Aqueous resin composition, water- and oil-repellent treatment agent, and article

Abstract

Provided is an aqueous resin composition containing a resin (A) that has an α-olefin copolymer (a1) and an acrylic polymer (a2), and an aqueous medium (B), said composition being characterized in that the α-olefin copolymer (a1) contains 4-methyl-1-pentene as an essential starting material, and the mass ratio (a1 / a2) of the α-olefin copolymer (a1) to the acrylic polymer (a2) is 1 / 100 to 40 / 100. The aqueous resin composition can impart excellent water- and oil-repellent properties to various substrates, and thus can be suitably used as a water- and oil-repellent treatment agent.

Description

Aqueous resin composition, water- and oil-repellent treatment agent, and article

[0001] The present invention relates to an aqueous resin composition, a water- and oil-repellent treatment agent, and an article.

[0002] It has been known that the use of fluorine compounds in surface treatments can impart water and oil repellency to surfaces. However, fluorine compounds have environmental concerns and require high-temperature heat treatment during use, so alternatives to fluorine compounds are being investigated.

[0003] In this situation, a water- and oil-repellent treating 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).

[0004] However, although this water- and oil-repellent treatment agent has excellent water repellency, it has the problem of insufficient oil repellency.

[0005] JP 2022-62389 A

[0006] The problem to be solved by the present invention is to provide an aqueous resin composition that has a small environmental impact and is capable of exhibiting excellent water repellency and oil repellency.

[0007] As a result of intensive research into solving the above-mentioned problems, the present inventors have found that an aqueous resin composition containing a resin having a specific α-olefin copolymer and an acrylic polymer, and an aqueous medium, can solve the above-mentioned problems.

[0008] That is, the present invention relates to an aqueous resin composition containing a resin (A) having an α-olefin copolymer (a1) and an acrylic polymer (a2), and an aqueous medium (B), wherein the α-olefin copolymer (a1) contains 4-methyl-1-pentene as an essential raw material, and the mass ratio (a1 / a2) of the α-olefin copolymer (a1) to the acrylic polymer (a2) is 1 / 100 to 40 / 100.

[0009] The aqueous resin composition of the present invention can impart excellent water and oil repellency to various substrates, and therefore can be suitably used as a water and oil repellent treatment agent.

[0010] The aqueous resin composition of the present invention is an aqueous resin composition containing a resin (A) having an α-olefin copolymer (a1) and an acrylic polymer (a2), and an aqueous medium (B), wherein the α-olefin copolymer (a1) contains 4-methyl-1-pentene as an essential raw material, and the mass ratio (a1 / a2) of the α-olefin copolymer (a1) to the acrylic polymer (a2) is 1 / 100 to 40 / 100.

[0011] The α-olefin copolymer (a1) contains 4-methyl-1-pentene as a monomer raw material, which allows the production of an aqueous resin composition having excellent water and oil repellency.

[0012] Examples of the monomer raw materials other than 4-methyl-1-pentene for the α-olefin copolymer (a1) include linear α-olefins such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene; and branched α-olefins such as 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4,4-dimethyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4-ethyl-1-hexene, and 3-ethyl-1-hexene. These monomer raw materials can be used alone or in combination of two or more.

[0013] Furthermore, as the monomer raw material for the α-olefin copolymer (a1), for example, monomers other than α-olefins, such as cyclic olefins, aromatic vinyl compounds, conjugated dienes, and functionalized vinyl compounds, can also be used.

[0014] The 4-methyl-1-pentene content in the monomer raw material of the α-olefin copolymer (a1) is preferably 60 to 95 mol %.

[0015] The glass transition temperature of the α-olefin copolymer (a1) is preferably 20 to 50° C. The glass transition temperature (Tg) in the present invention is a value measured and analyzed using a differential scanning calorimeter in accordance with JIS K 7121:1987.

[0016] The acrylic polymer (a2) can be obtained by polymerizing a (meth)acrylic monomer and, if necessary, other unsaturated monomers.

[0017] 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, dimethylamine, and the like. Examples of the (meth)acrylate include (meth)acrylates having a functional group such as methyl ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, γ-(meth)acryloxypropyl trimethoxysilane, 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.

[0018] Examples of the other unsaturated monomer include styrene compounds such as styrene, α-methylstyrene, paramethylstyrene, and chloromethylstyrene; and unsaturated carboxylic acids such as crotonic acid, maleic acid (anhydride), fumaric acid, citraconic acid (anhydride), mesaconic acid, itaconic acid (anhydride), and aconitic acid (anhydride). These other monomers can be used alone or in combination of two or more.

[0019] The acid value of the acrylic polymer (a2) is preferably from 1 to 25 mgKOH / g, more preferably from 5 to 20 mgKOH / g.

[0020] 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.

[0021] In the resin (A), the mass ratio (a1 / a2) of the α-olefin copolymer (a1) to the acrylic polymer (a2) is preferably 1 / 100 to 40 / 100, and more preferably 10 / 100 to 25 / 100, because this further improves the balance between water repellency and oil repellency.

[0022] The resin (A) is preferably in the form of resin particles dispersed in the aqueous medium (B), and the method for producing the resin (A) is preferably an underwater polymerization method, an emulsion polymerization method, or a suspension polymerization method.

[0023] Examples of methods for obtaining the resin particles by suspension polymerization include a method in which the monomer raw materials of the α-olefin copolymer (a1) and the acrylic polymer (a2), dissolved in an organic solvent, are added to an aqueous medium in which an emulsifier is dissolved, and the resulting suspension is emulsified and dispersed by mechanical shearing force, and heated together with an oil-soluble initiator at a temperature of 50 to 100°C to radically polymerize the monomer raw materials.

[0024] 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.

[0025] 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. It is preferable to use these polymerization initiators in an amount of 0.1 to 10% by mass relative to the total amount of the monomers that serve as raw materials for the polymer.

[0026] Since the dispersion stability of the 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.

[0027] Examples of the acidic compound 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.

[0028] Examples of the aqueous medium (B) include water, organic solvents miscible with water, 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, and using water alone is particularly preferred.

[0029] As the aqueous medium (B), it is convenient and preferable to use the aqueous medium used when producing the resin (A) by underwater polymerization, emulsion polymerization, or suspension polymerization.

[0030] The aqueous resin composition of the present invention is preferably an aqueous dispersion in which the resin (A) is dispersed as resin particles in the aqueous medium (B), and the volume average particle diameter of the resin particles is preferably 100 to 500 nm, more preferably 150 to 250 nm. Here, the volume average particle diameter in the present invention refers to a value measured by a method for determining particle size distribution based on the measurement principle of detecting dynamic scattered light of particles.

[0031] The aqueous dispersion can be easily obtained by the in-water polymerization method, emulsion polymerization method, or suspension polymerization method exemplified as the method for producing the resin (A).

[0032] Furthermore, if necessary, the amount of organic solvent in the aqueous resin composition of the present invention can be reduced by carrying out a solvent removal step.

[0033] The content of the resin (A) in the aqueous resin composition of the present invention is preferably 0.1 to 60% by mass.

[0034] The content of the aqueous medium (B) in the aqueous resin composition of the present invention is preferably 40 to 99.9% by mass.

[0035] Furthermore, the aqueous resin composition of the present invention may optionally contain additives such as water repellents, oil repellents, dispersants, curing catalysts, lubricants, fillers, thixotropy agents, tackifiers, waxes, heat stabilizers, light resistance stabilizers, fluorescent brighteners, and foaming agents, pH adjusters, leveling agents, antigelling agents, dispersion stabilizers, antioxidants, radical scavengers, heat resistance imparting 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 improvers, hollow foams, compounds containing crystal water, flame retardants, water absorbents, moisture absorbents, deodorizers, foam stabilizers, antifoaming agents, preservatives, antialgae agents, pigment dispersants, antiblocking agents, and hydrolysis inhibitors.

[0036] The aqueous resin composition of the present invention is suitably used as a water- and oil-repellent treatment agent, and can impart excellent water and oil repellency to various articles.

[0037] The water- and oil-repellent treatment agent has a weight per unit area of ​​0.1 to 2 g / m after drying. ２ It is preferable to apply the composition to various articles so that the composition becomes as follows.

[0038] The water- and oil-repellent treatment agent can impart water- and oil-repellency to various substrates such as cloth, metal, glass, film, and plastic, but is particularly suitable for use on cloth substrates.

[0039] Examples of the fabric substrate include fabrics made of fibers such as cotton, silk, wool, hemp, polyethylene, nylon, polyester, polyurethane, and rayon.

[0040] The present invention will be described in more detail below with reference to specific examples. The average particle size was measured using Nanotrac UPA-EX150 manufactured by Nikkiso Co., Ltd.

[0041] Example 1: Production and evaluation of aqueous resin composition (1) 101.6 parts by mass of ion-exchanged water was placed in a four-neck flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen inlet tube, and the temperature was raised to 70°C. In a separate container, 4.4 parts by mass of a nonionic emulsifier ("TDS-200D" manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and 9.4 parts by mass of an anionic emulsifier ("Newcol 707SF" manufactured by Nippon Nyukazai Co., Ltd.) were dissolved in 88.4 parts by mass of ion-exchanged water to prepare an aqueous emulsifier solution, and α-olefin copolymer (a1-1) ("Absortomer" manufactured by Mitsui Chemicals, Inc.) was added to the aqueous emulsifier solution. A mixture of 25 parts by mass of methyl methacrylate (EP-1001, 4-methyl-1-pentene: 72 mol%), 100 parts by mass of methylcyclohexane, 75.0 parts by mass of cyclohexyl methacrylate, 23.1 parts by mass of methyl methacrylate, 1.2 parts by mass of methacrylic acid, 0.1 parts by mass of glycidyl methacrylate, and 0.6 parts by mass of a silane coupling agent (KBM503 manufactured by Shin-Etsu Silicones Co., Ltd.) was charged and emulsified by stirring, and then further stirred at 8000 rpm for 15 minutes with a homogenizer to microemulsify the mixture. A solution of this microemulsion with 0.6 parts by mass of peroxide (Perbutyl H manufactured by NOF Corporation) in 12.5 parts by mass of ion-exchanged water and dihydrosulfite was added. A solution of 0.24 parts by weight of sodium formaldehyde and 0.12 parts by weight of sodium erythorbate in 12.5 parts by weight of ion-exchanged water was added dropwise over 3 hours, and the reaction was carried out at 67 to 73°C. After holding the mixture at 70°C for 120 minutes, 1.3 parts by weight of 25% aqueous ammonia and 0.74 parts by weight of ion-exchanged water were added at the same temperature for neutralization. The mixture was then desolvated at 65°C under reduced pressure (0.080 to 0.095 MPa) and cooled to obtain an aqueous resin composition (1) in the form of a water dispersion. This aqueous resin composition (1) had a nonvolatile content of 33% by weight, a pH of 7.1, a viscosity of 6.2 mPa·s, and a volume-average particle size of 172 nm.

[0042] (Example 2: Production and evaluation of aqueous resin composition (2)) An aqueous resin composition (2) which is a water dispersion was obtained in the same manner as in Example 1, except that TDS-200D used in Example 1 was changed to TDS-500F. This aqueous resin composition (2) had a nonvolatile content of 39 mass%, a pH of 7.3, a viscosity of 10.3 mPa s, and a volume average particle diameter of 196 nm.

[0043] (Example 3: Production and evaluation of aqueous resin composition (3)) An aqueous resin composition (3) which is a water dispersion was obtained in the same manner as in Example 1, except that the α-olefin copolymer (a1-1) used in Example 1 was changed to α-olefin copolymer (a1-2) ("Absortomer EP-1013" manufactured by Mitsui Chemicals, Inc., 4-methyl-1-pentene: 85 mol%) and cyclohexyl methacrylate was changed to n-butyl methacrylate. This aqueous resin composition (3) had a nonvolatile content of 31 mass%, a pH of 7.6, a viscosity of 8.2 mPa s, and a volume average particle diameter of 209 nm.

[0044] (Example 4: Production and evaluation of aqueous resin composition (4)) An aqueous resin composition (4) which is a water dispersion was obtained in the same manner as in Example 1, except that the α-olefin copolymer (a1-1) used in Example 1 was changed to the α-olefin copolymer (a1-2) and cyclohexyl methacrylate was changed to t-butyl methacrylate. This aqueous resin composition (4) had a nonvolatile content of 34 mass%, a pH of 7.0, a viscosity of 11.2 mPa s, and a volume average particle diameter of 236 nm.

[0045] (Example 5: Production and evaluation of aqueous resin composition (5)) An aqueous resin composition (5) as a water dispersion was obtained in the same manner as in Example 1, except that 25 parts by mass of the α-olefin copolymer (a1-1) used in Example 1 was changed to 12.5 parts by mass of the α-olefin copolymer (a1-2). This aqueous resin composition (5) had a nonvolatile content of 36% by mass, a pH of 7.8, a viscosity of 21.9 mPa s, and a volume average particle diameter of 183 nm.

[0046] (Example 6: Production and evaluation of aqueous resin composition (6)) An aqueous resin composition (6) which is a water dispersion was obtained in the same manner as in Example 1, except that the 25 parts by mass of the α-olefin copolymer (a1-1) used in Example 1 was changed to 3 parts by mass of the α-olefin copolymer (a1-2). This aqueous resin composition (6) had a nonvolatile content of 36% by mass, a pH of 8.6, a viscosity of 6.2 mPa s, and a volume average particle diameter of 196 nm.

[0047] (Example 7: Production and evaluation of aqueous resin composition (7)) An aqueous resin composition (7) which is a water dispersion was obtained in the same manner as in Example 1, except that the 25 parts by mass of the α-olefin copolymer (a1-1) used in Example 1 was changed to 6 parts by mass of the α-olefin copolymer (a1-2) and the amount of methacrylic acid was changed to 2.8 parts by mass. This aqueous resin composition (7) had a nonvolatile content of 35% by mass, a pH of 7.8, a viscosity of 13.5 mPa s, and a volume average particle diameter of 208 nm.

[0048] Comparative Example 1: Production and Evaluation of Aqueous Resin Composition (R1) An aqueous resin composition (R1) that is a water dispersion was obtained in the same manner as in Example 1, except that the α-olefin copolymer (a1-1) used in Example 1 was changed to polypropylene ("ELMODU S-400" manufactured by Idemitsu Petrochemical Co., Ltd.) The aqueous resin composition (R1) had a nonvolatile content of 40% by mass, a pH of 6.5, a viscosity of 11 mPa s, and a volume average particle diameter of 177 nm.

[0049] [Preparation of Test Sample] 0.5 g of the resin composition obtained above was dropped onto a 3 cm square alkali-free glass plate, treated at 2000 rpm for 20 seconds using a spin coater (MS-B150) manufactured by Mikasa Co., Ltd., and then dried in a dryer at 130°C for 10 minutes to obtain a test sample.

[0050] [Evaluation of Water Repellency] The water contact angle was measured by the sessile drop method using a contact angle meter (DMo-701 type) manufactured by Kyowa Interface Science Co., Ltd. Ion-exchanged water was used as the measurement solvent, and the measurement was carried out indoors at 20°C. The water repellency was evaluated based on the average value of the data measured five times. ◎: 105° or more ○: 95° or more and less than 105° △: 85° or more and less than 95° ×: Less than 85°

[0051] [Evaluation of oil repellency] The hexadecane contact angle was measured by the sessile drop method using a contact angle meter (DMo-701 type) manufactured by Kyowa Interface Science Co., Ltd. The measurement solvent used was hexadecane (special grade) manufactured by Kanto Chemical Co., Ltd. The measurement was carried out indoors at 20°C, and the oil repellency was evaluated based on the average value of the data measured five times. ◎: 20° or more ○: 15° or more and less than 20° △: 10° or more and less than 15° ×: Less than 10°

[0052] The resin compositions and evaluation results of Examples 1 to 7 and Comparative Example 1 are shown in Tables 1 and 2.

[0053]

[0054]

[0055] The abbreviations in the table are as follows: CHMA: cyclohexyl methacrylate MMA: methyl methacrylate MAA: methacrylic acid GMA: glycidyl methacrylate KBM503: 3-methacryloxypropyltrimethoxysilane

[0056] It was confirmed that the aqueous resin compositions of the present invention in Examples 1 to 7 were able to impart water repellency and oil repellency to the substrate.

[0057] On the other hand, Comparative Example 1 is an example in which the α-olefin copolymer (a1), which is an essential raw material of the present invention, was not used, and it was confirmed that the oil repellency was insufficient.

Claims

1. An aqueous resin composition comprising a resin (A) having an α-olefin copolymer (a1) and an acrylic polymer (a2), and an aqueous medium (B), wherein the α-olefin copolymer (a1) is made from 4-methyl-1-pentene as an essential raw material, and the mass ratio (a1 / a2) of the α-olefin copolymer (a1) to the acrylic polymer (a2) is 1 / 100 to 40 / 100.

2. The aqueous resin composition according to claim 1, wherein the α-olefin copolymer (a1) has a glass transition temperature of 20 to 50°C.

3. A water- and oil-repellent treatment agent containing the aqueous resin composition according to claim 1 or 2.

4. An article treated with the water- and oil-repellent treatment agent according to claim 3.

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