JP2005290582A - Water-repelling, oil-repelling and anti-staining apparel product and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a water-repelling and anti-staining apparel products that causes no damage of the color, elasticity, backing material, feeling, when the water-repelling and anti-staining treatment are carried out and can readily be cleaned, even when it is stained. <P>SOLUTION: Composite film including a substance 1 bearing at least fluorinated hydrocarbon group, hydrocarbon group and silyl group and substance 2 mainly including siloxane group is formed on the surface of apparel products. In particular, this composite film is formed in a thickness of several hundred to several ten nano meter level by allowing a chlorosilane compound including fluorocarbon group, hydrocarbon group and chlorosilyl group as main groups to react with a chlorosilane compound including chlorosilyl group as main component or allowing an alkoxysilane compound including fluorocarbon group, hydrocarbon group and alkoxysilyl group as main component to react with an alkoxysilane compound including alkoxysilyl group as main component. More preferably, a single molecular film at least including siloxane bonds has a thickness of several nano meter level. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a high-performance apparel product, that is, a highly functional fiber product subjected to water / oil repellent / antifouling treatment, and a fur / leather product subjected to water / oil repellent / antifouling treatment.

  In the present invention, “apparel products” refers to various fibers and yarns, fabrics, product materials such as fur and leather, and products made using them, that is, fibers such as clothes, footwear, and bags having sewing thread portions. Includes products, fur and leather products. In addition to clothing, clothing includes accessories such as hats, mufflers, neckerchiefs, gloves, socks, socks, shoes, ties, and belts.

In more detail, the textile products of the present invention include various suits sewn using various fabrics, cutter shirts, blouses, skirts, dresses, sportswear, ski wear, raincoats, mufflers, neckerchiefs, dresses, wedding dresses, kimonos ( Japanese clothes), white robes, surgical clothes, apron, underwear, cold clothes, and other shoes, shoes, bags, rucksacks, hats, gloves, socks, mufflers, etc.

The fur and leather products of the present invention include natural leather, natural fur products, artificial leather, shoes made from artificial fur, bags, gloves, hats, rucksacks, jackets, trousers, belts, jumpers, coats, etc. included.

  As in Patent Document 1, a mixed solution containing at least an alkoxysilane-based surfactant, a non-aqueous solvent that does not contain active hydrogen, and a silanol condensation catalyst is brought into contact with the substrate surface, and the interface is brought into contact with the substrate surface. A water-repellent monomolecular film composed of the surfactant molecules covalently bonded to the substrate surface via a siloxane bond by covalently bonding the surfactant molecule via a siloxane bond and then washing with a non-aqueous solvent. Methods for forming these coatings are known.

Further, as described in Document 2, 3 or 4, 5, 6, a mixed solution containing at least a chlorosilane surfactant and a non-aqueous solvent containing no active hydrogen is brought into contact with the substrate surface, and the substrate surface A method for forming a water-repellent monolayer film comprising the surfactant molecules covalently bonded to the surface of a substrate via a siloxane bond is known. It has been.

  However, in any of the methods, the treatment performance greatly depends on the surface condition of the base substrate, and even if the treatment is performed under the same conditions, the water / oil repellent / antifouling performance is not stable if the base material is different.

  Furthermore, the combination of an alkoxysilane surfactant and a silanol condensation catalyst has the major drawback of slow reaction and poor mass productivity.

JP-A-8-337654 JP-A-5-031441 JP 9-031215 JP-A-4-289273 JP-A-5-193556 JP-A-8-224536

An object of the present invention is to solve the above problems and achieve the following objects.
That is, an object of the present invention is to provide a high-performance water- and oil-repellent antifouling apparel product using a chemical adsorption method with little variation in water and oil repellent and antifouling performance.

It is another object of the present invention to provide a method for producing a water / oil repellent / antifouling apparel product that can provide stable water / oil / oil repellent / antifouling performance even if the base material is changed.
Still another object of the present invention is to provide a method for producing a water / oil / oil / repellency antifouling apparel product capable of high-speed reaction even when an alkoxysilane surfactant is used.

In order to achieve the above object, an apparel product of a first invention is an apparel product in which a highly durable antifouling coating is formed, and the coating comprises at least a fluorocarbon group, a hydrocarbon group, and a silyl group. It is characterized by being composed of a composite film containing a substance 1 containing as a main component and a substance 2 containing a siloxane group as a main component.

According to the apparel product of the first invention, it is possible to improve the disadvantage that the performance of the conventional water / oil repellent / antifouling chemical adsorption film greatly depends on the base substrate, and to stabilize the water / oil repellent / antifouling performance. High performance apparel products.

At this time, the substance 1 mainly composed of the fluorocarbon group, the hydrocarbon group, and the silyl group is converted into the silica film via the silyl group in the silica film composed of the substance 2 mainly composed of the siloxane group. And it is convenient to improve the wear resistance and washing durability when it is bonded and fixed to the surface of the apparel product.

In addition, a substance 1 mainly composed of a fluorocarbon group, a hydrocarbon group and a silyl group and a substance 2 mainly composed of a siloxane group are bonded to each other or individually on the surface of the apparel product via the silyl group and the siloxane group. When fixed, it is convenient for improving wear resistance and washing durability in addition to stabilization of water and oil repellent and antifouling performance.

Further, the molecular composition ratio of the substance 1 mainly composed of fluorocarbon group, hydrocarbon group and silyl group and the substance 2 mainly composed of siloxane group contained in the composite film is 1: 1 to 199: 1. This is advantageous in providing a high-performance apparel product that is stable in water and oil repellent and antifouling performance without impairing water and oil repellent and antifouling performance.

According to a second aspect of the present invention, there is provided a water repellent / oil repellent antifouling apparel product comprising: a substance having a fluorocarbon group, a hydrocarbon group and a chlorosilyl group as main components on the surface of the apparel product in a dry atmosphere; The method includes a step of bringing a composite film-forming solution obtained by mixing and diluting a substance containing alkenyl as a main component or a substance containing an alkoxysilyl group as a main component with a non-aqueous organic solvent to cause a reaction to form a film.

According to the method for producing a water and oil repellent and antifouling apparel product of the second aspect of the present invention, the conventional chemical adsorption film is weak against abrasion and improved in abrasion resistance and washing durability. A method for producing a water / oil repellent antifouling apparel product can be provided.

At this time, if the treatment is performed in a dry air or nitrogen gas atmosphere having a relative humidity of 35% or less, the influence of moisture in the air can be advantageously reduced.

In addition, the surface of the apparel product may contain a substance mainly composed of a fluorocarbon group, a hydrocarbon group and a chlorosilyl group and a substance mainly composed of a chlorosilyl group or a substance mainly composed of an alkoxysilyl group in a non-aqueous organic solvent. By using the mixed and diluted composite film forming solution to contact and react to form a film, and to wash away the excess solution on the surface of the apparel product using a solvent, the color, texture, and gloss of the underlying apparel product It is convenient because there is no loss of

Furthermore, CF ₃ — (CF ₂ ) _n — (CH ₂ ) ₂ —SiCl ₃ or [CF ₃ — (CF ₂ ) _n — (CH ₂ ) ₂ ] ₂ -SiCl ₂ , [CF _3- (CF ₂ ) _n — (CH ₂ ) ₂ ] ₃ —SiCl (n is 0 or an integer), and Cl ₃ Si as a substance mainly composed of a chlorosilyl group (OSiCl ₂ ) _m Cl (m is 0 or integer) or (AO) ₃ Si (OSi (OA) ₂ ) _m (OA) (m is 0 or integer, A is alkyl) When the molecular composition ratio at the time of mixing is 1: 1 to 199: 1, an apparel product excellent in water and oil repellency and antifouling properties can be produced.

According to a third aspect of the present invention, there is provided a method for producing an apparel product comprising: a substance mainly comprising a fluorocarbon group, a hydrocarbon group and an alkoxysilyl group; and a substance or chlorosilyl group comprising an alkoxysilyl group as a main component on the apparel product surface. The method includes a step of bringing a substance as a main component into contact with a complex film forming solution obtained by mixing and diluting a silanol condensation catalyst with a non-aqueous organic solvent to form a film.

According to the method for producing a water- and oil-repellent and antifouling apparel product of the third aspect of the invention, it is possible to improve the defect of being weak against abrasion of the conventional chemical adsorption film and to improve the abrasion resistance and washing durability. A method for producing a water / oil repellent antifouling apparel product can be provided. In addition, since this method can be manufactured in normal air, the capital investment can be reduced as compared with the second invention. That is, it is possible to provide a method for producing a lower cost water / oil / oil repellent and antifouling apparel product.

Furthermore, this method is suitable for the treatment of apparel products damaged by hydrochloric acid since no hydrochloric acid is generated during the treatment, as compared with the second invention.

In addition, the surface of the apparel product should not contain a substance mainly composed of fluorocarbon group, hydrocarbon group and alkoxysilyl group, a substance mainly composed of alkoxysilyl group or a substance mainly composed of chlorosilyl group and a silanol condensation catalyst. A composite film forming solution mixed and diluted with an aqueous organic solvent is contacted and reacted to form a film, and a step of washing and removing the excess solution on the surface of the apparel product with a solvent. This is convenient because it does not impair the color, texture, and gloss of the apparel product.

Further, CF ₃ — (CF ₂ ) _n — (CH ₂ ) ₂ —Si (OA) ₃ or [CF ₃ — (CF ₂ ) can be used as a substance mainly composed of a fluorocarbon group, a hydrocarbon group, and an alkoxysilyl group. _{n - (CH 2) 2]} 2 -Si (OA) 2, [CF 3 - with _{(CH 2) 2] 3 -SiOA} (n is 0 or an integer, a is an alkyl group), - (CF _{2) n} (AO) ₃ Si (OSi (OA) ₂ ) _m OA (where m is 0 or an integer, A is an alkyl group) or Cl ₃ Si as a substance mainly composed of an alkoxysilyl group Using (OSiCl ₂ ) _m Cl (m is 0 or an integer) and setting the molecular composition ratio at the time of mixing to 1: 1 to 199: 1, an apparel product having excellent water and oil repellency and antifouling properties can be produced. Convenient.

In addition, when a ketimine compound, or an organic acid, aldimine compound, enamine compound, oxazolidine compound, or aminoalkylalkoxysilane compound is used instead of a silanol condensation catalyst, the reaction rate can be increased compared with the case of using a silanol condensation catalyst, and mass production is possible. It is convenient to provide a method for producing a water / oil repellent / antifouling apparel product having excellent properties.

Furthermore, when a silanol condensation catalyst and a ketimine compound, or at least one selected from an organic acid, an aldimine compound, an enamine compound, an oxazolidine compound, and an aminoalkylalkoxysilane compound are mixed and used, each of them is further compared to the case where each is used alone. Conveniently, it is possible to provide a method for producing a water / oil repellent / antifouling apparel product having a high reaction rate and excellent mass productivity.

According to a fourth aspect of the present invention, there is provided a method for producing an apparel product comprising a substance having a fluorocarbon group, a hydrocarbon group and an alkoxysilyl group as main components and a ketimine compound as a catalyst, an organic acid, an aldimine compound, an enamine on the surface of the apparel product. The method includes a step of bringing a compound, an oxazolidine compound, and an aminoalkylalkoxysilane compound mixed and diluted with a non-aqueous organic solvent into contact to form a film.

According to the method for producing a water / oil / oil repellent / antifouling apparel product of the fourth aspect of the present invention, the drawback of slow reaction when using a combination of a conventional alkoxysilane surfactant and a silanol condensation catalyst is improved. Thus, it is possible to provide a method for producing a water / oil repellent / antifouling apparel product excellent in mass productivity. Moreover, since it can be manufactured in normal air, the capital investment can be reduced as compared with the second invention. That is, it is convenient to provide a method for producing a water / oil / oil / antifouling apparel product at a lower cost.

In addition, non-aqueous organic substances such as fluorocarbon, hydrocarbon and alkoxysilyl groups and ketimine compounds, or organic acids, aldimine compounds, enamine compounds, oxazolidine compounds and aminoalkylalkoxysilane compounds on the surface of apparel products When using at least a step of forming a film by bringing a solution mixed and diluted with a solvent into contact with each other and a step of washing and removing an excess solution on the surface of the apparel product using a solvent, the color tone, texture of the base apparel product, It is convenient because it does not interfere with the gloss.

At this time, CF ₃ — (CF ₂ ) _n — (CH ₂ ) ₂ —Si (OA) ₃ or [CF ₃ — () is used as a substance mainly composed of a fluorocarbon group, a hydrocarbon group, and an alkoxysilyl group. _{CF 2) n - (CH 2} ) 2] 2 -Si (OA) 2, [CF 3 - (CF 2) n - (CH 2) 2] 3 -SiOA (n is 0 or an integer, A is an alkyl group) Is advantageous in improving the water and oil repellency of the coating.

In addition, when a silanol condensation catalyst is used in combination with at least one selected from a ketimine compound or an organic acid, an aldimine compound, an enamine compound, an oxazolidine compound, and an aminoalkylalkoxysilane compound, the reaction rate is further increased compared to the case where each is used alone. It is convenient to provide a method for producing a water / oil / oil repellent / antifouling apparel product having excellent mass productivity.

As described above, the water / oil repellent / antifouling apparel product of the present invention and the manufacturing method thereof can provide a high performance water / oil repellent / antifouling apparel product with little variation in water / oil repellent / antifouling performance. effective.
In addition, there is an effect that it is possible to provide a method for producing a water / oil repellent / antifouling apparel product that can obtain stable water / oil repellent / antifouling performance without largely depending on the material of the base substrate.
Furthermore, even when an alkoxysilane surfactant is used, there is an effect that it is possible to provide a method for producing a water / oil / oil repellent antifouling apparel product capable of high-speed reaction, that is, excellent in mass productivity.

The present invention provides a high-performance water- and oil-repellent antifouling apparel product that is highly durable and has little variation in water and oil repellent and antifouling performance at low cost. Further, the present invention provides a method for producing a water / oil / oil / repellency antifouling apparel product capable of high-speed reaction even when an alkoxysilane surfactant is used, that is, excellent in mass productivity.

The water / oil repellent / antifouling apparel product of the first invention is an apparel product on which at least a highly durable antifouling film is formed, and the coating comprises at least a fluorocarbon group and a hydrocarbon group. It is a water / oil repellent / antifouling apparel product composed of a composite film comprising a substance 1 mainly composed of silyl groups and a substance 2 mainly composed of siloxane groups.

According to the apparel product of the first invention, it is possible to improve the conventional defect that the performance of the chemical adsorption film greatly depends on the base substrate, and to improve the performance of the apparel product with stable water / oil repellent / antifouling performance. Can be provided.

At this time, the substance 1 mainly composed of the fluorocarbon group, the hydrocarbon group, and the silyl group is converted into the silica film via the silyl group in the silica film composed of the substance 2 mainly composed of the siloxane group. When bonded and fixed to the surface of the apparel product, the stability of the water / oil repellent / antifouling performance can be improved and the wear resistance and washing durability can be improved.

In addition, a substance 1 mainly composed of a fluorocarbon group, a hydrocarbon group and a silyl group and a substance 2 mainly composed of a siloxane group are bonded to each other or individually on the surface of the apparel product via the silyl group and the siloxane group. When fixed, the water and oil repellency and antifouling performance can be improved, and the wear resistance and washing durability can be improved without impairing the texture, color tone and gloss of the base substrate.

Furthermore, the molecular composition ratio of the substance 1 mainly composed of a fluorocarbon group, a hydrocarbon group and a silyl group and the substance 2 mainly composed of a siloxane group contained in the composite film is 1: 1 to 199: 1. Accordingly, it is possible to provide a high-performance apparel product that has stable water and oil repellent and antifouling performance without impairing water and oil repellent performance, and high durability.

According to a second aspect of the present invention, there is provided a water repellent / oil repellent antifouling apparel product comprising: a substance having a fluorocarbon group, a hydrocarbon group and a chlorosilyl group as main components on the surface of the apparel product in a dry atmosphere; At least a step of bringing a composite film-forming solution obtained by mixing and diluting a substance containing as a main component or a substance containing an alkoxysilyl group as a main component with a non-aqueous organic solvent to cause a reaction to form a film.

In the method for producing a water / oil repellent / antifouling apparel product according to the second aspect of the present invention, the density of the substance mainly composed of fluorocarbon group, hydrocarbon group and chlorosilyl group in the water / oil repellent / antifouling coating Can improve the disadvantage of being weak against the wear of conventional chemical adsorption film, and manufacture apparel products with water and oil repellent and antifouling coatings with excellent wear resistance and washing durability it can.

At this time, if the treatment is performed in a dry air or nitrogen gas atmosphere having a relative humidity of 35% or less, the influence of moisture in the air can be reduced, and a stable water and oil repellent and antifouling treatment can be performed.

Further, as a substance mainly composed of a fluorocarbon group, a hydrocarbon group, and a chlorosilyl group, CF ₃ — (CF ₂ ) _n — (CH ₂ ) ₂ —SiCl ₃ or [CF ₃ — (CF ₂ ) _n — (CH ₂ ) ₂ ] ₂ -SiCl ₂ , [CF _3- (CF ₂ ) _n — (CH ₂ ) ₂ ] ₃ —SiCl (n is 0 or an integer), and Cl ₃ Si as a substance mainly composed of a chlorosilyl group (OSiCl ₂ ) _m Cl (m is 0 or integer) or (AO) ₃ Si (OSi (OA) ₂ ) _m (OA) (m is 0 or integer, A is alkyl) When the molecular composition ratio at the time of mixing is 1: 1 to 199: 1, an apparel product excellent in water / oil repellency / antifouling property can be produced.

According to a third aspect of the present invention, there is provided a method for producing an apparel product comprising: a substance mainly comprising a fluorocarbon group, a hydrocarbon group and an alkoxysilyl group; and a substance or chlorosilyl group comprising an alkoxysilyl group as a main component on the apparel product surface. A step of bringing a substance as a main component into contact with a complex film forming solution obtained by mixing and diluting a silanol condensation catalyst with a non-aqueous organic solvent to form a film.

In the method for producing a water / oil / oil / repellency / antifouling apparel product according to the third aspect of the present invention, the density of the substance mainly composed of a fluorocarbon group, a hydrocarbon group and a chlorosilyl group in the water / oil / oil / repellency / antifouling coating Can be improved by 2 to 3 times, which improves the weakness of conventional chemisorbed film against wear, and manufacture of apparel products with water and oil repellent and antifouling coatings with excellent wear resistance and washing durability Can provide a method.

In addition, since this method can be manufactured in normal air, the capital investment can be reduced as compared with the second invention. That is, it is possible to provide a method for producing a water / oil / oil / antifouling apparel product at a lower cost.

Furthermore, this method is applicable to the treatment of apparel products that are damaged by hydrochloric acid since no hydrochloric acid is generated during the treatment as compared with the second invention.

In addition, the surface of the apparel product should not contain a substance mainly composed of fluorocarbon group, hydrocarbon group and alkoxysilyl group, a substance mainly composed of alkoxysilyl group or a substance mainly composed of chlorosilyl group and a silanol condensation catalyst. Using a step of contacting and reacting a composite film forming solution mixed and diluted with an aqueous organic solvent to form a film, and a step of washing and removing an excess solution on the surface of the apparel product using a solvent, Water and oil repellent and antifouling treatment can be performed without interfering with the color tone, gloss and texture of the base apparel product.

Furthermore, CF ₃ — (CF ₂ ) _n — (CH ₂ ) ₂ —Si (OA) ₃ or [CF ₃ — (CF ₂ ) can be used as a substance mainly composed of a fluorocarbon group, a hydrocarbon group, and an alkoxysilyl group. _{n - (CH 2) 2]} 2 -Si (OA) 2, [CF 3 - with _{(CH 2) 2] 3 -SiOA} (n is 0 or an integer, a is an alkyl group), - (CF _{2) n} (AO) ₃ Si (OSi (OA) ₂ ) _m OA (where m is 0 or an integer, A is an alkyl group) or Cl ₃ Si as a substance mainly composed of an alkoxysilyl group When (OSiCl ₂ ) _m Cl (m is 0 or an integer) and the molecular composition ratio at the time of mixing is 1: 1 to 199: 1, the water and oil repellency is not impaired without impairing the water and oil repellency and antifouling performance. Apparel products with excellent antifouling properties are consistently safe It can be prepared.

Furthermore, when a ketimine compound, or an organic acid, an aldimine compound, an enamine compound, an oxazolidine compound, or an aminoalkylalkoxysilane compound is used instead of a silanol condensation catalyst, the reaction rate is doubled compared to when a silanol condensation catalyst is used. It is possible to provide a method for producing a water / oil repellent / antifouling apparel product that can be made to a certain extent and is excellent in mass productivity.

When the silanol condensation catalyst is mixed with at least one selected from ketimine compounds, organic acids, aldimine compounds, enamine compounds, oxazolidine compounds, and aminoalkylalkoxysilane compounds, the catalyst or the silanol condensation catalyst is used alone. Compared to the case, the reaction rate can be increased several times faster, and a method for producing a water / oil repellent / antifouling apparel product excellent in mass productivity can be provided.

According to a fourth aspect of the present invention, there is provided a method for producing an apparel product comprising a substance having a fluorocarbon group, a hydrocarbon group and an alkoxysilyl group as main components and a ketimine compound, or an organic acid, aldimine compound, enamine compound, oxazolidine on the apparel product surface. It includes at least a step of forming a film by contacting and reacting a solution obtained by mixing and diluting a compound and an aminoalkylalkoxysilane compound with a non-aqueous organic solvent.

According to the method for producing a water / oil / oil repellent / antifouling apparel product of the fourth aspect of the present invention, the drawback of slow reaction when using a combination of a conventional alkoxysilane surfactant and a silanol condensation catalyst is improved. Thus, it is possible to provide a method for producing a water / oil repellent / antifouling apparel product excellent in mass productivity.

Moreover, since it can be manufactured in normal air, the capital investment can be reduced as compared with the second invention. That is, it is possible to provide a method for producing a water / oil / oil / antifouling apparel product at a lower cost.

In addition, non-aqueous organic substances such as fluorocarbon, hydrocarbon and alkoxysilyl groups and ketimine compounds, or organic acids, aldimine compounds, enamine compounds, oxazolidine compounds and aminoalkylalkoxysilane compounds on the surface of apparel products By using at least the step of forming a film by bringing the solution mixed and diluted with the solvent into contact with each other and the step of washing and removing the excess solution on the surface of the apparel product with the solvent, the color tone and gloss of the base apparel product, Water and oil repellent antifouling apparel products can be manufactured without disturbing the texture.

Furthermore, CF ₃ — (CF ₂ ) _n — (CH ₂ ) ₂ —Si (OA) ₃ or [CF ₃ — (CF ₂ ) can be used as a substance mainly composed of a fluorocarbon group, a hydrocarbon group, and an alkoxysilyl group. _{) n - (CH 2) 2} ] 2 -Si (OA) 2, [CF 3 - with _{(CH 2) 2] 3 -SiOA} (n is 0 or an integer, a is an alkyl group) - (CF _{2) n} Excellent water and oil repellent antifouling apparel products can be manufactured.

Further, when a silanol condensation catalyst is used in combination with a ketimine compound or at least one selected from an organic acid, an aldimine compound, an enamine compound, an oxazolidine compound, and an aminoalkylalkoxysilane compound, the reaction rate can be further increased several times. Improves mass productivity of water / oil repellent and antifouling apparel products.

Hereinafter, embodiments of the water / oil repellent / antifouling apparel product of the present invention will be described in detail.

First, the water / oil repellent / antifouling apparel product of the first invention will be described together with the first production method (second invention).

(Embodiment 1)
Textile products are usually cotton, wool (wool, cashmere, Angola, etc.), hemp, silk, paper, natural fibers such as wood, recycled fibers such as rayon, polyester fibers, polyamide fibers, polyvinyl alcohol fibers, polyurethane fibers Made of synthetic fiber such as polyacrylonitrile fiber.

Fur and leather products include natural leather such as cattle, pigs, horses and deers, natural fur such as deer, sharks and minks, or artificial leather and artificial fibers made using synthetic polymers and synthetic fibers such as polyurethane. Made of fur. These fiber products, fur, and leather product surfaces contain active hydrogen such as hydroxyl groups and imino groups.

Therefore, CF ₃ — (CF ₂ ) _n — (CH ₂ ) ₂ —SiCl is a substance mainly composed of a fluorocarbon group, a hydrocarbon group, and a chlorosilyl group in a dry atmosphere (humidity of 35% or less is good). ₃ or a _{[(CH 2) 2 CF 3} - - (CF 2) n] 3 -SiCl (n is a positive _{number), [CF 3 - - (} CF 2) n (CH 2) 2] 2 -SiCl 2, As a substance having a chlorosilyl group as a main component, Cl ₃ Si (OSiCl ₂ ) _m Cl (m is 0 or an integer) is added to an organic solvent (eg, hexadecane) containing almost no non-aqueous water, for example, 0.01M each. / L and a concentration of 0.005 M / L are dissolved (in this case, the former and the latter have a molecular composition ratio of 2: 1) to prepare a composite film forming solution.

  Next, apparel products such as wool suits are thoroughly washed and dried, and then the composite film forming solution is applied to the surface in a dry atmosphere (humidity of 35% or less is good) and allowed to react for about 30 minutes.

At this time, the wool (silk and nylon is the same) fiber surface contains a large number of hydroxyl groups and imino groups, that is, active hydrogen, and is covered with adsorbed water. The hydroxyl group and adsorbed water undergo a dehydrochlorination reaction, and a —SiO— bond is formed in a state in which a substance mainly composed of a fluorocarbon group, a hydrocarbon group, and a chlorosilyl group and a substance mainly composed of a chlorosilyl group are mixed and reacted. To the surface of the wool fiber.

That is, the substance mainly composed of a fluorocarbon group, a hydrocarbon group, and a chlorosilyl group is changed to the substance 1 mainly composed of a fluorocarbon group, a hydrocarbon group, and a silyl group, and is changed through the -SiO- bond. Thus, the substance having the siloxane group as the main component is bonded to the surface of the wool fiber 3 or the substance 2 having the siloxane group as the main component. Through bonding, it binds to the surface of the wool fiber 3 and the substance 1 mainly composed of a fluorocarbon group, a hydrocarbon group, and a silyl group.

After that, when the excess composite film forming solution on the surface is removed by washing, a substance 1 having fluorocarbon groups, hydrocarbon groups, and silyl groups as main components and a substance 2 having siloxane groups as main components are included. In addition, a composite film 5 containing a hydroxyl group 4 can be formed on the surface of the wool fiber 3. (Fig. 1 (a))

In addition, when the washing process of the composite film forming solution is omitted and the non-aqueous organic solvent is evaporated, a substance 1 and a siloxane group having a fluorocarbon group, a hydrocarbon group, and a silyl group as main components having a thickness of several tens of nanometers A composite film containing the substance 2 containing as a main component was able to be formed on the wool fiber surface. In this case, the film thickness becomes thicker than when washed, and the texture is somewhat inferior to when washed and removed, but the advantage is that the manufacturing process can be shortened and a more durable film can be formed.

Thereafter, when taken out in the air and left for a certain period of time, the hydrochloric acid remaining in the film generated by the reaction becomes a catalyst, and most of the hydroxyl groups 4 remaining in the film undergo a dehydration reaction to form a polysiloxane bond and form a network of silica. The film 6 is changed.

As a result, a water-repellent / oil-repellent / anti-fouling composite film 7 having a high washing durability and comprising a substance 1 mainly composed of a fluorocarbon group, a hydrocarbon group and a silyl group and a substance 2 mainly composed of a siloxane group. (FIG. 1B), a highly durable water / oil repellent / antifouling suit can be produced.

In this case, the fluorocarbon group, the hydrocarbon group, and the silyl group in the film are the main components compared to the film made only of the substance mainly composed of the fluorocarbon group, the hydrocarbon group, and the alkoxysilyl group. The adsorption density of the substances to be improved can be improved 2 to 3 times.

In addition, if the molecular composition ratio of the substance mainly composed of fluorocarbon group, hydrocarbon group and rosilyl group and substance mainly composed of chlorosilyl group in the composite film forming solution is appropriately changed, the fluorocarbon contained in the composite film It is possible to change the molecular composition ratio of the substance 1 mainly composed of a group, a hydrocarbon group and a silyl group and the substance 2 mainly composed of a siloxane group.

Preferably it is 1: 1 to 199: 1 (more preferably 5: 1 to 10: 1), and by doing so, it is made of only a substance mainly composed of a fluorocarbon group, a hydrocarbon group and a chlorosilyl group. The wear resistance can be greatly improved compared to the case of the coated film.

In addition, when the substance which has a chlorosilyl group as a main component from 1: 1 increases, a water-repellent | oil-repellent | oil-repellent | antifouling function will fall rapidly. Further, when the amount of a substance having a chlorosilyl group as a main component was less than 199: 1, the washing durability was hardly improved.

Further, the water contact angle (water droplet contact angle) of the water / oil / oil / repellency wool fabric at this time depends on the composition of the substances 1 and 2, but the composition is within the range of 1: 1 to 199: 1. The water repellency performance was almost unchanged even when changed. In particular, it was 150 degrees or more stably at 5: 1 to 10: 1. Furthermore, a stable water / oil repellent / antifouling coating was obtained without depending on the material of the base material.

In general, examples of the substance mainly composed of a fluorocarbon group, a hydrocarbon group, and a chlorosilyl group include the following substances.
_{CF 3 - (CF 2) n} - (R) m -SiX p Cl 3-p
(Where n is 0 or an integer, preferably an integer of 1 to 22, R is an alkyl group, phenyl group, vinyl group, ethynyl group, a substituent containing silicon or an oxygen atom, m is 0 or 1, X is H, alkyl Group, alkoxyl group, fluorine-containing alkyl group or substituent of fluorine-containing alkoxy group, p is 0, 1 or 2)

More specifically, the following (1) to (9) are mentioned.
(1) CF ₃ CH ₂ O (CH ₂ ) ₁₅ SiCl ₃
(2) CF ₃ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ ) ₁₅ SiCl ₃
(3) CF ₃ (CH ₂ ) ₆ Si (CH ₃ ) ₂ (CH ₂ ) ₉ SiCl ₃
(4) CF ₃ COO (CH ₂ ) ₁₅ SiCl ₃
(5) CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ SiCl ₃
(6) CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ SiCl ₃
(7) CF ₃ (CF ₂ ) ₇ C ₆ H ₄ SiCl ₃
(8) [CF ₃ (CF ₂ ) ₃ (CH ₂ ) ₂ ] ₂ SiCl ₂
(9) [CF ₃ (CF ₂ ) ₃ (CH ₂ ) ₂ ] ₃ SiCl

In addition, as a substance having a chlorosilyl group as a main component, a compound represented by SiCl ₄ , SiHCl ₃ , SiH ₂ Cl ₂ , or Cl ₃ Si (OSiCl ₂ ) _m Cl (where m is an integer) can be used. It is.

Instead of a substance having a chlorosilyl group as a main component, a substance having an alkoxy group as a main component, for example, Si (OCH ₃ ) ₄ , Si (OC ₂ H ₅ ) ₄ , SiH (OCH ₃ ) ₃ , SiH ₂ ( OCH _{3) 2, or, (CH 3 O) 3 Si} (-OSi (OCH 3) 2) m -OCH 3 ( where, m is an integer) _{and, SiH (OC 2 H 5)} 3, SiH 2 (OC 2 H _{5) 2} or _{(C 2 H 5 O) 3} Si (-OSi (OC 2 H 5), 2) m -OC 2 H 5 ( where, m is an integer) can be used.

At this time, the substance having an alkoxy group as a main component does not naturally undergo a dehydrochlorination reaction, but hydrochloric acid generated by the reaction of a chemical adsorbent containing a fluorocarbon group and a chlorosilyl group serves as a catalyst to form a siloxane bond with the fiber surface. Form.

Further, instead of the chlorosilane-based chemical adsorbent, isocyanate-based chemical adsorbents in which all chlorosilyl groups are replaced with isocyanate groups, for example, (1) to (5) shown below can be mentioned.

(1) CF ₃ (CH ₂ ) _r SiX _p (NCO) _3-p
(2) CF ₃ (CH ₂ ) _r SiX _p (NCO) _3-p
(3) CF ₃ (CH ₂ ) _s O (CH ₂ ) _t SiX _p (NCO) _3-p
(4) CF ₃ (CH ₂ ) _u Si (CH ₃ ) ₂ (CH ₂ ) _v SiX _p (NCO) _3-p
(5) CF ₃ COO (CH ₂ ) _w SiX _p (NCO) _3-p
(However, as a preferable range, r is 1 to 25, s is 0 to 12, t is 1 to 20, u is 0 to 12, v is 1 to 20, and w is 1 to 25.)

More specifically, the following (1) to (7) are mentioned.
(1) CF ₃ CH ₂ O (CH ₂ ) ₁₅ Si (NCO) ₃
(2) CF ₃ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ ) ₁₅ Si (NCO) ₃
(3) CF ₃ (CH ₂ ) ₆ Si (CH ₃ ) ₂ (CH ₂ ) ₉ Si (NCO) ₃
(4) CF ₃ COO (CH ₂ ) ₁₅ Si (NCO) ₃
(5) CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (NCO) ₃
(6) CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (NCO) ₃
(7) CF ₃ (CF ₂ ) ₇ C ₆ H ₄ Si (NCO) ₃

Further, instead of a substance having a chlorosilyl group as a main component, Si (NCO) ₄ , SiH (NCO) ₃ , SiH ₂ (NCO) ₂ , or (NCO) ₃ Si (OSi (NCO) ₂ ) _m (NCO) (Where m is an integer) can be used.
Here, when an isocyanate-based chemical is used, there is an advantage that hydrochloric acid is not generated.

As a solvent for the composite film forming solution, it is possible to use a hydrocarbon solvent that does not contain water, or a fluorocarbon solvent or a silicone solvent. Considering ease of handling, about 50 to 150 ° C. is preferable.

On the other hand, when washing and removing using an organic solvent, those having a boiling point of 100 to 350 ° C. are suitable.

Specifically usable are petroleum naphtha, solvent naphtha, petroleum ether, petroleum benzine, isoparaffin, normal paraffin, decalin, industrial gasoline, nonane, octane, kerosene, dimethyl silicone, phenyl silicone, alkyl modified silicone, polyether silicone Etc.

In addition, as the fluorocarbon solvent, there are various chlorofluorocarbon solvents, Fluorinert (product of 3M), Afludo (product of Asahi Glass). In addition, these may be used individually by 1 type and may mix 2 or more types as long as it mixes well. Further, an organic chlorine solvent such as chloroform may be added. In this case, there is a function capable of forming a film while washing the base substrate.

In Embodiment 1, the treatment liquid is pretreated with a treatment liquid using only a substance mainly composed of chlorosilyl groups, and then a treatment liquid using a substance mainly composed of a fluorocarbon group, a hydrocarbon group, and a chlorosilyl group. Even with the method of treating with water, the water and oil repellent and antifouling treatment which is less dependent on the base material was possible.

Even in the case of polyvinyl chloride or polyfluorinated ethylene fiber having no active hydrogen on the surface, the same treatment is possible if a hydroxyl group is added to the fiber surface by corona treatment or plasma treatment containing oxygen.
(Embodiment 2)

Next, a second manufacturing method (third invention) of the water / oil repellent / antifouling apparel product of the first invention will be described.

For example, CF ₃ — (CF ₂ ) _n — (CH ₂ ) ₂ —Si (OA) or [CF ₃ — (CF ₂ ) can be used as a substance mainly composed of a fluorocarbon group, a hydrocarbon group, and an alkoxysilyl group. _{n - (CH 2) 2]} 2 -Si (OA) 2, [CF 3 - (CF 2) n - (CH 2) 2] 3 -SiOA (n is a positive number, a is an alkyl group) and an alkoxysilyl (AO) ₃ Si (OSi (OA) ₂ ) _m OA (m is 0 or an integer, and A is an alkyl group) is a non-aqueous organic solvent (for example, nonane). ) To a concentration of 0.01M / L and 0.001M / L respectively (in this case, the molecular composition ratio of the former and the latter is 10: 1), and further, one type is selected from the silanol condensation catalyst. Concentration of 0.002 to 0.0002 M / L So as to be added to create a composite film-forming solution.

  Next, the cotton fabric is thoroughly washed and dried, and then the composite film forming solution is applied to the surface in the air and allowed to react for 1 to 2 hours.

At this time, since the fiber surface of the cotton fabric contains a large number of hydroxyl groups, that is, active hydrogen, and is covered with adsorbed water, two -Si (OA) ₃ groups and the hydroxyl groups and adsorbed water of the two substances are formed on the fiber surface. As in the first embodiment, a substance 1 mainly composed of a fluorocarbon group, a hydrocarbon group, and a silyl group and a substance 2 mainly composed of a siloxane group are mixed by a dealcoholization reaction via a silanol catalyst. In this state, the fibers are bonded to the surface of the fiber through -SiO- bonds.

That is, a substance mainly composed of a fluorocarbon group, a hydrocarbon group, and an alkoxysilyl group is composed mainly of a fluorocarbon group, a hydrocarbon group, and a silyl group by a dealcoholization reaction in the presence of a silanol condensation catalyst. It changes to the substance 1 and binds to the fiber surface of the cotton fabric and the substance 2 mainly composed of siloxane groups through the —SiO— bond, while the substance mainly composed of alkoxysilyl groups is present in the presence of a catalyst. Below, it changes into the substance 2 which has a siloxane group as a main component by dealcoholization reaction, and has the fiber surface of a cotton fabric, a fluorocarbon group, a hydrocarbon group, and a silyl group as a main component through the -SiO- bond. Combines with substance 1.

After that, after taking out temporarily in the air and reacting with moisture in the air, the excess composite film forming solution on the surface is washed and removed, and the main components are fluorocarbon groups, hydrocarbon groups and silyl groups with a thickness of several nanometers. The composite film 5 containing the substance 1 and the substance 2 containing a siloxane group as a main component and partially containing the hydroxyl group 4 can be formed on the fiber surface of the cotton fabric. (Same as FIG. 1 (a))

When the non-aqueous organic solvent is evaporated by omitting the cleaning step, the substance 1 having a fluorinated carbon group, a hydrocarbon group, and a silyl group as main components and a siloxane group having a thickness of several tens of nanometers as a main component. A composite film containing the substance 2 and containing many hydroxyl groups can be formed on the fiber surface of the cotton fabric. In this case, the thickness becomes thicker than that obtained by washing, and the texture of the fabric is inferior to that obtained by washing and removal, but the advantages are that the process can be shortened and a film having higher washing durability can be formed.

Thereafter, when left in the air for a certain period of time, the dehydration reaction proceeds further due to the catalyst remaining in the film, and the substance 1 mainly composed of a fluorocarbon group, a hydrocarbon group, and a silyl group and a siloxane group are mainly contained. A highly durable water- and oil-repellent and antifouling composite film 7 comprising the substance 2 as a component can be produced, and a high-performance water and oil and oil repellent and antifouling cotton fabric can be produced as in Example 1 (FIG. 1 (b). )the same as).

In this case as well, the fluorocarbon group, hydrocarbon group, and silyl group in the film are the main components compared to the film made only of the substance mainly composed of the fluorocarbon group, hydrocarbon group, and alkoxysilyl group. It was possible to improve the adsorption density of the substance to 2 to 3 times.

Of course, an antifouling function can be imparted even if a film is formed only with a substance mainly composed of a fluorocarbon group, a hydrocarbon group and a chlorosilyl group, but the fluorocarbon group, hydrocarbon group and alkoxy of the composite film forming solution can be provided. If the molecular composition ratio of the substance mainly composed of silyl group and the substance mainly composed of alkoxysilyl group is appropriately changed, the substance 1 mainly composed of fluorocarbon group, hydrocarbon group and silyl group contained in the composite film It is possible to change the molecular composition ratio of the substance 2 mainly composed of siloxane groups.

Preferably 1: 1: 1 to 199: 1 (more preferably 5: 1 to 10: 1), so that only substances mainly composed of fluorocarbon groups, hydrocarbon groups and chlorosilyl groups are used. As compared with the case of the coating prepared in step 1, the wear resistance can be greatly improved.

In addition, when the substance which has a chlorosilyl group as a main component from 1: 1 increases, a water-repellent | oil-repellent | oil-repellent | antifouling function will fall rapidly. Further, when the amount of a substance having a chlorosilyl group as a main component was less than 199: 1, the washing durability was hardly improved.

In general, examples of the substance mainly composed of a fluorocarbon group, a hydrocarbon group, and an alkoxysilyl group include the following substances.
_{CF 3 - (CF 2) n} - (R) m -SiX p (OA) 3-p
(Where n is 0 or an integer, preferably an integer of 1 to 22, R is an alkyl group, phenyl group, vinyl group, ethynyl group, a substituent containing a silicon or oxygen atom, m is 0 or 1, X is H, An alkyl group, an alkoxy group, a fluorine-containing alkyl group or a substituent of a fluorine-containing alkoxy group, p is 0, 1 or 2, A is an alkyl group such as CH ₃ , C ₂ H ₅ , C ₃ H ₇ )

More specifically, the following substances (1) to (18) can be mentioned.
(1) CF ₃ CH ₂ O (CH ₂ ) ₁₅ Si (OCH ₃ ) ₃
(2) CF ₃ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ ) ₁₅ Si (OCH ₃ ) ₃
(3) CF ₃ (CH ₂ ) ₆ Si (CH ₃ ) ₂ (CH ₂ ) ₉ Si (OCH ₃ ) ₃
(4) CF ₃ COO (CH ₂ ) ₁₅ Si (OCH ₃ ) ₃
(5) CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OCH ₃ ) ₃
(6) CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (OCH ₃ ) ₃
(7) CF ₃ (CF ₂ ) ₇ C ₆ H ₄ Si (OCH ₃ ) ₃
(8) CF ₃ CH ₂ O (CH ₂ ) ₁₅ Si (OC ₂ H ₅ ) _{3
(9) CF 3 (CH 2} ) 2 Si (CH 3) 2 (CH 2) 15 Si (OC 2 H 5) 3
(99: 1) CF ₃ (CH ₂ ) ₆ Si (CH ₃ ) ₂ (CH ₂ ) ₉ Si (OC ₂ H ₅ ) ₃
(11) CF ₃ COO (CH ₂ ) ₁₅ Si (OC ₂ H ₅ ) ₃
(12) CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OC ₂ H ₅ ) ₃
(13) CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ SiCl ₃
(14) CF ₃ (CF ₂ ) ₇ C ₆ H ₄ Si (OC ₂ H ₅ ) ₃
(15) [CF ₃ (CF ₂ ) ₃ (CH ₂ ) ₂ ] ₂ Si (OCH ₃ ) ₂
(16) [CF ₃ (CF ₂ ) ₃ (CH ₂ ) ₂ ] ₂ Si (OC ₂ H ₅ ) ₂
(17) [CF ₃ (CF ₂ ) ₃ (CH ₂ ) ₂ ] ₃ SiOCH ₃
(18) [CF ₃ (CF ₂ ) ₃ (CH ₂ ) ₂ ] ₃ SiOC ₂ H ₅

Moreover, Si (OA) ₄ , SiH (OA) ₃ , SiH ₂ (OA) ₂ , or (AO) ₃ Si (OSi (OA) ₂ ) _m OA (provided that the alkoxysilyl group is a main component) m is an integer, and A is a compound represented by an alkyl group such as CH ₃ , C ₂ H ₅ , and C ₃ H ₇ .

More specifically, the following substances (1) to (8) can be mentioned.
(1) Si (OCH ₃ ) ₄
(2) SiH (OCH ₃ ) ₃
(3) SiH ₂ (OCH ₃ ) ₂
(4) (CH ₃ O) ₃ Si (OSi (OCH ₃ ) ₂ ) _m OCH ₃
(5) Si (OC ₂ H ₅ ) ₃
(6) SiH (OC ₂ H ₅ ) ₃
(7) SiH ₂ (OC ₂ H ₅ ) ₂
(8) (H ₅ C ₂ O) ₃ Si (OSi (OC ₂ H ₅ ) ₂ ) _m OC ₂ H ₅

On the other hand, instead of the substance having an alkoxysilyl group as a main component, SiCl ₄ , Cl ₃ Si (—OSiCl ₂ ) _m —Cl (where m is an integer), SiHCl ₃ , SiH ₂ Cl ₂ are mixed and used. In addition, the adsorption density of the chemical adsorbent molecules containing a fluorocarbon group and an alkoxysilyl group could be improved by 2 to 3 times.

At this time SiCl ₄ or _{Cl 3 Si (-OSiCl 2) m} -Cl ( where, m is an integer) and, SiHCl _3, the use of the SiH ₂ Cl _2, generating hydrochloric acid reacts with adsorbed water on the fiber surface However, this hydrochloric acid also serves as a catalyst, and there is an effect that the reaction rate can be further improved several times as compared with the case where only the silanol condensation catalyst is used.

Furthermore, carboxylic acid metal salts, carboxylic acid ester metal salts, carboxylic acid metal salt polymers, carboxylic acid metal salt chelates, titanate esters, and titanate ester chelates can be used as silanol condensation catalysts. More specifically, stannous acetate, dibutyltin dilaurate, dibutyltin dioctate, dibutyltin diacetate, dioctyltin dilaurate, dioctyltin dioctate, dioctyltin diacetate, stannous dioctanoate, lead naphthenate, cobalt naphthenate , Iron 2-ethylhexenoate, dioctyltin bisoctylthioglycolate, dioctyltin maleate, dibutyltin maleate polymer, dimethyltin mercaptopropionate polymer, dibutyltin bisacetylacetate, dioctyltin bisacetyl Laurate, tetrabutyl titanate, tetranonyl titanate and bis (acetylacetonyl) dipropyl titanate can be used.

In this case as well, a hydrocarbon-based solvent that does not contain water, a fluorocarbon-based solvent, or a silicone-based solvent can be used as the solvent for the composite film-forming solution, but the film is formed by evaporation. In this case, considering the ease of handling, the temperature is preferably about 50 to 150 ° C.

On the other hand, when washing and removing using an organic solvent, those having a boiling point of 100 to 350 ° C. are suitable for use.

Specifically usable are petroleum naphtha, solvent naphtha, petroleum ether, petroleum benzine, isoparaffin, normal paraffin, decalin, industrial gasoline, nonane, decane, kerosene, dimethyl silicone, phenyl silicone, alkyl modified silicone, polyether silicone. Etc. can be mentioned.

Fluorocarbon solvents include fluorocarbon solvents, Fluorinert (product of 3M), Afludo (product of Asahi Glass). In addition, these may be used individually by 1 type and may mix 2 or more types as long as it mixes well. Further, an organic chlorine solvent such as chloroform may be added.

Furthermore, as in the first embodiment, pretreatment is performed in advance using a treatment method using only a substance having an alkoxysilyl group as a main component, and then a fluorocarbon group, a hydrocarbon group, and a chlorosilyl group are the main components. Even if a film is formed by a treatment method using only a substance, a film excellent in water / oil repellent / antifouling function can be stably obtained.

Even in the case of polyvinyl chloride or polyfluorinated ethylene fiber having no active hydrogen on the surface, the same treatment is possible if a hydroxyl group is added to the fiber surface by corona treatment or plasma treatment containing oxygen.

On the other hand, when a ketimine compound or organic acid, aldimine compound, enamine compound, oxazolidine compound, aminoalkylalkoxysilane compound is used instead of the above-mentioned silanol condensation catalyst, the reaction time is reduced to about half (30 minutes) even at the same concentration. it can.

Furthermore, a silanol condensation catalyst and a ketimine compound, or an organic acid, an aldimine compound, an enamine compound, an oxazolidine compound, and an aminoalkylalkoxysilane compound can be used in a range of 1: 9 to 9: 1. )), The reaction time can be further increased several times (5 to 10 minutes), and the film forming time can be reduced to a fraction of a minute.
(Embodiment 3)

In Embodiment 2, only a substance mainly composed of a fluorocarbon group, a hydrocarbon group, and a chlorosilyl group is used, and a ketimine compound, an organic acid, an aldimine compound, an enamine compound, or an oxazolidine is used as a catalyst instead of a silanol condensation catalyst. Even when a compound or an aminoalkylalkoxysilane compound is used, the reaction time can be reduced to about half (30 minutes) even at the same concentration.

Further, a silanol condensation catalyst and a ketimine compound, or an organic acid, an aldimine compound, an enamine compound, an oxazolidine compound, and an aminoalkylalkoxysilane compound can be used in a range of 1: 9 to 9: 1. )), The reaction time can be further increased several times (5 to 10 minutes), and the film forming time can be reduced to a fraction of a minute.

In this method as well, in the case of polyvinyl chloride or polyfluorinated ethylene fiber that does not have active hydrogen on the surface, the same treatment is possible by adding a hydroxyl group to the fiber surface by corona treatment or plasma treatment containing oxygen It becomes.

Hereinafter, specific examples of the present invention will be described. In addition, this invention is not limited at all by these Examples.

CF as a substance mainly composed of a fluorocarbon group, a hydrocarbon group, and a chlorosilyl group in a dry atmosphere (humidity of 35% or less is preferable. _{3 - (CF 2) 7 -} (CH 2) 2 and -SiCl _3, and SiCl ₄ as a material mainly containing chlorosilyl groups, 5% chloroform containing dimethyl silicone solution containing little water which is a non-aqueous organic solvent The composite film forming solution was prepared by dissolving in a concentration of 0.01 M / L and 0.002 M / L (5: 1), respectively.

  Next, the silk fabric is thoroughly washed and dried, and then the composite film is formed on the surface in a dry atmosphere (humidity of 35% or less is preferable. If the temperature is higher than this, the film-forming substance is hydrolyzed and the film becomes cloudy). The solution was applied and allowed to react at room temperature for 30 minutes.

At this time, since the fiber surface of the silk fabric contains a large number of hydroxyl groups and imino groups, that is, active hydrogen, and is covered with adsorbed water, the ≡SiCl group of the two substances and the hydroxyl group or imino group adsorbed on the fiber surface. Water was dehydrochlorinated and bonded to the fiber surface of the silk fabric in a state where a substance mainly composed of a fluorocarbon group, a hydrocarbon group and a silyl group and a substance mainly composed of a siloxane group were mixed.

A substance mainly composed of a fluorocarbon group, a hydrocarbon group, and a chlorosilyl group is bonded to a fiber surface of a silk fabric or a substance mainly composed of a siloxane group via the silyl group, and the siloxane group is mainly composed of the siloxane group. The substance to be bonded was bonded to the fiber surface of the silk fabric and the substance mainly composed of a fluorocarbon group, a hydrocarbon group, and a silyl group through a siloxane group.

Thereafter, when the excess composite film forming solution on the surface is washed away with ethanol, a substance mainly composed of a fluorocarbon group, a hydrocarbon group, and a silyl group and a substance mainly composed of a siloxane group having a thickness of about 5 nm are obtained. A composite membrane containing the composite membrane could be formed on the fiber surface of the silk fabric.

In addition, when the water droplet contact angle, which is the basic performance, was measured, it was stably 150 ° C. or more even when the kind of silk fabric was changed or even within the same silk fabric. Also, the dry cleaning durability was 100 times or more.
Here, Si (OCH ₃ ) ₄ or Si (OC ₂ H ₅ ) ₄ was used in place of SiCl ₄ , and the other conditions were the same, but almost the same results were obtained.

Further, the non-aqueous organic solvent is evaporated without washing (in this case, when the silk fabric is heated at 60 to 90 ° C., the evaporation of the solvent can be accelerated and the evaporation time can be shortened). A composite film containing a substance mainly composed of a fluorocarbon group, a hydrocarbon group and a silyl group and a substance mainly composed of a siloxane group having a thickness of about 35 nm could be formed on the fiber surface of the silk fabric.

In addition, even if this water drop contact angle also changed the kind of cloth of silk fabric, or within the same silk fabric, it was stably 140-150 degree | times. Also, the dry cleaning durability was 100 times or more.

(Comparative Example 1)
In Example 1, a water / oil repellent / antifouling silk fabric was produced under the same conditions except for SiCl ₄ which is a substance mainly composed of a chlorosilyl group. When the water droplet contact angle, which is the basic performance, was measured, there was variation depending on the location within the same fabric, and it was 130 degrees at a bad place and 150 degrees or more at a good place. Also, the dry cleaning durability was examined, and it was about 50 times.

From the above experiments, when treated with a treatment liquid using only a substance mainly composed of a fluorocarbon group, a hydrocarbon group, and a silyl group, the water repellency effect varies greatly, and the washing durability is greatly inferior. Was confirmed.

First, a cotton and polyester blend fabric (52:48) was prepared, washed thoroughly and dried.

On the other hand, for example, 90 g of CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (Si (OC ₂ H ₅ ) ₃ ) as a main component having a fluorocarbon group, a hydrocarbon group and an alkoxysilyl group, Silicone solvent containing almost no water by weighing and mixing 5 g of Si (OC ₂ H ₅ ) ₄ as a substance having an alkoxysilyl group as a main component and 0.3 g of dibutyltin oxide as a silanol condensation catalyst. For example, it was dissolved in a dimethylpolysiloxane solvent (boiling point 195 ° C.) to a total concentration of about 0.2% by weight (preferably the concentration is about 0.05 to 1%) to obtain a composite film forming solution.

This composite film forming solution was applied to the surface of the cotton / polyester blend fabric in normal air (relative humidity 57%, 70% in another experiment), and allowed to react for about 1 hour. The solvent was evaporated.

At this time, the fiber surface of cotton and polyester blended fabric (cotton, hemp, paper is also the same with cellulose) contains many hydroxyl groups, so the fluorocarbon group, hydrocarbon group, and alkoxysilyl group are mainly used. The component material and the ≡Si (OC ₂ H ₅ ) group of the material mainly composed of an alkoxysilyl group and the hydroxyl surface and adsorbed water on the fiber surface of the polyester blend fabric are dealcoholized in the presence of a silanol condensation catalyst (this In the case of de-C ₂ H ₅ OH) reaction, and further, an unreacted fluorocarbon group, hydrocarbon group and alkoxysilyl group as a main component on the fiber surface of the cotton / polyester blend fabric and an alkoxysilyl group The main component of this substance also undergoes a dealcoholization reaction with moisture in the air and chemically bonds with the entire surface of the fiber surface of the cotton / polyester blended fabric, resulting in approximately 40 nm thick fluorocarbon group and carbon. Composite films comprising materials 2 composed mainly of substance 1 and siloxane groups containing hydrogen as a main component group and the silyl group was formed on the fiber surface of the cotton and polyester blend fabrics.

When the water droplet contact angle, which is the basic performance, was measured, it was stably about 150 degrees even if the type of the polyester blended fabric was changed. Also, the durability of washing with detergent and water was examined, but it was 100 times or more.

On the other hand, after the cloth is taken out in the air and left for about 2 hours, the excess composite film forming solution on the surface is removed by washing with ethanol. As a result, fluorocarbon groups, hydrocarbon groups and silyl groups having a thickness of about 5 nm are mainly formed. A composite film containing the substance 1 as a component and the substance 2 containing a siloxane group as a main component could be formed on the fiber surface of the cotton and polyester blend fabric.

In this case, when the water droplet contact angle, which is the basic performance, was measured, it was stably 150 degrees or more.
Also, the durability of washing with detergent and water was examined, but it was 100 times or more.
Further, here, SiCl ₄ was used in place of Si (OC ₂ H ₅ ) ₄ and the other conditions were the same, but almost the same results were obtained except that the reaction time was reduced to about 10 minutes. It was.

On the other hand, dibutyltin oxide, which is a silanol catalyst, was replaced with H3 from Japan Epoxy Resin, which is a ketimine compound, and the other conditions were the same, but the reaction time was reduced to about 30 minutes. Results were obtained.

Furthermore, the silanol catalyst was replaced with a mixture of ketimine compound Japan Epoxy Resin H3 and silanol catalyst dibutyltin bisacetylacetonate (mixing ratio is 1: 1), and other conditions were the same. The same results were obtained except that the reaction time could be shortened to about 5 to 10 minutes.

In this case, since the solvent is evaporated after the adsorption treatment, it is needless to say that when the heat treatment is further performed at about 80 ° C., the solvent is completely evaporated and the water / oil repellent / antifouling performance is stabilized.

First, deer skin gloves were prepared, washed thoroughly and dried.

On the other hand, as a substance mainly composed of a fluorocarbon group, a hydrocarbon group, and an alkoxysilyl group, for example, 10 g of CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (Si (OCH ₃ ) ₃ ), a ketimine compound (We tried using Japan Epoxy Resin H3 and Chisso Sila Ace S340, but the performance was almost the same.) Each was adjusted to 0.3 g, and a silicone solvent containing almost no water, for example, The solution was dissolved in a dimethylpolysiloxane (boiling point 153 ° C.) solvent to a concentration of about 0.2% by weight (preferably the concentration is about 0.05 to 1%) to obtain a film forming solution.

The film forming solution was applied to the surface of the deer skin glove in normal air (relative humidity 57%, 70% in another experiment). I let you.

At this time, since the deer skin surface contains a large number of hydroxyl groups and imino groups, the ≡Si (OCH ₃ ) group of the substance mainly composed of the fluorocarbon group, hydrocarbon group and alkoxysilyl group and the wool surface. The hydroxyl groups and adsorbed water of the alkenyl group undergo dealcoholization (in this case, de-CH ₃ OH) in the presence of a ketimine catalyst, and the unreacted fluorocarbon group, hydrocarbon group, and alkoxysilyl group on the deer skin surface are mainly used. From the substance 1 whose main component is a fluorocarbon group, a hydrocarbon group and a silyl group having a thickness of about 30 nm chemically bonded to the entire surface of the deer skin surface through a dealcoholization reaction with moisture in the air. A water / oil repellent antifouling film could be formed on the deer skin surface.
When the contact angle with water, which is the basic performance, was measured, it was stably about 150 degrees. Further, when the dry cleaning durability was examined, it was about 50 times.

On the other hand, after taking out in the air for 1 to 2 hours and washing and removing the excess film-forming solution on the surface with ethanol, the main component is a fluorocarbon group, a hydrocarbon group and a silyl group having a thickness of about 4 nm. A water / oil repellent antifouling film made of the substance 1 could be formed on the deer skin surface.
In addition, although this coating film was somewhat inferior in washing durability, when the contact angle with water, which is the basic performance, was measured, it was stably 150 ° C. or more. Further, when the dry cleaning durability was examined, it was about 50 times.

In addition, when an organic acid or an aldimine compound, an enamine compound, an oxazolidine compound, and an aminoalkylalkoxysilane compound are used alone at the same concentration instead of the above-mentioned ketimine compound, it is almost the same as when a ketimine compound is used. The reaction time was about 30 minutes.

On the other hand, a silanol condensation catalyst is added to a ketimine compound or an organic acid, an aldimine compound, an enamine compound, an oxazolidine compound, and an aminoalkylalkoxysilane compound at a mixing ratio of 1: 1 ((Here, H3 and dibutyltin bis from Japan Epoxy Resin Co., Ltd.) Acetylacetonate was mixed at a ratio of 1: 1, and the mixing ratio was 1: 9 to 9: 1. The effect was remarkable. The time could be shortened to 5-10 minutes.

Here, the ketimine compound that can be used is not particularly limited. For example, 2,5,8-triaza-1,8-nonadiene, 3,11-dimethyl-4,7,10-triaza-3 , 10-tridecadiene, 2,10-dimethyl-3,6,9-triaza-2,9-undecadiene, 2,4,12,14-tetramethyl-5,8,11-triaza-4,11-pentadeca Diene, 2,4,15,17-tetramethyl-5,8,11,14-tetraaza-4,14-octadecadiene, 2,4,20,22-tetramethyl-5,12,19-triaza- 4,19-trieicosadiene and the like.

Further, the organic acid that can be used is not particularly limited, but there are, for example, formic acid, acetic acid, propionic acid, lactic acid, malonic acid, and the like, which have almost the same effects.

(Comparative Example 2)
On the other hand, in Example 3, a film was formed under the same conditions except that dibutyltin bisacetylacetonate, which is a silanol condensation catalyst, was used instead of the ketimine compound. In this case, the contact angle of the water droplet did not increase to 150 degrees or more unless the reaction was performed for about 1 hour after contacting the adsorbed liquid.

Therefore, the above results revealed that ketimine compounds, organic acids, aldimine compounds, enamine compounds, oxazolidine compounds, and aminoalkylalkoxysilane compounds are more active than silanol condensation catalysts.

Furthermore, it was confirmed that the activity was further increased when one of a ketimine compound, organic acid, aldimine compound, enamine compound, oxazolidine compound, and aminoalkylalkoxysilane compound was mixed with a silanol condensation catalyst.

FIG. 3 is a schematic cross-sectional view of the surface of the wool fiber of the water / oil / oil / repellency antifouling suit of the present invention expanded to the molecular level, showing a water / oil / oil repellent / antifouling treatment step. Here, (a) is a conceptual cross-sectional view of the surface of a wool fiber showing a state in which a composite film that partially contains a hydroxyl group is formed in Example 1, and (b) is a composite film that has completed a dehydration reaction. It is a cross-sectional conceptual diagram of the wool fiber surface which shows the state made.

Explanation of symbols

1 Substance mainly composed of fluorocarbon group, hydrocarbon group and silyl group 2 Substance mainly composed of siloxane group 2
3 Wool fiber (surface)
4 Hydroxyl group 5 Composite film containing hydroxyl group 6 Reticulated silica film 7 Water / oil repellent / antifouling composite film

Claims (16)

An apparel product having a highly durable antifouling coating, wherein the coating is composed of at least a substance 1 mainly composed of a fluorocarbon group, a hydrocarbon group and a silyl group, and a substance 2 composed mainly of a siloxane group. Water and oil repellent antifouling apparel product characterized by being a composite film containing A substance 1 mainly composed of a fluorocarbon group, a hydrocarbon group and a silyl group is formed on the surface of the silica film and / or apparel product through the silyl group in a silica film composed of the substance 2 mainly composed of a siloxane group. The water / oil / oil repellent antifouling apparel product according to claim 1, wherein the apparel product is bonded and fixed to the water / oil repellent. A substance 1 mainly composed of a fluorocarbon group, a hydrocarbon group and a silyl group and a substance 2 mainly composed of a siloxane group are bonded to each other or individually on the surface of the apparel product via the silyl group and the siloxane group, respectively. The water / oil repellent / antifouling apparel product according to claim 1. The molecular composition ratio of the substance 1 mainly composed of a fluorocarbon group, a hydrocarbon group and a silyl group and the substance 2 mainly composed of a siloxane group contained in the composite film is 1: 1 to 199: 1. The water / oil repellent / antifouling apparel product according to claim 1. In an atmosphere having a relative humidity of 35% or less, the surface of the apparel product is mainly composed of a fluorocarbon group, a hydrocarbon group, and a chlorosilyl group as a main component, and a chlorosilyl group as a main component or an alkoxysilyl group as a main component. A method for producing a water / oil repellent / antifouling apparel product comprising the step of bringing a composite film forming solution mixed and diluted with a non-aqueous organic solvent into contact with each other to react to form a film. Mix and dilute a substance mainly composed of fluorocarbon group, hydrocarbon group and chlorosilyl group with a substance mainly composed of chlorosilyl group or a substance mainly composed of alkoxysilyl group on the surface of the apparel product with a non-aqueous organic solvent. 6. The method according to claim 5, comprising a step of bringing the composite film-forming solution into contact with each other to form a film, and a step of washing and removing an excess solution on the surface of the apparel product using a solvent. A method for producing water / oil repellent and antifouling apparel products. CF _3- (CF ₂ ) _n- (CH ₂ ) ₂ -SiCl ₃ or [CF _3- (CF ₂ ) _n- (CH ₂ ) as a substance mainly composed of a fluorocarbon group, a hydrocarbon group and a chlorosilyl group ₂ ] ₂ -SiCl ₂ , [CF ₃ — (CF ₂ ) _n — (CH ₂ ) ₂ ] ₃ —SiCl (n is 0 or an integer), and Cl ₃ Si (OSiCl) as a substance mainly composed of a chlorosilyl group. ₂ ) _m Cl (m is 0 or integer) or (AO) ₃ Si (OSi (OA) ₂ ) _m (OA) (m is 0 or integer, A is an alkyl group) The molecular composition ratio at the time of mixing is 1: 1 to 199: 1, and the method for producing a water / oil repellent / antifouling apparel product according to claim 5 or 6 is used. Non-aqueous system for substances with fluorocarbon group, hydrocarbon group and alkoxysilyl group as main component, alkoxysilyl group or chlorosilyl group as main component and silanol condensation catalyst on apparel product surface A method for producing a water / oil repellent / antifouling apparel product, comprising a step of bringing a composite film forming solution mixed and diluted with an organic solvent into contact with each other to form a film. Non-aqueous organic substance on the surface of apparel products with fluorocarbon group, hydrocarbon group and alkoxysilyl group as main components, alkoxysilyl group as main component or chlorosilyl group as main component and silanol condensation catalyst A composite film forming solution mixed and diluted with a solvent is brought into contact and reacted to form a film, and the excess solution on the surface of the apparel product is washed and removed using a solvent. A method for producing a water / oil repellent antifouling apparel product according to claim 8. CF ₃ — (CF ₂ ) _n — (CH ₂ ) ₂ —Si (OA) ₃ or [CF ₃ — (CF ₂ ) _n — as a substance mainly composed of a fluorocarbon group, a hydrocarbon group and an alkoxysilyl group. _{(CH 2) 2] 2 -Si} (OA) 2, [CF 3 - (CF 2) n - (CH 2) 2] 3 -SiOA (n is 0 or an integer, a is an alkyl group) with, alkoxysilyl (AO) ₃ Si (OSi (OA) ₂ ) _m OA (m is 0 or integer, A is an alkyl group) or Cl ₃ Si (OSiCl) ₂₎ m _Cl (m is used 0 or an integer), the molecular composition ratio at the time of mixing 1: 1 to 199: water-repellent, oil-repellent antifouling according to claim 8 and 9, characterized in that one Manufacturing method for apparel products. The water / oil repellent / antifouling property according to claim 8, wherein a ketimine compound or an organic acid, aldimine compound, enamine compound, oxazolidine compound, aminoalkylalkoxysilane compound is used instead of the silanol condensation catalyst. Manufacturing method for apparel products. The repellent agent according to any one of claims 8 to 11, wherein the silanol condensation catalyst is a ketimine compound or at least one selected from organic acids, aldimine compounds, enamine compounds, oxazolidine compounds, and aminoalkylalkoxysilane compounds. A method for producing water / oil repellent antifouling apparel products. A non-aqueous organic solvent containing a fluorocarbon group, hydrocarbon group, and alkoxysilyl group as a main component and a ketimine compound, or an organic acid, aldimine compound, enamine compound, oxazolidine compound, or aminoalkylalkoxysilane compound on the surface of the apparel product. A method for producing a water / oil repellent / antifouling apparel product comprising a step of bringing a mixed and diluted solution into contact with each other to form a film. A non-aqueous organic solvent containing a fluorocarbon group, hydrocarbon group, and alkoxysilyl group as a main component and a ketimine compound, or an organic acid, aldimine compound, enamine compound, oxazolidine compound, or aminoalkylalkoxysilane compound on the surface of the apparel product. 14. The water repellent method according to claim 13, comprising a step of contacting and reacting the mixed and diluted solution to form a film, and a step of cleaning and removing an excess solution on the surface of the apparel product using a solvent. Manufacturing method of oil repellent antifouling apparel products. CF ₃ — (CF ₂ ) _n — (CH ₂ ) ₂ —Si (OA) ₃ or [CF ₃ — (CF ₂ ) _n — as a substance mainly composed of a fluorocarbon group, a hydrocarbon group and an alkoxysilyl group. _{(CH 2) 2] 2 -Si} (OA) 2, [CF 3 - (CF 2) n - (CH 2) 2] 3 -SiOA (n is 0 or an integer, a is an alkyl group) characterized by using The method for producing a water / oil repellent / antifouling apparel product according to claim 13. The water repellent according to any one of claims 13 to 15, wherein the silanol condensation catalyst is mixed with at least one selected from a ketimine compound or an organic acid, an aldimine compound, an enamine compound, an oxazolidine compound, and an aminoalkylalkoxysilane compound. Manufacturing method of oil repellent antifouling apparel products.

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