Single component UV-light self-crosslinked acrylate copolymer coating and synthesis method and application
Technical field
The present invention relates to a kind of coating, especially relate to a kind of single component UV-light self-crosslinked acrylate copolymer coating and synthesis method and application.
Background technology
Yodo Sol GH 28 coating has excellent photostabilization and outdoor aging performance, and most of Yodo Sol GH 28s are low toxicities or nontoxic, can directly be used for food product pack and medical and hygiene article.Common Yodo Sol GH 28 does not have bridging property, and its coating is softening easily when being heated, and can dissolve when meeting the machine solvent to come off, thereby on using, be restricted.Existing terms of settlement is in Yodo Sol GH 28, to introduce crosslinked function, for example heat cross-linking (Chinese invention patent application CN101724173A; The open CN101338006A of Chinese invention patent), two component normal temperature crosslinked (Chinese invention patent CN100368485C).One Chinese patent application CN101935387 then proposes a kind of modification UV photocuring pure acrylic resin, utilizes the epoxy group(ing) in the Yodo Sol GH 28 on copolymer chain, to introduce acrylic double bond, makes coating curing thereby photopolymerization can take place this pair key.
The ultraviolet light irradiation curing technology has and advantage such as solidifies rapidly, the consolidation zone selectivity is strong and temperature is low, and extremely people pay close attention to.Need to add ultraviolet initiator and UV-light initiation auxiliary agent during traditional ultraviolet light irradiation is coating material solidified, mostly ultraviolet initiator is 2-hydroxy-2-methyl-1-phenyl-acetone, 1-hydroxyl-cyclohexyl benzophenone, UVNUL MS-40, benzoin methyl ether, Benzoin ethyl ether or st-yrax n-butyl ether etc.; UV-light causes auxiliary agent and is mostly triethylamine, diethylamine, trolamine or diethanolamine etc.Solidify the residual ultraviolet initiator in back easily to surface transport; Generate toxic by-products; Has stronger smell; And the easy flavescence of filming, big limitations the development space of UV-curing technology at some expensive goods (like food product pack, medical and hygiene article, cosmetic products and personal-care supplies).
Summary of the invention
The object of the invention be exactly provide in order to overcome the defective that above-mentioned prior art exists a kind of temperature tolerance good, do not contain micromolecular compound; Toxic by-products can be do not formed, single component UV-light self-crosslinked acrylate copolymer coating and the synthesis method and the application of different application requirement, stable performance can be adapted to.
The object of the invention can be realized through following technical scheme: a kind of single component UV-light self-crosslinked acrylate copolymer coating is characterized in that this coating comprises following component and weight part content:
UV-light reactive monomer 0.02~8;
Photo-crosslinking function monomer 2~20;
Other single functionality monomers 15~40;
Initiator 0.04~0.8;
Solvent 30~80.
Described coating comprises following component and weight part content:
UV-light reactive monomer 2~6;
Photo-crosslinking function monomer 8~16;
Other single functionality monomers 20~30;
Initiator 0.1~0.5;
Solvent 45~70.
Described coating comprises following component and weight part content:
UV-light reactive monomer 2~4;
Photo-crosslinking function monomer 10~12;
Other single functionality monomers 22~28;
Initiator 0.2~0.3;
Solvent 50~60.
Described UV-light reactive monomer is selected from the acrylic ester monomer that contains the UV-light active group or in the vinyl monomer one or more; Described photo-crosslinking function monomer is selected from one or more in acrylic ester monomer or the vinyl monomer; Described other single functionality monomers are selected from 3~8 kinds in acrylic ester monomer or the vinyl monomer.
Described UV-light reactive monomer is selected from one or more in 4-(2-hydroxyl-3-allyloxy-propoxy-) UVNUL MS-40,4-(2-hydroxyl-3-acryloxy-propoxy-) UVNUL MS-40,4-(2-hydroxy-3-methyl acryloxy-propoxy-) UVNUL MS-40,4-(2-acryloxy-ethyl) UVNUL MS-40,4-(2-methacryloxy-ethyl) UVNUL MS-40, the 4-acryloxy UVNUL MS-40; Described photo-crosslinking function monomer is selected from one or more in dimethylaminoethyl methacrylate, vinylformic acid-2-hydroxypropyl acrylate, methacrylic acid-2-hydroxypropyl acrylate, isobutyl acrylate, Propenoic acid, 2-methyl, isobutyl ester, isodecyl acrylate, isodecyl methacrylate, Isooctyl acrylate monomer or the Isooctyl methacrylate; Described other single functionality monomers are selected from vinylformic acid; Methacrylic acid; Vinylformic acid-2-hydroxyl ethyl ester; 2-hydroxyethyl methacrylate; Glycidyl acrylate; Glycidyl methacrylate; Methylene-succinic acid; Dibutyl maleate; Dioctyl maleate; Vinyl-acetic ester; Vinylbenzene; Acrylamide; Methacrylamide; Vinyl cyanide; Methyl acrylate; Methyl methacrylate; Ethyl propenoate; Jia Jibingxisuanyizhi; Bing Xisuandingzhi; Butyl methacrylate; In lauryl acrylate or the lauryl methacrylate(LMA) 3~8 kinds.
Described initiator is selected from benzoyl peroxide or Diisopropyl azodicarboxylate.
Described solvent is selected from one or more in ethanol, Virahol or the ethyl acetate.
A kind of preparation method of single component UV-light self-crosslinked acrylate copolymer coating; It is characterized in that; This method is that UV-light reactive monomer, photo-crosslinking function monomer, other single functionality monomers, initiator and solvent are dropped in the reaction kettle; Mix at 75 ℃~90 ℃ refluxing and stirring 5h~8h, promptly get product after the cooling.
A kind of application of single component UV-light self-crosslinked acrylate copolymer coating; It is characterized in that; Single component UV-light self-crosslinked acrylate copolymer coating is coated on the base material of product to be coated, volatilizes and in the ultraviolet light polymerization device, carry out that illumination is crosslinked to get final product behind the solvent.
The irradiation energy of described UV-light self-crosslinking is 500mJ, and through test, the degree of crosslinking of coating is 80% behind the ultraviolet light irradiation, and heat resistance improves 40 ℃.
The degree of crosslinking of ultraviolet light cross-linking coating is pressed the test of Suo Shi extraction process.
The heat resistance of coating is with the test of heat-sealing gradometer.
Compared with prior art, the mode with covalent linkage in polymerization process of the UV-light active group in the coating of the present invention combines with polymer chain, has avoided adding ultraviolet initiator and UV-light and has caused micromolecular that auxiliary agent causes and separate out and move.After the coating drying, coating forms cross-linked network fast under uv light irradiation.Diphenyl ketone type UV-light active group in the coating and the reaction of the non-pair of of bonding photo-crosslinking functional group form covalent linkage and produce crosslinkedly, and product of the present invention has the following advantages:
(1) through the design to the composition and the molecular structure of coating, form cross-linked network fast through ultraviolet light irradiation, heat resistance is significantly improved; (2) do not contain micromolecular compound, can not form toxic by-products; (3) can obtain suitable degree of crosslinking through the consumption of regulating the UV-light reactive monomer, the consumption and the monomeric consumption of other single functionalities of photo-crosslinking function monomer, to adapt to the different application requirement; (4) because the stable performance in coating of UV-light active group, under the lucifuge condition not can with other group generation crosslinking reactions, just self-crosslinking can take place only under action of ultraviolet light, at room temperature lucifuge was stored 6 months, it is stable that performance still keeps.
Embodiment
Below in conjunction with specific embodiment the present invention is elaborated.
Embodiment 1
The single component UV-light self-crosslinked acrylate copolymer coating of present embodiment is synthetic for raw material by following component (weight part):
Concrete building-up process is: mix stirring to make in UV-light reactive monomer, photo-crosslinking function monomer, other single functionality monomers, initiator and the solvent input reaction kettle; Agitation condition is at 80 ℃ of backflow 6h, obtains single component UV-light self-crosslinked acrylate copolymer coating after the cooling.
Above-mentioned gained single component UV-light self-crosslinked acrylate copolymer coating is coated with on base material, volatilizes that in the ultraviolet light polymerization device, to carry out illumination behind the solvent crosslinked, and the irradiation energy of UV-light self-crosslinking is 500mJ.Through test, the degree of crosslinking of coating is 80% behind the ultraviolet light irradiation, and heat resistance improves 40 ℃.
Embodiment 2
The single component UV-light self-crosslinked acrylate copolymer coating of present embodiment is synthetic for raw material by following component (weight part):
Building-up process is identical with embodiment 1.Gained single component UV-light self-crosslinked acrylate copolymer coating is coated with on base material, volatilizes that in the ultraviolet light polymerization device, to carry out illumination behind the solvent crosslinked, and the irradiation energy of UV-light self-crosslinking is 500mJ.Through test, the degree of crosslinking of coating is 60% behind the ultraviolet light irradiation, and heat resistance improves 20 ℃.
Embodiment 3
The single component UV-light self-crosslinked acrylate copolymer coating of present embodiment is synthetic for raw material by following component (weight part):
Building-up process is identical with embodiment 1.Gained single component UV-light self-crosslinked acrylate copolymer coating is coated with on base material, volatilizes that in the ultraviolet light polymerization device, to carry out illumination behind the solvent crosslinked, and the irradiation energy of UV-light self-crosslinking is 500mJ.Through test, the degree of crosslinking of coating is 90% behind the ultraviolet light irradiation, and heat resistance improves 40 ℃.
Embodiment 4
The single component UV-light self-crosslinked acrylate copolymer coating of present embodiment is synthetic for raw material by following component (weight part):
Building-up process is identical with embodiment 1.Gained single component UV-light self-crosslinked acrylate copolymer coating is coated with on base material, volatilizes that in the ultraviolet light polymerization device, to carry out illumination behind the solvent crosslinked, and the irradiation energy of UV-light self-crosslinking is 500mJ.Through test, the degree of crosslinking of coating is 69% behind the ultraviolet light irradiation, and heat resistance improves 30 ℃.
Embodiment 5
The single component UV-light self-crosslinked acrylate copolymer coating of present embodiment is synthetic for raw material by following component (weight part):
Building-up process is identical with embodiment 1.Gained single component UV-light self-crosslinked acrylate copolymer coating is coated with on base material, volatilizes that in the ultraviolet light polymerization device, to carry out illumination behind the solvent crosslinked, and the irradiation energy of UV-light self-crosslinking is 500mJ.Through test, the degree of crosslinking of coating is 65% behind the ultraviolet light irradiation, and heat resistance improves 30 ℃.
Embodiment 6
The single component UV-light self-crosslinked acrylate copolymer coating of present embodiment is synthetic for raw material by following component (weight part):
Concrete building-up process is: mix stirring to make in UV-light reactive monomer, photo-crosslinking function monomer, other single functionality monomers, initiator and the solvent input reaction kettle; Agitation condition is at 75 ℃ of backflow 5h, obtains single component UV-light self-crosslinked acrylate copolymer coating after the cooling.
Above-mentioned gained single component UV-light self-crosslinked acrylate copolymer coating is coated with on base material, volatilizes that in the ultraviolet light polymerization device, to carry out illumination behind the solvent crosslinked, and the irradiation energy of UV-light self-crosslinking is 200mJ.Through test, the degree of crosslinking of coating is 80% behind the ultraviolet light irradiation, and heat resistance improves 40 ℃.
Embodiment 7
The single component UV-light self-crosslinked acrylate copolymer coating of present embodiment is synthetic for raw material by following component (weight part):
Concrete building-up process is: mix stirring to make in UV-light reactive monomer, photo-crosslinking function monomer, other single functionality monomers, initiator and the solvent input reaction kettle; Agitation condition is at 90 ℃ of backflow 8h, obtains single component UV-light self-crosslinked acrylate copolymer coating after the cooling.
Above-mentioned gained single component UV-light self-crosslinked acrylate copolymer coating is coated with on base material, volatilizes that in the ultraviolet light polymerization device, to carry out illumination behind the solvent crosslinked, and the irradiation energy of UV-light self-crosslinking is 2000mJ.Through test, the degree of crosslinking of coating is 80% behind the ultraviolet light irradiation, and heat resistance improves 40 ℃.
Embodiment 8
The single component UV-light self-crosslinked acrylate copolymer coating of present embodiment is synthetic for raw material by following component (weight part):
Concrete building-up process is: mix stirring to make in UV-light reactive monomer, photo-crosslinking function monomer, other single functionality monomers, initiator and the solvent input reaction kettle; Agitation condition is at 75~80 ℃ of 5~6h that reflux, and obtains single component UV-light self-crosslinked acrylate copolymer coating after the cooling.
Above-mentioned gained single component UV-light self-crosslinked acrylate copolymer coating is coated with on base material, volatilizes that in the ultraviolet light polymerization device, to carry out illumination behind the solvent crosslinked, and the irradiation energy of UV-light self-crosslinking is 500~600mJ.Through test, the degree of crosslinking of coating is 85% behind the ultraviolet light irradiation, and heat resistance improves 45 ℃.
Embodiment 9
The single component UV-light self-crosslinked acrylate copolymer coating of present embodiment is synthetic for raw material by following component (weight part):
Concrete building-up process is: mix stirring to make in UV-light reactive monomer, photo-crosslinking function monomer, other single functionality monomers, initiator and the solvent input reaction kettle; Agitation condition is at 85~90 ℃ of 7~8h that reflux, and obtains single component UV-light self-crosslinked acrylate copolymer coating after the cooling.
Above-mentioned gained single component UV-light self-crosslinked acrylate copolymer coating is coated with on base material, volatilizes that in the ultraviolet light polymerization device, to carry out illumination behind the solvent crosslinked, and the irradiation energy of UV-light self-crosslinking is 1000~1200mJ.Through test, the degree of crosslinking of coating is 90% behind the ultraviolet light irradiation, and heat resistance improves 50 ℃.