Paste-like silicone composition, its method of manufacture and cosmetic

Abstract

To provide a paste-like silicone composition that has little secular change such as plasticity reversion, has little foreign odor, and is stable.SOLUTION: Provided is a paste-like silicone composition that contains (A) a crosslinked organopolysiloxane comprising a hydrosilylation reaction product of (A-1) an organohydrogenpolysiloxane having two or more hydrogen atoms bonded to silicon atoms in one molecule, and (A-2) an alkenyl group-containing organopolysiloxane having two or more C2-10 alkenyl groups bonded to silicon atoms in one molecule, and (B) an oil agent that is liquid at 25°C, where octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and dodecamethylcyclohexasiloxane contained in the composition are each less than 2,000 ppm.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a paste-like silicone composition, a method for producing the same, and a cosmetic composition. [Background technology]

[0002] As a method for stably blending silicone oils, hydrocarbon oils, ester oils, and the like into cosmetics and personal care compositions, organosiloxane polymers having a crosslinked structure have been proposed (Patent Documents 1, 2, and 3). This is already a known technology, and organosiloxane polymers having a crosslinked structure (hereinafter referred to as silicone crosslinks) are mainly obtained by a hydrosilylation reaction between organohydrogenpolysiloxanes and alkenyl group-containing organopolysiloxanes, and are blended into cosmetics and personal care compositions in a state of being mixed in advance with a portion of the oil agent to be used and made into a paste.

[0003] However, these prior arts do not specifically mention the low molecular weight siloxane components contained in the organohydrogenpolysiloxanes and alkenyl group-containing organopolysiloxanes used. Organohydrogenpolysiloxanes and alkenyl group-containing organopolysiloxanes are generally produced by hydrolyzing dimethylchlorosilane or siloxanes mainly composed of cyclic siloxane oligomers, and then redistributing the raw materials under strong acid or strong base. At this time, highly volatile low molecular weight siloxanes and hydrocarbons such as hexane and hexene often remain as unreacted residues, by-products, and impurities. These low molecular weight components not only cause unpleasant odors and irritation, but also cause a decrease in the thickening effect and plastic reversion. Here, plastic reversion refers to the increase in viscosity of the paste-like silicone composition over time, and the change in properties, specifically, the phenomenon of a smooth, fluid liquid paste changing into a non-fluid jelly-like state.This phenomenon is considered to be a physical phenomenon, and it is possible to return to the original paste state by remixing, etc., but it cannot be denied that the usability is significantly reduced.Therefore, in order to improve the quality of the paste-like silicone composition, it is necessary to manage the amount of highly volatile low molecular weight components.

[0004] In the above technical fields, highly volatile components are mainly those with a molecular weight of less than 300, and it is known that these can be removed by heating under reduced pressure, thin film distillation, steam distillation, column separation, etc. However, it is difficult to remove them after a crosslinked structure is formed by a hydrosilylation reaction, or after they are mixed with an oil agent to form a paste-like silicone composition. Not only does this make the manufacturing process complicated, but if the oil agent is volatile, the oil agent may also be removed by the above-mentioned treatment, and there is also a concern that the composition may change. Furthermore, in recent years, some countries and regions have begun to regulate the use and content of cyclic low molecular weight siloxanes in particular, and the presence of high levels of low molecular weight siloxanes in these regions is a cause for concern when it comes to use. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 01-207354 [Patent Document 2] Japanese Patent Application Publication No. 02-043263 [Patent Document 3] JP 2012-162700 A Summary of the Invention [Problem to be solved by the invention]

[0006] The present invention aims to provide a paste-like silicone composition that is stable and exhibits little change over time such as plastic reversion and little unpleasant odor, and also aims to provide a paste-like silicone composition that contains little cyclic low-molecular-weight siloxane components, which are restricted in some countries and regions. [Means for solving the problem]

[0007] In order to solve the above problems, the present invention provides a paste-like silicone composition comprising the following components (A) and (B), wherein the contents of octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane in the paste-like silicone composition are each less than 2,000 ppm: (A): The following components (A-1) and (A-2); (A-1) an organohydrogenpolysiloxane having two or more hydrogen atoms bonded to silicon atoms in each molecule; (A-2) an alkenyl group-containing organopolysiloxane having two or more alkenyl groups having 2 to 10 carbon atoms bonded to silicon atoms per molecule; a crosslinked organopolysiloxane comprising a hydrosilylation reaction product of (B): Oil that is liquid at 25℃

[0008] Such a paste-like silicone composition is stable and undergoes little change over time, such as reversion to plasticity, and has little unpleasant odor.

[0009] In this case, the component (A-1) is preferably an organohydrogenpolysiloxane represented by the following general formula (1). [ka] (In the above general formula (1), R 1 are independently selected from an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, and an aralkyl group having 7 to 30 carbon atoms; R 2 are independently 1or a hydrogen atom, provided that there are two or more R 2 is a hydrogen atom, and 3≦a≦100,000 and 1≦b≦50 are integers.

[0010] Such a paste-like silicone composition can further improve the effects of the present invention.

[0011] In this case, the component (A-2) is preferably an alkenyl-containing organopolysiloxane represented by the following general formula (2). [ka] (In the general formula (2), R 1 are independently selected from an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, and an aralkyl group having 7 to 30 carbon atoms; R 3 are independently 1 or an alkenyl group having 2 to 10 carbon atoms, provided that there are two or more R 3 is an alkenyl group, and c is an integer of 3≦c≦100,000 and 0≦d≦50.

[0012] Such a paste-like silicone composition can further improve the effects of the present invention.

[0013] In this case, it is preferable that d=0 in the general formula (2).

[0014] Such a paste-like silicone composition can further improve the effects of the present invention.

[0015] The present invention also provides a method for producing the above-mentioned paste-like silicone composition, comprising a step of obtaining component (A) by subjecting component (A-1) and component (A-2) to a hydrosilylation reaction in the presence of a hydrosilylation reaction catalyst, wherein the contents of octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane used as component (A-1) and component (A-2) are each 2,000 ppm or less.

[0016] This method of producing a paste-like silicone composition is preferred from the standpoint of ease of use and production.

[0017] At this time, the hydrosilylation reaction is preferably carried out in the presence of 0.01 to 100 mass % of the blended amount of component (B) blended into the paste-like silicone composition.

[0018] Such a method for producing a paste-like silicone composition is more preferable from the standpoint of ease of use and production.

[0019] The present invention also provides a cosmetic preparation that contains the above-described paste-like silicone composition.

[0020] Such a cosmetic composition would be stable, have good sensory properties, and be environmentally friendly. Effect of the Invention

[0021] According to the present invention, by using a raw material with a reduced content of cyclic low molecular weight siloxane, it is possible to provide a stable paste-like silicone composition that is less prone to change over time such as plastic reversion and has little odor.In addition, it is also effective in that it can be used without concerns in countries and regions that have recently regulated the use and content of cyclic siloxane.Furthermore, by blending this paste-like silicone composition, it is possible to provide a cosmetic that is stable, functional, and environmentally friendly. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0022] As described above, there has been a demand for the development of a paste-like silicone composition that is stable and exhibits little change over time, such as plastic reversion, and has little unpleasant odor.

[0023] As a result of intensive research into the above-mentioned problems, the present inventors discovered that unpleasant odors and reversion to plasticity could be suppressed by reducing the amounts of octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane contained in the paste-like silicone composition, and thus completed the present invention. Octamethylcyclotetrasiloxane has a molecular weight of 296, decamethylcyclopentasiloxane has a molecular weight of 370, and dodecamethylcyclohexasiloxane has a molecular weight of 444, so by controlling the amounts of these, highly volatile components with a molecular weight of less than 300 can be sufficiently removed.

[0024] That is, the present invention is a paste-like silicone composition comprising the following components (A) and (B), wherein the contents of octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane in the paste-like silicone composition are each less than 2,000 ppm: (A): The following components (A-1) and (A-2); (A-1) an organohydrogenpolysiloxane having two or more hydrogen atoms bonded to silicon atoms in each molecule; (A-2) an alkenyl group-containing organopolysiloxane having two or more alkenyl groups having 2 to 10 carbon atoms bonded to silicon atoms per molecule; a crosslinked organopolysiloxane comprising a hydrosilylation reaction product of (B): Oil that is liquid at 25℃

[0025] The present invention will be described in detail below, but the present invention is not limited thereto.

[0026] [Paste-like silicone composition] The paste-like silicone composition of the present invention contains the following components (A) and (B), and the contents of octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane in the paste-like silicone composition are each less than 2,000 ppm. Each component will be described below.

[0027] [Component (A)] The component (A) of the present invention is composed of the following components (A-1) and (A-2); (A-1) an organohydrogenpolysiloxane having two or more hydrogen atoms bonded to silicon atoms in each molecule; (A-2) an alkenyl group-containing organopolysiloxane having two or more alkenyl groups having 2 to 10 carbon atoms bonded to silicon atoms per molecule; The crosslinked organopolysiloxane is a hydrosilylation reaction product of the above. Furthermore, the above components (A-1) and (A-2) are preferably organopolysiloxanes in which the contents of octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane are each 2,000 ppm or less, and preferably 1,000 ppm or less.

[0028] The structure of the organohydrogenpolysiloxane (A-1) is not particularly limited, but is preferably one represented by the following formula (1). [ka] (In the above general formula (1), R 1 are independently selected from an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, and an aralkyl group having 7 to 30 carbon atoms; R 2 are independently 1 or a hydrogen atom, provided that there are two or more R 2 is a hydrogen atom, and 3≦a≦100,000 and 1≦b≦50 are integers.

[0029] In the above general formula (1), R 1 are independently a group selected from an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, and an aralkyl group having 7 to 30 carbon atoms, and the alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms. Examples of the alkyl group include chain alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, a lauryl group, a myristyl group, a palmityl group, and a stearyl group, and cycloalkyl groups such as a cyclopentyl group and a cyclohexyl group, and preferably a methyl group or an ethyl group.

[0030] The aryl group is preferably an aryl group having a carbon number of 6 to 20, more preferably 6 to 10. Examples of the aryl group include a phenyl group, a tolyl group, and a xylyl group, and the phenyl group is preferred. The aralkyl group is preferably an aralkyl group having a carbon number of 7 to 20, more preferably a carbon number of 7 to 10. Examples of the aralkyl group include a benzyl group and a phenethyl group, and a benzyl group is preferable.

[0031] R 2 is independently the above R 1 or a hydrogen atom, and two or more R 2 is a hydrogen atom, and is preferably 2 to 5 in number. In addition, in formula (1), a is an integer satisfying 3≦a≦100,000, preferably 5≦a≦1,000, and more preferably 10≦a≦500. b is an integer satisfying 1≦b≦50, preferably 1≦b≦30, and more preferably 2≦b≦10. It is also possible to use an organohydrogenpolysiloxane in which b=0 in combination.

[0032] The structure of the alkenyl-containing organopolysiloxane (A-2) is not particularly limited, but is preferably one represented by the following formula (2). [ka] (In the general formula (2), R1 are independently selected from an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, and an aralkyl group having 7 to 30 carbon atoms; R 3 are independently 1 or an alkenyl group having 2 to 10 carbon atoms, provided that there are two or more R 3 is an alkenyl group, and c is an integer of 3≦c≦100,000 and 0≦d≦50.

[0033] In the above general formula (2), R 1 is as described above, and R 3 is independently the above R 1 or an alkenyl group having 2 to 10 carbon atoms, and two or more R 3 is an alkenyl group. Examples of the alkenyl group include vinyl, allyl, propenyl, butenyl, pentenyl, and hexenyl groups, but vinyl is preferred because of its ease of hydrosilylation reaction with hydrogen atoms bonded to silicon and its good stability. c is an integer of 3≦c≦100,000, preferably 5≦c≦10,000, and more preferably 10≦c≦1,000. d is an integer of 0≦d≦50, preferably 0≦d≦10, and more preferably d=0. When d=0, the effects of the present invention can be further improved.

[0034] When obtaining component (A), it is also possible to use in combination an organohydrogenpolysiloxane having only one hydrogen atom bonded to a silicon atom per molecule, or an organopolysiloxane having only one alkenyl group bonded to a silicon atom per molecule.

[0035] [Component (B)] There are no particular limitations on component (B) so long as it is an oil that is liquid at 25°C. However, from the viewpoint of easy handling when made into a paste, it is preferable to use an oil having a kinetic viscosity of 1.0 to 10,000 mm at 25°C. 2Liquid oils having a viscosity of 1 / s are preferred, and preferred oils include the following silicone oils, hydrocarbon oils, ester oils, fluorine-based oils, natural animal and vegetable oils, and semi-synthetic oils. Note that in this specification, the kinetic viscosity refers to the kinetic viscosity at 25°C measured using a Cannon-Fenske viscometer as described in JIS Z 8803:2011.

[0036] Examples of silicone oils include alkyl-modified silicones such as dimethicone (INCI), ethyl methicone (INCI), ethyl trisiloxane (INCI), and hexyl dimethicone (INCI), long-chain alkyl-modified silicones such as caprylyl methicone (INCI), linear or branched organopolysiloxanes such as phenyl trimethicone (INCI), diphenylsiloxyphenyl trimethicone (INCI), diphenyl dimethicone (INCI), and tetraphenyl dimethyl disiloxane (INCI), and cyclotetrasiloxane (INCI). I), cyclic organopolysiloxanes such as cyclopentasiloxane (INCI), cyclohexasiloxane (INCI), cycloheptasiloxane (INCI), tetramethyltetraphenylcyclotetrasiloxane, etc., amino-modified organopolysiloxanes such as amodimethicone (INCI), aminopropyl dimethicone (INCI), etc., pyrrolidone-modified organopolysiloxanes such as PCA dimethicone (INCI), pyrrolidone carboxylic acid-modified organopolysiloxanes, amino acid-modified silicones, and fluorine-modified silicones.

[0037] Examples of the hydrocarbon oil include linear and cyclic hydrocarbon oils. Specific examples include isoparaffins such as olefin oligomers (INCI), (C13,14) isoparaffin (INCI), isododecane (INCI), undecane (INCI), dodecane (INCI), isohexadecane (INCI), hydrogenated polyisobutene (INCI), squalane (INCI), mineral oil (INCI), coconut alkanes (INCI), and (C13-15) alkanes (INCI).

[0038] Examples of ester oils include alkyl glycol monoisostearates such as diisobutyl adipate (INCI: Diisobutyl Adipate), dihexyldecyl adipate (display name), diheptylundecyl adipate (INCI: Diheptylundecyl Adipate), isostearyl isostearate (INCI: Isostearyl Isostearate), and isocetyl isostearate (INCI: Isocetyl Isostearate), trimethylolpropane triisostearate (INCI: Trimethylolpropane Triisostearate), glycol diethylhexanoate (INCI: Glycol Diethylhexanoate), cetyl ethylhexanoate (INCI: Cetyl Ethylhexanoate), trimethylolpropane triethylhexanoate (INCI: Trimethylolpropane Triethylhexanoate), and pentaerythrityl tetraethylhexanoate (INCI: Pentaerythrityl Tetraethylhexanoate). Tetraethylhexanoate, cetyl octanoate (INCI: Cetyl Ethylhexanoate), octyldodecyl esters such as stearoyloxystearate (INCI: Octyldodecyl Stearoyl Stearate), 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 Dicaprate), diisostearyl malate (INCI: Diisostearyl Malate), triethyl citrate (INCI: Triethyl Citrate), diethylhexyl succinate (INCI: Diethylhexyl Succinate), amyl acetate (INCI: Amyl Acetate) Acetate, Ethyl acetate (INCI:Etyl Acetate), Butyl acetate (INCI:ButylAceetate, Isocetyl Stearate, Butyl Stearate, Diisopropyl Sebacate, Diethylhexyl Sebacate, Cetyl Lactate, Myristyl Lactate, Isononyl Isononanoate, Isotridecyl Isononanoate, Isopropyl Palmitate, Ethylhexyl Isopalmitate, Hexyldecyl Palmitate myristates such as cholesteryl hydroxystearate (INCI: Isopropyl myristate), octyldodecyl myristate (INCI: Octyldodecyl myristate), and myristyl myristate (INCI: Myristyl myristate); ethylhexyl laurate (INCI: Ethylhexyl Laurate), hexyl laurate (INCI: Hexyl Laurate), dioctyldodecyl lauroyl glutamate (INCI: Dioctyldodecyl Lauroyl Glutamate), and isopropyl lauroyl sarcosine ester (INCI: Isopropyl Lauroyl Sarcosinate).

[0039] Furthermore, among the ester oils, examples of the glyceride oil include triethylhexanoin (INCI), tri(caprylic acid / capric acid)glyceryl (INCI: Caprylic / Capric Triglyceride), cocoglyceryl (INCI), (caprylic acid / capric acid / succinic acid) triglyceride (INCI: Caprylic / Capric / Succinic Triglyceride), (caprylic acid / capric acid)glycerides (INCI), etc.

[0040] Examples of the fluorine-based oil agent include perfluoropolyether, perfluorodecalin, and perfluorooctane.

[0041] In addition, examples of natural animal and vegetable oils and semi-synthetic oils include avocado oil (INCI: Persea Gratissima (Avocado) Oil), linseed oil (INCI: Linum Usitatissimum (Linseed) Seed Oil), almond oil (INCI: Prunus Amygdalus Dulcis (Sweet Almond) Oil), perilla oil (display name), olive oil (INCI: Olea Europaea (Olive) Fruit Oil), American grass oil (INCI: Torreya Californica (California Nutmeg) Oil), Japanese cypress oil (INCI: Cymbopogon Nardus (Citronella) Oil), torreya seed oil (INCI: Torreya Nucifera Seed Oil), apricot kernel oil (INCI: Kyonin Yu), sesame oil (INCI: Sesamum Indicum (Sesame) Seed Oil), and sesame oil (INCI: Sesamum Indicum (Sesame) Seed Oil). Oil), rice bran oil (INCI:Oryza Sativa (Rice) Bran Oil), camellia oil (INCI:Camellia Kissi Seed Oil), safflower oil (INCI:Carthamus Tinctorius (Safflower) Seed Oil), soybean oil (INCI:Glycine Soja (Soybean) Oil), tea seed oil (INCI:Camellia Sinensis Seed Oil), camellia oil (INCI:Camellia Japonica Seed Oil), evening primrose oil (INCI:Oenothera Biennis (Evening Primrose) Oil), rapeseed oil (INCI:RAPE SHUSHI YU), corn germ oil (INCI:Zea Mays (Corn) Germ Oil), rice germ oil (INCI:Oryza Sativa (Rice) Germ Oil), wheat germ oil (INCI:Triticum Vulgare (Wheat) Germ Oil) Persic oil (display name), palm oil (INCI:Elaeis Guineensis (Palm) Oil), palm kernel oil (INCI:Elaeis Guineensis (Palm) Kernel)Natural vegetable oils such as castor oil (INCI: Ricinus Communis (Castor) Seed Oil), sunflower oil (INCI: Helianthus Annuus (Sunflower) Seed Oil), grape seed oil (INCI: Vitis Vinifera (Grape) Seed Oil), jojoba seed oil (INCI: Simmondsia Chinensis (Jojoba) Seed Oil), macadamia seed oil (INCI: Macadamia Ternifolia Seed Oil), meadowfoam oil (INCI: Limnanthes Alba (Meadowfoam) Seed Oil), cottonseed oil (INCI: Gossypium Herbaceum (Cotton) Seed Oil), palm oil (INCI: Cocos Nucifera (Coconut) Oil), peanut oil, shark liver oil (INCI: Shark Liver Oil), cod liver oil (INCI: Cod Liver Oil), etc. Examples of such oils include natural animal oils such as INCI Fish Liver Oil, Turtle Oil, Mink Oil, and Egg Yolk Oil, and semi-synthetic oils and fats such as hydrogenated coconut oil and liquid lanolin.

[0042] The above-mentioned oils may be used alone or in combination, and among them, it is preferable to use silicone oil, hydrocarbon oil, or ester oil, and it is particularly preferable to use silicone oil or hydrocarbon oil. The amount of component (B) to be blended varies depending on component (A), but is preferably 1 to 98% by mass of the paste-like silicone composition, and more preferably 10 to 95% by mass.

[0043] Furthermore, the contents of octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane in the paste-like silicone composition of the present invention are each less than 2000 ppm, preferably less than 1500 ppm, more preferably less than 1000 ppm, and even more preferably less than 100 ppm. If any of the above cyclic siloxanes is more than 2000 ppm, there is a concern that the composition cannot be used in countries or regions that regulate the use or content of cyclic low molecular weight siloxanes.

[0044] [Cosmetics] Furthermore, examples of cosmetics containing the paste-like silicone composition of the present invention include skin care cosmetics such as milk lotions, creams, cleansing lotions, packs, massage products, beauty serums, beauty oils, detergents, deodorants, hand creams, lip creams, and wrinkle concealers; makeup cosmetics such as make-up bases, concealers, face powders, liquid foundations, oil-based foundations, blushers, eye shadows, mascara, eyeliners, eyebrows, and lipsticks; hair cosmetics such as shampoos, rinses, treatments, and setting agents; ultraviolet ray protective cosmetics such as sunscreen oils, sunscreen milk lotions, and sunscreen creams; antiperspirants, etc.

[0045] Furthermore, the form of these cosmetics can be selected from a variety of forms, including liquid, milky lotion, cream, solid, paste, gel, powder, press, multi-layer, mousse, spray, stick, and the like.

[0046] Furthermore, the form of these cosmetics can be selected from a variety of forms, including aqueous, oily, water-in-oil emulsion, oil-in-water emulsion, non-aqueous emulsion, and multiple emulsions such as W / O / W and O / W / O.

[0047] Furthermore, the paste-like silicone composition of the present invention can be used for applications beyond the cosmetic field, such as sealants, coating agents, greases, adhesives, defoamers, pharmaceuticals, insecticides, and herbicides, and can also be used to adjust the viscosity and improve the rheological properties of materials.

[0048] [Method of producing a paste-like silicone composition] The method for producing the paste-like silicone composition of the present invention includes a step of obtaining the component (A) by subjecting the component (A-1) and the component (A-2) to hydrosilylation reaction in the presence of a catalyst for hydrosilylation reaction, and is not particularly limited as long as the component (A-1) and the component (A-2) are each octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane with a content of 2,000 ppm or less, respectively, and for example, the paste-like silicone composition can be obtained by kneading the component (A) obtained in the step of obtaining the component (A) and the component (B) in a conventional manner. By reducing the amount of octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane remaining in the organohydrogenpolysiloxane or alkenyl group-containing organopolysiloxane that is the raw material for the crosslinked product in advance, unpleasant odors and plastic reversion can be suppressed.

[0049] [Method for producing component (A-1) and component (A-2)] The method for producing the organohydrogenpolysiloxane (A-1) or alkenyl-containing organopolysiloxane (A-2) is not particularly limited, but generally, they are obtained by hydrolyzing dimethyldichlorosilane, or further cracking the hydrolyzate in the presence of an alkali catalyst such as potassium hydroxide, and using siloxanes containing cyclic and / or acyclic siloxane oligomers as the main component as the raw material, and carrying out an equilibration reaction under an acid catalyst or an alkali catalyst. By subjecting the obtained polysiloxane to a treatment such as reduced pressure stripping, the contents of octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane can be reduced to 2,000 ppm or less, respectively.

[0050] [Production method of component (A)] The reaction between the organohydrogenpolysiloxane (A-1) and the alkenyl-containing organopolysiloxane (A-2), which are the components, can be carried out by hydrosilylation reaction in the presence of a hydrosilylation catalyst. This produces the component (A). The hydrosilylation catalyst is not particularly limited, but for example, the organohydrogenpolysiloxane (A-1) and the alkenyl-containing organopolysiloxane (A-2) may be reacted in the presence of a hydrosilylation catalyst such as a platinum compound, such as chloroplatinic acid, alcohol-modified chloroplatinic acid, or chloroplatinic acid-vinylsiloxane complex, or a rhodium compound. In this case, the reaction temperature is not particularly limited, but is preferably 40 to 120°C. The amount of the hydrosilylation catalyst added may be a known effective amount, and is usually 0.1 to 500 ppm, preferably 0.5 to 200 ppm, and more preferably 1 to 100 ppm, calculated as a platinum group metal relative to the total amount of (A-1) and (A-2). In the hydrosilylation reaction, the molar ratio of total alkenyl groups / total hydrosilyl groups is not particularly limited, but is preferably 1 / 10 to 10 / 1, and more preferably 8 / 10 to 3 / 1.

[0051] The hydrosilylation reaction may be carried out without a solvent, or an organic solvent or volatile dimethyl silicone may be used as necessary. Examples of such organic solvents include aliphatic alcohols such as methanol, ethanol, 2-propanol, butanol, etc.; aromatic hydrocarbons such as benzene, toluene, xylene, etc.; aliphatic or alicyclic hydrocarbons such as n-pentane, n-hexane, cyclohexane, etc.; halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, etc.; and ketone solvents such as acetone and methyl ethyl ketone. Among these, from the viewpoint of use in cosmetics, no solvent, ethanol, or 2-propanol are preferred. Volatile dimethyl silicones include those having a kinetic viscosity of 5 mm 2Examples of the reaction method include dimethyl polysiloxanes having a viscosity of 100 / s or less. These organic solvents and volatile dimethyl silicones can be removed by heating under reduced pressure after the reaction, if necessary. The reaction may be carried out in the presence of a liquid oil component (B), and since no other solvent is used, this method is most preferable in terms of usability and production. In this case, the reaction is preferably carried out in the presence of 0.01 to 100 mass%, more preferably 0.1 to 90 mass%, of the amount of component (B) blended in the paste-like silicone composition of the present invention. For example, the method includes a step of obtaining the component (A) by subjecting the component (A-1) and the component (A-2) to a hydrosilylation reaction in the presence of a catalyst for hydrosilylation reaction, and the hydrosilylation reaction in the step of obtaining the component (A) can be carried out in the presence of 0.01 to 100 mass% of the amount of component (B) blended in the paste-like silicone composition. EXAMPLES

[0052] The present invention will be specifically described below using examples and comparative examples, but the present invention is not limited to these. The measurement methods are as follows.

[0053] Cyclic siloxane content: 0.5 g of sample was mixed with 10 ml of acetone containing 20 ppm by mass of tetradecane as an internal standard (shaken for 6 hours), then centrifuged, and the acetone layer was collected and subjected to gas chromatography analysis to quantify each cyclic siloxane component. The results are shown in Table 1. -Consistency: Measured according to the method described in JIS K 2220:2013. Absolute viscosity: Measured by the method described in JIS K 7117-1:1999 using a B-type rotational viscometer (device name: TVB-10M type viscometer manufactured by Toki Sangyo Co., Ltd.). Dynamic viscosity: Measured at 25°C using a Cannon-Fenske viscometer as described in JIS Z 8803:2011. - Off-odor: A panel of nine people conducted a sensory evaluation of the odor, and the most common answer based on the following criteria is listed below. (1) None, (2) Slightly, (3) Yes Plastic return: The properties and the properties the next day were checked visually and by manually mixing with a spatula, and the condition was recorded using the following expressions. (1) None, (2) Slightly, (3) Yes

[0054] Example 1 A reaction vessel was charged with 40.9 parts by mass of the organohydrogenpolysiloxane (1) shown in Table 1 below, 10.8 parts by mass of the alkenyl-containing organopolysiloxane (6) shown in Table 1 below, and dimethylsiloxane (kinematic viscosity 2 mm) as a liquid oil agent at 25°C. 2 C. / s) and 0.02 parts by mass of a 1% by mass solution of chloroplatinic acid in divinyltetramethyldisiloxane as a hydrosilylation reaction catalyst were added, and the reaction was carried out at 70 to 80.degree. C. for 2 hours.

[0055] Next, the entire amount of the reaction mixture was mixed with the above dimethylsiloxane (kinetic viscosity 2 mm) using a three-roll mill. 2 The mixture was thoroughly kneaded with 155 parts by mass of ethyl alcohol / s to obtain a smooth paste-like silicone composition with a consistency of 270 and a reactant / liquid oil ratio of 20 / 80. There was no unpleasant odor, and the properties remained unchanged the next day. At this time, the contents of octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane in the paste-like silicone composition were each less than 100 ppm, and the content of dodecamethylcyclohexasiloxane was 100 ppm.

[0056] Example 2 A reaction vessel was charged with 40.9 parts by mass of the organohydrogenpolysiloxane (1) shown in Table 1 below, 10.0 parts by mass of the alkenyl-containing organopolysiloxane (7) shown in Table 1 below, and dimethylsiloxane (kinematic viscosity 2 mm) as a liquid oil agent at 25°C. 2 C. / s) and 0.02 parts by mass of a 1% by mass solution of chloroplatinic acid in divinyltetramethyldisiloxane as a hydrosilylation reaction catalyst were added, and the reaction was carried out at 70 to 80.degree. C. for 2 hours.

[0057] Next, the entire amount of the reaction mixture was mixed with the above dimethylsiloxane (kinetic viscosity 2 mm) using a three-roll mill. 2The mixture was thoroughly kneaded with 152.7 parts by mass of ethyl alcohol / s to obtain a smooth paste-like silicone composition with a consistency of 273 and a reactant / liquid oil ratio of 20 / 80. There was no unpleasant odor, and the properties remained unchanged the next day. At this time, the contents of octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane in the paste-like silicone composition were each less than 100 ppm, and the content of dodecamethylcyclohexasiloxane was 180 ppm.

[0058] Example 3 A reaction vessel was charged with 8.0 parts by mass of the organohydrogenpolysiloxane (3) shown in Table 1 below, 96.5 parts by mass of the alkenyl group-containing organopolysiloxane (9) shown in Table 1 below, and 0.03 parts by mass of a 1% by mass solution of chloroplatinic acid in divinyltetramethyldisiloxane as a hydrosilylation reaction catalyst, and the mixture was allowed to react at 70 to 80°C for 2 hours.

[0059] Next, the entire amount of the reaction product obtained was thoroughly kneaded with 185.8 parts by mass of isododecane as a liquid oil agent at 25°C using a three-roll mill to obtain a smooth paste-like silicone composition with a consistency of 318 and a reaction product / liquid oil agent mass ratio of 36 / 64. There was no unpleasant odor, and the properties remained unchanged the next day. At this time, the contents of octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane in the paste-like silicone composition were each less than 100 ppm.

[0060] Example 4 A reaction vessel was charged with 7.2 parts by mass of the organohydrogenpolysiloxane (5) shown in Table 1 below, 21.5 parts by mass of the alkenyl group-containing organopolysiloxane (9) shown in Table 1 below, 114.6 parts by mass of diphenylsiloxyphenyl trimethicone (display name: KF-56A manufactured by Shin-Etsu Chemical Co., Ltd.) which is a liquid oil at 25°C, and 0.02 parts by mass of a 1% by mass solution of chloroplatinic acid in divinyltetramethyldisiloxane as a hydrosilylation reaction catalyst, and the mixture was allowed to react at 70 to 80°C for 2 hours.

[0061] Next, the entire amount of the reaction product obtained was thoroughly kneaded with 143.7 parts by mass of the diphenylsiloxyphenyl trimethicone using a three-roll mill to obtain a fluid paste-like silicone composition with a viscosity of 78 Pa·s and a reaction product / liquid oil ratio of 10 / 90. There was no unpleasant odor, and the properties remained unchanged the next day. At this time, the contents of octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane in the paste-like silicone composition were each less than 100 ppm.

[0062] Reference Example 1 A reaction vessel was charged with 8.6 parts by mass of the organohydrogenpolysiloxane (4) shown in Table 1 below, 103.1 parts by mass of the alkenyl group-containing organopolysiloxane (10) shown in Table 1 below, and 0.03 parts by mass of a 1% by mass solution of chloroplatinic acid in divinyltetramethyldisiloxane as a hydrosilylation reaction catalyst, and the mixture was reacted at 70 to 80°C for 2 hours.

[0063] 26.4 parts by mass of the obtained reaction product was thoroughly kneaded with 46.9 parts by mass of isododecane as a liquid oil agent at 25°C using a three-roll mill to obtain a paste-like silicone composition with a consistency of 318 and a reaction product / liquid oil agent weight ratio of 36 / 64. Although there was a slight odor, the next day the composition was in a smooth paste state and no plastic return was observed. At this time, the content of octamethylcyclotetrasiloxane in the paste-like silicone composition was 1480 ppm, decamethylcyclopentasiloxane was 1960 ppm, and dodecamethylcyclohexasiloxane was 710 ppm.

[0064] Comparative Example 1 A reaction vessel was charged with 45.2 parts by mass of the organohydrogenpolysiloxane (2) shown in Table 1 below, 11.0 parts by mass of the alkenyl-containing organopolysiloxane (8) shown in Table 1 below, and dimethylsiloxane (kinematic viscosity 2 mm) as a liquid oil agent at 25°C. 2 C. / s) and 0.02 parts by mass of a 1% by mass solution of chloroplatinic acid in divinyltetramethyldisiloxane as a hydrosilylation reaction catalyst were added, and the reaction was carried out at 70 to 80.degree. C. for 2 hours.

[0065] 60.0 parts by mass of the resulting reaction product was mixed with the above dimethylsiloxane (kinetic viscosity 2 mm) using a three-roll mill. 2 The mixture was thoroughly kneaded with 89.9 parts by mass of ethyl alcohol / s to obtain a paste-like silicone composition with a consistency of 307 and a reactant / liquid oil ratio of 20 / 80. There was an unusual odor, and the next day, the composition hardened and reverted to plastic. At this time, the paste-like silicone composition contained 170 ppm of octamethylcyclotetrasiloxane, 2800 ppm of decamethylcyclopentasiloxane, and 1900 ppm of dodecamethylcyclohexasiloxane.

[0066] Example 1 4. Reference Example 1 The organopolysiloxane used in Comparative Example 1 is shown in Table 1 below, and the organopolysiloxane used in Examples 1 to 4. Reference Example 1 The results of Comparative Example 1 are summarized in Table 2 below.

[0067] [Table 1] Organopolysiloxanes (1) to (10) were used as samples for determining the cyclic siloxane content. D4: Octamethylcyclotetrasiloxane D5: Decamethylcyclopentasiloxane D6: Dodecamethylcyclohexasiloxane

[0068] [Table 2] The samples used to determine the cyclic siloxane content were those in Examples 1 to 4. Reference Example 1 The paste-like silicone composition of Comparative Example 1 was used. D4: Octamethylcyclotetrasiloxane D5: Decamethylcyclopentasiloxane D6: Dodecamethylcyclohexasiloxane

[0069] Example 1 to Example 2 in Table 2 4. Reference Example 1As shown in Fig. 1, the paste-like silicone composition of the present invention was stable, with little change over time such as plastic reversion and little unpleasant odor. In particular, Examples 1 to 4 had no unpleasant odor.

[0070] On the other hand, in Comparative Example 1, which is a paste-like silicone composition in which the content of any one of octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane exceeded 2,000 ppm, changes occurred over time, such as reversion to plasticity, and an unpleasant odor was produced, and the paste-like silicone composition was not stable.

[0071] The present invention is not limited to the above-described embodiment. The above-described embodiment is merely an example, and anything that has substantially the same configuration as the technical idea described in the claims of the present invention and exhibits similar effects is included in the technical scope of the present invention.

Claims

1. A paste-like silicone composition comprising the following components (A) and (B), wherein the contents of octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane in the paste-like silicone composition are each less than 2,000 ppm: (A): The following components (A-1) and (A-2); (A-1) an organohydrogenpolysiloxane having two or more hydrogen atoms bonded to silicon atoms in each molecule, and containing octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane in an amount of not more than 2,000 ppm each; (A-2) an alkenyl group-containing organopolysiloxane having two or more alkenyl groups having 2 to 10 carbon atoms bonded to silicon atoms per molecule, and having an octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane content of not more than 2,000 ppm each; a crosslinked organopolysiloxane comprising a hydrosilylation reaction product of (B): Oil that is liquid at 25°C

2. 2. The paste-like silicone composition according to claim 1, wherein the component (A-1) is an organohydrogenpolysiloxane represented by the following general formula (1): 【Chemistry 1】 (In the general formula (1), R １ are independently a group selected from an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, and an aralkyl group having 7 to 30 carbon atoms; R ２ are independently the R １ or a hydrogen atom, provided that two or more R ２ is a hydrogen atom, and is an integer satisfying the conditions of 3≦a≦100,000 and 1≦b≦50.

3. 3. The paste-like silicone composition according to claim 1, wherein the component (A-2) is an alkenyl group-containing organopolysiloxane represented by the following general formula (2): 【Chemistry 2】 (In the above general formula (2), R １ are independently a group selected from an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, and an aralkyl group having 7 to 30 carbon atoms; R ３ are independently the R １ or an alkenyl group having 2 to 10 carbon atoms, provided that there are two or more R ３ is an alkenyl group, and c is an integer of 3≦c≦100,000 and 0≦d≦50.

4. 4. The paste-like silicone composition according to claim 3, wherein in said general formula (2), d = 0.

5. 5. A method for producing a paste-like silicone composition according to any one of claims 1 to 4, comprising a step of obtaining component (A) by subjecting component (A-1) and component (A-2) to a hydrosilylation reaction in the presence of a hydrosilylation reaction catalyst, wherein the components (A-1) and (A-2) each have an octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane content of 2,000 ppm or less.

6. 6. The method for producing a paste-like silicone composition according to claim 5, wherein the hydrosilylation reaction is carried out in the presence of 0.01 to 100 mass% of the amount of component (B) blended in the paste-like silicone composition.

7. A cosmetic preparation comprising the paste-like silicone composition according to any one of claims 1 to 4.

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