Thickening agent and composition

Abstract

A thickening agent containing the reaction product of (A) one or more isocyanurate skeleton-containing polyisocyanates and (B) one or more amino-modified silicones represented by formula (1) (therein, each R1 independently represents a monovalent hydrocarbon group having 1-12 carbon atoms or an amino group represented by formula (2) (therein, Q represents a divalent group that has 2-8 carbon atoms and optionally contains therein a divalent amino group represented by -NH-), with at least one R1 in formula (1) being an amino group represented by formula (2); a is an integer of 0-100; b is an integer of 0-5; and c is an integer of 0-5), said thickening agent exhibiting excellent solubility in silicone oils and organic oils, and being capable of inducing the gelation thereof.

Description

Thickeners and compositions

[0001] The present invention relates to a thickener.

[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, coating materials, etc. For example, Patent Document 1 discloses a technique for forming a rigid polyurethane foam by reacting a polyol with a polyisocyanate compound in the presence of an amino-modified silicone.

[0003] Furthermore, Patent Document 2 discloses a composition containing an amino-modified silicone, a blocked polyisocyanate, and a polyol. In this document, 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. Furthermore, Patent Document 3 discloses a resin composition for coating in which the reaction product of an amino-modified silicone and a resin having an organic functional group and a hydroxyl group is reacted with an isocyanate compound.

[0004] However, there have been no examples to date of using a compound in which the isocyanurate skeleton has been modified with a monofunctional organopolysiloxane or a side-chain functional organopolysiloxane as a thickener.

[0005] International Publication No. 2008 / 062796 JP 2020-032658 A JP 2017-066284 A

[0006] The present invention has been made in view of the above circumstances, and aims to provide a thickener and composition that have excellent solubility in silicone oils and organic oils and are capable of thickening and gelling these.

[0007] As a result of extensive research into achieving the above object, the present inventors have found that the above problems can be solved by a reaction product of (A) an isocyanurate skeleton-containing polyisocyanate and (B) one or more specific amino-modified silicones, which led to the completion of the present invention.

[0008] Therefore, the present invention provides the following thickener: 1. (A) one or more isocyanurate skeleton-containing polyisocyanates, and (B) one or more amino-modified silicones represented by the following formula (1): [In the formula, R 1 are independently a monovalent hydrocarbon group having 1 to 12 carbon atoms, or an amino group represented by the following formula (2): -Q-NH2 (2) (wherein Q 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), and in formula (1), R 1 wherein one or more of the following are amino groups represented by the following formula (2): a is an integer of 0 to 100, b is an integer of 0 to 5, and c is an integer of 0 to 5. 2. A thickener according to 1, wherein the component (A) is one or more selected from the group consisting of a trimer of hexamethylene diisocyanate, a trimer of pentamethylene diisocyanate, and a trimer of toluene diisocyanate. 3. A thickener according to 1, wherein the component (B) is a compound represented by the following formula (3): (In the formula, R 2 are independently monovalent hydrocarbon groups having 1 to 12 carbon atoms, and R 3 is an amino group represented by the above formula (2), and R 4 are independently R 2 or R 3 where d is an integer of 0 to 10, e is an integer of 0 to 100, and d+e is an integer of 0 to 100. When d is 0, R 4 At least one of 3 (C) a primary alkylamine having 1 to 20 carbon atoms. 5. A composition comprising the thickener according to any one of 1 to 4 and an oil agent. 6. The composition according to 5, wherein the oil agent is selected from silicone oil, hydrocarbon oil, ester oil, glyceride oil, vegetable oil, mineral oil, other synthetic oil, organic solvent, and mixtures thereof.

[0009] According to the present invention, it is possible to provide a thickener and a composition that have excellent solubility in silicone oils and organic oils and are capable of gelling these oils.

[0010] The isocyanurate skeleton-containing organopolysiloxane obtained in Synthesis Example 2 1 1 is a H-NMR spectrum chart.

[0011] The present invention is a thickener comprising a reaction product of (A) one or more isocyanurate skeleton-containing polyisocyanates and (B) one or more amino-modified silicones represented by the following formula (1):

[0012] [Component (A)] Component (A) is an isocyanurate skeleton-containing polyisocyanate, and can be used alone or in combination of two or more. Examples include diisocyanate trimers. Of these, isocyanurate compounds such as hexamethylene diisocyanate trimers, pentamethylene diisocyanate trimers, and toluene diisocyanate trimers are preferred. Component (A) may be used alone or in combination with different isocyanurate skeleton-containing polyisocyanates. The number of repeating units of the isocyanurate skeleton in the isocyanurate skeleton-containing polyisocyanate is not particularly limited, but is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 2. Specific examples include isocyanurate skeleton-containing polyisocyanates represented by the following formula:

[0013] (wherein n is an integer of 1 to 5.)

[0014] [Component (B)] The component (B) is an amino-modified silicone represented by the following formula (1), and may be used alone or in combination of two or more types. [In the formula, R 1 are independently a monovalent hydrocarbon group having 1 to 12 carbon atoms, or an amino group represented by the following formula (2): -Q-NH (2) (wherein Q 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), and in formula (1), R 1 At least one of the groups is an amino group represented by the following formula (2), where a is an integer of 0 to 100, b is an integer of 0 to 5, and c is an integer of 0 to 5.

[0015] Specific examples of monovalent hydrocarbon groups having 1 to 12 carbon atoms include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl groups, aryl groups such as phenyl and tolyl groups, and aralkyl groups such as benzyl and phenethyl groups. Among these, methyl, ethyl, and phenyl groups are preferred, and methyl is more preferred. In formula (1), R 1 is an amino group represented by the above formula (2). Specific examples of formula (2) include the amino groups shown below.

[0016]

[0017] a is an integer of 0 to 100, preferably 0 to 30; b is an integer of 0 to 5; and c is an integer of 0 to 5.

[0018] Component (B) is preferably one or more amino-modified silicones represented by the following formula (3): (In the formula, R 2 are independently monovalent hydrocarbon groups having 1 to 12 carbon atoms, and R 3 is an amino group represented by the above formula (2), and R 4 are independently R 2 or R 3 where d is an integer from 0 to 10 and e is an integer from 0 to 100. Note that d+e is an integer from 0 to 100, and when d is 0, R 4 At least one of 3 It is.)

[0019] In the formula, R 2 are independently monovalent hydrocarbon groups having 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms. Specific examples include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl; 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 methyl is more preferred.

[0020] R 3 is an amino group represented by the above formula (2), and is the same as above. 4are independently R 2 or R 3 where d is an integer from 0 to 10, and e is an integer from 0 to 100. When d is 0, R 4 At least one of 3 d is preferably 0 to 5, and more preferably 0 to 2. If 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 in turn impairs usability. e is preferably 0 to 60 from the viewpoint of compatibility with oils.

[0021] Specific examples of component (B) include amino-modified silicones represented by the following formula: (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.)

[0022] The reaction product of the present invention may be a reaction product of the components (A) and (B) described above, plus a primary alkylamine having 1 to 20 carbon atoms, preferably 4 to 18 carbon atoms, as component (C), and the component (A) and the component (B) with the primary alkylamine having 1 to 20 carbon atoms (C). Examples of the primary alkylamine having 1 to 20 carbon atoms include methylamine, ethylamine, propylamine, butylamine, amylamine, hexylamine, heptylamine, octylamine, 1-aminoundecane, 1-aminodecane, dodecylamine, stearylamine, and 1-aminononadecane.

[0023] The ratio of the amounts of substances of component (B) to component (C) in the reaction product, (C) / (B), is preferably 0 to 10, more preferably 0 to 3. When component (C) is contained, it is preferably 0.5 to 2.

[0024] Furthermore, the reaction product of the present invention preferably does not contain a polyol as a reactant. Although a polyol forms a urethane bond by reacting with component (A), the urethane bond has weaker hydrogen bonding between functional groups than the urea bond formed by component (A) and component (B) or (C), and therefore may be less likely to exhibit thickening properties.

[0025] The reaction product of the present invention is a product of reaction between an isocyanurate group of one or more isocyanurate skeleton-containing polyisocyanates (A) and an amino group, and has the structure "-R'-NH-CO-NH-R'-". The same applies when component (C) is included.

[0026] [Physical Properties of Reaction Product] The melting point of the reaction product 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 in differential scanning calorimetry (DSC) as described in ISO Standard 11357-3:1999.

[0027] [Production Method] A reaction product of (A) an isocyanurate skeleton-containing polyisocyanate and (B) one or more specific amino-modified silicones. The reaction can be carried out by any known method without any particular limitation, and examples thereof include the following methods.

[0028] 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.

[0029] Next, the amino-modified silicone (B) is added dropwise using a dropping funnel and stirred to obtain a reaction product (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 determined 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.

[0030] In the production of the reaction product of the present invention, a known catalyst may be used as needed to ensure that the reaction between the isocyanate group and the active hydrogen group in the raw material proceeds smoothly. 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.

[0031] [Thickener] The reaction product of the present invention (isocyanurate skeleton-containing organopolysiloxane) has excellent solubility in silicone oils and organic oils and can thicken and gel them. Because of the above properties, this reaction product is effective as an active ingredient in thickeners and gelling agents. It is particularly suitable for thickening and gelling silicone oils, and can thicken and gel linear dimethylpolysiloxanes, which have traditionally been difficult to thicken and gel. Solubility can be confirmed using the methods described in the Examples below. Regarding thickening and gelling properties, it is preferable that the viscosity be increased to 10 times or more the solvent viscosity while maintaining fluidity, as measured by the methods described in the Examples below, and solidification (no fluidity) is more preferable. The present invention can be applied to fields where a thickening effect is expected, such as cosmetics.

[0032] [Composition] The composition of the present invention contains the above-mentioned thickener and an oil. The thickener of the present invention forms molecular aggregates in the oil via hydrogen bonds of the urea groups, thereby exhibiting the effect of thickening the oil. Examples of oils include silicone oils, organic oils such as hydrocarbon oils, ester oils, glyceride oils, vegetable oils, mineral oils, other synthetic oils, organic solvents, and mixtures thereof, and these can be used alone or in combination of two or more. Specific examples are as follows. Hereinafter, compound names may be written using the cosmetic label name or INCI (International Nomenclature of Cosmetic Ingredients). When the cosmetic label name and INCI correspond, the cosmetic label name or English name may be omitted.

[0033] 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.

[0034] 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).

[0035] 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.

[0036] 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).

[0037] 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.

[0038] 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.

[0039] The amount of the reaction product of components (A) and (B), or the amount of the reaction product of components (A), (B), or (C) in the composition is preferably 0.5 to 50 mass%, more preferably 5 to 30 mass%. The amount of the oil in the composition is preferably 50 to 99.5 mass%, more preferably 70 to 95 mass%.

[0040] 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.

[0041] [Synthesis of Thickener] The reaction raw materials used in the synthesis of the thickener of the present invention are shown below. Note that the melting points shown in the following synthesis examples correspond to the temperatures at the apex of the endothermic peak observed by differential scanning calorimetry (DSC) as described in ISO Standard 11357-3:1999.

[0042] (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.)

[0043]

[0044]

[0045]

[0046] (C) Alkylamine, butylamine, stearylamine

[0047] 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 an amino-modified silicone was added dropwise to the mixture at the molar ratio shown in Table 1 below while heating at 100°C. After the addition was complete, the mixture was aged at 100°C for 1 hour to obtain an isocyanate skeleton-containing organopolysiloxane. The resulting isocyanurate skeleton-containing organopolysiloxane was a colorless, translucent solid with a melting point of 82 to 88°C.

[0048] 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 obtained isocyanurate skeleton-containing organopolysiloxane was a colorless, translucent 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)

[0049] 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 obtained isocyanurate skeleton-containing organopolysiloxane was a colorless, translucent solid with a melting point of 62 to 70°C.

[0050] 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 resulting isocyanurate skeleton-containing organopolysiloxane was a colorless, transparent liquid.

[0051] 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 obtained isocyanurate skeleton-containing organopolysiloxane was a white solid.

[0052] 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 obtained isocyanurate skeleton-containing organopolysiloxane was a colorless, semitransparent solid.

[0053] Synthesis Example 7 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 obtained isocyanurate skeleton-containing organopolysiloxane was a pale yellow, transparent solid.

[0054] 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 obtained isocyanurate skeleton-containing organopolysiloxane was a white solid with a melting point of 98 to 101°C.

[0055] 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 obtained isocyanurate skeleton-containing organopolysiloxane was a colorless, transparent solid with a temperature of 98 to 103°C.

[0056] 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 obtained isocyanurate skeleton-containing organopolysiloxane was a colorless, semi-transparent solid at 90 to 100°C.

[0057] Synthesis Example 11 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 obtained isocyanurate skeleton-containing organopolysiloxane was a colorless, semi-transparent solid at 98 to 105°C.

[0058]

[0059] [Examples 1 to 5, Comparative Examples 1 to 3] The reaction product (isocyanurate skeleton-containing organopolysiloxane) was mixed with each of the various solvents shown in Table 2 so that the reaction product 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).

[0060] (Solubility; Transparency) Criteria: ◎: Clear and soluble 〇: Cloudy but uniformly dispersed ×: Separated, insoluble

[0061] (Thickening; gelling) 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 occurs "-" indicates that measurement was not performed. The viscosity was measured using a Brookfield viscometer at 25°C as described in JIS K 7117-1:1999.

[0062]

[0063]

[0064] 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 Linear methylphenyl polysiloxane (10 cs): manufactured by Shin-Etsu Chemical Co., Ltd. Polyalphaolefin (10 cs): trade name: Durasyn 170 (manufactured by Nippon Steel Chemical & Material Co., Ltd., kinematic viscosity at 25°C: 10 mm 2 / s) 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.

[0065] As is clear from the above results, it was confirmed that the thickener of the present invention has excellent solubility in silicone oil and can effectively thicken / gel various oil agents. On the other hand, inulin stearate of Comparative Example 1 was able to gel decamethylcyclopentasiloxane, but had poor solubility in linear dimethylpolysiloxane and was unable to gel. Furthermore, dibutyl lauroyl glutamide could not be dissolved in solvent at 100°C, and was unable to gel linear dimethylpolysiloxane with a high dynamic viscosity.

Claims

1. (A) one or more isocyanurate skeleton-containing polyisocyanates; and (B) one or more amino-modified silicones represented by the following formula (1): [In the formula, R 1 are independently a monovalent hydrocarbon group having 1 to 12 carbon atoms, or an amino group represented by the following formula (2): -Q-NH2 (2) (wherein Q 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), and in formula (1), R 1 wherein one or more of the following is an amino group represented by the following formula (2), a is an integer of 0 to 100, b is an integer of 0 to 5, and c is an integer of 0 to 5:

2. The thickener according to claim 1, wherein component (A) is at least one selected from the group consisting of a trimer of hexamethylene diisocyanate, a trimer of pentamethylene diisocyanate, and a trimer of toluene diisocyanate.

3. The component (B) is represented by the following formula (3): (In the formula, R 2 are independently monovalent hydrocarbon groups having 1 to 12 carbon atoms, and R 3 is an amino group represented by the above formula (2), and R 4 are independently R 2 or R 3 where d is an integer of 0 to 10, e is an integer of 0 to 100, and d+e is an integer of 0 to 100. When d is 0, R 4 At least one of 3 2. The thickener according to claim 1, which is one or more amino-modified silicones represented by the formula:

4. The thickener according to claim 1, wherein the reaction product is a reaction product of the components (A) and (B) with (C) a primary alkylamine having 1 to 20 carbon atoms.

5. A composition comprising the thickener according to any one of claims 1 to 4 and an oil agent.

6. The composition according to claim 5, wherein the oil is selected from the group consisting of silicone oil, hydrocarbon oil, ester oil, glyceride oil, vegetable oil, mineral oil, other synthetic oil, organic solvent and mixtures thereof.

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