Organopolysiloxane, method for producing the same, and dispersion liquid containing the organopolysiloxane as a dispersant

Abstract

Provided is a dispersant capable of imparting, to fillers, excellent dispersibility in liquid media.　The dispersant is an organopolysiloxane represented by formula (1) or (2). In formulae (1) and (2), R1 is a C1-C12 saturated hydrocarbon group; X is a group represented by formula (3), acryloyl, alkyl, carboxyl, vinyl, methacryl, aromatic group, amino, isocyanate, isocyanurate, epoxy, hydroxyl, or mercapto and at least one of the X moieties is a group represented by formula (3); m, l, and k are each 0-10; and j is 1-10. In formula (3), R2 is a C1-C12 saturated hydrocarbon group or a C6-C12 aromatic hydrocarbon group, Y is a C1-C8 divalent hydrocarbon group, and h is 4-400.

Description

Technical Field

[0001] The present invention relates to an organopolysiloxane having a partial structure in which T-structural units are continuously connected and a method for producing the same, and to a filler dispersion liquid comprising the organopolysiloxane as a dispersant capable of imparting excellent filler dispersibility in a liquid medium.

Background Art

[0002] Examples of products using liquid media such as hydrocarbons, alkanols, alkenols, fatty acids, unsaturated fatty acids, esters of fatty acids and hydroxyl group-containing compounds, esters of unsaturated fatty acids and hydroxyl group-containing compounds, and silicone oils, acrylic resins, epoxy resins, and urethane resins include cosmetics, liquid toners, oil-based inkjet inks, weak solvent-based paints, lubricating oils, detergents, heat conductive materials, conductive materials, and optical materials. Further, by dispersing fillers such as pigments in these liquid media, functions corresponding to the applications are imparted.

[0003] For example, in recent years, with the high density and high integration of printed circuit boards and hybrid ICs incorporating electronic components such as transistors, ICs, and memory elements, and the increase in the capacity of secondary batteries (cell type), in order to efficiently dissipate the heat generated from electronic and electrical devices such as electronic components and batteries, as a heat conduction material, a thermally conductive silicone composition composed of organopolysiloxane and thermally conductive fillers such as aluminum oxide powder and zinc oxide powder has been widely used. And in particular, in order to cope with a high heat dissipation amount, a thermally conductive silicone composition filled with a large amount of thermally conductive filler has been proposed. However, in order to reduce the thermal resistance or improve the thermal conductivity, even if the filling rate of the thermally conductive filler filled in the heat dissipation grease, heat dissipation sheet, etc. is improved, the viscosity of the resin composition used in the heat dissipation grease, heat dissipation sheet, etc. increases, and it becomes difficult to discharge the resin composition. Therefore, until now, various studies have been made on the combination of the thermally conductive fillers to be filled in order to reduce the thermal resistance or increase the thermal conductivity of the heat dissipation grease, heat dissipation sheet, etc. (see Patent Document 1, Patent Document 2, and Patent Document 3). However, in the combinations of the thermally conductive fillers conventionally studied, from the viewpoint of thermal conductivity, they were not sufficient, or even if the thermal conductivity was high, the viscosity was high, and there was nothing that could achieve both of these.

[0004] In order to solve that problem, Patent Document 4 describes that in a thermally conductive silicone composition filled with a thermally conductive filler, an organopolysiloxane having trimethoxysilyl at one end has a role of reducing the viscosity of the composition and imparting fluidity, and it is used as a dispersant to reduce the viscosity and impart fluidity.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

Patent Document 3

[0006] The present invention relates to an organopolysiloxane having a partial structure in which T-structural units are continuously connected and a method for producing the same, and relates to a filler dispersion liquid containing an organopolysiloxane having a partial structure in which T-structural units are continuously connected as a dispersant capable of imparting better filler dispersibility in a liquid medium than an organopolysiloxane having trimethoxysilyl at one end. The problem of the present invention is to provide a dispersant capable of imparting excellent filler dispersibility in a liquid medium. Another problem of the present invention is to provide a filler dispersion liquid in which the filler is stably dispersed, obtained by using the above dispersant. [Means for Solving the Problems]

[0007] As a result of intensive studies to solve the above problems, the present inventors have found that an organopolysiloxane having a partial structure in which T-structural units are continuously connected is useful as a dispersant, and have completed the present invention. That is, according to the present invention, an organopolysiloxane having a partial structure in which the following T-structural units are continuously connected is provided as a dispersant.

[0008] The present invention is as follows. Item 1. An organopolysiloxane represented by formula (1) or (2). TIFF0007704152000001.tif46168 TIFF0007704152000002.tif4669 In formulas (1) and (2), R 1 is independently a saturated hydrocarbon group having 1 to 12 carbon atoms, X is independently a group represented by formula (3), acryloyl, alkyl, carboxyl, vinyl, methacryl, aromatic group, amino, isocyanate, isocyanurate, epoxy, hydroxyl, or mercapto, and at least one X is a group represented by formula (3), m, l, and k are independently 0 to 10, j is 1 to 10; TIFF0007704152000003.tif2674 In formula (3), R 2 is independently a saturated hydrocarbon group having 1 to 12 carbon atoms, or an aromatic hydrocarbon group having 6 to 12 carbon atoms, Y is a divalent hydrocarbon group having 1 to 8 carbon atoms, h is 4 to 400.

[0009] Item 2. The organopolysiloxane according to Item 1, which is a reaction product of an organopolysiloxane represented by formula (4) and a trialkoxysilane. TIFF0007704152000004.tif2387 In formula (4), R 1 is independently a saturated hydrocarbon group having 1 to 12 carbon atoms, R 2 is independently a saturated hydrocarbon group having 1 to 12 carbon atoms, or an aromatic hydrocarbon group having 6 to 12 carbon atoms, Y is a divalent hydrocarbon group having 1 to 8 carbon atoms, h is 4 to 400.

[0010] Item 3. A method for producing the organopolysiloxane according to Item 2, which comprises reacting an organopolysiloxane represented by formula (4) with a trialkoxysilane.

[0011] Item 4. The organopolysiloxane according to Item 1, in which the organopolysiloxane represented by formula (4) according to Item 2 has reacted intermolecularly.

[0012] Item 5. The method for producing an organopolysiloxane according to Item 3, wherein the organopolysiloxane represented by the formula (4) according to Item 2 is reacted intermolecularly.

[0013] Item 6. The method for producing an organopolysiloxane according to Item 3 or 5, wherein an organometallic catalyst is used as a catalyst.

[0014] Item 7. The organopolysiloxane according to Item 1, which is a reaction product of the organopolysiloxane represented by the formula (5) and an alkoxysilane oligomer having vinyl. TIFF0007704152000005.tif2379 In the formula (5) R 2 is independently a saturated hydrocarbon group having 1 to 12 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms, h is from 4 to 400.

[0015] Item 8. The method for producing an organopolysiloxane according to Item 1, wherein the organopolysiloxane represented by the formula (5) according to Item 7 is reacted with an alkoxysilane oligomer having vinyl.

[0016] Item 9. A dispersant used for dispersing a filler in a liquid medium and comprising the organopolysiloxane according to Item 1.

[0017] Item 10. The dispersant according to Item 9, having a number average molecular weight (Mn) of 500 to 100,000.

[0018] Item 11. The dispersant according to Item 9 or 10, having a molecular weight distribution index (Mw / Mn) of 1.0 to 3.0.

[0019] Item 12. A filler dispersion liquid containing a filler, a liquid medium, and the organopolysiloxane according to Item 1.

[0020] Item 13. The filler dispersion liquid according to Item 12, wherein the content of the liquid medium is 4 to 50 parts by mass and the content of the dispersant is 0.1 to 20 parts by mass with respect to 100 parts by mass of the filler.

Advantages of the Invention

[0021] According to the present invention, a dispersant capable of stably dispersing a filler in a liquid medium can be provided. Furthermore, according to the present invention, a filler dispersion liquid in which the filler is stably dispersed, obtained by using the above dispersant, can be provided. The filler dispersion liquid of the present invention is useful, for example, as cosmetics, liquid developers, oil-based inkjet inks, ultraviolet curable inkjet inks, weak solvent-based paints, offset inks, lubricants, cleaning agents, insecticides, release agents, adhesives, heat conductive materials, conductive materials, optical materials, and the like.

Brief Description of the Drawings

[0022]

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Mode for Carrying Out the Invention

[0023] Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to the following embodiments.

[0024] <Dispersant> The dispersant of the present invention is an organopolysiloxane having a partial structure in which T structural units [R1SiO 3 / 2 represented by the formula (1) or (2) are continuously connected. TIFF0007704152000006.tif46168 TIFF0007704152000007.tif4669 In formulas (1) and (2), R 1 is independently a saturated hydrocarbon group having 1 to 12 carbon atoms, X is independently a group represented by formula (3), acryloyl, alkyl, carboxyl, vinyl, methacryl, aromatic group, amino, isocyanate, isocyanurate, epoxy, hydroxyl, or mercapto, and at least one X is a group represented by formula (3), m, l, and k are independently 0 to 10, j is 1 to 10.

[0025] TIFF0007704152000008.tif2674 In formula (3), R 2 is independently a saturated hydrocarbon group having 1 to 12 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms, Y is a divalent hydrocarbon group having 1 to 8 carbon atoms, h is 4 to 400.

[0026] The definitions of the M structural unit, D structural unit, T structural unit, and Q structural unit are related to the number of bonded oxygen atoms and are exemplified, for example, for silyl units as follows: M = monofunctional unit [R3SiO 1 / 2 , D = difunctional unit [R2SiO 2 / 2 , T = trifunctional unit [R1SiO 3 / 2 , Q = tetrafunctional unit [SiO 4 / 2 .

[0027] For an organopolysiloxane having a partial structure in which T structural units [R1SiO 3 / 2 represented by formula (1) or (2) are continuously connected, the T structural unit [R1SiO 3 / 2Structures that can be considered as partially structured parts connected continuously can be exemplified by Formula (7) or (8) as Formula (1), and Formula (9) as Formula (2), for the purpose of merely listing several possible possibilities.

[0028] TIFF0007704152000009.tif2872 TIFF0007704152000010.tif5994 TIFF0007704152000011.tif5992

[0029] In Formulas (7) to (9), R 1 is independently a monovalent saturated hydrocarbon group having 1 to 12 carbon atoms, X is independently a group represented by Formula (3), acryloyl, alkyl, carboxyl, vinyl, methacryl, aromatic group, amino, isocyanate, isocyanurate, epoxy, hydroxyl, or mercapto. And at least one X is a group represented by Formula (3).

[0030] TIFF0007704152000012.tif2674 In Formula (3), R 2 is independently a saturated hydrocarbon group having 1 to 12 carbon atoms, or an aromatic hydrocarbon group having 6 to 12 carbon atoms, Y is independently a divalent hydrocarbon group having 1 to 8 carbon atoms, h is independently 4 to 400.

[0031] The definition of the T structural unit, which is a partial structure in Formulas (7) to (9), is related to the number of alkoxy groups and is classified into, for example, four types of formulas represented by Formula (10). TIFF0007704152000013.tif6279

[0032] <Method for Producing Organopolysiloxane Having Partially Structured Part with Continuously Connected T Structural Units> The organopolysiloxane having a partial structure in which the T-structural units of the present invention are continuously connected can be synthesized from an organopolysiloxane having a trialkoxysilyl group at one end represented by the formula (4) and an alkoxysilane compound having three alkoxys. Further, the organopolysiloxane may be a compound in which the organopolysiloxane having a trialkoxysilyl group at one end represented by the formula (4) reacts intermolecularly. For the reaction, a solvent can be used as necessary, and as the catalyst, an acid catalyst such as hydrochloric acid or an alkali catalyst such as ammonia can be used for the purpose of hydrolysis, but it is preferable to use an organometallic catalyst.

[0033] TIFF0007704152000014.tif2387 In formula (4), R 1 is independently a saturated hydrocarbon group having 1 to 12 carbon atoms, R 2 is independently a saturated hydrocarbon group having 1 to 12 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms. Y is independently a divalent hydrocarbon group having 1 to 8 carbon atoms. h is independently 4 to 400.

[0034] One or more organopolysiloxanes having trialkoxysilyl at one end can be used. Further, the organopolysiloxane having trialkoxysilyl at one end can be produced by a conventionally known technique. For example, there is a method of synthesizing an organopolysiloxane having trialkoxysilyl at one end with an arbitrary molecular weight from an organopolysiloxane having hydrosilyl at one end with an arbitrary molecular weight and vinyltrialkoxysilane in the presence of a platinum catalyst. Examples of the organopolysiloxane having hydrosilyl at one end include FM-0105 (number average molecular weight (Mn) = about 500), FM-0111 (number average molecular weight (Mn) = about 1000), FM-0121 (number average molecular weight (Mn) = about 5000), FM-0125 (number average molecular weight (Mn) = about 10000), FM-0126 (number average molecular weight (Mn) = about 20000), FM-0127 (number average molecular weight (Mn) = about 30000), etc. manufactured by JNC Corporation. Examples of vinyltrialkoxysilane include vinyltrimethoxysilane (S210 manufactured by JNC Corporation) and vinyltriethoxysilane (S220 manufactured by JNC Corporation).

[0035] Regarding the organopolysiloxane having trialkoxysilyl at one end, examples of the trialkoxysilyl include trimethoxysilyl, triethoxysilyl, tripropoxysilyl, etc. Among these, from the viewpoints of the affinity between the dispersant, which is an organopolysiloxane having a partial structure in which the synthesized T structural units are continuously connected, and the filler, and the availability of vinylalkoxysilane, which is a raw material for producing the organopolysiloxane having trialkoxysilyl at one end, trimethoxysilyl is preferable.

[0036] The alkoxysilane compound having three alkoxys may be used singly or in combination of two or more. Examples of the alkoxysilane compound having three alkoxys include alkyl-containing alkoxysilane compounds, vinyl-containing alkoxysilane compounds, acryloyl-containing alkoxysilane compounds, methacryl-containing alkoxysilane compounds, aromatic group-containing alkoxysilane compounds, amino-containing alkoxysilane compounds, isocyanate-containing alkoxysilane compounds, isocyanurate-containing alkoxysilane compounds, epoxy-containing alkoxysilane compounds, and mercapto-containing alkoxysilane compounds.

[0037] Examples of the alkyl-containing alkoxysilane compounds include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, n-octyltriethoxysilane, and n-decyltrimethoxysilane. Examples of the vinyl-containing alkoxysilane compounds include vinyltrimethoxysilane and vinyltriethoxysilane. Examples of the acryloyl-containing alkoxysilane compounds include 3-acryloxypropyltrimethoxysilane. Examples of the methacryloyl-containing alkoxysilane compounds include 3-methacryloxypropyltrimethoxysilane and 3-methacryloxypropyltriethoxysilane. Examples of the aromatic group-containing alkoxysilane compounds include phenyltrimethoxysilane and phenyltriethoxysilane. Examples of the amino-containing alkoxysilane compounds include N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and N-phenyl-3-aminopropyltrimethoxysilane. Examples of the isocyanate-containing alkoxysilane compounds include 3-isocyanatopropyltriethoxysilane. Examples of the isocyanurate-containing alkoxysilane compounds include tris-(trimethoxysilylpropyl)isocyanurate. Examples of the epoxy-containing alkoxysilane compounds include 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-glycidoxypropyltriethoxysilane. Examples of the mercapto-containing alkoxysilane compounds include 3-mercaptopropyltrimethoxysilane.

[0038] The solvent may be one or more selected from non-polar solvents and polar solvents. Examples of non-polar solvents include hydrocarbons such as n-hexane, n-heptane, and isooctane, and aromatic hydrocarbons such as toluene and xylene. Examples of polar solvents include water; alcohols such as methanol, ethanol, and isopropanol; alcohol esters; ketones such as acetone, methyl ethyl ketone, and cyclohexanone; ethers such as diethyl ether, dibutyl ether, and tetrahydrofuran; esters such as ethyl acetate, isopropyl acetate, and butyl acetate; hydrogen cyanide hydrocarbons such as acetonitrile; amines; amides such as acetamide; halogenated hydrocarbons such as methylene chloride, chloroform, and hexafluoromethaxylene; and sulfur-containing compounds such as dimethyl sulfoxide. The amount of the solvent used is not particularly limited and may be appropriately adjusted. Usually, the concentration of the organosilicon compound subjected to the reaction is preferably 5 to 95% by mass, more preferably 20 to 80% by mass. Incidentally, the reaction in the production method of the present invention can also be carried out in a solvent-free system.

[0039] As the organometallic catalyst, it is also possible to use organotin compounds such as dibutyltin dilaurate and dibutyltin di-2-ethylhexoate, and organometallic compounds of bismuth, zinc, and zirconium, but it is preferable to use a titanium alkoxide compound as the catalyst. Examples of the titanium alkoxide compound include tetra(2-ethylhexyl) titanate, titanium tetra-n-butoxide, titanium tetraisopropoxide, titanium diisopropoxide bis(ethylacetoacetate), titanium tetraacetylacetonate, titanium di-2-ethylhexoxy bis(2-ethyl-3-hydroxyhexoxide), and titanium diisopropoxide bis(acetylacetonate). As the catalyst amount of the titanium alkoxide compound, 0.1 to 10 parts by weight can be used with respect to 100 parts by weight of the organopolysiloxane having trialkoxysilyl at one end. When the catalyst amount of the titanium alkoxide compound is less than 0.1 part by weight, the reaction is not completed, and when the catalyst amount is more than 10 parts by weight, there is a possibility of leading to another problem such as yellowing and coloring.

[0040] Moreover, the organopolysiloxane having a partial structure in which the T-structure units of the present invention are continuously connected can also be synthesized from an organopolysiloxane having a hydrosilyl group at one end represented by the formula (5) and an alkoxysilane oligomer having a vinyl group. For the reaction, the solvents described above can be used as necessary, and as the catalyst, it is preferable to use a transition metal catalyst such as a platinum catalyst or a rhodium catalyst. TIFF0007704152000015.tif2379 In formula (5), R 2 independently represents a saturated hydrocarbon group having 1 to 12 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms. h has 4 to 400 carbon atoms.

[0041] One or more organopolysiloxanes having a hydrosilyl group at one end can be used. Examples of the organopolysiloxane having a hydrosilyl group at one end include FM-0105 (number average molecular weight (Mn) = about 500), FM-0111 (number average molecular weight (Mn) = about 1000), FM-0121 (number average molecular weight (Mn) = about 5000), FM-0125 (number average molecular weight (Mn) = about 10000), FM-0126 (number average molecular weight (Mn) = about 20000), FM-0127 (number average molecular weight (Mn) = about 30000), etc., manufactured by JNC.

[0042] As the alkoxysilane oligomer having a vinyl group, it can be produced by hydrolysis and condensation of vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, etc., in the presence of an acid catalyst or an alkali catalyst according to a conventionally known technique. Examples of the alkoxysilane oligomer having a vinyl group include DYNASYLAN6490 and DYNASYLAN6498 manufactured by EVONIC.

[0043] Examples of the transition metal catalyst include platinum alone, platinum solid dispersed on a carrier such as alumina, silica, carbon black, etc.; chloroplatinic acid; complexes of chloroplatinic acid with alcohols, aldehydes, ketones, etc.; platinum-olefin complexes, platinum(0)-divinyltetramethyldisiloxane complexes; compounds other than platinum compounds such as RhCl(PPh3)3, RhCl33, RuCl3, IrCl3, FeCl3, AlCl3, PdCl2·H2O, NiCl2, TiCl4, etc.

[0044] The dispersant, which is an organopolysiloxane having a partial structure in which the T-structural units of the present invention are continuously connected, has a number average molecular weight (Mn) measured by gel permeation chromatography (GPC) method of 500 to 100,000, more preferably 1,000 to 60,000. If the molecular weight is too small, steric repulsion when dispersing the filler cannot be exerted, and a stable dispersion cannot be obtained. Also, if the molecular weight is too large, the wettability with the filler becomes insufficient, and the viscosity of the dispersion increases.

[0045] The dispersant, which is an organopolysiloxane having a partial structure in which the T-structural units of the present invention are continuously connected, can be synthesized from an organopolysiloxane having trialkoxysilyl at one end represented by the formula (4). The number average molecular weight and molecular weight distribution index (Mw / Mn) of the dispersant can be adjusted by using a required amount of an organopolysiloxane having trialkoxysilyl at one end having an arbitrary number average molecular weight and molecular weight distribution index (Mw / Mn). Also, the dispersant of the present invention can be synthesized from an organopolysiloxane having hydrosilyl at one end represented by the formula (6). The number average molecular weight and molecular weight distribution index (Mw / Mn) of the dispersant can be adjusted by using a required amount of an organopolysiloxane having hydrosilyl at one end having an arbitrary number average molecular weight and molecular weight distribution index (Mw / Mn).

[0046] The dispersant of the present invention is used to disperse fillers in a liquid medium. Examples of the liquid medium include hydrocarbons, alkanols, alkenols, fatty acids, unsaturated fatty acids, esters of fatty acids and hydroxyl group-containing compounds, esters of unsaturated fatty acids and hydroxyl group-containing compounds, silicone oils, acrylic resins, epoxy resins, urethane resins, and the like. These liquid media can be used alone or in combination of two or more. A preferred liquid medium as a heat conductive material is silicone oil.

[0047] Examples of hydrocarbons include hexane, hexene, 2-ethylhexane, heptane, heptene, cyclohexane, cyclohexane heptane, octane, octene, 2-ethylhexane, nonane, decane, isodecane, dodecane, isododecane, tridecane, undecane, octadecane, C8-20 isoparaffin, squalane, petrolatum, microcrystalline wax, hydrogenated polyisobutene, 1-octene, 2-octene, 1-nonene, 2-nonene, 1-decene, 2-decene, 1-undecene, 2-undecene, 1-dodecene, 2-dodecene, 1-tridecene, 2-tridecene, 1-tetradecene, 2-tetradecene, 1-pentadecene, 2-pentadecene, 1-hexadecene, 2-hexadecene, 1-heptadecene, 2-heptadecene, 1-octadecene, 2-octadecene, dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane, propylcyclohexane, and the like.

[0048] Examples of alkanols and alkenols include octanol, 2-ethylhexanol, nonanol, decanol, isodecanol, dodecanol, cetyl alcohol, stearyl alcohol, arachyl alcohol, behenyl alcohol, hexyl decanol, octyldodecanol, isocetyl alcohol, isostearyl alcohol, oleyl alcohol, and the like.

[0049] Examples of fatty acids and unsaturated fatty acids include octanoic acid, nonanoic acid, decanoic acid, dodecanoic acid, tridecanoic acid, stearic acid, oleic acid, 1,2-hydroxystearic acid, ricinoleic acid, ricinoleic acid, undecylenic acid, isononanoic acid, myristic acid, palmitic acid, myristic acid, 2-ethylhexanoic acid, etc.

[0050] Examples of esters of fatty acids and hydroxyl group-containing compounds, and esters of unsaturated fatty acids and hydroxyl group-containing compounds include methyl laurate, heptyl undecylenate, isononyl isononanoate, ethyl oleate, isopropyl myristate, isopropyl palmitate, butyl stearate, cetyl palmitate, myristyl myristate, octyldodecyl myristate, isopropyl isostearate, ethyl isostearate, cetyl 2-ethylhexanoate, hexyl isostearate, ethylene glycol di(2-ethylhexanoate), ethylene glycol dioleate, propylene glycol di(caprylic / capric acid), propylene glycol dioleate, trimethylolpropane triisostearate, pentaerythrityl tetra(2-ethylhexanoate), neopentyl glycol diheptanoate, isocetyl isostearate, 2-octyldodecyl dimethyloctanoate, myristyl lactate, trioctyldodecyl citrate, diisostearyl malate, di(2-ethylhexyl) succinate, diisopropyl adipate, diisobutyl adipate, cholesteryl stearate, etc. Further examples include fats and oils such as almond oil, avocado oil, olive oil, shea butter, shea butter oil, evening primrose oil, borage seed oil, camellia oil, babassu oil, peanut oil, rosehip oil, etc., which are triesters with glycerin; waxes such as beeswax, candelilla wax, carnauba wax, etc.

[0051] Examples of silicone oils include dimethyl silicone oil, methylphenyl silicone oil, methylhydrogen silicone oil, amino-modified silicone oil, epoxy-modified silicone oil, carboxy-modified silicone oil, carbinol-modified silicone oil, polyether-modified silicone oil, alkyl-modified silicone oil, fluorine-modified silicone oil, and the like.

[0052] Examples of acrylic resins include monofunctional (meth)acrylates, difunctional (meth)acrylates, polyfunctional (meth)acrylates having three or more functional groups, epoxy (meth)acrylates, urethane (meth)acrylates, polyester (meth)acrylates having two or more functional groups, and the like.

[0053] Examples of epoxy resins include combinations of a main agent such as phenolic glycidyl ethers such as bisphenol A, bisphenol F, and phenol novolac, and alcohol-based glycidyl ethers such as polypropylene glycol, with a curing agent. Examples of curing agents include amine compounds such as aliphatic polyamines, modified aliphatic polyamines, polyamide amines, polyamides, alicyclic polyamines, modified alicyclic polyamines, modified aromatic polyamines, and tertiary amines. These curing agents may be used alone or in combination of two or more. A reaction accelerator that promotes the reaction between the main agent and the curing agent can also be used. Examples of reaction accelerators include phenol, p-t-butylphenol, di-t-butylphenol, cresol, triphenyl phosphite, salicylic acid, triethanolamine, and the like. These reaction accelerators may be used alone or in combination of two or more.

[0054] Examples of the urethane resin include reaction products of a hydroxyl group-containing compound and a polyisocyanate compound, for example, a polyurethane obtained by reacting a short-chain glycol or a short-chain ether and an isocyanate compound as a hard segment, and a linear multi-block copolymer of a polyurethane obtained by reacting a long-chain glycol or a long-chain ether and an isocyanate compound as a soft segment. Further, reaction products (cured products) of a urethane prepolymer and a polyisocyanate compound can be mentioned.

[0055] Examples of the filler include inorganic pigments, organic pigments, extender pigments, fillers, inorganic fine particles, diamond, graphene, graphite, carbon black, carbon nanotubes, clay, conductive fillers, heat conductors, carbon fibers, glass fibers, cellulose, cellulose nanofibers, and the like. These fillers are particulate, powdery, or fibrous substances added to plastics, rubbers, paints, inks, etc. for improving strength and functionality and reducing costs. There are no particular restrictions on the crystal form, particle size, surface state, presence or absence of surface treatment, etc. of the filler. As the filler (heat conductor) of the heat conductive material, aluminum oxide, zinc oxide, aluminum nitride or boron nitride is preferable, and aluminum oxide is more preferable.

[0056] <Filler dispersion> The filler dispersion of the present invention contains a filler, a liquid medium, and a dispersant for dispersing the filler in the liquid medium. And the dispersant is a dispersant which is an organopolysiloxane having a partial structure in which the above-mentioned T structural units are continuously connected. As the liquid medium, the above-mentioned liquid medium is used. Among them, it is preferable to use silicone oil. In addition to the liquid medium, for example, various organic solvents, monomers, and liquid oligomers can also be used.

[0057] As the filler, the above-mentioned filler is used. Among them, aluminum oxide, zinc oxide, aluminum nitride or boron nitride is preferable, and aluminum oxide is more preferable.

[0058] The filler dispersion preferably contains 4 to 50 parts by mass, more preferably 5 to 30 parts by mass of the liquid medium with respect to 100 parts by mass of the filler. Further, the filler dispersion preferably contains 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass of the dispersant with respect to 100 parts by mass of the filler. When the content of the dispersant with respect to 100 parts by mass of the filler is less than 0.1 part by mass, it may be difficult to stably disperse the filler. On the other hand, when the content of the dispersant with respect to 100 parts by mass of the filler exceeds 10 parts by mass, an excessive dispersant that does not contribute to the dispersion of the filler will be included.

[0059] In the filler dispersion of the present invention, various additives such as other surfactants, plasticizers, and defoamers can be blended within a range that does not impair the purpose.

[0060] The filler dispersion of the present invention can be produced according to a known method for producing a filler dispersion. For example, a method of adding a filler to a liquid medium to which a dispersant has been added and then stirring and mixing, a method of adding a liquid medium and a dispersant to a filler and then stirring and mixing, etc. can be mentioned. As the dispersing equipment for stirring, mixing, or dispersing, known dispersers can be used. For example, a roll mill, a ball mill, a bead mill, a sand mill, a homogenizer, a disper, a rotating and revolving mixer, etc. can be mentioned. Also, the dispersion treatment can be carried out in an ultrasonic generating bath.

Examples

[0061] Hereinafter, the present invention will be described more specifically. In the examples, "parts" and "%" are all based on mass (parts by mass, mass%) unless otherwise specified. Also, the present invention is not limited by these examples in any way.

[0062] <Measurement of molecular weight> The molecular weight of the organopolysiloxane was measured by gel permeation chromatography (GPC), and the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) was defined as the molecular weight distribution index (Mw / Mn). Polystyrene was used as the standard sample, and the polystyrene-equivalent molecular weight was measured. The measurement of the polystyrene-equivalent molecular weight by the GPC method was carried out under the following measurement conditions. a) Measuring instrument: HPLC LC-2000Plus series manufactured by JASCO Corporation b) Column: Two Shodex KF-804L columns c) Oven temperature: 40 °C d) Eluent: Toluene at 0.7 mL / min e) Standard sample: Polystyrene f) Injection volume: 20 μL g) Concentration: 0.05 g / 10 mL h) Sample preparation: Using toluene as the solvent, it was stirred and dissolved at room temperature.

[0063] <Nuclear magnetic resonance spectrum (NMR)> JNM-ECZ400S manufactured by JEOL Ltd. was used. 29 For Si-NMR, the measurement was carried out without a solvent. 29 In Si-NMR, the peak detection magnetic fields derived from the T structural units generally appear on the high magnetic field side in the order of T3 > T2 > T1 > T0. Therefore, the formation of the organopolysiloxane having a partial structure in which the T structural units of the present invention are continuously connected is confirmed by the appearance of the peaks of the T1 to T3 structures.

[0064] <Synthesis Example 1: Synthesis of an organopolysiloxane having an alkoxysilyl group at one end with a number average molecular weight of 1500> In a 500 ml four-necked flask equipped with a stirrer, a thermometer and a reflux condenser, 300 g of polydimethylsiloxane (number average molecular weight (Mn) = 1300) having a hydrosilyl group at one end and 55 g of vinyltrimethoxysilane (S210 manufactured by JNC, molecular weight = 148.2) were weighed respectively. While stirring under a nitrogen atmosphere, the temperature was raised to 70 °C. After reaching 70 °C, 4 μL of Pt-VTSC-3.0X manufactured by Umicore Japan was added as a Karstedt catalyst, and the mixture was stirred at 70 °C for 1 hour. After cooling to room temperature, the reflux condenser was replaced with a distillation head having a collection flask. Next, under a reduced pressure condition of 5 kPaA using a vacuum pump, after heating at 150 °C for 1 hour, and further under a reduced pressure condition of 0.1 kPaA, heating at 150 °C for 2 hours to distill off the volatile substances remaining in the product, 338 g of a slightly yellow transparent liquid was obtained as polydimethylsiloxane having a trimethoxysilyl group at one end. GPC: number average molecular weight (Mn) = 1500, weight average molecular weight (Mw) = 1700, molecular weight distribution index (Mw / Mn) = 1.14. 29 Si-NMR: δ (ppm); 10.0 (M), 9.3 - 9.5 (M), -20.5 - -19.9 (D), -41.2 - -40.8 (T). TIFF0007704152000016.tif18168

[0065] <Synthesis Example 2: Synthesis of organopolysiloxane having an alkoxysilyl group at one end with a number average molecular weight of 6500> In a 2000 ml four-necked flask equipped with a stirrer, a thermometer and a reflux condenser, 1000 g of polydimethylsiloxane (number average molecular weight (Mn) = 5000) having a hydrosilyl group at one end and 45 g of vinyltrimethoxysilane (S210 manufactured by JNC, molecular weight = 148.2) were weighed respectively. Under a nitrogen atmosphere, the temperature was raised to 70 °C while stirring. After reaching 70 °C, 12 μL of Pt-VTSC-3.0X manufactured by Umicore Japan was added as a Karstedt catalyst, and the mixture was stirred at 70 °C for 1 hour. After cooling to room temperature, the reflux condenser was replaced with a distillation head having a collection flask. Next, under a reduced pressure condition of 5 kPaA using a vacuum pump, after heating at 150 °C for 1 hour, and further under a reduced pressure condition of 0.1 kPaA, heating at 150 °C for 2 hours to distill off the volatile substances remaining in the product, 1010 g of a slightly yellow transparent liquid was obtained as polydimethylsiloxane having a trimethoxysilyl group at one end. GPC: number average molecular weight (Mn) = 6500, weight average molecular weight (Mw) = 6900, molecular weight distribution index (Mw / Mn) = 1.05. 29 Si-NMR: δ (ppm); 8.6 (M), 7.9 - 8.2 (M), -22.2 - -21.3 (D), -42.5 - -42.2 (T). TIFF0007704152000017.tif18168

[0066] <Synthesis Example 3: Synthesis of organopolysiloxane having an alkoxysilyl group at one end with a number average molecular weight of 12000> In a 1000 ml four-necked flask equipped with a stirrer, a thermometer, and a reflux condenser, 659 g of polydimethylsiloxane (number average molecular weight (Mn) = 11100) having a hydrosilyl group at one end and 20 g of vinyltrimethoxysilane (S210 manufactured by JNC, molecular weight = 148.2) were weighed respectively. While stirring under a nitrogen atmosphere, the temperature was raised to 70 °C. After reaching 70 °C, 76 μL of Pt-VTSC-3.0X manufactured by Umicore Japan was added as a Karstedt catalyst, and the mixture was stirred at 70 °C for 1 hour. After cooling to room temperature, the reflux condenser was replaced with a distillation head having a collection flask. Next, under a reduced pressure condition of 0.3 kPaA using a vacuum pump, it was heated at 120 °C for 1 hour to distill off the volatile substances remaining in the product, thereby obtaining 663 g of a slightly yellow transparent liquid as polydimethylsiloxane having a trimethoxysilyl group at one end. GPC: number average molecular weight (Mn) = 11600, weight average molecular weight (Mw) = 12000, molecular weight distribution index (Mw / Mn) = 1.04. 29 Si-NMR: 7.3~8.1 (M), -22.8~-21.8 (D), -43.0~-42.7 (T). TIFF0007704152000018.tif18167

[0067] <Synthesis Example 4: Synthesis of organopolysiloxane having an alkoxysilyl group at one end with a number average molecular weight of 17000> Into a 1000 ml four-necked flask equipped with a stirrer, thermometer and reflux condenser, 697 g of polydimethylsiloxane having a hydrosilyl group at one end (number average molecular weight (Mn) = 17100) and 14 g of vinyltrimethoxysilane (S210 manufactured by JNC, molecular weight = 148.2) were weighed respectively. While stirring under a nitrogen atmosphere, the temperature was raised to 70 °C. After reaching 70 °C, 81 μL of Pt-VTSC-3.0X manufactured by Umicore Japan was added as a Karstedt catalyst, and the mixture was stirred at 70 °C for 1 hour. After cooling to room temperature, the reflux condenser was replaced with a distillation head having a collection flask. Next, under a reduced pressure condition of 0.3 kPaA using a vacuum pump, it was heated at 120 °C for 1 hour to distill off the volatile substances remaining in the product, and 703 g of a slightly yellow transparent liquid was obtained as polydimethylsiloxane having a trimethoxysilyl group at one end. GPC: number average molecular weight (Mn) = 16900, weight average molecular weight (Mw) = 17600, molecular weight distribution index (Mw / Mn) = 1.04. 29 Si-NMR: 7.9~8.6 (M), -22.2~-21.2 (D), -42.4~-42.2 (T). TIFF0007704152000019.tif18167

[0068] <Synthesis Example 5: Synthesis of an organopolysiloxane having a number average molecular weight of 7200 and a partial structure in which T structural units are continuously connected> Into a 100 ml two-necked flask equipped with a magnetic stirrer, thermometer and reflux condenser, 30 g of polydimethylsiloxane having a trimethoxysilyl group at one end (number average molecular weight (Mn) = 1500, weight average molecular weight (Mw) = 1700, molecular weight distribution index (Mw / Mn) = 1.14) and 11 mg of tetra(2-ethylhexyl) titanate (manufactured by Fujifilm Wako Pure Chemical Corporation, molecular weight = 564.8) were weighed respectively. While stirring under a nitrogen atmosphere, the temperature was raised, and the mixture was stirred at 60~70 °C for 4 hours. Then, a solution prepared by mixing 0.72 g of water with 10 g of tetrahydrofuran was fed at 70 °C over 5 minutes, and the mixture was stirred at 60 °C for 2 hours. Subsequently, a total of 681 mg of tetra(2-ethylhexyl) titanate was added in 5 portions over 22 hours at 60~70 °C. After cooling to room temperature, the reaction solution was transferred to a separatory funnel. 20 g of normal hexane and 20 g of water were added, and after shaking and allowing to stand, it was confirmed that the solution separated into two layers. After confirmation, the lower aqueous layer was withdrawn from the separatory funnel. Further, 50 g of water was added to the separatory funnel, shaken, allowed to stand, and after confirmation that the solution separated into two layers, the operation of withdrawing the lower aqueous layer from the separatory funnel was repeated twice. The 56 g of the oil layer remaining in the separatory funnel was transferred to a 100 ml two-necked flask equipped with a stir bar, thermometer, collection flask, and distillation head, and heated at 25 °C for 2 hours under reduced pressure conditions of 0.3 kPaA using a vacuum pump to distill off the volatile substances remaining in the product. 25 g of a slightly yellow transparent liquid remaining in the flask was obtained. GPC: Number average molecular weight (Mn) = 7200, weight average molecular weight (Mw) = 8700, molecular weight distribution index (Mw / Mn) = 1.21. 29 Si-NMR: δ (ppm); 6.9~7.5 (M), -22.9~ -22.2 (D), -48.7 (T), -57.3 (T), -67.4 (T). TIFF0007704152000020.tif63167

[0069] Figure 5 shows the 29 Si-NMR spectrum of the slightly yellow transparent liquid obtained in Synthesis Example 5, and Figure 1 shows the 29 Si-NMR spectrum of the polydimethylsiloxane having trimethoxysilyl at one end used in Synthesis Example 5. In the 29 Si-NMR spectrum of Figure 5, the peak at -41.2 ppm to -40.8 ppm derived from the T unit of the polydimethylsiloxane having trimethoxysilyl at one end disappeared, and broad peaks were newly confirmed at -48.7 ppm, -57.3 ppm, and -67.4 ppm. From the above analysis results, it is determined that the obtained slightly yellow transparent liquid is an organopolysiloxane having a number average molecular weight of 7200 and a partial structure in which T structural units are continuously connected.

[0070] <Synthesis Example 6: Synthesis of an organopolysiloxane having a number average molecular weight of 28000 and a partial structure in which T structural units are continuously connected> In a 100 ml two-necked flask equipped with a stirrer, thermometer and reflux condenser, 30 g of polydimethylsiloxane having trimethoxysilyl at one end (number average molecular weight (Mn) = 6500, weight average molecular weight (Mw) = 7200, molecular weight distribution index (Mw / Mn) = 1.12) and 11 mg of tetra(2-ethylhexyl) titanate (Fuji Film Wako Pure Chemical Industries, molecular weight = 564.8) were each weighed, and the temperature was raised with stirring under a nitrogen atmosphere and stirred at 60 °C for 2 hours. Then, a solution prepared by mixing 0.16 g of water with 10 g of tetrahydrofuran was fed at 60 °C over 5 minutes and stirred at 60 °C for 1 hour. Subsequently, a total of 681 mg of tetra(2-ethylhexyl) titanate was added in 5 portions over 18 hours at 60 - 70 °C. After cooling to room temperature, the reaction solution was transferred to a separatory funnel, 20 g of normal hexane and 30 g of water were added, shaken, and after allowing to stand and confirming separation into two layers, the lower aqueous layer was withdrawn from the separatory funnel. Further, 30 g of water was added to the separatory funnel, shaken, and after allowing to stand and confirming separation into two layers, the operation of withdrawing the lower aqueous layer from the separatory funnel was repeated twice. The 57 g of the oil layer remaining in the separatory funnel was transferred to a 100 ml two-necked flask equipped with a magnetic stirrer, thermometer, collection flask and distillation head, and under reduced pressure conditions of 0.3 kPaA using a vacuum pump, it was heated at 40 °C for 2 hours to distill off the volatile substances remaining in the product. 28 g of a colorless transparent liquid remaining in the flask was obtained. GPC: number average molecular weight (Mn) = 28000, weight average molecular weight (Mw) = 37500, molecular weight distribution index (Mw / Mn) = 1.34. 29 Si-NMR: δ (ppm); 7.8 - 8.5 (M), -22.2 - 21.3 (D), -56.7 (T), -66.1 (T).

[0071] TIFF0007704152000021.tif63168

[0072] Figure 6 shows the colorless transparent liquid obtained in Synthesis Example 6 29It shows an Si-NMR spectrum. Figure 2 shows the 29 Si-NMR spectrum of the polydimethylsiloxane having trimethoxysilyl at one end used in Synthesis Example 6. In the 29 Si-NMR spectrum of Figure 6, the peak at -42.5 ppm to -42.2 ppm derived from the T unit of the polydimethylsiloxane having trimethoxysilyl at one end disappeared, and broad peaks were newly confirmed at -56.7 ppm and -66.1 ppm. From the above analysis results, it is judged that the obtained colorless transparent liquid is an organopolysiloxane having a number average molecular weight of 28,000 and a partial structure in which T structural units are continuously connected.

[0073] <Synthesis Example 7: Synthesis of an organopolysiloxane having a number average molecular weight of 88,500 and a partial structure in which T structural units are continuously connected> Into a 100 ml three-necked flask equipped with a stirrer, a thermometer and a reflux condenser, 30 g of polydimethylsiloxane having trimethoxysilyl at one end (number average molecular weight (Mn) = 16,900, weight average molecular weight (Mw) = 17,600, molecular weight distribution index (Mw / Mn) = 1.04) and 11 mg of tetra(2-ethylhexyl) titanate (Fuji Film Wako Pure Chemical Industries, Ltd., molecular weight = 564.8) were weighed respectively. Under a nitrogen atmosphere, the temperature was raised with stirring and stirred at 60 to 70 °C for 4 hours. Then, a solution prepared by mixing 0.72 g of water with 10 g of tetrahydrofuran was fed at 70 °C over 5 minutes and stirred at 60 °C for 2 hours. Subsequently, a total of 681 mg of tetra(2-ethylhexyl) titanate was added in 5 portions over 22 hours at 60 to 70 °C. After cooling to room temperature, the reaction solution was transferred to a separatory funnel, 20 g of normal hexane and 20 g of water were added, shaken and then allowed to stand. After confirming that it was separated into two layers, the lower aqueous layer was withdrawn from the separatory funnel. Further, 50 g of water was added to the separatory funnel, shaken and then allowed to stand. After confirming that it was separated into two layers, the operation of withdrawing the lower aqueous layer from the separatory funnel was repeated twice. 52 g of the oil layer remaining in the separatory funnel was transferred to a 100 ml two-necked flask equipped with a stir bar, thermometer, collection flask, and distillation head, and heated at 25 °C for 2 hours under reduced pressure of 0.3 kPaA using a vacuum pump to distill off the volatile substances remaining in the product. 21 g of a yellow transparent liquid remaining in the flask was obtained. GPC: Number average molecular weight (Mn) = 85,500, weight average molecular weight (Mw) = 150,000, molecular weight distribution index (Mw / Mn) = 1.69. 29 Si-NMR: δ (ppm); 7.9 - 8.6 (M), -22.0 - -21.5 (D).

[0074] TIFF0007704152000022.tif63166

[0075] Figure 11 shows the 29 Si-NMR spectrum of the yellow transparent liquid obtained in Synthesis Example 7, and Figure 4 shows the 29 Si-NMR spectrum of the polydimethylsiloxane having trimethoxysilyl at one end used in Synthesis Example 7. In the 29 Si-NMR spectrum of Figure 11, disappearance of the peak at -42.4 ppm to -42.2 ppm derived from the T unit of the polydimethylsiloxane having trimethoxysilyl at one end was confirmed. From the above analysis results, it is determined that the obtained slightly yellow transparent liquid is an organopolysiloxane having a number average molecular weight of 85,500 and a partial structure in which T structural units are continuously connected.

[0076] <Synthesis Example 8: Synthesis of an organopolysiloxane having alkoxysilyl at one end with a molecular weight of 561> In a 500 ml four-necked flask equipped with a stirrer, a pressure-equalizing dropping funnel, a thermometer and a reflux condenser, 300 g of polydimethylsiloxane (molecular weight = 412.9) having a hydrosilyl group at one end and 26 g of vinyltrimethoxysilane (S210 manufactured by JNC, molecular weight = 148.2) were weighed respectively, and the temperature was raised to 70 °C while stirring under a nitrogen atmosphere. After reaching 70 °C, 1 μL of Pt-VTSC-3.0X manufactured by Yumicore Japan was added as a Karstedt catalyst. 129 g of vinyltrimethoxysilane was weighed into the pressure-equalizing dropping funnel and dropped into the reaction solution over 10 minutes, and the mixture was stirred at 70 °C for 1 hour. Further, 1 μL of Pt-VTSC-3.0X was added at 70 °C, and after stirring at 85 °C for 2 hours, it was cooled to room temperature, and the reflux condenser was replaced with a distillation head having a collection flask. Next, it was heated at 100 °C under a reduced pressure condition of 2.0 kPaA using a vacuum pump to distill off the volatile substances remaining in the product. Then, by further heating at 100 °C under a reduced pressure condition of 0.1 kPaA to distill off the volatile substances remaining in the product, 405 g of a colorless transparent liquid was obtained as polydimethylsiloxane (molecular weight = 561.1) having a trimethoxysilyl group at one end. 29 Si-NMR: δ (ppm); 7.7~9.1 (M), -22.2~-20.9 (D), -42.3~42.0 (T).

[0077] TIFF0007704152000023.tif18168

[0078] <Synthesis Example 9: Synthesis of an organopolysiloxane having a number average molecular weight of 4400 and a partial structure in which T structural units are continuously connected> Into a 300 ml four-necked flask equipped with a stirrer, a pressure-equalizing dropping funnel, a thermometer and a reflux condenser, 100 g of polydimethylsiloxane (molecular weight = 561) having trimethoxysilyl at one end and 0.3 g of tetra(t-butyl) titanate (Matsumoto Fine Chemical Co., molecular weight = 340.4) were weighed respectively, and the temperature was raised with stirring under a nitrogen atmosphere and stirred at 80 °C for 30 minutes. Then, a liquid obtained by mixing 31 g of water with 40 g of N, N-dimethylformamide was fed at 65 °C over 3 hours and stirred at 90 °C for 7 hours. After cooling to room temperature, the reflux condenser was replaced with a distillation head having a collection flask. Next, under a reduced pressure condition of 5.0 kPaA using a vacuum pump, it was heated at 100 °C to distill off the volatile substances remaining in the product. Then, under a reduced pressure condition of 0.1 kPaA, it was further heated at 125 °C to distill off the volatile substances remaining in the product. The white suspension remaining in the flask was transferred to a stainless steel holder equipped with a filtration filter with a filtration accuracy of 3 μm, and 72 g of a colorless transparent liquid was obtained by pressure filtration with nitrogen. GPC: number average molecular weight (Mn) = 4400, weight average molecular weight (Mw) = 4600, molecular weight distribution index (Mw / Mn) = 1.05. 29 Si-NMR: δ (ppm); 10.6~11.0 (M), -19.4~-18.7 (D), -55.1 (T), -64.7 (T).

[0079] TIFF0007704152000024.tif62167

[0080] Figure 13 shows the 29 Si-NMR spectrum of the colorless transparent liquid obtained in Synthesis Example 9, and Figure 12 shows the 29 Si-NMR spectrum of polydimethylsiloxane having trimethoxysilyl at one end used in Synthesis Example 9. In the 29 Si-NMR spectrum of Figure 13, the peak at -42.3 ppm to -42.0 ppm derived from the T unit of polydimethylsiloxane having trimethoxysilyl at one end disappeared, and broad peaks were newly confirmed at -55.1 ppm and -64.7 ppm. From the above analysis results, it is determined that the obtained colorless transparent liquid is an organopolysiloxane having a number average molecular weight of 4400 and a partial structure in which T structural units are continuously connected.

[0081] <Synthesis Example 10: Synthesis of an organopolysiloxane having a number average molecular weight of 6700 and a partial structure in which T structural units are continuously connected by reacting polydimethylsiloxane having trimethoxysilyl at one end with hexyltriethoxysilane> Into a 500 ml four-necked flask equipped with a stirrer, a pressure-equalizing dropping funnel, a thermometer, and a reflux condenser, 90 g of polydimethylsiloxane having trimethoxysilyl at one end (number average molecular weight (Mn) = 1500, weight average molecular weight (Mw) = 1700, molecular weight distribution index (Mw / Mn) = 1.14), 79 g of hexyltriethoxysilane (Tokyo Chemical Industry Co., Ltd., molecular weight = 248.4), and 10 g of tetra(2-ethylhexyl) titanate (Fuji Film Wako Pure Chemical Industries, Ltd., molecular weight = 564.8) were weighed respectively. While stirring under a nitrogen atmosphere, the temperature was raised, and stirring was carried out at 80 °C for 30 minutes. Then, a solution prepared by mixing 72 g of water with 90 g of N,N-dimethylformamide was fed at 80 °C over 3 hours, and stirring was carried out at 90 °C for 7 hours. After cooling to room temperature, the reflux condenser was replaced with a distillation head having a collection flask. Next, under a reduced pressure condition of 5.0 kPaA using a vacuum pump, heating was carried out at 100 °C to distill off the volatile substances remaining in the product. Then, under a reduced pressure condition of 0.1 kPaA, further heating was carried out at 125 °C to distill off the volatile substances remaining in the product. The yellow suspension remaining in the flask was transferred to a stainless steel holder equipped with a filtration filter with a filtration accuracy of 3 μm, and 130 g of a yellow transparent liquid was obtained by pressure filtration with nitrogen. GPC: number average molecular weight (Mn) = 6700, weight average molecular weight (Mw) = 9300, molecular weight distribution index (Mw / Mn) = 1.39. 29 Si-NMR: δ (ppm); 7.9~8.5 (M), -22.0~-21.3 (D).

[0082] TIFF0007704152000025.tif54166

[0083] Figure 14 shows the Si-NMR spectrum of the yellow transparent liquid obtained in Synthesis Example 10, and Figure 1 shows the 29 Si-NMR spectrum of the polydimethylsiloxane having trimethoxysilyl at one end used in Synthesis Example 10. In the 29 Si-NMR spectrum of Figure 14, disappearance of the peak at -41.2 ppm to -40.8 ppm derived from the T unit of the polydimethylsiloxane having trimethoxysilyl at one end was confirmed. 29 From the above analysis results, it is determined that the obtained yellow transparent liquid is an organopolysiloxane having a number average molecular weight of 6700 and a partial structure in which T structural units are continuously connected.

[0084] <Synthesis Example 11: Synthesis of an organopolysiloxane having a number average molecular weight of 6200 and a partial structure in which T structural units are continuously connected by reacting polydimethylsiloxane having trimethoxysilyl at one end with phenyltriethoxysilane> Into a 500 ml four-necked flask equipped with a stirrer, a pressure-equalizing dropping funnel, a thermometer and a reflux condenser, 90 g of polydimethylsiloxane having trimethoxysilyl at one end (number average molecular weight (Mn) = 1500, weight average molecular weight (Mw) = 1700, molecular weight distribution index (Mw / Mn) = 1.14), 77 g of phenyltriethoxysilane (Tokyo Chemical Industry Co., molecular weight = 240.4), and 10 g of tetra(2-ethylhexyl) titanate (Fuji Film Wako Pure Chemical Industries, molecular weight = 564.8) were weighed respectively, and the temperature was raised while stirring under a nitrogen atmosphere, and stirred at 80 °C for 30 minutes. Then, a solution prepared by mixing 72 g of water with 90 g of N, N-dimethylformamide was fed at 80 °C over 3 hours and stirred at 90 °C for 7 hours. ​After cooling to room temperature, the reflux condenser was replaced with a distillation head having a collection flask. Next, using a vacuum pump, it was heated at 100 °C under a reduced pressure condition of 5.0 kPaA to distill off the volatile substances remaining in the product. Then, it was further heated at 125 °C under a reduced pressure condition of 0.1 kPaA to distill off the volatile substances remaining in the product. The yellow suspension remaining in the flask was transferred to a stainless steel holder equipped with a filtration filter with a filtration accuracy of 3 μm, and 125 g of a yellow transparent liquid was obtained by pressure filtration with nitrogen. GPC: Number average molecular weight (Mn) = 6200, weight average molecular weight (Mw) = 7900, molecular weight distribution index (Mw / Mn) = 1.28. 29 Si-NMR: δ (ppm); 7.8~8.3 (M), -22.0~-21.6 (D).

[0085] TIFF0007704152000026.tif57166

[0086] Figure 15 shows the 29 Si-NMR spectrum of the yellow transparent liquid obtained in Synthesis Example 11, and Figure 1 shows the 29 Si-NMR spectrum of the polydimethylsiloxane having trimethoxysilyl at one end used in Synthesis Example 11. In the 29 Si-NMR spectrum of Figure 15, disappearance of the peak at -41.2 ppm to -40.8 ppm derived from the T unit of the polydimethylsiloxane having trimethoxysilyl at one end was confirmed. From the above analysis results, it is judged that the obtained yellow transparent liquid is an organopolysiloxane having a number average molecular weight of 6200 and a partial structure in which T structural units are continuously connected.

[0087] <Synthesis Example 12: Synthesis of an organopolysiloxane having a number average molecular weight of 8100 and a partial structure in which T structural units are continuously connected by reacting polydimethylsiloxane having trimethoxysilyl at one end with 3-methacryloxypropyltriethoxysilane> In a 300 ml four-necked flask equipped with a stirrer, a pressure-equalizing dropping funnel, a thermometer and a reflux condenser, 45 g of polydimethylsiloxane having trimethoxysilyl at one end (number average molecular weight (Mn) = 1500, weight average molecular weight (Mw) = 1700, molecular weight distribution index (Mw / Mn) = 1.14), 46 g of 3-methacryloxypropyltriethoxysilane (Tokyo Chemical Industry Co., Ltd., molecular weight = 290.4), and 0.7 g of tetra(t-butyl) titanate (Matsumoto Fine Chemical Co., Ltd., molecular weight = 340.4) were weighed respectively, and the temperature was raised with stirring under a nitrogen atmosphere and stirred at 80 °C for 30 minutes. Then, a liquid obtained by mixing 46 g of water with 40 g of N, N-dimethylformamide was fed at 80 °C over 3 hours and stirred at 90 °C for 7 hours. After cooling to room temperature, the reflux condenser was replaced with a distillation head having a collection flask. Next, under a reduced pressure condition of 5.0 kPaA using a vacuum pump, it was heated at 100 °C to distill off the volatile substances remaining in the product. Then, under a reduced pressure condition of 0.1 kPaA, it was further heated at 100 °C to distill off the volatile substances remaining in the product. The yellow suspension remaining in the flask was transferred to a stainless steel holder equipped with a filtration filter with a filtration accuracy of 3 μm, and 66 g of a yellow transparent liquid was obtained by pressure filtration with nitrogen. GPC: number average molecular weight (Mn) = 8100, weight average molecular weight (Mw) = 10600, molecular weight distribution index (Mw / Mn) = 1.32. 29 Si-NMR: δ (ppm); 7.9~8.6 (M), -22.0~-21.2 (D).

[0088] TIFF0007704152000027.tif53168

[0089] Figure 16 shows the 29 Si-NMR spectrum of the yellow transparent liquid obtained in Synthesis Example 12, and Figure 1 shows the 29 Si-NMR spectrum of polydimethylsiloxane having trimethoxysilyl at one end used in Synthesis Example 12. 29In the Si-NMR spectrum, the disappearance of the peak at -41.2 ppm to -40.8 ppm derived from the T unit of polydimethylsiloxane having trimethoxysilyl at one end was confirmed. From the above analysis results, it is determined that the obtained yellow transparent liquid is an organopolysiloxane having a number average molecular weight of 8100 and a partial structure in which T structural units are continuously connected.

[0090] <Preparation of Samples for Dispersibility Evaluation 1 - 2> In an ointment pot container, polydimethylsiloxane (KF-96-1000CS manufactured by Shin-Etsu Chemical Co., Ltd.), which is a silicone oil, as a liquid medium, and organopolysiloxanes synthesized in Synthesis Examples 1 to 7 and Synthesis Examples 9 to 10 as dispersants were weighed. Further, aluminum oxide with an average diameter of 13 μm (DAW-10 manufactured by Denka Co., Ltd.) was weighed as a dispersoid and stirred using a spatula. KF-96-1000CS, the organopolysiloxanes synthesized in Synthesis Examples 1 to 7 and Synthesis Examples 9 to 10, and aluminum oxide were weighed so as to have the blending amounts shown in Tables 1 to 4. Next, using a Sinky Corporation Awatori Renjiro vacuum type (model: ARV-310), it was kneaded at 2000 rpm for 1 minute under normal pressure conditions and at 2000 rpm for 1 minute under reduced pressure conditions to prepare a sample for dispersibility evaluation.

[0091] <Dispersibility Evaluation 1 - 2> The sample for dispersibility evaluation prepared as described above was evaluated for dispersibility by measuring the shear viscosity at different shear rates under the following conditions using a rheometer (MCR302 manufactured by Anton Paar). Plate shape: Circular flat plate, 25 mm φ Sample thickness: 1 mm Temperature: 25 ± 1 °C Shear rate: 0.01 - 100 S -1

[0092] For Examples 1 to 2 and Examples 6 to 8, as shown in Tables 1 to 4, an organopolysiloxane having a partial structure in which the T-structure units synthesized in Synthesis Examples 5 to 7 and Synthesis Examples 9 to 10 are continuously connected was used as a dispersant, and the shear viscosity at the shear rate was measured for evaluation. For Comparative Examples 1 to 4, as shown in Tables 1 to 4, an organopolysiloxane having an alkoxysilyl group at one end synthesized in Synthesis Examples 1 to 4 was used as a dispersant, and the shear viscosity at the shear rate was measured for evaluation. The results are shown in Tables 1 to 4 and FIG. 7.

[0093] Table 1. Dispersibility Evaluation Results 1-1 TIFF0007704152000028.tif73167

[0094] Table 2. Dispersibility Evaluation Results 1-2 TIFF0007704152000029.tif73167

[0095] Table 3. Dispersibility Evaluation Results 1-3 TIFF0007704152000030.tif73167

[0096] Table 4. Dispersibility Evaluation Results 1-4 TIFF0007704152000031.tif73167

[0097] Also, for Example 1, Examples 3 to 6, and Examples 9 to 10, as shown in Tables 5 to 8, an organopolysiloxane having a partial structure in which the T-structure units synthesized in Synthesis Example 5 and Synthesis Example 7 are continuously connected was used as a dispersant, and the proportion of the dispersant was changed, and the shear viscosity at the shear rate was measured for evaluation. The results are shown in Tables 5 to 8 and FIGS. 8 to 9.

[0098] Table 5. Dispersibility Evaluation Results 2-1 TIFF0007704152000032.tif62168

[0099] TIFF0007704152000033.tif61167

[0100] TIFF0007704152000034.tif61167

[0101] Table 8. Dispersion Evaluation Results 2 - 4 TIFF0007704152000035.tif61167

[0102] <Preparation of Sample for Dispersion Evaluation 3> In an ointment pot container, polydimethylsiloxane (KF - 96 - 300CS manufactured by Shin - Etsu Chemical Co., Ltd.), which is a silicone oil, as a liquid medium, and the organopolysiloxane synthesized in Synthesis Example 5 as a dispersant were weighed. Further, aluminum oxide with an average diameter of 5 μm (DAW - 03 manufactured by Denka Co., Ltd.) and aluminum oxide with an average diameter of 50 μm (DAW - 45 manufactured by Denka Co., Ltd.) were weighed as the dispersoid, and stirred using a spatula. KF - 96 - 300CS, the organopolysiloxane synthesized in Synthesis Example 5, and aluminum oxide were weighed so as to have the compounding amounts shown in Tables 9 to 12. Next, using a Sinky Corporation Awatori Renjiro vacuum type (model: ARV - 310), it was kneaded at 2000 rpm for 1 minute under normal pressure conditions and at 2000 rpm for 1 minute under reduced pressure conditions to prepare a sample for dispersion evaluation.

[0103] <Dispersion Evaluation 3> The sample for dispersion evaluation prepared as described above was evaluated by measuring the shear viscosity at different shear rates under the following conditions using a rheometer (MCR302 manufactured by Anton Paar). Plate shape: Circular flat plate 25 mmφ Sample thickness: 1 mm Temperature: 25 ± 1 °C Shear rate: 0.01 - 100 S -1

[0104] For Examples 11 to 12, as shown in Tables 9 to 12, the shear viscosity at the shear rate was measured using an organopolysiloxane having a partial structure in which the T - structural units synthesized in Synthesis Example 5 were continuously connected as a dispersant, and the evaluation was performed. The results are shown in Tables 9 to 12 and Figure 10.

[0105] Table 9. Dispersion Evaluation Results 3-1 TIFF0007704152000036.tif44167

[0106] TIFF0007704152000037.tif44167

[0107] Table 11. Dispersion Evaluation Results 3-3 TIFF0007704152000038.tif44167

[0108] Table 12. Dispersion Evaluation Results 3-4 TIFF0007704152000039.tif44168

[0109] The organopolysiloxane having a partial structure in which the T-structural units of the present invention are continuously connected has a lower shear viscosity suppressed in the range of shear rate: 0.001 to 0.06 S in the evaluation of dispersibility as compared with the organopolysiloxane having an alkoxysilyl group at one end, and it was confirmed that it is good as a dispersant. Further, it was confirmed that the dispersant, which is an organopolysiloxane having a partial structure in which the T-structural units are continuously connected, can suppress the shear viscosity at each shear rate to a low level according to the addition amount. -1 As a result, it was confirmed that it is good as a dispersant. Further, it was confirmed that the dispersant, which is an organopolysiloxane having a partial structure in which the T-structural units are continuously connected, can suppress the shear viscosity at each shear rate to a low level according to the addition amount.

Industrial Applicability

[0110] The organopolysiloxane having a partial structure in which the T-structural units of the present invention are continuously connected can be used as a dispersant for stably dispersing a filler in a liquid medium in fields such as cosmetics, liquid developers, oil-based inkjet inks, ultraviolet curable inkjet inks, weak solvent-based paints, offset inks, lubricants, detergents, insecticides, release agents, adhesives, heat conductive materials, conductive materials, and optical materials.

Claims

1. An organopolysiloxane represented by formula (1) or (2). In formulas (1) and (2), R １ is independently a saturated hydrocarbon group having 1 to 12 carbon atoms, X is independently a group represented by formula (3), acryloyl, alkyl, carboxyl, vinyl, methacryl, aromatic group, amino, isocyanate, isocyanurate, epoxy, hydroxyl, or mercapto, and at least one X is a group represented by formula (3), m, l, and k are independently 0 to 10, j is 1 to 10; In formula (3), R ２ is independently a saturated hydrocarbon group having 1 to 12 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms, Y is a divalent hydrocarbon group having 1 to 8 carbon atoms, h is 4 to 400.

2. The organopolysiloxane according to claim 1, which is a reaction product of an organopolysiloxane represented by formula (4) and a trialkoxysilane. In formula (4), R １ is independently a saturated hydrocarbon group having 1 to 12 carbon atoms, R ２ is independently a saturated hydrocarbon group having 1 to 12 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms, Y is a divalent hydrocarbon group having 1 to 8 carbon atoms, h is 4 to 400.

3. A method for producing the organopolysiloxane according to claim 2, comprising reacting an organopolysiloxane represented by formula (4) with a trialkoxysilane.

4. The organopolysiloxane according to claim 1, wherein the organopolysiloxane represented by formula (4) according to claim 2 reacts intermolecularly.

5. A method for producing the organopolysiloxane according to claim 3, comprising reacting the organopolysiloxane represented by formula (4) according to claim 2 intermolecularly.

6. The method for producing an organopolysiloxane according to claim 3 or 5, wherein an organometallic catalyst is used as a catalyst.

7. The organopolysiloxane according to claim 1, which is a reaction product of an organopolysiloxane represented by formula (5) and an alkoxysilane oligomer having vinyl. In formula (5) R ２ is independently a saturated hydrocarbon group having 1 to 12 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms, h is 4 to 400.

8. A method for producing the organopolysiloxane according to claim 1, comprising reacting the organopolysiloxane represented by formula (5) according to claim 7 with an alkoxysilane oligomer having vinyl.

9. A dispersant used for dispersing a filler in a liquid medium, comprising the organopolysiloxane according to claim 1.

10. The dispersant according to claim 9, having a number average molecular weight (Mn) of 500 to 100,000.

11. The dispersant according to claim 9 or 10, having a molecular weight distribution index (Mw / Mn) of 1.0 to 3.

0.

12. A filler dispersion liquid containing a filler, a liquid medium, and the organopolysiloxane according to claim 1.

13. The filler dispersion liquid according to claim 12, wherein the content of the liquid medium is 4 to 50 parts by mass and the content of the dispersant is 0.1 to 20 parts by mass with respect to 100 parts by mass of the filler.

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