Aqueous resin compositions, water-repellent and oil-repellent treatment agents, and articles

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

Technical Field

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

Background Art

[0002] Conventionally, it has been known that by using a fluorine compound for surface treatment, water and oil repellency is imparted to the surface. However, fluorine compounds have concerns about environmental impact, and also require heat treatment at high temperatures during use, etc., so alternatives to fluorine are being considered.

[0003] Under such circumstances, a water and oil repellent treatment agent for fabric containing a polyolefin resin and a polyolefin composite acrylic resin having an acrylic polymer, and an aqueous medium has been proposed (see, for example, Patent Document 1).

[0004] However, this water and oil repellent treatment agent has a problem that although it has excellent water repellency, its oil repellency is insufficient.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

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

Means for Solving the Problems

[0007] [[ID=四十九]] As a result of diligent research to solve the above 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 problems.

[0008] In other words, 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) uses 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. [Effects of the Invention]

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

[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) uses 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, thereby yielding an aqueous resin composition with excellent water-repellent and oil-repellent properties.

[0012] Examples of 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, 4,4-ethyl-1-hexene, and 3-ethyl-1-hexene. These monomer raw materials can be used individually or in combination of two or more.

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

[0014] The amount of 4-methyl-1-pentene 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 this invention is a value measured and analyzed using a differential scanning calorimetry analyzer in accordance with JIS K 7121:1987.

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

[0017] Examples of the (meth)acrylic monomers include (meth)acrylates having 3 or fewer carbon atoms, such as methyl (meth)acrylate, ethyl (meth)acrylate, and propyl (meth)acrylate; (meth)acrylates having 4 or more carbon atoms and possessing cyclic or linear alkyl groups, 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, and dimethylamide. Examples include (meth)acrylates having functional groups such as noethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, γ-(meth)acryloxypropyl trimethooxylan, 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; and (meth)acrylic acid. These (meth)acrylic monomers can be used individually or in combination of two or more, but it is preferable to use in combination (meth)acrylates having 3 or fewer carbon atoms and (meth)acrylates having cyclic or linear alkyl groups with 4 or more carbon atoms. Furthermore, it is preferable to use monomers having a carboxyl group, such as (meth)acrylic acid or unsaturated carboxylic acids described later.

[0018] Examples of the other unsaturated monomers include styrene compounds such as styrene, α-methylstyrene, paramethylstyrene, and chloromethylstyrene; unsaturated carboxylic acids such as crotonic acid, (anhydrous) maleic acid, fumaric acid, (anhydrous) citraconic acid, mesaconic acid, (anhydrous) itaconic acid, and (anhydrous) aconitic acid. 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 1 to 25 mgKOH / g, more preferably 5 to 20 mgKOH / g.

[0020] In the present invention, “(meth)acrylate” refers to one or both of methacrylate and acrylate, “(meth)acrylic acid” refers to one or both of methacrylic acid and acrylic acid, and “(anhydrous) maleic acid” refers to one 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, more preferably 10 / 100 to 25 / 100, because the balance of water repellency and oil repellency is further improved.

[0022] The resin (A) is preferably resin particles dispersed in the aqueous medium (B), and as its production method, an aqueous polymerization method, an emulsion polymerization method or a suspension polymerization method is preferable.

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

[0024] Examples of the emulsifier include anionic emulsifiers such as sulfuric acid esters of higher alcohols and their salts, alkylbenzene sulfonates, polyoxyethylene alkyl phenyl sulfonates, polyoxyethylene alkyl diphenyl ether sulfonates, sulfuric acid half ester salts of polyoxyethylene alkyl ethers, alkyl diphenyl ether disulfonates, and dialkyl ester sulfonates of succinic acid; nonionic emulsifiers such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene diphenyl ethers, polyoxyethylene - polyoxypropylene block copolymers, and acetylene diol - based emulsifiers; cationic emulsifiers such as alkyl ammonium salts; and zwitterionic emulsifiers such as alkyl (amide) betaines and alkyl dimethyl amine 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 peroxy pivalate, tert - butyl peroxy benzoate, tert - butyl peroxy - 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. Further, these polymerization initiators are preferably used in the range of 0.1 to 10% by mass based on the total of the monomers that are the raw materials of the polymer.

[0026] To further improve the dispersion stability of the 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 individually or in combination of two or more.

[0027] Examples of the aforementioned acidic compounds include carboxylic acid compounds such as formic acid, acetic acid, propionic acid, or 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 individually or in combination of two or more.

[0028] Examples of the aqueous medium (B) include water, a water-miscible organic solvent, 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, a mixture of water and a water-miscible organic solvent may be used, or a water-miscible organic solvent may be used alone. From the viewpoint of safety and environmental impact, water alone or a mixture of water and a water-miscible organic solvent is preferred, and the use of water alone is particularly preferred.

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

[0030] The aqueous resin composition of the present invention preferably is 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, and more preferably 150 to 250 nm. Here, the volume average particle diameter in the present invention refers to the value measured by a method that determines the particle size distribution using a measurement principle that detects the dynamic scattered light of particles.

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

[0032] Furthermore, the amount of organic solvent in the aqueous resin composition of the present invention can be reduced by performing a solvent removal process as needed.

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

[0034] 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, thixotropic agents, tackifiers, waxes, heat stabilizers, light stabilizers, fluorescent whitening agents, foaming agents, pH adjusters, leveling agents, gelation inhibitors, dispersion stabilizers, antioxidants, radical scavengers, heat resistance imparters, inorganic fillers, organic fillers, plasticizers, reinforcing agents, catalysts, antibacterial agents, antifungal agents, rust inhibitors, thermoplastic resins, thermosetting resins, pigments, dyes, conductivity imparters, antistatic agents, moisture permeability enhancers, hollow foams, water-containing compounds, flame retardants, water absorbents, moisture absorbers, deodorants, foam stabilizers, defoamers, preservatives, algaecides, pigment dispersants, blocking inhibitors, hydrolysis inhibitors, etc.

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

[0037] The aforementioned water-repellent and oil-repellent treatment agent has a basis weight of 0.1 to 2 g / m² after drying. 2 It is preferable to apply it to various articles in such a manner.

[0038] The aforementioned water- and oil-repellent treatment agent can impart water- and oil-repellent properties 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 base material include textiles made from fibers such as cotton, silk, wool, hemp, polyethylene, nylon, polyester, polyurethane, and rayon. [Examples]

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

[0041] (Example 1: Production and evaluation of aqueous resin composition (1)) 101.6 parts by mass of deionized water were placed in a four-necked flask equipped with a stirrer, reflux condenser, thermometer, and nitrogen blowing tube, and the temperature was raised to 70°C. In a separate container, 4.4 parts by mass of nonionic emulsifier (Daiichi Kogyo Seiyaku Co., Ltd. "TDS-200D") and 9.4 parts by mass of anionic emulsifier (Nippon Emulsifier Co., Ltd. "Newcol 707SF") were dissolved in 88.4 parts by mass of deionized water to prepare an emulsifier aqueous solution, to which α-olefin copolymer (a1-1) (Mitsui Chemicals, Inc. "Absortmer") was added. A mixture of 25 parts by mass of 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 silane coupling agent (KBM503, manufactured by Shin-Etsu Silicone Co., Ltd.) was charged and stirred to emulsify. This mixture was then further heated in a homogenizer at 8000 rpm for 15 minutes to achieve micro-emulsification. This micro-emulsified product was then mixed with a solution of 0.6 parts by mass of peroxide (Perbutyl H, manufactured by NOF Corporation) dissolved in 12.5 parts by mass of ion-exchanged water, and hyposulfite. 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 deionized water was added dropwise over 3 hours, and the reaction was carried out at 67-73°C. After holding at 70°C for 120 minutes, 1.3 parts by weight of 25% aqueous ammonia and 0.74 parts by weight of deionized water were added at the same temperature to neutralize the mixture. This mixture was desolvated under reduced pressure (0.080-0.095 MPa) at 65°C, and then cooled to obtain an aqueous resin composition (1), which is an aqueous dispersion. This aqueous resin composition (1) had a non-volatile 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 an aqueous dispersion, was obtained in the same manner as in Example 1, except that TDS-200D used in Example 1 was replaced with TDS-500F. This aqueous resin composition (2) had a non-volatile content of 39% by mass, a pH of 7.3, a viscosity of 10.3 mPa·s, and a volume-average particle size of 196 nm.

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

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

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

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

[0047] (Example 7: Production and evaluation of aqueous resin composition (7)) An aqueous resin composition (7), which is an aqueous dispersion, was obtained in the same manner as in Example 1, except that 25 parts by mass of α-olefin copolymer (a1-1) used in Example 1 was replaced with 6 parts by mass of 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 non-volatile content of 35% by mass, a pH of 7.8, a viscosity of 13.5 mPa·s, and a volume-average particle size of 208 nm.

[0048] (Comparative Example 1: Production and Evaluation of Aqueous Resin Composition (R1)) An aqueous resin composition (R1), which is an aqueous dispersion, was obtained in the same manner as in Example 1, except that the α-olefin copolymer (a1-1) used in Example 1 was replaced with polypropylene (Elmodu S-400, manufactured by Idemitsu Petrochemical Co., Ltd.). This aqueous resin composition (R1) had a non-volatile content of 40% by mass, a pH of 6.5, a viscosity of 11 mPa·s, and a volume-average particle size of 177 nm.

[0049] [Preparation of test samples] A test sample was obtained by dropping 0.5 g of the resin composition obtained above onto a 3 cm square alkali-free glass plate, processing it at 2000 rpm for 20 seconds using a Mikasa Corporation spin coater (MS-B150), and then drying it in a 130°C dryer for 10 minutes.

[0050] [Evaluation of water repellency] Water contact angles were measured using the droplet method with a contact angle meter (DMo-701 model) manufactured by Kyowa Interface Science Co., Ltd. Deionized water was used as the measurement solvent, and the measurements were performed in a room at 20°C. The water repellency was evaluated using the average value of five measurements. ◎: 105° or higher ○: 95° or more and less than 105° △: 85° or more and less than 95° ×: Less than 85°

[0051] [Evaluation of oil repellency] The contact angle of hexadecane was measured using the droplet method with a contact angle meter (DMo-701) manufactured by Kyowa Interface Science Co., Ltd. The measurement solvent used was hexadecane (special grade) manufactured by Kanto Chemical Co., Ltd., and the measurements were performed in a room at 20°C. The oil repellency was evaluated using the average value of five measurements. ◎: 20° or higher ○: 15° or more and less than 20° △: 10° or more and less than 15° ×: Less than 10°

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

[0053] [Table 1]

[0054] [Table 2]

[0055] The abbreviations used in the table are as follows: CHMA: Cyclohexyl methacrylate MMA: Methyl methacrylate MAA: Methacrylic acid GMA: Glycidyl methacrylate KBM503: 3-Methacryloxypropyltrimethoxysilane

[0056] The aqueous resin compositions of the present invention described in Examples 1 to 7 were confirmed to be able to impart water-repellent and oil-repellent properties 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 for water-repellent and oil-repellent treatment agents, comprising a resin (A) having an α-olefin copolymer (a1) and an acrylic polymer (a2), and an aqueous medium (B), The α-olefin copolymer (a1) uses 4-methyl-1-pentene as an essential raw material. The proportion of 4-methyl-1-pentene in the monomer raw material of the α-olefin copolymer (a1) is 60 to 95 mol%, The acrylic polymer (a2) has constituent units derived from at least one compound selected from the group consisting of n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, cyclohexyl (meth)acrylate, and hexyl (meth)acrylate. An aqueous resin composition for water-repellent and oil-repellent treatment agents, characterized in that 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 for water-repellent and oil-repellent treatment agents according to claim 1, wherein the glass transition temperature of the α-olefin copolymer (a1) is 20 to 50°C.

3. The aqueous resin composition for water-repellent and oil-repellent treatment according to claim 1 or 2, wherein the resin (A) in the aqueous resin composition for water-repellent and oil-repellent treatment is 0.1 to 60% by mass.

4. An article treated with the aqueous resin composition for water-repellent and oil-repellent treatment agents described in claim 1 or 2.

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