JP7790636B2 - Water- and oil-repellent treatment agent for fabric, and fabric - Google Patents

Description

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

Traditionally, textile products have been known to have their surfaces rendered water-repellent by treating them with fluorine-based water-repellent agents. However, there are concerns about the environmental impact of fluorine compounds, and because they require high-temperature heat treatment 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, which contains a polyolefin resin, a polyolefin-composite acrylic resin having an acrylic polymer, and an aqueous medium (see, for example, Patent Document 1).

However, although this water- and oil-repellent treatment agent has excellent water repellency, it has the problem of insufficient oil repellency.

JP 2022-62389 A

The problem that this invention aims to solve is to provide a water- and oil-repellent treatment agent for fabrics that does not contain fluorine compounds, which are of concern for their environmental impact, and that can exhibit excellent water and oil repellency.

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

That is, the present invention relates to a water- and oil-repellent treatment agent for fabrics, which contains a chlorinated polyolefin composite acrylic resin (A) having a chlorinated polyolefin resin (a1) and an acrylic polymer (a2), an aqueous medium (B), and a modified silicone oil (C), wherein the modified silicone oil (C) contains an amino-modified silicone oil (c1) and a polyether-modified silicone oil (c2).

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

The water- and oil-repellent treatment agent for fabrics of the present invention contains a chlorinated polyolefin composite acrylic resin (A) having a chlorinated polyolefin resin (a1) and an acrylic polymer (a2), an aqueous medium (B), and a modified silicone oil (C), wherein the modified silicone oil (C) contains an amino-modified silicone oil (c1) and a polyether-modified silicone oil (c2).

The chlorinated polyolefin resin (a1) is a chlorinated polyolefin resin. Examples of polyolefin resins include polypropylene, high-density polyethylene, ultra-high molecular weight polyethylene, linear low-density polyethylene, low-density polyethylene, very low-density polyethylene, ultra-ultra-low-density polyethylene, polymethylpentene, ethylene-propylene copolymer, propylene-1-butene random copolymer, propylene-ethylene-1-butene random copolymer, copolymers of propylene and an 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 chlorinated polyolefin resin (a1) may be partially modified with maleic acid.

The chlorinated polyolefin resin (a1) can be used alone or in combination of two or more types, but it is preferable that it contains a chlorinated polypropylene resin.

The degree of chlorination of the polyolefin resin (a1) is preferably 15 to 35%, more preferably 25 to 35%, as this further improves the balance between water dispersibility and oil repellency.

The softening point of the chlorinated polyolefin resin (a1) is preferably 50 to 75°C because it is easy to synthesize, and more preferably 50 to 70°C because it further improves the water dispersibility of the resin.

The acrylic polymer (a2) is obtained by polymerizing a (meth)acrylic monomer and, if necessary, other unsaturated monomers.

Examples of the (meth)acrylic monomer include (meth)acrylates having 3 or less carbon atoms, such as methyl (meth)acrylate, ethyl (meth)acrylate, and propyl (meth)acrylate; (meth)acrylates having a cyclic or linear alkyl group having 4 or more carbon atoms, such as 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; (meth)acrylamide, glycidyl (meth)acrylate, 2-methyl Examples of the (meth)acrylate include (meth)acrylates having functional groups such as aminoethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, γ-methacryloxypropyltrimethoxysilane, benzyl (meth)acrylate, diethylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, and glycerin di(meth)acrylate; (meth)acrylic acid, etc. These (meth)acrylic monomers can be used alone or in combination of two or more, but it is preferable to use the (meth)acrylate having 3 or less carbon atoms in combination with the (meth)acrylate having a cyclic or linear alkyl group having 4 or more carbon atoms in combination. It is also preferable to use a monomer having a carboxyl group, such as the above-mentioned (meth)acrylic acid or an unsaturated carboxylic acid described below.

Examples of the other unsaturated monomers include 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.

The acid value of the acrylic polymer (a2) may be 1 to 15 mg KOH/g, or 3 to 12 mg KOH/g.

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, and "(meth)maleic anhydride" refers to either or both of maleic anhydride and maleic acid.

In the chlorinated polyolefin composite acrylic resin (A), the mass ratio (a1/a2) of the chlorinated polyolefin resin (a1) to the acrylic polymer (a2) is preferably 5/95 to 40/60, and more preferably 5/95 to 30/70, since this further improves the balance between water repellency and oil repellency.

As a method for producing the chlorinated polyolefin composite acrylic resin (A), an underwater polymerization method or an emulsion polymerization method is preferred, as it allows the chlorinated polyolefin composite acrylic resin (A) to be obtained easily.

An example of a method for obtaining the chlorinated polyolefin composite acrylic resin (A) by emulsion polymerization is a method in which the monomer raw materials for the acrylic polymer (a2) are radically polymerized in an aqueous medium in the presence of the chlorinated polyolefin resin (a1), an emulsifier, and a polymerization initiator at a temperature of 50 to 100°C.

Examples of the emulsifier include anionic emulsifiers such as sulfate esters of higher alcohols and their salts, alkylbenzene sulfonates, polyoxyethylene alkylphenyl sulfonates, polyoxyethylene alkyl diphenyl ether sulfonates, sulfate half ester salts of polyoxyethylene alkyl ethers, alkyl diphenyl ether disulfonates, and succinic acid dialkyl ester sulfonates; nonionic emulsifiers such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene diphenyl ethers, polyoxyethylene-polyoxypropylene block copolymers, and acetylenic diols; cationic emulsifiers such as alkyl ammonium salts; and amphoteric emulsifiers such as alkyl(amido)betaines and alkyldimethylamine oxides. These emulsifiers can be used alone or in combination of two or more.

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. 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 serve as the raw materials for the polymer.

Since this further improves the dispersion stability of the chlorinated polyolefin composite acrylic resin (A), it is preferable to adjust the pH with a basic compound and/or an acidic compound. Examples of basic compounds 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 compound include carboxylic acid compounds such as formic acid, acetic acid, propionic acid, and lactic acid; monoesters and 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.

Examples of the aqueous medium (B) include water, water-miscible organic solvents, and mixtures thereof. Examples of water-miscible organic solvents 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 a water-miscible organic solvent may be used, or a water-miscible organic solvent alone may be used. From the standpoints of safety and environmental impact, water alone or a mixture of water and a water-miscible organic solvent is preferred, with water alone being particularly preferred.

It is simple and preferable to use the same aqueous medium (B) as that used when producing the chlorinated 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 chlorinated polyolefin composite acrylic resin (A) and the aqueous medium (B). Preferably, the water- and oil-repellent treatment agent is prepared by diluting with water an aqueous dispersion of the chlorinated polyolefin composite acrylic resin (A) dispersed in the aqueous medium (B), obtained by an emulsion polymerization method or the like.

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

The modified silicone oil (C) includes amino-modified silicone oil (c1) and polyether-modified silicone oil (c2).

The amino-modified silicone oil (c1) is a silicone having an amino group, but silicone oil having an aminopropyl group or an iminopropyl group is preferred, and silicone oil having an iminopropyl group is more preferred.

The functional group equivalent weight of the amino-modified silicone oil (c1) is preferably 1,000 to 7,000.

The polyether-modified silicone oil (c2) is a silicone having a polyether structure, and the HLB of the polyether-modified silicone oil (c2) is preferably 5 to 13.

In the modified silicone oil (C), the mass ratio (c1/c2) of the amino-modified silicone oil (c1) to the polyether-modified silicone oil (c2) is preferably 10/90 to 90/10, and more preferably 20/80 to 80/20.

The content of the amino-modified silicone oil (c1) is preferably 0.5 to 25% by mass, and more preferably 2 to 20% by mass, per 100% by mass of the acrylic polymer (A), as this further improves the balance between water repellency and oil repellency.

The content of the polyether-modified silicone oil (c2) is preferably 0.5 to 25 mass%, more preferably 2 to 20 mass%, relative to 100 parts by mass of the acrylic polymer (A), because this further improves the balance between water repellency and oil repellency.

In addition, the water- and oil-repellent treatment agent for fabrics of the present invention may also contain silicone oils other than the modified silicone oil (C).

The content of the chlorinated polyolefin composite acrylic resin (A) in the water/oil repellent treating agent for fabric of the present invention is preferably less than 10% by mass, more preferably less than 3% by mass, and is preferably 0.05% by mass or more, more preferably 0.1% by mass or more.

The aqueous medium (B) in the water- and oil-repellent treatment agent for fabrics of the present invention is preferably 90% by mass or more, more preferably 97% by mass or more, and is preferably less than 99.95% by mass, more preferably less than 99.9%.

The water- and oil-repellent treatment agent for fabrics of the present invention can also be used in combination with additives such as water repellents, oil repellents, dispersants, curing catalysts, lubricants, fillers, thixotropic agents, tackifiers, waxes, heat stabilizers, light-resistant stabilizers, fluorescent brighteners, foaming agents, pH adjusters, leveling agents, antigelling agents, 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 agents, antistatic agents, moisture permeability enhancers, oil repellents, hollow foams, compounds containing crystal water, flame retardants, water absorbents, moisture absorbents, deodorizers, foam stabilizers, antifoaming agents, antifungal agents, preservatives, anti-algae agents, pigment dispersants, antiblocking agents, and hydrolysis inhibitors, as needed.

The water- and oil-repellent treatment agent for fabrics of the present invention preferably contains a nonionic dispersant such as polyoxyalkylene alkyl ether, as this allows for a more uniform dispersion of each component. These nonionic dispersants can be used alone or in combination of two or more types.

The content of the nonionic dispersant in the water- and oil-repellent treatment agent for fabrics is preferably 0.1 to 10% by mass, and more preferably 0.2 to 5% by mass, per 100 parts by mass of the chlorinated polyolefin composite acrylic resin (A), since this makes the dispersion state of each component more uniform.

Examples of fabrics that can be treated with the water- and oil-repellent treatment agent for fabrics of the present invention include fabrics made of chemical fibers such as nylon, polyester, polyurethane, polypropylene, and rayon, and fabrics made from a blend of two or more of the above chemical fibers.

The present invention will be explained in more detail below with reference to specific examples.

(Synthesis Example 1: Synthesis of Water Dispersion (1) of Chlorinated Polyolefin Composite Acrylic Resin)
Into a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen inlet tube, 138 parts by mass of ion-exchanged water was placed, and the temperature was raised to 70°C. In a separate container, 6 parts by mass of nonionic emulsifier (Dai-ichi Kogyo Seiyaku Co., Ltd. "TDS-200D"), 4 parts by mass of anionic emulsifier (Dai-ichi Kogyo Seiyaku Co., Ltd. "Hitenol LA-12") were dissolved in 120 parts by mass of ion-exchanged water to prepare an emulsifier aqueous solution, to which 34 parts by mass of chlorinated polyolefin resin (a1-1) (Nippon Paper Industries Co., Ltd. "Superchlor 836S"; chlorination degree 27-29%, softening point 60-70 ° C.), 116 parts by mass of methylcyclohexane, 111 parts by mass of cyclohexyl methacrylate, 31 parts by mass of methyl methacrylate, and 1.5 parts by mass of methacrylic acid were added and stirred and emulsified, and then further stirred with a homogenizer at 8000 rpm for 15 min to perform micro-emulsification. This micro-emulsion and a solution of 0.8 parts by mass of ammonium persulfate in 34 parts by mass of ion-exchanged water were added dropwise over 2 hours, and the reaction was carried out at 67-73 ° C. After that, the mixture was held at 70°C for 120 minutes, and then 2 parts by mass of 25% aqueous ammonia and 300 parts by mass of ion-exchanged water were added at the same temperature for neutralization. The solvent was removed at 90°C under reduced pressure (0.080 to 0.095 MPa) and then cooled to obtain an aqueous dispersion of chlorinated polyolefin-composite acrylic resin (1). The properties of this aqueous dispersion were 40% by mass of nonvolatile content, pH 7.4, and viscosity 9 mPa s.

(Synthesis Example 2: Synthesis of Water Dispersion (2) of Chlorinated Polyolefin Composite Acrylic Resin)
A water dispersion (2) of chlorinated polyolefin composite acrylic resin was obtained in the same manner as in Synthesis Example 1, except that the chlorinated polyolefin resin (a1-1) used in Synthesis Example 1 was changed to a chlorinated polyolefin resin (a1-2) (Superchlorine 2030S manufactured by Nippon Paper Industries Co., Ltd.; chlorination degree 29 to 31%, softening point 55 to 65°C). The property values of this water dispersion were 40% by mass of nonvolatile content, pH 7.2, and viscosity 7 mPa s.

(Synthesis Example 3: Synthesis of aqueous dispersion (r1) of polyolefin-composite acrylic resin)
An aqueous dispersion (R1) of polyolefin-composite acrylic resin was obtained in the same manner as in Synthesis Example 1, except that the chlorinated polyolefin resin (a1-1) used in Synthesis Example 1 was changed to a polyolefin resin ("ELMODU S-400" manufactured by Idemitsu Petrochemical Co., Ltd.) The property values of this aqueous dispersion were 40% by mass of nonvolatile content, pH 7.0, and viscosity 11 mPa s.

(Example 1: Production and evaluation of water- and oil-repellent treatment agent for fabric (1))
To 64.1 parts by mass of the aqueous dispersion (1) of the chlorinated polyolefin composite acrylic resin obtained in Synthesis Example 1, 0.15 parts by mass of a dispersant ("Noigen XL-41" manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.; polyoxyalkylene branched decyl ether), 3 parts by mass of amino-modified silicone oil ("DOWSIL SF-8417" manufactured by Dow Toray Industries, Inc.), and 1 part by mass of polyether-modified silicone oil ("DOWSIL SF-8410" manufactured by Dow Toray Industries, Inc.) were added, and then the nonvolatile content was adjusted to 0.6% by mass with ion-exchanged water to obtain a water- and oil-repellent treatment agent (1) for fabrics.

(Example 2: Production and evaluation of water- and oil-repellent treatment agent for fabric (2))
A water- and oil-repellent treatment agent for fabrics (2) having a nonvolatile content of 0.6% by mass was obtained in the same manner as in Example 1, except that the amino-modified silicone oil used in Example 1 was changed from 3 parts by mass to 2 parts by mass, and the polyether-modified silicone oil was changed from 1 part by mass to 2 parts by mass.

(Example 3: Production and evaluation of water- and oil-repellent treatment agent for fabric (3))
A water- and oil-repellent treatment agent for fabrics (3) having a nonvolatile content of 0.6% by mass was obtained in the same manner as in Example 1, except that the amino-modified silicone oil used in Example 1 was changed from 3 parts by mass to 1 part by mass and the polyether-modified silicone oil was changed from 1 part by mass to 3 parts by mass.

(Example 4: Production and evaluation of water- and oil-repellent treatment agent for fabric (4))
A water- and oil-repellent treatment agent for fabrics (4) having a nonvolatile content of 0.6 mass% was obtained in the same manner as in Example 1, except that the aqueous dispersion of chlorinated polyolefin-composite acrylic resin (1) used in Example 1 was changed to the aqueous dispersion of chlorinated polyolefin-composite acrylic resin (2).

(Example 5: Production and evaluation of water- and oil-repellent treatment agent for fabric (5))
A water- and oil-repellent treatment agent for fabrics (5) having a nonvolatile content of 0.6 mass% was obtained in the same manner as in Example 1, except that the aqueous dispersion of chlorinated polyolefin-composite acrylic resin (1) used in Example 1 was changed to the aqueous dispersion of chlorinated polyolefin-composite acrylic resin (2), the amount of amino-modified silicone oil was changed from 3 parts by mass to 1 part by mass, and the amount of polyether-modified silicone oil was changed from 1 part by mass to 3 parts by mass.

(Comparative Example 1: Production and Evaluation of Water- and Oil-Repellent Treatment Agent for Fabric (R1))
To 64.1 parts by mass of the aqueous dispersion of the polyolefin-composite acrylic resin obtained in Synthesis Example 3, 0.15 parts by mass of a dispersant ("Noigen XL-41" manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.; polyoxyalkylene branched decyl ether) and 4 parts by mass of amino-modified silicone oil ("DOWSIL SF-8417" manufactured by Dow Toray Industries, Inc.) were added, and then the nonvolatile content was adjusted to 0.6% by mass with ion-exchanged water, followed by dilution to obtain a water/oil repellent treatment agent for fabric (R1).

[Preparation of test cloth]
The water- and oil-repellent treatment agent for fabrics obtained above was applied to a base fabric (high-density nylon fabric) by a mangle coater using the dip-nip method at a wet coating weight of 15.6 g/ ^m² , and the fabric was dried at 130°C for 5 minutes and then at 160°C for 5 minutes to obtain a test fabric.

[Evaluation of water repellency]
In accordance with Method A of JIS L1092:2009, a water repellency test was conducted in which the test cloth obtained above was stretched so as to be smooth, placed at an angle of 45 degrees, and several drops of water were dropped on it with a dropper to check the state of water on the surface of the test cloth. The water repellency was evaluated according to the following criteria.
G5: Water droplets do not separate, no traces left after wiping G4: Water droplets separate, no traces left after wiping G3: No bleeding when dripping, traces left after wiping G2: Traces left after dripping G1: Completely soaked

[Evaluation of oil repellency]
In accordance with AATCC 118, the test cloth obtained above was placed on a pin-embossed paper wiper, and one drop of n-hexadecane (oil repellency test grade 3) was dropped onto it, and the time until the n-hexadecane penetrated into the fabric was measured. Note that the longer the time until penetration, the higher the oil repellency. In addition, 60 seconds after dropping one drop of n-hexadecane onto the test cloth, the spread of the n-hexadecane along the warp and weft of the test cloth was measured with a ruler, and the area (mm ² ) was calculated using the ellipse area formula. Note that the smaller the area of the spread, the higher the oil repellency.

The formulations and evaluation results for Examples 1 to 5 and Comparative Example 1 above are shown in Table 1.

It was confirmed that the water- and oil-repellent treatment agents for fabrics of the present invention in Examples 1 to 5 can impart water and oil repellency.

Comparative Example 1 is an example in which chlorinated polyolefin resin, an essential raw material of the present invention, was not used, and it was confirmed that the oil repellency was insufficient.

Claims (6)

a chlorinated polyolefin composite acrylic resin (A) having a chlorinated polyolefin resin (a1) and an acrylic polymer (a2);
an aqueous medium (B);
A water- and oil-repellent treatment agent for fabrics containing a modified silicone oil (C),
the modified silicone oil (C) contains an amino-modified silicone oil (c1) and a polyether-modified silicone oil (c2),
The content of the chlorinated polyolefin composite acrylic resin (A) is 0.05% by mass or more and less than 10% by mass,
The water- and oil-repellent treating agent for fabrics, characterized in that the content of the polyether-modified silicone oil (c2) is 0.5 to 25 mass% based on 100 parts by mass of the chlorinated polyolefin-composite acrylic polymer (A) . The water- and oil-repellent treatment agent for fabrics according to claim 1, wherein the mass ratio (a1/a2) of the chlorinated polyolefin resin (a1) to the acrylic polymer (a2) is 5/95 to 40/60. The water- and oil-repellent treatment agent for fabrics according to claim 1, wherein the softening point of the chlorinated polyolefin resin (a1) is 50 to 75°C. The water- and oil-repellent treatment agent for fabrics according to claim 1, wherein the chlorination degree of the chlorinated polyolefin resin (a1) is 15 to 35%. The water- and oil-repellent treatment agent for fabrics according to claim 1, which contains a nonionic dispersant. A fabric treated with the water- and oil-repellent fabric treatment agent according to any one of claims 1 to 5.