JPH11100552A - Paint composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a water borne coating material having an excellent balance of high tension resistance and elasticity together with excellent quick drying property and water resistance at the initial stage under an adverse condition such as a low temp. or a high humidity condition. SOLUTION: An anionic film-forming synthetic resin emulsion comprising (1) a synthetic resin wherein solubilities in water of emulsion-forming monomers except anionic ones are from 0.01% to 1.50%, (2) a monomer mixture comprising at least 20 wt.% of an amine functional group contg. monomer with the amine functional group being 5-80% of the no. of equivalent of the carboxyl group of (1), (3) a volatile basic material in an amt. effective in increasing pH of the compsn. to the extent sufficiently high for substantially all the amine functional groups to be in a nonionic state, and (4) an epoxy resin with the no. of the epoxy group of 5-500% based on the no. obtd. by subtracting the no. of equivalent of (2) the amine functional group from the no. of equivalent of (1) the carboxyl functional group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is excellent in quick drying and initial water resistance at room temperature or lower, especially at low temperature or high humidity, and has a higher tensile strength (tensile strength) by adding a curing agent.
The present invention relates to a water-based coating composition which is excellent in production, storage stability and coating workability without increasing rubber elasticity.

[0002]

2. Description of the Related Art Conventionally, a quick-drying water-based coating composition has a high total solid content, minimizes water-soluble components such as surfactants and thickeners, and contains a large amount of a low-boiling alcohol such as methanol. A method for speeding drying is known.
Also, JP-A-3-157463 or JP-A-8-21
It is known to contain emulsion polymers, polyfunctional amines and volatile bases, as described in US Pat. No. 8037.

However, in the former method, the quick-drying property cannot be sufficiently improved, and the performance such as coating workability and storage stability tends to be impaired. When low-boiling alcohols such as methanol are added in an amount until the effect is exhibited,
He came into contact with the Fire Service Law and the Industrial Safety and Health Law. In the latter method, quick-drying properties or insufficient elasticity and tensile strength are required, and there has been a demand for a coating composition capable of achieving a balance between quick-drying properties and tensile strength.

Further, it is difficult for conventional reaction-curable elastic paints to improve the drying property, especially the quick drying property, in order to obtain a sufficient pot life. On the other hand, when a tough coating film (tensile strength) can be obtained by the reaction hardening action, the rubber elasticity must be significantly reduced. Therefore, there has been a demand for a coating composition that can achieve a balance between quick drying, high tensile strength, and high elasticity.

[0005]

DISCLOSURE OF THE INVENTION The present invention is excellent in quick drying, especially in low temperature and high humidity, and has a
It is an object of the present invention to provide a water-based coating composition having a property of obtaining a tougher coating film and having no significant decrease in rubber elasticity.

[0006]

According to the present invention, in order to solve the above-mentioned problems, in an anionic synthetic resin emulsion, water 100% of a monomer other than an anionic monomer among monomers constituting the emulsion is used. A polymer formed from a synthetic resin emulsion having a solubility per gram of 0.01 to 1.50 grams, a monomer mixture containing at least 20% by weight of an amine functional group-containing monomer, having an amine function based on the number of equivalents of carboxyl groups. A ratio of 5 to 80% of the equivalent number of groups, a sufficient amount of volatile base to raise the pH of the composition to a point where essentially all of the polyfunctional amine is in a nonionic state; To the number obtained by subtracting the number of equivalents of the amine functional group from the number of equivalents of the carboxyl group contained in
It is intended to include an epoxy resin having an epoxy group number of from 500% to 500%.

[0007] In this specification, "quick-drying" refers to the property of drying faster than conventional compositions.
"Synthetic resin emulsion" used in this specification
By means, for example, a water-insoluble polymer which can be produced by conventional polymerization techniques such as emulsion polymerization. Synthetic resin emulsions form films under application conditions,
Polymerized from any monomer or monomer mixture that produces a water-insoluble polymer.

[0008] The synthetic resin emulsion used in the aqueous coating composition of the present invention needs to be anionic stabilized. They also mean water-insoluble polymers which can be produced by conventional polymerization techniques such as, for example, emulsion polymerization. The present invention also provides more complex forms,
For example, it can be carried out using a core-shell particle polymer.

The anionic nature of synthetic resin emulsions can be obtained by several methods, the most common being the use of anionic surfactants during emulsion polymerization, or those surfactants after polymerization. Is added to the emulsion.

[0010] Nonionic surfactants can also be present in the synthetic resin emulsions during or after the polymerization of these anionically stabilized synthetic resin emulsions. Useful surfactants include: Condensation products of naphthenic sulfonic acid with low molecular weight formaldehyde, carboxylic acid polymers and copolymers with proper hydrophilic-lipophilic balance, higher alkyl sulfates such as sodium lauryl sulfate, dodecyl Alkylaryl sulfonates such as benzenesulfonate, sodium or potassium salts of isopropylbenzenesulfonic acid or isopropylnaphthalenesulfonic acid, sulfosuccinates such as sodium dioctylsulfosuccinate, alkali metal salts of higher alkylsulfosuccinates, for example octyl Sodium sulfosuccinate, sodium N-methyl-N-pammitoyltaurate (palmitoyltaura)
te), sodium oleyl isethionate, alkylaryl polyethoxyethanol sulfate or alkali metal salts of the same, such as sodium t-octylphenoxy-polyethoxyethanol sulfate having 1 to 5 oxyethylene units. There are various well-known anionic surfactants.

Another type of synthetic resin emulsion having anionic properties is that which results from the inclusion of small amounts of acidic groups in the polymer. Here, the acidic group can be in the form of a salt, for example, an alkali metal salt or an ammonium salt. Examples of such acidic groups are fragments of an incorporated initiator, maleic acid, vinyl sulfonic acid,
It is derived from crotonic acid, acrylic acid, methacrylic acid, itaconic acid and the like.

A third useful type of anionic synthetic resin emulsions are latex polymers containing neutralized basic monomers such as, for example, acrylamide, methacrylamide, and the like. The anionic nature of the synthetic resin emulsion may be more than one type.

The synthetic resin emulsion having an anionic property can be produced by a known method. Such a known method is described in Wiley, D.W. C. Black Ray (DC Blackl)
ey), “Emulsion polymerization: theory and practice (Emulsion)
Polymerization: Theory an
d Practice) ”and Interscience Publisher.
ishers) published in 1965. A. By FA Bovey et al., "Emulsion Polymerization (Emuls
ion Polymerization).

[0014] Synthetic resin emulsions are generally polymers or copolymers prepared, for example, from the following monomers: methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, methyl methacrylate. , Ethyl methacrylate,
Butyl methacrylate, styrene, butadiene, ethylene, vinyl acetate, "Versati
c) "vinyl ester (this vinyl ester of an acid (tertiary monocarboxylic acids of chain length _{C 9, C 10} and _{C 11)} is" vinyl versatate acid (vinyl Versatat
e)), vinyl chloride, vinylpyridine, vinylidene chloride, acrylonitrile, chloroprene, acrylic acid, methacrylic acid, itaconic acid, maleic acid and fumaric acid, α, β-ethylenically unsaturated monomers and the like. And especially polymers and copolymers of acrylates and methacrylates. They are described in "Emulsion Polymerization of Acrylic Monomers (Emulsio)" published in May 1966 by Rohm and Haas Company of Philadelphia, PA, USA.
n Polymerization of Acryl
ic Monomers).

As acrylates, ethyl acrylate, butyl acrylate, methyl methacrylate and 2-ethylhexyl acrylate are used, and as acrylates, copolymers using acrylic acid and methacrylic acid and further using styrene are preferable. used. The Tg of the synthetic resin emulsion is preferably from -50 ° C to 0 ° C.
It is in the range of ° C.

The synthetic resin emulsion is preferably polymerized from a monomer mixture containing butyl methacrylate,
The amount of butyl methacrylate is from 1 to 70% by weight of the monomer mixture, more preferably from 10 to 30% by weight. Also, the synthetic resin emulsion is preferably polymerized from a monomer mixture containing 2-ethylhexyl acrylate, and the amount of 2-ethylhexyl acrylate is 93 to 22% by weight of the monomer mixture;
More preferably, it is 43% by weight. As described above, the film-forming synthetic resin emulsion having an anionic property used in the present invention has a solubility of 100% in 100 g of water of monomers excluding the anionic monomer among the monomers forming the polymer. 01 to 1.
It needs to be 50 grams. The monomer excluding the anionic monomer is, as mentioned above as the second anionic introduction method, when the polymer is made anionic by including a small amount of an acidic group,
This means other monomers excluding such a monomer containing an acidic group. The solubility refers to that at 25 ° C. It is considered that the solubility has an additive property, and the solubility of the monomer mixture can be obtained by calculation if the ratio of each monomer is determined. Here, the solubility is a measure of the balance between hydrophilicity and hydrophobicity.By adjusting the balance between the hydrophilicity and the hydrophobicity of the mixture of monomers forming the synthetic resin emulsion using the solubility as a measure, the quick-drying property and the obtainability of the polymer are obtained. The physical properties of the resulting coating film can be adjusted.

The coating composition of the present invention comprises a water-soluble or water-dispersible polymer formed from a monomer mixture containing at least 20% by weight of the amine-functional monomer.

Monomers containing an amine function include, for example, the following: 1. The alkyl group may be straight-chain or branched and have 2-3 carbon atoms, and the nitrogen atom may be a primary, secondary or tertiary nitrogen atom Aminoalkyl vinyl ether or the same sulfide (U.S. Pat. No. 2,879,178).

Specific examples are: β-aminoethyl vinyl ether; β-aminoethyl vinyl sulfide; N-monomethyl-β-aminoethyl vinyl ether or the same sulfide; N-monoethyl-β-aminoethyl vinyl ether or N-monobutyl-β-aminoethyl vinyl ether or the same sulfide; and N-monomethyl-3-aminopropyl vinyl ether or the same sulfide.

2. Acrylamide or acrylate, such as dimethylaminoethyl acrylate or methacrylate; β-aminoethyl acrylate or methacrylate; N-β-aminoethyl acrylamide or methacrylamide; N- (monomethylaminoethyl) -acrylamide or methacrylamide There is.

3. N-acryloxyalkyl-oxazolidine and N-acryloxyalkyltetrahydro-
1,3-Oxazines and compounds corresponding to the above oxazolidines and oxazines, wherein the "alkyl" bond is replaced by alkoxyalkyl and poly (alkoxy-alkyl).

Examples of this compound are: oxazolidinylethyl methacrylate; oxazolidinylethyl acrylate; 3- (γ-methacryl-oxypropyl) -tetrahydro-1,3-oxazine; β
-Methacryloxyethyl) -2,2-pentamethylene-oxazolidine; 3-β-methacryloxyethyl-
2-methyl-2-propyloxazolidine; N-2-
(2-acryloxyethoxy) ethyl-oxazolidine; N-2- (2-methacryloxyethoxy) ethyl-oxazolidine; N-2- (2-methacryloxyethoxy) ethyl-5-methyl-oxazolidine; N-2
-(2-acryloxyethoxy) ethyl-5-methyl-
Oxazolidine; 3- [2- (2-methacryloxyethoxy) ethyl] -2,2-pentamethylene-oxazolidine; 3- [2- (2-methacryloxyethoxy)
Ethyl] -2,2-dimethyl-oxazolidine; and 3
-[2- (2-methacryloxyethoxy) ethyl]-
2-phenyl-oxazolidine.

4. Polymers of monomers that readily form amines upon hydrolysis are useful as the amine-containing component or to form polymers of the amine-containing component of the binder composition. Examples of such monomers are acryloxy-ketimines and -aldimines.

Illustrative compounds are as follows: 2- [4-
(2,6-dimethylheptylidene) -amino] -ethyl methacrylate; 3- [2- (4-methylpentyridine) -amino] -propyl methacrylate; β- (benzylideneamino-ethyl methacrylate; 3- [2-
(4-methylpentylidene) -amino] -ethyl methacrylate; 2- [4- (2,6-dimethylheptylidene) -amino] -ethyl acrylate; 12- (cyclopentylidene-amino) -dodecyl methacrylate; N
-(1,3-dimethylbutylidene) -2- (2-methacryloxyethoxy) -ethylamine; N- (benzylidene) -methacryloxyethoxyethylamine; N-
(1,3-dimethylbutylidene) -2- (2-acryloxyethoxy) -ethylamine; and N- (benzylidene) -2- (2-acryloxyethoxy) ethylamine.

In general, at least 20% by weight of the amine-containing polymers of the abovementioned monomers of categories 1, 2, 3 and 4 are present in neutral, alkaline or acidic aqueous media, depending on the particular polymer sought. Can be obtained by solution polymerization. Generally speaking, the polymerization is carried out in an aqueous medium containing a small amount of an organic or inorganic acid, such as acetic acid or hydrochloric acid. Amine-containing polymers are copolymers of up to 80% by weight of one or more monomers, for example methyl acrylate, acrylamide, methacrylamide and quaternary ammonium salts derived from amine monomers, for example 2-methacryloxyethyltrimethylammonium chloride. Is included. Small amounts of relatively insoluble comonomers can also be used to obtain water-soluble polymers. The insoluble polymer may contain higher amounts of these comonomers. Such monomers include, for example, (C ₁
To _C18 ) acrylates with alcohols and 1 to
Alcohols having 18 carbon atoms, especially (C ₁ -C
₄ ) Methacrylic esters with alkanols, styrene, vinyltoluene, vinyl acetate, vinyl chloride, vinylidene chloride, substituted styrene, butadiene, substituted butadiene, ethylene, and nitriles and amides of acrylic acid or methacrylic acid. The particular monomer or monomers used in preparing a given amine-containing polymer will depend on the proportion of amine-containing monomer used in preparing the copolymer. Preferably, comonomers having relatively high solubility in water are used exclusively for producing water-soluble polymers. These polymers are therefore polymers and copolymers of cationic and, optionally, non-ionic vinyl monomers. Examples of cationic monomers are amines, imines and quaternary ammonium salts; the other monomers mentioned are non-ionic. Thus, these water-soluble copolymers eliminate traces of acid groups that may be present due to impurities in the monomers used or due to some hydrolysis that occurs during synthesis, storage or use. If it does, it does not contain any other acid groups.

The viscosity average molecular weight of the insoluble amine-containing polymer is from about 5,000 to about 100,000, and preferably ranges from about 15,000 to 90,000. The molecular weight of the water-soluble polymer can cover a wide range. Typically, the viscosity average molecular weight is from about 5,000 to about 30
0000, and from about 40,000 to about 100,
A range of 000 is preferred. The amount of the amine-containing polymer ranges from about 0.1 to about 20% by weight of the total weight of the anionic synthetic resin emulsion and the amine-containing polymer.

Amine containing polymers are generally used as generally known in the art, for example, as taught in US Pat. No. 4,119,600.
Depending on the specific polymer sought, it can be obtained by solution polymerization in neutral, alkaline or acidic aqueous media. Generally speaking, the polymerization is carried out in an aqueous medium containing a small amount of an organic or inorganic acid, such as acetic acid or hydrochloric acid. Amine-containing polymers include up to 80% by weight of copolymers with one or more monoethylenically unsaturated monomers such as methyl acrylate, acrylamide and methacrylamide. Small amounts of relatively insoluble comonomers can also be used to obtain water-soluble polymers. Insoluble polymers may contain higher amounts of these comonomers. Such monomers include, by way of example, acrylic esters with (C ₁ -C ₁₈ ) alcohols and methacrylic esters with alcohols having 1 to 18 carbon atoms, in particular with (C ₁ -C ₄ ) alkanols , Styrene, vinyl toluene, vinyl acetate, vinyl chloride, vinylidene chloride, substituted styrene,
There are butadiene, substituted butadiene, ethylene, and the nitriles and amides of acrylic or methacrylic acid. The particular comonomer or comonomers used in making a given amine-containing polymer will depend on the proportion of amine-containing monomer used in making this copolymer. These polymers are therefore cationic,
And, optionally, a polymer or copolymer of a nonionic vinyl monomer. Examples of cationic monomers are amines and imines; other monomers mentioned are non-ionic. Therefore, these water-soluble copolymers may be due to impurities in the monomers used, or may be synthesized,
It contains no other acid groups except for traces of acid groups that may be present due to some hydrolysis occurring during storage or use.

A water-soluble or water-dispersible polymer formed from an anionic synthetic resin emulsion, a monomer mixture containing at least 20% by weight of amine functional monomers,
Compositions containing a sufficient amount of a volatile base to raise the pH of the composition to a point where essentially all of the polyfunctional amine is in a non-ionic state, for example, tradename E-2706
(Manufactured by Rohm and Haas).

The coating composition of the present invention requires a volatile base. The type and amount of volatile base used will typically be at least PH5, preferably PH7-9, up to the point where the amine functionality of the amine-containing polymer is deionized (deprotonated). Should be sufficient to avoid interaction with the anionic stabilized synthetic resin emulsions and other anionic components in the quick-drying coating composition.

After application, the volatile base evaporates, lowering the pH of the composition. When the pH of the composition drops to the point where protonation of the amine function begins to occur, the amine function becomes cationic. It is believed that this rapid drying is initiated by this conversion of the amine functionality to the cationic state in the presence of an anionically stabilized emulsion polymer, but the exact mechanism that produces this quick drying is It has not been established, and thus the present inventors do not limit its quick-drying with exact mechanistic theory.

Suitable bases include, but are not limited to,
There are ammonia, morpholine, alkylamines, 2-dimethylaminoethanol, N-methylmonophorin, ethylenediamine and mixtures thereof, with the preferred base being ammonia. The equivalent ratio of the amine to the acid in the synthetic resin emulsion is preferably amine / acid = 0.5 to 1.0.
It is.

The aqueous coating composition of the present invention may also contain a water-soluble or water-dispersible polyvalent metal in the form of a metal ion, salt, complex or oxide. The polyvalent metal may be added after blending the coating composition, but it is preferable to add other components after modifying the latex polymer with the polyvalent metal.
By pre-transforming the latex polymer with a polyvalent metal, the balance between the elongation and the tensile strength of the latex polymer film is maintained over a wider temperature range.

As a modification method, a polyvalent metal powder can be dispersed in water and added to the aqueous coating composition.
First, it is preferable that the polyvalent metal is made into a complex of a polyvalent metal ion or a salt is formed by the ion of the polyvalent metal and its counter ion to make the polyvalent metal water-soluble or water-dispersible. The complex of the polyvalent metal ion can be solubilized in an alkaline solution such as dilute aqueous ammonia having a pH of 9 to 10. Water-soluble or water-dispersible polyvalent metal at a temperature of 30 to
The latex polymer can be modified with a polyvalent metal by adding it to the latex polymer kept at 50 ° C.

Polyvalent metal ions such as calcium, aluminum, magnesium, zinc, barium, strontium and the like can be used. Complexes of polyvalent metal ions, such as zinc hexaammonia, zinc ammonium bicarbonate, and the like, and salts of polyvalent metal ions with counterions, such as chloride, acetate, and bicarbonate, can also be used. Zinc is the preferred polyvalent metal.

The polyvalent metal ion, salt, complex or oxide is present in an amount of about 0.1 to 1 based on the weight of the latex polymer solids.
Useful at the 0% level. Levels from about 0.3% to about 2.0% by weight, based on the weight of the polymer solids of the latex, are preferred. In addition, for example, pigments, binders, vehicles, extenders, dispersants, surfactants, coalescing agents, wetting agents, rheology modifying agents, thickeners, drying retarders,
Defoamer, colorant, wax, preservative, heat stabilizer, solvent,
Conventional paint components such as anti-skinning agents, desiccants and the like can also be used in the present invention. When choosing the type and amount of additives, the pH of the coating composition is changed to such an extent that storage stability is impaired, or until after application the pH does not drop sufficiently to initiate the polyamine protonation. Care must be taken to avoid missing the pH adjustment.

Further, the coating composition of the present invention contains an epoxy resin as a curing agent. By adding a curing agent, a coating composition capable of forming a tough and elastic coating film as well as improving quick drying and initial water resistance is obtained. As the curing agent, a curing agent that can undergo a room temperature crosslinking reaction, does not react with a volatile base, and does not hinder quick drying is preferable. What is a stable cold crosslinking reaction?
In general, reactions of an epoxy group or an azolidine group or an oxazoline group to a carboxyl group, reactions of a hydrazine group to a carbonyl group, and reactions of an isocyanate group to a hydroxy group are well known.

However, coating films bonded with metal ions and aziridine crosslinking have problems in mutagenicity and the like, and it is difficult to use them in coating films that substantially utilize a crosslinking reaction. Further, the reaction between the carbonyl group and the hydrazine group does not proceed so much in the presence of water, and the crosslink density decreases. The reaction between the carboxyl group and the oxazoline group is smaller at room temperature than the reaction between the carboxyl group and the epoxy group. Therefore, the latter combination is preferable. The reaction between the hydroxy group and the isocyanate group is not good because a pot life cannot be obtained when used as a paint.

The amount of the epoxy resin containing an epoxy group in the paint is determined from the number of carboxyl groups (A) of the anionic synthetic resin emulsion having a carboxyl group based on the amine functional group in the polymer containing the amine functional group-containing monomer. Equivalent number obtained by subtracting the equivalent number (B) of
The amount of the epoxy resin is adjusted so that the number of epoxy groups is 0.05 to 5 times that of (AB). The preferred amount is 0.1 to 3 based on the ratio of the number of unreacted carboxyl groups to the amine functional groups represented by (AB).
It is an epoxy resin with twice the number of epoxy groups.
By adding the epoxy resin in this ratio range, the volatile base in the coating composition evaporates quickly, and then the reaction hardening of the epoxy group and the carboxyl group in the anionic synthetic resin emulsion starts. When the number of epoxy groups, and hence the amount of epoxy resin, is added in a large amount exceeding the amount that can be reacted, the number of epoxy groups does not exceed the number of carboxyl groups, and the remaining epoxy resin becomes a diluent component.
However, since the amount of the epoxy resin is closely related to the quick drying, the optimum amount must be determined by experiment.

The coating composition of the present invention may contain an anionic surfactant neutralized with a volatile base as a pigment dispersant. The amount of the surfactant to be added is sufficient to disperse the pigment, and is usually 0.2 to 1.0% by weight of the active ingredient based on the pigment. Surfactants neutralized with a metal salt such as sodium or potassium, not a volatile base, are widely known, but they prevent the pH of the coating composition after coating from rapidly lowering and have an amine function. This is not preferred because the onset of protonation of the group is delayed, resulting in impaired drying properties.

As anionic surfactants neutralized with a volatile base, Orotan 901 (manufactured by Rohm and Haas Co.), Poise 532A (manufactured by Kao Corporation), Alastar 703S (manufactured by Arakawa Chemical Industries) ) Can be exemplified.

The aqueous coating compositions of the present invention have a pigment volume concentration (PVC) in the range of 20% to 70%, and typically have a solids content in the range of about 10 to about 70% by weight and a solids content of about 10 to about 70% by weight. 5
It is formulated to have a viscosity of 0 to about 5,000 poise. In general, the higher the solid content, the higher the quick-drying property. However, if the PVC becomes higher, the rubber elasticity is reduced, so that it is preferably 20% to 60%, and most preferably 25% to 45%.

The following are examples of pigments. There are titanium dioxide, calcium carbonate, and clay as white pigments, and iron oxide and known organic pigments can also be used as coloring pigments. There is no problem whether titanium dioxide is used alone or in combination with other inorganic or organic pigments. Further, the aqueous coating composition of the present invention can contain a filler such as silica sand, calcium carbonate, fiber and the like.

The coating composition of the present invention may further comprise, in addition to the above, low-boiling alcohols, film-forming auxiliaries, thickeners, viscosity modifiers, defoamers, preservatives, fungicides, and alga-proofing agents. Ingredients generally blended in paint production can also be used without impairing the features of the present invention.

The aqueous coating composition according to the present invention has the effects of low temperature sensitivity, high rubber elasticity, and excellent quick drying. In addition, 0 to 5 ° C., which has been difficult with an aqueous system conventionally,
It also has the effect that it is possible to apply and dry under such extremely low temperature and high humidity conditions of 80% to 90%. Here, "low temperature sensitivity" means that the temperature dependency is smaller than that of a conventional composition. As a measure of rubber elasticity, a value obtained by dividing the tensile strength at -20 ° C by the tensile strength at 20 ° C can be used. It is understood that the smaller the value, the higher the rubber elasticity. The paint can be applied using a roller, a tile gun, a pump, or the like, typically with a thickness of about 0.8 mm to about 3 mm.

[0045]

【Example】

Preparation of Monomer Mixture 1 To 3687.8 g of deionized water was added 3% of a 58% solution of ammonium polyoxyethylene nonylphenyl ether sulfate.
1.6 g was dissolved and the following monomer was slowly added to the stirred solution to prepare an emulsified monomer mixture 1.

Monomer weight (g) Total monomer weight (%) 2-ethylhexyl acrylate 4065.0 44.0 butyl methacrylate 2771.6 30.0 methyl methacrylate 2281.9 24.7 methacrylic acid 120.1 1.3 Total 9238.6 100.0

Polymerization Procedure Preparation of Emulsion Polymer In a suitable reaction vessel equipped with a thermometer, a cooler, and a stirrer, 70.1 g of ammonium polyoxyethylene nonylphenyl ether sulfate, and 318.0 g of deionized water.
g, and heated to 80-85 ° C. An aqueous solution of sodium carbonate (deionized water 169.
42.3 g of sodium carbonate dissolved in 4 g) and 531.2 g of the above-mentioned monomer emulsion were all charged, and the temperature was adjusted to 80 to 82 ° C. In this reaction solution,
Sodium persulfate (SPS) aqueous solution (deionized water 16
(33.1 g of SPS dissolved in 9.3 g). Within about 5 minutes, initiation of polymerization was confirmed by a 3-5 ° C temperature rise and a change in the appearance of the reaction mixture. After the end of the exotherm, the remaining monomer mixture and an aqueous solution of sodium persulfate (SPS) (SPS in 384.9 g of deionized water)
7.7 g) was gradually added to the reaction vessel.
2 so that the heat of the polymerization reaction can be removed by cooling.
Added in ~ 3 hours. The polymerization reaction temperature was maintained at 80 to 82 ° C by cooling if necessary. After the addition was completed, the reaction mixture vessel and feed tube were replaced with deionized water.
Rinse with 6 g and add to reaction vessel. The resulting emulsion polymer was cooled to a greenhouse or maintained at a suitable temperature to add a polyvalent metal aqueous solution, a water-dispersible amine-functional polymer.

Four emulsion polymers were prepared by the above operation, and Samples 1 to 4 were prepared according to the formulations shown in Table 1. The compounding was performed by maintaining the emulsion polymer at 40 ° C., adding an aqueous polyvalent metal solution to the reaction vessel, adjusting the pH to 9.0 to 10.0 using a 28% aqueous ammonia solution, and finally adding a water-dispersible amine. The reaction was performed by adding polyoxazolidinylethyl methacrylate (solid content: 27.5%), which is a functional group-containing polymer. Further, each of the samples 1 to 4 was poured into a petri dish coated with a release agent so as to form a film having a thickness of about 2 mm.
Dried for 2 days. Dry the film with a dumbbell.
The film was cut to a width of 25 inches, a tensile test was performed at a grip width of 1 inch and a tensile test speed of 2 inches / minute, and the elongation until the film was broken and the maximum strength were measured. Table 2 shows the results.

Preparation of Monomer Mixture 2 In 2748.5 g of deionized water, 47.0 g of a 24% solution of sodium dodecylbenzenesulfonate and 30.7% of sodium polyoxyethylene aryl ether sulfate.
55.0 g of the solution was dissolved, and the following monomer was slowly added to the stirred solution to prepare an emulsified monomer mixture 2.

Monomer weight (g) Weight (%) of all monomers 2-ethylhexyl acrylate 7564.8 80.0 butyl methacrylate 1036.8 11.0 methyl methacrylate 665.3 7.0 methacrylic acid 192.0 2.0 Total 9458.9 100.0

Polymerization Procedure Preparation of Emulsion Polymer In a suitable reaction vessel equipped with a thermometer, a cooler, and a stirrer, 24% sodium dodecylbenzenesulfonate was added.
1.4 g, 37.4 g of 30.7% sodium polyoxyethylene aryl ether sulfate, and 34 deionized water
A solution containing 90.6 g was charged and heated to 80-85 ° C. An aqueous ammonium carbonate solution (a solution prepared by dissolving 33.1 g of ammonium carbonate in 193.0 g of deionized water) and 544.3 g of the above-mentioned monomer emulsion were sequentially charged into this reaction vessel, and the temperature was set to 80 to 82. Adjusted to ° C. To this reaction vessel, all of an aqueous solution of ammonium persulfate (APS) (a solution of 34.1 g of APS dissolved in 129.6 g of deionized water) was added. The initiation of polymerization was confirmed by a temperature rise of 3-5 ° C. and a change in the appearance of the reaction mixture within about 5 minutes. After the exotherm had ceased, the remaining monomer mixture was added slowly. It was added in a few hours so that the heat of the polymerization reaction could be removed by cooling. The polymerization reaction temperature was maintained at 80 to 82 ° C by cooling if necessary. After the addition is completed, the reaction mixture container and the supply pipe are connected to deionized water 21.
Rinse with 7.9 g and add to reaction vessel. 45 reaction vessels
C., 130.5 g of 70% octylphenyl polyethoxyethanol was added, the vessel and feed tube were rinsed with 139.2 g of deionized water and added to the reaction vessel. The resulting emulsion polymer was cooled to room temperature or kept at a suitable temperature for adding a polyvalent metal aqueous solution and a water-dispersible amine-functional polymer. Nine emulsion polymers were prepared by the above operation, and the sample No. 5-1
3 was prepared. Note that the sample No. 11 to 13 are comparative examples. The blending is performed by maintaining the emulsion polymer at 40 ° C., adding the polyvalent metal aqueous solution to the reaction vessel, adjusting the pH to 9.0 to 10.0 using a 28% aqueous ammonia solution,
Finally, a water-dispersible amine functional group-containing polymer, polyoxazolidinylethyl methacrylate (solid content 27.5%)
%). Next, a film was prepared in the same manner as in the preparation of the emulsion polymer, and the elongation and the maximum strength were measured. Table 4 shows the results.

[0052]

[Table 1]

[0053]

[Table 2]

[0054]

[Table 3]

[0055]

[Table 4]

Sample No. 11 to 13 were applied to a glass plate using a 5 mil applicator in an environment of 5 ° C. and a relative humidity of 80%, and then rubbed with a finger, and the time until the film was completely covered and dried was measured. The results were as follows.

Sample No. Time to skinning Time to drying completion 11 40 minutes 70 minutes 12 40 minutes 60 minutes 13 10 minutes 40 minutes

Monomer mixture 1 followed by sample N
O. Emulsions having the compositions shown in Table 5 were synthesized in the same manner as when the emulsion polymers of Nos. 1 to 4 were prepared. The obtained emulsion is applied on a glass plate using a 5 mil applicator in an environment of 22 to 23 ° C. and a relative humidity of 60%, then rubbed with a finger, and the time until the film is completely covered and dried is measured. did. Table 6 shows the results.

[0059]

[Table 5]

The abbreviations in Table 5 are as follows. BA: butyl acrylate MMA: methyl methacrylate MAA: methacrylic acid 2-EHA: 2-ethylhexyl acrylate Sty: styrene BMA: butyl methacrylate SLS: sodium lauryl sulfate DS-4: sodium dodecylbenzene sulfonate CO-436: polyoxy Ammonium ethyl nonylphenyl sulfonate

[0061]

[Table 6-1]

[Table 6-2]

Hereinafter, a polymer sample having excellent tensile strength or elongation at break was selected from the above emulsion polymers.
Table 8 shows the storage stability in a state where the coating material is not contained and the curing agent is not contained, and Table 7 shows the coating formulation. next,
Polymer No. with excellent storage stability. The elongation and tensile strength of the coating film were measured by using 10 and changing the addition ratio of the epoxy resin as a curing agent. In addition, polymer sample NO. 4 and NO. Using No. 10, the type of the curing agent was changed, and the PVC of the paint was changed to perform an elongation test of the coating film.

[0063]

[Table 7] Ingredients Ingredients Emulsion polymer 1700 parts by weight Dispersant 4 parts by weight Titanium oxide 15 parts by weight Zinc white 4 parts by weight Calcium carbonate 840 parts by weight Thickener 21.3 parts by weight Antifreeze 30 parts by weight Film-forming aid 18 parts by weight Defoaming agent 6 parts by weight Total 2638.3 parts by weight PVC (pigment) Volume concentration)
Is about 25%. The solid content of the emulsion polymer is about 55%, although there is some variation depending on the emulsion polymer.
And

[0064]

[Table 8]

The storage stability test was carried out by applying a paint prepared based on the composition shown in Table 7 to a constant temperature bath at 20 ° C., a constant temperature bath at 50 ° C., and −5.
The viscosity after standing for one week in a constant temperature bath at ℃ was measured with a simple viscometer (Visco Tester). The viscosity of the paint placed at 50 ° C. and −5 ° C. was measured after returning the paint temperature to normal temperature at 20 ° C. for one day. Table 8
Among them, those stored at 20 ° C. were regarded as the viscosity over time, and those stored at −5 ° C. were subjected to the viscosity after storage at low temperature,
What was stored under the condition of 50 ° C. is defined as viscosity after aging at high temperature. In the storage stability test results shown in Table 8, ◎ indicates that the change in viscosity was less than 10% with respect to the viscosity immediately after production, and ○ indicates that the change in viscosity was 10% or more and 20% or less.
And that the X mark indicates that a change in viscosity of 20% or more occurred.

In the measurement of elongation and tensile strength due to the addition of the curing agent, the curing agent was added to the paint, mixed, and then applied on a release paper so as to have a thickness of 2 mm, and the conditions were set at 20 ° C. and 65 RH for 7 days. After curing, the test specimen was cut out with a dumbbell-shaped No. 3 punching die and subjected to an elongation test. The test method is 5.4 of JIS A6021 “Roof coating waterproofing material”.
According to the tensile performance. The tensile strength was determined by measuring the thickness and width of the sheet when punched into a dumbbell-shaped No. 3 mold with a micrometer, and converted based on the value showing the maximum tensile strength when an elongation test was performed. The amount of the curing agent added is a weight ratio with respect to the emulsion polymer sample, and the emulsion polymer sample refers to one containing a polymer containing an amine functional group-containing monomer and a volatile base. Glycerol polyglycidyl ether (glycerin diglycidyl ether) was used as the epoxy resin.

The amount of the curing agent depends on the number of carboxyl functional groups in the emulsion polymer and the number of amine functional groups in the amine functional group-containing polymer. Sample No. When the emulsion polymer of No. 10 was used, 1.06% by weight in the emulsion polymer
(192 / 18146.1) becomes methacrylic acid,
This number of moles corresponds to the number of equivalents of the carboxyl group. Sample No. When a coating material was prepared based on the composition table in Table 7 using 10 emulsion polymers, the emulsion polymer in 2638.3 parts by weight was 1700 parts by weight, which was about 18 parts by weight (0.21 parts by weight).
Eq.) Becomes methacrylic acid. Similarly, 1.06% by weight of the amine functional group-containing polymer is contained in the emulsion polymer, and 0.21 equivalent of the polymer is added. Accordingly, since about 55% (0.12 / 0.21) of the carboxyl groups are blocked by the amine functional group-containing polymer, the number of carboxyl groups corresponding to (AB) in the present specification is 0.09 equivalent. Becomes The epoxy resin is added in an amount of 0.14% by weight to the solid content of 1700 parts by weight in Table 7 to be added in an amount of 0.94 part by weight, and the molecular weight of glycerin diglycidyl ether is 204 in one molecule. Since the number of epoxy groups is 2, it is about 10% based on the number of epoxy groups that can react. Similarly, when 0.2% by weight of the epoxy resin is added to the solid portion of the emulsion polymer, about 20% is added to the number of carboxyl groups corresponding to (AB).

[0068]

[Table 9]

The composition when PVC was changed is shown in Table 10 below.
Shown in

[Table 10]

[0070]

[Table 11-1]

[Table 11-2] In the table, the NO. For example, A _{1 to} A ₈
Indicates the number counted from the left of the test result on the same line. In addition, the numerical values in two columns indicate the test results of the elongation (%) under 20 ° C. in the upper column and the test results of the tensile strength (kgf / cm ² ) in the lower column.

In addition, ED507 is an epoxy resin of Asahi Denka Kogyo Co., Ltd., trade name of Adekaglycirol ED507, 122W is an epoxy resin of Clariant Japan Co., Ltd., trade name of Beccopox. 122W, EP128 is an epoxy resin of Clariant Japan Co., Ltd., trade name Beccopox E
P128 and 0427 are epoxy resins of Asahi Denka Kogyo Co., Ltd., trade name Adeka Resin EP ES0427 and 1758
Is an epoxy resin of Asahi Denka Kogyo Co., Ltd., trade name of Adeka Resin EP R-1758, 1736 is an epoxy resin of Asahi Denka Kogyo Co., Ltd., trade name of Adeka Resin EP X-173
6, EX313 is an epoxy resin of Nagase Sangyo Co., Ltd., trade name Denacol EX313, EX810 is an epoxy resin of Nagase Sangyo Co., Ltd., trade name Denacol EX810,
EX212 is an epoxy resin of Nagase Sangyo Co., Ltd., trade name Denacol EX212, X09 is a urethane resin of Takeda Pharmaceutical Co., Ltd., trade name Takerac XW-75-X09,
XD220 is a polyisocyanate of Takeda Pharmaceutical Co., Ltd., a curing agent XD220 of trade name staphyloid, and Aqua 200 is a polyisocyanate of Nippon Polyurethane Industry Co., Ltd., trade name Aquanate 200.

In the examples of Table 11, those showing good values in both elongation and tensile strength were measured for the pot life after the addition of the curing agent.

[Table 12]

For measuring the pot life, after adding and mixing the curing agent, the container is sealed in a polyethylene container, placed at room temperature, and the viscosity is measured at regular intervals, and a tile gun (a type of air spray) and a pressure feeding machine are used. It was checked whether there was any problem in the workability when spray coating was performed using. In addition, when the change in viscosity occurred 20% or more as compared with immediately after the addition of the curing agent, one standard was used.

Further, in the above four examples, the drying property was confirmed under four conditions. Condition A is 20 ° C, 65
% RH, condition B is 20 ° C, 90% RH, condition C is 5 ° C,
65% RH, condition D is 5 ° C., 90% RH. In conducting the drying test, the prepared paint, curing agent, and coating base were allowed to stand for at least 24 hours under the temperature conditions for performing the drying test, and then subjected to the test. An asbestos slate plate to which a primer was applied was prepared as a coating base, and a test paint was applied in a thickness of 1 mm to evaluate the drying property. In the table, the touch for distinguishing the drying stage refers to touch drying, semi-curing refers to semi-curing drying, and curing refers to curing drying, and the standard is JIS K5.
We followed the 400 evaluation method. Water resistance refers to a stage in which water resistance is obtained, and indicates a stage in which no paint is eluted when a test plate coated with paint is immersed in water for 30 minutes. The numerical value indicating the measurement result is time.

[0075]

[Table 15]

[0076]

The coating composition of the present invention not only has excellent quick-drying properties and initial water resistance under normal temperature conditions, especially at low temperatures or high humidity conditions, but also has high tensile strength and reduces rubber elasticity. You can get something without. This solves the problem of a remarkable decrease in rubber elasticity when tough coating film properties (tensile strength or tensile strength) are obtained. Further, the paint of the present invention is a water-based paint having no problems in production stability, storage stability, and pot life during use. Accordingly, it has become possible to provide a coating material that is difficult to use and apply under low-temperature or high-humidity conditions and that has a good balance of elasticity and tensile strength.

[Table 13]

[Procedure amendment]

[Submission date] July 1, 1998

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claims

[Correction method] Change

[Correction contents]

[Claims]

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0006

[Correction method] Change

[Correction contents]

[0006]

According to the present invention, in order to solve the above-mentioned problems, in an anionic synthetic resin emulsion, water 100% of a monomer other than an anionic monomer among monomers constituting the emulsion is used. A polymer formed from a synthetic resin emulsion having a solubility per gram of 0.01 to 1.50 grams, a monomer mixture containing at least 20% by weight of an amine functional group-containing monomer, having an amine function based on the number of equivalents of carboxyl groups. A ratio of 5 to 80% of the equivalent number of groups, a sufficient amount of volatile base to raise the pH of the composition to a point where essentially all of the polyfunctional amine is in a nonionic state; To the number obtained by subtracting the number of equivalents of the amine functional group from the number of equivalents of the carboxyl group contained in
It is intended to include an epoxy resin having an epoxy group number of from 500% to 500%.

[Procedure amendment 3]

[Document name to be amended] Statement

[Correction target item name] 0028

[Correction method] Change

[Correction contents]

A water-soluble or water-dispersible polymer formed from an anionic synthetic resin emulsion, a monomer mixture containing at least 20% by weight of amine functional monomers,
Compositions containing a sufficient amount of a volatile base to raise the pH of the composition to a point where essentially all of the polyfunctional amine is in a non-ionic state, such as, for example, trade name E-2706
(Manufactured by Rohm and Haas).

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0029

[Correction method] Change

[Correction contents]

The coating composition of the present invention requires a volatile base. Type and amount of volatile base used, up to the point where the pH of the amine functional groups of the amine-containing polymer of the composition is non-ionized (deprotonated), typically at least pH 5, preferably pH 7 -9 to be sufficient to avoid interaction with the anionically stabilized synthetic resin emulsions and other anionic components in the quick-drying coating composition.

[Procedure amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0030

[Correction method] Change

[Correction contents]

After application, the volatile base evaporates and the composition
Decrease pH . When the pH of the composition drops to the point where protonation of the amine function begins to occur, the amine function becomes cationic. It is believed that this rapid drying is initiated by this conversion of the amine functionality to the cationic state in the presence of an anionically stabilized emulsion polymer, but the exact mechanism that produces this quick drying is It has not been established, and thus the present inventors do not limit its quick-drying with exact mechanistic theory.

[Procedure amendment 6]

[Document name to be amended] Statement

[Correction target item name] 0039

[Correction method] Change

[Correction contents]

The coating composition of the present invention may contain an anionic surfactant neutralized with a volatile base as a pigment dispersant. The amount of the surfactant to be added is sufficient to disperse the pigment, and is usually 0.2 to 1.0% by weight of the active ingredient based on the pigment. Surfactants neutralized with metal salts such as sodium and potassium, not volatile bases, are widely known, but they prevent the pH of a paint composition after coating from rapidly lowering and have an amine function. This is not preferred because the onset of protonation of the group is delayed, resulting in impaired drying properties.

[Procedure amendment 7]

[Document name to be amended] Statement

[Correction target item name] 0041

[Correction method] Change

[Correction contents]

The aqueous coating composition of the present invention has a pigment volume concentration (PVC) in the range of 20% to 70%, typically has a solid content in the range of 10 to 70%, and
Formulated so that the viscosity of the paint is 50-5,000 poise
Is done. In general, the higher the solid content, the higher the quick-drying property. However, if the PVC becomes high, the rubber elasticity will be reduced, so that it is preferably 20% to 60%,
Most preferably, it is 25% to 45%.

[Procedure amendment 8]

[Document name to be amended] Statement

[Correction target item name] 0056

[Correction method] Change

[Correction contents]

Sample No. 11-13 at 5 ℃, 80%
After application on a glass plate using a 5 mil applicator in an environment of RH , the film was rubbed with a finger, and the time until the film was skinned and dried was measured. The results were as follows.

[Procedure amendment 9]

[Document name to be amended] Statement

[Correction target item name] 0058

[Correction method] Change

[Correction contents]

Monomer mixture 1 followed by sample N
O. Emulsions having the compositions shown in Table 5 were synthesized in the same manner as when the emulsion polymers of Nos. 1 to 4 were prepared. The obtained emulsion was applied on a glass plate using a 5 mil applicator in an environment of 22 to 23 ° C. and 60% RH , and then rubbed with a finger, and the time required for skinning and drying the film was measured. . Table 6 shows the results.

[Procedure amendment 10]

[Document name to be amended] Statement

[Correction target item name] 0066

[Correction method] Change

[Correction contents]

In the measurement of elongation and tensile strength due to the addition of a curing agent, a curing agent was added to a paint, mixed, and then applied on a release paper so as to have a thickness of 2 mm, and then subjected to a condition of 20 ° C. and 65% RH . After curing for 7 days, the test specimen was cut out with a dumbbell-shaped No. 3 punching die and subjected to an elongation test. The test method is as described in JIS A6021 “Coating waterproofing material for roof”.
4 According to tensile performance. The tensile strength was determined by measuring the thickness and width of the sheet when punched into a dumbbell-shaped No. 3 mold with a micrometer, and converted based on the value showing the maximum tensile strength when an elongation test was performed. The amount of the curing agent added is a weight ratio with respect to the emulsion polymer sample, and the emulsion polymer sample refers to one containing a polymer containing an amine functional group-containing monomer and a volatile base. Glycerol polyglycidyl ether (glycerin diglycidyl ether) was used as the epoxy resin.

[Procedure amendment 11]

[Document name to be amended] Statement

[Correction target item name] 0073

[Correction method] Change

[Correction contents]

[0073] For measurement of pot life after the addition mixing a curing agent, sealed in a polyethylene container, placed at room temperature, the viscosity was measured at regular intervals, Tairugan (Air
When spray coating was performed using a spray gun) and a pressure feeding machine, it was checked whether there was any problem in workability. The viscosity change is 20% less than immediately after the addition of the curing agent.
The time when the above occurred was used as one standard.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C09D 133/14 C09D 133/14

Claims (2)

[Claims] 1. An anionic synthetic resin emulsion in which the monomers excluding the anionic monomer among the monomers constituting the emulsion have a solubility in water of 100 g of 0.01 to 1.50 g. A resin emulsion, a polymer formed from a monomer mixture containing at least 20% by weight of an amine functional group-containing monomer, wherein the ratio of the number of equivalents of the amine function to the number of equivalents of the carboxyl group is 5 to 80%, Amine functional groups contained from the equivalent number of carboxyl groups contained in the volatile base in an amount sufficient to raise the pH of the composition to a point where essentially all of the polyfunctional amine is in a nonionic state 5 after subtracting the equivalent number of
% To 500% of an epoxy resin having an epoxy group number. 2. The coating composition according to claim 1, wherein the coating composition further comprises an anionic pigment dispersant neutralized with a volatile base.