JP5754849B2 - Powder treatment agent, treated powder and powder dispersion in oil - Google Patents

Description

  The present invention relates to a powder treating agent, a treated powder treated with the powder treating agent, and a powder dispersion in oil obtained by dispersing the treated powder in an oil.

  Untreated powder tends to agglomerate due to the charge and polarity of the powder surface, a small amount of impurities, etc., which impairs the dispersibility and stability of the powder. Therefore, for example, it has been proposed to treat the surface of the powder with various treatment agents for the purpose of improving the dispersibility and stability of the powder and improving the touch when used in cosmetics. The treatment agent and the treatment method used for the surface treatment of the powder are selected according to the purpose in consideration of the surface properties of the powder to be treated, the characteristics with respect to the dispersion medium, and the like.

  As such a treatment, for example, a lipophilic treatment with an oil agent or a metal soap, a hydrophilic treatment with a surfactant or a water-soluble polymer, a water / oil repellent treatment with a silicone oil or the like has been known. Among these, silicone compounds that are particularly excellent in feel, water repellency, safety and the like are increasingly used as oil agents. Thus, surface treatment with methyl hydrogen siloxane (Patent Document 1) and surface modification method with linear one-terminal alkoxy-modified silicone (Patent Document 2) have been proposed as compatibility improvement of powders. Further, as an improvement in dispersibility in silicone oil, Patent Document 3 discloses a method in which a polyether-modified silicone having a HLB value (Hydrophile-Lipophile Balance) of 2 to 7 is used as a dispersion aid. Furthermore, Patent Document 4 discloses a modified powder using polyglycerin-modified silicone.

  However, although these surface-treated powders are all effective in improving the aggregation and sedimentation of the powder, the effects are not yet sufficient. In addition, depending on the treatment agent and treatment method, the powder and the treatment agent are separated at the time of use, and the powder is agglomerated over time, resulting in poor redispersibility, and the product quality and feeling of use are impaired. there were. Further, the modified powders shown in Patent Document 3 and Patent Document 4 are considered that hydrophilic groups such as polyether and polyglycerin are oriented on the surface of the powder, but the dispersion stability over time is insufficient. there were.

Japanese Patent No. 2719303 JP-A-7-196946 JP-A-10-167946 JP 10-316536 A

  The present invention has been made in view of the above circumstances, and has a powder processing agent that gives a powder having low cohesiveness and excellent dispersibility and stability over time, a processed powder treated with the powder processing agent, It is an object to provide a powder dispersion in oil obtained by dispersing treated powder in an oil agent.

（上記一般式（１）中、Ｘ及びＹはそれぞれ独立に、炭素数１〜１０の２価の炭化水素基であり、ｍは０〜４の整数であり、Ｚは下記一般式（２）で表される有機基を示す。）

（上記一般式（２）中、Ｒ^ａは炭素数２〜１２の２価の炭化水素基であり、ｍ’は１〜５の整数である。） In order to solve the above problems, according to the present invention, a glycerol group-containing substituent represented by the following general formula (1) is bonded to at least one silicon atom of an organopolysiloxane segment constituting the main chain. And a glycerol group-containing organopolysiloxane.

(In said general formula (1), X and Y are respectively independently C1-C10 bivalent hydrocarbon groups, m is an integer of 0-4, Z is following General formula (2). An organic group represented by

(In the general formula (2), R ^a is ^a divalent hydrocarbon group having 2 to 12 carbon atoms, and m ′ is an integer of 1 to 5.)

  Such a powder treatment agent is preferable in order to reduce the cohesiveness with respect to various powders and to give a powder excellent in dispersibility and stability over time.

（上記式（３）中、Ｒは互いに独立に、水素原子、ヒドロキシ基、炭素数１〜３のアルコキシ基、炭素数１〜３０のアルキル基、炭素数１〜３０のフロロアルキル基、炭素数６〜３０のアリール基、及び炭素数７〜３０のアラルキル基から選択される基であり、Ｒ^１０は前記一般式（１）で表される置換基であり、Ｒ^１１はＲ^１０又はＲから選択される有機基であり、Ａは下記一般式（４）

（上記一般式（４）において、Ｒ及びＲ^１０は上記の通りであり、Ｑは酸素原子、又は炭素数１〜３の２価の炭化水素基である。）
で表されるオルガノポリシロキサンセグメントであり、上記一般式（３）及び上記一般式（４）において、ａ、ｂ及びｃは互いに独立に０〜３の整数であり、ｅは０〜１００の整数であり、ｆは０〜２０，０００の整数であり、ｇは０又は１の整数であり、ｈは０又は１の整数であり、ｉは０〜１００の整数であり、ｊは０〜１０，０００の整数であり、但し、Ｒ^１１がＲ^１０である場合、１≦ａ＋ｂ＋ｃ＋ｅ＋ｇ＋ｉであり、Ｒ^１１がＲである場合、１≦ａ＋ｂ＋ｃ＋ｅ＋ｉである。） The glycerol group-containing organopolysiloxane is preferably a compound represented by the following average composition formula (3).

(In said formula (3), R is mutually independently a hydrogen atom, a hydroxy group, a C1-C3 alkoxy group, a C1-C30 alkyl group, a C1-C30 fluoroalkyl group, carbon number. R ¹⁰ is a group selected from an aryl group having 6 to 30 carbon atoms and an aralkyl group having 7 to 30 carbon atoms, R ¹⁰ is a substituent represented by the general formula (1), and R ¹¹ is R ¹⁰ or R A selected organic group, A is the following general formula (4)

(In the general formula (4), R and R ¹⁰ are as described above, and Q is an oxygen atom or a divalent hydrocarbon group having 1 to 3 carbon atoms.)
In the general formula (3) and the general formula (4), a, b and c are each independently an integer of 0 to 3, and e is an integer of 0 to 100 F is an integer of 0 to 20,000, g is an integer of 0 or 1, h is an integer of 0 or 1, i is an integer of 0 to 100, and j is 0 to 10 1 ≦ a + b + c + e + g + i when R ¹¹ is R ¹⁰ and 1 ≦ a + b + c + e + i when R ¹¹ is R. )

  Thus, examples of the glycerol group-containing organopolysiloxane include compounds represented by the above average composition formula (3).

  In addition, the present invention provides a treated powder characterized by being treated with 0.1 to 30 parts by mass of the powder treating agent with respect to 100 parts by mass of the powder.

  As described above, the powder treated with the powder treating agent of the present invention has less agglomeration and becomes a powder excellent in dispersibility and stability over time. Further, the powder thus treated can be blended as a filler in personal care, particularly in cosmetic compositions, various thermoplastic or thermosetting compositions, rubber compositions, and the like.

  The powder is preferably at least one of zinc oxide, titanium oxide, and extender.

  As the powder to be treated with the powder treating agent of the present invention, extender pigments such as mica and sericite, zinc oxide, titanium oxide and the like are preferable for cosmetic applications.

  Moreover, in this invention, the powder dispersion | distribution in oil formed by disperse | distributing the said process powder in an oil agent is provided.

  Thus, in the present invention, a powder-in-oil dispersion in which powder treated with the powder treating agent is dispersed in an oil agent, or the powder treating agent is dissolved or dispersed in an oil agent, and powder is added thereto. Provided is a powder dispersion in oil which is mixed and dispersed by adding a body.

  By treating the powder with the powder treating agent of the present invention, it is possible to obtain a powder with less aggregation and excellent dispersibility and stability over time.

2 is a 1H NMR measurement result of the reaction product obtained in Synthesis Example 1. FIG.

The present invention will be described in detail below.
As described above, there is a need for a powder processing agent that provides a powder with low cohesiveness and excellent dispersibility and stability over time.

  As a result of intensive investigations to achieve the above object, the present inventors have used a specific glycerol group-containing organopolysiloxane as a powder treating agent, so that the powder has less cohesiveness and excellent dispersibility. The inventors have found that the present invention can be provided, and have reached the present invention.

（上記一般式（１）中、Ｘ及びＹはそれぞれ独立に、炭素数１〜１０の２価の炭化水素基であり、ｍは０〜４の整数であり、Ｚは下記一般式（２）で表される有機基を示す。）

（上記一般式（２）中、Ｒ^ａは炭素数２〜１２の２価の炭化水素基であり、ｍ’は１〜５の整数である。） Hereinafter, the present invention will be described in more detail.
Powder processing agent The present invention relates to a glycerol group-containing organopolysiloxane in which a glycerol group-containing substituent represented by the following general formula (1) is bonded to at least one silicon atom of an organopolysiloxane segment constituting a main chain. The present invention relates to a powder processing agent characterized by containing polysiloxane.

(In said general formula (1), X and Y are respectively independently C1-C10 bivalent hydrocarbon groups, m is an integer of 0-4, Z is following General formula (2). An organic group represented by

(In the general formula (2), R ^a is ^a divalent hydrocarbon group having 2 to 12 carbon atoms, and m ′ is an integer of 1 to 5.)

  In the general formula (1), X and Y are each independently a divalent hydrocarbon group having 1 to 10 carbon atoms, and a linear or branched divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms. Or a divalent aromatic hydrocarbon group having 6 to 10 carbon atoms, more preferably an alkylene group or alkenylene group having 2 to 6 carbon atoms, especially 2 to 6 carbon atoms, or a phenylene group, among which an ethylene group, an ethylenylene group, A trimethylene group, a propylene group, a butylene group, an isobutylene group, a hexamethylene group, or a phenylene group is preferred. m represents an integer of 0 to 4, and 0 to 2 is more preferable.

In the general formula (2), R ^a is ^a divalent hydrocarbon group having 2 to 12 carbon atoms, a linear or branched divalent aliphatic hydrocarbon group having 2 to 12 carbon atoms, or 6 carbon atoms. Is preferably an alkylene group having 1 to 10 carbon atoms, particularly 2 to 6 carbon atoms, more preferably an alkylene group or alkenylene group, or a phenylene group. Among them, an ethylene group, an ethylenylene group, a trimethylene group, a propylene group, A butylene group, an isobutylene group, a hexamethylene group, or a phenylene group is more preferable. m ′ represents an integer of 1 to 5, more preferably 1 to 3, and most preferably 1.

The glycerol group-containing organopolysiloxane is preferably a compound represented by the following average composition formula (3).

  In the formula (3), R is independently of each other a hydrogen atom, a hydroxy group, an alkoxy group having 1 to 3 carbon atoms, an alkyl group having 1 to 30 carbon atoms, a fluoroalkyl group having 1 to 30 carbon atoms, or 6 carbon atoms. A group selected from an aryl group having ˜30 and an aralkyl group having 7 to 30 carbon atoms, specifically, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl Group, nonyl group, decyl group, stearyl group, cyclopentyl group, cyclohexyl group and other alkyl groups, trifluoropropyl group, heptadecafluorodecyl group and other aryl groups, phenyl group, tolyl group and other aryl groups, benzyl group, Examples include aralkyl groups such as phenethyl group. Especially, a C1-C15 alkyl group and a phenyl group are preferable, More preferably, it is a methyl group.

（一般式（４）において、Ｒ及びＲ^１０は上記の通りであり、Ｑは酸素原子、又は炭素数１〜３の２価の炭化水素基である。） R ¹⁰ is a substituent represented by the general formula (1), R ¹¹ is an organic group selected from R ¹⁰ or R, and A is an organopolysiloxane represented by the following general formula (4). It is a segment.

(In the general formula (4), R and ^{R 10} are as defined above, Q is an oxygen atom or a divalent hydrocarbon group having 1 to 3 carbon atoms.)

In the formula (3) and the general formula (4), a, b and c are each independently an integer of 0 to 3, e is an integer of 0 to 100, preferably 1 to 50, and f is 0 to 20 , Preferably an integer of 20 to 5,000, g is an integer of 0 or 1, h is an integer of 0 or 1, and i is an integer of 0 to 100, preferably 1 to 50. , J is an integer from 0 to 10,000, preferably from 20 to 2,000, provided that when R ¹¹ is R ¹⁰ , 1 ≦ a + b + c + e + g + i, and when R ¹¹ is R, 1 ≦ a + b + c + e + i is there. )

Method for producing glycerol group-containing organopolysiloxane The glycerol group-containing organopolysiloxane formed by bonding the glycerol group-containing substituent represented by the general formula (1) contained in the powder treatment agent of the present invention is an amino group. An amidocarboxylic acid-modified organopolysiloxane obtained by a method of reacting an organopolysiloxane having a reaction with a cyclic acid anhydride is used. The amidocarboxylic acid-modified organopolysiloxane can be obtained by the methods disclosed in JP-A-58-213025 and JP-A-10-158150. As the cyclic acid anhydride, one or more selected from phthalic anhydride, succinic anhydride, maleic anhydride, glutaric anhydride, and adipic anhydride can be used.

  The solvent in the reaction between the amidocarboxylic acid-modified organopolysiloxane and glycidol is not particularly limited. Solvent-free may be used, but to improve compatibility, hydrocarbon solvents such as hexane and toluene, ketone solvents such as acetone and methyl ethyl ketone, N, N-dimethylacetamide, N, N-dimethylformamide and N-methyl Examples include amide solvents such as 2-pyrrolidone, ether solvents such as tetrahydrofuran and 1,4-dioxane, alcohol solvents such as 2-propanol, ester solvents such as butyl acetate, and nitrile solvents such as acetonitrile and benzonitrile. It is done. Of these, tetrahydrofuran and acetonitrile are particularly preferable. If necessary, a Lewis acid catalyst or a base catalyst may be used, and triethylamine or an alkali metal hydroxide is particularly preferable. The addition amount of the catalyst is preferably 0.01 to 1 equivalent, more preferably 0.02 to 0.1 equivalent, relative to the carboxylic acid in the amide carboxylic acid-modified organopolysiloxane.

  The reaction temperature is 25 ° C. or higher and lower than the boiling point of glycidol, preferably 50 to 140 ° C., more preferably 60 to 110 ° C. The reaction time is preferably 2 to 15 hours, more preferably 3 to 8 hours.

  The reaction equivalent of the amidocarboxylic acid-modified organopolysiloxane and glycidol is preferably 0.1 to 3.0 equivalents, more preferably 1 to 2 equivalents, based on the carboxylic acid in the organopolysiloxane.

Treated powder The powder treating agent of the present invention is used for treating various powders and imparts non-aggregation and dispersibility to the powder.

  The powders treated with the powder treating agent of the present invention are inorganic powder, organic powder, surfactant metal salt powder (metal soap), colored pigment, pearl pigment, metal powder pigment, tar dye, natural dye Any of these may be used.

  Inorganic powders include titanium oxide, zirconium oxide, zinc oxide, cerium oxide, magnesium oxide, barium sulfate, calcium sulfate, magnesium sulfate, calcium carbonate, magnesium carbonate, talc, mica, kaolin, sericite, muscovite, synthetic mica Phlogopite, red mica, biotite, lithia mica, silicic acid, anhydrous silicic acid, aluminum silicate, magnesium silicate, magnesium magnesium silicate, calcium silicate, barium silicate, strontium silicate, metal tungstate, Examples thereof include hydroxyapatite, vermiculite, hydrite, bentonite, montmorillonite, hectorite, zeolite, ceramic powder, dicalcium phosphate, alumina, aluminum hydroxide, boron nitride, boron nitride and silica. For cosmetic applications, extender pigments such as mica and sericite, zinc oxide, and titanium oxide are preferred.

  Organic powders include polyamide powder, polyester powder, polyethylene powder, polypropylene powder, polystyrene powder, polyurethane powder, benzoguanamine powder, polymethylbenzoguanamine powder, tetrafluoroethylene powder, polymethyl methacrylate powder, cellulose powder, silk powder, 12 nylon Nylon powder such as Nylon and 6 nylon, styrene / acrylic acid copolymer, divinylbenzene, styrene copolymer, vinyl resin, urea resin, phenol resin, fluororesin, silicon resin, acrylic resin, melamine resin, epoxy resin, Examples thereof include polycarbonate resin, microcrystalline fiber powder, starch, lauroyl lysine and the like.

  Surfactant metal salt powder (metal soap) includes zinc stearate, aluminum stearate, calcium stearate, magnesium stearate, zinc myristate, magnesium myristate, zinc cetyl phosphate, calcium cetyl phosphate, zinc sodium cetyl phosphate, etc. Can be mentioned.

  As colored pigments, inorganic red pigments such as iron oxide, iron hydroxide and iron titanate, inorganic brown pigments such as γ-iron oxide, inorganic yellow pigments such as yellow iron oxide and loess, black iron oxide, carbon black Inorganic black pigments such as manganese violet, inorganic violet pigments such as cobalt violet, inorganic green pigments such as chromium hydroxide, chromium oxide, cobalt oxide and cobalt titanate, inorganic blue pigments such as bitumen and ultramarine blue, tar Examples include raked system dyes, raked natural dyes, and composite powders obtained by combining these powders.

  Pearl pigments include titanium oxide-coated mica, bismuth oxychloride, titanium oxide-coated bismuth oxychloride, titanium oxide-coated talc, fish scale foil, titanium oxide-coated colored mica, and metal powder pigments such as aluminum powder, copper powder, and stainless steel powder. Etc.

  As tar pigments, Red No. 3, Red No. 104, Red No. 106, Red No. 201, Red No. 202, Red No. 204, Red No. 205, Red No. 220, Red No. 226, Red No. 227, Red No. 228, Red 230, Red 401, Red 505, Yellow 4, Yellow 5, Yellow 202, Yellow 203, Yellow 204, Yellow 401, Blue 1, Blue 2, Blue 201, Blue 404 , Green No. 3, Green No. 201, Green No. 204, Green No. 205, Orange No. 201, Orange No. 203, Orange No. 204, Orange No. 206, Orange No. 207, etc. Natural pigments include carminic acid, laccaic acid, and calsamine , Bradylin, crocin and the like.

  These powders are used regardless of their shape (spherical, needle, plate, etc.), particle size (smoke, fine particles, pigment grade, etc.) and particle structure (porous, nonporous, etc.). can do. These powders may be combined with each other, or may be subjected to surface treatment with an oil agent, silicone other than the powder treatment agent of the present invention, or a fluorine compound.

The powder treatment agent containing the glycerol group-containing organopolysiloxane of the present invention can be treated on the powder surface by a known method. The treatment method can be appropriately selected from known methods, and examples thereof include the following methods.
1. A method in which a target powder is surface-treated by dispersing it in a medium selected from water or an organic solvent mixed with a powder treating agent.
2. A method of performing surface treatment using a pulverizer such as a ball mill or a jet mill after mixing powder and a powder treating agent.

In-oil powder dispersion The present invention also provides a powder-in-oil dispersion obtained by dispersing a treated powder treated with the powder treating agent of the present invention in an oil.
The powder dispersion in oil may be obtained by dispersing the powder treated with the powder treatment agent of the present invention in the oil agent, or by dissolving or dispersing the powder treatment agent of the present invention in the oil agent. Powder may be added and mixed and dispersed, and the form is a liquid dispersion. This powder dispersion in oil can be appropriately prepared by a known method such as the following method.
1. A method in which a treated powder treated with the powder treating agent of the present invention is added and dispersed in an oil such as ester oil or silicone oil.
2. A method in which the powder treating agent of the present invention is dissolved or dispersed in the above oil, and the powder is added thereto and mixed with a dispersing device such as a ball mill, a bead mill, or a sand mill.
The obtained powder dispersion in oil can be used and blended as it is.

  As the oil agent, dimethylpolysiloxane, methylphenylpolysiloxane, octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), dodecamethylcyclohexasiloxane (D6), decamethyltetrasiloxane (M3T) are used as silicone oils. , Higher alkoxy-modified silicones such as stearoxy silicone, higher fatty acid-modified silicones, fluorine-modified silicones, amino-modified silicones, alkyl-modified silicones, higher fatty acid ester-modified silicones, fluorine oils such as perfluoropolyether, perfluorodecalin, Examples of glyceride oils such as perfluorooctane include acetoglyceryl, glyceryl diisooctanoate, glyceryl triisostearate, glyceryl triisopalmitate, Examples of ester oils such as glyceryl r-2-ethylhexanoate, glyceryl monostearate, glyceryl di-2-heptylundecanoate, and glyceryl trimyristate include diisobutyl adipate, 2-hexyldecyl adipate, di-2 adipate -Heptylundecyl, N-alkylglycol monoisostearate, isocetyl isostearate, trimethylolpropane triisostearate, ethylene glycol di-2-ethylhexanoate, neopentyl glycol di-2-ethylhexanoate, 2-ethylhexanoic acid Cetyl, tri-2-ethylhexanoic acid trimethylolpropane, tetra-2-ethylhexanoic acid pentaerythritol, cetyl octoate, octyldodecyl gum ester, oleyl oleate, oleic acid Ludodecyl, decyl oleate, neopentyl glycol dicaprate, triethyl citrate, 2-ethylhexyl succinate, amyl acetate, ethyl acetate, butyl acetate, isocetyl stearate, butyl stearate, diisopropyl sebacate, di-2-ethylhexyl sebacate Cetyl lactate, myristyl lactate, isopropyl palmitate, 2-ethylhexyl palmitate, 2-hexyldecyl palmitate, 2-heptyl undecyl palmitate, cholesteryl 12-hydroxystearate, dipentaerythritol fatty acid ester, isopropyl myristate, myristine 2-octyldodecyl acid, 2-hexyldecyl myristate, myristyl myristate, hexyldecyl dimethyloctanoate, ethyl laurate, lauric acid Hexyl, N-lauroyl-L-glutamic acid-2-octyldodecyl ester, diisostearyl malate, dextrin palmitate, dextrin stearate, dextrin 2-ethylhexanoate palmitate, sucrose palmitate, sucrose As hydrocarbon oils such as stearic acid ester, monobenzolidene sorbitol, dibenzylidene sorbitol, etc., ozokerite, squalane, squalene, ceresin, paraffin, liquid paraffin, pristane, polyisobutylene, etc., alcohols include ethanol, propanol, ethylene Glycol, ethylene glycol monoalkyl ether, cyphoethylene glycol monoethyl ether, polyethylene glycol, propylene glycol, di- Natural animal and plant oils and fats such as propylene glycol, 1,3-butylene glycol, glycerin, diglycerin, polyglycerin, and semi-synthetic oils include avocado oil, linseed oil, almond oil, ibotarou, eno oil, olive oil, cocoa butter , Kapok wax, Kaya oil, Carnauba wax, Liver oil, Candelilla wax, Beef tallow, Beef leg fat, Beef bone fat, Hardened beef tallow, Kyonin oil, Whale wax, Hardened oil, Wheat germ oil, Sesame oil, Rice germ oil, Rice bran oil, Sugar cane Wax, sasanqua oil, safflower oil, shea butter, cinnamon oil, cinnamon oil, jojoballow, shellac wax, turtle oil, soybean oil, tea seed oil, camellia oil, evening primrose oil, corn oil, lard, rapeseed oil, Japanese kiri Oil, nukarou, germ oil, horse fat, persic oil, palm oil, palm kernel oil, castor oil, hydrogenated castor oil, Fruit oil methyl ester, sunflower oil, grape oil, bayberry wax, jojoba oil, macadamia nut oil, beeswax, mink oil, cottonseed oil, cotton wax, owl, owl kernel oil, montan wax, coconut oil, hardened coconut oil, tricoconut oil fatty acid glyceride, Ambition, groundnut oil, lanolin, liquid lanolin, reduced lanolin, lanolin alcohol, hard lanolin, lanolin acetate, lanolin fatty acid isopropyl, POE lanolin alcohol ether, POE lanolin alcohol acetate, lanolin fatty acid polyethylene glycol, POE hydrogenated lanolin alcohol ether, egg yolk Oil etc. are mentioned. However, POE means polyoxyethylene.

When the powder is treated with the powder treating agent containing the glycerol group-containing organopolysiloxane of the present invention, the powder treating agent is 0.1 to 30 parts by weight, preferably 0. Use 5 to 10 parts by mass.
The powder thus treated can be blended as a filler in personal care, particularly in cosmetic compositions, various thermoplastic or thermosetting compositions, rubber compositions, and the like.

  EXAMPLES Hereinafter, although a synthesis example, an Example, and a comparative example demonstrate this invention further, this invention is not limited at all by these.

で表される粘度３８ｍｍ^２／ｓ（２５℃）でアミン当量が２５００ｇ／ｍｏｌのアミノ変性オルガノポリシロキサン３００質量部、テトラヒドロフラン５０質量部、無水コハク酸１２質量部を５０℃にて３時間撹拌した。得られた反応混合物を減圧下、１１０℃でストリップすることにより、溶剤を取り除き、無色透明で粘度５５０ｍｍ^２／ｓ（２５℃）の液体を得た。この液体のカルボキシ当量２６３０ｇ／ｍｏｌであり、アミドカルボン酸へ変換されていることを確認した。
ここで得られた液体１５０質量部、グリシドール６質量部を別の反応器に入れ、１１０℃にて８時間攪拌した。得られた反応混合物を減圧下、１２０℃でストリップすることにより、未反応物を取り除き、淡黄色透明で粘度４４００ｍｍ^２／ｓ（２５℃）の液体を得た。１Ｈ ＮＭＲ（ＣＤＣｌ３ ４００ＭＨｚ Ｂｌｕｋｅｒ社）の測定結果（図１に示す）から得られた生成物のカルボン酸部分がグリセロールエステル化されていることを確認した。得られた反応生成物の構造式を以下に示す。

（Ｒ^ａ＝−ＣＨ_２−ＣＨ_２−，ｍ’＝１） (Synthesis Example 1)
The following average composition formula in the reactor

300 parts by mass of amino-modified organopolysiloxane having a viscosity of 38 mm ² / s (25 ° C.) and an amine equivalent of 2500 g / mol, 50 parts by mass of tetrahydrofuran, and 12 parts by mass of succinic anhydride were stirred at 50 ° C. for 3 hours. . The obtained reaction mixture was stripped at 110 ° C. under reduced pressure to remove the solvent to obtain a colorless and transparent liquid having a viscosity of 550 mm ² / s (25 ° C.). It was confirmed that the liquid had a carboxy equivalent of 2630 g / mol and was converted to an amide carboxylic acid.
150 parts by mass of the liquid obtained here and 6 parts by mass of glycidol were put into another reactor and stirred at 110 ° C. for 8 hours. The reaction mixture obtained was stripped at 120 ° C. under reduced pressure to remove unreacted substances, and a pale yellow transparent liquid having a viscosity of 4400 mm ² / s (25 ° C.) was obtained. From the measurement result (shown in FIG. 1) of 1H NMR (CDCl 3 400 MHz Bluker), it was confirmed that the carboxylic acid moiety of the product was glycerol esterified. The structural formula of the obtained reaction product is shown below.

(R ^a = —CH ₂ —CH ₂ —, m ′ = 1)

で表される粘度１１０ｍｍ^２／ｓ（２５℃）でアミン当量が５０９０ｇ／ｍｏｌのアミノ変性オルガノポリシロキサン１５０質量部、テトラヒドロフラン２０質量部、無水コハク酸３質量部を５０℃にて３時間撹拌した。得られた反応混合物を減圧下、１１０℃でストリップすることにより、溶剤を取り除き、無色透明で粘度１２６０ｍｍ^２／ｓ（２５℃）の液体を得た。この液体のカルボキシ当量５２４０ｇ／ｍｏｌであり、アミドカルボン酸へ変換されていることを確認した。
ここで得られた液体１２０質量部、グリシドール９質量部、トリエチルアミン０．２質量部、テトラヒドロフラン３０質量部を別の反応器に入れ、８０℃にて６時間攪拌した。得られた反応混合物を減圧下、１２０℃でストリップすることにより、溶剤、未反応物を取り除き、淡黄色透明で粘度１３４０００ｍＰａ・ｓ（２５℃）の液体を得た。１Ｈ ＮＭＲ（ＣＤＣｌ３ ４００ＭＨｚ Ｂｌｕｋｅｒ社）の測定結果から３．４〜４．３ｐｐｍ付近に特徴的なピークが認められ、得られた生成物のカルボン酸部分がグリセロールエステル化されていることを確認した。得られた反応生成物の構造式を以下に示す。

（Ｒ^ａ＝−ＣＨ_２−ＣＨ_２−，ｍ’＝３） (Synthesis Example 2)
The following average composition formula in the reactor

150 parts by mass of amino-modified organopolysiloxane having a viscosity of 110 mm ² / s (25 ° C.) and an amine equivalent of 5090 g / mol, 20 parts by mass of tetrahydrofuran, and 3 parts by mass of succinic anhydride were stirred at 50 ° C. for 3 hours. . The obtained reaction mixture was stripped at 110 ° C. under reduced pressure to remove the solvent to obtain a colorless and transparent liquid having a viscosity of 1260 mm ² / s (25 ° C.). It was confirmed that the liquid had a carboxy equivalent of 5240 g / mol and was converted to an amide carboxylic acid.
120 parts by mass of the liquid obtained here, 9 parts by mass of glycidol, 0.2 part by mass of triethylamine, and 30 parts by mass of tetrahydrofuran were put into another reactor and stirred at 80 ° C. for 6 hours. The obtained reaction mixture was stripped at 120 ° C. under reduced pressure to remove the solvent and unreacted substances, thereby obtaining a light yellow transparent liquid having a viscosity of 134,000 mPa · s (25 ° C.). From the measurement result of 1H NMR (CDCl3 400 MHz Bluker), a characteristic peak was observed in the vicinity of 3.4 to 4.3 ppm, and it was confirmed that the carboxylic acid moiety of the obtained product was glycerol esterified. The structural formula of the obtained reaction product is shown below.

(R ^a = —CH ₂ —CH ₂ —, m ′ = 3)

で表される粘度１２０ｍｍ^２／ｓ（２５℃）でアミン当量が７４５０ｇ／ｍｏｌのアミノ変性オルガノポリシロキサン１５０質量部、テトラヒドロフラン２０質量部、無水マレイン酸２質量部を５０℃にて３時間撹拌した。得られた反応混合物を減圧下、１１０℃でストリップすることにより、溶剤を取り除き、無色透明で粘度５５０ｍｍ^２／ｓ（２５℃）の液体を得た。この液体のカルボキシ当量７５５０ｇ／ｍｏｌであり、アミドカルボン酸へ変換されていることを確認した。ここで得られた液体１３０質量部、グリシドール２．５質量部、１，４−ジオキサン４０質量部を別の反応器に入れ、８０℃にて６時間攪拌した。得られた反応混合物を減圧下、１２０℃でストリップすることにより、溶剤、未反応物を取り除き、淡黄色透明で粘度２９００ｍｍ^２／ｓ（２５℃）の液体を得た。１Ｈ ＮＭＲ（ＣＤＣｌ３ ４００ＭＨｚ Ｂｌｕｋｅｒ社）の測定結果から３．４〜４．３ｐｐｍ付近に特徴的なピークが認められ、得られた生成物のカルボン酸部分がグリセロールエステル化されていることを確認した。得られた反応生成物の構造式を以下に示す。

（Ｒ^ａ＝−ＣＨ＝ＣＨ−，ｍ’＝１） (Synthesis Example 3)
The following average composition formula in the reactor

150 parts by mass of amino-modified organopolysiloxane having a viscosity of 120 mm ² / s (25 ° C.) and an amine equivalent of 7450 g / mol, 20 parts by mass of tetrahydrofuran, and 2 parts by mass of maleic anhydride were stirred at 50 ° C. for 3 hours. . The obtained reaction mixture was stripped at 110 ° C. under reduced pressure to remove the solvent to obtain a colorless and transparent liquid having a viscosity of 550 mm ² / s (25 ° C.). It was confirmed that the liquid had a carboxy equivalent of 7550 g / mol and was converted to an amide carboxylic acid. 130 parts by mass of the liquid obtained here, 2.5 parts by mass of glycidol, and 40 parts by mass of 1,4-dioxane were put into another reactor and stirred at 80 ° C. for 6 hours. The obtained reaction mixture was stripped at 120 ° C. under reduced pressure to remove the solvent and unreacted substances, thereby obtaining a pale yellow transparent liquid having a viscosity of 2900 mm ² / s (25 ° C.). From the measurement result of 1H NMR (CDCl3 400 MHz Bluker), a characteristic peak was observed in the vicinity of 3.4 to 4.3 ppm, and it was confirmed that the carboxylic acid portion of the obtained product was glycerol esterified. The structural formula of the obtained reaction product is shown below.

(R ^a = -CH = CH-, m '= 1)

で表される粘度３５ｍｍ^２／ｓ（２５℃）のメチルハイドロジェンオルガノポリシロキサン３００質量部、２−プロパノール１００質量部、下記平均組成式

で示されるアリルグリセロール４５質量部、塩化白金酸ジビニルテトラメチルジシロキサン錯体の１−ブタノール溶液（白金３質量％）０．０２質量部、酢酸カリウムの１０％エタノール溶液０．０４質量部を８０℃にて５時間撹拌した。得られた反応混合物を減圧下、１１０℃で３時間ストリップすることにより、溶剤を取り除き、無色微濁で粘度４５００ｍｍ^２／ｓ（２５℃）の液体を得た。 (Comparative Synthesis Example 1)
The following average composition formula in the reactor

300 parts by mass of methylhydrogenorganopolysiloxane having a viscosity of 35 mm ² / s (25 ° C.), 100 parts by mass of 2-propanol, and the following average composition formula

80 parts by weight of 45 parts by weight of allylglycerol represented by the formula, 0.02 parts by weight of 1-butanol solution (platinum 3% by weight) of chloroplatinic acid divinyltetramethyldisiloxane complex, and 0.04 parts by weight of 10% ethanol solution of potassium acetate. For 5 hours. The obtained reaction mixture was stripped under reduced pressure at 110 ° C. for 3 hours to remove the solvent, and a colorless and slightly turbid liquid having a viscosity of 4500 mm ² / s (25 ° C.) was obtained.

Example 1
After dissolving 8 g of the organopolysiloxane (powder treatment agent) obtained in Synthesis Example 1 in 52 g of decamethylcyclopentasiloxane, 40 g of titanium oxide (TTO-S-2: trade name manufactured by Ishihara Sangyo Co., Ltd.) In addition, it was dispersed using a bead mill to obtain a surface-treated titanium oxide dispersion (A).

(Example 2)
After dissolving 6 g of the organopolysiloxane (powder treating agent) obtained in Synthesis Example 1 in 44 g of decamethylcyclopentasiloxane, 50 g of zinc oxide (ZnO350: trade name of Osaka Sumitomo Cement Co., Ltd.) is added, and a bead mill is added. Was used to obtain a surface-treated zinc oxide dispersion (B).

(Example 3)
After dissolving 6 g of the organopolysiloxane (powder treating agent) obtained in Synthesis Example 2 in 54 g of decamethylcyclopentasiloxane, 40 g of titanium oxide (TTO-S-2: trade name of Ishihara Sangyo Co., Ltd.) was added. In addition, it was dispersed using a bead mill to obtain a surface-treated titanium oxide dispersion (C).

Example 4
After dissolving 8 g of the organopolysiloxane (powder treating agent) obtained in Synthesis Example 2 in 42 g of decamethylcyclopentasiloxane, 50 g of zinc oxide (ZnO350: trade name of Osaka Sumitomo Cement Co., Ltd.) was added, and the bead mill Was used to obtain a surface-treated zinc oxide dispersion (D).

(Example 5)
After dissolving 6 g of the organopolysiloxane (powder treating agent) obtained in Synthesis Example 3 in a mixed solution of 10 g of decamethylcyclopentasiloxane and 44 g of isododecane, titanium oxide (TTO-S-2: manufactured by Ishihara Sangyo Co., Ltd.) (Trade name) of 40 g was added and dispersed using a bead mill to obtain a surface-treated titanium oxide dispersion (E).

(Example 6)
After 6 g of the organopolysiloxane (powder treating agent) obtained in Synthesis Example 1 was dissolved in 2-propanol, 50 g of titanium oxide (TTO-S-1: trade name of Ishihara Sangyo Co., Ltd.) was added. Dispersion was performed, and the solvent was distilled off to obtain surface-treated titanium oxide (F).

(Example 7)
After dissolving 5 g of the organopolysiloxane (powder treating agent) obtained in Synthesis Example 2 in 2-propanol, 50 g of zinc oxide (ZnO350: trade name of Osaka Sumitomo Cement Co., Ltd.) is added and dispersed, and the solvent Was distilled off to obtain surface-treated zinc oxide (G).

(Comparative Example 1)
After dissolving 8 g of the organopolysiloxane obtained in Comparative Synthesis Example 1 in 52 g of decamethylcyclopentasiloxane, 40 g of titanium oxide (TTO-S-2: trade name manufactured by Ishihara Sangyo Co., Ltd.) is added and a bead mill is used. The surface-treated titanium oxide dispersion (H) was obtained.

(Comparative Example 2)
After dissolving 6 g of the organopolysiloxane obtained in Comparative Synthesis Example 1 in 44 g of decamethylcyclopentasiloxane, 50 g of zinc oxide (ZnO350: trade name of Osaka Sumitomo Cement Co., Ltd.) is added and dispersed using a bead mill. A surface-treated dispersion (I) of zinc oxide was obtained.

(Comparative Example 3)
6 g of polyether-modified silicone (KF6017: trade name manufactured by Shin-Etsu Chemical Co., Ltd.) is dissolved in 44 g of decamethylcyclopentasiloxane, and 50 g of zinc oxide (ZnO350: trade name of Osaka Sumitomo Cement Co., Ltd.) is added. Dispersion was performed using a bead mill to obtain a surface-treated zinc oxide dispersion (J).

(Comparative Example 4)
6 g of polyglycerin-modified silicone (KF6104: trade name manufactured by Shin-Etsu Chemical Co., Ltd.) is dissolved in 44 g of decamethylcyclopentasiloxane, and 50 g of zinc oxide (ZnO350: trade name of Osaka Sumitomo Cement Co., Ltd.) is added. Dispersion was performed using a bead mill to obtain a surface-treated dispersion (K) of zinc oxide.

(Comparative Example 5)
After dissolving 6 g of polyglycerin-modified silicone (KF6104: trade name manufactured by Shin-Etsu Chemical Co., Ltd.) in a mixed solution of 10 g of decamethylcyclopentasiloxane and 44 g of isododecane, titanium oxide (TTO-S-2: Ishihara Sangyo Co., Ltd.) ) (Trade name) 40 g was added and dispersed using a bead mill to obtain a surface-treated titanium oxide dispersion (L).

(Comparative Example 6)
After 6 g of polyether-modified silicone (KF6017: trade name manufactured by Shin-Etsu Chemical Co., Ltd.) is dissolved in 2-propanol, 50 g of titanium oxide (TTO-S-2: product name manufactured by Ishihara Sangyo Co., Ltd.) is added. And the solvent was distilled off to obtain surface-treated titanium oxide (M).

(Comparative Example 7)
Methyl hydrogen polysiloxane (KF99: trade name manufactured by Shin-Etsu Chemical Co., Ltd.) is dissolved in 2-propanol, and 50 g of zinc oxide (ZnO350: trade name manufactured by Sumitomo Osaka Cement Co., Ltd.) is added. It was dried at 0 ° C. to obtain surface-treated zinc oxide (N).

Dispersibility evaluation:
The treated powder of Examples 1 to 7 and Comparative Examples 1 to 7 and the powder dispersion in oil were mixed with decamethylcyclopentasiloxane so that the concentration of the powder was 5%. The sample was placed in a test tube and the sedimentation property after 2 days was visually observed according to the following evaluation criteria. The results are as shown in Table 1 below.
A: There is almost no sedimentation of the powder.
○: Slight sedimentation of powder can be confirmed.
(Triangle | delta): Powder has settled considerably.
X: Most of the powder is settling.

  As is apparent from Table 1, in Examples 1 to 7, even after 2 days, they were not agglomerated and uniform without settling, and the dispersibility was good. However, in Comparative Examples 1 to 7, all were non-uniform and settled.

  The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has any configuration that has substantially the same configuration as the technical idea described in the claims of the present invention and that exhibits the same effects. It is contained in the technical range.

Claims (5)

It contains glycerol group-containing organopolysiloxane in which a glycerol group-containing substituent represented by the following general formula (1) is bonded to at least one silicon atom of the organopolysiloxane segment constituting the main chain. A powder processing agent.

(In said general formula (1), X and Y are respectively independently C1-C10 bivalent hydrocarbon groups, m is an integer of 0-4, Z is following General formula (2). An organic group represented by

(In the general formula (2), R ^a is ^a divalent hydrocarbon group having 2 to 12 carbon atoms, and m ′ is an integer of 1 to 5.) The powder treatment agent according to claim 1, wherein the glycerol group-containing organopolysiloxane is a compound represented by the following average composition formula (3).

(In said formula (3), R is mutually independently a hydrogen atom, a hydroxy group, a C1-C3 alkoxy group, a C1-C30 alkyl group, a C1-C30 fluoroalkyl group, carbon number. R ¹⁰ is a group selected from an aryl group having 6 to 30 carbon atoms and an aralkyl group having 7 to 30 carbon atoms, R ¹⁰ is a substituent represented by the general formula (1), and R ¹¹ is R ¹⁰ or R A selected organic group, A is the following general formula (4)

(In the general formula (4), R and R ¹⁰ are as described above, and Q is an oxygen atom or a divalent hydrocarbon group having 1 to 3 carbon atoms.)
In the general formula (3) and the general formula (4), a, b and c are each independently an integer of 0 to 3, and e is an integer of 0 to 100 F is an integer of 0 to 20,000, g is an integer of 0 or 1, h is an integer of 0 or 1, i is an integer of 0 to 100, and j is 0 to 10 1 ≦ a + b + c + e + g + i when R ¹¹ is R ¹⁰ and 1 ≦ a + b + c + e + i when R ¹¹ is R. The compound represented by the general formula (3) contains at least one R ¹⁰ . )   A treated powder obtained by treating 0.1 to 30 parts by mass of the powder treating agent according to claim 1 or 2 with respect to 100 parts by mass of the powder.   The treated powder according to claim 3, wherein the powder is one or more of zinc oxide, titanium oxide, and extender.   A powder dispersion in oil obtained by dispersing the treated powder according to claim 3 or 4 in an oil agent.

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