CN103059787B - Thermally conductive adhesive composition, the bonding sheet material using said composition and thermal conductivity dicing die bonding film - Google Patents

Thermally conductive adhesive composition, the bonding sheet material using said composition and thermal conductivity dicing die bonding film Download PDF

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Publication number
CN103059787B
CN103059787B CN201210409530.2A CN201210409530A CN103059787B CN 103059787 B CN103059787 B CN 103059787B CN 201210409530 A CN201210409530 A CN 201210409530A CN 103059787 B CN103059787 B CN 103059787B
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composition
formula
thermally conductive
conductive adhesive
thermal conductivity
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CN103059787A (en
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市六信广
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Shin Etsu Chemical Co Ltd
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Shin Etsu Chemical Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C09J9/02—Electrically-conducting adhesives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/35—Heat-activated
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
    • H01L21/67005—Apparatus not specifically provided for elsewhere
    • H01L21/67011—Apparatus for manufacture or treatment
    • H01L21/67144—Apparatus for mounting on conductive members, e.g. leadframes or conductors on insulating substrates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/304—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being heat-activatable, i.e. not tacky at temperatures inferior to 30°C
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/314—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive layer and/or the carrier being conductive
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
    • H01L21/60—Attaching or detaching leads or other conductive members, to be used for carrying current to or from the device in operation
    • H01L2021/60007—Attaching or detaching leads or other conductive members, to be used for carrying current to or from the device in operation involving a soldering or an alloying process
    • H01L2021/60022—Attaching or detaching leads or other conductive members, to be used for carrying current to or from the device in operation involving a soldering or an alloying process using bump connectors, e.g. for flip chip mounting
    • H01L2021/60097—Applying energy, e.g. for the soldering or alloying process
    • H01L2021/6015—Applying energy, e.g. for the soldering or alloying process using conduction, e.g. chuck heater, thermocompression
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
    • H01L21/60—Attaching or detaching leads or other conductive members, to be used for carrying current to or from the device in operation
    • H01L2021/60277—Attaching or detaching leads or other conductive members, to be used for carrying current to or from the device in operation involving the use of conductive adhesives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/80—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
    • H01L2224/83—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
    • H01L2224/8319—Arrangement of the layer connectors prior to mounting
    • H01L2224/83191—Arrangement of the layer connectors prior to mounting wherein the layer connectors are disposed only on the semiconductor or solid-state body
    • 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
    • H01L2924/30—Technical effects
    • H01L2924/35—Mechanical effects
    • H01L2924/351—Thermal stress

Abstract

There is provided thermal conductivity high and heat dissipation characteristics is excellent, binding property is good and thermally conductive adhesive composition, the bonding sheet material using said composition and thermal conductivity dicing die bonding film excellent in reliability after humidity test.Thermally conductive adhesive composition, it contains: have in (A) polymer backbone that the epoxy resin in the polymkeric substance of the functional group can reacted with epoxy resin, (B) per molecule with at least 2 epoxy group(ing) and (C) silicon compound that the number-average molecular weight that a specific average group accepted way of doing sth represents is 500 ~ 10000 has carried out surface-treated, thermal conductivity is the inorganic filler of more than 10W/mK; Bonding sheet material, it possesses: the binder layer be made up of above-mentioned composition that base material and this base material are arranged; Thermal conductivity dicing die bonding film, it possesses: have the binder layer be made up of above-mentioned composition that the cutting film of adhesive layer of base material and its upper setting and the adhesive layer of this cutting film are arranged.

Description

Thermally conductive adhesive composition, the bonding sheet material using said composition and thermal conductivity dicing die bonding film
Technical field
The present invention relates to and be suitable for manufacturing semiconductor device, the semiconductor packages being especially suitable for use as resin die, thermal conductivity is high and heat dissipation characteristics excellent, for having the thermally conductive adhesive composition of strong adhesive power, the bonding sheet material of use said composition and thermal conductivity dicing die bonding film (dicing-die attach film) as the silicon (Si) of adherend and solder resist (solder resist).
Background technology
The manufacturing step of semiconductor device is as follows: by cutting (cut-out) step, the large diameter silicon wafers being formed with IC circuit is cut into semi-conductor chip, with fluid binder (the chip adhesive material of solidified nature, ダ イ ボ Application De material) etc. hot pressing on lead frame, be adhesively fixed (assembling, mount), carry out interelectrode wire-bonded (wire bonding), afterwards in order to treatability or not by outside atmosphere impact and seal.The non-hermetic seals type that this sealing form has the gas-tight seal such as metallic seal, ceramic seal type and carries out with resin, now, the transfer moudling of carrying out with resin of the latter, because of volume production excellent performance, cheapness, the most generally uses.But, although this resin-molded encapsulation has above-mentioned advantage, but then, in moisture-proof thermotolerance, thermal stress relaxation, thermal diffusivity etc., there is shortcoming.
Along with miniaturization and the multifunction of electric electronic Instrument in recent years, answer the requirement of the multifunction of electronic unit, distribution also more miniaturization, the densification of semiconductor device, because of semi-conductor chip maximization and there is the appearance of semiconductor device of laminate structures (stacked CSP, SiP) of face battle array adhesion type chip without lead frame and the structure (CSP) with size or chip, the thermal shockings (stress) in these encapsulation (PKG) are also day by day harsh.
And, in the semiconductor device to the printed circuit board load (mounting) process step, corresponding to the lead-free solder reflow resistance is at high temperature (265 ℃), has become increasingly harsh.Therefore, the material that requirement uses is started the most applicable and there is high-performance.Particularly, in encapsulation constituent material, because chip adhesive material can in larger scope control characteristic, can easily tackle these requirements, therefore as chip adhesive material, the material of the low elastic modulus of thermal shocking (stress) that can be corresponding harsh, high bonding, high heat resistance is needed.
In addition, the supporting substrate of mounting semiconductor chip also requires miniaturization, when carrying out mounting semiconductor chip with the tackiness agent of liquid state, cause electrode fouling because of the overlap (は body goes out) from die terminals or because of the in uneven thickness of bonding coat, chip is tilted, there is the situation that wire-bonded (wire bond) is bad, therefore also wish the tackiness agent membranization that can improve these shortcomings.
As these tackiness agents, develop the low modulus of elasticity materials importing siloxane structure in the resin of excellent heat resistance and polyimide or polyamidoimide at present.All propose silicone-modified polyamidoimide in patent documentation 1,2 etc., but they still have deficiency in low elasticity with in the binding property of adherend.
Propose mixing in silicone-modified polyamidoimide in patent documentation 3 and there is the compound of more than 2 Maleimido to improve hot properties, but this resin combination poor adhesion.
Thermotolerance bonding film that propose binding property, low elasticity and excellent heat resistance in patent documentation 4 and 5, that be made up of polyimide silicon and epoxy resin, the bounding force of this film improves, but low elasticityization is not enough.
Prior art document
Patent documentation
Patent documentation 1 Japanese Unexamined Patent Publication 3-189127 publication;
Patent documentation 1 Japanese Unexamined Patent Publication 4-264003 publication;
Patent documentation 3 Japanese Unexamined Patent Publication 10-60111 publication;
Patent documentation 4 Japanese Unexamined Patent Publication 7-224259 publication;
Patent documentation 5 Japanese Unexamined Patent Publication 8-27427 publication;
Patent documentation 6 Japanese Unexamined Patent Publication 2003-193016 publication.
Due to the miniaturization of semi-conductor chip in recent years and switching fast (namely running fast), the heat per unit area of generation has the tendency of increase, and in order to efficiently radiates heat, the adhesive film for semiconductor that thermal conductivity is high becomes the demand in market.
The simple composition that with the addition of the filler of high thermal conductivity coefficient in order to increase thermal conductivity is highly brittle, and cannot process film forming, is be not suitable for practical composition.In addition, if improve the processibility of film and add low viscosity composition in a large number, then before and after moisture absorption, bounding force reduces, and the reliability as semiconductor packages reduces.
Summary of the invention
The problem that invention will solve
The present invention carries out in view of the foregoing, in order to overcome above-mentioned defect, object is to provide: thermal conductivity is high and heat dissipation characteristics excellent, binding property is good and thermally conductive adhesive composition, the bonding sheet material using said composition and thermal conductivity dicing die bonding film excellent in reliability after humidity test.
For solving the means of problem
The present inventor conducts in-depth research to achieve these goals, found that: as high thermal conductivity filler, and it is effective for using with specific silicon compound the filler that its surface processes, thus completes the present invention.
That is, the first, the invention provides the thermally conductive adhesive composition containing following (A) ~ (C) composition:
(A) there is in polymer backbone polymkeric substance 100 mass parts of the functional group can reacted with epoxy resin;
(B) there is in per molecule epoxy resin 50 ~ 400 mass parts of at least 2 epoxy group(ing); And
(C) by the number-average molecular weight that a following average group accepted way of doing sth (I) represents be 500 ~ 10000 inorganic filler 1000 ~ 4000 mass parts that silicon compound has carried out surface-treated, thermal conductivity is more than 10W/mK,
In formula, R 1~ R 4the monovalent hydrocarbon that respective independent expression does not have the non-substituted of aliphatic unsaturated link(age) or replaces, a is the positive number of 0.1 ~ 0.7, and b is the positive number of 0.01 ~ 0.2, and c is the number of 0 ~ 0.9, and d is the number of 0 ~ 0.2, and condition meets a+b+c+d=1.
The second, the invention provides bonding sheet material, it possesses: the binder layer be made up of above-mentioned thermally conductive adhesive composition that base material and this base material are arranged.
3rd, the invention provides thermal conductivity dicing die bonding film, it possesses: have the binder layer be made up of above-mentioned thermally conductive adhesive composition that the cutting film of adhesive layer of base material and its upper setting and this adhesive layer of this cutting film are arranged.
Invention effect
Binder composition thermal conductivity of the present invention is high and heat dissipation characteristics excellent, excellent with the binding property of adherend.Nationality, by the bonding sheet material and the thermal conductivity dicing die bonding film that use binder composition of the present invention, can manufacture the resin encapsulated semiconductor device of high reliability.
Embodiment
The present invention will be described in more detail below.It should be noted that, that the weight-average molecular weight in this specification sheets and number-average molecular weight refer to measure under the following conditions respectively, that undertaken by gel permeation chromatography (GPC), take polystyrene as weight-average molecular weight and the number-average molecular weight of reference material.
[condition determination]
Developing solvent: tetrahydrofuran (THF) (THF);
Flow: 1mL/ minute;
Device: HLC-8320GPC (trade(brand)name, Tosoh Inc.);
Detector: differential refraction rate detector (RI);
Post: TSKgel GMH xL-L+TSKgel G4000H xL+ TSKgel G2000H xL+ TSKgel G2000H xL(trade(brand)name, Tosoh Inc.);
Column temperature: 40 DEG C;
Sample injection rate: 100 μ L (the THF solution of concentration 0.5 quality %).
Binder composition of the present invention contains (A) ~ (C) composition, keeps shape, form membranaceous film, solidify after heating through plasticized condition under normal temperature, therefore to the binding property that adherend display is excellent.The cured article excellent thermal conductivity of binder composition of the present invention.Use the thermal conductivity dicing die bonding film possessing the binder layer be made up of binder composition of the present invention and the reliability of semiconductor manufactured is excellent.
[there is in (A) polymer backbone the polymkeric substance of the functional group can reacted with epoxy resin]
In binder composition of the present invention, the polymkeric substance in polymer backbone with the functional group can reacted with epoxy resin is necessary, reason is as follows: in order to make the space between bonding film and substrate be less state during chip attachment, and the shear viscosity at least 1 temperature of bonding film between 130 ~ 170 DEG C needs 1 × 10 3~ 1 × 10 5in the scope of Pas, this point has obtained experiment to be proved.In order to above-mentioned shear viscosity is maintained within the limits prescribed, form in the composition of bonding film and need containing the high component of polymer of viscosity ratio monomer.(A) composition can be used alone a kind, also may be two kinds or more.In addition, in order to make firmly matrix (matrix) between epoxy resin (such as the epoxy resin of following (B) composition) contained in binder composition of the present invention, the functional group can reacted with epoxy resin is necessary.
(A) second-order transition temperature (Tg) of the polymkeric substance of composition is preferably more than 40 DEG C.When using Tg be the component of polymer making bonding film of more than 40 DEG C and this bonding film is processed into dicing die bonding film, the viscosity of this bonding film to cutting film can not be excessively strong, this bonding film is difficult to be attached to securely on cutting film, easily with the short period of time, this bonding film is peeled off from cutting film, therefore easily improve the production efficiency of semiconductor device fabrication.
(A) functional group can reacted with epoxy resin in composition such as has: at least a kind of functional group being selected from carboxyl, amino, imino-, epoxy group(ing), phenolic hydroxyl group and thiol group.
(A) polymkeric substance of composition is preferably 10 by the weight-average molecular weight of polystyrene conversion, 000 ~ 200,000, is more preferably 20,000 ~ 100,000, is more preferably 30,000 ~ 80,000.If weight-average molecular weight is in above-mentioned scope, then the easy composition by obtaining forms film, also easily obtain for fill the substrate surface with fine circuit pattern concavo-convex, there is enough flexible bonding film.
(A) polymkeric substance of composition such as has polyimide resin.(A) polymkeric substance of composition also can be used as the polyamic acid of the precursor of polyimide resin, but the byproduct water because of imidization (dehydration closed-loop) sometimes when being heating and curing of chip join step, thus produce the situations such as adhesive face stripping, therefore preferably use the polyimide resin of imidization (dehydration closed-loop) in advance.Polyamic acid such as has the compound shown in following general formula (1).Polyimide resin such as has the compound shown in following general formula (2).Polyamic acid and polyimide resin can contain diorganopolysiloxanecompositions key, in addition, from fusible angle, have phenolic hydroxyl group in preferred skeleton.
[chemical formula 1]
In formula, X is the quadrivalent organic radical group containing aromatic ring or aliphatic ring, and Y is the divalent organic group can with siloxane bond, and q is the integer of 1 ~ 300.
[chemical formula 2]
In formula, X is the quadrivalent organic radical group containing aromatic ring or aliphatic ring, and Y is the divalent organic group can with siloxane bond, and q is the integer of 1 ~ 300.
In above-mentioned general formula (1), q is the integer of 1 ~ 300, and be preferably the integer, the particularly integer of 5 ~ 300 of 2 ~ 300, the polyamic acid with this repeat number easily can be obtained by following method.In addition, the polyamic acid dehydration shown in above-mentioned general formula (1), closed loop can be obtained by ordinary method by the polyimide resin shown in above-mentioned general formula (2).
Polyamic acid shown in general formula (1) can conventionally, by making the tetracarboxylic dianhydride shown in following structural formula (3) with roughly equimolar ratio:
[chemical formula 3]
(wherein, X represents implication similar to the above.)
With the diamines shown in following structural formula (4):
(wherein, Y represents implication similar to the above.)
Reaction obtains in organic solvent.
Herein, the object lesson of the tetracarboxylic dianhydride shown in above formula (3) has following compound, but is not limited to these compounds.
[chemical formula 4]
It should be noted that, the tetracarboxylic dianhydride shown in these above formulas (3) can use one kind or two or more as required.
(a) diamino silicone compounds
From the angle of the solvability to organic solvent, the binding property to adherend, low elasticity, flexibility, it is desirable to preferably have 1 ~ 80 % by mole in the diamines shown in above formula (4), more preferably have 1 ~ 60 % by mole for the diamino silicone compounds shown in following structural formula (5).
[chemical formula 5]
In formula, R 1for the divalent organic group of carbonatoms 3 ~ 9, R 2and R 3respective is independently non-substituted or the monovalent hydrocarbon of the carbonatoms 1 ~ 8 of replacement, and r is the integer of 1 ~ 200.
In the siloxane diamine (or α, ω-diamino polysiloxane) shown in general formula (5), R 1the divalent organic group of shown carbonatoms 3 ~ 9 such as has-(CH 2) 3-,-(CH 2) 4-,-CH 2cH (CH 3)-,-(CH 2) 6-,-(CH 2) 8-wait alkylidene group;
[chemical formula 6]
、 、
Deng arylidene; By the alkylenearylene that these alkylidene groups and arylidene combine;-(CH 2) 3-O-,-(CH 2) 4the alkylidene oxides such as-O-(オ キ シ ア Le キ レ Application);
[chemical formula 7]
、
Deng oxidation arylidene (オ キ シ ア リ ー レ Application base); These alkylidene oxides and arylidene are combined such as:
[chemical formula 8]
Can containing the plain atom of ether oxygen atom (エ ー テ Le acid Deng alkylidene oxide arylidene etc.) bivalent hydrocarbon radical.
R 2or R 3the monovalent hydrocarbon of the carbonatoms 1 ~ 8 of shown non-substituted or replacement such as has: the C1-C8 alkyl such as methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, the tertiary butyl, hexyl, cyclohexyl, 2-ethylhexyl, octyl group; The C1-C8 alkenyls such as allyl group, propenyl, pseudoallyl, butenyl, isobutenyl, hexenyl; The C1-C8 aryl such as phenyl, tolyl, xylyl; The C1-C8 such as benzyl, phenylethyl aralkyl; Part or all group replaced by halogen atoms etc. such as fluorine, bromine, chlorine of the hydrogen atom be combined with the carbon atom of these groups, the haloalkyls etc. such as such as chloromethyl, bromotrifluoromethane, 3,3,3-trifluoro propyls.Wherein preferable methyl and phenyl.
Compound shown in below diamino silicone compounds shown in above formula (5) specifically has.
[chemical formula 9]
Diamino silicone compounds shown in these above formulas (5) can desirably be used alone a kind, also can use combination of more than two kinds.
B () does not have the diamine compound of phenolic hydroxyl group
Regulate the flexibility of resin combination from the cross-linking set controlled with epoxy resin and control the angle of the intermiscibility to epoxy resin, iting is desirable to preferably have 40 ~ 95 % by mole in the diamines shown in above formula (4), more preferably having 50 ~ 90 % by mole for not having the diamine compound of phenolic hydroxyl group.
In diamines shown in above formula (4), except the diamino silicone compounds shown in above formula (5), the diamines without phenolic hydroxyl group such as has: Ursol D, mphenylenediamine, 4,4'-diaminodiphenyl-methane, 4,4'-diamino-diphenyl ether, 2,2 '-bis-(4-aminophenyl) propane, 4,4'-diamino diphenyl sulfone, 4,4'-diamino-diphenyl sulfide, Isosorbide-5-Nitrae-bis-(3-amino-benzene oxygen) benzene, Isosorbide-5-Nitrae-bis-(4-amino-benzene oxygen) benzene, Isosorbide-5-Nitrae-bis-(p-aminophenyl alkylsulfonyl) benzene, Isosorbide-5-Nitrae-bis-(m-aminophenyl base alkylsulfonyl) benzene, Isosorbide-5-Nitrae-bis-(p-aminophenyl thioether) benzene, Isosorbide-5-Nitrae-bis-(m-aminophenyl base thioether) benzene, two [4-(4-amino-benzene oxygen) phenyl] propane of 2,2-, two [3-methyl-4-(4-amino-benzene oxygen) phenyl] propane of 2,2-, two [the chloro-4-of 3-(4-amino-benzene oxygen) phenyl] propane of 2,2-, two [4-(4-amino-benzene oxygen) phenyl] ethane of 1,1-, two [3-methyl-4-(4-amino-benzene oxygen) phenyl] ethane of 1,1-, two [the chloro-4-of 3-(4-amino-benzene oxygen) phenyl] ethane of 1,1-, two [3,5-dimethyl-4-(4-amino-benzene oxygen) phenyl] ethane of 1,1-, two [4-(4-amino-benzene oxygen) phenyl] methane, two [3-methyl-4-(4-amino-benzene oxygen) phenyl] methane, two [the chloro-4-of 3-(4-amino-benzene oxygen) phenyl] methane, two [3,5-dimethyl-4-(4-amino-benzene oxygen) phenyl] methane, two [4-(4-amino-benzene oxygen) phenyl] sulfone, two [4-(4-amino-benzene oxygen) phenyl] perfluoropropane of 2,2-etc. are containing the diamines etc. of aromatic ring.Preferred Ursol D, mphenylenediamine, 4,4'-diaminodiphenyl-methane, 4,4'-diamino-diphenyl ether, 1, two (3-amino-benzene oxygen) benzene, 1 of 4-, two (4-amino-benzene oxygen) benzene, 2 of 4-, two [4-(4-amino-benzene oxygen) phenyl] propane of 2-, 2,2-two [3-methyl-4-(4-amino-benzene oxygen) phenyl] propane etc.
C () has the diamine compound of phenolic hydroxyl group
In the present invention, from fusible angle, in the polymer backbone of preferred polyimide resin, there is phenolic hydroxyl group.The importing of phenolic hydroxyl group can realize by using the diamine compound with epoxy group(ing) with the phenolic hydroxyl group being hyperergy.This diamines such as has: the compound shown in following formula.
[chemical formula 10]
In formula, R 4independent is hydrogen atom; The halogen atoms such as fluorine atom, bromine atoms, atomic iodine; Or the monovalent hydrocarbon of the carbonatoms 1 ~ 8 that alkyl, alkenyl, alkynyl, trifluoromethyl, phenyl etc. are non-substituted or replace, n is the integer of 1 ~ 5, A and B separately can be identical or different.R is independently hydrogen atom, halogen atom or monovalent hydrocarbon that is non-substituted or that replace.
Herein, R 4the monovalent hydrocarbon of carbonatoms 1 ~ 8 that is non-substituted or that replace such as have: with above-mentioned R 2or R 3the alkynyls etc. such as the alkyl that illustrative alkyl is same and ethynyl, proyl, butynyl, hexin base.The monovalent hydrocarbon that is non-substituted or that replace of R also can be enumerated and above-mentioned R 4the alkyl that illustrative alkyl is same.
In the present invention, even if having in the diamine compound of phenolic hydroxyl group above-mentioned, the also particularly preferably diamine compound shown in following formula (6).
[chemical formula 11]
In formula, R 4same as described above.
It should be noted that, in the present invention, the combined amount with the diamine compound of phenolic hydroxyl group is preferably 5 ~ 60 % by mole of diamine compound total amount, is particularly preferably 10 ~ 50 % by mole.If combined amount is very few, then there is the situation that bounding force reduces; And if too much, then have the situation of the flexibility deficiency of binder layer.
D () has the monoamine compound of phenolic hydroxyl group
Import phenolic hydroxyl group in polymer backbone in order to from the polyimide resin to (A) composition, except the diamines of formula (4), the monoamine with phenolic hydroxyl group can also be used.This monoamine can enumerate following structure.
[chemical formula 12]
In formula, R 4same as described above, on each aromatic ring with substituting group can be all or part of identical, also can be all different.D can be used alone a kind, also may be two kinds or more.P is the integer of 1 ~ 3.
Use above-mentioned when having the monoamine of phenolic hydroxyl group, its combined amount is 1 ~ 10 % by mole relative to the diamine compound total amount of above formula (4), is preferably 2 ~ 8 % by mole.
Above-mentioned monoamine compound is not limited to the compound of structure above, and in addition, these monoamine compounds desirably can be used alone a kind, also two or more can be combinationally used.
About the formation reaction of polyamic acid and polyimide resin, object lesson has: be dissolved in solvent by above-mentioned starting raw material under an inert atmosphere, usually below 80 DEG C, preferably, makes it react at 0 ~ 40 DEG C, synthesizing polyamides acid.Further by making the polyamic acid of acquisition be warming up to usual 100 ~ 200 DEG C, preferably 150 ~ 200 DEG C, making the amide moieties dehydration closed-loop of polyamic acid, the polyimide resin of target can be synthesized.
As long as the organic solvent used in above-mentioned reaction is inertia to the polyamic acid obtained, and can not be the solvent that can dissolve above-mentioned starting raw material completely.Such as have: tetrahydrofuran (THF), 1,4-diox, cyclopentanone, pimelinketone, gamma-butyrolactone, N-Methyl pyrrolidone, N, N-N,N-DIMETHYLACETAMIDE, N, dinethylformamide and dimethyl sulfoxide (DMSO), preferred aprotic polar solvent, particularly preferably N-Methyl pyrrolidone, pimelinketone and gamma-butyrolactone.These solvents can use a kind or two or more combinationally used.
In order to make above-mentioned dehydration closed-loop easily carry out, it is desirable to use the azeotropy dehydrant such as toluene, dimethylbenzene.In addition, diacetyl oxide/pyridine mixing solutions also can be used to carry out dehydration closed-loop at low temperatures.
It should be noted that, in order to regulate the molecular weight of polyamic acid and polyimide resin, also can add the dicarboxylic anhydride such as maleic anhydride, Tetra hydro Phthalic anhydride; And aniline, n-butylamine, enumerate above there is one or both of the monoamine compounds such as the monoamine of phenolic hydroxyl group.Wherein, the addition of dicarboxylic anhydride, relative to the tetracarboxylic dianhydride of 100 mass parts above formulas (3), is generally 0 ~ 2 mass parts, and the addition of monoamine compound, relative to the diamines of 100 mass parts above formulas (4), is generally 0 ~ 2 mass parts.
(A) polymkeric substance of composition is except above-mentioned polyimide resin, also has phenoxy resin.This phenoxy resin such as has: derived from the bisphenol type phenoxy resin of Epicholorohydrin and dihydroxyphenyl propane or F etc.This phenoxy resin such as has: commodity are called PKHC, PKHH, PKHJ (by bar chemical company system), the commodity of bisphenol AF mixed type are called Epikote 4250, Epikote 4275, Epikote 1255HX30, use the Epikote 5580BPX40 (being Japanese chemical drug Inc.) of epoxy group(ing) bromine (smelly elementization エ Port キ シ), the commodity of bisphenol A-type are called YP-50, YP-50S, YP-55, YP-70 (be Dongdu and change into Inc.), JER E1256, E4250, E4275, YX6954BH30, YL7290BH30 (being Japan epoxy resin Inc.) etc.
[there is in (B) per molecule the epoxy resin of at least 2 epoxy group(ing)]
The molecular structure, molecular weight etc. of the epoxy resin of (B) composition are not particularly limited.(B) epoxy resin of composition is preferably 100 ~ 10000 by the weight-average molecular weight of polystyrene conversion, is more preferably 100 ~ 1000.(B) composition can be used alone a kind, also may be two kinds or more.
This epoxy resin such as has: two (4-hydroxy phenyl) methane, 2,2'-two (4-hydroxy phenyl) propane or this halid diglycidylether and their polycondensate (so-called bisphenol f type epoxy resin, bisphenol A type epoxy resin etc.); The diglycidylether, 1 of dicyclo oxygenated butadiene, vinyl cyclohexene dioxide, Resorcinol, 4-two (2,3-glycidoxy) benzene, 4,4'-two (2,3-glycidoxy) phenyl ether, 1,4-two (2,3-glycidoxy) tetrahydrobenzene, two (3,4-epoxy-6-methylcyclohexylmethyl) adipic acid ester (or salt), 1,2-dioxy base benzene or Resorcinol, polyphenol or polyvalent alcohol and epichlorohydrin and the glycidyl oxirane obtained or poly glycidyl ester; The novolak phenolics (or halogenation novolak phenolics) such as phenol novolacs (Off ェ ノ ー Le ノ ボ ラ ッ Network), cresol novolak (Network レ ゾ ー Le ノ ボ ラ ッ Network) and epichlorohydrin and the epoxy phenolics (that is, phenolic resin varnish type epoxy resin) that obtains; By the epoxidised epoxidized polyolefin of peroxidation method; Epoxidized polybutadiene; Naphthalene-ring containing epoxy resin; Biphenyl type epoxy resin; Phenol-aralkyl-type epoxy resin; Biphenyl-aralkyl type epoxy resin; Cyclopeutadiene type epoxy resin etc.
It should be noted that, having in above-mentioned per molecule also can suitably also with mono-epoxy compounds in the epoxy resin of at least 2 epoxy group(ing), and this mono-epoxy compounds such as has: Styrene oxide 98min., cyclohexene oxide, propylene oxide, methyl glycidyl ether, ethyl ether, phenyl glycidyl ether, glycidyl allyl ether, octylene oxide, oxidation laurylene etc.Mono-epoxy compounds can be used alone a kind, also may be two kinds or more.
Relative to the polymkeric substance of 100 mass parts (A) composition, the combined amount of (B) composition is generally 50 ~ 400 mass parts, is preferably 80 ~ 300 mass parts, is more preferably 150 ~ 250 mass parts, is particularly preferably 200 ~ 250 mass parts.If the combined amount of epoxy resin is very few, then there is the situation of poor adhesion; If too much, during for liquid-state epoxy resin, there is and the situation of operational difficulty excessive to the viscosity of film, during epoxy resin for solid state, have binder layer not form membranaceous situation.
[(C) with the silicon compound that the number-average molecular weight shown in an average group accepted way of doing sth (I) is 500 ~ 10000 carried out surface-treated, thermal conductivity is the inorganic filler of more than 10W/mK]
(C) in composition, the thermal conductivity of inorganic filler is generally more than 10W/mK, is preferably more than 20W/mK, is particularly preferably more than 30W/mK.It should be noted that, the thermal conductivity in this specification sheets is the value at 25 DEG C.If above-mentioned thermal conductivity is less than 10W/mK, then thermal diffusivity is not enough, and the temperature of semiconductor element and substrate has the possibility of rising.It should be noted that, be not particularly limited the upper limit of thermal conductivity, representational is below 500W/mK.The object lesson carrying out surface-treated inorganic filler with above-mentioned silicon compound such as has: the oxide powders such as alumina powder, Zinc oxide powder, magnesium oxide powder; The nitride such as aluminium nitride, hexagonal boron, cubic boron nitride, silicon nitride; The metal-powders such as aluminium powder form, copper powder, silver powder, bronze end, silicon metal powder; The carbon such as diamond powder, carbon nanotube system powder; The combination of more than two kinds of above-mentioned powder.Preferential oxidation aluminium powder form.(C) composition can be used alone a kind, also may be two kinds or more.(C) median size of composition is preferably 0.05 ~ 50 μm.
(C) in composition as silicon face treatment agent, inorganic filler carried out to surface-treated silicon compound represents with a following average group accepted way of doing sth (I), number-average molecular weight is the silicon compound of 500 ~ 10000:
(in formula, R 1~ R 4the monovalent hydrocarbon that respective independent expression does not have the non-substituted of aliphatic unsaturated link(age) or replaces, a is the positive number of 0.1 ~ 0.7, and b is the positive number of 0.01 ~ 0.2, and c is the number of 0 ~ 0.9, and d is the number of 0 ~ 0.2, and condition meets a+b+c+d=1.)
This silicon compound is as the surface treatment agent of inorganic filler and play a role with the bonding agent that adherend reacts.(C) inorganic filler of composition has carried out surface treatment this point with this silicon compound is necessary in the present invention.Namely, surface-treated inorganic filler is under the existence of this silicon compound, be heat-treated under high temperature, by the hydroxyl of the remained on surface of this inorganic filler and the dehydrogenation reaction of mineral acid (surface treatment agent residue) and this silicon compound, this surface is modified by this silicon compound.And, to modify in this silicon compound on this surface residual hydrogen atom and adherend reacts, therefore show firmly bounding force.From these angles, the surface treatment of (C) composition is necessary in the present invention.As long as this silicon compound meets above-mentioned important document, be not particularly limited, can synthesize by known method.This silicon compound can be used alone a kind, also may be two kinds or more.
When making (C) composition, preferably preferably 100 ~ 180 DEG C, more preferably 110 ~ 170 DEG C, be more preferably 120 ~ 160 DEG C temperature under, under the existence of above-mentioned silicon compound by inorganic filler thermal treatment preferably more than 10 minutes, more preferably 30 ~ 300 minutes, be more preferably 50 minutes ~ 180 minutes.If thermal treatment temp is in the scope of 100 ~ 180 DEG C, then the hydroxyl of the remained on surface of surface-treated inorganic filler and the reaction process of mineral acid and above-mentioned silicon compound are easily accelerated, and above-mentioned silicon compound is not easily deteriorated.In addition, if heat treatment time is more than 10 minutes, then the hydroxyl of the remained on surface of surface-treated inorganic filler and the reaction of mineral acid and above-mentioned silicon compound are easy to fully carry out.
Preferred above-mentioned silicon compound has at least 2 formula HR in per molecule 1that SiO represents, have be combined with Siliciumatom hydrogen atom, be positioned at unit (D in the middle of molecular chain hunit), there are at least 2 formula R in per molecule 2 3siO 1/2that represent, that not there is the hydrogen atom be combined with Siliciumatom unit.That is, preferably in this silicon compound, the hydrogen atom be combined with Siliciumatom exists only in the middle of molecular chain (that is, only at (HR 1siO) in unit), molecule chain end does not exist, molecule chain end (R 2 3siO 1/2) unit terminated.
In an above-mentioned average group accepted way of doing sth (I), when a is less than 0.1, be then difficult to obtain the bounding force to the excellence of adherend; During more than 0.7, then easily produce space in cured article, have the situation that the bounding force of adherend is reduced.
When b is less than 0.01, then easily produce space in cured article, have the situation that the bounding force of adherend is reduced; During more than 0.2, be then difficult to obtain the bounding force to the excellence of adherend.
When c is more than 0.9, then the consistency of above-mentioned silicon compound to epoxy resin-base easily reduces, and is difficult to obtain the bounding force to the excellence of adherend.
When d is more than 0.2, then easily cause viscosity to rise, be difficult to obtain the bounding force to the excellence of adherend.
The number-average molecular weight of above-mentioned silicon compound is generally 500 ~ 10000, is preferably 500 ~ 7500, is more preferably 1000 ~ 5000, and preferably this silicon compound is liquid value under room temperature (25 DEG C).When this number-average molecular weight is less than 500, the volatility of silicon compound easily raises, and has the situation being difficult to apply high temperature, surface treatment rate reduces, have the anxiety of bounding force reduction when therefore heat-treating inorganic filler surface.When this number-average molecular weight is greater than 10000, silicon compound easily forms high viscosity, has the situation that the wettability, the surface treatment rate that are difficult to guarantee to inorganic filler reduce.In addition, when this number-average molecular weight is greater than 10000, have that the residual silicon compound not having chemical bond between inorganic filler easily produces in a large number, the anxiety of bounding force reduction.
Above-mentioned silicon compound is preferably 0.1 ~ 1000mPas the viscosity of 25 DEG C, is more preferably 0.5 ~ 500mPas, is more preferably 0.5 ~ 300mPas.Preferably this silicon compound is liquid under room temperature (25 DEG C).
In an above-mentioned average group accepted way of doing sth (I), R 1~ R 4carbonatoms be preferably 1 ~ 10, be more preferably 1 ~ 6.R 1~ R 4object lesson such as have: the alkyl such as methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, the tertiary butyl, amyl group, neo-pentyl, hexyl, octyl group, nonyl, decyl; The cycloalkyl such as cyclohexyl; The aryl such as phenyl, tolyl, xylyl, naphthyl; The aralkyl such as benzyl, phenylethyl, phenyl propyl; Part or all group replaced by halogen atoms such as fluorine atom, chlorine atoms of the hydrogen atom of these non-substituted alkyl, such as 3,3,3-trifluoro propyls etc., preferred alkyl, aryl, 3,3,3-trifluoro propyls, more preferably methyl, phenyl, 3,3,3-trifluoro propyls.
The object lesson of above-mentioned silicon compound such as has: by (CH 3) HSiO unit, (CH 3) 2siO unit and (CH 3) 3siO 1/2unit form multipolymer, by (CH 3) HSiO unit, (CH 3) 3siO 1/2unit, (C 6h 5) 2siO unit, (CH 3) 2siO unit and CH 3siO 3/2unit form multipolymer, by (C 6h 5) HSiO unit, (CH 3) 3siO 1/2unit, (CH 3) 2siO unit and CH 3siO 3/2unit form multipolymer, by (CH 3) HSiO unit, (CH 3) 2siO unit and C 6h 5siO 3/2unit form multipolymer, by (CF 3c 2h 4) HSiO unit, (CH 3) 3siO 1/2unit, (CH 3) (CF 3c 2h 4) SiO unit and CH 3siO 3/2unit form multipolymer, by (CH 3) HSiO unit, (CH 3) 3siO 1/2unit, (CH 3) (CF 3c 2h 4) SiO unit, (CH 3) 2siO unit and CH 3siO 3/2unit form multipolymer, by (CH 3) 2hSiO 1/2unit, (CH 3) (CF 3c 2h 4) SiO unit and CH 3siO 3/2unit form multipolymer, by (CH 3) HSiO unit, (CH 3) 3siO 1/2unit, (CH 3) (CF 3c 2h 4) SiO unit and (CH 3) 2siO unit form multipolymer, by (CH 3) HSiO unit, (CH 3) 3siO 1/2unit, (CH 3) (CF 3c 2h 4) SiO unit, (CH 3) 2siO unit and CF 3c 2h 4siO 3/2unit form multipolymer, by (CH 3) HSiO unit, (CH 3) 3siO 1/2unit, (CH 3) 3siO 1/2unit, (CH 3) 2siO unit and CH 3siO 3/2unit form multipolymer, by (CH 3) HSiO unit, (CH 3) 3siO 1/2unit, (CH 3) 3siO 1/2unit, (C 6h 5) 2siO unit, (CH 3) 2siO unit and CH 3siO 3/2unit form multipolymer, by (C 6h 5) HSiO unit, (CH 3) 3siO 1/2unit, (CH 3) 2siO unit and CH 3siO 3/2the multipolymer etc. that unit is formed.
When surface treatment being carried out to inorganic filler with above-mentioned silicon compound, the usage quantity of this silicon compound relative to inorganic filler preferably at 0.05 ~ 5 quality %, more preferably in the scope of 0.1 ~ 3 quality %.If this usage quantity is in the scope of 0.05 ~ 5 quality %, be then difficult to produce a large amount of spaces, easily obtain the sufficient bounding force to adherend.
Relative to the polymkeric substance of 100 mass parts (A) composition, the combined amount of (C) composition is generally 1000 ~ 4000 mass parts, is preferably 1000 ~ 2000 mass parts, is particularly preferably 1100 ~ 1600 mass parts.If (C) combined amount of composition is very few, then there is the situation that cannot obtain the cured article with thermal conductivity necessary in industry.If (C) combined amount of composition is too much, then there is the composition of acquisition cannot form membranaceous, to be difficult to be used as film adhesive situation.
[(D) Epoxy cure catalysts]
Binder composition of the present invention can use Epoxy cure catalysts (D).This Epoxy cure catalysts (D) is not particularly limited, such as, have phosphorus series catalysts, amine series catalysts etc.(D) composition can be used alone a kind, also may be two kinds or more.
Herein, phosphorus series catalysts such as has: triphenyl phosphine, borphenyl triphenyl phosphate base phosphine, tetraphenyl borate tetraphenyl phosphine and under the compound that shows.
[chemical formula 13]
In formula, R 6~ R 13for halogen atoms such as hydrogen atom or fluorine, bromine, iodine; The alkyl of carbonatoms 1 ~ 8, alkenyl or alkynyl, trifluoromethyl or phenyl etc. are non-substituted or the monovalent hydrocarbon that replaces; Or the alkoxyl group of carbonatoms 1 ~ 8, all substituting groups can be identical, also can be different.
Herein, R 6~ R 13monovalent hydrocarbon have and above-mentioned R 4the alkyl that illustrative alkyl is same, the Alkoxy of carbonatoms 1 ~ 8 is if any methoxyl group, oxyethyl group, propoxy-, isopropoxy, butoxy etc.
Amine series catalysts such as has: the imdazole derivatives etc. such as Dyhard RU 100, glyoxal ethyline, 2-ethyl-4-methylimidazole, 1-cyano ethyl-glyoxal ethyline, 2-phenyl-4,5-bishydroxymethyl imidazoles.
(D) combined amount of composition, catalytic amount (namely as the significant quantity of catalyzer) can be such as 10 ~ 30 mass parts relative to (A) composition of 100 mass parts.
[solidifying agent of (E) epoxy resin]
According to circumstances, the solidifying agent of (E) epoxy resin can be used in binder composition of the present invention.This solidifying agent can use in the past known various solidifying agent used for epoxy resin, such as have: diethylenetriamine, triethylene tetramine, diethyl amino propylamine, N-aminoethyl piperazine, two (4-amino-3-methylcyclohexyl) methane, m-xylene diamine, menthanediamine (メ Application タ Application ジ ア ミ Application), 3, two (the 3-aminopropyl)-2 of 9-, 4,8, the amine compounds such as 10-tetra-oxaspiro (5,5) undecane, the modified aliphatic polyamines such as epoxy resin-diethylenetriamine adducts, amine-ethylene oxide adduct, cyano ethyl polyamines, dihydroxyphenyl propane, trishydroxymethyl allyl group oxygen base phenol, the phenol novolacs of low polymerization degree, epoxidation or butylation resol or with " SuPer Beckcite " 1001 [Japanese Reichhold chemical industry (strain) system], " Hitanol " 4010 [(strain) Hitachi system], Scado form is (Dutch Scado Zwoll society system) L.9, resol containing at least 2 phenolic hydroxyl groups in the molecule of the resol that the trade(brand)names such as Methylon 75108 (General Electric Inc. of the U.S.) are known etc., with " Beckamine " carbon resin that P.138 trade(brand)name such as [Japanese Reichhold chemical industry (strain) system], " Melan " [(strain) Hitachi system], " U-Van " 10R [Japan's high pressure industrial (strain) system] is known, the aminoresin such as melamine resin, aniline resin, formula HS (C 2h 4oCH 2oC 2h 4sS) sc 2h 4oCH 2oC 2h 4there is in per molecule shown in SH (integers of s=1 ~ 10) thio resin of at least 2 sulfydryls, organic acid or its acid anhydride (acid anhydrides) etc. such as Tetra hydro Phthalic anhydride, hexahydrophthalic anhydride, Tetra Hydro Phthalic Anhydride, pyromellitic dianhydride, methyl Na Dike acid, dodecyl succinic anhydride, hexachloroendomethylene-tetrahvdrophthalic anhydride.In above-mentioned solidifying agent, phenolic aldehyde system resin (phenol resol resins) makes composition of the present invention have good forming operation and excellent wet fastness, and nontoxicity, less expensive, be therefore wish to use.(E) solidifying agent of composition is not necessarily limited to a kind in use, may be two kinds or more according to its curing performance etc.
The usage quantity of this solidifying agent because of its concrete kind different, suitable combined amount is also different, in general, preferably relative to the above-mentioned epoxy resin of 100 mass parts in 0 ~ 100 mass parts, preferably in the scope of 5 ~ 50 mass parts.When the usage quantity of solidifying agent is less than 1 mass parts, then there is the situation being difficult to solidify composition of the present invention well.On the contrary, if more than 100 mass parts, then, except unfavorable economically, epoxy resin is diluted, and needs to solidify for a long time, and occurs that the physical property of cured article reduces disadvantageous like this situation sometimes.
Use in skeleton there is phenolic hydroxyl group polyimide resin as (A) composition time, (B) epoxy resin and (E) phenolic aldehyde system resin curing agent are important relative to the ratio of mixture ((B)+(E)/(A)) of (A) polyimide resin.Now, be utilize the reaction of phenolic hydroxyl group and epoxy group(ing) to be cured reaction, if epoxy group(ing) is very few, then have the anxiety with the bounding force deficiency of adherend; And too much, then flexible modulus situation about rising because of epoxy resin, is therefore not suitable for making soft adhesive sheet.Therefore, relative to 100 mass parts (A) polyimide resin, wish that the combined amount of (B) epoxy resin and (E) phenolic aldehyde system resin curing agent is 1 ~ 900 mass parts, be preferably 5 ~ 400 mass parts.
Herein, the polyimide resin total amount in (E) phenolic aldehyde system resin curing agent and (A) skeleton with phenolic hydroxyl group is not particularly limited relative to the stoichiometric ratio ((A)+(E)/(B)) of (B) epoxy resin, preferably in the scope of 0.7 ~ 1.3, more preferably 0.8 ~ 1.2.If exceed this scope, then there is the situation causing characteristic to change in time.
It should be noted that, though when without phenolic aldehyde system resin as epoxy curing agent, combined amount and the equivalence ratio of (A) polyimide resin and (B) epoxy resin also can be as described above.
[other compositions]
In the scope not damaging effect of the present invention, different according to object, the weighting agent beyond (C) compositions such as fine silica powder end, titanium oxide, carbon black, conductive particle can be added further in resin combination of the present invention, the tinting materials such as inorganic system or organic system pigment, dyestuff, wettability rising agent, antioxidant, the additive etc. of thermo-stabilizer etc.
[preparation method of binder composition and purposes]
Binder composition of the present invention can conventionally, be prepared by above-mentioned (A) ~ (C) composition and (D) composition as required, (E) composition and other compositions being mixed.
The using method of the binder composition of the present invention obtained above is as follows: such as, with suitable concentration, this binder composition is dissolved in the aprotic polar solvent such as toluene, pimelinketone, NMP (METHYLPYRROLIDONE), be coated on substrate, make it dry, pressing adherend is heating and curing.Can also by with proper concn, the binder composition be dissolved in solvent is coated on support base material (below sometimes referred to as base material), make it dry, it (is be configured as membranaceous said composition that acquisition possesses the binder layer be made up of said composition that base material and this base material are arranged, below referred to bonding film) bonding sheet material, clamp this bonding film with substrate and adherend, pressing, be heating and curing to bond.Above-mentioned base material can use polyethylene, polypropylene, polyester, polymeric amide, polyimide, polyamidoimide, polyetherimide, tetrafluoroethylene, paper, tinsel etc. or by the gains of their surperficial demoulding process.
Binder composition of the present invention is configured as membranaceous when obtaining bonding film, preferably at normal temperature ~ 200 DEG C, particularly 80 ~ 150 DEG C dry 1 minute ~ 1 hour, particularly 3 ~ 10 minute.
The thickness of this bonding film is not particularly limited, can selects according to object, be preferably 5 ~ 100 μm, particularly 5 ~ 40 μm.Bonding film under pressure 0.01 ~ 10MPa, particularly 0.1 ~ 2MPa after pressing, preferably solidify at temperature 100 ~ 200 DEG C, particularly 120 ~ 180 DEG C 30 minutes ~ 5 hours, particularly 1 ~ 4 hour.
The using method of the thermal conductivity dicing die bonding film using binder composition of the present invention as binder layer is as follows: the base material film of release adhesive oxidant layer side as required, by wafer hot pressing on the binder layer of dicing die bonding film, be fixed on dicing die bonding film.Hot pressing condition can carry out various selection according to the composition of binder layer, is generally 40 ~ 120 DEG C and 0.01 ~ 0.2MPa.Next, be fixed on cutting unit, after cutting, the chip being attached with binder layer taken out (pickup) after binder layer is peeled off, by this chip hot pressing on lead frame, making it bond by being heating and curing.This hot pressing condition can be identical with the hot pressing condition of binder layer with wafer, and in addition, the condition of being heating and curing can carry out various selection according to the composition of binder layer, is generally 120 ~ 250 DEG C.
Binder composition of the present invention not only can be used as dicing die bonding film in the manufacture of electronic unit, can also use in the various steps with bonding.
Embodiment
Below, illustrate that embodiment and comparative example are to specifically describe the present invention, but the present invention is not limited to following embodiment.
[material]
(A) have in polymer backbone the functional group that can react with epoxy resin, Tg is the polymkeric substance of more than 45 DEG C
The polyimide resin with phenolic hydroxyl group obtained in following synthesis example 1;
JER (registered trademark) 1256 (trade(brand)name, JER Inc. have the phenoxy resin of epoxy group(ing), weight-average molecular weight: 50000, Tg:100 DEG C).
(B) there is in per molecule the epoxy resin of at least 2 epoxy group(ing)
RE-310S: bisphenol A type epoxy resin (trade(brand)name, Japanese chemical drug (strain) Inc., weight-average molecular weight: 600).
(C) with the number-average molecular weight shown in an above-mentioned average group accepted way of doing sth (I) be 500 ~ 10000 silicon compound has carried out surface-treated, thermal conductivity is the inorganic filler of more than 10W/mK.
(C1) surface-treated aluminum oxide has been carried out with the silicon compound C1 of following formula: AO-502 (trade(brand)name, Admatechs Inc., aluminum oxide, thermal conductivity: 27W/mK)
[chemical formula 14]
That is, an average group accepted way of doing sth is used: (HR 1siO) a(R 2 3siO 1/2) b(R 3 2siO) c(R 4siO 3/2) d(in formula, R 1~ R 4represent methyl, a is 0.167, b be 0.167, c be 0.667, d is 0.) silicon compound that represents, number-average molecular weight: 700.
(C2) surface-treated aluminum oxide has been carried out with the silicon compound C2 of following formula: AO-502 (trade(brand)name, as mentioned above)
[chemical formula 15]
That is, an average group accepted way of doing sth is used: (HR 1siO) a(R 2 3siO 1/2) b(R 3 2siO) c(R 4siO 3/2) d(in formula, R 1~ R 4represent methyl, a is 0.409, b be 0.013, c be 0.579, d is 0.) silicon compound that represents, number-average molecular weight: 8400.
(C3) surface-treated aluminum oxide has been carried out with the silicon compound C3 of following formula: AO-502 (trade(brand)name, as mentioned above)
[chemical formula 16]
That is, an average group accepted way of doing sth is used: (HR 1siO) a(R 2 3siO 1/2) b(R 3 2siO) c(R 4siO 3/2) d(in formula, R 1~ R 4represent methyl, a is 0.469, b be 0.063, c be 0.469, d is 0.) silicon compound that represents, number-average molecular weight: 1700.
(C4) surface-treated aluminum oxide has been carried out with the silicon compound C4 of following formula: AO-502 (trade(brand)name, as mentioned above)
[chemical formula 17]
That is, an average group accepted way of doing sth is used: (HR 1siO) a(R 2 3siO 1/2) b(R 3 2siO) c(R 4siO 3/2) d(in formula, R 1~ R 4represent methyl, a is 0.691, b be 0.029, c be 0.279, d is 0.) silicon compound that represents, number-average molecular weight: 3400.
(C') (compare use) with shown in an above-mentioned average group accepted way of doing sth (I), number-average molecular weight be 500 ~ 10000 silicon compound beyond silicon compound has carried out surface-treated, thermal conductivity is the inorganic filler of more than 10W/mK; Or not with silicon compound carry out surface-treated, thermal conductivity is the inorganic filler of more than 10W/mK.
(C5) surface-treated aluminum oxide has been carried out with the silicon compound C5 of following formula: AO-502 (trade(brand)name, as mentioned above)
[chemical formula 18]
That is, an average group accepted way of doing sth is used: (HR 1siO) a(R 2 3siO 1/2) b(R 3 2siO) c(R 4siO 3/2) d(in formula, R 1~ R 4represent methyl, a is 0.083, b be 0.083, c be 0.833, d is 0.) silicon compound that represents, number-average molecular weight: 1400.
(C6) surface-treated AO-502 has been carried out with the silicon compound C6 of following formula
[chemical formula 19]
That is, an average group accepted way of doing sth is used: (HR 1siO) a(R 2 3siO 1/2) b(R 3 2siO) c(R 4siO 3/2) d(in formula, R 1~ R 4represent methyl, a is 0.154, b be 0.003, c be 0.843, d is 0.) silicon compound that represents, number-average molecular weight: 39800.
(C7) surface-treated aluminum oxide has been carried out with the silicon compound C7 of following formula: AO-502 (trade(brand)name, as mentioned above)
[chemical formula 20]
That is, an average group accepted way of doing sth is used: (HR 1siO) a(R 2 3siO 1/2) b(R 3 2siO) c(R 4siO 3/2) d(in formula, R 1~ R 4represent methyl, a is 0.500, b be 0.333, c be 0.167, d is 0.) silicon compound that represents, number-average molecular weight: 400.
(C8) surface-treated aluminum oxide has been carried out with the silicon compound C8 of following formula: AO-502 (trade(brand)name, as mentioned above)
[chemical formula 21]
That is, an average group accepted way of doing sth is used: (HR 1siO) a(R 2 3siO 1/2) b(R 3 2siO) c(R 4siO 3/2) d(in formula, R 1~ R 4represent methyl, a is 0.889, b be 0.111, c be 0, d is 0.) silicon compound that represents, number-average molecular weight: 900.
(C9) surface-treated aluminum oxide is not carried out with silicon compound: AO-502 (trade(brand)name, as mentioned above).
It should be noted that, (C1) ~ (C8) composition is above-mentioned silicon compound and the 100 mass parts aluminum oxide by 1.7 mass parts being corresponded to (C1) ~ (C8) composition: AO-502 (trade(brand)name, mix as mentioned above), at 150 DEG C, carry out thermal treatment in 60 minutes prepare.
(D) curing catalysts
DICY-7 (trade(brand)name, JER (strain) Inc., Dyhard RU 100).
[synthesis of polyimide resin]
[synthesis example 1]
Diamino siloxanes (the trade(brand)name: KF-8010 of 44.03 mass parts as the following structural formula of diamines is added to being equipped with the 25ml being connected to reflux cooler and being with in the detachable flask of 1L of cock water and basis weight receptor, thermometer and agitator, chemical company of SHIN-ETSU HANTOTAI system) and 100 mass parts as the 2-methyl-2-pyrrolidone of reaction solvent, stir at 80 DEG C, make this diamino silicone dispersion in reaction solvent.Dripping wherein by 38.72 mass parts is the 6FDA (2 of acid anhydrides, 2-two (3,4-dicarboxyphenyi) hexafluoropropane dianhydride) and 100 mass parts 2-methyl-2-pyrrolidones form solution, stirred at ambient temperature 2 hours, make diamines and anhydride reaction, the oligoamic acid of acid anhydrides is rich in synthesis thus.
[chemical formula 22]
Wherein, t=10.
Next, the aromatic diamine with phenolic hydroxyl group shown in 17.25 mass parts following formulas is added to being equipped with the 25ml being connected to reflux cooler and being with in the detachable flask of 1L of cock water and basis weight receptor, thermometer and agitator:
[chemical formula 23]
With 100 mass parts 2-methyl-2-pyrrolidones, this aromatic diamine is dispersed in 2-methyl-2-pyrrolidone.Drip wherein above-mentioned be rich in the oligoamic acid of acid anhydrides after, at room temperature stir 16 hours, synthesizing polyamides acid solution.Afterwards, in this solution, add raised temperature after 25ml dimethylbenzene, reflux 2 hours at about 180 DEG C.Confirm have a certain amount of water to store in water and basis weight receptor, and the outflow of non-water breakthrough, the effluent liquid stored in removing water and basis weight receptor, removes removal xylene simultaneously at 180 DEG C.After reaction terminates, in excessive methyl alcohol, drip the reaction solution of acquisition, polymkeric substance is separated out, drying under reduced pressure, obtain the polyimide resin in skeleton with phenolic hydroxyl group.The content of phenolic hydroxyl group is 20 % by mole relative to amine unit.In addition, weight-average molecular weight is 50000.
The infrared extinction spectrum of polyimide resin obtained is measured, do not occur indicating unreacted functional group, based on the absorption of polyamic acid, confirm at 1780cm -1and 1720cm -1there is the absorption based on acylimino at place, confirms at 3500cm -1there is the absorption based on phenolic hydroxyl group at place.
The polyimide resin of acquisition is cast on Teflon (registered trademark) film, make the polyimide film that thickness is 100 μm.With the thermomechanical trier TM-7000 of vacuum science and engineering Inc., under the condition of load 10g and heat-up rate 10 DEG C/min, measure the Tg of this polyimide film by thermo-mechanical analysis (TMA) method, result is 130 DEG C.
[preparation of binder composition and evaluating characteristics]
[embodiment 1 ~ 7, comparative example 1 ~ 7]
Combined amount shown according to the form below 1 or 2 by (A) component dissolves in polymer dilution solvent (pimelinketone), combined amount shown according to the form below 1 or 2 is added (B) composition, (C) composition or (C') composition, (D) composition and the methyl ethyl ketone (MEK) as rear interpolation solvent and is mixed in gained solution, prepares binder composition.
[making of bonding sheet material]
The binder composition of above-mentioned acquisition is coated in the PET film of thick 38 μm with the coating of fluorine silicon mold release agent, heat drying 10 minutes at 110 DEG C, makes the bonding sheet material possessing the binder layer (calling bonding film in the following text) of thickness about 25 μm.
[260 DEG C of shear adhesion power]
The bonding film of 3mm × 3mm is obtained above by the bonding sheet material made.The silicon wafer preparing 3mm × 3mm × thick 725 μm in addition and the surfaceness being coated with AUS308 (sun ink (strain) is made for trade(brand)name, solder resist) are the BT substrate (15mm × 15mm) of less than 5 μm.Above-mentioned bonding film and above-mentioned silicon wafer stack by this order by this BT substrate, make wholely below this silicon wafer to be covered by this bonding film, 170 DEG C, 0.67MPa, carry out chip attachment under the condition of 2 seconds.This laminate be made up of silicon wafer, bonding film and BT substrate is heated under the condition of 175 DEG C/4 hours, this bonding film is solidified, afterwards 260 DEG C temperature, under the height, the velocity of shear of 200 μm/second of BT substrate 50 μm, measure the bounding force of the solidification bonding film of acquisition.Result is as shown in table 1 or 2.
[260 DEG C of shear adhesion power after JEDEC L2]
By the above-mentioned laminate that is made up of silicon wafer, bonding film and BT substrate JEDEC L2 condition (85 DEG C, under the condition of 60%RH 168 hours) under preserve, following 3 IR refluxes by top temperature 260 DEG C, measure the bounding force of solidification bonding film afterwards under condition same as described above.Result is as shown in table 1 or 2.
[thermal conductivity]
By laminated for multiple above-mentioned bonding film, make be made up of this bonding film thick 50 μm, the discoid laminate of diameter 12.5mm.Between the Al plate this laminate being clipped in 2 thick 1mm, being heated to 175 DEG C makes this bonding film solidify, and presses the thermal conductivity that laser flash method (Laser flash method) measures solidification bonding film afterwards with xenon flash of light analyser (the Xenon flash analyzer) LFA 447 of NETZSCH company.Result is as shown in table 1 or 2.
[table 1]
[table 2]
。

Claims (8)

1. the thermally conductive adhesive composition containing following (A) ~ (C) composition:
(A) polyimide resin or bisphenol type phenoxy resin 100 mass parts;
(B) there is in per molecule epoxy resin 50 ~ 400 mass parts of at least 2 epoxy group(ing); And
(C) by the number-average molecular weight that a following average group accepted way of doing sth (I) represents be 500 ~ 10000 inorganic filler 1000 ~ 4000 mass parts that silicon compound has carried out surface-treated, thermal conductivity is more than 10W/mK,
In formula, R 1~ R 4the monovalent hydrocarbon that respective independent expression does not have the non-substituted of aliphatic unsaturated link(age) or replaces, a is the positive number of 0.1 ~ 0.7, and b is the positive number of 0.01 ~ 0.2, and c is the number of 0 ~ 0.9, and d is the number of 0 ~ 0.2, and condition meets a+b+c+d=1.
2. the thermally conductive adhesive composition of claim 1, wherein, above-mentioned (A) composition is the polymkeric substance containing at least a kind that is selected from polyimide resin, this polyimide resin is the closed loop derivative of reaction product, the i.e. polyamic acid of tetracarboxylic dianhydride and the diamine compound containing diamines shown in following formula (5)
In formula, R 1for the divalent organic group of carbonatoms 3 ~ 9, R 2and R 3respective is independently non-substituted or the monovalent hydrocarbon of the carbonatoms 1 ~ 8 of replacement, and r is the integer of 1 ~ 200.
3. the thermally conductive adhesive composition of claim 2, wherein, above-mentioned diamine compound contains the diamines that (6') following formula represents further,
In formula, R 4independent be the monovalent hydrocarbon of carbonatoms 1 ~ 8 of hydrogen atom, halogen atom or non-substituted or replacement, and n is the integer of 1 ~ 5, and A is independently
In formula, R 4same as described above, R is independently hydrogen atom, halogen atom or monovalent hydrocarbon that is non-substituted or that replace,
B is independently
In formula, R 4same as described above.
4. the thermally conductive adhesive composition of claim 3, wherein, the diamines that (6') above formula represents is the diamines that following formula (6) represents,
In formula, R 4same as described above.
5. the thermally conductive adhesive composition of claim 1, said composition is further containing (D) Epoxy cure catalysts.
6. the thermally conductive adhesive composition any one of Claims 1 to 5, said composition is shaped to membranaceous.
7. bonding sheet material, it possesses: the binder layer that the thermally conductive adhesive composition recorded any one of Claims 1 to 5 that base material and this base material are arranged is formed.
8. thermal conductivity dicing die bonding film, it possesses: have the binder layer that the thermally conductive adhesive composition recorded any one of Claims 1 to 5 that the cutting film of adhesive layer of base material and its upper setting and the adhesive layer of this cutting film are arranged is formed.
CN201210409530.2A 2011-10-24 2012-10-24 Thermally conductive adhesive composition, the bonding sheet material using said composition and thermal conductivity dicing die bonding film Expired - Fee Related CN103059787B (en)

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