JP2001302807A - Method for producing resin paste, and resin paste - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing resin paste, which improves the dispersibility of the filler for a resin paste and simplifies the production process. SOLUTION: This method for producing the resin paste is characterized by compounding a solution A comprising a heat-resistant resin, a solvent, a filler and a titanate-based coupling agent with a solution B comprising a heat- resistant resin, a solvent and a filler, and the resin paste.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a resin paste and a resin paste suitable for a coating method of a screen printing machine, a dispenser, a spin coater, etc., and more particularly to a method for producing a resin paste and a resin paste suitable for screen printing. About.

[0002]

2. Description of the Related Art In recent years, in the field of electronic components, polyimide resins and polyamide-imide resins have been used instead of epoxy resins as resins having excellent heat resistance, electrical properties and moisture resistance in order to respond to miniaturization, thinning and high speed. And a polyamide resin. These resins have a rigid resin structure and, when used as a thin film substrate, have a problem that the substrate after curing is greatly warped, and the cured film lacks flexibility and is inferior in flexibility.

Therefore, in order to improve low warpage and flexibility, a modified polyamideimide resin obtained by making a resin flexible and having a low elastic modulus (Japanese Patent Application Laid-Open No. 62-106960,
JP-A-8-12763, JP-A-7-196798
And the like) have been proposed. To these resins, by adding a high molecular weight epoxy resin to further impart heat resistance or by dispersing a filler to impart workability during application and shape retention after application, to impart printability, An insulating film and an insulating layer are formed directly on a substrate by a screen printing method. However, when an insulating film and an insulating layer are directly formed on a substrate by using a screen printing method, the wiring circuit on the substrate comes into direct contact with the screen plate, so that there is a problem that the wiring circuit is damaged or disconnected. In addition, with the recent miniaturization and thinning, the distance between the wirings has been reduced, the flow of the printing paste generated between the wirings has been increased, and a planetary mixer, A mechanical dispersing process such as a roll and a mill is required, and there is a problem in terms of manufacturing time and cost.

[0004]

SUMMARY OF THE INVENTION The present invention relates to a resin paste manufacturing method and a resin paste in which the dispersibility of a filler is improved and the manufacturing process is simplified.

[0005]

Means for Solving the Problems The present invention relates to the following inventions. A method for producing a resin paste in which a solution A containing a heat-resistant resin, a solvent and a filler is mixed with a solution A containing a heat-resistant resin, a solvent, a filler and a titanate coupling agent.

[0006] A method for producing the above resin paste, wherein the heat-resistant resin of the solution A and the solution B is a polyimide resin, a polyamideimide resin or a polyamide resin modified with a flexible and low modulus component.

The average surface area of the filler in the solution A is 50 m ^2.
/ G or more.

The average surface area of the filler in the solution B is 50 m ^2.
/ G or less.

[0009] The method for producing a resin paste as described above, wherein the titanate-based coupling agent of the solution A is a titanate-based coupling agent containing a phosphoric acid molecule in a side chain organic functional group of the hydrophobic group.

The method for producing a resin paste as described above, wherein the amount of the titanate-based coupling agent in the solution A is 0.1 to 5 parts by weight based on 100 parts by weight of the heat-resistant resin.

[0011] A resin paste obtained by any of the above production methods.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The resin paste of the present invention is obtained by mixing a solution A containing a heat-resistant resin, a solvent, a filler and a titanate coupling agent and a solution B containing a heat-resistant resin, a solvent and a filler. Can be

As the heat-resistant resin used in the resin paste of the present invention, a polyimide resin, a polyamide-imide resin and a polyamide resin modified with a flexible and low-modulus component are preferably used. The modified resin is not particularly limited as long as it has been subjected to various known modifications.
For example, those modified with a silicone resin, those modified with a polycarbonate resin, those modified with polybutadiene, and the like can be given. Among them, a polyamide imide resin modified with a polycarbonate resin is preferred.

The heat-resistant resin modified with a flexible and low-modulus component is, for example, a polyamideimide resin modified with a polycarbonate resin. It is obtained by reacting a dicarboxylic acid obtained by reacting a 6-hexanediol-based polycarbonate diol or the like with a carboxylic acid, a polyisocyanate and a trivalent carboxylic acid having an acid anhydride group or a derivative thereof.

As the solutions A and B in the present invention, solutions obtained by dissolving the above resin in a solvent having a relatively high boiling point such as γ-butyrolactone so that the resin content is preferably 30 to 55% by weight are used.

The filler having an average surface area of 50 m ² / g or more, which is preferably used in the solution A of the present invention, is not particularly limited as long as it can be dispersed in a solution containing the above-mentioned heat-resistant resin and a solvent to form a paste. Instead, various types are used. Examples include talc, calcium carbonate, alumina, titanium oxide, mica, aluminum carbonate, aluminum hydroxide, magnesium silicate, silica, barium sulfate, and the like.

The above filler may be used alone,
Several types may be used in combination.

The filler having an average surface area of 50 m ² / g or less used in the solution B of the present invention is not particularly limited as long as it can be dispersed in the above-mentioned solution containing a heat-resistant resin and a solvent to form a paste. Various things are used. For example, talc, calcium carbonate, alumina, titanium oxide,
Examples include mica, aluminum carbonate, aluminum hydroxide, magnesium silicate, silica, barium sulfate, short glass fibers, and various whiskers such as aluminum borate and silicon carbide.

The above filler may be used alone,
Several types may be used in combination.

As the filler in the present invention, a filler having an average surface area of 1 m ² / g or more is used. When the average surface area is less than 1 m ² / g,
The fluidity of the resin paste tends to be high, and the shape retention tends to be low. The upper limit is not particularly limited, but is usually 400 m ² /
g or less.

In the present invention, the total amount of the solution A and the solution B of the filler used is 100
It is preferable that the amount be 5 to 50 parts by weight based on parts by weight. 5
If it is less than parts by weight, shape retention tends to decrease,
If it exceeds 50 parts by weight, the leveling property and the defoaming property tend to decrease.

The amount of the filler of the solution A in the present invention is preferably 200 parts by weight or less based on 100 parts by weight of the heat-resistant resin. If it exceeds 200 parts by weight, the viscosity tends to increase and the dispersibility tends to decrease.

The amount of the filler of the solution B in the present invention is preferably 300 parts by weight or less based on 100 parts by weight of the heat-resistant resin. If it exceeds 300 parts by weight, the viscosity tends to increase and the dispersibility tends to decrease.

The titanate coupling agent used in the present invention is not particularly limited as long as it does not cause gelation when mixed with a solution containing a heat-resistant resin and a solvent. Is appropriately selected depending on the type of For example, when used for a modified polyimide resin, polyamideimide resin or polyamide resin, a titanate-based coupling agent containing a phosphoric acid molecule in a side chain organic functional group of a hydrophobic group is preferably used.

In the case of a polyimide resin, a polyamideimide resin or a polyamide resin modified with a flexible and low modulus component, for example, KR38S (Ajinomoto Co., Ltd.)
(Product name), KR138S (Ajinomoto Co., Ltd .: trade name), K
Titanate-based coupling agents such as R238S (Ajinomoto Co., Ltd .: trade name) and 338X (Ajinomoto Co., Ltd .: trade name) are preferably used. The titanate-based coupling agent may be used alone or in combination of several types.

The content of the titanate coupling agent is as follows:
In consideration of dispersibility and viscosity, the content is preferably 0.1 to 5 parts by weight based on 100 parts by weight of the heat-resistant resin. If the amount is less than 0.1 part by weight, the dispersibility tends to decrease, and if it exceeds 5 parts by weight, properties such as heat resistance and moisture resistance of the resin composition tend to decrease.

In order to improve workability at the time of coating and film properties before and after film formation, a colorant such as an epoxy resin, a phenol resin, a dye or a pigment, a heat stabilizer, and an antioxidant are added to the resin paste. , A flame retardant, a lubricant, an antifoaming agent, a leveling agent, and the like.

Of these, the use of an epoxy resin is preferred in terms of adhesion to a substrate and moisture resistance. When an epoxy resin is used in combination, the addition amount is preferably 1 to 50 parts by weight based on 100 parts by weight of the heat-resistant resin from the viewpoint of adhesion.

The resin paste of the present invention is suitably used as a film forming material for various electric products and electronic parts in coating methods such as screen printing, dispenser, and spin coating. Particularly, it is suitably used for screen printing.

The resin paste according to the present invention is suitable, for example, as an overcoat material for electronic components in the field of semiconductor devices 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. Used for It can also be used for varnishes for enameled wires, impregnated varnishes for electrical insulation, cast varnishes, varnishes for sheets combined with substrates such as mica, glass cloth, varnishes for MCL laminates, varnishes for friction materials, and the like.

[0031]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

Example 1 Plaxel CD was placed in a 3 liter four-necked flask equipped with a stirrer, a condenser equipped with an oil separator, a nitrogen inlet and a thermometer.
-220 (trade name of 1,6-hexanediol-based polycarbonate diol, manufactured by Daicel Chemical Industries, Ltd.) 20
00.0 g (100 mol), adipic acid 292.0 g
(2.00 mol) and 114.6 g of xylene,
On the way, the temperature was raised to 200 ° C. while removing by-product condensed water. Reaction at 200 ° C for 2 hours, acid value 49.7K
OH mg / g of dicarboxylic acid A was obtained.

Then, 4,4-liter flask equipped with a stirrer, a cooling tube, a nitrogen inlet tube and a thermometer was charged with 4,
40.0 g of 4'-diphenylmethane diisocyanate
(0.60 mol), 69.12 g of trimellitic anhydride
(0.36 mol) and 541.44 g (0.24 mol) of the dicarboxylic acid A obtained in the above synthesis and 60.56 g of γ-butyrolactone were added, and the temperature was raised to 160 ° C.
After reacting for 3 hours, a resin having a number average 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 40% by weight. The molar ratio of trimellitic anhydride / dicarboxylic acid A was 0.6 / 0.4.

0.1 part by weight of a titanate-based coupling agent KR138S (trade name of Ajinomoto Co., Inc.) based on 100 parts by weight of the solid content of the obtained resin solution, and KS as an antifoaming agent
0.1 parts by weight of -603 (Shin-Etsu Chemical Co., Ltd .: trade name) and 15 of Aerosil 380 (Nippon Aerosil Co., Ltd., trade name, average surface area: 380 m ² / g) as a filler.
0 parts by weight and 50 parts by weight of gamma butyrolactone as a diluting solvent were mixed and stirred with a stirrer for 1 hour to obtain a solution A.

0.1 part by weight of KS-603 (Shin-Etsu Chemical Co., Ltd .: trade name) as an antifoaming agent and LM as a filler are based on 100 parts by weight of the solid content of the obtained resin solution.
20 parts by weight of S300 (Fuji Talc Kogyo Co., Ltd., trade name, average surface area: 5 m ² / g) was mixed and stirred with a stirrer for 1 hour to obtain a solution B.

The obtained solution A and solution B were mixed at a weight ratio of A: B of 1:10, and Ep-1004 (Yuika Shell Epoxy Co., Ltd .: commercial product) was added to 100 parts by weight of the solid content of the resin solution. (Name, bisphenol A type epoxy resin) was added and stirred for 1 hour to obtain a resin paste.

Example 2 In Example 1, the titanate coupling agent KR13 was used.
A resin paste was obtained in exactly the same manner as in Example 1, except that 1S by weight was used for 8S (Ajinomoto Co., Ltd.).

Example 3 In Example 1, the titanate coupling agent KR13 was used.
A resin paste was obtained in exactly the same manner as in Example 1, except that 8S (Ajinomoto Co., Ltd .: trade name) was used in an amount of 3 parts by weight.

Example 4 In Example 1, the titanate coupling agent KR13 was used.
Except that 8S (Ajinomoto Co., Ltd .: trade name) was 5 parts by weight, the same operation as in Example 1 was performed to obtain a resin paste.

Comparative Example 1 A resin paste was obtained in the same manner as in Example 1, except that no titanate coupling agent was added.

Comparative Example 2 A polyamide-imide resin paste obtained by performing the same operation as in Comparative Example 1 was rolled with three rolls (feed roll gap: 10).
(0 μm, finish roll gap: 30 μm) once to obtain a resin paste.

The properties of the resin pastes and resin compositions obtained in the above Examples and Comparative Examples were measured by the following methods, and the results are shown in the table.

(1) Dispersibility Grain gauge (manufactured by Yoshimitsu Seiki Co., Ltd., 25 μm to 0 μm)
The point where two or more continuous lines of 10 mm or more began to be aligned was used as the value of the dispersed particle diameter, and those having a value of 10 μm or less and exceeding 0.10 μm were evaluated as x.

(2) Moisture resistance The obtained resin paste was printed on a copper foil with a printing machine (trade name: LS-34GX, manufactured by Neurong Co., Ltd.) and a mesh plate (150 mesh, manufactured by Murakami Co., Ltd.).
A 10 mm square was printed at 00 mm / sec to obtain a printed film before drying. The obtained printed film before drying is placed in an air atmosphere for 90 minutes.
After drying at 30 ° C. for 30 minutes, the coating obtained by heating and curing at 160 ° C. for 60 minutes in an air atmosphere was allowed to stand at 121 ° C. for 2 hours in saturated steam at 2 atm. The presence or absence was observed, and those without the sample were evaluated as ○ and those with the test were evaluated as ×.

[0045]

[Table 1]

As is apparent from the above results, Examples 1 to 4 to which a titanate-based coupling agent was added were superior to the Comparative Examples in that the dispersibility by a grain gauge was 10 μm or less and the moisture resistance was excellent. Further, Examples 1 to 4 were Comparative Examples 2 in which the dispersibility by a grain gauge was 10 μm or less and three passes were performed once.
Shows the same dispersibility as that of the resin paste.

[0047]

According to the resin paste of the present invention, a good filler dispersion state can be obtained without performing a mechanical dispersion step such as a three-roll process. The resin paste of the present invention has the above-mentioned excellent properties, and includes an overcoat material for an electronic component, a liquid sealing material, a varnish for an enameled wire, an impregnated varnish for electrical insulation, a varnish for a laminate, a varnish for a friction material, and a printed board. It is suitably used for an interlayer insulating film, a surface protective film, a solder resist film, an adhesive layer and the like in the field, and an electronic component such as a semiconductor element.

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Claims (7)

[Claims] 1. A solution A containing a heat-resistant resin, a solvent, a filler and a titanate-based coupling agent,
A method for producing a resin paste, comprising mixing a solution B containing a solvent and a filler. 2. The heat-resistant resin of the solution A and the solution B is a polyimide resin, a polyamideimide resin or a polyamide resin modified with a flexible and low modulus component.
A method for producing the resin paste as described above. 3. An average surface area of the filler of the solution A is 50 m.
^{3. The} method for producing a resin paste according to claim 1, wherein the amount is ² / g or more. 4. 4. An average surface area of the filler of the solution B is 50 m.
^The method for producing a resin paste according to claim 1 or 2, which is not more than ² / g. 5. The method for producing a resin paste according to claim 1, wherein the titanate-based coupling agent of the solution A is a titanate-based coupling agent containing a phosphoric acid molecule in a side chain organic functional group of the hydrophobic group. 6. The method for producing a resin paste according to claim 5, wherein the amount of the titanate coupling agent in the solution A is 0.1 to 5 parts by weight based on 100 parts by weight of the heat-resistant resin. 7. A resin paste obtained by the production method according to claim 1.