JPH04279667A - Method for producing oil-in-water organopolysiloxane emulsion - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention]

0001

[Field of Industrial Application] The present invention relates to a method for producing an oil-in-water organopolysiloxane emulsion, and in particular to a composition that allows easy production of an oil-in-water organopolysiloxane emulsion with a small average particle size and excellent stability. This relates to a manufacturing method. Among the emulsions produced according to the present invention are those suitable as fiber treatment agents.

0002

BACKGROUND OF THE INVENTION In order to improve the stability of organopolysiloxane emulsions, attempts have been made to reduce the particle size. This is largely due to requests from the textile processing field.

[0003] In the field of textile processing, various processing agents have been proposed to improve the properties of textile products made of various natural fibers and synthetic fibers, such as smoothness and flexibility, and to impart a good texture. As silicone-based fiber treatment agents, those containing dimethylpolysiloxane as a main component, those containing amino group-modified organopolysiloxane as a main component, and the like are known. These silicone fiber treatment agents are generally emulsified using an emulsifier and used as an oil-in-water emulsion.

[0004] When treating textile products with these emulsion-type fiber treatment agents, the treatment agent is diluted 10 to 100 times with water, subjected to strong mechanical shear such as stirring, circulation, squeezing, etc. Emulsions are often subjected to harsh conditions, such as being exposed to high temperatures or being used in combination with inorganic substances or other chemicals.

[0005] If the emulsion is destroyed under such conditions and the silicone component separates, the silicone will adhere unevenly to the surface of the textile product, and its strong water repellency may result in uneven dyeing. This can cause serious problems, such as the areas to which silicone is attached appear dark colored due to the difference in refractive index (so-called oil spot phenomenon).

[0006] For this reason, studies have been made to improve the stability of emulsions, and one way to improve stability is to reduce the particle size, and so-called microemulsions and methods for producing them have been proposed so far. ing.

For example, there is a method of obtaining a clear microemulsion through a four-step process using two types of surfactants with different solubility in organopolysiloxane (see US Pat. No. 4,146,499). emulsifier,
Emulsification method using a combination of organic acids and amines (U.S. Pat. No. 3,975,294 and U.S. Pat. No. 4,052,3)
(see Publication No. 31) has been proposed. However, these methods are complicated and require an extremely large amount of emulsifier, which impairs the excellent properties of silicone and makes it impossible to obtain sufficient flexibility, so they are not practical methods. do not have.

As another example, an organopolysiloxane containing a polar group is added with an insoluble emulsifier and water,
Once a translucent oil concentrate is produced, it is rapidly dispersed in water (phase inversion method), resulting in an average particle size of 0.3 μm.
Method for obtaining the following emulsion (Japanese Unexamined Patent Publication No. 60-1273
(Refer to Publication No. 27) has been proposed, but this method requires careful control of time and temperature between each step, making process control complicated, and the resulting emulsion product is also not good as a fiber treatment agent. It was not something that could give it a nice texture.

Still other examples include a method in which a siloxane raw material emulsion having trifunctional units is gradually dropped into an aqueous solution containing an emulsion polymerization catalyst (see JP-A-64-160); Method for neutralizing emulsions (Japanese Unexamined Patent Publication No. 63-27087
No. 5) has also been proposed, but emulsions made by either method have not been able to impart a satisfactory texture to textile products.

[0010]Also, an emulsion obtained by adding an organic acid to an emulsion of an amino group-containing organopolysiloxane and reacting it (Japanese Patent Application Laid-Open No. 2-284959) gives a relatively good texture, but it requires a reaction step. Therefore, the manufacturing process lacked simplicity.

[0011]

[Problems to be Solved by the Invention] In view of the above-mentioned circumstances, the present invention aims to provide an emulsion for treating fibers that has both a texture-improving effect such as excellent flexibility and excellent stability. This invention was made in an attempt to provide a composition and manufacturing method for easily manufacturing a small and highly stable organopolysiloxane emulsion product by a simple means.

0012

[Means for Solving the Problems] The present invention has solved the above-mentioned problems.
-c)/2 [In the formula, Q is -R3 -O(Cx H2xO
)y A (A is a hydrogen atom, an acyl group, or a monovalent hydrocarbon group, R3 is a divalent hydrocarbon group, x is an integer of 2 to 4, y
is an integer from 3 to 100. ), and R1 is
An unsubstituted or halogen-substituted monovalent hydrocarbon group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms, and R2
is an amino group-containing hydrocarbon group, an amino group-containing hydrocarbon group in which H of the amino group is replaced with an alkyl group or an aminoalkyl group, an amino group-containing hydrocarbon group in which the amino group is reacted with an epoxy compound, an organic acid, or an inorganic acid. group, an epoxy group-containing unsubstituted or heteroatom-substituted hydrocarbon group, an unsubstituted or heteroatom-substituted hydrocarbon group obtained by reacting an epoxy group with an amine, and 0.001≦a≦0.2, 1.6≦b ≦2
．． 0, 0.001≦c≦0.2, 1.8≦a+b+c≦
2.1. ] Organopolysiloxane represented by
100 parts by weight b) Emulsifier
5-100 parts by weight c) Water
20-200
The gist of the present invention is a method for producing an oil-in-water organopolysiloxane emulsion, which is characterized in that 0 parts by weight of the three components are charged at once and then emulsified.

In order to solve the above-mentioned problems, the present inventors conducted intensive research and found that a chain organopolysiloxane having a specific amount of polyether groups was mixed with a specific amount of an emulsifier and water, and the mixture was brought into contact with the mixture under stirring. Therefore, without going through the phase inversion process,
An oil-in-water type (hereinafter referred to as O/W type) microemulsion that can be easily mixed and emulsified and has an average particle size of 0.3 μm or less, which is a desirable particle size from the viewpoint of stability, is obtained. It was discovered that a microemulsion having excellent properties as a drug could also be obtained, and the present invention was completed after further investigation.

The present invention will be explained in detail below. The organopolysiloxane used in the present invention is represented by the above general formula. Q in the formula is -R3-O(Cx H2xO
)y is a polyoxyalkylene group represented by A,
The terminal capping group A is a hydrogen atom, an acyl group, or a monovalent hydrocarbon group such as methyl, ethyl, propyl, butyl, and R3 is -CH2 CH2 CH2 -, -C
It is a divalent hydrocarbon group such as H2 CH2 -. Further, x is an integer of 2 to 4, and y is an integer of 3 to 100, and integers of 3 to 20 are particularly preferred for fiber treatment. When x is 5 or more, hydrophilicity is insufficient and it is difficult to make a microemulsion, when x is 1, it is difficult to produce industrially, and when x is 2, or a mixture of 2 and 3. Particularly preferred is the case. When y is 2 or less, an emulsion with the desired fine particle size is produced without going through a phase inversion process.
It cannot be obtained by a step-by-step emulsification process, and if it exceeds 100, it becomes viscous or solid and has poor workability. Further, for fiber treatment, if the value of y is too large, the effect of imparting flexibility to the fibers will be reduced, so y is preferably 3 to 20.

R1 is an unsubstituted or halogen-substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, or an alkoxy group, such as an aliphatic group such as methyl, ethyl, propyl, butyl, hexyl, octyl, nonyl, dodecyl, or octadecyl. Monovalent hydrocarbon groups, aromatic monovalent hydrocarbon groups such as phenyl and tolyl, alicyclic monovalent hydrocarbon groups such as cyclopentyl and cyclohexyl, halogen-substituted monovalent hydrocarbon groups such as trichloropropyl, chloromethyl, chlorophenyl, and chloropropyl. Examples include hydrogen groups, alkoxy groups such as methoxy, ethoxy, propoxy, and butoxy. Among these, a methyl group is preferred as R1.

R2 is an amino group-containing hydrocarbon group, an amino group-containing hydrocarbon group in which H of the amino group is substituted with an alkyl group or an aminoalkyl group, or an amino group in which the amino group is reacted with an epoxy compound, an organic acid, an inorganic acid, etc. group-containing hydrocarbon group,
It is an unsubstituted or heteroatom-substituted hydrocarbon group containing an epoxy group.

The amino group-containing hydrocarbon group is -CH2
CH2CH2 NH2 , -CH2 CH2 CH2
CH2 NH2, those in which H of the amino group is substituted with an alkyl group or an aminoalkyl group include -CH2 C
H2 CH2 NHCH2 CH2 NH2 , -CH
-CH2 C
H2 CH2NHCH2 CH2 NH2 , -CH2
Those reacted with CH2 CH2 NH2, etc., and epoxy group-containing unsubstituted or heteroatom-substituted hydrocarbon groups include:

[0018]

[Chemical formula 1]

[0019]

[Case 2]

##STR1## and the hetero atom is particularly preferably an oxygen atom. As a result of reacting an epoxy group with an amine,

[0021]

[Chemical formula 3]

[0022]

[C4]

and NH2 -CH2 CH2 -NH
2, CH3-NH-CH3, etc. are exemplified.

[0024] Furthermore, if the content of the polyoxyalkylene group Q is too low, microemulsion cannot be formed by the bulk emulsification process without going through the phase inversion step described later, and if it is too large, the effect of imparting flexibility to textile products will be reduced. It is impractical and its amount is limited, and the general formula Qa R
a in 1bR2cSiO(4-a-b-c)/2
It is necessary that the value of a be 0.001≦a≦0.2. When R2 is an amino-containing group, it imparts excellent flexibility with a slimy feel, and when it is an epoxy-containing group, it imparts dry-touch flexibility. At this time, if R2 is less than 0.1 mol%, a sufficient introduction effect will not be obtained, and if it exceeds 20 mol%, discoloration will easily occur in the case of amino-containing groups, and compatibility with other drugs will occur in the case of epoxy-containing groups. When used in combination, the stability of the emulsion is deteriorated and scum and gel are likely to occur, so the value of c needs to be 0.001≦c≦0.2.

Furthermore, in order to impart good flexibility, the organopolysiloxane must have a linear structure (some branched structure is allowed), and a+b+c is 1.8.
It is necessary that the range is ≦a+b+c≦2.1.

The emulsifier used in the production of the organopolysiloxane emulsion of the present invention is not particularly limited, and examples include nonionic emulsifiers such as polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, sorbitan fatty acid ester, glycerin fatty acid ester; Examples include anionic emulsifiers such as sodium lauryl sulfate, sodium dodecylbenzenesulfonate, and sodium polyoxyethylene ether carboxylate; cationic emulsifiers such as quaternary ammonium salts; however, in order to obtain a transparent and stable emulsion, 50 of the amount of emulsifier
It is preferable that at least % by weight of the nonionic emulsifier is a nonionic emulsifier, and that the weighted average HLB of the nonionic emulsifier is within the range of 9 to 14.

[0027] Only one emulsifier may be used, or two emulsifiers may be used.
You may use a combination of two or more species. The amount added is the amount necessary to emulsify the organopolysiloxane, but if it is too small, the particle size will increase and the properties will deteriorate.
If the amount is too large, the flexibility will deteriorate, so it is necessary to use 5 to 100 parts by weight per 100 parts by weight of the organopolysiloxane. Preferably it is 5 to 50 parts by weight.

Regarding the amount of water used in the production method of the present invention, if it is too small, an O/W type emulsion cannot be obtained;
Too much amount is disadvantageous for storage and transportation of the product, so 20 to 200 parts by weight per 100 parts by weight of organopolysiloxane.
It is necessary that the amount is 0 parts by weight. Particularly preferably 10
It is 0 to 500 parts by weight.

The organopolysiloxane described above,
Emulsification can be achieved without going through a phase inversion process by placing a predetermined amount of emulsifier and water in a container all at once, and mixing and stirring with a stirrer such as a homomixer, or shaking with a shaker. , it is possible to obtain an O/W type emulsion having a desirable particle size, that is, an average particle size of 0.3 μm or less. The strength and time of stirring and shaking will vary depending on whether the mixture of organopolysiloxane and emulsifier has high or low hydrophilicity, but the lower the hydrophilicity, the longer and stronger stirring will be required. However, they can be mixed and dispersed using commercially available equipment such as a homomixer, homogenizer, sand grinder, or colloid mill.

The emulsion obtained by the method of the present invention has good stability over time, dilution stability and mechanical stability.

[0031] Textile products are treated with the organopolysiloxane emulsion obtained by the method of the present invention, by diluting this emulsion with water to an appropriate concentration to prepare a treatment solution, and treating it by methods such as dipping, padding, or spraying. This can be carried out by applying the liquid to the textile product, removing excess treatment liquid using a mangle, centrifuge, etc. to adjust the amount of adhering liquid, and then drying or heating. The heating temperature may normally be about 100 to 180°C, and the heating time may be about 2 to 30 minutes.

[0032] The organopolysiloxane emulsion of the present invention can improve the smoothness, flexibility, etc. and impart a good texture to any textile product when treated with the above-mentioned preferred ones for textile treatment. can do. For example, it can be applied to various textile products such as stuffed cotton made of polyester fibers, stuffed cotton made of acrylic fibers or nylon fibers, and natural fibers such as cotton fibers and wool fiber products. Further, these fiber products can be applied regardless of whether they are in the form of filaments, threads, fabrics, knitted fabrics produced using these fibers, or the like. Furthermore, it can also be applied to inorganic fibers such as glass fibers, carbon fibers, aramid fibers, etc.

[0033]

[Examples] Next, the present invention will be explained with reference to Examples and Comparative Examples. Note that parts in the examples represent parts by weight.

Example 1 Formula (average formula, same below)

[0035]

[C5]

Organopolysiloxane 100 represented by
1 part, 40 parts of polyoxyethylene tridecyl ether (HLB=11.5) as an emulsifier, 1 part of polyoxyethylene nonylphenyl ether sodium sulfate, and 190 parts of water were placed in a container, and the mixture was stirred for 15 minutes at 5,000 rpm using a homomixer. A transparent O/W type emulsion was obtained.

[0037] The average particle size of this emulsion is 0.016
μm, and remained stable with no change at all even after being left at 25° C. for 3 months. In addition, the average particle size is determined by COUL, a method of measuring the diffusion coefficient by photon correlation spectroscopy and calculating the particle size.
Measurement was carried out using COULTERN4 model manufactured by TER. In addition, this emulsion was diluted 50 times with water and 500 times diluted with water.
All diluted emulsions remained stable with no change at all even after being left at 25° C. for 24 hours. moreover,
This emulsion was diluted 50 times with water and stirred with a homomixer at 5,000 rpm for 10 minutes, and then
Even when the emulsion was left for 24 hours at ℃, there was no change at all and the emulsion remained stable.

Example 2 formula

[0039]

[C6]

Organopolysiloxane 100 represented by
1 part, 40 parts of polyoxyethylene tridecyl ether (HLB=11.5) as an emulsifier, 1 part of polyoxyethylene nonylphenyl ether sodium sulfate, and 190 parts of water were placed in a container, and the mixture was stirred for 15 minutes at 5,000 rpm using a homomixer. A transparent O/W type emulsion was obtained.

[0041] The average particle size of this emulsion is 0.015
μm, and remained stable with no change at all even after being left at 25° C. for 3 months. Also, the emulsion diluted 50 times with water and the one diluted 500 times are both 2
Even after being left at 5°C for 24 hours, the emulsion remained stable with no change at all. Furthermore, this emulsion was diluted 50 times with water and then mixed with a homomixer at 5,000 rpm for 10 minutes.
After stirring for a minute, the emulsion remained stable even when it was left at 25° C. for 24 hours without any change.

Example 3 formula

[0043]

[C7]

Organopolysiloxane 100 represented by
24 parts of polyoxyethylene nonylphenyl ether (HLB=8.9) as an emulsifier, 16 parts of polyoxyethylene lauryl ether (HLB=16.5) (weighted average HLB=11.94), polyoxyethylene nonylphenyl ether 1 part of sodium sulfate and 190 parts of water were placed in a container and stirred for 15 minutes at 5,000 rpm using a homomixer to obtain a transparent O/W type emulsion with an average particle size of 0.038 μm.

Example 4 formula

[0046]

[Chemical formula 8]

Organopolysiloxane 100 represented by
1 part, 20 parts of polyoxyethylene tridecyl ether (HLB=11.5) as an emulsifier, 1 part of polyoxyethylene nonylphenyl ether sodium sulfate, and 190 parts of water were placed in a container, and the mixture was stirred for 15 minutes at 5,000 rpm using a homomixer. A transparent O/W type emulsion with an average particle size of 0.012 μm was obtained.

Example 5 formula

[0049]

[Chemical formula 9]

Organopolysiloxane 100 represented by
parts, the same amount of the same emulsifier as in Example 1, and 195 parts of water.
A portion of the mixture was placed in a container and stirred for 15 minutes at 7,000 rpm using a homomixer to obtain a transparent emulsion with an average particle size of 0.015 μm.

Example 6 formula

[0052]

[Chemical formula 10]

Organopolysiloxane 100 represented by
1 part, 5 parts of polyoxyethylene tridecyl ether (HLB=13.5) as an emulsifier, and 228 parts of water were placed in a container, and stirred for 15 minutes at 7,000 rpm using a homomixer to form translucent particles with an average particle size of 0.1 μm. An O/W emulsion was obtained.

Example 7 formula

[0055]

[Chemical formula 11]

Organopolysiloxane 100 represented by
A container was charged with 40 parts of polyoxyethylene tridecyl ether (HLB=11.5) as an emulsifier and 190 parts of water, and stirred with a homomixer at 5,000 rpm for 15 minutes to form a transparent O with an average particle size of 0.03 μm. /W type emulsion was obtained.

Example 8 formula

[0058]

[Chemical formula 12]

Organopolysiloxane 100 represented by
40 parts of polyoxyethylene tridecyl ether (HLB=11.5) as an emulsifier and 190 parts of water were placed in a container and stirred for 15 minutes at 5,000 rpm using a homomixer to form transparent O with an average particle size of 0.032 μm. /W type emulsion was obtained.

Example 9 The same organopolysiloxane, emulsifier, and water as in Example 1 were placed in a container in the same amount as in Example 1, and the mixture was heated with a shaker for 20 minutes.
Shake at a strength of 0 times/min for 30 minutes, and the average particle size is 0.02.
A transparent O/W type emulsion of 3 μm was obtained.

Comparative example 1 formula

[0062]

[Chemical formula 13]

Organopolysiloxane 100 represented by
The same emulsifier and water as in Example 1 were added to the weight part and stirred for 15 minutes at 5,000 rpm using a homomixer.
The emulsion did not become uniform and separated.

Comparative example 2 formula

[0065]

[Chemical formula 14]

Organopolysiloxane 100 represented by
1 part, the same amount of the same emulsifier as in Example 1, 190 parts of water
A portion of the mixture was placed in a container and stirred for 20 minutes at 7,000 rpm using a homomixer to obtain a milky white emulsion with an average particle size of 0.8 μm.

[0067] This emulsion was diluted 50 times with water and stirred for 10 minutes at 5,000 rpm using a homomixer. After this product was left at 25°C for 24 hours, an oil film was observed on the liquid surface.

Example 10 The emulsions obtained in Examples 1 to 9 and Comparative Examples 1 to 2 were each diluted with water so that the siloxane content was 0.3% by weight, and cotton broadcloth and polyester/ After soaking cotton (65/35) blended broadcloth, the squeezing rate is 1.
Squeeze with a roll at 00%, then 100℃/
After drying for 2 minutes, heat treatment was further performed at 150° C. for 2 minutes.

The flexibility of the treated fabric obtained above was evaluated using a Uenoyama style hand meter (manufactured by Uenoyama Kiko Co., Ltd.), and the results are shown in Table 1. Note that the numerical values in the table represent the bending resistance of the cloth as flexibility (g), and the larger the numerical value, the poorer the flexibility.

[0070]

[Table 1]

As mentioned above, Examples 1, 2, 3, 4, 7,
It can be seen that the emulsions obtained in Nos. 8 and 9 have good flexibility. However, although the emulsions obtained in Examples 5 and 6 are microemulsions, they do not have much softening effect. From these facts, it can be seen that as a treatment agent for fibers, it is better that the polyoxyalkylene group is not too long.

[0072]

[Effects of the Invention] The present invention solves the disadvantages of the prior art and enables microemulsion of organopolysiloxane by a one-step emulsification method that does not require a phase inversion step, thereby greatly simplifying the emulsification process. This made manufacturing easier. In addition, the emulsion obtained by the production method of the present invention has good stability, and furthermore, this emulsion can be used to impart excellent texture to various textile products. was discovered. As described above, the present invention has a number of features, and its effects are extremely large.

Claims (3)

[Claims] [Claim 1] A) General formula Qa R1bR2cSiO
(4-a-b-c)/2 [In the formula, Q is -R3-O(Cx H2xO)y A(A
is a hydrogen atom, an acyl group or a monovalent hydrocarbon group, R3 is a divalent hydrocarbon group, x is an integer of 2 to 4, and y is 3 to 100
is an integer. ), and R1 has 1 to 2 carbon atoms.
0 unsubstituted or halogen-substituted monovalent hydrocarbon group or an alkoxy group having 1 to 20 carbon atoms, and R2 is an amino group-containing hydrocarbon group, an amino group in which H of the amino group is replaced with an alkyl group or an aminoalkyl group. Containing hydrocarbon groups, amino group-containing hydrocarbon groups made by reacting amino groups with epoxy compounds, organic acids or inorganic acids, unsubstituted or heteroatom-substituted hydrocarbon groups containing epoxy groups, unsubstituted by reacting epoxy groups with amines or a heteroatom-substituted hydrocarbon group,
0.001≦a≦0.2, 1.6≦b≦2.0, 0.0
01≦c≦0.2, 1.8≦a+b+c≦2.1. ] Organopolysiloxane 100
Part by weight b) Emulsifier
5-100 parts by weight c) Water
A method for producing an oil-in-water organopolysiloxane emulsion, which comprises adding 20 to 2000 parts by weight of the three components at once and then emulsifying them. 2. The method for producing an oil-in-water organopolysiloxane emulsion according to claim 1, wherein an organopolysiloxane in which Q is located at the end of a siloxane chain is used. 3. The oil-in-water organopolysiloxane according to claim 1, wherein 50% by weight or more of the blended amount of the emulsifier is a nonionic emulsifier, and the weighted average HLB of the nonionic emulsifier is 9 to 14. Method of manufacturing emulsion.