TW200848483A - Polyurethane imide resin and adhesive composition using this - Google Patents

Abstract

To provide a polyurethane imide resin and an adhesive composition containing thereof which are excellent in the adhesive strength and are suitable for an adhesive for use in circuit-connecting or semiconductor-mounting. The polyurethane imide resin is expressed by general formula (1) (wherein, R<SP>1</SP>is a divalent organic group containing an aromatic ring or an aliphatic ring; R < SP > 2 < /SP > is a divalent organic group having a molecular weight of 100-10,000; R < SP > 3 < /SP > is a tetravalent organic group containing 4 or more carbon atoms; and n and m are each an integer of 1-100). The adhesive composition contains the above polyurethane imide resin.

Description

200848483 IX. The invention relates to the circuit connection of the polyurethane urethane composition. [Prior Art] In the field of packaging materials, the packaging system is a ring. A composite epoxy resin composed of an oxygen tree agent or the like, but it is difficult to use a conductive silver paste because of the so-called low water absorption rate and low mounting method, and the oxygen resin is used for practical use and 'die bonding of epoxy resin. However, as it becomes a surface mounting method, it is a strong solution to this problem, and it is necessary to change, peel strength, and absorb water. The new mounting form of the semiconductor mounting field is affected by the coverage of the flexible circuit board. An imide resin, an adhesive composition using the polyresin, and an adhesive composition using the adhesive. Mostly, organic materials such as epoxy resin are used, and more than 90% of the resin is substituted into a resin encapsulating system grease, a hardener, various additives, and an inorganic cerium filling. Most of the epoxy resins are phenolic phenolic phenolic phenolic phenol type. Epoxy resin does not have the required characteristics to meet the elastic modulus characteristics. Therefore, many organic materials that replace this new high-performance ring are proposed as the wafer bonding (adhesive, epoxy resin, mixed silver powder). In the method of mounting the circuit board of the semiconductor element, the resilience of the silver paste is improved, and the adhesion and the elastic modulus of the bonding layer for wafer bonding after the hardening are improved. The direct view of the 1C wafer is carried on the printed circuit board. The flip-chip mounting method is known. The wafer-connected -4-200848483 terminal is provided with solder bumps for solder connection. Mode, which is based on the compression caused by the difference in thermal expansion coefficient of the plate. When exposed, the connection is reduced to reduce the connection reliability occurring at the connection interface. For the purpose of surface compression, generally, the bottom sealant material is injected into the gap of the wafer/substrate. The bottom sealant injection step has a complicated process, which is not conducive to the problem. In order to solve this problem, the orientation of the package function is recently used. On the other hand, in recent years, semiconductor and liquid crystal display electronic components have been connected to each other, and various adhesive applications have been used, and higher density and higher precision have been developed. Adhesion and reliability. In particular, when a liquid crystal display is connected to a printed circuit board by a TCP or FPC a FPC, and an isotropic conductive adhesive in the adhesive is used as a circuit connecting material, the wafer is not mounted on the substrate. In the past, the semiconductor germanium wafer was directly mounted on the substrate in a face-down manner. In the field of application of an isotropic conductive adhesive device, the circuit has been developed to a high density, and the pole spacing has become extremely narrow. Kaiping 05- 02 3 5 5 No. 8 uses a urethane ruthenium amide resin as a thin layer composite film and is conductively bonded. The problem arises when the wafer and the substrate are connected in various environments. Therefore, in order to review the method of epoxy resin, this production, cost-surface anisotropic conductive crystal mounting, in order to fix the material in the field of self-manufacturing, etc. Etc. 'Also on the adhesion of the adhesive to the TCP connection, the dispersion of conductive particles', the most recent semi-conductive wire, but the opposite of the so-called flip-chip agent, and in the precision of the electrode width and electricity similar to the invention JP 200848483 SUMMARY OF THE INVENTION However, the above-described resin encapsulation system, conductive adhesive for wafer bonding, and flip chip mounting have a problem of poor adhesion to the adherend, as in the field of precision electronic equipment described above, because The circuit has been developed to a higher density, and the electrode width and the electrode spacing have been extremely narrow. The connection conditions of the conventional epoxy resin-based circuit-connecting adhesive have caused problems such as dropping, peeling, and displacement of the circuit, and in order to improve Production efficiency, it is strongly required that the connection time is shortened to less than 1 sec., so low temperature rapid hardening becomes indispensable. The invention relates to a circuit connecting or an adhesive for a semiconductor mounting adhesive, and a binder composition using the same, and the invention provides an excellent low temperature connection and has a shortened connection time The adhesive composition of the above-mentioned adhesive and the adhesive composition for circuit connection using the same, and the connection reliability is also excellent. The invention described in the first application of the patent scope provides a kind of excellent adhesion. Polyurethane phthalimide resin. The invention described in the second aspect of the patent application is a product which can be easily obtained by attaching the invention described in the first aspect of the patent application to the polyurethane urethane resin. The invention described in the third aspect of the invention is a polyurethane-based imide resin which is excellent in solubility in the invention described in the first aspect of the invention. -6-200848483 The invention described in claim 4 is a polyurethane-based imide resin which is excellent in solubility in the invention described in the third aspect of the application. In the invention described in the fifth aspect of the invention, the patent application scope is disclosed in the patent application of the invention of the invention described in the first aspect of the patent application, which is excellent in solubility and easy to form a resin. The invention described in the items 6 to 9 provides an adhesive composition which can improve adhesion reliability. The invention described in the first and second aspects of the patent application is an adhesive composition which can be joined at a low temperature for a short period of time and which is excellent in adhesion, and the invention described in claim 12 of the patent application. An adhesive composition that imparts an isotropic conductivity is provided. The invention described in claim 13 is an adhesive composition for circuit connection excellent in connection reliability. The invention described in claim 1 is a polyurethane urethane resin represented by the general formula (I).

Ο 〇 [In the formula (I), R 1 is a divalent organic group containing an aromatic ring or an aliphatic ring, R 2 is a divalent organic group having a molecular weight of 1 〇〇 to 10,000, and R 3 is a valence of 4 or more carbons. The organic group, η and m are integers of 1 to 1 ]]. 200848483 The invention of claim 2, wherein the polyurethane urethane resin of claim 1 is oligomerized with polyurethane obtained from diisocyanate and diol. A block copolymer in which a chain is elongated with a tetracarboxylic dianhydride. The invention described in the third aspect of the patent application is as described in the first aspect of the patent application of the first aspect of the invention, wherein the polyalcoholate ylide resin of the first aspect of the invention has a general formula (in the formula, 10 mol% to 100 mol% of R1 has the following The structure shown by the general formula (II).

The invention described in claim 4, wherein the polyurethane of the above formula (I), R2 is from 1 〇mol% to 100% by weight. A divalent organic group having an average molecular weight of 100 to 10,000 formed by a repeating unit represented by the following general formula (III). —(GH2_GH2—〇)_ (HI) The invention described in claim 5, such as the polyurethane urethane resin of claim 1, wherein the average molecular weight is 5000 to 500,000, soluble. For ketone solvents. The invention described in claim 6 is an adhesive composition comprising a polyurethane urethane resin and a cubic crosslinkable resin. The invention described in claim 7 is an adhesive group -8- 200848483. The article 'characterized' contains the polyurethane urethane resin of the first aspect of the patent application. The invention of claim 8 is the adhesive composition of claim 7, which further comprises a three-dimensional crosslinkable resin. The invention of claim 9 is the adhesive composition of any one of claims 6 to 8, wherein the polyurethane urethane resin is a polyurethane The ester oligomer is a block copolymer in which a chain is elongated with a tetracarboxylic dianhydride. The adhesive composition according to any one of claims 6 to 8, wherein the three-dimensional crosslinkable resin is at least a radical polymer and contains light. A hardener that generates free radicals upon irradiation or heating. The invention of any one of claims 6 to 8, wherein the three-dimensional crosslinkable resin is at least an epoxy resin and contains latent hardening. Agent. The invention of claim 1, wherein the adhesive composition according to any one of claims 6 to 11 further contains conductive particles. The invention according to claim 13 is an adhesive composition for circuit connection, which is characterized in that the adhesive composition according to any one of claims 6 to 12 is used for a member for circuit connection. . BEST MODE FOR CARRYING OUT THE INVENTION The polyurethane urethane resin of the present invention is represented by the general formula (1 -9-200848483). In the general formula (I), R1 contains an aromatic ring or A divalent organic group of an aliphatic ring, R2 is a divalent organic group having a molecular weight of 100 to 10,000, and R3 is a tetravalent organic group containing 4 or more carbons, ! And m is 1~100

〇1% has the following general formula (the structure shown is preferred, ri-CH2 - TV (Π) The remaining diisocyanate residues can be cited as CH3 -^KCH2-&lt;Q^-

CH,

CH,

Ch2—

—ch2IT •ch2 CuXT&quot; etc. These may be used alone or in combination of two or more. The divalent organic group having an average molecular weight of 100 to 10,000 of R2 in the general formula (I) is a diol residue, and contains 10 m〇l% to 1〇〇m〇i% by the following general formula (III) an) CH2 - GH2-0), -10- 200848483 The structure of the repeating unit is preferably a structure, and the remaining diol residues may be exemplified by -(ch2-ch(ch3)-〇)-, -(ch2- Ch2-o)-, -(CH2-CH2-CH2-CH2-0)-, •(CH2-CH(CH3)-〇)a-(CH2-CH2-0)b-(a/b = 9 〜1 /1 to 9 mol of copolymer), -[C0-(CH2)4-C0-0-(CH2)2-0]-, -[C0-(CH2)4-C0-0-(CH2)2- 0-(CH2)2-0 small, -[C0-(CH2)4-C0-0-CH2-CH(CH3)-0]·, -[co-(ch2)4-co-o-(ch2) 4-o]-, -[co-(ch2)4-co-o-(ch2)6-o]-, -[C0-(CH2)4-C0-0-CH2-C(CH3)2-CH2 -0] -, -[co-(ch2)8-co-o-(ch2)6-o]-, -[co-(ch2)5-o]-, -[co-o-(ch2)6 -o]-, -R4(Si(CH3)2-0)-R4 (R4 is an organic group having a carbon number of 1 to 10), and the like may be used alone or in combination of two or more. The average molecular weight is preferably from 100 to 10,000, more preferably from 50,000 to 5,000. The tetravalent organic group having four or more carbons represented by R3 in the general formula (I) is a tetracarboxylic anhydride residue, and examples thereof include -11 - 200848483

These may be used alone or in combination of two or more. In the general formula (I), η and m must be an integer of from 1 to 100, and more preferably from 1 to 50. The polyurethane urethane resin of the present invention uses a polyurethane oligomer obtained by using @=gastric acid ester and a diol> dianhydride to make a chain extended chain copolymer good. , pj ψ\ Diisocyanate as a constituent of polyethylene urethane oligomers. Diphenylmethane-4,4,1 diisocyanate, diphenylmethane-2' _# _ 2,6 〆 4 — An savory vinegar, a bis- 2,4·—one savory vinegar, a savory vinegar, I,6 —hexamethylene diisocyanate, 3 singularity 1 / 4 ^ ^ 3,5,5-Dimethylcyclohexyl isocyanate, 1,1,-methylenebis(cyanocyclohexane), :I,3-bis(isocyanatomethyl)benzene, anthracene, 3 〆 bis (anthracene, methyl cyanate) cyclohexane, etc., these may be used singly or in combination. Monoalcohol can give a polyhydric alcohol having an average molecular weight of 1 〇〇~1 ,, and the primary bond 糸Ρ -12- 200848483 can be exemplified by polypropylene glycol, polyethyl alcohol, polypropylene glycol/polyethylene glycol copolymer, polytetramethylene. Alcohol, poly(ethylene adipate), poly(diethylene adipate), poly(propylene acrylate), poly(tetramethylene adipate), poly( Hexamethylene adipate), poly(p-pentamethylene adipate), poly(hexamethylene sebacate), poly-ε-caprolactone, poly(hexamethylene carbonate) Ester), poly(oxane), etc., which may be used singly or in combination. The tetracarboxylic dianhydride for extending the chain of the polyethylene glycol methacrylate may, for example, be pyromellitic dianhydride, 3,35,4,4'-diphenyltetracarboxylic dianhydride, 2 , 2',3,3'-diphenyltetracarboxylic dianhydride, 4,4' monohydroxydiphthalic anhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1,1 bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1 double (3,4 - 2 Carboxyphenyl)ethane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl) Milled dianhydride, 3,4,9,10-decanetetracarboxylic dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, 3,4,3',4' benzophenone tetracarboxylic dianhydride, 2,3,2',3' benzophenone tetracarboxylic dianhydride, 2,3,3',4' Benzophenone tetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,2,4,5-naphthalene Carboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,6-dichlorocaxi-1,4,5,8 - tetraresidic acid anhydride, 2,7 - chloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,3,6,7-tetrachloronaphthalene - 1,4,5,8 -4 Carboxylic dianhydride, phenanthrene-1,8,9,10-tetracarboxylic dianhydride, pyrazine-2,3,5,6-tetracarboxylic dianhydride, thiophene-2,3,4,5-tetracarboxylic acid Acid dianhydride, 2,3,3',4'-biphenyl-13- 200848483 tetracarboxylic dianhydride, 3,4,3,,4, monobiphenyltetracarboxylic dianhydride, 2,3, 2,3,2-biphenyltetracarboxylic dianhydride, bis(3,4-dichlorophenyl)dimethyl phthalane dianhydride, bis(3,4-dicarboxyphenyl)methylphenyl decane Dianhydride, bis(3,4-di residue phenyl)diphenyl fluorene dianhydride, 1,4-bis(3,4 di-resin phenyldimethylformamidinyl) phenyl diphenyl, 1 ,3-bis(3,4-dicarboxyphenyl)- 1,1,3,3-tetramethyldicyclohexane dianhydride, p-phenyl bis(trimellitic acid monoester anhydride), A Tetracarboxylic dianhydride, 1,2,3,4-butane tetracarboxylic dianhydride, decalin-1,4,5,8-tetracarboxylic dianhydride, 4,8-dimethyl-1 , 2,3,5,6,7-hexahydronaphthalene-1,2,5,6-tetracarboxylic dianhydride, cyclopentane-1,2 5 3,4 - tetracarboxylic dianhydride, pyrrole _ 2,3,4,5 -tetracarboxylic dianhydride, 1,2,3,4~cyclobutane tetracarboxylic dianhydride, bis(exocyclic) [2,2 , 1] heptane-2,3-dicarboxylic anhydride) hydrazine, bicyclo-(2,2,2)-octyl- 2,355,6-tetracarboxylic dianhydride, 2,2-bis (3,4 Mono-dicarboxyphenyl) hexafluoropropane dianhydride, 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]hexafluoropropane dianhydride, 4,4, one pair (3, 4-dicarboxyphenoxy)diphenyl sulfide dianhydride, 1,4-bis(2-hydroxyhexafluoroisopropyl)benzenedi(trimellitic anhydride), 1,3-bis(2-hydroxyhexafluoroisopropyl) Benzobis(trimellitic anhydride), 5-(2,5-dihydroxytetrahydrofuranyl)3-monomethyl-3-cyclohexene-1,2-dicarboxylic anhydride, tetrahydrofuran-2,3,4,5-four A carboxylic acid dianhydride or the like can be used singly or in combination.

The polyurethane urethane resin of the present invention can be synthesized by a general method such as a solution polymerization method. For example, in the solution polymerization method, the resulting polyurethane urethane resin dissolves in a solvent such as N - Methyl-2-pyrrolidone (NMP), etc., is dissolved in diisocyanate and diol, and reacted at 70 ° C -14 - 200848483 to 1 80 ° C for 1 hour to 5 hours to synthesize polyurethane urethane The resin is further added with tetracarboxylic dianhydride, and reacted at 70 ° C to 180 ° C for 1 hour to 10 hours to obtain a NMP solution of a polyurethane urethane resin. Further, depending on the situation, further adding a monohydric alcohol, an anthracene, an amine, an isocyanate, an acid anhydride or the like may continue the reaction, and the terminal of the polyurethane urethane ylide resin may be modified, and when synthesized, water, an alcohol, a tertiary amine may be used. Etc. as a catalyst. The obtained polyurethane urethane resin can be used to separate the polyurethane urethane resin by water reprecipitation according to the purpose. The composition ratio of the diisocyanate and the diol constituting the polyurethane oligomer is a heteropolycyanate of 1.0, and the diol component is preferably 0.1 mol% to 1.0 mol%, and the polyaminocarboxylic acid is formed. The composition ratio of the polyurethane urethane oligomer to the tetracarboxylic dianhydride of the ethyl ester quinone imine resin is 0.1% of the polyurethane urethane oligomer, and the tetracarboxylic dianhydride is 0.1. Mol%~ 2 · 0 m ο 1 % is preferred. The polyurethane urethane resin of the present invention is measured by gel permeation chromatography using tetrahydrofuran as a solvent for the purpose of imparting toughness and the like of the adhesive, and the average molecular weight of ruthenium converted by standard polystyrene is 5000. Preferably, 5,000 to 300,000 is preferred, and 10,000 to 10,000 00 is more preferable. When the average molecular weight is less than 50,000, the strength of the resin is low, and when it exceeds 50,000, the solubility of the resin is poor. The polyurethane urethane resin of the present invention is preferably a ketone solvent, and examples of the ketone solvent include acetone, methyl ethyl ketone, 2-pentanone, 3-pentanone, and 2 - ketone, methyl isobutyl ketone, 2-heptanone, 4-heptanone, diisobutyl ketone, acetonitrile acetone, isopropylideneacetone, diisopropylidene-15-200848483 ketone, isophorone , cyclohexanone, methylcyclohexanone, acetophenone, camphor, wherein acetone or methyl ethyl ketone is preferred because it has a low boiling point and is easily removed. The polyurethane urethane resin of the present invention described above can be used, for example, in a display system such as a semiconductor or a liquid crystal display, or as an adhesive for mounting a semiconductor element or a circuit. The polyurethane urethane resin of the present invention is excellent in adhesion alone, but it is preferable to use a combination of a three-dimensional crosslinkable resin and a curing agent for the purpose of improving connection reliability. Examples of the three-dimensional crosslinkable resin used in the present invention include an epoxy resin, a cyanate resin, a quinone imine resin, a radical polymer acrylate, a methacrylate, a maleic anhydride imide compound, and the like. These may be used together with a hardener, preferably an epoxy resin and a composition containing a latent hardener. Further, the three-dimensional crosslinkable resin is a radical polymer, and a composition containing a hardener which generates free radicals by light irradiation or heating is preferred. When it is an epoxy resin, a conventional imidazole type can be used as the hardener. A hardener or a mixture thereof of a lanthanide, a boron trifluoride-amine complex, an onium salt, an amine imide, a polyamine salt, a dicyanodiamide, or the like, and an epoxy resin may be used from bisphenol A, Bisphenol type epoxy resin derived from bisphenol F, bisphenol S, bisphenol AD, etc., phenolic resin for epoxy paint derived from phenolic resin for phenol paint, phenolic resin for phenol paint, naphthalene skeleton Epoxy resin 'glycidylamine type epoxy resin, glycidyl ether type epoxy resin, bisphenyl alicyclic type, etc. Each of the epoxy resins having two or more glycidyl groups in one molecule, other habits The known epoxy resin can be used alone or in combination to reduce the alkali metal ions, alkaline earth metal ions, halogen ions, especially chloride ions and hydrolyzed chlorine, etc. of the impurity ions in the epoxy resin used in these epoxy resins. High purity below 00 ppm to prevent electricity Shift and preventing the corrosion of metal conductor circuits touch, so good. As the hardener of the epoxy resin, a conventional imidazole-based, an anthraquinone-based, a boron trifluoride-amine complex, a phosphonium salt, an amine imine, a polyamine salt, a dicyanodiamide or the like can be used. The agent or a mixture thereof is preferably a latent curing agent. These curing agents are coated with a polyurethane-based or polyester-based polymer material and are microencapsulated, because the use time is prolonged. Examples of the cyanate resin include bis(4-cyanate phenyl)ethane, 2,2-bis(tetraphenylphosphonate) propane, and 2,2-bis(3,5-dimethyl- 4-cyanocyanide. Acid phenyl)methane, 2,2-bis(4-phenylene phenyl)-1,1,1,3,3,3-hexafluoropropane, α,α'-bis(4-c-cyanate) —m —diisopropylbenzene, a phenol and a cyanate ester of a dicyclopentadiene polymer, etc., and the prepolymer or the like may be used singly or in combination. Among them, 2,2-bis(4-cyanophenyl)propane, 2,2-bis(3,5-dimethyl-4-c-cyanate phenyl)methane, etc., because the dielectric properties of the cured product are particularly excellent, So good. A metal catalyst can be used as a hardener for the cyanate resin, and a metal catalyst such as manganese, iron, cobalt, nickel, copper, or zinc can be used. Specifically, 2-ethylhexanoate and naphthenic acid can be used. An organic metal complex such as an organic metal salt compound such as an acid salt or an acetamidine acetone complex. The amount of the metal-based reaction catalyst is preferably from 1 ppm to 3,000 ppm, more preferably from 1 ppm to 1000 ppm, and more preferably from 2 -17 to 200848483 ppm to 30,000 ppm, based on the cyanate ester compound. When the amount of the metal-based reaction catalyst is not p p m, the reactivity and the curability are insufficient. When the amount exceeds 300, the control of the reaction becomes difficult and the curing tends to be fast, but it is not determined. The radical polymer (radical polymerizable substance) used in the present invention has a functional group which is polymerized by radical polymerization, and has an acrylate resin, a maleic anhydride imide resin, and a Citraconimide. ) Resin or a restaurant may be used in combination of two or more kinds of nadiimide trees. Further, the radically polymerizable compound may be in any state of a monomer or an oligomer, or may be a monomer or an oligomer, and the (meth) acrylate resin herein means an acrylic resin or a methyl propyl ester (the same meaning is also described below). ). (Meth)acrylic resin (meth) acrylate is obtained by freely combining, (meth) acrylate is methyl (meth) acrylate methyl) acrylate, isopropyl (meth) acrylate, ( Methyl succinic acid isobutyl ester, ethylene glycol di(meth) acrylate, diethylene glycol methyl acrylate, trimethylolpropane tri(meth) acrylate methyl glycol tetra(meth) acrylate Ester, 2-(hydroxy-1,3-dipropylpropane, 2,2-bis[4-(acryloxymethoxy)phenyl]propane-double [4-(acryloxyethoxy)benzene Propane, dicyclopentene methyl acrylate, tricyclodecyl (meth) acrylate, tris(oxyethyl)trimeric isocyanate, ethyl urethane (methyl) propyl hydrazine, two Polyisocyanate ethylene oxide-modified diacrylate or the like may be used in combination of two or more kinds. If necessary, it can also be used without loss of hardening properties up to 1 ppm. Limited methylamine (for use in lipids, etc., poly(alkylene)&gt; ( ) propylene (tetradecyloxy, 2,2 yl (acrylic acid alone) Fan-18- 200848483 The use of a radical polymerization inhibitor such as hydroquinone or methyl ether hydroquinone, and the use of a hydrophilic polymer having a p-acid structure to enhance the adhesion to inorganic substances such as metals. The radical polymer material having a phosphate structure is used in an amount of from 1 part by weight to 1 part by weight, preferably from 0.5 part by weight to 5 parts by weight, and the radical polymer having a phosphate structure can be obtained from phosphoric anhydride. Reaction product with 2-hydroxyethyl (meth) acrylate 'specifically, there are mono (2-methylpropenyl hydroxyethyl) acid phosphate, bis (2-methyl propylene hydroxyethyl) The acid phosphate or the like may be used singly or in combination. The maleic anhydride imide resin has at least one maleic anhydride imide group in the molecule, and examples thereof include phenylmaleic anhydride imide and 1-methyl group. a 2,4 pair of maleic anhydride acetonitrile, N,N ' — m - phenyl bis-maleic anhydride, imine, N, N, - p - phenyl bis-maleic anhydride imide, hydrazine, hydrazine, - 4, 4 - phenyl bis-maleic anhydride imide ,Ν,Ν,— 4,4 — ( 3,3 —Dimethyldiphenyl)bismaleic acid imide, hydrazine, hydrazine, — 4,4—(3,3-dimethyldiphenyl Methane) bismaleic acid imide, hydrazine, hydrazine, — 4,4-(3,3-diethyldiphenylmethane) bismaleimide, imine, hydrazine, a 4, 4 — Diphenylmethane bismaleimide imide, hydrazine, hydrazine, - 4,4 diphenylpropane double maleic anhydride imide, hydrazine, hydrazine, - 4,4-diphenyl ether bis maleic anhydride Imineimide, anthracene, anthracene, — 4,4-diphenylphosphonium bismaleimide, 2,2-bis(4-(4-maleic acid acetimidate)phenyl)propane , 2,2-bis(3~s-butyl-3,4-(4-monomaleimide acetoxyphenoxy)phenyl)propane, 1,1 double 4 (4-maleic anhydride) Imine phenoxy)phenyl)decane, 4,4, a ring-crossed-bis(1(4-maleic anhydride imide *19&quot; 200848483 phenoxy)benzene Oxyl)-2-cyclohexylbenzene, 2,2-bis(4-(4-3⁄4 phthalic acid acetoxyphenoxy)phenyl) hexafluoropropane, etc., which are used in combination of two or more kinds. The Citraconimide resin has at least one citracinium imine group having at least one citrate imine group, and the compound of the stomach, the stomach and the hem imamine compound may be exemplified by phenyl citrate. , 1-methyl s 2 4 _ t citrate imine benzene, N, N' — m — phenyl phenyl sulphate, N, N, 〜 P — phenyl phenyl sulphate , N,N'-4,4-diphenylene quinone quinone, N,N'-4,4-(3,3-dimethyldiphenyl) bis citrate, N,N'-4,4-(3,3-dimethyldiphenylmethane) double-barrel, I,imine, N,N'-4,4-(3,3-diethyldiphenylmethane ) double sticks of urinary imine, N,N' - 4,4-diphenylmethane bis citrate, amide, N,N,~ 4 4,4 diphenylpropane bis citrate, N , N' — 4,4 —diphenyl-branched double-snap, sulphate, N,N'—4,4,2-diphenyl maple, double sylvestre, 2 2~隹隹5 (4 4, citrate, imidate, phenoxy)phenyl)propane, 2,2-bis(3-s-butyl-3,4-(4,1,1,1,1,1,1 End, 1,1 a pair of 4 (4 lysine, acetaminophen phenoxy) phenyl) brothel, 44, a ring of forked pair (1 - (4 citrate quinone acetoxy) benzene Oxy)-2-cyclohexylbenzene, 2,2-bis(4-mono(4-monohydrogenimidophenoxy)phenyl)hexafluoropropane, etc., may be used singly or in combination. A phenolphthalein imine compound having at least one indophenol quinone imine group in a molecule of a naphthylamine resin is polymerized, and the amine compound of the succinyl group is exemplified by phenyl phenolphthalein, 1 - Methyl 〜2 / M phenolphthalein benzene, N, N' — m — phenyl bisphenol quinone imine, N, N, __ p -20- 200848483 — phenyl bisphenol quinone imine, N,N5- 4,4-diphenylenebiquinone quinone imine, N,N'-4,4-(3,3-dimethyldiphenyl)biquinol quinone imine, N, N'-4,4-(3,3-dimethyldiphenylmethane)bisindole quinone imine, N,N'-4,4-(3,3-diethyldiphenylmethane) double Indophenol quinone imine, N,N,-4,4-diphenylmethanebisindole quinone imine, N,N,-4,4-diphenylpropane bismuth quinone imine, N,N' — 4,4 —Diphenyl ether biguanol quinone imine, N,N′—4,4 diphenyl phenyl bisphenol quinone imine, 2,2 —bis( 4 — (4 靛 靛 醯 醯 醯Amine phenoxy)phenyl)propane, 2,2-bis(3-s-butyl-3,4-(4-indolyl phenylenimine phenoxy)phenyl)propane, 1,1 - double 4 One (4 phenolphthalein phenyloxy) Phenyl) decane, 4,4' ring, a pair of di(1 - (4-aminoiminophenoxy) phenoxy) 2-cyclohexyl benzene, 2,2- bis (4) One (4 酣醯 酣醯 imine phenoxy) phenyl) hexafluoropropyl or the like may be used alone or in combination of two or more. When the above radical polymerizable compound is used, a curing agent (polymerization initiator) which generates free radicals by light irradiation or heating can be used, and the curing agent is not particularly limited as long as it is a compound which generates radicals by heat or light. The limitation is a peroxide, an azo compound, an appropriate choice for consideration of the connection temperature, connection time, storage stability, etc., and a half-life of 1 〇 hour from the viewpoint of high reactivity and preservation stability. An organic peroxide having a temperature of 40 ° C or more and a half-life of 1 minute and a temperature of 180 ° C or less is preferred. The half-life of 10 hours is 5 (TC or more, and the half-life of 1 minute is 1 70. The organic peroxide below °C is particularly preferred. When the connection time is 1 sec., the amount of the hardener to obtain a sufficient reaction rate is preferably 1% by weight to 20% by weight, and 2% by weight to 15% by weight. twenty one -

200848483 is especially good. The organic peroxide used in the present invention is specifically selected from the group consisting of dimercapto peroxide, peroxydicarbonate, peroxyesterified ketal, dialkyl peroxide, hydrogen peroxide, and methylidene. Etc. However, the peroxy ester, the dialkyl peroxide, the hydrogen peroxide, the base peroxide in the initiator, the chloride ion and the organic acid are 5 000, because the organic acid generated after the decomposition by heating is less, and can be suppressed. It is particularly good for the corrosion of the connection terminals of the circuit components of Jincheng.

Chlorobenzoquinone peroxide, 3,5,5-trimethylpentanium peroxide, oxide, lauryl peroxide, stearic acid peroxide, succinium oxide, benzoquinone peroxide toluene, benzoquinone Peroxide and the like. Examples of the peroxydicarbonate include di-n-propyl peroxyester, diisopropyl peroxydicarbonate, bis(4-t-butylcycloperoxydicarbonate, di-2-ethoxyl) Dimethoxy, di(2-ethylhexyl peroxy) dicarbonate, dimethoxy oxydicarbonate, bis(3-methyl-3-methoxybutyl peroxycarbonate, etc. Examples of peroxy esters include cumene peroxy neodecanoate, 1, tetramethylbutyl peroxy neodecanoate, 1-cyclohexyl-1 monomethyl oxidized neodecanoate, and t Based on oxidized neodecanoate, t-butyltrimethylacetate, 1,1,3,3-tetramethylbutylperoxy-2-carboxylate, 2,5-dimethyl-2, 5-(2-ethylhexyl peroxide), 1-cyclohexyl-1 monomethylethylperoxide 2-ethylhexyl-peroxy- 2-ethylhexanoate, t-butyl Base oxidizing compound, peroxyperoxymethane, ppm, genus, etc. 2,4 - dioctyl argon milling, bismuth carbonate, butyl phthalate), 1,3,3 - Base peroxyethylated) acid ester, t-2 B-22 - 200848483 base acid ester, t-butyl peroxyisobutyrate, 1,1 double (t-butyl peroxy) cyclohexane, t-hexyl peroxyisopropyl monocarbonate , t-butyl peroxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, 2,5-dimethyl-2,5-di (m-toluene) Peroxidation), t-butyl peroxyisopropyl monocarbonate, t-butyl peroxy-2-ethylhexyl monocarbonate, t-hexyl peroxybenzoate, t-butyl Base oxidized acetate or the like. The ketone ketals may be exemplified by 1,1 double (t-hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1 double (t-hexyl peroxide) ring. Alkane, 1,1 double (t-butyl peroxy)-3,3,5-trimethylcyclohexane, 1,1-(t-butylperoxy)cyclododecane, 2,2 — Bis (t-butyl peroxy) decane. Examples of the dialkyl peroxides include α,α '-bis(t-butylperoxy)diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-2 Examples of the hydrogen peroxide such as (t-butyl peroxide) hexane or t-butyl cumenyl peroxide include diisopropylbenzene hydroperoxide and cumene hydroperoxide. Examples of the methyl ketone peroxides include t-butyltrimethylformamido peroxide, bis(t-butyl)dimethylformamido peroxide, and t-butyltrivinylformamido. Peroxide, bis(t-butyl)divinylcarbenyl peroxide, tris(t-butyl)vinylcarbenyl peroxide, t-butyl triallylmethyl peroxyalkyl peroxide , bis(t-butyl)-propyl propyl lamethionate peroxide, bis(t-butyl)j: propyl -23-200848483 formazanyl peroxide. When the adherend is, for example, a connection terminal of a metal-type circuit component, in order to suppress uranium, the chloride ion and the organic acid contained in the hardener are preferably 5,000 ppm or less, and further decomposed by heating to produce less organic acid. In addition, in order to improve the stability of the adherend after production, it is preferable to have a weight retention ratio of 20% by weight or more after being left open at room temperature (25 ° C) for 24 hours under normal pressure. Mixed use. These hardening agents which generate free radicals may be used singly or in combination, and a decomposition accelerator, an inhibitor or the like may be used in combination. These hardeners are coated with a polyurethane-based or polyester-based polymer material and microencapsulated because of the prolonged usable time. So good. In the adhesive composition of the present invention, in order to improve adhesion and stress relaxation during curing, a polyvinyl butyral resin, a polyvinyl acetal resin, a polyester resin, a polyamide resin, and a poly Acrylic rubber may be used for the quinone imine resin, the xylene resin, the phenoxy resin, the polyurethane resin, the urea resin, etc., and such a polymer component preferably has a molecular weight of 10,000 to 10,000,000. The conductive particles used in the present invention are not particularly limited as long as they have electrical conductivity capable of obtaining electrical connection, and may be metal particles such as Au, Ag, Ni, Cu, Co, or solder, and carbon. When a conductive material of the above metal is coated with a non-conductive glass, ceramic, or a rubber material, in order to obtain sufficient conductivity, the thickness of the metal layer to be coated is preferably 1 〇〇A or more, and the conductive particles are adhered to each other. The agent component is used in the range of 体积·1% by volume to 3% by volume, and preferably used in the range of 0.1% by volume to 20,000% by volume. -24- 200848483 The adhesive composition of the present invention is a blending amount of a polyurethane urethane resin (A) and a three-dimensional crosslinkable resin (B) which are formed by the structure of the general formula (I). It can be used in parts by weight (A): (B) two 1:99 to 99: 1, preferably 10:90 to 90:10. An adhesive composition using a polyurethane urethane resin may be added with chelates and particles for the purpose of adding fluidity, physical properties, conductivity, anisotropy, and thermal conductivity. Such chelates and particles may be cerium oxide, antimony trioxide, gold, silver, copper, nickel, aluminum, stainless steel, carbon, ceramics, or the above metals, non-conductive glass, ceramics, rubber compounds. If the core is coated with the above metals and carbon, the amount of the filler and the particles used is not particularly limited, and the total amount of the adhesive composition containing the polyurethane urethane resin is not limited. 100% by volume, preferably 0.1 to 50% by volume. In the adhesive composition containing the polyurethane urethane ylide resin of the present invention, various polymers may be appropriately added for the purpose of improving the adhesion and the physical properties of the adhesive, and the polymer to be used is not particularly limited. As such a polymer, a phenoxy resin such as a bisphenol A type phenoxy resin, a bisphenol F type phenoxy resin, a bisphenol A · bisphenol F copolymerized phenoxy resin, or the like can be used. Methacrylic acid, polyacrylates, polyimines, polyurethanes, polyesters, polyvinyl butyrals, SBS and its epoxy modified bodies, s EB S and A modified body or the like may be used singly or in combination of two or more kinds, and it is preferred that these polymers contain a decane bond and a fluorine substituent, and these may be completely soluble in the mixed resin, or if The milk phase separation is white turbid and can be used as an adhesive composition for -25-200848483. The molecular weight of the above polymer is not particularly limited. The general amount is preferably from 5,000 to 150,000, and the 10,000 to 80,000 is particularly preferably less than 5,000, and the physical property is lowered, and more than 150,000 is compatible with other components. Poor tendency. The amount of use is preferably 20 parts by weight to 320 parts by weight relative to the amount of the adhesive group containing the polyurethane urethane resin, and when the amount used is less than 20 or more than 320 parts by weight, The adhesive containing the polyurethane urethane resin of the present invention having a reduced fluidity and adhesion may be appropriately added with a softener, an accelerator, an anti-aging agent, a coloring agent, and a coupling agent. The adhesive containing the polyurethane urethane resin of the present invention can be used in the form of a paste when it is liquid at room temperature (25 ° C), and can be used after heating in a room solid. The paste-like @solvent' is not particularly limited as long as it does not reflect the adhesive composition and the additive, and is not particularly limited. The boiling point at atmospheric pressure is 5 (TC~1 50 °C is preferred). , and the boiling point: &amp; T 'is placed at room temperature there is a risk of volatilization, open to the limit, and boiling point of 15 (above TC, it is difficult to volatilize the solvent, the reliability after adhesion will have a bad influence ΦInventive urethane resin containing urethane resin can be used in the form of a film, and the solution of the adhesive composition is coated with a solution of a fluorocarbon resin or a polyphenylene terephthalate. On a release substrate such as formic acid __film' release paper, or by immersing the solution in a non-woven fabric or the like, and placing it on a release substrate, and removing the solvent and other molecules, the hydrazine will have a weight of 100 Å. , the weight of the tendency. Agent composition, difficult agent group temperature, can Responsive, normal pressure (hidden 50〇c can be used as a substrate for the addition of ethylene glycol to the agent group. -26- 200848483 For the use of the film, the use of the film shape is more important from the viewpoint of handling and so on. For convenience, the adhesive composition containing the polyurethane urethane resin of the present invention can be used as an adhesive for different kinds of adhesives having different thermal expansion coefficients, which can be specifically used as a representative silver paste or silver. The circuit connecting material such as a film or an isotropic conductive adhesive is used for a semiconductor element adhesive such as an elastomer for c SP, a bottom sealant for CSP, a LOC tape, a wafer bonding adhesive, etc. The adhesive of the present invention is used. The composition is preferably used for a circuit connection member. The circuit connection member is composed of a substrate and an electrode. The substrate is not particularly limited as long as it is an electrode necessary for electrical connection, and is used for ITO or the like of a liquid crystal display. a glass substrate or a plastic substrate forming an electrode, a printed circuit board, a ceramic circuit board, a flexible circuit board, a semiconductor germanium wafer, etc., may be combined if necessary The conditions for the connection are not particularly limited, and the connection temperature is 9 (TC to 250 ° C, and the connection time is 1 second to 1 minute, and the application, the adhesive, and the substrate are appropriately selected according to the needs thereof, and may be performed according to the needs thereof. The post-hardening is carried out by heating and pressurization, and heat other than heat, such as light, ultrasonic waves, electromagnetic waves, etc., may be used depending on the necessity. The adhesive composition for circuit connection of the present invention may be appropriately added. An adhesion-imparting agent such as a filler, a softener, an accelerator, an anti-aging agent, a coloring agent, a flame retardant, a coupling agent, or a terpene resin. [Embodiment] -27- 200848483 (Example) The following is based on a sample The present invention will be specifically described, but the present invention is not limited thereto. (Example 1) Diphenylmethane-4,4'-diisocyanate (1() m〇1), diphenylmethane-2,4'-diisocyanate (1.0 丨) and an average molecular weight of 1000 Tetramethyl diol (0.8 mol) in 1-methyl-2-pyrrolidone was reacted at 100 ° C for 1 hour under a nitrogen atmosphere, at which time 4,4' monohydroxydi-benzene was added. Formic anhydride (丨.0 mol), triethylamine and 1-methyl-2-pyrrolidone were stirred at 1 ° C for 3 hours, and then benzyl alcohol was added and stirred at 100 ° C for 1 hour. The resulting solution was poured into a vigorously stirred water to filter the precipitate, which was dried in a vacuum at 80 ° C for 8 hours to obtain a polyamine urethane resin P UI - 1, and the obtained polyamine was obtained. The results of GPC measurement of ethyl carbazide imine resin were Mw=51000 and Mn=22000 in terms of polystyrene, and the polyurethane urethane resin was soluble in 40% by weight of solid content. Ketoethyl ketone. The obtained polyurethane quinone imine resin was dissolved in methyl ethyl ketone having a solid content concentration of 40% by weight, and ethyl urethane acrylate (IJ-iO 8 , manufactured by Shin-Nakamura Chemical Co., Ltd.) 1, 1 pair (t-hexyl peroxy) 3,3,5-trimethylcyclohexane (PERHEXA TMH, manufactured by Nippon Oil & Fat Co., Ltd.) as a hardener The solid weight ratio is formulated to disperse 1.25 vol% of the nickel layer with a thickness of 0.2 // m on the surface of the particle of the polystyrene core. The thickness of the outer layer of the nickel-28-200848483 layer is 0.0 2 # m The conductive particles of the gold layer having an average particle diameter of 5 ^ 2.5 were coated on a film of a thickness of 8 Å by using a coating device, and dried by hot air at 70 ° C for 10 minutes to obtain a thickness of the layer of 20 / / m film adhesive. (Example 2) The diol component of P UI·1 was changed to a methylene carbonate having an average molecular weight of 200%, and the same was obtained by the same synthesis as in Example 1, and the result of measurement by GPC was used for polystyrene. Converted to Mw = and Μη = 25000. This PUI-2 was prepared in the same manner as in Example 1 in accordance with Table 1, and a film-like adhesive having a thickness of 20 // m was formed. (Example 3) The diol component of PUI-1 was changed to a diol (0.4 mol) having an average molecular weight of 1,000 and a poly(hexa urate) having an average molecular weight of 2,000 (0 · 4 m ο 1 ). In the same manner, PUI_3 was synthesized in the same manner, and the result of GPC measurement was 55000 in terms of polystyrene, Mn = 25,000, and the polyethyl urethane imide was dissolved in 30% by weight of methyl ethyl ketone in a solid form. This PU1-3 was prepared in the same manner as in Example 1 in accordance with Table 1, and the film thickness of the layer was 20 #m. (Comparative Example 1) m, specific gravity of fluorine to adhesion (six PUI-2: 55000 to obtain copolytetramethyl carbon to obtain M w two resin to obtain viscous -29-200848483 instead of PUlq, using phenoxy resin (PKHC, a product name, a molecular weight of 45,000, and a methyl ethyl ketone solution (solid content: 4% by weight) manufactured by UNION CARBIDE Co., Ltd., and a film-like adhesive was obtained in the same manner as in Example 1. (Comparative Example 2) Instead of PUI- 1. A polyvinyl butyral resin (3 000 K, trade name, manufactured by Denki Kagaku Kogyo Co., Ltd., average polymerization degree 800, methyl ethyl ketone solution (solid content: 40% by weight)) was used, and the rest and Example 1 were used. In the same manner, a film-like adhesive was obtained. [Measurement of Adhesive Strength] Using a film-like adhesive obtained by the above-mentioned production method, a line width of 5 〇β m was formed by vapor deposition on a 40 // m polyacrylonitrile film. Spacing ni# ni, thickness 1 〇# m of copper circuit 5 〇〇 2 layer of flexible circuit board (FPC) 'with a thin layer of 0.2 // m indium oxide (I τ Ο ) glass (thickness) 1.1mm, surface resistance 20Ω/:]), using a hot pressing device (plus Method: Thermostatic type, manufactured by TOR AY ENGINEERING Co., Ltd.), heating and pressurizing at 170 ° C, 3 Mpa for 20 seconds, and connecting width to 2 mm, to produce a joint. The adhesion strength of the obtained joint was based on ns _ z 〇 2 3 7 After the Μ 〇 使用 使用 使用 使用 使用 TEN TEN TEN TEN TEN TEN TEN TEN TEN TEN TEN TEN TEN TEN TEN TEN TEN TEN TEN TEN TEN TEN TEN TEN TEN TEN TEN TEN TEN TEN TEN TEN TEN TEN TEN TEN TEN TEN TEN TEN TEN TEN TEN TEN TEN -30- 200848483 The results of the above-mentioned test results are shown in Table 1. [Table 1] Project Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 PUI-1 80 PUI-2 80 PUI -3 80 PKHC 80 3000K 80 U-108 20 20 20 20 20 TMN 3 3 3 3 3 Adhesive strength (N/m) 580 500 600 100 150 Using the polyurethane (B) of the general formula (I) of the present invention Examples 1 to 3 of the adhesive composition of the oxime imine resin have a high adhesive strength, and the adhesion strength is compared with Comparative Example 1 using phenoxy resin and Comparative Example 2 using polyvinyl butyral. Poor. The same 'three-dimensional cross-linking resin contains epoxy resin and In the case of a curing agent, the same effect can be obtained. As apparent from the above, the polyurethane urethane resin of the present invention and the adhesive composition containing the same have excellent adhesion, and are suitable for circuit connection or semiconductor. According to the present invention, it is possible to provide a low-temperature connection and a shortened connection time, and an adhesive property which is excellent in adhesion characteristics when the electrode width and the electrode interval are narrowed in accordance with the increase in density of the circuit. The composition of the agent and the adhesive composition for circuit connection using the same are excellent in connection reliability. -31 -

Claims (1)

200848483 X. Patent Application Range 1 · An adhesive composition characterized by comprising a polyurethane urethane resin and a three-dimensional crosslinkable resin. 2. The adhesive composition according to claim 1, wherein the polyurethane urethane resin is a block in which a polyurethane urethane oligomer is chain extended with a tetracarboxylic dianhydride. Copolymer. The adhesive composition according to claim 1 or 2, wherein the three-dimensional crosslinkable resin is at least a radical polymer and contains a hardener which generates free radicals by light irradiation or heating. 4. The adhesive composition of claim 1 or 2, wherein the three-dimensional crosslinkable resin is at least an epoxy resin and contains a latent hardening agent. 5. The adhesive composition according to claim 1 or 2, which further contains conductive particles. An adhesive composition for circuit connection, which is characterized in that the adhesive composition of claim 1 or 2 is used for a member for circuit connection. 7. An adhesive composition characterized by comprising a polyurethane urethane resin of the general formula (I), 〇〇 [In the formula (I), R1 is a divalent organic group containing an aromatic ring or an aliphatic ring, R2 is a divalent organic group having a molecular weight of 100 to 10,000, and R3 is 4 -32-200848483 〜1 〇〇 The tetravalent organic group above the integer carbon ^ η and m are -33- 200848483 The seven-character single-character table is the table of the generation of the map element table: the case map, the table, the One or two fingers / V ΓΧ Nothing. If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: -3-