JPS621656B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a resin composition, and more particularly to a resin composition that provides a resin molded article whose surface can be clearly marked with a laser. In recent years, when marking the surface of a molded product of an electronic component device made by sealing an electronic component such as a semiconductor element with epoxy resin, etc., a laser beam generated from a laser oscillator is passed through a die-cut mask and its optical image is In some cases, it has been put into practical use to focus the above-mentioned molded materials onto the molded product and apply predetermined markings thereon. This marking method uses the energy of a laser beam to destroy the surface layer of the molded product to a depth of several micrometers, roughening the surface, and visually marking it by contrasting the surface texture of the destroyed and undestructed parts. It is something that makes you aware. However, in conventional molded products,
There is a problem that the contrast between the destroyed part and the non-destructed part is not necessarily good, and therefore the marking cannot be clearly seen. This tendency is particularly noticeable when the molded product is colored such as white, gray, or black, and in a relatively dark atmosphere. The present invention has been made in view of the above, and includes:
An object of the present invention is to provide a thermosetting resin composition for molding that provides a resin molded article with clearly visible laser markings even in a relatively dark atmosphere. That is, the present invention provides an epoxy resin composition for a resin molded article whose surface is marked with a laser, containing an inorganic filler of 50% on the basis of the entire composition.
The present invention relates to a molding resin composition characterized in that it contains ~85% by weight and 0.05~3.0% by weight of a black organic dye consisting of an azo metal-containing compound. The resin composition of the present invention contains an inorganic filler and the above-mentioned specific black organic dye together with an epoxy resin, and also usually contains a curing agent and a curing accelerator, and if necessary, a mold release agent, a flame retardant, and a pigment. , silane coupling agent, etc. Conventionally, inorganic pigments such as metal oxides and ferrocyanides, and carbon black have been used as pigments in epoxy resin compositions, but in molded products obtained from such compositions, the laser can cause damage to the surface of the molded product, and The contrast with the parts is not clear and the markings are not clearly visible. However, according to the present invention, when the resin composition contains 0.05 to 3.0% by weight of the above-mentioned specific black organic dye, the contrast between the surface properties of the destroyed part and the non-destructed part of laser marking becomes clear, and the marking becomes clearly recognized. The marking is particularly clear when the black organic dye accounts for 0.1 to 1.0% by weight based on the total composition. When the black organic dye is less than 0.5% by weight, the contrast between the destroyed and non-destructive parts is not clear, while when it is contained more than 3.0% by weight, the reliability (moisture resistance) of the resin-sealed electronic component device is reduced, etc. It has its drawbacks. The black organic dye used in the present invention is one made of an azo metal-containing compound, that is, an azo metal-containing dye. As the azo dye, a monoazo dye is suitable. The metal components contained in the dye include copper,
Examples include potassium, sodium, chromium, cobalt, etc., with copper and chromium being particularly preferred. Further, the metal content of the dye is 0.01 to 20% by weight. Furthermore, the melting point of the dye is over 100℃, and the decomposition temperature is 200℃.
The above is desirable. Moreover, as the black organic dye, an oil-soluble dye is preferable. In the present invention, when the black organic dye is used, pigments conventionally added to resin compositions such as carbon black and titanium white (titanium oxide) may also be used together. The molding resin composition of the present invention contains an inorganic filler in an amount of 50 to 85% by weight based on the total composition. Examples of the inorganic filler include crystalline silica, amorphous silica, alumina, glass fiber, mica, talc, and clay. The inorganic filler preferably has a particle size of
149μm or more is 0.5% by weight or less, 46μm or less is 60~
95% by weight, 40-70% by weight below 10μm, and 3μm
It has a particle size distribution of 15-40% by weight. In addition to the curing agent and curing accelerator as described above, the composition of the present invention may also contain a flame retardant, a mold release agent, a pigment, a silane coupling agent, etc., as necessary. Examples of lasers include carbon dioxide lasers, semiconductor lasers, and YAG lasers. In the present invention, the intensity of the laser irradiated onto the resin molded article is usually an energy density of 0.2 to 0.5 joule/cm ² . The present invention will be explained below with reference to Examples. Examples 1 to 7, Comparative Examples 1 and 2 Epoxy resin (cresol novolak type resin with epoxy equivalent of 220 and softening point of 77°C) 16.0 parts Brominated epoxy resin (flame-retardant resin with epoxy equivalent of 275 and softening point of 80°C) 2.5 parts phenol novolak resin (phenol equivalent 105, softening point 75°C) 8.0 parts softener (2-methylimidazole) 0.4 parts flame retardant (antimony trioxide) 1.8 parts mold release agent (carnauba wax) 0.5 parts silane cup Ring agent (A-187 manufactured by Nippon Unicar Co., Ltd.) 0.5 parts Black organic dye (shown in Table 1 below) Inorganic filler (shown in Table 1 below)

【table】

[Table] When preparing the epoxy resin composition for molding with the above composition, the flame retardant and inorganic filler are treated with a silane coupling agent, the remaining materials are added thereto, pulverized and mixed, and then 80% The mixture was mixed for 10 minutes using a mixing roll heated to .degree. C., formed into a sheet, cooled, and pulverized to obtain a resin powder. A resin powder was obtained. In addition, in Table 1, each organic dye represented by the product name manufactured by Ciba Geigy is “MAPICO
All dyes are azo-based metal-containing dyes, except for ``BLACK'' which is phthalocyanine-based. This molding powder was molded into a disk with a matte finish of 12 μm in diameter and 5 mm in thickness using a transfer press. Molded product sample for marking (molding conditions −175
℃, 2 minutes, transfer pressure 90Kg/cm ² and post-curing
175℃, 10 hours). A carbon dioxide laser (manufactured by Shibuya Kogyo Co., Ltd.) was applied to this sample.
920 type laser mark, maximum energy density
0.4 Joul/cm ² ), the surface of the molded product was marked by irradiating a laser through a predetermined mask for 1/1,000,000 seconds. The results are also listed in Table 1. Examples 8 to 14 and Comparative Example 3 Bisphenol type epoxy resin (epoxy equivalent 450, softening point 45°C) 25.7 parts Diaminodiphenylmethane 3.0 parts Mold release agent (stearic acid) 0.5 parts Silane coupling agent (manufactured by Shin-Etsu Silicone Co., Ltd.) KBM403) 0.5 part black organic dye (shown in Table 2) Inorganic filler (shown in Table 2)

【table】

[Table] Molded product samples for marking were prepared from the compositions in Table 2 above according to the method of Example 1, and markings were applied to the surface of the molded products according to the same example. The results are also listed in Table 2. As is clear from Tables 1 and 2, the molded products obtained using the molding resin composition of the present invention have a brightness of markings measured using an SM color computer (manufactured by Suga Test Instruments Co., Ltd.) It can be seen that both color difference is superior to conventional products. As described above, molded products obtained using the resin composition of the present invention have excellent laser marking properties. It can be advantageously used in manufacturing sealed capacitors, capacitors, etc.

Claims (1)

[Claims] 1. In an epoxy resin composition for resin moldings whose surface is marked with a laser, 50 to 85% by weight of an inorganic filler and 0.05% of a black organic dye consisting of an azo metal-containing compound are added to the entire composition. A molding resin composition characterized by containing ~3.0% by weight.