Organopolysiloxanes and their manufacturing methods, dispersants containing the same, and dispersions containing organopolysiloxanes as dispersants.

Abstract

This invention provides a dispersant that imparts excellent filler dispersibility in liquid media, an organopolysiloxane, a method for manufacturing the same, and a dispersion containing the organopolysiloxane as a dispersant. An organopolysiloxane represented by formula (1) or (2), wherein R... 1 The group is a saturated hydrocarbon group of C1 to C12, where X is a group represented by formula (3), acryloyl, alkyl, carboxyl, vinyl, methacryloyl, aromatic, amino, isocyanate, isocyanurate, epoxy, hydroxy, or mercapto, and at least one X is a group represented by formula (3), where m, l, and k are 0 to 10, and j is 1 to 10. In formula (3), R... 2 Y is a C1-12 saturated hydrocarbon group or a C6-12 aromatic hydrocarbon group, Y is a C1-8 divalent hydrocarbon group, and h is 4-400.

Description

Technical Field

[0001] This invention relates to an organopolysiloxane having a partial structure consisting of continuously connected T-shaped structural units and a method for manufacturing the same, and to a filler dispersion comprising the organopolysiloxane as a dispersant capable of imparting excellent filler dispersibility in a liquid medium. Background Technology

[0002] Products using liquid media such as hydrocarbons, alkanols, enols, fatty acids, unsaturated fatty acids, esters of fatty acids and hydroxyl-containing compounds, esters of unsaturated fatty acids and hydroxyl-containing compounds, as well as silicone oils, acrylic resins, epoxy resins, and urethane resins, include cosmetics, liquid toners, oil-based inkjet inks, mild solvent-based coatings, lubricants, cleaning agents, heat-conducting materials, conductive materials, and optical materials. Furthermore, by dispersing fillers, primarily pigments, in these liquid media, functions corresponding to specific applications can be imparted.

[0003] For example, in recent years, with the increasing density / integration of printed circuit boards or hybrid ICs carrying electronic components such as transistors, integrated circuits (ICs), and memory elements, and the increasing capacity of secondary batteries (cell-type), thermally conductive silicone compositions containing thermally conductive fillers such as organopolysiloxanes, alumina powder, and zinc oxide powder are widely used as thermally conductive materials in order to efficiently dissipate heat generated from electronic components or batteries and other electronic / electrical devices. Furthermore, in particular, thermally conductive silicone compositions filled with a large amount of thermally conductive filler have been proposed to address high heat dissipation. However, even if the filling rate of the thermally conductive filler in thermal grease or heat sinks is increased to reduce thermal resistance or improve thermal conductivity, the viscosity of the resin composition used in the thermal grease or heat sink increases, making it difficult to spray the resin composition. Therefore, various studies have been conducted to date on combinations of thermally conductive fillers to reduce thermal resistance or improve thermal conductivity in thermal greases or heat sinks (see Patent Documents 1, 2, and 3). However, previous studies on combinations of thermally conductive fillers have either been insufficient in terms of thermal conductivity, or have been conducted on both high thermal conductivity and high viscosity, without taking both into account.

[0004] To address the aforementioned problem, Patent Document 4 describes an organopolysiloxane with a single trimethoxysilyl end in a thermally conductive silicone composition filled with a thermally conductive filler. This organopolysiloxane reduces the viscosity of the composition and imparts fluidity. Because it reduces viscosity or imparts fluidity, it can be used as a dispersant.

[0005] Existing technical documents

[0006] Patent documents

[0007] Patent Document 1: Japanese Patent Application Publication No. 2005-054099

[0008] Patent Document 2: Japanese Patent Application Publication No. 2004-091743

[0009] Patent Document 3: Japanese Patent Application Publication No. 2000-063873

[0010] Patent Document 4: Japanese Patent Application Publication No. 2019-077845 Summary of the Invention

[0011] The problem that the invention aims to solve

[0012] This invention relates to an organopolysiloxane having a partial structure consisting of continuously linked T-shaped structural units and a method for manufacturing the same, and to a filler dispersion comprising an organopolysiloxane having a partial structure consisting of continuously linked T-shaped structural units as a dispersant, wherein the dispersant is a dispersant that can impart superior filler dispersibility in a liquid medium compared to organopolysiloxanes having a single trimethoxysilyl end.

[0013] The objective of this invention is to provide a dispersant capable of imparting excellent dispersibility of fillers in a liquid medium. Furthermore, the objective of this invention is to provide a filler dispersion in which the filler is stably dispersed using said dispersant.

[0014] Technical means to solve the problem

[0015] The inventors conducted intensive research to solve the aforementioned problem and discovered that organopolysiloxanes with a partially structured T-shaped structural units are useful as dispersants, thus completing this invention.

[0016] That is, according to the present invention, an organopolysiloxane having a partial structure of continuously connected T-structure units as shown below can be provided as a dispersant.

[0017] The present invention includes the following items, etc.

[0018] Item 1. An organopolysiloxane, represented by formula (1) or formula (2).

[0019]

[0020] In equations (1) and (2),

[0021] R 1 It is independently a saturated hydrocarbon group having 1 to 12 carbon atoms.

[0022] X is independently a group represented by formula (3), acryloyl, alkyl, carboxyl, vinyl, methacryloyl, aromatic, amino, isocyanate, isocyanurate, epoxy, hydroxy, or mercapto, wherein at least one X is a group represented by formula (3).

[0023] m, l, and k are independently 0 to 10.

[0024] j is 1 to 10;

[0025]

[0026] In equation (3),

[0027] R 2 It is independently a saturated hydrocarbon group having 1 to 12 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms.

[0028] Y is a divalent hydrocarbon group with 1 to 8 carbon atoms.

[0029] h ranges from 4 to 400.

[0030] Item 2. The organopolysiloxane according to Item 1 is the reaction product of the organopolysiloxane represented by formula (4) and the trialkoxysilane.

[0031]

[0032] In equation (4),

[0033] R 1 It is independently a saturated hydrocarbon group having 1 to 12 carbon atoms.

[0034] R 2 It is independently a saturated hydrocarbon group having 1 to 12 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms.

[0035] Y is a divalent hydrocarbon group with 1 to 8 carbon atoms.

[0036] h ranges from 4 to 400.

[0037] Item 3. The method for manufacturing organopolysiloxane according to Item 2, wherein the organopolysiloxane represented by formula (4) is reacted with a trialkoxysilane.

[0038] Item 4. The organopolysiloxane according to Item 1 is formed by intermolecular reaction of the organopolysiloxane represented by formula (4) according to Item 2.

[0039] Item 5. The method for manufacturing organopolysiloxane according to Item 4, wherein the organopolysiloxane represented by formula (4) according to Item 2 is reacted intermolecularly.

[0040] Item 6. The method for manufacturing organopolysiloxane according to Item 3 or Item 5, wherein an organometallic catalyst is used as the catalyst.

[0041] Item 7. The organopolysiloxane according to Item 1, which is the reaction product of the organopolysiloxane represented by formula (5) and an alkoxysilane oligomer having vinyl groups.

[0042]

[0043] In equation (5),

[0044] R 2 It is independently a saturated hydrocarbon group having 1 to 12 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms.

[0045] h ranges from 4 to 400.

[0046] Item 8. The method for manufacturing organopolysiloxane according to Item 7, wherein the organopolysiloxane represented by formula (5) according to Item 7 is reacted with an alkoxysilane oligomer having vinyl groups.

[0047] Item 9. A dispersant comprising the organopolysiloxane according to Item 1 for dispersing filler in a liquid medium.

[0048] Item 10. The dispersant according to Item 9 has a number average molecular weight (Mn) of 500 to 100,000.

[0049] Item 11. The dispersant according to Item 9 or Item 10 has a molecular weight distribution index (Mw / Mn) of 1.0 to 3.0.

[0050] Item 12. A filler dispersion comprising a filler, a liquid medium, and an organopolysiloxane according to Item 1 as a dispersant.

[0051] Item 13. The filler dispersion according to Item 12, wherein the content of the liquid medium is 4 to 50 parts by mass relative to 100 parts by mass of the filler, and the content of the dispersant is 0.1 to 20 parts by mass.

[0052] The effects of the invention

[0053] According to the present invention, a dispersant capable of stably dispersing fillers in a liquid medium can be provided.

[0054] Furthermore, according to the present invention, a filler dispersion that stably disperses the filler can be provided using the aforementioned dispersant. The filler dispersion of the present invention is effective, for example, in cosmetics, liquid developers, oil-based inkjet inks, UV-curable inkjet inks, solvent-based coatings, lithographic inks, lubricants, cleaning agents, pesticides, release agents, adhesives, thermally conductive materials, conductive materials, optical materials, etc. Attached Figure Description

[0055] Figure 1 It is the slightly yellow, transparent liquid obtained in Synthesis Example 1, and is a polydimethylsiloxane with a single trimethoxysilyl terminal used in Synthesis Examples 5 and 10-12. 29 Si-Nuclear Magnetic Resonance (NMR) spectroscopy.

[0056] Figure 2 It is the slightly yellow, transparent liquid obtained in Synthesis Example 2, and is the polydimethylsiloxane with a single trimethoxysilyl terminal used in Synthesis Example 6. 29 Si-NMR spectroscopy.

[0057] Figure 3 It is the pale yellow transparent liquid obtained in Synthesis Example 3. 29 Si-NMR spectroscopy.

[0058] Figure 4 It is the slightly yellow, transparent liquid obtained in Synthesis Example 4, and is the polydimethylsiloxane with a single trimethoxysilyl terminal used in Synthesis Example 7. 29 Si-NMR spectroscopy.

[0059] Figure 5 It is the pale yellow transparent liquid obtained in Synthesis Example 5. 29 Si-NMR spectroscopy.

[0060] Figure 6 It is the colorless and transparent liquid obtained in Synthesis Example 6. 29 Si-NMR spectroscopy.

[0061] Figure 7 This is a graph showing the shear viscosity as the shear rate changes in the silicone dispersants of Examples 1-2, Examples 6-8, and Comparative Examples 1-4.

[0062] Figure 8 This is a graph showing the shear viscosity as the shear rate changes in the silicone dispersants of Examples 1 and 3-5.

[0063] Figure 9This is a graph showing the shear viscosity as the shear rate changes in the silicone dispersants of Examples 6 and 9-10.

[0064] Figure 10 This is a graph showing the shear viscosity as the shear rate changes in the silicone dispersants of Examples 11-12.

[0065] Figure 11 It is the yellow transparent liquid obtained in Synthesis Example 7. 29 Si-NMR spectroscopy.

[0066] Figure 12 It is the colorless, transparent liquid obtained in Synthesis Example 8, and is the polydimethylsiloxane with a single trimethoxysilyl terminal used in Synthesis Example 9. 29 Si-NMR spectroscopy.

[0067] Figure 13 It is the colorless and transparent liquid obtained in Synthesis Example 9. 29 Si-NMR spectroscopy.

[0068] Figure 14 It is the yellow transparent liquid obtained in Synthesis Example 10. 29 Si-NMR spectroscopy.

[0069] Figure 15 It is the yellow transparent liquid obtained in Synthesis Example 11. 29 Si-NMR spectroscopy.

[0070] Figure 16 It is the yellow transparent liquid obtained in Synthesis Example 12. 29 Si-NMR spectroscopy. Detailed Implementation

[0071] The embodiments of the present invention will be described below, but the present invention is not limited to the following embodiments.

[0072] <Dispersant>

[0073] The dispersant of the present invention is a T-structure unit [R1SiO] represented by formula (1) or formula (2). 3 / 2 [A partially structured organopolysiloxane formed by continuous interconnections.]

[0074]

[0075] In equations (1) and (2),

[0076] R 1 It is independently a saturated hydrocarbon group having 1 to 12 carbon atoms.

[0077] X is independently a group represented by formula (3), acryloyl, alkyl, carboxyl, vinyl, methacryloyl, aromatic, amino, isocyanate, isocyanurate, epoxy, hydroxy, or mercapto, wherein at least one X is a group represented by formula (3).

[0078] m, l, and k are independently 0 to 10.

[0079] j is 1 to 10.

[0080]

[0081] In equation (3),

[0082] R 2 It is independently a saturated hydrocarbon group having 1 to 12 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms.

[0083] Y is a divalent hydrocarbon group with 1 to 8 carbon atoms.

[0084] h ranges from 4 to 400.

[0085] The definitions associated with the M, D, T, and Q structural units are related to the number of oxygen atoms bound to them; for example, they can be illustratively represented as siloxane units below.

[0086] M = monofunctional unit [R3SiO] 1 / 2 ]、

[0087] D = Difunctional unit [R2SiO] 2 / 2 ]、

[0088] T = Trifunctional unit [R1SiO] 3 / 2 ]、

[0089] Q = Four functional units [SiO] 4 / 2 ].

[0090] Regarding the T-structure unit [R1SiO] represented by equation (1) or equation (2) 3 / 2 Organopolysiloxanes with a partially continuous structure are considered to be T-structure units [R1SiO] 3 / 2 For the purpose of merely exemplifying a few possible considerations, the structure of a continuous connected partial structure may be represented by equation (7) or equation (8) as equation (1) and equation (9) as equation (2).

[0091]

[0092]

[0093] In equations (7) to (9),

[0094] R1 It is independently a monovalent saturated hydrocarbon group having 1 to 12 carbon atoms.

[0095] X is independently a group represented by formula (3), acryloyl, alkyl, carboxyl, vinyl, methacryloyl, aromatic, amino, isocyanate, isocyanurate, epoxy, hydroxy, or mercapto.

[0096] Moreover, at least one X is a basis represented by equation (3).

[0097]

[0098] In equation (3),

[0099] R 2 It is independently a saturated hydrocarbon group having 1 to 12 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms.

[0100] Y is independently a divalent hydrocarbon group having 1 to 8 carbon atoms.

[0101] H independently ranges from 4 to 400.

[0102] The definition associated with the T structural unit, which is part of the structure in formulas (7) to (9), is related to the number of alkoxy groups, and can be classified, for example, into the four formulas represented by formula (10).

[0103]

[0104] <Method for manufacturing organopolysiloxanes with a partial structure consisting of continuously connected T-shaped structural units>

[0105] The organopolysiloxane of the present invention, having a partial structure formed by continuous T-units, can be synthesized from an organopolysiloxane with a single-terminal trialkoxysilyl group as represented by formula (4) and an alkoxysilane compound having three alkoxy groups. Alternatively, the organopolysiloxane can also be a compound formed by the intermolecular reaction of an organopolysiloxane with a single-terminal trialkoxysilyl group as represented by formula (4). In the reaction, a solvent can be used as needed. As a catalyst, acid catalysts such as hydrochloric acid for hydrolysis and base catalysts such as ammonia can also be used; an organometallic catalyst is preferred.

[0106]

[0107] In equation (4),

[0108] R 1 It is independently a saturated hydrocarbon group having 1 to 12 carbon atoms.

[0109] R 2 It is independently a saturated hydrocarbon group having 1 to 12 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms.

[0110] Y is independently a divalent hydrocarbon group having 1 to 8 carbon atoms.

[0111] h independently ranges from 4 to 400.

[0112] One or more organopolysiloxanes with a single-terminal trialkoxysilyl group can be used. Furthermore, organopolysiloxanes with a single-terminal trialkoxysilyl group can be manufactured using existing known techniques. For example, methods include synthesizing organopolysiloxanes with a single-terminal trialkoxysilyl group of arbitrary molecular weight from organopolysiloxanes with a single-terminal hydrosilyl group of arbitrary molecular weight and vinyltrialkoxysilanes in the presence of a platinum catalyst. Examples of organopolysiloxanes with a single silane terminal include: FM-0105 (number average molecular weight (Mn) = approximately 500), FM-0111 (number average molecular weight (Mn) = approximately 1000), FM-0121 (number average molecular weight (Mn) = approximately 5000), FM-0125 (number average molecular weight (Mn) = approximately 10000), FM-0126 (number average molecular weight (Mn) = approximately 20000), and FM-0127 (number average molecular weight (Mn) = approximately 30000). Examples of vinyltrialkoxysilanes include vinyltrimethoxysilane (S210, produced by JNC) and vinyltriethoxysilane (S220, produced by JNC).

[0113] Regarding organopolysiloxanes with a single-terminal trialkoxysilyl group, examples of trialkoxysilyl groups include trimethoxysilyl, triethoxysilyl, and tripropoxysilyl. Among these, trimethoxysilyl is preferred from the perspectives of the affinity between the synthesized organopolysiloxane with a partially structured T-unit continuously linked structure (i.e., dispersant and filler) and the ease of obtaining vinylalkoxysilanes, which are the raw materials for manufacturing organopolysiloxanes with a single-terminal trialkoxysilyl group.

[0114] Alkoxysilane compounds having three alkoxy groups may use one or more. Examples of alkoxysilane compounds having three alkoxy groups include: alkyl-containing alkoxysilane compounds, vinyl-containing alkoxysilane compounds, acryloyl-containing alkoxysilane compounds, methacryloyl-containing alkoxysilane compounds, aromatic-containing alkoxysilane compounds, amino-containing alkoxysilane compounds, isocyanate-containing alkoxysilane compounds, isocyanurate-containing alkoxysilane compounds, epoxy-containing alkoxysilane compounds, and mercapto-containing alkoxysilane compounds.

[0115] Examples of 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 vinyl-containing alkoxysilane compounds include vinyltrimethoxysilane and vinyltriethoxysilane. Examples of acryloyl-containing alkoxysilane compounds include 3-acryloyloxypropyltrimethoxysilane. Examples of methacryloxysilane compounds include 3-methacryloyloxypropyltrimethoxysilane and 3-methacryloyloxypropyltriethoxysilane. Examples of aromatic-containing alkoxysilane compounds include phenyltrimethoxysilane and phenyltriethoxysilane. Examples of amino-containing alkoxysilane compounds include N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and N-phenyl-3-aminopropyltrimethoxysilane. Examples of isocyanate-containing alkoxysilane compounds include 3-isocyanatepropyltriethoxysilane. Examples of isocyanurate-containing alkoxysilane compounds include tris-(trimethoxysilylpropyl)isocyanurate. Examples of epoxy-containing alkoxysilane compounds include 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-glycidoxypropyltriethoxysilane. Examples of mercapto-containing alkoxysilane compounds include 3-mercaptopropyltrimethoxysilane.

[0116] The solvent can be selected from one or more of non-polar 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; cyaninated hydrocarbons such as acetonitrile; amines; amides such as acetamide; halogenated hydrocarbons such as dichloromethane, chloroform, and hexafluoromethylene; and sulfur-containing compounds such as dimethyl sulfoxide. The amount of solvent used is not particularly limited, and can be adjusted appropriately. Generally, the concentration of the organosilicon compound imparted to the reaction is 5% to 95% by mass, preferably 20% to 80% by mass. Furthermore, the reaction in the manufacturing method of the present invention can also be carried out in a solvent-free system.

[0117] Organometallic catalysts can also be organotin compounds such as dibutyltin dilaurate or dibutyltin di-2-ethylhexanoate, or bismuth, zinc, and zirconium-based organometallic compounds. Titanium alkoxides are preferred as catalysts. Examples of titanium alkoxides include tetra(2-ethylhexyl)titanate, tetra-n-butoxide titanium, tetraisopropoxide titanium, diisopropoxybis(ethyl acetoacetate) titanium, tetraacetylacetone titanium, di-2-ethylhexoxybis(2-ethyl-3-hydroxyhexoxy) titanium, and diisopropoxybis(acetylacetone) titanium. The amount of titanium alkoxide catalyst can be 0.1 to 10 parts by weight relative to 100 parts by weight of an organopolysiloxane with a single trialkoxysilyl terminal. If the amount of titanium alkoxide catalyst is less than 0.1 parts by weight, the reaction is incomplete; if the amount of catalyst is more than 10 parts by weight, there is a possibility of other problems such as yellowing or discoloration.

[0118] Furthermore, the organopolysiloxane of the present invention, which has a partial structure formed by continuous T-structure units, can also be synthesized from an organopolysiloxane with a single hydrosilyl terminus represented by formula (5) and an alkoxysilane oligomer having a vinyl group. In the reaction, the solvent described above can be used as a catalyst, preferably a transition metal catalyst such as a platinum catalyst or a rhodium catalyst.

[0119]

[0120] In equation (5),

[0121] R 2 It is independently a saturated hydrocarbon group having 1 to 12 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms.

[0122] h ranges from 4 to 400.

[0123] One or more organopolysiloxanes with a single-terminal hydrosilyl group may be used. Examples of organopolysiloxanes with a single-terminal hydrosilyl group include: FM-0105 (number average molecular weight (Mn) = approximately 500), FM-0111 (number average molecular weight (Mn) = approximately 1000), FM-0121 (number average molecular weight (Mn) = approximately 5000), FM-0125 (number average molecular weight (Mn) = approximately 10000), FM-0126 (number average molecular weight (Mn) = approximately 20000), and FM-0127 (number average molecular weight (Mn) = approximately 30000).

[0124] Vinyl alkoxysilane oligomers can be manufactured by hydrolyzing and condensing vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, etc., in the presence of an acid catalyst or a base catalyst, according to existing known techniques. Examples of vinyl alkoxysilane oligomers include DYNASYLAN 6490 and DYNASYLAN 6498 from Evonik.

[0125] Examples of transition metal catalysts include: elemental platinum; substances obtained by dispersing platinum solid on supports such as alumina, silica, and carbon black; chloroplatinic acid; complexes of chloroplatinic acid with alcohols, aldehydes, ketones, etc.; platinum-olefin complexes; platinum(O)-divinyltetramethyldisiloxane complexes; and compounds other than platinum compounds such as RhCl(PPh3)3, RhCl3, RuCl3, IrCl3, FeCl3, AlCl3, PdCl2·H2O, NiCl2, and TiCl4.

[0126] The organopolysiloxane dispersant of the present invention, which has a partial structure consisting of continuously linked T-shaped structural units, has a number-average molecular weight (Mn) of 500 to 100,000, more preferably 1,000 to 60,000, as determined by gel permeation chromatography (GPC). If the molecular weight is too small, the steric repulsion during filler dispersion will be insufficient, resulting in a unstable dispersion. Conversely, if the molecular weight is too large, the wettability with the filler will be insufficient, leading to an increase in the viscosity of the dispersion.

[0127] The organopolysiloxane dispersant of the present invention, which has a partial structure consisting of continuously connected T-structure units, can be synthesized from organopolysiloxanes with a single end having a trialkoxysilyl group, as represented by formula (4). The number average molecular weight and molecular weight distribution index (Mw / Mn) of the dispersant can be adjusted by using a necessary amount of organopolysiloxanes with a single end having a trialkoxysilyl group and a molecular weight distribution index (Mw / Mn) of any number. Alternatively, the dispersant of the present invention can also be synthesized from organopolysiloxanes with a single end having a hydrosilyl group, as represented by formula (5). The number average molecular weight and molecular weight distribution index (Mw / Mn) of the dispersant can be adjusted by using a necessary amount of organopolysiloxanes with a single end having a hydrosilyl group and a molecular weight distribution index (Mw / Mn) of any number.

[0128] The dispersant of this invention is used to disperse fillers in a liquid medium. Examples of liquid media include: hydrocarbons, alkanols, enols, fatty acids, unsaturated fatty acids, esters of fatty acids and hydroxyl-containing compounds, esters of unsaturated fatty acids and hydroxyl-containing compounds, silicone oils, acrylic resins, epoxy resins, urethane resins, etc. These liquid media can be used alone or in combination of two or more. Silicone oil is a suitable liquid medium for use as a heat-conducting material.

[0129] Examples of hydrocarbons include: hexane, hexene, 2-ethylhexane, heptane, heptene, cyclohexane, cycloheptane, octane, octene, nonane, decane, isodecane, dodecane, isododecane, tridecane, undecane, octadecane, C8-20 isoalkanes, squalane, petrolatum, microcrystalline wax, hydrogenated polyisobutylene, 1-octene, 2-octene, 1-nonene, 2-nonene, 1-decene, 2-decene, 1-undecene, 2-undecene, 1-dodecene, 2-dodecene, 1-tetracene, 2-tetracene, 1-tetradecene, 2-tetradecene, 1-pentadecanene, 2-pentadecanene, 1-hexadecene, 2-hexadecene, 1-heptadecene, 2-heptadecene, 1-octadecene, 2-octadecene, dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane, propylcyclohexane, etc.

[0130] Examples of alkanols and enols include: octanol, 2-ethylhexanol, nonanol, decanol, isodecanol, dodecyl alcohol, cetyl alcohol, stearyl alcohol, arachidyl alcohol, docosyl alcohol, hexyldecyl alcohol, octyldodecyl alcohol, isocetyl alcohol, isostearyl alcohol, oleyl alcohol, etc.

[0131] Examples of fatty acids and unsaturated fatty acids include: caprylic acid, nonanoic acid, capric acid, dodecanoic acid, tridecanoic acid, stearic acid, oleic acid, 1,2-hydroxystearic acid, ricinoleic acid, ricinoleic acid, undecenoic acid, isononanoic acid, myristic acid, palmitic acid, 2-ethylhexanoic acid, etc.

[0132] Examples of esters containing fatty acids and hydroxyl-containing compounds, as well as esters containing unsaturated fatty acids and hydroxyl-containing compounds, include: methyl laurate, heptyl undecenoate, isononyl isononanoate, ethyl oleate, isopropyl myristate, isopropyl palmitate, butyl stearate, cetyl palmitate, myristyl myristate, octyl dodecyl myristate, isopropyl isostearate, ethyl isostearate, cetyl 2-ethylhexanoate, hexyl isostearate, and di-2-ethylhexanoic acid. Ethylene glycol, ethylene glycol dioleate, di(octyl-octanoic acid)propylene glycol, propylene glycol dioleate, trimethylolpropane triisostearate, pentaerythritol tetraethylhexanoate, neopentyl glycol diheptanoate, isocetyl isostearate, 2-octyl dodecyl dimethyl octanoate, myristyl lactate, trioctyl dodecyl citrate, diisostearate malate, di-2-ethylhexyl succinate, diisopropyl adipate, diisobutyl adipate, cholesterol stearate, etc. Further examples include: almond oil, avocado oil, olive oil, shea butter, shea butter oil, evening primrose oil, passionflower seed oil, camellia oil, babassu oil, peanut oil, rosehip oil, etc., which are triesters of glycerol; and waxes such as beeswax, wood wax, simonial wax, candelilla wax, carnauba wax, etc.

[0133] Examples of silicone oils include: dimethyl silicone oil, methylphenyl silicone oil, methylhydrosilicone oil, amino-modified silicone oil, epoxy-modified silicone oil, carboxyl-modified silicone oil, methanol-modified silicone oil, polyether-modified silicone oil, alkyl-modified silicone oil, and fluorine-modified silicone oil.

[0134] Examples of acrylic resins include: monofunctional (meth)acrylates, difunctional (meth)acrylates, trifunctional or more multifunctional (meth)acrylates, (meth)acrylate epoxy esters, (meth)acrylate urethanes, and difunctional or more polyester (meth)acrylates.

[0135] Examples of epoxy resins include combinations of main agents and hardeners such as bisphenol A, bisphenol F, phenolic varnishes (phenolic glycidyl ethers), and alcoholic glycidyl ethers (polypropylene glycol). Furthermore, examples of hardeners include aliphatic polyamines, modified aliphatic polyamines, polyamide amines, polyamides, alicyclic polyamines, modified alicyclic polyamines, modified aromatic polyamines, and tertiary amines. These hardeners can be used alone or in combination of two or more. Additionally, reaction accelerators that promote the reaction between the main agent and the hardener can be used. Examples of reaction accelerators include phenol, p-tertiary butylphenol, di-tertiary butylphenol, cresol, triphenyl phosphite, salicylic acid, and triethanolamine. These reaction accelerators can be used alone or in combination of two or more.

[0136] Examples of urethane resins include: reaction products of hydroxyl-containing compounds and polyisocyanate compounds; polyurethanes obtained by reacting short-chain diols or short-chain ethers (as hard segments) with isocyanate compounds; and linear multi-block copolymers of polyurethanes obtained by reacting long-chain diols or long-chain ethers (as short segments) with isocyanate compounds. Additionally, examples include reaction products (cured products) of urethane prepolymers and polyisocyanate compounds.

[0137] Examples of fillers include: inorganic pigments, organic pigments, extender pigments, fillers, inorganic microparticles, diamond, graphene, graphite, carbon black, carbon nanotubes, clay, conductive fillers, thermal conductive agents, carbon fibers, glass fibers, cellulose, cellulose nanofibers, etc. These fillers are particulate, powdered, or fibrous substances added to plastics, rubber, coatings, inks, etc., to improve strength or functionality and reduce costs. There are no particular restrictions on the crystal form, particle size, surface condition, or presence or absence of surface treatment of the filler. As a filler (thermal conductive agent) for thermal conductivity, alumina, zinc oxide, aluminum nitride, or boron nitride are preferred, with alumina being more preferred.

[0138] <Packaging Dispersion>

[0139] The filler dispersion of the present invention comprises a filler, a liquid medium, and a dispersant for dispersing the filler in the liquid medium. Furthermore, the dispersant is an organopolysiloxane having a partially structured form of continuously linked T-shaped structural units. The liquid medium is the aforementioned liquid medium. Silicone oil is preferred. Furthermore, in addition to a liquid medium, various organic solvents, monomers, and liquid oligomers may also be used.

[0140] The filler used is the aforementioned filler. Preferably, it is alumina, zinc oxide, aluminum nitride, or boron nitride, and more preferably alumina.

[0141] In the filler dispersion, the content of the liquid medium relative to 100 parts by weight of the filler is preferably 4 to 50 parts by weight, more preferably 5 to 30 parts by weight. Furthermore, in the filler dispersion, the content of the dispersant relative to 100 parts by weight of the filler is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight. If the content of the dispersant relative to 100 parts by weight of the filler is less than 0.1 parts by weight, it may be difficult to achieve stable dispersion of the filler. On the other hand, if the content of the dispersant relative to 100 parts by weight of the filler exceeds 10 parts by weight, it contains excess dispersant that does not contribute to the dispersion of the filler.

[0142] In the filler dispersion of the present invention, various additives such as other surfactants, plasticizers and defoamers can be formulated within a range that does not impair its purpose.

[0143] The filler dispersion of the present invention can be manufactured according to known methods for manufacturing filler dispersions. Examples include: adding filler to a liquid medium containing a dispersant and then mixing it; adding a liquid medium and a dispersant to the filler and then mixing it. Known dispersers can be used as the dispersing equipment for stirring, mixing, or dispersing. Examples include: roller mills, ball mills, bead mills, sand mills, homogenizers, dispersers, and rotary mixers. Alternatively, dispersion can be performed in an ultrasonic bath.

[0144] Example

[0145] The present invention will now be further described in detail. Furthermore, unless otherwise specified, "parts" and "%" in the embodiments refer to mass units (parts by mass, % by mass). In addition, the present invention is not limited to these embodiments in any way.

[0146] <Determination of molecular weight>

[0147] The molecular weight of organopolysiloxanes was determined by gel permeation chromatography (GPC), and the ratio of weight-average molecular weight (Mw) to number-average molecular weight (Mn) was set as the molecular weight distribution index (Mw / Mn). Polystyrene was used as a standard sample to determine the converted molecular weight of polystyrene.

[0148] Furthermore, the determination of the equivalent molecular weight of polystyrene based on the GPC method is carried out under the following test conditions:

[0149] a) Measuring instrument: High-pressure liquid chromatograph (HPLC) LC-2000 Plus series manufactured by Nippon Spectros Technology Co., Ltd.

[0150] b) Pipeline: Showa Denko (Shodex) KF-804L × 2 pipes

[0151] c) Oven temperature: 40℃

[0152] d) Eluent: Toluene 0.7 mL / min

[0153] e) Standard sample: Polystyrene

[0154] f) Injection volume: 20 μL

[0155] Concentration (g): 0.05 g / 10 mL

[0156] h) Sample preparation: Toluene was used as a solvent and dissolved by stirring at room temperature.

[0157] Nuclear Magnetic Resonance Spectroscopy (NMR)

[0158] It uses the JNM-ECZ400S manufactured by Nippon Electronics Co., Ltd. (Regarding...) 29 Solvent-free determination was performed using Si-NMR. 29 In Si-NMR, the peak detection magnetic field originating from the T-structure unit usually becomes the high magnetic field side in the order of T3 > T2 > T1 > T0. Therefore, the generation of the organopolysiloxane with a partial structure formed by continuous connection of T-structure units in this invention can be confirmed by the manifestation of the peak values ​​of the T1 to T3 structures.

[0159] <Synthetic Example 1: Synthesis of a single-terminal alkoxysilane with a number-average molecular weight of 1500>

[0160] Weigh out 300 g of polydimethylsiloxane (number average molecular weight (Mn) = 1300) and 55 g of vinyltrimethoxysilane (S210 manufactured by JNC, molecular weight = 148.2) with single-terminal hydrosilyl groups into a 500 ml four-necked flask equipped with a stirrer, thermometer, and reflux condenser. Under nitrogen atmosphere, heat to 70 °C while stirring. Once 70 °C is reached, add 3.0 x 4 μL of Pt-VTSC-1 (manufactured by Umicore Japan) as a Karstedt catalyst, and stir at 70 °C for 1 hour. Cool to room temperature and replace the reflux condenser with a distillation head equipped with a collection flask. Next, the product was heated at 150°C for 1 hour under reduced pressure of 5 kPaA using a vacuum pump, and then heated at 150°C for 2 hours under reduced pressure of 0.1 kPaA to remove the volatile substances remaining in the product by distillation, thereby obtaining 338 g of a slightly yellow transparent liquid, which is a polydimethylsiloxane with a single trimethoxysilyl end.

[0161] 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).

[0162]

[0163] <Synthetic Example 2: Synthesis of a single-terminal alkoxysilane with a number-average molecular weight of 6500>

[0164] Weigh out 1000 g of polydimethylsiloxane (number average molecular weight (Mn) = 5000) and 45 g of vinyltrimethoxysilane (S210 from JNC Corporation, molecular weight = 148.2) with single-terminal hydrosilyl groups into a 2000 ml four-necked flask equipped with a stirrer, thermometer, and reflux condenser. Heat to 70 °C under nitrogen atmosphere with stirring. Once 70 °C is reached, add 3.0 x 12 μL of Pt-VTSC- from Umicore Japan, a Karstedt catalyst, and stir at 70 °C for 1 hour. Cool to room temperature and replace the reflux condenser with a distillation head containing a collecting flask. Next, the product was heated at 150°C for 1 hour under reduced pressure of 5 kPaA using a vacuum pump, and then heated at 150°C for 2 hours under reduced pressure of 0.1 kPaA to remove the residual volatile substances by distillation, resulting in 1010 g of a slightly yellow transparent liquid, which is a polydimethylsiloxane with a single trimethoxysilyl end.

[0165] 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).

[0166]

[0167] <Synthetic Example 3: Synthesis of a single-terminal alkoxysilane with a number-average molecular weight of 12,000>

[0168] 659 g of polydimethylsiloxane (number average molecular weight (Mn) = 11100) and 20 g of vinyltrimethoxysilane (S210 from JNC Corporation, molecular weight = 148.2) with single-terminal hydrosilyl groups were weighed into a 1000 ml four-necked flask equipped with a stirrer, thermometer, and reflux condenser. The mixture was heated to 70 °C under nitrogen atmosphere with stirring. After reaching 70 °C, 3.0 x 76 μL of Pt-VTSC-3 from Umicore Japan, a Karstedt catalyst, was added, 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 with a collection flask. Then, the product was heated at 120 °C for 1 hour under reduced pressure of 0.3 kPaA using a vacuum pump to remove residual volatile substances by distillation, yielding 663 g of a pale yellow transparent liquid, which is polydimethylsiloxane with single-terminal trimethoxysilyl groups. Figure 3 It is the obtained slightly yellow and transparent liquid 29 Si-NMR spectroscopy.

[0169] 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).

[0170]

[0171] <Synthetic Example 4: Synthesis of a single-terminal alkoxysilane with a number-average molecular weight of 17,000>

[0172] 697 g of polydimethylsiloxane (number average molecular weight (Mn) = 17100) and 14 g of vinyltrimethoxysilane (S210 from JNC Corporation, molecular weight = 148.2) with single-terminal hydrosilyl groups were weighed into a 1000 ml four-necked flask equipped with a stirrer, thermometer, and reflux condenser. The mixture was heated to 70 °C under nitrogen atmosphere with stirring. After reaching 70 °C, 81 μL of Pt-VTSC-3.0 from Umicore Japan, a Karstedt catalyst, was added, 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 with a collection flask. Then, the product was heated at 120 °C for 1 hour under reduced pressure of 0.3 kPaA using a vacuum pump to remove residual volatile substances by distillation, yielding 703 g of a pale yellow transparent liquid, which is polydimethylsiloxane with single-terminal trimethoxysilyl groups.

[0173] 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).

[0174]

[0175] <Synthetic Example 5: Synthesis of an organopolysiloxane with a number average molecular weight of 7200 and a partial structure consisting of continuously linked T-units>

[0176] 30 g of polydimethylsiloxane (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 (Fujifilm Wako Pure Chemical Industries, Ltd., molecular weight = 564.8) with trimethoxysilyl groups at one end were weighed into a 100 ml two-necked flask equipped with a stirrer, thermometer, and reflux condenser. The mixture was stirred at 60°C–70°C for 4 hours under nitrogen atmosphere while being heated. Then, a liquid obtained by mixing 0.72 g of water with 10 g of tetrahydrofuran was added at 70°C for 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°C–70°C.

[0177] After cooling to room temperature, transfer the reaction solution to a separatory funnel, add 20g of n-hexane and 20g of water, shake, and let stand. Once separated into two layers, extract the lower aqueous layer from the separatory funnel. Then, add 50g of water to the separatory funnel, shake, and let stand. Once separated into two layers, extract the lower aqueous layer from the separatory funnel. Repeat this operation twice.

[0178] The remaining 56g of oil layer in the separatory funnel was transferred to a 100ml two-necked flask equipped with a stir bar, thermometer, collecting flask, and distillation head. The mixture was heated at 25°C for 2 hours under reduced pressure of 0.3kPaA using a vacuum pump, thereby removing the volatile substances remaining in the product by distillation. 25g of a slightly yellow, transparent liquid was obtained remaining in the flask.

[0179] 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).

[0180]

[0181] Figure 5 This refers to the slightly yellow, transparent liquid obtained in Synthesis Example 5. 29 Si-NMR spectroscopy, Figure 1 This refers to the polydimethylsiloxane with a single trimethoxysilyl terminal used in Synthesis Example 5. 29 Si-NMR spectroscopy. Figure 5 of 29In the Si-NMR spectrum, the peaks of -41.2 ppm to -40.8 ppm of the T units of polydimethylsiloxane with a single trimethoxysilyl end disappeared, and broad peaks were reconfirmed at -48.7 ppm, -57.3 ppm, and -67.4 ppm.

[0182] Based on the above analysis results, it can be determined that the obtained slightly yellow transparent liquid is an organopolysiloxane with a number average molecular weight of 7200 and a partial structure consisting of continuously connected T structural units.

[0183] <Synthetic Example 6: Synthesis of a partial structure of organopolysiloxane with a number average molecular weight of 28,000 and consisting of continuously linked T-structural units>

[0184] 30 g of polydimethylsiloxane (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 (Fujifilm Wako Pure Chemical Industries, Ltd., molecular weight = 564.8) with trimethoxysilyl groups at one end were weighed into a 100 ml two-necked flask equipped with a stirrer, thermometer, and reflux condenser. The mixture was stirred at 60 °C for 2 hours under nitrogen atmosphere while being heated. Then, a liquid obtained by mixing 0.16 g of water with 10 g of tetrahydrofuran was fed into the flask at 60 °C for 5 minutes, and the mixture was 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 °C to 70 °C.

[0185] After cooling to room temperature, transfer the reaction solution to a separatory funnel, add 20g of n-hexane and 30g of water, shake, and let stand. Once separated into two layers, extract the lower aqueous layer from the separatory funnel. Then, add 30g of water to the separatory funnel, shake, and let stand. Once separated into two layers, extract the lower aqueous layer from the separatory funnel. Repeat this operation twice.

[0186] The remaining 57g of oil layer in the separatory funnel was transferred to a 100ml two-necked flask equipped with a stir bar, thermometer, collecting flask, and distillation head. The mixture was heated at 40°C for 2 hours under reduced pressure of 0.3kPaA using a vacuum pump, thereby removing the volatile substances remaining in the product by distillation. 28g of a colorless, transparent liquid was obtained remaining in the flask.

[0187] GPC: Number average molecular weight (Mn) = 28000, weight average molecular weight (Mw) = 37500, molecular weight distribution index (Mw / Mn) = 1.34. 29Si-NMR: δ (ppm); 7.8~8.5(M), -22.2~-21.3(D), -56.7(T), -66.1(T).

[0188]

[0189] Figure 6 This refers to the colorless and transparent liquid obtained in Synthesis Example 6. 29 Si-NMR spectroscopy, Figure 2 This refers to the polydimethylsiloxane with a single trimethoxysilyl terminal used in Synthesis Example 6. 29 Si-NMR spectroscopy. Figure 6 of 29 In the Si-NMR spectrum, the peaks at -42.5 ppm to -42.2 ppm of the T units of polydimethylsiloxane with a single trimethoxysilyl end disappeared, and broad peaks were reconfirmed at -56.7 ppm and -66.1 ppm.

[0190] Based on the analysis results, it can be determined that the obtained colorless and transparent liquid is an organopolysiloxane with a number average molecular weight of 28,000 and a partial structure consisting of continuously connected T-structure units.

[0191] <Synthetic Example 7: Synthesis of an organopolysiloxane with a number average molecular weight of 88,500 and a partial structure consisting of continuously linked T-units>

[0192] 30 g of polydimethylsiloxane (number average molecular weight (Mn) = 16900, weight average molecular weight (Mw) = 17600, molecular weight distribution index (Mw / Mn) = 1.04) and 11 mg of tetra(2-ethylhexyl) titanate (Fujifilm Wako Pure Chemical Industries, Ltd., molecular weight = 564.8) with trimethoxysilyl groups at the single end were weighed into a 100 ml three-necked flask equipped with a stirrer, thermometer, and reflux condenser. The mixture was stirred at 60°C–70°C for 4 hours under nitrogen atmosphere while being heated. Then, a liquid obtained by mixing 10 g of tetrahydrofuran with 0.72 g of water was fed into the flask at 70°C for 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°C–70°C.

[0193] After cooling to room temperature, transfer the reaction solution to a separatory funnel, add 20g of n-hexane and 20g of water, shake, and let stand. Once confirmed to be separated into two layers, extract the lower aqueous layer from the separatory funnel. Then add 50g of water to the separatory funnel, shake, and let stand. Once confirmed to be separated into two layers, extract the lower aqueous layer from the separatory funnel. Repeat this operation twice.

[0194] The remaining 52g of oil layer in the separatory funnel was transferred to a 100ml two-necked flask equipped with a stir bar, thermometer, collecting flask, and distillation head. The mixture was heated at 25°C for 2 hours under reduced pressure of 0.3kPaA using a vacuum pump, thereby removing the volatile substances remaining in the product by distillation. 21g of a yellow, transparent liquid remained in the flask.

[0195] 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).

[0196]

[0197] Figure 11 The yellow transparent liquid obtained in Synthesis Example 7 represents 29 Si-NMR spectroscopy, Figure 4 This refers to the polydimethylsiloxane with a single trimethoxysilyl terminal used in Synthesis Example 7. 29 Si-NMR spectroscopy. Figure 11 of 29 In Si-NMR spectra, the disappearance of the peak at -42.4 ppm to -42.2 ppm from the T unit of polydimethylsiloxane with a single trimethoxysilyl end was confirmed.

[0198] Based on the above analysis results, it can be determined that the obtained yellow transparent liquid is an organopolysiloxane with a number average molecular weight of 85,500 and a partial structure consisting of continuously connected T structural units.

[0199] <Synthetic Example 8: Synthesis of an organopolysiloxane with a single alkoxysilyl terminus of molecular weight 561>

[0200] 300 g of polydimethylsiloxane (molecular weight = 412.9) and 26 g of vinyltrimethoxysilane (JNC S210, molecular weight = 148.2) with a single hydrosilyl end were weighed into a 500 ml four-necked flask equipped with a stirrer, a pressure equalizing dropping funnel, a thermometer, and a reflux condenser. The mixture was heated to 70 °C under nitrogen atmosphere with stirring. After reaching 70 °C, 1 μL of Pt-VTSC-3.0 (from Umicore Japan) was added as a Karstedt catalyst. 129 g of vinyltrimethoxysilane was weighed into the pressure equalizing dropping funnel and added dropwise to the reaction mixture over 10 minutes. The mixture was stirred at 70 °C for 1 hour. Then, 1 μL of Pt-VTSC-3.0 was added at 70 °C, and the mixture was stirred at 85 °C for 2 hours. After cooling to room temperature, the reflux condenser was replaced with a distillation head with a collecting flask. Next, the product was heated at 100°C under reduced pressure of 2.0 kPaA using a vacuum pump to remove residual volatile substances by distillation. Further heating at 100°C under reduced pressure of 0.1 kPaA was then performed to remove residual volatile substances by distillation, yielding 405 g of a colorless, transparent liquid, a polydimethylsiloxane (molecular weight = 561.1) with a single trimethoxysilyl terminal.

[0201] 29 Si-NMR: δ (ppm); 7.7~9.1(M), -22.2~-20.9(D), -42.3~-42.0(T).

[0202]

[0203] <Synthetic Example 9: Synthesis of an organopolysiloxane with a number average molecular weight of 4400 and a partial structure consisting of continuously linked T-units>

[0204] 100 g of polydimethylsiloxane (molecular weight = 561) with a single trimethoxysilyl end and 0.3 g of tetra(tributyl)titanate (Matsumoto Fine Chemical Co., Ltd., molecular weight = 340.4) were weighed into a 300 ml four-necked flask equipped with a stirrer, a pressure equalizing dropping funnel, a thermometer, and a reflux condenser. The mixture was stirred at 80 °C for 30 minutes under nitrogen atmosphere while the temperature was gradually increased. Then, the mixture was fed into a solution of 40 g of N,N-dimethylformamide and 31 g of water at 65 °C for 3 hours, and stirred at 90 °C for 7 hours.

[0205] After cooling to room temperature, the reflux condenser was replaced with a distillation head equipped with a collecting flask. The product was then heated at 100°C under reduced pressure of 5.0 kPaA using a vacuum pump to remove residual volatiles by distillation. Further heating at 125°C under reduced pressure of 0.1 kPaA was then performed to remove any remaining volatiles by distillation. The white suspension remaining in the flask was transferred to a stainless steel holder equipped with a 3 μm filter and filtered under pressure using nitrogen to obtain 72 g of a colorless, transparent liquid.

[0206] 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

[0207]

[0208] Figure 13 This refers to the colorless and transparent liquid obtained in Synthesis Example 9. 29 Si-NMR spectroscopy, Figure 12 This refers to the polydimethylsiloxane with a single trimethoxysilyl terminal used in Synthesis Example 9. 29 Si-NMR spectroscopy. Figure 13 of 29 In the Si-NMR spectrum, the peaks of -42.3 ppm to -42.0 ppm of the T units of polydimethylsiloxane with a single trimethoxysilyl end disappeared, and broad peaks were reconfirmed at -55.1 ppm and -64.7 ppm.

[0209] Based on the above analysis results, it can be determined that the obtained colorless and transparent liquid is an organopolysiloxane with a number average molecular weight of 4400 and a partial structure consisting of continuously connected T structural units.

[0210] <Synthetic Example 10: Reaction of a polydimethylsiloxane with a single trimethoxysilyl terminal with hexyltriethoxysilane to synthesize an organopolysiloxane with an average molecular weight of 6700 and a partially structured T-unit.>

[0211] In a 500ml four-necked flask equipped with a stir bar, a pressure-equalizing dropping funnel, a thermometer, and a reflux condenser, 90g of polydimethylsiloxane (number-average molecular weight (Mn) = 1500, weight-average molecular weight (Mw) = 1700, molecular weight distribution index (Mw / Mn) = 1.14), 79g of hexyltriethoxysilane (Tokyo Chemical Industry Co., Ltd., molecular weight = 248.4), and 10g of tetrakis(2-ethylhexyl) titanate (Fujifilm Wako Pure Chemicals Co., Ltd., molecular weight = 564.8) with trimethoxysilyl groups at one end were weighed separately. Under nitrogen atmosphere, the mixture was stirred and heated to 80°C for 30 minutes. Then, the mixture was fed into a solution of 90g of N,N-dimethylformamide mixed with 72g of water at 80°C for 3 hours, and stirred at 90°C for 7 hours.

[0212] After cooling to room temperature, the reflux condenser was replaced with a distillation head equipped with a collecting flask. The product was then heated to 100°C under reduced pressure (5.0 kPaA) using a vacuum pump to remove residual volatiles by distillation. Further heating to 125°C under reduced pressure (0.1 kPaA) was then performed to remove any remaining volatiles by distillation. The remaining yellow suspension in the flask was transferred to a stainless steel holder equipped with a 3 μm filter and filtered under pressure using nitrogen to obtain 130 g of a yellow, transparent liquid.

[0213] 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).

[0214]

[0215] Figure 14 The yellow transparent liquid obtained in Synthesis Example 10 represents 29 Si-NMR spectroscopy, Figure 1 This refers to the polydimethylsiloxane with a single trimethoxysilyl terminal used in Synthesis Example 10. 29 Si-NMR spectroscopy. Figure 14 of 29 In Si-NMR spectra, the disappearance of the peak from -41.2 ppm to -40.8 ppm of the T unit of polydimethylsiloxane with a single trimethoxysilyl end was confirmed.

[0216] Based on the above analysis results, it can be determined that the obtained yellow transparent liquid is an organopolysiloxane with a number average molecular weight of 6700 and a partial structure consisting of continuously connected T structural units.

[0217] <Synthetic Example 11: Reaction of a polydimethylsiloxane with a single trimethoxysilyl terminal with phenyltriethoxysilane to synthesize an organopolysiloxane with an average molecular weight of 6200 and a partially structured T-unit.>

[0218] In a 500ml four-necked flask equipped with a stir bar, a pressure-equalizing dropping funnel, a thermometer, and a reflux condenser, 90g of polydimethylsiloxane (number-average molecular weight (Mn) = 1500, weight-average molecular weight (Mw) = 1700, molecular weight distribution index (Mw / Mn) = 1.14), 77g of phenyltriethoxysilane (Tokyo Chemical Industry Co., Ltd., molecular weight = 240.4), and 10g of tetrakis(2-ethylhexyl) titanate (Fujifilm Wako Pure Chemicals Co., Ltd., molecular weight = 564.8) with trimethoxysilyl groups at one end were weighed separately. Under nitrogen atmosphere, the mixture was stirred and heated to 80°C for 30 minutes. Then, the mixture was fed into a solution of 90g of N,N-dimethylformamide mixed with 72g of water at 80°C for 3 hours, and stirred at 90°C for 7 hours.

[0219] After cooling to room temperature, the reflux condenser was replaced with a distillation head equipped with a collecting flask. The product was then heated to 100°C under reduced pressure (5.0 kPaA) using a vacuum pump to remove residual volatiles by distillation. Further heating to 125°C under reduced pressure (0.1 kPaA) was then performed to remove any remaining volatiles by distillation. The yellow suspension remaining in the flask was transferred to a stainless steel holder equipped with a 3 μm filter and filtered under pressure using nitrogen to obtain 125 g of a yellow, transparent liquid.

[0220] 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).

[0221]

[0222] Figure 15 The yellow transparent liquid obtained in Synthesis Example 11 represents 29 Si-NMR spectroscopy, Figure 1 This refers to the polydimethylsiloxane with a single trimethoxysilyl terminal used in Synthesis Example 11. 29 Si-NMR spectroscopy. Figure 15 of 29 In Si-NMR spectra, the disappearance of the peak from -41.2 ppm to -40.8 ppm of the T unit of polydimethylsiloxane with a single trimethoxysilyl end was confirmed.

[0223] Based on the above analysis results, it can be determined that the obtained yellow transparent liquid is an organopolysiloxane with a number average molecular weight of 6200 and a partial structure consisting of continuously connected T structural units.

[0224] <Synthetic Example 12: Reaction of a polydimethylsiloxane with a single trimethoxysilyl terminus with 3-methacryloyloxypropyltriethoxysilane to synthesize an organopolysiloxane with an average molecular weight of 8100 and a partially structured T-unit.>

[0225] In a 300 ml four-necked flask equipped with a stir bar, a pressure-equalizing dropping funnel, a thermometer, and a reflux condenser, 45 g of polydimethylsiloxane (quantity average molecular weight (Mn) = 1500, weight average molecular weight (Mw) = 1700, molecular weight distribution index (Mw / Mn) = 1.14), 46 g of 3-methacryloyloxypropyltriethoxysilane (Tokyo Chemical Industry Co., Ltd., molecular weight = 290.4), and 0.7 g of tetrakis(tributyl)titanate (Matsumoto Fine Chemical Co., Ltd., molecular weight = 340.4) with trimethoxysilyl groups at one end were weighed separately. Under nitrogen atmosphere, the mixture was stirred and heated to 80 °C for 30 minutes. Then, the mixture was fed into a solution of 40 g of N,N-dimethylformamide and 46 g of water at 80 °C for 3 hours, and stirred at 90 °C for 7 hours.

[0226] After cooling to room temperature, the reflux condenser was replaced with a distillation head equipped with a collecting flask. The product was then heated to 100°C under reduced pressure (5.0 kPaA) using a vacuum pump to remove residual volatiles by distillation. Further heating to 100°C under reduced pressure (0.1 kPaA) was then performed to remove any remaining volatiles by distillation. The remaining yellow suspension in the flask was transferred to a stainless steel holder equipped with a 3 μm filter and filtered under pressure using nitrogen to obtain 66 g of a yellow, transparent liquid.

[0227] 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).

[0228]

[0229] Figure 16 The yellow transparent liquid obtained in Synthesis Example 12 represents 29 Si-NMR spectroscopy, Figure 1This refers to the polydimethylsiloxane with a single trimethoxysilyl terminal used in Synthesis Example 12. 29 Si-NMR spectroscopy. Figure 16 of 29 In Si-NMR spectra, the disappearance of the peak from -41.2 ppm to -40.8 ppm of the T unit of polydimethylsiloxane with a single trimethoxysilyl end was confirmed.

[0230] Based on the above analysis results, it can be determined that the obtained yellow transparent liquid is an organopolysiloxane with a number average molecular weight of 8100 and a partial structure consisting of continuously connected T structural units.

[0231] <Preparation of Samples for Dispersion Evaluation 1-2>

[0232] In an ointment container, silicone oil (polydimethylsiloxane, KF-96-1000CS manufactured by Shin-Etsu Chemical Industry Co., Ltd.) as the liquid medium and organopolysiloxanes synthesized in Synthesis Examples 1-7 and 9-10 as the dispersant were measured. Alumina (DAW-10 manufactured by Denka Corporation), with an average diameter of 13 μm, as the dispersed phase, was then measured and stirred using a spatula. KF-96-1000CS, the organopolysiloxanes synthesized in Synthesis Examples 1-7, and 9-10, and the alumina were measured in the amounts shown in Tables 1-4. Subsequently, using a defoaming stirrer (Taro vacuum type, ARV-310) from THINKY Corporation, the mixture was kneaded at 2000 rpm for 1 minute under normal pressure and then at 2000 rpm for 1 minute under reduced pressure to prepare a dispersibility evaluation sample.

[0233] <Dispersion Evaluation 1 to Dispersion Evaluation 2>

[0234] Dispersion was evaluated as follows: for the dispersion evaluation sample prepared as described above, the shear viscosity at different shear rates was measured using a rheometer (MCR302 manufactured by Anton Paar) under the following conditions.

[0235] Plate shape: 25mm φ circular flat plate

[0236] Sample thickness: 1mm

[0237] Temperature: 25±1℃

[0238] Shearing speed: 0.01s -1 ~100S -1

[0239] Regarding Examples 1-2 and 6-8, the organopolysiloxanes with a partially structured T-shaped structure synthesized in Synthetic Examples 5-7 and 9-10, as shown in Tables 1-4, were used as dispersants, and their shear viscosity at the specified shear rate was measured for evaluation. Regarding Comparative Examples 1-4, the organopolysiloxanes with a single alkoxysilyl terminal synthesized in Synthetic Examples 1-4, as shown in Tables 1-4, were used as dispersants, and their shear viscosity at the specified shear rate was measured for evaluation. The results are shown in Tables 1-4 and... Figure 7 middle.

[0240] Table 1. Dispersion Evaluation Results 1-1

[0241]

[0242] Table 2. Dispersion Evaluation Results 1-2

[0243]

[0244] Table 3. Dispersion Evaluation Results 1-3

[0245]

[0246] Table 4. Dispersion Evaluation Results 1-4

[0247]

[0248] In addition, in Examples 1, 3-6, and 9-10, the organopolysiloxanes with a partially structured T-shaped unit synthesized in Synthesis Examples 5 and 7 were used as dispersants, as shown in Tables 5-8. The proportion of the dispersant was varied, and the shear viscosity at different shear rates was measured for evaluation. The results are shown in Tables 5-8 and... Figures 8-9 middle.

[0249] Table 5. Dispersion Evaluation Results 2-1

[0250]

[0251] Table 6. Dispersion Evaluation Results 2-2

[0252]

[0253] Table 7. Dispersion Evaluation Results 2-3

[0254]

[0255] Table 8. Dispersion Evaluation Results 2-4

[0256]

[0257] <Preparation of Samples for Dispersion Evaluation 3>

[0258] In an ointment container, silicone oil (polydimethylsiloxane, manufactured by Shin-Etsu Chemical Industry Co., Ltd., KF-96-300CS) as the liquid medium and organopolysiloxane synthesized in Synthesis Example 5 as the dispersant were measured. Then, alumina (DAW-03, manufactured by Denka Co., Ltd., with an average diameter of 5 μm) and alumina (DAW-45, manufactured by Denka Co., Ltd., with an average diameter of 50 μm) as the dispersed phase were measured and stirred with a spatula. KF-96-300CS, the organopolysiloxane synthesized in Synthesis Example 5, and alumina were measured in the amounts shown in Tables 9-12. Subsequently, using a defoaming stirrer (Taro vacuum type, model: ARV-310) from THINKY Corporation, the mixture was kneaded at 2000 rpm for 1 minute under normal pressure and then at 2000 rpm for 1 minute under reduced pressure to prepare a dispersibility evaluation sample.

[0259] <Dispersion Evaluation 3>

[0260] Dispersibility was evaluated as follows: for the dispersibility evaluation sample prepared as described above, the shear viscosity at different shear rates was measured using a rheometer (MCR302 manufactured by Anton Paar) under the following conditions.

[0261] Plate shape: 25mm φ circular flat plate

[0262] Sample thickness: 1mm

[0263] Temperature: 25±1℃

[0264] Shearing speed: 0.01s -1 ~100S -1

[0265] Regarding Examples 11 and 12, the organopolysiloxanes with a partially structured structure consisting of continuously linked T-shaped structural units synthesized in Synthesis Example 5 were used as dispersants, as shown in Tables 9 and 12, and their shear viscosity at a given shear rate was measured for evaluation. The results are shown in Tables 9 to 12. Figure 10 middle.

[0266] Table 9. Dispersion Evaluation Results 3-1

[0267]

[0268] Table 10. Dispersion Evaluation Results 3-2

[0269]

[0270] Table 11. Dispersion Evaluation Results 3-3

[0271]

[0272] Table 12. Dispersion Evaluation Results 3-4

[0273]

[0274] It was confirmed that, compared to organopolysiloxanes with a single alkoxysilyl terminal, the organopolysiloxanes of the present invention with a partially structured T-unit continuously linked structure exhibited better dispersibility at a shear rate of 0.001 s. -1 ~0.06S -1 The shear viscosity is suppressed to a low level within a certain range, making it a good dispersant. Furthermore, it has been confirmed that organopolysiloxanes with a partial structure consisting of continuously linked T-shaped structural units, as dispersants, can suppress the shear viscosity at various shear rates depending on the amount added.

[0275] Industrial availability

[0276] The organopolysiloxane of the present invention, which has a partial structure consisting of continuously connected T-shaped structural units, can be used as a dispersant to stably disperse fillers in liquid media in fields such as cosmetics, liquid developers, oil-based inkjet inks, UV-curable inkjet inks, weak solvent coatings, lithographic inks, lubricants, cleaning agents, insecticides, mold release agents, adhesives, thermally conductive materials, conductive materials, and optical materials.

Claims

1. An organopolysiloxane, represented by formula (1) or formula (2): In equations (1) and (2), R 1 It 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, methacryloyl, aromatic, amino, isocyanate, isocyanurate, epoxy, hydroxy, or mercapto, wherein 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 equation (3), R 2 It 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 with 1 to 8 carbon atoms. h ranges from 4 to 400.

2. The organopolysiloxane according to claim 1, wherein it is the reaction product of the organopolysiloxane represented by formula (4) and the trialkoxysilane; In equation (4), R 1 It is independently a saturated hydrocarbon group having 1 to 12 carbon atoms. R 2 It 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 with 1 to 8 carbon atoms. h ranges from 4 to 400.

3. The organopolysiloxane according to claim 1, wherein it is formed by an intermolecular reaction of the organopolysiloxane represented by formula (4); In equation (4), R 1 It is independently a saturated hydrocarbon group having 1 to 12 carbon atoms. R 2 It 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 with 1 to 8 carbon atoms. h ranges from 4 to 400.

4. The organopolysiloxane according to claim 1, wherein it is the reaction product of the organopolysiloxane represented by formula (5) and an alkoxysilane oligomer having vinyl groups; In equation (5), R 2 It is independently a saturated hydrocarbon group having 1 to 12 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms. h ranges from 4 to 400.

5. A method for manufacturing an organopolysiloxane, wherein the organopolysiloxane is the organopolysiloxane as described in claim 2, and the method involves reacting the organopolysiloxane represented by formula (4) as described in claim 2 with a trialkoxysilane.

6. A method for manufacturing an organopolysiloxane, wherein the organopolysiloxane is the organopolysiloxane as described in claim 3, and the method causes the organopolysiloxane represented by formula (4) as described in claim 3 to undergo an intermolecular reaction.

7. The method for manufacturing organopolysiloxane according to claim 5 or 6, wherein an organometallic catalyst is used as the catalyst.

8. A method for manufacturing an organopolysiloxane, wherein the organopolysiloxane is the organopolysiloxane as described in claim 4, the method comprising reacting the organopolysiloxane represented by formula (5) as described in claim 4 with an alkoxysilane oligomer having vinyl groups.

9. A dispersant comprising the organopolysiloxane as described in claim 1, for dispersing filler in a liquid medium.

10. The dispersant according to claim 9, wherein the quantity average molecular weight (Mn) is 500 to 100,000.

11. The dispersant according to claim 9 or 10, wherein the molecular weight distribution index (Mw / Mn) is 1.0 to 3.

0.

12. A filler dispersion comprising a filler, a liquid medium, and an organopolysiloxane as described in claim 1 as a dispersant.

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

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