CN1637034A - Polyurethane-imide resin,adhesive composition and adhesive composition for circuit connection - Google Patents
Polyurethane-imide resin,adhesive composition and adhesive composition for circuit connection Download PDFInfo
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- CN1637034A CN1637034A CNA2005100001931A CN200510000193A CN1637034A CN 1637034 A CN1637034 A CN 1637034A CN A2005100001931 A CNA2005100001931 A CN A2005100001931A CN 200510000193 A CN200510000193 A CN 200510000193A CN 1637034 A CN1637034 A CN 1637034A
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- polyurethane
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- 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
- C09J179/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09J161/00 - C09J177/00
- C09J179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C09J179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- 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
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
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- 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
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- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
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- 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
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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- 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
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
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- 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
- C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
- C09J9/02—Electrically-conducting adhesives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
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- Medicinal Chemistry (AREA)
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- Adhesives Or Adhesive Processes (AREA)
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Abstract
To provide a polyurethane imide resin, an adhesive composition and an adhesive composition for circuit-connecting or semiconductor-mounting. The polyurethane imide resin is expressed by general formula (1), wherein, 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 100-10,000; R[3]is a tetravalent organic group containing 4 or more carbon atoms; and n and m are each an integer of 1-100.
Description
Technical field
The present invention relates to polyurethane-imide resin, use the binder composition of this polyurethane-imide resin and use the adhesive composition for circuit connection of this binder composition.
Background technology
Use organic materialss such as Resins, epoxy at semiconductor applications more.In the packaged material field, package system 90% or just be replaced by resin packaging system more than it.Packaged material is the matrix material that is made of Resins, epoxy, solidifying agent, various additive, inorganic filler etc., uses the cresols novolac epoxy resin as Resins, epoxy more.But cresols lacquer resins type Resins, epoxy is satisfying aspect the such characteristic of low water absorption, low elasticity rate, do not possess the characteristic of requirement, thereby reply surface encapsulation mode is difficult.For this reason, proposed the novel high performance Resins, epoxy of many replacement cresols lacquer resins type Resins, epoxy, and reached practicability.
In addition, more organic materialss such as Resins, epoxy as the chips welding conductive adhesive, use and mix the silver paste that silver powder forms in Resins, epoxy.But, along with of the transfer of the installation method of semiconducter device on wiring substrate, to the anti-soft solder requirement enhancing of levelling property raising again of silver paste to the surface encapsulation method.In order to address this problem, the improvement of the voidage of the chips welding usefulness bonding coat after being cured, stripping strength, water-intake rate, spring rate etc.
In the semiconductor packages field, as adapting to the new packaged type that the cost degradation height becomes more meticulous, the upside-down method of hull section construction encapsulation of directly carrying the IC chip on printed-wiring board (PWB) or flexible wiring is just gazed at.As the upside-down method of hull section construction packaged type, known have soft solder projection (は ん だ バ Application プ), the mode of carrying out the soft solder ways of connecting or being electrically connected by conductive adhesive are set on the terminal of chip.In these modes, the stress based on the coefficient of thermal expansion differences of chip that connects and substrate is being exposed under the all-environment situation, has at linkage interface generation connection reliability and reduces such problem.Therefore, with for the stress that relaxes linkage interface is purpose, generally in the gap of chip/substrate, inject the mode of the end packing material of epoxy resin and study.But fill injection process and make process complications at the end, has disadvantageous problem aspect productivity, the cost.Should solve such problem, recently, use the upside-down method of hull section construction encapsulation of anisotropic conductive tackiness agent, just be gazed at from the viewpoint that the technology simplification is such with anisotropic conductive and sealing property.
On the other hand, in recent years, for fixing electronic unit, or use various jointing materials in order to carry out circuit to connect in fields such as semi-conductor, liquid-crystal displays.In these purposes, densification, height become more meticulous and more and more improve, and tackiness agent is also required higher bounding force and reliability.
Especially, as circuit connection material, in being connected of being connected of liquid-crystal display and TCP or FPC (flexibility printed circuit) and TCP, FPC and printed circuit board (PCB), use the anisotropic conductive tackiness agent that in tackiness agent, is dispersed with conducting particles.In addition, recently, even on substrate during the encapsulated semiconductor silicon chip, wire bonds that neither be in the past, and carry out also beginning to use the anisotropic conductive tackiness agent in this case to face down the directly so-called upside-down method of hull section construction encapsulation of encapsulated semiconductor silicon chip on substrate.In addition, in the precision electronic device field, the densification of circuit develops, and it is extremely narrow that electrode width and electrode space become.
Similar polyurethane-imide resin of the present invention is opened in the flat 05-023558 communique the spy and to be used as utilized thin film composite membranes.
Summary of the invention
But above-mentioned resin packaging system, chips welding encapsulate the such problem of the comprehensive deterioration of bounding force of existence and bonded body with conductive adhesive, upside-down method of hull section construction.In addition, as mentioned above, in the precision electronic device field, the densification of circuit develops, therefore it is extremely narrow that electrode width and electrode space become, and uses the circuit of epoxy resin in the past to connect condition of contact with tackiness agent, has problems such as distribution comes off, peels off, the position changing of the relative positions take place.Have, in order to boost productivity, strong request is to the shortening development that is less than or equal to 10 seconds tie-time again, and the low temperature rapidly-curable becomes essential.
The suitable circuit that the invention provides excellent in adhesiveness connects or the polyurethane-imide resin of semiconductor-sealing-purpose tackiness agent and use the binder composition of this polyurethane-imide resin.In addition, the invention provides the above-mentioned binder composition of bounding force, and use the adhesive composition for circuit connection of said composition with the shorteningization that can carry out good low temperature connection, can make the tie-time.Outside inferior, the connection reliability of these binder compositions is also good.
The invention of claim 1 record provides binding property good polyurethane-imide resin.
The invention of claim 2 record except that right requires the invention of 1 record, provides the polyurethane-imide resin that obtains easily.
The invention of claim 3 record except that right requires the invention of 1 record, provides solvability good polyurethane-imide resin.
The invention of claim 4 record except that right requires the invention of 1 record, provides solvability good polyurethane-imide resin.
The invention of claim 5 record except that right requires the invention of 1 record, provides solvability the good and easy polyurethane-imide resin of shaping resin.
The invention of claim 6～9 record provides the polyurethane-imide resin that can improve adhesion reliability.
Even claim 10 provides the binder composition that the low temperature short period of time also can be connected and binding property is good with the invention of 11 records.
The invention of claim 12 record provides the binder composition of giving anisotropic conductive.
The invention of claim 13 record provides connection reliability good adhesive composition for circuit connection.
The invention of claim 1 record is the polyurethane-imide resin with general formula (I) expression.
[in the formula (I), R
1Be the divalent organic base that contains aromatic ring or aliphatics ring, R
2Be that molecular weight is 100～10000 divalent organic base, R
3Be the quadrivalent organic radical that contains more than or equal to 4 carbon, n and m are 1～100 integers.]
The invention of claim 2 record is the polyurethane-imide resin of claim 1 record, it is characterized in that, it is to make segmented copolymer after the urethane oligomer that is obtained by vulcabond and dibasic alcohol carries out chain extension with the tetracarboxylic dianhydride.
The invention of claim 3 record is the polyurethane-imide resin of claim 1 record, wherein, in general formula (I), R
110mol%～100mol% have structure with general formula (II) expression.
The invention of claim 4 record is the polyurethane-imide resin of claim 1 record, it is characterized in that, and in general formula (I), R
210mol%～100mol% be to be 100～10000 divalent organic base by the molecular-weight average that the repeating unit with general formula (III) expression constitutes.
-(CH
2-CH
2-CH
2-CH
2-O)-?????????????????????(III)
The invention of claim 5 record is the polyurethane-imide resin of claim 1 record, it is characterized in that molecular-weight average is 5000～500000, dissolves in the ketone series solvent.
The invention of claim 6 record is a binder composition, it is characterized in that it contains polyurethane-imide resin and three-dimensional cross-linked property resin.
The invention of claim 7 record is the binder composition that contains the polyurethane-imide resin of claim 1 record.
The invention of claim 8 record is the binder composition of claim 7 record, and this binder composition also contains three-dimensional cross-linked property resin.
The invention of claim 9 record is the binder composition of each record in the claim 6～8, and wherein, polyurethane-imide resin is to make segmented copolymer after urethane oligomer carries out chain extension with the tetracarboxylic dianhydride.
The invention of claim 10 record is the binder composition of each record in the claim 6～8, and wherein, three-dimensional cross-linked property resin is free radical polyalcohol at least, contains by rayed or adds the solidifying agent of the free free radical of thermogenesis.
The invention of claim 11 record is the binder composition of each record in the claim 6～8, it is characterized in that three-dimensional cross-linked property resin is Resins, epoxy at least, contains the potentiality solidifying agent.
The invention of claim 12 record is the binder composition of each record in the claim 6～11, and this binder composition also contains conducting particles.
The invention of claim 13 record is an adhesive composition for circuit connection, and it uses the binder composition of each record in the claim 6～12 in the circuit connection member.
Embodiment
Polyurethane-imide resin of the present invention is the polyurethane-imide resin with general formula (I) expression.In general formula (I), R
1Be the divalent organic base that contains aromatic ring or aliphatics ring, R
2Be that molecular weight is 100～10000 divalent organic base, R
3Be the quadrivalent organic radical that contains more than or equal to 4 carbon, n and m are 1～100 integers.
R in the general formula (I)
1The divalent organic base that contains aromatic ring or aliphatics ring of expression is the vulcabond residue, and preferential the selection contained 10mol%～100mol% with general formula (II)
The structure of expression as remaining diisocyanate based, can be enumerated
Deng, these can use a kind or the combination more than or equal to 2 kinds of uses.
With the R in the general formula (I)
2The molecular weight of expression is that 100～10000 divalent organic base is a residue of dihydric alcohol, preferential select to contain 10mol%～100mol% with general formula (III)
-(CH
2-CH
2-CH
2-CH
2-O)-?????????????????????????(III)
The structure that the repeating unit of expression constitutes as remaining residue of dihydric alcohol, can be enumerated and has
-(CH
2-CH(CH
3)-O)-、
-(CH
2-CH
2-O)-、
-(CH
2-CH
2-CH
2-CH
2-O)-、
-(CH
2-CH (CH
3)-O)
a-(CH
2-CH
2-O)
b-(multipolymer of a/b=9～1/1～9mol%),
-[CO-(CH
2)
4-CO-O-(CH
2)
2-O]-、
-[CO-(CH
2)
4-CO-O-(CH
2)
2-O-(CH
2)
2-O]-、
-[CO-(CH
2)
4-CO-O-CH
2-CH(CH
3)-O]-、
-[CO-(CH
2)
4-CO-O-(CH
2)
4-O]-、
-[CO-(CH
2)
4-CO-O-(CH
2)
6-O]-、
-[CO-(CH
2)
4-CO-O-CH
2-C(CH
3)
2-CH
2-O]-、
-[CO-(CH
2)
8-CO-O-(CH
2)
6-O]-、
-[CO-(CH
2)
5-O]-、
-[CO-O-(CH
2)
6-O]-、
-R
4-(Si (CH
3)
2-O)-R
4-(R
4Be that carbonatoms is 1～10 organic radical) etc. the residue of repeating unit.These can use a kind or the combination more than or equal to 2 kinds of uses.Their molecular-weight average better is 100～10000, if 500～5000 better.
With the R in the general formula (I)
3The quadrivalent organic radical that contains more than or equal to 4 carbon of expression is the tetracarboxylic anhydride residue, for example can enumerate
Deng.These can use a kind or the combination more than or equal to 2 kinds of uses.
N in the general formula (I) and m are necessary it is 1～100 integer, are more preferably 1～50.
Polyurethane-imide resin of the present invention, the preferential use with the tetracarboxylic dianhydride makes the urethane oligomer that is obtained by vulcabond and dibasic alcohol carry out chain extension and the segmented copolymer that obtains.
Vulcabond as the urethane oligomer constituent, can ditan-4 be shown example, 4 '-vulcabond, ditan-2,4 '-vulcabond, Toluene-2,4-diisocyanate, 4-vulcabond, Toluene-2,4-diisocyanate, 6-vulcabond, 1,6-hexamethylene diisocyanate, 3-isocyanatomethyl-3,5,5-tri-methyl cyclohexane diisocyanate, 1,1 '-methylene-bis (4-isocyanato cyclohexanes), 1, two (isocyanatomethyl) benzene, 1 of 3-, two (isocyanatomethyl) hexanaphthenes of 3-etc.These can use separately or can and use.
As dibasic alcohol, the use molecular-weight average is 100～10000 polyalcohols, as backbone structure, polypropylene glycol, polyoxyethylene glycol, polypropylene glycol/ethylene glycol copolymer, poly-1 can example be shown, 4-butyleneglycol, poly-(hexanodioic acid ethyl), poly-(hexanodioic acid two ethyls), poly-(the inferior propyl ester of hexanodioic acid), poly-(hexanodioic acid four methylene esters), poly-(hexanodioic acid six methylene esters), poly-(the inferior peopentyl ester of hexanodioic acid), poly-(sebacic acid six methylene esters), poly-epsilon-caprolactone, poly-(carbonic acid six methylene esters), poly-(siloxanes) etc.These can use separately or can and use.
As the tetracarboxylic dianhydride who is used to make urethane oligomer generation chain extension, can pyromellitic acid dianhydride be shown example, 3,3 ', 4,4 '-the phenylbenzene tetracarboxylic dianhydride, 2,2 ', 3,3 '-the phenylbenzene tetracarboxylic dianhydride, 4,4 '-the hydroxyl diphthalic anhydrides, 2,2-two (3,4-two carboxyphenyls) propane two anhydrides, 2, two (2,3-two carboxyphenyls) propane two anhydrides of 2-, 1,1-two (2,3-two carboxyphenyls) ethane two anhydrides, 1, two (3,4-two carboxyphenyls) ethane two anhydrides of 1-, two (2,3-two carboxyphenyls) methane two anhydrides, two (3,4-two carboxyphenyls) methane two anhydrides, two (3,4-two carboxyphenyls) sulfone two anhydrides, 3,4,9, the 10-perylenetetracarboxylic dianhydride, two (3,4-two carboxyphenyls) ether anhydride, benzene-1,2,3, the 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-naphthalene tetracarboxylic acid dianhydride, 2,3,6,7-naphthalene tetracarboxylic acid dianhydride, 1,2,4,5-naphthalene tetracarboxylic acid dianhydride, 1,4,5,8-naphthalene tetracarboxylic acid dianhydride, 2,6-dichloronaphtalene-1,4,5, the 8-tetracarboxylic dianhydride, 2,7-dichloronaphtalene-1,4,5, the 8-tetracarboxylic dianhydride, 2,3,6,7-Tetrachloronaphthalene-1,4,5, the 8-tetracarboxylic dianhydride, luxuriant and rich with fragrance-1,8,9, the 10-tetracarboxylic dianhydride, pyrazine-2,3,5, the 6-tetracarboxylic dianhydride, thiophene-2,3,4, the 5-tetracarboxylic dianhydride, 2,3,3 ', 4 '-biphenyl tetracarboxylic dianhydride, 3,4,3 ', 4 '-biphenyl tetracarboxylic dianhydride, 2,3,2 ', 3 '-biphenyl tetracarboxylic dianhydride, two (3,4-two carboxyphenyls) dimethylsilane two anhydrides, two (3,4-two carboxyphenyls) tolyl silane two anhydrides, two (3,4-two carboxyphenyls) diphenyl silane two anhydrides, 1, two (3,4-two carboxyphenyl dimetylsilyl) benzene two anhydrides of 4-, 1,3-two (3,4-two carboxyphenyls)-1,1,3,3-tetramethyl-bicyclohexane two anhydrides, to benzene two (trimellitic acid one ester acid anhydrides), the ethylene-tetracarboxylic acid dianhydride, 1,2,3,4-ethylene-dimalonic acid dianhydride, naphthane-1,4,5, the 8-tetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5,6,7-hexahydro-naphthalene-1,2,5, the 6-tetracarboxylic dianhydride, pentamethylene-1,2,3, the 4-tetracarboxylic dianhydride, tetramethyleneimine-2,3,4, the 5-tetracarboxylic dianhydride, 1,2,3,4-tetramethylene tetracarboxylic dianhydride, two (outer-dicyclo [2,2,1] heptane-2, the 3-dicarboxylic anhydride) sulfone, dicyclo (2,2,2)-and Xin (7)-alkene-2,3,5, the 6-tetracarboxylic dianhydride, 2, two (3,4-two carboxyphenyls) HFC-236fa two anhydrides of 2-, 2,2-is two, and [4-(3,4-dicarboxyl phenoxy group) phenyl] HFC-236fa two anhydrides, 4,4 '-two (3,4-dicarboxyl phenoxy group) hexichol sulfide two anhydrides, 1, two (2-hydroxyl hexafluoro sec.-propyl) benzene of 4-two (trimellitic acid 1,2-anhydride), 1, two (2-hydroxyl hexafluoro sec.-propyl) benzene of 3-two (trimellitic acid 1,2-anhydride), 5-(2, the 5-dioxotetrahydrofuryl)-and 3-methyl-3-tetrahydrobenzene-1, the 2-dicarboxylic anhydride, tetrahydrofuran (THF)-2,3,4,5-tetracarboxylic dianhydride etc.These can use separately or can and use.
Polyurethane-imide resin of the present invention can be synthetic with usual methods such as solution polymerization process.For example, under the situation of solution polymerization process, the solvent that can dissolve the polyurethane-imide resin that generates for example N-N-methyl-2-2-pyrrolidone N-(NMP) dissolve vulcabond and dibasic alcohol in waiting, 70 ℃～180 ℃ reactions 1 hour～5 hours, come the synthesis of polyurethane oligopolymer, add the tetracarboxylic dianhydride again 70 ℃～180 ℃ reactions 1 hour to 10 hours, obtain the nmp solution of polyurethane-imide resin.In addition, according to circumstances, add univalent alcohol, oxime, amine, isocyanic ester, acid anhydrides etc. again and continue to react, also can modify the end of polyurethane-imide resin.Moreover, when synthetic, also can make water, alcohol, tertiary amine etc. as catalyzer.
According to purpose, resulting polyurethane-imide resin solution also can separate polyurethane-imide resin by the reprecipitation method that utilizes water etc.
Constitute the vulcabond of urethane oligomer and the ratio of components of dibasic alcohol, with respect to 1.0 parts of vulcabond, preferentially selecting glycol component is 0.1mol%～1.0mol%.Constitute the urethane oligomer of polyurethane-imide resin and tetracarboxylic dianhydride's ratio of components, with respect to 1.0 parts of urethane oligomers, preferentially selecting the tetracarboxylic dianhydride is 0.1mol%～2.0mol%.
Polyurethane-imide resin of the present invention, tackiness agent is given obdurability etc. is purpose, use better is 5000～500000 with tetrahydrofuran (THF) as the molecular-weight average of the polystyrene standard scaled value of the gel permeation chromatography of solvent, be more preferably 10000～300000, preferably 10000～100000.Less than 5000 o'clock, the intensity of resin was low at molecular-weight average, if surpass 500000, then dissolving resin is just bad.
Polyurethane-imide resin of the present invention, preferential selection can be dissolved in the polyurethane-imide resin of ketone series solvent, as the ketone series solvent, can enumerate acetone, ethyl methyl ketone, 2 pentanone, propione, methyl-n-butyl ketone, hexone, 2-heptanone, dipropyl ketone, valerone, hexanedione, mesityl oxide, phorone, different fluorine that ketone, pimelinketone, methylcyclohexanone, methyl phenyl ketone, camphor etc.Wherein especially acetone or ethyl methyl ketone boiling point are low, and solvent is removed easily, therefore preferential the selection.
Above Shuo Ming polyurethane-imide resin of the present invention for example in indicating systems such as semi-conductor or liquid-crystal display etc., can connect tackiness agent uses such as usefulness as the encapsulation or the circuit of semiconducter device.
Polyurethane-imide resin of the present invention, its independent binding property is good, but is purpose to improve connection reliability also, and preferential three-dimensional cross-linked property resin of combination and the solidifying agent selected uses.
The three-dimensional cross-linked property resin of Shi Yonging can be enumerated Resins, epoxy, cyanate ester resin, imide series resin, radical polymerization material acrylate acrylate maleimide compound etc. in the present invention.They and solidifying agent use together.The composition that wherein preferably contains Resins, epoxy and potentiality solidifying agent thereof especially.In addition, three-dimensional cross-linked property resin is the radical polymerization material, preferably contains the composition that produces the solidifying agent of free free radical by rayed or heating.In the occasion of Resins, epoxy, can use known imidazoles to be as solidifying agent, hydrazine system, boron trifluoride-amine complex, sulfonium salt, amine, imide, the salt of polyamines, the solidifying agent of Dyhard RU 100 etc. or its mixture.As Resins, epoxy, use or mixing are used by deutero-bisphenol-type epoxy resins such as dihydroxyphenyl propane, Bisphenol F, bisphenol S, bis-phenol D separately, by phenolic aldehyde line style resin, cresols lacquer resins deutero-epoxy novolac line style resin, naphthalene with naphthalene skeleton is a Resins, epoxy, its 1 intramolecularly of glycidyl amine type epoxy resin, Racemic glycidol ether type epoxy, biphenyl ester ring type etc. has the various Resins, epoxy more than or equal to 2 glycidyls, other known Resins, epoxy.In these Resins, epoxy, in order to prevent the corrosion of electromigration corrosion or metallic conductor circuit, preferentially use foreign ion alkalimetal ion, alkaline-earth metal ions, halide-ions, especially chlorion or water-disintegrable chlorine etc. ease down to the high purity product of being less than or equal to 300ppm.
As curing agent for epoxy resin, can use known imidazoles to be, hydrazine system, boron trifluoride-amine complex, sulfonium salt, amine, imide, the salt of polyamines, the solidifying agent of Dyhard RU 100 etc. or its mixture are preferentially selected the potentiality solidifying agent.Be covered these solidifying agent and form the solidifying agent of micro encapsulation with the polymer substance of polyurethane series, polyester system, owing to prolong the serviceable time, thereby preferential the selection.
As cyanate ester resin, can enumerate two (4-cyanato-benzene) ethane, 2, two (the 4-cyanato-benzene) propane, 2 of 2-, 2-two (3,5-dimethyl-4-cyanato-benzene) methane, 2, two (the 4-cyanato-benzene)-1,1 of 2-, 1,3,3,3-HFC-236fa, α, the cyanate esters of diisopropyl benzene, phenol addition Dicyclopentadiene (DCPD) polymkeric substance etc. between α '-two (4-cyanato-benzene) uses separately or mixes the prepolymer that uses them.Especially wherein, 2, two (the 4-cyanato-phenyl) propane and 2 of 2-, two (3,5-dimethyl-4-cyanato-phenyl) methane of 2-etc., because the dielectric characteristics of cured article is good especially, therefore preferential the selection.As the solidifying agent of cyanate ester resin, using metal is the catalysts class, uses metal catalyst classes such as manganese, iron, cobalt, nickel, copper, zinc.Specifically, use as organometallic complexs such as organometalate compound such as 2-ethylhexoate, naphthenate and acetylacetonate complex.
Metal is the use level of catalysts, with respect to cyanate compound, better is 1ppm～3000ppm, is more preferably 1ppm～1000ppm, preferably 2ppm～300ppm.At metal is the use level of catalysts during less than 1ppm, exists reactive and the solidified nature inadequate tendency that becomes, if surpass 3000ppm, the control of the reaction difficulty that just becomes can not limit the too fast tendency of curing.
The radical polymerization material (free-radical polymerised compound) that uses among the present invention is the compound that has by the functional group of radical polymerization, (methyl) acrylate resin, maleimide resin, citraconimide resin, endo-methylene group tetrahydro-phthalic imidine (Na ジ イ ミ De) resin etc. are arranged, can mix more than or equal to 2 kinds of uses.Free-radical polymerised compound can both use at any state of monomer, oligopolymer in addition, also can mix monomer and oligopolymer use.Here (methyl) acrylate resin is represented acrylate resin, methacrylate resin (following identical).
As (methyl) acrylate resin, make (methyl) acrylate carry out radical polymerization and obtain.As (methyl) acrylate, (methyl) methyl acrylate is arranged, (methyl) ethyl propenoate, (methyl) isopropyl acrylate, (methyl) isobutyl acrylate, ethylene glycol bisthioglycolate (methyl) acrylate, Diethylene Glycol two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, 1,4-butyleneglycol four (methyl) acrylate, 2-hydroxyl-1,3-two propylene acyloxy propane, 2, two [4-(acryloyl-oxy ylmethoxy) phenyl] propane of 2-, 2, two [4-(acryloyl-oxy base oxethyl) phenyl] propane of 2-, dicyclopentenyl (methyl) acrylate three decene bases (ト リ デ カ ニ Le) (methyl) acrylate, three (acryloxy ethyl) isocyanuric acid ester, carbamate (methyl) acrylate, isocyanuric acid oxyethane modification diacrylates etc., these can use a kind or mix more than or equal to 2 kinds of uses separately.In addition, as required, also can use the radical polymerization inhibitor of quinhydrones, methyl ether quinhydrones etc. in the scope of not damaging solidified nature.
Have again, have in use under the situation of free-radical polymerised material of phosphate ester structure, can improve bounding force inorganicss such as metals.Usage quantity with free-radical polymerised material of phosphate ester structure is 0.1 parts by weight～10 parts by weight, preferably 0.5 parts by weight～5 parts by weight.Free-radical polymerised material with phosphate ester structure obtains as the resultant of reaction of anhydrous phosphoric acid and (methyl) vinylformic acid 2-hydroxyl ethyl ester.Specifically, have list (2-methacryloxyethyl) acid phosphoric acid ester, two (2-methacryloxyethyl) acid phosphoric acid ester etc., can use separately also and can mix use.
As maleimide resin, it is the maleimide resin that has at least one dimaleoyl imino in the molecule.For example can enumerate phenyl maleimide, 1-methyl-2,4-bismaleimides benzene, N, N '-meta-phenylene bismaleimide, N, N '-TOPOT 2,2 maleimide, N, N '-4,4-biphenylene bismaleimides, N, N '-, 4,4-(3,3-dimethyl biphenylene) bismaleimides, N, N ', 4,4-(3, the 3-dimethyl diphenylmethane) bismaleimides, N, N '-, 4,4-(3,3-diethyl ditan) bismaleimides, N, N '-, 4,4-ditan bismaleimides, N, N '-, 4,4-diphenyl propane bismaleimides, N, N '-, 4,4-phenyl ether bismaleimides, N, N '-, 4,4-sulfobenzide bismaleimides, 2, two (4-(the 4-maleimide phenoxy group) phenyl) propane of 2-, 2, two (the 3-tertiary butyls-3 of 2-, 4-(4-maleimide phenoxy group) phenyl) propane, 1, two (4-(the 4-maleimide phenoxy group) phenyl) decane of 1-, 4,4 '-cyclohexylene-two (1-(4-maleimide phenoxy group) phenoxy group)-2-phenylcyclohexanes, 2, two (4-(4-maleimide phenoxy group) phenyl) HFC-236fa of 2-etc.These can use separately, also can mix more than or equal to 2 kinds of uses.
As the citraconimide resin, it is the resin that makes behind the citraconimide compound polymerization that has at least one citraconimide base in the molecule.As the citraconimide compound, for example can enumerate the phenyl citraconimide, 1-methyl-2,4-dual-citraconic imide benzene, N, N '-metaphenylene dual-citraconic imide, N, N '-TOPOT 2,2 citraconimide, N, N '-, 4,4-diphenylene dual-citraconic imide, N, N '-, 4,4-(3,3-dimethyl diphenylene) dual-citraconic imide, N, N '-, 4,4-(3, the 3-dimethyl diphenylmethane) dual-citraconic imide, N, N '-, 4,4-(3,3-diethyl ditan) dual-citraconic imide, N, N '-, 4,4-ditan dual-citraconic imide, N, N '-, 4,4-diphenyl propane dual-citraconic imide, N, N '-, 4,4-phenyl ether dual-citraconic imide, N, N '-, 4,4-sulfobenzide dual-citraconic imide, 2, two (4-(the 4-citraconimide phenoxy group) phenyl) propane of 2-, 2, two (the 3-tertiary butyls-3 of 2-, 4-(4-citraconimide phenoxy group) phenyl) propane, 1, two (4-(the 4-citraconimide phenoxy group) phenyl) decane of 1-, 4,4 '-cyclohexylene-two (1-(4-citraconimide phenoxy group) phenoxy group)-2-phenylcyclohexanes, 2, two (4-(4-citraconimide phenoxy group) phenyl) HFC-236fa of 2-etc.These can use separately, also can mix more than or equal to 2 kinds of uses.
As endo-methylene group tetrahydrophthalic acid imide resin, it is the resin that makes after the endo-methylene group tetrahydrophthalic acid imide compound polymerization that has at least one endo-methylene group tetrahydrophthalic acid imide in the molecule.As endo-methylene group tetrahydrophthalic acid imide compound, for example can enumerate phenyl endo-methylene group tetrahydrophthalic acid imide, 1-methyl-2,4-doube bridge methylene radical tetrahydrophthalic acid imide benzene, N, N '-metaphenylene doube bridge methylene radical tetrahydrophthalic acid imide, N, N '-TOPOT 2,2 endo-methylene group tetrahydrophthalic acid imide, N, N '-, 4,4-diphenylene doube bridge methylene radical tetrahydrophthalic acid imide, N, N '-, 4,4-(3,3-dimethyl diphenylene) doube bridge methylene radical tetrahydrophthalic acid imide, N, N '-, 4,4-(3, the 3-dimethyl diphenylmethane) doube bridge methylene radical tetrahydrophthalic acid imide, N, N '-, 4,4-(3,3-diethyl ditan) doube bridge methylene radical tetrahydrophthalic acid imide, N, N '-, 4,4-ditan doube bridge methylene radical tetrahydrophthalic acid imide, N, N '-, 4,4-diphenyl propane doube bridge methylene radical tetrahydrophthalic acid imide, N, N '-, 4,4-phenyl ether doube bridge methylene radical tetrahydrophthalic acid imide, N, N '-, 4,4-sulfobenzide doube bridge methylene radical tetrahydrophthalic acid imide, 2, two (4-(the 4-endo-methylene group tetrahydrophthalic acid imide phenoxy group) phenyl) propane of 2-, 2, two (the 3-tertiary butyls-3 of 2-, 4-(4-endo-methylene group tetrahydrophthalic acid imide phenoxy group) phenyl) propane, 1, two (4-(the 4-endo-methylene group tetrahydrophthalic acid imide phenoxy group) phenyl) decane of 1-, 4,4 '-cyclohexylene-two (1-(4-endo-methylene group tetrahydrophthalic acid imide phenoxy group) phenoxy group)-2-phenylcyclohexanes, 2, two (4-(4-endo-methylene group tetrahydrophthalic acid imide phenoxy group) phenyl) HFC-236fa of 2-etc.These can use separately, also can mix more than or equal to 2 kinds of uses.
State the occasion of free-radical polymerised compound in the use, use by rayed or add the solidifying agent (polymerization starter) of thermogenesis radical.As solidifying agent, so long as get final product by the compound of heat or light generation free radical, have no particular limits, superoxide is arranged, azo-compound etc., be considered as the connection temperature of purpose, tie-time, storage stability etc. and selecting aptly, but consider from hyperergy and storage stability aspect, the temperature of preferential 10 hours transformation period of selection is to be greater than or equal to 40 ℃, and the temperature of 1 minute transformation period is to be less than or equal to 180 ℃ organo-peroxide, and the temperature of especially preferentially selecting 10 hours transformation period is to be greater than or equal to 50 ℃, and the temperature of 1 minute transformation period is to be less than or equal to 170 ℃ organo-peroxide.Be defined as in the tie-time under 10 seconds the situation, in order to obtain sufficient reactivity, the use level of solidifying agent better is 1 weight %～20 weight %, especially preferably 2 weight %～15 weight %.As the concrete compound of the organo-peroxide that uses in the present invention, can from diacyl peroxide, peroxide two carbonic ethers, peroxy esters, ketal peroxide, dialkyl peroxide, hydrogen peroxide, silyl superoxide etc., select.Peroxy esters, dialkyl peroxide, hydrogen peroxide, silyl superoxide, because chlorion in the initiator or organic acid are less than or equal to 5000ppm, the organic acid that produces after thermal degradation is few, can suppress the corrosion of the splicing ear of the circuit block that forms with metal etc., so be preferential especially the selection.
As the diacyl peroxide class; can enumerate isobutyl peroxide, peroxidation 2; 4-dichloro-benzoyl, peroxidation 3,5,5-trimethyl acetyl, peroxidation decoyl, lauroyl peroxide, stearoyl, succinyl peroxide, benzoyl peroxide toluene, benzoyl peroxide etc.
As peroxide two carbonates, can enumerate di n propyl peroxy dicarbonate, diisopropyl peroxydicarbonate, two (4-tert-butylcyclohexyl) peroxide two carbonic ethers, two (2-oxyethyl group methoxy base peroxide) two carbonic ethers, two (2-ethylhexyl peroxide) two carbonic ethers, dimethoxy butyl two carbonic ethers, two (3-methyl-3-methoxy butyl peroxy) two carbonic ethers etc.
As the peroxy esters class; can enumerate cumenyl peroxide neodecanoic acid ester; 1; 1; 3; 3-tetramethyl butyl peroxide neodecanoic acid ester; 1-cyclohexyl-1-methylethyl peroxide neodecanoic acid ester; the own ester of peroxide neodecanoic acid uncle; the peroxide trimethylacetic acid tert-butyl ester; 1; 1; 3; 3-tetramethyl butyl peroxide-2-ethylhexanoate; 2; 5-dimethyl-2; 5-two (2-ethyl hexanoyl peroxide) hexane; 1-cyclohexyl-1-methylethyl peroxide-2-ethylhexanoate; uncle's hexyl peroxide-2-ethylhexanoate; t-butyl peroxy-2-ethylhexanoate; the t-butyl peroxy isobutyrate; 1; two (t-butyl peroxy) hexanaphthenes of 1-; uncle's hexyl peroxidation sec.-propyl one carbonic ether; t-butyl peroxy-3; 5; 5-tri-methyl hexanoic acid ester; t-butyl peroxy-laurate; 2; 5-dimethyl-2,5-two (toluoyl base peroxide) hexane; t-butyl peroxy sec.-propyl one carbonic ether; t-butyl peroxy-2-ethylhexyl one carbonic ether; the own ester of peroxybenzoic acid uncle; t-butyl peroxy-acetate etc.
As the peroxy ketal class, can enumerate 1, two (the uncle's hexyl peroxides)-3,3 of 1-, 5-trimethyl-cyclohexane, 1, two (the uncle's hexyl peroxide) hexanaphthenes, 1 of 1-, two (t-butyl peroxy)-3,3 of 1-, 5-trimethyl-cyclohexane, 1,1-(t-butyl peroxy) cyclododecane, 2, two (t-butyl peroxy) decane of 2-etc.
As the dialkyl peroxide class, can enumerate α, α '-two (t-butyl peroxy) diisopropyl benzene, two cumenyl superoxide, 2,5-dimethyl-2,5-two (t-butyl peroxy) hexane, tertiary butyl cumenyl superoxide etc.
As hydroperoxide kind, can enumerate hydroperoxidation diisopropylbenzene(DIPB), cumene hydroperoxide etc.
As the silyl peroxide, can enumerate tertiary butyl trimethyl silyl superoxide, two (tertiary butyl) dimetylsilyl superoxide, tertiary butyl trivinyl silyl superoxide, two (tertiary butyl) divinyl silyl superoxide, three (tertiary butyl) vinyl silyl superoxide, tertiary butyl triallyl silyl superoxide, two (tertiary butyl) diallyl silyl superoxide, three (tertiary butyl) allyl group silyl superoxide etc.
At bonded body is the occasion of the splicing ear of metal circuit block for example, in order to suppress its corrosion, preferentially being chosen in the chlorion and the organic acid that contain in the solidifying agent is to be less than or equal to 5000ppm, and more preferably is chosen in the few solidifying agent of organic acid that produces after the thermal degradation.In addition, consider from the stability of the bonded body that improves made, preferentially be chosen in following 24 hours open placement of room temperature (25 ℃), normal pressure after, have weight conservation rate more than or equal to 20 weight %.These solidifying agent can mix use aptly.
The solidifying agent that produces these free free radicals can be used alone or as a mixture, also can mixed decomposition promotor, use such as inhibitor.
In addition, form the solidifying agent of micro encapsulation with these solidifying agent of linings such as polymer substance of polyurethane series, polyester system, owing to prolong the serviceable time, therefore preferential the selection.
Binder composition of the present invention, in order to improve binding property, to give the stress retentivity when solidifying, also can and use the macromolecule component of polyvinyl butyral resin, vinyl-formal resin, vibrin, polyamide resin, polyimide resin, xylene resin, phenoxy resin, urethane resin, urea resin etc., acrylic rubber etc.It is 10000～10000000 that these macromolecule components are preferentially selected molecular weight.
The conducting particles that uses among the present invention as long as have the electroconductibility that can access electrical connection, has no particular limits, and the metallics of Au, Ag, Ni, Cu, Co, soft solder etc. or carbon etc. are arranged.In addition, also can use with the above-mentioned metallic conduction material conducting particles that dielectric glass, pottery, plastics etc. form that is covered.At this moment, in order to obtain sufficient electroconductibility, the preferential metal layer thickness of selecting to be covered is more than or equal to 100 .Relative binder constituents, conducting particles uses in the scope of 0.1 volume %～30 volume %, preferably can use in the scope of 0.1 volume %～20 volume %.
Binder composition of the present invention, the polyurethane-imide resin (A) that the structure of being represented by general formula (I) constitutes and the proportioning of three-dimensional cross-linked property resin (B), by weight with (A): (B)=can use preferably 10: 90～90: 10 in 1: 99～99: 1.
In using the binder composition of polyurethane-imide resin, with the raising of flowability or rerum natura, perhaps with additional guide electrically, the performance of anisotropic conductive, heat conductivity is purpose, can add filler or particle re-uses.As such filler or particle, can be silicon-dioxide, antimonous oxide, gold and silver, copper, nickel, aluminium, stainless steel, carbon, pottery or with above-mentioned metal, dielectric glass, pottery, plastics etc. as nuclear filler or the particle that above-mentioned metal or carbon forms that on this nuclear, be covered.The usage quantity of filler or particle has no particular limits, and relative 100 volume % contain the binder composition of polyurethane-imide resin, preferentially selects 0.1～50 volume %.
The binder composition that contains polyurethane-imide resin of the present invention is a purpose with the rerum natura that improves bounding force and tackiness agent, can add various polymkeric substance aptly.Employed polymkeric substance is not particularly limited.As such polymkeric substance, can use general phenoxy resin class, polymethacrylate, polyacrylate(s), polyimide, polyurethanes, polyester, polyvinyl butyral acetal class, SBS and epoxide modified body thereof, SEBS and modification bodies thereof etc. such as bisphenol A-type phenoxy resin or Bisphenol F type phenoxy resin, dihydroxyphenyl propane Bisphenol F copoly type phenoxy resin.These can use separately, perhaps mix more than or equal to 2 kinds of uses.And, in these polymkeric substance, can also contain siloxane bond or fluoro substituents.These polymkeric substance if dissolving fully mutually between the blended resin microphase-separated perhaps takes place forms the gonorrhoea state, just can be suitable as binder composition and use.The molecular weight of above-mentioned polymkeric substance is not particularly limited, and is more preferably 5000～150000 as general molecular-weight average, and especially preferably 10000～80000.In this value less than 5000 o'clock, the tendency that has the physicals of tackiness agent to reduce, and, if surpass 150000, the tendency of intermiscibility variation of composition with other is arranged then.Usage quantity contains the binder composition of polyurethane-imide resin with respect to 100 parts by weight, and preferential the selection is 20 parts by weight～320 parts by weight.Less than 20 parts by weight or when surpassing 320 parts by weight, tendency mobile and the binding property reduction is arranged in this usage quantity.
The binder composition that contains polyurethane-imide resin of the present invention also can add tenderizer, promotor, antiaging agent, tinting material, fire retardant, coupler aptly.
The binder composition that contains polyurethane-imide resin of the present invention under normal temperature (25 ℃) is aqueous situation, can use with pasty state.In room temperature is under the solid situation, except heating is used, also can use solvent to carry out gelatinization.As the solvent that can use, the reactivity of short of and binder composition and additive, and show sufficient deliquescent solvent is not just done special restriction, and preferentially selecting boiling point under the normal pressure (normal atmosphere) is 50 ℃～150 ℃ solvent.In addition, be when being less than or equal to 50 ℃ at boiling point, if place, the evaporable worry is just arranged, thereby the use under the open system is restricted in room temperature.In addition,, just be difficult to make solvent evaporates, and have the worry of the reliability after bonding being brought baneful influence if boiling point is greater than or equal to 150 ℃.
The binder composition that contains polyurethane-imide resin of the present invention also can be made film like and use.In binder composition, add formation solution such as solvent as required, with this solution coat on the separability base material of fluorine resin film, pet film, separate-type paper etc., perhaps make the above-mentioned solution of base material impregnation such as non-woven fabrics and be positioned on the separability base material, remove solvent etc. and can use as film.If the shape with film is used, consider from aspects such as operability, be more easily.
The binder composition that contains polyurethane-imide resin of the present invention can use as the tackiness agent of the different different types of bonded body of thermal expansivity.Specifically, can stick with paste as silver, silver-colored film, be that the circuit connection material, CSP of representative filled material, LOC adhesive tape, is that the semiconducter device tackiness agent of representative uses with chips welding with bonding material etc. with liner with elastomerics, CSP with anisotropic-electroconductive adhesive etc.
The preferential use binder composition of the present invention of selecting is used for the circuit connection member.The circuit connection member is made of substrate and electrode.As substrate, so long as form to be electrically connected substrate as essential electrode, just have no particular limits, have by ITO (indium tin oxide) etc. to be formed for the glass of electrode of liquid-crystal display or plastic base, printing distributing board, ceramic wiring board, flexible printing wiring board, semi-conductor silicon chip etc., be used in combination as required.
Condition during as connection has no particular limits, and connecting temperature is 90 ℃～250 ℃, and the tie-time is 1 second～10 minutes, selects aptly according to use, tackiness agent, substrate, also can carry out after fixing as required.In addition, although undertaken by heating and pressurizing when connecting, also can use the energy beyond the heat as required, for example light, ultrasonic wave, hertzian wave etc.
The also tackifier of absorb fillers, tenderizer, promotor, antiaging agent, tinting material, fire retardant, coupler, terpenic series resin etc. aptly in adhesive composition for circuit connection of the present invention.
Embodiment
Below, specifically describe the present invention according to embodiment, but the present invention is not subjected to the restriction of these embodiment.
Embodiment 1
In 1-Methyl-2-Pyrrolidone, under nitrogen atmosphere, make ditan-4 at 100 ℃, 4 '-vulcabond (1.0mol), ditan-2,4 '-vulcabond (1.0mol) and molecular-weight average are 1000 polytetramethylene glycol (0.8mol) reaction 1 hour, again to wherein adding 4,4 '-oxyphthalic acid acid anhydride (1.0mol), triethylamine and 1-Methyl-2-Pyrrolidone, stirred 3 hours at 100 ℃ again.Add benzylalcohol again, stirred 1 hour, finish reaction at 100 ℃.The solution that obtains is put into the water of high degree of agitation, and filtering precipitate in a vacuum, 80 ℃ of dryings 8 hours, obtains polyurethane-imide resin PUI-1.Measure the result of the polyurethane-imide resin obtain with GPC (gel permeation chromatography), by polystyrene conversion, Mw=51000, Mn=22000.In addition, this polyurethane-imide resin dissolves in the ethyl methyl ketone with solid component content 40 weight %.
The polyurethane-imide resin that obtains is dissolved in the ethyl methyl ketone with solid component concentration 40 weight %, compare to cooperate urethane acrylate (U-108 shown in the table 1 by solid weight, Xin Zhong village chemical industry Co., Ltd. system trade(brand)name), as 1 of solidifying agent, two (the uncle's hexyl peroxides)-3 of 1-, 3,5-trimethyl-cyclohexane (パ-ヘ キ サ TMH, NOF Corp's system trade(brand)name), cooperate the conducting particles that disperses 1.5 volume % again, this conducting particles is at the particle surface that is nuclear the nickel dam of thick 0.2 μ m to be set with the polystyrene, and the median size that forms at the metal level of the thick 0.2 μ m of arranged outside of this nickel dam is 5 μ m, proportion is 2.5 conducting particles.Use painting device to be coated on the fluorine resin film of thick 80 μ m, by 70 ℃, 10 minutes warm air dryings, the thickness that obtains binder layer was the film like tackiness agent of 20 μ m.
Embodiment 2
It is that 2000 poly-(carbonic acid six methylene esters) and embodiment 1 are synthetic in the same manner that the glycol component of PUI-1 is become molecular-weight average, obtains PUI-2.Result with GPC measures presses polystyrene conversion, Mw=55000, Mn=25000.
Make this PUI-2 and embodiment 1 in the same manner according to the cooperation of table 1, the thickness that obtains binder layer is the film like tackiness agent of 20 μ m.
Embodiment 3
With the glycol component of PUI-1 become molecular-weight average be 1000 polytetramethylene glycol (0.4mol), molecular-weight average be 2000 poly-(carbonic acid six methylene esters) (0.4mol) and embodiment 1 synthetic in the same manner, obtain PUI-3.Result with GPC measures presses polystyrene conversion, Mw=55000, Mn=25000.In addition, this imide-urethane resin dissolves in the ethyl methyl ketone with solid component content 40 weight %.
Make this PUI-3 and embodiment 1 in the same manner according to the cooperation of table 1, the thickness that obtains binder layer is the film like tackiness agent of 20 μ m.
Comparative Examples 1
Replace PUI-1 to use phenoxy resin (PKHC, ユ ニ オ Application カ-バ イ De corporate system trade(brand)name, molecular-weight average 45000, ethyl methyl ketone solution (solid component content 40 weight %)) and embodiment 1 similarly to obtain the film like tackiness agent.
Comparative Examples 2
Replace PUI-1 to use polyvinyl butyral resin (3000K, Deuki Kagaku Kogyo Co., Ltd's system trade(brand)name, mean polymerisation degree 800, ethyl methyl ketone solution (solid component content 40 weight %)) and embodiment 1 similarly to obtain the film like tackiness agent.
The mensuration of bond strength
The film like tackiness agent that use is obtained by above-mentioned manufacture method, to utilize evaporation on the Kapton of 40 μ m, to be formed with live width 50 μ m, spacing 100 μ m, 2 layers of flexible print wiring board (FPC) that the copper circuit of thick 10 μ m is 500 and be formed with glass (the thick 1.1mm of tin indium oxide (ITO) thin layer of 0.2 μ m, surface resistivity 20 Ω/), use thermo-compression bonding device (type of heating: constant hot type (コ Application ス Application ト ヒ one ト), east レ エ Application ジ ニ ア リ Application グ Co., Ltd. system), at 170 ℃, carry out 20 seconds heating and pressurizing with 3MPa, whole wide 2mm connect, and make linker.
Peel off the bond strength that method is measured resulting linker with the JIS-Z0237 standard with 90 degree, estimate.Here, the determinator of bond strength adopts Japan ボ Le De ウ イ Application system テ Application シ ロ Application UTM-4 (peeling rate 50mm/min, 25 ℃) of Co., Ltd..
Gathering above measurement result of carrying out is shown in Table 1.
Table 1
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative Examples 1 | Comparative Examples 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 |
| Bond strength (N/m) | ????580 | ????500 | ????600 | ????100 | ????150 |
Use the embodiment 1～3 of binder composition of the polyurethane-imide resin of general formula of the present invention (I) expression, the bond strength height.In contrast, use the Comparative Examples 1 of phenoxy resin, the Comparative Examples 2 of use polyvinyl butyral resin, adhesive strength deteriorates.
Similarly, in three-dimensional cross-linked property resin, contain Resins, epoxy and potentiality solidifying agent, also obtain same effect.
In sum, polyurethane-imide resin of the present invention and the binder composition that contains this polyurethane-imide resin circuit that is suitable for excellent in adhesiveness connects or the semiconductor-sealing-purpose tackiness agent.In addition, according to the present invention, can provide and can low temperature connect, make the tie-time shorteningization, even the binder composition that under electrode width that the densification by circuit causes, situation that electrode space narrows down, also has the characteristic of the excellent in adhesiveness that can tackle, and the adhesive composition for circuit connection that uses this binder composition, the connection reliability of these binder compositions is also good.
Claims (13)
1. polyurethane-imide resin with general formula (I) expression,
In the formula (I), R
1Be the divalent organic base that contains aromatic ring or aliphatics ring, R
2Be that molecular weight is 100～10000 divalent organic base, R
3Be the quadrivalent organic radical that contains more than or equal to 4 carbon, n and m are 1～100 integers.
2. polyurethane-imide resin according to claim 1 is characterized in that, it is to make segmented copolymer after the urethane oligomer that is obtained by vulcabond and dibasic alcohol carries out chain extension with the tetracarboxylic dianhydride.
3. polyurethane-imide resin according to claim 1 is characterized in that, in the general formula (I), and R
110mol%～100mol% have structure with following general formula (II) expression.
4. polyurethane-imide resin according to claim 1 is characterized in that, in the above-mentioned general formula (I), and R
210mol%～100mol% be to be 100～10000 divalent organic base by the molecular-weight average that the repeating unit with following general formula (III) expression constitutes.
-(CH
2-CH
2-CH
2-CH
2-O)-????(III)
5. polyurethane-imide resin according to claim 1 is characterized in that its molecular-weight average is 5000～500000, dissolves in the ketone series solvent.
6. a binder composition is characterized in that, it contains polyurethane-imide resin and three-dimensional cross-linked property resin.
7. binder composition that contains the described polyurethane-imide resin of claim 1.
8. binder composition according to claim 7 is characterized in that, it also contains three-dimensional cross-linked property resin.
9. according to each described binder composition in the claim 6～8, it is characterized in that above-mentioned polyurethane-imide resin is to make segmented copolymer after urethane oligomer carries out chain extension with the tetracarboxylic dianhydride.
10. according to each described binder composition in the claim 6～8, it is characterized in that above-mentioned three-dimensional cross-linked property resin is the radical polymerization material at least, contain by rayed or add the solidifying agent of the free free radical of thermogenesis.
11., it is characterized in that above-mentioned three-dimensional cross-linked property resin is Resins, epoxy at least, contains the potentiality solidifying agent according to each described binder composition in the claim 6～8.
12., it is characterized in that it also contains conducting particles according to the described binder composition of each claim in the claim 6～11.
13. an adhesive composition for circuit connection is characterized in that, it uses the described binder composition of each claim in the claim 6～12 in the circuit connection member.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004002923 | 2004-01-08 | ||
| JP2004002922 | 2004-01-08 | ||
| JP2004002923 | 2004-01-08 | ||
| JP2004-002922 | 2004-01-08 | ||
| JP2004-002923 | 2004-01-08 | ||
| JP2004002922 | 2004-01-08 |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009100016085A Division CN101445714B (en) | 2004-01-08 | 2005-01-06 | Polyurethane-imide resin, adhesive composition and adhesive composition for circuit connection |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1637034A true CN1637034A (en) | 2005-07-13 |
| CN1637034B CN1637034B (en) | 2010-04-28 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009100016085A Expired - Fee Related CN101445714B (en) | 2004-01-08 | 2005-01-06 | Polyurethane-imide resin, adhesive composition and adhesive composition for circuit connection |
| CN2005100001931A Expired - Fee Related CN1637034B (en) | 2004-01-08 | 2005-01-06 | Polyurethane-imide resin,adhesive composition and adhesive composition for circuit connection |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009100016085A Expired - Fee Related CN101445714B (en) | 2004-01-08 | 2005-01-06 | Polyurethane-imide resin, adhesive composition and adhesive composition for circuit connection |
Country Status (3)
| Country | Link |
|---|---|
| KR (2) | KR100792056B1 (en) |
| CN (2) | CN101445714B (en) |
| TW (2) | TW200848483A (en) |
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| CN101121101B (en) * | 2007-07-06 | 2010-06-02 | 清华大学 | Method for preparing polyurethane-imide permeable vaporizing aromatic/alkane separating membrane |
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| CN101501153B (en) * | 2006-08-04 | 2012-08-29 | 日立化成工业株式会社 | Film adhesive, adhesive sheet, and semiconductor device using the same |
| CN101657482B (en) * | 2007-04-19 | 2014-04-16 | Kaneka株式会社 | Novel polyimide precursor composition and use thereof |
| CN103936989A (en) * | 2013-01-21 | 2014-07-23 | 达兴材料股份有限公司 | Polyimide structure and polyimide resin composition |
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| US4929358A (en) * | 1989-08-09 | 1990-05-29 | Exxon Research And Engineering Company | Polyurethane-imide membranes and their use for the separation of aromatics from non-aromatics |
| US5098982A (en) * | 1989-10-10 | 1992-03-24 | The B. F. Goodrich Company | Radiation curable thermoplastic polyurethanes |
| JPH0523558A (en) * | 1989-12-19 | 1993-02-02 | Exxon Res & Eng Co | Production of thin supporting layer film |
| US4962271A (en) * | 1989-12-19 | 1990-10-09 | Exxon Research And Engineering Company | Selective separation of multi-ring aromatic hydrocarbons from distillates by perstraction |
| US5254659A (en) * | 1990-03-27 | 1993-10-19 | Hitachi, Ltd. | Insulating coating composition, solderable insulated wires, production process of the insulated wires and flyback transformers using the insulated wires |
| KR970006896B1 (en) * | 1993-11-10 | 1997-04-30 | 생산기술연구원 | Heat resistant polyuretane-imide resin adn their manufacturing method |
| SG76530A1 (en) * | 1997-03-03 | 2000-11-21 | Hitachi Chemical Co Ltd | Circuit boards using heat resistant resin for adhesive layers |
| GB9814835D0 (en) * | 1998-07-08 | 1998-09-09 | Europ Org For Nuclear Research | A thermal management board |
| US6403753B1 (en) * | 2000-01-18 | 2002-06-11 | Sandia Corporation | Method of making thermally removable polyurethanes |
| KR100545255B1 (en) * | 2003-04-29 | 2006-01-24 | (주)애드뷰 | Composition for photoinduced liquid crystal alignment comprising conductive polymers, the film for photoinduced liquid crystal alignment thereby, manufacturing method of the same and the liguid crystal cell comprising the film |
| JP2006241174A (en) * | 2005-02-07 | 2006-09-14 | Hitachi Chem Co Ltd | Film-formed adhesive for die-bonding, and adhesive sheet and semi-conductor device by using the same |
-
2004
- 2004-12-29 KR KR1020040115011A patent/KR100792056B1/en active IP Right Grant
- 2004-12-31 TW TW097124567A patent/TW200848483A/en unknown
- 2004-12-31 TW TW093141783A patent/TW200526710A/en not_active IP Right Cessation
-
2005
- 2005-01-06 CN CN2009100016085A patent/CN101445714B/en not_active Expired - Fee Related
- 2005-01-06 CN CN2005100001931A patent/CN1637034B/en not_active Expired - Fee Related
-
2007
- 2007-06-29 KR KR1020070065001A patent/KR100860892B1/en not_active IP Right Cessation
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Also Published As
| Publication number | Publication date |
|---|---|
| TW200526710A (en) | 2005-08-16 |
| TWI314567B (en) | 2009-09-11 |
| KR20050073528A (en) | 2005-07-14 |
| KR100792056B1 (en) | 2008-01-04 |
| CN101445714B (en) | 2013-03-20 |
| CN101445714A (en) | 2009-06-03 |
| CN1637034B (en) | 2010-04-28 |
| TW200848483A (en) | 2008-12-16 |
| KR20070077201A (en) | 2007-07-25 |
| KR100860892B1 (en) | 2008-09-29 |
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