Polyorganosiloxane and resin composition

Abstract

This polyorganosiloxane has a structure represented by formula (1). (In formula (1), each R independently is substituted with a substituent A, or is a C1-4 monovalent saturated hydrocarbon group, at least one R is substituted with the substituent A, and R' is a monovalent organic group having an aliphatic unsaturated bond. The substituent A is a monovalent organic group that has three to six conjugated aromatic six-membered rings, l is an integer greater than or equal to 1, and m and n are integers greater than or equal to 0. Additionally, in formula (1), the number of aliphatic unsaturated bonds is two or greater.)

Description

Polyorganosiloxanes and resin compositions

[0001] The present invention relates to polyorganosiloxanes and resin compositions containing polyorganosiloxanes.

[0002] In recent years, due to 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. For example, heat dissipation materials using fillers such as graphite are known for their high heat dissipation capabilities. Metal-based fillers, such as metal oxides like alumina and metals like aluminum, are also known. Generally, fillers have poor dispersibility in solvents, and graphite, in particular, which is a compound with a π-conjugated system, has poor dispersibility, making improvement in terms of heat dissipation desirable.

[0003] It is widely known that dispersants are used to improve the dispersibility of fillers. Polyorganosiloxanes having alkoxysilyl groups are often used as dispersants, and such polyorganosiloxanes may further have monovalent hydrocarbon groups having aliphatic unsaturated bonds such as vinyl groups, or alkoxysilyl-vinylene groups introduced (see, for example, Patent Documents 1 and 2). In addition, polyorganosiloxanes with polycyclic aromatic groups introduced (hereinafter also referred to as "polycyclic aromatic-introduced polyorganosiloxanes") are being investigated as dispersants in order to appropriately surface-treat fillers having π electrons such as nanocarbon and graphite (π-electron fillers) (see, for example, Patent Documents 3 and 4).

[0004] Furthermore, in order to improve the packing properties of metal-based fillers into silicone resins, polyorganosiloxanes with hydrogen-bonding functional groups introduced as dispersants are being investigated. As an example of a dispersant having hydrogen-bonding functional groups, Patent Document 5 discloses a polyorganosiloxane in which hydroxyl groups have been introduced into the silicone (hydroxyl group-introduced polyorganosiloxane).

[0005] Japanese Patent Publication No. 2006-274154, International Publication No. 2024 / 024454, Japanese Patent Publication No. 2018-197300, International Publication No. 2024 / 111519, Japanese Patent Publication No. 2022-081264

[0006] Polycyclic aromatic polyorganosiloxanes are adsorbed to π-electron fillers via π-π interactions, but these π-π interactions are relatively weak interactions that do not involve direct chemical bonding. Therefore, according to our research, when a resin composition containing a polycyclic aromatic polyorganosiloxane, a matrix resin, and a π-electron filler is exposed to harsh environments such as high temperatures, a reverse reaction of adsorption via π-π interactions occurs, resulting in the polycyclic aromatic polyorganosiloxane bleeding out.

[0007] Furthermore, hydroxyl-modified polyorganosiloxanes adsorb to metal-based fillers through hydrogen bonding interactions, but hydrogen bonding interactions are relatively weak interactions that do not involve direct chemical bonds. Therefore, according to the inventors' research, when a resin composition containing a hydroxyl-modified polyorganosiloxane, a matrix resin, and a metal-based filler is exposed to harsh environments such as high temperatures, a reverse reaction of adsorption due to hydrogen bonding interactions occurs, resulting in the hydroxyl-modified polyorganosiloxane bleeding out.

[0008] To address the above challenges, one possible approach is to increase the viscosity of polycyclic aromatic-introduced silicones by increasing their molecular weight to suppress bleed-out. However, if the viscosity is increased too much, cross-linking aggregation occurs due to the polycyclic aromatic-introduced silicone, preventing the compound from achieving its viscosity-reducing effect. Therefore, a method is needed for polycyclic aromatic-introduced silicones that achieves both viscosity-reducing effect and bleed-resistant properties. Similarly, for hydroxyl-introduced polyorganosiloxanes, one possible approach is to increase their viscosity by increasing their molecular weight to suppress bleed-out. However, if the molecular weight is increased too much, cross-linking aggregation occurs due to the hydroxyl-introduced polyorganosiloxane, preventing the compound from achieving its viscosity-reducing effect. Therefore, a method is needed for hydroxyl-introduced polyorganosiloxanes that achieves both viscosity-reducing effect and bleed-resistant properties.

[0009] Furthermore, while Patent Documents 1 and 2 describe mechanical strengths such as adhesion, elongation, and tensile strength, and the ability to minimize viscosity changes even after long-term storage, they do not describe or suggest that vinyl groups or vinylene groups can improve bleed resistance.

[0010] The object of this invention is to provide a polyorganosiloxane that can achieve both viscosity reduction and bleed resistance.

[0011] The inventors, through diligent research, concluded that the viscosity reduction effect and bleed resistance could be solved by introducing a certain amount of chemical bonding sites in addition to the polycyclic aromatic sites. Further research revealed that the above problems could be solved by introducing two or more aliphatic unsaturated bonds in a polyorganosiloxane containing three to six conjugated aromatic six-membered rings, and thus completed the present invention. Furthermore, the inventors, through diligent research, also discovered that the above problems could be solved by introducing two or more aliphatic unsaturated bonds in a polyorganosiloxane containing hydroxyl groups, and thus completed the present invention.

[0012] The gist of the present invention is as follows: [1] A polyorganosiloxane having a structure represented by the following formula (1). (In formula (1), each R is independently substituted with substituent A or is a monovalent saturated hydrocarbon group having 1 to 4 carbon atoms, at least one R is substituted with substituent A, and R' is a monovalent organic group having an aliphatic unsaturated bond. Substituents A are monovalent organic groups having 3 to 6 conjugated aromatic 6-membered rings, l is an integer of 1 or more, m and n are integers of 0 or more, and at least one of them is 1 or more. Also, in formula (1), the number of aliphatic unsaturated bonds is 2 or more.) [2] The polyorganosiloxane according to [1] above, wherein each R' independently comprises at least one selected from the group consisting of a vinyl group, an acryloyl group, and a methacryloyl group. [3] The polyorganosiloxane according to [1] or [2] above, wherein l + m + n is 10 or more and 500 or less. [4] A polyorganosiloxane according to any one of [1] to [3] above, wherein (m+n) / l is 0.001 or more and 0.5 or less. [5] A polyorganosiloxane according to any one of [1] to [4] above, represented by the following formula (2). (In formula (2), R, A, R', l, m and n are the same as above.) [6] A polyorganosiloxane according to any of [1] to [4] above, represented by the following formula (3). (In formula (3), R, A, R', l, m and n are the same as above.) [7] A polyorganosiloxane according to any of [1] to [4] above, represented by the following formula (4). (In formula (4), R, A, R', l, m, and n are the same as above, and k is an integer from 1 to 10.) [8] The polyorganosiloxane according to [7] above, wherein k in formula (4) is 1 or 2. [9] A resin composition comprising the polyorganosiloxane according to any one of [1] to [8] above, a polyorganosiloxane other than the polyorganosiloxane, and a π electron filler.

[10] The resin composition according to [9] above, further comprising a platinum catalyst.

[0013]

[11] A polyorganosiloxane having a structure represented by the following formula (51). (In formula (51), R is independently a monovalent saturated hydrocarbon group having 1 to 4 carbon atoms, R' is a monovalent organic group having an aliphatic unsaturated bond, and A is a monovalent organic group having at least one hydroxyl group. l is an integer of 1 or more, m and n are integers of 0 or more, and at least one of them is 1 or more. In formula (51), the number of aliphatic unsaturated bonds is 2 or more.)

[12] The polyorganosiloxane according to

[11] above, wherein R' is independently at least one selected from the group consisting of a vinyl group, an acryloyl group, and a methacryloyl group.

[13] The polyorganosiloxane according to

[11] or

[12] above, wherein l + m + n is 10 or more and 500 or less.

[14] The polyorganosiloxane according to any one of

[11] to

[13] above, wherein (m + n) / l is 0.001 or more and 0.5 or less.

[15] A polyorganosiloxane according to any one of

[11] to

[14] above, wherein A contains two or more hydroxyl groups.

[16] A polyorganosiloxane according to

[15] above, wherein the two hydroxyl groups in A constitute at least one of a 1,2-diol structure and a 1,3-diol structure.

[17] A polyorganosiloxane having a structure represented by the following formula (52). (In formula (52), l is an integer of 1 or more, and m is an integer of 2 or more.)

[18] A resin composition comprising a polyorganosiloxane according to any one of

[11] to

[17] above, a polyorganosiloxane other than the polyorganosiloxane, and a metal filler.

[19] The resin composition according to

[18] above, further comprising a platinum catalyst.

[0014] According to the present invention, it is possible to provide a polyorganosiloxane that can achieve both viscosity reduction and bleed resistance.

[0015] The present invention will be described below with reference to embodiments, but the present invention is not limited to the following embodiments. [Polyorganosiloxane] (First Embodiment) The polyorganosiloxane according to the first embodiment of the present invention (hereinafter sometimes referred to as "the polyorganosiloxane (A)") has a structure represented by the following formula (1). In formula (1), each R is independently substituted with substituent A or is a monovalent saturated hydrocarbon group having 1 to 4 carbon atoms, with at least one R being substituted with substituent A, and R' being a monovalent organic group having an aliphatic unsaturated bond. Substituent A is a monovalent organic group having 3 to 6 conjugated aromatic 6-membered rings, where l is an integer of 1 or more, and m and n are integers of 0 or more, with at least one of them being 1 or more. In formula (1), the number of aliphatic unsaturated bonds is 2 or more.

[0016] This polyorganosiloxane (A) enhances viscosity reduction while also exhibiting good bleed resistance. By enhancing viscosity reduction, this polyorganosiloxane (A) also facilitates the filling of fillers. The reason why it enhances viscosity reduction while maintaining good bleed resistance is not entirely clear, but it is presumed to be as follows: The polyorganosiloxane of the present invention has three to six conjugated aromatic six-membered rings, thereby possessing a large conjugated system in its molecular structure. As a result, this polyorganosiloxane (A) has high adsorption to fillers, especially fillers with a π-conjugated system structure, due to π-π interactions, which facilitates the dispersion of fillers and enhances viscosity reduction. Furthermore, because this polyorganosiloxane (A) has two or more aliphatic unsaturated bonds, it is easier for it to chemically bond to matrix resins and other materials to form a crosslinked network, thereby improving bleed resistance.

[0017] As described above, substituent A in formula (1) has three to six conjugated aromatic six-membered rings. Conjugation refers to the alternating arrangement of unsaturated and single bonds in the molecular structure, resulting in stabilization through p-orbital interactions and electron delocalization (spread throughout the entire conjugated system). If the number of aromatic six-membered rings is seven or more, the fluidity of the polyorganosiloxane (A) deteriorates, and it becomes unable to exhibit a thickening effect. If the number of aromatic six-membered rings is two or less, the adsorption to fillers decreases, and the dispersibility of fillers deteriorates. From the viewpoint of improving both adsorption to fillers and fluidity in a balanced manner and further improving the thickening effect, it is preferable that the number of aromatic six-membered rings be three to five, and more preferably four to five.

[0018] The three to six conjugated aromatic six-membered rings may include a condensed ring structure or may be a non-condensed ring structure composed of three to six aromatic six-membered rings, but it is preferred to include a condensed ring structure. When the three to six conjugated aromatic six-membered rings include a condensed ring structure, they may consist of one condensed ring structure composed of three to six aromatic six-membered rings, or may be a combination of a condensed ring structure and a non-condensed ring structure, or may be a combination of two or more condensed ring structures. In addition, the combination of a condensed ring structure and a non-condensed ring structure, or the combination of two or more condensed ring structures is preferably one in which the condensed ring structure and the non-condensed ring structure or the condensed ring structures are connected via a single bond. It is preferred that the three to six conjugated aromatic six-membered rings in A have at least a condensed ring structure, and more preferably, they consist of one condensed ring structure composed of three to six aromatic six-membered rings. When A in this polyorganosiloxane (A) includes a condensed ring structure, the adsorptivity to the filler is further improved, the dispersibility is enhanced, and it is easier to obtain a viscosity reduction effect.

[0019] The three to six conjugated aromatic six-membered rings in A may have a substituent. Examples of the substituent include an organic group having 1 to 10 carbon atoms. More specifically, hydrocarbon groups such as an alkyl group, an aralkyl group such as a benzyl group and a phenethyl group are included. Among these, a benzyl group and an alkyl group are preferred. When the substituent of the aromatic six-membered ring is an alkyl group, the alkyl group may be linear or may have at least one of a branched structure or a cyclic structure. Also, in the three to six conjugated aromatic six-membered rings, all the atoms constituting the ring are preferably carbon atoms.

[0020] When a conjugated aromatic six-membered ring of three to six atoms constitutes a single fused ring structure, examples of substituted compounds include anthracene, phenanthrene, triphenylene, pyrene, tetracene, picene, perylene, pentaphene, pentacene, or hexaphene. Among these, anthracene, triphenylene, pyrene, or perylene substituted compounds are preferred, anthracene, pyrene, or perylene substituted compounds are more preferred, pyrene or perylene substituted compounds are even more preferred, and pyrene substituted compounds are even more preferred. Here, "substituted compound" means that it may have substituents; for example, anthracene substituted compound means that it includes both anthracene and anthracene with substituents. However, the anthracene referred to here is not only a substituent, but also a compound in which one of the hydrogen atoms constituting the conjugated aromatic ring structure of three to six atoms is substituted by a bonding bond. The same applies to other substituted compounds described above or later. Furthermore, when a conjugated aromatic six-membered ring of three to six atoms has substituents, at least one of the hydrogen atoms constituting the conjugated aromatic six-membered ring of three to six atoms is substituted by the substituent. Examples of substituents include organic groups having 1 to 10 carbon atoms, and the details are as described above. The same applies to cases other than those described below, where a three to six aromatic six-membered ring is composed of a single fused ring structure.

[0021] When three or more and six or less conjugated aromatic six-membered rings have a non-condensed ring structure, for example, it is a structure in which a plurality of aromatic six-membered rings are connected by single bonds. Specifically, terphenyl substituents such as para-terphenyl substituents and meta-terphenyl substituents, quarterphenyl substituents, kinkiphenyl substituents, sexiphenyl substituents, triphenylbenzene substituents, tetraphenylbenzene substituents, etc. can be mentioned. Further, when three or more and six or less conjugated aromatic six-membered rings are a combination of a condensed ring structure and a condensed ring structure or a non-condensed ring structure, substituents of anthracene derivatives such as phenylanthracene substituents, diphenylanthracene substituents, naphthylanthracene substituents, etc., pyrenylbenzene substituents, phenylnaphthalene substituents, naphthylbenzene substituents, etc. can be mentioned. In addition, the substituent of the anthracene derivative preferably has a bonding hand on the anthracene skeleton, and the pyrenylbenzene substituent preferably has a bonding hand on the benzene skeleton.

[0022] From the viewpoint of easily improving the compatibility of this polyorganosiloxane (A) with the matrix resin, it is preferable that the three or more and six or less conjugated aromatic six-membered rings do not have a substituent other than the aromatic six-membered ring. Therefore, the three or more and six or less conjugated aromatic six-membered rings are preferably anthracene, triphenylene, pyrene, perylene, pyrenylbenzene, terphenylene, phenylanthracene, diphenylanthracene, naphthylanthracene, more preferably anthracene, pyrene, perylene, even more preferably pyrene or perylene, and even more preferably pyrene.

[0023] The specific structures of the three or more and six or less conjugated aromatic six-membered rings are as shown in the following formulas (5) to (15), but are not particularly limited. Among these, it is preferably any one of formulas (5), (7), and (8), and more preferably any one of formulas (5) and (7).

[0024] In the present invention, substituent A is preferably a group represented by Y-Z. Y is a divalent organic group bonded to a silicon atom of formula (1) and Z. Z is a conjugated aromatic six-membered ring consisting of three to six atoms, the details of which are as described above.

[0025] The divalent organic group Y bonded to the silicon atom is preferably a divalent organic group having 11 or fewer carbon atoms, and more preferably a divalent organic group having 10 or fewer carbon atoms. Thus, polyorganosiloxane (A) in which the number of carbon atoms of Y is below a certain level is preferable because it easily enhances the dispersibility of the filler. Furthermore, there is no particular lower limit to the number of carbon atoms of Y, but Y is preferably a divalent organic group having 4 or more carbon atoms, and more preferably a divalent organic group having 5 or more carbon atoms.

[0026] Y may be a hydrocarbon group, but it may also have a heteroatom. If Y has a heteroatom, it is preferable that at least one of the atoms constituting Y is a heteroatom, either at the α-position, β-position, or γ-position. This improves the fluidity of the polyorganosiloxane (A) and makes it easier to improve its compatibility with the matrix resin. From the viewpoint of improving fluidity and compatibility with the matrix resin, it is more preferable that at least one of the α-position or β-position atoms is a heteroatom. Here, the α-position atom is the atom constituting Y that is bonded to the aromatic ring of Y. The β-position atom is the atom constituting Y that is bonded to the α-position atom. The γ-position atom is the atom bonded to the β-position atom and is not the α-position atom. Note that the atom referred to here is not a hydrogen atom. Note that Y may also have heteroatoms in parts other than the α-position, β-position, and γ-position atoms. The heteroatoms in Y are not particularly limited, and examples include oxygen atoms, nitrogen atoms, sulfur atoms, and boron atoms. Among these, oxygen atoms and boron atoms are preferred from the viewpoint of effectively improving fluidity.

[0027] If Y has heteroatoms, Y will have structural units having heteroatoms. Examples of such structural units include B-O bonds in ethers, esters, amides, urethanes, thioethers, thioesters, and boronic acid esters. Among these, boronic acid esters, ethers, or esters are preferred from the viewpoint of improving adsorption to fillers and improving fluidity, and at least one of boronic acid esters and ethers is more preferred. Y may have structural units having two or more heteroatoms, for example, it may have an ether and a boronic acid ester, or it may have two or more ethers. As for ethers, cyclic ethers are particularly preferred. A cyclic ether is an ether having a structure in which the carbon of a cyclic hydrocarbon is replaced by oxygen, and among these, cyclic acetals are preferred.

[0028] Furthermore, Y has high acid and base resistance due to the presence of B-O bonds, particularly boronic acid esters, which helps prevent the decomposition of the polyorganosiloxane (A) by acidic or basic components derived from fillers, for example. The boronic acid ester preferably forms a cyclic ester in which O-B-O constitutes a ring. The cyclic ester composed of the boronic acid ester is preferably a 5- to 8-membered ring, but a 6-membered ring is more preferable. However, the B-O bond does not need to constitute a cyclic ester, and R １ -B-O is also acceptable. １ In -B-O, R １ This is a hydrocarbon group, preferably an alkyl group, and it is preferable that the O (oxygen atom) is bonded to another atom.

[0029] Furthermore, Y preferably has a skeleton represented by the following formulas (16), (17), or (18) from the viewpoint of improving adsorption to fillers and compatibility with resins. In equation (16), *1 and *2 are couplings, R ４ is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, preferably a hydrogen atom. Two R ４ They may be the same or different. ３is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, preferably a hydrocarbon group having 1 to 4 carbon atoms, more preferably a hydrocarbon group having 1 to 3 carbon atoms, and still more preferably an ethyl group. R ５ is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, preferably a hydrogen atom. The oxygen atom in formula (16) is preferably the above-mentioned β-position atom or γ-position atom, more preferably the β-position atom. In formula (17), *3 and *4 are bonds. The oxygen atom having the bond of *3 is preferably the above-mentioned α-position atom, β-position atom or γ-position atom. In formula (18), *5 and *6 are bonds, and R ７ is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, preferably a hydrogen atom. The two Rs ７ may be the same or different. R ６ is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, preferably a hydrocarbon group having 1 to 4 carbon atoms, more preferably a hydrocarbon group having 1 to 3 carbon atoms, and still more preferably an ethyl group. The boron atom in formula (18) is preferably the α-position atom. That is, the boron atom is preferably directly bonded to 3 to 6 conjugated aromatic 6-membered rings.

[0030] Y is preferably any structure represented by the following formulas (20) to (27) from the viewpoints of improving the adsorption to the filler and the compatibility with the matrix resin. In formulas (20) to (27), *7 is a bond that binds to 3 to 6 conjugated aromatic 6-membered rings, and *8 is a bond that binds to the silicon atom of formula (1). Among the above, the structures shown in formulas (20), (22), (26), and (27) are preferable, and among them, the structures shown in formulas (20) and (27) are more preferable.

[0031] Further, Y may be other than those having a heteroatom. Specifically, it may be a hydrocarbon group such as an alkylene group such as a methylene group or an ethylene group, or an arylene group such as a phenylene group.

[0032] In formula (1), R' is a monovalent organic group having an aliphatic unsaturated bond. Each R' in formula (1) may have two or more aliphatic unsaturated bonds, but it is preferable that each R' has one aliphatic unsaturated bond. By having one aliphatic unsaturated bond in each R', it becomes easier to separate the positions of multiple aliphatic unsaturated bonds, making it easier to form an appropriate crosslinking network. R' may be an alkenyl group, an acryloyl group (H ２ C=CH-C(=O)-), methacryloyl group (H ２ C = C(CH) ３ It is sufficient to have a reactive double bond group that can react with hydrosilyl groups, such as )-C(=O)-, which will be described later. In formula (1), R' preferably independently comprises at least one selected from the group consisting of vinyl group, acryloyl group, and methacryloyl group, with vinyl group being more preferred among these. These functional groups have excellent chemical stability and crosslinking reactivity, and make it easier to further improve bleed resistance. R' often has about 2 to 16 carbon atoms, preferably 2 to 10, and more preferably 2 to 8.

[0033] In R', the vinyl group, acryloyl group, or methacryloyl group may be bonded to the silicon atom via a single bond or a divalent organic group. The divalent organic group may be a hydrocarbon group which may have a heteroatom. An example of a heteroatom is an oxygen atom. The oxygen atom may, for example, form an -O- bond. Furthermore, an -O- bond may be present at the bonding position with the acryloyl group or methacryloyl group, forming an acryloyloxy group or a methacryloyloxy group. The acryloyloxy group or methacryloyloxy group may be bonded to the silicon atom via a hydrocarbon group which may have a heteroatom. The vinyl group may be bonded to the silicon atom via a single bond or a hydrocarbon group which may have a heteroatom. The hydrocarbon group which may have a heteroatom that bonds the acryloyloxy group, methacryloyloxy group, or vinyl group to the silicon atom is preferably one which does not have a heteroatom, and more preferably a divalent saturated aliphatic hydrocarbon group. The divalent saturated aliphatic hydrocarbon group preferably has 1 to 12 carbon atoms, more preferably 2 to 8, and even more preferably 2 to 4 carbon atoms. The divalent saturated aliphatic hydrocarbon group is preferably an alkylene group, and more preferably an alkylene group in which both ends of the carbon chain are bonded.

[0034] The preferred structure of R' is as shown in the following equations (30) to (32). In formulas (30), (31), and (32), X is either a single bond bonded to a silicon atom, or a hydrocarbon group bonded to a silicon atom that may have a heteroatom. Details of the hydrocarbon group that may have a heteroatom are as described above. In formulas (30) and (31), X is preferably a hydrocarbon group that may have a heteroatom, and in formula (32), X is preferably a single bond.

[0035] Preferred specific examples of R' are shown in the following equations (33) to (35). In formulas (33) to (35), * indicates the bonding position with the silicon atom.

[0036] In formula (1), at least one R is preferably a substituent A, which is preferably a group represented by Y-Z as described above, and the remaining R is a monovalent saturated hydrocarbon group having 1 to 4 carbon atoms. In formula (1), the number of substituents A is, for example, 1 to 8, preferably 1 to 5, more preferably 1 to 4, even more preferably 1 or 2, and most preferably 1. If there are multiple substituents A, the groups constituting each substituent A may be the same or different, but it is preferable that they be the same.

[0037] Examples of monovalent saturated hydrocarbon groups having 1 to 4 carbon atoms in R include alkyl groups such as methyl, ethyl, propyl, and butyl groups, with methyl groups being preferred. If there are multiple monovalent saturated hydrocarbon groups having 1 to 4 carbon atoms, these groups may be identical or different. Furthermore, it is preferable that 80 mol% or more of the multiple monovalent saturated hydrocarbon groups R in a single molecule are methyl groups, and more preferably 90 mol% or more are methyl groups. In addition, all of the multiple monovalent saturated hydrocarbon groups R having 1 to 4 carbon atoms may be methyl groups, but among these multiple R groups, the R bonded to the terminal silicon atom may include a butyl group or other non-methyl group, while the other R groups are methyl groups.

[0038] In formula (1), l may be an integer of 1 or more, but it is preferable to ensure a certain molecular weight or higher to improve compatibility with the matrix resin, thereby improving the viscosity reduction effect and bleed resistance. Specifically, l is preferably 8 or higher, more preferably 50 or higher, even more preferably 120 or higher, and even more preferably 170 or higher. Furthermore, by setting l to a certain level or lower, it is possible to prevent aggregation by cross-linking molecules, thereby improving the viscosity reduction effect. From this viewpoint, l is preferably 500 or lower, more preferably 450 or lower, even more preferably 350 or lower, even more preferably 300 or lower, and even more preferably 245 or lower.

[0039] As described above, in formula (1), the number of aliphatic unsaturated bonds is two or more. If the number of aliphatic unsaturated bonds is less than two, the polyorganosiloxane (A) cannot form a crosslinking network, and bleed-out cannot be sufficiently suppressed. From the viewpoint of improving bleed resistance, the number of aliphatic unsaturated bonds in the compound of formula (1) is preferably two or more, more preferably three or more, even more preferably four or more, and even more preferably five or more. On the other hand, from the viewpoint of easily ensuring a viscosity-reducing effect, the number of aliphatic unsaturated bonds in formula (1) may be 250 or less, preferably 200 or less, more preferably 120 or less, even more preferably 60 or less, even more preferably 40 or less, and even more preferably 10 or less. As described above, in formula (1), m and n may be integers of 0 or more. However, the number of aliphatic unsaturated bonds in each R' is typically one. Therefore, when m is 0, n may be an integer of 1 or more, and when n is 0, m may be an integer of 2 or more. When m is 0, if n is an integer greater than or equal to 1, the number of aliphatic unsaturated bonds in equation (1) becomes 2 or more, and bleed-out can be suppressed. When n is 0, if m is an integer greater than or equal to 2, the number of aliphatic unsaturated bonds in equation (1) becomes 2 or more, and bleed-out can be suppressed.

[0040] The number of silicon atoms to which R' is bonded in one molecule, i.e., the value of m+n, may be 1 or more, but from the viewpoint of improving bleed resistance, it is preferably 2 or more, more preferably 3 or more, even more preferably 4 or more, and even more preferably 5 or more. On the other hand, from the viewpoint of easily ensuring a viscosity-reducing effect, the number of silicon atoms to which R' is bonded in one molecule, i.e., the value of m+n, may be 250 or less, preferably 200 or less, more preferably 120 or less, even more preferably 60 or less, even more preferably 40 or less, and even more preferably 10 or less.

[0041] The polyorganosiloxane having the structure represented by formula (1) may have only the unit shown in parentheses for m, or only the unit shown in parentheses for n, or both the unit shown in parentheses for m and the unit shown in parentheses for n, but it is preferable that it has at least the unit shown in parentheses for m. In this case, it is preferable that it does not have the unit shown in parentheses for n. Therefore, in formula (1), it is preferable that m is 2 or more, and it is also preferable that m is 2 or more and n is 0. Furthermore, if n is 1 or more, m may be 0 as described above.

[0042] l+m+n represents the number of repeating units of the polyorganosiloxane (A) having the structure shown in formula (1). l+m+n is, for example, 10 or more and 520 or less. If l+m+n is above a certain level, a certain molecular weight is ensured, which improves compatibility with the matrix resin and makes the viscosity reduction effect and bleed resistance excellent. Also, by keeping l+m+n below a certain level, cross-linking aggregation between molecules of the polyorganosiloxane (A) does not occur, resulting in an excellent viscosity reduction effect. From these viewpoints, l+m+n is preferably 10 or more, more preferably 65 or more, even more preferably 130 or more, and even more preferably 200 or more. Furthermore, it is preferably 500 or less, more preferably 350 or less, even more preferably 300 or less, and even more preferably 250 or less.

[0043] In formula (1), the numbers of m and n should be within a certain range relative to the number of l. This makes it easier to further improve the viscosity-enhancing effect and bleed resistance. Specifically, the ratio of the total amount of m and n to l ((m+n) / l) should be, for example, 0.001 or more and 0.5 or less. From the viewpoint of excellent crosslinking reactivity and improved bleed resistance, the ratio ((m+n) / l) is preferably 0.001 or more, more preferably 0.003 or more, even more preferably 0.005 or more, even more preferably 0.008 or more, and even more preferably 0.02 or more. Also, from the viewpoint of increasing affinity with the matrix resin and making it easier to achieve an excellent viscosity-enhancing effect, the ratio ((m+n) / l) is preferably 0.5 or less, more preferably 0.4 or less, even more preferably 0.25 or less, and even more preferably 0.15 or less.

[0044] In formula (1), only one of the units shown in parentheses for m and the unit shown in parentheses for n is required. Therefore, in formula (1), either m / l or n / l should be between 0.001 and 0.5. Preferably, either m / l or n / l is 0.001 or higher, more preferably 0.003 or higher, even more preferably 0.005 or higher, even more preferably 0.008 or higher, even more preferably 0.02 or higher, and also preferably 0.5 or lower, more preferably 0.4 or lower, even more preferably 0.25 or lower, and even more preferably 0.15 or lower. Note that if m / l is within the above range, n / l may be 0, but n / l may be a value other than 0. Similarly, if n / l is within the above range, m / l may be 0, but m / l may be a value other than 0.

[0045] The polyorganosiloxane (A) may have substituent A (i.e., a conjugated aromatic six-membered ring of 3 to 6 atoms) at one end, at both ends, on a side chain, at one end and on a side chain, or at both ends and on a side chain, but it is preferable that it be at the end, and more preferably at one end. Furthermore, when the polyorganosiloxane (A) has substituent A on a side chain, substituent A is preferably bonded to a silicon atom in the unit shown in parentheses l. And R in the units shown in parentheses m and n is preferably a monovalent saturated hydrocarbon group having 1 to 4 carbon atoms.

[0046] The polyorganosiloxane (A) more preferably has the structure shown in formula (2), (3), or (4) below. Here, the polyorganosiloxane having the structure represented by formula (2) below has three to six aromatic six-membered rings conjugated at one end. In formula (2), R, A, R', l, m, and n are the same as above. However, in formula (2), R is preferably independently a monovalent saturated hydrocarbon group having 1 to 4 carbon atoms.

[0047] Furthermore, polyorganosiloxanes having the structure represented by the following formula (3) have three to six aromatic six-membered rings conjugated at both ends. In formula (3), R, A, R', l, m, and n are the same as described above. However, in formula (3), R is preferably independently a monovalent saturated hydrocarbon group having 1 to 4 carbon atoms.

[0048] Furthermore, polyorganosiloxanes having the structure represented by the following formula (4) have three to six aromatic six-membered rings conjugated to the side chain. In formula (4), R, A, R', l, m, and n are the same as above, and k is an integer from 1 to 10. However, each R is preferably independently a monovalent saturated hydrocarbon group having 1 to 4 carbon atoms. Also, k is preferably 1 to 8, more preferably 1 to 5, and even more preferably 1 or 2. The polyorganosiloxane (A), with its small k value, has excellent compatibility with matrix resins and the like, can form a crosslinked network more effectively, and can achieve a better viscosity reduction effect.

[0049] Of the polyorganosiloxanes (A) described above, it is preferable that they have the structure represented by formula (2) or (3), and more preferably that they have the structure represented by formula (2).

[0050] The polyorganosiloxane (A) may be a random polymer or a block polymer. Therefore, in formulas (1) to (3) above, the unit shown in parentheses l and the unit shown in parentheses m or n, or the unit shown in parentheses l, the unit shown in parentheses m, and the unit shown in parentheses n may exist in a blocky manner or randomly within the molecule. Also, in formula (4), the unit shown in parentheses k, the unit shown in parentheses l, and the unit shown in parentheses m or n, or the unit shown in parentheses k, the unit shown in parentheses l, the unit shown in parentheses m, and the unit shown in parentheses n may exist in a blocky manner or randomly within the molecule.

[0051] <Method for producing the polyorganosiloxane (A)> The polyorganosiloxane (A) can be produced by introducing substituent A (a group having 3 to 6 conjugated aromatic 6-membered rings) to a polyorganosiloxane and introducing an organic group R' (a monovalent organic group having an aliphatic unsaturated bond) to the side chain. The substituent A and organic group R are as described in formula (1) above.

[0052] The method for introducing substituent A to a polyorganosiloxane is not particularly limited and can be obtained by reacting a polyorganosiloxane having a generally available functional group with a compound having substituent A and a functional group that can react with the functional group of the polyorganosiloxane. Specifically, esterification reactions, acetalization reactions of aldehydes and diols, hydrosilylation reactions of hydrosilyl groups and carbon-carbon unsaturated bonds, and boric acid esterification reactions of boric acid and alcohols can be used.

[0053] In esterification reactions, a polyorganosiloxane having a hydroxyl group is reacted with a compound having a carboxyl group and substituent A (carboxylic acid). In this case, the carboxylic acid may be a carboxylic acid derivative; for example, a halocarbonyl group may be used instead of a carboxyl group. When using an acetalization reaction, a polyorganosiloxane having a diol structure is reacted with a compound having an aldehyde group and a group having substituent A. Alternatively, a polyorganosiloxane having a hydrosilyl group is reacted with a compound having a carbon-carbon unsaturated bond such as an acrylate group or a methacrylate group and a group having substituent A. Furthermore, in methods utilizing boric acid esterification reactions, a polyorganosiloxane having a hydroxyl group such as a diol is reacted with a boric acid group such as a dihydroxyboryl group or a hydroxyboryl group and a compound having substituent A. In the above methods, the diol structure is, for example, a 1,3-diol structure.

[0054] Furthermore, a method for introducing an organic group R' into the side chain is to use a cyclic polyorganosiloxane having an organic group R' and introduce a siloxane structure having an organic group R' into the chain. Examples of cyclic polyorganosiloxanes having an organic group R' include cyclotrisiloxane compounds, cyclotetrasiloxane compounds, and cyclopentasiloxane compounds. In addition to the organic group R', the cyclic polyorganosiloxane preferably has a monovalent saturated hydrocarbon group having 1 to 4 carbon atoms. The monovalent saturated hydrocarbon group having 1 to 4 carbon atoms referred to here is R other than A in formula (1) above, and the details are as described above. Specific examples of cyclic polyorganosiloxanes include 2,4,6-trimethyl-2,4,6-trivinylcyclotrisiloxane and 2,4,6,8-tetra(3-(meth)acrylooxypropyl)-2,4,6,8-tetramethylcyclotetrasiloxane.

[0055] A cyclic polyorganosiloxane having an organic group R' is preferably produced by reacting it with a starting polyorganosiloxane. In this case, the starting polyorganosiloxane may be a polyorganosiloxane to which substituent A has been introduced, or it may be a polyorganosiloxane before substituent A has been introduced, but it is preferable that it is a polyorganosiloxane to which substituent A has been introduced. Therefore, it is preferable to produce this polyorganosiloxane (A) by reacting a polyorganosiloxane having a functional group with a compound having substituent A and a functional group that can react with the functional group of the polyorganosiloxane, and then further reacting it with a cyclic polyorganosiloxane.

[0056] Furthermore, the polyorganosiloxane (A) may be chain-extended as appropriate using a chain extender. Chain extension makes it easier to increase the value of l in formula (1) of the polyorganosiloxane (A). The chain extender may be a linear polyorganosiloxane or a cyclic polyorganosiloxane, but a cyclic polyorganosiloxane is preferred. The cyclic polyorganosiloxane and linear polyorganosiloxane used for chain extension are compounds in which a monovalent saturated hydrocarbon group having 1 to 4 carbon atoms is bonded to the silicon atoms constituting the ring, and preferably alkyl-containing cyclic polyorganosiloxanes such as octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane. The monovalent saturated hydrocarbon group having 1 to 4 carbon atoms is R other than A in formula (1) above, and the details are as described above. The chain extender may be reacted with the starting material polyorganosiloxane together with a cyclic polyorganosiloxane having substituent A.

[0057] (Second Embodiment) The polyorganosiloxane according to the second embodiment of the present invention (hereinafter sometimes referred to as "the polyorganosiloxane (B)") has a structure represented by the following formula (51). In the following description, when referring to either the polyorganosiloxane (A) or the polyorganosiloxane (B), it is simply referred to as the polyorganosiloxane. (In formula (51), R is independently a monovalent saturated hydrocarbon group having 1 to 4 carbon atoms, R' is a monovalent organic group having an aliphatic unsaturated bond, and A is a monovalent organic group having at least one hydroxyl group. l is an integer of 1 or more. m and n are integers of 0 or more, with at least one of them being 1 or more. In formula (51), the number of aliphatic unsaturated bonds is 2 or more.)

[0058] This polyorganosiloxane (B) enhances viscosity reduction while also exhibiting good bleed resistance. By enhancing viscosity reduction, this polyorganosiloxane (B) also facilitates improved filler filling properties. The reason why it enhances viscosity reduction while maintaining good bleed resistance is not entirely clear, but it is presumed to be as follows: This polyorganosiloxane (B) has at least one hydroxyl group at its molecular end, resulting in excellent adsorption to fillers, especially metallic fillers. Furthermore, since the hydroxyl group does not form a direct bond with the filler, the filler interface becomes more flexible, thereby increasing the flexibility of the compound into which the filler is incorporated and allowing for an appropriate viscosity reduction effect. In addition, this polyorganosiloxane (B) has two or more aliphatic unsaturated bonds, which facilitates chemical bonding to matrix resins and other materials to form a crosslinked network, thereby improving bleed resistance.

[0059] As described above, A in formula (51) is a monovalent organic group having at least one hydroxyl group, but it is preferable that A has two or more hydroxyl groups. Having two or more hydroxyl groups results in better affinity to fillers, especially metal-based fillers. The number of hydroxyl groups in A may be six or less, preferably four or less, more preferably three or less, and most preferably two. Furthermore, from the viewpoint of ease of manufacture, it is also preferable that the number of hydroxyl groups in A be one or two.

[0060] Each hydroxyl group in A is preferably a hydroxyl group bonded to a carbon atom. More preferably, the two hydroxyl groups in A constitute at least one of a 1,2-diol structure and a 1,3-diol structure. Having these structures makes it easier for the polyorganosiloxane (B) to have better affinity with fillers, especially metal-based fillers, due to the chelating effect. Among these, the 1,3-diol structure is more preferred. The hydroxyl group may be a phenolic hydroxyl group directly bonded to an aromatic ring, or a hydroxyl group directly bonded to an aliphatic hydrocarbon. Among these, a hydroxyl group directly bonded to an aliphatic hydrocarbon is preferred. Furthermore, the above-mentioned 1,2-diol structure and 1,3-diol structure may also be composed of an aromatic ring or an aliphatic hydrocarbon.

[0061] In formula (51), A may consist of hydrocarbons other than the hydroxyl group, or it may have heteroatoms other than the hydroxyl group. The heteroatoms other than the hydroxyl group are not particularly limited, and examples include oxygen atoms, nitrogen atoms, sulfur atoms, and boron atoms. Among these, oxygen atoms and boron atoms are preferred, and oxygen atoms are more preferred. The number of carbon atoms in A is not particularly limited, but for example it is about 1 to 30, preferably 2 to 20, more preferably 4 to 16, and even more preferably 7 to 12. Having a certain number of carbon atoms in A makes it easier to adsorb the hydroxyl group onto the filler and facilitates the synthesis of the compound shown in formula (51).

[0062] If A in formula (51) has a heteroatom other than a hydroxyl group, then A has a structural unit having a heteroatom other than a hydroxyl group. Examples of such structural units include B-O bonds in ethers, esters, amides, urethanes, thioethers, thioesters, oxime esters (-C=N-O-C(=O)-), and boronic acid esters. Among these, B-O bonds such as ethers or boronic acid esters are preferred, and ethers are more preferred. Y may have two or more structural units having heteroatoms other than a hydroxyl group, for example, it may have an ether and a boronic acid ester, or it may have two or more ethers. The ether may be a cyclic ether. A cyclic ether is an ether having a structure in which the carbon of a cyclic hydrocarbon is replaced by oxygen, and among these, cyclic acetals are preferred. Furthermore, it is preferable that the boronic acid ester constitutes a cyclic ester in which O-B-O constitutes a ring. The cyclic ester composed of the boronic acid ester is preferably a 5- to 8-membered ring, but a 6-membered ring is more preferred. However, the B-O bond does not need to constitute a cyclic ester, R １０ -B-O is also acceptable. １０ In -B-O, R １０ This is a hydrocarbon group, preferably an alkyl group, and it is preferable that the O (oxygen atom) is bonded to another atom.

[0063] In the above formula (51), A may have a structure represented by D-E. D is an organic group having 1 or more carbon atoms, which may have a heteroatom, and is a linking group that connects E and a silicon atom. E is a hydroxyl group-containing unit having 1 to 10 carbon atoms and having one or more hydroxyl groups. In other words, E is a structure in which one or more hydroxyl groups are bonded to an organic group having 1 to 10 carbon atoms. The number of hydroxyl groups that E has may be 6 or less, preferably 4 or less, more preferably 3 or less, and most preferably 2, but 1 or 2 is also acceptable.

[0064] E is preferably a structure in which one or more hydroxyl groups are bonded to a hydrocarbon group having 1 to 10 carbon atoms, more preferably a structure in which one or more hydroxyl groups are bonded to a hydrocarbon group having 2 to 6 carbon atoms, and even more preferably a structure in which two hydroxyl groups are bonded to a hydrocarbon group having 2 to 6 carbon atoms. In this specification, E is a hydroxyl group-containing unit in which the portion bonded to D is one carbon atom, and it is preferable that the portion that includes all the hydroxyl groups contained in A and has the smallest number of carbon atoms be defined as a hydroxyl group-containing unit. More specifically, E in formula (51) is preferably a structure represented by the following formula (53) or (54), and more preferably a structure represented by the following formula (53).

[0065] In formula (53), each Z is independently a hydrocarbon group, a hydrogen atom, a hydroxyl group, or a group having a hydroxyl group, and at least one of the multiple Zs is a hydroxyl group or a group having a hydroxyl group. In formulas (53) and (54), * represents a bond that connects with D.

[0066] Examples of groups having a hydroxyl group in Z include groups in which a hydroxyl group is bonded to a hydrocarbon group having 1 to 4 carbon atoms. Here, the hydrocarbon group is preferably a divalent saturated hydrocarbon group, and Z is preferably "-CH ２ It is "OH". Also, in equation (53), one of the Z is -CH ２ It is OH, and the other is -CH ２ It is more preferable that the groups be OH or hydroxyl groups. In this case, the remaining Z may have a hydroxyl group, but it is preferable that it does not. With such a structure, the structure in formula (53) becomes a 1,2-diol structure and a 1,3-diol structure. Also, since the 1,3-diol structure is more preferable for E, two of the Z groups are -CH ２It is even more preferable that it be an OH group. In this case, the remaining Z may be a hydrogen atom or a hydrocarbon group, but a hydrocarbon group is preferred. Examples of hydrocarbon groups in Z include hydrocarbon groups having 1 to 4 carbon atoms, preferably alkyl groups such as methyl, ethyl, propyl, and butyl groups, with the ethyl group being more preferred.

[0067] Furthermore, among the structures represented by formula (53), those represented by formula (53-1) or formula (53-2) below are particularly preferred. In equations (53-1) and (53-2), * represents a bond that connects with D.

[0068] In formula (54), the two hydroxyl groups are preferably positioned at the ortho and meta positions relative to each other, but it is more preferable that they be positioned at the ortho position as shown in formula (54-1) below. In equation (54-1), * represents a bond that connects with D.

[0069] D is an organic group which may have a heteroatom. Therefore, D has a structural unit having a heteroatom. Details of the structural unit having a heteroatom are as described above. In particular, D is preferably a hydrocarbon group, or a hydrocarbon group having at least one of an ether bond and / or B-O, and a hydrocarbon group having an ether bond is more preferred. The hydrocarbon group in D is preferably a saturated hydrocarbon group. The number of carbon atoms in D is, for example, about 1 to 25, preferably 1 to 15, more preferably 1 to 10, even more preferably 2 to 8, and even more preferably 3 to 6. Having a carbon atom number in D within a certain range makes it easier to adsorb the hydroxyl group onto the filler and facilitates the synthesis of the compound shown in formula (51). Furthermore, D is a divalent organic group and is bonded to the silicon atom and E in formula (51).

[0070] D is preferably an alkylene group or an alkylene ether group, with an alkylene ether group being more preferred. The number of carbon atoms in the alkylene group is, for example, 1 to 10, preferably 2 to 8, and more preferably 3 to 6. The alkylene ether group has a structure in which an oxygen atom is located between two alkylene groups, and is "-R１ -O-R ２ Represented by -, R １ and R ２ Each of these is an alkylene group, R １ and R ２ The total number of carbon atoms is, for example, 2 to 10, preferably 2 to 8, and more preferably 3 to 6. １ and R ２ When the number of carbon atoms is two or more, it is preferable that the chain is linear and both ends are bonded. Among alkylene ether groups, "-CH ２ CH ２ CH ２ OCH ２ - is particularly preferred. Note that in formula (51), the above "-CH ２ CH ２ CH ２ OCH ２ The carbon atom at the left end of the "-" is bonded to a silicon atom, and the carbon atom at the right end is bonded to E. Furthermore, when bonded to the structure of formula (55) or (56) described later, the carbon atom at the left end is bonded to a silicon atom, and the carbon atom at the right end is bonded to the structure of formula (55) or (56). Note that when D is an alkylene group or an alkylene ether group, E is preferably the structure represented by formula (53), and more preferably the structure of formula (53-2).

[0071] D may include a cyclic acetal structure and a cyclic borate ester structure. The cyclic acetal structure and the cyclic borate ester structure are preferably bonded to the silicon atom via the alkylene group and alkylene ether group described above. Specifically, the cyclic acetal structure or cyclic borate ester structure in D is preferably a structure represented by the following formula (55) or formula (56).

[0072] In equation (55), *1 and *2 are couplings, R ４ is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, preferably a hydrogen atom. Two R ４ They may be the same or different. ３R is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, preferably a hydrocarbon group having 1 to 4 carbon atoms, more preferably a hydrocarbon group having 1 to 3 carbon atoms, and even more preferably an ethyl group. ５ *1 is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, preferably a hydrogen atom. *1 may be bonded to E. The structure of formula (55) may be bonded to the silicon bond via an alkylene group or alkylene ether group, and *2 may be bonded to an alkylene group or alkylene ether group. In formula (56), *3 and *4 are bonding hands. R ７ is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, preferably a hydrogen atom. Two R ７ They may be the same or different. ６ is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, preferably a hydrocarbon group having 1 to 4 carbon atoms, more preferably a hydrocarbon group having 1 to 3 carbon atoms, and even more preferably an ethyl group. *3 may be bonded to E. The structure of formula (56) may be bonded to the silicon bond via an alkylene group or alkylene ether group, and *4 may be bonded to an alkylene group or alkylene ether group. Furthermore, if D has the structure shown in formula (55) or formula (56), E may have the structure of formula (54), and more preferably the structure of formula (54-1).

[0073] Preferred specific examples of D are shown in the following formulas (57) to (59), and among them, having the structure shown in formula (57) is more preferable. In formulas (57) to (59), *5 is a bond that binds to E, and *6 is a bond that binds to the silicon atom in formula (51). The D shown in formula (57) is preferably bonded to the E shown in formula (53), more preferably to the E shown in formula (53-1) or (53-2), and even more preferably to the E shown in formula (53-2). The D shown in formula (58) or (59) is preferably bonded to the E shown in formula (54), and more preferably to the E shown in formula (54-1).

[0074] In formula (51), R' is a monovalent organic group having an aliphatic unsaturated bond. As explained in formula (1), each R' in formula (51) may have two or more aliphatic unsaturated bonds, but it is preferable that each R' has one aliphatic unsaturated bond. The R' in formula (51) is the same as the R' in formula (1), so its explanation is omitted.

[0075] Examples of monovalent saturated hydrocarbon groups having 1 to 4 carbon atoms in R of formula (51) include alkyl groups such as methyl, ethyl, propyl, and butyl groups, with methyl groups being preferred. Multiple R groups may be the same or different from each other. In a single molecule, it is preferable that 80 mol% or more of the R groups are methyl groups, and more preferably 90 mol% or more are methyl groups. Furthermore, all of the R groups may be methyl groups, but among the R groups, the R group bonded to the terminal silicon atom may include a butyl group or other non-methyl group, while the other R groups are methyl groups.

[0076] In formula (51), l may be an integer of 1 or more, but it is preferable to ensure a certain molecular weight or higher to improve compatibility with the matrix resin, thereby improving the viscosity reduction effect and bleed resistance. Specifically, l is preferably 8 or higher, more preferably 50 or higher, even more preferably 120 or higher, and even more preferably 170 or higher. Furthermore, by setting l to a certain level or lower, it is possible to prevent aggregation by cross-linking molecules, thereby improving the viscosity reduction effect. From this viewpoint, l is preferably 500 or lower, more preferably 450 or lower, even more preferably 350 or lower, even more preferably 300 or lower, and even more preferably 245 or lower.

[0077] As described above, in formula (51), the number of aliphatic unsaturated bonds is 2 or more. The number of aliphatic unsaturated bonds is the total number of aliphatic unsaturated bonds contained in R' in formula (51). If the number of aliphatic unsaturated bonds is less than 2, the polyorganosiloxane (B) cannot form a crosslinking network, and bleed-out cannot be sufficiently suppressed. From the viewpoint of improving bleed resistance, the number of aliphatic unsaturated bonds in the compound of formula (51) is preferably 2 or more, more preferably 3 or more, even more preferably 4 or more, and even more preferably 5 or more. On the other hand, from the viewpoint of easily ensuring a viscosity-reducing effect, the number of aliphatic unsaturated bonds in formula (51) may be 250 or less, preferably 200 or less, more preferably 120 or less, even more preferably 60 or less, even more preferably 40 or less, and even more preferably 10 or less. As described above, in formula (51), m and n may be integers of 0 or more. However, the number of aliphatic unsaturated bonds in each R' is typically 1. Therefore, when m is 0, n should be an integer greater than or equal to 1, and when n is 0, m should be an integer greater than or equal to 2.

[0078] The number of silicon atoms to which R' is bonded in one molecule of formula (51), i.e., the value of m+n, may be 1 or more, but from the viewpoint of improving bleed resistance, it is preferably 2 or more, more preferably 3 or more, even more preferably 4 or more, and even more preferably 5 or more. On the other hand, from the viewpoint of easily ensuring a viscosity-reducing effect, the number of silicon atoms to which R' is bonded in one molecule, i.e., the value of m+n, may be 250 or less, preferably 200 or less, more preferably 120 or less, even more preferably 60 or less, even more preferably 40 or less, and even more preferably 10 or less.

[0079] The polyorganosiloxane having the structure represented by formula (51) may have only the unit shown in parentheses for m, or only the unit shown in parentheses for n, or both the unit shown in parentheses for m and the unit shown in parentheses for n, but it is preferable that it has at least the unit shown in parentheses for m. In this case, it is preferable that it does not have the unit shown in parentheses for n. Therefore, in formula (51), it is preferable that m is 2 or more, and it is also preferable that m is 2 or more and n is 0. Furthermore, if n is 1 or more, m may be 0 as described above.

[0080] In this polyorganosiloxane (B), l+m+n represents the number of repeating units of this polyorganosiloxane (B) having the structure shown in formula (51). l+m+n is, for example, 10 or more and 520 or less. If l+m+n is above a certain level, by ensuring a molecular weight above a certain level, compatibility with the matrix resin can be improved, resulting in excellent viscosity reduction and bleed resistance. Also, by keeping l+m+n below a certain level, cross-linking aggregation between molecules of this polyorganosiloxane (B) does not occur, resulting in excellent viscosity reduction. From these viewpoints, l+m+n is preferably 10 or more, more preferably 65 or more, even more preferably 130 or more, and even more preferably 200 or more. Furthermore, it is preferably 500 or less, more preferably 350 or less, even more preferably 300 or less, and even more preferably 270 or less.

[0081] In formula (51), the numbers of m and n should be within a certain range relative to the number of l. This makes it easier to further improve the viscosity-enhancing effect and bleed resistance. Specifically, the ratio of the total amount of m and n to l ((m+n) / l) is preferably 0.001 or more and 0.5 or less. From the viewpoint of excellent crosslinking reactivity and improved bleed resistance, the ratio ((m+n) / l) is more preferably 0.003 or more, even more preferably 0.005 or more, even more preferably 0.008 or more, and even more preferably 0.02 or more. Furthermore, from the viewpoint of increasing affinity with the matrix resin and making it easier to achieve an excellent viscosity-enhancing effect, the ratio ((m+n) / l) is more preferably 0.4 or less, even more preferably 0.25 or less, and even more preferably 0.15 or less.

[0082] In formula (51), only one of the units shown in parentheses for m and the unit shown in parentheses for n is required. Therefore, in formula (1), it is preferable that either m / l or n / l is between 0.001 and 0.5. More preferably, either m / l or n / l is between 0.003 and 0.005, even more preferably 0.008 and 0.02, and even more preferably 0.4 or less, even more preferably 0.25 or less, and even more preferably 0.15 or less. Note that if m / l is within the above range, n / l may be 0, but n / l may be a value other than 0. Similarly, if n / l is within the above range, m / l may be 0, but m / l may be a value other than 0.

[0083] The polyorganosiloxane (B) preferably has the structure shown in formula (61), (62), (63), or (64) below, and more preferably has the structure shown in formula (61).

[0084] Furthermore, among the above, polyorganosiloxane (B) having a structure represented by the following formula (52) is even more preferred. In equation (52), l is the same as above. m is an integer greater than or equal to 2, but the preferred range for m is as described above.

[0085] The polyorganosiloxane (B) may be a random polymer or a block polymer. Therefore, in formula (51) above, the unit shown in parentheses l and the unit shown in parentheses m or n, or the unit shown in parentheses l, the unit shown in parentheses m, and the unit shown in parentheses n may exist in a blocky manner or randomly within the molecule. Also, in formulas (52), (61), (62), (63), and (64), the unit shown in parentheses l and the unit shown in parentheses m may exist in a blocky manner or randomly within the molecule.

[0086] <Method for producing the polyorganosiloxane (B)> The polyorganosiloxane (B) can be produced by introducing an organic group R' (a monovalent organic group having an aliphatic unsaturated bond) into the side chain of a polyorganosiloxane used as a raw material. The organic group R' is as described in formula (51) above.

[0087] One method for introducing an organic group R' into the side chain is to react a cyclic polyorganosiloxane having an organic group R' with a starting polyorganosiloxane to introduce a siloxane structure having an organic group R' into the chain. Examples of cyclic polyorganosiloxanes having an organic group R' include cyclotrisiloxane compounds, cyclotetrasiloxane compounds, and cyclopentasiloxane compounds. In addition to the organic group R', the cyclic polyorganosiloxane may also have a monovalent saturated hydrocarbon group having 1 to 4 carbon atoms. The monovalent saturated hydrocarbon group having 1 to 4 carbon atoms referred to here is R in formula (51) above, and its details are as described above. Specific examples of cyclic polyorganosiloxanes are as described in the first embodiment.

[0088] A cyclic polyorganosiloxane having an organic group R' may be reacted with a starting polyorganosiloxane. In this case, the starting polyorganosiloxane may be a polyorganosiloxane having a functional group A (organic group A) at its terminus, or it may be a polyorganosiloxane before the introduction of functional group A, but it is preferable that it be a polyorganosiloxane having functional group A at its terminus. Functional group A is A in formula (51) above, and its details are as described above. When reacting a cyclic polyorganosiloxane having an organic group R' with a polyorganosiloxane having functional group A at its terminus, the hydroxyl group of functional group A may be protected with a protecting group as appropriate, and the cyclic polyorganosiloxane having organic group R' may be reacted with the polyorganosiloxane having functional group A that has been protected with a protecting group. The protecting group may be composed of an acetal, a boronic acid ester, or the like. The protecting group can be removed after reacting with a cyclic polyorganosiloxane having an organic group R'.

[0089] Polyorganosiloxanes having functional group A at their termini may be obtained using known compounds, or by reacting a known polyorganosiloxane with a compound having functional group A. Specifically, they can be obtained by reacting a generally available polyorganosiloxane having a functional group with a compound having functional group A and a functional group that can react with the functional group of the polyorganosiloxane. Specifically, esterification reactions, acetalization reactions of aldehydes and diols, hydrosilylation reactions of hydrosilyl groups and carbon-carbon unsaturated bonds, and boric acid esterification reactions of boric acid and alcohols are good choices. For example, when using an acetalization reaction, a polyorganosiloxane having a diol structure can be reacted with a compound having an aldehyde group and a group having functional group A. In methods utilizing borate esterification reactions, it is preferable to react a polyorganosiloxane having a hydroxyl group, such as a diol, with a compound having a boric acid group, such as a dihydroxyboryl group or a hydroxyboryl group, and functional group A. When using an acetalization reaction or a borate esterification reaction, the hydroxyl group in functional group A may be protected with a protecting group as appropriate before being reacted with the polyorganosiloxane.

[0090] Furthermore, the polyorganosiloxane (B) may be chain-extended as appropriate using a chain extender. Chain extension makes it easier to increase the value of l in formula (51) of the polyorganosiloxane (B). The chain extender may be a linear polyorganosiloxane or a cyclic polyorganosiloxane, but a cyclic polyorganosiloxane is preferred. The cyclic polyorganosiloxane and linear polyorganosiloxane used for chain extension are compounds in which a monovalent saturated hydrocarbon group having 1 to 4 carbon atoms is bonded to the silicon atoms constituting the ring, and preferably alkyl-containing cyclic polyorganosiloxanes such as octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane. The monovalent saturated hydrocarbon group having 1 to 4 carbon atoms is R in formula (51) above, and its details are as described above. The chain extender may be reacted with the starting material polyorganosiloxane together with a cyclic polyorganosiloxane having functional group A.

[0091] [Filler] (First Embodiment) The polyorganosiloxane (A) according to the first embodiment can be used as a filler dispersant. A thermally conductive filler is preferably used as the filler. In the first embodiment, the filler may be a filler that does not have π electrons, or a π-electron filler which has π electrons, but a π-electron filler is preferred. The π-electron filler is preferably a conjugated filler in which the π electrons form a conjugated system. The π-electron filler preferably has a six-membered ring atomic structure as its constituent unit, and the six-membered ring atomic structure preferably has π electrons. Specific examples of π-electron fillers include boron nitride and carbon materials, and among these, carbon materials are preferred. By using a π-electron filler, the filler is more easily adsorbed onto substituent A, which is the linker of the polyorganosiloxane (A), and the dispersibility of the filler is improved.

[0092] Boron nitride forms a six-membered ring structure with boron atoms (B) and nitrogen atoms (N). Examples of boron nitride include hexagonal boron nitride, and more specifically, boron nitride nanotubes, boron nitride nanosheets, and hexagonal boron nitride particles. Boron nitride nanotubes are tubular materials formed from hexagonal boron nitride. The ideal structure of a boron nitride nanotube is one in which the planes of the six-membered ring network are parallel to the tube axis, resulting in a single-wall or multi-wall tube. Boron nitride nanotubes that are single-walled are called single-wall tubes, and those that are multi-wall tubes are called multi-wall tubes. Either single-wall tubes or multi-wall tubes may be used as boron nitride nanotubes, or they may be used in combination.

[0093] Boron nitride nanotubes, for example, have an average diameter of 1 nm to 70 nm and an average length of 100 nm to 50 μm. By keeping the average diameter and average length within the above range, it becomes easier to appropriately disperse the filler in the resin composition and increase the thermal conductivity of the resin composition. The average diameter of the boron nitride nanotubes is preferably 3 nm or more, more preferably 4 nm or more. Furthermore, the average diameter of the boron nitride nanotubes is preferably 10 nm or less, more preferably 8 nm or less. Furthermore, the average length of the boron nitride nanotubes is preferably 500 nm or more, more preferably 1 μm or more, preferably 20 μm or less, more preferably 8 μm or less, and even more preferably 5 μm or less.

[0094] Note that the diameter of a boron nitride nanotube refers to the outer diameter in the case of a single-walled tube, and the outer diameter of the outermost tube in the case of a multi-walled tube. The diameter and length of a boron nitride nanotube can be measured from images obtained by observation with an electron microscope, such as a TEM (transmission electron microscope), and the average diameter and average length can be determined by the arithmetic mean of any 50 nanotubes. The same applies to the diameter and length of carbon nanotubes, which will be discussed later.

[0095] Boron nitride nanosheets are formed from boron nitride and have an ultra-thin two-dimensional sheet structure, for example, having a structure in which a single or multiple layers of hexagonal boron nitride are laminated. Boron nitride nanosheets with an average thickness of 20 nm or less are used. From the viewpoint of improving thermal conductivity while making the resin composition into which the filler is compounded sufficiently flexible, the average thickness of the boron nitride nanosheet is preferably less than 10 nm, more preferably 6 nm or less, and even more preferably 4 nm or less. The lower limit of the average thickness of the boron nitride nanosheet is not particularly limited, but for example it is 1 nm. The size of the boron nitride nanosheet is not particularly limited, but the average longest diameter is, for example, 200 nm or more and 3 μm or less, preferably 500 nm or more and 2 μm or less. The thickness and longest diameter of boron nitride nanosheets can be measured in images obtained by observation with an electron microscope, such as a TEM (transmission electron microscope). The average thickness and average longest diameter of each boron nitride nanosheet can be determined by the arithmetic mean of any 50 images from the electron microscope. The same method can be used to determine the longest diameter and thickness of carbon nanosheets, as described later.

[0096] Hexagonal boron nitride particles are particulate boron nitride particles other than boron nitride nanosheets and boron nitride nanotubes, and their shape is not particularly limited; they may be flaky, spherical, polygonal, or irregularly shaped boron nitride particles. They may also be aggregated particles formed by the aggregation of multiple primary particles. The primary particle diameter of hexagonal boron nitride particles is not particularly limited and may be nano-sized or micro-sized. For example, the average primary particle diameter of hexagonal boron nitride particles may be, for example, 5 nm to 100 μm, preferably 10 nm to 50 μm, and more preferably 0.1 μm to 40 μm. The particle size of aggregated particles is also not particularly limited; the average particle size of aggregated particles may be, for example, 0.1 μm to 250 μm, more preferably 0.5 μm to 200 μm, and even more preferably 1 μm to 150 μm. The primary particle diameter of hexagonal boron nitride particles and the particle diameter of aggregated particles can be determined by measuring the maximum diameter of the particles in images obtained by observation using an electron microscope such as a TEM (transmission electron microscope) or SEM (scanning electron microscope). The average particle size, such as the average primary particle diameter, can be determined by the arithmetic mean of the maximum diameters of any 50 particles. The same applies to other fillers such as graphite particles, which will be discussed later.

[0097] Carbon materials are not particularly limited as long as they form a six-membered ring structure with carbon atoms and the six-membered ring structure has π electrons, but examples include carbon fibers, carbon nanotubes, carbon nanosheets, graphite, graphene, and carbon black.

[0098] Graphitized carbon fibers are preferred as the carbon fibers. Graphitized carbon fibers have graphite crystal planes (i.e., planes of the six-membered ring network) aligned along the fiber axis, and possess high thermal conductivity in that fiber axis direction. Graphitized carbon fibers with a high degree of graphitization are preferred. The fiber diameter of the graphitized carbon fibers is not particularly limited, but for example, the average diameter is 1 μm to 30 μm, preferably 5 μm to 20 μm. A fiber diameter within this range facilitates industrial production and makes it easier to increase the thermal conductivity of the resin composition. As described above, the average fiber length of the carbon fibers is preferably 10 μm to 600 μm, more preferably 15 μm to 500 μm, and even more preferably 20 μm to 300 μm. The average diameter and average fiber length of carbon fibers can be measured using images obtained from observations with an electron microscope, such as a TEM (transmission electron microscope) or SEM (scanning electron microscope). The arithmetic mean of the diameters and fiber lengths of any 50 carbon fibers can then be used as the average diameter and average fiber length.

[0099] Carbon nanotubes are materials having a structure in which a graphite sheet with a hexagonal network of carbon atoms is wound into a cylindrical shape. Those wound in a single layer are called single-wall carbon nanotubes, and those wound in multiple layers are called multi-wall carbon nanotubes. In this invention, the type of carbon nanotube is not particularly limited and may be single-wall carbon nanotubes, multi-wall carbon nanotubes, or combinations thereof. The average diameter of the carbon nanotubes is preferably 1 nm to 100 nm, and more preferably 2 nm to 15 nm. The average length of the carbon nanotubes is preferably 0.1 μm to 1000 μm, and more preferably 10 μm to 500 μm.

[0100] Carbon nanosheets have a structure in which hexagonal network-like arrangements of carbon atoms are aligned along the plane direction, and have an ultra-thin two-dimensional sheet structure. For example, they have a structure in which layers of hexagonal network-like arrangements of carbon atoms are stacked in single or multiple layers. For example, the average thickness of a carbon nanosheet is 20 nm or less, preferably 10 nm or less. The lower limit of the average thickness of a carbon nanosheet is not particularly limited, but for example it is 0.7 nm. The size of a carbon nanosheet is not particularly limited, but the average longest diameter is for example 0.2 μm to 3 μm, preferably 0.5 μm to 2.5 μm.

[0101] Graphite can be graphite particles. Graphite particles can be particles other than the carbon fibers, carbon nanotubes, and carbon nanosheets mentioned above, and their shape is not particularly limited; they may be flaky, spherical, polygonal, or irregularly shaped. They may also be aggregated particles formed by the aggregation of multiple primary particles. For example, the average primary particle diameter of the graphite particles may be, for example, 5 nm to 100 μm, preferably 10 nm to 50 μm, and more preferably 0.1 μm to 40 μm. The particle size of the aggregated particles is also not particularly limited; the average particle size of the aggregated particles may be, for example, 0.1 μm to 250 μm, more preferably 0.5 μm to 200 μm, and even more preferably 1 μm to 150 μm. Of course, graphite may be other than graphite particles, and may be fibrous materials such as the graphitized carbon fibers mentioned above.

[0102] Graphene has a hexagonal mesh-like planar layer and can be obtained, for example, by exfoliating the interlayers of graphite, which has a layered structure in which hexagonal mesh-like planar layers are stacked by van der Waals forces. The average thickness of graphene is, for example, 3 nm to 100 nm, preferably 7 nm to 50 nm. The average thickness can be measured, for example, in an image obtained by observation with a TEM (transmission electron microscope), and can be determined by the arithmetic mean of any 50 points in the electron microscope image.

[0103] In the first embodiment of the present invention, when a π-electron filler is used as the filler, it is more preferable to include at least one selected from the group consisting of boron nitride, carbon nanotubes, carbon fibers, graphite, and graphene, more preferably graphite, boron nitride, or both, and even more preferably graphite. Among π-electron fillers, using these fillers makes it easier to improve the thermal conductivity of the resin composition in which the filler is blended. Furthermore, since these fillers have excellent adsorption properties to the polyorganosiloxane (A), it is easier to blend the filler into the resin composition in a properly dispersed state.

[0104] Fillers that do not have π electrons are not particularly limited and include, for example, oxides, nitrides, carbides, and metal hydroxides. Examples of oxides include iron oxide, zinc oxide, aluminum oxide such as alumina, metal oxides such as magnesium oxide, titanium oxide, cerium oxide, and zirconium oxide, and oxides other than metal oxides such as silicon oxide (silica). Examples of nitrides include metal nitrides such as aluminum nitride, gallium nitride, chromium nitride, tungsten nitride, magnesium nitride, molybdenum nitride, and lithium nitride, and nitrides other than metal nitrides such as silicon nitride. Examples of carbides include metal carbides such as aluminum carbide, titanium carbide, and tungsten carbide, and carbides other than metal carbides such as silicon carbide and boron carbide. Examples of metal hydroxides include aluminum hydroxide, calcium hydroxide, and magnesium hydroxide.

[0105] When using fillers that do not have π electrons, it is preferable to use metal oxides, and more preferable to use aluminum oxide. The average primary particle size of the fillers that do not have π electrons is not particularly limited, but is preferably 0.1 μm to 100 μm, more preferably 0.5 μm to 50 μm, and even more preferably 0.5 μm to 15 μm. The above fillers may be used individually or in combination of two or more.

[0106] (Second Embodiment) The polyorganosiloxane (B) according to the second embodiment can also be used as a filler dispersant. A thermally conductive filler is preferably used as the filler. In the second embodiment, the filler may be a metal-based filler or not, but a metal-based filler is preferred. The polyorganosiloxane (B) has excellent adsorption properties to metal-based fillers, and when used with a metal-based filler, it can exert a more effective viscosity-reducing effect. The metal-based filler is a filler having a metal element, and may be a metal filler composed of the metal itself, or it may be a metal oxide, metal nitride, metal hydroxide, metal carbide, etc.

[0107] Examples of metal oxides include iron oxide, zinc oxide, aluminum oxide such as alumina, magnesium oxide, titanium oxide, cerium oxide, zirconium oxide, and manganese oxide such as manganese dioxide. Examples of metal nitrides include aluminum nitride, gallium nitride, chromium nitride, tungsten nitride, magnesium nitride, molybdenum nitride, and lithium nitride. Examples of metal carbides include aluminum carbide, titanium carbide, and tungsten carbide. Examples of metal hydroxides include aluminum hydroxide, calcium hydroxide, and magnesium hydroxide. Examples of metals include aluminum, titanium, iron, copper, silver, and gold. Metal fillers may be used individually or in combination of two or more types.

[0108] Preferred metal fillers include aluminum oxide, aluminum hydroxide, aluminum, manganese dioxide, zirconium oxide, and titanium oxide, with aluminum oxide and aluminum being more preferred among these.

[0109] The shape of the metallic filler is not particularly limited and may be any shape such as flake-like, spherical, polygonal, fibrous, or irregular, and may also be aggregated particles. The average primary particle diameter of the metallic filler is not particularly limited, but is preferably 0.1 μm to 200 μm, more preferably 0.5 μm to 100 μm, and even more preferably 0.5 μm to 50 μm. The particle size of the aggregated particles is also not particularly limited, and the average particle size of the aggregated particles is, for example, 0.1 μm to 250 μm, more preferably 0.5 μm to 200 μm, and even more preferably 1 μm to 150 μm. The primary particle diameter of the filler and the particle size of the aggregated particles can be determined by measuring the maximum diameter of the particles in an image obtained by observation with an electron microscope such as a TEM (transmission electron microscope) or SEM (scanning electron microscope). The average particle size, such as the average primary particle diameter, can be determined by the arithmetic mean of the maximum diameters of any 50 particles.

[0110] In addition, fillers other than metal fillers are not particularly limited, but include oxides other than metal oxides such as silicon oxide (silica), nitrides other than metal nitrides such as silicon nitride, carbides other than metal carbides such as silicon carbide and boron carbide, carbon materials, and diamond particles. Among these, boron nitride and carbon materials are preferred. Examples of boron nitride include hexagonal boron nitride, and more specifically, boron nitride nanotubes, boron nitride nanosheets, and hexagonal boron nitride particles. Hexagonal boron nitride particles are particulate boron nitride particles other than boron nitride nanosheets and boron nitride nanotubes, and their shape is not particularly limited; they may be flaky, spherical, polygonal, or irregularly shaped boron nitride particles. They may also be aggregated particles formed by the aggregation of multiple primary particles. Examples of carbon materials include carbon fibers such as graphitized carbon fibers, carbon nanotubes, carbon nanosheets, graphite such as graphite particles, graphene, and carbon black.

[0111] [Resin Composition] The present invention also provides a resin composition comprising the polyorganosiloxane, the filler described above, and a polyorganosiloxane other than the polyorganosiloxane (hereinafter also referred to as "polyorganosiloxane (X)"). The resin composition of the present invention, by comprising the polyorganosiloxane and the filler, allows the polyorganosiloxane to adsorb to the filler, and the polyorganosiloxane disperses the filler in the resin composition, thereby lowering the viscosity of the resin composition. Furthermore, the resin composition of the present invention, by comprising the filler, can impart, for example, excellent thermal conductivity to the resin composition. Moreover, since the polyorganosiloxane has two or more aliphatic unsaturated bonds in its molecule, it can appropriately form a crosslinking network in the resin composition and effectively suppress bleed-out. In the description of the resin composition, the resin composition comprising the polyorganosiloxane (A) will be described as the first embodiment, and the resin composition comprising the polyorganosiloxane (B) will be described as the second embodiment. Details of the fillers in the first and second embodiments are as described above. However, in the resin composition, polyorganosiloxane (A) and polyorganosiloxane (B) may be used in combination.

[0112] (First Embodiment) The content of the polyorganosiloxane (A) in the resin composition according to the first embodiment is, for example, 0.5 parts by mass or more and 50 parts by mass or less, preferably 1 part by mass or more and 40 parts by mass or less, and more preferably 3 parts by mass or more and 30 parts by mass or less, per 100 parts by mass of filler. When the content of the polyorganosiloxane (A) is above the lower limit, the filler is appropriately dispersed, making it easier to impart excellent thermal conductivity to the resin composition and to exhibit a viscosity-reducing effect. Furthermore, when the content of the polyorganosiloxane (A) is below the upper limit, it is easier to exhibit an effect commensurate with the content of the polyorganosiloxane (A), and bleed-out is less likely to occur.

[0113] The filler content in the resin composition according to the first embodiment is preferably 10% by mass or more and 95% by mass or less, based on the total amount of the resin composition. By keeping the filler content within the above range, it is possible to improve the thermal conductivity while maintaining a low viscosity of the resin composition. The filler content in the resin composition is more preferably 20% by mass or more and 90% by mass or less, and even more preferably 30% by mass or more and 85% by mass or less.

[0114] In the first embodiment, the filler preferably contains a π-electron filler as described above. In the resin composition, the filler may consist only of a π-electron filler, or a combination of a π-electron filler and a filler without π electrons may be used. The amount of π-electron filler in the resin composition is, for example, 1% by mass or more and 100% by mass or less, but preferably 10% by mass or more and 100% by mass or less, more preferably 30% by mass or more and 100% by mass or less, and even more preferably 50% by mass or more and 100% by mass or less.

[0115] (Second Embodiment) The content of the polyorganosiloxane (B) in the resin composition according to the second embodiment is, for example, 0.05 parts by mass or more and 40 parts by mass or less, preferably 0.1 parts by mass or more and 20 parts by mass or less, and more preferably 0.5 parts by mass or more and 15 parts by mass or less, per 100 parts by mass of filler. When the content of the polyorganosiloxane (B) is above the lower limit, the filler is appropriately dispersed, making it easier to impart excellent thermal conductivity to the resin composition and to exhibit a viscosity-reducing effect. Furthermore, when the content of the polyorganosiloxane (B) is below the upper limit, it is easier to exhibit an effect commensurate with the content of the polyorganosiloxane (B), and bleed-out is less likely to occur.

[0116] In the resin composition according to the second embodiment, the filler content is preferably 10% by mass or more and 95% by mass or less, based on the total amount of the resin composition. By keeping the filler content within the above range, it is possible to improve the thermal conductivity while maintaining a low viscosity of the resin composition. More preferably, the filler content in the resin composition according to the second embodiment is 20% by mass or more and 92% by mass or less, and even more preferably 30% by mass or more and 90% by mass or less.

[0117] In the second embodiment, the filler preferably includes a metal-based filler as described above. In the resin composition according to the second embodiment, the filler may consist only of a metal-based filler, or a combination of a metal-based filler and a filler other than a metal-based filler may be used. The amount of metal-based filler is, for example, 1% by mass or more and 100% by mass or less, of the total amount of filler contained in the resin composition, but preferably 10% by mass or more and 100% by mass or less, more preferably 30% by mass or more and 100% by mass or less, and even more preferably 50% by mass or more and 100% by mass or less.

[0118] [Polyorganosiloxane (X)] In each embodiment, a polyorganosiloxane (X) different from the polyorganosiloxane described herein may be used. The polyorganosiloxane (X) may serve as the matrix resin in the resin composition, and the filler may be dispersed in the polyorganosiloxane (X) and retained by the polyorganosiloxane (X).

[0119] Polyorganosiloxane (X) is a compound that does not have the structure of formula (1) described above in the first embodiment, and is typically a compound that does not have three to six conjugated aromatic six-membered rings. Polyorganosiloxane (X) is a compound that does not have the structure of formula (51) described above in the second embodiment, and is typically a compound that does not have a hydroxyl group. It is preferable that polyorganosiloxane (X) does not have either the structure of formula (1) or the structure of formula (51) described above. It is preferable that polyorganosiloxane (X) has a functional group that can react with the aliphatic unsaturated bond of R' described above, and such functional groups include acryloyl group, methacryloyl group, and hydrosilyl group. Among these, the hydrosilyl group is preferred. Note that the acryloyl group and methacryloyl group may react with the aliphatic unsaturated bond by radical reaction, for example. On the other hand, the hydrosilyl group may react with the aliphatic unsaturated bond by addition reaction. If polyorganosiloxane (X) contains a polyorganosiloxane having a functional group that can react with aliphatic unsaturated bonds such as a hydrosilyl group, then, for example during curing, the functional group of polyorganosiloxane (X) and the aliphatic unsaturated bonds of the polyorganosiloxane also react, effectively suppressing bleed-out.

[0120] The polyorganosiloxane (X) is preferably a curable polyorganosiloxane. In a curable polyorganosiloxane, the polyorganosiloxane (X) reacts with other components besides the polyorganosiloxane (A) to cure the resin composition. Examples of curable polyorganosiloxanes include condensation-curable polyorganosiloxanes and addition-curable polyorganosiloxanes, but addition-curable polyorganosiloxanes are preferred. Furthermore, the polyorganosiloxane (X) may have a branched structure or a linear structure.

[0121] Polyorganosiloxane (X) can be, for example, a polyorganosiloxane having an addition group. An addition group refers to a functional group that reacts by an addition reaction, and typical examples include alkenyl groups, methacryloyl groups, acryloyl groups, and hydrosilyl groups. Polyorganosiloxanes having an addition group are preferably used as addition-curable polyorganosiloxanes. Preferred examples of polyorganosiloxanes having an addition group include polyorganosiloxanes having alkenyl groups and polyorganosiloxanes having hydrosilyl groups.

[0122] Polyorganosiloxanes having alkenyl groups are addition-curing polyorganosiloxanes that harden when used in combination with polyorganosiloxanes having hydrosilyl groups. Polyorganosiloxanes having alkenyl groups may have one or more alkenyl groups in their molecule, preferably two or more. The alkenyl groups may be contained at the ends or in the middle of the molecular chain of the polysiloxane structure, or both ends and in the middle, but it is preferable that they be contained at least at the ends, and even more preferable that they be contained at both ends of the molecular chain of the polysiloxane structure. The alkenyl groups are not particularly limited, but examples include those having 2 to 8 carbon atoms, such as vinyl groups, allyl groups, butenyl groups, pentenyl groups, hexenyl groups, heptenyl groups, and octenyl groups. Among these, vinyl groups are preferred from the viewpoint of ease of synthesis and reactivity. Furthermore, the alkenyl group is preferably an alkenyl group directly bonded to a silicon atom.

[0123] In polyorganosiloxanes having alkenyl groups, examples of residual groups bonded to silicon atoms other than the alkenyl groups include alkyl groups having about 1 to 18 carbon atoms, such as methyl, ethyl, propyl, butyl, hexyl, and dodecyl groups; aryl groups having about 6 to 12 carbon atoms, such as phenyl groups; and aralkyl groups having about 7 to 18 carbon atoms, such as 2-phenylethyl and 2-phenylpropyl groups. Furthermore, substituted hydrocarbon groups such as chloromethyl and 3,3,3-trifluoropropyl groups are also given as specific examples. Of these, methyl groups are preferred from the viewpoint of ease of synthesis. It is also preferable that 80 mol% or more of the residual groups bonded to silicon atoms are methyl groups, more preferably 90 mol% or more are methyl groups, and even more preferably 100 mol% are methyl groups. Typically, polyorganosiloxanes having alkenyl groups do not contain hydrogen atoms as residual groups bonded to silicon atoms; that is, they do not contain hydrosilyl groups. Examples of polyorganosiloxanes having alkenyl groups include vinyl-terminated polydimethylsiloxanes, vinyl-terminated polyphenylmethylsiloxanes, vinyl-terminated dimethylsiloxane-diphenylsiloxane copolymers, vinyl-terminated dimethylsiloxane-phenylmethylsiloxane copolymers, vinyl-terminated dimethylsiloxane-diethylsiloxane copolymers, and other vinyl-terminated polyorganosiloxanes.

[0124] Polyorganosiloxanes having hydrosilyl groups are preferable to constitute an addition-curing type polyorganosiloxane that hardens when used in combination with the above-mentioned polyorganosiloxanes having alkenyl groups. Polyorganosiloxanes having hydrosilyl groups may have one or more hydrosilyl groups in the molecule. Hydrosilyl groups may be contained at the ends of the molecular chain of the polysiloxane structure, or in the middle of the molecular chain, or both ends and in the middle, but it is preferable to contain them at least at the ends, and more preferable to contain them at both ends of the molecular chain of the polysiloxane structure.Specific examples of residual groups that bond to silicon atoms other than the hydrosilyl groups in polyorganosiloxanes having hydrosilyl groups are as described for polyorganosiloxanes having alkenyl groups, and the explanation is omitted here. Furthermore, methyl groups are preferred as the residual groups, and the preferred proportion is as described for polyorganosiloxanes having alkenyl groups. Furthermore, polyorganosiloxanes containing hydrosilyl groups are typically preferable to be free of alkenyl groups.

[0125] Examples of polyorganosiloxanes having hydrosilyl groups include methylhydrosiloxane-dimethylsiloxane copolymer, polymethylhydrosiloxane, polyethylhydrosiloxane, and methylhydrosiloxane-phenylmethylsiloxane copolymer. These may or may not contain hydrosilyl groups at their terminal ends.

[0126] The polyorganosiloxane (X) may be a polyorganosiloxane that does not have an addition reaction group, for example, silicone oil. Examples of silicone oils include straight silicone oils such as dimethyl silicone oil (polydimethylsiloxane), polyphenylmethylsiloxane, dimethylsiloxane-diphenylsiloxane copolymer, and phenylmethylsiloxane oil such as dimethylsiloxane-phenylmethylsiloxane, as well as non-reactive modified silicone oils in which a non-reactive organic group is introduced into the main chain having a polysiloxane structure, the side chains attached to the main chain, or the ends of the main chain. A non-reactive organic group is an organic group that does not have an addition reaction group. Examples of non-reactive modified silicone oils include polyether-modified silicone oil, aralkyl-modified silicone oil, fluoroalkyl-modified silicone oil, long-chain alkyl-modified silicone oil, higher fatty acid ester-modified silicone oil, higher fatty acid amide-modified silicone oil, and phenyl-modified silicone oil. Among the above, straight silicone oil is preferred as the silicone oil, and among straight silicone oils, dimethyl silicone oil is more preferred. As the polyorganosiloxane (X), a combination of a polyorganosiloxane without an addition group and a polyorganosiloxane with an addition group may be used.

[0127] Furthermore, the polyorganosiloxane (X) may be other than those described above. In the first embodiment, for example, it may be a polyorganosiloxane having an alkoxy group or a polyorganosiloxane having a silanol group. In the second embodiment, for example, it may be a polyorganosiloxane having an alkoxy group.

[0128] Polyorganosiloxane (X) may be used alone from the above-mentioned types, or two or more types may be used in combination, but it is preferable to have a polyorganosiloxane having at least a hydrosilyl group as described above.

[0129] The polyorganosiloxane (X) has a number-average molecular weight of, for example, 1,000 to 50,000. Having a number-average molecular weight within this range allows for good coating and workability of the resin composition, while maintaining a consistent shape after coating or application, thus enabling the easy formation of a heat-dissipating material using the resin composition. Furthermore, it allows for lower viscosity of the resin composition, facilitates the appropriate dispersion and large-scale incorporation of fillers, and improves thermal conductivity. The number-average molecular weight of the polyorganosiloxane (X) is preferably 5,000 to 50,000, more preferably 7,000 to 40,000, and even more preferably 10,000 to 30,000. The number-average molecular weight is determined by gel permeation chromatography (GPC) measurement and converted to polystyrene equivalent.

[0130] The polyorganosiloxane (X) is preferably liquid at room temperature (25°C) and atmospheric pressure (1 atm). Being liquid makes it easier to improve the coating and workability of the resin composition. Furthermore, it allows for the proper dispersion of fillers while maintaining a low viscosity in the resin composition, making it easier to incorporate them in large quantities.

[0131] The resin composition may be curable or non-curable, but it is preferably curable. If it is curable, it may be a one-component curable or a two-component curable. If it is a one-component curable, the polyorganosiloxane (X) may contain a polyorganosiloxane as the main component and a polyorganosiloxane as the curing agent, and more specifically, it is preferable to contain a polyorganosiloxane having an alkenyl group and a polyorganosiloxane having a hydrosilyl group.

[0132] Furthermore, in the case of a two-component curing type, the resin composition may consist of either one of the two components. Therefore, the resin composition may contain either a polyorganosiloxane (X) as the main component or a polyorganosiloxane (X) as the curing agent. More specifically, the resin composition may contain either a polyorganosiloxane having an alkenyl group or a polyorganosiloxane having a hydrosilyl group. However, even in the case of a two-component curing type, the polyorganosiloxane (X) may contain, in addition to a polyorganosiloxane having an alkenyl group or a polyorganosiloxane having a hydrosilyl group, as long as curing does not progress. Also, in the case of a two-component curing type, the resin composition of the present invention may be obtained by mixing the first and second components.

[0133] In the case of a two-component type, it is preferable that both the first and second components consist of a resin composition containing the polyorganosiloxane, a filler, and polyorganosiloxane (X). Furthermore, it is preferable that the first component contains a polyorganosiloxane having an alkenyl group, and the second component contains a polyorganosiloxane having a hydrosilyl group.

[0134] Furthermore, the curable resin composition may contain a non-reactive polyorganosiloxane (X) as the polyorganosiloxane (X). For example, in addition to the above-mentioned polyorganosiloxane having an alkenyl group or a polyorganosiloxane having a hydrosilyl group, it may also contain a polyorganosiloxane that does not have an addition reaction group.

[0135] Furthermore, in the case of the non-curing type resin composition of the present invention, for example, silicone oil may be used as the polyorganosiloxane (X). Also, even in the case of the non-curing type, the polyorganosiloxane (X) may contain, in addition to silicone oil, a polyorganosiloxane having a functional group that can react with the aliphatic unsaturated bond of the polyorganosiloxane. Note that a portion of the polyorganosiloxane (X) may be a by-product generated in the process of producing the polyorganosiloxane. If the polyorganosiloxane (X) contains a by-product generated in the process of producing the polyorganosiloxane, it is preferable to further contain components other than the by-product.

[0136] The polyorganosiloxane (X) content in the resin composition is preferably 3% to 80% by mass, based on 100% by mass of the resin composition. By keeping the polyorganosiloxane (X) content within the above range, the thermal conductivity can be improved while appropriately retaining the filler with polyorganosiloxane (X). The polyorganosiloxane (X) content in the resin composition according to the first embodiment is more preferably 5% to 70% by mass, and even more preferably 10% to 60% by mass. Furthermore, the polyorganosiloxane (X) content in the resin composition according to the second embodiment is more preferably 5% to 70% by mass, and even more preferably 8% to 60% by mass.

[0137] (Curing Catalyst) The resin composition may further contain a curing catalyst. By containing a curing catalyst, the resin composition facilitates the formation of a crosslinked network with the polyorganosiloxane. Furthermore, if the polyorganosiloxane (X) is curable, the polyorganosiloxane (X) can be properly cured. Examples of curing catalysts include platinum catalysts, palladium catalysts, and rhodium catalysts, with platinum catalysts being preferred among these. As the platinum catalyst, any known catalyst may be used, but for example, platinum complexes of organosilicon compounds such as 1,3-diethenyl-1,1,3,3-tetramethyldisiloxane platinum complex are preferred. The content of the curing catalyst is usually 0.1 to 500 ppm, preferably 0.5 to 200 ppm, relative to the mass of the polyorganosiloxane (X). The curing catalyst is preferably used when the polyorganosiloxane (X) has a functional group that can react with the aliphatic unsaturated bond of R' described above, and in particular, it is preferable to use it when the polyorganosiloxane (X) contains a polyorganosiloxane having a hydrosilyl group.

[0138] (Additives) The resin composition of the present invention may contain additives other than the polyorganosiloxane, filler, polyorganosiloxane (X), and curing catalyst (other additives) as needed, to the extent that they do not impair the effects of the present invention. Specifically, additives such as alkoxysilane compounds, curing retarders, antioxidants, heat stabilizers, colorants, flame retardants, and antistatic agents may be included. Other additives may be used individually or in combination of two or more. The resin composition may be manufactured by mixing the polyorganosiloxane, filler, polyorganosiloxane (X), and additives as needed, by known methods.

[0139] The resin composition of the present invention has thermal conductivity and a viscosity-reducing effect, making it suitable for use as a heat dissipation material such as heat-dissipating silicone grease and heat-dissipating silicone sheet. Furthermore, the resin composition of the present invention is suitable for use in electronic devices to dissipate heat from various electronic components. Specifically, the resin composition of the present invention, when cured as needed, can be placed, for example, between an electronic component such as a semiconductor element and a heat sink to effectively dissipate heat generated from the electronic component. In addition, its high bleed resistance prevents bleed-out during use, making it less likely to contaminate electronic components.

[0140] The present invention will be described in more detail below with reference to examples, but the present invention is not limited in any way by these examples.

[0141] Synthesis Example 1 10 g of an organosiloxane compound having a silyl hydride group represented by formula (41) (l=10), 3 g of 1-pyrene methyl methacrylate as a monomer, 0.01 g of Karstedt catalyst (platinum-based catalyst) as a catalyst and solvent, and 50 g of toluene as a solvent were reacted at 100°C for 24 hours in a nitrogen atmosphere. Furthermore, 5 g of 2,4,6-trimethyl-2,4,6-trivinylcyclotrisiloxane and 0.1 g of p-toluenesulfonic acid monohydrate were added to the above reaction solution, and the reaction was further reacted at 100°C for 24 hours. The reaction solution was concentrated using a rotary evaporator and a vacuum dryer, and the concentrated residue was purified by silica gel column chromatography to obtain the polyorganosiloxane of Synthesis Example 1 (polyorganosiloxane (1)). １ ¹H NMR measurements confirmed that the following reaction proceeded and the target polyorganosiloxane was synthesized. A JEOL "ECX-400" NMR analyzer was used, with deuterated chloroform as the solvent, under the following conditions: sample concentration 5% by weight, temperature 25°C, measurement frequency 400 MHz, and 8 cumulative measurements. Similar reaction analysis was performed for other synthesis examples and comparative synthesis examples. １ This was confirmed by 1H NMR measurement. The reaction equation is as follows:

[0142]

[0143] Synthesis Example 2 10 g of an organosiloxane compound having a hydroxyl group represented by formula (42) (l=140), 0.6 g of 1-pylenebutanoic acid as monomer, 0.6 g of 2-methyl-6-nitrobenzoic anhydride, 0.4 g of 4-dimethylaminopyridine, and 200 g of tetrahydrofuran as a solvent were reacted in a nitrogen atmosphere at 25°C for 24 hours. The reaction mixture was concentrated using a rotary evaporator and a vacuum dryer, and purified by silica gel column chromatography. Then, 0.375 g of 2,4,6-trimethyl-2,4,6-trivinylcyclotrisiloxane, 0.1 g of p-toluenesulfonic acid monohydrate, and 10 g of toluene as a solvent were added, and the mixture was reacted further at 100°C for 24 hours. The reaction mixture was concentrated using a rotary evaporator and a vacuum dryer, and the concentrated residue was purified by silica gel column chromatography to obtain the polyorganosiloxane of Synthesis Example 2 (polyorganosiloxane (2)). The reaction equation is as follows:

[0144]

[0145] Synthesis Example 3 10 g of an organosiloxane compound having a 1,3-diol group represented by formula (43) (l=70), 0.5 g of 1-pyrenecarboxaldehyde as a monomer, 50 g of toluene as a solvent, and 0.1 g of a catalyst (Organo Corporation, "Amberlyst 15 dry") were reacted at 100°C for 24 hours in a nitrogen atmosphere. Furthermore, 0.75 g of 2,4,6-trimethyl-2,4,6-trivinylcyclotrisiloxane and 0.1 g of p-toluenesulfonic acid monohydrate were added to the reaction solution, and the reaction was continued at 100°C for another 24 hours. The reaction solution was concentrated using a rotary evaporator and a vacuum dryer, and the concentrated residue was purified by silica gel column chromatography to obtain the polyorganosiloxane of Synthesis Example 3 (polyorganosiloxane (3)). The reaction equation is as follows.

[0146]

[0147] Synthesis Example 4 10 g of an organosiloxane compound having a 1,3-diol group represented by formula (43) (l=210), 0.3 g of 9-anthracene carboxaldehyde as a monomer, 15 g of toluene as a solvent, and 0.1 g of a catalyst (Organo Corporation, "Amberlyst 15 dry") were reacted at 100°C for 24 hours in a nitrogen atmosphere. Furthermore, 0.25 g of 2,4,6-trimethyl-2,4,6-trivinylcyclotrisiloxane and 0.1 g of p-toluenesulfonic acid monohydrate were added to the reaction solution, and the reaction was continued at 100°C for another 24 hours. The reaction solution was concentrated using a rotary evaporator and a vacuum dryer, and the concentrated residue was washed with 30 g of acetone to obtain the polyorganosiloxane of Synthesis Example 4 (polyorganosiloxane (4)). The reaction equation is as follows.

[0148]

[0149] Synthesis Example 5: The synthesis was carried out in the same manner as in Synthesis Example 4, except that the monomer was changed to 0.3 g of 1-pyrenecarboxyaldehyde, to obtain the polyorganosiloxane of Synthesis Example 5 (polyorganosiloxane (5)). The reaction equation is the same as in Synthesis Example 3 and is therefore omitted.

[0150] Synthesis Example 6 The synthesis was carried out in the same manner as in Synthesis Example 4, except that the monomer was changed to 0.3 g of 3-perylene carboxyaldehyde, to obtain the polyorganosiloxane of Synthesis Example 6 (polyorganosiloxane (6)). The reaction equation is as follows.

[0151]

[0152] Synthesis Example 7 10 g of an organosiloxane compound having a 1,3-diol group represented by formula (43) (l=210), 0.3 g of 1-pyreneboronic acid as a monomer, and 15 g of toluene as a solvent were reacted at 100°C for 24 hours under a nitrogen atmosphere. Furthermore, 0.25 g of 2,4,6-trimethyl-2,4,6-trivinylcyclotrisiloxane and 0.1 g of p-toluenesulfonic acid monohydrate were added to the above reaction solution, and the reaction was further reacted at 100°C for 24 hours. The reaction solution was concentrated using a rotary evaporator and a vacuum dryer, and the concentrated residue was washed with 30 g of methanol and then with 30 g of acetone to obtain the polyorganosiloxane of Synthesis Example 7 (polyorganosiloxane (7)). The reaction equation is as follows.

[0153]

[0154] Synthesis Example 8 The synthesis was carried out in the same manner as in Synthesis Example 7, except that the monomer was changed to 0.4 g of 4-(1-pyrenyl)phenylboronic acid, to obtain the polyorganosiloxane of Synthesis Example 8 (polyorganosiloxane (8)). The reaction equation is as follows.

[0155]

[0156] Synthesis Example 9 The synthesis was carried out in the same manner as in Synthesis Example 7, except that the monomer was changed to 0.3 g of 2-p-terphenylboronic acid, to obtain the polyorganosiloxane of Synthesis Example 9 (polyorganosiloxane (9)). The reaction equation is as follows.

[0157]

[0158] Synthesis Example 10 The synthesis was carried out in the same manner as in Synthesis Example 7, except that the monomer was changed to 0.3 g of 5'-m-terphenylboronic acid, to obtain the polyorganosiloxane of Synthesis Example 10 (polyorganosiloxane (9)). The reaction equation is as follows.

[0159]

[0160] Synthesis Example 11 The synthesis was carried out in the same manner as in Synthesis Example 7, except that the monomer was changed to 0.4 g of 10-phenyl-9-anthraceneboronic acid, to obtain the polyorganosiloxane of Synthesis Example 11 (polyorganosiloxane (11)). The reaction equation is as follows.

[0161]

[0162] Synthesis Example 12 The synthesis was carried out in the same manner as in Synthesis Example 7, except that the monomer was changed to 0.4 g of 9,10-diphenylanthracene-2-boronic acid, to obtain the polyorganosiloxane (polyorganosiloxane (12)) of Synthesis Example 11. The reaction equation is as follows.

[0163]

[0164] Synthesis Example 13 The synthesis was carried out in the same manner as in Synthesis Example 7, except that the monomer was changed to 0.4 g of 10-(2-naphthyl)anthracene-9-boronic acid, to obtain the polyorganosiloxane (polyorganosiloxane (13)) from Synthesis Example 7. The reaction equation is as follows.

[0165]

[0166] Synthesis Example 14 The synthesis was carried out in the same manner as in Synthesis Example 7, except that 2,4,6-trimethyl-2,4,6-trivinylcyclotrisiloxane was replaced with 0.5 g of 2,4,6,8-tetra(3-acrylooxypropyl)-2,4,6,8-tetramethylcyclotetrasiloxane, to obtain the polyorganosiloxane of Synthesis Example 14 (polyorganosiloxane (14)). The reaction equation is as follows.

[0167]

[0168] Synthesis Example 15 The synthesis was carried out in the same manner as in Synthesis Example 7, except that 2,4,6-trimethyl-2,4,6-trivinylcyclotrisiloxane was replaced with 0.5 g of 2,4,6,8-tetra(3-methacrylateoxypropyl)-2,4,6,8-tetramethylcyclotetrasiloxane, to obtain the polyorganosiloxane of Synthesis Example 15 (polyorganosiloxane (15)). The reaction equation is as follows.

[0169]

[0170] Synthesis Example 16 was carried out in the same manner as in Synthesis Example 7, except that the amount of 2,4,6-trimethyl-2,4,6-trivinylcyclotrisiloxane was changed to 0.75 g, to obtain the polyorganosiloxane of Synthesis Example 16 (polyorganosiloxane (16)). The reaction equation is the same as in Synthesis Example 7 and is therefore omitted.

[0171] Synthesis Example 17 was carried out in the same manner as in Synthesis Example 7, except that the amount of 2,4,6-trimethyl-2,4,6-trivinylcyclotrisiloxane was changed to 1.25 g, to obtain the polyorganosiloxane of Synthesis Example 17 (polyorganosiloxane (17)). The reaction equation is the same as in Synthesis Example 7 and is therefore omitted.

[0172] Synthesis Example 18 was carried out in the same manner as in Synthesis Example 7, except that the amount of 2,4,6-trimethyl-2,4,6-trivinylcyclotrisiloxane was changed to 3.75 g and the amount of toluene was changed to 30 g, to obtain the polyorganosiloxane of Synthesis Example 18 (polyorganosiloxane (18)). The reaction equation is the same as in Synthesis Example 7 and is therefore omitted.

[0173] Synthesis Example 19 was carried out in the same manner as in Synthesis Example 7, except that the amount of 2,4,6-trimethyl-2,4,6-trivinylcyclotrisiloxane was changed to 6.25 g and the amount of toluene was changed to 40 g, to obtain the polyorganosiloxane of Synthesis Example 19 (polyorganosiloxane (19)). The reaction equation is the same as in Synthesis Example 7 and is therefore omitted.

[0174] Synthesis Example 20 was carried out in the same manner as in Synthesis Example 7, except that the amount of 2,4,6-trimethyl-2,4,6-trivinylcyclotrisiloxane was changed to 12.5 g and the amount of toluene was changed to 60 g, to obtain the polyorganosiloxane of Synthesis Example 20 (polyorganosiloxane (20)). The reaction equation is the same as in Synthesis Example 7 and is therefore omitted.

[0175] Synthesis Example 21 10 g of an organosiloxane compound having a 1,3-diol group represented by formula (43) (l=210), 0.3 g of 1-pyreneboronic acid as a monomer, and 15 g of toluene as a solvent were reacted at 100°C for 24 hours under a nitrogen atmosphere. Furthermore, 25 g of 2,4,6-trimethyl-2,4,6-trivinylcyclotrisiloxane, 12.5 g of octamethylcyclotetrasiloxane, and 0.1 g of p-toluenesulfonic acid monohydrate were added to the above reaction solution, and the reaction was further reacted at 100°C for 24 hours. The reaction solution was concentrated using a rotary evaporator and a vacuum dryer, and the concentrated residue was washed with 100 g of methanol and then with 100 g of acetone to obtain the polyorganosiloxane of Synthesis Example 21 (polyorganosiloxane (21)). The reaction equation is as follows.

[0176]

[0177] Synthesis Example 22 10 g of an organosiloxane compound having a 1,3-diol group represented by formula (43) (l=70), 0.9 g of 1-pyreneboronic acid as a monomer, and 45 g of toluene as a solvent were reacted at 100°C for 24 hours under a nitrogen atmosphere. Furthermore, 12.5 g of 2,4,6-trimethyl-2,4,6-trivinylcyclotrisiloxane and 0.1 g of p-toluenesulfonic acid monohydrate were added to the above reaction solution, and the reaction was further reacted at 100°C for 24 hours. The reaction solution was concentrated using a rotary evaporator and a vacuum dryer, and the concentrated residue was washed with 30 g of methanol and then with 30 g of acetone to obtain the polyorganosiloxane of Synthesis Example 22 (polyorganosiloxane (22)). The reaction formula is the same as in Synthesis Example 7 and is therefore omitted.

[0178] Synthesis Example 23 2.5 g of an organosiloxane compound having two hydroxyl groups represented by formula (44) (l=70), 0.6 g of 1-pylenebutanoic acid as monomer, 0.6 g of 2-methyl-6-nitrobenzoic anhydride, 0.4 g of 4-dimethylaminopyridine, and 200 g of tetrahydrofuran as solvent were reacted in a nitrogen atmosphere at 25°C for 24 hours. The reaction mixture was concentrated using a rotary evaporator and a vacuum dryer, purified by silica gel column chromatography, and then 0.2 g of 2,4,6-trimethyl-2,4,6-trivinylcyclotrisiloxane, 0.1 g of p-toluenesulfonic acid monohydrate, and 10 g of toluene as solvent were added, and the mixture was further reacted at 100°C for 24 hours. The reaction mixture was concentrated using a rotary evaporator and a vacuum dryer, and the concentrated residue was purified by silica gel column chromatography to obtain the polyorganosiloxane of Synthesis Example 23 (polyorganosiloxane (23)).

[0179]

[0180] Synthesis Example 24: The synthesis was carried out in the same manner as in Synthesis Example 23, except that the organosiloxane compound was changed to (l = 140) and the amount of 2,4,6-trimethyl-2,4,6-trivinylcyclotrisiloxane was changed to 0.1 g, to obtain the polyorganosiloxane of Synthesis Example 24 (polyorganosiloxane (24)). The reaction equation is the same as in Synthesis Example 23 and is therefore omitted.

[0181] Synthesis Example 25 10 g of an organosiloxane compound having a silyl hydride group represented by formula (45) (l=70, k=4), 3 g of 1-pyrene methyl methacrylate as a monomer, 0.01 g of Karstedt catalyst (platinum-based catalyst) as a solvent, and 50 g of toluene were reacted at 100°C for 24 hours in a nitrogen atmosphere. Furthermore, 1.5 g of 2,4,6-trimethyl-2,4,6-trivinylcyclotrisiloxane and 0.1 g of p-toluenesulfonic acid monohydrate were added to the above reaction solution, and the reaction was further reacted at 100°C for 24 hours. The reaction solution was concentrated using a rotary evaporator and a vacuum dryer, and the concentrated residue was purified by silica gel column chromatography to obtain the polyorganosiloxane of Synthesis Example 25 (polyorganosiloxane (25)). The reaction equation is as follows.

[0182]

[0183] Synthesis Example 26: The synthesis was carried out in the same manner as in Synthesis Example 25, except that the organosiloxane compound was exposed to (l=70, k=1), to obtain the polyorganosiloxane of Synthesis Example 26 (polyorganosiloxane (26)). The reaction equation is the same as in Synthesis Example 25 and is therefore omitted.

[0184] Comparative Synthesis Example 1 10 g of an organosiloxane compound having a 1,3-diol group represented by formula (43) (l=210), 0.3 g of 1-pyreneboronic acid as a monomer, and 15 g of toluene as a solvent were reacted at 100°C for 24 hours in a nitrogen atmosphere. The reaction solution was concentrated using a rotary evaporator and a vacuum dryer, and the concentrated residue was washed with 30 g of methanol and then with 30 g of acetone to obtain the polyorganosiloxane of Comparative Synthesis Example 1 (comparative polyorganosiloxane (1)). The reaction equation is as follows.

[0185]

[0186] Comparative Synthesis Example 2: The synthesis was carried out in the same manner as in Synthesis Example 7, except that the amount of 2,4,6-trimethyl-2,4,6-trivinylcyclotrisiloxane was changed to 0.125 g, to obtain the polyorganosiloxane of Comparative Synthesis Example 2 (Comparative Polyorganosiloxane (2)). The reaction equation is the same as in Synthesis Example 7 and is therefore omitted.

[0187] 10 g of an organosiloxane compound having a 1,3-diol group (l=210) represented by reference synthesis example formula (43), 0.25 g of 2,4,6-trimethyl-2,4,6-trivinylcyclotrisiloxane, 0.1 g of p-toluenesulfonic acid monohydrate, and 15 g of toluene as a solvent were reacted at 100°C for 24 hours under a nitrogen atmosphere. The reaction mixture was concentrated using a rotary evaporator and a vacuum dryer, and the concentrated residue was purified by silica gel column chromatography to obtain the polyorganosiloxane of the reference synthesis example (reference polyorganosiloxane). The reaction equation is as follows.

[0188] Synthesis Example 27: 10 g of an organosiloxane compound having a hydroxyl group represented by formula (70) (l=15), 3.5 g of 2,4,6-trimethyl-2,4,6-trivinylcyclotrisiloxane, 0.1 g of p-toluenesulfonic acid monohydrate, and 50 g of toluene as a solvent were reacted at 100°C for 24 hours under a nitrogen atmosphere. The reaction mixture was concentrated using a rotary evaporator and a vacuum dryer, and the concentrated residue was purified by silica gel column chromatography to obtain the polyorganosiloxane of Synthesis Example 27 (polyorganosiloxane (27)). １ ¹H NMR measurements confirmed that the following reaction proceeded and the target polyorganosiloxane was synthesized. A JEOL "ECX-400" NMR analyzer was used, with deuterated chloroform as the solvent, under the following conditions: sample concentration of 5% by weight, temperature of 25°C, measurement frequency of 400 MHz, and 8 integration cycles. The reaction equation is shown below.

[0189]

[0190] Synthesis Example 28: The synthesis was carried out in the same manner as in Synthesis Example 27, except that the organosiloxane compound was changed to one with l=70 and the amount of 2,4,6-trimethyl-2,4,6-trivinylcyclotrisiloxane was changed to 0.75 g, to obtain the polyorganosiloxane of Synthesis Example 28 (polyorganosiloxane (28)). The reaction equation is the same as in Synthesis Example 27 and is therefore omitted.

[0191] Synthesis Example 29: The synthesis was carried out in the same manner as in Synthesis Example 27, except that the organosiloxane compound was changed to one with l=140 and the amount of 2,4,6-trimethyl-2,4,6-trivinylcyclotrisiloxane was changed to 0.375 g, to obtain the polyorganosiloxane of Synthesis Example 29 (polyorganosiloxane (29)). The reaction equation is the same as in Synthesis Example 27 and is therefore omitted.

[0192] Synthesis Example 30 10 g of an organosiloxane compound having a 1,3-diol group represented by formula (71) (l=70), 0.75 g of 2,4,6-trimethyl-2,4,6-trivinylcyclotrisiloxane, 0.1 g of p-toluenesulfonic acid monohydrate, and 50 g of toluene as a solvent were reacted at 100°C for 24 hours in a nitrogen atmosphere. The reaction mixture was concentrated using a rotary evaporator and a vacuum dryer, and the concentrated residue was purified by silica gel column chromatography to obtain the polyorganosiloxane of Synthesis Example 30 (polyorganosiloxane (30)). The reaction equation is as follows.

[0193]

[0194] Synthesis Example 31 The synthesis was carried out in the same manner as in Synthesis Example 30, except that the organosiloxane compound was changed to one with (l=210) and the amount of 2,4,6-trimethyl-2,4,6-trivinylcyclotrisiloxane was changed to 0.25 g, to obtain the polyorganosiloxane of Synthesis Example 31 (polyorganosiloxane (31)). The reaction equation is the same as in Synthesis Example 30 and is therefore omitted.

[0195] Synthesis Example 32 The synthesis was carried out in the same manner as in Synthesis Example 31, except that 2,4,6-trimethyl-2,4,6-trivinylcyclotrisiloxane was replaced with 0.5 g of 2,4,6,8-tetra(3-acrylooxypropyl)-2,4,6,8-tetramethylcyclotetrasiloxane, to obtain the polyorganosiloxane of Synthesis Example 32 (polyorganosiloxane (32)). The reaction equation is as follows.

[0196]

[0197] Synthesis Example 33 was carried out in the same manner as in Synthesis Example 31, except that 2,4,6-trimethyl-2,4,6-trivinylcyclotrisiloxane was replaced with 0.5 g of 2,4,6,8-tetra(3-methacrylateoxypropyl)-2,4,6,8-tetramethylcyclotetrasiloxane, to obtain the polyorganosiloxane of Synthesis Example 33 (polyorganosiloxane (33)). The reaction equation is as follows.

[0198]

[0199] Synthesis Example 34 was carried out in the same manner as in Synthesis Example 31, except that the amount of 2,4,6-trimethyl-2,4,6-trivinylcyclotrisiloxane was changed to 0.75 g, to obtain the polyorganosiloxane of Synthesis Example 34 (polyorganosiloxane (34)). The reaction equation is the same as in Synthesis Example 30 and is therefore omitted.

[0200] Synthesis Example 35 was carried out in the same manner as in Synthesis Example 31, except that the amount of 2,4,6-trimethyl-2,4,6-trivinylcyclotrisiloxane was changed to 1.25 g, to obtain the polyorganosiloxane of Synthesis Example 35 (polyorganosiloxane (35)). The reaction equation is the same as in Synthesis Example 30 and is therefore omitted.

[0201] Synthesis Example 36 was carried out in the same manner as in Synthesis Example 31, except that the amount of 2,4,6-trimethyl-2,4,6-trivinylcyclotrisiloxane was changed to 3.75 g, to obtain the polyorganosiloxane of Synthesis Example 36 (polyorganosiloxane (36)). The reaction equation is the same as in Synthesis Example 30 and is therefore omitted.

[0202] Synthesis Example 37 was carried out in the same manner as in Synthesis Example 31, except that the amount of 2,4,6-trimethyl-2,4,6-trivinylcyclotrisiloxane was changed to 6.25 g, to obtain the polyorganosiloxane of Synthesis Example 37 (polyorganosiloxane (37)). The reaction equation is the same as in Synthesis Example 30 and is therefore omitted.

[0203] Synthesis Example 38 was carried out in the same manner as in Synthesis Example 31, except that the amount of 2,4,6-trimethyl-2,4,6-trivinylcyclotrisiloxane was changed to 12.5 g, to obtain the polyorganosiloxane of Synthesis Example 38 (polyorganosiloxane (38)). The reaction equation is the same as in Synthesis Example 30 and is therefore omitted.

[0204] Synthesis Example 39 15 g of an organosiloxane compound having a 1,3-diol group represented by formula (71) (l=210), 25 g of 2,4,6-trimethyl-2,4,6-trivinylcyclotrisiloxane, 12.5 g of octamethylcyclotetrasiloxane, 0.1 g of p-toluenesulfonic acid monohydrate, and 150 g of toluene as a solvent were reacted at 100°C for 24 hours in a nitrogen atmosphere. The reaction solution was concentrated using a rotary evaporator and a vacuum dryer, and the concentrated residue was washed with 100 g of methanol and then with 100 g of acetone to obtain the polyorganosiloxane of Synthesis Example 39 (polyorganosiloxane (39)). The reaction equation is as follows.

[0205]

[0206] Synthesis Example 40 was carried out in the same manner as in Synthesis Example 30, except that the amount of 2,4,6-trimethyl-2,4,6-trivinylcyclotrisiloxane was changed to 12.5 g, to obtain the polyorganosiloxane of Synthesis Example 40 (polyorganosiloxane (40)). The reaction equation is the same as in Synthesis Example 30 and is therefore omitted.

[0207] Comparative Synthesis Example 3 A commercially available organosiloxane compound represented by the following formula (72) (l=70) was obtained as a comparative polyorganosiloxane (3).

[0208] Comparative Synthesis Example 4 A commercially available organosiloxane compound represented by the following formula (71) (l=210) was obtained as a comparative polyorganosiloxane (4).

[0209] Comparative Synthesis Example 5: The synthesis was carried out in the same manner as in Synthesis Example 31, except that the amount of 2,4,6-trimethyl-2,4,6-trivinylcyclotrisiloxane was changed to 0.25 g, to obtain the polyorganosiloxane of Comparative Synthesis Example 5 (Comparative Polyorganosiloxane (5)). The reaction equation is the same as in Synthesis Example 30 and is therefore omitted.

[0210] The polyorganosiloxanes (1) to (26), comparative polyorganosiloxanes (1) and (2), and reference polyorganosiloxanes obtained in Examples 1 to 26, Comparative Examples 1 and 2, and Reference Example 1 were used to evaluate viscosity reduction and bleed resistance using the following evaluation methods.

[0211] [Thickness Reduction Evaluation Method 1] The materials used were as follows: (1) Filler: Graphite (average particle size 10 μm, flaky), 75 parts by mass (2) Matrix resin (polyorganosiloxane (X)): Polyorganosiloxane represented by the following formula (n=160), 100 parts by mass

[0212] (3) Dispersant: 11 parts by mass of the polyorganosiloxane obtained in each synthesis example.

[0213] (Procedure) A resin composition was prepared by kneading each material in the above-mentioned mass, and 30 g of the degassed resin composition was introduced into a cylindrical container with a diameter of 25 mm. Next, a piercing rod (with a diameter of 1.8 mm) having a disc-shaped member with a diameter of 2 mm and a thickness of 1 mm at its tip was pressed against the resin composition introduced into the container from the tip side of the piercing rod at a speed of 10 mm / min (piercing speed), and the load (mN) when the tip of the piercing rod reached a depth of 10 mm from the liquid surface was measured. Based on the measured load, the following evaluation criteria were used. The material of the piercing rod was stainless steel. The measurement was performed at 25°C, and the load measurement was performed using an IMADA "ZTS-5N". AA: 50 mN or less A: Greater than 50 mN and 70 mN or less B: Greater than 70 mN and 100 mN or less C: Greater than 100 mN

[0214] [Bleed Evaluation Method 1] The materials used were as follows: (1) Filler: Graphite (average particle size 10 μm, flaky), 75 parts by mass (2) Matrix resin (polyorganosiloxane (X)): 75 parts by mass of polyorganosiloxane (n=160) represented by the following formula,

[0215] 25 parts by mass of a polyorganosiloxane represented by the following formula (m=19, n=1).

[0216]

[0217] (3) Platinum catalyst: 1,3-diethenyl-1,1,3,3-tetramethyldisiloxane platinum complex, 0.01 parts by mass (4) Dispersant: Polyorganosiloxane obtained in each synthesis example, 11 parts by mass

[0218] Procedure A resin composition was prepared by kneading each material in the above proportions and molded into a sheet with a radius of 2 cm and a thickness of 2 mm. The sheet was heated at 150°C for 6 hours to cure, and then its weight was measured. The sheet was compressed to a thickness of 1 mm and heated at 150°C for 24 hours. After heating, the sheet was washed with cyclohexane to remove bleed components, dried, and then weighed. The ratio of weight loss to the total amount of matrix resin and dispersant used in composition preparation was calculated. Based on the calculated ratio (weight %), the following evaluation criteria were used: AA: 0.5% by weight or less A: Greater than 0.5% by weight and 0.75% by weight or less B: Greater than 0.75% by weight and 1% by weight or less C: Greater than 1% by weight.

[0219]

[0220] As is clear from the above examples, the polyorganosiloxane having three to six conjugated aromatic six-membered rings and two or more aliphatic unsaturated bonds exhibited a high viscosity-reducing effect while appropriately suppressing bleed-out. In contrast, the polyorganosiloxanes in Comparative Examples 1 and 2 lacked or had only one aliphatic unsaturated bond, and therefore could not properly form a cross-linked structure, failing to sufficiently suppress bleed-out. Furthermore, the polyorganosiloxane in the Reference Example lacked three to six conjugated aromatic six-membered rings, resulting in an insufficient viscosity-reducing effect on the graphite filler.

[0221] Examples 27-40, Comparative Examples 3-5: Using the polyorganosiloxanes (27)-(40) and comparative polyorganosiloxanes (3)-(5) obtained in Synthesis Examples 27-40 and Comparative Synthesis Examples 3-5, viscosity reduction and bleed resistance were evaluated using the following evaluation methods.

[0222] [Thickness Reduction Evaluation Method 2] The same procedure as in Thickness Reduction Evaluation Method 1 was followed, except that a resin composition was prepared by adding 650 parts by mass of aluminum oxide (average particle size 10 μm, spherical) instead of 75 parts by mass of graphite as a filler. The evaluation criteria in Thickness Reduction Evaluation Method 2 are as follows: AA: 75 mN or less A: Greater than 75 mN and 100 mN or less B: Greater than 100 mN and 150 mN or less C: Greater than 150 mN

[0223] [Bleed Evaluation Method 2] The same procedure as in Bleed Evaluation Method 1 was followed, except that a resin composition was used in which 650 parts by mass of aluminum oxide (average particle size 10 μm, spherical) was added instead of 75 parts by mass of graphite as a filler. The evaluation criteria in Bleed Evaluation Method 2 are as follows: AA: 0.5% by weight or less A: Greater than 0.5% by weight and 0.75% by weight or less B: Greater than 0.75% by weight and 1% by weight or less C: Greater than 1% by weight.

[0224]

[0225] As is clear from Examples 27 to 40 above, the polyorganosiloxane having a hydroxyl group at the terminal and two or more aliphatic unsaturated bonds in the side chain exhibited a high viscosity-reducing effect while appropriately suppressing bleed-out. In contrast, the polyorganosiloxane in Comparative Example 3 lacked both a hydroxyl group and aliphatic unsaturated bonds, resulting in insufficient viscosity reduction and bleed-out resistance. Furthermore, the polyorganosiloxanes in Comparative Examples 4 and 5 lacked or had only one aliphatic unsaturated bond, and therefore could not properly form a cross-linked structure, failing to adequately suppress bleed-out.

Claims

1. A polyorganosiloxane having a structure represented by the following formula (1). (In formula (1), each R is independently substituted with substituent A or is a monovalent saturated hydrocarbon group having 1 to 4 carbon atoms, with at least one R being substituted with substituent A, and R' being a monovalent organic group having an aliphatic unsaturated bond. Substituents A are monovalent organic groups having 3 to 6 conjugated aromatic 6-membered rings, l is an integer of 1 or more, and m and n are integers of 0 or more, with at least one of them being 1 or more. Also, in formula (1), the number of aliphatic unsaturated bonds is 2 or more.) 2. The polyorganosiloxane according to claim 1, wherein each R' independently comprises at least one selected from the group consisting of a vinyl group, an acryloyl group, and a methacryloyl group.

3. The polyorganosiloxane according to claim 1 or 2, wherein l + m + n is 10 or more and 500 or less.

4. The polyorganosiloxane according to claim 1 or 2, wherein (m+n) / l is 0.001 or more and 0.5 or less.

5. The polyorganosiloxane according to claim 1 or 2, which is represented by the following formula (2). (In formula (2), R, A, R', l, m and n are the same as described above.) 6. The polyorganosiloxane according to claim 1 or 2, represented by the following formula (3). (In equation (3), R, A, R', l, m, and n are the same as above.) 7. The polyorganosiloxane according to claim 1 or 2, represented by the following formula (4). (In equation (4), R, A, R', l, m, and n are the same as above, and k is an integer from 1 to 10.) 8. The polyorganosiloxane according to claim 7, wherein k in formula (4) is 1 or 2.

9. A resin composition comprising a polyorganosiloxane according to claim 1 or 2, a polyorganosiloxane other than the polyorganosiloxane, and a π-electron filler.

10. The resin composition according to claim 9, further comprising a platinum catalyst.

11. A polyorganosiloxane having a structure represented by the following formula (51). (In formula (51), R is independently a monovalent saturated hydrocarbon group having 1 to 4 carbon atoms, R' is a monovalent organic group having an aliphatic unsaturated bond, and A is a monovalent organic group having at least one hydroxyl group. l is an integer of 1 or more, m and n are integers of 0 or more, and at least one of them is 1 or more. In formula (51), the number of aliphatic unsaturated bonds is 2 or more.) 12. The polyorganosiloxane according to claim 11, wherein A contains two or more hydroxyl groups.

13. The polyorganosiloxane according to claim 12, wherein the two hydroxyl groups in A constitute at least one of a 1,2-diol structure and a 1,3-diol structure.

14. A polyorganosiloxane having a structure represented by the following formula (52). (In equation (52), l is an integer greater than or equal to 1, and m is an integer greater than or equal to 2.)

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