Organopolysiloxane and method for producing organopolysiloxane, and composition containing organopolysiloxane

Abstract

To provide an organopolysiloxane composition that enables maintenance of fluidity despite heavy filler loading, achieves favorable handling properties, and ensures suppression of oil bleed.SOLUTION: A composition is provided that contains an organopolysiloxane represented by formula (1). In formula (1), R1 independently denotes a saturated hydrocarbon group having 1 to 12 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms, n denotes an integer of 1 or more, m denotes 0 to 5, and X is, for example, the compound illustrated below.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an organopolysiloxane having a vinyl group at one end and a hydroxyl group at the other end, and a method for producing the same. The present invention also relates to an organopolysiloxane composition that not only maintains fluidity and is easy to work with even when filled with a large amount of filler, but also inhibits oil bleeding. [Background technology]

[0002] Products using liquid media such as hydrocarbons, alkanols, alkenols, 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, and urethane resins include cosmetics, liquid toners, oil-based inkjet inks, weak solvent paints, lubricating oils, cleaning agents, thermally conductive materials, electrically conductive materials, optical materials, etc. Furthermore, by dispersing fillers such as pigments in these liquid media, functions according to the intended use can be imparted.

[0003] For example, in recent years, with the increasing density and integration of printed circuit boards and hybrid ICs equipped with electronic components such as transistors, ICs, and memory elements, and the increasing capacity of secondary batteries (cell-type), thermally conductive silicone compositions composed of organopolysiloxanes and thermally conductive fillers such as aluminum oxide powder and zinc oxide powder have been widely used as thermal conductive materials to efficiently dissipate heat generated from electronic components, batteries, and other electronic and electrical devices. In particular, thermally conductive silicone compositions filled with large amounts of thermally conductive fillers have been proposed to accommodate high heat dissipation rates. However, even if the loading rate of thermally conductive fillers filled into thermal greases, thermally conductive sheets, etc. is increased to reduce thermal resistance or improve thermal conductivity, the viscosity of the resin compositions used in the thermal greases, thermally conductive sheets, etc. increases, making it difficult to discharge the resin compositions. For this reason, various combinations of thermally conductive fillers have been investigated to reduce the thermal resistance or increase the thermal conductivity of thermal greases, thermal sheets, and the like (see Patent Documents 1, 2, and 3). However, the combinations of thermally conductive fillers investigated to date have either been insufficient in terms of thermal conductivity or have high viscosity despite high thermal conductivity, and no combinations have been found that achieve both. Furthermore, increasing the filling rate of the thermally conductive filler significantly reduces the fluidity of the resin composition used in the thermal conductive material, making it difficult to dispense or apply the resin composition. This not only makes it difficult to conform to the fine irregularities on the surfaces of electronic components and heat sinks, but also increases the contact thermal resistance.

[0004] One known method for solving this problem is to use a dispersant to improve the dispersibility of the thermally conductive filler in the resin composition (see Patent Document 4). However, when the dispersant or additive described in Patent Document 4 is used, it does not react with the resin, so it can be liberated from the resin composition during use and cause oil bleeding, and an improvement was needed. The occurrence of oil bleeding can lead to poor conductivity due to contamination of electronic components or contact failure. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2005-054099 [Patent Document 2] Japanese Patent Application Laid-Open No. 2004-091743 [Patent Document 3] Japanese Patent Application Laid-Open No. 2000-063873 [Patent Document 4] Japanese Patent Publication No. 2022-081264 Summary of the Invention [Problem to be solved by the invention]

[0006] The present invention relates to an organopolysiloxane having a vinyl group at one end and a hydroxyl group at the other end, and a method for producing the same. An object of the present invention is to provide an organopolysiloxane composition that not only maintains fluidity and is easy to work with even when filled with a large amount of filler, but also inhibits oil bleeding. [Means for solving the problem]

[0007] As a result of extensive research aimed at solving the above problems, the present inventors have discovered that an organopolysiloxane composition containing an organopolysiloxane having a vinyl group at one end and a hydroxyl group at the other end, and a filler, is useful, and have thus completed the present invention. That is, according to the present invention, there is provided the organopolysiloxane shown below, which has a vinyl group at one end and a hydroxyl group at the other end.

[0008] The present invention includes the following items. Item 1. An organopolysiloxane represented by formula (1). TIFF2025165432000001.tif40154 In formula (1), R 1 are independently a saturated hydrocarbon group having 1 to 12 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms, n is an integer of 1 or more, and m is an integer of 0 to 5, X is a group represented by formula (2) or formula (3). TIFF2025165432000002.tif2772 TIFF2025165432000003.tif873

[0009] Item 2. The organopolysiloxane according to Item 1, which is a reaction product of an organopolysiloxane represented by formula (4) and a hydroxyl group-containing compound represented by formula (5) or formula (6). TIFF2025165432000004.tif36100 TIFF2025165432000005.tif2592 TIFF2025165432000006.tif1897 In equation (4), R 1 are independently a saturated hydrocarbon group having 1 to 12 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms, n is an integer of 1 or greater.

[0010] Item 3. A method for producing an organopolysiloxane, comprising reacting an organopolysiloxane represented by formula (4) according to item 2 with a compound having a hydroxyl group represented by formula (5) according to item 2 or formula (6) according to item 2 to produce the organopolysiloxane according to item 1.

[0011] Item 4. An organopolysiloxane composition containing the organopolysiloxane (A) according to Item 1 and a filler (B).

[0012] Item 5. The organopolysiloxane composition according to claim 4, further comprising a liquid medium (C). [Effects of the Invention]

[0013] The organopolysiloxane composition of the present invention maintains its fluidity even when filled with a large amount of thermally conductive filler, resulting in excellent workability. It also inhibits oil bleeding, preventing electrical conductivity problems due to contamination of electronic components and contact failure. [Brief explanation of the drawings]

[0014] [Figure 1] FIG. 1 is a conceptual diagram of an oil-bleed evaluation test. [Figure 2] 1 is a graph showing the shear viscosity when the shear rate is changed for the organopolysiloxane composition of Example 1 and the compositions of Comparative Examples 1 and 2. DETAILED DESCRIPTION OF THE INVENTION

[0015] Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to the following embodiments.

[0016] <Component (A): Organopolysiloxane having a vinyl group at one end and a hydroxyl group at the other end> The organopolysiloxane of the present invention is an organopolysiloxane having a vinyl group at one end and a hydroxyl group at the other end, and is represented by formula (1), and is component (A). TIFF2025165432000007.tif36139 In formula (1), R 1 are independently a saturated hydrocarbon group having 1 to 12 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms, n is an integer of 1 or more, and m is 0 to 5; X is a group having a terminal hydroxyl group and represented by formula (2) or (3). TIFF2025165432000008.tif2771 TIFF2025165432000009.tif872

[0017] <Method for producing organopolysiloxane having a vinyl group at one end and a hydroxyl group at the other end> The organopolysiloxane of the present invention having a vinyl group at one end and a hydroxyl group at the other end can be synthesized from an organopolysiloxane represented by formula (4) having a vinyl group at one end and a hydrosilyl group at the other end, and a compound represented by formula (5) or formula (6) having a hydroxyl group.

[0018] TIFF2025165432000010.tif3494 In equation (4), R 1 are independently a saturated hydrocarbon group having 1 to 12 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms, n is an integer of 1 or greater. TIFF2025165432000011.tif27101 TIFF2025165432000012.tif19109

[0019] The reaction of an organopolysiloxane represented by formula (4), which has a vinyl group at one end and a hydrosilyl group at the other end, with a compound represented by formula (5) or formula (6), which has a hydroxyl group, can be carried out in a solvent as needed, and a transition metal catalyst such as a platinum catalyst or a rhodium catalyst can be used as a catalyst. Furthermore, the compound represented by formula (5) or formula (6), which has a hydroxyl group, can be synthesized by introducing a protecting group using a conventionally known technique, then carrying out the reaction, and then removing the protecting group after the reaction. Examples of the protecting group include a trimethylsilyl group.

[0020] The organopolysiloxane having a vinyl group at one end and a hydrosilyl group at the other end can be used alone or in combination with two or more other types. Also, the organopolysiloxane having a vinyl group at one end and a hydrosilyl group at the other end can be produced by known techniques. For example, there is a method of synthesizing an organopolysiloxane having a vinyl group at one end and a hydrosilyl group at the other end and having a desired molecular weight from an organopolysiloxane having a vinyl group at one end and a silanol group at the other end and dimethylchlorosilane in the presence of triethylamine.

[0021] The solvent used in the reaction of an organopolysiloxane represented by formula (4) having a vinyl group at one end and a hydrosilyl group at the other end with a compound represented by formula (5) or (6) having a hydroxyl group can be at least one selected from nonpolar and polar solvents. Nonpolar solvents include hydrocarbons such as n-hexane, n-heptane, and isooctane, and aromatic hydrocarbons such as toluene and xylene. 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; cyanide hydrocarbons such as acetonitrile; amines; amides such as acetamide; halogenated hydrocarbons such as methylene chloride, chloroform, and hexafluorometa-xylene; and sulfur-containing compounds such as dimethyl sulfoxide. The amount of solvent used is not particularly limited and can be adjusted as needed. Generally, the amount of organosilicon compound to be reacted is 5 to 95% by mass, preferably 20 to 80% by mass. The reaction in the production method of the present invention can also be carried out in a solvent-free system.

[0022] The organopolysiloxane of the present invention having a vinyl group at one end and a hydroxyl group at the other end has a number average molecular weight (Mn) measured by gel permeation chromatography (GPC) of 500 to 200,000, and more preferably 1,000 to 100,000. If the molecular weight is too small, the steric repulsion generated when the filler is dispersed is not exerted, and a stable dispersion cannot be obtained. On the other hand, if the molecular weight is too large, the wettability with the filler becomes insufficient, resulting in an increase in the viscosity of the dispersion.

[0023] The organopolysiloxane of the present invention having a vinyl group at one end and a hydroxyl group at the other end can be synthesized from an organopolysiloxane represented by formula (4) having a vinyl group at one end and a hydrosilyl group at the other end, and a compound represented by formula (5) or formula (6) having a hydroxyl group. The number average molecular weight and molecular weight distribution index (Mw / Mn) of the organopolysiloxane of the present invention can be adjusted by using the required amount of an organopolysiloxane having a vinyl group at one end and a hydrosilyl group at the other end and having any desired number average molecular weight and molecular weight distribution index (Mw / Mn).

[0024] <Organopolysiloxane composition> The organopolysiloxane of the present invention having a vinyl group at one end and a hydroxyl group at the other end maintains fluidity even when filled with a large amount of filler, and is used to provide an organopolysiloxane composition that not only has good workability but also inhibits oil bleeding.

[0025] The organopolysiloxane composition of the present invention contains, as component (A), an organopolysiloxane for dispersing a filler, and as component (B), the filler. The organopolysiloxane is the aforementioned organopolysiloxane having a vinyl group at one end and a hydroxyl group at the other end. The organopolysiloxane composition of the present invention further contains, as component (C), a liquid medium.

[0026] <Filler; component (B)> Examples of fillers include inorganic pigments, organic pigments, extender pigments, bulking agents, inorganic fine particles, diamond, graphene, graphite, carbon black, carbon nanotubes, clay, conductive fillers, thermally conductive agents, carbon fibers, glass fibers, cellulose, and cellulose nanofibers. These fillers are particulate, powdery, or fibrous substances added to plastics, rubber, paints, inks, and the like to improve strength and functionality and reduce costs. There are no particular limitations on the crystal form, particle size, surface condition, or presence or absence of surface treatment of the filler. The filler (thermal conductive agent) for the thermally conductive material is preferably aluminum oxide, zinc oxide, aluminum nitride, or boron nitride, and more preferably aluminum oxide.

[0027] <Liquid medium; (C) component> Examples of liquid media include hydrocarbons, alkanols, alkenols, 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, and urethane resins. These liquid media can be used alone or in combination of two or more. Silicone oil is a liquid medium suitable for use as a thermally conductive material. In addition to liquid media, various organic solvents, monomers, and liquid oligomers can also be used. The solvent used in synthesizing the organopolysiloxane represented by formula (1) can also be used as the liquid medium.

[0028] Hydrocarbons include hexane, hexene, 2-ethylhexane, heptane, heptene, cyclohexane, cyclohexaneheptane, octane, octene, 2-ethylhexane, nonane, decane, isodecane, dodecane, isododecane, tridecane, undecane, octadecane, C8-20 isoparaffins, squalane, petrolatum, microcrystalline wax, hydrogenated polyisobutene, 1-octene, 2-octene, 1-nonene, 2-nonene, 1-decene Examples of the cyclohexane include cyclohexane, 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, and 2-octadecene.

[0029] Examples of alkanols and alkenols include octanol, 2-ethylhexanol, nonanol, decanol, isodecanol, dodecanol, cetyl alcohol, stearyl alcohol, arachyl alcohol, behenyl alcohol, hexyldecanol, octyldodecanol, isocetyl alcohol, isostearyl alcohol, and oleyl alcohol.

[0030] 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, and 2-ethylhexanoic acid.

[0031] 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(capryl-caprate), propylene glycol dioleate, trimethylolpropane triisostearate, pentaerythritol tetra-2-ethylhexanoate, neopentyl glycol diheptanoate, isocetyl isostearate, 2-dimethyloctanoate Examples of the fatty acids include octyldodecyl, myristyl lactate, trioctyldodecyl citrate, diisostearyl malate, di-2-ethylhexyl succinate, diisopropyl adipate, diisobutyl adipate, and cholesteryl stearate. Further examples include triesters with glycerin, such as almond oil, avocado oil, olive oil, shea butter, shea butter oil, evening primrose oil, passionflower seed oil, camellia oil, babassu oil, peanut oil, and rosehip oil; and waxes, such as beeswax, Japan wax, jojoba oil, candelilla wax, and carnauba wax.

[0032] 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, and fluorine-modified silicone oil.

[0033] Examples of acrylic resins include monofunctional (meth)acrylates, difunctional (meth)acrylates, trifunctional or higher polyfunctional (meth)acrylates, epoxy (meth)acrylates, urethane (meth)acrylates, and difunctional or higher polyester (meth)acrylates.

[0034] Examples of epoxy resins include combinations of a base resin, such as phenolic glycidyl ethers (e.g., bisphenol A, bisphenol F, and phenol novolac), or alcoholic glycidyl ethers (e.g., polypropylene glycol), with a curing agent. Examples of curing agents include amine compounds (e.g., aliphatic polyamines, modified aliphatic polyamines, polyamidoamines, 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 may also be used to accelerate the reaction between the base resin and the curing agent. Examples of reaction accelerators include phenol, pt-butylphenol, di-t-butylphenol, cresol, triphenyl phosphite, salicylic acid, and triethanolamine. These reaction accelerators may be used alone or in combination of two or more.

[0035] Examples of urethane resins include reaction products of hydroxyl group-containing compounds and polyisocyanate compounds, such as linear multiblock copolymers of polyurethane obtained by reacting a short-chain glycol or short-chain ether with an isocyanate compound as a hard segment and a long-chain glycol or long-chain ether with an isocyanate compound as a soft segment, and reaction products (cured products) of urethane prepolymers and polyisocyanate compounds.

[0036] Silicone oil is particularly preferred as the liquid medium. For purposes such as viscosity adjustment and curability, a crosslinking agent and an organopolysiloxane other than an organopolysiloxane having a vinyl group at one end and a hydroxyl group at the other end can be added to the composition to achieve crosslinking and curing. The curing mechanism is not particularly limited, and examples include a hydrosilylation reaction, a condensation reaction, and a free radical reaction with an organic peroxide. Among these, a hydrosilylation reaction is preferred because it cures quickly, does not generate by-products, has good reactivity with the vinyl group of component (A), provides a strong immobilization effect of component (A) through chemical bond formation in the cured product, and is particularly effective in suppressing bleed-out. When a hydrosilylation reaction is used, for example, an alkenyl-modified polysiloxane having an average of two or more alkenyl bonds per molecule, a silicon compound having an average of two or more silicon-hydrogen bonds per molecule, and a platinum-based catalyst can be used. Examples of commercially available two-component heat-curing liquid silicones that can be used include TSE3033 manufactured by Momentive Corporation and CY52-276 manufactured by Dow Toray Industries, Inc.

[0037] The organopolysiloxane composition containing a filler preferably contains 0.1 to 50 parts by mass, more preferably 0.5 to 20 parts by mass, of the organopolysiloxane of the present invention having a vinyl group at one end and a hydroxyl group at the other end per 100 parts by mass of filler. If the content of the organopolysiloxane having a vinyl group at one end and a hydroxyl group at the other end per 100 parts by mass of filler is less than 0.1 part by mass, it may be difficult to stably disperse the filler. On the other hand, if the content per 100 parts by mass of filler exceeds 10 parts by mass, an excess amount that does not contribute to the dispersion of the filler will be contained. Furthermore, the organopolysiloxane composition containing a filler preferably contains 0 to 50 parts by mass, more preferably 5 to 30 parts by mass, of the liquid medium per 100 parts by mass of filler.

[0038] The organopolysiloxane composition of the present invention can contain various additives such as surfactants, plasticizers, and antifoaming agents, provided that the intended purpose of the composition is not impaired.

[0039] The organopolysiloxane composition of the present invention can be cured to obtain a heat dissipation sheet.

[0040] The thermally conductive sheet is used by being interposed between electronic components and cooling members inside electronic devices, etc., to efficiently conduct heat generated by the electronic components to the cooling member. Specific examples of electronic components include CPUs, power amplifiers, and power supplies. Specific examples of cooling members include heat sinks.

[0041] The organopolysiloxane composition of the present invention can be produced according to known methods for producing filler dispersions. Examples include a method in which a filler is added to a liquid medium containing an organopolysiloxane having a vinyl group at one end and a hydroxyl group at the other end, followed by stirring and mixing; or a method in which a liquid medium and an organopolysiloxane having a vinyl group at one end and a hydroxyl group at the other end are added to the filler, followed by stirring and mixing. Known dispersing machines can be used as dispersing equipment for stirring, mixing, or dispersion. Examples include roll mills, ball mills, bead mills, sand mills, homogenizers, dispersers, and planetary mixers. Dispersion treatment can also be carried out in an ultrasonic bath. [Example]

[0042] The present invention will be described in more detail below. In the examples, "parts" and "%" are all by mass (parts by mass, % by mass) unless otherwise specified. The present invention is not limited to these examples.

[0043] <Molecular weight measurement> The molecular weight of the organopolysiloxane was measured by gel permeation chromatography (C) method, 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 in the GPC measurement, 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: 2 columns of Shodex KF-804L c) Oven temperature: 40 °C d) Eluent: Toluene 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.

[0044] <NMR (Nuclear Magnetic Resonance Spectrum)> The production of the organopolysiloxane having vinyl at one end and hydroxyl group at the other end of the present invention can be confirmed by 1 1H-NMR measurement. Using a 500 MHz NMR measuring device manufactured by JEOL Ltd., 1 For 1H-NMR, the measurement sample was dissolved in deuterated chloroform (manufactured by FUJIFILM Wako Pure Chemical Corporation) for measurement, 29 For Si-NMR, the measurement sample was dissolved in tetrahydrofuran (manufactured by FUJIFILM Wako Pure Chemical Corporation) for measurement.

[0045] <Synthesis Example 1: Synthesis of an organopolysiloxane having vinyl at one end and a carbinol group at the other end with a number average molecular weight of 4400> * 10 g of an organopolysiloxane having a vinyl group at one end and a hydrosilyl group at the other, expressed by formula (4) (number average molecular weight (Mn) = 3000, weight average molecular weight (Mw) = 3700, molecular weight distribution index (Mw / Mn) = 1.23), and 14.5 g of ethylene glycol monoallyl ether expressed by formula (6) (Tokyo Chemical Industry Co., Ltd., molecular weight = 102.1) were weighed into a 200 ml four-neck flask equipped with a stirrer, thermometer, and reflux condenser, and the mixture was heated to 70-75°C under a nitrogen atmosphere with stirring. Next, 5 μL of Pt-VTSC-3.0X manufactured by Umicore Japan was added as a Karstedt catalyst, and 20 g of an organopolysiloxane having a vinyl group at one end and a hydrosilyl group at the other end (number average molecular weight (Mn) = 3000, weight average molecular weight (Mw) = 3700, molecular weight distribution index (Mw / Mn) = 1.23) was added dropwise from the dropping funnel over 1 hour at 70 to 75°C, followed by stirring for an additional 3 hours at 70 to 80°C. Next, the mixture was heated at 120°C for 1 hour under reduced pressure of 0.1 kPaA using a vacuum pump to distill off the volatile substances remaining in the product, thereby obtaining 27 g of a pale yellow, transparent liquid remaining in the flask.

[0046] GPC: Number average molecular weight (Mn) = 4400, weight average molecular weight (Mw) = 6800, molecular weight distribution index (Mw / Mn) = 1.55. 1 H-NMR: δ(ppm); 6.1(m, 0.53H), 5.9(d, 0.56H), 5.7(d, 0.55H), 3.7(d, 2.00H), 3.5(d, 2.01H), 3.4(t, 2.01H), 1.9(br, 0.85H), 1.6(m, 2.20H), 1.3(m, 6.31H), 0.9(m, 4.72H), 0.5(m, 4.41H), 0.4(s, 1.46H), 0.1(m, 240.8H) 29 Si-NMR: δ(ppm);10.1(M), 9.6(M), -2.2(M), -20.3(D)

[0047] TIFF2025165432000013.tif51164

[0048] The pale yellow transparent liquid obtained in Synthesis Example 1 1 The H-NMR spectrum confirmed peaks associated with the progress of the hydrosilylation reaction (δ (ppm): 1.6 (m, 2.20H), 0.5 (m, 4.41H), 0.4 (s, 1.46H)), indicating that the product is an organopolysiloxane represented by formula (1), which has a vinyl group at one end and a carbinol group at the other end.

[0049] <Synthesis Example 2: Synthesis of organopolysiloxane having a number average molecular weight of 4000 and a vinyl group at one end and a diol group at the other end> Into a 200 ml four-neck flask equipped with a stirring blade, a thermometer, and a reflux condenser were weighed 20 g of an organopolysiloxane represented by formula (4) (number average molecular weight (Mn) = 3000, weight average molecular weight (Mw) = 3700, molecular weight distribution index (Mw / Mn) = 1.23) having a vinyl group at one end and a hydrosilyl group at the other, 49 g of trimethylolpropane allyl ether represented by formula (5) (molecular weight = 174.24), and 92 g of 4-methyltetrahydropyran as a solvent, and the mixture was heated to 70-75°C with stirring under a nitrogen atmosphere. Next, 12.5 μL of Pt-VTSC-3.0X manufactured by Umicore Japan was added as a Karstedt catalyst, and 40 g of an organopolysiloxane having a vinyl group at one end and a hydrosilyl group at the other end (number average molecular weight (Mn) = 3000, weight average molecular weight (Mw) = 3700, molecular weight distribution index (Mw / Mn) = 1.23) was added dropwise from the dropping funnel over 1 hour at 70 to 75°C, followed by stirring for an additional 3 hours at 75 to 85°C. Next, the product was heated at 120°C for 1 hour under reduced pressure of 0.1 kPaA using a vacuum pump to distill off any volatile substances remaining in the product, and the volatile substances were further distilled off using a thin-film still, yielding 56 g of a pale yellow, transparent liquid remaining in the flask.

[0050] GPC: Number average molecular weight (Mn) = 4000, weight average molecular weight (Mw) = 5200, molecular weight distribution index (Mw / Mn) = 1.30. 1H-NMR: δ(ppm); 6.1(m, 0.55H), 5.9(d, 0.53H), 5.7(d, 0.56H), 3.7(d, 2.00H), 3.6(d, 1.91H), 3.4(s, 1.88H), 3.4(t, 1.88H), 2.1(br, 1.86), 1.6(m, 2.01H), 1.3(m, 7.52H), 0.9(m, 7.35H), 0.5(m, 4.22H), 0.4(s, 0.89H), 0.1(m, 214.1H) 29 Si-NMR: δ(ppm);10.4(M), 9.9(M), -2.0(M), -20.3(D)

[0051] TIFF2025165432000014.tif55167

[0052] The pale yellow transparent liquid obtained in Synthesis Example 2 1 The H-NMR spectrum confirmed peaks (δ (ppm): 1.6 (m, 2.01H), 0.5 (m, 4.22H), 0.4 (s, 0.89H) associated with the progress of the hydrosilylation reaction, indicating that the product is an organopolysiloxane represented by formula (1), which has a vinyl group at one end and a diol group at the other end.

[0053] <Preparation of evaluation samples> The organopolysiloxane synthesized in Synthesis Example 1 was weighed into an ointment jar as component (A). Next, a vinyl-modified silicone (vinyl group content: 0.2 mmol / g) was weighed as component (C). Furthermore, aluminum oxide (DAW-03, manufactured by Denka Co., Ltd.) with an average diameter of 5 μm and aluminum oxide (DAW-45, manufactured by Denka Co., Ltd.) with an average diameter of 46 μm were weighed as component (B) and stirred with a spatula. Further weighed as component (C) were tetrakis(dimethylsiloxy)silane (manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight: 328.7), Karstedt catalyst (Pt-VTSC-3.0X, manufactured by Umicore Japan), and 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane (molecular weight: 240.5). The organopolysiloxane synthesized in Synthesis Example 1, the silicone modified with vinyl at both ends, tetrakis(dimethylsiloxy)silane, aluminum oxide, Karstedt catalyst, and 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane were weighed out in the amounts shown in Table 1. Next, using a Thinky Mixer Vacuum Type (Model: ARV-310) manufactured by Thinky Corporation, the mixture was kneaded at 2000 rpm for 1 minute under normal pressure and at 1000 rpm for 1 minute under reduced pressure to prepare a composition for evaluation.

[0054] <Liquidity evaluation> The dispersibility of the evaluation sample prepared as described above was evaluated by measuring the shear viscosity at different shear rates using a rheometer (MCR302, manufactured by Anton Paar) under the following conditions. Plate shape: circular flat plate 25mmφ Sample thickness: 1.0 mm Temperature: 25±1℃ Shear rate: 10S -1 , or 0.0001 to 100S -1

[0055] <Oil bleeding evaluation> 0.6 g of the evaluation sample prepared as described above was applied to a frosted glass plate, sandwiched between two other glass plates to a thickness of 1 mm, and heated and cured at 150°C for 3 hours. The length of oil bleed that had seeped out around the composition was measured, and the ratio to the width of the composition was calculated to evaluate the oil-bleed suppression effect. That is, as shown in Figure 1, the bleed length ratio was calculated using equation (7) using the bleed length L1 and the composition width L2. The smaller this ratio, the greater the oil-bleed suppression effect. (Bleed length ratio) = (L1-L2) / L2 (7)

[0056] For Example 1, the fluidity was evaluated by measuring the shear viscosity at a predetermined shear rate using the organopolysiloxane having a vinyl group at one end and a carbinol group at the other end synthesized in Synthesis Example 1, and oil-bleed was also evaluated. The results are shown in Table 1.

[0057] For Comparative Example 1, an evaluation sample was prepared in the same manner as in Example 1, but without using the organopolysiloxane used as component (A) in Example 1. For Comparative Example 2, an evaluation sample was prepared in the same manner as in Example 1, except that an organopolysiloxane having a carbinol group at one end and represented by formula (8) (FM-0421, manufactured by JNC Corporation, number average molecular weight (Mn) = 6100, weight average molecular weight (Mw) = 6400, molecular weight distribution index (Mw / Mn) = 1.05) was used as component (A') instead of the organopolysiloxane used as component (A) in Example 1.

[0058] TIFF2025165432000015.tif32127 For Comparative Examples 1 and 2, the fluidity was evaluated by measuring the shear viscosity at a predetermined shear rate, and further, the oil bleeding was evaluated. The results are shown in Table 1.

[0059] Table 1. Evaluation results 1 TIFF2025165432000016.tif119157

[0060] FIG. 2 is a graph showing the shear viscosity when the shear rate is changed for the organopolysiloxane composition of Example 1 and the compositions of Comparative Examples 1 and 2.

[0061] The organopolysiloxane of the present invention having a vinyl group at one end and a hydroxyl group at the other end (Example 1) showed a lower shear viscosity in a fluidity evaluation of the composition, confirming good fluidity, compared to a composition not using the organopolysiloxane (Comparative Example 1). Furthermore, the organopolysiloxane of the present invention having a vinyl group at one end and a hydroxyl group at the other end (Example 1) was confirmed to have a higher oil-bleed suppression effect than an organopolysiloxane having a hydroxyl group at one end (Comparative Example 2).

[0062] From the above, it can be concluded that the organopolysiloxane composition of the present invention is excellent in workability and in its ability to inhibit oil bleeding during use. [Industrial Applicability]

[0063] The organopolysiloxane of the present invention having a vinyl group at one end and a hydroxyl group at the other end can be used as a dispersant for stably dispersing fillers in fields such as cosmetics, liquid developers, oil-based inkjet inks, ultraviolet-curable inkjet inks, weak-solvent paints, offset inks, lubricants, cleaning agents, insecticides, release agents, adhesives, thermally conductive materials, electrically conductive materials, and optical materials. The organopolysiloxane composition of the present invention can also be used as a thermally conductive material to be interposed between heat-generating electronic components such as transistors, IC chips, and memory elements and cooling members such as heat sinks.

Claims

1. An organopolysiloxane represented by formula (1): In formula (1), R １ are independently a saturated hydrocarbon group having 1 to 12 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms, n is an integer of 1 or more, and m is an integer of 0 to 5, X is a group represented by formula (2) or formula (3).

2. 2. The organopolysiloxane according to claim 1, which is a reaction product of an organopolysiloxane represented by formula (4) and a compound having a hydroxyl group represented by formula (5) or formula (6). In formula (4), R １ are independently a saturated hydrocarbon group having 1 to 12 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms, n is an integer of 1 or more.

3. A method for producing an organopolysiloxane, comprising reacting an organopolysiloxane represented by formula (4) according to claim 2 with a compound having a hydroxyl group represented by formula (5) according to claim 2 or formula (6) according to claim 2 to produce the organopolysiloxane according to claim 1.

4. An organopolysiloxane composition comprising the organopolysiloxane (A) according to claim 1 and a filler (B).

5. The organopolysiloxane composition according to claim 4, further comprising a liquid medium (C).

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