WO2024010038A1

WO2024010038A1 - Resin dispersion composition

Info

Publication number: WO2024010038A1
Application number: PCT/JP2023/024963
Authority: WO
Inventors: 俊成水橋
Original assignee: 住友精化株式会社
Priority date: 2022-07-08
Filing date: 2023-07-05
Publication date: 2024-01-11

Abstract

The present invention provides an aqueous dispersion of an olefin/α,β-unsaturated carboxylic acid copolymer, the aqueous dispersion being capable of producing coated paper that is coated with the aqueous dispersion of an olefin/α,β-unsaturated carboxylic acid copolymer and has excellent gas barrier properties (in particular, excellent water vapor barrier properties). More specifically, the present invention provides an aqueous dispersion composition of an olefin/α,β-unsaturated carboxylic acid copolymer, wherein the value obtained by the calculation formula shown below is -0.4 or less. Formula: (Logη0.1 - Logη1000)/(Log0.1 - Log1000) In the formula, η0.1 represents the viscosity (Pa∙s) at the shear rate of 0.1 s-1; η1000 represents the viscosity (Pa∙s) at the shear rate of 1,000 s-1; and the logarithms in the formula are common logarithms.

Description

resin dispersion composition

The present disclosure relates to a resin dispersion composition, and more particularly to an aqueous dispersion composition of an olefin/α,β-unsaturated carboxylic acid copolymer.

In recent years, due to the move away from plastics, technological development has been progressing to switch from polyethylene laminated paper to emulsion coated paper. It is known that polyethylene laminated paper has a large amount of resin lamination and is difficult to recycle. On the other hand, it is known that emulsion coated paper can reduce the amount of resin lamination and is relatively easy to recycle.

In particular, it is known that paper coated with an aqueous dispersion of an olefin/α,β-unsaturated carboxylic acid copolymer can be made into coated paper with excellent heat-sealability and disintegration properties. . However, coated paper coated with an aqueous dispersion of an olefin/α,β-unsaturated carboxylic acid copolymer tends to have defects in the coating layer (for example, cracks during drying) and has gas barrier properties (water vapor barrier properties). (barrier properties, oxygen barrier properties, etc.) tend to be inferior.

Japanese Patent Application Publication No. 2004-059657 International Publication No. 2022/014548

The present inventors have developed a coated paper coated with an aqueous dispersion of an olefin/α,β-unsaturated carboxylic acid copolymer, which has excellent gas barrier properties (particularly water vapor barrier properties). Studies were conducted to provide an aqueous dispersion of an olefin/α,β-unsaturated carboxylic acid copolymer that can be produced.

The present inventors believe that if an aqueous dispersion of an olefin/α,β-unsaturated carboxylic acid copolymer has a relatively high shear rate dependence (the viscosity tends to decrease as the shear rate increases), They found a possibility to solve the problem and made further improvements.

This disclosure encompasses, for example, the subject matter described in the following sections.
Item 1.
An aqueous dispersion composition of an olefin/α,β-unsaturated carboxylic acid copolymer, the composition comprising:
An aqueous dispersion composition whose calculated value in the following formula is -0.4 or less.
Formula: (Logη ^0.1 - Logη ¹⁰⁰⁰ )/(Log0.1-Log1000)
However, η ^0.1 indicates the viscosity (Pa・s) at a shear rate of 0.1 s ⁻¹ , η ¹⁰⁰⁰ indicates the viscosity (Pa・s) at a shear rate of 1000 s ⁻¹ , and the logarithm in the equation is the common logarithm. show.
Item 2.
Furthermore, containing ammonia and/or organic amines,
The aqueous dispersion composition according to claim 1.
Item 3.
The aqueous dispersion composition according to claim 1 or 2, wherein the α,β-unsaturated carboxylic acid content in the olefin/α,β-unsaturated carboxylic acid copolymer is 10 to 25% by mass.
Item 4.
mixing an olefin/α,β-unsaturated carboxylic acid copolymer, a base, and an aqueous medium;
At the time of said mixing, the temperature is raised to 90°C or more at a temperature increase rate of 1°C/min or less,
A method for producing an aqueous dispersion composition of an olefin/α,β-unsaturated carboxylic acid copolymer.
Item 5.
A laminate comprising a paper base material and a film on the paper base material,
A laminate, wherein the film is formed using the aqueous dispersion composition of the olefin/α,β-unsaturated carboxylic acid copolymer according to any one of claims 1 to 3.

A coated paper coated with an aqueous dispersion of an olefin/α,β-unsaturated carboxylic acid copolymer that has excellent gas barrier properties (particularly water vapor barrier properties) can be produced.

The relationship between shear rate (Pa·s) and steady flow viscosity (s ⁻¹ ) is shown graphically for the aqueous dispersion composition of Example 1 and the aqueous dispersion composition of Comparative Example 1.

Hereinafter, each embodiment included in the present disclosure will be described in further detail. The present disclosure preferably includes, but is not limited to, an aqueous dispersion composition of an olefin/α,β-unsaturated carboxylic acid copolymer, and a laminate (especially coated paper) provided with the aqueous dispersion composition. Rather, the present disclosure encompasses everything disclosed herein and recognized by those skilled in the art. Note that the olefin/α,β-unsaturated carboxylic acid copolymer may be referred to as a copolymer (A).

The aqueous dispersion composition of copolymer (A) included in the present disclosure includes copolymer (A) and an aqueous medium (preferably water). Hereinafter, the aqueous dispersion composition included in the present disclosure may be referred to as the "composition of the present disclosure."

As mentioned above, the copolymer (A) is a copolymer of an olefin and an α,β-unsaturated carboxylic acid. One type of olefin may be used alone, or two or more types may be used in combination. Furthermore, α,β-unsaturated carboxylic acids and olefins may be used alone or in combination of two or more.

Examples of the α,β-unsaturated carboxylic acid include acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, and itaconic acid. Among these, (meth)acrylic acid (that is, methacrylic acid and/or acrylic acid) is more preferred.

Examples of olefins include ethylene, propylene, butene, isobutene, butadiene, isoprene, and styrene. Among these, ethylene, propylene, and styrene are preferred, and ethylene is more preferred.

More specifically, the copolymer (A) includes, for example, ethylene/α,β-unsaturated carboxylic acid copolymer, propylene/α,β-unsaturated carboxylic acid copolymer, styrene/α,β-unsaturated carboxylic acid copolymer, and styrene/α,β-unsaturated carboxylic acid copolymer. - Unsaturated carboxylic acid copolymers are preferred, and ethylene/(meth)acrylic acid copolymers are particularly preferred.

Note that in the composition of the present disclosure, the copolymer (A) can be used alone or in combination of two or more.

The composition of the present disclosure is an aqueous dispersion composition whose calculated value in the following calculation formula is -0.4 or less.
Formula: (Logη ^0.1 - Logη ¹⁰⁰⁰ )/(Log0.1-Log1000)
However, η ^0.1 indicates the viscosity (Pa·s) at a shear rate of 0.1 s ⁻¹ , and η ¹⁰⁰⁰ indicates the viscosity (Pa·s) at a shear rate of 1000 s ⁻¹ . Note that all logarithms in the formula are common logarithms.

The calculated value is preferably between -1 and -0.4. The upper or lower limits of the range are, for example, -0.95, -0.9, -0.85, -0.8, -0.75, -0.7, -0.65, -0.6, -0. It may be .55, -0.5, or -0.45. For example, the range is more preferably -0.9 to -0.45, even more preferably -0.8 to -0.5, and even more preferably -0.75 to -0.55. Even more preferred.

The calculated value is obtained by plotting the measured values of the aqueous composition on a graph in which the horizontal axis is the logarithm of the shear rate (s ^-1 ) and the vertical axis is the logarithm of the viscosity (Pa・s). It can be interpreted as representing (an approximate value of) the slope. The slope is negative, and therefore, the smaller the slope, the higher the dependence on shear rate (the viscosity tends to decrease as the shear rate increases). (See also Figure 1)

Note that η ^0.1 and η ¹⁰⁰⁰ are determined by measuring steady flow viscosity using a rheometer. More specifically, a rheometer made by TA Instruments, for example, is used, and an aluminum cone plate (diameter: 60 mm, cone angle: 2°, Gap: 62 μm) is used at 25° C. at a shear rate of 0.01 to The steady flow viscosity was measured in the range of 1,000 s ^-1 , and the steady flow viscosity values (Pa s) at shear rates of 0.1 s ^-1 and 1,000 s ^-1 were expressed as η ^0.1 and η ¹⁰⁰⁰ . do.

Although not particularly limited, η ^0.1 (Pa·s) of the composition of the present disclosure is preferably 10 or more, more preferably 10 to 1000. The upper or lower limits of the range are, for example, 15, 20, 25, 30, 35, 40, 45, 50, 60, 70, 80, 90, 100, 150, 200, 250, 300, 350, 400, 450, 500. , 600, 700, 800, or 900. For example, the range is more preferably 20 to 500, even more preferably 30 to 300, and most preferably 35 to 200. Further, η ¹⁰⁰⁰ (Pa·s) of the composition of the present disclosure is preferably about 0.01 to 1, more preferably about 0.05 to 0.5.

The present inventors have achieved excellent gas barrier properties (particularly water vapor barrier properties) by using an aqueous dispersion of an olefin/α,β-unsaturated carboxylic acid copolymer with a slope of -0.4 or less. We have discovered that it is possible to produce coated paper. The reason why such an effect is obtained is not clear, but it can be speculated as follows, for example. In other words, the fact that the slope is large means that shear force is applied during coating, so the viscosity of the composition is low and it can be applied smoothly, and the composition easily soaks into the paper. The viscosity of the composition quickly increases, making it difficult for it to soak into the paper, and the volatilization of water that has soaked into the paper becomes very slow, resulting in a long drying time (i.e., slow drying). It is speculated that defects such as cracks will be less likely to occur as a result. However, this is just speculation, and we do not wish to be bound by theory.

Copolymer (A) can be prepared by a known method or a method that can be easily derived from a known method. Alternatively, commercially available products can be purchased and used. For example, a commercially available ethylene/α,β-unsaturated carboxylic acid copolymer may be purchased and used. Commercially available products include, for example, Primacol 5980, Primacol 5990 (manufactured by SK Sogo Kagaku),
Examples include Nuclel N1860, Nuclel N1530H, and Nuclel N1560 (manufactured by Mitsui Dow Polychemicals Co., Ltd.).

It is preferable that the carboxyl group (derived from an α,β-unsaturated carboxylic acid) contained in the copolymer (A) is appropriately neutralized.

Usually, when the carboxyl groups of the copolymer (A) are in a free state, the hydrophilicity is relatively low, and when the carboxyl groups are in the salt state, the hydrophilicity is relatively high. Therefore, by neutralizing with a neutralizing agent (base), the neutralized carboxyl groups in the copolymer play the role of an emulsifier, making it possible to produce an aqueous dispersion relatively easily.

The degree of neutralization of the copolymer (A) in the composition of the present disclosure is not particularly limited, but is preferably, for example, 30 to 95 mol%, more preferably 40 to 90 mol%. The degree of neutralization is calculated from the molar amount of the neutralizing agent used relative to the molar amount of α,β-unsaturated carboxylic acid contained in the olefin/α,β-unsaturated carboxylic acid copolymer.

In the composition of the present disclosure and its manufacturing method, for example, ammonia and/or an organic amine can be preferably used as the neutralizing agent (base) for the neutralization. Examples of organic amines include methylamine, ethylamine, diethylamine, diethanolamine, triethanolamine, and the like. Note that ammonia can also be used in the form of, for example, ammonia gas or aqueous ammonia solution.

Further, other bases such as alkali metal hydroxides may be further used as long as the above-mentioned effects of the composition of the present disclosure are not impaired, but they should not be included in the composition of the present disclosure. is preferred. Further, examples of the alkali metal hydroxide include sodium hydroxide, potassium hydroxide, lithium hydroxide, and the like.

Further, the copolymer (A) preferably has an α,β-unsaturated carboxylic acid content of 10 to 25% by mass, more preferably 12 to 23% by mass, and even more preferably 15 to 20% by mass. .

Although not particularly limited, it is preferable that the copolymer (A) has a unit content derived from α,β-unsaturated carboxylic acid of, for example, about 2 to 15 mol%. The upper or lower limit of the range may be, for example, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, or 14 mol%. For example, the range may be about 3 to 12 mol%.

The α, β-unsaturated carboxylic acid content (mass %) and the α, β-unsaturated carboxylic acid-derived unit content (mol %) of the copolymer (A) were measured using an infrared spectrometer (IR). It is determined based on the peak intensity ratio of olefin-derived and carboxylic acid-derived peaks determined by .

Further, the copolymer (A) preferably has a weight average molecular weight of about 10,000 to 1,000,000, more preferably about 10,000 to 500,000, and even more preferably about 11,000 to 200,000. The weight average molecular weight of the copolymer (A) is determined by GPC. Specifically, a sample (copolymer (A)) obtained by heating and dissolving copolymer (A) in THF (tetrahydrofuran) at about 50° C. can be subjected to a column TOSOH TSKgel Multipore HXL-M2 for measurement.

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

The aqueous medium for the composition of the present disclosure is preferably water, and various types of water such as tap water, industrial water, ion-exchanged water, deionized water, and pure water can be used. Particularly preferred is deionized water or pure water.

Note that the composition of the present disclosure may contain other components as long as the effects are not impaired. For example, defoaming agents, viscosity modifiers, pH adjusters, surfactants, antifungal agents, etc., and if necessary, antioxidants, blocking improvers such as fatty acid amides, waxes, and silicone oils, alcohols, etc. May contain.

The composition of the present disclosure is useful, for example, as a binder or a coating agent. The composition of the present disclosure can be applied onto a base and dried to form a film, for example. As the base, for example, paper is preferably mentioned, and food and drink wrapping paper is more preferably mentioned. The film can prevent the food or drink from coming into direct contact with the paper (wrapping paper). Further, the film is preferable because it has little adverse effect on food and drink products.

The present disclosure also relates to a laminate comprising, for example, a paper base and a film on the paper base, the film being formed using the composition of the present disclosure. Preferably included.

The composition of the present disclosure can be prepared, for example, by mixing the copolymer (A), a base (preferably ammonia), and an aqueous medium (preferably water), applying pressure and/or heating as necessary, and dispersing the mixture. If necessary, the copolymer can be prepared by diluting the copolymer with water to a specific concentration.

However, as described above, the composition of the present disclosure is an aqueous dispersion composition in which the calculated value in the above calculation formula is -0.4 or less, and in preparing the aqueous dispersion composition that satisfies such calculated value. When copolymer (A), a base (preferably ammonia), and an aqueous medium (preferably water) are mixed and the copolymer (A) is dispersed, the temperature is raised at a relatively slow rate. It is desirable to mix while

More specifically, it is preferable to raise the temperature at a rate of 1°C/min or less, more preferably at a rate of about 0.01 to 1°C/min, 0.05 to 1°C/min, 0.1 to 1°C/min. It is more preferable to raise the temperature at a rate of 1° C./min or about 0.2 to 1° C./min. If the temperature is increased at a rate of 2° C./min or more, it becomes difficult to obtain an aqueous dispersion composition that satisfies the above calculated values, which is not preferable. Furthermore, it is preferable to raise the temperature to 90° C. or higher (for example, about 90 to 100° C.). Further, after raising the temperature to the desired temperature, it is preferable to carry out mixing while maintaining the temperature for about 1 to 3 hours. By preparing an aqueous composition through such operations, an aqueous dispersion composition that satisfies the above calculated values can be preferably obtained.

Incidentally, in the manufacturing process, a surfactant can be used in order to particularly assist in dispersion, within a range that does not impair the effects of the composition of the present disclosure. An aqueous dispersion composition containing the polymer (A) stably dispersed can be provided.

The present disclosure also includes a laminate including a paper base material and a film on the paper base material, the film being formed using the composition of the present disclosure. do. Preferably, such a laminate is coated paper. Further, the thickness of the film is preferably about 1 to 10 μm, more preferably about 2 to 8 μm, for example. The laminate can be prepared, for example, by applying the composition of the present disclosure onto a paper base and drying it.

The laminate (preferably coated paper) has a water vapor permeability (g/m ² ) measured according to JIS Z 0208, preferably 1000 or less, more preferably 800 or less, and 500 or less. is even more preferable.

Note that in this specification, the term "comprising" includes "consisting essentially of" and "consisting of". Further, the present disclosure includes all arbitrary combinations of the constituent elements described in this specification.

Further, the various characteristics (properties, structures, functions, etc.) described for each embodiment of the present disclosure described above may be combined in any manner in order to specify the subject matter included in the present disclosure. That is, the present disclosure encompasses all subject matter consisting of any and all combinations of the combinable features described herein.

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

<Evaluation method of shear rate dependence>
Steady flow viscosity was measured using a rheometer. More specifically, a rheometer manufactured by TA Instruments was used, and an aluminum cone plate (diameter: 60 mm, cone angle: 2°, Gap: 62 μm) was used at a shear rate of 0.01 to 1000 s ^-1 . Steady flow viscosity was measured.

Then, the steady flow viscosity values η ^0.1 and η ¹⁰⁰⁰ at shear rates of 0.1 s ^-1 and 1,000 s ^-1 are inserted into the following equation to calculate the shear rate dependence of the aqueous dispersion composition (emulsion). did. The smaller the calculated value, the higher the shear rate dependence. The calculated value is preferably -0.4 or less.

Formula: (Logη ^0.1 - Logη ¹⁰⁰⁰ )/(Log0.1-Log1000)

Note that all logarithms in the formula are common logarithms.

<Method for measuring moisture permeability of coated paper>
An aqueous dispersion composition (emulsion) was applied to a high-quality paper having a basis weight of 52 g/m ² to a coating thickness of 5 μm, and dried at 100° C. for 5 minutes to prepare a coated paper. The moisture permeability of the prepared coated paper was measured according to JIS Z 0208. More specifically, a moisture-absorbing material (calcium chloride) was placed in an aluminum cup, coated paper and an O-ring that kept the permeation area constant were layered in order, and the surrounding area was sealed with melted paraffin, and the test conditions ( The sample was placed in a constant temperature and humidity chamber adjusted to a temperature of 40°C (apparatus humidity: 90%), and the increase in mass after 24 hours was measured to calculate moisture permeability. The test jig used was one manufactured by Yasuda Seiki Seisakusho Co., Ltd.

(Example 1)
Ethylene/α,β-unsaturated carboxylic acid copolymer (EAA (ethylene/acrylic acid copolymer); acrylic acid content 20% by mass, melt index 300 g/10 min) was placed in a 1000 ml pressure vessel equipped with a stirrer. 88 g, 6.7 g of 28% aqueous ammonia as a neutralizing agent, and 205.3 g of water were charged and sealed. Thereafter, while stirring at 500 revolutions per minute, the temperature was raised from 25° C. to 95° C. at an average rate of 0.5° C./min, and the inside of the container was kept at 95° C. and stirred for 2 hours. Next, the mixture was cooled to 50° C. at room temperature, and the contents were filtered through an 80-mesh polyethylene mesh to obtain an aqueous dispersion composition.

(Example 2)
Ethylene/α,β-unsaturated carboxylic acid copolymer (EAA (ethylene/acrylic acid copolymer); acrylic acid content 15% by mass, melt index 60 g/10 min) was placed in a 1000 ml pressure vessel equipped with a stirrer. 60 g, 6.5 g of 28% ammonia water as a neutralizing agent, and 233.55 g of water were charged and sealed. Thereafter, while stirring at 500 revolutions per minute, the temperature was raised from 25° C. to 95° C. at an average rate of 0.3° C./min, and the inside of the container was kept at 95° C. and stirred for 2 hours. Next, the mixture was cooled to 50° C. at room temperature, and the contents were filtered through an 80-mesh polyethylene mesh to obtain an aqueous dispersion composition.

(Comparative example 1)
Ethylene/α,β-unsaturated carboxylic acid copolymer (EAA (ethylene/acrylic acid copolymer); acrylic acid content 20% by mass, melt index 300 g/10 min) was placed in a 1000 ml pressure vessel equipped with a stirrer. 88 g, 6.7 g of 28% ammonia water as a neutralizing agent, and 205.33 g of water were charged and sealed. Thereafter, while stirring at 500 revolutions per minute, the temperature was raised from 25° C. to 95° C. at an average rate of 2.0° C./min, and the inside of the container was kept at 95° C. and stirred for 2 hours. Next, the mixture was cooled to 50° C. at room temperature, and the contents were filtered through an 80-mesh polyethylene mesh to obtain an aqueous dispersion composition.

(Comparative example 2)
Ethylene/α,β-unsaturated carboxylic acid copolymer (EAA (ethylene/acrylic acid copolymer); acrylic acid content 20% by mass, melt index 300 g/10 min) was placed in a 1000 ml pressure vessel equipped with a stirrer. 75 g, 6.2 g of sodium hydroxide flakes as a neutralizing agent, and 218.80 g of water were charged and sealed. Thereafter, while stirring at 500 revolutions per minute, the temperature was raised from 25° C. to 95° C. at an average rate of 2.0° C./min, and the inside of the container was kept at 95° C. and stirred for 2 hours. Next, the mixture was cooled to 50° C. at room temperature, and the contents were filtered through an 80-mesh polyethylene mesh to obtain an aqueous dispersion composition.

(Comparative example 3)
Ethylene/α,β-unsaturated carboxylic acid copolymer (EAA (ethylene/acrylic acid copolymer); acrylic acid content 20% by mass, melt index 300 g/10 min) was placed in a 1000 ml pressure vessel equipped with a stirrer. 88 g, 4.0 g of sodium hydroxide flakes as a neutralizing agent, and 221.00 g of water were charged and sealed. Thereafter, while stirring at 500 revolutions per minute, the temperature was raised from 25° C. to 95° C. at an average rate of 2.0° C./min, and the inside of the container was kept at 95° C. and stirred for 2 hours. Next, the mixture was cooled to 50° C. at room temperature, and the contents were filtered through an 80-mesh polyethylene mesh to obtain an aqueous dispersion composition.

In each example, the α,β-unsaturated carboxylic acid content (mass%) in the ethylene/α,β-unsaturated carboxylic acid copolymer is determined by infrared spectroscopy (IR). It was calculated based on the acid-derived peak intensity ratio. Further, the weight average molecular weight of EAA used in each example is about 100,000 or less.

For each of the obtained aqueous dispersion compositions (emulsions), shear rate dependence and coated paper moisture permeability were measured. The above results are shown in Table 1. Table 1 shows the degree of neutralization (from the molar amount of the neutralizing agent used relative to the molar amount of α, β-unsaturated carboxylic acid contained in the ethylene/α, β-unsaturated carboxylic acid copolymer used). Calculation) is also shown.

In addition, Table 2 summarizes the steady flow viscosity values measured in the evaluation of shear rate dependence.

Further, for the aqueous dispersion composition of Example 1 and the aqueous dispersion composition of Comparative Example 1, the relationship between shear rate (Pa·s) and steady flow viscosity (s ⁻¹ ) is graphed and shown in FIG. 1.

Claims

An aqueous dispersion composition of an olefin/α,β-unsaturated carboxylic acid copolymer, the composition comprising:
An aqueous dispersion composition whose calculated value in the following formula is -0.4 or less.
Formula: (Logη 0.1 - Logη 1000 )/(Log0.1-Log1000)
However, η 0.1 indicates the viscosity (Pa・s) at a shear rate of 0.1 s −1 , η 1000 indicates the viscosity (Pa・s) at a shear rate of 1000 s −1 , and the logarithm in the equation is the common logarithm. show.
Furthermore, containing ammonia and/or organic amines,
The aqueous dispersion composition according to claim 1.
The aqueous dispersion composition according to claim 1 or 2, wherein the α,β-unsaturated carboxylic acid content in the olefin/α,β-unsaturated carboxylic acid copolymer is 10 to 25% by mass.
mixing an olefin/α,β-unsaturated carboxylic acid copolymer, a base, and an aqueous medium;
At the time of said mixing, the temperature is raised to 90 °C or higher at a temperature increase rate of 1 °C/min or less,
A method for producing an aqueous dispersion composition of an olefin/α,β-unsaturated carboxylic acid copolymer.
A laminate comprising a paper base material and a film on the paper base material,
A laminate, wherein the film is formed using the aqueous dispersion composition of the olefin/α,β-unsaturated carboxylic acid copolymer according to claim 1 or 2.