WO2016043149A1 - Procédé de formation d'un film de revêtement - Google Patents

Procédé de formation d'un film de revêtement Download PDF

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Publication number
WO2016043149A1
WO2016043149A1 PCT/JP2015/075980 JP2015075980W WO2016043149A1 WO 2016043149 A1 WO2016043149 A1 WO 2016043149A1 JP 2015075980 W JP2015075980 W JP 2015075980W WO 2016043149 A1 WO2016043149 A1 WO 2016043149A1
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coating
coating film
water
moisture
water separation
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Japanese (ja)
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環 川元
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Nippon Paint Holdings Co Ltd
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Nippon Paint Holdings Co Ltd
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Priority claimed from JP2015130811A external-priority patent/JP6560036B2/ja
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/12—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by mechanical means
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials

Definitions

  • the present invention relates to a coating film forming method in which a coating film is formed by application of a water-based coating composition.
  • Liquid coating compositions can generally be roughly classified into two types: a solvent-based coating composition containing an organic solvent and an aqueous coating composition containing water as a main solvent.
  • the water-based coating composition has a small amount of organic solvent compared to the solvent-based coating composition, and therefore has a low environmental load. Therefore, use of water-based paint compositions is required in various coating fields.
  • the water-based paint composition contains water having a low evaporation rate as a solvent. Therefore, in the formation of the coating film, it is strongly influenced by the environment during the coating and drying of the aqueous coating composition. Specifically, for example, when the aqueous coating composition is applied and dried in a low temperature environment of 5 ° C. or lower, the evaporation of water as a solvent is very slow. Also, for example, when the aqueous coating composition is applied and dried in a high humidity environment with a humidity of 80% or more, the evaporation of water as a solvent is very slow.
  • Patent Document 1 JP 2012-229302 A (Patent Document 1) describes an aqueous paint solidification accelerator for road marking containing calcium acetate particles or magnesium acetate particles (Claim 1). And in this patent document 1, by using the water-based paint solidification accelerator for road marking, it is described that the drying time of the water-based paint for road marking applied to the road surface can be shortened and the solidification of the paint can be promoted. Has been.
  • the road marking water-based paint solidification accelerator is a coating apparatus that simultaneously applies the road marking water-based paint solidification accelerator and the road marking water-based paint to the road surface as described in claim 7 or 8.
  • the transferred water marking solidifying accelerator is diffused in the container through which the spray of the water marking for road marking passes as described in claim 9, and the road marking is displayed on the water marking paint for road marking. It is painted using a special coating device such as a coating device that mixes water-based paint solidification accelerators.
  • Patent Document 2 describes an aqueous paint fixing agent for road marking containing water-insoluble inorganic compound particles capable of generating heat by reacting with water (Claim 1). .
  • the water marking agent for road marking is applied to the road surface together with the water marking paint for road marking, or is applied by being sprayed on the coating film of the waterborne coating for road marking applied to the road surface. ).
  • Patent Document 3 describes an aqueous road marking paint characterized in that it includes solid polymer particles or inorganic compound particles that can absorb water ( Claim 1).
  • Patent Document 3 also discloses a method for accelerating the drying of a water-based road marking paint applied to a surface, which is solid polymer particles or inorganic compound particles that can absorb water, and is applied to the surface together with the paint or applied. A method comprising spraying on the applied paint is also described (claim 2).
  • the invention described in Patent Document 3 does not describe the water removal step in the present invention.
  • the present invention solves the above-mentioned conventional problems, and its object is to achieve the object even under conditions where it is difficult to form a dry coating film by coating with an aqueous coating composition, such as a low temperature condition or a high humidity condition. It is providing the method which can form the coating film which has the function to do.
  • a painting process for painting a water-based paint composition The coating film obtained by the above coating is separated into a top layer containing water and a coating layer, a coating film separating step, and the top layer containing water is removed by a method other than drying.
  • Process A method for forming a coating film.
  • the uppermost layer containing moisture preferably further contains a moisture absorbent.
  • an aspect further including a moisture absorbent mixing step of adding a moisture absorbent to the aqueous coating composition before the coating step can be mentioned.
  • the coating film forming method for example, further including a water separation accelerator mixing step of adding a water separation accelerator to the aqueous coating composition before the coating step, The coating film separation step is brought about by the water separation accelerator.
  • a water separation accelerator mixing step for example, before the coating step, a water separation accelerator mixing step and a moisture absorbent mixing step are performed, Here, the water separation accelerator mixing step is performed before the moisture absorbent mixing step.
  • the water absorbent preferably has a water absorption of 1 g / g or more.
  • the moisture absorbent is preferably one or more selected from the group consisting of a superabsorbent resin, protein and polysaccharide.
  • the water separation promoter is preferably one or more selected from the group consisting of organic acids, inorganic acids, acid anhydrides, pH buffer solutions, metal salts, basic compounds, and polymer flocculants.
  • the water separation accelerator is preferably a polymer flocculant.
  • the polymer flocculant is preferably a polyhydroxysiloxane compound.
  • a water-removing process using a water-absorbing material wherein a water-absorbing material is used to remove moisture from the coating process obtained by coating the aqueous coating composition; A method of forming a coating film.
  • a water separation accelerator mixing step of adding a water separation accelerator to the aqueous coating composition before the coating step An embodiment is mentioned.
  • the water-absorbing material is one or more water-absorbing agents selected from the group consisting of a superabsorbent resin, protein and polysaccharide, or a sheet, film, membrane, comprising the water-absorbing agent, A strip or foam sheet is preferred.
  • the coating film forming method of the present invention is characterized in that moisture contained in the coating film formed from the aqueous coating composition is removed by a method other than drying. Therefore, even in a coating environment where it is difficult to evaporate an aqueous medium contained in a coating film formed from an aqueous coating composition, such as a low temperature condition and / or a high humidity condition, a coating having a target function is provided. A film can be formed.
  • the method of the present invention makes it possible to form a coating film in any environment without being influenced by the coating environment.
  • the coating film forming method of the present invention is a method for forming a coating film by coating an aqueous coating composition, wherein water contained in the coating film formed from the aqueous coating composition is removed by a method other than drying. It is characterized by. Although it does not specifically limit as an aqueous coating material composition used in the coating-film formation method of this invention, For example, the following aqueous coating material composition is mentioned.
  • Aqueous coating composition examples of the aqueous coating composition used in the method of the present invention include an aqueous coating composition containing an aqueous resin dispersion.
  • the aqueous resin dispersion contained in the aqueous resin dispersion aqueous coating composition is a film-forming resin component.
  • aqueous resin dispersion for example, an acrylic resin emulsion, an acrylic resin dispersion, a silicone-containing acrylic resin emulsion, a urethane resin emulsion, a vinyl acetate resin emulsion, a fluororesin emulsion, a vinyl chloride resin emulsion, and the like can be used. These resins may be used alone or in combination of two or more.
  • an acrylic resin emulsion, an acrylic resin dispersion, or a silicone-containing acrylic resin emulsion is preferably used.
  • An acrylic resin emulsion that can be used as an aqueous resin dispersion can be prepared by emulsion polymerization of a polymerizable monomer in an aqueous medium.
  • polymerizable monomers used in the preparation of acrylic resin emulsions ⁇ , ⁇ -ethylenically unsaturated monomers having a carboxyl group, ⁇ , ⁇ -ethylenically unsaturated monomers having a hydroxyl group, and other ⁇ , ⁇ -ethylenically unsaturated monomers are used. Saturated monomers are mentioned. These monomers can be appropriately selected according to the object to be coated with the aqueous coating composition and the application.
  • ⁇ -ethylenically unsaturated monomer having a carboxyl group acrylic acid, methacrylic acid, acrylic acid dimer, crotonic acid, 2-acryloyloxyethylphthalic acid, 2-acryloyloxyethyl succinic acid, ⁇ -carboxy- Polycaprolactone mono (meth) acrylate, isocrotonic acid, ⁇ -hydro- ⁇ -((1-oxo-2-propenyl) oxy) poly (oxy (1-oxo-1,6-hexanediyl)), maleic acid, fumarate Examples thereof include acid and itaconic acid. Among these, acrylic acid and methacrylic acid are preferable. In this specification, “(meth) acryl” means both acrylic and methacrylic.
  • an ⁇ , ⁇ -ethylenically unsaturated monomer having a hydroxyl group may be used as necessary.
  • the ⁇ , ⁇ -ethylenically unsaturated monomer having a hydroxyl group include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, allyl alcohol, methacrylic alcohol and / or (meth). Mention may be made of adducts of hydroxyethyl acrylate and ⁇ -caprolactone.
  • hydroxyethyl (meth) acrylate preferred are hydroxyethyl (meth) acrylate, hydroxybutyl (meth) acrylate and / or an adduct of hydroxyethyl (meth) acrylate and ⁇ -caprolactone.
  • ⁇ , ⁇ -ethylenically unsaturated monomers include (meth) acrylic acid esters (eg methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, (meth) acrylic acid n-butyl, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl methacrylate, phenyl acrylate, isobornyl (meth) acrylate, cyclohexyl methacrylate, (meth ) T-butyl cyclohexyl acrylate, dicyclopentadienyl (meth) acrylate, dihydrodicyclopentadienyl (meth) acrylate), polymerizable amide compounds (eg (meth) acrylamide, N-methylol (meth) ) Acryl
  • Dienes eg, butadiene, isoprene, etc.
  • polymerizable aromatic compounds eg, polymerizable nitriles, ⁇ -olefins, vinyl esters, and dienes. These can be appropriately selected according to the purpose.
  • a crosslinkable monomer may be used as the other ⁇ , ⁇ -ethylenically unsaturated monomer.
  • the crosslinkable monomer is a compound having two or more radically polymerizable ethylenically unsaturated groups in the molecule, such as divinylbenzene, ethylene glycol di (meth) acrylate, hexanediol di (meth) acrylate, Polyethylene glycol di (meth) acrylate, allyl (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexane di (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol di (meth) )
  • Divinyl compounds such as acrylate, and triallyl cyanurate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth)
  • emulsion polymerization in an aqueous medium is performed by, for example, dissolving an emulsifier in an aqueous medium containing water or a hydrophilic organic solvent such as water and alcohol or glycol, and heating. Under stirring, the polymerization can be carried out by dropping a monomer mixture obtained by mixing an ⁇ , ⁇ -ethylenically unsaturated monomer used as a raw material and a polymerization initiator. The monomer mixture obtained by mixing the ⁇ , ⁇ -ethylenically unsaturated monomer used as the raw material may be pre-emulsified using an emulsifier and water.
  • Polymerization initiators that can be suitably used for emulsion polymerization include azo oily compounds (for example, azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), and 2,2′- Azobis (2,4-dimethylvaleronitrile) and the like, and aqueous compounds (eg, anionic 4,4′-azobis (4-cyanovaleric acid), 2,2-azobis (N- (2-carboxyethyl)) -2-methylpropionamidine and cationic 2,2′-azobis (2-methylpropionamidine)); and redox oily peroxides (eg, benzoyl peroxide, parachlorobenzoyl peroxide, lauroyl peroxide and t-butyl perbenzoate) and aqueous peroxides (eg potassium persulfate and persulfate) Ammonium and the like) and the like.
  • azo oily compounds for example, azobisis
  • emulsifier those usually used by those skilled in the art can be used.
  • reactive emulsifiers such as Antox MS-60 (manufactured by Nippon Emulsifier Co., Ltd.), Eleminol JS-2 (manufactured by Sanyo Kasei Kogyo Co., Ltd.), Adekari Soap NE-20 (manufactured by Asahi Denka Co., Ltd.) and Aqualon HS-10 (Daiichi Kogyo Seiyaku Co., Ltd.) is particularly preferred.
  • a mercaptan such as lauryl mercaptan and a chain transfer agent such as ⁇ -methylstyrene dimer can be used as necessary.
  • the reaction temperature is determined by the initiator. For example, it is preferably 60 to 90 ° C. for an azo initiator and 30 to 70 ° C. for a redox system. In general, the reaction time is 1 to 8 hours.
  • the amount of initiator relative to the total amount of monomer mixture is generally from 0.1 to 5% by weight, preferably from 0.2 to 2% by weight.
  • the emulsion polymerization can be performed in multiple stages, for example, in two stages.
  • the two-stage emulsion polymerization first, a part of the mixture of ⁇ , ⁇ -ethylenically unsaturated monomers used as the raw material is emulsion polymerized, and then the remainder of the ⁇ , ⁇ -ethylenically unsaturated monomer mixture is further added.
  • it is a polymerization method in which emulsion polymerization is performed.
  • the volume average particle diameter of the acrylic resin emulsion is preferably 20 to 500 nm, and more preferably 50 to 200 nm.
  • the volume average particle diameter is a volume average particle diameter determined by a dynamic light scattering method. Specifically, an electrophoretic light scattering photometer ELS-800 (manufactured by Otsuka Electronics Co., Ltd.) is used. Can be measured.
  • the acrylic resin emulsion is preferably adjusted to pH 5 to 10 by neutralizing with a basic compound.
  • the basic compounds are ammonia, methylamine, ethylamine, dimethylamine, diethylamine, trimethylamine, triethylamine, dimethylethanolamine, diethanolamine, diethylaminoethanol, triethanolamine, tetraethylammonium hydroxide, propylamine, dipropylamine, tripropylamine.
  • Amines such as butylamine, dibutylamine and tributylamine, and hydroxides such as sodium hydroxide and potassium hydroxide.
  • the neutralization is preferably performed by adding the basic compound to the system before or after emulsion polymerization.
  • the acrylic resin dispersion can be prepared, for example, by preparing an acrylic resin by solution polymerization of the polymerizable monomer, and then dispersing the obtained acrylic resin in water. More specifically, the acrylic resin dispersion contains the above ⁇ , ⁇ -ethylenically unsaturated monomer having a carboxyl group as an essential component, and after performing solution polymerization together with other ⁇ , ⁇ -ethylenically unsaturated monomers. It can be prepared by neutralizing with a basic compound and dispersing in water.
  • the solution polymerization is generally a method in which the mixture of the polymerizable monomers is stirred while being dropped into an organic solvent together with a polymerization initiator under heating conditions.
  • Solution polymerization can be carried out, for example, under conditions of a polymerization temperature of 60 to 160 ° C. and a dropping time of 0.5 to 10 hours.
  • the polymerizable monomer can be polymerized in two stages. By polymerizing the polymerizable monomer in two stages, a core-shell type acrylic resin dispersion comprising a core part and a shell part can be obtained.
  • the polymerization initiator is not particularly limited as long as it is used for normal polymerization, and examples thereof include azo compounds and peroxides. Generally, the amount of the polymerization initiator with respect to 100 parts by mass of the monomer mixture is 0.1 to 18 parts by mass, preferably 0.3 to 12 parts by mass.
  • the solvent that can be used here is not particularly limited as long as it does not adversely affect the reaction, and examples thereof include alcohols, ketones, ethers, and hydrocarbon solvents. Furthermore, in order to adjust the molecular weight, a mercaptan such as lauryl mercaptan and a chain transfer agent such as ⁇ -methylstyrene dimer can be used as necessary.
  • the number average molecular weight of the acrylic resin thus obtained by solution polymerization is preferably 4,000 to 20,000.
  • the number average molecular weight of the acrylic resin obtained by solution polymerization can be measured by gel permeation chromatography (GPC) using a polystyrene standard sample standard.
  • An acrylic resin dispersion can be obtained by removing the solvent as necessary from the acrylic resin obtained by the solution polymerization and neutralizing it by adding a basic compound.
  • the basic compound include the basic compounds listed above.
  • the amount of the basic compound added is preferably such an amount that the neutralization rate of the carboxyl group of the acrylic resin obtained by the solution polymerization is 60 to 100%. When the neutralization rate is less than 60%, the water dispersibility of the acrylic resin dispersion becomes low and the storage stability may be poor.
  • the acrylic resin dispersion preferably has a volume average particle diameter determined by a dynamic light scattering method in the range of 10 to 1000 nm.
  • the acrylic resin dispersion preferably has a volume average particle diameter of 10 to 1000 nm, and more preferably 100 to 800 nm.
  • silicone-containing acrylic resin emulsion examples include a polymer obtained by polymerization of a monomer composition further containing an alkoxysilyl group-containing polymerizable monomer in addition to the polymerizable monomer used in the preparation of the acrylic resin emulsion. Can do.
  • the alkoxysilyl group-containing polymerizable monomer is not particularly limited as long as it is a polymerizable monomer containing an alkoxysilyl group having 1 to 14 carbon atoms.
  • trimethoxysilylpropyl (meth) acrylate, triethoxysilylpropyl (meth) acrylate, vinyltrimethoxysilane, vinyltriethoxysilane and the like can be mentioned.
  • an organic silicone unit may be introduced into the silicone-containing acrylic resin emulsion.
  • a method for introducing the organosilicone unit a mixture of an organosilicone compound (for example, organosilane, a hydrolyzate of organosilane, a condensate of organosilane, etc.) and an acrylic polymerizable monomer is subjected to emulsion polymerization, hydrolysis, condensation reaction and Examples include a method of performing radical polymerization, a method of copolymerizing a monomer having a silicone functional group, and a method of bonding an organosilicone compound to the surface of acrylic polymer particles by reacting an organosilicone compound with an acrylic polymer. . Two or more methods described above may be combined.
  • the organosilane is not particularly limited, and examples thereof include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane; Methoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, i-propyltrimethoxysilane, i-propyltriethoxysilane, n-butyltri Methoxysilane, n-butyltriethoxysilane, n-pentyltrimethoxysilane, n-hexyltrimethoxysilane, n-heptyltri
  • urethane resin emulsions in addition to the above, urethane resin emulsions, vinyl acetate resin emulsions, fluororesin emulsions, vinyl chloride resin emulsions and the like that are commonly used by those skilled in the art can also be used.
  • the amount of the aqueous resin dispersion contained in the aqueous coating composition is preferably 5 to 50 parts by mass with respect to 100 parts by mass of the aqueous coating composition as the resin solid content.
  • the aqueous resin dispersion may be a reaction curable resin that is cured by reacting with a curing agent, or may be a fusion resin that does not require a curing agent.
  • a curing agent for example, a carbodiimide curing agent, a melamine curing agent, an isocyanate curing agent, or the like can be used.
  • the aqueous coating composition in the present invention may contain other components as required in addition to the above components.
  • a film-forming aid for example, a film-forming aid, a thickener, a polyfunctional amine polymer, a coupling agent, a plasticizer, a crosslinked resin particle, a pigment, a surface conditioner, an antiseptic, an antifungal agent, an antifoaming agent, Examples thereof include a light stabilizer, an ultraviolet absorber, an antioxidant, and a pH adjuster.
  • the water-based paint composition contains water as a solvent.
  • the water-based coating composition may contain a hydrophilic organic solvent such as alcohol or glycol, if necessary, in addition to water.
  • the method for preparing the aqueous coating composition is not particularly limited, and can be prepared by stirring the above-described components with a stirrer or the like.
  • pigments or design materials are included in the aqueous coating composition, those having good dispersibility can be mixed with a stirrer, and as another method, a sand grind is added to a vehicle containing water, a surfactant or a dispersant. What was previously disperse
  • Coating Film Forming Method As one aspect of the coating film forming method of the present invention, A painting process for painting a water-based paint composition; The coating film obtained by the above coating is separated into a top layer containing water and a coating layer, a coating film separating step, and the top layer containing water is removed by a method other than drying. Process, The method of including is mentioned.
  • FIG. 1 is a schematic explanatory view showing this coating film forming method.
  • any method other than drying can be used.
  • the method of the present invention it is only necessary to include a moisture removing step of removing the uppermost layer containing moisture by a method other than drying, and in the method of the present invention, some moisture is removed by drying. It does not exclude that.
  • the coating film separation step the aspect in which the moisture contained in the coating film obtained by painting is evaporated somewhat corresponds to the method of the present invention as long as the water removal step is performed thereafter.
  • Arbitrary base material is mentioned as a to-be-coated object which coats water-based paint composition.
  • the substrate include metal, wood, plastics, rubber, stone, slate, concrete, mortar, fiber, paper, glass, porcelain, earthenware, film, and composites thereof. These substrates may be provided with a coating such as an undercoat coating as necessary.
  • any appropriate method can be used according to the type and shape of the article (base material) to be coated.
  • a method for applying the aqueous coating composition for example, commonly used coating methods such as dipping, brushing, flow coating, roller, roll coater, air spray, airless spray, curtain flow coater, roller curtain coater, die coater, etc. Can be used.
  • the aqueous coating composition is preferably applied so that the film thickness after removing water is 5 to 1000 ⁇ m, more preferably 20 to 300 ⁇ m.
  • the coating film obtained by coating the aqueous coating composition is separated into a water-containing uppermost layer and a coating film forming layer (coating film separation step).
  • coating film separation step examples include a method in which a coating film obtained by painting is allowed to stand for 2 seconds to 24 hours.
  • the uppermost layer containing moisture may contain only moisture, or may contain a moisture absorbent and / or a water separation accelerator described later. Further, the uppermost layer containing water may contain the above-mentioned additive contained in the aqueous coating composition, a slight amount of a film-forming component, and the like.
  • the coating film forming layer is a layer containing a coating film forming component contained in the aqueous coating composition.
  • the coating film forming component include the aqueous resin dispersion and other components as required.
  • the coating film forming layer may contain various additives in addition to the coating film forming component.
  • an aqueous coating composition As one means for bringing about and facilitating separation of the coating film obtained by coating into a water-containing uppermost layer and a film-forming layer, for example, before the coating step, an aqueous coating composition And a method of adding a water separation accelerator to the product (water separation accelerator mixing step).
  • the water separation accelerator include organic acids, inorganic acids, acid anhydrides, pH buffer solutions, metal salts, basic compounds, and polymer flocculants.
  • separation into the uppermost layer containing water and the coating film-forming layer means that an aqueous resin dispersion such as a resin emulsion is placed under a predetermined unstable condition, and a resin component, etc.
  • an aqueous resin dispersion such as a resin emulsion
  • a resin component etc.
  • the resin component constituting the aqueous resin dispersion and water are separated.
  • the basic mechanism of action is estimated as follows.
  • the water separation accelerator is a metal salt
  • the salt in the aqueous resin dispersion is fixed as hydrated water due to the strong hydration power of the salt, thereby reducing the stability of the aqueous resin dispersion.
  • the water separation accelerator is an organic acid, an inorganic acid, an acid anhydride, or a basic compound
  • a so-called coagulation action is considered to work. That is, the water separation accelerator exerts an electrical interaction with the ionic group of the aqueous resin dispersion by electrostatic attraction, so that the zeta potential on the surface of the aqueous resin dispersion particle is lowered and dehydrated. It is considered that the resin component becomes hydrophobic due to the coalescence of the particles, and the resin component of the aqueous resin dispersion is separated from the water.
  • the water separation accelerator is a polymer flocculant
  • the polymer chain of the polymer flocculant called a coagulation action together with these actions causes cross-linking adsorption to the resin component of the aqueous resin dispersion, and the polymer It is considered that separation of the resin component and moisture is promoted by bringing the aqueous resin dispersions together through a flocculant and making the resin component hydrophobic.
  • organic acid that can be used as a water separation accelerator
  • Monovalent carboxylic acids eg, acetic acid, benzoic acid, propionic acid, formic acid, etc.
  • Divalent carboxylic acids eg, maleic acid, fumaric acid, succinic acid, oxalic acid, etc.
  • Organic sulfonic acids for example, methanesulfonic acid, paratoluenesulfonic acid, benzenesulfonic acid, aminoethylsulfonic acid, etc.
  • Etc examples of the inorganic acid that can be used as the water separation accelerator include hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, and the like.
  • Examples of the acid anhydride that can be used as a water separation accelerator include those obtained by dehydration condensation of two molecules of the organic acid or inorganic acid.
  • Specific examples of the acid anhydride include, for example, acetic anhydride, benzoic anhydride, disulfuric acid (pyrosulfuric acid), pyrophosphoric acid (diphosphoric acid), diphosphorus pentoxide (phosphorus tetraoxide), and propionic anhydride.
  • an intramolecular dehydration condensate of the above divalent carboxylic acid can also be used. Examples of such condensates include maleic anhydride and fumaric anhydride.
  • Examples of the pH buffer that can be used as the water separation accelerator include acetate buffer, phosphate buffer, citrate buffer, Tris buffer, and borate buffer. Moreover, the buffer agent composition used for preparation of these pH buffer solutions may be added directly to the aqueous coating composition.
  • Examples of metal salts that can be used as a water separation accelerator include aluminum salts (eg, aluminum sulfate, polyaluminum chloride, etc.), iron salts (eg, polyferric sulfate, ferric chloride, etc.), sodium salts ( Examples thereof include sodium chloride, sodium sulfate, etc., calcium salts (eg, calcium chloride), magnesium salts (eg, magnesium chloride), and the like.
  • polymer flocculant that can be used as a water separation accelerator
  • cationic polymer flocculants dimethylaminoethyl methacrylate methylene chloride, diallyldimethylammonium chloride, aniline resin hydrochloride, polyamine derivatives, polythiourea acetate, polyethyleneaminotriazole, polyvinylbenzyltrimethylammonium chloride, polyethyleneimine, vinylpyridine
  • anionic polymer flocculants such as copolymer salts, sodium poly (meth) acrylate, maleic acid copolymer salt, itaconic acid copolymer salt, polyacrylamide partial hydrolyzate salt, sodium alginate, carboxy Methyl cellulose sodium salt, polyhydroxysiloxane compound, etc.
  • gelatin a copolymer of the above-mentioned anion unit and cation unit, etc. are used as the amphoteric polymer flocculant
  • polyacrylamide, polyoxyethylene, water-soluble urea, starch, etc. are appropriately used as the nonionic polymer flocculant. be able to.
  • the polyhydroxysiloxane compound which is a hydrolyzed condensate of alkoxysilane, has a relatively large pKa, so it does not cause abrupt aggregation that causes destabilization of the system, but has a relatively large polymer structure.
  • water separation accelerator that causes the above-mentioned cross-linking adsorption action more efficiently and causes rapid water separation by uniformly aggregating the entire system.
  • basic compounds that can be used as a water separation accelerator include ammonia, methylamine, ethylamine, dimethylamine, diethylamine, trimethylamine, triethylamine, dimethylethanolamine, diethanolamine, diethylaminoethanol, triethanolamine, tetraethylammonium hydroxide, Examples include amines such as propylamine, dipropylamine, tripropylamine, butylamine, dibutylamine and tributylamine, and hydroxides such as sodium hydroxide and potassium hydroxide. These water separation promoters may be used alone or in combination of two or more.
  • the water separation accelerator it is preferable to use at least one selected from the group consisting of organic acids (eg, acetic acid, propionic acid, etc.), acid anhydrides (eg, acetic anhydride, propionic anhydride, etc.) and polymer flocculants. .
  • the water separation accelerator it is more preferable to use an anionic polymer flocculant which is one type of polymer flocculant, and it is more preferable to use a polyhydroxysiloxane compound.
  • Preparation of a polyhydroxysiloxane compound more preferably used as a water separation accelerator is generally obtained by hydrolysis or condensation of a raw material selected from mono-, di-, tri-, and tetraalkoxysilanes alone or from a plurality thereof. .
  • a specific manufacturing method The well-known means described in patent 3599277, 5048395 grade
  • an amount that impairs the stability of the film-forming resin component is added. Specifically, it is preferably added in an amount of 0.01 to 50 parts by mass, more preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the aqueous coating composition. There exists a possibility that the effect as a water-separation promoter may not fully be exhibited as it is less than 0.01 mass part. If it exceeds 50 parts by mass, various coating film properties such as the curability and water resistance of the coating film may be deteriorated.
  • a method for adding a water separation accelerator to the aqueous coating composition a general mixing method can be used.
  • the uppermost layer containing water obtained by the coating film separating step is removed by a method other than drying (moisture removing step).
  • “removing the uppermost layer containing moisture by a method other than drying” means removing moisture contained in the coating film formed from the aqueous coating composition by a method other than drying after coating. Means. Specific examples of such a method include, for example, a method in which the uppermost layer containing moisture is washed away by gravity by tilting a coating film obtained by painting, or the uppermost layer containing a moisture absorbent is removed by hand or air. Examples of the removal method include removal or removal using an optional instrument as necessary, and a method of removing moisture by absorbing moisture in the uppermost layer into the moisture-absorbing material.
  • a water absorbent mixing step of adding a water absorbent to the aqueous coating composition may be performed before the coating step.
  • the moisture absorbent is contained in the uppermost layer containing moisture.
  • the moisture absorbent include an agent having a water absorption of 1 g / g or more. The amount of water absorption can be measured in accordance with the water absorption amount test method for high water absorption resin of JIS K 7223-1996.
  • the water absorbent include a highly water-absorbent resin, protein, polysaccharide and the like.
  • superabsorbent resins that can be used as moisture absorbents include polyacrylates (eg, sodium polyacrylate, potassium polyacrylate), polyvinyl alcohol, polyacrylamide, polyoxyethylene, polysulfonate, polyglutamic acid. Resins such as salts are listed.
  • the protein that can be used as a moisture absorbent include gelatin, glue, albumin, casein, gluten, and sericin.
  • a common material may be used for the water separation accelerator and the water absorbent. More specifically, a polymer flocculant which is an example of a water separation accelerator is used, and the same material may be used as a moisture absorbent.
  • a polymer flocculant, which is an example of a water separation accelerator is a component that causes separation of water from aqueous resin dispersion particles by, for example, salting out or coagulating action of added functional groups. This is because such an action is common in terms of action mechanism with the moisture absorption effect provided by the moisture absorbent in that water is fixed and separated and removed from the resin component.
  • the moisture absorbent is preferably in the form of particles or powder.
  • the particulate or powder moisture absorber include a moisture absorber having a volume average particle diameter of 100 nm to 1 mm.
  • the volume average particle diameter of the moisture absorbent can be measured by a laser light scattering method or the like. Specifically, it can be measured using a laser diffraction particle size distribution analyzer SALD-2200 (manufactured by Shimadzu Corporation). You may adjust a water
  • the water absorbent it is preferable to use at least one selected from the group consisting of proteins (for example, gelatin) and polysaccharides (for example, starch, hydroxyethyl cellulose, etc.).
  • proteins for example, gelatin
  • polysaccharides for example, starch, hydroxyethyl cellulose, etc.
  • the water absorbent When the water absorbent is added to the aqueous coating composition, it is preferably added in an amount of 0.1 to 100 parts by mass, and an amount of 0.1 to 30 parts by mass with respect to 100 parts by mass of the aqueous coating composition. It is more preferable to add at. If the amount is less than 0.1 parts by mass, moisture may not be sufficiently absorbed.
  • a general mixing method can be used as a method of adding a water absorbent to the aqueous coating composition.
  • the moisture absorbent may be subjected to an immersion treatment in which it is previously immersed in an organic solvent before being added to the aqueous coating composition.
  • the organic solvent for example, one or more selected from the group consisting of poorly water-soluble organic solvents and water-insoluble organic solvents can be used.
  • performing the immersion treatment for example, an aspect in which 0.5 to 10 parts by mass of the organic solvent is used for 1 part by mass of the moisture absorbent and the organic solvent is brought into contact with the organic solvent for 0.5 minutes to 24 hours. It is done.
  • the poorly water-soluble organic solvent means an organic solvent having a solubility at 20 ° C. of 10 mg / L or more and less than 10 g / L, and the water-insoluble organic solvent has a solubility at 20 ° C. of less than 10 mg / L. It means an organic solvent.
  • the water separation promoter mixing step is more preferably performed before the water absorbent mixing step.
  • a water-removing process using a water-absorbing material wherein a water-absorbing material is used to remove moisture from the coating process obtained by coating the aqueous coating composition;
  • the method of including is mentioned.
  • the moisture absorbing material is brought into contact with the moisture absorbing material from above the coating film obtained by painting to absorb moisture into the moisture absorbing material, thereby removing moisture.
  • FIG. 2 is a schematic explanatory view showing this coating film forming method.
  • the moisture-absorbing material used for removing moisture is not limited to the shape shown in FIG. 2, and any shape can be used.
  • the above-described moisture absorbent can be cited.
  • a material having a shape such as a sheet, a film, a membrane, a strip, and a foamed sheet, which is configured to include the moisture absorbent, can be used.
  • a material having such a shape for example, a material such as a commercially available sheet can be used.
  • the above-mentioned moisture absorbent can also be used after being processed into a shape such as a sheet or a film.
  • a water separation accelerator mixing step of adding a water separation accelerator to the aqueous coating composition may be further included before the coating step.
  • the water separation accelerator the water separation accelerator described above can be used.
  • the coating film forming method of the present invention is characterized by removing water contained in the aqueous coating composition by a method other than drying. Therefore, a coating film can be formed even in a coating environment where it is difficult to evaporate the aqueous medium contained in the aqueous coating composition, such as a low temperature condition and / or a high humidity condition. According to the method of the present invention, it is possible to form a coating film having a desired function in any environment without being influenced by the coating environment.
  • the coating film forming method of the present invention may be used for forming a single layer coating film or may be used for forming a multilayer coating film.
  • coat a coating composition further with respect to the coating film which performed the said water removal process are mentioned, for example.
  • the water removal step may be performed as necessary.
  • the coating film forming method of the present invention is used in the formation of a multilayer coating film, in addition to the above-mentioned advantages, there are further advantages such as prevention of problems such as mixed layers.
  • MKC silicate MS51 (condensate of tetramethoxysilane manufactured by Mitsubishi Chemical Co., SiO 2 content 51%, degree of condensation is 5 as an average value) 10.71 g of aluminum chelate D (aluminum chelate compound manufactured by Kawaken Fine Chemical Co., Ltd.) (76% isopropanol solution) 0.44 g and methanol 28.70 g were added and dissolved. After the temperature was raised to 40 ° C., 40.18 g of water was gradually added over 2 hours and stirred, followed by aging at 40 ° C. for 2 hours to obtain a polyhydroxysiloxane solution having a concentration of 9.6%.
  • Example 1 10 g of core-shell acrylic resin dispersion (manufactured by Nippon Paint Co., Ltd., solid content 44%, acid value 20 mg-KOH / g) was weighed in a glass bottle, and 0.18 g of special grade acetic anhydride (reagent) was added as a water separation accelerator, Homogenously mixed by shaking 10 times by hand at room temperature. Immediately thereafter, it was painted on a test piece at room temperature with a 10 mil doctor blade.
  • acetic anhydride acetic anhydride
  • a highly water-absorbent resin particle (trade name: Aquakeep 10SH-PF, manufactured by Sumitomo Seika Co., Ltd., water absorption: 500 g / g, volume average particle diameter: 26 ⁇ m) as a moisture absorbing material on the coating film 2 g was added. After 5 minutes, the uppermost layer containing moisture was removed with a finger to obtain a desired coating film having a dry film thickness of 100 ⁇ m.
  • the water absorption amount of the highly water-absorbent resin particles was measured in accordance with the water absorption amount test method for the highly water-absorbent resin of JIS K 7223-1996. Specifically, 0.2 g of the substance is put in a tea bag, immersed in deionized water for 3 hours, suspended for 10 minutes and drained immediately, and the weight is measured. It was.
  • Example 2 The moisture absorbent is gelatin (trade name; Cook Gelatin, manufactured by Morinaga & Co., Ltd., water absorption: 17 g / g, volume average particle size: 697 ⁇ m), and the timing of removing the uppermost layer containing moisture is 15 A coating film having a target dry film thickness of 100 ⁇ m was obtained in the same manner as in Example 1 except that the change was made after minutes.
  • the gelatin used was pulverized in advance using a pestle in a mortar for 2 minutes.
  • the water absorption of gelatin was determined in the same manner as in Example 1.
  • Example 3 10 g of the same dispersion as described in Example 1 was weighed into a glass bottle, 0.18 g of acetic anhydride was added as a water separation accelerator, and then the mixture was uniformly mixed by shaking by hand 10 times at room temperature. Immediately thereafter, it was painted on a test piece at room temperature with a 10 mil doctor blade. Fifteen minutes later, the test piece was tilted to remove the uppermost layer containing moisture, and a desired coating film having a dry film thickness of 100 ⁇ m was obtained.
  • Example 4 10 g of the same dispersion as described in Example 1 was weighed into a glass bottle, 0.18 g of acetic anhydride was added as a water separation accelerator, and then the mixture was uniformly mixed by shaking by hand 10 times at room temperature. Immediately thereafter, 8 g of gelatin was added as a water absorbent, and the mixture was shaken by reciprocating 10 times and mixed uniformly. Immediately after that, it was uniformly cast on the test piece at room temperature. After coating, the mixture was allowed to stand at room temperature for 1 hour, and the uppermost layer that contained water and became a film was removed with a spoon. Thus, a coating film having a target dry film thickness of 200 ⁇ m was obtained.
  • the gelatin shown above was filtered by impregnating 10 g of toluene in advance with 8 g of gelatin (trade name: Cook Gelatin, Morinaga & Co., Ltd., water absorption: 17 g / g). And then used.
  • Example 5 A target coating film having a dry film thickness of 200 ⁇ m was obtained in the same manner as in Example 4 except that the standing conditions were changed to a temperature of 5 ° C. and a humidity of 50%.
  • Example 6 A target coating film having a dry film thickness of 200 ⁇ m was obtained in the same manner as in Example 4 except that the standing conditions were changed to a temperature of 23 ° C. and a humidity of 83%.
  • Example 7 The target dry film was obtained in the same manner as in Example 4 except that the water absorbent was changed to 2 g of hydroxyethyl cellulose (trade name: SP-850, manufactured by Daicel, water absorption 20 g / g, volume average particle size: 92 ⁇ m). A 200 ⁇ m thick coating film was obtained.
  • the hydroxyethyl cellulose shown above was used after filtering what impregnated 2 g of hydroxyethyl cellulose in 4 g of toluene in advance. Further, the water absorption amount of hydroxyethyl cellulose was determined in the same manner as in Example 1.
  • Example 8 A coating film having a target dry film thickness of 200 ⁇ m was obtained in the same manner as in Example 4 except that 2.29 g of the polyhydroxysiloxane solution prepared in Production Example 1 was used as the water separation accelerator.
  • Comparative Example 1 10 g of the same dispersion as described in Example 1 was weighed in a glass bottle and coated on a test piece at room temperature with a 10 mil doctor blade. After coating, it was allowed to stand at room temperature for 1 hour to obtain a coating film having a dry film thickness of 100 ⁇ m. In addition, the water removal process was not performed.
  • Comparative Example 2 A coating film having a dry film thickness of 100 ⁇ m was obtained in the same manner as in Comparative Example 1 except that the standing conditions were changed to a temperature of 5 ° C. and a humidity of 50%. In addition, the water removal process was not performed.
  • Comparative Example 3 A coating film having a dry film thickness of 100 ⁇ m was obtained in the same manner as in Comparative Example 2 except that the standing time was changed to 5 hours.
  • Comparative Example 4 A coating film having a dry film thickness of 100 ⁇ m was obtained in the same manner as in Comparative Example 1 except that the standing conditions were changed to a temperature of 23 ° C. and a humidity of 83%. In addition, the water removal process was not performed.
  • Comparative Example 5 A coating film having a dry film thickness of 100 ⁇ m was obtained in the same manner as in Comparative Example 4 except that the standing time was changed to 5 hours. In addition, the water removal process was not performed.
  • the result of the comparative example 1 is an evaluation result of the coating film obtained by leaving it at room temperature for 1 hour after coating. From the results of Comparative Example 1, it can be seen that even when the room temperature condition is not used, when the water removal step is not performed, a good coating film cannot be obtained only by standing for 1 hour.
  • the results of Examples 1 to 8 are all evaluation results of the coating film immediately after being formed according to the above examples. In the examples of the present invention, it was confirmed that even when the same paint as in Comparative Example 1 was used, a good coating film could be formed by removing moisture by a method other than drying. .
  • the result of the comparative example 2 is an evaluation result of the coating film obtained by being allowed to stand for 1 hour in a coating environment where the evaporation of the aqueous medium is difficult under low temperature conditions.
  • the result of the comparative example 4 is an evaluation result of the coating film obtained by leaving still for 1 hour in the coating environment where the evaporation of the aqueous medium is difficult under high humidity conditions. In the coating environment of these comparative examples 2 and 4, even when it was allowed to stand for another 4 hours to promote the volatilization of water (Comparative Example 3 and Comparative Example 5), the coating film remained sticky. .
  • Example 5 and 6 in addition to being in the coating environment of Comparative Examples 2 and 4, since the coating film thickness is thick and the total water content in the coating film is large, doctor blade coating On the other hand, the coating film is formed by a coating method that is more disadvantageous in film formation. In Examples 5 and 6, it was confirmed that a good coating film without sticky feeling could be obtained even though the coating film was formed using a coating method with higher hurdles on film formation. .
  • a coating film having a desired function is formed even in a coating environment where it is difficult to evaporate an aqueous medium contained in an aqueous coating composition such as a low temperature condition and / or a high humidity condition. There is an advantage that it becomes possible to do.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Paints Or Removers (AREA)

Abstract

L'objectif de la présente invention est d'offrir un procédé grâce auquel il est possible de former un film de revêtement même sous des conditions, telles que des conditions de basse température et/ou des conditions très humides, dans lesquelles il est difficile de former un film de revêtement par revêtement avec une composition aqueuse de revêtement. La présente invention concerne un procédé de formation d'un film de revêtement, le procédé comprenant : une étape de revêtement pour le revêtement avec une composition aqueuse de revêtement; une étape de séparation du film de revêtement pour séparer le film de revêtement obtenu par ledit revêtement en une couche supérieure contenant de l'humidité et une couche de formation de film de revêtement; et une étape d'élimination de l'humidité pour éliminer la couche supérieure contenant de l'humidité par un procédé autre que le séchage.
PCT/JP2015/075980 2014-09-17 2015-09-14 Procédé de formation d'un film de revêtement Ceased WO2016043149A1 (fr)

Applications Claiming Priority (4)

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JP2014189017 2014-09-17
JP2014-189017 2014-09-17
JP2015-130811 2015-06-30
JP2015130811A JP6560036B2 (ja) 2014-09-17 2015-06-30 塗膜形成方法

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57130575A (en) * 1981-02-03 1982-08-13 Grace W R & Co Method of removing moisture from aqueous can end section lining compound
JPS61243866A (ja) * 1985-04-17 1986-10-30 アクゾ・ナ−ムロ−ゼ・フエンノ−トシヤツプ 道路マ−キング組成物の施与法
JPH08500405A (ja) * 1993-06-10 1996-01-16 プラスティルート ソシエテ アノニム 水平なマーキングを道路またはほかの交通区域へ塗布する方法と装置
JPH09235489A (ja) * 1996-02-26 1997-09-09 Rohm & Haas Co 水性道路マーキング塗料
JP2001214409A (ja) * 1999-12-03 2001-08-07 Rohm & Haas Co 屋外用コーティングの乾燥時間の短縮方法
JP2004148133A (ja) * 2002-09-05 2004-05-27 Sk Kaken Co Ltd 化粧面の形成方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57130575A (en) * 1981-02-03 1982-08-13 Grace W R & Co Method of removing moisture from aqueous can end section lining compound
JPS61243866A (ja) * 1985-04-17 1986-10-30 アクゾ・ナ−ムロ−ゼ・フエンノ−トシヤツプ 道路マ−キング組成物の施与法
JPH08500405A (ja) * 1993-06-10 1996-01-16 プラスティルート ソシエテ アノニム 水平なマーキングを道路またはほかの交通区域へ塗布する方法と装置
JPH09235489A (ja) * 1996-02-26 1997-09-09 Rohm & Haas Co 水性道路マーキング塗料
JP2001214409A (ja) * 1999-12-03 2001-08-07 Rohm & Haas Co 屋外用コーティングの乾燥時間の短縮方法
JP2004148133A (ja) * 2002-09-05 2004-05-27 Sk Kaken Co Ltd 化粧面の形成方法

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