JPH02289646A - Heat-resistant resin paste and ic using same paste - Google Patents

Abstract

PURPOSE:To obtain a heat-resistant resin paste useful as an interlaminar insulating film or surface protecting film of IC, having thixotropic properties, comprising two kinds of organic liquids, heat-resistant resin soluble in the organic liquids and fine particles of heat-resistant resin soluble only in one of the liquids. CONSTITUTION:A heat-resistant resin paste comprising a mixed organic liquid comprising (A) an organic liquid (e.g. N-methylpyrrolidone) and (B) an organic liquid (e.g. diethylene glycol dimethyl ether) more volatile than the component A, (C) a heat-resistant resin (e.g. preferably polyamide resin) soluble in the mixed organic liquids and (D) fine particles of heat-resistant resin soluble in the component A but not in the component B, preferably polyamide or polyimide having <=40mum average particle diameter prepared by nonaqueous dispersion polymerization method, prepared by dispersing the component D into a solution containing the components A, B and C, having >=1.5 thixotropic coefficient. IC having an interlaminar insulating film or surface protecting film prepare from the paste.

Description

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

(Prior art) Usually, the resin solution is... #chickentropy by itself
1. Not shown at all. Chickentropy is defined as a phenomenon in which the apparent viscosity temporarily decreases at the ninth stage of deformation even in an isothermal state. For example, under high shear speed during printing, the viscosity temporarily decreases and the base material flows. The screen printing paste K is required to not drip or flow after the K transition, which is an essential flow characteristic. A ninth method for imparting chicken-tropic properties to a resin solution is to disperse fine resin particles as a resin solution K filler and form it into a paste. Various types of such pastes are known.

As a resin solution used for applications that do not require much heat resistance. For example, rosin-modified phenolic resin. There are resin solutions such as rosin-modified maleic resins, melamine resins, and epoxy resins, and polyamic acid resins, which are precursors of polyimide resins, are available for applications that require high heat resistance. M-medium soluble polyimide resin, polyamideimide resin. Resin solutions such as polyamide resins are known. In addition, the resin fine particles that are dispersed in these resin solutions to form a paste are as follows. Aliphatic polyamide resin fine particles are used for applications that do not require much heat resistance. Melamine resin particles, epoxy resin particles, phenolic resin particles, etc. are known, and f! ! Polyimide resin particles and polyamide-imide resin particles are used for applications that require high heat resistance. Polyamide resin fine particles are known.

(Problem to be solved by the invention) Semiconductor element. Screen printing paste K, used for insulating and protective films on wiring boards, has a high degree of heat resistance and flexibility. Moisture resistance and corrosion resistance are required. For such applications K, as described above, a paste has been developed in which a filler of inorganic or organic fine particles is dispersed in a heat-resistant resin solution. However, inorganic fine particles are themselves hard and have a high specific gravity, which increases their volume occupancy in the paste, significantly impairing the inherent flexibility of the resin. If the film is not sufficiently malleable, cracks are likely to occur in the film, and inorganic fine particles can easily damage the surface of semiconductor devices. Insulating films and protective films using pastes containing inorganic particles lack reliability.

On the other hand, organic fine particles with excellent removability are being considered as a material that can be expected to solve the above problems, but
When dispersed as a filler, voids are likely to form at the interface between the binder resin and the particle surface, which gives flexibility. This directly causes a decrease in moisture resistance and corrosion resistance. In pastes using inorganic fine particles having poor affinity with resins, this problem increases. in this way. In conventional pastes in which K-fine particles remain as fillers in the film, the fillers remain regardless of whether they are inorganic or organic particles. The film is non-uniform and tends to have voids, and cannot necessarily be said to be satisfactory for Application K, which requires a high degree of flexibility, moisture resistance, and corrosion resistance.

The present invention solves this trench problem. Has thixotropic properties and heat resistance of the film. The present invention provides a heat-resistant resin paste with excellent malleability, moisture resistance, and corrosion resistance κ, and an IC using the same.

(Means for Solving the Problems) The present invention provides a first organic liquid (At). Second organic liquid (
As). The heat-resistant resin (B) and (AI)K, which are soluble in the mixed organic liquid of (At) and (Am), dissolve (At
) contains insoluble heat-resistant resin fine particles (C). (At)
．． This invention relates to a heat-resistant resin paste formed by dispersing (C) in a solution containing (As) and (B), and to 7'hICK using this heat-resistant resin paste.

The heat-resistant resin paste in the present invention mainly functions as a chicken trobby property imparting agent for the solution and paste containing (AI), (2), and (B), which mainly functions as a binder.
It is composed of. Put this paste K. (C)
When compounded, K disperses in a solution containing (AI)-(Ax) and (B) and exhibits thixotropic properties, and upon heating, (AI)K dissolves. A uniform film is formed with the final K (B). in this way. The heat-resistant resin paste of the present invention has excellent chicken tropism, which directly affects printing properties, and the resulting film is uniform without any holes or voids.
Provides excellent malleability, moisture resistance, and corrosion resistance.

(Function) The first organic liquid (AI) in the present invention K is a heat-resistant resin (B) soluble in the mixed organic liquid with the second organic liquid (As).
A material that dissolves the soluble heat-resistant resin fine particles (C) alone is used. Also, (AI) Id (At
) It also evaporates from the paste.<<. Those that are good solvents for (B) are preferred.

Second organic liquid (Ax) # in the present invention κ: t A heat-resistant resin (
Dissolve B). A material that does not dissolve the heat-resistant resin fine particles (C) when used alone is used. Also. (Ax) Fi(At
) is easier to evaporate from the paste than <. It may be a good or poor solvent for (B).

here. The degree of ease of evaporation from the paste of (As) and (A2), the boiling point of Vi (At) and (A!), the vapor pressure of (
It depends on the strength of affinity with B) and (C).

Generally, the boiling point is low. Organic liquids with higher vapor pressure and poorer affinity with resin are more likely to evaporate from the paste.

The combination of (Al) and (At) in the present invention varies depending on the types of (B) and (C) used, and any combination can be selected as long as the desired paste of the present invention can be obtained. Specifically, such (A1) and (Ax) are described in, for example, "Solvent Handbook" (Kodansha, published in 1976).
The organic liquids listed on pages 143 to 852 of . For example, N-methylpyrrolidone. Dimethylacetamide, dimethylformamide. 1,3-dimethyl-3.
4, 5. Nitrogen-containing compounds such as 6-tetrahydro-2 (IH)-pyrimidinone and 1,3-dimethyl-2-imidazolidinone. Sulfur compounds such as sulfolane and dimethyl sulfoxide, r-butyrolactone. γ-cabrolactone. α-Ftyrolactone. Lactones such as ε-cabrolactone, dioxane, 1,2-dimethoxyethane.
Ethers such as diethylene glycol dimethyl (or diethyl, dibropyl, siftyl) ether, triethylene glycol dimethyl (or diethyl, dibropyl, diptyl) ether, tetraethylene glycol dimethyl (or diethyl, dipropyl, diptyl) ether, methyl ethyl ketone, methyl isobutyl ketone. Ketones such as cyclohexanone and acetophenone, butanol.
Octyl alcohol, ethylene glycol, glycerin. Diethylene glycol heptanomethyl (or monoethyl)
ether. Alcohols such as triethylene glycol monomethyl (or monoethyl) ether and tetraethylene glycol monomethyl (or monoethyl) ether; phenols such as phenol, cresol, and xylenol. Ethyl acetate. Esters such as butyl acetate, ethyl cellosol acetate, butyl cellosol acetate. Hydrocarbons such as toluene, xylene, ethylbenzene, cyclohexane, trichloroethane. Halogenated hydrocarbons such as tetrachloroethane and monochlorobenzene, water, etc. are used.

Two or more types of each of (A1) and (A2) may be used. Heat-resistant resin CB soluble in mixed organic liquid of first organic liquid (81) and second organic liquid (At) in the present invention
) can be either a thermosetting resin or a thermoplastic resin. Examples of thermosetting soluble heat-resistant resins include: Terminal acetylenated polyimide resin, terminal maleimidated polyimide resin, terminal norbornened polyimide resin, BT
Resin (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name). Addition-polymerized polyimide resins such as Kelimide (manufactured by Lorne-Poulenc, trade name), melamine resins, phenol resins, epoxy resins, etc. are used. Examples of thermoplastic soluble heat-resistant resins include: The soluble heat-resistant resin listed in "Plastic Handbook" (Asakura Shoten, published in 1979), pages 308-618K, is used.

From the viewpoint of heat resistance and solubility. Preferably polyamide resin. Polyamideimide resin. Polyimide resin (including polyamic acid resin, which is a precursor of polyimide resin) is used.

A tetracarboxylic acid ester obtained by reacting a tetracarboxylic dianhydride with an alcohol and/or an alcohol derivative. A composition mixed with or reacted with a diamine or a polyamic acid ester oligomer may also be used. Also. A complex obtained by reacting the dianhydride with a solvent capable of forming a complex. Compositions mixed or reacted with diamines or polyamic acid oligomers may also be used. As for this solvent. Preferably N-
Methyl pyrrolidone. Pyridine. C-cabrolactam and the like are used.

Polyamide resin. As for polyamide-imide resin and polyimide resin. For example, polycarboxylic acid or its reactive acid derivative and diamine (for example, JP-A-63-205640
(described in Publication No. K) or those obtained by reacting the diamine with a diisocyanate obtained by reacting with phosgene or thionyl chloride are used. in particular. Soluble polyamide resin described in JP-A-57-64955, soluble polyamide-imide resin described in JP-A-1-40570, soluble polyimide resin described in JP-A-62-283154 Examples include.

Considering the film-forming properties and detachability, the molecular weight of the thermoplastic soluble heat-resistant resin (B) is preferably reduced viscosity (concentration: 0
．． 5 9/de, solvent: dimethylformamide, temperature =
30°C) of 0.3 or more. In addition, the thermal decomposition initiation temperature of the soluble heat-resistant resin (B) is . Preferably<Fi
The temperature is 250"C or higher, especially KIH, or 350°C or higher, and the soluble heat-resistant resin (H) can be used alone or in combination.

Although it dissolves in the first organic liquid (A1) in the present invention. The second organic liquid (As) K is insoluble and H (AIL
Heat-resistant resin fine particles (C) #'i dispersed in a solution containing (A2) and soluble heat-resistant resin CB), for example, fine particles obtained from the above-mentioned soluble heat-resistant resin CB) are used. From the viewpoint of heat resistance and solubility in (Ar)K, the above-mentioned polyamide resin is preferred. polyamideimide resin,
Polyimide resin (polyimide resin precursor Bo+J)
(containing amic acid resin) are used. Also. Ease and cost of synthesizing fine particles. Considering the chicken tropism. Preferably, a non-aqueous dispersion polymerization method (for example,
0-48531, JP-A-59-230018) and has a nine-average particle diameter of 40
Polyamide resins, polyamideimide resins, and polyimide resins having a diameter of μm or less are used. When the paste of the present invention is used for screen printing, the heat-resistant resin fine particles (C) preferably have an average particle diameter of 0.1 to 5 μm in consideration of the thixotropy of the paste, uniformity of the film, and harmony with the film thickness. Ru.

Such heat-resistant resin fine particles (C) Vi can be obtained by the non-aqueous dispersion polymerization method described above.

The heat-resistant resin fine particles (C) can be obtained by the above-mentioned non-aqueous dispersion polymerization method, but other methods are also available, such as mechanically pulverizing the powder recovered from the resin solution, or under high shear while adding a poor solvent to the resin solution. How to make K fine particles. There are methods such as drying sprayed oil droplets of resin solution to obtain fine particles. Any method can be used.

When using thermoplastic heat-resistant resin fine particles (C), the molecular weight of K should preferably be O. ，! The above are used.

The thermal decomposition initiation temperature of the thermosetting and thermoplastic heat-resistant resin particles (C) is preferably 250°C or higher, particularly preferably 3°C.
The temperature is 50°C or higher, and these can be used alone or in combination.

Preferred embodiments of the heat-resistant resin paste in the present invention are shown below. First, the combinations of the first organic liquid (A+) and the second organic liquid (As) are classified into the following two types K, for example.

(a) (A+) is N-methylpyrrolidone as described above;
Nitrogen-containing compounds such as dimethylacetamide, sulfur compounds such as dimethyl sulfoxide, lactones such as r-butyrolactone, and phenols such as xylenol. (At) is the above-mentioned q ethers such as diethylene glycol dimethyl ether, ketones such as cyclohexanone, esters such as butylcellosolp acetate, alcohols such as butanol, and hydrocarbons such as xylene (b) (AI) is the above-mentioned Ethers such as tetraethylene glycol dimethyl ether, ketones such as cyclohexanone. (A2) is the above-mentioned butylcellosolp acetate, esters such as ethyl acetate, and alcohols such as butanol and methyl lupitol. Examples of the soluble heat-resistant resin (B) and heat-resistant resin fine particles (C) that can be applied to the mixed organic liquid of the hydrocarbon type (a) such as xylene include the following.

As (B), for example, a heat-resistant resin having repeating units represented by the following formulas (1) to (10) is used.

(In the formula, X is 1CH2.0-1001 (wherein, 1 and R2 are hydrogen or a hydrocarbon group having 1 to 6 carbon atoms, and ) C}{3 CFs (3) The same applies to CFs), m is an integer from 1 to 100. ), m is an integer from 1 to ioo) ...(2) ...(5) ...(9) ...α0 (wherein, R3 and R4 are methyl, ethyl, probyl or As (C), for example, heat-resistant resin fine particles having a return unit in the formulas (b) to (b) (wherein is phenyl) may be mentioned.

CHs ... (8) (same in the following formulas) ... (to) (In the formula, Z is 1CHx, 10-1So2, 1001 The same is true in the formula below) (To) Examples of (B) and (C) that can be applied to the (b) type mixed organic liquid include the following.

is an integer) (As B3, For example, 2■, Kku represented by (self) As for (C), For example, in the above formula (1), X is A heat-resistant resin with a turning unit. Expressed by the above equation (6) Polysiloxane imide is used.

polyether amide Doimi Do, The above formula (5) ~Formula (9) (however, Formula (5), (6), (8) The X inside Liimide is used.

The ratio of (AI) to (AI) is preferably < Fi (AI) 1 0 to 70 parts by weight to (A.) 90 to 30 parts by weight.
;χ゛3 If (A1) is less than 10 parts by weight (Cl film-forming properties decrease, and if it exceeds 70 parts by weight (A!). (At)
(C) becomes easier to dissolve in a solution containing fB), and (C)
becomes difficult to disperse into the paste.

The boiling points of (Al) and (At) are preferably 100° C. or higher, considering the pot life of the paste during screen printing.

The concentrations of (Cl and fB) in the paste are preferably adjusted so that the paste has a viscosity of 30 to 10,000 Boas and a Chickentropy coefficient of 1.5 or more.

If the viscosity of the paste is less than 30 boas, sagging is likely to occur in the paste after printing, and if it exceeds 10,000 boas, printing workability decreases. Particularly preferably 300 to 5,
It is assumed to be 0 0 0 Boaz.

The ratio of (H) and (C) is. (C) 9 5 for iB) 5 to 70 parts by weight, assuming the total amount of Yoshitang Shikke is 100 parts by weight
~30 parts by weight are used. When the proportion of (C) is increased, thixotropy and dry film thickness can be increased.

The chicken tropy coefficient of the paste was measured using a FiE type viscometer (manufactured by Tokyo Keiki Co., Ltd., model EHD-U) in a sample amount of 0.49. Measurement was carried out at a measurement temperature of 25°C. Rotation speed: 1 rpm and 10 rpm
Apparent viscosity of paste m, η! and η1o, η1/
It is expressed as η weight ◎.

The total concentration of (C) and (B) in the paste is. Preferably, the weight is between tiio and 90%. If it is less than 10% by weight, it will be difficult to increase the dry thickness of the film, and if it exceeds 90% by weight, the fluidity of the paste will be impaired.

The dry film thickness and flexibility of the paste film in the present invention K vary depending on whether (B) and fcl are thermosetting or thermoplastic, respectively. General K thermosetting resins have a relatively low molecular weight and excellent solubility K. If thermosetting CB+ is used, the concentration of (B) in the paste can be increased, increasing the dry film thickness.

However, the removability of the cured product of thermosetting resin is significantly inferior to that of general K. On the other hand, the thermoplastic resin Fi solubility,
In terms of flexibility, it exhibits the opposite property to thermosetting resins. Therefore, one preferred combination of {B} and (C) is to use thermosetting (B) and dendritic (C).

(C) to (AI). The method for dispersing K in a solution containing (A!) and (B) is usually the following. Roll kneading and mixer mixing, which are used in the paint field, are applied. There is no particular restriction on the method as long as sufficient dispersion is achieved.

It is most preferable to cross-wire a plurality of times using three rolls K.

The chicken tropy coefficient of the paste in the present invention is 1.5
It is preferable to set it as above. If it is less than 1.5, sagging is likely to occur in the paste transferred to the base material. It is difficult to obtain sufficient pattern accuracy.

The paste of the present invention can be applied to a substrate and then subjected to final polishing preferably at a temperature of 150 to 500 DEG C. for 1 to 120 minutes to form a tough film.

The paste of the present invention may contain an antifoaming agent if necessary. Pigment. dye. Plasticizer. Antioxidants and the like may also be used together.

The heat-resistant resin paste of the present invention can be applied to monolithic ICs using silicon wafers as substrates, embedded ICs using ceramic substrates or glass substrates, thermal heads, and image sensors. Devices such as multi-chip high-density mounting boards. Interlayer insulation film and/or surface protection film for various wiring boards such as flexible wiring boards and rigid wiring boards, and various heat-resistant printing inks. Heat-resistant adhesives can be widely used and are extremely useful in industrial applications.

When the heat-resistant resin paste of the present invention is used as a protective film for semiconductor devices such as monolithic ICs, α-ray source materials such as uranium and thorium, sodium. Potassium, steel. It is preferable to reduce the content of ionic impurities such as iron. The total content of α-ray source materials such as uranium and thorium in the protective film is preferably less than 1 ppb, more preferably <Fi0.2
It is assumed to be less than ppb.

This is because the influence of α rays emitted from the protective film on malfunction of the device is reduced by K within the range of 0.2 to 1 ppb. Uranium in the resulting protective film. If the total content of α-ray source substances such as thorium exceeds 0.2 to 1 pI)b. Monomers used in the production of the resin, solvents, precipitants used in the purification of the resin, etc. Organic liquid (A+).
By purifying (As) etc., the total content of α-ray source substances such as siluran and thorium can be reduced. As for purification. Monomers and solvents used in resin production. Precipitating agents and organic liquids used in resin purification, etc. (A1). Distillation, sublimation, and recrystallization of (2), etc. By extraction etc. Also. It is convenient to carry out multiple steps of precipitating the synthesized resin solution into a purified poor solvent.

Also. Corrosion during use. In order to reduce leakage, the content of ionic impurities such as sodium, potassium, copper, iron, etc. is preferably 2 pI)m or less, more preferably tpI)m or less.
pm or less. If the total content of ionic impurities in the resulting paste exceeds 1 to 2 ppm, the total content of ionic impurities can be reduced by refining the monomers used in the production of the above resin in the same process as the above purification. can be reduced. It is not necessary to purify all of the monomers used. For example, purification may be carried out using only the monomer or only the monomer and the solvent K.

The IC used in the present invention includes a monolithic IC, a hybrid IC, a multi-layer high-density mounting board, and the like.

A monolithic ICFi, for example, one having the structure shown in FIG. 3K. The heat-resistant resin paste of the present invention is applied onto the #iLSI chip 2 and heated to form the heat-resistant resin film 1 (surface protection film).

In Fig. 3, l is a heat-resistant resin film, and 2 is an LSI chip. 3 bonding wires, 4 resin package, 5#
'i lead, 6 is a support.

For example, a hybrid IC has the structure shown in Figure 4. on the first layer wiring 11 and the resistance layer 12. The heat-resistant resin paste of the present invention is applied and heated to form a heat-resistant resin film 10 (interlayer insulation film). On top of this, second layer wiring 9 is formed.

In Figure 4, 7 is a diode chip and 8 is solder.
9 is the second layer wiring. 10 is a heat-resistant resin film, l1 is a first layer wiring, 12 is a resistive layer, and 13 is an alumina substrate.

The multi-chip high-density mounting board has, for example, the structure shown in FIG. Heat-resistant resin film 14 by coating and heating
By repeating the formation of (interlayer insulating film), etc., a 19th-order copper/heat-resistant resin multilayer interconnection layer is formed.The present invention will be explained with reference to a comparative example and an example K.

Comparative Example 1 (1) Preparation of heat-resistant resin Trimellitic anhydride 1'lO 1.00N
-Methylpyrrolidone 606 The above ingredients were stirred and put into a four-necked flask equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a moisture meter, and the temperature was raised to 160'CK without passing nitrogen gas. Gradually raise the K temperature. 205 while removing distilled water from the system.
℃, and the reaction was carried out in a temperature range of 205 to 210℃. The end point of the reaction was controlled by Gardner viscosity, and the reduced viscosity (using dimethylformamide as the solvent, sample concentration of 0.5 g/
0.4 1 (dl
/ 9) polyether amide imide resin was obtained. The N-methylpyrrolidone solution of the obtained polyetheramide-imide resin was diluted with N-methylpyrrolidone to a weight of about 25%, and this solution was poured into water that had been strongly stirred with a mixer to form a solid polyether. Amidimide resin was recovered. After washing this solid resin thoroughly with hot water.
It was washed by boiling with a large amount of water and methanol. After getting this. It was dried in a hot air dryer at 150° C. for 6 hours to obtain a powdery N-methylpyrrolidone K-soluble polyetheramide-imide resin having repeating units of the following formula.

(2) Preparation of fine resin particles Biromellitic dianhydride 2189 (1 mol) and N-methylpyrrolidone ( 16729 (0.03 g) of water was added, the temperature was raised to 50° C. while stirring, and the temperature was kept at the same temperature for 0.5 hours to completely dissolve and form a homogeneous solution. To this, 4.4'-diaminodiphenyl ether 1009 (0.5 mol) and 4.4'
-Diaminodiphenylmethane 999 (0.5 mol) was added, the temperature was immediately raised to 110°C, and the mixture was kept at the same temperature for 20 minutes to completely dissolve and form a homogeneous solution. Then, the temperature was raised to 200°C in about 2 hours. The reaction was allowed to proceed at the same temperature for 3 hours.

During the process, precipitation of polyimide resin particles was observed at about 140°C. Also, the reaction is in progress. The external pressure of the distilled water was immediately removed.

Fine particles of yellow-brown polyimide resin dispersed in N-methylpyrrolidone were obtained, which were recovered by filtration.
After repeating the acetone boiling process twice, the sample was boiled under reduced pressure. 200
It was dried at ℃ for 5 hours. The shape of these polyimide resin particles is almost spherical. It's porous. The average particle size (according to Coulter Electronics TA-1 [type K; the same applies hereinafter) is 8 μm, and the maximum particle size is 40 μm or less. This polyimide resin fine particle is insoluble in N-methylpyrrolidone and has a repeating unit of the following formula.

{3} Preparation of paste Soluble polyetheramide imide tree of powder prepared in (1) above @1 5 9. Add the polyimide resin fine particles 259 and N-methylpyrrolidone 609 prepared in (2) above. first. Roughly knead in a mortar. The mixture was then kneaded six times using a high-speed triple roll to obtain a paste in which fine resin particles were dispersed.

Comparative Example 2 {1} Preparation of heat-resistant resin fine particles using non-aqueous dispersion polymerization method (
b) Synthesis thermometer of dispersion stabilizer. Stirring machine. A four-hole flask K equipped with a ball condenser, ISOPAR-H (aliphatic hydrocarbon manufactured by Esso Standard Oil Co., Ltd., trade name) 185.79, lauryl methacrylate 106.89 and 2-hydroxyethyl methacrylate 6.19 were added. Get in. The temperature was raised to 100°C. While passing nitrogen gas. Pre-prepared lauryl methacrylate 106.99, 2-hydroxyethyl methacrylate 24.59. Benzoyl peroxide paste (benzoyl peroxide content: 50% by weight) A mixture of 2.4 and 9 was added dropwise over 2 hours while stirring. Continued 10
After keeping the temperature at 0°C for 1 hour, the temperature was raised to 140°C, and the reaction was carried out at the same temperature for 4 hours. This dispersion stabilizer solution had a nonvolatile content of 55% by weight when dried at 170°C for 2 hours, and the number average molecular weight of the dispersion stabilizer (determined by gel permeation chromatography using polystyrene of known molecular weight as a calibration curve). ) was 6a800.

(Note) Preparation of polyamide-imide resin particles While passing nitrogen gas through a 500-1 four-hole flask equipped with a thermometer, a stirrer, and a bulb-tube condenser. 35.1 g of 4,4'-diphenylmethane diisocyanate. M Rinichi 100 (manufactured by Nippon Polyurethane Co., Ltd. Aromatic polyisocyanate) 16.39
．． The dispersion stabilizer solution obtained in (a) above (non-volatile content: 4011
jl-1) 19g, ISOPAR-H 1 5 0
g, add 9.0g of N-methylpyrrolidone +380
The temperature was raised to 100° C. while stirring at rpm.

Next, 3 and 5 g of finely powdered trimellitic anhydride were added in advance, and the mixture was heated at 100°C for 1 hour and at 115°C for 1 hour. 1 hour at 125℃, 1 hour at 140℃. Sara K17
The temperature was raised to 0°C and the reaction was allowed to proceed for 2 hours. Continuous phase ISOP
Fine particles of brown polyamideimide resin dispersed in AR-H were obtained, which were recovered by filtration, further boiled with K water and methanol, P separated, and dried at 60°C under reduced pressure for 5 hours. I let it happen. The polyamide-imide resin fine particles were insoluble in solvent K, spherical in shape, and non-porous. The infrared absorption spectrum has 1780cm"" five imide bonds, 1650an""fish and 1540cm""! Absorption of amide bonds was observed. The average particle size of these polyamide-imide resin particles is approximately 3 μm, and the maximum particle size is 40 μm.
m or less.

(2) Preparation of paste Comparative Example 1, Powdered soluble polyetheramide imide resin 1 5 9 prepared in (1), above (1). Boria S doimide resin fine particles 259 and N-methylpyrrolidone 609 obtained in step (f) were added and first roughly kneaded in a mortar. Then, the mixture was kneaded six times using a pan-speed triple roll to obtain a paste in which polyamide-imide resin fine particles were dispersed.

Example 1 +11 Preparation of soluble heat-resistant resin (Bl) Place in flask K, stir, and gradually heat to K205°C without passing steal gas.
The temperature rose to . After keeping at the same temperature for about 1 hour. Cool to 175°C. At the same temperature, trimellitic anhydride was added over about 10 minutes. Then increase the temperature. The reaction can proceed in a temperature range of 205-210°C. The water distilled out after addition of trimellitic anhydride is quickly removed from the reaction system, and at the same time, the reaction is proceeded while additionally replenishing the distilled N-methylpyrrolidone.9. The end point of the reaction is controlled by Gardner viscosity. Reduced viscosity 0.5
A polyamideimide resin with a di!/9 ratio of 0 (di!/9) was obtained. From this solution, a powder is obtained: a repeating trimellitic anhydride of the following formula soluble in the mixed solvent of (A!) and (A2) in Table 1 192 1.04l4'-diaminodiphenylmethane 202 1.02N- Methylpyrrolidone 400 Combine the above ingredients except trimellitic anhydride with a stirrer,
Nitrogen introduction pipe. (2) Preparation of heat-resistant resin particles (C) Thermometer and stirrer equipped with a moisture meter. 3.3'4.4'-biphenyltetracarboxylic dianhydride 10.7119 (0.0
364 moles). 44'-diaminodiphenyl ether 7
．． 2899 (0.0364 mol) and 729 N-methylpyrrolidone were charged. The reaction was allowed to proceed for 10 hours at room temperature while stirring. The viscosity of the reaction system increased to a state K where stirring was difficult due to the formation of high molecular weight polyamic acid. A small amount of water was added and heated to 60°C to adjust the molecular weight.

Next, 529% of acetic anhydride and 269% of pyridine were added. It was left at room temperature for 12 hours. The resulting paste was poured into methanol and the precipitated solid resin in the form of fine particles was recovered. After thoroughly boiling and washing this solid resin with methanol,
After drying under reduced pressure at
I got it.

This polyimide resin is pulverized using a pulverizer, and the average particle size is 4.
．． 5 μm. (3) Preparation of heat-resistant resin paste The soluble polyamide-imide resin ( B) 159, polyimide thermal fat fine particles prepared in (2) above (C) 259, N-methylpyrrolidone (A+)
24g, diethylene glycol dimethyl ether (As
) 3 6 s was added and first coarsely kneaded in a mortar and then kneaded six times using a high-speed triple roll to obtain a heat-resistant resin paste in which polyimide resin fine particles were dispersed.

Example 2 The powdered soluble heat-resistant resin prepared in Example 1, (1)
B) 159, finely powdered heat-resistant resin particles with an average particle diameter of 3.5 μm. Polyimide-2080 (polyimide resin manufactured by Upjohn Co., Ltd., trade name) having repeating units of the following formula with a maximum particle size of 40 μm or less (C) 259, N-methylpyrrolidone 249 (A2), diethylene glycol dimethyl ether (As) 36 g was added, first roughly kneaded in a mortar, and then kneaded six times using a high-speed triple roll to disperse fine particles of polyimide 2080 and obtain a thoroughly heat-resistant resin paste. Polyimide-2080
teeth. It was soluble in N-methylpyrrolidone but insoluble in diethylene glycol dimethyl ether.

Example 3 (1) Preparation of soluble heat-resistant resin (B) 3,3: 10.7119 (0.0364 mol) of 4,4'-bi7enyltetracarboxylic dianhydride was added to a,
3S 4. 4'-Benzophenonetetracarboxylic dianhydride 11.7299 (0.0364 mol) A powder having repeating units of the following formula was prepared in exactly the same manner as in Example 1 and (2) except for changing K. Mixture K of (A1) and (A3) in Table 1 is a soluble polyimide resin (reduced viscosity: 0,
50d(/9) was obtained.

(2) Preparation of heat-resistant resin paste 12 g of the soluble polyimide resin (B) from (1) above was
Monomethylpyrrolidone (A+) 2 4 s. Dioxane (At) 12s to ethylene glycol dimethyl ether (As) 24s't-(I) Polyimide resin fine particles prepared in Examples 1 and (21) were added to the dissolved solution.
C) Add 289 and first roughly knead in a mortar. Then, the mixture was kneaded six times using a high-speed triple roll to obtain a heat-resistant resin paste in which polyimide resin fine particles were dispersed.

Example 4 {1} Preparation of soluble heat-resistant resin (B) Four-necked flask K￥ equipped with a thermometer, stirrer, and nitrogen inlet tube! 1.1,1,&3,3 while passing 1 elemental gas
-hexafluoro-2,2-bis(3.4-dicarbogysyphenyl)propanihydride 4 4.4 2 4 9
(0.1 mol) t 1,1,1,3,hawk 3-hexafluoro2.2-1:', *(4-7minophenyl)propane 33.426 g (0.1 mol) and N-methylpyrrolidone 441g was charged. This is my companion. The reaction proceeded for 6 hours at room temperature. The viscosity of the reaction system increased to a level where it was difficult to liquefy due to the formation of high molecular weight polyamic acid. After further reaction at 60°C for 4 hours. Cool. Acetic anhydride 143
g and pyridine 729 were added, and the mixture was left at room temperature for 12 hours. The resulting paste was poured into water and precipitated to collect nine fine particles of solid resin. After thoroughly boiling and washing this solid resin with methanol. A polyimide resin having a repeating unit of the following formula (reduced viscosity: 0.62 dJ!/Q) that is soluble in a mixed solvent of (Ar) and (A2) in Table 1 after drying under reduced pressure at 80°C for 10 hours. I got it.

Bis(4-(4-isocyanatophenoxy)phenyl)furopane 6119K.N-methylpyrrolidone 9.0g
was synthesized by a non-aqueous dispersion polymerization method by replacing N-methylpyrrolidone 1009 with an average particle diameter of IO μm. Maximum particle size 40μm
Polyamideimide resin fine particles having the following formula soluble in tetraethylene glycol dimethyl ether and insoluble in butyl cellosolve acetate K were obtained.

(2) Preparation of heat-resistant resin fine particles (C) Add 4,4'-diphenylmethane diisocyanate and MR-100 to (1) (portion) of Comparative Example 2 and add 2.2-(3) Preparation of heat-resistant resin paste as described above. (1) Soluble polyimide resin (B) 15G was added to tetraethylene glycol dimethyl ether (At) 42
9 and butyl cellosolp acetate (2) 1 8 gK
Add the polyamide-imide resin fine particles (Cl259) from (2) above to the M-dissolved solution K, and first roughly knead in a mortar, then knead by passing 6 times using a high-speed triple roll.The soluble polyamide-imide resin fine particles are dispersed. A heat-resistant resin paste was obtained.

Example 5 (1) Preparation of soluble heat-resistant resin (B) A four-necked flask equipped with a thermometer, a stirrer, and a nitrogen inlet tube K. While passing nitrogen gas, maleic anhydride (175.5%) was added.
9 and 500 g of A7 were charged and heated to reflux temperature K.

Next. Crack it in advance and then 2.2-bis (4-(4-
Aminophenoxy)phenyl]propane 346.59t
A solution dissolved in 670 g of acetone was added dropwise over about 1 hour. The reaction was carried out at reflux temperature for 0.5 hours to obtain a precipitate of bismaleamic acid. Next, a mixed solution of 2509 acetic anhydride, 30 g of iJ ethylamine, and 1.7 g of nickel acetate tetrahydrate was added at reflux temperature, and the mixture was allowed to react at this temperature for about 3 hours, and then cooled. Pour this solution into cold water. The obtained precipitate was thoroughly washed with K water. Filter this precipitate. Under reduced pressure,
Next, dry at 60°C for 10 hours.

100 g of the obtained powder was dissolved in acetone 2009K at 50°C and left as it was at room temperature for 24 hours.

The obtained crystals were collected by filtration under reduced pressure. After drying at 70° C. for 5 hours, a bismaleimide (B) insoluble in a mixed solvent of N-methylpyrrolidone and butylcellosolp acetate having repeating units of the following formula was obtained.

(2) Preparation of heat-resistant resin paste Soluble bismaleimide (B) of (1) above 37.59
, the polyimide resin fine particles used in Example 2 were soluble in N-methylpyrrolidone and made of butyl cellosol 4-tate K-2-2080(C)25
9,N-methylpyrrolidone (Ar) 18 g.
Butyl cellosolve acetate} (As) 1 9. 5
g was added thereto, first mixed roughly in a mortar, and then kneaded six times using a high-speed triple roll to obtain a heat-resistant resin paste in which soluble polyimide resin fine particles were dispersed.

Example 6 (1) Preparation of heat-resistant resin (B) A, Z 4. 4'-penzo7
Enonetetracarboxylic dianhydride 153.0589 (0
．． 475 mol), formula 3', <4'-biphenyltetracarboxylic dianhydride 139.9309 (0.475-r-
), [1,3-bis(i4-dicarpoxyphenylene)]
-L II 31 21.3269 (0.0500 mol) of 3-tetramethyldisiloxane dianhydride, 9Z6019 (ZOI mol) of ethanol, and 567 g of 1,3-dimethyl-2-imidazolidinone were charged. Stir,
Heat while heating. The temperature was raised to 100°C. The mixture was reacted at the same temperature for 4 hours to obtain a half ester of tetracarboxylic dianhydride. After cooling to 40 DEG C., 200.240 g of 44'-diaminodiphenyl ether (1,000 mol) and 850 g of triethylene glycol dimethyl ether were charged and dissolved to obtain a heat-resistant resin solution (resin concentration: 30 es by weight).

(2) Preparation of heat-resistant resin paste Heat-resistant resin solution of (1) above (resin concentration: 30% by weight) 5
Polyimide-2080 (C120G) used in Example 2 was added as 94C polyimide fine particles. First, it was roughly kneaded in a mortar, and then kneaded by passing it through six times using a high-speed triple roll to obtain a heat-resistant material in which soluble polyimide resin fine particles were dispersed. A resin paste was obtained.

Example 7 (1) Preparation thermometer of soluble heat-resistant resin (B). Stirring machine. Nitrogen introduction pipe. Four-necked flask K. with a moisture meter attached. 3,3S 4 purified by recrystallization from acetic anhydride
, 4'-benzophenonetetracarboxylic dianhydride 1
1.6029 (0.0360 mol). Recrystallized from a mixture of toluene and diethyl ether at a polymerization ratio of 1:1 [
1.3-bis(λ4-dicarboxyphenyl)-1.1
, 3.3-tetramethyldisiloxane] dianhydride 0.8
089 (0.0019 mol), recrystallized from a mixture of methanol and water at a polymerization ratio of 8:2 (methanol:water) 2
．． 4'-diaminodiphenyl ether 7.5899 (0
．． 0379 mol) and N-methylpyrrolidone 729 purified by vacuum distillation K were charged while passing nitrogen gas.

The mixture was allowed to react at room temperature for 10 hours with stirring, then the temperature was raised to 200°C, and the reaction was continued at the same temperature for 8 hours. During the reaction, water distilled out was immediately removed from the reaction system. The obtained solution was poured into methanol purified by distillation, and the precipitated solid resin was recovered. This solid resin was sufficiently boiled and washed with methanol purified by distillation, and then dried under reduced pressure at 80°C for 10 hours to produce a polyimide resin that is soluble in a mixed solvent of powdered N-methylpyrrolidone and diethylene glycol dimethyl ether and has a repeating unit of the following formula. I got it.

(2) Heat-resistant resin fine particles (C) were purified by recrystallization from acetic anhydride in a four-loop flask equipped with a crack thermometer, a stirrer, a nitrogen inlet tube, and a moisture meter.
, 11.1569 (0.0379 mol) of 3S 4,4'-biphenyltetracarboxylic dianhydride was recrystallized using a mixture of toluene and diethyl ether in a weight ratio of 1=1 [1.3 -bis(3,4-dicarboxy7
enyl)-1.1.3.3-tetramethyldisiloxane] dianhydride 0. 8 5 1 s (0.0020 mol), the weight ratio of methanol and water is 8 = 2 (methanol:
7.993 g (0.0399 mol) of 2.4' monocyamino di7enyl ether recrystallized using a mixture of water) and N-methylpyrrolidone 809 purified by vacuum distillation K.
was charged while passing nitrogen gas. 1 at room temperature under stirring.
After 9 hours of reaction. Raise the temperature to 200℃, and at the same temperature
The reaction proceeded for 0 hours. During the process, K was quickly removed from the water distilled out of the reaction system. The resulting solution was purified by vacuum distillation and diluted with 644 g of 7jN-methylpyrrolidone to obtain a solution with a resin concentration of approximately 25% by weight. This was spray-dried using a Mobil Minor type spray dryer manufactured by Ashizawa Waniro Atomizer Co., Ltd. to form fine particles, and then classified, and the average particle size was 4 μm and the maximum particle size was 40 μm or less. Polyimide resin fine particles having units were obtained. The reduced viscosity of this polyimide resin is 0.64 l/g
Met.

(3) Preparation of heat-resistant resin paste 17 g of N-methylpyrrolidone (A
+) and diethylene glycol dimethyl ether (Ax) purified by vacuum distillation 2 5 6 K dissolved in the 9 solution (2) above polyimide resin fine particles (C) 1 4
G was added and first roughly kneaded in a mortar and then kneaded six times using three high-speed rolls to obtain a heat-resistant resin paste in which polyimide resin fine particles were dispersed. The organic liquid (solvent) was removed from this paste, and the uranium and thorium contents were determined by activation analysis. Each is below the detection limit of 0.02ppb. and 0.05PPb or less. Also, sodium and potassium. The ionic impurity contents of copper and iron were each less than 2 PPm. Next, this paste was applied to the surface of a MOS type RAM with a density of 16K bits by screen printing, and heated at 100°C. is
o'C. 200℃. 0 at 250℃ and 350℃ respectively
．． Heat treatment was performed for 5 hours to form a polyimide protective 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-porosity glass as a sealing adhesive. The soft error rate of this semiconductor device was 30 fit.

The pastes obtained in Ratio Example 1.2 and Examples 1 to 6 were transferred onto a silicon single crystal wafer and screen printed so that the film thickness of the paste was approximately constant #1. 1 hour at 100℃.
The following properties of the film K obtained by baking at 200°C for 0.5 hours and then at 250°C for 0.5 hours were evaluated, and the results were shown in Table 1.
Shown below.

The uniformity of the film was determined by enlarging the surface and cross section of the film (1,000
Scanning electron micrographs (~10,000x) show bin holes. The presence or absence of voids was visually observed.

The bending resistance is 18 for the film K peeled off from the wafer.
The film was repeatedly bent at 0 degrees and evaluated by the number of times the film was bent until it broke.

The film thickness was measured using an electromagnetic film thickness meter.

Figure 1 shows scanning electron micrographs of cross sections of films obtained from Comparative Example 2 and Example 20 pastes. It is shown in Figure 2.

From Table 1, specific organic liquids (As, Ax). The heat-resistant resin pastes of Examples 1 to 4.6, in which a soluble heat-resistant resin (Bl) and heat-resistant resin fine particles (Cl) were combined. It is shown that the bending resistance, which is a measure of uniformity and flexibility, is extremely excellent. 9. Example 5 using a low molecular weight thermosetting resin as the soluble heat-resistant resin (B) has an even thicker It is shown that film formation can be achieved.

Furthermore, the heat-resistant resin pastes of Examples 1 to 6 have sufficient thixotropic properties.

The scanning electron micrograph of the cross section of the film obtained in Comparative Example 2 (Figure 1) shows that the spherical 7-Illust contained in the film remains for the entirety of the film, and many voids are observed. From the same cross-sectional photograph (Fig. 2) of the film obtained in Example 2, no residual filler or voids were observed. It is shown that the film is extremely uniform. Both Figures 1 and 2 are scanning electron micrographs in which the upper half is magnified by 1,000 times, and the lower half is magnified by 10,000 times, with the nine parts surrounded by a white frame in the upper half.

Here are the details. (Effects of the Invention) The heat-resistant resin paste of the present invention can be applied by screen printing, can form a uniform film with few pinholes and voids, and has a high degree of heat resistance. Provides flexibility, moisture resistance, and corrosion resistance. Also. It is possible to impart appropriate thixotropy, and excellent pattern accuracy can be obtained by printing.

[Brief explanation of drawings]

Figure 1 is a scanning electron micrograph showing the particle structure of the film obtained from the paste of Comparative Example 2. Figure 2 is. Example 2
A scanning electron micrograph showing the particle structure of the film obtained from the heat-resistant resin paste of the present invention, FIG. 3 is a cross-sectional view of a monolithic IC using the heat-resistant resin paste of the present invention, and FIG.
A cross-sectional view of a hybrid IC using the heat-resistant resin paste of the present invention and a cross-sectional view of a multi-chip high-density mounting board using the heat-resistant resin paste of the present invention. Explanation of symbols 1...Heat-resistant resin film 2...LI8 chip 3.
...Bonding wire 4...Resin package 6...Support 8...Solder 10...Heat-resistant resin film 12...Resistance layer 14...Heat-resistant resin film 16...Wiring layer l8...・Solder l9...Copper/heat-resistant resin multilayer wiring layer 20...Ceramic multilayer wiring board 5...Lead 7...Diode chip 9...Second layer wiring 11...First layer wiring l3. ...Alumina substrate 15...Wiring layer 17...LSI chip Fig. 3 9-2nd layer wiring diagram +! -First layer wiring 13・-Alumina substrate l6 Fig.

Claims (6)

[Claims] 1. First organic liquid (A_1), second organic liquid (A_1)
2) The heat-resistant resin (B) is soluble in the mixed organic liquid of (A_1) and (A_2), and the heat-resistant resin (B) is soluble in (A_1), but (A_
2) contains insoluble heat-resistant resin fine particles (C), and (A_1
), (A_2) and (B) in which (C) is dispersed. 2. The second organic liquid (A_2) is the first organic liquid (A_
2. The heat-resistant resin paste according to claim 1, which evaporates from the paste more easily than 1). 3. Soluble heat-resistant resin (B) and heat-resistant resin fine particles (C)
The heat-resistant resin paste according to claim 1 or 2, wherein is a polyamide resin, a polyamideimide resin, or a polyimide resin. 4. Claim 1, wherein the heat-resistant resin fine particles (C) are polyamide resin, polyamide amide resin, or polyimide resin obtained by a non-aqueous dispersion polymerization method and having an average particle diameter of 40 μm or less.
Heat-resistant resin paste according to 2 or 3. 5. 5. The heat-resistant resin paste according to claim 1, wherein the paste has a thixotropy coefficient of 1.5 or more. 6. An IC having an interlayer insulating film and/or a surface protection film obtained from the heat-resistant resin paste according to any one of claims 1 to 5.