CN108864401B - Polyurethane acrylate oligomer, preparation method thereof and water-based paint - Google Patents
Polyurethane acrylate oligomer, preparation method thereof and water-based paint Download PDFInfo
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- CN108864401B CN108864401B CN201810689855.8A CN201810689855A CN108864401B CN 108864401 B CN108864401 B CN 108864401B CN 201810689855 A CN201810689855 A CN 201810689855A CN 108864401 B CN108864401 B CN 108864401B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3225—Polyamines
- C08G18/3228—Polyamines acyclic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
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- 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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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Abstract
The invention belongs to the technical field of water-soluble oligomers, and particularly relates to a polyurethane acrylate oligomer, a preparation method thereof and a water-based paint. The polyurethane acrylate oligomer provided by the invention utilizes urea to form a polyurea chain segment, and then forms a hydrogen bond with a three-dimensional network structure through the polyurea chain segment and carboxyl, so that the aim of improving the thixotropy of the coating is fulfilled. The results of the examples show that when the urethane acrylate oligomer provided by the invention is used for water-based paint, the obtained coating has a flat appearance and no obvious sagging, and the glossiness of the coating is more than or equal to 90Gu60 degrees.
Description
Technical Field
The invention belongs to the technical field of water-soluble oligomers, and particularly relates to a polyurethane acrylate oligomer, a preparation method thereof and a water-based paint.
Background
The traditional coating contains volatile organic solvent (VOC), is easy to cause environmental pollution, cannot meet the new requirements of modern society on environment-friendly coatings, and is gradually replaced by ultraviolet curing coatings (UV coatings for short). The UV coating is a volatile organic solvent-free UV coating, has little pollution to the environment and reduces the construction toxicity; the curing speed is high, the curing can be realized by depending on ultraviolet irradiation, and the coating is nonflammable and non-explosive, so that the safety performance of the coating is greatly improved, and the coating becomes a main product for replacing the traditional coating. However, water in the existing UV coating is difficult to volatilize, so that the paint film before photocuring has good fluidity, and sagging is easily generated in the curing process to influence the paint film effect. In order to overcome the sagging problem, the conventional method is to improve the viscosity of the coating by adding a large amount of the sagging prevention agent, so that the sagging problem is eliminated, but the addition of the sagging prevention agent easily causes the reduction of the glossiness of the surface of the paint film.
Disclosure of Invention
The invention aims to provide a polyurethane acrylate oligomer and a preparation method thereof, and a water-based paint and a preparation method thereof.
In order to achieve the above object, the present invention provides a urethane acrylate oligomer polymerized from the following preparation raw materials, wherein the preparation raw materials comprise a main material and an auxiliary agent; the main material comprises diisocyanate, polyester polyol, dimethylolpropionic acid, urea and monohydroxy acrylate; the auxiliary agent comprises a polymerization inhibitor and a catalyst.
Preferably, the diisocyanate comprises one or more of toluene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate and dicyclohexylmethane diisocyanate;
the polyester polyol comprises a polycondensate of a polyol and a dibasic acid; the polyalcohol comprises one or more of dihydric alcohol, trihydric alcohol and tetrahydric alcohol;
the monohydroxy acrylate comprises one or more of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate and hydroxypropyl methacrylate.
Preferably, the mass ratio of the polyester polyol to the diisocyanate is 0.5-0.9: 1;
the mass ratio of the dimethylolpropionic acid to the diisocyanate is 0.12-0.20: 1;
the mass ratio of the urea to the diisocyanate is 0.027-0.042: 1;
the molar ratio of the monohydroxy acrylate to the diisocyanate is 1: 0.5-2.
Preferably, the polymerization inhibitor comprises hydroquinone and/or p-methoxyphenol.
Preferably, the catalyst comprises one or more of dibutyltin laurate, cobalt octoate and zinc naphthenate.
Preferably, the polymerization inhibitor accounts for 0.01-1% of the total mass of the raw materials for preparing the urethane acrylate oligomer; the catalyst accounts for 0.01-1% of the total mass of the raw materials for preparing the urethane acrylate oligomer.
The invention provides a preparation method of the polyurethane acrylate oligomer, which comprises the following steps:
(1) performing polycondensation reaction on a mixture of polyester polyol, dimethylolpropionic acid, urea and diisocyanate to obtain a polyurethane prepolymer;
(2) mixing the polyurethane prepolymer in the step (1) with monohydroxy acrylate and an auxiliary agent, and carrying out condensation reaction to obtain a polyurethane acrylate oligomer; the auxiliary agent comprises a polymerization inhibitor and a catalyst.
Preferably, the temperature of the polycondensation reaction in the step (1) and the condensation reaction in the step (2) is 60-100 ℃ independently; the time of the polycondensation reaction and the condensation reaction is independently 1-3 h.
The invention also provides a water-based paint which comprises 8-30 parts by mass of polyurethane acrylate oligomer, 10-60 parts by mass of reactive diluent, 2-10 parts by mass of photoinitiator, 1-18 parts by mass of paint auxiliary agent and 30-50 parts by mass of water; the urethane acrylate oligomer is the urethane acrylate oligomer in the technical scheme or the urethane acrylate oligomer prepared by the preparation method in the technical scheme.
Preferably, the coating auxiliary agent comprises one or more of a leveling agent, a defoaming agent, an ultraviolet light absorber and a water-based wetting agent;
the active diluent comprises one or more of hexanediol diacrylate, tripropylene glycol diacrylate, trimethylolpropane triacrylate and pentaerythritol tetraacrylate;
the photoinitiator comprises 2-hydroxy-2-methyl-1-phenyl acetone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-acetone, 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide, 2,4, 6-trimethylbenzoyl phenyl ethyl phosphonate, 2-dimethylamino-2-benzyl-1- [4- (4-morpholinyl) phenyl ] -1-butanone and one or more of 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-propanone.
The polyurethane acrylate oligomer provided by the invention is polymerized by the following preparation raw materials, wherein the preparation raw materials comprise a main material and an auxiliary agent; wherein the main materials comprise diisocyanate, polyester polyol, dimethylolpropionic acid, urea and monohydroxy acrylate; the auxiliary agent comprises a polymerization inhibitor and a catalyst. The invention uses urea to form a polyurea chain segment, and then forms a hydrogen bond with a three-dimensional network structure through the polyurea chain segment and carboxyl, thereby achieving the purpose of improving the thixotropy of the coating. The results of the examples show that when the urethane acrylate oligomer is used in a water-based paint, the obtained coating has a smooth appearance and no obvious sagging, and the glossiness of the coating is more than or equal to 90Gu60 degrees.
Detailed Description
The invention provides a polyurethane acrylate oligomer which is polymerized by the following preparation raw materials, wherein the preparation raw materials comprise a main material and an auxiliary agent; the main material comprises diisocyanate, polyester polyol, dimethylolpropionic acid, urea and monohydroxy acrylate; the auxiliary agent comprises a polymerization inhibitor and a catalyst.
The raw materials for preparing the urethane acrylate oligomer comprise main materials, wherein the main materials comprise diisocyanate, the diisocyanate preferably comprises one or more of toluene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate and dicyclohexylmethane diisocyanate, and more preferably isophorone diisocyanate, xylylene diisocyanate or hexamethylene diisocyanate.
The main material of the invention comprises polyester polyol. In the present invention, the polyester polyol includes a polycondensate of a polyol and a dibasic acid. In the present invention, the polyol preferably includes a diol, a triol, or a tetraol; further preferably, the dihydric or trihydric alcohol is included. In the present invention, the diol preferably comprises one or more of ethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 8-octanediol, 1, 9-nonanediol, and 1, 10-decanediol; the triol preferably comprises trimethylolpropane and/or glycerol; the tetrahydric alcohol preferably includes pentaerythritol. When the polyol is a mixture of several components, the mass ratio of the polyol is not particularly required in the invention.
In the present invention, the dibasic acid preferably includes one or more of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid and sebacic acid, and further preferably adipic acid.
In the present invention, the polyester polyol preferably includes a polycondensate of ethylene glycol and adipic acid, a polycondensate of 1, 2-propanediol and adipic acid, a polycondensate of 1, 3-propanediol and adipic acid, a polycondensate of 1, 4-butanediol and adipic acid, a polycondensate of 1, 5-pentanediol and adipic acid, and a polycondensate of 1, 6-hexanediol and adipic acid. In the present invention, the number average molecular weight of the polyester polyol is preferably 500 to 5000, and more preferably 1000 to 3000. In the embodiment of the invention, the polyester polyol is a commercial product with Huafeng group, type PE-1280S and number average molecular weight of 1300.
In the present invention, the mass ratio of the polyester polyol to the diisocyanate is preferably 0.5 to 0.9:1, and more preferably 0.6 to 0.8: 1. The present invention preferably employs the above-defined polyester polyol to facilitate control of the molecular weight and viscosity of the urethane acrylate oligomer.
In the present invention, the main material includes dimethylolpropionic acid. In the present invention, the mass ratio of the dimethylolpropionic acid to the diisocyanate is preferably 0.12 to 0.20:1, and more preferably 0.13 to 0.18: 1. According to the invention, dimethylolpropionic acid is preferably controlled within the range, so that the polyurethane acrylate oligomer can be prevented from being separated out in water, the water-based paint containing the polyurethane acrylate oligomer can be dried and cured easily, and the drying performance of the coating is improved.
In the invention, the main material comprises urea, and the urea is used for providing amide groups, thereby providing a foundation for forming a three-dimensional hydrogen bond network structure. In the present invention, the mass ratio of urea to diisocyanate is preferably 0.027 to 0.042:1, and more preferably 0.028 to 0.040: 1. The urea content is preferably controlled within the above range in the present invention, so that gelation of the urethane acrylate oligomer due to excessive viscosity can be avoided.
In the invention, the main material comprises monohydroxy acrylate, and the molar ratio of the monohydroxy acrylate to diisocyanate is preferably 1: 0.5-2; more preferably 1:1.0 to 1.5. In the present invention, the monohydroxy acrylate preferably includes one or more of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate and hydroxypropyl methacrylate, and more preferably hydroxyethyl acrylate. When the monohydroxy acrylate is a mixture of several components, the invention has no special requirements on the mass ratio of the components in the mixture. In the invention, the monohydroxy acrylate can be subjected to condensation reaction with isocyanate groups in the polyurethane prepolymer.
The raw materials for preparing the urethane acrylate oligomer also comprise an auxiliary agent, wherein the auxiliary agent comprises a polymerization inhibitor and a catalyst. In the present invention, the polymerization inhibitor preferably includes hydroquinone and/or p-methoxyphenol, and is further preferably hydroquinone; the polymerization inhibitor preferably accounts for 0.01-1% of the total mass of the raw materials for preparing the urethane acrylate oligomer, and more preferably accounts for 0.1-0.5%. The invention prevents double bonds in a reaction system from polymerization reaction by using the polymerization inhibitor.
The auxiliary agent comprises a catalyst, wherein the catalyst preferably comprises one or more of dibutyltin laurate, cobalt octoate and zinc naphthenate, and further preferably dibutyltin laurate. In the invention, the catalyst preferably accounts for 0.01-1% of the total mass of the raw materials for preparing the urethane acrylate oligomer, and more preferably 0.1-0.5%. The invention uses the catalyst to promote the condensation reaction between the monohydroxy acrylate and the polyurethane prepolymer.
In the present invention, the polymerization reaction includes a polycondensation reaction between a polyester polyol, dimethylolpropionic acid, urea and diisocyanate, a condensation reaction between a polycondensation reaction product and monohydroxyacrylate.
In the present invention, the urethane acrylate oligomer is a pale yellow solid in a paste form at room temperature.
The present invention does not require any particular source for the starting materials for the preparation, and commercially available products well known to those skilled in the art may be used unless otherwise specified.
The invention provides a preparation method of the polyurethane acrylate oligomer, which comprises the following steps:
(1) carrying out polycondensation reaction on a mixture of diisocyanate, polyester polyol, dimethylolpropionic acid and urea to obtain a polyurethane prepolymer;
(2) mixing the polyurethane prepolymer in the step (1) with monohydroxy acrylate and an auxiliary agent, and carrying out condensation reaction to obtain a polyurethane acrylate oligomer; the auxiliary agent comprises a polymerization inhibitor and a catalyst.
The invention carries out polycondensation reaction on a mixture of diisocyanate, polyester polyol, dimethylolpropionic acid and urea to obtain a polyurethane prepolymer. In the present invention, the method for preparing the mixture of diisocyanate, polyester polyol, dimethylolpropionic acid and urea preferably comprises adding diisocyanate dropwise to the mixture of polyester polyol, dimethylolpropionic acid and urea; the dripping mode of the diisocyanate is not particularly required in the invention, and the dripping mode known to the skilled person can be adopted.
In the present invention, the polycondensation reaction refers to a process in which hydroxyl groups in polyester polyol, dimethylolpropionic acid, and amine groups on amide groups in urea chemically react with isocyanate groups of diisocyanate to form a polymer.
In the invention, the temperature of the polycondensation reaction is preferably 60-100 ℃, more preferably 65-80 ℃, and more preferably 70-75 ℃; the reaction time is preferably 1 to 3 hours, more preferably 1.5 to 2.5 hours, and even more preferably 2 hours.
After the polyurethane prepolymer is obtained, the polyurethane prepolymer is mixed with monohydroxy acrylate and an auxiliary agent for condensation reaction to obtain a polyurethane acrylate oligomer. The invention has no special requirements on the mixing mode of the polyurethane prepolymer, the monohydroxy acrylate and the auxiliary agent, and adopts the mode known by the technical personnel in the field.
In the invention, the polyurethane prepolymer and the monohydroxy acrylate are subjected to condensation reaction under the action of an auxiliary agent, and an isocyanate group in the polyurethane prepolymer reacts with a hydroxyl group in the monohydroxy acrylate to generate a polyurethane acrylate oligomer. In the invention, the auxiliary agent comprises a polymerization inhibitor and a catalyst, and the components of the auxiliary agent are consistent with those of the auxiliary agent in the raw material for preparing the urethane acrylate oligomer in the technical scheme. In the invention, the condensation reaction temperature is preferably 60-100 ℃, more preferably 65-80 ℃, and more preferably 70-75 ℃; the reaction time is preferably 1 to 3 hours, more preferably 1.5 to 2.5 hours, and even more preferably 2 hours.
The invention also provides a water-based paint which comprises, by mass, 8-30 parts of a polyurethane acrylate oligomer, 10-60 parts of a reactive diluent, 2-10 parts of a photoinitiator, 1-18 parts of a paint auxiliary agent and 30-50 parts of water; the urethane acrylate oligomer is the urethane acrylate oligomer in the technical scheme or the urethane acrylate oligomer prepared by the preparation method in the technical scheme.
The water-based paint provided by the invention comprises 8-30 parts by mass of urethane acrylate oligomer, preferably 10-25 parts by mass; the polyurethane acrylic oligomer contains a polyurea chain segment and carboxyl, can form a three-dimensional network structure through hydrogen bonds, improves the thixotropy of the water-based paint, achieves the aim of preventing the water-based paint from sagging on a vertical surface, and simultaneously ensures that a paint film still has high glossiness.
Based on the mass part of the polyurethane acrylate oligomer, the water-based paint provided by the invention comprises 10-60 parts of reactive diluent, preferably 15-50 parts. In the present invention, the reactive diluent preferably comprises one or more of hexanediol diacrylate, tripropylene glycol diacrylate, trimethylolpropane triacrylate and pentaerythritol tetraacrylate; further preferably hexanediol diacrylate or tripropylene glycol diacrylate. When the active diluent is a mixture of several components, the invention has no special requirements on the mass ratio of the components in the mixture. In the present embodiment, the reactive diluent is preferably a commercially available product of Jiangsu Litian technologies, Inc. In the invention, the reactive diluent can adjust the viscosity of the water-based paint and simultaneously participate in UV curing to adjust the crosslinking density of a paint film, thereby providing favorable conditions for obtaining a compact paint film.
Based on the mass part of the polyurethane acrylate oligomer, the water-based paint provided by the invention comprises 2-10 parts of a photoinitiator, preferably 4-7 parts. In the present invention, the photoinitiator preferably comprises one or more of 2-hydroxy-2-methyl-1-phenyl acetone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-propanone, 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide, ethyl 2,4, 6-trimethylbenzoylphenylphosphonate, 2-dimethylamino-2-benzyl-1- [4- (4-morpholinyl) phenyl ] -1-butanone and 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-propanone, further preferred is 2-hydroxy-2-methyl-1-phenylpropanone or 1-hydroxycyclohexylphenylketone. When the photoinitiator is a mixture of several components, the mass ratio of the components in the mixture is not specially required. In the present examples, the photoinitiator is preferably a commercially available product of Tianjin Jiu chemical Co.
Based on the mass part of the polyurethane acrylate oligomer, the water-based paint provided by the invention comprises 1-18 parts of paint auxiliary agent, preferably 2-10 parts. In the invention, the coating auxiliary agent preferably comprises one or more of a leveling agent, a defoaming agent, an ultraviolet light absorber and a water-based wetting agent. When the coating additive is a mixture of several components, the invention has no special requirements on the mass ratio of the components in the mixture.
In the present invention, the leveling agent preferably includes a polysiloxane leveling agent; the polysiloxane leveling agent is preferably a product which is commercially available from BYK company and has the model number of 333. The present invention preferably utilizes a leveling agent to improve the surface smoothness and gloss of the aqueous coating.
In the present invention, the defoaming agent preferably includes a silicone compound defoaming agent; the silicone compound defoamer is preferably a 902W model commercially available product from Digao. The present invention preferably utilizes a defoamer to reduce and suppress foam generated by high speed agitation during the preparation of the waterborne coating.
In the present invention, the ultraviolet light absorber preferably includes one or more of 2, 4-dihydroxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2- (2 '-hydroxy-5' -methylphenyl) benzotriazole, 2- (2 '-hydroxy-3' -tert-butyl-5 '-methylphenyl) -5-chlorobenzotriazole and 2- (2' -hydroxy-3 ',5' -dipentylphenyl) benzotriazole, further preferably one or more of 2, 4-dihydroxy benzophenone, 2-hydroxy-4-n-octoxy benzophenone and 2-hydroxy-4-methoxy benzophenone. The present invention preferably utilizes an ultraviolet light absorber to improve the stability of the coating film in an environment containing ultraviolet light.
In the present invention, the aqueous wetting agent is preferably a commercially available product manufactured by Hamming corporation, model No. W-77. The present invention preferably utilizes an aqueous wetting agent to reduce the surface tension of the aqueous coating.
Based on the mass part of the polyurethane acrylate oligomer, the water-based paint provided by the invention further comprises 40-60 parts of water, preferably 45-55 parts of water. The present invention has no particular requirement for the water, and deionized water well known to those skilled in the art may be used.
In the present invention, the preparation method of the water-based paint preferably includes:
mixing a mixture containing a polyurethane acrylate oligomer, a reactive diluent and a photoinitiator with a coating auxiliary agent, and dispersing to obtain a base material;
and mixing the base material with water, and sieving to obtain the water-based paint.
According to the invention, the binder is preferably obtained by mixing a mixture containing the urethane acrylate oligomer, the reactive diluent and the photoinitiator with the coating auxiliary agent and dispersing the mixture. In the invention, the mixture containing the polyurethane acrylic oligomer, the reactive diluent and the photoinitiator is preferably prepared under a stirring condition, and the stirring speed is preferably 1800-2500 r/min, and more preferably 2000-2200 r/min; the stirring time is preferably 30-40 min, and more preferably 32-35 min.
In the invention, when the coating auxiliary agent is a mixture of several components, the addition sequence of the components of the coating auxiliary agent is not particularly required, and the method is well known to those skilled in the art.
In the present invention, the dispersion of the mixture comprising urethane acrylate oligomer, reactive diluent and photoinitiator after mixing with the coating adjuvant is preferably carried out under stirring conditions; the stirring speed is preferably 1800-2500 r/min, and more preferably 2000-2200 r/min; the stirring time is preferably 30-40 min, and more preferably 32-35 min.
After obtaining the base material, the base material is preferably mixed with water and sieved to obtain the water-based paint. The mixing mode of the base stock and the water is not particularly required in the invention, and the mixing mode known to the skilled person can be adopted. In the present invention, the mixing is preferably performed under stirring conditions; the stirring speed is preferably 1800-2500 r/min, and more preferably 2000-2400 r/min; the stirring time is preferably 30-40 min, and more preferably 32-35 min.
In the present invention, the mesh number of the screen mesh is preferably 400 to 600 meshes, and more preferably 450 to 550 meshes. The present invention does not require special embodiments of the screening, and can be practiced in a manner well known to those skilled in the art.
In the invention, the water-based paint is white emulsion and does not delaminate after being placed at room temperature for 3 months.
In the present invention, the mode of using the water-based paint preferably includes:
coating the water-based paint on a substrate to obtain a wet film;
and drying the wet film to obtain a dry film.
The present invention preferably applies the water-borne coating to a substrate to obtain a wet film. In the invention, the water-based paint is preferably applied by spraying, and the pressure of the spraying is preferably 1-4 kgf/cm2More preferably 2.5 to 3.5kgf/cm2(ii) a The invention has no special requirement on the spraying time, and can realize the control of the coating amount.
In the present invention, the substrate refers to an article to which a coating is to be applied. In the present invention, the base material preferably includes a cosmetic packaging material or a wine packaging material. The material of the packaging material is not particularly required in the invention, and the packaging material comprises but is not limited to glass products, plastic products, metal products or ceramic products.
After obtaining the wet film, the present invention preferably dries the wet film to obtain a dry film. In the invention, the drying is preferably ultraviolet irradiation curing (UV curing for short), and the UV energy range in the UV curing is preferably 500-1500 mj/cm2More preferably 600 to 1200mj/cm2More preferably 800 to 1000mj/cm2. The UV curing time is preferably 3-20 s, and more preferably 5-10 s. The present invention does not require special embodiments of the UV curing, and can be practiced in a manner well known to those skilled in the art.
In the invention, the thickness of the dry film (i.e. the coating) is preferably 20-25 μm, and more preferably 22-24 μm; the dry film is smooth in appearance and free of obvious sagging; testing the adhesive force of the coating according to GB/T9286-1998 standard, wherein the adhesive force of the dry film is 0 grade; testing the hardness of the dry film according to the GB/T6739-2006 standard, wherein the hardness of the dry film is more than or equal to 2H; testing the water resistance of the dry film by using the GB/T1733-1993 standard, wherein the testing time is 10 days, and the waterproof performance of the dry film is normal; the glossiness of the dry film is tested according to GB/T9754-2007 standard, and the glossiness of the dry film is more than or equal to 90Gu60 degrees.
In the above embodiments of the present invention, components or means which are not mentioned are commercially available products or means which are well known to those skilled in the art.
To further illustrate the present invention, a urethane acrylate oligomer, a method for preparing the same and a water-based paint according to the present invention will be described in detail with reference to examples, which should not be construed as limiting the scope of the present invention.
Example 1
Firstly, 39g of polyester polyol (manufacturer: Huafeng group, model PE-1280S, number average molecular weight 1300), 5.36g of dimethylolpropionic acid and 1.8g of urea are added, 44.4g of isophorone diisocyanate is dripped within 30min, and the temperature is raised to 70 ℃ and kept for 2 h; then 0.12g of hydroquinone, 12.8g of hydroxyethyl acrylate and 0.06g of dibutyltin dilaurate are added, the temperature is kept at 70 ℃ for 2 hours, and the temperature is naturally reduced to the room temperature, so that the urethane acrylate oligomer is obtained.
Mixing 20 parts by mass of urethane acrylate oligomer, 40 parts by mass of hexanediol diacrylate reactive diluent and 5 parts by mass of 2-hydroxy-2-methyl-1-phenyl acetone, and dispersing at high speed for 30min under the condition of 2000 r/min; then adding 1 part by mass of polysiloxane flatting agent (BYK, model 333), 1 part by mass of polysiloxane compound defoaming agent (Digao, model 902W) and 2 parts by mass of water-based wetting agent (Haiming, model W-77), and continuously dispersing at high speed for 30min under the condition of 2000 r/min; then adding 31 parts by mass of deionized water, dispersing at high speed for 30min under the condition of 2000r/min, and sieving by a 400-mesh sieve, wherein the sieved substance is the UV-curable coating.
Spraying the obtained UV-curable coating on an ABS plastic cover for UV curing, wherein the curing conditions are as follows: the energy range is 800mj/cm2The conveying speed is 30m/min, and a dry film with the thickness of 20 mu m is obtained after curing for 5 s.
Example 2
Firstly, 39g of polyester polyol (same as example 1), 6.7g of dimethylolpropionic acid and 1.2g of urea are added, 44.4g of isophorone diisocyanate is dripped, and the temperature is raised to 70 ℃ and kept for 2 h; then 0.2g of hydroquinone, 15.6g of hydroxyethyl acrylate and 0.12g of dibutyltin dilaurate are added, the temperature is kept at 70 ℃ for 2 hours, and the temperature is naturally reduced to the room temperature, so that the urethane acrylate oligomer is obtained.
Mixing 10 parts by mass of urethane acrylate oligomer, 40 parts by mass of hexanediol diacrylate reactive diluent and 6 parts by mass of 2-hydroxy-2-methyl-1-phenyl acetone, and dispersing at high speed for 30min under the condition of 2000 r/min; then adding 1 part by mass of polysiloxane flatting agent (BYK, model 333), 1 part by mass of polysiloxane compound defoaming agent (Digao, model 902W) and 2 parts by mass of water-based wetting agent (Haiming, model W-77), and continuously dispersing at high speed for 30min under the condition of 2000 r/min; then 40 parts by mass of deionized water is added, high-speed dispersion is carried out for 30min under the condition of 2000r/min, and the mixture is sieved by a 400-mesh sieve, wherein the undersize product is the UV-curable coating.
Spraying the obtained UV-curable coating on an ABS plastic cover for UV curing, wherein the curing conditions are as follows: the energy range is 800mj/cm2The conveying speed is 30m/min, solidAfter converting for 10s, a dry film having a thickness of 23 μm was obtained.
Example 3
Firstly, 26g of polyester polyol (same as example 1), 8g of dimethylolpropionic acid and 1.2g of urea are added, 44.4g of isophorone diisocyanate is dripped, and the temperature is raised to 70 ℃ and kept for 2 h; then 0.18g of hydroquinone, 10g of hydroxyethyl acrylate and 0.18g of dibutyltin dilaurate are added, the temperature is kept at 70 ℃ for 2h, and the mixture is cooled to room temperature by water, so as to obtain the urethane acrylate oligomer.
Mixing 25 parts by mass of urethane acrylate oligomer, 35 parts by mass of hexanediol diacrylate reactive diluent and 7 parts by mass of 2-hydroxy-2-methyl-1-phenyl acetone, and dispersing at high speed for 30min under the condition of 2000 r/min; then 0.5 part by mass of polysiloxane flatting agent (BYK, model 333), 1.2 parts by mass of polysiloxane compound defoaming agent (Digao, model 902W) and 2 parts by mass of water-based wetting agent (Haimines, model W-77) are added, and high-speed dispersion is continued for 30min under the condition of 2000 r/min; and then adding 35 parts by mass of deionized water, dispersing at a high speed for 30min under the condition of 2000r/min, and sieving by a 400-mesh sieve to obtain a UV-curable coating.
Spraying the obtained UV-curable coating on an ABS plastic cover for UV curing, wherein the curing conditions are as follows: the energy range is 900mj/cm2The conveying speed is 30m/min, and a dry film with the thickness of 25 mu m is obtained after 6 seconds of solidification.
Example 4
Firstly, 26g of polyester polyol (same as example 1), 6.7g of dimethylolpropionic acid and 1.8g of urea are added, 44.4g of isophorone diisocyanate is dripped, and the temperature is raised to 70 ℃ and kept for 2 h; then 0.24g of hydroquinone, 10.8g of hydroxyethyl acrylate and 0.2g of dibutyltin dilaurate are added, the temperature is kept at 70 ℃ for 2 hours, and the mixture is cooled to room temperature by water, so as to obtain the urethane acrylate oligomer.
Mixing 15 parts by mass of urethane acrylate oligomer, 32 parts by mass of hexanediol diacrylate reactive diluent and 4 parts by mass of 2-hydroxy-2-methyl-1-phenyl acetone, and dispersing at high speed for 30min under the condition of 2000 r/min; then adding 1.5 parts by mass of polysiloxane flatting agent (BYK, model 333), 1 part by mass of polysiloxane compound defoaming agent (Digao, model 902W) and 2.5 parts by mass of water-based wetting agent (Haimines, model W-77), and continuing to disperse at high speed for 30min under the condition of 2000 r/min; then 40 parts by mass of deionized water is added, high-speed dispersion is carried out for 28min under the condition of 2200r/min, and the mixture is sieved by a 400-mesh sieve, wherein the undersize product is the UV-curable coating.
Spraying the obtained UV-curable coating on an ABS plastic cover for UV curing, wherein the curing conditions are as follows: the energy range is 850mj/cm2The conveying speed is 30m/min, and a dry film with the thickness of 22 mu m is obtained after curing for 8 s.
Comparative example 1
26g of polyester polyol (manufacturer: Huafeng group, model PE-1280S, number average molecular weight 1300) and 8g of dimethylolpropionic acid are added firstly, 44.4g of isophorone diisocyanate is added dropwise, and the temperature is raised to 70 ℃ and kept for 2 hours. Then 0.18g of hydroquinone, 10g of hydroxyethyl acrylate and 0.18g of dibutyltin dilaurate are added, the temperature is kept for 2 hours at 70 ℃, and the temperature is reduced to room temperature, thus obtaining the oligomer.
Waterborne coatings and dry films were prepared according to the amount and method of example 2.
Comparative example 2
Using the oligomer prepared in comparative example 1, an aqueous coating material and a dry film were prepared in the same manner as in comparative example 1 except that the photoinitiator was used in an amount of 5.5 parts by mass, and 0.5 part by mass of an anti-sagging agent (Hemmins, model WT-105A) was added.
Performance testing and results
According to a conventional detection method in the field, detecting various performances of the dry films obtained in the examples 1-4 and the comparative examples 1-2, wherein the appearance of the dry film is tested by a visual detection method; the adhesion is tested according to the GB/T9286-1998 standard; the hardness is tested according to the GB/T6739-2006 standard; the water resistance is tested according to the GB/T1733-1993 standard; gloss was measured according to GB/T9754-2007 standard. The test results are shown in table 1.
TABLE 1 Dry film Performance test results for examples 1-4 and comparative examples 1-2
As shown in the test results in Table 1, compared with the traditional urethane acrylic acid, the urethane acrylate oligomer provided by the invention can overcome the problem of vertical surface sagging of a water-based paint and obviously improve the flatness and glossiness of a dry film.
As is clear from the above examples, the urethane acrylate oligomer obtained according to the present invention has good water dispersibility due to the polyurea segment and the carboxyl group, and can form a slight three-dimensional network structure in water due to the polyurea group and the carboxyl group, and the coating material containing the resin can effectively prevent sagging of the coating film before UV curing. The water paint prepared by the invention does not add the common anti-sagging agent, does not easily generate particles, is suitable for plastic surface vacuum coating paint with high gloss requirement, and can be used for vacuum coating bottom and top coats of cosmetics and wine packaging plastic products.
Although the present invention has been described in detail with reference to the above embodiments, it is only a part of the embodiments of the present invention, not all of the embodiments, and other embodiments can be obtained without inventive step according to the embodiments, and the embodiments are within the scope of the present invention.
Claims (9)
1. The polyurethane acrylate oligomer is polymerized from the following preparation raw materials, wherein the preparation raw materials comprise a main material and an auxiliary agent; the main material comprises diisocyanate, polyester polyol, dimethylolpropionic acid, urea and monohydroxy acrylate; the auxiliary agent comprises a polymerization inhibitor and a catalyst; the mass ratio of the polyester polyol to the diisocyanate is 0.5-0.9: 1; the mass ratio of the dimethylolpropionic acid to the diisocyanate is 0.12-0.20: 1; the mass ratio of the urea to the diisocyanate is 0.027-0.042: 1; the molar ratio of the monohydroxy acrylate to the diisocyanate is 1: 0.5-2;
the preparation method of the polyurethane acrylate oligomer comprises the following steps:
(1) performing polycondensation reaction on a mixture of polyester polyol, dimethylolpropionic acid, urea and diisocyanate to obtain a polyurethane prepolymer;
(2) mixing the polyurethane prepolymer in the step (1) with monohydroxy acrylate and an auxiliary agent, and carrying out condensation reaction to obtain a polyurethane acrylate oligomer; the auxiliary agent comprises a polymerization inhibitor and a catalyst.
2. The urethane acrylate oligomer of claim 1, wherein the diisocyanate comprises one or more of toluene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, and dicyclohexylmethane diisocyanate;
the polyester polyol comprises a polycondensate of a polyol and a dibasic acid; the polyalcohol comprises one or more of dihydric alcohol, trihydric alcohol and tetrahydric alcohol;
the monohydroxy acrylate comprises one or more of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate and hydroxypropyl methacrylate.
3. The urethane acrylate oligomer of claim 1 wherein the polymerization inhibitor comprises hydroquinone and/or p-methoxyphenol.
4. The urethane acrylate oligomer of claim 1 wherein the catalyst comprises one or more of dibutyltin dilaurate, cobalt octoate and zinc naphthenate.
5. The urethane acrylate oligomer according to claim 1, wherein the polymerization inhibitor accounts for 0.01-1% of the total mass of the raw materials for preparing the urethane acrylate oligomer; the catalyst accounts for 0.01-1% of the total mass of the raw materials for preparing the urethane acrylate oligomer.
6. A method for preparing the urethane acrylate oligomer according to any one of claims 1 to 5, comprising the steps of:
(1) performing polycondensation reaction on a mixture of polyester polyol, dimethylolpropionic acid, urea and diisocyanate to obtain a polyurethane prepolymer;
(2) mixing the polyurethane prepolymer in the step (1) with monohydroxy acrylate and an auxiliary agent, and carrying out condensation reaction to obtain a polyurethane acrylate oligomer; the auxiliary agent comprises a polymerization inhibitor and a catalyst.
7. The method according to claim 6, wherein the temperature of the polycondensation reaction of step (1) and the condensation reaction of step (2) is 60 to 100 ℃ independently; the time of the polycondensation reaction and the condensation reaction is independently 1-3 h.
8. The water-based paint comprises, by mass, 8-30 parts of a urethane acrylate oligomer, 10-60 parts of a reactive diluent, 2-10 parts of a photoinitiator, 1-18 parts of a paint auxiliary agent and 30-50 parts of water; the urethane acrylate oligomer is the urethane acrylate oligomer according to any one of claims 1 to 5 or the urethane acrylate oligomer prepared by the preparation method according to claim 6 or 7.
9. The water-based paint according to claim 8, wherein the paint auxiliary agent comprises one or more of a leveling agent, a defoaming agent, an ultraviolet light absorber and a water-based wetting agent;
the active diluent comprises one or more of hexanediol diacrylate, tripropylene glycol diacrylate, trimethylolpropane triacrylate and pentaerythritol tetraacrylate;
the photoinitiator comprises 2-hydroxy-2-methyl-1-phenyl acetone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-acetone, 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide, 2,4, 6-trimethylbenzoyl phenyl ethyl phosphonate, 2-dimethylamino-2-benzyl-1- [4- (4-morpholinyl) phenyl ] -1-butanone and one or more of 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-propanone. .
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