JPS6241271B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an aqueous coating composition for antifogging and promoting droplet flow, and more specifically, an acrylic copolymer obtained by polymerizing an acrylic monomer mixture in an aqueous medium containing a conductive copolymer. The present invention relates to an aqueous coating composition comprising an aqueous dispersion, which imparts antifogging properties and droplet promoting effects to agricultural plastic films or sheets. In recent years, the consumption of vegetables has increased, and greenhouse horticulture has become widespread to encourage cultivation, and plastic films or sheets are used as covering materials. This material includes polyvinyl chloride, polyethylene,
Polypropylene, polyester, ethylene-vinyl acetate copolymer, polyacrylic, polycarbonate, etc. are most commonly used. Since the surfaces of these films and sheets are hydrophobic, water condensed or attached to the surface covers the surface as fine water droplets, causing cloudiness or falling as large water droplets. As a result, light transmittance decreases, and the rate of temperature rise inside the greenhouse or tunnel decreases, resulting in delayed crop growth, falling water droplets inhibiting germination, and even worse, workability. occur. An effective way to improve these drawbacks is to make the film surface hydrophilic so that water droplets flow more easily (droplet flow promotion). Methods such as applying hydrophilic substances (water droplet prevention agents) such as various surfactants to films and sheets, or mixing them into materials and kneading them are used, and the latter method in particular is relatively widely used. (Tokuko Showa 38-)
4174, Tokuko Sho 38-3572). In this case, the incorporated water droplet preventive agent migrates to the surface, thereby improving leakage on the plastic surface and exhibiting antifogging properties and droplet promoting effects. However, when adding a water droplet preventive agent to a material, its effectiveness is limited by its dispersibility, surface migration, compatibility with the material, etc., depending on the compound, the compounded material, and its formulation. Furthermore, the amount of the compound to be added is limited due to the processability and physical properties of the film or sheet. Furthermore, when water droplets flow, the water droplet preventing agent dissolves and is washed away, resulting in a disadvantage that the antifogging properties and droplet promoting effects are not sustainable. On the other hand, conventional methods for forming a coating film on the surface of a film or sheet have been unsatisfactory in terms of adhesion to the object to be coated, antifogging properties, and droplet promoting effects. The inventors of the present invention have conducted extensive studies on an aqueous coating composition for antifogging and promoting droplet flow that does not have the above-mentioned drawbacks, and have found that it has the desired excellent coating performance, i.e., adhesion to plastic films and sheets, transparency, water resistance, Weather resistance, blocking resistance, anti-fogging properties, droplet promotion effect (effect that promotes water droplets created by condensed water vapor to flow down along the surface of the ground instead of falling directly to the ground) and their sustainability. The inventors have successfully developed an aqueous coating composition that can be applied to a water-based coating composition, which is provided as the present invention. That is, from one point of view, the present invention provides 100 to 25% by weight of one or more conductive vinyl monomers having a sulfonate or a quaternary ammonium salt, and a vinyl monomer copolymerizable therewith. Quantity 0-75
Monomer mixture (component A) consisting of 0.5 to % by weight
20.0 parts by weight, (a) 0 to 10% by weight of one or more α,β-unsaturated carboxylic acids and/or salts thereof having one or more carboxyl groups, and (b)
one or more acrylic acid alkyl esters, the alkyl group of which has from 1 to 12 carbon atoms, and/or methacrylic acid alkyl esters, whose alkyl group has from 1 to 12 carbon atoms; A monomer mixture consisting of 10 to 98% by weight of one or more types of copolymerizable vinyl monomers (c) and 0 to 80% by weight of one or more types of copolymerizable vinyl monomers (component B). ) 100 parts by weight, is a polymer obtained by polymerizing component B in a dispersion obtained by pre-polymerizing component A in an aqueous medium, and has an average molecular weight of 5000 to 150000 and a secondary transition temperature. Provided is an aqueous coating composition capable of imparting antifogging properties and a droplet promoting effect, which comprises an aqueous dispersion containing substantially the copolymer having a temperature of 0 to 80°C in the form of particles. The first feature of the present invention is that when imparting antifogging properties and droplet promoting effects, conventionally a hydrophilic substance (water droplet preventive agent) such as a low-molecular surfactant is applied to a plastic film or sheet. Alternatively, methods such as kneading directly into the resin have been used, but they have the disadvantage that they are not long-lasting and the water drop preventive agent on the surface (or floating on the surface) washes away with the water droplets, causing the effect to disappear. However, this drawback was overcome by copolymerizing the conductive vinyl monomer with a homopolymerizable or copolymerizable vinyl monomer to make it have a high molecular weight. The second feature is that the aqueous coating composition of the present invention utilizes the property of a conductive vinyl monomer homopolymer or copolymer to improve dispersion stability in dispersion polymerization, and uses the polymer as a dispersion stabilizer. The resulting coating composition contains substantially no emulsifier. As a result, the disadvantages of the emulsifier resulting in a decrease in the water resistance, weather resistance, and adhesion of the coating film to plastic films and sheets can be overcome. The third feature is that the composition of the present invention is an aqueous dispersion, so it is harmless to the human body and crops, and it can be diluted with water if necessary, and furthermore, a coating aid can be added if necessary. It is possible to appropriately coat existing films and sheets with an agricultural sprayer on-site, and it is also possible to line coat at the time of manufacturing films and sheets. The fourth feature is that the α,β carboxylic acid and its salt, the (meth)acrylic acid ester, and the copolymerizable vinyl compound of the present invention are each copolymerized by combining the above-mentioned vinyl monomers within the scope of the claims. This allows us to select the optimal formulation for the coating conditions, and at the same time to select each monomer so that the resulting coating film maintains the best balance of physical properties such as adhesion to the substrate, transparency, and weather resistance. It is possible to select the composition. In other words, there is a degree of freedom in selecting the optimum polymer composition for the coating method and physical properties depending on the application. The sulfonate or quaternary salt used in the present invention
Examples of the conductive vinyl monomer having an ammonium salt include monomers represented by general formulas () to (). General formula () However, in the formula, R ₁ = H, CH ₃ R ₂ = -OCH ₂ CH ₂ -,

[Formula] − NH−CH ₂ CH ₂ −CH ₂ −,

[Formula] R ₃ and R ₄ = CH ₃ , CH ₂ CH ₃ R ₅ = CnH2n+1 (n = 0 to 4),

[Formula] CH ₂ CH ₂ CH ₂ SO ₃ x = Cl, Br None (only when R ₅ = CH ₂ CH ₂ CH ₂ SO ₃ ). General formula () However, in the formula, n = 0,1 M = alkali metal such as Li, Na, K, etc. or NH ₄ general formula () However, in the formula, m = 0,1 n = 1 to 4 R ₁ = H, CH ₃ M = alkali metal such as Li, Na, K, etc. or NH ₄ Among these, 2-
Hydroxy-3-methacryloxypropyltrimethylammonium chloride, the sodium salt or ammonium salt of P-styrenesulfonic acid of the general formula () and sodium vinylbenzylsulfonate are particularly preferably used. In the present invention, it is necessary to add component A containing the conductive vinyl monomer in an amount of 0.5 to 20.0 parts by weight, preferably 2.0 to 10.0 parts by weight, per 100 parts by weight of component B. If the value is too small, the antifogging properties and droplet promoting effects will not be achieved. on the other hand,
If it exceeds 20 parts by weight, the viscosity of the aqueous dispersion increases and polymerization stability deteriorates, which is not preferable. The vinyl monomer copolymerizable with the conductive vinyl monomer is not particularly limited, but it is preferable to have a composition that is the same as or close to the composition of the monomer of component B. This increases the compatibility between the conductive polymer and the component B copolymer, thereby improving the adhesion to plastic films and sheets, resulting in a coating composition with excellent transparency. Furthermore, blocking resistance is improved by using a monomer composition that provides a polymer with a high secondary transition temperature as a copolymerizable vinyl monomer. The proportion of the vinyl monomer copolymerized with the conductive vinyl monomer is 0 to 75% by weight, preferably 20 to 67% by weight.
Good weight percentage. When this proportion is 20% by weight or more, the resulting copolymer will not be completely soluble in water.
A coating film with good water resistance and blocking resistance can be obtained. If it exceeds 75% by weight, the antifogging properties and the droplet promoting effect will decrease, which is not preferable. The coating composition of the present invention can be produced by using the homopolymer or copolymer of these conductive vinyl monomers as a dispersion stabilizer by utilizing the property of improving dispersion stability in dispersion polymerization. Although the resulting composition does not substantially contain an emulsifier, a small amount of a general emulsifier or protective colloid may be added for reinforcement if necessary. The α,β-unsaturated carboxylic acid or its salt having one or more carboxyl groups used in the monomer mixture as component B of the present invention (a) is, for example, acrylic acid, methacrylic acid, etc. acid, maleic acid,
Examples include itaconic acid, crotonic acid, fumaric acid, maleic anhydride, and their alkali metal salts and ammonium salts. Further, when using an α,β-unsaturated carboxylic acid having two or more carboxyl groups or a salt thereof, a half ester thereof may be used. These carboxylic acids or their salts mainly have the effect of improving adhesion to the film, and the amount used is 0.
A range of ~10% by weight is preferable. If it exceeds 10% by weight,
This is not preferred because the water resistance and blocking resistance of the resulting coating film are reduced. Furthermore, when producing this aqueous acrylic copolymer dispersion using a cationic conductive vinyl monomer having a quaternary ammonium salt, these carboxylic acids or their salts may reduce polymerization stability. It is best to avoid its use as it may cause In addition, (b) acrylic acid alkyl ester and methacrylic acid alkyl ester are those in which the alkyl group is methyl, ethyl, isopropyl, n-butyl, i-butyl, amyl, n-hexyl, 2-ethylhexyl, lariul group, etc. Certain acrylates and methacrylates. These are necessary components that influence the flexibility and blocking resistance of the resulting coating film and the secondary transition temperature of the resulting polymer. In particular, they are used in appropriate combinations in consideration of the secondary transition temperature. The amount used is preferably 10 to 98% by weight. Next, examples of the vinyl monomer (c) include the following (i) to (ix), but are not limited thereto. (i) Vinyl-substituted aromatic hydrocarbons such as styrene and α-ethylstyrene; (ii) α,β-unsaturated aliphatic nitriles such as acrylonitrile and methacrylonitrile; (iii) vinyl acetate and vinyl propionate. organic acid vinyl esters, (iv) vinyl halides such as vinyl chloride and vinylidene chloride, (v) α,β-unsaturated carboxylic acid amides such as acrylamide, methacrylamide, N-methoxyacrylamide, (vi) Hydroxyalkyl esters of α,β-unsaturated carboxylic acids such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate;α,β-unsaturated such as polyethylene glycol monomethacrylate and polypropylene glycol monomethacrylate. Hydroxy(oxyalkylene) esters of carboxylic acids, (vii) α,β-unsaturated carboxylic acid esters having epoxy groups such as glycidyl (meth)acrylate, (viii) dimethylaminoethyl (meth)acrylate, diethylaminoethyl ( (ix) Crosslinkable monomers such as ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, sorbitan trimethacrylate, divinylbenzene, etc. body. These copolymerizable vinyl monomers may be used alone or in combination of two or more, if necessary. The amount used is preferably 0 to 80% by weight. These are thought to mainly affect the hardness and secondary transition temperature of the coating film obtained, but the vinyl monomers listed in (vi) and (vii) are used in coating compositions for plastic films and sheets. will be involved in improving the adhesion of the In particular, (vi) hydroxyalkyl (oxyalkylene) esters of α,β-unsaturated carboxylic acids are highly effective, and further contribute to antifogging properties and droplet promoting effects,
It is desirable to use ~30% by weight, preferably 10-25% by weight. The target acrylic copolymer has an average molecular weight of 5,000 to 150,000, preferably 8,000 to 80,000, and a second-order transition temperature of 0 to 80°C, preferably 10 to 80°C.
The temperature is 60℃. If the average molecular weight is less than 5000, the properties as a coating film will be lost and sufficient film strength will not be obtained. When it exceeds 150,000, the adhesion to plastic films and sheets decreases. In addition, the average molecular weight here is a number average molecular weight. Also,
When the secondary transition temperature is 0° C. or lower, the coating film becomes sticky and has poor stain resistance. If the temperature is 80°C or higher, the coating film becomes hard and its flexibility decreases. These copolymers are substantially contained in an aqueous dispersion as particles. The term "substantially particles" refers to particles that can be confirmed under an electron microscope, and the particle size of the copolymer is preferably about 0.01 to 0.5 microns, most preferably 0.01 to 0.3 microns. It is sufficient that at least 90% of the particles have such a particle diameter. The amount charged during polymerization is adjusted so that the concentration of the above-mentioned copolymer in the aqueous dispersion according to the present invention is usually 30 to 50% by weight. Also, depending on each application, 3~
It is used after adjusting the concentration to 50% by weight. Next, a method for producing the aqueous coating composition of the present invention will be described. That is, a conductive vinyl monomer having a sulfonate or a quaternary ammonium salt.
A monomer mixture of 100 to 25% by weight and 0 to 75% by weight of a vinyl monomer copolymerizable with this is 100% by weight of component B.
Polymerize 0.5 to 20.0 parts by weight in an aqueous medium in advance. Since the polymerization system removes oxygen that inhibits the reaction,
The air in the reaction system was replaced with nitrogen gas, and an organic peroxide such as t-butyl hydroperoxide or 2,5-dimethyl-2,5-di(t-butylbenzyloxy)hexane was added as a polymerization initiator under a nitrogen stream. Redox initiators using oxides, hydrogen peroxide, potassium persulfate, ammonium persulfate, and combinations of these peroxides and various reducing agents, as well as 2,2'-
Polymerization can be initiated using a water-soluble azo compound such as azobis(2-amidinopropane) hydrochloride. The polymerization temperature, pressure within the polymerization system, and stirring method should be selected depending on the type of initiator, type of monomer, and combination. The polymerization temperature is generally 20 to 85°C when using a redox initiator, and 20 to 85°C when using a peroxide or azo initiator.
40-120°C is preferred. In the presence of the conductive polymer thus obtained, the monomer mixture of component B and an initiator are added dropwise to polymerize. The initiator and polymerization temperature used in this case may be the same as those used in producing the conductive polymer, but they do not necessarily have to be the same. The aqueous dispersion obtained in this way is stable as it is, but if necessary, it may be more stable if the pH is adjusted with ammonia, sodium hydroxide, potassium hydroxide, diethylamine, diethanolamine, etc. is improved and is suitable. The aqueous coating composition also includes colloidal silica,
Hot slip agents such as talc, natural waxes, anti-blocking agents such as fatty acid amides, plasticizers, antifogging agents, stabilizers, etc. may be added as necessary. When applying the aqueous dispersion of the present invention to films and sheets of existing greenhouses on-site or at low temperatures, a film-forming aid may be added as necessary to lower the film-forming temperature. It can be made into a liquid. Film-forming aids include butyl cellosolve acetate, butyl carbitol acetate, methyl cellosolve, ethyl cellosolve, butyl cellosolve,
Ethyl carbitol, butyl carbitol, isophorone, etc. are used. Various methods can be applied to apply the aqueous coating composition of the present invention to plastic films and sheets. For example, a method can be used in which the coating is applied using a coating device such as a roll coater, dip coater, or gravure coater, and then dried. In addition, when applying on-site to the films and sheets of existing greenhouses, it can be suitably done using an agricultural sprayer. In another aspect, the present invention provides a self-sprayable anti-fog and droplet promoting aqueous coating composition. Such compositions contain from 1 to 35 of the copolymers described above.
It is prepared by adding 3 to 60 parts by volume of propellant to 100 parts by volume of an aqueous dispersion containing % by weight.
If the amount of the copolymer is less than this range, the desired properties cannot be obtained, and if it is more than this range, the antifogging and droplet promoting effects will not be improved and there will be no merit. Moreover, if the amount of propellant used is less than this range, it will not be practically used up to the end, and if it is more than this range, coalescence of copolymer particles will be induced, resulting in an unstable composition. To prepare a self-sprayable composition, an aqueous dispersion of the copolymer prepared to a copolymer concentration of 30 to 50% by weight is diluted with water or an organic solvent, and the copolymer concentration is adjusted to 1 to 50% by weight. The composition is adjusted to 35% by weight and a propellant is added to make a self-sprayable composition. As the propellant in this invention, an organic compound having a low boiling point (for example, a boiling point of 0 to -50°C) is used, and specifically, hydrocarbons, halogenated hydrocarbons, dimethyl ether, etc., or mixtures thereof are used. Specific examples of hydrocarbons include propane, i-butane, and n-butane, and specific examples of halogenated hydrocarbons include trichlorofluoromethane, dichlorodifluoromethane, dichlorotetrafluoroethane, monochlorodifluoromethane, and trichlorotrifluoromethane. Fluoroethane, 1,1
-difluoroethane, 1,1-difluoro-1-
Examples include chloroethane, dichloromonofluoromethane, methylene chloride, and the like. The propellants used alone or in mixtures are chosen so as to give a pressure of 0.3 to 5 kg/cm ² , preferably 1 to 4.5 kg/cm ² at 20° C. in the aerosol container. Examples of the organic solvent used to dilute the aqueous dispersion include alcohols such as methanol, ethanol, and isopropanol; ketones such as acetone and methyl ethyl ketone; esters such as ethyl acetate, methyl acetate, and amyl acetate; methyl ethyl ether; Examples include ethers such as diethyl ether; aromatic hydrocarbons such as toluene and benzene; and aliphatic hydrocarbons such as n-pentane and n-hexane. Organic solvents contribute to increasing the drying rate of the coating. However, in consideration of harm to the human body and air pollution, it is desirable to keep the amount of solvent used to a minimum. When such an organic solvent is used, it is usually used in an amount of 10% by weight or less in the aqueous dispersion. The self-sprayable composition may contain not only hot slip agents, anti-blocking agents, plasticizers, antifogging agents, stabilizers, and film-forming auxiliary agents that are added to the above-mentioned ordinary aqueous dispersion as appropriate. Dispersants, antistatic agents, antifoaming agents, especially non-silicon antifoaming agents, antifreeze agents (polyethylene glycol, polypropylene glycol, etc.) to prevent coalescence of polymer particles and further stabilize the dispersion system; A viscosity improver (methylcellulose, carboxymethylcellulose, hydroxyethylcellulose), etc. can also be added. Such a composition is filled into a so-called aerosol sprayer, and is used for spray coating by ejecting it from a nozzle using its self-spraying ability. Therefore, there is no need to use a complicated coating device, so coating can be performed more easily on site. Whichever method is used for coating, it is sufficient to adjust the thickness of the coating to about 0.3 to 10 g solids ^per square meter of film or sheet surface. The features of the present invention will be explained below using examples. In addition, the sample sheet in the following examples has a thickness of
It was a 0.5 mm vinyl chloride sheet, and the state of water droplet adhesion was observed as follows. Observation of the state of water droplet adhesion to the sheet: The slope of the roof of the greenhouse was 30°, and the aqueous dispersion of the present invention was applied to a 300 x 500 mm vinyl chloride sheet using a bar coater, dried, and placed for 40 minutes. The state of adhesion of water droplets to the sheet after being left for one day was observed. Each antifogging property was evaluated in four stages as shown below. A: The entire surface of the sheet leaks uniformly, and the sheet is transparent. B: The cloudy part of the sheet due to small water droplets is about 1/2 of the entire surface.
Less than 3 C: The cloudy area due to small water droplets on the sheet is 2/2 of the entire surface.
Less than 3 D: The cloudy part due to small water droplets on the sheet is 2/2 of the entire surface.
3 or more Examples 1 In the case of Example 1, deionized water (added to a solid content concentration of 30%) into a 2L four-necked flask equipped with a reflux condenser, thermometer, stirrer, and dropping funnel. 944 ml) and 27 g of sodium p-styrene sulfonate (6 parts of vinyl monomer mixture) were added.
2-Hydroxyethyl methacrylate, methyl methacrylate, styrene, ethyl acrylate, acrylic acid (15:6.5:6.5:70:2 (weight ratio)) 450g of vinyl monomer mixture and t-dodecyl mercaptan
4.5g (1% by weight of the vinyl monomer mixture) was dissolved. 10.8g of this homogeneous mixture (40g of anti-conductive monomer)
% by weight) into the initial flask. The temperature of the system was raised to 85°C under stirring in a nitrogen stream. 2.25 g of potassium persulfate (based on the vinyl monomer mixture, 0.5% by weight) was dissolved in 120 ml of deionized water, and 12.2 g of the solution was added to initiate polymerization. 20 at 85℃
After polymerization for one minute, the remaining vinyl monomer mixture and the remaining catalyst aqueous solution were put into separate dropping funnels, and simultaneously added dropwise over 2 hours. After the dropwise addition was completed, stirring was continued at 85°C for another 2 hours. After the reaction was completed, an ammonia aqueous solution was added to adjust the pH of the system to 7.0. Solid content 30%, emulsion viscosity 610cP/30℃
(BL type viscometer, 60 rpm) Anionic aqueous dispersion was obtained.To 100 parts by weight of solid content of this anionic aqueous dispersion, 4.5 parts by weight of natural wax, 0.3 parts by weight of silica, and 0.03 parts by weight of finely powdered silica were blended. Add more deionized water to reduce the solids content.
It was set at 15%. The above-mentioned liquid mixture was applied to a vinyl chloride sheet (0.5 mm thick) using a Mayer bar No. 5 and air-dried. Table 1 shows the droplet acceleration test results for this coating sheet.
Shown below. Example 2 The amount of sodium p-styrene sulfonate added in Example 1 was 9 parts by weight based on the vinyl monomer mixture, and the composition of the copolymerizable vinyl monomer was changed to 2-hydroxyethyl methacrylate, methacrylic acid, Methyl, styrene, acrylic residual ethyl, acrylic acid (15/26/26/31/2 (weight ratio)), Example 1
Polymerization was carried out in the same manner as above. After neutralizing the obtained anionic aqueous dispersion with ammonia, 4.5 parts by weight of natural wax, 0.3 parts by weight of silica, 0.03 parts by weight of finely powdered silica, and 30.0 parts by weight of butyl cellosolve acetate were added to 100 parts by weight of the solid content, and further deionized. Add water to increase solids content to 15%
shall be. The above-mentioned liquid mixture was applied to a vinyl chloride sheet (0.5 mm thick) in the same manner as in Example 1 and air-dried. Table 1 shows the results of the droplet acceleration test for this coated sheet. Example 3 Isopropyl alcohol was further added to the liquid mixture in Example 2 in an amount equal to the solid content of the aqueous dispersion, and the mixture was applied in the same manner as in Example 1. The coated sheet was dried at 60°C for 10 seconds. Table 1 shows the results of the droplet acceleration test for this coated sheet. Example 4 In place of sodium p-styrenesulfonate in Example 1, 27 g of 2-hydroxy-3-methacryloxypropyltrimethylammonium chloride was used, and the composition of the copolymerizable vinyl monomer was changed to 2-hydroxyethyl methacrylate. , methyl methacrylate, styrene, and ethyl acrylate (15:27:27:31 (weight ratio)), and 2,2'-azobis(2-aminodipropane) was used instead of the polymerization initiator potassium persulfate. Hydrochloride 2.25g
Polymerization was carried out in the same manner as in Example 1, except that a cationic aqueous dispersion having a solid content of 30%, a pH of 3.8, and an emulsion viscosity of 13 cP/30°C was obtained. Wax, silica, and a film-forming agent were mixed in the same formulation as in Example 2, applied to a vinyl chloride sheet, and dried at 60°C for 1 minute. Table 1 shows the results of the droplet acceleration test for this coated sheet. Example 5 The composition of the copolymerizable vinyl monomers in Example 2 was changed to 2-hydroxyethyl methacrylate, polyethylene glycol monomethacrylate (molecular weight approximately 300), methyl methacrylate, styrene, ethyl acrylate, and acrylic acid (10/ 5/26/26/31/
2 (weight ratio)), the polymerization operation and formulation were exactly the same, and the mixture was coated on a vinyl chloride sheet and air-dried. Table 1 shows the droplet acceleration test results for this coating sheet.
Shown below. Example 6 A self-injectable composition was prepared by adding 30 parts by volume of dimethyl ether to 100 parts by volume of the aqueous dispersion of the present invention, which was made to have a solid content of 5% by weight by adding deionized water to the liquid mixture obtained in Example 2. I got something. This composition was filled into an aerosol sprayer. The internal pressure inside the atomizer container was 4.3 Kg/cm ² at 20°C. This was sprayed from the nozzle of a sprayer, sprayed onto a vinyl chloride sheet, and air-dried. Table 1 shows the droplet acceleration results of this coated sheet. Furthermore, when the above composition was left at room temperature for two months, the dispersion state was maintained well and solid content did not separate, and even when this composition was sprayed from a nozzle, the nozzle was not clogged. I was able to perform stable spray painting work without any problems.

[Table] Example 7 Aqueous dispersion of the present invention by adding deionized water to the liquid mixture obtained in Example 1 to make the solid content 3%
A self-injectable composition was obtained by adding 20 parts by volume of dichlorodifluoromethane to 100 parts by volume. The internal pressure inside the atomizer container was 3.0 Kg/cm ² at 20°C. This was spray coated in the same manner as in Example 6, and it was found that the droplet promoting effect was practically sufficient and the long-term stability was good. Example 8 Aqueous dispersion of the present invention by adding deionized water to the formulation obtained in Example 4 to make the solid content 1.5%
A self-injectable composition was obtained by adding 40 parts by volume of dichlorotetrafluoroethane to 100 parts by volume. The internal pressure inside the injector vessel was 2.5 Kg/cm ² at 20°C. This was evaluated in the same manner as in Example 6, and it was found that the droplet promoting effect and long-term stability were good. Example 9 Aqueous dispersion of the present invention by adding deionized water to the formulation obtained in Example 5 to make the solid content 4%
A self-injectable composition was obtained by adding 10 parts by volume of n-butane and 30 parts by volume of dimethyl ether to 100 parts by volume. The internal pressure inside the injector container is 3.9 at 20°C.
It was Kg/ ^cm2 . This was evaluated in the same manner as in Example 6, and as a result, the droplet promoting effect and long-term stability were good.

Claims (1)

[Scope of Claims] 1. One or more conductive vinyl monomers having a sulfonate or a quaternary ammonium salt 100
A monomer mixture consisting of ~25% by weight and 0 to 75% by weight of a vinyl monomer copolymerizable with this (component A)
0.5 to 20.0 parts by weight, (a) 0 to 10% by weight of one or more α,β-unsaturated carboxylic acids and/or salts thereof having one or more carboxyl groups, and (b) one or more acrylic acid alkyl esters, the alkyl group of which has from 1 to 12 carbon atoms, and/or methacrylic acid alkyl esters, whose alkyl group has from 1 to 12 carbon atoms; A monomer mixture (B Component) A copolymer consisting of 100 parts by weight, obtained by polymerizing component B in a dispersion obtained by previously polymerizing component A in an aqueous medium, and having an average molecular weight of 5000 to 150000, An aqueous coating composition for antifogging and promoting droplet flow comprising an aqueous dispersion containing substantially the copolymer having a second-order transition temperature of 0 to 80°C in the form of particles. 2 The conductive vinyl monomer is 2-hydroxy-3-
The composition according to claim 1, which is methacryloxypropyltrimethylammonium chloride, sodium salt or ammonium salt of p-styrenesulfonic acid, or sodium vinylbenzylsulfonate. 3 (c) As the copolymerizable vinyl monomer, an ethylene oxide adduct of methacrylic acid and/or a propylene oxide adduct of methacrylic acid (however, the number of moles of ethylene oxide and propylene oxide added is 1 to 15) ) 5 to 30% by weight
A composition according to claim 1 for use. 4 One or more conductive vinyl monomers having sulfonate or quaternary ammonium salt100
A monomer mixture consisting of ~25% by weight and 0 to 75% by weight of a vinyl monomer copolymerizable with this (component A)
0.5 to 20.0 parts by weight, (a) 0 to 10% by weight of one or more α,β-unsaturated carboxylic acids and/or salts thereof having one or more carboxyl groups, and (b) one or more acrylic acid alkyl esters, the alkyl group of which has from 1 to 12 carbon atoms, and/or methacrylic acid alkyl esters, whose alkyl group has from 1 to 12 carbon atoms; A monomer mixture (B Component) A copolymer consisting of 100 parts by weight, obtained by polymerizing component B in a dispersion obtained by previously polymerizing component A in an aqueous medium, and having an average molecular weight of 5000 to 150000, A self-sprayable antifogging and spraying agent prepared by adding 3 to 60 parts by volume of a propellant to 100 parts by volume of an aqueous dispersion containing 1 to 35% by weight of the copolymer having a secondary transition temperature of 0 to 80°C. Drop-promoting aqueous coating composition. 5. The composition according to claim 4, wherein the propellant is a low boiling point organic compound.