JPS6222823A - Sealing resin composition - Google Patents

Abstract

PURPOSE:The titled composition low in stress and excellent in moisture resistance and laser markability, prepared by mixing an epoxy resin with a novolak phenolic resin, a specified organic dye, crystalline thermoplastic resin nylon-12 and an inorganic filler. CONSTITUTION:A mixture formed by mixing an epoxy resin (A) having at least two epoxy groups in the molecule with a novolak phenol(-modified) resin (B) obtained from a phenol and (para)formaldehyde at a molar ratio of the epoxy groups of component A to the phenolic hydroxyl groups of component B of 0.1-10 is mixed with 0.01-10wt% organic dye (C) having at least one metal atom or ion in the molecule (e.g., a compound of formula I), 0.1-21wt% crystalline thermoplastic resin nylon-12 (D) having a group of formula II (wherein n>=1), 25-90wt% inorganic filler (E) (e.g., silica powder) and, optionally, a mold release, a flame retardant, a colorant, a silane coupling agent, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field of the Invention] The present invention relates to a sealing resin composition that is low in stress and has excellent moisture resistance and laser mark properties.

[Technical Background of the Invention and Problems thereof] In recent years, methods have been used to seal electronic components such as diodes, transistors, and integrated circuits using thermosetting resins. This resin sealing method is economically advantageous compared to hermetic sealing methods using glass, metal, or ceramic, and is therefore widely put into practical use. Thermosetting resins are used as sealing resins, and among them, reliability and
Epoxy resin compositions are most commonly used due to cost and other considerations. Incidentally, acid anhydrides, aromatic amines, novolak type phenolic resins, etc. are used as curing agents for epoxy resins, but epoxy resin compositions containing novolak type phenolic resins as curing agents do not require the use of other curing agents. It has superior moldability and moisture resistance compared to the
Since it is non-toxic and inexpensive, it is the most preferred and widely used material for semiconductor encapsulation.

However, conventional epoxy resin compositions using a novolac type phenolic resin as a curing agent have the disadvantage that they shrink during molding and curing, applying stress to the element, resulting in poor reliability of the encapsulated molded product. That is, when a molded product using the above resin composition is subjected to a wet air cycle test, bonding wire breakage, resin cracks, and element cracks occur.
It can no longer function as an electronic component. Particularly large element size (5ms+ x5mm 0 or more”) CPL
When used for sealing I, gate arrays, etc., the above phenomenon occurs significantly.

Furthermore, in order to mark the product name or manufacturer's name on the surface of a resin-sealed semiconductor product, a method of stamping with thermosetting ink is currently generally employed.

However, the disadvantage of this ink stamp is that it is relatively easily erased by organic solvents and is susceptible to friction. In order to compensate for this drawback and to improve the efficiency of the marking process, laser marking using a laser such as carbon dioxide gas has recently begun to be performed. However, when laser marks are made on conventional epoxy resin compositions, there is a drawback that the mark clarity is inferior to that of the ink marking method.

[Object of the Invention] The object of the present invention was made to eliminate the above-mentioned drawbacks, and it has low stress, excellent moisture resistance, and laser mark property, and has the inherent heat resistance of an epoxy resin composition. The object of the present invention is to provide a sealing resin composition that maintains mechanical properties and moldability.

[Summary of the Invention] As a result of intensive studies to achieve the above object, the present inventors have developed an organic dye having at least one metal atom or metal ion in its molecule and a crystalline thermoplastic resin nylon-12. The present invention has been completed based on the discovery that a sealing resin composition with low stress and excellent moisture resistance and laser marring properties can be obtained by blending the following.

That is, the present invention comprises: (A) an epoxy resin, (B) a novolac type phenolic resin, (C) an organic dye having at least one metal atom or metal ion in its molecule, and (D) a crystalline thermoplastic resin. This is a sealing resin composition characterized by containing nylon-12 and (E) an inorganic filler. Then, to this resin composition, (C) an organic dye having at least one metal atom or metal ion in the molecule was added in an amount of 0.0
1 to 10% by weight, (D) 0.1 to 20% of crystalline thermoplastic resin nylon-12, and (E) 2% of inorganic filler.
The sealing resin compositions each contain 5 to 90% by market weight. In addition, the molar ratio [(a)/(b)] between the epoxy group (a) of the epoxy resin (A) and the phenolic hydroxyl group (b) of the novolac type phenol resin (B) is 0.1 to 1.
A sealing resin composition in the range of 0 is particularly suitable.

<A) The epoxy resin used in the present invention is not particularly limited in molecular structure, molecular weight, etc., as long as it is a compound having at least two or more epoxy groups in its molecule, and includes a wide range of commonly used epoxy resins. can do. Examples include aromatic resins such as bisphenol type, alicyclic resins such as cyclohexane derivatives, and resins such as epoxy novolak resins represented by the following general formula, and these resins may be used alone or in combination of two or more.

(In the formula, R1 represents a hydrogen atom, a halogen atom, or an alkyl group, R2 represents a hydrogen atom or an alkyl group, and n represents an integer of 1 or more.) As the novolac type phenol resin (B) used in the present invention, phenol , Novola obtained by reacting phenols such as alkylphenols with formaldehyde or roseformaldehyde.

Tsuku-type phenolic resins and their modified 5i11! .

For example, epoxidized or butylated novolak type phenolic resins may be used, and these may be used alone or in combination of two or more. The blending ratio of the novolak-type phenolic resin is determined by the molar ratio of the epoxy m<a> of the (A>epoxy resin) and the phenolic hydroxyl group (b) of the novolak-type phenolic resin (B) [(a)/(b)]. is 0.1~
It is preferably within the range of 10. molar ratio is 0.1
If it is less than or exceeds 10, the moisture resistance, molding workability, and electrical properties of the cured product will deteriorate, and either case is not preferable. Therefore, it is better to limit it to the above range.

The organic dye (C) having at least one metal atom or metal ion in its molecule used in the present invention is not particularly limited in its molecular structure, as long as it meets the above conditions. Specific compounds include glue Om complex salt (M2" = Mn2", Ca'", 3r2
+, etc.) 7, and these may be used alone or in combination of two or more. And especially these organic dyes are A
It is preferable that the molecule does not contain halogen atoms such as chlorine or bromine because it does not affect the characteristics of the conductive element. The blending ratio of the organic dye is 0.01 to 10 to the resin composition.
It is preferable to contain % barium.

If the total amount is less than 0.01% by weight, there will be no effect on the laser mark 1, and if it exceeds 10@ffi%, the bulk will increase and the moldability will be poor, making it unsuitable for practical use.

(D) Crystalline thermoplastic resin nylon used in the present invention
12 is represented by the following general formula (%, where n represents an integer of 1 or more), and as long as it has this group, there are no particular restrictions on the molecular structure, molecular weight, etc., and it is generally used. τ can be broadly included. The blending amount of the thermoplastic resin nylon-12 of Crystal 1 is 0.1 to 0.1 to the resin composition.
It is preferable to contain 20m%. The blending amount is 0.
If it is less than 1% by weight, it will not be effective in reducing stress, and if it exceeds 1% by weight, the bulk will be too large and the moldability will be poor, making it unsuitable for practical use.

Furthermore, the inorganic filler (E) used in the present invention includes inorganic fibers such as silica powder, alumina, antimony trioxide, talc, calcium carbonate, titanium white, clay, asbestos, mica, red iron oxide, glass fiber, and carbon fiber. These can be used alone or in combination of two or more. Among these fillers, silica powder and alumina are particularly preferred. The blending ratio of the inorganic filler is preferably 25 to 90% by weight based on the resin composition.

If the blending ratio is less than 25% by weight, there will be no effect on moisture resistance, heat resistance, mechanical properties, or moldability, and if it exceeds 90% by weight, bulk will increase and moldability will be poor, making it unsuitable for practical use.

The sealing resin composition of the present invention comprises an epoxy resin, a novolak phenolic resin, an organic dye having at least one metal atom or metal ion in the molecule, a crystalline thermoplastic resin nylon-12, and an inorganic filler. If necessary, release agents such as natural waxes, gold salts of straight chain fatty acids, acid amides, esters, and paraffins, chlorinated paraffin, bromotoluene, hexabromobenzene, and antimony trioxide may be added. Flame retardants such as, carbon black, colorants such as iron oxide, silane coupling agents, etc. may be appropriately added and blended.

As a general method of combining the encapsulating resin composition of the present invention with a molding material, the above-mentioned components selected at a predetermined composition ratio are mixed sufficiently uniformly using a mixer, etc., and then melt-mixed using hot rolls. A molding material can be produced by processing or mixing using a kneader or the like, then cooling and solidifying, and pulverizing into an appropriate size.

When the encapsulating resin composition according to the present invention is applied to encapsulating, coating, insulating, etc. electronic/electrical components, excellent characteristics and reliability can be imparted.

[Effects of the Invention] The encapsulating resin composition of the present invention contains a crystalline thermoplastic resin nylon-12 and an organic dye having at least one metal atom or metal ion in its molecule. Because of the stress, it will not shrink during molding and hardening and stress will not be applied to the element, and it has excellent moisture resistance, eliminating the occurrence of bonding wire breakage, resin cracks, and element cracks during hot and cold cycle tests. Furthermore, it has excellent laser marking properties, and marks with good clarity can be obtained. Of course, since it maintains the heat resistance, mechanical properties and workability of the epoxy resin composition, sufficient reliability can be obtained when this composition is used for sealing electronic and electrical parts.

[Examples of the Invention] The present invention will be specifically explained with reference to Examples, but the present invention is not limited to the following Examples.

In Examples and Comparative Examples, "%" means "% by weight".

Example Talesol novolac epoxy resin (epoxy f11
215) 16%, 9% novolak type phenolic resin (phenolized jl 107), 1% chromium complex salt of organic dye of the following formula, 125% crystalline thermoplastic resin nylon and 69% silica powder were mixed at room temperature. , then 90-95℃
After cross-cooling the mixture, it was pulverized to produce a molding material. 1
The prepared molding material was tabletted, preheated, injected into a mold heated to 170°C by transfer molding, and cured to obtain a molded product (sealed product). About this molded product Mechanical properties, glass transition temperature, humidity air cycle, moisture resistance,
The results are shown in Table 1.

Comparative example Talesol novolak epoxy resin (epoxy fl
215) 20%, 10% of novolac type phenolic resin (phenolized fi 107), and 70% of silica powder were processed in the same manner as in the example to produce a molding material, which was used to make a molded article. The product was tested for the same characteristics as in the example. The results are shown in Table 1.

Table 1 *1: Shows the measured temperature *2: 2 on the bottom of a 30x25x 5mm molded product
5x25x3+nm copper plate is embedded and molded at =40℃
We investigated resin cracks after 15 cycles of 15 cycles of 30 minutes each in a constant temperature bath of +200℃. *3: Using the molding material, we transfer-molded an electrical component with two aluminum wirings at 170℃ for 3 minutes. , and then cured at 180° C. for 8 hours. The 100 sealed electrical components thus obtained were subjected to a moisture resistance test in high-pressure steam at 120°C, and 50% of the electrical components were disconnected due to aluminum corrosion.
*4: From Table 1, 100 sealed electrical components sealed under the same conditions as those used in the humidity test were laser marked using a CO2 laser and visually evaluated for sharpness. It is clear that the present invention was superior in low stress, moisture resistance, and laser mark property compared to the comparative example, and the remarkable effects of the present invention were recognized.

Claims (1)

[Scope of Claims] 1 (A) Epoxy resin, (B) Novolac type phenolic resin, (C) Organic dye having at least one metal atom or metal ion in the molecule, (D) Crystalline thermoplastic resin A sealing resin composition comprising nylon-12 and (E) an inorganic filler. 2 Based on the resin composition, (C) 0.01 to 10% by weight of an organic dye having at least one metal atom or metal ion in the molecule, and (D) the crystalline thermoplastic resin nylon-12. The sealing resin composition according to claim 1, which contains 0.1 to 20% by weight of the inorganic filler and 25 to 90% by weight of the inorganic filler (E). 3 (A) Epoxy group (a) of epoxy resin and (B) phenolic hydroxyl group (b) of novolac type phenol resin
The sealing resin composition according to claim 1 or 2, wherein the molar ratio [(a)/(b)] of the sealing resin composition is in the range of 0.1 to 10.