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
  • C08G77/04—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
  • C09K5/14—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
  • 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
  • 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
  • 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
  • C08L83/06—Polysiloxanes containing silicon bound to oxygen-containing groups
• • 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
  • 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
  • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
• • 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 present inventors have made intensive studies to achieve the above objects, and found that a side-chain alkyl represented by the formula (1) in which an alkyl group is introduced via a chain derived from an alkyl group or a methacryl group
• 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 [9].
• 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 an alkyl group I having 1 to 14 carbon atoms
• R 3 is an alkyl group II having 15 to 18 carbon atoms
• R 5 and R 6 are each independently a hydrogen atom or a methyl group
• R 4 is an ethyl group
• w, x, y, z represent the number of units of each structural unit
• w, x, y, z are Each may be 0, x and y are not 0 at the same time, and the ratio of the sum of x and y to the sum of w, x, y, and z is 80 to 100%.
• [2] The side according to [1] above, wherein in formula (1), the ratio of x to the sum of w, x, y, and z is 20 to 80%, and the ratio of y is 15 to 75%.
• 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 an alkyl group I having 1 to 14 carbon atoms
• R 3 is an alkyl group II having 15 to 18 carbon atoms
• R 5 and Each R6 is independently a hydrogen atom or a methyl group
• R4 is an ethyl group.
• w, x, y, and z represent the number of units of each structural unit, w, x, y, and z may each be 0, and x and y are not 0 at the same time;
• the ratio of the sum of x and y to the sum of y and z is 80-100%.
• 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 ".
• the structural unit in parentheses indicated by y may be described as "structural unit having R 3 "
• the 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 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.
• alkyl groups are introduced via chains derived from acrylic or methacrylic groups. Since the chains derived from acrylic groups or methacrylic groups have oxygen bonds, grains between polymers are likely to be formed by hydrogen bonds, which is thought to further improve thermal conductivity. In addition, it is believed that 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. In this way, it is presumed that the thermal conductivity is improved because many alkyl groups capable of enhancing phonon propagation are introduced via chains derived from acryl groups or methacryloyl groups.
• 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 an alkyl group I having 1 to 14 carbon atoms. By introducing such a long-chain alkyl group I into the side chain, the thermal conductivity can be increased.
• R 2 is preferably an alkyl group having 6 to 12 carbon atoms, more preferably an alkyl group having 8 to 12 carbon atoms, and even more preferably an alkyl group having 12 carbon atoms.
• x represents the number of structural units having R 2 , preferably 0 to 100, more preferably 5 to 80, even more preferably 10 to 60.
• the ratio of x to the sum of w, x, y and z is 0 to 100%, preferably 60 to 100%, more preferably 80 to 100%.
• formula (1) has a structural unit having R 3 described later, for example, when the ratio of y to the sum of w, x, y, and z is 15 to 75%, the ratio of x is 20 to 80%. Even in such a case, the thermal conductivity can be increased.
• the alkyl group I represented by R 2 is preferably a linear alkyl group from the viewpoint of improving thermal conductivity.
• Linear alkyl groups include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group and n-tetradecyl group can be mentioned.
• 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 C 15-18 alkyl group II.
• the side chain-type alkyl-modified silicone resin of the present invention can be improved in thermal conductivity by introducing an alkyl group II.
• 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 0 to 100, more preferably 10 to 70, even more preferably 20 to 50.
• the ratio of y to the sum of w, x, y and z is 0 to 100%, preferably 15 to 75%, more preferably 20 to 70%.
• 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 alkyl groups in the side chain type 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 and y may each be 0, but x and y are not 0 at the same time, preferably both x and y are not 0. That is, it is preferable to introduce both the alkyl group I and the alkyl group II, which makes it easier to improve the thermal conductivity.
• the alkyl group II represented by R 3 is preferably a linear alkyl group from the viewpoint of improving thermal conductivity.
• linear alkyl groups include n-pentadecyl, n-hexadecyl, n-heptadecyl and n-octadecyl groups.
• 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.
• R5 and R6 are each independently a hydrogen atom or a methyl group. Above all, from the viewpoint of improving thermal conductivity, both R5 and R6 are preferably methyl groups.
• 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 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.
• an organopolysiloxane compound having a hydrosilyl group represented by the following formula (2) is treated with an alkyl (meth)acrylate I represented by the following formula (3) and an alkyl (meth)acrylate represented by the following formula (4) in the presence of a platinum catalyst.
• a method comprising the step of reacting with at least one selected from meth)acrylates II may be mentioned.
• part or all of the hydrosilyl group (SiH) of formula (2) reacts with at least one of alkyl (meth)acrylate I and alkyl (meth)acrylate II to form formula (1) ) can form a structural unit having R2 and a structural unit having R3 .
• the amount of R 2 and R 3 introduced can be adjusted to a desired amount by adjusting the blending amount of alkyl (meth)acrylate I and alkyl (meth)acrylate II.
• 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.
• 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.
• ethylene, methyl methacrylate, ethyl methacrylate, methyl acrylate, or ethyl acrylate may be further added and reacted in order to reduce the number of remaining hydrosilyl groups in formula (2), if necessary.
• a structural unit having R 4 in formula (1) is formed.
• a structural unit having R2 in formula (1) is 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 type of the insulating thermally conductive filler may be used alone, or two or more types 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, it can be used for various heat dissipation applications as heat dissipating 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 21 and Comparative Compounds 1 to 10 shown below.
• Compound 2 was a side chain type alkyl-modified silicone resin having the structure shown in Table 1.
• 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.
• Compound 8 was a side chain type alkyl-modified silicone resin having the structure shown in Table 1.
• Compound 9 was a side chain type alkyl-modified silicone resin having the structure shown in Table 1.
• Compound 10 was a side-chain alkyl-modified silicone resin having the structure shown in Table 1.
• Compound 11 was a side chain type alkyl-modified silicone resin having the structure shown in Table 1.
• Compound 13 was a side chain type alkyl-modified silicone resin having the structure shown in Table 1.
• Compound 16 was a side-chain alkyl-modified silicone resin having the structure shown in Table 1.
• Compound 17 was a side-chain alkyl-modified silicone resin having the structure shown in Table 1.
• Compound 18 was a side chain type alkyl-modified silicone resin having the structure shown in Table 1.
• Compound 19 was a side chain type alkyl-modified silicone resin having the structure shown in Table 1.
• Compound 20 was a side-chain alkyl-modified silicone resin having the structure shown in Table 1.
• Comparative compound 1 As comparative compound 1, commercial product 1 (“KF-96-50cst” manufactured by Shin-Etsu Chemical Co., Ltd.) having the following structure was used.
• Comparative compound 2 As comparative compound 2, commercial product 2 (“KF-96-200cst” manufactured by Shin-Etsu Chemical Co., Ltd.) having the following structure was used.
• Comparative compound 3 As comparative compound 3, commercial product 3 (“KF-96-1000cst” manufactured by Shin-Etsu Chemical Co., Ltd.) having the following structure was used.
• Comparative compound 4 As comparative compound 4, 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 3 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 lower thermal conductivity than the compounds of the examples, or deteriorated with time, making it difficult to achieve both high thermal conductivity and flexibility.

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