JP2006077143A - Aqueous coating composition containing polymer emulsion - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an aqueous coating composition for coating inside of a can imparting a coating film excellent in workability, resistance to steam sterilization completely free from constituents derived from BPA (Bisphenol A) and substantially free from surfactant which impairs resistance of the cured coating film to the steam sterilization after baking and not causing change of flavor and taste of a drink, and to provide a coated can having a coated inner surface coated with the aqueous coating composition for coating inside of a can. <P>SOLUTION: The invention relates to the aqueous coating composition comprising a composite polymer (J) obtained by polymerizing a monomer emulsion (2) comprising a component (A) to be emulsified containing an ethylenic unsaturated monomer (A1), a COOH group containing component (E) containing an acrylic copolymer (E1) having COOH group, a basic compound (F) and water (G) by using a water insoluble polymerization initiator (H), in the presence of an aqueous polymer solution or emulsion (1) comprising a COOH group containing component (B) containing an acrylic copolymer (B1) with 20,000-100,000 of number average molecular weight and containing COOH groups, a basic compound (C) and water (D), wherein the composite polymer (J) has 50-120°C of a glass transition temperature. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an aqueous coating composition, and more particularly to an aqueous coating composition suitably used for coating an inner surface of a can containing a beverage or food. More specifically, the present invention relates to an aqueous coating composition that has excellent hygiene, steam sterilization resistance, processability, adhesion, and low flavor component adsorption performance, and is excellent in flavor retention of contents, and cans using the same The present invention relates to a coated can formed by coating an inner surface.

The BPA type epoxy resin synthesized from bisphenol A (hereinafter abbreviated as BPA) and epichlorohydrin has the function of forming a coating film excellent in steam sterilization resistance, workability and adhesion. It is suitably used for coating paints.
Conventionally, water-dispersed acrylic modified epoxy resins in which a BPA type epoxy resin is modified with an acrylic resin and a carboxyl group or the like is introduced into the molecule are mainly used for water-based coatings for can inner surface coating.

Other than BPA type epoxy resins, examples of resins having processability and adhesion similar to those of BPA type epoxy resins include emulsion type acrylic resins synthesized by emulsion polymerization. Emulsion type acrylic resin synthesized by emulsion polymerization method is generally known to have a very high molecular weight compared to acrylic resin synthesized by solution polymerization method. It is thought that processability and adhesion can be obtained.
However, since a surfactant is generally used in the emulsion polymerization method, the surfactant is contained in the cured coating film. Since this surfactant causes deterioration of the steam sterilization resistance of the cured coating film, at present, an emulsion type acrylic resin synthesized by an emulsion polymerization method has not been used for a paint for coating inner surfaces of cans.

Therefore, instead of using a surfactant that causes deterioration of steam sterilization resistance, instead of using a water-based acrylic polymer having a carboxyl group and a crosslinkable functional group other than a carboxyl group and a base compound, a mixture of acrylic monomers Is dispersed in an aqueous medium in advance to obtain an aqueous dispersion of monomer (pre-emulsion), and the aqueous dispersion of monomer is radically polymerized in the presence of a separately prepared aqueous resin having a carboxyl group ( Hereinafter, a pre-emulsification method) has been proposed (see Patent Document 1: Japanese Patent Application Laid-Open No. 2002-155234).
That is, Patent Document 1 states that a soap-free acrylic resin emulsion obtained by dropwise polymerization of an aqueous dispersion of an acrylic monomer in the presence of an aqueous resin having a carboxyl group can be used in an aqueous coating composition for cans. Are listed.
Patent Document 1 describes an aqueous coating composition for cans that is capable of forming a coating film excellent in processability, adhesion, and boiling resistance.
However, depending on the type of contents, the paint for cans may be subjected to a steam sterilization process that is more severe than boiling. When a can coated with an aqueous coating composition obtained by the method disclosed in Patent Document 1 is steam sterilized, the coating film may be whitened or blistered (dotted peeling).

Moreover, it is disclosed by patent document 1 that it is preferable to form a coating film with a component with low glass transition temperature from a viewpoint of the workability improvement of a cured coating film.
However, when a coating film is formed with a component having a low glass transition temperature, the cured coating film tends to adsorb flavor components other than water contained in the beverage, and has a flavor retention property that changes the aroma and taste of the beverage. There is a problem that decreases.
In addition, when a component with a high glass transition temperature is used, the adsorption performance of the coating film is lowered, and changes in fragrance and taste can be suppressed. However, the stability of the emulsion is lowered, and it becomes easy to generate shakiness or the workability is lowered.
JP 2002-155234 A

  The object of the present invention is to form a good emulsion without using any BPA-derived components, and substantially not using a surfactant that deteriorates the steam sterilization resistance of the cured coating film after baking, An aqueous coating composition for coating the inner surface of a can that is excellent in bactericidal properties, processability, and adhesion, and does not cause a change in the scent or taste of the beverage, and can coat the inner surface of the can. It is to provide a coated can.

  That is, the first invention is a COOH group-containing component (B) containing an acrylic copolymer (B1) having a COOH group having a number average molecular weight of 20,000 to 100,000, a basic compound (C), water (D In the presence of an aqueous solution or emulsion (1) of a polymer containing), an emulsified component (A) containing an ethylenically unsaturated monomer (A1) and an acrylic copolymer (E1) having a COOH group A glass transition temperature of 50 to 120 ° C. formed by radical polymerization of a monomer emulsion (2) containing a COOH-containing component (E), a basic compound (F), and water (G) with a water-insoluble initiator. It is a water-based coating composition characterized by containing the composite polymer (J).

  In the second invention, the ethylenically unsaturated monomer (A1) is at least one amide monomer selected from the group consisting of N-alkoxyalkyl (meth) acrylamide, N-hydroxyalkyl (meth) acrylamide and (meth) acrylamide. A water-based paint composition according to the first invention, characterized by containing a seed.

  The third invention is an amide system in which the acrylic copolymer (B1) having a COOH group is selected from the group consisting of N-alkoxyalkyl (meth) acrylamide, N-hydroxyalkyl (meth) acrylamide and (meth) acrylamide. The water-based coating composition according to any one of the first and second inventions, which contains at least one monomer.

  According to a fourth invention, the acid value of the acrylic copolymer (B1) having a COOH group is 150 to 500 (mgKOH / g), according to any one of the first to third inventions. It is an aqueous coating composition.

  A fifth invention is the water-based paint composition according to any one of the first to fourth inventions, characterized in that it contains at least one component selected from the group consisting of phenol resins and amino resins.

  A sixth invention is the water-based paint composition according to any one of the first to fifth inventions, characterized in that it is for covering the inner surface of a can.

  A seventh invention is a coated can characterized by coating the inner surface of the can with the aqueous paint composition according to any one of the first to sixth inventions.

  The eighth invention relates to a COOH group-containing component (B) containing an acrylic copolymer (B1) having a COOH group having a number average molecular weight of 20,000 to 100,000, a basic compound (C), and water (D). COOH group containing an emulsion component (A) containing an ethylenically unsaturated monomer (A1) and an acrylic copolymer (E1) having a COOH group in an aqueous solution or emulsion (1) of the polymer contained A glass transition temperature characterized by adding a monomer emulsion (2) containing a component (E), a basic compound (F) and water (G), and performing radical polymerization with a water-insoluble initiator (H). It is a manufacturing method of the emulsion of 50-120 degreeC complex polymer (J).

  The present invention is superior in hygiene, steam sterilization resistance, processability, adhesiveness, and can form a coating film that does not cause a change in the scent and taste of beverages, and is excellent in stability. A coating composition can be provided.

The emulsion of the composite polymer (J) contained in the aqueous coating composition of the present invention essentially requires a relatively high molecular weight acrylic copolymer containing a COOH group, instead of using a so-called general surfactant. COOH group-containing component is used as a kind of polymer emulsifier, and an emulsified component (A) containing an ethylenically unsaturated monomer (A1) is converted into a COOH group containing an acrylic copolymer (E1) having a COOH group. The component (E), the basic compound (F), and water (G) are preliminarily formed into a monomer emulsion and then radically polymerized in an aqueous medium. Is.
The composite polymer (J) in the first invention is a state in which the polymer formed from the emulsified component (A) and the COOH group-containing components (B) and (E) are combined, that is, integrated. The water-based coating composition of the first invention, which is a polymer having a specific Tg, can be expressed in a simplified manner that the composite polymer (J) is dispersed in an aqueous medium.

<Emulsified component (A)>
First, the emulsified component (A) will be described.
The emulsified component (A) is mainly composed of a mixture of ethylenically unsaturated monomers (A1), and the mixture is insoluble or hardly soluble in water. Usually, solution polymerization using an organic solvent, interface It is subjected to emulsion polymerization using an activator.
In the present invention, a monomer mixture insoluble or hardly soluble in water is radically polymerized in water using a relatively high molecular weight COOH group-containing component without using a so-called general low molecular weight surfactant. There is a feature. In the present invention, as described above, the emulsified component (A) is used after being previously emulsified with the COOH group-containing component (E).
In addition to the ethylenically unsaturated monomer (A1), the emulsified component (A) is, for example, a polyester resin, an acrylic-modified polyester resin, a cellulose resin, polyvinyl alcohol or a derivative thereof mixed with the monomer (A1). It can also use for radical polymerization as an emulsification component.

Of the emulsified component (A), the ethylenically unsaturated monomer (A1) will be described.
The ethylenically unsaturated monomer (A1) is an ethylenically unsaturated monomer that is emulsified when acrylic emulsion polymerization is performed using an ethylenically unsaturated monomer or a surfactant used in normal acrylic solution polymerization. The thing similar to a monomer can be used.
Examples of the ethylenically unsaturated monomer (A1) include
Ethylenically unsaturated monomers having a carboxyl group such as (meth) acrylic acid, (anhydrous) itaconic acid, (anhydrous) maleic acid,
Methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, hexyl ( Alkyl (meth) acrylates such as (meth) acrylate and ethylhexyl (meth) acrylate,
Hydroxyl groups such as hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, hydroxypentyl (meth) acrylate, and hydroxyhexyl (meth) acrylate An ethylenically unsaturated monomer having
Aromatic monomers such as styrene and methylstyrene,
N-hydroxyalkyl (meth) acrylamides such as N-hydroxymethyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N-hydroxybutyl (meth) acrylamide,
N-methoxymethyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, N- (n-, iso) butoxymethyl (meth) acrylamide, N-methoxyethyl (meth) acrylamide, N-ethoxyethyl (meth) acrylamide N-alkoxyalkyl (meth) acrylamides such as N- (n-, iso) butoxyethyl (meth) acrylamide,
(Meth) acrylamide etc. are mentioned.
The ethylenically unsaturated monomer (A1) contains at least one amide monomer selected from the group consisting of N-alkoxyalkyl (meth) acrylamide, N-hydroxyalkyl (meth) acrylamide and (meth) acrylamide. Is preferred.

When the ethylenically unsaturated monomer (A1) contains at least one amide monomer selected from the group consisting of N-alkoxyalkyl (meth) acrylamide, N-hydroxyalkyl (meth) acrylamide and (meth) acrylamide, A crosslinkable functional group can be introduced into a composite polymer emulsion obtained by radical polymerization of the emulsified component (A).
By introducing a crosslinkable functional group, the composite polymer emulsion has self-crosslinkability. By the baking process after coating, the composite polymer emulsion causes a crosslinking reaction to form a strong coating film.

  The ethylenically unsaturated monomer (A1) does not contain an amide monomer selected from the group consisting of N-alkoxyalkyl (meth) acrylamide, N-hydroxyalkyl (meth) acrylamide and (meth) acrylamide. A crosslinkable functional group derived from the amide monomer as described above using the monomer (A1) and the acrylic copolymer (E1) having a COOH group, which will be described later, and the acrylic copolymer (B1) having a COOH group. If one containing no group is used, an amide-free complex polymer emulsion can be obtained.

<COOH group-containing component (B)>
Next, the COOH group-containing component (B) containing the acrylic copolymer (B1) having a COOH group having a number average molecular weight of 20,000 to 100,000 will be described.
The COOH group-containing component (B) functions as an emulsifier component with respect to the emulsified component (A) as in the later-described COOH group-containing component (E).
The COOH group-containing component (E) described later is a hydrophobic ethylenically unsaturated monomer (A1) or a mixture (A) of an ethylenically unsaturated monomer (A1) and a polyester resin or the like used as needed in advance. It is positioned as an auxiliary emulsifier for allowing the radical polymerization to proceed uniformly and stably.
On the other hand, the COOH group-containing component (B) forms micelles with the emulsified component (A) containing the ethylenically unsaturated monomer (A1) as droplets when radically polymerizing the emulsified component (A). The polymerization is started with the radical polymerization initiator incorporated in the micelle. That is, the COOH group-containing component (B) provides a place for polymerization in water to the ethylenically unsaturated monomer (A1) that is insoluble or hardly soluble in water.
Accordingly, the COOH group-containing component (B) has a great influence on the polymerization rate, molecular weight, particle size, emulsion stability, coating film physical properties, etc., and is therefore positioned as one of the most important components for the present invention.

  The number average molecular weight of the acrylic copolymer (B1) having a COOH group is important to be 20,000 to 100,000, and the number average molecular weight is preferably 30,000 to 70,000. When the number average molecular weight is less than 20,000, the stability of the composite polymer emulsion obtained by polymerizing the monomer emulsion (2) comprising the emulsified component (A) and the COOH group-containing component (E) is inferior. Settling occurs. When the number average molecular weight exceeds 100,000, the viscosity of the aqueous solution or emulsion (1) of the acrylic copolymer (B1) becomes high, so that the emulsion polymerization itself becomes non-uniform and a gel is easily generated.

  As the COOH group-containing component (B) containing the acrylic copolymer (B1) having a COOH group, in addition to the acrylic copolymer (B1), a polyester resin containing a COOH group, an acrylic-modified polyester resin In addition, components that can be dissolved or dispersed in water, such as cellulose resin, polyvinyl alcohol, or a derivative thereof, can also be used.

In general, an emulsifier in emulsion polymerization plays a role of emulsifying a hydrophobic component in an aqueous medium. Therefore, it is essential to have a hydrophilic part and a hydrophobic part.
The acrylic copolymer (B1) having a COOH group has a COOH group as a hydrophilic portion. The acrylic copolymer (B1) having a COOH group is obtained by copolymerizing an ethylenically unsaturated monomer having a COOH group. The ethylenically unsaturated monomer having a COOH group is preferably contained in an amount of at least 10% by weight, more preferably 20 to 80% by weight, based on 100% by weight of the monomer used for copolymerization.
It is also important that the acrylic copolymer (B1) having a COOH group has a hydrophobic portion. Therefore, it is preferable to have an ethylenically unsaturated monomer having an aromatic ring or an ethylenically unsaturated monomer having an alkyl chain having 6 or more carbon atoms in the copolymer component.

  The acrylic copolymer (B1) having a COOH group can be obtained by solution polymerization in a solvent by a usual method. If possible, synthesis by polymerization in an aqueous medium or synthesis by bulk polymerization is possible. It is.

Examples of the ethylenically unsaturated monomer having a COOH group that is a copolymerization component of the acrylic copolymer (B1) having a COOH group include (meth) acrylic acid, (anhydrous) itaconic acid, and (anhydrous) maleic acid. .
When the acrylic copolymer (B1) having a COOH group does not have a crosslinkable functional group other than the COOH group, the acrylic copolymer (B1) is obtained by bulk polymerization without using an organic solvent. Can be synthesized.

In general, emulsion polymerization is often performed in the absence of an organic solvent, and even when an organic solvent is present, it is often preferable that the proportion of the organic solvent in the entire system is not so large. When the proportion of the organic solvent is large, the conversion rate of the polymerization may be deteriorated, or the physical properties of the coating film may be deteriorated.
Therefore, in order to use the acrylic copolymer (B1) obtained by solution polymerization as an emulsifier when radically polymerizing the emulsified component (A), an organic solvent during polymerization of the acrylic copolymer (B1) is used. It is often necessary to distill off.
As a method of distilling off the organic solvent, a method of removing the solvent using a normal decompression method is used.

Moreover, as components other than the ethylenically unsaturated monomer having a COOH group that can constitute the acrylic copolymer (B1) having a COOH group, the same components as the ethylenically unsaturated monomer (A1) can be exemplified.
For example, the acrylic copolymer (B1) having a COOH group contains at least one amide monomer selected from the group consisting of N-alkoxyalkyl (meth) acrylamide, N-hydroxyalkyl (meth) acrylamide and (meth) acrylamide. It can also be set as the copolymer formed by copolymerizing the seed-containing monomer.
An amide monomer selected from the group consisting of N-alkoxyalkyl (meth) acrylamides and N-hydroxyalkyl (meth) acrylamides may undergo a self-crosslinking reaction when forming a cured coating film, or the COOH group-containing component (B). It can also be cross-linked with a COOH group, a phenol resin or the like described later. They also undergo a crosslinking reaction with (meth) acrylamide.
Thereby, the sclerosis | hardenability of a cured coating film and another physical property improve more.

The acid value of the acrylic copolymer (B1) having a COOH group is preferably 150 to 500 (mgKOH / g). More preferably, it is 200-450 (mgKOH / g).
When the acid value is less than 150 (mgKOH / g), there is a disadvantage that the emulsifying power is lowered during the radical polymerization and the emulsion polymerization becomes unstable. When the acid value is greater than 500 (mgKOH / g), the water resistance of the coating film tends to decrease.
In the first invention, the COOH group-containing component (B) is dissolved or dispersed in water using a basic compound (C) and water (D), as will be described later. The monomer emulsion (2) composed of the emulsified component (A) and the COOH group-containing component (E) is added to the solution, but it is preferable that the monomer emulsion (2) be dissolved in water.

<COOH group-containing component (E)>
Next, the COOH group-containing component (E) will be described.
The COOH group-containing component (E) is used for pre-emulsifying the emulsified component (A). The COOH group-containing component (E) is a COOH group-containing component essentially comprising an acrylic copolymer having a COOH group, as in the case of the COOH group-containing component (B), and an acrylic copolymer having a COOH group. In addition to the above, if necessary, a polyester resin or the like can also be contained as in the case of the COOH group-containing component (B).
Examples of the acrylic copolymer (E1) having a COOH group include those similar to the acrylic copolymer (B1) having a COOH group, and can be obtained by the same method.

In the case of the present invention, it is considered that the acrylic copolymer (B1) having a COOH group having a number average molecular weight of 20,000 to 100,000 existing in the reaction vessel mainly forms micelles as a reaction field during radical polymerization. Accordingly, the number average molecular weight of the acrylic copolymer (E1) having a COOH group in the COOH group-containing component (E) used for the pre-emulsification of the component to be emulsified (A) is not particularly limited. Considering easiness and the like, the number average molecular weight is preferably 2000 to 30000, and more preferably 5000 to 20000. If the number average molecular weight is less than 2000, the emulsifying power during pre-emulsification tends to be reduced, which tends to cause lumps and sediment during polymerization. When the number average molecular weight is larger than 30000, the viscosity of the monomer emulsion (2) becomes high and workability at the time of radical polymerization is deteriorated.
The acid value of the acrylic copolymer (E1) having a COOH group in the COOH group-containing component (E) is preferably 20 to 400 (mgKOH / g), and preferably 100 to 300 (mgKOH / g). It is more preferable that When the acid value is less than 20 (mgKOH / g), the emulsifying power during pre-emulsification tends to be reduced, and it tends to cause blisters and sediment during polymerization. When the acid value is larger than 400 (mgKOH / g), the water resistance of the coating film tends to decrease.

<Basic compounds (C), (F)>
In the first invention, the basic compound (C) neutralizes part or all of the COOH groups in the COOH group-containing component (B), and converts the aqueous solution or emulsion (1) of the COOH group-containing component (B). It is used to obtain.
In the first invention, the basic compound (F) neutralizes part or all of the COOH groups in the COOH group-containing component (E), and the neutralized product of the monomer emulsion (A) to be emulsified (A) It is used to obtain 2).

Examples of the basic compounds (C) and (F) used in the present invention include organic amine compounds, ammonia, alkali metal hydroxides, etc. Examples of organic amine compounds include monomethylamine, dimethylamine, Trimethylamine, monoethylamine, diethylamine, triethylamine, monopropylamine, dipropylamine, monoethanolamine, diethanolamine, triethanolamine, N, N-dimethyl-ethanolamine, N, N-diethyl-ethanolamine, 2-dimethylamino- 2-methyl-1-propanol, 2-amino-2-methyl-1-propanol, N-methyldiethanolamine, N-ethyldiethanolanine, monoisopropanolamine, diisopropanolamine triisopropanolamine, etc. It is below.
Examples of the alkali metal hydroxide include lithium hydroxide, sodium hydroxide, and potassium hydroxide.
These basic compounds (C) and (F) are preferably used in an amount of 20 to 70 mol% with respect to 100 mol% of the COOH groups in the COOH group-containing components (B) and (E), respectively.

<Water (D), (G)>
When the composite polymer (J) is polymerized, the water (D) forms an aqueous solution or emulsion (1) of the polymer together with the COOH group-containing component (B) and the basic compound (C). Water (D) is preferably 100 to 1000 parts by weight and more preferably 200 to 600 parts by weight with respect to 100 parts by weight of the emulsified component (A).
Water (G) forms a monomer emulsion (2) together with the emulsified component (A), the COOH group-containing component (E), and the basic compound (F). Water (G) is preferably 1 to 50 parts by weight and more preferably 5 to 30 parts by weight with respect to 100 parts by weight of the emulsified component.

<Monomer emulsion (2)>
The monomer emulsion (2) used in the present invention will be described. As described above, the monomer emulsion (2) is a pre-emulsifier for the COOH group-containing component (E) when radically polymerizing the emulsified component (A), which essentially contains the ethylenically unsaturated monomer (A1) that is hydrophobic. As a pre-emulsion in advance using a basic compound (F) and water (G), and used when obtaining a composite polymer (J) emulsion described later.
(A), (E), (F), and (G) can be mixed at once, but the COOH group-containing component (E) is neutralized with the basic compound (F) in advance to form water (G). It is preferable to dissolve or disperse and emulsify the emulsified component (A) with this neutralized aqueous solution or dispersion. At the time of emulsification, from the viewpoint of the stability of the dispersion state of the monomer emulsion (2), it is preferable to stir at high speed or to apply a high share.

  The emulsified component (A) containing the ethylenically unsaturated monomer (A1) contains a COOH group-containing component (B), a basic compound (C), and water (D) as it is without making it a pre-emulsion. Although it can be added to an aqueous solution or emulsion (1) of the polymer to be radically polymerized, it is easier to obtain an emulsion having a smaller particle diameter if it is pre-emulsified and added as a monomer emulsion (2) in advance. In particular, when the emulsified component (A) contains a hydrophobic resin such as a polyester resin in addition to the ethylenically unsaturated monomer (A1), a stable emulsion is more likely to be obtained when the pre-emulsion is used.

  A water-soluble solvent can be added for the purpose of assisting emulsification when the monomer emulsion (2) is obtained. In general, emulsion polymerization is often performed in the absence of a solvent, but a water-soluble solvent may serve to supplement emulsification.

<Polymerization initiator (H)>
The polymerization initiator used in the present invention will be described. The polymerization initiator is roughly classified into a water-soluble initiator and a water-insoluble initiator. Each polymerization initiator reacts with an ethylenically unsaturated monomer to produce a polymer that is a collection of molecules of various degrees of polymerization. Focusing on molecules having a relatively low degree of polymerization, a large difference appears in the properties when a water-soluble initiator is used and when a water-insoluble initiator is used.
When a water-soluble initiator is used, the molecule produced as a result of polymerization has a hydrophilic portion and a hydrophobic portion, and exhibits a kind of surfactant property. Such a surfactant property appears remarkably in a molecule having a relatively low degree of polymerization contained in the polymer. As a result, the coating film formed from the coating containing the composite polymer obtained using the water-soluble initiator has a surfactant-like nature of the relatively low degree of polymerization contained in the composite polymer. When retort processing, it is easy to whiten.
On the other hand, when a water-insoluble initiator is used, the molecule produced as a result of polymerization does not have a hydrophilic portion and a hydrophobic portion, so compared to using a water-soluble initiator. A coating film excellent in retort resistance, specifically, a coating film that is not easily whitened even by retort treatment can be formed.
Moreover, in the system which can take an emulsion structure like this invention, the influence on the viscosity of an initiator composition is also large. When a water-soluble initiator is used, molecules with a low degree of polymerization rich in surfactant properties are located on the surface of the polymer particles constituting the emulsion, and molecules with a low degree of polymerization protrude into the liquid medium water. Viscosity. On the other hand, when a water-insoluble initiator is used, the polymer particles do not exhibit surfactant properties, so a low-viscosity emulsion can be obtained, and because of the low viscosity, high solidification (high solid differentiation) is achieved. It becomes possible.

The radical polymerization initiator can be contained in the emulsified component (A), can be contained in the reaction tank together with the COOH group-containing component (B), or the like. A radical polymerization initiator may be separately added to the reaction vessel when or after the addition. The polymerization initiator may be added intermittently or continuously, or may be added all at once.
Examples of water-insoluble initiators include cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, ketone peroxide such as methylcyclohexanone peroxide, acetylacetone peroxide, and 1,1 bis (t-butylperoxy). 3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 2,2-bis (t-butylperoxy) octane, n-butyl-4,4-bis (t-butyl) Peroxy) valerate, peroxyketals such as 2,2-bis (t-butylperoxy) butane, di-t-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, α, α'-bis (T-Butylperoxy-i-propyl) benzene, 2,5-dimethyl 2,5-di (t-butylperoxy) hexane, 2,5-dimethyl2,5-di (t-butylperoxy) hexyne-3 and other dialkyl peroxides, acetyl peroxide, i-butyryl peroxide, Diacyl peroxides such as octanoyl peroxide decanoyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, oxalic acid peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, di- i-propyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-n-propyl peroxydicarbonate, bis- (4-t-butylcyclohexyl) peroxydicarbonate, dimyristyl peroxydicarbonate, The Peroxydicarbonates such as 2-ethoxyethyl peroxydicarbonate, dimethoxy-i-propyl peroxydicarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate, diallyl peroxydicarbonate, t-butyl Peroxyacetate, t-butylperoxy-i-butyrate, t-butylperoxypivalate, cumylperoxyneodecanoate, t-butylperoxylaurate, t-butylperoxybenzoate, cumylperoxyoctate Various peroxide initiators such as peroxyesters such as t-hexylperoxypivalate and cumylperoxyneohexanoate,

  Azobis-i-butyronitrile, azobismethylbutyronitrile, azobis- (2,4-dimethylvaleronitrile), 2,2′-azobis- (4-methoxy-2,4-dimethylvaleronitrile), 1,1 ′ Various azo initiators such as azobis- (cyclohexane-1-carbonitrile) and dimethyl 2,2′-azobisisobutyrate are used, and peroxide initiators are preferable.

<Composite polymer (J)>
As described above, the composite polymer (J) in the present invention is formed from the emulsified component (A), the COOH group-containing component (B), and the COOH group-containing component (E).

  In the present invention, it is important that the Tg of the composite polymer (J) is 50 to 120 ° C, and Tg is more preferably 60 to 100 ° C. When an aqueous coating composition containing a composite polymer (J) having a Tg of less than 50 ° C. is used for inner coating of a beverage can or the like, the flavor components of the contents are adsorbed, and the taste and aroma of the contents change. A decrease in flavor retention occurs. On the other hand, in the case of an aqueous coating composition containing a composite polymer (J) having a Tg exceeding 120 ° C., the processability of the coating film tends to be inferior.

In the case of the first invention, the Tg of the composite polymer (J) can be determined according to a conventional method using each Tg of the constituent components and the composition ratio. For example, an acrylic copolymer (B1) having a COOH group not containing a polyester resin or the like as an emulsifier component but using only an ethylenically unsaturated monomer (A1) without containing a polyester resin or the like as an emulsified component (A). In the case of the first invention using only (E1), each monomer constituting the acrylic copolymer (B1), each monomer constituting the acrylic copolymer (E1), and an ethylenically unsaturated monomer From the Tg of each homopolymer that can be formed from (A1) and the composition ratio of each monomer constituting the composite polymer, it can be determined by calculation according to a conventional method.
In addition, when a polyester resin or the like is contained as an emulsified component (A) or an emulsifier component, it is similarly determined based on the Tg of the polyester resin or the like and the ratio of the polyester resin or the like contained in the composite polymer. it can.

That is, in other words, in the present invention, the Tg of the entire composite polymer (J) is 50 to 50 by controlling the Tg and composition ratio of the emulsified component (A), the COOH group-containing component (B), and (E). It is important to control the temperature to be 120 ° C.
The Tg of the polymer that can be formed from the emulsified component (A) that is considered to mainly constitute the core portion of the composite polymer is the emulsifier component (B) and (E) that are considered to mainly constitute the shell portion of the composite polymer. It is preferable that it is relatively higher than the Tg in view of the corrosion resistance and adhesion of the cured coating film. Specifically, the Tg of the composite polymer (J) and the entire polymer composition is 50 to 120 ° C., and the Tg of the polymer that can be formed from the emulsified component (A) is 50 to 130 ° C., and the emulsifier component (B ) And (E) each Tg is preferably 30 to 90 ° C.

In general, emulsion polymerization in which a monomer is polymerized using an emulsifier micelle in an aqueous medium can obtain a high molecular weight polymer that cannot be obtained by solution polymerization because of its unique polymerization mechanism.
Also in the case of the present invention, the composite polymer (J) is a composite polymer that is higher than the case of mere solution polymerization, although the Tg required from the components and compositions constituting these is relatively high at 50 to 120 ° C. Since (J) has a high molecular weight, as a result, the aqueous coating composition containing the composite polymer (J) was able to form a coating film with good processability and low flavor component adsorptivity. It is considered a thing.

In the present invention, the COOH group-containing component (B) is preferably 5 to 300 parts by weight, more preferably 10 to 200 parts by weight, with respect to 100 parts by weight of the emulsified component (A). More preferably, it is -100 weight part.
When the amount of COOH group-containing component (B), which is an emulsifier component containing a relatively high molecular weight COOH group-containing acrylic copolymer (B1), relative to 100 parts by weight of the emulsified component (A) is less than 5 parts by weight, The emulsified component (A) and the composite polymer (J) after polymerization tend to be difficult to be emulsified. Moreover, when there are more COOH group containing components (B) which are emulsifier components with respect to 100 weight part of emulsified components (A) than 300 weight part, the improvement of the workability of the coating film after baking hardening cannot be expected so much.
The emulsified component (A) is a component having a very high molecular weight by radical polymerization, and this contributes to the improvement of the workability of the cured coating film. Therefore, when the amount of the COOH group-containing component (B) as an emulsifier component is more than 300 parts by weight, the emulsified component (A) is relatively reduced, and as a result, it is difficult to expect improvement in the workability of the cured coating film. .

In the present invention, the COOH group-containing component (E) is preferably 0.1 to 50 parts by weight and preferably 0.5 to 20 parts by weight with respect to 100 parts by weight of the emulsified component (A). More preferred.
As described above, the COOH group-containing component (E) functions as an emulsifier for pre-emulsifying the emulsified component (A) in advance. When the COOH group-containing component (E) is less than 0.1 parts by weight, the stability of the monomer emulsion (2) is deteriorated and the particle diameter of the composite polymer tends to be increased. When the amount of the COOH group-containing component (E) is more than 50 parts by weight, the viscosity of the monomer emulsion (2) becomes high, and the coating workability tends to deteriorate.

  The aqueous coating composition of the present invention further includes phenol resin, amino resin, polyvinyl alcohol in addition to the above-mentioned composite polymer (J) emulsion for the purpose of improving the curability and adhesion of the coating film as necessary. One or more curing agents such as polyvinyl alcohol derivatives can be added.

  The phenol resin and amino resin can react with the COOH group in the COOH group-containing components (B) and (E) in addition to the self-crosslinking reaction. When the emulsified component (A), the COOH group-containing component (B), or (E) has an OH group, the phenol resin or amino resin can also react with these OH groups. Further, when the ethylenically unsaturated monomer (A1) contains an amide monomer or the acrylic copolymer (B1) or (E1) has a crosslinkable functional group derived from the amide monomer, a phenol resin And amino resins can also react with these crosslinkable functional groups.

Examples of the phenol resin used in the present invention include trifunctional phenol compounds such as coalic acid, m-metacresol and 3,5-xylenol, and bifunctional phenol compounds such as o-cresol, p-cresol and p-tert-butylphenol. A product obtained by reacting formaldehyde with an alkali catalyst.
As the amino resin used in the present invention, urea, melamine, and benzoguanamine are added with formalin.
As the phenol resin and amino resin, those obtained by etherifying some or all of the added methylol groups with alcohols having 1 to 12 carbon atoms are also preferably used.
When using a phenol resin or an amino resin, it is preferable to add 0.5 to 20 parts by weight, more preferably 2 to 10 parts by weight, based on 100 parts by weight of the resin solid content of the composite polymer emulsion. .

If necessary, a lubricant such as wax may be added to the aqueous coating composition of the present invention for the purpose of preventing the coating film from being damaged in the can-making process.
Examples of waxes include animal and plant waxes such as carnauba wax, lanolin wax, palm oil, candelilla wax, and rice wax, petroleum waxes such as paraffin wax, microcrystalline wax, and petrolatum, polyolefin wax, and Teflon (registered trademark) wax. A synthetic wax or the like is preferably used.

A hydrophilic organic solvent can be added to the aqueous coating composition of the present invention for the purpose of improving paintability.
Examples of hydrophilic organic solvents include ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol mono (iso) propyl ether, ethylene glycol di (iso) propyl ether, ethylene glycol mono (iso ) Butyl ether, ethylene glycol di (iso) butyl ether, ethylene glycol mono-tert-butyl ether, ethylene glycol monohexyl ether, 1,3-butylene glycol-3-monomethyl ether, 3-methoxybutanol, 3-methyl-3-methoxybutanol , Diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl Ether, diethylene glycol diethyl ether, diethylene glycol mono (iso) propyl ether, diethylene glycol di (iso) propyl ether, diethylene glycol mono (iso) butyl ether, diethylene glycol di (iso) butyl ether, diethylene glycol monohexyl ether, diethylene glycol dihexyl ether, triethylene glycol dimethyl ether, Propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono (iso) propyl ether, propylene glycol mono (iso) butyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol di (iso) propyl ether, Pyrene glycol di (iso) butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono (iso) propyl ether, dipropylene glycol mono (iso) butyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether Various ether alcohols or ethers such as diethylene glycol di (iso) propyl ether and dipropylene glycol di (iso) butyl ether;
Alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol, isobutyl alcohol, sec-butyl alcohol, tert-butyl alcohol, furfuryl alcohol;
Ketones such as methyl ethyl ketone, dimethyl ketone, diacetone alcohol;
Glycols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol;
Examples include esters or ester alcohols such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, 1-methoxy-2-propyl acetate, and propylene glycol monomethyl ether acetate, and these are used in combination of one or more. But you can use it.

  In addition, for the purpose of improving the paintability, the water-based coating composition of the present invention may contain a hydrophobic organic solvent, various auxiliary agents such as a surfactant and an antifoaming agent.

The aqueous coating composition of the present invention can be widely used not only for the following cans but also for general metal materials or metal products, etc., and is suitably used as a coating for inner and outer surfaces of cans containing beverages and foods, It is particularly suitable for can inner coating.
As the material of the can, aluminum, tin-plated steel plate, chrome-treated steel plate, nickel-treated steel plate or the like is used, and these materials may be subjected to surface treatment such as zirconium treatment or phosphoric acid treatment.

As a coating method of the aqueous coating composition of the present invention, spray coating such as air spray, airless spray, electrostatic spray and the like is desirable, but roll coater coating, dip coating, electrodeposition coating, and the like can also be applied.
The water-based paint composition of the present invention can form a film even after the volatile components are volatilized after being applied, but in order to obtain excellent steam sterilization resistance, workability, and adhesion, it is better to add a baking process. good. As conditions for baking, baking at a temperature of 150 ° C. to 280 ° C. for 10 seconds to 30 minutes is desirable.

  The present invention will be described below with reference to synthesis examples, comparative synthesis examples, examples, and comparative examples. In the examples, “part” represents “part by weight” and “%” represents “% by weight”.

[Synthesis Example 1] Synthesis of an acrylic copolymer (B1) having a COOH group 200 parts of n-butanol was charged in a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a dropping tank, and a nitrogen gas introduction tube. The temperature was raised to 90 ° C. While maintaining the temperature in the reaction vessel at 90 ° C., a mixture composed of 80 parts of methacrylic acid, 70 parts of styrene, 40 parts of ethyl acrylate, 10 parts of N-butoxymethylacrylamide and 2 parts of benzoyl peroxide was added from the dropping tank over 4 hours. Continuous dripping.
After 1 hour and 2 hours from the end of dropping, 0.2 parts of benzoyl peroxide was added, and the reaction was continued for 3 hours from the end of dropping. The number average molecular weight was 25000, the glass transition temperature was 75 ° C., the acid value was 261 (mgKOH / g ), An acrylic copolymer having a solid content of 50% was obtained.
Next, 24.8 parts of dimethylethanolamine was added and stirred for 10 minutes, and then 775 parts of ion-exchanged water was added for water dispersion.
Thereafter, a total of 400 parts of n-butanol and ion exchange water were distilled off under reduced pressure to obtain an aqueous solution of an aqueous acrylic copolymer having a COOH group having a nonvolatile content of 25%. This is designated as an aqueous acrylic copolymer (B1) aqueous solution.

[Synthesis Example 2] Synthesis of Acrylic Copolymer (B2) Having COOH Group In a reaction vessel equipped with a stirrer, thermometer, reflux condenser, dropping tank and nitrogen gas introduction tube, 100 parts of ethylene glycol monobutyl ether, ions 100 parts of exchange water was charged and the temperature was raised to 90 ° C. While maintaining the temperature in the reaction vessel at 90 ° C., a mixture of 96 parts of methacrylic acid, 40 parts of styrene, 54 parts of ethyl acrylate, 10 parts of N-butoxymethylacrylamide and 2 parts of benzoyl peroxide was added from the dropping tank over 4 hours. Continuous dripping.
After 1 hour and 2 hours from the end of dropping, 0.2 part of benzoyl peroxide was added, and the reaction was continued for 3 hours from the end of dropping. The number average molecular weight was 55000, the glass transition temperature was 66 ° C., the acid value was 313 (mgKOH / g ), An acrylic copolymer having a solid content of 50% was obtained.
Next, after adding 29.8 parts of dimethylethanolamine and stirring for 10 minutes, 370.2 parts of ion-exchanged water was added to disperse in water, and an aqueous acrylic copolymer having a COOH group having a nonvolatile content of 25%. An aqueous solution of was obtained. This is designated as an aqueous acrylic copolymer (B2) aqueous solution.

[Synthesis Example 3] Synthesis of Acrylic Copolymer (E1) Having COOH Group 200 parts of n-butanol was charged into a reaction vessel equipped with a stirrer, thermometer, reflux condenser, dropping tank and nitrogen gas introduction tube. The temperature was raised to 105 ° C. While maintaining the temperature in the reaction vessel at 105 ° C., a mixture of 80 parts of methacrylic acid, 70 parts of styrene, 40 parts of ethyl acrylate, 10 parts of N-butoxymethylacrylamide and 10 parts of benzoyl peroxide was added from the dropping tank over 4 hours. Continuous dripping.
1.0 part of benzoyl peroxide was added after 1 hour and 2 hours from the end of the dropping, and the reaction was continued for 3 hours after the end of the dropping. The number average molecular weight was 5000, the glass transition temperature was 75 ° C., the acid value was 261 (mgKOH / g ), An acrylic copolymer having a solid content of 50% was obtained.
Next, 24.8 parts of dimethylethanolamine was added and stirred for 10 minutes, and then 642 parts of ion-exchanged water was added for water dispersion.
Thereafter, a total of 400 parts of n-butanol and ion-exchanged water were distilled off under reduced pressure to obtain an aqueous acrylic copolymer aqueous solution having a COOH group having a nonvolatile content of 30%. Let this be aqueous | water-based acrylic copolymer (E1) aqueous solution.

[Synthesis Example 1 for Comparative Example] Synthesis of Acrylic Copolymer (B3) Having COOH Group In a reaction vessel equipped with a stirrer, thermometer, reflux condenser, dropping tank, and nitrogen gas introduction tube, 200 parts of n-butanol The temperature was raised to 105 ° C. While maintaining the temperature in the reaction vessel at 105 ° C., a mixture comprising 76 parts of methacrylic acid, 30 parts of styrene, 84 parts of ethyl acrylate, 10 parts of N-butoxymethylacrylamide and 4 parts of benzoyl peroxide was added from the dropping tank over 4 hours. Continuous dripping.
After 1 hour and 2 hours from the end of the dropping, 0.4 parts of benzoyl peroxide was added, and the reaction was continued for 3 hours after the end of the dropping. The number average molecular weight was 10000, the glass transition temperature was 43 ° C., the acid value was 248 (mgKOH / g ), An acrylic copolymer having a solid content of 50% was obtained.
Next, 23.6 parts of dimethylethanolamine was added and stirred for 10 minutes, and then 776 parts of ion exchange water was added to disperse in water.
Thereafter, a total of 400 parts of n-butanol and ion exchange water were distilled off under reduced pressure to obtain an aqueous acrylic copolymer aqueous solution having a COOH group having a nonvolatile content of 25%. This is designated as an aqueous acrylic copolymer (B3) aqueous solution.

[Synthesis Example 2 for Comparative Example] Synthesis of Acrylic Copolymer (E2) Having COOH Group In a reaction vessel equipped with a stirrer, thermometer, reflux condenser, dropping tank and nitrogen gas inlet tube, 200 parts of n-butanol The temperature was raised to 105 ° C. While maintaining the temperature in the reaction vessel at 105 ° C., a mixture of 80 parts of methacrylic acid, 70 parts of styrene, 40 parts of ethyl acrylate, 10 parts of N-butoxymethylacrylamide and 10 parts of benzoyl peroxide was added from the dropping tank over 4 hours. Continuous dripping.
After 1 hour and 2 hours from the end of dropping, 3.0 parts of benzoyl peroxide was added, respectively, and the reaction was continued for 3 hours from the end of dropping. The number average molecular weight was 1500, the glass transition temperature was 75 ° C. ), An acrylic copolymer having a solid content of 50% was obtained.
Next, 24.8 parts of dimethylethanolamine was added and stirred for 10 minutes, and then 642 parts of ion-exchanged water was added for water dispersion.
Thereafter, a total of 400 parts of n-butanol and ion-exchanged water were distilled off under reduced pressure to obtain an aqueous acrylic copolymer aqueous solution having a COOH group having a nonvolatile content of 30%. This is designated as an aqueous acrylic copolymer (E2) aqueous solution.

[Example 1]
The COOH group-containing acrylic copolymer (E1) aqueous solution obtained in Synthesis Example 3 (3.3 parts) (solid content: about 1.0 part) and ion-exchanged water (10.7 parts) were mixed, and styrene (39.0 parts) was mixed there. A monomer emulsion (2-1) was prepared by adding and stirring a mixture of ethylenically unsaturated monomers consisting of 23.5 parts of ethyl acrylate and 7.5 parts of N-butoxymethylacrylamide.
In a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a dropping tank, and a nitrogen gas introduction tube, 116 parts of COOH group-containing acrylic copolymer (B1) aqueous solution (solid content 29 parts) obtained in Synthesis Example 1 and 80 parts of ion-exchanged water was charged, and the temperature was raised to 90 ° C. with stirring while introducing nitrogen gas.
Next, the above-mentioned monomer emulsion (2-1) is charged into the dropping tank 1, and 0.2 part of benzoyl peroxide dissolved in 6 parts of toluene is charged into the dropping tank 2, and each of them is simultaneously added to the reaction vessel over 3 hours. While maintaining the temperature at 90 ° C., the solution was added dropwise with stirring to obtain a composite polymer emulsion having a theoretical Tg of 54 ° C.
Thereafter, 113.8 parts of ion-exchanged water, 50 parts of n-butanol and 50 parts of ethylene glycol monobutyl ether were added, the contents were taken out by filtration through a 5 μm filter, and an aqueous coating composition (1%) having a nonvolatile content of 20%. )

[Example 2]
A COOH group-containing acrylic copolymer (E1) aqueous solution obtained in Synthesis Example 3 (3.3 parts) (solid content of about 1.0 part) and ion-exchanged water (10.7 parts) were mixed, and 55 parts of styrene and acrylic resin were mixed there. A monomer emulsion (2-2) was prepared by adding and stirring a mixture of ethylenically unsaturated monomers consisting of 7.5 parts of ethyl acid and 7.5 parts of N-butoxymethylacrylamide.
In a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a dropping tank, and a nitrogen gas introduction tube, 116 parts of COOH group-containing acrylic copolymer (B1) aqueous solution (solid content 29 parts) obtained in Synthesis Example 1 and 80 parts of ion-exchanged water was charged, and the temperature was raised to 90 ° C. with stirring while introducing nitrogen gas.
Next, the above-mentioned monomer emulsion (2-2) is charged into the dropping tank 1, and 0.2 part of benzoyl peroxide dissolved in 6 parts of toluene is charged into the dropping tank 2, and each of them in the reaction vessel is simultaneously taken for 3 hours. While maintaining the temperature at 90 ° C., the solution was added dropwise with stirring to obtain a composite polymer emulsion having a theoretical Tg of 77 ° C.
Thereafter, 113.8 parts of ion-exchanged water, 50 parts of n-butanol and 50 parts of ethylene glycol monobutyl ether were added, and the content was taken out by filtration through a 5 μm filter. The aqueous coating composition (2 )

[Example 3]
In the same manner as in Example 1, except that the COOH group-containing acrylic copolymer (B2) aqueous solution obtained in Synthesis Example 2 was used instead of the COOH group-containing acrylic copolymer (B1) aqueous solution, the polymer composition An aqueous coating composition (3) having a theoretical Tg of 51 ° C. and a non-volatile content of 20% was obtained.

[Example 4]
A polymer composition having a theoretical Tg of 54 ° C. and a non-volatile content of 20% was prepared in the same manner as in Example 1 except that 2,2′-azobisisobutyronitrile was used instead of benzoyl peroxide. A coating composition (4) was obtained.

[Example 5]
The aqueous COOH group-containing acrylic copolymer (E1) obtained in Synthesis Example 3 (3.3 parts) (solid content: about 1.0 part) and ion-exchanged water (10.7 parts) were mixed, and 27.8 parts of styrene were mixed there. The monomer emulsion (2-3) was prepared by adding and stirring a mixture of ethylenically unsaturated monomers consisting of 16.8 parts of ethyl acrylate and 5.4 parts of N-butoxymethylacrylamide.
In a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a dropping tank, and a nitrogen gas introduction tube, 200 parts of COOH group-containing acrylic copolymer (B1) aqueous solution obtained in Synthesis Example 1 (solid content 49 parts) and 16 parts of ion-exchanged water was charged, and the temperature was raised to 90 ° C. with stirring while introducing nitrogen gas.
Next, the monomer emulsion (2-3) is charged into the dropping tank 1, and 0.2 part of benzoyl peroxide dissolved in 6 parts of toluene is charged into the dropping tank 2, and simultaneously in the reaction vessel over 3 hours. While maintaining the temperature at 90 ° C., the solution was added dropwise with stirring to obtain a composite polymer emulsion having a theoretical Tg of 59 ° C.
Thereafter, 113.8 parts of ion-exchanged water, 50 parts of n-butanol and 50 parts of ethylene glycol monobutyl ether were added, and the content was removed by filtration through a 5 μm filter. )

[Example 6]
To 33 parts (solid content: about 10 parts) of the COOH group-containing acrylic copolymer (E1) aqueous solution obtained in Synthesis Example 3, 39.0 parts of styrene, 23.5 parts of ethyl acrylate, N-butoxymethylacrylamide, 7. A monomer emulsion (2-4) was prepared by adding and stirring 5 parts of a mixture of ethylenically unsaturated monomers.
In a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a dropping tank, and a nitrogen gas introduction tube, 80 parts of COOH group-containing acrylic copolymer (B1) aqueous solution (solid content 20 parts) obtained in Synthesis Example 1 and 97 parts of ion-exchanged water was charged, and the temperature was raised to 90 ° C. with stirring while introducing nitrogen gas.
Next, the monomer emulsion (2-4) is charged into the dropping tank 1, and 0.2 part of benzoyl peroxide dissolved in 6 parts of toluene is charged into the dropping tank 2, and each of them is simultaneously added to the reaction vessel over 3 hours. While maintaining the temperature at 90 ° C., the solution was added dropwise with stirring to obtain a composite polymer emulsion having a theoretical Tg of 54 ° C.
Thereafter, 113.8 parts of ion-exchanged water, 50 parts of n-butanol and 50 parts of ethylene glycol monobutyl ether were added, the contents were taken out by filtration through a 5 μm filter, and an aqueous coating composition having a nonvolatile content of 20% (6 )

[Example 7] (Phenolic resin added)
In a normal state where 200 parts of the aqueous coating composition (1) obtained in Example 1 was stirred, 8 parts of a 20% butanol solution of PR-C-101 (Sumitomo Bakelite Co., Ltd., phenol resin) was added, The content was removed by filtration through a 5 μm filter to obtain an aqueous coating composition (7) having a nonvolatile content of 20%.

[Example 8] (Addition of amino resin)
8 parts of 20% ethylene glycol monobutyl ether solution of Mycoat 106 (manufactured by Nippon Cytec Co., Ltd., amino resin) was added in a normal state where 200 parts of the aqueous coating composition (1) obtained in Example 1 was stirred. The content was removed by filtration through a 5 μm filter to obtain an aqueous coating composition (8) having a nonvolatile content of 20%.

[Comparative Example 1]
The aqueous COOH group-containing acrylic copolymer (E1) obtained in Synthesis Example 3 (3.3 parts) (solid content: about 1.0 part) and ion-exchanged water (10.7 parts) were mixed, and 23.5 parts of styrene were mixed there. A monomer emulsion (2-5) was prepared by adding and stirring a mixture of ethylenically unsaturated monomers consisting of 39 parts of ethyl acrylate and 7.5 parts of N-butoxymethylacrylamide.
In a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a dropping tank, and a nitrogen gas introduction tube, 116 parts of COOH group-containing acrylic copolymer (B1) aqueous solution (solid content 29 parts) obtained in Synthesis Example 1 and 80 parts of ion-exchanged water was charged, and the temperature was raised to 90 ° C. with stirring while introducing nitrogen gas.
Next, the monomer emulsion (2-5) is charged into the dropping tank 1, and 0.2 part of benzoyl peroxide dissolved in 6 parts of toluene is charged into the dropping tank 2, and each of them in the reaction vessel is simultaneously taken for 3 hours. While maintaining the temperature at 90 ° C., the solution was added dropwise with stirring to obtain a composite polymer emulsion having a theoretical Tg of 33 ° C.
Thereafter, 113.8 parts of ion-exchanged water, 50 parts of n-butanol and 50 parts of ethylene glycol monobutyl ether were added, and the content was taken out by filtration through a 5 μm filter. )

[Comparative Example 2]
In the same manner as in Example 1, except that the COOH group-containing acrylic copolymer (B3) aqueous solution obtained in Comparative Synthesis Example 1 was used instead of the COOH group-containing acrylic copolymer (B1) aqueous solution, the polymer An aqueous coating composition (10) having a theoretical Tg of 45 ° C. and a nonvolatile content of 20% was obtained.

[Comparative Example 3]
In the same manner as in Example 1, except that the COOH group-containing acrylic copolymer (E2) aqueous solution obtained in Comparative Synthesis Example 2 was used instead of the COOH group-containing acrylic copolymer (E1) aqueous solution, the polymer An aqueous coating composition (11) having a theoretical Tg of 54 ° C. and a nonvolatile content of 20% was obtained.

[Comparative Example 4]
A water-based coating composition (12) having a theoretical Tg of 54 ° C. and a non-volatile content of 20% was obtained in the same manner as in Example 1 except that ammonium persulfate was used instead of benzoyl peroxide. .

[Evaluation of coating film]
Using each of the aqueous coating compositions obtained in Examples 1 to 8 and Comparative Examples 1 to 4, it was applied to an aluminum plate having a thickness of 0.26 mm so as to have a thickness of 5 to 6 μm, and a gas oven was used. A test panel for evaluation was obtained by baking at an atmospheric temperature of 200 ° C. for 3 minutes, and the performance of the coating film was evaluated as follows. The results are shown in Table 2.
Each evaluation method will be described below.

<Appearance of coating film> The test panel is visually evaluated.
(Double-circle): A coating film is smooth and there is no fuzz and foaming.
○: Slightly fine but has no problem in practical use.
Δ: There are many irregularities in the coating film, and there is a problem in practical use.
X: Remarkably uneven on the entire surface of the coating film.

<Curing property> Gauze is wound around a 2 pound hammer, impregnated with MEK, reciprocated on the coating film of the test panel, and the number of times until the underlying aluminum is exposed is determined.
◎: 200 times or more ○: 100 times or more and less than 200 times Δ: 50 times or more and less than 100 times x: Less than 50 times

<Corrosion resistance> The test panel was cut to 40 × 80 mm, the coating film was made outside (convex), DuPont impact (1/2 inch, 500 g, 30 cm) was applied, and then the test panel was immersed in a commercially available sports drink. The retort treatment was performed in a retort kettle at 125 ° C. for 30 minutes. Then, it preserve | saved at 50 degreeC for 3 days with being immersed. After 4 days, it was taken out and evaluated for blisters on the flat surface portion and DuPont impact portion.
◎: No blister occurred ○: Blister occurred in DuPont impact area, less than 5mm △: Blister occurred in DuPont impact area, 5mm or more ×: Blister occurred in flat area

<Retort resistant adhesion> Retort treatment was performed in a retort kettle at 130 ° C for 1 hour while the test panel was immersed in water. After cross-cutting the coated surface, a cellophane pressure-sensitive adhesive tape was applied, and the coated surface was evaluated after peeling strongly.
◎: No peeling ○: Less than 5% peeling Δ: 5-50% peeling ×: 50% or more peeling

<Retort whitening resistance> While the test panel was immersed in water, retort treatment was performed at 130 ° C. for 1 hour in a retort kettle, and the appearance of the coating film was visually evaluated.
◎: Untreated coating and no change ○: Very thin whitening △: Slightly white ×: Remarkably whitening

<Processability> The test panel is cut into a size of 30 mm x 50 mm, the coating is on the outside, the test part is folded in advance by hand so that the width is 30 mm, and the thickness is between these two folded test pieces. After sandwiching two 0.26mm aluminum plates and dropping a 1kg load from a height of 40cm onto the bent part and completely bending it, the end of the bent part was energized for 6.0V x 6 seconds, and a workability of 15mm wide current. The value (mA) was measured.
A: Less than 1.0 mA B: 1.0 mA or more and less than 10 mA Δ: 10 mA or more and less than 20 mA x: 20 mA or more

<Processability after retorting> While the test panel was immersed in water, retorting was performed in a retort kettle at 130 ° C for 1 hour.
The treated test panel was cut into a size of 30 mm × 50 mm, the coating film was on the outside, and it was previously folded by hand so that the test site had a width of 30 mm. After sandwiching two 26mm aluminum plates and dropping a 1kg load from a height of 40cm onto the bent part and completely bending it, the end of the bent part was energized for 6.0V x 6 seconds, and a workability of 15mm width ( mA) was measured.
A: Less than 10 mA B: 10 mA to less than 20 mA Δ: 20 mA to less than 50 mA x: 50 mA or more

<Water flavor property> Each water-based paint composition was coated on both sides of 0.1 mm aluminum foil and cured by heating at 200 ° C. for 2 minutes (film thickness 5 to 6 microns), and then the coated plate was 10 cm × 25 cm (both sides 500 cm ^2). ). This coated plate is put into a heat-resistant bottle together with 500 g of tap water treated with activated carbon, subjected to a retort treatment at 125 ° C. for 30 minutes, and then a flavor test is performed. As a comparison for the flavor test, a blank without a coated plate is also processed at the same time.
◎: Tasteless ○: Slightly tasting △: Tasteful ×: Slightly tasting <Flavor resistant adsorptivity> A test panel of 100 mm × 160 mm and 100 μg of limonene in a desiccator with a capacity of 12 liters. A solution dissolved in diethyl ether is put so as not to touch the coating plate, and a desiccator is covered and sealed, and left at 25 ° C. for 24 hours. After standing, take out the painted plate, immediately put the coated plate in carbon disulfide and leave it for 1 hour, extract the limonene adsorbed on the coating surface, and determine the amount of limonene (μg) adsorbed by gas chromatography It was.
A: Less than 100 μg ○: 100 μg or more to less than 500 μg Δ: 500 μg or more to less than 2000 μg x: 2000 μg or more

Claims (8)

A polymer comprising a COOH group-containing component (B), a basic compound (C), and water (D) containing an acrylic copolymer (B1) having a COOH group having a number average molecular weight of 20,000 to 100,000 In the presence of an aqueous solution or emulsion (1), an emulsified component (A) containing an ethylenically unsaturated monomer (A1), a COOH group-containing component (E1) containing an acrylic copolymer (E1) having a COOH group ), A basic compound (F), and a monomer emulsion (2) containing water (G) by radical polymerization with a water-insoluble initiator (H), a composite polymer having a glass transition temperature of 50 to 120 ° C. An aqueous coating composition comprising (J). The ethylenically unsaturated monomer (A1) contains at least one amide monomer selected from the group consisting of N-alkoxyalkyl (meth) acrylamide, N-hydroxyalkyl (meth) acrylamide and (meth) acrylamide. The water-based coating composition according to claim 1. The acrylic copolymer (B1) having a COOH group contains at least one amide monomer selected from the group consisting of N-alkoxyalkyl (meth) acrylamide, N-hydroxyalkyl (meth) acrylamide and (meth) acrylamide. The aqueous coating composition according to any one of claims 1 to 2, wherein the aqueous coating composition is a copolymer obtained by copolymerizing a monomer to be polymerized. The aqueous coating composition according to any one of claims 1 to 3, wherein the acrylic copolymer (B1) having a COOH group has an acid value of 150 to 500 (mgKOH / g). 5. The aqueous coating composition according to claim 1, comprising at least one component selected from the group consisting of a phenol resin and an amino resin. The water-based coating composition according to any one of claims 1 to 5, which is used for coating the inner surface of a can. A coated can characterized by coating the inner surface of the can with the aqueous paint composition according to any one of claims 1 to 6. A polymer comprising a COOH group-containing component (B), a basic compound (C), and water (D) containing an acrylic copolymer (B1) having a COOH group having a number average molecular weight of 20,000 to 100,000 In aqueous solution or emulsion (1), an emulsified component (A) containing an ethylenically unsaturated monomer (A1), a COOH group-containing component (E) containing an acrylic copolymer (E1) having a COOH group, a base A monomer emulsion (2) containing a water-soluble compound (F) and water (G), and radical polymerization with a water-insoluble initiator (H), having a glass transition temperature of 50 to 120 ° C. A method for producing an emulsion of a composite polymer (J).