JP7528702B2 - Water and oil repellent treatment for fabrics - Google Patents

Description

The present invention relates to a water- and oil-repellent treatment for fabrics.

Conventionally, textile products have been known in which water repellency has been imparted to the surface by treating the textile products with fluorine-based water repellents. However, there are concerns about the environmental impact of fluorine compounds, and because they require heat treatment at high temperatures during use, treatment agents that do not contain fluorine compounds are being investigated.

In this context, a water- and oil-repellent treatment agent for fabrics has been proposed that contains an acrylic resin made from (meth)acrylic esters with alkyl groups having 6 to 24 carbon atoms and (anhydride) maleic acid as essential raw materials, a basic compound, and an aqueous medium (see, for example, Patent Document 1).

However, when the water-repellent treatment agent described in Patent Document 1 is used on high-density fabrics, the water-repellent properties are sometimes not fully achieved.

International Publication No. 2018/180538

The problem that the present invention aims to solve is to provide a water- and oil-repellent treatment for fabrics that does not contain fluorine compounds, which are of concern for their environmental impact, and that has excellent dye uniformity and excellent water- and oil-repellency even when used on high-density fabrics.

As a result of intensive research into solving the above problems, the inventors have discovered that a water- and oil-repellent treatment agent for fabrics containing a specific polyolefin-composite acrylic resin and an aqueous medium can solve the above problems.

That is, the present invention relates to a water- and oil-repellent treatment agent for fabrics that contains a polyolefin composite acrylic resin (A) having a polyolefin resin (a1) and an acrylic polymer (a2), and an aqueous medium (B), characterized in that the alkyl (meth)acrylate in the monomer raw material of the acrylic polymer (a2) is 40 to 99 mass % and the (meth)acrylic acid is 0.5 to 5 mass %.

The water- and oil-repellent treatment agent for fabrics of the present invention can impart excellent water- and oil-repellency to a substrate, and can therefore be suitably used as a water-repellent treatment agent for fabrics made of fibers such as cotton, silk, wool, hemp, polyethylene, nylon, polyester, polyurethane, and rayon. It is particularly suitable as a water-repellent treatment agent for high-density fabrics.

The water- and oil-repellent treatment agent for fabrics of the present invention is a water- and oil-repellent treatment agent for fabrics that contains a polyolefin composite acrylic resin (A) having a polyolefin resin (a1) and an acrylic polymer (a2), and an aqueous medium (B), in which the alkyl (meth)acrylate in the monomer raw material of the acrylic polymer (a2) is 40 to 99% by mass, and (meth)acrylic acid is 0.5 to 5% by mass.

Examples of the polyolefin resin (a1) include polypropylene, high-density polyethylene, ultra-high molecular weight polyethylene, linear low-density polyethylene, low-density polyethylene, very low-density polyethylene, ultra-low-density polyethylene, polymethylpentene, ethylene-propylene copolymer, propylene-1-butene random copolymer, propylene-ethylene-1-butene random copolymer, copolymer of propylene and α-olefin having 5 to 12 carbon atoms, propylene-non-conjugated diene copolymer, ethylene-non-conjugated diene copolymer, ethylene-propylene-non-conjugated diene copolymer, polybutene, ethylene-vinyl acetate copolymer, ethylene-vinyltrimethoxysilane copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-methyl methacrylate copolymer, styrene-butadiene block copolymer, and hydrogenated products thereof. The polyolefin resin (a1) can be used alone or in combination of two or more kinds.

The melting point of the polyolefin resin (a1) is preferably 50 to 100°C, and more preferably 60 to 90°C, because this provides excellent processability into fabrics and more effective expression of water repellency and oil repellency.

The weight average molecular weight of the polyolefin resin (a1) is preferably 20,000 to 100,000, and more preferably 30,000 to 60,000, since this further improves water repellency.

The average molecular weight of the resin in the present invention is a value calculated in terms of polystyrene based on gel permeation chromatography (hereinafter abbreviated as "GPC").

In addition, the polyolefin resin (a1) is preferably polypropylene, as this further improves water repellency.

The acrylic polymer (a2) is obtained by polymerizing an alkyl (meth)acrylate, (meth)acrylic acid, and, if necessary, other unsaturated monomers.

Examples of the alkyl (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, cyclohexyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isobornyl (meth)acrylate, lauryl (meth)acrylate, and stearyl (meth)acrylate. These alkyl (meth)acrylates can be used alone or in combination of two or more.

In addition, it is preferable to use 50 to 95% by mass of alkyl (meth)acrylate having 6 or more carbon atoms, as this further improves water repellency.

As the alkyl (meth)acrylate, it is preferable to use methyl methacrylate, since this has a better affinity with fabrics.

The alkyl (meth)acrylate in the monomer raw material of the acrylic polymer (a2) is 40 to 99% by mass, preferably 60 to 90% by mass.

The amount of (meth)acrylic acid in the monomer raw material of the acrylic polymer (a2) is 0.5 to 5 parts by mass, but 0.8 to 3.5% by mass is preferred because this further improves the permeability into the fabric.

Examples of the other unsaturated monomers include (meth)acrylamide, glycidyl (meth)acrylate, 2-methylaminoethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, γ-methacryloxypropyltrimethoxylane, benzyl (meth)acrylate, and diethylene glycol. Examples of the monomers include acrylic acid esters such as butyl di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, and glycerin di(meth)acrylate; styrene compounds such as styrene, α-methylstyrene, paramethylstyrene, and chloromethylstyrene; and unsaturated carboxylic acids such as maleic acid (anhydride), fumaric acid, citraconic acid (anhydride), mesaconic acid (anhydride), itaconic acid (anhydride), and aconitic acid (anhydride). These other monomers can be used alone or in combination of two or more.

In the present invention, "(meth)acrylate" refers to either or both of methacrylate and acrylate, "(meth)acrylic acid" refers to either or both of methacrylic acid and acrylic acid, "(meth)maleic anhydride" refers to either or both of maleic anhydride and maleic acid, and "(meth)acryloyl group" refers to either or both of methacryloyl group and acryloyl group.

The amount of the other unsaturated monomer used is the remainder obtained by subtracting the proportions of the alkyl (meth)acrylate and (meth)acrylic acid from the total of 100% by mass of the unsaturated monomer raw materials.

The mass ratio of the polyolefin resin (a1) to the acrylic polymer (a2) [(a1)/(a2)] is preferably in the range of 10/90 to 40/60, and more preferably in the range of 20/80 to 35/65, since this further improves the uniformity of dyeing on the fabric.

As a method for producing the polyolefin-composite acrylic resin (A), the underwater polymerization method or the emulsion polymerization method is preferred because the polyolefin-composite acrylic resin (A) can be easily obtained.

As a method for obtaining the polyolefin hybrid acrylic resin (A) by emulsion polymerization, for example, a method in which the monomer raw material of the acrylic polymer (a2) is radically polymerized in an aqueous medium in the presence of the polyolefin resin (a1), an emulsifier, and a polymerization initiator at a temperature of 50 to 100°C can be mentioned.

Examples of the emulsifier include anionic emulsifiers such as sulfate esters and salts thereof of higher alcohols, alkylbenzene sulfonates, polyoxyethylene alkylphenyl sulfonates, polyoxyethylene alkyl diphenyl ether sulfonates, sulfate half ester salts of polyoxyethylene alkyl ethers, alkyl diphenyl ether disulfonates, and dialkyl succinate sulfonates; nonionic emulsifiers such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene diphenyl ethers, polyoxyethylene-polyoxypropylene block copolymers, and acetylene diols; cationic emulsifiers such as alkyl ammonium salts; and amphoteric emulsifiers such as alkyl (amide) betaines and alkyl dimethyl amine oxides. These emulsifiers can be used alone or in combination of two or more. The monomer (a1) can also be used as an emulsifier.

Examples of the polymerization initiator include azo compounds such as 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2-methylbutyronitrile), and azobiscyanovaleric acid; organic peroxides such as tert-butyl peroxypivalate, tert-butyl peroxybenzoate, tert-butylperoxy-2-ethylhexanoate, di-tert-butyl peroxide, cumene hydroperoxide, benzoyl peroxide, and tert-butyl hydroperoxide; and inorganic peroxides such as hydrogen peroxide, ammonium persulfate, potassium persulfate, and sodium persulfate. These polymerization initiators can be used alone or in combination of two or more kinds. It is preferable to use these polymerization initiators in an amount of 0.1 to 10% by mass based on the total amount of the monomers that are the raw materials for the polymer.

Since the dispersion stability of the polyolefin composite acrylic resin (A) is further improved, it is preferable to adjust the pH with a basic compound and/or an acidic compound. Examples of the basic compound include organic amines such as methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, 2-aminoethanol, and 2-dimethylaminoethanol; inorganic basic compounds such as ammonia (water), sodium hydroxide, and potassium hydroxide; and quaternary ammonium hydroxides such as tetramethylammonium hydroxide, tetra-n-butylammonium hydroxide, and trimethylbenzylammonium hydroxide. These basic compounds can be used alone or in combination of two or more.

Examples of the acidic compounds include carboxylic acid compounds such as formic acid, acetic acid, propionic acid, and lactic acid; monoesters or diesters of phosphoric acid such as monomethyl phosphate and dimethyl phosphate; organic sulfonic acid compounds such as methanesulfonic acid, benzenesulfonic acid, and dodecylbenzenesulfonic acid; and inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid. Among these, carboxylic acid compounds are preferred. These acidic compounds can be used alone or in combination of two or more.

The aqueous medium (B) may be water, an organic solvent miscible with water, or a mixture thereof. Examples of organic solvents miscible with water include alcohols such as methanol, ethanol, n-propanol, and isopropanol; ketones such as acetone and methyl ethyl ketone; polyalkylene glycols such as ethylene glycol, diethylene glycol, and propylene glycol; alkyl ethers of polyalkylene glycols; and lactams such as N-methyl-2-pyrrolidone. In the present invention, water alone may be used, or a mixture of water and an organic solvent miscible with water may be used, or an organic solvent miscible with water alone may be used. From the standpoint of safety and environmental burden, water alone or a mixture of water and an organic solvent miscible with water is preferred, and water alone is particularly preferred.

It is simple and preferable to use the aqueous medium (B) that is the same as that used when producing the polyolefin-composite acrylic resin (A) by the underwater polymerization method and emulsion polymerization method.

The water- and oil-repellent treatment agent for fabrics of the present invention contains the polyolefin composite acrylic resin (A) and the aqueous medium (B), and it is preferable that the polyolefin composite acrylic resin (A) is obtained by an emulsion polymerization method or the like and dispersed in the aqueous medium (B).

In addition, if necessary, the amount of organic solvents in the water/oil repellent treatment agent for fabrics of the present invention can be reduced by undergoing a solvent removal process.

In addition, the water- and oil-repellent treatment agent for fabrics of the present invention can be used in combination with additives such as water-repellents, oil-repellents, dispersants, curing catalysts, lubricants, fillers, thixotropic agents, tackifiers, waxes, heat stabilizers, light-resistance stabilizers, fluorescent whitening agents, and foaming agents, pH adjusters, leveling agents, gelling inhibitors, dispersion stabilizers, antioxidants, radical scavengers, heat-resistance agents, inorganic fillers, organic fillers, plasticizers, reinforcing agents, catalysts, antibacterial agents, mildew inhibitors, rust inhibitors, thermoplastic resins, thermosetting resins, pigments, dyes, conductivity-imparting agents, antistatic agents, moisture permeability enhancers, oil-repellents, hollow foams, compounds containing crystal water, flame retardants, water-absorbing agents, moisture absorbents, deodorizers, foam stabilizers, defoamers, antifungal agents, preservatives, anti-algae agents, pigment dispersants, antiblocking agents, and hydrolysis inhibitors, as necessary.

The water- and oil-repellent treatment agent for fabrics of the present invention can improve water- and oil-repellency without containing halogen compounds, and therefore preferably contains silicone oils such as dimethyl silicone oil, methylphenyl silicone oil, methylhydrogen silicone oil, and amino-modified silicone oil. Among these, amino-modified silicone oils are more preferred, and amino-modified silicone oils having a primary diamine structure are even more preferred. These silicone oils can be used alone or in combination of two or more kinds.

The content of the silicone oil in the water/oil repellent treatment agent for fabrics is preferably 1 to 10% by mass, more preferably 2 to 8% by mass, because this can further improve water repellency, oil repellency, and flexibility.

The water- and oil-repellent treatment agent for fabrics of the present invention preferably contains a cationic dispersant, since it can make the dispersion state of each component more uniform, and more preferably contains alkyltrimethylammonium, dialkyldimethylammonium chloride, alkyltrimethylammonium chloride, etc. These cationic dispersants can be used alone or in combination of two or more kinds.

The content of the cationic dispersant in the water/oil repellent treatment agent for fabrics is preferably 0.05 to 3 mass %, and more preferably 0.1 to 2 mass %, because this makes the dispersion state of each component more uniform.

Examples of fabrics that can be treated with the water- and oil-repellent fabric treatment agent of the present invention include fabrics made of fibers such as cotton, silk, wool, hemp, polyethylene, nylon, polyester, polyurethane, and rayon.

The present invention will be described in more detail below with reference to specific examples. The average molecular weight was measured under the following GPC measurement conditions.

[GPC measurement conditions]
Measurement device: High-speed GPC device ("HLC-8220GPC" manufactured by Tosoh Corporation)
Column: The following columns manufactured by Tosoh Corporation were used, connected in series.
"TSKgel G5000" (7.8mm I.D. x 30cm) x 1 "TSKgel G4000" (7.8mm I.D. x 30cm) x 1 "TSKgel G3000" (7.8mm I.D. x 30cm) x 1 "TSKgel G2000" (7.8mm I.D. x 30cm) x 1 Detector: RI (differential refractometer)
Column temperature: 40°C
Eluent: tetrahydrofuran (THF)
Flow rate: 1.0 mL/min Injection volume: 100 μL (sample concentration 4 mg/mL in tetrahydrofuran solution)
Standard sample: A calibration curve was prepared using the following monodisperse polystyrene.

(Monodisperse polystyrene)
"TSKgel Standard Polystyrene A-500" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene A-1000" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene A-2500" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene A-5000" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-1" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-2" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-4" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-10" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-20" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-40" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-80" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-128" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-288" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-550" manufactured by Tosoh Corporation

(Example 1: Production and evaluation of water- and oil-repellent treatment agent for fabric (1))
Into a four-neck flask equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen inlet tube, 130 parts by mass of soft water was charged and heated to 70°C. 32 parts by mass of polypropylene resin (Idemitsu Petrochemical Co., Ltd. "Elmodu S-400") and 110 parts by mass of methylcyclohexane were charged, and 96.7 parts by mass of cyclohexyl methacrylate, 29.8 parts by mass of methyl methacrylate, 20 parts by mass of methacrylic acid, 1 part by mass of γ-methacryloxypropyltrimethoxylane, 1 part by mass of lauryl mercaptan, 16 parts by mass of KF-96 (Shin-Etsu Chemical Co., Ltd.), 6 parts by mass of Noigen TSD-200D (Dai-ichi Kogyo Seiyaku Co., Ltd.), 12 parts by mass of Newcol 707-SF (Nippon Nyukazai Co., Ltd.), and 115 parts by mass of soft water were added dropwise to the flask, and 0.8 parts by mass of PZ-69 (NOF Corporation), and 0.3 parts by mass of SFS (Sumitomo Seika Co., Ltd.) were added dropwise over 3 hours, and the reaction was carried out at 70 ° C. Hold for 120 minutes after neutralization. The solvent was removed (about 60 minutes) and the mixture was cooled under reduced pressure (0.080 to 0.095 MPa) at 60°C to obtain an aqueous dispersion of polyolefin composite acrylic resin (A-1) with a non-volatile content of 27.2% by mass. 93.3 parts by mass of this aqueous dispersion was mixed with 4 parts by mass of amino-modified silicone oil ("DOWSIL SF-8417" manufactured by Dow Toray Co., Ltd.), 0.7 parts by mass of alkyl trimethyl ammonium, and 2 parts by mass of methanol, and then diluted with ion-exchanged water to a non-volatile content of 6% by mass to obtain a water- and oil-repellent treatment agent for fabric (1).

(Example 2: Production and evaluation of water- and oil-repellent treatment agent for fabric (2))
A four-neck flask equipped with a stirrer, reflux condenser, thermometer and nitrogen blowing tube was charged with 130 parts by mass of soft water and heated to 70 ° C. 32 parts by mass of polypropylene resin (Idemitsu Petrochemical Co., Ltd. "Elmodu S-400") and 110 parts by mass of methylcyclohexane were charged, and 96.7 parts by mass of cyclohexyl methacrylate, 29.8 parts by mass of methyl methacrylate, 20 parts by mass of methacrylic acid, 1 part by mass of γ-methacryloxypropyltrimethoxylane, 1 part by mass of lauryl mercaptan, 6 parts by mass of Noigen TSD-200D (Dai-ichi Kogyo Seiyaku Co., Ltd.), 12 parts by mass of Newcol 707-SF (Nippon Nyukazai Co., Ltd.), and 115 parts by mass of soft water were added dropwise to the flask, and 0.8 parts by mass of PZ-69 (Nippon Oil & Fats Co., Ltd.) and 0.3 parts by mass of CP (remarks required) were added dropwise over 3 hours, and the reaction was carried out at 70 ° C. After neutralization, the mixture was held for 120 minutes. The mixture was desolvated (about 60 minutes) and cooled at 60°C under reduced pressure (0.080 to 0.095 MPa) to obtain an aqueous dispersion of polyolefin composite acrylic resin (A-1) with a non-volatile content of 27.2% by mass. 93.3 parts by mass of this aqueous dispersion was mixed with 4 parts by mass of amino-modified silicone oil (Dow Toray Co., Ltd.'s "DOWSIL SF-8417"), 0.7 parts by mass of alkyl trimethyl ammonium, and 2 parts by mass of methanol, and then diluted with ion-exchanged water to a non-volatile content of 6% by mass to obtain a water- and oil-repellent treatment agent for fabrics (2).

(Comparative Example 1: Production and Evaluation of Water- and Oil-Repellent Treatment Agent for Fabric (R1))
In a four-neck flask equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen inlet tube, 400 parts by mass of soft water, 5 parts by mass of acrylic acid, 45 parts by mass of 3-(acryloylamino)propyltrimethylammonium chloride, and 50 parts by mass of acrylamide were charged and heated to 65 ° C. 0.72 parts by mass of ammonium persulfate and 0.08 parts by mass of preservative MBS were added and reacted at 65 ° C. An aqueous acrylic resin composition with a non-volatile content of 5% by mass was obtained. 93.3 parts by mass of this aqueous acrylic resin composition was mixed with 4 parts by mass of amino-modified silicone oil (Dow Toray Co., Ltd. "DOWSIL SF-8417"), 0.7 parts by mass of alkyl trimethylammonium, and 2 parts by mass of methanol, and then the non-volatile content was diluted to 6% by mass with ion-exchanged water to obtain a water- and oil-repellent treatment agent for fabrics (R1).

[Preparation of Water- and Oil-Repellent Treated Substrate]
The water- and oil-repellent treating agent for fabric obtained above was applied to a base fabric (high-density nylon fabric or high-density polyester fabric) using a mangle coater in an amount of 1 g/ ^m2 after drying, and the fabric was dried at 120°C for 5 minutes and then at 150°C for 10 minutes to obtain a water- and oil-repellent treated substrate.

[Evaluation of dye uniformity]
The dyeing uniformity was evaluated according to the following criteria obtained above.
5: No uneven dyeing 4: Small uneven dyeing 3: Large uneven dyeing 2: Small oil stains 1: Large oil stains

[Evaluation of water repellency]
The water repellency of the water repellent treated substrate obtained above was evaluated according to JIS L1092 and the following criteria.
5: Water droplets do not split, no traces left after wiping 4: Water droplets separate, no traces left after wiping 3: No bleeding when dripping, traces left after wiping 2: Traces of seepage left after dripping 1: Completely soaked

[Evaluation of oil repellency]
The oil repellency of the water-repellent treated substrate obtained above was evaluated according to the following criteria in accordance with AATCC118.
5: No oil spread, no bleeding after wiping 4: Oil spread, no bleeding after wiping 3: No oil spread, bleeding after wiping 2: Oil spread, bleeding after wiping 1: Oil spread within 1 minute after dropping (incomplete)
0: Complete seepage within 1 minute after oil droplet dripping

The compositions and evaluation results of Examples 1 and 2 and Comparative Example 1 above are shown in Table 1.

The abbreviations in the table are as follows.
S-400: "Elmodu S-400" manufactured by Idemitsu Petrochemical Co., Ltd.
CHMA: Cyclohexyl methacrylate MMA: Methyl methacrylate MAA: Methacrylic acid AA: Acrylic acid MPTMS: γ-Methacryloxypropyltrimethoxylane DMAPPA: 3-(acryloylamino)propyltrimethylammonium chloride AM: Acrylamide

It was confirmed that the water- and oil-repellent treatment agents for fabrics of the present invention in Examples 1 and 2 have excellent dye uniformity and can impart excellent water and oil repellency.

On the other hand, Comparative Example 1 is an example that does not contain polyolefin resin (a1), and it was confirmed that the dyeing levelness was poor and the water repellency was also insufficient.

Claims (5)

A method for producing a water- and oil-repellent treatment agent for fabrics, which contains a polyolefin-composite acrylic resin (A) having a polyolefin resin (a1) and an acrylic polymer (a2), an aqueous medium (B) , and an amino-modified silicone oil having a primary diamine structure , and which does not contain a fluorine compound, wherein the water- and oil-repellent treatment agent for fabrics is obtained by radical polymerization of the monomer raw material for the acrylic polymer (a2) in the presence of the polyolefin resin (a1), and is characterized in that the alkyl (meth)acrylate in the monomer raw material for the acrylic polymer (a2) is 40 to 99 mass % . 2. The method for producing a water- and oil-repellent treating agent for fabric according to claim 1, wherein the melting point of the polyolefin resin (a1) is 50 to 90° C. 3. The method for producing a water- and oil-repellent treating agent for fabric according to claim 1, wherein the weight average molecular weight of the polyolefin resin (a1) is from 20,000 to 100,000. The method for producing a water- and oil-repellent treatment agent for fabric according to any one of claims 1 to 3, wherein the mass ratio [(a1)/(a2)] of the polyolefin resin (a1) to the acrylic polymer (a2 ) is in the range of 10/90 to 40/60. The method for producing the water- and oil-repellent treating agent for fabric according to any one of claims 1 to 4 , further comprising the step of: