JP2007284468A - Resin composition and film-forming material comprising the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition improving fluidity by mixing a resin solution of a polyimide resin, a polyamide-imide resin or a polyamide resin and a modified polyimide resin, polyamide-imide resin or polyamide resin with inorganic fillers having different average particle diameters and further improving the printing operation efficiency without producing defoamed marks or pinholes when bubbles included during screen printing are defoamed and to provide a film-forming material comprising the resin composition. <P>SOLUTION: The resin composition is obtained by combining the resin solution with the two or more kinds of inorganic fillers having the different average particle diameters. The film-forming material comprises the resin composition. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a resin composition having thixotropy suitable for a coating method such as a screen printer, a dispenser, and a spin coater, and a film forming material including the same.

  In recent years, in the field of electronic parts, polyimide resin, polyamideimide resin, and polyamide resin have been used instead of epoxy resin as a resin that excels in heat resistance, electrical properties, and moisture resistance in order to respond to miniaturization, thinning, and high speed. Has been. These resins have a rigid resin structure, and when used as a thin film substrate, the cured substrate is greatly warped, and the cured film lacks flexibility and has poor flexibility.

Therefore, in order to improve low warpage and flexibility, modified polyamideimide resins in which the resin is made flexible and have a low elastic modulus have been proposed in Patent Documents 1, 2, 3 and the like.
Japanese Patent Application No. 60-244066 Japanese Patent Laid-Open No. 08-012763 JP 07-196798 A

  In these resins, an inorganic filler, an organic filler or the like is dispersed in a resin solution in order to improve printability and workability. Moreover, although a large amount of inorganic fillers, organic fillers, and the like are used for improving electrical characteristics, thixotropic property increases and fluidity decreases due to the large amount of fillers.

  When thixotropy increases and fluidity decreases, bubbles entrained during screen printing are difficult to escape, and bubbles remain in the film after the resin is cured, thereby reducing long-term reliability such as a moisture resistance test. In addition, when bubbles entrained during screen printing are defoamed, the flowability is reduced and defoaming traces are generated. Occurs.

  The present invention provides fluidity by mixing polyimide resins, polyamideimide resins, polyamide resins and modified polyimide resins, polyamideimide resins, and polyamide resin resin solutions having different average molecular diameters with different molecular weights. To provide a resin composition with improved printing workability and a film-forming material containing the same, without generating defoaming traces or pinholes when bubbles are removed during screen printing. It is intended.

The present invention relates to a resin composition comprising a resin solution combined with two or more inorganic fillers having different average particle diameters.
The present invention also relates to the resin composition, wherein the resin solution is a polyimide resin, a polyamideimide resin, a polyamide resin and a modified polyimide resin, a polyamideimide resin, or a polyamide resin.

Moreover, this invention relates to the said resin composition whose average particle diameter of an inorganic filler is 10 micrometers or less.
Moreover, this invention relates to the said resin composition whose 1 or more types of the inorganic filler from which an average particle diameter differs is a talc.

Moreover, this invention relates to the said resin composition whose fall rate of the average particle diameter after dispersion | distribution of the talc of an inorganic filler is less than 30%.
Moreover, this invention relates to the said resin composition whose total addition amount of an inorganic filler is 50-300 weight part with respect to 100 weight part of resin solution solid content.
Furthermore, this invention relates to the film forming material containing the said resin composition.

  The resin composition of the present invention and the film-forming material containing the resin composition improve the electrical characteristics by controlling the dispersion state when talc is dispersed, and further improve the fluidity during screen printing. Excellent moisture resistance and printing workability without generating defoaming traces and pinholes generated when foaming.

  Examples of the resin solution of the present invention include thermosetting and thermoplastic resins, and phenoxy resin, acrylic resin, and the like are preferably used as the thermoplastic resin. As the thermosetting resin, an epoxy resin, a phenol resin, a polyimide resin, a polyamideimide resin, a polyamide resin, or the like is preferably used. Preferably, polyimide resin, polyamideimide resin, polyamide resin, modified polyimide resin, polyamideimide resin, and polyamide resin are preferably used in consideration of heat resistance and electrical characteristics.

  The modified resin is not particularly limited as long as various known modifications are made, and examples thereof include those modified with a silicone resin, those modified with a polycarbonate resin, and those modified with a polybutadiene. Can do. Among them, a polyamideimide resin modified with a polycarbonate resin is preferable.

  For example, in the case of a polyamideimide resin modified with a polycarbonate resin, a 1,6-hexanediol-based polycarbonate which is a flexible and low elastic modulus component is used as the resin modified with a flexible and low elastic modulus component. It can be obtained by reacting a dicarboxylic acid obtained by reacting a diol or the like with a carboxylic acid, a polyisocyanate and a trivalent carboxylic acid having an acid anhydride group or a derivative thereof.

  The total amount of the inorganic filler used in the present invention is preferably 50 to 300 parts by weight with respect to 100 parts by weight of the resin solution solid content. When the total addition amount of the inorganic filler exceeds 300 parts by weight, the flexibility of the resin film tends to decrease and the warpage tends to increase, such being undesirable. If the total added amount of the inorganic filler is less than 50 parts by weight, it is difficult to obtain an improvement in fluidity, which is not preferable.

  The inorganic filler used in the present invention is not particularly limited. For example, calcium carbonate, alumina, titanium oxide, mica, talc, aluminum carbonate, aluminum borate, aluminum hydroxide, magnesium hydroxide, magnesium silicate, aluminum silicate, Fused silica, crushed silica, fumed silica, barium sulfate, short glass fibers, various whiskers such as aluminum borate and silicon carbide are used. Moreover, several types of these may be used in combination, and are not particularly limited.

  The average particle size of the inorganic filler used in the present invention is preferably 10 μm or less, and several types may be used in combination as long as the average particle size is 10 μm or less, and the shape of the filler is not particularly limited. If the average particle diameter of the inorganic filler exceeds 10 μm, it is not preferable because the inorganic filler straddles between the circuits and the electrical characteristics deteriorate.

  In addition, if the average particle size of the inorganic filler exceeds 10 μm, thixotropic properties are reduced, the fluidity during screen printing is increased, the flow between circuits is increased, and the subsequent IC mounting process and the like are adversely affected. Absent.

It is preferable to use talc for one or more of the inorganic fillers used in the present invention. If talc is not used, fluidity and defoaming properties during screen printing are undesirably reduced.
The amount of talc added is preferably 10 parts by weight or more, more preferably 10 parts by weight to 50 parts by weight, and particularly preferably 10 parts by weight to 30 parts by weight with respect to 100 parts by weight of the inorganic filler.

  The change rate of the average particle diameter after dispersion of talc of the inorganic filler used in the present invention is preferably within 30%, particularly preferably from 5% to 20%. If the change rate of the average particle diameter after dispersion of talc exceeds 30%, the electrical characteristics and the appearance after screen printing are undesirably lowered. When the rate of change of the average particle diameter after dispersion of talc is less than 5%, the secondary aggregates of talc are not dispersed and the electrical characteristics are adversely affected.

  Each of the resin compositions of the present invention is suitably used as a film forming material. In order to improve the workability at the time of coating and the film properties before and after the film formation, this resin composition includes epoxy resins, surfactants such as leveling agents, colorants such as dyes and pigments, and heat stabilizers. Antioxidants, flame retardants, antifoaming agents, and lubricants can also be added.

  The resin composition and the film-forming material containing the resin composition according to the present invention have the above-described excellent characteristics, and include an overcoat material for electronic parts, a liquid sealing material, an varnish for enameled wire varnish, an insulating varnish for laminates, It is suitably used for electronic components such as varnishes, varnishes for friction materials, interlayer insulating films, surface protective films, solder resist films, adhesive layers and the like in the field of printed circuit boards, and semiconductor elements.

The resin paste obtained by pasting the resin composition according to the present invention is suitably used for coating methods such as screen printing, dispenser and spin coating as film forming materials for various electric products and electronic parts. It is particularly suitable for screen printing.
The resin paste is suitably used as, for example, an overcoat material for electronic parts such as semiconductor elements and printed circuit boards, a liquid sealing material, an interlayer insulating film, a surface protective film, a solder resist layer, an adhesive layer, and the like.

  Furthermore, it can also be used for varnish for enameled wire, impregnated varnish for electrical insulation, cast varnish, mica, glass varnish, varnish for MCL laminate, friction material varnish, and the like.

EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not restrict | limited to these.
Example 1
Plaxel CD-220 (manufactured by Daicel Chemical Industries, Ltd., 1,6-hexanediol-based polycarbonate diol) was added to a 3 liter four-necked flask equipped with a stirrer, a condenser with an oil separator, a nitrogen inlet tube and a thermometer. Product name) 2000.0 g (100 mol), adipic acid 292.0 g (2.00 mol) and xylene 114.6 g were charged, and the temperature was raised to 200 ° C. while removing by-product condensed water. The mixture was reacted at 200 ° C. for 2 hours to obtain dicarboxylic acid A having an acid value of 49.7 KOH mg / g.

  Subsequently, 150.0 g (0.60 mol) of 4,4′-diphenylmethane diisocyanate and trimellitic anhydride 69 were added to a 2 liter four-necked flask equipped with a stirrer, a condenser tube, a nitrogen inlet tube and a thermometer. .12 g (0.36 mol), 541.44 g (0.24 mol) of dicarboxylic acid A obtained in the above synthesis and 760.56 g of γ-butyrolactone were charged, the temperature was raised to 160 ° C., and the resulting resin was reacted. Was diluted with γ-butyrolactone to obtain a polycarbonate-modified polyamideimide resin solution having a nonvolatile content of 40% by weight.

A silicone-based antifoaming agent (trade name: KS-603, manufactured by Shin-Etsu Chemical Co., Ltd.) is blended in an amount of 0.3 parts by weight with respect to 100 parts by weight of the solid content of the obtained polycarbonate-modified polyamideimide resin solution. The mixture was stirred for 10 minutes, and further 80 parts by weight of talc (manufactured by Fuji Talc Co., Ltd., trade name: LMS-300) was blended, and using a bead mill (trade name: OB mill 0.5N1 type, manufactured by Turbo Industry Co., Ltd.). 80% of 1.0 mm zirconia beads were filled, and the treatment was performed twice at a rotor speed of 2000 min ⁻¹ and a flow rate of 0.5 L per minute to obtain a polycarbonate-modified polyamideimide resin talc dispersion solution A.

A silicone-based antifoaming agent (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KS-603) is blended in an amount of 0.3 parts by weight with respect to 100 parts by weight of the obtained polycarbonate-modified polyamideimide resin solution at 20 ° C. For 10 minutes, and further 220 parts by weight of barium sulfate (manufactured by Sakai Chemical Industry Co., Ltd., trade name: B-30), and a bead mill (trade name: OB mill 0.5N1 type, manufactured by Turbo Industry Co., Ltd.) Was filled with 80% of 1.0 mm zirconia beads, and the treatment was performed once at a rotor speed of 2000 rpm and a flow rate of 0.5 L per minute to obtain a polycarbonate-modified polyamideimide resin barium sulfate dispersion solution B.

  The obtained dispersion solution was blended with liquid A: 100 and liquid B: 100, a solvent such as γ-butyrolactone was added as necessary, and the mixture was stirred at 50 ° C. for 1 hour, and further bisphenol A type epoxy resin (oiled shell) 20 parts by weight of Epoxy Corporation trade name Ep-1004) was added and stirred at 20 ° C. for 1 hour to obtain a polycarbonate-modified polyamideimide resin paste.

Example 2
Except for changing the number of times of bead milling of the polycarbonate-modified polyamideimide resin talc dispersion solution A of Example 1 to 3, the same operation as in Example 1 was performed to obtain a polycarbonate-modified polyamideimide resin paste.

Comparative Example 1
Except for changing the number of times of bead milling of the polycarbonate-modified polyamideimide resin talc dispersion solution A of Example 1 to 4, the same operation as in Example 1 was performed to obtain a polycarbonate-modified polyamideimide resin paste.

Comparative Example 2
Except that the number of bead mill treatments of the polycarbonate-modified polyamideimide resin talc dispersion solution A in Example 1 was changed to 8, the same operation as in Example 1 was performed to obtain a polycarbonate-modified polyamideimide resin paste.

  The characteristics of the polycarbonate-modified polyamideimide resin paste and the polyamideimide resin composition obtained in each of the above Examples and Comparative Examples were measured by the following methods, and the results are shown in Table 1.

(1) Average particle size reduction rate The obtained polycarbonate-modified polyamide-imide resin talc dispersion paste was measured using a particle size distribution analyzer (trade name: LMS-350, manufactured by Seishin Enterprise Co., Ltd.), and the value of normal distribution 50% was the average particle The average particle diameter of the inorganic filler before dispersion was 100%, and the ratio was taken as the ratio. The average particle diameter of the used talc (trade name: LMS-300, manufactured by Fuji Talc Co., Ltd.) was 5.5 μm as the standard product average particle diameter.

(2) Electrical properties The resulting polycarbonate-modified polyamideimide resin composition was printed on a polyimide substrate so as to cover a copper electrode tin-plated in a comb shape with a line width of 15 μm and a space width of 15 μm. Product, product name: LS-34GX) and a mesh plate (Murakami Co., Ltd., 150 mesh), printed at a printing speed of 100 mm / sec, and heat-cured at 120 ° C. for 60 minutes in an air atmosphere to be a polycarbonate-modified polyamideimide resin film A polyimide base comb electrode was obtained.

The resulting polyimide base comb-shaped electrode with a polycarbonate-modified polyamideimide resin film was subjected to a continuous resistance measuring machine (product name: Ion Migrator Tester MIG-8600) and an unsaturated pressure cooker (manufactured by Hirayama Manufacturing Co., Ltd.). Using a product name: HASTPC-422R8D), resistance was measured under conditions of a temperature of 110 ° C., a humidity of 85%, an applied voltage of 40 V, and an applied time of 100 hours. Three each of the obtained polycarbonate-modified polyamideimide resin compositions were measured, and when the resistance value became 1 × 10 ⁻⁶ Ω or less, conduction was defined as a yield ratio 100 hours after voltage application.

(3) Printing workability On a 2 mm glass plate, the obtained polycarbonate-modified polyamide-imide resin paste is printed on a printing machine (Neurong Co., Ltd., trade name: LS-34GX) and a mesh plate (Murakami Co., Ltd., 150 mesh). ) Was printed at a printing speed of 100 mm / sec, and cured by heating at 120 ° C. for 60 minutes in an air atmosphere to obtain a polycarbonate-modified polyamideimide resin film.

  The obtained polycarbonate-modified polyamide-imide resin film was observed with a universal projector (Nikon Corporation, magnification: 100 times) to observe the surface of the resin film. Resin film without bubble traces, pinholes and bubbles was marked with ◯, and those with bubble traces, pinholes and bubbles were marked with x.

From the above results, the following was found.
Examples 1 and 2 improve the electrical characteristics by dispersing the talc average particle size reduction rate within 30%, further improve the fluidity, improve the screen printing operation, and defoaming traces generated during defoaming and Excellent printing workability without generating pinholes.

The resin composition for screen printing of the present invention and the film-forming material containing the resin composition have the above-mentioned excellent characteristics, such as an overcoat material for electronic parts, a liquid sealing material, an varnish for varnish electrical insulation for enameled wire, and a laminate. It can also be applied to electronic parts such as varnishes for plates, varnishes for friction materials, interlayer insulating films, surface protective films, solder resist films, adhesive layers and semiconductor elements in the printed circuit board field.

Claims (7)

  A resin composition comprising a resin solution combined with two or more inorganic fillers having different average particle diameters.   The resin composition according to claim 1, wherein the resin solution is a polyimide resin, a polyamideimide resin, a polyamide resin, a modified polyimide resin, a polyamideimide resin, or a polyamide resin.   The resin composition according to claim 1 or 2, wherein the average particle size of the inorganic filler is 10 µm or less.   The resin composition according to any one of claims 1 to 3, wherein one or more inorganic fillers having different average particle sizes are talc.   The resin composition according to any one of claims 1 to 4, wherein a decrease rate of the average particle diameter after dispersion of talc of the inorganic filler is within 30%.   The resin composition according to any one of claims 1 to 5, wherein the total amount of the inorganic filler added is 50 to 300 parts by weight with respect to 100 parts by weight of the resin solution solid content. The film forming material containing the resin composition in any one of Claims 1-6.