JPH01149864A - Room temperature curing emulsion coating - Google Patents

Abstract

PURPOSE:To obtain the title one-pack type emulsion coating, containing a polymer emulsion containing an epoxy resin in particles and a copolymer having a crosslinking accelerator or amino groups which are crosslinking points on the outer layer of the particles as a vehicle and having excellent operability. CONSTITUTION:The aimed emulsion coating, containing an polymer emulsion obtained by emulsion polymerizing (A) an ethylenically unsaturated monomer without containing amino group in the molecule with (B) a water-insoluble epoxy resin (e.g., aliphatic epoxy resin), e.g., at 100:100-100:5 ratio, and then emulsion polymerizing the resultant polymer with (C) 1-25wt.% (in other ethylenically unsaturated monomers) amino group-containing ethylenically unsaturated monomer (e.g., dimethylaminoethyl acrylate) and (D) other ethylenically unsaturated monomers as a vehicle, having excellent storage stability and capable of imparting films having excellent durability.

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention is directed to a copolymer containing an epoxy resin inside the particles and having an amino group in the outer layer of the particles that can act as a crosslinking accelerator or a crosslinking point for the epoxy resin. The present invention relates to an emulsion paint whose vehicle is a polymer-containing polymer emulsion that crosslinks at room temperature.

[Prior art and its problems]

Currently, many polymer emulsions are used as vehicles for emulsion paints, and it is well known that the durability of paint films can be improved by crosslinking the polymer emulsions used as vehicles by some method. Various cross-linking methods have already been proposed, and some have already been put into practical use.

The most well-known and practically used crosslinking method is to add melamine to a polymer emulsion made by copolymerizing monomers with various reactive groups such as N-methylol acrylamide, acrylamide, and β-hydroxyethyl acrylate. There are some that are crosslinked by blending aminoplasts such as resins.

However, in this case, almost no crosslinking occurs when drying at room temperature, so its use is limited to applications such as industrial coatings that can be dried by heating. By the way, emulsion paints are the most commonly used architectural paints and are applied by drying at room temperature, but carboxyl group-containing monomers are copolymerized with carboxyl group-containing monomers, which can be crosslinked at room temperature. A relatively common method is to add a polyvalent metal salt such as zinc white to a xylated polymer emulsion to ionically crosslink carboxyl groups and metal ions. However, in this case, it has the disadvantage that it is easily hydrolyzed by water, alkali, etc., and for this reason, it is not sufficiently effective when applied to base materials such as mortar and concrete, for which emulsion paints are often used; It is hydrolyzed and used in floor polishes and other products that take advantage of the removable properties of the paint film.

On the other hand, a method of crosslinking by mixing and blending an emulsified dispersion of epoxy resin or a water-soluble epoxy resin with a carboxylated polymer emulsion has been carried out, in which the glycidyl groups of the epoxy resin and the carboxyl groups in the polymer It is known that a crosslinking reaction can be carried out using an amino compound as a promoter.

However, if the emulsified dispersion of epoxy resin or water-soluble epoxy resin and Cal? A crosslinking method using a xylated emulsion polymer in combination also has limitations in the stability of the formulation, and poses a problem of so-called pot life. For this reason, epoxy resins and/or crosslinking accelerators are generally added at the time of use.
It is a two-component type that is mixed and used, but it has the disadvantage of poor workability during use.

In addition, when using an emulsified dispersion of epoxy resin, the epoxy resin and carboxylated polymer are separate particles, so an emulsifier layer that stabilizes the dispersed particles by adsorbing to the particle surface is used. On the other hand, when a water-soluble epoxy resin is used, this problem is less likely to occur, but the stability of the formulation decreases and the pot life is shortened. There are problems in handling as the length is short.

As a method for solving such problems, for example, Japanese Patent Publication No. 59-52188 discloses a method of emulsion copolymerizing ethylene and vinyl acetate in the presence of a polyvinyloxy compound. It is stated that it is good to produce an ethylene-vinyl acetate copolymer emulsion containing a xyl resin, blend it with a pigment dispersion, and then add a curing accelerator of an organic amino compound before use as a paint. In this case, the epoxy compound exists uniformly in the ethylene-vinyl acetate copolymer particles in a dispersed state, and the epoxy compound in the particles is protected by the ethylene-vinyl acetate copolymer. It has also been shown that the pot life will be longer and better coating performance will be obtained even if . However, even in this method, a curing accelerator must be added before use.
Since it is a so-called two-component paint, the work of mixing the two components at the painting site is complicated, and when a curing accelerator made of water-insoluble amino resin is used, it is especially difficult to use epoxy resin. Since the resin-containing polymer emulsion and the water-dispersed curing accelerator are mixed in the form of particles, there is a risk that the coating film performance will be insufficient if the polymer and curing accelerator are not sufficiently compatible. Furthermore, when a water-soluble low molecular weight amino compound curing accelerator is used, when a paint is applied to a porous base material such as cement mortar or concrete, water permeates into the base material and Dissolved curing agents may permeate along with the curing agent, and if it has a low molecular weight, it may evaporate and be lost during drying, resulting in the disadvantage that sufficient performance cannot be achieved.

The present invention was made to solve the following problems: - A room-temperature curing method that can be used in liquid form, is stable, has excellent storage stability, and provides a good crosslinked coating film even at room temperature. The purpose of the present invention is to provide emulsion paints with high compatibility.

[Failure to solve the problem]

In the present invention, (IL) an ethylenically unsaturated monomer that does not contain an amino group in its molecule is emulsion polymerized in the presence of a water-insoluble epoxy resin to produce an emulsion polymer as seed particles, and then (b) A polymer emulsion obtained by emulsion polymerizing an ethylenically unsaturated monomer containing an amino group and another ethylenically unsaturated monomer copolymerizable therewith in the presence of the emulsion polymer. It is an emulsion paint that cures at room temperature as a vehicle.

The polymer emulsion used in the present invention is the above-mentioned (a)
) and (b) are obtained in the same emulsified fine particles, the part containing the water-insoluble epoxy resin as a crosslinking agent, and the amino group-containing ethylenically unsaturated monomer (which also serves as a crosslinking accelerator or crosslinking point). This layered structure provides a stable emulsion polymer that can be used in one-component form.

The structure of the polymer emulsion used in the present invention will be explained in more detail below.

The water-insoluble epoxy resin-containing emulsion polymer used as seed particles in the production of a polymer emulsion is obtained by dissolving the water-insoluble epoxy resin in an ethylenically unsaturated monomer used for emulsion polymerization, and then emulsion polymerizing it by a known method. In particular, it is easily obtained.

Another method is to add and disperse a water-insoluble epoxy resin in an aqueous phase containing an emulsifier, and then perform emulsion polymerization while adding an ethylenically unsaturated monomer.

Here, the weight ratio of the ethylenically unsaturated monomer and the water-insoluble epoxy resin is preferably 100:100 to 100:5; if the epoxy resin exceeds this value, a large amount of the epoxy resin will not be incorporated into the emulsion polymer particles. Otherwise, problems arise in that the stability of the produced emulsion polymer decreases and the occurrence of aggregates increases during emulsion polymerization. On the other hand, if the ratio of the epoxy resin decreases, the content of the epoxy resin in the final emulsion will naturally decrease, making it impossible to obtain a sufficient crosslinking effect.

The most useful water-insoluble epoxy resin is epichlorohydrin-bisphenol A type epoxy resin, which is the main type of commercially available epoxy resin. Can be used if it is soluble in any of the saturated monomers,
As these, aliphatic epoxy resins and epoxidized urethane resins are also useful.

Epoxy resins that are highly water-soluble or hydrophilic cannot be used in the present invention because they are difficult to penetrate into the emulsion polymer particles and tend to exist in the aqueous phase or on the surface of the polymer particles.

Next, as the amino group-containing ethylenically unsaturated monomer used in the second stage emulsion polymerization, which is step (b), N-methylaminoethyl acrylate or methacrylate,
Alkylamino esters of acrylic acid or methacrylic acid such as dimethylaminoethyl acrylate or methacrylate, monovinylpyridines such as vinylpyridine, vinyl ethers having an alkylamino group such as dimethylaminoethyl vinyl ether, N-(2-dimethylaminoethyl) Among these, dimethylaminoethyl acrylate or methacrylate are particularly useful for copolymerization with other ethylenically unsaturated monomers, such as unsaturated amides having an alkylamino group such as acrylamide or methacrylamide. be.

These amino group-containing ethylenically unsaturated monomers are used at a ratio of 1 to 25% by weight in the ethylenically unsaturated monomers used in the second stage emulsion polymerization, but the amount of copolymerization is less than this. On the other hand, when used in a larger amount, these amino group-containing ethylenically unsaturated monomers have strong hydrophilic properties, so the hydrophilicity of the copolymer also decreases. This results in a drawback that the water resistance of the resulting emulsion polymer film decreases.

Copolymerization using ethylenically unsaturated carboxylic acid as part of the ethylenically unsaturated monomer is important for the reasons described below, but ethylenically unsaturated carboxylic acid is ), it may be used in the next emulsion polymerization step (b), or it may be used in both.

As described above, the ethylenically unsaturated carboxylic acids used as important components in the ethylenically unsaturated monomer in step (a) and/or (b) include ethylenic acids such as acrylic acid, methacrylic acid, and crotonic acid. Ethylenically unsaturated dibasic carboxylic acids such as unsaturated-basic carboxylic acid, itaconic acid, maleic acid, and fumaric acid, and one or more of these are used. Additionally, monoalkyl esters of ethylenically unsaturated dibasic caldic acids can also be used.

The use of these ethylenically unsaturated carboxylic acids not only serves as a crosslinking point with the epoxy resin, but also has the effect of improving the mechanical stability of emulsion polymers, as is well known. Since the crosslinking point with the epoxy resin is also available, the amount used does not necessarily have to be in an equivalent relationship with the reactive group of the epoxy resin, but the amount used is not necessarily in an equivalent relationship with the reactive group of the epoxy resin. If the amount is less than 1 to 10% by weight of the total amount of each ethylenically unsaturated monomer in These ethylenically unsaturated calcium compounds are undesirable because they reduce water resistance and alkali resistance. In the present invention, phosphoric acid is used during the emulsion polymerization of seed particles and/or during the subsequent emulsion polymerization.

Other ethylenically unsaturated monomers used in the polymer emulsion of the present invention include acrylic esters such as methyl acrylate, ethyl acrylate, and butyl acrylate; methacrylic esters such as methyl methacrylate and ethyl methacrylate. esters of maleic acid, fumaric acid, and tetraconic acid; vinyl acetate, vinyl zolopionate,
Vinyl esters such as tertiary vinyl carboxylate; aromatic vinyl compounds such as styrene and vinyltoluene; heterocyclic vinyl compounds such as vinylpyrrolidone; vinyl chloride;
Acrylonitrile, vinyl ether, vinyl ketone, vinylamide, etc.; halogenated vinylidene compounds such as vinylidene chloride, vinylidene fluoride; α-olefins such as ethylene and propylene; dienes such as butadiene, etc. Amides of α, β-ethylenically unsaturated acids such as amide and maleic acid amide; substituted amides of unsaturated caldenic acids such as N-methylol acrylamide or methacrylamide, diacetone acrylamide; diallylphthale), divinylbenzene, allyl acrylate Monomers having two or more unsaturated bonds in one molecule, such as trimethylolpronotrimethacrylate, etc., can also be used. Furthermore, those having an unsaturated group, a sulfonic acid group, a sulfate group, such as vinyl sulfonic acid, styrene sulfonic acid, allyl alkyl itaconate sulfate, and alkali salts thereof can also be used.

Next, a method for emulsion polymerization of the polymer emulsion used in the present invention will be described.

An emulsion polymer containing a water-insoluble epoxy resin serving as seed particles is produced by a known emulsion polymerization method using a radical generation initiator from an ethylenically unsaturated monomer mixture in which an epoxy resin is dissolved in water in the presence of an emulsifier. do. Alternatively, an epoxy resin may be added to an aqueous phase in which an emulsifier is dissolved, and after emulsion dispersion, an ethylenically unsaturated monomer mixture and a radical generation initiator may be added, and emulsion polymerization may be carried out by a known method.

Next, the emulsion polymer obtained above is added to the aqueous phase, an ethylenically unsaturated monomer mixture and a radical generation initiator are added in the same manner, and emulsion polymerization is carried out by a known method to form a polymer emulsion. In this case, an additional emulsifier may be added in addition to the emulsion polymer of the seed particles to stabilize the polymerization system, such as to prevent the formation of aggregates during emulsion polymerization.

The above method is a method in which seed particles are separately produced and used for emulsion polymerization in the next step. It can also be produced by emulsion polymerization by adding an ethylenically unsaturated monomer mixture and a radical generation initiator to be used in the next step of emulsion polymerization. That is, in an aqueous phase in which an emulsifier is dissolved, an ethylenically unsaturated monomer mixture serving as seed particles is emulsion polymerized using a radical generation initiator in the presence of an epoxy resin, and then the ethylenically unsaturated monomer mixture in the next step is polymerized using a radical generation initiator. A polymer emulsion used in the present invention is obtained by adding a polymer mixture and a radical generation initiator and carrying out emulsion polymerization.

The weight ratio of all ethylenically unsaturated monomers in the water-insoluble epoxy resin second particle production process (2) and the latter stage emulsion polymerization process (b) needs to be 2:100 to 50 to 100. When the ratio of epoxy resin is less than 2:100, a sufficient crosslinking effect cannot be obtained, and when the ratio is more than 50:100, the stability of the resulting emulsion polymer decreases, and unreacted epoxy resin remains. Emulsion polymers have the disadvantage that the resulting film is excessively soft.

Examples of emulsifiers used in the production of the polymer emulsion used in the present invention include anionic compounds such as sodium alkylbenzene sulfonate, sodium diuryl sulfate, sodium dioctyl sulfosuccinate, and alkylphenyl polyoxyethylene sulfate sodium salt or ammonium salt. Emulsifier, phoroxyethylene alkyl phenyl ether, polyoxyethylene alkyl ether,
Examples include those commonly used in emulsion polymerization, such as polyoxyethylene-4-lioxypropylene block copolymers. The amount of emulsifier used is in the range of 0.5 to 15% by weight based on the total weight of the water-insoluble epoxy resin and ethylenically unsaturated monomer in the emulsion polymerization process (,) of the emulsion polymer that becomes the seed particles. It is preferable to use a larger amount of emulsifier, since this may result in a decrease in the water resistance of the final polymer emulsion, and a smaller amount of emulsifier may result in poor stability during emulsion polymerization and poor stability of the resulting emulsion polymer. stability may decrease. Furthermore, the additional amount of emulsifier used in the next emulsion polymerization step (b) should be 10% by weight or less based on the solid weight of the emulsion polymer in the seed particles, in order to reduce the generation of new particles. desirable.

In addition, as the radical generation initiator used in emulsion polymerization to obtain a polymer emulsion, those used in ordinary emulsion polymerization are used, and these include potassium persulfate, ammonium persulfate, and azobisisobutylnitrile. and its hydrochloride, and cumene hydro A? -oxide, t@rt-butyl hydroperoxide, and other organic peroxides can also be used if necessary. Furthermore, a known redox initiator is also used in which these persulfates or peroxides are used in combination with metal ions such as iron ions and reducing agents such as sodium sulfooxylate formaldehyde, sodium pyrosulfite, and L-ascorbic acid. be able to.

From a practical point of view, the concentration during emulsion polymerization is preferably such that the final emulsion has a solid content concentration of 25 to 65% by weight, and also to prevent the formation of ethylenically unsaturated monomers and radicals in the reaction system. The initiator can be added by any known method such as batch charging, continuous dropwise addition, and divided addition.

The temperature during emulsion polymerization may be within the range used in known emulsion polymerizations, and the emulsion polymerization is performed under normal pressure or under pressure when a gaseous ethylenically unsaturated monomer is used.

The room temperature curable emulsion paint of the present invention is produced in exactly the same manner as in the production of conventional emulsion paints using the above-specified polymer emulsion as a vehicle. i.e. pigments, fillers, aggregates, dispersants, wetting agents, thickeners and/or rheology control agents, defoamers, plasticizers, coalescents, organic solvents, preservatives, anti-padding agents, -modifiers. They are selected and combined according to their purpose, such as anti-corrosion agents and anti-corrosion agents, and are made into paints using normal methods.

The paint of the present invention thus obtained has good storage stability, there is no need to worry about pot life during painting work, it can be applied in the same way as conventional emulsion paints, and it has excellent durability by simply drying at room temperature. Of course, the room-temperature-curing emulsion paint of the present invention can also be used in a heating drying process, and a good cross-linked paint film can also be obtained by this, so it is suitable for on-site painting. In addition, it is useful as an energy-saving (low-temperature curing) paint in various industrial coatings in factories.

[Examples, etc.]

The present invention will be explained in more detail with reference to examples below, but the present invention is not limited only to the following examples.
All parts and parts below are based on weight.

Example 1. Comparative example 1. Comparative Example 2 The following raw materials were charged and dissolved in a 1.5 t reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer.

Deionized water 324.0 parts Emulgun 931 (Kao product: nonionic emulsifier) 16.0 parts Neodan R (Daiichi Kogyo Seiyaku product: anionic emulsifier) 4.0 parts rlQ) Next, put the following mixture into the dropping funnel. Ta.

Ebicuron 850 (Dainippon Ink & Chemicals ■Product: epoxy resin) 40.0 parts Butyl acrylate
200.0 parts methyl methacrylate
192.0 parts acrylic acid
While feeding 8.0 parts of nitrogen gas and stirring, the internal temperature of the reactor was raised to 60°C, 40 parts of a 2% potassium persulfate aqueous solution dissolved in deionized water was added, and then added dropwise. Added 20% of the epoxy resin and monomer mixture in the funnel. While controlling the temperature rise due to polymerization heat using a water pass and maintaining the internal temperature at 80'C, the remaining epoxy resin/monomer mixture and 2% potassium persulfate aqueous solution 8
0 part was added dropwise over 2 hours to polymerize. After further holding at 80° C. for 2 hours, the mixture was cooled to room temperature, filtered through a 200-mesh filter cloth, and taken out to obtain an emulsion polymer serving as seed particles.

This product had a nonvolatile content concentration of 50.3% and a pH of 2.8.

The emulsion polymer 45 obtained above was placed in a similar 1.5 t reactor.
2 parts and 125 parts water. Next, the following ethylenically unsaturated monomer mixture was prepared and placed in the dropping funnel.

Ethyl acrylate 120.0 parts Methyl methacrylate 74.0 parts Dimethylaminoethyl methacrylate 4.0 parts Acrylic acid 2.0 parts While feeding nitrogen gas and stirring, the internal temperature of the reactor was raised to 70°C. Then, 60 parts of a prepared aqueous solution of potassium dithipersulfate and the above monomer mixture were added dropwise to a separate dropping funnel for polymerization. These drops were carried out for 2 hours while maintaining the internal temperature at 70°C. Furthermore, after holding at the same temperature for 2 hours, it was cooled to room temperature for 2 hours.
The mixture was filtered through a 00 mesh filter cloth to obtain a polymer emulsion (E-1) used in the present invention. The obtained polymer emulsion (E-1) had a nonvolatile content concentration of 50.2 cm, a voice of 5.9, and a viscosity of 120 cps (BM type rotational viscometer, p-tar A
2. Number of revolutions: 6 Orpm. (measured at 25°C). Next, when this emulsion was adjusted to 9.5 with aqueous ammonia and stored at 50° C. for 1 month, both were stable without any changes such as aggregation. In addition, each emulsion before and after voice adjustment was applied onto a glass plate using a 3 mil applicator, and after drying at room temperature of approximately 25°C for 48 hours, a rubbing test was performed on the surface with a cloth soaked in toluene. As a result, although some damage was observed on the surface after 50 rubbings, it was found that the coatings did not dissolve and disappear, showing good solvent resistance, and that a crosslinked film was formed.

On the other hand, as Comparative Example 1, the epoxy resin, the ethylenically unsaturated monomer used in the seed particles, and the ethylenically unsaturated monomer used in the second stage polymerization were mixed to have the same composition as in Example 1. A polymer emulsion (RE-1) is obtained by carrying out emulsion polymerization under the same emulsion polymerization conditions as with the seed particles.
I got it. The obtained polymer emulsion (RE-1) had a nonvolatile content of 50.2%, a pH of 5.8, and a viscosity of 180 cP.
It was s. As in Example 1, we performed a toluene rubbing test (toluene rubbing test) on the film and a storage test at 50°C using the film as it was and the film with - adjusted to 9.5. As a result, the solvent resistance of the film was both It was good, but the one with pH 5.8 was stored at 50℃ for 2 weeks, and the one with pH 9.5 was stored at 50℃.
After 3 days, the mixture agglomerated and had poor stability.

Furthermore, as Comparative Example 2, a polymer emulsion (RE-
2) was obtained. However, in this case, in order to set the nonvolatile content concentration to 50%, the amount of deionized water charged was also reduced by a corresponding amount for emulsion polymerization. The resulting polymer emulsion (RE
-2) had a nonvolatile content concentration of 50.0%, a pH of 6.0, and a viscosity of 150 cPa.

The stability of the unadjusted product and the product adjusted to pH 9.5 was good even after 1 month at 50°C, but the film was dissolved and lost in the toluene rubbing test.

Using each of the polymer emulsions obtained above, emulsion paints were produced according to the following formulations.

[Composition]

water 10
0 parts water-dispersible soybean lecithin (dispersant)
3z ethylene glycol (antifreeze agent) 2
01 Dibutyl phthalate (plasticizer) 11N
Polymer emulsion 3201 Non-volatile content concentration: 58% Pigment volume concentration = 50% The test results of each paint and coating performance are as shown in Table-1.

Table 1 [Test method] Base material: Commercially available cement/asbestos board Paint application method: Two coats with a brush, 200fi7/d Drying = 23°C, 7 days at 60°RH Paint viscosity: Stomer type viscometer by. Measurement temperature: 25°C.

Water resistance: Soaked in water for 2 weeks (approximately 20°C).

Alkali resistance: Immersed in 2% NaOHy Ca (OH) 2 saturated aqueous solution for 2 weeks (approximately 20°C).

Solvent resistance: Rub the coated surface 100 times by hand using absorbent cotton impregnated with toluene.

Weather resistance: 1. on the Sunshine Weather Meter.
000 hours exposure.

The paint of Example 1 had good stability and film performance, but the paint of Comparative Example 1 had excellent film performance but poor stability, while the paint of Comparative Example 2 had good stability. However, the coating performance was poor.

Example 2. Comparative Example 3 The following raw materials were charged into the same reaction apparatus as in Example 1 and dissolved.

Deionized water 332.0 parts Emuldan 931 16.0 parts Neuff
yEA-1204, 0 parts Hytenol N-082, 0 parts Next, while introducing nitrogen gas and stirring, the following pre-dissolved epoxy resin/monomer mixture was charged.

Epicron 1050 (Inu Nippon Ink Chemical Industry Product: Edexy resin) 24.0 parts Butyl acrylate
50.0 parts methyl methacrylate
47.0 parts methacrylic acid
3.0 parts Then, after adjusting the internal temperature to 30°C, 1
0.5 parts of an aqueous solution of TiF@C15.6H20 was added, and further 50 parts of an aqueous solution of ammonium di-thipersulfate and 50 parts of an aqueous solution of sodium di-thibirosulfite were added. Multipolymerization started at K, generating heat and producing an emulsion polymer that became seed particles. After the heat generation stopped, the internal temperature was maintained at 50°C for 1 hour, and then the following monomers prepared in advance were added. The mixture, 50 parts of an aqueous ammonium dithipersulfate solution, and 50 parts of a 2% aqueous sodium pyrosulfite solution were added dropwise over 2 hours to polymerize.

Butyl acrylate 80.0 parts Ethyl acrylate 79.0 parts Methyl methacrylate 129.0 parts Dimethylaminoethyl methacrylate 9.0 parts Methacrylic acid
3.0 parts After further holding at 50°C for 2 hours, it was cooled to room temperature, and -I was diluted with 8.5 parts of ammonia water.
After adjusting the temperature, it was filtered through a 200 mesh filter cloth and taken out to obtain a polymer emulsion (E-2) used in the present invention. This product had a nonvolatile content concentration of 45.3 cm, a viscosity of 100 ePa, and good storage stability at 50° C. for 1 month.

On the other hand, as Comparative Example 3, the same as above but excluding the jepoxy resin was subjected to emulsion polymerization in the same manner as above to obtain a polymer emulsion (RE-3). This one has a non-volatile content of 44.
0%, viscosity 70 cPs (measured at 25° C. using a BM rotational viscometer, rotor A1, rotation speed 6 Orpm), and - was similarly adjusted to 8.5.

The polymer emulsion (E-2) of this example and the polymer emulsion (R
E-3) was applied to a glass plate in the same manner as in Example 1 to form a film.

Next, a toluene rubbing test similar to that in Example 1 was conducted, and the result was that the polymer emulsion (E-2) of this example
The coating was slightly damaged by toluene rubbing, but in the comparative polymer emulsion (RE-3), most of the rubbed portion of the coating was dissolved and lost due to this. Also,
A similarly prepared film was immersed in water at 25°C for 48 hours and changes in state were observed. The film of the polymer emulsion (E-2) of this example showed extremely little whitening and swelling.
It showed good water resistance, but the comparative polymer emulsion (
The film of RE-3) showed significant whitening and swelling and was poor in water resistance.

Each of the above polymer emulsions was used to form a paint in the same formulation as in Example 1. The test results for paint and coating performance are shown in Table 2.

Table-2 [Test method is the same as Table-1. ] The paint of Example 2 was good in both paint stability and film performance.

The following raw materials were charged and dissolved in the same reaction apparatus as in Example 1.

Deionized water 500.0 parts Emuldan 931 30.0 parts Hitenol N-081.0 parts While feeding nitrogen gas and stirring, raise the temperature to (9q) 60°C, then add Evicron 850 to ioo ,.

A mixture of 0 parts and 10 parts of Noigun EA-120 was gradually added over 30 minutes, and the mixture was further stirred for 1 hour to disperse the epoxy resin. Subsequently, the following monomer mixture was added.

Butyl acrylate 50.0 parts Styrene 45.0 parts Methacrylic acid
After adding 5.0 parts of the above monomer mixture, 25 parts of a 2% potassium persulfate aqueous solution was added, and while the temperature was maintained at 70° C. by cooling or heating as appropriate, the mixture was maintained for 4 hours to react.

Next, the following monomer mixture and 50 parts of 2q6 hydrium persulfate aqueous solution were added dropwise over 2 hours to polymerize.

Butyl acrylate iio, o parts Methyl methacrylate 75.0 parts Dimethylaminoethyl acrylate 10.0 parts Methacrylic acid
5.0 parts The mixture was further maintained at 70° C. for 2 hours, cooled to room temperature, filtered through a 200 mesh filter cloth, and taken out. The obtained polymer emulsion (E-3) had a nonvolatile content concentration of 43.0%, a pH of 6.7, and a viscosity of 80 eP.
It was s. This emulsion had good storage stability at 50°C even after one month, and as in Example 1, the toluene resistance of the film coated on a glass plate at 25°C was also good.

Next, as Comparative Example 4, Ciepiclon 850 was removed from the above, and the amount of deionized water was reduced by 132 parts in order to set the nonvolatile content concentration of the polymer emulsion to 43 parts.
Other than that, a polymer emulsion (RE-4) was synthesized in the same manner, and a commercially available epoxy resin emulsion (Epiclon 8
5-75W: 15 parts of Dainippon Ink Chemicals KK product) were added and mixed. The resulting formulation had a non-volatile content of 47,
0% pH 6.7, viscosity 120 ePs. This material agglomerated after 2 days at 50°C, and as a result of the toluene resistance test of the film by the same method as above, -partial dissolution,
Damage due to swelling was observed.

Both of the above were made into a paint using the same paint formulation as in Example 1, and the physical properties of the paint and the paint film were tested, and the results are as shown in Table 3.

Table-3 [Test method is the same as Table-1 except for the following] 0 Washing resistance;
A Gardner-type washer was used to abrade the painted surface 1000 times using a mixed aqueous solution of 1.5% Marcel soap and 10% polishing sand.

The coating material of Example 3 had good stability and physical properties of the coating film, but the coating material of Comparative Example 4 had poor stability and physical properties of the coating film.

Using the polymer emulsion (E-2) synthesized in Example 2 and the polymer emulsion (RE-3) of Comparative Example 3, paints were prepared according to the following formulation.

Tamorure 31 (25%) (dispersant) 7.2
7.2 7.2 Ethylene glycol 1
5 15 15 polymer emulsion (E-2)
451--Polymer emulsion (RE-
3) -465-same as above-
-459 Ammonia water (28ch) 7 7
7 Non-volatile content concentration: 51 Pigment weight concentration (PWC): 55% The stability of the above coating material and the physical properties of the coating film applied to the polished mild steel plate were as shown in Table 4.

Table-4 Judgment: ◎Excellent, ○Good, △Slightly inferior. x Defective.

[Test method] Base material: Polished mild steel plate Coating amount: 25μ (by Percoater 460) Drying:
23°C for 5 days Preparation of specimen: After drying, the back and sides of the specimen were sealed with acrylic lacquer (clear) and then tested.

Adhesiveness: Make a hole with a knife with a 1mm gap in an area of 10m+aX 10zrn, and use commercially available sellotape.
Sellotape peel test.

Water resistance: A cross-cut specimen was immersed in water for one week, and two coats of rust, blisters, and other changes in condition were observed.

Salt water resistance: Similarly immersed in 5% food water for one week.

Salt water spray resistance: A similar specimen was exposed in a salt water spray tester for 96 hours.

A polymer emulsion (E-4) was synthesized in the same manner as in Example 2 except that the epoxy resin was changed from Eviclon 1050 to Eviclon 850, the amount used was 20 parts, and styrene was substituted for methyl methacrylate. Next is this polymer emulsion.

A sprayed tile pode coat was prepared as follows using a commercially available acrylic-styrene emulsion for sprayed tiles, Ponko 5410 (manufactured by Dainippon Ink & Chemicals KK).

Example 5 Comparative Example 7 Potassium tripolyphosphate (5q6 aqueous solution) 4
6.0 46.0 Ethylene glycol
4.0 4.0 Polymer emulsion (E-4
) (45chi) 152.5 - Commercial product Ponko) 54
10 (50%) -137.2 Ammonia water (28%) 1.5 1.5 Non-volatile content concentration = 85% Pigment weight concentration = 92% A commercially available vinyl chloride-vinyl acetate copolymer solution was applied as a sealer to a commercially available cement/asbestos board. After drying, spray the above paint using a tile gun at a pressure of 2.5.
Application amount 2yu/? in kg/ai? I sprayed the ball so that it was just the right amount. After drying at room temperature for 24 hours, top coat with commercially available acrylic lacquer/enamel (coating amount: 2oog/
m'), and was further dried at room temperature for 5 days.

The results of testing the physical properties of the coating film for each of the coated plates obtained above were as shown in Table 5.

Table-5 East adhesion: According to JIS-A-6910.

Example 5 had excellent adhesion and good durability.

To the paints of Example 1 and Comparative Examples 2 and 3, the same amount of 5 liters of Kansui stone and 1 mixture of 3 liters, respectively, were added and mixed. Comparative example 8. A ricin paint of Comparative Example 9 was obtained.

Apply amount 1 kg/n to commercially available cement/asbestos board with ricin gun? Each piece was spray-painted with glue paint so that it would look like this, and then dried at room temperature for 5 days.

When the performance of each coating film was compared, the results were as shown in Table 6.

Table 6 Example 6 had good paint stability and film performance. Monomer composition: (Composition of emulsion polymer serving as seed particles) Epicron 850 40.0 parts 2-ethylhexyl acrylate 42, 0 styrene
40.0 Methyl methacrylate
15,0 methacrylic acid
3,0 (second stage monomer composition) 2-ethylhexyl acrylate 126.0 parts Methyl methacrylate 157.5 Dimethylaminoethyl methacrylate 12.0 Acrylic acid
Polymerization was carried out in the same manner as in the synthesis of the polymer emulsion binder in Example 2, except for the changes described in 4.5, to obtain a polymer emulsion binder (E-5). Water was further added to the obtained polymer emulsion (E-5) to adjust the nonvolatile content concentration to 45.0%. The viscosity of this product is 120e
Ps had good storage stability at 50°C even after one month.

On the other hand, as Comparative Example 10, a product similar to the above but excluding the jepoxy resin was synthesized in the same manner. The obtained polymer emulsion (
RE-5) has a nonvolatile content of 44. O%.

The viscosity was 100 cPg t p' 8.5. ,
Aqueous gloss ints were prepared using the respective polymer emulsions according to the following formulations.

[Composition]

water
10.0 parts ethylene glycol 2.
6 Noidan EA-1200, 3 Pestside FX O
, 01JR-60OA (Titanium oxide: Teikoku Kako KK product) 36.0 Ammonia water (28T)
0.15 polymer emulsion (44)
113.6 Texanol 7.0
8N-Deformer 121
0.3 Cellosize QP-4400 (3%) 9.2 Non-volatile content concentration: 47 cm Pigment volume concentration (PVC): 20 cm The results of the physical property tests for each paint and coating film were as shown in Table 7.

〔Test method〕

Paint viscosity: Based on a stormer type viscometer. Measurement temperature: 25°C Gloss: Paint was applied onto a glass plate using a 3m11 applicator, and after drying for one day, the gloss was measured using a Murakami gloss meter at angle of incidence/angle of reflection ==60°/60°.

Water resistance: Paint the flexible board twice with a brush, dry for one day, and then immerse in water for 96 hours (sealed with acrylic/urethane on the back) Alkali resistance: A sample similar to the above was coated with Ca (OH) 2
Immersed in a saturated aqueous solution (sealed with acrylic-urethane on the back side) Accelerated heat and humidity resistance: Paint was applied to a thickness of approximately 1+1 ulH on a flexible board sealed with solvent-based acrylic, and after drying for 7 days, the upper side was wetted with water. The condition of the paint film was determined 7 days after irradiation with an infrared lamp at a distance of 50 m.

Solvent resistance: The surface of the same specimen as in the water and alkali resistance tests was rubbed 100 times by hand using absorbent cotton impregnated with toluene.

Weather resistance: 1.0 on the Sunshine Uniday Meter
00 hours exposure.

As mentioned above, the Example 70 gloss paint has good gloss,
It showed the durability of the coating film.

A polymer emulsion (E-6) was obtained in the same manner as in Example 7, except that Epiclon 850 was replaced with Eviclon 1050. The following paints were prepared using the obtained polymer emulsion (E-6) and the epoxy resin-free polymer emulsion (RE-5) used in Comparative Example 10, respectively.

[Composition]

Example 8 Comparative Example 11 Polymer emulsion (E-6) 89 parts -
Polymer emulsion (RE-5) 9
1 part Texanol 22 Water 2
- Pigment weight concentration: Non-volatile matter concentration of 3 pieces = 40 pieces The results of the physical property test for each paint and coating film are as shown in Table 8.

Table-8 [Test method] Base material: Untreated dull steel plate (JIS-G-3141-D)
, used after degreasing with toluene.

Application: Apply to a film thickness of 20μ (dry) using a percoater.

Drying: 3 days at room temperature.

Gloss: Paint is applied on a glass plate using a 3 mil asolicator, and after drying for one day, the incident angle/reflection angle is measured using a Murakami gloss meter.
Measured at 60°760°.

Water Resistance 2 The specimen painted under the above conditions was coated with acrylic lacquer and immersed in water for 48 hours to seal the back and sides.

Salt water spray resistance: After making a cross cut on the painted surface of a similar specimen, it was placed in a salt water spray tester and exposed for 48 hours.

Solvent resistance: Painted specimen (unsealed) immersed in gasoline for 24 hours.

Adhesiveness = 10mm x 10m door with 1mm x 1mm spacing, then apply commercially available sellotape.
Next, remove the cellophane tape and measure the number of pieces remaining in the cut area.

The paint of Example 8 was found to be stable and excellent in gloss and film durability.

In the polymer emulsion used in Example 2, the composition of the emulsion polymer serving as the seed particles was changed as follows, and the amount of deionized water was changed to 158 parts.

Evicron 850 24.0 parts Butyl acrylate 40.0 Ethyl acrylate 20.0 Methyl methacrylate
38.0 Methacrylic acid 2
．． Furthermore, the monomer composition for the second stage dropwise polymerization is ethyl acrylate 120.0 parts butyl acrylate 150.0 methyl methacrylate
21.0 Dimethylaminoethyl methacrylate 6
．． 0 methacrylic acid 3,0.

A polymer emulsion (K-7) obtained by emulsion polymerization using the same K except for the above had a nonvolatile content of 55.2%, a pH of 8.5, and a viscosity of 600 eP@. Moreover, as Comparative Example 12, the same emulsion polymerization as above except for the jepoxy resin was carried out.

The obtained polymer emulsion (RE-6) had a nonvolatile content of 5
4.0%, PH8.5, viscosity 480 egg.

・Using each of the obtained polymer emulsions, the following coating composition was carried out to prepare a main ingredient (Podey Coat) for a multilayer elongated coating agent.

[Composition]

Polymer emulsion (E-7) 371.8
Part - Polymer emulsion (RE-6)
-37B, 7 parts Demol EP (dispersant, Kao KK product)
7.7 7.7 Ethylene glycol
5.5 5.5 Cell Top HP-10
35,55,5 Charcoal MS-100312,4312,4 Thai Bake R
-5507,77,7 5% High Metrose 90SH-1500036,53
6.5 total 1,102.51,109.4NY
(Non-volatile content concentration)% 78.6 78.1p
vc (pigment volume concentration) 50.0 50. O
pwc (pigment weight concentration) 70.2 70.
2 The physical properties of the coating film of the above formulation were tested in accordance with JIS-A-6021K, and the results were as shown in Table 9.

Table 9 [Test method] Screen preparation conditions: Coating film thickness: approx. 1 zx (dry) drying: 30 days at room temperature Punching: No. 3 dumbbell tensile test conditions: (based on JIS A-6021) )
measurement ! ...Tensilon tensile speed: -200 speeds/-h Measurement temperature: -20°C, -10°C.

20°C, 60°C treated specimen: Heat treatment...80°C x 7 days alkali treatment.
...0.1% NaOH.

Saturated Ca (OH) 2
0°C indicates between the marked lines. The coating film of Example 9 has excellent strength and elongation, and is heat resistant.

Alkali resistance was also good.

Example 1. Comparative example 1. Each polymer emulsion (E-1), (RE-1) 9 (RE-2) used in Comparative Example 2
) according to the following formulations, respectively, Example 10. Comparative example 13. A single layer elastic paint of Comparative Example 14 was obtained.

[Composition]

Potassium tripolyphosphate (5q6 aqueous solution)
4.54 Noidan EA-1202,27 Ethylene Glycol 22.72
water 7
9.96 Adekane) B-1903,64 Polymer emulsion (50%) 69
2.95 Texanol 12.4
9 xylene 3.187 detonol uw-42o/water = y25.22 total
1,063.00 Non-volatile concentration (NY) 54.596 Pigment volume concentration (PVC)
15.2% Pigment Weight Concentration (PWC) 39.6%
The physical property test results for each paint and coating film were as shown in Table 10.

/ / 7/ / / 7/ Table 10 [Test method] Paint viscosity = BH type 4 rpm Paint viscosity (CP-) Paint film was applied to a glossy glass plate with a 3ml applicator,
Measure the 60° reflectance after drying for one day.

JIS A6910: Elongation rate: A test piece was prepared so that the coating film thickness was approximately 1st grade when dry, then cured according to the JIS elongation test method, and punched out with a No. 2 dumbbell. .

(Coating → Curing for 7 days → Curing for 7 days on the back side → Punching) Deterioration during elongation: The above specimen was punched out using a No. 1 dumbbell as a test piece.

Adhesion strength: Acryday as an undercoat agent.

Apply 53-448 for 3 hours. After drying, test the sample according to the test method. After applying and curing for 14 days Co-translated, used for adhesion strength after immersion in water The four sides of the specimen Painted with vinyl chloride resin 3 days before completion I painted it with paint. Adhesive is 2 Using liquid epoxy adhesive Ta.

Resistance to repeated heating and cooling: (18Hrs-+ in 20±2℃ water - 20±3℃X3Hrs-+ 50±3℃X3Hrs)×10 cycles Water permeability (-
)...Conforms to JIS extensibility test method Impact resistance...
l Weather resistance...l Coating film strength: Displays the coating film strength at the time of measuring the JIS A6910 elongation rate.

Accelerated weathering resistance: 2 after irradiating a coating similar to the one whose elongation rate was measured using a standard weather meter for 500 hours.
Measurement of strength and elongation of the coating film at 0°C. The coating of Example 10 had good stability, and the physical properties of the coating film were also good as shown in Table 10. Comparative Example 13 had relatively good physical properties of the coating film, but had poor coating stability, and agglomerated during a two-week storage stability test at 50°C.

The polymer emulsion (E-5) used in Example-7 and the polymer emulsion (RE-5) used in Comparative Example-10
) were used to formulate the following paints.

[Composition]

Example-11 Comparative Example-15 Polymer emulsion (E-5) 100.0 parts - Polymer emulsion (RE-5)
102.3 parts Butyl cellosolve
3.5 3.5 Texanol
1.5 1.5 Each of the above-mentioned paints was spray-coated onto a commercially available flexible board to a dry film thickness of 40 microns, and then dried at 70°C for 20 minutes to obtain a coated board. The physical property test results of these coating films were as shown in Table 11.

Table 11 [Test method] Normal adhesion: 10×10 pieces of 2 goblets are made on the coated surface using a razor blade, and a sellotape peeling test is performed.

(Coating film) Water resistance: A pressure test specimen was immersed in water at 20°C for one month to observe loss of gloss, whitening, blisters, etc. on the painted surface.

Alkali resistance: Immerse in 5-strong soda solution at 20°C for 7 days and observe changes in the state of the coated surface.

Humid and heat resistance: Changes in the condition of the coated surface after being left for one month under conditions of 50°C and 98% RH or higher.

Hot water cycle test: The specimen is immersed in hot water at 70°C for 2 hours and then dried in a dryer at 50°C for 2 hours. Repeat this operation 10 times and observe changes in the coating surface.

Boiling water resistance: immerse in boiling water for 2 hours and check the condition of the painted surface.

Freeze-thaw cycle: Immerse the specimen in water at 20-30°C for 2 hours and immediately freeze at -20°C. Repeat this process 10 times to check for cracks, peeling, etc. on the painted surface.

The coating film of Example-11 showed extremely good durability, with a rating of 70
It was found that even low-temperature treatment such as drying at 20 minutes at 0.degree. C. resulted in good crosslinking properties.

[Effects of the present invention]

The emulsion coating material of the present invention using a novel crosslinkable polymer emulsion as a vehicle can be cured by mold cutting and at room temperature, and provides a cured coating film with excellent storage stability and good durability.

Claims (1)

[Claims] (1) (a) An ethylenically unsaturated monomer that does not contain an amino group in its molecule is subjected to emulsion polymerization in the presence of a water-insoluble epoxy resin to produce an emulsion polymer as seed particles, and then (b)
In the presence of the emulsion polymer, a polymer emulsion obtained by emulsion polymerization of an ethylenically unsaturated monomer containing an amino group and another ethylenically unsaturated monomer copolymerizable therewith is used as a vehicle. Room-temperature curing emulsion paint.