JPS5922822B2 - Organopolysiloxane composition for textile treatment - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel organopolysiloxane compositions for treating fibers.

Conventionally, silicone oil has been known as a treatment agent for imparting flexibility to textile products such as woven and knitted fabrics, and this agent is said to impart flexibility to textile products by reducing the frictional resistance between their filaments. It has characteristics.

This silicone oil is generally in the form of a solvent solution, which is dissolved or dispersed in an aromatic hydrocarbon such as toluene or xylene, or an organic solvent such as a chlorinated hydrocarbon, or in the form of an emulsion, which is dispersed in water in the form of droplets. It is used as a mold.

However, with this type of treatment agent, the silicone oil simply exists (adheres) on the surface of the textile product in an oily state, so it is difficult to improve the stretchability and elasticity of the textile product and give it a bulky feel. It has the disadvantage of being difficult.

On the other hand, as a treatment agent for imparting the above-mentioned properties to textile products, there are known compositions that crosslink and cure on the surface of textile products to form a film that adheres to the product. In order to provide good stretchability, elasticity, and bulkiness, it is necessary for the crosslinked and cured rubber film to exhibit excellent rubber elasticity. A composition prepared by diluting and dissolving a composition consisting of a blocked diorganopolysiloxane with a very high degree of polymerization, a crosslinking agent, and a curing catalyst in an organic solvent has been proposed (Japanese Patent Publication No. 15597/1983).
(See Publication No. 48-38036, etc.).

However, this method requires a long time to prepare because extremely high viscosity silicone oil is dissolved in an organic solvent, and it is difficult to measure and charge high viscosity silicone oil, which has almost no fluidity, into a dissolution tank. There are process difficulties.

In addition, as an emulsion-type treatment agent, a so-called cyclic siloxane containing octoorganocyclotetrasiloxane as a main component, which is well known in the industry, is added to water, emulsified, and polymerized using a strong acid or strong base. A diorganopolysiloxane latex with an extremely high degree of polymerization obtained by emulsion polymerization, a crosslinking agent, and a curing catalyst is known (Japanese Patent Publication No. 53-978).
(see publication).

However, the diorganopolysiloxane latex that makes up the composition is special because it is synthesized using strong acids and strong bases as catalysts, and compared to the case where an emulsion is obtained by emulsifying ordinary low-viscosity oil. In addition to the polymerization time required for the polymerization of cyclic siloxane from several hours to several tens of hours, the properties of fiber products treated with this composition are lower than those of the solvent type described above. Possibly due to the lack of penetrating properties, it has the disadvantage of poor properties despite the use of diorganopolysiloxane with an extremely high degree of polymerization as a raw material.

Furthermore, the above-mentioned solvent-type processing agent is further diluted with a solvent to a viscosity that allows normal emulsification,
Attempts have also been made to emulsify and use a product obtained by emulsification, but this has not produced the desired effect.

The present invention aims to provide a novel organopolysiloxane composition for textile treatment which eliminates the disadvantages and disadvantages of conventional silicone-based fiber treatment agents, and which is composed of (a) the general formula (in which R1 and R2 represents the same or different monovalent hydrocarbon groups.

However, 50 mol% or more of all monovalent hydrocarbon groups are methyl groups.

m is a positive integer), and the viscosity at 25°C is 10~
A diorganopolysiloxane with a molecular weight of 100,000 cS in which both ends of the molecular chain are capped with hydroxyl groups, (b) one hydroxyl group directly bonded to a silicon atom in component (a) above is directly bonded to a silicon atom. A sufficient amount to provide 0.1 to 20 hydrogen atoms of the general formula (wherein R3, R4, R5 and R6 are the same or different unsubstituted-valent hydrocarbon groups having 1 to 20 carbon atoms or halogen Represents a substituted-valent hydrocarbon group.

However, 50 mol% or more of all monovalent hydrocarbon groups are methyl groups.

n is a positive integer), and the viscosity at 25°C is 10~
100,000 cS diorganopolysiloxane in which both ends of the molecular chain are capped with diorganomonohydrodiene siloxane units; (c) 1 to 200 parts by weight per 100 parts by weight of the total amount of components (a) and (b) It has at least 3 hydrogen atoms directly bonded to silicon atoms in one molecule, and 50 mol% or more of the organic groups bonded to silicon atoms are methyl groups in the weight part,
An organhydrodiene polysiloxane in which the remaining organic groups are unsubstituted-valent hydrocarbon groups or halogen-substituted-valent hydrocarbon groups having 1 to 20 carbon atoms and a viscosity of 10 to 100,000 cS at 25°C; ) Total amount of the above components (a), (b) and (c) 10
It consists of 0.1 to 100 parts by weight of a metal organic acid salt relative to 0 parts by weight.

When manufacturing a solvent-type treatment agent, there are operational problems in dissolving extremely high viscosity diorganopolysiloxanes in organic solvents, but the present invention is capable of dissolving relatively low-viscosity diorganopolysiloxanes. In addition, emulsion-type treatment agents have a unique manufacturing process in which diorganopolysiloxane latex is prepared by emulsion polymerization, and the polymer emulsion component is applied to the fiber surface. It eliminates various drawbacks such as inferior properties of treated textile products due to inferior permeability compared to solution-type products, and can be manufactured using only the general emulsification method commonly used in the industry. The present invention aims to provide a composition that exhibits excellent processing effects and can impart stretchability, elasticity, and bulkiness to textile products.

The composition according to the present invention has the same or better effects than conventional solvent-type processing agents using silicone oil with an extremely high degree of polymerization.

That is, the composition of the present invention is diluted with an appropriate amount of water to form an aqueous solution, the target textile product is immersed in the solution, and then the composition is dried and heat-cured by a conventional method to form an essentially linear chain. A dehydrogenation reaction occurs by using an arbitrary reaction catalyst between the terminal functional groups (: 25i-OH and \NiniS i -H) of the polymer components (a) and (b). As a result, the linear component becomes polymerized, and this reacts with the crosslinking agent, resulting in a treatment that is similar to when a composition using a diorganopolysiloxane with an extremely high degree of polymerization and a crosslinking agent is used. This may be due to the fact that the same or better effect is obtained, and the use of relatively low molecular weight siloxane improves the wetting and penetrating properties of the fibers. The unexpected effect is that better stretchability, elasticity, and bulkiness are imparted compared to those using a polysiloxane latex with a high degree of polymerization as a linear component.

In other words, it is superior to a system using an extremely high molecular weight diorganopolysiloxane obtained by an emulsion polymerization method using a composition emulsified using raw materials with a viscosity within a range that can be emulsified by a normal emulsification process. Stretchability, elasticity, and bulkiness can be imparted to textile products.

Furthermore, since it can be produced by a common emulsification method, the polymerization time and special polymerization reaction tank required for the emulsion polymerization method are not required.

In addition, the composition of the present invention can be used not only as a treatment agent for fibers, but also as a treatment agent for glass sleeves, a coating material for gasket base materials, and has good water repellency and a soft texture due to its film-forming properties. Since it has imparting properties, it can be widely applied as a treatment agent for imparting water resistance and flexibility.

Hereinafter, the organopolysiloxane composition for fiber treatment according to the present invention will be explained in detail.

First, the diorganopolysiloxane as component (a) used in the present invention has both ends of the molecular chain represented by the above-mentioned general formula (1) blocked with hydroxyl groups.

Examples of the monovalent hydrocarbon group represented by R1 and R2 in the formula include alkyl groups such as methyl group, ethyl group, propyl group, butyl group, alkenyl groups such as vinyl group and allyl group, phenyl group, benzyl group, etc. aryl groups, or groups in which the hydrogen atoms of these groups are partially substituted with halogen atoms, etc.; however, in the present invention, monovalent hydrocarbon groups bonded to the silicon atoms in the siloxane (
50 mol% or more of R1, R2) is required to be a methyl group.

The type of monovalent hydrocarbon group other than the methyl group is not particularly limited, but preferably has 2 to 2 carbon atoms.
It is desirable that the value be 0.

In addition, this component (A) has a viscosity of 10 to 1 at 25°C.
It is essential that it be in the range of 00,000cS.

This is because emulsification becomes difficult if the viscosity becomes too high.

Such diorganopolysiloxane as component (a) can be synthesized by various conventionally known methods, including, for example, adding a cyclic polysiloxane such as octamethylcyclotetrasiloxane to an acid or a base. Examples include a method of polymerization using a catalyst.

Next, the diorganopolysiloxane as the (oral) component used in the present invention is represented by the general formula (11), in which both ends of the molecular chain are blocked with diorganomonohydrodiene siloxane units.

R3, R' ff R' and R6 in the formula each represent the same or different unsubstituted-valent hydrocarbon group or halogen-substituted-valent hydrocarbon group having 1 to 20 carbon atoms, and this includes the above-mentioned R1, R2 The groups exemplified above can include groups similar to zo.

Note that for this component (b), as well as for the component (a), it is required that 50 mol% or more of all monovalent hydrocarbon groups bonded to silicon atoms be methyl groups.

In addition, this component (b) has a viscosity of 10 to Z at 25°C.
It is essential that it be in the range of oo, 0OOcS.

Such diorganopolysiloxane, which is component (b), uses a cyclic siloxane such as tetramethyldisiloxane and octamethylcyclotetrasiloxane as starting materials, and polymerizes them using an acidic substance such as sulfuric acid or activated clay as a catalyst. It can be synthesized by performing an equilibration reaction.

The amount of component (b) used is an amount sufficient to provide 0.1 to 20 hydrogen atoms directly bonded to silicon atoms for each hydroxyl group directly bonded to silicon atoms in component (a) above. Good results cannot be obtained outside this range.

Furthermore, the organohydrodiene polysiloxane as component (iii) used in the present invention has at least three hydrogen atoms directly bonded to silicon atoms in one molecule, and has a viscosity that allows emulsification at room temperature (specifically The viscosity at 25° C. is required to be 100,000 cS or less).

In addition, this organohydrodiene polysiloxane is
At least 50 mol% of the organic groups bonded to silicon atoms are methyl groups, and organic groups other than this methyl group have a carbon atom number of 1.
~20 unsubstituted or halogen-substituted-valent hydrocarbon groups are essential.

Such organohydrodiene polysiloxanes are
For example, the formula (wherein R7 is a monovalent organic group, a and b are each 0
≦a≦30〈b≦3, where a + b is 0 < a
+ b≦3).

This component (iii) can be obtained, for example, by polymerizing a mixture of octamethylcyclotetrasiloxane, tetramethylcyclotetrasiloxane and hexamethyldisiloxane in any molar ratio in the presence of an acid catalyst, or by polymerizing water glass, silica tetrachloride, etc. It can be obtained by a method of hydrolyzing a component such as SiO2 Genkichi hexamethyldisiloxane or tetramethyldisiloxane in an acidic atmosphere.

It is essential that the above-mentioned component (c) is used in an amount of 1 to 200 parts by weight, preferably 2.5 to 100 parts by weight, based on 100 parts by weight of the total amount of components (a) and (b). be done.

Next, the metal organic acid salt as component (2) is essential because the composition of the present invention can quickly crosslink and cure to form a rubber film, and contains soot, lead, zinc, cobalt, etc. , manganese, chromium, and other organic acid salts.

These metal organic acid salts are usually dissolved in an organic solvent, dissolved in water, or dispersed in water using any emulsifier appropriately selected from nonionic, anionic, and cationic emulsifiers, or self-emulsifying type. It may be used as a

It is essential to use component 2) in an amount of 0.1 to 100 parts by weight based on 100 parts by weight of the total amount of components iv), b), and c) described above.

The composition according to the present invention can be prepared by simply uniformly mixing the components (a) to (a) above, but when the composition is used by emulsifying it in water, various emulsifiers may be used. The emulsifier may be any of nonionic, anionic and cationic emulsifiers, and may be selected from those known in the art, including, for example, polyoxyethylene alkyl phenyl ether, quaternary emulsifier, etc. Examples include ammonium salts and sodium alkylbenzenesulfonates.

The amount of the emulsifier used is approximately 1 to 50 parts by weight based on 100 parts by weight of the total amount of polysiloxane.

When actually treating target textile products using the organopolysiloxane composition according to the present invention, it is possible to use conventional methods such as impregnation, brush coating, spray coating, etc. in either solvent type or emulsion type. For example, in the treatment of textile products, the composition obtained as described above is diluted to a predetermined concentration using an organic solvent or water as necessary, and then the textile product is immersed therein. After impregnation, the silicone composition may be cured by appropriately squeezing with a mangle or the like and heating.

The curing temperature is usually about 100 to 180°C, and the heating time for curing is arbitrary within a range that does not deteriorate the properties of the textile product.

When the composition of the present invention is heated as described above, the terminal hydroxyl group and the terminal hydrogen atom in the composition are polymerized by a dehydrogenation reaction, and at the same time, a siloxane having at least three '3 S i -H bonds in one molecule is formed. A cured film is formed on the surface of the textile product by the dehydration reaction with the crosslinking agent, and as a result, the textile product is given excellent bulkiness, anti-elasticity, and elasticity.

Although the packaging form of the composition according to the present invention is arbitrary, from the standpoint of product shelf life, reactivity, etc., components (a), (b), and (c) or organic solvent solutions or The first package is an emulsion prepared by dispersing them in water, and the second package is often the component or its organic solvent solution, aqueous solution, or aqueous dispersion.In actual use, the first and second packages are combined. It is desirable to prepare a treatment bath by mixing and use it.

Next, examples of the present invention will be given, and all parts in each example indicate parts by weight.

In addition, all Me in the molecular formula represents a methyl group.

Examples 1 to 3 Viscosity 10 with both ends of the molecular chain represented by the molecular formula blocked with hydroxyl groups
00 cS (25°C) dimethylpolysiloxane (this will be referred to as siloxane A), methylhydrodiene polysiloxane with a viscosity of 20 cs (25°C) in which both ends of the molecular chain shown in the molecular formula are blocked with dimethylhydrogensilyl groups. (Siloxane B
) and methylhydrodienepolysiloxane (denoted as siloxane C) having the molecular formula and a viscosity of 50 cs (25°C) were used in the proportions shown in Table 1 below. After adding 3 parts of a nonionic emulsifier consisting of ethylene alkylphenyl ether, emulsification was performed using a homogenizer to prepare an aqueous emulsion.

Next, a treatment bath was prepared by mixing an aqueous dispersion of a reaction catalyst containing 10% zinc acetate in the proportions shown in Table 2 below into the aqueous emulsion obtained above.

Experiment 1 A polyester/cotton (70/30) blended knit cloth was dipped in the treatment bath obtained above, squeezed with a mangle, then heated at 100°C for 3 minutes using a baking machine, and further heated at 150°C for 2 minutes. Processed.

When we investigated various physical properties of the treated fabric obtained above, we found that
The results shown in Table 2 below were obtained.

154- Experiment 2 A polyester/cotton (65/35) blended broadcloth was immersed in the same treatment bath as used in Experiment 1 and treated in exactly the same manner, and the softness and wateriness of the treated cloth were examined. The results are shown in Table 3 below.

Example 2 Viscosity 50 with both ends of the molecular chain shown in the molecular formula blocked with hydroxyl groups
00 cs dimethyl polysiloxane, 7.5 parts of methylhydrodiene polysiloxane with a viscosity of 20 cS (25°C), both ends of the molecular chain shown by the molecular formula are blocked with dimethylhydrodienesilyl groups, and After adding 3 parts of a nonionic emulsifier consisting of polyoxyethylene alkylphenyl ether and 67 parts of water to a mixture consisting of 15 parts of methylhydrodiene polysiloxane and having a viscosity of 50 cS (25°C), the mixture was emulsified using a homogenizer. An aqueous emulsion was prepared.

Next, add 1 part of zinc acetate to 10 parts of the aqueous emulsion obtained above.
A treatment bath was prepared by mixing 5 parts of an aqueous dispersion of a reaction catalyst containing 0%.

A polyester/cotton (70/30) blended knit cloth was dipped in the treatment bath obtained above (coating amount 100%), then squeezed with a mangle, and then heated at 100℃ using a baking machine for 30 minutes.
Heat treatment was performed for 1 minute, and further heat treatment was performed for 2 minutes at 160°C.

When we investigated various physical properties of the treated fabric obtained above, we found that
The results shown in Table 4 below were obtained.

For comparison purposes, 5 parts of latex containing 30% dimethylpolysiloxane, 5 parts of the same 30% emulsion of Siloxane C used in Example 1, 5 parts of metal organic acid salt, and 85 parts of water were uniformly mixed. A treatment bath was prepared and used to treat a blended knit fabric in the same manner as above, and the results are shown in Table 4.

Example 3 After uniformly mixing the same siloxane A, siloxane B, siloxane C, dibutyltin dilaurate, and toluene as those used in Example 1 in the proportions shown in Table 5 below, cotton knitted fabric was padded. The physical properties of this treated cotton knitted fabric are shown in Table 5 below.

Example 4 A treatment solution was prepared by mixing 13 parts of the emulsion composition prepared in Experiment 163, 6 parts of the emulsified dispersion of zinc acetate, and 81 parts of water, and a polyester/cotton blended broad (70
/30) after dipping (siloxane adhesion amount 3.2%)
) The treatment was carried out in the same manner as in Example 1.

The various physical properties of this treated fabric and after washing it five times at home were examined and the results are shown in Table 6 below.

Claims (1)

[Scope of Claims] 1 (a) General formula (wherein and R2 represent the same or different types of monovalent hydrocarbon groups. However, 50 mol% or more of all monovalent hydrocarbon groups are methyl groups. m is a positive integer), and the viscosity at 25°C is 10~
A diorganopolysiloxane with a molecular weight of 100,000cS, in which both ends of the molecular chain are capped with hydroxyl groups, (b) one hydroxyl group in component (a) above that is directly bonded to a silicon atom is directly bonded to a silicon atom. A sufficient amount to provide 0.1 to 20 hydrogen atoms of the general formula (wherein R3, R4, R5 and R6 are the same or different unsubstituted-valent hydrocarbon groups having 1 to 20 carbon atoms or halogen Represents a substituted-valent hydrocarbon group. However, 50 mol% or more of all monovalent hydrocarbon groups are methyl groups. n is a positive integer), and the viscosity at 25 ° C.
100,000 cS diorganopolysiloxane in which both ends of the molecular chain are blocked with diorganomonohydrodiene siloxane units, (c) 1 to 200 parts by weight per 100 parts by weight of the total amount of components (a) and (b) above It has at least 3 hydrogen atoms directly bonded to silicon atoms in one molecule, and 50 mol% or more of the organic groups bonded to silicon atoms are methyl groups in the weight part,
An orgasohydrodiene polysiloxane in which the remaining organic groups are unsubstituted-valent hydrocarbon groups or halogen-substituted-valent hydrocarbon groups having 1 to 20 carbon atoms, and have a viscosity of 10 to 100,000 cS at 25°C; and B) Total amount of the above components (a), (b) and (c) 10
An organopolysiloxane composition for fiber treatment comprising 0.1 to 100 parts by weight of a metal organic acid salt relative to 0 parts by weight.