Isocyanurate skeleton-containing organopolysiloxane

Abstract

An isocyanurate skeleton-containing organopolysiloxane composed of: an isocyanurate skeleton represented by formula (1) (therein, Q is a divalent hydrocarbon group having 2-10 carbon atoms, X is a divalent group that has 2-8 carbon atoms and optionally contains therein a divalent amino group represented by -NH-, n is an integer of 1-5, and * is a free radical that bonds to the * moiety in formula (2), (3), (4), or (5)) and one or more chains selected from among organopolysiloxane chains represented by formulas (2), (3), (4), and (5).

Description

Isocyanurate skeleton-containing organopolysiloxane

[0001] The present invention relates to an organopolysiloxane containing an isocyanurate skeleton.

[0002] Polyisocyanates are highly reactive and produce tough crosslinked polymers with polyols and amino compounds, and are therefore widely used in the fields of curing agents and coatings. For example, Patent Document 1 describes a technique for forming a rigid polyurethane foam by reacting a polyol with a polyisocyanate compound in the presence of an amino-modified silicone. Patent Document 2 describes a composition containing an amino-modified silicone, a blocked polyisocyanate, and a polyol. The composition, in which the amino-modified silicone, the blocked polyisocyanate, and the polyol are dispersed, is reacted on a substrate, and the reaction product is used as a mold release agent. Patent Document 3 also describes a resin composition for coatings in which the reaction product of an amino-modified silicone and an organofunctional resin is reacted with an isocyanate compound. However, there has been no description of a composition in which an isocyanurate skeleton is modified with a monofunctional organopolysiloxane or a side-chain functional organopolysiloxane, nor has there been any description of an isocyanurate skeleton-containing organopolysiloxane in which a portion of the isocyanurate skeleton is crosslinked with a polysiloxane.

[0003] International Publication No. 2008 / 062796 JP 2020-032658 A JP 2017-066284 A

[0004] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide an isocyanurate skeleton-containing organopolysiloxane that has excellent solubility in silicone oils and organic oils and is capable of thickening and gelling these oils.

[0005] As a result of extensive research into achieving the above object, the present inventors have discovered that an isocyanurate skeleton-containing organopolysiloxane having an isocyanurate skeleton and a polysiloxane structure as constituent units can solve the above problems, leading to the completion of the present invention.

[0006] Accordingly, the present invention provides the following isocyanurate skeleton-containing organopolysiloxane and thickener: 1. A compound represented by the following formula (1): (wherein Q is a divalent hydrocarbon group having 2 to 10 carbon atoms, X is a divalent group having 2 to 8 carbon atoms which may contain a divalent amino group represented by —NH— within the group, n is an integer from 1 to 5, and * is a free group which bonds to * in the following formula (2), (3), (4), or (5)), and one or more organopolysiloxane chains selected from the following formulas (2), (3), (4), and (5): (wherein R independently represents a monovalent hydrocarbon group having 1 to 10 carbon atoms; R 1 is an alkyl group having 1 to 4 carbon atoms, and p is an integer from 1 to 100. * is a free group that bonds to * in the above formula (1). (In the formula, R is the same as above, q is 1 to 5, r is an integer of 0 to 100, and the position of the siloxane unit bracketed by q may be anywhere in the molecular chain. * is a free radical that bonds to each different * in formula (1) above.) (In the formula, R is the same as above. * is a free group that bonds to * in formula (1) above.) (In the formula, R is the same as above, and s is an integer of 1 to 100. Note that each * is a free group bonding to a different * in formula (1) above.) 2. The isocyanurate skeleton-containing organopolysiloxane according to 1, which is composed of an isocyanurate skeleton represented by formula (1) above and an organopolysiloxane chain represented by formula (2) or (5) above. 3. The isocyanurate skeleton-containing organopolysiloxane according to 1, which is composed of an isocyanurate skeleton represented by formula (1) above and an organopolysiloxane chain represented by formula (4) or (5). 4. The isocyanurate skeleton-containing organopolysiloxane according to 1, which is composed of an isocyanurate skeleton represented by formula (1) above and an organopolysiloxane chain represented by formula (2). 5. The ratio (5) / (2) of the amount of substance of the organopolysiloxane chain represented by formula (2) to the amount of substance of the organopolysiloxane chain represented by formula (5) constituting the isocyanurate skeleton-containing organopolysiloxane is 0 to 1. The isocyanurate skeleton-containing organopolysiloxane according to any one of 1 to 4. 6. A thickener comprising the isocyanurate skeleton-containing organopolysiloxane according to any one of 1 to 5.

[0007] The present invention provides an isocyanurate skeleton-containing organopolysiloxane that has excellent solubility in silicone oils and organic oils and is capable of gelling them. Because of its properties, this isocyanurate skeleton-containing organopolysiloxane is effective as a gelling agent and thickener.

[0008] The isocyanurate skeleton-containing organopolysiloxane obtained in Synthesis Example 2 1 1 is a H-NMR spectrum chart.

[0009] The present invention will be described in detail below. However, the present invention is not limited to the following embodiments. The isocyanurate skeleton-containing organopolysiloxane of the present invention is an isocyanurate skeleton-containing organopolysiloxane composed of the following isocyanurate skeleton and one or more organopolysiloxane chains selected from the following organopolysiloxane chains:

[0010] [Isocyanurate skeleton] The isocyanurate skeleton is represented by the following formula (1): (In the formula, Q is a divalent hydrocarbon group having 2 to 10 carbon atoms, X is a divalent group having 2 to 8 carbon atoms which may contain a divalent amino group represented by —NH— within the group, n is an integer from 1 to 5, and * is a free group which bonds to * in the following formula (2), (3), (4), or (5).)

[0011] In formula (1), Q is a divalent hydrocarbon group having 2 to 10 carbon atoms. Specific examples include alkyl groups such as ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, and decamethylene, and a 4-methyl-1,3-phenylene group represented by the following formula (6): Of these, pentamethylene, hexamethylene and 4-methyl-1,3-phenylene groups are preferred, with pentamethylene and hexamethylene groups being more preferred.

[0012] In formula (1), X is a divalent group having 2 to 8 carbon atoms which may contain a divalent amino group represented by -NH- within the group. Specific examples include alkylene groups such as ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, and octamethylene. Examples of groups containing a divalent amino group represented by -NH- include groups shown in formulas (7) and (8) below. Of these, a trimethylene group is preferred.

[0013] In formula (1), n ​​is an integer of 1 to 5, preferably 1 to 3. The repeating units may be arranged in a linear or branched chain. For example, when n = 4, formula (1) has the following linear and branched structures: * is a free group that bonds to * in the following formula (2), (3), (4) or (5).

[0014] [Polysiloxane Structure] The organopolysiloxane chain bonded to the isocyanurate skeleton represented by formula (1) above is one or more selected from organopolysiloxane chains represented by formulas (2), (3), (4), and (5). Of these, an organopolysiloxane chain represented by formula (2) or (5), an organopolysiloxane chain represented by formula (4) or (5), and an organopolysiloxane chain represented by formula (2) are preferred. The molar ratio (5) / (2) of the organopolysiloxane represented by formula (2) to the organopolysiloxane represented by formula (5) above that constitutes the isocyanurate skeleton-containing organopolysiloxane is preferably 0 to 1, more preferably 0 to 0.5. When formula (5) is included, it is preferably greater than 0 and not greater than 1, more preferably greater than 0 and not greater than 0.5. (wherein R independently represents a monovalent hydrocarbon group having 1 to 10 carbon atoms; R 1 is an alkyl group having 1 to 4 carbon atoms, and p is an integer from 1 to 100. * is a free group that bonds to * in the above formula (1).

[0015] R is independently a hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 3, and specific examples thereof include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl, aryl groups such as phenyl and tolyl, and aralkyl groups such as benzyl and phenethyl. Of these, methyl, ethyl, and phenyl groups are preferred, and it is more preferred that all R are methyl groups.

[0016] R 1 is an alkyl group having 1 to 4 carbon atoms, and specific examples include a methyl group, an ethyl group, a propyl group, and a butyl group. Of these, a methyl group and a butyl group are preferred. p is an integer of 1 to 100, and preferably an integer of 1 to 30. Note that * in formula (2) is a free group that bonds to * in formula (1).

[0017] (In the formula, R is the same as above, q is 1 to 5, r is an integer of 0 to 100, and the position of the siloxane unit bracketed by q may be anywhere in the molecular chain. * is a free radical that bonds to each different * in formula (1) above.)

[0018] R is the same as above, and specific and preferred examples can be the same as those described in formula (2) above. q is an integer of 1 to 5, preferably 1 or 2, and r is an integer of 0 to 100, preferably 1 to 60. The siloxane units bracketed by q may be located anywhere along the molecular chain. * denotes a free radical that bonds to different *'s in formula (1) above. When q is 3 or greater, a structure is formed in which two or more (1)'s react with one (3).

[0019] (In the formula, R is the same as above. * is a free group that bonds to * in formula (1) above.)

[0020] In formula (4), R is the same as above, and specific and preferred examples thereof are the same as those described in formula (2) above.

[0021] (In the formula, R is the same as above, and s is an integer of 1 to 100. Each * represents a free group that bonds to a different * in formula (1) above.)

[0022] In formula (5), R is the same as above, and specific and preferred examples include those described in formula (2) above. s is an integer of 1 to 100, preferably 1 to 60. Furthermore, the two * symbols in formula (5) above are free groups that bond to different * symbols in formula (1).

[0023] [Production Method] The isocyanurate skeleton-containing organopolysiloxane of the present invention can be obtained by reacting an isocyanurate skeleton-containing polyisocyanate (A) with an amino-modified silicone (B). This reaction is not particularly limited and any known method can be used, but the following method is exemplified.

[0024] The isocyanurate skeleton-containing polyisocyanate (A) is weighed into a reaction vessel, and a reaction solvent is added as appropriate. Examples of reaction solvents include hydrocarbon solvents such as toluene and xylene, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, ester solvents such as ethyl acetate, butyl acetate, and pentyl acetate, alcohol solvents such as isopropanol, ether solvents such as dioxane, dibutyl ether, and tetrahydrofuran, glycol ester solvents such as propylene glycol monomethyl ether acetate, amide solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone, and dimethyl sulfoxide. Among these, toluene, tetrahydrofuran, and isopropanol are preferred as reaction solvents. Furthermore, no solvent is preferred.

[0025] Next, the amino-modified silicone (B) is added dropwise using a dropping funnel and stirred to obtain an isocyanurate skeleton-containing organopolysiloxane. The molar ratio (A) / (B) of the isocyanate groups in the isocyanurate skeleton-containing polyisocyanate (A) to the amino groups in the amino-modified silicone (B) is not particularly limited, but is preferably 0.3 to 3, more preferably 0.8 to 1.2. If the resulting isocyanurate skeleton-containing organopolysiloxane is solid, the reaction can be efficiently promoted by diluting it with the reaction solvent or by melting it by heating. The reaction proceeds satisfactorily at room temperature, but may be heated as needed, preferably to a temperature of 50 to 130°C, more preferably 80 to 100°C. The reaction time is selected depending on the raw materials used, but is preferably 0.1 to 24 hours, more preferably 0.5 to 3 hours. Alternatively, an isocyanurate skeleton-containing organopolysiloxane can be obtained by measuring out an amino-modified silicone into a reaction vessel and adding an isocyanurate skeleton-containing polyisocyanate thereto. After the reaction, residual isocyanate groups may be quenched by adding an alcohol or amine. Specific examples of alcohols include methanol, ethanol, propanol, and butanol, which can be removed by vacuum distillation in a post-processing step. Specific examples of amines include propylamine, butylamine, 2-methylpropanamine, and n-octylamine.

[0026] In the production of the isocyanurate skeleton-containing organopolysiloxane of the present invention, a known catalyst may be used as needed to ensure smooth reaction between the isocyanate groups and active hydrogen groups in the raw materials. Examples of such catalysts include N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethylpropylenediamine, N,N,N',N",N"-pentamethyldiethylenetriamine, N,N,N',N",N"-pentamethyl-(3-aminopropyl)ethylenediamine, N,N,N',N",N"-pentamethyldipropylenetriamine, N,N,N',N'-tetramethylguanidine, 1,3 , 5-tris(N,N-dimethylaminopropyl)hexahydro-S-triazine, 1,8-diazabicyclo[5.4.0]undecene-7, triethylenediamine, N,N,N',N'-tetramethylhexamethylenediamine, N-methyl-N'-(2-dimethylaminoethyl)piperazine, N,N'-dimethylpiperazine, dimethylcyclohexylamine, N-methylmorpholine, N-ethylmorpholine, bis(2-dimethylaminoethyl) tertiary amines such as tertiary amines (aminoethyl) ether, N,N-dimethyllaurylamine, 1-methylimidazole, 1,2-dimethylimidazole, 1-isobutyl-2-methylimidazole, and 1-dimethylaminopropylimidazole; quaternary ammonium salts such as tetraalkylammonium halides (tetramethylammonium chloride), tetraalkylammonium hydroxides (tetramethylammonium hydroxide salts), and tetraalkylammonium organic acid salts (tetramethylammonium 2-ethylhexanoate); and organometallic catalysts such as stannous diacetate, stannous dioctoate, stannous dioleate, stannous dilaurate, dibutyltin oxide, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dichloride, dioctyltin dilaurate, lead octoate, lead naphthenate, nickel naphthenate, and cobalt naphthenate.

[0027] Examples of the isocyanurate skeleton-containing polyisocyanate (A) include isocyanurates represented by the following formulas, which are obtained by trimerizing isocyanates such as hexamethylene diisocyanate, pentamethylene diisocyanate, and toluene diisocyanate. Different isocyanurate skeleton-containing polyisocyanates may be used in combination.

[0028] (wherein n is an integer of 1 to 5.)

[0029] The amino-modified silicone (B) may be one or more of the types represented by the following formula (9), and different amino-modified silicones may be used in combination.

[0030] (R is the same as above, R 2 is the following formula (10) -X 1 -NH2 (10) is an amino group-containing group represented by the formula (10), 1 is a divalent group having 2 to 8 carbon atoms which may contain a divalent amino group represented by -NH- in the middle of the group. 3 are independently R or R 2 where d is an integer of 0 to 5 and e is an integer of 0 to 100. When d is 0, R 3 At least one of 2 It is.)

[0031] R is the same as above, and specific and preferred examples thereof are the same as those described in the formula (2) above. 2 is an amino group-containing group represented by the above formula (10), and in formula (10), X 1 is a divalent group having 2 to 8 carbon atoms, preferably 2 to 5 carbon atoms, which may contain a divalent amino group represented by --NH-- in the middle of the group.

[0032] R 2 Specific examples of the amino group include the following amino groups.

[0033] R 3 are independently R or R 2and d is an integer of 0 to 5, more preferably 0 to 2. e is an integer of 0 to 100, preferably 0 to 60. When d is 0, R 3 At least one of 2 When d exceeds 10, the crosslink density of the three-dimensional crosslinked structure of the reaction product of polyisocyanate and amino-modified silicone increases, resulting in poor solubility in oils and a high melting point, which makes it difficult to use. From the viewpoint of compatibility with oils, e is preferably 0 to 60. Note that d and e are appropriately selected depending on p, q, r, and s. Specific examples of the amino-modified silicone (B) include amino-modified silicones represented by the following formula:

[0034] (In the formula, in an amino-modified silicone containing two or more types of siloxane units, the bonding of the respective siloxane units may be block or random.)

[0035] [Physical Properties of Isocyanurate Skeleton-Containing Organopolysiloxane] The melting point of the isocyanurate skeleton-containing organopolysiloxane is preferably 30 to 150° C., more preferably 50 to 90° C. The melting point is a value corresponding to the temperature at the apex of the endothermic peak observed by differential scanning calorimetry (DSC) as described in ISO Standard 11357-3:1999.

[0036] The isocyanurate skeleton-containing organopolysiloxane of the present invention has a wide range of solubility in silicone oils and organic oils. Solubility can be confirmed by the method described in the Examples below. Hereinafter, the names of compounds may be referred to as their cosmetic names or INCI (International Nomenclature of Cosmetic Ingredients). When the cosmetic name corresponds to the INCI, the cosmetic name or English name may be omitted.

[0037] Further examples include oils, particularly silicone oils, organic oils such as hydrocarbon oils, ester oils, glyceride oils, vegetable oils, mineral oils, other synthetic oils, organic solvents, and mixtures thereof, which may be used alone or in combination of two or more. They are particularly suitable for thickening and gelling silicone oils, and can also thicken and gel linear dimethylpolysiloxanes, which have traditionally been difficult to thicken and gel.

[0038] Silicone Oils Examples of silicone oils include trisiloxane (labeled as "Trisiloxane" in INCI), volatile dimethicone (labeled as "Dimethicone" in INCI), low-viscosity dimethicone (labeled as "Dimethicone" in INCI), cyclotetrasiloxane (labeled as "Cyclotetrasiloxane" in INCI), cyclopentasiloxane (labeled as "Cyclopentasiloxane" in INCI), cyclohexasiloxane (labeled as "Cyclohexasiloxane" in INCI), methyl trimethicone (labeled as "Methyl Trimethicone" in INCI), and caprylyl methicone (labeled as "Caprylyl Methicone" in INCI). Methicone), Phenyl Trimethicone (Inci: Phenyl Trimethicone), Methylphenyl Polysiloxane (Inci: Diphenyl Dimethicone), Diphenylsiloxy Phenyl Trimethicone (Inci: Diphenylsiloxy Phenyl Trimethicone), Ethyl Methicone (Inci: Ethyl Methicone), Ethyl Trisiloxane (Inci: Ethyl Trisiloxane), Hydrogen Dimethicone (Inci: Hydrogen Examples of suitable silicone rubbers include low-viscosity to high-viscosity linear or branched dimethicones such as amodimethicone (display name (INCI: Amodimethicone)), aminopropyl dimethicone (display name (INCI: Aminopropyl Dimethicone)), highly polymerized gummy dimethicone (display name (INCI: Dimethicone)), gummy amodimethicone (display name (INCI: Amodimethicone)), and gummy dimethylsiloxane-methylphenylsiloxane copolymers, as well as cyclic organopolysiloxane solutions of silicone gums and rubbers, amino acid-modified silicones, fluorine-modified silicones, silicone resins, and silicone resin solutions.

[0039] Examples of hydrocarbon oils include linear, branched, and volatile hydrocarbon oils, such as ozokerite (INCI), olefin oligomers (display name), isododecane (INCI), hydrogenated polyisobutene (INCI), squalane (INCI), squalene (INCI), ceresin (INCI), paraffin (INCI), polyethylene (INCI), polyethylene-polypropylene wax, ethylene / propylene / styrene copolymer, butylene / propylene / styrene copolymer, pristane (INCI), polyisobutylene, microcrystalline wax (INCI), and petrolatum (INCI).

[0040] Examples of ester oils include diisobutyl adipate (INCI: Diisobutyl Adipate), diethylhexyl adipate (INCI: Diethylhexyl Adipate), diheptylundecyl adipate (INCI: Heptylundecyl Adipate), n-alkylene (20-30) glycol monoisostearate, isocetyl isostearate (INCI: Isocetyl Isostearate), trimethylolpropane triisostearate (INCI: Trimethylolpropane Triisostearate), ethylene glycol di-2-ethylhexanoate, and cetyl 2-ethylhexanoate (INCI: Cetyl Ethylhexanoate), Trimethylolpropane Triethylhexanoate (INCI: Trimethylolpropane Triethylhexanoate), Pentaerythrityl Tetraethylhexanoate (INCI: Pentaerythrityl Tetraethylhexanoate), Octyldodecyl myristate (INCI: Octyldodecyl Myristate), Oleyl oleate (INCI: Oleyl Oleate), Octyldodecyl oleate (INCI: Octyldodecyl Oleate), Decyl oleate (INCI: Decyl Oleate), Neopentyl Glycol Dioctanoate (INCI: Neopentyl Glycol Diethylhexanoate), neopentyl glycol dicaprate (INCI: Neopentyl Glycol Dicarate), triethyl citrate (INCI: Triethyl Citrate), diethylhexyl succinate (INCI: Diethylhexyl Succinate), amyl acetate (INCI: Amyl Acetate), ethyl acetate (INCI: Ethyl Acetate), butyl acetate (INCI: Butyl Acetate), isocetyl stearate (INCI: Isocetyl Isostearate), butyl stearate (INCI: Butyl Stearate), diisopropyl sebacate (INCI: Diisopropyl Sebacate),Diethylhexyl Sebacate (INCI: Diethylhexyl Sebacate), Cetyl Lactate (INCI: Cetyl Lactate), Myristyl Lactate (INCI: Myristyl Lactate), Isononyl Isononanoate (INCI: Isononyl Isononanoate), Isotridecyl Isononanoate (INCI: Isotridecyl Isononanoate), Isopropyl Palmitate (INCI: Isopropyl Palmitate), Ethylhexyl Palmitate (INCI: Ethylhexyl Palmitate), Hexyldecyl Palmitate (INCI: Hexyldecyl Palmitate), Cholesteryl Hydroxystearate (INCI: Cholesteryl Hydroxystearate), Isopropyl Myristate (INCI: Isopropyl Myristate), Octyldodecyl Myristate (INCI: Octyldodecyl Myristate), 2-Hexyldecyl Myristate, Myristyl Myristate (INCI: Myristyl Myristate), Hexyldecyl Dimethyloctanoate, Ethyl Laurate (INCI: Ethylhexyl Laurate), Hexyl Laurate (INCI: Hexyl Laurate), di(phytosteryl / octyldodecyl) lauroyl glutamate (INCI: Phytosteryl / Octyldodecyl Lauroyl Glutamate), isopropyl lauroyl sarcosinate (INCI: Isopropyl Lauroyl Sarcosinate), diisostearyl malate (INCI: Diisostearyl Malate), etc.

[0041] Examples of glyceride oils include glyceryl acetate (INCI: Glyceryl Acetate), triethylhexanoin (INCI), glyceryl triisostearate (INCI: Glyceryl Isostearate), triisopalmitin (INCI), glyceryl stearate (INCI: Glyceryl Stearate), glyceryl diisostearate (INCI: Glyceryl Diisostearate), trimyristin (INCI), and glyceryl isostearate / myristic acid (INCI: ISOSTEARIC / MYRISTIC GLYCERIDES).

[0042] Vegetable oils Examples of vegetable oils include olive oil, mustard oil, palm oil, sunflower oil, coconut oil, camellia oil, cacao oil, etc. Mineral oils Examples of mineral oils include crude oil, naphtha, petroleum ether, liquid paraffin, etc.

[0043] Organic Solvents The organic solvent is not particularly limited as long as it is an organic compound that has a boiling point of approximately 200°C or less under atmospheric pressure (1013 hPa) and is used to dissolve resins and the like. Examples of the organic solvent include chain aliphatic hydrocarbons such as pentane, hexane, heptane, and octane; alicyclic hydrocarbons such as cyclohexane, nonane, and decalin; aromatic hydrocarbons such as benzene, toluene, and xylene; heterocyclic hydrocarbons such as pyridine; ethers such as diethyl ether and dipropyl ether; esters such as ethyl acetate, propyl acetate, and butyl acetate; nitriles such as acetonitrile; and ketones such as methyl ethyl ketone and methyl isobutyl ketone.

[0044] [Thickener] The isocyanurate skeleton-containing organopolysiloxane of the present invention has excellent solubility in silicone oils and organic oils and can thicken and gel them. Because of the above properties, this isocyanurate skeleton-containing organopolysiloxane is effective as a thickener and gelling agent. The present invention can be applied to fields where a thickening effect is expected, such as cosmetics. Regarding its thickening and gelling properties, it is preferable that the viscosity be increased to 10 times or more the viscosity of the solvent while maintaining fluidity, as measured by the method described in the Examples below, and more preferable that it solidifies (has no fluidity).

[0045] The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to the following examples. In the following examples, "%" in the composition means % by mass unless otherwise specified.

[0046] [Synthesis of Isocyanurate Skeleton-Containing Organopolysiloxane] The reaction raw materials used in the synthesis of the isocyanurate skeleton-containing organopolysiloxane of the present invention are shown below. Note that the melting points shown in the following synthesis examples are values ​​corresponding to the temperatures at the apexes of the endothermic peaks observed by differential scanning calorimetry (DSC) as described in ISO Standard 11357-3:1999.

[0047] (A) Isocyanurate skeleton-containing polyisocyanate: Hexamethylene diisocyanate trimer (trade name: Duranate TPA-100, manufactured by Asahi Kasei Corporation, NCO content: 23.1% by mass) (B) Amino-modified silicone (all manufactured by Shin-Etsu Chemical Co., Ltd.)

[0048]

[0049]

[0050]

[0051] Synthesis Example 1 A reaction vessel was charged with an isocyanurate-containing polyisocyanate (NCO content: 23.1%), which is a trimer of hexamethylene diisocyanate, and while heating at 100°C, an amino-modified silicone was added dropwise in the substance amount ratio (molar ratio) shown in Table 1. After completion of the addition, the mixture was aged at 100°C for 1 hour to obtain an isocyanate skeleton-containing organopolysiloxane. The target isocyanurate skeleton-containing organopolysiloxane was a colorless, semi-transparent solid with a melting point of 82 to 88°C. 1 H-NMR (400MHz, CDCl3, 25°C, ppm): 0.06 (101.8H), 0.52 (11.3H), 0.88 (11. 2H), 1.31 (31.0H), 1.49 (12.9H), 1.64 (13.7H), 3.12 (12.0H), 3.90 (8.1H)

[0052] Synthesis Example 2 An isocyanurate skeleton-containing organopolysiloxane was obtained by charging and reacting the components in the amount ratios shown in the table below in the same manner as in Synthesis Example 1. The target isocyanurate skeleton-containing organopolysiloxane was a colorless, semi-transparent solid with a melting point of 82 to 88°C. 1 H-NMR (400MHz, CDCl3, 25°C, ppm): 0.06 (196.8H), 0.52 (12.4H), 0.88 (9. 4H), 1.32 (25.9H), 1.52 (13.1H), 1.64 (6.9H), 3.13 (12.0H), 3.90 (6.8H)

[0053] Synthesis Example 3 An isocyanurate skeleton-containing organopolysiloxane was obtained by charging and reacting the components in the amount ratios shown in the table below in the same manner as in Synthesis Example 1. The target isocyanurate skeleton-containing organopolysiloxane was a colorless, semi-transparent solid with a melting point of 62 to 70°C. 1 H-NMR (400MHz, CDCl3, 25°C, ppm): 0.06 (552.4H), 0.52 (11.7H), 0.85 (9. 8H), 1.30 (28.4H), 1.51 (12.7H), 1.64 (8.3H), 3.14 (12.0H), 3.89 (7.1H)

[0054] Synthesis Example 4 A reaction vessel was charged with an isocyanurate-containing polyisocyanate, which is a trimer of pentamethylene diisocyanate, in the amount of substances shown in the table below, and an amino-modified silicone was added dropwise while heating at 100° C. After all of the amino-modified silicone had been added dropwise, the mixture was aged at 100° C. for 1 hour to obtain an isocyanate skeleton-containing organopolysiloxane. The target isocyanurate skeleton-containing organopolysiloxane was a colorless, transparent liquid. 1 H-NMR (400MHz, CDCl3, 25°C, ppm): 0.06 (1016.7H), 0.52 (11.2H), 0.85 (9. 1H), 1.31 (28.3H), 1.51 (12.5H), 1.62 (8.0H), 3.15 (12.0H), 3.91 (6.9H)

[0055] Synthesis Example 5 An isocyanurate skeleton-containing organopolysiloxane was obtained by charging and reacting the components in the amount ratios shown in the table below in the same manner as in Synthesis Example 1. The target isocyanurate skeleton-containing organopolysiloxane was a white solid. 1 H-NMR (400MHz, CDCl3, 25°C, ppm): 0.07 (343.3H), 0.55 (6.8H), 1.29 (14.1H), 1.52 (12.5H), 1.62 (7.1H), 3.13 (12.0H), 3.91 (6.7H)

[0056] Synthesis Example 6 An isocyanurate skeleton-containing organopolysiloxane was obtained by charging and reacting the components in the amount ratios shown in the table below in the same manner as in Synthesis Example 1. The target isocyanurate skeleton-containing organopolysiloxane was a colorless, translucent solid. 1 H-NMR (400MHz, CDCl3, 25°C, ppm): 0.05 (274.0H), 0.55 (6.8H), 1.30 (13.5H), 1.52 (12.1H), 1.62 (6.6H), 3.14 (12.0H), 3.94 (6.6H)

[0057] Synthesis Example 7 An isocyanurate skeleton-containing organopolysiloxane was obtained by charging and reacting the components in the ratios shown in the table below in the same manner as in Synthesis Example 1. The target isocyanurate skeleton-containing organopolysiloxane was a pale yellow, transparent solid. 1 H-NMR (400MHz, CDCl3, 25°C, ppm): 0.06 (64.2H), 0.56 (6.9H), 1.31 (12.7H), 1.52 (12.0H), 1.62 (6.3H), 3.14 (12.0H), 3.95 (6.6H)

[0058] Synthesis Example 8 An isocyanurate skeleton-containing organopolysiloxane was obtained by charging and reacting the components in the amount ratios shown in the table below in the same manner as in Synthesis Example 1. The target isocyanurate skeleton-containing organopolysiloxane was a white solid with a melting point of 98 to 101°C. 1H-NMR (400MHz, CDCl3, 25°C, ppm): 0.06 (85.1H), 0.55 (6.2H), 1.30 (11.8H), 1.56 (12.7H), 1.62 (6.0H), 3.14 (12.0H), 3.95 (6.1H)

[0059] Synthesis Example 9 An isocyanurate skeleton-containing organopolysiloxane was obtained by charging and reacting the components in the amount ratios shown in the table below in the same manner as in Synthesis Example 1. The target isocyanurate skeleton-containing organopolysiloxane was a colorless, transparent solid with a temperature of 98 to 103°C. 1 H-NMR (400MHz, CDCl3, 25°C, ppm): 0.06 (218.4H), 0.52 (9.9H), 0.87 (6.2 H), 1.32 (21.0H), 1.52 (12.7H), 1.64 (6.3H), 3.12 (12.0H), 3.90 (6.5H)

[0060] Synthesis Example 10: An isocyanurate skeleton-containing organopolysiloxane was obtained by charging and reacting the components in the amount ratios shown in the table below in the same manner as in Synthesis Example 1. The target isocyanurate skeleton-containing organopolysiloxane was a colorless, transparent solid at 94 to 100°C. 1 H-NMR (400MHz, CDCl3, 25°C, ppm): 0.06 (412.6H), 0.52 (10.1H), 0.88 (6. 3H), 1.32 (20.3H), 1.52 (12.1H), 1.66 (6.3H), 3.12 (12.0H), 3.91 (6.0H)

[0061]

[0062] [Examples 1 to 5, Comparative Examples 1 to 3] An isocyanurate skeleton-containing organopolysiloxane was mixed into each of the various solvents shown in Tables 2 and 3 so that the amount was 10% by mass. The resulting mixture was heated at 100°C and evaluated for solubility according to the following criteria. The mixture was then allowed to cool to room temperature, and the thickening properties of the mixture were evaluated according to the following criteria. As comparative examples, similar evaluations were also performed on inulin stearate and dibutyl lauroyl glutamide, which are commonly used thickening / gelling agents for oils. Note that, because dibutyl lauroyl glutamide did not dissolve in any of the solvents (Comparative Example 2), a similar evaluation was performed at 150°C (Comparative Example 3).

[0063] (Solubility; Transparency) Criteria: ◎: Clear and soluble 〇: Cloudy but uniformly dispersed ×: Separated, insoluble

[0064] (Thickening property; gelling property) Criteria: ◎: Solidification (no fluidity) ◯: Fluidity exists, but viscosity increases to 10 times or more the solvent viscosity ×: Fluidity exists, but viscosity increases to 10 times or less the solvent viscosity, and separation The viscosity was measured at 25°C using a B-type viscometer as described in JIS K 7117-1:1999.

[0065]

[0066]

[0067] As is clear from the above results, it was confirmed that the isocyanurate skeleton-containing organopolysiloxane of the present invention has excellent solubility in silicone oil and can effectively thicken and gel silicone oil. On the other hand, while the inulin stearate of Comparative Example 1 was able to thicken and gel KF-995, it had poor solubility in linear dimethylpolysiloxane and was unable to thicken or gel. Furthermore, dibutyl lauroyl glutamide could not be dissolved in solvents at 100°C, and was unable to thicken or gel linear dimethylpolysiloxanes of KF-96L-2cs or higher.

[0068] The raw materials used in the examples are as follows: KF-995: Decamethylcyclopentasiloxane KF-96L-2cs: Kinematic viscosity at 25°C 2 mm 2 / s linear dimethylpolysiloxane KF-96A-6cs: kinematic viscosity at 25 ° C. 6 mm 2 / s linear dimethylpolysiloxane KF-96A-200cs: kinematic viscosity at 25 ° C 200 mm 2 / s linear dimethylpolysiloxane KF-56A: kinematic viscosity at 25 ° C 15 mm 2 / s linear methylphenylpolysiloxane: These are manufactured by Shin-Etsu Chemical Co., Ltd. The kinematic viscosity is a value measured at 25°C using a Cannon-Fenske viscometer according to the method described in JIS Z 8803:2011.

Claims

1. The following formula (1) (wherein Q is a divalent hydrocarbon group having 2 to 10 carbon atoms, X is a divalent group having 2 to 8 carbon atoms which may contain a divalent amino group represented by —NH— within the group, n is an integer from 1 to 5, and * is a free group which bonds to * in the following formula (2), (3), (4), or (5)), and one or more organopolysiloxane chains selected from the following formulas (2), (3), (4), and (5): (wherein R independently represents a monovalent hydrocarbon group having 1 to 10 carbon atoms; R 1 is an alkyl group having 1 to 4 carbon atoms, and p is an integer from 1 to 100. * is a free group that bonds to * in the above formula (1). (In the formula, R is the same as above, q is 1 to 5, r is an integer of 0 to 100, and the position of the siloxane unit bracketed by q may be anywhere in the molecular chain. * is a free radical that bonds to each different * in formula (1) above.) (In the formula, R is the same as above. * is a free group that bonds to * in formula (1) above.) (In the formula, R is the same as above, and s is an integer of 1 to 100. Each * represents a free group that bonds to a different * in formula (1) above.) 2. The isocyanurate skeleton-containing organopolysiloxane according to claim 1, which is composed of an isocyanurate skeleton represented by the above formula (1) and an organopolysiloxane chain represented by the above formula (2) or (5).

3. The isocyanurate skeleton-containing organopolysiloxane according to claim 1, which is composed of an isocyanurate skeleton represented by the above formula (1) and an organopolysiloxane chain represented by the above formula (4) or (5).

4. The isocyanurate skeleton-containing organopolysiloxane according to claim 1, which is composed of an isocyanurate skeleton represented by the above formula (1) and an organopolysiloxane chain represented by the above formula (2).

5. The isocyanurate skeleton-containing organopolysiloxane according to claim 1, wherein the molar ratio (5) / (2) of the organopolysiloxane chain represented by formula (2) to the molar ratio (5) of the organopolysiloxane chain represented by formula (5) is 0 to 1.

6. A thickener comprising the isocyanurate skeleton-containing organopolysiloxane according to any one of claims 1 to 5.

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