+

WO1999048990A1 - Composition de resine adhesive - Google Patents

Composition de resine adhesive Download PDF

Info

Publication number
WO1999048990A1
WO1999048990A1 PCT/JP1999/001490 JP9901490W WO9948990A1 WO 1999048990 A1 WO1999048990 A1 WO 1999048990A1 JP 9901490 W JP9901490 W JP 9901490W WO 9948990 A1 WO9948990 A1 WO 9948990A1
Authority
WO
WIPO (PCT)
Prior art keywords
polymer
group
norbornene
adhesive resin
molecular weight
Prior art date
Application number
PCT/JP1999/001490
Other languages
English (en)
Japanese (ja)
Inventor
Junji Kodemura
Masato Sakamoto
Original Assignee
Nippon Zeon Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP09541298A external-priority patent/JP3918290B2/ja
Priority claimed from JP10367998A external-priority patent/JP3952102B2/ja
Priority claimed from JP12002898A external-priority patent/JP3975551B2/ja
Application filed by Nippon Zeon Co., Ltd. filed Critical Nippon Zeon Co., Ltd.
Publication of WO1999048990A1 publication Critical patent/WO1999048990A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J165/00—Adhesives based on macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
    • C08G61/04—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms
    • C08G61/06—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds
    • C08G61/08—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring

Definitions

  • the present invention relates to an adhesive resin composition, and more particularly, it is excellent in adhesiveness, heat resistance, moisture resistance, low water absorption, dielectric properties, and long-term reliability based on a polymer having an alicyclic structure.
  • Adhesive resin composition The adhesive resin composition of the present invention has good adhesiveness to fine uneven surfaces such as a wiring board and an electronic component, and can satisfy evaluation criteria by a temperature cycle test and a high-temperature and high-humidity test. Therefore, the adhesive resin composition of the present invention can be used for, for example, bonding and bonding of electronic components to a wiring board, sealing and insulating of electronic components, connection between substrates, interlayer insulating films, transport of electronic components, and the like. It can be suitably applied to the field.
  • the present invention also relates to a novel alicyclic structure-containing polymer having excellent adhesion. Background art
  • semiconductor there is a method in which a conductive conductive resin ball having elasticity is interposed between an electrode of an integrated circuit element and a conductive pattern on a wiring board, and pressure welding is performed by utilizing the compressive stress of an insulating resin.
  • an ultraviolet curing resin or a thermosetting resin is usually used as the insulating resin.
  • insulating resin For bonding between substrates, technology using insulating resin as a connection medium has been developed. Specifically, a technology has been developed to connect the film carrier of a tape carrier package (TCP) and the electrodes of the circuit board using a photocurable insulating resin. Force on the surface of the lead, which has many irregularities formed during processing. The irregularities on the surface of the lead come into contact with the surface of the electrode to form a number of electrical contacts. The periphery of the lead is filled with insulating resin, and the resin is fixed to the circuit board by the adhesive force and shrinkage of the resin.
  • TCP tape carrier package
  • an ultraviolet curable resin is generally used as an adhesive.
  • an ultraviolet-curing resin or a thermosetting resin is often used as a sealing material.
  • An alicyclic structure-containing polymer such as a norbornene-based polymer is a thermoplastic resin material having excellent heat resistance, low water absorption, and dielectric properties.
  • an alicyclic structure-containing polymer having no polar group even when used alone, does not have sufficient performance with respect to adhesion and compatibility with other materials. Therefore, various proposals have been made to enhance the adhesiveness of the polymer having an alicyclic structure.
  • Japanese Patent Application Laid-Open No. 62-27412 discloses an alicyclic structure-containing polymer obtained by adding a polar group such as an epoxy group to an addition copolymer of ethylene and tetradecacene dodecene. It has been pointed out that it is useful as an insulating material for electronic components and an adhesive resin material because of its excellent heat resistance, moisture resistance, low water absorption, and dielectric properties.
  • the conventional alicyclic structure-containing polymer having only a polar group cannot exhibit sufficient adhesiveness in bonding a wiring board or an electronic component having fine irregularities.
  • Circuit boards with semiconductor components mounted on a wiring board using a polymer containing a cyclic structure as the adhesive resin layer have passed the long-term reliability tests such as the temperature cycle test (TCT) and the high-temperature high-humidity test. There was a problem that goes down.
  • TCT temperature cycle test
  • Japanese Patent Application Laid-Open No. 5-148347 reports an example in which an amino group-containing ethylenically unsaturated compound is subjected to a graft reaction with an addition copolymer of a norbornene-based monomer and ethylene.
  • WQ 9 6 Z 3 7 5 No. 28 discloses an example in which an addition polymer of a norbornene-based monomer is modified by a maleic anhydride by a graft reaction, and further reacted with an amino group-containing polymer.
  • the former although an effect of improving the adhesive strength to a certain extent can be seen, it does not have sufficient adhesive strength required for electronic components and the like. In the latter, the fluidity at the time of melting is not excellent, and the wettability with respect to an electronic component having fine irregularities is not sufficient. Therefore, adhesives with satisfactory performance could not be obtained.
  • Japanese Patent Application Laid-Open No. 6-107004 discloses that a random addition copolymer or a ring-opened polymer of a norbornene-based monomer or a hydrogenated product thereof can be used as a carboxylic acid containing an ethylenically unsaturated group, an anhydride thereof, And an alicyclic structure-containing polymer modified with any modifier selected from ethylenically unsaturated carboxylic acid hydroxyalkyl esters.
  • these polymers are described as being effective as adhesives, the types of polar groups contained are limited, and they are not sufficient to be required in the field of precision electronic components. There was a problem that it did not have adhesiveness. Disclosure of the invention
  • An object of the present invention is to provide a polymer having fine irregularities while maintaining various properties such as heat resistance, moisture resistance, low water absorption, and dielectric properties of an alicyclic structure-containing polymer.
  • An object of the present invention is to provide an adhesive resin composition having excellent adhesiveness and excellent long-term reliability.
  • Means for Solving the Problems The inventor of the present invention has eagerly solved the above-mentioned problems of the prior art. However, it has fine irregularities while maintaining various properties such as excellent heat resistance, moisture resistance, low water absorption, and dielectric properties (low dielectric constant and low dielectric loss tangent) inherent to the alicyclic structure-containing polymer. It has been found that it has excellent adhesion to wiring boards and electronic components.
  • the adhesive resin composition of the present invention is preferably used as a varnish that can be applied on a wiring substrate or the like to form an adhesive resin layer, or as an adhesive sheet.
  • a norbornene-based polymer having a specific structure in the side chain is excellent in adhesiveness and fluidity, and is a particularly excellent material in bonding electronic parts and the like.
  • the present invention has been completed based on these findings.
  • an adhesive resin composition containing an alicyclic structure-containing polymer and a low molecular weight compound having a molecular weight of 300 to 3,000.
  • a varnish obtained by dissolving or dispersing the adhesive resin composition in an organic solvent.
  • norpolne having an organic group in a side chain is provided.
  • GPC gel permeation chromatography
  • the alicyclic structure-containing polymer used in the resin composition of the present invention has an alicyclic structure in a main chain and / or a side chain, and has a main chain in view of mechanical strength and heat resistance. Those containing an alicyclic structure are preferred.
  • the alicyclic structure include a saturated cyclic hydrocarbon (cycloalkane) structure and an unsaturated cyclic hydrocarbon (cycloalgen) structure. From the viewpoints of dielectric properties, heat resistance, etc., the cycloaliphatic structure has a cycloalkane structure.
  • the number of carbon atoms constituting the alicyclic structure is not particularly limited, but is usually in the range of 4 to 30, preferably 5 to 20, and more preferably 5 to 15
  • the mechanical strength, heat resistance, and formability are highly balanced and suitable.
  • the proportion of the repeating unit having an alicyclic structure in the alicyclic structure-containing polymer used in the present invention can be appropriately selected according to the purpose of use, but is usually 30% by weight or more. It is preferably at least 50% by weight, more preferably at least 70% by weight. If the proportion of the repeating unit having an alicyclic structure in the alicyclic structure-containing polymer is too small, the dielectric properties, heat resistance, and long-term reliability are poor, which is not preferable. The remainder other than the repeating unit having an alicyclic structure in the alicyclic structure-containing polymer is particularly limited. No, it is appropriately selected according to the purpose of use.
  • the alicyclic structure-containing polymer examples include (1) a norbornene-based polymer, (2) a monocyclic cyclic olefin-based polymer, (3) a cyclic conjugated gen-based polymer, 4) Vinyl alicyclic hydrocarbon polymers, and (5) hydrogenated products thereof.
  • a thermoplastic norpolene-based resin such as a norbornene-based polymer and a hydrogenated product thereof, and a cyclic conjugated diene-based polymer and a hydrogenated product thereof are preferable, and a norbornene-based polymer and a hydrogenated product thereof are more preferable. preferable.
  • a norbornene-based monomer can be prepared by a method disclosed in Japanese Patent Application Laid-Open No. HEI 3-148882 / Japanese Patent Application Laid-Open No. HEI 3-1-21337. What polymerized is used. Specific examples include a ring-opened polymer of a norbornene-based monomer and a hydrogenated product thereof, an addition polymer of a norbornene-based monomer, and an addition copolymer of a norbornene-based monomer and a vinyl compound.
  • hydrogenated norbornene-based monomer, addition polymer of norbornene-based monomer, and copolymer with norbornene-based monomer can be used to achieve a high balance between heat resistance, dielectric properties, and adhesion.
  • an addition copolymer with a natural vinyl compound and a hydrogenated product of a norbornene-based open polymer is particularly preferred.
  • norbornene-based monomers include, for example, bicyclo [2.2.1] heptane-2-ene (common name: norbornene), 5-methyl-bicyclo [2.2.1] hepter-2-ene, 5, 5 — dimethyl-bicyclo [2.2.1] heptane 2-ene, 5-ethyl-bicyclo [2.2.1] heptanyl-2-ene, 5-butyl-bicyclo [2 .
  • the norponene-based monomer may have a polar group.
  • the polar group include an atomic group having a hetero atom or a hetero atom.
  • the hetero atom include an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, and a halogen atom, and from the viewpoint of adhesiveness, an oxygen atom and a nitrogen atom are preferable.
  • a polar group examples include an epoxy group, a carboxyl group, Examples thereof include a droxyl group, an oxy group, an ester group, a carbonyloxycarbonyl group, a silanol group, a silyl group, an amino group, a nitrile group, a sulfone group, and an amide group.
  • norbornene-based monomer having a polar group examples include, for example, 5—methoxycarbone-rubicicyclo [2.2.1] heptane 2—ene, 5—cyanobicyclo [2.2.1] heptane 1 2 — ene, 5 — methyl 1 5 — methoxycarbonirubiciclo [2.2.1] To 2 — ene, 5 — methoxycarbonirubicyclo [2.2.1] heptoto 2 — ene , 5-ethoxycarbonylbicyclo [2.2.2.
  • the norbornene-based polymer means a homopolymer and a copolymer.
  • the proportion of the norbornene-based monomer unit in the norpolene-based polymer is appropriately selected depending on the purpose of use, but is usually 30% by weight or more, preferably 50% by weight or more, and more preferably 7% by weight or more. It is 0% by weight or more, whereby various properties such as fluidity, heat resistance, dielectric properties, and long-term reliability are highly balanced.
  • Vinyl compounds copolymerizable with norbornene monomers include, for example, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1 —Pentene, 4-methyl— 1 pentene, 4—methyl 1—hexene, 4,4-dimethyl-1—hexene, 4,4-dimethyl-1 pentene, 4-ethyl-1—hexene, 3-ethyl — 1 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1 —hexadecene, 1-year-old decene, 1 eicosene, etc.
  • Olefins cyclobutene, cyclopentene, cyclohexene, 3,4-dimethylcyclopentene, 3-methylcyclohexene, 2- (2-methylbutyl) 1-1 -Cyclohexene, cyclooctene, 3a, 5,6,7a -tetrahydro-1,4,7-methano-1H-cyclopentane such as 1H-indene; 1,4-hexadiene, 4-methyl--1,4- Non-conjugated gens such as xadiene, 5-methyl-1,4-hexadiene and 1,7-octadiene; These vinyl compounds are Each can be used alone or in combination of two or more.
  • the content of other monomers in the norbornene-based polymer can be appropriately selected according to the purpose of use.
  • the content is usually 70% by weight or less, preferably 50% by weight. When it is at most 30% by weight, more preferably at most 30% by weight, heat resistance is excellent, so that it is preferable.
  • the content of the other monomer when the content of the other monomer is preferably 50% by weight or less, more preferably 20% by weight or less, and particularly preferably 10% by weight or less, It is suitable because it has excellent heat resistance.
  • the amount of the norbornene-based monomer unit bonded is preferably 50% by weight or more, more preferably 80% by weight or more, and particularly preferably 90% by weight or more. .
  • the polymerization method of the norbornene-based monomer or the norbornene-based monomer and the copolymerizable vinyl compound and the hydrogenation method are not particularly limited, and can be performed according to known methods.
  • the ring-opening polymer of a norbornene-based monomer is composed of a norbornene-based monomer, a ring-opening polymerization catalyst, a metal halide such as ruthenium, rhodium, palladium, osmium, iridium, and platinum, a nitrate or acetylacetylone compound, and a reducing agent.
  • a catalyst system comprising a metal halide such as titanium, vanadium, zirconium, tungsten, molybdenum or an acetylacetonate compound and an organic aluminum compound, in a solvent or in a solvent.
  • ring-opening polymerization usually in the absence of a solvent, at —50 ° C .: a polymerization temperature of up to 100 ° C. and a polymerization pressure of 0 to 50 kg Zcm 2.
  • molecular oxygen, alcohol, ether, peroxide, power By adding a third component such as rubonic acid, acid anhydride, acid chloride, ester, ketone, nitrogen-containing compound, sulfur-containing compound, halogen-containing compound, molecular iodine, and other Lewis acids, polymerization activity and The selectivity of ring-opening polymerization can be improved.
  • An addition polymer of a norbornene-based monomer or an addition copolymer of a norbornene-based monomer and a vinyl-based compound can be obtained, for example, by mixing a monomer component in a solvent or without a solvent with a titanium, zirconium, or vanadium compound and an organoaluminum. in the presence of a catalyst system comprising a compound, can be obtained usually one 5 0 ° C ⁇ 1 0 0 ° C of the polymerization temperature, 0 at 5 0 kg polymerization pressure of Z cm 2, the method of copolymerizing .
  • the hydrogenated norbornene-based polymer can be obtained by a method in which a ring-opened polymer is hydrogenated with hydrogen in the presence of a hydrogenation catalyst according to a conventional method.
  • the hydrogenation catalyst include a homogeneous catalyst composed of a palladium or nickel compound and organoaluminum, and a heterogeneous catalyst in which a palladium or nickel compound is supported on a carrier such as alumina or silica.
  • the hydrogenation rate is usually at least 50%, preferably at least 70%, more preferably at least 90%, whereby a hydrogenated polymer having excellent fluidity, heat resistance and the like can be obtained. it can.
  • norbornene polymers can be used alone or in combination of two or more.
  • Examples of the monocyclic cyclic olefin polymer include, for example, monocyclic cyclic olefins such as cyclohexene, cycloheptene and cyclooctene disclosed in JP-A-64-62616. An addition polymer of a system monomer can be used.
  • An addition polymer of a system monomer can be used.
  • cyclic conjugated gen-based polymer examples include, for example, cyclopentene, cyclohexene and cyclohexene disclosed in Japanese Patent Application Laid-Open Nos. 6-13657 and 7-258318.
  • a polymer obtained by addition-polymerizing a cyclic conjugated monomer such as 1,2- or 1,4-monomers and a hydrogenated product thereof can be used.
  • vinyl alicyclic hydrocarbon-based polymer examples include, for example, vinyl alicyclic hydrocarbon monomers such as vinylcyclohexene and vinylcyclohexane disclosed in JP-A-51-9989.
  • Polymers and their hydrogenated products such as styrene and ⁇ -methylstyrene disclosed in JP-A-63-43910 and JP-A-64-17606. Any hydrogenated product of the aromatic ring portion of the polymer of the vinyl aromatic monomer can be used.
  • an alicyclic structure-containing polymer having a polar group more preferably an active hydrogen-containing polar group is used.
  • a polymer having an alicyclic structure is used.
  • the polar group include a hetero atom, an atomic group having a hetero atom, and the like.
  • the hetero atom include an oxygen atom, a nitrogen atom, a sulfur atom, a gay atom, a halogen atom, and the like. From the viewpoint of adhesiveness, an oxygen atom and a nitrogen atom are preferable.
  • the polar group include an epoxy group, a carboxyl group, a hydroxyl group, an oxy group, an ester group, a carbonyloxycarbonyl group, a silanol group, a silyl group, an amino group, a nitrile group, a sulfone group, Amide groups and the like.
  • epoxy group, carboxyl group, hydroxy group, carbonyloxycarbonyl group, amino group And a amide group are preferred, and a carboxyl group and a hydroxy group are particularly preferred.
  • the above-mentioned polar group-containing norbornene-based monomer may be used alone, or a polymer obtained by (co) polymerizing with another norponene-based monomer or a vinyl compound.
  • a polymer having an alicyclic structure in which a polar group is introduced into a norbornene-based polymer by a modification reaction can be introduced with a high molecular weight and a large number of polar groups, so that it is suitable when high adhesive strength is required.
  • Such a polar group-modified alicyclic structure-containing polymer is not particularly limited, and a polymer subjected to a modification reaction by an ordinary method is used. Specific examples include a chlorinated product of an alicyclic structure-containing polymer, a chlorosulfonated product, and a modified product of a polar group-containing unsaturated compound, and preferably, a graph of a polar group-containing unsaturated compound. It is a denatured product.
  • Examples of the unsaturated compound having a polar group include glycidyl acrylate, glycidyl methacrylate, glycidyl p-styrylcarboxylate, end-cis-bicyclo [2,2,1] hept-5-ene 1,2,3-dicarboxylic acid, endo-cis-bicyclo [2,2,1] hept-15-en-2- (methyl) _2,3-dicarboxylic acid, arylglycidyl ether, 2-methylarylligre Unsaturated epoxy compounds such as sigil ether, glycidyl ether of o-aryl phenol, glycidyl ether of m-aryl phenol, and dalicydyl ether of p-aryl phenol; acrylic acid, methacrylic acid, ethyl acrylate Acid, maleic acid, fumaric acid, itaconic acid, endocysic acid mouth [2.2.1] hept-5
  • radical initiator for example, organic peroxides, organic peresters and the like are preferably used.
  • radical initiators include benzoylperoxide, dichlorobenzoylperoxide, dicumylperoxide, di-tert-butylperoxide, 2,5— Dimethyl 2,5—di (peroxy dobenzoate) hexine—3,1,1,4-bis (t ert —butylperoxyisopropyl) benzene, lauroylperoxide, tert —butylperacetate, 2,5 —dimethyl-1,2,5-di (tert —butylperoxy) hexine-1,2,5 —dimethyl2, 5-di (tert-butylperoxy) hexane, tert-butylperbenzoate, tert-butylperphenylacetate, tert-butylperisobutyrate, tert-butylper-sec-butylate, tert-butylperpirate, Cumyl perpiparate and tert-
  • radical initiators can be used alone or in combination of two or more.
  • the proportion of the radical initiator used is usually 0.001 to 30 parts by weight, preferably 0.01 to 20 parts by weight, based on 100 parts by weight of the unmodified alicyclic structure-containing polymer. And more preferably in the range of 0.1 to 10 parts by weight.
  • the graft denaturation reaction is not particularly limited and can be performed according to a conventional method.
  • the reaction temperature is usually 0 to 400 ° C, preferably 60 to 350 ° C, and the reaction time is generally 1 minute to 24 hours, preferably 30 minutes to 10 hours. is there.
  • the graft modification rate of the graft modified product of the alicyclic structure-containing polymer is appropriately selected depending on the purpose of use, but is usually 0.1 to 1 based on the total number of units of one monomer in the polymer.
  • the range is 100 mol%, preferably 0.2 to 50 mol%, more preferably 1 to 30 mol%.
  • the graft modification rate of the modified norportene-based polymer is within this range, the adhesiveness, the dielectric properties, and the long-term reliability are highly balanced and suitable.
  • Graph The power factor is represented by the following equation (1).
  • X is the total number of moles of the grafted monomer modified residues, which can be determined by NMR.
  • Y is equal to the weight average molecular weight (Mw) of the polymer / molecular weight of the monomer. In the case of copolymerization, the molecular weight of the monomer is the average molecular weight of the monomer.
  • the alicyclic structure-containing polymer having a hydroxyl group or a carboxyl group which is suitable in the present invention, is an unsaturated epoxy compound, an unsaturated carboxylic anhydride compound, and an unsaturated ester compound as described above.
  • a method of reacting an active hydrogen-containing compound (b) a method of reacting an alkali metal salt or an alkaline earth metal salt of an active hydrogen-containing compound, followed by hydrolysis Can also be obtained by
  • the active hydrogen-containing compound is not particularly limited as long as it is a substance capable of nucleophilic attack on electropositive carbon, and is at least selected from the group consisting of a hydroxyl group, an amino group, a mercapto group, and a carboxyl group.
  • a compound having one kind of functional group is preferably used.
  • active hydrogen-containing compounds include: water; ammonia; methanol, ethanol, 1-propanol, 2-propanol, allylic alcohol, 1-butanol, 2-butanol, 1-methyl-1 1-propanol, 2-methyl-2-propanol, methallyl alcohol, 1-pentanol, 2-pentanol, 3-pentol, 2-methyl-1-butanol, 3-methyl-1-butanol, 2 —Me Chill-2—butanol, 3—Methyl-2-butanol, 2,2—Dimethyl-1-propanol, 3—Methyl-2-buten-1-ol, 3—Methyl-3—buten-1-ol, cyclopentanol, 1 Alcohols such as hexanol, cyclohexanol, geraniol, citronellol, benzyl alcohol, furfuryl alcohol, ethylene glycol, propylene glycol, and glycerin; mono
  • 1 and 8 Nuff evening lick anhydride, 3—Ami ⁇ 2 — Naphth toy acid, 3 — Amino-1,2, 7 — Naphthalenedisulfonic acid, 7 — Amino 1, 3 — Naphine rangedulphonic acid, 2 — Amino a — (Methoxyi Mino) _ 4 monothiazoleacetic acid, 1 —amino-1-cyclohexane carboxycarboxylic acid, 1 amino 1-cyclopentane Examples thereof include carboxyl lic acid, aminocarboxylates such as 1-amino-1-cyclopropanecarboxylic acid, isodipecotic acid, nicobetic acid, pipecolinic acid, and p-aminobenzoic acid.
  • active hydrogen-containing compounds can be used alone or in combination of two or more.
  • the amount of the active hydrogen-containing compound used is appropriately selected depending on the reaction conditions, but is based on the oxy group, epoxy group, oxycarbonyl group, carbonyloxy group or carbonyloxycarbonyl group introduced in the graft reaction. Usually, it is in the range of 0.1 to 100 equivalents, preferably 0.3 to 50 equivalents, and more preferably 0.5 to 20 equivalents.
  • the reaction of the active hydrogen-containing compound can be carried out according to a conventional method.After the completion of the graft reaction, the graft-modified polymer may be isolated and reacted, or the active hydrogen may be directly added to the reaction solution after the completion of the graft reaction.
  • the reaction can also be carried out by adding a contained compound.
  • the reaction conditions are such that the reaction temperature is generally 0 to 250 t :, preferably 50 to 200 ° C, and the reaction time is usually 10 minutes to 15 hours, preferably 30 minutes to 5 hours.
  • Examples of the alkali metal salt or alkaline earth metal salt of the active hydrogen-containing compound include compounds of the above-mentioned active hydrogen-containing compound such as lithium, sodium, potassium and calcium salts.
  • the reaction of an alkali metal salt or an alkaline earth metal salt of an active hydrogen-containing compound may be carried out according to a conventional method. After the completion of the graft reaction, the graft-modified polymer may be isolated and reacted. The reaction can also be carried out by adding an active hydrogen-containing compound directly to the reaction solution after completion of the reaction.
  • the reaction conditions are such that the reaction temperature is usually 150 to 200 ° C, preferably 0 to 100 ° C, and the reaction time is usually 10 minutes to 24 hours, preferably 30 minutes to 10 hours. is there.
  • the hydrolysis can be usually carried out by adding a hydrolysis reagent to the reaction solution after the reaction of the alkali metal salt or the alkaline earth metal salt of the active hydrogen-containing compound.
  • the hydrolysis reagent is not particularly limited, and for example, water, dilute hydrochloric acid, a saturated aqueous solution of ammonium chloride, and organic acids can be used.
  • the reaction temperature is usually 50 to 100 ° C, preferably 0 to 50 ° C
  • the reaction time is usually 1 to 24 hours, preferably 10 to 10 hours. Time.
  • the proportion of the polar group in the polar group-containing alicyclic structure-containing polymer may be appropriately selected according to the purpose of use, but is usually 0.1 to 100 mol% based on all repeating units of the polymer. When it is in the range of preferably 0.2 to 50 mol%, more preferably 1 to 30 mol%, the adhesiveness and long-term reliability are highly balanced and suitable.
  • the molecular weight of the alicyclic structure-containing polymer (including the polar group-containing alicyclic structure-containing polymer) used in the present invention is appropriately selected depending on the purpose of use.
  • the gel-permeation-number average molecular weight of polystyrene measured by gel permeation / chromatography is 5,000 or more, preferably 5,000 to 50,000. It is preferably in the range of 0,000, more preferably 8,000 to 200,000, and particularly preferably in the range of 10,000 to 100,000. If the number average molecular weight of the alicyclic structure-containing polymer is excessively small, long-term reliability is poor, which is not preferable. On the other hand, when the number average molecular weight of the alicyclic cyclic structure-containing polymer is excessively large, the adhesiveness to circuit boards and electronic components having fine irregularities is reduced.
  • the glass transition temperature (T g) of the alicyclic structure-containing polymer used in the present invention may be appropriately selected according to the purpose of use. Higher is preferred, usually The temperature is at least 50 ° C, preferably at least 70 ° C, more preferably at least 100 ° C.
  • the norbornene-based polymer having an organic group in a side chain according to the present invention has a weight average molecular weight (M w) in terms of polystyrene of 1,000 to 1,000,000,000 as measured by GPC.
  • M w weight average molecular weight
  • the organic group in the side chain contains 3 to 30 carbon atoms, and contains a carboxyl group and at least one other polar group, respectively.
  • Such an organic group-containing norbornene-based polymer can be produced by, for example, a method of reacting an active hydrogen-containing compound after the above-described graft modification, which will be described in more detail here.
  • the organic group-containing norbornene-based polymer of the present invention has a carboxyl group and at least one other polar group, each having an organic group having 3 to 30 carbon atoms in the side chain. . If the number of carbon atoms in the organic group is too small, the adhesiveness is reduced, and if the number of carbon atoms is too large, the fluidity of the polymer, such as the melt viscosity and the solution viscosity, is reduced, and neither is preferable. Therefore, as described above, when the number of carbon atoms in the organic group is usually 3 to 30, preferably 4 to 25, and more preferably 5 to 20, the adhesiveness and fluidity of the polymer are Highly balanced and suitable.
  • At least one other polar group in the organic group is preferably at least one selected from oxygen, nitrogen, and sulfur for the purpose of further improving the adhesion improved by the carboxyl group.
  • Those containing at least one heteroatom are selected.
  • Specific examples of the polar group containing a hetero atom include an ester bond, an amide bond, A polar group having a mid bond, a sulfide bond, an ether bond, a thioether bond and the like can be mentioned, and a polar group having an ester bond or an amide bond is preferable from the viewpoint of adhesiveness.
  • the method for producing the organic group-containing norbornene-based polymer is not particularly limited.
  • a carbon-carbon unsaturated compound capable of forming a carboxyl group is introduced into a norbornene-based polymer and a hydrogenated product thereof by a graft reaction.
  • polymerization is performed using a norbornene-based monomer having a polar group other than a carboxyl group, and a part of the polar group site of a norbornene-based polymer or a hydrogenated product thereof is oxidized.
  • (V) Among the norbornene-based monomers, a carboxyl-containing norbornene-based polymer polymerized by using a carboxyl-containing norbornene-based monomer or a carboxyl group of a hydrogenated product thereof A method in which a part of the position is protected with a known protecting group, or is converted to an intended organic group by reduction using a suitable reducing agent,
  • the norbornene-based polymer having a carbon-carbon unsaturated bond may be a norbornene-based monomer having a side chain having an unsaturated bond such as a vinyl group or a vinylidene group outside the ring or a dicyclopentene. It can be obtained by the above polymerization method using a norbornene-based monomer having a carbon-carbon unsaturated bond which does not participate in the polymerization reaction, such as orange, but the unsaturated compound is introduced at a high modification rate.
  • the method of introducing a polar group by the above-mentioned method (I) or (II) is most preferable from the viewpoints of improving the adhesion and increasing the selectivity of the polymer.
  • a carboxylic acid anhydride having a carbon-carbon unsaturated bond hereinafter referred to as a carboxylic acid anhydride or a hydrogenated product thereof.
  • unsaturated monomer a carboxylic acid anhydride having a carbon-carbon unsaturated bond
  • unsaturated monomer a method of reacting with an active hydrogen-containing compound, or (2 ') an alkali metal salt or alkaline earth metal of an active hydrogen-containing compound after the reaction of (1).
  • a conventionally known graft reaction can be used.
  • 1) a method of irradiating a gamma ray or an electron beam in the presence of a norbornene-based polymer and an unsaturated monomer 2) a method of irradiating a norbornene-based polymer with a radiation and then coexistence of an unsaturated monomer, (3) A method in which a norbornene-based polymer and an unsaturated monomer coexist in a solution state, a melted state, a dispersed state, or an impregnated state, and a reaction is performed in the presence or absence of a radical generator. be able to.
  • the polymerization in the impregnated state means that the norbornene-based polymer is dispersed in water or a solvent in a powder or pellet state, and the dispersed norbornene-based polymer and the radical generator are immiscible with each other.
  • a norbornene-based polymer and an unsaturated monomer coexist in a solution state (solution method), a molten state (melting method) or an impregnated state (impregnation method), and in the presence or absence of a radical generator.
  • a solution method a molten state
  • an impregnated state impregnated state
  • a radical generator a radical generator for reacting both is preferable, and a solution method is most preferable.
  • unsaturated monomers include, for example, acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, Anhydrides such as isocrotonic acid and nadic acid (that is, endo-cis-bicyclo [2,2,1] hept-5-ene-2,3-dicarboxylic acid) can be mentioned.
  • anhydrides of dicarboxylic acids such as maleic acid, itaconic acid, tetrahydrofuric acid, and nadic acid are preferable.
  • Maleic anhydride is most preferred from the viewpoint that the graft reaction rate can be relatively freely controlled and purification after the reaction is relatively easy.
  • These unsaturated monomers can be used alone or in combination of two or more.
  • radical generator As the radical generator, the above-mentioned organic peroxides, organic peresters, azo compounds and the like can be used.
  • the amount of the radical generator used is the same as described above.
  • Solvents used in the above reaction include, for example, aromatic hydrocarbon solvents such as benzene, toluene, and xylene; aliphatic hydrocarbon solvents such as pentane, hexane, heptane, octane, nonane, and decane; cyclohexane , Methylcyclohexane, decahydronaphthalene, etc. Alicyclic hydrocarbon solvents; chlorinated hydrocarbon solvents such as benzene, dichlorobenzene, trichlorobenzene, methylene chloride, chloroform, carbon tetrachloride, and tetrachloroethylene; .
  • aromatic hydrocarbon solvents such as benzene, toluene, and xylene
  • aliphatic hydrocarbon solvents such as pentane, hexane, heptane, octane, nonane, and decane
  • solvents can be appropriately selected depending on the unsaturated monomer used, reaction conditions and the like.
  • the radical generator can be charged and reacted with the unsaturated monomer at a time, or the reaction can be carried out while appropriately adjusting the concentration of the radical generator in the reaction system. If it is not necessary to broaden the molecular weight distribution, the latter reaction method is preferred.
  • the polymerization can be carried out in a molten state without a solvent or in the presence of a small amount of a solvent, for example, 30 parts by weight or less of a solvent per 100 parts by weight of a norbornene-based polymer.
  • the graft denaturation rate is not particularly limited, and the graft denaturation reaction can be performed in the same manner as the above-described graft denaturation reaction.
  • the reaction of the above (2) or (2 ′) is carried out to produce a norbornene-based polymer having an organic group in a target side chain. be able to.
  • the modified polymer may be isolated and reacted with an active hydrogen-containing compound or an alkali metal salt or an alkaline earth metal salt of the active hydrogen-containing compound.
  • the solution after the completion of the reaction in (1) can be directly reacted with an alkali metal salt or an alkaline earth metal salt of an active hydrogen-containing compound or an active hydrogen-containing compound.
  • the reaction amount of the active hydrogen-containing compound can be freely defined as necessary based on this.
  • the reaction amount of the active hydrogen-containing compound in the reaction (2) or (2 ′) is usually 0.1 to: L 00 equivalent, preferably 0 to the polar group introduced after the reaction (1). It is preferably 3 to 50 equivalents, more preferably 0.5 to 20 equivalents, most preferably 1.0 to 10 equivalents. If the reaction equivalent is too small, sufficient adhesive strength cannot be obtained, and if it is too large, unreacted active hydrogen-containing compounds remain at the time of polymer isolation, and neither is preferred.
  • the active hydrogen-containing compound used in the reaction (2) is not particularly limited as long as it is a substance capable of nucleophilic attack on the electropositive carbon, but is not limited to a hydroxyl group, an amino group, a mercapto group, a carboxyl group, and Compounds having at least one kind of polar group selected from the group consisting of sulfoxyl groups are preferred.
  • Examples of such compounds include water, alcohols, phenols, amines, thiols, organic acids (eg, aminocarboxylic acids, aminosulfonic acids, mercaptocarbonic acids, etc.). Among them, water, alcohols, phenols, amines, thiols, and aminocarboxylic acids described above can be used.
  • aminosulfonic acids and mercaptocarboxylic acids include 2-amino-1-naphthylene sulphonic acid, 4-amino-1-naphthalene sulphonic acid, and 5-amino-1-na-na.
  • Phthalene sulphonic acid 8—amino-2—naphthyl lensulphonic acid, 3—amino-2—naphthoic acid, 3—aminol 2,7—naphthenic range sulphonic acid, 7—ami ⁇ ⁇ 1, 3 —Naphthalenedisulfonic acid, mercaptoaceti 2-Mercaptonicotinic acid, 2-Mercaptobenzoic acid, 3-Mercaptopropionic acid, 2-Mercaptopropionic acid, Mercaptosuccinic acid, N-(2 —Mercaptopropionyl) glycine and the like.
  • the reaction of the active hydrogen-containing compound in the method (2) can be performed according to the method described above.
  • the alkali metal salt or alkaline earth metal salt of the active hydrogen-containing compound used in the reaction (2 ′) include, for example, lithium, sodium, potassium, and calcium salts of the above active hydrogen-containing compound.
  • the reaction of the alkali metal salt or alkaline earth metal salt of the active hydrogen-containing compound and the hydrolysis in the post-treatment step can be carried out according to the above-mentioned methods.
  • the reaction solution is filtered as necessary, and the filtrate is dropped into a poor solvent such as acetone to coagulate the resin.
  • an active hydrogen-containing norbornene-based polymer can be obtained. However, some or all of these steps may be omitted as necessary.
  • the ratio (modification rate) of the organic group in the norbornene-based polymer thus obtained may be appropriately selected depending on the purpose of use, and is usually 0.1 to 10 per repeating unit of the polymer. When it is in the range of 0 mol%, preferably in the range of 0.2 to 50 mol%, and more preferably in the range of 1 to 30 mol%, the adhesiveness and the fluidity are highly balanced and suitable.
  • the molecular weight of the organic group-containing norbornene polymer of the present invention is not particularly limited and may be appropriately selected depending on the purpose of use.
  • the weight average molecular weight (Mw) in terms of polystyrene measured by GPC is usually 1,0. 0 0 to 1, 0 0 0, 0 0 0, preferably 5, 0 0 0 to 5 0 0, 0 0 0, more preferably in the range of 100,000 to 100,000.
  • the polystyrene-equivalent number average molecular weight of the organic group-containing norbornene-based polymer measured by GPC is preferably as described above.
  • the glass transition temperature (T g) of the organic group-containing norbornene polymer of the present invention may be appropriately selected according to the purpose of use, but is usually 50 to 300 ° C., and preferably 100 to 280 ° C. ° C, particularly preferably in the range of 120 to 250 ° C. When Tg is in this range, the adhesiveness and the fluidity are highly balanced and suitable.
  • the melt flow rate of the organic group-containing norbornene polymer of the present invention depends on the intended use.
  • the range may be appropriately selected, but is usually in the range of 1 to 10 OgZ10 minutes, preferably in the range of 5 to 70 g / 10 minutes. If the melt flow rate is too high, the fluidity during melting of the polymer will decrease, and the interfacial wettability with the adherend as the adhesive will decrease. If the melt flow rate is too low, the polymer will overflow as the adhesive. Inconvenience occurs. Therefore, when the melt flow rate is within the above range, the adhesiveness is excellent and suitable.
  • the present invention is characterized in that by admixing a low molecular weight compound having a specific molecular weight range to the alicyclic structure-containing polymer, the adhesiveness and long-term reliability are improved.
  • a low molecular weight compound having a specific molecular weight range to the alicyclic structure-containing polymer
  • the adhesiveness and long-term reliability are improved.
  • the detailed mechanism is not clear at this stage, the addition of a low molecular weight compound reduces the viscosity of the alicyclic structure-containing polymer, and the resin composition with respect to the fine uneven surface of the adherend. It is presumed that the wettability of the material was improved, and the adhesion between the adherends was improved.
  • the molecular weight of the low molecular weight compound is from 300 to 3,000, preferably from 350 to 100 in terms of polystyrene as measured by gel permeation chromatography (GPC). It is in the range of 2,000, more preferably 350 to 1,000. If the molecular weight of the low molecular weight compound to be blended is too small, the mechanical strength, heat resistance, and long-term reliability are poor, and the low molecular weight compound bleeds out. Conversely, if the molecular weight of the low molecular weight compound is too large, resin flowability, adhesiveness, and long-term reliability are poor.
  • the low molecular weight compound used in the present invention is not particularly limited, and examples thereof include oligomers of polymerizable monomers such as ethylene, propylene and butadiene; hydrocarbon compounds such as paraffin oil and wax; '-Methylene-bis (4-methyl-6-t-butylphenol), 4,4'-butylidene-bis (6-t-butyl-m-cresol), 4,4'-thiobis (3-methyl-6-t-butylphenol) , 1, 1, 3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 2-(4, 6-diphenyl-1, 3, 5-triazine-2-yl) One 5 — [(hexyl) oxy] monophenol, 2 — Hydroxy-1 41 n-octyloxybenzophenone, 2 — [2 — Hydroxy-1 3, 5 — Bis (a, 'di Tylbenzyl) phenyl] 1-2H-benzotriazole, 2— (3,5
  • a hindered compound can be used as the low molecular weight compound. Adhesion and long-term reliability can be improved by incorporating a hindered compound.
  • the hindered compound has excellent compatibility with the alicyclic structure-containing polymer, improves the adhesiveness, and, by adding the hindered compound, lowers the viscosity of the alicyclic structure-containing polymer, and It is presumed that the wettability of the resin composition with respect to the fine uneven surface was improved to improve the adhesion between the adherends.
  • the hindered compound used in the present invention is not particularly limited, and at least a hindered structure having a polar group and not having a hydrogen atom at the carbon atom at position 3] of the polar group is present in the molecule.
  • An organic compound having one can be used.
  • the polar group having a hindered structure include a hydroxyl group, an amino group, a carboxyl group, an ester group, an oxy group, and the like. Among these, a hydroxyl group and a amino group are preferred. preferable.
  • hindered compound examples include a hindered phenol compound and a hindered amide compound.
  • Specific examples of hindered phenol compounds include 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane and 4,4'butylidenebis (3-methyl-6 — Tert —butyl phenol), 2,2-thiobis (4-methyl-6-tert—butyl phenol), n-octyldecyl-3 — (4′-hydroxy-3 ′, 5′-tert-butyl 'Phenyl) propionate, tetrakis [methylene-1 3 — (3', 5 'di-tert-butyl-4'-hydroxyphenyl) propionate] methane, pentaerythritol-tetrakis [3 — (3, 5-di-tert-butyryl 4-hydroxyphenyl) propionate], triethylene glycol monobis [3-(3-tert-butyl
  • hindered amide compounds include bis (2,2,6,6, —tetramethyl-4-piperidyl) sebaguete, bis (1,2,2,6,6) -pentymethyl-4 —Piperidyl) sebacate, 1 [2-1 ⁇ 3 — (3,5 —di-tert-butyl-4-hydroxydroxyphenyl) propionyloxy ⁇ ethyl] 1 4— ⁇ 3-(3, 5 —di-tert -Butyl-4 —hydroxyphenyl) propionyloxy ⁇ 1,2,2,6,6, —tetramethylpiperidine, 8—benzyl-1,7,7,9,9—tetramethyl-3-octyl—1,2,3— Triaza spiro [4,5] pentane-2,4-dione, 4-benzyloxy-2,2,6,6—tetramethylpiperidine, dimethyl succinate —2— (2-hydroxyshetyl) Droxy—2,2,6,6, —
  • esters such as dioctyl phthalate and glycerin distearate, (sub) phosphites, and hindered compounds are preferred.
  • the low molecular weight compounds can be used alone or in combination of two or more.
  • the compounding amount of the low molecular weight compound is appropriately selected according to the purpose of use, but is usually 3 to 50 parts by weight, preferably 4 to 100 parts by weight per 100 parts by weight of the alicyclic structure-containing polymer resin. When the amount is in the range of 30 parts by weight, more preferably in the range of 5 to 15 parts by weight, the adhesiveness and long-term reliability are highly balanced and suitable. You. If the compounding ratio of the low molecular weight compound is too small, long-term reliability is reduced. If the compounding ratio of the low molecular weight compound is too large, heat resistance and the like will be reduced.
  • the adhesive resin composition of the present invention comprises an alicyclic structure-containing polymer and a low molecular weight compound as essential components, and optionally, other polymers such as elastomers and resins and other compounding agents. Can be.
  • the addition amount of the other polymer and other compounding agents is appropriately selected within a range that does not impair the purpose of the present invention.
  • Elastomer is a polymer having a glass transition temperature (T g) of 40 ° C. or less, and includes ordinary rubbery polymers and thermoplastic elastomers.
  • T g glass transition temperature
  • the glass transition temperature of the block copolymerized rubbery polymer or the like is 2 or more
  • the glass transition temperature of the present invention is 40 ° C or less if the lowest glass transition temperature is 40 ° C or less. It can be used as a rubbery polymer.
  • elastomers include isoprene rubber, its hydrogenated product; chloroprene rubber, its hydrogenated product; ethylene-propylene copolymer, ethylene, ⁇ -olefin copolymer, propylene ' ⁇ -o Saturated polyolefin rubbers such as olefin copolymers; ethylene / propylene / gen copolymers, ⁇ -olefin / olefin / gen copolymers, gen copolymers, isobutylene / isoprene copolymers, isobutylene / gen copolymers Gen-based copolymers such as coalesced products, their halides, hydrogenated gen-based polymers or their halides; acrylonitrile-butadiene copolymers, their hydrogenated products; vinylidene fluoride Tefylene trifluoride copolymer, vinylidene fluoride Fluorine rubber such as pyrene
  • Group vinyl monomers ⁇ conjugated random copolymers, hydrogenated products of these; styrene ⁇ butadiene ⁇ styrene ⁇ rubber; styrene ⁇ isoprene ⁇ styrene ⁇ rubber; styrene ⁇ ethylene ⁇ butadiene ⁇ styrene ⁇ rubber Aromatic pinyl-based monomers ⁇ Linear or radial block copolymers of conjugated gens, styrene-based thermoplastic elastomers such as their hydrogenated products, urethane-based thermoplastic elastomers, and polyamide-based thermoplastics Elastoma, 1, 2 —Polybutadiene-based thermoplastic elastomer And thermoplastic elastomers such as vinyl chloride-based thermoplastic elastomers, fluorine-based thermoplastic elastomers, and the like.
  • a copolymer of an aromatic vinyl monomer and a conjugated diene monomer, and a hydrogenated product thereof are used in the thermoplastic resin containing an alicyclic structure. It has good dispersibility with fat and is preferable.
  • the copolymer of the aromatic vinyl monomer and the conjugated diene monomer may be a block copolymer or a random copolymer. From the viewpoint of heat resistance, those in which a portion other than the aromatic ring is hydrogenated are more preferable.
  • styrene-butadiene block copolymer styrene-butadiene-styrene-block copolymer, styrene-isoprene-block copolymer, styrene-isoprene-styrene-block copolymer, styrene-butadiene ⁇ Random copolymers and their hydrogenated products.
  • polymers include, for example, low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear low-density polyethylene, ultra-low-density polyethylene, polypropylene, syndiotactic polypropylene, polybutene, polypentene, and ethylene glycol.
  • Polyolefins such as copolymers of ethylene and vinyl acetate; Polyesters such as polyethylene terephthalate and polybutylene terephthalate; Polyamides such as Nylon 6 and Nylon 66; Polycarbonates , Polyimide, other resins such as epoxy resin; and the like.
  • compounding agents include fillers, flame retardants, heat stabilizers, weather stabilizers, leveling agents, lubricants, and the like.
  • a curing agent, a curing accelerator, and a curing aid suitable for each polar group of the alicyclic structure-containing polymer are used. May be appropriately blended.
  • the filler can be blended especially for the purpose of improving mechanical strength (toughness) and further improving adhesive strength by reducing the coefficient of linear expansion.
  • Filer Examples include inorganic or organic fillers.
  • the inorganic filler examples include, but are not particularly limited to, calcium carbonate (light calcium carbonate, heavy or finely divided calcium, special power rutile-based filler), clay (aluminum silicate; nepheline syenite fine) Powder, calcined clay, silane-modified clay) talc, silica, alumina, kelp earth, kay sand, pumice powder, pumice balloon, slate powder, mica powder, asbestos (asbestos), alumina colloid (alumina sol), Aluminum White, Aluminum Sulfate, Barium Sulfate, Lithobon, Calcium Sulfate, Molybdenum Disulfide, Graphite (Graphite), Glass Fiber, Glass Beads, Glass Flake, Foamed Glass Beads, Flyash Ball, Volcanic Glass Hollow Body, synthetic inorganic hollow body, single crystal calcium titanate, carbon fiber, charcoal Hollow spheres, anthracite powder, artificial cryolite (cryolite),
  • organic filler examples include polyethylene fiber, polypropylene fiber, polyester fiber, polyamide fiber, fluorine fiber, epoxy powder, thermosetting resin hollow sphere, Saran hollow sphere, shellac, wood flour, cork Powder, polyvinyl alcohol fiber, cellulose powder, wood pulp and the like.
  • the filler may have conductivity, especially when the electronic components are bonded and electrically joined to each other, and the following conductive particles can be preferably blended.
  • the adhesive resin composition of the present invention may contain conductive particles (conductive filler).
  • the type of the conductive particles is not particularly limited, and is appropriately selected depending on the types of the base polymer and the adherend.
  • the conductive particles include: (1) metal particles such as nickel, aluminum, silver, copper, tin, lead, gold, zinc, platinum, cobalt, and alloys thereof (eg, solder); (2) aggregated metal particles; Molten metal particles, conductive carbon black, conductive carbon particles such as carbon fiber, styrene, phenolic, epoxy resin particles, or composite particles of these resin particles and solder Metal-coated resin particles treated with metal plating such as Ni and Au, composite resin particles obtained by dispersing metal particles in flexible resin such as polyurethane-based resin and composited, and Microcapsule capsule Type conductive particles.
  • metal particles such as nickel, aluminum, silver, copper, tin, lead, gold, zinc, platinum, cobalt, and alloys thereof (eg, solder); (2) aggregated metal particles; Molten metal particles, conductive carbon black, conductive carbon particles such as carbon fiber, styrene, phenolic, epoxy resin particles, or composite particles of these resin particles and solder Metal-coated resin particles treated with metal plating such as Ni
  • the micro force cell type conductive particles are formed by forming an insulating resin layer on the surface of the conductive particles.
  • an insulating resin layer For example, (i) nickel, aluminum, silver, copper, tin, lead, gold, zinc, Metal particles such as platinum, cobalt, and their alloys (for example, solder) whose surfaces are coated with an insulating resin.
  • Metal particles such as platinum, cobalt, and their alloys (for example, solder) whose surfaces are coated with an insulating resin.
  • Metals whose resin particles are treated with metal plating such as Ni or Au examples thereof include those in which the surface of coated resin particles is coated with an insulating resin, and those in which (H i) composite resin particles obtained by combining a resin and metal particles are coated with an insulating resin.
  • the insulating resin include a thermoplastic resin and a thermosetting resin.
  • the method for producing the microphone opening capsule type conductive filler is not particularly limited, and a known method can be adopted. Specifically, a method of forming a conductive intermediate layer on a spherical core material resin and coating an insulating thermoplastic resin thereon, or a method of coating an insulating thermoplastic resin on the surface of the spherical conductive fine particles.
  • the surface of conductive particles is coated by plasma polymerization or plasma CVD polymerization. Examples of the method include a method of forming an insulating film of a thermoplastic resin or a thermosetting resin, and a method of in-situ polymerization of a monomer on the surface of conductive fine particles to polymerize and coat.
  • the insulating resin examples include thermoplastic resins such as acrylic resin, styrene resin, acrylic / styrene resin, polyamide resin, and polyurethane resin; epoxy / amin-based cured products, Examples of such materials include hardened resins based on min and thermosetting resins such as divinyl benzene polymer. It is preferable that these insulating resins have heat resistance enough to withstand the thermocompression bonding temperature between the chip and the substrate.
  • the thickness of the coating layer made of an insulating resin is preferably 3 m or less. The lower limit of the thickness of the insulating resin layer depends on the manufacturing method, but is usually about 0.05 zm.
  • the shape of the conductive particles is not particularly limited, but is preferably spherical, granular, or flat in order to obtain a sufficient surface contact effect between the terminals by heating and pressing.
  • the average particle size of the conductive filler used in the present invention may be appropriately selected according to the purpose of use, and is an average particle size of (major axis / short axis) / 2, usually 0.1 to 30. ⁇ , preferably in the range of 1 to 20 ⁇ , more preferably in the range of 5 to 15 m.
  • These conductive particles are preferably those that are easily dispersed uniformly in the alicyclic structure-containing polymer of the base polymer, and those that have excellent adhesion to the electrode material of the semiconductor component or the electrode of the substrate.
  • the mixing ratio of the conductive particles is appropriately selected depending on the purpose of use, but is usually 1 to 100 parts by weight, preferably 2 to 70 parts by weight, per 100 parts by weight of the alicyclic structure-containing polymer. When the amount is in the range of 3 to 50 parts by weight, more preferably, the dielectric properties, adhesiveness, and long-term reliability are highly balanced. Conductive particles The mixing ratio is usually 5 to 30 parts by weight. If the blending ratio of the conductive particles is too small, the bonding between the terminals becomes insufficient, and it is particularly difficult to cope with fine pitch. If the mixing ratio of the conductive particles is too large, there is a possibility that the adhesive strength is reduced and the lateral insulation property is impaired.
  • the terminal spacing has been reduced, and it has been required to respond to finer pitch electrodes and to ensure high reliability of connection parts.
  • conventional anisotropic conductive materials cannot sufficiently cope with fine pitch formation. Due to the development of fine pitch, for example, in the case of a beam lead type semiconductor chip, the beam lead width is 50 to 100 m, and the lead interval is about 50 to 100 m. .
  • the adhesive resin composition of the present invention can meet these demands because the base polymer has excellent dielectric properties.
  • microcapsule-type conductive particles as the conductive particles, high filling of the conductive particles becomes possible, and this also makes it possible to respond to the fine pitch of the electrodes. become.
  • the form of use of the adhesive resin composition of the present invention can be appropriately selected according to the purpose of use, but when used for bonding fine uneven surfaces such as circuit boards and electronic components, it is used in the form of a varnish or sheet. It is preferred that
  • the varnish of the present invention is prepared by dissolving or dispersing the adhesive resin composition or the organic group-containing norbornene-based polymer in an organic solvent.
  • the organic solvent is not particularly limited as long as it dissolves or disperses the components. Examples thereof include aromatic hydrocarbons such as toluene, xylene, and ethylbenzene; and n-pentane, hexane, heptane, and other aliphatic hydrocarbons.
  • Organic solvents can be used alone or in combination of two or more.
  • the amount of the organic solvent used may be an amount ratio sufficient to uniformly dissolve or disperse the alicyclic structure-containing polymer, the low-molecular weight compound, and other components contained as necessary. It is used in a range where the partial concentration is 1 to 80% by weight, preferably 5 to 60% by weight, and more preferably 10 to 50% by weight.
  • the sheet of the present invention can be obtained by molding the adhesive resin composition or the organic group-containing norbornene-based polymer into a sheet.
  • the sheet may be formed by a conventional method, such as a method in which the varnish of the present invention is applied to a smooth surface such as a mirror-finished metal plate or a resin carrier film, and then the solvent is dried.
  • a method in which the adhesive resin composition or the organic group-containing norbornene-based polymer of the present invention is melt-extruded from a T-die or the like is selected.
  • the thickness of the sheet of the present invention is appropriately selected depending on the purpose of use, but is usually 1 to 1000 mm, preferably 5 to 500 / zm, more preferably 10 to 100 / zm. When it is in the range of 0 / xm, adhesiveness and long-term reliability are highly balanced and suitable.
  • the adhesive resin composition of the present invention an organic group-containing norbornene-based polymer, Varnishes and sheets have excellent adhesiveness and long-term reliability, so they can be used for various types of adhesive applications.
  • a method for bonding the adherends for example, (1) applying the varnish of the present invention to one adherend, drying the solvent to form an adhesive resin layer, (2) laminating the sheet of the present invention on one of the adherends, placing the other adherend on the other adherend, and then performing thermocompression bonding. And the like.
  • the adherend is not particularly limited. However, when the adherend is a wiring board or an electronic component having a fine uneven surface, the improvement effect of the present invention is remarkably exhibited and it is preferable. is there.
  • Examples of a wiring board or an electronic component having a fine uneven surface on its surface include, for example, a wiring board in which metal conductor wiring and electrodes are formed on an organic or inorganic material substrate (for example, a multilayer wiring board, a high-density wiring board).
  • Printed circuit boards such as density mounting boards, flexible printed boards, silicon wafer boards, ceramic boards), central processing units (CPU), IC chips such as semiconductor memory (DRAM), and LSI chips And semiconductor packages such as ball grid arrays (BGA) and chip size packages (CSP).
  • the adhesive resin composition and the organic group-containing norbornene-based polymer of the present invention can be used as an adhesive resin material in electronics packaging technology.
  • the adhesive resin composition of the present invention is suitable for use in, for example, fields such as adhesion and bonding of electronic components to a circuit board, sealing and insulation of electronic components, connection between substrates, interlayer insulating films, and transport of electronic components. Can be applied.
  • the glass transition temperature was measured by the DSC method.
  • the molecular weight was measured as a polystyrene-equivalent value by gel 'permeation' chromatography (GPC) using chloroform or toluene as a solvent.
  • Adhesive strength was determined by sandwiching the adhesive resin composition between a strip-shaped glass epoxy substrate (FR-4) having a thickness of 0.8 mm and a silicon wafer, and pressing with a hot press at 200 ° C. The bonding area is 10 ⁇ 10 mm. The shear strength of this sample was measured by a tensile tester and was used as the bond strength. The adhesive strength was evaluated according to the following criteria.
  • the glass transition temperature (T g) of the adhesive resin composition was measured, and the heat resistance was evaluated based on the following criteria.
  • TCT temperature cycle test
  • a semiconductor chip was heated and pressed on the above-mentioned glass epoxy substrate via an adhesive resin composition to prepare a sample.
  • the temperature cycle of “room temperature (5 minutes) ⁇ 130 ° C (15 minutes) ⁇ room temperature (5 minutes)” is defined as one cycle, and by repeating this, a temperature shock is applied to check for the occurrence of defects (peeling).
  • the following criteria were used for evaluation. However, when a hindered compound is blended, the temperature cycle of “130 ° C (15 minutes) — room temperature (5 minutes) — 135 ° C (15 minutes) — room temperature (5 minutes)” was reduced to one cycle, and the conditions were stricter.
  • ⁇ Failure was observed at 150 HR or more and less than 250 HR
  • ⁇ Failure was observed at 100 HR or more and less than 150 HR
  • X At less than 100 HR The occurrence of defects was observed.
  • ⁇ No occurrence of defects of 300 HR or more was observed, ⁇ : Defects were observed in the range of 20 OHR or more and less than 30 OHR, ⁇ : Defects were observed in the range of 100 HR or more and less than 200 HR, X: Defective in less than 100 HR Development was observed.
  • the adhesive strength when the (10) organic group-containing norbornene-based polymer was used was measured according to the method described below.
  • a varnish was prepared by dissolving the norbornene-based polymer obtained in each example in an organic solvent, and then formed into a film (thickness: 50 m) by a cast film forming method. Cut to range.
  • Commercially available glass epoxy resin substrate (AN SI standard: FR-4) with a thickness of 0.8 cm, height of 8 cm, and width of lcm, and fine wiring of 0.5 mm, thickness of 8 cm, width of 1 cm
  • FR-4 glass epoxy resin substrate
  • a sample was prepared by calo-thermal fusion bonding at 250 ° C. and 30 kg Z cm 2 with a hot press. The peel strength obtained by the tensile test of the sample was defined as the adhesive strength.
  • ETD 8 - E Chi Rutetorashikuro [4.4.1 2 '5.17, 10.0] - 3 - dodecene
  • a maleic anhydride-modified polymer was obtained in the same manner as in Synthesis Example 1, except that 8 parts of maleic anhydride was changed to 2 parts and 4 parts of dicumyl peroxide to 1 part. To 100 parts of the obtained polymer, 3 parts of isopropyl alcohol was added, and a decomposition reaction was performed at 135 ° C. for 1 hour to obtain a maleic acid half-ester-modified polymer (B). Table 1 shows the physical properties.
  • An epoxy-modified polymer (D) was obtained in the same manner as in Synthesis Example 1 except that maleic anhydride (8 parts) was replaced with acrylglycidyl ether (10 parts). Table 1 shows the physical properties.
  • An epoxy-modified polymer was synthesized in the same manner as in Synthesis Example 4, and 100 parts of the obtained polymer was added with 3 parts of ammonia and subjected to a decomposition reaction at 135 ° C for 1 hour to give an alcohol-modified polymer.
  • a polymer (E) was obtained. Table 1 shows the physical properties.
  • Li-based living anion polymerization catalyst [n-BuLiZ tetramethylene diamine (TM EDA: living anion stabilizing agent)] described in JP-A-7-2588318 1 Z 1 (molar ratio)] to polymerize 1,3-cyclohexadiene (C-HD) to prepare a 1,4-addition polymer, and then hydrogenate the polymer to obtain a hydrogenated polymer. Coalescence was obtained.
  • a maleic acid half-ester modified polymer (G) was obtained in the same manner as in Synthesis Example 2 except that this polymer was used. Table 1 shows the physical properties.
  • Example 2 A sample was prepared and evaluated in the same manner as in Example 1 except that the low molecular weight compounds shown in Table 2 were used. Table 2 shows the results. In these examples, elution of low molecular weight components from the adhesive resin layer was not observed.
  • Example 2 The xylene solution of the polymer and the low molecular weight compound used in Example 2 was applied directly on a glass epoxy substrate, and then heated at 160 for 1 hour in nitrogen. Let dry. A semiconductor component (125 m pitch, 360 pins) having silicon as a base was placed thereon, and heated and pressed in the same manner as in Examples 1 to 13 to perform each test. Excellent results were shown as in Example 2. No elution of low molecular weight components from the adhesive resin layer was observed.
  • Example 14 Each test was performed in the same manner as in Example 14 except that the xylene solution of the polymer and the low molecular weight compound used in Example 6 was used. Excellent results were shown as in Example 6. Also, no elution of low molecular weight components from the adhesive resin layer was observed.
  • Example 1 Each test was performed in the same manner as in Example 1 except that the acrylic amide-modified polymer (H) obtained in Synthesis Example 8 was used instead of the polymer (A). Although the adhesive strength and heat resistance were excellent, the results of the temperature cycle test (TCT) and the high temperature and high humidity test were somewhat unsatisfactory.
  • TCT temperature cycle test
  • Example 2 A sample was prepared and evaluated in the same manner as in Example 1 except that dimethyl phthalate was used instead of dioctyl fluorate 1. Table 2 shows the results. The adhesive strength was remarkably reduced, the heat resistance was unsatisfactory, and the elution of low molecular weight components from the adhesive resin layer was observed, confirming that the reliability was reduced.
  • Example 2 A sample was prepared and evaluated in the same manner as in Example 1, except that 10 parts of dioctyl phthalate was used instead of triethyl phosphate. Table 2 shows the results. Significant decrease in various physical properties, and elution of low molecular weight components from the adhesive resin layer was observed, and reliability was reduced. Was confirmed.
  • Example 1 was repeated except that 10 parts of octyl phthalate was replaced by Mitsui High Wax 4002E (Mitsui Petrochemical, molecular weight 3,200, acid value 20 KOHmg g Zg). A sample was prepared and evaluated in the same manner. Table 2 shows the results. It was confirmed that various properties other than heat resistance were significantly reduced, and that reliability was reduced.
  • Mitsui High Wax 4002E Mitsubishi Chemical Company, molecular weight 3,200, acid value 20 KOHmg g Zg
  • a hindered compound was added to 100 parts of the polymers (A) to (H) obtained in Synthesis Examples 1 to 8 at the compounding ratio shown in Table 3, and then the resin component amount was reduced to 30%.
  • PET polyethylene terephthalate
  • the obtained sheet was peeled off from the PET film, placed on a glass epoxy substrate, and a semiconductor component (125-m pitch, 360-pin) with silicon as the base was placed on top of it, and was placed at 200 ° C. Bonding was performed by heating for 30 seconds and thermocompression bonding.
  • the samples thus obtained were examined for initial adhesion and heat resistance, and for the occurrence of defects in the temperature cycle test (TCT) and the high-temperature and high-humidity test. The evaluation results are shown in Table 3, and this sample showed excellent results. No elution of the hindered compound from the adhesive resin layer was observed.
  • Xylene solution of the polymer and the hindered compound used in Example 17 was directly applied on a glass epoxy substrate and dried in nitrogen at 160 (: 1 hour. On top of this, a silicon-based semiconductor component (125 / xm pitch, 360 pin ) was placed thereon, and then heat-pressed and subjected to each test in the same manner as in Examples 17 to 31. Excellent results were shown in the same manner as in Examples 17 to 31. No elution of the hindered compound was observed.
  • Example 32 Each test was performed in the same manner as in Example 32 except that the xylene solution of the polymer and the hindered compound used in Example 21 was used. Excellent results were shown as in Examples 17 to 31. No elution of the hindered compound from the adhesive resin layer was observed.
  • Example 17 A sample was prepared and evaluated in the same manner as in Example 17 except that the blending ratio of IR GANOX 245 of the hindered compound was changed from 10 parts to 1 part. Table 3 shows the results. It was confirmed that the physical properties were significantly reduced and the reliability was reduced.
  • Example 19 A sample was prepared and evaluated in the same manner as in Example 19 except that the mixing ratio of TINUVIN 756 of the hindered compound was changed from 10 parts to 1 part. Table 3 shows the results. It was confirmed that the physical properties were significantly reduced and the reliability was reduced.
  • IRGANO X 245 triethylene glycol monobis [3- (tert-butyl-5-methyl-4-hydroxyphenyl) propionate]
  • Example 34 100 parts by weight of the norbornene maleic anhydride polymer obtained in Synthesis Example 10 was used instead of the norbornene maleic anhydride polymer obtained in Synthesis Example 9 to obtain a solvent.
  • To t — butyl pen The same operation was performed except that the amount of Zen was 900 parts by weight and the amount of methanol was 2.5 parts by weight.
  • the obtained polymer was 96 parts by weight.
  • Result of IR measurement of the polymer was confirmed the existence of Karubome butoxy group (1 7 4 0 cm 1 1 5 2 cm _1) and carboxyl group (1 7 2 5 cm 3 2 0 0 cm 1).
  • iH NMR CDC13, room temperature
  • Example 35 100 parts by weight of the maleic anhydride-modified norbornene-based copolymer obtained in Synthesis Example 11 was replaced by 100 parts by weight of the norbornene-maleic anhydride-based polymer obtained in Synthesis Example 10 The same operation was performed except that it was used. The obtained copolymer was 93 parts by weight. The glass transition temperature of the copolymer was 122 ° C., and Example 3 was carried out using the polymer.
  • Example 35 100 parts by weight of the maleic anhydride-modified norbornene-based copolymer obtained in Synthesis Example 12 was replaced with the norbornene-maleic anhydride-based polymer obtained in Synthesis Example 10 in the same manner as in Example 35. The same operation was performed except that it was used. The obtained copolymer was 97 parts by weight. The glass transition temperature of the copolymer was 109 ° C., and the adhesive strength measured using the polymer in the same manner as in Example 34 was 66 kg Zcm 2. [Example 38]
  • Example 35 instead of the norbornene maleic anhydride polymer obtained in Synthesis Example 10, 100 parts by weight of the maleic anhydride-modified norpoleneene copolymer obtained in Synthesis Example 13 was used. The same operation was carried out except for the case. The obtained copolymer was 99 parts by weight. The glass transition temperature of the copolymer was 90 ° C., and the adhesive strength measured using the polymer in the same manner as in Example 34 was 69 kg / cm 2.
  • Example 35 the same operation was performed using various alcohols instead of methanol.
  • Table 4 shows the results. Table 4
  • Example 35 the same operation was performed using various amines instead of methanol. Table 5 shows the results. Table 5
  • Example 35 A similar operation was performed as in Example 35 except that 11 parts by weight of p-aminobenzoic acid was used instead of methanol.
  • the obtained polymer was 95 parts by weight.
  • IR measurement of the polymer it was found that the amide group (325 cm--1, 690 cm-1, 1,400 cm-1) and the carboxyl group (172,4 cm-1, 1, The presence of 3250 cm-1) was confirmed.
  • 1 H-NMR (CDC13, room temperature) measurement of the polymer the presence of a phenyl group was confirmed ( ⁇ 57.6 to 8.lppm).
  • Example 41 100 parts by weight of the maleic anhydride-modified norportene-based copolymer obtained in Synthesis Example 14 was used instead of the maleic anhydride-modified norportene-based copolymer obtained in Synthesis Example 10 The same operation was performed except that was used.
  • the obtained copolymer was 92 parts by weight.
  • 1H-NMR (CD 13, room temperature) measurement of the copolymer the presence of a phenyl group was confirmed ( ⁇ 57.6 to 8.2 ppm). Judging from the overall integral ratio, it was confirmed that almost 100% of the maleic anhydride sites of the original copolymer were converted to amide groups and carboxyl groups.
  • the softening temperature of the copolymer was 120 ° C., and the adhesive strength measured using the polymer in the same manner as in Example 34 was 150 kg / cm 2 or more (base fracture). .
  • the hydrogenated ring-opening polymer used in Synthesis Examples 8, 11, 12, and 13 and the synthesis were prepared according to the method described in Examples of JP-A-6-100744.
  • the adhesive strength of each of the addition copolymers used in Example 14 obtained by modifying 3.6 kg of each of the copolymers with 2-hydroxyhexyl acrylate was measured.
  • To each polymer 40 g of 2-hydroxyl acrylate (manufactured by Wako Pure Chemical Industries, Ltd.), 4 g of perhexin 25B (manufactured by Nippon Oil & Fats Co., Ltd.), and 4 g of divinylbenzene were used. In addition, it was melt mixed at 250 ° C. Table 6 shows the results. Table 6
  • the modified polymer in Comparative Example 7 was The modified polymer of Comparative Example 8 has insufficient adhesive strength, and the modified polymer of Comparative Example 8 has a low melt flow rate and poor fluidity. Can be confirmed to have excellent adhesive strength.
  • the adhesive resin composition which is excellent in adhesiveness, heat resistance, moisture resistance, low water absorption, dielectric properties, and long-term reliability based on an alicyclic structure containing polymer is provided. .
  • the adhesive resin composition of the present invention has good adhesiveness to fine uneven surfaces such as wiring circuits and electronic components, and can satisfy evaluation criteria by a temperature cycle test and a high-temperature high-humidity test.
  • the adhesive resin composition of the present invention has excellent repairability in electronics mounting.
  • the adhesive resin composition of the present invention can be used, for example, in the fields of adhesion and bonding of electronic components to circuit boards, sealing and insulation of electronic components, connection between substrates, interlayer insulating films, transport of electronic components, and the like. It can be applied particularly favorably.
  • an organic group-containing norbornene-based polymer that has excellent low water absorption, dielectric properties, and heat resistance, has excellent adhesiveness and fluidity, and is suitable for bonding electronic components. You.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Composition de résine adhésive qui comporte un polymère acyclique et un composé ayant un poids moléculaire bas de 300 à 3.000, ainsi qu'un polymère norbornène ayant des groupes organiques dans les chaînes latérales. Ladite composition est caractérisée en ce que le polymère possède un poids moléculaire moyen en poids (Mw) tel que déterminé par chromatographie sur gel (GPC) en termes de polystyrène de 1.000 à 1.000.000, et en ce que les groupes organiques dans les chaînes latérales possèdent chacun de 3 à 30 atomes de carbone, un groupe carboxyle et au moins un autre groupe polaire.
PCT/JP1999/001490 1998-03-24 1999-03-24 Composition de resine adhesive WO1999048990A1 (fr)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
JP09541298A JP3918290B2 (ja) 1998-03-24 1998-03-24 接着性樹脂組成物
JP10/95412 1998-03-24
JP10/103679 1998-03-31
JP10367998A JP3952102B2 (ja) 1998-03-31 1998-03-31 有機基含有ノルボルネン系重合体
JP10/120028 1998-04-14
JP12002898A JP3975551B2 (ja) 1998-04-14 1998-04-14 樹脂組成物

Publications (1)

Publication Number Publication Date
WO1999048990A1 true WO1999048990A1 (fr) 1999-09-30

Family

ID=27307808

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP1999/001490 WO1999048990A1 (fr) 1998-03-24 1999-03-24 Composition de resine adhesive

Country Status (1)

Country Link
WO (1) WO1999048990A1 (fr)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001018112A3 (fr) * 1999-09-09 2001-09-20 Baxter Int Melanges de cyclo-olefines et procede de collage par solvants de polyolefines
US6297322B1 (en) 1999-09-09 2001-10-02 Baxter International Inc. Cycloolefin blends and method for solvent bonding polyolefins
US6613187B1 (en) 1999-09-09 2003-09-02 Baxter International Inc Solvent bonding method for polyolefin materials
US6964798B2 (en) 1993-11-16 2005-11-15 Baxter International Inc. Multi-layered polymer based thin film structure for medical grade products
US7238164B2 (en) 2002-07-19 2007-07-03 Baxter International Inc. Systems, methods and apparatuses for pumping cassette-based therapies
US7384783B2 (en) 2004-04-27 2008-06-10 Baxter International Inc. Stirred-tank reactor system
US8870812B2 (en) 2007-02-15 2014-10-28 Baxter International Inc. Dialysis system having video display with ambient light adjustment
US9474842B2 (en) 2000-02-10 2016-10-25 Baxter International Inc. Method and apparatus for monitoring and controlling peritoneal dialysis therapy
CN113512361A (zh) * 2021-02-22 2021-10-19 烟台大学 一种高粘接强度虫胶及其制备方法
US11179516B2 (en) 2017-06-22 2021-11-23 Baxter International Inc. Systems and methods for incorporating patient pressure into medical fluid delivery

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5076144A (fr) * 1973-10-11 1975-06-21
JPS5131800A (en) * 1974-09-13 1976-03-18 Showa Denko Kk Kaikanjugotai no shoributsuosandehenseisuru hoho
JPS5240561A (en) * 1975-09-27 1977-03-29 Nippon Zeon Co Ltd Novel hydrocarbon resin compositions
JPS52101300A (en) * 1976-02-23 1977-08-25 Showa Denko Kk Preparation of ring opening polymers
JPS54149800A (en) * 1978-05-16 1979-11-24 Showa Denko Kk Modification of ring-opening polymer
JPS6254744A (ja) * 1985-09-04 1987-03-10 Idemitsu Petrochem Co Ltd 粘着剤組成物
JPH0395286A (ja) * 1989-09-07 1991-04-19 Mitsui Petrochem Ind Ltd 環状オレフィン系樹脂用接着剤
JPH05214079A (ja) * 1992-01-31 1993-08-24 Nippon Zeon Co Ltd 反応性ケイ素基含有ノルボルネン系ポリマーの製造方法

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5076144A (fr) * 1973-10-11 1975-06-21
JPS5131800A (en) * 1974-09-13 1976-03-18 Showa Denko Kk Kaikanjugotai no shoributsuosandehenseisuru hoho
JPS5240561A (en) * 1975-09-27 1977-03-29 Nippon Zeon Co Ltd Novel hydrocarbon resin compositions
JPS52101300A (en) * 1976-02-23 1977-08-25 Showa Denko Kk Preparation of ring opening polymers
JPS54149800A (en) * 1978-05-16 1979-11-24 Showa Denko Kk Modification of ring-opening polymer
JPS6254744A (ja) * 1985-09-04 1987-03-10 Idemitsu Petrochem Co Ltd 粘着剤組成物
JPH0395286A (ja) * 1989-09-07 1991-04-19 Mitsui Petrochem Ind Ltd 環状オレフィン系樹脂用接着剤
JPH05214079A (ja) * 1992-01-31 1993-08-24 Nippon Zeon Co Ltd 反応性ケイ素基含有ノルボルネン系ポリマーの製造方法

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6964798B2 (en) 1993-11-16 2005-11-15 Baxter International Inc. Multi-layered polymer based thin film structure for medical grade products
WO2001018112A3 (fr) * 1999-09-09 2001-09-20 Baxter Int Melanges de cyclo-olefines et procede de collage par solvants de polyolefines
US6297322B1 (en) 1999-09-09 2001-10-02 Baxter International Inc. Cycloolefin blends and method for solvent bonding polyolefins
US6613187B1 (en) 1999-09-09 2003-09-02 Baxter International Inc Solvent bonding method for polyolefin materials
US10322224B2 (en) 2000-02-10 2019-06-18 Baxter International Inc. Apparatus and method for monitoring and controlling a peritoneal dialysis therapy
US9474842B2 (en) 2000-02-10 2016-10-25 Baxter International Inc. Method and apparatus for monitoring and controlling peritoneal dialysis therapy
US7867189B2 (en) 2002-07-19 2011-01-11 Baxter International Inc. System including machine interface for pumping cassette-based therapies
US7238164B2 (en) 2002-07-19 2007-07-03 Baxter International Inc. Systems, methods and apparatuses for pumping cassette-based therapies
US7384783B2 (en) 2004-04-27 2008-06-10 Baxter International Inc. Stirred-tank reactor system
US8870812B2 (en) 2007-02-15 2014-10-28 Baxter International Inc. Dialysis system having video display with ambient light adjustment
US9799274B2 (en) 2007-02-15 2017-10-24 Baxter International Inc. Method of controlling medical fluid therapy machine brightness
US11179516B2 (en) 2017-06-22 2021-11-23 Baxter International Inc. Systems and methods for incorporating patient pressure into medical fluid delivery
CN113512361A (zh) * 2021-02-22 2021-10-19 烟台大学 一种高粘接强度虫胶及其制备方法

Similar Documents

Publication Publication Date Title
US6833180B1 (en) Adhesive for semiconductor part
KR100483017B1 (ko) 전극의 접속구조 및 전극의 접속방법
US6472082B2 (en) Modified thermoplastic norbornene polymer and process for the production thereof
EP2166036A1 (fr) Composition de résine, matière d'enrobage, couche isolante et dispositif semi-conducteur
TW200303708A (en) Method for connecting electrodes, surface-treated wiring board and adhesive film used in the method, and electrodes-connected structure
WO1999048990A1 (fr) Composition de resine adhesive
US11195769B2 (en) Thermosetting composition for use as underfill material, and semiconductor device
KR100580887B1 (ko) 지환족구조함유 수지조성물
JP6153827B2 (ja) 異方性導電材料、接続構造体及び接続構造体の製造方法
JP3952102B2 (ja) 有機基含有ノルボルネン系重合体
JPH11343310A (ja) 絶縁体用硬化性樹脂組成物および絶縁体
CN101944659B (zh) 电路连接材料、使用其的薄膜状电路连接材料、电路构件的连接构造及其制造方法
WO1998059004A1 (fr) Materiau de protection de composants electroniques
CN101690425A (zh) 电路部件的连接结构
JP2006335861A (ja) 接着剤、接着剤フィルム、半導体部品パッケージ、および半導体部品パッケージの製造方法
EP1274808B1 (fr) Paté de fixation d'une puce semiconductrice et dispositif semiconducteur
JP3918290B2 (ja) 接着性樹脂組成物
JP4735606B2 (ja) 異方性導電材
JP2005197089A (ja) 回路接続材料、これを用いたフィルム状回路接続材料、回路部材の接続構造及びその製造方法
KR20140018901A (ko) 반도체 소자 접착용 수지 페이스트 조성물 및 반도체 장치
JP4075132B2 (ja) 樹脂組成物
JP3978862B2 (ja) シート及びその製造方法
JP2006193666A (ja) 半導体用接着フィルム、半導体用接着フィルム付きキャリア材料および半導体装置
JP3975551B2 (ja) 樹脂組成物
JP4862259B2 (ja) 抵抗ペーストおよび多層配線板

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): KR US

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
NENP Non-entry into the national phase

Ref country code: KR

122 Ep: pct application non-entry in european phase
点击 这是indexloc提供的php浏览器服务，不要输入任何密码和下载