JPH04285665A - Organopolysiloxane emulsion composition - Google Patents

Abstract

PURPOSE:To obtain an organopolysiloxane composition capable of maintaining low viscosity even when content of the organopolysiloxane is increased and, simultaneously, having excellent storage stability, dilution stability and mechanical stability. CONSTITUTION:An O/W type organopolysiloxane emulsion composition consisting of (A) 100 pts.wt. of an organopolysiloxane expressed by the average composition formula, R<1>a SiO(4-a)/2, (B) 1-50 pts.wt. of a polyoxyethylene alkyl ether expressed by the general formula, R<2>O(C2H4O)nH, (C) 0.01-10 pts.wt. of a polyoxyethyele alkyl ether sulfide expressed by the general formula R<3>O(C2 H4O)nSO3M and water.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to organopolysiloxane compositions, and more particularly to O/W type organopolysiloxane emulsion compositions having excellent storage stability, dilution stability and mechanical stability.

0002

BACKGROUND OF THE INVENTION Organopolysiloxane emulsion compositions are used in many fields as fiber treatment agents, mold release agents, and the like. Conventional organopolysiloxane emulsion (
(hereinafter simply referred to as emulsion), when the content of organopolysiloxane, which is the dispersoid, is increased, the viscosity of the emulsion increases, making it difficult to extract from the container, and it takes a long time to dilute with water etc. etc,
There was a drawback in terms of workability. Therefore, in the past, the upper limit of the organopolysiloxane content in an emulsion composition was generally considered to be 40%.

0003

[Problems to be Solved by the Invention] Furthermore, since the organopolysiloxane as a dispersoid has strong hydrophobicity, when the emulsion composition is stored, the organopolysiloxane separates and the emulsion is destroyed, resulting in poor storage stability. It lacks. Furthermore, when diluting the emulsion, the emulsion is destroyed, resulting in a lack of dilution stability, and when stirring, the emulsion is also destroyed, resulting in a lack of mechanical stability.

[0004] As a method to improve these drawbacks, organopolysiloxane emulsion compositions have been developed using the so-called emulsion polymerization method, in which a low-molecular cyclic organopolysiloxane is used as a starting material and polymerized in an emulsion dispersion system using a strong acid or a strong alkali as a catalyst. Methods of manufacturing things
95, Japanese Patent Publication No. 44-20116) is known and has already been widely put into practical use, but even in the case of this emulsion composition, the storage stability and dilution stability are considerably improved, but the strong mechanical shearing force The stability against

[0005] Furthermore, in the above production method, the emulsifier that can be used is limited to anionic or cationic surfactants, so when the obtained emulsion composition is used in combination with other drugs, the surfactant The disadvantage is that the use of the emulsion composition is limited due to the ionicity of the emulsion composition.

Furthermore, in the above production method, about 10% of the starting material, low-molecular-weight cyclic siloxane, remains unpolymerized, so when the resulting emulsion is used, it volatilizes and becomes white due to thermal oxidation in the drying process. powder is produced,
This has disadvantages such as adhesion to surrounding surfaces, causing a repelling phenomenon on the paint, and causing contact failures in nearby electrical equipment.

[0007] It has also been proposed to improve mechanical stability by adding sodium polyoxyethylene alkylphenyl ether sulfate to an aqueous emulsion of diorganopolysiloxane (Japanese Patent Publication No. 53-13).
501). In this case, although the mechanical stability is certainly improved, the effect of suppressing the increase in viscosity accompanying the increase in the organopolysiloxane content is poor.

As a result of intensive studies to solve the above drawbacks, the present inventors have developed an O/W type organopolysiloxane consisting of organopolysiloxane of a certain composition, polyoxyethylene alkyl ether, polyoxyethylene alkyl ether sulfate, and water. The emulsion composition can maintain low viscosity even if the content of organopolysiloxane is increased more than before, and also has excellent storage stability, dilution stability, mechanical stability, etc. as an emulsion. Heading The present invention has been arrived at.

Therefore, an object of the present invention is to provide an organopolysiloxane emulsion composition that can maintain a low viscosity even when the content of organopolysiloxane is increased and has excellent storage stability, dilution stability, and mechanical stability. Our goal is to provide the following.

0010

[Means for Solving the Problems] The above objects of the present invention are (
A): 100 parts by weight of an organopolysiloxane represented by the average composition formula R1 a SiO(4-a)/2, (B): Polyoxyethylene alkyl ether 1 represented by the general formula R2 O(C2 H4 O) m H ~50 parts by weight, (c): polyoxyethylene alkyl ether sulfate represented by the general formula R3O(C2H4O)nSO3M 0.01~
This was achieved using an O/W type organopolysiloxane emulsion composition consisting of 10 parts by weight and (d) water.

The above average compositional formula R1 a SiO(4-a
)/2 In the organopolysiloxane as component (a), R1 in the formula represents a hydrogen atom or a monovalent organic group, and a has a value of 1.9 to 2.1.

Specific examples of R1 include alkyl groups such as methyl group, ethyl group, isopropyl group, t-butyl group, octyl group, lauryl group, and stearyl group, alkenyl groups such as vinyl group and allyl group, and phenyl group. , tolyl group, aryl group such as naphthyl group, aralkyl group such as 2-phenylethyl group, cycloalkyl group such as cyclopentyl group, cyclohexyl group, epoxy group, amino group, methacryloxy group, carboxyl group, cyano group, polyoxyalkylene Examples include, but are not limited to, a mercapto group, a hydroxy group, and an alkoxy group such as a methoxy group and an ethoxy group. In particular, it is preferable that 90 mol% or more is a methyl group.

[0013] The above general formula R2 O (C2 H4 O
) m In the polyoxyethylene alkyl ether as component (b) represented by H, R2 in the formula represents a monovalent hydrocarbon group having 12 to 22 carbon atoms. Specific examples of R2 include, but are not limited to, saturated hydrocarbon groups such as lauryl, tridecyl, tetradecyl, cetyl, and stearyl, and unsaturated hydrocarbon groups such as oleyl. It's not something you can do.

Further, m represents the number of moles of ethylene oxide added. The number of m is not particularly limited as long as it is 1 or more, but
From the viewpoint of the emulsifying dispersibility of organopolysiloxane in water, the number is preferably 5 to 20. The above component (b) can also be used in combination of two or more.

Component (B) is preferably blended in an amount of 1 to 50 parts by weight, particularly preferably 5 to 30 parts by weight, per 100 parts by weight of the organopolysiloxane (I).

If it is less than 1 part by weight, it is not possible to obtain an emulsion composition with good emulsification and dispersion stability, and if it is more than 50 parts by weight, a large amount of component (b) remains as a non-volatile component. This will impede the characteristics.

The polyoxyethylene alkyl ether sulfate as component (c) that can be used in the present invention is:
It is represented by the general formula R3 O(C2 H4 O)n SO3 M, and R3 in the formula has 12 to 22 carbon atoms.
is a monovalent hydrocarbon group, and is the same as R2 above. Similarly to m above, n in the formula represents the number of moles of ethylene oxide added, and is not particularly limited as long as it is 1 or more. From the viewpoint, it is preferable to set it as 1-10.

M in the formula represents an alkali metal or an ammonium group. Specific examples of M include sodium,
Examples include, but are not limited to, potassium and mixtures thereof.

The amount of polyoxyethylene alkyl ether sulfate as component (c) is 0.01 to 1 part by weight per 100 parts by weight of organopolysiloxane as component (a).
The amount is preferably 0 parts by weight, particularly preferably 0.1 to 5 parts by weight. When the amount is less than 0.01 parts by weight, there is no effect on reducing the viscosity and improving the mechanical stability of the emulsion composition, and when it is more than 10 parts by weight, the viscosity of the emulsion composition increases.

There is no particular restriction on the amount of water as component (2) used in the present invention, but it is 50 to 30 parts by weight per 100 parts by weight of the organopolysiloxane as component (a).
It is preferable to set it as 0 parts by weight, and in particular, since the emulsion composition of the present invention has the effect of suppressing an increase in viscosity, it can be reduced to 50 to 150 parts by weight.

The organopolysiloxane emulsion composition of the present invention comprises organopolysiloxane as component (a) produced by a known method, and polyoxyethylene alkyl ether as component (b) and polyoxyethylene as component (c) as emulsifiers. It can be produced by adding an alkyl ether sulfate and emulsifying and dispersing the resulting mixture in water using a high shear emulsifying and dispersing machine such as a homomixer, colloid mill, or high-pressure homogenizer.

[0022] There are no particular restrictions on the emulsifying machine, equipment, and manufacturing method used in this case, and they may be selected depending on the viscosity of the organopolysiloxane used as the dispersoid. In addition, only the polyoxyethylene alkyl ether of the component (B) is first added as an emulsifier to the organopolysiloxane of the component (A), and the polyoxyethylene alkyl ether of the component (B) is emulsified and dispersed in water to form an emulsion.
The emulsion composition of the present invention can also be produced by adding and mixing the component polyoxyethylene alkyl ether sulfate. Incidentally, known preservatives, penetrants, etc. can also be added to the emulsion composition of the present invention.

[0023]

[Effects of the Invention] The organopolysiloxane emulsion composition of the present invention does not cause an increase in viscosity even when the organopolysiloxane content is increased, so it is extremely easy to handle, such as being able to be easily extracted from a container. For example, when used as a fiber treatment agent, the workability is extremely good.

Furthermore, since the content of organopolysiloxane can be increased, it is possible to use it as a highly concentrated organopolysiloxane composition, which not only greatly expands the range of uses but also reduces transportation costs. Can be done. Furthermore, the organopolysiloxane emulsion composition of the present invention has excellent storage stability, dilution stability, and mechanical stability.

[0025]

EXAMPLES The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited thereto.

[0026]

[Example 1] Preparation of emulsion A In a 2 liter beaker, the viscosity at 25°C was 100.
500 g of dimethylpolysiloxane of 0 cs, 25 g of polyoxyethylene lauryl ether (added with 5 moles of ethylene oxide), 25 g of polyoxyethylene lauryl ether (added with 20 moles of ethylene oxide), and sodium polyoxyethylene lauryl ether sulfate (added with 5 moles of ethylene oxide). 0.5g of the product) was mixed uniformly using a homomixer, and then 500g of water was gradually added to perform emulsification and dispersion.Then, the resulting dispersion was passed through a high-pressure homogenizer once at a pressure of 300Kg/cm2, Emulsion A having an organopolysiloxane content of 47.6% by weight was obtained.

[0027]

Comparative Example 1 Preparation of Emulsion B Emulsion B was prepared in exactly the same manner as in Example 1, except that the sodium polyoxyethylene lauryl ether sulfate used in Example 1 was not used.

Next, the following tests were conducted on the obtained emulsions A and B. (1) Emulsion viscosity: The viscosity of the emulsion composition at 25° C. was measured using a BM rotational viscometer. (2) Storage stability: 100 g of the emulsion was placed in a glass bottle, left at room temperature, and visually observed. (3) Dilution stability: 2 g of the emulsion was placed in a 200 ml beaker, diluted with 98 g of water, and the surface condition was visually observed after leaving to stand for 24 hours. (4) Mechanical stability: Put 4 g of the emulsion in a 300 ml beaker, dilute with 196 g of water, stir with a homomixer at 5000 rpm for 10 minutes, and then
The surface condition when the bubbles disappeared was visually observed. The test results are shown in Table 1.

[0029]

[Table 1] ──────────────────────────
──────────
Example 1
Comparative example 2
(Emulsion A)
(Emulsion B)──────────────
──────────────────────── (1)
Emulsion viscosity 150cp
3800cp────────────
──────────────────────────(
2) Storage stability No separation for more than 6 months Separation after 2 months──────
──────────────────────────
────(3) Dilution stability
Good, oil floating────────────────────
──────────────── (4) Mechanical stability
Good
There is oil floating──────────
──────────────────────────

[0030]

[Example 2] Preparation of emulsion composition C In a 1 liter beaker, dimethylpolysiloxane 500 having silanol groups at both ends and having a viscosity of 20,000 cs at 25° C.
g, 60 g of polyoxyethylene tridecyl ether (adduct of 10 moles of ethylene oxide), 1 g of sodium polyoxyethylene tridecyl ether sulfate (adduct of 5 moles of ethylene oxide), and 60 g of water were mixed and passed through a colloid mill to concentrate. An emulsified dispersion was obtained.

Next, 496.8 g of the obtained emulsified dispersion
was placed in a 1 liter beaker, then stirred and diluted by adding 352 g of water, resulting in an organopolysiloxane content of 47.5
An emulsion of % by weight was obtained.

[0032]

[Example 3] Preparation of emulsion composition D An emulsion composition was prepared in the same manner as in Example 2, except that 60 g of polyoxyethylene tridecyl ether (10 mole adduct of ethylene oxide) used in Example 2 was changed to 10 g. Obtained.

[0033]

[Example 4] Preparation of emulsion composition E 1 g of sodium polyoxyethylene tridecyl ether sulfate (5 moles of ethylene oxide adduct) used in Example 2 was
An emulsion composition was obtained in the same manner as in Example 2 except that the emulsion composition was changed to g.

[0034]

[Comparative Example 2] Preparation of emulsion composition F In a 2 liter beaker, 500 octamethylcyclotetrasiloxane was added.
Then, 50 g of a 10% by weight aqueous dodecylbenzenesulfonic acid solution was gradually added to emulsify and disperse the mixture while stirring with a homomixer, and then 450 g of water was further added to obtain an emulsified dispersion.

[0035] The obtained emulsified dispersion was heated at 50°C for 24 hours to carry out a polymerization reaction, and then the obtained polymerization reaction product was
The mixture was cooled to 5°C, and then neutralized by adding a 10% by weight aqueous sodium carbonate solution. While stirring the resulting neutralized product, 10 g of sodium polyoxyethylene nonylphenyl ether sulfate (3 mole adduct of ethylene oxide) was added and mixed uniformly, until the organopolysiloxane content was 49.
．． A 3% by weight emulsion composition was obtained.

[0036]

[Comparative Example 3] Preparation of emulsion composition G Same as Example 1 except that sodium polyoxyethylene lauryl ether sulfate used in Example 1 was replaced with sodium polyoxyethylene nonylphenyl ether sulfate (3 mole ethylene oxide adduct). An emulsion composition was obtained in exactly the same manner.

[0037]

[Example 5] Preparation of emulsion composition H In a 2 liter beaker, the following structural formula was added.

[Chemical formula 1]

500 g of epoxy-modified organopolysiloxane shown below, 15 g of polyoxyethylene lauryl ether (adduct of 5 moles of ethylene oxide), polyoxyethylene lauryl ether (20 g of ethylene oxide),
50 g of molar adduct) and 1 g of sodium polyoxyethylene lauryl ether sulfate (5 molar adduct of ethylene oxide) were charged and mixed uniformly using a homomixer, and then 500 g of water was gradually added to perform emulsification and dispersion.

The obtained emulsified dispersion was passed once through a high-pressure homogenizer at a pressure of 300 kg/cm to obtain an emulsion composition having an organopolysiloxane content of 46.9% by weight. The emulsion compositions (C, D, E, F, G, and H) prepared in Examples 2 to 5 and Comparative Examples 2 to 3 were tested in exactly the same manner as described above. The results are shown in Table 2.

[Table 2]

Claims (1)

[Claims] Claim 1: (A): Average composition formula R1 a SiO(4-a)/2 (wherein R1 represents a hydrogen atom or a monovalent organic group, and a has a value of 1.9 to 2.1. Organopolysiloxane 100 represented by
Parts by weight, (b): Represented by the general formula R2O(C2H4O)mH (wherein R2 represents a monovalent hydrocarbon group having 12 to 22 carbon atoms, and m is an integer of 1 or more.) 1 to 50 parts by weight of polyoxyethylene alkyl ether; An O/W type organopolysiloxane emulsion consisting of 0.01 to 10 parts by weight of a polyoxyethylene alkyl ether sulfate (representing an ammonium group, and n is an integer of 1 or more), and (d): water. Composition.