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
  • C09J171/00—Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
  • C09J171/02—Polyalkylene oxides
• • 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
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/32—Polymers modified by chemical after-treatment
  • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
  • C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon
• • 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
• • 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
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
  • C09K5/08—Materials not undergoing a change of physical state when used
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L101/00—Compositions of unspecified macromolecular compounds
  • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
  • C08L101/10—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing hydrolysable silane groups

Definitions

• the present invention relates to a heat conductive composition, and more particularly to a moisture-curing heat conductive composition that does not release an outgas containing a compound that adheres to a laser diode of an optical pickup device as a foreign substance.
• a heat radiation material having high thermal conductivity is applied to a laser diode mounted on an optical pickup device for reading an optical disk in order to suppress a temperature rise of the laser diode during light output (Patent Document 1).
• Patent Document 1 a heat radiation material having high thermal conductivity is applied to a laser diode mounted on an optical pickup device for reading an optical disk in order to suppress a temperature rise of the laser diode during light output.
• the heat dissipation material is heated to 60 ° C. to 90 ° C. by light emission of the laser diode, foreign matter is formed at the light emitting point of the laser diode.
• the output of the laser diode becomes unstable and the reliability of the optical pickup device is greatly reduced.
• An object of the present invention is to provide a moisture-curing heat conductive composition that does not form foreign matter at the light emitting point of a laser diode and has excellent curability.
• the present inventors have found that the aldehyde having 4 to 8 carbon atoms contained in the outgas generated from the thermally conductive composition heated to 60 ° C. to 90 ° C. by the light emission of the laser diode adheres to the light emitting point of the laser diode. And found out that foreign matter is generated.
• the present inventors when the content of the organometallic catalyst having a hydrocarbon group having 4 to 8 carbon atoms is 0.02% by mass or less based on the total mass of the composition, It has been found that no foreign matter derived from aldehyde gas having 4 to 8 carbon atoms is formed at the light emitting point of the laser diode when the product is heated to 60 ° C. to 90 ° C.
• the curing catalyst (B) includes an organometallic catalyst having a hydrocarbon group having 1 to 3 carbon atoms, an organometallic catalyst having a hydrocarbon group having 9 to 20 carbon atoms, and / or an amine catalyst.
• the heat conductive composition as described in [1].
• Composition Composition.
• the heat conductive composition according to [1] which is a heat conductive adhesive for optical pickups.
• the heat conductive composition of the present invention does not generate aldehyde gas having 4 to 8 carbon atoms and has excellent curability, it is preferably used as a moisture curable heat conductive composition for optical pickups. be able to.
• the present invention is a thermally conductive composition containing (A) a polymer having a crosslinkable silyl group, (B) a curing catalyst, and (C) a thermally conductive filler.
• the polymer (A) having a crosslinkable silyl group has a polyoxyalkylene, polyisobutylene, acrylate copolymer or the like as a main chain skeleton, and a crosslinkable silyl group at the terminal and side chain.
• the crosslinkable silyl group is a silicon atom to which at least one hydroxyl group or hydrolyzable group is bonded.
• hydrolyzable group examples include a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, a mercapto group, an alkenyloxy group, and a carboxyl group. .
• an alkoxy group is preferable and a dialkoxy group is more preferable in terms of mild hydrolyzability and easy handling.
• Examples of the polymer (A) having a crosslinkable silyl group include polypropylene glycol having a crosslinkable silyl group, polyethylene glycol having a crosslinkable silyl group, a propylene glycol-ethylene glycol copolymer having a crosslinkable silyl group, and a crosslinkable property.
• Examples thereof include polyisobutylene having a silyl group and an acrylate copolymer having a crosslinkable silyl group.
• a polyalkylene glycol having a crosslinkable silyl group is preferable because it is easily available.
• the polymer (A) having a crosslinkable silyl group used in the present invention is preferably a number average molecular weight (Mn) of 500 to 20,000, more preferably 500 to 10,000, from the viewpoints of physical properties and workability of the thermally conductive composition. ).
• Mn number average molecular weight
• the number average molecular weight (Mn) in the present invention is a polystyrene equivalent value measured by gel permeation chromatography (GPC).
• the oxyalkylene polymer (A) having a crosslinkable silyl group can be produced by a conventionally known method. Moreover, in the heat conductive composition of this invention, the polymer (A) which has a crosslinkable silyl group may be used independently, and may use 2 or more types together. Examples of such polypropylene glycol having a crosslinkable silyl group include MS polymer and silyl grade manufactured by Kaneka Corporation. Specific examples include MS polymer S203 and silyl SAT350.
• the content of the polymer (A) having a crosslinkable silyl group is usually 5% by mass or more, preferably 8% by mass or more, more preferably 10% by mass or more based on the total mass of the heat conductive composition. .
• the content of the polymer (A) having a crosslinkable silyl group is usually 50% by mass or less, preferably 30% by mass or less, more preferably 20% by mass or less, based on the total mass of the heat conductive composition. is there.
• content of a component (A) exceeds 50 mass%, there exists a possibility that sufficient heat conductivity improvement effect may not be acquired.
• the content of the component (A) is less than 5% by mass, sufficient adhesiveness may not be obtained.
• the heat conductive composition of this invention contains a curing catalyst (B) in addition to the polymer (A) which has the said crosslinkable silyl group.
• the curing catalyst (B) used in the heat conductive composition of the present invention includes an organometallic catalyst, an amine-based catalyst, a low molecular weight polyamide resin obtained from an excess polyamine and a polybasic acid, and an excess polyamine and an epoxy compound.
• the known silanol condensation catalyst such as the reaction product of Among these, an organometallic catalyst and an amine catalyst are preferable from the viewpoint of availability and reaction acceleration.
• These curing catalysts may be used alone or in combination of two or more.
• organometallic catalyst examples include tin octylate, tin naphthenate, tin neodecanoate, tin stearate, dibutyltin dioctoate, dibutyltin dilaurate, dioctyltin dilaurate, dioctyltin diversate, dibutyltin bistriethoxysilicate, dibutyltin dioleylmaline.
• organic tin compounds such as dibutyltin diacetylacetonate, bismuth, barium, calcium, indium
• a titanium chelate compound coordinated with a chelating agent such as ⁇ -diketone or ⁇ -ketoester can also be used as the organometallic catalyst.
• ⁇ -diketones include 2,4-pentanedione, 2,4-hexanedione, 2,4-heptanedione, dibenzoylmethane, thenoyltrifluoroacetone, 1,3-cyclohexanedione, 1-phenyl1,3-
• ⁇ -ketoesters include methyl acetoacetate, ethyl acetoacetate, propyl acetoacetate, butyl acetoacetate, methyl pivaloyl acetate, methyl isobutyroyl acetate, methyl caproyl acetate, and methyl lauroyl acetate.
• organometallic catalysts may be used alone or in combination of two or more.
• an organic tin compound is preferable from the viewpoint of reaction promotion.
• Representative commercial products of the above metal catalysts include, for example, Neostan U-220 (dibutyltin), U-810 (dioctyltin), U-50 (tineodecanoate), Neostan U600 (bismuth tris (2) manufactured by Nitto Kasei Co., Ltd. -Ethyl hexanoate)) and the like.
• amine catalyst examples include butylamine, octylamine, laurylamine, dibutylamine, monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, Amines such as triethylenediamine, guanidine, diphenylguanidine, 2,4,6-tris (dimethylaminomethyl) phenol, morpholine, N-methylmorpholine, 1,8-diazabicyclo (5.4.0) undecene-7 (DBU) Or a salt of these with a carboxylic acid or the like.
• amine catalysts may be used alone or in combination of two or more.
• DBA manufactured by San Apro Co., Ltd. may be mentioned.
• the organometallic catalyst having a hydrocarbon group having 4 to 8 carbon atoms such as tin octylate, dibutyltin dioctoate, dibutyltin dilaurate, and bismuth tris (2-ethylhexanoate) is used at 60 ° C to 90 ° C.
• an aldehyde gas having 4 to 8 carbon atoms can be generated.
• the aldehyde gas having 4 to 8 carbon atoms adheres to the light emitting point of the laser diode, and foreign matters derived from the aldehyde gas may be generated.
• the content of the organometallic catalyst having a hydrocarbon having 4 to 8 carbon atoms in the curing catalyst (B) is usually 0.001 to 0.02% by mass, preferably 0.000, based on the total amount of the heat conductive composition.
• the content is 001 mass% to 0.01 mass%, more preferably 0.001 mass% to 0.008 mass%.
• the content of the organometallic catalyst having a hydrocarbon group having 4 to 8 carbon atoms is within the above range, even when the composition of the present invention is heated to 60 ° C. to 90 ° C. due to the laser diode emitting light. No foreign matter derived from aldehyde gas having 4 to 8 carbon atoms adheres to the light emitting point of the laser diode.
• the content of the organometallic catalyst having a hydrocarbon group having 1 to 3 carbon atoms and / or the organometallic catalyst having a hydrocarbon group having 9 or more carbon atoms in the curing catalyst (B) is usually heat conductive.
• the content is 0.01% by mass to 2.0% by mass, preferably 0.01% by mass to 1.0% by mass, more preferably 0.01% by mass to 0.5% by mass, based on the total amount of the composition.
• the content of the curing catalyst (B) in the heat conductive composition of the present invention is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, based on the total mass of the heat conductive composition. is there.
• the content of the curing catalyst (B) is preferably 2.0% by mass or less, more preferably 1.0% by mass or less, based on the total weight of the heat conductive composition.
• the content of the curing catalyst (B) exceeds 2.0% by mass, the curing rate may be increased and the workability may be hindered.
• content of a curing catalyst (B) is less than 0.01 mass%, there exists a possibility that sclerosis
• the heat conductive composition of this invention contains a heat conductive filler (C) in addition to the polymer (A) which has a crosslinkable silyl group, and a curing catalyst (B).
• the thermally conductive filler include, but are not limited to, aluminum oxide, aluminum powder, zinc oxide, aluminum nitride, boron nitride, carbon fiber, magnesium oxide, and aluminum hydroxide.
• aluminum oxide is preferable from the viewpoint of filler stability (hygroscopicity) and cost, and spherical aluminum oxide is more preferable from the viewpoint of high filler filling.
• a heat conductive filler may be used independently or may use 2 or more types together.
• the aluminum oxide etc. which are marketed as the DAM series and DAW series from Denki Kagaku Kogyo Co., Ltd. are mentioned, for example.
• the content of the heat conductive filler (C) in the heat conductive composition of the present invention is usually 50% by mass or more, preferably 70% by mass or more, more preferably 80% by mass based on the total mass of the heat conductive composition. That's it. Moreover, content of a heat conductive filler (C) is 95 mass% or less normally based on the total weight of a heat conductive composition, Preferably it is 90 mass% or less, More preferably, it is 85 mass% or less. When the content of the heat conductive filler (C) exceeds 95% by mass, the viscosity may be remarkably increased. Moreover, when content of a heat conductive filler (C) is less than 50 mass%, there exists a possibility that sufficient heat conductivity improvement effect may not be acquired.
• the heat conductive composition of the present invention may contain, in addition to the above components (A) to (C), usual additives such as an adhesion-imparting agent, a plasticizer and a colorant.
• adhesion imparting agent examples include amino acids such as N- ( ⁇ -aminoethyl) -N ′-( ⁇ -trimethoxysilylpropyl) -ethylenediamine and N- ( ⁇ -aminoethyl) - ⁇ -aminopropyltrimethoxysilane.
• examples thereof include mercaptoalkoxysilanes such as alkoxysilane, 3-mercaptopropylmethyldimethoxysilane, and 3-mercaptopropyltrimethoxysilane. Of these, aminosilane compounds are preferred.
• an adhesiveness-imparting agent 0.01% to 2.0% by mass of the adhesiveness-imparting agent may be contained based on the total mass of the heat-conductive composition. .
• plasticizer thickening agent, viscosity modifier
• known paraffinic, naphthenic, polybutene and other hydrocarbons can be used as long as the flash point, viscosity, paint adhesion, etc. are not affected.
• phthalic acid diesters such as diisononyl phthalate (DINP)
• epoxidized hexahydrophthalic acid diesters alkylene dicarboxylic acid diesters, alkylbenzenes, and the like can also be used within a range that does not impair curability.
• colorants include colorants (Bengara, titanium oxide, carbon black, other color pigments, dyes, etc.), organic solvents (acetone, methyl ethyl ketone, ligroin, ethyl acetate, tetrahydrofuran, n-hexane, heptane as necessary.
• UV absorbers / light stabilizers benzotriazoles, hindered amines, etc.
• antioxidants hinderedered phenols, etc.
• thixotropic agents colloidal silica, organic bentonite, fatty acid amide, hydrogenated castor oil, etc.
• Solvents alicyclic hydrocarbons, aromatic hydrocarbons, etc. can be used in an appropriate amount range.
• the heat conductive composition for the laser diode mounted on the optical pickup device can be preferably used as a product.
• the heat conductive composition of this invention has the favorable surface tack property after hardening, it is excellent in workability
• Each of the thermally conductive compositions of the present invention is a conventional kneader, such as T. Using K Hibismix 2P-1, etc., it can be produced by mixing the above components (A) to (C) and other additives as required.
• the preparation method of the heat conductive composition of this invention is not limited to what was mentioned above.
• the thermally conductive composition of the present invention can be applied to a laser diode holder mounted on an optical disk reader and cured by moisture in the air.
• Neostan U220 Dibutyltin diacetylacetonate (Note 8) Nitto Kasei Co., Ltd.
• Neostan 810 Dioctyltin dilaurate (Note 9) Nitto Kasei Co., Ltd.
• Neostan U600 Bismuth tris (2-ethylhexanoate)
• Viscosity measurement The viscosity (Pa ⁇ s) of the heat conductive composition was measured with a cone plate viscometer (BROOKFIELD VISCOMETER DV-II + Pro). Measurement conditions: cone model number CP52, rotation speed 0.1 rpm
• GC-MS analyzer QP2010 (manufactured by Shimadzu Corporation)
• Column type TC-1 (30m ⁇ 0.25mm ID 1.0 ⁇ m)
• Analysis conditions After holding at 40 ° C. for 3 minutes, the temperature was raised to 280 ° C. at a heating rate of 10 ° C./min, and held at 280 ° C. for 8 minutes.
• Vaporization temperature 240 ° C., ion source 230 ° C.
• EI injection volume 1 mL

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• 2011
  • 2011-02-09 JP JP2011026308A patent/JP5743584B2/ja active Active
• 2012
  • 2012-02-08 WO PCT/JP2012/052846 patent/WO2012108458A1/ja not_active Ceased

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