CN113652134A - Stain-resistant matte aqueous coating composition and method for forming stain-resistant matte coating film - Google Patents
Stain-resistant matte aqueous coating composition and method for forming stain-resistant matte coating film Download PDFInfo
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Abstract
The present invention relates to a stain-resistant matte water-based coating composition having stain resistance and weather resistance in combination over a long period of time and also having excellent substrate following properties, a method for forming a stain-resistant matte coating film using the same, and a coated article. The aqueous coating composition for stain-resistant matting is characterized by containing an aqueous resin (A), a pigment component (B) and a glycol ether compound (C), wherein the glass transition temperature of the aqueous resin (A) is 10 ℃ or higher, the copolymerization ratio of an aromatic vinyl compound is 40 mass% or lower, the pigment component (B) contains a coloring pigment (B1), a flake-like extender pigment (B2) and an extender pigment (B3) other than (B2), the amount of (B1) is 5 parts by mass or higher, the amount of (B2) is 50 parts by mass or higher, the amount of (B3) is 20 parts by mass or higher, and the pigment volume concentration is 35% or higher within the range of 5 to 25 parts by mass, based on 100 parts by mass of the solid content of the aqueous resin (A).
Description
The application is a divisional application of Chinese patent application No. 201510489689.3 with the same name of invention, and the original application date is 2015, 8 months and 11 days.
Technical Field
The present invention relates to a stain-resistant matte aqueous coating composition and a method for forming a stain-resistant matte coating film using the same.
Background
In recent years, the demand of customers for interior and exterior wall coatings of buildings and the like has diversified, and awareness of finish gloss that affects the appearance impression has been changing. In particular, glossy finish having a high-grade appearance has been preferred for outer walls, but there is an increasing demand for so-called matte finish having a low gloss with a glossy and dark appearance.
In general, a matte finish for forming a matte finish can be designed by: a method of utilizing a difference in refractive index of the resin; a method of adding wax; and a method of adding a matting pigment such as silica or an extender pigment to form irregularities on the surface of the coating film.
However, the method using the difference in refractive index of the resin has a limit in the matting effect, and it is difficult to form complete matting with a 60-degree specular gloss of 5 or less. In addition, the method of adding waxes has problems of poor stain resistance and low hiding property. Therefore, various methods of adding a matting pigment have been developed, and for example, patent document 1 discloses a matting aqueous coating composition containing titanium dioxide, porous calcium carbonate, and an aqueous resin.
According to the aqueous coating composition described in patent document 1, although a coating film having low gloss and high diffuse reflectance can be obtained, the amount of the matting pigment to be added must be increased in order to eliminate gloss, and therefore, even if matting occurs, the elongation and breaking strength of the coating film become low, and the coating film cannot follow the deformation of the substrate, and cracks or peeling may occur.
In order to solve such a problem, patent document 2 discloses an aqueous matting coating composition containing a carbonyl group-containing copolymer emulsion having a glass transition temperature in a specific range, a specific amount of a polyhydrazide compound, and a pigment component having a pigment volume concentration in a specific range, and patent document 3 discloses an aqueous coating composition having a pigment volume concentration in a specific range, which contains a synthetic resin emulsion having a glass transition temperature in a specific range, and an organic powder as a matting agent.
The coatings described in patent documents 2 and 3 can exhibit a matte appearance and have excellent conformability to a substrate, but when applied to outdoor coating such as an exterior wall, there is a problem that the coating film is easily contaminated by exposure over a long period of time, and therefore, development of a water-based matte coating having excellent stain resistance is required.
Documents of the prior art
Patent document
Patent document 1: japanese unexamined patent publication No. 2012-92289
Patent document 2: japanese unexamined patent publication No. 11-21514
Patent document 3: japanese unexamined patent application publication No. 2005-320496
Disclosure of Invention
Problems to be solved by the invention
An object of the present invention is to provide: a matte water-based paint composition having stain resistance and weather resistance for a long period of time and excellent in substrate followability, and a method for forming a coating film using the same.
Means for solving the problems
The present inventors have made intensive studies on the above-mentioned problems, and as a result, have found that a coating film having a matte effect and excellent stain resistance, weather resistance and substrate following property can be obtained by blending a pigment component having a specific composition and a glycol ether compound in specific amounts in a specific aqueous resin, and have completed the present invention.
Namely, the present invention relates to a contamination-resistant matte aqueous coating composition, a method for forming a contamination-resistant matte coating film, and a coated article obtained by the method for forming a contamination-resistant matte coating film,
the aqueous coating composition for flatting with stain resistance comprises an aqueous resin (A), a pigment component (B) and a glycol ether compound (C), and is characterized in that the glass transition temperature of the resin of the aqueous resin (A) is 10 ℃ or higher, the copolymerization ratio of an aromatic vinyl compound in the solid content of the aqueous resin (A) is 40 mass% or lower,
the pigment component (B) contains a color pigment (B1), a flaky extender pigment (B2) and an extender pigment (B3) other than (B2),
the contents of the coloring pigment (b1), the flaky extender pigment (b2), the extender pigment (b3) and the glycol ether compound (C) are based on 100 parts by mass of the solid content of the aqueous resin (A),
(b1) is more than 5 parts by mass of the total weight of the composition,
(b2) is more than 50 parts by mass of the total weight of the composition,
(b3) is more than 20 parts by mass of the total weight,
(C) in the range of 5-25 parts by mass, the pigment volume concentration is more than 35%; the method for forming a contamination-resistant matte coating film is characterized by applying the contamination-resistant matte aqueous coating composition.
Effects of the invention
The stain-resistant matte aqueous coating composition of the present invention can stably provide the appearance of a matte atmosphere, and is resistant to cracking and the like even in a severe environment such as outdoor exposure by using a coating film having a high matte degree, excellent in weather resistance, and has stain resistance against rain water and the like.
Detailed Description
The stain-resistant matte aqueous coating composition of the present invention contains an aqueous resin (a), a pigment component (B), and a glycol ether compound (C).
< Water-based resin (A) >
The aqueous resin (a) in the present invention may be water-soluble or water-dispersible, and any conventionally known resin may be used without particular limitation as long as it has a coating film-forming ability, and examples thereof include: acrylic resin, silicone resin, urethane resin, fluorine resin, polyvinyl acetate resin, epoxy resin, phenol resin, polyester resin, alkyd resin, polycarbonate resin, melamine resin, and the like, and these may be used alone or in combination of 2 or more. These resins may be modified as in urethane-modified acrylic resins, may be graft-polymerized resins, or may be in the form of dispersed particles.
When the aqueous resin (a) is in the form of dispersed particles, it may have a multilayer structure such as a single-layer structure (homogeneous granular structure) or a core-shell structure, and in the case of the core-shell structure, the core and/or the shell may be crosslinked.
In the present invention, the aqueous resin (A) is characterized in that the glass transition temperature of the resin is 10 ℃ or higher and the copolymerization ratio of the aromatic vinyl compound in the solid content of the aqueous resin (A) is 40 mass% or less.
In the present specification, the glass transition temperature (Tg) of the resin can be calculated, for example, by the following FOX formula.
1/Tg＝W1/Tg1+W2/Tg2+···+Wn/Tgn
In the above formula FOX, Tg is the glass transition temperature (K) of a polymer composed of n monomers, Tg1, Tg2, · · Tgn are the glass transition temperatures (K) of homopolymers of the monomers, W1, W2 · Wn are the mass fractions of the monomers, and W1+ W2+ · · Wn is 1.
When the glass transition temperature of the resin of the aqueous resin (a) is less than 10 ℃, the stain resistance of the matte coating film becomes insufficient, which is not preferable.
More preferably, the glass transition temperature of the resin of the aqueous resin (A) is in the range of 15 to 60 ℃.
When the copolymerization ratio of the aromatic vinyl compound in the solid content of the aqueous resin (a) exceeds 40 mass%, the coating film formed from the coating composition of the present invention is undesirably low in both substrate tracking property and weather resistance.
In the present invention, specific examples of the aqueous resin (a) include: aromatic vinyl compounds, (meth) acryloyl group-containing compounds, and copolymers of other polymerizable unsaturated monomers.
Examples of the aromatic vinyl compound include: styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2, 4-dimethylstyrene, ethylstyrene, p-tert-butylstyrene, α -methylstyrene, α -methyl-p-methylstyrene, vinylethylbenzene, vinylxylene, vinylnaphthalene, diphenylethylene, and the like.
Examples of the (meth) acryloyl group-containing compound include compounds having 1 (meth) acryloyl group in 1 molecule, for example: (meth) acryloyl monomers having a linear or branched alkyl group such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, and stearyl (meth) acrylate; alicyclic alkyl group-containing (meth) acryloyl monomers such as cyclohexyl (meth) acrylate and isobornyl (meth) acrylate; aralkyl group-containing (meth) acryl monomers such as benzyl (meth) acrylate; (meth) acryl monomers having an alkoxyalkyl group such as 2-methoxyethyl (meth) acrylate and 2-ethoxyethyl (meth) acrylate; fluorine-containing (meth) acryloyl monomers such as hexafluoroisopropyl (meth) acrylate, perfluorooctyl methyl (meth) acrylate, and perfluorooctyl ethyl (meth) acrylate; an amino group-containing (meth) acryloyl monomer such as N, N-diethylaminoethyl (meth) acrylate; (meth) acrylamide; hydroxyl group-containing (meth) acryloyl monomers such as hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate, modified products of epsilon-caprolactone of the hydroxyalkyl (meth) acrylate, and (meth) acrylic acid esters containing polyoxyethylene having a hydroxyl group at the molecular end; carboxyl group-containing (meth) acryloyl monomers such as (meth) acrylic acid and β -carboxyethyl acrylate; carbonyl group-containing (meth) acryloyl monomers such as acetoacetoxyethyl (meth) acrylate and diacetone (meth) acrylamide; epoxy group-containing (meth) acryl monomers such as glycidyl (meth) acrylate, β -methylglycidyl (meth) acrylate, 3, 4-epoxycyclohexylmethyl (meth) acrylate, 3, 4-epoxycyclohexylethyl (meth) acrylate, and 3, 4-epoxycyclohexylpropyl (meth) acrylate; isocyanate group-containing (meth) acryloyl monomers such as isocyanatoethyl (meth) acrylate; alkoxysilyl group-containing (meth) acryl monomers such as γ -methacryloxypropyltrimethoxysilane and γ -methacryloxypropyltriethoxysilane; and (meth) acryloyl monomers having an oxidative curable group such as dicyclopentenyloxyethyl (meth) acrylate, dicyclopentenyloxypropyl (meth) acrylate, and dicyclopentenyl (meth) acrylate.
Examples of the compound having at least 2 (meth) acryloyl groups in 1 molecule include: allyl (meth) acrylate, ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 1, 3-butanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, 1, 4-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, glycerol di (meth) acrylate, 1,1, 1-trihydroxymethyl ethane tri (meth) acrylate, 1,1, 1-trihydroxymethyl propane tri (meth) acrylate, and the like.
These (meth) acryloyl group-containing compounds may be used singly or in combination of 2 or more.
In addition, as other polymerizable unsaturated monomers, there may be mentioned: (meth) acrylonitrile; vinyl ester compounds such as vinyl acetate and vinyl propionate; polyvinyl compounds having at least 2 polymerizable unsaturated groups in 1 molecule, such as triallylisocyanurate, diallyl terephthalate, and divinylbenzene; allyl alcohol; carboxyl group-containing polymerizable unsaturated monomers such as maleic acid and crotonic acid; carbonyl group-containing polymerizable unsaturated monomers such as (meth) acrolein, formylstyrene, C4-7 vinyl alkyl ketones (e.g., vinyl methyl ketone, vinyl ethyl ketone, vinyl butyl ketone, etc.), acetoacetoxyallyl esters, etc.; polymerizable unsaturated monomers containing an epoxy group such as allyl glycidyl ether; isocyanate group-containing polymerizable unsaturated monomers such as m-isopropenyl- α, α -dimethylbenzyl isocyanate; alkoxysilyl group-containing polymerizable unsaturated monomers such as vinyltrimethoxysilane and vinyltriethoxysilane; fluorovinyl ethers such as fluoroalkyl trifluorovinyl ether and perfluoroalkyl trifluorovinyl ether; the epoxy group-containing polymerizable unsaturated monomer or the hydroxyl group-containing polymerizable unsaturated monomer, and the oxidative curing group-containing polymerizable unsaturated monomer such as a reaction product of an unsaturated fatty acid, may be used singly or in combination of 2 or more.
In the present invention, the aqueous resin (a) preferably has a hydrolyzable silyl group. This makes it possible to exhibit stain resistance to form a coating film from an early stage.
Examples of the monomer used for introducing the hydrolyzable silyl group into the aqueous resin (a) include: alkoxysilyl group-containing polymerizable unsaturated monomers such as vinyltrimethoxysilane, vinyltriethoxysilane, gamma-methacryloxypropyltrimethoxysilane and gamma-methacryloxypropyltriethoxysilane may be used singly or in combination of 3 or more.
The method of polymerizing the monomer is not particularly limited, and for example, the monomer may be (co) polymerized in the presence of a polymerization initiator and an emulsifier according to a general emulsion polymerization method.
The polymerization initiator is capable of initiating addition polymerization of the monomer by radical decomposition in the presence of heat or a reducing agent, and both an inorganic initiator and an organic initiator can be used.
As the emulsifier, known per se emulsifiers can be used, and specific examples thereof include: an anionic surfactant, a nonionic surfactant, a zwitterionic surfactant, or a reactive surfactant containing both a polymerizable unsaturated group and an anionic group or a nonionic group in a molecule may be used.
The amount of the polymerizable unsaturated monomer used is usually 0.5 to 6% by mass, preferably 1 to 4% by mass based on the total mass of the total polymerizable unsaturated monomer.
When the aqueous resin (A) has an acid group, the acid group may be substituted with an amine such as methyl amine, dimethyl amine, trimethyl amine, ethyl amine, diethyl amine, triethyl amine, dimethylaminoethanol, 2-methyl-2-amino-1-propanol; the alkali such as ammonia is partially or substantially completely neutralized.
The (co) polymerization of the monomers may be carried out using a chain transfer agent, a pH adjuster, or a solvent, as required.
The aqueous resin (A) produced as described above may have an average particle diameter of usually 50 to 500nm, preferably 100 to 400nm, and more preferably 100 to 300 nm.
In the present specification, the average particle diameter of the aqueous resin (a) is a value measured at room temperature (about 20 ℃) by diluting a sample with deionized water to a concentration suitable for measurement using a Coulter counter N4 (trade name, product of Beckman Coulter co., ltd., particle size distribution measuring instrument).
< pigment component (B) >
The pigment component (B) used in the aqueous coating composition of the present invention contains a coloring pigment (B1), a flaky extender pigment (B2), and an extender pigment (B3) other than (B2).
In the present invention, the coloring pigment (b1) is used for imparting chroma and hiding property to a coating film formed from the aqueous coating composition of the present invention, and known coloring pigments for coating materials are exemplified, and specifically, the following are exemplified: white pigments such as titanium oxide, zinc oxide, aluminum oxide, magnesium oxide, antimony oxide, zirconium oxide, aluminum nitride, boron nitride, and lead white (zinc carbonate); colored pigments such as iron oxide, perylene pigment, azo pigment, yellow lead, red iron oxide, vermilion, titanium red, cadmium red, quinacridone red, isoindolinone, benzimidazolinone, phthalocyanine green, phthalocyanine blue, cobalt blue, indanthrene blue, ultramarine, and prussian blue; bright pigments such as aluminum pigment, copper, zinc, brass, nickel, alumina coated with titanium oxide or iron oxide, mica coated with titanium oxide or iron oxide, and hologram pigment; black pigments such as carbon black, and the like, and these may be used alone or in combination of 2 or more.
Specific examples of the flaky extender pigment (b2) include: talc, mica, glass flake, and the like, and these may be used alone or in combination of 2 or more.
The flaky extender pigment (b2) has the effect of providing a stain-resistant matte coating film having excellent crack resistance even under severe conditions such as outdoors.
(b2) The other extender pigments (b3) may be any known extender pigments. Specifically, calcium carbonate, barium sulfate, kaolin clay, and the like can be used, and these may be used alone or in combination of 2 or more. The pigment (b3) has an effect of imparting a matte effect to the formed coating film.
In the present invention, the total amount a of the oil absorption of the pigment component (B) is 80ml or less, preferably 10 to 70ml, per 100 parts by mass of the solid content of the aqueous resin (a). When the total amount a of the oil absorption is within this range, the crack resistance of the formed coating film is effectively improved.
In the present specification, the total amount a (ml) of oil absorption of the pigment component (B) is the amount (ml) of boiled linseed oil absorbed per 100 parts by mass of the solid content of the aqueous resin (a) in the aqueous coating composition of the present invention, and can be calculated as follows.
A (ml) ([ oil absorption of pigment (b 1)/100 × mass of aqueous resin (a) solid content per 100 parts by mass of pigment (b1) ] + [ oil absorption of pigment (b 2)/100 × mass of aqueous resin (a) solid content per 100 parts by mass of pigment (b2) ] + · [ oil absorption of pigment (bn)/100 × mass of aqueous resin (a) solid content per 100 parts by mass of pigment (bn) ]
Oil absorption (ml/100g) was measured according to JIS K5101-13-2: the value obtained by the method described in 2004 is a value represented by the amount (ml) of boiled linseed oil absorbed by 100g of the pigment.
In the present invention, the proportions of the colored pigment (b1), the flaky extender pigment (b2) and the extender pigment (b3) used are different depending on the target color tone and the degree of matting, and the solid content of the aqueous resin (a) is usually used as a reference
The amount of the coloring pigment (b1) is 5 parts by mass or more, preferably 10 to 120 parts by mass,
the flaky extender pigment (b2) is 50 parts by mass or more, preferably 60 to 200 parts by mass,
the content of the extender pigment (b3) is not less than 20 parts by mass, and preferably may be in the range of 20 to 150 parts by mass.
When the amount of the pigment (b1) is less than 5 parts by mass, the hiding power of the formed coating film is poor, when the amount of the pigment (b2) is less than 50 parts by mass, the weather resistance, stain resistance and substrate follow-up property of the formed coating film are insufficient, and when the amount of the pigment (b3) is less than 20 parts by mass, the formed coating film may have uneven gloss, which is not preferable.
In the present invention, the pigment volume concentration of the pigment component (B) is 35% or more, preferably in the range of 35 to 60%.
When the pigment volume concentration is less than 35%, the matte finish film may have insufficient matte and stain resistance, which is not preferable.
In the present specification, the "pigment volume concentration" is a volume ratio of the pigment component to a total solid content of the total resin component and the total pigment in the coating material.
The pigment specific gravity as a base for calculating the volume of the pigment was obtained based on "handbook of paint raw materials, 6 th edition" (japan society of societies, the paint industry), and the specific gravity of the solid resin component was set to a value of approximately 1.
< diol ether Compound (C) >
The aqueous coating composition of the present invention contains a glycol ether compound (C).
The diol ether compound (C) has the effect of improving film-forming properties and improving substrate conformability.
Specific examples of such a glycol ether compound (C) include: ethylene glycol monomethyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, triethylene glycol monomethyl ether, tripropylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monoethyl ether, tripropylene glycol monoethyl ether, ethylene glycol monopropyl ether, propylene glycol monopropyl ether, diethylene glycol monopropyl ether, dipropylene glycol monopropyl ether, triethylene glycol monopropyl ether, tripropylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monobutyl ether, diethylene glycol monobutyl ether, dipropylene glycol monobutyl ether, triethylene glycol monobutyl ether, ethylene glycol dimethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, triethylene glycol dimethyl ether, tripropylene glycol dimethyl ether, propylene glycol dimethyl ether, Ethylene glycol diethyl ether, propylene glycol diethyl ether, diethylene glycol diethyl ether, dipropylene glycol diethyl ether, triethylene glycol diethyl ether, tripropylene glycol diethyl ether, ethylene glycol dipropyl ether, propylene glycol dipropyl ether, diethylene glycol dipropyl ether, dipropylene glycol dipropyl ether, triethylene glycol dipropyl ether, tripropylene glycol dipropyl ether, ethylene glycol dibutyl ether, propylene glycol dibutyl ether, diethylene glycol dibutyl ether, dipropylene glycol dibutyl ether, triethylene glycol dibutyl ether, tripropylene glycol dibutyl ether, tetrahydrofuran, dioxane, dimethoxyethane, polyethylene oxide, ethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, etc., and these may be used singly or in combination of 2 or more. Among them, a compound having a boiling point of 200 ℃ or higher is particularly preferably used.
The content of the glycol ether compound (C) is preferably 5 to 25 parts by mass, more preferably 7 to 20 parts by mass, based on 100 parts by mass of the solid content of the aqueous resin (a).
When the content of the glycol ether compound (C) is less than 5 parts by mass, the following property to the substrate to form a coating film is not sufficient, while when it exceeds 25 parts by mass, the stain resistance of the formed coating film becomes insufficient, and when the coating is superimposed, problems occur in appearance such as uneven gloss.
< aqueous coating composition >
In the aqueous coating composition of the present invention, an inorganic matting agent such as silica, alumina, or glass beads, or an organic matting agent such as a polycarbonate resin, an acrylic resin, a polyurethane resin, or a polyamide resin may be used within a range not impairing the effects of the present invention. The shape of the matting agent may be amorphous, spherical, polyhedral, or the like, without limitation.
Further, known additives for coating materials such as a modifying resin other than the aqueous resin (a), a crosslinking agent, an ultraviolet absorber, a light stabilizer, hollow particles, an alkyl silicate, an aggregate, fibers, a plasticizer, a leveling agent, a sagging inhibitor, a fluorescent brightener, a silane coupling agent, a thickener, a neutralizer, an antistatic agent, a softener, an antibacterial agent, a perfume, a curing catalyst, a pH adjuster, a humidity adjuster, powdered or particulate activated carbon, photocatalytic titanium oxide, an aqueous water repellent, a dispersant, a defoaming agent, an antiseptic, a mildewproofing agent, an antifreezing agent, a film forming aid, zinc whiskers, a curing accelerator, an aldehyde adsorbent, a wax, and a flame retardant may be contained as necessary.
Among them, examples of the light stabilizer include: bis (1,2,2,6, 6-pentamethyl-4-piperidyl) sebacate, methyl (1,2,2,6, 6-pentamethyl-4-piperidyl) sebacate, bis (2,2,6, 6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6, 6-pentamethyl-4-piperidyl) 2- (3, 5-di-tert-butyl-4-hydroxybenzyl) -2-n-butylmalonate, dimethyl succinate-1- (2-hydroxyethyl) -4-hydroxy-2, 2,6, 6-tetramethylpiperidine polycondensate, poly [ 16- (1,1,3, 3-tetramethylbutyl) imino-1, 3, 5-triazine-2, 4-diyl ], [ (2,2,6, 6-tetramethyl-4-piperidyl) imino ] -hexamethylene [ (2,2,6, 6-tetramethyl-4-piperidyl) imino ], [ 2- [ 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyloxy ] ethyl ] -4- [ 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyloxy ] -2,2,6, 6-tetramethylpiperidine, (mixed 1,2,2,6, 6-pentamethyl-4-piperidyl/tridecyl) -1,2,3, 4-butanetetracarboxylate, mixed [ 1,2,2,6, 6-pentamethyl-4-piperidyl/beta ], hindered amine-based light stabilizers such as β, β' -tetramethyl-3, 9- [ 2,4,8, 10-tetraoxaspiro (5,5) undecane ] diethyl ] 1-1,2,3, 4-butanetetracarboxylate and tetrakis (2,2,6, 6-tetramethyl-4-piperidyl) -1,2,3, 4-butanetetracarboxylate, and these can be used alone or in combination of 2 or more.
The amount of the light stabilizer is 0.5 to 10 parts by mass, preferably 1 to 5 parts by mass, based on 100 parts by mass of the solid content of the aqueous resin (A).
The above-described stain-resistant matte aqueous coating composition of the present invention is a hard coating film even under normal temperature drying conditions, specifically, the press-in hardness of the formed coating film is 5N/mm or more, and particularly, may be in the range of 7 to 35N/mm, and can exhibit stain resistance from the initial stage after coating.
In the present specification, the indentation hardness of the coating film is a value obtained by measuring the martensite hardness at indentation to a maximum load of 25mN using a Fischer durometer HM 2000S.
< method for Forming coating film Using stain-resistant matte Water-based coating composition >
The water-based coating composition for matting having stain resistance of the present invention can form a matting coating film having excellent stain resistance by being applied to the surface of a substrate.
The surface of the substrate to which the aqueous coating composition of the present invention can be applied is not particularly limited, and examples thereof include: a surface of a base material such as a metal processing material such as a gypsum board, a concrete slab, a concrete block, an exterior wall decorative panel, a mortar board, a slate board, a PC board, an ALC board, a cement calcium silicate board, a brick, glass, wood, stone, a plastic molding, a ceramic ware, a ceramic tile, an iron material, an aluminum frame, or the like; coating surfaces of acrylic resin, acrylic urethane resin, fluororesin, silicone resin, silicone acrylic resin, vinyl acetate resin, epoxy resin, and the like, provided on these substrates; and a wallpaper surface formed of polyvinyl chloride, polyolefin, paper, cloth, or the like.
The surface of these substrates may be pretreated with a blocking agent or the like.
The aqueous coating composition of the present invention can form a coating film which is excellent in weather resistance and stain resistance against rainwater and the like, and has appropriate substrate following properties and light extinction properties, and therefore, can be preferably applied to the outer wall of a building.
Specific examples of the building outer wall include: examples of materials constituting the outer wall surfaces of various buildings such as buildings, houses, facilities, and warehouses include general outer wall materials such as inorganic outer wall materials including ceramic outer wall panels, mortar, concrete, and slates, metal outer wall materials including iron, aluminum, and metal outer wall materials, wood outer wall materials including natural wood and plywood, and materials having a used coating film provided on the surface thereof.
The aqueous coating composition of the present invention can be coated by coating means known per se, and can be suitably selected from coating methods such as roll, air spray, airless spray, sand blast gun, universal gun, brush, and roll coater, for example, depending on the type and use of the substrate. The aqueous coating composition of the present invention can be applied repeatedly over a plurality of times without impairing the appearance of the coating film.
The drying to form a coating film may be performed by drying at room temperature, but may be performed by heating or forced drying depending on the composition of the coating composition used, the coating environment, and the like.
The thickness of the dry film can be adjusted as appropriate depending on the substrate to be used and the coating environment.
The water-based coating composition of the present invention may be applied in advance with a primer coating on the surface of a substrate according to circumstances, and then applied to the resulting primer coated surface.
The primer coating can be appropriately selected depending on the type and/or state of the substrate surface, and examples thereof include a coating containing an aqueous or solvent-based resin as a resin binder, the aqueous or solvent-based resin being composed of resin types such as an acrylic resin, an acrylic silicone resin, a fluorine-based resin, a polyvinyl acetate-based resin, a polyolefin-based resin, a silicone resin, a polyurethane-based resin, an epoxy-based resin, a phenol-based resin, a polyester-based resin, an alkyd-based resin, a melamine-based resin, and a biodegradable resin, and a water-based coating containing an aqueous resin is preferably used.
The aqueous coating composition of the present invention imparts a matte effect and satisfies both stain resistance and weather resistance, but since the coating film also has flexibility, an undercoat coating composition having a coating film-forming elongation of 50% or more can be used as an undercoat coating, and can be sufficiently applied to a substrate surface that deforms greatly together with the undercoat coating composition.
The coating of the above-mentioned coating material for forming an undercoat can be carried out by coating means known per se, and can be suitably selected and used from coating methods such as roll, air spray, airless spray, sand blast gun, universal gun, brush, and roll coater, for example, depending on the use of the substrate. The formed undercoat coating film is preferably dried at room temperature, but may be dried by heating or forced drying depending on the kind of undercoat coating material, coating environment, and the like.
Examples
The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. In the following examples, "parts" and "%" mean "parts by mass" and "% by mass", respectively.
Production of aqueous resin
Production example 1
350 parts of deionized water and 10 parts of Newcol 707SF (Note 1) were charged into a reaction vessel equipped with a thermometer, a thermostat, a stirrer, and a dropping device, and the mixture was stirred and mixed in a nitrogen stream to raise the temperature to 85 ℃. Subsequently, a 3% portion of a pre-emulsion obtained by emulsifying the components having the following composition and 80 parts of a 2.5% ammonium persulfate aqueous solution were added to the reaction vessel and held at 85 ℃ for 20 minutes.
Then, the remaining pre-emulsion and 80 parts of a 2.5% aqueous ammonium persulfate solution were added dropwise to the reaction vessel over 4 hours, followed by aging for 2 hours after completion of the addition. Then, the mixture was cooled to 30 ℃ and adjusted to have a solid content of 47% and a pH of 8.0 using ammonia water and deionized water. Then, the mixture was discharged through a 200-mesh nylon cloth while filtering the mixture, to obtain an aqueous resin (A-1) having an average particle diameter of 180nm and a glass transition temperature of 27 ℃.
(Note 1) Newcol 707 SF: trade name, anionic surfactant having polyoxyethylene chain manufactured by Nippon emulsifier Co., Ltd., and nonvolatile fraction of 30%.
Production examples 2 to 4
Aqueous resins (a-2) to (a-4) were synthesized in the same manner as in production example 1, except that the monomer composition in production example 1 was changed to the composition shown in table 1 below.
[ Table 1]
Production of a white pigment in the form of a dispersed paste
Production example 5
Each component shown below was sequentially charged into a stainless steel vessel while stirring, and the mixture was stirred for 30 minutes by a homogenizer manufactured by PRIMIX corporation until uniform to obtain a white pigment dispersion paste (B-1).
(Note 2) Suraoff 72N: trade name, manufactured by Enviro Chemicals of Japan, antiseptic,
(Note 3) SP-600: trade name, manufactured by Daicel chemical industries, hydroxyethyl cellulose-based tackifier,
(Note 4) DISPER BYK-190: trade name, BYK-Chemie, Inc., pigment dispersant, pigment powder, and pigment powder,
(Note 5) BYK-028: trade name, BYK-Chemie, Inc., antifoaming agent,
(Note 6) TI-PURE R-706: trade name, manufactured by DuPont, titanium dioxide, specific gravity 4.0, oil absorption 14(ml/100g),
(Note 7) TTK Talc: trade name, bamboo chemical industry product, talc, specific gravity 2.7, oil absorption 27(ml/100g),
(Note 8) Super S: trade name, manufactured by pill tail calcium corporation, ground calcium carbonate, specific gravity of 2.7, and oil absorption of 23(ml/100 g).
Production examples 6 to 9
White pigment dispersion pastes (B-2) to (B-5) were obtained in the same manner as in production example 5, except that the pigment compositions in production example 5 were blended as shown in table 2 below.
[ Table 2]
(Note 9) Super # 1700: trade name, manufactured by pill tail calcium corporation, ground calcium carbonate, specific gravity of 2.7, and oil absorption of 32(ml/100 g).
Production of Black pigment paste
Production example 10
The following components were sequentially charged into a stainless steel container while stirring, and stirred for 10 minutes by a homogenizer manufactured by PRIMIX corporation until uniform, and then dispersed for 1 hour by a paint shaker to obtain a black dispersion liquid.
Then, 130 parts of deionized water, 1 part of ethylene glycol, 100 parts of TTK Talc (note 7), and 50 parts of Super S (note 8) were added to 124 parts of the obtained black dispersion, and the mixture was stirred with a homogenizer (PrIMIX corporation) for 30 minutes until uniform, to obtain a black pigment dispersion paste (B-6).
(Note 10) TAROX BL-500: trade name, manufactured by titanium industries, black iron oxide pigment, specific gravity of 5.0, oil absorption of 28(ml/100 g).
Production of aqueous coating materials
Examples 1 to 8 and comparative examples 1 to 7
Each component shown in Table 3 below was sequentially charged into a stainless steel vessel while stirring, and the mixture was stirred for 15 minutes by a homogenizer manufactured by PRIMIX corporation until the mixture became homogeneous, thereby obtaining water-based paints (C-1) to (C-15).
In addition, the property values of each aqueous coating material are shown in table 3.
Evaluation test
The aqueous coating materials obtained in examples and comparative examples were subjected to the following evaluations. The results are shown in Table 3.
(v 1) finishing
On a flexible board (600X 900X 4mm), in an amount of 100g/m2The method (1) uses an Eco catching Sealer (manufactured by Kansai Paint Co., Ltd., aqueous cationic emulsion Sealer) coated on a rough roller, dries at 23 ℃ and 50% relative humidity for 18 hours, and then coats at a coating amount of 120g/m2The evaluation paint was applied to the entire surface of the flexible sheet using a rough roller. After drying under the same conditions for 4 hours, a coating amount was 120g/m in a part thereof2In the manner of (1) the same coating was repeatedly applied using a blanket roll. Further, the film was dried at 23 ℃ and 50% relative humidity for 7 days, and then the state of the surface of the film was visually evaluated.
O: no color unevenness, no visible repeated coating part,
And (delta): when observed obliquely, the film had uneven gloss and the repeatedly applied portions were visible,
X: the color unevenness was remarkable, and the repeatedly coated portions were observed from any angle.
(. 2) stain resistance
On a flexible plate (90X 300X 4mm), in an amount of 100g/m2In the mode of using an intermediate roughing roller coating "Eco Cand (ii) a water-based cationic emulsion-based Sealer manufactured by Kansai Paint corporation, and dried at a temperature of 23 ℃ and a relative humidity of 50% for 18 hours.
Then, the amount of coating per 1 time was l20g/m2The flexible board obtained was treated with the coating material for evaluation 2 times, dried at 23 ℃ and 50% relative humidity for 7 days, and used as a test board for contamination resistance. The test panels were then placed 30 ° south of the kanji Paint company in the tokyo field for 12-month exposure. After exposure, the brightness in the L.a.. b.. b.color system was measured by a color difference meter (CR-300, manufactured by Konicaminolta Co., Ltd.), and the contamination resistance was evaluated from the absolute value (. DELTA.L) of the brightness difference before and after exposure.
O: delta L is less than 5,
And (delta): Δ L is 5 or more and less than 9,
X: Δ L is 9 or more.
(v 3) substrate followability
On a flexible plate (70X 150X 4mm), in an amount of 100g/m2The brush was coated with an Eco catching Sealer (manufactured by Kansai Paint Co., Ltd., aqueous cationic emulsion Sealer), dried at 23 ℃ and 50% relative humidity for 18 hours, and then coated with 900g/m of a coating amount using a Mastic roll (Mastic roll)2A main material of a waterproof multilayer coating material E specified in JIS A6909 was coated and dried under the same conditions for 24 hours. Then, the coating amount per 1 pass was set to 120g/m2The coating was evaluated by repeating coating 2 times at coating intervals of 4 hours using a brush. Then, the plate was dried at 23 ℃ and 50% relative humidity for 7 days to prepare a test plate. The test panels obtained by the above method were subjected to a warm-cold repeated test in which water was immersed (23 ℃) for 18 hours → -20 ℃ in air for 3 hours → 50 ℃ in air for 3 hours for 1 cycle in total of 10 cycles, and then cracks on the coating film surface were visually observed.
O: no crack is generated,
And (delta): slight cracks were observed,
X: cracks were observed over the entire surface of the coating film.
Weather resistance of (v 4)
On a flexible plate (70X 150X 4mm), in an amount of 100g/m2The coating was applied to an Eco catching Sealer (aqueous cationic emulsion Sealer, manufactured by Kansai Paint Co., Ltd.) by a brush, dried at 23 ℃ and 50% relative humidity for 18 hours, and then applied by a brush in an amount of 120g/m per 1 pass2The coating was repeatedly applied 2 times at coating intervals of 4 hours to evaluate the coating. Subsequently, the resultant was dried at 23 ℃ and 50% relative humidity for 7 days to obtain a flexible sheet as a weather-resistant test sheet. The resultant was subjected to a xenon lamp method test as defined in JIS K5600-7-7, irradiated for 1000 hours, and then evaluated for the state of powdering of the coating film surface as defined in JIS K5600-8-6.
Very good: a powdering grade of 1 or less, no swelling, peeling, cracking, etc., no significant change in color compared with the sample,
O: a powdering grade of 2 or less, no swelling, peeling, cracking, etc., a slight change in color from that of the sample,
And (delta): a powdering grade of 3 or less, no swelling, peeling, cracking, etc., a greater change in color than that of the sample,
X: the powdering grade was 4 or more, and the change in color was more remarkable than that of the sample plate, or abnormalities such as swelling, peeling, and cracking were observed.
Claims (8)
1. A room-temperature-drying type stain-resistant matte water-based paint composition for buildings, which comprises a water-based resin (A), a pigment component (B) and a glycol ether compound (C),
the glass transition temperature of the resin of the aqueous resin (A) is 10 ℃ or higher, and the copolymerization ratio of the aromatic vinyl compound in the solid content of the aqueous resin (A) is 40 mass% or less,
the pigment component (B) contains an extender pigment (B3) other than the coloring pigment (B1), talc (B2) and (B2),
the contents of the coloring pigment (b1), talc (b2), extender pigment (b3) and glycol ether compound (C) are based on 100 parts by mass of the solid content of the aqueous resin (A),
(b1) is more than 5 parts by mass of the total weight of the composition,
(b2) is more than 50 parts by mass of the total weight of the composition,
(b3) is more than 20 parts by mass of the total weight,
(C) the pigment volume concentration is more than 35% within the range of 5-25 parts by mass.
2. The stain-resistant matte aqueous coating composition according to claim 1, wherein the aqueous resin (A) has a hydrolyzable silyl group.
3. The stain-resistant matte aqueous coating composition according to claim 1 or 2, wherein the total amount of oil absorption with respect to the pigment component (B) is 80ml or less per 100 parts by mass of the solid content of the aqueous resin (a).
4. The stain-resistant matte waterborne coating composition of any one of claims 1 to 3, further comprising a light stabilizer.
5. The stain-resistant matte aqueous coating composition according to any one of claims 1 to 4, wherein the press-in hardness for forming a coating film is 5N/mm or more.
6. A method for forming a pollution-resistant matte coating film, characterized by coating a substrate surface with the pollution-resistant matte aqueous coating composition according to any one of claims 1 to 5.
7. A method for forming a contamination-resistant matte coating film, comprising applying an undercoating material having a coating film elongation of 50% or more to a substrate surface, and applying the contamination-resistant matte aqueous coating composition according to any one of claims 1 to 5.
8. A coated article obtained by the method of claim 6 or 7.
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| CN201510489689.3A CN105368239A (en) | 2014-08-12 | 2015-08-11 | Pollution resistant matting aqueous paint composition and forming method thereof |
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| JP2019519642A (en) * | 2016-05-24 | 2019-07-11 | ビーエーエスエフ コーティングス ゲゼルシャフト ミット ベシュレンクテル ハフツングＢＡＳＦ Ｃｏａｔｉｎｇｓ ＧｍｂＨ | Coating compositions with improved stain resistance and (self) cleaning properties and coatings produced therefrom and methods of using them |
| CN106118327A (en) * | 2016-06-30 | 2016-11-16 | 遵义市恒新化工有限公司 | A kind of building external paint and preparation method thereof |
| JP6668489B2 (en) * | 2016-09-23 | 2020-03-18 | 積水化成品工業株式会社 | Polymer particle dispersion, polymer particles used therefor, dispersant and dispersion medium, and uses thereof |
| JP6978214B2 (en) * | 2017-03-24 | 2021-12-08 | 株式会社日本触媒 | Film forming aid and paint containing this film forming aid |
| JP2020097708A (en) * | 2018-12-19 | 2020-06-25 | 関西ペイント株式会社 | Aqueous coating composition |
| CN109735249B (en) * | 2018-12-27 | 2021-04-30 | 合肥乐凯科技产业有限公司 | Matte paint protective film |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1121514A (en) * | 1997-06-30 | 1999-01-26 | Kansai Paint Co Ltd | Water-based flat coating material and process for finish coating therewith |
| CN1236380A (en) * | 1996-09-06 | 1999-11-24 | 奥里卡澳大利亚有限公司 | Stain resistant water-borne coating composition |
| CN1517373A (en) * | 2003-01-13 | 2004-08-04 | 广州宏昌胶粘带厂 | Composition of elastic organic silicon phenylpropyl resin emulsion for paint and its preparation method |
| CN101333408A (en) * | 2007-06-29 | 2008-12-31 | 关西涂料株式会社 | Aqueous primer composition and coating method using the composition |
| US20100255328A1 (en) * | 2007-12-12 | 2010-10-07 | Yasuhiro Tomizaki | Water-based paint compositions |
| CN102702909A (en) * | 2012-06-06 | 2012-10-03 | 吉林大学 | Aqueous anti-stone-bumping automobile prime coat material and preparation method thereof |
| CN103183995A (en) * | 2013-03-18 | 2013-07-03 | 福建省利得彩环保科技有限公司 | Water-based paint composition |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3119684B2 (en) * | 1991-07-24 | 2000-12-25 | 旭硝子株式会社 | Aqueous dispersion |
| JP4695829B2 (en) * | 2002-12-27 | 2011-06-08 | エスケー化研株式会社 | Water-based paint composition |
| JP2005075839A (en) * | 2003-08-29 | 2005-03-24 | Suzuka Fine Co Ltd | Coating composition |
| JP5121152B2 (en) * | 2005-07-07 | 2013-01-16 | エスケー化研株式会社 | Painting method |
| CN101346445B (en) * | 2005-12-27 | 2012-07-04 | Sk化研株式会社 | Coating agent |
| JP5405791B2 (en) * | 2008-04-22 | 2014-02-05 | アイカ工業株式会社 | Water-based coating composition |
| CN101812260B (en) * | 2010-04-12 | 2013-07-03 | 中华制漆（深圳）有限公司 | Multifunctional water-based white primer and preparation method thereof |
| JP5470314B2 (en) * | 2010-09-29 | 2014-04-16 | 日本ペイント株式会社 | Water-based paint composition |
| CN102153949B (en) * | 2011-01-30 | 2013-11-20 | 上海三瑞化学有限公司 | As-cast finish concrete simulated coating |
| WO2013108880A1 (en) * | 2012-01-18 | 2013-07-25 | 三菱レイヨン株式会社 | Method for producing vinyl polymer and resin composition for water-based antifouling paint containing vinyl polymer |
| MY167572A (en) * | 2012-02-28 | 2018-09-20 | Kaneka Corp | Coating composition and coating film obtained from coating composition |
-
2014
- 2014-08-12 JP JP2014164409A patent/JP6351035B2/en not_active Ceased
-
2015
- 2015-08-06 MY MYPI2015702586A patent/MY181333A/en unknown
- 2015-08-11 CN CN201510489689.3A patent/CN105368239A/en active Pending
- 2015-08-11 CN CN202110985691.5A patent/CN113652134B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1236380A (en) * | 1996-09-06 | 1999-11-24 | 奥里卡澳大利亚有限公司 | Stain resistant water-borne coating composition |
| JPH1121514A (en) * | 1997-06-30 | 1999-01-26 | Kansai Paint Co Ltd | Water-based flat coating material and process for finish coating therewith |
| CN1517373A (en) * | 2003-01-13 | 2004-08-04 | 广州宏昌胶粘带厂 | Composition of elastic organic silicon phenylpropyl resin emulsion for paint and its preparation method |
| CN101333408A (en) * | 2007-06-29 | 2008-12-31 | 关西涂料株式会社 | Aqueous primer composition and coating method using the composition |
| US20100255328A1 (en) * | 2007-12-12 | 2010-10-07 | Yasuhiro Tomizaki | Water-based paint compositions |
| CN102702909A (en) * | 2012-06-06 | 2012-10-03 | 吉林大学 | Aqueous anti-stone-bumping automobile prime coat material and preparation method thereof |
| CN103183995A (en) * | 2013-03-18 | 2013-07-03 | 福建省利得彩环保科技有限公司 | Water-based paint composition |
Non-Patent Citations (1)
| Title |
|---|
| 王锡娇著: "《涂料与颜料标准应用手册 上》", 30 April 2005, 军事谊文出版社 * |
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| CN105368239A (en) | 2016-03-02 |
| MY181333A (en) | 2020-12-21 |
| JP2016040349A (en) | 2016-03-24 |
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