JP3495110B2 - Amino group-containing organopolysiloxane microemulsion and process for producing the same - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an amino group-containing organopolysiloxane microemulsion and a process for producing the same. More specifically, the present invention has excellent storage stability, dilution stability, mechanical stability, and thermal stability at high temperatures, has a transparent appearance, and can be suitably used as a fiber treatment agent, The present invention relates to an amino group-containing organopolysiloxane microemulsion and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, amino group-containing organopolysiloxane emulsions have been prepared by mixing liquid amino group-containing organopolysiloxane with a surfactant, for example, a homomixer,
It is produced by emulsifying and dispersing in water with a device capable of applying high shearing force such as a colloid mill or a stirring device such as a propeller blade. However, the amino group-containing organopolysiloxane emulsion produced by this conventional method has a large average particle size of 0.5 μm or more,
Poor storage stability, dilution stability, especially stability against mechanical shearing.For example, when used as a fiber treatment agent, when the processing speed is high, emulsion breakage occurs due to rolls rotating at high speed, resulting in uneven processing and stains on the rolls. There was a drawback that the problem of was likely to occur.

As a method for producing an amino group-containing organopolysiloxane emulsion, an emulsion polymerization method is also well known, in which a low molecular weight cyclic siloxane and aminosilane are used as starting materials, and a high alkali is used as a catalyst to polymerize and polymerize in an emulsion dispersion system. (Japanese Patent Publication No. 56-38609). According to this method, the average particle size of the obtained emulsion can be made as small as 0.1 to 0.2 μm, and the storage stability and dilution stability are considerably improved, but the stability against mechanical shearing is increased. Was still insufficient.

Further, an amino group-containing organopolysiloxane emulsion is prepared by adding a organopolysiloxane to a mixture of a surfactant soluble in water or a polyhydric alcohol and a polyhydric alcohol to obtain a precursor composition. It can also be manufactured (Japanese Patent Publication No. 4-49581). The composition in this method is translucent or transparent, and although the average particle size of the emulsion obtained by adding water to it is 0.5 μm or less, the storage stability, dilution stability and mechanical stability are insufficient. Met.

In addition to the above, as an amino group-containing organopolysiloxane microemulsion and a method for producing the same, a method of adding a surfactant and an acidic substance to the amino group-containing organopolysiloxane and heating the entire system to 50 ° C. or higher is known. (Japanese Patent Laid-Open No. 2-503204 and Japanese Patent Laid-Open No. 2-284959). However, the microemulsion produced by this method has an average particle size of 0.1 μm.
It is as small as the following, storage stability, dilution stability and mechanical stability are fairly good, but storage stability under high temperature conditions such as 50 to 90 ° C, thermal stability, mechanical stability, dilution stability , Transparency was insufficient.

[0006]

In view of such circumstances, the present invention has excellent storage stability, dilution stability, mechanical stability, and thermal stability at high temperatures, and has a transparent appearance. However, it is an object of the present invention to provide an amino group-containing organopolysiloxane microemulsion which can be suitably used as a fiber treating agent and a method for producing the same.

[0007]

As a result of various studies on the method for overcoming the drawbacks of the prior art, the present inventors have made a specific acid coexist in addition to an amino group-containing organopolysiloxane, a surfactant and water. By emulsification, it is possible to obtain a microemulsion with far superior performance in storage stability, thermal stability, mechanical stability, dilution stability, and transparency compared to the microemulsion obtained by conventional methods. The present invention has been completed and further studies have been made to complete the present invention.

That is, the present invention provides the following formula:

[Chemical formula 2] {In the formula, R ¹ is a hydrogen atom, a hydroxyl group, a monovalent hydrocarbon group having 1 to 20 carbon atoms or the following formula: —OR ′ (wherein
R ′ represents a group represented by a monovalent hydrocarbon group having 1 to 20 carbon atoms, and A represents the following formula: —R ² (NR ³ R
⁴ ) _z NR ⁵ R ⁶ (in the formula, R ² and R ⁴ independently of each other represent a divalent hydrocarbon group having 1 to 6 carbon atoms;
³ , R ⁵ and R ⁶ each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, and z represents an organic functional group represented by 0) to 5). , And x and y have the following conditions: 0 <x ≦ 3, 0 ≦
y <3, 0 <x + y ≦ 3, and the proportion of amino groups in the molecular weight of the compound of formula I is NH ₂
When producing an emulsion comprising 100 parts by weight of an amino group-containing organopolysiloxane represented by 0.25% by weight or more}, 10 to 1000 parts by weight of a surfactant, and 40 to 500,000 parts by weight of water, From the group consisting of glutamic acid and aspartic acid in an amount corresponding to 0.1 chemical equivalent or more in terms of hydrogen ion with respect to the nitrogen atom in the amino group-containing organopolysiloxane molecule.
The present invention relates to a method for producing an amino group-containing organopolysiloxane microemulsion, which comprises adding an acid containing an amino group or a substituted amino group in a molecule to be neutralized.

The amino group-containing organopolysiloxane used in the present invention is not particularly limited as long as it is represented by the above formula I. In the formula I, the group R ¹ is a hydrogen atom, a hydroxyl group, a monovalent hydrocarbon group having 1 to 20 carbon atoms, for example, an alkyl group such as a methyl group, an ethyl group, a propyl group, an octyl group, a lauryl group, a vinyl group or an allyl group. Alkenyl groups such as groups, phenyl groups, tolyl groups, aryl groups such as naphthyl groups, cyclopentyl groups, cycloalkyl groups such as cyclohexyl groups, or groups in which some or all of their hydrogen atoms are replaced with halogen atoms, or The following formula: -OR
′ ′ (Wherein R ′ represents a monovalent hydrocarbon group having 1 to 20 carbon atoms (for example, those exemplified for R ¹ ) ′).

The group A has the following formula: -R ² (NR ³ R ⁴ ).
_z NR ⁵ R ⁶ is an organic functional group, and R ² and R ⁴ are independently of each other a divalent hydrocarbon group having 1 to 6 carbon atoms, for example, methylene group, ethylene group, propylene group, hexamethylene. Group, phenylene group, etc., R ³ ,
R ⁵ and R ⁶ are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms (for example, those exemplified for R ¹ ) and z is an integer of 0 to 5. As the organic functional group _{A, -C 3 H 6 NH 2} , -C
_{3 H 6 NHC 2 H 4 NH} 2, -C 6 H 12 NHC 2 H 4 N
_{H 2, -C 3 H 6 (} NHC 2 H 4) 2 NH 2, -C 2 H
₄ NHC ₂ H ₄ NH ₂ , -C ₂ H ₄ NHC ₂ H ₄ N (C
H ₃ ) _{2 and the} like can be mentioned, but the present invention is not limited thereto.

Note that x and y in the above formula I are numbers satisfying the following conditions: 0 <x ≦ 3, 0 ≦ y <3, 0 <x + y ≦ 3.

Further, in the present invention, it is essential that the amino group in the amino group-containing organopolysiloxane molecule represented by the formula I is 0.25% by weight or more in terms of NH ₂ . The reason is that when the amount of amino groups is out of this range, the hydrophilicity of the amino group-containing organopolysiloxane is insufficient, and the transparency of the microemulsion produced is deteriorated.

As a typical specific example of the amino group-containing organopolysiloxane represented by the above formula I, the following formula:

[Chemical formula 3] Where R ¹ and A represent the same meaning as defined for formula I, R ² represents the meaning of R ¹ or A, m
Is 0 to 25,000, preferably 10 to 2000, more preferably 80 to 750, and n has the same numerical value range as m, but the proportion of amino groups in the molecule is 0.25 % by weight or more in terms of NH _2. However, the present invention is not limited to this, and an amino group-containing organopolysiloxane having a branched structure can also be used. Further, the amino group-containing organopolysiloxane of the formula I is generally one in which the end of the polysiloxane chain is blocked with a trialkylsilyl group such as a trimethylsilyl group, but a part or all of the alkyl group is a hydroxyl group or an alkoxy group. It may be blocked with a trialkylsilyl group substituted with a group or an amino group-containing group.

The surfactant used in the present invention is
Various conventionally known substances such as nonionic surfactants, anionic surfactants, cationic surfactants, zwitterionic surfactants, and silicone surfactants 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 or sucrose fatty acid ester, and anionic surfactants. Agents such as alkyl sulfates, alkylphenyl sulfonates or polyoxyethylene alkylphenyl sulfates, cationic surfactants such as alkyltrimethylammonium chloride, dialkyldimethylammonium chloride, benzyltrimethylammonium chloride, zwitterionic surfactants, etc. Agents, such as alkyl betaines or alkyl amino acids, may be used, and one or more of them may be used, but among them, combination with other ionic components HL terms of the non-ionic preferably the use of surfactants, in particular surfactants used
It is preferable to select the total B (hydrophilic group / lipophilic group balance) value to be 8 to 15.

The amount of the above surfactant added is 10 to 1 with respect to 100 parts by weight of the amino group-containing organopolysiloxane.
000 parts by weight, preferably 10 to 100 parts by weight.
If the amount of the surfactant added is less than 10 parts by weight, a transparent microemulsion cannot be obtained, and the stability of the microemulsion increases as the amount added increases. However, when the amount of the surfactant exceeds 1000 parts by weight, the characteristics of the amino group-containing organopolysiloxane are impaired, and when the resulting microemulsion is used as a fiber treating agent, for example,
There arises such an adverse effect that the unique texture of the amino group-containing organopolysiloxane cannot be obtained.

The acid used in the present invention is an acid containing an amino group or a substituted amino group in the molecule, such as glutamic acid, aspartic acid, sulfamic acid, oxyglutamic acid and the like. These acids may be used alone or in combination of two or more. When these specific acids are used, the storage stability, dilution stability, mechanical stability, thermal stability and transparency of the amino group-containing organopolysiloxane microemulsion are better than those when other acids are used. It can be further improved. Further, the acid used in the present invention is originally low in metal corrosiveness and low in volatility, and therefore, for example, in the fiber treatment step, the metal surface of the inner surface of the pipe, the treatment device, the storage device, and the used device is not corroded or rusted by the acid. Hard to occur.

The amount of the above-mentioned acid added is an amount corresponding to 0.1 chemical equivalent or more in terms of hydrogen ion with respect to the nitrogen atom in the amino group-containing organopolysiloxane molecule. here,
When the added acid is an acid having a basic group such as an amino group in the molecule, the difference between the valence of the acid and the valence of the base is defined as the effective valence of the acid. For example, glutamic acid is a monovalent acid because it has two carboxyl groups which are monovalent acids and one amino group which is a monovalent base in the molecule. By the addition of an acid, the amino group in the amino group-containing organopolysiloxane reacts with hydrogen ions to form an amine salt, whereby the hydrophilicity of the amino group-containing organopolysiloxane is increased and a microemulsion can be obtained. Therefore, if the amount of the acid added is smaller than the above amount, the amino group-containing organopolysiloxane is insufficient in hydrophilicity, resulting in a cloudy emulsion. Further, the upper limit of the amount of the acid added is not particularly limited, but usually, it is not used in excess of 1 chemical equivalent in terms of hydrogen ion.

In the amino group-containing organopolysiloxane microemulsion of the present invention, other additives such as silane compounds, crosslinking agents, preservatives, salts and dimethylpolysiloxane, epoxy group-containing organopolysiloxane, carboxy group-containing organopolysiloxane are added. Various polysiloxanes such as siloxanes, polysiloxane / polyoxyalkylene copolymers, silanol group-containing organopolysiloxanes and the like can be contained within a range not impairing the effects of the present invention.

In the present invention, the method for emulsifying and dispersing the amino group-containing organopolysiloxane in water is not particularly limited. For example, the amino group-containing organopolysiloxane, the surfactant, water and other optional additives may be added to the propeller blade or It consists of mixing and homogenizing with a stirring device such as a homomixer. In addition, the neutralization method is not particularly limited, and for example, a method of stirring the acid as it is or after adding an aqueous solution of the acid after emulsification, a mixture of an amino group-containing organopolysiloxane, a surfactant and other additives as desired. Examples include a method in which an aqueous solution of an acid is added dropwise to the emulsion to simultaneously emulsify and neutralize. Here, water is added alone or in the form of an aqueous solution of an acid, but since a microemulsion is formed, the final amount of water added is 40 to 5000 with respect to 100 parts by weight of the amino group-containing organopolysiloxane.
It is appropriately selected from the range of 00 parts by weight.

[0020]

EXAMPLES Next, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples, and those embodying the technical idea of the present invention are within the scope of the present invention. Contained within. Example 1 The following formula:

[Chemical 4] The amino group-containing organopolysiloxane 120 represented by
g, polyoxyethylene lauryl ether {ethylene oxide (EO) addition mole number 8 moles, HLB = 13.1}
70 g was charged into a 1 liter beaker and uniformly mixed with a homomixer at 5000 rpm for 5 minutes, and then, under the same stirring, 700 g of water was added to 8.8 g of L-glutamic acid (based on the nitrogen atom in the amino group-containing organopolysiloxane molecule). Then, an aqueous solution in which 0.4 equivalent of hydrogen ion (corresponding to hydrogen ion equivalent) was dissolved and stirred for 20 minutes to obtain a microemulsion. This is called microemulsion A.

Example 2 Aspartic acid as an acid in place of L-glutamic acid
A microemulsion was obtained in the same manner as in Example 1 except that 0 g (corresponding to 0.4 chemical equivalent in terms of hydrogen ion relative to nitrogen atom in the amino group-containing organopolysiloxane molecule) was used. This is called microemulsion B.

Example 3 1.0 g of γ-glycidoxypropyltrimethoxysilane was added to 800 g of the microemulsion A obtained in Example 1.
g was added and completely dissolved by stirring. This is called microemulsion C.

Example 4 (However, Reference Example) The following equation:

[Chemical formula 5] The amino group-containing organopolysiloxane 120 represented by
g, polyoxyethylene nonyl phenyl ether (EO
70g of added moles 7mol, HLB = 11.6) was charged into a 1 liter beaker and 5,000 rp with a homomixer.
After uniformly mixing for 5 minutes at m, water 550 was added under the same stirring.
An aqueous solution in which 3.8 g of sulfamic acid (corresponding to 0.5 chemical equivalent in terms of hydrogen ion with respect to nitrogen atom in amino group-containing organopolysiloxane molecule) was dissolved in g, and stirred for 20 minutes, microemulsion Got
This is called microemulsion D.

[0024]

Example 5 (however, reference example) With respect to 800 g of the microemulsion D obtained in Example 4, {N-β- (aminoethyl) -γ-aminopropyl}
-0.2 g of trimethoxysilane was added and completely dissolved by stirring. This is called microemulsion F.

Example 6 The following equation:

[Chemical formula 6] The amino group-containing organopolysiloxane 150 represented by
90 g of polyoxyethylene tridecyl ether (10 moles of EO added, HLB = 13.7) were charged into a 1-liter beaker, and a homomixer was operated at 5000 rpm.
After homogeneously mixing for 5 minutes, 700 g of water under the same stirring
An aqueous solution in which 11.7 g of glutamic acid (corresponding to 0.2 chemical equivalent in terms of hydrogen ion to nitrogen atom in amino group-containing organopolysiloxane molecule) was dissolved was added,
The mixture was stirred for 20 minutes to obtain a microemulsion. This is called microemulsion G.

Comparative Example 1 As Example 1 except that the acid was changed to 6.3 g of 35% hydrochloric acid (equivalent to 0.4 chemical equivalent in terms of hydrogen ion relative to nitrogen atom in amino group-containing organopolysiloxane molecule). A microemulsion was prepared in a similar manner. This is called microemulsion H.

Comparative Example 2 The same as Example 3 except that the acid was 4.5 g of acetic acid (corresponding to 0.5 chemical equivalent in terms of hydrogen ion to nitrogen atom in amino group-containing organopolysiloxane molecule). The method produced a microemulsion. This is called Micro Emulsion I.

Comparative Example 3 The same as Example 4 except that 1.8 g of formic acid (corresponding to 0.5 chemical equivalent in terms of hydrogen ion relative to nitrogen atom in amino group-containing organopolysiloxane molecule) was used as the acid. The method produced a microemulsion. This is called Micro Emulsion J.

Comparative Example 4 The same as Example 5 except that 2.9 g of propionic acid (corresponding to 0.5 chemical equivalent in terms of hydrogen ion relative to nitrogen atom in amino group-containing organopolysiloxane molecule) was used as the acid. A microemulsion was produced by the method described in 1. This is called microemulsion K.

Comparative Example 5 2.6 g of phosphoric acid (0.2 g in terms of hydrogen ion with respect to nitrogen atom in amino group-containing organopolysiloxane molecule) was used.
A microemulsion was produced in the same manner as in Example 6 except that the chemical equivalent was used). This is called microemulsion L.

Examples 1 to 6 (however, see Examples 4 and 5)
Consideration) and the microemulsions A to G and HL obtained in Comparative Examples 1 to 5 were evaluated for transparency, storage stability (50 ° C., 70 ° C.), mechanical stability, and dilution stability. . The results are shown in Tables 1 and 2. The evaluation method and criteria of each characteristic are as follows.

Evaluation method Transparency: Visual observation of the appearance of the microemulsion immediately after production. Storage stability (50 ° C, 30 days): 100 g of the microemulsion was placed in a 200 ml sealed glass bottle, and 5
Let stand in a constant temperature bath at 0 ° C and visually observe the appearance after 30 days. Storage stability (70 ° C, 7 days): 100 g of the microemulsion was placed in a 200 ml sealed glass bottle, and 70
Let stand in a constant temperature bath at ℃ and visually observe the appearance after 7 days. Mechanical stability: The microemulsion was diluted to 2% with water, stirred with a homomixer at 8000 rpm for 10 minutes, and then visually observed. Dilution stability (50 ° C, 7 days): Dilute the microemulsion to 2% with water, put it in a 200 ml sealed glass bottle, leave it in a constant temperature bath at 50 ° C, and visually observe the appearance after 7 days. .

Evaluation Criteria ⊚: Colorless and transparent appearance (light transmittance 80 to 10)
0T%) O: Appearance that is pale white and slightly turbid (light transmittance of 50 to 80)
T%) Δ: Appearance slightly clouded (light transmittance 20 to 50 T%) ×: White appearance (light transmittance 0 to 20 T%) or separation is observed

[0035]

[Table 1]

[0036]

From the above results, in the production of the amino group-containing organopolysiloxane microemulsion, in the present invention, by applying the technique of using an acid containing an amino group or a substituted amino group in the molecule, the conventional method is used. Compared with the amino group-containing organopolysiloxane microemulsion obtained by, the amino group-containing organopolysiloxane microemulsion has far superior performances in storage stability, dilution stability, mechanical stability, thermal stability and transparency. It was confirmed that an emulsion was obtained. In particular, the microemulsion of the present invention has outstanding storage stability and dilution stability at high temperatures.

[0038]

As described in detail above, the amino group-containing organopolysiloxane microemulsion obtained according to the present invention is higher than that produced by the conventional method, especially under high temperature conditions of 50 to 90 ° C. It has excellent storage stability, dilution stability, mechanical stability, thermal stability, and transparency. Therefore, the amino group-containing organopolysiloxane microemulsion of the present invention is particularly useful as a fiber treating agent and the like.

Continuation of the front page (56) Reference JP-A-8-72748 (JP, A) JP-A-6-220722 (JP, A) JP-A-3-170557 (JP, A) JP-A-3-119060 (JP , A) JP 60-181322 (JP, A) JP 1-306682 (JP, A) JP 6-220723 (JP, A) JP 2-284959 (JP, A) JP 6-170212 (JP, A) JP-A-5-139941 (JP, A) JP-A-5-209058 (JP, A) Special Table 2-503204 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08G 77/00-77/62 C08L 83/00-83/16 D06M 15/00-15/72 WPI / L (QUESTEL) CA (STN) REGISTRY (STN)

Claims (2)

(57) [Claims] 1. The following formula I: {In the formula, R ¹ is a hydrogen atom, a hydroxyl group, a monovalent hydrocarbon group having 1 to 20 carbon atoms or the following formula: —OR ′ (wherein
R ′ represents a group represented by a monovalent hydrocarbon group having 1 to 20 carbon atoms), A represents the following formula: —R ² (NR ³ R ⁴ ) _z NR ⁵ R ⁶ (in the formula,
R ² and R ⁴ independently of each other have 1 to 6 carbon atoms.
Represents a divalent hydrocarbon group, R ³ , R ⁵ and R ⁶ independently of each other represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, and z represents an integer of 0 to 5. ) Represents an organic functional group, and x and y have the following conditions: 0 <x ≦ 3, 0 ≦ y <3, 0 <
x + y ≦ 3, and the proportion of amino groups in the molecular weight of the compound of formula I is 0.2 in terms of NH _2.
5% by weight or more} 100 parts by weight of an amino group-containing organopolysiloxane represented by
In producing an emulsion consisting of 0 part by weight and 40 to 500000 parts by weight of water, an amount equivalent to 0.1 chemical equivalent or more in terms of hydrogen ion relative to the nitrogen atom in the amino group-containing organopolysiloxane molecule is produced. , Glutamine
A method for producing an amino group-containing organopolysiloxane microemulsion, which comprises adding an acid having an amino group or a substituted amino group in a molecule selected from the group consisting of an acid and aspartic acid to neutralize the molecule. 2. An amino group-containing organopolysiloxane microemulsion produced by the method according to claim 1.