JPH0446449B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a method for manufacturing electronic components such as ICs, LSIs, and tantalum capacitors. [Prior art and its problems] The above-mentioned electronic components have their electronic elements encapsulated in a case, but if room-temperature curable or heat-curable resin is used for encapsulation, it takes time to harden. However, workability is poor, and when a thermoplastic or thermosetting resin is used, the heat applied during solidification or curing, or the heat generated during the curing reaction adversely affects electronic devices, which is not desirable. On the other hand, ultraviolet curable resin compositions do not have the above-mentioned drawbacks and have good workability, but conventional ultraviolet curable resin compositions require continuous irradiation with ultraviolet rays until curing is completed, and therefore, they do not have the disadvantages of electronic devices. This was undesirable because the portions that would become hard could not be cured because they could not be continuously irradiated with ultraviolet rays. For example, acrylic ultraviolet curable resins and one-component epoxy resins have been conventionally used. With ultraviolet curing systems, parts that are in the shadow of electronic elements and cannot be irradiated with ultraviolet rays will not be cured, so heat curing is also used. For example, if TB3013C (Note 1) is filled into a case with a depth of 10 mm, after irradiating it with ultraviolet rays (Note 2) for 30 seconds,
Requires heat curing for 15 minutes or 80℃. On the other hand, one-component epoxy resin, such as LGX-910-
1 (Note 3) requires heat curing at 120℃ for 15 minutes or at 90℃ for 30 minutes. (Note 1) Manufactured by ThreeBond Co., Ltd. (Note 2) Cyuadrite HMW-244 (Oak Seisakusho Co., Ltd.) Distance 15cm (Note 3) Manufactured by ThreeBond Co., Ltd. In addition, anaerobic UV curing resins have a slow curing speed and are It has the disadvantage that completely cured parts may remain. Further, the moisture-curable ultraviolet curable resin does not cure under moisture in a sealed state, and even if it cures, it takes a long time. The present invention solves this problem by using a cationically polymerizable ultraviolet curable epoxy resin. (Means for Solving the Problems) The present invention provides ultraviolet rays that, once the inside of the case of an electronic component is irradiated with ultraviolet rays, the reaction automatically proceeds through cationic polymerization and cures naturally without the need for irradiating ultraviolet rays. The case is filled with a curable epoxy resin composition, irradiated with ultraviolet rays, and then an electronic device is inserted into the case to allow the resin composition to harden naturally. In the examples, the ultraviolet rays are applied after the resin composition is filled into the case, but the ultraviolet rays may be applied before or during the filling of the case. [Function] Due to the propagation reactivity of its cationic polymerization system, the above-mentioned UV-curable epoxy resin composition automatically undergoes cationic polymerization and progresses naturally even without UV irradiation once it is irradiated with UV rays. It hardens, and the shadowed portion of the electronic device hardens without continuous irradiation with ultraviolet rays, allowing the electronic device to be completely fixed and sealed within the case. [Example] A case 1 as shown in the first diagram is filled with an ultraviolet curable epoxy resin composition 2 as shown in the second diagram,
As shown in the third diagram, this resin composition 2 has ultraviolet 3
irradiate. As shown in FIG. 4, when an electronic element 4 is inserted into the case 1 with the resin composition 2 in an uncured state, the resin composition 2 including the part that will be in the shadow of the electronic element 4 is Everything is completely cured,
The electronic device 4 is fixedly sealed within the case 1. Note that even after the electronic element 4 is inserted, curing can be accelerated by irradiating it with ultraviolet rays 3 as shown by the dotted line in Figure 4. The ultraviolet curable epoxy resin composition 2 is one that once irradiated with ultraviolet rays, the reaction proceeds automatically and cures naturally even without irradiation of ultraviolet rays due to the propagation reactivity of its cationic polymerization system. The specific composition is as follows. Epicoat 828 (Bisphenol A type epoxy resin manufactured by Yuka Ciel Epoxy Co., Ltd.) ...60 parts by weight Bakelite ERL-4206 (Union Carbide, cycloaliphatic epoxy resin ...40 parts by weight for 100 parts by weight of epoxy resin) So, Table 1
Add and mix predetermined amounts of various organosilicon compounds shown in , and further add 0.4 of UVE-1014 (manufactured by General Electric Co., Ltd., 50% propylene carbonate solution of triarylsulfonium salt) as a cationic polymerization catalyst to each of these mixtures. Samples 1, 2, 3, and 4 were prepared by adding and mixing parts by weight.

[Table] More specifically, the epoxy resin used in the epoxy resin composition of the present invention includes conventionally known aromatic epoxy resins, alicyclic epoxy resins, and aliphatic epoxy resins. Particularly preferred aromatic epoxy resins are polyglycidyl ethers of polyhydric phenols having at least one aromatic nucleus or their alkylene oxide adducts, such as bisphenol A or its alkylene oxide adducts and epichlorohydrin. Examples include glycidyl ether and epoxy novolak resin produced by reaction with Particularly preferable alicyclic epoxy resins include polyglycidyl ethers of polyhydric alcohols having at least one alicyclic ring, or compounds containing cyclohexene or cyclopentene rings, which are epoxidized with a suitable oxidizing agent such as hydrogen peroxide or acetic acid. There are cyclohexene oxide- or cyclopentene oxide-containing compounds that can be obtained. A typical example of polyglycidyl ether is hydrogenated bisphenol A.
Or glycidyl ether produced by reacting the alkylene oxide adduct with epichlorohydrin. Furthermore, representative examples of cyclohexene oxide or cyclopentene oxide-containing compounds include those represented by the following formula.

【formula】

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【formula】

【formula】

【formula】

Particularly preferable aliphatic epoxy resins are aliphatic polyhydric alcohols or their alkylene oxide adducts, polyglycidyl ethers, representative examples of which are diglycidyl ether of 1,4-butanediol and 1,6-hexane. 1 for aliphatic polyhydric alcohols such as diglycidyl ether of diol, triglycidyl ether of glycerin, triglycidyl ether of trimethylolpropane, diglycidyl ether of polyethylene glycol, diglycidyl ether of polypropylene glycol, ethylene glycol, propylene glycol, and glycerin. Examples include polyglycidyl ethers of polyether polyols obtained by adding a species or two or more alkylene oxides (ethylene oxide, propylene oxide). Although some of these aromatic epoxy resins, alicyclic epoxy resins, and aliphatic epoxy resins can be used alone in the present invention, it is desirable to blend them appropriately depending on the desired properties. The energy ray-sensitive sensitizer used in the present invention that decomposes under energy ray irradiation and releases a catalyst having the effect of causing polymerization or crosslinking of the cationically polymerizable resin is not particularly limited, but particularly preferred ones are those that can be polymerized by irradiation. It belongs to a group of double salts, which are onium salts that release Lewis acids with initiation potential. Such compounds basically have the general formula [R ¹ _a , R ² _b , R ³ _c , R ⁴ _d Z] ^+m [MY _o+n ] ^{-m [} wherein the cation is onium and Z is N≡
N, S, Se, Te, P, As, Sb, Bi, O, halogen (eg I, Br, Cl), R ¹ , R ² , R ³ .
R ⁴ is an organic group which may be the same or different.
a, b, c, and d are each integers of 0 to 3, and a+b+c+d is equal to the valence of Z. M is a metal or metalloid that is the central atom of the halide complex, and B, P, As, Sb, Fe,
Sn, Bi, Al, Ca, In, Ti, Zn, So, V, Cr,
Mn, Co, etc. x is a halogen, m is the net charge of the halide complex ion, and n is the number of halogen atoms in the halide complex ion. ]. Such catalyst precursors are known per se,
For example, compounds where Z is N≡N are
It is described in No. 3708296, No. 3949143, No. 3794576, etc. Other onium catalyst precursors are described in Belgian Patent No. 828841, Belgian Patent No. 828669, French Patent No. 2270269, etc. The above diazonium compounds are described in the above US patents.
It can be obtained by the method described in No. 3708296, No. 3949143, etc. Compounds where Z is S, Se, Te are described in J. Knapozyk et al., JACS, 91 , 145,
(1969), J.Organic of ALMeycook et al.
Chamistry, 35, No. 8, 2532 (1970), Goethals et al., Bul.Soc.Chim.Belg., 73 , 546 (1964), HM
It can be produced by the method described in Leicoetar et al., JACS, 51 , 3587 (1929). Z is P, N, As,
Representative onium salts such as Sb and Bi are J.Goardeler
Methoden der Organishen Chamie, 11/12 ,
591-640 (1958), K. Sasse's 12/1, 79-112
(1963). A typical onium salt where Z is halogen is OAPtsyna
Dokl.Adad.Nauk., SSSK, 163 , 383
(1965), M. Draxler et al. JACS, 75 , 2705
(1953) and others. (Example 1) An electronic element 4 of a hetantal capacitor is enclosed in an aluminum case 1 of 4.1φ×5 mm. Composition of the UV-curable epoxy resin 2 used: 100 parts by weight of Epicoat 828 (Bisphenol A type epoxy resin manufactured by Yuka Ciel Epoxy Co., Ltd.) 2 parts by weight of KBM 202 (Diphenyldimethoxysilane manufactured by Shin-Etsu Chemical Co., Ltd.) ・ UVE- 1014 0.2 parts by weight (General Electric Co., Ltd. Triarylsulfonium salt propylene carbonate 50%
Solution) ・Quartz powder 50 parts by weight Manufacturing process 1 Resin casting into aluminum case 2 Ultraviolet irradiation Approximately 40 ^mw / cm ² × 10 seconds (The lamp is a high-pressure mercury lamp with an output of 4 kW.The energy amount is measured using an ultraviolet light meter manufactured by Oak Seisakusho Co., Ltd. M-01 machine
Measured by UV-25 sensor) 3 After inserting the capacitor, leave it at room temperature. Results When the case was cut after 60 minutes, the resin had hardened uniformly, and a complete capacitor encapsulation part had been manufactured. In addition, when considering mass production, after inserting the element, 10
It was found that this can be achieved by UV irradiation for ~30 seconds. (Example 2) Same as Example 1 except that the case material is PBT. Composition of the UV-curable epoxy resin 2 used: 100 parts by weight of Epicoat 828 (Bisphenol A type epoxy resin manufactured by Yuka Ciel Epoxy Co., Ltd.) 2 parts by weight of KBM 202 (Diphenyldimethoxysilane manufactured by Shin-Etsu Chemical Co., Ltd.) ・ UVE- 1014 0.1 part by weight (General Electric Co., Ltd. Triarylsulfonium salt propylene carbonate 50%
Solution) The manufacturing process was the same as in Example 1. Results After 5 minutes, a good encapsulated part was obtained. Effects According to this method, there is no need for a heating process, etc.
Epoxy resin cast electronic components can be obtained efficiently and with energy savings. [Effects] As described above, according to the present invention, electronic components can be firmly sealed in a case by using an ultraviolet curable resin composition and simply irradiating it with ultraviolet rays once, resulting in good workability and the ability to prevent electronic components caused by heat. This can prevent adverse effects on the element.

[Brief explanation of the drawing]

1 to 4 are explanatory diagrams sequentially showing the method of the present invention. 1... Case, 2... Ultraviolet curable resin composition, 3... Ultraviolet light, 4... Electronic element.

Claims (1)

[Claims] 1 A cationically polymerizable ultraviolet curable epoxy resin composition consisting of an epoxy resin, a cationic polymerization catalyst that releases a Lewis acid upon irradiation with ultraviolet rays, and an organosilicon compound is filled into the case of an electronic component, and this resin composition is A method of manufacturing an electronic component, which comprises irradiating an object with ultraviolet rays, inserting an electronic element into the case with an uncured ultraviolet curable epoxy resin composition, and curing the resin composition.