JP2002363424A - Resin paste and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin paste excellent in printability by enabling a high- filling of a filler excellent in shape retaining property and having surface area of >=50 m2/g by formulating a titanate based coupling agent which includes a phosphoric acid molecule in a side chain organic functional group as a hydrophobic group, to a solution of a heat resistant resin such as a polyimide resin, a polyamide imide resin, or a polyamide resin, modified by a flexibilizing and low-modulus component and to provide a method for producting the same. SOLUTION: The resin paste and the method for producting the same characteristically formulate the titanate based coupling agent including the phosphoric acid molecule on the side chain group as the hydrophobic group to the solution including the resin and the solvent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin paste suitable for a coating method such as a screen printing machine, a dispenser and a spin coater, and a method for producing the same. In particular, the present invention relates to a resin pace suitable for screen printing and a method for producing the same.

[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 is used. 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
Publication). 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 the insulating film and the insulating layer are directly formed on the substrate by using the screen printing method, the wiring circuit on the substrate comes into direct contact with the screen plate, so that the wiring circuit has a problem such as a flaw or disconnection. In addition, with the recent miniaturization and thinning, there is a problem that the distance between the wirings is reduced and the flow of the resin paste generated between the wirings is increased. Also,
If a large amount of filler with a small particle size is used to reduce the flow of the resin paste, the viscosity and thixotropic properties of the resin paste will increase and the paste will flow out and retain its shape, but will have problems with plate separation, resolution, and leveling. There is.

[0004]

DISCLOSURE OF THE INVENTION The present invention relates to a method for preparing a resin by adding a titanate coupling agent to a resin solution of a polyimide resin, a polyamideimide resin, or a polyamide resin modified with a flexible and low-modulus component. The present invention relates to a resin paste improved in flow-out, shape retention, plate separation, resolution, and leveling by suppressing the viscosity and thixotropic properties of a resin paste filled with a small-diameter filler at a high level, and a method for producing the same.

[0005]

SUMMARY OF THE INVENTION The present invention relates to the following. (1) A method for producing a resin paste, comprising mixing a filler and a titanate-based coupling agent into a solution containing a heat-resistant resin and a solvent to form a resin paste. (2) The method for producing a resin paste according to (1), wherein the surface area of a part or all of the filler contained in the resin paste is 50 m ² / g or more. (3) The filler having an average filler surface area of 50 m ² / g or more contained in the resin paste has a heat-resistant resin solid content of 100.
The method for producing a resin paste according to (2), wherein the amount is 15 parts by weight to 30 parts by weight with respect to parts by weight. (4) A titanate-based coupling agent containing a phosphoric acid molecule in the side chain organic functional group of the hydrophobic group of the titanate-based coupling agent of the resin paste (1), (2).
Or the method for producing a resin paste according to (3). (5) The content of the titanate coupling agent in the resin paste is 0.5 to 100 parts by weight of the heat-resistant resin solids.
The method for producing a resin paste according to (4), wherein the amount is from 5 parts by weight to 5 parts by weight. (6) A resin paste obtained by the production method according to any one of (1) to (5).

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The resin paste of the present invention is obtained by blending a filler and a titanate coupling agent into a resin solution containing a heat-resistant resin and a solvent.

The heat-resistant resin used in the resin paste of the present invention is preferably a resin having excellent heat resistance, and is preferably a polyimide resin, a polyamideimide resin, or a polyamide resin modified with a flexible and low-modulus component. Used. The modified resin is not particularly limited as long as it is various known modifications, and examples thereof include those modified with a silicone resin, those modified with a polycarbonate resin, those modified with polybutadiene, and the like. Can be. Among them, a polyamide imide resin modified with a polycarbonate resin is preferred.

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

The solution containing the heat-resistant resin and the solvent in the present invention is a solution 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. Is used.

The filler having an average surface area of 50 m ² / g or more used in the resin paste 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. Various things 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,
In some cases, several types may be used in combination.

Filler used for resin paste of the present invention
50m average surface area ²/ G or less
-Dispersed in a solution containing the above-mentioned heat-resistant resin and solvent
Without limitation, as long as it forms a paste.
Seeds are used. For example, talc, calcium carbonate
Aluminum, titanium oxide, mica, aluminum carbonate
Aluminum hydroxide, magnesium silicate, silicon
Mosquito, barium sulfate, short glass fiber and aluminum borate
And various whiskers such as silicon carbide.

The above filler may be used alone,
In some cases, several types may be used in combination.

As the filler in the present invention, a filler having an average surface area of the filler of 1 m ² / g or more and a particle characteristic is preferably used. When the average surface area is 1 m ² / g or less, the fluidity of the resin paste tends to increase, and the shape retention tends to decrease. The upper limit is not particularly limited, but is usually 40.
0 m ² / g or less.

In the present invention, the total amount of the filler used is:
It is preferably 25 to 55 parts by weight based on 100 parts by weight of the resin solid content of the solution containing the heat resistant resin and the solvent. If the amount is less than 25 parts by weight, the shape retention tends to decrease.
If it exceeds 5 parts by weight, the leveling property and the defoaming property tend to decrease.

In the present invention, the amount of the filler used in the resin paste is 10% of the solid content of the solution containing the heat-resistant resin and the solvent.
It is preferable that the amount be 100 parts by weight or less based on 0 parts by weight. If it exceeds 100 parts by weight, the viscosity tends to increase and the dispersibility tends to decrease.

The titanate-based 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. It is appropriately selected depending on the type. 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.

Examples of the polyimide resin, polyamide imide resin and polyamide resin modified with a flexible and low modulus component include KR38S (Ajinomoto Co., Ltd .: trade name) and KR138S (Ajinomoto Co., Ltd .: trade name) ), KR
Titanate-based coupling agents such as 238S (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 some cases, may be used in combination.

The content of the titanate coupling agent is as follows:
In consideration of dispersibility and viscosity, the content is preferably 0.5 to 5% by weight based on 100 parts by weight of the resin solid content of the solution containing the heat-resistant resin and the solvent. If the amount is less than 0.5 part by weight, the printing properties tend to decrease, and if it exceeds 5 parts by weight, the 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, etc.
Heat stabilizers, antioxidants, flame retardants, lubricants, defoamers, leveling agents and the like can also be added.

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 with respect to 100 parts by weight of the heat-resistant resin in view 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.

[0024]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

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.) 2
000.0 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, 2 liter four-necked flask equipped with a stirrer, a cooling pipe, a nitrogen introducing pipe 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), 541.44 g (0.24 mol) of the dicarboxylic acid A obtained in the above synthesis and 760.56 g of γ-butyrolactone were added, and the temperature was raised to 160 ° C., followed by a reaction for 3 hours. 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 40% by weight. The molar ratio of trimellitic anhydride / dicarboxylic acid A was 0.6 / 0.4.

0.5 part by weight of a titanate 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 a defoaming agent
0.1 parts by weight of -603 (Shin-Etsu Chemical Co., Ltd .: trade name), and 21 of Aerosil 380 (Nippon Aerosil Co., Ltd., trade name, average surface area: 380 m ² / g) as a filler.
15 parts by weight of LMS300 (trade name, average surface area: 5 m ² / g) as a combined filler
Parts by weight and 50 parts by weight of gamma butyrolactone as a diluting solvent were mixed and stirred for 1 hour with a stirrer to obtain a resin paste.

The obtained polyamideimide resin solution A and polyamideimide resin solution B were mixed at a ratio of 1:10, and Ep-100 was added to 100 parts by weight of the solid content of the used resin solution.
4 (Yuka Kasper Epoxy Co., Ltd .: trade name, bisphenol A type epoxy resin) was added at 20% by weight, and stirred for 1 hour to obtain a resin paste.

Example 2 In Example 1, a titanate coupling agent KR13 was used.
8S (Ajinomoto Co .: trade name) except for 1 part by weight,
The same operation as in Example 1 was performed to obtain a resin paste.

Example 3 In Example 1, a titanate coupling agent KR13 was used.
Except that 3 parts by weight of 8S (Ajinomoto Co., Ltd .: trade name) was used.
The same operation as in Example 1 was performed to obtain a resin paste.

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

Comparative Example 1 In Example 1, a titanate coupling agent KR13 was used.
A resin paste was obtained in exactly the same manner as in Example 1, except that 0.05 parts by weight of 8S (Ajinomoto Co., Ltd .: trade name) was used.

Comparative Example 2 The titanate coupling agent KR13 in Example 1
8S (Ajinomoto Co .: trade name) except for 7 parts by weight,
The same operation as in Example 1 was performed to obtain a resin paste.

Comparative Example 3 A resin paste was obtained in the same manner as in Example 1 except that no titanate coupling agent was added.

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) Viscosity The viscosity was measured using an E-type viscometer (Toki Sangyo Co., Ltd., trade name: RE
25 ° C. using −80 U, cone 3 ° × R9.7)
The viscosity was measured at 10 rpm for 3 minutes.

(2) Thixotropic Thixotropic is an E-type viscometer (Toki Sangyo Co., Ltd., trade name: R
E-80U, cone 3 ° × R9.7) at 25
At 10 ° C. and 1 rpm for 3 minutes each, and 1 rpm
Was divided by the measured viscosity at 10 rpm to give the degree of thixotropicity.

(3) Printability On a polyimide film of 100 μm, the obtained polyamideimide resin paste was applied with a printing machine (trade name: LS-34GX, manufactured by Neurong Co., Ltd.) and a mesh plate (150 mesh, manufactured by Murakami Co., Ltd.). Printing speed 100mm
/ Sec, and dried at 90 ° C. for 30 minutes in an air atmosphere, and then heat-cured at 160 ° C. for 60 minutes in an air atmosphere to obtain a polyamideimide resin film, which is a universal projector (manufactured by Nikon Corporation, magnification: 50). ×), the surface state of the polyamideimide resin coating was evaluated as ○: no irregularities on the surface, ×: irregularities on the surface.

(4) Shape Retention A polyamide-imide resin paste obtained was printed on a copper circuit (circuit width: 50 μm, circuit interval: 50 μm) using a 18 μm copper foil on a 100 μm polyimide film by using a printing machine (available from Neuron Corporation). Product name: LS-34GX)
And mesh plate (150 mesh manufactured by Murakami Co., Ltd.)
Prints 10mm square at a printing speed of 100mm / sec.
After drying at 90 ° C for 30 minutes in an air atmosphere,
A polyamide-imide resin film obtained by heating and curing at 0 ° C. for 60 minutes was used as a universal projector (Nikon Corporation, magnification 5
(0x), the printed edge portion was observed, and the length of the resin film oozing out at the time of the copper circuit was defined as shape retention.

(5) Moisture resistance The obtained resin paste is printed on a copper foil at a printing speed of 1 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 polyamide-imide resin film obtained by heating and curing at 160 ° C. for 60 minutes in an air atmosphere is subjected to 121 ° C.
At 100 ° C. in saturated steam at 2 atm for 100 hours to observe the surface of the polyamide-imide resin film to observe the presence or absence of peeling and swelling.

[0041]

[Table 1]

[0042]

[Table 2]

As is clear from the above results, Comparative Example 1
3 and 0.05 parts by weight and 7 parts by weight of the titanate-based coupling agent were not added to the resin paste, and the phosphoric acid side chain organic functional group was phosphoric acid-free. In Examples 1 to 4 in which 0.5 to 5 parts by weight of a titanate-based coupling agent containing a molecule was added, the viscosity and the thixotropic degree were reduced, and the printability, shape retention, and moisture resistance were excellent.

[0044]

The resin paste of the present invention has a surface area of 50 m, which is excellent in shape retention, by using a titanate coupling agent containing a phosphoric acid molecule in a side chain organic functional group of a hydrophobic group.
High filling of ² / g or more filler is possible, and a resin paste having excellent printability is obtained. Therefore, the resin paste of the present invention has the above excellent properties, an overcoat material for electronic components, a liquid sealing material, a varnish for enameled wire, an electrical insulation impregnated varnish, a laminate varnish, a friction material varnish, Interlayer insulation film, surface protection film, etc. in the printed circuit board field, etc.
It is suitably used for an electronic component such as a solder resist film, an adhesive layer, and a semiconductor element.

Claims (6)

[Claims] 1. A method for producing a resin paste, comprising mixing a filler and a titanate-based coupling agent into a solution containing a heat-resistant resin and a solvent to form a resin paste. 2. The method for producing a resin paste according to claim 1, wherein the surface area of a part or the entire amount of the filler contained in the resin paste is 50 m ² / g or more. 3. The method according to claim 1, wherein the filler having an average filler surface area of 50 m ² / g or more contained in the resin paste is 15 to 30 parts by weight based on 100 parts by weight of the heat-resistant resin solid content. 3. The method for producing a resin paste according to item 2. 4. The resin according to claim 1, wherein the resin is a titanate coupling agent containing a phosphoric acid molecule in a side chain organic functional group of a hydrophobic group of the titanate coupling agent of the resin paste. Method of producing paste. 5. The method for producing a resin paste according to claim 4, wherein the amount of the titanate coupling agent in the resin paste is 0.5 to 5 parts by weight based on 100 parts by weight of the heat-resistant resin solids. . 6. A resin paste obtained by the production method according to claim 1.