JPS5950179B2 - Silicone emulsion composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a silicone emulsion composition obtained by emulsion polymerization, which has excellent stability especially when used in combination with cationic or nonionic substances.

Polyorganosiloxanes are generally insoluble in water.

To disperse this in water, the polyorganosiloxane obtained by polymerizing a low molecular weight polyorganosiloxane with an acidic or alkaline catalyst in advance is mixed with an emulsifier and water, and the mixture is emulsified using an emulsifying machine. There is a method in which low molecular weight organosilicon compounds are subjected to emulsion polymerization in the presence of water and a substance that serves as an emulsifier and a polymerization catalyst. The former method, that is, the method of emulsifying polyorganosiloxane, produces a stable oil-in-water emulsion of polyorganosiloxane when the degree of polymerization is relatively low (below 1000), but when the degree of polymerization exceeds 1000, , it is difficult to obtain a stable emulsion. On the other hand, the method of obtaining polyorganosiloxane by emulsion polymerization from a low-molecular-weight organosilicon compound makes it relatively easy to obtain a stable oil-in-water emulsion of polyorganosiloxane with an arbitrary degree of polymerization. . However, the emulsifier/polymerization catalyst used in this emulsion polymerization is alkylbenzenesulfonic acid (Japanese Patent Publication No. 41-13995), alkyl hydrogen sulfate (Japanese Patent Publication No. 43-18800), and polyoxyethylene alkyl sulfate ester (Japanese Patent Publication No. 46-1989). 41
038), all of which are anionic surfactants,
Since the resulting emulsions are all anionic, their range of use is limited. For example, it is known to use silicone emulsions as fabric softeners, but these anionic emulsions
Dyeing and softening cannot be done at the same time using cationic dyes. It is also known that silicone treatment is applied to fabrics to give them water repellency, flexibility, wrinkle resistance, elasticity, and stretch back properties, but most fibers do not have a negative charge in the presence of water. In such an emulsion, the silicone simply adheres to the surface of the fibers due to ion repulsion, and does not exhibit a uniform and strong bond. On the other hand, a method in which a low molecular weight organosiloxane is emulsified using a cationic surfactant such as a quaternary ammonium salt as an emulsifier, and then a strong mineral acid or a strong alkali is added as a polymerization catalyst to emulsify it
4-2041), which produces salt as a by-product when the catalyst is neutralized after the polymerization is completed, which significantly impairs the stability of the emulsion.

The present invention covers these matters. To provide a cation-modified silicone emulsion composition which improves the disadvantages of the above, exhibits excellent stability when used in combination with cationic or nonionic substances, and provides strong bonding to fiber surfaces. That is, the present invention provides an anionic silicone emulsion (
0.5 to 20 parts by weight of a water-soluble or water-dispersible ethylene oxide-adducted alkylamine derivative (B) per 100 parts by weight of polyorganosiloxane in the prisoner component is added to 9. This is a silicone emulsion composition prepared by adjusting the composition to 9. The component used in the present invention is an anionic silicone emulsion containing as a component a polyorganosica xane obtained by emulsion polymerization of a low-molecular organosilicon compound with an anionic surfactant. , there are no particular restrictions on its configuration.

Further, the polyorganosiloxane in the (self) component is not particularly limited, and is a monofunctional unit [RlR2R3SiO.

．． , ], difunctional unit [R4R5SiO], trifunctional unit [R6SiO, . , ] and tetrafunctional units [SiO2
) (wherein Rl, R2, R3, R
4, R5, and R6 are each a group selected from a hydrogen atom or a monovalent hydrocarbon group, and may be the same or different. ). It may also contain a hydroxyl group at the end of the molecule. In order to easily obtain a stable emulsion with a desired degree of polymerization, 80% by weight or more of the polyorganosiloxane is difunctional siloxane units, and among these, 80% or more of the polyorganosiloxane is (CH3)2Si0. It is desirable to consist of units from the viewpoint of industrial availability of raw organosilicon compounds and the effect of imparting flexibility to fibers. However, polyorganosiloxanes containing up to 80% by weight of difunctional siloxane units, such as emulsions of resinous polyorganosiloxanes, are also acceptable as the carrier component of the present invention. The polyorganosiloxane in the silicone emulsion of the present invention is selected to have any degree of polymerization.

Further, the concentration of polyorganosiloxane can be arbitrarily selected, but a value of 10 to 50% by weight is most advantageous in obtaining a stable emulsion. Such an anionic silicone emulsion can be obtained by a conventionally known emulsion polymerization method. Component (B) used in the present invention is an additive for making the anionic emulsion containing polyorganosiloxane cationic, and is a water-soluble or water-dispersible alkylamine with ethylene oxide added and its derivatives. A surfactant selected from, for example, polyoxyethylene anhydroalkylamine,
These include polyoxyethylene oleylamine, polyoxyethylene tallow alkylamine, and polyoxyethylene tallow alkylpropylene diamine.

Primary amines, tertiary amines, diamines, and quaternary ammonium salts to which ethylene oxide is not added do not give satisfactory results for this purpose. Also, even if ethylene oxide is added, if it is not easily dissolved or dispersed in water, when added to an anionic emulsion,
Damage to the stability of the mulch. In preparing the polyorganosiloxane emulsion composition of the present invention,
The surfactant (B) is added in an amount of 0.5 to 20 parts by weight based on 100 parts by weight of the polyorganosiloxane in the (self) component.

If component (B) is less than 0.5 parts by weight, the effect of cationic modification, which is the objective of the present invention, will be small, while if it exceeds 20 parts by weight, the viscosity of the emulsion will increase and silicone will coagulate, resulting in stabilization of the emulsion. This is because the quality decreases. Moreover, the composition obtained in this way has a pH of 7 to 7.
It is necessary to adjust the distance to a range of 9, and more preferably to a range of 7 to 8.

Generally, when neutralizing an emulsion obtained by emulsion polymerization using an anionic emulsifier, a trace amount of amine, such as triethanolamine, is added to make it weakly alkaline with a pH of 7 or higher, but it is not excessively alkaline, that is, alkaline with a pH of 9 or higher. In this case, even if component (B) is added, the emulsion remains anionic and the effect of cationic modification cannot be obtained. The polyorganosiloxane emulsion composition of the present invention exhibits cationic properties. This means that
When an electrode is inserted into an emulsion using direct current electrolysis, the emulsion aggregates at the H electrode and polyorganosiloxane precipitates, but this can be proven by the fact that no aggregation or precipitation occurs at the electrode. The emulsion composition of the present invention has excellent stability when used in combination with cationic or nonionic substances, such as cationic dyes or other cationic fiber treatment agents. Since the organosiloxane ionically attracts and strongly bonds with the fiber surface, polyorganosiloxane treatment can impart excellent water repellency, flexibility, wrinkle resistance, elasticity, and stretch back properties to the fiber.

Furthermore, the cation-modified silicone emulsion composition of the present invention thus obtained can be used in combination with an emulsion in which polyorganosiloxane is emulsified with a nonionic emulsifier, without emulsion polymerization, to treat textiles.

Next, the present invention will be explained in further detail by giving examples of the present invention.

In the examples, all parts are parts by weight. Example 1 35 parts of octamethylcyclotetrasiloxane, 64 parts of water.
After uniformly stirring 4 parts of dodecylbenzenesulfonic acid and 0.6 parts of dodecylbenzenesulfonic acid with a homomixer, Manton-Gorlin (M
An emulsion was obtained by emulsifying at a pressure of 6,500 psi using a pressure homogenizer manufactured by Ant On Gaulln.

The emulsion was heated to 75°C with stirring and held for 3 hours, then cooled and held at room temperature for an additional 4 hours to complete the polymerization, and triethanolamine was added with stirring to pH the emulsion. was adjusted to 7.5. This product was found to be polydimethylsiloxane with a viscosity of 250,000 cp by destroying the emulsion with isopropyl alcohol, drying the oil layer at 150° C. for 3 to 4 hours to remove the alcohol, and measuring the viscosity. Sample A-L1 in which 2 parts of various surfactants were added to 100 parts of the emulsion thus obtained as shown in Table 1.
and Sample M without any additives was prepared.

The following experiments were conducted on these samples.

Experiment 1 Stability test in combination with cationic substances 100 g of each of the above samples was placed in a 300Tn1 beaker, and 2 g of the cationic surfactant dodecyltrimethylammonium chloride (manufactured by NOF Corporation, trade name: Cation BB) was added.
9 was added and the change in appearance was observed.

Judgment Criteria ◎: No changes such as oil interference streaks or oil floating substances are observed in the emulsion.

0: Slight oil interference marks, oil floating matter, etc. are observed in the emulsion.

Δ: Oil is floating on the surface of the sample due to the destruction of the emulsion.

×: The emulsion was completely destroyed, and oil was deposited on the surface and the wall of the beaker.

Experiment 2 Mechanical stability test Each sample was diluted 10 times with city water, stirred for 5 minutes at 5,000 rpm using a homomixer, and then left in a 100-go cylindrical drip load for 72 hours to separate the upper layer and 29 samples were each taken from the lower layer and the nonvolatile content was measured, and the difference (T
-B) was determined.

Experiment 3 Glass fiber applicability test Sample 1.59 was added to a mixed solution of 309 water-soluble phenolic resin (Sumitomo Durez Co., Ltd. trade name Sumilite Resin PR-51404, non-volatile content 50%) (500 y of water) to prepare a treatment solution. Mixed and untreated glass cloth (Nittobo Co., Ltd. product name WE-18G-10)
4) was impregnated, air-dried, and then heat-treated in a dryer at 200° C. for 5 minutes, and the coatability was evaluated.

Judgment Criteria ◎: Phenol resin is applied evenly and processed well.

△: There are some pockmarks and the coating is uneven.

×: A lump of phenolic resin was formed or untreated portions were observed, and the treatment was non-uniform. Experiment 4 Investigation of texture The texture of the glass cloth treated in Experiment 3 was investigated by touch.

Experiment 5 Water repellency test 2.0° × 2 with glass cloth treated by Experiment 3
．． A sample of 0 cnL was prepared and floated in a 0.1% aqueous solution of sodium dialkyl sulfosuccinate (trade name: Pellex 0TP, manufactured by Kao Atlas Co., Ltd.) at a liquid temperature of 40° C., and the time until sedimentation was measured.

In addition, the value was the average value for five test pieces. The results of these experiments 1 to 5 are shown in Table 2.

As is clear from Table 2, compositions A-D of the present invention are:
It has excellent stability in combination with cationic substances, mechanical stability of emulsion, applicability to glass fibers, texture, and water repellency. Example 2 (1) 200 samples of various emulsions obtained in Example 1
9, (2) (CH3)3Si00.5 units and (C
H3) Consists of HSlO units and has a viscosity of 30 cSt (25°C
), 30 parts of methylhydrodiene polysiloxane, 3 parts of octadecynoletrimethynoleammonium chloride (manufactured by NOF Corporation, trade name: Cation AB), and 6 parts of water.
200 g of cationic emulsion consisting of 7 parts, (3)
Nonionic emulsion 1009 consisting of 30 parts of dibutyltin dilaurate, 3 parts of polyoxyethylene sorbitan monooleate (20 moles of EO added, manufactured by Kao Atlas Co., Ltd., trade name Tween 80), and 67 parts of water was placed in 12 beakers. The mixture was stirred and mixed, and the stability in combination with cationic and nonionic substances was examined using the same criteria as in Experiment 1 of Example 1.

The results are shown in Table 3. As is clear from Table 3, the treatment liquids 1 to 4 of the present invention have excellent stability in combination with cationic and nonionic substances.

Treatment liquids 5 and 6 using Comparative Samples E and K had poor stability when used in combination, and the following texture test and water repellency test could not be conducted. Next, the treatment liquids 1 to 4 were diluted 8 times with water, and a double-thread cotton gear bagine that had been desized and refined in advance was immersed therein and squeezed with a mangle to give a coating weight of 70%.

After preliminary drying at room temperature for 30 minutes, heat treatment was performed at 165° C. for 5 minutes to obtain a test piece. This was subjected to a texture test and a water repellency test according to JISLlOO4 in the same manner as in Example 1.
As comparative examples, (2) component 4009 and (3) component 1
Table 3 shows the results of a comparison using treatment liquid 7 consisting of 009. As is clear from Table 3, treatment liquids 1 to 4 of the present invention are excellent in both texture and water repellency.

Example 3 344,800 parts of octamethylcyclotetrasiloxane,
Tetravinyltetramethylcyclotetrasiloxane 0.
200 parts of chloroplatinic acid, 0.024 parts of chloroplatinic acid, 64.376 parts of water, and 0.600 parts of octylbenzenesulfonic acid were subjected to emulsion polymerization in the same manner as in Example 1, and by adding triethanolamine, the pH was adjusted to 7. An emulsion of O was obtained.

To 100 parts of the obtained emulsion, 3 parts of polyoxyethylene tallow alkylpropylene diamine (number of moles of EO added: 10 moles) was added. This emulsion 100
Component (2) of Example 2 was added in 4 parts. Dilute this 5 times and use a bar coater. 4614 on glassine paper and heat-treated at 180° C. for 1 minute.
The obtained test piece had excellent release properties.

Example 4 34.28 parts of octamethylcyclotetrasiloxane, 0.72 parts of methyltriethoxysilane, 64.40 parts of water and 0.60 parts of dodecylbenzenesulfonic acid were added in Example 1.
Emulsion polymerization was carried out in the same manner as above, and neutralized with ethanolamine to obtain an emulsion with a pH of 7.8.

2 parts of polyoxyethylene tallow alkylamine (5 moles of added EO) were added to 100 parts of the obtained emulsion. When 1 part of this emulsion was added to 100 parts of hydraulic cement and hardened by adding water, this cement had excellent water grinding properties. Example 5 39.95 parts of a mixed cyclic siloxane consisting of 3.5% hexamethylcyclotrisiloxane, 75.5% octamethylcyclotetrasiloxane, and 21% decamethylcyclopentasiloxane, 0.05 part hexamethyldisiloxane, lauryl 8 parts of a 20% aqueous solution of hydrogen sulfate and 52 parts of water were subjected to emulsion polymerization in the same manner as in Example 1 to obtain 100 parts of an emulsion.

Claims (1)

[Scope of Claims] 1. 0.5 to 20 parts by weight of water-soluble or water-dispersible oxidation per 100 parts by weight of polyorganosiloxane in component (A) is added to the anionic silicone emulsion (A) obtained by emulsion polymerization. A silicone emulsion composition prepared by adding an ethylene-added alkylamine derivative (B) and further adjusting the pH of the emulsion to 7 to 9. 2. The composition according to claim 1, wherein 80% by weight or more of the polyorganosiloxane in component (A) consists of difunctional siloxane units. 80% by weight of polyorganosiloxane in component 3(A)
The composition according to claim 1, wherein the composition comprises (CH_3)_2SiO units.