Classifications

• • 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
  • C09K5/14—Solid materials, e.g. powdery or granular
• • 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
  • C08G77/04—Polysiloxanes
  • C08G77/12—Polysiloxanes containing silicon bound to hydrogen
• • 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
  • 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
  • C08K5/01—Hydrocarbons
• • 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
  • C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon 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
  • 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
  • C09K5/10—Liquid materials
• • 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
  • C08K2201/00—Specific properties of additives
  • C08K2201/001—Conductive additives

Definitions

• the present invention relates to a side-chain alkyl-modified silicone resin and a resin composite material containing the side-chain alkyl-modified silicone resin.
• Heat-dissipating silicone greases are used to dissipate heat generated from various electronic devices, and are generally materials containing silicone resins (matrix resins) and fillers, and are required to have high thermal conductivity and flexibility. .
• a filler with high thermal conductivity increase the filling rate of the filler, and improve the thermal conductivity of the matrix resin.
• Non-Patent Document 1 examples of introducing an alkyl group into a silicone chain (Patent Documents 1 to 5) and introducing a liquid crystal site into a silicone chain (Non-Patent Document 1) have also been reported as methods of improving the thermal conductivity of a matrix resin. ing.
• Patent Documents 1 to 5 do not describe the relationship between the type of alkyl group to be introduced into the silicone resin, the introduction rate of the alkyl group, and the thermal conductivity. It is not clear whether it improves the thermal conductivity of In Non-Patent Document 1, crystallinity is improved by introducing a liquid crystal moiety into a silicone chain to improve thermal conductivity. As described above, there are almost no examples of specific methods for improving the thermal conductivity of the silicone resin itself, and solutions are lacking. Accordingly, an object of the present invention is to provide a silicone resin having high thermal conductivity while maintaining flexibility.
• the inventors of the present invention have made intensive studies to achieve the above object, and found that a side-chain alkyl represented by the formula (1), in which two types of long-chain alkyl groups with different carbon numbers are introduced in specific amounts, respectively.
• the inventors have found that the above problems can be solved by a modified silicone resin, and completed the present invention. That is, the present invention relates to the following [1] to [8].
• a side chain type alkyl-modified silicone resin represented by the following general formula (1).
• R 1 is a hydrogen atom or an alkenyl group
• R 2 is a long-chain alkyl group I having 6 to 14 carbon atoms
• R 3 is a long-chain alkyl group II having 15 to 18 carbon atoms.
• R 4 is an ethyl group
• w, x, y, and z represent the number of units of each structural unit, w and z may each be 0, and the total of w, x, y, and z is
• the proportion of x is 5-80%
• the proportion of y is 15-80%
• the total proportion of x and y is 80-100%
• x/y is 0.1-10.
• [5] The side chain according to any one of [1] to [4] above, wherein the ratio of z to the sum of w, x, y, and z in formula (1) is more than 0% and 20% or less. type alkyl-modified silicone resin.
• [6] The side chain type alkyl-modified silicone resin according to any one of [1] to [4] above, wherein the ratio of z to the sum of w, x, y and z in formula (1) is 0%. .
• [7] The side chain type alkyl-modified silicone resin according to any one of [1] to [6] above, which has a weight average molecular weight of 5,000 to 20,000.
• the side chain type alkyl-modified silicone resin of the present invention is represented by the following general formula (1).
• R 1 is a hydrogen atom or an alkenyl group
• R 2 is a long-chain alkyl group I having 6 to 14 carbon atoms
• R 3 is a long-chain alkyl group II having 15 to 18 carbon atoms.
• R 4 is an ethyl group
• w, x, y, and z represent the number of units of each structural unit
• w and z may each be 0, and the total of w, x, y, and z is , the proportion of x is 5-80%, the proportion of y is 15-80%, the total proportion of x and y is 80-100%, and x/y is 0.1-10.
• the structural unit in parentheses indicated by w may be described as "structural unit having R 1 "
• the structural unit in parentheses indicated by x may be described as "structural unit having R 2 ".
• structural unit in parentheses indicated by y may be described as "structural unit having R 3 "
• structural unit in parentheses indicated by z may be described as “structural unit having R 4 ".
• side-chain type refers to a type in which the chemical species is attached to the central portion of the polymer backbone molecule.
• the side chain type alkyl-modified silicone resin of the present invention has the structure of general formula (1), it maintains flexibility and improves thermal conductivity. Although the reason why the thermal conductivity is improved is not clear, it is presumed as follows. In order to improve the thermal conductivity of resin, it is effective to increase phonon propagation in polymer chains. An alkyl chain formed from a C--C--C bond has a wider bond angle and less strain than a silicone chain formed from a Si--O--Si bond, thereby improving phonon propagation. Furthermore, as shown in formula (1), since the long-chain alkyl group is introduced into the side chain of the silicone chain, the introduction rate of the alkyl group can be increased compared to introducing it into the terminal.
• the thermal conductivity is improved because many long-chain alkyl groups capable of enhancing phonon propagation are introduced.
• the alkyl group introduced into the side chain increases the radius of gyration of the polymer molecule and lengthens the molecular retention length, thereby improving the thermal conductivity.
• R1 is a hydrogen atom or an alkenyl group.
• the alkenyl group is preferably an alkenyl group having 2 to 10 carbon atoms, such as vinyl group, allyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, and the like. can be mentioned.
• w represents the number of structural units having R 1 , preferably 0-10, more preferably 0-5.
• the ratio of w to the sum of w, x, y, and z is preferably 0% or more than 0% and 20% or less, more preferably 0% or 0 % and 10% or less.
• the ratio of w is within this range, aggregation of the side chain type alkyl-modified silicone resin can be suppressed, and good flexibility can be maintained.
• R 1 represents a hydrogen atom or an alkenyl group bonded to a silicon atom, it is a highly reactive site. Therefore, the side chain type alkyl-modified silicone resin of the present invention having R 1 can form a cured product by an addition reaction with an alkenyl group-containing organopolysiloxane or hydrogen organopolysiloxane.
• R 2 is a long-chain alkyl group I having 6 to 14 carbon atoms.
• the side chain type alkyl-modified silicone resin of the present invention can increase the thermal conductivity by allowing such a long-chain alkyl group I to be present in the side chain in a specific proportion.
• R 2 is preferably a long-chain alkyl group having 6 to 12 carbon atoms, more preferably a long-chain alkyl group having 8 to 12 carbon atoms.
• x represents the number of structural units having R 2 , preferably 3-100, more preferably 5-80, even more preferably 10-40. Also, in formula (1), the ratio of x to the sum of w, x, y, and z is 5 to 80%. By adjusting the ratio of x to such a range, the thermal conductivity of the side chain type alkyl-modified silicone resin can be easily increased.
• the proportion of x is preferably 10-80%, more preferably 20-60%.
• the long-chain alkyl group I represented by R 2 is preferably a linear long-chain alkyl group from the viewpoint of improving thermal conductivity.
• Linear long-chain alkyl groups include n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group and n-tridecyl group. , n-tetradecyl group.
• a plurality of R 2 in formula (1) may be the same or different, but are preferably the same from the standpoint of ease of production.
• R 3 is a long-chain alkyl group II having 15 to 18 carbon atoms.
• the side chain-type alkyl-modified silicone resin of the present invention can increase the thermal conductivity while maintaining flexibility by allowing such long-chain alkyl groups II to exist in the side chains in a specific ratio.
• R 3 is preferably a long-chain alkyl group having 16 to 18 carbon atoms, more preferably a long-chain alkyl group having 18 carbon atoms.
• y represents the number of structural units having R 3 , preferably 5-100, more preferably 10-70, even more preferably 20-50.
• the ratio of y to the sum of w, x, y and z is preferably 15 to 80%. By adjusting the ratio of y to such a range, the thermal conductivity of the side chain type alkyl-modified silicone resin can be easily increased.
• the ratio of y is preferably 15 to 75%, more preferably 20 to 75%, from the viewpoint of improving the handling property by making the property liquid at room temperature (23° C.) while increasing the thermal conductivity.
• the ratio of the sum of x and y to the sum of w, x, y, and z is 80 to 100%. If the total ratio of x and y is less than 80%, the number of long-chain alkyl groups in the side-chain alkyl-modified silicone resin will decrease, resulting in a decrease in thermal conductivity.
• the total ratio of x and y is preferably 85-100%, more preferably 90-100%, still more preferably 95-100%.
• x/y (ratio of x to y) in formula (1) is 0.1-10.
• x/y is preferably 0.2-8, more preferably 0.4-5.
• the side chain type alkyl-modified silicone resin tends to become liquid at room temperature (23° C.), resulting in good handleability. If x/y is less than these upper limits, thermal conductivity tends to increase.
• the long-chain alkyl group II represented by R 3 is preferably a linear long-chain alkyl group from the viewpoint of improving thermal conductivity.
• linear long-chain alkyl groups include n-pentadecyl group, n-hexadecyl group, n-heptadecyl group and n-octadecyl group.
• a plurality of R 3 in formula (1) may be the same or different, but are preferably the same from the standpoint of ease of production.
• R4 is an ethyl group.
• z represents the number of structural units having R 4 , preferably 0-10, more preferably 0-5.
• the ratio of z to the sum of w, x, y, and z is preferably 0% or more than 0% and 20% or less, more preferably 0%. Or it is more than 0% and 10% or less.
• the ratio of the structural unit having R 1 , the structural unit having R 2 , the structural unit having R 3 , and the structural unit having R 4 may be as described above,
• the arrangement of structural units in the molecular chain is not limited. That is, each structural unit may exist in a molecule in a block-like manner, or may exist randomly.
• the weight average molecular weight of the side chain type alkyl-modified silicone resin of the present invention is not particularly limited, but is preferably 5,000 to 20,000, more preferably 7,000 to 18,000. When the weight-average molecular weight is within such a range, the viscosity can be adjusted appropriately and the flexibility can be easily maintained.
• the weight average molecular weight is a value determined by gel permeation chromatography (GPC) measurement and polystyrene conversion.
• the method for producing the side chain type alkyl-modified silicone resin of the present invention is not particularly limited.
• a method comprising reacting with a hydrocarbon I having 6 to 14 carbon atoms having a heavy bond and a hydrocarbon II having 15 to 18 carbon atoms having an unsaturated double bond.
• m is 10 to 200, preferably 10 to 120, more preferably 15 to 80.
• part or all of the hydrosilyl group (SiH) of formula (2) has a hydrocarbon I having 6 to 14 carbon atoms having an unsaturated double bond and an unsaturated double bond
• a structural unit having R 2 and a structural unit having R 3 in formula (1) can be formed by reacting with a hydrocarbon II having 15 to 18 carbon atoms.
• the amounts of R 2 and R 3 introduced can be adjusted to desired amounts by adjusting the amounts of hydrocarbon I and hydrocarbon II to be blended.
• the reaction temperature and reaction time may be appropriately adjusted.
• the reaction temperature is preferably 40 to 120° C., and the reaction time is preferably 1 to 24 hours. You may perform reaction in presence of a solvent.
• the type of solvent is not particularly limited, and may be appropriately adjusted according to the type of hydrocarbon having an unsaturated double bond, but toluene is preferred from the viewpoint of solubility of the synthesized product, reaction temperature, and the like.
• the hydrocarbon I having 6 to 14 carbon atoms and having an unsaturated double bond is preferably an ⁇ -olefin having 6 to 14 carbon atoms, specifically 1-hexene, 1-heptene, 1-octene, 1- nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, and 1-tetradecene.
• ⁇ -olefins having 5 to 18 carbon atoms are preferable. Octadecene may be mentioned.
• ethylene may be further added for reaction in order to reduce the number of remaining hydrosilyl groups in formula (2), if necessary.
• a structural unit having R 4 in formula (1) can be formed.
• the side chain type alkyl-modified silicone resin represented by formula (1) can be obtained.
• R 1 is an alkenyl group
• a hydrocarbon having two unsaturated double bonds preferably a hydrocarbon having 4 to 18 carbon atoms having unsaturated double bonds at both ends is added to obtain a hydrosilyl group. It may be reacted with a group.
• the resin composite material of the present invention contains the side chain type alkyl-modified silicone resin represented by the general formula (1) and an insulating thermally conductive filler.
• a side-chain alkyl-modified resin serves as a matrix resin, and an insulating thermally conductive filler is dispersed in the matrix resin.
• the side chain type alkyl-modified silicone resin of the present invention is excellent in thermal conductivity, so that the combined use of an insulating thermally conductive filler improves the thermal conductivity more effectively.
• the content of the side-chain alkyl-modified silicone resin in the resin composite material is not particularly limited, and may be appropriately adjusted while considering the dispersibility and thermal conductivity of the insulating thermally conductive filler, preferably 10 to 97. % by mass, more preferably 50 to 95% by mass.
• the resin composite material of the present invention contains an insulating thermally conductive filler.
• the insulating properties and thermal conductivity of the resin composite material can be improved.
• the average particle diameter of the insulating thermally conductive filler is not particularly limited, it is preferably 0.1 ⁇ m or more and 250 ⁇ m or less, and more preferably 0.2 ⁇ m or more and 100 ⁇ m or less.
• the average particle size can be measured by, for example, a laser diffraction method, and the particle size (d50) when the cumulative volume is 50% may be taken as the average particle size.
• the insulating thermally conductive filler has, for example, an insulating property with a volume resistivity of preferably 1.0 ⁇ 10 10 ⁇ cm or more at 20° C., and a thermal conductivity with a thermal conductivity of preferably 10 W/m ⁇ K or more. have Volume resistivity can be measured according to JIS C2141.
• the thermal conductivity can be measured, for example, by a periodic heating thermoreflectance method using a thermal microscope manufactured by Bethel Co., Ltd. on a cross section of the filler cut by a cross section polisher.
• the content of the insulating thermally conductive filler is not particularly limited, but is preferably 10 to 97 parts by mass, more preferably 50 to 95 parts by mass with respect to 100 parts by mass of the side chain type alkyl-modified silicone resin.
• the content of the insulating thermally conductive filler is at least these lower limits, the thermal conductivity of the resin composite material is enhanced.
• the content of the insulating thermally conductive filler is not more than these upper limits, it is possible to prevent the resin composite material from becoming unnecessarily hard or from being difficult to handle.
• the type of insulating thermally conductive filler is not particularly limited, but examples thereof include aluminum oxide, magnesium oxide, boron nitride, boron nitride nanotubes, aluminum nitride, and diamond.
• One of the insulating thermally conductive fillers may be used alone, or two or more thereof may be used in combination.
• the resin composite material may contain other silicone resins other than the side chain type alkyl-modified silicone resin represented by the general formula (1), if necessary, as long as the effects of the present invention are not impaired.
• Other silicone resins may be silicone resins having reactive groups such as alkenyl groups, hydrosilyl groups, and alkoxy groups, or silicone resins having no reactive groups. When containing other silicone resins, the content thereof is preferably 50% by mass or less, more preferably 30% by mass or less, and even more preferably 10% by mass or less, relative to the resin composite material.
• the resin composite material of the present invention may contain additives such as dispersants, antioxidants, heat stabilizers, colorants, flame retardants, and antistatic agents, if necessary.
• the application of the resin composite material of the present invention is not particularly limited, but for example, it can be used for various heat dissipation applications as heat dissipation silicone grease.
• the resin composite material can be placed between an electronic component such as a semiconductor element and a heat sink to effectively dissipate heat generated from the electronic component.
• the evaluation method for each compound (silicone resin) in each example and comparative example is as follows.
• the thermal conductivity of each compound of each example and comparative example was measured by TCi manufactured by C-Therm, and evaluated based on the following evaluation criteria. (evaluation) AA: 0.165 W/mK or more A: 0.160 W/mK or more and less than 0.165 W/mK B: 0.150 W/mK or more and less than 0.160 W/mK C: 0.150 W/ less than mK
• the side chain type alkyl-modified silicone resins used in Examples and Comparative Examples were prepared as Compounds 1 to 5 and Comparative Compounds 1 to 18 shown below.
• Compound 3 was a side chain type alkyl-modified silicone resin having the structure shown in Table 1.
• Compound 4 was a side chain type alkyl-modified silicone resin having the structure shown in Table 1.
• Compound 5 was a side chain type alkyl-modified silicone resin having the structure shown in Table 1.
• Comparative compound 3 As comparative compound 3, commercial product 1 (“KF-96-50cst” manufactured by Shin-Etsu Chemical Co., Ltd.) having the following structure was used.
• Comparative compound 4 As comparative compound 4, commercial product 2 (“KF-96-200cst” manufactured by Shin-Etsu Chemical Co., Ltd.) having the following structure was used.
• Comparative compound 5 As comparative compound 5, commercial product 3 (“KF-96-1000cst” manufactured by Shin-Etsu Chemical Co., Ltd.) having the following structure was used.
• Comparative compound 6 As comparative compound 6, commercial product 4 (“KF-96H-6000cst” manufactured by Shin-Etsu Chemical Co., Ltd.) having the following structure was used.
• Example 1 Thermal conductivity, initial shape, solubility in silicone, and change over time (gelation) were evaluated using Compound 1, which is the side chain type alkyl-modified silicone resin of the present invention produced as described above, as a sample. Table 2 shows the results.
• the compound (side-chain alkyl-modified silicone resin) of each example that satisfies the requirements of the present invention had high thermal conductivity, and had good solubility in silicone and good results of change over time. was excellent.
• the compounds of each comparative example had a lower thermal conductivity than the compounds of the examples.

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• 2022
  • 2022-03-29 JP JP2023511423A patent/JPWO2022210782A1/ja active Pending
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