CN108864401A - A kind of urethane acrylate oligomer and preparation method thereof and a kind of water paint - Google Patents
A kind of urethane acrylate oligomer and preparation method thereof and a kind of water paint Download PDFInfo
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- CN108864401A CN108864401A CN201810689855.8A CN201810689855A CN108864401A CN 108864401 A CN108864401 A CN 108864401A CN 201810689855 A CN201810689855 A CN 201810689855A CN 108864401 A CN108864401 A CN 108864401A
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- diisocyanate
- urethane acrylate
- oligomer
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- acrylate oligomer
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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
-
- 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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- 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)
- Macromonomer-Based Addition Polymer (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention belongs to water-soluble oligomer technical fields, and in particular to a kind of urethane acrylate oligomer and preparation method thereof and a kind of water paint.Urethane acrylate oligomer provided by the invention forms polyureas segment using urea, then the hydrogen bond of tridimensional network is formed by polyureas segment and carboxyl, achievees the purpose that improve paint thixotropy.Embodiment the result shows that, when urethane acrylate oligomer provided by the invention is used for water paint, gained appearance of coat is smooth, without obvious sagging, and 60 ° of glossiness >=90Gu of coating.
Description
Technical field
The invention belongs to water-soluble oligomer technical fields, and in particular to a kind of urethane acrylate oligomer and its system
Preparation Method and a kind of water paint.
Background technique
Traditional coating contains volatile organic solvent (VOC), easily causes environmental pollution, is not able to satisfy modern society to ring
The new demand of friendly coating is gradually replaced by ultraviolet-curing paint (abbreviation UV coating).UV coating is a kind of without volatility
Organic solvent, environmental pollution is small, reduces construction toxicity；Curing rate is fast, and hardening can be realized by ultraviolet light, and
It is nonflammable, non-explosive, the security performance of coating is greatly improved, therefore, becomes the major product of substitution traditional coating.But at present
UV coating in shipwreck to volatilize, the paint film mobility before leading to photocuring is preferable, it is easy in the curing process generate stream
It hangs, influences paint film effect.To overcome flowing down problems, conventional method is to improve viscosity of the coating by adding a large amount of anti-sagging agent,
The glossiness that surface of the paint film is easily lead to eliminate flowing down problems, but after addition anti-sagging agent reduces.
Summary of the invention
The purpose of the present invention is to provide a kind of urethane acrylate oligomers and preparation method thereof and a kind of aqueous painting
Material and preparation method thereof, when urethane acrylate oligomer provided by the invention is as water paint raw material, can be improved aqueous
The thixotropy of coating achievees the purpose that prevent paint film in facade sagging, while paint film being made still to have high gloss.
In order to achieve the above object, the present invention provides a kind of urethane acrylate oligomer, by including preparation below
Polymerizable raw material forms, and the raw material for preparing includes major ingredient and auxiliary agent；The major ingredient includes diisocyanate, polyester polyol, two
Hydroxymethyl propionic acid, urea and monohydroxy acrylate；The auxiliary agent includes polymerization inhibitor and catalyst.
Preferably, the diisocyanate includes toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, two methylene of benzene
In group diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate and dicyclohexyl methyl hydride diisocyanate
One or more；
The polyester polyol includes the condensation polymer of polyalcohol and binary acid；The polyalcohol includes dihydric alcohol, trihydroxylic alcohol
One or more of with tetrahydroxylic alcohol；
The monohydroxy acrylate includes hydroxy-ethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, methyl
One or more of hydroxypropyl acrylate.
Preferably, the mass ratio of the polyester polyol and diisocyanate is 0.5~0.9:1；
The mass ratio of the dihydromethyl propionic acid and diisocyanate is 0.12~0.20:1；
The mass ratio of the urea and diisocyanate is 0.027~0.042:1；
The molar ratio of the monohydroxy acrylate and diisocyanate is 1:0.5~2.
Preferably, the polymerization inhibitor includes hydroquinone and/or p methoxy phenol.
Preferably, the catalyst includes one or more of dibutyl tin laurate, cobalt octoate and zinc naphthenate.
Preferably, the polymerization inhibitor accounts for the 0.01~1% of urethane acrylate oligomer preparation total mass of raw material；It is described
Catalyst accounts for the 0.01~1% of urethane acrylate oligomer preparation total mass of raw material.
The present invention provides the preparation methods of urethane acrylate oligomer described in above-mentioned technical proposal, including walk as follows
Suddenly：
(1) mixture of polyester polyol, dihydromethyl propionic acid, urea and diisocyanate is subjected to polycondensation reaction, obtained
To base polyurethane prepolymer for use as；
(2) base polyurethane prepolymer for use as of the step (1) is mixed with monohydroxy acrylate and auxiliary agent, be condensed anti-
It answers, obtains urethane acrylate oligomer；The auxiliary agent includes polymerization inhibitor and catalyst.
Preferably, the temperature of the condensation reaction of the polycondensation reaction and step (2) of the step (1) independently is 60~100
℃；The time of polycondensation reaction and condensation reaction independently is 1~3h.
The present invention also provides a kind of water paints, and in terms of mass parts, including 8~30 parts of urethane acrylates are oligomeric
Object, 10~60 portions of reactive diluents, 2~10 parts of photoinitiators, 1~18 part of coating additive and 30~50 parts of water；The polyurethane
Acrylate oligomer is preparation side described in urethane acrylate oligomer described in above-mentioned technical proposal or above-mentioned technical proposal
The urethane acrylate oligomer that method is prepared.
Preferably, the coating additive includes one of levelling agent, defoaming agent, UV absorbers and aqueous wetting agent
Or it is several；
The reactive diluent includes hexanediyl ester, three polypropyleneglycol diacrylates, trimethylolpropane
One or more of triacrylate and pentaerythritol tetraacrylate；
The photoinitiator includes 2- hydroxy-2-methyl -1- phenylacetone, 1- hydroxycyclohexyl phenyl ketone, 2- methyl -
2- (4- morpholinyl) -1- [4- (methyl mercapto) phenyl] -1- acetone, 2,4,6- trimethylbenzoy-dipheny phosphine oxide, 2,4,
6- trimethylbenzoyl phenyl phosphinic acid ethyl ester, 2- dimethylamino -2- benzyl -1- [4- (4- morpholinyl) phenyl] -1- butanone and
One or more of 2- hydroxy-2-methyl -1- [4- (2- hydroxyl-oxethyl) phenyl] -1- acetone.
Urethane acrylate oligomer provided by the invention prepares raw material by including that the polymerizable raw material below for preparing forms
Including major ingredient and auxiliary agent；Wherein major ingredient includes diisocyanate, polyester polyol, dihydromethyl propionic acid, urea and monohydroxy third
Olefin(e) acid ester；Auxiliary agent includes polymerization inhibitor and catalyst.The present invention forms polyureas segment using urea, then passes through polyureas segment and carboxyl
The hydrogen bond for forming tridimensional network achievees the purpose that improve paint thixotropy.Embodiment the result shows that, by above-mentioned polyurethane third
When olefin(e) acid ester oligomer is used for water paint, gained appearance of coat is smooth, without obvious sagging, and glossiness >=90Gu of coating
60°。
Specific embodiment
The present invention provides a kind of urethane acrylate oligomers, by including that the polymerizable raw material below for preparing forms, institute
Stating and preparing raw material includes major ingredient and auxiliary agent；The major ingredient includes diisocyanate, polyester polyol, dihydromethyl propionic acid, urea
With monohydroxy acrylate；The auxiliary agent includes polymerization inhibitor and catalyst.
The raw material for preparing of urethane acrylate oligomer provided by the invention includes major ingredient, and the major ingredient includes two isocyanides
Acid esters, it is different that the diisocyanate preferably includes toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, phenylenedimethylidyne two
One of cyanate, hexamethylene diisocyanate, isophorone diisocyanate and dicyclohexyl methyl hydride diisocyanate
Or several, more preferably isophorone diisocyanate, benzene dimethylene diisocyanate or hexamethylene diisocyanate.
Major ingredient of the present invention includes polyester polyol.In the present invention, the polyester polyol includes polyalcohol and two
The condensation polymer of first acid.In the present invention, the polyalcohol preferably includes dihydric alcohol, trihydroxylic alcohol or tetrahydroxylic alcohol；Further preferably packet
Include the dihydric alcohol or trihydroxylic alcohol.In the present invention, the dihydric alcohol preferably includes ethylene glycol, 1,2-PD, 1,3- the third two
One in alcohol, 1,4- butanediol, 1,5- pentanediol, 1,6-HD, 1,8- ethohexadiol, 1,9- nonanediol and 1,10- decanediol
Kind is several；The trihydroxylic alcohol preferably includes trimethylolpropane and/or glycerine；The tetrahydroxylic alcohol preferably includes Ji Wusi
Alcohol.When the polyalcohol is the mixture of several components, the present invention does not have particular/special requirement to the mass ratio of the polyalcohol.
In the present invention, the binary acid preferably includes ethanedioic acid, malonic acid, succinic acid, glutaric acid, adipic acid and the last of the ten Heavenly stems two
One or more of acid, further preferably adipic acid.
In the present invention, the polyester polyol preferably include the condensation polymer of ethylene glycol and adipic acid, 1,2-PD with
The condensation polymer of adipic acid, the condensation polymer of 1,3- propylene glycol and adipic acid, 1,4- butanediol and adipic acid condensation polymer, 1,5- penta 2
The condensation polymer of the condensation polymer of alcohol and adipic acid, 1,6-HD and adipic acid.In the present invention, the number of the polyester polyol is equal
Molecular weight is preferably 500~5000, and more preferably 1000~3000.In embodiments of the present invention, the polyester polyol is China
Peak group, model PE-1280S, the commercial product that number-average molecular weight is 1300.
In the present invention, the mass ratio of the polyester polyol and diisocyanate is preferably 0.5~0.9:1, further
Preferably 0.6~0.8:1.Polyester polyol is preferably carried out above-mentioned restriction by the present invention, is conducive to control urethane acrylate
The molecular weight and viscosity of oligomer.
In the present invention, the major ingredient includes dihydromethyl propionic acid.In the present invention, the dihydromethyl propionic acid and two different
The mass ratio of cyanate is preferably 0.12~0.20:1, further preferably 0.13~0.18:1.The present invention is preferably by dihydroxy first
Base propionic acid is controlled in above range, be can be avoided urethane acrylate oligomer and is precipitated in water, moreover it is possible to make to contain the poly- ammonia
The water paint of ester acrylate oligomer is easily dried solidification, improves the drying property of coating.
In the present invention, the major ingredient includes urea, provides amide groups using urea, to form the three-dimensional netted knot of hydrogen bond
Structure provides basis.In the present invention, the mass ratio of the urea and diisocyanate is preferably 0.027~0.042:1, further
Preferably 0.028~0.040:1.The present invention preferably controls urea content in above range, and being avoided that viscosity is excessive causes to gather
Urethane acrylate oligomer gel.
In the present invention, the major ingredient includes monohydroxy acrylate, the monohydroxy acrylate and diisocyanate
Molar ratio be preferably 1:0.5~2；Further preferably 1:1.0~1.5.In the present invention, the monohydroxy acrylate is excellent
Choosing include one of hydroxy-ethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate and hydroxy propyl methacrylate or
It is several, more preferably hydroxy-ethyl acrylate.When the monohydroxy acrylate is the mixture of several components, the present invention is to described
The mass ratio of each component does not have particular/special requirement in mixture.In the present invention, the monohydroxy acrylate can be pre- with polyurethane
Condensation reaction occurs for the isocyanate groups in aggressiveness.
The raw material for preparing of urethane acrylate oligomer of the present invention further includes auxiliary agent, and the auxiliary agent includes polymerization inhibitor
And catalyst.In the present invention, the polymerization inhibitor preferably includes hydroquinone and/or p methoxy phenol, further preferably
Hydroquinone；The polymerization inhibitor preferably accounts for the 0.01~1% of urethane acrylate oligomer preparation total mass of raw material, further
Preferably 0.1~0.5%.The present invention prevents the double bond in reaction system from polymerization reaction occurs using polymerization inhibitor.
Auxiliary agent of the present invention includes catalyst, and the catalyst preferably includes dibutyl tin laurate, cobalt octoate and ring
One or more of alkanoic acid zinc, further preferably dibutyl tin laurate.In the present invention, the catalyst preferably accounts for poly-
Urethane acrylate oligomer prepares 0.01~1%, further preferably the 0.1~0.5% of total mass of raw material.The present invention utilizes
Catalyst promotes the condensation reaction between monohydroxy acrylate and base polyurethane prepolymer for use as.
In the present invention, the polymerization reaction include polyester polyol, dihydromethyl propionic acid, urea and diisocyanate it
Between polycondensation reaction, the condensation reaction between polycondensation product and monohydroxy acrylate.
It in the present invention, is light yellow solid paste under the urethane acrylate oligomer room temperature.
Unless otherwise specified, the present invention does not have particular/special requirement to the source for preparing raw material, using those skilled in the art
Commercial product known to member.
The present invention provides the preparation methods of urethane acrylate oligomer described in above-mentioned technical proposal, including walk as follows
Suddenly：
(1) mixture of diisocyanate, polyester polyol, dihydromethyl propionic acid and urea is subjected to polycondensation reaction, obtained
To base polyurethane prepolymer for use as；
(2) base polyurethane prepolymer for use as of the step (1) is mixed with monohydroxy acrylate and auxiliary agent, be condensed anti-
It answers, obtains urethane acrylate oligomer；The auxiliary agent includes polymerization inhibitor and catalyst.
The mixture of diisocyanate, polyester polyol, dihydromethyl propionic acid and urea is carried out polycondensation reaction by the present invention,
Obtain base polyurethane prepolymer for use as.In the present invention, the diisocyanate, polyester polyol, dihydromethyl propionic acid and urea is mixed
The preparation method for closing object preferably includes the mixture that diisocyanate is added dropwise to polyester polyol, dihydromethyl propionic acid and urea
In；The present invention does not have particular/special requirement to the dropwise addition mode of the diisocyanate, using dropwise addition well known to those skilled in the art
Mode.
In the present invention, the polycondensation reaction refer to polyester polyol, amide in hydroxyl and urea in dihydromethyl propionic acid
The isocyanate groups of amido and diisocyanate on base chemically react, and generate the process of polymer.
In the present invention, the temperature of the polycondensation reaction is preferably 60~100 DEG C, and further preferably 65~80 DEG C, more
Preferably 70~75 DEG C；The time of reaction is preferably 1~3h, further preferably 1.5~2.5h, more preferably 2h.
After obtaining base polyurethane prepolymer for use as, the present invention mixes the base polyurethane prepolymer for use as and monohydroxy acrylate and auxiliary agent
It closes, carries out condensation reaction, obtain urethane acrylate oligomer.The present invention is to the base polyurethane prepolymer for use as, monohydroxy propylene
The hybrid mode of acid esters and auxiliary agent does not have particular/special requirement, using mode well known to those skilled in the art.
In the present invention, the base polyurethane prepolymer for use as and monohydroxy acrylate be condensed anti-under the action of auxiliary agent
It answers, the isocyanate groups in base polyurethane prepolymer for use as are reacted with the hydroxyl in monohydroxy acrylate, generate polyurethane acroleic acid
Ester oligomer.In the present invention, the auxiliary agent includes polymerization inhibitor and catalyst, component and the above-mentioned technical proposal institute of the auxiliary agent
It is consistent to state the adjuvant component that urethane acrylate oligomer is prepared in raw material.In the present invention, the temperature of the condensation reaction
Preferably 60~100 DEG C, further preferably 65~80 DEG C, more preferably 70~75 DEG C；The time of reaction is preferably 1~3h,
Further preferably 1.5~2.5h, more preferably 2h.
The present invention separately provides a kind of water paint, and in terms of mass parts, including 8~30 parts of urethane acrylates are oligomeric
Object, 10~60 portions of reactive diluents, 2~10 parts of photoinitiators, 1~18 part of coating additive and 30~50 parts of water；The polyurethane
Acrylate oligomer is preparation side described in urethane acrylate oligomer described in above-mentioned technical proposal or above-mentioned technical proposal
The urethane acrylate oligomer that method is prepared.
In terms of mass parts, water paint provided by the invention includes 8~30 parts of urethane acrylate oligomers, preferably
10~25 parts；Contain polyureas segment and carboxyl in the polyurethane acroleic acid oligomer, can be formed by hydrogen bond three-dimensional netted
Structure improves the thixotropy of water paint, achievees the purpose that prevent water paint in facade sagging, while paint film being made still to have height
Glossiness.
On the basis of the urethane acrylate oligomer of the mass parts, water paint provided by the invention include 10~
60 portions of reactive diluents, preferably 15~50 parts.In the present invention, the reactive diluent preferably includes hexanediyl
One of ester, three polypropyleneglycol diacrylates, trimethylolpropane trimethacrylate and pentaerythritol tetraacrylate or
It is several；Further preferably hexanediyl ester or three polypropyleneglycol diacrylates.The reactive diluent is several
When the mixture of component, the present invention does not have particular/special requirement to the mass ratio of each component in the mixture.In the embodiment of the present invention
In, the reactive diluent is preferably the commercial product of Jiangsu Litian Technology Co., Ltd.In the present invention, the activity dilution
Agent can adjust the viscosity of water paint, simultaneously participate in the paint film that UV solidifies to adjust the crosslink density of paint film, to obtain fine and close and mention
For advantage.
On the basis of the urethane acrylate oligomer of the mass parts, water paint provided by the invention include 2~
10 parts of photoinitiators, preferably 4~7 parts.In the present invention, the photoinitiator preferably includes 2- hydroxy-2-methyl -1- phenyl
Acetone, 1- hydroxycyclohexyl phenyl ketone, 2- methyl -2- (4- morpholinyl) -1- [4- (methyl mercapto) phenyl] -1- acetone, 2,4,
6- trimethylbenzoy-dipheny phosphine oxide, 2,4,6- trimethylbenzoyl phenyl phosphinic acid ethyl ester, 2- dimethylamino -2-
Benzyl -1- [4- (4- morpholinyl) phenyl] -1- butanone and 2- hydroxy-2-methyl -1- [4- (2- hydroxyl-oxethyl) phenyl] -1- third
One or more of ketone, further preferably 2- hydroxy-2-methyl -1- phenylacetone or 1- hydroxycyclohexyl phenyl ketone.
When the photoinitiator is the mixture of several components, the present invention does not have special want to the mass ratio of each component in the mixture
It asks.In embodiments of the present invention, the photoinitiator is preferably the commercial product of Tianjin Jiuri Chemical Co., Ltd..
On the basis of the urethane acrylate oligomer of the mass parts, water paint provided by the invention include 1~
18 parts of coating additives, preferably 2~10 parts.In the present invention, the coating additive preferably includes levelling agent, defoaming agent, ultraviolet
One or more of light absorber and aqueous wetting agent.When the coating additive is the mixture of several components, the present invention couple
The mass ratio of each component does not have particular/special requirement in the mixture.
In the present invention, the levelling agent preferably includes polysiloxane leveling agents；The polysiloxane leveling agents are preferably
The production of BYK company, the commercial product of model 333.The present invention improves the surface smoothness of water paint preferably by levelling agent
And glossiness.
In the present invention, the defoaming agent preferably includes polysiloxane compound defoaming agent；The polysiloxane compound
Defoaming agent is preferably Digao company, the commercial product of model 902W.The present invention reduces preferably by defoaming agent and inhibits aqueous
The coating foam as caused by high-speed stirred during the preparation process.
In the present invention, the UV absorbers preferably include 2,4-DihydroxyBenzophenone, the just pungent oxygen of 2- hydroxyl -4-
Base benzophenone, ESCALOL 567,2- (2'- hydroxyl -5'- aminomethyl phenyl) benzotriazole, 2- (2'- hydroxyl
Base -3'- tert-butyl -5'- aminomethyl phenyl) -5- chlorinated benzotriazole and 2- (2'- hydroxyl -3', 5'- diamyl phenyl) benzo three
One or more of azoles, further preferably 2,4-DihydroxyBenzophenone, 2-hydroxy-4-n-octoxybenzophenone and 2-
One or more of hydroxyl -4- methoxy benzophenone.The present invention improves film preferably by UV absorbers and is containing
Stability in the environment of ultraviolet light.
In the present invention, the aqueous wetting agent is preferably the production of this company of hamming, the commercial product of model W-77.This
Invention reduces the surface tension of water paint preferably by aqueous wetting agent.
On the basis of the urethane acrylate oligomer of the mass parts, water paint provided by the invention further includes 40
~60 parts of water, preferably 45~55 parts.The present invention does not have particular/special requirement to the water, is gone using well known to those skilled in the art
Ionized water.
In the present invention, the preparation method of the water paint preferably includes：
Mixture comprising urethane acrylate oligomer, reactive diluent and photoinitiator and coating additive are mixed
It closes, obtains base-material after dispersion；
The base-material is mixed with water, water paint is obtained after sieving.
The present invention is preferably by the mixture comprising urethane acrylate oligomer, reactive diluent and photoinitiator and painting
Expect auxiliary agent mixing, obtains base-material after dispersion.In the present invention, it is described comprising polyurethane acroleic acid oligomer, reactive diluent and
The mixture of photoinitiator is preferably prepared under agitation and is obtained, and the speed of the stirring is preferably 1800~2500r/min,
Further preferably 2000~2200r/min；The time of the stirring is preferably 30~40min, further preferably 32~
35min。
In the present invention, when the coating additive is the mixture of several components, the present invention is to the coating additive each group
The order of addition divided does not have particular/special requirement, using mode well known to those skilled in the art.
In the present invention, mixture and painting comprising urethane acrylate oligomer, reactive diluent and photoinitiator
The dispersion carried out after material auxiliary agent mixing, preferably carries out under agitation；The speed of the stirring is preferably 1800~2500r/
Min, further preferably 2000~2200r/min；The time of the stirring is preferably 30~40min, and further preferably 32
~35min.
After obtaining base-material, the present invention preferably mixes base-material with water, and water paint is obtained after sieving.The present invention is to the base
The hybrid mode of material and water does not have particular/special requirement, using hybrid mode well known to those skilled in the art.In the present invention,
The mixing preferably carries out under agitation；The speed of the stirring is preferably 1800~2500r/min, further preferably
2000~2400r/min；The time of the stirring is preferably 30~40min, further preferably 32~35min.
In the present invention, the mesh number of sieving sieve is preferably 400~600 mesh, further preferably 450~550
Mesh.The present invention does not have particular/special requirement to the specific embodiment of the sieving, is using mode well known to those skilled in the art
It can.
In the present invention, the water paint be white milky liquid, be placed at room temperature for 3 months it is not stratified.
In the present invention, the usage mode of the water paint preferably includes：
Water paint is coated on substrate, wet film is obtained；
The wet film is dried, dry film is obtained.
Water paint is preferably coated on substrate by the present invention, obtains wet film.In the present invention, the painting of the water paint
It covers mode preferably to spray, the pressure of the spraying is preferably 1~4kgf/cm2, further preferably 2.5~3.5kgf/cm2；
The present invention does not have particular/special requirement to the time of the spraying, is able to achieve the control of above-mentioned coated weight.
In the present invention, the substrate refers to the product of coating to be coated.In the present invention, the substrate preferably includes to make up
Product packaging material or Wine packaging material.The present invention does not have particular/special requirement, including but not limited to glass to the material of the packaging material
Glass product, plastic products, metal product or ceramic.
After obtaining wet film, the present invention is preferably dried the wet film, obtains dry film.In the present invention, the drying
Preferably ultraviolet radiation-curable (abbreviation UV solidification), the UV solidify in the energy range of UV be preferably 500~1500mj/
cm2, further preferably 600~1200mj/cm2, more preferably 800~1000mj/cm2.The UV cured time is preferably
3~20s, further preferably 5~10s.The present invention does not have particular/special requirement to the cured specific embodiment of the UV, using this
Mode known to the technical staff of field.
In the present invention, the thickness of the dry film (i.e. coating) is preferably 20~25 μm, and further preferably 22~24 μm；
The flat appearance of the dry film, without obvious sagging；It is of the present invention with the adhesive force of GB/T9286-1998 standard testing coating
The adhesive force of dry film is 0 grade；With the hardness of GB/T6739-2006 standard testing dry film, hardness >=2H of dry film of the present invention；
With the water resistance of GB/T1733-1993 standard testing dry film, the testing time is 10 days, the waterproof performance of dry film of the present invention
Normally；With the glossiness of GB/T9754-2007 standard testing dry film, the glossiness of dry film of the present invention >=90Gu60 °.
In above embodiment of the present invention, unmentioned component or mode are all made of well known to those skilled in the art
Commercial product or well known mode.
In order to further illustrate the present invention, low to a kind of urethane acrylate provided by the invention below with reference to embodiment
Polymers and preparation method thereof and a kind of water paint are described in detail, but cannot be interpreted as them to protect model to the present invention
The restriction enclosed.
Embodiment 1
39g polyester polyol (manufacturer is first added：Hua Feng group, model PE-1280S, number-average molecular weight 1300),
5.36g dihydromethyl propionic acid and 1.8g urea drip 44.4g isophorone diisocyanate in 30min, are warming up to 70 DEG C of guarantors
Warm 2h；0.12g hydroquinone, 12.8g hydroxy-ethyl acrylate and 0.06g dibutyl tin dilaurate are added, is continued at 70 DEG C
2h is kept the temperature, room temperature is down to naturally, obtains urethane acrylate oligomer.
By the hexanediyl ester reactive diluent of the urethane acrylate oligomer of 20 mass parts, 40 mass parts
It is mixed with the 2- hydroxy-2-methyl -1- phenylacetone of 5 mass parts, high speed dispersion 30min under the conditions of 2000r/min；It adds
The polysiloxane leveling agents (BYK, model 333) of 1 mass parts, 1 mass parts polysiloxane compound defoaming agent (Digao company,
Model 902W) and 2 mass parts aqueous wetting agents (hamming this, model W-77), continue high speed dispersion under conditions of 2000r/min
30min；Then the deionized water of 31 mass parts is added, under conditions of 2000r/min, high speed dispersion 30min crosses 400 meshes,
Screenings is the coating of UV curable.
The coating of gained UV curable is sprayed at progress UV solidification, condition of cure on ABS plastic lid：Energy range is
800mj/cm2, conveying speed 30m/min obtains the dry film with a thickness of 20 μm after solidifying 5s.
Embodiment 2
39g polyester polyol (with embodiment 1), 6.7g dihydromethyl propionic acid and 1.2g urea is first added, it is different that 44.4g is added dropwise
Isophorone diisocyanate is warming up to 70 DEG C of heat preservation 2h；Add 0.2g hydroquinone, 15.6g hydroxy-ethyl acrylate and 0.12g
Dibutyl tin dilaurate continues to be down to room temperature naturally in 70 DEG C of heat preservation 2h, obtain urethane acrylate oligomer.
By the hexanediyl ester reactive diluent of the urethane acrylate oligomer of 10 mass parts, 40 mass parts
It is mixed with the 2- hydroxy-2-methyl -1- phenylacetone of 6 mass parts, under conditions of 2000r/min, high speed dispersion 30min；Again
The polysiloxane leveling agents (BYK, model 333) of 1 mass parts, polysiloxane compound defoaming agent (the Digao public affairs of 1 mass parts are added
Department, model 902W) and 2 mass parts aqueous wetting agents (hamming this, model W-77) continue high speed under the conditions of 2000r/min and divide
Dissipate 30min；Then the deionized water of 40 mass parts is added, under the conditions of 2000r/min, high speed dispersion 30min crosses 400 meshes,
Screenings is the coating of UV curable.
The coating of gained UV curable is sprayed at progress UV solidification, condition of cure on ABS plastic lid：Energy range is
800mj/cm2, conveying speed 30m/min obtains the dry film with a thickness of 23 μm after solidifying 10s.
Embodiment 3
26g polyester polyol (with embodiment 1), 8g dihydromethyl propionic acid and 1.2g urea is first added, the different Buddhist of 44.4g is added dropwise
That ketone diisocyanate, is warming up to 70 DEG C of heat preservation 2h；Add 0.18g hydroquinone, 10g hydroxy-ethyl acrylate and 0.18g bis-
Dibutyl tin laurate continues in 70 DEG C of heat preservation 2h, and water cooling to room temperature obtains urethane acrylate oligomer.
By the hexanediyl ester reactive diluent of the urethane acrylate oligomer of 25 mass parts, 35 mass parts
It is mixed with the 2- hydroxy-2-methyl -1- phenylacetone of 7 mass parts, under conditions of 2000r/min, high speed dispersion 30min；Again
The polysiloxane leveling agents (BYK, model 333) of 0.5 mass parts, the polysiloxane compound defoaming agent (enlightening of 1.2 mass parts are added
Gao company, model 902W) and 2 mass parts aqueous wetting agents (hamming this, model W-77) continue high under the conditions of 2000r/min
Speed dispersion 30min；Then the deionized water of 35 mass parts is added, under the conditions of 2000r/min, high speed dispersion 30min crosses 400
Mesh, screenings are the coating of UV curable.
The coating of gained UV curable is sprayed at progress UV solidification, condition of cure on ABS plastic lid：Energy range is
900mj/cm2, conveying speed 30m/min obtains the dry film with a thickness of 25 μm after solidifying 6s.
Embodiment 4
26g polyester polyol (with embodiment 1), 6.7g dihydromethyl propionic acid and 1.8g urea is first added, it is different that 44.4g is added dropwise
Isophorone diisocyanate is warming up to 70 DEG C of heat preservation 2h；Add to 0.24g hydroquinone, 10.8g hydroxy-ethyl acrylate and
0.2g dibutyl tin dilaurate continues in 70 DEG C of heat preservation 2h, and water cooling to room temperature obtains urethane acrylate oligomer.
By the hexanediyl ester reactive diluent of the urethane acrylate oligomer of 15 mass parts, 32 mass parts
It is mixed with the 2- hydroxy-2-methyl -1- phenylacetone of 4 mass parts, under conditions of 2000r/min, high speed dispersion 30min；Again
The polysiloxane leveling agents (BYK, model 333) of 1.5 mass parts, the polysiloxane compound defoaming agent (Digao of 1 mass parts are added
Company, model 902W) and 2.5 mass parts aqueous wetting agents (hamming this, model W-77) continue high under the conditions of 2000r/min
Speed dispersion 30min；Then the deionized water of 40 mass parts is added, under the conditions of 2200r/min, high speed dispersion 28min crosses 400
Mesh, screenings are the coating of UV curable.
The coating of gained UV curable is sprayed at progress UV solidification, condition of cure on ABS plastic lid：Energy range is
850mj/cm2, conveying speed 30m/min obtains the dry film with a thickness of 22 μm after solidifying 8s.
Comparative example 1
26 grams of polyester polyol (manufacturers are first added：Hua Feng group, model PE-1280S, number-average molecular weight 1300), 8 grams
Dihydromethyl propionic acid, then 44.4 grams of isophorone diisocyanate are added dropwise, it is warming up to 70 DEG C and keeps the temperature 2 hours.It adds to 0.18
Gram hydroquinone, 10 grams of hydroxy-ethyl acrylates, 0.18 gram of dibutyl tin dilaurate continue to keep the temperature 2 hours at 70 DEG C, are down to room
Temperature obtains oligomer.
Water paint and dry film are prepared according to the dosage of embodiment 2, method.
Comparative example 2
The oligomer prepared using comparative example 1 prepares water paint and dry film, difference according to the method for comparative example 1
The dosage for being photoinitiator is 5.5 mass parts, adds the anti-sagging agent (hamming this, model WT-105A) of 0.5 mass parts.
Performance detection and result
According to the detection method of this field routine, the items of Examples 1 to 4 and 1~2 gained dry film of comparative example are detected
Can, wherein dry film appearance is tested by ocular estimate；Adhesive force is according to GB/T9286-1998 standard testing；Hardness is according to GB/
T6739-2006 standard testing；Water resistance is according to GB/T1733-1993 standard testing；Glossiness is marked according to GB/T9754-2007
Quasi- test.Test result is as shown in table 1.
1~2 dry film the performance test results of 1 Examples 1 to 4 of table and comparative example
By 1 test result of table it is found that urethane acrylate oligomer provided by the invention, relative to traditional polyurethane
For acrylic acid, facade flowing down problems existing for water paint can be overcome, hence it is evident that improve the flatness and glossiness of dry film.
As seen from the above embodiment, urethane acrylate oligomer produced by the present invention is due to containing polyureas segment and carboxylic
Base not only has good water dispersible, can also form slight three-dimensional netted knot by polyureas group and carboxyl in water
Structure, the sagging of film before the coating containing the resin can effectively prevent non-UV from solidifying.Water paint prepared by the present invention, no
Common anti-sagging agent is added, particle is not likely to produce, is suitable for the exigent plastic surface vacuum metallizing coating of gloss, such as may be used
For cosmetics and the vacuum coating bottom of Wines packing plastic products, finishing coat.
Although above-described embodiment is made that detailed description to the present invention, it is only a part of the embodiment of the present invention,
Rather than whole embodiments, people can also obtain other embodiments under the premise of without creativeness according to the present embodiment, these
Embodiment belongs to the scope of the present invention.
Claims (10)
1. a kind of urethane acrylate oligomer, by including that the polymerizable raw material below for preparing forms, the raw material for preparing includes
Major ingredient and auxiliary agent；The major ingredient includes diisocyanate, polyester polyol, dihydromethyl propionic acid, urea and monohydroxy acrylic acid
Ester；The auxiliary agent includes polymerization inhibitor and catalyst.
2. polyurethane acroleic acid oligomer as described in claim 1, which is characterized in that the diisocyanate includes toluene two
Isocyanates, methyl diphenylene diisocyanate, benzene dimethylene diisocyanate, hexamethylene diisocyanate, different Fo Er
One or more of ketone diisocyanate and dicyclohexyl methyl hydride diisocyanate；
The polyester polyol includes the condensation polymer of polyalcohol and binary acid；The polyalcohol includes dihydric alcohol, trihydroxylic alcohol and four
One or more of first alcohol；
The monohydroxy acrylate includes hydroxy-ethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, metering system
One or more of sour hydroxypropyl acrylate.
3. polyurethane acroleic acid oligomer as claimed in claim 1 or 2, which is characterized in that the polyester polyol and two different
The mass ratio of cyanate is 0.5~0.9:1；
The mass ratio of the dihydromethyl propionic acid and diisocyanate is 0.12~0.20:1；
The mass ratio of the urea and diisocyanate is 0.027~0.042:1；
The molar ratio of the monohydroxy acrylate and diisocyanate is 1:0.5~2.
4. polyurethane acroleic acid oligomer as described in claim 1, which is characterized in that the polymerization inhibitor includes hydroquinone
And/or p methoxy phenol.
5. polyurethane acroleic acid oligomer as described in claim 1, which is characterized in that the catalyst includes two fourth of lauric acid
One or more of Ji Xi, cobalt octoate and zinc naphthenate.
6. polyurethane acroleic acid oligomer as described in claim 1, which is characterized in that the polymerization inhibitor accounts for polyurethane acroleic acid
Ester oligomer prepares the 0.01~1% of total mass of raw material；The catalyst accounts for urethane acrylate oligomer, and to prepare raw material total
The 0.01~1% of quality.
7. the preparation method of any one of claim 1~6 urethane acrylate oligomer, includes the following steps：
(1) mixture of polyester polyol, dihydromethyl propionic acid, urea and diisocyanate is subjected to polycondensation reaction, is gathered
Urethane performed polymer；
(2) base polyurethane prepolymer for use as of the step (1) is mixed with monohydroxy acrylate and auxiliary agent, carries out condensation reaction, obtains
To urethane acrylate oligomer；The auxiliary agent includes polymerization inhibitor and catalyst.
8. preparation method as claimed in claim 7, which is characterized in that the polycondensation reaction of the step (1) and the contracting of step (2)
The temperature for closing reaction independently is 60~100 DEG C；The time of polycondensation reaction and condensation reaction independently is 1~3h.
9. a kind of water paint, in terms of mass parts, including 8~30 parts of urethane acrylate oligomers, 10~60 parts of activity are dilute
Release agent, 2~10 parts of photoinitiators, 1~18 part of coating additive and 30~50 parts of water；The urethane acrylate oligomer is power
Benefit requires any one of 1~6 urethane acrylate oligomer or the preparation method of claim 7 or 8 to be prepared
Urethane acrylate oligomer.
10. water paint as claimed in claim 9, which is characterized in that the coating additive includes levelling agent, defoaming agent, purple
One or more of outer light absorber and aqueous wetting agent；
The reactive diluent includes hexanediyl ester, three polypropyleneglycol diacrylates, trimethylolpropane tris third
One or more of olefin(e) acid ester and pentaerythritol tetraacrylate；
The photoinitiator includes 2- hydroxy-2-methyl -1- phenylacetone, 1- hydroxycyclohexyl phenyl ketone, 2- methyl -2-
(4- morpholinyl) -1- [4- (methyl mercapto) phenyl] -1- acetone, 2,4,6- trimethylbenzoy-dipheny phosphine oxide, 2,4,6-
Trimethylbenzoyl phenyl phosphinic acid ethyl ester, 2- dimethylamino -2- benzyl -1- [4- (4- morpholinyl) phenyl] -1- butanone and 2-
One or more of hydroxy-2-methyl -1- [4- (2- hydroxyl-oxethyl) phenyl] -1- acetone.
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