CN107805437B - Water-based wood paint for color correction and preparation method thereof - Google Patents
Water-based wood paint for color correction and preparation method thereof Download PDFInfo
- Publication number
- CN107805437B CN107805437B CN201711138395.1A CN201711138395A CN107805437B CN 107805437 B CN107805437 B CN 107805437B CN 201711138395 A CN201711138395 A CN 201711138395A CN 107805437 B CN107805437 B CN 107805437B
- Authority
- CN
- China
- Prior art keywords
- water
- aqueous
- emulsion
- acrylic emulsion
- preparing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/10—Homopolymers or copolymers of methacrylic acid esters
- C09D133/12—Homopolymers or copolymers of methyl methacrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Paints Or Removers (AREA)
Abstract
The invention provides a water-based wood paint for color correction and a preparation method thereof, wherein the water-based wood paint comprises the following components in percentage by mass: 15-45 wt% of water-based acrylic emulsion, 45-65 wt% of ethanol, 2-10 wt% of cosolvent and 0-5 wt% of water-based color concentrate; the water-based acrylic emulsion is of a core-shell structure, and a shell layer of the water-based acrylic emulsion is provided with-OH active groups. The water-based wood paint provided by the invention has the characteristics of convenience in construction, good color correction effect and the like.
Description
Technical Field
The invention relates to the field of wood lacquer, in particular to water-based wood lacquer for color modification and a preparation method thereof.
Background
The coating is mainly divided into clear water coating, solid color coating, transparent color coating and special effect coating. Among them, clear water coating is also called transparent coating or natural color coating. Solid-color paint is paint in which the color of the substrate cannot be seen after painting, and includes white and other series of colors. The transparent coating not only changes the color of the wood, but also can see the wood grains. The special effect coating mainly comprises modeling coating, leather imitation, water washing and whitening effect and the like. The transparent color painting is the most common painting style, and the wood grain lines can be revealed through bottom coloring, and the layering sense can be embodied through the color difference of the bottom color and the surface color. The wood ware is protected, meanwhile, the wood ware is endowed with great aesthetic feeling, and an excellent decorative effect is achieved. The transparent color coating is the main coating form in the furniture field, and accounts for about 60 to 70 percent of the total amount of the furniture coating field.
At present, the water-based wood coating can achieve better effects in the aspects of clear water coating, solid color coating and special effect coating, and can basically meet the general requirements of furniture factories. However, in the aspect of transparent color coating, an application bottleneck still exists, and the method is not suitable for the factory-scale production of furniture at present, which undoubtedly hinders the market large-scale application of the water-based wood coating.
At present, the main problems of the water-based wood coating when applied to transparent color coating are as follows: the wet film is poor in transparency, the dry film and the wet film have large color difference, and the method is not suitable for the production of contrast color sample plates in furniture factories, so that the operability is reduced, and the construction time is increased; the compatibility with aqueous color concentrates is poor, the color is not easy to be adjusted, particles and residues are caused by adding the aqueous color concentrates, and the operation safety is not high; particles are formed due to paint mist during color correction, so that the color correction effect is influenced; the primer has poor matching performance with single-component and double-component waterborne woodware bottoms, surfaces or solvent-based primers, and has the defects of bottom biting, cracking, poor adhesion and the like; the drying speed is slow, the construction interval time is longer, and the construction efficiency is reduced. Due to the above problems, the development of the application of the waterborne wood coating is greatly limited in recent years. Therefore, the development of the colored coating and the matching product system of the water-based wood coating is an urgent need for the development of the water-based wood coating.
In the field, most of the color-modifying paint products used in the traditional transparent color coating process are solvent-type alkyd resin, non-drying vegetable oil and the like. Among them, patent applications relating to alkyd resin based color correction paints, such as CN 101472686a, require the addition of a diluting solvent in use, and have a bad influence on the health of the workers. While the non-drying vegetable oil products and the water-based modified products thereof have good color spreading effect (documents such as patent applications CN1810898A, CN101608079A, CN101386726A and the like), the problems of slow drying, poor color fixing and color retention, poor compatibility with water-based paint, incapability of being well combined with water-based primer or water-based finish paint, high possibility of color cross and color development in subsequent coating and the like exist. Currently, most of waterborne color-modifying paints adopt polyurethane dispersions, such as the solution disclosed in patent application CN 105440925 a, but have the problems of slow drying speed, poor compatibility with waterborne primers, top coats and solvent-based primers, and poor adhesion. In addition, there is another emulsion type alkali-soluble acrylic emulsion for translucent color correction, such as the solution disclosed in patent application CN 104592828A, but the problems of poor color development, poor water resistance, poor adhesion on solvent-type primer, swelling wood surface, etc. exist, and it is difficult to achieve higher decoration requirements.
Disclosure of Invention
The invention provides the water-based wood paint for color correction and the preparation method thereof, which are used for making up the defects in the prior art.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a water-based wood paint for color correction, which comprises the following components in percentage by mass: 15-45 wt% of water-based acrylic emulsion, 45-65 wt% of ethanol, 2-10 wt% of cosolvent and 0-5 wt% of water-based color concentrate; the water-based acrylic emulsion is of a core-shell structure, and a shell layer of the water-based acrylic emulsion is provided with-OH active groups.
The aqueous wood lacquer adopts the aqueous acrylic emulsion with a core-shell structure and-OH active groups on the shell layer, and the aqueous acrylic emulsion is adopted in the formula system of the invention, so that the compatibility of each component in the formula system can be improved, particularly the compatibility with ethanol and aqueous color concentrates, and the obtained aqueous wood lacquer has good color repairing effect and convenient construction. More preferably, the mass of the-OH active groups in the aqueous acrylic emulsion is 0.1-0.2% of the total mass of the monomers used for preparing the aqueous acrylic emulsion.
According to the water-based wood paint disclosed by the invention, preferably, the lowest film-forming temperature of the water-based acrylic emulsion is 30-50 ℃; the inventors of the present application have found that an aqueous acrylic emulsion having such a minimum film-forming temperature is preferable not only for better hardness but also for film formation without adding a large amount of a film-forming aid; the emulsion with too low minimum film-forming temperature has lower film-forming hardness, and the excessively high minimum film-forming temperature needs to add more film-forming auxiliary agents for film forming.
The water-based wood lacquer disclosed by the invention is preferably used, the core layer of the water-based acrylic emulsion with the core-shell structure has a Tg value of 60-90 ℃, and the shell layer of the water-based acrylic emulsion has a Tg value of 0-20 ℃; the preferable water-based acrylic emulsion is added into the formula system of the water-based wood lacquer and is matched with other components, so that the drying speed of color correction can be increased, and the construction is more convenient.
Preferably, the mass of the core layer of the water-based acrylic emulsion is 30-50% of the total mass of the core layer and the shell layer.
The water-based wood paint disclosed by the invention has the advantages that the solid content of the water-based acrylic emulsion is 35-45 wt%, the use requirement can be met, and the preparation is easy.
Preferably, the aqueous acrylic emulsion is a single-component anionic acrylic polymer emulsion.
In a preferred embodiment of the waterborne wood lacquer, the core layer monomers for preparing the core layer of the waterborne acrylic emulsion comprise methyl methacrylate, butyl acrylate and acrylic acid; further preferably, the mass percentages of the methyl methacrylate, the butyl acrylate and the acrylic acid in the core layer monomer are respectively 40-46%, 4-10% and 0.5-2.5% in sequence based on the total mass of the monomers used for preparing the core layer and the shell layer of the aqueous acrylic emulsion.
In a preferred embodiment of the aqueous wood lacquer, shell monomers used for preparing the shell of the aqueous acrylic emulsion comprise methyl methacrylate, butyl acrylate and hydroxyethyl methacrylate; further preferably, the mass percentages of the methyl methacrylate, the butyl acrylate and the hydroxyethyl methacrylate in the shell layer monomer are respectively 17-24%, 25-32% and 0.5-1.5% in sequence based on the total mass of the monomers used for preparing the core layer and the shell layer of the aqueous acrylic emulsion.
In a further preferred embodiment of the aqueous wood lacquer, the core layer monomer for preparing the core layer of the aqueous acrylic emulsion comprises methyl methacrylate, butyl acrylate and acrylic acid; the shell monomers used for preparing the shell of the aqueous acrylic emulsion comprise methyl methacrylate, butyl acrylate and hydroxyethyl methacrylate. In the aqueous wood lacquer formula system, the aqueous acrylic emulsion prepared by combining and matching the optimized shell layer monomers and the optimized core layer monomers is adopted, so that the compatibility of each component in the formula system with ethanol and aqueous color concentrates can be improved, the color correction drying speed is high, and the construction is convenient; the wood grain color-changing agent has good wettability, uniform color-changing, no flower and no orange peel, can well bring pigment into ducts and grains on the surface of wood during the color-changing process, has uniform color, and can fully improve the color difference and contrast of wood grains; in addition, the paint has excellent adhesion, transparency and water resistance on both water-based primer and solvent-based primer. Further preferably, based on the total mass of the monomers used for preparing the core layer and the shell layer of the aqueous acrylic emulsion, the mass percentages of the methyl methacrylate, the butyl acrylate and the acrylic acid in the core layer monomer are respectively 40-46%, 4-10% and 0.5-2.5%; based on the total mass of monomers used for preparing a core layer and a shell layer of the water-based acrylic emulsion, the mass percentages of methyl methacrylate, butyl acrylate and hydroxyethyl methacrylate in the shell layer monomers are respectively 17% -24%, 25% -32% and 0.5% -1.5% in sequence, and the monomers with the optimal proportion are adopted, so that the emulsion with the optimal lowest film forming temperature can be prepared.
As a specific implementation mode, the aqueous acrylic emulsion with the core-shell structure can be prepared by a two-step emulsion polymerization method, and can be specifically obtained by a two-step dropwise addition reaction. The aqueous acrylic emulsion with the core-shell structure can be obtained by a two-step emulsion polymerization method existing in the field, and in a preferred embodiment, the raw materials for preparing the shell layer of the aqueous acrylic emulsion with the core-shell structure preferably comprise: 0.1-0.5 wt% of emulsifier, 75-80 wt% of shell monomer, 0.1-0.3 wt% of initiator and 20-25 wt% of water (the mass percentages are based on the total mass of shell raw materials); the raw materials used in preparing the core layer of the composite material comprise: 0.1-0.5 wt% of emulsifier, 75-80 wt% of core layer monomer, 0.1-0.3 wt% of initiator and 20-25 wt% of water (the mass percentages are based on the total mass of the core layer raw materials). The following also provides a specific preparation method of the core-shell structure water-based acrylic emulsion by the preferred two-step emulsion polymerization, which comprises the following steps:
preparing a shell layer pre-emulsion: adding an emulsifier accounting for 40-50% of the total mass of the emulsifier used for preparing the shell, water accounting for 5-15% of the total mass of the water used for preparing the shell and a shell monomer into a pre-emulsification kettle for mixing and pre-emulsification for 30-60 min;
preparing a nuclear layer pre-emulsion: adding an emulsifier accounting for 20-40% of the total mass of the emulsifier used for preparing the core layer, water accounting for 5-15% of the total mass of the water used for preparing the core layer and a core layer monomer into another pre-emulsification kettle for mixing and pre-emulsification for 30-60 min;
adding the rest of the emulsifier for preparing the nuclear layer, the rest of the water for preparing the nuclear layer and the pre-prepared 1-10 wt% of the pre-emulsion for the nuclear layer as seed emulsion into a reaction kettle, adding an initiator accounting for 40-60% of the total mass of the initiator for preparing the nuclear layer under stirring when the temperature is raised to 50-90 ℃ to initiate polymerization, wherein the reaction time is 15-60 min;
after the seed emulsion reaction is finished, dropwise adding the rest of the nuclear layer pre-emulsion and the rest of the initiator for preparing the nuclear layer, wherein the dropwise adding time is 1-3 h; after the dripping is finished, preserving the heat for 0.5 to 1 hour;
then, dropwise adding a pre-prepared shell pre-emulsion and an initiator for preparing the shell, wherein the dropwise adding time is 1-3 h; after the dripping is finished, preserving the heat for 0.5 to 3 hours;
cooling to below 45 deg.C, adding neutralizer to neutralize until pH of emulsion is 7-9, filtering and discharging.
The emulsifier, the initiator, the neutralizer and the like used in the preparation of the aqueous acrylic emulsion with the core-shell structure can all adopt corresponding reagents commonly used in the field, and the preparation method is not particularly limited. As a preferred embodiment, the emulsifier used for preparing the aqueous acrylic emulsion with the core-shell structure can be, but is not limited to, one or more of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, fatty alcohol-polyoxyethylene ether and its salt, fatty alcohol ether phosphate and its salt, and the like. The initiator used may be, but is not limited to, one or more of ammonium persulfate, sodium persulfate, and potassium persulfate. The neutralizing agent used may be, but is not limited to, one or more of amines (e.g., ammonia) or alkali metal hydroxides (e.g., sodium hydroxide). The shell monomers used preferably include methyl methacrylate, butyl acrylate and hydroxyethyl methacrylate; the core layer monomers used preferably include methyl methacrylate, butyl acrylate and acrylic acid.
In a preferred embodiment, the waterborne wood lacquer further comprises the following components in percentage by mass: 1.3 to 5.8 weight percent of water-based additive and 1.6 to 35.7 weight percent of deionized water.
In a preferred embodiment of the aqueous wood lacquer, the aqueous auxiliary agent comprises one or more of a defoaming agent, a substrate wetting agent, a leveling agent, a pH regulator, a thickening agent and a bactericide.
In a preferred embodiment of the waterborne wood lacquer, the mass percent of the waterborne color concentrate is 1-5 wt%.
The water-based wood paint disclosed by the invention comprises the following components in percentage by mass in a preferred embodiment: 15-45 wt% of water-based acrylic emulsion, 45-65 wt% of ethanol, 2-10 wt% of cosolvent, 1.3-5.8 wt% of water-based assistant, 1-5 wt% of water-based color concentrate and 1.6-35.7 wt% of deionized water.
In a further preferred embodiment, the aqueous wood lacquer disclosed by the invention comprises the following components in percentage by mass: 20-40 wt% of water-based acrylic emulsion, 50-60 wt% of ethanol, 4-8 wt% of cosolvent, 2.5-4.5 wt% of water-based assistant, 1.5-4.5 wt% of water-based color concentrate and 3-22 wt% of deionized water.
The water-based wood paint disclosed by the invention comprises the following components in percentage by mass in a preferred embodiment: 15-45 wt% of water-based acrylic emulsion, 45-65 wt% of ethanol, 2-10 wt% of cosolvent, 0.1-1 wt% of defoaming agent, 0.3-1 wt% of base material wetting agent, 0.1-0.5 wt% of flatting agent, 0.5-1.5 wt% of pH regulator, 0.2-1.5 wt% of thickening agent, 0.1-0.3 wt% of bactericide, 1-5 wt% of water-based color concentrate and 1.6-35.7 wt% of deionized water.
In a further preferred embodiment, the aqueous wood lacquer disclosed by the invention comprises the following components in percentage by mass: 20-40 wt% of water-based acrylic emulsion, 50-60 wt% of ethanol, 4-8 wt% of cosolvent, 0.2-0.8 wt% of defoaming agent, 0.4-0.8 wt% of base material wetting agent, 0.3-0.4 wt% of flatting agent, 0.55-1.25 wt% of pH regulator, 0.5-1.1 wt% of thickening agent, 0.15-0.25 wt% of bactericide, 1.5-4.5 wt% of water-based color concentrate and 3-22 wt% of deionized water.
In a preferred embodiment of the waterborne wood lacquer, the defoaming agent is polyether siloxane copolymer. As a preferred embodiment, the anti-foaming agent preferably includes, but is not limited to, one or more of Tego-805, Tego-810, Tego-815, Tego-825, Tego-902w, and Tego-1488, all of which are commercially available.
In the water-based wood lacquer, the substrate wetting agent is polyether siloxane copolymer in a preferred embodiment. As a preferred embodiment, the substrate wetting agent preferably includes, but is not limited to, one or more of Byk-346 produced by Picker chemistry, Byk-348, and Surfgnol-104E, Surfgnol-104 BC produced by gas chemistry, and the like;
in a preferred embodiment of the aqueous wood lacquer, the leveling agent is organic modified polydimethylsiloxane. The leveling agent preferably comprises one or more of Tego-410, Tego-450, Tego-245 and the like which are derived from industrial production.
In the preferred embodiment of the aqueous wood lacquer according to the present invention, the pH regulator preferably includes one or more of, but is not limited to, ammonia, ethanolamine, diethanolamine, triethanolamine, N-dimethylethanolamine, triethylamine, 2-amino-2-methyl-1-propanol, sodium hydroxide and potassium hydroxide.
In the water-based wood lacquer, in a preferred embodiment, the thickener is one or more of alkali swelling thickener, polyurethane associative thickener and hydroxyethyl cellulose.
In the aqueous wood lacquer according to the present invention, in a preferred embodiment, the cosolvent preferably includes but is not limited to one or more of dipropylene glycol methyl ether, dipropylene glycol butyl ether, ethylene glycol butyl ether, tripropylene glycol butyl ether, diethylene glycol butyl ether and ethylene glycol hexyl ether, preferably one or both of dipropylene glycol methyl ether and ethylene glycol butyl ether.
The second aspect of the present invention provides a method for preparing the above-mentioned aqueous wood lacquer, comprising the following steps: mixing the aqueous acrylic emulsion and other components, dispersing and filtering. Preferably, the other components are added into the aqueous acrylic emulsion at the dispersion speed of 600-1200r/min, mixed and dispersed for 15-30min, and filtered by a 200-400 mesh filter screen.
"a plurality" of "one or more" as used herein means "two or more".
The technical scheme provided by the invention has the following beneficial effects:
the water-based wood paint provided by the invention is green and environment-friendly, is convenient to construct and has good wettability. The preparation method is simple and easy to implement and convenient to operate.
The waterborne wood lacquer provided by the invention takes the waterborne acrylic emulsion as a film forming material, has good compatibility with other components (particularly ethanol and waterborne color concentrate) in a formula system, can form a uniform and continuous paint film, and provides gloss, hardness and water resistance. The water-based wood paint provided by the invention has excellent color development and quick drying time. The color-repairing effect on the solvent-based primer or the water-based primer is very ideal.
Detailed Description
In order to better understand the technical solution of the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
The part of the assay referred to in the following examples is described below:
solid content, wt%: drying 1g of the emulsion for 30min at 150 ℃, and testing the dry weight;
tg, DEG C: calculating by adopting an FOX formula;
minimum film formation temperature, DEG C, according to GB 9267-2008.
Example 1:
preparation of aqueous acrylic emulsion A:
(1) preparation of the first-step pre-emulsion (core-layer pre-emulsion): respectively adding 240g of methyl methacrylate, 54g of butyl acrylate, 6g of acrylic acid, 1.5g of sodium dodecyl sulfate and 90g of deionized water into a 1L reaction kettle for pre-emulsification for 30 min;
preparation of the second-step pre-emulsion (shell pre-emulsion): respectively adding 114g of methyl methacrylate, 180g of butyl acrylate, 3g of hydroxyethyl methacrylate, 1.5g of sodium dodecyl sulfate and 90g of deionized water into a 1L reaction kettle for pre-emulsification for 30 min;
(2) preparing a seed emulsion: adding 1.2g of sodium dodecyl sulfate, 680g of water and 18g of first-step pre-emulsion (nuclear layer pre-emulsion) which is completely pre-emulsified into a 3L reaction kettle, starting stirring and heating, adding 12g of initiator aqueous solution containing 1.5g of ammonium persulfate when the temperature is raised to 85 ℃ to initiate polymerization, wherein the reaction time is 15 min;
(3) after the seed emulsion reaction is finished, simultaneously dropwise adding the rest of the first-step pre-emulsion (nuclear layer pre-emulsion) and 10g of initiator aqueous solution containing 0.75g of ammonium persulfate, wherein the dropwise adding time is 1.5 h;
(4) after the dropwise addition, the temperature is kept for 0.5 h;
(5) continuously dropwise adding the second-step pre-emulsion (shell layer pre-emulsion) and 10g of initiator aqueous solution containing 0.75g of ammonium persulfate, wherein the dropwise adding time is 1.5 h;
(6) after the dropwise addition, the temperature is kept for 1h, the temperature is reduced to below 45 ℃, ammonia water is used for neutralization, and then the materials are filtered and discharged.
An aqueous acrylic emulsion A having the following characteristic data was obtained:
solid content: 40 wt.% (drying at 150 ℃ for 30min)
Tg: core layer Tg of 60 deg.c, shell layer Tg of 5 deg.c, core layer accounting for 50 wt% of the total mass (based on the total mass of core layer and shell layer),
-OH content: 0.1% by weight (theoretical value, based on the total monomer amount)
Minimum film formation temperature: 30 deg.C
The waterborne wood color-modifying paint is prepared according to the following formula, wherein the following specific weights are all in percentage by mass:
example 2:
preparation of aqueous acrylic emulsion B:
(1) preparation of the first-step pre-emulsion (core-layer pre-emulsion): respectively adding 270g of methyl methacrylate, 24g of butyl acrylate, 6g of acrylic acid, 1.5g of sodium dodecyl sulfate and 90g of deionized water into a 1L reaction kettle for pre-emulsification for 30 min;
preparation of the second-step pre-emulsion (shell pre-emulsion): respectively adding 144g of methyl methacrylate, 150g of butyl acrylate, 3g of hydroxyethyl methacrylate, 1.5g of sodium dodecyl sulfate and 90g of deionized water into a 1L reaction kettle for pre-emulsification for 30 min;
(2) preparing a seed emulsion: adding 1.2g of sodium dodecyl sulfate, 680g of water and 18g of first-step pre-emulsion (nuclear layer pre-emulsion) which is completely pre-emulsified into a 3L reaction kettle, starting stirring and heating, adding 12g of initiator aqueous solution containing 1.5g of ammonium persulfate when the temperature is raised to 85 ℃ to initiate polymerization, wherein the reaction time is 15 min;
(3) after the seed emulsion reaction is finished, simultaneously dropwise adding the rest of the first-step pre-emulsion (nuclear layer pre-emulsion) and 10g of initiator aqueous solution containing 0.75g of ammonium persulfate, wherein the dropwise adding time is 1.5 h;
(4) after the dropwise addition, the temperature is kept for 0.5 h;
(5) continuously dropwise adding the second-step pre-emulsion (shell layer pre-emulsion) and 10g of initiator aqueous solution containing 0.75g of ammonium persulfate, wherein the dropwise adding time is 1.5 h;
(6) after the dropwise addition, the temperature is kept for 1h, the temperature is reduced to below 45 ℃, ammonia water is used for neutralization, and then the materials are filtered and discharged.
An aqueous acrylic emulsion B having the following characteristic data was obtained:
solid content: 40 wt.% (150 ℃/30min)
Tg: core layer Tg of 85 deg.c, shell layer Tg of 20 deg.c, core layer accounting for 50 wt% of the total mass (based on the total mass of core layer and shell layer),
-OH content: 0.1% by weight (theoretical value, based on the total monomer amount)
Minimum film formation temperature: 50 deg.C
The waterborne wood color-modifying paint is prepared according to the following formula, wherein the following specific weights are all in percentage by mass:
| item | Specific gravity of | Function of | Suppliers of goods |
| Aqueous acrylic emulsion B | 30％ | Emulsion and method of making | Wanhua chemistry |
| Ethanol | 55％ | / | / |
| Ethylene glycol butyl ether | 6％ | Cosolvent | Dow |
| Tego-805 | 0.3％ | Defoaming agent | Winning and creating industry |
| Byk-346 | 1％ | Substrate wetting agent | Chemistry of Pico |
| Tego-410 | 0.5％ | Leveling agent | Winning and creating industry |
| Aqueous ammonia | 1％ | pH regulator | Chemical engineering of Hebei rhizoma Ligustici |
| U604 | 1.5％ | Polyurethane associative thickener | Wanhua chemistry |
| KATHON LX150 | 0.1％ | Bactericide | Dow |
| Water-based color essence | 3％ | Colour(s) | Iridescence chemical of color |
| Deionized water | 1.6％ | / | / |
Example 3:
preparation of aqueous acrylic emulsion C:
(1) preparation of the first-step pre-emulsion (core-layer pre-emulsion): respectively adding 180g of methyl methacrylate, 16g of butyl acrylate, 4g of acrylic acid, 1g of sodium dodecyl sulfate and 60g of deionized water into a 1L reaction kettle for pre-emulsification for 30 min;
preparation of the second-step pre-emulsion (shell pre-emulsion): respectively adding 200g of methyl methacrylate, 182g of butyl acrylate, 3g of hydroxyethyl methacrylate, 2g of sodium dodecyl sulfate and 120g of deionized water into a 1L reaction kettle for pre-emulsification for 30 min;
(2) preparing a seed emulsion: adding 1.2g of sodium dodecyl sulfate, 680g of water and 18g of first-step pre-emulsion (nuclear layer pre-emulsion) which is completely pre-emulsified into a 3L reaction kettle, starting stirring and heating, adding 12g of initiator aqueous solution containing 1.5g of ammonium persulfate when the temperature is raised to 85 ℃ to initiate polymerization, wherein the reaction time is 15 min;
(3) after the seed emulsion reaction is finished, simultaneously dropwise adding the rest of the first-step pre-emulsion (nuclear layer pre-emulsion) and 10g of initiator aqueous solution containing 0.75g of ammonium persulfate, wherein the dropwise adding time is 1.5 h;
(4) after the dropwise addition, the temperature is kept for 0.5 h;
(5) continuously dropwise adding the second-step pre-emulsion (shell layer pre-emulsion) and 10g of initiator aqueous solution containing 0.75g of ammonium persulfate, wherein the dropwise adding time is 1.5 h;
(6) after the dropwise addition, the temperature is kept for 1h, the temperature is reduced to below 45 ℃, ammonia water is used for neutralization, and then the materials are filtered and discharged.
An aqueous acrylic emulsion C having the following characteristic data was obtained:
solid content: 40 wt.% (150 ℃/30min)
Tg: core layer Tg of 90 deg.c, shell layer Tg of 20 deg.c, core layer accounting for 33 wt% of the total mass (based on the total mass of core layer and shell layer),
-OH content: 0.1% by weight (theoretical value, based on the total monomer amount)
Minimum film formation temperature: 40 deg.C
The waterborne wood color-modifying paint is prepared according to the following formula, wherein the following specific weights are all in percentage by mass:
example 4:
preparation of aqueous acrylic emulsion D:
(1) preparation of the first-step pre-emulsion (core-layer pre-emulsion): respectively adding 270g of methyl methacrylate, 24g of butyl acrylate, 6g of acrylic acid, 1.5g of sodium dodecyl sulfate and 90g of deionized water into a 1L reaction kettle for pre-emulsification for 30 min;
preparation of the second-step pre-emulsion (shell pre-emulsion): respectively adding 144g of methyl methacrylate, 150g of butyl acrylate, 9g of hydroxyethyl methacrylate, 1.5g of sodium dodecyl sulfate and 90g of deionized water into a 1L reaction kettle for pre-emulsification for 30 min;
(2) preparing a seed emulsion: adding 1.2g of sodium dodecyl sulfate, 680g of water and 18g of first-step pre-emulsion (nuclear layer pre-emulsion) which is completely pre-emulsified into a 3L reaction kettle, starting stirring and heating, adding 12g of initiator aqueous solution containing 1.5g of ammonium persulfate when the temperature is raised to 85 ℃ to initiate polymerization, wherein the reaction time is 15 min;
(3) after the seed emulsion reaction is finished, simultaneously dropwise adding the rest of the first-step pre-emulsion (nuclear layer pre-emulsion) and 10g of initiator aqueous solution containing 0.75g of ammonium persulfate, wherein the dropwise adding time is 1.5 h;
(4) after the dropwise addition, the temperature is kept for 0.5 h;
(5) continuously dropwise adding the second-step pre-emulsion and 10g of initiator aqueous solution containing 0.75g of ammonium persulfate, wherein the dropwise adding time is 1.5 h;
(6) after the dropwise addition, the temperature is kept for 1h, the temperature is reduced to below 45 ℃, ammonia water is used for neutralization, and then the materials are filtered and discharged.
An aqueous acrylic emulsion D having the following characteristic data was obtained:
solid content: 40 wt.% (150 ℃/30min)
Tg: core layer Tg of 85 deg.c, shell layer Tg of 20 deg.c, core layer accounting for 50 wt% of the total mass (based on the total mass of core layer and shell layer),
-OH content: 0.2% by weight (theoretical value, based on the total monomer amount)
Minimum film formation temperature: 50 deg.C
The waterborne wood color-modifying paint is prepared according to the following formula, wherein the following specific weights are all in percentage by mass:
| item | Specific gravity of | Function of | Suppliers of goods |
| Aqueous acrylic emulsion C | 15％ | Emulsion and method of making | Wanhua chemistry |
| Ethanol | 45％ | / | / |
| Dipropylene glycol butyl ether | 2％ | Cosolvent | Dow |
| Tego-805 | 0.3％ | Defoaming agent | Winning and creating industry |
| Byk-346 | 1％ | Substrate wetting agent | Chemistry of Pico |
| Tego-410 | 0.5％ | Leveling agent | Winning and creating industry |
| Aqueous ammonia | 1％ | pH regulator | Chemical engineering of Hebei rhizoma Ligustici |
| U604 | 1.5％ | Polyurethane associative thickener | Wanhua chemistry |
| KATHON LX150 | 0.1％ | Bactericide | Dow |
| Water-based color essence | 5％ | Colour(s) | Iridescence chemical of color |
| Deionized water | 28.6％ | / | / |
The preparation methods of the waterborne wood color-modifying paint of the embodiments 1 to 4 are as follows: firstly, adding the water-based acrylic emulsion into a container, adjusting the dispersion speed to 1000r/min, then sequentially adding the ethanol, the cosolvent, the water-based auxiliary agent, the water-based color concentrate, the deionized water and other residual raw materials, keeping the dispersion speed unchanged after the addition for continuously dispersing for 30min, and filtering by using a 325-mesh filter screen to obtain the water-based wood color-correcting paint.
Comparative example
The aqueous wood refinish paint of the comparative example was prepared according to substantially the same formulation as in example 1, except that the aqueous acrylic emulsion a in the comparative example was replaced with a conventional emulsion (Lacper 4501, core-shell structure, no-OH reactive groups, wanhua chemistry). The comparative example was prepared in the same manner as in example 1.
The aqueous woodenware color-modifying paint prepared in the examples 1 to 4 and the aqueous woodenware color-modifying paint prepared in the comparative example are tested according to GB/T23999-2009< < aqueous woodenware paint for indoor decoration >, and the performance test results are shown in the following table:
as is apparent from the table above, each index of each embodiment of the water-based wood lacquer for color correction of the invention meets the requirements of national standard (GB/T23999-2009); the problems of easy blooming, non-uniformity and poor water resistance of large-area color correction of the water-based wood paint are solved, the adhesive force between a color correction layer and a bottom finish paint is very excellent, the operation is simple, the environment is protected, the safety is realized, and the drying speed is high. The products of the embodiments 1 to 4 of the invention do not gel after being stored for one month at 50 ℃, and the color is evenly repaired without flower and orange peel, and the components of the aqueous acrylic emulsion and the components of ethanol, aqueous color concentrate and the like in the formula system have good compatibility.
It will be appreciated by those skilled in the art that modifications or adaptations to the invention may be made in light of the teachings of the present specification. Such modifications or adaptations are intended to be within the scope of the present invention as defined in the claims.
Claims (21)
1. The water-based wood paint for color correction is characterized by comprising the following components in percentage by mass:
20-45 wt% of water-based acrylic emulsion, 45-65 wt% of ethanol, 2-10 wt% of cosolvent, 0-5 wt% of water-based color concentrate, 1.3-5.8 wt% of water-based auxiliary agent and 1.6-35.7 wt% of deionized water;
the water-based acrylic emulsion is of a core-shell structure, and a shell layer of the water-based acrylic emulsion is provided with-OH active groups;
the mass of-OH active groups in the water-based acrylic emulsion is 0.1-0.2% of the total mass of monomers used for preparing the water-based acrylic emulsion.
2. The aqueous wood lacquer according to claim 1, wherein the core-shell structure aqueous acrylic emulsion has a core layer with a Tg value of 60-90 ℃ and a shell layer with a Tg value of 0-20 ℃.
3. The aqueous wood lacquer according to claim 1, wherein the mass of the core layer of the aqueous acrylic emulsion is 30-50% of the total mass of the core layer and the shell layer.
4. The aqueous wood lacquer according to claim 1, wherein the solid content of the aqueous acrylic emulsion is 35 to 45 wt%.
5. The aqueous wood lacquer according to claim 1, wherein the minimum film forming temperature of the aqueous acrylic emulsion is 30-50 ℃; the water-based acrylic emulsion is a single-component anionic acrylic polymer emulsion.
6. The aqueous wood lacquer according to claim 1, wherein the core layer monomers used for preparing the core layer of the aqueous acrylic emulsion comprise methyl methacrylate, butyl acrylate and acrylic acid.
7. The aqueous wood lacquer according to claim 6, wherein the mass percentages of the methyl methacrylate, the butyl acrylate and the acrylic acid in the core layer monomer are respectively 40-46%, 4-10% and 0.5-2.5% in sequence based on the total mass of the monomers used for preparing the core layer and the shell layer of the aqueous acrylic emulsion.
8. The aqueous wood lacquer according to claim 1, wherein the shell monomers for preparing the shell of the aqueous acrylic emulsion comprise methyl methacrylate, butyl acrylate and hydroxyethyl methacrylate.
9. The aqueous wood lacquer according to claim 8, wherein the mass percentages of the methyl methacrylate, the butyl acrylate and the hydroxyethyl methacrylate in the shell layer monomer are respectively 17-24%, 25-32% and 0.5-1.5% in sequence based on the total mass of the monomers used for preparing the core layer and the shell layer of the aqueous acrylic emulsion.
10. The aqueous wood lacquer according to any one of claims 1 to 9, wherein the aqueous acrylic emulsion with the core-shell structure is prepared by a two-step emulsion polymerization method.
11. The aqueous wood lacquer according to claim 10, wherein the shell layer of the core-shell aqueous acrylic emulsion is prepared from the following raw materials: based on the total mass of raw materials used for preparing the shell layer, 0.1 to 0.5 weight percent of emulsifier, 75 to 80 weight percent of shell layer monomer, 0.1 to 0.3 weight percent of initiator and 20 to 25 weight percent of water.
12. The aqueous wood lacquer according to claim 10, wherein the core-shell structure aqueous acrylic emulsion is prepared from the following raw materials: based on the total mass of raw materials used for preparing the core layer, 0.1 to 0.5 weight percent of emulsifier, 75 to 80 weight percent of core layer monomer, 0.1 to 0.3 weight percent of initiator and 20 to 25 weight percent of water.
13. The aqueous wood lacquer according to claim 10, wherein the preparation of the aqueous acrylic emulsion with the core-shell structure comprises the following steps:
preparing a shell layer pre-emulsion: mixing an emulsifier accounting for 40-50% of the total mass of the emulsifier used for preparing the shell layer, water accounting for 5-15% of the total mass of the water used for preparing the shell layer and a shell layer monomer for pre-emulsification for 30-60 min;
preparing a nuclear layer pre-emulsion: mixing an emulsifier which accounts for 20-40% of the total mass of the emulsifier used for preparing the core layer, water which accounts for 5-15% of the total mass of the water used for preparing the core layer and a core layer monomer for pre-emulsification for 30-60 min;
adding the rest of emulsifier for preparing the nuclear layer, the rest of water for preparing the nuclear layer and 1-10 wt% of the nuclear layer pre-emulsion serving as seed emulsion into a reaction kettle, adding an initiator accounting for 40-60% of the total mass of the initiator for preparing the nuclear layer under stirring when the temperature is raised to 50-90 ℃ to initiate polymerization, wherein the reaction time is 15-60 min;
after the seed emulsion reaction is finished, dropwise adding the rest of the nuclear layer pre-emulsion and the rest of the initiator for preparing the nuclear layer, wherein the dropwise adding time is 1-3 h; after the dripping is finished, preserving the heat for 0.5 to 1 hour;
then, dropwise adding a pre-prepared shell pre-emulsion and an initiator for preparing the shell, wherein the dropwise adding time is 1-3 h; after the dripping is finished, preserving the heat for 0.5 to 3 hours;
cooling to below 45 deg.C, adding neutralizer to neutralize until pH of the emulsion is 7-9.
14. The aqueous wood lacquer according to any one of claims 1 to 9, wherein the aqueous auxiliary agent comprises one or more of a defoamer, a substrate wetting agent, a leveling agent, a pH adjuster, a thickener and a bactericide.
15. The aqueous wood lacquer according to claim 14, wherein the aqueous color concentrate is 1-5 wt% by mass.
16. The aqueous wood lacquer according to any one of claims 1 to 9, wherein the aqueous wood lacquer consists of the following components in percentage by mass: 20-45 wt% of water-based acrylic emulsion, 45-65 wt% of ethanol, 2-10 wt% of cosolvent, 1.3-5.8 wt% of water-based assistant, 1-5 wt% of water-based color concentrate and 1.6-35.7 wt% of deionized water.
17. The aqueous wood lacquer according to claim 16, wherein the aqueous wood lacquer comprises the following components in percentage by mass: 20-40 wt% of water-based acrylic emulsion, 50-60 wt% of ethanol, 4-8 wt% of cosolvent, 2.5-4.5 wt% of water-based assistant, 1.5-4.5 wt% of water-based color concentrate and 3-22 wt% of deionized water.
18. The aqueous wood lacquer according to claim 16, wherein the aqueous wood lacquer comprises the following components in percentage by mass: 20-45 wt% of water-based acrylic emulsion, 45-65 wt% of ethanol, 2-10 wt% of cosolvent, 0.1-1 wt% of defoaming agent, 0.3-1 wt% of base material wetting agent, 0.1-0.5 wt% of flatting agent, 0.5-1.5 wt% of pH regulator, 0.2-1.5 wt% of thickening agent, 0.1-0.3 wt% of bactericide, 1-5 wt% of water-based color concentrate and 1.6-35.7 wt% of deionized water.
19. The aqueous wood lacquer according to claim 16, wherein the aqueous wood lacquer comprises the following components in percentage by mass: 20-40 wt% of water-based acrylic emulsion, 50-60 wt% of ethanol, 4-8 wt% of cosolvent, 0.2-0.8 wt% of defoaming agent, 0.4-0.8 wt% of base material wetting agent, 0.3-0.4 wt% of flatting agent, 0.55-1.25 wt% of pH regulator, 0.5-1.1 wt% of thickening agent, 0.15-0.25 wt% of bactericide, 1.5-4.5 wt% of water-based color concentrate and 3-22 wt% of deionized water.
20. The method for preparing the aqueous wood lacquer according to any one of claims 1 to 19, comprising the following steps: mixing the aqueous acrylic emulsion and other components, dispersing and filtering.
21. The method as claimed in claim 20, wherein the other components are added to the aqueous acrylic emulsion at a dispersion speed of 600-1200r/min, mixed and dispersed for 15-30min, and filtered through a 200-400 mesh filter screen.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711138395.1A CN107805437B (en) | 2017-11-16 | 2017-11-16 | Water-based wood paint for color correction and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711138395.1A CN107805437B (en) | 2017-11-16 | 2017-11-16 | Water-based wood paint for color correction and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107805437A CN107805437A (en) | 2018-03-16 |
| CN107805437B true CN107805437B (en) | 2021-02-02 |
Family
ID=61580746
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711138395.1A Active CN107805437B (en) | 2017-11-16 | 2017-11-16 | Water-based wood paint for color correction and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107805437B (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110551245B (en) * | 2018-06-04 | 2022-01-25 | 阜阳师范学院 | Core-shell emulsion and preparation method thereof |
| CN110551246A (en) * | 2018-06-04 | 2019-12-10 | 阜阳师范学院 | Acrylate emulsion and preparation method thereof |
| CN108948931A (en) * | 2018-06-25 | 2018-12-07 | 安徽华利达户外用品有限公司 | A kind of garden rattan chair durability environ mental protective paint |
| CN109135483A (en) * | 2018-07-02 | 2019-01-04 | 万华化学集团股份有限公司 | A kind of anti-muscle priming paint and preparation method thereof that rises of aqueous wooden ware |
| CN109468044A (en) * | 2018-10-31 | 2019-03-15 | 聂阳含 | A kind of two-component high definition is aqueous to repair coloured gold oil and preparation method thereof |
| CN110172295A (en) * | 2019-04-25 | 2019-08-27 | 合肥科天水性科技有限责任公司 | One kind repairing color composition and its preparation method and application |
| CN110922524B (en) * | 2019-11-19 | 2022-05-03 | 合众（佛山）化工有限公司 | Special water-based acrylic resin for color correction and preparation method thereof |
| CN112718427A (en) * | 2021-01-27 | 2021-04-30 | 上海展辰涂料有限公司 | Coating method for imitating dyed veneer by using water-based paint |
| CN113913068A (en) * | 2021-09-26 | 2022-01-11 | 台州学院 | Water-based wood paint capable of removing formaldehyde |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008038115A (en) * | 2006-08-10 | 2008-02-21 | Asahi Kasei Chemicals Corp | Acrylic aqueous emulsion |
| CN104592828A (en) * | 2014-12-26 | 2015-05-06 | 三棵树涂料股份有限公司 | Water-based wood paint for padding and preparation method thereof |
| CN105237675A (en) * | 2015-10-15 | 2016-01-13 | 三棵树涂料股份有限公司 | Polyacrylic woodware emulsion with core-shell bi-crosslinking structure and preparation method thereof |
| CN106590238A (en) * | 2016-11-09 | 2017-04-26 | 河北晨阳工贸集团有限公司 | Aqueous woodenware statin topcoat and preparation method thereof |
| CN106866869A (en) * | 2017-02-23 | 2017-06-20 | 同光（江苏）新材料科技有限公司 | A kind of preparation method of core shell structure hydroxyl acrylic emulsion |
-
2017
- 2017-11-16 CN CN201711138395.1A patent/CN107805437B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008038115A (en) * | 2006-08-10 | 2008-02-21 | Asahi Kasei Chemicals Corp | Acrylic aqueous emulsion |
| CN104592828A (en) * | 2014-12-26 | 2015-05-06 | 三棵树涂料股份有限公司 | Water-based wood paint for padding and preparation method thereof |
| CN105237675A (en) * | 2015-10-15 | 2016-01-13 | 三棵树涂料股份有限公司 | Polyacrylic woodware emulsion with core-shell bi-crosslinking structure and preparation method thereof |
| CN106590238A (en) * | 2016-11-09 | 2017-04-26 | 河北晨阳工贸集团有限公司 | Aqueous woodenware statin topcoat and preparation method thereof |
| CN106866869A (en) * | 2017-02-23 | 2017-06-20 | 同光（江苏）新材料科技有限公司 | A kind of preparation method of core shell structure hydroxyl acrylic emulsion |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107805437A (en) | 2018-03-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107805437B (en) | Water-based wood paint for color correction and preparation method thereof | |
| CN101205267B (en) | Phosphorous-containing organic polymer and compositions and processes including same | |
| CN100376607C (en) | Latex type hydroxy acryl acid resin possessing core-shell configuration | |
| CN104487509B (en) | Aqueous adhesive composition | |
| CN100387653C (en) | Monocomponent self-cross-linking epoxy acrylic acid composite emulsion , its preparation method and uses | |
| CN100560621C (en) | Filming flow type polyacrylacid ester soap-free emulsion and synthesis technique and the application in printing ink thereof | |
| CN101081957A (en) | Automobile finishing varnish containing water dispersible acrylic ester and preparation method thereof | |
| US20170275407A1 (en) | Finely divided aqueous emulsion polymers and use thereof for hydrophobic coatings | |
| CN105646762A (en) | High-solid-content high-gloss quick-drying water-soluble hydroxy acrylic resin and preparation method thereof | |
| EP2791180B1 (en) | Use of aqueous polymer dispersions for improving resistance to chemical influences | |
| CN108276890B (en) | Water-based automobile intermediate coating composition and preparation method thereof | |
| CN105504137A (en) | Heat and cold resisting water-soluble air-drying acrylic resin and preparing method thereof | |
| CN110982371A (en) | Environment-friendly water-based high-gloss high-fullness high-temperature baking varnish | |
| CN112266677B (en) | Hydroxyl acrylic acid dispersoid and acrylic acid anticorrosive paint | |
| US4016127A (en) | Emulsion copolymers of acrolein and their use in treating leather | |
| CN102226051A (en) | Glaze coloring agent for waterborne woodenware coating and preparation method thereof | |
| CN103012805B (en) | Method for preparing emulsion for self-crosslinked waterborne wood coating | |
| CN102408827B (en) | Aqueous ultraviolet-curing transparent prime coat and preparation method thereof | |
| CN109694639A (en) | A kind of Water-based glass baking paint and preparation method thereof | |
| US6242531B1 (en) | Acrylic aqueous miniemulsion copolymer thickeners and latex paints containing said thickeners | |
| CN104045761B (en) | Dumb light damage resistant water-base resin and its preparation method | |
| JP4121176B2 (en) | Water-based paint composition and coating method using the same | |
| CN110885406B (en) | Preparation method of acrylic emulsion, acrylic emulsion and application thereof | |
| CN111116831B (en) | Preparation method of hydroxyl acrylic emulsion | |
| CN108442141A (en) | A kind of environment-friendly type printing and dyeing special-purpose high temperature foaming slurry and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: The invention relates to an aqueous wood paint for color trimming and a preparation method thereof Effective date of registration: 20211123 Granted publication date: 20210202 Pledgee: Bank of China Limited by Share Ltd. Yantai branch Pledgor: Wanhua Chemical Group Co.,Ltd. Registration number: Y2021980013026 |
|
| PC01 | Cancellation of the registration of the contract for pledge of patent right | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Date of cancellation: 20220622 Granted publication date: 20210202 Pledgee: Bank of China Limited by Share Ltd. Yantai branch Pledgor: Wanhua Chemical Group Co.,Ltd. Registration number: Y2021980013026 |