JPH0655817B2 - Method for producing aminosilicone fine particle emulsion - Google Patents

Description

TECHNICAL FIELD The present invention is excellent in storage stability, dilution stability, mechanical stability, has a transparent appearance, and has a fiber treatment agent, a release agent, and a polishing agent. The present invention relates to a method for producing an aminosilicone fine particle emulsion which can be preferably used as

2. Description of the Related Art Conventionally, as a method for producing an aminosilicone emulsion, a conventional method for producing an aminosilicone emulsion has been described. There is known a method of producing by emulsifying and dispersing in water with such a stirring device.

However, the aminosilicone emulsion produced by such a method has a large average particle size of 0.5 μm or more and is poor in storage stability, dilution stability, particularly stability due to mechanical shear. In the case of processing, when the processing speed is high, there is a drawback that the roll rotating at a high speed causes emulsion breakage, which easily causes problems such as processing unevenness and roll contamination.

Further, as a method for producing an aminosilicone emulsion, a low molecular weight cyclic siloxane and an aminosilane are used as starting materials, and a polymer is polymerized in an emulsification system using a strong alkali as a catalyst to produce a polymer.
No. 38,609) is also well known. According to this method, the particle size of the obtained emulsion is 0.1 to 0.2.
Although it can be made as small as μm, the storage stability and the dilution stability are considerably improved, but the stability against a strong mechanical shear is still insufficient. Further, the emulsion polymerization method has an essential disadvantage in that about 10% of the low molecular weight cyclic siloxane as a starting material remains unpolymerized in the manufacturing method, and the residual low molecular weight siloxane has a problem when the resulting emulsion is used. It may lead to various inconveniences during use, such as volatilization and generation of white powder due to thermal oxidation in the drying process, cissing of paint due to adhesion to the surrounding surface, contact failure of electrical equipment existing in the surroundings, etc. There was a problem that there is a property.

Therefore, development of a method for producing an aminosilicone fine particle emulsion having high stability and good usability has been desired.

The present invention has been made in view of the above circumstances, storage stability,
It is an object of the present invention to provide a method for producing an aminosilicone fine particle emulsion which has excellent dilution stability and mechanical stability and is easy to use.

Means and Actions for Solving the Problem The present inventor has conducted extensive studies to achieve the above object, and as a result, the following general formula (1) [Wherein R ¹ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, a hydroxyl group or -OR '(R' is a monovalent hydrocarbon group having 1 to 20 carbon atoms), and A is a formula -R. ² (NR ³ R ⁴ ) _z NR
⁵ R ⁶ (R ² and R ⁴ are each a divalent hydrocarbon group having 1 to 6 carbon atoms, and R ³ , R ⁵ and R ⁶ are each a hydrogen atom or a monovalent hydrocarbon having 1 to 20 carbon atoms. Group, z is 0 to 5
Represents an integer of), an aminoalkyl group represented by
0 <x ≦ 3, 0 ≦ y <3, 0 <x + y ≦ 3. ] And / or an aminosilicone represented by the above formula (1) An epoxy-modified amino silicone which is a reaction product with a monoepoxy compound represented by (wherein R ⁷ represents a monovalent organic group) is used as a starting material, and a surfactant is added to the starting material ((1)). Formulated aminosilicone, epoxy-modified aminosilicone) in an amount of 10 parts by weight or more based on 100 parts by weight in total, and after homogeneous mixing at room temperature, water is gradually added to aminosilicone and / or epoxy-modified Aminosilicone is emulsified and dispersed in water at room temperature, and then an acidic substance is added to this aqueous emulsified dispersion solution in an amount of 0.1 mol with respect to N atoms in the starting material (aminosilicone of the formula (1), epoxy-modified aminosilicone) molecule. After adding so that the equivalent amount or more, heat aging is performed (50
The average particle size is 0.1.
It has been found that an aminosilicone fine particle emulsion having a storage stability, a dilution stability, a mechanical stability, a high usability, and a transparent appearance can be obtained at a particle size of not more than μm.

That is, the aminosilicone fine particle emulsion obtained by the above method has an average particle size of 0.1 μm as described above.
Since it is the following, the emulsion particles are very fine, and thus various types of stability are remarkably improved as compared with an emulsion produced by a conventional method. For example, regarding storage qualitativeness, phenomena such as emulsion separation do not occur even at room temperature for one year or more, and are stable over a long period of about twice or more compared to conventional ones. Further, the dilution stability is extremely good without the occurrence of oil spots and the like. In particular, in terms of mechanical stability, there is no problem such as the conventional one in which the emulsion is broken by the high-speed rotating roll, the processing is uneven, and the roll is dirty. Moreover, since the aminosilicone fine particle emulsion produced by the present invention is made into fine particles and the appearance becomes transparent or translucent from the conventional cloudy liquid, the appearance is not impaired when other combined components are transparent, etc. It is a fine particle emulsion with high usability because it has properties suitable for applications such as fiber treatment agents, release agents, and polishes.

Hereinafter, the present invention will be described in more detail.

As described above, the method for producing the aminosilicone fine particle emulsion according to the present invention comprises 10 parts by weight of the aminosilicone and / or the epoxy-modified aminosilicone with a surfactant, based on 100 parts by weight of the total amount of the aminosilicone and the epoxy-modified aminosilicone. Amino silicone and / or epoxy-modified amino silicone is emulsified and dispersed in water by adding at least 1 part by weight, and then an acidic substance is added to the emulsified and dispersed aqueous solution in an amount of 0.1 to N atom in amino silicone and epoxy-modified amino silicone molecule. After adding a molar equivalent or more, heat aging is performed.

In this case, the aminosilicone used as a starting material in the present invention is represented by the following general formula (1) It is shown by.

Here, in the formula, R ¹ is a methyl group, an ethyl group, a propyl group,
Alkyl group such as octyl group, lauryl group, alkenyl group such as vinyl group, allyl group, aryl group such as phenyl group, tolyl group, naphthyl group, cycloalkyl group such as cyclopentyl group, cyclohexyl group, or part thereof. Or a monovalent hydrocarbon group having 1 to 20 carbon atoms, such as a group in which all hydrogen atoms are replaced by halogen atoms, a hydroxyl group or -OR '
(R 'is a monovalent hydrocarbon group having 1 to 20 carbon atoms).

Also, A is an aminoalkyl group of the formula _{^{-R 2 (NR 3 R 4)}} z NR 5 R 6, R 2, R 4 are each a methylene group, an ethylene group, a propylene group, hexamethylene group,
A divalent hydrocarbon group having 1 to 6 carbon atoms such as a phenylene group, R ³ , R ⁵ and R ⁶ are each a hydrogen atom or the above R ¹
And a monovalent hydrocarbon group having 1 to 20 carbon atoms, z is 0
Is an integer of ~ 5. And view the such aminoalkyl _{groups, -C 3 H 6 NH 2,} -C 3 H 6 NHC 2 H 4 NH
_{2, -C 6 H 12 NHC 2} H 4 NH 2, -C 3 H 6 (NH
_{C 2 H 4) 2 NH 2} , -C 3 H 6 (NHC 2 H 4) 3 N
_{H 2, -C 2 H 4 NHC} 2 H 4 NH 2, -CH 2 NHC
₂ H ₄ N (C ₄ H ₉ ) ₂ , However, the present invention is not limited to these.

Note that x and y are 0 <x ≦ 3, 0 ≦ y <3, 0 <x + 1.
≦ 3.

As the aminosilicone of the formula (1), a silicone chain having a terminal blocked with a trimethylsilyl group is generally used, but if necessary, a terminal blocked with a hydroxyl group or an alkoxy group may also be used. obtain.

Further, in the present invention, as the starting material, the amino silicone of the above formula (1) and the following formula It is also possible to use an epoxy-modified aminosilicone obtained by reacting with a monoepoxy compound represented by

Here, the substituent R ⁷ in the above monoepoxy compound is a monovalent organic group containing no epoxy group, preferably a linear or branched hydrocarbon group, but a polyoxyalkylene group The compound represented by the following formula can be exemplified as the monoepoxy compound.

To obtain the above epoxy-modified amino silicone, (1)
The compounding ratio of the aminosilicone of the formula and the epoxy compound is 0.01 to 20 mol amount, particularly 0.1 to 10 mol amount of the epoxy group in the monoepoxy compound with respect to one nitrogen atom contained in the aminosilicone. It is preferable to set it as follows.

The aminosilicone of the formula (1) and the above monoepoxy compound are mixed in the following reaction formula by heating them to about 40 to 80 ° C. The reaction represented by (1) occurs, and an epoxy-modified aminosilicone in which the active hydrogen group of the amino group in the aminosilicone molecule is block-modified with an epoxy compound is produced as a reaction product.

In the present invention, as the starting material, 1 of each of the aminosilicone of the formula (1) and the above epoxy-modified aminosilicone
The seeds may be used alone or in combination of two,
Further, amino silicone and epoxy-modified amino silicone may be used in combination (hereinafter, starting materials are generically referred to as amino silicones).

In the method for producing an aminosilicone fine particle emulsion of the present invention, first, a surfactant is added to the above starting material to disperse aminosilicones in water.

Here, the surfactant used is not particularly limited, and various conventionally known surfactants such as nonionic surfactants, anionic surfactants, cationic surfactants and zwitterionic surfactants are used. Things can be used. Specific examples of the surfactant include nonionic surfactants such as polyoxyethylene alkylphenyl ether, polyoxyethylene alkyl ether, polyoxyethylene alkyl ester, sorbitan fatty acid ester and sucrose fatty acid ester, alkyl sulfate, alkyl Anionic surfactants such as phenyl sulfonate and polyoxyethylene alkylphenyl sulfate, cationic surfactants such as alkyltrimethylammonium chloride, dialkyldimethylammonium chloride and benzyltrimethylammonium chloride, amphoteric properties such as alkylbetaine and alkylamino acid Ionic surfactants and the like,
One or more of these may be used, but among them, it is preferable to use a nonionic surfactant from the viewpoint of the combined use with other ionic components, and in particular, one or two of the surfactants used. It is preferable to use it so that the total HLB value of at least one species is 12 to 15.

The amount of the surfactant added is 10
10 parts by weight or more with respect to 0 parts by weight, preferably 10 to 1
If the addition amount is less than 10 parts by weight, a fine particle emulsion having an average particle size of 0.1 μm or less cannot be obtained, and if it is more than 10 parts by weight, production of the fine particle emulsion may be carried out. It remains as a non-volatile component during the treatment of fibers and the like, and hinders the properties of amino silicones.

In the present invention, regarding the method of emulsifying and dispersing the aminosilicones in water, the aminosilicones and the surfactant are mixed and homogenized at room temperature with a stirring device such as a propeller blade or a homomixer, and water is gradually added thereto with stirring. Is used to produce an O / W type emulsion. The amount of water used may be adjusted on the basis of the desired aminosilicone concentration.
It is 100 to 1000 parts by weight with respect to 00 parts by weight.

Next, in the present invention, the pH is adjusted by adding an acidic substance to aminosilicones that are emulsified and dispersed in water.When an acidic substance is added, the amino group in the aminosilicone reacts with the acidic substance to form an amine salt. As a result, the hydrophilicity of the aminosilicone is increased, and a fine particle emulsion can be formed by subsequently performing a heat aging step described later.

In this case, examples of the acidic substance include inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, propionic acid acetate, lauric acid,
Examples thereof include organic acids such as stearic acid, and lower fatty acids such as formic acid and acetic acid are preferable in terms of reactivity and handling.

Further, the amount of the acidic substance used is in the range of 0.1 molar equivalent or more, preferably 0.1 to 1 molar equivalent, and less than 0.1 molar equivalent with respect to the nitrogen atom in the aminosilicone molecule. Therefore, the hydrophilicity of aminosilicones is insufficient, and a fine particle emulsion having an average particle size of 0.1 μm or less cannot be obtained. The amount of the acidic substance used is not particularly limited as long as it is 0.1 molar equivalent or more, but the acidic substance may be volatilized or may be generated as a volatilized component during the treatment of the fiber and the like, which may lead to deterioration of the properties of the aminosilicone. Therefore, it is more preferably 0.1 to 1 molar equivalent.

In the present invention, the acidic substance is added to the emulsion-dispersed aqueous solution of aminosilicones in this manner, and then the mixture is heated for aging. By carrying out this heat aging step, the reaction between the amino group in the amino silicone and the acidic substance described above, that is, the hydrophilization of the amino silicone is promoted. Due to the hydrophilicity of the amino silicones and the heat energy generated by heating, the emulsion particles are shredded by water molecules,
The emulsion particles are subdivided into fine particles.

Here, the heat aging is performed at 50 to 90 ° C, particularly 60 to 80 ° C.
It is preferable to carry out the treatment for 1 hour or longer, especially for 3 to 20 hours. Temperature is lower than 50 ℃, aging time is 1
If the time is not reached, a satisfactory fine particle emulsion may not be obtained, and if the temperature is higher than 90 ° C, the emulsion may be broken.

The heat aging is preferably performed while stirring the emulsified dispersion liquid of aminosilicones with a stirring device such as a propeller blade.

The aminosilicone fine particle emulsion obtained by the method of the present invention described above can be used as it is as a fiber treatment agent, a release agent, a polish, etc. for various purposes, but other aqueous treatment agents may be used as necessary. , For example water repellent,
Antistatic agents for water absorption processing, flame retardants, etc. may be added and used.

EFFECTS OF THE INVENTION As described above, according to the production method of the present invention, an aminosilicone fine particle emulsion having an average particle size of 0.1 μm or less and excellent in storage stability, dilution stability and mechanical stability can be obtained. Further, since the emulsion obtained by the method of the present invention has a transparent or translucent appearance, it does not impair the appearance even when used in combination with other transparent components, and has good permeability, and therefore, for example, fibers are treated. In this case, even thick cloth can be uniformly processed to the inside, and it is also possible to sufficiently impart aminosilicon characteristics such as flexibility.
It is useful as a fiber treatment agent, a release agent, a polish, and the like.

Examples and Comparative Examples Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.

Example 1 The following formula 150 g of amino silicone and 50 g of polyoxyethylene phenyl ether (HLB = 13.3) are added.
After charging in a beaker and homogenously mixing for 5 minutes at room temperature with a homomixer (made by Tokushu Kika Kogyo Co., Ltd.) at 5000 rpm,
Under the same stirring, 800 g of water was gradually added to uniformly emulsify and disperse (Emulsion A).

Further, under the same stirring, 4.6 g of acetic acid (1.0 molar equivalent to N atom in aminosilicone) was added, and then 10
Stirring was continued for a minute (emulsion B).

This emulsion B was transferred to a flask having a capacity of 2 and aged with heating at 80 ° C. for 4 hours under stirring with a propeller blade of 100 rpm to obtain an aminosilicone fine particle emulsion (emulsion C).

Comparative Example 1 As an example of the emulsion polymerization method, 140.6 g of octamethylcyclotetrasiloxane, 7.8 g of N-β (aminoethyl) -γ-aminopropylmethyldimethoxysilane, 1.5 g of hexamethyldisiloxane, lauryltrimethyl. 50 g of ammonium chloride was charged into a 2 beaker and homogenized for 5 minutes at a homomixer of 5000 rpm.
Under the same stirring, 781 g of water was gradually added to uniformly emulsify and disperse, and then transferred to a flask having a capacity of 2 and propeller blade 1
Under stirring at 00 rpm, 1 g of potassium hydroxide dissolved in 19 g of water was added. Then, the mixture was heated at 80 ° C. for 40 hours to carry out a polymerization reaction, kept at 30 ° C. for 10 hours, and then neutralized with 2 g of acetic acid (emulsion D).

[Comparative Example 2] An emulsion was prepared in the same manner as in Example 1 except that 0.3 g of acetic acid (0.065 molar equivalent relative to N atoms in aminosilicones) was used (emulsion E).

[Comparative Example 3] An emulsion was prepared in the same manner as in Example 1 except that the amount of the surfactant was 10 g (emulsion F).

Table 1 shows the evaluation results of the emulsions obtained in Example 1 and Comparative Examples 1 to 3.

From the results shown in Table 1, when produced by the conventional emulsion polymerization method (Comparative Example 1), and when the addition amount of the acidic substance or the addition amount of the surfactant is outside the range of the present invention (Comparative Examples 2 and 3), A fine particle emulsion having an average particle size of 0.1 μm or less cannot be obtained, and the emulsion has a milky white appearance and low storage stability and mechanical stability. However, the emulsion produced by the method of the present invention (Example 1, Emulsion C) has an average particle size of 0.1 μm or less and has a transparent appearance, is stable for a long time of about 2 times or more and has excellent storage stability, and has diluting stability that no oil spots occur. It was confirmed that it was good and mechanical stability was also good.

[Comparative Example 4] In Example 1, the aminosilicone, the surfactant and the water were charged, the temperature was raised to 80 ° C, and the mixture was uniformly mixed at 500 rpm for 5 minutes, and further homomixer 5000 rpm.
After uniformly mixing for 5 minutes, the same amount of acetic acid was added and stirring was continued for another 10 minutes (emulsion G).

This emulsion G was transferred to a flask and heated at 80 ° C. for 4 hours (emulsion H).

The evaluation results of these emulsions G and H are shown below.

Emulsion G Appearance Blue-white translucent liquid Average particle size 0.15 μm Storage stability 6 months Separation / diluting stability Good mechanical stability With interference film Emulsion H Appearance Blue-white translucent liquid Average particle size 0.12 μm Storage stability 6 months Separation Dilution stability Good mechanical stability With interference film From the above results, when heat is applied before adding an acidic substance (acetic acid), the affinity between aminosilicone and surfactant decreases and the emulsion particle size increases. However, it is recognized that even if an oxidizing substance is added later and heated, there is a limit to the atomization, and the particle size of the final emulsion does not become 0.1 μm or less.

Example 2 The following formula An emulsion was produced in the same manner as in Example 1 except that 150 g of the aminosilicone represented by 1) was used and 1.3 g of formic acid (0.5 molar equivalent to N atom in aminosilicone) was used as the acidic substance.

Example 3 The following formula 150g of aminosilicone and 15.0g of polyoxyethylene lauryl ether (HLB = 14.0)
Was used and 1.1 g of formic acid (0.1 molar equivalent to N atom in aminosilicone) was used as an acidic substance, and an emulsion was produced in the same manner as in Example 1.

Example 4 A glass reactor having a capacity of 1 equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen gas inlet was used in Example 1 and 300 g of aminosilicone and the formula were used. 11.4 g of monoepoxy compound represented by (1.0 molar equivalent to N atom in aminosilicone) was charged,
When reacted at 60 ° C for 5 hours under aeration of nitrogen gas,
Nonvolatile matter (105 ° C / 3Hrs) 97.6%, viscosity 154
00 cs of aminosilicone was obtained. An emulsion was produced using this aminosilicone in the same manner as in Example 1.

The evaluation results of the emulsions obtained in Examples 2 to 4 are second
Shown in the table.

From the results shown in Table 2, it was found that the emulsion obtained by the method of the present invention has an average particle size of 0.1 μm or less, has a transparent appearance, and is excellent in various stability.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Noriyuki Maiya, 13-1 Isobe, Annaka-shi, Gunma Shin-Etsu Chemical Co., Ltd. Silicone Electronic Materials Research Laboratory (56) References -503204 (JP, A) International publication 88/8436 (WO, A)

Claims (1)

[Claims] 1. The following general formula (1) [Wherein R ¹ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, a hydroxyl group or -OR '(R' is a monovalent hydrocarbon group having 1 to 20 carbon atoms), and A is a formula -R ² (NR ³ R ⁴ ) _z NR
⁵ R ⁶ (R ² and R ⁴ are each a divalent hydrocarbon group having 1 to 6 carbon atoms, and R ³ , R ⁵ and R ⁶ are each a hydrogen atom or a monovalent hydrocarbon having 1 to 20 carbon atoms. Group, z is 0 to 5
Is an aminoalkyl group represented by
<X ≦ 3,0 ≦ y <3,0 <x + y ≦ 3. ] And / or an aminosilicone represented by the above formula (1) (Wherein R ⁷ represents a monovalent organic group), an epoxy-modified aminosilicone which is a reaction product with a monoepoxy compound represented by the formula: 10 parts by weight or more and uniformly mixed at room temperature, water is gradually added to emulsify and disperse the aminosilicone and / or the epoxy-modified aminosilicone at room temperature, and then the acidic substance is added to the aqueous solution of the emulsified dispersion. A method for producing an aminosilicone fine particle emulsion, which comprises adding 0.1 molar equivalent or more to N atom in silicone and epoxy-modified aminosilicone molecule, and then heat aging at 50 to 90 ° C. for 1 hour or more.