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CN101400715B - Liquid epoxy resin composition and adhesive using same - Google Patents

Liquid epoxy resin composition and adhesive using same Download PDF

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Publication number
CN101400715B
CN101400715B CN200780008387.3A CN200780008387A CN101400715B CN 101400715 B CN101400715 B CN 101400715B CN 200780008387 A CN200780008387 A CN 200780008387A CN 101400715 B CN101400715 B CN 101400715B
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epoxy resin
seconds
liquid epoxy
resin composition
adhesive
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CN101400715A (en
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谷口昌
渡边裕一
菊池秀树
松村泰男
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Somar Corp
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Somar Corp
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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Abstract

一种液态环氧树脂组合物，其至少含有环氧树脂和固化剂，150℃下固化60秒时的粘合强度(A)与150℃下固化1小时的粘合强度(B)的关系为0.6B<A。一种粘合剂，优选含有150℃下固化60秒时的粘合强度(A)与150℃下固化1小时的粘合强度(B)的关系为0.6B<A的液态环氧树脂组合物。A liquid epoxy resin composition, which contains at least epoxy resin and curing agent, the relationship between the adhesive strength (A) when curing for 60 seconds at 150°C and the adhesive strength (B) when curing for 1 hour at 150°C is: 0.6B<A. An adhesive, preferably containing a liquid epoxy resin composition in which the relationship between the bonding strength (A) when curing for 60 seconds at 150°C and the bonding strength (B) curing for 1 hour at 150°C is 0.6B<A .

Description

液态环氧树脂组合物及使用该组合物的粘合剂Liquid epoxy resin composition and adhesive using same

技术领域 technical field

本发明涉及一种适合用于表面安装的液态环氧树脂组合物以及使用该组合物的粘合剂，尤其涉及在将半导体、电子部件等部件固定到各种印刷基板上时，在很短的固化时间内使装载到各种印刷基板上的电子部件等可以保持不发生移位或剥离的状态，并且即便对于小型化的电子部件也能可靠地粘合固定的液态环氧树脂组合物以及使用该组合物的粘合剂。The present invention relates to a liquid epoxy resin composition suitable for surface mounting and an adhesive using the composition, especially relates to when fixing parts such as semiconductors and electronic parts to various printed substrates It is a liquid epoxy resin composition that can keep electronic components mounted on various printed circuit boards without displacement or peeling during the curing time, and can reliably adhere and fix even miniaturized electronic components, and its use The binder of the composition.

背景技术 Background technique

一直以来，使用含有环氧树脂组合物的粘合剂作为用于将表面安装用部件粘合固定在印刷基板上的粘合剂。作为这样的粘合剂，例如，公开了含有环氧树脂、胺类固化剂、作为触变剂(チキソ付

Figure G2007800083873D0001182737QIETU
Figure G2007800083873D0001182742QIETU
)的亲水性硅石微粒的粘合剂(参照专利文件1)、以及含有液态环氧树脂、胺类潜在固化剂、煅烧滑石、有机类流变添加剂的粘合剂(参照专利文件2)。Conventionally, adhesives containing epoxy resin compositions have been used as adhesives for bonding and fixing surface mount components to printed circuit boards. As such an adhesive, for example, an epoxy resin, an amine curing agent, a thixotropic agent (チキソフ
Figure G2007800083873D0001182737QIETU
Figure G2007800083873D0001182742QIETU
) of hydrophilic silica particles (refer to Patent Document 1), and a binder containing liquid epoxy resin, amine latent curing agent, calcined talc, and organic rheological additives (refer to Patent Document 2).

最近，含有半导体的电子部件以数据的大容量化、处理速度高速化等性能提高为目的，逐渐小型化、高密度化，反而还追求低成本化，进而开发出与以往不同的电子部件。由于这些电子部件表面(粘合面)的状态也越来越多样化，因此使用专利文件1、专利文件2中记载的粘合剂和其他以往粘合剂有时不能获得足够的粘附力，产业界迫切希望开发出能够发挥与电子部件的种类无关的稳定的粘附力的树脂组合物(粘合剂)。Recently, electronic components containing semiconductors have been gradually reduced in size and high in density for the purpose of increasing data capacity, increasing processing speed, and other performance improvements. On the contrary, they are also pursuing cost reduction, and electronic components that are different from conventional ones have been developed. Since the state of the surface (adhesive surface) of these electronic components is also becoming more and more diverse, the adhesives described in Patent Document 1 and Patent Document 2 and other conventional adhesives may not be able to obtain sufficient adhesive force. The world has been eager to develop a resin composition (adhesive) capable of exhibiting stable adhesive force regardless of the type of electronic component.

但是，以往一直采用JIS K6850作为此种粘附力的测定方法，在评价包括还使用了铝以外的其他材料作为表面安装用部件的片式电容器等在内的各种电子部件的耐久性时，已知使用该方法评价粘附力不能获得可信性高的评价。因此，对于含有片式电容器等的各种电子部件，一直采用使用推拉力计(push-pull gauge)进行测定的方法(参照专利文件3、4)。不言而喻，期待一种采用该方法评价时显示出一定水平以上的粘合强度的粘合剂。However, JIS K6850 has been used in the past as the measurement method of such adhesion force. When evaluating the durability of various electronic components including chip capacitors that use materials other than aluminum as surface mount components, It is known that evaluation of adhesive force by this method cannot obtain highly reliable evaluation. Therefore, a method of measuring various electronic components including chip capacitors and the like using a push-pull gauge has been used (see Patent Documents 3 and 4). Needless to say, an adhesive that exhibits a certain level or higher of adhesive strength when evaluated by this method is desired.

专利文件1：日本特开平04-33916号公报Patent Document 1: Japanese Patent Application Laid-Open No. 04-33916

专利文件2：日本特开平07-316400号公报Patent Document 2: Japanese Patent Application Laid-Open No. 07-316400

专利文件3：日本特开平03-39378号公报Patent Document 3: Japanese Patent Application Laid-Open No. 03-39378

专利文件4：日本特开平10-27956号公报Patent Document 4: Japanese Patent Application Laid-Open No. 10-27956

发明内容 Contents of the invention

本发明以这些问题点作为课题，即、提供一种在短的固化时间内具有高粘附力、即便对于小型化的电子部件也能可靠地粘合固定、且可以获得与电子部件种类无关的足够的粘合强度的液态环氧树脂组合物以及使用该组合物的粘合剂。The present invention aims at these problems, that is, to provide a high adhesive force within a short curing time, which can be reliably bonded and fixed even to miniaturized electronic components, and which can be obtained regardless of the type of electronic components. A liquid epoxy resin composition of sufficient bond strength and an adhesive using the composition.

本发明人等为解决上述技术问题进行了深入的研究，结果发现，使用至少含有环氧树脂和固化剂的、固化时间和粘附力满足特定关系的液态环氧树脂组合物的粘合剂，在短时间内具有高粘附力，与尺寸和种类无关，对各种电子部件均可以获得高粘合强度，从而完成本发明。The inventors of the present invention have carried out in-depth research to solve the above-mentioned technical problems, and found that, using an adhesive of a liquid epoxy resin composition that contains at least an epoxy resin and a curing agent, a curing time and an adhesive force satisfy a specific relationship, It has high adhesive force in a short time, regardless of size and kind, and can obtain high adhesive strength to various electronic parts, thereby completing the present invention.

另外已知，关于适宜用于表面安装的液态环氧树脂组合物及使用该组合物的粘合剂，在含有片式电容器等的各种电子部件的性能评价时，以往使用被用作固化时间测定指标的凝胶化时间，因而不能提供具有充分性能的组合物。作为其理由之一，凝胶化时间只不过是显示交联开始时间的指标，对于含有片式电容器等的各种电子部件，粘合材料的固化时间通常在150℃下为60秒左右，因而，对于在这种条件下也能以显示出足够粘合强度的状态固化的环氧树脂组合物，研究结果显示，如果是可以满足以后述的反应率(reaction rate)规定的关系的初期反应率高的环氧树脂组合物，则可以与尺寸和种类无关，对各种电子部件均获得高粘合强度，从而完成了本发明。In addition, it is known that liquid epoxy resin compositions suitable for surface mounting and adhesives using the compositions have conventionally been used as the curing time when evaluating the performance of various electronic components including chip capacitors. The gelation time of the index was measured, so a composition with sufficient performance could not be provided. As one of the reasons, the gelation time is only an index showing the time at which crosslinking starts, and for various electronic components including chip capacitors, the curing time of the adhesive material is usually about 60 seconds at 150°C, so , for the epoxy resin composition that can also be cured in a state showing sufficient adhesive strength under this condition, the research results show that if the initial reaction rate can satisfy the relationship specified in the reaction rate (reaction rate) described later A high epoxy resin composition can obtain high adhesive strength to various electronic components regardless of the size and type, thereby completing the present invention.

即，本发明提供以下的液态环氧树脂组合物及使用该组合物的粘合剂。That is, the present invention provides the following liquid epoxy resin composition and an adhesive using the composition.

(1)一种液态环氧树脂组合物，其至少含有(a)环氧树脂、(b)固化剂，其特征在于，在涂布有阻焊剂(solder mask)和预涂熔剂(preflux)的基板上，使用分配器将该液态环氧树脂组合物以每点的涂布直径为0.7±0.15mm涂布2点后，将作为被粘合物的2012型矩形陶瓷电容器粘于涂布处，粘上后30秒内使基板表面温度升温至150℃后，保持60秒或1小时使之固化后放冷至23℃，在通过粘合试验来进行试验时，150℃的温度下保持时间为60秒时的粘附力(A)与保持1小时的粘附力(B)满足式0.6B<A规定的关系，所述粘合试验为使用推拉力计测定沿与部件长轴垂直的方向推动剥离时的强度。(1) A liquid epoxy resin composition, which contains at least (a) epoxy resin, (b) curing agent, is characterized in that, is coated with solder resist (solder mask) and pre-coating flux (preflux) On the substrate, use a dispenser to apply the liquid epoxy resin composition at a coating diameter of 0.7±0.15mm for 2 dots, and then stick a 2012-type rectangular ceramic capacitor as the adherend to the coating place, After sticking, raise the surface temperature of the substrate to 150°C within 30 seconds, hold it for 60 seconds or 1 hour to solidify, and let it cool to 23°C. When testing by adhesion test, the holding time at 150°C is The adhesion force (A) at 60 seconds and the adhesion force (B) maintained for 1 hour satisfy the relationship specified by the formula 0.6B<A. Strength when pushing to peel.

(2)根据前述(1)所述的液态环氧树脂组合物，其特征在于，前述粘附力(A)为30N以上。(2) The liquid epoxy resin composition according to (1) above, wherein the adhesive force (A) is 30N or more.

(3)根据前述(1)或(2)所述的液态环氧树脂组合物，其特征在于，将150℃的温度下使固化0秒、30秒、60秒、90秒时的液态环氧树脂组合物的各反应率分别计为α(0)、α(30)、α(60)、α(90)时，它们的关系由下式表示：(3) The liquid epoxy resin composition according to the aforementioned (1) or (2), wherein the liquid epoxy resin composition is cured at a temperature of 150° C. for 0 seconds, 30 seconds, 60 seconds, or 90 seconds. When each reaction rate of the resin composition is calculated as α(0), α(30), α(60), α(90) respectively, their relationship is expressed by the following formula:

[数1][number 1]

X＝[α(30)-α(0)]/[α(90)-α(60)]X=[α(30)-α(0)]/[α(90)-α(60)]

(式中，X为3以上、15以下)。(In the formula, X is not less than 3 and not more than 15).

(4)根据前述(1)～(3)中任一项所述的液态环氧树脂组合物，其特征在于，将130℃的温度下使固化0秒、30秒、60秒、90秒时的液态环氧树脂组合物的各反应率分别计为β(0)、β(30)、β(60)、β(90)时，它们的关系由下式表示：(4) The liquid epoxy resin composition according to any one of the aforementioned (1) to (3), wherein the epoxy resin composition is cured at a temperature of 130° C. for 0 seconds, 30 seconds, 60 seconds, or 90 seconds. When each reaction rate of the liquid epoxy resin composition is calculated as β (0), β (30), β (60), β (90) respectively, their relationship is expressed by the following formula:

[数2][number 2]

Y＝[β(30)-β(0)]/[β(90)-β(60)]Y=[β(30)-β(0)]/[β(90)-β(60)]

(式中，Y为2以上、10以下)。(In the formula, Y is 2 or more and 10 or less).

(5)根据前述(1)～(4)中任一项所述的液态环氧树脂组合物，其特征在于，150℃的温度下固化30秒的反应率γ(150)与80℃的温度下固化30秒的反应率γ(80)的比值Z〔γ(150)/γ(80)〕为10以上。(5) The liquid epoxy resin composition according to any one of the aforementioned (1) to (4), wherein the reaction rate γ(150) and the temperature of 80° C. The ratio Z[γ(150)/γ(80)] of the reaction rate γ(80) under curing for 30 seconds is 10 or more.

(6)根据前述(1)～(5)中任一项所述的液态环氧树脂组合物，其特征在于，采用依据JIS K6911的方法固化的试验片(固化条件：120℃下1小时，进而150℃下1小时)在20℃下的弯曲弹性模量为5×108～5×1010Pa的范围。(6) The liquid epoxy resin composition according to any one of the aforementioned (1) to (5), wherein a test piece cured according to the method of JIS K6911 is used (curing conditions: 1 hour at 120° C., Further, the flexural modulus at 20° C. at 150° C. for 1 hour) is in the range of 5×10 8 to 5×10 10 Pa.

(7)一种粘合剂，其特征在于，含有前述(1)～(6)中任一项所述的液态环氧树脂组合物。(7) An adhesive characterized by comprising the liquid epoxy resin composition described in any one of (1) to (6) above.

本发明中的反应率是指，使用后述的Mac Science公司(现为Bruker AXS公司(日本))生产的差示扫描量热计(DSC)，按照该装置所附的DSC小泽法(小沢法)软件的手册导出反应预测公式，基于该公式算出的特定时间下的反应率。另外，在计算反应率时，以新版热分析(小澤丈夫·神戸博太郎著·講談社サイエンテイフイツク

Figure G2007800083873D0004183124QIETU
)、T.OZAWA，J.Thermal Anal.2.301(1970)为参考。按照上述手册的记载，改变DSC的升温速度，求出各项物性数据，由该数据计算反应率。此时，通过利用在考虑到作为粘合剂的粘合操作性、耐用性而采用的特定温度下的各时间的反应率，可以有效地作为即使对更小型化、更高集成化的电子部件也可以在很短的固化时间内可靠地粘合固定、并且具有高粘附力的粘合组合物的筛选指标，从而完成本发明。用该方法求得的反应率与以凝胶化时间作为指标测定的推测固化程度的以往方法相比，误差减少，特别是如用于将片式电容器等表面安装用部件粘附固定于印刷基板上的粘合剂之类的、要求在短时间内固化的领域内使用时，能够更加正确地预测短时间内的固化程度，因而是优选的。The reaction rate in the present invention refers to the use of a differential scanning calorimeter (DSC) produced by Mac Science Corporation (now Bruker AXS Corporation (Japan)) described later, according to the DSC Ozawa method (Ozawa Ozawa) attached to the device. The manual of the software) derives the reaction prediction formula, and the reaction rate at a specific time is calculated based on the formula. In addition, when calculating the reaction rate, the new version of thermal analysis (written by Mr.
Figure G2007800083873D0004183124QIETU
), T. OZAWA, J. Thermal Anal. 2.301 (1970) for reference. According to the description in the above-mentioned manual, the temperature increase rate of DSC was changed, and the data of various physical properties were obtained, and the reaction rate was calculated from the data. At this time, by utilizing the reaction rate at each time at a specific temperature adopted in consideration of the adhesion workability and durability of the adhesive, it can be effectively used as an electronic component even for smaller and higher integration. It is also a screening index of an adhesive composition that can be reliably bonded and fixed within a short curing time and has a high adhesive force, thereby completing the present invention. The reaction rate obtained by this method has less error than the conventional method of estimating the degree of curing by using the gelation time as an indicator, especially for the adhesion and fixation of surface mount components such as chip capacitors to printed circuit boards. When used in a field requiring short-term curing, such as adhesives on the surface, it is preferable to predict the degree of curing in a short time more accurately.

本发明的液态环氧树脂组合物及使用该液态环氧树脂组合物的粘合剂，即具有快速固化性，还具有高粘合强度，同时可以防止伴随内部应力增加而发生的破裂等，因此可同时提高成品率和产品可靠性。这样，本发明的液态环氧树脂组合物可以提供特别是在将电子部件(包括半导体)等表面安装在印刷基板上时非常有用的粘合剂。The liquid epoxy resin composition of the present invention and the adhesive using the liquid epoxy resin composition have rapid curing properties and high adhesive strength, and can prevent cracks and the like from increasing internal stress. Therefore, Yield rate and product reliability can be improved at the same time. Thus, the liquid epoxy resin composition of the present invention can provide an adhesive that is very useful especially when surface-mounting electronic components (including semiconductors) and the like on a printed substrate.

具体实施方式 Detailed ways

以下，具体说明本发明的液态环氧树脂组合物及使用该液态环氧树脂组合物的粘合剂的最佳实施方式，但本发明并不限定于如下所述的方式。Hereinafter, although the liquid epoxy resin composition of this invention and the best mode of the adhesive agent using this liquid epoxy resin composition are demonstrated concretely, this invention is not limited to the form mentioned below.

环氧树脂epoxy resin

作为本发明中使用的环氧树脂，是1分子中具有2个以上的环氧基的树脂，例如可列举：双酚A型环氧树脂、双酚F型环氧树脂、酚醛型(phenol novolac)或甲酚醛型环氧树脂、脂环式环氧树脂、氢化双酚A型或AD型环氧树脂、丙二醇二缩水甘油醚、季戊四醇多缩水甘油醚等脂肪族类环氧树脂、由脂肪族或芳香族羧酸与环氧氯丙烷制得的环氧树脂、由脂肪族或芳香族胺与环氧氯丙烷制得的环氧树脂、杂环环氧树脂、含螺环的环氧树脂、环氧改性树脂、双酚S型环氧树脂、双苯酚(biphenol)型环氧树脂等。其中，优选常温下为液态的环氧树脂，但即使是常温下为固态，也可以通过将其溶解于常温下为液态的环氧树脂中而使用。另外，这些环氧树脂可以单独使用，也可以组合2种以上使用。从固化物的粘合性、电绝缘性、机械特性的平衡考虑，优选双酚A型环氧树脂和双酚F型环氧树脂。尤其优选双酚A型环氧树脂与双酚F型环氧树脂的混合物。The epoxy resin used in the present invention is a resin having two or more epoxy groups in one molecule, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type (phenol novolac type) ) or cresol type epoxy resin, alicyclic epoxy resin, hydrogenated bisphenol A type or AD type epoxy resin, propylene glycol diglycidyl ether, pentaerythritol polyglycidyl ether and other aliphatic epoxy resins, by aliphatic Or epoxy resins made from aromatic carboxylic acids and epichlorohydrin, epoxy resins made from aliphatic or aromatic amines and epichlorohydrin, heterocyclic epoxy resins, spiro-ring-containing epoxy resins, Epoxy-modified resins, bisphenol S-type epoxy resins, biphenol-type epoxy resins, and the like. Among these, epoxy resins that are liquid at normal temperature are preferable, but even if they are solid at normal temperature, they can be used by dissolving them in epoxy resins that are liquid at normal temperature. In addition, these epoxy resins may be used individually or in combination of 2 or more types. In view of the balance of adhesiveness, electrical insulation, and mechanical properties of the cured product, bisphenol A type epoxy resin and bisphenol F type epoxy resin are preferable. Especially preferred are mixtures of bisphenol A type epoxy resins and bisphenol F type epoxy resins.

固化剂Hardener

作为本发明的液态环氧树脂组合物中使用的固化剂，优选采用潜在性固化剂。作为潜在性固化剂，可以列举：用常温下为固态的改性胺化合物通过加热而活化的固化剂、以及在所期望的温度下可溶解或破坏的微囊中包含例如酸酐、咪唑类、酚类化合物、酰胺类等固化剂的微囊型潜在性固化剂等。这些固化剂可以单独使用，但从调节固化时间(反应性)和固化物的物性方面考虑，也可以组合2种以上使用。As the curing agent used in the liquid epoxy resin composition of the present invention, a latent curing agent is preferably used. Examples of latent curing agents include: curing agents activated by heating with a modified amine compound that is solid at room temperature, and microcapsules that are soluble or destroyed at a desired temperature containing, for example, acid anhydrides, imidazoles, phenols, etc. Microcapsule-type latent curing agent for curing agents such as compounds, amides, etc. These curing agents may be used alone, but may be used in combination of two or more from the viewpoint of adjusting the curing time (reactivity) and the physical properties of the cured product.

从固化时间(反应性)的调节和作为粘合剂时的粘度调节方面考虑，上述固化剂中更优选使用胺类潜在性固化剂。作为胺类潜在性固化剂，可以列举：2-十七烷基咪唑、2-苯基-4-甲基-5-羟甲基咪唑、2-苯基-4-苯甲基-5-羟甲基咪唑、2，4-二氨基-6-[2-甲基咪唑基-(1)]-乙基-5-三嗪以及该2，4-二氨基-6-[2-甲基咪唑基-(1)]-乙基-5-三嗪的异氰尿酸加合物等咪唑化合物等。Among the above-mentioned curing agents, it is more preferable to use an amine latent curing agent from the viewpoint of adjustment of curing time (reactivity) and viscosity adjustment when used as an adhesive. Examples of amine latent curing agents include: 2-heptadecylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4-benzyl-5-hydroxyl Methylimidazole, 2,4-diamino-6-[2-methylimidazolyl-(1)]-ethyl-5-triazine and the 2,4-diamino-6-[2-methylimidazole Imidazole compounds such as isocyanuric acid adducts of -(1)]-ethyl-5-triazine, etc.

作为胺加合物类化合物，例如，可以使用アミキユアPN-23、アミキユアPN-40J、アミキユアMY-24(均为味の

Figure G2007800083873D0005074655QIETU
フアインテクノ公司制造。アミキユア是注册商标)、ノバキユアHX-3721、ノバキユアHX-3741(均为旭化成ケミカルズ公司制造，ノバキユア为注册商标)等各种市售品。另外，作为螺缩醛类化合物，例如，可以列举CTU、ATU、CTU胍胺(均为味の
Figure 2007800083873100002G2007800083873D0005074655QIETU
フアインテクノ公司制造。)等。特别是，从固化物的粘合性良好、低温时的固化性和保存稳定性的平衡考虑，优选胺加合物类化合物。As the amine adduct compound, for example, Amiquia PN-23, Amiquia PN-40J, Amiquia MY-24 (both Miの
Figure G2007800083873D0005074655QIETU
Made by Fine Technology Co., Ltd. Various commercial products such as Amiquia (a registered trademark), Nobakua HX-3721, and Nobakua HX-3741 (all manufactured by Asahi Kasei Chemicals Co., Ltd., Nobakua is a registered trademark). In addition, as the spirocetal compound, for example, CTU, ATU, CTU guanamine (both are 味の
Figure 2007800083873100002G2007800083873D0005074655QIETU
Made by Fine Technology Co., Ltd. )wait. In particular, amine adduct-based compounds are preferable in view of good adhesiveness of the cured product, and a balance between curability at low temperature and storage stability.

所述潜在性固化剂，以常温下粉末状或混合在环氧树脂中的糊状等进行市售，优选其质量平均粒径在15μm以下，更优选在10μm以下。若粒径超过15μm，则短时间内的反应性、粘合强度难以提高，因而是不优选的。从快速固化性和粘合性的方面考虑，优选使用5μm以下的潜在性固化剂。The latent curing agent is commercially available in the form of powder or paste mixed with epoxy resin at room temperature, and preferably has a mass average particle size of 15 μm or less, more preferably 10 μm or less. When the particle size exceeds 15 μm, it is not preferable since the short-time reactivity and adhesive strength are difficult to improve. From the viewpoint of rapid curing and adhesiveness, it is preferable to use a latent curing agent with a thickness of 5 μm or less.

另外，固化剂的使用比例，相对于前述环氧树脂100质量份，优选为20～60质量份，更优选为36～50质量份的范围。这是由于，若不足20质量份，则固化性显著降低；若超过60质量份，则固化物的耐湿性和电学性能降低，同时粘度显著上升。这些潜在性固化剂可以单独使用，也可以组合2种以上使用。另外，在选择固化剂时，考虑到低温固化速度，利用采用推拉力计测定的粘合试验进行试验时，自然需要选择充分的量，以使150℃的温度下保持时间为60秒时的粘附力(A)和1小时保持时的粘附力(B)满足式0.6B<A所规定的关系。在将2种以上组合使用时，需要按照使仅使用一种固化剂时在150℃下30秒内具有50％以上反应率的固化剂在固化剂总量中占有优选至少50质量％以上、更优选60质量％的比例来选择固化剂。另外，由于双氰胺类固化剂在150℃下的固化速度一般较慢，故对于本发明的组合物，不优选作为主要的固化剂原料使用双氰胺类固化剂。当然，只要在满足作为本发明的组合物的要件的范围之内，出于提高保存稳定性、增强粘合强度的目的，当然可以添加双氰胺类固化剂。Moreover, the usage ratio of a hardening|curing agent is preferably 20-60 mass parts with respect to 100 mass parts of said epoxy resins, More preferably, it is the range of 36-50 mass parts. This is because if it is less than 20 parts by mass, the curability will significantly decrease; if it exceeds 60 parts by mass, the moisture resistance and electrical properties of the cured product will decrease, and the viscosity will increase significantly. These latent curing agents may be used alone or in combination of two or more. In addition, when selecting a curing agent, considering the low-temperature curing speed, it is naturally necessary to select a sufficient amount when using an adhesion test measured by a push-pull meter to make the viscosity when the holding time is 60 seconds at a temperature of 150°C. The adhesion force (A) and the adhesion force (B) when kept for 1 hour satisfy the relationship specified by the formula 0.6B<A. When two or more types are used in combination, it is necessary to make the curing agent having a reaction rate of 50% or more in 30 seconds at 150° C. account for at least 50 mass % or more of the total amount of curing agents, preferably at least 50 mass % or more, when only one curing agent is used. The curing agent is preferably selected at a ratio of 60% by mass. In addition, since the curing speed of dicyandiamide curing agent is generally slow at 150°C, it is not preferred to use dicyandiamide curing agent as the main curing agent raw material for the composition of the present invention. Of course, as long as the requirements of the composition of the present invention are satisfied, a dicyandiamide-based curing agent can of course be added for the purpose of improving storage stability and enhancing adhesive strength.

其他成分other ingredients

本发明的液态环氧树脂组合物中，根据需要可以加入其他添加剂。作为添加剂，例如，可以列举：熔融硅石(silica)、结晶性硅石、低α射线硅石、玻璃鳞片、玻璃珠、玻璃囊、滑石、氧化铝、硅酸钙、氢氧化铝、碳酸钙、硫酸钡、氧化镁、氮化硅、硼氮化物等无机填充剂、包括丙烯酸类树脂或聚酯类树脂、硅类树脂等树脂颗粒的填充剂、分子中至少具有一个环氧基、在常温常压下为低粘度的化合物，具体有苯基缩水甘油醚、聚乙二醇缩水甘油醚、聚丙二醇缩水甘油醚、甲基缩水甘油醚、丙基缩水甘油醚、季戊四醇聚缩水甘油醚、山梨醇聚缩水甘油醚、n-丁二醇缩水甘油醚、2-乙基己基缩水甘油基醚等反应性稀释剂、三苯基磷等的磷化合物、如三乙胺、四乙醇胺、1，8-二氮杂-二环[5.4.0]-7-十一碳烯(DBU)、N，N-二甲基苄胺、1，1，3，3-四甲基胍、2-乙基-4-甲基咪唑、N-甲基哌啶等的叔胺类化合物、例如1，8-二氮杂-二环[5.4.0]-7-十一碳烯基四苯基硼酸酯等硼类化合物等固化促进剂、腈橡胶、丁二烯橡胶等压力缓和剂、硅烷类偶联剂、钛酸酯类偶联剂、铝类偶联剂等偶联剂、染料和颜料等着色剂、抗氧化剂、耐湿性提高剂、触变剂、稀释剂、消泡剂、均化剂以及其他各种树脂。In the liquid epoxy resin composition of this invention, other additives can be added as needed. Examples of additives include fused silica, crystalline silica, low α-ray silica, glass flakes, glass beads, glass capsules, talc, alumina, calcium silicate, aluminum hydroxide, calcium carbonate, barium sulfate , magnesium oxide, silicon nitride, boron nitride and other inorganic fillers, fillers including acrylic resin or polyester resin, silicon resin and other resin particles, with at least one epoxy group in the molecule, under normal temperature and pressure It is a low viscosity compound, specifically phenyl glycidyl ether, polyethylene glycol glycidyl ether, polypropylene glycol glycidyl ether, methyl glycidyl ether, propyl glycidyl ether, pentaerythritol polyglycidyl ether, sorbitol polyglycidyl ether Glyceryl ether, reactive diluents such as n-butanediol glycidyl ether, 2-ethylhexyl glycidyl ether, phosphorus compounds such as triphenylphosphine, triethylamine, tetraethanolamine, 1,8-diazepine Hetero-bicyclo[5.4.0]-7-undecene (DBU), N,N-dimethylbenzylamine, 1,1,3,3-tetramethylguanidine, 2-ethyl-4- Tertiary amine compounds such as methylimidazole and N-methylpiperidine, boron compounds such as 1,8-diaza-bicyclo[5.4.0]-7-undecenyl tetraphenyl borate Compounds and other curing accelerators, nitrile rubber, butadiene rubber and other pressure relieving agents, silane coupling agents, titanate coupling agents, aluminum coupling agents and other coupling agents, dyes and pigments and other coloring agents, anti-corrosion Oxidizing agents, moisture resistance enhancers, thixotropic agents, thinners, defoamers, leveling agents, and various other resins.

其中，为改善组合物的粘度调节性，特别是在使用丝网印刷和分配器将本发明的液态环氧化树脂组合物作为粘合剂涂布时，反应性稀释剂是有效的。另外，从环氧树脂和填充剂的粘合性方面考虑，优选使用硅烷类偶联剂。反应性稀释剂的配合比例可以根据目标粘合剂的粘度适当选择，通常相对于环氧树脂100质量份，为0～20质量份的范围。另外，偶联剂的配合比例，通常相对于填充剂100质量份为0.25～2.0质量份的范围。但是，也可以将填充剂的表面事先用偶联剂处理后使用。Among them, a reactive diluent is effective for improving the viscosity controllability of the composition, especially when the liquid epoxy resin composition of the present invention is applied as an adhesive using screen printing and a dispenser. In addition, it is preferable to use a silane-based coupling agent from the viewpoint of the adhesiveness between the epoxy resin and the filler. The compounding ratio of a reactive diluent can be suitably selected according to the viscosity of the adhesive of interest, Usually, it is the range of 0-20 mass parts with respect to 100 mass parts of epoxy resins. In addition, the compounding ratio of a coupling agent is usually the range of 0.25-2.0 mass parts with respect to 100 mass parts of fillers. However, it is also possible to treat the surface of the filler with a coupling agent beforehand and use it.

本发明的液态环氧树脂组合物，可以通过混合环氧树脂、固化剂、根据需要加入的填充剂等各种添加剂而得到，本发明的粘合剂含有由这些成分构成的液态环氧树脂组合物。The liquid epoxy resin composition of the present invention can be obtained by mixing various additives such as an epoxy resin, a curing agent, and fillers added as needed. The adhesive of the present invention contains a liquid epoxy resin composition composed of these components. things.

由上述环氧树脂、固化剂及根据需要选用的填充剂等各种添加剂构成的液态环氧树脂组合物，在利用下述粘合试验进行试验时，60秒后的粘附力(A)和1小时后的粘附力(B)的关系满足0.6B<A。本发明发现，只要具有能满足这种关系的粘合特性，则作为生产包括片式电容器等各种电子部件时使用的粘合剂用原料的液态环氧树脂组合物就具有充分的实用性，基于该事实完成了本发明。When the liquid epoxy resin composition composed of the above-mentioned epoxy resin, curing agent and various additives such as fillers selected according to needs is tested by the following adhesion test, the adhesion force (A) and The relationship of the adhesive force (B) after 1 hour satisfies 0.6B<A. The present invention has found that as long as it has adhesive properties that satisfy this relationship, it has sufficient practicality as a liquid epoxy resin composition as a raw material for adhesives used in the production of various electronic components including chip capacitors, The present invention has been accomplished based on this fact.

即，本发明发现，通常，作为用于将表面安装部件粘附固定在印刷基板上的粘合剂，考虑到其生产性，需要能在150℃、60秒左右的短时间内固化，这时，如果某种程度反应率不够高，则有可能不能满足耐湿性等的要求水平，因而，需要通常固化结束1小时后的粘合强度的至少50％以上的强度、优选60％以上的强度，从而完成本发明。That is, the present inventors have found that generally, as an adhesive for adhering and fixing a surface mount component to a printed circuit board, it is necessary to be curable at 150° C. in a short period of time of about 60 seconds in consideration of its productivity. , if the reaction rate is not high enough to a certain extent, it may not be able to meet the required level of moisture resistance, etc. Therefore, usually at least 50% or more of the adhesive strength after curing is completed, preferably 60% or more. The present invention has thus been accomplished.

[粘合试验][Adhesion test]

将液态环氧树脂组合物用分配器在涂布有阻焊剂和预涂熔剂的基板上以1点的涂布直径为0.7±0.15mm涂布2点后，将作为被粘合物的2012型矩形陶瓷电容器安装在该组合物上。在安装后用30秒将基板的表面温度升至150℃后，保持60秒或1小时使固化，然后放冷至23℃，以推拉力计测定沿与部件长轴垂直的方向推动剥离时的强度。Use a dispenser to apply the liquid epoxy resin composition on the substrate coated with solder resist and pre-coated flux. After coating 2 points with a coating diameter of 0.7±0.15mm at 1 point, the 2012 type as the adherend Rectangular ceramic capacitors are mounted on this composition. After installation, it takes 30 seconds to raise the surface temperature of the substrate to 150°C, keep it for 60 seconds or 1 hour to solidify, then let it cool to 23°C, and use a push-pull gauge to measure the peeling force along the direction perpendicular to the long axis of the component. strength.

通过前述粘附力的关系满足0.6B<A，从而可以获得某种程度的粘附力，所述程度为即便在较短固化时间内也可以使电子部件等无移位或剥离地进入下一工序，在粘附力不满足所述关系的情况下，至得到所需粘附力为止的固化时间需要较长的时间，因而生产性降低，故是不优选的。尤其是在将电子部件等表面安装到印刷基板上时，由于优选在短时间内达到所需的强度水平，因而优选60秒后的粘附力(A)为30N以上，更优选为40N以上。By satisfying the relationship of the aforementioned adhesion force of 0.6B<A, it is possible to obtain a certain degree of adhesion force that allows electronic parts, etc. In the process, when the adhesive force does not satisfy the above-mentioned relationship, it takes a long time to cure until the desired adhesive force is obtained, which lowers productivity, which is not preferable. Especially when surface-mounting electronic components or the like on a printed circuit board, since it is preferable to achieve the required strength level in a short time, the adhesion (A) after 60 seconds is preferably 30N or more, more preferably 40N or more.

另外，本发明的液态环氧树脂组合物，将150℃下固化0秒、30秒、60秒、90秒时的液态环氧树脂组合物的各反应率分别计为α(0)、α(30)、α(60)、α(90)时，优选它们的关系(X)满足下式(I)。满足该关系的液态环氧树脂组合物中，固化操作时受周围环境的影响更少，且短时间内可以发挥一定水平以上的粘附力，因而是优选的。In addition, for the liquid epoxy resin composition of the present invention, each reaction rate of the liquid epoxy resin composition when curing at 150° C. for 0 second, 30 seconds, 60 seconds, and 90 seconds is respectively calculated as α(0), α( 30), α(60), and α(90), it is preferable that their relationship (X) satisfies the following formula (I). A liquid epoxy resin composition that satisfies this relationship is less affected by the surrounding environment during the curing operation and can exhibit a certain level or more of adhesive force in a short period of time, so it is preferable.

[数3][number 3]

X＝[α(30)-α(0)]/[α(90)-α(60)](I)X=[α(30)-α(0)]/[α(90)-α(60)](I)

(式中，X为3以上、15以下)(In the formula, X is 3 or more and 15 or less)

此时，虽然其理由尚未确定，但若X值不足3则固化物的耐湿性和绝缘性低下；超过15则固化速度过快，固化物容易发生变形。从固化物的耐湿性、绝缘性和变形抑制性的方面考虑，优选在5～15的范围内。At this time, although the reason has not been determined, if the X value is less than 3, the moisture resistance and insulation of the cured product will be low; if it exceeds 15, the curing speed will be too fast, and the cured product will easily deform. It is preferable to exist in the range of 5-15 from the viewpoint of the moisture resistance of hardened|cured material, insulation, and deformation|transformation suppression.

进而，本发明的液态环氧树脂组合物，将130℃的温度下固化0秒、30秒、60秒、90秒时的液态环氧树脂组合物的各反应率分别计为β(0)、β(30)、β(60)、β(90)时，优选它们的关系(Y)满足下式(II)。这是由于，满足这样关系的组合物适合在操作保证温度较低的特殊半导体包装的粘合操作中使用。Furthermore, in the liquid epoxy resin composition of the present invention, each reaction rate of the liquid epoxy resin composition when curing at a temperature of 130° C. for 0 seconds, 30 seconds, 60 seconds, and 90 seconds is respectively calculated as β(0), In the case of β(30), β(60), and β(90), it is preferable that their relationship (Y) satisfies the following formula (II). This is because a composition that satisfies such a relationship is suitable for use in bonding operations for special semiconductor packages where the operating guarantee temperature is low.

[数4][number 4]

Y＝[β(30)-β(0)]/[β(90)-β(60)]     (II)Y＝[β(30)-β(0)]/[β(90)-β(60)] (II)

(式中，Y为2以上、10以下)(In the formula, Y is 2 or more and 10 or less)

此时，Y不足2则固化物的耐湿性和绝缘性降低，超过10则固化速度过快，固化物容易发生变形。从固化物的耐湿性、绝缘性和变形抑制性的方面考虑，优选为2～7的范围。At this time, if Y is less than 2, the moisture resistance and insulation of the cured product will decrease, and if it exceeds 10, the curing speed will be too fast, and the cured product will easily deform. The range of 2-7 is preferable from the viewpoint of the moisture resistance, insulation, and deformation|transformation suppression properties of hardened|cured material.

本发明的液态环氧树脂组合物满足前述150℃下的各时间的反应率的关系X即可，但是，近年来，从包括全球变暖等环境问题及节约能源的观点出发，固化温度有降低的倾向，因此，通过控制更低的温度、尤其是130℃下的液态环氧树脂组合物的反应率、各时间点的反应率满足关系Y，从而可以获得固化温度无论是高温还是低温，粘合性、固化性均良好的液态环氧树脂组合物，因而是优选的。The liquid epoxy resin composition of the present invention may satisfy the above-mentioned relationship X of the reaction rate at each time at 150° C. However, in recent years, from the viewpoint of environmental problems including global warming and energy conservation, the curing temperature has decreased. Therefore, by controlling the reaction rate of the liquid epoxy resin composition at a lower temperature, especially at 130°C, the reaction rate at each time point satisfies the relationship Y, so that whether the curing temperature is high or low temperature, the viscosity A liquid epoxy resin composition having good compatibility and curability is preferable.

另外，本发明的液态环氧树脂组合物优选在150℃下固化30秒时的反应率γ(150)与80℃下固化30秒时的反应率γ(80)之比Z〔γ(150)/γ(80)〕为10以上。如果比值不足10，则80℃下反应就开始进行，因而保存性低下，或者150℃下60秒后的反应率降低，即，保存时和/或使用时的稳定性降低，因而是不优选的。从长期保存性及粘合性、快速固化性方面考虑，特别优选为12以上。In addition, the liquid epoxy resin composition of the present invention is preferably the ratio Z[γ(150) of the reaction rate γ(150) when curing for 30 seconds at 150°C to the reaction rate γ(80) when curing for 30 seconds at 80°C /γ(80)] is 10 or more. If the ratio is less than 10, the reaction starts at 80°C, so the storage stability is low, or the reaction rate after 60 seconds at 150°C is low, that is, the stability during storage and/or use is low, so it is not preferable. . In view of long-term storage properties, adhesiveness, and rapid curing properties, it is particularly preferably 12 or more.

前述式(I)中求得的X值在3以上、15以下、前述式(II)中求得的Y值在2以上、10以下，以及150℃的反应率和80℃的反应率之比Z为10以上的液态环氧树脂组合物，由于其初期(0秒～30秒)反应率高，因此在60秒后易于获得高粘附力，而且由于80℃的反应率低因而长期保存稳定性优异。其结果为，含有这种液态环氧树脂组合物的粘合剂不仅保存稳定性高，而且使用时也可以在短时间内将电子部件等被粘合物牢固地粘合，以较高地水平兼顾了保存性和粘合性这两种相反的效果。The X value obtained in the aforementioned formula (I) is between 3 and 15, the Y value obtained in the aforementioned formula (II) is between 2 and 10, and the ratio of the reaction rate at 150°C to the reaction rate at 80°C The liquid epoxy resin composition with Z being 10 or more has a high initial reaction rate (0 seconds to 30 seconds), so it is easy to obtain high adhesion after 60 seconds, and it is stable for long-term storage due to the low reaction rate at 80°C excellent. As a result, the adhesive containing this liquid epoxy resin composition not only has high storage stability, but also can firmly bond electronic parts and other adherends in a short period of time during use, achieving a high level of stability. There are two opposite effects of preservation and adhesion.

进而，本发明的液态环氧树脂组合物优选在下述的弹性模量测定试验中的弹性模量在5×108～5×1010Pa的范围内。Furthermore, the liquid epoxy resin composition of the present invention preferably has an elastic modulus in the elastic modulus measurement test described below in the range of 5×10 8 to 5×10 10 Pa.

[弯曲弹性模量试验][Bending modulus of elasticity test]

根据JIS K 6911的方法测定弯曲弹性模量。并且，试验片使用在120℃固化1小时后又在150℃固化1小时的样品。The flexural modulus of elasticity was measured according to the method of JIS K 6911. In addition, as a test piece, what was cured at 150 degreeC for 1 hour after hardening at 120 degreeC for 1 hour was used.

弯曲弹性模量不足5×108Pa而作为粘合剂使用时，在基板上表面安装的电子部件等容易发生位置偏移，其结果可能对操作不良等产品品质产生不良影响，另外，若超过5×1010Pa，则可能容易发生电子部件等由于冲击而脱落，导致产品品质变差，因而是不优选的。从产品品质方面考虑，优选弹性模量在1×109～7×109Pa的范围内。When the flexural modulus of elasticity is less than 5×10 8 Pa and used as an adhesive, positional displacement of electronic components etc. mounted on the upper surface of the substrate is likely to occur, and as a result, product quality such as handling failure may be adversely affected. If the pressure is less than 5×10 10 Pa, electronic components and the like may easily fall off due to impact, resulting in deterioration of product quality, which is not preferable. From the viewpoint of product quality, the elastic modulus is preferably in the range of 1×10 9 to 7×10 9 Pa.

粘合剂Adhesive

本发明的粘合剂可以通过将前述环氧树脂、固化剂、根据需要使用的填充剂等各种添加剂按照一定比例混合而得到，若环氧树脂在常温下为液态时可以直接混合而成，若环氧树脂在常温下为固态时可以将环氧树脂或者全部成分在溶剂中均匀混合而制成，但从保存稳定性和短时间的固化性方面考虑，优选按照以下方法配制。The adhesive of the present invention can be obtained by mixing various additives such as the aforementioned epoxy resin, curing agent, and filler used according to needs according to a certain ratio. If the epoxy resin is in a liquid state at normal temperature, it can be directly mixed. If the epoxy resin is solid at room temperature, it can be prepared by uniformly mixing the epoxy resin or all components in a solvent, but from the perspective of storage stability and short-term curing, it is preferable to prepare according to the following method.

(1)将液态环氧树脂或预先溶于甲苯、乙醇、溶纤剂、四氢呋喃、N-甲基-2-吡咯烷酮、二甲基甲酰胺等有机溶剂的环氧树脂、固化剂及填充剂等填充在搅拌机(例如行星式混合机或万能搅拌机等以往制造粘合剂时所使用的搅拌机)中。(1) Liquid epoxy resin or epoxy resin pre-dissolved in organic solvents such as toluene, ethanol, cellosolve, tetrahydrofuran, N-methyl-2-pyrrolidone, dimethylformamide, curing agent and filler, etc. It is filled in a mixer (such as a planetary mixer, a universal mixer, etc., which are conventionally used in the production of adhesives).

(2)在混合温度5～40℃、优选室温(23℃左右)的温度条件下均匀混合。另外，作为填充剂优选硅石，此时的配合量可以根据固化剂的碱性来适当选择，通常相对于固化剂1质量份，为0.05质量份以上，优选为0.07～0.5质量份的范围。硅石的配合量如果不足0.05质量份，则既使添加了硅石也难以得到均一的分散性等，因而是不优选的，另外，配合量过多也不优选。(2) Mix uniformly at a mixing temperature of 5 to 40°C, preferably at room temperature (about 23°C). In addition, silica is preferable as a filler, and the compounding amount at this time can be appropriately selected according to the basicity of the curing agent, and is usually 0.05 mass parts or more, preferably 0.07 to 0.5 mass parts, per 1 mass part of the curing agent. If the compounding quantity of silica is less than 0.05 mass part, since it will become difficult to obtain uniform dispersibility etc. even if silica is added, it is unpreferable, and it is also not preferable that the compounding quantity is too much.

本发明的粘合剂可适用于分配(dispense)方式、点转录方式、丝网印刷方式等各种涂布方法。作为示例，以分配方式说明使用本发明粘合剂的电子部件的固定方法。The adhesive of the present invention can be applied to various coating methods such as a dispense method, a dot transfer method, and a screen printing method. As an example, a method of fixing an electronic component using the adhesive of the present invention will be described in a dispensing manner.

(1)粘合剂的涂布(1) Coating of adhesive

在具有电路图的基板的电子部件的安装部位，用分配器涂布粘合剂。作为分配器，可以是螺栓式(通过螺栓的旋转排出粘合剂的方式)、空气式(用空气压力排出的方式)的任意一种方式。Adhesive is applied with a dispenser to the mounting portion of the electronic component on the substrate with the circuit pattern. The dispenser may be any of a bolt type (discharge adhesive by rotation of the bolt) and an air type (discharge by air pressure).

(2)电子部件的固定(2) Fixing of electronic components

然后，将电子部件放置在前述粘合剂上，在130～180℃的温度下固化30～60秒左右，固定部件。Then, the electronic component is placed on the aforementioned adhesive, and cured at a temperature of 130-180° C. for about 30-60 seconds to fix the component.

使用本发明的粘合剂时，由于加热后60秒内的粘附力和/或反应率高，可以在较短的固化时间内可靠地固定电子部件，因而成品率高，并且由于可以缩短进入下一道工序的时间，故工作效率、生产性均优异。另外，在下一道工序，例如焊接浸渍(solder dipping)工序中，由于粘合剂的形状没有改变，故可以抑制电子部件倾斜、移位等的发生，而且由于不易吸水，也可以防止电学性能下降。When using the adhesive of the present invention, due to the high adhesion and/or reaction rate within 60 seconds after heating, electronic parts can be reliably fixed in a short curing time, so the yield is high, and since the entry into The time for the next process is reduced, so the work efficiency and productivity are excellent. In addition, in the next process, such as the solder dipping process, since the shape of the adhesive does not change, the occurrence of tilting, displacement, etc. of electronic components can be suppressed, and the electrical performance can also be prevented from deteriorating because it is not easy to absorb water.

实施例Example

以下，使用实施例具体说明本发明的液态环氧树脂组合物和使用该液态环氧树脂组合物的粘合剂，但本发明的液态环氧树脂组合物和使用该液态环氧树脂组合物的粘合剂并不限于这些实施例。Hereinafter, the liquid epoxy resin composition of the present invention and the adhesive using the liquid epoxy resin composition will be specifically described using examples, but the liquid epoxy resin composition of the present invention and the adhesive using the liquid epoxy resin composition Adhesives are not limited to these examples.

另外，对于实施例和比较例的粘合剂，评价了粘附力、反应率、弹性模量的3个项目。这些项目采用以下方法进行评价。In addition, three items of adhesive force, reaction rate, and elastic modulus were evaluated for the adhesives of Examples and Comparative Examples. These items were evaluated using the following methods.

[粘附力(N)][Adhesion (N)]

在预先涂有阻焊剂并在其上涂有预涂熔剂的基板上，用分配器将本发明的液态环氧树脂组合物(粘合剂)以一点的涂布直径为0.7±0.15mm涂布2点。在该粘合剂上安装2012型矩形陶瓷电容器之后，30秒内将基板表面温度升至150℃，然后保持60秒(A)及1小时(B)使之固化(固化炉：静止式回流熔炉SAR-401A(奥原电气公司制))。将(A)和(B)的试验片放冷至室温(23℃)，用推拉力计测定沿与部件长轴垂直的方向推动时的剥离强度。部件数设为10，记录其平均值。On the substrate coated with solder resist in advance and coated with pre-coated flux thereon, the liquid epoxy resin composition (adhesive) of the present invention is coated with a coating diameter of 0.7 ± 0.15 mm with a dispenser 2:00. After mounting a 2012-type rectangular ceramic capacitor on the adhesive, raise the substrate surface temperature to 150°C within 30 seconds, and then hold it for 60 seconds (A) and 1 hour (B) to cure it (curing furnace: static reflow furnace SAR-401A (manufactured by Okuhara Electric Co., Ltd.). Let the test pieces (A) and (B) cool to room temperature (23°C), and use a push-pull gauge to measure the peel strength when pushed in a direction perpendicular to the long axis of the component. The number of parts is set to 10, and the average value is recorded.

[反应率][response rate]

按照如下步骤计算。Follow the steps below to calculate.

<1>示差扫描量热计(使用Mac Science公司制造的示差扫描量热计DSC3100/3200)，按照该装置所附手册的记述，根据各种样品的等速升温数据(升温速度5℃/分钟，10℃/分钟，20℃/分钟)计算达到整个峰的热量、峰温度及峰值的变化率。这里所说的变化率为达到峰温度时的热量除以整个峰的热量所得的值。<1> Differential scanning calorimeter (using the differential scanning calorimeter DSC3100/3200 manufactured by Mac Science Company), according to the description of the manual attached to the device, according to the constant rate heating data of various samples (heating rate 5 ℃ / min , 10°C/min, 20°C/min) to calculate the heat reaching the entire peak, the peak temperature and the rate of change of the peak. The rate of change referred to here is a value obtained by dividing the calorific value when reaching the peak temperature by the calorific value of the entire peak.

<2>以上述升温速度的常用对数值为纵轴，峰温度的倒数为横轴，制成小泽曲线(ozawa plot)，然后求出各样品的活化能、频率因子和反应次数。<2> Take the common logarithm of the above-mentioned heating rate as the vertical axis, and the reciprocal of the peak temperature as the horizontal axis to make an ozawa plot, and then calculate the activation energy, frequency factor and reaction times of each sample.

<3>根据上述<2>中求得的活化能、频率因子及反应次数制成反应预测图，根据此图求出80℃、130℃及150℃的各温度下0秒、30秒、60秒和90秒后的反应率。<3> According to the activation energy, frequency factor and reaction times obtained in the above <2>, a reaction prediction diagram is made, and according to this diagram, 0 seconds, 30 seconds, and 60 seconds at each temperature of 80°C, 130°C and 150°C are obtained. seconds and the response rate after 90 seconds.

<4>进而，根据0秒、30秒、60秒和90秒后的各个反应率，按照下式求出150℃的结果X和130℃的结果Y。<4> Furthermore, from the respective reaction rates after 0 second, 30 seconds, 60 seconds, and 90 seconds, the result X at 150°C and the result Y at 130°C were obtained according to the following formula.

[式5][Formula 5]

X或Y＝(30秒固化时的反应率-0秒时的反应率)/(90秒固化时的反应率-60秒固化时的反应率)X or Y=(reaction rate when curing in 30 seconds-reaction rate when curing in 0 seconds)/(reaction rate when curing in 90 seconds-reaction rate when curing in 60 seconds)

<5>求出150℃下固化30秒时的反应率与80℃下固化30秒时的反应率之比Z(150℃/80℃)。<5> The ratio Z (150°C/80°C) of the reaction rate when curing at 150°C for 30 seconds to the reaction rate when curing at 80°C for 30 seconds was obtained.

[弯曲弹性模量(Pa)][Bending modulus of elasticity (Pa)]

依照JIS K 6911测定。另外，试验片使用120℃下固化1小时后再于150℃下固化1小时制得的样品。Measured in accordance with JIS K 6911. In addition, as a test piece, what was cured at 120 degreeC for 1 hour and then cured at 150 degreeC for 1 hour was used.

实施例1Example 1

将双酚A型环氧树脂(日本Epoxy resins公司生产，商品名：Epikote828)50质量份、双酚F型环氧树脂50质量份、固化剂(咪唑类胺加合物固化剂，味の

Figure 2007800083873100002G2007800083873D0005074655QIETU
フアインテクノ公司制造，商品名：アミキユアPN-H，平均粒径10μm)35质量份及硅石粉末(日本アエロジル公司生产，商品名：アエロジル#300)3质量份搅拌混合，制成环氧树脂溶液。之后，向其中加入硅石粉末(一次粒径：约10nm)7质量份作为触变剂，用匀浆机混合，配制液态环氧树脂组合物。此时获得的液态环氧树脂组合物可以作为粘合剂使用。其物性如表1所示。Bisphenol A type epoxy resin (produced by Japan Epoxy resins company, trade name: Epikote828) 50 mass parts, bisphenol F type epoxy resin 50 mass parts, curing agent (imidazole amine adduct curing agent, taste の
Figure 2007800083873100002G2007800083873D0005074655QIETU
35 parts by mass of 35 parts by mass of silica powder (manufactured by Japan Aerosil Corporation, trade name: Aerosil #300) were stirred and mixed to prepare an epoxy resin solution. Thereafter, 7 parts by mass of silica powder (primary particle diameter: about 10 nm) was added thereto as a thixotropic agent, and mixed with a homogenizer to prepare a liquid epoxy resin composition. The liquid epoxy resin composition obtained at this time can be used as an adhesive. Its physical properties are shown in Table 1.

实施例2Example 2

除了将实施例1中的固化剂变更为咪唑类胺加合物固化剂(味の

Figure 2007800083873100002G2007800083873D0005074655QIETU
フアインテクノ公司生产，商品名：アミキユアPN-23J，平均粒径为3μm)20质量份和脂肪族胺类胺加合物(味の
Figure 2007800083873100002G2007800083873D0005074655QIETU
フアインテクノ公司生产，商品名：アミキユアMY-24，平均粒径为8～10μm)15质量份之外，其他与实施例1相同，配制由液态环氧树脂组合物构成的粘合剂。其物性如表1所示。In addition to changing the curing agent in Example 1 to an imidazole amine adduct curing agent (味の
Figure 2007800083873100002G2007800083873D0005074655QIETU
Produced by Fine Technology Co., Ltd., trade name: Amikuyua PN-23J, average particle diameter is 3 μm) 20 parts by mass and aliphatic amine amine adduct (味の
Figure 2007800083873100002G2007800083873D0005074655QIETU
Produced by Fine Technology Co., Ltd., trade name: Amiquiyua MY-24, average particle size: 8-10 μm) 15 parts by mass, the other is the same as Example 1, and prepares an adhesive composed of a liquid epoxy resin composition. Its physical properties are shown in Table 1.

实施例3Example 3

除了将实施例1中的固化剂变更为咪唑类胺加合物固化剂(味の

Figure 2007800083873100002G2007800083873D0005074655QIETU
フアインテクノ公司生产，商品名：アミキユアPN-23，平均粒径为10μm)30质量份和脂肪族胺类胺加合物类固化剂(味の
Figure 2007800083873100002G2007800083873D0005074655QIETU
フアインテクノ公司生产，商品名：アミキユアMY-24，平均粒径为8～10μm)10质量份之外，其他与实施例1相同，配制由液态环氧树脂组合物构成的粘合剂。其物性如表1所示。In addition to changing the curing agent in Example 1 to an imidazole amine adduct curing agent (味の
Figure 2007800083873100002G2007800083873D0005074655QIETU
Produced by Fine Technology Co., Ltd., trade name: Amikuyua PN-23, average particle diameter is 10 μm) 30 parts by mass and aliphatic amine amine adduct type curing agent (味の
Figure 2007800083873100002G2007800083873D0005074655QIETU
Produced by Fine Technology Co., Ltd., trade name: Amiquiyua MY-24, average particle size: 8-10 μm) 10 parts by mass, the other is the same as Example 1, and prepares an adhesive composed of a liquid epoxy resin composition. Its physical properties are shown in Table 1.

实施例4Example 4

除了将实施例1中的固化剂变更为咪唑类胺加合物固化剂(味の

Figure 2007800083873100002G2007800083873D0005074655QIETU
フアインテクノ公司生产，商品名：アミキユアPN-40J，平均粒径为3μm)30质量份和脂肪族胺类胺加合物类固化剂(味の
Figure 2007800083873100002G2007800083873D0005074655QIETU
フアインテクノ公司生产，商品名：アミキユアMY-24，平均粒径为8～10μm)10质量份之外，其他与实施例1相同，配制由液态环氧树脂组合物构成的粘合剂。其物性如表1所示。In addition to changing the curing agent in Example 1 to an imidazole amine adduct curing agent (味の
Figure 2007800083873100002G2007800083873D0005074655QIETU
Produced by Fine Technology Co., Ltd., trade name: Amikuyua PN-40J, average particle diameter is 3 μm) 30 parts by mass and aliphatic amine amine adduct type curing agent (味の
Figure 2007800083873100002G2007800083873D0005074655QIETU
Produced by Fine Technology Co., Ltd., trade name: Amiquiyua MY-24, average particle size: 8-10 μm) 10 parts by mass, the other is the same as Example 1, and prepares an adhesive composed of a liquid epoxy resin composition. Its physical properties are shown in Table 1.

实施例5Example 5

除了将实施例1中的固化剂变更为微囊型固化剂(旭化成ケミカルズ公司制造，商品名：ノバキユアHX-3722，平均粒径为2μm)35质量份之外，其他与实施例1相同，配制由液态环氧树脂组合物构成的粘合剂。其物性如表1所示。Except that the curing agent in Example 1 is changed to 35 parts by mass of a microcapsule-type curing agent (manufactured by Asahi Kasei Chemical Corporation, trade name: ノバキユア HX-3722, the average particle diameter is 2 μm), the others are the same as in Example 1, and the preparation Adhesives composed of liquid epoxy resin compositions. Its physical properties are shown in Table 1.

比较例1Comparative example 1

除了将实施例1中的固化剂变更为咪唑类胺加合物固化剂(味の

Figure 2007800083873100002G2007800083873D0005074655QIETU
フアインテクノ公司生产，商品名：アミキユアPN-40J，平均粒径为3μm)10质量份和脂肪族胺类胺加合物(味の素フアインテクノ公司生产，商品名为アミキユアMY-24，平均粒径为8～10μm)30质量份以外，其他与实施例1相同，配制由液态环氧树脂组合物构成的粘合剂。另外，该组合物中，低温固化性的アミキユアPN-40J的量比在更高温度下显示固化性的低温固化性固化剂アミキユアMY-24的量少，不超过全部固化剂量的25质量％，因此该组合物的粘附力关系不满足0.6B<A。其物性如表1所示。In addition to changing the curing agent in Example 1 to an imidazole amine adduct curing agent (味の
Figure 2007800083873100002G2007800083873D0005074655QIETU
Produced by Fain Techno Company, trade name: Amiku Yua PN-40J, average particle diameter is 3 μm) 10 parts by mass and aliphatic amine amine adduct (produced by Ajinomoto Fain Techno Company, trade name is Amikyua MY-24, average particle diameter is 8～ 10 μm) except for 30 parts by mass, the same as in Example 1, and an adhesive composed of a liquid epoxy resin composition was prepared. In addition, in this composition, the amount of the low-temperature curable Amiquia PN-40J is less than the amount of the low-temperature curable curing agent Amiquia MY-24 that exhibits curability at a higher temperature, and does not exceed 25% by mass of the total curing amount, Therefore, the adhesion relation of this composition does not satisfy 0.6B<A. Its physical properties are shown in Table 1.

比较例2Comparative example 2

除了将实施例1中的固化剂变更为双氰胺类微囊型固化剂(旭化成ケミカルズ公司生产，商品名：ノバキユアHX-3613，平均粒径为5μm)35质量份之外，其他与实施例1相同，配制由液态环氧树脂组合物构成的粘合剂。其物性如表1所示。Except that the curing agent in Example 1 is changed to dicyandiamide microcapsule curing agent (produced by Asahi Kasei Chemical Corporation, trade name: ノバキユア HX-3613, the average particle diameter is 5 μm) 35 parts by mass, other and the embodiment 1, prepare an adhesive composed of a liquid epoxy resin composition. Its physical properties are shown in Table 1.

[表1][Table 1]

Figure G2007800083873D00141
Figure G2007800083873D00141

根据表1可知，本发明的粘合剂与比较例1和2相比在短时间内的粘附力高。另外，实施例1～5的粘合剂与比较例1和2相比，80℃下时反应率被控制得的较低。因此，保存稳定性提高，而且使用时瞬间发生固化反应，短时间内可以获得牢固的粘附力。因此成品率提高，并且可以得到高品质的产品。As can be seen from Table 1, the adhesive of the present invention has higher adhesion in a short time than Comparative Examples 1 and 2. In addition, compared with Comparative Examples 1 and 2, the reaction rate of the adhesives of Examples 1 to 5 was controlled to be lower at 80°C. Therefore, the storage stability is improved, and the curing reaction occurs instantaneously when used, and a strong adhesive force can be obtained in a short time. Therefore, the yield is improved, and a high-quality product can be obtained.

工业适用性Industrial applicability

本发明的液态环氧树脂组合物及使用该液态环氧树脂组合物的粘合剂可以在短时间内将半导体、电子部件等固定在电路基板上，可以缩短进入下一工序的时间，因而可以提高工作效率和生产性，并且可以获得保存稳定性高的粘合。若使用这样的粘合剂进行生产，则可以提高成品率，获得高品质的产品。所以，本发明的液态环氧树脂组合物及使用该液态环氧树脂组合物的粘合剂在半导体、电子部件的安装领域非常有效。The liquid epoxy resin composition of the present invention and the adhesive using the liquid epoxy resin composition can fix semiconductors, electronic components, etc. on the circuit board in a short time, and can shorten the time to enter the next process, so it can Work efficiency and productivity can be improved, and adhesion with high storage stability can be obtained. If such an adhesive is used for production, the yield rate can be improved and high-quality products can be obtained. Therefore, the liquid epoxy resin composition of the present invention and an adhesive using the liquid epoxy resin composition are very effective in the field of mounting semiconductors and electronic components.

Claims (7)

1. liquid epoxy resin composition, it contains (a) epoxy resin, (b) solidifying agent at least, it is characterized in that,
Said epoxy resin is the resin that has the epoxy group(ing) more than 2 in 1 molecule; It is to be selected from bisphenol A type epoxy resin; Bisphenol f type epoxy resin; Phenolic or cresol-novolak type epoxy resin; Alicyclic epoxy resin; Hydrogenated Bisphenol A 99 type or AD type epoxy resin; Propylene glycol diglycidylether; Aliphatic category epoxy resin such as tetramethylolmethane polyglycidyl ether; The epoxy resin that makes by aliphatics or aromatic carboxylic acid and epoxy chloropropane; The epoxy resin that makes by aliphatics or aromatic amine and epoxy chloropropane; The heterocyclic ring epoxy resins; The epoxy resin that contains volution; Epoxy modified resin; Bisphenol-s epoxy resin; The independent or epoxy resin more than 2 kinds in the biphenol type epoxy resin
Said solidifying agent is made up of amine potentiality solidifying agent independent or more than 2 kinds; And when combination more than 2 kinds is used, make when only using a kind of said solidifying agent at 150 ℃ of solidifying agent that have 50% above reactivity in following 30 seconds and in the solidifying agent total amount, occupy more than at least 50 quality %, and the content of said solidifying agent in compsn; With respect to epoxy resin 100 mass parts; Be 20 mass parts～60 mass parts, the mass median diameter of said solidifying agent is below 15 μ m
Said compsn has following performance:
On the substrate that is coated with solder resist and prefluxing; After using divider that this liquid epoxy resin composition is 2 of 0.7 ± 0.15mm coatings with every coating diameter; To stick at coating place as 2012 type rectangular ceramic electrical condensers of adherend; Be stained with make substrate surface temperature be warming up to 150 ℃ in back 30 seconds after; Put after keeping making it in 60 seconds or 1 hour solidifying and be chilled to 23 ℃; When making an experiment through bond test, the adhesive power when 150 ℃ following hold-time of temperature is 60 seconds (A) satisfies the relation that formula 0.6B＜A stipulates with the adhesive power (B) of maintenance in the time of 1 hour, the intensity when said bond test is peeled off with the direction promotion of parts axis for using pull and push dynamometer to measure the edge.
2. the described liquid epoxy resin composition of claim 1 is characterized in that, aforementioned adhesive power (A) is more than the 30N.
3. claim 1 or 2 described liquid epoxy resin compositions; It is characterized in that; When each reactivity that makes the liquid epoxy resin composition of curing in the time of 0 second, 30 seconds, 60 seconds, 90 seconds under 150 ℃ the temperature was counted α (0), α (30), α (60), α (90) respectively, their relation was expressed from the next:
[several 1]
X＝[α(30)-α(0)]/[α(90)-α(60)]
In the formula, X is more than 3, below 15.
4. claim 1 or 2 described liquid epoxy resin compositions; It is characterized in that; When each reactivity that makes the liquid epoxy resin composition of curing in the time of 0 second, 30 seconds, 60 seconds, 90 seconds under 130 ℃ the temperature was counted β (0), β (30), β (60), β (90) respectively, their relation was expressed from the next:
[several 2]
Y＝[β(30)-β(0)]/[β(90)-β(60)]
In the formula, Y is more than 2, below 10.
5. claim 1 or 2 described liquid epoxy resin compositions; It is characterized in that the ratio Z (γ (150)/γ (80)) of the reactivity γ (80) when solidifying 30 seconds under reactivity γ (150) when solidifying 30 seconds under 150 ℃ the temperature and 80 ℃ the temperature is more than 10.
6. claim 1 or 2 described liquid epoxy resin compositions is characterized in that, adopting the bending elastic modulus of method solidified test film under 20 ℃ according to JIS K6911 is 5 * 10 8～5 * 10 10The scope of Pa, said condition of cure be 120 ℃ following 1 hour, and then 150 ℃ following 1 hour.
7. a tackiness agent is characterized in that, contains claim 1 or 2 described liquid epoxy resin compositions.
CN200780008387.3A 2006-01-17 2007-01-17 Liquid epoxy resin composition and adhesive using same Active CN101400715B (en)

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JP2006009303 2006-01-17
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PCT/JP2006/301894 WO2007083397A1 (en) 2006-01-17 2006-02-03 Liquid epoxy resin composition and adhesive using the same
JPPCT/JP2006/301894 2006-02-03
PCT/JP2007/050614 WO2007083673A1 (en) 2006-01-17 2007-01-17 Liquid epoxy resin composition and adhesive using same

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WO2016186127A1 (en) * 2015-05-20 2016-11-24 積水化学工業株式会社 Sealant for liquid crystal display element, vertical conduction material, and liquid crystal display element
JP6813313B2 (en) * 2016-09-09 2021-01-13 旭化成株式会社 Thermosetting adhesive
CN106987095B (en) * 2017-05-16 2018-09-28 广东博汇新材料科技股份有限公司 High transparency epoxy resin composition for prepreg and preparation method thereof
CN111518499A (en) * 2020-06-08 2020-08-11 武汉市三选科技有限公司 Underfill adhesive with stable adhesive force at high temperature and preparation method thereof

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