JP2022017964A - Paper coating agent - Google Patents

Abstract

To provide a new paper coating agent which can efficiently impart excellent oil resistance and water resistance to paper.SOLUTION: An aqueous composition contains (A) a copolymer containing an α,β-unsaturated carboxylic acid or its ester as a constitutional unit, and (B) a long chain fatty acid ester.SELECTED DRAWING: None

Description

The present disclosure relates to a paper coating agent, a paper to which the paper-taing agent is applied, a product using the paper, and the like.

Conventionally, in order to impart oil resistance and water resistance to paper (particularly food packaging paper), for example, aluminum foil, film or the like has been coated or laminated on one or both sides of paperboard. However, these conventional methods have poor work efficiency because they require coating over multiple layers and require a binder, a sealant, or the like for laminating.

For example, in order to develop oil resistance, a fluorine-based oil-resistant agent, particularly a perfluorofluorine-based oil-resistant agent, is used. However, perfluorofluorine-based compounds generate perfluorooctanoic acid and perfluorosulfonic acid by heat treatment, so there is a concern about safety. Therefore, fluorine-based resins with improved safety are being developed, but their oil resistance is insufficient and their safety remains uncertain. Further, since the fluorine-based compound repels printing ink due to its high oil resistance, there is a problem that white spots occur when gravure printing or the like is performed on the treated paper.

Further, for example, as a non-fluorine-based oil-resistant agent, for example, a polyvinyl alcohol-based resin is widely used. Polyvinyl alcohol is a hydrophilic resin and forms a stubborn film, so it is known that excellent oil resistance can be obtained by preventing oil from penetrating. Acrylic and urethane emulsions are also known to have excellent oil resistance.

However, the polyvinyl alcohol-based resin tends to foam during coating, and therefore tends to generate pinholes. In order to suppress the occurrence of pinholes on the coated surface, it is necessary to defoam by devising equipment and adding a defoaming agent. In addition, since the polyvinyl alcohol-based resin has a small contact angle with oil, it has the disadvantages that the oil adhering to the film surface spreads and the appearance is poor, and that it has poor water resistance and is difficult to use in a high humidity environment. .. Further, while acrylic and urethane are excellent in oil resistance, they are inferior in water resistance, and there is a concern that they absorb water or dissolve in water.

Patent No. 29704943 Japanese Unexamined Patent Publication No. 7-60905

The present inventors have proceeded with research in order to develop a new paper coating agent capable of efficiently imparting excellent oil resistance and water resistance to paper.

The present inventors have excellent oil resistance and an aqueous composition containing (A) a copolymer containing α, β-unsaturated carboxylic acid or an ester thereof as a constituent unit, and (B) a long-chain fatty acid ester. We have found that it may be useful as a coating agent that imparts water resistance to paper, and have made further improvements.

The present disclosure includes, for example, the subjects described in the following sections.
Item 1.
An aqueous composition containing (A) a copolymer containing α, β-unsaturated carboxylic acid or an ester thereof as a constituent unit, and (B) a long-chain fatty acid ester.
Item 2.
The α, β-unsaturated carboxylic acid is at least one selected from the group consisting of acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, and itaconic acid.
Item 2. The aqueous composition according to Item 1, wherein the ester of the α, β-unsaturated carboxylic acid is an alkyl ester having 1 to 10 carbon atoms of the α, β-unsaturated carboxylic acid.
Item 3.
A copolymer containing α, β-unsaturated carboxylic acid or an ester thereof as a constituent unit
Further, it is a copolymer containing at least one of ethylene, propylene, butene, isobutene, butadiene, isoprene, and styrene as a constituent unit.
Item 2. The aqueous composition according to Item 1 or 2.
Item 4.
An aqueous composition containing an ethylene / α, β-unsaturated carboxylic acid copolymer, and a montanic acid ester.
Item 5.
Ethylene / α, β-unsaturated carboxylic acid copolymer,
A copolymer containing 8% by mass or more of α, β-unsaturated carboxylic acid.
Item 4. The composition according to Item 4.
Item 6.
Item 4. The composition according to Item 4 or 5, wherein 0.1 to 200 parts by mass of a montanic acid ester is contained with respect to 100 parts by mass of an ethylene / α, β-unsaturated carboxylic acid copolymer.
Item 7.
Item 6. The composition according to any one of Items 4 to 6, wherein the montanic acid ester is an ester of montanic acid and ethylene glycol.
Item 8.
Item 6. The composition according to any one of Items 1 to 7, wherein the α, β-unsaturated carboxylic acid is (meth) acrylic acid.
Item 9.
The copolymer and the ester are dispersed and contained.
Item 2. The composition according to any one of Items 1 to 8.
Item 10.
Item 6. The composition according to any one of Items 1 to 9, which is a paper coating agent.

An aqueous composition capable of efficiently imparting excellent oil resistance and water resistance to paper is provided. The composition is suitable as a paper coating agent. In addition, paper coated with the composition (preferably food packaging paper) is provided.

Hereinafter, each embodiment included in the present disclosure will be described in more detail. The present disclosure discloses an aqueous composition capable of efficiently imparting oil resistance and water resistance to paper, use of the aqueous composition as a paper coating agent, and paper coated with the composition (preferably food wrapping paper). Etc., but are not limited thereto, and the present disclosure includes all disclosed in the present specification and recognized by those skilled in the art.

The composition included in the present disclosure is an aqueous composition and contains (A) a copolymer containing α, β-unsaturated carboxylic acid or an ester thereof as a constituent unit, and (B) a long-chain fatty acid ester. Further, the aqueous solution here means that it contains an aqueous dispersion medium, and the aqueous dispersion medium is particularly preferably water or an aqueous solution. In the present specification, the composition may be referred to as the composition of the present disclosure. The composition of the present disclosure is preferably an aqueous dispersion. A copolymer containing α, β-unsaturated carboxylic acid or an ester thereof as a constituent unit may be referred to as a copolymer (A), and a long-chain fatty acid ester may be referred to as an ester (B).

The copolymer (A) is a copolymer containing one or more α, β-unsaturated carboxylic acids as a constituent unit, and is, for example, (i) one or more α, β-unmodified. It may be a polymer of a saturated carboxylic acid or an ester thereof and one or more kinds of α, β-unsaturated carboxylic acid or a monomer other than the ester thereof, and (ii) two or more kinds of α, β. -It may be a polymer of unsaturated carboxylic acid or an ester thereof. In the case of "two or more kinds of α, β-unsaturated carboxylic acid or its ester", if only two or more kinds of α, β-unsaturated carboxylic acid are used, two or more kinds of α, β-unsaturated carboxylic acid The case of only an ester and the case of one or more kinds of α, β-unsaturated carboxylic acid and one or more kinds of α, β-unsaturated carboxylic acid ester are included.

Examples of the α, β-unsaturated carboxylic acid include acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid and the like. Of these, (meth) acrylic acid (ie, methacrylic acid and / or acrylic acid) is more preferred. Examples of the ester of the α, β-unsaturated carboxylic acid include an alkyl ester having 1 to 10 carbon atoms (1, 2, 3, 4, 5, 6, 7, 8, 9, or 10). The alkyl moiety of the alkyl ester may be straight chain or branched chain. Specific examples of the α, β-unsaturated carboxylic acid ester include methyl ester, ethyl ester, butyl (particularly n-butyl) ester, and 2-ethylhexyl ester. Examples of the α, β-unsaturated carboxylic acid ester include 2-methylaminoethyl ester and hydroxyethyl ester (particularly 2-hydroxyethyl ester). Among these, as the ester of α, β-unsaturated carboxylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate and the like are more preferable.

Examples of the monomer other than the α, β-unsaturated carboxylic acid or its ester include ethylene, propylene, butene, isobutene, butadiene, isoprene, and styrene.

More specifically, the copolymer (A) includes, for example, a copolymer of ethylene / α, β-unsaturated carboxylic acid or an ester thereof, and a co-polymer of styrene / α, β-unsaturated carboxylic acid or an ester thereof. Polymers and the like are preferably mentioned. Of these, ethylene / α, β-unsaturated carboxylic acid copolymers are more preferable. More specifically, for example, ethylene / (meth) acrylic acid copolymer, styrene / (meth) acrylic acid ester copolymer, styrene / (meth) acrylic acid / (meth) acrylic acid ester copolymer, etc. Is more preferably mentioned.

The copolymer (A) can be prepared by a known method or a method easily conceived from a known method. It is also possible to purchase and use a commercially available product. For example, as commercially available products of ethylene / α, β-unsaturated carboxylic acid copolymer, for example, Primacol 5980, Primacol 5990 (manufactured by Dow Chemical Japan Co., Ltd.), Nuclel AN4221C, Nucrel N5130H, Nucrel N2060, Nuclel Examples thereof include N2050H and Nuclel N1560 (manufactured by Mitsui DuPont Polychemical Co., Ltd.).

As the ethylene / α, β-unsaturated carboxylic acid copolymer, an ethylene / (meth) acrylic acid copolymer is particularly preferable.

The copolymer (A) is not particularly limited, but it is preferable that the contained carboxyl group (derived from α, β-unsaturated carboxylic acid) is appropriately neutralized.

Usually, when the carboxyl group of the copolymer (A) is in the free state, the hydrophilicity is relatively low, and when the carboxyl group is in the salt state, the hydrophilicity is relatively high. Therefore, by neutralizing with a base, the neutralized carboxyl group in the copolymer acts as an emulsifier, and an aqueous dispersion can be easily produced.

As the base for neutralization, for example, ammonia, an organic amine, an alkali metal hydroxide and the like are preferably used.

Examples of the organic amine include methylamine, ethylamine, diethylamine, diethanolamine, triethanolamine and the like. Examples of the alkali metal hydroxide include sodium hydroxide, potassium hydroxide, lithium hydroxide and the like. Further, ammonia can also be used in the form of, for example, ammonia gas or an aqueous solution of ammonia. These bases can be used alone or in combination of two or more.

The copolymer (A) preferably contains 20 to 100% of the carboxyl groups neutralized, more preferably 35 to 100% neutralized, and 40 to 70% neutralized. Is more preferable. That is, the degree of neutralization of the copolymer (A) is preferably 20 to 100%, more preferably 35 to 100%, and even more preferably 40 to 70%. The upper limit or the lower limit of the range (20 to 100%) is, for example, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, or 95%. You may. For example, it may be 40 to 95%. The% is the molar% of the carboxyl group unit.

Further, although not particularly limited, the copolymer (A) preferably has an α, β-unsaturated carboxylic acid content of, for example, 8% by mass or more, and more preferably 8 to 50% by mass. preferable. The upper or lower limit of the range is, for example, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, It may be 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, or 49% by mass. For example, it may be 9 to 49% by mass. The α, β-unsaturated carboxylic acid content here is the content of the α, β-unsaturated carboxylic acid-derived unit.

In particular, when the copolymer (A) is an ethylene / α, β-unsaturated carboxylic acid copolymer, the non-polar property derived from the ethylene unit and the polar property derived from the α, β-unsaturated carboxylic acid. In order to have a good balance of properties, those having an α, β-unsaturated carboxylic acid content of 8 to 24% by mass are preferable. The upper or lower limit of the range may be, for example, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, or 23% by mass. The range may be, for example, 18 to 23% by mass. When the content of α, β-unsaturated carboxylic acid is 8% by mass or more, the dispersibility in an aqueous dispersion medium is further improved due to the non-polar property derived from the ethylene unit, and the efficiency is excellent. An aqueous dispersion composition can be obtained. Further, since the content of α, β-unsaturated carboxylic acid is less than 24% by mass, the blocking resistance of the film (coating film) prepared when the obtained aqueous dispersion composition is used as a coating agent is improved. Even better.

The method for preparing the aqueous composition containing the copolymer (A) is not particularly limited. For example, the copolymer (A) is dispersed in an aqueous dispersion medium with stirring at a temperature of 70 to 130 ° C. (in the presence of a predetermined amount of base, if necessary when neutralizing). By cooling the copolymer (A) (neutralized when a base is used) to room temperature while continuing stirring of the aqueous dispersion medium, an aqueous composition of the copolymer (A) is obtained in the form of an aqueous dispersion.

Although not particularly limited, the average particle size of the copolymer (A) in the aqueous composition is preferably, for example, about 5 to 2000 nm, and more preferably about 10 nm to 1000 nm.

The copolymer (A) content in the composition of the present disclosure is preferably, for example, 5 to 50% by mass. The upper or lower limit of the range is, for example, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, or 49% by mass. May be. For example, the range may be 10 to 30% by mass.

The copolymer (A) can be used alone or in combination of two or more.

The ester (B) is preferably an ester of a long-chain fatty acid and an alkyl alcohol.

Examples of long-chain fatty acids include 8 to 30 carbon atoms (8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26). , 27, 28, 29, or 30), and straight-chain or branched-chain fatty acids are more preferred. Further, the long-chain fatty acid may be a saturated or unsaturated fatty acid, and is more preferably a saturated fatty acid. More specifically, long-chain fatty acids include, for example, capric acid, capric acid, lauric acid, myristic acid, palmitanic acid, stearic acid, oleic acid, linoleic acid, arachidic acid, arachidonic acid, behenic acid, lignoseric acid, and serotin. Acids, montanic acid, or melic acid can be mentioned, with montanic acid being particularly preferred.

The alkyl alcohol has, for example, carbon atoms 1 to 30 (1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18). , 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, or 30) Linear or branched chain alkyl alcohols are available, with straight chain alkyl alcohols being more preferred. The alkyl alcohol is preferably a monohydric or divalent alcohol.

As the ester (B), one type alone or two or more types can be used in combination. Therefore, for example, a composition containing two or more kinds of esters of a long-chain fatty acid and an alkyl alcohol can also be used as the ester (B). For example, a wax ester or the like can be preferably used as the ester (B). Although not particularly limited, for example, jojoba oil can be preferably used as the wax ester.

As described above, where the montanic acid ester is one of the particularly preferable esters (B), the montanic acid ester is particularly preferably a mono or diester of montanic acid and glycol. More specifically, for example, an ester of montanic acid and ethylene glycol, propylene glycol, or butylene glycol is preferable, and an ester of montanic acid and ethylene glycol is preferable, and montanic acid and ethylene glycol are used. It is more preferable that it is a monoester of.

The ester (B) can be synthesized and prepared, for example, by a known method or a method easily conceived from a known method, or a commercially available product can be purchased and used. Examples of commercially available products include cybinol A730T and A350T manufactured by Saiden Chemical Co., Ltd. and BYK-498 manufactured by Big Chemie Co., Ltd. as montanic acid esters. These can be used alone or in combination. All of the commercially available products mentioned here are commercially available products in which a montanic acid ester (more specifically, a monoester of ethylene glycol and montanic acid) is dispersed in water or an aqueous solution.

The ester (B) may be used as it is, or may be emulsified and dispersed in an aqueous dispersion medium by using a small amount of a surfactant or the like, if necessary, and used as an aqueous dispersion.

The content ratio of the copolymer (A) and the ester (B) in the composition of the present disclosure is preferably about 0.1 to 200 parts by mass of the ester (B) with respect to 100 parts by mass of the copolymer (A). .. The upper or lower limit of the range is, for example, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 105, 106, 107, 108, 109, 110, 111, 112, 113, 114, 115, 116, 117, 118, 119, 120, 121, 122, 123, 124, 125, 126, 127, 128, 129, 130, 131, 132, 133, 134, 135, 136, 137, 138, 139, 140, 141, 142, 143, 144, 145, 146, 147, 148, 149, 150, 151, 152, 153, 154, 155, 156, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 178, 179, 180, 181, 182, 183, 184, 185, 186, 187, 188, 189, 190, 191, 192, 193, It may be 194, 195, 196, 197, 198, or 199 parts by mass. For example, the range may be 1 to 150 parts by mass or 5 to 100 parts by mass.

In the composition of the present disclosure, it is particularly preferable to use an ethylene / α, β-unsaturated carboxylic acid copolymer and a montanic acid ester as the copolymer (A) and the ester (B). When using the combination, the above content ratio is particularly preferable.

The composition of the present disclosure may contain components other than the copolymer (A) and the ester (B) as long as the effects are not impaired. Examples of such other components include waxes other than the ester (B). Examples of such waxes include polyolefin waxes such as microcrystallin wax, polyethylene wax, carboxyl group-containing polyethylene wax, polypropylene wax, and ethylene-propylene copolymer wax, and fatty acids such as candelilla wax, rice wax, and stearic acid. Examples thereof include fatty acid amides such as stearic acid amide, stearic acid bisamide, oleic acid amide and palmitic acid amide, and fatty acid metal salts such as zinc stearate and calcium stearate.

Further, as described below, the aqueous composition of the composition of the present disclosure can be prepared, for example, by dispersing the copolymer (A) and the ester (B) in an aqueous dispersion medium. Ingredients contained in may also be included in the compositions of the present disclosure.

Such other components may be used alone or in combination of two or more.

Further, as the other component, for example, a pigment may be mentioned. Specific examples thereof include inorganic pigments such as silica, calcium carbonate, kaolin clay, talc, titanium oxide, satin white, aluminum hydroxide and colloidal silica, and organic pigments such as plastic beads and starch particles. Although not particularly limited, the particle size of the pigment is preferably 1 to 12 μm. In addition to the pigment, a water resistant agent, a defoaming agent, a dispersant, a water retaining agent, a thickener, a lubricant, a wetting agent, a preservative, an antistatic agent, a printability improving agent and the like may be appropriately used.

The composition of the present disclosure is, for example, a mixture of an aqueous dispersion of the copolymer (A) (neutralized with a base if necessary) and an aqueous dispersion of the ester (B) or the ester (B). This allows it to be prepared.

The above-mentioned other components may be blended after the mixing, or may be blended in advance with any of the dispersions (preferably the copolymer (A) aqueous dispersion) before the mixing.

In the present invention, the aqueous dispersion medium is generally ordinary tap water or deionized water, but for example, for the purpose of further improving the stability of the aqueous dispersion medium, polyvinyl alcohol, sodium polyacrylate, carboxymethyl cellulose, hydroxyethyl cellulose. Water whose viscosity has been adjusted by adding a water-soluble resin such as the above may be used. The aqueous dispersion medium may contain an antifoaming agent, a viscosity modifier, an antifungal agent and the like in addition to the above-mentioned components as long as the effects of the present invention are not impaired. Further, if necessary, an antioxidant, a fatty acid amide, a slipping property improving agent such as silicone oil, a surfactant and the like may be blended.

The composition of the present disclosure can be preferably used as a coating agent for paper (preferably food packaging paper). The film (coating film) obtained by applying the composition of the present disclosure to paper (dried as necessary) is excellent in adhesiveness and heat seal strength. Further, the composition of the present disclosure is also excellent in coatability. Therefore, (i) a coating agent for materials other than paper such as steel plates and aluminum plates, (ii) various ink binders, (iii) plastic films such as polypropylene, polyethylene and polyester, surface-treated paper or aluminum foil. Etc., can be used as a heat sealant, (iv) fiber treatment agent, or the like. Furthermore, the film prepared from the compositions of the present disclosure can impart water resistance and oil resistance to the surface of each material.

The method of applying the composition of the present disclosure to each material is not particularly limited, and examples thereof include coating. More specific coating methods of the compositions of the present disclosure include general coating methods such as blade coaters, roll coaters, reverse roll coaters, air knife coaters, bar coaters, curtain coaters, lip coaters, rod coaters, and die coaters. , Gravure coater, Champ flex coater and other coating methods. For application, for example, an off-machine coater or an on-machine coater can also be used.

In addition, in this specification, "includes" also includes "consisting essentially" and "consisting of" (The term "comprising" includes "consisting essentially of" and "consisting of."). In addition, the present disclosure includes all combinations of the constituent elements described herein.

In addition, the various characteristics (property, structure, function, etc.) described for each embodiment of the present disclosure described above may be combined in any way in specifying the subject matter included in the present disclosure. That is, the present disclosure includes all subjects consisting of any combination of each of the combinable properties described herein.

Hereinafter, embodiments of the present disclosure will be described in more detail with reference to examples, but the embodiments of the present disclosure are not limited to the following examples.

Evaluation items and methods thereof (1) Oil resistance A resin-containing aqueous dispersion on high-quality paper (commercially available, basis weight 209 g / m ² ) using a bar coater so that the thickness of the film after drying is about 12 μm. Was applied. This was dried at 80 ° C. for 2 minutes using a hot air dryer, and J-TAPPI pulp and paper test method No. The oil resistance value was determined by 41: 2000 (paper and paperboard-oil resistance test method kit method).
(2) Water resistance The resin-containing aqueous dispersion was dried at 80 ° C. with a hot air dryer and molded at 130 ° C. to form a 1 mm thick sheet by a hot press machine. The molded sheet was cut into 2 cm squares, and the cut test pieces were immersed in pure water for 7 days.
Weight increase rate (%) obtained from the film weight before and after immersion by the following formula: Weight increase rate (%) = (Weight after immersion-Weight before immersion) / (Weight before immersion) x 100

[Production Example 1 of Neutralized Ethylene / Acrylic Acid Copolymer]
Ethylene / acrylic acid copolymer (trade name: Primacol 5980i, manufactured by SK Global chemial, acrylic acid content 20% by mass, melt flow rate 300 g / 10) in a separable flask with a capacity of 500 ml equipped with a stirring blade with a diameter of 50 mm. Minutes) 112 g, 11.3 g of 28% ammonia water (corresponding to 60% neutralization) and 276.7 g of water as an aqueous dispersion medium were charged and heated under stirring to raise the temperature. After raising the temperature of the contents to 95 ° C. and continuing stirring at that temperature for 4 hours, the contents are cooled to room temperature while continuing stirring, and ethylene / acrylic acid having a resin concentration of 28% and a medium particle size of 100 nm is used. An aqueous dispersion of the copolymer was obtained.

(Example 1)
50 g of the aqueous dispersion of the ethylene / acrylic acid copolymer obtained in Production Example 1 (resin content concentration 28% by mass) and Cybinol A350T (Siden Chemical Industry Co., Ltd.) which is a montanic acid ester aqueous dispersion (solid content 25%). (Manufactured by Co., Ltd.) 11.2 g was mixed and dispersed to obtain an ethylene-based resin aqueous dispersion. The obtained ethylene-based resin aqueous dispersion was evaluated according to the performance evaluation method, and the results are shown in Table 1.

(Example 2)
50 g of the aqueous dispersion of the ethylene / acrylic acid copolymer obtained in Production Example 1 (resin concentration 28% by mass) and Cybinol A350T (Siden Chemical Industry Co., Ltd.) which is a montanic acid ester aqueous dispersion (solid content 25%). (Manufactured by Co., Ltd.) 28 g was mixed and dispersed to obtain an ethylene-based resin aqueous dispersion. The obtained ethylene-based resin aqueous dispersion was evaluated according to the performance evaluation method, and the results are shown in Table 1.

(Example 3)
50 g of the aqueous dispersion of the ethylene / acrylic acid copolymer obtained in Production Example 1 (resin concentration 28% by mass) and Cybinol A350T (Siden Chemical Industry Co., Ltd.) which is a montanic acid ester aqueous dispersion (solid content 25%). Co., Ltd.) 56 g was mixed and dispersed to obtain an ethylene-based resin aqueous dispersion. The obtained ethylene-based resin aqueous dispersion was evaluated according to the performance evaluation method, and the results are shown in Table 1. Cybinol A350T is a monoester of ethylene glycol and montanic acid.

(Comparative Example 1)
The aqueous dispersion (resin concentration 28% by mass) of the ethylene / acrylic acid copolymer obtained in Production Example 1 was evaluated according to the performance evaluation method, and the results are shown in Table 1.

(Comparative Example 2)
Neocryl A-2092 (manufactured by DSM Coating Resins), which is an acrylic emulsion, was evaluated according to the performance evaluation method, and the results are shown in Table 1.

(Comparative Example 3)
Neoletz R600 (manufactured by DSM Coating Resins), which is a urethane emulsion, was evaluated according to the performance evaluation method, and the results are shown in Table 1.

As shown in Table 1, the aqueous dispersion of the resins of Examples 1 to 3 (copolymer containing α, β-unsaturated carboxylic acid as a constituent unit) has an oil resistance value (kit value) measured by the kit method. ) 11 or more and water resistance of ± 5%, showing good oil resistance and water resistance. On the other hand, Comparative Example 3 in which the long-chain fatty acid ester (specifically, montanic acid ester) was not blended had a good water resistance of + 1.8%, but on the other hand, it had an oil resistance value of 6 and was inferior in oil resistance. .. Further, when the acrylic resin or the urethane resin was used, both had an oil resistance value of 12, and the oil resistance was excellent, but the water resistance was very poor.

Claims (10)

An aqueous composition containing (A) a copolymer containing α, β-unsaturated carboxylic acid or an ester thereof as a constituent unit, and (B) a long-chain fatty acid ester. The α, β-unsaturated carboxylic acid is at least one selected from the group consisting of acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, and itaconic acid.
The aqueous composition according to claim 1, wherein the ester of the α, β-unsaturated carboxylic acid is an alkyl ester having 1 to 10 carbon atoms of the α, β-unsaturated carboxylic acid. A copolymer containing α, β-unsaturated carboxylic acid or an ester thereof as a constituent unit
Further, it is a copolymer containing at least one of ethylene, propylene, butene, isobutene, butadiene, isoprene, and styrene as a constituent unit.
The aqueous composition according to claim 1 or 2. An aqueous composition containing an ethylene / α, β-unsaturated carboxylic acid copolymer, and a montanic acid ester. Ethylene / α, β-unsaturated carboxylic acid copolymer,
A copolymer containing 8% by mass or more of α, β-unsaturated carboxylic acid.
The composition according to claim 4. The composition according to claim 4 or 5, wherein 0.1 to 200 parts by mass of a montanic acid ester is contained with respect to 100 parts by mass of an ethylene / α, β-unsaturated carboxylic acid copolymer. The composition according to any one of claims 4 to 6, wherein the montanic acid ester is an ester of montanic acid and ethylene glycol. The composition according to any one of claims 1 to 7, wherein the α, β-unsaturated carboxylic acid is (meth) acrylic acid. The copolymer and the ester are dispersed and contained.
The composition according to any one of claims 1 to 8. The composition according to any one of claims 1 to 9, which is a paper coating agent.