CN109896776B - Stone paint composition - Google Patents
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- CN109896776B CN109896776B CN201811513486.3A CN201811513486A CN109896776B CN 109896776 B CN109896776 B CN 109896776B CN 201811513486 A CN201811513486 A CN 201811513486A CN 109896776 B CN109896776 B CN 109896776B
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Abstract
The invention relates to a stone paint composition, which is characterized by comprising a latex emulsion, cellulose ether, sand and water, wherein the cellulose ether contains hydroxyalkyl alkyl cellulose and hydroxyalkyl cellulose which are in crosslinking combination in a weight ratio of 70-99. According to the present invention, a stone paint composition having satisfactory levels of physical properties such as dispersibility and storage stability and excellent in water resistance and spray workability can be provided.
Description
Technical Field
The present specification claims the benefit of the application date of korean patent application No. 10-2017-016986, which was filed on 11.12.2017 to the korean patent office, the entire contents of which are incorporated herein by reference. The present invention relates to a Stone paint composition (Stone paint composition), and more particularly, to a Stone paint composition having excellent physical properties such as water resistance and spray workability by containing cellulose ether containing hydroxyalkyl alkylcellulose and hydroxyalkyl cellulose in a specific weight ratio.
Background
In general, expensive natural marble, granite, or the like is widely used as interior, exterior, or floor finishing materials of buildings in order to impart a high-grade feel to the buildings. Such natural marbles or granite exhibit high decorativeness and a high-grade atmosphere due to various types of beautiful colors and patterns. However, the finishing materials for interior and/or exterior of buildings using natural marble or granite have the following problems: not only is the material itself expensive, but the transportation and construction costs are high due to the heavy weight.
As one of economical solutions to such problems, stone paint has been proposed. The stone paint is a multi-color pattern paint having a composite color in which two or more colors are mixed to exhibit various colors, and can exhibit high-grade patterns and textures such as natural granite or marble having various types of beautiful colors and patterns. Further, the stone paint can be simply and easily coated by a general coating apparatus, and thus can exhibit texture like natural stone by an economical and effective method, and thus is widely used in the field of construction and construction.
For example, as a conventional art for a coating composition capable of exhibiting the pattern of a natural marble, patent document 1 (korean registered patent No. 10-0912387) describes a coating composition comprising an acrylic emulsion, quartz sand, an acrylic sheet, a mica sheet, an additive and water. Patent document 1 describes that a coating composition capable of expressing the beautiful appearance of natural marble can be provided by including natural stone materials and polymer resin sheets of various sizes and colors in the coating material. However, the coating composition provided by patent document 1 has disadvantages of reduced workability, storage stability, and water resistance.
The addition of cellulose derivatives as thickeners to compositions of mineral varnish is thus considered. The cellulose derivative exerts an effect of imparting physical properties such as thickening property, water retentivity, rheology improvement, etc. to the mineral varnish.
As a conventional technique for the above-mentioned mineral varnish containing a cellulose derivative, patent document 2 (korean laid-open patent No. 10-2005-0024076) describes a multicolor pattern coating composition comprising an inner phase composition and an outer phase composition, the inner phase composition being prepared by mixing water, a cellulose-based thickener, a dispersant, a polymeric pigment dispersant, titanium dioxide (TiO) 2 ) Mica (Mica), calcium carbonate (CaCO) 3 ) Clay (Clay), acrylic acid-styrene emulsion as emulsion resin, urethane thickener, clay thickener, coagulant, defoamer, pH regulator, preservative, antibacterial agent; the outer phase composition is produced by mixing water, a pH adjuster, a synthetic clay mineral, a thickener, a urethane thickener, barium sulfate, a carboxylated styrene acrylate copolymer, a preservative, butyl benzyl phthalate, and a defoaming agent.
In general, hydroxyethyl cellulose is mainly used as a cellulose-based thickener in a multicolor pattern paint, i.e., a stone paint. However, since such a stone paint has a low water resistance although it is excellent in workability, there is a disadvantage that a water-whitening phenomenon (water-whitening) occurs in which the appearance becomes white when the coated object after coating is exposed to rain or water, and there is a problem that the dispersibility and the storage stability are also lowered.
As a conventional method for solving such a problem, patent document 3 (WO 2016036642 A1) describes a stone paint containing latex emulsion (latex emulsion), a rheology modifier (cellulose ether), a coating film formation aid, an antibacterial agent (biocide), a neutralizer, a solvent, and sand, and examples of the rheology modifier (cellulose ether) include methyl hydroxyethyl cellulose (MHEC), methyl hydroxypropyl cellulose (MHPC), methyl Cellulose (MC), and a combination thereof. According to patent document 3, a stone paint improved in water whitening (water whitening) phenomenon can be provided, but the stone paint has a disadvantage that the spray workability, dispersibility, and storage stability are deteriorated.
Therefore, it is a real situation that research is required for a cellulose ether for stone paint which has dispersibility and storage stability of a certain level or more required for stone paint and can impart excellent water resistance to avoid a water whitening phenomenon and at the same time can impart excellent spray workability.
Documents of the prior art
Patent document
Patent document 1: KR 100912387B
Patent document 2: KR 1020050024076A
Patent document 3: WO2016036642 A1
Disclosure of Invention
Problems to be solved
The present invention provides a stone paint composition having satisfactory levels of dispersibility and storage stability and excellent water resistance and spray workability by comprising a cellulose ether containing a hydroxyalkyl alkylcellulose bonded by crosslinking and a hydroxyalkyl cellulose bonded by crosslinking in a weight ratio of 70 to 99.
Means for solving the problems
In order to solve the above problems, the present invention provides a stone paint composition comprising a latex emulsion, a cellulose ether, sand and water, wherein the cellulose ether contains a hydroxyalkyl alkylcellulose to be crosslinked and a hydroxyalkyl cellulose to be crosslinked at a weight ratio of 70 to 99.
The cross-linked hydroxyalkyl alkylcellulose may include at least one of cross-linked Hydroxypropyl methylcellulose (HPMC) and cross-linked Hydroxyethyl methylcellulose (HEMC).
The cross-linked hydroxypropylmethylcellulose may have a methyl substitution rate of 5 to 24 wt% and a hydroxypropyl substitution rate of 3 to 10 wt%, the cross-linked hydroxyethylmethylcellulose may have a methyl substitution rate of 5 to 25 wt% and a hydroxyethyl substitution rate of 3 to 10 wt%, and the cross-linked hydroxyethylcellulose may have a hydroxyethyl substitution rate of 40 to 80 wt%.
The cross-linked hydroxyalkyl alkylcellulose and the cross-linked hydroxyalkyl cellulose may be cross-linked with each other using an aldehyde compound as a medium, and the content of the aldehyde compound (moiey) contained in the cross-linked hydroxyalkyl alkylcellulose and the cross-linked hydroxyalkyl cellulose may be 0.001 to 0.06 wt%, based on 100 wt% of the sand.
The cellulose ether may be contained in an amount of 0.1 to 1.0% by weight based on the total weight of the stone paint composition.
The latex emulsion may include one or more selected from the group consisting of an acrylic emulsion and a vinyl acetate emulsion.
The content of the sand may be 60 to 90 wt% and the particle size of the sand may be 0.01 to 1.0mm, based on the entire weight of the stone paint composition.
The stone paint composition of the present invention may further comprise one or more additives selected from the group consisting of wetting agents, dispersing agents, defoaming agents, antifreezing agents, preservatives, pH adjusters, and coating film forming aids.
Effects of the invention
The stone paint composition of the present invention can provide a stone paint composition having satisfactory levels of physical properties such as dispersibility and storage stability and excellent in water resistance and spray workability by containing a cellulose ether containing a hydroxyalkyl alkylcellulose and a hydroxyalkyl cellulose bound by crosslinking at a weight ratio of 70 to 99.
Detailed Description
The invention relates to a stone paint composition comprising a latex emulsion, a cellulose ether, sand and water, characterized in that the cellulose ether comprises a cross-linked hydroxyalkyl alkylcellulose and a cross-linked hydroxyalkyl cellulose in a weight ratio of 70 to 99.
In the case where the non-crosslinked hydroxyalkyl alkylcellulose or the non-crosslinked hydroxyalkyl cellulose is contained as the above-mentioned cellulose ether, there is provided a stone paint composition which is lowered in dispersibility, may cause problems such as generation of lumps (lumps), and remarkably lowered in storage stability. Further, even when the cellulose ether to be crosslinked is used, if the weight ratio of the hydroxyalkyl alkylcellulose to be crosslinked and contained in the cellulose ether to the hydroxyalkyl alkylcellulose to be crosslinked is out of the above range, there is a problem that a paint composition having at least one of very poor physical properties of water resistance and spray workability is obtained.
For example, a stone paint composition containing only a hydroxyalkyl alkylcellulose in a crosslinking bond has a problem of remarkably reduced spray workability although it is excellent in water resistance and viscosity efficiency. Further, a stone paint containing only the hydroxyalkyl cellulose in a crosslinked state has a problem that the water resistance and the viscosity efficiency are lowered although the spraying workability is excellent. In this way, when at least one of the water resistance and the spray workability does not exhibit physical properties at a certain level or more, the composition cannot be suitably used for a stone paint application.
The weight ratio of the cross-linked hydroxyalkyl alkylcellulose to the cross-linked hydroxyalkyl cellulose of the present invention is 70 to 99. Specifically, the above weight ratio may be 75 to 90. When the components are mixed in such a weight ratio and used as a thickener for stone paint, a stone paint composition which is excellent in water resistance without generating a water-whitening phenomenon, is excellent in spray workability, and exhibits satisfactory levels of thickening properties, other physical properties such as color reducing power, dispersibility, and storage stability, can be provided.
The cross-linked hydroxyalkyl alkylcellulose may include at least one of cross-linked Hydroxypropyl methylcellulose (HPMC) and cross-linked Hydroxyethyl methylcellulose (HEMC). In the hydroxyalkyl alkylcelluloses and hydroxyalkylcelluloses, the hydroxyalkyl group may be a C1-C6 hydroxyalkyl group, specifically a C1-C3 hydroxyalkyl group, more specifically a hydroxyethyl group or a hydroxypropyl group. Further, the alkyl group may be a C1-C6 alkyl group, specifically a C1-C3 alkyl group, and more specifically a methyl group.
The cross-linked hydroxypropylmethylcellulose may have a methyl substitution rate of 5 to 24% by weight and a hydroxypropyl substitution rate of 3 to 10% by weight, the cross-linked hydroxyethylmethylcellulose may have a methyl substitution rate of 5 to 25% by weight and a hydroxyethyl substitution rate of 3 to 10% by weight, and the cross-linked hydroxyethylcellulose may have a hydroxyethyl substitution rate of 40 to 80% by weight. In the case of the cellulose ether having a methyl group, a hydroxypropyl group, and a hydroxyethyl group substitution ratio within the above-mentioned ranges, it is preferable to add the cellulose ether in the weight ratio of the present invention because the stone paint composition can be provided with excellent water resistance and spray workability.
The term "substitution ratio" refers to the ratio of the sum of the atomic weights of the elements constituting each substituent (R) to the sum of the atomic weights of the elements constituting the repeating units of the substituted cellulose as shown in the following chemical formula 1.
Chemical formula 1
In the formula, R is respectively-H and CH independently 3 、-CH 2 CH 2 OH or-CH 2 CHOHCH 3 And n is an integer of 1 or more.
In the present specification, the hydroxyalkyl alkylcellulose to be crosslinked and the hydroxyalkyl cellulose to be crosslinked may be obtained by crosslinking and bonding the hydroxyalkyl alkylcellulose and the hydroxyalkyl cellulose, respectively, with an aldehyde compound as a medium. That is, the crosslinked hydroxyalkyl alkylcellulose or the crosslinked hydroxyalkyl cellulose can be obtained by chemically modifying the hydroxyalkyl alkylcellulose or the hydroxyalkyl cellulose with an aldehyde compound.
The aldehyde compound may include glyoxal (glyoxal), polyglycolide (polyglyoxal), formaldehyde (formaldehyde), pyruvaldehyde (pyruvaldehyde), malonaldehyde (malonaldehyde), succinaldehyde (succinaldehyde), or a combination thereof.
Specifically, the method of crosslinking and bonding the hydroxyalkyl alkylcellulose and the cellulose ether such as the hydroxyalkyl cellulose includes the following methods: a method of adding an aldehyde compound to a moist cellulose ether after synthesis and before pulverization, and pulverizing the resultant mixture after heat treatment; and a method of adding a liquid aldehyde compound to dried and pulverized powdered cellulose ether and performing heat treatment. Examples of the method for crosslinking and bonding the wet cellulose ether include the following methods: spraying liquid aldehyde compound onto the cellulose ether in the rotating state while rotating the cellulose ether in the wet state at high speed, and then performing heat treatment and pulverizing.
The cellulose ether subjected to the above-mentioned crosslinking-bonding process may contain an aldehyde compound moiety. The cross-linked hydroxyalkyl alkylcellulose and the cross-linked hydroxyalkyl cellulose may each contain 1.0 to 3.0% by weight of an aldehyde moiety. When the content of the aldehyde compound portion is within the above range, a mineral varnish which is not expensive to produce and is industrially usable, that is, a mineral varnish having excellent physical properties such as storage stability, dispersibility, color development characteristics, uniform coating film formation ability, and workability can be obtained.
The content of the aldehyde compound moiety in the above-mentioned crosslinked cellulose ether can be calculated according to the following numerical formula 1.
Mathematical formula 1
Content of aldehyde moiety (% by weight) = { total weight of aldehyde moiety/total weight of cross-linked cellulose ether } × 100
Further, the content of the aldehyde compound portion contained in the crosslinked hydroxyalkyl alkylcellulose and the crosslinked hydroxyalkyl cellulose may be 0.001 to 0.06 wt%, specifically 0.001 to 0.02 wt%, respectively, based on 100 wt% of the sand. When the content of the aldehyde compound is within the above range, a paint stone composition having dispersibility and storage stability at a level required for paint stone and excellent water resistance and spray workability can be obtained. More specifically, when the content of the aldehyde compound portion may be 0.001 to 0.009 wt% based on 100 wt% of the sand, an optimal paint composition excellent in all of thickening properties, water resistance, color reducing power, spray workability, dispersibility, and storage stability can be provided.
On the other hand, the content of the cellulose ether may be 0.1 to 1.0% by weight, specifically 0.15 to 0.8% by weight, and further 0.2 to 0.6% by weight, based on the total weight of the stone paint composition. When the content of the cellulose ether is within the above range, an economical stone paint composition having excellent physical properties such as water resistance and spray workability can be provided.
The latex emulsion contained together with the cellulose ether as a constituent component of the stone paint composition of the present invention is a binder resin which adheres to a coating object such as general concrete or mortar to form a coating film which is cured by volatilization of water at normal temperature.
The latex emulsion may include one or more selected from the group consisting of an acrylic emulsion and a vinyl acetate emulsion. Such an acrylic emulsion or a vinyl acetate emulsion can be produced by emulsion-polymerizing an acrylic monomer composition or a vinyl acetate monomer composition in an aqueous medium (e.g., water) in the presence of a polyvinyl alcohol.
The polyvinyl alcohol-based material may include an anion-modified polyvinyl alcohol such as a sulfonic acid-modified polyvinyl alcohol, a carboxylic acid-modified polyvinyl alcohol, or a combination thereof.
The acrylic monomer composition may include an acrylic monomer, and the vinyl acetate monomer composition may include a vinyl acetate monomer. The acrylic monomer composition and the vinyl acetate monomer composition may further contain other components.
The vinyl acetate monomer may include vinyl acetate, and the acrylic monomer may include ethyl acrylate, ethyl methacrylate, methyl acrylate, methyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, cyclohexyl acrylate, alkoxyethyl acrylate, or a combination thereof.
The other component may contain a monomer copolymerizable with each of the vinyl acetate monomer and the acrylic monomer (e.g., divinylbenzene, divinyl adipate, ethylene glycol di (meth) acrylate, and diethylene glycol di (meth) acrylate); water-soluble oligomers (e.g., 2-methacrylamide-2-methylpropanesulfonic acid copolymer, sodium methacrylate-4-styrenesulfonate copolymer, polyvinylpyrrolidone, poly (meth) acrylate salt); polymerization initiators (e.g., potassium persulfate, sodium persulfate, ammonium persulfate, hydrogen peroxide); polymerization regulators (e.g., methanol, ethanol, propanol, acetone, dodecyl mercaptan); emulsifiers (e.g., sodium lauryl sulfate) and combinations thereof.
The latex emulsion may be contained in an amount in the range generally used in the art, and specifically, may be contained in an amount in the range of 10 to 40 wt% with respect to the weight of the entire stone paint composition. In the case where the content of the latex emulsion is within the above range, a high-quality stone paint excellent in coating film formation ability and durability can be provided.
In the present invention, the sand is added to impart a pattern and texture such as natural granite or marble, and two or more kinds of sand having different colors from each other may be used, and sand having different particle sizes from each other may be blended.
The sand may be used without limitation as long as it is generally used in the art, and may include, for example, natural sand, artificial sand, reclaimed sand, or a combination thereof. The sand may include color sand (stone sand), quartz sand (quartz sand), or a combination thereof, and may be used by combining sand having various colors such as black sand, gray sand, white sand, and red sand, thereby exhibiting various textures and colors.
The content of the sand may be 60 to 90% by weight based on the entire weight of the stone paint composition. If the content of the sand is within the above range, the sand can be uniformly dispersed in the stone paint, and a high-quality coating film free from the problem of sand falling off at the contact interface which may occur when a coating film is formed can be obtained.
The sand may have a particle size of 0.01 to 1.0mm, and sand having various sizes within the above range may be used in combination. In the case of sand having a particle size within the above range, a high-quality coating film can be obtained which is excellent in visibility and which is free from the problem of sand falling at the contact interface when the coating film is formed.
As described above, the stone paint composition of the present invention can exhibit various colors and textures of natural stone by using sands having various colors and particle sizes in combination.
The content of water used in the stone paint composition of the present invention may be within the content range generally used in the art, and specifically, may be in the range of 5 to 50% by weight with respect to the entire weight of the stone paint composition. In the case where the above-mentioned water content is within the above-mentioned range, the powder-form material used as the raw material for the stone paint can be sufficiently dispersed, and the thickening effect can be improved, and therefore, it is preferable.
In addition, the stone paint composition of the present invention may further comprise one or more additives selected from the group consisting of wetting agents, dispersing agents, defoaming agents, antifreezing agents, preservatives, pH adjusters, and coating film forming aids. The content of the additive is not particularly limited, but may be 0.1 to 10% by weight based on the total weight of the paint composition.
Specifically, as the wetting agent, wetting agents generally used in the art may be used without limitation, and examples thereof include Carbowet 106 from Air products (Air products), BYK-3400 from ALTANA (ALTANA), and TRITON from DOW (DOW) TM CF-10 or a combination thereof.
As the above-mentioned dispersant, a dispersant generally used in the art may be used without limitation, and for example, sodium citrate, calcium stearate, zinc stearate, distearyldimethylammonium chloride, or a combination thereof may be contained.
As the above-mentioned defoaming agent, defoaming agents generally used in the art may be used without limitation, and for example, dimethylpolysiloxane, silicone, silica, sorbitan monostearate, silicone resin, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, mineral oil, stearin oxide, or a combination thereof may be contained.
As the above-mentioned antifreezing agent, an antifreezing agent generally used in the art may be used without limitation, and for example, ethylene glycol, propylene glycol, sodium chloride, calcium chloride, or a combination thereof may be contained.
As the preservative, preservatives generally used in the art can be used without limitation, and examples thereof include methyl mercaptan, ethyl mercaptan, 1-propyl mercaptan, 2-propyl mercaptan, butyl mercaptan, tert-butyl mercaptan, amyl mercaptan, coenzyme A, glutathione, cysteine, 2-mercaptoethanol, dithioerythritol, 2-mercaptoindole, transglutaminase, and combinations thereof.
As the pH adjuster, a pH adjuster generally used in the art may be used without limitation, and for example, anhydrous ammonia, ammonium phosphate, dimethylethanolamine, formic acid, sodium bicarbonate, triethylamine, or a combination thereof may be included.
As the coating film forming aid, a coating film forming aid generally used in the art can be used without limitation, and for example, texanol of Eastman chemical company (Eastman chemical company) can be contained TM (2,2,4-trimethyl-1, 3-pentanediol monoisobutyrate), butyl carbitol from Dow, dipropylene glycol butoxy ether from Lyondell Chemical Company, or combinations thereof.
As a method for producing the stone paint composition of the present invention, a generally known method can be used without limitation. For example, a method of charging the latex emulsion, cellulose ether, sand and water into a mixing device such as a mixer, and then mixing them uniformly by stirring can be used.
The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.
Example 1
Using the compositions shown in table 1 below, stone paint compositions were produced.
Specifically, water, an antiseptic, an antifreeze, a coating film formation aid, and an antifoaming agent were first put into a mixer and mixed at 500rpm for 10 minutes. To this, cellulose ether was put and stirred at 900rpm for 10 minutes, then a pH adjuster was put and stirred at 1100rpm for 5 minutes, then a latex emulsion was put and stirred at 1400rpm for 10 minutes, and then colored sand was put and stirred at 900rpm for 15 minutes, thereby producing a uniformly mixed stone paint composition.
At this time, as the cellulose ether, hydroxypropyl methyl cellulose (HPMC) bonded by crosslinking and Hydroxyethyl cellulose (HEC) bonded by crosslinking (meldonia mc-50 US) (lesday microchemical corporation) were usedPrecision chemistry, HECELLOSE TM B100K) at a weight ratio of 90. Wherein the HPMC and the HEC are formed by chemically modifying hydroxypropyl methylcellulose and hydroxyethyl cellulose with glyoxal respectively. The content of glyoxal moiety contained in HPMC was 2.0 wt%, and the content of glyoxal moiety was 0.0055 wt% based on 100 wt% of color sand. The content of glyoxal moiety contained in the HEC was 0.5 wt%, and the content of glyoxal moiety was 0.0014 wt% based on 100 wt% of the colored sand.
Examples 2 to 3
A stone paint composition was produced in the same manner as in example 1, except that the composition was changed to the composition shown in table 1. In this case, the same HPMC and HEC as in example 1 were mixed at the same weight ratio to obtain the cellulose ether.
[ Table 1]
| Form a composition | Example 1 | Example 2 | Example 3 |
| Water (I) | 7.0% by weight | 7.0% by weight | 7.0% by weight |
| Latex-based emulsion | 17.1% by weight | 17.1% by weight | 17.1% by weight |
| PH regulator | 0.1% by weight | 0.1% by weight | 0.1% by weight |
| Preservative | 0.4% by weight | 0.4% by weight | 0.4% by weight |
| Antifreezing agent | 1.0% by weight | 1.0% by weight | 1.0% by weight |
| Defoaming agent | 0.2% by weight | 0.2% by weight | 0.2% by weight |
| Coating film forming aid | 1.0% by weight | 1.0% by weight | 1.0% by weight |
| Color sand (# 20 to #120 mesh) | 73.0% by weight | 72.8% by weight | 72.6% by weight |
| Cellulose ethers | 0.2% by weight | 0.4% by weight | 0.6% by weight |
| Is totaled | 100.0% by weight | 100.0% by weight | 100.0% by weight |
* Latex-based emulsion (latex-based emulsion): acrylic emulsion (Pasteur, acronal S559, acrylic resin content 50 wt%)
* pH adjuster (pH control agent): AMP-95 (ANGUS Co., ltd.)
* Preservative (preservative): troysan 174 (Troy chemical Co., ltd.)
* Antifreeze (anti-freezing agent): ethylene glycol (Dajing Huajin)
* Antifoam (defoamer): SN Defoamer 313K (San Nopco, inc.)
* Coating film formation aid (coalescent): texanol (Istman chemical Co., ltd.)
* Color sand (color sand) #20 mesh (0.864 mm) #120 mesh (0.117 mm): quartz sand (Kyungin Materials)
Examples 4 to 14 and comparative examples 1 to 8
A stone paint composition was produced by the same method and composition as in example 1, except that cellulose ethers mixed in the weight ratios shown in table 2 below were used.
[ Table 2]
| HPMC 2) | HPMC 3) | HPMC 4) | HPMC 5) | HEC 6) | HEMC 7) | NSAT 8) | |
| Amount of crosslinking 1) | 0.5 | 2.0 | 4.0 | 0.0 | 0.5 | 2.0 | 0.0 |
| Example 1 | 0 | 90 | 0 | 0 | 10 | 0 | 0 |
| Example 4 | 0 | 70 | 0 | 0 | 30 | 0 | 0 |
| Example 5 | 0 | 75 | 0 | 0 | 25 | 0 | 0 |
| Example 6 | 0 | 85 | 0 | 0 | 15 | 0 | 0 |
| Example 7 | 0 | 95 | 0 | 0 | 5 | 0 | 0 |
| Example 8 | 0 | 0 | 0 | 0 | 30 | 70 | 0 |
| Example 9 | 0 | 0 | 0 | 0 | 25 | 75 | 0 |
| Example 10 | 0 | 0 | 0 | 0 | 15 | 85 | 0 |
| Example 11 | 0 | 0 | 0 | 0 | 10 | 90 | 0 |
| Example 12 | 0 | 0 | 0 | 0 | 5 | 95 | 0 |
| Example 13 | 70 | 0 | 0 | 0 | 30 | 0 | 0 |
| Example 14 | 0 | 0 | 70 | 0 | 30 | 0 | 0 |
| Comparative example 1 | 100 | 0 | 0 | 0 | 0 | 0 | 0 |
| Comparative example 2 | 0 | 0 | 0 | 0 | 100 | 0 | 0 |
| Comparative example 3 | 50 | 0 | 0 | 0 | 50 | 0 | 0 |
| Comparative example 4 | 30 | 0 | 0 | 0 | 70 | 0 | 0 |
| Comparative example 5 | 0 | 0 | 0 | 0 | 50 | 50 | 0 |
| Comparative example 6 | 0 | 0 | 0 | 50 | 50 | 0 | 0 |
| Comparative example 7 | 0 | 0 | 0 | 0 | 50 | 0 | 50 |
| Comparative example 8 | 0 | 0 | 0 | 70 | 30 | 0 | 0 |
1) Crosslinking amount: the content of glyoxal moiety contained in each of HPMC, HEMC, HEC, and NSAT described in table 2 is shown in% by weight.
2) HPMC: hydroxypropyl methylcellulose (lecytose PMC-50 US), cross-linked, was present in an amount of 0.5 wt.% glyoxal fraction (the amount of the above fraction corresponds to 0.0014 wt.% when based on 100 wt.% sand).
3) HPMC: hydroxypropyl methylcellulose (lecytose PMC-50 US), cross-linked, was present in an amount of 2.0 wt.% glyoxal fraction (the above fraction corresponds to 0.0055 wt.% when based on 100 wt.% sand).
4) HPMC: hydroxypropyl methylcellulose (lochia precision chemical, inc. Of MECELLOSE PMC-50 US) was cross-linked and bound, and the content of glyoxal fraction was 4.0 wt% (corresponding to 0.011 wt% when based on 100 wt% of sand).
5) HPMC: uncrosslinked and bound hydroxypropylmethylcellulose (Lentian Seiki Chemicals, inc., MECELOSE PMC-50U), the glyoxal moiety content was 0% by weight.
6) HEC: cross-linked hydroxyethyl cellulose (Letian Koshi chemical Co., ltd., HECELLOSE) TM B100K), the content of glyoxal moieties was 0.5 wt% (when based on 100 wt% of sand, the content of the moieties corresponded to 0.0014 wt%).
7) HEMC: crosslinked hydroxyethylmethylcellulose (Lentian Seiki Chemicals, mecellose EMB-30 US), the content of glyoxal moieties was 2.0% by weight (the content of the above moieties corresponds to 0.0055% by weight when based on 100% by weight of sand).
8) NSAT: commercially available associative thickeners (Ashland Inc., USA, aquaflow) TM NHS-300)。
< evaluation method >
1. Viscosity of the Stone Lacquer composition (Stormer viscocity, KU)
The viscosities of the stone paint compositions manufactured according to the above examples 1 to 14 and comparative examples 1 to 8 were measured at 23 ℃ using a stormer viscometer (Nordic Scientific), and the results thereof are shown in the following table 3. The thickening property was evaluated as being more excellent as the viscosity number was higher.
2. Water resistance
The stone paint compositions manufactured according to the above examples 1 to 14 and comparative examples 1 to 8 were applied to a fiber cement board (fiber cement board) and dried for 1 day. Next, the dried fiber cement sheet was put into water and the color change of the surface contacting the water was observed with the naked eye. In this case, the water resistance was relatively evaluated in 5 grades as described below, and the smaller the color change, the more excellent the water resistance.
Very good: very excellent, o: excellent, Δ: in general, X: poor, XX: very poor
3. Color reducing power
After the water resistance was observed according to the above evaluation method 2, the fiber cement board was visually observed to reduce the color to the original color when dried again after being exposed to water. In this case, the color reducing power was evaluated in 5 grades as follows, and the smaller the difference between the "color of the cement board before water was poured in the coating and drying process" in the "2. Water resistance" evaluation process and the "color of the cement board after the re-drying process" in the "3. Color reducing power" evaluation method "means that the color reducing power is more excellent.
Very good: very excellent,. Smallcircle: excellent, Δ: in general, X: poor, XX: very poor
4. Spray operability
Using the stone paint compositions manufactured according to the above examples 1 to 14 and comparative examples 1 to 8, the amount of sprayed (spray out) within 5 minutes at the time of spraying operation was visually observed. In this case, the spraying workability was relatively evaluated in 5 steps as follows, and the larger the amount of the above-mentioned spray (spray out) is, the more excellent the spraying workability is.
Very good: very excellent,. Smallcircle: excellent, Δ: in general, X: difference, XX: very poor
5. Dispersibility
After the cellulose ethers mixed at the mixing ratios of examples 1 to 14 and comparative examples 1 to 8 were added to water and stirred, the degree of dispersion of the cellulose ethers in water was visually observed. In this case, the dispersibility is relatively evaluated on a 5-point scale as described below, and the more favorable the dispersibility, the more excellent the dispersibility, the more the cellulose ether is dispersed in water without producing lumps.
Very good: very excellent,. Smallcircle: excellent, Δ: in general, X: poor, XX: very poor
6. Storage stability
The change in viscosity of the stone paint compositions produced in examples 1 to 14 and comparative examples 1 to 8 was measured and confirmed by a viscometer (krebsviscometer from Sheen Instruments Limited) after the compositions were stored for 30 days. In this case, the storage stability was relatively evaluated in 5 grades as described below, and the smaller the difference in viscosity before and after storage, the more excellent the storage stability was.
Very good: very excellent, o: excellent, Δ: in general, X: poor, XX: very poor
[ Table 3]
| Viscosity (KU) | Water resistance | Color reducing power | Operability of spraying | Dispersibility | Storage stability | |
| Example 1 | 100.3 | ○ | ○ | ○ | ○ | ○ |
| Example 2 | 105.4 | ○ | ○ | ○ | ○ | ○ |
| Example 3 | 110.8 | ○ | ○ | ○ | ○ | ○ |
| Example 4 | 102.4 | ◎ | ○ | ○ | ○ | ○ |
| Example 5 | 101.1 | ○ | ◎ | ○ | ○ | ○ |
| Example 6 | 102.1 | ○ | ○ | ○ | ○ | ○ |
| Example 7 | 103.8 | ◎ | ○ | ◎ | ○ | ○ |
| Example 8 | 100.1 | ○ | ○ | ○ | ○ | ○ |
| Example 9 | 101.3 | ○ | ◎ | ○ | ○ | ○ |
| Example 10 | 102.4 | ○ | ○ | ○ | ○ | ○ |
| Example 11 | 104.4 | ○ | ○ | ○ | ○ | ○ |
| Example 12 | 104.3 | ◎ | ○ | ◎ | ○ | ○ |
| Example 13 | 102.7 | ◎ | ○ | ○ | △ | △ |
| Example 14 | 102.1 | ◎ | ○ | ○ | ◎ | △ |
| Comparative example 1 | 104.5 | ○ | △ | XX | △ | △ |
| Comparative example 2 | 97.1 | XX | X | ○ | △ | △ |
| Comparative example 3 | 103.7 | X | X | △ | △ | △ |
| Comparative example 4 | 99.1 | X | X | △ | △ | △ |
| Comparative example 5 | 104.6 | X | X | X | △ | △ |
| Comparative example 6 | 102.1 | ○ | ○ | ○ | XX | XX |
| Comparative example 7 | 73.1 | △ | △ | X | X | X |
| Comparative example 8 | 62.7 | XX | XX | XX | XX | XX |
From the above table 3, it is understood that the stone paint compositions produced in examples 1 to 14 according to the present invention exhibit excellent physical properties at satisfactory levels in terms of thickening properties, water resistance, color reducing power, spray workability, dispersibility and storage stability, and are suitable for use in stone paint applications. On the other hand, in the case of the stone paint compositions produced according to comparative examples 1 to 8, at least one or more of water resistance, color reducing power, spray workability, dispersibility, and viscosity stability, which are physical properties required for stone paints, are remarkably poor, and thus they cannot be used for commercial purposes.
The embodiments disclosed in the present invention are provided for illustration and not for limiting the technical spirit of the present invention, the scope of the present invention should be construed by the scope of the claims, and all technical spirit within the equivalent scope thereof should be construed as being included in the scope of the present invention.
Claims (8)
1. A stone paint composition is characterized by comprising latex emulsion, cellulose ether, sand and water,
the cellulose ether contains a cross-linked hydroxyalkyl alkylcellulose and a cross-linked hydroxyalkyl alkylcellulose in a weight ratio of 70,
the cross-linked hydroxyalkyl alkylcellulose and the cross-linked hydroxyalkyl cellulose are formed by respectively cross-linking and linking the hydroxyalkyl alkylcellulose and the hydroxyalkyl cellulose by taking an aldehyde compound as a medium,
the content of the aldehyde compound portion contained in the crosslinked hydroxyalkyl alkylcellulose and the crosslinked hydroxyalkyl cellulose is 0.001 to 0.06% by weight, respectively, based on 100% by weight of the sand.
2. The stone paint composition as claimed in claim 1, wherein the cross-linked hydroxyalkyl alkylcellulose comprises at least one of cross-linked hydroxypropyl methylcellulose and cross-linked hydroxyethyl methylcellulose, the cross-linked hydroxyalkyl cellulose comprising cross-linked hydroxyethyl cellulose.
3. The stone paint composition as claimed in claim 2, wherein the cross-linked hydroxypropylmethylcellulose has a methyl substitution rate of 5 to 24% by weight and a hydroxypropyl substitution rate of 3 to 10% by weight, the cross-linked hydroxyethylmethylcellulose has a methyl substitution rate of 5 to 25% by weight and a hydroxyethyl substitution rate of 3 to 10% by weight, and the cross-linked hydroxyethylcellulose has a hydroxyethyl substitution rate of 40 to 80% by weight.
4. The stone paint composition as claimed in claim 1, wherein the cellulose ether is present in an amount of 0.1 to 1.0% by weight, based on the total weight of the stone paint composition.
5. The stone paint composition as claimed in claim 1, wherein the latex emulsion comprises one or more selected from the group consisting of acrylic emulsion and vinyl acetate emulsion.
6. The stone-paint composition as claimed in claim 1, wherein the sand is present in an amount of 60 to 90% by weight relative to the total weight of the stone-paint composition.
7. The stone paint composition as claimed in claim 1, wherein the sand has a particle size of 0.01 to 1.0mm.
8. The stone paint composition as claimed in claim 1, further comprising one or more additives selected from the group consisting of wetting agents, dispersants, defoamers, antifreeze agents, preservatives, pH adjusters, and coating film forming aids.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2017-0169676 | 2017-12-11 | ||
| KR20170169676 | 2017-12-11 | ||
| KR10-2018-0148224 | 2018-11-27 | ||
| KR1020180148224A KR20190069298A (en) | 2017-12-11 | 2018-11-27 | Stone paint composition |
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| Publication Number | Publication Date |
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| CN109896776A CN109896776A (en) | 2019-06-18 |
| CN109896776B true CN109896776B (en) | 2022-12-09 |
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| CN101805547A (en) * | 2010-04-07 | 2010-08-18 | 丹尼斯克（张家港）亲水胶体有限公司 | Method for preparing aqueous latex paint by using modified cellulose gum |
| CN102876143A (en) * | 2012-08-31 | 2013-01-16 | 芜湖县双宝建材有限公司 | Marble paint and preparation method thereof |
| CN103602197B (en) * | 2013-11-29 | 2016-02-03 | 江门市华石涂料有限公司 | A kind of true mineral varnish and preparation method thereof |
| CN107141869B (en) * | 2017-04-19 | 2019-08-13 | 广东南天涂料有限公司 | A kind of colorful imitation stone lacquer and preparation method thereof |
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