CN1117113C - Preparation of polyimide resin and polyamine acid as adhesive - Google Patents
Preparation of polyimide resin and polyamine acid as adhesive Download PDFInfo
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- CN1117113C CN1117113C CN 00104040 CN00104040A CN1117113C CN 1117113 C CN1117113 C CN 1117113C CN 00104040 CN00104040 CN 00104040 CN 00104040 A CN00104040 A CN 00104040A CN 1117113 C CN1117113 C CN 1117113C
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Abstract
The present invention relates to a preparation method of polyamine acid and polyimide. The products have excellent heat resistance, mechanical physical properties and excellent adhesion properties to various base materials, and are soluble and suitable for being used as binding agents or adhesive tapes of electronic parts. Besides the raw materials of tetracarboxylic dianhydride and aromatic diamine used for preparing the polyimide, diamine containing a siloxane structure represented by the chemical formula (I), and alkyl or aryl cyclohexylidene diphenylamine represented by the chemical formula (II) or the chemical formula (III) are also used for preparing the polyamine acid through reaction. The polyamine acid is used for preparing the polyimide through thermal or chemical imidization.
Description
The present invention relates to the manufacture method of new type polyimide parent polyamino acid and polyimide, in more detail, relate to use the tetracarboxylic dianhydride and, as diamines, contain the diamines of alicyclic group on the side chain and contain the diamines of siloxane structure, make and have all excellent polyamino acid of thermotolerance, solvability and binding property and the manufacture method of polyimide resin.
Generally, so-called polyimide is meant that a tetracarboxylic dianhydride and diamines react in organic solvent, obtain polyimide parent polyamino acid after, make its imidization by thermal condensation or chemical condensation, and the high heat resistance resin of making.
Polyimide resin, excellences such as its thermotolerance, chemical resistant properties, electrical insulating property and mechanical characteristics can be used as multiple uses such as electronic material, tackiness agent, coating, matrix material, fiber and mould material.
Generally, the polyimide that requirement has the thermotolerance purposes, not only imide ring itself has upright and outspoken structure, and, by the linear structure of main chain, the interchain tamped density is strengthened, thereby have good heat-resistant quality, this is its advantage, still, therefore be difficult in solvent, dissolve, have heating and be difficult to the fused characteristic, the polyimide of manufacturing, its processibility is low, low with other raw-material adhesion characteristics, this is its shortcoming.
Particularly, polyimide structures as film with excellent heat resistance, because of the interchain tamped density that linear structure caused of main chain, with its heat-resistant quality of the left and right sides, the カ プ ト Application (Kapton) of commercial use, ユ ピ レ Network ス (Upilex) film are exactly this example of structure.Kapton makes from PMDA (1,2,4,5-pyromellitic acid dianhydride)-ODA (oxydiphenyl amine) monomer, and Upilex be from BPDA (3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride)-PPD (P-pHENYLENE dI AMINE) monomer makes.By cooperating of above-mentioned monomer and PMDA-PPD, can obtain having the polyimide of excellent heat resistance.Yet, these polyimide resins, and since upright and outspoken, interchain tamped density height, processibility reduces, and the flowability under the high temperature is poor, and adhesion characteristic is bad.
In order to improve these shortcomings, the report that has proposes, and imports the method for polar group on main polymer chain or the side chain, imports the method for bulky binding group or side-chain radical, the method for increase main polymer chain flexibility etc.
Particularly, the research of carrying out for the dissolution characteristics that improves polyimide resin, Network ロ サ キ etc. are at Macromolecules, have delivered with the aliphatics cyclic acid anhydride in 1994,27,1117 and have made monomer, and the polyimide of making solubility is coated with the method for feed liquid.In addition, Qin Jin etc. are at Polymer Chem.Ed., have also reported in 1993,31,2345～2351, use cyclic diamine to make the method for soluble polyimide.Yet the almost soluble polyimide of modification because of its thermostability and mechanical-physical etc. obviously reduce, has problem during actual the use in this way.
In addition, in USP 5859181, USP 5942592, USP 5094919, for solvability and the adhesion characteristic that improves polyimide resin, the diamine compound with siloxane structure is imported main polymer chain, confirmed that the solvability of this polymkeric substance and adhesion characteristic are improved.Yet, using the occasion of diamines with siloxane structure, it is limited that the polymkeric substance by the heavy addition alkyl structure improves dissolution characteristics, during heavy addition, thermotolerance and mechanical-physical reduction, polymerizations etc. go wrong.
In order to address the above problem, the object of the invention provides all better than the thermotolerance of original polyimide resin and mechanical-physical, soluble and various body material adhesion characteristic excellence, be particularly suitable for doing the electronics polyimide resin of the tackiness agent used of parts or self adhesive tape etc. in addition.
As one of method of achieving the above object, the invention discloses the manufacture method of a kind of polyamino acid and polyimide, the feature of this method is, the tetracarboxylic dianhydride more than at least a kind and, aromatic diamine more than at least a kind and, more than at least a kind contain with the diamines of the siloxane structure of following chemical formula (I) expression and, the diamines with following chemical formula (II) or chemical formula (III) expression more than at least a kind reacts.
[Formula I]
(in the above-mentioned chemical formula (I), R4 is the alkylidene group of 1～20 carbonatoms, and n ' is 1～20 integer).
[Formulae II] [Formulae II I]
During above-mentioned chemical formula (II) reached (III), R was selected from-CH
3,-CH
2CH
3,-C (CH
3)
3, C (CH
3)
2(CH
2CH
3), the base of phenyl.
Specifically describe the present invention below.
Among the present invention, for the physical properties (thermotolerance, mechanical-physical character and adhesion characteristic etc.) of improving the polyimide that generally has the linear molecule structure, in general use aromatic diamine, also use diamines with chemical formula (I) structure and, alkyl or aryl cyclohexylene bisaniline compounds with chemical formula (II), (III) structure, to make polyamino acid or polyimide.
The tetracarboxylic dianhydride's who uses as the present invention exemplary can be enumerated the structure with following chemical formula (IV) expression, and they can also can mix use separately more than 2 kinds.
[Formula I V]
In the formula, R1 represents-O-,-CO-, SO
2-,-C (CF
3)
2-, alkylidene group, alkylidene group dicarbapentaborane, phenylene, phenylene alkylidene group, phenylene two alkylidene groups etc., n4 is 0 or 1, n5 is 0 or 1, n6 is 1 or 2, n5+n6=2.
As the object lesson of aromatic tetracarboxylic acid's acid anhydride of representing with chemical formula (IV), can enumerate pyromellitic dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 3,3 ', 4, the 4-biphenyl tetracarboxylic dianhydride, 2,3 ', 3,4 '-biphenyl tetracarboxylic dianhydride, 2,2 ', 6,6 '-biphenyl tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic acid dianhydride, 1,2,5,6-naphthalene tetracarboxylic acid dianhydride, 2,2-two (3,4-dicarboxyl phenyl) propane dianhydride, two (3,4-dicarboxyl phenyl) sulfone dianhydride, two (3,4-dicarboxyl phenyl) ether dianhydride, 3,4,9,10-phenylene tetracarboxylic dianhydride, naphthalene-1,2,4, the 5-tetracarboxylic dianhydride, naphthalene-1,4,5, the 8-tetracarboxylic dianhydride, benzene-1,2,3, the 4-tetracarboxylic dianhydride, ethylene glycol bis (1,2, the 4-benzenetricarboxylic anhydride) etc., these compounds can separately or mix more than 2 kinds and use.
Except that above-mentioned aromatic tetracarboxylic acid's dianhydride, the tetracarboxylic acid of aliphatics or alicyclic structure also can use in not reducing the stable on heating scope of polyimide.
As the tetracarboxylic acid object lesson of aliphatics or alicyclic structure, can enumerate 5-(2,5-two positive four (hydrol) Ha イ De ロ one Le)-3-methyl-3-hexanaphthene-1,2-dicarboxylic anhydride, 4-(2,5-two positive tetrahydrofuran (THF)-3-yls)-1,2,3,4 ,-tetraline (テ ト ラ リ Application)-1,2-dicarboxylic anhydride, fourth ring (2,2,2)-and 7-alkene-2,3,5, the 6-tetracarboxylic dianhydride, 1,2,3,4-pentamethylene tetracarboxylic dianhydride etc., these compounds can separately or mix more than 2 kinds and use.
Object lesson as the used aromatic diamine of the present invention, can enumerate, 3,3 '-benzidine, 3,4 '-benzidine, 4,4 '-benzidine, 3,3 '-diaminodiphenyl-methane, 3,4 '-diaminodiphenyl-methane, 4,4 '-diaminodiphenyl-methane, 2,2-(3,3 '-diamino-diphenyl) propane, 2,2-(3,4 '-diamino-diphenyl) propane, 2,2-(4,4 '-diamino-diphenyl) propane, 2,2-(3,3 '-diamino-diphenyl) HFC-236fa, 2,2-(3,4 '-diamino-diphenyl) HFC-236fa, 2,2-(4,4 '-diamino-diphenyl) HFC-236fa, 3,3 '-oxydiphenyl amine, 3,4 '-oxydiphenyl amine, 4,4 '-oxydiphenyl amine, 3,3 '-diamino-diphenyl sulphur, 3,4 '-diamino-diphenyl sulphur, 4,4 '-diamino-diphenyl sulphur, 3,3 '-diaminodiphenylsulfone(DDS), 3,4 '-diaminodiphenylsulfone(DDS), 4,4 '-diaminodiphenylsulfone(DDS), 1, two [1-(3-the aminophenyl)-1-methylamine] benzene of 3-, 1, two [1-(4-the aminophenyl)-1-methylamine] benzene of 3-, 1, two [1-(3-the aminophenyl)-1-methylamine] benzene of 4-, 1, two [1-(4-the aminophenyl)-1-methylamine] benzene of 4-, 1, two (3-amino-benzene oxygen) benzene of 3-, 1, two (4-amino-benzene oxygen) benzene of 3-, 1, two (3-amino-benzene oxygen) benzene of 4-, 1, two (4-amino-benzene oxygen) benzene of 4-, 3,3 '-two (3-amino-benzene oxygen) phenyl ether, 3,3 '-two (4-amino-benzene oxygen) phenyl ether, 3,4 '-two (3-amino-benzene oxygen) phenyl ether, 3,4 '-two (4-amino-benzene oxygen) phenyl ether, 4,4 '-two (3-amino-benzene oxygen) phenyl ether, 4,4 '-two (4-amino-benzene oxygen) phenyl ether, 3,3 '-two (3-amino-benzene oxygen) biphenyl, 3,3 '-two (4-amino-benzene oxygen) biphenyl, 3,4 '-two (3-amino-benzene oxygen) biphenyl, 3,4 '-two (4-amino-benzene oxygen) biphenyl, 4,4 '-two (3-amino-benzene oxygen) biphenyl, 4,4 '-two (4-amino-benzene oxygen) biphenyl, 2, two [4-(3-amino-benzene oxygen) phenyl] sulfones of 2-, 2, two [4-(4-amino-benzene oxygen) phenyl] sulfones of 2-, 2, two [3-(3-amino-benzene oxygen) phenyl] propane of 2-, 2, two [3-(4-amino-benzene oxygen) phenyl] propane of 2-, 2, two [4-(3-amino-benzene oxygen) phenyl] propane of 2-, 2, two [4-(4-amino-benzene oxygen) phenyl] propane of 2-, 2, two [3-(3-amino-benzene oxygen) phenyl] HFC-236fa of 2-, 2, two [3-(4-amino-benzene oxygen) phenyl] HFC-236fa of 2-, 2, two [4-(3-amino-benzene oxygen) phenyl] HFC-236fa of 2-, 2, two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa of 2-, 9, two (3-aminophenyl) fluorenes of 9-, 9, two (4-aminophenyl) fluorenes of 9-, 3,3 '-dimethyl-4,4 '-benzidine, 2,2 '-two (trifluoromethyl) p-diaminodiphenyl, 2, two [4-(4-amino-2-trifluoromethoxy phenoxy base) phenyl] HFC-236fa of 2-, 1, the 2-phenylenediamine, 1, the 3-phenylenediamine, 1,4-phenylenediamine etc.
In the present invention, as mentioned above, used with chemical formula (II) or (III) expression structure alkyl or aryl cyclohexylene pentanoic, therefore, contain bulky side-chain radical (side group) on the main polymer chain, so, the effect that can obtain excellent thermotolerance and improve with the body material binding property.
The concrete example of diamines as the used siloxane structure of the present invention with chemical formula (I) structure, can enumerate, two (gamma-amino propyl group) tetramethyl disiloxane (GAPD, n=1), two (gamma-amino propyl group) polydimethyl sily oxide (PSX-4, n=4), two (gamma-amino propyl group) polydimethyl sily oxide (PSX-8, n=8) etc., these compounds can separately or mix more than 2 kinds and use.
The diamines that contains siloxane structure can be given the upright and outspoken structure of polyimide with flexibility, make binding property and the solvable characteristic in the solvent is increased, during the polyamino acid polymerization, the content of reactant in organic solvent is increased, in addition, when the tackiness agent, owing to can make itself and the bounding force increase of various body materials, particularly, has the adhesion characteristic of body materials such as improvement and silicon chip, chip insulation film and lead frame in field of electronic materials.
Therefore, adopt aromatic tetracarboxylic acid's dianhydride and above-mentioned various diamines, aggregate into polyimide.At this moment, as solvent, can adopt, N-methyl-pyrrolidone (NMP), N, dinethylformamide (DMF), N, N-N,N-DIMETHYLACETAMIDE (DMAc), dimethyl sulfoxide (DMSO) (DMSO), sulfoxide, hexamethyl phosphoric triamide, 1,3-dimethyl-non-proton property polar solvents such as 2-imidazoles, phenol solvents such as phenol, cresols, xylenol, para-chlorophenol.In addition, as required, can also use ether solvents such as Diethylene Glycol, dme, aromatic solvents such as benzene,toluene,xylene, methylethylketone, acetone, tetrahydrofuran (THF), diox, Monoethylene Glycol (MEG) dme, diglyme, methylcyclohexane, cellosolve acetic ester, methyl alcohol, ethanol, Virahol, methylene dichloride, chloroform, trieline, oil of mirbane etc.
As the general polymerization method of polyimide, promptly the hot-imide method at first after the polyamino acid polymerization as parent, with this solution coat, heats, and carries out the method for imidization with heat.When manufacturing polyimide parent of the present invention is polyamino acid, suitable molecular weight and relative viscosity according to polyamino acid, in-10 ℃～100 ℃ temperature range, tetracarboxylic dianhydride and above-mentioned various diamines, behind the input reactor, add solvent, one side high degree of agitation in nitrogen environment, make its reaction on one side, make polyamino acid, the reaction times is ideal less than 10 hours (better is less than 5 hours).
In hot imide method, in order to make polyamino acid be transformed into polyimide, after the polyamino acid coating or coating, be heated to 250～500 ℃, make imidization, at this moment, in drying process,, be dissolved in polyamino acid under the state of solvent in order to promote imidization, add tertiary amines such as pyridine, triethylamine, Tributylamine, isoquinoline 99.9, aceticanhydride, propionic anhydride, st-yrax acid anhydrides and dehydration closed-loop agent, closed loop catalyzer etc.
In addition, when polyimide is solvable in solvent, as method with chemical imidization manufactured polyimide, be tetracarboxylic dianhydride and diamines, after solvent drops into reactor, at Tributylamine, triethylamine, triphenyl phosphite, isoquinoline 99.9, under pyridines etc. exist or in the presence of dehydration catalysts such as tosic acid, be heated to more than 100 ℃ and (it is desirable to more than 180 ℃), directly make the method for polyimide, after tetracarboxylic acid-2-acid anhydride and organic solvent dropped into together, by reacting below 100 ℃, after obtaining the parent polyamino acid of polyimide, add aceticanhydride, propionic anhydride, acid anhydrides such as st-yrax acid anhydrides, dehydration closed-loop agent such as carbodiimide compound such as dicyclohexyl carbodiimide, as required, add pyridine, different quinoline, imidazoles, closed loop catalyzer such as triethylamine, method of (room temperature～100 ℃) closed loop etc. at a lower temperature.
The ideal consumption of the diamines that contains chemical formula (I) structure siloxanes that the present invention uses, 0.1～50% (mole) for the diamines total amount, yet, when consumption is lower than 0.1% (mole), solvability and poor adhesion, when consumption surpassed 50% (mole), binding property improved, yet the polymerization degree of polymkeric substance is difficult to improve.
In addition, the alkyl of expression or 0.01% (mole)～40% (mole) that the consumption of cyclohexylene pentanoic is the diamines total amount are ideal with chemical formula (II) or (III), when consumption is lower than 0.01% (mole), thermotolerance improves, but the solvability variation, when consumption during greater than 40% (mole), solvability improves, but the thermotolerance variation, cost rises.
Generally, the self adhesive tape that electronic component is used, be mainly used on the parts in addition of the lead frame periphery that constitutes semiconductor device, for example, terminal pin, semi-conductor tower carry substrate, heat liberation board, semi-conductor chip self bonding etc. of usefulness, with the TAB (tape bonds automatically) of the FPC that is suitable for 2 layers of structure (softish printed wiring) plectane and 2 layers of structure Copper Foil, in the self adhesive tape that its cohesive force is big is also included within self adhesive tape.
The self adhesive tape of using as electronic component, can enumerate, lead frame is self adhesive tape of using of self adhesive tape, lead frame semiconductor chip adhesive band, the lead frame backing plate of usefulness etc. fixedly, transaction capabilities when general requirement is pasted, self-evident, the stability and the reliability of products that also require to paste back semi-conductor assembling procedure.
Particularly, still have adhesion properties, also require to have thermostability in high temperature operations such as thereafter electric wire connection, epoxy moulding even paste operation at high temperature in semi-conductor assembling operation.General polyimide, paste the flowability and the bonding characteristic of operation in order to increase its high temperature, require its second-order transition temperature and melt temperature low, make loss of thermal resistance therefrom, like this in high temperature operations such as electric wire connection, epoxy moulding, its thermotolerance still can't be guaranteed, yet, for polyimide with 3 yuan of network molecular structures, make the temperature flowing increase by not reducing second-order transition temperature, can guarantee the high temperature bond characteristic, self-evident, also can guarantee the reliability in the high temperature operations such as electric wire connection, epoxy moulding, this is its advantage.
The polyimide self adhesive tape that the polyimide that obtains from the present invention is made, it is the above-mentioned fluid binder of coating on the single face of base film or two sides, make its drying, also can be on self adhesive tape, pressing thickness is that the polyimide adhesive of 1～150 μ m (that better is 5～50 μ m) is made.As used base film this moment, can enumerate, have as heat-resistant film: heat-resistant resin films such as polyimide, polyvinylene sulphur, polyethers, polyethylene terephthalate, fluoro-resin, or Resins, epoxy-woven fiber glass, Resins, epoxy-polyimide-compound heat-resistant film such as woven fiber glass, yet polyimide film is special ideal.The thickness of thermotolerance film, 5～150 μ m are suitable, during in particular as the self adhesive tape of LOC, as base film, mainly are to use the polyimide film of 25 μ m or 50 μ m.In addition,, also can use, carry out chemically treated film with plasma body, corona discharge or silane etc. on the base film surface in order to improve the bounding force between base film and the polyimide adhesive.But only with the adhesive sheet that polyimide adhesive constituted, when making as purpose, base film surface available silicon alkanes releasing agent carries out the demoulding to be handled, and makes the thick separability film of about 1～200 μ m.
On the other hand, resulting polyamino acid of the present invention or polyimide, owing to have excellent thermotolerance and physical strength simultaneously, so, also can be used as the heat-resistant film material and use.
Below, by embodiment and comparative example, be described more specifically the present invention,
[embodiment 1]
In the reactor that agitator, reflux cooler and nitrogen inlet are housed, at first as oxydiphenyl amine 2.8g (0.014 mole), the trimethylammonium cyclohexylene pentanoic 4.31g (0.014 mole) of diamines, the N-N-methyl-2-2-pyrrolidone N-solvent that two (3-aminopropyl) tetramethyl disiloxane 1.45g (0.00585 mole) puts into 173.07g, in 15 ℃ with its dissolving after, drop into 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride 10.74g (0.03 mole), high degree of agitation is 5 hours in nitrogen environment, synthetic polyamino acid.
In the polyamino acid that obtains, add 50ml toluene and 3.0g tosic acid,, carried out imidization reaction 6 hours while separate the moisture that carries out being generated along with reaction in 190 ℃ of heating.Then, the polyimide polymer fluid is injected in the methyl alcohol,, obtain pulverous polyimide, measure resulting polyimide infrared absorption spectrum, at 1718cm the precipitate and separate that obtains, pulverizing, clean and dry
-1And 1783cm
-1Can confirm that typical imide absorbs.
[embodiment 2]
In the reactor that agitator, reflux cooler and nitrogen inlet are housed, at first as oxydiphenyl amine 2.8g (0.014 mole), the trimethylammonium cyclohexylene pentanoic 4.31g (0.014 mole) of diamines, the N-N-methyl-2-2-pyrrolidone N-solvent that two (3-aminopropyl) tetramethyl disiloxane 1.45g (0.00585 mole) puts into 173.07g, in 15 ℃ with its dissolving after, drop into pyromellitic acid anhydride 6.54g (0.03 mole), high degree of agitation is 5 hours in nitrogen environment, synthetic polyamino acid.
In the polyamino acid that obtains, add 50ml toluene and 3.0g tosic acid,, carried out imidization reaction 6 hours while separate the moisture that carries out being generated along with reaction in 190 ℃ of heating.Then, the polyimide polymer fluid is injected in the methyl alcohol,, obtain pulverous polyimide, measure resulting polyimide infrared absorption spectrum, at 1718cm the precipitate and separate that obtains, pulverizing, clean and dry
-1And 1783cm
-1Can confirm that typical imide absorbs.
[embodiment 3]
In the reactor that agitator, reflux cooler and nitrogen inlet are housed, at first as oxydiphenyl amine 2.8g (0.014 mole), the trimethylammonium cyclohexylene pentanoic 4.31g (0.014 mole) of diamines, the N-N-methyl-2-2-pyrrolidone N-solvent that two (3-aminopropyl) tetramethyl disiloxane 1.45g (0.00585 mole) puts into 173.07g, in 15 ℃ with its dissolving after, drop into 3,3 ', 4,4 '-oxygen biphenyl dicarboxylic acid dianhydride 9.30g (0.03 mole), high degree of agitation is 5 hours in nitrogen environment, synthetic polyamino acid.
In the polyamino acid that obtains, add 50ml toluene and 3.0g tosic acid,, carried out imidization reaction 6 hours while separate the moisture that carries out being generated along with reaction in 190 ℃ of heating.Then, the polyimide polymer fluid is injected in the methyl alcohol,, obtain pulverous polyimide, measure resulting polyimide infrared absorption spectrum, at 1718cm the precipitate and separate that obtains, pulverizing, clean and dry
-1And 1783cm
-1Can confirm that typical imide absorbs.
[embodiment 4]
In the reactor that agitator, reflux cooler and nitrogen inlet are housed, at first as oxydiphenyl amine 2.8g (0.014 mole), the trimethylammonium cyclohexylene pentanoic 4.31g (0.014 mole) of diamines, the N-N-methyl-2-2-pyrrolidone N-solvent that two (3-aminopropyl) tetramethyl disiloxane 1.45g (0.00585 mole) puts into 173.07g, in 15 ℃ with its dissolving after, drop into 3,3 ', 4,4 '-hexichol tetracarboxylic dianhydride 8.82g (0.03 mole), high degree of agitation is 5 hours in nitrogen environment, synthetic polyamino acid.
In the polyamino acid that obtains, add 50ml toluene and 3.0g tosic acid,, carried out imidization reaction 6 hours while separate the moisture that carries out being generated along with reaction in 190 ℃ of heating.Then, the polyimide polymer fluid is injected in the methyl alcohol,, obtain pulverous polyimide, measure resulting polyimide infrared absorption spectrum, at 1718cm the precipitate and separate that obtains, pulverizing, clean and dry
-1And 1783cm
-1Can confirm that typical imide absorbs.
[embodiment 5]
Stir in the reactor of trembling device, reflux cooler and nitrogen inlet being equipped with, at first as oxydiphenyl amine 2.8g (0.014 mole), the trimethylammonium cyclohexyl pentanoic 4.31g (0.014 mole) of diamines, the N-N-methyl-2-2-pyrrolidone N-solvent that two (3-aminopropyl) tetramethyl-trisiloxanes 1.45g (0.00585 mole) puts into 173.07g, in 15 ℃ with its dissolving after, drop into hexafluoro tetracarboxylic dianhydride 8.82g (0.03 mole), high degree of agitation is 5 hours in nitrogen environment, synthetic polyamino acid.
In the polyamino acid that obtains, add 50ml toluene and 3.0g tosic acid, in 190 ℃ of heating, separate along with reaction carry out imidization reaction 6 hour on one side.Then, the polyimide polymer fluid is injected in the methyl alcohol,, must measure resulting polyimide infrared absorption spectrum, at 1718cm to pulverous polyimide the precipitate and separate that obtains, pulverizing, clean and dry
-1With 1783
-1Can confirm that typical imide absorbs.
[embodiment 6]
In the reactor that agitator, reflux cooler and nitrogen inlet are housed, at first as oxydiphenyl amine 2.8g (0.014 mole), the 4-methyl cyclohexylene pentanoic 3.91g (0.014 mole) of diamines, the N-N-methyl-2-2-pyrrolidone N-solvent that two (3-aminopropyl) tetramethyl disiloxane 1.45g (0.00585 mole) puts into 173.07g, in 15 ℃ with its dissolving after, drop into 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride 10.74g (0.03 mole), high degree of agitation is 5 hours in nitrogen environment, synthetic polyamino acid.
In the polyamino acid that obtains, add 50ml toluene and 3.0g tosic acid,, carried out imidization reaction 6 hours while separate the moisture that carries out being generated along with reaction in 190 ℃ of heating.Then, the polyimide polymer fluid is injected in the methyl alcohol,, obtain pulverous polyimide, measure resulting polyimide infrared absorption spectrum, at 1718cm the precipitate and separate that obtains, pulverizing, clean and dry
-1And 1783cm
-1Can confirm that typical imide absorbs.
[embodiment 7]
In the reactor that agitator, reflux cooler and nitrogen inlet are housed, at first as oxydiphenyl amine 2.8g (0.014 mole), the 4-methyl cyclohexylene pentanoic 3.91g (0.014 mole) of diamines, the N-N-methyl-2-2-pyrrolidone N-solvent that two (3-aminopropyl) tetramethyl disiloxane 1.45g (0.00585 mole) puts into 173.07g, in 15 ℃ with its dissolving after, drop among the pyromellitic dianhydride 6.54g (0.03 mole), high degree of agitation is 5 hours in nitrogen environment, synthetic polyamino acid.
In the polyamino acid that obtains, add 50ml toluene and 3.0g tosic acid,, carried out imidization reaction 6 hours while separate the moisture that carries out being generated along with reaction in 190 ℃ of heating.Then, the polyimide polymer fluid is injected in the methyl alcohol,, obtain pulverous polyimide, measure resulting polyimide infrared absorption spectrum, at 1718cm the precipitate and separate that obtains, pulverizing, clean and dry
-1And 1783cm
-1Can confirm that typical imide absorbs.
[embodiment 8]
In the reactor that agitator, reflux cooler and nitrogen inlet are housed, at first as oxydiphenyl amine 2.8g (0.014 mole), the 4-methyl cyclohexylene pentanoic 3.91g (0.014 mole) of diamines, the N-N-methyl-2-2-pyrrolidone N-solvent that two (3-aminopropyl) tetramethyl disiloxane 1.45g (0.00585 mole) puts into 173.07g, in 15 ℃ with its dissolving after, drop into 3,3 ', 4,4 '-oxygen di-O-phthalic acid dianhydride 9.30g (0.03 mole), high degree of agitation is 5 hours in nitrogen environment, synthetic polyamino acid.
In the polyamino acid that obtains, add 50ml toluene and 3.0g tosic acid,, carried out imidization reaction 6 hours while separate the moisture that carries out being generated along with reaction in 190 ℃ of heating.Then, the polyimide polymer fluid is injected in the methyl alcohol,, obtain pulverous polyimide, measure resulting polyimide infrared absorption spectrum, at 1718cm the precipitate and separate that obtains, pulverizing, clean and dry
-1And 1783cm
-1Can confirm that typical imide absorbs.
[comparative example 1]
In the reactor that agitator, reflux cooler and nitrogen inlet are housed, at first the oxydiphenyl amine 6.0g as diamines is put into the N-N-methyl-2-2-pyrrolidone N-solvent of 157.59g, in 15 ℃ with its dissolving after, drop into 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride 10.74g (0.03 mole), high degree of agitation is 5 hours in nitrogen environment, synthetic polyamino acid.
[comparative example 2]
In the reactor that agitator, reflux cooler and nitrogen inlet are housed, at first the N-N-methyl-2-2-pyrrolidone N-solvent of putting into 157.59g as the oxydiphenyl amine 6.0g (0.03 mole) of diamines, in 15 ℃ with its dissolving after, drop into pyromellitic acid anhydride 6.54g (0.03 mole), high degree of agitation is 5 hours in nitrogen environment, synthetic polyamino acid.
[comparative example 3]
In the reactor that agitator, reflux cooler and nitrogen inlet are housed, at first trimethylammonium cyclohexylene pentanoic 6.16g (0.02 mole), 1 as diamines, two (4-amino-benzene oxygen) the benzene 2.92g (0.01 mole) of 3-put into the N-N-methyl-2-2-pyrrolidone N-solvent of 173.07g, in 15 ℃ with its dissolving after, drop into 3,3 ', 4,4 '-oxygen biphenyl dicarboxylic acid dianhydride 8.58g (0.03 mole), high degree of agitation is 5 hours in nitrogen environment, synthetic polyamino acid.
In the polyamino acid that obtains, add 50ml toluene and 3.0g tosic acid,, carried out imidization reaction 6 hours while separate the moisture that carries out being generated along with reaction in 190 ℃ of heating.Then, the polyimide polymer fluid is injected in the methyl alcohol,, obtain pulverous polyimide, measure resulting polyimide infrared absorption spectrum, at 1718cm the precipitate and separate that obtains, pulverizing, clean and dry
-1And 1783cm
-1Can confirm that typical imide absorbs.
[comparative example 4]
In the reactor that agitator, reflux cooler and nitrogen inlet are housed, at first as 1 of diamines, 3-two (4-amino-benzene oxygen) benzene 5.84g (0.02 mole), two (3-aminopropyl) tetramethyl disiloxane 2.48g (0.01 mole) put into the N-N-methyl-2-2-pyrrolidone N-solvent of 173.07g, in 15 ℃ with its dissolving after, drop into 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride 10.74g (0.03 mole), high degree of agitation is 5 hours in nitrogen environment, synthetic polyamino acid.
In the polyamino acid that obtains, add 50ml toluene and 3.0g tosic acid,, carried out imidization reaction 6 hours while separate the moisture that carries out being generated along with reaction in 190 ℃ of heating.Then, the polyimide polymer fluid is injected in the methyl alcohol,, obtain pulverous polyimide, measure resulting polyimide infrared absorption spectrum, at 1718cm the precipitate and separate that obtains, pulverizing, clean and dry
-1And 1783cm
-1Can confirm that typical imide absorbs.
The polyamino acid relative viscosity that obtains in the foregoing description 1～8 and the comparative example 1～4 (in N,N-dimethylacetamide, polyamino acid is diluted to 0.05% (weight)) is shown in table 1 respectively.
Then, synthetic polyamino acid solution in embodiment 1～8 and the comparative example 1～4, on sheet glass, be coated with respectively with knife coater, with Vacuumdrier in 80 ℃ of dryings 10 minutes remove desolvate after, take off film from sheet glass, again respectively at 150 ℃ of dryings 5 minutes, in 200 ℃ of dryings 5 minutes, the most finally 300 ℃ make hot amidation 1 hour, make the polyimide film of thickness 50 μ m.
In order to estimate the thermal properties of the film that obtains like this, measure 5% heat decomposition temperature with thermogravimeter, time spent differential thermal component analysis instrument is measured second-order transition temperature; In order to estimate physical strength, the tensile strength when normal temperature is measured coefficient of elasticity and fracture is shown in following table 1 respectively.
[table 1]
| Routine number | Relative viscosity (dl/g) | 5% heat decomposition temperature (℃) | Second-order transition temperature (℃) | Tensile strength (kgf/mm 2) | Modulus of elasticity (kgf/mm 2) |
| Embodiment 1 | 2.35 | 573 | 305 | 10.8 | 500 |
| Embodiment 2 | 2.52 | 568 | 342 | 13.5 | 400 |
| Embodiment 3 | 2.13 | 564 | 290 | 11.5 | 480 |
| Embodiment 4 | 2.40 | 582 | 283 | 10.9 | 440 |
| Embodiment 5 | 1.84 | 560 | 310 | 12.6 | 430 |
| Embodiment 6 | 1.73 | 531 | 276 | 11.9 | 425 |
| Embodiment 7 | 2.68 | 574 | 265 | 10.3 | 395 |
| Embodiment 8 | 2.27 | 581 | 245 | 12.3 | 340 |
| Comparative example 1 | 2.55 | 593 | 269 | 13.4 | 540 |
| Comparative example 2 | 1.92 | 557 | 249 | 15.3 | 430 |
| Comparative example 3 | 1.74 | 557 | 246 | 10.1 | 320 |
| Comparative example 4 | 1.24 | 485 | 247 | 5.4 | 173 |
In addition, the polyimide that obtains in embodiment 1～8 and comparative example 3 and 4, with the polyimide that obtains in comparative example 1 and 2 (polyimide that this imidization obtains is insoluble to solvent), be coated on the Upilex-S polyimide film with knife coater, then, polyimide solution in 230 ℃ of dryings 30 minutes, polyimide respectively with 80 ℃ * 10 minutes, 110 ℃ * 10 minutes, 150 ℃ * 10 minutes, 200 ℃ * 10 minutes condition is in addition after the drying, the most finally 300 ℃ were carried out hot-imide 1 hour, and the thickness of making the polyimide bonding coat is the self adhesive tape of 20 μ m.
In 350 ℃, pressure 5kg/cm
2Condition under the pressurization 10 minutes, respectively Copper Foil, nickel-ferro alloy plate, PIK-3000 solution (Hitachi chemical goods) are bonded in through back on the plate of coating in normal temperature, carry out the T-Peel test with the speed of 50mm/min, the evaluation result of bounding force reaches the solvability to solvent, is shown in following table 2 respectively.
[table 2]
| Solubleness (◎: dissolving fully, *: insoluble) | Bounding force (Kgf/cm) | |||||||
| NMF | DMAc | DMF | DMSO | Cu | NiFe | PIX-3400 | ||
| Embodiment | 1 | ◎ | ◎ | ◎ | ◎ | 1.30 | 1.40 | 1.35 |
| 2 | ◎ | ◎ | ◎ | ◎ | 1.35 | 1.50 | 1.45 | |
| 3 | ◎ | ◎ | ◎ | ◎ | 1.10 | 1.24 | 1.20 | |
| 4 | ◎ | ◎ | ◎ | ◎ | 1.10 | 1.54 | 1.15 | |
| 5 | ◎ | ◎ | ◎ | ◎ | 1.50 | 1.21 | 1.24 | |
| 6 | ◎ | ◎ | ◎ | ◎ | 1.10 | 1.12 | 1.34 | |
| 7 | ◎ | ◎ | ◎ | ◎ | 1.97 | 1.78 | 1.49 | |
| 8 | ◎ | ◎ | ◎ | ◎ | 2.12 | 1.79 | 1.49 | |
| Comparative example | 1 | × | × | × | × | 0.25 | 0.30 | 0.20 |
| 2 | × | × | × | × | 0.47 | 0.57 | 0.40 | |
| 3 | ◎ | ◎ | ◎ | ◎ | 0.42 | 0.29 | 0.27 | |
| 4 | ◎ | ◎ | × | × | 1.94 | 1.75 | 1.49 | |
The NMP:N-N-methyl-2-2-pyrrolidone N-
DMAc:N, the N-N,N-DIMETHYLACETAMIDE
DMF:N, dinethylformamide
DMSO: dimethyl sulfoxide (DMSO)
From the foregoing description and comparative example finding, polyamino acid of the present invention and polyimide resin have excellent thermotolerance and mechanical-physical character, simultaneously, to the solvency power and the high temperature adhesives excellence of solvent, be very useful as the tackiness agent of electronic component or self adhesive tape etc.
Claims (5)
1. the manufacture method of a polyamino acid is characterized in that, reacts by following compounds and makes:
Tetracarboxylic dianhydride more than at least a kind and,
Aromatic diamine more than at least a kind and,
Contain more than at least a kind with the diamines of the siloxane structure of following chemical formula (I) expression and,
Alkyl or aryl cyclohexylene pentanoic more than at least a kind with following chemical formula (II) or chemical formula (III) expression,
Wherein account for 0.1～50% mole of diamines total amount with the diamines of the siloxane structure of chemical formula (I) expression, with chemical formula (II) or (III) consumption of the alkyl or aryl cyclohexylene pentanoic of expression be 0.01～40% mole of diamines total amount,
[Formula I]
In the above-mentioned chemical formula (I), R4 is the alkylidene group of 1～20 carbonatoms, and n ' is 1～20 integer,
[Formulae II] [Formulae II I]
During above-mentioned chemical formula (II) reached (III), R was selected from-CH
3,-CH
2CH
3,-C (CH
3)
3, C (CH
3)
2(CH
2CH
3) or phenyl.
2. the manufacture method of a polyimide is characterized in that making following compounds to react, and again the gained polyamino acid is carried out imidization and makes:
Tetracarboxylic dianhydride more than at least a kind and,
Aromatic diamine more than at least a kind and,
Contain more than at least a kind with the diamines of the siloxane structure of following chemical formula (I) expression and,
Diamines more than at least a kind with following chemical formula (II) or chemical formula (III) expression,
Wherein account for 0.1～50% mole of diamines total amount with the diamines of the siloxane structure of chemical formula (I) expression, with chemical formula (II) or (III) consumption of the alkyl or aryl cyclohexylene pentanoic of expression be 0.01～40% mole of diamines total amount,
[Formula I]
In the above-mentioned chemical formula (I), R4 is the alkylidene group of 1～20 carbonatoms, and n ' is 1～20 integer,
[Formulae II] [Formulae II I]
During above-mentioned chemical formula (II) reached (III), R was selected from-CH
3,-CH
2CH
3,-C (CH
3)
3, C (CH
3)
2(CH
2CH
3) or phenyl.
3. according to the polyimide manufacture method of record in the claim 2, it is characterized in that, under 250～500 ℃ high temperature, implement hot-imide.
4. according to the polyimide manufacture method of record in the claim 2, it is characterized in that in the presence of the dehydration closed-loop agent, the temperature in room temperature～100 ℃ is implemented chemical imidization.
5. according to the polyimide manufacture method of record in the claim 4, it is characterized in that the dehydration closed-loop agent is the compound that is selected from aceticanhydride, propionic anhydride, st-yrax acid anhydrides, the dicyclohexyl carbodiimide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00104040 CN1117113C (en) | 2000-03-14 | 2000-03-14 | Preparation of polyimide resin and polyamine acid as adhesive |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00104040 CN1117113C (en) | 2000-03-14 | 2000-03-14 | Preparation of polyimide resin and polyamine acid as adhesive |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1313350A CN1313350A (en) | 2001-09-19 |
| CN1117113C true CN1117113C (en) | 2003-08-06 |
Family
ID=4577190
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 00104040 Expired - Fee Related CN1117113C (en) | 2000-03-14 | 2000-03-14 | Preparation of polyimide resin and polyamine acid as adhesive |
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| Country | Link |
|---|---|
| CN (1) | CN1117113C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106463706A (en) * | 2014-06-05 | 2017-02-22 | 宇部兴产株式会社 | Electrode manufacturing method |
-
2000
- 2000-03-14 CN CN 00104040 patent/CN1117113C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106463706A (en) * | 2014-06-05 | 2017-02-22 | 宇部兴产株式会社 | Electrode manufacturing method |
| CN106463706B (en) * | 2014-06-05 | 2019-06-18 | 宇部兴产株式会社 | The manufacturing method of electrode |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1313350A (en) | 2001-09-19 |
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