JPH0235071B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] This field relates to a fiber treatment agent whose main ingredient is a microemulsion of an organopolysiloxane, and more specifically, to a fiber treatment agent whose main ingredient is a microemulsion of an organopolysiloxane obtained by emulsion polymerization. be. [Prior art] Conventionally, natural fibers such as cotton, hemp, silk, wool, angora, and mohair, recycled fibers such as rayon and Bemberg, semi-synthetic fibers such as acetate, polyester, polyamide, polyacrylonitrile, and polychloride have been used. vinyl, vinylon, polyethylene,
To impart flexibility, smoothness, wrinkle resistance, elongation-recovery properties, water repellency, etc. to fiber materials such as synthetic fibers such as polypropylene and spandex, and inorganic fibers such as glass fibers, carbon fibers, and silicone carbide fibers. Then, the organopolysiloxane is emulsified using one or more of anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants using a homogenizer, colloid mill, line mixer, propeller mixer, etc. Emulsions with an average particle diameter of 0.3 μm or more emulsified using a machine, and emulsions with an average particle diameter of 0.3 μm or more produced by emulsion polymerization of cyclic dimethylpolysiloxane have been used.
(See Publication No. 20116). In addition, the average particle diameter obtained by emulsifying polyorganosiloxane having polar groups or silanol groups under specific conditions is
It has been proposed that microemulsions with a diameter of less than 0.3 μm be used for the care of textile products (Japanese Patent Publication No.
60-127327). [Problems to be Solved by the Invention] However, the emulsion of organopolysiloxane with an average particle diameter of 0.3 μm or more obtained by the above method does not require stirring, circulation, or processing that is required when processing it into fibers. Stability during processes such as squeezing the liquid (mechanical stability), stability due to dilution (20 to 100 times dilution with water, etc.), and stability when used in combination with various additives (formulation stability) The emulsion breaks down and the organopolysiloxane floats on the treatment bath due to insufficient
This has a serious disadvantage in that it forms oil droplets (referred to as oil spots) on the fiber material and causes stains. In addition, although the organopolysiloxane microemulsion with an average particle diameter of less than 0.3 μm obtained by the above method has some improvement in various stability, it is still insufficient, and it still does not form into oil droplets. , it has the disadvantage of staining. The present invention aims to eliminate the above-mentioned drawbacks, and has as its main ingredient a microemulsion of organopolysiloxane obtained by emulsion polymerization, which has excellent mechanical stability, dilution stability, and formulation stability. To provide a fiber treatment agent that does not generate oil spots. [Means for solving the problems and their effects] The above object is to provide a microemulsion obtained by dropping a crude emulsion of a cyclic organopolysiloxane into water containing an emulsion polymerization catalyst and subjecting it to emulsion polymerization. With a fiber treatment agent based on an organopolysiloxane microemulsion, the average particle size of the microemulsion is 0.15 μm or less, and the viscosity of the organopolysiloxane extract at 25°C is at least 100 centistokes. achieved. To explain this, the organopolysiloxane microemulsion used in the present invention is obtained by dropping a crude emulsion of a cyclic organopolysiloxane with a low degree of polymerization into water containing an emulsion polymerization catalyst and carrying out emulsion polymerization. The average particle size of the emulsion after emulsion polymerization is
Must be 0.15μm or less, preferably 0.12μm
m or less. This is because if the average particle diameter is larger than 0.15 μm, mechanical stability, dilution stability, and blending stability will decrease, and oil spots will occur if the fiber material is processed for a long time. The viscosity of the organopolysiloxane extract at 25°C after emulsion polymerization is at least 100 centistokes, preferably 1000 cs or more, more preferably 10000 to 1000 cs.
It is 300000cs. This is because if the viscosity of the organopolysiloxane is less than 100 centistokes, flexibility and smoothness cannot be imparted to the fiber material. The present emulsion can be obtained, for example, by gradually dropping a crude emulsion consisting of a cyclic organopolysiloxane with a low degree of polymerization, a surfactant, and water into water containing an emulsion polymerization catalyst and subjecting it to emulsion polymerization. A typical example of a cyclic organopolysiloxane that is a raw material in a crude emulsion has the formula There is a cyclic organopolysiloxane shown by
In the above formula, R is a monovalent hydrocarbon group, which includes alkyl groups such as methyl group, ethyl group, propyl group, butyl group, 2-phenylethyl group, 2-phenylethyl group,
- Substituted alkyl groups such as phenylpropyl group, 3,3,3-trifluoropropyl group, vinyl group, alkenyl group such as propenyl group, aryl group or substituted aryl group such as phenyl group, tolyl group are exemplified. and the R's in the molecule may be the same or different. n is an integer from 3 to 10. The cyclic organopolysiloxane is 1
It may be a species or a combination of two or more species. In addition to these cyclic organopolysiloxanes,
A small amount of hydrolyzable groups such as diorganopolysiloxane with hydroxyl group capped at both ends, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, trimethoxyvinylsilane, γ-glycidoxypropyltrimethoxysilane, etc. You may add silanes having the following properties. Further, hexaorganodisiloxane may be added as a terminal capping agent for controlling viscosity. A surfactant is required to form the organopolysiloxane into a crude emulsion, and includes anionic surfactants, cationic surfactants, and nonionic surfactants. Examples of anionic surfactants include hexylbenzenesulfonic acid, octylbenzenesulfonic acid,
Alkylbenzenesulfonic acids such as decylbenzenesulfonic acid, dodecylbenzenesulfonic acid _, cetylbenzenesulfonic _acid , myristylbenzenesulfonic acid, _CH3 ( _{CH2 ) 6CH2O} ( _C2H4O ) _2SO3H , _CH3 (CH ₂ ) ₈ CH ₂ O (C ₂ H ₄ O) ₈ SO ₃ H, CH ₃ (CH ₂ ) ₁₉ CH ₂ O (C ₂ H ₄ O) ₄ SO ₃ H, CH ₃ (CH ₂ ) ₈ CH Examples include sulfuric _acid esters of polyoxyethylene monoalkyl ethers such _as 2C6H4O( _{C2H4 ) 2SO3H ,} and _{alkylnaphthylsulfonic} acids. Examples of cationic surfactants include octyltrimethylammonium hydroxide, dodecyltrimethylammonium hydroxide, hexadecyltrimethylammonium hydroxide, octyldimethylbenzylammonium hydroxide, decyldimethylbenzylammonium hydroxide, didodecyldimethylammonium hydroxide, and dioctadecyl Examples include quaternary ammonium hydroxides and salts thereof such as dimethylammonium hydroxide, tallow trimethylammonium hydroxide, and coconut oil trimethylammonium hydroxide. Examples of nonionic surfactants include polyoxyalkylene alkyl ether, polyoxyalkylene alkyl phenol ether, polyoxyalkylene alkyl ester, polyoxyalkylene sorbitan alkyl ester, polyethylene glycol, polypropylene glycol, and diethylene glycol. One kind of surfactant or two or more kinds of surfactants may be used except for a combination of an anionic surfactant and a cationic surfactant. That is, one type or a combination of two or more types of anionic surfactants,
One type or combination of two or more types of nonionic surfactants, one type or combination of two or more types of cationic surfactants, a combination of two or more types of anionic surfactants and nonionic surfactants, cationic surfactants Combinations of two or more surfactants and nonionic surfactants may be used. The amount of these surfactants used in the crude emulsion may be an amount sufficient to form an emulsion, and varies depending on the type of surfactant and is not particularly limited, but is preferably 2 to 50% by weight. The amount of water used in the crude emulsion is preferably such that the concentration of organopolysiloxane is 10 to 60% by weight. The crude emulsion is prepared by uniformly mixing the above-mentioned organopolysiloxane, surfactant, and water and passing it through an emulsifying machine such as a homogenizer, colloid mill, or line mixer. The microemulsion used in the present invention is obtained by gradually adding the crude emulsion to a separately prepared aqueous solution containing an emulsion polymerization catalyst and subjecting it to emulsion polymerization. Examples of the polymerization catalyst include anionic catalysts and cationic catalysts. Examples of anionic catalysts include mineral acids such as hydrochloric acid and sulfuric acid, and sulfuric acid of alkylbenzenesulfonic acid and polyoxyethylene monoalkyl ether, which are exemplified as surfactants. Examples include esters and alkylnaphthylsulfonic acids. Examples of cationic catalysts include alkali metal hydroxides such as potassium hydroxide and sodium hydroxide, and quaternary ammonium hydroxides and salts thereof as exemplified as surfactants. However, since the quaternary ammonium salt has a low catalytic effect, it is used in combination with an alkali metal hydroxide to activate it. Note that due to the ionic nature of the surfactant and the catalyst, if an anionic surfactant is used in the crude emulsion, an anionic catalyst is used when producing the microemulsion. Furthermore, when a cationic surfactant is used in the crude emulsion, a cationic catalyst is used in producing the microemulsion. Furthermore, when a nonionic surfactant is used in the crude emulsion, an anionic or cationic catalyst is used for producing the microemulsion. The amount of the emulsion polymerization catalyst used varies depending on the type of catalyst and is not particularly limited, but in the case of mineral acid or alkali metal catalysts, it is preferably 0.2 to 5.0 parts by weight based on 100 parts by weight of organopolysiloxane in the crude emulsion. , more preferably 0.5 to 3.0 parts by weight. In addition, in the case of alkylbenzenesulfonic acid, sulfuric ester of polyoxyethylene monoalkyl ether, alkylnaphthylsulfonic acid, quaternary ammonium hydroxide and its salt, 0.5 to 50 parts by weight per 100 parts by weight of organopolysiloxane in the crude emulsion. part by weight, more preferably 1.0 to 30 parts by weight. Here, in order to improve the stability during emulsion polymerization, a nonionic surfactant as exemplified as the surfactant used in the crude emulsion may be further added. The temperature of the catalyst aqueous solution when dropping the crude emulsion is
40-95°C is preferred. The dropping speed depends on the type of catalyst,
It depends on the concentration and the temperature of the catalyst aqueous solution, and if the catalyst concentration is high or the temperature of the catalyst aqueous solution is high, it can be dropped faster, but in general, dropping over 30 minutes will result in smaller particles. This is preferable from the viewpoint of producing microemulsions. After dropping, emulsion polymerization is performed at a temperature of 0 to 90℃ until the specified viscosity is reached, and the average particle size is 0.15μ.
Microemulsions of less than m can be prepared. After emulsion polymerization, it is preferable to neutralize the catalyst with an alkali when an anionic polymerization catalyst is used, or with an acid when a cationic polymerization catalyst is used. Note that the concentration of organopolysiloxane during emulsion polymerization is not particularly limited, but is 5 to 50%
Weight percent is preferred. The fiber treatment agent according to the present invention may further include water, a resin treatment agent such as glyoxal resin, melamine resin, urea resin, polyester resin, or acrylic resin, organohydrodiene polysiloxane, organoalkoxysilane, and an interface. Activators, preservatives, coloring agents, etc. may be added. In order to treat fiber materials with the fiber treatment agent according to the present invention, methods such as spraying, roll deposition, brushing, or dipping may be used. The amount of adhesion varies depending on the fiber material and is not particularly limited, but it is from 0.01 to 0.01 in terms of organopolysiloxane content on the fiber material.
A range of 10.0% by weight is typical. The fiber material is then treated by leaving it at room temperature, blowing hot air, heat treatment, etc. Fiber materials include wool, silk, hemp,
Natural fibers such as cotton, angora, mohair, asbestos, recycled fibers such as rayon, Bemberg, semi-synthetic fibers such as acetate, polyester polyamide, polyacrylonitrile, polyvinyl chloride, vinylon, polyethylene, polypropylene, spandex. Examples include inorganic fibers such as synthetic fibers, glass fibers, carbon fibers, and silicone carbide fibers; examples include stable, filament, tow, top, and thread; examples include knitted fabrics, woven fabrics, nonwoven fabrics, and paper; is exemplified. [Example] Next, the present invention will be explained with reference to an example. In the middle part of the example, it means parts by weight, and the viscosity is the value at 25°C. Example 1 In a beaker of 2, 850 parts of water, 10 parts of dodecylbenzenesulfonic acid, and 4 parts of cyclic dimethylsiloxane were added.
600 parts of the liquid was added and stirred uniformly. This mixture was processed using a homogenizer emulsifying machine to produce 400Kg/cm ²
A crude emulsion was obtained by passing the emulsion 4 times at a pressure of . Next, 1300 parts of water and 180 parts of dodecylbenzenesulfonic acid were introduced into another 5 four-necked flask, dissolved, and maintained at a liquid temperature of 85° C. with gentle stirring. The previously prepared crude emulsion was gradually added dropwise to this dodecylbenzenesulfonic acid aqueous solution over a period of 2 hours. After the dropwise addition, the mixture was cooled and further maintained at 48°C for 2 hours to carry out emulsion polymerization. After polymerization, the pH was adjusted to 7.0 with a 50% by weight aqueous solution of sodium hydroxide to obtain Emulsion A. Emulsion A was a slightly yellow, transparent, homogeneous liquid, and did not change at all even after being left at room temperature for one year. The average particle diameter of the emulsion A obtained is
−elatic light scattering Model M2000
(Malrer, USA) was used to measure the
It was a 0.05 μm microemulsion (emulsion A). When the microemulsion was destroyed with methanol and the oil was extracted, the viscosity was
It was confirmed that it was a dimethylpolysiloxane of 60,000 centistokes with hydroxyl groups blocked at both ends. This emulsion A was diluted with water so that the silicone concentration was 2% by weight, and 400 c.c.
I put it in a stainless steel square pouch measuring 35cm x 3cm.
Two rubber rolls with a diameter of 6 cm (nip pressure 0.5 Kg/cm ² ) were assembled one above the other, and the height was adjusted so that the lower roll entered the emulsion liquid by approximately 0.5 cm, and at a speed of 20 revolutions/minute. The mechanical stability of the microemulsion due to the rotation of the rubber roll was visually observed by rotating the roller for 8 hours, and the results are shown in Table 1. In addition, the emulsion after rubber roll treatment is
25 c.c. was collected and centrifuged (3500 rpm), and the results are shown in Table 1. In addition, emulsion A was diluted with water so that the silicone concentration was 5% by weight, and 500 c.c. was put into a household juicer mixer and heated at a speed of 4000 rpm.
Treated for 60 minutes. The appearance of the emulsion after treatment was visually observed, and the results are shown in Table 2. Using a simple air sprayer, spray the emulsion after the Juicer mixer treatment onto a black-dyed 100% rayon nonwoven fabric, dry at room temperature,
Heat treatment was performed at ℃ for 3 minutes. The presence or absence of oil spots on the obtained treated cloth was determined visually, and the feel of the cloth was determined by touch, and the results are shown in Table 2. In addition, emulsion A was diluted with water so that the silicone concentration was 1% by weight, and
using a homomixer at a speed of 8000 revolutions/minute for 10 minutes. The appearance of the emulsion after treatment was observed and the average particle diameter was measured, and the results are shown in Table 4. A 65% polyester/35% cotton blend fabric was immersed in the homomixer-treated emulsion for 10 seconds, squeezed with a squeezing roller, dried at room temperature, and then heat-treated in an oven at 150°C for 5 minutes. The oil spots and texture of the obtained treated cloth were examined, and the results are shown in Table 4. Comparative Example 1 350 parts of dimethylpolysiloxane endblocked with trimethylsilyl groups at both ends (viscosity: 350 centistokes), 30 parts of polyoxyethylene alkyl ether, and water.
After uniformly mixing 30 parts, emulsify using a colloid mill, and uniformly disperse this in 590 parts of water.
A mechanically emulsified emulsion (emulsion B) having an average particle diameter of 1.5 μm was obtained. Emulsion B was a milky white homogeneous liquid. Emulsion B was diluted with water to a silicone concentration of 2% by weight, and tested for mechanical stability using a rubber roll in exactly the same manner as in Example 1. The results are shown in Table 1. In addition, Emulsion B was diluted with water so that the silicone concentration was 5% by weight, and the mechanical stability was tested using a household juicer mixer in exactly the same manner as in Example 1. The results are shown in Table 2. Comparative Example 2 300 parts of cyclic dimethylsiloxane tetramer, 20 parts of dodecylbenzenesulfonic acid and 670 parts of water were uniformly stirred and mixed using a homogenizer emulsifier.
It was passed four times at a pressure of 400 Kg/cm ² . The obtained emulsion was held at 85°C for 2 hours, and then held at 48°C for an additional 2 hours to obtain an emulsion polymerized emulsion (emulsion C) having an average particle size of 0.3 μm. Emulsion C was a milky white homogeneous liquid. Emulsion C was diluted with water to a silicone concentration of 2% by weight, and tested for mechanical stability using a rubber roll in exactly the same manner as in Example 1. The results are shown in Table 1. Further, Emulsion C was diluted with water so that the silicone concentration was 5% by weight, and the mechanical stability was tested using a household juicer mixer in exactly the same manner as in Example 1. The results are shown in Table 2.

【table】

【table】

[Table] Comparative Example 3 Average composition of 100 parts each of dimethylpolysiloxane endblocked with silanol groups at both terminals and having a viscosity of 50 centistokes, 100 centistokes, and 1000 centistokes 40 parts of a polyether-modified methylpolysiloxane surfactant represented by: were mixed, and then 20 parts of water was added and mixed to obtain three types of oil concentrates. Each oil concentrate was treated with the nonionic surfactant Triton.
X405 [octylphenoxypolyethoxy (40) ethanol, 70% in water, manufactured by Rohm & Haus Company, USA] was rapidly dispersed in an aqueous solution consisting of 80 parts of octylphenoxypolyethoxy (40) and 760 parts of water to obtain 10 parts by weight of each dimethylpolysiloxane. A milky white homogeneous emulsion was obtained containing %. An emulsion of dimethylpolysiloxane with a viscosity of 50 centistokes (emulsion D) and an emulsion of dimethylpolysiloxane with a viscosity of 100 centistokes (emulsion E)
had an average particle size of 0.18 μm, but
The dimethylpolysiloxane separated and floated to the surface after being left alone for several days. The dimethylpolysiloxane emulsion (emulsion F) with a viscosity of 1000 centistokes had an average particle size of 1.73 μm, and the dimethylpolysiloxane separated and floated to the surface after being left at room temperature for 2 hours. Example 2 400 parts of cyclic dimethylsiloxane tetramer, 10 parts of hexamethyldisiloxane, 560 parts of water, and 45 mole ethylene oxide adduct of octylphenol
After uniformly mixing 30 parts, the mixture was passed through a homogenizer emulsifying machine three times under a pressure of 450 kg/cm ² to obtain a crude emulsion. Next, 130 parts of dodecylbenzenesulfonic acid and 870 parts of water were put into another 4-necked flask and dissolved, and the mixture was maintained at a liquid temperature of 80°C with gentle stirring. The previously prepared crude emulsion was gradually added dropwise to this dodecylbenzenesulfonic acid aqueous solution over a period of 2 hours. After dropping, the mixture was cooled and kept at the same temperature for an additional 3 hours to carry out emulsion polymerization. After polymerization, the pH was adjusted to 7.0 with a 10% by weight aqueous solution of sodium hydroxide. The obtained microemulsion had an average particle diameter of 0.08 μm and a transmittance (580 nm) of 91%. When this microemulsion was disrupted with methanol, the extracted oil was confirmed to be dimethylpolysiloxane with a viscosity of 280 centistokes and endblocked with trimethylsilyl groups at both ends. This microemulsion was a slightly yellow, transparent, homogeneous liquid, and did not change at all even after being left at room temperature for one year. This emulsion was diluted with water so that the silicone concentration was 1% by weight, and this was used in Example 1.
Mechanical stability with Juicer mixer in
The oil spots on the fabric treated with the emulsion and the texture of the treated fabric after the juicer mixer treatment were investigated. As a result, the mechanical stability with the Juicer mixer was good and no oil floating was observed, and the cloth treated with the emulsion after the mixer treatment did not have oil spots and had a good feel. Example 3 300 parts of cyclic dimethylsiloxane tetramer and 2 parts of β-glycidoxyethyltrimethoxysilane were mixed, and 300 parts of water and 30 parts of polyoxyethylene nonylphenol ether (20 moles of ethylene oxide) were dissolved in advance. After uniformly mixing the mixture with the previously reserved liquid, the mixture was treated twice with a homogenizer at a pressure of 400 kg/cm ² to obtain a crude emulsion. Next, 50 parts of beef tallow trimethylammonium chloride, 20 parts of polyoxyethylene nonylphenol ether added with 20 moles of ethylene oxide, 3 parts of granular sodium hydroxide, and 290 parts of water were uniformly mixed in a four-necked flask, and a liquid The temperature was maintained at 85°C with gentle stirring. The previously prepared crude emulsion was gradually added dropwise to this mixture over a period of 2 hours. After the dropwise addition, the mixture was kept at the same temperature for an additional 5 hours for emulsion polymerization. After polymerization, the pH was adjusted to 7.0 with acetic acid. What was obtained was a microemulsion (emulsion G) with an average particle diameter of 0.04 μm. When this microemulsion was destroyed with methanol, the extracted oil had a viscosity of approximately 800,000 centistokes. This microemulsion was a pale blue, transparent, homogeneous liquid, and did not change at all even after being left at room temperature for one year. Next, 3 parts of this microemulsion, 10 parts of 50% by weight glyoxal resin aqueous solution, 1 part of amine catalyst and 86 parts of water were uniformly mixed and left to stand for 24 hours, and the stability of the combination with glyoxal resin and amine catalyst was examined with the naked eye. Observed by. There was no floating resin or oil, and the stability was good. Add to this a men's shirt made of a blend of 65% polyester and 35% cotton.
After being immersed for a second, it was squeezed with a squeezing roller, dried at room temperature, and then heat-treated in an oven at 150°C for 3 minutes. The resulting treated fabric had no oil spots and had good wrinkle resistance in a hand test, and was suitable as a fabric finishing agent. In addition, as in Example 1, this microemulsion was diluted with water so that the silicone concentration was 1% by weight, treated with a homomixer, and the appearance was observed, the average particle diameter was measured, and the oil spots after the blended fabric treatment were measured. The results are shown in Table 4. Example 4 400 parts of octamethyltetrasiloxane, 570 parts of water, and an equal weight mixture of tallow trimethylammonium hychloride and coconut oil dimethylammonium
After uniformly mixing 30 parts, the mixture was passed through a homogenizer emulsifying machine three times under a pressure of 350 kg/cm ² to obtain a crude emulsion. Separately, 130 parts of an equal weight mixture of beef tallow trimethylammonium chloride and coconut oil dimethylammonium, 870 parts of water, and 4 parts of granular sodium hydroxide were added to a four-necked flask in step 3, uniformly dissolved, and heated to a liquid temperature of 85°C. The mixture was maintained with gentle stirring. The crude emulsion prepared earlier was gradually added dropwise to this aqueous solution over a period of 2 hours. After dropping, the mixture was kept at the same temperature for an additional 3 hours to effect emulsion polymerization. After polymerization, the pH was adjusted to 7.0 using glacial acetic acid. What was obtained was a microemulsion with an average particle size of 0.10 μm. When this microemulsion was destroyed with methanol, it was confirmed that the extracted oil was dimethylpolysiloxane with a viscosity of 1200 centistokes and hydroxyl group-blocked at both ends. This microemulsion was a pale blue transparent homogeneous liquid, and did not change at all even after being left at room temperature for one year. This microemulsion has a silicone concentration of 2.
Dilute with water to make 100% wool by weight
After adhering 3% by weight of silicone to hand knitting yarn, it was dried at room temperature and then heat-treated at 130°C for 3 minutes. The resulting treated yarn has no oil spots and has significantly improved smoothness compared to hand-knitted yarn (refined yarn) that is not treated with silicone.
It had good elasticity and elasticity, and was able to be processed into a soft texture. Example 5 After uniformly mixing 100 parts of octamethyltetrasiloxane, 100 parts of water, and 50 parts of hexadecyltrimethylammonium chloride, the mixture was passed through a homogenizer emulsifier three times under a pressure of 350 kg/cm ² to obtain a crude emulsion. Ta. Separately, 248 parts of water and 2 parts of granular sodium hydroxide were added to a four-necked flask (No. 2) and dissolved uniformly, and the mixture was maintained at a liquid temperature of 85° C. with gentle stirring. The crude emulsion prepared earlier was gradually added dropwise to this aqueous solution over a period of 2 hours. 30 more after dripping
The mixture was kept at the same temperature for several minutes to carry out emulsion polymerization. After polymerization, the pH was adjusted to 7.0 using acetic acid. What was obtained was a microemulsion with an average particle size of 0.075 μm. When this microemulsion was destroyed with methanol, it was confirmed that the extracted oil was dimethylpolysiloxane with a viscosity of 1200 centistokes and hydroxyl group-blocked at both ends. This microemulsion was a pale blue transparent homogeneous liquid, and did not change at all even after being left at room temperature for one year. This microemulsion has a silicone concentration of 2.
Dilute with water to make 100% wool by weight
After adhering 3% by weight of silicone to hand knitting yarn, it was dried at room temperature and then heat-treated at 130°C for 3 minutes. The resulting treated yarn has no oil spots and has significantly improved smoothness compared to hand-knitted yarn (refined yarn) that is not treated with silicone.
It had good elasticity and elasticity, and was able to be processed into a soft texture. Comparative example 4 Average composition formula (CH ₃ ) ₃ SiO [(CH ₃ ) ₂ SiO] ₉₆ [CH ₃ QSiO] ₂ Si (CH ₃ ) ₃ [In the formula, Q is -CH ₂ CH (CH ₃ )
CH ₂ NHCH ₂ CH ₂ NH ₂ Amino-modified organopolysiloxane represented by
100 parts were placed in a beaker equipped with a stirrer running at 350 rpm. 29 parts of Tergitol TMN-6 (trimethyl nonyl polyethylene glycol ether, manufactured by Union Carbide Corporation) and Triton X405
(1.4 parts of octylphenoxy polyethoxy (40) ethanol, 70% aqueous solution, manufactured by Rohm and Haas Company) was added. Then, 18 parts of water was added with stirring, followed by mixing for 15 minutes to obtain an oil concentrate. An emulsion (Emulsion H) containing about 5% by weight of the organopolysiloxane was prepared by rapidly dispersing this oil concentrate in 2000 parts of water by hand stirring. Average composition formula (CH ₃ ) ₃ Si[(CH ₃ ) ₂ SiO] ₄₀₀ [CH ₃ QSiO] ₈ Si(CH ₃ ) ₃ [In the formula, Q is −CH ₂ CH ₂ CH ₂ NHCH ₂ CH ₂ NH ₂ ] Amino-modified organopolysiloxane represented by
100 parts were placed in a beaker equipped with a stirrer running at 350 rpm. Tajitor TMN-6 Part 29 and Triton
1.4 parts of X405 was added. Then add water while stirring.
After adding 18 parts, it was mixed for 15 minutes to obtain an oil concentrate.
An emulsion containing about 5% by weight of the organopolysiloxane (Emulsion I) was prepared by rapidly dispersing this oil concentrate in 2000 parts of water by hand stirring. Average compositional formula (CH ₃ ) ₃ SiO[(CH ₃ ) ₂ SiO] ₉₅ [CH ₃ QSiO] ₃ Si(CH ₃ ) ₃ [In the formula, Q is -CH ₂ CH ₂ SCH ₂ COOH] Carboxyl 100 parts of modified organopolysiloxane and nonionic surfactant Triton X-
100 (octylphenoxypolyethoxy(10) ethanol, manufactured by Rohm and Haas Company) and 29 parts of water were added and mixed to prepare an oil concentrate. This oil concentrate was rapidly dispersed in 2000 parts of water to prepare an emulsion containing about 5% by weight of the organopolysiloxane (Emulsion J). Average composition formula (CH ₃ ) ₃ SiO [(CH ₃ ) ₂ SiO] ₄₀₀ [CH ₃ QSiO] ₈ Si(CH ₃ ) ₃ [In the formula, Q is −CH ₂ (CH ₂ ) ₈ CH ₂ COOH] 100 parts of the carboxyl-functional organopolysiloxane shown, 10 parts of the nonionic surfactant Tergitol TMN-6, and 10 parts of Tergitol TMN-10.
10 parts of water was added and mixed to prepare an oil concentrate. An emulsion containing about 5% by weight of the organopolysiloxane (Emulsion K) was prepared by rapidly dispersing this oil concentrate in 2000 parts of water. The appearance of Emulsion H to Emulsion K was visually observed during emulsion production and after being left at room temperature, and the results are shown in Table 3. About Emulsion H ~ Emulsion K
The average particle diameter was measured using Ondsi-elaticlight scattering Model M2000 (manufactured by Malrer, USA),
The results are shown in Table 3. Dilute Emulsion H to Emulsion K with water so that the silicone concentration is 1% by weight,
The 500c.c. is heated at 8000rpm using a homomixer for 10
Processed for minutes. The appearance of the treated emulsion was visually observed and the average particle size was measured. Further, a 65% polyester/35% cotton blend fabric was immersed in the homomixer-treated emulsion for 10 seconds, squeezed with a squeezing roller, dried at room temperature, and then heat-treated in an oven at 150°C for 5 minutes. The oil spots and texture of the treated fabrics were examined and the results are shown in Table 4.

【table】

【table】

【table】

[Table] [Effects of the Invention] The fiber treatment agent of the present invention is a microemulsion obtained by emulsion polymerization of organopolysiloxane, and the average particle diameter of the microemulsion is 0.15 μm or less, and the viscosity of the organopolysiloxane extract at 25°C is at least
Since the main ingredient is a microemulsion of organopolysiloxane with a density of 100 centistokes,
It has excellent mechanical stability, dilution stability and formulation stability, and is characterized by being able to process fibers without producing oil spots, making it extremely useful industrially.

Claims (1)

[Claims] 1 A microemulsion obtained by dropping a crude emulsion of a cyclic organopolysiloxane into water containing an emulsion polymerization catalyst and emulsion polymerization, wherein the average particle size of the microemulsion is
0.15 μm or less, and the viscosity of the organopolysiloxane extract at 25°C is at least 100 μm.
A fiber treatment agent whose main ingredient is centistokes, an organopolysiloxane microemulsion.