CN1241605A - Underfill encapsulant compositions for use in electronic devices - Google Patents
Underfill encapsulant compositions for use in electronic devices Download PDFInfo
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- CN1241605A CN1241605A CN 99111272 CN99111272A CN1241605A CN 1241605 A CN1241605 A CN 1241605A CN 99111272 CN99111272 CN 99111272 CN 99111272 A CN99111272 A CN 99111272A CN 1241605 A CN1241605 A CN 1241605A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/01—Chemical elements
- H01L2924/01019—Potassium [K]
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/01—Chemical elements
- H01L2924/01087—Francium [Fr]
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/10—Details of semiconductor or other solid state devices to be connected
- H01L2924/102—Material of the semiconductor or solid state bodies
- H01L2924/1025—Semiconducting materials
- H01L2924/10251—Elemental semiconductors, i.e. Group IV
- H01L2924/10253—Silicon [Si]
Abstract
A curable underfill encapsulant composition, suitable for use in semiconductor packaging, comprises one or more mono- or polyfunctional maleimide compounds, or one or more mono- or polyfunctional vinyl compounds other than maleimide compounds, or a combination of maleimide and vinyl compounds, with a free radical curing agent, and optionally, one or more fillers.
Description
The present invention is supported that by government the initial contract number that it is authorized by United States Air Force is F33615-96-C5117, and government has certain right for the present invention.
The present invention relates to gap filler (underfill) encapsulant composition, said composition be suitable for to be done in microelectronic device protection and is strengthened interconnected between electronic component and the substrate.
Microelectronic device contains millions of circuit elements, mainly be the transistor that assembles in unicircuit (IC) sheet and also have resistor, electrical condenser and other element that the interconnection formation circuit of these electronic components also finally is connected to or is supported on carrier or the substrate (as printed circuit board (PCB)).
Integrated circuit component can comprise single nude film, single diaphragm seal or encapsulation multistage, and single nude film can be connected on the lead frame, is sealed successively and be connected on the printed circuit board (PCB) maybe can be directly connected on the printed circuit board (PCB).
No matter element is connected to the nude film on the lead frame or is connected on the printed circuit board (PCB) or the encapsulation on other substrate, connect and all carry out at electric terminals on the electronic component and the respective electrical terminal on the substrate, make a kind of method of these connections and used metal or the polymeric material that is used to impact on element or the substrate terminal, the aligning terminal also connects together, and the assembly that heating obtains is to soft heat metal or polymeric material and solidify this junction.
In manufacturing step subsequently, make the circulation of electronic package through rising or reduction temperature, because the difference of the thermal expansivity of electronic component, interconnected material and substrate, this thermal cycling can be oppressed the element of assembly and be made its damage, damage for fear of this, (hereinafter being called gap filler or gap filler sealing agent) filled up to strengthen interconnected and to absorb the stress of some thermal cyclings with polymeric encapsulant in the space between element and substrate.
Two outstanding purposes of gap filler technology are as the known package (wherein substrate is connected on the lead frame) and the ball grid array (encapsulation of wherein one or more substrates is connected on the printed circuit board (PCB)) of flip-chip in industry.
The gap filler sealing can be carried out after metal or the interconnected soft heat of polymerization, or can carry out simultaneously with soft heat.If gap filler carries out after being sealed in interconnected soft heat, the gap filler sealing agent of having measured will be along the circumferential distribution of one or more electronic packages, and element connects material inside to the boundary of capillarity of substrate gap.Reach the sealing agent viscosity of best boundary of capillarity if desired, can preheat substrate.After filling up the space, additional slit packing seal agent can to help to reduce the fatigue lifetime of concentrating and prolong unit construction of pressure, subsequently, be solidified the gap filler sealing agent, to reach best final performance along whole assembly peripheral distribution.
If the soft heat that gap filler sealing and binding substances or polymerization are coupled to each other is carried out simultaneously, can comprise that then the gap filler sealing agent of fusing assistant (if binding substances is the material that is coupled to each other) at first is used for substrate or element; Then, the terminal of element and substrate is aligned and contacts, and heating component is with soft heat metal or the interconnected material of polymerization.During this heat-processed, the soft heat of the curing of gap filler sealing agent and metal or polymerization interconnecting material is carried out simultaneously.
For the monolithic encapsulation that relates to commodity in enormous quantities, the inefficacy substrate can go out of use and not have significantly sacrificing, yet, it then is expensive discarding the multi-disc encapsulation of having only an inefficacy sheet, this failed element is reworked will the industry interests be arranged, nowadays, one of main surging force is that development not only can be satisfied the gap filler sealing agent that strengthens all interconnected demands in the semi-conductor industry, and be can reprocess promptly do not destroy substrate and mechanicalness is removed the gap filler sealing agent of failed element.
Conventional gap filler technology is used low viscosity thermosetting organic substance, and the most widely used is epoxy/acid anhydride system.In order to obtain required mechanical property, higher molecular weight thermoplasticity material is for the encapsulated substance preferred compositions, yet even these materials have high viscosity solid film form, this is a defective for manufacturing process.Therefore, need the novel sealing agent composition that is easy to allocate to meet the automated manufacturing process and can reprocess.
The present invention relates to curable gap filler encapsulant composition, comprise the one or more compounds that contain one or more maleimide functionality, or contain one or more compounds of one or more vinyl functionality, or contain the mixture of maleimide or vinyl functionality compound, radical initiator and/or light trigger and choose any one kind of them or multiple filler.
The following sense maleimide compound that refers to of compound that contains a maleimide functionality, the multifunctional maleimide compound of the following finger of compound that contains a plurality of maleimide functionality, the following functional ethylene's based compound that refers to of compound that contains a vinyl functionality, contain the following polyfunctional vinyl compound that refers to of compound of a plurality of vinyl functionality, functionality is defined herein as the two keys between carbon and the carbon.
By selecting wherein mainly to measure a functional compound for composition, composition is designed to and can reprocesses.
The ability of processing these thermoplasticity compositions that are used for the gap filler sealing agent is by living oligomer or the prepolymer that uses lower molecular weight and makes them solidify realization on the spot after being used for electronic assemblies.Lower molecular weight shows as than low viscosity and is easy to use on the substrate.
In another embodiment, the present invention is the curing sealant composition that obtains after the curable gap filler encapsulant composition of narration just solidifies.
In another embodiment, the present invention is an electronic package, comprise electronic component with polynary electric terminal, each terminal by metal polymeric material is electric or mechanical connection (metal or polymeric material are also referred to as interconnected or interconnecting material at this) to substrate, this substrate has the polynary electric terminal corresponding to the electronic component terminal.With sealing agent be allocated in solidify betwixt then between electronic component and the substrate to strengthen binding substances or polymkeric substance interconnected.Wherein solidify the gap filler sealing agent by the preparation of compositions that comprises following ingredients: one or more one or multifunctional maleimide compound, or one or more one or polyfunctional vinyl compound except that maleimide compound, or the mixture of maleimide and vinyl compound, free radical curing agent and/or light trigger and choose any one kind of them or multiple filler.
The maleimide and the vinyl compound that are used for gap filler encapsulant composition of the present invention are curable compounds, mean that they can be meant crosslinked or noncrosslinking polymerization as the curing that is used for this place with crosslinked or noncrosslinking form polymerization.Knownly in the art be, the crosslinked bridged bond connection that is the chain of two polymkeric substance by element, molecular radical or compound, and normally under heating, take place, increase along with cross-linking density, the character of material can be varied to thermoset from thermoplasticity, and it must strengthen bonding strength, heat and resistance and for the resistibility of solvent and other chemical.
Selection by wisdom and one an amount of or polyfunctional compound can prepare the polymkeric substance of a wide region cross-linking density to the toughness glassy polymers from sticking, elastic, and the polyfunctional compound's of reaction ratio is high more, cross-linking density is big more.Thermoplastic properties if desired, prepare gap filler sealing agent of the present invention with the restriction cross-linking density from a functional compound, yet, can add a small amount of polyfunctional compound to give composition some crosslinked and intensity, the amount that the polyfunctional compound is provided is limited to the amount that does not reduce required thermoplastic properties, in these parameters, the intensity of independent gap filler sealing agent and the purposes that elastic force can be applicable to the specific usage period.
The glass transition temperature that also can control cross-linking density and obtain a wide region in solidifying gap filler is with tolerance subsequent handling and service temperature.For the gap filler sealing agent that is designed to reprocess, select Tg to be lower than metal or the interconnected reflowing temperature of polymerization, if add gap filler after the soft heat of interconnecting material, then low Tg can make sealant material softening and adhere on electronic component and the substrate and do not influence interconnected.
If before soft heat, add gap filler, reach same effect.During the interconnecting material soft heat, after interconnected curing, keep close contact with interconnected, good stress transfer and long-term reliability is provided.
In these cases, when essential reprocessing assembly, electronic component can be prized substrate and can be heated any residue gap filler sealing agent softening and be easy to remove to it.
In gap filler encapsulant composition of the present invention, maleimide compound and vinyl compound can be used alone or unite use, maleimide or vinyl compound, or they both will be present in the amount of 2-98% (weight) based on the existing of organic compound (not comprising any filler) and solidify in the gap filler encapsulant composition.
The gap filler encapsulant composition will further comprise at least a radical initiator, this initiator be defined as be resolve into have one or more not sharing electrons, the chemical substance of high reactivity and normally short-lived molecule fragment, this initiator can be by chain mechanism initiating chamical reaction.Radical initiator is according to maleimide or vinyl compound, or the weight of maleimide or vinyl compound both (not comprising any filler) exists with the amount of 0.1-10%, preferred 0.1-3.0%.Radically curing mechanism produces fast setting and curing preceding storage period of limit for length's composition is provided, preferred radical initiator comprises that superoxide (as Peroxycaprylic acid butyl ester and dicumyl peroxide) and azo-compound are (as 2,2 '-azo two (2-methyl-propionitrile) and 2,2 '-azo two (2-methyl-butyronitrile)).
On the other hand, the gap filler encapsulant composition can contain the light trigger that replaces radical initiator and can cause solidification process by the UV radiation subsequently.Light trigger is according to maleimide or vinyl compound, or the weight of maleimide or vinyl compound both (not comprising any filler) exists with the amount of 0.1-10%, preferred 0.1-3.0%.Photoinitiation and free radical initiation are and conform with demand in these cases, for example, can be caused solidification process and in the free radical initiation step, can be utilized heating to realize that the curing of free radical is to finish curing by the UV irradiation.
Usually, these compositions will solidify in 80 ℃ of-180 ℃ of temperature ranges, and reached curing at 5 minutes to 4 hours, self-evident, the encapsulant composition time and the temperature of cure profile separately is variable, and the purpose of different compositions is that the cure profile that is suitable for actual industrial manufacturing process can be provided.
Even when the gap filler sealing agent needs thermoplastic properties, behind the electronic package that is used for element and substrate, by using lower molecular weight living oligomer or prepolymer and make its curing reach easy purposes on the spot, the material that its uncured state is used has high working ability and the solidification heat plasticity sealing agent that obtains provides mechanical property.
For the operation of some gap fillers, use inert inorganic filler to regulate thermal expansivity with more near the parameter of substrate.The example of suitable thermal conductance filler comprises silicon-dioxide, graphite, aluminium nitride, silicon carbide, boron nitride, diamond powder and clay.Filler generally exists in the amount of total gap filler encapsulant composition with 20-80%.
The symbol C (O) that this specification sheets uses in full is meant carbonyl group.
Maleimide compound
Be applicable to that the maleimide compound of circuit component composition of the present invention has the structure of following formula representative:
[M-X
m]
n-Q or [M-Z
m]
n-K, in these specific chemical formulas, when subscript " n " when being integer 1, compound is a functional compound; When subscript " n " was integer 2-6, compound was the polyfunctional compound.
Chemical formula [M-X
m]
nThe compound of-Q representative is for wherein:
M is the maleimide amine moiety with following formula structure:
R wherein
1Be H or C
1-C
5Alkyl; X is selected from the have structure aromatic yl group of aromatic yl group of (I)-(V):
With Q be straight or branched alkyl, alkoxyl group, alkylamine, alkyl sulfide, alkylidene group, alkylidene group oxygen base, alkylene amines, alkylidene group sulphur, aryl, aryloxy or the aryl sulphur that in chain, has about at the most 100 atoms, its chain can contain promising side chain or as saturated or the unsaturation ring or the heterocyclic substituent of a skeleton part in the chain, and any heteroatoms wherein can or cannot directly be connected with X;
Or Q is the carbamate with following formula structure:
Wherein, R
2Be alkyl, aryl or aralkyl group independently of one another with 1-18 carbon atom; R
3Be in chain, to have the alkyl or the alkoxyl group of 100 atoms at the most, can contain aryl substituent in the chain; X is O, S, N or P; With n be 0-50;
Or Q is the ester with following formula structure:
R wherein
3Be to have the alkyl or the alkoxyl group of 100 atoms at the most in chain, its chain can contain aryl substituent;
Or Q is the siloxanes with following formula structure:
-(CR
1 2)
e-[SiR
4 2-O]
f-SiR
4 2-(CR
1 2)
g-
The R in each position wherein
1Substituting group is the R in H or the alkyl group with 1-5 carbon atom and each position independently
4Substituting group is alkyl group or the aromatic yl group with 1-5 carbon atom independently, and e and g are that 1-10 and f are 1-50 independently; With
M be 0 or 1 and n be 1-6.
Preferred X is structure (II), (III), (IV) or (V), is more preferably structure (II).
Preferred Q is straight or branched alkyl, alkoxyl group, alkylidene group or the alkene oxygen base that has about at the most 100 atoms in chain, described is the saturated of side chain or unsaturation ring or heterocyclic substituent, or described siloxanes, more preferably described straight or branched alkyl or siloxanes.
Chemical formula [M-Z
m]
nThe compound of-K representative is for wherein:
M is the maleimide amine moiety with following formula structure:
R wherein
1Be H or C
1-C
5Alkyl;
Z is straight or branched alkyl, alkoxyl group, alkylamine, alkyl sulfide, alkylidene group, alkylidene group oxygen base, alkylene amines, alkylidene group sulphur, aryl, aryloxy or the aryl sulphur that has about at the most 100 atoms in chain, its chain can contain promising side chain or as saturated or the unsaturation ring or the heterocyclic substituent of a skeleton part in the chain, and any heteroatoms wherein can or cannot directly be connected with K;
Or Z is the carbamate with following formula structure:
Wherein, R
2Be alkyl, aryl or aralkyl group independently of one another with 1-18 carbon atom; R
3Be in chain, to have the alkyl or the alkoxyl group of 100 atoms at the most, can contain aryl substituent in the chain; X is O, S, N or P; With n be 0-50; Or Z is the ester with following formula structure:
R wherein
3Be to have the alkyl or the alkoxyl group of 100 atoms at the most in chain, its chain can contain aryl substituent;
Or Z is the siloxanes with following formula structure:
-(CR
1 2)
e-[SiR
4 2-O]
f-SiR
4 2-(CR
1 2)
g-
The R in each position wherein
1Substituting group is the R in H or the alkyl group with 1-5 carbon atom and each position independently
4Substituting group is alkyl group or the aromatic yl group with 1-5 carbon atom independently, and e and g are that 1-10 and f are 1-50 independently;
K be selected from have structure (VI)-(XIII) aromatic yl group aromatic yl group (though the key that has only that can show be connected on the aromatic group K, it be considered to the representative as described with the defined any amount of additional key of n):
Wherein P is 1-100
Wherein P is 1-100;
R wherein
5, R
6And R
7Be straight or branched alkyl, alkoxyl group, alkylamine, alkyl sulfide, alkylidene group, alkylidene group oxygen base, alkylene amines, alkylidene group sulphur, aryl, aryloxy or the aryl sulphur that in chain, has about at the most 100 atoms, its chain can contain promising side chain or as saturated or the unsaturation ring or the heterocyclic substituent of a skeleton part in the chain, and any heteroatoms wherein can or cannot directly be connected with aromatic nucleus; Or R
5, R
6And R
7Be to have structure-(CR
1 2)
e-[SiR
4 2-O]
f-SiR
4 2-(CH
3)
g-siloxanes, R wherein
1Substituting group is the R in H or the alkyl group with 1-5 carbon atom and each position
4Substituting group is alkyl group or the aromatic yl group with 1-5 carbon atom independently, and e is that 1-10 and f are 1-50;
With
With m be 0 or 1 and n be 1-6.
Preferred Z is straight or branched alkyl, alkoxyl group, alkylamine or the alkylidene group oxygen base that has about at the most 100 atoms in chain, described is the saturated of side chain or unsaturation ring or heterocyclic substituent, or described siloxanes and more preferably described straight or branched alkyl or siloxanes.
Preferred K is structure (VIII), (X) or (XI), is more preferably structure (X) or (XI), most preferably is structure (X).
Preferred, in particular as reprocessing sealing agent maleimide compound be N-butyl phenyl maleimide and N-ethylphenyl maleimide.
Vinyl compound
Vinyl compound (except the maleimide) has structure at this:
Or
In these specific structures, when subscript " n " when being integer 1, compound is a functional compound; When subscript " n " was integer 2-6, compound was the polyfunctional compound.
In these structures, R
1And R
2Be H or alkyl, or form 5-9 person's ring jointly with the carbon that forms vinyl groups with 1-5 carbon atom; B is C, S, N, O, C (O), O-C (O), C (O)-O, C (O) NH or C (O) N (R
8), R wherein
8Be C
1-C
5Alkyl; M is 0 or 1; N is 1-6; With X, Q, Z and K as mentioned above.
Preferred B is O, C (O), O-C (O), C (O)-O, C (O) NH or C (O) N (R
8); More preferably B is O, C (O), O-C (O), C (O)-O or C (O) N (R
8).
Other component
According to the character of gap filler sealing agent bonded substrate, sealing agent also can contain coupling agent, here used coupling agent is to contain and the chemical substance of the polymerizable functional group of maleimide and the reaction of other vinyl compound, and described functional group can with the metal hydroxides condensation that is present in substrate surface.Described coupling agent is well-known with the preferred amounts that is used for the composition of specific substrate in the art.Suitable coupling agents is silane, silicon ester, acrylate metal salt or methylacrylic acid metal-salt, titanate and the compound that contains chelating ligand (as phosphine, mercaptan and acetylacetic ester).When coupling agent exists, can reach 10%, the amount of preferred 0.1-3.0% by general its amount of weight of maleimide and other functional ethylene based compound.
In addition, encapsulant composition can contain the promising curing sealant that obtains provides additional flexibility and flexible compound, this compounds can be any thermoset or the thermoplasticity material with 50 ℃ or lower Tg, generally be that freely to rotate with chemical bond be the polymkeric substance of feature, ester and the ether group that these chemical bonds for example can be by adjacent carbon one carbon single bond of the two keys of carbon one carbon that exists, existence and do not have ring structure and exist and obtain.Suitable described properties-correcting agent comprises polyacrylic ester, poly-(divinyl), poly-THF (polymeric tetrahydrofuran (THF)), CTBN (butyronitrile of carboxy blocking) rubber and polypropylene glycol.When the malleablization compound exists, can reach about 15% by its amount of weight of maleimide and other functional ethylene based compound.
If oxyalkylene segment is not the part in the maleimide compound structure, then siloxanes can be added in the gap filler prescription to give its elasticity.Suitable siloxanes is available from the end capped polydimethylsiloxane of iso-butylene oxygen base propyl group of the company that learns a skill in federalization and the end capped polydimethylsiloxane of aminopropyl.
Also can add other additive (as adhesion promotor) as needs, the type of used adhesion promotor and amount are known for those skilled in the art.
Embodiment
Prepare various maleimides and vinyl compound and it is mixed with encapsulant composition, the viscosity and the thixotropy index of research uncured composition, cure profile, second-order transition temperature, thermal expansivity, thermomechanical analysis and the re-workability of research curing composition.
Embodiment 1
The end capped dimerization diamines of preparation benzoylamino bismaleimides
In the 500mL three-necked bottle that is equipped with feed hopper, magnetic agitation, internal temperature probe and nitrogen inlet/outlet, (sold with Versamine 552 by Henkel, 20.0g 37mmol) is dissolved in ether (Et with the dimerization diamines
2O, 200mL) in, follow tempestuously and to stir, add NaOH
Aq(use 100mL H
2The 11.7mL of O dilution, the solution of 6.25M, 73mmol).This solution is positioned under the stable nitrogen gas stream and ice bath in, follow stirring that it is cooled to 3 ℃, (13.6g, ether 73mmol) (50mL) solution add in the feed hopper with paranitrobenzoyl chloride, in 60 minutes, this solution is added in reactor, keep internal temperature T＜10 ℃, after dropwising, to react on～3 ℃ of following stirrings 60 minutes, then, make temperature rise to room temperature and stirred 4 hours, solution is transferred in the separating funnel and with distilled water (300mL), 5%HCl
Aq(300mL), NaCl
Aq(250mL) and distilled water (2 * 250mL) wash isolating organic layer, tell organic layer, with anhydrous magnesium sulfate to its drying, filter and solvent removed in vacuo, obtain thickness yellow oily dinitro compound (30.0g, 96%), this compound exhibits goes out satisfied
1H NMR and IR spectrum.
Magnetic agitation is being equipped with; in the 250mL three-necked bottle of reflux exchanger and nitrogen inlet/outlet; with above-mentioned dinitro compound (5.0g; 5.9mmol) be dissolved in methyl alcohol (MeOH) (25mL) and tetrahydrofuran (THF) (THF) (5mL) in; under the nitrogen protection situation; add this solution; follow to stir and add 5%pd-C (0.96g); add ammonium formiate (3.4g; 55mmol) and at room temperature stirring reaction is 2 hours, observes carbonic acid gas immediately and emits, and filters this solution; remove a large amount of filter solvents by Rotary Evaporators; the toughening oil that obtains is dissolved in the ether (150mL), and with distilled water (150mL) washing, separation is also used anhydrous magnesium sulfate drying; solvent removed in vacuo; obtain the pale brown look oily of viscosity diamines (3.9g, 84%), this compound exhibits goes out satisfied
1H NMR and IR spectrum.
In being equipped with magnetic agitation, feed hopper and nitrogen inlet/outlet 250mL three-necked bottle, (0.5g 5.1mmol) is dissolved in the acetone (10mL), and this solution is being cooled off on the ice bath and placing under the nitrogen with maleic anhydride, with above-mentioned diamines (2.0g, 2.60mmol) acetone (10mL) solution add in the feed hopper, in 30 minutes, drip this solution, stirring reaction is 30 minutes in ice bath, then, make it be warmed to room temperature, stirred 4 hours, in the slurry that obtains, add diacetyl oxide (Ac
2O) (1.54mL, 160mmol), triethylamine (Et
3N) (0.23mL, 1.63mmol) and sodium acetate (NaOAc) (0.16g, 1.9mmol), slurry to the gentle reflux that obtains of heating reaches 5 hours, the cooling reactant is to room temperature, rotary evaporation removes and desolvates, and obtains brown oil, and this thing is dissolved in CH
2Cl
2(250mL), and, when needs, destroy emulsion by adding sodium-chlor with distilled water (200mL), saturated sodium bicarbonate (200mL) and distilled water (200mL) washing.Isolate organic layer, use anhydrous magnesium sulfate drying, solvent removed in vacuo obtains brown solid bismaleimides (2.0g, 83%), and this resin shows gratifying
1H NMR,
13C NMR and IR spectrum, this spectrum show has slight acetate to pollute.
Embodiment 2
Preparation 20-dimaleoyl imino-10,11-dioctyl-eicosane (and isomer)
Being equipped with drying tube, thermometer, feed hopper, mechanical stirrer at a slow speed, with in many necks of 5L bottle of nitrogen purging, with maleic anhydride (98.06g, 1.02 equivalents, right-NH
2) be dissolved in the 500mL tetrahydrofuran (THF) (THF), beginning to stir and with dry ice/water-bath Quench solution, beginning slowly adding is dissolved in dimerization diamines among the 250mLTHF (Versamine 552, Henkel, 245.03g, 0.4477mo1), the reinforced time after reinforced the finishing, was removed ice bath in 1 hour, by feed hopper at a slow speed, float towards bonded with 375mLTHF and to solidify diamines, after 1 hour, around flask, reappose ice bath, adding 1-hydroxybenzothiazole (96.79g, 0.80 equivalent, right-NH
2), it is flushed in the flask that has 50mLTHF, when temperature reaches 5 ℃, beginning slowly be added in dicyclohexyl carbodiimide (DCC) among the 250mLTHF (188.43g, 1.02 equivalents, right-NH
2), temperature between charge period remains on below 10 ℃, after adding DCC, with 80mLTHF rinsing feed hopper at a slow speed, remove ice bath, monitor reaction by IR, when it seems that different imide has changed into maleimide when (adding the complete back of DCC about 4 hours), filtering mixt with THF rinsing solid, is placed refrigerator overnight with organic solution.
From refrigerator, take out solution and make it be warmed to room temperature, (0.0513g) is added in the solution with quinhydrones, makes temperature maintenance at evaporation section THF below 28 ℃, in Rotary Evaporators, with the extremely about 800mL of solution concentration, the visible particle thing is placed refrigerator overnight with solution.
From refrigerator, take out solution and make it warm, leach solid, use the THF rinsing, filtrate transferring to is equipped with mechanical stirrer, is connected in the 2L multinecked flask of the vacuum system of trap and the Glass tubing that is connected by the pipe arrangement that is connected to drying tube, at room temperature, remove remaining THF and during churning in solution, rouse air filled cavity by vacuumizing, with the semi-solid refrigerator overnight of placing of the pale brown look of the milk that obtains.
From refrigerator, take out semi-solid and make it warm, this semisolid is dissolved in (4 * 250mL) wash to remove I-hydroxybenzotriazole (HOBT) among methyl alcohol and each 450mL of hexane and with 50% methanol.Use the hexane extraction product, behind the adding 300mL hexane, do not observe separation, (3 * 250mL) purging compounds are placed refrigerator overnight with organic phase to add entry.
From refrigerator, take out described material, occur two-layer, the upper strata is clarification and xanchromatic, bottom is safran and muddiness, in this material impouring separating funnel, top layer is hexane and required product, and (6 * 200mL) extractions are easy to separate bottom with hexane, the extraction liquid that merges also filters with anhydrous magnesium sulfate drying, with hexane rinsing solid, be no more than under 24 ℃ the temperature, rotary evaporation removes and desolvates to the volume of about 750mL, under the room temperature, remove remaining solvent with vacuum/pneumatic pump, obtain required product, yield is 67%.
Embodiment 3
Preparation butadiene-acrylonitrile bismaleimides
Feed hopper is being equipped with; mechanical stirrer; in the 3L four-necked bottle of internal temperature probe and nitrogen inlet/outlet; amino-terminated butadiene-acrylonitrile (is sold with Hycar resin 1300 * 42 ATBN by BF Goodrich; wherein m that indicates in the structure and n are the integer (450g for molecular-weight average 3600; 500mmol; based on amine equivalent weight AEW=450g) be dissolved in the chloroform (1000mL); the solution that adding was stirred under nitrogen protection also cools off in ice bath; will be at the maleic anhydride (98.1g in the chloroform (50mL); 1mmol) be written in the feed hopper; in 30 minutes, add this solution in the reaction solution; keep internal reaction temperature and be lower than 10 ℃; the slurry that stirring obtains in ice bath 30 minutes; then it is warmed to room temperature and stirred 4 hours, in the slurry that obtains, add diacetyl oxide (Ac
2O) (653.4g, 6mol), triethylamine (Et
3N) (64.8g, 0.64mol) and sodium acetate (NaOAc) (62.3g, 0.76mol), reaction solution is heated to gentle reflux reaches 5 hours, make reaction be cooled to room temperature, (2 * 1L) extractions, solvent removed in vacuo obtains maleimide end-sealed butadiene acrylonitrile for water (1L), saturated sodium bicarbonate (1L) and water immediately.
Embodiment 4
Preparation is from three (epoxypropyl) isocyanuric acid ester deutero-, three (maleimides)
Mechanical stirrer is being equipped with, in the 2L three-necked bottle of internal temperature probe and nitrogen inlet/outlet, with three (epoxypropyl) isocyanuric acid ester (99.0g, 0.33mol) be dissolved among the THF (500mL), in this solution, add hydroxy phenyl maleimide (189.2g, 1mol) with benzyl dimethyl amine (1.4g, 0.05% (weight)), heat this solution (500mL) and reach 7 hours to 80 ℃, cool off this solution to room temperature, filter, with 5% aqueous hydrochloric acid and distilled water (1L) washing and filtering thing, the solid state triazine (maleimide) that obtains, vacuum-drying under the room temperature.
Embodiment 5
Preparation dimaleoyl imino ethyl palmitate
In the 2L three-necked bottle that is equipped with mechanical stirrer, internal temperature probe, feed hopper and nitrogen inlet/outlet, (274.9g 1mol) is dissolved in Et with palmityl chloride
2Among the O (500mL), (84.0g, distilled water 1mol) (500mL) solution, and make this solution ice bath cooling in nitrogen is with hydroxyethyl maleimide (141g, Et 1mol) to follow vigorous stirring to add sodium bicarbonate
2O (100mL) solution is written in the feed hopper, in 30 minutes, add this solution in the reaction solution, keep internal reaction temperature between charge period and be lower than 10 ℃, in ice bath, stirred this solution 30 minutes, make it be warmed to room temperature and restir 4 hours then, this solution is transferred in the separating funnel, (2 * 500mL) wash isolating organic layer with distilled water (500mL), 5% aqueous hydrochloric acid (500mL) and distilled water, separate organic layer, with anhydrous magnesium sulfate drying, filtration and solvent removed in vacuo, obtain aliphatic maleimide.
Embodiment 6
Preparation is from 5-isocyanato-1-(isocyanato methyl)-1,3,3-trimethyl-cyclohexane deutero-bismaleimides
Mechanical stirrer is being equipped with; in the 1L three-necked bottle of feed hopper and nitrogen inlet/outlet; with 5-isocyanato-1-(isocyanato methyl)-1; 3; 3-trimethyl-cyclohexane (111.15g; 0.5mol) be dissolved among the THF (500mL); make reaction place nitrogen protection; and under agitation; when being heated to 70 ℃, solution adds dibutyl tin dilaurate (cat.Sn ") (6.31g; 10mmol); (141g; 1mol) (100mL) is written in the feed hopper; added this solution in the isocyanate solution; the mixture that obtains 70 ℃ of heating 4 hours is warmed to room temperature and solvent removed in vacuo with reaction solution, and the oil of remnants is dissolved in CH will to be dissolved in hydroxyethyl maleimide among the THF in 30 minutes
2Cl
2(1L), and with 10% aqueous hydrochloric acid (1L) and distilled water (2 * 1L) washings, isolating organic layer with dried over mgso, filter and solvent removed in vacuo, obtain maleimide.
Embodiment 7
Preparation is from two polymerization oleic acid glycol deutero-dimerization divinyl ethers
Be equipped with mechanical stirrer to be filled with in the 2L three-necked bottle of nitrogen, (1.15g 5mmol) is dissolved in propyl vinyl ether (24.4g with two (benzonitrile) Palladous chlorides, 3mol) (sell with Pripol2033 by Unichema with the oleic acid dimer diol, 284.4g, 500mmol) in, at room temperature, stirred this solution three days, then, pour gac (20g) into and stirred the slurry that filtration obtains 1 hour, vacuum is removed excessive propyl vinyl ether, obtains the yellow oily divinyl ether.
Embodiment 8
Preparation is from two polymerization oleic acid glycol deutero-dimerization diacrylates
Mechanical stirrer is being equipped with, in the 1L three-necked bottle that is filled with nitrogen of feed hopper and internal temperature probe, the oleic acid dimer diol (is sold with Pripol 2033 by Unichema, 284.4g, 500mmol) be dissolved in the anhydrous propanone (500mL), with triethylamine (101.2g, 1mol) be added in this solution and cooling this solution to 4 ℃ in ice bath, to be dissolved in the acrylate chloride (90.5g in the anhydrous propanone (100mL), 1mol) add in the feed hopper, in the reaction soln that in 60 minutes, its adding is being stirred and keep internal temperature＜10 ℃, on ice bath, stirred this solution 2 hours, make it be warmed to room temperature then and stirred 4 hours, remove a large amount of solvents by rotary evaporation, residual oil is dissolved in CH
2Cl
2(1L), and with 5% aqueous hydrochloric acid (800mL) and water (2 * 800mL) washings, isolating organic layer with anhydrous magnesium sulfate drying, filter and solvent removed in vacuo, obtain the oily diacrylate.
Embodiment 9
Preparation N-ethylphenyl maleimide
Be dissolved in 4-7 base aniline (12.12g) in the 50mL anhydrous diethyl ether and slowly be added in the 100ml anhydrous ether solution of 9.81g maleic anhydride that stirring, in ice bath, after adding finishes, stirred reaction mixture 30 minutes, little yellow crystals is filtered and drying, diacetyl oxide (200mL) is used to dissolve maleinamic acid and 20g sodium acetate.Reacting by heating mixture in 160 ℃ of oil baths, reflux after 3 hours, cooling solution is to room temperature, it is positioned in the 1L beaker in frozen water, vigorous stirring 1 hour, the suction filtration product and in hexane recrystallization, at the crystalline material that 50 ℃ of following vacuum dried overnight are collected, FTIR and NMR analyze the feature that has shown ethyl maleimide.
Embodiment 10
Preparation two (thiazolinyl thioether)
In the 3L three-necked bottle that is equipped with mechanical stirrer and Dean-Stark water distilling apparatus, dimeracid (is sold with trade mark Empol 1024 by Unichema, 574.6g, 1mol) and propargyl alcohol (112.1g 2mol) is dissolved in the toluene (1L), adds the vitriol oil (6mL) this solution 6 hours to the component distillation that refluxes and goes out 36mL water, make solution be cooled to room temperature, (2 * 1L) washings, anhydrous magnesium sulfate drying and solvent removed in vacuo obtain oily intermediate alkynes propyl ester to water.
In being equipped with the 1L three-necked bottle that is filled with nitrogen of reflux exchanger, mechanical stirrer and internal temperature probe, (650.7g 1mol) is dissolved among the THF (200mL), adds lauryl mercaptan (404.8g with this ester intermediate, 2mol) with 2,2`-azo two (2, the 4-methyl pentane nitrile) (is sold with trade mark Vazo 52 by Dupont, 11g), follow and be stirred in heating obtains in the oil bath mixture to 70 and ℃ reach 7 hours, make reaction be cooled to room temperature, solvent removed in vacuo obtains oily mercaptan.
Embodiment 11
The gap filler encapsulant composition
By organic composition is mixed, then with the composition high speed shear that has cilicon oxide filler to admixing uniform preparation gap filler encapsulant composition, the composition that obtains is little yellow slurry, by the brookfield viscosity instrument, measure viscosity with the 2.54cm rotor under 25 ℃, 0.5 rotating speed, organic composition, silicon oxide by weight proportion, brookfield viscosity and thixotropy index are reported as follows at this:
Composition 11-A:
3,5-dimethylphenyl maleimide 20.1g (0.1mol)
Hydroxybutyl vinyl ether 11.6g (0.1mol)
TSL 8330 00.32g (1wt%)
Cross thylhexoic acid tert-butyl ester 00.32g (1wt%)
By 60% (weight) silicon oxide, the ratio of 40% (weight) organic composition is mixed organic composition with cilicon oxide filler, and brookfield viscosity is 21000cp, and thixotropy index is 2.1.
Composition 11-B:
N-ethylphenyl maleimide 20.1g (0.1mol)
P t butylbenzoic acid vinyl ester 20.4g (0.1mol)
TSL 8330 00.4g (1wt%)
Cross the thylhexoic acid tert-butyl ester
By 67% (weight) silicon oxide, the ratio of 33% (weight) organic composition is mixed organic composition with cilicon oxide filler, and brookfield viscosity is 15600cp, and thixotropy index is 2.1.
Composition 11-C:
N-dodecylphenyl maleimide 34.1g (0.1mol)
Methylacrylic acid isobornyl thiocyanoacetate 22.2g (0.1mol)
TSL 8330 00.56g (1wt%)
Cross the thylhexoic acid tert-butyl ester
By 60% (weight) silicon oxide, the ratio of 40% (weight) organic composition is mixed organic composition with cilicon oxide filler, and brookfield viscosity is 14300cp, and thixotropy index is 2.5.
Composition 11-D:
N-ethylphenyl maleimide 20.1g (0.1mol)
N-caprolactam 13.9g (0.1mol)
TSL 8330 00.4g (1wt%)
Cross the thylhexoic acid tert-butyl ester
By 61% (weight) silicon oxide, the ratio of 39% (weight) organic composition is mixed organic composition with cilicon oxide filler, and brookfield viscosity is 21000cp, and thixotropy index is 2.4.
Composition 11-E:
N-dodecylphenyl maleimide 34.1g (0.1mol)
T-butyl styrene 16.0g (0.1mol)
TSL 8330 00.5g (1wt%)
Cross the thylhexoic acid tert-butyl ester
By 60% (weight) silicon oxide, the ratio of 40% (weight) organic composition is mixed organic composition with cilicon oxide filler, and brookfield viscosity is 21000cp, and thixotropy index is 2.3.
Embodiment 12
Thermal expansivity and glass transitional region
Thermal expansivity (CTE) is meant that given scantling has different expansion ratios with the different material of variation of temperature, the expansion ratio of any given material all varies with temperature, if the CTE difference of the element that combines, then the circulation change of temperature can produce bending, crack or leafing, in general semiconductor subassembly, the CTE of integrated circuit block 2 or 3ppm/ ℃ of scope in; For the organic circuit board substrate, CTE is higher than 30ppm/ ℃; For weld, CTE is 26-28ppm/ ℃, and in order to strengthen weld, the gap filler sealing agent is preferably near the CTE of solder joint.
When polymkeric substance was heated, it can transit to soft rubbery state from hard vitreous state by transitional region.This zone is called gamma transition zone or Tg, if the expansion of polymkeric substance and the relation of temperature are plotted figure, then the gamma transition zone is the boundary between lesser temps/glassy zone thermal expansivity and comparatively high temps/rubber areas thermal expansivity, and in the aforementioned region, rate of expansion significantly increases.The second-order transition temperature of preferred polymers is higher than common experiential operating temperature of operating period subsequently, reprocessing if desired, and its second-order transition temperature is lower than any rework temperature.
For each composition among the composition 11-A to 11-E, with the thermomechanical analysis solidified sample to measure second-order transition temperature (Tg) and thermal expansivity (CTE), each equal portions composition of 2ml is injected the hole of silicon-dioxide/rubber model, and solidify to form 4mm diameter and the high resin cylinder of 5mm, one from-50 ℃ to 200 ℃ the successive temperature range, 5 ℃/minute speed heats these samples to raise, Tg is measured as the temperature when 0 ℃ (sample is softening under this temperature), and is measured as the flex point in expansion and temperature curve.CTE is measured as the slope of expansion curve in ppm/ ℃ of unit, and the Tg of composition 11-A to 11-E is reported as follows:
| Sample | ??CTE?ppm/℃ | ???Tg℃ |
| ????11-A | ????32 | ????144 |
| ????11-B | ????36 | ????165 |
| ????11-C | ????37 | ????160 |
| ????11-D | ????30 | ????125 |
| ????11-E | ????40 | ????110 |
Embodiment 13
Re-workability
Each composition of test 11-A to 11-E is as being tried vehicle 250 * 250 mils
2Silicon mold and composition are attached to uses ability on the FR-4 circuit board substrates again, 1ml equal portions gap filler sample and 0.002g, 3 mil granulated glass sphere spacers are admixed (getting the interconnected place of solder joint or polymkeric substance), be assigned between mold and the FR-4 circuit card, and under 125 ℃, solidified 20 minutes, in order to reprocess, 200 ℃ hot plate heating components 1 minute, mechanicalness is removed mold, on the FR-4 circuit card, stay the gap filler resistates, circuit card is cooled to room temperature, is used to dissolve the resistates of removing on the circuit card in the methyl iso-butyl ketone (MIBK) on the porosity.The reprocessing recovery time is 2 minutes, and all samples has all shown re-workability.
In contrast, with epoxy adhesive (by Ablestik Laboratories, RanchoDominguez, California, sell with trade mark Ablebond XP-11 as gap filler) carry out same processes, though integrated circuit block can be removed from circuit card,, there is not serious scratch or impression damage circuit card just resistates can not be cleaned out.
This embodiment shows that these compositions can and can satisfy operational standard as the gap filler sealing agent by reprocessing.
Embodiment 14
Re-workability
In this embodiment, with tin/lead welding 250 * 250 mils of naming a person for a particular job
2The silicon mold is connected on the substrate of binding substances soft mode dressing, after the binding substances soft heat, respectively gap filler 11-A to 11-E is distributed along one side of each mold and substrate separately, and be heated to 80 ℃ with start capillary action and be full of mold and substrate between the slit.
In order to reprocess, 200 ℃ hot plate heating components 1 minute, after mechanicalness is removed mold from the circuit card, under this temperature, gap filler is softening, binding substances is interconnected to be merged, and stays binding substances and gap filler resistates on the FR-4 circuit card, is used to remove gap filler and cleaning circuit plate to do not observe residual materials under opticmicroscope at the methylethyl ketone solvent on the porosity.
Embodiment 15
The reprocessing gap filler that contains polyfunctional monomer
By organic composition is mixed, the composition high speed shear by will having silica filler is to admixing the gap filler encapsulant composition that uniform preparation contains simple function and polyfunctional compound then, and the composition that obtains is little yellow slurry.
Composition 15-A:
N-4-butyl phenyl maleimide 22.9g (64.9%)
4-hydroxybutyl vinyl ether 11.6g (32.9%)
Triethylene glycol divinyl ether 0.2g (0.57wt%)
Formyl radical oxygen base propyl trimethoxy silicane 0.3g (0.85wt%)
Dicumyl peroxide 0.3g (0.85wt%)
(production number is FB-6S by 66% (weight) silicon oxide (68.5g), sell by Denka), the ratio of 34% (weight) organic composition, organic composition is mixed with cilicon oxide filler, CTE is measured as 34ppm/ ℃, Tg is 135 ℃, and solidified sample such as embodiment 13 do not observe residual materials under opticmicroscope.
Embodiment 16
UV and thermosetting composition
Composition 16-A
The gap filler encapsulant composition makes its mixing and prepares by following following ingredients manually acutely mixed to obtaining even paste:
Bismaleimides is (by polytetrahydrofuran-two-to amino
The benzoic ether preparation is sold with Versalink P-650 by Henkel) 1.01g
The cyclohexanedimethanol divinyl ether
(international extraordinary product) 0.19g
α, alpha, alpha-dimethyl oxygen base-α-phenyl acetophenone
(selling with Irgacure 651) 0.06g by Ciba special chemical article company
Hydrophilic fused silica
(selling～5 microns by Denka) 3.78g
To place 250 mils * 250 mil silicon plastic films on the FR-4 veneer sheet with the sealing of above-mentioned paste and with pulsed xenon UV source (RC-500B pulse UV cure system, xenon main office) 30 seconds kinds of irradiation, sealing agent demonstrates hard, abundant solidified surface, plastic film is fixed firmly on the laminate sheet material for sealed dose when firmly, subsequently, place 175 ℃ of thermostat containers to reach 20 minutes the sample assembly, make the plastic film of sealing be cooled to room temperature, then, from veneer sheet, it is removed by force, detect the plastic film periphery, the uncured sealing agent of veneer sheet/tackiness agent interface or tackiness agent/air surface interface do not occupy the zone.
Composition 16-B
The gap filler encapsulant composition makes its mixing and prepares by following following ingredients manually acutely mixed to obtaining even paste:
Bismaleimides is (by polytetrahydrofuran-two-to amino
The benzoic ether preparation is sold with Versalink P-650 by Henkel) 1.01g
The cyclohexanedimethanol divinyl ether
(international extraordinary product) 0.19g
2 ethyl hexanoic acid tert-butyl ester 0.03g
Hydrophilic fused silica
(selling～5 microns by Denka) 3.78g
To be put in 250 mils * 250 mil silicon plastic films on the FR-4 veneer sheet with the sealing of above-mentioned paste and place 150 ℃ of thermostat containers to reach 30 minutes, make assembly to be measured be cooled to room temperature and from veneer sheet, plastic film removed by force, detect plastic film periphery, veneer sheet/tackiness agent interface or tackiness agent/air surface interface uncured sealing agent do not occupy the zone.
According to this specification sheets, the various embodiments of the inventive method comprise those that (but being not limited to this) following label part is demarcated:
1. curable gap filler encapsulant composition comprise and have molecular formula as herein described M-Xm] maleimide of n-Q, wherein X is selected from the group of the aromatic group with following array structure:
With
2. according to part 1 curable gap filler encapsulant composition, wherein Q is straight or branched alkyl, alkoxyl group, alkylidene group or the alkylidene group oxygen base that has about at the most 100 atoms in chain, its chain can contain promising side chain or as saturated or the unsaturation ring or the heterocyclic substituent of a skeleton part in the chain.
3. according to part 1 curable gap filler encapsulant composition, wherein Q is the straight or branched alkyl that has about at the most 100 atoms in chain, its chain can contain promising side chain or as saturated or the unsaturation ring or the heterocyclic substituent of a skeleton part in the chain.
4. according to part 1 curable gap filler encapsulant composition, wherein Q is the carbamate with following formula structure:
Wherein, R
2Be alkyl, aryl or aralkyl group independently of one another with 1-18 carbon atom; R
3Be in chain, to have the alkyl or the oxyalkyl chain of 100 atoms at the most, can contain aryl substituent in the chain; X is O, S, N or P; With n be 0-50.
5. according to part 1 curable gap filler encapsulant composition, wherein Q is the ester with following formula structure:
R wherein
3Be to have the alkyl or the oxyalkyl chain of 100 atoms at the most in chain, its chain can contain aryl substituent.
6. according to part 1 curable gap filler encapsulant composition, wherein Q is the siloxanes with following formula structure:
-(CR
1 2)
e-[SiR
4 2-O]
f-SiR
4 2-(CR
1 2)
g-
The R in each position wherein
1Substituting group is the R in H or the alkyl group with 1-5 carbon atom and each position independently
4Substituting group is alkyl group or the aromatic yl group with 1-5 carbon atom independently, and e and g are that 1-10 and f are 1-50 independently.
7. curable gap filler encapsulant composition comprise and have molecular formula as herein described M-Zm] maleimide of n-K, wherein Z is straight or branched alkyl, alkoxyl group, alkylidene group or the alkylidene group oxygen base that has about at the most 100 atoms in chain, and its chain can contain promising side
Chain or as saturated or the unsaturation ring or the heterocyclic substituent of a skeleton part in the chain.
8. according to part 7 curable gap filler encapsulant compositions, wherein Z is the straight or branched alkyl that has about at the most 100 atoms in chain, its chain can contain promising side chain or as saturated or the unsaturation ring or the heterocyclic substituent of a skeleton part in the chain.
9. according to part 7 curable gap filler encapsulant compositions, wherein Z is the carbamate with following formula structure:
Wherein, R
2Be alkyl, aryl or aralkyl group independently of one another with 1-18 carbon atom; R
3Be in chain, to have the alkyl or the oxyalkyl chain of 100 atoms at the most, can contain aryl substituent in the chain; X is O, S, N or P; With n be 0-50.
10. according to part 7 curable gap filler encapsulant compositions, wherein Z is the ester with following formula structure:
R wherein
3Be to have the alkyl or the oxyalkyl chain of 100 atoms at the most in chain, its chain can contain aryl substituent.
11. according to part 7 curable gap filler encapsulant compositions, wherein Z is the siloxanes with following formula structure:
-(CR
1 2)
e-[SiR
4 2-O]
f-SiR
4 2-(CR
1 2)
g-
The R in each position wherein
1Substituting group is the R in H or the alkyl group with 1-5 carbon atom and each position independently
4Substituting group is alkyl group or the aromatic yl group with 1-5 carbon atom independently, and e and g are that 1-10 and f are 1-50 independently.
12. according to part 7 curable gap filler encapsulant compositions, wherein K is
Wherein, p is 1-100.
13. according to part 7 curable gap filler encapsulant compositions, wherein K is
R wherein
5, R
6And R
7Be straight or branched alkyl, alkoxyl group, alkylamine, alkyl sulfide, alkylidene group, alkylidene group oxygen base, alkylene amines, alkylidene group sulphur, aryl, aryloxy or the aryl sulphur that in chain, has about at the most 100 atoms, its chain can contain promising side chain or as saturated or the unsaturation ring or the heterocyclic substituent of a skeleton part in the chain, and any heteroatoms wherein can or cannot directly be connected with aromatic nucleus.
14. according to part 7 curable gap filler encapsulant compositions, wherein K is
15. comprising, curable gap filler encapsulant composition has molecular formula as herein described
Vinyl compound, wherein B is selected from O, C (O), O-C (O), C (O)-O, C (O) NH or C (O) N (R
8).
16. according to part 15 curable gap filler encapsulant compositions, wherein X is selected from the group of the aromatic group with following array structure:
With
17. according to part 15 curable gap filler encapsulant compositions, wherein X is:
18. according to part 15 curable gap filler encapsulant compositions, wherein Q is straight or branched alkyl, alkoxyl group, alkylidene group or the alkylidene group oxygen base that has about at the most 100 atoms in chain, its chain can contain promising side chain or as saturated or the unsaturation ring or the heterocyclic substituent of a skeleton part in the chain.
19. according to part 15 curable gap filler encapsulant compositions, wherein Q is the straight or branched alkyl that has about at the most 100 atoms in chain, its chain can contain promising side chain or as saturated or the unsaturation ring or the heterocyclic substituent of a skeleton part in the chain.
20. according to part 15 curable gap filler encapsulant compositions, wherein Q is the carbamate with following formula structure:
Wherein, R
2Be alkyl, aryl or aralkyl group independently of one another with 1-18 carbon atom; R
3Be in chain, to have the alkyl or the oxyalkyl chain of 100 atoms at the most, can contain aryl substituent in the chain; X is O, S, N or P; With n be 0-50.
21. according to part 15 curable gap filler encapsulant compositions, wherein Q is the ester with following formula structure:
R wherein
3Be to have the alkyl or the oxyalkyl chain of 100 atoms at the most in chain, its chain can contain aryl substituent.
22. according to part 15 curable gap filler encapsulant compositions, wherein Q is the siloxanes with following formula structure:
-(CR
1 2)
e-[SiR
4 2-O]
f-SiR
4 2-(CR
1 2)
g-
The R in each position wherein
1Substituting group is the R in H or the alkyl group with 1-5 carbon atom and each position independently
4Substituting group is alkyl group or the aromatic yl group with 1-5 carbon atom independently, and e and g are that 1-10 and f are 1-50 independently.
23. curable gap filler encapsulant composition comprises having molecular formula
Vinyl compound, wherein B is selected from O, C (O), O-C (O), C (O)-O, C (O) NH and C (O) N (R
8).
24. according to part 23 curable gap filler encapsulant compositions, wherein Z is straight or branched alkyl, alkoxyl group, alkylidene group or the alkylidene group oxygen base that has about at the most 100 atoms in chain, its chain can contain promising side chain or as saturated or the unsaturation ring or the heterocyclic substituent of a skeleton part in the chain.
25. according to part 23 curable gap filler encapsulant compositions, wherein Z is the straight or branched alkyl that has about at the most 100 atoms in chain, its chain can contain promising side chain or as saturated or the unsaturation ring or the heterocyclic substituent of a skeleton part in the chain.
26. according to part 23 curable gap filler encapsulant compositions, wherein Z is the carbamate with following formula structure:
Wherein, R
2Be alkyl, aryl or aralkyl group independently of one another with 1-18 carbon atom; R
3Be in chain, to have the alkyl or the oxyalkyl chain of 100 atoms at the most, can contain aryl substituent in the chain; X is O, S, N or P; With n be 0-50.
27. according to part 23 curable gap filler encapsulant compositions, wherein Z is the ester with following formula structure:
R wherein
3Be to have the alkyl or the oxyalkyl chain of 100 atoms at the most in chain, its chain can contain aryl substituent.
28. according to part 23 curable gap filler encapsulant compositions, wherein Z is the siloxanes with following formula structure:
-(CR
1 2)
e-[SiR
4 2-O]
f-SiR
4 2-(CR
1 2)
g-
The R in each position wherein
1Substituting group is the R in H or the alkyl group with 1-5 carbon atom and each position independently
4Substituting group is alkyl group or the aromatic yl group with 1-5 carbon atom independently, and e and g are that 1-10 and f are 1-50 independently.
29. according to part 23 curable gap filler encapsulant compositions, wherein K is
Wherein, p is 1-100.
30. according to part 23 curable gap filler encapsulant compositions, wherein K is
R wherein
5, R
6And R
7Be straight or branched alkyl, alkoxyl group, alkylamine, alkyl sulfide, alkylidene group, alkylidene group oxygen base, alkylene amines, alkylidene group sulphur, aryl, aryloxy or the aryl sulphur that in chain, has about at the most 100 atoms, its chain can contain promising side chain or as saturated or the unsaturation ring or the heterocyclic substituent of a skeleton part in the chain, and any heteroatoms wherein can or cannot directly be connected with aromatic nucleus.
31. according to part 23 curable gap filler encapsulant compositions, wherein K is
Claims (5)
1. curable gap filler encapsulant composition comprises maleimide compound and the curing initiator that is selected from the mixture of radical initiator, light trigger and radical initiator and light trigger, and maleimide compound has molecular formula [M-X
m]
n-Q, wherein:
(a) M is the maleimide amine moiety with following formula structure:
R wherein
1Be H or alkyl with 1-5 carbon atom;
(b) X is the aromatic yl group that is selected from the aromatic yl group with following array structure independently of one another:
With
(c) Q is straight or branched alkyl, alkoxyl group, alkylamine, alkyl sulfide, alkylidene group, alkylidene group oxygen base, alkylene amines, alkylidene group sulphur, aryl, aryloxy or the aryl sulphur that has about at the most 100 atoms in chain, its chain can contain promising side chain or as saturated or the unsaturation ring or the heterocyclic substituent of a skeleton part in the chain, and any heteroatoms wherein can or cannot directly be connected with X; Or
(d) Q is the carbamate with following formula structure:
Wherein, R
2Be alkyl, aryl or aralkyl group independently of one another with 1-18 carbon atom; R
3Be in chain, to have the alkyl or the oxyalkyl chain of 100 atoms at the most, can contain aryl substituent in the chain; X is O, S, N or P; With n be 0-50; Or
(e) Q is the ester with following formula structure:
R wherein
3Be to have the alkyl or the alkoxyl group of 100 atoms at the most in chain, its chain can contain aryl substituent; Or
(f) Q is the siloxanes with following formula structure:
-(CR
1 2)
e-[SiR
4 2-O]
f-SiR
4 2-(CR
1 2)
g-
The R in each position wherein
1Substituting group is the R in H or the alkyl group with 1-5 carbon atom and each position independently
4Substituting group is alkyl group or the aromatic yl group with 1-5 carbon atom independently, and e and g are that 1-10 and f are 1-50 independently;
(g) m is 0 or 1; With
(h) n is 1-6.
2. according to the composition of claim 1, wherein maleimide compound has molecular formula [M-Z
m]
n-K, wherein:
(a) M is the maleimide amine moiety with following formula structure:
R wherein
1Be H or alkyl with 1-5 carbon atom;
(b) Z is straight or branched alkyl, alkoxyl group, alkylamine, alkyl sulfide, alkylidene group, alkylidene group oxygen base, alkylene amines, alkylidene group sulphur, aryl, aryloxy or the aryl sulphur that has about at the most 100 atoms in chain, its chain can contain promising side chain or as saturated or the unsaturation ring or the heterocyclic substituent of a skeleton part in the chain, and any heteroatoms wherein can or cannot directly be connected with K; Or
(c) Z is the carbamate with following formula structure:
Wherein, R
2Be alkyl, aryl or aralkyl group independently of one another with 1-18 carbon atom; R
3Be in chain, to have the alkyl or the oxyalkyl chain of 100 atoms at the most, can contain aryl substituent in the chain; X is O, S, N or P; With n be 0-50; Or
(d) Z is the ester with following formula structure:
R wherein
3Be to have the alkyl or the alkoxyl group of 100 atoms at the most in chain, its chain can contain aryl substituent; Or
(e) Z is the siloxanes with following formula structure:
-(CR
1 2)
e-[SiR
4 2-O]
f-SiR
4 2-(CR
1 2)
g-
The R in each position wherein
1Substituting group is the R in H or the alkyl group with 1-5 carbon atom and each position independently
4Substituting group is alkyl group or the aromatic yl group with 1-5 carbon atom independently, and e and g are that 1-10 and f are 1-50 independently;
(f) K is the aromatic yl group that is selected from the aromatic yl group with following formula structure:
Wherein P is 1-100;
Wherein P is 1-100;
R wherein
5, R
6And R
7Be straight or branched alkyl, alkoxyl group, alkylamine, alkyl sulfide, alkylidene group, alkylidene group oxygen base, alkylene amines, alkylidene group sulphur, aryl, aryloxy or the aryl sulphur that in chain, has about at the most 100 atoms, its chain can contain promising side chain or as saturated or the unsaturation ring or the heterocyclic substituent of a skeleton part in the chain, and any heteroatoms wherein can or cannot directly be connected with aromatic nucleus; Or
R
5, R
6And R
7Be to have structure-(CR
1 2)
e-[SiR
4 2-O]
f-SiR
4 2-(CH
3)
g-siloxanes, R wherein
1Substituting group is the R in H or the alkyl group with 1-5 carbon atom and each position
4Substituting group is alkyl group or the aromatic yl group with 1-5 carbon atom independently, and e is that 1-10 and f are 1-50;
With
(g) m is 0 or 1; With
(n) n is 1-6.
3. curable gap filler composition comprises vinyl compound and the curing initiator that is selected from the mixture of radical initiator, light trigger and radical initiator and light trigger, and the vinyl compound compound has molecular formula
Wherein:
(a) R
1And R
2Be H or alkyl, or form 5-9 person's ring jointly with the carbon that forms vinyl group with 1-5 carbon atom;
(b) B is C, S, N, O, C (O), O-C (O), C (O)-O, C (O) NH or C (O) N (R
8), R wherein
8It is alkyl with 1-5 carbon atom;
(c) X is the aromatic yl group that is selected from the aromatic yl group with following array structure independently of one another:
With
(d) Q is straight or branched alkyl, alkoxyl group, alkylamine, alkyl sulfide, alkylidene group, alkylidene group oxygen base, alkylene amines, alkylidene group sulphur, aryl, aryloxy or the aryl sulphur that has about at the most 100 atoms in chain, its chain can contain promising side chain or as saturated or the unsaturation ring or the heterocyclic substituent of a skeleton part in the chain, and any heteroatoms wherein can or cannot directly be connected with X; Or
(e) Q is the carbamate with following formula structure:
Wherein, R
2Be alkyl, aryl or aralkyl group independently of one another with 1-18 carbon atom; R
3Be in chain, to have the alkyl or the alkoxyl group of 100 atoms at the most, can contain aryl substituent in the chain; X is O, S, N or P; With n be 0-50; Or
(f) Q is the ester with following formula structure:
R wherein
3Be to have the alkyl or the alkoxyl group of 100 atoms at the most in chain, its chain can contain aryl substituent; Or
(g) Q is the siloxanes with following formula structure:
-(CR
1 2)
e-[SiR
4 2-O]
f-SiR
4 2-(CR
1 2)
g-
The R in each position wherein
1Substituting group is the R in H or the alkyl group with 1-5 carbon atom and each position independently
4Substituting group is alkyl group or the aromatic yl group with 1-5 carbon atom independently, and e and g are that 1-10 and f are 1-50 independently;
(h) m is 0 or 1; With
(i) n is 1-6.
4. according to the composition of claim 1, therein ethylene based compound compound has molecular formula
Wherein:
(a) R
1And R
2Be H or alkyl, or form 5-9 person's ring jointly with the carbon that forms vinyl group with 1-5 carbon atom;
(b) B is C, S, N, O, C (O), O-C (O), C (O)-O, C (O) NH or C (O) N (R
8), R wherein
8It is alkyl with 1-5 carbon atom;
(c) Z is straight or branched alkyl, alkoxyl group, alkylamine, alkyl sulfide, alkylidene group, alkylidene group oxygen base, alkylene amines, alkylidene group sulphur, aryl, aryloxy or the aryl sulphur that has about at the most 100 atoms in chain, its chain can contain promising side chain or as saturated or the unsaturation ring or the heterocyclic substituent of a skeleton part in the chain, and any heteroatoms wherein can or cannot directly be connected with K; Or
(d) Z is the carbamate with following formula structure:
Wherein, R
2Be alkyl, aryl or aralkyl group independently of one another with 1-18 carbon atom; R
3Be in chain, to have the alkyl or the oxyalkyl chain of 100 atoms at the most, can contain aryl substituent in the chain; X is O, S, N or P; With n be 0-50; Or
(e) Z is the ester with following formula structure:
R wherein
3Be to have the alkyl or the oxyalkyl chain of 100 atoms at the most in chain, its chain can contain aryl substituent;
(f) Z is the siloxanes with following formula structure:
-(CR
1 2)
e-[SiR
4 2-O]
f-SiR
4 2-(CR
1 2)
g-
The R in each position wherein
1Substituting group is the R in H or the alkyl group with 1-5 carbon atom and each position independently
4Substituting group is alkyl group or the aromatic yl group with 1-5 carbon atom independently, and e and g are that 1-10 and f are 1-50 independently;
(g) K is the aromatic yl group that is selected from the aromatic yl group with following formula structure:
Wherein P is 1-100;
Wherein P is 1-100;
R wherein
5, R
6And R
7Be straight or branched alkyl, alkoxyl group, alkylamine, alkyl sulfide, alkylidene group, alkylidene group oxygen base, alkylene amines, alkylidene group sulphur, aryl, aryloxy or the aryl sulphur that in chain, has about at the most 100 atoms, its chain can contain promising side chain or as saturated or the unsaturation ring or the heterocyclic substituent of a skeleton part in the chain, and any heteroatoms wherein can or cannot directly be connected with aromatic nucleus; Or
R
5, R
6And R
7Be to have structure-(CR
1 2)
e-[SiR
4 2-O]
f-SiR
4 2-(CH
3)
g-siloxanes, R wherein
1Substituting group is the R in H or the alkyl group with 1-5 carbon atom and each position
4Substituting group is alkyl group or the aromatic yl group with 1-5 carbon atom independently, and e is that 1-10 and f are 1-50;
With
(h) m is 0; With
(i) n is 1-6.
5. curable encapsulant compositions comprises vinyl compound and the curing initiator described in the maleimide compound described in claim 1 or 2, the claim 3 or 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 99111272 CN1241605A (en) | 1998-07-02 | 1999-06-30 | Underfill encapsulant compositions for use in electronic devices |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US09/110,047 | 1998-07-02 | ||
| CN 99111272 CN1241605A (en) | 1998-07-02 | 1999-06-30 | Underfill encapsulant compositions for use in electronic devices |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1241605A true CN1241605A (en) | 2000-01-19 |
Family
ID=5274986
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 99111272 Pending CN1241605A (en) | 1998-07-02 | 1999-06-30 | Underfill encapsulant compositions for use in electronic devices |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1241605A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1109086C (en) * | 2000-07-19 | 2003-05-21 | 湖北省化学研究所 | Reaction-type flame-retarding adhesive for flexible PCB and its preparing process |
| CN101402775B (en) * | 2007-10-01 | 2013-01-09 | 山荣化学株式会社 | Inorganic filler and organic filler-containing curable resin composition, resist film coated printed wiring board, and method for producing the same |
-
1999
- 1999-06-30 CN CN 99111272 patent/CN1241605A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1109086C (en) * | 2000-07-19 | 2003-05-21 | 湖北省化学研究所 | Reaction-type flame-retarding adhesive for flexible PCB and its preparing process |
| CN101402775B (en) * | 2007-10-01 | 2013-01-09 | 山荣化学株式会社 | Inorganic filler and organic filler-containing curable resin composition, resist film coated printed wiring board, and method for producing the same |
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