JP4406468B1 - Water-based quick-drying paint composition - Google Patents

Abstract

【Task】
To provide an aqueous quick-drying paint composition that does not generate odor during work, is environmentally friendly, can effectively use industrial waste, and is excellent in quick-drying, which is a drawback of aqueous paints.
[Solution]
The present invention relates to a water-based quick-drying paint composition comprising a resin emulsion obtained by emulsion polymerization of an ethylenically unsaturated monomer composition, a fired shell and a emulsifier, using a water-dispersible polyester as a protective colloid. Related to things. The fired shell is preferably a fired scallop shell. It is preferable to use 1 mass%-50 mass% of scallop shell baked products with respect to the resin emulsion.
[Selection figure] None

Description

  The present invention relates to a water-based quick-drying coating composition.

  In recent years, water-based solvent-based paints are strongly desired from the viewpoint of reducing the burden on nature and the human environment. However, water-based paints usually have a great disadvantage that they are inferior in quick-drying properties compared to solvent-based paints, so that there are many restrictions in use. Therefore, various improvement means suitable for the intended use have been proposed. For example, in applications such as road surface display paints, floor polishes, printing inks, etc., many have been proposed that use an ion complex of an anionic polymer and a cationic polymer by using a volatile base and changing pH. (For example, refer to Patent Documents 1 to 3). These quick-drying systems require a volatile base, have a strong odor during work, and further gelation progresses from the surface of the applied paint, so when a thick film is applied, only the paint surface layer forms a film. There is a problem that gelation of the intermediate layer is significantly delayed. In order to solve the above problem, a method of spraying an inorganic substance that reacts with water and generates heat on a paint applied to a road surface has been proposed (see, for example, Patent Document 4). There has been proposed a method in which a soluble metal compound aqueous solution is sprayed on a coated paint (see, for example, Patent Document 5). However, it is necessary to completely cover the surface of the coating film, and the work process for spraying increases, so that workability is difficult. By the way, paints containing shell powder such as scallops have been proposed for the purpose of imparting functions such as adsorption removal of harmful chemical substances and antibacterial properties (see, for example, Patent Documents 6 to 10).

JP 2002-309158 A JP2004-168998 JP 2001-329182 A JP2004-244467 JP2008-7745 JP-A-8-12906 JP2001-9978 JP 2003-73626 A JP2009-13376 Table 2004-089092

  Accordingly, the present invention has been made to solve the above-described problems, does not generate odor during work, is environmentally friendly, can effectively use industrial waste, and is a drawback of water-based paints. An object of the present invention is to provide a water-based quick-drying paint composition having excellent quick-drying properties.

  Therefore, as a result of intensive studies to solve the above problems, the present inventors have made a resin emulsion obtained by emulsion polymerization of an ethylenically unsaturated monomer composition using a water-dispersible polyester as a protective colloid and a shell. The present inventors have found that the above-mentioned problems can be solved by using a fired product and an emulsifier, and have completed the present invention.

  That is, the present invention comprises a water-based quick-drying characterized by containing a resin emulsion obtained by emulsion polymerization of an ethylenically unsaturated monomer composition, a fired shell and an emulsifier, using a water-dispersible polyester as a protective colloid. It is a coating composition.

  In the present invention, the fired shell is preferably a fired scallop shell.

  It is preferable to use 1 mass%-50 mass% of scallop shell baked products with respect to the resin emulsion.

  The emulsifier is preferably a nonionic emulsifier.

  The nonionic emulsifier is preferably used in an amount of 10% by mass to 40% by mass with respect to the fired shell.

  It is preferable to use 5 mass%-70 mass% of water dispersible polyester with respect to an ethylenically unsaturated monomer composition.

  According to the present invention, it is possible to provide a water-based quick-drying paint composition that is environmentally friendly, can effectively use industrial waste, and is excellent in quick-drying, which is a drawback of water-based paints.

  Hereinafter, the present invention will be described in detail.

  The water-based quick-drying coating composition according to the present invention contains a resin emulsion obtained by emulsion polymerization of an ethylenically unsaturated monomer composition using a water-dispersible polyester as a protective colloid. The amount of the water-dispersible polyester is preferably 5% by mass to 70% by mass, and more preferably 10% by mass to 50% by mass with respect to the ethylenically unsaturated monomer composition. When the water-dispersible polyester is less than 5% by mass, the stability of the resin emulsion is difficult, and when it exceeds 70% by mass, the water resistance of the film may be lowered.

  The resin emulsion in the present invention can be obtained by radical polymerization of an ethylenically unsaturated monomer in the presence of a water-dispersible polyester. The ethylenically unsaturated monomer used in the present invention may be any monomer having at least one polymerizable vinyl group, and has, for example, a linear, branched or cyclic alkyl chain (meth). Representative examples of acrylic esters, aromatic vinyl compounds such as styrene and α-methylstyrene, heterocyclic vinyl compounds such as vinylpyrrolidone, hydroxyalkyl (meth) acrylates, alkylamino (meth) acrylates, vinyl acetate and vinyl alkanoates Vinyl esters, monoolefins (ethylene, propylene, butylene, isobutylene, etc.), conjugated diolefins (butadiene, isoprene, chloroprene, etc.), α, β-unsaturated mono- or dicarboxylic acids (acrylic acid, methacrylic acid, Crotonic acid, itaconic acid, maleic acid, fumaric acid, etc.) Vinyl cyanide compounds such as acrylonitrile, carbonyl group-containing ethylenically unsaturated monomers acrolein and diacetone acrylamide, etc., sulfonic acid group-containing ethylenically unsaturated monomers such as p- toluenesulfonic acid. These ethylenically unsaturated monomers may be used singly or in combination of two or more. Among these, methyl methacrylate, n-butyl (meth) acrylate, 2-ethylhexyl acrylate, styrene, hydroxyethyl (meth) acrylate, vinyl acetate, and ethylene are preferable from the viewpoint of easy radical polymerization and durability.

  If necessary, epoxy group-containing α, β-ethylenically unsaturated compounds such as glycidyl (meth) acrylate, hydrolyzable alkoxysilyl group-containing α such as vinyltriethoxysilane and γ-methacryloxypropyltrimethoxysilane , Β-ethylenically unsaturated compounds, cross-linkable monomers such as polyfunctional vinyl compounds (ethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, allyl (meth) acrylate, divinylbenzene, diallyl phthalate, etc.) You may introduce | transduce into a copolymer.

  The water dispersible polyester is a known one obtained by neutralizing a polymer obtained by polymerizing a polybasic acid and a polyol. Here, the water-dispersible polyester is one having a hydrophobic part (hydrophobic part) and a hydrophilic part (hydrophilic part) in the polyester molecule, and the hydrophilic part around the hydrophobic part in water. Is a particle that surrounds and stably disperses. The reason why the water-dispersible polyester improves the quick-drying property of the water-based coating composition is that the calcium component contained in the shell baked product and the functional group (carboxyl group, sulfonic acid group, etc.) of the water-dispersible polyester This is presumed to be a chelate effect.

  Examples of the polybasic acid component include terephthalic acid, isophthalic acid, phthalic acid, naphthalene dicarboxylic acid, adipic acid, succinic acid, sebacic acid, dodecanedioic acid or esterified products thereof (such as dimethyl ester). You may use individually by 1 type and may be used in combination of 2 or more type.

  Typical examples of the polyol component include ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, cyclohexane dimethanol, bisphenol, and the like. These may be used individually by 1 type and may be used in combination of 2 or more type.

  Of these, a water-dispersible polyester in which the polybasic component is terephthalic acid or isophthalic acid and the polyol component is ethylene glycol, propylene glycol or 1,6-hexanediol is preferred from the viewpoint of water dispersion stability.

  In order to further improve the water dispersibility of the polyester, a polymerization component having a hydrophilic group such as a carboxyl group or a sulfonic acid group may be copolymerized.

  As specific examples of these, in order to introduce a carboxyl group into a polyester molecule, for example, (anhydrous) trimellitic acid, (anhydrous) pyromellitic acid, trimesic acid, or an esterified product thereof (such as methyl ester) is polymerized. What is necessary is just to neutralize the obtained polymer with an amino compound, ammonia, an alkali metal salt, etc. using it for a part of component. Of these, (anhydrous) trimellitic acid is preferable from the viewpoint of water dispersibility.

  In order to introduce a sulfonic acid group into a polyester molecule, for example, 5-sulfoisophthalic acid, sulfoterephthalic acid, 4-sulfophthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid or an esterified product thereof (dimethyl) An alkali metal salt such as an ester) or an ammonium salt may be used as part of the polymerization component. Of these, 1,3-dimethyl 5-sulfoisophthalate is preferable from the viewpoint of water dispersibility.

  As the water-dispersible polyester used in the present invention, commercially available polyesters may be used as they are, for example, plus coat Z-561, Z-730 and RZ-142 (manufactured by Kyoyo Chemical Co., Ltd.), pesresin A-110 A-210 and A-620 (manufactured by Takamatsu Yushi Co., Ltd.), Bayronal (registered trademark) MD-1200, MD-1220, MD-1250, MD-1335, MD-1400, MD-1480 and MD-1500 (Toyo Spinning Co., Ltd.).

  As described above, the resin emulsion in the present invention can be obtained by radical polymerization of an ethylenically unsaturated monomer composition in the presence of a water-dispersible polyester. The polymerization reaction is carried out by a batch type, semi-continuous type or continuous type method using an atmospheric pressure reactor or a pressure resistant reactor. The reaction temperature is usually 10 to 100 ° C., but 30 to 90 ° C. is common. The reaction time is not particularly limited, and may be appropriately adjusted according to the amount of each component and the reaction temperature. In radical polymerization, the water-dispersible polyester, which is a protective colloid, contributes to the stability of the emulsion particles. An anionic emulsifier, a nonionic emulsifier, and a reactive emulsifier may be used as necessary. What is necessary is just to adjust suitably the kind and usage-amount of an emulsifier according to various conditions including the usage-amount of water-dispersible polyester, and the monomer composition to superpose | polymerize.

  Examples of the emulsifier used for such radical polymerization include nonionic emulsifiers such as polyoxyalkylene alkyl ether, polyoxyalkylene alkylphenol ether, polyoxyalkylene fatty acid ester, polyoxyalkylene sorbitan fatty acid ester, alkyl sulfate ester salt, alkylbenzene. Anionic emulsifiers such as sulfonates, alkylsulfosuccinates, alkyldiphenyl ether disulfonates, polyoxyalkylene alkyl sulfates, polyoxyalkylene alkyl phosphates and the like can be mentioned. These may be used individually by 1 type and may be used in combination of 2 or more type. In addition, water-soluble polymers such as polyvinyl alcohol, methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, and polyvinyl pyrrolidone may be used as long as the water resistance of the obtained water-based coating composition is not impaired.

  The polymerization initiator used in the radical polymerization may be a known and conventional one, and examples thereof include hydrogen peroxide, ammonium persulfate, potassium persulfate, sodium persulfate, and t-butyl hydroperoxide. If necessary, these polymerization initiators may be combined with sodium sulfoxylate formaldehyde, ascorbic acid, sulfites, tartaric acid or salts thereof for redox polymerization. Moreover, you may use alcohol and mercaptans as a chain transfer agent as needed.

  The water-based quick-drying paint composition of the present invention includes resins such as acrylic resins, ethylene-vinyl acetate resins, vinyl acetate resins, epoxy resins, amino resins, and urethane resins within a range that does not impair the effects of the present invention. Components, isocyanate and epoxy crosslinkers, viscosity improvers, colorants, antiblocking agents, antifoaming agents, film forming aids and other additives, and calcium carbonate, titanium oxide, silica sand, cement, colored aggregates, shielding It is also possible to mix inorganic substances such as thermal pigments and hollow balloons.

  The water-based quick-drying coating composition according to the present invention contains a shell baked product. Known baked shellfish, oysters, sea bream, etc. are known as fired shells, but they are easily available because they are generated in large quantities as industrial waste. In that respect, a scallop shell fired product is preferably used. The scallop shell calcined product is mainly composed of a composite of calcium oxide and calcium carbonate, but has properties different from synthesized calcium oxide and calcium carbonate because of its porosity and antibacterial / antifungal effects. As the scallop shell fired shell, a commercially available one can be used, and examples thereof include shell fill (manufactured by Nippon Natural Materials Co., Ltd.). As its general properties, pH is 10.0 or more, Ca content is 50% or more, and most of them are calcined products of calcium. The particle size is 5-30 μm, which is considerably larger than general calcium carbonate.

  The amount of the scallop shell baked product is preferably 1% by mass to 50% by mass and more preferably 4% by mass to 30% by mass with respect to the resin emulsion. When the scallop shell burned product is less than 1% by mass, the interaction with the resin emulsion is weak and sufficient quick-drying property cannot be obtained, and when it exceeds 50% by mass, an emulsifier is added to significantly reduce the stability of the resin emulsion. Even so, it may be difficult to easily adjust the gelation time.

  The drying property of the water-based quick-drying coating composition according to the present invention is adjusted by the amount of the emulsifier added. Examples of the emulsifier include nonionic and anionic emulsifiers. Among them, the nonionic emulsifier is preferable in terms of imparting stability to the resin emulsion.

  The nonionic emulsifier to be added may be a known one, and examples thereof include polyoxyalkylene alkyl ether, polyoxyalkylene alkylphenol ether, polyoxyalkylene fatty acid ester, polyoxyalkylene sorbitan fatty acid ester and the like. Among them, polyoxyethylene alkyl ether is preferable, and those having HLB of 13 to 19 are preferable. If the HLB is lower than 13, the water dispersibility of the emulsifier is poor, and if it is higher than 19, the water resistance of the coating film may be lowered. The addition amount of the nonionic emulsifier is preferably 10% by mass to 40% by mass and more preferably 15% by mass to 35% by mass with respect to the scallop shell calcined product. If the amount is less than 10% by mass, the drying property may be too early and the workability may be hindered. If the amount exceeds 40% by mass, the drying delay effect is too great, and it is difficult to obtain sufficient drying property.

  The anionic emulsifier to be added may be a known one, for example, alkyl sulfate ester salt, alkyl benzene sulfonate, alkyl sulfosuccinate, alkyl diphenyl ether disulfonate, polyoxyalkylene alkyl sulfate, polyoxyalkylene alkyl phosphate. Esters can be used as appropriate.

  The non-volatile content of the water-based quick-drying coating composition of the present invention is preferably used in the range of 30% to 80%. If it is lower than 30%, the quick-drying property is slow, and if it is higher than 80%, the pot life of the coating composition is shortened and the viscosity becomes high, so that workability may be hindered.

Applications of the water-based quick-drying paint composition according to the present invention include roofing waterproof protection that is easily affected by rainfall during construction and color coating of outdoor facilities such as sidewalks and parks in parks. In other words, it can be said that it is a great merit that the drying time can be freely controlled by adding the shell baked product to the aqueous resin emulsion in advance during the rainy season when construction and weather are unstable on a day with a high probability of precipitation. Moreover, as a construction method, it can construct with a general-purpose construction tool such as a roller brush, a hammer, a spray, etc., and the usage amount is 0.1 to 0.3 kg / m ² for a coating material alone, dry silica sand, etc. Even when aggregates are added, the coating is a thin layer of 1.0 to 2.0 kg / m ² .

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. The physical properties and evaluation methods of the aqueous resin emulsions prepared in Examples and Comparative Examples were as follows.

(Non-volatile content)
About 1 g of resin was weighed on an aluminum dish having a diameter of 5 cm, dried at 105 ° C. for 1 hour, and the remainder was calculated.

(viscosity)
Using a Brookfield rotational viscometer, the liquid temperature was 23 ° C., the rotational speed was 60 rpm, Measured with 2 rotors.

(Minimum deposition temperature, MFT)
It measured according to JIS K 6828.

(Drying time)
Even if the coating composition prepared by the formulation shown in Table 2 and Table 3 is applied on a slate plate at about 1 kg / m ² and left at 23 ° C. × 65% RH, water is allowed to flow over the coating surface. The time during which the paint did not flow out was defined as the drying time.

(Synthesis Example 1)
In a four-necked flask reactor equipped with a stirrer, a thermometer and a reflux condenser, 138 parts by mass of plus coat Z-730 (nonvolatile content 25% by mass), plus coat Z-561 (nonvolatile content) as a water-dispersible polyester resin. 25 mass%) 207 mass parts and ion-exchange water 33 mass parts were charged, and it heated up at 80 degreeC. 150 parts by mass of styrene, 115 parts by mass of methyl methacrylate, 81 parts by mass of 2-ethylhexyl acrylate, 7 parts by mass of 2-hydroxyethyl methacrylate, 3 parts by mass of an anionic emulsifier (Hitenol 08E manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), ion-exchanged water 110 parts by mass were premixed and emulsified with a homomixer. 0.4 parts by mass of potassium persulfate was added to the reactor, and at the same time, the ethylenically unsaturated monomer emulsion was also added dropwise and added dropwise over 3 hours. In addition, 0.8 parts by mass of potassium persulfate dissolved in 46 parts by mass of ion exchange water was added dropwise over 3 hours. The internal temperature during the reaction was kept at 80 ° C. After completion of the dropwise addition of the emulsion and the polymerization initiator, the mixture was reacted at 80 ° C. for 1 hour and then cooled to room temperature. 99 parts by mass of 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate (CS-12 manufactured by Chisso Corporation) was added as a film forming aid to obtain an aqueous resin emulsion. The properties of the obtained aqueous resin emulsion A were a non-volatile content of 50.0% by mass, a viscosity of 300 mPa · s, a pH of 7.2, and an MFT of 0 ° C.

(Synthesis Example 2)
A pressure vessel equipped with a stirrer and a thermometer is charged with 300 parts by mass of Z-561 (nonvolatile content 25% by mass) and 250 parts by mass of ion-exchanged water as water-dispersible polyester, and the inside of the pressure vessel is replaced with nitrogen gas. The inside was heated to 80 ° C. After pressurizing to 4.0 MPa with ethylene, 350 parts by mass of vinyl acetate was added dropwise over 5 hours. At the same time, 2.5 parts by mass of potassium persulfate was dissolved in water and added. During this time, the temperature in the reaction vessel was kept at 80 ° C., and further stirring was continued until the vinyl acetate concentration in the reaction solution became 0.5% by mass or less. Then, the unreacted ethylene gas was removed and the mixture was cooled to 25 ° C. did. The properties of the obtained aqueous resin emulsion B were a non-volatile content of 47.0% by mass, a viscosity of 80 mPa · s, a pH of 3.8, and an MFT of 0 ° C. The structural unit derived from ethylene was 18 parts by mass and the structural unit derived from vinyl acetate was 82 parts by mass with respect to 100 parts by mass of the copolymer.

Example 1
100 parts by weight of the aqueous resin emulsion A obtained in Synthesis Example 1 and 7 parts by weight of a 25% by weight aqueous solution of polyoxyethylene alkyl ether of HLB18.5 as a nonionic emulsifier are mixed, and the scallop shell calcined product (Nippon Natural Materials Co., Ltd.) is stirred. 10 parts by weight of a company-made shell fill (particle size: 5 μm) was added to obtain an aqueous coating composition. The drying time was 20 minutes.

(Example 2)
100 parts by weight of the aqueous resin emulsion B obtained in Synthesis Example 2 and 8 parts by weight of a 25% by weight polyoxyethylene alkyl ether aqueous solution of HLB18.5 as a nonionic emulsifier are mixed and stirred with scallop shell baked material (Nippon Natural Materials Co., Ltd.) 10 parts by weight of a company-made shell fill (particle size: 5 μm) was added to obtain an aqueous coating composition. The drying time was 40 minutes.

(Example 3)
100 parts by weight of the aqueous resin emulsion A obtained in Synthesis Example 1 and 4 parts by weight of a 25% by weight aqueous solution of polyoxyethylene alkyl ether of HLB18.5 as a nonionic emulsifier are mixed, and the scallop shell calcined product (Nippon Natural Materials Co., Ltd.) is stirred. 4 parts by weight of a company-made shell fill (particle size: 5 μm) was added to obtain an aqueous coating composition. The drying time was 25 minutes.

Example 4
100 parts by weight of the aqueous resin emulsion A obtained in Synthesis Example 1 and 5 parts by weight of a 25% by weight aqueous solution of HLB18.5 polyoxyethylene alkyl ether as a nonionic emulsifier are mixed, and the scallop shell calcined product (Nippon Natural Materials Co., Ltd.) is stirred. 4 parts by weight of a company-made shell fill (particle size: 5 μm) was added to obtain an aqueous coating composition. The drying time was 50 minutes.

(Comparative Example 1)
When 100 parts by mass of the aqueous resin emulsion A obtained in Synthesis Example 1 was stirred, 10 parts by mass of a scallop shell calcined product (shell fill made by Nippon Natural Materials Co., Ltd., particle size 5 μm) was added. The composition gelled.

(Comparative Example 2)
When only the aqueous resin emulsion A obtained in Synthesis Example 1 was applied, the drying time was 300 minutes or more.

(Comparative Example 3)
In Example 1, a styrene-acrylic acid ester copolymer emulsion (Polysol AP-4750, Showa High Polymer Co., Ltd., 46% non-volatile content, MFT 0 ° C.) was used in place of the aqueous resin emulsion A, and a nonionic emulsifier was not used. In the same manner as in Example 1, a water-based coating composition was obtained. The drying time was 180 minutes.

(Comparative Example 4)
In Example 2, instead of the aqueous resin emulsion B, an ethylene-vinyl acetate copolymer (Polysol P-3N made by Showa High Polymer, nonvolatile content 50%, MFT 2 ° C.) was used, and a nonionic emulsifier was not used. A water-based coating composition was obtained in the same manner as in Example 2. The drying time was 170 minutes.

  As shown in Table 2, the aqueous coating compositions obtained in Examples 1 to 4 were excellent in quick drying and workability with a drying time of 20 to 50 minutes. On the other hand, the water-based paint compositions obtained in Comparative Examples 1 to 4 shown in Table 3 are gelled before being applied, or processed products having a long drying time and excellent quick drying and workability. It was not obtained.

Claims (6)

A water-based quick-drying coating composition comprising a resin emulsion obtained by emulsion polymerization of an ethylenically unsaturated monomer composition using a water-dispersible polyester as a protective colloid, a shell baked product, and an emulsifier. The water-based quick-drying paint composition according to claim 1, wherein the fired shell is a fired scallop shell. The water-based quick-drying paint composition according to claim 2, wherein the fired scallop shell is used in an amount of 1 to 50% by weight based on the resin emulsion. The water-based quick-drying coating composition according to any one of claims 1 to 3, wherein the emulsifier is a nonionic emulsifier. The water-based quick-drying coating composition according to claim 4, wherein the nonionic emulsifier is used in an amount of 10% by mass to 40% by mass with respect to the fired shell. The water-based speed according to claim 1, wherein the water-dispersible polyester is used in an amount of 5% by mass to 70% by mass with respect to the ethylenically unsaturated monomer composition. Dry paint composition.