TWI287030B - Resin composition, heat-resistant resin paste and semiconductor device using these and method of preparing the same - Google Patents

Abstract

There are disclosed a resin composition comprising (A) a heat-resistant resin soluble in a solvent at a room temperature, (B) a heat-resistant resin which is insoluble in a solvent at a room temperature but becomes soluble by heating, and (C) a solvent; a heat-resistant resin paste further containing (D) particles or liquid state material D showing rubber elasticity; and a semiconductor device using the same and a method for producing the same.

Description

[Technical Field] The present invention relates to a resin composition, a heat resistant resin paste, and a semiconductor device using the resin composition and the heat resistant resin paste, and a method of manufacturing the same, It is a resin composition excellent in adhesion, heat resistance and flexibility. It can be widely used in coating materials such as semiconductor devices, adhesives, stress buffer materials, and the elastic modulus can be arbitrarily controlled and the temperature dependence of the elastic modulus. A small heat-resistant resin is a suitable heat-resistant resin paste for forming such a heat-resistant resin, a semiconductor device using the resin composition, a heat-resistant resin paste, and a method for producing the same. [Technical Background of the Invention] In recent years, as electronic components have become smaller and thinner, it has become an important issue to review how stress is applied to materials suitable for such components. For example, high stress cushioning is required for materials that directly coat electronic parts. In particular, although the size of the entire part is reduced in size, the wafer to be mounted is increased in size and thickness, and is more susceptible to damage due to stress during hardening or hardening. Therefore, the resin body is required to have low stress. In particular, a product in which a plurality of bare wafers are mounted on the same substrate as a 1C board or a lead frame lacking a resin dam is formed, and a little stress at the time of hardening may cause wiring breakage or slab bending, and lead frame deformation. In the formation of a resin dam in which a plurality of bare wafer products or lead frames are mounted on the same substrate as the 1C board, an epoxy resin or the like is conventionally used, but the stress accompanying shrinkage of the resin during hardening is large, and the heat cycle after hardening Problems such as wire breakage or hardened material breakage may occur in the test or the solder reflow test. In addition, regarding the deformation of the resin dam formed on the lead frame, from the scale of the private paper 1 that is deformed, the National Standard (CNS) A4 specification _ (21G X 297 publicly loved the reading of the back of the Jingyin? "

This page is printed by the Intellectual Property Office of the Ministry of Economic Affairs. Employees' Consumer Cooperatives Printed 1287030 A7 B7 V. INSTRUCTIONS (2) The problem of poor forming during the flow of mold resin to the mold. In order to solve such a problem, an attempt has been made to add a ruthenium-rubber elastomer to an epoxy resin composition to impart flexibility and cushioning stress in JP-A-2-31152. There are problems such as a decrease in adhesion to the substrate and a decrease in resin strength. Also, surface mounting of CSP (wafer size package) or bare chip mounting

In the type of conductor device, the stress caused by the difference between the thermal expansion coefficient of the semiconductor component and the mounting substrate causes the solder joint to undergo plastic deformation, which may cause fatigue damage. Therefore, an insertion type selection 彳1 or a stress buffer layer is provided between the semiconductor element and the mounting substrate, and the stress caused by the difference in thermal expansion coefficient of the mounting substrate is reduced. For example, the semiconductor device disclosed in Japanese Laid-Open Patent Publication No. Hei No. Hei 10-79362 increases the bump stress by the bump. Moreover, in the thermal cycle test or the solder reflow test dream, a stress buffer layer or adhesion formed by a low elastic material I If having a difference in thermal expansion coefficient between the wafer and the mounting substrate is used for the purpose of high reliability of the chip package. Floor. That is, since the bare wafer is mounted in the semiconductor device without a structure capable of buffering stress, an underfill resin layer is provided between the semiconductor element and the mounted substrate to reduce the stress caused by the difference in thermal expansion coefficient of the mounted substrate. 11彳疋 In the above-mentioned structure of the bump stress buffer solder joint stress, the 'opposite stress set' bump body' leads to the problem of poor connection winter. Also, in the method of using the underfill resin, it is necessary to be in the semiconductor The narrow gap between the device|| and the mounting substrate fills the tree wax, and the filling operation is troublesome, and it is difficult to fill the entire gap with the resin, and the manufacturing efficiency of the semiconductor device is lowered. ) Weaving grid (g 2g7^y 2 312417 1287030 B7 V. Inventive Note (3) CSP - Example 〇bga (ball grid array) to ensure the wire (four) on the wafer from the title (ΓΓ 黏 粘) How to balance the adhesion between the electrodes and the TAB tape and the elastic material of the evening. The purpose of the smear of the smear is to use the low-level crystals that have been completely separated so far. The process and the packaging process are as follows. The size of the same size of the circle will make the package in the wafer state I will be the wafer level CSP process macro. According to this technology, the film can not only reduce the manufacturing cost of the piece, but also shorten the wiring length. Reduced package Medium signal delay or noise, which is advantageous for speeding up the operation. / In this package, in order to ensure high reliability, it is necessary to use thermal expansion of the slow (four) wafer and the mounted substrate in the same way as the conventional CSP of "GA". A stress relaxation layer or an adhesive layer formed by a low coefficient of elasticity. In the wafer layer: in the process of under-CSP, in order to connect the electrodes in the wafer to the external mounting substrate, the sputtering method or the electro-deposition method is used. A metal layer called a rewiring layer is formed on the stress buffer layer, so that not only low elasticity but also resistance to sputtering or plating is required. However, the low elastic material used in the //GA is low in elasticity, but Poor heat resistance, low resistance to sputtering or electroplating, so unsuitable for wafer level CSP process. On the other hand, 'Although it is attempted to add an early elastic component with rubber elasticity to the epoxy resin to reduce the defect rate, Buffering stress (Japanese Patent Publication No. 61_4 8 5 4 4)? However, the incorporation of these components has a problem of lowering the heat resistance of the resin. Generally, the thermoplastic resin having high heat resistance has a resin elastic modulus. This paper makes high-scale national standards applicable country (CNS) A4 Regulation (21〇; < 297 male f) Note page

3 312417 Ϊ Ϊ 287030 A7 V. INSTRUCTIONS (4) Intensity and fragility, when applied to electronic parts, in the case of hardening of the substrate after the hardening or thermal shock test, the possibility of resin breakage and other defects may occur. Japanese Laid-Open Patent Publication No. W23824 proposes a method of co-polymerizing a monomer having rubber elasticity in a resin. However, these methods lead to a decrease in heat resistance of the resin body, which is not preferable. In recent years, polyimine, polyamine or polyamine resins which are excellent in heat resistance and mechanical properties have been widely used in the field of electronics for surface protective films or insulating iridium of semiconductor elements. , , , , 该 该 该 该 该 该 该 该 该 该 该 该 该 该 该 该 该 该 该 该 该 该 该 该 该 该 该 该 该 该 该 该 该 该 该 该 该 该 该 该 该 该 该 该 该A screen printing method, a spray method, a film lamination method, etc. The material which can be screen-printed is a varnish which is heat-resistant polyimine resin or the like which is a bonding material, and is used as a paste. The filler of the material provides the effect of imparting thixotropy to the paste. The filler has a method of using fine particles or heat-resistant non-soluble polyimide particles. However, the particles are at the filler interface during heat drying. In order to solve these problems, a heat-resistant resin paste disclosed in Japanese Patent Publication No. Hei 2-289646 has been developed. The resin paste is used in a binding material of poly-proline. A paste in which a polyphthalic acid filler has been dispersed, and the filler is first dissolved in heat drying, and then the phase is dissolved in the bonding material to uniformly coat the socks during the formation of the crucible. Amination requires a hardening condition of 3 〇〇 or more, and has a high modulus of elasticity and poor flexibility. Also, the same is true for other polyimides. (CNS) A4 specification (21G X 297 public) — 4 312417

U-------------------t--------- (Please read the back of the box first ¥¥& this page) nnn , -nn < age

Please read the note on the back first «' 1287030 _ A7 V. Invention (5') ~^ B --- |, a transfer coating method The coating efficiency of a heat resistant resin solution is usually at 〇% |, lower (〇% The environmental aspects and the cost side of the above-mentioned uncoated on the substrate are also used. In other respects, the screen printing method using the metal plate or the mesh plate has eight parts in a short period of time, and the heat resistance can be efficiently applied. The advantage of resin. Further, the spraying method has the advantage of efficiently applying heat-resistant trees and fats only in a necessary portion in a non-contact manner. The heat-resistant resin paste of the coating type which is excellent in coating efficiency, such as screen printing or jet printing, is formed by using the heat resistance of the solvent dissolved in the solvent during heating and drying in JP-A No. Hei. Report of the heat-resistant resin paste of the pattern. However, the heat-resistant resin has a large modulus of elasticity, and there is a problem that it cannot be used as a stress buffering material having a difference in thermal expansion coefficient between the substrate and the mounting substrate. With the low cost of electronic equipment, there is a strong demand for semiconductor devices that have the same reliability and low cost per CSP. For those who are cost-effective, semiconductors are mounted on semiconductor wafers. After the reduction, the wafer is broken and a so-called wafer|level CSP of a semiconductor device is obtained. The reason for the low cost is that the package process can be batch-processed on the wafer, and In the wafer-cut semiconductor component, the number of steps can be reduced as compared with the processed CSP. Specifically, it is electrically plated on a semiconductor wafer as disclosed in Japanese Laid-Open Patent Publication No. Hei 10-79362. | Copper binding posts, after resin encapsulation, grinding the resin to the steel terminal studs to expose it, loading the solder balls on the exposed copper terminal studs, and cutting the semiconductor wafer into individual semiconductor devices. ^ Paper scale applicable to China Standard (CNS) A4 size (210 x 297 mm) ~ ------------ 312417

5 1287030 A7 --.B7 V. INSTRUCTIONS (6 However, in the manufacturing method of the wafer level CSp proposed in the prior art, a special mold is required in many cases in which a method of encapsulating a resin is used. Further, an insulating layer is formed on the wafer surface. The method of using the spin coating step has a large material loss and a problem that the cost is very high before the mass production technique is established. The object of the present invention is to solve the above problems and provide heating only under 25 ° C. In the step, a film having high strength, low modulus of elasticity, and excellent flexibility can be obtained, in particular, a resin composition which can be obtained only by a solvent drying step of 25 Å or less without a hydrazine imidization step. An object of the present invention is to provide a resin which is insoluble in a polar solvent at room temperature, but which is soluble by heating, imparts thixotropy to the composition of the tree, and is formed by a resin such as a net brush or spray coating. The object of the present invention is to provide a coating film which can obtain the same characteristics of the tree pond as the polyimine by heating the spine of only 250 t or less, in particular, without the need to undergo the imidization step. A resin composition of a film having high strength and flexibility can be obtained by a solvent drying step of 25 or less (rc), and a semiconductor device using the resin composition. Another object of the present invention is to provide a semiconductor device which can be widely used. A coating material such as a mold and a stress-relieving material can be opened into a resin film which is arbitrarily controllable in elasticity and excellent in heat resistance, and has thixotropic properties and is suitable for heat-resistant coating methods such as screen printing or spray coating. The present invention is to provide a coating for a semiconductor device or the like which can be widely used for a heat-resistant resin paste which is thixotropy and suitable for a coating method which is superior in efficiency such as screen printing or spray coating. Materials, Adhesives, S-Standard Scales for Chinese Specifications (2!〇χ 297 公爱;

6 312417 7 1287030 A7 _B7 V. INSTRUCTION DESCRIPTION (7) Stress buffer #material, a semiconductor device of a resin film whose modulus of elasticity is arbitrarily controllable and excellent in heat resistance. Another object of the present invention is to provide a semiconductor insulating resin and a resin layer which are used for preventing a metal wiring or a solder joint portion from being damaged by thermal stress of a semiconductor device having a resin layer. A semiconductor device using the resin. Another object of the present invention is to provide a semiconductor device manufacturing method and a semiconductor device which can minimize material loss, prevent poor connection, and have excellent reliability. [Disclosure of the Invention] The resin composition of the present invention is characterized by containing (A) a heat-resistant resin which is soluble in a solvent at room temperature, and (B) a heat-resistant resin which is insoluble in a solvent at room temperature but which is soluble by heating and C) Solvent. Further, the resin composition of the present invention contains (A ') an aromatic thermosensitive plastic resin which is soluble in a polar solvent at room temperature, and (B,) an aromatic thermoplastic which is insoluble in a polar solvent at room temperature but which is soluble by heating. Resin and (c,) organic solvent. Further, the heat-resistant resin paste of the present invention is characterized in that it contains (A" a heat-resistant resin A, (B") which is soluble in a (C,) solvent at room temperature and heat-drying at room temperature. It is insoluble in (C,,) solvent, heat-resistant resin 6", (C") solvent which is soluble at the time of heat drying, and (D) particles or liquid d which shows rubber elasticity. The resin for semiconductor insulation of the present invention is characterized in that the resin layer has an elastic modulus of 25 to 3.0 GPa at 25 <>c and the elastic modulus of the above resin layer at i5 〇<t is applicable to the Chinese National Standard (CNS)_A4. Specifications (10) Despise public love 312417 Note page

1287030 A7 V. INSTRUCTION OF THE INVENTION (8) The elastic layer ratio of the resin layer is preferably from 10 to 100% at -65 ° C, and the glass transition temperature of the above resin layer is preferably 180 ° C or more. The semiconductor device of the present invention is characterized by using the above resin composition, heat-resistant resin paste, and resin for conductor insulation. A method of manufacturing a semiconductor device according to the present invention includes a step of forming a plurality of resin layers on a semiconductor substrate on which a first wiring layer is formed, and forming an electrode on the semiconductor substrate and a second wiring layer electrically conducting on the resin layer. a step of removing the external electrode tab mounting portion on the second wiring layer, forming a protective layer, and forming an external electrode tab on the protective layer. The method for fabricating a semiconductor device according to the present invention is characterized in that a resin layer is formed on a semiconductor substrate on which a first wiring layer is formed, and a step is formed on the portion of the tree moon layer to reach the above-mentioned wiring layer. In the step of forming a hole, a step of forming an external connection joint on the resin layer and forming a second wiring layer electrically connected to the second wiring layer is further formed. The semiconductor device manufacturing method of the present invention further includes a resin having a modulus of 0.2 to 3.0 GPa at 25 t, a glass transition temperature of i8 (rc or more, and a weight reduction temperature of 30 (rc or more is printed on the semiconductor in which the first wiring layer is formed). a step of forming a resurfacing resin layer on the wafer; forming an electrode of the semiconductor wafer and a second wiring layer electrically conducting on the tree raft layer, and printing the resin on the second wiring layer a step of forming a protective layer of the second wiring layer of the plurality of layers; a step of reaching the through hole of the second wiring layer on the protective layer of the second wiring layer; and the step of forming the through-hole electrode joint : and the feeding conductor wafer paper size is applicable to China 312417 (please read the phonetic transcription on the back first? Write this page >

1287030 A7 B7

5. Description of the Invention (l〇) wherein R1, R2, R3 and R4 each independently form a halogen atom, a carbon atom number of 1 to 9, a carbon atom, and a number of 1 to 9 alkoxy or proenzyme or

Sub, X is a single bond, 0-, -S_, -Cf - η, . A ’ 0)-, -so2·, -s(= 〇)- or 棊, as shown in the following formula, each of the overlapping units may also be different from each other. —C— wherein R and R are each independently a hydrogen atom, a pyridyl group, a trifluoromethyl group, a dichloromethyl group, a permeate atom or a phenyl group. (2) a component of the following &) and/or a diamine compound; (a) an aromatic diamine compound other than the general formula (I), (b) an aliphatic or alicyclic diamine a compound, (3) consisting of the following component (c) and/or (an acid compound formed by a phantom; (c) a dicarboxylic acid or a reactive acid derivative thereof, (d) a tricarboxylic acid or a reactive acid thereof In the present invention, when the resin (B') is a polyether amidoximine or a polyether decylamine, the constituents (1), (2) and (3) or (1) and (3) The resin obtained by the reaction is preferably (1) the aromatic diamine compound represented by the above general formula (I); (2) formed by the following constituents (a) and/or (b) a diamine compound, (a) an aromatic diamine compound other than the general formula (I), (b) an aliphatic or alicyclic diamine compound, (3) consisting of the following constituent (c) and/or (d) The acid compound formed and the four-needle acid or the reactive acid derivative represented by the following general formula (Π) are packed into a package---- (please read the precautions on the back and fill in the form) This page) nn f. H 1 I i- Ministry of Economic Affairs Intellectual Property Office staff consumption The size of the paper printed by the Society is applicable to the Chinese National Standard (CNS) A4 specification (210 297 297 mm) 10 312417 1287030 A7 B7 5. The compound of the invention (11); (C) the dicarboxylic acid or its reactive acid derivative (d) tricarboxylate or its reactive acid derivative 〇〇(II) Η Ο (please read the notes on the back and fill out this page) δ where Υ is a single bond, _〇_, _s', _c(=o)-, _so2-, _s(= 〇)-, a group represented by the following formula, a divalent aromatic hydrocarbon group, an aliphatic hydrocarbon group or an alicyclic hydrocarbon group, each of which may be different from each other. In the formula, R5 and R6 are the same as those described above. In the present invention, when the resin (B) is a polyether quinone, the following components (1), (2) and (3) or (1) and 3) The resin obtained by the reaction is preferably (1) the aromatic diamine compound represented by the above general formula (I); (2) the second component (a) and/or (b) Amine compound; printed by the Ministry of Economic Affairs Intellectual Property Office employee consumption cooperative (a) an aromatic diamine compound other than the general formula (I), (b) an aliphatic or alicyclic diamine compound, (3) from the above general formula (II) A compound formed by the tetracarboxylic dianhydride or a reactive acid derivative thereof. The room temperature in the present invention means a temperature condition when the treatment is carried out without specifying or adjusting a specific temperature, or when the sample or the substance is placed indoors. There are no special restrictions, but the temperature is preferably in the range of 10 to 40 ° C. This paper scale applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 11 312417 1287030 A7 B7 V. Description of the invention (I2) Further, 'heating is to raise the temperature to a room depth or more, and there is no particular limitation on the temperature, but it is preferable to raise the temperature to 50 ° C or more. The polyether amidoximine or polyether decylamine of the present invention is exemplified by an ether group having the following: - hydrazine and a guanamine or quinone imine group of the formula (i), (ii) or (iii) The resin made by the unit is ideal. Ο C 〇 Η - II I -N Z1—C-N_ (i) (Please read the notes on the back and fill out this page)

In the formula, Z1 is a trivalent aromatic hydrocarbon group, an aliphatic hydrocarbon group or an alicyclic hydrocarbon group, and -m (ii) wherein Z2 is a divalent aromatic hydrocarbon group, an aliphatic hydrocarbon group or an alicyclic hydrocarbon group,

(iii) ------ ------------ #Zi is a tetravalent aromatic hydrocarbon group, aliphatic hydrocarbon group or lipid raft in the printed version of the Intellectual Property Office of the Ministry of Economic Affairs. Hydrocarbyl group. Further, the polyether oximine in the present invention is preferably a resin obtained by containing an ether group of the above formula and a quinone imine group of the above formula (iii) as a reversing unit. The polar solvent in the present invention is not particularly limited as long as it is a solvent composed of a polar molecule, and examples thereof include a protic solvent such as an alcohol or a carboxylic acid which can be easily released by dissociation (H + ) or dissociation. The proton-producing non-paper scale applies to the National Standard (CNS) A4 specification (210 x 297 mm) 12 312417 1287030 A7

V. Description of the invention (U) Protic solvent, etc. The latter ones are acetonitrile, dimethoxyethane, dimethylformamide (DMF), bis, yttrium (DMSO), dimethyl hexamethylphosphonate (HMPA), N-methyl-2- Aprotic solvent such as fluorenone (NMP), dimethylacetamide (DMAc), r · butyrolactone, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol II C-, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, tri-6 glycol diethyl ether, triethylene glycol dipropyl ether, triethylene glycol dibutyl ether, tetraethylene glycol dimethyl _, Tetraethylene glycol diethyl ether, tetraethylene glycol dipropyl ether, tetraethylene glycol dibutyl hydrazine, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, triethylene glycol An ether such as dimethyl ether, triethylene glycol monomethyl ether, diethylene glycol monoethyl ether, tetraethylene glycol monomethyl ether or tetraethylene glycol monoethyl ether. Please read the back note first.

II In the present invention, the aromatic diamine compound having an ether bond represented by the above general formula (I) may, for example, be 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-amine) Phenyloxy)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] 戍 戍 4 4 [4-(4-aminophenoxy) Benzyl] code, bis[4-(4-aminophenoxy)benzene tomb]ether, 4,4'-carbonylbis(p-phenylene oxide)diphenylamine, 4,4'-bis ( 4-aminophenoxy)biphenyl or the like. Among them, 2,2-bis[4-(4-aminophenoxy)phenyl]propane is ideal. Two or more kinds of the above aromatic diamine compounds may be used in combination as necessary.

I 1 ί

Ministry of Economic Affairs Intellectual Property Bureau Employees Consumption Co., Ltd. Printed Paper Size Applicable to China National Standard (CNS) A4 Specification (210 X 297 mm) 13 312417 1287030 A7 V. Invention Description p) (Please read the note on the back first) The amount of the aromatic diamine compound represented by the general formula (I) in the present invention is preferably from 0.1 to 99.9 mol%, more preferably from 15 to 99.9% mol%, based on the total amount of the diamine component. Good for 30 to 99.9 moles. In the present invention, the aromatic diamine compound shown in the above general formula (1) may, for example, be m-phenylenediamine, p-phenylenediamine, diamino-m-xylene. , diamino-p-xylene, 14 naphthalene diamine, 2,6-naphthalenediamine, 2,7-naphthalenediamine, 4,4,-diaminodiphenyl maple, 3,3,-di Aminobiphenyl maple, 3,4,-diaminodiphenyl hydrazine, 4,4-diaminodiphenyl ether, 3,3-diaminodiphenyl ether, 3,4,-diamino Diphenyl ether, 3,4'-diaminobiphenyl, 4,4, diaminobenzophenone, 3,3,-diaminobenzophenone, o-toluidine, 2,4_ Toluene diamine, 13-bis(3-aminophenoxy)benzene, 1,4-bis(3-aminophenoxy)benzene, iota, 3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, bis[4-(3^.aminophenoxy)phenyl] code, 4,4, bis(4-aminophenoxy) linkage Benzene, 4,4,-diaminodiphenyl sulfide, 3,3,-diaminodiphenyl sulfide, 3,4, diaminodiphenyl sulfide, 2,2-dual (4 -aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-methylphenyl)propane, 2,2.bis(3-amino-4-methylphenyl)hexafluoropropane, 2,2\dimethyl- Benzidine, 2,2,_bis(trifluoromethyl)benzidine, 4,4'-diamino-3,3',5,5'-tetramethyldiphenylmethane, 4,4,- Diamino-3,3',5,5,-tetraethyldiphenylmethane, 4,4'-diamino-3,3,5,5,-tetra-n-propyldiphenylmethane, 4,4'-Diamino-3,3,5,5,4-tetraisopropyldiphenylmethane, 4,4,diamino-3,3',5,5,-tetrabutyl Phenylmethane, 4,4,-diamino-3,3'-dimethyl-5,5'-diethyldiphenylmethane, 4,4'-diamino-3,3, dimethyl 5-,5'-diisopropyldiphenylmethane, 4,4'-diamino-3,3,-diethyl-5,5'-diisopropyldiphenylmethane, 4, 4'_Diamino-3,5-dimethyl 312417 Table paper scale applicable to China National Standard (CNS) A4 specification (210><297 mm) 1287030 A7 B7 V. Description of invention (15) Base -3%5 '_Diethyldiphenylmethane, 4,4'-monoamino-3,5-dimethyl-3',5'-diethyldiphenylmethane, 4,4'-diamino- 3,5-diethyl_3,,5,_ diiso Diphenylmethane, 4,4,-diamino-3,5-diethyl "·3,5,-dibutyldiphenylmethane, 4,4,-diamino-3,5 -diisopropyl-3',5,dibutyldiphenylmethane, 4,4'-diamino-3,3'-diisopropyl-5,5'-dibutyldiphenylmethane , 4,4'·diamino-3,3'-dimethyl-5,5'-dibutyldiphenyl f, 4,4'-diamino-3,3,diethyl- 5,5'-dibutyldiphenylmethane, 44,-amino--3,3'-diethyldiphenylmethane, 4,4'-diamino-3,3,-diethyl Diphenylmethane, 4,4'-diamino-3,3'-di-n-propyldiphenylmethane, 4,4,-diamino-3 3,3'-diisopropyldiphenyl Burning, 4,4, diamino-3,3,-dibutyldiphenylmethane, 4,4'-diamino-3,3',5-trimethyldiphenylmethane, 4,4 '-Diamino-3,3',5·triethyldiphenylmethane, 4,4,-diamino-3,3,5-tri-n-propyldiphenylmethane, 4,4' -diamino-3,3',5-triisopropyldiphenylcarbamate, 4,4'-diamino-3,3',5-tributyldiphenylcarbamate, 4,4 '-Diamino-3-methyl-3'-ethyldiphenylmethane, 4,4'-diamino-3 -methyl-3,-isopropyldiphenylmethane, 4,4'-diamino-3-ethyl-3'-isopropyldiphenylmethane, 4,4,diamino-3- Ethyl-3,-butyldiphenylmethane, 4,4,-diamino-3-isopropyl-3'-butyldiphenylmethane, 4,4'-diamino-2,2 , _bis(3,3,5,5,·tetramethyldiphenyl)isopropane, 4,4′·diamino 2,2,-bis (3,3,,5,5,_ Tetraethyldiphenyl)isopropane, 4,4,-diamino-2,2,-bis(3,3%5,5'-tetra-n-propyldiphenyl)isopropane, 4,4' _Diamino-2,2,-indole (3,3,5,5'-tetraisopropyldiphenyl)isopropane, 454,-diamino-2,2,-bis (3,3 ,,5,5,-Tetrabutyldiphenyl)isopropane, 4,4,-diamino-3,3,5,5,-tetramethyldiphenyl ether, 4,4'-di Amino-3,3',5,5'-tetraethyldiphenyl ether, this paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) _ 15 312417 • L---- ---------装--- (Please read the note on the back to write this page) Order: Line · Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed 1287030 A7 V, invention description to), 4, 4 - January female Base_3,3,5,5-tetra-n-propyldiphenyl ether, 4,4,-diamino-3,3',5,5'-tetraisopropyldiphenyl ether, 4,4 , diamino-3,3,5,5,-tetrabutyldiphenyl ether, 4,4,-diamino-3,3',5,5, tetramethyldiphenyl maple, 4, 4'-Diamino-3,3',5,5丨-tetraethyldiphenyl maple, 4,4, diamine, 3,5,5'-tetra-n-propyl, maple, 4,4 -monoamine-3,3',5,5' tetraisopropyldiphenyl maple, 4,4'-diamino-3,3,5,5-tetrabutyldiphenyl maple, 4,4, _Diamino-3,3',5,5'-tetramethyldiphenyl ketone, 4,4,-diamino-3,3,55,5,-tetraethyldiphenyl ketone, 4 , 4'-Diamino-3,3',5,5'-tetra-n-propyldiphenyl-, 4,4,-diamino-3,3',5,5'-tetraisopropyl Diphenyl ketone, 4,4'diamine _3,3,,5,5,-tetrabutyl bis-based, 4,4-amino group _3,3,5,5,_4 Methyl phenyl toluidine, 4,4'·diamino-3,3',5,5'-tetraethylbenzamide, 4,4,-diamino-3,3,5,5 , - tetra-n-propyl abbreviated aniline, 4,4'-diamino-3,3,5,5,_tetraisopropylbenzamide, 4,4,diamino-3, 3% 5,5'-tetrabutyl Toluene aniline, m-toluenediamine, 4,4,-diaminodiphenylethane, 154_bis(4-aminoethyl) benzene (BAP), upper 3_bis (4-amino group Alkenyl) benzene, aminophenoxy)benzene, 1,4-bis(3-aminophenoxy)benzene, 1,4,bis(4-aminophenoxy)benzene, 2,2- Bis[4-(3-aminophenoxy)phenyl]propane, bis[4-(3-aminophenoxy)phenyl] meth] (m-APPS), bis[4-(4-aminobenzene) Oxy)phenyl] code '22 bis[4-(4-amine basic oxy) benzyl] hexafluoropropene and the like. Two or more kinds of the above-mentioned aromatic two-face compound may be used in combination as necessary. In the present invention, the total amount of the aromatic diamine compound other than the aromatic diamine compound represented by the formula (I) is preferably from 〇 to 99.9 mol%, more preferably 15 to the total amount of the diamine component. 99.9% of the mole, preferably 3〇 to 99 9 mole%. The scale applies to the national standard (CNS) A4i (210 X 297 mm) '-*--- 16 312417 l·----------^ Install (please read the note on the back first) Page) Order · Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed 1287030 A7 V. Inventive Note (17) In the present invention, the above aliphatic or alicyclic diamine compound is bonded to an aliphatic or alicyclic ring as long as it is an amine group. The compound of the hydrocarbon is not particularly limited, and examples thereof include 1,2-diaminoethane, i,3-diaminopropane, l4-diaminobutane, and 1,5-diaminopentane. Alkane, diaminohexane, amine heptane, 1,8-diamino octyl, decyl diamine decane, hydrazine, ... diamine ketone, U1-diaminoundecane, two Aminododecane, 3 9 bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro[5,5]undecane (ATU), methylcyclopentanediamine ( Aliphatic diamine compound such as MPMD), trimethylcyclohexanediamine (TMD), 1,2-diaminocyclohexane, methylidenediamine cyclohexamethylenetetramine (pA(:M) An alicyclic diamine compound such as an amine-derived amine (NBD A), and a diamine-based anthracycline' main chain is an epoxy epoxide or an epoxy A diamine compound of a copolymer of a fired, an epoxy bromide and a propylene oxide, wherein the main chain is a rubber diamine compound, and if necessary, two or more of the above aliphatic or alicyclic diamine compounds may be used in combination. In the invention, the amount of the aliphatic or alicyclic diamine compound is preferably from 至1 to 95% by mole, more preferably from 0.1 to 90% by mole, based on the total amount of the diamine component. 0 to 1 to 8 5 mol%. In the present invention, the aliphatic or alicyclic diamine compound (b) is preferably one having a diaminocyclooxane represented by the following general formula (m). -R7-T卜〇j~Sh-R8-NH2 R10 /n R12 wherein R7 and R8 are a divalent hydrocarbon group, and R9 to R12 are an alkyl group having a carbon number of 9 or a phenylene group or an alkyl group. Substituted phenylene, η is 1 to -l·------------ loaded - (please read the phonetic on the back? iHi write this page) · · Ministry of Economic Affairs Intellectual Property Office staff Printed by the Consumer Cooperative (III) This paper scale applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 17 312417 1287030 A7 B7 V. Inventive Note C8) 30 integer. (Please read the following notes on the back page.) The diamine-based cyclodecanes shown in the above general formula (dish) can be cited as X-22-161AS, X-22-161A, x manufactured by Shin-Etsu Chemical Co., Ltd. -22_161 B; BY16-8 53U, BY16-853, BY-16-853B manufactured by Donglian·Taike Oxan Company; TSL9386, TSL9346, TSL93 06 manufactured by Toshiba Ketone Co., Ltd.; F2 manufactured by Unica Corporation of Japan -053-01 and so on. Two or more kinds of diaminocyclopentane may be used in combination as necessary. In the present invention, the total amount of the diamine-based oxoxime to the diamine component is preferably from 0.1 to 99.9 mol%, more preferably from 0.1 to 95 mol%, most preferably from 〇 j to 90 mol%. In the present invention, the upper disc dicarboxylic acid or its reactive acid derivative may be exemplified by oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, and gly. Aliphatic dicarboxylic acids such as diacid, suberic acid, azelaic acid, klysic acid, undecanoic acid, dodecanoic acid, tridecyl diacid, cyclohexane dicarboxylic acid, dimer acid, benzene Acid, isophthalic acid, terephthalic acid, naphthalene dicarboxylic acid, hydroxydiphenyl acid, 4,4, diphenyl ether dicarboxylic acid, 4,4'-diphenyl maple dicarboxylic acid, 4,4 An aromatic dicarboxylic acid such as diphenyldicarboxylic acid and a reactive acid derivative of the same, and the like, wherein terephthalic acid, isophthalic acid and reactive acid derivatives of the acids are readily available. More ideal. When necessary, two or more kinds of the above dicarboxylic acids or reactive acid derivatives thereof may be used in combination. In the present invention, the bis-acid or the reactive acid derivative is preferably used in an amount of from 80 to 150 mol% based on the total amount of the diamine component, more preferably from 9 Å to 50 mol%. The above-mentioned tri-hypo-acid or its reactive acid derivative can be exemplified by stupid tri-acid, and the paper size is used in Chinese National Standard (CNS) A4 specification (210 X 297 mm) 18 312417 1287030 A7.

V. INSTRUCTIONS C9) 3,3,4,-benzophenone tris(tetra), 2,3,4,-diphenyltrisinic acid, 2,3,6_吼. Three anti-acids, 3,4,4,-benzoanilide tri-, a methoxy_3,4,4'-diphenyl ether tricarboxylic acid, 2, _ chloro anilide _3, 4, 4. Tricarboxylic acid and the like. The reactive derivative of the above-mentioned tricarboxylic acid is the above-mentioned aromatic tricarboxylic acid anhydride, the compound, the vinegar, the decylamine, the money salt, etc., and examples thereof include trimellitic anhydride, trimellitic anhydride monochloride, 1, 4_2. Carboxyl group _3_N, n_: methylaminoformamidine, 1'4-dimethylacetate-3 benzoic acid, m-di-rebel carbonyl phenoxybenzene, 2,6-dicarboxy_3_carbonyl Oxypyridine, M-carboxyaminocarbazinyl, an ammonium salt formed by the above aromatic tribasic acid and ammonium, methylamine, triethylamine, etc., among which trimellitic anhydride and trimellitic acid monochloride More preferably 0 (Please read the note on the back first nn I item Hi write this page > Binding: If necessary, two or more kinds of the above-mentioned tricarboxylic anhydride or its reactive acid derivative may be used in combination. The acid or the reactive acid derivative is preferably used in an amount of from 80 to 150 moles per gram of the total amount of the diamine component, more preferably from 90 to 150 mole %. The Ministry of Economy, Intellectual Property Office, Staff Consumer Cooperative, prints the above general formula. (Π) The tetracarboxylic dianhydride or a reactive acid derivative thereof may, for example, be 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2,3,3,-biphenyl. Tetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-dual (2 , 3_Dicarboxyphenyl)propane dianhydride, 1,1 bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane Anhydride, bis(2,3-tricarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl) Alkane dianhydride, bis(3,4-dicarboxyphenyl) dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, 3,4,3',4'-benzophenone tetracarboxylate Acid dianhydride, 2,3,2,,3'-benzophenone tetracarboxylic dianhydride, 2,3,3, this paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 19 312417 1287030 A7 B7 Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed 5, Invention Description (20), 4'_Diphenyl f-ketotetracarboxylic dianhydride, bis(3,4-dicarboxyphenyl) dimethyl decane Diacetate, bis(3,4-dicarboxyphenyl)▼-phenyl phthalane dianhydride, bis(3,4,dicarboxyphenyl)diphenylnonane dianhydride, 1,4-bis(3,4- Dicarboxyphenyldiylphenylindenyl)phthalic anhydride, 1,3_bis(3,4-dicarboxyphenyltetramethyldicyclohexanone dianhydride 2,2-bis(3,4-diphenylene) Hexafluoropropane dianhydride, 2,2·double £4-(3,4-dicarboxyloxy)benzyl]hexafluoropropane dianhydride, 2,2-bis[4_(3,4-diwei) Tetraphthalic acid dianhydride such as phenoxy)phenyl]propane dianhydride or 4,4-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride, and reactive acid derivatives thereof Among them, 3, 4, 3, 4, and 2, The tetracarboxylic dianhydride or the bis(3,4-dicarboxyphenyl) ether dianhydride is preferably used in combination of two or more kinds of the above tetracarboxylic acids or reactive acid derivatives thereof. The (c,) organic solvent is not particularly limited, and examples thereof include nitrogen-containing compounds such as N-methylpyrrolidone and dimethylacetamide, bis-methylmethylguanamine, and cyclobutane, dimethyl amide. Sulfur-containing compounds such as maple, 7-butyrolactone, _-valerolactone, r-caprolactone, 7-heptanolactone, α-acetyl-r-butyrolactone, ε-caprolactone and the like Ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, acetophenone, ethylene glycol, glycerol, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, two Ethylene glycol dipropyl ether, diethylene glycol dibutyl _, triethylene glycol dimethyl ether, triethylene diether diethyl ether, triethylene glycol dipropyl ether, triethylene glycol dibutyl ether, tetraethylene glycol Dimethyl ether, tetraethylene glycol diethyl ether, tetraethylene diether dipropyl ether, tetraethylene glycol dibutyl _, diethylene glycol methyl ether, diethyl ether monoethyl ether, triethylene glycol monomethyl ether, three Ethylene glycol monoethyl ether, tetraethylene glycol monoterpene _ Tetraethylene glycol monoethyl ether, etc. _ class. (C') The amount of organic solvent, for the total amount of resin 1 〇〇 by weight --- (Please read the back of the note on this page).. Line. This paper scale applies to China National Standard (CNS) A4 Specification (210 X 297 mm 312417 1287030 Ministry of Economic Affairs Intellectual Property Bureau Consumer Co., Ltd. Printed A7 V. Invention Description P) Goodly 100 to 3 500 parts by weight, more preferably 15 to 1 part by weight. In the present invention, when a polyether amidoximine or a polyether decylamine is obtained, the tetracarboxylic acid or a reactive acid derivative thereof is preferably used in an amount of from 〇j to 90 mol% for the total amount of the diamine component, and is preferably used. 0·1 to "〇莫耳〇/〇. In the present invention, when the polyether oximine is obtained, the tetracarboxylic acid or its reactive acid derivative is preferably used in an amount of from 8 to 2 mol%, more preferably from 90 to 180 mol%, based on the total amount of the monoamine component. . In the present invention, the acid compound formed by the above dicarboxylic acid or a reactive acid derivative thereof and tricarboxylic acid oxime or a reactive acid derivative thereof, alone or in combination, is preferably used in an amount of from 8 to 14 for the total amount of the diamine compound. 〇莫耳0/〇, better use 9〇 to 120mol%. When the acid compound is used in an amount equivalent to the total amount of the diamine compound, the compound having the highest molecular weight tends to be obtained. In the present month, the above-mentioned monodecanoic acid or its reactive acid derivative, Pantraic acid or its reactive acid derivative, alone or in combination, and the general formula (π) read acid dianhydride or its reactive acid-derived yang In combination with the acid compound formed, it is preferred to use 8 to 14 mole % for the total investigation of the diamine compound, and more preferably 9 to 120 mole %. When these acid compounds are used in the total amount of the diamine compound, there is a tendency that the compound having the highest molecular number is found. In the present invention, a known method in which a diamine component and an acid component are reacted can be used for the synthesis, and a known method is used without particular limitation. The reaction is carried out in an organic solvent, such as Νmethylpyrrolidone, dimethylacetamide, dimethylformamide, and keto-3,4,5,6-tetraar-2 ( 1Η)-pyrimidine_,1>3_dimethyl-2-imidazolidin nitrogen-containing compound 'cyclobutene code, dimethyl hydrazine, etc. containing sulfonate' ____ r • Ding paper size applicable to Chinese national standards (cns ) a4 A 21 312417 -b-----I--I----- (Please read the note on the back first to write this page) A 5J· 1287030 A7 B7 V. Description of the invention (22 丁肉酉曰, r-heptanolactone, α _ acetyl group _ 7 - butane I 曰, e - 己内酷 笠 酉曰, methyl ethyl methyl _, methyl isobutyl dimethyl ketone: ketone, stupid B- and other ketones, ethylene glycol, glycerol, =; r, diethylene glycol di-mystery, diethylene glycol dipropylene, diethylene glycol monobutyl ether, triethylene glycol dipropyl _, Triethylene glycol dibutyl, di-, triethylene glycol diether, tetraethylene, -,,,, tetraethylene glycol dimethyl ether, tetraethylene glycol, diacetyl, tetraethylene diether, dipropylene , tetraethylene glycol dibutyl mystery, diethylene glycol monomethyl bond, monoethylene ether monoethyl ether, triethylene glycol - formazan, tetraethylene Phenols such as diethylene glycol monoethyl ketone and tetramethyl phenol, 6 acid rrs... cresol - ^ ^ 曰乙丁丁, ethyl cellosolve ethyl ester (solvent, toluene, xylene, diethyl Tobacco such as benzene and cyclohexane, three gases, such as sulphur, tetrachloroethane, methane, sulphur, chlorobenzene, etc. These solvents can be used alone. These reactions can be used in combination in the above organic solvent with a diamine compound and an acid compound at -78 phantom 0 (rc, preferably, to (10). In this reaction, a total of one amine compound can also be added. The inorganic acid accepting agent is in an amount of from 9 to 4 mol%. The inorganic acid accepting agent may, for example, be a tertiary amine such as triethylamine, tripropylamine, tributylamine, triamylamine or pyridine, propylene oxide, Phenyl oxirane, 1,2-epoxide, etc. such as hexylene oxide. As the reaction progresses, the reaction solution will slowly increase in viscosity, and at this time, it will be formed as a polyether amidoxime precursor. Polylysine. The polylysine is ruthenium imidized via a dehydration ring to obtain a polyether amidoxime. The dehydration ring is heat treated at 80 to 4 art. Thermal closed-loop method for reaction, chemical closed-loop method for dehydration using dehydrating agent, etc. This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 public) 22 312417 1287030 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative prints A7 5. Description of the invention (23) The thermal closed-loop method is preferably carried out by removing the water formed by the dehydration reaction outside the system. At this time, the reaction liquid is at 80 to 400 ° C, preferably 1 to 25 ° C. Heating is carried out. At this time, a solvent such as benzene, toluene or xylene which is azeotroped with water may be used in combination to azeotropically remove water. The chemical ring closure method is carried out in the presence of a chemical dehydrating agent at a temperature of from 12 Torr to preferably from 1 Torr to 80 °C. As the chemical dehydrating agent, an acid anhydride such as acetic anhydride, propionic anhydride, butyric anhydride or benzoic anhydride, or a carbodiimide compound such as dicyclohexylcarbodiimide is preferably used. In this case, it is preferred to use a cyclization reaction which promotes the cyclization reaction of 疋, isoquine, dimethylamine, diethylamine, amine Q, and ρ. The chemical dehydrating agent is used in an amount of from 9 600 to 600 mol% for the total amount of the diamine compound, and the substance which promotes the cyclization reaction is used in an amount of from 40 to 300 mol% based on the total amount of the diamine compound. Further, a dehydration catalyst such as a triphenyl phthalate, a tricyclohexylphosphonium phosphate, a dibasic acid-filled acid, a phthalic acid or a phosphorus pentoxide such as a boron compound such as boric acid or boric anhydride may be used. The reaction solution obtained by the dehydration reaction is compatible with the above organic solvent such as a lower alcohol such as methanol, water or a mixture thereof, and a large excess amount is added to a solvent in which the resin is a weak solvent, and a precipitate of the resin can be obtained. The polyether amidoximine of the present invention is obtained by filtering the precipitate and drying the solvent. The polyether oximine in the present invention can be obtained by the same synthesis method as the polyether amidoxime. The polyether amidoxime or polyether decylamine which is soluble in a polar solvent at room temperature obtained by the above method and insoluble in a polar solvent at room temperature, but can be heated by heating/polyamine amidoxime, poly The ether decylamine or polyether quinone imine is not particularly limited in any combination, and may be any compounding amount. For room temperature - l ·---------- installed - (please read the phonetic transcription on the back page) Book: This paper scale applies to China National Standard (CNS) A4 specifications (21〇 297 mm) 23 312417 1287030 A7 B7 Ministry of Economic Affairs, Intellectual Property Bureau, Consumer Cooperatives, Printing 5, Inventions (24) Total amount of polyether amidoxime or polyether-toxic amine resin dissolved in polar solvent 100 weight a portion, which is insoluble in a polar solvent at room temperature, 彳m but soluble in a polyether amidoxime imine, a polyether guanamine or a polyether to make a 25 boat ^ brother makeup is preferably 10 to 300 parts by weight, more It is preferably from 1 to 200 parts by weight. The resin composition of the present invention, that is, the polyether amidoxime amide or polyether decylamine which is soluble in a polar solvent at room temperature and obtained by the method of sulphur, gamma, and workmanship, and is insoluble in polar at room temperature. The method for producing the resin composition of the resin and the organic solvent, such as a polyether amidoxime, a polyether phthalamide or a polyether phthalimide, which are soluble in a solvent, is not particularly limited, for example, It can be dissolved in a paint of a solvent by dispersing a polyamine or a polyetheramine which is soluble in a polar solvent at room temperature, and is added to a polyether amidoxime which is insoluble in a polar solvent at room temperature but is soluble by heating. The imine, the polyether decylamine or the polyether quinone imine is heated at 5 Torr to 200 ° C to be uniformly dissolved and then allowed to cool, whereby a paste containing a resin composition of two kinds of resins can be obtained. The resin composition of the present invention is preferably one which contains a low elastic filler and/or a liquid rubber having rubber elasticity. The low-elastic filler or the liquid rubber having rubber elasticity used in the present invention is not particularly limited, and examples thereof include fillers of elastomers such as acrylic rubber, fluorine rubber, silicone rubber, and butadiene rubber, or the like. Rubber, etc. In view of the heat resistance of the resin composition, ruthenium rubber is preferred. Further, it is preferred that the filler be chemically modified with a cyclic cyano group. A modifier in which an epoxy group is substituted with a functional group such as an amino group, a propenyl group, a vinyl group or a phenyl group can be used. By adding these low-elastic fillers to the resin composition or the heat-resistant thermoplastic resin, the elastic paper size can be adjusted without any loss of heat resistance and adhesion (10) X 297 mm) 24 312417 ( Please read the note on the back first --- write this page) - Line - 25 1287030

Low, and controllable elastic modulus The resin composition of the present invention _ the surface of the chemically modified rubber elastic low elastic filler preferably has an average particle diameter of (M to 5 - spherical % amorphous microparticles) If the average grain yield is less than @^ @, there will be agglomeration between the particles, which tends to be difficult to disperse sufficiently. Moreover, if it exceeds 50#m, the surface of the coated sputum is rough, and it is difficult to make a uniform coating film. L. In the resin composition of the present invention, the amount of the rubber-elastic low-level filler which is chemically modified on the surface is preferably from 5 to 900 parts by weight based on 100 parts by weight of the total amount of the aromatic thermoplastic resin. More preferably, it is used in an amount of from 5 to 800 parts by weight. In the present invention, when the rubber-elastic low-elastic filler having a chemically modified surface is used as the rubber, the modulus of elasticity can be controlled to be in the range of 0.2 to 3.0 GPa. 'The elastic modulus at 15 〇t is within 10 to 1% of the value of _65 C. When it is fabricated as a semiconductor device, it is evaluated as a reliability of -551 to 15 〇. It becomes effective during the temperature thermal cycle test The characteristics of the glass transition temperature are § § 18 (rc or more, heat; | decomposition temperature is 30 (TC or more can maintain heat resistance, become a low-elasticity tree fat-removing composition. 2 resin composition in the present invention, That is, the polyether amidoxime or polyether guanamine which is soluble in a polar solvent at room temperature according to the above method, and the polyether guanamine which is insoluble in a polar solvent at room temperature but is soluble by heating. Two kinds of resins, such as yg imine, polyether amide or polyether phthalimide, resin composition with low elasticity, filler and organic solvent, can be applied to Chinese national standards on the scale of aromatic thermoplastic paper ( CNS) A4 specification (210 X 297 public love f ' ----- 312417

1287030 A7 ^ -----——---__ _ V. Inventive Note P ) ^ ^ ^ ' = Low-elastic filler is added to the moon, (4) Kay machine, three rollers, ball, comet mixer A dispersing machine such as a dispersion n or a homogenizer is kneaded and transferred to obtain a resin composition. -L---------------- (Please read the phonetic on the back first? Things ^|| Write this page) Coloring agents and coupling agents can also be added to the resin composition of the present invention. Adding: agent, resin modifier. Examples of the colorant include carbon black, a dye, a pigment, and the like. Examples of the coupling agent include (4) a salt-based coupling agent, a money-based coupling agent, a titanate-based coupling agent, and a thio-based coupling agent. The above additive is preferably used in an amount of 50 parts by weight or less based on the total amount of the aromatic thermoplastic resin. Next, the heat resistant resin paste of the present invention will be described. The heat-resistant resin of the present invention may be a paste obtained by smearing the above resin composition, but the following paste is preferred. That is, the heat-resistant resin paste of the present invention contains (A") a heat-resistant resin a, which is dissolved in a (C,) solvent at room temperature and at the time of heat drying, and (B) is at a standstill. (c) solvent, heat-resistant resin B which is soluble at the time of heat drying, and (C) solvent C and the Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative print (D) show rubber elastic particles or Liquid material d Further, the heat-resistant resin paste of the present invention contains (A,,) heat-resistant resin A, and (B") heat-resistant resin B'' as aromatic tetra-retensive dianhydride and aromatic two The aromatic polyimine resin obtained by the reaction of the amine, and the component of the rubber elastic particle of (D) which is the main component of the rubber elastic is preferably an anthracene rubber. Further, the heat resistant resin paste of the present invention has heat resistance of (B,,). Resin B, which is a 3,4,3',4'-benzophenone tetracarboxylic dianhydride containing 50% molar or more, is applicable to China National Standard (CNS) A4 specification (210 X 297 mm). 26 312417 1287030 A7 B7 V. Description of invention 疒) Group of four acid dianhydrides, with 4,4,_ containing more than 50% Mo Amino diphenyl ether aromatic diamine = square obtained from reaction of an aromatic polyimide-based resin, (c ") of the master; valley agent is 7 * - g-butyrolactone are ideal purpose. In the present invention, (A,) is a heat-resistant resin wax which is dissolved in a (C,) solvent at a temperature at room temperature and during heat drying, and a heat-resistant resin paste film is formed by screen printing or the like. When heat drying is carried out to form a case, it is possible to form a phase-matching phase with the heat-resistant resin B of (B,,) after the addition of (4). That is, it is preferable that the temperature can be sufficiently dissolved in the solvent at the time of heat drying, and the temperature at the time of heat drying can be sufficiently compatible with the heat resistant resin B. Specifically, it is preferred to use a heat resistant resin having a mercaptoamine group, a quinone group, a vine group or a base. Further, specifically, it is a polyimine resin, a polyamide amine resin, a polyamine resin, a polyester resin, a polynuclear resin or the like. As the polyimine resin and the polyamidoximine resin, a resin which is partially imidized by polyamidic acid or polylysine as the precursor may also be used. In consideration of heat resistance, the heat-resistant resin a" of (A") has a 5% thermal weight reduction temperature of 30 (TC or more is preferable. If it is less than 3 〇 (rc, then 1 high 1 || heat treatment step) For example, there is a tendency to generate external gas when the solder ball is loaded, and the tendency of the semiconductor device to obtain reliability of the semiconductor device 1 11 Considering the ease of synthesis, heat resistance, and preservation stability of the paste, it is more difficult to use the polyimide resin. Ideally, the aromatic polyamidiamine type cellulite (for example, the polymerization of the aromatic tetracarboxylic dianhydride and the aromatic diamine), the polyglycolic acid, and the polyphosphonium amide are imidized. Polyimine, etc.) is particularly desirable. In the present invention (B,,) is insoluble at room temperature (C 勹 solvent, in the application of capital paper scale applicable Chinese National Standard (CNS) A4 specification (2) 297 297 public " 27 312417

--------- Pack (please read the back >8 note ^5 matters · write this page) Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed 1287030 V. Invention description p ) | The heat-resistant resin B" which is soluble in temperature is used for denaturation. 疋In order to impart a poor agent, although the heat-resistant resin A of (A") is used, it is used in 々|榭/皿] Further, the heat-resistant resin of (B) is used as a resin which is insoluble in (C,,) solvent from the 丨>, but the two are subjected to heat drying; the properties of the respective solvents. The heat resistance of the heat-resistant resin A (盥) of (A) is from the viewpoint of the uniformity of the film obtained by adding the heat-resistant resin paste of this (4) to the mechanical properties of the film. The resin B" has a compatible phase after heating and drying, and the heat-resistant resin |B" of the heat-resistant resin ("A") of the heat-resistant resin (B) is preferably formed after heating and drying. The homogeneous phase may further contain a residual organic solvent after heat drying. The heat resistant resin B" of (B") is preferably a heat resistant resin having a mercaptoamine group, an oxime imide group, an ester group or an ether group. The heat resistant resin is preferably a polyimine resin or a precursor thereof, a polyamidoximine resin or the precursor or a polyamide resin from the viewpoint of heat resistance and mechanical properties. Or a precursor thereof, a polyamidamine oxime amine resin or a precursor thereof or a polyamide resin thereof, which is a polyimine resin or a ruthenium ruthenium resin thereof, a polyamidoximine resin or a precursor thereof Or use in polyamine resin. Also, each cockroach can also be a poly-branched acid. The acid-imidized resin (that is, the heat-resistant resin B" of (B") is selected from the group consisting of a fine particle state and being insoluble before being dried by heating in the (C") solvent of the heat-sensitive resin paste of the present invention. . 312417

28 1287030 A7 B7 V. OBJECTS OF THE INVENTION (29) The specifics of the heat-resistant resin B" of the above (B") (including the combination with the solvent I) can be exemplified in JP-A-246777. The (π)|heat-resistant resin Β specific resin of the specific example, or 34_I benzophenone tetracarboxylic dianhydride / 4,4,-diaminodiphenyl ether (1/1 •• Moerbi) | Polydecanoic acid (solvent is r_butyrolactone), 3,3,,4,4,_biphenyltetracarboxylic dianhydride / |3,4,3',4'-diphenyl Methyl ketone tetracarboxylic acid dianhydride / 4,4,-diaminodiphenyl ether (〇5 | / 〇 · 5 / 1 ; Mo ratio) poly-proline (solvent is butyrolactone) and the like. These are examples of the embodiments of the present invention, and the present invention is not limited to the examples. The page considers (C") the stability of the solvent, the heat-resistant resin β of (Β), and the solubility and productivity of the solvent (,), which is (耐热)) Contains 50. /3,4,3,,4,_dibenzidine tetracarboxylic dianhydride of aromatic tetracarboxylic dianhydride and 4,4,diaminodiamine containing 50% or more An aromatic polyimine resin obtained by reacting an aromatic diamine of a phenyl ether, (c. a solvent is a combination of 7" - butyrolactone. The heat drying temperature of the heat resistant resin paste of the above combination is usually From 5 〇 to 350 C, it is reasonable to raise the temperature from the low temperature to the high temperature in this range. Further, the heat resistant resin B" using CB") and the heat resistant resin A" of (A") have phases. The nature of the solution is ideal. Specifically, the difference between the solubility parameters of the heat-resistant resin B" of (B") and the heat-resistant resin A" of (A") is preferably 2.0 or less, and more preferably the following composition. The solubility parameter here is the value calculated based on the method disclosed in P〇lym_Eng.Sci., vol l4, pages 147 to 154 [unit. 1 paper size suitable for national standard (CNS) A4 specifications (10) 297 297 liters) 29 312417 1287030 A7

V. INSTRUCTIONS (30) The Ministry of Economic Affairs, Intellectual Property Office, Staff and Consumers Cooperative, printed and manufactured. The aromatic tetracarboxylic dianhydride used in the heat-resistant resin of the present invention has pyromellitic dianhydride, 3,3', 4, 4' -biphenyltetracarboxylic dianhydride, 2,2,3,3,_biphenyltetracarboxylic dianhydride, 2,3,3',4,biphenyltetracarboxylic dianhydride, 2,2-dual ( 3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane Anhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)methane Anhydride, bis(3,4-dicarboxyphenyl) dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, bis(3,4-di-(phenyl)- dianhydride Benzene-1,2,3,4 _ tetra-rebel dianhydride, 3,4,3,,4,_benzophenone tetracarboxylic dianhydride, 2,3,2,,3,_benzol Ketotetracarboxylic dianhydride, 2,3,3',4'-dibenzophenone tetracarboxylic acid dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7_ Naphthalenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, i,4,5,8-naphthalenetetracarboxylic dianhydride, 2,6-di-naphthalene-1,4,5 , 8, tetracarboxylic acid Anhydride, 2,7-di-naphthalene-1,4,5,8-tetrazoic acid dixanthine, 2,3,6,7-tetrachloronaphthalene-1,4,5,8·tetradecanoic acid diif, Phenanthrene-1,8,9,10-tetraweileric dianhydride, bis(3,4-diphenylene)dimethyl oxalate dianhydride, bis(3,4-dicarboxyphenyl)methylbenzene Base phthalic anhydride, bis(3,4-dicarboxyphenyl)diphenylnonane dianhydride, 1,4-bis(3,4-dicarboxyphenyldimethylformamido) methicone, 1, 3_bis(3,4-diweiphenyl)_ΐ, ι,3,3·tetramethyldicyclohexanone dianhydride, p-phenyl bis(trimellitic acid monoester anhydride, 2,2-double (3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]hexafluoropropane dianhydride, 2,2-double [ 4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, 4,4-bis(3,4-dipropionyloxy)-phenyl sulfide diano, iota, 4_bis ( 2-based hexa- isopropyl) benzene bis(trimellitic anhydride), 1,3-bis(2-hydroxyhexafluoroisopropyl)benzene bis(trimellitic anhydride), 1,2-(vinyl) bis(trimellitic) Acid dianhydride), iota, 3-(cyclopropane) bis (terephthalic acid S dianhydride), 1,4-(cyclobutane) bis (trimellitic acid) paper The scale applies to the Chinese National Standard (CNS) A4 specification (210 X 297 public interest) (please read the note on the back II I. Install---write this page). 30 312417 1287030 A7 V. Description of invention (31) Anhydride) I,5 (cyclopentane) bis(trimellitic phthalate dianhydride), 1,6-(cyclohexane) bis(p-benzoic acid i phthalic anhydride), i,7-(cycloheptane) double (trimellitic phthalate dianhydride), 1,8_ (cyclooctane) bis (p-triester dianhydride),! , 9_(cyclodecane) bis(trimellitic phthalate dianhydride), Μ〇_(cyclopentane) bis(trimellitic phthalate dianhydride), —(cyclododecane) bis(trimellitic acid) Ester dianhydride), Μ6-(cyclohexadecane) bis (trimellitic acid two needles), $ ($18 octasole) bis (metaphthalic acid acetal dianhydride), etc., which can be used alone' It can also be used in combination of 2 or more types. The above-mentioned aromatic tetracarboxylic dianhydride may be used in a range of not more than 50% by mole of the aromatic tetracarboxylic dianhydride for tetracarboxylic dianhydride other than the aromatic tetracarboxylic dianhydride. Examples of the tetraphthalic acid dianhydride include ethylene tetracarboxylic dianhydride, tetra-butane tetracarboxylic dianhydride, pyrazine-2,3,5,6-tetracarboxylic dianhydride, and thiophene-2,3. 4,5_tetracarboxylic acid monophthalic anhydride decalin-1,4,5,8-tetradecanoic acid dianhydride, 4,8-dimethyl q 2 3 5,6,7-hexahydronaphthalene_1, 2,5,6-tetracarboxylic dianhydride, cyclopentane_1,2,3,4-tetracarboxylic dianhydride, pyrrolidine-2,3,4,5·tetracarboxylic dianhydride' 1,2 , 3,4-cyclobutane tetracarboxylic dianhydride, bis(exo-bicyclo[2.2.1]heptane-2,3-dicarboxylic anhydride) code, bicyclo[2 2.2]octyl(7)-ene _2,3,5,6-tetracarboxylic dianhydride, 5-(2,5-dioxotetrahydrofuranyl)-3-methyl_3_cyclohexene_ι,2-dicarboxylic anhydride, tetrahydrofuran 2, 3, 4 Hong tetracarboxylic dianhydride and the like. In the present invention, the acid anhydride used in the heat-resistant resin a" of (A") is made of 1,4-bis(2-hydroxy-6) from the viewpoint of not impairing heat resistance and obtaining a resin film at a low drying temperature. Fluoroisopropyl) benzene bis(trimellitic anhydride), 13_bis(2-hydroxyhexafluoroisopropyl)benzene bis(trimellitic anhydride), 1,2·(ethylene) bis(p-diester dianhydride), 1,3 -(cyclopropane) bis(trimellitic phthalate dianhydride), hydrazine, 4 _ (cyclobutane (please read the note on the back first. d. - f write this page). Printed by the Intellectual Property Office of the Ministry of Economic Affairs The paper scale applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm). 31 312417 1287030 A7 B7 V. Description of invention (32) 'Alkane' bis(trimellitic phthalate dianhydride), 1,5-(ring Pentane) bis(trimellitic phthalate dianhydride), 1,6-(cyclohexane) bis(trimellitic phthalate dianhydride), L7-(cycloheptane) bis (trimellitic phthalic anhydride) ), 1,8_(cyclooctane) bis(trimellitic phthalate dianhydride), i,9-(cyclodecane) bis(trimellitic phthalate dianhydride), 1,10-(cyclopentane) double (trimellitic phthalate dianhydride), 1,12-( Dodecane) bis(trimellitic phthalate dianhydride), l5l6_(cyclohexadecane) bis(trimellitic phthalate dianhydride), 1,18-(cyclooctadecane) bis(trimellitic acid ester) Dibenzoic acid esters such as dianhydride are preferred. The aromatic diamine is, for example, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 3,3,-diaminodiphenyl ether, 4,45-diaminodiphenyl ether, 3 ,4,-Diaminodiphenyl ether, 3,3'-diaminodiphenylmethane, 3,4,-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane , 3,35-diaminodiphenyldifluoromethane, 4,4'-diaminodiphenyldifluoromethane, 3,3'-diaminodiphenyl maple, 3,4,-diamine Diphenyl maple, 4,4'-diaminodiphenyl hydrazine, 3,3, diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 4,4'-diamine Diphenyl sulfide, 3,3'-diaminodiphenyl ketone, 3,4,-diaminodiphenyl ketone, 4,4'-diaminodiphenyl ketone, 2,2- Bis(3-aminophenyl)propane, 2,2-(3,4,-diaminodiphenyl)propane, 2,2-bis(4-aminophenyl)propane, 2,2-double (3-aminophenyl)hexafluoropropane, 2,2-(3,4'-diaminodiphenyl)hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, 1,3·bis(3-aminophenoxy)benzene, 1,4-bis(4-dibenzylphenoxy)benzene, 3,3'-[1,4-phenylenebis(1-A) Ethyl fork)] diphenylamine, 3,4'-[1,4-phenylenebis(1-methylethylidene)]diphenylamine, 4,4'-[1,4-phenylenebis(1_methyl) Ethyl)) bisaniline, 2,2-bis[4-(3-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane L- ----------Install·-- (Please read the note on the back first to write this page). The Ministry of Economic Affairs, Intellectual Property Bureau, Staff and Consumer Cooperatives, printed Thai paper scale, applicable to China National Standard (CNS) A4 specification ( 210 x 297 mm) 32 312417 1287030 A7 B7 V. INSTRUCTIONS (33) Burned, bis[4-(3-aminophenoxy)phenyl] sulfide, bis[4-(4-aminophenoxy) Phenyl]sulfide, bis[4-(3-aminophenoxy)phenyl] code, bis[4-(4-aminophenoxy)phenyl] code, 1,2-diamine 4-carboxybenzene, 1,3-diamino-5-carboxybenzene, 1,3-diamino-4-carboxybenzene, 1,4-diamino-6-carboxybenzene, 1,5- Diamino-6-carboxybenzene, 1,3-diamino-4,6-dicarboxybenzene, 1,2-diamino-3,5-di-sulfobenzene, 4-(3,5-di Aminophenoxy Benzoic acid, 3-(3,5-diaminophenoxy)benzoic acid, 2-(3,5-diaminophenoxy)benzoic acid, 3,3-dicarboxy-4,4'-diamine Biphenyl, 3,3'-diamino-4,4'-dicarboxybiphenyl, 2,2-bis(4-carboxy-3-aminophenyl)propane, 2,2-dual (4_ Carboxy-3-aminophenyl)hexafluoropropane, bis(4-carboxy-3-aminophenyl)methanone, bis(4-carboxy-3-aminophenyl) sulfide, bis(4-carboxyl) 3-aminophenyl)-, bis(4-carboxy-3-aminophenyl) code, bis(4-carboxy-3-aminophenyl)methane, 4-[(2,4-diamine) 5-(pyrimidinyl)methyl]benzoic acid, p-(3,6-diamino-S.tricin-2-yl)benzoic acid, bis(4-carboxy-3-aminophenyl)di Fluoromethane, 2,2-bis(4-amino-3-carboxyphenyl)propane, 2,2-bis(4-amino-3-carboxyphenyl)hexafluoropropane, bis(4-amino- 3-carboxyphenyl)one, bis(4-amino-3-carboxyphenyl) sulfide, bis(4-amino-3-carboxyphenyl)ether, bis(4-amino-3-carboxybenzene) , bis(4-amino-3-carboxyphenyl)methane, bis(4-amino-3-carboxyphenyl)difluoromethane, 1,2-diamino-4-hydroxybenzene, 1 , 3 -diamino-5 - Benzobenzene, 1,3 -diamino-4-transphenyl, 1,4-diamino-6-hydroxybenzene, 1,5-diamino-6-hydroxybenzene, 1,3-diamine -4,6 dihydroxybenzene, 1,2-diamino-3,5-dihydroxy stupid, 4-(3,5-diaminophenoxy)phenol, 3-(3,5-diamino group Phenoxy)phenol, 2-(3,5-diaminophenoxy)phenol '3,3'-dihydroxy-4,4'-diaminobiphenyl, 3,3, diamino-4 , 4'-di-rebel biphenyl, 2,2-bis(4-hydroxy-3-aminophenyl)propane, 2,2-bis (4- this paper scale applies to China National Standard (CNS) A4 specification ( 210 X 297 mm) • l·------------ crack (please write this page first) · Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative print 33 312417 1287030 A7 B7 V. Description of the invention (34) transyl-3-aminophenyl)hexafluoropropane, bis(4-hydroxy-3-aminophenyl)one, bis(4-hydroxy-3-aminophenyl) sulfide, Bis(4-hydroxy-3-aminophenyl)ether, bis(4-carbo-3-aminophenyl) code, bis(4-3⁄4-yl-3-aminophenyl)methanone, 4- [(2,4-diamino]5-glycosyl)methyl] Benzine-p-(3,6-diamino-§-tris-2-yl)phenol, bis (4 -hydroxy-3-aminophenyl)difluoromethane, 2,2-bis(4-amino-3-ylhydroxyphenyl)propane, 2,2-bis(4-amino-3-hydroxyphenyl)hexa Fluoropropane, bis(4-amino-3-hydroxyphenyl)one, bis(4-amino-3-hydroxyphenyl) sulfide, bis(4-amino-3-hydroxyphenyl)ether, double (4-Amino-3-hydroxyphenyl) code, bis(4-amino-3-hydroxyphenyl)methane, bis(4-amino-3-hydroxyphenyl)difluoromethane, (please read first) Note on the back of this page) i Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing

(CF2)20(CF2)50(CH2)i

OH NH OH 2 <〇TM〇Λ (CF2)2OCF2CFO(CF2)20CFCF2O(CF2): CF3 CFa {CF^20(CF^20(CF^20(CF^20(CF2y τ

OH nh5

OH NH., etc., these may be used in combination of 2 or more types. The diamine compound in the production of the polyimine-based resin may be used in addition to the above-mentioned aromatic diamine, for example, 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diamine. Butane, 1,5-diaminopentane, 1,6-diaminohexane, iota, 7-diaminoheptane, 1,8-diaminooctane, 1,9-diamine Base decane, 1,1 〇 _ two paper scales applicable to China National Standard (CNS) A4 specifications (210 x 297 mm) 34 312417 1287030 Ministry of Economic Affairs Intellectual Property Bureau employees consumption cooperatives printed five, invention description (35 amine Kwai, 1,11-diamino + 栌, 1,3_bis(3-aminopropyl)tetramethyl oxime, calcined 1,3 bis (3-aminopropyl) tetramethyl A diamine compound other than an aliphatic diamine or a diamine (tetra) oxy-aromatic diamine, such as a polyoxyalkylene, is preferably used in the total amount of the mono-amine compound from the viewpoint of heat resistance. 50% by weight or less. When the polyimine resin used in the present invention is used, the aromatic tetra-retensive dianhydride and the diamine compound are reacted in almost the same molar concentration, and the film characteristics are ideal. End point The polymethylene imine resin of the desired molecular weight, the molar ratio of the acid component to the amine component is preferably a slight excess (about !01 to 1.10), or is blocked as the end of the acid component and the amine component. For example, a dicarboxylic acid anhydride such as maleic anhydride, phthalic anhydride or tetrahydrobenzene monocarboxylic anhydride, a tricarboxylic acid monoanhydride such as trimellitic anhydride, an amine such as aniline or a lower amine, and any one of an acid component or an amine component. The ear 'preferably used is 0.01 to 〇10 mol. The molecular weight of the polyimine resin used in the present invention is preferably 5,000 to 80,000 in terms of number average molecular weight. If it is less than 5 Å, the mechanical properties tend to decrease. If it exceeds 8 〇, 〇〇〇, there is a tendency that the viscosity of the solution in the synthesis is excessively increased and the workability is lowered. The number average molecular weight is a gel permeation chromatography method based on polystyrene having a known molecular weight as a calibration curve. The obtained polystyrene-converted value can be measured according to the following conditions. The following examples were measured according to the following conditions: Apparatus · Hitachi 655A type column: Gelpak GL- manufactured by Hitachi Chemical Co., Ltd. S300, the paper scale applies to Chinese national standards (CN-specification (21G x 297 public meals) (please read the note on the back to write this page) Binding: 1287030 A7 B7 V. Invention description (36) ^ ^ MDT-S ( 300mmx8mmp ) 2 eluents · tetrahydrofuran / dimethylformamide = 1 / 1 (capacity), H3PO4 (0.06 m / liter) / LiBr · Η 20 (0·03 m / liter) flow : 1 ml/min detector: UV (270 nm) The reaction of the aromatic tetracarboxylic dianhydride with the diamine compound is carried out in an organic solvent. As the organic solvent, for example, N-methylpyrrolidone, dimethylthiamine, dimethylformamide, 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidine can be used. Nitrogen-containing compounds such as ketones, 1,3-dimethyl-2- oxolone, sulfur-containing compounds such as cyclobutyl and dimethyl sulfoxide, 7-butyrolactone, γ-valerolactone, 7 _ Lactones such as lactone, r-heptanolactone, α-acetyl-r-butyrolactone, ε-caprolactone, dioxane, 1,2-dimethoxyethane diethylene glycol Dimethyl (or diethyl, dipropyl, dibutyl) ether, triethylene glycol dif (or diethyl, dipropyl, dibutyl) ether, tetraethylene glycol dif group ( Or an ether such as diethyl, dipropyl or dibutyl) ether, a ketone such as methyl ethyl ketone, formazan ketone, cyclohexanone or acetophenone, butanol, octanol or ethylene Alcohol, glycerol, diethylene glycol monomethyl (or monoethyl ether), triethylene glycol monomethyl (or monoethyl ether), tetraethylene glycol monomethyl (or monoethyl ether) Alcohols, phenols such as phenol, cresol, xylenol, ethyl acetate, butyl acetate, ethyl cellosolve acetate (cellosolve is a commodity) Name), esters such as butyl cellosolve acetate (solvent for commercial use), hydrocarbons such as toluene, xylene, diethylbenzene, cyclohexane, trichloroethane, tetra-ethane, mono-benzene, etc. Alizarinated hydrocarbons, etc. These may be used singly or in combination. In consideration of solubility, low hygroscopicity, low-temperature hardenability, and environmental safety, the use of lactones, ethers, and ketones is more appropriate than the Chinese National Standard (CNS) A4 specification (210 X 297 mm). 312417 fPlease read the note on the back first; N--- write this page) Order: Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed 1287030 A7 ------------ mutual 7 five , invention description (37) ^ " ideal. The reaction temperature is usually 8 (TC or less, preferably 〇 to 6 (rc is carried out. As the reaction is more 'reaction, the liquid is slowly 増#. At this time, a polyamine which is a precursor of the polyimide imine resin is formed. The polyimine resin can be obtained by subjecting the above reactant (polyimine precursor) to dehydration ring closure. The dehydration ring closure can be used up to 25 Torr. The heat treatment method (thermal imidization) or the use of a dehydrating agent can be used. The method to be carried out (chemical iodization). The heat treatment is carried out at 120 to 250 ° C, and it is preferred to remove the water formed by the dehydration reaction to the outside of the system. In this case, benzene, toluene, or the like may be used. The azeotropic removal of water by xylene, etc. The dehydration ring closure method using a dehydrating agent is preferably carried out using a saponin compound such as dicyclohexylcarbenium imine or the like. In this case, if necessary, 13 bis-isoquinoline can also be used. Dehydration catalysts such as dimethylamine, amine π hydrazine, and miso. Dehydrating agents or dehydration catalysts are preferably used in the range of 1 to S mole for the aromatic tetracarboxylic dianhydride 1 mole. To reduce the manufacturing steps. Number, improve economy, at 12〇 The method of heat treatment from °c to 250 C (thermal imidization) is preferred. The polyamidoximine resin of the present invention or a precursor thereof may be produced from the above-mentioned polyimine resin or its precursor. Part or all of the tetracarboxylic dianhydride is produced by substituting a trivalent tricarboxylic anhydride of a benzoic anhydride derivative such as trimellitic anhydride or a trimellitic anhydride chloride or the derivative. The diamine is produced by substituting an aromatic diisocyanate. The aromatic diisocyanate which can be used is a compound obtained by reacting the above aromatic diamine with carbon helium or gasified hydrazine gas. Phonetic? Matters written on this page) Order · Ministry of Economic Affairs Intellectual Property Bureau employees consumer cooperatives printed this paper scale applies China National Standard (CNS) A4 specifications (210 x 297 mm), -- 37 312417 1287030

Ministry of Economic Affairs, Intellectual Property Bureau, Staff Consumers Co., Ltd. Printing 5, Invention Description (38) The polyamidimide resin in the present invention uses aromatic tetracarboxylic acid dioxins and diisophthalic acid as an essential component. The polyamidoximine resin obtained by the reaction of the amine compound is preferred. The above compounds can be used as the diamine compound other than the aromatic tetracarboxylic acid dianhydride and the dioxonium isophthalate. The molar ratio of the diamine compound is preferably from 1 to 1% by mole. Since the resin paste of the present invention is used as an adhesive for a semiconductor device, it has resistance to a sealing material. The tendency of the solubility is lowered; if the content of the diterpene isophthalate is too large, the moisture resistance of the adhesive layer formed by the resin paste of the present invention tends to decrease, so it is preferably from 10 to 80 mol%. Preferably, it is 20 to 70 mol%. The polyamidoximine resin can be synthesized from a mixture ratio of an aromatic tetracarboxylic dianhydride and a diamine compound, an organic solvent used, a synthesis method, and the above polyimine resin. Obtained by the same operation The polyamine resin in the present invention may be an aromatic dicarboxylic acid such as terephthalic acid, isophthalic acid or phthalic acid, a derivative such as a dichloride or an anhydride, and the aromatic diamine compounded above. Or the aromatic diisocyanate is reacted and produced. The (C") solvent used in the present invention may be a solvent disclosed in the "Handbook of Solvents" (Kodansha, 1976), pages 143 to 852. For example, N-A can be used. Pyrrolidone, dimethylacetamide, dimethylformamide, 13-dimethyl-3,4,5,6-tetrahydro-2 (1H>pyrimidinone, 1,3_dimethyl-2_ A nitrogen-containing compound such as an imidazolidinone, a sulfur-containing compound such as cyclobutyl or dimethyl sulfoxide, 7-butyrolactone, r-valerolactone, r-caprolactone, r-heptanolactone, and ethyl hydrazine. L-butyrolactone, ε-caprolactone and other lactones, dioxane, Μ-dimethoxy acetonitrile paper size applicable to China National Standard (CNS) a4 specification (210 X 297 mm) 38 312417

(Please read the notes on the back of the J first - π write this page) Order: 1287030 A7 V. Description of invention (39), dibutyl) ether • l·---I--I------ (Please read the note on the back mil to write this page) Alkane, diethylene glycol dimethyl (or diethyl, dipropyl glycol dimethyl (or diethyl, dipropyl, dibutyl) Ethers such as ether 'tetraethylene glycol dimethyl (or diethyl, dipropyl, dibutyl) ether, carbonates such as ethylene carbonate 'propylene carbonate, methyl ethyl methyl ketone Isobutyl phthalate, cyclohexanone, phenylethyl ketone, etc., butanol, octanol, ethylene glycol, glycerol, diethylene glycol monomethyl (or monoethyl) ether, triethylene glycol Alcohols such as monomethyl (or monoethyl) ether, tetraethylene glycol monomethyl (or monoethyl ether), phenols such as phenol, cresol, xylenol, ethyl acetate, butyl acetate, and B Base cellosolve acetate acetate, butyl cellosolve acetate and other esters, hydrocarbons such as toluene, xylene, diethylbenzene, hexane, halogenated hydrocarbons such as 2 ethane, tetra-ethane, monochlorobenzene Etc. These can be used alone or in combination. The service life of the paste during screen printing, (C,,) solvent is preferably at least 10 (TC or more, more preferably 150 to 3 〇 (rc. - ###################################### C,,) Solvent to use a non-nitrogen-containing solvent such as r • butyl hydrazine, 丄 丄, ~ 卜知 / _ 戊内 g曰, γ _ caprolactone, 7 _ _ _ _ _ _ _ _ Slightly soil 7 Ding Nai Ri' ε-caprolactone and other lactones, dioxane, 1,2-dimethoxyethane, diethylene glycol dimethyl (or diethyl, dipropyl, Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed monobutyl) _, triethylene glycol dimethyl (or diethyl, dipropyl, dibutyl ether, tetraethylene glycol dimethyl (or diethyl, Dipropyl: ^-butyl) scales and other scales, vinyl acrylate, propylene carbonate and other carbon methyl ketone T-ethyl ethyl ketone, methyl: butyl ketone, ring, benzene, benzene The heat-resistant resin paste of the present invention may be prepared by mixing (A"), (B") heat-resistant resin B, and (c,) solvent, and cooling: (A,,) heat-resistant resin A" and (C,,)>? Add:: Dissolved paper size ^Fresh (CNS)^^(2)Q χ 297 public $ agent ♦ liquid analysis 39 312417 40 1287030 B7 V. Invention description (4〇) Dispersion (B,,) heat-resistant resin (B,,):::: The temperature is as long as it is (A") heat-resistant resin A, , : 2: thermal resin B" and (C,,) solvent The mixture can be made into two, which is not particularly limited, and is usually carried out under stirring; from ° to 250 c. It is preferably dissolved in U to 5 hours, more preferably in a small amount, and then heated to dissolve. The conditions for cooling the solution are not particularly limited as long as the resin B" is in the mixture of the heat-resistant resins A" and (c") of the (A") solvent, and the conditions of the second::=, precipitation, and dispersion. , through the temperature of the dissolution of less than 2 (rc to (10). c. It is ideal to place it for 1 hour to 6G under the falling of the sandalwood or standing still. For a short time, the cooling condition of the microparticles is under the condition of TC to 8 (the condition of placing 5 i 8G hours at a certain temperature of TC is preferable. From the heating dissolution temperature to A but to -m; to (10) The speed of c can be arbitrarily 'but it is easy to cool by rapid cooling: I precipitates the agglomerated particles, so it is usually cooled at a speed of ° to l ° c / min under stirring. Manufacture atmosphere to dry nitrogen It is preferable to carry out the heat-resistant resin which comprises the (B") in the solution of the heat resistant resin A" and (C") solvent of (A,). The raw material of B" is reacted at a temperature of the heat-resistant resin B" in which the (A") heat-resistant resin a" and (C,) solvent are dissolved (the heat-resistant resin B" which does not precipitate (B"), and is synthesized. (B") heat-resistant resin B" of 丨, and then heat-dissipating (B") heat-resistant resin b in a solution of (A") heat-resistant tree|fat A" and (C") solvent by cooling , and manufactured by the raw material of the heat resistant resin B" constituting (B") Use the above-mentioned paper size to apply the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 312417 f Please read the note on the back first. Write this page) Loading · !287030 Α7

礞 I I 41 41 312417 1287030 A7 V. INSTRUCTIONS (42) Rubber-elastic particles are added to the heat-resistant resin to control the modulus of elasticity without impairing the heat resistance and adhesion of the resin. Particles with rubber elasticity are available in the market for idling speed π] I, another fruit, and the company's trade name is Dreyfe E-601, Dreyfe E_6〇〇, etc., Shin-Etsu Chemical Industry ( The company's trade name is ketone rubber powder _£]^1>594, 〖MM%, shi ketone composite powder KMP-600, KMP-605 and so on. The resin film obtained from the heat-resistant resin paste in the present invention can be arbitrarily controlled to have a modulus of elasticity in the range of 0.2 to 3.0 GPa, and the modulus of elasticity at 15 〇r is 10 to 100% of the modulus of elasticity at _65 ° C. Resin paste is ideal. If it exceeds 3.0 GPa, the stress buffering is insufficient, and cracks may occur in the joint portion such as solder, which may impair the reliability. If it is less than 2 GPa, the wiring layer tends to be broken due to deformation. If the elastic modulus of TC is less than 10% of the elastic modulus of _65t, the solder ball joint portion or the like is likely to be deformed in the thermal shock cycle test, and the reliability tends to be lowered. In the present invention, the heat resistant resin paste is used. The obtained resin film is preferably a heat-resistant resin paste having a glass transition temperature of 180 ° C or more and a 5% weight loss temperature of 3 ° C or more. If the glass transition temperature is less than 180 ° C or 5% by weight, the temperature is not lowered. When the temperature is over 300 ° C, the resin tends to decompose during the sputtering process. In the present invention, the heat resistant resin paste preferably has a viscosity of 1 to 1, 〇〇〇Pa · s and a thixotropic coefficient of 1.2 or more. When the denaturation coefficient is 1.2 or more, good screen printing property is obtained. If the thixotropy coefficient is less than 1.2, sufficient printability and resolution tend not to be obtained. The thixotropy coefficient is preferably 2.0 to 10.0. .〇, the pattern formed has a tendency to blur. This paper scale applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm).

I

I Order # 42 312417 1287030 Ministry of Economic Affairs Intellectual Property Bureau Consumer Cooperatives Print A7 V. Invention Description (4 degrees viscosity is 10Pa · s to l, 〇〇〇pa · δ is ideal. Less than 1〇Pa · s is not easy to obtain When the film thickness and the resolution are sufficient, if the film thickness exceeds 1 〇〇〇Pa · s, the workability tends to decrease during pattern formation. It is more desirable from 5 〇pa · s to 700 Pa · s, and from 100 Pa · s to 60. 〇pa · s is the most ideal. The thixotropy coefficient is the number of revolutions lmijrl and lOmin measured using an E-type viscometer (made by Dechik Co., Ltd., EHD_u type), a sample volume of 0.4 g, and a measurement temperature of 25 t. -i is the ratio of apparent viscosity 0i to 0 1〇, expressed as π 1/?? 1〇. The apparent viscosity of the number of revolutions OJmiir1 is expressed as “〇5. The viscosity can be controlled by the solid concentration of the resin paste, ( The amount of the heat-resistant resin Β") is controlled. The larger the value, the greater the viscosity. The present invention is a heat-resistant resin which can be dissolved in a mixture by a temperature at room temperature and heat drying. A", (Β,,) is insoluble in solvent at room temperature, and the temperature is heated and dried. The elastic modulus of the resin film obtained by the combination of the heat-resistant resin B" and (D) showing the rubber elastic particle or the liquid material D can be arbitrarily controlled in the range of 0.2 to 3_0 GPa, and the elastic modulus at 15 〇t. At -65 ° (: 10 to 10% of the modulus of elasticity. The glass transition temperature of the resin film obtained from the heat-resistant resin paste of the present invention is 180 ° C or more, and the 5% weight loss temperature is 3 〇 or more, for The process of sputtering, plating resistance formation, electroplating or electroless plating, resistance stripping, thin film metal etching, solvent treatment, solder ball loading, etc. used in the fabrication of a semiconductor device is superior in resistance to the process of the present invention (A). Resin a,, (B,,) heat-resistant resin B,, (C") solvent and (D) showing the rubber elastic particle or liquid mixture ratio, for (A") heat resistance Resin A, 1 part by weight of (B,,) heat-resistant paper size suitable for wealth (33⁄4: grid X 297T11-^^--- (please read the back of the note before you fill out this Page) Clothing 1287030 A7

44 312417 1287030 A7 V. Inventive Note (d The crosslinking agent of the obtained functional group is added in an amount of 1 to 30 parts by weight based on the total amount of the heat-resistant resin paste. It has a chemical bond with a base group or a carboxyl group. The functional group-based crosslinking agent is reacted with a heat-resistant resin having two or more functional groups in the molecule of the compound, at least one of which has a hydroxyl group or a carboxyl group in the molecular main chain, and a residual functional group and the above molecule A heat-resistant resin having a hydroxyl group or a carboxyl group in the main chain is preferably reacted or reacted between the functional groups. The functional group is required to have two or more functional groups, and the molecular structure and molecular weight are not particularly limited. Examples of the reactive functional group include an epoxy group, an isocyanate group, a methyl saccharide group, etc., a carboxyl group-reactive functional group, an ethylene group, an oxetyl group, and the like. A siloxane group, an ethoxy group, and the like, a crosslinking agent which can be imparted to a cured product of a heat-resistant resin paste, and a coupling agent excellent in storage stability of a resin paste as a crosslinking agent The coupling agent is preferably a decane coupling agent, a titanate coupling agent, an aluminum coupling agent, etc. Among them, a decane coupling agent is more preferable. Examples of the decane coupling agent include r_(2-aminoethyl)amine. Propyl triheptyloxydecane, r-(2.aminoethyl)aminopropylmethyldimethoxydecane, soil: propyleneoxypropyl triinocyloxycyclohexane, butyl acrylate Oxy: group: methoxy money, rM propyl trimethoxy money, vinyl triethyl = I Shi Xixuan, 7 · anilinopropyl trioxyl, vinyl triline, plant Propyl f-based di-foxy money

丨甲... Oxygen Xixue a glycidoxypropyl tri-foxydipropyl I This paper scale is suitable for national standards (CNS) A4 specifications (2) Gx297 public ~ ~ a ^ 兀 7 312417 ---- I--------------t-----! (Please read the notes on the back and fill out this page) 45 1287030 46 A7 V. INSTRUCTIONS (46) - Urea-based Triethoxy decane, methacryloxypropyl methyl dimethoxy decane, and the like. For a heat-resistant resin having a hydroxyl group in the main chain of the molecule, it is preferred to use a decane coupling agent having an epoxy group and a methoxyalkyl group in the molecule, and further using r-glycidoxypropyltrimethoxydecane. ideal. The heat-resistant resin paste obtained by the combination has a relaxed crosslinked structure due to the heat-cured material, and is used in a resin-encapsulated semiconductor device, and is not dissolved in the encapsulating material constituting resin at the molding temperature of the encapsulating material, and is resistant to soldering. Excellent reflowability and high adhesion to semiconductor wafers or leadframes (especially thermocompression bonding). In the present invention, the aromatic thermoplastic resin which is insoluble in the polar solvent at room temperature but which is soluble by heating can impart thixotropic properties to the resin composition, and can form a precise pattern by screen printing and spray coating. In the present invention, the modulus at 25 ° C can be arbitrarily controlled in the range of 〇. 2 to 3.0 GPa, and 15 (the modulus of elasticity of rC is preferably in the range of 10 to 100% at an elastic ratio of -65 Ct. Among them, the glass transition temperature (Tg) is above l8〇r, and the thermal decomposition temperature is preferably above 300 ° C. The resin composition of the present invention has a viscosity in the range of 1 to 1 Q〇〇pa · s, When the denaturation coefficient is 1 or more, it is preferable to form a precise pattern. If the viscosity of the resin composition is less than 1 pa · s, it is difficult to maintain the shape of the resin composition at the time of printing, and the drawing of the resin composition is severe. In addition, if it exceeds 1000 Pa·s, the resin composition becomes hard, and the operation at the time of printing is extremely difficult, and it is difficult to form a fine pattern. The paper (CNS) A4 specification (2) 0 x 297 Meal 7 312417 Please read the back note first

Item I fill in 1287030 A7 B7 V. Invention description (,. The thixotropy coefficient is better in the range, better in the 15 to 15 consumption. If the thixotropy coefficient is less than 12, even if the precise pattern is formed, it will collapse. There is a tendency that a precise pattern is not easily formed. The method of obtaining a precise pattern using the resin of the present invention and the method of obtaining a resin film pattern by the persistent tree moon paste are not particularly limited, and examples thereof include a screen printing method and a spray coating method. , a flood casting method, a curtain flow coating method, a letterpress printing method, a gravure printing method, a lithography method, etc. A semiconductor device using the resin composition of the present invention or a semiconductor device using a resin film obtained from a weather resistant resin paste may be used. After the substrate or the lead frame is coated or adhered with the resin composition of the present invention or the heat resistant resin paste, the wafer is bonded. For example, the resin composition yarn of the present invention or the heat resistant tree sap: paste may be coated on the surface of the half (four) part. The resin composition or the heat-resistant resin paste may be coated or adhered to the surface of the wafer and adhered to the substrate or the lead frame. Drying can be carried out according to a known method. At this time, the coating film can be obtained only by a heating process of 250 ° C or less or a solvent drying process which is not accompanied by hydrazine imidization and is below 250 ° C. The glass transition temperature is § § 180. (: above, the thermal decomposition temperature is above 300 ° C, and has sufficient heat resistance. Moreover, since the elastic modulus of the coating film can be controlled within the range of 0.2 to 3. OGPa, it can be corresponding A semiconductor device using the resin composition of the present invention or a heat-resistant resin paste can be formed by coating and drying a semiconductor substrate having a plurality of identical structure wirings, and forming a resin composition or a heat-resistant resin paste of the present invention. a step of forming a resin layer; forming the above-mentioned semiconductor substrate on the above-mentioned resin substrate, applying the Chinese National Standard (CNS) A4 specification (210 X 297 mm) on the above-mentioned resin substrate. 47 312417 5. Electrode and electrical conduction of the invention (48) a step of rewiring; a step of forming a protective layer on the rewiring; a step of forming an external electrode joint on the protective layer; and then, if necessary, cutting The semiconductor substrate is not particularly limited, and examples thereof include a germanium wafer in which a memory circuit is formed, a germanium wafer in which a logic circuit has been formed, and the like. The method of applying the resin layer is not particularly limited. Printing or spray coating is preferred. In the present invention, the method of drying the resin layer can be carried out according to a known method. In this case, only a heating step of 250 ° C or less or a non-imidization and not more than 250 ° C is used. In the solvent drying step, a resin layer can be obtained. According to this, the resin layer can be formed without damaging the substrate on which the wiring has been formed. The formed resin layer has a glass transition temperature Tg of 18 〇 ° C or higher and thermal decomposition. The heat resistance at temperatures above 300 °C is ideal. In addition, the weight loss of 5% is more than 300C. The heat resistance is sufficient, and the sputtering resistance and plating resistance necessary for the rewiring forming step are also provided. , alkali resistance, etc. Since the modulus of elasticity of the resin layer can be arbitrarily controlled in the range of 0.2 to 3. OGPa, it can correspond to all semiconductor devices. According to this, the amount of unevenness of the germanium wafer can also be reduced. The semiconductor device manufactured by this method can be expected to have an improvement in manufacturing yield and can improve productivity. Next, a semiconductor insulating resin of the present invention, a semiconductor device using the resin, and a method for producing the same will be described. A method of manufacturing a semiconductor device according to the present invention, comprising the steps of forming a plurality of resin layers by using the resin composition or a heat-resistant resin paste on a semiconductor substrate on which a wiring has been formed; and forming the semiconductor paper on the resin layer for use in China National Standard (CNS) A4 Specification (210 X 297 mm) 48 312417 1287030 A7 B7 V. INSTRUCTION DESCRIPTION (49) Steps of Electrodes on the Substrate and Electrical Conduction of the Second Wiring Layer; Removal of Loading on the Second Wiring Layer a step of forming a protective layer with a portion of the external electrode tab; and a step of forming an external electrode tab on the protective layer. The method for producing a semiconductor device according to the present invention includes the step of forming a resin layer by using the above-described resin composition or heat-resistant resin paste on a semiconductor substrate on which wiring is formed, and providing a through hole reaching the wiring layer in one of the resin layers And a step of forming an external connection joint and a second wiring layer electrically connected to the wiring layer on the resin layer. The method for producing a semiconductor device of the present invention further comprises the above resin composition or heat resistance which has an elastic modulus of 25 to 3.0 GPa at 25 t, a glass transition temperature of i8 〇〇c or more, and a 5% weight loss temperature of 300 ° C or more. a resin paste printed on a semiconductor wafer on which an electronic circuit has been formed to form a plurality of resin layers; a step of forming an electrode of the semiconductor wafer and a second wiring layer electrically conducting on the resin layer; a step of printing the resin on the wiring layer to form a plurality of protective layers of the second wiring layer; and providing a step of reaching the through hole of the second wiring layer on the protective layer of the second wiring layer; forming an external electrode joint in the through hole And a process of cutting the semiconductor wafer to obtain individual semiconductor devices. Next, an embodiment of the present invention will be described with reference to the drawings. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a cross-sectional view showing the manufacturing process of a semiconductor device in accordance with an embodiment of the present invention. Fig. 1(a) is a general structural diagram of a semiconductor wafer. The semiconductor wafer 3 of the present invention is not limited as long as it has been formed with an electronic circuit or a semiconductor component, and the semiconductor wafer of any kind or size is applicable to the CNS A4. Specifications (21G X 297 public f) 49 312417 ------------ (Please read the notes on the back and fill out this page) --- 丨..----1---- Ministry of Economic Affairs, Intellectual Property Bureau, Staff Consumer Cooperative, Printed 1287030 A7

50 312417 1287030 51 A7 B7 V. Inventive Note (5ι) The modulus of elasticity is 〇·2 to 3.0 GPa, and the elastic modulus of the above resin layer at 150 ° C is 1 〇 to 1 弹性 at -65 ° C. %, and the glass transition temperature of the resin layer is preferably above 180 °C. Examples of the resin forming the resin layer include the above-described resin composition and heat-resistant resin paste. The resin having a low modulus of elasticity is preferably an rubber such as an acrylic rubber, a fluorine-containing rubber, a butadiene rubber or a ruthenium rubber, or an elastomer, and is preferably in the form of such particles. The modulus of elasticity here is the storage modulus and is measured using a viscoelasticity measuring device. The present invention was measured using a viscoelastic analyzer RSAII manufactured by Leometallic Scientific FE Co., Ltd. at a temperature of 5 ° C / min and at a frequency of 1 Hz. The edge portion of the resin layer formed on the semiconductor substrate has a maximum angle of 45 degrees or less, more preferably 5 degrees or more and 30 degrees, which is formed by the connection between the planar portion of the semiconductor substrate and the resin layer in the thickness direction of the edge portion of the resin layer. the following. When the maximum angle formed by the above is more than 45 degrees, it is difficult to form the second wiring layer by sputtering, vapor deposition, plating, or the like on the resin layer. The elastic modulus of the resin layer 1 at 150 ° C needs to be 10 to 100% of the elastic modulus at _65 ° C. If the semiconductor device is cycled at a temperature of _65 to 15 ° C repeatedly if it is less than 10%, the resin layer The elastic modulus rapidly increases at a low temperature, and inelastic deformation is likely to occur at the joint portion of the solder ball or the like, resulting in a decrease in reliability. Therefore, it is preferably from 50 to 90%. The glass transition temperature of the resin forming the resin layer 1 is preferably at least 18 Å. If the glass transition temperature of the resin layer is less than 18 (TC, it is shot off on the resin layer). Since the resin is exposed to high temperature during the formation of the second wiring layer 6, the K degree is applied to the National Standard (CNS). A4 specification (210x297 public) __ 312417 items

Page Order 1287030 A7 B7 V. INSTRUCTIONS (52) There are problems such as thermal decomposition of the resin. The glass transition temperature is better than 200 °c. The 5% weight reduction temperature of the resin forming the resin layer 1 is preferably at 300 ° C or more. When the 5% weight loss temperature is less than 300 °C, the resin is exposed to a high temperature during the sputtering of the second wiring layer 6, and the resin may be thermally decomposed or the like. Further, it is preferable that the drying or curing temperature of the resin is 250 ° C or less to reduce the deterioration of the characteristics of the semiconductor element. The resin used in the present invention is preferably a resin paste form in which a resin layer is formed by printing or spray coating, drying or hardening in the step of forming a plurality of resin layers to facilitate formation of a resin layer. Further, it is preferable that the viscosity of the resin paste is from 1 to 1000 Pa·s and the thixotropy coefficient of the above resin paste is from 12 to 150. Here, the thixotropic coefficient (TI value) is the ratio of the apparent viscosity π 1 to π 1 回转 of the number of revolutions Imin·1 and 10 min·1, expressed as π π Γ〇. If the viscosity of the resin paste is less than IPa · s, it will flow excessively when the resin layer is formed, and the pattern is difficult to be precise and high in density. Moreover, if it exceeds 1 〇〇〇 Pa · S ′, the viscosity is too high, and there is a concern that the insulating layer is formed poorly. The method of forming the resin layer is not particularly limited, and any method for forming the resin layer may be a method of forming a resin layer by spin coating on the surface of a semiconductor substrate, and laminating a film-form resin formed on the surface of the semiconductor substrate to form a resin layer. Further, a method of forming a resin layer by screen printing or metal printing on a surface of a semiconductor substrate or a method of forming a resin layer by spraying a resin paste on a surface of a semiconductor substrate is preferable because the material is worn out and steps are small. This paper scale applies to China National Standard (CNS) A4 specification (21〇χ 297 mm) 312417 (please read the note on the back and fill out this page). · Department of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Print 52 1287030 A7 B7 V. INSTRUCTION OF THE INVENTION (53) The resin layer 1 can also be formed by printing a resin using a metal mask. At this time, in order to thicken the resin layer 1, it is also possible to repeatedly print a plurality of times. The thickness of the resin layer 1 is preferably thicker than the stress cushioning point, and is not particularly limited, and is preferably 50 to 100/zm; if it is less than 50//ΠΙ, the stress absorption effect is lacking. If more than 1 〇〇 #m can improve the stress absorption effect, it is preferable, but the thickness of the conductor device is too thick and it is not easy to be thin. The printing position of the resin layer 1 is preferably at least completely covering the electronic circuit on the semiconductor wafer 3, and at least the position of the dicing region 8 is preferably removed. Fig. 1(c) is a view showing the formation of a hole at a desired position of the resin layer 1. The formation of the pores of the resin layer 1 allows the electrode pad 5 to be exposed by laser processing. Fig. 1(d) is a view showing the formation of the second wiring layer 6 on the resin layer 1. In the method of forming the second wiring layer 6, for example, a sputtering metal film such as chromium is formed on the resin layer 1 by using a laser device, and an electrode resistance is applied to the sputtering metal crucible to expose a portion of the steel plating wiring to be formed. • Development processing, forming a plating resistor layer, electrolytically plating the exposed portion of the sputtered metal film, and forming a steel wiring. After the steel wiring reaches a desired thickness, the plating resistance is peeled off, and then the exposed portion of the metal is removed. Alternatively, as long as at least the electronic circuit can be completely covered at the printing position of the resin layer 1, and at least the electrode pad 5 is removed, the second wiring layer 6 can be formed even without forming a hole by laser or the like. The bottom of the resin layer ι formed by printing has fluidity, and the shape of the opening of the metal mask is not completely reproduced, and it becomes a slack shape. As long as the wiring is formed in this part, even if the laser hole is not used, the electrode pad 5 and the external electrode connector 7 can be formed. The paper size is appropriate (2) 0 x 297 Γ 312417 ----------- (Read first On the back of the phonetic? Matters fill out this page) Order: ----------•MW, Ministry of Economic Affairs, Intellectual Property Bureau, employee consumption cooperatives, printing 53 1287030 A7 ------- B7____ __ V. Invention Description (54) The second wiring layer 6 electrically connected. For example, a resin is printed on the resin layer 1 in a range in which the electronic circuit is completely covered, at least the electrode pad 5 is removed, a sputtered metal film such as chromium is formed by a sputtering apparatus, and an electrode resistor is coated on the sputtered metal film. A part of the copper plating wiring is formed to perform exposure and development processing to form a plating resistive layer, and the exposed portion of the i-sputtered metal film is electrolytically plated to form a copper wiring. After the steel wiring reaches a desired thickness, the plating resistance is removed, and the sputtering metal is removed. The exposed portion of the film. Fig. 1(e) is a view showing the formation of the second wiring layer protective layer 2. It is preferable to print the position of the second wiring layer protective layer 2 so as to at least completely cover the second wiring layer 6, and at least to remove the dicing region 8. The thickness of the second wiring layer protective layer 2 is not particularly limited, and is preferably from 1 〇 to 50 mA. Further, the resin forming the second wiring layer protective layer 2 is preferably formed of the same composition as the resin forming the resin layer 1, and the composition ratio is also preferably the same. For example, the second wiring layer protective layer 2 and the resin layer 1 are formed of the same composition, and the content of the filler is changed to make the value of the modulus of elasticity different. The second wiring layer The protective layer 2 and the resin layer 1 are formed of the same composition, and have good compatibility with each other and excellent adhesion. Fig. 1(f) is a view in which a hole is formed at a desired position on the second wiring layer protective layer 2 to form an external joint. The hole in which the second wiring layer protective layer 2 is formed can be exposed to the second wiring layer 6 by laser processing. Fig. 1(g) is a view showing that the semiconductor wafer 3 is cut in the dicing region 8 to form individual semiconductor devices. The solder balls loaded to the external joints can be made after pelletizing before the wafer is diced. [Embodiment] (Please read the phonetic transcription on the back side and then fill out the form page.) Order: Ministry of Economic Affairs, Intellectual Property Office, Staff Consumer Cooperative, Printed Paper Size Applicable to China National Standard (CNS) A4 Specification (210 x 297 mm) 54 312417 1287030 A7

312417 Please read the note on the back first.

I

55 1287030 A7 V. INSTRUCTIONS (56) Diamine knocking alpha lacquer. The obtained polyamic acid varnish was further removed at 1 90 ° C to produce a polyether amidoxime varnish. In the polyether amidoxime varnish varnish, the person who is in the water will separate, pulverize, and dry the precipitate, and the dish will not be dissolved in a polar solvent, but the polyether amide can be dissolved by heating. Amine powder. In a nitrogen gas machine, a thermometer, a scrambler, and a nitrogen gas were introduced into a 4-neck flask of 3 ml of a cooling tube with an oil-water separator, and the obtained polymer was dissolved in a polar solvent at a temperature. 15 g of the ether amidoximeimine powder, the above obtained poly-proline amide powder which is insoluble in a polar solvent at room temperature but soluble by heating, 15 g of vinegar, 7 g of vinegar, stirred in #1 5 〇C is heated for 1 hour, at this time, the unevenness at room temperature can be homogenized by heating. After the heating is stopped, the mixture is allowed to cool to room temperature while stirring, and the viscosity and contact of the paste obtained by the yellow-brown paste Q containing the two resins are obtained. The denaturation coefficient (τι value) was measured by a cV 〇 ammeter manufactured by Jiasko International Co., Ltd. The obtained paste was screen-printed on a tantalum wafer (LS-manufactured by Zhongchang Precision Industry Co., Ltd. with calibration device) 34GX), mesh-free metal plate made of nickel alloy with additives (made by Mesh Industrial Co., Ltd., thickness 5〇#m, pattern size 8mmx 8mm) and Bamarex metal doctor blade (Imported by Ba Industrial Co., Ltd.) Evaluate printability. After printing, pattern optics The bleed and relaxation were observed by microscopic observation. The obtained paste was applied to the Teflon substrate at 25 Torr. (: The organic solvent was dried by heating to form a film having a film thickness of 25 // m. The film was dynamically viscous. Elastic spectrometer (manufactured by Iwamoto Manufacturing Co., Ltd.) to determine the tensile modulus (25 paper scales applicable to Chinese national standards (CNS>A4 specifications (2)〇x 297 public))" ----- 56 312417 --- (Please read the note on the back m to write this page) . · Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed 1287030 A7 B7 V. Invention Description (57) C l〇Hz), _65 C and 15〇°C Rate (frequency 1 〇 Hz, temperature increase rate 2 ° C / min) and glass transition temperature (frequency 1 〇 Hz, temperature increase rate 2 points). Further, the thermal decomposition start temperature was measured via a thermal balance. The following steps were performed: a step of coating a plurality of resin layers by screen printing on a semiconductor substrate on which a wiring has been formed, and drying; forming an electrode on the semiconductor substrate and rewiring the electrical conduction on the resin layer; on the rewiring a step of forming a protective layer; a step of forming an external electrode joint on the protective layer. Then, pelletizing is performed to fabricate a semiconductor device. The semiconductor device is subjected to a thermal cycle test (_55〇c/3〇-125° C/min, 1000 cycles) to study the resin layer. Whether or not the fracture occurred, the occurrence of the fracture was indicated by Ο, and the occurrence of the fracture was indicated by χ, and the semiconductor device was evaluated in this way. The evaluation results of the above resin composition and semiconductor device are shown in the table. Example 2 In addition to the synthesis of Example 1, The diamine compound which is soluble in the polar solvent amidoximeimine at room temperature is changed to bis[4_(4-aminophenoxy)phenyl] code (BAPS) 93.3 g (216 mmol), 1 The production of the resin composition semiconductor device was evaluated in the same manner as in Example i except that 3.0 g of bis(aminopropyl)tetramethylbicyclooxane (24 mmol) was used. The results are shown in Table 1. Example 3 In addition to changing the diamine compound synthesized in Example 1 to be soluble in a polar solvent in a polyacrylamide imine, 2,2-bis[4-(4-amino-phenyl)phenyl Propane (ΒΑΡΡ) 78·7 g (192 mmol), 1,3-double (amine-based paper andamp; scale applicable to China National Standard (CNS) A4 specification (210 297 297 mm) ^ 3124Ϊ7 Read the back first Note: Please fill in this page. Continue II. Order 1287030 Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed A7 --------J _____ V. Invention Outline (58 ) "~—— Base) Tetramethyl 2 Cyclopentane 6 gram (24 mmol) 4 *, diamine mediphenyl 4.8 gram (24 mmol) 'acid compound changed to isophthalic dichloride 24.8 g (122 mmol) The production of the semiconductor composition of the resin composition was evaluated in the same manner as in the Example except that the trimellitic anhydride vaporized w gram (122 mmol) was used. The results are shown in Table i. Example 4 In addition to the synthesis of Example 1, The diamine compound in the polyether amidoxime imine which is insoluble in the polar solvent at room temperature but is soluble by heating is changed to double [4_ ('Aminophenoxy)phenyl] code (BAps) 93 3 g (216 mmol), 1,3-bis(aminopropyl) tetramethylbicyclooxane 6 〇g (24 m The production of the resin composition semiconductor device was evaluated in the same manner as in Example 1. The results are shown in Table 1. Example 5 The synthesis of Example 1 was insoluble in a polar solvent at room temperature but was heated. The diamine compound in the soluble polyether amidoxime is changed to 2,2_bis[4-(4-aminophenoxy)phenyl]propane (BAPP) 78.7 g (1 92 mmol) , 1,3-bis(aminopropyl)tetramethylbicyclooxane 6 gram (24 millimolar), 4,4, diaminodiphenyl 4.8 grams (24 millimolar), The acid compound was changed to isophthalic acid dichloride (12.4 g (61 mmol), trimellitic anhydride chloride 12·8 g (61 mmol), 3,4,3,,4,-benzoic pyromellitic acid The production of the resin composition semiconductor device was evaluated in the same manner as in Example 1 except that the dianhydride (BTDA) was 39.4 g (122 mmol). The results are shown in Table 1. -read-------*?- ! Parameters. (Please read the notes on the back of this page and then fill in) Example 6

This paper scale is applicable to China National Standard (CNS) A4 specification (210 X 297 mm). 58 312417 1287030 59 A7 B7 V. Inventive Note (59) The polyether oxime which is soluble in polar solvent at room temperature obtained in Example 1 Ammonia imine, and a yellow-brown paste of two kinds of resins such as polyether amidoxime, which is insoluble in a polar solvent at room temperature but which is soluble in heat, and an average particle diameter of 100 g (nonvolatile content: 30 g) 2wm, an epoxy group-modified surface of an anthrone rubber filler E_6〇1 (manufactured by Tosoh Corp.) was mixed with 3 drums to obtain a yellow-brown paste. The evaluation of the dispersibility of the paste was carried out to confirm the presence or absence of agglomeration (uniform unevenness) when the film was allowed to stand for 1 week, and the results are shown in Table i. f. Example 7 A resin composition semiconductor device was carried out in the same manner as in Example 6 except that the average particle diameter in Example 6 was 2 μm, and the fluorenone rubber filler of the epoxy group-modified surface was changed to 15 g. The results of the evaluation were as shown in the table. Example 8 except that the average particle diameter in Example 6 was 2 μm, and the fluorenone rubber filler of the epoxy-modified surface was changed to 20 g, and Examples ^ Evaluation of the fabrication of the resin composition semiconductor device was carried out in the same manner. The result is shown in Table ι. Example 9 A resin composition semiconductor device was produced in the same manner as in Example 6 except that the average particle diameter in Example 6 was 2/Zm, and the Monternet rubber filler on the surface-modified surface was changed to 25 g. Evaluation. The results are shown in Table i. Example 10 * ___ This paper size applies to the National Standard (CNS) A4 specification (210 X 297 mm) 312417 item 1287030 A7 B7 V. Inventive Note (60) The average particle size in Example 6 is 2 / / m, The production of the resin composition semiconductor device was evaluated in the same manner as in Example 6 except that the fluorenone rubber filler on the epoxy-modified surface was changed to 30 g. The results are shown in Table 1. Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperatives Printed Semiconductor Devices Evaluation Thermal Decomposition Start Temperature [t] Glass Transfer Temperature (Tg) [°C ] 150°C/-65eC Elasticity Change Rate [%] Elasticity [GPa] Printability (with or without bleed * relaxation) TI value viscosity [Pa · s] Dispersion filler 4 Chemical modification of filler surface 1 Low elastic filler Dong Sheng II is insoluble in 1 polar solvent at room temperature, but via heating Soluble resin 5E 1E 缪ml· 踝ml· 150Ϊ -65〇C 25〇C Aggregate sedimentation P* average particle size [// m] mw® Tetrazoic acid tricarboxylic acid 1 Dicarboxylic acid aliphatic diamine Aromatic diamines of general formula (I) General formula (1) Tricarboxylic acid dicarboxylic acid aliphatic diamines A wide range of aromatic diamines other than formula (I) General formula (I) 〇440 240 00 K) tn K) 00 580 1 1 1 1 1 100 :〇1 〇1 1 〇〇1 1 1 〇Η·* 〇[430 230 <1 00 N) υα to 00 〇540— 1 1 1 1 1 100 〇1 〇 1 1 〇〇1 〇1 〇Ν> 〇435 230 00 to «-Λ CO NJ to 00 Ui 560, 1 1 1 1 1 lOOj ;〇1 〇I 1 〇〇〇〇〇〇〇440 230 00 K>K> 00 560 1 1 1 1 100 〇I Ο Ο 1 〇〇I 1 1 〇〇430 [240 00 l〇•认U) to 2.8 3.8 520 1 1 1 I 1 100 〇〇〇Ο 〇〇〇1 1 1 〇〇 ο» ON 〇420 220 On to N) 2.9 K> Ui ON 540 ο — 〇u> o 〇1 〇1 1 〇〇1 1 1 〇415 215 -α u% — 00 N> 〇〇580 to ο 琳 o 〇1 〇1 1 〇〇1 1 1 〇〇410 210 ON <1 — ro — 00 — 00 550 Ο 〇o 〇1 Ο 1 1 〇〇1 1 ί 〇00 〇405 205 0.8 ls> — o to 530 Μ n 1 1 1 1 1 1 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o & & — — — — — — — — — — (Please read the precautions on the back and fill out this page.) Order · Line Qin Ben Paper Scale Applicable to China National Standard (CNS) A4 Specification (210 X 297 mm) 60 312417 61 1287030 A7 I^ ----~_____ V. Inventive Note (61) It is advisable to apply Example 11 under a nitrogen gas stream with a thermometer, a stirrer, a nitrogen inlet pipe, and an oil-water separator. But in a 1 liter 4-neck flask, put 2 2-bis[4-(4-aminophenoxy)phenyl]propane (BaPP) 98 4 g (240 mmol) diamine compound, Add methyl 2_[! pyrrolidone (NMp) 7 gram grams to dissolve. Next, add bis(3,4-dicarboxyphenyl)ether dianhydride 8 〇 6 g (26 〇 mmol) of the acid compound while stirring at no more than 2 〇〇 c. Stir at room temperature for 1 hour. Thereafter, a dehydration reaction was carried out at 19 ° C for 6 hours to produce a polyether oxime varnish. Water is poured into the polyether oxime varnish, and the obtained sediment is separated, pulverized, and dried to obtain a polyether quinone powder which is insoluble in polarity at room temperature and which is soluble in the granules by heating. The resin was treated in the same manner as in Example 1 except that the polyether amidoximine powder which was insoluble in a polar solvent at room temperature but dissolved by heating was changed to the polyether quinone powder obtained above. Production evaluation of the composition semiconductor device. The results are shown in Table 2. Example 12 In addition to changing the diamine compound synthesized in Example 1 to a polyether [4_(4-aminophenoxy)benzene] group in a polyether | amidoxime imine soluble in a polar solvent at room temperature ( BAPS) 93.3 grams (216 millimoles) and 13 pairs (aminopropyl) four! Only methyl bicyclohexene oxime 6 gram grams (24 millimoles), will be insoluble at room temperature | solvent However, the production of the tree I I lipid composition semiconductor device was carried out in the same manner as in Example 之外 except that the polyether acrylonitrile powder which was dissolved by heating was changed to the polyether quinone powder obtained in Example I. 11 Example 11 | (cns)A4 Secret (2) (4) 97 )——----1 312417

-----------镄(Please read the phonetic on the back first? Then fill out this page) Order · 11 ! 62 1287030 V. Description of the invention (62; except that the synthesis of Example 1 is soluble at room temperature The diamine compound in the polyether amidoxime imine of the polar solvent was changed to 2,2-bis[4-(4-aminophenoxy)phenyl]propane (ΒΑΡΡ) 78·7 g (192 mmol) ), 13_bis(aminopropyl)tetramethylbicyclooxane 6·〇g (24 mmol) and 44, diaminodiphenyl ether 4.8 g (24 mmol), acid compound Changed to 24.8 g (122 mmol) of isophthalic acid dichloride, 25 6 g (122 mmol) of trimellitic anhydride vapor, polyether amidoxime which is insoluble in polar solvent at room temperature but soluble by heating The preparation of the resin composition semiconductor device was carried out in the same manner as in Example 1 except that the obtained imine powder was changed to the obtained poly-imine powder. The results are shown in Table 2. Example 14 Example 11 Synthesis of a diamine compound in a polyether oxime imine which is insoluble in a polar solvent at room temperature but soluble by heating is changed to bis[4·(4-amine Phenoxy)phenyl] code (BAPS) 93 3 g (216 mmol) and 1,3-bis(aminopropyl) tetramethylbicyclohexyloxy 6 〇 gram (2 4 mmol) The production of the resin composition semiconductor device was evaluated in the same manner as in Example 1. The results are shown in Table 2. Example 15 The synthesis of Example 11 was insoluble in a polar solvent at room temperature but was heated. The diamine compound in the dissolved polyether oximine is changed to 2,2_bis[4_(4-aminophenoxy)phenyl]propene (β APP) 78 7 g (I% mmol), 1,3-bis(aminopropyl)tetramethylbicyclooxane 6·〇g (24 mmol) and 4,4,-diaminodiphenyl ether 4.8 g (24 mmol) The evaluation of the production of the resin composition semiconductor device was carried out in the same manner as in Example 1. """" - . . - _ This paper scale applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 312417 --- ----i -------- Line 1 (please read the notes on the back and fill out this page) 1287030 — A B7 V. Description of the invention (63 / The results are shown in Table 2. In addition to the implementation Example 6 In the case of the resin, the resin can be insoluble in the polar solvent, but the polyether is obtained by heating the sub-mold, and the L is changed to the polyether oxime obtained in the eleventh embodiment: the resin composition semiconductor device is the same as the ruthenium The results of the evaluation are shown in Table 2. The results are shown in Table 2. In addition to the fact that in Example 6, the A gp _ ^ is obtained, the dish is not in the polar solvent but the P is heated by heating. The imine was changed to the polyether decylamine obtained in Example 11, and the average particle diameter was 2 "m, and the ruthenium rubber-filled ruthenium of the ruthenium and enamel-modified surface was changed to 15 g, and Example 6 The production evaluation of the resin composition abundance conductor device was carried out in the same manner. The results are shown in Table 2. 18, except that the polylysine imine obtained by inactivating the polar solvent at room temperature in the polar solvent was changed to the poly-hydrazine, imine obtained in Example η, and the average particle diameter was 2 " m, The evaluation of the production of the resin composition semiconductor device was carried out in the same manner as in Example 6 except that the epoxy group-modified surface (tetra) gel was changed to 20 g. The results are shown in Table 2. In addition to changing the polyether amidoxime imine which was insoluble in a polar solvent at room temperature but soluble in heating to the polyether quinone imine obtained in Example u, the average particle diameter was 2 " m, a ring The composition of the wax was evaluated in the same manner as in Example 6 except that the oxime rubber of the oxy-modified surface was changed to 25 g, and ^ ^ ^ ^ < t was evaluated. The results are shown in Table 2. W Zhang scale suitable wealth _ home standard (10) χ tear public 6 312417

i --------^--------in (Please read the notes on the back and fill out this page) 63 1287030 A7

Nil — ϋ nnnnn ϋ · n I (please read the notes on the back and fill out this page). Line 1287030 A7 B7 V. Description of invention (65) Evaluation of the thermal decomposition of printed semiconductor devices by the Intellectual Property Office of the Ministry of Economic Affairs Temperature rc] Glass transition temperature (Tg) [°C] Rate of change in modulus of elasticity at 150 °C / -65 °C [%] Elasticity [GPa] Printability (with or without bleed/relaxation) TI value viscosity [Pa · s The chemically modified low-elastic filler of the surface of the filler of the dispersing filler is insoluble in the polar solvent at room temperature, but the resin can be dissolved by heating, 萆 笛 Q] 缫jing h 150 ° C -65 ° C 25〇C Aggregate sedimentation P* average particle size [//111] New 1Φ tetracarboxylic acid 1 aliphatic diamine general aromatic diamine other than formula (I) general formula (I) tricarboxylic acid dicarboxylic acid aliphatic Diamines General aromatic diamines other than formula (I) General formula (I) 〇450 240 00 K> Uk ro Ki VO Ui 570 ' 1 1 1 1 1 100 〇II 〇Ο 1 I 1 〇 — — 〇 1440 [ 230 , 00 to u u>ts> 2.9 — 540 t 1 1 1 1 [1〇〇] 〇1 1 〇〇1 〇1 〇Η-Λ 〇440 235 00 Ui LO to Ki 4.4 4.4 550 1 1 1 1 1 Ll〇〇J 〇1 1 〇〇Ο Ο 〇〇1—* 〇430 230 00 Ni Ut K>N> VO Ut ^70 1 1 1 1 1 100 Ο 〇1 〇〇1 1 1 〇〇 440 240 00 K) to to s〇U) SO 530 1 1 1 1 1 10〇J Ο 〇〇〇〇1 1 1 〇—KJt 〇420 225 σ> to N> VO to Ui 3.8 550 澌新〇讲— 〇Ui ο Ο 1 1 〇〇1 1 1 〇—Os 〇415 215 'vj 00 K) K) o N> 570 ΪΟ 〇 — Ut ο 〇1 1 〇〇1 1 i 〇ι—* &lt ;1 〇410 210 On to — 00 — U> SO 560 Νί 〇 tear · ί〇ο ( ο 〇I 1 Ο 〇1 1 1 〇— 00 〇405 205 '-I o 00 K) H-* o Private— 530 to •ο琳Νί Ui ο 〇1 1 〇〇1 1 1 〇0 "400 1200 〇ts>uu>K> 00 Ki 570 to *ρ u> ο to ο 〇1 1 〇〇1 1 1 〇to Oj cannot be made j 1 440 1 240__ 00 K) u» u> N) to 00 — b 550 | 1 1 1 1 1 100 1 1 1 〇〇1 1 1 〇rrt thin chamber K)

This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm). 65 312417 Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperative Printed 1287030

Synthesis Example 1 (heat-resistant resin Α''-π was placed in a 00 ml 4-neck flask with a mixer, a thermometer, a nitrogen gas introduction tube, and a cooling water pipe with an oil-water separator, and was placed in a nitrogen gas while being placed 3, 4, 3',4 _benzimidoxime dianhydride (hereinafter referred to as btda) 96 7 g (0.3 m), 4,4 amino diphenyl ether (hereinafter referred to as DDE) 36 g (0.18 m), 2,2,-bis[4-(4-aminophenoxy)phenyl]propane (hereinafter abbreviated as ΒΑΡΡ) 43·1 g (〇·ι〇5 mol), ι,3-bis (3-amine) Propyl) tetramethylbicyclooxane 3.73 g (〇·〇15 mol) and r_butyrolactone 3815 g. After stirring at 60 to 65 ° C for 2 hours, the number average When the molecular weight reached about 50,000 (polystyrene-converted value), the reaction was terminated by cooling. The resulting solution was released with 7-butyrolactone to obtain a polyimide concentration of 30% by weight of a polyimide precursor (heat resistant resin person). "-丨" solution. Synthetic example 2 (resistance to fight for damage R', _n in women's clothing mixer, thermometer, nitrogen inlet pipe and cooling water pipe with oil-water separator 1,000 ml 4 long neck The middle side is filled with BTDA 109.6 g (〇·4 mol), DDE 76.1 g (〇·38 mol), 1,3-bis(3_aminopropyl)tetramethylbicyclooxane 4 97 g (〇〇2 mol) and r-butyrolactone 405.2 g. After the reaction at 60 to 65 ° C for 2 hours under scramble, the number average molecular weight reached about 35,000 (polystyrene equivalent) The reaction was terminated by cooling, and the resulting solution was released with 7-butyrolactone to obtain a solution of a polyimine precursor (heat-resistant resin Β'ι) having a resin concentration of 30% by weight. Moisture Resistant Resin a"-i/Fluidity; ^ This paper size depends on the ® ® _ Standard (CNS) A4 specification (21G x 297 public) ~ 66 312417

1287030 A7

V. INSTRUCTIONS (67) In the cooling tube equipped with a stirrer, a thermometer, a nitrogen inlet pipe and an oil-water separator, the above-mentioned heat-resistant resin B is just placed in the milliliter 4 π flask. -1 polyimine precursor (resin concentration: 30% by weight) 150 g 'and the above heat resistant resin A] polyimine precursor solution (resin concentration of 30% by weight) 35 gram, mixed and 6〇 to 65. (: stirring was continued for 1 hour, and a uniform solution was prepared. Further stirring was continued for 6 hours at 6 to 65 t, and the dispersed heat-resistant resin B-1 polyimine precursor particles were precipitated in the solution. The microparticles were used γ _ A concentration of butyrolactone, a polyamidene heat-resistant resin paste with a viscosity of 480 Pa · s and a thixotropy coefficient (hereinafter referred to as a τι value) of 3.0, and a polyimide resin (1) The heat-resistant resin B, -: l polyimine precursor particles are insoluble in γ-butyrolactone at room temperature and soluble at 80 ° C. The above-mentioned polyimide-based heat-resistant resin paste ( 1) Apply a thickness of 5 〇em on a glass plate (thickness of about 23⁄4 m) with a stick coater to heat dry, at 80 ° C for 5 minutes, l ° ° Cl 〇 minutes, 150 ° C for 10 minutes, 200. (^15 In a minute, more than 30 (TC 60 minutes heat treatment, a glass plate with a polyimine-based resin composition (1) is obtained. The cured film is almost uniform and transparent, and the heat resistance in the polyimide-based heat-resistant resin paste Resin Β''-polyimide precursor particles are dissolved in r-butyrolactone during heating, and more with heat-resistant trees The lipid A,,-1 polyimine precursors are dehydrated and closed together, and are mutually soluble in the state of being a polyimine resin. Gold Example 3 (heat-resistant resin A''-2, with a mixer, thermometer installed The nitrogen-introducing tube and the cooling tube with the oil-water separator are placed in a 1,000-ml 4-neck flask with nitrogen gas. (Please read the back note and fill out this page.) ίί· Ministry of Economic Affairs Intellectual Property Office Staff Cooperative Printed paper size applies to China National Standard (CNS) A4 specification (210 X 297 mm) 67 312417 1287030 A7 B7 V. Invention description (68) BTDA 77.3 g (0·24 m), 1,10_ (ring sunflower Alcohol) bis(trimellitic phthalate dianhydride) 31.4 g (〇·06 Mohr), DDE 36.0 g (0·18 mol), ΒΑ ΡΡ 43·1 g (〇·ι〇5 mol), 13 _Bis(3-aminopropyl)tetramethylbicyclohexene oxide 3.73 g (〇·015 mol) and ^-butyrolactone 381·5 g. Under stirring, at 60 to 65. (: proceed After the reaction for 2 hours, the reaction was terminated by cooling while the number average molecular weight reached about 60,000 (polystyrene equivalent). The solution was released with 7-butyrolactone, and a solution of a t-imine precursor (heat-resistant resin α"_2) having a resin concentration of 30 篁 was obtained. Logic (heat resistance-resin matrix paste: heat-resistant resin α, , -2/resistance resin Β, η Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed in a 1,000 ml 4-neck flask equipped with a blender, thermometer, nitrogen inlet tube and cooling tube with nitrogen gas The above-mentioned heat-resistant resin Β'1 polyimine precursor (resin concentration: 30% by weight) of 100 gram and the above-mentioned heat-resistant resin Α, -2 polyimine precursor solution (resin concentration is 30% by weight) 4 gram gram, mixed and 60 to 65. (: Stirring for 1 hour) to prepare a homogeneous and transparent solution. Stirring was further continued at 60 to 65 ° C for 34 hours to precipitate the dispersed heat-resistant resin B" polyimine precursor particles in the solution. The butyrolactone is released to obtain a polyimide-based heat-resistant resin paste having a viscosity of 450 Pa·s and a thixotropic coefficient (hereinafter referred to as TI value) of 5 5 (2). Polyimide-based heat-resistant resin paste (2) The heat-resistant resin B''-1 polyimine precursor precursor fine particles are insoluble in r - butyrolactone at room temperature, and soluble at 80 ° C. The above polyethylenimine heat-resistant resin paste (2) Applying a glass plate (thickness of about 2 mm) with a bar coater to heat and dry the thickness to 50//m. This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm). 312417 1287030 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed A7 --------- B7 -----___ V. Invention description (69) at 8 (TC 5 minutes, 10 (TC 10 minutes, 15 (rc 1 minute, 2 〇〇. 〇i 5 minutes, more than 250. 60 minutes for heat treatment 'obtained with a polyimide resin composition (2) Glass plate. The cured film is almost uniform and transparent, and the heat-resistant resin polyimine precursor particles in the polyimide-based heat-resistant resin paste are dissolved in r_butyrolactone during heating, and more with heat-resistant resin. a,, _2 Polyimine precursors are dehydrated and closed together, and are mutually soluble in the state of being a polyimine resin. Gold Example 4 (heat resistant resin a)-3) is equipped with a stirrer, a thermometer, a nitrogen introduction tube And the cooling pipe with the oil-water separator, the 4ml 4-portion flask is filled with BTDA 32.2 g (0.1 m) in the middle of the nitrogen gas,;!, 〇 ( (cyclohexane) double (bias) Triglyceride

Diacetate) 52·2 g (0.1 mol), DDE 36.0 g (〇·ΐ8 Mo), BAPP 43·1 g (〇·ΐ〇5 mol), ι,3-bis (3-aminopropyl) Base) tetramethylbicyclohexyloxylate 3.73 grams (0.015 moles) and butyrolactone 381.5 grams. After the reaction was carried out at 60 to 65 ° C for 2 hours with stirring, the reaction was terminated while cooling at a number average molecular weight of about 45,000 (polystyrene equivalent). The resulting solution was released with 7-butyrolactone to obtain a solution of a polyimine precursor (heat resistant resin α, ...) having a resin concentration of 30% by weight. 1 Preparation 3 (heat-resistant resin base paste: heat-resistant resin α,, -3 / resistance _ lipid Β,, _η in the installation of a mixer, thermometer, nitrogen inlet pipe and cooling pipe 1, 〇 00 ml 4 The heat-resistant resin B_1 polyimine precursor (resin concentration of 3 〇 wt%) of 250 gram and the above heat-resistant resin A_3 polyimine precursor solution were placed in the long neck of the flask. (Resin-concentrated paper scale applies to China National Standard (CNS) A4 specification (21〇x 297 mm) 312417

69 1287030 A7

5. Description of the invention (7 〇) 30% by weight) 250 gram, mixed and continuously mixed at 60 to 65 ° C for 1 hour to make a uniform and transparent solution. Further, when the mixture was further stirred at 6 to 65 ° C for 14 hours, the dispersion of the heat-resistant resin B" polyimine precursor particles was precipitated in the solution. The fine particles were released with 7 -butyrolactone to obtain a viscosity of 400 Pa. · s, thixotropy coefficient (hereinafter referred to as TI value) of 4 5 polyiminoimide heat-resistant resin paste (3). Polyglycerol heat-resistant resin paste (3) in the heat-sensitive resin Β '' -1 Polyimine precursor particles are insoluble in butyl vinegar at room temperature 'Soluble at 80 ° C. The above polyimine-based heat-resistant resin paste (3) is on a glass plate (thickness about 2 mm) Coating with a bar coater to heat dry after drying to a thickness of 50 / / m ' at 80 ° C for 5 minutes, 1 ° ° c 1 〇 minutes, 150 ° C for 10 minutes, 200 ° C for 15 minutes, more than 250 ° C Heat treatment was carried out for 60 minutes to obtain a glass plate with a polyimine-based resin composition (3). The cured film was almost uniformly transparent. The heat-resistant resin B in the polyamidene-based heat-resistant resin paste, -1 was polymerized. The yttrium imide precursor particles are dissolved in 7 - butyrolactone during heating, and are dehydrated and closed together with the heat-resistant resin A"-3 polyimine precursor. In a state polyimide resin compatible with each other. Please read back &

Order

Ministry of Economic Affairs, Intellectual Property Bureau, Consumer Cooperatives, Printing Synthetic Example 5 (Heat Resistant Rouge A"-4, 1,000 ml 4-necked neck with cooling tube equipped with a blender, thermometer, nitrogen inlet tube and oil-water separator BAPP 65.69 g (0.16 mol), bis(3,4-dicarboxyphenyl) dianhydride (hereinafter referred to as DSDA) 143.22 g (0.40 mol), isophthalic acid醯肼3 8.84 g (0.20 mol), 1,3-bis(3-aminopropyl)tetramethylbicyclooxane 9.93 g (0.04 mol) and r-butyrol 478 g. The scale applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 70 312417 1287030 A7

V. INSTRUCTION OF THE INVENTION (71) The reaction was carried out at 50 to 60 ° C for 1 hour with stirring, and then the temperature was raised to 195 C ' at the same temperature to carry out a reaction, and the number average molecular weight reached 27, 〇〇〇 (polystyrene equivalent). The reaction was terminated by cooling. The distilled water is quickly discharged from the reaction system. The resulting solution was released with r-butyrolactone to obtain a solution of a polyimine resin (heat resistant resin a'4) having a resin concentration of 30% by weight. Gold Example 6 (heat-resistant tree wax b,, -2) is placed in a cooling tube equipped with a stirrer, a thermometer, a nitrogen inlet pipe, and an oil-water separator, and a 4-liter long-necked flask is placed under a nitrogen gas. BAPP 102.64 g (〇·25 mol), bis(3,4-dicarboxyphenyl)ether dianhydride (hereinafter abbreviated as ODPA) 77.55 g (〇·25 mol) and r_butyrolactone 335 g. The reaction was carried out at 50 to 606 C for 1 hour, and the temperature was raised to 195 C, and the reaction was carried out at the same temperature. When the number average molecular weight reached 2,8 (polystyrene equivalent), the reaction was terminated by cooling. On the way, the distilled water is quickly discharged outside the reaction system. The obtained solution was released with 7-butyrolactone, and a polyimine resin (heat-resistant resin B, _2) having a sap concentration of 30% by weight was obtained, and a solution was printed by the Ministry of Economic Affairs, Ministry of Finance and Fisheries. M-Case 4 (heat-resistant tree ^ heat-resistant wax A'4 / 埶柹 埶柹 B B,, -2) 1 installed with a mixer, thermometer, nitrogen inlet tube and cooling tube 4 kinds of long-necked flasks were placed in the above-mentioned heat-resistant resin B - 2 polyimine resin solution (resin concentration: 3 〇 wt%) 2 〇〇 g ' and the above heat-resistant resin a, _4 醯Amine ylide resin solution (Resin paper size applicable to China National Standard (CNS) A4i_ (21〇χ 297 public)---- 71 312417 1287030 A7 B7 V. Invention description (72) The concentration is 30% by weight) 466.67 g, mixed and stirred at 180 ° C for 1 hour to prepare a homogeneous and transparent solution. When the solution which was cooled at 23 ° C for 1 hour was allowed to stand at 23 ° C for 1 month, the dispersed polyimine resin fine particles were precipitated in the solution. The fine particles were released with T-butyrolactone to obtain a polyimide-based resin paste (4) having a viscosity of 380 Pa·s and a thixotropic coefficient (hereinafter referred to as TI value) of 2.5. The polyimine resin fine particles recovered have a maximum particle diameter of 5 // m or less, are insoluble in r -butyrolactone at room temperature, and are soluble at 150 ° C. The polyimine-based heat-resistant resin paste (4) was coated on a glass plate (thickness of about 23⁄4 m) with a bar coater to have a thickness of 5 Å/m after heat drying, at 140 ° C for 15 minutes, 200. °C for 15 minutes, more than 30 (TC 60 minutes for heat treatment, to obtain a glass plate with a polyimine-based resin composition (4). The cured film is almost uniform and transparent, and the polyimide-based heat-resistant resin paste ( 4) The fine particles of the polyimine resin (heat-resistant resin B,, -2) are dissolved in r-butyrolactone during the hardening process, and more with the polyamide amide resin (heat-resistant resin a, -4) ) compatible with each other.

Synthesis Example 7 (resistance to waxy A, _U in a women's machine with a blender, a thermometer, a nitrogen inlet pipe, and a cooling pipe with an oil-water separator, and a 4-liter long-necked flask with nitrogen gas Into BAPP 89.09 g (0.217 m), DSDA 119.59 g (0.334 m), 2,2-bis(4-pyrimidin-3-aminophenyl) hexafluoropropyl (hereinafter referred to as HAB-6卩) 42.85 Gram (〇.117 mol) and 7^-butyrolactone 377 g. Under the mixing reaction, the reaction was carried out at 50 to 60 ° C for 1 hour, then the temperature was raised to 195 C 'reaction at the same temperature. When the number average molecular weight reaches 26, 〇〇〇 (polystyrene-converted value) is cooled and the reaction is terminated. On the way, the paper size that has been distilled is used to pass the 1f national standard (CNS) A4 specification (210 X 297). 312417 • -----------· ! I (Please read the notes on the back and fill out this page) Order · Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed 72 1287030 A7 Ministry of Economics The property bureau employee consumption cooperative printed five, the invention description) water rapid discharge reaction outside the system. The resulting solution was dissolved in y-butyrolactone to obtain a solution of a polyimine resin (heat-resistant resin VIII, -5) having a resin concentration of 40% by weight. Resin matrix paste: 埶 埶 resin a" -5 / 埶 埶 固体 固体 固体 固体 固体 固体 固体 固体 固体 固体 固体 固体 固体 固体 固体 固体 固体 固体 固体 固体 固体 固体 固体 固体 固体 固体 固体 固体 固体 固体 固体 固体 固体 固体 固体 固体 固体 固体 固体The 1,000 ml 4-neck flask equipped with a stirrer, a thermometer, a nitrogen introduction tube, and a cooling tube was heated to 180 ° C. The mixture was stirred at the same temperature for 1 hour to form a homogeneous solution, and then the above heat-resistant resin A was added. -5 polyimine resin solution (resin concentration of 4% by weight) 300 grams, and then it was stirred for 1 hour at 180. Then, it was cooled at 60 ° C for about 1 hour, and at 60 ° it was stirred for 1 day in the solution. The polyimine resin fine particles were precipitated to obtain a dispersed paste, and 48 g of 7-glycidoxypropyltrimethoxydecane was added to the paste, and the mixture was thoroughly mixed at room temperature, and then released with 7 · butyl acetal. The resin concentration was 36% by weight, and the obtained polyimine-based heat-resistant resin paste (5) had a viscosity of 150 Pa·s and a TI value of 3.5. The above polyimine-based heat-resistant resin paste (5) was glass. The thickness of the plate (thickness is about 2 mm) coated with a bar coater to heat and dry is 50 / / m, heat treatment at 140 ° C for 15 minutes, 200 ° C for 15 minutes, and more at 300 ° C for 60 minutes 'to obtain a glass plate with a polyimine-based resin composition (5). The cured film is almost uniform and transparent, The fine particles of the polyimine resin (heat-resistant resin B''-2) in the polyimide-based heat-resistant resin paste (5) are dissolved in 7-butyrolactone during the hardening process, and more with the polyimide resin ( Heat-resistant resin A'5) is compatible with each other. 0 This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm). 7 3 312417 C Please read the notes on the back first.

-A 1287030 A7 B7 V. INSTRUCTIONS (74) Example 21 ------------Read (please read the notes on the back and then fill out this page) Amine heat-resistant resin paste (〗 〖) (resin degree of mineralization is 30% 篁%) Adding ketone rubber elastomer fine particles with an average particle diameter of the surface-introduced epoxy group (Donglian • Ceramic Press) 40 parts by weight of "East-filler E-601" manufactured by Keto Co., Ltd.) and 70 parts by weight of butyrolactone were kneaded by three rolls to prepare a heat-resistant resin paste. The obtained heat-resistant resin paste (6) was defoamed, and then coated with a bar coater on a 5 inch wafer to have a thickness of 50 #m after heating and drying at 80 ° C for 5 minutes and 100 ° C for 10 minutes. Heat treatment was carried out at 150 ° C for 10 minutes, at 200 ° C for 15 minutes, and at 300 ° C for 60 minutes to obtain a tantalum wafer with a polyimide composition (6). The elastic modulus, the mechanical strength of the film, and the glass transition temperature were measured using the obtained polyimine-based resin composition (6). The modulus of elasticity was measured by a viscoelastic analyzer RSAll manufactured by Leometallic Scientific FE Co., Ltd. in air at a heating rate of 5 rpm and a frequency of 1 Hz. The mechanical strength of the film was measured by an iron Xilong universal testing machine UCT-5T manufactured by 〇ientecli. The glass transition temperature was measured by the Thermomechanical Analysis Device TMA/SS 6100 manufactured by Seiko Instruments Inc., printed by the Consumer Intellectual Property Office of the Ministry of Economic Affairs. Using the obtained heat-resistant resin paste (6) on a 8-inch wafer with a screen printing machine (manufactured by Zhongchang Precision Industry Co., Ltd., ls_34 GX with calibration device), nickel alloy plated with additives, no mesh An eye-metal version (manufactured by Net Industries, Inc., '100 Um thick, pattern size 8 mm x 8 mm) and a Bamarex metal doctor blade (Imported from Ba Industrial Co., Ltd.) to produce a resin film pattern to evaluate printability. The printed pattern was observed by an optical microscope for pattern flow and blur. 74 312417 The Chinese standard (cns) A4 specification (210 X 297 public) 1287030 A7 b/ 5, invention description (75) Carry out the following steps ··············································· a step of coating a plurality of resin layers by screen printing on a semiconductor substrate on which wiring is formed and drying; forming an electrode on the semiconductor substrate and a rewiring layer electrically conducting on the resin layer, forming a rewiring on the wiring a step of forming a protective layer; a step of forming an external electrode joint on the protective layer; a step of removing a portion where the solder ball is loaded, forming a protective layer; and a step of loading a solder ball. After dicing, a semiconductor device was fabricated. The semiconductor device was subjected to an iqoo cycle at a temperature cycle test of _65 t / 15 minutes and 150 C / 15 minutes, and it was evaluated that the semiconductor device was not abnormal. The evaluation results of the resin film and the semiconductor device obtained by the above heat resistant resin paste (6) are shown in Table 3. Example 22 A surface having an average particle diameter of 2 m was introduced in 23 parts by weight of the polyilylimide-based heat-resistant resin paste (2) (resin concentration: 30% by weight) of the s. Epoxy ketone rubber elastomer microparticles (East Lian Kee Co., Ltd.) "East-filled material E-601") 3 〇 weight and ester 50 parts by weight, mixed with 3 rollers The heat-resistant resin paste (7) was prepared, and the same operation as in Example 21 was carried out except for the final heating temperature of the Ministry of Economic Affairs, Intellectual Property Office, and the Consumer Cooperatives. The evaluation results of the resin film and the semiconductor device obtained by the above heat resistant resin paste (7) are shown in Table 3. Example 23 A surface of the epoxy group was introduced by adding an average particle to the 266 parts by weight of the polyilylimide-based heat-resistant resin paste (3) (resin concentration: 30% by weight) obtained in Preparation Example 3 Ketone rubber elastomer microparticles (Donglian • Tao Lishi Xi'an paper scale applicable to China National Standard (CNS) A4 specification (210x297 public) 75 312417 1287030 A7 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing 5, invention description (76 / "East-filler E-601" manufactured by Keto Co., Ltd.) 2 parts by weight and r-butyrolactone 26 parts by weight, and kneaded with 3 rollers to prepare a heat-resistant resin paste (8). The evaluation results of the resin film and the semiconductor device obtained by the above heat-resistant resin paste (8) are shown in Table 3. Example 24 The polyimine-based heat-resistant resin obtained in Preparation Example 4 was evaluated. The paste (4) (resin concentration: 30% by weight) is 200 parts by weight, and the surface-introduced epoxy group fluorene ketone rubber elastomer fine particles having an average particle diameter of 2 // m (Donglian • terracotta ketone) ) The company's "East Connected Filler E-601") 40 weight points and The resin film and the semiconductor device obtained from the heat-resistant resin paste (9) were evaluated in the same manner as in Example 21 except that the heat-resistant resin paste (9) was prepared by kneading three heat-resistant resin pastes (9). The evaluation results are shown in Table 3. Example 25 The average particle diameter was added to 176 parts by weight of the polyilylimide-based heat-resistant resin paste (5) (resin concentration: 36% by weight) obtained in Preparation Example 5 Microparticles of an epoxy group-based ketone rubber elastomer introduced on the surface of 2 (East-filled material E-601 manufactured by Tosoh Corp.) 4 〇 weight fraction and r-butyrolactone 95 In the same manner as in Example 21, the evaluation was carried out in the same manner as in Example 21, except that the heat-resistant resin paste (1 〇) was mixed and kneaded by three rolls. The evaluation results of the resin film and the semiconductor device obtained by the heat-resistant resin paste (10) are shown in the table. (3) In Example 26, an average particle diameter of 2 sheets of paper was added to the polystyrene-based heat-resistant resin paste (2) obtained in Preparation Example 2 (resin concentration of 30% by weight) of 3 16 parts by weight. The scale applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 76 312417 Please CAUTIONS on the back of reading

Page IIII ί 1287030 A7 __B7_ V. Inventive Note (77) The surface of the epoxy group-inducing ketone rubber elastomer microparticles (East Lianke Ketone Ketone Co., Ltd. In the same manner as in Example 22, the evaluation was carried out in the same manner as in Example 22 except that the heat-resistant resin paste (11) was prepared by kneading three rolls. The evaluation results of the resin film and the semiconductor device obtained from the heat resistant resin paste (11) are shown in Table 3. (Please read the precautions on the back and fill out this page) 4 丨 丨 'Ministry of Economics Intellectual Property Bureau Employees Consumption Cooperative Printed This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 77 312417 1287030 A7 B7 V. INSTRUCTIONS (78) Ministry of Economic Affairs, Intellectual Property Bureau, Staff and Consumer Cooperatives, Printed Articles, XS SO Οι lyriik w 1Φ, 13⁄4 οσ / -S c, οί^ 〇〇雀 On ^ u% o °^ Q (〇 9 u» o O〇ο 己(§) to u» o° 13⁄4 ο δ 1 Ο Ul o° H hH 舜/—NP 攀 w Sound photo 5 福 耀 诨 ' ' w ^ 4 聱 箨 Φ 1Φ m瘅戽萆鼯ω 戽W 萆>># m 蕃,, Ά本〇私Μ Ο to oo Os o On o 00 — o to La Ut 〇/—s Os Os 〇a \MN# 1 — &gt V# \» 菌 - NJ }^f 本〇Ο Lh ί〇Κ) ο 〇Η-^ o UJ oo to Lh o /-s Ui 〇ω Κ0 1 Η-Α > 1 to K) to J55r 〇Ο Ο tSJ ο ο 〇 00 — N-4 — • Private ΛΛ o u> Lh o 00 s—^ to 00 〇® α 祖 > 1 u> Η to OJ u>〇<1 to ΟΝ ΚΜ ON o On 〇00 — o to o o /"S v〇私〇〇ωNJ 藤κ>> sM I Η to Ui Lh νο Ο κ> Ui Ui Os 〇〇\ o oo — •o U> K) 1—* ooy—so ON 〇 ω I Κ>> Jj mold Lf* Μ th J^Sr L#% ο 私Ο to to <-Λ 'sD to u> K) Os to Vi ON o /^N hk U\ SO Ln ω I ·—a >s# 1 Ov Η KJ 〇n el n flf 1 nn ϋ ni ϋ « eMmr» 1 HF 1 1 i AJ — · n 1 n> nn I ni Is m (Please read the notes on the back first) Fill in this page) This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 78 312417 1287030 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative print 79 A7 B7 V., invention description (79) ^In addition to implementation The heat-resistant resin paste (6) of Example 21 was replaced by the polyanilin-based heat-resistant resin paste (1) obtained in the preparation example, and was evaluated in the same manner as in Example 2. As a result, a defect occurred in the temperature cycle test of the semiconductor device. Further, the evaluation results of the above-mentioned polyimine-based heat-resistant tree wax f(1) and the semiconductor device are shown in Table 4. The heat-resistant resin paste (7) of Example 22 was evaluated in the same manner as in the actual use of the imine-based heat-resistant resin paste (7) obtained in Preparation Example 2. As a result, a defect occurred in the temperature cycle test of the semiconductor device. Further, the results of evaluation of the lipid raft and the semiconductor device obtained from the above polyimine-based heat-resistant resin f (2) are shown in Table 4. f In addition to the heat-resistant resin paste (8) of Example 21, which was replaced by the polyimine-based heat-resistant resin paste (5) obtained in Preparation Example 5i, it was estimated to be (4). As a result, the temperature cycle of the semiconductor device is poor. Moreover, the evaluation results of the above-mentioned polyimide-based heat-resistant lipid film and semiconductor device are shown in Table 4, and (5) the tree of the tree was compared with the heat-resistant resin paste (6) of Example 21 as a synthesis example' , except for the substitution of the solution 2, the same operation as in Example 22: row °. Eight results are that the pattern will flow during screen printing, and the device cannot be fabricated. Further, the results of the evaluation of the heat-resistant resin Α, ,··2 are shown in Table 4.什之树~ Membrane evaluation 'paper scale applies Chinese National Standard (CNS) A4 specification (21GX 297 public love ―) 312417 -------i ^ · ---* — 1--I (please read first Note on the back side of this page) 1287030 A7 B7 V. Inventive Note (80) Comparative Example 6 The heat-resistant resin paste (8) of Example 23 was added to the heat-resistant resin A''-3 solution obtained in Synthesis Example 3. Iroki, except for the resin paste having a viscosity of 350 Pa · s and a u value of 5.0, was evaluated in the same manner as in Example 23. As a result, the modulus of elasticity was 2.8 GPa at -65 ° C, and the amount of change in modulus of elasticity at 150 ° C was 7%. Further, the glass transition temperature was lowered to 16 ° C, and the surface of the resin film was broken during the sputtering process when the semiconductor device was fabricated. As a result, a semiconductor device cannot be fabricated. Further, the evaluation results of the resin film obtained from the above resin paste are shown in Table 4. . ------------ (Jing Xian read the phonetic on the back? Please fill out this page again.) Line!! Ministry of Economic Affairs, Intellectual Property Bureau, Staff and Consumer Cooperatives, Printed Paper Scale Applicable to China National Standard (CNS) A4 Specification (21〇X 297 mm) 80 312417 1287030 A7 B7 V. Invention Description (81 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative system

It 麦Μ m WW 谇*"d P KJi ΙΦ 〇° Μ /—S 〇° C difficult. se w os H-» <-Λ o W OO P3 δ ro Lh O〇ο δ I Os U% 〇° H h-< hemp/-NP • 09 rhinoceros s pants s generation -3⁄4 爷 m ΙΦ s 戽 戽 a a % Λ s» m > Μ on 寐 cage han m treatment Ln private IM Toto 00 u» NJ Ol OJ — u> LO *〇私00o 〇H-* : ο ο ω t > ττ η Xuan Zang ·—» o KJt 4^ ί—* K) κ> LA to u> — u>u> C/lo 1m o Η·* ο ο 〇ϋ \0 λ > VJ 1 to Yu UJ * o Ό KJ\ Κ) σ> ο <i to u>U> U» U% o ^J\ o Η-ι ο ο ® Sf 1 Μ > \* f Ot 4^ 1 1 1 ♦—* 〇o U> SO Ο to ο L#i On u> — •V〇K>< 1 U) o 1-^ fc·^ ON o /^S > I to 'w^ o ►—* ο ο 1 > \β 廉κ> Ui 1 牦1 '-I o u> 00 ο Os 〇 K> to Ui to 00 Ul 〇u> oi > N s net o ♦—»· ο ο 1 > 1 u> 〇 (please read the notes on the back and fill out this page)

This paper scale is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) 81 312417 1287030 A7 B7 V. Invention Description (82 Exemption Example 27 Polyurethane heat-resistant resin paste (Hitachi Chemical Industry Co., Ltd.) Manufactured by the company, GH-P500) 233 parts by weight (resin concentration of 3% by weight) was added to the surface of the oxime ketone rubber elastomer fine particles with an average particle size of 2 / / m (Donglian • terracotta 30 parts by weight of ketone (manufactured by the company) and 30 parts by weight of 7-butyrolactone, and kneaded with 3 rolls to prepare a heat-resistant resin paste. After defoaming, a plurality of electronic circuits are formed on one surface of a ray wafer having a diameter of 8 inches and a thickness of 600 m, and an electronic circuit is turned on the same surface, and a plurality of electrodes are connected to the outside of the periphery of the electronic circuit to remove Protecting the electrode portion of the polyimide film of the electronic circuit, removing at least the electrode on the semiconductor substrate on which the electronic circuit surface is formed, at least using a metal mask on the electronic circuit, and printing a plurality of island shapes at 25 (TC hardening) 1 hour, A resin layer is formed on the resin layer of the above-mentioned semiconductor substrate, and a metal sputter film such as chromium-copper or chrome-platinum-steel of 〇1 to 2//111 is formed. Here, road-steel is used to form 0 5/m Next, in order to form the second wiring layer, a plating resistor having a thickness of 10 to 40/zm is formed on the sputtered metal film. The thickness of the plating resistor is selected in accordance with the thickness of the desired electrolytic copper plating. A 2 〇wmi resistor is formed, and after plating, a plating resistor is developed, and the exposed portion of the sputtered metal film is electroplated with electrolytic steel. After the electric iron is completed, the remaining plating resistor is peeled off to form a second wiring layer. The second wiring layer is removed. A part of the solder ball is placed, and a protective layer is formed on the second wiring layer. A nickel-aluminum plating layer of 0.3/zm is formed on the electroplated steel plate having a diameter of 4〇0#, and the ball is loaded. The semiconductor substrate is cut into individual pieces by a 矽 wafer dicing device, and the half-size paper size is obtained by the Chinese National Standard (CNS) A4 specification (2) G x 297 publicity) " Please read the back note and fill out this page. read

I I ίtr i I 82 312417 1287030 A7

V. Description of the invention (S3) Conductor placement. At this time, the elastic modulus was measured by a viscoelastic analyzer RSAn manufactured by Leometallic Scientific FE Co., Ltd. at a temperature of 5 rpm and a frequency of i Hz. The glass transition temperature was measured using a thermal mechanical analysis device TMA/SS6100 manufactured by Seiko Instruments. The viscosity was measured by an e-type viscometer (manufactured by Tokyo Bartock (ed.), EHD-U type), and measured by the number of revolutions OJmiiT1 (25 ° C). Further, the thixotropic coefficient (hereinafter referred to as the enthalpy value) is the ratio of the apparent viscosity of the reciprocating number 11^11-1 to 1〇miiri, 7^1 and 77IO, to ? 7l/?7l〇 indicates. Example 28 To 30 g of 1 - amidoximeimide powder, 7 g of butyl vinegar was added and stirred, and the mixture was heated at 250 ° C for 1 hour. After the heating was stopped, the mixture was naturally allowed to cool to room temperature while stirring to obtain a yellow-brown paste. Next, a yellow-brown paste of 1 gram (non-volatile fraction of 30 grams) was added to an anthrone rubber-filled material having an average particle diameter of 2 vm and an epoxy-modified surface (East Lian In the same manner as in Example 1, a semiconductor device was obtained in the same manner as in Example 1 except that the resin paste was obtained by kneading and dispersing three rolls with 25 rolls of "East Filling Material E-601". Please read the > main item on the back

The Ministry of Economic Affairs, Intellectual Property Office, Consumer Cooperatives, Printing Example 29, the resin paste obtained in Example 28 was directly coated with a resin layer on the same semiconductor substrate as in Example 27 using a spray nozzle (inner diameter: 150/zm), A semiconductor device was obtained in the same manner as in Example 27. Example 30 The Chinese National Standard (CNS) was applied in accordance with the same paper size as in Example 2 except that the epoxy-modified surface of the epoxidized surface of Example 28 was changed from 25 gram to 30 gram. ) A4 size (210 X 297 mm) 83 312417 1287030 A7 B7 V. Method of Invention (84) A semiconductor device is obtained.

A semiconductor device was obtained in the same manner as in Example 27, except that only the polyimide-based heat-resistant resin paste of Example 27 was used. Comparative Example 8 The heat-resistant resin paste obtained in Example 27 was blended with cerium oxide micropowder (manufactured by Sakamoto Aiqiqi Co., Ltd., Irooch 200) to adjust the viscosity to 1000 Pa · s, and the TI value exceeded 1. A semiconductor device was obtained in the same manner as in Example 27 except for 〇. In Comparative Example 8, the viscosity of the heat-sensitive resin paste was 1200 Pa·s, and the TI value was 10.2. Comparative Example 9 The same procedure as in Example 28 except that the yellow-brown paste obtained in Example 28 was blended with cerium oxide micropowder (manufactured by Nippon Aurora Co., Ltd., Irooch 200) to adjust the viscosity to more than 1000 Pa·s. The semiconductor device is obtained by the same operation. Comparative Example 10 A semiconductor device was fabricated in the same manner as in Example 28 except that the oxime ketone rubber filler of the epoxy group-modified surface of Example 28 was replaced with an acrylic rubber filler having an average particle diameter of 2 // m. Comparative Example 11 A semiconductor device was obtained in the same manner as in Example 28 except that the epoxy group-modified epoxy resin of the epoxy group-modified surface of Example 28 was changed from 25 g to 30 g. This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 public) 84 312417 ------------ Continued (please read the notes on the back and fill out this page) ------ Ministry of Economic Affairs, Intellectual Property Bureau, Staff Consumer Cooperative, Printed 1287030

5. Description of the Invention (85) The semiconductor devices of the embodiments 27 to 30 and the comparative examples 7 to u are mounted on an external electrode of a semiconductor device having a thickness of 1.6 mm and a size of 3 mm × 3 mm. The substrate was formed on the substrate (manufactured by Hitachi Chemical Co., Ltd., trade name Mcl E_67). Then, it was put into the thermal shock test machine 'for -65 °C / 15 minutes' 15 〇 c / 15 minutes temperature cycle test 1000 cycles, and secondly, the electrical resistance of the solder joint was measured 'more polished semiconductor device' observation Defects in the solder joint and observation of peeling and breakage inside the semiconductor device. Table 5 shows the evaluation results of the tree I layer characteristics of the examples and the comparative examples, the temperature cycle resistance of the semiconductor device, and the process of fabricating the semiconductor device. Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperatives Printed Table 5 Project Example Comparative Example 27 28 , .......' L- 29 30 7 8 9 10 11 Elasticity Rate -65〇C 1.3 1.2 1.2 0.6 3.4 1.0 3.4 2.9 0.2 25〇C 1.0 1.0 1.0 0.5 3.1 0.8 3.1 2.5 0.1 15〇t: 0.7 0.8 0.8 0.3 2.5 0.6 2.5 0.2 0.1 Elasticity ξ (150°C/- ! (%) 65 °〇54 67 67 50 74 60 78 7 50 Viscosity (Pa · s) 250 530 530 560 380 1200 > 1000 540 580 Depreciation 6.0 4.2 4.2 4.0 3.0 10.2 3.9 3.8 4.2 Glass transfer Wei (.C) 220 205 205 200 285 280 240 160 180 5% by weight Reducing temperature (°C) 405 405 405 400 425 420 440 380 395 Resin forming method Printing printing Jet printing Printing printing Printing printing resin layer forming OK OK OK OK OK OK Printing OK NG OK OK Temperature cycling resistance (defective/testing) Number) 0/20 0/20 0/20 0/20 5/20 — * — 5/20 In Comparative Example 10, the modulus of elasticity is 2.9 GPa at -65 ° C, 0.2 GPa at 150 ° C, and the modulus of elasticity changes. The amount is 7%. In addition, the glass transition temperature becomes lower. This paper scale applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm). 85 312417 1287030 Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperative Printed Β7 Β7 V. Inventive Note (86) 160 °c, there is no sputtering resistance during the process of fabricating a semiconductor device, and the fabrication steps of the second wiring cannot be performed. In the semiconductor device, it is understood from Table 5 that the semiconductor insulating resin shown in Examples 27 to 30 can be used to improve the resistance in the process of fabricating a semiconductor device, and the reliability of the semiconductor device can be greatly improved. Polyimide-based heat-resistant resin paste (manufactured by Hitachi Chemical Co., Ltd., GH-P500) 233 parts by weight (the resin has a concentration of 3 〇, the average particle size is 2 // m, and an epoxy group is introduced on the surface.矽 ketone rubber elastomer granules ("East Bean Filling Material E-601" manufactured by Tosoh Pharma Press Co., Ltd.) 30 parts by weight and 7 - butyrolactone 5 〇 by weight, mixed with 3 rollers Refining, preparation of heat-resistant resin paste. After the obtained heat-resistant resin paste is defoamed, a plurality of electronic circuits are formed on one side of the wafer having a diameter of 8 inches and a thickness of 600 //m, and the electronic circuit is turned on the same surface, and the periphery of the electronic circuit is connected to the outside. The plurality of electrodes are removed from the electrode portion of the polyimide film of the protective electronic circuit, and at least 80 minutes after the spin coating on the semiconductor substrate on which the electronic circuit surface is formed, i 〇 (TC 10 minutes, 15 〇) The resin layer is obtained by heat treatment at ° C for 10 minutes, at 200 ° C for 15 minutes, and at 250 ° C for 60 minutes. Next, the electrode portion of the semiconductor element is exposed by laser processing. The resin layer is formed on the semiconductor substrate. a metal sputter film such as chromium-copper or chrome-in-one copper, etc. Here, chrome-copper of 〇5//nl is formed. Then, 1 〇 to 40//m thick is formed on the above-mentioned galvanic metal film. The plating resistance. The thickness of the plating resistor is matched with the thickness of the desired electrolytic copper plating. 'This is 20 em. After exposure, the plating resistance will be imaged, and the sputtering metal will be used. The Chinese national standard (CNS) ) A4 specifications (2) 297 297 public) 86 312417

Printed by the Ministry of Economic Affairs, Intellectual Property Office, Staff and Consumers Co., Ltd. 87 1287030 A7 ____B7______ V. INSTRUCTIONS (87) The exposed portion of the film is electroplated with electrolytic copper. After the plating is completed, the residual resistor is peeled off to form a second wiring layer. The portion where the solder ball is placed on the second wiring layer is removed, and a protective layer is formed on the second wiring layer. A nickel-aluminum plating layer of 〇.3/zm was formed on the electroplated steel plate on which the solder balls (400 #m in diameter) were placed. The semiconductor substrate was cut into individual pieces by a silicon wafer dicing apparatus to obtain a semiconductor device. At this time, the modulus of elasticity was measured by a viscoelastic analyzer RSAII manufactured by Leometallic Scientific FE Co., Ltd. at a heating rate of 5 ° C / min and a frequency of 1 Hz. The glass transition temperature was measured by a thermomechanical analyzer TMA/SS6100 manufactured by Seiko Instruments Co., Ltd. The value of the modulus of elasticity of the resin used at -65 ° C, 25 ° C, 150 ° C after heat treatment, -65 ° C and 15 ° ° (: the rate of change of modulus of elasticity, the value of glass transition temperature as shown 1 shows. Example 32 70 g of r-butyrolactone was added to 30 g of polyether amidoxime powder and stirred, and heated at 150 ° C for 1 hour. After heating was stopped, the mixture was naturally allowed to cool to room temperature with stirring. Obtain a yellow-brown paste. Next, 100 g of a yellow-brown paste (30 g of non-volatile matter) is added to the anthraquinone rubber filler with an average particle diameter of 2 em and an epoxy-modified surface (East L. (manufactured by the company, East Co., Ltd., E-601) 25 g, kneaded and dispersed with three rolls, and after obtaining a resin paste, a semiconductor device was obtained in the same manner as in Example 31. Example 33 Example 3 1 The heat-resistant resin paste obtained is coated on a polytetrafluoroethylene plate with a bar coater to have a thickness of 1 〇〇 #m after heating and drying, and is applicable to the Chinese National Standard (CNS) A4 specification (210 X) on 8 paper scales. 297 public) 312417

1287030 Α7 Β7 V. Inventive Note (88) 加热C5 minutes, 100°C for 10 minutes, 150°C for 10 minutes, and 200°c for 15 minutes, heat treatment was carried out to obtain a film-like resin. This resin was laminated on the same semiconductor substrate as in Example 31, and further heat-treated at 250 ° C for 60 minutes, and then a semiconductor device was obtained in the same manner as in Example 31. (Example 34) A semiconductor device was obtained in the same manner as in Example 32 except that the oxime ketone rubber filler of the epoxy group-modified surface of Example 32 was changed from 25 gram to 30 gram. Comparative Example 12 A semiconductor device (with not added fluorenone rubber elastomer fine particles) was obtained in the same manner as in Example 31 except that the polyimine-based heat-resistant resin paste of Example 31 was used. Comparative Example 13 A semiconductor device was fabricated in the same manner as in Example 32 except that the shredded rubber filler of the bad oxygen-modified surface of Example 32 was replaced with an acrylic rubber filler having an average particle diameter of 2/zm. Comparative Example 14 Printing by the Ministry of Economic Affairs, Intellectual Property Office, Employees' Consumption Cooperative, except that the ketal rubber filler of the Example 3 2 was changed from 25 gram to 30 gram in the same manner as in Example 32. A semiconductor device is obtained. The semiconductor devices of the above-described Embodiments 31 to 34 and Comparative Examples 12 to 14 were mounted on a substrate on which electrodes were formed at positions corresponding to external electrode tabs of a semiconductor device having a thickness of 1.6 mm and a size of 30 mm × 30 mm. (Manufactured by Yuli Chemical Industry Co., Ltd., trade name MCL Ε_67). The paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) 88 312417 1287030 A7 V. Invention description (89), put into the thermal shock test machine, who is "Μ进仃-65〇C15 minutes 15〇.

The temperature cycle test was 1000 cycles. Gan "knife M ± clothing second, measuring the electrical resistance of the solder joint, polishing the semiconductor device, observing the poor condition of the known tin joint and observing the inside of the semiconductor device. Peeling and breaking The results are shown in Table 6.

Tpc ° Please read the back © Note

Page 205 225 200 285 Resin formation method Rotary coating resin layer formation οκ Temperature cycle resistance _ (defective/experimental) 0/20 160 180 Spin coating OK 0/20 Lamination OK 0/20 Rotary coating OK 0/20 Spin coating OK 5/20 Rotary coating spin coating QK 5/20 Schedule 6 Example

Elasticity change (°/〇) (150°C /-65°C) Glass transfer temperature (°C) 220 54 50 74 7 50 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed in Comparative Example 13, the elastic rate is _ 65 ° C is 2.9 GPa, 15 (TC is 0.2 GPa, the modulus of elasticity change is 7%. In addition, the glass transition temperature is lowered to 1 60 ° C ' in the process of fabricating a semiconductor device without sputtering resistance, can not In the process of fabricating the second wiring, the semiconductor device cannot be obtained. On the other hand, it can be understood that the resins shown in Examples 31 to 34 can be used to improve the resistance of the semiconductor device and greatly improve the semiconductor device. Embodiment 35 An embodiment of the present invention will be described with reference to Fig. 1. Polyurethane-based heat-resistant resin paste (manufactured by Hitachi Chemical Co., Ltd.) GH_ This paper scale applies Chinese National Standard (CNS) A4 size (210 X 297 mm) 89 312417 1287030

P500) 233 parts by weight (resin concentration of 3% by weight) was added to the granules of the fluorenone rubber elastomer having an average particle diameter of .2/zm and introduced into the epoxy group on the surface (Donglian • terracotta ketone) The company manufactures, East Connected Filler E-6〇l) 3 () weight fraction and r· Butyrolactone 50 parts by weight, and is kneaded by three drums to perform defoaming to obtain a heat resistant resin paste. The obtained heat-resistant resin paste was coated on a polytetrafluoroethylene substrate with a bar coater to have a thickness of 25 μm after heat drying, at 80 ° C for 5 minutes, at 100 ° C for 10 minutes, and at 15 (rc 1 minute). 2〇(Γ(: 15 minutes, more than 250°C for 60 minutes, heat treatment, to obtain a resin film. The resin of the Ministry of Economic Affairs, Intellectual Property Bureau, the staff of the consumer cooperatives, the elastic modulus of the film produced by Leometallic Scientific FE Co., Ltd. The elastic analyzer RSAII was measured at a temperature rise of 5 ° C / min and a frequency of 1 Hz. The glass transfer temperature was measured by a thermomechanical analyzer TMA/SS6100 manufactured by Seiko Instruments Co., Ltd. The diameter of the electronic circuit was 8 inches and thickness. On the semiconductor wafer 3 of 6〇〇//m, a screen printing machine (LS-34GX manufactured by Zhongchang Precision Industry Co., Ltd. with calibration device) and a metal mask (manufactured by Net Industries, Ltd., thickness 100/zm) are used for printing. The heat-resistant resin paste has a thickness of 5 Å/zm after heat drying. The printing position is the same as that of the semiconductor device, and the range of the dicing region 8 is removed. At 80 ° C for 5 minutes, i 〇 (TC 10 minutes, 15 (Γ (: 1〇) The resin was heated at 200 ° C for 15 minutes and further at 25 (rc for 60 minutes to obtain a resin layer 1 (Fig. 1 (b)). The state of the resin layer 1 was laser-processed until the electrode pad 5 was exposed. The diameter is 5〇em (Fig. 1(c)). A chromium sputtered metal film having a thickness of 〇5//111 is formed on the resin layer 1 by a sputtering apparatus, and a thickness of the electrode is coated on the sputtered metal film. This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 90 312417 (please read the notes on the back and then write this page) Order -------- ----- 1287030 A7 -- V. Description of invention (91 Resistor' is formed by electro-exposure processing in the copper plating wiring part to form an electrode resistance layer, and copper wiring is formed by electrolytic electrowinning in the exposed part of the carbon-emitting metal enamel' copper wiring reaches 15^m After that, the plating resistor is peeled off, and the exposed portion of the metal film is removed to form the second wiring layer 6 (jth (10). In the resin layer 1J1 in which the second wiring layer 6 is formed, the screen printing machine, the medium length precision industry Manufactured by the company, ls_34gx with calibration device, metal mask (made by Mesh Industrial Co., Ltd.) thickness 4G//m The heat-resistant resin paste is printed to have a thickness of 20 after heat drying. The printing position is the same as that of the semiconductor device, and the range of the dicing region 8 is removed, and 5 minutes, i〇〇°c ίο minutes, 15 (rc 10 minutes, 20 (rc 15 minutes more than 25 〇 c 6 〇 minutes heat treatment, obtain the second wiring layer of the protective layer 2 (the first!)). In the second wiring layer of the protective layer desired position The outer joint 7 is obtained by laser processing until the second wiring layer 6 is exposed, and the diameter is 3 〇〇 jWm (Fig. 1 (f)). The semiconductor wafer 3 is cut in the dicing region 8, and the individual semiconductors are mounted on the external splicing joints 7 of the semiconductor device to mount solder balls having a diameter of 〇4 mm, and then the semiconductor device is mounted at a size of 3 mm 3 . A substrate on which an electrode is formed at a position corresponding to an external electrode joint of a semiconductor device having a thickness of 1.6 mm (manufactured by Hitachi Chemical Co., Ltd., trade name MCL Ε-67). Next, it was placed in a thermal shock tester and was carried out at -65. (: 15 minutes, 150 ° C 15 minutes for 1 cycle of temperature cycle test 1000 cycles. This paper scale applies to China National Standard (CNS) A4 specifications (210 X 297 public) 91

Page 4 312417 1287030 A7 B7 92 V. Description of the invention (Example 3 6) In a polyether amidoxime powder 3 () 8 g and stirred, heated at 15 ° C for 1 hour - 丁内知 70 publicly cool to To the dish, obtain a yellow-brown paste. Then add 100 grams (non-volatile 30 grams) to the ketone rubber filler with an average particle size of 2 and then brown = agent-modified surface, and 111'% by oxygen. Filling material £-601) 25 mm j1 ± ( } 1 % After obtaining the resin paste, according to the embodiment, the device was obtained in the same manner as in Example 35. In addition to the example of Example 36, A silicone device was changed from 25 gram to 30 gram* of the surface-modified ketone rubber filler, and the semiconductor device was obtained in the same manner as in Example 36 except for the brother and the brother. Comparative Example 15 Except that only the embodiment was used. A semiconductor device was obtained in the same manner as in Example 35 except for a polyethylenimine-based heat-resistant resin paste of 35. Comparative Example 16 The average particle diameter of the anthrone rubber filler of the epoxy group-modified surface of Example 36 was used. Replaced with 2 // m acrylic rubber filler, with Example 3 6 A semiconductor device was fabricated in the same manner. Comparative Example 1 7 The same procedure as in Example 36 was carried out except that the oxime ketone rubber filler of the epoxy group-modified surface of Example 36 was changed from 25 gram to 30 gram. Obtaining a semiconductor device. 312417

S Project Example Comparative Example 35 36 37 15 16 17 Elasticity (GPa, 25 ° C) 1.0 1.0 1.0 3.1 2.5 0.1 5% weight reduction temperature) 405 405 405 425 420 395 Glass transfer temperature (°c) 220 220 220 285 160 180 Resin layer formation OK OK OK OK OK Temperature cycle resistance (bad number/test number) 0/20 0/20 0/20 5/20 — 5/20 Defective — — — Solder joint — Wiring is broken 1287030 A7 ----------Β7 _ V. DESCRIPTION OF THE INVENTION (93) Evaluation of the elastic modulus and glass transition temperature of the semiconductor devices of Examples 3 to 37 and Comparative Examples 1 to 5 In the temperature cycle test and the resin layer formation property, the semiconductor device was polished even when the defect occurred, and the solder joint portion or the inside of the semiconductor device was observed to be peeled off and broken. The results are shown in Table 7. As a result, in Examples 35 to 37, the defects of the solder joint portion and the peeling and breaking of the inside of the semiconductor device were not observed until the 1 〇〇〇 cycle. In Comparative Example 1, the glass transition temperature was lowered to 16 〇〇c, and the sputtering resistance was not obtained in the process of fabricating the semiconductor device, and the second wiring layer fabrication step could not be performed, and the semiconductor device could not be obtained. As is apparent from Table 7, by using the resin layers shown in Examples 35 to 37, the durability in the process of fabricating a semiconductor device can be improved, and the reliability of the semiconductor device can be greatly improved. [Industrial Applicability] According to the resin composition of the present invention, it is possible to obtain a resin having the same resin properties as that of polyimine without accompanying the imidization process, and having excellent strength and flexibility. membrane. Further, a fine pattern can be formed by screen printing or sputter coating, and the semiconductor device using the resin composition of the present invention can impart good characteristics. This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 public) ---- 312417 --------------- (Please read the notes on the back and fill in this Page 1 订 经济 经济 经济 93 93 12 93 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 The elastic modulus can be arbitrarily controlled, and a resin film excellent in heat resistance can be formed, which has thixotropic properties and can be applied to a coating method excellent in efficiency such as screen printing or sputter coating. The semiconductor device of the present invention has thixotropy and can be widely used as a coating material, a binder, and a stress buffering material for a semiconductor device obtained by applying a heat-resistant resin paste having a coating method superior in coating efficiency such as screen printing or sputtering. For example, a resin film having an excellent modulus of elasticity and having excellent heat resistance can be arbitrarily controlled. According to the present invention, since the resin layer has a low modulus of elasticity, the stress applied to the external electrode joint after mounting is excellent in cushioning property, and the resistance in the step of forming the second wiring layer by screen printing is due to the heat resistance of the resin layer. Advantageously, the solvent resistance is superior in the step of forming the second wiring layer by electroplating. Further, by using the resin having the above characteristics, a semiconductor device excellent in reliability can be obtained without using an underfill resin. The present invention provides a semiconductor device manufacturing method in which a resin layer and a wiring protective layer are excellent in adhesion, and a semiconductor device having excellent reliability and reliability is formed in a batch on a semiconductor wafer. --------------- (Please read the notes on the back and fill out this page) Order · Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed This paper scale applies to China National Standard (CNS) A4 size (210 X 297 mm) 94 312417

Claims (1)

1287030 Patent Application No. 90105091, the scope of application of the patent application (January 15, 1996) 1 · A resin paste characterized by containing (A) a polyether amidoxime or an imide soluble in a polar solvent at a temperature or a heat-resistant resin of polyether amide, (B) a sulphur-resistant resin of polyether amidoxime, polyether amide or polyether oxime which is insoluble in a polar solvent at a temperature but soluble by heating And (C) organic solvents. 2. The resin paste of claim 1, wherein the resin (4) is an aromatic diamine compound represented by the following formula (1); (4). Let NH2(1) 弋 R, R, r3 and r4 each independently be a hydrogen atom, and be printed by the Central Bureau of Standards and Staff Welfare Committee of the Ministry of Economic Affairs: 1 to 9 alkyl groups, carbon atoms to 9 alkoxy groups or A halogen atom, X is a single bond, -0_, _s_, _c(=〇)..._s〇2_, _S(==〇)- or a base represented by the following formula, and each of the repetitive units may not be ◎, stolen or A R6, Han and 11 are each independently a hydrogen atom, an alkyl group, a trifluoromethyl paper scale & ((10))----^—— --__ 1 ^241 amend this 1287030 H3 trichloromethyl, letter a halogen atom or a phenyl group; (2) a diamine compound formed from the following constituents (a) and/or (b); (a) an aromatic diamine compound other than the general formula (I), (b) An aliphatic or alicyclic diamine compound, and (3) an acid compound formed from the following components (c) and/or (d); (c) a dicarboxylic acid or a reactive acid derivative thereof, (d) TriWereic acid or a reactive acid derivative thereof, or those obtained by reacting the above (1) and (3). 3. The resin paste of claim 1, wherein the resin (B) is an aromatic diamine compound represented by the following general formula (I); -NH, (I) In the printed version of the Central Bureau of Standards and Staff Welfare Committee of the Ministry of Economic Affairs, 'R1, R2, R3 and R4 are each independently a hydrogen atom, a carbon atom with a carbon number of 1 to 9, and a carbon number of 丨 to 9 Alkoxy or a halogen atom, X is a single bond, -〇_, -C(=〇)_, _s〇2_, -s(= 〇)—or a group represented by the following formula, R. and R6 are each independently a hydrogen atom, an alkyl group, a trifluoromethyl nonylmethyl group, a halogen atom or a phenyl group; the paper scale applies to the Chinese national standard (cns) Mia^ T^7〇X297 公楚y 31241 Amendment 1287030 Η3 (2) An aromatic diamine compound which is a compound of the following formula (a) and/or (b); (4) an aromatic diamine compound other than the general formula (1); (b) an aliphatic or alicyclic diamine compound, and (3) a compound represented by the following formula (4) and/or (4). And compounds derived from the following; 35 or its reactive acid-derived (C) diterpene acid or its reactive acid derivative, (d) diacid or its reactive acid derivative (II) where Y is a single bond, _0_, _s...c(=〇) _, _s〇2, _heart Ο): a group represented by the following formula or a divalent aromatic smoky group, an aliphatic smoky group Or an alicyclic hydrocarbon group, each of which may be different from each other; or -C-In the Central Standards Bureau Staff Welfare Committee Printed Form, R5 and R6 have the same meaning as the above; or (1) and (3) above The person who performed the reaction. 4. The resin paste of claim i, wherein the resin (β) is (1) an aromatic diamine compound represented by the following general formula (I); and 31241 amendment 1287030 The number is from 1 to 9 and the alkoxy group having a carbon number of i to 9 or a halogen atom, and X is a single bond, -〇-, ..._c(==0)_, _s〇2_, -S(= = 〇) The basis of one or the following formula may be different from each other; or ◊ In the printed version of the Central Bureau of Standards Staff Welfare Committee of the Ministry of Economic Affairs, R5 and R6 are each independently a hydrogen atom or an alkyl group. Trifluoromethyltrichloromethyl, halogen atom or phenyl; (2) February (a), which is formed by the following constituents (a) and/or (b) a compound of a diamine compound, (b) an aliphatic or alicyclic diamine compound, and (3) a tetradecanoic acid derivative represented by the following general formula (π); 9 > (XX) a compound; or an anhydride or a reactive acid form, Y is a single bond, ~)_S〇2_, _s(= 〇), a group represented by the following formula or a divalent argon furnace, a core group, an aliphatic hydrocarbon group or This paper scale applies to the Chinese National Standard (CNS) Α4 specification (210 X 297 mm) 31241 revision! 287〇3〇 The lipid oxime hydrocarbon group may be different from each other in the repeating unit -c. or wherein R5 and R6 have the same meaning as the above; or the above (1) and (3) are reacted. The resin paste of any one of claims 2 to 4, wherein the aliphatic or alicyclic:amine compound is cleaved to contain a diamine-based oxime represented by the following formula (m) (III) H2N-Bubu 丨 · · · · · · · · · · · · · · · · · · · · · · · R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R An alkyl substituted phenylene group, 11 being an integer from i to 30. 6. If the resin paste of any of the scopes 2 to 4 of the patent application is printed, the resin composition of the Central Bureau of Standards of the Ministry of Economic Affairs printed in the Ministry of Economic Affairs, the resin composition further contains a rubber elastic low elastic filler or liquid. Rubber. • A resin paste as claimed in claim 6 wherein the resin composition comprises a chemically modified, low-elastic filler having rubber elasticity. " • A resin paste according to item 6 of the patent application, wherein the surface of the low elastic filler is chemically modified by an epoxy group. This paper scale applies to the Chinese National Standard (CNS) A4 specification (210X297 mm). 5 31241 Amendment 3287030 _ H3. If the patent application scope is 7th, the surface of the sound surface is "the moon", where the low elastic filled surface The epoxy group is modified by the epoxy group. 10. The average grain kneading system of the material of the patent application is the 〇.] to... _ (4) The resin paste of the 1G item of the patent scope is filled, wherein Arbitrarily controlled in the range of 〇. 2 to 3 birds, in _: * The car's modulus of elasticity for -65t is 1 () to _ ^ application for patents" 11 (4) paste, wherein the resin consists of 5 glass The transfer temperature (Tg) is 8 (above rc, and the thermal decomposition temperature is more than c. 13. The resin paste of claim 12, wherein the resin has a viscous viscosity in the range of 1 to iOOOPa. The thixotropy system is in the range of 2 or more, and can form a fine pattern. 14. The resin paste of the scope of the application of the fifth to fourth items is used in semiconductor devices. 1 5 · Heat resistance Resin paste, which is characterized by the Ministry of Economic Affairs, Central Bureau of Standards, Staff Welfare Committee Printing a resin paste as claimed in claim 1 and (D) a rubber-elastic particle or a liquid material. 16) The heat-resistant resin paste of claim 15 wherein the heat resistance is The heat-resistant resin b of the resin A and (B) is an aromatic polyamidene resin (D) obtained by reacting an aromatic tetracarboxylic acid dioxene with an aromatic diamine, and the main component of the rubber-elastic particle The component is a zeitosterone rubber. 17. The heat-resistant resin paste of the 15th article of the patent application scope, wherein the paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm). 1287030 The heat resistant resin B is an aromatic tetracarboxylic dianhydride containing 50% by mole or more of 3,4,3,4,2-dibenzophenonetetracarboxylic dianhydride, and contains 50% by mole or more. 4, the aromatic polyimine resin obtained by reacting the aromatic diamine of diaminodiphenyl ether, and the main solvent of (c) is 7-butyrolactone. 1. The heat-resistant resin paste according to the fifteenth aspect of the invention, wherein the particles of the elastic rubber particles have an average particle diameter of from 〇1 to 5〇#m. 1. The heat-resistant resin paste of claim 15 wherein the resin film obtained from the heat-resistant resin paste is arbitrarily controllable in a range of from 0.2 to 3 · 〇GP a The elastic modulus at 150 °C is 1 〇 to 1 〇〇% of the elastic modulus at -6 5 C. 20. The heat-resistant resin paste of claim 15, wherein the resin film obtained from the heat-resistant resin paste has a glass transition temperature of 18 or more, and a 5% weight loss temperature of 300 ° C or more. 2 1 ·If the patent scope is 苐1 5, the thermal resin is poor, and the viscosity of the resin paste is 1 to 1〇〇〇pa · s and the thixotropy coefficient is 1.2 or more. 22·If the patent application scope The heat-resistant resin paste of item 15 is used for the resin film of a semiconductor device. The Ministry of Economic Affairs Central Bureau of Standards and Staff Welfare Committee prints a 23-type semiconductor insulating resin, which is characterized by the formation of the patent scope 1 The resin layer formed by the resin paste of any one of item 4 has an elastic modulus at 25 ° C of 0.2 to 3.0 GPa, and the above resin layer is 15 Å. The elastic modulus of 〇 is elastic at -65 ° C. The resin for semiconductor insulation according to claim 23, wherein the glass transition temperature of the resin layer is 180 ° C or higher. The paper scale is applicable to the Chinese National Standard (CNS). A4 size (210X297 mm) 7 3124〗 correction The present invention relates to the semiconductor insulating tree of the 23rd or the 24th item of the patent, wherein the 5% weight reduction temperature of the resin layer is 〇 °C or more. 2 "Patent scope 23 Item or the semiconductor of the 24th item, the moon, the towel, the drying or hardening temperature of the above resin layer is less than 25 generations. 27· The resin for semiconductor insulation of the application No. 23 is used for formation. A resin layer of a semiconductor device. 28. A method for manufacturing a semiconductor device, comprising: forming a plurality of layers on a semiconductor substrate on which a first wiring layer is formed, by any one of claims 1 to 4 Step 1 of forming a resin layer formed by the resin paste, forming a step of forming an electrode on the semiconductor substrate and a conductive layer on the semiconductor substrate, and removing the external electrode joint on the second wiring layer The step of forming a protective layer and the step of forming an external electrode joint on the protective layer. The method of manufacturing the semiconductor device according to claim 28, wherein the resin layer has a modulus of elasticity at 251. 2 to 3 〇GPa, and the above-mentioned resin layer has a modulus of elasticity at 155°: _65<) (: 1 to 100% of the modulus of elasticity 〇 3 〇 · The semiconductor device of claim 28 or 29 In the method of forming a plurality of resin layers, a resin paste which can form a resin layer by printing or sputtering coating, drying or hardening is used. 31. The semiconductor device according to claim 3 Manufacturing method, 31241 Amends the above-mentioned resin paste of 1287030 to have a viscosity at 25 ° C of 1 to i000 Pa·s and the above-mentioned resin has a thixotropic coefficient of from 1.2 to 15.0. 32. A method of producing a semiconductor device, comprising: forming a resin layer formed of a resin paste according to any one of the above claims to claim 4 on a semiconductor substrate on which a first wiring layer is formed; a step of providing a through hole reaching the wiring layer in one of the resin layers, and forming an external bonding joint on the resin layer and a second wiring layer that conducts the first wiring layer. The method of manufacturing a semiconductor device according to claim 32, wherein the resin layer is obtained by laminating a film-like resin on the semiconductor substrate. The method of manufacturing a semiconductor device according to claim 32, wherein the resin layer is obtained by spin coating a paste-like resin on the semiconductor substrate. The Employees' Welfare Committee of the Central Bureau of the Ministry of Economic Affairs prints a manufacturing method for a semiconductor device, which is characterized in that it has a modulus of elasticity of 〇·2 to 3.0 GPa at 25 C and a glass transition temperature of 18 〇〇c or more. The 5% weight reduction temperature is at 300. The resin obtained by the resin paste according to any one of the above claims 1 to 4 is printed on the semiconductor wafer on which the first wiring layer is formed, and a plurality of resin layers are formed on the resin layer. a step of forming a second electrode of the semiconductor wafer and conducting a second layer, and a wire layer; and printing the resin on the second wiring layer to form a plurality of second wiring layer protective layers; (2) a step of providing a through hole reaching the second wiring layer on the protective layer of the wiring layer; a step of forming an external electrode joint in the through hole; and applying the Chinese National Standard (CNS) A4 specification (210×297 mm) to the paper size. 31241 Amendment 1287030