CN1317350C - B-stageable die attach adhesives - Google Patents

B-stageable die attach adhesives Download PDF

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Publication number
CN1317350C
CN1317350C CNB2003801040805A CN200380104080A CN1317350C CN 1317350 C CN1317350 C CN 1317350C CN B2003801040805 A CNB2003801040805 A CN B2003801040805A CN 200380104080 A CN200380104080 A CN 200380104080A CN 1317350 C CN1317350 C CN 1317350C
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curable
composition
temperature
solid
under
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CN1717461A (en
Inventor
D·D·福瑞
刘圃伟
B·P·德洛斯桑托斯
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Henkel American Intellectual Property LLC
Dial Corp
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Henkel Corp
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    • H01L24/83—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector
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    • H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L24/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L24/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
    • H01L24/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
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    • H01L2224/83855—Hardening the adhesive by curing, i.e. thermosetting
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Abstract

The present invention relates to b-stageable die attach adhesives, methods of preparing such adhesives, methods of applying such adhesives to the die and other substrate surfaces, and assemblies prepared therewith for connecting microelectronic circuitry. The adhesive comprises a) a solid component heat-curable at a first temperature, b) a liquid component, which is either heat-curable at a second temperature or curable upon exposure to radiation in the electromagnetic spectrum, and c) a heat cure catalyst for the solid curable component.

Description

The B stageable die attach adhesives
The data of related application
According to 35U.S.C. § 119 (e), the application requires the right of priority of the U.S. Provisional Application No.60/428724 of submission on November 25th, 2002 to submit day to, and its disclosure is passed through with reference to introducing at this.
Background of invention
Invention field
The present invention relates to b rank small pieces (die) and connect tackiness agent, prepare the method for this tackiness agent, this tackiness agent is applied to method on small pieces and other substrate surface, with the assembly that is connected microelectronic circuit with its preparation.
The brief description of correlation technique
Bismaleimides is commercially available in occupation of important position and many bismaleimidess in the thermosetting resin field.Bismaleimides has been used to produce moulded product and adhesive bond point, heat-resisting composite, and high temperature coating.Recently, Henkel Loctite Corporation commercialization part based on many products of some bismaleimides, be used to connect semi-conductor chip to circuit card, on microelectronics industry, these products are good in the coml acceptance.In one or more United States Patent(USP) Nos.s 5789757 (Husson), 6034194 (Dershem), 6034195 (Dershem) and 6187886 (Husson), contain these products.The small pieces that are desirable to provide b rank form connect material, as the variant that its wafer applies or substrate applies.But when the reactive adhesive that distributes liquid form, when connecting tackiness agent comprising small pieces, this variant has saved existing many storages, distribution, processing and processing problems.
It is not a new commercial object that the b rank apply tackiness agent itself in advance.For example, has huge business in the screw thread snap close tackiness agent that applies in advance that HenkelLoctite uses in joint nut and bolt assembly, this tackiness agent involves (methyl) acrylate chemistry, can pass through or photo-curing mechanism, thermofixation mechanism or its combination and optional auxiliary anaerobic curing mechanism curing.Also referring to United States Patent(USP) Nos. 2928446,4325985,4632944 and 5300608.
In addition, Henkel Loctite has also designed and has developed the bottom that applies in advance and filled (underfill) capsule (referring to international patent application No.PCT/US00/07494).
Yet, up to now, do not exist based on liquid and solid curable components bonded b rank heat curable composition, perhaps be used for commercial manufacturing goods, as semi-conductor chip or semiconductor wafer, it has this b stageable die attach adhesives that is applied in advance on it, is used to safeguard that the microelectronics Packaging of flowable small pieces connection tackiness agent or assembling terminal user apply under the situation that does not need intermediate processing steps.
Summary of the invention
The present invention relates to b rank curable compositions, it is included in heat-setting solid ingredient under first temperature; Thermal curable or under second temperature when being exposed to the liquid ingredient of the radiation curable in the electromagnetic spectrum scope; With the thermal curing catalyst that is used for this solid curable components.
The present invention further provides the heat-setting method for compositions in preparation b rank, this method comprises and is provided at heat-setting solid ingredient under first temperature, thermal curable or under second temperature when being exposed to the liquid ingredient of the radiation curable in the electromagnetic spectrum scope and being used for the thermal curing catalyst of this solid curable components; Be mixed together this solid curable components, liquid curable component and thermal curing catalyst.Method herein can further comprise said composition is exposed to solidifies under the advantageous conditions the liquid curable component, said composition is exposed to be enough to make under the solid curable components fused temperature condition and said composition is exposed to be enough to make under the solid curable components solidified temperature condition of this fusing.
The present invention still further provides a kind of substrate, and to another substrate, as the method on circuit card or another chip small pieces, this method comprises and applies composition of the present invention to one of substrate as chip small pieces (chip die) adhering junction; The substrate that has applied composition is exposed under the condition that the liquid curable component that makes wherein advantageously is cured, thereby forms b rank curable film; This b rank curable film is exposed under the solid curable components fused temperature condition that is enough to make wherein; Connect each substrate, form assembly, wherein separate substrate by the composition that applies in advance; And curable film is exposed to is enough to make under the solid curable components solidified temperature condition of this fusing.
In addition or additionally, this b rank heat curable composition can be applied on suprabasil one or more metallized contact mat in advance.
The thermofixation condition of b rank film can comprise makes this assembly experience interior about 0.25 minute-Yue 2 minutes time period of temperature of about 150 ℃-Yue 200 ℃ of scopes.
The accompanying drawing summary
Fig. 1 is before assembling with substrate, the synoptic diagram of the semi-conductor chip in one embodiment of the invention.
Fig. 2 is the synoptic diagram of circuit module, and this circuit module comprises the semi-conductor chip that is assembled into suprabasil Fig. 1.
Fig. 3 is the synoptic diagram of circuit module, and this circuit module is included in the further embodiment of the present invention, is assembled into the semi-conductor chip on the chip scale package.
Fig. 4 is the synoptic diagram that the chip stacked small pieces are used.
Detailed Description Of The Invention
As the heat-setting component of solid, especially it is desirable to epoxides, episulfide, Maleimide, clothing health acid imide and endo-methylene group tetrahydrochysene O-phthalic acid imide (nadimide).
The epoxy resin that is solid state can comprise the epoxide of simple function: C4-C 28The alkyl contracting The water glycerin ether; C2-C 28Alkyl-and alkene base shrink glyceride; And C1-C 28Alkyl-and single-Phenol shrink glycerin ether; And multi-functional epoxy compound: burnt catechol, resorcinol, quinhydrones, 4,4`-dioxydiphenyl methane (or Bisphenol F, as be available commercially from Japanese Nippon Kayuku RE-303-S or RE-404-S), 4,4`-dihydroxy-3,3`-dimethyl diphenyl methane, 4,4`-Dihydroxy diphenyl dimethylmethane (or bis-phenol A), 4,4`-dihydroxy diphenylmethyl methylmethane, 4,4`-dihydroxy-phenyl-cyclohexane, 4,4`-dihydroxy-3,3`-dimethyl diphenyl propane, The polyglycidyl ether of 4,4`-dihydroxydiphenylsulisomer and three (4-hydroxyphenyl) methane; The transition metal network The polyglycidyl ether of compound; The chlorination of above-described diphenol and brominated product; Linear phenolic aldehyde The polyglycidyl ether of varnish; Many shrinks glycerine of the diphenol that the ether by the esterification diphenol obtains Ether, the ether of wherein said diphenol passes through with alkylene dihalide or dihalo alkyl ether-ether aromatics carboxylic Acid salt and obtain; Belong to by condensation phenols and the long-chain halogen alkane that contains at least two halogen atoms Hydrocarbon and the polyglycidyl ether of the polyphenol that obtains; N, the N`-diglycidylaniline; N, N`-two Methyl-N, N`-diglycidyl-4,4`-MDA; N, N, N`, N`-four shrinks Glyceryl-4, the 4`-MDA; N, N`-diglycidyl-4-aminophenyl shrinks Glycerin ether; Two-PABA N, N, N`, N`-four glycidyl group-1, the inferior propyl ester of 3-; Can Molten fusible novolac epoxy resin; Cresols can molten novolac epoxy resin; And combination.
In the middle of these solid-state commercially available epoxy resin, being applicable to of the present inventionly has: phenols chemical combination Many shrinks glyceryl derivative of thing is as with trade name EPON, such as EPON 1009F[bis-phenol A Epoxy resin (CAS No.25036-25-3)], EPON 1001F, EPON 1002F, EPON 1004F, EPON 1007F, EPON 3001, EPON 3002, EPON 2002, EPON 2003, EPON2004, EPON 2005, EPON 2012, EPON 2014, EPON 2024 and EPON 2042 Available from Resolution Performance; With trade names DER, as DER 331, DER 332, DER 383, DER 354 and DER542 are available from Dow Chemical Co.; With trade name ARALDITE, Such as ARALDITE[phenol-4,4`-two (the inclined to one side ethylidene of 1-methyl) and (chloromethyl) oxirane (CAS No.25068-38-6)], ARALDITE ECN 1299[formaldehyde, have (chloromethyl) ring The polymer of oxidative ethane and 2-methylphenol, fusing point 85-100 ℃ (CSA No.29690-82-2)] With ARALDITE ECN 1285[formaldehyde, have (chloromethyl) oxirane and 2-methylphenol Polymer, fusing point 80-90 ℃ (CSA No.29690-82-2)] and ARALDITE GT 7097 US[(phenol, 4-(1,1-dimethyl ethyl) has (chloromethyl) oxirane and 4,4`-pair The polymer of (the inclined to one side ethylidene of 1-methyl), fusing point 113-123 ℃ (CAS No.67924-34-9)) Available from New York Vantico Inc., Brewster; With with BREN available from Japanese Nippon Kayaku, Those. Other suitable epoxy resin comprises the poly-epoxidation by polyalcohol and the preparation of similar thing Many shrinks glyceryl derivative of thing and lacquer resin, wherein the latter is with trade name DEN, Be available commercially from Dow Chemical Company such as DEN431, DEN438 and DEN439.
Amine, amino alcohol and polycarboxylic many shrinks glyceryl adduct also can be used for the present invention, its Be purchased resin and comprise the Chemicals available from BP, the GLYAMINE 135 of LTD, GLYAMINE 125 With GLYAMINE 115; ARALDITE MY 720, ARALDITE available from Vantico Inc. MY721, ARALDITE MY0500 and ARALDITE MY0510.
Certainly, the combination of different rings epoxy resins also is required for herein application.
Except epoxide, same episulfide also is required, and no matter they are all or part of episulfide, condition is that they are solid-state.Episulfide can be purchased or be prepared by known synthetic method by corresponding epoxy easily.
Solid-state maleimide, endo-methylene group tetrahydro-phthalic imidine and clothing health imide comprise those compounds with following structure I, II and III respectively:
Wherein:
m＝1-15，
p＝0-15，
Each R 2Be independently selected from hydrogen or low alkyl group and
J contains the unit price of organic or organo-siloxane base or multivalence part and two or more combination wherein.
The representative more specifically of solid-state maleimide, clothing health imide and endo-methylene group tetrahydro-phthalic imidine comprises corresponding to those of structure I, II or III, wherein
m＝1-6，
p＝0，
R 2Be independently selected from hydrogen or low alkyl group and
J is unit price or multivalence group, it is selected from alkyl, substituted hydrocarbon radical, contain heteroatomic alkyl, what replace contains heteroatomic alkyl, alkylene, replace alkylene, contain heteroatomic alkylene, what replace contains heteroatomic alkylene, polysiloxane, synthesis of polysiloxane-polyurethane block copolymer, the combination of wherein two or more, described unit price or multivalence group randomly contain one or more connection bases, and described connection base is selected from covalent linkage,-O-,-S-,-NR-,-O-C (O)-,-O-C (O)-O-,-O-C (O)-NR-,-NR-C (O)-,-NR-C (O)-O-,-NR-C (O)-NR-,-S-C (O)-,-S-C (O)-O-,-S-C (O)-NR-,-S (O)-,-S (O) 2-,-O-S (O) 2-,-O-S (O) 2-O-,-O-S (O) 2-NR-,-O-S (O)-,-O-S (O)-O-,-O-S (O)-NR-, O-NR-C (O)-, O-NR-C (O)-O-,-O-NR-C (O)-NR-,-NR-O-C (O)-,-NR-O-C (O)-O-,-NR-O-C (O)-NR-,-O-NR-C (S)-, O-NR-C (S)-O-, O-NR-C (S)-NR-, NR-O-C (S)-,-NR-O-C (S)-O-, NR-O-C (S)-NR-,-O-C (S)-,-O-C (S)-O-,-O-C (S)-NR-,-NR-C (S)-,-NR-C (S)-O-,-NR-C (S)-NR-,-S-S (O) 2-,-S-S (O) 2-O-,-S-S (O) 2-NR-,-NR-O-S (O)-,-NR-O-S (O)-O-,-NR-O-S (O)-NR-,-NR-O-S (O) 2-,-NR-O-S (O) 2-O-,-NR-O-S (O) 2-NR-,-O-NR-S (O)-,-O-NR-S (O)-O-,-O-NR-S (O)-NR-,-O-NR-S (O) 2-O-,-O-NR-S (O) 2-NR-,-O-NR-S (O) 2-,-O-P (O) R 2-,-S-P (O) R 2-, NR-P (O) R 2-, wherein each R is hydrogen, alkyl or substituted alkyl and two or more combination wherein independently.
Recognize easily as those skilled in the art, when containing one or more above-described connections bases, one or more above-described unit prices or multivalence group form maleimides, when endo-methylene group tetrahydro-phthalic imidine or the imido side group of clothing health " J ", can produce various connection bases, as oxygen base alkyl, alkylthio, aminoalkyl group, carboxyalkyl, oxygen base alkenyl, the sulfo-alkenyl, amino alkenyl, the carboxyl alkenyl, oxygen base alkynyl, the sulfo-alkynyl, amino alkynyl, the carboxyl alkynyl, oxygen basic ring alkyl, the sulfo-cycloalkyl, amino cycloalkyl, the carboxyl cycloalkyl, oxygen basic ring thiazolinyl, the sulfo-cycloalkenyl group, amino cycloalkenyl group, the carboxyl cycloalkenyl group, heterocycle, oxygen base heterocycle, the sulfo-heterocycle, amino-heterocycles, the carboxyl heterocycle, oxygen Ji Fangji, thioaryl, aminoaryl, the carboxyl aryl, heteroaryl, oxygen base heteroaryl, thio ceteroary, aminoheteroaryl, the carboxyl heteroaryl, oxygen base alkaryl, the sulfo-alkaryl, amino alkaryl, the carboxyl alkaryl, oxygen base aralkyl, the sulfo-aralkyl, amino aralkyl, the carboxy arene alkyl, oxygen base aromatic yl alkenyl, the thioaryl alkenyl, the aminoaryl alkenyl, the carboxyl aromatic yl alkenyl, oxygen base alkenyl aryl, sulfo-alkenyl aryl, amino alkenyl aryl, carboxyl alkenyl aryl, oxygen base aromatic yl polysulfide yl, the thioaryl alkynyl, the aminoaryl alkynyl, the carboxyl aromatic yl polysulfide yl, oxygen base alkynyl aryl, sulfo-alkynyl aryl, amino alkynyl aryl or carboxyl alkynyl aryl, oxygen base alkylidene group, the sulfo-alkylidene group, amino alkylidenyl, the carboxyl alkylidene group, oxygen base alkenylene, the sulfo-alkenylene, amino alkenylene, the carboxyl alkenylene, oxygen base alkynylene, the sulfo-alkynylene, amino alkynylene, the carboxyl alkynylene, oxygen basic ring alkylidene group, sulfo-ring alkylidene group, amino ring alkylidene group, carboxyl ring alkylidene group, oxygen basic ring alkenylene, sulfo-ring alkenylene, amino ring alkenylene, carboxyl ring alkenylene, oxygen base arylidene, the sulfo-arylidene, amino arylidene, the carboxyl arylidene, oxygen base alkyl arylene, the alkylthio arylidene, the aminoalkyl group arylidene, the carboxyalkyl arylidene, oxygen base aryl alkylene, the thioaryl alkylidene group, the aminoaryl alkylidene group, the carboxyl aryl alkylene, oxygen Ji Fangji alkenylene, the thioaryl alkenylene, the aminoaryl alkenylene, carboxyl aryl alkenylene, oxygen base alkenyl arylidene, sulfo-alkenyl arylidene, amino alkenyl arylidene, carboxyl alkenyl arylidene, oxygen Ji Fangji alkynylene, the thioaryl alkynylene, the aminoaryl alkynylene, carboxyl aryl alkynylene, oxygen base alkynyl arylidene, sulfo-alkynyl arylidene, amino alkynyl arylidene, carboxyl alkynyl arylidene, heteroarylidene, oxygen base heteroarylidene, the sulfo-heteroarylidene, amino heteroarylidene, the carboxyl heteroarylidene, contain heteroatomic two-or multivalence loop section, contain two of oxygen heteroatom-or multivalence loop section, sulfur-bearing is heteroatomic two-or the multivalence loop section, contain amino heteroatomic two-or multivalence loop section, contain carboxyl heteroatomic two-or multivalence loop section, disulphide, sulphonamide and analogue.
In another embodiment, the maleimide, endo-methylene group tetrahydro-phthalic imidine or the clothing health imide that take in application in practice of the present invention have structure I, II or III, m=1-6 wherein, p=0-6, J is selected from straight chain saturated alkyl or branched-chain alkyl, its randomly contain the optional aryl moiety that replaces as the substituting group on alkyl chain or as a part of main chain of alkyl chain and wherein alkyl have about 20 carbon atoms at most;
Siloxanes with following structure :-(C (R 3) 2) d-[Si (R 4) 2-O] f-Si (R 4) 2-(C (R 3) 2) e-,-(C (R 3) 2) d-C (R 3)-C (O) O-(C (R 3) 2) d-[Si (R 4) 2-O] f-Si (R 4) 2-(C (R 3) 2) e-O (O) C-(C (R 3) 2) e-or-(C (R 3) 2) d-C (R 3)-O (O) C-(C (R 3) 2) d-[Si (R 4) 2-O] f-Si (R 4) 2-(C (R 3) 2) e-C (O) O-(C (R 3) 2) e-, wherein:
Each R 3Be hydrogen, alkyl or substituted alkyl independently,
Each R 4Be hydrogen, low alkyl group or aryl independently,
d＝1-10，
E=1-10 and
f＝1-50；
Polyoxyalkylene with following structure:
[(CR 2) r-O-] f-(CR 2) s-
Wherein:
Each R is hydrogen, alkyl or substituted alkyl independently,
r＝1-10，
S=1-10 and
F as defined above;
Aryl with following structure:
Figure C20038010408000181
Wherein:
Each Ar be have a 3-10 carbon atom single replace, two replace or trisubstituted aromatics or hetero-aromatic ring and
Z is:
Saturated straight chain alkylidene group or branched alkylidene, it randomly contains saturated rings part as the substituting group on alkylidene chain or as a part of main chain of alkylidene chain, or
Polyoxyalkylene with following structure:
[(CR 2) r-O-] q-(CR 2) s-
Wherein:
Each R is hydrogen, alkyl or substituted alkyl independently, r and s as defined above and
Q drops in the 1-50 scope;
Two or trisubstituted aromatics part with following structure:
Figure C20038010408000182
Wherein:
Each R is hydrogen, alkyl or substituted alkyl independently,
T drops in the 2-10 scope,
U drops in the 2-10 scope,
Ar as defined above;
Aryl with following structure:
Wherein:
Each R is hydrogen, alkyl or substituted alkyl independently,
t＝2-10，
K=1,2 or 3,
G=1-is about 50,
Each Ar as defined above,
E is-O-or-NR 5-, R wherein 5Be hydrogen or low alkyl group; With
W is straight or branched alkyl, alkylidene group, oxygen base alkylidene group, alkenyl, alkenylene, oxygen base alkenylene, ester or polyester, the siloxanes with following structure :-(C (R 3) 2) d-[Si (R 4) 2-O] f-Si (R 4) 2-(C (R 3) 2) e-,-(C (R 3) 2) d-C (R 3)-C (O) O-(C (R 3) 2) d-[Si (R 4) 2-O] f-Si (R 4) 2-(C (R 3) 2) e-O (O) C-(C (R 3) 2) e-or-(C (R 3) 2) d-C (R 3)-O (O) C-(C (R 3) 2) d-[Si (R 4) 2-O] f-Si (R 4) 2-(C (R 3) 2) e-C (O) O-(C (R 3) 2) e-, wherein:
Each R 3Be hydrogen, alkyl or substituted alkyl independently,
Each R 4Be hydrogen, low alkyl group or aryl independently,
d＝1-10，
E=1-10 and
F=1-50; Or
Polyoxyalkylene with following structure, it randomly contains the substituting group that is selected from hydroxyl, alkoxyl group, carboxyl, nitrile, cycloalkyl or cycloalkenyl group:
[(CR 2) r-O-] f-(CR 2) s-
Wherein:
Each R is hydrogen, alkyl or substituted alkyl independently,
r＝1-10，
S=1-10 and
F as defined above;
Carbamate groups with following structure:
R 7-U-C(O)-NR 6-R 8-NR 6-C(O)-(O-R 8-O-C(O)-NR 6-R 8-NR 6-C(O)) v-U-R 8-
Wherein:
Each R 6Be hydrogen or low alkyl group independently,
Each R 7Be alkyl, aryl or aralkyl independently with 1-18 carbon atom,
Each R 8For have the alkyl or the oxyalkyl chain of about 100 atoms at most in chain, it is randomly replaced by Ar,
U is-O-,-S-,-N (R)-or-P (L) 1,2-, wherein R as defined above and wherein each L be independently=O ,=S ,-OR or-R; With
V＝0-50；
Many cycloalkenyls; Or
The mixture of wherein two or more.
That certainly selects to can be used as the solid curable components contains maleimide, endo-methylene group tetrahydro-phthalic imidine and the imido compound of clothing health, so that they are 90 ℃ to 160 ℃ for solid-state and fusing point.
Especially required maleimide as solid ingredient in the b stageable die attach adhesives of the present invention comprises for example having the maleimide of following structure:
Figure C20038010408000211
As the liquid curable component, especially required is epoxide, episulfide, maleimide, endo-methylene group tetrahydro-phthalic imidine, clothing health imide, (methyl) acrylate, maleic acid ester, fumarate, Vinyl Ether, vinyl acetate, allyl group acid amides, vinylbenzene and derivative thereof, poly-(alkenylene), norbornene, thiol-ene (thiolene) and analogue.
Spendable herein liquid epoxide comprises equally with trade(brand)name EPON, is available commercially from those of Resolution Performance as EPON825, EPON826, EPON828, EPON862, EPON8019, EPON8101, EPON8112, EPON813, EPON8131, EPON8132, EPON8133, EPON815C and EPON824.
For containing maleimide, endo-methylene group tetrahydro-phthalic imidine and/or the imido compound of clothing health, if contain maleimide, the functional group of endo-methylene group tetrahydro-phthalic imidine and/or the imido compound of clothing health is connected respectively on the monoradical J, perhaps separately by multivalence group J, each monoradical or multivalence group have enough length and the feasible maleimide that contains of the degree of branching, endo-methylene group tetrahydro-phthalic imidine and/or the imido compound of clothing health are liquid, and then this compound is suitable for use as the liquid curable component.
Contain in the enumerating more specifically of maleimide, endo-methylene group tetrahydro-phthalic imidine and/or the imido compound of clothing health at structure I, II and III this, each R is hydrogen or low alkyl group independently,-J-comprises branched-chain alkyl, alkylidene group or alkylidene oxide material, it has enough length and the degree of branching makes that maleimide, endo-methylene group tetrahydro-phthalic imidine and/or clothing health imide compound are liquid, with m be 1,2 or 3.
The maleimide that contains that can be used as liquid ingredient of the present invention; endo-methylene group tetrahydro-phthalic imidine or the imido compound of clothing health can be selected from United States Patent(USP) Nos. 5789757 (Husson); 6034194 (Dershem); describe among 6034195 (Dershem) and 6187886 (Husson) and claimed those; the disclosure of each piece is introduced by reference at this; with United States Patent(USP) Nos. 6063828 (Ma); 6265530 (Herr); described in 6281314 (Tong) and 6136566 (Ma) those, the disclosure of each piece are introduced by reference at this equally.
Can from many different compounds, select (methyl) acrylate.As used herein, with regard to monomer with contain monomeric component, use term (methyl) vinylformic acid and (methyl) acrylate with the free burial ground for the destitute.Term (methyl) vinylformic acid and (methyl) acrylate comprise those vinylformic acid, methacrylic acid, acrylate and methacrylic ester.
(methyl) acrylate component can comprise one or more members that are selected from the monomer that following formula represents:
Figure C20038010408000231
Wherein G is hydrogen, halogen or the alkyl with 1-4 carbon atom, R 1Have 1-16 carbon atom and be alkyl, cycloalkyl, alkenyl, cycloalkenyl group, alkaryl, aralkyl or aryl, it is randomly replaced by silane, silicon, oxygen, halogen, carbonyl, hydroxyl, ester, carboxylic acid, urea, urethanum, carbamate, amine, acid amides, sulphur, sulphonate or sulfone or inserts;
Urethane acrylate that following formula is represented or uride acrylate:
Figure C20038010408000232
Wherein:
G is hydrogen, halogen or the alkyl with 1-4 carbon atom;
R 8Expression by-O-atom and-divalent aliphatic of the one or more carbon atom bondings shown in X-atom or the group place, alicyclic, aromatics or araliphatic group;
X is-O-,-NH-or-N (alkyl)-, wherein alkyl has 1-8 carbon atom;
Z is 2-6; With
R 9Be, aromatics alicyclic to the z valency on one or more NH bases or araliphatic group by one or more carbon atom bondings; With
Be selected from following two-or three-(methyl) acrylate: polyoxyethylene glycol two (methyl) acrylate, dihydroxyphenyl propane two (methyl) acrylate, tetrahydrofuran (THF) two (methyl) acrylate, hexylene glycol two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate or its combination.
Suitable polymerisable (methyl) acrylate monomer comprises triglycol two (methyl) acrylate, tripropylene glycol two (methyl) acrylate, Tetraglycol 99 two (methyl) acrylate, glycol ether two (methyl) acrylate, 1,4-butyleneglycol two (methyl) acrylate, 1,6-hexylene glycol two (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, Dipentaerythritol monohydroxy five (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, dihydroxyphenyl propane b-oxide two (methyl) acrylate, TriMethylolPropane(TMP) b-oxide three (methyl) acrylate, TriMethylolPropane(TMP) propoxide three (methyl) acrylate and dihydroxyphenyl propane diepoxide two (methyl) acrylate.
In addition, can use (methyl) acrylate monomer of simple function, comprising tetrahydrofuran (THF) (methyl) acrylate and two (methyl) acrylate, (methyl) vinylformic acid citronellyl acrylate, (methyl) Propylene glycol monoacrylate, (methyl) vinylformic acid tetrahydrochysene dicyclopentadienyl ester, triglycol (methyl) acrylate, triglycol (methyl) acrylate and combination thereof.
Certainly, also can use (methyl) acroleic acid esterification siloxanes, condition is when solidified, and siloxane main chain does not have to get final product to the effect that minimizes (methyl) acrylate greatly.
Be applicable to that other (methyl) acrylate herein is included in disclosed in the U.S. Patent No. 6211320 (Dershem) and claimed low viscous acrylate, its disclosure is specially introduced by reference at this.
Fumarate comprises those that contain following formula:
Figure C20038010408000241
Maleic acid ester comprises those that contain following formula:
Figure C20038010408000242
For fumarate and maleic acid ester each, R can be from the R of above definition 1The middle selection.
Vinyl ether and vinyl ester comprise those that contain following formula:
Figure C20038010408000243
Wherein
Q is 1,2 or 3,
Each R is independently as above R 1In definition, each Q is independently selected from-O-,-O (O) C-,-C (O)-or-C (O)-O-and
Y the same with respect to X definition among structure I, II and the III.
The vinyl ether that is comprised by above formula and the example of vinyl ester comprise, stearyl vinyl ether, docosyl vinyl ether or ester, eicosyl vinyl ether or ester, Isoeicosane base vinyl ether or ester, isotetracosane base vinyl ether or ester, poly-(tetrahydrofuran (THF)) divinyl ether or ester, Tetraglycol 99 divinyl ether or ester, three-2,4,6-(1-vinyl oxygen base butane-)-4-Oxy-1,3,5-triazine, two-1, (1-vinyl oxygen base butane-4-)-oxygen base carbonyl benzene (or is called two (4-vinyl oxygen Ji Dingji) isophthalic acid esters to 3-; With trade(brand)name VECTOMER4010 available from Allied-Signal Inc., Morristown, NJ), the divinyl ether by the preparation of the vinyl permutoid reaction between the glycol of low-stage ethylene base ether and higher molecular weight.Required especially divinyl resin comprises stearyl vinyl ether or ester, docosyl vinyl ether or ester, eicosyl vinyl ether or ester, Isoeicosane base vinyl ether or ester, poly-(tetrahydrofuran (THF)) divinyl ether or ester, the divinyl ether by the preparation of the vinyl permutoid reaction between the glycol of low-stage ethylene base ether and higher molecular weight.
As the allyl group acid amides, can select all cpds, as satisfying those of the above criterion that " J " in maleimide, endo-methylene group tetrahydro-phthalic imidine and/or the clothing health imide listed.For example, in enumerating more specifically, corresponding to those of following structure:
Wherein
R` is hydrogen, C 1-Yue C 18Alkyl or oxygen base alkyl, allyl group, aryl or substituted aryl,
M be 1-6 and
X such as above definition to J.
Contain cinnamic component and comprise those that contain following formula, it is connected on the X defined above:
Wherein n is 1-6.
The norbornene component comprises those that contain following formula, and it is connected on the X defined above:
Figure C20038010408000261
Wherein m is 1-6.
The thiol-ene component comprises those that contain following formula, and it is connected on the X defined above:
Wherein m is 1-6.
First temperature when solid ingredient is curable should more than or equal to the solid ingredient fusion-that is, from solid-state temperature (or temperature range) when becoming liquid state.In general, this temperature should be higher than about 100 ℃ but it is desirable to temperature in about 100 ℃-Yue 300 ℃ of scopes.When within the scope of the present invention composition of preparation, one group of specific especially therein physical function parameter be required or situation about being prescribed under, these differing temps scopes provide the possibility of makers-up's wide region.
Thermal curing catalyst can be included in the composition, the temperature when reduce to solidify taking place or be selected for when taking place to solidify the reinforcement state of cure when suitable temperature condition.
Thermal curing catalyst can be selected from free radical catalyst, negatively charged ion solidifying agent, cation curing agent and combination thereof.For example, free radical catalyst can be selected from superoxide, azo-compound and combination thereof.Especially the peroxide catalyst of ideal comprises dicumyl peroxide, dibenzoyl peroxide, peroxidation 2-butanone, t-butylperoxyl benzoate, di-t-butyl peroxide, 2, two (t-butyl peroxy)-2 of 5-, 5-dimethylhexane, two (t-butyl peroxy sec.-propyl) benzene and tertbutyl peroxide, comprise 2 with azo-compound, 2`-azo two (2-methyl propionitrile), 2,2`-azo two (2-methylbutyronitrile) and 1,1`-azo two (cyclohexanenitrile).
The commercially available example of these free radical catalysts comprises those that promoted by Akzo Nobel, as following superoxide diisobutyryl peroxide (CAS No.3437-84-1), cross the withered ester of neodecanoic acid (CAS No.36748-47-0), cross two carbonate mixtures (CAS No.105-64-6; 19910-65-7; 78350-78-4); cross neodecanoic acid 2; 4; 2-trimethylammonium 2-pentyl ester (CASNo.51240-95-0); cross the withered ester of new enanthic acid (CAS No.68299-16-1); cross two carbonic acid di-secondary butyl esters (CAS No.19910-65-7); cross the neodecanoic acid tert-butyl ester (CAS No.26748-41-4); cross two dibutyl carbonates (CAS No.16215-49-9); cross two carbonic acid, two cetyl (CASNo.26332-14-5); cross two carbonic acid two (4-tertiary butyl cyclohexyl) (CASNo.15520-11-3); cross two carbonic acid two (2-ethylhexyl) (CAS No.16111-62-9); cross two carbonic acid, two myristins (CAS No.53220-22-7); cross the new enanthic acid tert-butyl ester (CASNo.26748-38-9); cross PIVALIC ACID CRUDE (25) tert-pentyl ester (CAS No.29240-17-3); cross the PIVALIC ACID CRUDE (25) tert-butyl ester (CAS No.927-07-1); peroxidation two-(3; 5; the 5-trimethyl acetyl) (CASNo.3851-87-4); dilauroyl peroxide (CAS No.105-74-8), dioctanoyl peroxide (CAS No.762-16-3), didecanoyl peroxide (CAS No.762-12-9); 2; 5-dimethyl-2,5-two (2-ethyl hexanoyl base peroxide) hexane (CAS No.13052-09-0), peroxide-2 ethyl hexanoic acid tert-pentyl ester (CAS No.686-31-7); peroxide-2 ethyl hexanoic acid the tert-butyl ester (CASNo.3006-82-4); dibenzoyl peroxide (CAS No.94-36-0), 1,1-two (t-butyl peroxy)-3; 3; 5-trimethyl-cyclohexane (CAS No.6731-36-8), 2,2-two [4; 4-two-(t-butyl peroxy cyclohexyl) propane] (CAS No.1705-60-8); 1,1-two (tert-pentyl peroxide)-hexanaphthene (CAS No.15667-10-4), 1; 1-two (t-butyl peroxy)-hexanaphthene (CASNo.3006-86-8); peroxide-2-ethylhexyl carbonic acid tert-pentyl ester (CAS No.70833-40-8), peroxide-3,5; the 5-tri-methyl hexanoic acid tert-butyl ester (CAS No.13122-18-4); peroxide-2-tolyl acid the tert-butyl ester (CAS No.22313-62-8), 2,2-two (t-butyl peroxy) butane (CASNo.2167-23-9); the peroxy isopropyl base carbonic acid tert-butyl ester (CAS No.2372-21-6); the peroxide 2-ethylhexyl carbonic acid tert-butyl ester (CAS No.34443-12-4), peroxybenzoic acid tert-pentyl ester (CASNo.4511-39-1), t-butyl peroxy-acetate (CAS No.107-71-1); 4; 4-two (t-butyl peroxy) butyl valerate (CAS No.995-33-5), t-butylperoxyl benzoate (CASNo.614-45-9), peroxidation two tert-pentyls (CAS No.10508-09-5); dicumyl peroxide (CAS No.80-43-3); two (t-butyl peroxy sec.-propyl) benzene (CASNo.25155-25-3), 2,5-dimethyl-2; 5-two (t-butyl peroxy) hexane (CASNo.78-63-7); tert-butyl peroxide cumyl (CAS No.3457-61-2), 2,5-dimethyl-2; 5-two (t-butylperoxy) hexin-3 (CAS No.1068-27-5); di-t-butyl peroxide (CAS No.110-05-4), 3,6; 9-triethyl-3; 6,9-trimethylammonium-1,4; 7-three peroxonane (CAS No.24748-23-0); 1,1,3; 3-tetramethyl butyl hydroperoxide (CAS No.5809-08-5); diisopropyl benzene list hydroperoxide (CASNo.26762-93-6), cumyl hydroperoxide (CAS No.80-15-9), tert-butyl hydroperoxide (CAS No.75-91-2); and t-amyl hydroperoxide (CAS No.3425-61-4); with following azo-compound 2, two (isopropyl cyanide) (the CAS No.78-67-1) of 2`-azo, 2; two (2-methylbutyronitrile) (the CAS No.13472-08-7) and 1 of 2`-azo, two (1-cyclohexanenitrile) (the CAS No.2094-98-6) of 1`-azo.
Thermal curing catalyst also can be the negatively charged ion solidifying agent, as broadly be described as nitric heterocyclic compound, amine compound, amide compound, imidazolium compounds and bonded thereof those.The more specifically example of nitric heterocyclic compound comprises:
1,5-diazabicyclo [4.3.0] ninth of the ten Heavenly Stems-5-alkene
1,8-diazabicyclo [5.4.0] undecane-5-alkene (DBU)
Figure C20038010408000283
1,5,7-three azabicyclos [4.4.0] last of the ten Heavenly stems-5-alkene
Figure C20038010408000291
Rubane
1,4-diazabicyclo [2.2.2] octane
The more specifically example of amine compound comprises aliphatic polyamines, aromatic polyamine, alicyclic polyamine, as diethylenetriamine, Triethylenetetramine (TETA), diethyl amino propylamine, benzyldimethylamine, m-xylene diamine, diamino-diphenylamine, quinoxaline, isophorone diamine,  alkene menthene diamines and combination thereof.
The example more specifically of amide compound is functionalized acid amides, Dyhard RU 100.
The example more specifically of imidazolium compounds comprises different imidazoles, imidazoles, 2-ethyl-4-methylimidazole, 2, the 4-methylimidazole, butyl imidazole, 2-heptadecene base-4-methylimidazole, glyoxal ethyline, 2-undecenyl imidazoles, 1-vinyl-glyoxal ethyline, the 2-undecyl imidazole, 2-heptadecyl imidazoles, the 2-phenylimidazole, 1 benzyl 2 methyl imidazole, 1-propyl group-glyoxal ethyline, the 1-1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecyl imidazole, 1-cyanoethyl-2-phenylimidazole, 1-guanamines base ethyl-glyoxal ethyline, the adduct of imidazoles and Methylimidazole, the adduct of imidazoles and trimellitic acid, 2-n-heptadecane base-4-methylimidazole, phenylimidazole, benzyl imidazole, 2-methyl-4, the 5-diphenyl-imidazole, 2,3,5-triphenyl imidazoles, 2-styryl imidazoles, 1-(dodecylbenzyl)-glyoxal ethyline, 2-(2-hydroxyl-4-tert-butyl-phenyl)-4, the 5-diphenyl-imidazole, 2-(2-p-methoxy-phenyl)-4, the 5-diphenyl-imidazole, 2-(3-hydroxyphenyl)-4, the 5-diphenyl-imidazole, 2-(to dimethylaminophenyl)-4, the 5-diphenyl-imidazole, 2-(2-hydroxyphenyl)-4, the 5-diphenyl-imidazole, two (4,5-phenylbenzene-2-imidazoles)-benzene-1,4,2-naphthyl-4, the 5-diphenyl-imidazole, 1 benzyl 2 methyl imidazole, 2-is to methoxyl-styrene imidazoles and combination thereof.
Thermal curing catalyst also can be a cation curing agent, as broadly be described as organic acid, acid anhydrides and lewis acidic those.Organic acid comprises phenols, thiophenol, mercaptan, carboxylic acid and combination thereof.Acid anhydrides especially comprises hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, 5-(2,5-dioxy base tetrahydrochysene)-3-methyl-3-tetrahydrobenzene-1,2-carboxylic acid anhydride, and combination.Lewis acid comprises known in the art as lewis acidic various materials, and the example is phosphine, alkylogen, phosphoric acid ester, boron trifluoride etherate and analogue.
Liquid ingredient or be different from thermal curable under second temperature of first temperature perhaps ought be exposed to the radiation curable in the electromagnetic spectrum.Second temperature usually in about 50 ℃-Yue 150 ℃ of scopes, but ideally temperature less than about 100 ℃.
As mentioned above, another thermal curing catalyst can be included in the said composition temperature when reducing liquid ingredient and take place to solidify or be selected for when curing takes place accelerating liquid component solidified degree when suitable temperature condition.Those thermal curing catalysts of more than quoting are suitable as another thermal curing catalyst, and condition is the reaction of their catalytic fluid components under specified temperature or reacts with liquid ingredient.
Under the situation of solidified liquid component, light trigger also should be included in the said composition wishing for some commercial applications by being exposed under the radiation in the electromagnetic spectrum.Should be conceived to the radiation scope selective light initiator in the electromagnetic spectrum in the time will causing curing.For example, suitable radiation scope comprises UV, UV/VIS, VIS, IR, electron beam, X-ray and microwave radiation line in electromagnetic spectrum.
The representative example of UV and UV/VIS light trigger comprises with trade(brand)name " IRGACURE " and " DAROCUR " and is available commercially from Ciba Specialty Chemicals, Tarrytown, those of New York, be in particular " IRGACURE " 184 (1-hydroxycyclohexylphenylketone), 907 (2-methyl isophthalic acids-[4-(methylthio group) phenyl]-2-morpholinyl third-1-ketone), 369 (2-benzyl-2-N, N-dimethylamino-1-(4-morpholinyl phenyl)-1-butanone), 500 (combinations of 1-hydroxycyclohexylphenylketone and benzophenone), 651 (2,2-dimethoxy-2-phenyl acetophenone), 1700 (two (2,6-dimethoxy benzoyl-2,4, the combination of phosphine oxide and 2-hydroxy-2-methyl-1-phenyl-third-1-ketone) and 819[two (2 the 4-tri-methyl-amyl), 4, and " DAROCUR " 1173 (2-hydroxy-2-methyl-1-phenyl-1-propane) and 4265 (2 6-trimethylbenzoyl phenyl phosphine oxide)], 4, the combination of 6-trimethylbenzoyl diphenyl phosphine oxide and 2-hydroxy-2-methyl-1-phenyl-third-1-ketone); And visible light [indigo plant] light trigger, d1-camphorquinone and " IRGACURE " 784DC.Certainly, also can use the combination of these materials herein.
Other light trigger that can be used for herein comprises pyruvic acid alkane ester, as Pyruvic Acid Methyl ester, ethyl ester, propyl ester and butyl ester and pyruvic acid aromatic ester, as phenyl ester, benzyl ester and its suitable substitutive derivative.
The light trigger that is particularly suited for herein using comprises ultraviolet initiator; as 2; the 2-dimethoxy-the 2-phenyl acetophenone (for example; " IRGACURE " 651); with the 2-hydroxy-2-methyl-the 1-phenyl-1-propane (for example; " DAROCUR " 1173); two (2,4, the 6-trimethylbenzoyl) phenyl phosphine oxide (for example; " IRGACURE " 819); with two (2,6-dimethoxy benzoyl-2,4; the 4-tri-methyl-amyl) combination of the ultraviolet initiator of phosphine oxide and 2-hydroxy-2-methyl-1-phenyl-third-1-ketone (for example; and two (5-2, the 4-cyclopentadiene-1-yl)-two [2 of visible light initiator " IRGACURE " 1700); 6-two fluoro-3-(1H-pyrroles-1-yl) phenyl] titanium (for example, " IRGACURE " 784DC).
Can from trade(brand)name " ESACURE " and " SARCAT " available from Sartomer, Inc., Exton selects extra light trigger in those of Pennsylvania.Example comprises " ESACURE " KB1 (benzil dimethyl ketal), " ESACURE " EB3 (mixture of bitter almond oil camphor and butyl ether), " ESACURE " TZT (blend of trimethylammonium benzophenone), " ESACURE " KIP100F (hydroxyketone), " ESACURE " KIP150 (polymkeric substance hydroxyketone), " ESACURE " KT37 (blend of " ESACURE " TZT and KIP150), " ESACURE " KT046 (triphenylphosphine oxide, the blend of " ESACURE " KIP150 and TZT), " ESACURE " X33 (2-and 4-isopropyl thioxanthone, the blend of 4-(dimethylamino) ethyl benzoate and " ESACURE " TZT).
Certainly, skilled those skilled in the art can optionally use the combination of this light trigger.
In addition, light trigger can be a cation light initiator, in case be exposed under the suitable radiation condition liquid ingredient polymerization of its energy catalysis present composition.Be used for required cation light initiator of the present invention and comprise triarylsulfonium salt and the diaryl group iodized salt that contains non-nucleophilic counter ion, with aryl two nitrogen salts, the example comprises 4-anisole phosphofluoric acid two nitrogen salts, benzene Tetrafluoroboric acid two nitrogen salts, the phenylbenzene iodine chloride, phenylbenzene phosphofluoric acid salt compounded of iodine, 4,4-dioctyl oxygen base phenylbenzene phosphofluoric acid salt compounded of iodine, triphenyl Tetrafluoroboric acid sulfonium salt, diphenylmethyl phenyl phosphofluoric acid sulfonium salt, phenyl xylyl hexafluoroarsenate sulfonium salt, with phenylbenzene sulfo-Phenoxyphenyl hexafluoro-antimonic acid sulfonium salt, with be available commercially from those of Sartomer, as " SARCAT " CD1010[triaryl hexafluoro-antimonic acid sulfonium salt (50% Texacar PC)], " SARCAT " DC1011[triaryl phosphofluoric acid sulfonium salt (the inferior n-propyl of 50% carbonic acid)], " SARCAT " DC1012[diaryl hexafluoro-antimonic acid salt compounded of iodine], " SARCAT " K185[triaryl phosphofluoric acid sulfonium salt (50% Texacar PC)].
Based on the gross weight of composition, this heat-setting composition in b rank can further comprise the filler in about 20-90wt% scope.
The filler that takes in practice of the present invention randomly can be conduction (conduction and/or heat conduction) filler.
The conductive filler material that takes in practice of the present invention comprises, the graphite of the graphite of silver, nickel, gold, cobalt, copper, aluminium, graphite, silver coating, nickel coating for example, and the alloy of this metal, and analogue, with and composition thereof.Can use the filler of powder and laminar form herein.During sheet form, the thickness of filler can be less than about 2 microns, and wherein planar dimension is about 25 microns of about 20-.The surface-area of thin slice as used herein can be about 0.15-5.0m 2/ g and bulk density are the about 5.5g/cc of about 0.4-.During powder type, the diameter of filler particles can be about 0.5-30 micron, 20 microns according to appointment.
The heat conductive filler that takes in practice of the present invention comprises, for example aluminium nitride, boron nitride, silicon carbide, diamond, graphite, beryllium oxide, magnesium oxide, silicon oxide, aluminum oxide and analogue.
Conduction and/or heat conductive filler be by the mixture process with sequestrant, reductive agent, non-ionic lubricant or this reagent, should make the metal ion that is substantially free of catalytic activity.This processing is disclosed in the U.S. Patent No. 5447988, specially it is introduced by reference at this in full.
Randomly, except conductive fillers or as Gong the alternate scheme of conductive fillers, also can use both non-conductive, also athermanous filler.This filler can be given the physicals of prescription some other requiredly, for example thermal expansion that reduces of curing composition, the specific inductivity of reduction, improved toughness, hydrophobicity of increase or the like.The example of this filler comprises perfluorinated hydrocarbon polymkeric substance (that is, TEFLON), thermoplastic polymer, thermoplastic elastomer, mica, fumed silica, glass powder, spacer element or the like.
Can be in the process of using this integrated package, can realizing between chip small pieces and the substrate fully bonding and any thickness or the consumption of suitable performance be provided betwixt, the heat-setting composition in b rank is applied in advance or (a) at least a portion apparent surface of circuit chip go up or (b) on the adhesive pad of at least a portion substrate.
Said composition can be substantially free of non-reactive solvent or thinner, or depends on and can comprise non-reactive solvent or thinner by employed composition.When adding thinner, required is that thinner is a reactive diluent, and it combines with the compound that contains maleimide, forms compositions of thermosetting resin.This reactive diluent comprises simple function and multi-group alcohol's acrylate and methacrylic ester, herein than the vinyl compound that describes in greater detail, styrene monomer (that is, be derived from vinyl benzyl chloride with single-, two-or the ether of the oxy-compound reaction of trifunctional) and analogue.
The coupling agent that exemplifies that takes in practice of the present invention comprises silicon ester, metal acrylate salt (for example aluminium methacrylate), titanic acid ester (for example methacryloxyethyl etheric acid three titanium isopropylates), but or contain the compound (for example, phosphine, mercaptan, acetylacetic ester and analogue) of copolymerization group and chelating ligand.In general, use at least a coupling agent (based on the gross weight of organic phase) in about 0.1-10wt% scope, wherein preferably in about 0.5-2wt% scope.
But some required coupling agents contain the functional group's (for example vinyl segment, acrylate part, methacrylic acid ester moiety, vinylbenzene part, cyclopentadiene part or the like) and the silicon ester functional group of copolymerization.Silicon ester in coupling agent part can with the metal hydroxides condensation on the mineral surface that is present in substrate, but the functional group of copolymerization simultaneously can with other reactive component copolymerization in the binder composition of the present invention.An example of this coupling agent is an oligomeric silicic acid ester coupling agent, as poly-(methoxy-ethylene radical siloxane).
Other especially required coupling agent comprises those that show with following structural table:
A a-L-Z b
Wherein each A is the group of free redical polymerization independently, and each L is covalent linkage or multivalence organic group independently; Each Z is the reactive part that forms hydrogen bond and/or covalent linkage with the substrate that has free hydroxyl group in its surface independently, and a is that 1-200 and b are 1-200.
The group A of free redical polymerization, comprise the optional maleimide that replaces, the optional vinyl ether that replaces, the optional vinyl thioether that replaces, the optional vinyl ester that replaces, the optional fumarate that replaces, the optional vinyl thioesters that replaces, the optional diallyl acid amides that replaces, the optional styrenic functionality that replaces, optional polybutadiene-base that replaces or the like.When passing through the free radical inhibitors catalysis of a small amount of, these functional groups can be by free radical mechanism and bismaleimides or acrylate resin system co-curing.Perhaps, under the situation of not using radical initiator, if this system is exposed under solidification value, ultraviolet radiation or the analogue of rising, this functional group also can with maleimide or acrylate resin system co-curing.
B of the present invention rank heat curable composition can further contain other additive, as defoamer, flow agent, dyestuff and pigment.
With reference to the accompanying drawings, wherein in several width of cloth views, similarly marker characteristic is meant similar parts, and Fig. 1 and 2 has described circuit module 50.In general, circuit module 50 comprises that small pieces connection tackiness agent is applied to semi-conductor chip and carrier substrates such as the circuit board substrate 70 on the small pieces dorsal part 60 in advance.
Circuit chip 60 comprises chip small pieces 62.Chip small pieces 62 can be by any material manufacturing known in the art.For example, chip small pieces 62 can be by silicon, germanium or analogue manufacturing.Chip small pieces 62 also available energy suppress the passivating material of environmental corrosion, for example polyimide-, polyphenyl and tetramethylene-or silicon nitride-based material coating.
Substrate 70 also can be by any material manufacturing known in the art.For example, substrate 70 can be by ceramic bases (comprising Al 2O 3, silicon nitride (SiN 3) and mullite (Al 2O 3-SiO 2)); The substrate of heat stable resin such as polyimide or ribbon; At the bottom of the glass enhanced epoxy group(ing); Acrylonitrile-butadiene-styrene (ABS) (ABS) substrate; With the resol substrate, plate the metallic substance of Ag, Pd, flash distillation Au etc. such as the substrate that Cu, Alloy42 etc. make by having various surface finishing agents such as point-like.Substrate 70 is included in the circuit on the substrate surface 74, comprising a plurality of circuit adhesive pads 76.
Chip small pieces 62 comprise the first and second relative surfaces, comprising chip surface 64 as first surface be connected the surface 68 as second surface.Provide circuit on chip surface 64, wherein affiliated chip surface 64 comprises a plurality of circuit contact mats, and as metallized adhesive pad 66, it is with predetermined arranged in patterns.These electrical contact pads can be connected on the adhesive pad 76 of substrate 70.By each contact mat 66 on the chip small pieces 62 and the bonding between the contact mat 76 in the substrate 70 (for example setting up), thereby be provided at circuit and being electrically connected and engagement (engagement) between the circuit in the substrate 70 on the chip small pieces 62 by wiring 80.Can after solidifying small pieces connection material, to contact mat 76, be electrically connected thereby set up by bonding wiring 80.Although in order to describe the present invention, accompanying drawing of the present invention has been described be bonded on the chip small pieces 62 two wirings 80 and two corresponding contact mats 76 in substrate 70, but the quantity that is appreciated that wiring bonding and contact mat 76 can change according to the ad hoc structure of specific required application and circuit chip and concrete structure described herein not will be understood that it is restriction the present invention.
In the present invention, chip small pieces 62 are included in the metallized electrical pickoff that is contact mat 66 forms on the chip surface 64 and are included in before chip small pieces 62 and substrate 70 assemblings, are applied to the b stageable die attach adhesives 90 on the relative connection surface 68 in advance.After under being exposed to suitable condition of cure, b rank small pieces connection material 90 provides has the circuit module 50 that high bond strength is adhered in the substrate 70 for chip small pieces 62.In general, be enough to promote b stageable die attach adhesives 90 to carry out under the temperature condition that b rank solidified raises, connect for chip small pieces 62 and be adhered in the substrate 70 by the completely solidified material that forms solid form, thereby take place this bonding by being exposed to.
The present invention further provides the circuit module 50 of assembling form, as shown in Figure 2, its chips small pieces 62 link to each other with substrate 70, and are exposed under the appropriate condition, cause that b stageable die attach adhesives 90 connects chip small pieces 62 and is adhered in the substrate 70.In addition, chip small pieces 62 then can with substrate 70 by being electrically connected of between contact mat 66 and contact mat 76, setting up, for example by welding or otherwise bonding wiring 80 betwixt, thereby be electrically connected.
In one embodiment, therefore the present invention provides the manufacturing goods of chip small pieces form, first surface that can provide with another chip small pieces of planning to be electrically connected or the engagement of carrier substrates electricity is provided for it, with with the first surface opposing second surface, and have b stageable die attach adhesives at least a portion of being placed in one.Directly on the chip die surfaces, provide b stageable die attach adhesives, saved adjust volume and temperature the production problem and deposit, processing and shelf lives problem, these are equally usually with flowing or the small pieces of liquid connect tackiness agent and consider.That is to say that the terminal user no longer needs to use complicated adjustment equipment and cryogenic storage container to be used to apply this material.In addition, the terminal user now can used according to the invention or semi-conductor chip or semiconductor wafer, described semi-conductor chip or semiconductor wafer have and are applied to the wherein lip-deep b stageable die attach adhesives of at least a portion in advance, and are more prone to and increase output ground assembled semiconductor device.
The package design technical requirements that the semi-conductor chip that applies in advance with the b stageable die attach adhesives also can make the final user implement more to seal.That is to say that owing to is connected tackiness agent with many known small pieces and compares, therefore the outflow from this b stageable die attach adhesives and ooze out decline can be implemented in the tolerance limit (tolerance) that more seals between die edge and the bonding point.In addition, existing stackable semiconductor chip so that the total size of semiconducter device can descend, perhaps keeps identical at least basically, but can significantly increase the performance of stacked semi-conductor chip on length and width.Referring to, for example United States Patent(USP) Nos. 5323060,5286679,5140404 and 6465893, each piece disclose heat-resisting at this by with reference to introducing.
In addition, the small pieces of many routines connect tackiness agent to be benefited from the machining control of more sealing and avoids joint-cutting wriggling in the thin small pieces process of bonding and the adhesive pad that contact to pollute, but when use b stageable die attach adhesives of the present invention, does not need this protection.Moreover it provides much bigger design flexibility of package design teacher and ability.
B stageable die attach adhesives of the present invention can apply by ornamental engraving printing, screen printing or spraying.
Under the situation of the wafer of precut, wafer can connect adhesive coated with small pieces of the present invention equably, solidifies afterwards at ornamental engraving printing or screen printing.In the wafer cutting process, the sawdust of cutting cuts by the solidified small pieces fully then and connects binder layer and wafer.
Arrive under the situation of the wafer that cuts in ornamental engraving printing or screen printing, make ornamental engraving or screen cloth and have the hole that the part of being designed to is coated with single small pieces or semi-conductor chip.Specifically, use the grid of ornamental engraving or screen cloth, the original place is kept small pieces of the present invention and is connected tackiness agent.That is to say that do not wish that small pieces connect tackiness agent and enter in the street (street) of cutting, this will help the small pieces in the small pieces placement process to separate.The width of planning grid, perhaps opposite, the size of hole so that after small pieces are arranged, can realize the wet tack line of target, is connected tackiness agent can form desired height below small pieces rule (fillet) with small pieces.
Under ornamental engraving printing or the screen printing situation on the laminated substrates, make the hole that ornamental engraving or screen cloth have the part of being designed to coating die pad, specifically, after small pieces are arranged, use the grid of ornamental engraving or screen cloth, the original place is kept small pieces and is connected tackiness agent.The width of planning grid, perhaps opposite, the size of hole is so that after small pieces are arranged, can realize the wet tack line of target, be connected tackiness agent with small pieces and can below small pieces, form the rule of desired height and have minimum to not connected the wetting of tackiness agent by the small pieces of conduction connection.
Under situation about being applied on the laminated substrates, available small pieces of the present invention connect tackiness agent and realize " zero stand-off tack line ".For example, can under the situation that does not have the solder mask layer on the die pad, at first make layered product.Therefore, the height in die pad zone is lower than non-bonding die pad zone relatively, and its degree of depth equals the thickness of solder mask layer, typically is about 1mil.Use ornamental engraving printing, screen printing or spraying then, connect tackiness agent with small pieces and fill these recessed die pad.
Preferably, apply an amount of b stageable die attach adhesives of the present invention, flush with the solder mask layer up to the surface that applies tackiness agent.Recessed die pad does not connect tackiness agent with small pieces fully and fills; And be to use an amount of small pieces to connect tackiness agent, and so that in small pieces are arranged, the die pad bottom of exposure before small pieces connection adhesive flow covers to the small pieces below.This method is convenient to the semiconductor packages producer under the situation that does not change the tack line tackiness agent, realizes thinner packaged piece.
Perhaps, b stageable die attach adhesives of the present invention can be used as substituting of solder mask, no matter in die pad intra-zone or outside, or both of these case.
Under the situation of spraying, thin semiconductor wafer is to be coated with small pieces thereon to connect at the bottom of the ideal basis of tackiness agent.These thin semiconductor wafers have the typical thickness of about 2-3mil.Although in case carried suitably, promptly be bonded on the flex substrate and seal or molding on (overmold), mechanically robust then, the thin small pieces embrittlement of the form of not carrying that obtains by these wafers and broken quite easily.Therefore, advantageously, when so operating, apply small pieces and connect tackiness agent adopts minimum to the method on the LED reverse mounting type power.
Use any aforesaid method apply b stageable die attach adhesives of the present invention on wafer or small pieces after, dry adhesive then, desolvate to remove (if the words that exist), or cooling, with fixed tackiness agent (if the words that under the temperature condition that gentleness raises, apply).
Can be under about 100 ℃ temperature about 30 minutes typical time of drying, but can select to be lower than any temperature of the curing starting point of curable components in the b stageable die attach adhesives.Time span can become the time that requires when inviscid according to the surface that small pieces under selected temperature connect tackiness agent and change.
Small pieces connect adhesive surface inviscid (by or dry or cooling) afterwards any moment, the bonding of small pieces can take place.
The condition that is suitable for solidifying the b stageable die attach adhesives comprises makes tackiness agent experience of the present invention at least about 175 ℃ but less than about 2 minutes of the about 0.5-of about 300 ℃ temperature.Typical small pieces bonding set(ting)value be under the situation of 7.6mm * 7.6mm small pieces, the coating amount of use 500cN, about 10 seconds time under about 100 ℃ temperature.Can be in every way, for example adopt online fast setting station, those as being made by Nihon Sanso are installed in the heating zone on the small pieces bonder, perhaps the IR that is provided by EFOS Novacure IR unit restraints, with the heating that realizes that this is quick, the time length is short.
(, as described below under stacked die package situation with reference to figure 4; Referring to United States Patent(USP) Nos. 5323060,5286679,5140404 and 6465893, the disclosure of each piece is specially introduced by reference at this), can be advantageously before small pieces be arranged, by making thermal pulse through small pieces chucks (die collet) (this is the feature that exists in the small pieces bonder of film), as making those, thereby heating small pieces by ESC.Under the situation of thin small pieces, described thin small pieces since in the grinding technics process accumulation of residual mechanical stress cause typically warpage, usually make small pieces annealing and and then reduce warpage being higher than under a certain temperature heating small pieces.
Be noted that chip small pieces 62 described herein can be used as independent chip small pieces and provide, perhaps can be used as chip scale package, provide as being described as 160 form among Fig. 3.Therefore, in Fig. 3, provide the circuit module 150 that comprises chip scale package 160.Chip scale package known in the art is used for being electrically connected of circuit and circuit board substrate.In embodiments of the invention, circuit module 150 comprises and is similar to the such structure of embodiment shown in Figure 2 that different is to replace chip small pieces 62 with chip scale package 160.For example, circuit module 150 comprises circuit board substrate 70, and described circuit board substrate 70 comprises contact mat 76 thereon.Substrate 70 is connected on the chip scale package 160, and described chip scale package 160 can comprise the carrier substrates that for example is connected to separately or chip small pieces on the layer (interposer layer) during the feast, and this is well known in the art.In this embodiment, can on this carrier substrates of separating or during the feast the layer on contact mat 66 is being provided and/or is connecting up 80, its mode is similar in the explanation of front about circuit chip 60 listed.In addition, chip scale package 160 is connected material 90 by small pieces be connected in the substrate 70, its mode is similar to the explanation of front.
In the associated viscera of using at stacked small pieces, Fig. 4 has described at the schematic cross-section of two small pieces of stacked die package 350 inner stacks and has comprised another chip small pieces 62A that the semi-conductor chip (it has chip small pieces 62 and b stageable die attach adhesives 90 of the present invention placed on it) of small pieces junction circuit chip 360 forms that apply in advance and the small pieces junction circuit chip 360 that applies in advance will be connected thereto.
Circuit chip 360 comprises chip small pieces 62 (with reference to figure 1, with above-mentioned the same).Be similar to chip small pieces 62, another chip small pieces 62A can be by any material manufacturing known in the art and can be by identical or different material manufacturing.
Another chip small pieces 62A comprises the first and second relative surfaces, and as first surface, this surface is the connection surface of chip small pieces 62 comprising chip surface 64A.Electrical contact pad so that predetermined pattern is arranged as metallized contact mat 66A, can be connected with contact mat or another chip small pieces (all not shown) of substrate.With each contact mat 66 on the chip small pieces 62 and the bonding between the contact mat 66A on another chip small pieces 62A (as by connect up 80 set up), be provided at circuit and electrical connection and engagement between the circuit on another chip small pieces 62A on the chip small pieces 62.Can be before the b stageable die attach adhesives solidifies, perhaps preferred after, 80 be bonded on the contact mat 66A by connect up, thereby set up electrical connection.Perhaps, can 80 be bonded to directly on the contact mat in the substrate 70, be electrically connected thereby set up by connecting up.Although for purpose of the present invention is described, accompanying drawing of the present invention has been described be bonded on the chip small pieces 62 two wirings 80 and two corresponding contact mat 66A on another chip small pieces 62A, but be appreciated that, the quantity of wiring bonding and contact mat 66A can change according to the ad hoc structure of specific required purposes and circuit chip and concrete structure described herein should not be construed as limiting the invention (referring to U.S. Patent No. 5323060).
With reference to embodiment subsequently, the present invention will become and be more readily understood.
Embodiment
Embodiment 1:
With the component of listing below the described consumption use, preparation b stageable die attach adhesives.Prepare maleimide according to the operation of listing in the U.S. Patent No. 5973166, its disclosure is introduced by reference at this.
Dodecyl bismaleimides 69.3g
X-BMI 1 10.8g
RICON?130 2 2.9g
2-phenoxy group acrylate 15.8g
Coupling agent 31.0
Superoxide 40.2g
1X-BMI (10,1 of 11-dioctyl eicosane, 20-bismaleimide sulfonamide derivatives), according to the operation preparation of listing in the U.S. Patent No. 5973166, its disclosure is introduced by reference at this.
220% polyhutadiene (being available commercially from Sartomer) with maleic anhydride graft.
3(β-3,4-epoxycyclohexyl) ethyl trimethoxy silane
4Cross two carbonic acid two (4-tertiary butyl cyclohexyl)
At room temperature add after each component, thoroughly mix the b stageable die attach adhesives, on glass slide, distribute, and be heated to 90 ℃ temperature 10 minutes, then be heated to 125 ℃ temperature 1 minute.
The temperature that heating b stageable die attach adhesives to 125 is ℃-130 ℃ was less than 60 seconds and place silicon chip thereon.By 1 hour time period of heating under 150 ℃ temperature, silicon chip is connected on the glass slide then.
Then, on gauged Dage 4000 small pieces shearing test instrument, estimate the room temperature small pieces of this b stageable die attach adhesives and shear and the shearing of hot small pieces.Observe the room temperature small pieces and shear, and observe hot small pieces and be cut into 45+/-19 greater than 100kg-f.
Embodiment 2:
With the component of listing below the described consumption use, preparation b stageable die attach adhesives.As mentioned above, prepare maleimide according to the operation of listing in the U.S. Patent No. 5973166.
Dodecyl bismaleimides 68.6g
X-BMI 10.7g
RICON?130 23.0g
2-phenoxy group acrylate 15.6g
Coupling agent 0.8
Superoxide 512g
5The cumyl hydroperoxide
At room temperature add after each component, thoroughly mix the b stageable die attach adhesives, on glass slide, distribute, and be heated to 90 ℃ temperature 10 minutes, then be heated to 125 ℃ temperature 1 minute.
The temperature that heating b stageable die attach adhesives to 125 is ℃-130 ℃ was less than 60 seconds and place silicon chip thereon.By 1 hour time period of heating under 150 ℃ temperature, silicon chip is connected on the glass slide then.
Then, on gauged Dage 4000 small pieces shearing test instrument, estimate the room temperature small pieces of this b stageable die attach adhesives and shear and the shearing of hot small pieces.Observe the room temperature small pieces and shear, and observe hot small pieces and be cut into 63+/-23 greater than 100kg-f.
Embodiment 3:
With the component of listing below the described consumption use, the b stageable die attach adhesives of silver is filled in preparation.The same with embodiment 1, prepare maleimide according to the operation of listing in the U.S. Patent No. 5973166.
Dodecyl bismaleimides 9.4g
X-BMI 3.35g
BMI citraconoyl amine 5.7g
RICON?130 2.9g
2-phenoxy group acrylate 4.9g
Coupling agent 0.25
Superoxide 60.1g
Silver fillers 775.5g
6Cross two carbonic acid two (4-tertiary butyl cyclohexyl)
7Granularity is between 1 to 50 micron
At room temperature add after each component, thoroughly mix the b stageable die attach adhesives, on glass slide, distribute, and be heated to 90 ℃ temperature 10 minutes, then be heated to 125 ℃ temperature 1 minute.
The temperature that heating b stageable die attach adhesives to 125 is ℃-130 ℃ was less than 60 seconds and place silicon chip thereon.By 1 hour time period of heating under 150 ℃ temperature, silicon chip is connected on the glass slide then.
Then, on gauged Dage 4000 small pieces shearing test instrument, estimate the room temperature small pieces of this b stageable die attach adhesives and shear and the shearing of hot small pieces.Observe the room temperature small pieces and shear, and observe hot small pieces and be cut into 51+/-13 greater than 100kg-f.
Embodiment 4:
Component to list below the described consumption use prepares the b stageable die attach adhesives that another fills silver.The same with embodiment 1 once more, prepare maleimide according to the operation of listing in the U.S. Patent No. 5973166.
Dodecyl bismaleimides 7.6g
X-BMI 2g
RICON?130 1.3g
Dicyclopentadienyl MA 4.5g
Dihydroxyphenyl propane two (methyl) acrylate 2.3g
Coupling agent 1.3g
Superoxide 1g
Silver fillers 80g
At room temperature add after each component, thoroughly mix the b stageable die attach adhesives, and the viscosity of mensuration 1rpm is 349000cps.This b stageable die attach adhesives is assigned on the glass slide, and was heated to 125 temperature 5 minutes.
The temperature of heating b stageable die attach adhesives to 175 1 hour.This moment, make the solidified small pieces connect adhesive cools, and to measure its volume resistance be 0.00023 Ω-cm to room temperature.
This b stageable die attach adhesives screen printing on ceramic bases, and is heated to 125 ℃ temperature 5 minutes.Make this b stageable die attach adhesives cool to room temperature.Heat the temperature of this b stageable die attach adhesives to 125, make the solid ingredient fusing, so that can place silicon chip thereon.By 1 hour time period of heating under 175 ℃ temperature, this assembly is bonded together.
Then, on gauged Dage 4000 small pieces shearing test instrument, estimate the hot small pieces of this b stageable die attach adhesives under 275 and shear.Observe hot small pieces and be cut into 46+/-Yue 10.

Claims (42)

1. composition that the b rank are curable, it comprises:
A. heat-setting solid ingredient under first temperature;
B. thermal curable or or under second temperature when the liquid ingredient that be exposed to the radiation curable in the electromagnetic spectrum scope; With
C. the thermal curing catalyst that is used for this solid curable components,
Wherein thermal curing catalyst is selected from free radical catalyst, negatively charged ion solidifying agent, cation curing agent and combination thereof, and wherein free radical catalyst is to be selected from superoxide, azo-compound and bonded member thereof.
2. the composition of claim 1, wherein the negatively charged ion solidifying agent is to be selected from nitric heterocyclic compound, amine compound, imidazolium compounds and bonded member thereof.
3. the composition of claim 1, wherein the negatively charged ion solidifying agent is to be selected from nitric heterocyclic compound, amine compound, imidazolium compounds and bonded member thereof, wherein nitric heterocyclic compound is the member who is selected from following:
1,5-diazabicyclo [4.3.0] ninth of the ten Heavenly Stems-5-alkene
Figure C2003801040800002C2
1,8-diazabicyclo [5.4.0] undecane-5-alkene (DBU)
1,5,7-three azabicyclos [4.4.0] last of the ten Heavenly stems-5-alkene
Figure C2003801040800003C1
Rubane
Figure C2003801040800003C2
1,4-diazabicyclo [2.2.2] octane.
4. the composition of claim 3, wherein amine compound is to be selected from aliphatic polyamines, aromatic polyamine, alicyclic polyamine and bonded member thereof.
5. the composition of claim 3, wherein amine compound is to be selected from diethylenetriamine, Triethylenetetramine (TETA), diethyl amino propylamine, benzyldimethylamine, m-xylene diamine, diamino-diphenylamine, quinoxaline, isophorone diamine,  alkene diamines and bonded member thereof.
6. the composition of claim 3, wherein imidazolium compounds is to be selected from different imidazoles, imidazoles, 2-ethyl-4-methylimidazole, 2, the 4-methylimidazole, butyl imidazole, 2-heptadecene base-4-methylimidazole, glyoxal ethyline, 2-undecenyl imidazoles, 1-vinyl-glyoxal ethyline, the 2-undecyl imidazole, 2-heptadecyl imidazoles, the 2-phenylimidazole, 1 benzyl 2 methyl imidazole, 1-propyl group-glyoxal ethyline, the 1-1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecyl imidazole, 1-cyanoethyl-2-phenylimidazole, 1-guanamines base ethyl-glyoxal ethyline, the adduct of imidazoles and Methylimidazole, the adduct of imidazoles and trimellitic acid, 2-n-heptadecane base-4-methylimidazole, phenylimidazole, benzyl imidazole, 2-methyl-4, the 5-diphenyl-imidazole, 2,3,5-triphenyl imidazoles, 2-styryl imidazoles, 1-(dodecylbenzyl)-glyoxal ethyline, 2-(2-hydroxyl-4-tert-butyl-phenyl)-4, the 5-diphenyl-imidazole, 2-(2-p-methoxy-phenyl)-4, the 5-diphenyl-imidazole, 2-(3-hydroxyphenyl)-4, the 5-diphenyl-imidazole, 2-(to dimethylaminophenyl)-4, the 5-diphenyl-imidazole, 2-(2-hydroxyphenyl)-4, the 5-diphenyl-imidazole, two (4,5-phenylbenzene-2-imidazoles)-benzene-1,4,2-naphthyl-4, the 5-diphenyl-imidazole, 1 benzyl 2 methyl imidazole, 2-is to methoxyl-styrene imidazoles and bonded member thereof.
7. composition that the b rank are curable, it comprises:
A. heat-setting solid ingredient under first temperature;
B. thermal curable or or under second temperature when the liquid ingredient that be exposed to the radiation curable in the electromagnetic spectrum scope; With
C. the thermal curing catalyst that is used for this solid curable components,
Wherein thermal curing catalyst is selected from free radical catalyst, negatively charged ion solidifying agent, cation curing agent and combination thereof, and wherein cation curing agent is to be selected from organic acid, acid anhydrides, Lewis acid and bonded member thereof.
8. the composition of claim 7, wherein organic acid is to be selected from phenols, thiophenol, mercaptan, carboxylic acid and bonded member thereof.
9. composition that the b rank are curable, it comprises:
A. heat-setting solid ingredient under first temperature;
B. thermal curable or or under second temperature when the liquid ingredient that be exposed to the radiation curable in the electromagnetic spectrum scope; With
C. the thermal curing catalyst that is used for this solid curable components,
Further comprise second thermal curing catalyst that the liquid curable component is used.
10. the composition of claim 9, wherein solidify to carry out under the temperature of this liquid curable component in about 50 ℃-Yue 150 ℃ of scopes and solidify under the temperature of this solid curable components in about 100 ℃-Yue 300 ℃ of scopes and carry out by first thermal curing catalyst by second thermal curing catalyst.
11. the composition of claim 9, wherein solidify by second thermal curing catalyst that this liquid curable component is carried out under less than about 100 ℃ temperature and solidify this solid curable components and be higher than under about 100 ℃ temperature and carry out by first thermal curing catalyst.
12. the composition that the b rank are curable, it comprises:
A. heat-setting solid ingredient under first temperature;
B. thermal curable or or under second temperature when the liquid ingredient that be exposed to the radiation curable in the electromagnetic spectrum scope; With
C. the thermal curing catalyst that is used for this solid curable components,
Wherein the liquid curable component comprises epoxide, episulfide, maleimide, endo-methylene group tetrahydro-phthalic imidine, clothing health imide, (methyl) acrylate, Vinyl Ether, vinyl acetate, vinylbenzene and derivative thereof, poly-(alkenylene), allyl group acid amides, norbornene, thiol-ene and combination thereof.
13. the composition of claim 12, the temperature when wherein the melting range of solid curable components solidifies less than this solid curable components.
14. the composition of claim 12, the temperature when wherein the melting range of solid curable components solidifies with this solid curable components is substantially the same.
15. the composition of claim 12 further comprises reactive diluent.
16. the composition of claim 12, wherein said composition is substantially free of non-reactive solvent.
17. the composition of claim 12 further comprises solvent.
18. the composition of claim 12 further comprises filler.
19. the composition of claim 18, wherein filler is a conductive fillers.
20. the composition of claim 18, wherein filler heat conduction.
21. the composition of claim 18, wherein filler conduction.
22. the composition of claim 18, wherein filler is non-conductive fillers.
23. the composition of claim 18, wherein the particle size of filler is less than about 50 microns.
24. the composition of claim 12 further comprises light trigger.
25. the composition of claim 24, the wherein catalyzer that causes of the radiation in UV, the UV/VIS, VIS, IR, electron beam, X-ray and the microwave range that are selected from electromagnetic spectrum of light trigger.
26. the composition that the b rank are curable, it comprises:
A. heat-setting solid ingredient under first temperature;
B. thermal curable or or under second temperature when the liquid ingredient that be exposed to the radiation curable in the electromagnetic spectrum scope; With
C. the thermal curing catalyst that is used for this solid curable components,
Wherein the solid curable components comprises epoxide, episulfide, maleimide, endo-methylene group tetrahydro-phthalic imidine, clothing health imide, (methyl) acrylate, Vinyl Ether, vinyl acetate, vinylbenzene and derivative thereof, poly-(alkenylene), allyl group acid amides, norbornene, thiol-ene and bonded thereof one or more.
27. the composition that the b rank are curable, it comprises:
A. heat-setting solid ingredient under first temperature;
B. thermal curable or or under second temperature when the liquid ingredient that be exposed to the radiation curable in the electromagnetic spectrum scope; With
C. the thermal curing catalyst that is used for this solid curable components,
Wherein the liquid curable component is to comprise the following compound that contains maleimide, contain the imido compound of clothing health or contain the compound of endo-methylene group tetrahydro-phthalic imidine:
Figure C2003801040800006C1
Wherein:
m＝1-15，
p＝0-15，
Each R 2Be independently selected from hydrogen or low alkyl group and
J contains the unit price of organic or organic siloxane group or multivalence part and two or more combination wherein.
28. the composition that the b rank are curable, it comprises:
A. heat-setting solid ingredient under first temperature;
B. thermal curable or or under second temperature when the liquid ingredient that be exposed to the radiation curable in the electromagnetic spectrum scope; With
C. the thermal curing catalyst that is used for this solid curable components,
Wherein the liquid curable component is the compound that contains maleimide that comprises structure I, II and III, contains the imido compound of clothing health or contain the compound of endo-methylene group tetrahydro-phthalic imidine, wherein
m＝1-6，
p＝0，
R 2Be independently selected from hydrogen or low alkyl group and
J is unit price or multivalence group, it is selected from alkyl, substituted hydrocarbon radical, contain heteroatomic alkyl, what replace contains heteroatomic alkyl, alkylene, replace alkylene, contain heteroatomic alkylene, what replace contains heteroatomic alkylene, polysiloxane, synthesis of polysiloxane-polyurethane block copolymer, the combination of wherein two or more, described unit price or multivalence group randomly contain one or more connection bases, and described connection base is selected from covalent linkage,-O-,-S-,-NR-,-O-C (O)-,-O-C (O)-O-,-O-C (O)-NR-,-NR-C (O)-,-NR-C (O)-O-,-NR-C (O)-NR-,-S-C (O)-,-S-C (O)-O-,-S-C (O)-NR-,-S (O)-,-S (O) 2-,-O-S (O) 2-,-O-S (O) 2-O-,-O-S (O) 2-NR-,-O-S (O)-,-O-S (O)-O-,-O-S (O)-NR-,-O-NR-C (O)-,-O-NR-C (O)-O-,-O-NR-C (O)-NR-,-NR-O-C (O)-,-NR-O-C (O)-O-,-NR-O-C (O)-NR-,-O-NR-C (S)-,-O-NR-C (S)-O-,-O-NR-C (S)-NR-,-NR-O-C (S)-,-NR-O-C (S)-O-,-NR-O-C (S)-NR-,-O-C (S)-,-O-C (S)-O-,-O-C (S)-NR-,-NR-C (S)-,-NR-C (S)-O-,-NR-C (S)-NR-,-S-S (O) 2-,-S-S (O) 2-O-,-S-S (O) 2-NR-,-NR-O-S (O)-,-NR-O-S (O)-O-,-NR-O-S (O)-NR-,-NR-O-S (O) 2-,-NR-O-S (O) 2-O-,-NR-O-S (O) 2-NR-,-O-NR-S (O)-,-O-NR-S (O)-O-,-O-NR-S (O)-NR-,-O-NR-S (O) 2-O-,-O-NR-S (O) 2-NR-,-O-NR-S (O) 2-,-O-P (O) R 2-,-S-P (O) R 2-,-NR-P (O) R 2-, wherein each R is hydrogen, alkyl or substituted alkyl and two or more combination wherein independently.
29. the composition that the b rank are curable, it comprises:
A. heat-setting solid ingredient under first temperature;
B. thermal curable or or under second temperature when the liquid ingredient that be exposed to the radiation curable in the electromagnetic spectrum scope; With
C. the thermal curing catalyst that is used for this solid curable components,
Wherein the solid curable components be at room temperature for the solid-state compound that contains maleimide, contain the imido compound of clothing health or contain the compound of endo-methylene group tetrahydro-phthalic imidine.
30. the composition of claim 29 wherein contains the compound of maleimide, the compound that contains the imido compound of clothing health or contain endo-methylene group tetrahydro-phthalic imidine is solid and comprises:
Wherein:
m＝1-15，
p＝0-15，
Each R 2Be independently selected from hydrogen or low alkyl group and
J contains the unit price of organic or organic siloxane group or multivalence part and two or more combination wherein.
31. the composition that the b rank are curable, it comprises:
A. heat-setting solid ingredient under first temperature;
B. thermal curable or or under second temperature when the liquid ingredient that be exposed to the radiation curable in the electromagnetic spectrum scope; With
C. the thermal curing catalyst that is used for this solid curable components,
Wherein liquid ingredient comprises the compound that contains maleimide, contain the imido compound of clothing health or contain one or more of compound of endo-methylene group tetrahydro-phthalic imidine, described these compounds comprise the maleimide amine functional group that is connected on the monoradical respectively, clothing health imide functionality or endo-methylene group tetrahydro-phthalic imidine functional group, the perhaps maleimide amine functional group that separates by the multivalence group, clothing health imide functionality or endo-methylene group tetrahydro-phthalic imidine functional group, each monoradical or multivalence group have enough length and the feasible compound that contains maleimide of the degree of branching, the compound that contains the imido compound of clothing health or contain endo-methylene group tetrahydro-phthalic imidine is respectively liquid.
32. a method for compositions for preparing claim 12, its step comprises:
A. be provided at heat-setting solid curable components under first temperature, thermal curable or under second temperature when being exposed to the liquid ingredient of the radiation curable in the electromagnetic spectrum scope and being used for the thermal curing catalyst of this solid curable components; With
B. be mixed together this solid curable components, liquid curable component and thermal curing catalyst.
33. the method for claim 32 further comprises:
C. said composition is exposed to the liquid curable component is solidified under the advantageous conditions.
34. the method for claim 33 further comprises:
D. said composition being exposed to is enough to make under the solid curable components fused temperature condition.
35. the method for claim 34 further comprises:
E. said composition being exposed to is enough to make under this fused solid curable components solidified temperature condition.
36. with first kind of substrate adhering junction to the second kind of suprabasil method, described method comprises:
A. the composition that applies claim 12 is in described first kind of substrate or described second kind of substrate one or both of;
The substrate that b. will apply composition is exposed under the condition that the liquid curable component that makes wherein advantageously is cured, thereby forms b rank curable film;
C. the b rank curable film among the b. is exposed under the solid curable components fused temperature condition that is enough to make wherein;
D. connect described first kind of substrate and described second kind of substrate, form assembly, wherein separate first kind of substrate and described second kind of substrate by the composition that in a., applies; With
E. the curable film among the c. being exposed to is enough to make under this fused solid curable components solidified temperature condition.
37. the method for claim 36, wherein said first kind of substrate is the chip small pieces.
38. the method for claim 36, wherein said first kind of substrate and described second kind of substrate are the chip small pieces.
39. the method for claim 36, wherein said first kind of substrate is circuit card.
40. the method for claim 36, wherein said first kind of substrate is the circuit card with solder mask.
41. the method for claim 36, wherein said first kind of substrate is the circuit card with solder mask.
42. the goods of a manufacturing, it is included as adheres to and is electrically connected with second half conductor chip or carrier substrates and a kind of semi-conductor chip of providing, this semi-conductor chip has first and second surfaces, wherein first surface has thereon the heat-setting composition in b rank that the electrical pickoff arranged with predetermined pattern has the claim 12 that places on its one deck or the part in order to electricity engagement and the second surface that provides respectively with second half conductor chip or carrier substrates.
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JP2019511587A (en) * 2016-02-04 2019-04-25 ヘンケル アイピー アンド ホールディング ゲゼルシャフト ミット ベシュレンクテル ハフツング Peelable adhesive and its high temperature use
JP6900517B2 (en) * 2017-07-31 2021-07-07 ヘレウス ドイチェラント ゲーエムベーハー ウント カンパニー カーゲー Composition for manufacturing water-based coating material
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