JPH10158515A - Production of organopolysiloxane emulsion - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing an organopolysiloxane emulsion in having no slippery and water-repelling properties without deteriorating the flexibility inherent in a silicone. SOLUTION: This method for producing an organopolysiloxane emulsion comprises reacting a colloidal or transparent cationic silicone emulsion having a particle diameter of <0.1μm with an alkoxy silane or alkoxysiloxane in an amount of 3-100 pts.wt. per pt.wt. of the silicone content of the silicone emulsion, or comprises reacting a colloidal or transparent cationic or nonionic urethane resin having a particle diameter of <0.1μm with an alkoxy silane or alkoxysiloxane in an mount of 3-100 pts.wt. per pt.wt. of the urethane content of the urethane resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an organopolysiloxane emulsion, and more particularly to a method for producing an organopolysiloxane emulsion which is effectively used as a fiber treatment agent for imparting a dry texture. It is.

[0002]

2. Description of the Related Art Organopolysiloxanes conventionally used as fiber treatment agents impart flexibility, water repellency and smoothness when treated on fibers. This smoothness and flexibility gives a slimy touch peculiar to silicone, and, depending on the type of fabric, causes slippage, slippage, and slippage where misalignment occurs. In addition, by having water repellency,
There are some difficulties in using the inner. Therefore, as the taste of the texture shifts from a slimy feeling to a dry feeling, the solution is being addressed by using a combination of an anti-slip agent, an acrylic resin for eliminating the slimy feeling, and a water-soluble resin for eliminating the water repellency. It is the current situation.

However, even when an organopolysiloxane emulsion is treated on a fiber in combination with a finishing agent such as an anti-slip agent, an acrylic resin, or a water-soluble resin, a touch having a water-repellent property and a slippery characteristic of silicone can be completely achieved. Can not be dispelled. In particular, since the conventional silicone emulsion has a large particle size of 10 to 0.1 μm, when it is processed into a fiber, the permeability into the fiber is not sufficient, and most of the emulsion remains attached to the fiber surface. It hinders the action of a combined finishing agent such as an anti-slip agent, an acrylic resin, and a water-soluble resin, and is one of the causes that a dry texture cannot be imparted.

As a measure for solving such a drawback, the inventor of the present invention has disclosed in Japanese Patent Application No. Hei 5-276084 (Japanese Patent Application Laid-Open No.
No. 68), and showed the future direction of amino-modified silicone widely used as a fiber treatment agent, especially regarding the elimination of the texture of slipperiness and slimy feeling. Removal of the slimy feeling is still insufficient, and it is desired to provide a dry texture having the above-mentioned properties without impairing a soft texture.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned state of the art, and its object is to completely eliminate slippage and sliminess without impairing the inherent flexibility of silicone. An object of the present invention is to produce an organopolysiloxane emulsion which can be removed and impart water absorption.

[0006]

That is, the present invention relates to a colloidal or transparent cationic silicone emulsion having a particle size of less than 0.1 μm, wherein alkoxysilane or alkoxysiloxane is added to 3 parts by weight of the silicone component of the silicone emulsion. A method for producing an organopolysiloxane emulsion, wherein the reaction is carried out in an amount of from 100 to 100 parts by weight.

The present invention also relates to a colloidal or transparent cationic or nonionic urethane resin having a particle size of less than 0.1 μm, wherein alkoxysilane or alkoxysiloxane is added to the urethane resin in an amount of 3 to 10 parts by weight based on 1 part by weight of the urethane component of the urethane resin.
A method for producing an organopolysiloxane emulsion, wherein 0 parts by weight are reacted.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The method for producing an organopolysiloxane emulsion of the present invention comprises: (A) preparation of a cationic silicone emulsion or a cationic or nonionic urethane resin. (B) Selection of alkoxysilane or alkoxysiloxane. And (C) a reaction step of mixing a cationic silicone emulsion or a cationic or nonionic urethane resin with an alkoxysilane or alkoxysiloxane.

In step (A), a cationic silicone emulsion having good flexibility and a cationic or nonionic urethane resin are prepared. Here, the cation means a case where the emulsifier is a cation and a case where the silicone oil or the urethane resin has an amino group. Examples of the preparation of the cationic silicone emulsion include an emulsion produced by the condensation reaction of a cationic surfactant and an alkali catalyst using octamethylcyclotetrasiloxane (commonly called D ₄ ) alone or in combination with an alkoxysilane, or-(CH ₂ ) in the molecule. Examples include an amino-modified silicone oil containing a ₃ NH ₂ group or an emulsion of an oil in which the amino group is blocked with a nonionic surfactant. Examples of the adjustment of the urethane resin include an isocyanate and a polyether polyol, or a water-soluble urethane resin obtained by reacting an amino alcohol with the isocyanate.

The particle diameter of the emulsion prepared here is 0.1%.
If it is at least μ, the reaction with the alkoxysilane or alkoxysiloxane in the subsequent step (C) will not proceed smoothly, and the product of the reaction product will gel, making it difficult to produce a stable product. In order to obtain a colloidal or transparent emulsion having a particle size of less than 0.1 µ, any conventionally known method can be employed. For example, a large amount of a surfactant is used, and a high-pressure homogenizer (Sanwa Kikai Co., Ltd.) is used as an emulsifier. By using an emulsification method in which a pressure of 400 kg / cm ² or more is added to an ordinary emulsion.

The silicone or urethane content is 5 to 60 parts by weight, preferably 10 to 40 parts by weight of 100 parts by weight of the emulsion, and the emulsifier is 5 to 30 parts by weight based on 100 parts by weight of the silicone or urethane. (Hereinafter, simply referred to as “parts” indicates parts by weight). If the solid content of the silicone or urethane is less than 5 parts, the reaction described below is difficult to perform, and if it exceeds 60 parts, the product viscosity increases, and it is difficult to obtain a stable product.

The silicone used in the present invention includes a series of modified silicones represented by dimethylpolysiloxane oil and amino-modified silicone oil, and silicone elastomers having these structures.

The urethane used in the present invention is a reaction of a polyfunctional isocyanate compound such as hexamethylene diisocyanate or isophorone diisocyanate with a polyol such as polyethylene glycol or polyethylene polypropylene copolymer or an amino group-containing polyol such as N-methyldiethanolamine. There are things.

The emulsifier used in the present invention includes:
Nonionic surfactants such as polyoxyethylene alkyl ether and polyoxyethylene alkyl phenyl ether; and cationic surfactants such as alkyl ammonium salt and alkyl benzyl ammonium salt.

As the alkoxysilane in the step (B),
It has the following structural formula, and specifically, a functional alkoxysilane coupling agent such as an alkylalkoxysilane such as methyltrimethoxysilane and tetramethoxysilane, γ-glycidoxypropyltrimethoxysilane, and vinyltrimethoxysilane. Is mentioned.

[0016]

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The alkoxysiloxane used in the step (B) has the following structural formula, and specific examples thereof include polyalkoxydimethylsiloxane having a large number of alkoxy groups at the molecular terminals.

[0018]

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In the reaction of the step (C), 3 to 100 parts by weight of alkoxysilane or alkoxysiloxane is added to 1 part by weight of silicone in the cationic silicone emulsion.
Parts, preferably 5 to 100 parts, more preferably 30 to 1 part.
After mixing at room temperature, the mixture is heated to 50 to 90 ° C. with stirring and reacted for 3 to 48 hours, and then cooled. If the amount of the alkoxysilane or alkoxysiloxane is less than 3 parts per 1 part of the silicone, the silicone touch remains.
Even when the reaction is performed in excess of 00 parts, there is almost no difference in physical properties.

The alkoxysilane or alkoxysiloxane is used in an amount of 3 to 100 parts, preferably 5 to 1 part by weight of the urethane component of the cationic or nonionic urethane resin.
-100 parts, more preferably 30-100 parts, are mixed at room temperature, heated to 50-90 ° C. with stirring, reacted for 3-48 hours, and then cooled. If the amount of the alkoxysilane or alkoxysiloxane is less than 3 parts by weight per 1 part by weight of the urethane component, the physical properties of the urethane resin, especially the fastness to dyeing friction against disperse dyes, are greatly reduced. Almost not seen.

In order to uniformly and completely react the cationic silicone emulsion or the cationic or nonionic urethane resin with the alkoxysilane or alkoxysiloxane, heating at 50 to 90 ° C. and uniform stirring in the pH range of 4 to 7 are required. is necessary. The apparatus used for this reaction is not particularly limited, but may be a reaction vessel equipped with a heating device.
It is desirable to have a stirrer rotating at 0 to 60 rpm. To advance the reaction smoothly, after previously reacting a portion of the alkoxysilane or alkoxysiloxane with the cationic silicone emulsion or the cationic or nonionic urethane resin, a surfactant is further added, and the remaining alkoxysilane is added. Alternatively, it is preferable to react with an alkoxysiloxane.

[0022]

EXAMPLES The present invention will now be described specifically with reference to examples, but the present invention is not limited to these examples.

Example 1 The polymerization viscosity of silicone is 1200 cs, and
A 15% amino-modified silicone oil nonionic emulsion containing (CH ₂ ) ₃ NH ₂ groups and terminated with trimethylsiloxane units having an amine value of 16 was prepared at room temperature. 10 parts of vinyltrimethoxysilane was added to 100 parts of this emulsion at room temperature,
After reacting for 5 hours, 5 parts of nonylphenol-based nonionic activator (HLB15), 100 parts of vinyltrimethoxysilane and 200 parts of water were added, and the mixture was further added at 60 ° C. × 10.
After reacting for an hour, it was cooled to 40 ° C. or lower to obtain a stable emulsion.

Example 2 Amino-modified silicone oil having amino groups blocked (KF
877 (Shin-Etsu Silicone Co., Ltd.) 100 parts were emulsified in the same manner as in Example 1 to obtain a 15% stable emulsion. 100 parts of this emulsion was mixed with vinyltrimethoxysilane 1
10 parts and 200 parts of water were added and reacted in the same manner as in Example 1 to obtain a stable emulsion.

Example 3 Hexamethylene diisocyanate (HDI), polyethylene glycol (molecular weight: 400), and methyldiethanolamine were reacted in a conventional manner to obtain a 30% aqueous urethane resin (100 parts) and vinyltrimethoxysilane (20%).
0 parts, nonylphenol-based nonionic activator (HL
B. 15) and 500 parts of water were reacted in the same manner as in Example 1 to obtain a stable emulsion.

Example 4 To 100 parts of the urethane resin of Example 3, 10 parts of an alkoxysiloxane (NUC Silicone FZ3704 manufactured by Nippon Unicar) was added at room temperature, and the mixture was heated and stirred at 70 ° C. for 5 hours.
Further, 20 parts of a nonylphenol-based nonionic activator, 100 parts of the above alkoxysiloxane and 400 parts of water were added, and
After reacting at 0 ° C. for 48 hours, the mixture was cooled to 40 ° C. or lower to obtain a stable emulsion.

Comparative Examples 1 to 5 The amino-modified silicone emulsion of Example 1 was replaced with the amino-modified silicone emulsion of Comparative Example 1 and Example 1.
The reaction product of 0 part and 10 parts of vinyltrimethoxysilane was used in Comparative Example 2, the amino-modified silicone emulsion in which the amino group was blocked in Example 2 was used in Comparative Example 3, and the urethane resin in Example 3 was used in Comparative Examples 4 and 3. Comparative Example 5 was obtained by adding 10 parts of vinyltrimethoxysilane, 10 parts of nonylphenol-based nonionic activator (HLB14) and 100 parts of water to 100 parts of the urethane resin obtained in Example 1 and reacting in the same manner as in Example 1. And

Next, the test cloths (cotton broad 50th cloth) to which the processing baths (3% by weight solution) of the emulsions of Examples 1 to 4 were applied were referred to as processing Nos. (Ii) to (v). Comparative Examples 1 to 5
Nos. (Vi) to (x) were tested for slipperiness, dry feeling, and water absorption. A blank that was not treated on the test cloth was designated as a treatment No. (i), and the test was also performed.

The slip-out test was performed according to JIS L-1096.
The slippage value was measured according to the 21st seam slippage method B (measuring load: 10 kg), the hand test was measured by handling, and the water absorption was measured by dropping a water droplet and absorbing it. The processing conditions of the test cloth are as follows: once dipping, once drawing, drawing ratio 100%, drying 110 ° C × 3 minutes, heat treatment 160 ° C ×
Two minutes.

Table 1 shows the treatment bath compositions of treatment Nos. (I) to (x) and the results of slipperiness, dry feeling, and water absorption.

[0031]

[Table 1]

As can be seen from the results of the slipperiness test shown in Table 1, it is recognized that the product of the present invention does not slip the fiber as in the case of the original fabric in terms of the slippage value. In addition, it is also recognized that the product of the present embodiment is dry in terms of the texture of the fiber, and that the water absorption is similar to that of the original fabric.
The anti-slip property, dry feeling, and water absorption were better than the formulation of the comparative example.

Next, the test cloth polyester tropical (Foro
n Rubin S-4GFL (disperse dye) 4% o. w. f.
(Dyed cloth) was subjected to the same processing as in the above-mentioned treatment Nos. (Ii) to (x), and the dyeing rub fastness was tested. A blank that was not treated on the test cloth was designated as a treatment No. (i), and the test was also performed.

The dye rub fastness test was conducted according to JIS L-084.
The measurement was carried out at a measurement load of 200 g × 100 times in accordance with No. 9, and the results were shown in the first to fifth grades.

Table 2 shows the compositions of the processing solutions No. (i) to (x) and the results of the color fastness to rubbing.

[0036]

[Table 2]

As can be seen from the results of the dyeing rub fastness test shown in Table 2, the ordinary urethane resin has poor fastness to disperse dyes and is difficult to use for polyester dyeing cloths. Can be used.

[0038]

According to the present invention, an organopolysiloxane emulsion produced according to the present invention can be used for fabrics in which a cationic silicone emulsion exhibiting a water-repellent and slimy texture is treated on fibers to cause misalignment, slippage, and slippage. With good water absorption, without promoting their action,
A dry texture can be imparted on the fiber.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI D06M 15/653 D06M 15/653

Claims (6)

[Claims] 1. A colloidal or transparent cationic silicone emulsion having a particle size of less than 0.1 μm, wherein alkoxysilane or alkoxysiloxane is added in an amount of 3 to 100 parts by weight based on 1 part by weight of silicone in said silicone emulsion.
A method for producing an organopolysiloxane emulsion, comprising reacting parts by weight. 2. A method in which a colloidal or transparent cation or nonionic urethane resin having a particle diameter of less than 0.1 μm is reacted with 3 to 100 parts by weight of alkoxysilane or alkoxysiloxane per 1 part by weight of the urethane component of the urethane resin. A method for producing an organopolysiloxane emulsion. 3. The method for producing an organopolysiloxane emulsion according to claim 1, wherein said alkoxysilane is an alkylalkoxysilane or a functional alkoxysilane coupling agent. 4. The method for producing an organopolysiloxane emulsion according to claim 1, wherein the alkoxysiloxane is a polyalkoxydimethylsiloxane. 5. The method for producing an organopolysiloxane emulsion according to claim 1, wherein the reaction is carried out while heating and stirring. 6. A fiber treatment agent for imparting a dry texture, comprising an organopolysiloxane produced by the production method according to claim 1. Description: