JP6839336B2 - Textile processing agents and processing formulations and textile fabrics and textile products treated with them. - Google Patents

Description

The present invention relates to a fiber processing agent and a processing formulation that impart excellent water repellency, and a fiber cloth and a textile product using the same.

Conventionally, a fluorine-based water repellent is known as a water repellent. This water repellent exhibits good water repellency when treated on a base material such as textile products, and is used in many products such as carpets, textiles, paper and leather.

Based on recent research results, it is referred to as perfluorooctanoic acid (hereinafter referred to as "PFOA") and perfluorooctanesulfonic acid (hereinafter referred to as "PFOS"), which are a type of long-chain fluoroalkyl compounds contained in fluorine-based water repellents. ) Has a stable structure, is not easily decomposed in the environment, and has a high accumulation property, so it is known that it is widely present in water and wildlife, and there is a concern about the burden on the environment. It has been announced on April 14, 2003 that the EPA (US Environmental Protection Agency) will step up its scientific research, especially for PFOA.

At present, there is concern that fluorine-based compounds may accumulate in the environment, and PFOA-, PFOS-free fluorine-based water repellents and non-fluorine-based water repellents have been proposed. So far, there are various techniques for water-repellent processing related to textile products, and various processing agents and processing techniques associated therewith have been put out. As known techniques, those described in Patent Documents 1 to 3 below. Can be mentioned.

In recent years, environmentally friendly PFOA, PFOS-free fluorine-based water repellents and non-fluorine-based water repellents have been reported. For example, at least one of a water repellent which is a compound of high melting point paraffin of Patent Document 1 and a (meth) acrylic acid ester having 10 to 24 carbon atoms, a silicon-based compound of Patent Document 2, a wax-based compound, and a wax-zirconium-based compound. There is a water repellent agent containing a cross-linking agent as a main component, and a water repellent agent of a polymer compound containing a (meth) acrylic acid ester having 12 or more carbon atoms as a monomer in the ester portion of Patent Document 3. However, all of them are inferior in water repellency to conventional fluorine-based water repellents, and none of them are satisfactory.

Japanese Patent Publication No. 2012-52062 Japanese Unexamined Patent Publication No. 2006-124866 Japanese Unexamined Patent Publication No. 2006-328624

To provide PFOA, a PFOS-free fluorine-based water repellent and a non-fluorine-based water repellent that imparts excellent water repellency to textile fabrics, textile products, etc., and a method for processing textile fabrics using the same. The purpose.

The inventor has been diligently studying the above problems, and by adding the polymer (A) of glycidyl (meth) acrylic acid ester to the water-repellent compound (B), the water-repellent compound (B). ) It was found that the water repellency was improved as compared with the single substance.

In the present invention, a fiber processing agent and a processing formulation obtained by blending a polymer (A) of glycidyl (meth) acrylic acid ester and a water-repellent compound (B), and a fiber cloth and fiber processed using the same. It is a product.

The polymer (A) of glycidyl (meth) acrylic acid ester is a fiber processing agent of an aqueous emulsion which is a polymer of a repeating unit (meth) acrylic acid ester containing 90% by weight or more of glycidyl (meth) acrylate. is there.

In the present invention, the solid content ratio of the polymer (A) of glycidyl (meth) acrylic acid ester to the water-repellent compound (B) is 0.5: 99.5 to 35.0: 65.0. Processing agents, processing formulations, and textile fabrics and textile products processed using them.

The water-repellent compound (B) is a fiber processing agent which is a fluorine-based water repellent and a non-fluorine-based water repellent.

The fiber processing agent of the present invention is an excellent PFOA, PFOS-free fluorine-based water repellent and non-fluorine-based water repellent by blending the polymer (A) of glycidyl (meth) acrylic acid ester. It has water repellency and can be used as an alternative to conventional fluorine-based water repellents containing PFOA and PFOS.

By processing with the fiber processing agent according to the present invention, it is possible to impart excellent water repellency to fiber fabrics, textile products and the like.

A fiber processing agent and a processing formulation obtained by blending a polymer (A) of a glycidyl (meth) acrylic acid ester and a compound (B) having water repellency, and a fiber cloth and a textile product processed using the same.

The polymer (A) of the glycidyl (meth) acrylic acid ester used in the present invention is a repeating unit (meth) acrylic acid ester containing 90% by weight or more of the glycidyl (meth) acrylic acid ester in the solid content. An aqueous emulsion of the polymer, preferably containing a polymer of a (meth) acrylic acid ester as a repeating unit in an amount of 95% by weight based on the solid content. Further, as a component other than the polymer (A) of the glycidyl (meth) acrylic acid ester, a (meth) acrylate ester monomer having no reactive group is preferable.

The (meth) acrylate ester monomer having no reactive group is methyl (meth) acrylate, ethyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, hexadecyl (meth). Acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, behenyl (meth) acrylate, isostearyl methacrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, benzyl (meth) acrylate, isobonyl (meth) Acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, tricyclopentanyl (meth) acrylate, adamantyl (meth) acrylate, 2-methyl-2 -There are adamantyl (meth) acrylates and the like, which may be used alone or in combination of two or more.

Water repellency when the ratio of the polymer of the repeating unit (meth) acrylic acid ester contained in the polymer (A) of the glycidyl (meth) acrylic acid ester used in the present invention is less than 90% by weight in the solid content. Does not improve.

The solid content ratio of the glycidyl (meth) acrylic acid ester polymer (A) to the water-repellent compound (B) is preferably in the range of 0.5: 99.5 to 35.0: 65.0. From 0: 95.0 to 15.0: 85.0, the water repellency is improved as compared with the water-repellent compound (B) alone.

When the ratio of the polymer (A) of the glycidyl (meth) acrylic acid ester is less than 0.5 in the solid content ratio of the polymer (A) of the glycidyl (meth) acrylic acid ester and the compound (B) having water repellency. , Water repellency does not improve.

When the ratio of the glycidyl (meth) acrylic acid ester polymer (A) exceeds 35.0 in the solid content ratio of the glycidyl (meth) acrylic acid ester polymer (A) and the water-repellent compound (B), Water repellency is reduced.

As a method for producing the polymer (A) of glycidyl (meth) acrylic acid ester and the compound (B) having water repellency, a known emulsion polymerization method can be used. For example, a monomer batch charging method in which monomers are collectively charged, a monomer dropping method in which monomers are continuously dropped, and the like can be mentioned.

The surfactant used for emulsion polymerization is not particularly limited, and for example, a nonionic surfactant, a cationic surfactant, a polymer surfactant and the like can be used. These may be used alone or in combination of two or more.

Examples of the cationic surfactant include various quaternary salts such as alkyltrimethylammonium salt, alkyldimethylbenzylammonium salt, dialkyldimethylammonium salt, alkylpyridinium chloride salt, and quaternary products of polyoxyethylene alkylamine. An amine salt obtained by neutralizing an amine such as an alkylamine salt, an alkyldimethylamine salt, a polyoxyethylene alkylamine salt, or the like with an appropriate acid can be used. Examples of the counter ion include, but are not limited to, chlorine ion, bromine ion, sulfate ion, formate ion, acetate ion, methyl sulfate ion, ethyl sulfate ion and the like. These may be used alone or in combination of two or more.

Examples of nonionic surfactants include fatty acid esters such as various higher fatty acid glycerins, polyoxyethylene alkyl ethers, polyoxypropylene alkyl ethers, polyoxyethylene fatty acid esters, fatty acid alkanolamides, alkyl glucosides, higher alcohols, and pluronics. A type activator, alkyldimethylamine-N-oxide and the like can be used. These may be used alone or in combination of two or more.

As the polymerization initiator used for emulsion polymerization, a general radical initiator can be used. Radical polymerization initiators include water-soluble or oil-soluble persulfates, peroxides, and azobis compounds. Specifically, potassium persulfate, sodium persulfate, ammonium persulfate, hydrogen peroxide, benzoyl peroxide, t-butyl hydroperoxide, t-butyl peroxybenzoate, 2,2-azobisisobutyronitrile, 2 , 2-Azobis (2-diaminopropane) hydrogen peroxide, 2,2-azobis (2,4-dimethylvaleronitrile) and the like, and these may be used alone or in combination of two or more.

Each of the above-mentioned components is emulsified and dispersed, and after a reaction, a product is obtained. The reaction method is carried out by adding a polymerization initiator. The emulsified and dispersed components are placed in a reaction vessel and reacted with oxygen removed by nitrogen purging.

Water is preferable as the diluting solvent for emulsification and dispersion. Further, water and an organic solvent may be mixed if necessary. The organic solvent at this time is not particularly limited as long as it is an organic solvent miscible with water, but for example, alcohols such as methanol and ethanol, ketones such as acetone and methyl ethyl ketone, propylene glycol, dipropylene glycol, and tri. Examples thereof include glycols such as propylene glycol. The ratio of water to the organic solvent is not particularly limited.

Examples of the water-repellent compound (B) include PFOA, PFOS-free fluorine-based water repellent, and fiber processing agent which is a non-fluorine-based water repellent.

There are cross-linking agents and resins as combined processing agents for improving washing durability performance. Examples thereof include blocked isocyanate-based cross-linking agents, isocyanate-based cross-linking agents, epoxy-modified cross-linking agents, carbodiimide-based cross-linking agents, oxazoline-based cross-linking agents, glioxal resins, and melamine-based resins. Such cross-linking agents and resins may be used alone or in combination of two or more.

Further, in the present invention, additives such as an antifungal agent, an antioxidant, a light stabilizer, an antistatic agent, a conductive agent, a flame retardant, and a pigment may be contained or used in combination, if necessary.

The fiber fabric used in the present invention includes synthetic fibers such as polyester, nylon, acrylic and polyurethane, recycled fibers such as rayon, bamboo fiber and soybean protein fiber, semi-synthetic fibers such as acetate, cotton, linen, silk and hair. It may be composed of any of the natural fibers, or may be a combination of a plurality of fibers such as a blended fiber, a blended spinn, a mixed weave, and a mixed knitting of these fibers, and is not particularly limited. Absent.

Further, the form may be any of woven fabric, knitted fabric, non-woven fabric, staples, threads and the like, and is not particularly limited.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

Washing durability test method The processed cloths obtained in Examples and Comparative Examples were washed 10 times based on the JIS L-0217 103 method (using a 2-tank electric washing machine and using an attack made by Kao Co., Ltd. as a detergent. After that, the water repellency of the naturally dried cloth (hereinafter referred to as "L-10 cloth") and the processed cloth before washing (hereinafter referred to as "L-0 cloth") was evaluated by the following methods. ..

Evaluation method of water repellency The test was carried out according to the spray method of JIS L-1092. The results were visually evaluated according to the following grades.
Water repellency: Condition 5: No wetness adhered to the surface 4: Slightly adhered to the surface Wetness 3: Partial wetness on the surface 2: Wetness on the surface 1: Wetness on the entire surface Item 0: Both front and back sides are completely moist.

(Synthesis Example 1)
In a 500 ml flask, add 150 g of distilled water while stirring 90 g of glycidyl glycidyl (meth) acrylate, 3 g of polyoxyethylene (10 mol) lauryl ether, 1 g of stearyltrimethylammonium chloride, and 10 g of tripropylene glycol monoethyl ether. Emulsify and disperse while keeping the temperature at 50-60 ° C. This emulsion was reacted at 60 ° C. for 6 hours in a nitrogen atmosphere, and finally distilled water was added to prepare an aqueous dispersion containing 100% by weight of glycidyl (meth) acrylate and having a polymer concentration of 30% by weight.

(Synthesis Example 2)
In a 500 ml flask, while stirring 81 g of glycidyl glycidyl (meth) acrylate, 9 g of isobonyl (meth) acrylate, 3 g of polyoxyethylene (10 mol) lauryl ether, 1 g of stearyltrimethylammonium chloride, and 10 g of tripropylene glycol monoethyl ether, while stirring. 150 g of distilled water is added, and the mixture is emulsified and dispersed while maintaining the liquid temperature at 50 to 60 ° C. This emulsion was reacted at 60 ° C. for 6 hours in a nitrogen atmosphere, and finally distilled water was added to prepare an aqueous dispersion containing 90% by weight of glycidyl (meth) acrylate and having a polymer concentration of 30% by weight.

(Synthesis Example 3)
In a 500 ml flask, stir 78 g of glycidyl glycidyl (meth) acrylate, 12 g of isobonyl (meth) acrylate, 3 g of polyoxyethylene (10 mol) lauryl ether, 1 g of stearyltrimethylammonium chloride, and 10 g of tripropylene glycol monoethyl ether. 150 g of distilled water is added, and the mixture is emulsified and dispersed while maintaining the liquid temperature at 50 to 60 ° C. This emulsion was reacted at 60 ° C. for 6 hours in a nitrogen atmosphere, and finally distilled water was added to prepare an aqueous dispersion containing 89% by weight of glycidyl (meth) acrylate and having a polymer concentration of 30% by weight.

(Synthesis Example 4)
In a 500 ml flask, add 150 g of distilled water while stirring 75 g of stearyl acrylate, 3 g of 2-hydroxyethyl acrylate, 1 g of stearyltrimethylammonium chloride, 3 g of polyoxyethylene (10 mol) lauryl ether, and 10 g of tripropylene glycol monoethyl ether. Emulsify and disperse while keeping the liquid temperature at 50-60 ° C. This emulsion was radically polymerized at 60 ° C. for 6 hours in a nitrogen atmosphere, and finally distilled water was added to prepare an aqueous dispersion having a polymer concentration of 30% by weight as a non-fluorinated water repellent.

(Example 1)
The polymer (A) of the glycidyl (meth) acrylic acid ester of Synthesis Example 1 and the water-repellent compound (B) of Synthesis Example 4 are mixed so as to have the following solid content ratio, and the resin concentration is 30% by mass. The dispersion was adjusted.
(A) Polymer of Synthesis Example 1: (B) Polymer of Synthesis Example 4 = 0.5: 99.5

(Example 2)
The polymer (A) of the glycidyl (meth) acrylic acid ester of Synthesis Example 1 and the water-repellent compound (B) of Synthesis Example 4 are mixed so as to have the following solid content ratio, and the resin concentration is 30% by mass. The dispersion was adjusted.
(A) Polymer of Synthesis Example 1: (B) Polymer of Synthesis Example 4 = 35.0: 65.0

(Example 3)
The polymer (A) of the glycidyl (meth) acrylic acid ester of Synthesis Example 2 and the water-repellent compound (B) of Synthesis Example 4 are mixed so as to have the following solid content ratio, and the resin concentration is 30% by mass. The dispersion was adjusted.
(A) Polymer of Synthesis Example 2: (B) Polymer of Synthesis Example 4 = 35.0: 65.0

(Example 4)
The polymer (A) of the glycidyl (meth) acrylic acid ester of Synthesis Example 1 and the water-repellent compound (B) of Synthesis Example 4 are mixed so as to have the following solid content ratio, and the resin concentration is 30% by mass. The dispersion was adjusted.
(A) Polymer of Synthesis Example 1: (B) Polymer of Synthesis Example 4 = 10.0: 90.0

(Example 5)
Palladium ECO-100 (paraffin-based water repellent: manufactured by Ohara Palladium Chemical Co., Ltd.) as the polymer (A) of the glycidyl (meth) acrylic acid ester obtained in Synthesis Example 1 and the water-repellent compound (B). , Solid content 40%) was mixed so as to have the following solid content ratio, and a dispersion liquid having a resin concentration of 30% by mass was adjusted.
(A) Polymer of Synthesis Example 1: (B) Palladium ECO-100 = 10.0: 90.0

(Example 6)
As the polymer (A) of the glycidyl (meth) acrylic acid ester of Synthesis Example 1 and the water-repellent compound (B), Neoseed NR-158 (acrylic water repellent: manufactured by Nicca Chemical Co., Ltd., solid content) 35%) was mixed so as to have the following solid content ratio, and a dispersion having a resin concentration of 30% by mass was prepared.
(A) Polymer of Synthesis Example 1: (B) Neoseed NR-158 = 35.0: 65.0

(Example 7)
As the polymer (A) of the glycidyl (meth) acrylic acid ester of Synthesis Example 1 and the water-repellent compound (B), Unidyne TG-5601 (PFOA, PFOS-free fluorine-based water repellent: Daikin Industries, Ltd.) , 30% solid content) was mixed so as to have the following solid content ratio, and a dispersion having a resin concentration of 30% by mass was adjusted.
(A) Polymer of Synthesis Example 1: (B) Unidyne TG-5601 = 10.0: 90.0

(Comparative Example 1)
A dispersion having a resin concentration of 30% by mass was prepared using the polymer of Synthesis Example 4 as the water-repellent compound (B).

(Comparative Example 2)
The polymer (A) of the glycidyl (meth) acrylic acid ester of Synthesis Example 1 and the water-repellent compound (B) of Synthesis Example 4 are mixed so as to have the following solid content ratio, and a resin concentration of 30% by mass is dispersed. The liquid was adjusted.
(A) Polymer of Synthesis Example 1: (B) Polymer of Synthesis Example 4 = 0.4: 99.6

(Comparative Example 3)
The polymer (A) of the glycidyl (meth) acrylic acid ester of Synthesis Example 1 and the water-repellent compound (B) were mixed so as to have the following solid content ratio to prepare a dispersion having a resin concentration of 30% by mass. ..
(A) Polymer of Synthesis Example 1: (B) Polymer of Synthesis Example 4 = 40.0: 60.0

(Comparative Example 4)
The polymer (A) of the glycidyl (meth) acrylic acid ester of Synthesis Example 3 and the water-repellent compound (B) of Synthesis Example 4 are mixed so as to have the following solid content ratio, and a resin concentration of 30% by mass is dispersed. The liquid was adjusted.
(A) Polymer of Synthesis Example 3: Polymer of (B) Synthesis Example 4 = 0.5: 99.5

(Comparative Example 5)
The polymer (A) of the glycidyl (meth) acrylic acid ester of Synthesis Example 3 and the water-repellent compound (B) of Synthesis Example 4 are mixed so as to have the following solid content ratio, and a resin concentration of 30% by mass is dispersed. The liquid was adjusted.
(A) Polymer of Synthesis Example 3: (B) Polymer of Synthesis Example 4 = 35.0: 65.0

(Comparative Example 6)
As the water-repellent compound (B), Palladium ECO-100 (paraffin-based water repellent: manufactured by Ohara Palladium Chemical Co., Ltd.) was used to prepare a dispersion having a resin concentration of 30% by mass.

(Comparative Example 7)
As the water-repellent compound (B), Neoseed NR-158 (acrylic water repellent: manufactured by Nicca Chemical Co., Ltd., solid content 35%) was used to prepare a dispersion having a polymer concentration of 30% by mass.

(Comparative Example 8)
As the water-repellent compound (B), Unidyne TG-5601 (PFOA, PFOS-free fluorine-based water repellent: manufactured by Daikin Industries, Ltd., solid content 30%) was used to prepare a dispersion having a polymer concentration of 30% by mass. It was adjusted.

[Water repellency evaluation 1]
The dispersions obtained in Examples 1 to 7 and Comparative Examples 1 to 8 are diluted with distilled water to 5%, soaked in 100% cotton cloth and 100% polyester cloth, squeezed with a roll, and wet pickup is 100. The fabric was then dried at 110 ° C. for 2 minutes and then heat treated at 170 ° C. for 2 minutes for padding. The water repellency of the L-0 cloth and the L-10 cloth was evaluated for the cloth treated in this way. The results are shown in Table 1.

[Water repellency evaluation 2]
Distill 5% of the dispersions obtained in Examples 1 to 7 and Comparative Examples 1 to 8 and 1% of a blocked isocyanate-based cross-linking agent (manufactured by Ohara Palladium Chemical Co., Ltd., Paracat PGE: the same applies hereinafter). Dilute with water. Soak 100% cotton cloth and 100% polyester cloth and squeeze with a roll to make the wet pickup 100% by mass, then dry the cloth at 110 ° C for 2 minutes and heat treat at 170 ° C for 2 minutes. Processing was performed. The water repellency of the L-0 cloth and the L-10 cloth was evaluated for the cloth treated in this way. The results are shown in Table 2.

Comparing Examples 1 to 4 with Comparative Example 1, it can be seen that the water repellency of Examples 1 to 4 is improved by blending the polymer (A) of glycidyl (meth) acrylic acid ester.

Comparing Comparative Example 1 and Comparative Example 2, it can be seen that there is no difference in water repellency.

Comparing Example 1 and Comparative Example 4, the water repellency is lowered, and in Example 2 and Comparative Example 5, the water repellency is further lowered.

Comparing Example 5 and Comparative Example 6, it can be seen that the water repellency of Example 5 is improved as compared with Comparative Example 6 by blending the polymer (A) of glycidyl (meth) acrylic acid ester.

Comparing Example 6 and Comparative Example 7, it can be seen that the water repellency of Example 6 is improved as compared with Comparative Example 7 by blending the polymer (A) of glycidyl (meth) acrylic acid ester.

Comparing Example 7 and Comparative Example 8, it can be seen that the water repellency of Example 7 is improved as compared with Comparative Example 8 by blending the polymer (A) of glycidyl (meth) acrylic acid ester.

By processing with the fiber processing agent of the present invention, it is possible to impart excellent water repellency to fiber fabrics, textile products and the like.

Claims (2)

A fiber processing agent obtained by blending a polymer (A) of a glycidyl (meth) acrylic acid ester and a compound (B) having water repellency, and a textile fabric and a textile product processed using the same. The polymer (A) of glycidyl (meth) acrylic acid ester is an aqueous emulsion of a polymer of (meth) acrylic acid ester of a repeating unit containing 90% by weight or more of glycidyl (meth) acrylate, and has water repellency. The compound (B) is a fluorine-based water repellent or a non-fluorine-based water repellent. A fiber in which the solid content ratio of the polymer (A) of the glycidyl (meth) acrylic acid ester of claim 1 to the water-repellent compound (B) is 0.5: 99.5 to 35.0: 65.0. Processing agents, and textile fabrics and textile products processed with them.