JPH10316717A - Epoxy resin emulsion and production of water-based coating material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an epoxy resin emulsion improved in application properties, film performances, dispersedness and viscosity stability by neutralizing an epoxy acrylate composition obtained by radical-polymerizing an acrylic monomer in the presence of a bisphenol copolymer epoxy resin having a specified epoxy value and emulsifying the neutralized composition in water. SOLUTION: An acrylic monomer essentially consisting of a carboxylic acid component is radial-polymerized in the presence of a bisphenol epoxy resin containing bisphenol A and bisphenol F in a molar ratio of 2/8 to 8/2 and having a number-average molecular weight of 7,000-5,000, a weight-average molecular weight of 30,000-70,000, an epoxy value of 8-30 milliequivalents per 100 g of the resin and a phenolic hydroxyl value of 5 milliequivalents per 100 g of the resin to obtain an epoxy acrylate mixture comprising 75-95 pts.wt. epoxy resin and 5-25 pts.wt. acrylic resin per 100 pts.wt. resin. This is neutralized with a basic compound and then emulsified in water to obtained an emulsion having a mean particle diameter of 0.1-0.8 μm.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an epoxy resin emulsion and a method for producing a water-based paint using the same, and more particularly, to reducing an organic solvent (VOC) during the production and use of a water-based paint. Therefore, use a high-molecular-weight epoxy resin that can be used in applications requiring high processability such as easy open end (EOE), while limiting the amount of solvent used to a low level, and furthermore, do not impair the corrosion resistance of the coating film. Production method for obtaining an epoxy resin emulsion having a particle size range in which good coatability and coating film performance can be obtained, and excellent dispersibility and viscosity stability, and a water-based paint using the same. A method for producing the same.

[0002]

2. Description of the Related Art It has been widely known to use a combination of an epoxy resin and an acrylic resin for a water-based paint or the like.

For example, JP-A-63-275675 discloses a thermosetting resin as a coating film-forming component containing an epoxy resin component and a curing agent resin component, and a carboxyl group as a polymer dispersant. A carboxyl group in the acrylic resin in the form of at least one amine salt selected from the group consisting of alkylamines having a branched alkyl group and heterocyclic amines, and a coating resin component. A water-based paint for cans is described, characterized in that it is present in an amount giving an acid value of from 2 to 30 on the basis and at least the thermosetting resin is present in the form of an O / W emulsion.

It is already known to produce an epoxy resin emulsion by graft polymerizing a carboxyl group-containing acrylic monomer onto an epoxy resin.

[0005] JP-B-63-17869 entitled "Resin composition and its production method" discloses an average molecular weight of 350 to 20,000.
No. 3, pp. 139-143, and a graft modified product obtained by addition polymerization of a carboxylic acid functional monomer to an aliphatic skeleton carbon atom of a diepoxy resin and a modification technique.

Japanese Patent Publication No. 62-38363 discloses "Resin Blend Composition and Method for Producing the Same", which describes an aliphatic skeleton carbon atom of an epoxy resin modified with a terminator which erases at least a part of the epoxy group of the aromatic diepoxy resin. At least in part, there is described a graft modified product obtained by addition polymerization of a carboxylic acid functional monomer and a modification technique.

[0007] JP-B-63-33765 discloses a "water-holding thermoplastic polyhydroxyether composition" which comprises a monomeric ethylenically unsaturated hydrocarbon containing a carboxyl group as an essential component in a thermoplastic polyhydroxyl ether (commonly known as phenoxy resin). Methods for grafting bodies and producing colloidal dispersions are described.

JP-A-3-76770, "Epoxy resin composition for coatings" discloses that 5 to 100% of the bisphenol skeleton of the epoxy resin is a bisphenol F skeleton, and 96% or more of the bisphenol F is a binuclear body. A coating composition containing a bisphenol type epoxy resin and a curing agent is described.

Japanese Patent Application Laid-Open No. 7-292072 entitled "Epoxy resin composition for coatings" discloses a bisphenol type epoxy resin containing 10 to 40% of a bisphenol F component which is a binuclear op isomer and a curing agent. Are described.

[0010]

An organic coating for protecting a metal is required to have a combination of workability and corrosion resistance.
For example, in the production of can lids and can bodies, processing on painted metal plates is performed, and in the case of can lids such as easy open end,
It undergoes severe processing such as score processing and rivet processing, and in the case of can bodies, it undergoes severe drawing processing such as advanced drawing processing, multiple neck-in processing, bead processing, so it has sufficient workability and even after processing It is required to have excellent corrosion resistance. For such applications, for example, the use of a high-molecular-weight epoxy resin having a number average molecular weight of 7,000 or more is essential.

Conventionally, in the production of an aqueous dispersion using a high-molecular-weight epoxy resin as described above, a large amount of an organic solvent of 100 to 200 parts by weight per 100 parts by weight of epoxy acrylate is used, or an acrylic modified amount is used. There has been no other method but to increase the amount of the acrylate, for example, to increase the acrylic content in the epoxy acrylate to 30% or more to produce an aqueous dispersion.

In the former case, a large amount of an organic solvent is used, which is disadvantageous from an economical and environmental point of view. In addition, an unnecessary organic solvent unnecessary for the final aqueous composition is removed by a vacuum distillation method. It requires an extra process of extracting with.

In the case of the latter, there is a problem that the water resistance and corrosion resistance required for a can lid or the like cannot be achieved because the hydrophilic acrylic component is increased.

The present invention is intended for use in which high workability is required, such as easy open end (EOE), in which the amount of solvent used is reduced to reduce VOC during production and use of water-based paints. Uses a high molecular weight epoxy resin that can be applied and further limits the amount of acrylic used to the extent that the corrosion resistance of the coating is not impaired.It is a particle size range where good paintability and coating performance can be obtained, and dispersibility and viscosity stability It is an object of the present invention to provide a production method for obtaining an epoxy resin emulsion having excellent properties. The invention also provides Mn 7000-15
Epoxy resin of bisphenol A and bisphenol F having a molecular weight of 30,000 to 70,000 can be obtained by using an acrylic resin by using a minimum amount of an organic solvent which is economically advantageous and necessary for coating a final aqueous coating composition. Denature,
It is an object to provide a method for producing an aqueous dispersion. More specifically, an object of the present invention is to produce an aqueous dispersion by limiting the amount of an organic solvent used to 20 to 70 parts by weight per 100 parts by weight of epoxy acrylate.

[0015]

According to the present invention, the number average molecular weight of bisphenol A and bisphenol F in a molar ratio of 2: 8 to 8: 2 is from 7,000 to 15,
000, weight average molecular weight of 30,000 to 70,000
0, an acrylic resin containing a carboxylic acid component as an essential component in the presence of a bisphenol type epoxy resin having an epoxy value of 8 to 30 meq per 100 g of resin and a phenolic hydroxyl value of 5 meq or less per 100 g of resin. By radical polymerization of the system monomer, epoxy resin of 75 to 95 parts by weight of epoxy resin component and 5 to 25 parts by weight of acrylic resin component per 100 parts by weight of resin, and 20 to 70 parts by weight of organic solvent component per 100 parts by weight of resin An acrylate mixture is prepared, the epoxy acrylate mixture is neutralized with a basic compound, and then water is added to emulsify the mixture.
A method of making a 1 to 0.8 micron epoxy resin emulsion is provided.

In the manufacturing method of the present invention, The copolymerized epoxy resin is (A) bisphenol A
And / or a copolymerized epoxy resin derived from diglycidyl ether of bisphenol F and (B) bisphenol F, bisphenol A or a mixture thereof. Bisphenol F of the copolymerized epoxy resin is o-
2. containing at least 40 mol% of o and op methylene conjugates and having a binuclear content of 96% by weight or more;
The epoxy resin has a molar ratio of 100: 70 to 100: 9.
3. is derived from the diglycidyl ether of bisphenol and bisphenol 5; 4. When the epoxy resin has a desired molecular weight, epoxy value, and phenolic hydroxyl value, a solvent is added, and the reaction is stopped by cooling to prepare the epoxy resin; The acrylic monomer is methacrylic acid 40 to 70
5. a monomer mixture consisting of 30% by weight, 30-50% by weight of styrene, and 0.1-20% by weight of ethyl acrylate; That the radical polymerization of the acrylic monomer having the carboxylic acid component as an essential component is performed using a peroxide-based initiator, in particular that the peroxide-based initiator is benzoyl peroxide, 7. The above-mentioned peroxide initiator is used in an amount of 8 per acrylic monomer.
7. to be used in an amount of from 15 to 15% by weight; 8. the radical polymerization is performed in a temperature range of 110 ± 5 ° C .; 9. the radical polymerization is carried out up to a conversion such that the monomer concentration becomes 6000 ppm or less; 10. neutralization of the epoxy acrylate mixture with a basic compound so as to neutralize 40 to 80 mol% of the carboxylic acid component; 11. the basic compound is dimethylethanolamine; 20. neutralization of the epoxy / acrylate mixture with a basic compound in a temperature range of 105 ± 10 ° C .; The emulsification comprises continuously adding at least 60 parts of water per 100 parts by weight of epoxy acrylate at a rate of 10 to 50 parts per hour while maintaining the neutralized epoxy acrylate at a temperature of 85 ± 10 ° C. It is preferable to carry out the phase conversion from a water-in-oil emulsion to an oil-in-water emulsion.

According to the present invention, there is further provided a method for producing a water-based paint, which comprises adding a wax component after producing the above-mentioned epoxy resin emulsion, and a method for producing a thermosetting resin containing a methylol group after producing the above-mentioned epoxy resin emulsion. A method for producing a water-based paint to which a resin component is added is provided.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION

[Action] In the present invention, an acrylic monomer having a carboxylic acid component as an essential component is grafted to an epoxy resin in an organic solvent, and a basic compound and water are added to the graft to carry out phase conversion to an emulsion. But as an epoxy resin,
A copolymerized epoxy resin of bisphenol A and bisphenol F having a number average molecular weight (Mn) of 7000 to 15000 and a weight average molecular weight (Mw) of 30,000 to 70000 is selected.
It has a remarkable feature in producing an aqueous dispersion by limiting the amount to 20 to 70 parts by weight per 0 parts by weight.

In the present invention, by using the above-mentioned high molecular weight epoxy resin, a coating film to be formed can be imparted with properties such as high workability, corrosion resistance and extraction resistance. The acrylic emulsion can be used for a water-based paint such as a can lid with an easy-open function (hereinafter, EOE).

When a high molecular weight epoxy resin is used, the viscosity of the resin becomes high, and it is extremely difficult to carry out uniform acrylic modification with a small amount of an organic solvent. In fact, during the production of the aqueous dispersion, the epoxy acrylate became a high-concentration, high-viscosity mass, making it impossible to obtain an aqueous dispersion having good dispersibility and dispersion stability. In the present invention, a copolymerized epoxy resin having bisphenol A and bisphenol F in a specific molar ratio is used as the epoxy resin, and more preferably, a predetermined amount of oo, op-methylene bond is used as the epoxy resin. By using a copolymer of bisphenol F and bisphenol A containing a polymer and increasing the molecular weight of the epoxy resin, an epoxy resin having a low melt viscosity and low solution viscosity can be obtained. As a result, the amount of solvent used during the polymerization reaction of the epoxy resin, the acrylic modification reaction, and the emulsification can be reduced.

More specifically, the amount of the organic solvent used is from 20 to 7 per 100 parts by weight of the epoxy acrylate.
By limiting the amount to 0 parts by weight, it is possible to produce an aqueous dispersion having good dispersibility and stability, thereby reducing the amount of solvent volatilized at the time of coating and reducing the coating cost.

Further, in the present invention, the acrylic content in the epoxy acrylate is 5 to 25%, particularly 10%.
Another important factor is that excellent self-emulsifiability is obtained while maintaining a relatively low range of from 20% to 20%, and the water resistance of the coating film is improved by reducing the acrylic content in the epoxy acrylate. It has features.

The present inventors have proposed that the acrylic modification of the copolymerized epoxy resin is carried out by radically polymerizing an ethylenically unsaturated monomer containing (meth) acrylic acid as an essential component in the presence of the copolymerized epoxy resin. , The terminal phenolic hydroxyl group of the epoxy resin inhibits radical polymerization,
It was found that the rate of acrylic modification was reduced. By optimizing the relationship among the molecular weight of the copolymerized epoxy resin, the epoxy value, and the terminal phenolic hydroxyl value, it was possible to increase the acrylic modification ratio and prepare an epoxy-acrylate mixture having excellent emulsifiability.

In the present invention, the above epoxy acrylate solution is produced, and this solution is passed through a water-in-oil dispersion,
By inverting the dispersion to an oil-in-water dispersion, the median diameter is reduced to 0.1. Epoxy resin emulsions of 1 to 0.8 μm could be obtained. This dispersion is not only excellent in dispersion stability because the epoxy resin emulsion is maintained at a fine and appropriate particle size, but also provides a coating film excellent in coating workability, and dense and excellent in smoothness. This also brings the advantage.

In the present invention, the molar ratio of bisphenol A to bisphenol F of the copolymerized epoxy resin is from 2: 8 to
It is important to be within the range of 8: 2. Below this range, the corrosion resistance of the coating film decreases, the dissolution property increases, retort whitening and the like occur, and the coating film performance deteriorates. If the ratio exceeds the above, it is not preferable that the resin viscosity increases and the amount of solvent used increases.

It is important that the copolymerized epoxy resin has a number average molecular weight (Mn) of 7000 to 15000 and a weight average molecular weight (Mw) of 30,000 to 70,000. Corrosion resistance decreases, dissolution increases, retort whitening occurs, etc., and the coating film performance becomes inferior.On the other hand, if it exceeds the above range, the resin viscosity increases, or the amount of solvent for coating increases or Or, in case of extreme, emulsification is not possible.

The epoxy value of the copolymerized epoxy resin is 8 to 3
It is also important to be within the range of 0 milliequivalents. Below this range, the emulsifiability tends to be poor, whereas above this range the molecular weight tends to be small and the coating properties tend to be poor. Further, it is also important that the phenolic hydroxyl value of the copolymerized epoxy resin is 5 meq or less. If the phenolic hydroxyl value exceeds this range, the polymerization rate and the modification rate of the acryl deteriorate, and the emulsifying property tends to deteriorate. There is.

It is important that the epoxy resin content in 100 parts of the epoxy acrylate composition is in the range of 75 to 95 parts. If the amount falls below this range, the coating film performance will deteriorate, If it exceeds, the emulsifiability becomes inferior. It is also important that the acrylic resin is in the range of 5 to 25 parts. If the amount falls below this range, the emulsifiability becomes poor, while if it exceeds the above range, the coating film performance deteriorates.

In the present invention, the epoxy acrylate 10
It is important that the amount of the organic solvent component per 0 part is in the range of 20 to 70 parts. If the amount is below this range, the emulsifiability becomes poor. This results in a decrease in the critical film thickness, deterioration of skinning properties, and the like.

The particle size of the epoxy resin emulsion is 0.
It is important that the thickness is in the range of 1 to 0.8 μm.
Deterioration of skinning and the like are likely to occur. On the other hand, when it exceeds the above range, the emulsion becomes unstable, the coating film performance deteriorates, thin coating becomes impossible, and the paint tends to be dartant.

As described above, low V during coating production and use
To reduce the amount of solvent used to achieve OC,
Uses high-molecular-weight epoxy resin applicable to applications requiring high workability such as open-end (EOE), and further limits the amount of acrylic used to the extent that the corrosion resistance of the coating is not impaired. It is a particle diameter range in which the properties and coating film performance can be obtained, and it is possible to provide an epoxy resin emulsion excellent in dispersibility and viscosity stability.

[Production of copolymerized epoxy resin] (1) Bisphenol F: Bisphenol F is derived from the reaction between phenol and formaldehyde. The reaction is carried out in an excess of phenol such as a phenol / formaldehyde molar ratio of 3 to 6, and the catalyst may be a strong acid such as oxalic acid, hydrochloric acid, sulfuric acid, paratoluenesulfonic acid, or phosphoric acid, or a salt of a divalent metal. And oxides are used. The reaction temperature is suitably from 40 to 120 ° C., and the reaction time is suitably from about 30 minutes to 4 hours. As formaldehyde, a 30 to 55% aqueous solution (formalin) is usually used, and phenol having a melting point of 40.9 ° C. is usually mixed with a small amount of water and handled in a liquid state. The pH during the reaction is adjusted to an appropriate pH of 1 to 7, and under acidic conditions of pH 1 to 4, bisphenol F having a high content of p-methylene bond is produced.
n, Ca, Mg, Zn, Cd, Pb, Cu, Co, Ni
When a divalent metal salt or oxide such as
Bisphenol F having a high methylene bond content is obtained.
Particularly suitable divalent metal salts for obtaining o-methylene bonds are acetates such as Zn, Mn and Mg.

Water is separated and removed from the reaction suspension, and if necessary, the catalyst is neutralized and the product is washed with water. It is then generally dehydrated by atmospheric distillation and the residual phenol is removed by vacuum distillation. The obtained bisphenol F contains 2,
In addition to the three types of binuclear phenols, 2′-, 2,4′-, and 4,4′-dihydroxydiphenylmethane, polynuclears such as trinuclear and tetranuclear are included. Is purified by a vacuum distillation method. Furthermore, it is also possible to isolate each of the three binuclear phenols using a distillation method or a recrystallization method from a solvent. Bisphenol F
For purification of, a distillation purification method is usually used, but a recrystallization method from a solvent may be used. Alcohols such as butanol, acetone, benzene,
Toluene or the like, or a mixed solvent thereof is used.
A dimethylene ether bond by-produced in a small amount during the production of bisphenol F can be converted to a methylene bond by providing a heating stage at 150 to 160 ° C. during purification.

By analyzing the obtained bisphenol F by high performance liquid chromatography (HPLC), three types of binuclear phenols can be separated from polynuclears such as trinuclear and quadrinuclear, and the binuclear purity and oo, op, pp
Can be determined respectively. Silica or the like treated with dichlorodibutylsilane is used for the stationary phase, and methanol /
Water, acetonitrile / water, a mixture of methanol / acetonitrile / water and the like are used. Ultraviolet absorption (UV) is used as a detector, and the content of each component in bisphenol F is determined on the assumption that each peak area is proportional to the weight concentration of each component. In addition, bisphenol F
The ratio of oo, op, and pp methylene bonds therein can be quantitatively evaluated.

Bisphenol F is represented by the following chemical formula (1): HO-Φ-CH ₂ -Φ-OH ‥‥ (1) wherein Φ represents a phenylene group.

The bisphenol F used in the present invention comprises o-
Those containing 40 mol% or more of o and op methylene bonds are preferred. Below this range, the viscosity of the epoxy resin increases, which increases the amount of solvent for coating, or, in extreme cases, makes it impossible to emulsify. Bisphenol F preferably used for the purpose of the present invention has an ortho-para methylene bond of 40%.
~ 60 mol%, with para-para-methylene linkages of 2
It is a mixture containing 0 to 50 mol% and 10 to 20 mol% of ortho-ortho-methylene bonds.

(2) Copolymerization The epoxy resin used in the present invention is a copolymerization epoxy resin derived from bisphenol A, bisphenol F and epichlorohydrin, and contains bisphenol A and bisphenol F in the above-mentioned quantitative ratio. When the content of bisphenol F in the copolymerized epoxy resin exceeds the above range, the viscosity of the coating material decreases, but the glass transition point (Tg) of the resin decreases and the heat resistance and water resistance of the coating film deteriorate. become. The tendency of the coating film to be whitened by the retort treatment is increased, and the corrosion resistance of the coating film is reduced because water and ions are easily transmitted. If the content of bisphenol F is smaller than the above range, the viscosity of the resin solution is significantly increased, and the amount of solvent used for coating is increased,
Alternatively, the emulsifying property is deteriorated. Also, when the average molecular weight exceeds the above-mentioned range, the amount of the solvent used in coating is significantly increased, or the emulsifiability is deteriorated. When the average molecular weight is less than the above range, the processability of the coating film becomes insufficient and the processing is performed. Corrosion resistance becomes poor. In addition, as the average molecular weight decreases, the low-temperature and short-time curing properties of the coating material also become inferior. If the amount of the curing agent added is increased in order to compensate for the insufficient curability, the processability and dissolution properties will deteriorate.

The copolymerized epoxy resin is bisphenol A
And a one-stage polymerization method (taffy method) of bisphenol F and epichlorohydrin, but in order to obtain a high molecular weight copolymerized epoxy resin having an average molecular weight in the above range, bisphenol A and / or bisphenol A It is preferably derived by a two-stage polymerization method (fusion method) of the diglycidyl ether of F with bisphenol F, bisphenol A or a mixture thereof.

The copolymerized epoxy resin polymerized by the one-stage polymerization method tends to have a broad molecular weight distribution expressed by weight average molecular weight / number average molecular weight, and has a low elution property due to a large amount of low molecular weight components. Because it contains many components,
As a result, the viscosity of the resin solution is increased, which results in an increase in the amount of solvent used.

In order to obtain a high molecular weight copolymerized epoxy resin having a number average molecular weight of 8,000 to 15,000, the purity of the raw materials used in the two-stage polymerization method is important. As bisphenol A, a high-purity product having a melting point of 155 to 157 ° C. is preferably used, and as the diglycidyl ether of bisphenol A, a high-purity product is preferably used.
30 poise (25 ° C), epoxy equivalent 175 to 190
Liquid bisphenol A type epoxy resin is preferred.

The binuclear purity of the bisphenol F used is even more important, suitable bisphenol F having a binuclear purity of 96% or more, preferably 98% or more. When the purity of the raw material used is poor, the molecular weight distribution becomes large, and even if the weight average molecular weight becomes large, it contains a considerably low degree of polymerization component and the number average molecular weight often does not reach the above range.

Further, in order to obtain a copolymerized epoxy resin having a number average molecular weight in the above range, (A) diglycidyl ether of bisphenol A and / or bisphenol F and (B) bisphenol F, bisphenol A or a mixture thereof are used. A: B = 100: 70 to 10
It is preferable to use a molar ratio of 0:95. Below this range, the molecular weight will decrease and the coating performance will deteriorate, whereas above the above range, the phenolic hydroxyl number will increase and the emulsifiability will tend to deteriorate.

The copolymerized epoxy resin used in the present invention has a content of a component having a molecular weight of 1,000 or less of less than 2%, and a coating film obtained therefrom has excellent dissolution properties and flavor properties. Conventional paint for cans requires a high-temperature, long-term curing reaction to suppress dissolution, but using a resin with a small amount of dissolution components enables low-temperature, short-time baking. Was.

The copolymerized epoxy resin used in the present invention has a narrow molecular weight distribution represented by weight average molecular weight / number average molecular weight, and has
The following is preferred. When the molecular weight distribution exceeds 5, the resin viscosity becomes high, and the effect of reducing the viscosity by adding bisphenol F is offset.

Another reason that the water-based coating composition of the present invention exhibits excellent low-temperature short-time curability is a copolymerized epoxy resin. The copolymerized epoxy resin has a high molecular weight, and not only for obvious reasons that the film performance is remarkably improved only by a small amount of crosslinking reaction, but also for the copolymerized epoxy resin, oo and op There is another reason that this is involved in the curing reaction because bisphenol F having a high content of methylene complex is used and the p-position showing high reactivity is vacant. Vacant p- on the copolymerized epoxy resin skeleton
In addition to reacting directly with a methylol group or an etherified methylol group, it seems to react via formaldehyde which is a by-product during the curing reaction.

The reason why the copolymerized epoxy resin used in the present invention contains bisphenol A and bisphenol F in a specific molar ratio has been described above, but there is another reason for controlling the reactivity. When bisphenol F is contained more than the above range, it reacts sensitively to a slight difference in the baking conditions of the paint, and it is difficult to obtain a coated film of a constant quality. The distortion is large, and the adhesiveness and workability become poor. When the content of bisphenol F is lower than the above range, the low-temperature short-time curability becomes insufficient.

The polymerization reaction is carried out by a continuous system using an extruder or a batch system using a reactor. In the case of a continuous process, the preferred polymerization temperature is 170 to 250 ° C., and the preferred reaction time is 0.01 to 0.06 hours. In the case of a batch type, a temperature range of 140 to 220 ° C. and a reaction time of 1 to 8 hours are preferable.

Although the polymerization reaction can be carried out in the absence of a solvent, it is generally preferred to carry out the reaction in the presence of a solvent. Suitable solvents for use in the polymerization include, for example, glycol ethers, alcohols, ketones, acetates, aromatic hydrocarbons, and any combination thereof. Particularly preferred solvents are
For example, C1 -C1 of acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, diacetate alcohol, mono- or dialkylene glycol
4 Alkyl ethers such as n-
Methyl ether, methyl ether of ethylene glycol, n-butyl ether of propylene glycol, methyl ether of propylene glycol, n-butyl ether of diethylene glycol, methyl ether of diethylene glycol, n-butyl ether of dipropylene glycol or methyl ether of dipropylene glycol, 3- Includes methyl-3-methoxybutanol, propylene glycol diacetate, n-butanol, sec-butanol, isopropanol, butyl acetate, toluene, xylene and any combination thereof.

The solvent in the polymerization system is preferably used in an amount of 0.1 to 20 parts, especially 1 to 15 parts, per 100 parts of the raw material mixture of the epoxy resin, and immediately after the desired copolymerized epoxy resin is prepared, In particular, in a batch method, the reaction can be stopped by diluting with a solvent and cooling. When stirring becomes difficult, the reaction can be further advanced by diluting with a solvent to lower the viscosity.

Suitable catalysts for use in the polymerization reaction include, for example,
Includes phosphonium compounds such as phosphonium carboxylate, phosphonium carboxylate carboxylic acid complexes, phosphonium halides, phosphonium biscarbonates, phosphonium phosphates, and any combination thereof. Particularly suitable catalysts include, for example, ethyltriphenylphosphonium acetate complex, ethyltriphenylphosphonium phosphate, tetrabutylphosphonium acetate complex, tetrabutylphosphonium phosphate and any combination thereof.

Further, a catalyst represented by the following formula (2) is also suitable. ^{- Z'R 1 R 2 R 3 P} + -Z-P + R 1 R 2 R 3 Z'- ‥ (2) ( In the formula, each of R ^1, R ² and R ³ are aromatic groups independently or Z is — (C (R ⁴ ) ₂ ) _2;
Each R ⁴ is independently hydrogen or a hydrocarbyl group containing 1 to 20, more preferably 1 to 10, most preferably 1 to 4 carbon atoms or an inert substituted hydrocarbyl group; Z ′ Is any suitable anion). Suitable inert substituents for Z are, for example, -CO-
Includes Cl, -CN and -OH.

Particularly preferred catalysts for use in the present invention are:
For example, tetramethylenebis (triphenylphosphonium chloride), tetramethylenebis (triphenylphosphonium iodide), tetramethylenebis (triphenylphosphonium bromide), pentamethylenebis (triphenylphosphonium chloride), pentamethylenebis (triphenylphosphonium) Iodide), pentamethylenebis (triphenylphosphonium bromide), hexamethylenebis (triphenylphosphonium iodide),
Hexamethylenebis (triphenylphosphonium chloride), hexamethylenebis (triphenylphosphonium bromide), heptamethylenebis (triphenylphosphonium chloride), heptamethylenebis (triphenylphosphonium bromide), tetramethylenebis (triphenylphosphonium acetate / acetic acid) Complex), pentamethylenebis (triphenylphosphonium acetate / acetic acid complex), hexamethylenebis (triphenylphosphonium acetate / acetic acid complex), heptamethylenebis (triphenylphosphonium acetate / acetic acid complex), tetramethylene bis (triphenylphosphonium phosphate) ), Pentamethylenebis (triphenylphosphonium phosphate), hexamethylenebis (triphenylphosphonium phosphate) ), Heptamethylenebis (triphenylphosphonium) phosphate, tetramethylenebis (triphenylphosphonium) bicarbonate, pentamethylenebis (triphenylphosphonium) bicarbonate, hexamethylenebis (triphenylphosphonium) bicarbonate, heptamethylenebis (Triphenylphosphonium) bicarbonate, tetramethylenebis (triphenylphosphonium) oxalate, pentamethylenebis (triphenylphosphonium) oxalate, hexamethylenebis (triphenylphosphonium)
Oxalates, heptamethylenebis (triphenylphosphonium) oxalates, and combinations thereof.

Further, those preferably used as a catalyst are phosphonium compounds having three phenyl groups bonded to a phosphorus atom and one cycloalkyl group bonded to a phosphorus atom. It does not matter what the anion part of the phosphonium compound is. Particularly suitable such anions are
For example, halides such as chloride, bromide or iodide; carboxylate such as formate, acetate, oxalate, trifluoroacetate, carboxylate-carboxylate complex such as acetate-acetic acid complex; conjugate base of inorganic acid such as bicarbonate and tetrafluoroborate Or a conjugate base of phenol, such as phenate or an anion derived from bisphenol or biphenol (eg, bisphenol A or bisphenol F), or a combination thereof. This cycloalkyltriphenylphosphonium catalyst has the following formula (3)

Embedded image (Wherein Q is preferably 3-8 in the cycloalkyl ring,
More preferably, it is a cycloalkyl, alkyl or halo-substituted cycloalkyl group having 4-7, most preferably 5-6 carbon atoms; each R is independently hydrogen, halogen, or preferably 1-12 More preferably a hydrocarbyl group having 1 to 6, most preferably 1 to 3 carbon atoms;
Z is an anion such as chloride, bromide or iodide, a carboxylate such as formate, acetate, oxalate, trifluoroacetate, or a carboxylate-carboxylate complex such as acetate-acetic acid complex; a conjugate base of an inorganic acid such as bicarbonate or tetracarbonate Fluoroborate or biphosphate;
And conjugate bases of phenol, such as phenate or anions derived from bisphenol or biphenol (eg, bisphenol A or bisphenol F) and combinations thereof.

Particularly suitable such catalysts are, for example, cyclopropyltriphenylphosphonium iodide, cyclopropyltriphenylphosphonium bromide, cyclopropyltriphenylphosphonium chloride, cyclopropyltriphenylphosphonium acetate, cyclopropyltriphenylphosphonium acetate.acetic acid Complex,
Cyclopropyltriphenylphosphonium phosphate, cyclopropyltriphenylphosphonium heptanoate, cyclopropyltriphenylphosphonium oxalate, cyclobutyltriphenylphosphonium iodide, cyclobutyltriphenylphosphonium bromide, cyclobutyltriphenylphosphonium chloride,
Cyclobutyltriphenylphosphonium acetate, cyclobutyltriphenylphosphonium acetate-acetic acid complex, cyclobutyltriphenylphosphonium phosphate, cyclobutyltriphenylphosphonium heptanoate, cyclobutyltriphenylphosphonium oxalate, cyclopentyltriphenylphosphonium iodide, cyclopentyltri Phenylphosphonium bromide, cyclopentyltriphenylphosphonium chloride, cyclopentyltriphenylphosphonium acetate, cyclopentyltriphenylphosphonium acetate / acetic acid complex, cyclopentyltriphenylphosphonium phosphate, cyclopentyltriphenylphosphonium heptanoate, cyclopentyltriphenylphosphonium oxalate , Cyclopropyltriphenylphosphonium iodide, cyclopropyltriphenylphosphonium bromide, cyclopropyltriphenylphosphonium chloride, cyclopropyltriphenylphosphonium acetate, cyclopropyltriphenylphosphonium acetate / acetic acid complex, cyclopropyltriphenylphosphonium phosphate, cyclopropyltriacetate Phenylphosphonium heptanoate, cyclopropyltriphenylphosphonium oxalate, cyclohexyltriphenylphosphonium iodide, cyclohexyltriphenylphosphonium bromide, cyclohexyltriphenylphosphonium chloride, cyclohexyltriphenylphosphonium acetate, cyclohexyltriphenylphosphonium acetate / acetic acid complex , Cyclohexyltriphenylphosphonium phosphate, cyclohexyltriphenylphosphonium oxalate, cycloheptyltriphenylphosphonium iodide, cycloheptyltriphenylphosphonium bromide, cycloheptyltriphenylphosphonium chloride, cycloheptyltriphenylphosphonium acetate, cycloheptyltriphenylphosphonium acetate Acetic acid complex, cycloheptyltriphenylphosphonium phosphate, cycloheptyltriphenylphosphonium heptanoate, cycloheptyltriphenylphosphonium oxalate, cyclooctyltriphenylphosphonium iodide, cyclooctyltriphenylphosphonium bromide, cyclooctyltriphenylphosphonium chloride, cycle Includes cyclooctyltriphenylphosphonium acetate, cyclooctyltriphenylphosphonium acetate / acetic acid complex, cyclooctyltriphenylphosphonium phosphate, cyclooctyltriphenylphosphonium heptanoate, cyclooctyltriphenylphosphonium oxalate and combinations thereof.

The catalyst is used in an amount sufficient to catalyze the reaction between the diglycidyl ether of bisphenol and bisphenol.
It is preferred to use 3 to 2 parts, especially 0.04 to 1 part.

[Production of Epoxy Acrylate] According to the present invention, an acrylic monomer containing a carboxylic acid component as an essential component is subjected to radical polymerization in the presence of the bisphenol-type epoxy resin thus produced. An epoxy-acrylate mixture is prepared having 75 to 95 parts by weight of an epoxy resin component and 5 to 25 parts by weight of an acrylic resin component per 100 parts by weight, and 20 to 70 parts by weight of an organic solvent component per 100 parts by weight of the resin.

It is essential that the acrylic monomer used contains a carboxylic acid component in order to impart self-emulsifying properties. As the ethylenically unsaturated carboxylic acid,
Specifically, acrylic acid, methacrylic acid, maleic acid,
Α, β-unsaturated carboxylic acids such as fumaric acid, itaconic acid, citraconic acid and tetrahydrophthalic acid; unsaturated carboxylic acids such as bicyclo [2,2,1] hept-2-ene-5,6-dicarboxylic acid; Α, β unsaturated carboxylic acid anhydrides such as maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, and bicyclo [2,2,
1] anhydride of unsaturated carboxylic acid such as hept-2-ene-5,6-dicarboxylic anhydride, monomethyl maleate,
Monoethyl maleate, ethyl fumarate, methyl itaconate, ethyl citraconic acid, methyl tetrahydrophthalic anhydride, bicyclo [2,2,1] hept-2-ene-
Half esters such as methyl 5,6-dicarboxylate and the like can be mentioned. Among them, acrylic acid (AA),
Methacrylic acid (MAA), especially methacrylic acid, is preferred.

In addition to the above carboxylic acid components, acrylic acid and methacrylic acid esters can be used.
Such an ester monomer becomes a soft segment of the graft polymer chain. Examples of the ester monomer include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate,
N-Amyl (meth) acrylate, isoamyl (meth) acrylate, n-hexyl (meth) acrylate, (meth)
2-ethylhexyl acrylate, (meth) acrylic acid n
Octyl and the like. However, the above (meth) acrylic acid means acrylic acid or methacrylic acid. The above (meth) acrylates may be used alone or in combination, or may be used in combination with other monomers.
It may be a copolymer. A preferred ester is ethyl acrylate (EA).

In order to improve the coating properties, it is preferable to use a vinyl hydrocarbon monomer, especially a vinyl aromatic monomer such as styrene and vinyl toluene, together with these monomers. Styrene is particularly preferred.

The preferred acrylic monomer used in the present invention comprises a combination of methacrylic acid, ethyl acrylate, and styrene.

It is preferable that methacrylic acid is in the range of 40 to 70% based on the whole acrylic monomer. If it is below this range, the emulsifiability becomes inferior. Workability, water resistance, and adhesion will be poor.

The styrene content is preferably in the range of 30 to 50% based on the entire acrylic monomer. If the styrene content is less than this range, the processability, water resistance, and adhesion will be poor. If it exceeds, the emulsifiability becomes inferior.

Ethyl acrylate is preferably in the range of 0.1 to 20% based on the whole acrylic monomer, and below this range, the processability, water resistance, and adhesion of the coating film are inferior. On the other hand, when it exceeds the above range, the flavor property of the coating film becomes inferior.

The graft polymerization of the acrylic monomer onto the copolymerized epoxy resin is carried out in an organic solvent of the kind and amount described above under an inert atmosphere in the presence of a peroxide initiator. The acrylic monomer and the initiator can be added to the reaction system in a state of being dissolved in an organic solvent, and nitrogen gas can be used to maintain the reaction system in an inert atmosphere.

Examples of the organic peroxide include dicumyl peroxide, di-t-butyl peroxide, 2,2
5-dimethyl-2,5-bis (t-butylperoxy)
Hexane, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3, 1,3-bis (t-butylperoxyisopropyl) benzene, 1,1-bis (t-butylperoxy) ) Balalate, benzoyl peroxide, t-butylperoxybenzoate, acetyl peroxide, isobutyl peroxide, octanoyl peroxide, decanoyl peroxide,
Examples include lauroyl peroxide, 3,3,5-trimethylhexanoyl peroxide, 2,4-dichlorobenzoyl peroxide, and m-toluyl peroxide. Benzoyl peroxide is particularly preferred.

The amount of the peroxide initiator is preferably in the range of 8 to 15% by weight per acrylic monomer,
Below this range, the acrylic modification rate is inferior and the emulsifiability deteriorates.On the other hand, above the above range, dead-end polymerization tends to occur, the acrylic modification rate decreases, the emulsifiability deteriorates, and the solvent An increase in the amount and deterioration of the dissolution property of the coating film are likely to occur.

In the present invention, other conditions of the radical polymerization should be determined so as to satisfy the above-mentioned conditions. Generally, however, the reaction temperature is controlled within a narrow range of 110 ± 5 ° C. It is preferable that the degree of acryl modification of the epoxy resin can be increased.

That is, if the radical polymerization temperature falls below the range of 110 ± 5 ° C., the acrylic modification rate becomes poor and the emulsifying property deteriorates, while if it exceeds the above range, the acrylic polymerization rate decreases and the emulsifying property decreases. It tends to worsen and the odor of the monomer also increases.

It was also found that controlling the concentration of the residual monomer to a certain level or less greatly affected the quality of emulsification. 6000ppm monomer concentration after radical polymerization
If the ratio exceeds the above range, the final emulsifiability of the epoxy acrylate and its dispersion stability tend to decrease. The concentration of the residual monomer may be adjusted by appropriately setting the above-described polymerization conditions and performing the reaction so that the monomer is sufficiently converted.

[Neutralization and Phase Inversion] According to the present invention, the thus-prepared epoxy-acrylate mixture is neutralized with a basic compound, and then emulsified by adding water.

A basic compound is used to neutralize the carboxylic acid component in the epoxy acrylate to form a self-emulsifying composition. As the basic compound, amines,
For example, aliphatic, alicyclic, aromatic primary, secondary or tertiary
Secondary amines can be used.

Specific examples of the amines include branched alkylamines such as isopropylamine, sec-butylamine, tert-butylamine, isoamylamine and the like having 3 to 6 carbon atoms, especially 3 to 4 carbon atoms. And heterocyclic amines such as saturated heterocyclic amines containing one nitrogen atom such as pyrrolidine, piperidine and morpholine, and alkanolamines such as mono-, di- or tri-ethanolamine. A particularly preferred amine is dimethylethanolamine.

The amount of the neutralizing agent used is an amount sufficient to neutralize 40 to 80 mol%, particularly preferably 50 to 70 mol%, of the carboxylic acid of the epoxy acrylate. The above-mentioned basic compound is preferably added to the reaction system as an aqueous solution in terms of the uniformity of the neutralization reaction.

The amount of the neutralizing agent is from 40 to 80 of the carboxylic acid component.
%, The emulsifiability becomes inferior. On the other hand, when it exceeds the above range, the particle size is decreased, and the viscosity of the coating material, the limit thickness of the coating material and the skinning tendency are unpreferably increased.

In the present invention, neutralization of the above epoxy-acrylate mixture with a basic compound is 105 ± 10%.
It is preferable to carry out in a temperature range of ° C.

In this neutralization reaction, the neutralization temperature was 105 ±
When the temperature falls below the range of 10 ° C., the viscosity increases and the emulsifying property deteriorates due to the temperature decrease. On the other hand, when the temperature exceeds the above range, the gelation due to the esterification reaction and the emulsifying property deteriorates due to the thickening. .

By this neutralization reaction, a water-in-oil emulsion is first formed, and then the phase is changed to an oil-in-water emulsion by adding water.

The emulsification according to the invention comprises maintaining the neutralized epoxy acrylate at a temperature of 85 ± 10 ° C. while maintaining at least 6 per 100 parts by weight of epoxy acrylate.
It is preferably carried out by continuously adding 0 parts of water at a rate of 10 to 50 parts by weight per hour to invert the phase from a water-in-oil emulsion to an oil-in-water emulsion.

When the emulsification temperature falls below the above-mentioned range of 85 ± 10 ° C., the viscosity increases and the emulsifying property deteriorates due to the temperature decrease. It tends to cause non-uniformity and aggregation after emulsification.

The rate of addition of water is preferably in the range of 10 to 50 parts / hour. If the rate is less than this range, the particle diameter increases, the emulsifying property deteriorates, and the stability of the emulsion decreases. On the other hand, if it exceeds the above range, the particle size tends to increase, the emulsifiability deteriorates, and the stability of the emulsion tends to decrease.

Thereafter, if necessary, a lubricant, a viscosity modifier,
A leveling agent, a wetting improver, a side improver, and other additives may be added to adjust the viscosity or the solid content by adding amine water or water, and the solvent may be removed by solvent removal or solvent replacement. The addition of the resole type phenolic resin and the lubricant is not limited to this order, and can be performed before and after dispersion.

[Use] According to the present invention, an epoxy acrylate emulsion useful as a coating material such as a paint or an adhesive is thus formed. This epoxy acrylate emulsion does not contain an emulsifier and the like, and the organic solvent is suppressed to a low concentration, so that it is particularly excellent in water resistance.

For use as a water-based paint, it is preferable to add a wax component in order to improve the slipperiness of the coating film and to improve the moldability in can making and lid making.

The waxes include, for example, liquid paraffin of C ₁₆ or more, microcrystalline wax, natural paraffin, synthetic paraffin, polyolefin wax and their partial oxides, or aliphatic hydrocarbon waxes such as fluorides and chlorides. , C ₁₆ or more higher aliphatic alcohols and higher fatty acid wax, fatty acid amide wax, C ₁₀ or more fatty acid metal soap wax,
Fatty acid ester waxes, carnauba wax, lanolin and the like. Suitable waxes are carnauba wax and / or lanolin, particularly preferably emulsions of carnauba and / or lanolin.

The wax is added in an amount of 0.1 to 2.0 per 100 parts of the resin of the epoxy resin emulsion.
Parts, especially 0.5 to 1.5 parts.

For use as a water-based paint, it is effective to include a curing agent for epoxy acrylate. As such a curing agent, a resin curing agent, particularly, a resol type phenol resin or a melamine resin, etc. Molecular hardeners are advantageously used. Above all, a resol type phenol resin is preferable in terms of high-speed curability.

(1) Resol type phenol resin The resol type phenol resin used in the present invention is obtained by reacting phenols with formaldehyde or a functional derivative thereof in the presence of a basic catalyst and, if necessary, etherifying with alcohol. Can be

Examples of suitable phenols are as follows, and include any combination of the following phenols:
lower alkyl-substituted bifunctional phenols such as o-cresol, p-cresol, p-tert-butylphenol, p-ethylphenol, 2,3-xylenol, 2,5-xylenol; p-tert-amylphenol, p-cresol Other bifunctional phenols such as nonylphenol, p-phenylphenol and p-cyclohexylphenol; trifunctional such as phenol (phenyl carbonate), m-cresol, m-ethylphenol, 3,5-xylenol and m-methoxyphenol Phenols; monofunctional phenols such as 2,4-xylenol and 2,6-xylenol; 2.2'-bis (4-hydroxyphenyl) propane (bisphenol A), 2,2'-bis (4-hydroxy Phenyl) butane (bisphenol B), bisphenol F, 1,1'-bi (4-hydroxyphenyl)
Ethane, 4-hydroxyphenyl ether, P- (4-
Polycyclic polyphenols such as hydroquine) phenol;

The most preferred phenol constituting the resole type phenol resin used in the present invention is bisphenol F. Bisphenol F may be a purified product having a high binuclear content or a crude product containing polynuclear bodies. When special attention is required for the dissolution property, a phenol / novolak having a high polynuclear content such as trinuclear or tetranuclear may be preferably used.

In applications where low-temperature short-time curability is particularly necessary, o
Bisphenol F having a high content of -o and op methylene bonds is preferable, and preferably, the amount of oo and op methylene bonds in all methylene bonds of bisphenol F is 60% or more, more preferably 68%. The above is used.
This is because when the ratio of the o-bond is high, the p-position showing higher reactivity to formaldehyde than the o-position is vacant, and the methylol group coordinated to the p-position shows high reactivity. .

In order to further improve the curability at a low temperature for a short time, bisphenol F having a high o-o methylene bond content is used.
Preferably, the amount of o-o methylene bond in the total methylene bond of bisphenol F is 10% or more, more preferably 17% or more, and most preferably 23% or more. The reason why the o-o methylene conjugate is highly reactive is that one hydrogen of the phenolic OH group forms a strong intramolecular hydrogen bond to dissociate the other hydrogen, exhibiting a very high acidity, and This is because the phenol resin itself has autocatalytic curing.

It is considered that a structure similar to the resole type phenol resin obtained from the reaction of bisphenol F with formaldehyde can be directly derived from phenol and formaldehyde in the presence of an alkali catalyst. The resin contains a large amount of a low-molecular-weight monocyclic phenol methylol compound, and when it is used as a paint for can-making, the result is poor elution.

Formaldehyde is generally used in the form of an aqueous solution such as formalin, but functional derivatives such as paraformaldehyde, polyoxymethylene and trioxane can also be used.

The methylolation reaction may vary depending on the composition of the phenol, but it is generally preferable to use 1 to 10 mol, particularly 3 to 7 mol, of formaldehyde per mol of the phenol.

As the basic catalyst, sodium hydroxide,
Alkali metal hydroxides such as potassium hydroxide, alkali carbonates such as sodium carbonate and potassium carbonate, alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide, and ammonia are used. These basic catalysts are preferably used in an amount of 0.2 to 3 mol, particularly 0.5 to 2 mol, per mol of phenols.

The methylolation reaction is preferably performed in an aqueous medium, and the reaction conditions are not particularly limited, but are generally room temperature to 100 ° C., particularly 40 to 80 ° C., for 0.5 to 10 hours, particularly 1 to 5 hours. A degree of reaction is desirable. The concentration of phenols in the reaction system is suitably from 10 to 50%.

To separate the resole phenolic resin from the final reaction product, the reaction mixture is neutralized with an acid such as hydrochloric acid, sulfuric acid, phosphoric acid, p-toluenesulfonic acid, oxalic acid, acetic acid, and the like. Precipitate and filter if necessary, wash with water,
Dry and collect in solid form. Alternatively,
The reaction mixture after the neutralization, methyl ethyl ketone, ketones such as cyclohexanone, alcohols such as butanol,
Alternatively, the desired product can be recovered by extracting the mixture with a mixed solvent such as toluene and xylene.

The alkyl etherification of the methylol group of the resole type phenol resin is carried out by subjecting the methylol group in the resin to a condensation reaction with an alcohol in the presence of an etherification catalyst, particularly an acid catalyst.

The alcohols include methanol, ethanol, n- or iso-propanol, n-, iso-
Although-, tert-butanol and the like can be used, alcohols having 3 to 6 carbon atoms, particularly butanol, are preferable.

As the etherification catalyst, phosphoric acid, sulfuric acid,
Hydrochloric acid, aromatic sulfonic acid (for example, p-toluenesulfonic acid), oxalic acid, acetic acid and the like can be used. In synthesizing this resin, a dissolved methylol group-containing thermosetting resin and an alcohol are reacted in an appropriate solvent in the presence of the catalyst. The amount of the catalyst used is such that the pH of the reaction system is 4-6.
The reaction temperature is preferably in the range of 70 to 90 ° C. As the solvent, an excess of alcohol, toluene, xylene or the like is used alone or in combination.
It is advantageous to carry out the reaction while removing water by-produced in the above-mentioned reaction. For this purpose, the reaction is carried out while removing water in the reaction system from the system in the form of azeotropic distillation with a solvent. It is desirable. Of course, if the amount of alcohol in the system is insufficient, it may be added to the reaction system.

The production of the phenolic resin and the alkyl etherification can be carried out in the same step or in separate steps. For example, the reaction between phenols and formaldehyde is carried out in a medium containing alcohol in the presence of an alkali catalyst, and after the desired methylolated resin is obtained, an acid catalyst is added to the system and the pH is adjusted to the above-mentioned range. The alkyl etherification reaction can be performed while maintaining. Alternatively, the formed methylolated resin may be separated by a means known per se, and this may be subjected to alkyl etherification in another system.

The obtained alkyl etherified resin may be neutralized, washed with water and dried to form a resin component for forming a coating film.
The salt or the like generated by the neutralization may be removed by any means and used as it is in the form of a resin solution.

(2) Aqueous paint The paint of the present invention is useful as a paint for various substrates, but is particularly useful as a paint for can making. This paint can be applied to the can material at any stage.

This paint can be applied to a coil coating on a can lid, and is applied to pure aluminum, an aluminum alloy or the like to obtain a coated metal material having a high workability. The material for the coating can is stamped, press-formed, or further scored, button-formed, attached with a tab, etc., and formed into a can lid or an easy-open can lid. Of course, the order is reversed, and the paint is applied to a can body, a can lid or a can after can-making,
The paint may be baked, and the paint may be provided as a single coat or a double coat.

Of course, this paint can also be used for painting the can body. In the case of a three-piece can having a side seam, a black plate, various coated steel plates, such as tin, chrome,
Plated steel plate whose surface is plated with aluminum, zinc, etc., steel plate whose surface is chemically or cathodically treated with chromic acid and / or phosphoric acid, etc .; light metal plate such as aluminum; resin film such as polyolefin, paper board, etc. A material for cans such as a composite metal material in which aluminum foil or the like is adhered and laminated on the surface of an organic substrate is applied in advance with the paint, then baked, and then joined by means such as soldering, welding, or joining with an adhesive, It will be a can body. In the case of a two-piece can, a painted metal plate is subjected to deep drawing or thinning deep drawing to obtain a painted can body.

In the case of a seamless can body, the material for the can may be subjected to squeezing or squeezing-ironing, and the paint may be applied to the formed can body and baked.

The coating material of the present invention can be prepared by any means such as dip coating, roller coating, spray coating, brush coating, electrostatic coating, electrodeposition coating, wire coating, flow coating, doctor coating and the like. It can be applied to the body, can lid or can. The paint thickness is generally 1 on a dry basis.
It can be in the range of -20 microns, especially 3-15 microns.

The baking condition of the paint is characterized in that it can be baked at a low temperature for a short time, and varies depending on the blending amount of the epoxy acrylate or resol type phenol resin in the above-mentioned paint. From the temperature of 300 ° C. and the baking time of 10 to 600 seconds, a condition for achieving sufficient curing in terms of chemical resistance and hot water resistance may be selected.

[0109]

The present invention will be specifically described below with reference to examples. “%” And “parts” used in this example are based on weight unless otherwise indicated.

(1) Analysis of epoxy resin [Molecular weight] The molecular weight of the epoxy resin was measured by GPC (gel permeation chromatography) using tetrahydrofuran (THF) as a developing solvent. The calibration curve is a polystyrene standard sample (F
-128, F-40, F-10, F-4, F-2, F-
1, A-2500, A-500). The number average molecular weight (Mn) and the weight average molecular weight (Mw) were calculated for the molecular weight of the epoxy resin with the part having a molecular weight of 200 or more as a calculation target. 4 mg of epoxy resin for T
The sample solution was adjusted at a rate of dissolving in 1 ml of HF, the amount of sample injected was 100 μl, and the flow rate of the solvent was 1 ml / min.
The measurement was performed at 0 ° C. GPC and column were HLC-8020 manufactured by Tosoh and TSK-GEL (G1000HX
L, G2000HXL, G3000HXL, G4000
HXL) and the analysis time was 50 minutes. When the sample to be measured contained a large amount of solvent other than THF, the sample solution was adjusted after removing most of the solvent by drying.

[Epoxy value] (a) Glacial acetic acid 250 ml was added to 13 ml of a 60% aqueous solution of perchloric acid.
ml and 50 ml of acetic anhydride were added and mixed well, cooled to room temperature, and glacial acetic acid was added to make the total volume 1 l. To complete the reaction between acetic anhydride and water, the mixture was allowed to stand for 8 hours thereafter. The standardization was performed by dissolving 0.4 g of potassium hydrogen phthalate in 50 ml of glacial acetic acid and titrating it using a crystal violet (CV) as an indicator until it became blue-green. (B) Etraethylammonium bromide (TEAB) 10
400 ml of glacial acetic acid was added to 0 g and dissolved with stirring at room temperature to prepare a TEAB solution. (C) Dissolve 0.1 g of CV in 100 ml of glacial acetic acid,
The indicator was adjusted. 50ml of 2-3g epoxy resin
The sample bottle was accurately weighed, and 20 ml of methyl chloride was added and dissolved. The dissolution was carried out by stirring with a clean magnetic stirrer, and the stirring was continued during the titration. Add 10 ml of TEAB solution and CV indicator to the epoxy resin solution from 8 to 1
0 drops were added and titrated with the perchloric acid standard solution of (a). The end point is the point where the blue-green color lasts for 30 seconds.

The epoxy value was calculated from the following equation. N _e: normality V _e perchloric acid standard solution: ml number of perchloric acid standard solution required for the titration W _e: g number of epoxy resin samples (if the sample contains a solvent, at 180 ° C. After drying for 1 hour, the value calculated from the obtained solid content was used.)

[Phenolic hydroxyl value] In a 250 ml cylindrical glass container provided with two holes for nitrogen purge and titration burette at the top of the container, magnetic cstallar and 75 ml of pyridine were put, and stirred for 2 to 3 minutes. And a nitrogen purge was performed. A saturated benzene solution of the azo violet indicator was added in the pyridine until the solution turned straw-colored. This was titrated with a 0.1N tetrabutylammonium hydroxide (TBAH) solution to a blue end point.
Usually, this titration requires a few drops. Subsequently, a nitrogen purge was continued for 2 to 3 minutes, and then 2-3 g of the epoxy resin sample was accurately weighed into the pre-titrated pyridine, and dissolved by stirring under a nitrogen purge. In addition, 0.1
Titrated with N-TBAH solution to blue endpoint. Care was taken that the TBAH solution was not hydrated to ensure accuracy in the measurements.

Phenolic hydroxyl value (milliequivalent /
100 g resin) was calculated from the following equation. N _p : normality of TBAH solution V _p : total number of TBAH solution required for titration V ₀ : number of ml of TBAH solution required for preliminary titration W _p : number of g of epoxy resin sample (sample contains solvent If so, it was dried at 180 ° C. for 1 hour, and a value calculated from the obtained solid content was used.)

[Epoxy Equivalent] The epoxy equivalent was calculated by the following equation.

[Phenolic hydroxyl equivalent] The phenolic hydroxyl value was calculated from the following formula.

(2) Analysis of Epoxy Resin Emulsion [Solid Content] About 0.5 g of the epoxy resin emulsion was accurately weighed into an aluminum dish, and the solid content was calculated from the weight before and after drying at 200 ° C. for 10 minutes.

[Particle Size] The particle size of the epoxy resin emulsion was measured using SALD-3000 manufactured by Shimadzu Corporation. After preliminarily diluting 1 ml of the sample emulsion in 20 ml of ion-exchanged water, the sample was put into the circulating system of the measuring section. 1.60-0.10i was selected as the refractive index, and sonication was performed for 1 minute before measurement. The particle diameter in the examples is shown by median diameter (μm).

[Viscosity] The viscosity of the epoxy resin emulsion was measured using a B-type viscometer using a # 2 rotor and 30 rpm.
For 25 minutes at 25 ° C.

[Storage Stability] The storage stability was evaluated by measuring the particle size and viscosity after storing the epoxy resin emulsion at 50 ° C. for 2 weeks. For those with poor storage stability, sedimentation of particles and separation of liquid are observed. Particularly bad ones were gels without fluidity.

(3) Evaluation of coating film performance [Retort resistance] Half of the coated plate cut out to an appropriate size was immersed in distilled water and subjected to a retort treatment at 125 ° C. for 30 minutes to evaluate the appearance of the coating film. went. Those with good retort resistance have no change in appearance, while those with poor retort resistance cause whitening or blistering of the coating film.

[Retort dissolution property] The coated plate was immersed in distilled water using distilled water at a rate of 1 ml per 1 cm ^{2 of the} coating film surface, and potassium permanganate of the retort eluate subjected to retort treatment at 125 ° C for 30 minutes was used. The consumption was measured. The procedure for measuring potassium permanganate consumption is described in the Ministry of Health and Welfare Notification No. 20
The procedure specified in the issue was followed.

[Bending workability] The coated plate is 35 m in size.
mx 35 mm, cut the sheet so that the painted surface is on the outside, and fold it in half from the center at right angles to the rolling direction of the plate so that the test site becomes 35 mm. Weight is 3.3 between two aluminum plates
A weight of 35 kg was dropped from a height of 35 cm to perform bending. The workability was evaluated by applying a current of 6.0 volts to the bending tip for 5 seconds and then measuring a current value flowing in a 1.5 cm width of the processed portion.

[Corrosion resistance] A coated plate was sized 50 mm x 50
mm, and a 300 g weight was dropped from a height of 40 cm using a DuPont impact tester, and processed so that the coating film surface side became convex. Protect the uncoated side and edges with vinyl tape and use a corrosion model solution (0.5% salt + 0.
(5% citric acid aqueous solution), and observed for corrosion after storage at 50 ° C. for 4 days.

Example 1 A bisphenol A type liquid epoxy resin (LER) was placed in a reactor equipped with a stirrer, a cooling pipe, a nitrogen inlet, various measuring units, a monomer inlet, a metering pump, and a heating / cooling jacket.
(Epoxy equivalent 180 g / equivalent) 100 parts, bisphenol F (binuclear purity 99%, op-form 52%, oo-form 14%) 50 parts, ethyltriphenylphosphonium acetate monoacetic acid complex (70 in methanol) % Solution) 0.
15 parts and 17.3 parts of propylene glycol diacetate were added, the temperature was increased to 170 ° C. while stirring, and the temperature was kept at the same temperature to polymerize the copolymerized epoxy resin. During the polymerization, 42.0 parts of butyl carbitol was added when the Mw reached 42,000 while monitoring the molecular weight, and the polymerization reaction was stopped by cooling. The time required for the polymerization was 4.5 hours.

The temperature in the reactor was cooled to 115 ° C., and under a nitrogen purge, 13.3 parts of methacrylic acid (MAA), 10.6 parts of styrene (ST), and ethyl acrylate (EA)
2.6 parts, benzoyl peroxide (BPO) (25% water content)
A premixed solution of 4.0 parts and 28.7 parts of butyl carbitol was charged into the epoxy resin solution at a rate of 2.0 parts per minute to perform radical polymerization. The temperature was maintained at 115 ° C. during the reaction, and aging was performed for 1 hour after the completion of the monomer addition to complete the reaction. Next, the temperature in the reactor was cooled to 105 ° C., the nitrogen purge was stopped, and 17.9 parts of a 50% aqueous solution of dimethylethanolamine was added. Neutralized. Thereafter, 160 parts of ion-exchanged water was added at a rate of 40 parts per hour, and emulsification was performed while maintaining the temperature at 85 ° C. during the addition. The stirring torque gradually increased during the addition of water. The torque peaked when about 80 parts of ion-exchanged water was added, and thereafter, the stirring torque decreased. This point was the phase transition point from the water-in-oil emulsion to the oil-in-water emulsion. After adding 160 parts of ion-exchanged water, 150 parts of ion-exchanged water is further added over 30 minutes, and the internal temperature is gradually lowered by 5 minutes.
It cooled so that it might become 0 degrees C or less. The particle size of the completed epoxy resin emulsion was 0.46 μm.

Analysis of the copolymerized epoxy resin revealed that Mn1
The following values were obtained: 0,700, Mw 46,300, epoxy value 17.9 meq / 100 g resin, phenolic hydroxyl value 1.0 meq / 100 g resin. The residual monomer concentration of the epoxy acrylate before neutralization was 5000 ppm as analyzed by gas chromatography. The viscosity at 25 ° C. when the obtained epoxy resin emulsion was diluted to a solid content (NV) of 29% was 260 cps. As a result of storing the emulsion at 50 ° C. for 2 weeks, no change in state was observed, and no abnormalities such as separation and sedimentation occurred. The particle size after the storage test was 0.49 μm, and the viscosity at 25 ° C. was 235 cps.

The above emulsion of 29% NV was coated on an aluminum plate (5182H1) under the condition of a dry coating amount of 100 mg / dm ^2.
Nine materials, phosphoric acid chromate treatment, plate thickness 0.26 mm) were applied and baked in a conveyor type gas heating oven. The baking condition is 270 ° C, the discharge nozzle internal pressure is 150mmH ₂
O, the passage time through the heating zone was 20 seconds.

In the evaluation of the coating film performance, the retort resistance was good and the appearance of the coating film was not changed, and the consumption of potassium permanganate in the eluate was 5.2 ppm in the retort elution.
And a low value of 0.58 mA in bending workability. No corrosion was observed after storage in the corrosion resistance test.

Examples 2 to 5 and Comparative Examples 1 to 5 The experiments of Examples 2 to 5 and Comparative Examples 1 to 5 were performed using the same materials as those used in Example 1. A similar operation was performed. The molar ratio of bisphenol A type liquid epoxy resin to bisphenol F, the amount of catalyst used, reaction conditions, and the like are finely adjusted so that the molar ratio of bisphenol A component to bisphenol F component in the epoxy resin is 60:40 to 4
In the range of 0:60, various copolymerized epoxy resins having different Mn, Mw, epoxy value, and phenolic hydroxyl value were polymerized. After the acrylic modification, 65 mol% of the methacrylic acid component was neutralized with dimethylethanolamine, and ion-exchanged water was added to prepare various epoxy resin emulsions.

The details of the epoxy resin emulsion composition, the analysis results of the epoxy resin, the analysis results of the emulsion, and the evaluation results of the coating film performance are shown in Tables 1 and 2.

With the copolymerized epoxy resins of Examples 2 to 5, as shown in Table 1, a good epoxy resin emulsion having excellent storage stability and coating properties can be produced, and the retort resistance and retort resistance can be improved. Dissolution, bending processability,
The results obtained were excellent in coating film performance such as corrosion resistance and the like.

On the other hand, the copolymerized epoxy resins having comparatively large molecular weights of Comparative Examples 1 and 5 showed poor emulsifiability. In these, the emulsified state of the epoxy resin emulsion was extremely poor, and it was judged that coating was impossible. Evaluation of coating film performance was not performed. Comparative Example 2 was an example in which a good epoxy resin emulsion was not obtained in Comparative Example 1, and the same epoxy resin as that of Comparative Example 1 was used, and an attempt was made to produce an epoxy resin emulsion by increasing the amount of solvent used. is there. Butyl carbitol was used to increase the amount of solvent used. Generally, the emulsifying property is improved by increasing the amount of the solvent used, but the Mw, epoxy value, and phenolic hydroxyl value of the epoxy resin are inappropriate, and the emulsified state is improved, but the storage stability is improved. An epoxy resin emulsion having excellent properties and coatability was not obtained.
In the evaluation of the coating film performance, it is considered that the particle size was too large, but results inferior in retort resistance, bending workability, and corrosion resistance were obtained.

With the copolymerized epoxy resins having comparatively small molecular weights of Comparative Examples 3 and 4, it was easy to prepare an epoxy resin emulsion, and an epoxy resin emulsion excellent in storage stability and coating properties was obtained. Retort resistance, retort elution, because the molecular weight of the resin is too small,
As a result, the film performance such as bending workability and corrosion resistance was inferior.

Example 6 The reactor used in Example 1 was used.
Bisphenol F liquid epoxy resin (epoxy equivalent: 170 g / equivalent) derived from bisphenol F having 49% body and 11% oo body, 100 parts bisphenol A (p-
38.8 parts of bis-nucleus purity (99% of binuclear body, 49% of op-form, oo-form 1)
17.3) 17.3 parts, ethyltriphenylphosphonium acetate monoacetic acid complex (70% solution in methanol)
0.18 parts, propylene glycol diacetate
8 parts were charged, the temperature was raised to 180 ° C. while stirring, and the temperature was kept at the same temperature to polymerize the copolymerized epoxy resin. During the polymerization, 45.6 parts of butyl carbitol was charged when the Mw reached 38,000 while monitoring the molecular weight, and the polymerization reaction was stopped by cooling. The time required for the polymerization was 4.1
It was time.

The temperature in the reactor was cooled to 115 ° C., and under a nitrogen purge, 14.0 parts of methacrylic acid and 8.2 parts of styrene.
Parts, ethyl acrylate 1.1 parts, benzoyl peroxide (2
A premixed solution of 3.7 parts (5% water content) and 16.6 parts of butyl carbitol was charged into the epoxy resin solution at a rate of 1.1 parts per minute to perform radical polymerization. During reaction 115
C., and the mixture was aged for 1 hour after completion of the addition of the monomer to complete the reaction. Next, the temperature in the reactor was cooled to 105 ° C., the nitrogen purge was stopped, and 17.4 parts of a 50% aqueous solution of dimethylethanolamine was added. Neutralized. Thereafter, 160 parts of ion-exchanged water was added at a rate of 45 parts per hour, and emulsification was performed while maintaining the temperature at 85 ° C. during the addition. The stirring torque gradually increased during the addition of water. The torque peaked when about 100 parts of ion-exchanged water was added, and thereafter, the stirring torque decreased. This point was the phase transition point from the water-in-oil emulsion to the oil-in-water emulsion. After adding 160 parts of ion-exchanged water,
160 parts of ion-exchanged water was added over 30 minutes, and the internal temperature was gradually cooled to 50 ° C. or lower. The particle size of the completed epoxy resin emulsion is 0.57μm
Met.

From the analysis of the copolymerized epoxy resin, Mn9,
800, Mw 42,100, epoxy value 20.4 meq / 100 g resin, phenolic hydroxyl value 0.9
A value of meq / 100 g resin was obtained. The residual monomer concentration of the epoxy acrylate before neutralization was 4700 ppm as analyzed by gas chromatography.

The obtained epoxy resin emulsion was subjected to NV
The viscosity at 25 ° C. when diluted to 29% is 375 p
s. As a result of storing the emulsion at 50 ° C. for 2 weeks, no change in state was observed, and no abnormalities such as separation and sedimentation occurred. Particle size after storage test is 0.59μ
m and the viscosity at 25 ° C. was 291 cps.

An emulsion of NV 29% was coated on an aluminum plate (5182H1) under the condition of a dry coating amount of 100 mg / dm ^2.
Nine materials, phosphoric acid chromate treatment, plate thickness 0.26 mm) were applied and baked in a conveyor type gas heating oven. The baking conditions are 270 ° C and the discharge nozzle internal pressure is 150mmH.
₂ O, the passage time through the heating zone was 20 seconds.

In the evaluation of the coating film performance, the retort resistance was good and no change in the appearance of the coating film was observed. In the retort dissolution, the consumption amount of potassium permanganate in the eluate was 6.7 ppm.
And a low value of 1.02 mA in bending workability. No corrosion was observed after storage in the corrosion resistance test.

Examples 7 to 10 In the experiments of Examples 7 to 10, the same operations as in Example 6 were performed using the same materials as those used in Example 6. Bisphenol F type liquid epoxy resin and bisphenol A
The molar ratio of bisphenol A component and bisphenol F component in the epoxy resin is 25:75 to 3 by finely adjusting the molar ratio of bisphenol F, the amount of catalyst used, and the reaction conditions.
In the range of 0:70, various copolymerized epoxy resins having different Mn, Mw, epoxy value, and phenolic hydroxyl value were polymerized. After acrylic modification, 60 mol% of the methacrylic acid component was neutralized with dimethylethanolamine, and ion-exchanged water was added to prepare various epoxy resin emulsions.

Table 3 shows the details of the epoxy resin emulsion composition, the analysis results of the epoxy resin, the analysis results of the emulsion, and the evaluation results of the coating film performance. With the copolymerized epoxy resins used in Examples 7 to 10, an epoxy resin emulsion having excellent storage stability and coatability was obtained, and excellent results were also obtained in evaluation of coating film performance.

Examples 11 to 15 In the same manner as in Example 1, 100 parts of a bisphenol A type liquid epoxy resin (epoxy equivalent: 180 g / equivalent) contained a pp binuclear substance in a quantitative ratio as shown in Table 4. 99%
The above bisphenol A, binuclear content 99%, o-
Combination of 53% p-form and 17% oo-form bisphenol F, the molar ratio of liquid epoxy resin to bisphenol,
The amount of the catalyst used, the reaction conditions and the like are finely adjusted, and the molar ratio of the bisphenol A component to the bisphenol F component in the epoxy resin is in the range of 75:25 to 70:30, and Mn, Mw,
Various copolymerized epoxy resins having different epoxy values and phenolic hydroxyl values were polymerized. Next, the epoxy resin / acrylic resin / solvent usage ratio is 80/20/60.
Acrylic modification was carried out under the conditions of
% And neutralized water was added to prepare various epoxy resin emulsions.

Table 4 shows the details of the epoxy resin emulsion composition, the analysis results of the epoxy resin, the analysis results of the emulsion, and the evaluation results of the coating film performance. Also in the copolymerized epoxy resin used in Examples 11 to 15,
An epoxy resin emulsion having excellent storage stability and coatability was obtained, and excellent results were also obtained in evaluation of coating film performance.

Example 16 In the same manner as in Example 1, a bisphenol F type liquid epoxy resin (epoxy) derived from bisphenol F having a binuclear content of 99%, an op-form 53% and an oo-form 17% was used. (Equivalent 170 g / equivalent) 100 parts, pp binucleate content 99
% Of bisphenol A, bisphenol F (binuclide content 99%, op-form 53%, oo-form 1
7%) 21.2 parts, using an ethyltriphenylphosphonium acetate monoacetic acid complex as a catalyst and propylene glycol diacetate as a reaction solvent, the temperature was raised to 170 ° C and 3.2.
After reacting for hours, Mn 14,100, Mw 69,30
A copolymerized epoxy resin having 0, an epoxy value of 10.5 meq / 100 g resin, and a phenolic hydroxyl value of 1.2 meq / 100 g resin was polymerized. Termination of the polymerization of the epoxy resin was performed by lowering the temperature by adding butyl carbitol.

After the temperature was lowered to 110 ° C., while maintaining the same temperature, 65% of methacrylic acid was added to the epoxy resin solution.
40.7 parts of an acrylic monomer composed of 34% of styrene and 1% of ethyl acrylate, 1 per acrylic monomer
A homogeneous mixed solution of 2.5% benzoyl peroxide (containing 25% water) and butyl carbitol was added dropwise over 45 minutes, and the mixture was aged for 1 hour to complete the acrylic modification reaction.

Then, a 50% aqueous solution of dimethylethanolamine in an amount to neutralize 50 mol% of methacrylic acid was added, and the mixture was stirred for 5 minutes and mixed uniformly. Thereafter, half the amount of 320 parts of ion-exchanged water was dropped over 4 hours, and the phase was changed from a water-in-oil emulsion to an oil-in-water emulsion to emulsify the epoxy resin emulsion. During that time, care was taken so that the temperature inside the reactor did not drop below 80 ° C. The other half of the ion-exchanged water was dropped in 30 minutes, during which the reactor internal temperature was gradually lowered to 50 ° C. or lower.

When the temperature inside the reactor reached 50 ° C., a carnauba wax emulsion (H-367) manufactured by Chukyo Yushi Co., Ltd. with a wax content of 0.7 part per 100 parts of the resin content in the epoxy resin emulsion was used. 1.0 part of a resole resin solution (Hitanol 4010) manufactured by Hitachi Chemical Co., Ltd. was added as a resin component, and 1% of isobutanol was added to the final water-based paint as a leveling agent and a wettability improver, and the solid content was reduced to 29%. % To adjust the aqueous paint.

The obtained water-based paint has a particle size of 0.43 μm.
And the viscosity at 25 ° C. was 195 cps. The storage stability is also good, and the particle size after the storage test is 0.44 μm.
The viscosity at 25 ° C. was 188 cps, and hardly changed.

In the evaluation of the performance of the coating film, the retort resistance was good, the appearance of the coating film was not changed, and the eluate consumption of potassium permanganate was 7.8 ppm in the retort dissolution property.
And also a low value of 0.32 mA in bending workability. No corrosion was observed after storage in the corrosion resistance test.

Comparative Examples 6 to 10 In Table 5, Comparative Examples 6 to 10 will be described. Comparative Example 6 is an example in which the molar ratio of the bisphenol A component to the bisphenol F component in the epoxy resin is 85:15, and the amount of the bisphenol A component is excessive. Mn of epoxy resin is 11,0
Although the Mw was 47,900, the epoxy value was 14.0 meq / 100 g resin, and the phenolic hydroxyl value was 1.1 meq / 100 g resin, the bisphenol A component amount was excessive. Because
The viscosity during the polymerization of the epoxy resin, the acrylic modification reaction, and the neutralization / emulsification process becomes very high, resulting in poor emulsification,
Only emulsions that were impossible to evaluate for coating and coating performance were obtained.

In Comparative Example 7, the molar ratio of the bisphenol A component to the bisphenol F component in the epoxy resin was 15:85.
This is an example in which the amount of the bisphenol F component is excessive. Although the Mn of the epoxy resin was 11,100, the Mw was 48,700, the epoxy value was 13.3 meq / 100 g resin, and the phenolic hydroxyl value was 1.0 meq / 100 g resin, Excessive bisphenol F content resulted in poor coating film performance. Although an epoxy resin emulsion excellent in storage stability and coatability was obtained, in the evaluation of the coating film performance, the coating film was whitened by the retort treatment, and the retort elution property was 15.1 ppm.
And the bending workability was good, but the corrosion resistance was extremely poor.

Comparative Examples 8 and 9 are examples in which the epoxy resin polymerized in Example 1 was used and the amount of solvent used was changed. In Comparative Example 8, after the polymerization reaction of the copolymerized epoxy resin, instead of stopping the reaction by adding butyl carbitol, the epoxy resin was once taken out of the reactor and quenched to terminate the reaction. This is an example in which the use of the solvent is restricted and the amount of solvent used is significantly reduced. The ratio of epoxy resin / acrylic resin / solvent usage is 85/15/19. Acrylic modification, neutralization, and emulsification were attempted in the same manner as in Example 1. However, the viscosity was very high, and the compatibility between the acrylic monomer and the epoxy resin tended to be poor in the acrylic modification step. Did not enter the epoxy acrylate and became incapable of emulsification.

Comparative Example 9 is an example in which the amount of solvent used was greatly increased, contrary to Comparative Example 8. As the solvent increase, butyl carbitol was used, and the epoxy resin / acrylic resin / solvent usage ratio was 85/15/80. The viscosity during the production of the epoxy resin emulsion is generally low, with a particle size of 0.08 μm
Was obtained. The viscosity of NV 29% was very high, exceeding 1000 cps. The particles were easily fused to each other due to an excessive amount of the solvent, and changed to a purine state in a storage test. In addition, the coatability is poor, and 1
In the case of coating and baking at a concentration of 00 mg / dm ² , intense armpits occurred, and a coated plate capable of evaluating coating film performance could not be obtained.

Comparative Example 10 is an example in which bisphenol F having a low o-form content was used as the bisphenol F component in the epoxy resin. Mn of epoxy resin is 10,800, Mw
45,500, epoxy value 16.7 meq / 10
Despite the fact that the 0 g resin and the phenolic hydroxyl value were appropriate as 0.9 meq / 100 g resin, the o-form content in the bisphenol F component was too low, so that the polymerization of the epoxy resin, the acrylic modification reaction, and The viscosity during the neutralization / emulsification step was extremely high, resulting in poor emulsification, and only an emulsion which could not be evaluated for coating and coating film performance was obtained.

[0156]

[Table 1]

[0157]

[Table 2]

[0158]

[Table 3]

[0159]

[Table 4]

[0160]

[Table 5]

[0161]

According to the present invention, the amount of solvent used is limited to a low VOC during production and use of a water-based paint,
Uses a high molecular weight epoxy resin that can be used for applications requiring high workability such as easy open end (EOE), and further limits the amount of acrylic used within the range that does not impair the corrosion resistance of the coating film. It is possible to provide an epoxy resin emulsion having an excellent dispersibility and viscosity stability in a particle diameter range in which excellent paintability and coating film performance can be obtained. According to the present invention, the epoxy acrylate emulsion can be prepared in a small number of steps and with good workability.
It can be manufactured economically.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C09D 151/08 C09D 201/06 191/06 C08J 3/03 201/06

Claims (17)

[Claims] A bisphenol A and a bisphenol F in a molar ratio of 2: 8 to 8: 2 having a number average molecular weight of 7,000 to 15,000 and a weight average molecular weight of 30,000.
A carboxylic acid component in the presence of a bisphenol-type copolymerized epoxy resin having an epoxide value of from 8 to 30 meq. And a phenolic hydroxyl value of not more than 5 meq. By radical polymerization of an acrylic monomer containing, as an essential component, 75 to 95 parts by weight of an epoxy resin component and 5 to 25 parts by weight of an acrylic resin component per 100 parts by weight of a resin, and 20 organic solvent components per 100 parts by weight of a resin. To 70 parts by weight of an epoxy acrylate composition, neutralizing the epoxy acrylate composition with a basic compound, and adding water to emulsify the mixture to obtain an average particle diameter of 0.1 to 0. A process for producing an 8 micron epoxy resin emulsion. 2. The bisphenol-type copolymerized epoxy resin is a copolymerized epoxy resin derived from (A) a diglycidyl ether of bisphenol A and / or bisphenol F and (B) bisphenol F, bisphenol A or a mixture thereof. A method for producing an epoxy resin emulsion according to claim 1. 3. The bisphenol-type copolymerized epoxy resin, wherein bisphenol F contains at least 40 mol% of oo and op methylene conjugates, and has a binuclear content of 96%
3. The method for producing an epoxy resin emulsion according to claim 1, wherein the amount is not less than% by weight. 4. 4. The epoxy resin according to claim 1, wherein said bisphenol-type copolymerized epoxy resin is derived from diglycidyl ether of bisphenol and bisphenol in a molar ratio of 100: 70 to 100: 95. Emulsion manufacturing method. 5. When the bisphenol-type copolymerized epoxy resin has a desired molecular weight, epoxy value, and phenolic hydroxyl value, a solvent is added to the reaction system,
The product is prepared by cooling to stop the reaction.
5. The method for producing an epoxy resin emulsion according to any one of claims 1 to 4. 6. The acrylic monomer is methacrylic acid 4
The method for producing an epoxy resin emulsion according to any one of claims 1 to 5, wherein the monomer mixture comprises 0 to 70% by weight, 30 to 50% by weight of styrene, and 0.1 to 20% by weight of ethyl acrylate. 7. The epoxy resin according to claim 1, wherein radical polymerization of an acrylic monomer containing the carboxylic acid component as an essential component is carried out using a peroxide initiator. Emulsion manufacturing method. 8. The method according to claim 7, wherein the peroxide initiator is benzoyl peroxide. 9. The method according to claim 7, wherein the peroxide initiator is used in an amount of 8 to 15% by weight per acrylic monomer. 10. The method for producing an epoxy resin emulsion according to claim 1, wherein the radical polymerization is performed in a temperature range of 110 ± 5 ° C. 11. The radical polymerization wherein the monomer concentration is 60
The method for producing an epoxy resin emulsion according to any one of claims 1 to 10, wherein the conversion is performed up to a conversion rate of 00 ppm or less. 12. The neutralization of the epoxy acrylate mixture with a basic compound by the carboxylic acid component of 40 to 8%.
The method is performed so as to neutralize 0 mol%.
12. The method for producing an epoxy resin emulsion according to any one of claims 1 to 11. 13. The method for producing an epoxy resin emulsion according to claim 1, wherein the basic compound is dimethylethanolamine. 14. The method for producing an epoxy resin emulsion according to claim 1, wherein the neutralization of the epoxy acrylate mixture with a basic compound is performed in a temperature range of 105 ± 10 ° C. 15. The emulsification continues with at least 60 parts water per 100 parts epoxy acrylate at a rate of 10 to 50 parts per hour while keeping the neutralized epoxy acrylate at a temperature of 85 ± 10 ° C. 3. The method according to claim 1, wherein the water-in-oil emulsion is phase-converted from a water-in-oil emulsion to an oil-in-water emulsion.
5. The method for producing an epoxy resin emulsion according to any one of 4. 16. A method for producing a water-based paint, comprising adding a wax component after producing an epoxy resin emulsion by the production method according to any one of claims 1 to 15. 17. A method for producing a water-based paint, comprising adding a methylol group-containing thermosetting resin component after producing an epoxy resin emulsion by the production method according to any one of claims 1 to 15.