JP2003113338A - Heat-resistant block copolyimide composition for screen printing use and composition of ink using the polyimide and method of forming coating film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyimide screen printing varnish composition and a polyimide paste composition excellent in dense fine pattern design and continuous printability by screen printing method without using any photoresist method and photoprinting method and capable of easily forming adhesive layer or protective layer with high heat resistance and high electrical insulation. SOLUTION: The polyimide screen printing varnish comprises a solvent- soluble block copolyimide resin component, electrical insulating inorganic filler and/or resin-coated inorganic filler (in the form of microparticles 0.001-100 μm in mean size) and resin filler of either epoxy resin, maleimide resin, polyurethane resin, polyimide, polyamide or triazine compound (in the form of microparticles 0.05-100 μm in mean size) which is sparingly soluble to the polyimide solution at <=50 deg.C; wherein the fillers account for 2-50 wt.% of the resin on a solid basis, and the varnish varies in viscosity and thixotropy depending on the particle shape, kind and compounding ratio of the fillers. The objective polyimide composition is suitable for screen printing.

Description

Detailed Description of the Invention

[0001]

INDUSTRIAL APPLICABILITY The present invention has excellent mechanical properties and flexibility, and has heat resistance and insulation properties.
In the field of electronics, flexible wiring boards used for operation panels of various electronic devices, silicon wafers used in semiconductor devices, semiconductor chips, semiconductor device peripheral components, semiconductor chip disposal substrates, heat sinks, lead pins, The present invention relates to a polyimide screen printing varnish for the purpose of forming a pattern on an electronic component for use in protecting, insulating and adhering a semiconductor itself.

[0002]

2. Description of the Related Art Conventionally, in screen printing on polyimide, a high-concentration solution of partially imidized polyamic acid is applied to a substrate through a template, and the patterned coating film is completely imidized on the substrate. It is known that the method of conversion (Tokuhyo 10-502869). The formed coating film is subjected to high temperature treatment (240 to 350) for imidization.
C) is required. As a method for improving these, a screen printing forming method using a polyimide compound has been demanded.

The demand for polyimide flexible printed circuit boards has increased with the advancement of high performance materials. Currently, as a polyimide printed circuit board, an adhesive type in which a copper plate and a polyimide film are heat-bonded using an epoxy-based or polyimide-based adhesive and a non-adhesive type that does not use these are made. Further, it is used as a non-conductor, a cushioning material, and an insulating coating film in the semiconductor manufacturing process. The pattern formation in the polyimide coating film is performed by coating the substrate with a polyamic acid precursor for photoresist, dissolving the exposed or unexposed portion by ultraviolet light exposure and development, and further imidizing the remaining polyamic acid. Be seen. Also,
The photoresist coating film is exposed to a UV pattern on the partially imidized polyamic acid coating film to dissolve the photosensitive or non-photosensitive portion of the photoresist coating film, and also the polyamic acid coating film under the photoresist. The pattern can be formed photographically by dissolving and imidizing the rest of the polyamic acid. However, in any method, exposure to ultraviolet rays is included and several steps are required for pattern processing.

Conventionally, as a method of forming a protective layer on a semiconductor, it has been put into practical use to spin coat a varnish for a protective film such as polyamic acid on a wafer to form a thin film. However, this thin film needs to be polyimidized,
There were many steps and the device was expensive. Furthermore, this varnish can form a thin film having a thickness of several μm.
It is difficult to control a thick film of 0 μm or more. Further, since a thin film cannot be formed only on a necessary portion of the semiconductor, additional steps such as photoetching and formation of a desired protective film pattern have been required.

The first type of varnish used for the polyimide layer is used in the state of polyamic acid. However, since the polyamic acid is supplied by being dissolved in a polar solvent, it is heated by ring closure (imide). Process) is required. During the imidization reaction, a large shrinkage of the formed polyimide resin causes a serious problem of workability, and it is particularly difficult to form a dense patterned protective layer on a semiconductor wafer or the like. In addition, there are many problems such that the polyamic acid is easily hydrolyzed, the polyamic acid is likely to be deposited due to the moisture absorption of the varnish, and the storage stability of the varnish is poor because the ring-opening reaction proceeds slowly at room temperature.

The second form is used as a ring-closed polyimide that has been imidized, but since this polyimide has low solubility, the solid content cannot be increased and varnishing is difficult. Also, due to its low solubility, it is difficult to control the viscosity due to the limited amount of filler component added.
There are problems such as difficulty in obtaining thixotropy.

On the other hand, as another method, there has been proposed a method of forming a resin pattern by exposure using a polyimide resin having photosensitivity. However, this method has a problem that the material for imparting photosensitivity is limited, and in many cases, it cannot be applied by a wet method and is expensive.

[0008]

The conventional polyimide is
Since the polyamic acid has to be processed and is hardly soluble in a solvent, formation processing and screen printing processing are difficult, and there is a problem in using it as a screen printing paste. The present invention has good screen printability, and
A polyimide screen printing varnish for electronic parts, which can be cured at a low temperature of 250 ° C. or less, has heat resistance, flexibility, high insulation and adhesiveness when cured, and can form a fine pattern by a simple method. provide. This was invented in order to solve problems such as a decrease in adhesiveness of a polyimide varnish which has been obtained with a thixotropic property by adding an inorganic filler for improving printability.

(Constitution of the Invention)

[Means for Solving the Problems] In order to achieve the above object, the inventors of the present invention have conducted diligent research and completed the production of a block copolymerized polyimide which is soluble in a solvent. I solved the point. This block-copolymerized polyimide varnish has no bleeding on the surface of the substrate using a mesh or a metal mask in an environment where the room temperature and humidity are 50% or less, and the target pattern is continuously applied 100 times or more without changing the pattern size. The feature is that it can be applied by printing. Printing in which the solid content is high (25 to 50%) and the weight ratio of the polyimide resin and the resin filler, (epoxy resin, maleimide resin, polyurethane resin, polyimide, polyamide, triazine compound epoxy resin) is 100: 5 to 70. A resin composition for use, which provides a film having excellent heat resistance, flexibility, and adhesiveness with adhesive sheets. Further, the present invention provides a composition of a heat-resistant resin paste which can form a reliable and uniform thick film pattern having no voids and bubbles, has little dust and ionic impurities, and is excellent in productivity. Furthermore, since high temperature treatment (240 to 350 ° C.) for imidization is not required, 25
It can be cured at a low temperature of 0 ° C or lower.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The solvent used in the block copolymerization polyimide polymerization reaction of the present invention will be explained. The screen-printing polyimide used in the present invention is a solvent-soluble block copolymerized polyimide, and an organic solvent is used for the polymerization reaction. As these solvents, N, N-dimethylformamide (DMF), N , N-dimethylacetamide (DMAc), dimethyl sulfoxide (DMS)
O), N-methylpyrrolidone (NMP), γ-butyrolactone (γBL), anisole, cyclohexanone, tetramethylurea, sulfolane and the like are used. Preferably, NMP or γBL is used.

Tetracarboxylic acid dianhydride and aromatic diamine are added to these solvents in approximately equimolar amounts and heated in the presence of a catalyst to carry out a dehydration imidization reaction to directly produce a polyimide solution. The catalyst is a two-component composite catalyst. γ-Valerolactone or crotonic acid is mixed with pyridine or N-methylmorpholine. The mixing ratio is 1:
1-5 (molar equivalent), preferably 1: 1-2. When water is present, it exhibits a catalytic action as an acid-base double salt, and when the imidization is completed and water goes out of the reaction system, the catalytic action is lost. The amount of this catalyst used is 1 / 100-1 / 5 mol, preferably 1/5, of the tetracarboxylic dianhydride.
It is 0-1 / 10 mol. The general manufacture of solvent soluble block polyimide compounds is described in US Pat. No. 5,502,14.
No. 3 is described.

The tetracarboxylic dianhydride used in the present invention is pyromellitic dianhydride, 3,3 ', 4,4'.
-Biphenyltetracarboxylic dianhydride, bis (3,4
-Dicarboxyphenyl) ether dianhydride, 3,
3 ', 4,4'-benzophenone tetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride And the like, aromatic dianhydrides, 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, bicyclo [2.2. Oct-7-en-
Aliphatic dianhydrides such as 2,3,5,6-tetracarboxylic dianhydride can be mentioned. These are alone 2
A polyimide composition can be obtained by mixing more than one kind.

The aromatic diamine is not particularly limited, but m-phenylenediamine, p-phenylenediamine, 2,4-diaminotoluene, 4,4'-diamino-
3,3'-dimethyl-1,1'-biphenyl, 4,4 '
-Diamino-3,3'-dimethoxy-1,1'-biphenyl, 4,4'-diamino-3,3'-dihydroxy-
1,1'-biphenyl, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenyl ether, 4,
4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide,
2,2-bis (4-aminophenyl) propane, 2,2
-Bis (4-aminophenyl) hexafluoropropane, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis ( 4-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) biphenyl, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4-
(4-Aminophenoxy) phenyl] hexafluoropropane, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, 3,5-diaminobenzoic acid, 2, 5
-Diaminopyridine, 2,6-diaminopyridine, 2,
6-diamino-4-methylpyridine, 4,4 ′-(9-
Fluorenylidene) dianiline, diaminosiloxane compounds and the like are used. These may be used alone or as a mixture of two or more kinds to form a polyimide composition. The feature of the direct imidization method using a polymerization catalyst is that the solubility is enhanced and the adhesiveness is imparted by using a block copolymer rather than mixing three or more components to form a random copolymer. To improve the physical characteristics.

First, an acid dianhydride and an aromatic diamine are heated in a polar solvent in the presence of an acid catalyst to form an imide oligomer, and then an acid dianhydride and / or an aromatic diamine is added to the imide oligomer. A polyimide is produced by a two-step reaction. This method can prevent random copolymerization due to the exchange reaction between amic acids. As a result, a wide variety of block copolymerized polyimides can be produced, from soft elastomeric polyimides to hard structural polyimides.

Next, the characteristics of the polyimide obtained as described above will be described. 1) Thermal properties Glass transition temperature: 180-350 ° C Thermal decomposition initiation temperature: 400-550 ° C 2) Electrical properties Volume resistance value: 10 (exp17) ohms or more Dielectric constant: 2.5-3.5 3) Machine Properties Tensile strength: 10-25kgf / mm2 Tensile elongation: 20-200% Tensile modulus: 200-350kf / mm2 4) Chemical properties Water absorption rate: 0.2-1% PCT: 16H-100H Solder resistance: Alkali resistance at 260 ° C. for 60 seconds or more: Immersion reaction has already been performed in the block copolymerized polyimide solution in which the weight loss after immersion in 5% caustic soda for 30 minutes is 1-3%. The block copolymerized polyimide used in the present invention does not decompose into water as a polyimide solution having good storage stability as a polyimide solution that does not require imidization reaction. Exhibit excellent properties as a screen printing varnish, not limited to this, for example, a conductive planar heating element and the electrode material of the capacitor type battery, an electrically conductive material, also use as electrical resistance materials possible.

The polyimide of the present invention is a block copolymerized polyimide, and the properties of the polymer required for the screen printing method can be imparted by selecting the copolymerization component. For example, by introducing an adhesive group, the affinity and adhesiveness to metal particles and inorganic particles can be increased (USP 5,502,143).

In the present invention, in order to improve thixotropy, heat resistance and adhesion, the maleimide resin compound added to the block copolymerized polyimide solution is 4,4'-
Bismaleimidodiphenylmethane, bis (4-maleimido-3-methylphenyl) methane, 2,2-bis (4-
Maleimidophenyl) propane, 4,4'-bismaleimide diphenyl ether, 3,4'-bismaleimide diphenyl ether, 4,4'-bismaleimide diphenyl sulfone, 3,3'-bismaleimide diphenyl sulfone, bis [4- (3- Maleimidophenoxy) phenyl] sulfone, 1,3-bis (4-maleimidophenoxy) benzene, 1,4-phenylene bismaleimide,
2,2-bis (4-maleimidophenyl) hexafluoropropane and 2,2-bis [4- (4-maleimidophenoxy) phenyl] hexafluoropropane.
In addition to the maleimide resin compound, it is any of polyurethane resin, polyimide, polyamide, and triazine compound. These are fine particles having an average particle size of 0.05 μm to 100 μm, preferably 2 to 50% by weight, and more preferably 2 to 10 parts by weight, based on the solid polyimide resin. It is characterized by being melted.

An insulating inorganic filler is preferably used in the screen printing polyimide varnish of the present invention. As the insulating inorganic filler that can be used, there are Aerosil, spherical silica, talc, alumina, quartz powder, calcium carbonate, magnesium oxide, mica and the like, and they can be used alone or in combination of two or more kinds. Preferable insulating inorganic fillers include erosil, spherical silica, alumina powder and the like. The average particle size of the insulating filler is
The thickness is preferably 0.01 μm to 100 μm, more preferably 0.05 μm to 40 μm. Particle size is 0.01μm
When it is less than the above range, the thickening effect is large and it is difficult to control the viscosity of the varnish. Further, the amount of the insulating inorganic filler with respect to the resin solid content is preferably 2 to 50 parts by weight, and more preferably 2 to 10 parts by weight.

In screen printing using the paste-like polyimide composition of the present invention, a polyimide film pattern can be obtained by simply removing the solvent. Desolvation is performed at 30 to 250 ° C. in an oven or a hot plate depending on the coating film thickness, but may be a constant temperature over the entire treatment time, or may be performed while gradually raising the temperature. it can. The maximum temperature in the desolvation treatment is in the range of 90 ° C to 220 ° C, and it is preferable to heat for 5 to 60 minutes in an inert atmosphere such as air or nitrogen. A method for producing a polyimide solution used in the present invention,
The characteristics will be specifically described in Examples. The present invention is not limited to these examples because polyimides having various characteristics can be obtained by combining acid dianhydride and aromatic diamine.

[0020]

EXAMPLES The present invention will now be described in more detail with reference to examples. Synthesis Example 1 A 3 liter separable three-necked flask equipped with a stainless steel anchor type stirrer is equipped with a ball cooling tube equipped with a water separation trap. Bicyclo [2.2.
2] Oct-7-ene-2,3,5,6-tetracarboxylic dianhydride (BCD) 198.55 g (800 mmol), 3,4′-diaminodiphenyl ether 80.0
8 g (400 mmol), γ-valerolactone 12.0
1 g (120 mmol), pyridine 18.98 g (24
0 mmol), γ-butyrolactone (γBL) 671
g, and 80 g of toluene are charged. Room temperature, under nitrogen atmosphere, 1
After stirring at 80 rpm for 30 minutes, raise the temperature to 180 ° C. and
Stir for hours. During the reaction, the toluene-water azeotrope was removed. Then, the mixture was cooled to room temperature, and 128.89 g (4: 3,3 ', 4,4'-benzophenone tetracarboxylic acid dianhydride)
00 mmol), 2,6-diaminopyridine 43.65
g (400 mmol), bis [4- (3-aminophenoxy) phenyl] sulfone 173.00 g (400 mmol), γBL 200 g, and toluene 80 g were added, and 18
The reaction was carried out for 7 hours while stirring at 0 ° C and 180 rpm.
By removing the refluxed substance outside the system, a polyimide solution having a concentration of 40% was obtained. When the molecular weight of the thus obtained polyimide was measured by gel permeation chromatography (manufactured by Tosoh Corporation), the styrene-equivalent molecular weights were number average molecular weight (Mn) 22,000 and weight average molecular weight (M
w) 45,000, Z average molecular weight (Mz) 76,000
0 and Mw / Mn = 2.02. This polyimide was poured into methanol, made into a powder, and subjected to thermal analysis. Glass transition temperature (Tg) is 277.5 ° C, decomposition start temperature is 41
It was 7.0 ° C.

Synthesis Example 2 A 2-liter separable three-necked flask equipped with an anchor type stirrer made of stainless steel was equipped with a condenser tube with a ball equipped with a water separation trap. 3,3 ', 4,4'
-Benzophenone tetracarboxylic dianhydride 32.22
g (100 mmol), 2,4-diaminotoluene 6.
11 g (50 mmol), γ-valerolactone 1.50
g (15 mmol), pyridine 2.37 g (30 mmol), γBL 150 g, and toluene 30 g are charged. After stirring at 180 rpm for 30 minutes at room temperature under a nitrogen atmosphere,
It heated up at 180 degreeC and stirred for 1 hour. During the reaction, the toluene-water azeotrope was removed. Then cool to room temperature3.
14.71 g (50 mmol) of 3 ', 4,4'-biphenyltetracarboxylic dianhydride (BPDA), 2,2-
Bis [4- (4-aminophenoxy) phenyl] hexafluoropropane 25.93 g (50 mmol), 2,
5.46 g (50 mmol) of 6-diaminopyridine, γ
BL35g, toluene 30g are added, 180 degreeC, 180
The reaction was carried out for 5 hours while stirring at rpm. A reflux solution was removed from the system to obtain a polyimide solution having a concentration of 30%.
When the molecular weight of the thus obtained polyimide was measured by gel permeation chromatography (manufactured by Tosoh Corporation), the styrene-equivalent molecular weights were number average molecular weight (Mn) 22,000, weight average molecular weight (Mw) 42,
2,000, Z average molecular weight (Mz) 72,000, Mw / M
It was n = 1.91. This polyimide was poured into methanol, made into a powder, and subjected to thermal analysis. Glass transition temperature (Tg)
Was 276.9 ° C. and the decomposition initiation temperature was 464.3 ° C.

Synthesis Example 3 49.64 g (200 mmol) of BCD, 45.65 g (300 mmol) of 3,5-diaminobenzoic acid, 5.01 g (50 mmol) of γ-valerolactone, 7.91 g (100 mmol) of pyridine, N-methylpyrrolidone (NMP) 408 g, toluene 40 g and BPDA8
8.27 g (300 mmol), bis [4- (3-aminophenoxy) phenyl] sulfone 43.25 g (10
0 mmol), 2,2-bis [4- (4-aminophenoxy) phenyl] propane 41.05 g (100 mmol), γBL175 g, and toluene 40 g were used, and a polyimide solution having a concentration of 30% was prepared in the same manner as in Synthesis Example 1. Got Further, its molecular weight, glass transition point and thermal decomposition initiation temperature were measured. The results are shown in Table 1.

Synthesis Example 4 176.53 g (600 mmol) of BPDA, bis [4
-(3-Aminophenoxy) phenyl] sulfone 86.
50 g (200 mmol), diaminosiloxane (Mw
830) 83.00 g (100 mmol), γ-valerolactone 9.01 g (90 mmol), pyridine 14.
24 g (180 mmol), NMP 750 g, toluene 80 g and BTDA 96.67 g (300 mmol),
48.87 g (400 mmol) of 2,4-diaminotoluene, 82.10 g (200 mmol) of 2,2-bis [4- (4-aminophenoxy) phenyl] propane, N
A polyimide solution having a concentration of 40% was obtained by the same method as in Synthesis Example 1 using 62 g of MP and 40 g of toluene. Also,
Its molecular weight, glass transition point and thermal decomposition initiation temperature were measured. The results are shown in Table 1.

Synthesis Example 5 64.45 g (200 mmol) BTDA, 48.87 g (100 mmol) 2,4-diaminotoluene, γ-
Valerolactone 3.00 g (30 mmol), pyridine 4.75 g (60 mmol), γBL 400 g, toluene 40 g and BTDA 32.22 g (100 mmol), bis [4- (3-aminophenoxy) phenyl].
Sulfone 60.55 g (140 mmol), 3,5-diaminobenzoic acid 4.56 g (30 mmol), 2,6-
Diaminopyridine 3.27 g (30 mmol), γBL
A polyimide solution having a concentration of 25% was obtained by the same method as in Synthesis Example 1 using 99.4 g and 40 g of toluene. Also,
Its molecular weight, glass transition point and thermal decomposition initiation temperature were measured. The results are shown in Table 1.

[0025]

[Table 1]

Example 1 Polyimide varnish synthesized in Synthesis Example 1 was mixed with silica fine powder (trade name AEROSIL 20 manufactured by Nippon Aerosil Co., Ltd.).
0 and primary particles having an average particle size of 0.016 μm) were added, and then sufficiently mixed with a NR-120A ceramic three-roll mill manufactured by Noritake Co., Ltd. to obtain a polyimide paste for screen printing of the present invention.

For Examples 2 to 9, the resin solid content concentration (% by weight) of the polyimide varnish used, the primary particle average particle diameter of the filler to be added, the type of silica and resin farah, and the polyimide resin solid content of 100 parts by weight. The amount of addition (parts by weight) is shown in Table 2, and is prepared in the same manner as in Example 1.

[0028]

[Table 2]

(Evaluation of Screen Printability) In the examples, screen printing was carried out by using MT-550TVC screen printing machine manufactured by Microtec Co., Ltd. using a test screen mask of PII, and the characteristics of the following items were evaluated. 1) Regarding the pattern shape, a fine pattern (L (line width) / S (line interval) = 30, 40,
50, 60, 70, 80, 100, 150, 200, using a test printing screen (400 mesh stainless steel, emulsion thickness 16 μm), screen printing was continuously performed 10 shots on the SUS plate, and then at room temperature. 5-10
Leveling was performed for minutes, and the organic solvent component was dried by heating in a hot air oven at 90 ° C., 180 ° C., and 250 ° C. for 20 minutes each, and the shape of the pattern was evaluated visually and by an optical microscope. Evaluation is based on the pattern "bluish or sagging defect (paste spreads in the pattern width direction, defect in the bridge state connected to the adjacent pattern)", "blurring defect (printed pattern smaller than the specified size, pattern ”,“ Void or chip ”, and“ Rolling property (when the squeegee moves, the paste is on the screen in the forward direction of the squeegee,
(Poor rotation condition when rotating and flowing in a substantially cylindrical state) ”. The results are shown in Table 3.

[0030]

[Table 3]

2) Continuous printability The continuous printability (the target pattern can be continuously screen-printed 100 times with almost no change in the pattern size) was evaluated by continuously printing the above pattern and the 10th shot from the start of printing. After that, the pattern was extracted every 10 shots up to 100 shots, dried under the same conditions as in the case of the pattern evaluation, and then the shape of the same pattern as above was visually observed and observed with an optical microscope. The results are shown in Table 4. In the table, ◯ marks of the continuous shots indicate that the pattern has a good shape, and X marks indicate that the pattern has a bad pattern. However, when the pattern shape was significantly deteriorated, printing was stopped.

[0032]

[Table 4] As can be seen from the results of Table 3 and Table 4, the polyimide varnish for screen printing of the present invention was excellent in pattern shape and continuous printability.

[0033]

EFFECT OF THE INVENTION The polyimide varnish for screen printing of the present invention is excellent in pattern shape and continuous printability, and it is possible to easily form an adhesive layer or a protective layer excellent in heat resistance and high insulation by screen printing. You can In particular, the conventional image formation of the surface protective film and the polyimide film for the interlayer insulating film has been performed by the photoetching method using the photoresist, but in recent years, the technology of the photoprinting method using the photosensitive polyimide has made great progress. The image forming process has been simplified, and the application of polyimide in the electronics field has spread. However, most of polyimides have been used in spinner spin coating, which is inferior in coating efficiency, regardless of photosensitivity and non-photosensitivity. Therefore, improvement of coating efficiency and further simplification of the image forming process have been problems. Therefore, as one of the solutions, the screen printing method of the present invention is proposed. Since this method directly forms an image on a substrate using a screen without performing steps such as exposure, development or etching, it is a simpler image forming method than the photoetching method and the photoprinting method. .

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Hiroyuki Ishii             205, 4-3, Isogo-ku, Yokohama-shi, Kanagawa             Room (72) Inventor Xuhua             34-30 Machiyamachi, Kanazawa-ku, Yokohama-shi, Kanagawa             202 rooms (72) Inventor Hiroshi Itaya             2-125 Minato-shinden, Ichikawa City, Chiba Prefecture F-term (reference) 4J039 AE05 AE08 AE09 AE13 BA13                       BA22 BA32 BA35 BC05 BC12                       BC13 BC16 BC20 BC29 BC31                       BC36 BC37 BC50 BC51 BC52                       BC54 BC55 BE12 CA07 CA08                       EA37 EA47 GA10                 4J043 PA09 QB15 QB26 RA39 SA06                       SB02 TA22 TA71 UA032                       UA121 UA122 UA131 UA132                       UA361 UB052 UB062 UB121                       UB122 UB301 UB302 XA13                       XB19 XB37 ZA33 ZB50

Claims (12)

[Claims] 1. A solvent-soluble block copolymer polyimide composition for screen printing, which is obtained by polycondensing a tetracarboxylic dianhydride and an aromatic diamine in the presence of an acid catalyst composed of a lactone and a base. 2. A tetracarboxylic dianhydride and an aromatic diamine are added at 160 to 200 ° C. in the presence of a binary catalyst of γ-valerolactone and pyridine or / and methylmorpholine.
To produce an imidized oligomer, and then tetracarboxylic dianhydride and / or aromatic diamine is added in a molar ratio of total acid dianhydride to aromatic diamine of 1: 0.95 to 1:
A block copolymerized polyimide resin composition obtained by heating and dehydrating in addition to 1.05. 3. The tetracarboxylic dianhydride is pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride. Anhydride, 3,3 ', 4,4'-benzophenone tetracarboxylic acid dianhydride, bicyclo [2.
2.2] It is selected from octo-7-ene-2,3,5,6-tetracarboxylic dianhydride and 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride. Characterize. 4. The aromatic diamine of the block polyimide resin component is m-phenylenediamine, p-phenylenediamine, 2,4-diaminotoluene, 4,4′-
Diamino-3,3'-dimethyl-1,1'-biphenyl, 4,4'-diamino-3,3'-dihydroxy-
1,1'-biphenyl, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether,
3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide, 2,2-bis (4-aminophenyl)
Propane, 2,2-bis (4-aminophenyl) hexafluoropropane, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy)
Benzene, 4,4'-bis (4-aminophenoxy) biphenyl, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] Hexafluoropropane,
Bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, 3,5-diaminobenzoic acid, 2,6-diaminopyridine, 2,6-diamino-4. -Methylpyridine,
4,4 '-(9-fluorenylidene) dianiline, diaminosiloxane compounds and the like can be mentioned. 5. The organic solvent used in the reaction includes N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, sulfolane, 1,3-dimethyl-2-imidazolidone and the like. Aprotic polar solvent, phenolic solvent such as phenol, cresol, xylenol, p-chlorophenol, tetramethylurea, butyrolactone, anisole, cyclohexanone, lactone solvent and the like. Further, two or more kinds of solvents are mixed and used. 6. The solvent is a lactone solvent, sulfolane, anisole, cyclohexanone, glyme solvent, glycol monomethyl ethers, glycol diethyl ethers, glycol monoethyl ethers, glycol monoacetylated products, glycol diacetylated products. A polyimide screen printing varnish comprising at least one selected from the group consisting of, cellosolves, and cyclic ethers. 7. In order to improve the printability of the heat-resistant resin varnish, the block copolymerized polyimide solution contains an insulating inorganic filler and / or a resin-coated inorganic filler and / or a resin filler in a part by weight based on the resin solid content. The printing varnish according to claim 1, wherein the adhesive composition is used. 8. The block copolymerized polyimide solution according to claim 1, comprising an insulating inorganic filler and / or a resin-coated inorganic filler, and fine particles having an average particle size of 0.001 μm to 100 μm (erosil, aluminum oxide, titanium dioxide, etc.). It is characterized in that it is contained in an amount of 2 to 50% by weight with respect to the resin solid, and the viscosity and thixotropy change depending on the shape, type and blending ratio of the filler. 9. The resin filler added to the block copolymerized polyimide solution according to claim 1, has an average particle size of 0.05 μm to
One of 100 μm fine particle epoxy resin, maleimide resin, polyurethane resin, polyimide, polyamide, and triazine compound, which is characterized by being hardly soluble in a polyimide solution at 50 ° C. or lower. Each filler is 2 to 50% by weight based on the solid resin. 10. The styrene-equivalent weight molecular weight of the polyimide of claim 1 is 25,000 to 400,000, preferably 30,000 to 200,000, and its thermal decomposition initiation temperature is 450.
A heat-resistant polyimide composition having a temperature of ℃ or higher. 11. A polyimide screen printing varnish wherein the block copolymerized polyimide solution of claim 1 contains from about 100 ppm to about 10% by weight of a surfactant. 12. The polyimide screen printing paste according to claim 11 forms a thick film high-definition pattern having no defects such as dripping and bleeding on the surface of a substrate by using a metal mask or a screen stencil metal mesh as a member in the printing process. It features a printing method. The proper printing condition for screen printing is that the clearance is 1/300 of the inner size of the screen frame.
Squeegee printing pressure is 100 ~ 300g / cm, squeegee angle is 65 ~ 75 °, squeegee speed is 40 ~ 15
0 mm / sec is preferable.