JP2007246897A - Heat-resistant resin paste, method for producing heat-resistant resin paste and semiconductor device having insulation film or protection film derived from heat-resistant resin paste - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a heat-resistant resin paste exhibiting excellent rheological properties in screen printing or dispense method and having excellent wettability to a substrate, a method for producing the heat-resistant resin paste in high efficiency and a semiconductor device having an insulation film or a protection film derived from the heat-resistant resin paste. <P>SOLUTION: The heat-resistant resin paste is produced by compounding (a) a heat-resistant resin solution containing the first organic solvent (A1) and a heat-resistant resin (B) soluble in (A1), (b) a heat-resistant resin filler dispersion containing the first organic solvent (A1), the second organic solvent (A2) and a heat-resistant resin (C) insoluble in the mixture of (A1) and (A2), and a siloxane resin (D) containing a silicone diamine compound having 2-51 siloxane bonds in the molecule. The amount of the silicone diamine in the siloxane resin (D) is 1-80 pts. mol based on 100 pts. mol of total diamine. The invention further provides a semiconductor device having an insulation film or a protection film derived from the heat-resistant resin paste. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention has excellent rheological properties in screen printing methods and dispensing methods, has excellent wettability with respect to various substrates, and is a heat resistant resin suitable for applications such as coating materials, adhesives, stress relaxation materials for semiconductor devices, etc. The present invention relates to a paste, a manufacturing method thereof, and a semiconductor device having an insulating film or a protective film obtained from the heat-resistant resin paste.

  Since heat-resistant resins such as polyimide resins are excellent in heat resistance and mechanical properties, they are already widely used in the field of electronics as surface protective films and interlayer insulating films for semiconductor elements.

  Recently, screen printing and dispensing methods that do not require complicated processes such as exposure, development, and etching have been focused on as image forming methods for polyimide-based resin films for surface protective films, interlayer insulating films, and stress relieving materials. Has been.

  In the screen printing method and the dispensing method, a heat-resistant resin paste having a base resin, a filler, and a solvent as constituent components and having thixotropic properties is used. Most of the heat-resistant resin pastes that have been developed so far use silica fine particles or non-soluble polyimide fine particles as a filler to impart thixotropic properties, so that many voids and bubbles remain at the filler interface during heating and drying. However, problems such as low film strength and poor electrical insulation have been pointed out.

  Therefore, there is no such problem. By combining a special organic filler (soluble filler), base resin, and solvent that dissolves the filler first when heated and dried and is compatible with the base resin to form a film. Has disclosed a heat-resistant resin paste capable of forming a polyimide pattern excellent in (see Patent Document 1).

  The characteristics required for pastes in the screen printing method and the dispensing method are pattern forming properties such as printing or coating width (line / space), film thickness, shape, etc., rheological characteristics typified by thixotropic properties, and coated substrates The wettability between the paste and the paste greatly affects the pattern formation.

In general, a leveling agent is added to the paste to improve the wettability on the coated substrate. However, the leveling effect is low, the compatibility with the paste, and the heating device used for drying and curing. It has various problems such as contamination.
JP-A-2-289646

  In heat-resistant resin pastes, excellent pattern formability is required, that is, rheological properties typified by thixotropy at the time of coating, and further improved wettability between the coated substrate and the paste, after printing and coating In addition, it is required that a predetermined portion can be covered without causing shrinkage, repelling, or pinholes during drying or curing.

  The present invention includes a heat-resistant resin paste having excellent rheological properties in a screen printing method or a dispensing method, and having excellent wettability with respect to a substrate, and a method for efficiently producing the heat-resistant resin paste. An object of the present invention is to provide a semiconductor device having an insulating film or a protective film obtained from the above heat-resistant resin paste.

  In the heat-resistant resin paste by the screen printing method or the dispensing method, the present inventors disperse a siloxane resin having a silicone diamine compound as a constituent, so that the formed pattern is immediately after formation or after being left, and during drying / curing. The present inventors have found that patterning defects caused by shrinkage and repelling can be improved, and the present invention has been completed.

  The present invention includes (a) a heat-resistant resin solution containing a heat-resistant resin (B) soluble in the first organic solvent (A1) and (A1), (b) the first organic solvent (A1), A heat-resistant resin filler dispersion containing a heat-resistant resin (C) insoluble in the second organic solvent (A2) and a mixed solvent of (A1) and (A2), and having 2 to 51 siloxane bonds in the molecule A heat-resistant resin paste formed by blending a siloxane resin (D) having a silicone diamine compound as a component, wherein the silicone diamine content in the siloxane resin (D) is 1 to 80 parts per 100 parts by mole of the total diamine. It is a heat-resistant resin paste that is a molar part.

  Moreover, as one aspect, the present invention is the above heat resistant resin paste in which the heat resistant resin (B) and the heat resistant resin (C) are a polyamide resin, a polyamideimide resin, a polyimide resin, or a precursor thereof.

Moreover, as one aspect, the present invention provides a siloxane resin (D) having a silicone diamine compound in the structure represented by the following general formula (I):

(Wherein R ₁ and R ₂ are each independently a divalent organic group, and n is an integer of 1 to 50), or the silicone diamine and other diamines, The following general formula (II)

(In the formula, Z represents a single bond, —O—, —S—, —SO ₂ —, —C (═O) —, —S (═O) —, —CH ₂ —, —CH (CH ₃ ) —). , -C (CH ₃ ) _2- ) and the above heat-resistant resin paste, which is a polyimide resin obtained by reacting with an aromatic tetracarboxylic dianhydride represented by a polar solvent, or a precursor thereof. It is.

  In one embodiment, the present invention provides a siloxane resin (D) having a silicone diamine compound as a constituent, a silicone diamine represented by the above general formula (I), or the silicone diamine and other diamines, and acid anhydrides. The heat-resistant resin paste is a polyamideimide resin obtained by reacting a trivalent polycarboxylic acid having a physical group or a reactive derivative thereof in a polar solvent, or a precursor thereof.

  Moreover, as one aspect, the present invention provides a siloxane resin (D) having a silicone diamine compound as a constituent, a silicone diamine represented by the above general formula (I), or the silicone diamine and other diamines, and a dicarboxylic acid. Or it is said heat resistant resin paste which is a polyamide-type resin formed by making it react with the reactive derivative in a polar solvent.

  As one aspect of the present invention, the heat-resistant resin paste has a heat-resistant resin paste in which the amount of the siloxane resin (D) having a silicone diamine compound is 1 to 20 parts by weight with respect to 100 parts by weight of the resin Resin paste.

  As one aspect, the present invention is the above heat-resistant resin paste in which the second organic solvent (A2) is more easily evaporated from the paste than the first organic solvent (A1).

  As one aspect of the present invention, the heat-resistant resin (C) is a polyamide resin, a polyamideimide resin, a polyimide resin or a precursor thereof having an average particle size of 40 μm or less obtained by a non-aqueous dispersion polymerization method. This is a heat-resistant resin paste.

As one aspect, the present invention is the above heat-resistant resin paste having a contact angle on a silicon, SiO ₂ film, polyimide resin, ceramic, or metal surface of 20 ° or less at room temperature.

  Moreover, this invention is said heat resistant resin paste whose thixotropy coefficient of said heat resistant resin paste is 1.5-10.0 as one aspect | mode.

  The present invention also includes (a) a heat resistant resin solution containing a heat resistant resin (B) soluble in the first organic solvent (A1) and (A1), and (b) the first organic solvent (A1). , A second organic solvent (A2), and a heat resistant resin filler dispersion containing a heat resistant resin (C) insoluble in a mixed solvent of (A1) and (A2), and 2 to 51 siloxane bonds in the molecule It is a manufacturing method of the heat resistant resin paste characterized by mix | blending the siloxane resin (D) which has the silicone diamine compound which has this in a structure.

  As a further aspect, the present invention provides a paste in which a filler of a heat resistant resin (C) is dispersed in a solution containing the first organic solvent (A1), the second organic solvent (A2) and the heat resistant resin (B). Heat-resistant, characterized in that a siloxane resin (D) having a silicone diamine compound as a constituent is dissolved in (A1), (A2), or a mixed solvent of (A1) and (A2) and added to the mixture It is a manufacturing method of a resin paste.

  Moreover, this invention is an insulating film obtained from the said heat resistant resin paste or the heat resistant resin paste manufactured by the manufacturing method of the said heat resistant resin paste.

  Furthermore, this invention is a semiconductor device which has a protective film obtained from the said heat resistant resin paste or the heat resistant resin paste manufactured by the manufacturing method of the said heat resistant resin paste.

  The heat-resistant resin paste according to the present invention and the heat-resistant resin paste obtained by the method for producing the heat-resistant resin paste described above are thixotropic properties capable of forming a precise pattern when used as a paste used in a screen printing method or a dispensing method. The semiconductor device has excellent rheological properties and excellent wettability with respect to various substrates, and also exhibits excellent effects in a semiconductor device having an insulating film or protective film obtained from a heat-resistant resin paste.

  The heat-resistant resin paste according to the present invention comprises (a) a first heat-resistant resin solution containing a heat-resistant resin (B) soluble in (A1) and (A1), and (b) a first organic solvent. A heat-resistant resin filler dispersion containing a heat-resistant resin (C) insoluble in the solvent (A1), the second organic solvent (A2), and the mixed solvent of (A1) and (A2); It is a heat resistant resin paste formed by blending a siloxane resin (D) having a silicone diamine compound having a single siloxane bond, and the silicone diamine content in the siloxane resin (D) is 100 mol parts of the total diamine. On the other hand, the heat-resistant resin paste is 1 to 80 mol parts.

  In the heat resistant resin paste of the present invention, (a) is a heat resistant resin solution in which (B) is dissolved, and (b) is a heat resistant resin filler dispersion in which (C) is dispersed as a filler. is there.

  Moreover, since the heat resistant resin paste of the present invention contains the filler (C), it has thixotropic properties in the coating process. And by heating at a high temperature after applying the above heat-resistant resin paste, the filler of (C) is dissolved in (A1) and (A2) in the heat-resistant resin paste, and finally a uniform film with (B) Form. (B) and (C) may be in a state in which (B) is dissolved in (a) and in a state in which (C) is dispersed in (b). Although the same resin or different resins may be used, it is preferable to use the same resin. In any case, (A1) uses a good solvent for (B) and (C), and (A2) uses a poor solvent for (B) and (C).

  Moreover, (D) contained in the said heat resistant resin paste can provide wettability with respect to a board | substrate at the time of printing and application | coating.

  As described above, the heat-resistant resin paste in the present invention is excellent in thixotropy and wettability with various substrates that affect the pattern forming property in the screen printing method and the dispensing method. , Uniform without voids, excellent flexibility, moisture resistance and corrosion resistance can be obtained.

  In the heat-resistant resin paste of the present invention, examples of (B) and (C) include polyester resins, polyether resins, polyamide resins, polyimide resins, polyamideimide resins, or precursors thereof. A polyamide resin, a polyimide resin, a polyamideimide resin or a precursor thereof is preferable in that it has heat resistance necessary for high heat applied in a semiconductor manufacturing process such as reflow, and these are used alone or in combination of two or more. Can be used in combination.

  Examples of the method for obtaining a polyamide resin, a polyimide resin, a polyamideimide resin or a precursor thereof as (B) and (C) include an aromatic, aliphatic or alicyclic diamine compound and a tetracarboxylic dianhydride. Polyimide resin by reaction, aromatic aliphatic or alicyclic diamine compound and tricarboxylic acid or its reactive acid derivative to react polyamideimide resin, or aromatic, aliphatic or alicyclic diamine compound and dicarboxylic acid The method of obtaining a polyamide resin by reaction with an acid or its reactive acid derivative is mentioned.

  The above reaction can be carried out without solvent or in the presence of an organic solvent. The reaction temperature is preferably 25 to 250 ° C., and the reaction time can be appropriately selected depending on the scale of the batch, the reaction conditions employed, and the like.

  There is no restriction | limiting in particular as said organic solvent used when manufacturing such (B) and (C), For example, ethers, such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether, and triethylene glycol diethyl ether Solvents, sulfur-containing solvents such as dimethyl sulfoxide, diethyl sulfoxide, dimethyl sulfone, sulfolane, ester solvents such as γ-butyrolactone, cellosolve acetate, ketone solvents such as cyclohexanone, methyl ethyl ketone, N-methylpyrrolidone, dimethylacetamide, dimethyl Nitrogen-containing solvents such as propylene urea, aromatic hydrocarbon solvents such as toluene and xylene, etc. are mentioned, and these may be used singly or in combination of two or more. It can be.

  The number average molecular weight of (B) and (C) is preferably 1,000 to 30,000. If the number average molecular weight of (B) and (C) is less than 1,000, the viscosity of the heat-resistant resin paste using these will be low, causing paste sagging during screen printing and dispensing, and not satisfying the patterning property. Tend. If the number average molecular weight of (B) and (C) exceeds 30,000, the viscosity of the heat-resistant resin paste using them becomes too high, or stringing problems tend to occur and patterning defects tend to occur. is there.

  Here, the number average molecular weight is a polystyrene conversion value obtained by gel permeation chromatography using polystyrene having a known molecular weight as a calibration curve. For example, it can be measured under the following conditions. The following examples are measured under the following conditions.

Apparatus: Hitachi 655A type (manufactured by Hitachi, Ltd.)
Column: Two GelPak GL-S300M-5 (NMP) (manufactured by Hitachi Chemical Co., Ltd.) Eluent: N-methyl-2-pyrrolidone H ₃ PO ₄ (0.06 mol / liter)
Flow rate: 1 ml / min Detector: UV (270 nm)
In the heat resistant resin paste of the present invention, the filler (C) is preferably a non-aqueous dispersion polymerization method (for example, Japanese Patent Publication No. Sho), considering the ease of synthesis of the heat resistant resin filler dispersion, cost, and thixotropy. 60-048531 and JP-A-59-230018) having an average particle size of 40 μm or less is preferable, and the heat-resistant resin paste according to the present invention is applied to a screen printing method or a dispensing method. When used, considering the thixotropy of the heat-resistant resin paste, the uniformity of the film and the film thickness, (C) is a polyamide resin, a polyamideimide resin and a polyimide resin having an average particle diameter of 0.1 to 5 μm. Alternatively, it is preferable to use fine particles of these precursors.

  In addition to the non-aqueous dispersion polymerization method described above, the filler of (C) is, for example, a method of mechanically pulverizing a powder recovered from a resin solution, a method of drying spray oil droplets of a resin solution to obtain a filler, There is a method of making fine particles under high shear while adding a poor solvent to the resin solution containing (C), and any method is used.

  The heat-resistant resin (C) is not particularly limited as long as the filler can be formed by the above-described method, and the component (C) can be synthesized as a heat-resistant resin having the same component as the component (B). it can.

  (A) used by this invention melt | dissolves (B) obtained as mentioned above. This may be obtained by dissolving (B) obtained in the presence of a solvent, or may be prepared by dissolving (B) separately prepared in (A1), and is prepared without particular limitation. can do.

  Moreover, (b) used for this invention disperse | distributes (C) obtained by making it as a filler as a filler. In the reaction, a mixed solvent of (A1) and (A2) may be used to deposit a filler, and the liquid in which the filler is dispersed may be used as it is. Can be prepared by precipitating fillers or by separately dispersing (C) as a filler using a mixed solvent of (A1) and (A2). It can be prepared without limitation.

  In the heat resistant resin paste of the present invention, (A1) can dissolve (B) at room temperature, and (C) can be present as a filler in a mixed solvent with (A2) without being dissolved at room temperature. A solvent which dissolves (C) at a temperature at the time of heat drying at 150 to 300 ° C. or at a heat curing at 350 to 450 ° C. is suitable.

  Examples of (A1) having the above characteristics include protic solvents that dissociate and release protons easily, such as alcohols and carboxylic acids, and aprotic solvents that dissociate and do not generate protons. Specifically, when (B) and (C) are polyimides, for example, dimethylpropylene urea can be suitably used as (A1).

  In addition, (C) (same as (B), the same applies hereinafter) may be used in the mixed solvent of (A1) and (A2) at the time of heat drying at 150 to 300 ° C. or at the time of heat curing at 350 to 450 ° C. In order to dissolve at a temperature of (1), one method is to reduce the amount of (A2) in the mixed solvent of (A1) and (A2). (A2) evaporates from the paste more than (A1). What is easy to do is preferable. Here, the degree of easiness of evaporation from the pastes (A1) and (A2) depends on the boiling points and vapor pressures of (A1) and (A2).

  Therefore, (A1) and (A2) used in (b) preferably have a boiling point of 100 to 350 ° C. in consideration of the usable time of the heat resistant resin paste during screen printing, and 150 to 300 More preferably, the difference between the boiling points of (A1) and (A2) Δbp [Δbp = bp (good solvent) −bp (poor solvent)] is preferably 5 ° C. or more, more preferably 20 ° C. or more, 40 degreeC or more is especially preferable. On the other hand, if Δbp does not satisfy 5 ° C., (A1) volatilizes before (C) dissolves, and (C) and the siloxane resin (D) are incompatible with each other after film formation, and an interface is formed. Strength and insulation may be reduced.

  In the above (b), for example, when a resin different from (B) is used as (C), (A2) is not used by utilizing the difference in solubility between (B) and (C) with respect to (A1). It can also be prepared. That is, (A1) in which (B) is dissolved at room temperature and (C) is not dissolved may be selected. For example, after (A1) is heated to dissolve (C), this solution (C) can be deposited as a filler by cooling.

Examples of (D) in the heat-resistant resin paste of the present invention include polyester resins, polyether resins, polyamide resins, polyimide resins, polyamideimide resins, or precursors thereof, but the high heat applied during the semiconductor manufacturing process. On the other hand, it is preferable to use a polyamide resin, a polyimide resin, a polyamideimide resin, or a precursor thereof because it has necessary heat resistance. As a method for obtaining these resins, the general formula (I)

(Wherein R ₁ and R ₂ are each independently a divalent organic group, and n is an integer of 1 to 50), or the silicone diamine and other diamines, The following general formula (II)

(In the formula, Z represents a single bond, —O—, —S—, —SO ₂ —, —C (═O) —, —S (═O) —, —CH ₂ —, —CH (CH ₃ ) —). A method of obtaining a polyimide resin or a precursor thereof by reacting with a tetracarboxylic dianhydride represented by —C (CH ₃ ) ₂ — in a polar solvent, represented by the general formula (I) Method of obtaining polyamideimide resin or precursor thereof by reacting silicone diamine or silicone diamine and other diamines with a trivalent polycarboxylic acid having an acid anhydride group or a reactive derivative thereof in a polar solvent Or a method of obtaining a polyamide resin by reacting the silicone diamine represented by the general formula (I) or the silicone diamine and other diamines with a dicarboxylic acid or a reactive derivative thereof in a polar solvent. The silicone diamine can be used in the above reaction alone or in combination with other diamines as two or more diamines.

In the silicone diamine represented by the general formula (I), R ₁ and R ₂ are divalent organic groups, preferably an organic group having 1 to 8 carbon atoms, specifically a branched or straight chain alkylene group. , -Ph-. Moreover, it is preferable that the repeating number n in General formula (I) is 1-50. If n is less than 1, the wettability of the obtained heat-resistant resin paste on the substrate tends to be insufficient, and if it exceeds 50, the compatibility of (a) and (b) with (D). Tends to decrease and the two layers are separated. In addition, from the viewpoint of wettability of the heat-resistant resin paste on the substrate, the number of repetitions n is particularly preferably 3 or more.

  Here, the silicone diamine represented by the general formula (I) used for producing (D) is not particularly limited, and is a commercially available product, for example, trade names KF-8010, X-22-161A, X- 22-161B (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) or the like can be used.

  Moreover, there is no restriction | limiting in particular also about the other diamines which can be used together with the said silicone diamine, For example, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 3,3'- diaminodiphenyl ether, 4,4 '-Diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenyldifluoromethane, 4,4 '-Diaminodiphenyldifluoromethane, 3,3'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfide, 3,4'-diaminodiphe Sulfides, 4,4′-diaminodiphenyl sulfide, 3,3′-diaminodiphenyl ketone, 3,4′-diaminodiphenyl ketone, 4,4′-diaminodiphenyl ketone, 2,2-bis (3-aminophenyl) propane 2,2- (3,4'-diaminodiphenyl) propane, 2,2-bis (4-aminophenyl) propane, 2,2-bis (3-aminophenyl) hexafluoropropane, 2,2-bis ( 4-aminophenyl) hexafluoropropane and the like.

In addition, the tetracarboxylic dianhydride represented by the general formula (II) used when producing a polyimide resin as (D) is not particularly limited, and for example, 3,3 ′, 4,4′-biphenyl. Tetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 2,2-bis (3 , 4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, ( 3,4-dicarboxyfe Sulfone dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, 3,4,3 ′, 4′-benzophenonetetracarboxylic dianhydride, 2,3,2 ′, 3′- Examples thereof include benzophenone tetracarboxylic dianhydride and 2,3,3 ′, 4′-benzophenone tetracarboxylic dianhydride. In the present invention, pyromellitic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, 1,2 , 5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 1,4,5 , 8-Naphthalenetetracarboxylic dianhydride can be used in combination with the tetracarboxylic acid dihydrate represented by the above general formula (II).
In addition, the trivalent carboxylic acid having an acid anhydride group or a derivative thereof used when producing a polyamideimide resin as (D) is not particularly limited, and examples thereof include general formulas (III) and (IV).

(Wherein, A represents —O—, —S—, —SO ₂ —, —C (═O) —, —S (═O) —, —CH ₂ —). Trimellitic anhydride or a derivative thereof is preferable in terms of heat resistance and cost. For example, when polyamideimide is obtained using trimellitic anhydride, the following general formula (V)

(Wherein, a, b and c are each independently an integer of 1 to 100, and R ₁ and R ₂ are each independently a hydrogen atom, an aryl group or an alkyl group) and a trimellit The following general formula (VI) obtained by reacting an acid anhydride in the absence of a solvent or in an organic solvent

(Wherein, a, b, and c are each independently an integer of 1 to 100, and R ₁ and R ₂ are each independently a hydrogen atom, an aryl group, or an alkyl group), or a general A compound obtained by dehydrating and ring-closing the compound represented by the formula (VI) or a derivative thereof can be obtained.

  In addition, the dicarboxylic acid or derivative thereof used when preparing the polyamide resin as (D) is not particularly limited, and examples thereof include aliphatic dicarboxylic acids (succinic acid, glutaric acid, adipic acid, azelaic acid, suberic acid, Sebacic acid, decanedioic acid, dodecanedioic acid, dimer acid, etc.) and aromatic dicarboxylic acids (isophthalic acid, terephthalic acid, phthalic acid, naphthalenedicarboxylic acid, oxydibenzoic acid, etc.).

  The amount of silicone diamine represented by the general formula (I) forming the silicone diamine compound is 1 to 80 parts by mole and 5 to 80 parts by mole with respect to 100 parts by mole of the total diamine of (D). Is preferably 5 to 50 parts by mole, more preferably 10 to 50 parts by mole, and particularly preferably 20 to 30 parts by mole. If the amount of silicone diamine is less than 5 mole parts, especially less than 1 mole part, the heat-resistant resin paste using this has insufficient wettability with the coated substrate, and a pattern formed by screen printing or dispensing is formed. Immediately after standing or after standing, there is a tendency that patterning defects due to shrinkage or repelling that occur during drying and curing tend to occur. When the amount exceeds 80 parts by mole, the above heat-resistant resin paste using the same has a decrease in rheological characteristics represented by a thixotropy coefficient, and the resolution tends to decrease due to paste sagging or the like. Moreover, there is a possibility that the heat resistance of the heat-resistant resin paste is lowered or phase separation occurs.

  Examples of the polar solvent for producing the above (D) include ether solvents such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, dimethyl sulfoxide, diethyl sulfoxide, dimethyl sulfone, sulfolane and the like. Sulfur-containing solvents, ester solvents such as γ-butyrolactone and cellosolve acetate, ketone-based solvents such as cyclohexanone and methyl ethyl ketone, nitrogen-containing solvents such as N-methylpyrrolidone, dimethylacetoacedo and dimethylpropyleneurea, toluene and xylene And the like, and these can be used singly or in combination of two or more. The said polar solvent can be selected according to (D) to manufacture, and if necessary, use the same solvent as (A1) and (A2) used for the heat resistant resin paste of this invention. Can do.

  The number average molecular weight of the (D) is preferably 2,000 to 20,000, and if it is less than 2,000, the heat resistance of the heat resistant resin paste may be lowered, and 20,000 If it exceeds 1, the heat-resistant resin paste may become highly viscous or insolubilized and separated.

  In addition, each polyimide resin precursor or polyamideimide resin precursor used as the above-mentioned (B), (C), and (D) used for the heat resistant resin paste of the present invention is a polyimide resin or Polyamideimide resin can be used, and dehydration ring closure can be performed by a general method. For example, a thermal ring closure method in which dehydration ring closure is performed by heating under normal pressure or reduced pressure, a chemical ring closure method using a dehydrating agent such as acetic anhydride in the presence or absence of a catalyst, and the like can be used.

  In the case of the thermal ring closure method, it is preferably carried out while removing water generated by the dehydration reaction out of the system. At this time, it is carried out by heating the reaction solution to 80 to 400 ° C, preferably 100 to 250 ° C. At this time, a solvent that azeotropes with water such as benzene, toluene, xylene or the like may be used in combination to remove water azeotropically.

  In the case of the chemical ring closure method, the reaction is carried out at 0 to 120 ° C, preferably 10 to 80 ° C in the presence of a chemical dehydrating agent. As the chemical dehydrating agent, for example, acid anhydrides such as acetic anhydride, propionic anhydride, butyric anhydride, and benzoic acid, and carbodiimide compounds such as dicyclohexylcarbodiimide are preferably used. At this time, it is preferable to use together a substance that promotes the cyclization reaction, such as pyridine, isoquinoline, trimethylamine, triethylamine, aminopyridine, imidazole.

  The chemical dehydrating agent is used in an amount of 90 to 600 mol% based on the total amount of the diamine compound, and the substance that promotes the cyclization reaction is used in an amount of 40 to 300 mol% based on the total amount of the diamine compound. Further, a dehydration catalyst such as triphenyl phosphite, tricyclohexyl phosphite, triphenyl phosphate, phosphorus compounds such as phosphoric acid and phosphorus pentoxide, and boron compounds such as boric acid and boric anhydride may be used.

  The reaction solution that has been imidized by the dehydration reaction is compatible with an organic solvent in the reaction solution such as a lower alcohol such as methanol, water, or a mixture thereof, and is a poor solvent for the resin. A polyimide resin or a polyamide-imide resin is obtained by pouring into an excess solvent to obtain a resin precipitate, filtering this, and drying the solvent. Considering reduction of remaining ionic impurities, etc., the above-described thermal ring closure method is preferable.

  The blending ratio of (A1), (A2), (B) and (C) in the heat resistant resin paste of the present invention is 10 to 300 parts by weight of (C) with respect to 100 parts by weight of (B), (A1 ) And (A2) is preferably 50 to 3,000 parts by weight, (C) is 20 to 200 parts by weight, and (A1) and (A2) are 75 to 2,000 parts by weight in total. More preferably, (C) is 20 to 200 parts by weight, and (A1) and (A2) are particularly preferably 100 to 1,000 parts by weight in total.

  (B) If the amount of (C) is less than 10 parts by weight with respect to 100 parts by weight, the thixotropy when applied by the screen printing method or the dispensing method is insufficient, and the printability tends to be impaired. On the other hand, if the amount exceeds 300 parts by weight, the fluidity of the paste is impaired, so that the printability and applicability tend to decrease.

  Moreover, when the total amount of (A1) and (A2) is less than 50 parts by weight relative to 100 parts by weight of (B), the fluidity of the heat-resistant resin paste tends to be impaired. On the other hand, when the amount exceeds 3,000 parts by weight, the viscosity of the heat-resistant resin paste becomes low, and it becomes difficult to form a paste sag or thick film, and the pattern formability tends to deteriorate.

  In the heat resistant resin paste of the present invention, the blending ratio of (A1) and (A2) is preferably 10 to 70 parts by weight of (A1) with respect to 100 parts by weight of the total amount of (A1) and (A2). It is preferable that When (A1) is less than 10 parts by weight, (C) abnormally precipitates and the film formability tends to be inferior. When it exceeds 70 parts by weight, when preparing (b), (C) is easily dissolved in the mixed solvent of (A1) and (A2), and as a result, (C) is not solidly dispersed in the paste. The thixotropy of the above heat-resistant resin paste is lowered, paste sagging or the like occurs during screen printing or application by a dispensing method, and the pattern formability tends to be lowered.

  In the heat resistant resin paste of the present invention, the content of (D) is 1 to 20 with respect to 100 parts by weight of the total amount of (B), (C), and (D) in the heat resistant resin paste. It is preferably part by weight, more preferably 2 to 20 parts by weight, further preferably 2 to 16 parts by weight, particularly preferably 2 to 10 parts by weight, and particularly 3 to 5 parts by weight. Is preferable. When the content of (D) is less than 1 part by weight, the wettability with the coated substrate is not sufficient, and a pattern formed by a screen printing method or a dispensing method occurs immediately after formation or after standing, and is dried or cured. There is a tendency for patterning defects to occur due to shrinkage or repelling. When it exceeds 20 parts by weight, the heat resistance and rheological properties such as thixotropy are reduced, and the resolution tends to decrease due to paste sagging.

  In the heat-resistant resin paste of the present invention, (B), (C), and (D) are uniformly dispersed and do not separate into several layers even when left for a long time.

  The heat-resistant resin paste of the present invention has high wettability with silicon wafers, ceramic substrates, glass substrates, glass epoxy substrates, metal substrates typified by Ni, Cu, and Al substrates, and PI coating substrates, all at room temperature. If the contact angle is 20 ° or less, the obtained film is uniform without shrinkage, repellency, or pinholes. If the contact angle exceeds 20 °, the heat-resistant resin paste repels on the substrate, resulting in patterning defects. When the droplet of the heat-resistant resin paste is dropped on various substrates, a tangent line is drawn from the contact point of the droplet and the substrate, and the contact angle is defined as the contact angle. The “room temperature” mainly refers to a temperature around 25 ° C.

  Moreover, it is preferable that the heat resistant resin paste of this invention makes the thixotropic coefficient in 25 degreeC into the range of 1.5-10.0. The reason is that if the thixotropic coefficient is 1.5 or more, sufficient resolution can be easily obtained by screen printing, while if it is 10.0 or less, the workability during printing is further improved. is there.

Therefore, the thixotropy coefficient at 25 ° C. of the heat-resistant resin paste of the present invention is preferably 1.5 to 8.0, more preferably 1.8 to 7.5, and more preferably 2.0 to 7 in consideration of the above characteristics. 0.0 is particularly preferred. Here, the viscosity and the thixotropy coefficient are measured on a 0.2 g sample using an E-type viscometer (Tokyo Keiki Co., Ltd., EHD-U type). The thixotropy coefficient is expressed as a ratio of the apparent viscosity with a rotational speed of 1 min ⁻¹ and 10 min ⁻¹ .

Moreover, it is preferable that the viscosity at 25 degrees C of the heat resistant resin paste of this invention is 10-1,000 Pa.s. This is because if it is 10 Pa · s or more, sufficient film thickness and resolution can be easily obtained, while if it is 1,000 Pa · s or less, transferability and printing workability are excellent. Therefore, the viscosity at 25 ° C. of the heat-resistant resin paste of the present invention is preferably 50 to 900 Pa · s, more preferably 100 Pa · s to 800 Pa · s, and particularly preferably 120 to 700 Pa · s in view of these characteristics. . The viscosity is expressed in terms of the apparent viscosity using the E-type viscometer with a rotation speed of 0.5 min- ¹ . The viscosity and the thixotropy coefficient can be controlled by, for example, the solid content concentration of the resin paste and the amount of particles contained in the paste. The larger these are, the larger the viscosity and the thixotropy coefficient are.

  Further, the heat-resistant resin paste of the present invention has a glass transition temperature and a thermal decomposition temperature after film formation of 150 ° C. or higher and 350 ° C. or higher, respectively. When the glass transition temperature is 150 ° C. or higher and the thermal decomposition temperature is 350 ° C. or higher, it is stable against the heat applied to the semiconductor packaging process and the heat generated during operation.

  If the glass transition temperature is less than 150 ° C. and the thermal decomposition temperature is less than 350 ° C., the structure may change during the assembly process or operation, or decomposition may start, which may cause defects such as strain or disconnection. The glass transition temperature is the temperature measured using the TMA method. The thermal decomposition temperature is measured using TG-DTA, and a temperature with a weight loss of 5% is defined as the thermal decomposition temperature.

  The method for producing the heat-resistant resin paste of the present invention is not particularly limited, and can be produced by preparing (a), (b) and (D) and then mixing them.

  Moreover, (D) is used as a resin solution previously dissolved in (A1), (A2), or a mixed solvent of (A1) and (A2), so that (D) can be used in the above heat-resistant resin paste. It can be uniformly dispersed. If (D) is added as a solid, the dispersion of (D) will not be uniform, and when the resulting heat-resistant resin paste is used for printing / coating, there will be insufficient wettability on the substrate. May end up.

  In the resin solution of (D), the same solvent as (A1) or (A2) may be used as the polar solvent used in preparing (D). In that case, the resin of (D) above The solution can be prepared simultaneously with the resin preparation of (D).

  Moreover, the heat resistant resin paste of this invention can mix each component by using a well-known mixing apparatus.

  Further, as a method for producing the heat-resistant resin paste of the present invention, (D) is mixed with a paste-like mixture in which (C) is dispersed in a solution containing (A1), (A2), and (B). It can produce by doing.

  The heat-resistant resin paste of the present invention may contain additives such as a colorant and a coupling agent, and a resin modifier, if necessary, in addition to the above components. Examples of the colorant include carbon black, dyes, and pigments. Examples of the coupling agent include silane-based, titanium-based, and aluminum-based, and silane-based coupling agents are most preferable.

  The additive is preferably used in an amount of 50 parts by weight or less based on 100 parts by weight of the total amount of (B) and (C). When the amount of the additive exceeds 50 parts by weight, the physical properties of the obtained coating film tend to be lowered.

  For the purpose of reducing the elastic modulus of the resulting resin film, a low-elastic filler or liquid rubber having rubber elasticity can be added to the heat-resistant resin paste of the present invention. The low-elastic filler or liquid rubber having rubber elasticity is not particularly limited, and examples thereof include elastic fillers such as acrylic rubber, fluorine rubber, silicone rubber, and butadiene rubber, and these liquid rubbers. Here, silicone rubber is preferred in consideration of the heat resistance of the resin composition.

  The surface of the filler is preferably chemically modified with an epoxy group.

  What was modified with functional groups, such as an amino group, an acryl group, a vinyl group, a phenyl group, can be used instead of said epoxy group. By adding these low-elasticity fillers to a thermoplastic resin having heat resistance, it becomes possible to achieve low elasticity and control the elastic modulus without impairing heat resistance and adhesion.

  The average particle size of the low elastic filler having rubber elasticity whose surface is chemically modified, which can be used in the present invention, is preferably from 0.1 to 50 μm and finely divided into a spherical shape or an irregular shape. If the average particle size is less than 0.1 μm, aggregation between particles occurs, and it tends to be difficult to sufficiently disperse. Moreover, when it exceeds 50 micrometers, there exists a tendency for the surface of a coating film to become rough and to obtain a uniform coating film to be difficult.

  In the heat resistant resin paste according to the present invention, the amount of the low elastic filler having rubber elasticity whose surface is chemically modified is 5 to 900 parts by weight with respect to 100 parts by weight of the total amount of (B) and (C). It is preferable to be 5 to 800 parts by weight.

  In the case where a low-elasticity filler having a rubber elasticity or a liquid rubber is blended in the heat-resistant resin paste, the heat-resistant resin paste can be kneaded and stirred with a dispersing machine such as a raking machine, a three-roll, a ball mill, a planetary mixer, a disper, or a homogenizer.

  The heat-resistant resin paste according to the present invention is not particularly limited, but is a power device, a SAW filter, a solar cell, a monolithic IC, a hybrid IC, a thermal head, an image sensor, a multi-chip high-density mounting substrate, etc., a flexible wiring plate It is used industrially as an insulating film, protective film, stress relaxation film, heat-resistant adhesive, and various thermal printing inks for semiconductor devices such as rigid wiring boards.

  Hereinafter, although the specific example regarding the heat resistant resin paste of this invention is shown, it is not limited to this.

(Synthesis Example 1) Preparation of heat resistant resin solution (a) (polyimide precursor)
3,4,3 ′, 4′-benzophenone tetracarboxylic dianhydride (hereinafter referred to as “4,4′-benzophenone tetracarboxylic dianhydride”) in a 1 liter four-necked flask equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a cooling tube with an oil / water separator 96.7 g (300 mmol) (referred to as BTDA), 60.1 g (300 mmol) of 4,4′-diaminodiphenyl ether (hereinafter referred to as DDE) and 600 g of dimethylpropylene urea (hereinafter referred to as DMPU) were charged. After stirring at 70 to 90 ° C. for 5 to 7 hours, the reaction was stopped by cooling to obtain a polyimide precursor solution. Even when this solution was allowed to stand at room temperature, no polyimide precursor was deposited.

(Synthesis Example 2) Preparation of heat-resistant resin filler dispersion (b) (polyimide precursor)
Under a nitrogen stream, 96.7 g (300 mmol) of BTDA, 60.1 g (300 mmol) of DDE, 350 g of DMPU and γ were added to a 1-liter four-necked flask equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a condenser tube with an oil / water separator. -350 g of butyrolactone was charged. When the mixture was stirred at 70 to 90 ° C. for 5 to 7 hours, the polyimide precursor resin fine particles were precipitated and dispersed in the solution. Thereafter, the reaction was stopped by cooling to obtain a polyimide precursor filler dispersion. The polyimide precursor filler dispersion dissolved when heated to 150 ° C.

Synthesis Example 3 Preparation of (D) (Polyimide Precursor)
Under a nitrogen stream, BTDA 96.7 g (300 mmol), DDE 45.1 g (225 mmol), siloxane diamine ( Product name: BY16-871, manufactured by Toray Dow Corning Co., Ltd., Mw = 248) 18.6 g (75 mmol) and DMPU 600 g were charged. After stirring at 70 to 90 ° C. for 5 to 7 hours, the reaction was stopped by cooling to obtain a polyimide precursor solution having a number average molecular weight of 1200. Even when this solution was allowed to stand at room temperature, no polyimide precursor was deposited.

Synthesis Example 4 Preparation of (D) (Polyimide Precursor)
Under a nitrogen stream, BTDA 96.7 g (300 mmol), DDE 45.1 g (225 mmol), siloxane diamine ( Trade name: KF-8010, manufactured by Shin-Etsu Chemical Co., Ltd., Mw = 900) 67.5 g (75 mmol) and DMPU 800 g were charged. After stirring at 70 to 90 ° C. for 5 to 7 hours, the reaction was stopped by cooling to obtain a polyimide precursor solution having a number average molecular weight of 4500. Even when this solution was allowed to stand at room temperature, no polyimide precursor was deposited.

Synthesis Example 5 Preparation of (D) (Polyimide Precursor)
Under a nitrogen stream, 96.7 g (300 mmol) of BTDA, 33.0 g (165 mmol) of DDE, siloxane diamine (with a thermometer, a stirrer, a nitrogen inlet tube, and a condenser tube with an oil / water separator were attached under a nitrogen stream Trade name: KF-8010, Shin-Etsu Chemical Co., Ltd., Mw = 900) 121.5 g (135 mmol) and DMPU 1000 g were charged. After stirring at 70 to 90 ° C. for 5 to 7 hours, the reaction was stopped by cooling to obtain a polyimide precursor solution having a number average molecular weight of 3200. Even when this solution was allowed to stand at room temperature, no polyimide precursor was deposited.

Synthesis Example 6 Preparation of (D) (Polyimide Precursor)
Under a nitrogen stream, BTDA 96.7 g (300 mmol), DDE 55.9 g (279 mmol), siloxane diamine ( Product name: KF-8010, Shin-Etsu Chemical Co., Ltd., Mw = 900) 18.9 g (21 mmol) and DMPU 650 g were charged. After stirring at 70 to 90 ° C. for 5 to 7 hours, the reaction was stopped by cooling to obtain a polyimide precursor solution having a number average molecular weight of 5300. Even when this solution was allowed to stand at room temperature, no polyimide precursor was deposited.

Synthesis Example 7 Preparation of (D) (Polyimide Precursor)
Under a nitrogen stream, BTDA 96.7 g (300 mmol), DDE 51.1 g (255 mmol), siloxane diamine ( Trade name: KF-8008, manufactured by Shin-Etsu Chemical Co., Ltd., Mw = 11,400) 513.0 g (45 mmol) and DMPU 2500 g were charged. After stirring at 70 to 90 ° C. for 5 to 7 hours, the reaction was stopped by cooling to obtain a polyimide precursor solution having a number average molecular weight of 28000. When this solution was allowed to stand at room temperature, a polyimide precursor was precipitated and separated into two layers.

Synthesis Example 8 Preparation of (D) (Polyimide Precursor)
Under a nitrogen stream, 96.7 g (300 mmol) BTDA, 58.3 g (291 mmol), DDE 58.3 g (291 mmol), siloxane diamine ( Product name: KF-8010, Shin-Etsu Chemical Co., Ltd., Mw = 900) 8.1 g (9 mmol) and DMPU 620 g were charged. After stirring at 70 to 90 ° C. for 5 to 7 hours, the reaction was stopped by cooling to obtain a polyimide precursor solution having a number average molecular weight of 22,000. Even when this solution was allowed to stand at room temperature, no polyimide precursor was deposited.

Synthesis Example 9 Preparation of (D) (Polyimide Precursor)
Under a nitrogen stream, 96.7 g (300 mmol) of BTDA, 6.0 g (30 mmol) of DDE, siloxane diamine (with a thermometer, a stirrer, a nitrogen inlet tube, and a condenser tube with an oil / water separator were attached under a nitrogen stream. Trade name: KF-8010, Shin-Etsu Chemical Co., Ltd., Mw = 900) 227.3 g (270 mmol) and DMPU 1250 g were charged. After stirring at 70 to 90 ° C. for 5 to 7 hours, the reaction was stopped by cooling to obtain a polyimide precursor solution having a number average molecular weight of 1800. Even when this solution was allowed to stand at room temperature, no polyimide precursor was deposited.

  Specific examples of the heat-resistant resin paste of the present invention are shown in Examples 1 to 5 and Reference Examples 1 to 6.

Example 1
In a 1 liter four-necked flask equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a cooling tube with an oil / water separator, under a nitrogen stream, 200 g of the polyimide precursor solution (a) obtained in Synthesis Example 1 above, the above synthesis 400 g of the polyimide precursor filler dispersion (b) obtained in Example 2 and 24 g of the polyimide precursor solution (D) obtained in Synthesis Example 4 were added and stirred, and a heat resistant resin paste containing three types of resins. Got.

The viscosity and thixotropy coefficient of the obtained heat-resistant resin paste were measured with a high viscosity viscometer (trade name RE-80U, manufactured by Toki Sangyo Co., Ltd.). The viscosity and the rotational speed 0.5 min ^-1 values, is thixotropic factor was the ratio of the values of 1min ^-1 and 10min ^-1.

  In addition, the obtained heat-resistant resin paste is dropped onto a silicon wafer and a glass substrate, and a tangent is drawn from the contact point between the droplet and the substrate using a solid-liquid interface analyzer (trade name DropMaster 300, manufactured by Kyowa Interface Science Co., Ltd.). The angle between the tangent and the substrate was measured as the contact angle. The drop amount was 1.5 μl, the angle 30 seconds after the drop was measured with n = 10, and the average value was taken as the contact angle.

  Further, the obtained heat-resistant resin paste is applied on a semiconductor substrate with a plurality of 10 mm × 10 mm square resin layers by a screen printing machine (manufactured by Neurong Precision Industry Co., Ltd.), and heated at 250 ° C. to remove an organic solvent. A film having a thickness of 50 μm was formed by drying. The occurrence of repellency and pinholes in the formed resin layer was visually observed, and then the size of the resin layer was measured with a universal projector to obtain dimensional accuracy. In order to obtain a heat-resistant resin paste excellent in screen printability, this dimensional accuracy needs to be within ± 10%. Compatibility was confirmed by visual observation of separation after standing for 24 hours.

  Moreover, in order to evaluate heat resistance, the obtained heat-resistant resin paste was apply | coated to the thickness of about 100 micrometers on a polyimide film (Brand name Upilex S, Ube Industries, Ltd. product), and 100 degreeC / 10 under nitrogen stream. Minutes, 150 ° C./10 minutes, 350 ° C./1 hour, and then peeled from Upilex S to obtain a 30 μm thick film. The glass transition temperature of this film was measured using a thermomechanical analyzer (trade name Thermo Plus 2, manufactured by Rigaku Corporation). In addition, a 5% weight reduction temperature of this film was measured using a differential thermobalance (trade name Thermo Plus 2, manufactured by Rigaku Corporation) to obtain a thermal decomposition temperature.

(Example 2)
300 g of the polyimide precursor solution (a) obtained in Synthesis Example 1 above in a 1 liter four-necked flask equipped with a thermometer, a stirrer, a nitrogen introduction tube, and a cooling tube with an oil / water separator under a nitrogen stream, the above synthesis 150 g of the polyimide precursor filler dispersion (b) obtained in Example 2 and 81 g of the polyimide precursor solution (D) obtained in Synthesis Example 4 were added and stirred, and the heat resistant resin paste containing three types of resins. Got. The obtained heat-resistant resin paste was evaluated in the same manner as in Example 1.

(Example 3)
300 g of the polyimide precursor solution (a) obtained in Synthesis Example 1 above in a 1 liter four-necked flask equipped with a thermometer, a stirrer, a nitrogen introduction tube, and a cooling tube with an oil / water separator under a nitrogen stream, the above synthesis 300 g of the polyimide precursor filler dispersion (b) obtained in Example 2 and 90 g of the polyimide precursor solution (D) obtained in Synthesis Example 4 were added and stirred, and the heat resistant resin paste containing three types of resins. Got. The obtained heat-resistant resin paste was evaluated in the same manner as in Example 1.

Example 4
In a 1 liter four-necked flask equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a cooling tube with an oil / water separator, under a nitrogen stream, 200 g of the polyimide precursor solution (a) obtained in Synthesis Example 1 above, the above synthesis 300 g of the polyimide precursor filler dispersion (b) obtained in Example 2 and 15 g of the polyimide precursor solution (D) obtained in Synthesis Example 5 were added and stirred, and the heat resistant resin paste containing three types of resins. Got. The obtained heat-resistant resin paste was evaluated in the same manner as in Example 1.

(Example 5)
In a 1 liter four-necked flask equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a cooling tube with an oil / water separator, under a nitrogen stream, 200 g of the polyimide precursor solution (a) obtained in Synthesis Example 1 above, the above synthesis 400 g of the polyimide precursor filler dispersion (b) obtained in Example 2 and 30 g of the polyimide precursor solution (D) obtained in Synthesis Example 6 were added and stirred, and a heat resistant resin paste containing three types of resins. Got. The obtained heat-resistant resin paste was evaluated in the same manner as in Example 1.

(Reference Example 1)
In a 1 liter four-necked flask equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a cooling tube with an oil / water separator, under a nitrogen stream, 200 g of the polyimide precursor solution (a) obtained in Synthesis Example 1 above, the above synthesis 400 g of the polyimide precursor filler dispersion (b) obtained in Example 2 and 24 g of the polyimide precursor solution (D) obtained in Synthesis Example 3 were added and stirred, and the heat resistant resin paste containing three types of resins. Got. The obtained heat-resistant resin paste was evaluated in the same manner as in Example 1.

(Reference Example 2)
300 g of the polyimide precursor solution (a) obtained in Synthesis Example 1 above in a 1 liter four-necked flask equipped with a thermometer, a stirrer, a nitrogen introduction tube, and a cooling tube with an oil / water separator under a nitrogen stream, the above synthesis 300 g of the polyimide precursor filler dispersion (b) obtained in Example 2 and 90 g of the polyimide precursor solution (D) obtained in Synthesis Example 7 were added and stirred, and the heat resistant resin paste containing three types of resins. Got. The obtained heat-resistant resin paste was evaluated in the same manner as in Example 1.

(Reference Example 3)
In a 1 liter four-necked flask equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a cooling tube with an oil / water separator, under a nitrogen stream, 200 g of the polyimide precursor solution (a) obtained in Synthesis Example 1 above, the above synthesis 300 g of the polyimide precursor filler dispersion (b) obtained in Example 2 and 3 g of the polyimide precursor solution (D) obtained in Synthesis Example 8 were added and stirred, and the heat resistant resin paste containing three types of resins. Got. The obtained heat-resistant resin paste was evaluated in the same manner as in Example 1.

(Reference Example 4)
400 g of the polyimide precursor solution (a) obtained in Synthesis Example 1 above in a 1 liter four-necked flask equipped with a thermometer, a stirrer, a nitrogen introduction tube, and a cooling tube with an oil / water separator under a nitrogen stream, the above synthesis 200 g of the polyimide precursor filler dispersion (b) obtained in Example 2 and 108 g of the polyimide precursor solution (D) obtained in Synthesis Example 9 were added and stirred, and a heat resistant resin paste containing three types of resins. Got. The obtained heat-resistant resin paste was evaluated in the same manner as in Example 1.

(Reference Example 5)
400 g of the polyimide precursor solution (a) obtained in Synthesis Example 1 above and the above synthesis in a 1 liter four-necked flask equipped with a thermometer, a stirrer, a nitrogen introduction tube, and a cooling tube with an oil / water separator under a nitrogen stream. 200 g of the polyimide precursor filler dispersion (b) obtained in Example 2 was added and stirred to obtain a heat-resistant resin paste containing two types of resins. The obtained heat-resistant resin paste was evaluated in the same manner as in Example 1.

(Reference Example 6)
150 g of the polyimide precursor solution (a) obtained in Synthesis Example 1 above in a 1 liter four-necked flask equipped with a thermometer, a stirrer, a nitrogen introduction tube, and a cooling tube with an oil / water separator under a nitrogen stream, the above synthesis 450 g of the polyimide precursor filler dispersion (b) obtained in Example 2 and 240 g of the polyimide precursor solution (D) obtained in Synthesis Example 4 were added and stirred, and the heat resistant resin paste containing three types of resins. Got. The obtained heat-resistant resin paste was evaluated in the same manner as in Example 1.

Hereinafter, the characteristics and evaluation results of the heat-resistant resin pastes obtained in Examples 1 to 5 and Reference Examples 1 to 6 are shown in Table 1 and Table 2, respectively.

  As shown in Table 1, the heat-resistant resin pastes obtained in Examples 1 to 5 have a viscosity and thixotropy coefficient excellent in screen printability, and are compatible with wettability to various substrates and screen printability. It was confirmed to be excellent. The glass transition temperature of the resin film obtained by drying or drying and curing by heating after coating was 150 ° C. or higher, and the thermal decomposition temperature was 350 ° C. or higher.

  In contrast to the above, the heat-resistant resin pastes obtained in Reference Examples 1, 3, and 5 had viscosity, thixotropy, and heat resistance excellent in screen printability, but poor wettability, repelling and pinning Many holes were generated, dimensional accuracy was poor, and patterning defects occurred. In addition, the heat-resistant resin paste obtained in Reference Examples 2 and 4 had excellent viscosity and thixotropy coefficient for screen printing, and was excellent in compatibility, wettability, and heat resistance, but the compatibility was poor, Two layers were separated by allowing to stand.

  Furthermore, although the heat resistant resin paste obtained in Reference Example 6 had good wettability, the viscosity and thixotropic coefficient were low, paste sagging occurred, dimensional accuracy was poor, and heat resistance was also low.

Claims (14)

  (A) a first heat-resistant resin solution containing a heat-resistant resin (B) soluble in the first organic solvent (A1) and (A1); and (b) a first organic solvent (A1) and a second organic solvent. (A2) and a heat-resistant resin filler dispersion containing a heat-resistant resin (C) insoluble in a mixed solvent of (A1) and (A2), and a silicone diamine compound having 2 to 51 siloxane bonds in the molecule It is a heat resistant resin paste formed by blending a siloxane resin (D) having a structure, and the silicone diamine content in the siloxane resin (D) is 1 to 80 parts by mole with respect to 100 parts by mole of all diamines. , Heat resistant resin paste.   The heat resistant resin paste according to claim 1, wherein the heat resistant resin (B) and the heat resistant resin (C) are a polyamide resin, a polyamideimide resin, a polyimide resin, or a precursor thereof. A siloxane resin (D) having a silicone diamine compound as a component is represented by the following general formula (I):

(Wherein R ₁ and R ₂ are divalent organic groups, and n is an integer of 1 to 50), or the silicone diamine and other diamines, and the following general formula (II)

(In the formula, Z represents a single bond, —O—, —S—, —SO ₂ —, —C (═O) —, —S (═O) —, —CH ₂ —, —CH (CH ₃ ) —). _{3. A} polyimide resin obtained by reacting an aromatic tetracarboxylic dianhydride represented by —C (CH ₃ ) ₂ — in a polar solvent or a precursor thereof. Heat resistant resin paste.   A siloxane resin (D) having a silicone diamine compound as a constituent is a silicone diamine represented by the above general formula (I), or the silicone diamine and other diamines, and a trivalent polycarboxylic acid having an acid anhydride group. 3. The heat-resistant resin paste according to claim 1 or 2, which is a polyamide-imide resin or a precursor thereof obtained by reacting a reactive derivative thereof with a polar solvent.   A siloxane resin (D) having a silicone diamine compound as a constituent contains a silicone diamine represented by the above general formula (I), or the silicone diamine and other diamines, and a dicarboxylic acid or a reactive derivative thereof in a polar solvent. The heat-resistant resin paste according to claim 1, which is a polyamide-based resin obtained by reacting with the above.   The content of the siloxane resin (D) having a silicone diamine compound as a component is 1 to 20 parts by weight with respect to 100 parts by weight of the resin contained in the heat-resistant resin paste. The heat-resistant resin paste described.   The heat-resistant resin paste according to any one of claims 1 to 6, wherein the second organic solvent (A2) is more easily evaporated from the heat-resistant resin paste than the first organic solvent (A1).   The heat-resistant resin (C) is a polyamide resin, a polyamideimide resin, a polyimide resin or a precursor thereof having an average particle size of 40 μm or less obtained by a non-aqueous dispersion polymerization method. The heat-resistant resin paste described. The contact angle of the heat resistant resin paste is 20 ° or less at room temperature in any of silicon, SiO ₂ film, polyimide resin, ceramic, and metal surface, and the heat resistant resin according to any one of claims 1 to 8. paste.   The heat-resistant resin paste according to any one of claims 1 to 9, wherein the heat-resistant resin paste has a thixotropic coefficient of 1.5 to 10.0.   (A) a first heat-resistant resin solution containing a heat-resistant resin (B) soluble in the first organic solvent (A1) and (A1), and (b) a first organic solvent (A1) and a second organic solvent. (A2) and a heat-resistant resin filler dispersion containing a heat-resistant resin (C) insoluble in a mixed solvent of (A1) and (A2), and a silicone diamine compound having 2 to 51 siloxane bonds in the molecule The manufacturing method of the heat resistant resin paste characterized by mix | blending the siloxane resin (D) which has a structure.   A silicone diamine compound is added to a paste-like mixture in which a filler of a heat resistant resin (C) is dispersed in a solution containing the first organic solvent (A1), the second organic solvent (A2) and the heat resistant resin (B). The siloxane resin (D) having the structure of (A1), (A2), or a mixed solvent of (A1) and (A2) is previously added after being dissolved and blended. Manufacturing method of heat resistant resin paste.   The insulating film obtained from the heat resistant resin paste in any one of Claims 1-10, or the heat resistant resin paste manufactured by the method of Claim 11 and 12.   The semiconductor device which has a protective film obtained from the heat resistant resin paste in any one of Claims 1-10, or the heat resistant resin paste manufactured by the method of Claim 11 and 12.