JP2005054090A - Oil-in-water modified silicone emulsion composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To mainly contain (A) a long-chain alkyl-modified silicone and / or a long-chain alkyl aralkyl co-modified silicone, (B) an oxyethylene adduct of an alkyl alcohol having 8 to 11 carbon atoms in the alkyl group, and (C) water. An oil-in-water modified silicone emulsion composition characterized by comprising the components.
[MEANS FOR SOLVING PROBLEMS] The oil-in-water modified silicone emulsion composition of the present invention is characterized by excellent stability and less environmental burden and human problems. Such an oil-in-water modified silicone emulsion composition of the present invention can be suitably used as a mold release agent for die casting, and can also be used as various mold release agents.
[Selection figure] None

Description

  INDUSTRIAL APPLICABILITY The present invention is an oil-in-water mold that is effectively used as an aqueous mold release agent that is excellent in stability and has a low environmental impact, and that is particularly suitable for metal casting molds and provides lubricity and mold release properties. The present invention relates to a modified silicone emulsion composition.

  Silicone emulsions modified with long-chain alkyl groups or aralkyl groups are paintable and excellent in heat resistance, lubricity, and mold release properties, making them very suitable as mold release agents for aluminum die casting and magnesium die casting. Widely used in parts, home appliances, precision equipment parts, etc.

  Examples of the emulsifier used in the silicone emulsion include a surfactant composed of a nonionic surfactant, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, or a mixture thereof. Among these, nonionic surfactants are suitably used for silicone emulsions used for mold release agents for die casting.

  However, in recent years, there has been a demand for the selection of a surfactant having a low environmental load. For example, alkyl polyethers having an alkyl group having 12 to 15 carbon atoms are considered to be PRTR as chemical substances that are concerned about environmental impact. (Pollutant Release and Transfer Register) has been certified as a required designated chemical substance and its use has been restricted. Alkyl ester type, sorbitan ester type, sorbitan ester ether type are known as nonionic surfactants corresponding to such restrictions, but emulsion creaming, oil separation, water separation, etc. may occur, In actual use, there is a problem that the dilution stability at a low concentration is inferior.

In addition, as a well-known document relevant to this invention, there exist the following.
JP-A-4-844633

  The present invention has been made in view of the above circumstances, and is an oil-in-water mold that is excellent in stability and has a small environmental load, and is particularly suitably applied to a metal casting mold to provide lubricity and releasability. It is an object to provide a modified silicone emulsion composition.

As a result of intensive studies to achieve the above object, the present inventors have found that the above problem can be solved by using an oxyethylene adduct of an alkyl alcohol having 8 to 11 carbon atoms in the alkyl group as a surfactant. I found it.
That is, (A) a long-chain alkyl-modified silicone and / or a long-chain alkylaralkyl co-modified silicone, (B) an oxyethylene adduct of an alkyl alcohol having 8 to 11 carbon atoms in the alkyl group, and (C) water as a main component Since the oil-in-water long-chain alkyl-modified and / or long-chain alkylaralkyl co-modified silicone emulsion composition is excellent in stability and has a low environmental impact, and has excellent lubricity and releasability, a release agent, In particular, it has been found that it can be suitably used as a mold release agent for die casting, and the present invention has been made.

  Therefore, the present invention provides (A) a long-chain alkyl-modified silicone and / or a long-chain alkylaralkyl co-modified silicone, (B) an oxyethylene adduct of an alkyl alcohol having 8 to 11 carbon atoms in the alkyl group, and (C) An oil-in-water modified silicone emulsion composition comprising water as a main component is provided.

  The oil-in-water modified silicone emulsion composition of the present invention is characterized by excellent stability and less environmental burden and human problems. Such an oil-in-water modified silicone emulsion composition of the present invention can be suitably used as a mold release agent for die casting, and can also be used as various mold release agents.

Hereinafter, the present invention will be described in more detail.
Component (A), long-chain alkyl-modified silicone and / or long-chain alkyl aralkyl co-modified silicone, is the main component of the present invention, and is excellent in heat resistance, lubricity and releasability, so it is suitable for aluminum die casting and magnesium die casting. The long-chain alkyl-modified silicone and the long-chain alkylaralkyl co-modified silicone can be represented by the following formulas (1) and (2).

（式中、Ｒは炭素数１〜７の１価炭化水素基、Ｒ¹は炭素数８〜２０のアルキル基、Ｒ²は炭素数８〜２０のアラルキル基、ＡはＲ又はＲ¹、ＢはＲ、Ｒ¹又はＲ²であり、ｎは１〜４００の整数、ｍは０〜４００の整数、ｎ＋ｍは１〜４００の整数であり、ｐ、ｑは１〜４００の整数、ｒは０〜４００の整数、ｐ＋ｑ＋ｒは２〜４００の整数である。）

Wherein R is a monovalent hydrocarbon group having 1 to 7 carbon atoms, R ¹ is an alkyl group having 8 to 20 carbon atoms, R ² is an aralkyl group having 8 to 20 carbon atoms, A is R or R ¹ , B Is R, R ¹ or R ² , n is an integer of 1 to 400, m is an integer of 0 to 400, n + m is an integer of 1 to 400, p and q are integers of 1 to 400, and r is 0 An integer of ˜400, p + q + r is an integer of 2 to 400.)

  In the above formula, R is the same or different monovalent hydrocarbon group having 1 to 7 carbon atoms, specifically, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, etc. Saturated alicyclic hydrocarbon groups such as saturated hydrocarbon group, cyclopentyl group and cyclohexyl group, and aromatic hydrocarbon groups such as phenyl group and tolyl group are exemplified, and methyl group is particularly preferable.

R ¹ is the same or different alkyl group having 8 to 20 carbon atoms, specifically, octyl group, nonyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, An octadecyl group, a nonadecyl group, an eicosyl group and the like are exemplified, and a dodecyl group and a tetradecyl group are particularly preferable.

R ² is the same or different aralkyl group having 8 to 20 carbon atoms, specifically, benzyl group, 4-methylbenzyl group, p-methoxybenzyl group, diphenylmethyl group, 2-phenylethyl group, 2- Examples thereof include a phenylpropyl group and a 3-phenylpropyl group, and a 2-phenylpropyl group is particularly preferable.

A is R or R ¹ and B is R, R ¹ or R ² . n is an integer of 1 to 400, preferably an integer of 20 to 50, m is an integer of 0 to 400, preferably 0 to 20, and n + m is an integer of 1 to 400, preferably 30 to 100. It is an integer. p and q are integers of 1 to 400, preferably 10 to 50, r is an integer of 0 to 400, preferably 0 to 20, and p + q + r is an integer of 2 to 400, preferably 10 It is an integer of 100.
As the component (A), one type may be used alone, or two or more types may be mixed and used.

  The oxyethylene adduct of alkyl alcohol having 8 to 11 carbon atoms in the alkyl group (B) is a characteristic component of the present invention. This component (B) is an emulsifier for the component (A), and has the advantages of improving the stability of the emulsion composition of the present invention and reducing the burden on the environment and the human body. Moreover, it functions to improve the stability when the emulsion composition of the present invention is mixed with other components. (B) As a component, the polyoxyethylene linear alkyl ether and / or polyoxyethylene branched alkyl ether represented by following formula (3) are preferable.

式中、Ｒ³は炭素数８〜１１の直鎖型あるいは分岐型のアルキル基であり、好ましくはノルマルデシル基である。ｙは１〜２０の整数であり、好ましくは２〜１２の整数である。

In the formula, R ³ is a linear or branched alkyl group having 8 to 11 carbon atoms, preferably a normal decyl group. y is an integer of 1-20, preferably an integer of 2-12.

  Specific examples of the component (B) include polyoxyethylene (5) isononyl ether (manufactured by Nippon Emulsifier, RAA-03001, HLB12.2), polyoxyethylene (3) decyl ether (manufactured by Aoki Oil, Fine Surf D1303, HLB9.0), polyoxyethylene (5) decyl ether (manufactured by Aoki Oil, Fine Surf D1305, HLB11.9), polyoxyethylene (10) decyl ether (manufactured by Aoki Oil, Finesurf D1310, HLB14.7), poly Examples thereof include oxyethylene (8) isoundecyl ether (manufactured by Kao, Emulgen 1108, HLB 13.5).

  As the component (B), one type of polyoxyethylene alkyl ether may be used alone, or a mixture of two or more types may be used, for example, an ethylene oxide adduct having an addition mole number of 2 to 10 mol and 10 to 20 mol. A mixture prepared by mixing an ethylene oxide adduct so as to have an average HLB of 10 to 15 can be used.

  Although the compounding quantity of (B) component is not specifically limited, It is preferable that it is 0.1-50 mass parts with respect to 100 mass parts of (A) component, More preferably, it is 1-20 mass parts. If the blending amount is less than 0.1 parts by mass, the stability of the emulsion composition, the dilution stability in water and the dispersibility in other components may be reduced, and if it exceeds 50 parts by mass, the use is limited. There is a risk.

  The water of component (C) is a dispersion medium, and for example, pure water, ion exchange water, tap water, and the like can be used. Although content of (C) component is not restrict | limited in particular, it is preferable that it is 10-2000 mass parts with respect to 100 mass parts of (A) component, More preferably, it is 50-1000 mass parts. If the amount is less than 10 parts by mass, the stability of the emulsion composition and the dispersibility in other components may be reduced, and if it exceeds 2000 parts by mass, the long-term stability may be deteriorated.

  The silicone-modified emulsion composition of the present invention consists essentially of components (A) to (C), but various additives can be blended so long as the object of the present invention is not impaired. Examples of such additives include anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants other than the component (B), aqueous polymers, rust inhibitors, fungicides, preservatives, pH Examples include regulators.

  In the present invention, it is preferable to use an anionic surfactant (D). In addition to improving the stability of the emulsion composition, the anionic surfactant functions to improve the efficiency of wastewater treatment using an emulsion breaker. Specific examples include fatty acid metal soaps, alkyl sulfate salts, alkyl ether sulfate salts, and alkylbenzene sulfonates. (D) It is preferable that the compounding quantity of a component is 0.001-20 mass parts with respect to 100 mass parts of (A) component. If the blending amount is less than 0.001 part by mass, the effect of improving the stability of the emulsion composition or the wastewater treatment property may not be obtained, and if it exceeds 20 parts by mass, the use may be limited.

  Moreover, it is preferable to use a rust preventive agent (E). A rust preventive agent is for preventing those corrosions, when using the emulsion composition of this invention using metal machines and piping. Specific examples include ethylenediamine tetraacetic acid, hydroxyethyliminodiacetic acid, dihydroxyethyl glycol and the like. (E) It is preferable that the compounding quantity of a component is 0.001-20 mass parts with respect to 100 mass parts of (A) component. If the blending amount is less than 0.001 part by mass, the antirust effect may not be obtained, and if it exceeds 20 parts by mass, the use may be limited.

  Furthermore, it is preferable to use a preservative (F). The preservative is for preventing the occurrence of mold and the like when the emulsion composition of the present invention is stored for a long period of time. Specific examples include benzoic acid, sodium benzoate, methylisothiazolone compounds, bromonitroalcohol compounds, and the like. (F) It is preferable that the compounding quantity of a component is 0.001-2 mass parts with respect to 100 mass parts of (A) component. When the blending amount is less than 0.001 part by mass, the antiseptic effect may not be obtained, and when it exceeds 2 parts by mass, the use may be limited.

  Moreover, it is preferable to mix | blend a pH adjuster (G). The pH adjuster is for keeping the pH of the emulsion composition of the present invention neutral, and prevents the corrosion of the emulsion composition of the present invention when used using a metal machine or piping. Is to do. Specific examples include monosodium phosphate, disodium phosphate, sodium bicarbonate, sodium carbonate and the like, and these can be used alone or in combination of two or more. It is preferable that the compounding quantity of (G) component is 0.001-2 mass part with respect to 100 mass parts of (A) component. If the blending amount is less than 0.001 part by mass, the effect of preventing corrosion may not be obtained, and if it exceeds 2 parts by mass, the use may be limited.

  The method for preparing the oil-in-water modified silicone emulsion composition of the present invention is not particularly limited, but after mixing the components (A), (B), (C) and other components as necessary, using a homomixer or the like. A method of emulsifying and emulsifying at high speed is preferably used. In the present invention, the average particle size of the emulsion is usually 0.15 μm or more, preferably 0.15 to 0.5 μm.

  EXAMPLES Hereinafter, although a preparation example, an Example, and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. In addition, in the following example, a part shows a mass part. In the formula, Me represents a methyl group, and Ph represents a phenyl group.

で表されるアルキル変性シリコーン１００部と（Ｂ）成分としてポリオキシエチレン（５）デシルエーテル（青木油脂製、ファインサーフＤ１３０５、ＨＬＢ１１．９）９．０部を混合した後、（Ｃ）イオン交換水４．０部を加えてホモミキサーで乳化した。更にイオン交換水８２．６部を加えて希釈攪拌後、（Ｄ）ドデシルエーテルスルホン酸ナトリウム２．０部、（Ｅ）エチレンジアミンテトラアセチックアシッド２．０部、（Ｆ）メチルイソチアゾロン化合物０．１部、（Ｇ）リン酸二ナトリウム０．２部及びリン酸一ナトリウム０．１部を添加し、水中油型アルキル変性シリコーンエマルジョン組成物を調製した。 [Example 1]
(A) The following formula as a component

After mixing 100 parts of alkyl-modified silicone represented by the formula (B) and 9.0 parts of polyoxyethylene (5) decyl ether (manufactured by Aoki Oil, Fine Surf D1305, HLB 11.9), (C) ion exchange 4.0 parts of water was added and emulsified with a homomixer. Further, 82.6 parts of ion-exchanged water was added and diluted and stirred. Then, (D) 2.0 parts of sodium dodecyl ether sulfonate, (E) 2.0 parts of ethylenediaminetetraacetic acid, (F) methyl isothiazolone compound 0.1 Part, (G) disodium phosphate 0.2 part and monosodium phosphate 0.1 part were added to prepare an oil-in-water alkyl-modified silicone emulsion composition.

[Example 2]
Component (B) is composed of 4.2 parts of polyoxyethylene (3) decyl ether (manufactured by Aoki Oil, Fine Surf D1303, HLB9.0) and polyoxyethylene (10) decyl ether (manufactured by Aoki Oil, Fine Surf D1310, HLB14. 7) An oil-in-water alkyl-modified silicone emulsion composition was prepared in the same manner as in Example 1 except that the mixture was changed to 4.8 parts.

[Example 3]
(B) The oil-in-water alkyl-modified silicone was carried out in the same manner as in Example 1 except that the component was changed to 9.0 parts of polyoxyethylene (5) isononyl ether (manufactured by Nippon Emulsifier, RAA-03001, HLB12.2). An emulsion composition was prepared.

[Example 4]
(B) An oil-in-water alkyl-modified silicone emulsion was prepared in the same manner as in Example 1 except that the component was changed to 9.0 parts of polyoxyethylene (8) isoundecyl ether (Kao, Emulgen 1108, HLB 13.5). A composition was prepared.

で表されるアルキルアラルキル共変性シリコーン１００部に変更した以外は実施例１と同様に行い、水中油型アルキルアラルキル共変性シリコーンエマルジョン組成物を調製した。 [Example 5]
(A) component is represented by the following formula

An oil-in-water alkylaralkyl co-modified silicone emulsion composition was prepared in the same manner as in Example 1 except that the alkyl aralkyl co-modified silicone represented by the formula (1) was changed to 100 parts.

[Example 6]
Component (B) is composed of 4.2 parts of polyoxyethylene (3) decyl ether (manufactured by Aoki Oil, Fine Surf D1303, HLB9.0) and polyoxyethylene (10) decyl ether (manufactured by Aoki Oil, Fine Surf D1310, HLB14. 7) An oil-in-water alkylaralkyl co-modified silicone emulsion composition was prepared in the same manner as in Example 5 except that the mixture was changed to 4.8 parts.

[Example 7]
(B) The component was changed to 9.0 parts of polyoxyethylene (5) isononyl ether (manufactured by Nippon Emulsifier, RAA-03001, HLB12.2) in the same manner as in Example 5, and the oil-in-water type alkylaralkyl was prepared. A modified silicone emulsion composition was prepared.

[Example 8]
(B) The oil-in-water alkylaralkyl co-modification was performed in the same manner as in Example 5 except that the component was changed to 9.0 parts of polyoxyethylene (8) isoundecyl ether (Kao, Emulgen 1108, HLB13.5). A silicone emulsion composition was prepared.

[Comparative Example 1]
(B) As an emulsifier instead of the component, polyoxyethylene (6) oleate (manufactured by NOF Corporation, Nonion O-6, HLB 13.5) was used in the same manner as in Example 1 except that it was changed to 9.0 parts. An alkyl-modified silicone emulsion composition was prepared.

[Comparative Example 2]
(B) The oil-in-water type alkyl modification was performed in the same manner as in Example 1 except that polyoxyethylene sorbitan oleate (Nippon Emulsifier, New Coal 82, HLB 12.0) 9.0 parts was used as an emulsifier instead of the component (B). A silicone emulsion composition was prepared.

[Comparative Example 3]
(B) As an emulsifier instead of the component, polyoxyethylene (6) oleate (manufactured by NOF Co., Ltd., Nonion O-6, HLB 13.5) was used in the same manner as in Example 5 except that it was changed to 9.0 parts. An alkyl aralkyl co-modified silicone emulsion composition was prepared.

[Comparative Example 4]
(B) An oil-in-water alkyl aralkyl was prepared in the same manner as in Example 5 except that polyoxyethylene sorbitan oleate (manufactured by Nippon Emulsifier, New Coal 82, HLB 12.0) was replaced with 9.0 parts instead of component (B). A co-modified silicone emulsion composition was prepared.

  Using the oil-in-water modified silicone emulsion compositions of Examples 1 to 8 and Comparative Examples 1 to 4, the average particle size, high temperature stability, and dilution stability were evaluated by the following methods. These results are shown in Tables 1 and 2.

[Average particle size of emulsion]
The emulsion composition was measured using an N4 PLUS Submicron Particle Size Analyzer manufactured by BECKMAN COULTER.

[High temperature stability]
The emulsion composition was sealed in a 100 cc glass bottle and allowed to stand in a high temperature bath at 50 ° C. for 1 month. The emulsion after one month was visually observed and evaluated according to the following criteria.
(Double-circle): It was uniform similarly to immediately after preparation, and high temperature stability was favorable.
○: Some creaming was observed at the top.
Δ: A considerable amount of creaming was observed.
X: It separated into two layers.

[Dilution stability]
An aqueous solution of 2% by mass of an emulsion was prepared in a 200 cc beaker, the state after standing for 22 hours was observed, and evaluated according to the following criteria.
(Double-circle): It was uniform similarly to immediately after preparation, and dilution stability was favorable.
○: Some oil spots were observed on the liquid surface.
(Triangle | delta): Creaming was recognized by the liquid level upper part.
X: The oil was separated over the entire liquid surface.

Claims (9)

  (A) Long chain alkyl-modified silicone and / or long-chain alkyl aralkyl co-modified silicone, (B) oxyethylene adduct of alkyl alcohol having 8 to 11 carbon atoms in alkyl group, and (C) water as main component. An oil-in-water modified silicone emulsion composition characterized by the above. The oil-in-water modified silicone emulsion composition according to claim 1, wherein the long-chain alkyl-modified silicone as the component (A) is an organopolysiloxane represented by the following formula (1).

(In the formula, R is a monovalent hydrocarbon group having 1 to 7 carbon atoms, R ¹ is an alkyl group having 8 to 20 carbon atoms, A is R or R ¹ , n is an integer of ¹ to 400, and m is 0. An integer of ˜400, n + m is an integer of 1 to 400.) The oil-in-water modified silicone emulsion composition according to claim 1, wherein the long-chain alkylaralkyl co-modified silicone of component (A) is an organopolysiloxane represented by the following formula (2).

(Wherein R is a monovalent hydrocarbon group having 1 to 7 carbon atoms, R ¹ is an alkyl group having 8 to 20 carbon atoms, R ² is an aralkyl group having 8 to 20 carbon atoms, B is R, R ¹ or R ² and p and q are integers of 1 to 400, r is an integer of 0 to 400, and p + q + r is an integer of 2 to 400.)   The oxyethylene adduct of an alkyl alcohol having 8 to 11 carbon atoms in the alkyl group as component (B) is a polyoxyethylene linear alkyl ether, a polyoxyethylene branched alkyl ether or a mixture thereof. Or the oil-in-water modified silicone emulsion composition of 3 or 3.   5. The component according to claim 1, wherein 0.1 to 50 parts by mass of component (B) and 10 to 2000 parts by mass of component (C) are blended with respect to 100 parts by mass of component (A). Oil-in-water modified silicone emulsion composition.   The oil-in-water modified silicone emulsion composition according to any one of claims 1 to 5, further comprising 0.001 to 20 parts by mass of (D) an anionic surfactant with respect to 100 parts by mass of component (A). .   Furthermore, the oil-in-water modified silicone emulsion composition of any one of Claims 1 thru | or 6 which contains 0.001-20 mass parts of (E) antirust agents with respect to 100 mass parts of (A) component.   The oil-in-water modified silicone emulsion composition according to any one of claims 1 to 7, further comprising (F) a preservative in an amount of 0.001 to 2 parts by mass with respect to 100 parts by mass of the component (A). Furthermore, the oil-in-water modified silicone emulsion composition of any one of Claims 1 thru | or 8 which contains 0.001-2 mass parts of (G) pH adjusters with respect to 100 mass parts of (A) component.