JP2022017966A - Resin-containing composition - Google Patents

Abstract

To provide a composition which is widely usable as a coating agent of various materials (for example, polymer film, functional paper and functional film) and contains a copolymer containing an α,β-unsaturated carboxylic acid or its ester as a constitutional unit.SOLUTION: There is provided an aqueous dispersion composition of a copolymer containing a nonionic surfactant having an HLB of 7 or less, and containing an α,β-unsaturated carboxylic acid or its ester as a constitutional unit.SELECTED DRAWING: None

Description

The present disclosure relates to a composition containing a resin (particularly a copolymer containing α, β-unsaturated carboxylic acid or an ester thereof as a constituent unit). The contents of all documents described in this specification are incorporated herein by reference.

An aqueous dispersion of a copolymer containing α, β-unsaturated carboxylic acid or an ester thereof (for example, ethylene / α, β-unsaturated carboxylic acid copolymer) has a film having good thermal adhesion. Since it can be formed, it is used in a wide range of applications such as coating agents, heat sealants, delatac agents, inmold labels, percoat agents, fiber treatment agents and various binders.

The copolymer containing α, β-unsaturated carboxylic acid or an ester thereof used for such various uses is used in a solid state or in a state of being dissolved or dispersed in a solvent or water. In some cases. The former is often used in the latter state because it is difficult to form a thin film like a laminate coating agent and there are problems such as recent reduction of plastics. Among the latter, water-based ones that do not require the use of solvents, especially water-dispersed ones, have come to be widely used, especially from the viewpoint of resource saving, safety and environmental problems.

As the copolymer resin aqueous dispersion containing α, β-unsaturated carboxylic acid or an ester thereof as a constituent unit, for example, an ethylene / acrylic acid copolymer is neutralized with ammonia, amine, alkali metal hydroxide or the like. Aqueous dispersions are known (for example, Patent Documents 1 to 3).

Further, in particular, when a copolymer aqueous dispersion containing α, β-unsaturated carboxylic acid or an ester thereof as a constituent unit is used as a coating agent, the base material to be coated is added to the conventional metal such as aluminum or steel plate. Recently, polymer films such as polyethylene, polypropylene, nylon, and polyvinyl alcohol films, sterilized papers and oil-resistant papers made by lamicking (especially vapor-depositing) the polymers or supporting inorganic minerals on the surface of the substrate. Functional papers and functional films such as paper, water resistant paper, and gas barrier paper have appeared and are diversifying (for example, Patent Documents 4 to 6). However, the surface of such a polymer film, functional paper, or functional film often has low adhesiveness, and for this reason, a conventional α, β-unsaturated carboxylic acid or an ester thereof is a constituent unit. In many cases, it was difficult to obtain a good coating by using the copolymer aqueous dispersion contained in the above.

Japanese Unexamined Patent Publication No. 50-135141 Japanese Patent No. 6426751 Japanese Patent No. 4364983 Japanese Unexamined Patent Publication No. 2001-303475 Japanese Patent No. 4934970 Japanese Unexamined Patent Publication No. 2001-254292

Therefore, the present inventors have an α, β-unsaturated carboxylic acid that can be widely used as a coating agent for various materials (for example, a polymer film, or a functional paper or a functional film) due to its excellent adhesiveness. Studies were conducted to develop a composition containing a copolymer containing an acid or an ester thereof as a constituent unit.

The present inventors particularly by incorporating a nonionic surfactant having an HLB of 7 or less into an aqueous dispersion composition of a polymer containing α, β-unsaturated carboxylic acid or an ester thereof as a constituent unit. We found the possibility of preparing a composition that enables a coating showing excellent adhesiveness, and further studies were conducted.

The present disclosure includes, for example, the subjects described in the following sections.
Item 1.
An aqueous dispersion composition of a copolymer containing α, β-unsaturated carboxylic acid or an ester thereof as a constituent unit, which contains a nonionic surfactant having an HLB of 7 or less.
Item 2.
Item 2. The composition according to Item 1, wherein the nonionic surfactant having an HLB of 7 or less is a surfactant having a symmetrical chemical structure.
Item 3.
A copolymer containing α, β-unsaturated carboxylic acid or an ester thereof as a constituent unit
Item 2. The composition according to any one of Items 1 or 2, which is a copolymer containing at least one of ethylene, propylene, butene, isobutene, butadiene, isoprene, and styrene as a constituent unit.
Item 4.
Item 6. The composition according to any one of Items 1 to 3, wherein the nonionic surfactant having an HLB of 7 or less is an acetylene glycol-based surfactant.
Item 5.
The acetylene glycol-based surfactant has the formula (I) :.

Item 4. The composition according to Item 4, wherein m and n are the same or different, and represent 0 or a positive number, and are compounds having an HLB of 7 or less.
Item 6.
Equation (I):

(In the formula, m and n are the same or different and indicate 0 or a positive number.) A compound having an HLB of 7 or less is represented by
It contains 2 to 15 parts by mass with respect to 100 parts by mass of the copolymer containing α, β-unsaturated carboxylic acid or an ester thereof as a constituent unit.
An aqueous dispersion composition of a copolymer containing α, β-unsaturated carboxylic acid or an ester thereof as a constituent unit.
Item 7.
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 6. The composition according to any one of Items 1 to 6, 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 8.
A copolymer containing α, β-unsaturated carboxylic acid or an ester thereof as a constituent unit is a polymer containing α, β-unsaturated carboxylic acid or an ester thereof having a neutralization degree of 40 to 70% as a constituent unit. , The composition according to any one of Items 1 to 7.
Item 9.
Item 6. The composition according to any one of Items 1 to 8, wherein the copolymer containing α, β-unsaturated carboxylic acid or an ester thereof as a constituent unit is an ethylene / α, β-unsaturated carboxylic acid copolymer.
Item 10.
Item 9. The composition according to Item 9, wherein the ethylene / α, β-unsaturated carboxylic acid copolymer is an ethylene / (meth) acrylic acid copolymer.
Item 11.
Item 6. The composition according to any one of Items 1 to 10, which is a coating composition.

A composition containing a copolymer containing an α, β-unsaturated carboxylic acid or an ester thereof as a constituent unit, which enables a coating exhibiting excellent adhesiveness, is provided. The composition is particularly useful as a coating agent. When the composition is used as a coating agent, the adhesiveness is particularly excellent. Therefore, a composition containing a conventional α, β-unsaturated carboxylic acid or a copolymer containing an ester thereof as a constituent unit should be coated with a good coating. A good coating can be applied even to difficult materials.

Furthermore, the composition having a more specific composition is more preferable because it exhibits excellent coatability in addition to excellent adhesiveness.

Hereinafter, each embodiment included in the present disclosure will be described in more detail. The present disclosure preferably includes, but is not limited to, an aqueous dispersion composition of a copolymer containing α, β-unsaturated carboxylic acid or an ester thereof as a constituent unit and its use, and the present disclosure is not limited thereto. All disclosed herein and recognizable by those of skill in the art are included.

The aqueous dispersion composition of the copolymer containing α, β-unsaturated carboxylic acid or an ester thereof included in the present disclosure as a constituent unit contains a nonionic surfactant having an HLB of 7 or less. In the present specification, the composition included in the present disclosure may be referred to as "the composition of the present disclosure". Further, a copolymer containing α, β-unsaturated carboxylic acid or an ester thereof as a constituent unit may be referred to as a copolymer (A).

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. In particular, an ethylene / α, β-unsaturated carboxylic acid copolymer is preferable.

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, a commercially available product of an ethylene / α, β-unsaturated carboxylic acid copolymer can be purchased and used. Examples of commercially available products include Primacol 5980, Primacol 5990 (manufactured by Dow Chemical Japan Co., Ltd.), Nuclel AN4221C, Nucrel N5130H, Nucrel N2060, Nucrel N2050H, Nucrel N1560 (manufactured by Mitsui DuPont Polychemical Co., Ltd.) and the like. Can be mentioned.

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.

It is preferable that 20 to 100% of the carboxyl groups of the copolymer (A) are neutralized, more preferably 35 to 100% is neutralized, and 40 to 70% is neutralized. Is even 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, it has a non-polar property derived from the ethylene unit and a 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.

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 to room temperature while continuing stirring of the aqueous dispersion medium, an aqueous composition of the copolymer (A) (neutralized when a base is used) 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, more preferably about 10 to 1000 nm, more preferably about 10 to 500 nm, or more preferably about 10 to 300 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 10-40% by weight or 15-35% by weight.

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

Water is preferable as the aqueous medium of the composition of the present disclosure, and various types of water such as tap water, industrial water, ion-exchanged water, deionized water, and pure water can be used. Deionized water or pure water is particularly preferable.

As described above, the composition of the present disclosure contains a nonionic surfactant having an HLB (hydrophilic new oil balance) of 7 or less. The HLB of the surfactant is preferably 2-7. The upper limit or adjustment of the range may be, for example, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, or 6.5. For example, the range may be 2.5 to 6.5.

Preferred examples of the surfactant include a fluorine-based surfactant, a siloxane-based surfactant, an acrylic-based surfactant, and an acetylene glycol-based surfactant having an HLB of 7 or less. As the surfactant, a surfactant used as a surface conditioner (antifoaming agent, leveling agent) in the technical field is preferable.

Examples of the fluorine-based surfactant include Florard FC-430 and FC170 manufactured by Sumitomo 3M Ltd. and Megafuck F177 and F471 manufactured by Dainippon Ink and Chemicals Co., Ltd.

Further, as the fluorine-based surfactant, for example, a fluorinated alkyl ester is preferable. Preferred examples of the siloxane-based surfactant include BYK-333 and BYK-077 manufactured by Big Chemie. As the acrylic surfactant, for example, BYK-380 manufactured by Big Chemie, Disparon L-1984-50, L-970 manufactured by Kusumoto Kasei Co., Ltd. and the like are preferably mentioned. As the acetylene glycol-based surfactant, for example, surfinol manufactured by Nisshin Kagaku Kogyo Co., Ltd. (more specifically, for example, surfinol 420, etc.) is preferably mentioned. Among these surfactants, acetylene glycol-based surfactants are particularly preferable.

Further, although not particularly limited, among nonionic surfactants having an HLB of 7 or less, a surfactant having a symmetrical chemical structure is preferable. When a chemical structural formula is drawn, a compound that can draw a line-symmetrical or point-symmetrical chemical structural formula is assumed to have a “bilaterally symmetric chemical structure”.

Among the acetylene glycol-based surfactants, more specifically, the formula (I):

(In the formula, m and n are the same or different and indicate 0 or a positive number.) A compound having an HLB of 7 or less, which is represented by 0 or a positive number, is particularly preferable.

m and n represent 0 or positive numbers that are the same or different, and more specifically, integers of 0 to 25 that are the same or different (0, 1, 2, 3, 4, 5, 6, 7, 8, 9). 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, or 25) are shown. It is more preferable that m + n ≦ 40. Further, it is preferable that m = n. The HLB represented by the compound represented by the formula (I) can be adjusted by the number of repetitions (m, n) of the ethylene oxide unit (-CH ₂ -CH ₂ -O-) in the formula (I). Therefore, a compound represented by the formula (I) having a repetition number (m, n) having an HLB of 7 or less can be selected and used in the composition of the present disclosure. When m = n = 0, the HLB becomes about 4, and as m and n increase, the HLB gradually increases.

As the compound represented by the formula (I), a commercially available product can be purchased and used, and as the compound represented by the formula (I) of m = n = 0, for example, Surfinol 104 (104E, 104H, 104A, 104PA, 104S, etc.) (HLB4) can be mentioned. Further, examples of the compound represented by the formula (I) in which m and n are positive numbers and having an HLB of 7 or less include, for example, Surfinol 420 (HLB4), Surfinol SE, and Surfinol SE-F (all HLB6). Examples thereof include Surfinol DF110D (HLB3) (both from Nissin Chemical Industry Co., Ltd.). The surfinol series products other than these (for example, surfinol 440, surfinol 465, surfinol 485, etc.) are also compounds represented by the formula (I), but since the HLB is larger than 7, the composition of the present disclosure is disclosed. Not suitable for use in things.

The content ratio of the copolymer (A) to the nonionic surfactant having an HLB of 7 or less in the composition of the present disclosure is such that the excellent adhesiveness of the composition of the present disclosure is not impaired. However, there are no particular restrictions. For example, it is preferable that the copolymer (A) contains about 0.5 to 15 parts by mass of a nonionic surfactant having an HLB of 7 or less with respect to 100 parts by mass. The upper or lower limit of the range (0.5 to 15 parts by mass) is, for example, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5.5, 6, 6 .5, 7, 7.5, 8, 8.5, 9, 9.5, 10, 10.5, 11, 11, 5, 12, 12.5, 13, 13.5, 14, or 14. It may be 5 parts by mass. For example, the range may be 2 to 14 parts by mass.

When an acetylene glycol-based surfactant (particularly a compound represented by the formula (I)) is used as the nonionic surfactant having an HLB of 7 or less, the surfactant is used in the composition of the present disclosure. It is preferable that the copolymer (A) is contained in an amount of 2 to 15 parts by mass with respect to 100 parts by mass. In this case, the composition of the present disclosure can exhibit excellent coatability in addition to excellent adhesiveness. The upper or lower limit of the range (2 to 15 parts by mass) is, for example, 2.5, 3, 3.5, 4, 4.5, 5.5, 6, 6.5, 7, 7.5, 8. , 8.5, 9, 9.5, 10, 10.5, 11, 11, 5, 12, 12.5, 13, 13.5, 14, or 14.5 parts by mass. For example, the range may be 2.5 to 14 parts by mass.

The composition of the present disclosure may contain other components as long as the effect is not impaired. For example, defoamers, viscosity regulators (eg, water-soluble resins such as polyvinyl alcohol, sodium polyacrylate, carboxymethyl cellulose, hydroxyethyl cellulose, etc.), pH regulators, surfactants, antifungal agents, etc., and if necessary, It may contain an antioxidant, a fatty acid amide, a wax, a blocking property improving agent such as silicone oil, alcohols and the like.

As a method for producing the composition of the present disclosure, for example, a copolymer (A) aqueous dispersion composition neutralized as necessary and a nonionic surfactant having an HLB of 7 or less are used (necessarily). A method of mixing and dispersing (with other components as well) can be mentioned.

The film obtained from the compositions of the present disclosure (eg, obtained by coating) has excellent adhesiveness. In particular, it has excellent heat seal strength. Further, in the composition of the present disclosure, when an acetylene glycol-based surfactant (particularly a compound represented by the formula (I)) is used as the nonionic surfactant having an HLB of 7 or less, the surfactant is said. When the agent is contained in an amount of 2 to 15 parts by mass with respect to 100 parts by mass of the copolymer (A), the coatability is also excellent. Because of these effects, the compositions of the present disclosure can be used not only as a coating agent for metal plates (for example, steel plates, aluminum plates, etc.), but also as an adhesive layer, polypropylene, polyethylene, which have been difficult to coat in the past. , Polyester and other plastic films, surface-treated paper, aluminum foil, etc. can also be used as coating agents, heat sealants, binders, and the like. Alternatively, it can also be used as a fiber treatment agent.

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 their methods (1) Coatability A coating machine on kraft paper coated with a gas barrier agent (Nippon Paper Industries, Ltd. Shield Plus Premier coated paper) so that the thickness of the film after drying is 10 μm. An aqueous dispersion composition of each ethylene / α and β-unsaturated carboxylic acid copolymer was applied using (trade name; Barcoater No. 16, manufactured by Nippon Cedars Service Co., Ltd.). This was left at room temperature to remove water, and a film was obtained. The obtained film (coating of a copolymer containing α, β-unsaturated carboxylic acid or an ester thereof as a constituent unit) was visually evaluated. The evaluation criteria are as follows.
◯: Continuous film △: Partially discontinuous film (spots are present)
×: Discontinuous film

(2) A coating machine (trade name; bar coater) on kraft paper coated with an adhesive gas barrier agent (Nippon Paper Industries, Ltd. Shield Plus Premier coated paper) so that the thickness of the film after drying is 10 μm. An aqueous dispersion composition of a copolymer containing α, β-unsaturated carboxylic acid or an ester thereof as a constituent unit was applied using No. 16, manufactured by Nippon Cedars Service Co., Ltd.

This is dried at 105 ° C. for 1 minute using a hot air dryer, and a substrate having a film of an aqueous dispersion composition of a copolymer containing each α, β-unsaturated carboxylic acid or an ester thereof as a constituent unit is 25 mm. It was cut out to the width and used as a test piece.

The coated surfaces of this test piece are pasted together, and a heat seal tester (trade name; thermal tilt tester manufactured by Toyo Seiki Co., Ltd.) is used to set the conditions of this tester to a seal temperature of 80 ° C to 120 ° C and a seal pressure of 2 kg. The seal time was set to / cm ² and the sealing time was 3 seconds, and heat sealing was performed. After leaving the sealed test piece for one day, a tensile tester (trade name; Autograph AGS-D type, manufactured by Shimadzu Corporation) was used to set the tensile speed to 50 mm / min and the tensile angle to 180 degrees. We confirmed that the paper was broken. Then, it was evaluated according to the following criteria. (If the paper is torn, it means that the paper is torn without peeling, and if the paper is not torn, it means that the paper is peeled off without tearing, so the paper is torn. However, it can be evaluated as having high adhesiveness.)
Paper material breakage; 〇 Paper material breakage only at a high temperature of 120 ° C seal temperature; △
No paper tear (no adhesiveness); ×

In the following example, an ethylene / α, β-unsaturated carboxylic acid copolymer was used as a copolymer containing α, β-unsaturated carboxylic acid or an ester thereof as a constituent unit.

[Production Example 1: Production of Neutralized Ethylene / Acrylic Acid Copolymer]
Ethylene / acrylic acid copolymer (EAA) (trade name: Primacol 5980, manufactured by LG Global Co., Ltd., acrylic acid content 20% by mass,) in a 500 ml capacity separable flask equipped with a stirring blade having a diameter of 50 mm. 112 g of melt flow rate (300 g / 10 min), 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 to obtain a neutralized aqueous dispersion of ethylene / acrylic acid copolymer. Obtained.

[Production Example 2: Production of Neutralized Ethylene / Methacrylic Acid Copolymer]
Ethylene / methacrylic acid copolymer (EMAA) (trade name: Nuclel N2060, manufactured by Mitsui Dow Chemical Co., Ltd., methacrylic acid content 20% by mass,) in a separable flask having a capacity of 500 ml equipped with a stirring blade having a diameter of 50 mm. 62.5 g of melt flow rate (60 g / 10 min), 3.6 g of potassium hydroxide (corresponding to 50% neutralization) and 140.4 g of water as an aqueous dispersion medium were charged, and the temperature was raised by heating under stirring. After raising the temperature of the contents to 98 ° C. and continuing stirring at that temperature for 8 hours, the contents were cooled to room temperature while continuing stirring, and an aqueous dispersion of a neutralized ethylene / methacrylic acid copolymer was prepared. Got

(Example 1)
50 g of an aqueous dispersion of an ethylene / acrylic acid copolymer (concentration of the copolymer: 28% by mass) and 0.84 g of acetylene glycol-based surfactant Surfinol 420 (Nisshin Kagaku Kogyo Co., Ltd.) were mixed and dispersed. , An aqueous dispersion composition of an ethylene / acrylic acid copolymer was obtained. The obtained aqueous dispersion composition was evaluated according to the performance evaluation method. The results are shown in Table 1.

(Example 2)
50 g of an aqueous dispersion of ethylene / methacrylic acid copolymer (concentration of 28% by mass of the copolymer) obtained in Production Example 2 and acetylene glycol-based surfactant Surfinol 420 (Nisshin Chemical Industry Co., Ltd.) 0 .84 g was mixed and dispersed to obtain an aqueous dispersion composition of an ethylene / methacrylic acid copolymer. The obtained aqueous dispersion composition was evaluated according to the performance evaluation method. The results are shown in Table 1.

(Comparative Example 1)
50 g of an aqueous dispersion of an ethylene / acrylic acid copolymer (concentration of the copolymer: 28% by mass) and 0.84 g of acetylene glycol-based surfactant Surfinol 440 (Nisshin Kagaku Kogyo Co., Ltd.) are mixed and dispersed. , An aqueous dispersion composition of an ethylene / acrylic acid copolymer was obtained. The obtained aqueous dispersion composition was evaluated according to the performance evaluation method. The results are shown in Table 1.

(Comparative Example 2)
50 g of an aqueous dispersion of an ethylene / acrylic acid copolymer (concentration of the copolymer: 28% by mass) and 0.84 g of acetylene glycol-based surfactant Surfinol 465 (Nisshin Kagaku Kogyo Co., Ltd.) were mixed and dispersed. , An aqueous dispersion composition of an ethylene / acrylic acid copolymer was obtained. The obtained aqueous dispersion composition was evaluated according to the performance evaluation method. The results are shown in Table 1.

(Comparative Example 3)
50 g of an aqueous dispersion of an ethylene / acrylic acid copolymer (concentration of the copolymer: 28% by mass) and 0.84 g of acetylene glycol-based surfactant Surfinol 485 (Nisshin Kagaku Kogyo Co., Ltd.) are mixed and dispersed. , An aqueous dispersion composition of an ethylene / acrylic acid copolymer was obtained. The obtained aqueous dispersion composition was evaluated according to the performance evaluation method. The results are shown in Table 1.

(Reference example 1)
50 g of an aqueous dispersion of an ethylene / acrylic acid copolymer (concentration of the copolymer: 28% by mass) and 0.14 g of acetylene glycol-based surfactant Surfinol 420 (Nisshin Kagaku Kogyo Co., Ltd.) were mixed and dispersed. , An aqueous dispersion composition of an ethylene / acrylic acid copolymer was obtained. The obtained aqueous dispersion composition was evaluated according to the performance evaluation method. The results are shown in Table 1.

(Reference example 2)
An aqueous dispersion of an ethylene / acrylic acid copolymer (the copolymer concentration: 28% by mass) was evaluated according to the performance evaluation method. The results are shown in Table 1.

Claims (11)

An aqueous dispersion composition of a copolymer containing α, β-unsaturated carboxylic acid or an ester thereof as a constituent unit, which contains a nonionic surfactant having an HLB of 7 or less. The composition according to claim 1, wherein the nonionic surfactant having an HLB of 7 or less is a surfactant having a symmetrical chemical structure. A copolymer containing α, β-unsaturated carboxylic acid or an ester thereof as a constituent unit
The composition according to any one of claims 1 or 2, which is a copolymer containing at least one of ethylene, propylene, butene, isobutene, butadiene, isoprene, and styrene as a constituent unit. The composition according to any one of claims 1 to 3, wherein the nonionic surfactant having an HLB of 7 or less is an acetylene glycol-based surfactant. The acetylene glycol-based surfactant has the formula (I) :.

The composition according to claim 4, wherein m and n are the same or different, and represent 0 or a positive number, and are compounds having an HLB of 7 or less. Equation (I):

(In the formula, m and n are the same or different and indicate 0 or a positive number.) A compound having an HLB of 7 or less is represented by
It contains 2 to 15 parts by mass with respect to 100 parts by mass of the copolymer containing α, β-unsaturated carboxylic acid or an ester thereof as a constituent unit.
An aqueous dispersion composition of a copolymer containing α, β-unsaturated carboxylic acid or an ester thereof as a constituent unit. 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 composition according to any one of claims 1 to 6, 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 is a polymer containing α, β-unsaturated carboxylic acid or an ester thereof having a neutralization degree of 40 to 70% as a constituent unit. , The composition according to any one of claims 1 to 7. The composition according to any one of claims 1 to 8, wherein the copolymer containing α, β-unsaturated carboxylic acid or an ester thereof as a constituent unit is an ethylene / α, β-unsaturated carboxylic acid copolymer. .. The composition according to claim 9, wherein the ethylene / α, β-unsaturated carboxylic acid copolymer is an ethylene / (meth) acrylic acid copolymer. The composition according to any one of claims 1 to 10, which is a coating composition.