CN103059787A - Thermal conductive adhesive composition, bonding sheet by using composition and thermal conductive cutting chip foil - Google Patents

Thermal conductive adhesive composition, bonding sheet by using composition and thermal conductive cutting chip foil Download PDF

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Publication number
CN103059787A
CN103059787A CN2012104095302A CN201210409530A CN103059787A CN 103059787 A CN103059787 A CN 103059787A CN 2012104095302 A CN2012104095302 A CN 2012104095302A CN 201210409530 A CN201210409530 A CN 201210409530A CN 103059787 A CN103059787 A CN 103059787A
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composition
formula
epoxy
conductive adhesive
sio
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CN103059787B (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 potential barriers, e.g. a 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 potential barriers, e.g. a 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

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Computer Hardware Design (AREA)
  • Power Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
  • Die Bonding (AREA)
  • Dicing (AREA)

Abstract

The invention provides a thermal conductive adhesive composition with high thermal conductivity and excellent heat dissipation characteristic, good adhesiveness and excellent reliability after a moisture resistance test, a bonding sheet by using the composition and a thermal conductive cutting chip foil. The thermal conductive adhesive composition comprises (A) a polymer having a functional group capable of reacting with an epoxy resin in a polymer skeleton, (B) an epoxy resin having at least two epoxy groups in every molecule, and (C) an inorganic filler which is surface-treated by a silicon compound represented by a specific average composition formula with a number average molecular weight of 500 to 10,000 and has a thermal conductivity of 10W/mK. The bonding sheet comprises a substrate and an adhesive layer consisting of the above composition disposed on the substrate. The thermal conductive cutting chip foil comprises a substrate, a cutting foil of an adhesive layer disposed on the substrate, and the adhesive layer consisting of the above composition which is disposed on the adhesive layer of the cutting foil.

Description

Bonding sheet material and the thermal conductivity dicing die bonding film used of thermally conductive adhesive composition, use said composition
Technical field
The thermally conductive adhesive composition that the present invention relates to be suitable for that semiconductor packages, the thermal conductivity making semiconductor device, be especially suitable for use as resin die are high and heat dissipation characteristics is excellent, has strong adhesive power for silicon (Si) and solder resist (solder resist) as adherend, use the bonding with sheet material and thermal conductivity dicing die bonding film (dicing-die attach film) of said composition.
Background technology
The manufacturing step of semiconductor device is as follows: the major diameter silicon wafer that will be formed with the IC circuit by cutting (cut-out) step is cut into semi-conductor chip, fluid binder (chip adhesive material with solidified nature, ダ イ ボ Application De material) etc. hot pressing is on lead frame, (assembling is adhesively fixed, mount), carry out interelectrode wire-bonded (wire bonding), afterwards for treatability or be not subjected to the impact of outside atmosphere and seal.The non-gas-tight seal type that this sealing form has the gas-tight seal type such as metallic seal, ceramic seal and carries out with resin, now, the latter's the transfer moudling of carrying out with resin is the most generally used because of volume production excellent performance, cheapness.Yet, although this resin-molded encapsulation has above-mentioned advantage, but then, at aspect existent defects such as moisture-proof thermotolerance, thermal stresses retentivity, thermal diffusivities.
Along with in recent years miniaturization and the multifunction of electric electronic Instrument, answer the requirement of the multifunction of electronic unit, the distribution of semiconductor device is more miniaturization, densification also, because of the maximization of semi-conductor chip and have appearance without the semiconductor device of the laminate structures (folded formula CSP, SiP) of the face battle array adhesion type chip of lead frame and unidimensional structure (CSP) or chip, the thermal shocking (stress) in these encapsulation (PKG) is also day by day harsh.
Moreover, in the semiconductor device to a printed circuit board mounted (mounting) process step, corresponding to the lead-free solder (Pb free base ー は san da) in reflow resistance properties (resistance to re-flow ー sex) is also a high temperature (265 ℃), increasingly harsh.Therefore, begin material that requirement uses the most suitable and have a high-performance.Particularly, in the encapsulation constituent material, because the chip adhesive material can be in larger scope control characteristic, can easily tackle these requirements, therefore as the chip adhesive material, low elastic modulus, the height of thermal shocking (stress) that need to be corresponding harsh is bonding, the material of high heat resistance.
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, because the overlap (the は body goes out) from die terminals causes electrode fouling or tilts because bonding coat in uneven thickness makes chip, the bad situation of wire-bonded (wire bond) occurs, therefore also wish to improve the tackiness agent membranization of these shortcomings.
As these tackiness agents, having developed to the resin of excellent heat resistance at present is the low modulus of elasticity materials that imports siloxane structure in polyimide or the polyamidoimide.All proposed silicone-modified polyamidoimide in the patent documentation 1,2 etc., but they still have deficiency in low elasticity with aspect the binding property of adherend.
Proposed in silicone-modified polyamidoimide, to mix the compound with 2 above maleimide amino in the patent documentation 3 and improved hot properties, but this resin combination poor adhesion.
Proposed in the patent documentation 4 and 5 binding property, low elasticity and excellent heat resistance, by the thermotolerance bonding film that polyimide silicon and Resins, epoxy consist of, the bounding force of this film improves, but low elasticityization is not enough.
The prior art document
Patent documentation
Patent documentation 1 Japanese kokai publication hei 3-189127 communique;
Patent documentation 1 Japanese kokai publication hei 4-264003 communique;
Patent documentation 3 Japanese kokai publication hei 10-60111 communiques;
Patent documentation 4 Japanese kokai publication hei 7-224259 communiques;
Patent documentation 5 Japanese kokai publication hei 8-27427 communiques;
Patent documentation 6 TOHKEMY 2003-193016 communiques.
Because the in recent years miniaturization of semi-conductor chip and fast switching (i.e. fast operation), the unit surface heat of generation has the tendency of increase, and for efficiently radiates heat, the adhesive film for semiconductor that thermal conductivity is high becomes the demand in market.
The simple composition that has added the filler of high thermal conductivity coefficient in order to increase thermal conductivity is highly brittle, and can't process film forming, is to be not suitable for practical composition.In addition, if improve the processibility of film and add in a large number the low viscosity composition, then bounding force reduces before and after the moisture absorption, reduces as the reliability of semiconductor packages.
Summary of the invention
The problem that invention will solve
The present invention In view of the foregoing carries out, in order to overcome defects, purpose is to provide: thermal conductivity is high and heat dissipation characteristics is excellent, binding property is good and humidity test after the reliability excellence thermally conductive adhesive composition, use the bonding with sheet material and thermal conductivity dicing die bonding film of said composition.
Be used for solving the means of problem
The inventor conducts in-depth research to achieve these goals, found that: as the high thermal conductivity filler, using the filler that its surface has been carried out processing with specific silicon compound is effectively, thereby has finished the present invention.
That is, the first, the invention provides the thermally conductive adhesive composition that contains following (A)～(C) composition:
(A) have in the polymer backbone can with polymkeric substance 100 mass parts of the functional group of Resins, epoxy reaction;
(B) have Resins, epoxy 50～400 mass parts of at least 2 epoxy group(ing) in the per molecule; And
(C) with the number-average molecular weight of a following average group accepted way of doing sth (I) expression be 500～10000 silicon compound to have carried out surface-treated, thermal conductivity be above inorganic filler 1000～4000 mass parts of 10W/mK,
Figure 2012104095302100002DEST_PATH_IMAGE001
In the formula, R 1～R 4Independent expression does not have the monovalence alkyl of the non-substituted of aliphatic unsaturated link(age) or replacement separately, and a is 0.1～0.7 positive number, and b is 0.01～0.2 positive number, and c is 0～0.9 number, and d is 0～0.2 number, and condition is to satisfy a+b+c+d=1.
The second, the invention provides the bonding sheet material of using, it possesses: the binder layer that is made of above-mentioned thermally conductive adhesive composition that arranges on base material and this base material.
The 3rd, the invention provides the thermal conductivity dicing die bonding film, it possesses: have the binder layer that is made of above-mentioned thermally conductive adhesive composition that arranges on this adhesive layer of the cutting film of adhesive layer of the upper setting of base material and its and this cutting film.
The invention effect
Binder composition thermal conductivity of the present invention is high and heat dissipation characteristics is excellent, and is excellent with the binding property of adherend.Nationality can be made the resin encapsulated semiconductor device of high reliability by using the bonding with sheet material and thermal conductivity dicing die bonding film of binder composition of the present invention.
Embodiment
Below the present invention will be described in more detail.Need to prove, that the weight-average molecular weight in this specification sheets and number-average molecular weight refer to respectively to measure under the following conditions, by gel permeation chromatography (GPC) weight-average molecular weight and number-average molecular weight that carry out, take polystyrene as reference material.
[condition determination]
Developing solvent: tetrahydrofuran (THF) (THF);
Flow: 1mL/ minute;
Device: HLC-8320GPC (trade(brand)name, Tosoh company system);
Detector: differential refraction rate detector (RI);
Post: TSKgel GMH XL-L+TSKgel G4000H XL+ TSKgel G2000H XL+ TSKgel G2000H XL(trade(brand)name, Tosoh company system);
Column temperature: 40 ℃;
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 under the normal temperature, forms membranaceous film, and heating is solidified by plasticized condition, therefore adherend is shown excellent binding property.The cured article excellent thermal conductivity of binder composition of the present invention.Use possesses the thermal conductivity dicing die bonding film of the binder layer that is made of binder composition of the present invention and the reliability of semiconductor made is excellent.
[(A) have in the polymer backbone can with the polymkeric substance of the functional group of Resins, epoxy reaction]
In binder composition of the present invention, have in the polymer backbone to be necessary with the polymkeric substance of the functional group of Resins, epoxy reaction, the reasons are as follows: be less state in order to make the space between bonding film and the substrate during chip attachment, the shear viscosity of bonding film under at least 1 temperature between 130～170 ℃ need to be 1 * 10 3～1 * 10 5In the scope of Pas, this point be experimental results show that.For above-mentioned shear viscosity is kept within the limits prescribed, need to contain the high component of polymer of viscosity ratio monomer in the composition of formation bonding film.(A) composition can use separately a kind, also can will also use more than 2 kinds.In addition, in order to make firmly matrix (matrix) between the Resins, epoxy contained in binder composition of the present invention (for example Resins, epoxy of following (B) composition), can be necessary with the functional group of Resins, epoxy reaction.
(A) second-order transition temperature of the polymkeric substance of composition (Tg) is preferably more than 40 ℃.Use Tg be component of polymer more than 40 ℃ make bonding film, and when this bonding film is processed into dicing die bonding film, this bonding film can be excessively not strong to the viscosity of cutting film, this bonding film is difficult to be attached to securely on the cutting film, easily with the short period of time this bonding film is peeled off from the cutting film, therefore easily improved the production efficiency of semiconductor device fabrication.
(A) can for example have with the functional group of Resins, epoxy reaction in the composition: at least a kind of functional group that is selected from carboxyl, amino, imino-, epoxy group(ing), phenolic hydroxyl group and thiol group.
(A) polymkeric substance of composition is preferably 10,000～200 by the weight-average molecular weight of polystyrene conversion, and 000, more preferably 20,000～100,000, be more preferably 30,000～80,000.If weight-average molecular weight in above-mentioned scope, is then easily formed by the composition that obtains film, also easily obtain to be used for filling the bonding film concavo-convex, that have enough flexibilities of the substrate surface with fine circuit pattern.
(A) polymkeric substance of composition for example has polyimide resin.(A) polymkeric substance of composition also can use the polyamic acid as the precursor of polyimide resin, but when being heating and curing of chip join step sometimes because of imidization (dehydration closed-loop) by-product water, thereby produce adhesive face and the situation such as peel off, therefore preferably use the in advance polyimide resin of imidization (dehydration closed-loop).Polyamic acid for example has the compound shown in the following general formula (1).Polyimide resin for example has the compound shown in the following general formula (2).Polyamic acid and polyimide resin can contain the diorganopolysiloxanecompositions key, in addition, from fusible angle, have phenolic hydroxyl group in the preferred skeleton.
[Chemical formula 1]
Figure 760357DEST_PATH_IMAGE002
In the formula, X is the quadrivalent organic radical group that contains aromatic ring or aliphatic series ring, and Y is for having the divalent organic group of siloxane bond, and q is 1～300 integer.
[Chemical formula 2]
In the formula, X is the quadrivalent organic radical group that contains aromatic ring or aliphatic series ring, and Y is for having the divalent organic group of siloxane bond, and q is 1～300 integer.
In the above-mentioned general formula (1), q is 1～300 integer, is preferably 2～300 integer, 5～300 integer particularly, and the polyamic acid with this repeat number can easily obtain by following method.In addition, the polyimide resin shown in the above-mentioned general formula (2) can obtain the dehydration of the polyamic acid shown in the above-mentioned general formula (1), closed loop by ordinary method.
Polyamic acid shown in the general formula (1) can be according to ordinary method, by making the tetracarboxylic dianhydride shown in the following structural formula (3) with equimolar ratio roughly:
[chemical formula 3]
Figure 926765DEST_PATH_IMAGE004
(wherein, X represents and above-mentioned same implication.)
With the diamines shown in the following structural formula (4):
Figure 2012104095302100002DEST_PATH_IMAGE005
(wherein, Y represents and above-mentioned same implication.)
In organic solvent, react and obtain.
Herein, the object lesson of the tetracarboxylic dianhydride shown in the following formula (3) has following compound, but is not limited to these compounds.
[chemical formula 4]
Figure 644185DEST_PATH_IMAGE006
Need to prove, the tetracarboxylic dianhydride shown in these following formulas (3) can use one kind or two or more as required.
(a) diamino silicone compounds
From to the solvability of organic solvent, binding property, the low elasticity to adherend, the angle of flexibility, wish to preferably have in the diamines shown in the following formula (4) 1～80 % by mole, more preferably have 1～60 % by mole to be the diamino silicone compounds shown in the following structural formula (5).
[chemical formula 5]
In the formula, R 1Be the divalent organic group of carbonatoms 3～9, R 2And R 3Independent separately is non-substituted or the monovalence alkyl of the carbonatoms 1～8 of replacement, and r is 1～200 integer.
In the siloxane diamine shown in the general formula (5) (or α, ω-diamino polysiloxane), R 1The divalent organic group of shown carbonatoms 3～9 for example has-(CH 2) 3-,-(CH 2) 4-,-CH 2CH (CH 3)-,-(CH 2) 6-,-(CH 2) 8-wait alkylidene group;
[chemical formula 6]
Figure 977078DEST_PATH_IMAGE008
、
Figure 2012104095302100002DEST_PATH_IMAGE009
、
Figure 227668DEST_PATH_IMAGE010
Deng arylidene; The alkylidene group arylidene that these alkylidene groups and arylidene are combined;-(CH 2) 3-O-,-(CH 2) 4The alkylidene oxides such as-O-(オ キ シ ア Le キ レ Application);
[chemical formula 7]
Figure 2012104095302100002DEST_PATH_IMAGE011
、
Figure 50131DEST_PATH_IMAGE012
Deng oxidation arylidene (オ キ シ ア リ ー レ Application base); These alkylidene oxides and arylidene are for example combined:
[chemical formula 8]
Figure 2012104095302100002DEST_PATH_IMAGE013
Can contain the plain atom of ether oxygen atom (エ ー テ Le acid Deng alkylidene oxide arylidene etc.) bivalent hydrocarbon radical.
R 2Or R 3The monovalence alkyl of the carbonatoms 1～8 of shown non-substituted or replacement is such as having: 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; The group that part or all of the hydrogen atom of being combined with the carbon atom of these groups replaced by halogen atoms such as fluorine, bromine, chlorine etc., for example chloromethyl, bromotrifluoromethane, 3,3, the haloalkyls such as 3-trifluoro propyl etc.Wherein preferable methyl and phenyl.
Compound shown in below diamino silicone compounds shown in the following formula (5) specifically has.
[chemical formula 9]
Figure 254847DEST_PATH_IMAGE014
Diamino silicone compounds shown in these following formulas (5) can use a kind separately according to hope, also can use the combination more than 2 kinds.
(b) do not have the diamine compound of phenolic hydroxyl group
Regulate the flexibility of resin combination and control to the angle of the intermiscibility of Resins, epoxy from control and the cross-linking set of Resins, epoxy, wish to preferably have in the diamines shown in the following formula (4) 40～95 % by mole, more preferably have 50～90 % by mole for not having the diamine compound of phenolic hydroxyl group.
In the diamines shown in the following formula (4); except the diamino silicone compounds shown in the following formula (5); the diamines that does not have phenolic hydroxyl group for example has: Ursol D; mphenylenediamine; 4; the 4'-diaminodiphenyl-methane; 4; 4'-diamino-diphenyl ether; 2; 2 '-two (4-aminophenyl) propane; 4; the 4'-diamino diphenyl sulfone; 4; 4'-diamino-diphenyl sulfide; 1; two (3-amino-benzene oxygen) benzene of 4-; 1; two (4-amino-benzene oxygen) benzene of 4-; 1; two (p-aminophenyl alkylsulfonyl) benzene of 4-; 1; two (the m-aminophenyl base alkylsulfonyl) benzene of 4-; 1; two (p-aminophenyl thioether) benzene of 4-; 1; two (the m-aminophenyl base thioether) benzene of 4-; 2; 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 [3-chloro-4-(4-amino-benzene oxygen) phenyl] propane of 2-; 1; 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 [3-chloro-4-(4-amino-benzene oxygen) phenyl] ethane of 1-; 1; 1-two [3; 5-dimethyl-4-(4-amino-benzene oxygen) phenyl] ethane; two [4-(4-amino-benzene oxygen) phenyl] methane; two [3-methyl-4-(4-amino-benzene oxygen) phenyl] methane; two [3-chloro-4-(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 etc. of 2,2-contain the diamines of aromatic ring etc.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, 2 of 2-, two [3-methyl-4-(4-amino-benzene oxygen) phenyl] propane of 2-etc.
(c) has the diamine compound of phenolic hydroxyl group
Among the present invention, from fusible angle, has phenolic hydroxyl group in the polymer backbone of preferred polyimide resin.The importing of phenolic hydroxyl group can be by realizing with having the diamine compound that is the phenolic hydroxyl group of hyperergy with epoxy group(ing).This diamines for example has: the compound shown in the following formula.
[Chemical formula 1 0]
Figure 2012104095302100002DEST_PATH_IMAGE015
In the formula, R 4Independent is hydrogen atom; The halogen atoms such as fluorine atom, bromine atoms, iodine atom; The perhaps monovalence alkyl of the non-substituted or carbonatoms 1～8 that replaces such as alkyl, alkenyl, alkynyl, trifluoromethyl, phenyl, n is 1～5 integer, A and B separately can be identical or different.R independently is hydrogen atom, halogen atom or monovalence alkyl non-substituted or that replace.
Herein, R 4Monovalence the alkyl non-substituted or carbonatoms 1～8 that replaces for example have: with above-mentioned R 2Or R 3The alkynyls such as the alkyl that illustrative alkyl is same and ethynyl, proyl, butynyl, hexin base etc.The monovalence alkyl non-substituted or that replace of R also can be enumerated and above-mentioned R 4The alkyl that illustrative alkyl is same.
Among the present invention, even in above-mentioned diamine compound with phenolic hydroxyl group, the also diamine compound shown in the following formula (6) particularly preferably.
[Chemical formula 1 1]
In the formula, R 4Same as described above.
Need to prove, in the present invention, the combined amount with 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, the situation that then has bounding force to reduce; And if too much, the situation of the flexibility deficiency of binder layer is arranged then.
(d) has the monoamine compound of phenolic hydroxyl group
In order in the polymer backbone of the polyimide resin of (A) composition, to import phenolic hydroxyl group, except the diamines of formula (4), can also use the monoamine with phenolic hydroxyl group.This monoamine can be enumerated following structure.
[Chemical formula 1 2]
Figure 2012104095302100002DEST_PATH_IMAGE017
In the 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 use separately a kind, also can will also use more than 2 kinds.P is 1～3 integer.
When using above-mentioned monoamine with phenolic hydroxyl group, its combined amount is 1～10 % by mole with respect to the diamine compound total amount of following formula (4), is preferably 2～8 % by mole.
Above-mentioned monoamine compound is not limited to the compound of said structure formula, and in addition, these monoamine compounds can use separately a kind according to hope, also can will be used in combination more than 2 kinds.
About the formation reaction of polyamic acid and polyimide resin, object lesson has: under inert atmosphere above-mentioned starting raw material is dissolved in the solvent, usually makes its reaction below 80 ℃, under preferred 0～40 ℃, synthesizing polyamides acid.Further be warming up to common 100～200 ℃, preferred 150～200 ℃ by the polyamic acid that makes acquisition, make the amide moieties dehydration closed-loop of polyamic acid, can synthesize the polyimide resin of target.
The organic solvent that uses in the above-mentioned reaction can not be the solvent that can dissolve above-mentioned starting raw material fully as long as the polyamic acid that obtains is inertia.For example 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 non-proton property polar solvent, particularly preferably N-Methyl pyrrolidone, pimelinketone and gamma-butyrolactone.These solvents can use a kind or will be used in combination more than 2 kinds.
For above-mentioned dehydration closed-loop is easily carried out, wish to use the azeotropy dehydrants such as toluene, dimethylbenzene.In addition, also can use diacetyl oxide/pyridine mixing solutions to carry out at low temperatures dehydration closed-loop.
Need to prove, in order to regulate the molecular weight of polyamic acid and polyimide resin, also can add the dicarboxylic anhydrides such as maleic anhydride, Tetra hydro Phthalic anhydride; And one or both of aniline, n-butylamine, the monoamine compounds such as monoamine with phenolic hydroxyl group enumerated above.Wherein, the addition of dicarboxylic anhydride is generally 0～2 mass parts with respect to the tetracarboxylic dianhydride of 100 mass parts following formulas (3), and the addition of monoamine compound is generally 0～2 mass parts with respect to the diamines of 100 mass parts following formulas (4).
(A) polymkeric substance of composition also has phenoxy resin except above-mentioned polyimide resin.This phenoxy resin is such as having: derived from the bisphenol type phenoxy resin of Epicholorohydrin and dihydroxyphenyl propane or F etc.This phenoxy resin for example has: commodity are called PKHC, PKHH, PKHJ (by bar chemical company system), the commodity of dihydroxyphenyl propane Bisphenol F mixed type are called Epikote 4250, Epikote 4275, Epikote 1255HX30, use the Epikote 5580BPX40 (be Japanese chemical drug company system) 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 company's system), JER E1256, E4250, E4275, YX6954BH30, YL7290BH30 (being Japan epoxy resin company system) etc.
The Resins, epoxy of at least 2 epoxy group(ing) [(B) have in the per molecule]
The molecular structure of the Resins, epoxy of (B) composition, molecular weight etc. are not particularly limited.(B) Resins, epoxy of composition is preferably 100～10000 by the weight-average molecular weight of polystyrene conversion, and more preferably 100～1000.(B) composition can use separately a kind, also can will also use more than 2 kinds.
This Resins, epoxy for example has: two (4-hydroxy phenyl) methane, 2, two (4-hydroxy phenyl) propane of 2'-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 oxidation divinyl, vinyl cyclohexene dioxide, Resorcinol, 4-two (2, the 3-glycidoxy) benzene, 4,4'-two (2, the 3-glycidoxy) phenyl ether, 1,4-two (2, the 3-glycidoxy) tetrahydrobenzene, two (3,4-epoxy-6-methyl cyclohexane ylmethyl) adipic acid ester (or salt), 1,2-dioxy base benzene or Resorcinol, polyphenol or polyvalent alcohol and Epicholorohydrin condensation and the epoxy glycidyl ether or the poly glycidyl ester that obtain; The epoxy phenolics (that is, phenolic resin varnish type epoxy resin) that the phenolic varnish type resol (perhaps halogenation phenolic varnish type resol) such as phenol phenolic varnish (Off ェ ノ ー Le ノ ボ ラ ッ Network), cresols phenolic varnish (Network レ ゾ ー Le ノ ボ ラ ッ Network) obtain with the Epicholorohydrin condensation; By the epoxidised epoxidation polyolefine of peroxidation method; Epoxidized polybutadiene; Naphthalene-ring containing Resins, epoxy; Biphenyl type epoxy resin; Phenol-aralkyl-type epoxy resin; Biphenyl-aralkyl-type epoxy resin; Cyclopeutadiene type Resins, epoxy etc.
Need to prove, have in above-mentioned per molecule in the Resins, epoxy of at least 2 epoxy group(ing) and also can suitably and use mono-epoxy compounds, this mono-epoxy compounds is such as having: 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 use separately a kind, also can will also use more than 2 kinds.
With respect to the polymkeric substance of 100 mass parts (A) composition, (B) combined amount of composition is generally 50～400 mass parts, is preferably 80～300 mass parts, and more preferably 150～250 mass parts are particularly preferably 200～250 mass parts.If the combined amount of Resins, epoxy is very few, the situation of poor adhesion is arranged then; If too much, during for liquid-state epoxy resin, the excessive and situation of operational difficulty of the viscosity that pair film arranged during for the Resins, epoxy of solid state, has binder layer not form membranaceous situation.
[being that to have carried out surface-treated, thermal conductivity be the above inorganic filler of 10W/mK for 500～10000 silicon compound with the number-average molecular weight shown in the average group accepted way of doing sth (I) (C)]
(C) thermal conductivity of inorganic filler is generally more than the 10W/mK in the composition, is preferably more than the 20W/mK, is particularly preferably more than the 30W/mK.Need to prove, the thermal conductivity in this specification sheets is the value under 25 ℃.If the not enough 10W/mK of above-mentioned thermal conductivity, then thermal diffusivity is not enough, and the temperature of semiconductor element and substrate has the possibility of rising.Need to prove, the upper limit of thermal conductivity is not particularly limited, and representational is below the 500W/mK.Carry out the object lesson of surface-treated inorganic filler with above-mentioned silicon compound such as having: 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 is powder; The combination more than 2 kinds of above-mentioned powder.The preferential oxidation aluminium powder form.(C) composition can use separately a kind, also can will also use more than 2 kinds.(C) median size of composition is preferably 0.05～50 μ m.
(C) in the composition as the silicon face treatment agent, inorganic filler is carried out the surface-treated silicon compound take following average composition formula (I) expression, the number-average molecular weight silicon compound as 500～10000:
Figure 997992DEST_PATH_IMAGE018
(in the formula, R 1～R 4Independent expression does not have the monovalence alkyl of the non-substituted of aliphatic unsaturated link(age) or replacement separately, and a is 0.1～0.7 positive number, and b is 0.01～0.2 positive number, and c is 0～0.9 number, and d is 0～0.2 number, and condition is to satisfy a+b+c+d=1.)
This silicon compound plays a role as the surface treatment agent of inorganic filler with the bonding agent of adherend reaction.(C) to have carried out the surface treatment this point with this silicon compound be necessary to the inorganic filler of composition in the present invention.Namely, the surface-treated inorganic filler is in the presence of this silicon compound, under high temperature, be heat-treated, the dehydrogenation reaction of the hydroxyl of the remained on surface by this inorganic filler and mineral acid (surface treatment agent residue) and this silicon compound, this surface is modified by this silicon compound.And, modified should this silicon compound on surface in residual hydrogen atom and adherend reaction, therefore show firmly bounding force.From these angles, (C) surface treatment of composition is necessary in the present invention.As long as this silicon compound satisfies above-mentioned important document, then be not particularly limited, can synthesize by known method in the past.This silicon compound can use separately a kind, also can will also use more than 2 kinds.
When making (C) composition, preferably preferred 100～180 ℃, more preferably 110～170 ℃, be more preferably under 120～160 ℃ the temperature, in the presence of above-mentioned silicon compound that inorganic filler thermal treatment is preferred more than 10 minutes, more preferably 30～300 minutes, be more preferably 50 minutes～180 minutes.If thermal treatment temp is in 100～180 ℃ scope, then the reaction process of the hydroxyl of the remained on surface of surface-treated inorganic filler and mineral acid and above-mentioned silicon compound is easily accelerated, and above-mentioned silicon compound is difficult for deteriorated.In addition, if heat treatment time is more than 10 minutes, then the reaction of the hydroxyl of the remained on surface of surface-treated inorganic filler and mineral acid and above-mentioned silicon compound is easy to fully carry out.
Preferred above-mentioned silicon compound has at least 2 formula HR in per molecule 1That SiO represents, have the hydrogen atom of being combined with Siliciumatom, be positioned at the unit (D in the middle of the molecular chain HThe unit), in per molecule, have at least 2 formula R 2 3SiO 1/2Unit expression, that do not have the hydrogen atom of being combined with Siliciumatom.That is, preferably in this silicon compound, it is middle (that is, only at (HR that the hydrogen atom of being combined with Siliciumatom exists only in molecular chain 1SiO) in the unit), molecule chain end does not exist, molecule chain end (R 2 3SiO 1/2) unit terminated.
In the above-mentioned average group accepted way of doing sth (I), during a less than 0.1, then be difficult to obtain the bounding force to the excellence of adherend; Surpass at 0.7 o'clock, then easily produce the space in the cured article, the situation of the bounding force reduction of pair adherend is arranged.
During b less than 0.01, then easily produce the space in the cured article, the situation of the bounding force reduction of pair adherend is arranged; Surpass at 0.2 o'clock, then be difficult to obtain the bounding force to the excellence of adherend.
C surpasses at 0.9 o'clock, and then above-mentioned silicon compound easily reduces the intermiscibility of epoxy resin-base, is difficult to obtain the bounding force to the excellence of adherend.
D surpasses at 0.2 o'clock, then easily causes viscosity rise, is 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, and more preferably 1000～5000, preferably this silicon compound is liquid value room temperature (25 ℃) is lower.This number-average molecular weight was less than 500 o'clock, and the volatility of silicon compound easily raises, and the situation that is difficult to apply high temperature, the reduction of surface treatment rate is arranged when therefore the inorganic filler surface being heat-treated, and the anxiety of bounding force reduction is arranged.This number-average molecular weight was greater than 10000 o'clock, and silicon compound easily forms high viscosity, had to be difficult to guarantee the wettability to inorganic filler, the situation that the surface treatment rate reduces.In addition, this number-average molecular weight is greater than 10000 o'clock, have and inorganic filler between do not have that the residual silicon compound of chemical bond produces easily in a large number, the anxiety of bounding force reduction.
Above-mentioned silicon compound is preferably 0.1～1000mPas 25 ℃ viscosity, and more preferably 0.5～500mPas is more preferably 0.5～300mPas.Preferred this silicon compound is lower to liquid in room temperature (25 ℃).
In the above-mentioned average group accepted way of doing sth (I), R 1～R 4Carbonatoms be preferably 1～10, more preferably 1～6.R 1～R 4Object lesson such as having: 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; The group that part or all of the hydrogen atom of the alkyl that these are non-substituted replaced by halogen atoms such as fluorine atom, chlorine atoms, for example 3,3,3-trifluoro propyl etc., preferred alkyl, aryl, 3,3,3-trifluoro propyl, more preferably methyl, phenyl, 3,3,3-trifluoro propyl.
The object lesson of above-mentioned silicon compound for example has: by (CH 3) HSiO unit, (CH 3) 2SiO unit and (CH 3) 3SiO 1/2The multipolymer of cell formation, by (CH 3) HSiO unit, (CH 3) 3SiO 1/2Unit, (C 6H 5) 2SiO unit, (CH 3) 2SiO unit and CH 3SiO 3/2The multipolymer of cell formation, by (C 6H 5) HSiO unit, (CH 3) 3SiO 1/2Unit, (CH 3) 2SiO unit and CH 3SiO 3/2The multipolymer of cell formation, by (CH 3) HSiO unit, (CH 3) 2SiO unit and C 6H 5SiO 3/2The multipolymer of cell formation, by (CF 3C 2H 4) HSiO unit, (CH 3) 3SiO 1/2Unit, (CH 3) (CF 3C 2H 4) SiO unit and CH 3SiO 3/2The multipolymer of cell formation, 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 3/2The multipolymer of cell formation, by (CH 3) 2HSiO 1/2Unit, (CH 3) (CF 3C 2H 4) SiO unit and CH 3SiO 3/2The multipolymer of cell formation, by (CH 3) HSiO unit, (CH 3) 3SiO 1/2Unit, (CH 3) (CF 3C 2H 4) SiO unit and (CH 3) 2The multipolymer of SiO cell formation, 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 3/2The multipolymer of cell formation, by (CH 3) HSiO unit, (CH 3) 3SiO 1/2Unit, (CH 3) 3SiO 1/2Unit, (CH 3) 2SiO unit and CH 3SiO 3/2The multipolymer of cell formation, 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 3/2The multipolymer of cell formation, by (C 6H 5) HSiO unit, (CH 3) 3SiO 1/2Unit, (CH 3) 2SiO unit and CH 3SiO 3/2The multipolymer of cell formation etc.
When with above-mentioned silicon compound inorganic filler being carried out surface treatment, the usage quantity of this silicon compound with respect to inorganic filler preferably at 0.05～5 quality %, more preferably in the scope of 0.1～3 quality %.If this usage quantity in the scope of 0.05～5 quality %, then is difficult to produce a large amount of spaces, easily obtain the sufficient bounding force to adherend.
With respect to the polymkeric substance of 100 mass parts (A) composition, (C) combined amount of 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, the situation of the cured article that can't obtain to have thermal conductivity necessary on the industry is arranged then.If (C) combined amount of composition is too much, then there is the composition of acquisition can't form membranaceous, as to be difficult to be used as film adhesive situation.
[(D) epoxy resin cure catalyzer]
Binder composition of the present invention can use epoxy resin cure catalyzer (D).This epoxy resin cure catalyzer (D) is not particularly limited, such as phosphorus series catalysts, amine series catalysts etc. are arranged.(D) composition can use separately a kind, also can will also use more than 2 kinds.
Herein, the phosphorus series catalysts for example has: triphenyl phosphine, borphenyl triphenyl phosphate base phosphine, tetraphenyl borate tetraphenyl phosphine and the lower compound that shows.
[Chemical formula 1 3]
Figure 2012104095302100002DEST_PATH_IMAGE019
In the formula, R 6～R 13Be the halogen atoms such as hydrogen atom or fluorine, bromine, iodine; Non-substituted or the monovalence alkyl that replaces such as the alkyl of carbonatoms 1～8, alkenyl or alkynyl, trifluoromethyl or phenyl; The perhaps alkoxyl group of carbonatoms 1～8, all substituting groups can be identical, also can be different.
Herein, R 6～R 13The monovalence alkyl have and above-mentioned R 4The alkyl that illustrative alkyl is same, the alkoxyl group of carbonatoms 1～8 is such as having: methoxyl group, oxyethyl group, propoxy-, isopropoxy, butoxy etc.
The amine series catalysts for example has: Dyhard RU 100, glyoxal ethyline, 2-ethyl-4-methylimidazole, 1-cyano ethyl-glyoxal ethyline, 2-phenyl-4, the imdazole derivatives such as 5-dihydroxyl Methylimidazole etc.
(D) combined amount of composition, the catalytic amount significant quantity of catalyzer (namely as) for example (A) composition with respect to 100 mass parts can be 10～30 mass parts.
[(E) solidifying agent of Resins, epoxy]
According to circumstances, can use the solidifying agent of (E) Resins, epoxy in the binder composition of the present invention.This solidifying agent can use the various solidifying agent of in the past known used for epoxy resin, for example 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-aminopropyls)-2 of 9-, 4,8, the amine compounds such as 10-four oxaspiros (5,5) undecane; The modified aliphatic polyamines such as Resins, epoxy-diethylenetriamine adducts, amine-ethylene oxide adduct, cyano ethyl polyamines; Dihydroxyphenyl propane, trishydroxymethyl allyl group oxygen base phenol, the phenol resol 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, the resol that contains at least 2 phenolic hydroxyl groups in the molecule of the resol that the trade(brand)names such as Methylon 75108 (U.S. General Electric company system) are known etc.; With " Beckamine " known carbon resins of trade(brand)name such as [Japanese Reichhold chemical industry (strain) system], " Melan " [(strain) Hitachi system], " U-Van " 10R [Japan's high pressure industry (strain) system] P.138; The aminoresin such as melamine resin, aniline resin; Formula HS (C 2H 4OCH 2OC 2H 4SS) sC 2H 4OCH 2OC 2H 4The thio resin that has at least 2 sulfydryls in the per molecule shown in the SH (integers of s=1～10); The organic acids such as Tetra hydro Phthalic anhydride, hexahydrophthalic anhydride, Tetra Hydro Phthalic Anhydride, pyromellitic acid acid anhydride, methyl Na Dike acid, dodecyl succinic anhydride, hexachloroendomethylene-tetrahvdrophthalic anhydride or its acid anhydride (acid anhydrides) etc.In the above-mentioned solidifying agent, phenolic aldehyde is that resin (phenol novolac resin) makes composition of the present invention have good forming operation and excellent wet fastness, and nontoxicity, and is less expensive, therefore is to wish to use.(E) solidifying agent of composition is not necessarily limited to a kind in use, can more than 2 kinds and use according to its curing performance etc.
The usage quantity of this solidifying agent is different because of its concrete kind, and suitable combined amount is also different, in general, preferably with respect to the above-mentioned Resins, epoxy of 100 mass parts in 0～100 mass parts, preferably in the scope of 5～50 mass parts.During usage quantity less than 1 mass parts of solidifying agent, the situation that is difficult to solidify well composition of the present invention is arranged then.On the contrary, if surpass 100 mass parts, then except unfavorable economically, Resins, epoxy is diluted, and need to solidify for a long time, and the disadvantageous like this situation of physical property reduction of cured article occur sometimes.
Use the polyimide resin that has phenolic hydroxyl group in the skeleton during as (A) composition, (B) Resins, epoxy and (E) phenolic aldehyde be resin curing agent with respect to the ratio of mixture ((B)+(E)/(A)) of (A) polyimide resin be important.At this moment, be to utilize the reaction of phenolic hydroxyl group and epoxy group(ing) to be cured reaction, if epoxy group(ing) is very few, the anxiety with the bounding force deficiency of adherend is arranged then; And too much, then therefore flexible modulus situation about rising because of Resins, epoxy is not suitable for making soft adhesive sheet.Therefore, with respect to 100 mass parts (A) polyimide resin, wish (B) Resins, epoxy and (E) phenolic aldehyde be that the combined amount of resin curing agent is 1～900 mass parts, be preferably 5～400 mass parts.
Herein, (E) phenolic aldehyde is resin curing agent and (A) has the polyimide resin total amount of phenolic hydroxyl group in the skeleton and be not particularly limited with respect to the stoichiometric ratio ((A)+(E)/(B)) of (B) Resins, epoxy, preferably in 0.7～1.3 scope, more preferably 0.8～1.2.If surpass this scope, the situation that causes characteristic to change in time then arranged.
Need to prove, even in the situation that without phenolic aldehyde be resin as epoxy curing agent, (A) polyimide resin also can be with above-mentioned same with combined amount and the equivalence ratio of (B) Resins, epoxy.
[other compositions]
In the scope of not damaging effect of the present invention, different according to purpose, can further in resin combination of the present invention, add (C) compositions such as fine silica powder end, titanium oxide, carbon black, conductive particle weighting agent in addition, the tinting materials such as inorganic system or organic system pigment, dyestuff, the wettability rising agent, antioxidant, the additive of thermo-stabilizer etc. etc.
[preparation method of binder composition and purposes]
Binder composition of the present invention can be according to ordinary method, by above-mentioned (A)～(C) composition and (D) composition as required, (E) composition and other compositions are mixed to prepare.
The using method of the binder composition of the present invention that the above obtains is as follows: for example, this binder composition is dissolved in the non-proton property polar solvents such as toluene, pimelinketone, NMP (METHYLPYRROLIDONE) with suitable concentration, be coated on the substrate, make its drying, the pressing adherend is heating and curing.The binder composition that is dissolved in proper concn in the solvent can also be coated on the support base material (following sometimes referred to as base material), make its drying, it (is to be configured as membranaceous said composition that acquisition possesses the binder layer that is made of said composition that arranges on base material and this base material, the below is referred to as bonding film) the bonding sheet material of using, clamp this bonding film with substrate and adherend, pressing, be heating and curing that it is bonding to come.The gains that above-mentioned base material can use polyethylene, polypropylene, polyester, polymeric amide, polyimide, polyamidoimide, polyetherimide, tetrafluoroethylene, paper, tinsel etc. or their the surperficial demoulding is processed.
Binder composition of the present invention is configured as membranaceous when obtaining bonding film, preferably in normal temperature～200 ℃, particularly 80～150 ℃ lower dry 1 minute～1 hour, particularly 3～10 minutes.
Thickness to this bonding film is not particularly limited, and can select according to purpose, is preferably 5～100 μ m, particularly 5～40 μ m.Bonding film is after pressing under pressure 0.01～10MPa, the particularly 0.1～2MPa, preferably 100～200 ℃ of temperature, particularly 120～180 ℃ of lower curing 30 minutes～5 hours, particularly 1～4 hour.
As follows as the using method of the thermal conductivity dicing die bonding film of binder layer with binder composition of the present invention: the base material film of release adhesive layer one side as required, the wafer hot pressing on the binder layer of dicing die bonding film, is fixed on the dicing die bonding film.The hot pressing condition can be carried out various selections according to the composition of binder layer, is generally 40～120 ℃ and 0.01～0.2MPa.Next, be fixed on the cutting unit, the chip that will be attached with binder layer after the cutting is peeled off rear taking-up (pickup) from binder layer, on lead frame, makes it bonding by being heating and curing this chip hot pressing.This hot pressing condition can be identical with the hot pressing condition of wafer and binder layer, and in addition, the condition of being heating and curing can be carried out various selections according to the composition of binder layer, is generally 120～250 ℃.
Binder composition of the present invention not only can be used as dicing die bonding film in the manufacturing of electronic unit, can also use in following bonding various steps.
Embodiment
Below, embodiment and comparative example are shown specifically describing the present invention, but the present invention is not limited to following embodiment.
[material]
(A) have in the polymer backbone can with the functional group of Resins, epoxy reaction, Tg is the polymkeric substance more than 45 ℃
The polyimide resin with phenolic hydroxyl group that obtains in the following synthesis example 1;
JER (registered trademark) 1256 (trade(brand)name, JER company system, the phenoxy resin with epoxy group(ing), weight-average molecular weight: 50000, Tg:100 ℃).
(B) has the Resins, epoxy of at least 2 epoxy group(ing) in the per molecule
RE-310S: bisphenol A type epoxy resin (trade(brand)name, Japanese chemical drug (strain) company system, weight-average molecular weight: 600).
(C) be that to have carried out surface-treated, thermal conductivity be the above inorganic filler of 10W/mK for 500～10000 silicon compound with the number-average molecular weight shown in the above-mentioned average composition formula (I).
(C1) the silicon compound C1 with following formula has carried out surface-treated aluminum oxide: AO-502 (trade(brand)name, Admatechs company system, aluminum oxide, thermal conductivity: 27W/mK)
[Chemical formula 1 4]
Figure 427574DEST_PATH_IMAGE020
That is, use an average group accepted way of doing sth: (HR 1SiO) a(R 2 3SiO 1/2) b(R 3 2SiO) c(R 4SiO 3/2) d(in the formula, R 1～R 4The expression methyl, a is that 0.167, b is that 0.167, c is that 0.667, d is 0.) expression silicon compound, number-average molecular weight: 700.
(C2) with the silicon compound C2 of following formula carried out surface-treated aluminum oxide: AO-502 (trade(brand)name, as mentioned above)
[Chemical formula 1 5]
Figure 2012104095302100002DEST_PATH_IMAGE021
That is, use an average group accepted way of doing sth: (HR 1SiO) a(R 2 3SiO 1/2) b(R 3 2SiO) c(R 4SiO 3/2) d(in the formula, R 1～R 4The expression methyl, a is that 0.409, b is that 0.013, c is that 0.579, d is 0.) expression silicon compound, number-average molecular weight: 8400.
(C3) with the silicon compound C3 of following formula carried out surface-treated aluminum oxide: AO-502 (trade(brand)name, as mentioned above)
[Chemical formula 1 6]
That is, use an average group accepted way of doing sth: (HR 1SiO) a(R 2 3SiO 1/2) b(R 3 2SiO) c(R 4SiO 3/2) d(in the formula, R 1～R 4The expression methyl, a is that 0.469, b is that 0.063, c is that 0.469, d is 0.) expression silicon compound, number-average molecular weight: 1700.
(C4) with the silicon compound C4 of following formula carried out surface-treated aluminum oxide: AO-502 (trade(brand)name, as mentioned above)
[Chemical formula 1 7]
Figure 2012104095302100002DEST_PATH_IMAGE023
That is, use an average group accepted way of doing sth: (HR 1SiO) a(R 2 3SiO 1/2) b(R 3 2SiO) c(R 4SiO 3/2) d(in the formula, R 1～R 4The expression methyl, a is that 0.691, b is that 0.029, c is that 0.279, d is 0.) expression silicon compound, number-average molecular weight: 3400.
(C') (relatively use) with shown in the above-mentioned average composition formula (I), number-average molecular weight is that to have carried out surface-treated, thermal conductivity be the above inorganic filler of 10W/mK for silicon compound beyond 500～10000 the silicon compound; Perhaps not with silicon compound carry out surface-treated, thermal conductivity is the inorganic filler more than the 10W/mK.
(C5) with the silicon compound C5 of following formula carried out surface-treated aluminum oxide: AO-502 (trade(brand)name, as mentioned above)
[Chemical formula 1 8]
Figure 794282DEST_PATH_IMAGE024
That is, use an average group accepted way of doing sth: (HR 1SiO) a(R 2 3SiO 1/2) b(R 3 2SiO) c(R 4SiO 3/2) d(in the formula, R 1～R 4The expression methyl, a is that 0.083, b is that 0.083, c is that 0.833, d is 0.) expression silicon compound, number-average molecular weight: 1400.
(C6) the silicon compound C6 with following formula has carried out surface-treated AO-502
[Chemical formula 1 9]
Figure 2012104095302100002DEST_PATH_IMAGE025
That is, use an average group accepted way of doing sth: (HR 1SiO) a(R 2 3SiO 1/2) b(R 3 2SiO) c(R 4SiO 3/2) d(in the formula, R 1～R 4The expression methyl, a is that 0.154, b is that 0.003, c is that 0.843, d is 0.) expression silicon compound, number-average molecular weight: 39800.
(C7) with the silicon compound C7 of following formula carried out surface-treated aluminum oxide: AO-502 (trade(brand)name, as mentioned above)
[Chemical formula 2 0]
That is, use an average group accepted way of doing sth: (HR 1SiO) a(R 2 3SiO 1/2) b(R 3 2SiO) c(R 4SiO 3/2) d(in the formula, R 1～R 4The expression methyl, a is that 0.500, b is that 0.333, c is that 0.167, d is 0.) expression silicon compound, number-average molecular weight: 400.
(C8) with the silicon compound C8 of following formula carried out surface-treated aluminum oxide: AO-502 (trade(brand)name, as mentioned above)
[Chemical formula 2 1]
Figure 2012104095302100002DEST_PATH_IMAGE027
That is, use an average group accepted way of doing sth: (HR 1SiO) a(R 2 3SiO 1/2) b(R 3 2SiO) c(R 4SiO 3/2) d(in the formula, R 1～R 4The expression methyl, a is that 0.889, b is that 0.111, c is that 0, d is 0.) expression silicon compound, number-average molecular weight: 900.
(C9) not with silicon compound carry out surface-treated aluminum oxide: AO-502 (trade(brand)name, as mentioned above).
Need to prove, (C1)～(C8) composition is by with above-mentioned silicon compound and 100 mass parts aluminum oxide: the AO-502 (trade(brand)names of 1.7 mass parts corresponding to (C1)～(C8) composition, mix as mentioned above), under 150 ℃, carry out thermal treatment in 60 minutes and prepare.
(D) curing catalysts
DICY-7 (trade(brand)name, JER (strain) company system, Dyhard RU 100).
[synthesizing of polyimide resin]
[synthesis example 1]
To the 25ml that connected reflux cooler being housed with adding 44.03 mass parts in the detachable flask of 1L of cock water and basis weight receptor, thermometer and agitator as the diamino siloxanes (trade(brand)name: KF-8010 of the following structural formula of diamines, chemical company of SHIN-ETSU HANTOTAI system) and 100 mass parts as the 2-methyl-2-pyrrolidone of reaction solvent, 80 ℃ of lower stirrings, this diamino siloxanes is dispersed in the reaction solvent.Be the 6FDA (2 of acid anhydrides to wherein dripping by 38.72 mass parts, 2-two (3, hexafluoropropane dianhydride) and the solution that consists of of 100 mass parts 2-methyl-2-pyrrolidones 4-dicarboxyl phenyl), stirred 2 hours under the room temperature, make diamines and anhydride reaction, thus the synthetic amido acid oligopolymer that is rich in acid anhydrides.
[Chemical formula 2 2]
Figure 121413DEST_PATH_IMAGE028
Wherein, t=10.
Next, to the 25ml that connected reflux cooler being housed with adding the aromatic diamine with phenolic hydroxyl group shown in the 17.25 mass parts following formulas in the detachable flask of 1L of cock water and basis weight receptor, thermometer and agitator:
[Chemical formula 2 3]
Figure 2012104095302100002DEST_PATH_IMAGE029
With 100 mass parts 2-methyl-2-pyrrolidones, this aromatic diamine is dispersed in the 2-methyl-2-pyrrolidone.After wherein dripping the above-mentioned amido acid oligopolymer that is rich in acid anhydrides, at room temperature stirred the synthesizing polyamides acid solution 16 hours.Afterwards, add the temperature that raises behind the 25ml dimethylbenzene in this solution, about 180 ℃ of lower backflows 2 hours.Confirming has a certain amount of water to store in the water and basis weight receptor, and the not outflow of water breakthrough, removes the effluent liquid that stores in the water and basis weight receptor, lower to removal xylene at 180 ℃ simultaneously.After reaction finishes, drip the reaction solution that obtains in excessive methyl alcohol, polymkeric substance is separated out, drying under reduced pressure obtains to have in the skeleton polyimide resin of phenolic hydroxyl group.The content of phenolic hydroxyl group is 20 % by mole with respect to amine unit.In addition, weight-average molecular weight is 50000.
Infrared extinction spectrum to the polyimide resin that obtains is measured, occur expression have unreacted functional group, based on the absorption of polyamic acid, confirm at 1780cm -1And 1720cm -1There is the absorption based on acylimino at the place, confirms at 3500cm -1There is the absorption based on phenolic hydroxyl group at the place.
The polyimide resin that obtains is cast on Teflon (registered trademark) film, and making thickness is the polyimide film of 100 μ m.With the heat engine tool trier TM-7000 of vacuum science and engineering company system, under the condition of 10 ℃/minute of load 10g and heat-up rates, measure the Tg of this polyimide film by thermo-mechanical analysis (TMA) method, the result is 130 ℃.
[preparation of binder composition and evaluating characteristics]
[embodiment 1～7, comparative example 1～7]
Combined amount is dissolved in (A) composition in the polymkeric substance diluting solvent (pimelinketone) shown in the according to the form below 1 or 2, combined amount shown in the according to the form below 1 or 2 is added (B) composition, (C) composition or (C') composition, (D) composition and mix the preparation binder composition as the methyl ethyl ketone (MEK) of rear interpolation solvent in the gained solution.
[bonding making with sheet material]
The binder composition of above-mentioned acquisition is coated on the PET film of the thick 38 μ m that apply with the fluorine silicon mold release agent, 110 ℃ of lower heat dryings 10 minutes, makes and possess the approximately bonding sheet material of using of the binder layer of 25 μ m (calling bonding film in the following text) of thickness.
[260 ℃ of shear adhesion power]
By the bonding bonding film that obtains 3mm * 3mm with sheet material of making above.The surfaceness of preparing in addition the silicon wafer of 3mm * 3mm * thick 725 μ m and being coated with AUS308 (trade(brand)name, solder resist, sun printing ink (strain) system) is the following BT substrate of 5 μ m (15mm * 15mm).On this BT substrate, above-mentioned bonding film and above-mentioned silicon wafer are sequentially stacked by this, the following whole of this silicon wafer covered by this bonding film, under 170 ℃, 0.67MPa, 2 seconds condition, carry out chip attachment.To under 175 ℃/4 hours condition, be heated by this laminate that silicon wafer, bonding film and BT substrate consist of, this bonding film is solidified, afterwards 260 ℃ temperature, measure the bounding force of the curing bonding film that obtains under the height of BT substrate 50 μ m, the velocity of shear of 200 μ m/ seconds.The result is shown in table 1 or 2.
[260 ℃ of shear adhesion power behind the JEDEC L2]
The above-mentioned laminate that will be made of silicon wafer, bonding film and BT substrate is lower preservation of JEDEC L2 condition (under 85 ℃, the condition of 60%RH 168 hours), next 3 IR refluxes by 260 ℃ of top temperatures are measured the bounding force that solidifies bonding film afterwards under condition same as described above.The result is shown in table 1 or 2.
[thermal conductivity]
A plurality of above-mentioned bonding films are laminated, make the thick 50 μ m that consisted of by this bonding film, the discoid laminate of diameter 12.5mm.This laminate is clipped between the Al plate of 2 thick 1mm, be heated to 175 ℃ this bonding film is solidified, xenon flash of light analyser (the Xenon flash analyzer) LFA 447 with NETZSCH company presses the thermal conductivity that laser flash method (Laser flash method) is measured the curing bonding film afterwards.The result is shown in table 1 or 2.
[table 1]
Figure 2012104095302100002DEST_PATH_IMAGE031
[table 2]
Figure DEST_PATH_IMAGE033
。

Claims (8)

1. the thermally conductive adhesive composition that contains following (A)～(C) composition:
(A) have in the polymer backbone can with polymkeric substance 100 mass parts of the functional group of Resins, epoxy reaction;
(B) have Resins, epoxy 50～400 mass parts of at least 2 epoxy group(ing) in the per molecule; And
(C) with the number-average molecular weight of a following average group accepted way of doing sth (I) expression be 500～10000 silicon compound to have carried out surface-treated, thermal conductivity be above inorganic filler 1000～4000 mass parts of 10W/mK,
Figure 2012104095302100001DEST_PATH_IMAGE002
In the formula, R 1～R 4Independent expression does not have the monovalence alkyl of the non-substituted of aliphatic unsaturated link(age) or replacement separately, and a is 0.1～0.7 positive number, and b is 0.01～0.2 positive number, and c is 0～0.9 number, and d is 0～0.2 number, and condition is to satisfy a+b+c+d=1.
2. the thermally conductive adhesive composition of claim 1, wherein, above-mentioned (A) composition is to contain at least a kind the polymkeric substance that is selected from polyimide resin, this polyimide resin is tetracarboxylic dianhydride and the reaction product that contains the diamine compound of diamines shown in the following formula (5), is the closed loop derivative of polyamic acid
Figure 2012104095302100001DEST_PATH_IMAGE004
In the formula, R 1Be the divalent organic group of carbonatoms 3～9, R 2And R 3Independent separately is non-substituted or the monovalence alkyl of the carbonatoms 1～8 of replacement, and r is 1～200 integer.
3. the thermally conductive adhesive composition of claim 2, wherein, above-mentioned diamine compound further contains the diamines of following formula (6') expression,
Figure 2012104095302100001DEST_PATH_IMAGE006
In the formula, R 4Independent is the monovalence alkyl of the carbonatoms 1～8 of hydrogen atom, halogen atom or non-substituted or replacement, and n is 1～5 integer, and A independently is
In the formula, R 4Same as described above, R independently is hydrogen atom, halogen atom or monovalence alkyl non-substituted or that replace,
B independently is
In the formula, R 4Same as described above.
4. the thermally conductive adhesive composition of claim 3, wherein, the diamines of following formula (6') expression is the diamines of following formula (6) expression,
Figure DEST_PATH_IMAGE012
In the formula, R 4Same as described above.
5. the thermally conductive adhesive composition of claim 1, said composition further contains (D) epoxy resin cure catalyzer.
6. each thermally conductive adhesive composition in the claim 1～5, said composition is shaped to membranaceous.
7. the bonding sheet material of using, it possesses: the binder layer that the thermally conductive adhesive composition by each record in the claim 1～5 that arranges on base material and this base material consists of.
8. thermal conductivity dicing die bonding film, it possesses: have the binder layer that the thermally conductive adhesive composition by each record in the claim 1～5 that arranges on the adhesive layer of the cutting film of adhesive layer of base material and its upper setting and this cutting film consists of.
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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