Side-chain alkyl-modified silicone resin

Abstract

A side chain alkyl-modified silicone resin according to the present invention is represented by general formula (1) below. (In formula (1), R1 is a hydrogen atom or an alkyl group; R2 is an alkyl group I having a carbon number of 1 to 14; R3 is an alkyl group II having a carbon number of 15 to 18; R5 and R6 are independent hydrogen atoms or methyl groups, respectively; R4 is a methyl group or an ethyl group; w, x, y, and z represent unit numbers of component units, where w, x, y, and z may be 0, x and y are never simultaneously 0, and the percentage ratio of the total of x and y to the total of w, x, y, and z is 80% to 100%.)　According to the present invention, a silicone resin can be provided which has high heat conductivity while maintaining flexibility.

Description

[Technical Field]

[0001] 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. [Background technology]

[0002] In recent years, with the increasing heat generation associated with the high integration of circuits in electronic devices, thermal management has become crucial, leading to a growing demand for heat dissipation materials. Silicone grease for heat dissipation is used to dissipate heat generated by various electronic devices and is generally a material containing silicone resin (matrix resin) and fillers, requiring high thermal conductivity and flexibility. To improve the thermal conductivity of silicone grease for heat dissipation, methods such as using fillers with high thermal conductivity, increasing the filler density, and improving the thermal conductivity of the matrix resin can be considered. However, while boron nitride, aluminum nitride, and diamond are known as fillers with high thermal conductivity, these fillers have poor compatibility and dispersibility with silicone resin, and increasing the filler density tends to reduce flexibility. Furthermore, increasing the filler density increases the specific gravity of composite materials such as heat-dissipating silicone grease, making it impossible to lighten electronic devices. On the other hand, as a method to improve the thermal conductivity of the matrix resin, examples have been reported in which alkyl groups are introduced into the silicone chain (Patent Documents 1-5), and in which liquid crystal portions are introduced into the silicone chain (Non-Patent Document 1). [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 10-110179 [Patent Document 2] Japanese Patent Application Publication No. 11-049958 [Patent Document 3] Japanese Patent Publication No. 2005-154532 [Patent Document 4] Japanese Patent Publication No. 2007-277387 [Patent Document 5] Japanese Patent Publication No. 2009-209230 [Non-patent literature]

[0004] [Non-Patent Document 1] Ying Li, Chenggong Li, Liang Zhang, Wenying Zhou., Journal of Materials Science:Materials in Electronics,Published online:18 March 2019 (https: / / doi.org / 10.1007 / s10854-019-01150-1) [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] However, Patent Documents 1 to 5 do not describe the relationship between the type and rate of alkyl groups introduced into the silicone resin and the thermal conductivity, and it is not clear how to specifically improve the thermal conductivity of the silicone resin. Furthermore, Non-Patent Document 1 improves thermal conductivity by increasing crystallinity by introducing liquid crystal portions into the silicone chain, but the resin becomes solid due to excessive crosslinking and loses its flexibility. As described above, there are very few examples of specific methods for improving the thermal conductivity of silicone resin itself, and solutions are scarce. Therefore, the objective of this invention is to provide a silicone resin that maintains flexibility while having high thermal conductivity. [Means for solving the problem]

[0006] As a result of diligent research to achieve the above objective, the present inventors have found that the above problems can be solved by a side-chain type alkyl-modified silicone resin represented by formula (1), in which an alkyl group is introduced via a chain derived from an alkyl group or a methacrylic group, and have completed the present invention. In other words, the present invention relates to the following [1] to [9].

[0007] [1] A side-chain alkyl-modified silicone resin represented by the following general formula (1). [ka] (In equation (1), R 1 R is a hydrogen atom or an alkenyl group, 2 is an alkyl group I having 1 to 14 carbon atoms, and R 3 R is an alkyl group II with 15 to 18 carbon atoms. 5 and R 6 Each is independently a hydrogen atom or a methyl group, and R 4 (where is an ethyl group, and w, x, y, and z represent the number of units of each constituent unit. w, x, y, and z may each be 0, but x and y cannot be 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 80-100%.) [2] The side-chain alkyl-modified silicone resin 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%. [3] The R 2 and R 3 A side-chain alkyl-modified silicone resin according to [1] or [2] above, wherein the alkyl group is a linear alkyl group. [4] A side-chain alkyl-modified silicone resin according to any of [1] to [3] above, wherein in formula (1), the proportion of w to the sum of w, x, y, and z is greater than 0% and less than or equal to 20%. [5] A side-chain alkyl-modified silicone resin according to any of [1] to [3] above, wherein the ratio of w to the sum of w, x, y, and z in formula (1) is 0%. [6] A side-chain alkyl-modified silicone resin according to any of [1] to [5] above, wherein in formula (1), the proportion of z to the sum of w, x, y, and z is greater than 0% and less than or equal to 20%. [7] In the formula (1), the ratio of z to the sum of w, x, y, and z is 0%, and the side-chain type alkyl-modified silicone resin according to any one of the above [1] to [5]. [8] The weight average molecular weight is 5,000 to 20,000, and the side-chain type alkyl-modified silicone resin according to any one of the above [1] to [7]. [9] A resin composite material containing the side-chain type alkyl-modified silicone resin according to any one of the above [1] to [8] and an insulating thermal conductive filler.

Effect of the Invention

[0008] According to the present invention, it is possible to provide a silicone resin having a high thermal conductivity while maintaining flexibility.

Modes for Carrying Out the Invention

[0009] [Side-chain type alkyl-modified silicone resin] The side-chain type alkyl-modified silicone resin of the present invention is represented by the following general formula (1).

Chemical formula

[0010] The side-chain alkyl-modified silicone resin of the present invention has the structure of general formula (1), thereby improving thermal conductivity while maintaining flexibility. The reason for the improved thermal conductivity is not clear, but it is presumed to be as follows. To improve the thermal conductivity of resins, increasing phonon propagation in polymer chains is effective. Alkyl chains formed from CCC bonds exhibit better phonon propagation than silicone chains formed from Si-O-Si bonds because they have wider bond angles and less strain. Furthermore, as shown in equation (1), alkyl groups are introduced into the side chains of the silicone chain, allowing for a higher alkyl group introduction rate than if they were introduced at the ends. In addition, alkyl groups are introduced via chains derived from acrylic or methacrylic groups. Since chains derived from acrylic or methacrylic groups have oxygen bonds, hydrogen bonding facilitates the formation of grains between polymers, which is thought to further improve thermal conductivity. Moreover, the introduction of alkyl groups into the side chains is thought to increase the radius of gyration of the polymer molecules and lengthen the molecular duration, thereby improving thermal conductivity. Thus, it is presumed that the thermal conductivity is improved because a large number of alkyl groups, which can enhance phonon propagation, are introduced via chains derived from acrylic or methacryloyl groups.

[0011] <R 1 > In equation (1), R 1 is a hydrogen atom or an alkenyl group. Preferably, the alkenyl group has 2 to 10 carbon atoms, and examples include vinyl group, allyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, and the like. In equation (1), w is R1 This represents the number of units of the constituent unit having the specified characteristic, and is preferably 0 to 10, and more preferably 0 to 5. Furthermore, in formula (1), the ratio of w to the sum of w, x, y, and z is preferably 0% or greater than 0% and 20% or less, and more preferably 0% or greater than 0% and 10% or less. When the ratio of w is within this range, aggregation of the side-chain alkyl-modified silicone resin can be suppressed and flexibility can be well maintained.

[0012] R 1 Since represents a hydrogen atom or alkenyl group bonded to a silicon atom, it becomes a highly reactive site. Therefore, the side-chain type alkyl-modified silicone resin of the present invention is R 1 By having this feature, it is possible to form cured products by addition reactions with alkenyl group-containing organopolysiloxanes, hydrogen organopolysiloxanes, and the like. In equation (1), R 1 It does not have to exist (i.e., w=0). 1 If it is not present, the formation of aggregates can be effectively suppressed.

[0013] <R 2 > In equation (1), R 2 This 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. 2 It 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.

[0014] In equation (1), x is R 2 This represents the number of units of the constituent unit having the specified property, and is preferably 0 to 100, more preferably 5 to 80, and even more preferably 10 to 60. In equation (1), the ratio of x to the sum of w, x, y, and z is 0 to 100%, preferably 60 to 100%, and more preferably 80 to 100%. Equation (1) is R, which will be discussed later. 3 When a constituent unit has such a configuration, for example, if the ratio of y to the sum of w, x, y, and z is 15-75%, the ratio of x may be in the range of 20-80%, and even in such cases, the thermal conductivity can be increased.

[0015] R 2 The alkyl group I represented by is preferably a linear alkyl group from the viewpoint of improving thermal conductivity. Examples of 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. In equation (1), multiple R 2 They may be the same or different, but it is preferable that they be the same for ease of manufacture and other reasons.

[0016] <R 3 > In equation (1), R 3 This is an alkyl group II having 15 to 18 carbon atoms. The side-chain type alkyl-modified silicone resin of the present invention can have its thermal conductivity increased by introducing alkyl group II. R 3 It is preferably a long-chain alkyl group having 16 to 18 carbon atoms, and more preferably a long-chain alkyl group having 18 carbon atoms.

[0017] In equation (1), y is R 3 This represents the number of units of the constituent unit having the specified property, preferably 0 to 100, more preferably 10 to 70, and even more preferably 20 to 50. Furthermore, in formula (1), the ratio of y to the sum of w, x, y, and z is 0 to 100%, preferably 15 to 75%, and more preferably 20 to 70%. Setting the ratio of y above these lower limits makes it easier to increase the thermal conductivity of the side-chain alkyl-modified silicone resin. Setting the ratio of y below these upper limits makes it easier for the side-chain alkyl-modified silicone resin to become liquid at room temperature (23°C), resulting in better handling.

[0018] Furthermore, in formula (1), the ratio of the sum of x and y to the sum of w, x, y, and z is 80-100%. If the ratio of the sum of x and y is less than 80%, the number of alkyl groups in the side-chain alkyl-modified silicone resin decreases, which reduces the thermal conductivity. The ratio of the sum of x and y is preferably 85-100%, more preferably 90-100%, and even more preferably 95-100%.

[0019] In formula (1), x and y may each be 0, but x and y cannot be 0 at the same time, and it is preferable that both x and y are not 0. That is, it is preferable to introduce both alkyl group I and alkyl group II, which makes it easier to improve the thermal conductivity.

[0020] R 3 The alkyl group II represented by is preferably a linear alkyl group from the viewpoint of improving thermal conductivity. Examples of linear alkyl groups include n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, and n-octadecyl group. In equation (1), multiple R 3 They may be the same or different, but it is preferable that they be the same for ease of manufacture and other reasons.

[0021] <R 5 , R 6 > R 5 and R 6 Each is independently a hydrogen atom or a methyl group. In particular, from the viewpoint of improving thermal conductivity, R 5 and R6 It is preferable that both are methyl groups.

[0022] <R 4 > In equation (1), R 4 is an ethyl group. In formula (1), z is R 4 This represents the number of units of the constituent unit having the specified characteristic, and is preferably 0 to 10, and more preferably 0 to 5. Furthermore, in equation (1), the ratio of z to the sum of w, x, y, and z is preferably 0% or greater than 0% and 20% or less, and more preferably 0% or greater than 0% and 10% or less. When producing the side-chain alkyl-modified silicone resin of the present invention, R 4 By introducing R, 1 This makes it easier to adjust the amount of R. 1 If the amount is adjusted appropriately, then R 4 It is not necessary to introduce this (i.e., z=0 is acceptable).

[0023] The side-chain type alkyl-modified silicone resin of the present invention is R 1 A constituent unit having R 2 A constituent unit having R 3 A constituent unit having R 4 The proportion of constituent units having the above-mentioned properties is sufficient, and the arrangement of each structural unit within the molecular chain is not limited. That is, each structural unit may exist in a block-like manner within the molecule, or it may exist randomly.

[0024] <Molecular weight> The weight-average molecular weight of the side-chain alkyl-modified silicone resin of the present invention is not particularly limited, but is preferably 5,000 to 20,000, and more preferably 7,000 to 18,000. Having a weight-average molecular weight within this range allows for adjustment to an appropriate viscosity and facilitates the maintenance of flexibility. The weight-average molecular weight is determined by gel permeation chromatography (GPC) measurement and converted to polystyrene equivalent.

[0025] [Method for producing side-chain alkyl-modified silicone resin] The method for producing the side-chain alkyl-modified silicone resin of the present invention is not particularly limited. For example, one method may include reacting an organopolysiloxane compound having a hydrosilyl group represented by the following formula (2) with at least one selected from alkyl (meth)acrylate I represented by the following formula (3) and alkyl (meth)acrylate II represented by the following formula (4) in the presence of a platinum catalyst. [ka] (In formula (2), m is between 10 and 200, preferably between 10 and 120, and more preferably between 15 and 80.) [ka] (R in equation (3)) 2 and R 5 (This is equivalent to the one in equation (1)) [ka] (R in equation (4)) 3 and R 6 (This is equivalent to the one in equation (1))

[0026] By incorporating such a process, some or all of the hydrosilyl group (SiH) in formula (2) reacts with at least one of alkyl (meth)acrylate I and alkyl (meth)acrylate II to form R in formula (1). 2 A constituent unit having R 3 A constituent unit having R can be formed. 2 and R 3 The amount introduced can be adjusted to the desired amount by adjusting the blending amounts of alkyl (meth)acrylate I and alkyl (meth)acrylate II. In this process, the reaction temperature and reaction time can be adjusted as appropriate. For example, the reaction temperature is preferably 40 to 120°C, and the reaction time is preferably 1 to 24 hours. The reaction may be carried out in the presence of a solvent. The type of solvent is not particularly limited and can be adjusted as appropriate depending on the type of hydrocarbon having an unsaturated double bond, but toluene is preferred from the viewpoint of the solubility of the synthesized product and the reaction temperature.

[0027] After the above reaction, if necessary, ethylene, methyl methacrylate, ethyl methacrylate, methyl acrylate, or ethyl acrylate may be added and the reaction continued to reduce the number of remaining hydrosilyl groups in formula (2). If ethylene is added and the reaction is carried out, R in formula (1) will be reduced. 4 A constituent unit having is formed. When methyl methacrylate, ethyl methacrylate, methyl acrylate, and ethyl acrylate are added and reacted, R in formula (1) is formed. 2 A constituent unit having the above characteristics is formed. As described above, a side-chain type alkyl-modified silicone resin represented by formula (1) can be obtained. 1 When an alkenyl group is used, a hydrocarbon having two unsaturated double bonds, preferably a hydrocarbon with 4 to 18 carbon atoms having unsaturated double bonds at both ends, is added and reacted with the hydrosilyl group.

[0028] [Resin composite materials] The resin composite material of the present invention contains a side-chain alkyl-modified silicone resin represented by the general formula (1) described above and an insulating thermal conductive filler. In this resin composite material, the side-chain alkyl-modified resin serves as the matrix resin, and the insulating thermal conductive filler is dispersed in the matrix resin. As described above, the side-chain alkyl-modified silicone resin of the present invention has excellent thermal conductivity, and by using an insulating thermal conductive filler in combination, the thermal conductivity can be improved more effectively.

[0029] The content of the side-chain alkyl-modified silicone resin in the resin composite material is not particularly limited and can be adjusted as appropriate while considering the dispersibility and thermal conductivity of the insulating thermal conductive filler, but is preferably 10 to 97% by mass, and more preferably 50 to 95% by mass.

[0030] <Insulating thermal conductive filler> The resin composite material of the present invention contains an insulating thermal conductive filler. By including an insulating thermal conductive filler, the insulating and thermal conductive properties of the resin composite material can be improved.

[0031] The average particle size of the insulating thermal conductive filler is not particularly limited, but is preferably 0.1 μm to 250 μm, and more preferably 0.2 μm to 100 μm. The average particle size can be measured, for example, by laser diffraction, and the particle diameter (d50) when the cumulative volume is 50% can be used as the average particle size.

[0032] The insulating thermal conductive filler preferably has a volume resistivity of 1.0 × 10⁻⁶ at 20°C, for example. 10 It has insulating properties of Ω·cm or higher, and preferably a thermal conductivity of 10 W / m·K or higher. Volume resistivity can be measured in accordance with JIS C2141. Thermal conductivity can be measured, for example, on a filler cross-section machined with a cross-section polisher, using a thermal microscope manufactured by Bethel Co., Ltd., by the periodic heating thermoreflectance method.

[0033] The content of the insulating thermal conductive filler is not particularly limited, but is preferably 10 to 97 parts by mass, and more preferably 50 to 95 parts by mass, per 100 parts by mass of the side-chain alkyl-modified silicone resin. If the content of the insulating thermal conductive filler is above these lower limits, the thermal conductivity of the resin composite material will increase. On the other hand, if the content of the insulating thermal conductive filler is below these upper limits, it is possible to prevent the resin composite material from becoming excessively hard or having poor handling properties.

[0034] The types of insulating thermal conductive fillers are not particularly limited, but examples include aluminum oxide, magnesium oxide, boron nitride, boron nitride nanotubes, aluminum nitride, and diamond. The insulating thermal conductive filler may be used alone or in combination of two or more types.

[0035] <Other ingredients> The resin composite material may optionally contain other silicone resins other than the side-chain alkyl-modified silicone resin represented by the general formula (1) described above, as long as they do not impair the effects of the present invention. Other silicone resins may include silicone resins having reactive groups such as alkenyl groups, hydrosilyl groups, and alkoxy groups, or silicone resins that do not have reactive groups. If other silicone resins are included, their content 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. Furthermore, the resin composite material of the present invention may optionally contain additives such as dispersants, antioxidants, heat stabilizers, colorants, flame retardants, and antistatic agents.

[0036] The applications of the resin composite material of the present invention are not particularly limited, but it can be used as a heat-dissipating silicone grease for various heat dissipation applications. For example, 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 by the electronic component. [Examples]

[0037] The present invention will be clarified below by providing specific examples and comparative examples of the present invention. However, the present invention is not limited to the following examples.

[0038] The evaluation methods for each compound (silicone resin) in each example and comparative example are as follows.

[0039] [Thermal conductivity] The thermal conductivity of each compound in each example and comparative example was measured using a TCi device manufactured by C-Therm, and evaluated based on the following evaluation criteria. (evaluation) AA...0.165W / mK or more A...0.160W / mK or more and less than 0.165W / mK B...0.150W / mK or more and less than 0.160W / mK C···0.150W / mK or less

[0040] [Initial shape] The properties of each compound (silicone resin) in each example and comparative example were evaluated as "A" if it was liquid at room temperature (23°C) and "B" if it was solid.

[0041] [Solubility in silicone] At 25°C, 3g of each compound from the examples and comparative examples was mixed with 7g of silicone to confirm the solubility of each compound. Dimethyl silicone oil (Shin-Etsu Chemical Co., Ltd. "KF-96-100cst") was used as the silicone. The results were evaluated as "A" if the substance dissolved and "C" if it did not dissolve.

[0042] [Changes over time (gelation)] For each compound (silicone resin) in each example and comparative example, the presence or absence of gelation was confirmed after 24 hours at 120°C and 85% humidity. (evaluation) A. No gelation was observed. C...Gelation was confirmed.

[0043] The side-chain alkyl-modified silicone resins used in the examples and comparative examples were prepared as compounds 1-21 and comparative compounds 1-10, as shown below.

[0044] (Compound 1) Compound 1 was prepared as follows. 5 g of an organopolysiloxane compound (m=56) having a hydrosilyl group represented by formula (2), and an alkyl methacrylate (R) of formula (3). 2 is a methyl group, R 5 7.5 g of compound (which has a methyl group) was reacted in dry toluene, under a nitrogen atmosphere, and in the presence of a platinum catalyst at 90°C for 12 hours. After the reaction, the solvent was removed using an evaporator and a vacuum dryer to obtain compound 1. Compound 1 was analyzed by Si-NMR to confirm that a side-chain alkyl-modified silicone resin with the structure described in Table 1 could be produced. The other compounds described later were identified using the same method.

[0045] (Compound 2) Compound 2 was prepared as follows. 5 g of an organopolysiloxane compound (m=24) having a hydrosilyl group represented by formula (2), and an alkyl methacrylate (R) of formula (3). 2 is an n-hexyl group, R 5 Compound 2 was obtained by reacting 12.2 g of compound (methyl group) in dry toluene, a nitrogen atmosphere, and a platinum catalyst at 90°C for 12 hours, and then removing the solvent using an evaporator and a vacuum dryer. Compound 2 was a side-chain alkyl-modified silicone resin with the structure described in Table 1.

[0046] (Compound 3) Compound 3 was prepared as follows. 5 g of an organopolysiloxane compound (m=35) having a hydrosilyl group represented by formula (2), and an alkyl methacrylate (R) of formula (3). 2 is an n-hexyl group, R 5 12.49 g of compound (methyl group) was reacted in dry toluene, under a nitrogen atmosphere and in the presence of a platinum catalyst at 90°C for 12 hours. After the reaction, the solvent was removed using an evaporator and a vacuum dryer to obtain compound 3. Compound 3 was a side-chain alkyl-modified silicone resin with the structure described in Table 1.

[0047] (Compound 4) Compound 4 was prepared as follows: 5 g of an organopolysiloxane compound (m=56) having a hydrosilyl group represented by formula (2), and an alkyl methacrylate (R) of formula (3). 2 is an n-hexyl group, R 5 12.81 g of compound 4 (which has a methyl group) was reacted in dry toluene, under a nitrogen atmosphere, and in the presence of a platinum catalyst at 90°C for 12 hours. After the reaction, the solvent was removed using an evaporator and a vacuum dryer to obtain compound 4. Compound 4 was a side-chain alkyl-modified silicone resin with the structure shown in Table 1.

[0048] (Compound 5) Compound 5 was prepared as follows: 5 g of an organopolysiloxane compound (m=56) having a hydrosilyl group of formula (2), and an alkyl methacrylate (R) of formula (3). 2 R is a branched alkyl group with 8 carbon atoms. 5 Compound 5 was obtained by reacting 14.9 g of compound (methyl group) in dry toluene, a nitrogen atmosphere, and a platinum catalyst at 90°C for 12 hours. After the reaction, the solvent was removed using an evaporator and a vacuum dryer. Compound 5 was a side-chain type alkyl-modified silicone resin with the structure shown in Table 1.

[0049] (Compound 6) Compound 6 was prepared as follows: 5 g of an organopolysiloxane compound (m=56) having a hydrosilyl group represented by formula (2), and an alkyl methacrylate (R) of formula (3). 2 is an n-octyl group, R 5 14.9 g of compound (methyl group) was reacted in dry toluene, under a nitrogen atmosphere and in the presence of a platinum catalyst at 90°C for 12 hours. After the reaction, the solvent was removed using an evaporator and a vacuum dryer to obtain compound 6. Compound 6 was a side-chain type alkyl-modified silicone resin with the structure described in Table 1.

[0050] (Compound 7) Compound 7 was prepared as follows: 5 g of an organopolysiloxane compound (m=56) having a hydrosilyl group represented by formula (2), and an alkyl methacrylate (R) of formula (3). 2 is an ethyl group, R 5 8.59 g of compound (methyl group) was reacted in dry toluene, under a nitrogen atmosphere and in the presence of a platinum catalyst at 90°C for 12 hours. After the reaction, the solvent was removed using an evaporator and a vacuum dryer to obtain compound 7. Compound 7 was a side-chain type alkyl-modified silicone resin with the structure shown in Table 1.

[0051] (Compound 8) Compound 8 was prepared as follows: 5 g of an organopolysiloxane compound (m=56) having a hydrosilyl group represented by formula (2), and an alkyl methacrylate (R) of formula (3). 2 is an n-butyl group, R 5 10.7 g of compound (methyl group) was reacted in dry toluene, under a nitrogen atmosphere and in the presence of a platinum catalyst at 90°C for 12 hours. After the reaction, the solvent was removed using an evaporator and a vacuum dryer to obtain compound 8. Compound 8 was a side-chain type alkyl-modified silicone resin with the structure shown in Table 1.

[0052] (Compound 9) Compound 9 was prepared as follows: 5 g of an organopolysiloxane compound (m=56) having a hydrosilyl group represented by formula (2), and an alkyl methacrylate (R) of formula (3). 2 is an n-hexyl group, R5 12.81 g of (the methyl group) was reacted at 90 °C in the presence of a platinum catalyst to obtain Compound 9. Compound 9 was a side-chain type alkyl-modified silicone resin having the structure described in Table 1.

[0053] (Compound 10) Compound 10 was produced as follows. 5 g of an organopolysiloxane compound having a hydrosilyl group represented by Formula (2) (m = 56) and 14.92 g of an alkyl methacrylate of Formula (3) (R 2 is an n-octyl group, R 5 is a methyl group) were reacted at 90 °C for 12 hours in dry toluene under a nitrogen atmosphere in the presence of a platinum catalyst. After the reaction, the solvent was removed with an evaporator and a vacuum dryer to obtain Compound 10. Compound 10 was a side-chain type alkyl-modified silicone resin having the structure described in Table 1.

[0054] (Compound 11) Compound 11 was produced as follows. 5 g of an organopolysiloxane compound having a hydrosilyl group represented by Formula (2) (m = 56) and 19.14 g of an alkyl methacrylate of Formula (3) (R 2 is an n-dodecyl group, R 5 is a methyl group) were reacted at 90 °C for 12 hours in dry toluene under a nitrogen atmosphere in the presence of a platinum catalyst. After the reaction, the solvent was removed with an evaporator and a vacuum dryer to obtain Compound 11. Compound 11 was a side-chain type alkyl-modified silicone resin having the structure described in Table 1.

[0055] (Compound 12) Compound 12 was produced as follows. 5 g of an organopolysiloxane compound having a hydrosilyl group of Formula (2) (m = 56) and an alkyl methacrylate of Formula (4) (R 3 is an n-octadecyl group, R 625.48 g of (the methyl group) was reacted at 90 °C for 12 hours in dry toluene under a nitrogen atmosphere and in the presence of a platinum catalyst. After the reaction, the solvent was removed using an evaporator and a vacuum dryer to obtain Compound 12. Compound 12 was a side-chain type alkyl-modified silicone resin having the structure described in Table 1.

[0056] (Compound 13) Compound 13 was produced as follows. 5 g of an organopolysiloxane compound having a hydrosilyl group represented by formula (2) (m = 56) and 12.81 g of an alkyl methacrylate of formula (3) (R 2 is an n-hexyl group, R 5 is a methyl group) were reacted at 90 °C for 12 hours in dry toluene under a nitrogen atmosphere and in the presence of a platinum catalyst. After the reaction, the solvent was removed using an evaporator and a vacuum dryer to obtain Compound 13. Compound 13 was a side-chain type alkyl-modified silicone resin having the structure described in Table 1.

[0057] (Compound 14) Compound 14 was produced as follows. 5 g of an organopolysiloxane compound having a hydrosilyl group represented by formula (2) (m = 56) and 19.14 g of an alkyl methacrylate of formula (3) (R 2 is an n-dodecyl group, R 5 is a methyl group) were reacted at 90 °C for 12 hours in dry toluene under a nitrogen atmosphere and in the presence of a platinum catalyst. After the reaction, the solvent was removed using an evaporator and a vacuum dryer to obtain Compound 14. Compound 14 was a side-chain type alkyl-modified silicone resin having the structure described in Table 1.

[0058] (Compound 15) Compound 15 was produced as follows. 2 g of the organopolysiloxane compound of formula (2) (m = 56), 5 g of an alkyl methacrylate of formula (3) (R 2 is an n-hexyl group, R 5 is a methyl group), and 5 g of an alkyl methacrylate of formula (4) (R 3 is an n-octadecyl group, R 60.4 g of (methyl group) was reacted with dry toluene, a nitrogen atmosphere, and a platinum catalyst at 90°C for 12 hours. After the reaction, the solvent was removed using an evaporator and a vacuum dryer to obtain compound 15. Compound 15 was a side-chain type alkyl-modified silicone resin with the structure shown in Table 1.

[0059] (Compound 16) Compound 16 was prepared as follows. 2 g of the organopolysiloxane compound of formula (2) (m=56) and the alkyl methacrylate (R) of formula (3) 2 is an n-hexyl group, R 5 (4) 4.74g of methyl group and alkyl methacrylate (R 3 is an n-octadecyl group, R 6 0.96 g of (methyl group) was reacted with dry toluene, a nitrogen atmosphere, and a platinum catalyst at 90°C for 12 hours. After the reaction, the solvent was removed using an evaporator and a vacuum dryer to obtain compound 16. Compound 16 was a side-chain type alkyl-modified silicone resin with the structure shown in Table 1.

[0060] (Compound 17) Compound 17 was prepared as follows. 2 g of the organopolysiloxane compound of formula (2) (m=56) and the alkyl methacrylate (R) of formula (3) 2 is an n-hexyl group, R 5 (4) 4.35g of methyl group and alkyl methacrylate (R 3 is an n-octadecyl group, R 6 1.73 g of (methyl group) was reacted with dry toluene, a nitrogen atmosphere, and a platinum catalyst at 90°C for 12 hours. After the reaction, the solvent was removed using an evaporator and a vacuum dryer to obtain compound 17. Compound 17 was a side-chain type alkyl-modified silicone resin with the structure shown in Table 1.

[0061] (Compound 18) Compound 18 was prepared as follows: 2 g of the organopolysiloxane compound of formula (2) (m=56) and the alkyl methacrylate (R) of formula (3) 2is an n-dodecyl group, R 5 (R) 6.21g of methyl group and alkyl methacrylate of formula (4) 3 is an n-octadecyl group, R 6 Compound 18 was obtained by reacting 2.11 g of (methyl group) with dry toluene, a nitrogen atmosphere, and a platinum catalyst at 90°C for 12 hours. After the reaction, the solvent was removed using an evaporator and a vacuum dryer. Compound 18 was a side-chain type alkyl-modified silicone resin with the structure shown in Table 1.

[0062] (Compound 19) Compound 19 was prepared as follows: 2 g of the organopolysiloxane compound of formula (2) (m=56) and the alkyl methacrylate (R) of formula (3) 2 is an n-dodecyl group, R 5 3.9g of methyl group and alkyl methacrylate (R) of formula (4) 3 is an n-octadecyl group, R 6 5.38 g of (methyl group) was reacted with dry toluene, a nitrogen atmosphere, and a platinum catalyst at 90°C for 12 hours. After the reaction, the solvent was removed using an evaporator and a vacuum dryer to obtain compound 19. Compound 19 was a side-chain type alkyl-modified silicone resin with the structure shown in Table 1.

[0063] Compound 20 was prepared as follows. 2 g of the organopolysiloxane compound of formula (2) (m=56) and the alkyl methacrylate (R) of formula (3) 2 is an n-dodecyl group, R 5 (R) 2.17g of methyl group and alkyl methacrylate of formula (4) 3 is an n-octadecyl group, R 6 7.69 g of (methyl group) was reacted with dry toluene, a nitrogen atmosphere, and a platinum catalyst at 90°C for 12 hours. After the reaction, the solvent was removed using an evaporator and a vacuum dryer to obtain compound 20. Compound 20 was a side-chain type alkyl-modified silicone resin with the structure shown in Table 1.

[0064] Compound 21 was prepared as follows. 5 g of an organopolysiloxane compound (m=56) having a hydrosilyl group represented by formula (2), and an alkyl methacrylate (R) of formula (3). 2 is an n-octyl group, R 5 Compound 21 was obtained by reacting 13 g of (methyl group) in dry toluene, a nitrogen atmosphere, and a platinum catalyst at 90°C for 12 hours. After the reaction, the solvent was removed using an evaporator and a vacuum dryer. Compound 21 was a side-chain type alkyl-modified silicone resin with the structure shown in Table 1.

[0065] (Comparative compound 1) As comparative compound 1, we used commercially available product 1 (Shin-Etsu Chemical Co., Ltd.'s "KF-96-50cst") having the following structure. [ka]

[0066] (Comparative compound 2) As comparative compound 2, we used commercially available product 2 (Shin-Etsu Chemical Co., Ltd.'s "KF-96-200cst") which has the following structure. [ka]

[0067] (Comparative compound 3) As comparative compound 3, we used commercially available product 3 (Shin-Etsu Chemical Co., Ltd.'s "KF-96-1000cst") which has the following structure. [ka]

[0068] (Comparative compound 4) As comparative compound 4, we used a commercially available product 4 (Shin-Etsu Chemical Co., Ltd.'s "KF-96H-6000cst") having the following structure. [ka]

[0069] (Comparative compound 5) A hydrosilyl group-containing organopolysiloxane compound represented by formula (2) (m=24) was designated as comparative compound 5.

[0070] (Comparative compound 6) A hydrosilyl group-containing organopolysiloxane compound represented by formula (2) (m=56) was designated as comparative compound 6.

[0071] (Comparative compound 7) Comparative compound 7 was prepared as follows. 5 g of an organopolysiloxane compound (m=56) having a hydrosilyl group represented by formula (2), and an alkyl methacrylate (R) of formula (3). 2 is an n-hexyl group, R 5 Comparative compound 7 was obtained by reacting 2.42 g of (methyl group) in the presence of a platinum catalyst at 90°C. Comparative compound 7 was a side-chain type alkyl-modified silicone resin with the structure shown in Table 2.

[0072] (Comparative compound 8) Comparative compound 8 was prepared as follows. 5 g of an organopolysiloxane compound (m=56) having a hydrosilyl group represented by formula (2), and an alkyl methacrylate (R) of formula (3). 2 is an n-dodecyl group, R 5 Comparative compound 8 was obtained by reacting 5.06 g of (methyl group) in the presence of a platinum catalyst at 90°C. Comparative compound 8 was a side-chain type alkyl-modified silicone resin with the structure shown in Table 2.

[0073] (Comparative compound 9) Comparative compound 9 was prepared as follows. 5 g of an organopolysiloxane compound (m=56) having a hydrosilyl group represented by formula (2), and an alkyl methacrylate (R) of formula (3). 2 is an n-dodecyl group, R 5 Comparative compound 9 was obtained by reacting 9.03 g of (methyl group) in the presence of a platinum catalyst at 90°C. Comparative compound 9 was a side-chain type alkyl-modified silicone resin with the structure shown in Table 2.

[0074] (Comparative compound 10) Comparative compound 10 was prepared as follows. 5 g of an organopolysiloxane compound (m=56) having a hydrosilyl group represented by formula (2), and an alkyl methacrylate (R) of formula (3). 2 5.4 g of (R5 is an n-dodecyl group, R5 is a methyl group) was reacted at 90°C in the presence of a platinum catalyst. Subsequently, the alkyl methacrylate (R5) of formula (3) was reacted. 3 The number of carbon atoms is 30, R 6 10.2 g of (methyl group) was reacted at 120°C in the presence of a platinum catalyst to obtain comparative compound 10. Comparative compound 10 was a side-chain type alkyl-modified silicone resin with the structure shown in Table 2.

[0075] [Example 1] Compound 1, a side-chain alkyl-modified silicone resin of the present invention manufactured as described above, was used as a sample, and its thermal conductivity, initial shape, solubility in silicone, and changes over time (gelation) were evaluated. The results are shown in Table 3.

[0076] [Examples 2-21, Comparative Examples 1-10] Each evaluation was performed in the same manner as in Example 1, except that each compound listed in Table 3 was used instead of compound 1. The results are shown in Table 3.

[0077] [Table 1]

[0078] [Table 2]

[0079] [Table 3]

[0080] The compounds of each example (side-chain alkyl-modified silicone resin) that satisfy the requirements of the present invention exhibited high thermal conductivity and excellent flexibility, as evidenced by good solubility in silicone and favorable results over time. On the other hand, the compounds in each comparative example had lower thermal conductivity or showed worse results over time compared to the compounds in the examples, making it difficult to achieve both high thermal conductivity and flexibility.

Claims

1. A side-chain type alkyl-modified silicone resin represented by the following general formula (1). 【Chemistry 1】 (In equation (1), R １ is a hydrogen atom, R ２ is an alkyl group I having 1 to 14 carbon atoms, and R ３ R is an alkyl group II having 15 to 18 carbon atoms. ５ and R ６ Each is independently a hydrogen atom or a methyl group, R ４ (where is an ethyl group, w, x, y, and z represent the number of units of each constituent unit, w, x, y, and z may each be 0, x and y cannot be 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 80-100%).

2. The side-chain alkyl-modified silicone resin according to claim 1, 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%.

3. The aforementioned R ２ and R ３ The side-chain type alkyl-modified silicone resin according to claim 1 or 2, wherein is a linear alkyl group.

4. A side-chain alkyl-modified silicone resin according to any one of claims 1 to 3, wherein in formula (1), the proportion of w to the sum of w, x, y, and z is greater than 0% and less than or equal to 20%.

5. A side-chain type alkyl-modified silicone resin according to any one of claims 1 to 3, wherein in formula (1), the ratio of w to the sum of w, x, y, and z is 0%.

6. A side-chain alkyl-modified silicone resin according to any one of claims 1 to 5, wherein in formula (1), the proportion of z to the sum of w, x, y, and z is greater than 0% and less than or equal to 20%.

7. A side-chain alkyl-modified silicone resin according to any one of claims 1 to 5, wherein in formula (1), the proportion of z to the sum of w, x, y, and z is 0%.

8. A side-chain type alkyl-modified silicone resin according to any one of claims 1 to 7, wherein the weight-average molecular weight is 5,000 to 20,000.

9. A resin composite material comprising a side-chain alkyl-modified silicone resin according to any one of claims 1 to 8 and an insulating thermal conductive filler.

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