Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/48—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
  • C08G77/58—Metal-containing linkages
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/38—Polysiloxanes modified by chemical after-treatment
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/48—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
  • C08G77/56—Boron-containing linkages
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/05—Alcohols; Metal alcoholates
  • C08K5/057—Metal alcoholates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/54—Silicon-containing compounds
  • C08K5/541—Silicon-containing compounds containing oxygen
  • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
  • C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L83/00—Compositions of 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; Compositions of derivatives of such polymers
  • C08L83/04—Polysiloxanes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L85/00—Compositions of macromolecular compounds obtained by reactions forming a linkage in the main chain of the macromolecule containing atoms other than silicon, sulfur, nitrogen, oxygen and carbon; Compositions of derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D183/00—Coating compositions 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; Coating compositions based on derivatives of such polymers
  • C09D183/14—Coating compositions 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; Coating compositions based on derivatives of such polymers in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
  • C08K3/013—Fillers, pigments or reinforcing additives

Definitions

• the present invention relates to a heat-resistant and heat-conductive material composed of an organic / inorganic cut material.
• heat-resistant and heat-conductive materials are used for semiconductor parts, electrophotographic parts and the like.
• heat-resistant heat conductive material a material obtained by filling a good heat conductive material into silicone rubber in terms of heat resistance has been used (for example, see Patent Documents 1 to 4).
• Patent Literature 1 Japanese Patent Publication No. 6-7101051
• Patent Document 2 Patent No. 27329792
• Patent Document 3 Patent No. 27 55 59 03
• Patent Document 4 Patent No. 27 55 59 04
• the present invention solves the above-mentioned problems by providing an organic / inorganic compound obtained by heating and gelling a sol solution containing a metal or metalloid alkoxide, an organic silicon compound, and a good thermal conductive material. It provides a heat-resistant and heat-conductive material made of a hybrid material.
• the organic silicon compound is desirably an organosiloxane having a functional group capable of reacting with a metal or metalloid alkoxide at one or both ends.
• the organic silicon compound is desirably a polyorganosiloxane having a functional group capable of reacting with a metal or metalloid alkoxide at one or both terminals having a weight average molecular weight of 400 or more.
• the organosilicon compound is a polyorganosiloxane having a weight-average molecular weight of 1500 or more and having a functional group capable of reacting with a metal or metalloid alkoxide at one or both terminals. Desirably.
• the organic / inorganic hybrid material is synthesized by a condensation reaction involving hydrolysis of a functional group capable of reacting with a metal or metalloid alkoxide at one or both terminals of the organic silicon compound and a metal or metalloid alkoxide. Is desirable.
• the above-mentioned condensation reaction is desirably carried out in a state where the viscosity of the above-mentioned organic silicon compound is reduced by heating to 80 ° C. or more.
• the metal of the above metal alkoxide is one or more of boron, aluminum, gay element, titanium, vanadium, manganese, iron, conjugate, germanium, yttrium, zirconium, niobium, lanthanum, cerium, tantalum, and tungsten. It is desirable to use the above metal.
• the good thermal conductive material is desirably fine particles of one or more metals and Z or metal oxides and Z or metal nitrides and / or metal carbides.
• the heat-resistant heat conductive material composed of the above-mentioned organic / inorganic hybrid improves the thermal conductivity of the above-mentioned organic / inorganic hybrid and imparts heat dissipation properties.
• ceramic fine particles such as boron nitride are added, the heat dissipation properties are improved. Excellent material is obtained.
• the heat resistant heat conductive material of the present invention it is possible to provide a heat resistant conductive member in which a high heat conductive filler is highly blended.
• the material has low hardness and high heat resistance of 200 ° C. or more.
• FIG. 1 is a cross-sectional view of a heat dissipation device of an IC package. Explanation of reference numerals
• the heat-resistant heat-conductive material of the present invention is an organic-inorganic hybrid material obtained by heating and gelling a sol liquid containing a metal or metalloid alkoxide, an organic silicon compound, and a good heat-conductive material. Consists of
• Examples of the metal or metalloid of the metal or metalloid alkoxide used in the present invention include boron, aluminum, silicon, titanium, vanadium, manganese, iron, cobalt, zinc, germanium, yttrium, zirconium, niobium, and lanthanum.
• Metals or metalloids that can form alkoxides such as cerium, cadmium, tantalum, and tungsten are mentioned, and particularly desirable metals are titanium, zirconium, and silicon.
• alkoxide is not particularly limited, and includes, for example, methoxide, ethoxide, propoxide, butoxide and the like.
• the metal or metalloid alkoxide is desirably chemically modified with a chemical modifier such as acetoacetate such as methyl acetoacetate, ethyl acetoacetate, and isopropyl acetoacetate.
• a chemical modifier such as acetoacetate such as methyl acetoacetate, ethyl acetoacetate, and isopropyl acetoacetate.
• organosilicon compound of the present invention for example, a metal or metalloid alkoxide at one or both terminals such as a dialkyldialkoxysilane, desirably at one or both terminals silanolpolydimethylsiloxane can be used.
• a metal or metalloid alkoxide at one or both terminals such as a dialkyldialkoxysilane, desirably at one or both terminals silanolpolydimethylsiloxane
• polyorganosiloxanes having various functional groups can be used.
• dialkyldialkoxysilane examples include dimethyldimethoxysilane, dimethyldimethoxysilane, getylethoxysilane, getyldipropoxysilane, getyldibutoxysilane, dipropyldimethoxysilane, dipropyldiethoxysilane, and dipropyldiproposilane.
• polyorganosiloxane those having a weight average molecular weight in the range of 400 to 800,000 are generally used, but those having a weight average molecular weight of 1,500 or more from the viewpoint of heat resistance. Is preferred.
• polyorganosiloxane having a weight average molecular weight in the range of 400 to 1500 is used. It is desirable to use. Further, under high temperature conditions of 200 or more, it is desirable to use a polyorganosiloxane having a weight average molecular weight of 1500 to 800 New When the weight average molecular weight of the organosiloxane exceeds 15,000, the viscosity becomes high and the synthesis becomes difficult, so that it is necessary to dilute the organosiloxane with a solvent.
• the weight average molecular weight of the organosiloxane is 80,000 or more, the viscosity of the sol becomes too high and the workability deteriorates.
• the weight average molecular weight of the organosiloxane is 15,000 or less, the heat resistance of the obtained organic / inorganic hybrid material is poor.
• the functional group capable of reacting with a metal or metalloid alkoxide at one or both terminals of the polyorganosiloxane is, for example, a functional group (Chemical Formulas 1 to 13) shown below. Note that R and R 'in the chemical formula represent methylene, alkylene, and alkyl.
• Halogen atoms such as Cl and Br
• the polyorganosiloxane having such a functional group easily reacts smoothly with a metal or metalloid alkoxide.
• Examples of the good thermal conductive material used in the present invention include metal powders such as copper, aluminum, silver, and stainless steel, metal oxide powders such as iron oxide, aluminum oxide, titanium oxide, silicon oxide, and cerium oxide.
• Metal nitrides such as boron nitride, aluminum nitride, chromium nitride, silicon nitride, tungsten nitride, magnesium nitride, molybdenum nitride, lithium nitride, etc., silicon carbide, zirconium carbide, tantalum carbide, titanium carbide, iron carbide, boron carbide, etc. And usually have a particle size of about 0.1 ⁇ m to 30 ⁇ m.
• the organic / inorganic hybrid material of the present invention is obtained by a condensation reaction involving hydrolysis of a functional group capable of reacting with a metal or metalloid alkoxide at one or both terminals of the organic silicon compound with a metal or metalloid alkoxide. Synthesized by The condensation reaction is carried out in a state where the viscosity of the silicon compound is reduced by heating to 80 ° C. or higher.
• an organic / inorganic hybrid material To produce an organic / inorganic hybrid material, first, a hydrolyzate of a desired metal or metalloid alkoxide is reacted with an organic component such as the above-mentioned organic silicon compound to prepare an organic / inorganic hybrid sol solution. I do.
• the organic component may be added to the alkoxide before hydrolysis or may be added to the hydrolyzed alkoxide. No.
• the metal or metalloid alkoxide or, if desired, the metal or metalloid alkoxide modified with the chemical modifier is dropped into the solution of the organic gay compound.
• acetone, toluene, xylene, tetrahydrofuran and the like are generally used in addition to various alcohols such as methanol and ethanol.
• the organic silicon compound solution is desirably heated and distilled to remove excess water and low molecular weight components.
• water is removed, when a metal or metalloid alkoxide is added to the solution of the organic silicon conjugate, hydrolysis of the metal or metalloid alkoxide due to residual moisture can be prevented, and the metal or metalloid alkoxide is dropped. It is possible to increase the speed to synthesize organic and inorganic hybrid materials in a short period of time, and effectively eliminate problems such as stickiness of organic-inorganic hybrid materials due to residual low molecular weight components and deterioration of mechanical strength. You can do it.
• the organic gay compound solution be subjected to acid treatment by adding hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid and the like.
• the acid is usually added to the organic silicon compound solution so that the pH of the organic silicon compound solution is in the range of 4 to 7.
• the chemical modifier is used in an amount of 1.5 mol or less, preferably 0.5 mol or more, per 1 mol of the metal alkoxide. Used in.
• the amount of the metal or metalloid alkoxide to be added to the organic silicon compound is usually in the range of 1: 0.1 to 1:10 in molar ratio.
• the content of the organic silicon compound is preferably about 80% by volume based on the metal or metalloid alkoxide. If the metal or metalloid component is more than the above ratio, the metal or metalloid component forms agglomerates, and swells and pores are formed in the obtained organic / inorganic hybrid material. Synergistic effects of inorganic components do not appear, approaching the characteristics of organic components.
• the above-mentioned organic / inorganic hybrid sol may be added with the above-mentioned good thermal conductive material.
• the amount of the good thermal conductive material is usually about 0.590% by mass based on the organic / inorganic hybrid. Since the organic'inorganic hybrid sol liquid of the present invention has excellent filler dispersibility, the good thermal conductive material can be easily and uniformly dispersed.
• fine particles having a particle diameter of about several meters also act as a thickener, so that they thicken the sol solution and give thixotropic viscosity characteristics. Therefore, a thick coating film can be easily formed.
• a filler such as an antioxidant, an ultraviolet absorber, a preservative, a viscosity modifier, and the like may be added to the organic / inorganic hybrid sol liquid, if desired, in addition to the good thermal conductive material.
• the organic / inorganic hybrid sol solution obtained as described above is a sol solution which does not become cloudy and has a long pot life.
• the sol solution is applied on a substrate and gelled by heating.
• the sol liquid is shaped by casting, extrusion, or the like, and fired under a certain atmosphere.
• an organic / inorganic hybrid having a predetermined shape can be formed on the surface of the core-type substrate by being applied to the surface of the member serving as the core-type substrate and gelling by heating.
• the heating conditions are usually from 60 ° C. to 450 ° C. for 20 seconds to 8 hours.
• the heat-resistant heat conductive material of the present invention is made of the above-mentioned organic'inorganic hybrid material.
• the heat-resistant heat conductive material of the present invention is excellent in heat resistance, conductivity, elasticity, and adhesion.
• the pH of the solution A was 5.
• Solution A was prepared by adding 0.08 mol of hydrochloric acid to a solution of 0.8 mol of dimethylethoxysilane and 2.5 mol of absolute ethanol.
• the pH of the solution A was 5.
• the solution B was allowed to flow down while stirring the solution A to prepare a sol solution.
• Alumina having a particle size of 0.5 to 20 m was added to the obtained sol solution.
• the amount of alumina added was 85% by mass with respect to the organic / inorganic octaip contained in the sol.
• the above sol was poured into a PFA Petri dish, pre-baked at 150 ° C for 3 hours, and then heated to 250 ° C. As a result, a heat-resistant sheet having a thickness of 0.2 mm was obtained.
• Two-component cured silicone rubber was coated on a metal plate with a doctor blade, and peroxide cross-linking was performed in a continuous furnace. After secondary vulcanization, a 0.3 mm thick insulating film was produced. When the insulation properties were evaluated, it was reduced to 10 12 ⁇ ⁇ cm or less at 200 ° C, causing a problem with the insulation properties at high temperatures.
• the above alumina was added to the silicone rubber raw material, and kneaded using a three-roll mill.
• the obtained rubber raw material was extruded using a T die to obtain a sheet molded body.
• This sheet was subjected to peroxide cross-linking in a continuous furnace to produce a heat conductive sheet after secondary vulcanization.
• only 75% by mass of alumina could be added.
• This film has a thermal conductivity of 1.4 wZm ⁇ K and a heat resistance of 180 ° C, which is inferior to the sheet of Example 1 in heat radiation.
• Silanol polydimethylsiloxane at both ends (weight average molecular weight: 6000, manufactured by GE Toshiba Silicone) 0.33 mol of anhydrous ethanol 2.0 mol solution, further add hydrochloric acid 0.03 mol, heat and stir, While removing the low molecular weight components, a solution of silanol polydimethylsiloxane at both ends was prepared. The pH of the solution was 5.
• the resulting boron nitride mixed hybrid was deposited on a metal roll surface to a thickness of 0.6 mm by dispenser coating. This roll was heated in an air atmosphere at 80 ° C for 30 minutes, at 180 ° C for 2 hours, and at 200 ° C for 30 minutes to obtain a fixing roll having a 0.6 mm organic-inorganic hybrid coating formed thereon. .
• good image quality was obtained. The time required to raise the temperature to the specified temperature was reduced to 2/3.
• Alumina and the like were added to silicone rubber, and a 0.6 mm thick film was formed on the surface of a metal roll using a flow coater, molded at 180 ° C, and subjected to secondary vulcanization to produce a silicone rubber roll. This roll was covered with a PFA tube to obtain a fixing port.
• Example 4 This roll satisfies the current fixing characteristics, but has high image quality due to the hardness of the PFA surface layer. In addition to the problem of heat treatment, the heat conductivity was poor, and the heating time was inferior to that of Example 3. (Example 4)
• Fig. 1 shows an embodiment of a heat dissipation device for an IC package.
• the heat dissipation device (1) is formed on a printed wiring board (2), a central processing unit (CPU) (3) installed on the printed wiring board (2), and an upper surface of the CPU (3).
• the heat radiating film (4) and the heat radiating plate (5) placed on the upper surface of the heat radiating film (4), and the CPU (3) and the heat radiating film (4) are composed of the substrate ( 2 ) and the heat radiating plate (4). 5 ) Between Porto (6) and Nut (F).
• Example 3 To the gel synthesized in Example 3, 80% by mass of alumina was added and kneaded using a propeller stirrer. The gel was deposited on the lower surface of the heat radiating plate (5) (the surface in contact with the CPU (3)) by screen printing, and a film was formed to a thickness of 0.1 mm under the firing conditions of Example 3.
• the heat radiating device (1) has a good heat radiating effect, has a small amount of heat storage, and has high durability. In addition, it has low hardness and shows a suitable setting, and it can be a good heat dissipating material because of its good adhesion.
• the heat-resistant and heat-conductive material comprising the organic-inorganic hybrid material of the present invention is particularly applied to heat-resistant rollers used in electrophotographic printing apparatuses, heat-resistant heat-conductive members as electric members, heat dissipation materials, and the like.

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• 2003
  • 2003-09-03 JP JP2003310797A patent/JP2004250665A/ja active Pending
• 2004
  • 2004-01-05 WO PCT/JP2004/000007 patent/WO2004067606A1/ja not_active Ceased
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