JPH0686575B2 - Method for producing oil-in-water type organopolysiloxane emulsion - Google Patents

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 oil-in-water type organopolysiloxane emulsion, and in particular, a composition which can easily obtain an oil-in-water type organopolysiloxane emulsion having a small average particle size and excellent stability. The present invention relates to a manufacturing method. Among the emulsions produced according to the present invention are those suitable for fiber treating agents.

[0002]

2. Description of the Related Art In order to improve the stability of organopolysiloxane emulsions, studies have been conducted to reduce the particle size. This is largely due to the request from the fiber processing field.

In the field of fiber treatment, various treatment agents have been proposed in order to improve the properties of a fiber product composed of various natural fibers and synthetic fibers, such as smoothness and flexibility, and to impart a good texture. Known silicone-based fiber treatment agents include those containing dimethylpolysiloxane as a main component and those containing amino group-modified organopolysiloxane as a main component. These silicone fiber treating agents are generally emulsified with an emulsifier and used as an oil-in-water emulsion.

When treating textiles with these emulsion type fiber treatment agents, the treatment agents may be diluted 10 to 100 times with water, or may be subjected to a strong mechanical share such as stirring, circulation and squeezing. The emulsion is often subjected to severe conditions such as being exposed to high temperatures and being used in combination with inorganic substances and other drugs.

When the emulsion is broken under these conditions and the silicone component is separated, the silicone adheres unevenly to the surface of the textile product, and due to its strong water repellency, the dyeing may not be performed uniformly. However, serious troubles occur such that only the part to which silicone is attached looks dark due to the difference in refractive index (so-called oil spot phenomenon).

For this reason, studies have been conducted to increase the stability of emulsions, but one method of improving the stability is to reduce the particle size, and so-called microemulsions and their production methods have been proposed so far. ing.

For example, a method of obtaining a clear microemulsion through a four-step process using two kinds of surfactants having different solubilities in organopolysiloxane (see US Pat. No. 4,146,499) is limited. Emulsifier,
Emulsification method by combination of organic acid and amine (US Pat. No. 3,975,294 and US Pat. No. 4,052,3)
No. 31) are proposed. However, in these methods, the process is complicated, and since an extremely large amount of an emulsifier is required, the excellent properties of silicone are impaired by that amount and sufficient flexibility cannot be obtained. Absent.

As another example, a polar group-containing organopolysiloxane is added with an insoluble emulsifier and water,
Once a semi-transparent oil concentrate has been produced, it is rapidly dispersed in water (phase inversion method) to give an average particle size of 0.3 μm.
A method for obtaining the following emulsion (JP-A-60-1273)
No. 27 gazette) has been proposed, but since this method requires careful attention to control of time and temperature between each step, process control is complicated, and the obtained emulsion product is also good as a fiber treatment agent. It was not able to give a nice texture.

As still another example, a method of gradually dropping a siloxane raw material emulsion having a trifunctional unit into an aqueous solution containing an emulsion polymerization catalyst (see JP-A-64-160), a carboxyl group-containing organopolysiloxane. Method for neutralizing emulsion (Japanese Patent Laid-Open No. 63-27087)
No. 5, gazette) is also proposed, but the emulsions obtained by any of the methods could not impart a satisfactory texture to the fiber product.

The emulsion obtained by adding an organic acid to an emulsion of an amino group-containing organopolysiloxane and reacting it (JP-A-2-284959) gives a relatively good texture, but requires a reaction step. Therefore, the manufacturing process lacks convenience.

[0011]

SUMMARY OF THE INVENTION In view of the above situation, the present invention has a particle size including an emulsion for fiber treatment which has a feeling improving effect such as excellent flexibility and an excellent stability. The object of the present invention is to provide a composition and a manufacturing method for easily manufacturing a small and stable organopolysiloxane emulsion product by a simple means.

[0012]

SUMMARY OF THE INVENTION The present invention has solved the above-mentioned problems by: a) General formula Q _a R ¹ _b R ² _c SiO _{(4-abc) / 2} [wherein Q is
Is —R ³ —O (C _x H _2x O) _y A (A is a hydrogen atom, an acyl group or a monovalent hydrocarbon group, R ³ is a divalent hydrocarbon group,
x is an integer of 2 to 4, and y is an integer of 3 to 100. ), R ¹ 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 R ² is an amino group-containing hydrocarbon group or amino group. Amino group-containing hydrocarbon group in which H of the group is substituted with an alkyl group or aminoalkyl group, amino group-containing hydrocarbon group obtained by reacting an amino group with an epoxy compound, an organic acid or an inorganic acid, an epoxy group-containing unsubstituted or hetero atom A 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. ] 100 parts by weight b) emulsifier 5 to 100 parts by weight c) water 20 to 2000 parts by weight, and after emulsifying all three components in a batch, an oil-in-water organopolysiloxane emulsion characterized by The main point is the manufacturing method.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a chain-like organopolysiloxane having a specific amount of a polyether group is mixed with a specific amount of an emulsifier and water and contacted with 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 for stability, is obtained. It was found that a microemulsion having excellent properties as an agent can be obtained, and further studies were conducted to complete the present invention.

The present invention will be described in detail below. The organopolysiloxane used in the present invention is represented by the above general formula. Q in the formula is ^{_{-R 3 -O (C x H 2x}} O) y A
Is a polyoxyalkylene group represented by, and A of the terminal blocking group is a hydrogen atom, an acyl group, or a monovalent hydrocarbon group such as methyl, ethyl, propyl, or butyl,
R ³ is a divalent hydrocarbon group such as —CH ₂ CH ₂ CH ₂ — and —CH ₂ CH ₂ —. X is an integer of 2 to 4, y
Is an integer of 3 to 100, and is particularly 3 for fiber treatment.
It is preferably an integer of -20. When x is 5 or more, the hydrophilicity is insufficient and it is difficult to form a microemulsion, and when x is 1, industrial production is difficult.
Is particularly preferably 2 or a mixture of 2 and 3. When y is 2 or less, the desired emulsion having a minute particle size cannot be obtained in the one-step emulsification step without undergoing the phase inversion step, and when it exceeds 100, it becomes viscous or solid and workability is improved. Is bad. Further, for fiber treatment, if the value of y is too large, the effect of imparting flexibility to the fiber is reduced, so y is preferably 3 to 20.

R ¹ is an unsubstituted or halogen-substituted monovalent hydrocarbon group having 1 to 20 carbon atoms or an alkoxy group, for example, a fat such as methyl, ethyl, propyl, butyl, hexyl, octyl, nonyl, dodecyl, octadecyl and the like. Tribe 1
Valent hydrocarbon groups, aromatic monovalent hydrocarbon groups such as phenyl and tolyl, alicyclic monovalent hydrocarbon groups such as cyclopentyl and cyclohexyl, trichloropropyl, chloromethyl,
Halogen substitution such as chlorophenyl and chloropropyl 1
Examples thereof include a valent hydrocarbon group and an alkoxy group such as methoxy, ethoxy, propoxy and butoxy. Above all, R
Preferred as ¹ is a methyl group.

R ² 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 is reacted with an epoxy compound, an organic acid, an inorganic acid or the like. Amino group-containing hydrocarbon group,
It is an epoxy group-containing unsubstituted or heteroatom-substituted hydrocarbon group.

As the amino group-containing hydrocarbon group, --CH _{2
CH 2 CH 2 NH 2, -CH} 2 CH 2 CH 2 CH 2 NH 2
, H of an amino group is substituted with an alkyl group or an aminoalkyl group, for example, -CH ₂ CH ₂ CH ₂ NHCH
_{2 CH 2 NH 2, -CH 2} CH 2 CH 2 N (CH 3)
_2, an epoxy compound an amino group, an organic acid, glycidol as obtained by reacting inorganic acid and acetic acid, such as phosphoric acid and _{-CH 2 CH 2 CH 2 NHCH 2} CH 2 NH 2, -C
As the one obtained by reacting H ₂ CH ₂ CH ₂ NH _2, etc., and the epoxy group-containing unsubstituted or heteroatom-substituted hydrocarbon group,

[0018]

[Chemical 1]

[0019]

[Chemical 2]

The hetero atom is preferably an oxygen atom. What reacted epoxy group with amine

[0021]

[Chemical 3]

[0022]

[Chemical 4]

Etc. and NH ₂ --CH ₂ CH ₂ --NH ₂ , C
Examples thereof include those obtained by reacting with H ₃ —NH—CH _{3 and the} like.

Further, if the content of the polyoxyalkylene group Q is small, microemulsification cannot be carried out by the batch emulsification process which does not go through the phase inversion step described later, and if it is too large, the effect of imparting flexibility to the fiber product is deteriorated. It is not practical and its amount is limited, and the above general formula Q _a R ¹ _b
In R ² _c SiO _{(4-abc) / 2} , the value of a is 0.001 ≦
It is necessary to satisfy a ≦ 0.2. When R ² is an amino-containing group, it imparts excellent slimy flexibility, and when it is an epoxy-containing group, it imparts dry touch flexibility. At this time, if R ² is less than 0.1 mol%, a sufficient introduction effect cannot be obtained, and if R ² is more than 20 mol%, discoloration is likely to occur in the case of an amino-containing group, and that of other agents in the case of an epoxy-containing group. When used together, the stability of the emulsion is deteriorated and scum and gel are easily generated, so the value of c is 0.0.
It is necessary to satisfy 01 ≦ c ≦ 0.2.

Further, in order to impart good flexibility, the organopolysiloxane needs to have a linear structure (some branched structure is allowed), and a + b + c is 1.8.
It is necessary to be in the range of ≦ 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 thereof include nonionic emulsifiers such as polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, sorbitan fatty acid ester and glycerin fatty acid ester; Anionic emulsifiers such as sodium lauryl sulfate, sodium dodecylbenzene sulfonate and sodium polyoxyethylene ether carboxylic acid; and cationic emulsifiers such as quaternary ammonium salts are mentioned, but in order to obtain a transparent and stable emulsion, 50 of the emulsifier content
It is preferable that the weight% or more is a nonionic emulsifier, and the weighted average HLB of the nonionic emulsifier is in the range of 9 to 14.

Only one type of emulsifier may be used, or 2
You may use it in combination of 2 or more types. The addition amount is an amount necessary for emulsifying the organopolysiloxane, but if it is too small, the particle size becomes large and the characteristics deteriorate, and if it is too large, the flexibility deteriorates. It is necessary to set 5 to 100 parts by weight to 100 parts by weight. It is preferably 5 to 50 parts by weight.

If the amount of water used in the production method of the present invention is too small, an O / W type emulsion cannot be obtained.
20 to 200 per 100 parts by weight of organopolysiloxane, since too much is disadvantageous for storage and transportation of products.
It should be 0 parts by weight. Particularly preferably 10
0 to 500 parts by weight.

The organopolysiloxane described above,
It is possible to emulsify without passing through a phase inversion step by charging a predetermined amount of emulsifier and water into a container all at once and mixing and stirring with a stirrer such as a homomixer or shaking with a shaker or the like. It is possible to obtain an O / W type emulsion having a desired particle size, that is, an average particle size of 0.3 μm or less. Regarding the strength and time of stirring and shaking, the stirring and shaking conditions change depending on whether the mixture of the organopolysiloxane and the emulsifier has high or low hydrophilicity, but the lower the hydrophilicity, the longer the time required for strong stirring. However, it can be mixed and dispersed using a commercially available device such as a homomixer, a homogenizer, a sand grinder, a colloid mill.

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

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

The organopolysiloxane emulsion of the present invention improves the smoothness, flexibility, etc. of any fiber product and gives a good texture when any of the above-mentioned preferred ones for fiber treatment is used. can do. For example, the present invention can be applied to various textile products such as cotton stuffing made of polyester fiber, stuffing cotton made of acrylic fiber or nylon fiber, or natural fiber such as cotton fiber and wool fiber product. In addition, these fiber products can be applied in any form such as filament, thread, cloth, and knitted fabric produced by using these fibers. further,
It can also be applied to inorganic fibers such as glass fibers, carbon fibers, aramid fibers and the like.

[0033]

EXAMPLES Next, the present invention will be described with reference to Examples and Comparative Examples. The parts in the examples represent parts by weight.

Example 1 Formula (average formula, the same applies hereinafter)

[0035]

[Chemical 5]

Organopolysiloxane 100 represented by
Parts, 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 are charged into a container and stirred with a homomixer at 5,000 rpm for 15 minutes. A transparent O / W type emulsion was obtained.

The average particle size of this emulsion is 0.016.
It was μm, and it was stable without any change even after standing at 25 ° C. for 3 months. The average particle size is calculated by measuring the diffusion coefficient by photon correlation spectroscopy and calculating the particle size by COUL.
It was measured by COULTERN type 4 manufactured by TER. Also, this emulsion diluted with water 50 times and 500
All the two-fold diluted emulsions were stable without any change even after standing at 25 ° C. for 24 hours. further,
A 50-fold dilution of this emulsion was stirred with a homomixer at 5,000 rpm for 10 minutes, and
The emulsion was stable without any change even when left at 24 ° C. for 24 hours.

Example 2 Formula

[0039]

[Chemical 6]

Organopolysiloxane 100 represented by
Parts, 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 are charged into a container and stirred with a homomixer at 5,000 rpm for 15 minutes. A transparent O / W type emulsion was obtained.

The average particle size of this emulsion is 0.015
It was μm, and it was stable without any change even after standing at 25 ° C. for 3 months. Also, this emulsion was diluted 50 times with water and 500 times with both emulsions.
Even after standing at 5 ° C. for 24 hours, the emulsion was stable without any change. Further, this emulsion was diluted 50 times with water and homogenized with a homomixer at 5,000 rpm for 10 times.
After stirring for 1 minute, the emulsion was stable even when left at 25 ° C. for 24 hours.

Example 3 Formula

[0043]

[Chemical 7]

Organopolysiloxane 100 represented by
Parts, 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 charged into a container and stirred with a homomixer at 5,000 rpm for 15 minutes to obtain a transparent O / W type emulsion having an average particle size of 0.038 μm.

Example 4 Formula

[0046]

[Chemical 8]

Organopolysiloxane 100 represented by
Parts, 20 parts of polyoxyethylene tridecyl ether (HLB = 11.5) as an emulsifier, 1 part of polyoxyethylene nonyl phenyl ether sodium sulfate, 190 parts of water are charged into a container and stirred with a homomixer at 5,000 rpm for 15 minutes. As a result, a transparent O / W type emulsion having an average particle size of 0.012 μm was obtained.

Example 5 Formula

[0049]

[Chemical 9]

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

Example 6 Formula

[0052]

[Chemical 10]

Organopolysiloxane 100 represented by
Parts, 5 parts of polyoxyethylene tridecyl ether (HLB = 13.5) as an emulsifier, and 228 parts of water were charged into a container, and the mixture was stirred with a homomixer at 7,000 rpm for 15 minutes to give a semitransparent average particle size of 0.1 μm. An O / W type emulsion was obtained.

Example 7 Formula

[0055]

[Chemical 11]

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

Example 8 Formula

[0058]

[Chemical 12]

Organopolysiloxane 100 represented by
Parts, 40 parts of polyoxyethylene tridecyl ether (HLB = 11.5) as an emulsifier, and 190 parts of water are charged into a container and stirred with a homomixer at 5,000 rpm for 15 minutes to obtain transparent O having an average particle size of 0.032 μm. A / W emulsion was obtained.

Example 9 The same amount of organopolysiloxane, emulsifier, and water as in Example 1 was charged into a container in the same amounts as in Example 1, and the mixture was stirred at 20 on a shaker.
Shake for 30 minutes at 0 times / minute strength, average particle size 0.02
A transparent O / W type emulsion of 3 μm was obtained.

Comparative Example 1 Formula

[0062]

[Chemical 13]

Organopolysiloxane 100 represented by
The same amount of the same emulsifier and water as in Example 1 was mixed in parts by weight, and the mixture was stirred with a homomixer at 5,000 rpm for 15 minutes.
It did not become a uniform emulsion and separated.

Comparative Example 2 Formula

[0065]

[Chemical 14]

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

A 50-fold dilution of this emulsion was stirred with a homomixer at 5,000 rpm for 10 minutes. An oil film was observed on the liquid surface of this product after standing at 25 ° C. for 24 hours.

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

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

[0070]

[Table 1]

As described 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 are not so soft. From these, it is understood that the polyoxyalkylene group should not be too long as a treating agent for fibers.

[0072]

INDUSTRIAL APPLICABILITY The present invention solves the disadvantages of the prior art and enables microemulsification of organopolysiloxane by a one-step emulsification method that does not require a phase inversion step, thereby greatly simplifying the emulsification step. Made easy. Further, the emulsion obtained by the production method of the present invention has good stability, and further, by treating various fiber products with the emulsion, excellent texture can be imparted. Was found. As described above, the present invention has a number of features, and its effect is extremely large.

Continuation of front page (51) Int.Cl. ⁵ Identification number Reference number within the agency FI Technical display location D06M 15/647 (72) Inventor Yoshio Okamura 2-13-1, Isobe, Annaka-shi, Gunma Shin-Etsu Chemical Co., Ltd. Company Silicon Electronic Materials Technology Laboratory (56) References Tokuhyo Hei 2-503204 (JP, A)

Claims (3)

[Claims] 1. A) General formula Q _a R ¹ _b R ² _c SiO
_{(4-abc) / 2} [wherein Q is —R ³ —O (C _x H _2x O) _y A (A is a hydrogen atom, an acyl group or a monovalent hydrocarbon group, and R ³ is a divalent hydrocarbon. Group, x is an integer of 2 to 4, y is an integer of 3 to 100), and R ¹ is an unsubstituted or halogen-substituted monovalent hydrocarbon group having 1 to 20 carbon atoms or 1 carbon atom. Is an alkoxy group of 20 to 20, R ² 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, an amino group is an epoxy compound, an organic acid or an inorganic group. An amino group-containing hydrocarbon group reacted with an acid, 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 and 1.8 ≦ a + b + c ≦ 2.1. ] 100 parts by weight of organopolysiloxane b) emulsifier 5 to 100 parts by weight c) water 20 to 2000 parts by weight, all of the three components are collectively charged and then emulsified to obtain an oil-in-water organopolysiloxane emulsion. Production method. 2. The method for producing an oil-in-water organopolysiloxane emulsion according to claim 1, wherein the organopolysiloxane in which Q is located at the terminal of the siloxane chain is used. 3. The oil-in-water organopolysiloxane according to claim 1, wherein 50% by weight or more of the compounding amount of the emulsifier is a nonionic emulsifier, and the weight average HLB of the nonionic emulsifier is 9-14. Method for producing emulsion.