JPS6221028B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to paints. More specifically, the present invention provides water reducible paints.
coating). A “water-reducible paint” (hereinafter referred to as “water-reducible paint”) as used throughout this book is a colloidal dispersion dispersed in an organic solvent and water; Resin concentration means that which can be diluted with water or a solvent and which, when diluted with a coalescing solvent, will form a durable coating when applied to a substrate surface. Other names for "water-reducible coatings" are waterborne wating, water-soluble paint
such as solubilized wating and water-dilutable coatings. Also,
The present invention relates to specific resins that are water reducible and are formulated to provide a final coating with good adhesion and water resistance. Paint resins are generally insoluble in water. Therefore, in actual use, the coating resin must be dissolved in a suitable organic solvent or dispersed in water together with auxiliary agents such as emulsifiers or surfactants in order to provide a coating suitable for application. Nakatsuta.
Significant disadvantages of organic solvent solutions include their inherent potential toxicity, flammability and environmental pollution. Environmental regulations generally apply to paint users rather than paint manufacturers. Coatings can generally be produced with little or no discharge of solvent into the environment. However, in order for these paints to be applied to or cured on finished products such as automobiles and refrigerators, most of the solvent must be evaporated. Due to this fact, various environmental laws and regulations apply to paint users. The most common systems developed by coating companies to meet environmental regulations are water-floating, powder, electrodepositable, high solids, solvent-qualified and polymer-monomer formulations for UV-curable coatings. . It is expected that water-reducing paints or water-floating paints will occupy the majority of the paint market share in the future. Although there are very few water-floating paints that do not contain organic solvents, some environmental regulations require that volatile components be
Water diluted paints containing less than % are exempted. Aqueous dispersion paints or latex-type paints contain molecular weight polymers dispersed as emulsions in an aqueous medium. In general, acrylic latex paints exhibit excellent toughness, good chemical and water resistance, and excellent durability. However, the industrial use of such coatings is limited by certain technical drawbacks. That is, external thickeners require viscosity control, have poor pigment dispersibility, poor gloss, are prone to foaming, have complex compositions, and are difficult to use due to problems such as wetting of the support. is limited. Similarly, aqueous dispersions such as those described above, when used to make coatings, generally cure resins when additional hardeners and water-insoluble coatings are required to break up residual floaters. Requires a hardening agent to Otherwise,
The paints made from aqueous dispersions will be easily washed away by washing with water. On the other hand, water-reducible polymers are considered to be ultrafine particles with a molecular weight between that of emulsion polymers and true solutions. These polymers contain polar groups. The polar group confers solubility. The polymer is a mixture of an emulsion polymer and a solution polymerized polymer. This is because said polymers have properties of both types. The affinity of a resin for water can be controlled by the degree of solvation of polar groups (eg, carboxylic acid moieties in the case of acrylic polymers) in the polymer backbone. Solvation is carried out by adjusting the pH and/or by adding water-miscible polar solvents. Water-reducible resins are alkali-soluble (contains acidic groups), acid-soluble (contains basic groups), or nonionic (contains amide or hydroxyl groups along with acid or basic components). be able to. The resins of the present invention are of acidic or nonionic type. Paints made from water-reducible resins have advantages over emulsion-type paints. Paints made from water-reducible resins have good flow and leveling properties. Pigment dispersibility is also good. The composition of the coating composition is not very complicated, and the gloss of the final coating film is also good. Another important advantage of water-reducible type paints is that they can be prepared with little use of surfactants or emulsifiers. The use of large amounts of emulsifiers or surfactants impairs the physical properties of the final coating. Representative examples of resins currently used in water-reducible paints include alkyd resins (eg, US Pat. No. 4,051,089), styrene acrylic resins, acrylic resins, and polyester resins. The present invention relates to an acrylic type resin. U.S. patents disclosing this water-reducible acrylic resin include: U.S. Pat. No. 3,862,071, which discloses acrylate-acrylic acid copolymers and metallic flake pigments; Patent No. 3904569
(which discloses an aqueous dispersion containing a carboxylic acid-containing resin and an aliphatic polyamine) water-reducible acrylic resin having both hard and soft segments and to which a plasticizer is added. is disclosed in US Pat. No. 4,064,092. There are two divisional applications for this U.S. patent (application number 827196, patent number 4097440, filing date,
August 23, 1977). Adhesion and water resistance have been problems with water-reducing resins. The resin has an affinity for water. Paints made from such resins therefore swell upon contact with water. Adhesion can be improved by adding plasticity (eg miscible phthalates). However, some plasticizers can be extracted with water or soapy water. There are various monomers known as fixing agents. Examples include vinylpyridine, 2-ethylhexyl methacrylate, methacrylic acid, dimethylaminoethyl methacrylate and isobutoxymethacryamide. N-vinyl-2-pyrrolidone is known as a hydrophilic fixing agent monomer. N-vinyl-2-pyrrolidone is one of the polymers.
~20% consists of monomeric units, giving the polymer strength,
It is known that it can impart dye receptivity and hardness. Similarly, it is known that N-vinyl-2-pyrrolidone can alter the water-swelling equilibrium, melting point, dielectric properties or surface activity. Similarly, vinylpyrrolidone copolymers are known to provide smooth continuous coatings with good hardness, stiffness and grease resistance properties. The present inventor has carried out extensive trial production and research for many years in order to obtain a water-reducible acrylate paint resin that has extremely good adhesion to metal surfaces and water resistance that prevents powdering and cracking, and has developed the present invention. I was able to complete it. The inventors have found that in certain types of acrylate polymers, from about 0.5% to about 5%
It has been discovered that the incorporation of N-vinyl-2-pyrrolidone achieves the above objectives better than other fixing agents previously used. Accordingly, the present invention provides resins suitable for use in water-reducible compositions. The resin contains, based on 100% by weight monomer units in the polymer, (i) about 0.5% to about 5% N-vinyl-2-pyrrolidone, (ii) about 2% to about 15% acrylic acid, methacrylic acid, an unsaturated carbonyl compound selected from the group consisting of fumaric acid, itaconic acid, maleic acid and maleic anhydride; and (iii) methyl acrylate in an amount sufficient to achieve a 100% standard for monomer units. , ethyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, isodecyl methacrylate, 2-ethylhexyl methacrylate, butyl acrylate, butyl methacrylate and isobutyl methacrylate, and/or (b) A monomer selected from the group consisting of styrene, a styrene derivative in which hydrogen at the α-position of a vinyl group or a benzene nucleus is substituted with a methyl group, and methyl methacrylate, the maximum possible copolymerization amount of which is monomer (a). It consists of about 97% of monomer (2) and about 95% of monomer (b). The total amount of monomer units is, of course, 100%. Generally speaking, harder coatings contain about 20% to about 30% of monomers from groups (iii) and (b), such as styrene, and about 60% to about 30% of at least two monomers from groups (a). Manufactured from resin containing 75%. By using the resin of the present invention, a water-reducible coating composition can be produced that can provide a water-insoluble dry coating film with excellent adhesion and water resistance even without a curing agent or hardener. I can do it. The resins of this invention can be prepared by reacting monomers in an aqueous emulsion medium. The principle of emulsion polymerization is disclosed in the following literature: “Synthetic Rubber” by Whitby, John.
Wiley & Sons, 1954, Chapter 8;
“Emulsion Polymerization”, Bovey FA et al., “High Polymers” volume, Interscience
Publishers (1955); US Patent No. 3714122
Specification, column 5, lines 41-67 and column 6, lines 11-59. Emulsion polymerization is generally well known in the art. The polymerization reaction between monomers takes place in fine monomer droplets. The fine monomer droplets are obtained by mechanical stirring under the action of an emulsifier or surfactant which forms a film around these droplets. The emulsifier aggregates to form micelles in which both monomer and catalyst are dispersed. Setsuken or emulsifier micelles are the locus of polymerization in the early stages. Using free radical catalysts. During the reaction
Regulate PH and temperature. PH can be easily adjusted with inorganic bases such as sodium hydroxide, potassium hydroxide and ammonium hydroxide. The reaction temperature is usually within the range of 5°C to 80°C. Modifiers such as mercaptans and divinylbenzene are often used to control polymer chain growth and average molecular weight. When synthesizing the resins of the present invention, monomers are mixed with water, surfactants, chelating agents, modifiers, and free radical catalysts. Mix these ingredients and at a temperature of about 52°C, 2 to 7, preferably
React for 8 to 16 hours at a pH of 2.5 to 6. The resins of this invention can be recovered by coagulation techniques well known in the emulsion polymerization art. A suitable flocculant and suitable flocculation conditions are selected depending on the properties of the resin. After removing as much unreacted monomer as possible by steam stripping or other suitable methods, the reaction product mixture is mixed with an aqueous flocculant solution with stirring to form a slurry of resin particles.
The resin slurry thus obtained is filtered and the filter cake is dried in conventional resin processing equipment. Examples of the present invention used aqueous solutions of aluminum sulfate and sulfuric acid mixtures to coagulate at temperatures ranging from about 60°C to 85°C, and the resins were air dried at a temperature of about 60°C. The film-forming water-reducible composition is formed using a mixture of a resin, a suitable coalescing solvent, and a volatile amine. The dry resins mentioned above are preferred as starting materials for this mixture. However, the emulsification reaction product from the resin production reaction can be used as is without going through the intermediate aggregation step and drying step. In such operations, if enough amine is used, the complex will automatically become in the water-reduced form. Suitable coalescing solvents are those that have an affinity for both the resin polymer and water, such as alcohols, glycol ethers, and ketones.
Suitable solvents have higher boiling points than water. Therefore, the solvent is the last solvent to be emitted from the applied coating. In fact, by neutralizing the carboxyl groups of the resin with a suitable volatile amine, the mixture becomes reducible with water. Add the amine or any other volatile base to the resin solvent mixture. The neutralized carboxylic acid groups impart water affinity to the resin. In fact, the resin is suspended between both the solvent phase and the aqueous phase. The amine is selected from primary, secondary, and tertiary amines having a melting point within the range of about -40°C to about 25°C and a boiling point within the range of about 50°C to about 150°C. After adding the amine, water can be added as a diluent. When water is added, a suitable dispersion with a PH value of about 8 to about 14 is produced. A resin polymer dissolved in an organic solvent undergoes a phase transformation in water to form stable colloidal particles or micelles. The coating compositions below are representative of compositions of the present invention. Ingredient parts by weight Resin 20-30 Amine 1-3 Defoamer 0.2-0.5 Water-soluble solvent (e.g. butyl cellosolve) 10-11 Water-insoluble solvent (e.g. MIBK) 2-4 Water 45-60 In the above composition, "resin" ” means a carboxylated vinylpyrrolidone copolymer as described above. "MIBK" means methyl isobutyl ketone. "Butyl cellosolve" is the trade name of Union Carbide Corporation for ethylene glycol monobutyl ether.
Water-insoluble solvents can be used to reduce the viscosity of the composition. It can also be carried out outside the above range of ratios. For example, when producing a resin using acrylic acid content, the amount of solvent can be significantly reduced while the amount of water can be significantly increased. However, when performing this operation, the water sensitivity of the final coating is increased. But this is not a good thing. The above formulations cover a good range of practical coatings. Paints according to the above formulation produce clear coatings with good adhesion and water resistance. Similarly, the coatings can be mixed with aqueous dispersion (latex) type compositions and various pigments and plasticizers. Preferred resins for use in the water-reducible compositions of the present invention are those that require a minimum number of monomers for their synthesis. Of course, this simplifies the manufacture of the resin. Coalescing solvents are typically ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether,
Diethylene glycol monobutyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol diethyl ether, ethylene glycol monomethyl ether acetate, dipropylene glycol methyl ether, methyl ethyl ketone, propylene glycol ethyl ether, propylene glycol isopropyl ether, propylene glycol butyl ether,
selected from the group consisting of acetone, methylpropylketone and diacetone alcohol. Of the various solvents that can be used, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether and diethylene glycol monobutyl ether are generally preferred. Solvents and resins are typically around 25°C
The mixture is mixed for about 20 to about 60 minutes at a temperature of ~80°C. Representative examples of the various volatile amines that can be used to form water-reducing compositions include primary amines such as ethylamine, propylamine, butylamine, isoamylamine, amylamine, hexylamine, heptylamine, and ethanolamine; diethylamine; , ethylethanolamine and morpholine; and tertiary amines such as dimethylethanolamine, trimethylamine, triethylamine and N-methylmorpholine. The pH value of the final aqueous dispersion is about 8 to about 14.
Add enough amine to give . Water-insoluble solvents are generally mineral spirits,
selected from the group consisting of ketones (eg MIBK), aromatic solvents and acetates. The solvent is either a true solvent for the resin or one that forms a true solvent for the resin when mixed with a water-soluble solvent. The amount of water used depends on whether a viscosity or low viscosity dispersion is required or whether a solids content or low solids content is required. It also depends on the type of coalescing solvent used and the amount used. Water is usually about
Mixed with the amine neutralizing composition at a temperature of 25°C to about 80°C. The water to solvent volume ratio is preferably about 4 to 1. Here, the term "solvent" refers to all volatile organic solvents (water-soluble solvents, water-insoluble solvents and amines). Increasing the level of acidic monomer allows the use of lower levels of solvent. but,
This creates water sensitivity in the coating. Solvent levels can be similarly reduced by substituting plasticizers for some solvents. Water, amines and coalescing solvents typically range from about 20°C to about
It is evaporated from the applied paint at a temperature of 100°C, preferably within the range of about 25°C to about 50°C. Coatings prepared by applying the coatings of this invention to a support are typically dried for about 8 to about 24 hours. Hereinafter, the present invention will be explained in more detail with reference to Examples. However, the following examples are for the purpose of illustrating the invention, and the invention is not limited thereto. All parts and percentages are by weight unless otherwise specified. Example 1 Capacity 0.95 clamped on rotating wheel polymerizer
The polymerization was carried out in a glass bottle. The polymerizer wheel was placed in a water bath maintained at a temperature of 52°C. Fill each glass bottle with the ingredients,
It was purged with nitrogen gas and capped with a perforated lid with a rubber disk seal. By using a perforated lid, a hypodermic needle can be inserted into the bottle and a sample taken. Polymerizations were carried out in two vials for each formulation. The conversion rate at a given polymerization time was determined by measuring the total solids content of the sample at that time and estimating the conversion rate from the linear relationship between total solids content and conversion rate. Total solids content was determined by drying a weighed sample of latex in an aluminum pan of known weight with an infrared lamp until the sample was dry. Polymerization within the bottle proceeds to almost completion. Table 1 shows the reaction components, reaction conditions, and physical properties of the final product.

【table】

Table: Example 2 The resin prepared in Example 1 above was separated from the reaction product mixture by coagulation and drying. The two glass bottles were mixed together before agglomeration. The coagulant in each case was a mixture consisting of 6 g aluminum sulfate, 3 g sulfuric acid (95-98%) and 4000 ml water. The solidification temperatures are shown in Table 2.
The slurry produced from each coagulation run was passed through a cloth-lined Buchner funnel. After filtration, the resin cake was washed twice with cold soft water. The resin was then dried in an oven at 60°C.

[Table] Example 3 A film-forming water-reducible paint was prepared by mixing the following components (A) to (E) in the proportions in parts by weight shown in Table 5 below. The resulting composition (latex-free) was a water-insoluble, water-reducible paint that gave a dry film with good adhesion. (A) Resin in Table 3 below

[Table] Mixtures of various water-reducible compositions and aqueous dispersions or latex-type paints were prepared.
The polymers emulsified in the latex used were selected from those shown in Table 4 below.

Table: The presence of 2-ethylhexyl acrylate produces a relatively soft polymer. A resin latex mixture was prepared by mixing the water-reducible paint described above with latex, water, and a small amount of defoamer. A pigment consisting of a titanium dioxide slurry (solids content 60%) was added to these paint mixtures. The resulting mixture was applied to a phosphorylated test steel plate using a No. 30 wire coated applicator bar to obtain a film having a thickness in the range of 0.8 to 2.5 mils (0.02 to 0.06 mm). The applicator stick is RD
It was manufactured by Specialty Company, Webster, New York. It was also representative of what is normally used to apply the test paint. The paint was then allowed to dry for 2 hours at room temperature, and
The remaining solvent was removed by drying for 30 minutes in an oven at a temperature of 49°C to 54°C. Test results for formulations for water-reducible compositions, resin latex mixtures, pigment-containing mixtures, and coatings made with pigment-containing mixtures are shown in Table 5 below.

[Table] Gloss is the ability of a surface to reflect light regularly. As mentioned here, gloss is the gloss of an object (light reflected regularly or specularly from a coated sample at an angle of incidence of 60°) as measured by a Hunter Glossmeter (ASTM method D-523). strength). The brittleness, elasticity, adhesion, and elasticity of the coating film were tested by backside impact. In this test, a weight was dropped onto a test panel (coated side facing down) on an anvil surface or impact surface. This test was conducted on an instrument such as a Parlin-du Pont type impact tester or ball bearing impactor. The inches listed in Table 5 are the various heights at which the weights rose above the test panel. A coating passes this test if it does not loosen, crack appreciably, or flake off. Higher backside impact resistance means a better coating. Samples H and J (approximately 50/50 and 25/75 mixtures of water-reducible resin and latex resin, respectively) had similar results to control sample V, which was composed of the same latex, but other latexes It gave better results than the control sample U consisting of. The water-reducible resins in Samples H and J (2731) were produced by a continuous monomer addition method. On the other hand, the other two types of resins were produced by batch reaction methods. The continuous addition method produces a resin polymer that is close in composition to the proportions of the filled feedstock. In a batch process, the more reactive monomer (e.g. methacrylic acid) reacts more rapidly than other monomers, and the particular monomer unit is relatively low in a polymer molecule and another polymer molecule in which the particular monomer unit is low. generate. The carboxyl groups are therefore said to be "blocked" as opposed to evenly distributed. Continuous monomer addition techniques are known in the polymerization art, and examples of such techniques are disclosed in US Pat. No. 3,324,066 and US Pat. No. 3,966,661.
Emulsion polymerization is carried out by the following steps: (1) An initial increment of monomer that is only a fraction of the total charge (e.g. 5 to 20 increments of monomer).
(2) forming an aqueous dispersion in which the increment contains at least a portion of the acrylate monomer and an unsaturated carbonyl compound; (3) Add the remainder of the monomers together with the catalyst and emulsifier to the dispersion incrementally or continuously (e.g. 8-16% per hour). Another method for synthesizing homogeneous resin polymers is to use a mixture of acrylic acid and methacrylic acid as the carbonyl compound in a batch reaction system. Acrylic acid reacts more slowly than methacrylic acid. It thus helps to distribute the carbonyl groups in the polymer. This method is substantially less effective than the continuous monomer addition method. The data shows that: That is, (1) it is preferable to produce the water-reducible resin by a continuous monomer addition method; (2) the weight ratio of the water-reducible resin to the latex resin is about
Preferably, a mixture of 30:70 to about 70:30 is produced; and (3) high gloss is produced by using a "soft" latex and resin mixture containing 2-ethylhexyl acrylate (2457C). can. Since the titanium dioxide pigment is added to the resin-latex mixture, the adhesion of the final coating is adversely affected. Plasticizers are considered to be undesirable ingredients.
This is because the plasticizer is extracted from the coating by the solvent. However, for applications other than solvent-resistant coatings, plasticizers are not harmful. Coatings using plasticizers should contain from about 5 to about 10 wt% plasticizer as a preferred proportion for formulations such as in Example 3. The plasticizer used is liquid at room temperature and has a sufficiently low boiling point (preferably at least 100°C, more preferably at least 150°C). This prevents the plasticizer from volatilizing from the final coating. The plasticizer used must allow for water insolubility of the final dry coating. Furthermore, the plasticizer must be compatible with the water-reducible resin. For this property, a solubility parameter within the range of about 8 to about 11 is required. Such solubility parameters are “The
Encyclopedia of Polymer Science and
Technology”, vol. 3, p. 854, 1965 John
It is of the type described in Wiley and Sons. The parameters can be easily determined by the following equation. δ=(ΣF)V ΣF/MW/d where δ is the solubility parameter and ΣF is the sum of the appropriate molar attraction constants of the groups as determined by Small, PA [“J.Appl.
Chem."3, 71, (1953) V is the molar volume at 25°C, MW is the molecular weight, and d is the density at 25°C. Various plasticizers can be used for this purpose.
The plasticizer is compatible (or miscible) with the boiling point mentioned above.
For example, plasticizers can be used in the Federation series on coating technology entitled “Plasticizers” published in April 1974.
Types listed in Unit 22 of Series) may be used. Typical examples of various plasticizers include phosphoric acid esters, phthalic anhydride and trimellitic acid esters, N-cyclohexyl-p-toluenesulfonamide, diverdyl sebacate, diethylene glycol dibenzoate, di-t-octyl phenyl ether, Dipropanediol dibenzoate, N-ethyl-p-toluenesulfonamide, isopropylidene diphenoxypropanol, alkylated naphthalene, polyethylene glycol dibenzoate, op-toluenesulfonamide, trimethylpentanediol dibenzoate and trimethylpentanediol mono Cyclic plasticizers such as isobutyrate monobenzoate. Typical examples of various acrylic plasticizers are adipic acid esters, azelaic acid esters, citric acid esters, acetyl citrate esters, myristic acid esters, phosphoric acid esters, ricinoleic esters, and acetyl ricinoleic esters. , sebacic acid esters, stearic acid esters, epoxidized esters, 1,4-butanediol dicaprylate, butoxyethyl pelargonate di[(butoxyethoxy)ethoxy]methane, dibutyl tartrate, diethylene glycol dipelargonate, diiso -Octyl diglycolate, isodecyl nonanoate, tetraethylene glycol di(2-ethylbutyrate), triethylene glycol di(2-ethylhexanoate), triethylene glycol dipelargonate and 2,2,4-trimethyl -1,3-pentanediol diisobutyrate and the like. Although the practical mechanics of water-reducing resins are not completely understood, they can be made substantially water-insoluble by applying the coating of the present invention and drying the applied coating to remove water, amines, and coalescing solvents. A coating film of is formed on the support. Application is carried out by any conventional method such as brushing or spraying.
The coating thickness generally ranges from about 1 to about 30 mils (0.025 to 30 mils).
0.762 mm), preferably 1 to about 5 mils (0.025 to 0.13
mm). Typical uses of the paint of the present invention include metal decorative paints, pigment-containing paints such as underground sealants, and paints for metal cans. The resins of the invention can likewise be used in printing inks. When used in printing inks, the loading of unsaturated carbonyl compounds (eg methacrylic acid) is relatively low (10-15%). This gives better water solubility. The scope of the present invention includes water-reducing resins such as those described above,
Also included are paints containing, in addition to solvent and water, other conventional paint ingredients such as pigments, alkyds, oils (eg pine oil) and thickeners. Although certain representative embodiments and details have been shown for the purpose of illustrating the invention, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit or scope of the invention. .

Claims (1)

[Scope of Claims] 1. A film-forming, water-reducible paint comprising (A) a resin, (B) a coalescing agent, and (C) a volatile amine, wherein the resin contains 100% by weight of monomer units in the resin. (i) 0.5-5% N-vinyl-2-pyrrolidone; (ii) 2-15% acrylic acid, methacrylic acid, fumaric acid, itaconic acid, maleic acid and maleic anhydride. an unsaturated carbonyl compound selected from the group consisting of: (iii) an amount sufficient to achieve a 100% standard for monomer units; At least two acrylate monomers selected from the group consisting of methacrylate, 2-ethylhexyl methacrylate, butyl acrylate, butyl methacrylate and isobutyl methacrylate, and/or (ro)styrene, the α-position of a vinyl group, or a benzene nucleus A monomer selected from the group consisting of styrene derivatives and methyl methacrylate in which the hydrogen of The above-mentioned water-reducible paint is a polymer composed of a certain monomer. 2 The fusion solvent is ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, diethylene glycol monoethyl ether acetate,
Claims selected from the group consisting of diethylene glycol diethyl ether, ethylene glycol monomethyl ether acetate, dipropylene glycol methyl ether, methyl ethyl ketone, propylene glycol ethyl ether, propylene glycol isopropyl ether, propylene glycol butyl ether, acetone, methylpropyl ketone and diacetone alcohol The film-forming water-reducing paint according to item 1. 3. The volatile amine is from the group consisting of ethylamine, propylamine, butylamine, isoamylamine, amylamine, hexylamine, heptylamine, ethanolamine, diethylamine, ethylethanolamine, morpholine, dimethylethanolamine, trimethylamine, triethylamine and N-methylmorpholine. A film-forming water-reducible paint according to claim 2, which is selected. 4. The film-forming water-reducible paint according to claim 3, wherein the starting material for forming the mixture is an emulsification reaction product of a resin-forming reaction. 5. A film-forming, water-reducible paint according to claim 3, wherein the resin (A) is in dry form. 6. The film-forming, water-reducible paint according to claim 5, wherein sufficient water is added to provide a water to solvent volume ratio of 4:1. 7 further contains a defoamer and a water-insoluble solvent,
The ingredients are in the following proportions: Resin 20-30 parts Amine 1-3 parts Defoamer 0.2-0.5 parts Water-soluble solvent 10-11 parts Water-insoluble solvent 2-4 parts Water 45-60 parts by weight The film-forming water-reducible paint according to claim 6. 8. The film-forming water-reducible paint according to claim 7, wherein the resin used is produced by a continuous monomer addition method. 9 The resin is isobutyl methacrylate 71
%, 2-ethylhexyl methacrylate 24%,
A film-forming, water-reducible paint according to claim 8, comprising 3% methacrylic acid and 2% N-vinyl-2-pyrrolidone. 10. The film-forming water-reducible paint according to claim 8, wherein a latex paint is added. 11. The film-forming water-reducible paint according to claim 10, wherein the weight ratio of water-reducible resin solids to latex resin solids is from 30:70 to 70:30. 12 The water-reducing resin contains 71% isobutyl methacrylate, 24% 2-ethylhexyl methacrylate, 3% methacrylic acid, and N-vinyl methacrylate.
Claim 1 consisting of 2% 2-pyrrolidone
The film-forming water-reducible paint according to item 1. 13. The coating film forming method according to claim 12, wherein the latex resin comprises 47.5% n-butyl methacrylate, 48% 2-ethylhexyl methacrylate, 2.5% methacrylic acid, and 2% N-vinyl-2-pyrrolidone. Water-reducing paint. 14 Titanium dioxide pigment is added, the water-soluble solvent is ethylene glycol monobutyl ether, the water-insoluble solvent is methyl isobutyl ketone, the amine is triethylamine, and the component classification is as follows: Part Water-reducing resin 12.5 Defoaming agent 1 Ethylene glycol monobutyl ether 8.5 Methyl isobutyl ketone 5 Triethylamine 1 Latex (solid content 40%) 31.25 Water 41.25 TiO ₂ slurry (60%) 20.8 Claim 13 which exists in Film-forming, water-reducing paint. 15 The resin is isobutyl methacrylate 40
~42%, 2-ethylhexyl methacrylate 27
28% styrene, 2-5% N-vinyl-2-pyrrolidone and 3% methacrylic acid.