JP6481879B2 - Water repellent agent for fabric and fabric - Google Patents

Description

  The present invention relates to a water repellent treatment agent that imparts water repellency to a fabric.

  2. Description of the Related Art Conventionally, a fiber product in which water repellency is imparted to its surface by treating a fluorine-based water repellent with a fiber product or the like is known. However, since fluorine compounds are concerned about environmental burdens and require heat treatment at high temperature during use, a treatment agent not containing fluorine compounds has been studied.

  Among these, a non-fluoropolymer having a repeating unit derived from a long-chain alkyl (meth) acrylate monomer, a surfactant containing a surfactant compound having one or both of an amide group and an amino group, and water A surface treatment agent containing a liquid medium containing a liquid has been proposed (for example, see Patent Document 1).

  However, the fiber product obtained using the surface treating agent described in Patent Document 1 has a problem that the washing resistance is insufficient.

JP2015-120893A

  The problem to be solved by the present invention is a water-repellent treatment agent for fabrics that does not contain a fluorine compound that is likely to be an environmental load and can maintain the same excellent water repellency as before the washing treatment even after the washing treatment. Is to provide.

  As a result of studies by the present inventors to solve the above-mentioned problems, a water repellent treatment agent for fabrics containing an acrylic resin containing a specific monomer as an essential raw material, a basic compound, and an aqueous medium is the above-mentioned problem. It was found that can be solved.

  That is, the present invention relates to an acrylic resin (A) having (meth) acrylic acid ester (a1) and (maleic anhydride) (a2) having an alkyl group having 6 to 24 carbon atoms as an essential raw material, and basic. The present invention relates to a water-repellent treatment agent for fabrics, comprising a compound (B) and an aqueous medium (C).

  Since the water-repellent treatment agent for fabrics of the present invention can impart excellent water repellency, it is suitable for water-repellent treatment agents for fabrics composed of fibers such as cotton, silk, wool, hemp, nylon, polyester, polyurethane, and rayon. Can be used.

  The water repellent agent for fabrics of the present invention is an acrylic resin (A) containing (meth) acrylic acid ester (a1) and (anhydrous) maleic acid (a2) having an alkyl group having 6 to 24 carbon atoms as essential raw materials. ), A basic compound (B), and an aqueous medium (C).

  In the present invention, the notation of “(meth) acrylic acid ester” represents one or both of “acrylic acid ester” and “methacrylic acid ester”, and the notation of “(anhydrous) maleic acid”. Represents one or both of “maleic acid” and “maleic anhydride”. In addition, the alkyl group in the present invention includes a cycloalkyl group.

  First, the acrylic resin (A) will be described. The acrylic resin (A) contains (meth) acrylic acid ester (a1) and (anhydrous) maleic acid (a2) having an alkyl group having 6 to 24 carbon atoms as essential raw materials.

  Examples of the (meth) acrylic acid ester (a1) having an alkyl group having 6 to 24 carbon atoms include cyclohexyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isobornyl (meth) ) Acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, etc., and (meth) acrylic acid having an alkyl group having 6 to 14 carbon atoms among them because of improved washing resistance. Esters are preferred. In addition, these (meth) acrylic acid alkyl esters (a1) can be used alone or in combination of two or more.

  Moreover, as a raw material of the said acrylic resin (A), in addition to the said (meth) acrylic acid ester (a1) and the said (anhydrous) maleic acid (a2), another monomer (a3) as needed is included. Can be used.

  Examples of the other monomer (a3) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, (meth) acrylamide, and glycidyl (meth) acrylate. 2-methylaminoethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, tetrahydrofurfuryl Monomers having a functional group such as (meth) acrylate, γ-methacryloxypropyltrimethoxysilane, vinyltriethoxysilane, benzyl (meth) acrylate, diethylene glycol di (meth) acrylate, di (meth) acrylic acid , 4-butanediol, di (meth) acrylic acid-1,6-hexanediol, trimethylolpropane tri (meth) acrylate, glycerin di (meth) acrylate, α-methylstyrene, paramethylstyrene, chloromethylstyrene , (Meth) acrylic acid, fumaric acid, (anhydrous) citraconic acid, mesaconic acid, (anhydrous) itaconic acid, (anhydrous) aconitic acid and the like. These other monomers (a3) can be used alone or in combination of two or more.

  The amount of the (meth) acrylic acid ester (a1) used is preferably in the range of 45 to 95% by mass in the monomer component that is the raw material of the acrylic resin (A) because the washing resistance is further improved. The range of 55-85 mass% is more preferable.

  The amount of the (anhydrous) maleic acid (a2) used is preferably in the range of 5 to 55% by mass in the monomer component that is the raw material of the acrylic resin (A) because the washing resistance is further improved. The range of 15-45 mass% is more preferable.

  In addition, the usage-amount of the other monomer (a3) used as needed is said (meth) acrylic acid ester (a1) from the total 100 mass% of the monomer component which is the raw material of the said acrylic resin (A). ) And (anhydrous) maleic acid (a2), and the remainder is removed.

  Further, the weight average molecular weight of the acrylic resin (A) is in the range of 5,000 to 150,000, more preferably in the range of 10,000 to 100,000, since the washing resistance is further improved. Here, the weight average molecular weight is a value in terms of polystyrene based on gel permeation chromatography (hereinafter abbreviated as “GPC”) measurement.

  The acid value of the acrylic resin (A) is preferably in the range of 50 to 630, more preferably in the range of 170 to 520, since the washing resistance is further improved. In addition, in this invention, an acid value is an acid value calculated | required by calculation from the monomer composition which is a raw material.

  The acrylic resin (A) includes, for example, the (meth) acrylic acid ester (a1) and the (anhydrous) maleic acid (a2), and if necessary, other monomers (a3) in an organic solvent. It can be produced by radical polymerization at a temperature of 60 to 140 ° C. in the presence of a polymerization initiator. The organic solvent may be removed by a solvent removal step after radical polymerization.

  Examples of the organic solvent include aromatic solvents such as toluene and xylene; alicyclic solvents such as cyclohexanone; ester solvents such as butyl acetate and ethyl acetate; isobutanol, normal butanol, isopropyl alcohol, sorbitol, and propylene. Cellosolve solvents such as glycol monomethyl ether acetate; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone can be used. These solvents 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), azobiscyanovaleric acid; tert-butylperoxy Pivalate, tert-butylperoxybenzoate, tert-butylperoxy-2-ethylhexanoate, di-tert-butyl peroxide, di-tert-butyl hydroperoxide, cumene hydroperoxide, benzoyl peroxide, tert -Organic peroxides such as butyl hydroperoxide; inorganic peroxides such as hydrogen peroxide, ammonium persulfate, potassium persulfate, and sodium persulfate. These polymer initiators can be used alone or in combination of two or more. Moreover, it is preferable to use the said polymerization initiator within the range of 0.1-10 mass% with respect to the sum total of the monomer used as the raw material of the said acrylic resin (A).

  Examples of the basic compound (B) include organic amines such as methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, 2-aminoethanol, 2-dimethylaminoethanol; ammonia, sodium hydroxide, potassium hydroxide Inorganic basic compounds such as tetramethylammonium hydroxide, tetra-n-butylammonium hydroxide, and quaternary ammonium hydroxide of trimethylbenzylammonium hydroxide. Of these, organic amines and ammonia (ammonia water may be used) are preferably used. These basic compounds can be used alone or in combination of two or more.

  Examples of the aqueous medium (C) include water, organic solvents miscible with water, and mixtures thereof. Examples of the organic solvent 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, only water may be used, a mixture of water and an organic solvent miscible with water may be used, or only an organic solvent miscible with water may be used. From the viewpoint of safety and load on the environment, water alone or a mixture of water and an organic solvent miscible with water is preferable, and it is particularly preferable to use only water.

  The water-repellent treatment agent for a fabric of the present invention contains the acrylic resin (A), the basic compound (B), and the aqueous medium (C), and the acrylic obtained by the above-described method. It is preferable that the resin (A) is dissolved or dispersed in the aqueous medium (C).

  As a method of dissolving or dispersing the acrylic resin (A) in the aqueous medium (C), since the washing resistance is further improved, the acid group of the acrylic resin (A) is changed to the basic compound (B). A method of mixing the neutralized solution with the aqueous medium (C) is preferable.

  Further, the water repellent agent for fabrics of the present invention may contain a water repellent, a curing catalyst, a lubricant, a filler, a thixotropic agent, a tackifier, a wax, a heat stabilizer, a light-resistant stabilizer, a fluorescent agent as necessary. Additives such as brighteners, foaming agents, pH adjusters, leveling agents, anti-gelling agents, dispersion stabilizers, antioxidants, radical scavengers, heat resistance imparting agents, inorganic fillers, organic fillers, plasticizers , Reinforcing agent, catalyst, antibacterial agent, antifungal agent, rust preventive agent, thermoplastic resin, thermosetting resin, pigment, dye, conductivity imparting agent, antistatic agent, moisture permeability improver, oil repellent agent, hollow foam , Water-containing compound, flame retardant, water-absorbing agent, moisture-absorbing agent, deodorant, foam stabilizer, anti-foaming agent, antifungal agent, antiseptic, algal inhibitor, pigment dispersant, anti-blocking agent, hydrolysis inhibitor Etc. can be used together.

  As the water repellent agent, silicone oils such as dimethyl silicone oil, methyl phenyl silicone oil, methyl hydrogen silicone oil, and modified silicone oil are preferable because they can improve water repellency without containing a halogen compound.

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

  Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. In addition, the weight average molecular weight of an acrylic resin is measured on the following GPC measurement conditions.

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

(Monodispersed 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: Synthesis and evaluation of water repellent agent (1) for fabric)
A 4-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen blowing tube was charged with 95 parts by mass of n-butyl acetate and heated to 120 ° C., to which 61.5 parts by mass of maleic anhydride and lauryl methacrylate 184 were added. A dissolved mixture of 0.5 part by mass, 75 parts by mass of n-butyl acetate and 3 parts by mass of t-butyl peroxybenzoate was added dropwise over 2 hours, and the reaction was performed at 120 to 125 ° C. Then, after hold | maintaining at 120 degreeC for 2 hours, temperature was lowered | hung to 90 degreeC, 25 mass% ammonia water 85.3 mass part and ion-exchange water 1700 mass part were added, and neutralization and water dissolution were performed. The temperature was kept at 90 ° C., and n-butyl acetate was removed from the solvent while reducing the pressure in the flask (0.080 to 0.095 MPa). After removing the solvent, the mixture was cooled and ion exchanged water was added to obtain a water repellent (1) for fabric having a nonvolatile content of 18% by mass. The weight average molecular weight of the acrylic resin (A-1) in the water repellent agent (1) for fabric was 50,000.

(Example 2: Synthesis and evaluation of water repellent agent (2) for fabric)
A 4-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen blowing tube was charged with 95 parts by mass of n-butyl acetate, and the temperature was raised to 120 ° C., to which 86.1 parts by mass of maleic anhydride, cyclohexyl methacrylate 159 .9 parts by mass, a dissolved mixture of n-butyl acetate 75 parts by mass and t-butyl peroxybenzoate 3 parts by mass was added dropwise over 2 hours, and the reaction was performed at 120 to 125 ° C. Then, after hold | maintaining at 120 degreeC for 2 hours, temperature was lowered | hung to 90 degreeC, 25 mass% ammonia water 119.4 mass parts and 1700 mass parts of ion-exchange water were added, and neutralization and water dissolution were performed. The temperature was kept at 90 ° C., and n-butyl acetate was removed from the solvent while reducing the pressure in the flask (0.080 to 0.095 MPa). After removing the solvent, the mixture was cooled and ion-exchanged water was added to obtain a water repellent (2) for fabric having a nonvolatile content of 18% by mass. The weight average molecular weight of the acrylic resin (A-2) in the water repellent agent (2) for this fabric was 55,000.

(Example 3: Preparation and evaluation of water repellent agent (3) for fabric)
18 parts by mass of silicone oil ("TSF451-100" manufactured by Momentive Performance Materials Japan) is added to 100 parts by mass of the water-repellent agent for fabric (2) obtained above, and stirred until uniform. A water repellent agent (3) for fabric was obtained.

(Comparative Example 1: Synthesis and evaluation of water repellent agent (R1) for fabric)
In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen blowing tube, 115.2 parts by mass of stearyl acrylate, 240 parts by mass of ion-exchanged water, 33 parts by mass of tripropylene glycol, dimethylaminopropylamide stearate 6. 08 parts by mass, polyoxyethylene isotridecyl ether (oxyethylene repeating unit number 18) 5.43 parts by mass, polyoxyethylene isotridecyl ether (oxyethylene repeating unit number 3) 1.71 parts by mass, acetic acid 2 .4 parts by mass was charged and emulsified and dispersed with ultrasound at 60 ° C. for 15 minutes with stirring. After replacing the inside of the reaction flask with nitrogen, a solution of 0.24 parts by mass of lauryl mercaptan, 0.48 parts by mass of 2,2-azobis (2-amidinopropane) dihydrochloride, and 9 parts by mass of water was added at 60 ° C. By reacting for 5 hours, a water repellent (R1) for fabric having a nonvolatile content of 30% by mass was obtained.

(Comparative Example 2: Synthesis and evaluation of water repellent agent (R2) for fabric)
A 4-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen blowing tube was charged with 95 parts by mass of n-butyl acetate and heated to 120 ° C., to which 98.4 parts by mass of maleic anhydride, n-butyl A dissolved mixture of 147.6 parts by mass of methacrylate, 75 parts by mass of n-butyl acetate and 3 parts by mass of t-butyl peroxybenzoate was added dropwise over 2 hours, and the reaction was performed at 120 to 125 ° C. Then, after hold | maintaining at 120 degreeC for 2 hours, temperature was lowered | hung to 90 degreeC, 25 mass% ammonia water 136.5 mass parts and ion-exchange water 1700 mass parts were added, and neutralization and water dissolution were performed. The temperature was kept at 90 ° C., and n-butyl acetate was removed from the solvent while reducing the pressure in the flask (0.080 to 0.095 MPa). After removing the solvent, the mixture was cooled and ion-exchanged water was added to obtain a water repellent (1) for fabric having a nonvolatile content of 25% by mass. The weight average molecular weight of the acrylic resin (RA-2) in the water repellent agent for fabric (R2) was 50,000.

[Production of water repellent base material]
The water repellent agent for fabric obtained above is diluted with ion-exchanged water to a non-volatile content of 1% and dried on a base fabric (T / C) with a mangle coating machine to a basis weight of 0.5 g / m ^2. And then dried at 120 ° C. for 5 minutes and further at 150 ° C. for 5 minutes to obtain a water-repellent treated substrate.

[Evaluation of water repellency (washing resistance)]
The water-repellent treated substrate obtained above was repeatedly subjected to washing treatment 30 times in accordance with JIS L1092 6.2.1C method. The water repellency treatment (spray test) of JIS L1092 was performed on each water repellent treatment substrate before and after the washing treatment, and the water repellency (washing resistance) was evaluated according to the following criteria.
◎: Grade 4 or higher ○: Grade 3 △: Grade 2 ×: Grade 1

  Table 1 shows the compositions and evaluation results of Examples 1 to 3 and Comparative Examples 1 and 2 described above.

  It was confirmed that the water repellent agent for fabrics of Examples 1 to 3 of the present invention can impart excellent water repellency even after washing.

  On the other hand, although the comparative example 1 is an example which does not contain (anhydrous) maleic acid in the monomer component which is a raw material of an acrylic resin, it was confirmed that the water repellency at the initial stage and after washing is insufficient. .

  Comparative Example 2 is an example that does not contain a (meth) acrylic acid ester having an alkyl group having 6 to 24 carbon atoms in the monomer component that is a raw material of the acrylic resin, but has a water repellency after washing. It was confirmed that it was insufficient.

Claims (4)

  An acrylic resin (A) using as an essential raw material (meth) acrylic acid ester (a1) and (anhydrous) maleic acid (a2) having an alkyl group having 6 to 24 carbon atoms, a basic compound (B), A water repellent agent for fabrics, comprising an aqueous medium (C).   The (meth) acrylic acid ester (a1) in the monomer component that is a raw material of the acrylic resin (A) is in the range of 45 to 95% by mass, and the (anhydrous) maleic acid (a2) is in the range of 5 to 55. The water repellent agent for fabrics according to claim 1, which is in a range of mass%.   The water-repellent agent for fabric according to claim 1 or 2, wherein the acrylic resin (A) has a weight average molecular weight of 5,000 to 150,000.   A fabric treated with the water-repellent agent for fabric according to any one of claims 1 to 3.