JPH04153261A - Heat-resistant resin paste and ic prepared by using same - Google Patents

Abstract

PURPOSE:To obtain a heat-resistant resin paste suitable as an overcoating material for screen printing by dispersing resin particles or inorganic particles in a solution prepared by dissolving an aromatic polyamic acid (derivative) prepared by a specified process in a nonnitrogenous solvent. CONSTITUTION:A heat-resistant resin paste is obtained by dispersing resin particles (e.g. polyamide resin particles) and/or inorganic particles (e.g. silica) in a solution prepared by dissolving an aromatic polyamic acid obtained by reacting 2,4'-diaminodiphenyl ether with a tetrabasic acid dianhydride of formula I (wherein X is -O-, -CO-, -SO2-, a group of formula II or a single bond) and/or its reactive derivative (particularly desirably a tetrabasic acid ester) or its derivative in a nonnitrogenous solvent (e.g. gamma-butyrolactone or cyclohexanone). This paste can be applied by screen printing, excels in the stability on the press in repeated printing and nonswellability and insolubility in an emulsifier and is desirable as an overcoating material for screen printing.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a novel heat-resistant resin paste suitable as an overcoat material for screen printing and an IC using the same.

(Prior Art) Usually, a resin solution itself exhibits almost no chicken tropism. Chickentropy is defined as a phenomenon in which the viscosity temporarily decreases during deformation even under isothermal conditions.9For example, under high shear speeds during printing, the viscosity temporarily decreases and the base material flows. This flow characteristic is essential for screen printing pastes, which are required to not sag or flow after transfer. One method for imparting chicken tropism to a resin solution is to disperse fine resin particles and/or inorganic particles as fillers in the resin solution and form it into a paste. Various types of such pastes are known.

Examples of resin solutions used in applications that do not require high heat resistance include rosin-modified phenolic resins, rosin-modified maleic resins, and melamine resins.

Resin solutions such as epoxy resins are known for use in applications requiring high heat resistance, such as polyamic acid resins, which are precursors of polyimide resins, and solvent-soluble polyimide resins. In addition, as resin particles that are dispersed in these resin solutions to form a paste, aliphatic polyamide resin particles, melamine resin particles, epoxy resin particles, phenolic resin particles, etc. are known for applications that do not require much heat resistance. For applications that require a high degree of heat resistance, use polyimide resin particles.

Polyamideimide resin fine particles, polyamide resin fine particles, and the like are known. On the other hand, as inorganic fine particles, 9 synthetic silica is used for applications that require insulation.

Alumina fine particles are known, and silver, copper, nickel fine particles, etc. are known for applications requiring conductivity.

(Problem to be Solved by the Invention) For applications that require a high degree of heat resistance, such as when the surface covered by the paste is a semiconductor chip, heat-resistant resin fine particles and/or the above-described polyamic acid resin solution or polyimide resin solution are used.
Alternatively, a base paste in which inorganic fine particles are dispersed is used. Furthermore, these resins having high heat resistance are used in a highly polar nitrogen-containing solvent KI@, such as tJfN-methylpyrrolidone, which has poor solubility.

However, screen printing pastes obtained using nitrogen-containing bath additives have the disadvantage that, due to the high hygroscopicity of nitrogen-containing solvents, the paste sticks to the screen during printing, clogging the screen and making printing impossible. . Moreover, this paste has the disadvantage that the excellent solubility of the nitrogen-containing # agent causes the emulsion forming the screen printing plate to swell or bathe, shortening the life of the plate.

The present invention aims to solve these problems, and preferably provides a heat-resistant resin paste having thixotropic properties and an IC using the same.

(Means for solving 11 problems) Fi44'-diaminodiphenyl ether of the present invention.

-Math+1+ CH.

(wherein, X is -o-, -co-, -so, -c- or C
H1 indicates a single bond that does not contain any of these. The present invention relates to a heat-resistant resin paste made by dissolving fine resin particles and/or inorganic fine particles in a dilute solution dissolved in a solvent.

Examples of the tetrabasic dianhydride represented by formula +11 in the present invention include 1, 4,4'-oxycyphthalanhydride, 3. xtt'-benzophenonetetracarboxylic dianhydride, bis(3,4-dicarboxyphenyl)sulfone hydrate, 2,2-bis(λ4-dicarboxyphenyl)propane, 11.3.3'4. 4'-biphenyltetracarboxylic dianhydride and the like are used. As reactive derivatives of these tetrabasic acid dianhydrides, 9, for example, V
Xj Basic acids, tetrabasic acids...lights, esters, amide ammonium salts, etc. are used. % of tetrabasic acids are preferably used. Two or more of the tetrabasic acid dianhydrides and/or their reactive derivatives can be used as necessary.

The aromatic polyamic acid or its derivative in the present invention includes 44'-diaminodiphenyl ether and one formula CI+
It is obtained by reacting with a tetrabasic acid dianhydride represented by and/or a reactive derivative thereof.

44'-diaminodiphenyl ether! : − Formula (
The proportion of the tetrabasic acid dianhydride and/or its reactive derivative represented by 11 can be arbitrarily determined depending on the purpose. In order to obtain a high molecular weight product, the ratio of i'12,4'-diaminodiphenyl ether and the tetrabasic acid dianhydride represented by the general formula (I) and/or its reactive derivative is approximately equimolar. is preferred.

The reaction temperature is preferably in the range of -10 to 60°C.

Furthermore, in the present invention, known diamines,
For example, p-phenylenecyamine, 9m-phenylenediamine, p-xylylenediamine.

m-xylylenediamine, 1.5-diaminonaphthalene, 3.3'-dimethylbenzidine, 3.3'-dimethoxybenzidine, 4.4'-(or a, 4'-3,3'-
2,4'-,2,2'-)diaminodiphenylmethane,
44'-(or 4'-, 3,3'-, 42'-)diaminodiphenyl ether, 4,4'-(also Fi 4'-)
3,3'-2,4'-2,f-)diaminodiphenylsulfone.

44'-(or 3.4'-3,3'-, Su4'-, Su2'-)diaminodiphenylsulfi)", 4.4
'-Benzphenonediamine, 44'-di(4-aminophenoxy)phenylsulfone, 1,1,1,3,
3.3-hexafluoro-42-bis(4-aminophenyl)furopane, 2-bis(4-(4-aminophenoxy)phenyl)propane, &3-dimethyl-4.4'
-diaminodiphenylmethane, aa;s,s'-tetramethyl-44'-diaminodiphenylmethane, 4.4'
-di(3-aminophenoxy)phenylsulfone, 31
3'-diaminodiphenylsulfone, 2-bis(4-
aminophenyl)propane, below - formula (II) (Rt
and Tori are divalent hydrocarbon groups, 几3 and R4 are monovalent hydrocarbon groups, and R1 and R, , R, and R4 may be the same or different, respectively (, m is an integer of 1 or more )
A diamine represented by, preferably.

- In the formula (If), 几 and R each have 1 to 5 carbon atoms.
an alkylene group, a phenylene group, or an alkyl-substituted phenylene group, and R3 and R are an alkyl group having 1 to 5 carbon atoms, a phenyl group, or an alkyl-substituted phenyl group. I can do it. The ratio of these diamines to the total diamines is desirably F130 or less. If this ratio exceeds 30 mol.

Solubility order Fi of aromatic polyamic acid or its derivative
This is not preferable because it adversely affects heat resistance.

However, in the present invention, if necessary.

Pyromellitic dianhydride, 2,2-bis[4-(2゜3
-IJ-tλ4-dicarboxyphenoxy)phenyl]
Propani anhydride, 1,1. R3,3,3-hexafluoro-2,2-bisI: 4-(Z3- or 3,4-dicarboxyphenoxy)phenyl]propanihydride, binu(exo-bicycloCZ2,1)heptane-2, 3-
known acid dianhydrides such as dicarboxylic acid anhydrides) sulfones,
Terephthalic acid, isophthalic acid.

Known dicarboxylic acids such as phthalic acid, diimide dicarboxylic acids obtained by reacting the above-mentioned known diamines with tetrabasic dianhydrides or reactive derivatives of tetrabasic dianhydrides;
The following formula is represented by the following formula (wherein and R6 represent a monovalent hydrocarbon group, R,, and asV'i may be the same or different, and n is O or an integer of Fi1 or more) Basic acid dianhydride, preferably - in formula (III) R, and R
6 is a methyl group, n! A tetrabasic acid dianhydride which dissolves in dO, 1 or Fi2 can be used in combination as an acid component. The proportion of these tetrabasic acid dianhydrides, dicarboxylic acids and diimidodicarboxylic acids to the total acid component is 3.
It is preferably 0 molti or less. If this ratio exceeds 30 moles, it is undesirable because it will adversely affect the solubility or heat resistance of the aromatic polyamic acid or its derivative.

Examples of nitrogen-free solvents in the present invention include 9, for example, γ-
Butyrolactone, r-valerolactone.

Lactones such as γ-caprolactone, E-caprolactone, and α-acetyl-γ-butyrolactone.

Cyclohexane, alicyclic ketones such as 4-methylcyclohexanone, tetrahydrofuran, dioxane, 1.2
- Ethers such as dimethoxyethane, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, and phenol.

Phenols such as cresol and xylenol, chlorinated aromatic solvents such as m-chlorophenol and p-chlorophenol, propylene carbonate, dimethyl sulfoxide, and sulfolane are used.

In particular, when considering the on-machine stability of the paste during repeated printing, it is preferable that the boiling point is in the range of 150 to 350°C. If the temperature is less than 150°C, the volatilization of the bath agent from the paste will occur violently during printing, resulting in poor on-machine stability of the paste during repeated printing, and if it exceeds 35°C, the solvent will remain in the baked film. Consider problems that are likely to persist. Boiling point is 150℃
Examples of non-nitrogen-containing solvents in the range of ~350°C include 9% of lactones such as r-7 tyrolactone, r-valerolactone, γ-caprolactone, 6-caprolactone, α-acetyl-γ-butyrolactone, cyclohexanone, 4 −
Alicyclic ketones such as methylcyclohexanone or ethers such as diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, and tetraethylene glycol dimethyl ether are preferably used. These compounds can be used alone or in combination.

The aromatic polyamic acid or its derivative in the present invention is dissolved in a non-nitrogen-containing solvent to form a solution. Such solutions can be obtained directly by synthesizing aromatic polyamic acids or derivatives thereof in the non-nitrogen-containing solvents described above, and can also be obtained by containing compounds such as N-methylpyrrolidone, N,N-dimethylacetamide, etc. Even if the aromatic polyamic acid or its derivatives synthesized in an ordinary chemical are poured into a reagent such as methanol or water, recovered as a solid resin, and then dissolved in the above-mentioned non-nitrogen-containing solvent. good.

Concentration of aromatic polyamic acid or its derivative in solution (
The resin concentration is preferably 5 to 80% by weight and 10 to 60% by weight. If it exceeds 80% by weight, fluidity will be impaired when it is made into a paste, and if it is less than 5% by weight, it will be difficult to form a thick film.

The fine resin particles and inorganic fine particles in the present invention are particles that can be dispersed in a solution of the above-mentioned aromatic polyamic acid or its derivative to form a paste, and preferably have a Chickentropy coefficient of 1.5 or more. There are no particular restrictions.

As such resin particles, from the viewpoint of heat resistance, particles of polyamide resin, polyamideimide resin, polyimide resin, etc. are preferably used.

Examples of polyamide resins, polyamide-imide resins, and polyimide resins include polycarboxylic acids or their reactive acid derivatives and diamines (e.g., JP-A-63-205640
The diisocyanate obtained by reacting a diamine with phosgene or thionyl chloride can be used.

Resin fine particles are prepared using a non-aqueous dispersion polymerization method (% Kosho 60-4).
No. 8531, Japanese Unexamined Patent Publication No. 59-230018),
Precipitation polymerization method (% 1980-108030, JP 60-221425), method of mechanically pulverizing powder recovered from resin bath liquid, adding resin bath liquid to poor bath medium under high shear Any method can be used, including a method of forming fine particles, a method of drying sprayed oil droplets of a resin solution to obtain fine particles, and the like.

The thermal decomposition initiation temperature of the fine resin particles is preferably 250°C or higher, particularly preferably 350°C or higher.

However, examples of inorganic fine particles include 9.

Warping force (SiOz) - Alumina (A/z03), Titania (TiCh), Oxide 17T (Taxes)
, zirconia (ZrO2), silicon nitride (Si3N4)
l Barium titanate (Bad-Tie), barium carbonate (BaCOl), + lead tanate (PbO-TiOx)
), lead zirconate titanate (PZT).

Lanthanum lead zirconate titanate (PLZT), gallium oxide (Gazes), spinel (Mg 0-klz C
h) -Mullite (3Aj, Os・2StO2)-
Cordierite (2MgO-2AlzOs-s Si
O*), talc (3Mg0-4SiO,・H,0),
Aluminum titanate (TiO, -AI!203), ittria-containing zirconia (Yz03-ZrOz), barium silicate (Ba0.8Si02), etc.? , green inorganic fine particles, silver (Ag), copper (Cu), nickel (Ni).

Titanium blank (TiO2), tin oxide (SnQ, ), 7
Conductive inorganic fine particles such as tin-containing labeled tin (SbrI-8nO2) and tin-containing indium oxide (Sn'-InzOs) are used. Two or more types of resin fine particles and/or inorganic fine particles may be used as necessary. Also.

A mixture of resin fine particles and inorganic fine particles may be used.

As the resin fine particles and inorganic fine particles in the present invention, those having particle characteristics of an average particle size of 30 μm or less and a maximum particle size of 40 μm or less are preferably used. Average particle size is 3
If it exceeds 0 μm, it will be difficult to obtain a paste with a Chickentropy coefficient of 1.5 or more, and if the maximum particle size exceeds 40 μm, the appearance and adhesion of the coating film will tend to be insufficient.

The ratio of the aromatic polyamic acid or its derivative to the resin fine particles and/or the inorganic fine particles is preferably 5 to 5 parts by weight, with the total amount being 100 parts by weight.
Resin fine particles and/or inorganic fine particles 9 to 85 parts by weight
The amount is in the range of 5 to 15 parts by weight. Increasing the proportion of fine resin particles and/or fine inorganic particles can increase chicken tropism and dry metal thickness.

The total concentration of aromatic polyamic acid or its derivative, resin particles and/or inorganic particles in the paste is preferably 10 to 950 to 95 parts by weight.

If it is less than 10% by weight, the dry thickness of the film increases and K<<
If it exceeds 95% by weight, the fluidity of the paste will be impaired.

It is preferable that the heat-resistant resin paste in the present invention has a chicken tropy coefficient of 1.5 or more. If it is less than 1.5, the printed paste has been transferred to the base material.

It does not provide printability that shows sufficient turning accuracy for practical use without dripping or smearing. Further, the viscosity of the paste is preferably adjusted to 30 to 10,000 poise.

If the viscosity of the paste is less than 30 poise, the paste tends to sag after printing.

If it exceeds 10,000 poise, printing workability will decrease.

Particularly preferably, it is 300 to 5000 poise. Here, the chicken tropy coefficient of the paste was measured using an E-type viscometer (manufactured by Tokyo Keiki Co., Ltd., model EHD-U) at a sample amount of o, 4 g, and a measurement temperature of 25°C.

Apparent viscosity of paste at rotational speed l rpm and l Q rpHm.

η! And η! It is expressed as the ratio of O, l/η10. Also.

Paste viscosity fin, apparent viscosity at rotation speed 0.5 rpm.

η. , is expressed as .

As a method for dispersing resin particles and/or inorganic particles in a solution of aromatic polyamic acid or its derivatives, roll kneading, mixer mixing, etc., which are used in the paint field, are usually applied, and are methods that ensure sufficient dispersion. There are no particular restrictions. Most preferred is multiple kneading using three rolls.

The paste of the present invention is applied to a substrate and then finally
A film can be formed by baking at 0 to 400°C for 1 to 100 minutes.

The paste of the present invention contains an antifoaming agent if necessary.

Pigments, dyes, plasticizers, antioxidants, etc. may be used in combination.

The heat-resistant resin paste of the present invention is suitable for devices such as monolithic ICs using silicon wafers, ceramic substrates, and glass substrates, such as hybrid ICs, thermal heads, image sensors, multi-chip high-density mounting boards, and flexible wiring boards.

Interlayer insulation films and/or various wiring boards such as rigid wiring boards
Or surface protective film, heat-resistant printing ink.

It can be widely used in heat-resistant adhesives, etc., and is extremely useful industrially.

When the heat-resistant resin paste of the present invention is used as a protective film of a semiconductor device such as a monolithic IC, alpha-ray source materials such as uranium, thorium, sodium, potassium, chlorine, etc.
It is preferable to reduce the content of ionic impurities such as steel and iron. The total content of α-ray source materials such as uranium and thorium in the protective film is preferably less than IP ppb, more preferably less than Fio, 2 ppb. This is 0.2 to 1
This is because the influence of α rays emitted from the protective film etc. on malfunction of the device decreases rapidly when the ppb level is reached. When the total content of α-ray substances such as uranium and thorium in the obtained protective film exceeds 0.2 to 1 ppb, the aromatic polyamic acid or its derivative and the monomer used in the production of the resin fine particles, By smoothing and purifying bath additives, precipitants used in resin purification, non-nitrogen-containing m-agents, etc., the total content of α-ray source substances such as siluran and thorium can be reduced.

For purification, aromatic polyamic acid or its derivatives and monomers and solvents used in the production of resin fine particles are used.

Distillation, sublimation, recrystallization, extraction, etc. of precipitants, non-nitrogen-containing m-agents, etc. used in the purification of resins, etc.

It is also advantageous to perform the step of precipitating the synthesized resin liquid into the purified molten shell multiple times.

Furthermore, by smoothing and sufficiently refining inorganic fine particles using well-known methods, the total content of α-ray source substances such as uranium and thorium can be reduced.

In general, inorganic fine particles containing a small amount of α-ray source substances such as uranium and thorium hardly exist in nature. Examples of purified inorganic fine particles include synthetic silica (Sin) obtained by oxidizing purified silicon tetrachloride in a gas-phase oxygen flame or oxidizing with plasma, and synthetic silica obtained by gelling silicon. can be mentioned. Also, Aj
203. Metal oxides such as TiO2° Tag o, ZrOx, and metal nitrides such as Si and N4 can also be mentioned.

Further, in order to reduce corrosion and leakage during use, the content of ionic impurities such as sodium, potassium, chlorine, copper, and iron is preferably 2 ppm or less.

More preferably it is i ppm or less. If the total content of ionic impurities in the resulting protective film exceeds 1 to 21) m, the above-mentioned aromatic polyamic acid or its derivatives and the monomers used in the production of the resin fine particles may be added to the above-mentioned monomers in advance. The total content of ionic impurities can be reduced by manufacturing the n-type material in the same process as the ff-manufacturing process.

Purification does not necessarily have to be carried out on all of the seven snails used.

For example, purification may be performed only on the monomer or only on the monomer and the bath agent. In addition, the total content of ionic impurities can be reduced by sufficiently purifying inorganic fine particles by the above-mentioned nine round method.

Examples of the IC in the present invention include a monolithic IC, a hybrid IC, and a multi-chip high WV mounting board.

A monolithic IC 1 has a structure shown in FIG. 1, for example, and is coated on a heat-resistant resin paste dLsI according to the present invention and heated to form a heat-resistant resin film 1 (surface protection film).

In FIG. 1, 1 is a heat-resistant resin film, 2 is an LSI chip, 3 is a bonding wire, 4 is a resin package, 5 is a lead, and 6 is a support body.

The hybrid IC has the structure shown in FIG. 2, in which a heat-resistant resin paste according to the present invention is coated on the first layer wiring 11 and the resistance layer 12 and heated to form a heat-resistant resin film 10 (interlayer (insulating film). A second layer wiring 9 is formed on this.

In Figure 2, 7 is a diode chip, 8 is solder,
9 is a second layer wiring, and 10 is a heat-resistant resin film.

11 is a first layer wiring, 12 is a resistance layer, and 13 is an alumina substrate.

The multi-chip high-density mounting board 9 has the structure shown in FIG. 3, for example, by forming wiring layers 15 and 16 on the ceramic multilayer wiring board 20 by a known method.1 Applying the heat-resistant resin paste of the present invention. .

By repeating the formation of the heat-resistant resin film 14 (interlayer insulating film) by heating, etc., the steel/heat-resistant resin multilayer wiring layer 19 is formed. In FIG. 3, 17 is an LSI chip, and 18 is soldered.

(Example) Next, one embodiment of the present invention will be specifically explained using an example and a comparative example.

In addition, in the following Examples and Comparative Examples, the non-swellability or non-solubility of the paste with respect to the emulsion of the plate during printing was evaluated by the emulsion swelling rate of the plate expressed by the following formula. The emulsion for the plate was New Suhar L (product name manufactured by Tokyo Process Service Co., Ltd.), and the emulsion pattern width for the 9th plate was determined by a universal projector and a profile projector ■-12 type manufactured by Kon Co., Ltd.).
Measured using

A: Emulsion pattern of the plate before contacting the paste @ (
100 μm width) B: Emulsion pattern width of the plate after 10 days of contact with the paste Example 1 (1) Preparation of aromatic polyamic acid solution While passing nitrogen gas into the flask, λa, '4.4'-benzophenonetetracarboxylic dianhydride 0.1 mol, 2.4'-
Diaminodiphenyl ether 0.1 mol triethylene glycol dimethyl ether 2969 (moisture 0.02%
) was prepared. The reaction was then continued at room temperature for 10 hours.
Greasing I! A 15% by weight aromatic polyamine citric acid solution was obtained. The number average molecular weight (determined by gel permeation chromatography using polystyrene of known molecular weight as a calibration curve; the same applies hereinafter) of this aromatic polyamic acid was found to be 31,000.

(2) Preparation of resin fine particles using non-aqueous dispersion polymerization method (a)
Synthesis of dispersion stabilizer In a four-loaf flask equipped with a thermometer, a stirrer, and a 9-ball condenser, 185.79° lauryl methacrylate (10a8 g) and methacrylic acid (Aliphatic hydrocarbon manufactured by Esso Standard Oil Co., Ltd., trade name) were added. -2-hydroxyethyl algt was added and the temperature was raised to 100°C. 106.9g of lauryl methacrylate was smoothened and prepared by passing nitrogen gas through it.

A mixture of 2459° 2-hydroxyethyl methacrylate and 2.49° benzoyl peroxide paste (benzoyl peroxide content 50% by weight) was added dropwise over 2 hours while stirring. Subsequently, the mixture was kept at 100°C for 1 hour, then raised to 140°C, and reacted at the same temperature for 4 hours. This dispersion stabilizer bath solution was dried at 170°C for 2 hours, and the nonvolatile content was 55% by weight.
Therefore, the number average molecular weight of the dispersion stabilizer 9 was 67.000.

(b) Preparation of polyamide-imide resin fine particles While passing nitrogen gas through a 500-meter four-bottle flask equipped with a basin meter, a stirrer, and a bulb/tube condenser, 4゜4'-diphenylmethane diisocyanate 35.19゜MR- 100 (manufactured by Nippon Polyurethane Co., Ltd., aromatic polyisone eye) 16
．． 39. Each dispersion stabilizer solution obtained in (a) above (non-volatile content: 4
0 weight t%) 199゜l5OPAR-H150g, N
- Add 9.09 tylpyrrolidone, 380 rp
The temperature was raised to m'C < uA, t, Nacala ioo°C.

Next, 3 and 5 g of tomotrimellitic anhydride, which had been pulverized in advance, was added thereto, and the mixture was heated at 100°C for 1 hour.

The reaction was continued at 115°C for 1 hour, at 125°C for 1 hour, at 140°C for 1 hour, and further heated to 170°C for 2 hours. After dispersing in the continuous phase 180PA-HCF, fine particles of brown polyamideimide resin were obtained.

This was collected by filtration, boiled with water and methanol, separated by F, and dried under reduced pressure at 60° C. for 5 hours. The shape of the polyamide-imide resin fine particles was spherical and non-porous. In the infrared absorption spectrum, imide bond absorption was observed at F'11780, and amide bond absorption was observed at F'1650 and 1540 cm. The average a diameter of the polyamide-imide resin fine particles (according to TA-n type manufactured by Coulter Electronics Co., the same applies hereinafter) is approximately 3 μm, #
The large particle diameter was 40 μm or less.

(3) Preparation of heat-resistant resin paste Aromatic polyaminic acid liquor prepared in (1) above (Seishu! 1 degree 15] il 1%) 80 gK above (2+, 1 sip)
Add 20 g of the constant polyamideimide resin fine particles obtained in .

First, it was roughly kneaded in a mortar, and then kneaded six times using a high-speed triple roll to obtain a heat-resistant resin paste in which polyamide-imide resin fine particles were dispersed. Apparent viscosity η, 5 is 920 poise, 1
Apparent viscosity η1Fi650 poise at rpm, lorp
The apparent viscosity η1o in m was found to be 222 hoas, and the chicken tropy coefficient ga/η10 was found to be 29. When this paste was screen printed to a thickness of about 30 μm on an aluminum substrate with a smooth surface, no rolling, dripping, or running was observed.

We are confident that this base lj will not clog the screen due to a solid layer of paste even after repeated printing over 200 times, and the paste will have excellent on-machine stability during printing. The emulsion swelling rate of the plate of this paste was 3, and the emulsion had excellent non-swelling and non-dissolving properties.

In addition, this paste was processed at 100℃ for a working time of 200℃, and at 200℃ for 0.
．． It was confirmed that the film baked for 5 hours and then for 0.5 hour at 250°C retained the good pattern accuracy before baking.

Implementation % J2 fl) Preparation of aromatic polyamic acid solution 3.3:4
．． 4'-benzophenone tetracarboxylic dianhydride
, 4'-oxidiphthalic anhydride, except that triethylene glycol dimethyl ether 2969 was replaced with tetraethylene glycol dimethyl ether 2899.
．． The procedure was carried out in exactly the same manner as in (1) to obtain an aromatic polyamic acid bath solution having a resin a degree of 15% by weight. The number average molecular weight of this aromatic polyamic acid was 35,000.

(2) Preparation of polyimide resin fine particles using precipitation polymerization method Pyromellitic dianhydride 2189 (1 mol) and N-methylpyrrolidone (moisture 0.03%) 16729 were added, heated to 50° C. with stirring, and kept at the same temperature for 0.5 hours to completely dissolve and form a uniform bath liquid. To this, 4,4'-diaminodiphenyl ether xoog (o, s mol) and 44'-
Diaminodiphenylmethane 999 (0.5 mol) was added, the temperature was immediately raised to 110"CK at fc, and kept at the same temperature for 20 minutes to ensure complete dissolution and a homogeneous solution. Then, the temperature was raised to 200 °C in about 2 hours. 1 and react at the same temperature for 3 hours.

During the process, precipitation of fine particles of polyimide resin was observed at approximately 140°C. In the first reaction, the distilled water was removed from the system in a corner f.

Since fine particles of yellow-brown polyimide resin dispersed in N-methylpyrrolidone were obtained, 7"L of the fine particles were collected by filtration, and after rinsing with acetone twice, under reduced pressure,
Dry at 00℃ for 5 hours. The shape of these polyimide resin fine particles is almost spherical, porous, and the average particle diameter is 8 μm.
m, the maximum particle diameter was 40 μm or less.

(3) Preparation of heat-resistant resin paste To 779 of the aromatic polyamic acid solution (resin #15% by weight) prepared in (1) above, add 239 of the polyimide fat particles prepared in (2) above, and place in a mortar. Roughly knead with
The mixture was then kneaded six times using a high-speed triple roll to obtain a heat-resistant resin paste in which fine polyimide resin particles were dispersed. The apparent viscosity η of this paste was measured with an E-type viscometer at fcOls rpm. , the apparent viscosity at Irpm is '7+Fi540 poise, the apparent viscosity η10 at 10 rpm is 160 poise, and the chicken tropy coefficient η1/η10 is 3.4. This paste was screen printed on an aluminum substrate with a smooth surface to a thickness of approximately 30 μm.

No one was found to have hurt anyone. This paste is 2
Even after repeated printing of VC over 00 times, the screen does not become clogged due to paste sticking, and the paste has excellent on-machine stability during printing.

The plate of this paste had an emulsion We warm wettability of 4, and was found to have excellent non-swelling and non-dissolving properties with respect to the emulsion.

ifc, this paste at 100°C' for 1 hour, 200
℃ for 0.5 hours, 250℃ for 0.5 hours, further [350℃
It was confirmed that the film that was applied for 0.5 hours retained the good pattern accuracy before baking.

3 (1) Preparation of aromatic polyamine citrate solution A 94-bottle flask equipped with a thermometer, a stirrer, 1 gi conductor tube, and a cooling tube P"Di: 3.3't4'-Hyphenyltetracarboxylic acid ester solution Acid dianhydride 0.1 mol, ethanol 0.1
Add mole and ξ-caprolactone 1269, stir, heat, and raise to 100°C. The mixture was reacted at the same temperature for 4 hours to obtain a mixture of tetracarboxylic dianhydride and its ester. After cooling 40'cK, 2.4'-
0.1 mol of diaminodiphenyl ether was charged and dissolved to obtain an aromatic boria S succinic acid ester solution having a resin concentration of 30% by weight. The number average molecular weight of this aromatic polyamine citrate was 3,200.

(2) Preparation of heat-resistant resin paste.
Add 25 g of the polyamide-imide fine particles obtained in (b), and first roughly knead in a mortar, then knead by passing six times using a high-speed triple roll to obtain a heat-resistant resin paste in which polyamide-imide resin fine particles are dispersed.

Apparent viscosity η of this paste at 0.5 rpm measured with an E-type viscometer. The apparent viscosity η1 at 5idl 270 poise and 1 rpm was 670 poise, the apparent viscosity ηIo at 1Q rpm was 125 poise, and the chicken tropy coefficient ηl/η1o was 5.4. When this paste was screen printed to a thickness of about 30 μm on an aluminum substrate with a smooth surface, no dripping or running was observed. This paste did not cause clogging of the screen due to paste sticking even after repeated printing over 200 times, and was found to have excellent on-machine stability during printing. The emulsion swelling rate of this paste plate is 15 cm.
It also has excellent non-wetting and non-solubility properties in emulsions.

Now, heat this paste at 100℃ for 1 hour, then heat it at 200℃ for 0.
．． It was confirmed that the film baked for 5 hours and then for 0.5 hours at 250°C retained the previous good pattern.

Example 4 (1) Preparation of aromatic polyaminic acid solution While passing nitrogen gas through a 500-barrel four-bottle flask equipped with a stirrer, a stirrer, and a nitrogen inlet tube, add 3:44'-benzophenonetetracarboxylic acid dihydrate. 0.1 mole of anhydride, 0.1 mole of 2.4'-diaminodiphenyl ether, and 1209 g of N-methylpyrrolidone (moisture 0.01%) were charged.The reaction was then allowed to proceed at room temperature for 10 hours.The viscosity of the reaction system Due to the raw bottom of the high molecular weight polyamic acid, the amount of water increases to the point where it is difficult to stir.At this point, a small amount of water is added to the reaction system.
One molecular weight was prepared by heating to 0°C. The number average molecular weight of the obtained aromatic polyamic acid is s zo o .

I failed. A solution of this aromatic polyamic acid in N-methylpyrrolidone (resin concentration 20% by weight) was diluted with N-methylpyrrolidone to about 10% by weight. Then, this solution was poured into methanol which had been vigorously stirred with a mixer to recover the solid aromatic polyamic acid. This solid polyamic acid was thoroughly boiled and washed with methanol.

After removing it, it was dried at 60°C for 5 hours.

Get powdered aromatic polyamic acid. This aromatic polyamic acid had a number average molecular weight of 27,000 yen, and was dissolved in triethylene glycol dimethyl ether to prepare an aromatic polyamic acid solution having a resin concentration of 15% by weight.

(2) Preparation of heat-resistant resin paste Aerosil 200 (Nippon Aeronle Co., Ltd., trade name: Sin, fine particles, average particle size 0.0
1 6μm) 7g, mix in a mortar first,
Next, the SiQ was kneaded by passing it through six times using a high-speed triple roll.
A heat-resistant resin paste in which fine particles were dispersed was obtained. Q of this paste measured with an E-type viscometer, apparent viscosity η at 5 rpm. , H860 Poise.

Apparent viscosity η1H545 poise at 1 rpm, 10r
The apparent viscosity in pm is η + oH 177 Boas.

The chicken tropy coefficient was η1/ri1oIri3.1. Apply this paste to a thickness of approximately 30 μm on a smooth aluminum substrate.
When I screen-printed it with a thick thickness, there was no flow, flow, etc. #ig
It did not fit. This paste has been repeatedly stamped over 200 times; it does not cause screen clogging due to paste sticking, and the paste has excellent on-machine stability during printing. The emulsion swelling rate of the plate of this paste was 3, and it was found to have excellent non-swelling and non-dissolving properties for the emulsion.

In addition, this paste was heated at 1100°C for 1 hour, and at 200°C for 0.
．． 5 hours, 0.5 hours at 250°C, and 0.5 hours at 350°C.
After 5 hours of baking, it was confirmed that the film retained the previous good pattern of baking.

Example 5 (1) Preparation of aromatic polyamic acid solution Purified by recrystallization from acetic anhydride in a 500 mm four-loop flask equipped with a thermometer, stirrer, and nitrogen inlet tube.
-benzophenonetetracarboxylic dianhydride 0.047
5 mol, 3.3:4.4'-biphenyltetracarboxylic dianhydride 0.0475 mol.

[1,3-bis(14-dicarboxyphenyl)-1,1,3,3-tetramethyldisiloxane] dianhydride o recrystallized from a mixture of toluene and diethyl ether at a polymerization ratio of 1:1. , oos mole, recrystallized from a mixture of methanol and water at a polymerization ratio of 8=2 (methanol:water), fc
0.1 mol of 2.4'-diaminodiphenyl ether and 291 g of 9γ-caprolactone purified by vacuum distillation were charged while passing nitrogen gas. Press down, 10 at room temperature
Advance the time reaction.

Obtain a 15% by weight aromatic polyamic acid solution. The number average molecular weight of this aromatic polyamic acid is 42
,000.

(2) Preparation of polyimide resin fine particles using spray drying method 3. Purified polyimide resin particles were purified by recrystallization from acetic anhydride in a four-loaf flask equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a moisture meter.
, 3:44'-biphenyltetracarboxylic dianhydride 0
．． 0379 mol, recrystallized using a mixture of toluene and diethyl ether in a weight ratio of 1=1*(:1.3-bis(3,4-dicarboxyphenyl)-1,1,3,3
-Tetramethyldisiloxane] dianhydride 0.0020 mol, weight ratio of methanol and water 8 = 2 (methanol:
0.0399 mol of 44'-diaminodiphenyl ether recrystallized using a mixture of water) and 80 g of N-methylpyrrolidone purified by distillation under reduced pressure were charged while passing nitrogen gas. The reaction was then continued at room temperature for 10 hours.Then, the temperature was raised to 200"cK, and the reaction was continued at the same temperature for 10 hours.During the process, water that distilled out was immediately removed from the reaction system.The resulting solution was diluted with 644 g of N-methylpyrrolidone purified by vacuum distillation to obtain a solution with a resin concentration of 2-5% by weight. This was spray-dried using a Mobil Minor type spray dryer manufactured by Ashizawa Waniro Atomizer Co., Ltd. to form fine particles. 9 to obtain polyimide resin fine particles having an average particle diameter of 4 μm and a maximum particle diameter of 40 μm or less.

(3) Preparation of heat-resistant resin paste
Add 20 g of the polyimide resin fine particles of the above (2) to 809 with a resin concentration of 155% by weight, and first roughly knead in a mortar, then knead by passing 6 times using a high-speed triple roll to obtain a heat-resistant mixture in which the polyimide resin fine particles are dispersed. Get the resin paste. This paste was measured with an E-type viscometer and the apparent viscosity at 0.5 rpm was 1520 poise, and the apparent viscosity at l rpm was η
l is 790 poise.

l Q Apparent viscosity ηxai220 poise at rpm, chicken tropy coefficient η1/η! 0 is 3.6, which is 9 h.

This paste was screen printed to a thickness of about 30 μm on an aluminum substrate with a smooth surface, and no sag or flow was observed. Even after repeated printing over 200 times, this paste does not cause screen clogging due to paste sticking.

The on-machine stability of the paste during printing was outstanding. The emulsion expansion ff4 rate of this paste plate is 5 Ruri,
It was also found to have excellent non-swelling and non-dissolving properties in emulsions.

In addition, this paste was heated to 100℃ for 1 hour, and then heated to 200℃ for 0.
．． 5 hours, 0.5 hours at 250°C, and 0.5 hours at 350°C.
It was confirmed that the film baked for 5 hours retained the good turning accuracy before baking. When the non-nitrogen-containing solvent (r-caprolactone) was removed from this paste and the contents of uranium and thorium were investigated by activation analysis, they were found to be below the detection limit of 0.02 ppb and 0.05 ppb, respectively.
Rarely below ppb.

However, the content of ionic impurities of sodium, potassium, chlorine, copper, and iron is less than 2 ppm each. This paste was lightly applied to the surface of an MO8 type AM with a channel width of 16 by Nuclean printing, and then heated at 100°C for 1
time, 150°C, 200'C, 0.5 hour at 250°C,
Further, heat treatment was performed at 350° C. for 1 hour to form a polyimide antifa film having a thickness of about 20 μm. The obtained semiconductor element was then sealed at about 450° C. using a ceramic package using low melting point glass as a sealing adhesive. The soft error rate of this semiconductor device was 30 fits.

Comparative Example 1 (1) Preparation of aromatic polyamic acid solution While passing nitrogen gas through a 500 d four-bottle flask equipped with a thermometer, stirrer, and nitrogen inlet tube, pyromellitic dianhydride (0) was added.
．． 1 mol, 4.4'-diaminodiphenyl ether 0.
1 mol, N-methylpyrrolidone (water 0.03%) 23
I prepared 79. Under this pressure, the reaction proceeded at room temperature for 10 hours. The viscosity of the reaction system increased to such a level that stirring was difficult due to the formation of high molecular weight polyamic acid. Here, a small amount of water was added to the reaction system and then heated to 60°C to prepare a molecular weight of 9, thereby obtaining an aromatic polyamic acid solution containing 15% by weight of AI resin. The number average molecular weight of this aromatic polyamic acid was 33,000.

(2) Preparation of heat-resistant resin paste Add (2) of the aromatic polyamic acid solution prepared in the above (1) (refined fat #11 degree 15% by weight) 809 to 7M column 1.

Add the polyamideimide resin fine particles 209 obtained in Naka),
The mixture was roughly kneaded in a mortar and then kneaded six times using a high-speed triple roll to obtain a heat-resistant resin paste in which fine polyamide-imide resin particles were dispersed.

This paste was measured with an E-type viscometer, and the apparent viscosity at 0.5 rpm was 980 poise, the apparent viscosity at 1 rpm was 610 poise, the apparent viscosity at IQ rpm was η1゜ti196 Boise, and the chicken tropy coefficient I met with η1/ηxotill. This paste was screen printed to a thickness of about 30 μm on an aluminum substrate with a smooth surface.However, until the 8th printing, no sagging or running was observed and normal printing was possible, but after the 8th printing, the printing screen The paste solidified on the paper, causing blisters and making it impossible to print. This indicates that the on-machine stability of the paste during printing is poor. In addition, the emulsion swelling rate of this paste plate was 60%, and the emulsion had poor non-swelling and non-dissolving properties.

(Effects of the Invention) The heat-resistant resin paste of the present invention can be applied by screen printing, and has excellent on-machine stability during repeated printing on a 1% screen and non-swelling properties for the emulsion contained in the plate forming material. Or it has excellent non-solubility. In addition, it is possible to impart appropriate chicken tropism, and an excellent pattern n degree can be obtained by filtering and printing.

[Brief explanation of the drawing]

FIG. 1 is a cross-sectional view of an example of a monolink IC using the heat-resistant resin paste of the present invention, FIG. 2 is a cross-sectional view of a row of hybrid ICs using the heat-resistant resin paste of the present invention, and FIG. This is a cross-sectional view of an example of a multi-chip high-density mounting board using resin paste. Explanation of symbols 1...Heat-resistant resin film 2...LSI chip 3.
・・Bonding wire 4・Resin handle cage 5・
・Lead 6・・Support 7・Iode chip 8・Solder 9・Second layer wiring
10...Heat-resistant resin film 11...First layer wiring
12... Resistance layer 13... Alumina substrate 14...
・Heat-resistant resin film 15...Wiring layer 16...
・Wiring layer 17...LSI chip 18...Solder 19...Copper/M resin multilayer wiring layer 20...Ceramic multilayer wiring board

Claims (1)

[Claims] 1,2,4'-diaminodiphenyl ether and the general formula (I) ▲There are numerical formulas, chemical formulas, tables, etc.▼(I) (wherein, X is -O-, -CO-, - Obtained by reacting with a tetrabasic acid dianhydride and/or its reactive derivative represented by SO_2-, ▲There are mathematical formulas, chemical formulas, tables, etc. ▼ or a single bond that does not contain any of these A heat-resistant resin paste comprising resin fine particles and/or inorganic fine particles dispersed in a solution of aromatic polyamic acid or its derivative dissolved in a nitrogen-free solvent. 2. The heat-resistant resin paste according to claim 1, wherein the nitrogen-free solvent is a lactone, an alicyclic ketone, or an ether. 3. The resin fine particles and/or inorganic fine particles have an average particle diameter of 30
Claim 1 or 2: The particles are resin fine particles and/or inorganic fine particles having a particle characteristic of µm or less and a maximum particle diameter of 40 µm or less.
Heat-resistant resin paste as described. 4. The heat-resistant resin paste according to claim 1, 2 or 3, wherein the paste has a thixotropy coefficient of 1.5 or more. 5. An IC having an interlayer insulating film and/or a surface protective film obtained from the heat-resistant resin paste according to any one of claims 1 to 4.