Side-chain alkyl-modified organosilicon resins

Abstract

The side-chain alkyl-modified organosilicon resin of the present invention is represented by the following general formula (1). (In formula (1), R 1 R is a hydrogen atom or an alkenyl group. 2 I and R are alkyl groups having 1 to 14 carbon atoms. 3 It is an alkyl group II with 15 to 18 carbon atoms, R 5 and R 6 Each is independently a hydrogen atom or a methyl group, R 4 The components are methyl or ethyl, w, x, y, and z represent the number of units in each constituent unit, w, x, y, and z can each be 0, x and y cannot both be 0, and the total of x and y is 80-100% relative to the total of w, x, y, and z. According to the present invention, an organosilicon resin with high thermal conductivity while maintaining flexibility can be provided.

Description

Technical Field

[0001] This invention relates to side-chain alkyl-modified silicone resins and resin composites comprising the side-chain alkyl-modified silicone resins. Background Technology

[0002] In recent years, the increasing heat generated by highly integrated circuits in electronic devices has made thermal management crucial, leading to a surge in demand for heat dissipation materials. Silicone thermal greases are used to dissipate heat generated by various electronic devices and are typically materials containing silicone resin (base resin) and fillers, requiring high thermal conductivity and flexibility. To improve the thermal conductivity of silicone thermal greases, considerations include using fillers with high thermal conductivity, increasing the filler filler ratio, and improving the thermal conductivity of the base resin.

[0003] However, while boron nitride, aluminum nitride, and diamond are known fillers with high thermal conductivity, these fillers exhibit poor solubility and dispersibility in silicone resins, and increasing the filler content tends to decrease flexibility. Furthermore, increasing the filler content increases the specific gravity of composite materials such as silicone greases for heat dissipation, thus hindering the weight reduction of electronic devices.

[0004] On the other hand, as a method to improve the thermal conductivity of the matrix resin, examples of introducing alkyl groups into the silicone chain (Patent Documents 1-5) and examples of introducing liquid crystal sites into the silicone chain (Non-Patent Document 1) have also been reported.

[0005] Existing technical documents

[0006] Patent documents

[0007] Patent Document 1: Japanese Patent Application Publication No. 10-110179

[0008] Patent Document 2: Japanese Patent Application Publication No. 11-049958

[0009] Patent Document 3: Japanese Patent Application Publication No. 2005-154532

[0010] Patent Document 4: Japanese Patent Application Publication No. 2007-277387

[0011] Patent Document 5: Japanese Patent Application Publication No. 2009-209230

[0012] Non-patent literature

[0013] Non-patent literature 1: Ying Li, Chenggong Li, Liang Zhang, Wenying Zhou., Journal of Materials Science: Materials in Electronics, Published online: 18March 2019 (https: / / doi.org / 10.1007 / s10854-019-01150-1) Summary of the Invention

[0014] The problem that the invention aims to solve

[0015] However, in Patent Documents 1-5, there is no description of the type of alkyl group introduced into the silicone resin, the introduction rate of the alkyl group, or its relationship with thermal conductivity. Specifically, it is unclear how to operate to improve the thermal conductivity of the silicone resin. Furthermore, although in Non-Patent Document 1, thermal conductivity is improved by increasing crystallinity by introducing silicone chains into the liquid crystal site, the resin becomes solid due to excessive cross-linking and loses its flexibility.

[0016] As mentioned above, there are almost no examples and solutions available regarding specific methods to improve the thermal conductivity of silicone resins themselves.

[0017] Therefore, in this invention, the objective is to provide an organosilicon resin that maintains flexibility while having high thermal conductivity.

[0018] Methods for solving problems

[0019] In order to achieve the above-mentioned objective, the inventors have repeatedly conducted in-depth research and found that the above-mentioned problem can be solved by introducing alkyl side-chain type alkyl-modified organosilicon resin of formula (1) through a chain derived from alkyl or methacryloyl group, thereby completing the present invention.

[0020] That is, the present invention relates to the following [1] to [9].

[0021] [1] The side-chain alkyl-modified organosilicon resin shown in the following general formula (1).

[0022]

[0023] (In equation (1), R) 1 R is a hydrogen atom or an alkenyl group. 2 I and R are alkyl groups having 1 to 14 carbon atoms. 3 It is an alkyl group II with 15 to 18 carbon atoms, R 5 and R 6 Each is independently a hydrogen atom or a methyl group, R 4For ethyl, w, x, y, z represent the number of units in each constituent unit. w, x, y, z can each be 0, but x and y cannot both be 0. The ratio of the sum of x and y to the sum of w, x, y, z is 80% to 100%.

[0024] [2] According to the side-chain alkyl modified organosilicon resin described in [1] above, in the above formula (1), the ratio of x to the total of w, x, y, and z is 20 to 80%, and the ratio of y to the total of w, x, y, and z is 15 to 75%.

[0025] [3] According to the side-chain alkyl-modified organosilicon resin described in [1] or [2] above, the above R 2 and R 3 It is a straight-chain alkyl group.

[0026] [4] The side-chain alkyl-modified organosilicon resin according to any one of [1] to [3] above, wherein the proportion of w to the total of w, x, y and z in formula (1) is more than 0% and less than 20%.

[0027] [5] The side-chain alkyl-modified organosilicon resin according to any one of [1] to [3] above, in formula (1), the ratio of w to the total of w, x, y and z is 0%.

[0028] [6] The side-chain alkyl-modified organosilicon resin according to any one of [1] to [5] above, wherein the ratio of z to the total of w, x, y and z in formula (1) is more than 0% and less than 20%.

[0029] [7] The side-chain alkyl-modified organosilicon resin according to any one of [1] to [5] above, in formula (1), the ratio of z to the total of w, x, y and z is 0%.

[0030] [8] The side-chain alkyl-modified organosilicon resin according to any one of [1] to [7] above has a weight-average molecular weight of 5,000 to 20,000.

[0031] [9] A resin composite material comprising the side-chain alkyl-modified organosilicon resin described in any one of [1] to [8] above, and an insulating and thermally conductive filler.

[0032] The effects of the invention

[0033] According to the present invention, an organosilicon resin with high thermal conductivity can be provided while maintaining flexibility. Detailed Implementation

[0034] [Side-chain alkyl-modified silicone resin]

[0035] The side-chain alkyl-modified organosilicon resin of the present invention is represented by the following general formula (1).

[0036]

[0037] In equation (1), R 1 R is a hydrogen atom or an alkenyl group. 2 I and R are alkyl groups having 1 to 14 carbon atoms. 3 It is an alkyl group II with 15 to 18 carbon atoms, R 5 and R 6 Each is independently a hydrogen atom or a methyl group, R 4 It is an ethyl group. w, x, y, z represent the number of units in each constituent unit. w, x, y, z can each be 0, x and y cannot both be 0. The ratio of the sum of x and y to the sum of w, x, y, z is 80 to 100%.

[0038] Additionally, in this specification, the constituent unit within the parentheses indicated by w is sometimes described as "having R". 1 The constituent unit of "x" is sometimes written as "having R". 2 The constituent unit of y is sometimes written as "having R". 3 The constituent unit of z is sometimes written as "having R". 4 "The constituent units".

[0039] Furthermore, in this specification, the term "side chain type" refers to a type in which a chemical species is bonded to the central portion of the polymer backbone molecule.

[0040] The side-chain alkyl-modified silicone resin of the present invention has a structure of general formula (1), thereby improving thermal conductivity while maintaining flexibility. The reason for the improved thermal conductivity is uncertain, but is presumed to be as follows.

[0041] To improve the thermal conductivity of the resin, enhancing the phonon propagation of the polymer chain is effective. Compared to organosilicon chains formed by Si-O-Si bonds, alkyl chains formed by CCC bonds exhibit improved phonon propagation due to their wider bond angles and lower strain. Furthermore, as shown in formula (1), the alkyl group is introduced into the side chain of the organosilicon chain, thus increasing the alkyl group incorporation rate compared to incorporation into the terminal chain. In addition, the alkyl group is introduced via chains derived from acryloyl or methacryloyl groups. It can be considered that chains derived from acryloyl or methacryloyl groups, due to the presence of oxygen bonds, readily form inter-polymer grains through hydrogen bonds, further improving thermal conductivity. Moreover, it can be considered that the rotation radius and molecular length of the polymer molecule increase due to the alkyl group introduced into the side chain, thereby improving thermal conductivity.

[0042] Thus, it is presumed that the thermal conductivity is increased because alkyl groups that enhance phonon propagation are introduced in large quantities via chains derived from acryloyl or methacryloyl groups.

[0043] <R 1 >

[0044] In equation (1) R 1 It can be a hydrogen atom or an alkenyl group. As an alkenyl group, it is preferred to be an alkenyl group with 2 to 10 carbon atoms, and examples include vinyl, allyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, etc.

[0045] In equation (1), w represents having R 1 The number of constituent units is preferably 0 to 10, more preferably 0 to 5.

[0046] Furthermore, in formula (1), the ratio of w to the total of w, x, y, and z is preferably 0% or more than 0% and less than 20%, more preferably 0% or more than 0% and less than 10%. If the ratio of w is in such a range, the aggregation of side-chain alkyl-modified silicone resin can be suppressed, and the softness can be well maintained.

[0047] R 1 This indicates that the hydrogen atom or alkenyl group is bonded to the silicon atom, thus becoming a highly reactive site. Therefore, the side-chain alkyl-modified organosilicon resin of the present invention, through having R 1 This allows the formation of cured products obtained by addition reactions with alkenyl-containing organopolysiloxanes, hydrogen-containing organopolysiloxanes, etc.

[0048] In equation (1) R 1 It can be non-existent (i.e., it can be w = 0). In R 1 In the absence of these substances, the formation of aggregates can be effectively suppressed.

[0049] <R 2 >

[0050] In equation (1) R 2 It is an alkyl group (I) with 1 to 14 carbon atoms. By introducing such a long-chain alkyl group (I) into the side chain, the thermal conductivity can be improved. 2 Preferably, it is 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.

[0051] In equation (1), x represents having R 2 The number of constituent units is preferably 0 to 100, more preferably 5 to 80, and even more preferably 10 to 60.

[0052] In formula (1), the ratio of x to the total of w, x, y, and z is 0 to 100%, preferably 60 to 100%, and more preferably 80 to 100%.

[0053] In equation (1), R is given later. 3 In the case of constituent units, for example, when the ratio of y to the total of w, x, y, z is 15 to 75%, the ratio of x can be in the range of 20 to 80%, which can also improve thermal conductivity.

[0054] From the perspective of improving thermal conductivity, R 2 The alkyl group I shown is preferably a straight-chain alkyl group. Examples of straight-chain alkyl groups include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, and n-tetradecyl.

[0055] In equation (1), multiple R 2 They can be the same or different, but considering ease of manufacturing, it is preferable to be the same.

[0056] <R 3 >

[0057] In equation (1) R 3 The alkyl group consists of 15 to 18 carbon atoms. The side-chain alkyl-modified silicone resin of this invention improves thermal conductivity by introducing alkyl groups.

[0058] R 3 Preferably, it is a long-chain alkyl group with 16 to 18 carbon atoms, and more preferably, it is a long-chain alkyl group with 18 carbon atoms.

[0059] In equation (1), y represents having R 3 The number of constituent units is preferably 0 to 100, more preferably 10 to 70, and even more preferably 20 to 50.

[0060] Furthermore, in formula (1), the ratio of y to the total of w, x, y, and z is 0 to 100%, preferably 15 to 75%, and more preferably 20 to 70%. By setting the ratio of y above these lower limits, the thermal conductivity of the side-chain alkyl-modified silicone resin is easily improved. Furthermore, by setting the ratio of y below these upper limits, the side-chain alkyl-modified silicone resin readily becomes liquid at room temperature (23°C), resulting in good workability.

[0061] Furthermore, in formula (1), the ratio of the total of x and y to the total of w, x, y, and z is 80-100%. If the ratio of the total of x and y is less than 80%, the number of alkyl groups in the side-chain alkyl-modified silicone resin decreases, thus reducing the thermal conductivity. The ratio of the total of x and y is preferably 85-100%, more preferably 90-100%, and even more preferably 95-100%.

[0062] In equation (1), x and y can each be 0, but x and y cannot be 0 at the same time; preferably, neither x nor y is 0. That is, it is preferable to introduce both alkyl I and alkyl II, thereby making it easier to improve the thermal conductivity.

[0063] From the perspective of improving thermal conductivity, R 3 The alkyl group II shown is preferably a straight-chain alkyl group. Examples of straight-chain alkyl groups include n-pentadecanyl, n-hexadecyl, n-heptadecyl, and n-octadecyl.

[0064] In equation (1), multiple R 3 They can be the same or different, but considering ease of manufacturing, it is preferable to be the same.

[0065] <R 5 R 6 >

[0066] R 5 and R 6 Each can be independently a hydrogen atom or a methyl group. From the viewpoint of improving thermal conductivity, R is preferred. 5 and R 6 Both are methyl groups.

[0067] <R 4 >

[0068] In equation (1) R 4 It is an ethyl group. In formula (1), z represents having R 4 The number of constituent units is preferably 0 to 10, more preferably 0 to 5.

[0069] Furthermore, in equation (1), the ratio of z to the total of w, x, y, z is preferably 0% or more than 0% and less than 20%, more preferably 0% or more than 0% and less than 10%.

[0070] In manufacturing the side-chain alkyl-modified organosilicon resin of the present invention, by introducing R... 4 This makes it easy to adjust R. 1 The amount. It should be noted that in the manufacturing process of side-chain alkyl-modified silicone resins, if R... 1 If the amount of R is adjusted appropriately, then 4 It is optional to import it (i.e., z = 0 is acceptable).

[0071] The side-chain alkyl-modified organosilicon resin of the present invention only needs to have R 1 The constituent units, having R 2 The constituent units, having R 3 The constituent units, having R 4 The proportions of the constituent units can be as described above, and there are no restrictions on the arrangement of the structural units within the molecular chain. That is, the structural units within the molecule can exist in a block or randomly.

[0072] <Molecular weight>

[0073] 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, more preferably 7,000 to 18,000. If the weight-average molecular weight is within this range, it can be adjusted to a suitable viscosity, making it easy to maintain flexibility. The weight-average molecular weight is a value obtained by gel permeation chromatography (GPC) and converted from polystyrene.

[0074] [Manufacturing method of side-chain alkyl-modified organosilicon resin]

[0075] The method for manufacturing the side-chain alkyl-modified organosilicon resin of the present invention is not particularly limited. Examples include a method comprising reacting an organopolysiloxane compound having a hydrogenated silane as shown in formula (2) with at least one selected from (meth)acrylate alkyl ester I as shown in formula (3) and (meth)acrylate alkyl ester II as shown in formula (4) in the presence of a platinum catalyst.

[0076]

[0077] (In formula (2), m is 10 to 200, preferably 10 to 120, and more preferably 15 to 80.)

[0078]

[0079] R in equation (3) 2 and R 5 (Same meaning as equation (1))

[0080]

[0081] R in equation (4) 3 and R 6 (Same meaning as equation (1))

[0082] By employing such a process, part or all of the hydrosilyl (SiH) of formula (2) can react with at least one of (meth)acrylate alkyl ester I and (meth)acrylate alkyl ester II to form the R of formula (1). 2 The constituent units and having R 3 The constituent unit. At this time, R 2 and R 3 The amount introduced can be adjusted to the desired amount by adjusting the mixing ratio of (meth)acrylate I and (meth)acrylate II.

[0083] In this process, the reaction temperature and reaction time can be adjusted appropriately. For example, the reaction temperature is preferably 40-120°C and the reaction time is preferably 1-24 hours.

[0084] The reaction can be carried out in the presence of a solvent. There are no particular restrictions on the type of solvent, as long as it is appropriately adjusted according to the type of hydrocarbon with unsaturated double bonds. However, considering the solubility of the synthesized product and the reaction temperature, toluene is preferred.

[0085] Following the above reaction, if necessary to reduce the number of residual hydrosilyl groups in formula (2), ethylene, methyl methacrylate, ethyl methacrylate, methyl acrylate, and ethyl acrylate can be further added to react them. When ethylene is added and the reaction is carried out, the group with R in formula (1) is formed. 4 The constituent unit. When methyl methacrylate, ethyl methacrylate, methyl acrylate, and ethyl acrylate are added and reacted, the unit with R in formula (1) is formed. 2 The constituent units.

[0086] By operating as described above, the side-chain alkyl-modified organosilicon resin shown in formula (1) can be obtained. It should be noted that when R... 1 In the case of an alkenyl group, it is preferable to add a hydrocarbon having two unsaturated double bonds, preferably a hydrocarbon with 4 to 18 carbon atoms having unsaturated double bonds at both ends, to react with a hydrosilyl group.

[0087] [Resin Composite Materials]

[0088] The resin composite material of the present invention contains a side-chain alkyl-modified silicone resin as shown in the above general formula (1) and an insulating and thermally conductive filler. In this resin composite material, the side-chain alkyl-modified resin forms the matrix resin, and the insulating and thermally conductive filler is dispersed in the matrix resin.

[0089] As described above, the side-chain alkyl-modified silicone resin of the present invention has excellent thermal conductivity, and therefore, by using it in conjunction with insulating thermally conductive fillers, the thermal conductivity is improved more effectively.

[0090] There is no particular limitation on the content of side-chain alkyl-modified organosilicon resin in the resin composite material. It can be adjusted appropriately while taking into account the dispersibility and thermal conductivity of the insulating and thermally conductive filler. It is preferably 10-97% by mass, and more preferably 50-95% by mass.

[0091] <Insulating and Thermally Conductive Filler>

[0092] The resin composite material of the present invention contains an insulating and thermally conductive filler. By including the insulating and thermally conductive filler, the insulation and thermal conductivity of the resin composite material can be improved.

[0093] The average particle size of the insulating thermally conductive filler is not particularly limited, but is preferably 0.1 μm or more and 250 μm or less, and more preferably 0.2 μm or more and 100 μm or less.

[0094] It should be noted that the average particle size can be determined by methods such as laser diffraction, as long as the particle size (d50) at 50% of the cumulative volume is set as the average particle size.

[0095] The insulating and thermally conductive filler preferably has a volume resistivity of 1.0 × 10⁻⁶ at 20°C. 10 The insulation properties are above Ω·cm, and the thermal conductivity is preferably above 10 W / m·K.

[0096] Volume resistivity can be determined according to JIS C2141.

[0097] Thermal conductivity can be measured, for example, on the cross-section of a filler that has been machined using a cross-section polisher, by using a Veter thermomicroscope manufactured by Veter Corporation, via the periodic heating thermoreflectance method.

[0098] There is no particular limitation on the content of the insulating and thermally conductive filler, but it is preferably 10 to 97 parts by weight, more preferably 50 to 95 parts by weight, relative to 100 parts by weight of the side-chain alkyl-modified silicone resin. If the content of the insulating and thermally conductive filler is above these lower limits, the thermal conductivity of the resin composite material is improved. On the other hand, if the content of the insulating and thermally conductive filler is below these upper limits, excessive hardening of the resin composite material or deterioration of its workability can be prevented.

[0099] There are no particular limitations on the types of insulating and thermally conductive fillers; examples include alumina, magnesium oxide, boron nitride, boron nitride nanotubes, aluminum nitride, and diamond.

[0100] Insulating and thermally conductive fillers can be used alone or in combination with two or more types.

[0101] <Other Ingredients>

[0102] The resin composite material may, as needed and without impairing the effects of the present invention, contain other silicone resins besides the side-chain alkyl-modified silicone resin shown in the above general formula (1).

[0103] Other organosilicon resins can be organosilicon resins with reactive groups such as alkenyl, hydrogenated silyl, and alkoxy groups, or organosilicon resins without reactive groups.

[0104] When other silicone resins are contained, their content relative to the resin composite material is preferably 50% by mass or less, more preferably 30% by mass or less, and even more preferably 10% by mass or less.

[0105] In addition, the resin composite material of the present invention may contain additives such as dispersants, antioxidants, heat stabilizers, colorants, flame retardants, and antistatic agents as needed.

[0106] The application of the resin composite material of the present invention is not particularly limited, but it can be used as a silicone grease for heat dissipation in various heat dissipation applications. For example, the above-mentioned resin composite material can be disposed between electronic components such as semiconductor elements and heat sinks to effectively dissipate heat generated by the electronic components.

[0107] Example

[0108] The present invention will be made clear below by providing specific embodiments and comparative examples. It should be noted that the present invention is not limited to the following embodiments.

[0109] The evaluation methods for each compound (organosilicon resin) in each embodiment and comparative example are described below.

[0110] Thermal conductivity

[0111] The thermal conductivity of each compound in each example and comparative example was measured using TCi manufactured by C-Therm, and the evaluation was based on the following evaluation criteria.

[0112] (evaluate)

[0113] AA...0.165W / mK or higher

[0114] A... 0.160 W / mK or higher and less than 0.165 W / mK

[0115] B... ≥0.150W / mK and <0.160W / mK

[0116] C is less than 0.150 W / mK

[0117] [Initial Shape]

[0118] If the compounds (organosilicon resins) of each embodiment and comparative example are liquid at room temperature (23°C), they are rated as "A"; if they are solid, they are rated as "B".

[0119] [Solubility in organosilicon]

[0120] The solubility of each compound was confirmed by mixing 3g of the compounds from each example and comparative example with 7g of organosilicon at 25°C. It should be noted that dimethyl silicone oil (Shin-Etsu Chemical Co., Ltd. "KF-96-100cst") was used as the organosilicon.

[0121] The dissolved case is rated as "A", and the undissolved case is rated as "C".

[0122] [Changes over time (gelation)]

[0123] Regarding the compounds (silicone resins) of each example and comparative example, the presence or absence of gelation after 24 hours at 120°C and 85% humidity was confirmed.

[0124] (evaluate)

[0125] A·· Gelification not confirmed.

[0126] C·· confirmed gelation.

[0127] 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 shown below.

[0128] (Compound 1)

[0129] Compound 1 was manufactured as described below.

[0130] Mix 5g of the organopolysiloxane compound (m=56) with hydrogenated silanes as shown in formula (2) with the alkyl methacrylate (R) of formula (3). 2 For methyl, R 5 7.5 g of (methyl) was reacted at 90 °C for 12 hours in anhydrous toluene, nitrogen atmosphere and in the presence of platinum catalyst. After the reaction, the solvent was removed by evaporator and vacuum dryer to obtain compound 1.

[0131] Compound 1 was analyzed by Si-NMR, confirming its suitability for manufacturing side-chain alkyl-modified organosilicon resins with the structures described in Table 1. It should be noted that the compounds described later were also identified using the same method.

[0132] (Compound 2)

[0133] Compound 2 was manufactured as described below.

[0134] Mix 5g of the organopolysiloxane compound (m=24) with hydrogenated silanes as shown in formula (2) with the alkyl methacrylate (R) of formula (3). 2 For the positive base, R 5 Compound 2 was obtained by reacting 12.2 g of methyl group (methyl group) at 90 °C for 12 hours under anhydrous toluene, nitrogen atmosphere and platinum catalyst. After the reaction, the solvent was removed by evaporator and vacuum dryer.

[0135] Compound 2 is a side-chain type alkyl-modified organosilicon resin with the structure described in Table 1.

[0136] (Compound 3)

[0137] Compound 3 was manufactured as described below.

[0138] Mix 5g of the organopolysiloxane compound (m=35) with hydrogenated silanes as shown in formula (2) with the alkyl methacrylate (R) of formula (3). 2 For the positive base, R 5 12.49 g of (methyl) was reacted at 90 °C for 12 hours in the presence of anhydrous toluene, nitrogen atmosphere and platinum catalyst. After the reaction, the solvent was removed by evaporator and vacuum dryer to obtain compound 3.

[0139] Compound 3 is a side-chain type alkyl-modified organosilicon resin with the structure described in Table 1.

[0140] (Compound 4)

[0141] Compound 4 was manufactured as described below.

[0142] Mix 5g of the organopolysiloxane compound (m=56) with hydrogenated silanes as shown in formula (2) with the alkyl methacrylate (R) of formula (3). 2 For the positive base, R 5 12.81 g of (methyl) was reacted at 90 °C for 12 hours in anhydrous toluene, nitrogen atmosphere and in the presence of platinum catalyst. After the reaction, the solvent was removed by evaporator and vacuum dryer to obtain compound 4.

[0143] Compound 4 is a side-chain type alkyl-modified organosilicon resin with the structure described in Table 1.

[0144] (Compound 5)

[0145] Compound 5 was manufactured as described below.

[0146] Mix 5g of the organopolysiloxane compound (m=56) of formula (2) with the alkyl methacrylate (R) of formula (3). 2 It is a branched alkyl group with 8 carbon atoms, R 5Compound 5 was obtained by reacting 14.9 g of (methyl) at 90 °C for 12 hours under anhydrous toluene, nitrogen atmosphere, and platinum catalyst. The solvent was removed by evaporation and vacuum drying. Compound 5 is a side-chain alkyl-modified organosilicon resin with the structure described in Table 1.

[0147] (Compound 6)

[0148] Compound 6 was manufactured as described below.

[0149] Mix 5g of the organopolysiloxane compound (m=56) with hydrogenated silanes as shown in formula (2) with the alkyl methacrylate (R) of formula (3). 2 For octylene, R 5 Compound 6 was obtained by reacting 14.9 g of methyl group at 90 °C for 12 hours under anhydrous toluene, nitrogen atmosphere and platinum catalyst. After the reaction, the solvent was removed by evaporator and vacuum dryer.

[0150] Compound 6 is a side-chain alkyl-modified organosilicon resin with the structure described in Table 1.

[0151] (Compound 7)

[0152] Compound 7 was manufactured as described below.

[0153] Mix 5g of the organopolysiloxane compound (m=56) with hydrogenated silanes as shown in formula (2) with the alkyl methacrylate (R) of formula (3). 2 For ethyl, R 5 Compound 7 was obtained by reacting 8.59 g of (methyl) at 90 °C for 12 hours under anhydrous toluene, nitrogen atmosphere, and platinum catalyst. The solvent was removed by evaporation and vacuum drying. Compound 7 is a side-chain alkyl-modified organosilicon resin with the structure described in Table 1.

[0154] (Compound 8)

[0155] Compound 8 was manufactured as described below.

[0156] Mix 5g of the organopolysiloxane compound (m=56) with hydrogenated silanes as shown in formula (2) with the alkyl methacrylate (R) of formula (3). 2 It is n-butyl, R 5 Compound 8 was obtained by reacting 10.7 g of (methyl) at 90 °C for 12 hours under anhydrous toluene, nitrogen atmosphere, and platinum catalyst. The solvent was removed by evaporation and vacuum drying. Compound 8 is a side-chain alkyl-modified organosilicon resin with the structure described in Table 1.

[0157] (Compound 9)

[0158] Compound 9 was manufactured as described below.

[0159] Mix 5g of the organopolysiloxane compound (m=56) with hydrogenated silanes as shown in formula (2) with the alkyl methacrylate (R) of formula (3). 2 For the positive base, R 5 Compound 9 was obtained by reacting 12.81 g of (methyl) at 90 °C in the presence of a platinum catalyst. Compound 9 is a side-chain alkyl-modified organosilicon resin with the structure described in Table 1.

[0160] (Compound 10)

[0161] Compound 10 was manufactured as described below.

[0162] Mix 5g of the organopolysiloxane compound (m=56) with hydrogenated silanes as shown in formula (2) with the alkyl methacrylate (R) of formula (3). 2 For octylene, R 5 Compound 10 was obtained by reacting 14.92 g of (methyl) at 90 °C for 12 hours under anhydrous toluene, nitrogen atmosphere, and platinum catalyst. The solvent was removed by evaporation and vacuum drying. Compound 10 is a side-chain alkyl-modified organosilicon resin with the structure described in Table 1.

[0163] (Compound 11)

[0164] Compound 11 was manufactured as described below.

[0165] Mix 5g of the organopolysiloxane compound (m=56) with hydrogenated silanes as shown in formula (2) with the alkyl methacrylate (R) of formula (3). 2 It is n-dodecyl, R 5 19.14 g of (methyl) was reacted at 90 °C for 12 hours under anhydrous toluene, nitrogen atmosphere, and in the presence of a platinum catalyst. The solvent was removed by evaporation and vacuum drying to obtain compound 11. Compound 11 is a side-chain alkyl-modified organosilicon resin with the structure described in Table 1.

[0166] (Compound 12)

[0167] Compound 12 was manufactured as described below.

[0168] Mix 5g of the organopolysiloxane compound (m=56) of formula (2) with the alkyl methacrylate (R) of formula (4). 3 It is an octadecyl group, R 6Compound 12 was obtained by reacting 25.48 g of (methyl) at 90 °C for 12 hours under anhydrous toluene, nitrogen atmosphere, and platinum catalyst. The solvent was removed by evaporation and vacuum drying. Compound 12 is a side-chain alkyl-modified organosilicon resin with the structure described in Table 1.

[0169] (Compound 13)

[0170] Compound 13 was manufactured as described below.

[0171] Mix 5g of the organopolysiloxane compound (m=56) with hydrogenated silanes as shown in formula (2) with the alkyl methacrylate (R) of formula (3). 2 For the positive base, R 5 Compound 13 was obtained by reacting 12.81 g of (methyl) at 90 °C for 12 hours under anhydrous toluene, nitrogen atmosphere, and platinum catalyst. The solvent was removed by evaporation and vacuum drying. Compound 13 is a side-chain alkyl-modified organosilicon resin with the structure described in Table 1.

[0172] (Compound 14)

[0173] Compound 14 was manufactured as described below.

[0174] Mix 5g of the organopolysiloxane compound (m=56) with hydrogenated silanes as shown in formula (2) with the alkyl methacrylate (R) of formula (3). 2 It is n-dodecyl, R 5 Compound 14 was obtained by reacting 19.14 g of (methyl) at 90 °C for 12 hours under anhydrous toluene, nitrogen atmosphere, and platinum catalyst. The solvent was removed by evaporation and vacuum drying. Compound 14 is a side-chain alkyl-modified organosilicon resin with the structure described in Table 1.

[0175] (Compound 15)

[0176] Compound 15 was manufactured as described below.

[0177] Mix 2g of the organopolysiloxane compound (m=56) of formula (2) with the alkyl methacrylate (R) of formula (3). 2 For the positive base, R 5 5g of methyl methacrylate (R) and alkyl methacrylate of formula (4) 3 It is an octadecyl group, R 6 0.4 g of (methyl) was reacted at 90 °C for 12 hours under anhydrous toluene, 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 15. Compound 15 is a side-chain alkyl-modified organosilicon resin with the structure described in Table 1.

[0178] (Compound 16)

[0179] Compound 16 was manufactured as described below.

[0180] Mix 2g of the organopolysiloxane compound (m=56) of formula (2) with the alkyl methacrylate (R) of formula (3). 2 For the positive base, R 5 4.74 g of methyl methacrylate (R) and alkyl methacrylate of formula (4) 3 It is an octadecyl group, R 6 0.96 g of (methyl) was reacted at 90 °C for 12 hours under anhydrous toluene, 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 16. Compound 16 is a side-chain alkyl-modified organosilicon resin with the structure described in Table 1.

[0181] (Compound 17)

[0182] Compound 17 was manufactured as described below.

[0183] Mix 2g of the organopolysiloxane compound (m=56) of formula (2) with the alkyl methacrylate (R) of formula (3). 2 For the positive base, R 5 4.35g of methyl methacrylate (R) and alkyl methacrylate of formula (4) 3 It is an octadecyl group, R 6 1.73 g of (methyl) was reacted at 90 °C for 12 hours under anhydrous toluene, 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 17. Compound 17 is a side-chain alkyl-modified organosilicon resin with the structure described in Table 1.

[0184] (Compound 18)

[0185] Compound 18 was manufactured as described below.

[0186] Mix 2g of the organopolysiloxane compound (m=56) of formula (2) with the alkyl methacrylate (R) of formula (3). 2 It is n-dodecyl, R 5 6.21g of methyl methacrylate (R) and alkyl methacrylate of formula (4) 3 It is an octadecyl group, R 6 2.11 g of (methyl) was reacted at 90 °C for 12 hours under anhydrous toluene, 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 18. Compound 18 is a side-chain alkyl-modified organosilicon resin with the structure described in Table 1.

[0187] (Compound 19)

[0188] Compound 19 was manufactured as described below.

[0189] Mix 2g of the organopolysiloxane compound (m=56) of formula (2) with the alkyl methacrylate (R) of formula (3). 2 It is n-dodecyl, R 5 3.9g of methyl group and alkyl methacrylate (R) of formula (4) 3 It is an octadecyl group, R 6 5.38 g of (methyl) was reacted at 90 °C for 12 hours under anhydrous toluene, 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 19. Compound 19 is a side-chain alkyl-modified organosilicon resin with the structure described in Table 1.

[0190] Compound 20 was manufactured as described below.

[0191] Mix 2g of the organopolysiloxane compound (m=56) of formula (2) with the alkyl methacrylate (R) of formula (3). 2 It is n-dodecyl, R 5 2.17 g of methyl methacrylate (R) and alkyl methacrylate of formula (4) 3 It is an octadecyl group, R 6 7.69 g of (methyl) was reacted at 90 °C for 12 hours under anhydrous toluene, 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 20. Compound 20 is a side-chain alkyl-modified organosilicon resin with the structure described in Table 1.

[0192] Compound 21 was manufactured as described below.

[0193] Mix 5g of the organopolysiloxane compound (m=56) with hydrogenated silanes as shown in formula (2) with the alkyl methacrylate (R) of formula (3). 2 For octylene, R 5 13g of (methyl) was reacted at 90°C for 12 hours under anhydrous toluene, nitrogen atmosphere, and in the presence of a platinum catalyst. The solvent was removed using an evaporator and a vacuum dryer after the reaction to obtain compound 21. Compound 21 is a side-chain alkyl-modified organosilicon resin with the structure described in Table 1.

[0194] (Compare compound 1)

[0195] As a comparative compound 1, a commercially available compound 1 (Shin-Etsu Chemical Co., Ltd. "KF-96-50cst") with the following structure was used.

[0196]

[0197] (Compare compound 2)

[0198] As a comparative compound 2, a commercially available compound 2 (Shin-Etsu Chemical Co., Ltd. "KF-96-200cst") having the following structure was used.

[0199]

[0200] (Compare compound 3)

[0201] As a comparative compound 3, a commercially available compound 3 (Shin-Etsu Chemical Co., Ltd. "KF-96-1000cst") with the following structure was used.

[0202]

[0203] (Compare compound 4)

[0204] As a comparative compound 4, a commercially available compound 4 (Shin-Etsu Chemical Co., Ltd. "KF-96H-6000cst") with the following structure was used.

[0205]

[0206] (Compare compound 5)

[0207] The organopolysiloxane compound (m=24) with hydrogenated silanes shown in formula (2) is designated as comparative compound 5.

[0208] (Compare compound 6)

[0209] The organopolysiloxane compound (m = 56) with hydrogenated silanes shown in formula (2) is designated as comparative compound 6.

[0210] (Compare compound 7)

[0211] Comparative compound 7 was prepared as described below.

[0212] Mix 5g of the organopolysiloxane compound (m=56) with hydrogenated silanes as shown in formula (2) with the alkyl methacrylate (R) of formula (3). 2 For the positive base, R 5 Comparative compound 7 was obtained by reacting 2.42 g of (methyl) at 90 °C in the presence of a platinum catalyst. Comparative compound 7 is a side-chain alkyl-modified organosilicon resin with the structure described in Table 2.

[0213] (Compare compound 8)

[0214] Comparative compound 8 was prepared as described below.

[0215] Mix 5g of the organopolysiloxane compound (m=56) with hydrogenated silanes as shown in formula (2) with the alkyl methacrylate (R) of formula (3). 2 It is n-dodecyl, R 5 Comparative compound 8 was obtained by reacting 5.06 g of (methyl) at 90 °C in the presence of a platinum catalyst. Comparative compound 8 is a side-chain alkyl-modified organosilicon resin with the structure described in Table 2.

[0216] (Compare compound 9)

[0217] Comparative compound 9 was prepared as described below.

[0218] Mix 5g of the organopolysiloxane compound (m=56) with hydrogenated silanes as shown in formula (2) with the alkyl methacrylate (R) of formula (3). 2 It is n-dodecyl, R 5 Comparative compound 9 was obtained by reacting 9.03 g of (methyl) at 90 °C in the presence of a platinum catalyst. Comparative compound 9 is a side-chain alkyl-modified organosilicon resin with the structure described in Table 2.

[0219] (Compare compound 10)

[0220] Comparative compound 10 was prepared as described below.

[0221] Mix 5g of the organopolysiloxane compound (m=56) with hydrogenated silanes as shown in formula (2) with the alkyl methacrylate (R) of formula (3). 2 5.4 g of (r is n-dodecyl, R5 is methyl) was reacted at 90 °C in the presence of a platinum catalyst. Then, the alkyl methacrylate (R) of formula (3) was reacted. 3 The number of carbon atoms is 30, R 6 Comparative compound 10 was obtained by reacting 10.2 g of (methyl) at 120 °C in the presence of a platinum catalyst. Comparative compound 10 is a side-chain alkyl-modified organosilicon resin with the structure described in Table 2.

[0222] [Example 1]

[0223] Compound 1, the side-chain alkyl-modified organosilicon resin of the present invention manufactured as described above, was used as a sample, and various evaluations were performed related to thermal conductivity, initial shape, solubility in organosilicon, and changes over time (gelation). The results are shown in Table 3.

[0224] [Examples 2-21, Comparative Examples 1-10]

[0225] Instead of compound 1, the compounds listed in Table 3 were used, and the evaluations were performed in the same manner as in Example 1. The results are shown in Table 3.

[0226] [Table 1]

[0227]

[0228] [Table 2]

[0229]

[0230] [Table 3]

[0231] Table 3

[0232]

[0233] The compounds (side-chain alkyl-modified silicone resins) of the embodiments that satisfy the requirements of the present invention have high thermal conductivity, and in addition, they have good solubility in silicone and good results over time, thus exhibiting excellent softness.

[0234] On the other hand, the compounds of the comparative examples have lower thermal conductivity or worse results over time compared with the compounds of the examples, making it difficult to achieve both high thermal conductivity and flexibility.

Claims

1. The side-chain alkyl-modified organosilicon resin represented by the following general formula (1), In equation (1), R 1 R is a hydrogen atom or an alkenyl group. 2 I and R are alkyl groups having 1 to 14 carbon atoms. 3 It is an alkyl group II with 15 to 18 carbon atoms, R 5 and R 6 Each is independently a hydrogen atom or a methyl group, R 4 For ethyl, w, x, y, z represent the number of units in each constituent unit. w, x, y, z can each be 0, x and y cannot both be 0 at the same time, and the ratio of the sum of x and y to the sum of w, x, y, z is 80 to 100%.

2. The side-chain alkyl-modified organosilicon resin according to claim 1, wherein in formula (1), the ratio of x to the total of w, x, y, and z is 20-80%, and the ratio of y to the total of w, x, y, and z is 15-75%.

3. The side-chain alkyl-modified organosilicon resin according to claim 1 or 2, wherein R 2 and R 3 It is a straight-chain alkyl group.

4. The side-chain alkyl-modified organosilicon resin according to claim 1 or 2, wherein in formula (1), the proportion of w relative to the total of w, x, y, z is greater than 0% and less than 20%.

5. The side-chain alkyl-modified organosilicon resin according to claim 1 or 2, wherein the ratio of w to the total of w, x, y and z in formula (1) is 0%.

6. The side-chain alkyl-modified organosilicon resin according to claim 1 or 2, wherein the ratio of z to the total of w, x, y and z in formula (1) is greater than 0% and less than 20%.

7. The side-chain alkyl-modified organosilicon resin according to claim 1 or 2, wherein the ratio of z to the total of w, x, y and z in formula (1) is 0%.

8. The side-chain alkyl-modified organosilicon resin according to claim 1 or 2, wherein the weight-average molecular weight is 5,000 to 20,000.

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

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