更佳。二聚酸聚醯胺(B)的含量過少的話,有時會有樹脂組成物的熔融黏度上昇,且成形時的流動性惡化的情況,過多的話,有時會有在切削油浸漬下等長期試驗環境下之絕緣性惡化的情況。In the resin composition of the present invention, when the total amount of polyester resin (A) and dimer acid polyamide (B) is 100 mass parts, the content of dimer acid polyamide (B) is preferably 10 mass parts More preferably, it is more than 50 mass parts, and it is more preferably 20 mass parts or more and 40 mass parts or less. If the content of dimer acid polyamide (B) is too small, the melt viscosity of the resin composition may increase and the fluidity during molding may deteriorate. Insulation deterioration in the test environment.
<環氧樹脂(C)> 本發明之樹脂組成物含有環氧樹脂(C)。本發明所使用的環氧樹脂(C)若為1分子中具有1個以上之環氧基的化合物,則無特別限制。宜為數目平均分子量450~40,000之範圍內,且1分子中平均具有1.1個以上之環氧基的樹脂。可列舉例如:雙酚A二環氧丙醚、雙酚S二環氧丙醚、酚醛清漆樹脂環氧丙醚、溴化雙酚A二環氧丙醚等環氧丙醚型;六氫苯二甲酸環氧丙基酯、二聚酸環氧丙基酯等環氧丙基酯型;三環氧丙基異氰尿酸酯、環氧丙基乙內醯脲、四環氧丙基二胺基二苯基甲烷、三環氧丙基對胺基苯酚、三環氧丙基間胺基苯酚、二環氧丙苯胺、二環氧丙基甲苯胺、四環氧丙基間二甲苯二胺、二環氧丙基三溴苯胺、四環氧丙基雙胺基甲基環己烷等環氧丙基胺型;3,4-環氧環己基甲基羧酸酯、環氧化聚丁二烯、環氧化大豆油等脂環族或脂肪族環氧化物型等。可單獨使用它們,或合併使用2種以上。 <Epoxy resin (C)> The resin composition of this invention contains an epoxy resin (C). The epoxy resin (C) used in the present invention is not particularly limited as long as it is a compound having one or more epoxy groups in one molecule. It is preferably a resin having a number average molecular weight of 450 to 40,000 and having an average of 1.1 or more epoxy groups per molecule. Examples include glycidyl ether types such as bisphenol A diglycidyl ether, bisphenol S diglycidyl ether, novolak resin glycidyl ether, brominated bisphenol A diglycidyl ether, and hexahydrobenzene Glycidyl ester type such as glycidyl diformate and glycidyl dimer acid; triglycidyl isocyanurate, glycidyl hydantoin, tetraglycidyl di Aminodiphenylmethane, triglycidyl p-aminophenol, triglycidyl m-aminophenol, diglycidyl aniline, diglycidyl toluidine, tetraglycidyl m-xylene Amine, Diglycidyl tribromoaniline, tetraglycidyl bisaminomethyl cyclohexane and other glycidyl amine types; 3,4-epoxycyclohexyl methyl carboxylate, epoxidized polybutylene Cycloaliphatic or aliphatic epoxide type such as diene, epoxidized soybean oil, etc. These can be used individually or in combination of 2 or more types.
環氧樹脂(C)的軟化點宜為70℃以上,為80℃以上再更佳。軟化點低的話,有時會有在高溫(70℃以上)環境下之物性惡化的情況。The softening point of the epoxy resin (C) is preferably above 70°C, more preferably above 80°C. If the softening point is low, the physical properties may deteriorate in a high-temperature (70°C or higher) environment.
環氧樹脂(C)的數目平均分子量宜為450以上,為600以上更佳,為1000以上再更佳。數目平均分子量過小的話,有時會有樹脂組成物變得容易軟化,機械物性降低的情況。又,宜為40,000以下,為30,000以下更佳,為20,000以下再更佳。數目平均分子量過大的話,有時會有和聚酯樹脂(A)及二聚酸聚醯胺(B)之相容性降低,並損及密接性的情況。The number average molecular weight of the epoxy resin (C) is preferably not less than 450, more preferably not less than 600, and more preferably not less than 1000. When the number average molecular weight is too small, the resin composition may be easily softened and mechanical properties may be lowered. Moreover, it is preferably 40,000 or less, more preferably 30,000 or less, and more preferably 20,000 or less. When the number average molecular weight is too large, the compatibility with the polyester resin (A) and the dimer acid polyamide (B) may decrease, and the adhesiveness may be impaired.
本發明中,藉由將環氧樹脂(C)摻合於樹脂組成物中,在進行電氣電子零件之封裝時,可賦予良好的初始密接性、對切削油浸漬等環境負荷之密接耐久性、低黏度化所致之成形時的流動性之改善等優良的特性。據認為環氧樹脂(C)會發揮作為聚酯樹脂(A)與二聚酸聚醯胺(B)的相容劑之效果,此外會發揮因官能基導入所帶來的對基材之潤濕性改善的效果,進而改善絕緣性。本發明之樹脂組成物中的環氧樹脂(C)的含量,相對於聚酯樹脂(A)及二聚酸聚醯胺(B)的合計100質量份,宜為5質量份以上,為10質量份以上更佳,為20質量份以上再更佳。環氧樹脂(C)的摻合量未達5質量份時,有時會有作為聚酯樹脂(A)與二聚酸聚醯胺(B)的相容劑之作用亦無法展現的情況。又,宜為50質量份以下,為40質量份以下更佳。摻合50質量份以上之環氧樹脂(C)時,有時會有樹脂組成物之生產性差,此外封裝體之耐熱性等特性差的情況。In the present invention, by blending the epoxy resin (C) into the resin composition, it is possible to impart good initial adhesion, adhesion durability against environmental loads such as cutting oil immersion, and Excellent characteristics such as improvement of fluidity during molding due to low viscosity. It is thought that the epoxy resin (C) will function as a compatibilizer for the polyester resin (A) and the dimer acid polyamide (B), and it will also exert the moisturizing effect on the substrate due to the introduction of the functional group. Moisture improvement effect, thereby improving insulation. The content of the epoxy resin (C) in the resin composition of the present invention is preferably 5 parts by mass or more, 10 parts by mass relative to the total of 100 parts by mass of the polyester resin (A) and dimer acid polyamide (B). More preferably, it is more than 20 parts by mass, and even more preferably more than 20 parts by mass. When the compounding quantity of an epoxy resin (C) is less than 5 mass parts, the action|action as a compatibilizer of a polyester resin (A) and dimer acid polyamide (B) may not be exhibited also in some cases. Moreover, it is preferably at most 50 parts by mass, more preferably at most 40 parts by mass. When 50 parts by mass or more of the epoxy resin (C) is blended, the productivity of the resin composition may be poor, and properties such as heat resistance of the package may be poor.
<賦黏劑(D)> 本發明之樹脂組成物也可更含有賦黏劑(D)。本發明所使用的賦黏劑(D)無特別限制,可使用酚化合物、二甲苯改性酚醛樹脂、萜烯改性酚醛樹脂、將萜烯改性酚醛樹脂予以氫化處理而成的氫化萜烯改性酚醛樹脂等。 <Tackifier (D)> The resin composition of the present invention may further contain a tackifier (D). The tackifier (D) used in the present invention is not particularly limited, and phenolic compounds, xylene-modified phenolic resins, terpene-modified phenolic resins, and hydrogenated terpene obtained by hydrogenating terpene-modified phenolic resins can be used. Modified phenolic resin, etc.
本發明所使用的賦黏劑(D)之SP值宜為9.0(cal/cm 3) 1/2以上。SP值低的話,有時會有對燈油、切削油等之耐油性、機械特性差的情況。 The SP value of the tackifier (D) used in the present invention is preferably 9.0 (cal/cm 3 ) 1/2 or more. If the SP value is low, oil resistance to kerosene, cutting oil, etc., and mechanical properties may be poor.
本發明所使用的賦黏劑(D)宜具有羥基。賦黏劑(D)藉由具有羥基,可改善和基材之密接性並使絕緣性改善。賦黏劑(D)的羥值宜為1~500KOHmg/g,為30~400KOHmg/g更佳,為50~300KOHmg/g再更佳。The tackifier (D) used in the present invention preferably has a hydroxyl group. By having a hydroxyl group, the tackifier (D) can improve the adhesion with the substrate and improve the insulation. The hydroxyl value of the tackifier (D) is preferably 1-500KOHmg/g, more preferably 30-400KOHmg/g, even more preferably 50-300KOHmg/g.
本發明中,藉由將賦黏劑(D)摻合於樹脂組成物中,在電氣電子零件之封裝時,可賦予良好的黏接性。據認為賦黏劑(D)會發揮因官能基導入所帶來的對基材之潤濕性改善的效果。本發明中的賦黏劑(D)之摻合量,相對於聚酯樹脂(A)及二聚酸聚醯胺(B)的合計100質量份,宜為5質量份以上,為10質量份以上更佳,為20質量份以上再更佳。又,宜為50質量份以下,為40質量份以下再更佳。賦黏劑(D)的摻合比率過低的話,有時會有無法展現良好的黏接性之情況。又,賦黏劑(D)的摻合比率過高的話,有時會有伴隨彈性模量的上昇,樹脂柔軟性降低並對黏接性造成不良影響、或賦黏劑(D)的官能基和摻合物進行反應並使樹脂脆化的情況。In the present invention, by blending the tackifier (D) into the resin composition, good adhesiveness can be imparted in the encapsulation of electric and electronic parts. It is considered that the tackifier (D) exerts the effect of improving the wettability of the substrate due to the introduction of the functional group. The blending amount of the tackifier (D) in the present invention is preferably at least 5 parts by mass and 10 parts by mass with respect to the total of 100 parts by mass of the polyester resin (A) and dimer acid polyamide (B). More preferably, it is more preferably 20 parts by mass or more. Moreover, it is preferably at most 50 parts by mass, more preferably at most 40 parts by mass. When the blending ratio of the tackifier (D) is too low, good adhesiveness may not be exhibited in some cases. In addition, if the blending ratio of the tackifier (D) is too high, the flexibility of the resin may be lowered with an increase in the elastic modulus, which may adversely affect the adhesiveness, or the functional group of the tackifier (D) may A condition that reacts with the blend and embrittles the resin.
<抗氧化劑(E)> 本發明之樹脂組成物也可更含有抗氧化劑(E)。本發明所使用的抗氧化劑(E)若為可防止聚酯樹脂(A)之氧化者,則無特別限制,可使用受阻酚系抗氧化劑、磷系抗氧化劑、硫醚系抗氧化劑等。例如,受阻酚系可列舉:1,3,5-參(3,5-二(三級丁基)-4-羥基苄基)異氰尿酸酯、1,1,3-三(4-羥基-2-甲基-5-三級丁基苯基)丁烷、1,1-雙(3-三級丁基-6-甲基-4-羥基苯基)丁烷、3,5-雙(1,1-二甲基乙基)-4-羥基苯丙酸、季戊四醇肆(3,5-二(三級丁基)-4-羥基苯基)丙酸酯、3-(1,1-二甲基乙基)-4-羥基-5-甲基苯丙酸、3,9-雙[1,1-二甲基-2-[(3-三級丁基-4-羥基-5-甲基苯基)丙醯氧基]乙基]-2,4,8,10-四氧雜螺[5.5]十一烷、1,3,5-三甲基-2,4,6-參(3’,5’-二(三級丁基)-4’-羥基苄基)苯;磷系可列舉:3,9-雙(對壬基苯氧基)-2,4,8,10-四氧雜-3,9-二磷雜螺[5.5]十一烷、3,9-雙(十八烷氧基)-2,4,8,10-四氧雜-3,9-二磷雜螺[5.5]十一烷、三(單壬基苯基)亞磷酸酯、三苯氧基膦、亞磷酸異癸酯、亞磷酸異癸基苯酯、亞磷酸二苯基-2-乙基己酯、二壬基苯基雙(壬基苯基)酯亞磷酸、1,1,3-參(2-甲基-4-二(十三烷基)亞磷酸酯-5-三級丁基苯基)丁烷、參(2,4-二(三級丁基)苯基)亞磷酸酯、新戊四醇雙(2,4-二(三級丁基)苯基亞磷酸酯)、2,2’-亞甲基雙(4,6-二(三級丁基)苯基)2-乙基己基亞磷酸酯、雙(2,6-二(三級丁基)-4-甲基苯基)新戊四醇二亞磷酸酯;硫醚系可列舉:4,4’-硫代雙[2-三級丁基-5-甲基苯酚]雙[3-(十二烷基硫代)丙酸酯]、硫代雙[2-(1,1-二甲基乙基)-5-甲基-4,1-伸苯基]雙[3-(十四烷基硫代)-丙酸酯]、新戊四醇肆(3-正十二烷基硫代丙酸酯)、雙(十三烷基)硫代二丙酸酯,可單獨使用它們,或可複合使用。 <Antioxidant (E)> The resin composition of the present invention may further contain an antioxidant (E). The antioxidant (E) used in the present invention is not particularly limited as long as it can prevent oxidation of the polyester resin (A), and hindered phenolic antioxidants, phosphorus antioxidants, thioether antioxidants and the like can be used. For example, hindered phenols include: 1,3,5-paraffin (3,5-bis(tertiary butyl)-4-hydroxybenzyl) isocyanurate, 1,1,3-tris(4- Hydroxy-2-methyl-5-tertiary butylphenyl) butane, 1,1-bis(3-tertiary butyl-6-methyl-4-hydroxyphenyl) butane, 3,5- Bis(1,1-dimethylethyl)-4-hydroxyphenylpropionic acid, pentaerythritol tetrakis(3,5-bis(tertiary butyl)-4-hydroxyphenyl)propionate, 3-(1, 1-Dimethylethyl)-4-hydroxy-5-methylphenylpropanoic acid, 3,9-bis[1,1-dimethyl-2-[(3-tertiary butyl-4-hydroxy- 5-methylphenyl)propionyloxy]ethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane, 1,3,5-trimethyl-2,4,6 - Refer to (3',5'-bis(tertiary butyl)-4'-hydroxybenzyl)benzene; phosphorus system can include: 3,9-bis(p-nonylphenoxy)-2,4,8 ,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis(octadecyloxy)-2,4,8,10-tetraoxa-3,9 -Diphosphaspiro[5.5]undecane, tris(monononylphenyl)phosphite, triphenoxyphosphine, isodecylphosphite, isodecylphenylphosphite, diphenylphosphite- 2-ethylhexyl ester, dinonylphenyl bis(nonylphenyl)phosphite, 1,1,3-paraffin(2-methyl-4-bis(tridecyl)phosphite-5 -Tertiary butylphenyl) butane, ginseng (2,4-bis(tertiary butyl)phenyl) phosphite, neopentylthritol bis(2,4-bis(tertiary butyl)phenyl) Phosphite), 2,2'-methylene bis(4,6-bis(tertiary butyl)phenyl) 2-ethylhexyl phosphite, bis(2,6-bis(tertiary butyl) )-4-methylphenyl) neopentylthritol diphosphite; thioether can be listed: 4,4'-thiobis[2-tertiary butyl-5-methylphenol]bis[3- (Dodecylthio)propionate], Thiobis[2-(1,1-dimethylethyl)-5-methyl-4,1-phenylene]bis[3-(deca Tetraalkylthio)-propionate], neopentylthritol tetra(3-n-dodecylthiopropionate), bis(tridecyl)thiodipropionate, they can be used alone , or can be used in combination.
抗氧化劑(E)的含量相對於聚酯樹脂(A)及二聚酸聚醯胺(B)的合計100質量份,宜為0.1質量份以上,為0.2質量份以上更佳,為0.3質量份以上再更佳。含量過少的話,有時會有對高溫下之長期耐久性造成不良影響的情況。又,宜為5質量份以下,為3質量份以下更佳,為1質量份以下再更佳。含量過多的話,有時會有對黏接性、阻燃性等造成不良影響的情況。The content of the antioxidant (E) is preferably 0.1 parts by mass or more, more preferably 0.2 parts by mass or more, and 0.3 parts by mass relative to the total of 100 parts by mass of the polyester resin (A) and dimer acid polyamide (B). The above is even better. If the content is too small, it may adversely affect the long-term durability at high temperature. Moreover, it is preferably at most 5 parts by mass, more preferably at most 3 parts by mass, and even more preferably at most 1 part by mass. When the content is too large, it may adversely affect adhesiveness, flame retardancy, and the like.
<樹脂組成物> 本發明之樹脂組成物係至少含有前述聚酯樹脂(A)、二聚酸聚醯胺(B)、及環氧樹脂(C),並因應需要含有賦黏劑(D)、抗氧化劑(E)之組成物。在此,封裝係指為了使精密零件等防塵、防水而以不接觸外部環境氣體的方式無間隙地包覆。本發明之樹脂組成物由於長期可靠性優良,故適於精密零件之中尤其電氣電子零件之封裝用途。 <Resin composition> The resin composition of the present invention contains at least the aforementioned polyester resin (A), dimer acid polyamide (B), and epoxy resin (C), and if necessary, contains tackifier (D), antioxidant (E ) composition. Here, the term "encapsulation" refers to covering without gaps so as not to expose precision parts and the like to dust and water. The resin composition of the present invention is suitable for encapsulation of electrical and electronic parts among precision parts because of its excellent long-term reliability.
本發明之樹脂組成物中,也可將不屬於本發明之聚酯樹脂(A)、二聚酸聚醯胺(B)、環氧樹脂(C)、賦黏劑(D)中任一者之聚酯、聚醯胺、聚烯烴、聚碳酸酯、丙烯酸系樹脂、乙烯乙酸乙烯酯等其它樹脂;異氰酸酯化合物、三聚氰胺等硬化劑;滑石(talc)、雲母等填充材;碳黑、氧化鈦等顏料;三氧化銻、溴化聚苯乙烯等阻燃劑,以不損及本發明之效果的範圍予以摻合,亦完全無礙。藉由摻合這些成分,有時會有改良黏接性、柔軟性、耐久性等之情況。此時的聚酯樹脂(A)相對於本發明之樹脂組成物整體,宜含有50質量%以上,含有55質量%以上更佳,含有60質量%以上再更佳。聚酯樹脂(A)的含量未達50質量%的話,會有聚酯樹脂(A)本身具有的優良之對電氣電子零件的黏接性、黏接耐久性、柔軟性降低的傾向。In the resin composition of the present invention, any one of the polyester resin (A), dimer acid polyamide (B), epoxy resin (C), and tackifier (D) that does not belong to the present invention can also be used Polyester, polyamide, polyolefin, polycarbonate, acrylic resin, ethylene vinyl acetate and other resins; isocyanate compounds, melamine and other hardeners; talc (talc), mica and other fillers; carbon black, titanium oxide Pigments such as antimony trioxide, brominated polystyrene and other flame retardants are blended within the range that does not impair the effect of the present invention, and there is no problem at all. Adhesiveness, flexibility, durability, etc. may be improved by blending these components. At this time, the polyester resin (A) is preferably contained at least 50% by mass, more preferably at least 55% by mass, and even more preferably at least 60% by mass, based on the entire resin composition of the present invention. If the content of the polyester resin (A) is less than 50% by mass, the excellent adhesiveness, adhesion durability, and flexibility to electrical and electronic parts that the polyester resin (A) itself possesses tend to decrease.
此外,本發明之樹脂組成物要求耐候性時,宜添加光安定劑。光安定劑可列舉例如:苯并三唑系光安定劑、二苯甲酮系光安定劑、受阻胺系光安定劑、鎳系光安定劑、苯甲酸酯系光安定劑等。苯并三唑系光安定劑可列舉:2-(3,5-二(三級戊基)-2’羥基苯基)苯并三唑、2-(2-羥基-5-三級辛基苯基)苯并三唑、2-(2’-羥基-3’-三級丁基-5’-甲基苯基)-5-氯苯并三唑、2-(2H-苯并三唑-2-基)對甲酚、2-(2’-羥基-5’-甲基苯基)苯并三唑、2,4-二(三級丁基)-6-(5-氯苯并三唑-2-基)苯酚、2-[2-羥基-3,5-二(1,1-二甲基苄基)]-2H-苯并三唑等。二苯甲酮系光安定劑可列舉:2-羥基-4-(辛氧基)二苯甲酮、2,4-二羥基二苯甲酮、2-羥基-4-甲氧基二苯甲酮、2-羥基-4-甲氧基二苯甲酮、2-羥基-4-甲氧基-二苯甲酮-5-磺酸、2-羥基-4-正十二烷氧基二苯甲酮、雙(5-苯甲醯基-4-羥基-2-甲氧基苯基)甲烷、2-2’-二羥基-4-甲氧基二苯甲酮、2,2’-二羥基-4,4’-二甲氧基二苯甲酮等。受阻胺系光安定劑可列舉:雙(2,2,6,6-四甲基-4-哌啶基)癸二酸、琥珀酸二甲酯/1-(2-羥基乙基)-4-羥基-2,2,6,6-四甲基哌啶聚縮物、聚[{6-(1,1,3,3-四甲基丁基)胺基-1,3,5-三𠯤-2,4-二基}{(2,2,6,6-四甲基-4-哌啶基)亞胺基}六亞甲基(2,2,6,6-四甲基-4-哌啶基)亞胺基}]、1,3,5-參(3,5-二(三級丁基)-4-羥基苄基)-均三𠯤-2,4,6(1H,3H,5H)三酮、參(4-三級丁基-3-羥基-2,6-二甲基苄基-均三𠯤-2,4,6-(1H,3H,5H)三酮等。鎳系光安定劑可列舉:[2,2’-硫代-雙(4-三級辛基酚根)]-2-乙基己基胺-鎳-(II)、鎳二丁基二硫代胺甲酸鹽、[2’,2’-硫代-雙(4-三級辛基酚根)]正丁基胺-鎳等。苯甲酸酯系光安定劑可列舉:2,4-二(三級丁基)苯基-3,5’-二(三級丁基)‐4’‐羥基苯甲酸酯等。這些光安定劑可單獨使用或複合使用。添加時的添加量相對於樹脂組成物整體,宜為0.1質量%以上且5質量%以下。未達0.1質量%的話,有時會有缺乏耐侯性效果之情況。超過5質量%的話,有時會有對黏接性等造成不良影響之情況。In addition, when the resin composition of the present invention requires weather resistance, it is advisable to add a light stabilizer. Examples of the photostabilizer include benzotriazole-based photostabilizers, benzophenone-based photostabilizers, hindered amine-based photostabilizers, nickel-based photostabilizers, and benzoate-based photostabilizers. Benzotriazole-based light stabilizers include: 2-(3,5-bis(tertiary pentyl)-2'hydroxyphenyl)benzotriazole, 2-(2-hydroxy-5-tertiary octyl Phenyl)benzotriazole, 2-(2'-hydroxy-3'-tertiary butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2H-benzotriazole -2-yl) p-cresol, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2,4-bis(tertiary butyl)-6-(5-chlorobenzo Triazol-2-yl)phenol, 2-[2-hydroxy-3,5-bis(1,1-dimethylbenzyl)]-2H-benzotriazole and the like. Benzophenone-based light stabilizers include: 2-hydroxy-4-(octyloxy)benzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone Ketone, 2-Hydroxy-4-methoxybenzophenone, 2-Hydroxy-4-methoxy-benzophenone-5-sulfonic acid, 2-Hydroxy-4-n-dodecyloxydiphenyl Methanone, bis(5-benzoyl-4-hydroxy-2-methoxyphenyl)methane, 2-2'-dihydroxy-4-methoxybenzophenone, 2,2'-bis Hydroxy-4,4'-dimethoxybenzophenone, etc. Hindered amine light stabilizers include bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacic acid, dimethyl succinate/1-(2-hydroxyethyl)-4 -Hydroxy-2,2,6,6-tetramethylpiperidine polycondensate, poly[{6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-tri 𠯤-2,4-diyl}{(2,2,6,6-tetramethyl-4-piperidinyl)imino}hexamethylene(2,2,6,6-tetramethyl- 4-piperidinyl)imino}], 1,3,5-ginseng (3,5-di(tertiary butyl)-4-hydroxybenzyl)-same tris-2,4,6(1H ,3H,5H)trione, ginseng(4-tertiary butyl-3-hydroxy-2,6-dimethylbenzyl-same-tri-2,4,6-(1H,3H,5H)trione etc. Nickel-based light stabilizers include: [2,2'-thio-bis(4-tertiary octylphenolate)]-2-ethylhexylamine-nickel-(II), nickel dibutyldi Thioamine formate, [2',2'-thio-bis(4-tertiary octylphenolate)] n-butylamine-nickel, etc. Benzoate-based light stabilizers include: 2, 4-di(tertiary butyl)phenyl-3,5'-bis(tertiary butyl)-4'-hydroxybenzoate, etc. These light stabilizers can be used alone or in combination. When adding The amount is preferably not less than 0.1% by mass and not more than 5% by mass relative to the entire resin composition. If it is less than 0.1% by mass, the effect of weather resistance may sometimes be lacking. If it exceeds 5% by mass, there may be adverse Potential adverse effects such as contact.
決定聚酯樹脂(A)之組成及組成比的方法可列舉例如:將聚酯樹脂(A)溶解於氘代氯仿等溶劑並進行測定之 1H-NMR或 13C-NMR、在聚酯樹脂(A)之甲醇醇解作用後進行測定之氣相層析所為之定量(以下有時簡稱為甲醇醇解作用-GC法)等。本發明中,有可溶解聚酯樹脂(A)而且適於 1H-NMR測定之溶劑時,則設定為以 1H-NMR來決定組成及組成比。無適當的溶劑時或僅以 1H-NMR測定無法決定組成比時,則設定為採用或併用 13C-NMR、甲醇醇解作用-GC法。 Methods for determining the composition and composition ratio of the polyester resin (A) include, for example, 1 H-NMR or 13 C-NMR in which the polyester resin (A) is dissolved in a solvent such as deuterated chloroform and measured, (A) Quantification by gas chromatography for measurement after methanolysis (hereinafter sometimes referred to as methanolysis-GC method), etc. In the present invention, when there is a solvent that can dissolve the polyester resin (A) and is suitable for 1 H-NMR measurement, the composition and composition ratio are determined by 1 H-NMR. When there is no suitable solvent or when the composition ratio cannot be determined only by 1 H-NMR measurement, 13 C-NMR and methanolysis-GC method are used or used in combination.
本發明之樹脂組成物在230℃的熔融黏度宜為5~1000dPa・s,可藉由適當地調整聚酯樹脂(A)、二聚酸聚醯胺(B)、環氧樹脂(C)、賦黏劑(D)、抗氧化劑(E)的種類及摻合比率來達成。例如,提高和聚酯樹脂(A)共聚合之聚醚二醇的共聚合比率、或降低聚酯樹脂(A)之分子量,會有朝降低本發明之樹脂組成物的熔融黏度之方向發揮作用的傾向,提高聚酯樹脂(A)的分子量,會有朝提高本發明之樹脂組成物的熔融黏度之方向發揮作用的傾向。另外,此處在230℃的熔融黏度係如下般進行測定而得的值。亦即,將樹脂組成物乾燥至含水率0.1%以下,然後利用島津製作所股份有限公司製流動測試儀(型號CFT-500C),使加溫至230℃且安定的樹脂組成物,以98N/cm 2之壓力通過具有1.0mm孔徑之厚度10mm的模具時的黏度之測定值。為1000dPa・s以上之高熔融黏度的話,雖然可獲得高樹脂凝聚力、耐久性,但封裝複雜的形狀之零件時需要高壓的射出成型,故有時會有發生破壞零件的情況。藉由使用具有1000dPa・s以下,宜為900dPa・s以下的熔融黏度之封裝用樹脂組成物,可用0.1~20MPa之較低的射出壓力獲得電氣絕緣性優良的封裝體(模具零件),同時亦不會損及電氣電子零件之特性。又,考慮封裝用樹脂組成物之注射操作的觀點,雖然在230℃的熔融黏度愈低愈佳,但考慮樹脂組成物之黏接性、凝聚力的話,下限宜為5dPa・s以上,為10dPa・s以上再更佳,為30dPa・s以上更佳,為50dPa・s以上最佳。 The melt viscosity of the resin composition of the present invention at 230°C is preferably 5~1000dPa・s, which can be obtained by properly adjusting polyester resin (A), dimer acid polyamide (B), epoxy resin (C), The type and blending ratio of tackifier (D) and antioxidant (E) can be achieved. For example, increasing the copolymerization ratio of the polyether diol copolymerized with the polyester resin (A) or reducing the molecular weight of the polyester resin (A) will act in the direction of lowering the melt viscosity of the resin composition of the present invention. There is a tendency to increase the molecular weight of the polyester resin (A), which tends to work in the direction of increasing the melt viscosity of the resin composition of the present invention. In addition, the melt viscosity at 230 degreeC here is the value measured as follows. That is, the resin composition was dried to a water content of 0.1% or less, and then heated to 230°C and stabilized with a flow tester (model CFT-500C) manufactured by Shimadzu Corporation, at a rate of 98N/cm The measured value of the viscosity when the pressure of 2 passes through a mold with a thickness of 10mm and a hole diameter of 1.0mm. If the melt viscosity is higher than 1000dPa・s, high resin cohesion and durability can be obtained, but when packaging parts with complex shapes, high-pressure injection molding is required, so parts may be damaged. By using a resin composition for encapsulation with a melt viscosity of 1000dPa・s or less, preferably less than 900dPa・s, a package (mold part) with excellent electrical insulation can be obtained at a relatively low injection pressure of 0.1~20MPa. Will not damage the characteristics of electrical and electronic components. Also, considering the injection operation of the resin composition for encapsulation, the lower the melt viscosity at 230°C, the better, but considering the adhesiveness and cohesion of the resin composition, the lower limit is preferably 5dPa・s or more, and 10dPa・ s or more is even better, 30dPa・s or more is more preferable, and 50dPa・s or more is the best.
本發明中,特定構件與封裝用樹脂組成物之封裝性,係藉由製作於金屬配線印刷基板上以形成封裝用樹脂組成物黏接而成的測定用樣本片,並測定其絕緣電阻值來判定。測定用試驗片之製作方法、絕緣電阻值之測定方法,係依循後述實施例所記載之方法來實施。In the present invention, the encapsulation properties of the specific member and the encapsulating resin composition are determined by manufacturing a measurement sample piece bonded with the encapsulating resin composition on a metal wiring printed circuit board, and measuring the insulation resistance value thereof. determination. The method of making the test piece for measurement and the method of measuring the insulation resistance value are carried out in accordance with the method described in the examples described later.
本發明之封裝用樹脂組成物,係藉由對已設置電氣電子零件之模具注射來成型。更具體而言,使用螺桿型之熱熔成型加工用器具(applicator)時,可於160~280℃前後進行加熱熔融,並通過射出噴嘴注入至模具,其後經過一定的冷卻時間後,將成型物從模具去除來獲得成型物。The resin composition for encapsulation of the present invention is molded by injection into a mold in which electrical and electronic components are placed. More specifically, when using a screw-type applicator for hot melt molding, it can be heated and melted at around 160~280°C, and injected into the mold through the injection nozzle, and then after a certain cooling time, the molding The object is removed from the mold to obtain a molded object.
熱熔成型加工用器具的型號並無特別限制,可列舉例如:Nordson公司製ST2、井元製作所製立式擠壓成型機IMC-18F9、日精樹脂工業公司製混合式小型立式射出成形機STX20等。 [實施例] The model of the hot-melt molding processing equipment is not particularly limited, and examples thereof include: ST2 manufactured by Nordson Corporation, vertical extrusion molding machine IMC-18F9 manufactured by Imoto Seisakusho, hybrid small vertical injection molding machine STX20 manufactured by Nissei Plastic Industry Co., Ltd., etc. . [Example]
為了更詳細地說明本發明而於下列舉實施例、比較例,但本發明不受實施例任何限定。另外,實施例、比較例所記載的各測定值係利用下列方法測得。In order to demonstrate this invention in more detail, although an Example and a comparative example are given below, this invention is not limited to an Example at all. In addition, each measured value described in an Example and a comparative example was measured by the following method.
<熔點、玻璃轉移溫度之測定> 以Seiko電子工業股份有限公司製之差示掃描熱量分析計「DSC220型」,將測定樣本5mg放入鋁盤,壓蓋密封,一次以20℃/min之昇溫速度加熱至230℃並熔融。然後,使用液態氮以20℃/min冷卻至-130℃,保持5分鐘後,從-130℃至230℃以20℃/min之昇溫速度進行測定。將得到的曲線中如圖1所示之於DSC表現反曲點的部分之得自於反曲點前的基線之切線(1)與得自於反曲點後的基線之切線(2)的交點定義為玻璃轉移溫度(Tg),並將吸熱峰部之極小點(圖內×記號)定義為熔點(Tm)。 <Measurement of melting point and glass transition temperature> Using the differential scanning calorimeter "DSC220" manufactured by Seiko Electronics Co., Ltd., put 5 mg of the measurement sample into an aluminum pan, seal it with a gland, and heat it up to 230°C at a heating rate of 20°C/min and melt it. Then, it was cooled to -130°C with liquid nitrogen at 20°C/min, held for 5 minutes, and measured at a heating rate of 20°C/min from -130°C to 230°C. In the obtained curve, as shown in Figure 1, the part of the DSC showing the inflection point is obtained from the tangent line (1) of the baseline before the inflection point and the tangent line (2) obtained from the baseline after the inflection point The intersection point is defined as the glass transition temperature (Tg), and the minimum point of the endothermic peak portion (marked with x in the figure) is defined as the melting point (Tm).
<聚合物的SP值> 聚合物的SP值藉由係利用Fedors之方法,將構成聚合物之單體之原子、原子團及聚合物聚合時所生成的鍵結之原子及原子團的已知之凝聚能量密度、莫耳分子容積積代入下式來算出。 δ=(Σe i/Σv i) 1/2(cal/cm 3) 1/2δ:SP值((cal/cm 3) 1/2) e i:原子及原子團的凝聚能量密度(cal/mol) v i:原子及原子團的莫耳分子容積(cm 3/mol) e i及v i使用Polym. Eng. Sci., 14[2], 147-154(1974)所記載之值。 <SP value of polymer> The SP value of a polymer is determined by the known aggregation energy of the atoms and atomic groups of the monomers constituting the polymer and the bonded atoms and atomic groups formed when the polymer is polymerized using the Fedors method. The density and the molar molecular volume were substituted into the following formula to calculate. δ=(Σe i /Σv i ) 1/2 (cal/cm 3 ) 1/2 δ: SP value ((cal/cm 3 ) 1/2 ) e i : Condensation energy density of atoms and atomic groups (cal/mol ) v i : molar molecular volume (cm 3 /mol) of atoms and atomic groups (cm 3 /mol) e i and v i use the values described in Polym. Eng. Sci., 14[2], 147-154 (1974).
<熔融特性(流動性)試驗> 聚酯樹脂(A)及樹脂組成物的熔融黏度之評價方法 利用島津製作所製之流動測試儀(CFT-500C型),於已設定至230℃的加熱體中央之缸體中填充已乾燥至含水率0.1%以下之聚酯樹脂(A)或樹脂組成物。填充經過1分鐘後,藉由柱塞對樣本施加荷重,以壓力1MPa從缸體底部之模具(孔徑:1.0mm,厚度:10mm)擠壓熔融的樣本,記錄柱塞的降下距離及降下時間,並算出熔融黏度。 基於熔融黏度如下般評價樹脂組成物的熔融特性。 評價基準 ◎:於230℃之熔融黏度未達500dPa・s 〇:於230℃之熔融黏度為500dPa・s以上且未達800dPa・s △:於230℃之熔融黏度為800dPa・s以上且未達1000dPa・s ×:於230℃之熔融黏度為1000dPa・s以上 <Melt characteristics (fluidity) test> Evaluation method of melt viscosity of polyester resin (A) and resin composition Using a flow tester (CFT-500C) manufactured by Shimadzu Corporation, fill the cylinder in the center of the heating body set to 230°C with the polyester resin (A) or resin composition that has been dried to a moisture content of 0.1% or less. After filling for 1 minute, apply a load to the sample by the plunger, extrude the molten sample from the mold (hole diameter: 1.0mm, thickness: 10mm) at the bottom of the cylinder with a pressure of 1MPa, and record the drop distance and time of the plunger. and calculate the melt viscosity. Based on the melt viscosity, the melting properties of the resin composition were evaluated as follows. Evaluation Benchmark ◎: The melt viscosity at 230°C does not reach 500dPa・s 〇: Melt viscosity at 230°C is more than 500dPa・s and less than 800dPa・s △: Melt viscosity at 230°C is above 800dPa・s and less than 1000dPa・s ×: Melt viscosity at 230°C is above 1000dPa・s
<切削油膨潤特性(切削油浸漬後的膨潤率)> 利用使用了立式射出成形機(日精樹脂股份有限公司製TH40E)之射出成形製作100mm×100mm×2mmt之樹脂組成物的平板。 射出成形條件設定為:成形樹脂溫度210℃、成型壓力20MPa、冷卻時間30秒、射出速度10mm/秒。從成形後的平板,使用試驗片沖孔刃片沖切出3支基於JIS K6251之啞鈴狀3號試驗片。然後,將試驗片於常溫(約25℃)浸漬在切削油(NIKKOCASTY公司製 HANGSTERFER S-500)中4週,在取出後立刻以游標卡尺測定試驗片的全長(約100mm),並利用下式求得切削油膨潤率。 切削油膨潤率(%)=(浸漬後之試驗片的全長(mm)-浸漬前之試驗片的全長(mm))÷浸漬前之試驗片的全長(mm)×100 基於切削油膨潤率如下般評價樹脂組成物的耐油性。 評價基準 ◎:切削油膨潤率未達0.5% 〇:切削油膨潤率為0.5%以上且未達1.0% ×:切削油膨潤率為1.0%以上 <Swelling properties of cutting oil (swelling ratio after immersion in cutting oil)> A flat plate of the resin composition of 100 mm×100 mm×2 mmt was produced by injection molding using a vertical injection molding machine (TH40E manufactured by Nissei Plastics Co., Ltd.). The injection molding conditions were set as follows: a molding resin temperature of 210°C, a molding pressure of 20 MPa, a cooling time of 30 seconds, and an injection speed of 10 mm/sec. From the formed flat plate, three dumbbell-shaped No. 3 test pieces based on JIS K6251 were punched out using a test piece punching blade. Then, the test piece was immersed in cutting oil (HANGSTERFER S-500 manufactured by NIKKOCASTY Co., Ltd.) at room temperature (about 25° C.) for 4 weeks, and the full length (about 100 mm) of the test piece was measured with a vernier caliper immediately after taking it out, and calculated by the following formula The swelling rate of cutting oil is obtained. Swelling rate of cutting oil (%)=(full length of test piece after immersion (mm) - full length of test piece before immersion (mm))÷full length of test piece before immersion (mm)×100 The oil resistance of the resin composition was evaluated as follows based on the cutting oil swelling ratio. Evaluation Benchmark ◎: Cutting oil swelling rate less than 0.5% 〇: Cutting oil swelling rate is 0.5% or more and less than 1.0% ×: Cutting oil swelling ratio is above 1.0%
<機械特性(切削油浸漬後的拉伸延伸性保持率)> 利用使用了立式射出成形機(日精樹脂股份有限公司製TH40E)之射出成形製作100mm×100mm×2mmt之樹脂組成物的平板。 射出成形條件設定為:成形樹脂溫度210℃、成型壓力20MPa、冷卻時間30秒、射出速度10mm/秒。從成形後的平板,使用沖切機沖切出3支基於JIS K6251之啞鈴狀3號試驗片。然後,將試驗片於常溫(約25℃)浸漬在切削油中4週,浸漬後,將表面的切削油擦去,使用AUTOGRAPH(股份有限公司島津製作所公司製AG-IS),以夾具間成為20mm的方式挾持啞鈴狀3號試驗片,並測定機械特性。拉伸速度設定為500mm/分鐘。拉伸延伸性保持率係使用下式算出。 拉伸延伸性保持率(%)=(切削油浸漬4週後之拉伸延伸性/成形初期之拉伸延伸性)×100 基於拉伸延伸性保持率如下般評價樹脂組成物的機械特性。 評價基準 ◎:拉伸延伸性保持率為90%以上 ○:拉伸延伸性保持率為70%以上至未達90% △:拉伸延伸性保持率為50%以上至未達70% ×:拉伸延伸性保持率未達50% <Mechanical properties (retention rate of tensile elongation after cutting oil immersion)> A flat plate of the resin composition of 100 mm×100 mm×2 mmt was produced by injection molding using a vertical injection molding machine (TH40E manufactured by Nissei Plastics Co., Ltd.). The injection molding conditions were set as follows: a molding resin temperature of 210°C, a molding pressure of 20 MPa, a cooling time of 30 seconds, and an injection speed of 10 mm/sec. From the formed flat plate, three dumbbell-shaped No. 3 test pieces based on JIS K6251 were punched out using a punching machine. Then, the test piece was immersed in cutting oil at room temperature (about 25° C.) for 4 weeks. After immersion, the cutting oil on the surface was wiped off, and using AUTOGRAPH (manufactured by Shimadzu Corporation AG-IS Co., Ltd.) The dumbbell-shaped No. 3 test piece was clamped in a 20 mm manner, and its mechanical properties were measured. The stretching speed was set at 500 mm/min. Tensile elongation retention was calculated using the following formula. Tensile elongation retention (%)=(tensile elongation after cutting oil immersion for 4 weeks/tensile elongation at the initial stage of forming)×100 Based on the retention of tensile elongation, the mechanical properties of the resin composition were evaluated as follows. Evaluation Benchmark ◎: Tensile elongation retention rate of more than 90% ○: Tensile elongation retention rate of 70% or more to less than 90% △: Tensile elongation retention rate of 50% or more to less than 70% ×: Tensile elongation retention rate is less than 50%
<絕緣特性(切削油浸漬後的絕緣電阻值)> 於焊接有氯乙烯製之外徑約1.45mm的絕緣電線之已印刷40mm×40mm× 1.6mm厚度之金屬配線的基板(基板:玻璃環氧樹脂)上,使用小型電動射出成型機(CANON ELECTRONICS股份有限公司製LS-300i)成形樹脂組成物,製得將金屬配線印刷部分及氯乙烯絕緣電線的一部分予以封裝而成的成形物。成形條件設定為:成形樹脂溫度230℃、成型壓力15MPa、冷卻時間10秒、射出速度6mm/秒。使用超絕緣電阻計SM-8220(日置電機股份有限公司製),以500V之施加電壓測定成形初期之樣本及將試驗片於常溫(約25℃)浸漬在切削油中4週並於浸漬後將表面的切削油擦去之樣本的絕緣電阻值。 基於絕緣電阻值如下般評價樹脂組成物的絕緣性。 評價基準 ◎:絕緣電阻值為100MΩ以上 ○:絕緣電阻值為70MΩ以上至未達100MΩ △:絕緣電阻值為50MΩ以上至未達70MΩ ×:絕緣電阻值未達50MΩ 另外,表2中,E+N表示10的N次方。例如:2.86E+03表示2.86×10的3次方(約為2860)。又,本測定中,2.09E+00為檢測極限最小值,≦2.09E+00表示為檢測極限以下。 <Insulation properties (insulation resistance value after cutting oil immersion)> A small electric injection molding machine (CANON ELECTRONICS Co., Ltd. Co., Ltd. LS-300i) molded resin composition, which is a molded product in which the printed part of the metal wiring and a part of the vinyl chloride insulated wire are encapsulated. The molding conditions were set as follows: a molding resin temperature of 230° C., a molding pressure of 15 MPa, a cooling time of 10 seconds, and an injection speed of 6 mm/sec. Using a super insulation resistance meter SM-8220 (manufactured by Hioki Electric Co., Ltd.), measure the sample at the initial stage of molding with an applied voltage of 500V, and immerse the test piece in cutting oil at room temperature (about 25°C) for 4 weeks. Insulation resistance value of samples wiped off by cutting oil on the surface. The insulation of the resin composition was evaluated as follows based on the insulation resistance value. Evaluation Benchmark ◎: The insulation resistance value is above 100MΩ ○: The insulation resistance value is more than 70MΩ to less than 100MΩ △: The insulation resistance value is above 50MΩ to less than 70MΩ ×: The insulation resistance value is less than 50MΩ In addition, in Table 2, E+N represents 10 to the Nth power. For example: 2.86E+03 means 2.86×10 to the third power (about 2860). In addition, in this measurement, 2.09E+00 is the minimum value of the detection limit, and ≦2.09E+00 means below the detection limit.
<聚酯樹脂(A)之製造例> 於裝備了攪拌機、溫度計、餾出用冷卻器之反應罐內添加對苯二甲酸1080質量份、間苯二甲酸582質量份、1,4-丁烷二醇1893質量份、鈦酸四丁酯1.9質量份,並於170~220℃實施2小時之酯化反應。酯化反應結束後,投入數目平均分子量1000的聚四亞甲基二醇「PTMG1000」(三菱化學公司製)1500質量份及受阻酚系抗氧化劑「IRGANOX 1330」(Ciba-Geigy公司製)3質量份,昇溫至255℃同時將反應系內慢慢地減壓,歷時60分鐘調整為255℃、665Pa。然後,再於133Pa以下實施30分鐘之聚縮合反應,獲得聚酯樹脂(A-1)。該聚酯樹脂(A-1)的熔融黏度、熔點、玻璃轉移溫度、SP值如表1所示。又,利用和聚酯樹脂(A-1)同樣的方法合成聚酯樹脂(A-2)、(A-3)。各別的組成及物性值如表1所示。 <Manufacturing example of polyester resin (A)> Add 1,080 parts by mass of terephthalic acid, 582 parts by mass of isophthalic acid, 1,893 parts by mass of 1,4-butanediol, and tetrabutyl titanate into a reaction tank equipped with a stirrer, a thermometer, and a cooler for distillation. 1.9 parts by mass, and carry out the esterification reaction at 170~220°C for 2 hours. After the esterification reaction, 1500 parts by mass of polytetramethylene glycol "PTMG1000" (manufactured by Mitsubishi Chemical Corporation) with a number average molecular weight of 1000 and 3 parts by mass of hindered phenolic antioxidant "IRGANOX 1330" (manufactured by Ciba-Geigy Co., Ltd.) Parts, while raising the temperature to 255°C, the pressure in the reaction system was gradually reduced, and adjusted to 255°C and 665Pa over 60 minutes. Then, polycondensation reaction was carried out at 133 Pa or less for 30 minutes to obtain polyester resin (A-1). Table 1 shows the melt viscosity, melting point, glass transition temperature, and SP value of the polyester resin (A-1). Moreover, polyester resin (A-2), (A-3) was synthesize|combined by the method similar to polyester resin (A-1). The respective compositions and physical properties are shown in Table 1.
[表1]
表1中的縮寫如下所述。 TPA:對苯二甲酸 IPA:間苯二甲酸 AA:己二酸 NDC:2,6-萘二甲酸 EG:乙二醇 BD:1,4-丁烷二醇 CHDM:環己烷二甲醇 PTMG1000:聚四亞甲醚二醇(數目平均分子量1000) PTMG2000:聚四亞甲醚二醇(數目平均分子量2000) The abbreviations in Table 1 are as follows. TPA: Terephthalic acid IPA: Isophthalic acid AA: adipic acid NDC: 2,6-naphthalene dicarboxylic acid EG: ethylene glycol BD: 1,4-butanediol CHDM: Cyclohexanedimethanol PTMG1000: polytetramethylene ether glycol (number average molecular weight 1000) PTMG2000: polytetramethylene ether glycol (number average molecular weight 2000)
藉由以表2所記載之比例,使用雙軸擠壓機於模具溫度160℃~220℃中熔融混練聚酯樹脂(A)、二聚酸聚醯胺(B)、環氧樹脂(C)、賦黏劑(D)、抗氧化劑(E)來獲得樹脂組成物(S1)~(S18)。利用另外記載的方法評價樹脂組成物的熔融黏度、切削油膨潤性、機械特性、絕緣性。評價結果如下表2所示。By using the proportions recorded in Table 2, use a twin-screw extruder to melt and knead polyester resin (A), dimer acid polyamide (B), and epoxy resin (C) at a mold temperature of 160°C~220°C , tackifier (D), and antioxidant (E) to obtain resin compositions (S1)-(S18). The melt viscosity, cutting oil swelling property, mechanical properties, and insulation properties of the resin composition were evaluated by methods described separately. The evaluation results are shown in Table 2 below.
[表2-1]
[表2-2]
表2所使用的二聚酸聚醯胺(B)、環氧樹脂(C)、賦黏劑(D)、抗氧化劑(E)係為如下。 二聚酸聚醯胺(B-1):PA673,Henkel公司製,軟化點:185℃,Tg:-45℃ 二聚酸聚醯胺(B-2):PA6839,Henkel公司製,軟化點:195℃,Tg:-30℃ 聚醯胺(B-3):GLAMIDE T-802,東洋紡(股)製,熔點:220℃,Tg:50℃ 環氧樹脂(C-1):jER(註冊商標)1007K,三菱化學(股)製,軟化點:128℃ 環氧樹脂(C-2):EPICLON(註冊商標)HP-7200HHH,DIC(股)製,軟化點:105℃ 賦黏劑 (D-1):YSPOLYSTARK125,YASUHARA CHEMICAL(股)製,羥值:約200KOHmg/g,SP值:9.3(cal/cm 3) 1/2,Tg:約70℃ 賦黏劑(D-2):YSPOLYSTART160,YASUHARA CHEMICAL(股)製,羥值:約60KOHmg/g,SP值:8.8(cal/cm 3) 1/2,Tg:約100℃ 抗氧化劑(E-1):IRGANOX(註冊商標)1010,BASF JAPAN(股)製 抗氧化劑(E-2):LUSMITLG,第一工業製藥(股)製 The dimer acid polyamide (B), epoxy resin (C), tackifier (D), and antioxidant (E) used in Table 2 are as follows. Dimer acid polyamide (B-1): PA673, manufactured by Henkel Corporation, softening point: 185°C, Tg: -45°C Dimer acid polyamide (B-2): PA6839, manufactured by Henkel Corporation, softening point: 195°C, Tg: -30°C Polyamide (B-3): GLAMIDE T-802, manufactured by Toyobo Co., Ltd., melting point: 220°C, Tg: 50°C Epoxy resin (C-1): jER (registered trademark ) 1007K, manufactured by Mitsubishi Chemical Corporation, softening point: 128°C epoxy resin (C-2): EPICLON (registered trademark) HP-7200HHH, manufactured by DIC Corporation, softening point: 105°C tackifier (D- 1): YSPOLYSTARK125, manufactured by YASUHARA CHEMICAL Co., Ltd., hydroxyl value: about 200KOHmg/g, SP value: 9.3 (cal/cm 3 ) 1/2 , Tg: about 70°C Tackifier (D-2): YSPOLYSTART160, YASUHARA CHEMICAL Co., Ltd., hydroxyl value: about 60KOHmg/g, SP value: 8.8 (cal/cm 3 ) 1/2 , Tg: about 100°C Antioxidant (E-1): IRGANOX (registered trademark) 1010, BASF Antioxidant (E-2) manufactured by JAPAN Co., Ltd.: LUSMITLG, manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.
由表2可明瞭,實施例1~12之樹脂組成物係熔融黏度、切削油膨潤性、機械特性、絕緣性之各種特性均為優良之結果。另一方面,比較例1不含二聚酸聚醯胺,故耐油性差,又,熔融特性及絕緣性亦差。比較例2~4不含環氧樹脂,故絕緣性差。比較例5使用的聚酯樹脂之SP值低,故耐油性降低。比較例6使用的聚醯胺不具有二聚酸成分,而熔融特性及絕緣性差。 [產業上利用性] It can be seen from Table 2 that the resin compositions of Examples 1 to 12 have excellent results in terms of melt viscosity, swelling property of cutting oil, mechanical properties, and insulation properties. On the other hand, since Comparative Example 1 does not contain dimer acid polyamide, it is poor in oil resistance, and also poor in melting properties and insulation. Since Comparative Examples 2 to 4 did not contain epoxy resin, their insulating properties were inferior. Since the SP value of the polyester resin used in Comparative Example 5 was low, the oil resistance was lowered. The polyamide used in Comparative Example 6 did not contain a dimer acid component, but had poor melting properties and insulating properties. [industrial availability]
本發明之樹脂組成物由於電子電子基板封裝時的熔融黏度低,對玻璃環氧樹脂基板、或PBT基板之黏接強度非常優良,且耐油性優良,故作為電氣電子零件封裝用樹脂組成物係為有用。又,本發明之電氣電子零件封裝體尤其黏接性、切削油膨潤性優良,故會抑制來自電氣電子零件之漏電,非常有用。本發明之電氣電子零件封裝體,例如作為汽車、通信、電腦、家電用途之各種連接器、導線(harness)、或電子零件、具有印刷基板之開關、感測器之模具成型品係為有用。The resin composition of the present invention has low melt viscosity when encapsulating electronic and electronic substrates, excellent bonding strength to glass epoxy resin substrates or PBT substrates, and excellent oil resistance, so it can be used as a resin composition system for encapsulating electrical and electronic parts. for useful. In addition, the electric and electronic component package of the present invention is especially excellent in adhesiveness and swelling property of cutting oil, so it can suppress leakage from electric and electronic components, which is very useful. The electrical and electronic component package of the present invention is useful as molded products of various connectors, harnesses for automobiles, communications, computers, and home appliances, or electronic components, switches with printed boards, and sensors, for example.
[圖1]圖1表示利用差示掃描熱量分析計測得的圖表之示意圖。[ Fig. 1] Fig. 1 is a schematic diagram showing a graph measured by a differential scanning calorimeter.
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