Water-repellent and oil-repellent fiber treating agent

Abstract

To provide a surface treatment agent exhibiting superior water-repellent and oil-repellent properties as a substitute for fluorine compound-based surface treatment agents.SOLUTION: It has been discovered that incorporation of an adduct (A) of a compound selected from polyalkyleneimine and alkylene polyamine with an aliphatic isocyanate, together with an oxide compound (B) selected from citric acid and oxyacids of phosphorus, enables maintenance of superior water-repellent and oil-repellent properties while preventing coloration.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a water- and oil-repellent fiber treating agent containing an adduct of a compound selected from polyalkyleneimine and alkylenepolyamine with an aliphatic isocyanate, and an acid compound selected from citric acid and phosphorus oxyacids, and to fibers treated with the water- and oil-repellent fiber treating agent. [Background technology]

[0002] As a surface treatment agent that imparts water and oil repellency, a fluorine-containing polymer, for example, a polymer of a polymerizable compound having a perfluoroalkyl group or a perfluoroalkenyl group, is known.

[0003] These polymers of fluorine compounds have the advantage of being excellent in properties such as heat resistance, oxidation resistance, and weather resistance, and are widely used as surface treatment agents for textiles, leather, paper, and mineral substrates.

[0004] On the other hand, fluorine compound-based surface treatment agents are considered to be PFAS (perfluoroalkyl and polyfluoroalkyl substances), and there are concerns that they may be harmful to humans due to their environmental persistence and bioaccumulation. Therefore, there is a demand for surface treatment agents with excellent water and oil repellency to replace fluorine compound-based surface treatment agents.

[0005] As a fiber treatment agent, an adduct of polyalkyleneimine and aliphatic isocyanate has been disclosed as a treatment agent having excellent water repellency. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 2020 / 022367 Summary of the Invention [Problem to be solved by the invention]

[0007] While adducts of polyalkyleneimines and aliphatic isocyanates are useful as fiber treatment agents, they have the problem of discoloration of treated articles. [Means for solving the problem]

[0008] As a result of extensive research into the above-mentioned problems, the present inventors have found that by containing an adduct (A) of an aliphatic isocyanate with a compound selected from polyalkyleneimine and alkylenepolyamine, and an acid compound (B) selected from citric acid and phosphorus oxyacid, it is possible to prevent discoloration while maintaining excellent water and oil repellency.

[0009] The present invention can also be described as follows. Item 1. A water- and oil-repellent fiber treatment agent comprising (A) an adduct of a compound selected from polyalkyleneimine and alkylenepolyamine with an aliphatic isocyanate, and (B) an acid compound selected from citric acid and phosphorus oxyacid. Item 2. The water- and oil-repellent fiber treatment agent according to Item 1, wherein the adduct (A) of a compound selected from polyalkyleneimine and alkylenepolyamine with an aliphatic isocyanate is an adduct of a compound selected from polyethyleneimine, polypropyleneimine, ethylenediamine, diethylenetriamine, triethylenetetramine, and tetraethylenepentamine with an alkyl isocyanate having an alkyl group having 6 or more carbon atoms. Item 3. The water- and oil-repellent fiber treatment agent according to Item 1, which contains a liquid medium. Item 4. The water- and oil-repellent fiber treatment agent according to Item 3, wherein the liquid medium is water. Item 5. The water- and oil-repellent fiber treatment agent according to Item 1, comprising 0.1 to 20 parts by mass of an acid compound (B) selected from citric acid and a phosphorus oxygen acid relative to 100 parts by mass of the adduct (A) of an aliphatic isocyanate with a compound selected from polyalkyleneimines and alkylenepolyamines. Item 6. Fibers surface-treated with the water- and oil-repellent fiber treatment agent according to any one of items 1 to 5. [Effects of the Invention]

[0010] The present invention contains an adduct (A) of a compound selected from compounds selected from polyalkyleneimines and alkylenepolyamines with an aliphatic isocyanate, and an acid compound (B) selected from citric acid and phosphorus oxyacids, thereby preventing discoloration while maintaining excellent water and oil repellency, and is therefore extremely useful as a fiber treatment agent. DETAILED DESCRIPTION OF THE INVENTION

[0011] The present invention will be described in detail below. In this specification, a numerical value connected with "~" means a numerical range including the numerical values ​​before and after "~" as the lower limit and upper limit. When multiple lower limit values ​​and multiple upper limit values ​​are listed separately, any lower limit value and upper limit value can be selected and connected with "~".

[0012] The water- and oil-repellent fiber treatment agent of the present invention contains (A) an adduct of a compound selected from compounds selected from polyalkyleneimines and alkylenepolyamines with an aliphatic isocyanate, and (B) an acid compound selected from citric acid and phosphorus oxyacids.

[0013] The polyalkyleneimine in the adduct (A) is preferably a polyalkyleneimine having an alkylene group structural unit and an amino group structural unit in the main chain, the alkylene group having 2 to 6 carbon atoms, more preferably a polyalkyleneimine having 2 to 4 carbon atoms, further preferably polyethyleneimine or polypropyleneimine, and particularly preferably polyethyleneimine. The polyalkyleneimine may be a copolymer, such as a copolymer of ethyleneimine and propyleneimine. The polyalkyleneimine may also be an adduct to which ethylene oxide, propylene oxide, or the like has been added.

[0014] The number average molecular weight of the polyalkyleneimine is preferably, but not limited to, a lower limit of about 100 and an upper limit of about 20000. The number average molecular weight can be measured by gel permeation chromatography (GPC).

[0015] Polyalkyleneimines are generally produced by ionic polymerization of alkyleneimines such as ethyleneimine and propyleneimine, or by polymerizing alkyloxazolines and then partially or completely hydrolyzing the polymers.

[0016] The alkylene polyamine in the adduct (A) may be a polyalkylene polyamine having at least two alkylene groups in the molecule, preferably an alkylene polyamine in which the alkylene group has 2 to 6 carbon atoms, and more preferably an alkylene polyamine in which the alkylene group has 2 to 4 carbon atoms. Specific examples of the alkylene polyamine in the adduct (A) include ethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine, and hexamethylene diamine, with ethylene diamine, diethylene triamine, triethylene tetramine, and tetraethylene pentamine being particularly preferred. Commercially available alkylene polyamines can be used.

[0017] The aliphatic isocyanate in the adduct (A) is preferably an alkyl(mono)isocyanate or an alkenyl(mono)isocyanate, and particularly preferably an alkyl(mono)isocyanate. The alkyl group in the alkyl(mono)isocyanate and the alkenyl group in the alkenyl(mono)isocyanate preferably have 6 to 30 carbon atoms, more preferably 8 to 24 carbon atoms, and even more preferably 10 to 20 carbon atoms.

[0018] Specific examples of the aliphatic isocyanate include octyl isocyanate, dodecyl isocyanate, tetradecyl isocyanate, hexadecyl isocyanate, and octadecyl isocyanate.

[0019] The adduct (A) of a compound selected from polyalkyleneimine and alkylenepolyamine with an aliphatic isocyanate can be obtained by reacting a compound selected from polyalkyleneimine and alkylenepolyamine with an aliphatic isocyanate. The reaction may be carried out in an inert gas atmosphere such as nitrogen.

[0020] In the adduct (A) of a compound selected from polyalkyleneimine and alkylenepolyamine with an aliphatic isocyanate, the reaction of the compound selected from polyalkyleneimine and alkylenepolyamine with an aliphatic isocyanate is preferably carried out in water or an organic solvent, and examples of the organic solvent include, but are not limited to, aromatic hydrocarbons such as toluene and xylene, aliphatic hydrocarbons such as hexane, ester-based aliphatic hydrocarbons such as ethyl acetate and butyl acetate, and alicyclic hydrocarbons such as cyclohexane. These solvents may be used alone or in combination of two or more.

[0021] Furthermore, the compound selected from polyalkyleneimine and alkylenepolyamine is preferably reacted with the aliphatic isocyanate so that the ratio of the amino groups (-NH groups, -NH2 groups) of the compound selected from polyalkyleneimine and alkylenepolyamine to the isocyanate groups of the aliphatic isocyanate is 0.6:1 to 0.95:1, and more preferably 0.7:1 to 0.9:1.

[0022] The reaction temperature is preferably 10° C. to 150° C., more preferably 20° C. to 100° C. The reaction time depends on the reaction temperature, but is generally 0.1 to 5 hours.

[0023] The content of the adduct (A) of a compound selected from polyalkyleneimine and alkylenepolyamine with an aliphatic isocyanate in the water- and oil-repellent fiber treatment agent is preferably 1 to 95 mass%, more preferably 2 to 60 mass%, and may be 3 to 40 mass%.

[0024] The water- and oil-repellent fiber treating agent of the present invention contains an acid compound (B) selected from citric acid and phosphorus oxygen acids.

[0025] Examples of phosphorus oxyacids used in the present invention include phosphoric acids such as phosphoric acid, hypophosphorous acid, phosphorous acid, orthophosphoric acid, and hypophosphoric acid, and condensed phosphoric acids such as metaphosphoric acid, pyrophosphoric acid (diphosphoric acid), tripolyphosphoric acid, polyphosphoric acid, and ultraphosphoric acid.

[0026] The content of the acid compound (B) selected from citric acid and phosphorus oxygen acids in the water- and oil-repellent fiber treatment agent is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, even more preferably 0.1 to 8 parts by mass, and particularly preferably 0.1 to 5 parts by mass, relative to 100 parts by mass of the adduct (A) of polyalkyleneimine and aliphatic isocyanate.

[0027] The water- and oil-repellent fiber treatment agent preferably contains a liquid medium, and examples thereof include water or an organic solvent. Examples of organic solvents include toluene, xylene, benzene, acetonitrile, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, glyme (ethylene glycol dimethyl ether), diglyme (diethylene glycol dimethyl ether), THF (tetrahydrofuran), acetone, methyl ethyl ketone, cyclohexanone, ethyl acetate, butyl acetate, propylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol, tripropylene glycol, and ethanol. Water and an organic solvent may be mixed as needed. The liquid medium in the water- and oil-repellent fiber treatment agent may be the liquid medium used in the reaction of the adduct (A) of a polyalkyleneimine and an aliphatic isocyanate.

[0028] The content of the liquid medium in the water- and oil-repellent fiber treatment agent is preferably 4.9 to 98.9 mass %, more preferably 39.9 to 95 mass %, and may be 59.9 to 90 mass %.

[0029] In the water- and oil-repellent fiber treatment agent, the adduct (A) of a compound selected from polyalkyleneimine and alkylenepolyamine with an aliphatic isocyanate may be dissolved or dispersed in a liquid medium. This is because, after an object is treated with the water- and oil-repellent fiber treatment agent, the surface of the object is coated with the adduct (A) of a compound selected from polyalkyleneimine and alkylenepolyamine with an aliphatic isocyanate, thereby exhibiting water and oil repellency.

[0030] The water- and oil-repellent fiber treating agent may further contain a surfactant. The inclusion of a surfactant can improve the dispersibility of the adduct (A) of a compound selected from polyalkyleneimine and alkylenepolyamine with an aliphatic isocyanate in the liquid medium in the water- and oil-repellent fiber treating agent, thereby increasing its penetration into fibers.

[0031] As the surfactant, anionic surfactants, nonionic surfactants, and cationic surfactants can be used, and commercially available products may also be used.

[0032] Examples of the anionic surfactant include alkylbenzene sulfonates, alkyl sulfates, polyoxyethylene alkyl ether sulfates, and fatty acid salts.

[0033] Examples of nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene polycyclic phenyl ethers, polyoxyalkylene alkyl ethers, sorbitan fatty acid esters, and polyoxyethylene sorbitan fatty acid esters.

[0034] Examples of cationic surfactants include monostearyltrimethylammonium chloride, monostearyldimethylmonoethylammonium ethyl sulfate, mono(stearyl)monomethyldi(polyethylene glycol)ammonium chloride, monofluorohexyltrimethylammonium chloride, di(tallow alkyl)dimethylammonium chloride, and dimethylmonococonutamine acetate, and it is more preferable to use quaternary ammonium chloride.

[0035] The surfactant is preferably contained in an amount of 0.1 to 20 parts by mass, more preferably 0.3 to 15 parts by mass, per 100 parts by mass of the adduct (A) of a compound selected from polyalkyleneimine and alkylenepolyamine with an aliphatic isocyanate.

[0036] The water- and oil-repellent fiber treatment agent may contain additives such as antifoaming agents, preservatives, pH adjusters, thickeners, pigments, drying speed adjusters, film-forming aids, antifreeze agents, ultraviolet absorbers, antioxidants, antibacterial agents, preservatives, insect repellents, fragrances, and flame retardants, as needed.

[0037] The method for producing the water- and oil-repellent fiber treatment agent is not particularly limited, and any stirring device for uniformly mixing and dispersing can be used, such as an agitator, a homomixer, a pipeline mixer, a blender, a clearmix, etc. The adduct (A) of a compound selected from polyalkyleneimine and alkylenepolyamine with an aliphatic isocyanate, the acid compound (B), the liquid medium, the surfactant, etc. can be added all at once or in portions, as desired, depending on the state of dissolution and dispersion.

[0038] A method for producing a water- and oil-repellent fiber treatment agent may involve using an aqueous dispersion obtained by reacting a compound selected from polyalkyleneimine and alkylenepolyamine with an aliphatic isocyanate, and adding an acid compound (B), a liquid medium, a surfactant, and the like to the aqueous dispersion.

[0039] As a method for treating with the water- and oil-repellent fiber treatment agent, any conventional method can be used without limitation. For example, the object can be treated with the water- and oil-repellent fiber treatment agent by immersion, spraying, coating, adhesion, etc., and then dried. Furthermore, after drying, heat treatment may be performed as necessary.

[0040] The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to the following examples as long as it does not deviate from the gist of the invention.

[0041] Example 1 First, an aqueous dispersion of alkyl isocyanate-added polyalkyleneimine was prepared by adding 7.4 parts by mass of polyethyleneimine (number average molecular weight 1800) as the polyalkyleneimine, 7.4 parts by mass of a 63% aqueous solution of monostearyltrimethylammonium chloride as a cationic surfactant, and 201.2 parts by mass of water as a solvent to a vessel of a predetermined size, followed by stirring and mixing to obtain an aqueous polyethyleneimine solution.

[0042] On the other hand, 42 parts by mass of octadecyl isocyanate as an alkyl isocyanate was dissolved in 42 parts by mass of ethyl acetate as a solvent to obtain 84 parts by mass of an octadecyl isocyanate solution.

[0043] Next, the octadecyl isocyanate solution was added to the above polyethyleneimine aqueous solution, and the mixture was stirred for 30 minutes at 25°C to 40°C using a Clearmix. This resulted in an aqueous dispersion of octadecyl isocyanate-added polyethyleneimine (hereinafter referred to as Emulsion A). The volume-based D50 of the octadecyl isocyanate-added polyethyleneimine (abbreviated as PEI+ODI) in Emulsion A was 0.3 μm, and the solids content was 15.3 mass%.

[0044] <Particle size distribution> The D50 of the octadecyl isocyanate-added polyethyleneimine in emulsion A was calculated from the particle size distribution curve measured using a laser diffraction / scattering particle size distribution analyzer (LA-950V2, manufactured by Horiba, Ltd.).

[0045] <Evaluation> In order to evaluate the colorability and water and oil repellency of Examples 1 to 3 and Comparative Examples 1 to 4, coating films were prepared as follows. Using the combinations of adduct (A) and acid compound (B) shown in Table 1, solutions were prepared in Examples 1 to 3 and Comparative Examples 1 to 4 by adding 2% by mass of acid compound (B) to the solid content (100% by mass) of the active ingredient. This solution was coated onto aluminum foil with an applicator, heated and dried at 120°C for 15 minutes, and a coating film with a thickness of 10 μm was obtained. The film was stored in a constant temperature and humidity room (23°C, 50%) for one day, and the contact angle was measured.

[0046] <Colorability> The coloration of the coating film (test piece) was evaluated by visually inspecting the coating film after heating, based on the following criteria. 〇: No visible coloration ×: Visually colored

[0047] <Contact angle> For the coating films obtained in the examples and comparative examples, contact angles (25°C) were measured to evaluate water and oil repellency. Specifically, the water- and oil-repellent surface of each coating film was used as the test surface, and the contact angles of pure water (approximately 1-2 μl), hexadecane (approximately 1-2 μl), and diiodomethane (approximately 1-2 μl) were measured using a contact angle measuring device (fully automated contact angle meter "DMo-702" manufactured by Kyowa Interface Science Co., Ltd.). Measurement results were obtained three times, and the average value of the contact angles after 1 minute is shown in the results. The results are shown in Table 1. It can be said that a sample has water and oil repellency if the contact angle for water is 80° or greater, the contact angle for hexadecane is 30° or greater, and the contact angle for diiodomethane is 60° or greater. The larger the contact angle (unit: °), the better the water and oil repellency.

[0048] [Table 1]

[0049] Table 1 shows that the coating films obtained in Examples 1 to 3, compared to Comparative Examples 1 to 4, are not colored and have both water and oil repellency, making them useful as water- and oil-repellent surface treatment agents. [Industrial Applicability]

[0050] The surface treatment agent of the present invention has excellent water and oil repellency and is therefore very useful as a surface treatment agent for fibers.

Claims

1. A water- and oil-repellent fiber treatment agent comprising: (A) an adduct of a compound selected from polyalkyleneimine and alkylenepolyamine with an aliphatic isocyanate; and (B) an acid compound selected from citric acid and a phosphorus oxyacid.

2. 2. The water- and oil-repellent fiber treating agent according to claim 1, wherein the adduct (A) of a compound selected from polyalkyleneimine and alkylenepolyamine with an aliphatic isocyanate is an adduct of a compound selected from polyethyleneimine, polypropyleneimine, ethylenediamine, diethylenetriamine, triethylenetetramine, and tetraethylenepentamine with an alkyl isocyanate having an alkyl group having 6 or more carbon atoms.

3. The water- and oil-repellent fiber treating agent according to claim 1, which contains a liquid medium.

4. 4. The water- and oil-repellent fiber treating agent according to claim 3, wherein the liquid medium is water.

5. 2. The water- and oil-repellent fiber treatment agent according to claim 1, comprising 0.1 to 20 parts by mass of an acid compound (B) selected from citric acid and a phosphorus oxygen acid relative to 100 parts by mass of the adduct (A) of an aliphatic isocyanate with a compound selected from a polyalkyleneimine and an alkylenepolyamine.

6. A fiber surface-treated with the water- and oil-repellent fiber treatment agent according to any one of claims 1 to 5.

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