JPWO2006115124A1 - Resin composition and semiconductor device using the same - Google Patents

Abstract

An object of the present invention is to provide a resin composition excellent in pattern embedding property, adhesiveness, heat resistance, flexibility and printability, and a semiconductor device using the resin composition. A) Aromatic thermoplastic resin soluble in polar solvent at room temperature, (B) Aromatic thermoplastic resin insoluble in polar solvent at room temperature but soluble by heating, (C) Average particle size of 0. In a resin composition comprising a rubber-elastic filler having a particle size distribution of 1 to 6 μm and a particle size distribution of 0.01 to 15 μm, and (D) a polar solvent, using a rheometer, a shear stress of 13 Pa, Viscosity measured at a frequency of 5 Hz and 50 Hz is less than 400 Pa · s and 3 Pa · s or more, respectively, and a ratio of the viscosities (viscosity at a frequency of 5 Hz (Pa · s) / viscosity at a frequency of 50 Hz (Pa · s)) ) Is 2 The resin composition as described above and a semiconductor device using the same are provided.

Description

  The present invention relates to a resin composition excellent in pattern embedding property, adhesion, heat resistance, flexibility and printability, and a semiconductor device using the same.

  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 that do not require complicated processes such as exposure, development, and etching have attracted attention as image forming methods for polyimide-based resin films for surface protective films, interlayer insulating films, and stress relieving materials. .

  In the screen printing 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, the filler is first dissolved at the time of heating and drying, and it becomes a characteristic by combining it with a special organic filler (soluble filler), base resin, and solvent that are compatible with the base resin to form a film. A heat-resistant resin paste capable of forming an excellent polyimide pattern has been disclosed (see Japanese Patent Application Laid-Open No. 2-289646). In addition, there is a technique for adding a low elastic filler, liquid rubber, or the like to the paste for use as a stress relaxation material for wafer level CSP (see International Publication No. 01-066665).

  However, when the low elastic paste is used as a stress relieving material for a metal post type wafer level CSP, the metal post embedding property is poor and the reliability of the completed semiconductor device is lowered. Therefore, when a low-viscosity paste is used to improve the metal post embedding property, shape retention after printing is lowered. Therefore, it is necessary to manage the viscosity so that both the metal post embedding property and the shape retention property after printing can be achieved.

  The objective of this invention is providing the resin composition excellent in pattern embedding property, adhesiveness, heat resistance, flexibility, and printability, and a semiconductor device using the same.

  In order to solve the above problems, the inventors reduced the viscosity of the resin composition measured at a frequency of about 5 Hz and 50 Hz under a constant shear stress to such an extent that the metal post embedding at the time of printing is excellent. By increasing the difference between the viscosity measured at a frequency of about 5 Hz and the viscosity measured at a frequency of about 50 Hz, both pattern embedding and shape retention after printing are satisfied, and adhesion, heat resistance, and flexibility are satisfied. The present inventors have found that a resin composition satisfying these characteristics can be obtained, and have reached the present invention.

  That is, the present invention is characterized by the following items (1) to (5).

  (1) (A) an aromatic thermoplastic resin soluble in a polar solvent at room temperature, (B) an aromatic thermoplastic resin insoluble in a polar solvent at room temperature, but soluble by heating, (C) average In a resin composition comprising a rubber elastic filler having a particle size of 0.1 to 6 μm and a particle size distribution of 0.01 to 15 μm and (D) a polar solvent, a shear stress is measured using a rheometer. The viscosity measured at a frequency of 5 Hz and 50 Hz under a condition of 13 Pa is less than 400 Pa · s and 3 Pa · s or more, respectively, and the ratio of the viscosities (viscosity at a frequency of 5 Hz (Pa · s) / viscosity at a frequency of 50 Hz). (Pa · s)) relates to a resin composition of 2 or more.

  (2) (A) an aromatic thermoplastic resin that is soluble in a polar solvent at room temperature, and (B) an aromatic thermoplastic resin that is insoluble in a polar solvent at room temperature, but soluble by heating, is a polyamide resin, It is related with the resin composition of the said (1) description which is a polyimide resin, a polyamideimide resin, or these precursors.

  (3) The present invention relates to the resin composition as described in (1) or (2) above, wherein the surface of a filler having rubber elasticity is chemically modified.

  (4) The resin composition according to (3), wherein the chemical modification is modification with an epoxy group.

  (5) It is related with the semiconductor device using the resin composition in any one of said (1)-(4).

  The resin composition of the present invention as described above is excellent in pattern embedding, adhesion, heat resistance, flexibility and printability. In particular, since the resin composition of the present invention satisfies both contradictory properties of pattern embedding property and shape retention after printing, a precise and complicated pattern is known, for example, screen printing or dispensing coating. It can be formed by a method. Furthermore, a semiconductor device using the resin composition of the present invention gives good characteristics.

  In addition, this application is a Japanese patent application previously filed by the same applicant, ie, 2005-120985 (filing date: April 19, 2005) and 2005-198002 (filing date: July 6, 2005). ), Which is incorporated herein by reference.

FIG. 1 is a schematic diagram when screen-printing a resin composition on a semiconductor substrate on which wiring is formed. FIG. 1 (a) is before printing, and FIG. 1 (b) is after printing. In FIG. 1, 1 is a resin composition, 2 is a squeegee, 3 is a printing mask, 4 is a wiring forming portion, 5 is a scribe line portion, and 6 is a silicon wafer. FIG. 2 is a cross-sectional view showing an example of a semiconductor package using the heat resistant resin composition of the present invention for a stress relaxation layer. In FIG. 2, 11 is a solder ball, 12 is a copper post, 13 is a stress relaxation layer, 14 is a copper wiring, 15 is a silicon wafer, 16 is a polyimide insulating film, and 17 is an electrode.

  The resin composition of the present invention comprises (A) an aromatic thermoplastic resin that is soluble in a polar solvent at room temperature, and (B) an aromatic thermoplastic resin that is insoluble in a polar solvent at room temperature but is soluble by heating. And (C) a resin composition comprising a rubber elastic filler having an average particle size of 0.1 to 6 μm and a particle size distribution of 0.01 to 15 μm, and (D) a polar solvent. The viscosity measured at a frequency of 5 Hz and 50 Hz under the condition of using a shear stress of 13 Pa is less than 400 Pa · s and 3 Pa · s or more, respectively, and the ratio of the viscosities (viscosity at a frequency of 5 Hz (Pa · s) / Its viscosity (Pa · s) at a frequency of 50 Hz is 2 or more, and according to this, it is excellent in pattern embedding property, adhesiveness, heat resistance, flexibility and printability. Resin composition and resin composition A semiconductor device using the same can be provided.

  In the present invention, the viscosity measured at a frequency of 5 Hz under a shear stress of 13 Pa using a rheometer needs to be less than 400 Pa · s, preferably less than 280 Pa · s, more preferably 250 Pa · s. It is less than s, more preferably less than 220 Pa · s, and particularly preferably less than 200 Pa · s. When the viscosity measured at a frequency of 5 Hz is 400 Pa · s or more, the pattern embedding property of a metal post or the like tends to be inferior. Further, under the same conditions, the viscosity measured at a frequency of 50 Hz needs to be 3 Pa · s or more, preferably 6 Pa · s or more, more preferably 9 Pa · s or more, and particularly preferably 12 Pa · s. That's it. If the viscosity measured at a frequency of 50 Hz is less than 3 Pa · s, the shape retention after printing tends to be inferior. Furthermore, the ratio of the viscosity measured at a frequency of 5 Hz to the viscosity measured at a frequency of 50 Hz (viscosity at 5 Hz (Pa · s) / viscosity at 50 Hz (Pa · s)) needs to be 2 or more, preferably It is 2.1 or more, More preferably, it is 2.2 or more, More preferably, it is 2.3 or more, Most preferably, it is 2.4 or more. If this ratio is less than 2, it tends to be difficult to achieve both pattern embedding properties such as metal posts and shape retention after printing.

  The viscosity at each frequency is insoluble in the resin composition (hereinafter referred to as NV), (A) an aromatic thermoplastic resin soluble in a polar solvent at room temperature, or (B) insoluble in a polar solvent at room temperature. It can be controlled by adjusting the molecular weight of a soluble aromatic thermoplastic resin by heating. Specifically, when the molecular weight of NV or various aromatic thermoplastic resins is decreased, the viscosity at each frequency tends to decrease.

  The viscosity can be measured at room temperature using a rheometer (dynamic viscoelasticity measuring device). Examples of such a device include a rheometer manufactured by BOHLIN INSTRUMENTS, CSR-10 type. Etc.

  In the present invention, (A) an aromatic thermoplastic resin that is soluble in a polar solvent at room temperature and (B) an aromatic thermoplastic resin that is insoluble in a polar solvent at room temperature but soluble by heating are particularly limited. However, it is preferably a polyamide resin, a polyimide resin, a polyamideimide resin or a precursor thereof. In particular, the component (B) preferably imparts thixotropy to the resin composition of the present invention and enables precise pattern formation by screen printing, dispensing application, or the like. The “room temperature” refers to a temperature condition in the case where the solvent temperature is not specified or adjusted, and is left indoors, and is not particularly limited, but a temperature within a range of 10 to 40 ° C. It is preferable that The “heating” is to raise the temperature of the solvent to preferably 80 ° C. or higher, more preferably 80 ° C. to 200 ° C., and still more preferably 100 to 180 ° C. When the heating temperature is less than 80 ° C., the (C) filler is not sufficiently dispersed, and the surface flatness of the resulting coating film tends to decrease.

  Examples of the method for obtaining the polyamide resin, polyimide resin, polyamideimide resin, or precursors thereof include aromatic, aliphatic or alicyclic diamine compounds, dicarboxylic acids or reactive acid derivatives thereof and / or tricarboxylic acids. Alternatively, a known method such as a method of reacting with the reactive acid derivative and / or tetracarboxylic dianhydride may be used, and can be appropriately selected depending on the reactivity of each raw material. The reaction can be carried out without solvent or in the presence of an organic solvent. The reaction temperature 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.

  The organic solvent for producing the component (A) and the component (B) is not particularly limited, and examples thereof include ether solvents such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether, and triethylene glycol diethyl ether. Sulfur-containing solvents such as dimethyl sulfoxide, diethyl sulfoxide, dimethyl sulfone and sulfolane, ester solvents such as γ-butyrolactone and cellosolve acetate, ketone solvents such as cyclohexanone and methyl ethyl ketone, N-methylpyrrolidone, dimethylacetamide, 1,3- Examples thereof include nitrogen-containing solvents such as dimethyl-3,4,5,6-tetrahydro-2 (1H) -pyrimidinone, and aromatic hydrocarbon solvents such as toluene and xylene. Combinations or more types can be used, preferably used to select a solvent which dissolves the resulting resin.

  Moreover, there is no restriction | limiting in particular also in the method of dehydrating and ring-closing a polyimide resin precursor or a polyamideimide resin precursor, respectively, and a general method can be used. 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 poured into a large excess solvent that is compatible with the above organic solvent such as a lower alcohol such as methanol, water, or a mixture thereof, and is a poor solvent for the resin. A precipitate of resin is obtained, this is filtered off, and the solvent is dried to obtain a polyimide resin or a polyamideimide resin. Considering reduction of remaining ionic impurities, etc., the above-described thermal ring closure method is preferable.

  In the resin composition of the present invention, the blending amounts of the component (A) and the component (B) are not particularly limited and may be arbitrary, but preferably (B) with respect to 100 parts by weight of the component (A). 10 to 300 parts by weight of component, more preferably 10 to 200 parts by weight of component (B) is added to 100 parts by weight of component (A). When the blending amount of the component (B) is less than 10 parts by weight, the thixotropic property of the obtained resin composition tends to be lowered, and when it is more than 300 parts by weight, the obtained film properties tend to be lowered.

  The filler having rubber elasticity (C) in the present invention is not particularly limited as long as it can lower the elastic modulus of the resin composition, but acrylic rubber, fluorine rubber, silicone rubber, butadiene rubber, etc. Examples thereof include elastic fillers and liquid rubbers thereof. In consideration of the heat resistance of the resin composition of the present invention, silicone rubber is preferable. For example, Trefill E series (trade name, manufactured by Toray Dow Corning Silicone Co., Ltd.) can be used. (C) It is preferable that the average particle diameter of a component is 0.1-6 micrometers, It is more preferable that it is 0.2-5 micrometers, It is especially preferable that it is 0.3-4 micrometers. When the average particle size is less than 0.1 μm, aggregation between particles occurs, and it tends to be difficult to sufficiently disperse the filler. When the average particle size exceeds 6 μm, it is difficult to introduce a filtration step, There is a tendency for surface flatness to decrease. The shape is preferably finely divided into a spherical shape or an indefinite shape. Furthermore, the particle size distribution of the component (C) is preferably 0.01 to 15 μm, more preferably 0.02 to 15 μm, and particularly preferably 0.03 to 15 μm. When particles having a particle size of less than 0.01 μm are present, aggregation between particles tends to occur, and it is difficult to sufficiently disperse the filler. When particles having a particle size exceeding 15 μm are present, a filtration step may be introduced. It becomes difficult and the surface flatness of the resulting coating film tends to be lowered.

  Moreover, it is preferable that the surface of the filler which is (C) component is chemically modified with the functional group. Examples of such a functional group include an epoxy group, an amino group, an acrylic group, a vinyl group, and a phenyl group, and an epoxy group is preferable. For example, the trefill E-series silicone rubber of Trefill E series has a surface modified with an epoxy group and is suitable as the component (C).

  The component (C) is preferably used in an amount of 5 to 900 parts by weight, preferably 5 to 800 parts by weight, based on 100 parts by weight of the total amount of the aromatic thermoplastic resin including the component (A) and the component (B). More preferably it is used. By adding such a filler (C) to a thermoplastic resin having heat resistance, it becomes possible to make the resin composition low elastic without impairing the heat resistance and adhesion of the resin composition, and its elastic modulus. Can be controlled.

  The (D) polar solvent in the present invention is not particularly limited as long as it is a solvent composed of a polar molecule. For example, N-methylpyrrolidone, dimethylacedamide, dimethylformamide, 1,3-dimethyltetrahydro-2 ( 1H) -nitrogen compounds such as -pyrimidinone, sulfur-containing compounds such as sulfolane and dimethyl sulfoxide, γ-butyrolactone, γ-valerolactone, γ-caprolactone, γ-heptalactone, α-acetyl-γ-butyrolactone, ε-caprolactone, etc. Lactones, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ketones such as acetophenone, ethylene glycol, glycerin, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, Ethylene glycol dibutyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol dipropyl ether, triethylene glycol dibutyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, tetraethylene glycol dipropyl ether, tetraethylene glycol Examples include ethers such as dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, tetraethylene glycol monomethyl ether, and tetraethylene glycol monoethyl ether.

  The blending amount of the component (D) may be appropriately determined in consideration of the viscosity of the resin composition of the present invention, and is not particularly limited. However, with respect to 100 parts by weight of the total resin in the resin composition of the present invention, It is preferable to mix | blend 100-3500 weight part, and it is more preferable to mix | blend 150-1000 weight part.

  Moreover, you may add additives, such as a coloring agent and a coupling agent, and a resin modifier to the resin composition of this invention as needed. 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 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 Methoxysilane, 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 tris (acetylacetonate), aluminum = monoisopropoxymonooroxyethyl acetoacetate, aluminum-di-n-butoxide-mono-ethylacetoacetate, aluminum-di-iso-propoxide-mono-ethylacetoacetate, etc. Aluminum chelate compound, aluminum isopropylate, mono-sec-butoxyaluminum diisopropylate, aluminum-sec- Chireto, 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 used in an amount of 50 parts by weight or less based on 100 parts by weight of the total amount of the aromatic thermoplastic resin including the component (A) and the component (B). When there is more addition amount of the said additive than 50 weight part, there exists a tendency for the coating-film physical property obtained to fall.

  Moreover, you may add a radiation polymerizable compound to the resin composition of this invention.

（式中、Ｒ_７は水素又はメチル基を示し、ｑ及びｒは１以上の整数である。）
で表される化合物、ジオール類、一般式（ＩＩ）

（式中、ｎは０〜１の整数であり、Ｒ_１は炭素原子数が１〜３０の２価あるいは３価の有機性基である。）
で表されるイソシアネート化合物、一般式（ＩＩＩ）

（式中、Ｒ_２は水素又はメチル基であり、Ｒ_３はエチレン基あるいはプロピレン基である）
で表される化合物からなるウレタンアクリレート又はウレタンメタクリレート、一般式（ＩＶ）

（式中、Ｒ_１は炭素原子数が２〜３０の２価の有機基を示す）
で表されるジアミン、および一般式（Ｖ）

（式中、ｎは０〜１の整数である）
で表される化合物からなる尿素メタクリレート、官能基を含むビニル共重合体に少なくとも１個のエチレン性不飽和基と、オキシラン環、イソシアネート基、水酸基、カルボキシル基等の官能基を少なくとも１個有する化合物を付加反応させて得られる放射線重合性共重合等などが挙げられ、これらは単独で又は二種類以上を組み合わせて使用することができる。There is no restriction | limiting in particular as a radiation polymerizable compound, For example, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, pentenyl Acrylate, tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane diacrylate, Trimethylolpropane triacrylate, trimethylolpropane dimethac Rate, trimethylolpropane trimethacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, pentaerythritol triacrylate, penta Erythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, styrene, divinylbenzene, 4-vinyltoluene, 4-vinylpyridine, N-vinylpyrrolidone, 2-hydroxyethyl Acrylate, 2-hydroxyethyl methacrylate, 1,3-acryloyloxy-2-hydroxyprop , 1,2-methacryloyloxy-2-hydroxypropane, methylenebisacrylamide, N, N- dimethyl acrylamide, N- methylol acrylamide, tris (beta-hydroxyethyl) triacrylate isocyanurate represented by the following general formula (I)

(In the formula, R ₇ represents hydrogen or a methyl group, and q and r are integers of 1 or more.)
A compound represented by the formula: diols, general formula (II)

(In the formula, n is an integer of 0 to ₁ , and R ₁ is a divalent or trivalent organic group having 1 to 30 carbon atoms.)
Isocyanate compound represented by general formula (III)

(Wherein R ₂ is hydrogen or a methyl group, and R ₃ is an ethylene group or a propylene group)
Urethane acrylate or urethane methacrylate comprising a compound represented by formula (IV)

(Wherein R ₁ represents a divalent organic group having 2 to 30 carbon atoms)
A diamine represented by formula (V)

(Where n is an integer from 0 to 1)
A compound having at least one ethylenically unsaturated group and at least one functional group such as an oxirane ring, an isocyanate group, a hydroxyl group, and a carboxyl group in a vinyl copolymer containing a functional group and a urea copolymer comprising the compound represented by The radiation-polymerizable copolymer etc. which are obtained by carrying out addition reaction of these etc. are mentioned, These can be used individually or in combination of 2 or more types.

  The amount of the radiation polymerizable compound used is preferably 50 parts by weight or less based on 100 parts by weight of the total amount of the aromatic thermoplastic resin including the component (A) and the component (B). When there is more addition amount of the said additive than 50 weight part, there exists a tendency for the coating-film physical property obtained to fall.

  Moreover, the photoinitiator which produces | generates a free radical by irradiation of actinic light can also be added to the resin composition of this invention. Examples of such a photopolymerization initiator include benzophenone, N, N′-tetramethyl-4,4′-diaminobenzophenone (Michler ketone), N, N′-tetraethyl-4,4′-diaminobenzophenone, 4- Methoxy-4′-dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2,2-dimethoxy-1,2-diphenylethane-1-one, 1- Aromatic ketones such as hydroxy-cyclohexyl-phenyl-ketone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropanone-1, 2,4-diethylthioxanthone, 2-ethylanthraquinone, phenanthrenequinone , Benzoin methyl ether, benzoin ethyl ether, benzoin Benzoin ether such as nyl ether, benzoin such as methyl benzoin and ethyl benzoin, benzyl derivatives such as benzyl dimethyl ketal, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4 , 5-di (m-methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-phenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer 2-mer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer, 2,4-di (p-methoxyphenyl) -5-phenylimidazole dimer, 2- (2,4-dimethoxy) 2,4,5-triarylimidazole dimer such as phenyl) -4,5-diphenylimidazole dimer , 9-phenyl acridine, 1,7-bis (9,9'-acridinyl) including acridine derivatives heptane, and the like. These may be used alone or in combinations of two or more. Although there is no restriction | limiting in particular as the usage-amount of the said photoinitiator, Usually, it is 0.01-30 weight part with respect to 100 weight part of said radiation polymerizable compounds.

  The method for forming a precise pattern using the resin composition of the present invention is not particularly limited, for example, screen printing method, dispensing method, potting method, curtain coating method, letterpress printing method, intaglio printing method, A lithographic printing method and the like can be mentioned, but in consideration of workability and the like, a screen printing method or dispense coating is preferable.

  The semiconductor device using the resin composition of the present invention is, for example, after applying the resin composition of the present invention to a substrate or a lead frame or pasting a resin film made of the resin composition of the present invention to form a resin layer, It is obtained by bonding a chip on a resin layer. Needless to say, the resin composition of the present invention may be applied to the chip surface or a resin film made of the resin composition of the present invention may be attached to the chip surface and then adhered to the substrate or the lead frame. The coating and drying can be performed by a known method. At this time, the resin layer can be obtained in a solvent drying step at 250 ° C. or less without imidization. It is preferable that the formed resin layer has a glass transition temperature Tg of 180 ° C. or higher and a thermal decomposition temperature of 300 ° C. or higher because of sufficient heat resistance. Further, since the tensile elastic modulus of the resin layer can be controlled in the range of 0.2 to 3.0 GPa, it can be applied to any semiconductor device.

  A semiconductor device using the resin composition of the present invention is, for example, a step of forming a resin layer by applying and drying the resin composition of the present invention on a semiconductor substrate on which a plurality of wirings having the same structure is formed, if necessary A step of forming a rewiring electrically connected to the electrode on the semiconductor substrate on the resin layer, a step of forming a protective layer on the rewiring or the resin layer as necessary, and the protection as necessary. A process of forming external electrode terminals on the layer and then a process of dicing as necessary are manufactured. Although it does not restrict | limit especially as said semiconductor substrate, For example, a silicon wafer etc. are mentioned. The method for applying the resin layer is not particularly limited, but screen printing or dispensing application is preferable. The drying method of a resin layer can be performed by a well-known method. Further, since it has sputtering resistance, plating resistance, alkali resistance, etc. required in the process of forming the rewiring, it can be applied to any semiconductor device. In addition, the amount of warpage of the silicon wafer can be reduced. A semiconductor device manufactured by this method can be expected to improve yield, and productivity can be improved.

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

<Synthesis of Component (A) and Component (B)>
(Synthesis Example 1)
2,2-bis [4- (4-aminophenoxy) phenyl] propane in a 0.5 liter four-necked flask equipped with a thermometer, stirrer, nitrogen inlet tube, and cooling tube with an oil / water separator under a nitrogen stream 45.92 g (112 mmol) (hereinafter referred to as BAPP) was added, and 50 g of N-methyl-2-pyrrolidone (hereinafter referred to as NMP) was added and dissolved. Next, 23.576 g (112 mmol) of trimellitic anhydride chloride (hereinafter referred to as TAC) was added while cooling so as not to exceed 20 ° C. After stirring at room temperature for 1 hour, 13.5744 g (134.4 mmol) of triethylamine (hereinafter referred to as TEA) was added while cooling so as not to exceed 20 ° C., and reacted at room temperature for 3 hours to produce a polyamic acid varnish. did. The obtained polyamic acid varnish was further subjected to a dehydration reaction at 190 ° C. for 6 hours to produce a polyamideimide resin varnish. A precipitate obtained by pouring the varnish of the polyamideimide resin into water was separated, pulverized and dried to obtain a polyamideimide resin powder (PAI-1) soluble in a polar solvent at room temperature. It was 88,000 when the weight average molecular weight of the obtained polyamidoimide resin (PAI-1) was measured in standard polystyrene conversion using gel permeation chromatography (henceforth GPC).

(Synthesis Example 2)
Under a nitrogen stream, 45.92 g (112 mmol) of BAPP was placed in a 0.5 liter four-necked flask equipped with a thermometer, a stirrer, a nitrogen introducing tube, and a cooling tube with an oil / water separator, and NMP 50 g was added and dissolved. Next, 23.576 g (112 mmol) of TAC was added while cooling so as not to exceed 20 ° C. After stirring at room temperature for 1 hour, 13.5744 g (134.4 mmol) of TEA was added while cooling so as not to exceed 20 ° C., and the mixture was reacted at room temperature for 3 hours to produce a polyamic acid varnish. The resulting polyamic acid varnish was further subjected to a dehydration reaction at 190 ° C. for 3 hours to produce a polyamideimide resin varnish. A precipitate obtained by pouring the varnish of the polyamideimide resin into water was separated, pulverized and dried to obtain a polyamideimide resin powder (PAI-2) soluble in a polar solvent at room temperature. It was 68,000 when the weight average molecular weight of the obtained polyamidoimide resin (PAI-2) was measured in standard polystyrene conversion using GPC.

(Synthesis Example 3)
Under a nitrogen stream, 45.92 g (112 mmol) of BAPP was placed in a 0.5 liter four-necked flask equipped with a thermometer, a stirrer, a nitrogen introducing tube, and a cooling tube with an oil / water separator, and NMP 50 g was added and dissolved. Next, while cooling so as not to exceed 20 ° C., 14.1456 g (67.2 mmol) of TAC and 14.2566 g of 3,4,3 ′, 4′-benzophenonetetracarboxylic dianhydride (hereinafter referred to as BTDA) (44 .8 mmol) was added. After stirring at room temperature for 1 hour, 8.145 g (80.64 mmol) of TEA was added while cooling so as not to exceed 20 ° C., and reacted at room temperature for 3 hours to produce a polyamic acid varnish. The obtained polyamic acid varnish was further subjected to a dehydration reaction at 190 ° C. for 6 hours to produce a polyamideimide resin varnish. A precipitate obtained by pouring the varnish of the polyamideimide resin into water is separated, pulverized, and dried to obtain a polyamideimide resin powder (PAI-3) that is insoluble in a polar solvent at room temperature, but is heated by heating. Obtained. It was 90,000 when the weight average molecular weight of the obtained polyamidoimide resin (PAI-3) was measured in standard polystyrene conversion using GPC.

(Synthesis Example 4)
Under a nitrogen stream, 45.92 g (112 mmol) of BAPP was placed in a 0.5 liter four-necked flask equipped with a thermometer, a stirrer, a nitrogen introducing tube, and a cooling tube with an oil / water separator, and NMP 50 g was added and dissolved. Next, 14.1456 g (67.2 mmol) of TAC and 14.256 g (44.8 mmol) of BTDA were added while cooling so as not to exceed 20 ° C. After stirring at room temperature for 1 hour, 8.145 g (80.64 mmol) of TEA was added while cooling so as not to exceed 20 ° C., and reacted at room temperature for 3 hours to produce a polyamic acid varnish. The resulting polyamic acid varnish was further subjected to a dehydration reaction at 190 ° C. for 3 hours to produce a polyamideimide resin varnish. A precipitate obtained by pouring the varnish of the polyamideimide resin into water is separated, pulverized, and dried to obtain a polyamideimide resin powder (PAI-4) that is insoluble in a polar solvent at room temperature, but is heated by heating. Obtained. It was 60,000 when the weight average molecular weight of the obtained polyamidoimide resin (PAI-4) was measured in standard polystyrene conversion using GPC.

<Manufacture of resin composition>
(Production Example 1)
110 g of polyamideimide resin powder (PAI-1) soluble at room temperature obtained in Synthesis Example 1 under a nitrogen stream in a 1 liter four-necked flask equipped with a thermometer, stirrer, nitrogen introducing tube and cooling tube, 33 g of polyamideimide resin powder (PAI-3) soluble in the polar solvent obtained in Synthesis Example 3 at room temperature but soluble by heating, 300 g of γ-butyrolactone (hereinafter referred to as γ-BL) and triethylene 129 g of glycol dimethyl ether (hereinafter referred to as DMTG) was added and the temperature was raised to 130 ° C. with stirring. After stirring at 130 ° C. for 2 hours, heating was stopped and the mixture was allowed to cool to room temperature while stirring to obtain a yellow resin composition. To the obtained yellow resin composition, Trefill E-601 (trade name, Toray Dow Corning Silicone Co., Ltd., silicone rubber powder, average particle size: about 2 μm, particle size distribution 1 to 10 μm, hereinafter referred to as E-601. ) Add 61.3g, knead and disperse with a planetary mixer, fill into filter KST-47 (manufactured by Advantech Co., Ltd.), insert a silicone rubber piston, and at a pressure of 3.0 kg / cm ² The resin composition (P-1) was obtained by filtration under pressure. Several g of the obtained resin composition was weighed on a metal petri dish, and the nonvolatile content concentration (hereinafter referred to as NV) was measured under the following conditions. The composition and properties are summarized in Table 1.

NV (%) = (resin composition amount after heat drying (g) / resin composition amount before heat drying (g)) × 100
Drying conditions: 150 ° C.-1 hour + 250 ° C.-2 hours

(Production Example 2)
110 g of polyamideimide resin powder (PAI-2) soluble at room temperature obtained in Synthesis Example 2 under a nitrogen stream in a 1 liter four-necked flask equipped with a thermometer, stirrer, nitrogen introduction tube and cooling tube, Add 33 g of polyamideimide resin powder (PAI-3), 300 g of γ-BL and 129 g of DMTG, which are insoluble at room temperature in the polar solvent obtained in Synthesis Example 3, but rise to 130 ° C. with stirring. Warm up. After stirring at 130 ° C. for 2 hours, heating was stopped and the mixture was allowed to cool to room temperature while stirring to obtain a yellow resin composition. After adding 61.3g of E-601 to the obtained yellow resin composition and kneading and dispersing with a planetary mixer, it was filled in a filter KST-47 (manufactured by Advantech) and a silicon rubber piston was inserted. And pressure filtration at a pressure of 3.0 kg / cm ² to obtain a resin composition (P-2). NV of the obtained resin composition was measured in the same manner as in Production Example 1. The composition and properties are summarized in Table 1.

(Production Example 3)
110 g of polyamideimide resin powder (PAI-1) soluble at room temperature obtained in Synthesis Example 1 under a nitrogen stream in a 1 liter four-necked flask equipped with a thermometer, stirrer, nitrogen introducing tube and cooling tube, 33 g of soluble polyamideimide resin powder (PAI-4), 300 g of γ-BL and 129 g of DMTG are added to the polar solvent obtained in Synthesis Example 4 at room temperature but heated to 130 ° C. with stirring. Warm up. After stirring at 130 ° C. for 2 hours, heating was stopped and the mixture was allowed to cool to room temperature while stirring to obtain a yellow resin composition. 61.3 g of E-601 was added to the obtained yellow resin composition, kneaded and dispersed with a planetary mixer, then filled into a filter KST-47 (manufactured by Advantech), and a silicon rubber piston was inserted, The resin composition (P-3) was obtained by pressure filtration at a pressure of 3.0 kg / cm ² . NV of the obtained resin composition was measured in the same manner as in Production Example 1. The composition and properties are summarized in Table 1.

(Production Example 4)
110 g of polyamideimide resin powder (PAI-2) soluble at room temperature obtained in Synthesis Example 2 under a nitrogen stream in a 1 liter four-necked flask equipped with a thermometer, stirrer, nitrogen introduction tube and cooling tube, 33 g of soluble polyamideimide resin powder (PAI-4), 300 g of γ-BL and 129 g of DMTG are added to the polar solvent obtained in Synthesis Example 4 at room temperature but heated to 130 ° C. with stirring. Warm up. After stirring at 130 ° C. for 2 hours, heating was stopped and the mixture was allowed to cool to room temperature while stirring to obtain a yellow resin composition. 61.3 g of E-601 was added to the obtained yellow resin composition, kneaded and dispersed with a planetary mixer, then filled into a filter KST-47 (manufactured by Advantech), and a silicon rubber piston was inserted, The resin composition (P-4) was obtained by pressure filtration at a pressure of 3.0 kg / cm ² . NV of the obtained resin composition was measured in the same manner as in Production Example 1. The composition and properties are summarized in Table 1.

(Production Example 5)
In Production Example 1, instead of Trefil E-601, Trefill E-600 whose surface is not chemically modified (trade name, Toray Dow Corning Silicone Co., Ltd., silicone rubber powder, average particle size: about 2 μm, A resin composition (P-5) was obtained in the same manner as in Production Example 1 except that the particle size distribution was 1 to 10 μm, hereinafter referred to as E-600). NV of the obtained resin composition was measured in the same manner as in Production Example 1. The composition and properties are summarized in Table 1.

(Production Example 6)
In Production Example 1, instead of Trefil E-601, Trefil R-902A (trade name, silicone rubber powder, average particle size: about 8 μm, particle size distribution 1-30 μm, hereinafter R, Toray Dow Corning Silicone Co., Ltd., R Except for using -902A, a resin composition (P-6) was obtained in the same manner as in Production Example 1. NV of the obtained resin composition was measured in the same manner as in Production Example 1. The composition and properties are summarized in Table 1.

(Example 1)
After adding 18 g of 1,3-dimethyltetrahydro-2 (1H) -pyrimidinone (hereinafter referred to as DMPU) to 100 g of the resin composition (P-1) obtained in Production Example 1, a revolving revolving vacuum deaerator ( Defoamed by Nippon Applied Technology Co., Ltd. (AR-360M type) to obtain a resin composition (P-7).

<Rheological properties>
About the obtained resin composition (P-7), the viscosity (rheological characteristic) was measured. For this measurement, using a rheometer manufactured by BOHLIN INSTRUMENTS, model CSR-10, a shear stress of 13 Pa was applied for 60 seconds, and the frequency was varied from 50 Hz to 5 Hz with the shear stress fixed at 13 Pa. did. At this time, sampling points during measurement were 15 points, and each measurement waiting time was 30 seconds. The results are shown in Table 2.

<Paste characteristics>
A semiconductor substrate on which wiring and copper posts are formed using the obtained resin composition (P-7) (pitch size 5.3 mm × 6.3 mm, scribe line 100 μm, copper post diameter: 300 μm, copper post height: 100 μm) On the screen printing machine (manufactured by Neurong Seimitsu Kogyo Co., Ltd., LS-34GX with alignment device), nickel alloy laser etching metal plate (manufactured by Process Lab Micron Co., Ltd., thickness 200 μm, opening size 5 mm × 6 mm, Using a nylon J squeegee (manufactured by Neurong Seimitsu Co., Ltd.) with a pitch size of 5.3 mm × 6.3 mm), the printability (paste characteristics) was evaluated.

The evaluation was performed by evaluating the paste embedding property in the wiring and the shape retention after printing using the following criteria using an optical microscope. The results are shown in Table 2.
・ Paste embedding in wiring and copper posts ◎: No voids due to poor filling ○: Little voids due to poor filling (void generation rate: less than 10% of the total number of copper posts)
Δ: Some voids due to poor filling (void generation rate: 10-50% of the total number of posts)
×: Void generated due to poor filling almost all over the surface (void generation rate: 50% or more of the total number of copper posts)
* Passes ◎ and ○ above ・ Shape retention after printing ◎: Scribe line formation ○: Scribe line is formed but there is a slight inflow △: Scribe line crushing occurs in part ×: Scribe line crushing (almost entire surface) )
* Passes ◎ and ○ above

  Moreover, NV of the obtained resin composition (P-7) was measured in the same manner as in Production Example 1. The results are shown in Table 2.

<Film characteristics>
Furthermore, the obtained resin composition (P-7) was apply | coated on the Teflon (trademark) board | substrate, it heated at 250 degreeC, the organic solvent was dried, and the film with a film thickness of 25 micrometers was formed. With respect to this film, the tensile elastic modulus (25 ° C., 10 Hz) and the glass transition temperature (frequency 10 Hz, temperature increase rate 2 ° C./min) were measured with a dynamic viscoelastic spectrometer (manufactured by Iwamoto Seisakusho Co., Ltd.). Further, the thermal decomposition starting temperature was measured with a thermobalance under the conditions of a temperature rising rate: 10 ° C./min and an atmosphere: air. The results are shown in Table 2.

<Manufacture and evaluation of semiconductor devices>
Moreover, the process of apply | coating the obtained resin composition (P-7) to the semiconductor substrate with which wiring was formed in multiple times by screen printing, and drying and forming a resin layer, on the said semiconductor substrate on the said semiconductor substrate Forming a rewiring electrically conductive with the electrode, forming a protective layer on the rewiring, forming an external electrode terminal on the protective layer, and further dicing to manufacture a semiconductor device .

  This semiconductor device was subjected to a heat cycle test (−55 ° C./30 min ← → 125 ° C./30 min, 1000 cycles) to examine whether cracks occurred in the resin layer. The results are shown in Table 2. In addition, when description of the evaluation result in a table | surface is "1/10", for example, it shows that one crack generate | occur | produced among 10 samples.

(Example 2)
Resin composition in exactly the same manner as in Example 1 except that the resin composition (P-5) obtained in Production Example 5 was used instead of the resin composition (P-1) used in Example 1. (P-8) and a semiconductor device were manufactured. The obtained resin composition (P-8) and semiconductor device were evaluated in the same manner as in Example 1. The results are shown in Table 2.

(Example 3)
A resin composition (P-9) and a semiconductor device were produced in the same manner as in Example 1 except that the amount of DMPU added in Example 1 was changed to 25 g. The obtained resin composition (P-9) and semiconductor device were evaluated in the same manner as in Example 1. The results are shown in Table 2.

Example 4
A resin composition (P-10) and a semiconductor device were produced in exactly the same manner as in Example 1 except that the amount of DMPU added in Example 1 was changed to 35.5 g. The obtained resin composition (P-10) and semiconductor device were evaluated in the same manner as in Example 1. The results are shown in Table 2.

(Example 5)
Except for using the resin composition (P-2) obtained in Production Example 2 instead of the resin composition (P-1) used in Example 1, and making the amount of DMPU 8 g, completely the same as Example 1 Similarly, a resin composition (P-11) and a semiconductor device were produced. The obtained resin composition (P-11) and semiconductor device were evaluated in the same manner as in Example 1. The results are shown in Table 2.

(Example 6)
A resin composition (P-12) and a semiconductor device were produced in exactly the same manner as in Example 5, except that the amount of DMPU added in Example 5 was 16 g. The obtained resin composition (P-12) and semiconductor device were evaluated in the same manner as in Example 1. The results are shown in Table 2.

(Example 7)
A resin composition (P-13) and a semiconductor device were produced in the same manner as in Example 5, except that the amount of DMPU added in Example 5 was 25 g. The obtained resin composition (P-13) and semiconductor device were evaluated in the same manner as in Example 1. The results are shown in Table 2.

(Example 8)
Except that the resin composition (P-3) obtained in Production Example 3 was used instead of the resin composition (P-1) used in Example 1, and that the amount of DMPU was 16 g, it was exactly the same as Example 1. Similarly, a resin composition (P-14) and a semiconductor device were produced. The obtained resin composition (P-14) and semiconductor device were evaluated in the same manner as in Example 1. The results are shown in Table 2.

Example 9
Except for using the resin composition (P-4) obtained in Production Example 4 in place of the resin composition (P-1) used in Example 1, and changing the amount of DMPU to 8 g, completely the same as Example 1 Similarly, a resin composition (P-15) and a semiconductor device were produced. The obtained resin composition (P-15) and semiconductor device were evaluated in the same manner as in Example 1. The results are shown in Table 2.

(Example 10)
A resin composition (P-16) and a semiconductor device were produced in exactly the same manner as in Example 9, except that the amount of DMPU added in Example 9 was 16 g. The obtained resin composition (P-16) and semiconductor device were evaluated in the same manner as in Example 1. The results are shown in Table 2.

(Comparative Example 1)
A semiconductor device was fabricated in exactly the same manner as in Example 1, except that the resin composition (P-1) obtained in Production Example 1 was used as it was instead of the resin composition (P-7) used in Example 1. The resin composition (P-1) and the obtained semiconductor device were evaluated in the same manner as in Example 1. The results are shown in Table 2.

(Comparative Example 2)
A resin composition (P-17) and a semiconductor device were produced in the same manner as in Example 1 except that the amount of DMPU added in Example 1 was changed to 8 g. The obtained resin composition (P-17) and semiconductor device were evaluated in the same manner as in Example 1. The results are shown in Table 2.

(Comparative Example 3)
A resin composition (P-18) and a semiconductor device were produced in exactly the same manner as in Example 1 except that the amount of DMPU added in Example 1 was changed to 48 g. The obtained resin composition (P-18) and semiconductor device were evaluated in the same manner as in Example 1. The results are shown in Table 2.

(Comparative Example 4)
A resin composition (P-19) and a semiconductor device were produced in exactly the same manner as in Example 9, except that the amount of DMPU added in Example 9 was changed to 35.5 g. The obtained resin composition (P-19) and semiconductor device were evaluated in the same manner as in Example 1. The results are shown in Table 2.

(Comparative Example 5)
110 g of polyamideimide resin powder (PAI-1) soluble at room temperature obtained in Synthesis Example 1 under a nitrogen stream in a 1 liter four-necked flask equipped with a thermometer, stirrer, nitrogen introducing tube and cooling tube, 300 g of γ-BL and 129 g of DMTG were added and the temperature was raised to 130 ° C. while stirring. After stirring at 130 ° C. for 2 hours, heating was stopped and the mixture was allowed to cool to room temperature while stirring to obtain a yellow resin composition. After adding 61.3g of E-601 to the obtained yellow resin composition and kneading and dispersing with a planetary mixer, it was filled in a filter KST-47 (manufactured by Advantech) and a silicon rubber piston was inserted. After pressure filtration at a pressure of 3.0 kg / cm ^2, the mixture was defoamed with a rotation / revolution type vacuum defoaming machine (manufactured by Nippon Applied Technology Co., Ltd., AR-360M type), and the resin composition (P-20) was obtained. Obtained. Using the obtained resin composition (P-20) instead of the resin composition (P-7) in Example 1, a semiconductor device was produced in exactly the same manner as in Example 1. The obtained resin composition (P-20) and semiconductor device were evaluated in the same manner as in Example 1. The results are shown in Table 2.

(Comparative Example 6)
110 g of polyamideimide resin powder (PAI-1) soluble at room temperature obtained in Synthesis Example 1 under a nitrogen stream in a 1 liter four-necked flask equipped with a thermometer, stirrer, nitrogen introducing tube and cooling tube, Add 33 g of polyamideimide resin powder (PAI-3), 300 g of γ-BL and 129 g of DMTG, which are insoluble at room temperature in the polar solvent obtained in Synthesis Example 3, but rise to 130 ° C. with stirring. Warm up. After stirring at 130 ° C. for 2 hours, heating was stopped and the mixture was allowed to cool to room temperature while stirring to obtain a yellow resin composition. The obtained yellow resin composition is filled in a filter KST-47 (manufactured by Advantech Co., Ltd.), a silicon rubber piston is inserted, and after filtration under pressure at a pressure of 3.0 kg / cm ² , a rotation-revolving vacuum Defoaming was performed using a defoaming machine (AR-360M type, manufactured by Nippon Applied Technology Co., Ltd.) to obtain a resin composition (P-21). Using the obtained resin composition (P-21) instead of the resin composition (P-7) in Example 1, a semiconductor device was produced in exactly the same manner as in Example 1. The obtained resin composition (P-21) and semiconductor device were evaluated in the same manner as in Example 1. The results are shown in Table 2.

(Comparative Example 7)
A resin composition (exactly the same as in Example 1) except that the resin composition (P-6) obtained in Production Example 6 was used instead of the resin composition (P-1) used in Example 1. P-22) and a semiconductor device were manufactured. The obtained resin composition (P-22) and semiconductor device were evaluated in the same manner as in Example 1. The results are shown in Table 2.

Claims (5)

  (A) Aromatic thermoplastic resin soluble in polar solvent at room temperature, (B) Aromatic thermoplastic resin insoluble in polar solvent at room temperature, but soluble by heating, (C) Average particle size A resin composition comprising a rubber-elastic filler having a particle size distribution of 0.01 to 15 μm and (D) a polar solvent, and having a shear stress of 13 Pa using a rheometer The viscosity measured at a frequency of 5 Hz and 50 Hz is less than 400 Pa · s and 3 Pa · s or more, respectively, and the ratio of the viscosities (viscosity at a frequency of 5 Hz (Pa · s) / viscosity at a frequency of 50 Hz (Pa · A resin composition in which s)) is 2 or more.   (A) an aromatic thermoplastic resin that is soluble in a polar solvent at room temperature, and (B) an aromatic thermoplastic resin that is insoluble in a polar solvent at room temperature, but is soluble by heating, is a polyamide resin or a polyimide. The resin composition according to claim 1, which is a resin, a polyamideimide resin, or a precursor thereof.   The resin composition according to claim 1 or 2, wherein a surface of the filler having rubber elasticity is chemically modified.   The resin composition according to claim 3, wherein the chemical modification is modification with an epoxy group.   The semiconductor device using the resin composition of any one of Claims 1-4.

Images