CN101864269A - Thermal conductive adhesive - Google Patents
Thermal conductive adhesive Download PDFInfo
- Publication number
- CN101864269A CN101864269A CN201010163171A CN201010163171A CN101864269A CN 101864269 A CN101864269 A CN 101864269A CN 201010163171 A CN201010163171 A CN 201010163171A CN 201010163171 A CN201010163171 A CN 201010163171A CN 101864269 A CN101864269 A CN 101864269A
- Authority
- CN
- China
- Prior art keywords
- conductive adhesive
- thermal conductive
- formula
- mass parts
- methyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
- C09J183/04—Polysiloxanes
-
- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- 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
- C09J179/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09J161/00 - C09J177/00
- C09J179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C09J179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- 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
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K7/00—Constructional details common to different types of electric apparatus
- H05K7/20—Modifications to facilitate cooling, ventilating, or heating
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Die Bonding (AREA)
Abstract
A kind of thermal conductive adhesive that has the excellent heat conductivity and heat generating components and heat release parts are had the electrical insulating property of excellent cementability is provided.This thermal conductive adhesive contains: (A) contain repeating unit shown in the following formula (1) (in the formula (1), W represents 4 valency organic groups, and X represents divalent organic group, Y represent divalence polysiloxane residue shown in the following formula (2) (in the formula (2), R
1Replacement or the unsubstituted monovalence alkyl of representing carbonatoms 1～8 independently of one another, R
2Represent free-radical polymerised group, a and b are respectively 1～20 integer, and a+b is 2～21), 0.05≤m≤0.8,0.2≤n≤0.95, m+n=1) and weight-average molecular weight be 5,000～150,000 polyimide polyorganosiloxane resin 100 mass parts; (B) heat conductivity filler 100～10,000 mass parts of electrical insulating property; And (C) organic solvent.[Chemical formula 1]
[Chemical formula 2]
Description
Technical field
The present invention relates to thermal conductive adhesive, relate in particular to the thermal conductive adhesive that is applicable to bonding electronic component and heat release parts (thermal component) or heat generating components.
Background technology
In recent years, along with for example central arithmetic processing apparatus (CPU) of computer and high performance, miniaturization and the densification of chipset of electronic component, electronic component and the thermal value that the parts of this electronic component are installed increase.So, to keep electronic component and the aspect of performance of the parts of this electronic component is being installed, the cooling of electronic component is unusual important techniques.Usually, can contact by the good material that makes electronic component and heat conductivity and improve the exothermal efficiency of electronic component.Therefore, the demand for the exothermic material with good heat conductivity (TIM) increases gradually.
Exothermic material for example places between the electronic component and cooling system (for example scatterer (heat sink)), plays the effect that the heat that will be sent by electronic component is passed to cooling system effectively.Exothermic material is divided into sheet forming composition and paste composition according to its shape or using method.The sheet forming composition for example is divided into, elastomerics (rubber-like polymer substance) type heat release sheet and thermal softening type phase transformation sheet (phase changesheet has used the sheet material because of the exothermic material of undergoing phase transition of temperature change).Paste composition for example is divided into, and non-curing heat release lubricating oil and coating the time are pasty state and heat release gel or the exothermicity caking agent by thermal treatment generation gelation or elastomericsization for example.
These exothermic material be generally the organic polymer material middle-high density be filled with the matrix material of heat-conducting substance.The thermal conductivity of organic polymer material is usually little, and its difference because of the organic polymer material kind has very big difference.So the thermal conductivity of exothermic material depends on the volume filling ratio of heat-conducting substance in organic polymer material to a great extent.Therefore, it is very important how filling heat-conducting substance in large quantities in organic polymer material.
The exothermicity caking agent not only will have high heat conductivity, and requires it to have bonding force under various environment or stress.Fill the heat conductivity material in organic polymer material more to high-density, the exothermicity of exothermic material is just high more.But fill the heat conductivity material in organic polymer material more to high-density, it is crisp more that exothermic material itself also can become, flexible or low more with the bonding force of adherend.
As the organic polymer material of exothermicity caking agent, known have Resins, epoxy, organosilicon polymer, a polyimide etc., though the Resins, epoxy cementability is good, aspect heat-resisting, weather resistance, there is defective.Therefore, consider aspects such as coating, the flexibility after the curing or thermostability, preferably use organosilicon polymer (reference example such as following patent documentation 1 and 2) heat-conducting substance.Yet the exothermic material of use organosilicon polymer can not satisfy the requirement of this two aspect of cementability and exothermicity sometimes.
In addition, when using thermotolerance,, can't fill heat-conducting substance, therefore have to be dissolved in the solvent etc. and fill because polyimide resin is a solid through the polyimide improved.For fear of this operation, must fill heat-conducting substance by polyamic acid solution as precursor, must be heated to usually more than 300 ℃ when solidifying, inevitably to producing thermal load on every side owing to polyamic acid solution.
In addition; be also known as the purpose of the surface protection of part such as the distribution that reaches semiconductor element and printed circuit board (PCB); use the method for polyimide polyorganosiloxane resin, its under super-humid conditions with the adaptation of body material and weather resistance than silicon rubber height (for example, with reference to following patent documentation 3).The method (for example, referring to Patent Document 4) that the composition that will contain this polyimide polyorganosiloxane resin uses as the semi-conductor caking agent is also disclosed.But use the thermal conductive adhesive of these polyimide polyorganosiloxane resins, especially require the research of the thermal conductive adhesive of electrical insulating property not launch as yet.
The prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2006-342200 communique
Patent documentation 2: Japanese Patent Publication 61-3670 communique
Patent documentation 3: TOHKEMY 2002-012667 communique
Patent documentation 4: TOHKEMY 2006-005159 communique
Summary of the invention
The problem that invention will solve
The object of the present invention is to provide and a kind ofly have good heat conductivity and to by sticky object heat generating components and heat release (putting Hot) parts electrical insulating property thermal conductive adhesive (being also referred to as the heat release thickener) for example with good bonding.
The method of dealing with problems
The present invention includes following thermal conductive adhesive.
A kind of thermal conductive adhesive, it contains following compositions:
(A) contain repeating unit shown in the following formula (1) and weight-average molecular weight be 5,000～150,000 polyimide polyorganosiloxane resin 100 mass parts,
(B) heat conductivity filler 100～10,000 mass parts of electrical insulating property and
(C) organic solvent,
[Chemical formula 1]
(in the formula (1), W represents 4 valency organic groups, and X represents divalent organic group, and Y represents divalence polysiloxane residue shown in the following formula (2), 0.05≤m≤0.8,0.2≤n≤0.95, m+n=1)
[Chemical formula 2]
(in the formula (2), R
1Replacement or the unsubstituted monovalence alkyl of representing carbonatoms 1～8 independently of one another, R
2Represent free-radical polymerised group, a and b are respectively 1～20 integer, and a+b is 2～21).
In an embodiment of the invention, above-mentioned thermal conductive adhesive also contains (D) peroxycarbonates 0.1～10 mass parts.Peroxycarbonates plays a role as the solidifying agent of the polymerizing curable that promotes free-radical polymerised group.
In an embodiment of the invention, R
2Be vinyl, propenyl, (methyl) acryloxy propyl group, (methyl) acryloxy ethyl, (methyl) acryloyl-oxy ylmethyl or styryl, more preferably vinyl.
In an embodiment of the invention, above-mentioned thermal conductive adhesive is more than the 3MPa to the bonding strength of copper coin, preferred 5～10MPa.
Thermal conductive adhesive of the present invention is placed when heating on the copper coin, and this thermal conductive adhesive takes place to flow, and expands at the copper coin moistened surface.So,, carry out bonding well by thermal treatment and copper coin driving fit.
Thermal conductive adhesive of the present invention is applied to adherend (by body), and when heating was solidified it, caking agent took place to flow, and in the expansion of adherend moistened surface, and made solvent evaporates, so the heat conductivity filler exposes the surface at the caking agent cured article.Therefore can obtain good heat conductivity.
The present invention also provides the electronic unit that comprises following electronic component, and described electronic component is to utilize the material that is obtained by above-mentioned thermal conductive adhesive curing to be bonded on heat release parts or the heat generating components.
The effect of invention
Polyimide polyorganosiloxane resin, heat conductivity filler and the organic solvent of thermal conductive adhesive of the present invention by containing ad hoc structure has good heat conductivity and to had good cementability by sticky object.
Embodiment
Below, illustrate in greater detail with regard to thermal conductive adhesive of the present invention.
(A) polyimide polyorganosiloxane resin
The polyimide polyorganosiloxane resin has repeating unit shown in the following formula (1).
[chemical formula 3]
W in the formula (1) is 4 valency organic groups.W can be selected from for example pyromellitic acid dianhydride, 2,3,3 ', 4 '-biphenyl tetracarboxylic dianhydride, 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, 3,3 ', 4,4 '-phenyl ether tetracarboxylic dianhydride, 3,3 ', 4,4 '-diphenylsulfone acid dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, ethylene glycol bisthioglycolate trimelitic dianhydride (エ チ レ Application グ リ コ one Le PVC ス ト リ メ リ Star ト Suan Er No water thing), 4, the two O-phthalic acid dianhydrides of 4 '-hexafluoro propylidene (ヘ キ サ Off Le オ ロ プ ロ ピ リ デ Application PVC ス Off タ Le acid two No water things), 2, the residue of two [4-(3,4-phenoxy group dicarboxylic acid) phenyl] the propionic acid dianhydrides of 2-.
X in the formula (1) is a divalent organic group.X is for for example by the diamines deutero-group of the polyimide resin that can be used for habitually practising.This diamines can be the combination more than a kind or 2 kinds that is selected from for example aliphatie diamine and aromatic diamine.Aliphatie diamine for example, 1,4-butanediamine, 1,4-diamino-cyclohexane, 4,4 '-diamino-dicyclohexyl methane.Aromatic diamine for example, phenylenediamine, 4,4 '-diamino-diphenyl ether, 2, two (4-aminophenyl) propane of 2-.X is preferably by aromatic diamine deutero-group shown in the following formula (3).
[chemical formula 4]
B in the formula (3) is any the represented group in following formula (4), (5) and (6).
[chemical formula 5]
[chemical formula 6]
[chemical formula 7]
Y in the formula (1) is the divalence polysiloxane residue of following formula (2) expression.
[chemical formula 8]
R in the formula (2)
1Be carbonatoms 1～8, preferred 1～4 replacement or unsubstituted monovalence alkyl.R
1For for example, methyl, ethyl.
R in the formula (2)
2Be free-radical polymerised group.R
2For for example, vinyl, propenyl, (methyl) acryloxy propyl group, (methyl) acryloxy ethyl, (methyl) acryloyl-oxy ylmethyl or styryl.Be easy to the acquisition aspect from raw material and consider, preferred R
2Be vinyl.As long as this free-radical polymerised group polysiloxane that is the polyimide polyorganosiloxane resin partly, can be in any part in for example end and central part.
A in the formula (2) and b are respectively 1～20, preferred 3～20 integer.A+b adds up to 2～21.Here, if among a, the b any one greater than 20 or a+b greater than 21, then with by the bonding force of convered structure weaken.
In order to embody the effect that this repeating unit brings, m in the formula (1) and the pass of n are 0.05≤m≤0.8,0.2≤n≤0.95, preferred 0.05≤m≤0.5,0.5≤n≤0.95.In the time of in this scope, can obtain by the good cementability of convered structure.
M+n in the formula (1) adds up to 1.
The weight-average molecular weight of polyimide polyorganosiloxane resin is 5,000～150,000, preferred 20,000～150,000, more preferably 20,000～100,000, preferred especially 20,000～50,000.This be because: if molecular weight is lower than above-mentioned lower limit, then can't embody obdurability, and, then be difficult to mix with aftermentioned heat conductivity filler if molecular weight is higher than the above-mentioned upper limit as resin.
Above-mentioned polyimide polyorganosiloxane resin can be by for example following known method preparation.
At first, in solvent, add the diamines of the tetracarboxylic dianhydride of the W that is used to derive, the X that is used to derive and the diamino polysiloxane of the Y that is used to derive, for example react under 0～50 ℃ at low temperature then.Above-mentioned solvent is for being selected from the combination more than a kind or 2 kinds in for example N-N-methyl-2-2-pyrrolidone N-(NMP), pimelinketone, gamma-butyrolactone and the N,N-dimethylacetamide (DMAc).In addition, remove, can be used in combination aromatic hydrocarbon based, for example toluene, dimethylbenzene for the water that can be by azeotropic generates during easily with inferior amidation.By above-mentioned reaction, can make polyamic acid as the precursor of polyimide resin.Subsequently, this polyamic acid solution is warming up to preferred 80～200 ℃, preferred especially 140～180 ℃ temperature.Heat up by this, the sour acid amides generation dehydration closed-loop of polyamic acid reacts, and can obtain the solution of polyimide polyorganosiloxane resin.This solution is dropped into solvent for example in water, methyl alcohol, ethanol or the acetonitrile time, generate throw out.The throw out of this generation is carried out drying, obtain the polyimide polyorganosiloxane resin.
The total amount of diamines and diamino polysiloxane is preferably 0.95～1.05, is preferably 0.98～1.02 scope especially with respect to tetracarboxylic dianhydride's molar ratio.
In order to adjust the molecular weight of polyimide polyorganosiloxane resin, can in above-mentioned solution, add two functionality carboxylic acids (for example Tetra hydro Phthalic anhydride) and a functionality amine (for example aniline).The addition of these compounds for example is respectively 2 moles below the % with respect to tetracarboxylic dianhydride and diamines.
Also can in the imidization process, add dewatering agent and imidization catalyst, optionally, carry out inferior amidation by about 50 ℃, heating.Dewatering agent is for example acid anhydrides, for example diacetyl oxide, propionic anhydride and trifluoroacetic anhydride.With respect to 1 mole of diamines, the consumption of dewatering agent is for example 1～10 mole.Imidization catalyst is for example tertiary amine, for example pyridine, collidine (Collidine), lutidine (lutidine) and triethylamine.The consumption of imidization catalyst is for example 0.5～10 mole with respect to 1 mole of used dewatering agent.
Use under multiple diamines and/or multiple tetracarboxylic dianhydride's the situation, can adopt for example following method: make method, the limit of its copolymerization condensation make more than 2 kinds diamines or tetracarboxylic dianhydride individually carry out the method that coronite is added successively after in advance whole raw materials being mixed.But reaction method is not subjected to the special qualification of these examples.
(B) the heat conductivity filler of electrical insulating property
The heat conductivity filler of electrical insulating property is for example metal oxide and ceramic powder.This metal-powder is for example Zinc oxide powder, alumina powder.Ceramic powder is for example silicon carbide powder, alpha-silicon nitride powders, boron nitride powder, aluminium nitride powder.The heat conductivity filler can suitably be selected from stability or cost aspect.
The shape of heat conductivity filler is not particularly limited, and for example is granular, dendroid, laminar (Off レ one Network shape) and amorphous.Can use the mixture of the heat conductivity filler powder that has these shapes more than a kind or 2 kinds.The size distribution of heat conductivity filler is not particularly limited, for example 90 weight % above in 0.05～100 mu m range, more than the preferred 95 weight % in this scope.The median size of heat conductivity filler is not particularly limited, and for example is in 1～50 mu m range.As the heat conductivity filler, can use single distribution (Unit one distribution) the heat conductivity filler of (unimodality).But for make the heat conductivity filler in caking agent with the high-density homodisperse, compare with the heat conductivity filler that uses single distribution, the multiple heat conductivity filler combination that shape is different with particle diameter is the method better effects if that multimodality distributes.
With regard to the use level ratio of above-mentioned heat conductivity filler in the thermal conductive adhesive of the present invention, with respect to per 100 mass parts polyimide polyorganosiloxane resins is 100～10,000 mass parts, preferred 200～6,000 mass parts, more preferably 200～2,000 mass parts, preferred especially 200～1,500 mass parts.If the ratio of the use level of above-mentioned heat conductivity filler is lower than above-mentioned lower limit, can't obtain sufficient heat conductivity when then using thermal conductive adhesive of the present invention.Otherwise,, when then using thermal conductive adhesive of the present invention, and can't be obtained sufficient adhesion strength between convered structure if the ratio of the use level of above-mentioned heat conductivity filler is higher than the above-mentioned upper limit.
(C) organic solvent
Organic solvent preferably has consistency with (A) composition, to the not influence of the condition of surface of (B) composition.Organic solvent for example for be selected from ethers, ketone, ester class, cellosolve (cellosolve) class, amides and aromatic hydrocarbon based in the combination more than a kind or 2 kinds.Ethers for example comprises, tetrahydrofuran (THF) and methyl-phenoxide (anisole).Ketone comprises for example pimelinketone, 2-butanone, methyl iso-butyl ketone (MIBK), 2-heptanone, methyln-hexyl ketone and methyl phenyl ketone.The ester class comprises for example butylacetate, methyl benzoate and gamma-butyrolactone.The cellosolve class comprises for example acetate of butyl carbitol, butyl cellosolve acetate and propylene glycol monomethyl ether.Amides comprises for example N, dinethylformamide, N,N-dimethylacetamide and N-N-methyl-2-2-pyrrolidone N-.Aromatic hydrocarbon based for example toluene, the dimethylbenzene of comprising.Organic solvent is preferably selected from ketone, ester class, cellosolve class and amides.Organic solvents in particular is preferably acetate of butyl carbitol, gamma-butyrolactone, propylene glycol monomethyl ether and N-N-methyl-2-2-pyrrolidone N-.These solvents can use separately, also can will be used in combination more than 2 kinds.
With regard to the amount of organic solvent, consider for example solvability, the operability when thermal conductive adhesive is coated with or the thickness of tunicle of polyimide polyorganosiloxane resin, the amount of polyimide polyorganosiloxane resin is 10～60 quality %, preferably uses in 20～50 quality % scopes with respect to the total amount of this resin and solvent usually.Can make higher concentration earlier when preserving composition, redilution becomes desired concentration during use.
Thermal conductive adhesive of the present invention also can contain (D) peroxycarbonates as optional member.In the presence of peroxycarbonates, even in lower temperature, the free-radical polymerised group that is connected with Siliciumatom in the polyimide polyorganosiloxane resin also can solidify rapidly, and performances such as solvent resistance improve.Peroxycarbonates can be enumerated, single peroxycarbonates such as tert-butyl hydroperoxide sec.-propyl carbonic ether, tert-butyl hydroperoxide 2-ethylhexyl carbonic ether, t-amyl peroxy 2-ethylhexyl carbonic ether; Two (2-ethylhexyl) peroxycarbonates, 1, two (the tert-butyl hydroperoxide carbonyl oxygen base) hexanes of 6-, two (4-tert-butylcyclohexyl) peroxy dicarbonate, two (2-ethoxyethyl group) peroxy dicarbonates, two (n-propyl) peroxy dicarbonate, diisopropyl peroxydicarbonate etc.With regard to peroxycarbonates, from solidified nature, consider with the aspects such as storage stability of the consistency of polyimide polyorganosiloxane resin and caking agent, preferred tert-butyl hydroperoxide 2-ethylhexyl carbonic ether, t-amyl peroxy 2-ethylhexyl carbonic ether, 1, two (the tert-butyl hydroperoxide carbonyl oxygen base) hexanes of 6-, two (4-tert-butylcyclohexyl) peroxy dicarbonate.
With respect to 100 mass parts polyimide polyorganosiloxane resins, the amount of peroxycarbonates is preferably 0.1～10 mass parts, 0.5～5 mass parts more preferably.If use level surpasses the above-mentioned upper limit, then the high-temp resisting high-humidity resisting of the storage stability of thermal conductive adhesive of the present invention and cured article has the trend of reduction.
The polyimide polyorganosiloxane resin by thermofixation given play to excellent thermotolerance, physical strength, solvent resistance, to the adaptation of various body materials.
The condition of cure of caking agent of the present invention is not particularly limited, 80 ℃～300 ℃ scope, preferably 100 ℃～200 ℃ scope.If be cured being lower than under the condition of above-mentioned lower limit, then the time of thermofixation overspending is impracticable.Making it possible to by selection component and composition to be lower than when being cured under the low temperature of above-mentioned lower limit, may have problems aspect the maintenance stability of caking agent.In addition, thermal conductive adhesive of the present invention is different with polyamic acid solution in the past, there is no need to be cured by long-time heating under the high temperature more than 300 ℃, therefore can suppress the thermal degradation when of body material.
Except mentioned component, thermal conductive adhesive of the present invention in the scope of the effect that does not influence the object of the invention and thermal conductive adhesive, also can add for example be selected from protective agent, UV light absorber, improved in adhesion agent, fire retardant, tensio-active agent, storage stability activator, ozone deterioration preventing agent, photostabilizer, tackifier, softening agent, silane coupling agent, antioxidant, thermo-stabilizer, radioactive rays screening agent, nucleator, slipping agent, pigment and the rerum natura conditioning agent more than a kind or 2 kinds.
Thermal conductive adhesive of the present invention preferably has the viscosity of 0.5～2000Pas at 25 ℃, more preferably has the viscosity of 1.0～1000Pa.s.
The thermal conductivity of thermal conductive adhesive of the present invention (W/mK) is preferably more than 0.5, more preferably more than 1.0, be preferably more than 3 especially.
Thermal conductive adhesive of the present invention is preferably more than 3, more preferably more than 5, be preferably more than 6 especially to the bonding strength (MPa) of copper coin.Bonding strength place 240 hours under 80 ℃, the hot and humid atmosphere of 95RH after is preferably same as described above.
Thermal conductive adhesive of the present invention is preferred for for example causing because of the brightness height caking agent of the big led chip of thermal value, or follows miniaturization, lightweight and cause the caking agent of the semiconductor element that the unit surface thermal value is big.
Below, the present invention is described in detail by embodiment, but the present invention is not subjected to the restriction of embodiment.
1. the polyimide polyorganosiloxane resin is synthetic
According to method shown in the following synthesis example 1～4, make 4 kinds of polyimide polyorganosiloxane resins.
Synthesis example 1
In the flask that stirrer, thermometer and nitrogen displacement apparatus are housed, add 4, two O-phthalic acid dianhydride 88.8g (0.2mol) of 4 '-hexafluoro propylidene and N-N-methyl-2-2-pyrrolidone N-500g.Then, with diamino siloxanes 142.2g (0.16mol) and 2 shown in the formula (7), two [4-(4-amino-benzene oxygen) phenyl] the propane 16.4g (0.04mol) of 2-are dissolved among the N-N-methyl-2-2-pyrrolidone N-100g, are prepared into solution.This drips of solution is added in the above-mentioned flask.During dripping, the temperature of conditioned reaction system makes it to be no more than 50 ℃.After dripping end, at room temperature restir is 10 hours.Then, after installation on this flask has the reflux cooler of moisture receptor, add dimethylbenzene 50g, be warming up to 150 ℃, kept this temperature 6 hours.Its result obtains filemot solution.
[chemical formula 9]
The above-mentioned brown solution that obtains is cooled to room temperature (25 ℃), drops in the methyl alcohol and carry out redeposition.190g gained throw out is carried out drying, measure its line absorption spectrum.Its result, do not occur based on unreacted polyamic acid absorption (1,640cm
-1), confirm 1 780cm
-1With 1,720cm
-1Absorption based on imide is arranged.Subsequently, by using the gel permeation chromatography (GPC) of tetrahydrofuran (THF) as solvent, measure weight-average molecular weight (polystyrene conversion), the result is 33,000.With products known as polyimide polyorganosiloxane resin (I).
Synthesis example 2
In the flask that stirrer, thermometer and nitrogen displacement apparatus are housed, add 4, two O-phthalic acid dianhydride 88.8g (0.2mol) of 4 '-hexafluoro propylidene and N-N-methyl-2-2-pyrrolidone N-500g.Then, with diamino siloxanes 165.3g (0.1mol) and 2 shown in the formula (8), two [4-(4-amino-benzene oxygen) phenyl] the propane 41.1g (0.1mol) of 2-are dissolved among the N-N-methyl-2-2-pyrrolidone N-100g, are prepared into solution.This drips of solution is added in the above-mentioned flask.During dripping, the temperature of conditioned reaction system makes it to be no more than 50 ℃.After dripping end, at room temperature restir is 10 hours.Then, after installation on this flask has the reflux cooler of moisture receptor, add dimethylbenzene 50g, be warming up to 150 ℃, kept this temperature 6 hours.Its result obtains filemot solution.
[Chemical formula 1 0]
The above-mentioned brown solution that obtains is cooled to room temperature (25 ℃), drops in the methyl alcohol and carry out redeposition.240g gained throw out is carried out drying, measure its line absorption spectrum.Its result, do not occur based on unreacted polyamic acid absorption (1,640cm
-1), confirm 1 780cm
-1With 1,720cm
-1Absorption based on imide is arranged.Subsequently, by using the gel permeation chromatography (GPC) of tetrahydrofuran (THF) as solvent, measure weight-average molecular weight (polystyrene conversion), the result is 33,000.With products known as polyimide polyorganosiloxane resin (II).
Synthesis example 3 (relatively using)
In the flask that stirrer, thermometer and nitrogen displacement apparatus are housed, add 4, two O-phthalic acid dianhydride 88.8g (0.2mol) of 4 '-hexafluoro propylidene and N-N-methyl-2-2-pyrrolidone N-500g.Then, with diamino siloxanes 263.1g (0.08mol) and 2 shown in the formula (9), two [4-(4-amino-benzene oxygen) phenyl] the propane 49.3g (0.12mol) of 2-are dissolved among the N-N-methyl-2-2-pyrrolidone N-100g, are prepared into solution.This drips of solution is added in the above-mentioned flask.During dripping, the temperature of conditioned reaction system makes it to be no more than 50 ℃.After dripping end, at room temperature restir is 10 hours.Then, after installation on this flask has the reflux cooler of moisture receptor, add dimethylbenzene 50g, be warming up to 150 ℃, kept this temperature 6 hours.Its result obtains filemot solution.
[Chemical formula 1 1]
The above-mentioned brown solution that obtains is cooled to room temperature (25 ℃), drops in the methyl alcohol and carry out redeposition.330g gained throw out is carried out drying, measure its line absorption spectrum.Its result, do not occur based on unreacted polyamic acid absorption (1,640cm
-1), confirm 1 780cm
-1With 1,720cm
-1Absorption based on imide is arranged.Subsequently, by using the gel permeation chromatography (GPC) of tetrahydrofuran (THF) as solvent, measure weight-average molecular weight (polystyrene conversion), the result is 35,000.With products known as polyimide polyorganosiloxane resin (III).
Synthesis example 4 (relatively using)
In the flask that stirrer, thermometer and nitrogen displacement apparatus are housed, add 4, two O-phthalic acid dianhydride 88.8g (0.2mol) of 4 '-hexafluoro propylidene and N-N-methyl-2-2-pyrrolidone N-500g.Then, with diamino siloxanes 244.8g (0.08mol) and 2 shown in the formula (10), two [4-(4-amino-benzene oxygen) phenyl] the propane 49.3g (0.12mol) of 2-are dissolved among the N-N-methyl-2-2-pyrrolidone N-100g, are prepared into solution.This drips of solution is added in the above-mentioned flask.During dripping, the temperature of conditioned reaction system makes it to be no more than 50 ℃.After dripping end, at room temperature restir is 10 hours.Then, after installation on this flask has the reflux cooler of moisture receptor, add dimethylbenzene 50g, be warming up to 150 ℃, kept this temperature 6 hours.Its result obtains filemot solution.
[Chemical formula 1 2]
The above-mentioned brown solution that obtains is cooled to room temperature (25 ℃), drops in the methyl alcohol and carry out redeposition.340g gained throw out is carried out drying, measure its line absorption spectrum.Its result, do not occur based on unreacted polyamic acid absorption (1,640cm
-1), confirm 1 780cm
-1With 1,720cm
-1Absorption based on imide is arranged.Subsequently, by using the gel permeation chromatography (GPC) of tetrahydrofuran (THF) as solvent, measure weight-average molecular weight (polystyrene conversion), the result is 35,000.With products known as polyimide polyorganosiloxane resin (IV)
2. the preparation of caking agent
Use following raw material.
(A) polyimide polyorganosiloxane resin: use the polyimide polyorganosiloxane resin (I) that obtains in the above-mentioned synthesis example 1～4, (II), (III) or (IV).
(B) the heat conductivity filler of electrical insulating property:
(B1) heat conductivity filler A: the aluminum oxide of median size 10 μ m (proportion 3.98)
(B2) heat conductivity filler B: the aluminum oxide of median size 1 μ m (proportion 3.98)
(C) organic solvent: acetate of butyl carbitol (BCA)
(D) peroxycarbonates: tert-butyl hydroperoxide-2-ethylhexyl carbonic ether
[embodiment 1～4 and comparative example 1～2]
With the heat conductivity filler (B1 and B2) of a kind of, (B) electrical insulating property in (A) polyimide polyorganosiloxane resin (I)～(IV), (C) organic solvent and (D) peroxycarbonates add in the rotation revolution mixing tank according to mass ratio shown in the table 1, stir, carry out deaeration then, obtain caking agent.
3. evaluation experimental
For the caking agent of embodiment 1～4 and comparative example 1～2 gained, carry out the evaluation experimental of viscosity, thermal conductivity and bonding strength according to following method.In addition, for thermoset single-liquid type polysiloxane rubber C (commercially available product) and D (commercially available product), carry out evaluation experimental (respectively as a comparative example 3 and comparative example 4) according to order same as described above.The result is as shown in table 2.
(1) viscosity
The viscosity of each caking agent is measured at 25 ℃ with BH type rotational viscosimeter.
(2) thermal conductivity
Each caking agent is poured in the ditch of teflon (trade mark) (Du Pont corporate system) plate,, then, this caking agent 150 ℃ of heating 1 hour, is made 80 ℃ of dryings 30 minutes
Test film.Measure the thermal diffusivity and the specific heat capacity of this test film with laser flash heat conduction analyser (LFA447, NETZSCH company), obtain thermal conductivity.
(3) bonding strength
Each caking agent is coated on copper coin with the surface covered of 20mm * 20mm (on 100mm * 25mm * 1mm), makes it fit with another copper coin of identical size.With the copper coin of this applying 80 ℃ of dryings 30 minutes, then, under the pressure of 4MPa in 150 ℃ dry 2 minutes again, 150 ℃ of heating 1 hour, obtain test film then.With the shear bond strength of autoplotter (Autograph) (STROGRAPH V10-D (the smart machine corporate system of Japan)) with the velocity determination test film of 5mm/min.
In addition, the test film that obtains is as described above exposed 240 hours (hot and humid experiment) under 80 ℃/95%RH, measure shear bond strength (after the hot and humid experiment) according to method same as described above.
[table 2]
By The above results as can be seen, caking agent I～IV has suitable viscosity, and thermal conductivity is 1.1～3.1W/mK, and good, bonding strength is 6 good～11MPa, and bonding strength does not reduce substantially before and after hot and humid experiment.
Claims (6)
1. thermal conductive adhesive, it contains following compositions:
(A) containing repeating unit shown in the following formula (1) and weight-average molecular weight is 5,000～150,000 polyimide polyorganosiloxane resin 100 mass parts;
(B) heat conductivity filler 100～10,000 mass parts of electrical insulating property; And
(C) organic solvent,
[Chemical formula 1]
In the formula (1), W represents 4 valency organic groups, and X represents divalent organic group, and Y represents divalence polysiloxane residue shown in the following formula (2), 0.05≤m≤0.8,0.2≤n≤0.95, and m+n=1,
[Chemical formula 2]
In the formula (2), R
1Replacement or the unsubstituted monovalence alkyl of representing carbonatoms 1～8 independently of one another, R
2Represent free-radical polymerised group, a and b are respectively 1～20 integer, and a+b is 2～21.
2. thermal conductive adhesive according to claim 1, wherein, R
2Be selected from vinyl, propenyl, (methyl) acryloxy propyl group, (methyl) acryloxy ethyl, (methyl) acryloyl-oxy ylmethyl and styryl.
3. thermal conductive adhesive according to claim 1, it also contains (D) peroxycarbonates of 0.1～10 mass parts.
4. thermal conductive adhesive according to claim 2, it also contains (D) peroxycarbonates of 0.1～10 mass parts.
5. according to each described thermal conductive adhesive in the claim 1～5, its bonding strength to copper coin is more than the 3MPa.
6. one kind comprises the electronic unit that is bonded in the electronic component on heat release parts or the heat generating components by following substances, and described material obtains each described thermal conductive adhesive curing in the claim 1～5.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009098418A JP5489261B2 (en) | 2009-04-14 | 2009-04-14 | Thermally conductive adhesive |
| JP098418/09 | 2009-04-14 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101864269A true CN101864269A (en) | 2010-10-20 |
| CN101864269B CN101864269B (en) | 2014-05-21 |
Family
ID=42956203
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201010163171.8A Expired - Fee Related CN101864269B (en) | 2009-04-14 | 2010-04-14 | Thermal conductive adhesive |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP5489261B2 (en) |
| KR (1) | KR101625688B1 (en) |
| CN (1) | CN101864269B (en) |
| TW (1) | TWI476261B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103074029A (en) * | 2011-10-25 | 2013-05-01 | 上海本诺电子材料有限公司 | Organosilicon polyimide conductive adhesive for LED |
| CN108203576A (en) * | 2016-12-20 | 2018-06-26 | 原子能机构和替代性可再生资源署 | Adhesive composition and use thereof in electronics |
| CN110016136A (en) * | 2017-12-05 | 2019-07-16 | 信越化学工业株式会社 | Novel tetracarboxylic dianhydride, polyimide resin and its manufacturing method, photosensitive resin composition, pattern forming method |
| CN110317453A (en) * | 2018-03-29 | 2019-10-11 | 信越化学工业株式会社 | Silicone-modified polyimides resin combination |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5562574B2 (en) * | 2009-04-14 | 2014-07-30 | 信越化学工業株式会社 | Thermally conductive adhesive |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1042168A (en) * | 1988-09-26 | 1990-05-16 | M&T化学有限公司 | Polyimide Film Die Attach Adhesives |
| CN1134967A (en) * | 1994-03-31 | 1996-11-06 | 西方化学公司 | Polyimidesiloxane adhesive |
| JP2005330421A (en) * | 2004-05-21 | 2005-12-02 | Shin Etsu Chem Co Ltd | Partially blocked polyimide-polysiloxane copolymer, method for producing the same and resin composition containing the copolymer |
| JP2008308618A (en) * | 2007-06-15 | 2008-12-25 | Shin Etsu Chem Co Ltd | Adhesive composition and adhesive film |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04222889A (en) * | 1990-12-25 | 1992-08-12 | Sumitomo Bakelite Co Ltd | Electrically conductive resin paste |
| JPH04345682A (en) * | 1991-05-21 | 1992-12-01 | Sumitomo Bakelite Co Ltd | Adhesive for hermetic sealing |
| JP2716611B2 (en) * | 1991-10-29 | 1998-02-18 | 住友ベークライト株式会社 | High thermal conductive film adhesive that can be thermocompressed |
| JPH05335354A (en) * | 1992-06-02 | 1993-12-17 | Sumitomo Bakelite Co Ltd | Semiconductor device with adhesive |
| JPH08283692A (en) * | 1995-04-17 | 1996-10-29 | Kanegafuchi Chem Ind Co Ltd | Electronic module |
| US5773561A (en) * | 1996-08-02 | 1998-06-30 | International Business Machines Corporation | Polymer sealants/adhesives and use thereof in electronic package assembly |
| JP2000212518A (en) * | 1999-01-26 | 2000-08-02 | Nitto Denko Corp | Thermal bonding sheet |
| JP2003138241A (en) * | 2001-08-21 | 2003-05-14 | Hitachi Chem Co Ltd | Heat-resistant adhesive and laminate using the same adhesive-applied heatsink and adhesive-applied metallic foil |
| JP2004137411A (en) * | 2002-10-18 | 2004-05-13 | Sumitomo Bakelite Co Ltd | Adhesive film for semiconductor, semiconductor device, and method of manufacturing semiconductor device |
| KR20090051250A (en) * | 2006-08-31 | 2009-05-21 | 니폰 쇼쿠바이 컴파니 리미티드 | Salt for near infrared ray absorbing composition and near infrared ray absorbing pressure sensitive adhesive composition |
| JP4590443B2 (en) * | 2007-09-05 | 2010-12-01 | 信越化学工業株式会社 | Thermosetting polyimide silicone resin composition |
-
2009
- 2009-04-14 JP JP2009098418A patent/JP5489261B2/en not_active Expired - Fee Related
-
2010
- 2010-04-13 TW TW099111420A patent/TWI476261B/en not_active IP Right Cessation
- 2010-04-13 KR KR1020100033603A patent/KR101625688B1/en not_active Expired - Fee Related
- 2010-04-14 CN CN201010163171.8A patent/CN101864269B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1042168A (en) * | 1988-09-26 | 1990-05-16 | M&T化学有限公司 | Polyimide Film Die Attach Adhesives |
| CN1134967A (en) * | 1994-03-31 | 1996-11-06 | 西方化学公司 | Polyimidesiloxane adhesive |
| JP2005330421A (en) * | 2004-05-21 | 2005-12-02 | Shin Etsu Chem Co Ltd | Partially blocked polyimide-polysiloxane copolymer, method for producing the same and resin composition containing the copolymer |
| JP2008308618A (en) * | 2007-06-15 | 2008-12-25 | Shin Etsu Chem Co Ltd | Adhesive composition and adhesive film |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103074029A (en) * | 2011-10-25 | 2013-05-01 | 上海本诺电子材料有限公司 | Organosilicon polyimide conductive adhesive for LED |
| CN103074029B (en) * | 2011-10-25 | 2016-06-08 | 上海本诺电子材料有限公司 | organosilicon polyimide conductive adhesive for LED |
| CN108203576A (en) * | 2016-12-20 | 2018-06-26 | 原子能机构和替代性可再生资源署 | Adhesive composition and use thereof in electronics |
| CN110016136A (en) * | 2017-12-05 | 2019-07-16 | 信越化学工业株式会社 | Novel tetracarboxylic dianhydride, polyimide resin and its manufacturing method, photosensitive resin composition, pattern forming method |
| CN110016136B (en) * | 2017-12-05 | 2021-09-24 | 信越化学工业株式会社 | Novel tetracarboxylic dianhydride, polyimide resin, method for producing same, photosensitive resin composition, and method for forming pattern |
| CN110317453A (en) * | 2018-03-29 | 2019-10-11 | 信越化学工业株式会社 | Silicone-modified polyimides resin combination |
| CN110317453B (en) * | 2018-03-29 | 2024-02-13 | 信越化学工业株式会社 | Organosilicon modified polyimide resin composition |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI476261B (en) | 2015-03-11 |
| KR20100113985A (en) | 2010-10-22 |
| JP5489261B2 (en) | 2014-05-14 |
| KR101625688B1 (en) | 2016-05-30 |
| JP2010248348A (en) | 2010-11-04 |
| CN101864269B (en) | 2014-05-21 |
| TW201102417A (en) | 2011-01-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101864268B (en) | Thermal conductive adhesive | |
| CN1206259C (en) | Adhesive polyimide resin and adhesive laminate | |
| TWI822976B (en) | Polyamic acid resin, polyimide resin and resin composition containing thereof | |
| CN1101438C (en) | Die attach adhesive composition | |
| AU729554B2 (en) | Anisotropic conductive adhesive compositions | |
| CN101864269B (en) | Thermal conductive adhesive | |
| CN102421849B (en) | Thermosetting polyimide resin composition, cured product, and adhesive | |
| CN103228753A (en) | Adhesive composition, adhesive sheet, and semiconductor device using the adhesive composition or the adhesive sheet | |
| Na et al. | Enhanced thermal conductivity of fluorinated epoxy resins by incorporating inorganic filler | |
| CN102791819A (en) | Heat-resistant adhesive | |
| CN111944312B (en) | Responsive heat-conducting polyimide precursor gel, preparation method thereof and responsive heat-conducting polyimide honeycomb structure | |
| CN109642027A (en) | Hardening resin composition, solidfied material, bonding agent, adhesive film, covering layer film, flexible copper-clad laminate and circuit substrate | |
| CN103666244A (en) | Composition for an FPCB coverlay and method for producing the same | |
| CN103059787B (en) | Thermally conductive adhesive composition, the bonding sheet material using said composition and thermal conductivity dicing die bonding film | |
| JP4771414B2 (en) | Polyimide silicone resin and thermosetting composition containing the same | |
| JP5352527B2 (en) | Novel polyimide and method for producing the same | |
| JP2009132830A (en) | Adhesive composition and dicing die attach film | |
| JP3569938B2 (en) | Paste composition and semiconductor device using the same | |
| JP4491898B2 (en) | Maleimide resin and process for producing the same | |
| JP3622952B2 (en) | Maleimide resin and method for producing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20140521 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |