JP2008280509A - Heat resistant resin paste - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a heat resistant resin paste excellent in pattern embedding property, adhesiveness, heat resistance, flexibility, printing performance and shape retention of printed matters. <P>SOLUTION: The heat resistant resin paste is composed of first organic solvent (A1) and second organic solvent (A2) containing a soluble heat resistant resin (B) in a mixture of organic solvents (A1) and (A2), and an insoluble heat resistant resin filler (C) in a mixture of the first organic solvent (A1) and the second organic solvent (A2) wherein the heat resistant filler (C) is dispersed in a solvent containing the first organic solvent (A1), the second organic solvent (A2) and the heat-resistant resin (B). The resin paste is characterized by a viscosity of 40-200 Pa s at 25°C, a thixotropy coefficient of 1.5-6.0 and 22-35 wt.% concentration of a nonvolatile matter. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a heat-resistant resin paste, and more particularly to a heat-resistant resin paste excellent in pattern embedding property, adhesion, heat resistance, flexibility, printability, and printed shape retention.

  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 methods and dispense coating methods that do not require complicated processes such as exposure, development, or etching as image forming methods for polyimide-based resin films for surface protective films, interlayer insulating films, stress relieving materials, etc. It is attracting attention.

  In the screen printing method and the dispense coating 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 developed so far use inorganic fillers such as silica fillers and non-soluble polyimide fillers as fillers for imparting thixotropic properties. Since it remains as a filler, it has been pointed out that many voids and bubbles are easily formed at the interface between the base resin and the filler surface, the film strength is reduced, and the electrical insulation is poor.

  In response to the above problems, a heat-resistant resin paste has been developed in which a soluble organic filler that does not remain as a filler in the coating forms a homogeneous phase with the base resin during heat drying, and is combined with the base resin and solvent. (See Patent Documents 1 and 2).

However, depending on the shape of the target printed matter, due to the characteristics of the heat-resistant resin paste, repelling, dripping or blurring may occur, or the resin paste from the screen printing plate may not be easily removed. In some cases, the printed matter could not be obtained. For this reason, it was necessary to optimize the characteristics of the heat-resistant resin paste.
Japanese Patent No. 2697215 Japanese Patent No. 3087290

  An object of the present invention is to provide a heat-resistant resin paste that is excellent in pattern embedding, adhesion, heat resistance, flexibility, printability, and shape retention of printed matter.

  The present invention provides (1) a first organic solvent (A1), a second organic solvent (A2), a mixed organic solvent of the first organic solvent (A1) and the second organic solvent (A2), and a heat resistant A heat-resistant resin filler (C) that is insoluble in the organic solvent (B), the mixed organic solvent of the first organic solvent (A1) and the second organic solvent (A2), and the first organic solvent (A1), A heat-resistant resin paste in which a heat-resistant resin filler (C) is dispersed in a solution containing the second organic solvent (A2) and the heat-resistant resin (B), the viscosity at 25 ° C. being 40 to 200 Pa · s, The present invention relates to a heat-resistant resin paste having a thixotropic coefficient of 1.5 to 6.0 and a nonvolatile content concentration of 22 to 35% by weight.

  The present invention also relates to (2) the heat-resistant resin paste according to (1), wherein the first organic solvent (A1) contains a nitrogen-containing compound.

  The present invention also relates to (3) the heat-resistant resin paste according to (2), wherein the nitrogen-containing compound is a polar nitrogen-containing cyclic compound.

  The present invention also relates to (4) the heat resistant resin paste according to any one of (1) to (3), wherein the second organic solvent (A2) contains a lactone.

  The present invention also relates to (5) the heat resistant resin paste according to the above (4), wherein the lactone contains γ-butyrolactone.

  Moreover, this invention is as described in any one of said (1)-(5) whose (6) said heat resistant resin (B) and heat resistant resin filler (C) are polyimide resins or its precursor. The present invention relates to a heat resistant resin paste.

In addition, the present invention provides (7) a diamine in which the polyimide resin of the heat-resistant resin filler (C) or a precursor thereof contains an aromatic diamine represented by the following general formula (I); It relates to the heat resistant resin paste according to the above (6), which is obtained by reacting an aromatic tetracarboxylic dianhydride represented by II) or a tetracarboxylic acid containing a derivative thereof.

(In the formula (I), R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 9 carbon atoms, an alkoxy group having 1 to 9 carbon atoms or a halogen atom. And X is a chemical bond, —O—, —S—, —SO ₂ —, —C (═O) —, —S (═O) —, or a group represented by the following formula (Ia): Either)

(In Formula (Ia), R ⁵ and R ⁶ are each independently any one of a hydrogen atom, an alkyl group, a trifluoromethyl group, a trichloromethyl group, a halogen atom or a phenyl group)

(In the formula (II), Y is any of —O—, —S—, —SO ₂ —, —C (═O) —, and —S (═O) —).
In the present invention, (8) the refractory resin filler (C) is mixed with a diamine and a tetracarboxylic acid in the presence of a mixed solvent of the first organic solvent (A1) and the second organic solvent (A2). It is related with the heat resistant resin paste of the said (7) description obtained by making acids react.

  The present invention also relates to (9) the heat-resistant resin paste according to any one of (1) to (8), further comprising a pigment (D).

  The present invention also relates to (10) the heat resistant resin paste according to (9), wherein the pigment (D) is a white powder.

  The present invention also relates to (11) the heat-resistant resin paste according to (9) or (10), wherein the average particle size of the pigment (D) is less than 10 μm.

  ADVANTAGE OF THE INVENTION According to this invention, the heat resistant resin paste excellent in pattern embedding property, adhesiveness, heat resistance, flexibility, printability, and the shape retention of printed matter can be provided.

  The heat resistant resin paste of the present invention comprises (1) a first organic solvent (A1), a second organic solvent (A2), a mixed organic of the first organic solvent (A1) and the second organic solvent (A2). A heat-resistant resin (B) that is soluble in a solvent, a mixed organic solvent of the first organic solvent (A1) and the second organic solvent (A2), and a heat-resistant resin filler (C) that is insoluble in the organic solvent, the first organic solvent A heat-resistant resin paste in which a heat-resistant resin filler (C) is dispersed in a solution containing (A1), a second organic solvent (A2), and a heat-resistant resin (B).

  The heat resistant resin paste of the present invention has a viscosity at 25 ° C. of 40 to 200 Pa · s, preferably 50 to 200 Pa · s, more preferably 50 to 190 Pa · s, and particularly preferably 50 to 180 Pa · s. s. When the viscosity of the heat resistant resin paste is less than 40 Pa · s, the shape retention of the obtained printed matter is lowered, and when it exceeds 200 Pa · s, the ability of the heat resistant resin paste to be removed from the screen printing plate is lowered. The viscosity is a value measured using an E-type viscometer (manufactured by Tokyo Keiki Co., Ltd., RE-80U type) at a sample amount of 0.2 g, a measurement temperature of 25 ° C., and a rotation speed of 0.5 rpm.

  As a method of adjusting the viscosity of the heat resistant resin paste to the above range, a method of changing the molecular weight of the heat resistant resin (B) and the heat resistant resin filler (C), a method of changing the nonvolatile content concentration of the heat resistant resin paste, Examples thereof include a method of increasing viscosity (aging) or decreasing viscosity (cooking) under a predetermined temperature environment.

The heat resistant resin paste of the present invention has a thixotropic coefficient of 1.5 to 6.0, preferably 1.5 to 5.5, more preferably 2.0 to 5.5, particularly preferably. It is 2.0-5.0. If the thixotropy coefficient is less than 1.5, the printability is lowered, and if it exceeds 6.0, the workability is lowered and it is difficult to produce a heat-resistant resin paste. The thixotropy coefficient is an apparent viscosity of a paste having a rotational speed of 1 rpm and 10 rpm, measured by using an E-type viscometer (manufactured by Tokyo Keiki Co., Ltd., RE-80U type) at a sample amount of 0.2 g and a measurement temperature of 25 ° C., η ₁ and eta ₁₀ ratio, a thixotropic coefficient expressed as η _{1 /} η ₁₀ as a method of adjusting the above-described range, a method of changing the amount of the heat-resistant resin filler (C), a nonvolatile concentration of the heat-resistant resin paste And a method of adding a pigment.

  The heat-resistant resin paste of the present invention has a nonvolatile content concentration of 22 to 35% by weight, preferably 23 to 35% by weight, more preferably 23 to 34% by weight, and particularly preferably 23 to 33% by weight. It is. If the non-volatile content concentration is less than 22% by weight, the shape retention of the obtained printed matter is lowered, and if it exceeds 35% by weight, the printability is lowered.

  The first organic solvent (A1) used in the present invention is not particularly limited, and examples thereof include diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, and triethylene. Ethers such as glycol dipropyl ether, triethylene glycol dibutyl ether, tetraethylene glycol dimethyl ether, dioxane, 1,2-dimethoxyethane; sulfur-containing compounds such as dimethyl sulfoxide, diethyl sulfoxide, dimethyl sulfone, sulfolane; γ-butyrolactone, γ -Valerolactone, γ-caprolactone, cellosolve acetate, ethyl cellosolve, acetate Esters such as lucerosolve, ethyl acetate, butyl acetate; ketones such as cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone; N-methylpyrrolidone, N, N′-dimethylacetamide, N, N′-dimethylformamide, 1,3 -Nitrogen-containing compounds such as dimethyl-3,4,5,6-tetrahydro-2 (1H) -pyrimidinone, 1,3-dimethyl-2-imidazolidinone; aromatic hydrocarbons such as toluene and xylene These can be used alone or in combination of two or more.

  The (A1) first organic solvent preferably contains a nitrogen-containing compound. The nitrogen-containing compound is not particularly limited as long as it contains a nitrogen atom, and examples thereof include the nitrogen-containing compounds described above. Among them, a nitrogen-containing cyclic compound having polarity is more preferable, and N-methylpyrrolidone is preferred. 1,3-dimethyl-3,4,5,6-tetrahydro-2 (1H) -pyrimidinone and the like are particularly preferable.

  The blending amount of the polar nitrogen-containing cyclic compound is preferably 40% by weight or more, more preferably 50% by weight or more based on the total amount of the first organic solvent (A1) and the second organic solvent (A2). More preferably, it is particularly preferably 60% by weight or more. If the blending amount of the polar nitrogen-containing cyclic compound is less than 40% by weight, the solubility of the heat resistant resin (B) is lowered, and the resulting coating film properties tend to be lowered.

  The second organic solvent (A2) used in the present invention is not particularly limited, and examples thereof include ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether; dimethyl sulfoxide, diethyl sulfoxide, dimethyl Sulfur-containing compounds such as sulfone and sulfolane; esters such as γ-butyrolactone and cellosolve acetate; ketones such as cyclohexanone and methyl ethyl ketone; N-methylpyrrolidone, dimethylacetoacetate, 1,3-dimethyl-3,4,5, Nitrogen-containing compounds such as 6-tetrahydro-2 (1H) -pyrimidinone; aromatic hydrocarbons such as toluene and xylene, and the like. These may be used alone or in combination of two or more. Kill.

  The second organic solvent (A2) preferably contains a lactone. Examples of lactones include γ-butyrolactone, γ-valerolactone, γ-caprolactone, γ-heptalactone, α-acetyl-γ-butyrolactone, ε-caprolactone, and the like, among which γ-butyrolactone is preferable.

  The blending amount of the lactone is preferably 10 to 60% by weight based on the total amount of the first organic solvent (A1) and the second organic solvent (A2) containing the lactone. More preferably, it is more preferably 15 to 55% by weight, still more preferably 15 to 50% by weight. If the blending amount of the lactone is less than 10%, the thixotropic property of the obtained paste tends to be lowered, and if it exceeds 60% by weight, the solubility of the heat resistant resin (B) and the heat resistant resin filler (C) is lowered. However, the properties of the resulting coating film tend to deteriorate.

The boiling point of the mixed organic solvent of the first organic solvent (A1) and the second organic solvent (A2) used in the present invention is 100 ° C. or higher in consideration of the pot life during application of the heat-resistant resin paste. Is preferred. By appropriately selecting the kind and blending amount of the first organic solvent (A1) and the second organic solvent (A2), the boiling point of the mixed organic solvent is set to fall within the above temperature range.
The heat resistant resin (B) used in the present invention is soluble in a mixed organic solvent of the first organic solvent (A1) and the second organic solvent (A2). The heat-resistant resin (B) may be either a thermosetting resin or a thermoplastic resin. Examples of the thermosetting resin include terminal acetylenic polyimide resin, terminal maleimidated polyimide resin, and BT resin (Mitsubishi Gas Chemical Co., Ltd.). And addition polymerization type polyimide resins such as Kelimide (trade name, manufactured by Rhône-Poulenc), melamine resin, phenol resin, epoxy resin and the like. Examples of the thermoplastic resin include polyamide resin, polyimide resin, polyamideimide resin, polyimide resin precursor, and the like. Among these, a polyimide resin or a precursor thereof is preferable from the viewpoint of heat resistance.

  The polyimide resin or a precursor thereof is obtained by, for example, reacting a diamine such as an aromatic diamine compound, an aliphatic diamine compound or an alicyclic diamine compound with a tetracarboxylic acid such as tetracarboxylic dianhydride or a derivative thereof. It is obtained.

Examples of diamines include m-phenylenediamine, p-phenylenediamine, 4,4′-diaminodiphenylpropane, 4,4′-diaminodiphenylmethane, benzidine, 4,4′-diaminodiphenyl sulfide, and 4,4′-. Diaminodiphenyl sulfone, 3,3′-diaminodiphenyl sulfone, 4,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl ether, 4,4′-diamino-p-terphenyl, 2,6, -diaminopyridine, bis (4-aminophenyl) phosphine oxide, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2 -Bis [3-methyl-4- (4-aminophenoxy) phenyl] propane 2,2-bis [4- (4-aminophenoxy) phenyl] butane, 2,2-bis [3-methyl-4- (4-aminophenoxy) phenyl] butane, 2,2-bis [3,5- Dimethyl-4- (4-aminophenoxy) phenyl] butane, 2,2-bis [3,5-dibromo-4- (4-aminophenoxy) phenyl] butane, 1,1,1,3,3,3- Hexafluoro-2,2-bis [4- (4-aminophenoxy) phenyl] propane, 1,1,1,3,3,3-hexafluoro-2,2-bis [3-methyl-4- (4 -Aminophenoxy) phenyl] propane, 1,1-bis [4- (4-aminophenoxy) phenyl] cyclohexane, 1,1-bis [4- (4-aminophenoxy) phenyl] cyclopentane, bis [4- ( 4-aminofe Noxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] ether, 4,4′-carbonylbis (p-phenyleneoxy) dianiline, 4,4′-bis (4-aminophenoxy) biphenyl, etc. Examples thereof include aromatic diamine compounds and siloxane diamine compounds such as diaminopolysiloxanes represented by the following general formula (III).

In formula (III), R ⁷ and R ⁸ are divalent hydrocarbon groups having 1 to 30 carbon atoms, and R ⁹ , R ¹⁰ , R ¹¹ and R ¹² are monovalent hydrocarbon groups having 1 to 30 carbon atoms. Show. n is an integer of 1 or more. R ⁷ and R ⁸ are preferably an alkylene group having 1 to 5 carbon atoms, a phenylene group, or an alkyl-substituted phenylene group. R ⁹ , R ¹⁰ , R ¹¹ and R ¹² are preferably an alkyl group having 1 to 5 carbon atoms, an alkoxy group, a phenyl group, or an alkyl-substituted phenyl group. n is preferably 1 to 100. Specific examples of the diaminopolysiloxane represented by the following general formula (III) include compounds of the following formulas (1) to (5).

  In formulas (1) to (5), n is an integer of 1 to 100.

  These diamines can be used alone or in combination of two or more.

The tetracarboxylic acids are preferably those obtained by reacting an aromatic tetracarboxylic dianhydride represented by the following general formula (II) or a tetracarboxylic acid containing a derivative thereof.

In formula (II), Y is any of —O—, —S—, —SO ₂ —, —C (═O) —, and —S (═O) —.

  Specific examples of the aromatic tetracarboxylic dianhydride or derivatives thereof include 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride. Anhydride, 2,3,3′4′-biphenyltetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, 3,4,3 ′, 4′-benzophenone tetracarboxylic dianhydride, 2,3,2 ′, 3′-benzophenone tetracarboxylic dianhydride, 2,3,3 ′, 4′-benzophenone tetracarboxylic acid Examples thereof include tetracarboxylic dianhydrides such as dianhydrides and derivatives thereof. Among these, it is preferable to use 3,4,3 ', 4'-benzophenonetetracarboxylic dianhydride or a derivative thereof.

  The reaction of diamines and tetracarboxylic acids can be carried out in the presence of an organic solvent. The organic solvent is not particularly limited, and examples thereof include ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether, and triethylene glycol diethyl ether; sulfur-containing compounds such as dimethyl sulfoxide, diethyl sulfoxide, dimethyl sulfone, and sulfolane; -Esters such as butyrolactone and cellosolve acetate; ketones such as cyclohexanone and methyl ethyl ketone; N-methylpyrrolidone, dimethylacetamide, 1,3-dimethyl-3,4,5,6-tetrahydro-2 (1H) -pyrimidinone, etc. Nitrogen-containing compounds; aromatic hydrocarbon solvents such as toluene and xylene can be used, and these can be used alone or in combination of two or more. Among these, it is preferable to use the first organic solvent (A1) in order to obtain a heat resistant resin paste, and a nitrogen-containing compound is more preferable.

  The reaction temperature of diamines and tetracarboxylic acids is preferably 25 ° C. 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.

  As a method of obtaining a polyimide resin, there is a method of dehydrating and ring-closing a polyimide resin precursor, and a general method can be used for this method. For example, a thermal cyclization method in which dehydration cyclization is performed by heating under normal pressure or reduced pressure, a chemical cyclization method using a chemical 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. The reaction is preferably performed at 80 to 400 ° C, more preferably 100 to 250 ° C. Further, a solvent such as benzene, toluene, xylene and the like that azeotropes with water may be used in combination to remove water azeotropically. In the case of the chemical ring closure method, the reaction is preferably performed at 0 to 120 ° C, more preferably at 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. In addition, it is preferable to use a substance that promotes the ring-closing reaction such as pyridine, isoquinoline, trimethylamine, triethylamine, aminopyridine, imidazole. The chemical dehydrating agent is preferably used in an amount of 90 to 600 mol% based on the total amount of diamines, and the substance that promotes the ring closure reaction is preferably used in an amount of 40 to 300 mol% based on the total amount of diamines. 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. In view of reduction of remaining ionic impurities, the above-described thermal ring closure method is preferable.

The blending amount of the heat resistant resin (B) is preferably 5 to 95 parts by weight, more preferably 10 to 90 parts by weight with respect to 100 parts by weight of the total amount of the heat resistant resin (B) and the heat resistant resin filler (C). More preferably, it is 20 to 80 parts by weight. When the blending amount of the heat-resistant resin (B) is less than 5 parts by weight, the solubility of the resin component in the solvent tends to be reduced and it tends to be difficult to form a paste. Tend to decrease.
The heat resistant resin filler (C) used in the present invention is insoluble in the mixed organic solvent of the first organic solvent (A1) and the second organic solvent (A2). The heat-resistant resin filler (C) is not particularly limited and may be either a thermosetting resin or a thermoplastic resin. Examples of the thermosetting resin include terminal acetylenic polyimide resin, terminal maleimide polyimide resin, and BT resin. Examples include addition polymerization type polyimide resins such as (trade name, manufactured by Mitsubishi Gas Chemical Co., Ltd.) and Kelimide (trade name, manufactured by Rhône-Poulenc), melamine resin, phenol resin, and epoxy resin. Examples of the thermoplastic resin include polyamide resin, polyimide resin, polyamideimide resin, polyimide resin precursor, and the like. Among these, a polyimide resin or a precursor thereof is preferable from the viewpoint of heat resistance.

A method for obtaining a polyimide resin or a precursor thereof as the heat-resistant resin filler (C) is, for example, a diamine such as an aromatic diamine compound, an aliphatic diamine compound or an alicyclic diamine compound, and a tetracarboxylic dianhydride or its The method by reaction with tetracarboxylic acids, such as a derivative, is mentioned. The diamines and tetracarboxylic acids to be used are not particularly limited, and those similar to those exemplified in the method for producing the heat resistant resin (B) can be used, but the first organic solvent (A1) and the second one can be used. In consideration of the solubility of the organic solvent (A2) in the mixed organic solvent, diamines containing the aromatic diamine represented by the following general formula (I) and the aromatic represented by the general formula (II) It is preferable to use tetracarboxylic acids containing tetracarboxylic dianhydride or derivatives thereof.

In formula (I), R ¹ , R ² , R ³ , and R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 9 carbon atoms, an alkoxy group having 1 to 9 carbon atoms, or a halogen atom. Yes, X is any of a chemical bond, —O—, —S—, —SO ₂ —, —C (═O) —, —S (═O) —, or a group represented by the following formula (Ia) It is.

In formula (Ia), R ⁵ and R ⁶ are each independently any one of a hydrogen atom, an alkyl group, a trifluoromethyl group, a trichloromethyl group, a halogen atom or a phenyl group.

R ¹ , R ² , R ³ , and R ⁴ are each independently a hydrogen atom; methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tertiary butyl group, pentyl group, hexyl group, C1-C9 alkyl groups such as heptyl, octyl and nonyl groups; methoxy, ethoxy, propoxy, butoxy, tertiary butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy An alkoxy group having 1 to 9 carbon atoms such as a group, nonyloxy group; or a halogen atom such as chlorine, bromine, iodine or fluorine, and X is a chemical bond (ie, biphenyl), —O—, —S—, _{-SO 2 -, - C (=} O) -, - S (= O) -, or any one of groups represented by the formula (Ia). In formula (Ia), R ⁵ and R ⁶ are each independently a hydrogen atom; an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group, a pentyl group; a trifluoromethyl group, a trichloromethyl group, chlorine , Bromine, iodine, a halogen atom such as fluorine, or a phenyl group. Specific examples of the aromatic diamine represented by the general formula (I) include 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy). ) Phenyl] hexafluoropropane, 2,2-bis [3-methyl-4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] butane, 2,2 -Bis [3-methyl-4- (4-aminophenoxy) phenyl] butane, 2,2-bis [3,5-dimethyl-4- (4-aminophenoxy) phenyl] butane, 2,2-bis [3 , 5-dibromo-4- (4-aminophenoxy) phenyl] butane, 1,1,1,3,3,3-hexafluoro-2,2-bis [4- (4-aminophenoxy) phenyl] propane, 1,1 1,3,3,3-hexafluoro-2,2-bis [3-methyl-4- (4-aminophenoxy) phenyl] propane, 1,1-bis [4- (4-aminophenoxy) phenyl] cyclohexane 1,1-bis [4- (4-aminophenoxy) phenyl] cyclopentane, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] ether, 4, Examples include 4′-carbonylbis (p-phenyleneoxy) dianiline, 4,4′-bis (4-aminophenoxy) biphenyl, and among these, 2,2-bis [4- (4-aminophenoxy) phenyl Propane is most preferred.

  The reaction of diamines and tetracarboxylic acids can be carried out in the presence of an organic solvent, and a mixed solvent of the first organic solvent (A1) and the second organic solvent (A2) is used as the organic solvent. It is more preferable to use a mixed solvent of the first organic solvent (A1) and the second organic solvent (A2) containing lactones. The blending amount of the lactone is preferably 30 to 90% by weight with respect to the total amount of the first organic solvent (A1) and the second organic solvent (A2) containing the lactone, It is more preferably 90% by weight, even more preferably 40 to 85% by weight, and particularly preferably 45 to 50% by weight. When the blending amount of the lactone is less than 30% by weight, it takes time to deposit the heat-resistant resin filler and tends to be inferior in workability, and when it exceeds 90% by weight, synthesis of the heat-resistant resin filler tends to be difficult. It is in. The reaction temperature is preferably 10 to 120 ° C, more preferably 15 to 100 ° C. When the reaction temperature is less than 10 ° C., the reaction does not proceed sufficiently, and when it exceeds 120 ° C., precipitation of the heat-resistant resin filler tends to be insufficient. The reaction time can be appropriately selected depending on the scale of the batch and the reaction conditions employed. The method for obtaining the polyimide resin is as described above.

The blending amount of the heat resistant resin filler (C) is preferably 5 to 95 parts by weight, more preferably 10 to 90 parts by weight with respect to 100 parts by weight of the total amount of the heat resistant resin (B) and the heat resistant resin filler (C). Parts, more preferably 20 to 80 parts by weight. When the blending amount of the heat-resistant resin filler (C) is less than 5 parts by weight, the printability tends to decrease, and when it exceeds 95 parts by weight, the solubility of the resin component in the solvent decreases and the paste It tends to be difficult.
A pigment (D) can be added to the heat resistant resin paste of the present invention. Although there is no restriction | limiting in particular as a pigment (D), It is preferable that it is a white type powder, for example, titanium dioxide and boron nitride can be used. The average particle size of the pigment (D) is preferably less than 10 μm, more preferably 0.01 to 8 μm, further preferably 0.03 to 7 μm, and 0.05 to 5 μm. Particularly preferred. If the average particle size of the pigment (D) is 10 μm or more, the resulting coating film may become brittle.

  The blending amount of the pigment (D) is 50% by weight or less based on the total amount of the first organic solvent (A1), the second organic solvent (A2), the heat resistant resin (B) and the heat resistant resin filler (C). Is preferable, 45% by weight or less is more preferable, 40% by weight or less is further preferable, and 35% by weight or less is particularly preferable. If the amount of the pigment (D) exceeds 50% by weight, the resulting coating film may become brittle.

  The heat resistant resin paste of the present invention is obtained by dispersing the heat resistant resin filler (C) in a solution containing the first organic solvent (A1), the second organic solvent (A2) and the heat resistant resin (B). It is a heat resistant resin paste. As a method for obtaining such a heat-resistant resin paste, for example, a heat-resistant resin solution in which the heat-resistant resin (B) is dissolved in an organic solvent, and a heat-resistant resin filler dispersion solution in which the heat-resistant resin filler (C) is dispersed in an organic solvent are used. The method of mixing is mentioned. In the heat resistant resin solution, it is preferable that the heat resistant resin (B) is dissolved in an organic solvent containing the first organic solvent (A1), and the heat resistant resin filler dispersion is composed of a heat resistant resin filler (C ) Is preferably dispersed in an organic solvent containing the second organic solvent (A2) and the heat-resistant resin (B). Mixing of the heat resistant resin solution and the heat resistant resin filler dispersion is preferably performed at 10 to 180 ° C, and more preferably 15 to 160 ° C. When the mixing temperature is less than 10 ° C., the heat-resistant resin solution and the heat-resistant resin filler dispersion tend not to be sufficiently mixed, and when the temperature exceeds 180 ° C., the heat-resistant resin filler tends to dissolve in the organic solvent. In this case, the printability or application property tends to be lowered.

After mixing the heat resistant resin solution and the heat resistant resin filler dispersion, in order to adjust the nonvolatile content concentration of the heat resistant resin paste to a desired value, an organic solvent may be further added and diluted. The organic solvent is preferably a mixed organic solvent of the first organic solvent (A1) and the second organic solvent (A2).
If necessary, an antifoaming agent, a dye, a plasticizer, an antioxidant, a coupling agent, a resin modifier, and the like can be added to the heat resistant resin paste of the present invention. There is no restriction | limiting in particular as said additive, For example, although a silane type, a titanium type, an aluminum type etc. are mentioned as a coupling agent, A silane type coupling agent is the most preferable.

  The silane coupling agent is not particularly limited, and examples thereof include vinyltrichlorosilane, vinyltris (β-methoxyethoxy) silane, vinyltriethoxysilane, vinyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, and γ-methacrylate. Roxypropylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxy Silane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltri Toxisilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-ureidopropyltriethoxysilane, 3-ureidopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane 3-aminopropyl-tris (2-methoxy-ethoxy-ethoxy) silane, N-methyl-3-aminopropyltrimethoxysilane, triaminopropyl-trimethoxysilane, 3-4,5-dihydroimidazol-1-yl -Propyltrimethoxysilane, 3-methacryloxypropyl-trimethoxysilane, 3-mercaptopropyl-methyldimethoxysilane, 3-chloropropyl-methyldimethoxysilane, 3-chloropropyl-dimethoxysilane 3-cyanopropyl-triethoxysilane, hexamethyldisilazane, N, O-bis (trimethylsilyl) acetamide, methyltrimethoxysilane, methyltriethoxysilane, ethyltrichlorosilane, n-propyltrimethoxysilane, isobutyltrimethoxysilane, Amyltrichlorosilane, octyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, methyltri (methacryloyloxyethoxy) silane, methyltri (glycidyloxy) silane, N-β (N-vinylbenzylaminoethyl) -γ-aminopropyl Trimethoxysilane, octadecyldimethyl [3- (trimethoxysilyl) propyl] ammonium chloride, γ-chloropropylmethyldichlorosilane, γ-chloropropylmethyl Dimethoxysilane, γ-chloropropylmethyldiethoxysilane, trimethylsilyl isocyanate, dimethylsilyl isocyanate, methylsilyl triisocyanate, vinylsilyl triisocyanate, phenylsilyl triisocyanate, tetraisocyanate silane, ethoxysilane isocyanate, etc. can be used. These may be used alone or in combination of two or more.

  The titanium-based coupling agent is not particularly limited. For example, isopropyl trioctanoyl titanate, isopropyl dimethacrylisostearoyl titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl isostearoyl diacryl titanate, isopropyl tri (dioctyl phosphate) titanate, Isopropyltricumylphenyl titanate, isopropyltris (dioctylpyrophosphate) titanate, isopropyltris (n-aminoethyl) titanate, tetraisopropylbis (dioctylphosphite) titanate, tetraoctylbis (ditridecylphosphite) titanate, tetra (2, 2-Diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titane , Dicumylphenyloxyacetate titanate, bis (dioctylpyrophosphate) oxyacetate titanate, tetraisopropyl titanate, tetranormal butyl titanate, butyl titanate dimer, tetra (2-ethylhexyl) titanate, titanium acetylacetonate, polytitanium acetylacetonate , Titanium octylene glycolate, Titanium lactate ammonium salt, Titanium lactate, Titanium lactate ethyl ester, Titanium triethanolamate, Polyhydroxy titanium stearate, Tetramethyl orthotitanate, Tetraethyl orthotitanate, Tetrapropyl orthotitanate, Tetraisobutyl orthotitanate , Stearyl titanate, cresyl titanate monomer, cresyl titanate Nate polymer, diisopropoxy-bis (2,4-pentadionate) titanium (IV), diisopropyl-bis-triethanolamino titanate, octylene glycol titanate, tetra-n-butoxytitanium polymer, tri-n-butoxytitanium A monostearate polymer, tri-n-butoxytitanium monostearate, etc. can be used, and these 1 type (s) or 2 or more types can also be used together.

  The aluminum coupling agent is not particularly limited. For example, ethyl acetoacetate aluminum diisopropylate, aluminum tris (ethyl acetoacetate), alkyl acetoacetate aluminum diisopropylate, aluminum monoacetyl acetate bis (ethyl acetoacetate), Aluminum such as aluminum tris (acetylacetonate), aluminum monoisopropoxymonooroxyethyl acetoacetate, aluminum-di-n-butoxide-mono-ethylacetoacetate, aluminum-di-iso-propoxide-mono-ethylacetoacetate Chelate compound, aluminum isopropylate, mono-sec-butoxyaluminum diisopropylate, aluminum-sec-butyl Rate, such as aluminum alcoholates of aluminum ethylate or the like can be used, may be used in combination one or more of them.

  The additive is preferably blended in an amount of 50 parts by weight or less based on 100 parts by weight of the total amount of the heat resistant resin (B) and the heat resistant resin filler (C). When there are more addition amounts of the said additive than 50 weight part, the coating film obtained may become weak.

  The heat-resistant resin paste of the present invention includes various semiconductor devices, semiconductor packages, thermal heads, image sensors, multichip high-density mounting substrates, various devices such as diodes, capacitors, and transistors, and various wiring boards such as flexible wiring boards and rigid wiring boards. It can be used for protective films such as protective films, insulating films, adhesives, various heat-resistant printing inks, etc., and is extremely useful industrially.

  The method for obtaining a precise pattern with the heat-resistant resin paste of the present invention is not particularly limited. For example, a screen printing method, a dispense coating method, a potting method, a curtain coating method, a relief printing method, an intaglio printing method, and a lithographic printing method. Etc.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these.

[Synthesis of heat-resistant resin solution]
(Synthesis Example 1)
96 3,4,3 ', 4'-benzophenone tetracarboxylic dianhydride was added to 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. 0.7 g (0.3 mol), 4,4′-diaminodiphenyl ether 55.4 g (0.285 mol), 1,3-bis (3-aminopropyl) tetramethyldisiloxane 3.73 g (0.015 Mol) and 1,3-dimethyl-3,4,5,6-tetrahydro-2 (1H) -pyrimidinone, and stirred at 70 to 90 ° C. for about 6 hours, and then cooled to stop the reaction. A heat resistant resin solution (PI-1) having a molecular weight of 25,000 (measured by GPC method and calculated using a standard polystyrene calibration curve) was obtained.

[Synthesis of heat-resistant resin filler dispersion]
(Synthesis Example 2)
96.7 g of 3,4,3 ′, 4′-benzophenonetetracarboxylic dianhydride was added to a 1 liter four-necked flask equipped with a thermometer, a stirrer, a nitrogen introducing tube, and a cooling tube with an oil / water separator. 0.3 mol), 61.5 g (0.15 mol) of 2,2-bis [4- (4-aminophenoxy) phenyl] propane, and 27.0 g (0.135 mol) of 4,4′-diaminodiphenyl ether. ), 3.73 g (0,015 mol) of 1,3-bis (3-aminopropyl) tetramethyldisiloxane, 1,3-dimethyl-3,4,5,6-tetrahydro-2 (1H) -pyrimidinone Was charged with 308.59 g of γ-butyrolactone and stirred at 70 to 90 ° C. for 5 hours, and a polyimide precursor filler having a number average molecular weight of 24,000 was precipitated in the solution. Thereafter, the reaction was stopped by cooling to obtain a heat resistant resin filler dispersion (PIF-1).

(Synthesis Example 3)
96.7 g of 3,4,3 ′, 4′-benzophenonetetracarboxylic dianhydride was added to a 1 liter four-necked flask equipped with a thermometer, a stirrer, a nitrogen introducing tube, and a cooling tube with an oil / water separator. 0.3 mol), 61.5 g (0.15 mol) of 2,2-bis [4- (4-aminophenoxy) phenyl] propane, and 27.0 g (0.135 mol) of 4,4′-diaminodiphenyl ether. ), 3.73 g (0,015 mol) of 1,3-bis (3-aminopropyl) tetramethyldisiloxane, 1,3-dimethyl-3,4,5,6-tetrahydro-2 (1H) -pyrimidinone Was charged with 133.25 g of γ-butyrolactone and 308.59 g of γ-butyrolactone, and stirred at 70 to 90 ° C. for 15 hours. As a result, a polyimide precursor filler having a number average molecular weight of 60,000 was precipitated in the solution. Thereafter, the reaction was stopped by cooling to obtain a heat-resistant resin filler dispersion (PIF-2).

[Synthesis of heat-resistant resin paste]
Example 1
300 g of the heat-resistant resin solution (PI-1) obtained in Synthesis Example 1 was added to 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. After adding 400 g of the heat-resistant resin filler dispersion (PIF-1) obtained in Synthesis Example 2 and stirring at 50 to 70 ° C. for 2 hours, 1,3-dimethyl-3,4,5,6-tetrahydro-2 The mixture was diluted with a mixed solvent of (1H) -pyrimidinone / γ-butyrolactone = 70/30 (weight ratio) to obtain a heat resistant resin paste (PIP-1) having a nonvolatile content concentration of 25.0% by weight.

  The following evaluation was performed about the obtained heat resistant resin paste (PIP-1).

(Viscosity and thixotropy coefficient)
The viscosity and thixotropy coefficient of the heat-resistant resin paste (PIP-1) were measured using an E-type viscometer (manufactured by Tokyo Keiki Co., Ltd., RE-80U type) at a sample amount of 0.2 g and a measurement temperature of 25 ° C. The viscosity was measured at a rotation speed of 0.5 rpm, and the thixotropy coefficient was evaluated by the apparent viscosity of a paste having a rotation speed of 1 rpm and 10 rpm, the ratio of η ₁ and η ₁₀ and η ₁ / η ₁₀ .

(Non-volatile content)
The nonvolatile content concentration was measured under the following conditions by weighing several grams of the heat resistant resin paste (PIP-1) on a metal petri dish.

Nonvolatile content concentration (% by weight) = (resin composition amount after heat drying (g) / resin composition amount before heat drying (g)) × 100
Heating and drying conditions: 1 hour at 150 ° C + 2 hours at 250 ° C (printing characteristics)
A heat-resistant resin paste (PIP-1) is screen-printed on a silicon wafer (manufactured by Neurong Precision Industry Co., Ltd., LS-34GX with alignment device), polyarylate screen mesh plate (NBC Corporation, V-screen, 280 Mesh, emulsion thickness: 10 μm, opening diameter: 200 μm), a silicon rubber squeegee was used for screen printing, and printing characteristics were evaluated according to the following contents according to repelling, bleeding, opening area, and number of continuously printable sheets.

  Haki: Evaluation was made based on the presence or absence of an uncoated portion of the paste on the silicon wafer at the portion corresponding to the opening of the screen mesh plate.

  Smudge: An evaluation was made based on whether or not a paste was applied on a silicon wafer other than the opening of the screen mesh plate (a portion where no paste was originally applied).

  Opening area: The diameter of the paste application part (circle) on the silicon wafer was measured.

  Number of continuously printable sheets: Evaluation was made based on the number of printed sheets that can maintain the same opening area as the initial printability in the above-described state without repellency and blurring.

(Coating properties)
A heat-resistant resin paste (PIP-1) was applied on a Teflon (registered trademark) substrate, heated at 250 ° C. for 30 minutes to dry the organic solvent, and a coating film having a thickness of 25 μm was formed. The tensile elastic modulus (25 ° C., 10 Hz) and glass transition temperature (frequency 10 Hz, temperature rising rate 2 ° C./min) were measured using a dynamic viscoelastic spectrometer (manufactured by Iwamoto Seisakusho Co., Ltd.). Moreover, the tensile strength and elongation at break were measured by an autograph (trade name: AGS-1000G, manufactured by Shimadzu Corporation).

  In addition, using a thermobalance (TG / DTA220 type, manufactured by Seiko Instruments Inc.), using a sample amount of 10 mg, a heating rate of 10 ° C./min (30 to 600 ° C.), alumina as a reference, and in an air atmosphere The thermal decomposition start temperature (5% weight loss temperature) was measured.

(Temperature cycle resistance)
A step of applying a heat-resistant resin paste (PIP-1) to a semiconductor substrate on which wiring has been formed by applying a resin layer a plurality of times by screen printing and drying, electrically conducting on the resin layer with an electrode on the semiconductor substrate A step of forming the rewiring, a step of forming a protective layer on the rewiring, and a step of forming an external electrode terminal on the protective layer were performed and diced to produce a semiconductor device. This semiconductor device was put into a thermal shock tester, and a temperature cycle test was performed for 1000 cycles at -55 ° C for 30 minutes and 125 ° C for 30 minutes to examine whether cracks occurred in the resin layer. . The number of samples was evaluated and the number of cracks generated / number of samples was shown.

(Example 2)
300 g of the heat-resistant resin solution (PI-1) obtained in Synthesis Example 1 was added to 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. After adding 400 g of the heat-resistant resin filler dispersion (PIF-1) obtained in Synthesis Example 2 and stirring at 50 to 70 ° C. for 2 hours, 1,3-dimethyl-3,4,5,6-tetrahydro-2 The mixture was diluted with a mixed solvent of (1H) -pyrimidinone / γ-butyrolactone = 70/30 (weight ratio) to obtain a heat-resistant resin paste (PIP-2) having a nonvolatile content concentration of 23.0% by weight.

  The obtained heat-resistant resin paste (PIP-2) was evaluated in the same manner as in Example 1. The results are summarized in Table 1.

(Example 3)
300 g of the heat-resistant resin solution (PI-1) obtained in Synthesis Example 1 was added to 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. After adding 400 g of the heat-resistant resin filler dispersion (PIF-1) obtained in Synthesis Example 2 and stirring at 50 to 70 ° C. for 2 hours, 1,3-dimethyl-3,4,5,6-tetrahydro-2 The mixture was diluted with a mixed solvent of (1H) -pyrimidinone / γ-butyrolactone = 70/30 (weight ratio) to obtain a heat-resistant resin paste (PIP-3) having a nonvolatile content concentration of 26.5% by weight.

  The obtained heat resistant resin paste (PIP-3) was evaluated in the same manner as in Example 1. The results are summarized in Table 1.

Example 4
Titanium dioxide (trade name, manufactured by DuPont, Ti-Pure R-350, average particle size: 0.3 μm) was added to the heat-resistant resin paste (PIP-1) having a nonvolatile content concentration of 25.0% by weight obtained in Example 1. 35 g was added and stirred at 50 to 70 ° C. for 1 hour to obtain a heat-resistant resin paste (PIP-4) having a nonvolatile content concentration of 28.5% by weight.

  The obtained heat resistant resin paste (PIP-4) was evaluated in the same manner as in Example 1. The results are summarized in Table 1.

(Example 5)
300 g of the heat-resistant resin solution (PI-1) obtained in Synthesis Example 1 was added to 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. After adding 400 g of the heat-resistant resin filler dispersion (PIF-2) obtained in Synthesis Example 3 and stirring at 50 to 70 ° C. for 2 hours, 1,3-dimethyl-3,4,5,6-tetrahydro-2 The mixture was diluted with a mixed solvent of (1H) -pyrimidinone / γ-butyrolactone = 70/30 (weight ratio) to obtain a heat-resistant resin paste (PIP-5) having a nonvolatile content concentration of 22.5% by weight.

  The obtained heat resistant resin paste (PIP-5) was evaluated in the same manner as in Example 1. The results are summarized in Table 1.

(Example 6)
The heat-resistant resin paste (PIP-1) having a nonvolatile content concentration of 25.0% by weight obtained in Example 1 was stirred at 5000 rpm for 5 minutes using a high-speed stirrer to reduce the viscosity. A heat-resistant resin paste (PIP-6) having a concentration of 25.0% by weight was obtained.

  The obtained heat resistant resin paste (PIP-6) was evaluated in the same manner as in Example 1. The results are summarized in Table 1.

(Example 7)
300 g of the heat-resistant resin solution (PI-1) obtained in Synthesis Example 1 was added to 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. After adding 400 g of the heat-resistant resin filler dispersion (PIF-2) obtained in Synthesis Example 3 and stirring at 50 to 70 ° C. for 2 hours, 1,3-dimethyl-3,4,5,6-tetrahydro-2 The mixture was diluted with a mixed solvent of (1H) -pyrimidinone / γ-butyrolactone = 70/30 (weight ratio) to obtain a heat-resistant resin paste (PIP-7) having a nonvolatile content concentration of 25.0% by weight.

  The obtained heat resistant resin paste (PIP-7) was evaluated in the same manner as in Example 1. The results are summarized in Table 1.

(Comparative Example 1)
300 g of the heat-resistant resin solution (PI-1) obtained in Synthesis Example 1 was added to 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. After adding 400 g of the heat-resistant resin filler dispersion (PIF-1) obtained in Synthesis Example 2 and stirring at 50 to 70 ° C. for 2 hours, 1,3-dimethyl-3,4,5,6-tetrahydro-2 The mixture was diluted with a mixed solvent of (1H) -pyrimidinone / γ-butyrolactone = 70/30 (weight ratio) to obtain a heat-resistant resin paste (PIP-8) having a nonvolatile content concentration of 20.0% by weight.

  The obtained heat resistant resin paste (PIP-8) was evaluated in the same manner as in Example 1. The results are summarized in Table 2.

(Comparative Example 2)
300 g of the heat-resistant resin solution (PI-1) obtained in Synthesis Example 1 was added to 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. 400 g of the heat-resistant resin filler dispersion (PIF-1) obtained in Synthesis Example 2 was added, stirred at 50 to 70 ° C. for 2 hours, and heat-resistant resin paste (PIP-9) having a nonvolatile content concentration of 30.0% by weight. Got.

  The obtained heat resistant resin paste (PIP-9) was evaluated in the same manner as in Example 1. The results are summarized in Table 2.

(Comparative Example 3)
300 g of the heat-resistant resin solution (PI-1) obtained in Synthesis Example 1 was added to 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. After adding 400 g of the heat-resistant resin filler dispersion (PIF-2) obtained in Synthesis Example 3 and stirring at 50 to 70 ° C. for 2 hours, 1,3-dimethyl-3,4,5,6-tetrahydro-2 The mixture was diluted with a mixed solvent of (1H) -pyrimidinone / γ-butyrolactone = 70/30 (weight ratio) to obtain a heat-resistant resin paste (PIP-10) having a nonvolatile content concentration of 26.5% by weight.

  The obtained heat resistant resin paste (PIP-10) was evaluated in the same manner as in Example 1. The results are summarized in Table 2.

(Comparative Example 4)
The heat-resistant resin solution (PI-1) obtained in Synthesis Example 1 was converted into 1,3-dimethyl-3,4,5,6-tetrahydro-2 (1H) -pyrimidinone / γ-butyrolactone = 70/30 (weight ratio) ) To obtain a heat-resistant resin paste (PIP-11) having a nonvolatile content concentration of 25.0% by weight.

  The obtained heat resistant resin paste (PIP-11) was evaluated in the same manner as in Example 1. The results are summarized in Table 2.

(Comparative Example 5)
300 g of the heat-resistant resin solution (PI-1) obtained in Synthesis Example 1 was added to 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. After adding 400 g of the heat-resistant resin filler dispersion (PIF-1) obtained in Synthesis Example 2 and stirring at 50 to 70 ° C. for 2 hours, 1,3-dimethyl-3,4,5,6-tetrahydro-2 The mixture was diluted with a mixed solvent of (1H) -pyrimidinone / γ-butyrolactone = 70/30 (weight ratio) to obtain a heat-resistant resin paste (PIP-12) having a nonvolatile content concentration of 40.0% by weight.

The obtained heat resistant resin paste (PIP-12) was evaluated in the same manner as in Example 1. The results are summarized in Table 2.

  In Table 2, “no printing” of repellency and blurring means that the paste could not be printed on the silicone wafer without passing through the screen mesh plate. Further, “not measurable” of the opening area means that the opening is not formed or the opening cannot be measured because printing is impossible. Further, “non-manufacturable” in temperature cycle resistance means that a measurement sample could not be prepared by screen printing.

  The heat-resistant resin paste of the present invention is excellent in pattern embedding property, adhesiveness, heat resistance, flexibility, printability, and printed shape retention. Furthermore, it is possible to form a precise pattern by screen printing, dispensing application, etc., and the semiconductor device using the heat-resistant resin paste of the present invention gives good characteristics.

Claims (11)

A first organic solvent (A1),
A second organic solvent (A2),
A heat resistant resin (B) soluble in a mixed organic solvent of the first organic solvent (A1) and the second organic solvent (A2),
A heat-resistant resin filler (C) insoluble in the mixed organic solvent of the first organic solvent (A1) and the second organic solvent (A2),
A heat resistant resin paste in which a heat resistant resin filler (C) is dispersed in a solution containing a first organic solvent (A1), a second organic solvent (A2) and a heat resistant resin (B),
A heat-resistant resin paste having a viscosity of 40 to 200 Pa · s at 25 ° C., a thixotropic coefficient of 1.5 to 6.0, and a nonvolatile content concentration of 22 to 35% by weight.   The heat-resistant resin paste according to claim 1, wherein the first organic solvent (A1) contains a nitrogen-containing compound.   The heat-resistant resin paste according to claim 2, wherein the nitrogen-containing compound is a polar nitrogen-containing cyclic compound.   The heat-resistant resin paste according to any one of claims 1 to 3, wherein the second organic solvent (A2) contains a lactone.   The heat-resistant resin paste according to claim 4, wherein the lactone contains γ-butyrolactone.   The heat resistant resin paste according to any one of claims 1 to 5, wherein the heat resistant resin (B) and the heat resistant resin filler (C) are a polyimide resin or a precursor thereof. The polyimide resin of the heat-resistant resin filler (C) or its precursor is a diamine containing an aromatic diamine represented by the following general formula (I), and an aromatic tetra represented by the following general formula (II) The heat-resistant resin paste according to claim 6, which is obtained by reacting a carboxylic acid dianhydride or a tetracarboxylic acid containing a derivative thereof.

(In the formula (I), R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 9 carbon atoms, an alkoxy group having 1 to 9 carbon atoms or a halogen atom. And X is a chemical bond, —O—, —S—, —SO ₂ —, —C (═O) —, —S (═O) —, or a group represented by the following formula (Ia): Either)

(In Formula (Ia), R ⁵ and R ⁶ are each independently any one of a hydrogen atom, an alkyl group, a trifluoromethyl group, a trichloromethyl group, a halogen atom or a phenyl group)

(In the formula (II), Y is any of —O—, —S—, —SO ₂ —, —C (═O) —, and —S (═O) —).   The heat-resistant resin filler (C) is obtained by reacting diamines and tetracarboxylic acids in the presence of a mixed solvent of the first organic solvent (A1) and the second organic solvent (A2). The heat resistant resin paste according to claim 7.   Furthermore, the heat resistant resin paste as described in any one of Claims 1-8 formed by containing a pigment (D).   The heat-resistant resin paste according to claim 9, wherein the pigment (D) is a white powder.   The heat-resistant resin paste according to claim 9 or 10, wherein an average particle diameter of the pigment (D) is less than 10 µm.