KR101625687B1 - Thermal conductive adhesive - Google Patents
Thermal conductive adhesive Download PDFInfo
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- KR101625687B1 KR101625687B1 KR1020100033602A KR20100033602A KR101625687B1 KR 101625687 B1 KR101625687 B1 KR 101625687B1 KR 1020100033602 A KR1020100033602 A KR 1020100033602A KR 20100033602 A KR20100033602 A KR 20100033602A KR 101625687 B1 KR101625687 B1 KR 101625687B1
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- conductive adhesive
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- VOFNEFZJOBFWHS-UHFFFAOYSA-N Cc(cc1Cc(cc(C)cc2Cc3cc(C)c(C)c(C)c3)c2O)cc(Cc2cc(C)c(C)c(C)c2)c1O Chemical compound Cc(cc1Cc(cc(C)cc2Cc3cc(C)c(C)c(C)c3)c2O)cc(Cc2cc(C)c(C)c(C)c2)c1O VOFNEFZJOBFWHS-UHFFFAOYSA-N 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/0001—Technical content checked by a classifier
- H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
Abstract
The present invention provides an electrically insulating thermally conductive adhesive having excellent heat conductivity and excellent adhesion to a heat generating member and a heat dissipating member.
(A) 100 parts by mass of a polyimide silicone resin having a repeating unit represented by the following general formula (1) and having a weight average molecular weight of 5,000 to 150,000
(B) 100 to 10,000 parts by mass of an electrically insulating thermally conductive filler and
(C) Organic solvents
And a thermally conductive adhesive.
≪ Formula 1 >
X is a divalent group having a phenolic hydroxyl group, Y is a divalent silicon residue represented by the following formula (2), Z is a divalent group other than X and Y, Q, and r are 0.15? P? 0.6, 0.05? Q? 0.8, 0? R? 0.75, and p + q + r = 1,
(2)
(Wherein R 1 and R 2 are each independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms and a is an integer of 1 to 20)
Description
TECHNICAL FIELD [0001] The present invention relates to a thermally conductive adhesive, and more particularly to a thermally conductive adhesive suitable for bonding an electronic element and a heat radiating member or a heat generating member.
In recent years, heat generation of electronic elements and members mounted with the electronic elements has been increased due to high performance, miniaturization, and high density of electronic elements, for example, a central processing unit (CPU) and a chip set of a computer. Therefore, cooling of the electronic device has become a very important technique for maintaining the performance of the electronic device and the member on which the electronic device is mounted. The heat dissipation efficiency of an electronic device is generally improved by contacting a material having good thermal conductivity with the electronic device. Therefore, there is an increasing demand for a heat-radiating material (TIM) having excellent thermal conductivity.
The heat-radiating material is placed between, for example, an electronic device and a cooling system (for example, a heat sink), and plays a role of effectively transferring the heat generated from the electronic device to the cooling system. The heat-radiating material is classified into a sheet-shaped molding and a paste-like composition from its shape or use. Sheet-shaped products are classified into, for example, a heat-radiating sheet of an elastomer (elastic polymer material) type and a phase change sheet of a hot-smelting type (a sheet which uses a heat-radiating material that varies phase by temperature). The paste-like composition is classified into, for example, a non-curing type heat dissipating grease and a heat dissipating gel or a heat dissipating adhesive which is a paste when applied and gelled or elastomerized by, for example, heat treatment.
These heat-radiating materials are generally composite materials filled with a high-density heat conductive material in an organic polymer material. The thermal conductivity of the organic polymer material is generally small and does not vary greatly depending on the type of organic polymer material. Therefore, the thermal conductivity of the heat radiation material largely depends on the volume filling rate of the thermally conductive material in the organic polymer material. Thus, it was important how much the thermally conductive material to charge in the organic polymer material.
The heat-radiating adhesive is required to have high thermal conductivity and to have an adhesive force under various environments or stresses. The higher the density of the thermally conductive material in the organic polymer material is, the better the heat radiation property of the heat radiation material is. However, the higher the density of the thermally conductive material in the organic polymer material, the more vulnerable the heat-radiating material itself, and the poorer the adhesive force with the flexible or adherend.
As the organic polymer material of the heat-releasing adhesive, epoxy resin, silicone polymer, polyimide and the like are known. However, the epoxy resin has good adhesiveness but has a defect in heat resistance and durability. Therefore, a silicone polymer is preferably used in view of wettability to a thermally conductive material or flexibility or thermal stability after curing (for example, see Patent Documents 1 and 2 below). However, both the adhesive property and the heat radiation property are not satisfied with the heat radiation material using the silicone polymer.
In addition, in the case of using polyimide having improved heat resistance, since the polyimide resin is solid, it can not be filled with the thermally conductive material. In order to avoid this, it is necessary to fill the thermally conductive material in the polyamic acid solution serving as the precursor, and heating thereof at 300 DEG C or higher is usually required for its hardening, so thermal load to the surroundings can not be avoided.
In addition, it is known to use polyimide silicone resin for protecting the surface of wiring parts such as semiconductor elements and printed boards, and it has higher adhesion and durability to substrates under high humidity conditions than silicone rubber (for example, Patent Document 3 ). And a composition containing the polyimide silicone resin is used as an adhesive for semiconductors (for example, see Patent Document 4). However, heat conductive adhesives using these polyimide silicone resins, in particular thermally conductive adhesives requiring electrical insulation, have not been studied.
An object of the present invention is to provide an electrically insulating thermally conductive adhesive (also referred to as a heat dissipating paste) having excellent thermal conductivity and excellent adhesion to an adherend, for example, a heat generating member and a heat dissipating member.
The present invention is the following thermally conductive adhesive.
(A) 100 parts by mass of a polyimide silicone resin having a repeating unit represented by the following formula (1) and having a weight average molecular weight of 5,000 to 150,000,
(B) 100 to 10,000 parts by mass of an electrically insulating thermally conductive filler and
(C) Organic solvents
And a thermally conductive adhesive.
(Wherein W is a divalent organic group, X is a divalent group having a phenolic hydroxyl group, Y is a divalent silicon residue represented by the following formula (2), and Z is a divalent organic group other than X and Y Q, and r are 0.15? P? 0.6, 0.05? Q? 0.8, 0? R? 0.75, and p + q + r = 1,
(Wherein R 1 and R 2 are independently of each other a substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms, and a is an integer of 1 to 20).
In one embodiment of the present invention, the thermally conductive adhesive further comprises (D) the thermosetting resin preferably in an amount of 0.1 to 20 parts by mass.
In one embodiment of the present invention, the thermosetting resin is reactive with the phenolic hydroxyl group in the formula (1).
In one embodiment of the present invention, the thermally conductive adhesive has an adhesive strength to a copper plate of 3 Mpa or more, preferably 5 to 10 Mpa.
When the thermally conductive adhesive of the present invention is placed on a copper plate and heated, the thermally conductive adhesive flows to wet and spread on the surface of the copper plate. Therefore, by the heat treatment, it is brought into close contact with the copper plate, resulting in good adhesion.
When the thermally conductive adhesive of the present invention is applied to an adherend and heated for curing, the adhesive flows and the surface of the adherend is wetted and spread and the solvent volatilizes. Therefore, the thermally conductive filler is applied on the surface of the adhesive cured product Exposed. Therefore, good thermal conductivity is obtained.
The present invention also provides an electronic device bonded to a heat radiating member or a heat generating member by a material obtained by curing the thermally conductive adhesive.
The thermally conductive adhesive of the present invention has excellent thermal conductivity by including a polyimide silicone resin having a specific structure, a thermally conductive filler, and an organic solvent, and has excellent adhesion to the adherend.
Hereinafter, the thermally conductive adhesive of the present invention will be described in more detail.
(A) a polyimide silicone resin
The polyimide silicone resin has a repeating unit represented by the following formula (1).
≪ Formula 1 >
W in formula (1) is a tetravalent organic group. W is, for example, pyromellitic dianhydride, 2,3,3 ', 4'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-biphenyltetracarboxylic dianhydride, 3 ', 4,4'-diphenyl ether tetracarboxylic acid dianhydride, 3,3', 4,4'-diphenylsulfonetetracarboxylic dianhydride, 3,3 ', 4,4'-benzophenonetetracar Hexafluoropropylidenebisphthalic acid dianhydride, 2,2-bis [4- (3,4-phenoxydicarboxylic acid) phenyl] propane, The acid can be selected from the residue of the anhydride.
X in formula (1) is a divalent organic group having a phenolic hydroxyl group. X is derived, for example, from a diamine having a phenolic hydroxyl group. X is, for example, a group represented by the following formulas (3) to (8).
Y in formula (1) is a divalent silicon residue represented by the following formula (2).
(2)
Formula 2 of R 1, R 2 are independently containing from 1 to 8 carbon atoms, preferably a divalent substituted or unsubstituted hydrocarbon group of 1 to 4 ring one another. R 1 and R 2 are, for example, a methyl group and an ethyl group.
In formula (2), a is an integer of 1 to 20, preferably 3 to 20. When a is larger than 20, the adhesion to the adherend is weakened.
Z in formula (1) is a divalent organic group other than X and Y. Z is derived from, for example, a diamine used in a conventional polyimide resin. The diamine is, for example, a combination of one or two or more selected from aliphatic diamines and aromatic diamines. The aliphatic diamines are, for example, tetramethylenediamine, 1,4-diaminocyclohexane and 4,4'-diaminodicyclohexylmethane. The aromatic diamines are, for example, phenylenediamine, 4,4'-diaminodiphenyl ether, and 2,2-bis (4-aminophenyl) propane. Z is preferably a group derived from an aromatic diamine represented by the following formula (9).
B in the formula (9) is a group represented by any one of the following formulas (10), (11) and (12)
P, q and r in the general formula (1) are in the range of 0.15? P? 0.6, 0.05? Q? 0.8, 0? R? 0.75, preferably 0.2? q? 0.75, and 0? r? 0.6. Within this range, good adhesiveness to the adherend can be obtained.
The sum of p + q + r in formula (1) is 1.
The weight average molecular weight of the polyimide silicone resin is 5,000 to 150,000, preferably 20,000 to 150,000. This is because if the molecular weight is smaller than the lower limit, the toughness as a resin is not exhibited. If the molecular weight is larger than the upper limit, mixing with the thermally conductive filler described later becomes difficult.
The polyimide silicone resin can be produced by, for example, a known method described below.
First, a tetracarboxylic acid dianhydride for deriving W, a diamine for deriving X and Z, and a diaminopolysiloxane for deriving Y are introduced into a solvent and reacted at a low temperature, for example, at 0 to 50 ° C . The solvent is a combination of one or more selected from N-methyl-2-pyrrolidone (NMP), cyclohexanone,? -Butyrolactone and N, N-dimethylacetamide (DMAc). Further, aromatic hydrocarbons such as toluene and xylene can be used in combination in order to facilitate removal of water generated at imidization by azeotropic distillation. By this reaction, a polyamic acid which is a precursor of the polyimide resin is produced. Next, the solution of the polyamic acid is heated to a temperature of preferably 80 to 200 占 폚, particularly preferably 140 to 180 占 폚. By this temperature elevation, the acid amide of polyamic acid undergoes dehydration ring closure reaction to obtain a solution of polyimide silicone resin. Tin minerals are formed when the solution is poured into a solvent, for example, water, methanol, ethanol or acetonitrile. The resulting precipitate is dried to obtain a polyimide silicone resin.
The molar ratio of the sum of the diamine and the diaminopolysiloxane to the tetracarboxylic acid dianhydride is preferably in the range of 0.95 to 1.05, particularly preferably 0.98 to 1.02.
To adjust the molecular weight of the polyimide silicone resin, a bifunctional carboxylic acid such as anhydrous phthalic acid and a monofunctional amine such as aniline may be added into the solution. The addition amounts of these compounds are, for example, not more than 2 mol% with respect to tetracarboxylic acid and diamine, respectively.
Imidization can be carried out by adding a dehydrating agent and an imidization catalyst in the imidization process and heating them at about 50 캜 as necessary. The dehydrating agent is, for example, an acid anhydride, for example, acetic anhydride, propionic anhydride and trifluoroacetic anhydride. The amount of the dehydrating agent to be used is, for example, 1 to 10 moles per 1 mole of diamine. The imidation catalysts are, for example, tertiary amines, such as pyridine, collidine, lutidine and triethylamine. The amount of the imidation catalyst to be used is, for example, 0.5 to 10 moles relative to 1 mole of the dehydrating agent used.
When a plurality of diamines and / or a plurality of tetracarboxylic acid dianhydrides are used, for example, there can be used a method in which the raw materials are mixed in advance and then subjected to air condensation, a method in which two or more diamines or tetracarboxylic acids are sequentially added can do. However, the reaction method is not particularly limited to this example.
(B) an electrically insulating thermally conductive filler
The electrically insulating thermally conductive filler is, for example, a metal oxide and a ceramic powder. The metal powder is, for example, zinc oxide powder or alumina powder. The ceramic powder is, for example, silicon carbide powder, silicon nitride powder, boron nitride powder, and aluminum nitride powder. The thermally conductive filler can be appropriately selected in terms of stability or cost.
The shape of the thermally conductive filler is not particularly limited, and examples thereof include granular, woody, flaky, and indefinite shapes. One kind or a mixture of two or more kinds of thermally conductive filler powders having these shapes may be used. The particle diameter distribution of the thermally conductive filler is not particularly limited, but is, for example, in the range of 0.05 to 100 탆 at 90 wt% or more, preferably 95 wt% or more. The average particle diameter of the thermally conductive filler is not particularly limited, but is, for example, in the range of 1 to 50 mu m. As the thermally conductive filler, for example, a single distribution (single-stick) may be used. However, in order to uniformly disperse the thermally conductive filler in the adhesive at a high density, it is more effective to use a thermally conductive filler having a single distribution in which a plurality of thermally conductive fillers having different shapes and particle diameters are combined to form a multi-bendable distribution.
The proportion of the thermally conductive filler in the thermally conductive adhesive of the present invention is 100 to 10,000 parts by mass, preferably 200 to 6,000 parts by mass, per 100 parts by mass of the polyimide silicone resin. When the ratio of the amount of the thermally conductive filler to the amount of the thermally conductive filler is less than the lower limit, sufficient thermal conductivity can not be obtained when the thermally conductive adhesive of the present invention is used. When the ratio of the amount of the thermally conductive filler to the amount of the thermally conductive filler exceeds the upper limit, when the thermally conductive adhesive of the present invention is used, sufficient adhesion strength with the object to be adhered is not obtained.
(C) Organic solvents
It is preferable that the organic solvent has compatibility with the component (A) and does not affect the surface state of the component (B). The organic solvent is a combination of one or more selected from, for example, ethers, ketones, esters, cellosolves, amides and aromatic hydrocarbons. The ethers include, for example, tetrahydrofuran and anisole. The ketones include, for example, cyclohexanone, 2-butanone, methylisobutylketone, 2-heptanone, 2-octanone and acetophenone. The esters include, for example, butyl acetate, methyl benzoate and? -Butyrolactone. Cellosolves include, for example, butyl carbitol acetate, butyl cellosolve acetate and propylene glycol monomethyl ether acetate. Amides include, for example, N, N-dimethylformamide, N, N-dimethylacetamide and N-methyl-2-pyrrolidone. Aromatic hydrocarbons such as toluene and xylene. The organic solvent is preferably selected from ketones, esters, cellosolves and amides. The organic solvent is particularly preferably butylcarbitol acetate,? -Butyrolactone, propylene glycol monomethyl ether acetate and N-methyl-2-pyrrolidone. These solvents may be used alone or in combination of two or more.
The amount of the organic solvent is generally in the range of 10 to 20 parts by weight based on the total amount of the polyimide silicone resin, the amount of the polyimide silicone resin, and the amount of the solvent in consideration of the solubility of the polyimide silicone resin, 60% by mass, preferably 20% by mass to 50% by mass. The composition may be stored at a relatively high concentration for storage and may be diluted to a desired concentration at the time of use.
The thermally conductive adhesive of the present invention may further contain (D) a thermosetting resin. The thermosetting resin reacts with the phenolic hydroxyl group to form a crosslinked structure. When the thermally conductive adhesive contains a thermosetting resin, for example, a solvent resistance performance is exhibited. The thermosetting resin is preferably an epoxy resin. Examples of the epoxy resin include one or two or more of bisphenol A type epoxy resin, bisphenol F type epoxy resin, triphenylmethane type epoxy resin, cyclic aliphatic epoxy resin, glycidyl ester type resin and glycidyl amine type resin to be. The bisphenol A type epoxy resin is, for example, phenol novolak type epoxy resin, cresol novolak type epoxy resin, and diglycidyl bisphenol A. The bisphenol F type epoxy resin is, for example, diglycidyl bisphenol F. The triphenylmethane type epoxy resin is, for example, triphenylolpropane triglycidyl ether. The cyclic aliphatic epoxy resin is, for example, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate. The glycidyl ester resin is, for example, diglycidyl phthalate, diglycidyl hexahydrophthalate, and dimethyl glycidyl phthalate. The glycidylamine resin may be, for example, tetraglycidyldiaminodiphenylmethane, triglycidyl-p-aminophenol, diglycidyl aniline, diglycidyl toluidine, tetraglycidylbisaminomethylcyclo Hexane. If necessary, a monofunctional epoxy compound containing one epoxy group in one molecule may be further added to the thermally conductive adhesive. In addition, a carbon-functional silane may be added for the purpose of improving adhesion with a substrate.
The amount of the epoxy resin is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 15 parts by mass or less, based on 100 parts by mass of the polyimide silicone resin. When the blending amount exceeds the upper limit, the adhesive strength, heat resistance and the like of the thermally conductive adhesive of the present invention tend to be lowered.
The thermally conductive adhesive of the present invention may contain various curing accelerators for the purpose of promoting the reaction of the epoxy resin. The curing accelerator is, for example, one or two or more of organic phosphine compounds, amino compounds and imidazole compounds. Organophosphine compounds are, for example, triphenylphosphine and tricyclohexylphosphine. The amino compound is, for example, trimethylhexamethylenediamine, diaminodiphenylmethane, 2- (dimethylaminomethyl) phenol, 2,4,6-tris (dimethylaminomethyl) phenol and triethanolamine. The imidazole compound is, for example, 2-methylimidazole, 2-ethylimidazole, 2-undecylimidazole, 2-ethyl-4-methylimidazole and 2-phenyl- Is hydroxymethylimidazole.
The amount of the curing accelerator is preferably 0 to 5 parts by mass based on 100 parts by mass of the total amount of the polyimide silicone resin and the epoxy resin. If the blending amount exceeds the upper limit, the available time tends to deteriorate.
The polyimide silicone resin exhibits excellent heat resistance, mechanical strength, solvent resistance, and adhesion to various substrates by thermosetting.
The curing conditions of the adhesive of the present invention are not particularly limited, but are in the range of 80 占 폚 to 300 占 폚, preferably 100 占 폚 to 200 占 폚. In the case of curing at a temperature lower than the lower limit, it takes too much time for heat curing, which is not practical. If components and compositions are selected so as to cure at a lower temperature than the lower limit, there is a possibility that the storage stability of the adhesive may become problematic. Further, unlike the conventional polyamic acid solution, the thermally conductive adhesive of the present invention does not require heating for a long time at a high temperature of 300 占 폚 or higher for curing, and therefore thermal degradation of the substrate can be suppressed.
The thermally conductive adhesive of the present invention may contain, in addition to the above-mentioned components, an antioxidant, an ultraviolet absorber, an adhesion improver, a flame retardant, a surfactant, a storage stability improver, an ozone deterioration inhibitor, a light stabilizer, a thickener, a plasticizer, One or two or more selected from an antioxidant, an antioxidant, a heat stabilizer, a radiation shielding agent, a nucleating agent, a lubricant, a pigment and a physical property regulating agent may be added to the object of the present invention and the effect of the heat conductive adhesive agent.
The thermally conductive adhesive of the present invention has a viscosity at 25 占 폚, preferably 0.5 to 2000 Pa 占 퐏, preferably 1.0 to 1000 Pa 占 퐏.
The thermal conductivity (W / mK) of the thermally conductive adhesive of the present invention is preferably 0.5 or more, more preferably 1.0 or more, particularly preferably 3 or more.
The bonding strength (MPa) of the thermally conductive adhesive of the present invention to the copper plate is preferably 3 or more, more preferably 5 or more, particularly preferably 6 or more. The bonding strength (MPa) after 240 hours at 80 ° C and 95 RH in a high-temperature and high-humidity atmosphere is preferably the same as described above.
The thermally conductive adhesive of the present invention is preferably used as an adhesive for an LED chip having a large heat generation amount due to high brightness, for example, and as an adhesive for a semiconductor device having a large heating value per unit area accompanied by miniaturization and weight reduction.
Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.
1. Synthesis of polyimide silicone resin
Three kinds of polyimide silicone resins were prepared as shown in Synthesis Examples 1 to 3 below.
Synthetic example One
88.8 g (0.2 mol) of 4,4'-hexafluoropropylidene bisphthalic acid dianhydride and 500 g of n-methyl-2-pyrrolidone were placed in a flask equipped with a stirrer, a thermometer and a nitrogen replacement device. Next, 33.6 g (0.04 mole) of the diaminosiloxane represented by the formula (13), 17.3 g (0.08 mole) of 4,4 ', - (3,3'-dihydroxy) diaminobiphenyl and 2,2- A solution prepared by dissolving 32.8 g (0.08 mol) of [4- (4-aminophenoxy) phenyl] propane in 100 g of n-methyl-2-pyrrolidone was prepared. The solution was dropped into the flask. During the dropwise addition, the temperature of the reaction system was adjusted so as not to exceed 50 캜. After the dropwise addition, the mixture was further stirred at room temperature for 10 hours. Next, after a reflux condenser equipped with a water receiver was attached to the flask, 50 g of xylene was added, the temperature was raised to 150 캜, and the temperature was maintained for 6 hours. As a result, a yellowish brown solution was obtained.
The resulting yellowish brown solution was cooled to room temperature (25 ° C) and re-precipitated by charging it into methanol. 140 g of the obtained precipitate was dried, and its linear absorption spectrum was measured. As a result, absorption based on unreacted polyamic acid (1,640 cm -1 ) was not observed, and absorption based on imide groups was confirmed at 1,780 cm -1 and 1,720 cm -1 . Next, the weight average molecular weight (in terms of polystyrene) was measured by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent and found to be 30,000. The product is called a polyimide silicone resin (I).
Synthesis Example 2
88.8 g (0.2 mol) of 4,4'-hexafluoropropylidene bisphthalic acid dianhydride and 500 g of n-methyl-2-pyrrolidone were placed in a flask equipped with a stirrer, a thermometer and a nitrogen replacement device. Next, 67.2 g (0.08 mole) of the diaminosiloxane represented by the above formula (13), 17.3 g (0.08 mole) of 4,4 ', - (3,3'-dihydroxy) diaminobiphenyl, A solution in which 16.4 g (0.04 mol) of bis [4- (4-aminophenoxy) phenyl] propane was dissolved in 100 g of n-methyl-2-pyrrolidone was prepared. The solution was dropped into the flask. During the dropwise addition, the temperature of the reaction system was adjusted so as not to exceed 50 캜. After the dropwise addition, the mixture was further stirred at room temperature for 10 hours. Next, after a reflux condenser equipped with a water receiver was attached to the flask, 50 g of xylene was added, the temperature was raised to 150 캜, and the temperature was maintained for 6 hours. As a result, a yellowish brown solution was obtained.
The resulting yellowish brown solution was cooled to room temperature (25 ° C) and re-precipitated by charging it into methanol. 160 g of the obtained precipitate was dried, and its linear absorption spectrum was measured. As a result, absorption based on unreacted polyamic acid (1,640 cm -1 ) was not observed, and absorption based on imide groups was confirmed at 1,780 cm -1 and 1,720 cm -1 . Next, the weight average molecular weight (in terms of polystyrene) was measured by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent and found to be 34,000. The product is called a polyimide silicone resin (II).
Synthesis Example 3
88.8 g (0.2 mol) of 4,4'-hexafluoropropylidene bisphthalic acid dianhydride and 600 g of n-methyl-2-pyrrolidone were placed in a flask equipped with a stirrer, a thermometer and a nitrogen replacement device. Next, 244.8 g (0.08 mole) of the diaminosiloxane represented by the general formula (14), 17.3 g (0.08 mole) of 4,4 ', - (3,3'-dihydroxy) diaminobiphenyl, A solution of 16.4 g (0.04 mol) of [4- (4-aminophenoxy) phenyl] propane dissolved in 100 g of n-methyl-2-pyrrolidone was prepared. The solution was dropped into the flask. During the dropwise addition, the temperature of the reaction system was adjusted so as not to exceed 50 캜. After the dropwise addition, the mixture was further stirred at room temperature for 10 hours. Next, after a reflux condenser equipped with a water receiver was attached to the flask, 50 g of xylene was added, the temperature was raised to 150 캜, and the temperature was maintained for 6 hours. As a result, a yellowish brown solution was obtained.
The resulting yellowish brown solution was cooled to room temperature (25 ° C) and re-precipitated by charging it into methanol. 300 g of the obtained sediment was dried, and its linear absorption spectrum was measured. As a result, absorption based on unreacted polyamic acid (1,640 cm -1 ) was not observed, and absorption based on imide groups was confirmed at 1,780 cm -1 and 1,720 cm -1 . Next, the weight average molecular weight (in terms of polystyrene) was measured by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent and found to be 36,000. The product is called a polyimide silicone resin (III).
2. Manufacture of adhesives
The following materials were used.
(A) Polyimide silicone resin: The polyimide silicone resin (I), (II) or (III) obtained in Synthesis Examples 1 to 3 was used.
(B) electrically insulating thermally conductive filler:
(B1) Thermally conductive filler A: alumina having an average particle diameter of 10 占 퐉 (specific gravity: 3.98)
(B2) Thermally conductive filler B: alumina having an average particle diameter of 1 占 퐉 (specific gravity: 3.98)
(C) Organic solvent: butyl carbitol acetate (BCA)
(D) Thermosetting resin: diglycidyl toluidine (DGT)
[Examples 1 to 4 and Comparative Examples 1 to 2]
(B), thermally conductive fillers (B1) and (B2), (C) an organic solvent, and (D) a thermosetting resin as shown in Table 1, , And the mixture was stirred so as to be homogeneous and defoamed to obtain an adhesive.
3. Evaluation test
The adhesives obtained in Examples 1 to 4 and Comparative Examples 1 and 2 were evaluated for viscosity, thermal conductivity and adhesive strength according to the following methods. Evaluation tests were conducted on silicone rubber C (commercial product) and D (commercially available product) each of heat-curable one-component type silicone rubber (Comparative Example 3 and Comparative Example 4, respectively). The results are shown in Table 2.
(1) Viscosity
The viscosity of each adhesive is measured at 25 ° C using a BH type rotational viscometer.
(2) Thermal conductivity
Each of the adhesives was introduced into the grooves of a plate of Teflon (trademark) (manufactured by Du Pont), dried at 80 ° C for 30 minutes, and then the adhesive was heated at 150 ° C for 1 hour to prepare test pieces of 10 mmφ × 1 mm . The thermal diffusivity and the specific heat capacity of the test piece were measured using a laser flash method LFA447 (manufactured by NETZSCH), and the thermal conductivity was obtained.
(3) Adhesive strength
Each adhesive is applied to a copper plate (100 mm × 25 mm × 1 mm) with a coating area of 20 mm × 20 mm and bonded to another copper plate of the same size. The bonded copper plate is dried at 80 캜 for 30 minutes, further dried at 150 캜 for 2 minutes under a pressure of 4 MPa, and heated at 150 캜 for 1 hour to obtain a test piece. The shear bond strength of the specimen is measured at a speed of 5 mm / min using an autograph (STROGRAPH V10-D (manufactured by Toyo Seiki Co., Ltd.)).
Further, the test piece obtained in the same manner as above was exposed to 80 ° C / 95% RH for 240 hours (high temperature and high humidity test), and the shear bond strength (after high temperature and high humidity test) was measured in the same manner as above.
From the above results, the adhesives I to III had appropriate viscosity, good thermal conductivity of 1.1 to 3.0 W / mK, good bonding strength of 8 to 15 MPa, and almost no decrease in bonding strength before and after the high temperature and high humidity test I did.
Claims (8)
(B) 100 to 10,000 parts by mass of an electrically insulating thermally conductive filler
(C) an organic solvent, and
(D) 0 to 20 parts by mass of a thermosetting resin
And a thermally conductive adhesive.
≪ Formula 1 >
X is a divalent group having a phenolic hydroxyl group, Y is a divalent silicon residue represented by the following formula (2), Z is a divalent group other than X and Y, Q, and r are 0.15? P? 0.6, 0.05? Q? 0.8, 0? R? 0.75, and p + q + r = 1,
(2)
(Wherein R 1 and R 2 are independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms, and a is an integer of 1 to 20)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009098430A JP5562574B2 (en) | 2009-04-14 | 2009-04-14 | Thermally conductive adhesive |
| JPJP-P-2009-098430 | 2009-04-14 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR20100113984A KR20100113984A (en) | 2010-10-22 |
| KR101625687B1 true KR101625687B1 (en) | 2016-05-30 |
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|---|---|---|---|
| KR1020100033602A KR101625687B1 (en) | 2009-04-14 | 2010-04-13 | Thermal conductive adhesive |
Country Status (4)
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| JP (1) | JP5562574B2 (en) |
| KR (1) | KR101625687B1 (en) |
| CN (1) | CN101864268B (en) |
| TW (1) | TWI468483B (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SG190423A1 (en) * | 2010-12-01 | 2013-06-28 | Toray Industries | Adhesive composition, adhesive sheet, and semiconductor device using the adhesive composition or the adhesive sheet |
| MY170959A (en) | 2012-04-10 | 2019-09-20 | Sumitomo Bakelite Co | Semiconductor device, die attach material, and method for manufacturing semiconductor device |
| EP3426746B1 (en) | 2016-03-08 | 2021-07-14 | Honeywell International Inc. | Phase change material |
| EP3498776B1 (en) * | 2016-08-08 | 2023-03-08 | Toray Industries, Inc. | Resin composition, sheet obtained therefrom, laminate, power semiconductor device, plasma processing apparatus, and process for producing semiconductor |
| JP2018093030A (en) * | 2016-12-01 | 2018-06-14 | 三菱電機株式会社 | Electronic device and electronic device manufacturing method |
| FR3060601B1 (en) * | 2016-12-20 | 2018-12-07 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | ADHESIVE COMPOSITION AND ITS USE IN ELECTRONICS |
| US11041103B2 (en) | 2017-09-08 | 2021-06-22 | Honeywell International Inc. | Silicone-free thermal gel |
| US11072706B2 (en) * | 2018-02-15 | 2021-07-27 | Honeywell International Inc. | Gel-type thermal interface material |
| JP2019172892A (en) * | 2018-03-29 | 2019-10-10 | 信越化学工業株式会社 | Silicone-modified polyimide resin composition |
| TWI661022B (en) * | 2018-05-30 | 2019-06-01 | 律勝科技股份有限公司 | Adhesive composition and adhesive sheet and cured product thereof |
| US11373921B2 (en) | 2019-04-23 | 2022-06-28 | Honeywell International Inc. | Gel-type thermal interface material with low pre-curing viscosity and elastic properties post-curing |
| CN115216267B (en) * | 2022-08-16 | 2023-08-22 | 西卡(江苏)工业材料有限公司 | Environment-friendly high-adhesion high-thermal-conductivity organic silicon pouring sealant and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008248114A (en) * | 2007-03-30 | 2008-10-16 | Shin Etsu Chem Co Ltd | Adhesive composition |
Family Cites Families (10)
| 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 |
| JPH0344040A (en) * | 1989-07-12 | 1991-02-25 | Hitachi Ltd | Semiconductor device and its manufacture |
| 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 |
| US6218496B1 (en) * | 1994-03-31 | 2001-04-17 | Occidental Chemical Corporation | Polyimidesiloxane adhesive |
| 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 |
| JP4535245B2 (en) * | 2004-05-21 | 2010-09-01 | 信越化学工業株式会社 | Partially-blocked polyimide-polysiloxane copolymer, process for producing the same, and resin composition containing the copolymer |
| JP2006253449A (en) * | 2005-03-11 | 2006-09-21 | Omron Corp | Lead frame module |
| JP5183076B2 (en) * | 2006-02-16 | 2013-04-17 | 信越化学工業株式会社 | Manufacturing method of semiconductor device |
| JP4548855B2 (en) * | 2007-09-05 | 2010-09-22 | 信越化学工業株式会社 | Thermosetting polyimide silicone resin composition and cured film thereof |
| JP5489261B2 (en) * | 2009-04-14 | 2014-05-14 | 信越化学工業株式会社 | Thermally conductive adhesive |
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2009
- 2009-04-14 JP JP2009098430A patent/JP5562574B2/en active Active
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- 2010-04-13 TW TW99111421A patent/TWI468483B/en not_active IP Right Cessation
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008248114A (en) * | 2007-03-30 | 2008-10-16 | Shin Etsu Chem Co Ltd | Adhesive composition |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101864268A (en) | 2010-10-20 |
| TWI468483B (en) | 2015-01-11 |
| JP5562574B2 (en) | 2014-07-30 |
| KR20100113984A (en) | 2010-10-22 |
| CN101864268B (en) | 2014-01-22 |
| TW201114869A (en) | 2011-05-01 |
| JP2010248349A (en) | 2010-11-04 |
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