CN1837260A - polyamide resin modified by polyoxy yalkylene amine and its composites - Google Patents

polyamide resin modified by polyoxy yalkylene amine and its composites Download PDF

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Publication number
CN1837260A
CN1837260A CN 200510056952 CN200510056952A CN1837260A CN 1837260 A CN1837260 A CN 1837260A CN 200510056952 CN200510056952 CN 200510056952 CN 200510056952 A CN200510056952 A CN 200510056952A CN 1837260 A CN1837260 A CN 1837260A
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resin
polyoxy
alkylamine
polyamide resin
formula
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CN100457802C (en
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黄坤源
杜安邦
巫胜彦
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CHANGCHUN ARTIFICIAL RESIN FACTORY Co Ltd
Chang Chun Plastics Co Ltd
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CHANGCHUN ARTIFICIAL RESIN FACTORY Co Ltd
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Abstract

The invention discloses a modified polyamide resin and its component through arsenic polyoxy alkylamine, which comprises the following parts: arsenic polyoxide alkylamine resin, heat hard resin, rubber elastic body and inorganic filler. The invention possesses high heat resistance and cohesion property, which is fit for circuit board and integrated circuit component.

Description

Stretch the polyamide resin and the constituent thereof of alkylamine modification through polyoxy
Technical field
The invention relates to a kind of polyamide resin composition, particularly about a kind of polyamide resin composition of stretching the alkylamine modification with polyoxy.
Background technology
Owing to the slimming of electronic and communication facility and the requirement of microminiaturization, also towards microminiaturization and slimming development, the circuit of employed wired circuit board also more trends towards granular to the encapsulation volume of unicircuit in the equipment in recent years.In various wired circuit boards, flexible printed wiring board can significantly reduce the volume and the weight of electronic component, is a kind of wired circuit board commonly used.
Usually the structure of flexible printed wiring board comprises insulating substrate and metal conductor layer, and insulating substrate and metal conductor layer with the bonding formation circuit of tackiness agent laminated plates, are used the material of Copper Foil as metal level usually.Polyimide resin has good thermotolerance, chemical resistance, mechanicalness and good electrical properties, is a kind of insulating substrate material commonly used.Metal level engages the tackiness agent that uses normally Resins, epoxy or acryl resin solid with insulating substrate.The thermotolerance of these tackiness agents is not good, breaks easily in follow-up resin heat embrittlement making processes, reduces the stability of flexible printed wiring board size.
Polyamide resin has excellent electrical properties, mechanical properties and high heat resistance, so the heat-resisting solid of Chang Zuowei printed circuit board (PCB) uses.As the polyamide resin of heat-resisting solid is interlayer adhesive coating as the printed wiring laminated plates, and it is formation by using polyamide resin and thermosetting resin mixture to impose on the required base material.The interlayer adhesive coating is bonding with insulating substrate in the laminated plates and Copper Foil, and this interlayer adhesive coating can be possessed its resin flow reaching adhesion insulating substrate and Copper Foil, and can fill up the recessed crack in the copper foil circuit.In order to allow the interlayer circuit card keep required flowability, the binding temperature of insulating substrate and Copper Foil preferably can carry out at lesser temps, avoids reducing flowability and hardening after the too high slaking of resin Yin Wendu.
Except printed circuit board (PCB), CSP in the large-scale integrated circuit encapsulation technology (chip sizepackage) encapsulation is widely used because reducing the required area of encapsulation.The CSP encapsulation has short wire length, produces less inductance, therefore can improve the usefulness of large-scale integrated circuit, is usually used in the encapsulation of mobile phone or camera etc., even also uses this type of encapsulation technology in dynamic RAM (DRAM).
In the CSP encapsulation technology, a kind of bonding wire type (wire-bonding type) encapsulation is arranged.Bonding wire is used in patch type CSP encapsulation, will electrically connect as the circuit card and the chip of polyimide resin system, then with resin-sealed.This type of CSP encapsulating structure is simple, and can be produced by the change of existing ball grid array (BGA) technology, is therefore used widely now.
CSP encapsulation is made at first and is produced through hole at polyimide base material, electroplating ventilating hole for example, it on the adhesive coating of coating can with Copper Foil via the heating adhesion, next step uses as existing method production laminated plates such as pressurizations, then forms circuit, cloth is planted golden projection etc.In the adhesion step of polyimide base material and Copper Foil, use polyamide resin as the lead coating material usually, because of it has excellent electrical properties, mechanical properties and high heat resistance.The tackiness agent that Resins, epoxy, polyamic acid and polyamic acid and bismaleimide amine mixt also can be used as other parts uses.Along with the micro of CSP encapsulation volume, the circuit card of CSP is seen meticulous more, and the adhesive requirement of the thermotolerance of tackiness agent and copper is also higher.
In existing tackiness agent, the Resins, epoxy tackiness agent is not high to the tolerance level of welding compound, and lacks the thermal stability that can tolerate reflow (reflow) processing procedure.Use thermoplastic polyimide resin, polyamic acid and composition thereof has excellent heat-resistant quality, need the high-temperature maturing processing as 300 ℃ to 400 ℃, and its tackiness to Copper Foil or resin is not good.
In order to strengthen the tackiness to Copper Foil or resin base material, Hitachi chemical (Hitachi Chemical) company proposes to use siloxanes (siloxane) with polyamide modified, to improve heat-resistant quality.Yet the reaction of siloxanes and resin is difficult for carrying out, and cost is higher.
Polyamide resin composition can provide between pi substrate layer and Copper Foil powerful tackiness, with as the interlayer adhesive coating.How providing the polyamide resin with desired characteristic as heat-resisting tackiness agent, is the problem that encapsulation field needs to be resolved hurrily.
Summary of the invention
For overcoming the shortcoming of above-mentioned prior art, main purpose of the present invention is to provide a kind of then property good polyamide resin and constituent thereof.
Another object of the present invention is to provide a kind of polyamide resin and constituent thereof of high heat resistance.
A further object of the present invention is to provide a kind of polyamide resin and constituent thereof that low temperature is fitted that be used for.
For reaching above-mentioned purpose, the invention provides and a kind ofly stretch the polyamide resin of alkylamine modification by polyoxy, it is by stretch the polyamic acid suc as formula (1) that alkylamine and many phenyl diamine compounds mixture and triphen six anhydride reactions obtain as polyoxy:
R wherein 1For
Figure A20051005695200082
Or
Wherein, n is 2 to 3;
The polyoxy that the di-isocyanate reaction of the polyamic acid of formula (1) and formula (2) obtains is as the formula (3) stretched the polyamide resin of alkylamine modification:
Figure A20051005695200092
Wherein, R 2Be C 1-3Stretch alkyl;
Figure A20051005695200093
The present invention also provides a kind of polyamide resin composition, and it comprises that above-mentioned polyoxygenated stretches the polyamide resin of alkylamine modification, thermosetting resin and rubber elastomer.This resin combination also comprises inorganic filler.Polyamide resin composition of the present invention has high heat resistance and high then property, does not need high temperature to fit and can realize fitting, and is used for following of wiring board and integrated circuit component.
Embodiment
Below by specific specific examples explanation the specific embodiment of the present invention embodiment.
Polyoxy of the present invention is stretched the polyamide resin of alkylamine modification, is by polyamic acid compound and the preparation of two isocyanide esters.Polyamic acid compound of the present invention has the structure suc as formula (1):
Wherein, R 1For
Figure A20051005695200095
Figure A20051005695200101
Or
Figure A20051005695200102
Wherein, n is 2 to 3, i.e. n=2～3;
Figure A20051005695200111
Wherein, R 2Be C 1-3Stretch alkyl, and be preferably C 1Stretch alkyl.
In one embodiment of the invention, the polyamic acid compound of above-mentioned formula (1) can be by stretch alkylamine (PolyoxyAlkylene Amine) suc as formula the polyoxy of (4):
Figure A20051005695200112
Wherein n be 2 to 3, suc as formula (5) 2, two (4-(the 4-amido phenoxy group) phenyl) propane of 2-(bis (4-(4-aminophenoxy) phenyl) propane, many phenyl diamine compounds BAPP):
Figure A20051005695200113
And triphen six acid anhydrides (trimellitic anhydride, TMA) reaction and get.Wherein, polyoxy is stretched alkylamine and can commercially be obtained, and as Jeffamine D-230, n is 2 to (being n=2～3) and molecular weight 230 in its representative formula (4), is produced by U.S. Huntsman company.
The above-mentioned method for preparing the polyamic acid compound can be as described in the reaction formula 1:
Reaction formula 1
Figure A20051005695200114
Figure A20051005695200121
In the formula, R 1As above-mentioned definition.Then stretch alkyl-modified polyamide resin suc as formula the polyoxy of (3) by the polyamic acid and formula (2) the two isocyanide ester prepared in reaction of formula (1), shown in reaction formula 2:
Reaction formula 2
Figure A20051005695200122
In the formula, R 1And R 2As above-mentioned definition.Of the present invention to stretch the polyamide-imide resin molecular weight ranges of alkylamine modification through polyoxy about 25,000 to 150,000, more excellently is about 50,000 to 120,000.
In an embodiment of the present invention, it is as described below to stretch the method for making of polyamide-imide resin of alkylamine modification through polyoxy.To stretch alkylamine as many phenyl diamine compounds of BAPP and polyoxy and be dissolved in non-protonic solvent.The example of this non-protonic solvent comprises but the non-N-of being limited to N-methyl-2-2-pyrrolidone N-(NMP), N,N-DIMETHYLACETAMIDE (DMAC), dimethyl formamide (DMF) and composition thereof.Then add triphen six acid anhydrides (TMA), heating is reacted.Utilize the backflow that adds organic solvent that water byproduct is taken out of, organic solvent includes but not limited to toluene.This moment, precursor polyamic acid (PAA) endless loop dehydration became the polyimide resin that end contains COOH.Sustained reaction steams toluene up to confirming anhydrous being taken out of, stopped reaction, and reaction mixture temperature reduced to room temperature.
Then get as 4, the vulcabond of 4 '-diphenylmethanediisocyanate (MDI) adds in the above-mentioned reaction mixture, slowly temperature is raise and reacts, and has the carbonic acid gas bubble during attentive response and emerges.Reacted 2 hours, obtaining product is the polyamide resin (PAI) of stretching alkylamine through the modification polyoxygenated.
Polyamide resin composition of the present invention comprises that the polyoxygenated of 40 to 80 weight parts stretches the polyamide resin of alkylamine modification and the thermosetting resin of 20 to 45 weight parts.This thermosetting resin can be the Resins, epoxy with two epoxy group(ing).The example of this thermosetting resin includes but not limited to that phosphorous resene, phenolic varnish (Cresol-novolac) Resins, epoxy, bromine are Resins, epoxy, the mixture of above-mentioned resin etc.
Polyamide composition of the present invention also comprises the rubber elastomer of 5 to 30 weight parts and the inorganic filler of 0 to 15 weight part.The example of this rubber elastomer includes but not limited to, the acrylonitrile-butadiene rubber of the acrylonitrile-butadiene rubber of acrylic-nitrile rubber, divinyl rubber, C-terminal, amido end, acrylonitrile-butadiene rubber, silicone rubber and the resemblance thereof of epoxy group(ing) end.The example of this inorganic filling includes but not limited to, silicon oxide (SiO 2), aluminum oxide (Al 2O 3), aluminium hydroxide (Al (OH) 3), magnesium hydroxide (Mg (OH) 2), weisspiessglanz (Sb 2O 5), lime carbonate (CaCO 3), magnesiumcarbonate (MgCO 3), Calucium Silicate powder, magnesium oxide (MgO), zinc oxide (ZnO), talcum (Talc), mica (Mica), melamine pyrophosphate (melamine pyrophosphate), melamine polyphosphate (melamine polyphosphate) and resemblance thereof.
Polyamide resin composition of the present invention also comprises stiffening agent.The example of this stiffening agent includes but not limited to, and 2-ethyl-4-methylimidazole (2-Ethyl-4-Methyl Imidazole), methylimidazole (2-Methylimidazole, 2-MI).
The polyamide resin composition of the present invention that comprises mentioned component, the tackiness agent when can be used for printed circuit board (PCB) resin substrate and Copper Foil and fitting is when also can be used for encapsulate as CSP, as the tackiness agent of following semi-conductor chip.Polyamide resin composition of the present invention has high adhesion to Copper Foil, and thermotolerance is good, and can finish adhesion in lower temperature of reaction and fit.By appended embodiment and explanation thereof, advantage that more can clearer understanding polyamide resin composition of the present invention.
Embodiment
The raw material explanation
Polyoxy is stretched alkylamine: as the formula (4), wherein n is 2 to 3.
BAPP:2, two (the 4-4-amido phenoxy group) phenyl of 2-) propane, shown in (5).
TMA: triphen six acid anhydrides
MDI:4,4 '-diphenylmethanediisocyanate is shown in (2).
NMP:N-methyl-2-alkyl pyrrolidone.
BE501:Bis A Type Resins, epoxy, epoxy equivalent (weight) 500, the Changchun artificial resin is produced.
Rubber: Nippon Zeon 1072 (butadiene-acrylonitrile of C-terminal, carboxy-endbutadiene-acrylonitrile).
2-MI: methylimidazole.
Synthesis example
In that 13.12 BAPP (0.032 mole) that restrain stretch alkylamine 1.84g (0.008 mole) with polyoxy and 65 NMP that restrain are solvent with inserting in the four neck reactors of stirrer, stir to make the BAPP dissolving.
The NMP that get 16.13 TMA (0.084 mole) that restrain and 25 grams are in four neck reactors, and temperature maintenance was reacted 1 hour in 80 ℃.Reactor is loaded onto Dean stack de-watering apparatus, get 30 gram toluene and insert in the reactor, temperature rises to 190 ℃, utilizes refluxing toluene that water is taken out of, and this moment, proparea thing polyamic acid (PAA) endless loop dehydration became the polyimide resin that end contains COOH.Sustained reaction steams toluene up to confirming anhydrous being taken out of, and stopped reaction is also reduced to room temperature with reaction mixture temperature.
The MDI (0.048 mole) that weighs 12 grams adds in the above-mentioned reaction mixture, and temperature slowly rises to 190 ℃, has the carbonic acid gas bubble to produce in the attentive response.Reacted 2 hours, obtaining product is the polyamide resin (PAI) of stretching the alkylamine modification through polyoxygenated.
Embodiment 1
That gets in the above-mentioned synthesis example 73 grams stretches alkylamine modification PAI resin through polyoxy, and its solid type part is 30%, gets the rubber varnishes of 6 grams, and it is that the described rubber of raw material is dissolved among the NMP, and the solid type part of rubber is 20%.Get the BE-501 of 21 grams and the 2-MI of 0.5 gram and be put in the beaker, use stirrer to stir and it was uniformly dispersed in 20 minutes with 500rpm.Solid type part of varnish this moment (vamish) is 41.4%, then adds 10% talcum based on the solid type part of varnish, and promptly weight is the talcum of 4.14 grams.Adding the talcum rear stirrer stirred 30 minutes with 500rpm.Deaeration was left standstill 4 hours then.
Above-mentioned synthetic varnish is coated on the Copper Foil, baking oven with 130 ℃ through 5 minutes, then 180 ℃ through heating in 10 minutes with removal of solvents, obtaining resin thickness is 12.5 microns.Then at 160 ℃ and 100kg/cm 2Applying Copper Foil under the pressure is resin layer, the dual platen of both sides Copper Foil in the middle of becoming.This dual platen enter again 260 ℃ of high temperature oven d being full of nitrogen through 1 hour and 280 ℃ through heat hardening in 2 hours, make the character excellence, have high then intensity and high heat-stable double-surface flexible circuit card.
Embodiment 2 to embodiment 8
Embodiment 2 to 8 prepares the double-surface flexible circuit card with the method shown in the embodiment 1, and each embodiment component proportions is as shown in table 1.
Table 1
Form (g) Modification PAI Thermosetting resin BE501 Rubber 2-MI The varnish gross weight The solid type part of varnish Talcum (g)
Embodiment 1 73.0 21.0 6.0 0.5 100 44.1％ 4.41
Embodiment 2 67.0 25.4 7.6 0.5 100 47.0％ 4.70
Embodiment 3 63.0 21.0 16.0 0.5 100 43.1％ 4.31
Embodiment 4 57.5 35.9 6.6 0.8 100 54.5％ 5.45
Embodiment 5 52.5 31.5 16.0 0.8 100 50.5％ 5.05
Embodiment 6 51.5 35.9 12.6 0.8 100 53.9％ 5.39
Embodiment 7 48.0 42.0 10.0 1.0 100 58.4％ 5.84
Embodiment 8 42.0 42.0 16.0 1.0 100 57.8％ 5.78
Comparative example
Use Hitachi to change into the KS6500 resin of (Hitachi Chemical) in the comparative example, make double surface soft board in the mode of embodiment 1.
Utilize following method to test, the results are shown in table 2.
(1) Copper Foil is followed intensity: according to IPC TM-650 2.4.9
(2) heat-resisting test: according to IPC TM-650 2.4.13
Table 2
Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Embodiment 6 Embodiment 7 Embodiment 8 Comparative example
Copper Foil is followed intensity (kg/cm) 1.32 1.28 1.33 1.59 1.67 1.74 1.83 1.94 1.01
Heat-resisting test (288 ℃ 30 seconds) By By By By By By By By By
Heat-resisting test (340 ℃ of 10 sand) By By By By By By By By By
Resin of the present invention as shown in Table 2 has preferable Copper Foil and follows intensity.And can be by heat-resisting test.

Claims (19)

1. a polyoxy is stretched the polyamide resin of alkylamine modification, it is characterized in that, this resin is the polyamic acid by formula (1):
Wherein, R 1For
Figure A2005100569520002C2
Figure A2005100569520003C1
Or
Figure A2005100569520003C2
Wherein, n is 2 to 3 integer;
And the vulcabond of formula (2):
Figure A2005100569520003C3
Wherein, R 2Be C 1-3Stretch alkyl;
The polyoxy that reaction obtains is as the formula (3) stretched the polyamide resin of alkylamine modification:
Figure A2005100569520003C4
Wherein, R 1And R 2As defined above, and m be 25 to 150 integer.
2. resin as claimed in claim 1 is characterized in that, this R 2Be C 1Stretch alkyl.
3. resin as claimed in claim 1 is characterized in that, the polyamic acid of this formula (1) is the mixture and the acquisition of triphen six anhydride reactions of being stretched alkylamine and many phenyl diamine compounds by polyoxy.
4. resin as claimed in claim 3 is characterized in that, stretch in the mixture of alkylamine and many phenyl diamine compounds at this polyoxy, this polyoxy stretch alkylamine be 99 to 80 the mole %, this many phenyl diamine compounds is 1 to 20 mole of %.
5. resin as claimed in claim 3 is characterized in that, it is as the formula (4) that this polyoxy is stretched alkylamine:
Wherein, n is 2 to 3 integer.
6. resin as claimed in claim 3 is characterized in that, this many phenyl diamine compounds is as the formula (5):
Figure A2005100569520004C1
7. resin as claimed in claim 1 is characterized in that, the molecular weight ranges of the polyamide resin of this formula (3) expression is 25,000 to 150,000.
8. resin as claimed in claim 7 is characterized in that, the molecular weight ranges of the polyamide resin of this formula (3) expression is 50,000 to 120,000.
9. a polyamide resin composition is characterized in that, this resin combination comprises:
The polyoxy as claimed in claim 1 of 40 to 80 weight parts is stretched the polyamide resin of alkylamine modification;
The thermosetting resin of 20 to 45 weight parts; And
The rubber elastomer of 5 to 20 weight parts.`
10. resin combination as claimed in claim 9 is characterized in that this resin combination also comprises the inorganic filler of 0 to 15 weight part.
11. resin combination as claimed in claim 9 is characterized in that, this thermosetting resin is the Resins, epoxy with two epoxy group(ing).
12., it is characterized in that this thermosetting resin is that to be selected from phosphorous resene, phenolic varnish, Resins, epoxy, bromine be a kind of in Resins, epoxy and composition thereof as claim 9 or 11 described resin combinations.
13. resin combination as claimed in claim 9, it is characterized in that this rubber elastomer is a kind of in acrylonitrile-butadiene rubber, silicone rubber of acrylonitrile-butadiene rubber, the epoxy group(ing) end of acrylonitrile-butadiene rubber, the amido end of acrylic-nitrile rubber, divinyl rubber, C-terminal and composition thereof.
14. resin combination as claimed in claim 10, it is characterized in that this inorganic filler is to be selected from a kind of in silicon oxide, aluminum oxide, aluminium hydroxide, magnesium hydroxide, weisspiessglanz, lime carbonate, magnesiumcarbonate, Calucium Silicate powder, magnesium oxide, zinc oxide, talcum, mica, melamine pyrophosphate, melamine polyphosphate and composition thereof.
15. resin combination as claimed in claim 9 is characterized in that, this resin combination also comprises stiffening agent.
16. resin combination as claimed in claim 15 is characterized in that, this stiffening agent is 2-ethyl-4-methylimidazole or diformazan imidazoles.
17. a polyamide resin composition that uses polyoxy as claimed in claim 9 to stretch the alkylamine modification prepares the method for flexible circuit board, it is characterized in that this method comprises the following steps:
Polyoxy being stretched the polyamide resin composition of alkylamine modification coats on the tinsel; And
Add the heat abstraction solvent.
18. method as claimed in claim 17 is characterized in that, this method also comprises the following steps:
The polyamide resin composition of stretching the alkylamine modification at polyoxy is not fitted the face of tinsel with pressuring method another tinsel of fitting; And
Heat hardening resin combination under nitrogen is to make the double-surface flexible circuit card of tinsel-resin-metal paper tinsel.
19., it is characterized in that this tinsel is to be selected from Copper Foil, aluminium foil, nickel foil and Alloy Foil to constitute a kind of in the group as claim 17 or 18 described methods.
CNB2005100569526A 2005-03-24 2005-03-24 polyamide resin modified by polyoxy yalkylene amine and its composites Active CN100457802C (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20220041809A1 (en) * 2019-01-25 2022-02-10 Lg Chem, Ltd. Diamine compound, and polyimide precursor and polyimide film using same

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US4935490A (en) * 1988-04-13 1990-06-19 E. I. Dupont De Nemours And Company Highly soluble aromatic polyimides
CA1330865C (en) * 1989-01-31 1994-07-26 George Dennison Fulford Process for producing alumina from bauxite
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20220041809A1 (en) * 2019-01-25 2022-02-10 Lg Chem, Ltd. Diamine compound, and polyimide precursor and polyimide film using same
US11926706B2 (en) * 2019-01-25 2024-03-12 Lg Chem, Ltd. Diamine compound, and polyimide precursor and polyimide film using same

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