JP2005344076A - Aba type glycerol-modified silicone - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a new silicone having excellent surface active action. <P>SOLUTION: The glycerol-modified silicone comprises constituent units A and B bonded in A-B-A in which A is an organosiloxane residue represented by general formula (1) and B is a glycerol derivative residue represented by general formula (2) (R<SP>1</SP>s are each independently a 1-10C alkyl group, cycloalkyl group, aryl group or aralkyl group which may be substituted with a halogen; X is an integer of 0-100; α is 1 or 2; R<SP>2</SP>s are each independently a 1-11C alkylene group; is an integer of 1-11). <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a novel ABA-type glycerin-modified silicone. The glycerin-modified silicone has a surface activity and is useful as a paint additive and an agrochemical spreading agent.

  When applying agricultural chemicals to crops for the purposes of weeding, pest control and disease prevention, the efficacy of the agricultural chemicals on the crops will be reduced. Spreading agents containing surfactants are used for the purpose of allowing agricultural chemicals to uniformly adhere to agricultural crops as soon as possible after spraying, and to penetrate the medicinal components into the leaves before it rains. As the surfactant, in addition to polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene higher fatty acid ester, and the like, silicone surfactants are used because of their low toxicity and high surface activity. Among these active agents, polyether-modified silicone having a trisiloxane skeleton in the main chain has the highest surface activity and has already been put into practical use as a spreading agent for agricultural chemicals (Patent Document 1). Further, the above silicone has a drawback that the surface activity is lowered when the pH is acidic or basic, but it is improved by changing the structure of the siloxane chain (Patent Document 2).

On the other hand, sprays based on hydrocarbon oils and plant extracts are known to have an effect of controlling pests by closing the pores of pests and an effect of improving the penetration of pesticides into the leaves (non- Patent Document 1). However, hydrocarbon oils, in particular plant extracts, have high surface tension and poor wettability to hydrophobic leaf surfaces, and it has been proposed to reduce surface tension by adding alkyl-modified silicone (Patent Document) 3). RE Gaskin et al. Reported that when alkyl silicone was used in the SPRAY OILS-BEYOND 2000 (Published by University of Western Sydney) medium, the spreadability of the plant extract was remarkably improved and effective in pest control. doing.

Furthermore, in recent reports, silicones having 3 or more hydroxyl groups and silicones having 2 hydroxyl groups and polyoxyethylene groups have the ability to reduce surface tension, and saccharides are exemplified as functional groups having hydroxyl groups. (Patent Document 4).

Japanese Examined Patent Publication No. 6-55642 Japanese Unexamined Patent Publication No. 2000-327787 European Patent Publication No. 0648413A1 Special Table 2003-533558 J. Agric. Food Chem., 34 (2), 235 "SPRAY OILS-BEYOND 2000", Western Sydney University, 2002

  However, the above conventional silicone-based spreading agent needs further improvement in terms of surface activity. Accordingly, an object of the present invention is to provide a silicone surfactant having a higher surface activity than conventional spreading agents.

Bは下記式で表されるグリセリン誘導体残基であり、

式中、Ｒ¹は、互いに独立に、ハロゲンで置換されていてよい炭素数１〜１０の、アルキル基、シクロアルキル基、アリール基もしくはアラルキル基であり、Ｘは０〜１００の整数であり、αは１又は２であり、Ｒ²は、互いに独立に、炭素数２〜１１のアルキレン基であり、ｓは１〜１１の整数である。 That is, the present invention relates to a glycerin-modified silicone in which structural units A and B are bonded by ABA.
However, A is an organosiloxane residue represented by the following formula (1),

B is a glycerin derivative residue represented by the following formula,

In the formula, R ¹ independently of each other is an alkyl group, cycloalkyl group, aryl group or aralkyl group having 1 to 10 carbon atoms which may be substituted with halogen, and X is an integer of 0 to 100, α is 1 or 2, R ² is independently an alkylene group having 2 to 11 carbon atoms, and s is an integer of 1 to 11.

  The glycerin-modified silicone has a surface active action and is added to agricultural chemicals, paints and the like to spread them widely and uniformly on the substrate.

In the glycerin-modified silicone represented by ABA of the present invention, A is an organosiloxane residue represented by the following formula (1).

In the above formula (1), R ¹ is independently an alkyl group, cycloalkyl group, aryl group or aralkyl group having 1 to 10 carbon atoms which may be substituted with halogen. Examples thereof include methyl groups, ethyl groups, propyl groups, butyl groups, pentyl groups, hexyl groups, heptyl groups, octyl groups, nonyl groups, decyl groups and other alkyl groups; cyclopentyl groups, cyclohexyl groups and other cycloalkyl groups. An aryl group such as a phenyl group or a tolyl group; an aralkyl group such as a benzyl group or a phenethyl group; a group in which a part of hydrogen is substituted with a halogen such as a trifluoropropyl group or a nonafluorooctyl group; A methyl group and a butyl group are preferred.

x is an integer of 0 or more and 100 or less, preferably 0 to 20, and more preferably 0 to 10. α is 1 or 2. The organosiloxane residue can be derived, for example, from an α-organohydrogensiloxane having a SiH group at the terminal, as will be described later with respect to the method for producing the silicone of the present invention.

式中、Ｒ²は、互いに独立に、炭素数２〜１１のアルキレン基であり、例えば、エチレン基、プロピレン基、ブチレン基、ペンチレン基、ウンデセン基が挙げられる。好ましくはＲ²は炭素数２〜５のアルキレン基であり、より好ましくは３、即ち、プロピレン基である。また、ｓは１以上１１以下の整数であり、好ましくは１〜７であって、さらに好ましくは２〜４である。 In the glycerin-modified silicone represented by ABA of the present invention, B is a glycerin derivative residue represented by the following formula (2).

In the formula, R ² is independently an alkylene group having 2 to 11 carbon atoms, and examples thereof include an ethylene group, a propylene group, a butylene group, a pentylene group, and an undecene group. R ² is preferably an alkylene group having 2 to 5 carbon atoms, more preferably 3, that is, a propylene group. Moreover, s is an integer of 1 or more and 11 or less, preferably 1 to 7, and more preferably 2 to 4.

The combination of x and s may be arbitrary within the above range. For example, as an agrochemical spreader application, when α is 1, x is 3 and s is 3 or 4. When α is 1, a combination of x of 20 to 60 and s of 3 or 4 is particularly suitable for coating additive use.

The glycerin derivative residue can be derived from a glycerin derivative having an unsaturated bond, particularly an allyl group at the terminal. The polyglycerin skeleton of the glycerin derivative residue is a straight chain polymerized by terminal OH groups of all glycerin, and includes a branch polymerized by OH groups bonded to secondary carbon. There may be.

上式で、R²はプロピレン基であり、Sは１〜８である。 Preferably, B is a linear polyglycerin derivative residue represented by the following formula.

In the above formula, R ² is a propylene group, and S is 1-8.

The ABA type silicone of the present invention can be produced by addition reaction of α-organohydrogensiloxane having a SiH group at its terminal and glycerin or polyglycerin having two aliphatic unsaturated bonds in one molecule. it can. Examples of the α-organohydrogensiloxane having a SiH group at the terminal include compounds represented by AH in which H is bonded to the organosiloxane residue A described above. For example, shown ^{below, MD H M, MM H,} MD 3 M H, can be used MD ₉ M ^H. However, in this specification, the (H ₃ C) ₃ SiO _1/2 group is represented as M, the (H ₃ C) ₂ SiO group is represented as D, and one of the methyl groups in M and D is hydrogen. Certain units are denoted as ^MH and ^DH . Units in which one of the methyl groups is substituted with the substituent ^R are denoted as M ^R and D ^R , respectively.

As glycerin or polyglycerin having two aliphatic unsaturated bonds in one molecule, those in which a part of R ² in B, preferably the terminal, is an unsaturated bond can be used. For example, the following triglycerin derivatives and tetraglycerin derivatives are preferable, and the following can be used.

A glycerin derivative having two aliphatic unsaturated bonds in the molecule is obtained by reacting glycerin or polyglycerin such as diglycerin or triglycerin with allyl glycidyl ether in the presence of an alkali catalyst such as potassium hydroxide. Can be obtained at The reaction temperature is preferably controlled at 60 to 120 ° C. After the reaction, the target product can be obtained by neutralizing the alkali catalyst and distilling off the low boiling point.

The α-organohydrogensiloxane and the glycerin derivative having an unsaturated group are in a molar ratio of SiH group / CH═CH ₂ group of 0.5 or more and less than 1.5, preferably 0.8 or more and less than 1.2. Addition reaction with.

The addition reaction is preferably performed in the presence of a platinum catalyst or a rhodium catalyst. Examples of preferable catalysts include chloroplatinic acid, alcohol-modified chloroplatinic acid, chloroplatinic acid-vinylsiloxane complex, and the like. The amount of the catalyst used may be the minimum amount effective as a catalyst, but the amount of platinum or rhodium is preferably 50 ppm or less, and particularly preferably 20 ppm or less.

You may perform the said addition reaction in an organic solvent as needed. Examples of the organic solvent include aliphatic alcohols such as methanol, ethanol, 2-propanol and butanol, aromatic hydrocarbons such as toluene and xylene, and aliphatic or alicyclic hydrocarbons such as n-pentane, n-hexane and cyclohexane. , Halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride and the like.

Although the addition reaction conditions are not particularly limited, the reaction is preferably performed for 1 to 10 hours under reflux.

After the addition reaction, removal of the allyl ether group with weak hydrochloric acid or alkylation by hydrogenation reaction may be performed by a known method. Moreover, you may add tocopherol and BHT as antioxidant.

An infrared spectrum example of the ABA glycerin-modified silicone of the present invention obtained by the above method is shown in FIG. The glycerin-modified silicone has a surface active action, and is particularly excellent in compatibility with an oily substance and lowers its interfacial tension. Therefore, it is suitable as an agrochemical spreading agent, paint additive, metal oil additive and the like.

The glycerin-modified silicone is used by adding it to a commercially available agrochemical oil or agrochemical formulation at a desired concentration. Or you may mix with the oil agent which should be spread | dispersed previously. The amount of the oil is appropriately adjusted to 4 to 10,000 parts by mass with respect to 1 part by mass of the glycerin-modified silicone of the present invention. If the amount is less than the lower limit, the glycerin-modified silicone may not be sufficiently dissolved. On the other hand, when the upper limit is exceeded, the effect of lowering the interfacial tension of the glycerin-modified silicone may be insufficient.

Any oil agent can be used as long as it has an effect of exterminating pests and an effect of improving the penetration of agricultural chemicals into the leaves. Examples thereof include vegetable oils extracted from plant seeds and animal oils such as beef tallow, and these hydrides or esterified products are used. In addition, mineral oils such as machine oil and spindle oil, which are collectively referred to as hydrocarbon oils, are also used.

For example, natural animal and vegetable oils and semi-synthetic fats and oils include avocado oil, linseed oil, almond oil, ibotarou, eno oil, olive oil, cacao butter, kapok wax, kayak oil, carnauba wax, liver oil, candelilla wax, beef tallow, beef leg fat , Beef bone fat, hydrogenated beef tallow, kyounin oil, whale wax, hydrogenated oil, wheat germ oil, sesame oil, rice germ oil, rice bran oil, sugarcane wax, sasanqua oil, safflower oil, shea butter, cinnamon oil, cinnamon oil, jojo Barrow, 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, castor oil fatty acid methyl ester, sunflower oil, grape oil, bayberry wax, jojoba oil, macadamia Ritz oil, beeswax, mink oil, cottonseed oil, cotton wax, owl, owl kernel oil, montan wax, coconut oil, hydrogenated coconut oil, tricoconut oil fatty acid glyceride, sheep oil, peanut oil, lanolin, liquid lanolin, reduced lanolin, lanolin alcohol , Hard lanolin, lanolin acetate, lanolin fatty acid isopropyl, hexyl laurate, POE lanolin alcohol ether, POE lanolin alcohol acetate, lanolin fatty acid polyethylene glycol, POE hydrogenated lanolin alcohol ether, egg yolk oil and the like.

Avocado oil, almond oil, olive oil, sesame oil, rice bran oil, safflower oil, soybean oil, corn oil, rapeseed oil, persic oil, castor oil, sunflower oil, grape seed oil, cottonseed oil, preferably having a low melting point and liquid at room temperature More preferable are low-priced oils such as safflower oil, soybean oil, corn oil, rapeseed oil, castor oil, sunflower oil, and cottonseed oil.

Examples of the hydrocarbon oil include petroleum-based oils generally called machine oil or spindle oil by those skilled in the art, which are appropriately selected from products of various viscosities and used suitably. In addition, there are ozokerite, α-olefin oligomer, squalane, ceresin, paraffin, paraffin wax, liquid paraffin (mineral oil), polybutene, liquid isoparaffin, microcrystalline wax, petrolatum, etc., among them at room temperature like natural animal and vegetable oils. Liquid α-olefin oligomers, squalane, ceresin, liquid paraffin and liquid isoparaffin are preferred, and liquid paraffin is more preferred.

Similarly, fatty acids, higher alcohols and ester oils which are constituents of vegetable oils can be used as oil agents, but are preferably selected from those which are liquid at room temperature from the viewpoint of use. In the present invention, the oil agent may be a mixture of two or more kinds.

In addition to the oil agent, it may further contain an agrochemical or various additives. Usable agrochemicals include, but are not limited to, herbicides, fungicides, and insecticides. You may mix | blend the antifoamer for suppressing foaming at the time of mixing this agrochemical, for example, the silicone type antifoamer which consists of silicone oil, a silica, etc. Further, a solvent such as hexane may be blended to form a solution, or LPG or the like may be added and sealed in a can and provided in the form of a spray for spreading on the leaf surface on a small scale. Good.

The spreading agent of the present invention may be a self-emulsifying type spreading agent that becomes emulsified in addition to an aqueous pesticide when used, or an emulsifying type spreading agent containing water from the beginning. . In that case, one or more surfactants for emulsifying and dispersing the oil agent and the glycerin-modified silicone of the present invention in water or an aqueous composition are used. Surfactants include anionic, cationic, nonionic and amphoteric active agents, and are not particularly limited, but some agrochemicals are acidic substances, so they must be nonionic. Is preferred.

Nonionic surfactants include sorbitan fatty acid ester, glycerin fatty acid ester, polyglycerin fatty acid ester, propylene glycol fatty acid ester, polyethylene glycol fatty acid ester, sucrose fatty acid ester, polyoxyethylene alkyl ether, polyoxypropylene alkyl ether, poly Oxyethylene polyoxypropylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyoxyethylene propylene glycol fatty acid ester, Polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil, poly Oxyethylene phytostanol ether, polyoxyethylene phytosterol ether, polyoxyethylene cholestanol ether, polyoxyethylene cholesteryl ether, linear or branched polyoxyalkylene-modified organopolysiloxane, linear or branched polyoxyalkylene alkyl Examples include co-modified organopolysiloxanes, alkanolamides, sugar ethers, and sugar amides. Two or more of the nonionic surfactants may be combined. In addition, the addition amount of a nonionic surfactant is 1-50 mass% of a spreading agent total mass, Preferably it is 2-40 mass%, More preferably, it is 5-30 mass%. When the amount is lower than the lower limit, the dispersibility of the oil agent in water is lowered, and when the amount is higher than the upper limit, the solubility of the glycerin-modified silicone is lowered, and the interfacial tension lowering effect of the silicone cannot be sufficiently exhibited. There is.

In the case of an emulsification type containing water, a predetermined amount of water is added to the above-mentioned oil agent, the glycerin-modified silicone of the present invention, and the nonionic surfactant as an emulsifier, and a propeller mixer, anchor mixer, paddle mixer, homomixer is added. And emulsification with a stirring mixer such as a line mixer, colloid mill, or homogenizer. The amount of water is 1000 parts by mass with respect to a total of 100 parts by mass of components other than water, and preferably 800 parts by mass or less. If the amount of water exceeds the above upper limit, the concentration of the oil agent becomes too low, and in order to obtain a desired effect, it must be distributed many times and is not economical.

A small amount of preservatives and bactericides may optionally be added to the emulsified spreading agent for the purpose of preserving. Examples of the preservative / disinfectant include sodium hypochlorite, sorbic acid, potassium sorbate, salicylic acid, sodium salicylate, benzoic acid, sodium benzoate, parabens, isothiazoline compounds and the like. These addition amounts are preferably 0.001 to 1.0 parts by mass, more preferably 0.005 to 0.8 parts by mass with respect to 100 parts by mass of the agrochemical spreading agent composition of the present invention.

Furthermore, if desired, stabilizers such as polyvinyl alcohol, methyl cellulose, carboxymethyl cellulose, sodium carboxymethyl cellulose, sodium polyacrylate, xanthan gum and the like may be optionally added.

When spraying the agricultural chemical spreader on agricultural products, in either case of emulsification type or self-emulsification type, dilute with water and mix with stirring to make a uniform emulsion, then use sprayer, spreader, etc. And then sprayed. The stirring and mixing may be a generally used stirring mixer, such as a propeller mixer, an anchor mixer, a paddle mixer, a homomixer, or a line mixer. Concentration emulsions can be made. At this time, additives such as spreading agents and antifoaming agents may be used.

Examples Hereinafter, the present invention will be described by way of examples, but the present invention is not limited thereto. The interfacial tension in the examples is a value at 25 ° C., and the interfacial tension with air was measured by a droplet method (fully automated interfacial tension system PD-W type manufactured by Kyowa Interface Chemical Co., Ltd.). The interfacial tension of dimethylpolysiloxane (viscosity at 25 ° C. of 30 mm ² / s) measured by this method was 18.2 mN / m. In the table, the symbol D or I in parentheses indicates solubility, D is in a finely dispersed state, I is insoluble, and those not specifically described indicate transparent dissolution.

Preparation of glycerin derivative having two aliphatic unsaturated bonds in the molecule The glycerin derivative (hereinafter referred to as diallylated glycerin) was prepared by the method described above. That is, in the presence of a potassium hydroxide catalyst, polyglycerol and allyl glycidyl ether were reacted at 60 to 120 ° C., and then the catalyst was neutralized, and then the low boiling point was distilled off.

The physical properties of the resulting triglyceryl diallyl ether were a pale yellow liquid having a viscosity of 330 mm ² / s, a hydroxyl value of 523 KOHmg / g, and an unsaturation of 6.13 meq / g. The hydroxyl value and the degree of unsaturation were almost as theoretical values (525 and 6.24, respectively). Similarly, tetraglyceryl diallyl ether was prepared. The physical property value was a pale yellow liquid having a viscosity of 1397 mm ² / s, a hydroxyl value of 533 KOH mg / g, and an unsaturation of 5.05 meq / g.

Using the diallylated glycerin obtained, ABA-type glycerin-modified silicones in Examples were prepared. The preparation was carried out in a reactor equipped with a stirrer, a thermometer, and a reflux pipe in an amount of polyglyceryl diallyl ether in an amount such that the molar ratio of terminal unsaturated groups to SiH groups of the organohydrogensiloxane was 1.0, An effective amount of catalyst was added and reacted while dropping organohydrogensiloxane, and then the reaction solution was distilled at 100 ° C. under reduced pressure to distill off the solvent.
For example, the glycerin-modified silicone of Example 3 is charged with 100 g of triglyceryl diallyl ether, 300 g of isopropyl alcohol and 0.05 g of an IPA solution containing 0.5% by weight of chloroplatinic acid, and 210 g of MD ₃ M ^H at 60 ° C. with stirring. Then, the reaction mixture was obtained by evaporating the solvent at 100 ° C. under reduced pressure. Similarly, ABA glycerin-modified silicones having different siloxane polymerization degrees and glycerin polymerization degrees were synthesized.

The obtained ABA-type silicone of Example 3 was analyzed by ²⁹ Si-NMR using deuterated chloroform as a solvent. As a result, Me ₃ SiO— group and —CH _{2 were} mixed at a ratio of 1: 1 to 7.52 ppm and 7.11 ppm. since the signal was observed by Me ₂ SiO- -OMe ₂ SiO- group at 2 to 1 ratio on the signal observed -21.4ppm and -21.6ppm by group, it siloxane structure is MD ₃ M ^R confirmed. Further, it at ¹ H-NMR integral values of 0.1ppm signal by Me ₃ SiO- groups and -Me ₂ SiO- group for the integral values 2H of 0.5ppm signal by -CH ₂ Me ₂ SiO- group is 33H From the results, it was confirmed that 1 mol of MD ₃ ^MH was bonded to 1 mol of allyl group. In addition, since the integral value of the signal (m, 3.3-3.9 ppm) of the glycerin chain including the hydrogen of the hydroxyl group with respect to the integral value 2H of the 0.5 ppm signal due to the —CH ₂ Me ₂ SiO— group is 11H, It was confirmed that 2 mol of siloxane was bonded.

Furthermore, as a result of IR measurement by the KBr plate method, strong absorption due to OH stretching vibration was observed in the vicinity of 3400 cm ⁻¹ , which confirmed that the product was a compound having a glycerin group.

Examples 1-11
The results of measuring the properties of the 11 types of prepared ABA glycerin-modified silicones are shown in the table below.

上表において、グリセリン質量％は、出発反応混合物総重量中のジアリル化グリセリンの質量％である。粘度はキャノンヘンスケ粘度計により、比重は浮きばかり法により、屈折率はアッベ計により夫々測定した。

In the above table, glycerin mass% is mass% of diallylated glycerin in the total weight of the starting reaction mixture. The viscosity was measured with a Canon Henske viscometer, the specific gravity was measured with the float method, and the refractive index was measured with an Abbe meter.

Examples 12 to 16 Oily composition A composition in which the obtained glycerin-modified silicone was mixed at 10% by mass in an oil was prepared, and the interfacial tension of the composition was measured. The results are shown in Table 2 below.

表２において、各油剤の下に記載されているのは、油剤単独の界面張力である。該値に比べて、各実施例組成物の界面張力が、著しく低いことが分かる。特に、実施例14および16の界面張力は、一般的なシリコーンオイルの界面張力に匹敵するほどであった。なお、これらの組成物において、ＡＢＡ型シリコーンが完全に溶解しておらず僅かに分散している状態（Ｄ）であっても、界面張力の測定値は再現性がよく、何ら問題はなかった。
表３においてさらに低濃度での測定を行ったところ流動パラフィンにおいては１質量%の添加で著しい効果が見られ、菜種油では５質量%の添加で著しい効果が見られた。特に、実施例９の変性シリコーンの界面張力低下能が高く、いずれの油剤においても僅か１質量％の添加で著しく低下している。

In Table 2, what is described under each oil agent is the interfacial tension of the oil agent alone. It can be seen that the interfacial tension of each example composition is significantly lower than that value. In particular, the interfacial tension of Examples 14 and 16 was comparable to that of general silicone oil. In these compositions, even when the ABA-type silicone was not completely dissolved but slightly dispersed (D), the measured values of the interfacial tension had good reproducibility, and there was no problem. .
When the measurement was performed at a lower concentration in Table 3, the liquid paraffin showed a remarkable effect with the addition of 1% by mass, and the rapeseed oil showed a remarkable effect with the addition of 5% by mass. In particular, the modified silicone of Example 9 has a high interfacial tension reducing ability, and in any oil agent, it is significantly reduced by addition of only 1% by mass.

In Examples 14 and 16, the change in interfacial tension depending on the concentration of ABA type silicone was examined. The results are shown in the table below.

流動パラフィンにおいては、１質量%の添加で著しい効果が見られ、菜種油では５質量%の添加で著しい効果が見られた。特に、実施例９の変性シリコーンの界面張力低下能が高く、いずれの油剤においても僅か１質量％の添加で著しく低下した。

In liquid paraffin, a remarkable effect was observed when 1% by mass was added, and in rapeseed oil, a significant effect was observed when 5% by mass was added. In particular, the modified silicone of Example 9 had a high ability to lower the interfacial tension, and in any of the oils, it was remarkably reduced by addition of only 1% by mass.

Comparative Examples 1-6
Silicone having no glycerin derivative residue or non-ABA type silicone was prepared and measured for each physical property, and further mixed with an oil agent in the same manner as in Example, and the interfacial tension of the mixture was measured. The results are shown in the table below.

表４に示したとおり、他の構造ではいずれも本発明のABA型グリセリン変性シリコーンと比較して界面張力の低下効果に劣った。特にトリグリセリンモノアリルエーテルにより変性した比較例５は、ＡＢ型のグリセリン変性シリコーンであるが、油剤との相溶性に劣り、油剤中で沈殿してしまったために、界面張力の測定ができなかった。

As shown in Table 4, all other structures were inferior in the interfacial tension reducing effect as compared with the ABA glycerin-modified silicone of the present invention. In particular, Comparative Example 5 modified with triglycerin monoallyl ether is an AB type glycerin-modified silicone. However, the interfacial tension could not be measured because of poor compatibility with the oil and precipitation in the oil. .

Examples 17 to 20 Emulsified composition Next, a composition having the composition shown in Table 5 was prepared, water was added so that components other than water were 10%, and the mixture was uniformly stirred and mixed. An emulsified composition was prepared. The composition was applied to the leaves with a spray, and after moisture was dried, the surface of the leaves was observed to visually observe the adhesion state of the oil, and evaluated according to the following criteria.
○: Oil agent attachment range is 95% or more of the total leaf surface area. Δ: Oil agent attachment range is 70 to 95% of the leaf total surface area.
X: The adhesion range of the oil agent is 70% or less of the total leaf surface area.

上表から、本発明の乳化型組成物は、油剤が葉一面に広がって付着し、散布効率が高いことが分かった。

From the above table, it was found that in the emulsified composition of the present invention, the oil spreads and adheres to the entire surface of the leaf, and the spraying efficiency is high.

   The novel ABA glycerin-modified silicone of the present invention is an excellent surfactant. Moreover, since it is excellent in compatibility with an oil agent, it is suitable for an agrochemical spreader, a paint spreader, etc. as an oil-based composition or an emulsion type composition.

4 is an IR chart of ABA-type glycerin-modified silicone of Example 3.

Claims (10)

A glycerin-modified silicone in which structural units A and B are bonded by ABA,
However, A is an organosiloxane residue represented by the following formula (1),

B is a glycerin derivative residue represented by the following formula,

In the formula, R ¹ independently of each other is an alkyl group, cycloalkyl group, aryl group or aralkyl group having 1 to 10 carbon atoms which may be substituted with halogen, and X is an integer of 0 to 100, α is 1 or 2, R ² is independently an alkylene group having 2 to 11 carbon atoms, and s is an integer of 1 to 11. The glycerin-modified silicone according to claim 1, wherein the structural unit B is a glycerin derivative residue represented by the following formula:

Wherein, R ² is a propylene group, s is 1-8. A surfactant comprising the glycerin-modified silicone according to claim 1. An agrochemical spreading agent comprising the glycerin-modified silicone according to claim 1 or 2. The agrochemical spreading agent according to claim 4, further comprising 4 to 10,000 parts by mass of at least one oil agent based on 1 part by mass of glycerin-modified silicone. The pesticide spreading agent according to claim 4 or 5, further comprising an emulsifier. The pesticide spreading agent according to claim 6, further comprising water and in an emulsified form. The agrochemical spreading agent according to any one of claims 4 to 7, wherein the oil agent is a plant extract oil. A paint additive comprising the glycerin-modified silicone according to claim 1 or 2. The method for producing a glycerin-modified silicone according to claim 1 or 2, comprising addition reaction of α-organohydrogensiloxane and a glycerin derivative each having an aliphatic unsaturated bond at both ends.

Images