JP2006008886A - Resin composition, and coating material containing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition improved in productivity and reliability by shortening the defoaming time and reducing the amount of the defoaming agent exuding from a resin coating into the surroundings, and to provide a coating material using the same. <P>SOLUTION: The resin composition is prepared by adding a silicone defoaming agent and a solvent, wherein a non-silicone defoaming agent is not separated, and the non-silicone defoaming agent to a resin solution containing a polyimide resin, polyamide-imide resin, and polyamide resin, high in heat resistance and modified by flexibility-increasing and elasticity-decreasing components. The coating material uses the resin composition, with the defoaming time shortened, with the amount reduced of the defoaming agent exuding from the resin coating into the surroundings, and with productivity and reliability improved. <P>COPYRIGHT: (C)2006,JPO&NCIPI

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 components, 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 response 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, modified polyamideimide resins (Patent Documents 1, 2, and 3) in which the resin is made flexible and have a low elastic modulus have been proposed in order to improve low warpage and flexibility. In order to improve printability and workability in these resins, inorganic fillers, organic fillers, and the like are directly dispersed in a resin solution.

  When a coating method using a screen printing machine is used, a silicone-based antifoaming agent is generally used in order to improve foam entrainment during screen printing and foam removal after film formation. Oozes out on the film surface or the periphery of the film during curing, and causes a problem that adversely affects the circuit bonding process with a resin or the like thereafter. When a non-silicone antifoaming agent is used alone, the entrainment of bubbles during screen printing and the ability to remove bubbles after film formation are reduced. In addition, the solvents used in the synthesis of polyimide resins, polyamideimide resins, and polyamide resins are poorly mixed with non-silicone antifoaming agents, improving foam entrainment during screen printing and foam removal after film formation. Therefore, it is necessary to add a large amount, and there is a problem that adversely affects moisture resistance and heat resistance.

JP 62-106960 A Japanese Patent Laid-Open No. 8-12763 JP-A-7-196798

  The resin composition of the present invention and the resin film thereof can shorten the defoaming time by adding both a solvent that does not separate the silicone-based antifoaming agent and the non-silicone-based antifoaming agent and the non-silicone-based antifoaming agent. By improving the productivity and further adding a non-silicone antifoaming agent, the amount of silicone antifoaming agent added can be reduced, and the antifoaming agent that exudes to the edge of the resin film can be reduced. The present invention provides a resin resin composition having excellent reliability and a film forming material including the resin resin composition, in which repelling or the like is reduced during component sealing or circuit bonding in the process.

The present invention relates to the following inventions.
<1> A resin composition having thixotropy in which an inorganic filler or the like is dispersed by adding a solvent in which a silicone-based antifoaming agent and a non-silicone-based antifoaming agent and a non-silicone-based antifoaming agent are added together to a resin solution containing a solvent. object.
<2> The resin composition according to <1>, wherein the resin solution containing a solvent is a polyimide resin, a polyamideimide resin, a polyamide resin and a modified polyimide resin, a polyamideimide resin, or a polyamide resin.
<3> The resin composition according to the above <1> or <2>, wherein the solvent from which the non-silicone antifoaming agent is not separated has a vapor pressure at 20 ° C. of 0.1 mmHg or less.
<4> A film-forming material comprising the resin composition according to any one of <1> to <3>, wherein a contact angle with a sealing material is 35 ° or less.

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

As the heat resistant resin used in the resin composition of the present invention, a polyimide resin, a polyamide imide resin, or a polyamide resin, which is a resin excellent in heat resistance and modified with a flexible and low elastic modulus component, is preferably used. . The modified resin is not particularly limited as long as it has various known modifications, 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.
Moreover, it is preferable that the resin composition of this invention is a paste-form.

  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-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 present invention also provides a polyimide resin, a polyamideimide resin, a polyamide resin, and a non-silicone defoamer and a non-silicone defoamer that do not separate from each other using a solvent having a vapor pressure at 20 ° C. of 0.1 or less. Modified polyimide resin, polyamideimide resin, a polyimide resin having a thixotropic property, which is added to a resin solution of a polyamide resin and dispersed with an inorganic filler, a polyamideimide resin, a polyamide resin, a modified polyimide resin, and a polyamideimide resin The present invention provides a film forming material characterized in that a contact angle with a resin composition of a polyamide resin and a sealing material is 35 ° or less.

  Examples of the resin used in the present invention include a thermosetting system and a thermoplastic resin. As the thermoplastic resin, a phenoxy resin, an acrylic resin, and the like are preferably used. 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 type of the antifoaming agent used in the present invention is not particularly limited, and a silicone-based antifoaming agent and a non-silicone-based antifoaming agent are used. . Several of these may be used in combination, and the blending amount and blending ratio are not particularly limited, and can be changed in a timely manner in consideration of the bubble entrainment property and bubble removal property during screen printing. For example, as a silicone type antifoaming agent, KS-602A (made by Shin-Etsu Chemical Co., Ltd .: trade name), KS-603 (made by Shin-Etsu Chemical Co., Ltd .: trade name), KS-608 (made by Shin-Etsu Chemical Co., Ltd.) : Product name), FA600 (manufactured by Shin-Etsu Chemical Co., Ltd .: product name), BYK-A506 (manufactured by Big Chemie Japan Co., Ltd .: product name), BYK-A525 (manufactured by Big Chemie Japan Co., Ltd .: product name), BYK- A530 (BIC Chemie Japan Co., Ltd .: trade name), as non-silicone antifoaming agent, BYK-A500 (BIC Chemie Japan Co., Ltd .: trade name), BYK-A500 (BIC Chemie Japan Co., Ltd .: trade name) ), BYK-A501 (BIC Chemie Japan Co., Ltd .: trade name), BYK-A515 (BIC Chemie JA Made emissions Co., Ltd. trade name), BYK-A555 (BYK Chemie Japan Co., Ltd .: trade name), etc., are preferably used. There is no restriction | limiting in particular also about the compounding quantity and compounding ratio.

  As a solvent that the non-silicone antifoaming agent used in the present invention does not separate, it is preferable that the vapor pressure at 20 ° C. is less than 0.1 mmHg for the purpose of expressing excellent continuous printing at the time of screen printing. If the vapor pressure at 20 ° C. exceeds 0.1 mmHg, when screen printing is continuously performed, the solvent is volatilized, the viscosity of the resin composition is increased, and the plate separation property at the time of screen printing is lowered. Examples of the solvent having a vapor pressure of 0.1 or less at 20 ° C. include triethylene glycol monomethyl ether, polyethylene glycol monomethyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, dipropylene glycol monobutyl ether, diethylene glycol monohexyl ether, and diethylene glycol monoacetate. Butyl ether or the like is preferably used. These solvents may be used alone or in combination of several kinds, and the mixing ratio is not particularly limited.

  The amount of the solvent that does not separate the antifoaming agent used in the present invention can be changed from time to time in consideration of continuous printability at the time of screen printing, bubble entrapment property at the time of screen printing, and bubble removal properties. When the total amount of solvent is 100% by weight, the range of 25 to 55% by weight is preferable. If it is less than 25% by weight, the foam entrainment property and foam removal property are reduced. If it exceeds 55% by weight, the solid content of the resin solution containing the solvent must be 60% by weight or more, and the solid content is 60% by weight. When a resin solution containing a solvent is synthesized by the above method, the viscosity of the resin solution increases and synthesis becomes difficult.

  The inorganic filler used in the present invention is not particularly limited. For example, calcium carbonate, alumina, titanium oxide, mica, aluminum carbonate, aluminum hydroxide, magnesium silicate, aluminum silicate, fused silica, crushed silica, fumed silica, sulfuric acid Various whiskers such as barium, short glass fiber, aluminum borate and silicon carbide are used. Moreover, several of these may be used in combination, and the blending amount and blending ratio are not particularly limited.

  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 or pigments, and heat stabilizers. Antioxidants, flame retardants, and lubricants can also be added.

Each of the resin compositions according to the present invention is combined with a base material such as an overcoat material for electronic parts, a liquid sealing material, an varnish for enameled wire, an impregnating varnish for electrical insulation, a casting varnish, mica, glass cloth, etc. Sheet varnish, MCL laminate varnish, friction material varnish, interlayer insulating film, surface protective film, solder resist layer, adhesive layer, etc. in the printed circuit board field, etc. It is suitably used as a forming material.
The film forming material containing the resin composition of the present invention preferably has a contact angle with the encapsulant of 35 ° or less. When the contact angle with the sealing material is larger than 35 °, the sealing material is insufficiently spread and the periphery of the IC connection portion cannot be sufficiently covered. The contact angle with the sealing material can be measured with a contact angle measuring device (manufactured by Kyowa Interface Science).

  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 the dicarboxylic acid A obtained in the above synthesis and 570 g of γ-butyrolactone were charged, heated to 160 ° C., reacted for 3 hours, and number averaged A resin having a molecular weight of 12,000 was obtained. The obtained resin was diluted with γ-butyrolactone to obtain a polycarbonate-modified polyamideimide resin solution having a nonvolatile content of 55% by weight. The molar ratio of trimellitic anhydride / dicarboxylic acid A was 0.6 / 0.4.
40% by weight of barium sulfate (product name: B-30, manufactured by Sakai Chemical Industry Co., Ltd.) and 100% by weight of the silicone-based antifoaming agent (Shin-Etsu Chemical Co., Ltd.) Company name: KS-603) 0.5% by weight, non-silicone antifoam (Bicchemy Japan Co., Ltd. product name: A-555) 2.5% by weight, non-silicone antifoam A non-separated solvent, diethylene glycol monobutyl ether acetate, was blended to 25% of the total amount of solvent, and Ep-1004 (manufactured by Yuka Shell Epoxy Co., Ltd.) with respect to 100 parts by weight of the resin content of the polycarbonate-modified polyamideimide resin solution. 20 parts by weight of a trade name, bisphenol A type epoxy resin) was added and stirred for 1 hour to obtain a polyamideimide resin composition.

Example 2
The same procedure as in Example 1 was carried out except that the solvent in which the non-silicone antifoaming agent was not separated in Example 1 and diethylene glycol monobutyl ether acetate was blended so as to be 40% of the total solvent amount, and the polyamideimide resin composition I got a thing.

Example 3
The same procedure as in Example 1 was carried out except that the solvent in which the non-silicone antifoaming agent was not separated in Example 1 and diethylene glycol monobutyl ether acetate was blended so as to be 55% of the total solvent amount. A composition was obtained.

Comparative Example 1
The same procedure as in Example 1 was carried out except that the solvent in which the non-silicone antifoaming agent was not separated in Example 1 and diethylene glycol monobutyl ether acetate was blended so as to be 20% of the total amount of the solvent. A composition was obtained.

Comparative Example 2
The same procedure as in Example 1 was carried out except that the solvent for separating the non-silicone antifoaming agent in Example 1 and γ-butyrolactone was blended so as to be 40% of the total solvent amount, and the polyamideimide resin composition I got a thing.

Comparative Example 3
In Example 1, the non-silicone antifoaming agent was not added, the silicone antifoaming agent was added at 3% by weight, and the non-silicone defoaming agent was not separated, and diethylene glycol monobutyl ether acetate was made 40% of the total solvent amount. Except for the blending, the same operation as in Example 1 was performed to obtain a polyamideimide resin composition.

Comparative Example 4
In Example 1, 3% by weight of a non-silicone antifoaming agent was added without adding a silicone-based antifoaming agent, and the solvent in which the non-silicone defoaming agent was not separated, diethylene glycol monobutyl ether acetate was increased to 40% of the total amount of the solvent. Except for the blending, the same operation as in Example 1 was performed to obtain a polyamideimide resin composition.

The properties of the polyamideimide resin compositions obtained in the above Examples and Comparative Examples were measured by the following methods, and the results are shown in Table 1.
Repelling at the periphery of the film Printing speed of the resulting polyamideimide resin composition on a 2 mm glass plate with a printing machine (product name: LS-34GX, manufactured by Neurong Co., Ltd.) and a mesh plate (150 mesh, manufactured by Murakami Co., Ltd.) Color check solution (product name: Super Check UP-ST, manufactured by Marktec Co., Ltd.) is applied to the polyamideimide resin film obtained by printing 10mm square at 100mm / sec and heating and curing at 120 ° C for 60 minutes in an air atmosphere. After spraying for 2 seconds and allowing to stand at room temperature for 30 minutes in an air atmosphere, the amount of repellency around the polyamideimide resin coating on the glass plate was measured with a universal projector (Nikon Corporation magnification 50 ×).
Wetting with sealing material (contact angle)
The obtained polyamide-imide resin composition is applied onto a rough surface of an electrolytic copper foil having a thickness of 35 μm or a polyimide film having a thickness of 50 μm, dried at 90 ° C. for 15 minutes, and then 120 minutes at 120 ° C. in an air atmosphere. Or it heated at 160 degreeC for 60 minutes, and 10 microliters of epoxy-type sealing materials [Hitachi Chemical Industry Co., Ltd. brand name CEL-C-5020] are dripped on the obtained coating film (thickness 20-30 micrometers), The contact angle with the cured film was measured using a contact angle measuring device (manufactured by Kyowa Interface Science). Moreover, the interface of a sealing material and a cured film was observed using the universal projector (Nikon Corporation magnification 50 times). The observation criteria are as follows.
: No boundary between encapsulant and cured film ×: There is boundary between encapsulant and cured film

  In Examples 1 to 3, the defoaming time and the amount of repelling are improved by adding 25 to 55% of the total amount of the solvent in which the non-silicone defoamer and the non-silicone defoamer are not separated, and The contact angle with the sealing material is small, and wettability is improved.

The resin composition of the present invention and the resin coating thereof have a short defoaming time by adding together a solvent that does not separate a silicone-based antifoaming agent, a non-silicone-based antifoaming agent, and a non-silicone-based antifoaming agent. Can improve productivity. Furthermore, the antifoaming agent that exudes to the edge of the resin film is reduced, and repellency and the like are reduced at the time of component sealing and circuit adhesion in the subsequent process, and excellent in reliability.
The resin composition for screen printing and the film-forming material of the present invention have the above-mentioned excellent characteristics, such as an overcoat material for electronic parts, a liquid sealing material, an varnish for enameled wire varnish for electrical insulation, and a varnish for laminates. It is suitably used for electronic components such as 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.

Claims (4)

A resin composition having thixotropy in which an inorganic filler or the like is dispersed by adding both a solvent in which a silicone-based antifoaming agent and a non-silicone-based antifoaming agent and a non-silicone-based antifoaming agent are added to a resin solution containing a solvent. The resin composition according to claim 1, wherein the resin solution containing a solvent is a polyimide resin, a polyamideimide resin, a polyamide resin and a modified polyimide resin, a polyamideimide resin, or a polyamide resin. The resin composition according to claim 1 or 2, wherein the solvent from which the non-silicone antifoaming agent does not separate has a vapor pressure at 20 ° C of 0.1 mmHg or less. The contact angle with a sealing material shows 35 degrees or less, The film forming material containing the resin composition in any one of Claims 1-3 characterized by the above-mentioned.