TWI331166B - Film-like adhesive, adhesive sheet, and semiconductor device using same - Google Patents

Description

133. The invention relates to a film-like adhesive used for attaching a semiconductor element to an adherend such as a support member for mounting a semiconductor element, and an adhesive sheet using the same. And a semiconductor device. [Prior Art] A silver paste is mainly used in the case of bonding a semiconductor element to a die bonding adhesive for forming a die bonding layer for a semiconductor element mounting supporting member such as a lead frame. However, in the case of silver paste, with the increase in the size of semiconductor elements or the miniaturization and high performance of semiconductor packages in recent years, the following problems are apt to occur. For example, the bleeding after wafer bonding due to spreading properties causes defects in wire bonding due to tilt of the semiconductor element, and the film thickness of the wafer bonding layer is insufficient. And the problem of voids in the wafer bonding layer. Due to such problems, it is difficult to satisfy the requirements for miniaturization and densification of the support member for miniaturization and high performance of the semiconductor package. Therefore, in recent years, it has been advantageous in terms of miniaturization and densification of the support member, and the film-like adhesive is widely used as an adhesive for wafer bonding (refer to, for example, Sakamoto Kai-Ping No. 3-192178, Japanese Patent Laid-Open Bulletin No. 4-234472). This film-like adhesive is used, for example, in a method of manufacturing a semiconductor package (semiconductor device) of an individual bonding method or a wafer back side bonding method. -5- (2) 1331166

In the individual joining method, first, a reel-like film-like adhesive is cut or punched and cut into individual sections to adhere the single piece to the supporting member. Next, the film-like adhesive on the supporting member is adhered (wafer bonded) to the supporting member by dicing the individually wafer-formed semiconductor elements. Thereafter, a semiconductor device can be manufactured through a wire bond step, a sealing step, or the like (for example, see Japanese Patent Laid-Open Publication No. Hei 9-17810). However, in the case of the individual joining method, it is necessary to cut out the film-like adhesive to adhere to a dedicated assembly device for the supporting member, so that there is a problem that the manufacturing cost is increased as compared with the case of using the silver paste. On the other hand, in the wafer back side bonding method, first, a film-like adhesive is bonded to the back side of the semiconductor wafer, and a dicing tape is bonded to the bonded film-like adhesive. Then, a film-like adhesive semiconductor element can be obtained by dicing a semiconductor wafer to be individually diced, and pick-up is adhered to the supporting member (wafer bonding). Thereafter, the semiconductor device is fabricated through a wire bonding step, a sealing step, and the like. In the case of the wafer back side bonding method, it is not necessary to cut the film-like adhesive into a dedicated assembly device for supporting the bonding member. For example, it is possible to use the assembly device of the conventional silver paste as it is, or to perform the joining using a partially modified device such as a hot plate. Therefore, in the assembly method using a film-like adhesive, the method of controlling the production cost relatively inexpensively has been attracting attention (see, for example, Japanese Patent Application Laid-Open No. Hei-4-196246). -6 - (3) 『1331166 However, at present, the support device has a plurality of semiconductor elements laminated due to the multi-functionality, and the semiconductor device of the so-called 3D package is rapidly increasing. Therefore, in the semiconductor device of such a 3D package, since the overall thickness of the semiconductor device is reduced, the semiconductor wafer is further thinned.

Further, when the semiconductor wafer is further thinned, the semiconductor wafer is transported during the manufacturing of the semiconductor device by the wafer back side bonding method, or the semiconductor wafer is bonded to the back side of the semiconductor wafer. The problem of round breakage is becoming more and more significant. Therefore, techniques for preventing the wafer from cracking, for example, bonding a polyolefin-based protective tape (back grinding tape) on the surface of a semiconductor wafer, have been widely used. However, the softening temperature of the back honing zone is generally due to the low temperature (for example, 1 〇〇 °c or less). In the case of using the back honing tape, the film-like adhesive can be used at a specific softening temperature (for example, 1 oo °c). Lower temperatures are desirable for the bonder on the back side of the semiconductor wafer. Further, with the extremely thinning of the semiconductor wafer, the warpage of the semiconductor wafer is likely to occur due to thermal stress, so that the film-like adhesive which is bonded at as low temperature as possible is suppressed in terms of the warpage. I am strongly hoped. As described above, in the production of a semiconductor device such as a bonding property at a low temperature in a film-like adhesive, the properties of the process are ensured. Further, in order to secure the reliability of the semiconductor device as a film-like adhesive, it is desirable to have sufficient reflow resistance. Therefore, in order to make the processability and the reflow-resistant solderability, CS > (4) "331166" is a thermoplastic resin with a relatively low glass transition temperature, and a film-like adhesive combined with a thermosetting resin is proposed. (For example, Patent No. 3 0 1 4 5 7 8). [Summary of the Invention]

However, in the conventional film-like adhesive, as the thermoplastic resin Tg used becomes lower, the adhesive strength tends to decrease upon heating, and even if the thermosetting resin is combined, there is a limit to the improvement in characteristics. In order to coexist with the high degree of processability and reflow resistance, there is a need for further improvement. The present invention has been made in view of the above-described problems of the prior art, and it is an object of the invention to provide a film-like adhesive which can provide a high degree of reliability in semiconductor devices such as process characteristics at low temperatures and reflow solderability. Further, it is an object of the present invention to provide an adhesive sheet which can simplify the manufacture of a semiconductor device. Further, an object of the present invention is to provide a semiconductor device which is excellent in adhesion strength upon heating, heat resistance and moisture resistance. The inventors of the present invention have been able to provide the following solutions by solving the above-mentioned problems. The present invention provides a semiconductor device in which a semiconductor element is adhered to a film-like adhesive used for an adherend, and is provided with a selected uric acid. An adhesive layer of at least one resin of ethyl phthalimide resin, polyurethane amide amine imide resin, and polyurethane urethane-polyurethane amide amine amide resin Film adhesive. According to an embodiment of the present invention, the adhesive layer preferably contains a polyurethane quinone imine resin, and the polyurethane urethane resin contains a partial structure represented by the following formula (la). The polymer is better. -8 - (5) 1331166

Wherein Rla represents a divalent organic group containing an aromatic ring or a linear, branched or cyclic aliphatic hydrocarbon, and R2a represents a divalent organic group having a molecular weight of ι〇〇~ι〇〇〇〇, R3a A tetravalent organic group having a total carbon number of 4 or more, and nla represents an integer of 1 to 100. The polyurethane quinone imine resin is preferably an urethane oligomer having an isocyanate group at the terminal formed by the reaction of a diisocyanate with a diol, and is obtained by chain extension of tetracarboxylic dianhydride. Moreover, according to another embodiment of the present invention, the adhesive layer preferably contains a polyurethane amidoxime resin, and the polyurethane amidoxime resin contains the following formula (lb) The polymer of the partially constructed structure is better. [Chemical 2]

(1b) 1331166 (6) [In the formula, Rb is a divalent organic group containing an aromatic ring or a linear, branched or cyclic aliphatic hydrocarbon, and R2b is a 2-valent organic group having a molecular weight of 100 to loooo, and R3b represents The trivalent organic group having a total carbon number of 4 or more, and nlb represents an integer of 1 to 100. The polyurethane amidoxime amide resin is obtained by chain extension of a tricarboxylic acid anhydride obtained by reacting a diisocyanate with a diol to form an urethane oligomer having an isocyanate group at the terminal. Further, according to still another embodiment of the present invention, the adhesive layer is preferably a polyurethane-containing imidate-polyurethane amide amine imide resin. - Polyurethane amidoxime imide resin 'preferably, a polymer having a partial structure represented by the following formula (la) is preferred 'the polyurethane quinone imine-polyurethane amidoxime oxime The imine resin 'is more preferably a polymer having a partial structure represented by the following formula (lb). [Chemical 3]

(1a) [In the formula, R is a divalent organic group containing an aromatic ring or a linear, branched or cyclic aliphatic hydrocarbon, R2a represents a divalent organic group having a molecular weight of 100 to 10,000, and R3a represents a total carbon. Number 4 or more of the tetravalent organic group 'nla table-10- 『1331166

[In the formula, R 2 is a divalent organic group containing an aromatic ring or a linear, branched or cyclic aliphatic hydrocarbon, R 2b represents a divalent organic group having a molecular weight of 100 to 10,000, and R 3b represents a total carbon number of 4 or more. The trivalent organic group, nlb represents an integer of 1 to 100.] The polyurethane quinone imine-polyurethane amide amide amide resin has a terminal formed by reacting a diisocyanate with a diol. An isocyanate-based urethane oligomer obtained by chain extension of tetracarboxylic dianhydride and tricarboxylic anhydride. The diisocyanate is preferably a compound represented by the following formula (10). [Chemical 5]

OCN

NCO (1〇) The diol is preferably a compound represented by the following formula (20): - (20) 1331166 (6) [Chem. 6] HO-^CH2CH2CH2CH20^-Η [wherein, η20 represents 1 to 100. The integer. The compound shown is preferably the tetracarboxylic dianhydride containing the following formula (30).

The tricarboxylic anhydride is preferably a compound having the formula (4〇):

The weight average molecular weight of the polyurethane quinone imine resin, the polyamine methylamine resin, and the polyurethane quinone imine-polyamine imide resin, each of which is 10,000 of the adhesive layer, and further contains Thermosetting succinate ethylamine amidoxime urethane amide amide 醯 ~ 30,000 is preferred. Preferably, the thermosetting -12-(9) 1331166-based resin preferably contains an epoxy resin. Further, the adhesive layer may further contain a chelating agent. In the hair-like adhesive, the main temperature of the adhesive layer is preferably -100 to 50 ° C in the dynamic viscoelasticity measurement, and the storage elastic modulus of the adhesive layer at 20 ° C is 1〇. 〇〇 MPa or less is preferred. Further, while heating to 18 ° C, the flow rate of the adhesive layer (2000 μπι is preferably good) at 9.8 MPa, and further, after heating at 18 (TC for 1 hour, heating) In the meantime, it is preferable that 50 to 2000 μm of the adhesive layer is applied at 9.8 MPa for 90 seconds. In the present invention, a wiring-attached organic substrate can be used for bonding the semiconductor element to be adhered. Further, the present invention relates to a dicing sheet comprising a single-sided agent for a base film and an adhesive sheet provided on the adhesive film-like adhesive. The adhesive layer is preferably a release adhesive. Further, the present invention relates to a semiconductor device in which a support member and a wafer-bonding layer to which the semiconductor is adhered are formed by bonding a layer of the film-like adhesive to a semiconductor device in which at least one of the supporting members is mounted. Further, the present invention relates to a semiconductor device in which at least two components are mounted on a supporting member, and the supporting member and the wafer bonding layer of the semiconductor, and the film dispersion peak-viscoelasticity measurement of the two semiconductor elements The same flow rate of 50~180 °C for 90 seconds, (obj ec ts set the ray hardened semiconductor element on the adhesive layer to bond the semiconductor components of the wafer to be adhered to each other. 13- (10) 1331166

At least one of the wafer bonding layers is a semiconductor device by a wafer bonding layer. The disclosure of the present invention is related to the subject matter recited in 2005-2005-030759, 2005: 2005-043135, 2005/2005-043139, and 2005 2 } 2005-〇494〇7 Quoted and used here. [Best Mode for Carrying Out the Invention] Hereinafter, the proper implementation of the present invention will be described in detail. However, - the implementation. The film-like adhesive of the present invention is used for an adhesive for wafer bonding, such as a support member for semiconductor mounting. • Fig. 1 and Fig. 2 show a cross-sectional view of the present invention. The film shown in Fig. 1 is formed of a polyurethane resin, a resin of at least one resin, and a resin of at least one resin of polyurethane phthalimide-polyurethane. The adhesive layer 10 may contain a layer selected from the group consisting of polyaluminum amide amine imide resin and polyurethane amide amine imide resin. The adhesive layer 10 may contain one or two kinds of the film adhesives. The formation of the P February 7曰 application for the Japanese special application on the 18th of this month! The application for the special request on the 18th] The application for the purpose of the application on the 24th, the disclosure of the content, In view of the necessity, the present invention is not limited to the following agents, and is used for adhering a semiconductor element, that is, an adhesive 1 a for a film-like adhesive, which is selected from g-formic acid. Ethyl amidoxime imide tree ethyl benzoate anthraquinone imide tree film adhesive layer 1 bismuth urethane quinone imine resin, and polyurethane quinone imine 2 or more resins . Further, the above polyurethane quinone imine-14-(11) (11) 1331166 resin, polyurethane amidoxime imine resin 'and/or polyurethane quinone imine-polyamine Ethyl formate amide amine imide resin. The thickness of the adhesive layer 10 is preferably about 5 to ΙΟΟμηι. In addition, when the film-like adhesive la is stored and transported, it is a strip having a width of about 1 to 20 mm, or a sheet having a width of about 1 to 5 cm, so that it is wound around the core. good. The film-like adhesive lb shown in Fig. 2 has the same adhesive layer 1 as the film-like adhesive la of Fig. 1 and is provided on both surfaces of the base film 20. The base film 20 is not particularly limited as long as it can be heated when the adhesive layer 10 is formed. For example, a polyester film, a polypropylene film, a polyethylene terephthalate film, and a polyphthalate film can be suitably used. Amine film, polyether quinone film, polyether naphthalate film, methyl pentene film. The base film 20 may be a multilayer film in which two or more kinds of these films are combined. Further, the surface of the base film 20 can be treated, for example, by a release agent such as a polyoxygen. In the film-like adhesives la and lb, in order to prevent damage or contamination of the adhesive layer 10, an over cover film may be further provided to cover the adhesive layer 10. In this case, the film-like adhesive can be used for wafer bonding after peeling off the upper cover film. Adhesive layer 1 lanthanide, selected from polyurethane quinone imine resin, polyurethane amide amine imide resin and polyurethane quinone imine-polyurethane amide At least one resin of an amine resin. "Polyurethane quinone imine resin" means a resin formed by a polymer having an urethane group and a quinone group in the main chain. "Polyurethane amide -15 - (12 (12) 1331166 Resin" means a resin having a urethane group, a guanamine group and a base polymer in the main chain. "Polyurethane oxime-polyurethane amide amide amide resin" means a partial structure having an amine ester group and a quinone imine group in the main chain, and a urethane group in the main chain. The polymer of the amide group and the quinone imine moiety is formed into a resin. The adhesive layer 10 has a urethane group and an oxime imine group, and further has a guanamine group depending on the case, so that the processability and the reflow resistance can be highly coexisted below. "Polyurethane quinone imine resin , polyurethane amide amine amide amine resin, and polyurethane quinone imine-polyurethane amide amine amide resin) also known as "polyurethane bismuth amide resin J The adhesive layer 10 is selected from the group consisting of polyurethane quinone imine resin, polyurethane amide amine imide resin, and polyurethane quinone imine-polyurethane amide amine amide The resin of at least one type of the amine resin can provide a film-like adhesive excellent in processability such as low-temperature bonding property, and can provide peeling of the wafer bonding layer at a reflow soldering temperature of about 60 ° C. Or a film-like adhesive having a high adhesive strength, which is destroyed by a conventional technique, in which a support member for mounting a semiconductor element is attached to a surface of a wiring-attached organic substrate, which is caused by a difference in height of the wiring. The case of a bumpy surface, wafer bonding It is necessary to sufficiently fill the concave portion of the uneven surface (embedded). Such charging is extremely important in order to ensure the moisture resistance reliability of the semiconductor device and the insulation reliability between the wirings. In the assembly process, the wafer bonding layer flows and is filled in the concave portion on the surface of the supporting member by heat and pressure at the time of transfer molding.

-16- C S (13) 『1331166

However, in the manufacture of the semiconductor device of the above-described 3D package, in particular, at the stage of the die casting, the wafer bonding layer interposed between the semiconductor element and the supporting member in the lowermost stage (hereinafter referred to as "the lowermost wafer bonding" The layer") is subject to most thermal history. As a result, the fluidity is lowered, so that it is difficult to sufficiently ensure the embedding property of the concave portion of the surface of the mounting member. That is, in the case where the plurality of semiconductor elements are laminated on the supporting member, it is necessary to perform heating a plurality of times in order to bond the wafers of the respective semiconductor elements, but when the number of the semiconductor elements is increased, the wafer bonding layer is also subjected to The heat process increases. Therefore, the curing of the wafer bonding layer is performed, and the fluidity of the lowermost wafer bonding layer at the stage of die casting is liable to be lowered. Further, in the case of a conventional film-like adhesive, when a material having a large fluidity is used in a long-time thermal process in the manufacture of a semiconductor device such as a 3D package, voids may be changed in the wafer bonding layer. More tendencies. When a large number of voids occur in the wafer bonding layer, the semiconductor device is resistant to reflow solderability, moisture resistance reliability, and insulation reliability between wirings. The adhesive layer 1 contains, selected from the group consisting of polyurethane quinone imine resin, polyurethane amide amine imide resin, and polyurethane quinone imine-polyurethane amide amine hydrazine The resin of at least one of the imide resins can sufficiently fill the concave portion of the surface of the support member even when heated by the sealing material after being subjected to an extremely large thermal process. Moreover, the voids in the wafer bonding layer can be sufficiently suppressed. From the viewpoint of fluidity and voids at the time of die casting, the adhesive layer 10 contains a resin selected from the group consisting of polyurethane quinone imine, and polyurethane urethane-polyurethane amide. It is preferred that at least one resin of the imine tree-17-(14)(14)1331166 fat is preferred. The reason why the effect of the present invention can be obtained by the use of a polyurethane quinone imide resin is not clear. The inventors of the present invention presume that, in the case of a film containing a polyurethane bismuth imino resin, when heated to a temperature higher than the glass transition temperature, the degree of filling of the concave portion on the surface of the support member can be made to flow. However, excessive fluidity which causes voids in the wafer bonding layer is not caused. In general, when a film containing a thermoplastic resin as a main component is heated to a temperature above the glass transition temperature and pressurized, the film can be largely flowed by micro brown movement of a molecular chain in the thermoplastic resin. On the other hand, in the case of a film containing a polyurethane urethane-based resin having a urethane group-containing polymer, the urethane gene has a relatively high polarity and hydrogen bonding property, so The molecular chain is caused to be agglomerated by the interaction between the molecular chains caused by the interaction of the urethane groups in the resin and the like. As a result, in the film containing the polyurethane quinone-based resin, the fluidity at a temperature exceeding the glass transition temperature is suppressed to some extent. From this, it is considered that the film containing the polyurethane quinone imide resin exhibits the above-mentioned moderate fluidity when heated to a temperature higher than the glass transition temperature. Further, in the case where a polyurethane quinone imine resin is formed of a polymer having an urethane group and a guanamine group, the interaction between the guanamine groups can be expected, and a guanamine group can also be expected. Interaction with urethane groups. Further, in the case of a usual polyimine-based resin which does not have a urethane group, the interaction between the above molecular chains is hard to appear, or even weak. Therefore, it is believed that the flow of temperature above the glass transition temperature -18 - (15) (15) 311 166 is too large. The problem of voids in the wafer bonding layer is apt to occur. Polyurethane quinone imine resin, that is, polyurethane quinone imine resin 'polyurethane amide amide imimine resin, and polyurethane quinone imine-polyurethane B The preferred embodiment of the ester amidoxime imide resin is as follows. With these forms, the above-described effects of the present invention can be made more remarkable. (Polyurethane quinone imine resin) The polyurethane quinone imine resin preferably contains a polymer (block copolymer) mainly composed of a partial structure represented by the formula (la).

In the formula (1, nla represents an integer of 1 to 100. Such a block copolymer] has an isocyanate group at the end formed by, for example, a reaction of a diisocyanate having 2 isocyanate groups and a diol having 2 hydroxyl groups. An urethane oligomer obtained by chain extension of tetracarboxylic dianhydride. In the formula (la), 11|3 represents an aliphatic hydrocarbon having an aromatic ring or a linear chain, a branched chain or a ring. The divalent organic group 13 can contain both an aromatic ring and an aliphatic hydrocarbon. In particular, Rla has an aromatic ring of -19 - (16) 1331166. Further, the plural Rla in the formula (la) can be mutually Same or different.

Rla has, for example, 'benzene residue, toluene residue, xylene residue 'naphthalene residue, straight chain, branched chain' or cyclic alkylene group, or a mixed group thereof, preferably a xylene residue, Diphenylmethane residue. Specifically, RIa is preferably a divalent group obtained by introducing a diisocyanate into a polymer by a reaction with a polyhydric alcohol and an acid anhydride described later. In this diisocyanate, for example, diphenylmethane-4,4'-diisocyanate 'diphenylmethane-2,4'. diisocyanate, toluene-2,4-diisocyanate, toluene-2,6 can be exemplified. -diisocyanate ' 1,6-hexylene diisocyanate, 3-isocyanato methyl-3,5,5-trimethylcyclohexyl isocyanate, 1,1·-methylene double (4- Isocyanatocyclohexane), 1,3-bis(isocyanatomethyl)benzene, 1,3-bis(isocyanatomethyl)cyclohexane. Among these, a divalent group derived from a compound represented by the formula (10) (comparable with diphenylmethyl-4,4'-diisocyanate and diphenylmethane-2,4,diisocyanate) is preferred. . The compound represented by the formula (10) is preferred because it can obtain a polyurethane quinone imine resin having better heat resistance. Moreover, since the reactivity between the monomers at the time of synthesizing the urethane oligomer is also high, the polyurethane urethane resin having a higher gastric percentage can be obtained, and the polyurethane urethane is obtained. It is also easy to control the molecular weight of 55 B resin. [化10]

OCN

NCO (10) In the formula (la), 1123 is a divalent organic compound having a molecular weight of 100 to 10,000. -20. ( (17) > 1331166 The plural R2a in the formula (la) may be the same or different from each other. R2a has, for example, a polyether residue, a polyester residue, a polycarbonate residue, a caprolactone residue, a polyoxyalkylene residue, preferably a polyether residue. For example, R2a can be introduced into the polymer by reacting with the above diisocyanate by an average molecular weight of from 100 to 10,000. The diol may, for example, be polypropylene glycol, polyethylene glycol, polypropylene glycol/polyethylene glycol, polytetramethylene glycol, poly(ethylene adipate), poly Φ diacid Ethylene ester), poly(propylene adipate), poly(hexane dicarboxylate), poly(hexanediol adipate), poly(pentyl adipate), poly(sebacic acid) Hexyl ester), poly-ε-caprolactone, poly(carbon. hexyl ester), poly(oxane). Among these, it is preferred that the poly-1,4:butanediol represented by the formula (20) is 2 -. The poly-1,4-butanediol represented by the formula (20) is preferred because it can provide a semi-conductive with better heat resistance and moisture resistance. Further, an excellent film-like adhesive can be obtained by temperature bonding property and low stress property. [Chemical "] H〇-fcH2CH2CH2CH2〇-^—Η (20) \ η20 The ratio of diisocyanate to dibasic when the urethane oligomer is obtained, relative to the diisocyanate 1·0 molar diol 〇 . 1~1.0 Mo Jia. The plural R3a in the formula (la) wherein R3a is a tetravalent organic group (la) having a total carbon number of 4 or more may be the same or different from each other. -21 - , Polyol, Noodle -, Alcohol (butane butyrate acid valence matrix loading from low

The ear of alcohol is a compound of the formula c S (18) (18) p31166 R3a, such as an aromatic ring residue, a linear chain, a branched chain or a cyclic aliphatic hydrocarbon residue, an ether residue, a thioether residue, a carbonyl group. Residue, sulfonate residue, decane residue, ester residue, preferably ether residue. For example, R3a is obtained by reacting a tetracarboxylic dianhydride with an urethane oligomer having an isocyanate group at the terminal and introducing it into a polymer. In terms of the tetracarboxylic dianhydride, for example, pyromellitic dianhydride, 3,3',4,4 diphenyltetracarboxylic dianhydride, 2,2',3,3'-diphenyltetra Carboxylic dianhydride, 4,4'-oxidized diphthalic anhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxybenzene Propane dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, double (2, 3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)leaf phthalic anhydride, 3,4,9,10-anthracene Tetracarboxylic dianhydride 'bis(3,4-dicarboxyphenyl)ether dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, 3,3',4,4'-diphenyl Ketotetracarboxylic dianhydride, 2,2',3,3'-diphenyl ketone tetracarboxylic dianhydride, 2,3,3',4·-diphenyl ketone tetracarboxylic dianhydride, 1,2 , 5,6-naphthalenetetracarboxylic dianhydride '2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride '1,4,5,8- Naphthalene tetracarboxylic dianhydride, 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride , 2,3,6,7-tetrachloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, phenanthrene-1,8,9,10-tetracarboxylic dianhydride, Pyrazine-2,3,5,6-tetracarboxylic dianhydride' thiophene-2,3,4,5-tetracarboxylic dianhydride, 2,3,3',4,biphenyltetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2,3,3'-biphenyltetracarboxylic dianhydride, bis(3,4-dicarboxyphenyl) Methyl decane dianhydride 'bis(3,4-dicarboxyphenyl)methylphenyl decane dianhydride, bis(3,4-dicarboxyphenyl)diphenyl phthalane dianhydride, I,4-dual (3 , 4-dicarboxyphenyldimethylmonodecyl)benzenedi-22-(20)r1331166 These are 4 valences of 4,4·-diphthalic anhydride from formula (30) The base is good. The 4,4·-oxydiphthalic anhydride represented by the formula (30) is preferable because it can obtain more excellent moisture resistance reliability and heat resistance of the semiconductor device. [化 12]

The ratio of the polyurethane oligomer to the tetracarboxylic dianhydride at the time of obtaining the polyurethane quinone imine resin, relative to the polyurethane urethane 10 moles to the tetracarboxylic acid The anhydride is preferably 0.1 to 2.0 moles. (polyurethane amide amine imide resin) Polyurethane amide amine imine resin, which is composed of a polymer having a partial structure represented by formula (1 b ) (block copolymerization) Things) are better.

Oyc NH o R2b/ o o=c

NH η R1

Ν \ϊ/ -24- (21) ^1331166 In the formula (lb), nlb represents an integer from 1 to 100. Such a block copolymer, for example, an amine urethane oligomer having an isocyanate group formed by reacting a diisocyanate having two isocyanate groups with a diol having two hydroxyl groups, and is chained with a tricarboxylic anhydride Extend it.

In the formula (1b), 11115 is a divalent organic group containing an aromatic ring or a linear, branched or cyclic aliphatic hydrocarbon. Rlb can contain both aromatic and aliphatic hydrocarbons. In particular, Rlb preferably contains an aromatic ring. Further, the plural Rlbs in the formula (lb) may be the same or different from each other. R1 b is, for example, a benzene residue, a toluene residue, a xylene residue, a naphthalene residue, a linear chain, a branched chain, or a cyclic alkylene group, or a mixed group thereof, preferably a xylene residue, Diphenylmethane residue. Specifically, Rb is preferably a divalent group which is introduced into the polymer by reacting a diisocyanate with a polyhydric alcohol and an acid anhydride described later. In terms of the diisocyanate, for example, diphenylmethane·4,4′·diisocyanate, diphenylmethane-2,4′-diisocyanate, toluene-2,4-diisocyanate, toluene-2,6 may be exemplified. -diisocyanate, 1,6-hexylene diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate, 1,1'-methylenebis(4-isocyanate Hexacyclohexane), 1,3-bis(isocyanatomethyl)benzene, 1,3·bis(isocyanatomethyl)cyclohexane. Among these, a divalent group derived from a compound represented by the formula (10) (corresponding to diphenylmethane-4,4'-diisocyanate and diphenylmethane-2,4'-diisocyanate) is preferred. The compound represented by the formula (1 〇 ) is preferred because it can obtain a polyurethane amide amine imide resin which is more excellent in heat resistance. Moreover, the reactivity between the monomers at the time of the -25-(22)1331166 urethane oligo oligopolymer is also high, so that a more efficient polyurethane amidoxime imine can be obtained. The control of the molecular weight of the resin, polyurethane, amidoxime imine resin is also easy. [Chem. 1 4]

(10) In the formula (lb), R2b is a divalent organic group having a molecular weight of 100 to 1 0000, and a plurality of R2b in the formula (lb) may be the same or different from each other. R2b is, for example, a polyether residue, a polyester residue, a polycarbonate residue, a polycaprolactone residue, a polyoxyalkylene residue, preferably a polyether residue. For example, R2b can be obtained by an average molecular weight of 100. The ～100 diol is introduced into the polymer by reaction with the above diisocyanate. In terms of the diol, for example, polypropylene glycol, polyethylene glycol, polypropylene glycol/polyethylene glycol copolymer, poly-1,4-butanediol, poly(ethylene adipate), poly(two) may be exemplified. Ethylene adipate), poly(propylene adipate), poly(butylene adipate), poly(hexanediol adipate), poly(pentylene glycol adipate) (hexamethylene sebacate), poly-ε-caprolactone, poly(hexylene carbonate), poly(oxane). Among these, a divalent group derived from poly-I,4-butanediol represented by the formula (20) is preferred. The polyfluorene, 4-butanediol represented by the formula (20) is preferred because it can obtain good heat resistance and moisture resistance reliability of the semiconductor device. Further, an excellent film-like adhesive can be obtained by low-temperature bonding property and low stress property. -26- (24) 『1331166 (3,4-Dicarboxyphenyl)-(4-carboxyphenyl)ethane anhydride, (2,3-dicarboxyphenyl)-(2-carboxyphenyl)methane Anhydride, 2-(3',4·-dicarboxyphenyl)-5-(3,-carboxyphenyl)-1,3,4-oxadiazole anhydride, 2-(3,,4-dicarboxylic acid Diphenyl ether)-5-(4·-carboxydiphenyl ether)-13,4-oxadiazole anhydride, 2-(3',4,-dicarboxyphenyl)-5-carboxybenzimidazole anhydride ,2-(3,,4--dicarboxyphenyl)-5-carboxybenzoxazole anhydride, 2-(3,,4'-dicarboxyphenyl)-5-carboxybenzothiazole anhydride, 2, 3,5-pyridine tricarboxylic anhydride.

Among these, the trivalent group derived from the 1,2,4·benzenetricarboxylic acid-1,2-anhydride represented by the formula (4〇) is preferably I, 2, 4· represented by the formula (4〇). The benzenetricarboxylic acid-i,2-anhydride has better moisture resistance reliability for semiconductor devices. [化16] 0

The ratio of the polyurethane oligomer and the tricarboxylic anhydride at the time of obtaining the polyurethane amidoxime imide resin is 1.0 mol with respect to the polyurethane oligomer, and 0.1 to 13 2.0 Moore is better. (polyurethane quinone imine-polyurethane amidoxime amide resin) Polyurethane quinone imine/polyurethane amide amide amide resin, containing the above formula (la The partially constructed structure shown in the above formula (lb) is preferably composed of a polymer (block copolymer) of -28-(25) 1331166. Such a block copolymer is an amine urethane oligomer having an isocyanate group at the end of a reaction between a diisocyanate having two isocyanate groups and a diol having two hydroxyl groups, and a tetracarboxylic acid The anhydride and the tricarboxylic anhydride are obtained by chain extension.

The ratio of polyurethane oligomers to tetracarboxylic dianhydride and tricarboxylic anhydride in the case of obtaining a polyurethane quinone imine-polyurethane amidoxime resin, relative to the poly The urethane oligomer 1 is preferably 0.1 to 2.0 moles based on the total of the tetracarboxylic dianhydride and the tricarboxylic anhydride. The ratio of tetracarboxylic dianhydride to tricarboxylic anhydride, the sum of the two is 1.0 mole, the tetracarboxylic dianhydride is 0.05 to 0.95 moles, and the tricarboxylic anhydride is preferably 0.05 to 0.95 moles, tetracarboxylic acid The dianhydride is 0.20 to 0.80 moles, and the tricarboxylic anhydride is preferably 0.20 to 0.80 moles. When the ratio of the tetracarboxylic dianhydride becomes high, the acid anhydride group of the polyurethane quinone imine-polyamidoximine resin (copolymer) has an increased number of acid anhydride groups. Further, when the ratio of the tricarboxylic anhydride becomes high, the carboxyl group of the polyurethane quinone imine-polyurethane amidoxime imide resin (copolymer) increases in the acid terminal. In this case, when the urethane oligomer is chain-extended, the acid anhydride group is more reactive with the isocyanate terminal group of the urethane oligomer than the carboxyl group. However, the film-like adhesive further contains a thermosetting resin, and when the epoxy resin contains an epoxy resin, the reactivity with the epoxy resin is higher than that of the acid anhydride group. Therefore, when the ratio of the tetracarboxylic dianhydride becomes high, the reactivity of the polyurethane quinone imine-polyurethane amide amine imide resin (copolymer) with the epoxy resin is low. Anhydride -29-(27)1331166 is determined by, for example, "DSC-7 name" manufactured by Perkinelmer Co., Ltd. Further, tetracarboxylic dianhydride and tricarboxylic anhydride are each in tetracarboxylic dianhydride or tricarboxylic anhydride. [Melting point—(10°°C for more than 12 hours, preferably by heating and drying. Polyurethane quinone imine resin is obtained by a usual method such as solution polymerization using the above (see, for example, 1 to 4) (Reference 1): "J.Appl.Polym.Sci." J.Hao, W.Wang, L.Jiang and X.Cai by p.773, 2001 1 (Reference 2): Factory j ".Appl .Polym ICKim, JHKim, KHLe e and TTMak by p.3502, 2002 (Reference 3): "Sakamoto Rubber Association", Yamada Yukihiro and Yusuke Sei, 72, p.74, 1999 Year (Dream Reference 4): "Polymer Internationa" Liu Wang and Fang-Jung Huang, Vol.46, p. 1998 In the case of solution polymerization, first A solvent obtained by dissolving the produced ester quinone imine resin, for example, a reaction liquid obtained by dissolving a diisocyanate and a diol in N-pyridine ketone to obtain a reaction liquid, at 50 ° C to 2 0 0 ° C After 30 minutes to 5 minutes, an urethane oligomer is formed. Further, the reaction solution is added and/or the tricarboxylic anhydride is at 7 ° C to 2 5 Ot: after 1 hour to 1 〇 small" (commodity use) Before, the raw material of the temperature of 2 0 ) ] 6C can be referred to the following reference, B. J i an g > -Vo 1 . 8 1 , .S c i. j , , V01.86, Tian Yingjie, Jia [", Tzοn g-.280-284, polyethylene methyl-2-pyrrole. Then, while heating, the tetracarboxylic dianhydride can be heated to enter -31 - (28) 1331166 urethane The isocyanate group of the oligomer is reacted with an acid anhydride group of an acid anhydride, whereby a polyurethane quinone imine tree can be formed by the reaction, and in the solution polymerization method, a third-order amine or the like is used as a catalyst in the reaction. Liquid addition is possible. However, in the case where the polyurethane foaming resin is combined with the thermosetting resin in the adhesive layer 1 , the kinetic property is adjusted in consideration of heating to adjust the touch. Whether or not the medium is added, and the amount of addition is good. The weight average molecular weight of the polyurethane urethane-based resin in the adhesive layer 10 is 10,000 to 300,000 in terms of film formation property and fluidity at the time of heating. good. In order to improve the toughness of the adhesive layer, the average molecular weight is preferably 30,000 to 200,000, and 70,000 to 150,000, and the weight average molecular weight is gel permeation chromatography. In the polystyrene conversion measured by C-R4A) manufactured by Shimadzu Corporation, the temperature at which the film-like adhesive of the present invention is bonded is preferably a heat-resistant temperature or a softening temperature of the surface honing tape, and is preferably cut. It is preferable that the heat resistance temperature or the softening temperature of the sheet is less than or equal to the temperature at which the warpage of the semiconductor wafer can be suppressed. The temperature to be bonded is preferably 10 to 100 ° C, more preferably 80 ° C. When the temperature is such that the bonding can be carried out, the glass transition temperature (Tg) of the polyurethane resin is adjusted to a temperature of from 100 to 50 ° C, more preferably from -80 to 30 ° C. When the Tg exceeds 50 °C, the possibility that the film-like adhesive bondable temperature exceeds 100 °C becomes high, and when the Tg is not reached, the film-like adhesive tends to deteriorate reasonably. In addition, it is determined based on the DSC curve of the nitrogen atmosphere measurement at a temperature increase rate of about 5 mg/min. The DSC is determined, for example, as a carboxyl ester. The addition of imine to the amount of 1 is the best. (Example 値. For the back in the cut. 20 20 ~ ester 醯 good, the agent 100 ° C Tg ′, use the surrounding -32- (29) (29)

1331166

"DSC-7 type" manufactured by Perkinelmer Co., Ltd. (in addition to the above polyamines, the thermosetting resin is further included as a thermosetting resin) means that it is crosslinked into a resin by heating. In terms of thermosetting resin, fat 'cyanate resin, bis-m-butylene imidate resin' melamine resin, alkyd resin, polyester resin, diallyl phthalate resin diphenol formaldehyde Resin, xylene resin, furan resin, ketone resin 'triallyl isocyanurate ester, containing tris(2-hydroxyethyl)isocyanurate (fat, triallyl trimellitate resin, two In view of the fact that the thermosetting tree adhesion force due to the trimerization of the group diamino cyanide is variable, the epoxy group thermosetting resin may be used alone or in combination of two types in the epoxy resin to use a molecular group. In particular, in terms of curability, the epoxy group-containing epoxy group-containing epoxy resin may, for example, be bisphenol/bisphenol F or the like. Epoxy propyl ether, oxypropyl ether, ethylene oxide adduct of bisphenol A Di-epoxypropyl ether, phenol novolak resin phenol novolac resin polyepoxypropyl ether, bispolyepoxypropyl ether, naphthalene glycol diepoxypropyl product name). Further, in the present invention, the crosslinkable compound may, for example, be an epoxy tree resin, a phenol resin, a urethane acrylic resin, an unsaturated, a polyoxyxylene resin, a meta-phenylene ester or a polyurethane. Ester resin, polyisocyanate tree ISOCYANUR ATE) tree cyclopentadiene resin, aromatic fat. Among these, high temperature grease is preferred. In addition, these are used. It is preferred to have at least two epoxy or hardener properties therein. Epoxy propyl ether type, bisphenol AD, bisphenol S hydrogenation plus bisphenol A bicyclo or propylene oxide adduct polyepoxypropyl ether, formazan phenol varnish resin ether, bicyclo Pentadiene type -33- (30) epoxy resin. Further, as the epoxy group-containing resin other than the epoxidized propyl ether type, for example, a di-glycidyl ester of a dimer acid, a trifunctional or a tetrafunctional polyepoxypropylamine 'naphthalene polyepoxypropane" may be mentioned. Amine. In the case of the epoxy resin, these may be used alone or in combination of two or more. The epoxy resin' can prevent the electromigration or prevent the corrosion of the metal conductor circuit. 'The use of alkali metal ions, alkaline earth metal ions, halide ions, chloride ions and hydrolyzable chlorine can reduce the purity of high purity products. It is better. In particular, an epoxy resin having a hydrolyzable chlorine content of 300 ppm or less is preferred. The content ratio of the thermosetting resin in the adhesive layer 1 is preferably 0.01 to 200 parts by weight based on 100 parts by weight of the polyurethane quinone imide resin, and more preferably 0 to 1 to 100 parts by weight. When the content ratio of the thermosetting resin is less than 0.01 part by weight or more than 200 parts by weight, the film-like adhesive tends to have low outgassing properties, film formability, toughness, heat resistance and the like. In the case of using a thermosetting resin, it is preferred that the adhesive layer 1 is further composed of a hardener or a catalyst containing a thermosetting resin. In this case, a hardener and a hardening accelerator, or a catalyst and a catalyst may be used as needed. In addition, the hardening accelerator may also function as a hardener. The amount of the hardener and the hardening accelerator added, and the presence or absence of the addition, are preferably considered in consideration of fluidity during heating and heat resistance after curing. When the epoxy resin is used as the thermosetting resin, a suitable curing agent may, for example, be a phenol compound, an aliphatic amine, an alicyclic amine, an aromatic polyamine, a polyamine, an aliphatic acid anhydride or a fat. Cyclic anhydride 'aryl-34- (31) 1331166

Aromatic anhydride, dicyandiamide, organic acid dioxane, boron trifluoride amine complex, imidazole, grade 3 amine. Among these, a phenol compound is preferred, and a phenol compound having at least two phenolic hydroxyl groups is particularly preferred. Examples of such a phenolic compound include a phenol novolak resin, a cresol novolak resin, a tertiary butyl phenol novolak resin, a dicyclopentadiene cresol novolak resin, and a dicyclopentadiene phenol novolac resin. Resin, xylylene modified phenol novolak resin, naphthol compound, three phenol compounds 'four phenol novolak resins, bisphenol A novolak resin, poly·p-vinylphenol resin, phenol aralkyl resin. Further, the number average molecular weight of the phenolic compounds is preferably from 400 to 1,500. Therefore, when the semiconductor device is heated, it is preferable to reduce the occurrence of heat removal and gas removal due to contamination such as a semiconductor element or a device. In the case of using a hardening accelerator for a phenol compound as a curing agent, for example, an imidazole, a dicyandiamide derivative, a dicarboxylic acid diterpene, a triphenylphosphine, a tetraphenylphosphonium tetraphenyl boron can be exemplified. Acid ester, 2-ethyl-4-methylimidazolium-tetraphenylborate, 1,8-diazabicyclo[5.4.0]undecene-7-tetraphenylborate The layer of the agent may further contain a chelating agent. The hydrazine agent may, for example, be a metal cerium such as silver powder, gold powder, copper powder or nickel powder, alumina, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium citrate, magnesium citrate, and oxidation. Non-metallic inorganic cerium, calcium, magnesium oxide, aluminum oxide, aluminum nitride, crystalline cerium oxide, amorphous cerium oxide, boron nitride, titanium dioxide, glass, iron oxide, ceramics, etc., carbon, rubber An organic chelating agent such as a sputum. For the adhesive layer containing the chelating agent, for example, a mixture of chelating agents is added to other components such as polyurethane-35-(32) (32) 1331166 ethyl quinone imide resin, and a grinding machine is used. A three-roller, a ball mill or the like can be kneaded by a suitable combination and can be formed using a prepared varnish. The above-mentioned sputum agent can be flexibly applied in response to the desired function. For example, a metal chelating agent can be added for the purpose of imparting conductivity, thermal conductivity, and thixotropic properties to a film-like adhesive. The non-metallic inorganic chelating agent can be added for the purpose of imparting thermal conductivity, low thermal expansion property, and low moisture absorption to the film-like adhesive. The organic chelating agent can be added for the purpose of imparting toughness to the film-like adhesive. These metal chelating agents, non-metallic inorganic ceraming agents and organic ceraming agents may be used singly or in combination of two or more. In particular, the dispersibility with respect to the resin varnish is good, and the insulating property can be imparted, and the high adhesion force at the time of heating is preferable. The average particle diameter of the chelating agent is preferably ΙΟμηη or less, more preferably 5 μηι or less. Further, the maximum particle size of the chelating agent is preferably 25 μm or less, more preferably 20 μπ ΐ or less. When the average particle diameter of the chelating agent exceeds 1 〇μπι, or the maximum particle diameter exceeds 25 μαι, the effect of improving the toughness tends to decrease. In terms of the lower limit of the average particle diameter and the maximum particle diameter, it is preferably about Ο.ΟΟΙμηι, and the Ο.ΟΙμιη is better. The oxime agent has an average particle diameter of ΙΟμηη or less, and the maximum particle size is preferably 25 μηη or less. When the maximum particle diameter is 25 μmτ or less, when a ruthenium having an average particle diameter of more than 1 Ομηι is used, the adhesive strength tends to decrease. On the other hand, when a ruthenium having an average particle diameter of ΙΟμπι or less and a maximum particle diameter of more than 25 μm is used, the variation in the particle size distribution becomes large, and the variation in the adhesion strength becomes large, and the surface becomes thick when the thin adhesive layer is formed. And there is a tendency to decrease the adhesion strength -36- (33) 1331166. The average particle diameter and the maximum particle diameter of the chelating agent were measured by using a scanning electron microscope (SEM) and measuring the average enthalpy and maximum enthalpy of the particle size of about 200 sputum agents. In the measurement method using S EM, for example, an adhesive layer (wafer bonding layer) which is heat-hardened (preferably at 150 to 200 ° C for 1 to 10 hours) is cut and its cross section is SEM. The method of observation.

The content ratio of the sputum can be determined according to the desired characteristics or function. The content of the chelating agent is preferably from 1 to 50% by volume, more preferably from 2 to 40% by volume, even more preferably from 5 to 30% by volume, based on the total of the adhesive layer. When the adhesive layer is made to have a high modulus of elasticity by the increase of the enthalpy, the dicing property (cutting property of the dicing blade), the wire bonding property (ultrasonic efficiency), and the adhesion at the time of heating It is advantageous to increase the strength effectively. However, when the enthalpy is excessively increased, the low-temperature bondability and the adhesive strength are lowered, and the reliability including the reflow-resistant solderability is lowered. In the adhesive layer 1 各种, various coupling agents may be added in order to enhance the interface bonding between the different materials. The coupling agent may, for example, be a decane type, a titanium type or an aluminum type, and among them, the effect is high, and a decane-based coupling agent is preferred. The content ratio of the coupling agent is preferably 0.01 to 20 parts by weight based on 1 part by weight of the polyurethane quinone imide resin in terms of interface bonding, heat resistance and cost. Further, in the adhesive layer 10, an ion trapping agent which is excellent in insulation reliability when absorbing ionic impurities and absorbing moisture can be added. The ion scavenger may, for example, be used to prevent triterpene thiol compounds and bisphenol-based reduction.

-37- (34) (34) 1331166 The copper ionizing agent for copper ionization leakage is a known ion sorbent such as a known compound, a cone system, or a lanthanide magnesium aluminum compound. The content ratio of the ion scavenger is preferably 0.01 to 10 parts by weight based on 100 parts by weight of the polyurethane quinone imide resin, in terms of the effect, heat resistance, cost, and the like. The adhesive layer 10 may be suitably added with a softening agent, an anti-aging agent, a coloring agent, a flame retardant, a terpene-based resin, or the like, and a thermoplastic polymer component. In the case of a thermoplastic polymer component, in order to impart adhesiveness or stress relaxation during curing, a polyvinyl butyral resin, a polyvinyl formal resin, a polyester resin, and a polyamide resin are used. An amine resin, a xylene resin, a phenoxy resin, a polyurethane resin, an acrylic rubber or the like can be suitably used. The thermoplastic plastic component is preferably a molecular weight of 5,000 to 500,000. The adhesive layer 10 is preferably in the dynamic viscoelasticity measurement with a main dispersion peak temperature of -100 to 50 ° C, more preferably -80 ° C to 30 ° C. Here, the above-mentioned main dispersion peak temperature, in the adhesive layer, in the sample size of 35 mm x 10 mm, the temperature rise rate of 5 ° C / min 'frequency 1 Hz, the measurement temperature -150 ~ 300 ° C, under the conditions of the tensile mode dynamic In the measurement of viscoelasticity, it is shown that ta η δ is the maximum temperature. Further, in the case where tanS shows a complex maximum enthalpy, the temperature at which the maximum maximum enthalpy is displayed in these is taken as the main dispersion peak temperature. The dynamic viscoelasticity measurement can be carried out, for example, using a viscoelastic analyzer "RSA-2" (trade name) manufactured by R h e 〇 m e t r i c s. When the temperature of the main dispersion peak is less than - loot, the film adhesive is rationally deteriorated. When the temperature exceeds 50 ° C, the bonding of the semiconductor elements is feasible or -38- (35) (35) 1331166 has more than 1 001 The situation. Further, by using a glass transition temperature of -1 〇〇 〜5 〇t: of the polyurethane quinone imide resin, generally, the main dispersion peak temperature of the adhesive layer 10 can be made at -100 to 501. Within the scope. In the case where a thermosetting resin and/or a chelating agent is added to the adhesive layer 1 , the amount of the additive is adjusted so that the main dispersion peak temperature of the adhesive layer 1 is in the range of -100 to 50 ° C. It is better. The adhesive layer 1 〇 has a storage elastic modulus at 20 ° C in the dynamic viscoelasticity measurement preferably in the range of 100 MPa or less, more preferably 500 MPa or less. Here, the storage modulus at 20 ° C means the meaning of the storage modulus at 20 ° C in the case where the adhesive layer 1 〇 is subjected to the same conditions as in the case of obtaining the main dispersion peak temperature. . When the storage modulus exceeds 1,000 MPa, there is a tendency that the bonding temperature exceeds 1 〇〇 ° C. Further, the storage modulus is preferably 0.01 MPa or more. A polyurethane urethane resin having a glass transition temperature of -100 to 50 ° C and a weight average molecular weight of 10,000 to 300,000 is usually used in the adhesive layer 1 at 20 ° C. The storage modulus is adjusted to be less than 1 〇〇〇Μ P a . It is preferable to add a thermosetting resin and/or a chelating agent to the adhesive layer 1 to adjust the amount thereof to be added so that the storage elastic modulus of the adhesive layer 10 at 20 ° C is preferably 1000 MPa or less. The adhesive layer 10 is preferably heated at a temperature of 180 ° C and pressurized at 9.8 MPa for 90 seconds, preferably 50 to 2000 μm, more preferably 100 to ΙΟΟΟμί. Thereby, particularly good characteristics can be obtained in terms of the filling of the concave portion on the surface of the supporting member or the point of suppressing the voids in the wafer bonding layer. Here, the above flow rate can be self-made to a thickness of 40μπι ± 5μιη -39- (36) 1331166

The adhesive layer was cut out into test pieces of a size of 1 〇 m m x 10 m m to be measured. That is, on the test piece, a film of l〇mmxl〇mmx50 pm thick was subjected to registration or a piece of the same size was placed in a state of being attached with a PET substrate, and held in two sheets of Slide gIass (manufactured by MATSUNAMI Co., Ltd.). Between 76mmx26mmxl.O~1.2mm thick). Next, the entire Slide glass holding the test piece was heated on a hot plate at 180 °C while applying a load of 10 kgf/cm2 (9.8 MPa) for 90 seconds of heating and pressurization. The maximum enthalpy of the bulging amount from the adhesive layer of the above uPilex film or PET substrate after heating and pressurization is taken as the flow rate. Further, the amount of bleeding of the adhesive layer means the distance from the end portion of the adhesive layer which has been exuded to the Upilex film or the PET substrate. The amount of exudation of the adhesive layer can be measured by observation with an optical microscope. When the flow rate is less than 50 μm, the heat and pressure during die casting tend to make it difficult to fill the uneven surface of the supporting member. On the other hand, when the flow rate exceeds 2000 μm, the adhesive layer can be largely flown by heating at the time of wafer bonding or wire bonding, and the bubbles remaining on the uneven surface of the supporting member tend to be incorporated. When the bubble is entangled, even if heat and pressure are applied in the die casting step, the bubble is not completely removed, but remains in the wafer bonding layer in the form of voids, and the void is used in reflow soldering. Starting point to promote foaming. Here, even if the polyurethane having a weight average molecular weight of 10,000 to 300,000 is used, the polyurethane urethane resin is used.

C B -40 - (37) (37)

The glass transition temperature of 1331166 can be controlled from 100 to 2000 μm in a range of 1 〇〇 to 50 °c. In general, in the case of using a film shape of a polyimide resin having no functional group having a high polarity such as an ester group in the main chain, if the glass transition temperature of the polyimide resin is -, the flow rate becomes large, so that It is difficult to control it at 2000μηη. On the other hand, in the case of using a polyurethane urethane-based bead-like adhesive, the glass transition temperature is even at _100 - by molecular chain interaction due to the urethane group. The fluidity above temperature is at a certain level. In order to make the flow rate of the adhesive layer 10 easily within the above range, the adhesive layer 1 is entangled at 180 ° C for 1 hour while heating to 180 ° C, at 9.8 MPa. The 90 second force [quantity ' is preferably 50 to 2000 μm, and more preferably 100 to ΙΟΟΟμηη for charging the concave portion of the surface of the support member, or obtaining particularly good characteristics at the point where the wafer joint gap is suppressed. This flow rate, g I ass (MATSUNA Μ I system, 7 6 mnm X 2 6 mm X 1 · 0 〜1 . on top, to hold 10mmxl0mmx40±5pm thick adhesive layer at a set surface temperature at 180 °C The coating layer on the hot plate for 1 hour can be measured in the same manner as described above. When the flow rate is as described above, the adhesion to the uneven surface of the supporting member is lowered, and the foaming tends to be easily formed during welding. 1 〇 Add a thermosetting resin and/or a bismuth shape to adjust the amount of addition so that the above flow rate is preferably 50 to 200 μm. In particular, in the case of adding a thermosetting resin,

: The flow rate is in the "100 ° ~ 5 0 t of the amine carbamate adhesive": the film of the trapped grease - 50 ° C, "inhibition in glass:, after I think 〇 ^, and then rolling The flow of time L. By this, • the layer in the layer is in the state of Slide 2 mm thick) ^, the adhesion after the ;; outside the range or in the reflow of the charge, the range is hot so that the adhesion CS -41 - (38) 1331166

Since the fluidity of the coating layer tends to be lowered, it is preferable not only to increase the amount of the thermosetting resin but also to optimize the structure and the number of functional groups. For example, the amount of addition of the thermosetting resin is reduced, or the number of functional groups is decreased, and the decrease in the above flow rate can be suppressed. Further, in the case where an epoxy resin is used as the thermosetting resin, a reactive terminal group such as an urethane group, an isocyanate or an acid anhydride in the polyurethane quinone imide resin may be used, and an epoxy resin may be used. In the case where the crosslinking reaction of the epoxy group is carried out, the crosslinking reaction is also one of the causes of the flow reduction. Therefore, in this case, it is preferable to adjust the above flow rate by controlling the average molecular weight of the polyurethane quinone imine resin or the like. When the average molecular weight of the polyurethane quinone imine resin is increased, the number of reactive terminal groups is reduced, so that the reaction with the epoxy group can be suppressed, and the decrease in the flow rate can be suppressed. From such a viewpoint, the weight average molecular weight of the polyurethane quinone imine resin is 50,000 to 200,000 more. The film adhesive of the above may be used, for example, a polyurethane urethane resin may be used. It can be manufactured by using a varnish containing a thermosetting resin, a chelating agent and other ingredients as needed. In this method, first, a mixture which is mixed in an organic solvent is kneaded to prepare a varnish. The kneading used for preparing the varnish can be carried out by a suitable combination of a usual mixer, a pulverizer, a three-light and a ball mill dispersing machine. Next, the prepared varnish is applied onto a substrate film and dried by heating to form an adhesive layer, whereby a film-like adhesive can be obtained. The heat drying can be carried out under conditions in which the organic solvent can be sufficiently vaporized in the varnish. However, it is usually carried out at 5 Torr to 2 Torr for 0.1 to 90 minutes. The organic solvent in the varnish is right to dissolve or disperse the material uniformly.

S-42- (39) 1331166 is unlimited. The organic solvent may, for example, be dimethylformamide '-methylacetamide' N-methyl-2-pyrrolidone, dimethyl hydrazine, monoethyl dimethyl ether, toluene, benzene, Xylene, methyl ethyl ketone, methyl isobutyl ketone 'tetrahydrofuran, ethyl cellosolve, ethyl cellosolve acetate vinegar 'butyl cellosolve, dioxane 'cyclohexanone, ethyl acetate and the like. However, when the adhesive layer contains a thermosetting resin such as an epoxy resin, there may be Φ such as dimethylformamide 'dimethylammoniumamine, Ν-methyl-2_pyrrolidone, and the like. The amine solvent promotes the tendency of the crosslinking reaction of the thermosetting resin. Therefore, in order to optimize the flow rate of the above-mentioned adhesive layer, it is preferable to select an organic solvent in consideration of such a tendency. - For the base film formed of the adhesive layer, the same material as the base film 20 of Fig. 2 can be used. After the formation of the adhesive layer, the material of the substrate may be removed as a film-like adhesive. Further, it is also possible to use a film-like adhesive having a base film without removing the base film. Fig. 3 is a cross-sectional view showing one embodiment of the adhesive sheet according to the present invention. The adhesive sheet 7 shown in Fig. 3 is formed by laminating the adhesive layer 10 on the adhesive layer 30 of the dicing sheet 5 on which the adhesive layer 30 is provided on one side of the base film 20, and the film-like adhesive is laminated. The composition. The adhesive layer 10 and the base film 20 may be the same as those of the film-like adhesives la and lb described above. Further, in the adhesive sheet 7, it is preferable that the adhesive layer 1'' is formed in a shape close to the semiconductor wafer to be bonded thereto (precut according to specifications). Thus, the adhesive sheet 7 is provided as a dicing -43- (40) 1331166

The film-like adhesive layer 30 of the film and the film-like adhesive of the present invention which is an adhesive for bonding wafers laminated on the adhesive layer 30. Thereby, the adhesive sheet 7 is used as a dicing film in the dicing step, and can be used as a wafer bonding film in the wafer bonding step. By the use of the adhesive sheet 7, the manufacturing process of the semiconductor device can be greatly simplified. For example, after the dicing of the adhesive sheet 7 is performed on the side of the film-like adhesive on the back side of the semiconductor wafer in a state of being bonded to the semiconductor wafer, the semiconductor element with the film-like adhesive is self-cut. The sheet 5 is diced and can be used in accordance with the wafer bonding step. The adhesive layer 30 can be formed of a pressure sensitive or radiation hardening type adhesive. The adhesive layer 30 is preferably formed of a radiation-curable adhesive. The radiation hardening type adhesive has a high adhesive force at the time of dicing, and only shows a low adhesive force by the radiation before the dicing, and the adhesive force is controlled to easily. Here, the radiation-hardening type adhesive refers to an adhesive which undergoes a crosslinking reaction when irradiated with radiation such as ultraviolet rays, and which has an adhesive property which can be changed before and after irradiation of radiation. In the case where the adhesive layer 30 is formed of a radiation-curable adhesive, the adhesive layer 30 preferably has a sufficient adhesion force to prevent the semiconductor element from being scattered during dicing. Further, in the adhesive layer 30, when the semiconductor element is taken after radiation irradiation, it is preferable to have a low adhesion which does not damage the semiconductor element. More specifically, the adhesive sheet is formed on the back side of the semiconductor wafer. 7 bonding to make the adhesive layer 10 in close contact - 44 - (41) (41) 1331166 Shape 'make the film-like adhesive relative to the semiconductor wafer at 90 ° C. The peel strength is A, and after the UV irradiation, the 90° peeling strength of the film adhesive of the adhesive layer after the UV irradiation is 25° with respect to the film adhesive of the adhesive layer is B. Preferably, the ratio of 1 N/m or more is preferably 5 N/m or more, more preferably i〇N/m or more. When the A-B is less than 1 N/m, the semiconductor element may be damaged during the pick-up, or the peeling may occur in the interface between the semiconductor wafer and the film-like adhesive at the time of picking, and there is a tendency to be properly taken. Fig. 4 is a cross-sectional view showing a method of measuring the peeling strength at 90 °C at 25 °C with respect to the film-like adhesive of the semiconductor wafer. The film peeling strength at 25 ° C with respect to the film-like adhesive 1 with respect to the semiconductor wafer 3 can be determined by the second method. First, on the back side (back honing treatment surface) of the semiconductor wafer 3 laminated on the support 4, the film-like adhesive 1 of 1 cm width is heated to 8 (TC) to make the adhesive The layer is laminated in such a manner as to be in close contact with the semiconductor wafer 3. Next, as shown in Fig. 4, the peeling force when the film-like adhesive 1 is peeled off in the direction of 90 (in the direction of the arrow in the drawing) is measured. The speed is preferably 100 mm/min. Fig. 5 is a cross-sectional view showing the measurement method of the peeling strength at 90 °C with respect to the adhesive layer of the film-like adhesive at 25 ° C. In contrast to the film-like adhesive 1 The 90° peel strength of the adhesive layer at 25° C. can be determined by the second method. First, the back side (back honing treatment surface) of the semiconductor wafer 3 laminated on the support 4 will be 1 The adhesive sheet having a width of cm is laminated while the side of the film-like adhesive 1 is adhered to the semiconductor wafer 3 while being heated to 80 ° C. 'The exposure amount is 500 mJ/cm 2 -45 - (42 (42) 1331166 UV irradiation. Then 'measured as shown in Fig. 5 to make the dicing sheet 5 in the direction of 90. In the direction indicated by the arrow in the figure, the peeling force is peeled off. At this time, the peeling speed is preferably in the range of iOOmm/min. The adhesive layer 30 is formed of a radiation-curable adhesive, and the adhesive is contained as The polymer of the polymer elastomer is preferably one of those of the radiation polymerizable oligomer. The polymer is preferably an acrylic polymer, and the acrylic polymer may, for example, be (meth) acrylate or a (meth) acrylate copolymer of a monomer unit mainly composed of a derivative, a mixture of the copolymers, etc. Further, in the present specification, (meth)acrylic acid or (meth) acrylate means that each of them is A The meaning of both the acryl and the acrylate, or both of the methacrylate and the acrylate. For the above (meth) acrylate copolymer, for example, the alkyl group has a carbon number of 1 to 15 (methyl group). At least one of the alkyl acrylate monomers (monomer a), and selected from the group consisting of glycidyl (meth) acrylate, dimethylaminoethyl (meth) acrylate '(meth) acrylate Aminoethyl vinegar, (A At least one monomer (monomer b) in a group consisting of 2-hydroxyethyl acrylate, vinyl acetate, styrene and ethylene chloride, and selected from the group consisting of acrylic acid, methylenediic acid and maleic acid a copolymer of at least one monomer (monomer c) in a group. The copolymerization ratio of the above monomer a, monomer b and monomer c, when the whole is 100, the weight ratio is monomer a/monomer b/ The monomer c = 35~99/丨~60/0~5 is preferred. Further, the monomer c is not contained as a monomer unit, and the monomer a/monomer 5 = 70 to 95/5 to 30 is good.

^ S -46 - (43) (43) 1331166 When the ratio of the monomer b exceeds 60% by weight, the adhesive layer 30 becomes a completely compatible system, and the elastic modulus of the adhesive layer 30 after radiation irradiation exceeds 10 MPa. As a result, there is a tendency that sufficient expansion or seizure cannot be obtained. On the other hand, when the monomer b is less than 1% by weight, since the adhesive layer 30 becomes a non-uniform dispersion system, there is a tendency that good adhesion is not obtained. In the case where (meth)acrylic acid is used as the monomer c, the ratio of (meth)acrylic acid is preferably 5% by weight or less based on the entire copolymer. When the ratio of (meth)acrylic acid exceeds 5% by weight, the adhesive layer 30 tends to be in a completely soluble state, and sufficient swelling property or skidability may not be obtained. The weight average molecular weight of the above (meth) acrylate copolymer is preferably 2·0χ105~ΙΟ.ΟχΙΟ5, and 4·Οχ1〇5 ～8·0χ105 is more preferable. The radiation polymerizable oligomer which is combined with the above polymer as a polymer elastomer is an oligomer which is polymerized by irradiation with radiation such as ultraviolet rays. Specific examples of the radiation polymerizable oligomer include an urethane acrylate oligomer, an epoxy modified urethane acrylate oligomer, an epoxy acrylate oligomer, and the like. There is at least one or more oligomers having a carbon-carbon double bond. In the above, it is preferred to use an urethane acrylate-based oligomer in view of the fact that various oligos can be selected depending on the intended purpose. An urethane acrylate-based oligomer, for example, a terminal isocyanurate ethyl ester prepolymer which is obtained by reacting a polyol polyol compound with a polyvalent isocyanate compound to make an acrylate having a hydroxyl group or It is obtained by reaction of methacrylic acid vinegar or the like. The aspect of the polyol compound may, for example, be a vinegar type or

< S -47- (44) 1331166

A polyether type polyol compound. As the polyvalent isocyanate compound, for example, 2,4·tolylene-based diisocyanate, 2,6-methylphenylene diisocyanate, and 1,3-xylylene diisocyanate 1,4- Xylylene diisocyanate, diphenylmethane-4,4-diisocyanate. In the case of an acrylate or methacrylate having a hydroxyl group, for example, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropylmethyl group can be exemplified. Acrylate, polyethylene glycol acrylate, polyethylene glycol methacrylate. The molecular weight of the radiation-polymerizable oligomer is usually from about 3,000 to 30,000, preferably from 3,000 to 10,000, more preferably from 5,000 to 10,000, and most preferably from 4,000 to 8,000. The radiation-polymerizable oligomer is preferably dispersed uniformly in the adhesive layer 30. The dispersed particle diameter is preferably from 1 to 30 μm, more preferably from 1 to ΙΟμη. Here, the dispersed particle size means that the cross section of the adhesive layer 30 is observed by an optical microscope at a magnification of 600 times, and the particle diameter of the oligomer dispersed in the field of view of the microscope is measured and determined. Further, the state of the uniform-dispersion means that the distance between adjacent particles is 〇. 1~1 〇μιη state sound. In the adhesive layer 30, the ratio of the radiation polymerizable oligomer is preferably from 2 to 2 parts by weight, based on 100 parts by weight of the polymer as the polymer elastomer, preferably from 50 to 150 parts by weight. . The ratio of the radiation-polymerizable oligomer may be less than 20 parts by weight or more than 200 parts by weight, and the adhesion between the adhesive layer 30 and the film-like adhesive may be lowered before the radiation irradiation, or 'the adhesion may be after the radiation irradiation The tendency that force cannot be fully reduced. -48 - (45) (45) 1331166 Further, when the ratio of the radiation polymerizable oligomer is within the above range, the moderate elastic modulus after the irradiation of the radiation can be maintained. Thereby, in the expanding step, the desired wafer interval can be easily obtained, and the deformation of the wafer body or the like does not occur, and the drawing can be stably performed. Further, the adhesive layer 30 may contain other components as necessary. In the film-like adhesive of the present invention, a semiconductor element such as 1C or LSI is used as an adhesive for wafer bonding in a semiconductor mounting support member. The semiconductor mounting support member suitable for wafer bonding using the film-like adhesive of the present invention may, for example, be a lead frame such as a 42 alloy lead frame or a lead frame, or the like, or a lead frame such as a lead frame. Or a plastic film formed of a polyimide resin, an epoxy resin, a polyimide film reinforced with a glass nonwoven substrate, a plastic film such as an epoxy resin, a ceramic such as alumina, and a film of the present invention. The adhesive is an organic substrate provided with an organic photoresist layer on the surface thereof, and the wafer bonding of the wiring-attached organic substrate formed by the uneven surface due to the difference in wiring width can be particularly suitably used. Here, the wiring-attached organic substrate is an organic substrate in which a glass fiber reinforced resin, a thermoplastic resin, a thermosetting resin or the like is mainly used, and a wiring pattern formed by a conductor on the surface thereof is provided. The meaning. Further, the film-like adhesive of the present invention is used in a semiconductor device (Stacked-PKG) of a 3D package having a structure in which a plurality of semiconductor elements are laminated on a support member, and the adjacent semiconductor elements are bonded to each other. Adhesive to use. In the use of the film-like adhesive of the present invention, a semiconductor device comprising the film-like adhesive of the present invention, 49 - (46) (46) 1331166, will be specifically described using the drawings. However, the use of the film-like adhesive of the present invention is not limited to the semiconductor device of the embodiment described below. Fig. 6 is a cross-sectional view showing an embodiment of a semiconductor device according to the present invention. In the semiconductor device i〇〇a shown in FIG. 6, the semiconductor device 8a is adhered to the connection terminal of the support member 6»the semiconductor element 8a through the wafer bonding layer i3 formed by the film-like adhesive of the present invention (not shown). The metal wire 13 is electrically connected to an external connection terminal (not shown). Further, the semiconductor element 8a, the metal wire 13, and the like have a structure sealed by the sealing material layer 14. Fig. 7 is a cross-sectional view showing another embodiment of the semiconductor device according to the present invention. In the semiconductor device 1b shown in Fig. 7, the semiconductor element 8a of the first stage is adhered to the supporting member 12 via the wafer bonding layer 11a formed by the film-like adhesive of the present invention. The semiconductor element 8b is adhered to the wafer bonding layer lib formed by the film-like adhesive of the present invention on the semiconductor element 8a. Further, the entire structure is sealed by the sealing material layer 14. The connection terminals (not shown) of the semiconductor element 8a and the semiconductor element 8b are electrically connected to the external connection terminals through the respective metal wires 13a and 13b. The semiconductor device of the present invention is formed by using the film-bonding adhesive for wafer bonding of the present invention to form a wafer bonding layer, and has sufficient reflow resistance, moisture resistance reliability, and insulation reliability between wirings. The semiconductor device (semiconductor package) shown in FIGS. 6 and 7 can be connected to the substrate by the use of the film bonding step of the film-like adhesive of the present invention, and is provided with a metal wire in the vicinity of -50-(47) (47) 1331166. Manufactured by a manufacturing method of a wire bonding step, a step of sealing a sealing material, and the like. In the wafer bonding step, first, a semiconductor element in which a film-like adhesive is laminated is placed on a supporting member so as to hold a film-like adhesive between the supporting member and the supporting member. Then, in this state, the entire body is heated and pressurized, and the semiconductor element can be adhered to the supporting member. The conditions for heating in the wafer bonding step are usually 20 1 to 300 seconds at 20 to 250 ° C. Fig. 8 and Fig. 9 are cross-sectional views showing a method of laminating a film-like adhesive on a semiconductor wafer. The film-like adhesive 1 is placed on the support 4 as shown in Fig. 8. The back side of the semiconductor wafer 3 (the side opposite to the support 4) can be laminated by extrusion of the roll 2. Alternatively, as shown in Fig. 9, the film-like adhesive 1 may be laminated while holding the support 4, the semiconductor wafer 3, and the film-like adhesive 1 in the opposite pair of rolls 2 facing each other. The roller 2 is preferably heated to about 80 °C. Further, the roller 2 is preferably moved at a feed speed of about 0.5 m/min with respect to the film-like adhesive at a pressure of about 4 kgf/cm, and is preferably provided by the present invention. The film-like adhesive used may correspond to an extremely thin wafer or an adhesive of a 3D package in which a plurality of semiconductor elements are laminated. When the film-like adhesive is bonded to the back side of the wafer, the film-like adhesive is usually heated to the temperature of melting, but when the film-like adhesive of the present invention is used, it can be honed on the back side of the extremely thin wafer. It is possible to fit the temperature on the back side of the wafer with a lower temperature than the softening temperature of the dicing tape. As a result, the thermal stress applied to the wafer can be reduced, and the warpage of the wafer that is thinned and thinned can be solved.

S -51 - (48) 1331166 questions. Further, according to the present invention, the fluidity of the adhesive layer can be precisely controlled. Further, the film-like adhesive according to the present invention can improve heat resistance and moisture resistance reliability because high adhesive strength at a high temperature can be ensured.

Further, the film-like adhesive of the present invention can ensure stable characteristics even in the assembly heat process with respect to the package, so that the semiconductor manufacturing step can be adapted to the heat treatment for a long time. At the time of die-casting of the sealing material, the concave portion of the surface of the supporting member can be sufficiently filled by heat and pressure, and the void can be sufficiently suppressed in the wafer bonding layer. By optimizing the pressure-sensitive adhesive layer (addition of other components, optimization of film composition, etc.), thermal stress such as warpage of the wafer can be further reduced, and wafer flying during dicing can be suppressed. The adhesiveness (easily peelable from the dicing tape), the workability in the manufacture of the semiconductor device, and the low heat and gas removal can be further improved. Further, according to the present invention, the film-like adhesive can be provided and cut ( The dicing sheet to which the sheet is attached. The adhesive sheet according to the present invention can be simplified until the dicing step, that is, the joining step of the dicing tape can be omitted. Further, according to the present invention, A semiconductor device using the film-shaped adhesive is provided. The semiconductor device of the present invention can be simplified in terms of manufacturing steps, and is a semiconductor device having excellent reliability. The semiconductor device of the present invention has a thermal expansion coefficient in a support member for mounting a semiconductor element. The difference between the heat resistance and the moisture resistance required for the case where a large semiconductor element is mounted is sufficiently resistant to reflow soldering. [Humidity reliability] and insulation reliability between wirings. -52- (49) 1331166 [Embodiment] [Embodiment] Hereinafter, the present invention will be more specifically described by way of examples and comparative examples. However, the present invention is not Limited to these examples. (Synthesis example)

<Synthesis of Polyurethane Ethylimine Resin (PUI-1)> In a 300 mL flask equipped with a thermometer, a stirrer 'cooling tube, and a nitrogen inflow tube, 'diphenylmethane-4, 4'- 9.34 g of diisocyanate (manufactured by Wako Pure Chemical Industries, Ltd.), 29.87 g of polytetramethylene glycol having an average molecular weight of 2,000 (manufactured by Wako Pure Chemical Industries, Ltd.), and N-methyl-2-pyrrolidone (dehydration grade) 1 0 5 g was used as a reaction liquid, and the reaction was carried out for 1 hour while heating at 100 ° C under a nitrogen atmosphere to form an urethane oligomer having an isocyanate group at the terminal.

Next, 5.79 g of 4,4-dioxyphthalic anhydride (the compound represented by the above formula (30a)) which was heat-treated for 12 hours was added to the reaction liquid in an oven at 170 ° C in advance. Further, the reaction was carried out for 3 hours while heating to 160 ° C to obtain a solution of polyurethane quinone imine resin (PUI-1). When the GPC of the obtained polyurethane bismuth imide resin was measured, Mn = 64,300 in terms of polystyrene, and Mw = 142,500. <Synthesis of Polyurethane Ethylimine Resin (PUI-2)> In a -53-(50) 1331166 300 mL flask equipped with a thermometer, a stirrer, a cooling tube, and a nitrogen inflow tube, diphenyl was charged. Methane·4,4′-diisocyanate 4·67§ (manufactured by Wako Pure Chemical Industries, Ltd.), diphenylmethane·2,4′-diisocyanate 4_67g (manufactured by BASF), 1,4-butylene with an average molecular weight of 2,000 Alcohol 29_87g (manufactured by Wako Pure Chemical Industries, Ltd.) and N-methyl-2-pyrrolidone (dehydrated grade) 105g were used as a reaction liquid 'under a nitrogen atmosphere' while heating to 1 ° C for 1 hour. The reaction produces an urethane oligomer having an isocyanate group at the end.

Next, 5.79 g of 4,4·-diphthalic anhydride, which was heat-treated in an oven at 17 ° C for 12 hours, was added to the reaction liquid, and further heated to 160 ° C for 3 hours. The reaction was carried out to obtain a solution of polyurethane quinone imine resin (PUI-2). When the GPC of the obtained polyurethane bismuth imide resin was measured, it was Mn = 53800 and Mw = 1 18200 in terms of polystyrene. <Synthesis of Polyurethane Ethylimine Resin (PUI-3)> In a 300 ml flask equipped with a thermometer, a stirrer, a cooling tube, and a nitrogen inflow tube, diphenylmethane-4,4·- was charged. 9.34 g of diisocyanate (manufactured by Wako Pure Chemical Industries, Ltd.), 29.87 g of polytetramethylene glycol having an average molecular weight of 2,000 (manufactured by Wako Pure Chemical Industries, Ltd.), and N-methyl-2-pyrrolidone (dehydration grade) 105 g was used as a reaction liquid, and the reaction was carried out for 1 hour while heating to 100 ° C under a nitrogen atmosphere to obtain a solution of an amino acetate oligomer having an isocyanate group at the end. Then, 5.79 g of 4,4'-oxydiphthalic anhydride which was previously heat-treated in a 170 ° C oven for 12 hours was added to the reaction liquid, and further, -54 - (51) (51) was added.

1331166 A reaction was carried out for 3 hours while heating to 1 60 ° C. A solution of a polyurethane urethane resin was obtained. The resulting solution was stirred while stirring, and the resulting precipitate was filtered off. Further, the precipitate was washed with 3 L of methanol, and then air-dried overnight, and dried in a vacuum dryer at 60 ° C for 12 hours to obtain a powdery polyurethane resin. The powdery polyurethane quinone imine resin is redissolved in hexanone to obtain a polyglycolate imine resin (PU1-3) dissolved in the GPC of the obtained polyurethane urethane resin. In terms of ethylene, Mn = 67900 and Mw = 1 5 1400. <Synthesis of Polyimine Resin (PI-A)> A thermometer, a stirrer, a cooling tube, and a nitrogen gas were introduced into a 3 〇OmL flask, and 2,2-bis(cardamine phenoxyphenyl) was charged. 2-73g (0.02mol), polyoxyalkylene diamine 24.00g (Shinjuku Polysaccharide "KF-8010" (trade name), molecular weight: 900) ( 0.0 8 mo 1 ) N-methyl-2-pyrrolidine Ketone (dehydration grade) 1 76 5 g The reaction solution was premixed. After the polyoxyalkylene diamine was dissolved, the flask was cooled in an ice bath to obtain a ruthenium diphenyl phthalic anhydride which was purified by recrystallization from acetic anhydride (the difference between the endothermic start temperature of DSC and the endothermic peak :: 5 It) 1, (0.1 mol) is added in small amounts. After 8 hours of reaction at room temperature, a base of 117.7 g of a nitrogen gas was blown in while it was heated at 18 ° C, and the xylene was azeotropically removed together with water to obtain a polyimine (PI - A ). Solution. When the 〇 p c of the obtained polyimine resin was measured, the ester oxime and 5L were in the imine in the cyclohexane. The polyphenylene tube is made of propane oxygen and is stirred with the ester 2 『40g added by the resin. The poly-55- (52) 1331166 styrene is converted to Μη = 1 2300, Mw = 28700. <Synthesis of Polyimine Resin (PI-B)> In a 300 mL flask equipped with a thermometer 'mixer, a cooling tube and a nitrogen inflow tube, 2.12 g of 1,12-diaminododecane was charged (〇. 〇45 mol), polyether diamine ("ED2000" (trade name), manufactured by BASF, molecular weight. 1923) 5.77 g (O.Olmol) ' 1,3 - bis(3-aminobisyl)tetramethyldioxalate

An alkane ("TS-7100" (trade name) manufactured by Shin-Etsu Chemical Co., Ltd.) 3.35 g (0.045 mol) and 113 g of N-methyl-2-pyrrolidone were stirred. After dissolving 1,12-diaminododecane and polyether diamine, the flask was cooled in an ice bath while being refined by 4,4'- (4, which was recrystallized from cerium acetate in advance). 4'·isopropylidenediphenoxy)bis(phthalic anhydride) (difference between the endothermic start temperature of DSC and the endothermic peak: 2.5 ° C) 15.62 g (0.1 m ο 1 ) was added in a small amount. After reacting at room temperature for 8 hours, 75.5 g of xylene was added, and while nitrogen gas was blown in, it was heated at 180 ° C, and xylene was azeotropically removed together with water to obtain a polyimide resin (PI-B). ) a solution. When the GPC of the obtained polyimine resin was measured, it was changed to polystyrene to Mn = 16300 and Mw = 42,600. <Synthesis of Polyimine Resin (Pl-c)> In a 3 mL flask equipped with a thermometer, a stirrer, a cooling tube, and a nitrogen inflow tube, 1,12-two-membered dodecane 2.71 g (0.045 mol), polyether diamine ("AD2000" (trade name), manufactured by B ASF, molecular weight: 1923) 5.77 g (0.01 m〇l) ' 1,3: bis(3-amino-56-(53) (53) 1331166 propyl) tetramethyldioxane ("TS-7100" (trade name) manufactured by Shin-Etsu Chemical Co., Ltd.) 3.35 g (0.045 mol) 'Loaded in 4,4 purified by recrystallization from acetic anhydride '- (4,4'-isopropylidenediphenoxy) bis(phthalic anhydride) (the difference between the endothermic onset temperature of DSC and the endothermic peak 二.5) 1 5.62g ( 〇. 1 mol ) And 113 g of N-methyl-2-pyrrolidone was used as a reaction liquid, and while the nitrogen gas was blown in, the reaction was carried out while heating at 1801 while stirring. The produced water was removed in the reaction liquid to obtain a solution of a polyimine resin (PI - C ). When the GPC of the obtained polyimine resin was measured, it was Mn = 22,600 in terms of polystyrene.

Mw = 1 2 1 400. <Synthesis of Polyimine Resin (PI-D)> In a 300 mL flask equipped with a thermometer, a stirrer, a cooling tube, and a nitrogen inflow tube, 2,2-bis(4-aminophenoxyl) was charged. The reaction liquid of 13.67 g (0,1 mol) of phenyl)propane and 124 g of N-methyl-2-pyrrolidone was stirred. After dissolving 2,2·bis(4-aminophenoxyphenyl)propane, the flask was cooled in an ice bath while recrystallizing from acetic anhydride to bismuthyl dibenzoate The dianhydride (difference between the endothermic start temperature of DSC and the endothermic peak: 5 ° C) 17.40 g (0.1 mol) was added in a small amount in the reaction solution. After reacting at room temperature for 8 hours, 8 3 g of xylene was added, and while nitrogen gas was blown in, it was heated at 180 t: to azeotropically remove xylene together with water to obtain a polyimine resin (PI-D). ) a solution. When measuring the GPC of the obtained polyimine resin, it is Mn = 22,800 in terms of polystyrene.

< S -57- (54) (54) 1331166

Mw = 121000. (Example 1) A solution of the above-mentioned polyurethane quinone imine resin (P u I - 1 ) and the materials shown in Table 1 (epoxy resin, hardener, hardening accelerator and hydrazine) were used. The varnish was prepared by uniformly mixing to obtain the composition (parts by weight) shown in Table 1. The varnish was applied to a substrate film (release agent treated PET) in a thickness of 40 μm, heated in an oven at 80 ° C for 30 minutes, and further at 150 ° C. 30 minutes heating to remove Ν Μ P. Next, after cooling to room temperature, the base film was peeled off to obtain a film-like adhesive. (Examples 2, 3 and 4) A film-like adhesive having a thickness of 40 μm containing a polyurethane quinone imine resin was obtained in the same manner as in Example 1 except that the varnish prepared by the materials and compositions shown in Table 1 was used. -58- (55) 1331166 Table 1

Ingredient Example 1 Example 2 Example 3 Example 4 Polyurethane quinone imine resin PUI-1 PUI-1 PUI-2 PUI-3 (parts by weight 1 (1〇〇) (100) (100) ( 100) Epoxy resin ESCN195 ESCN195 ESCN195 ESCN195 (parts by weight) (Π.7) (5.0) (Π.7) (5-0) Hardener TrisP-PA-TrisP-PA TrisP-PA (parts by weight) (8.2) (8.2) (8.2) Hardening accelerator TPPK — TPPK TPPK (parts by weight) (0.1) (0.1) (ol) Lubricant HP-P1 HP-P1 HP-P1 HP-P1 (% by volume) (10) (10 (10) (10) Coating solvent NMP NMP NMP CHN * Polyurethane quinone imine resin (removal solvent)

(Comparative Examples 1, 2, 3 and 4) A film-like adhesive having a thickness of 40 μm of a polyimide resin was obtained in the same manner as in Example 1 except that the varnish prepared by the materials shown in Table 2 and the mixing ratio were used. -59- (56) 1331166 Table 2

Ingredient Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Polyimine resin PI-A PI-B PI-C PI-D (parts by weight *) (100) (100) (100) (100) Epoxy resin ESCN195 ESCN195 ESCN195 ESCN195 (parts by weight) (Π-7) (11.7) (11.7) (11.7) Hardener TrisP-PA TrisP-PA TrisP-PA TrisP-PA (parts by weight) (8.2) (8.2) (8.2) ( 8.2) Hardening accelerator TPPK TPPK TPPK TPPK (parts by weight) (0.1) (0.1) (0.1) (0.1) Lubricant HP-P1 HP-P1 HP-P1 HP-P1 (% by volume) (1〇) (ίο (10) (10) Coating solvent NMP NMP NMP NMP * Polyimine resin (removal solvent)

Further, the specific contents of the raw materials shown in Tables 1 and 2 are as follows. • "ESCN-195" (trade name): Sumitomo Chemical Co., Ltd., cresol novolac type solid epoxy resin (epoxy equivalent: 200, molecular weight: 77 8 ) . "Tris P-PA" (trade name) : manufactured by Honshu Chemical Co., Ltd., trisphenol novolak (OH equivalent: 141, molecular weight: 4 24 ), • TPPK: Tokyo Chemical Co., Ltd., tetraphenyl phenyl tetraphenyl borate • NMP: manufactured by Kanto Chemical Co., Ltd., N-methyl- 2-pyrrolidone • CHN: manufactured by Kanto Chemical Co., Ltd., cyclohexanone • “HP-P1” (trade name): water island alloy iron, boron nitride (average particle size: 1 · 0 μ m; maximum particle size: 5 · 1 μ m ) (Evaluation of film adhesive) -60- (57) 1331166 The film properties of Examples 1 to 4 and Comparative Examples 1 to 4 were evaluated by the following method to evaluate the storage modulus at 20 ° C. , main indexing, wafer scatter, flow rate, peeling strength of the film-like adhesive state and reflow resistance. Evaluation is shown in Table 3. Adhesive, enthalpy temperature, die casting

<Storage modulus at 20 ° C> Film-like adhesive sheet cut to a size of 35 mm x 10 mm, using a viscoelastic analyzer "rs A-2 name" manufactured by Rheometrics at a heating rate of 5 ° C / min, frequency 1 Hz, the measurement temperature was measured at 300 ° C, and the storage modulus was determined at 20 ° C. As a test" (commodity - 1 5 0 〇C ~

<main dispersion peak temperature> The temperature at which the tan 値 is measured in the measurement when the storage modulus is obtained is taken as the main dispersion peak temperature of the film-like adhesive, and the complex maximum is found in tanS, so that The temperature of the big sputum is shown as the main dispersion peak temperature. δ is extremely large. In addition, the largest pole & wafer scatter during dicing > on the back side of the germanium wafer (5inch ^ 300μπι) placed on the support table (the support table and the opposite side of the surface) It is laminated with light (temperature: 8 〇 C 'line pressure: 4 kgf/cm, feed speed) and laminated (the same method as shown in Fig. 9). The wafer is opposite to the film-like adhesive. 0』 'Thickness I-like adhesion: 0.5 m/. Next, the cut -61 - (58) 1331166 (dicing) tape (AD-80H adhesive re-peeling mold made by Electric Chemical Industry Co., Ltd.) was laminated. Thereafter, using a dicer, the dicing speed was 10 mm / sec, and the number of rotations was 30,000 rpm, and the wafer scattering at the time of 5 mm x 5 mm dicing was observed. If the ratio at which the wafer scattering occurs is less than 1% of the total wafer, the wafer is scattered. However, the scattering of the residue after the wafer is cut at the end of the wafer is not evaluated. >

A film-like adhesive with a PET substrate (50 μm thick) was cut out to a size of 10 nm x 10 mm to prepare a test piece. The test piece was held between two S 1 ideg 1 as s (MATSUNA ΜI, 7 6 mm X 2 6 mm, thickness 1.0 to 1.2 mm), and l〇〇kgf/ was applied to the entire hot plate at 180 °C. The weight of cm2 is simultaneously heated for 90 seconds. After heating, the amount of exudation of the film-like adhesive from the PET substrate was observed with a graduated optical microscope. The maximum amount of bleeding is used as the initial flow rate. Further, on the same Slide glass as described above, the test piece ‘ was placed in the opposite direction to the side of the Slide glass, and heated on a hot plate having a surface temperature of 180 ° C for 1 hour. Thereafter, the same Slide glass as described above was subjected to registration on the test piece, and a load of 10 〇〇kgf/cm 2 was applied to the whole on a hot plate of 180 t while heating for 90 seconds. The amount of exudation of the film-like adhesive from the PET substrate was observed by an optical microscope after heating. The maximum amount of exudation is used as the flow after heating

-62- ¢5 (59) 1331166 <Peel strength> The peel strength between the semiconductor element (tantalum wafer) 8 and the film-like adhesive 1 was measured in the following manner using the adhesion evaluation device as shown in Fig. 1 . The adhesion evaluation device shown in Fig. 1 is attached to the front end of the rod of the push-pull measuring tool 24, and the handle 26 is provided around the fulcrum 27 as a device having a variable angle.

First, a semiconductor substrate 8 having protrusions is wafer-bonded to a support substrate 1 on which a photoresist layer having a thickness of 15 μm is laminated on a single surface of a thickness of 0.1 mm on a support substrate 1 having a thickness of 0.4 μm and 5 mm×5 mm. . Specifically, a film-like adhesive 1 having a size of 5 mm×5 mm is sandwiched between the semiconductor element 8 and the semiconductor element 8 on the surface of the resistive solder resist layer side of the support substrate 12, and the main dispersion peak temperature of the film-like adhesive 1 is + l The temperature of 〇〇 ° C was heated, and wafer bonding was performed by pressurizing at a pressure of 500 gf per semiconductor element for 3 seconds. Thereafter, a pressure of 9.8 MPa was applied while heating to 180 ° C for 10 seconds. Further, the film-like adhesive 1 was heated and cured at 180 ° C for 5 hours, and then heated on a hot plate 25 of 260 ° C for 30 seconds. Thereafter, the peeling strength was measured by the push-pull gauge 24 when the handle 26 was hung in the protruding portion of the semiconductor element 8 and the handle 26 was moved at 0.5 mm/sec. <State of film-like adhesive after die casting> Support member-63- (60) having a photoresist layer having a thickness of 15 μm and a copper wiring (wiring height of 1 2 μm) on one side of an organic substrate having a thickness of 0.1 mm ) 1331166

On the other hand, a 6.5 mm x 6.5 mm-sized semiconductor element (germanium wafer) was wafer bonded at a thickness of 280 μm. Specifically, a film-like adhesive of 6.5 mm x 6.5 mm is sandwiched between the semiconductor element and the semiconductor element on the surface of the resistive solder resist layer of the supporting member, and the main dispersion peak temperature of the film-like adhesive is + l 〇〇 ° The temperature of C is heated, and at the same time, each semiconductor element is 300 gf (the film-like adhesive is not embedded in the wiring on the supporting member, and the load is adjusted to maintain the load in a tented state) under the pressure of 3 seconds. The wafer is bonded by pressurization. Next, the entire sealing body was covered with a die-casting material (metal mold temperature: 180 ° C, curing time: 2 minutes), and then the sealing material was cured by heating in an oven at 180 ° C for 5 hours. A semiconductor device (CSP96 pin, sealing area: l〇mmxlOmm, thickness: 0.8 mm) was obtained. The initial state of the wafer bonding layer in the obtained semiconductor device was observed using an ultrasonic sounding and mapping device "HYE-FOUCUS" (trade name, manufactured by Hitachi, Ltd.). In the wafer bonding layer, the presence of voids is hardly confirmed, and the concave portion on the surface of the supporting member can be expressed as "good" by the normal tamper, and it can be confirmed that the void is not confirmed or not in the concave portion. After the semiconductor device was heated to a temperature of 180 ° C for 1 hour, the state of the wafer bonding layer after die casting was further observed, and the state after heating was observed in the same manner as described above. Sex> On a single side of an organic substrate having a thickness of 0.1 mm, a thickness of Ι5μm is -64- (61) 1331166

A semiconductor element (sand wafer) having a thickness of 280 μm and a size of 6.5 mm x 6.5 mm was wafer bonded to a support member of a photoresist solder resist layer and a copper wiring (wiring height of 1 2 μηι). Specifically, a film-like adhesive having a size of 6 mm 5 mm x 6.5 mm is held between the semiconductor element and the surface of the photoresist member on the side of the photoresist layer of the supporting member, and heated to a main dispersion peak temperature of the film adhesive + 100 ° C At the same time, the semiconductor elements are pressed for 3 seconds under the pressure of 300 gf each of the semiconductor elements (the film-like adhesive is not embedded in the wiring on the supporting member, and the load can be adjusted in such a manner as to maintain the state of being opened into a tent). Wafer bonding 进而 and then 'by 3 minutes heating at 17 ° C, after the thermal process corresponding to wire bonding, by die casting (metal mold temperature: 1 80 ° C 'cure time · 2 After the whole was covered with a sealing material, the sealing material was hardened by heating at 180 ° C for 5 hours in an oven to obtain a semiconductor device (CSP96 pin 'sealing area: l〇mmxlOmm, thickness: 0.8 mm). The obtained semiconductor device ' was set to 30. (:, 60% R Η constant temperature and humidity device after 1 92 hours of moisture absorption treatment, tamUR Α IR reflow soldering device (semiconductor package surface peak temperature of it, temperature profile: The surface temperature of the package is used as a reference, and the thermal process corresponding to the reflow soldering step is performed after three times of repeated input in accordance with JEDE (adjusted by the specification). Then, the ultra-chopper detection imaging device "hye_FOUCUSj (trade name '日乜Manufactured by the manufacturer, we investigated the peeling of the wafer bonding layer and the presence or absence of damage. In the ffij 'cut the center of the semiconductor device to cut the slice -65- (62) (62) 1331166 face grinding, use 01 in pus The metallographic microscope was used to observe the cross section of the semiconductor device to investigate the presence or absence of peeling and destruction of the wafer bonding layer. In the observation by the ultrasonic detecting and mapping device and the observation by the metal microscope, the peeling and destruction of the unidentified wafer bonding layer was "Good", and it was confirmed that the peeling and the damage were [bad], and the reflow resistance was evaluated.

•66- (63)1331166

Comparative Example 4 2310 120 不良 Poor (unfilled) Poor (unfilled) Poor defect Comparative Example 3 1560 cn 2100 230 Poor (foaming) 〇 \ Poor Comparative Example 2 1630 m Lotus 420 不良 Poor (not replenished) c ^l Poor Comparative Example 1 CN Deer 2600 630 Bad (foaming) 1 Poorly defective Example 4 r-cn 1 蕻800 420 实施 Example 3 Inch 1 壊 320 180 Inch Example 2 CM \〇cn 1 揉360 230 ON Example 1 C^i cn 1 薜400 210 ΟΟ Component 2〇°C Storage Elasticity (MPa) Main Dispersion Peak 値 Temperature (°C) Whether or not the wafer scatters after initial heating, initial heating, peel strength (N/chip) Flow after heating m) State after die casting 1 Reflow-resistant solderability -67- (65) Table 4

Ingredient Example 5 Example 6 Polyurethane Amidoximeimide Resin PUAI-1 PUAI-1 (parts by weight*) (1〇〇) (100) Epoxy Resin ESCN195 ESCN195 (parts by weight) (11.7) ( 5.0) Hardener TrisP-PA — (parts by weight) (8.2) Hardening accelerator TPPK — (parts by weight) (0-D 塡 HP-P1 HP-P1 (% by volume) (1〇) (5) Coating Solvent NMP NMP * Polyurethane Amidoximeimide Resin (Removal of Solvent) 1331166 In addition, the specific contents of the raw materials shown in Table 4 are as described above. The film-like adhesives of Examples 5 and 6 are in the same examples. 1 to 4, and evaluations were carried out in the same manner as in Comparative Examples 1 to 4. The evaluation results are summarized in Table 5. -69 - 1331166 σ υ Table 7 Component Example 7 Example 8 Example 9 Example 10 Example 11 Storage at 20 ° C Elasticity (MPa) 28 25 20 15 22 Main dispersion peak temperature (°c) -36 -38 -42 -53 -44 Whether the wafer is scattered or not, /", 赃Μ Flow (/im) Initial 610 790 830 850 550 After heating 110 150 210 366 250 After the die-casting state, good good good good after good good good good peeling strength (N / c Hip ) 20 26 25 24 22 Resistant to reflow solderability at the beginning of good refraction, good after good heat, good and good [a brief description of the drawing] [Fig. 1] Fig. 1 is an implementation of a film-like adhesive related to the present invention [Fig. 2] Fig. 2 is a cross-sectional view showing an embodiment of a film-like adhesive relating to the present invention. [Fig. 3] Fig. 3 is an embodiment of an adhesive sheet relating to the present invention. Fig. 4 is a cross-sectional view of the method for measuring peel strength. Fig. 5 is a cross-sectional view of the method for measuring peel strength.

<S - 75 · (72) 1331166 [Fig. 6] Fig. 6 is a cross-sectional view showing an embodiment of a semiconductor device according to the present invention. [Fig. 7] Fig. 7 is a cross-sectional view showing another embodiment of the semiconductor device according to the present invention. [Fig. 8] Fig. 8 is a cross-sectional view showing a method of laminating a film-like adhesive on a semiconductor wafer. [Fig. 9] Fig. 9 is a cross-sectional view showing a method of laminating a film-like adhesive on a semiconductor wafer. [Fig. 1] Fig. 10 is a cross-sectional view showing a method of measuring peel strength in the embodiment. [Description of main component symbols] 1 ' 1 a, 1 b : film adhesive 2 〇 : base film 5 : dicing sheet 4 : support 6 : support member 1 1 a, 1 1 b : wafer bonding layer 1 4 : Sealing material layer 2 4 : Push-pull measuring device 2 7 : Pivot point 1 〇: Adhesive layer 3 〇: Adhesive layer 3 : Semiconductor wafer 100a, 10b: Semiconductor device 8, 8 a : Semiconductor element 13, 13a , 13b: metal wire 1 2: support member 26: handle 25: hot plate -76-

Claims (1)

1331166 * X. Patent Application No. 95 1 28 708 Patent Application 'Chinese Patent Application Revision Amendment January 7, 1999 Revision 1. A film-like adhesive for adhering semiconductor components to an adherend The film-like adhesive used is characterized in that it comprises a resin selected from the group consisting of polyurethane quinone imine resin, polyurethane amide amine imide resin, and polyurethane quinone imine-polyamine. An adhesive layer of at least one resin of ethyl formate amide amine imide resin, wherein the polyurethane urethane resin contains a polymer having a partial structure represented by the following formula (la), Wherein Rla represents a divalent organic group containing an aromatic ring or a linear, branched or cyclic aliphatic hydrocarbon, R2a represents a molecular weight of 100 to 1 〇〇〇〇5: a divalent organic group, and R3a represents a total a tetravalent organic group having a carbon number of 4 or more, n1 a $ is an integer of 1 to 100, wherein the polyurethane amidoxime imide resin contains a polymer having a partial structure represented by the following formula (lb), 1331166 ο ο (1b) [wherein, R lb represents a divalent organic group containing an aromatic ring or a linear chain, a branched chain or a ring @ aliphatic hydrocarbon, and R 2b represents a molecular weight of 1 〇〇 to 1 〇〇〇〇 2 The organic group, R3b represents a trivalent organic group having a total carbon number of 4 or more, and nlb represents an integer of 1 to 100]. 2. The film-like adhesive according to claim 1, wherein the _ adhesive layer contains a polyurethane quinone imine resin. 3. The film-like adhesive according to claim 2, wherein the polyurethane urethane resin contains an urethane oligosaccharide having an isocyanate group at a terminal formed by reacting a diisocyanate with a diol. A polymer, a chain-stretched block copolymer of tetracarboxylic dianhydride. 4. The film-like adhesive according to claim 3, wherein the diisocyanate contains a compound represented by the following formula (10), [Chemical 2] 5. The film-like adhesive according to claim 3, wherein the diol comprises a compound represented by the following formula (20), -2- 1331166 [Chemical 3] HO CH2CH2CH2CH20 (20) [wherein, n2 <) represents an integer of 1 to 100]. 6. The film-like adhesive according to claim 3, wherein φ the tetracarboxylic dianhydride contains a compound represented by the following formula (30), [Chemical 4] 7. The film-like adhesive according to claim 2, wherein the polyurethane urethane resin has a weight average molecular weight of 10,000 to 300,000. 8. The film-like adhesive according to claim 1, wherein the adhesive layer contains a polyurethane amidoxime resin. 9. The film-like adhesive according to claim 8, wherein the polyurethane amidoxime resin contains an amine carbamate having an isocyanate group formed by reacting a diisocyanate with a diol. An ester oligomer, a chain-copolymerized block copolymer with a tricarboxylic anhydride. 10. The film-like adhesive according to claim 9, wherein the diisocyanate contains a compound represented by the following formula (10), -3- 1331166 [chemical 6] ocn-0~CH2^O^nc〇 ( The film-like adhesive according to claim 9, wherein the diol contains a compound represented by the following formula (20), [Chem. 7] ^〇~^ΌΗ2〇Η2〇Η2〇Η2〇~^-Η (20) [wherein η20 represents an integer from 1 to 100]. The film-like adhesive according to claim 9, wherein the tricarboxylic anhydride contains a compound represented by the following formula (40), [Chem. 8] (40) 1 3. The film-like adhesive according to claim 8, wherein the polyurethane amide amine imide resin has a weight average molecular weight of 10,000 to 30,000. 14. The film-like adhesive according to claim 1, wherein the adhesive layer comprises polyurethane quinone imine-polyurethane amide amine imide resin. The film-like adhesive according to claim 14, wherein the polyurethane urethane-polyurethane amide amine imide resin has the following formula (la) a partially constructed polymer, Wherein Rla represents an aromatic ring or a divalent organic group of a linear, branched or cyclic aliphatic hydrocarbon, R2a represents a divalent organic group having a molecular weight of 100 to 10,000, and R3a represents a total carbon number of 4 or more. The valence organic group, nla represents an integer from 1 to 100]. The film-like adhesive according to claim 14, wherein the polyurethane urethane-polyurethane amide amine imide resin contains the following formula (lb); Partially constructed polymer, [10] (1b) -5- 1331166 [wherein Rb represents a divalent organic group containing an aromatic ring or a linear, branched or cyclic aliphatic hydrocarbon, and R2b represents a divalent organic compound having a molecular weight of 100 to 10? The group, R3b represents a trivalent organic group having a total carbon number of 4 or more, and nib represents an integer of 1 to 100]. The film-like adhesive according to claim 14, wherein the polyurethane urethane-polyurethane amide amine imide resin is contained, and the diisocyanate and the diol are contained. An urethane oligomer having an isocyanate group at the end of the reaction, a tetracarboxylic dianhydride and a chain-copolymerized chain copolymer with a tricarboxylic anhydride. The film-like adhesive according to claim 17, wherein the diisocyanate contains a compound represented by the following formula (10), [Chemical 11] OCN NCO (1〇) 19. The film-like adhesive according to claim 17, wherein the diol comprises a compound represented by the following formula (20), [Chemical 12] HO CH2CH2CH2CH20 (20) [wherein, n2 <) represents an integer of 1 to 100]. 20. The film-like adhesive according to claim 17, wherein the tetracarboxylic dianhydride comprises a compound represented by the following formula (30), -6- 1331166 [Chem. 13] The film-like adhesive according to claim 17, wherein the tricarboxylic anhydride contains a compound represented by the following formula (40), [Chem. 14] The film-like adhesive according to claim 14, wherein the polyurethane urethane-polyurethane amide amide resin has a weight average molecular weight of 10,000 to 300,000. The film-like adhesive according to any one of claims 1 to 22, wherein the adhesive layer further contains a thermosetting resin. 24. The film-like adhesive according to claim 23, wherein the thermosetting resin contains an epoxy resin. The film-like adhesive according to any one of claims 1 to 22, wherein the adhesive layer further contains a chelating agent. The film-like adhesive according to any one of claims 1 to 22, wherein the adhesive layer has a main dispersion peak temperature of 100 to 50 ° C in the dynamic viscoelasticity measurement. The film-like adhesive described in any one of the above-mentioned claims, wherein the storage modulus of the adhesive layer in the dynamic viscoelasticity of the adhesive layer is less than 1000 MPa. 28. The film-like adhesive according to any one of claims 1 to 22, wherein the flow rate of the adhesive layer is 9.8 MPa at 90 sec while being heated to 18 〇t: 50~2000μΐη. 29. The film-like adhesive according to any one of claims 1 to 22, wherein after heating at 180 ° C for 1 hour, and further heating to 180 ° C, at 9.8 MPa for 90 seconds The flow rate of the adhesive layer at the time of pressing is 50 to 2000 μm. The film-like adhesive according to any one of claims 1 to 2, wherein the adherend is a wiring organic substrate. 31. An adhesive sheet characterized by comprising a dicing sheet provided with an adhesive layer on one side of a substrate film, and in the first to third items of the patent application scope provided on the adhesive layer Any of the film-like adhesives described. The adhesive sheet according to the invention of claim 3, wherein the adhesive layer is formed by a radiation hardening type adhesive. A semiconductor device characterized in that, in a semiconductor device in which at least one semiconductor element is mounted on a supporting member, a wafer bonding layer in which the supporting member and the semiconductor element are bonded is as claimed in claims 1 to 30 A wafer bonding layer formed by the film-like adhesive described in any one of the above. A semiconductor device characterized in that, in a semiconductor device in which at least two semiconductor elements are mounted on a supporting member, a wafer bonding layer for bonding the supporting member and the -8 - 1331166 semi-conducting chip-bonding member to each other, and A layer formed of a film-like adhesive according to any one of claims 1 to 3, wherein at least one of the wafer bonding layers is adhered between the two semiconductor elements.