KR20030059520A - Method for the preparation of an anionic type release emulsion of silicone - Google Patents

Abstract

The present invention relates to a method for preparing an anionic silicone release emulsion, and more particularly, a specific organopolysiloxane, a nonionic surfactant, an anionic surfactant, and water are introduced into a reactor in a predetermined amount and in a predetermined order, and using an emulsifier. Anionic silicone release emulsions having excellent stability and simple manufacturing are prepared by diluting a mixture obtained by emulsifying and dispersing a water-in-oil emulsion (W / O) emulsion into an oil-in-water emulsion (O / W) emulsion with water to prepare a silicone release emulsion. It relates to a manufacturing method of.

Description

Method for the preparation of an anionic type release emulsion of silicone

The present invention relates to a method for preparing an anionic silicone release emulsion, and more particularly, a specific organopolysiloxane, a nonionic surfactant, an anionic surfactant, and water are introduced into a reactor in a predetermined amount and in a predetermined order, and using an emulsifier. By adding water to the mixture obtained by emulsifying and dispersing a water-in-oil emulsion (W / O) emulsion into an oil-in-water emulsion (O / W) emulsion to prepare a silicone release emulsion, the anionic silicone is simple and has excellent stability. A method for producing a release emulsion.

Silicone release emulsions are useful as release agents for synthetic resins, rubber, paper, molds, etc., and are useful as softeners and leveling agents for natural fibers, organic fibers such as synthetic fibers, inorganic fibers such as glass fibers, and the like. It is considered an important issue.

There are many conventional techniques for silicone release emulsions, among which US Pat. No. 4,620,878 discloses a method of preparing an emulsion using an emulsifier and water in an organopolysiloxane, but this is a problem of inferior stability of the prepared emulsion. There is.

In addition, US Pat. No. 5,861,458, US Pat. No. 6,107,399, Canadian Pat. No. 2,183,299, and the like describe a method for preparing a silicone release emulsion by polymerization of diorganopolysiloxane, but this improves the stability of the silane monomer rotor polysiloxane. Including the polymerization process to be prepared, there is a disadvantage that the process is complicated and the manufacturing time is long.

Accordingly, the present inventors have put certain organopolysiloxane, nonionic surfactant, anionic surfactant, water into the reactor in a certain amount and order in order to compensate for the drawbacks of the conventional silicone release emulsion, and emulsified using an emulsifier. The present invention was completed by adding water to a mixture obtained by dispersing the water-in-oil (W / O) emulsion into a phase-transferring emulsion-in-water (O / W) emulsion to prepare a silicone release emulsion.

Accordingly, an object of the present invention is to provide a method for preparing an anionic silicone release emulsion having a simple manufacturing process and excellent stability.

In the present invention, 10 to 65 parts by weight of organopolysiloxane, 0.1 to 10 parts by weight of nonionic surfactant, and 0.1 to 10 parts by weight of anionic surfactant are added to the reactor and stirred, followed by 2 to 10 parts by weight of water (pre-mix). An anionic system prepared by adding 45-65 parts by weight of dilution to a mixture obtained by adding and emulsifying and dispersing using an emulsifier to phase-transfer a water-in-oil emulsion (W / O) emulsion into an oil-in-water emulsion (O / W) emulsion. A method for producing a silicone release emulsion is characterized by the above.

Referring to the present invention in more detail as follows.

The method for producing an anionic silicone release emulsion of the present invention is an organopolysiloxane, an anionic surfactant having a higher hydrophilicity than the nonionic surfactant with a nonionic surfactant having a HLB (Hydrophile Lipophile Balance) value of 11 to 15 as a surfactant and Water-in-oil emulsion was prepared by adding water and water in a certain order, and then emulsified and dispersed by mechanical high shear using an emulsifier to prepare an oil-in-water silicone release emulsion. .

Hereinafter, the components used in the preparation of the anionic silicone release emulsion of the present invention will be described in more detail.

In the present invention, the organopolysiloxane having a role of exhibiting the releasability is preferably a viscosity (25 ° C.) of 100 to 50,000 Cst, and a mixture of one or two or more of the organopolysiloxanes represented by the following general formula (1) is used. It is preferable to contain 10-65 weight part in all anionic silicone mold release emulsions, and if the content is less than 10 weight part, there exists a problem that a mold release effect falls, and when it exceeds 65 weight part, the stable O / W type emulsion is manufactured. There is a problem that is difficult to do.

In Formula 1, R includes an alkyl group or an aryl group or includes all of them, m is an integer of 0 to 50, n is an integer of 5 to 200.

Especially as organopolysiloxane represented by the said Formula (1), it is preferable to use polydimethylsiloxane, an alkyl-group containing polysiloxane (decyl-modified polysiloxane or dodecyl-modified polysiloxane).

In the present invention, the nonionic surfactant is contained 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight in the total anionic silicone release emulsion, and if the content is less than 0.1 parts by weight, the stability of the emulsion becomes insufficient, and 10 parts by weight. When the amount is exceeded, there is a problem that the releasability and heat resistance of the organopolysiloxane emulsion obtained are lowered. The nonionic surfactants are those having a HLB (Hydrophile Lipophile Balance) value of 11 to 15, and are polyoxyalkylene alkyl ethers, polyoxyalkenylene sorbitan alkyl esters, polyoxyalkylene alkyl esters, and polyoxyalkylene alkylphenol ethers. It may be selected from among those, more preferably alcohol ethoxylate-based or polyoxyethylated alkyl alcohol type is preferred.

Here, the HLB (Hydrophile Lipophile Balance) is a numerical value indicating the hydrophilicity or hydrophobicity of the surfactant proposed by Griffin, ATLAS, USA. That is, the HLB value of a nonionic surfactant is shown by the numerical value of 0-20, and the calculation method is as follows.

HLB value of nonionic surfactant

= (Molecular weight of hydrophilic moiety ÷ surfactant molecular weight) × 100/5

= (Hydrophilic weight ÷ (hydrophobic weight + hydrophilic weight)) × 100/5

Therefore, in case of paraffin without any hydrophilic group, the HLB value is 0, and only the hydrophilic group like polyethylene glycol has an HLB value of 20, and in the case of polyoxyethylene lauryl ether, there are various kinds of polyoxyethylene groups depending on the amount of the hydrophilic group. It has an HLB value. In addition, the anionic or cationic surfactants cannot be calculated for the HLB value because the hydrophilic groups of the surfactants are different and the proportion of the hydrophilic groups is larger than that of the nonionic surfactants. Therefore, for the ionic surfactant, a method of emulsifying the standard material (oil or wax) to emulsify and experimentally determining the HLB value according to the degree of emulsification is used.

And, in the present invention, the anionic surfactant used together with the nonionic surfactant as the emulsifier contains 0.1 to 10 parts by weight, preferably 0.1 to 5 parts by weight in the total anionic silicone release emulsion, and if the content is 0.1 If it is less than the part, the stability of the emulsion becomes insufficient, and if it exceeds 10 parts by weight, there is a problem that the releasability and heat resistance of the resulting organopolysiloxane emulsion are lowered. As the anionic surfactant, it is preferable to use a hydrophilic one having a higher hydrophilicity than the nonionic surfactant used together. This means that a surfactant having a high hydrophilicity is strongly adsorbed to water and a surfactant having a relatively small hydrophilicity is adsorbed toward the oil. This is because a more stable emulsion can be formed. Such anionic surfactants include alkyl sulfates (e.g. lauryl sulfate), alkylbenzenesulfonic acids and salts (e.g. hexylbenzenesulfonic acid, octylbenzenesulfonic acid, decylbenzenesulfonic acid, dodecylbenzenesulfonic acid, cetylbenzenesulfonic acid And myristylbenzenesulfonic acid), sulfate esters of monoalkyl polyoxyethylene ethers, alkylnaphthylsulfonic acids, alkali metal sulforesinates, alkali metal alkyl sulfonates, ester sulfates and alkylarylsulfonates, More preferably, the alkoxylate sulfonate series is preferable.

In particular, the present invention uses a nonionic surfactant together with an anionic surfactant having a higher hydrophilicity than the nonionic surfactant as a surfactant to be used as an emulsifier to prepare an emulsion, thereby making the hydrophilic anionic surfactant strongly resistant to water. Nonionic surfactants which adsorb and have relatively small hydrophilicity are adsorbed towards the organopolysiloxane oil to form a more stable emulsion, which is characterized by improving the stability of the final silicone release emulsion produced.

In the present invention, the water (pre-mix) emulsifying and dispersing the organopolysiloxane in water is preferably contained in 2 to 10 parts by weight in the total anionic silicone release emulsion, if the content is less than 2 parts by weight of hydrophobic oil Since the amount of phosphorus organopolysiloxane is too large, the emulsion does not phase change from water-in-oil type (W / O) to oil-in-water type (O / W), and water does not become a continuous phase. When the amount exceeds 10 parts by weight, the concentration of organopolysiloxane is increased. Too low, there is a problem that the efficiency of emulsification is lowered.

If described in more detail with respect to the production method of the anionic silicone release emulsion of the present invention using the above components.

First, an organopolysiloxane, a nonionic surfactant, and an anionic surfactant are added to a reactor, mixed, and then stirred at a stirring speed of 200 to 600 rpm at room temperature (25 ° C.) for 10 minutes to 2 hours, and then water is added thereto. And gently stirred at a stirring speed of 10 to 150 rpm for 10 minutes to 2 hours to prepare an emulsion in water (W / O).

The prepared oil-in-water (W / O) emulsion was emulsified and dispersed by applying a mechanical high shear using an emulsifier to phase-transfer the oil-in-water (W / O) emulsion into an oil-in-water (O / W) emulsion. Anionic silicone release emulsion may be prepared by adding ˜65 parts by weight of water (Dilution) and stirring at 300 to 500 rpm for 30 minutes to 4 hours. In the emulsifier, a homer mixer, azihom mixer ^TM , a combi mixer ^TM , a colloid mill, or the like may be used. In addition, there is a problem that the emulsion becomes unstable if the amount of water to be diluted after the phase transition by applying mechanical high shear is out of the above range.

As described above, the present invention mixes an organopolysiloxane, a nonionic surfactant, an anionic surfactant having a higher hydrophilicity than the nonionic surfactant, water, and the like in a predetermined amount and a certain order to prepare a water-in-oil emulsion, and then use an emulsifier. By emulsifying and dispersing the mechanical high shear to give an oil-in-water emulsified emulsion release emulsion, it has the characteristics, while improving the stability has a simple manufacturing process advantages.

The anionic silicone release emulsion prepared by the method of the present invention as described above was excellent in stability of the emulsion with an average particle diameter of 200 to 300 nm.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited by Examples.

Example 1

Next, organopolysiloxane (viscosity 390 Cst / 25 ° C), nonionic surfactant, and anionic surfactant were added to the reactor in the content shown in Table 1, stirred at 200 to 400 rpm with a mixer, and then the stirring speed was 1 to 150 rpm. Lowered and slowly added dropwise water (pre-mix). Subsequently, this is emulsified and dispersed with a colloid mill (premier), followed by phase change. After adding water (dilution) thereto, the stirring speed is increased to 300 to 500 rpm, and the mixture is stirred for 5 hours to prepare an anionic silicone release emulsion. It was.

The average particle diameter of the anionic silicone mold release emulsion prepared by the above method was measured by a "laser light scattering particle size analysis measuring apparatus (manufactured by Melbourne)", and the average particle diameter was 220 nm. In addition, the anionic silicone release emulsion was centrifuged at 12000 rpm for 15 minutes at 25 ° C. with a centrifuge to obtain a stable milky white emulsion in which only 5-7% of the total emulsion was separated. For reference, existing products are separated by more than 14-20%. Even if the emulsion was left at room temperature for 12 months, no separation of layers was observed and it was confirmed that the emulsion showed excellent stability.

Comparative Example 1

Anionic silicone releasing emulsion was prepared in the same manner as in Example 1 with the amounts shown in Table 1. At this time, the viscosity of the organopolysiloxane was 390 Cst / 25 degreeC.

The average particle diameter of the anionic silicone mold release emulsion prepared in the same manner as in Example 1 was measured, the average particle diameter was 520 nm. In addition, the anionic silicone release emulsion was centrifuged at 12,000 rpm for 15 minutes at 25 ° C. with a centrifuge to obtain a milky white emulsion in which 25 to 40% of the total emulsion was separated. This emulsion was left at room temperature for 1 month, and two layers of separation were confirmed.

Example 2

Anionic silicone releasing emulsion was prepared in the same manner as in Example 1 with the amounts shown in Table 1. At this time, the viscosity of the organopolysiloxane was 12000 Cst / 25 degreeC.

The average particle diameter of the anionic silicone releasing emulsion prepared in the same manner as in Example 1 was measured, the average particle diameter was 230 nm. In addition, the anionic silicone release emulsion was centrifuged at 12,000 rpm for 15 minutes at 25 ° C. with a centrifuge to obtain a stable milky white emulsion in which only 2 to 3% of the total emulsion was separated. Even if the emulsion was left at room temperature for 12 months, no separation of layers was observed and it was confirmed that the emulsion showed excellent stability.

Comparative Example 2

Anionic silicone releasing emulsion was prepared in the same manner as in Example 1 with the amounts shown in Table 1. At this time, the viscosity of the organopolysiloxane was 12000 Cst / 25 ℃, the stirring speed was 300 ~ 400 rpm, 1 ~ 150 rpm.

The average particle diameter of the anionic silicone release emulsion prepared in the same manner as described above was measured in the same manner as in Example 1, the average particle diameter was 550 nm. In addition, the anionic silicone release emulsion was centrifuged at 12,000 rpm for 15 minutes at 25 ° C. with a centrifuge to obtain a milky white emulsion in which 65 to 85% of the total emulsion was separated. This emulsion was left at room temperature for 1 month, and two layers of separation were confirmed.

Example 3

Anionic silicone releasing emulsion was prepared in the same manner as in Example 1 with the amounts shown in Table 1. At this time, the viscosity of the organopolysiloxane was 500 Cst / 25 ℃, the stirring speed was 300 ~ 400 rpm, 1 ~ 150 rpm.

The average particle diameter of the anionic silicone release emulsion prepared in the same manner as described above was measured in the same manner as in Example 1, the average particle diameter was 190 nm. In addition, the anionic silicone release emulsion was centrifuged at 12000 rpm for 15 minutes at 25 ° C. with a centrifuge to obtain a stable milky white emulsion in which only 5-7% of the total emulsion was separated. Even if the emulsion was left at room temperature for 12 months, no separation of layers was observed and it was confirmed that the emulsion showed excellent stability.

Comparative Example 3

Anionic silicone releasing emulsion was prepared in the same manner as in Example 1 with the amounts shown in Table 1. At this time, the viscosity of the organopolysiloxane was 500 Cst / 25 ℃, the stirring speed was 300 ~ 400 rpm, 1 ~ 150 rpm.

The average particle diameter of the anionic silicone release emulsion prepared in the same manner as in Example 1 was measured, the average particle diameter was 480 nm. In addition, the anionic silicone release emulsion was centrifuged at 12,000 rpm for 15 minutes at 25 ° C. with a centrifuge to obtain a milky white emulsion in which 65 to 85% of the total emulsion was separated. This emulsion was left at room temperature for 1 month, and two layers of separation were confirmed.

Comparative Example 4

Anionic silicone releasing emulsion was prepared in the same manner as in Example 1 with the amounts shown in Table 1. At this time, the viscosity of the organopolysiloxane was 500 Cst / 25 ℃, the stirring speed was 300 ~ 400 rpm, 1 ~ 150 rpm.

The average particle diameter of the anionic silicone releasing emulsion prepared in the same manner as in Example 1 was measured, the average particle diameter was 450 nm. In addition, the anionic silicone release emulsion was centrifuged at 12000 rpm for 15 minutes at 25 ° C. with a centrifuge to obtain a milky white emulsion in which 30-40% of the total emulsion was separated. This emulsion was left at room temperature for 1 month, and two layers of separation were confirmed.

Comparative Example 5

Anionic silicone releasing emulsion was prepared in the same manner as in Example 1 with the amounts shown in Table 1. At this time, the viscosity of the organopolysiloxane was 500 Cst / 25 ℃, the stirring speed was 300 ~ 400 rpm, 1 ~ 150 rpm.

The average particle diameter of the anionic silicone release emulsion prepared in the same manner as in Example 1 was measured, the average particle diameter was 510 nm. In addition, the anionic silicone release emulsion was centrifuged at 12000 rpm for 15 minutes at 25 ° C. with a centrifuge to obtain a milky white emulsion in which 30-40% of the total emulsion was separated. This emulsion was left at room temperature for 1 month, and two layers of separation were confirmed.

As described above, in the method for preparing an anionic silicone release emulsion according to the present invention, an organopolysiloxane, a nonionic surfactant, an anionic surfactant having a higher hydrophilicity than the nonionic surfactant, water, and the like are mixed in a predetermined content and in a certain order. After the water-in-oil emulsion is prepared by emulsifying and dispersing the mechanical high shear using an emulsifier to produce an oil-in-water silicone release emulsion has the characteristics, while improving the stability, the manufacturing process has a simple advantage.

Claims (5)

10 to 65 parts by weight of organopolysiloxane, 0.1 to 10 parts by weight of the nonionic surfactant, and 0.1 to 10 parts by weight of the anionic surfactant are added to the reactor and stirred, and then emulsified by adding 2 to 10 parts by weight of water (pre-mix). Anion, characterized in that prepared by adding 45 to 65 parts by weight of water (dilution) to the mixture obtained by phase-transferring an oil-in-water (W / O) emulsion into an oil-in-water (O / W) emulsion by emulsion dispersion. Method for producing a silicone release emulsion. The method of claim 1, wherein the organopolysiloxane is a viscosity (25 ℃) of 100 to 50,000 Cst of the organopolysiloxane represented by the following formula (1) or a mixture of two or more kinds of anionic silicone release emulsion, characterized in that Manufacturing method. Formula 1 In Formula 1, R includes an alkyl group or an aryl group or includes all of them, m is an integer of 0 to 50, n is an integer of 5 to 200. The method of claim 1, wherein the nonionic surfactant has a HLB (Hydrophile Lipophile Balance) of 11 to 15, characterized in that the manufacturing method of the anionic silicone release emulsion. The method of claim 1 or 3, wherein the nonionic surfactant is selected from polyoxyalkylene alkyl ethers, polyoxyalkenylene sorbitan alkyl esters, polyoxyalkylene alkyl esters and polyoxyalkylene alkylphenol ethers. A method for producing an anionic silicone release emulsion. The method of claim 1, wherein the anionic surfactant is lauryl sulfate, alkylbenzene sulfonic acid, sulfate ester of monoalkyl polyoxyethylene ether, alkyl naphthyl sulfonic acid, alkali metal sulforesinate, alkali metal alkyl sulfonate, ester Method for producing an anionic silicone release emulsion, characterized in that selected from sulfate and alkylarylsulfonate.