CN105602430A - Pre-coated composition, UV cured product and preparation method of UV solidified product - Google Patents
Pre-coated composition, UV cured product and preparation method of UV solidified product Download PDFInfo
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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
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
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- 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
- C09D169/00—Coating compositions based on polycarbonates; Coating compositions based on derivatives of polycarbonates
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- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2475/04—Polyurethanes
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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Abstract
The invention provides a pre-coated composition, a UV cured product and a preparation method of UV cured product. The pre-coated composition is prepared from, by weight, 60-80% of water-based thermosetting resin emulsion, 10-25% of water-based UV resin emulsion and 1-15% of a curing agent. The water-based thermosetting resin emulsion comprises water-based thermosetting resin, the water-based UV resin emulsion comprises water-based UV resin, the particle size of the water-based thermosetting resin emulsion is smaller than 100 nm, and the particle size of the water-based UV resin emulsion is smaller than 150 nm. Because a functional double bond of the water-based UV resin within the particle size range can react with a functional double bond in pre-coated UV paint under the action of an initiator in the pre-coated UV paint, the water-based thermosetting resin emulsion within the particle size range can react with the curing agent to improve adhesive force between a pre-coated layer and a UV coating.
Description
Technical field
The present invention relates to ultraviolet curing technology field, in particular to the pre-coating composition of one, UV cured article andPreparation method.
Background technology
Ultraviolet-curing paint (UV coating) contains VOC (VOC) and initator, and has environment dirtDye little, curing rate fast, save the energy, cured product performance good, be suitable for the advantages such as high-speed automated production. Because UV is coated withExpect unique technology and application advantage, be widely applied to rapidly the industry-by-industries such as electronic product, machine-building, anti-corrosion of metalAnd field, be described as brand-new environmental friendly material.
Develop into the fields such as plastics, metal, pottery, glass during when UV cured article, the intrinsic defect of some UV coating is also got overCome to be displayed manyly. Wherein, the topmost problem of UV coating industry is the adhesion problem of UV coating. UV coatingBe difficult to adhere at plastics, metal, pottery, these level and smooth substrate surfaces of glass, become the bottleneck that hinders UV coating continuation development.For example, in the time that UV coating is fixed on PET material, because PET is the material of low pole, directly enter on PET film surfaceThe coating of row UV coating declines the adhesive force that causes UV coating.
In order to improve the adhesive force between substrate layer and UV coating, the patent application document that application number is CN201210408829.6In a kind of environment-friendly water-based high adhesion force PET precoated shet coating composition and preparation, purposes are disclosed. This coating composition comprises as followsEach component of parts by weight: 60～75 parts of water-base resins, 0～15 part of cosolvent, 0～20 part of deionized water, wherein cosolvent,The parts by weight of deionized water are 0 part when different. But the precoated shet that utilizes aforementioned coating composition to form need carry out UV and solidify,Thereby can only be coated with by off-line, cause operation loaded down with trivial details.
Application number is to disclose a kind of water for UV light-curable ink priming coat in the patent application document of CN201310365498.7Property PET bottom-coating and its preparation method and application. In the coating of every 100 weight portions, comprise each component of following parts by weight:Aqueous polyester resin 40～75 parts by weight; Cosolvent 3～15 parts by weight; Deionized water 5～57 parts by weight; Defoamer 0.1～0.5Parts by weight. But in above-mentioned preparation method, need PET to carry out sided corona treatment, thereby be also not suitable for online coating.
Summary of the invention
Main purpose of the present invention is to provide a kind of pre-coating composition, UV cured article and preparation method thereof, existing to solveIn technology, UV coating is difficult to be attached to the problem of substrate surface.
To achieve these goals, according to an aspect of the present invention, provide a kind of pre-coating composition, comprised weight percentThan being 60%～80% water-based thermosetting resin emulsion, water-based UV resin emulsion and the weight hundred that percentage by weight is 10%～25%Proportion by subtraction is 1%～15% curing agent, and water-based thermosetting resin emulsion comprises water-based thermosetting resin, and water-based UV resin emulsion comprises waterProperty UV resin, and the particle diameter of water-based thermosetting resin emulsion is less than 100nm, and the particle diameter of water-based UV resin emulsion is less than 150nm.
Further, water-based thermosetting resin is anionic resin, and the number-average molecular weight of water-based thermosetting resin is 1000～20000,Be preferably 1000～5000, the weight average molecular weight of water-based thermosetting resin is 5000～50000, is preferably 10000～30000, water feverGu the vitrification point of resin is 20～120 DEG C, be preferably 20～70 DEG C.
Further, in water-based thermosetting resin emulsion, the content of water-based thermosetting resin is 30%～60%, now water-based thermosetting resin breastThe acid number of liquid is 5～10mgKOH/g.
Further, water-based thermosetting resin is selected from water-borne acrylic resin, waterborne polyurethane resin and waterborne, polycarbonate resinAny one or more.
Further, the number-average molecular weight of water-based UV resin is 1000～20000, is preferably 3000～10000, water-based UV treeThe vitrification point of fat is less than 20 DEG C.
Further, in water-based UV resin emulsion, the content of water-based UV resin is 30%～60%, now water-based UV resin breastThe acid number of liquid is 10～20mgKOH/g.
Further, water-based UV resin is selected from water-based unsaturated polyester resin and/or waterborne epoxy acrylate.
According to a further aspect in the invention, provide a kind of preparation method of UV cured article, comprised the following steps: by above-mentionedPre-coating composition is arranged on plastic basis material layer; Pre-coating composition is dried to processing, obtains lamination layer structure, whereinPre-coating composition forms precoated shet; UV coating is arranged on the surface of precoated shet, forms UV coating; To precoated shet andUV coating is carried out UV and is solidified processing, and precoated shet forms UV and solidifies bottom, UV coating formation UV cured skin.
Further, plastic basis material layer is pet layer, before UV coating is arranged to the step on plastic basis material layer surface, and systemPreparation Method also comprises the step of lamination layer structure being carried out successively to stretch processing and heat treatment; The preferably preliminary drying temperature of stretch processingBe 90 DEG C～110 DEG C, the preliminary drying time is 20s～40s, and stretching ratio is 4～15 times; Preferably the setting temperature of heat treatment is 160 DEG C～200 DEG C, shaping time is 10s～30s.
In accordance with a further aspect of the present invention, provide a kind of UV cured article, UV cured article is prepared by above-mentioned preparation methodForm.
Apply technical scheme of the present invention, this pre-coating composition comprises that percentage by weight is 60%～80% water-based thermosetting resin breastThe curing agent that the water-based UV resin emulsion that liquid, percentage by weight are 10%～25% and percentage by weight are 1%～15%, water feverGu resin emulsion comprises water-based thermosetting resin, water-based UV resin emulsion comprises water-based UV resin, and water-based thermosetting resin emulsionParticle diameter is less than 100nm, and the particle diameter of water-based UV resin emulsion is less than 150nm, due to the water-based UV resin of above-mentioned particle size rangeUnder the enough effects with the functional pair of key initator in precoating UV coating in precoating UV coating of the functional pair of bond energy, react,By improving the density of precoated shet when the film forming, improve adhesive force between precoated shet and UV coating; And, above-mentioned particle diameter modelThe water-based thermosetting resin emulsion enclosing can, with curing agent by reacting to each other, improve cohesive force and the resistance to water of this pre-coating compositionAnd the density of precoated shet when film forming, thereby further improve adhesive force between precoated shet and UV coating.
Except object described above, feature and advantage, the present invention also has other object, feature and advantage. BelowWith reference to figure, the present invention is further detailed explanation.
Brief description of the drawings
The Figure of description that forms a part of the present invention is used to provide a further understanding of the present invention, schematic reality of the present inventionExecute example and explanation thereof for explaining the present invention, do not form inappropriate limitation of the present invention. In the accompanying drawings:
Fig. 1 shows the structural representation of a kind of UV cured article that embodiment of the present invention provides.
Detailed description of the invention
It should be noted that, in the situation that not conflicting, the feature in embodiment and embodiment in the present invention can combine mutually.Describe below with reference to the accompanying drawings and in conjunction with the embodiments the present invention in detail.
In order to make those skilled in the art person understand better the present invention program, below in conjunction with the accompanying drawing in the embodiment of the present invention,Technical scheme in the embodiment of the present invention is clearly and completely described, and obviously, described embodiment is only the present inventionThe embodiment of a part, instead of whole embodiment. Based on the embodiment in the present invention, those of ordinary skill in the art are not havingHave and make the every other embodiment obtaining under creative work prerequisite, all should belong to the scope of protection of the invention.
It should be noted that term " first ", " second " etc. in description of the present invention and claims and above-mentioned accompanying drawingBe for distinguishing similar object, and needn't be used for describing specific order or precedence. Should be appreciated that the data of such useSuitably exchanging in situation, so that embodiments of the invention described herein. In addition, term " comprises " and " having "And their any distortion, intention is to cover not exclusive comprising, for example, the process that comprised series of steps or unit,Those steps or unit that method, system, product or equipment are not necessarily limited to clearly list, but can not comprise clearly rowThat go out or for these processes, method, product or equipment intrinsic other step or unit.
From background technology, in prior art, UV coating is difficult at plastics, metal, pottery, these level and smooth substrate surfaces of glassAdhere to, become the bottleneck that hinders UV coating continuation development. The present inventor studies for the problems referred to above, provides oneKind of pre-coating composition, comprises that percentage by weight is that 60%～80% water-based thermosetting resin emulsion, percentage by weight are 10%～25%Water-based UV resin emulsion and the percentage by weight curing agent that is 1%～15%, water-based thermosetting resin emulsion comprises water-based thermosetting treeFat, water-based UV resin emulsion comprises water-based UV resin, and the particle diameter of water-based thermosetting resin emulsion is less than 100nm, water-based UVThe particle diameter of resin emulsion is less than 150nm.
The functional pair of bond energy due to the water-based UV resin of above-mentioned particle size range in above-mentioned pre-coating composition of the present invention is enough and pre-Be coated with under the effect of the functional pair of key initator in precoating UV coating in UV coating and react, pre-by improving when the film formingThe density of coating, has improved adhesive force between precoated shet and UV coating; And, the water-based thermosetting resin breast of above-mentioned particle size rangeLiquid can be with curing agent by reacting to each other, precoated shet while improving the cohesive force of this pre-coating composition and resistance to water and film formingDensity, thus adhesive force between precoated shet and UV coating further improved.
And in online coating process, the precoated shet being formed by pre-coating composition can not rupture, it is at 90 DEG C～110 DEG CAt temperature, can realize the stretching of 4～15 times, and then make above-mentioned pre-coating composition in use without carrying out the processing such as corona, justCan be applicable to, in online coating process, simplify operation, improve the UV cured article that formed by above-mentioned pre-coating compositionEntirety yield.
In pre-coating composition provided by the invention, preferably, water-based thermosetting resin can be anionic resin, and water-basedThe number-average molecular weight of thermosetting resin is 1000～20000, is preferably 1000～5000, and the weight average molecular weight of water-based thermosetting resin is5000～50000, be preferably 10000～30000; And preferably, the vitrification point of water-based thermosetting resin is 20～120 DEG C,Be preferably 20～70 DEG C. Select anionic resin can effectively improve the stability of emulsion, and make on water-based thermosetting resin hasState preferred number-average molecular weight and weight average molecular weight, not only can make the precoated shet forming all have well plastic basis material and UV layerAdhesive force, can also have good resistance to water, and the water-based thermosetting resin with above-mentioned vitrification point can make dry after shapeThe UV becoming solidifies bottom good percentage elongation and surface drying.
Above-mentioned water-based thermosetting resin emulsion can adopt conventional water-based thermosetting resin content in prior art emulsion. Preferably, waterIn solid resin emulsion hot in nature, the content of water-based thermosetting resin is 30%～60%. Water-based thermosetting resinous acid value is set in above-mentioned scope,Not only can make it take into account good hydrophily and resistance to water, can also make the precoated shet forming have plastic basis material and UV coatingGood adhesive force; And preferably, the particle diameter of water-based thermosetting resin emulsion is less than 100nm, water-based thermosetting resin emulsionPH value is 7～9, and the particle diameter of water-based thermosetting resin emulsion and pH value are set in above-mentioned preferred scope and can be effectively improvedThe stability of emulsion, and effectively increased holding time of emulsion.
In pre-coating composition provided by the invention, preferably, water-based thermosetting resin is selected from water-borne acrylic resin, water-based is poly-Any one or more in ammonia ester resin and waterborne, polycarbonate resin. Functional pair of key in the water-based thermosetting resin of mentioned kindAll can be effectively react with under the effect of the functional pair of key initator in precoating UV coating in precoating UV coating, fromAnd improve the adhesive force between precoated shet and UV coating.
In pre-coating composition provided by the invention, preferably, the number-average molecular weight of water-based UV resin is 1000～20000,Be preferably 3000～10000; And preferably, the vitrification point of water-based UV resin is less than 20 DEG C. Having above-mentioned number divides equallyThe water-based UV resin of son amount can improve the resistance to water of resin effectively, and has the water-based UV resin energy of above-mentioned vitrification pointEnough make the precoated shet forming have good percentage elongation.
Can be the emulsion of the conventional water-based UV of prior art resin content for the application's water-based UV resin emulsion, preferably,In water-based UV resin emulsion, the content of water-based UV resin is 30%～60%. Water-based UV resinous acid value is set in to above-mentioned scopeIn can effectively improve resin hydrophily, and form precoated shet plastic basis material and UV coating are had to good adhesive force; AndAnd preferably, the particle diameter of water-based UV resin emulsion is less than 150nm, the pH value of water-based UV resin emulsion is 6～8, by waterProperty UV resin emulsion particle diameter and pH value be set in the stability that can effectively improve emulsion in above-mentioned preferred scope, and increaseAdd the holding time.
Preferably, water-based UV resin is selected from water-based unsaturated polyester resin and/or waterborne epoxy acrylate. The water of mentioned kindProperty UV resin all can react with curing agent effectively, thereby has improved cohesive force and the resistance to water of this pre-coating composition, and thenFurther improve adhesive force between precoated shet and UV coating.
In pre-coating composition provided by the invention, curing agent can be selected according to prior art, be preferably isocyanates,Any one or more in oxazoline, melamine, carbon imines. Add curing agent can make pre-water-based thermosetting resin and water feverGu resin solidification, thereby mechanical property, heat resistance, resistance to water and the corrosion resistance of pre-coating composition are improved. And, pre-Coating composition can also comprise that percentage by weight is 1%～5% cosolvent, cosolvent be preferably methyl alcohol, ethanol, isopropyl alcohol,Any one or more in EGME, butyl glycol ether, propylene-glycol ethyl ether, diethylene glycol ether. Above-mentioned cosolvent canEffectively increase water-based thermosetting resin and the solubility of water-based UV resin in deionized water, thereby more effectively improved water-basedThermosetting resin and water-based UV resin are for the effect that improves adhesive force between precoated shet and UV coating.
In pre-coating composition provided by the invention, preferably, pre-coating composition also comprises that percentage by weight is 0.5%～5%Adhesion promoter, levelling agent that percentage by weight is 0.1%～2% and the percentage by weight antitack agent that is 0.1%～0.5% inAny one or more. Adopt above-mentioned adhesion promoter can further improve adhesive force between precoated shet and UV coating; Above-mentioned streamFlat agent, as a kind of coating additive, can reduce the surface tension of coating effectively, improves the permeability of coating, improves its levellingProperty, uniformity and spreadability, thus make pre-coating composition in drying and forming-film process, form one smooth, smooth, uniformFilm; And above-mentioned antitack agent can be used for reducing the tack of coating.
In above-mentioned preferred pre-coating composition, adhesion promoter can be appointing in acrylic resin, saturated polyester resinOne or more; More preferably, the glass transition temperature of adhesion promoter is 0 DEG C～50 DEG C, molecular weight 1000～20000.The glass transition temperature of adhesion promoter and molecular weight are limited to above-mentioned parameter scope and can make the precoated shet forming after dryPlastic basis material and UV coating are all had to good adhesive force. Above-mentioned levelling agent can be that organic silicon modified by polyether, acrylate are commonAny one or more in aggressiveness and polyoxyethylene alkyl ether. Above-mentioned antitack agent can be polysiloxanes, mineral oils and wax emulsionIn any one or more.
According to another aspect of the present invention, also provide a kind of preparation method of UV cured article, comprised the following steps: by upperAfter the pre-coating composition dilution of stating, be arranged on plastic basis material layer, in the solution after dilution, solid content is preferably 5%～10%; To in advanceCoating composition is dried processing, obtains lamination layer structure, and wherein pre-coating composition forms precoated shet; UV coating is arrangedOn the surface of precoated shet, form UV coating; Precoated shet and UV coating are carried out to the curing processing of UV, and precoated shet forms UVSolidify bottom, UV coating formation UV cured skin. Wherein, the diluent of pre-coating composition dilution is preferably to deionizationWater, the thickness that UV solidifies bottom is preferably 0.05～0.3 μ m.
This preparation method is by above-mentioned pre-coating composition is arranged on plastic basis material layer, and by dry pre-coating composition shapeBecome precoated shet, thus by functional pair of key in the functional pair of key and UV coating in water-based UV resin in precoated shet at UVReaction in coating under the effect of initator, has improved adhesive force between precoated shet and UV coating; Also by the water-based in precoated shetReacting to each other of thermosetting resin and curing agent, has improved cohesive force and the resistance to water of this precoated shet, thereby has further improved precoatingAdhesive force between layer and UV coating, so improved plastic basis material layer and the UV cured skin that solidify to form between adhesive force;And in online coating process, the precoated shet being formed by pre-coating composition can not rupture, it is at 90 DEG C～110 DEG CAt temperature, can realize the stretching of 4～15 times, and then make above-mentioned pre-coating composition in use without carrying out the processing such as corona, justCan be applicable to, in online coating process, simplify operation, improve the UV cured article that formed by above-mentioned pre-coating compositionEntirety yield.
One preferred embodiment in, plastic basis material layer is pet layer, UV coating is being arranged to plastic basis material layer surfaceStep before, first lamination layer structure is carried out to stretch processing and heat treatment successively. Because above-mentioned pre-coating composition can be fittedFor online coating process, thereby by lamination layer structure is carried out to stretch processing and heat treatment successively, realize precoatingThe online coating of feed composition.
Above-mentioned preferred embodiment in, more effectively, the preliminary drying temperature of stretch processing is 90 DEG C～110 DEG C, the preliminary drying timeFor 20s～40s, stretching ratio is 4～15 times. The process conditions of stretch processing are set within the scope of above-mentioned parameter and can be being ensuredOn the basis that lamination layer structure is effectively stretched, effectively reduce the impact that in drawing process, lamination layer structure is subject to, as higherTemperature and longer time can cause plastic basis material layer crystalline polamer to occur as PET. And, more effectively, heat treatmentSetting temperature is 180 DEG C～220 DEG C, and shaping time is 10s～30s. The process conditions of heat treatment are set in to above-mentioned parameter scopeIn can ensure, on the basis that lamination layer structure is finalized, effectively to reduce the impact that in type-approval process, lamination layer structure is subject to,As the distortion of plastic basis material layer, and cause the heat endurance variation of plastic basis material layer.
According to a further aspect of the invention, provide a kind of UV cured article being prepared from by above-mentioned preparation method, as figureShown in 1, comprise that the plastic basis material layer 10, the UV that are cascading solidify bottom 20 and UV cured skin 30. Wherein, UVSolidify bottom 20 and solidify to process and form by precoated shet being carried out to UV, UV cured skin 30 is by UV coatingCarry out UV solidify process and form.
Because this UV cured article is prepared from by above-mentioned preparation method, thereby by improving between precoated shet and UV coatingAdhesive force, has improved UV and solidified the adhesive force between bottom 20 and UV cured skin 30, and then it is curing also to have improved UVAdhesive force between top layer 30 and plastic basis material layer 10, has finally improved the reliability of UV cured article; Solid owing to forming UVTo change the water-based thermosetting resin of bottom 20 can react to each other with curing agent, improved this UV and solidified the cohesive force of bottom 20 and water-fastProperty, thereby further improve the adhesive force between UV cured skin 30 and plastic basis material layer 10, also further improve UVThe reliability of cured article; And, utilize the UV cured article that above-mentioned preparation method is prepared to there is high surface tension value,More than at least can reaching 40 dyne, thereby can not cause the contraction of recoat material face, but also can increase recoat materialAdherence effect, and then be applicable to the application such as photocuring and thermosetting material recoat.
Further illustrate below in conjunction with embodiment and comparative example pre-coating composition and the UV cured article that the application provides. Wherein,In embodiment 1 to 7, in pre-coating composition, kind and the percentage by weight of each component are as shown in the table:
Embodiment 1
In the pre-coating composition of the present embodiment, the percentage by weight of each component is in table 1, the preparation method of UV cured article comprise withLower step:
1, provide component and percentage by weight pre-coating composition as shown in table 1, wherein, the particle diameter of water-based thermosetting resin emulsionFor 80nm, the particle diameter of water-based UV resin emulsion is 120nm, and the number-average molecular weight of water-based thermosetting resin is 30000, and weight average dividesSon amount is 70000, and vitrification point is 150 DEG C, and the number-average molecular weight of water-based UV resin is 35000, and vitrification point is 50 DEG C,In water-based thermosetting resin emulsion, the content of water-based thermosetting resin is 30%, and now the acid number of described water-based thermosetting resin emulsion is12mgKOH/g, in water-based UV resin emulsion, the content of water-based UV resin is 30%, now the acid of water-based UV resin emulsionValue is 23mgKOH/g;
2, pre-coating composition is diluted to 5% solid content, is applied on untreated pet layer, through excess temperature with 200 order steel ridersSpend 60 DEG C, time 30s continuous drying, obtains lamination layer structure, and wherein pre-coating composition forms precoated shet;
3, under the condition of 4 times of 90 DEG C of preliminary drying temperature, preliminary drying time 20s, stretching ratio, the composite bed that step 2 is obtainedStructure is carried out stretch processing;
4, under the condition of 160 DEG C of temperature, time 10s, the lamination layer structure after the stretching that step 3 is obtained is shapedProcess, then coating UV coating, UV coating formed, then through energy 500mJ/cm2UV solidifies, solid to form respectively UVChange bottom and UV cured skin.
Embodiment 2
In the pre-coating composition of the present embodiment, the percentage by weight of each component is in table 1, the preparation method of UV cured article comprise withLower step:
1, provide component and percentage by weight pre-coating composition as shown in table 1, wherein, the particle diameter of water-based thermosetting resin emulsionFor 80nm, the particle diameter of water-based UV resin emulsion is 120nm, and the number-average molecular weight of water-based thermosetting resin is 25000, and weight average dividesSon amount is 55000, and vitrification point is 150 DEG C, and the number-average molecular weight of water-based UV resin is 30000, and vitrification point is 70 DEG C,Described in water-based thermosetting resin emulsion, the content of water-based thermosetting resin is 30%, and now the acid number of described water-based thermosetting resin emulsion is12mgKOH/g, in water-based UV resin emulsion, the content of water-based UV resin is 30%, now the acid of water-based UV resin emulsionValue is 25mgKOH/g;
2, pre-coating composition is diluted to 8% solid content, is applied on untreated pet layer, through excess temperature with 200 order steel ridersSpend 80 DEG C, time 60s continuous drying, obtains lamination layer structure, and wherein pre-coating composition forms precoated shet;
3, under the condition of 4 times of 90 DEG C of preliminary drying temperature, preliminary drying time 20s, stretching ratio, the composite bed that step 2 is obtainedStructure is carried out stretch processing;
4, under the condition of 160 DEG C of temperature, time 10s, the lamination layer structure after the stretching that step 3 is obtained is shapedProcess, then coating UV coating, UV coating formed, then through energy 500mJ/cm2UV solidifies, solid to form respectively UVChange bottom and UV cured skin.
Embodiment 3
In the pre-coating composition of the present embodiment, the percentage by weight of each component is in table 1, the preparation method of UV cured article comprise withLower step:
1, provide component and percentage by weight pre-coating composition as shown in table 1, wherein, the particle diameter of water-based thermosetting resin emulsionFor 60nm, the particle diameter of water-based UV resin emulsion is 100nm, and the number-average molecular weight of water-based thermosetting resin is 1000, weight average moleculeAmount is 5000, and vitrification point is 20 DEG C, and the number-average molecular weight of water-based UV resin is 1000, and vitrification point is 15 DEG C, waterDescribed in solid resin emulsion hot in nature, the content of water-based thermosetting resin is 30%, and now the acid number of described water-based thermosetting resin emulsion is5mgKOH/g, in water-based UV resin emulsion, the content of water-based UV resin is 30%, now the acid of described water-based UV resin emulsionValue is 10mgKOH/g;
2, pre-coating composition is diluted to 10% solid content, is applied on untreated pet layer, through excess temperature with 200 order steel ridersSpend 80 DEG C, time 60s continuous drying, obtains lamination layer structure, and wherein pre-coating composition forms precoated shet;
3, under the condition of 10 times of 110 DEG C of preliminary drying temperature, preliminary drying time 40s, stretching ratio, what step 2 was obtained is compoundLayer structure carried out stretch processing;
4, under the condition of 200 DEG C of temperature, time 30s, the lamination layer structure after the stretching that step 3 is obtained is shapedProcess, then coating UV coating, UV coating formed, then through energy 500mJ/cm2UV solidifies, solid to form respectively UVChange bottom and UV cured skin.
Embodiment 4
In the pre-coating composition of the present embodiment, the percentage by weight of each component is in table 1, the preparation method of UV cured article comprise withLower step:
1, provide component and percentage by weight pre-coating composition as shown in table 1, wherein, the particle diameter of water-based thermosetting resin emulsionFor 30nm, the particle diameter of water-based UV resin emulsion is 60nm, and the number-average molecular weight of water-based thermosetting resin is 20000, weight average moleculeAmount is 50000, and vitrification point is 120 DEG C, and the number-average molecular weight of water-based UV resin is 20000, and vitrification point is 15 DEG C,Described in water-based thermosetting resin emulsion, the content of water-based thermosetting resin is 60%, and now the acid number of described water-based thermosetting resin emulsion is10mgKOH/g, described in described water-based UV resin emulsion, the content of water-based UV resin is 60%, now described water-based UVThe acid number of resin emulsion is 20mgKOH/g;
2, pre-coating composition is diluted to 5% solid content, is applied on untreated pet layer, through excess temperature with 200 order steel ridersSpend 80 DEG C, time 60s continuous drying, obtains lamination layer structure, and wherein pre-coating composition forms precoated shet;
3, under the condition of 15 times of 110 DEG C of preliminary drying temperature, preliminary drying time 40s, stretching ratio, what step 2 was obtained is compoundLayer structure carried out stretch processing;
4, under the condition of 160 DEG C of temperature, time 10s, the lamination layer structure after the stretching that step 3 is obtained is shapedProcess, then coating UV coating, UV coating formed, then through energy 500mJ/cm2UV solidifies, solid to form respectively UVChange bottom and UV cured skin.
Embodiment 5
In the pre-coating composition of the present embodiment, the percentage by weight of each component is in table 1, the preparation method of UV cured article comprise withLower step:
1, provide component and percentage by weight pre-coating composition as shown in table 1, wherein, the particle diameter of water-based thermosetting resin emulsionFor 30nm, the particle diameter of water-based UV resin emulsion is 60nm, and the number-average molecular weight of water-based thermosetting resin is 5000, weight average moleculeAmount is 30000, and vitrification point is 70 DEG C, and the number-average molecular weight of water-based UV resin is 10000, and vitrification point is 15 DEG C,Described in water-based thermosetting resin emulsion, the content of water-based thermosetting resin is 40%, and now the acid number of described water-based thermosetting resin emulsion is6.2mgKOH/g, described in described water-based UV resin emulsion, the content of water-based UV resin is 40%, now described water-based UVThe acid number of resin emulsion is 15mgKOH/g;
2, pre-coating composition is diluted to 5% solid content, is applied on untreated pet layer, through excess temperature with 200 order steel ridersSpend 70 DEG C, time 45s continuous drying, obtains lamination layer structure, and wherein pre-coating composition forms precoated shet;
3, under the condition of 10 times of 100 DEG C of preliminary drying temperature, preliminary drying time 30s, stretching ratio, what step 2 was obtained is compoundLayer structure carried out stretch processing;
4, under the condition of 180 DEG C of temperature, time 20s, the lamination layer structure after the stretching that step 3 is obtained is shapedProcess, then coating UV coating, UV coating formed, then through energy 500mJ/cm2UV solidifies, solid to form respectively UVChange bottom and UV cured skin.
Embodiment 6
In the pre-coating composition of the present embodiment, the percentage by weight of each component is in table 1, the preparation method of UV cured article comprise withLower step:
1, provide component and percentage by weight pre-coating composition as shown in table 1, wherein, the particle diameter of water-based thermosetting resin emulsionFor 30nm, the particle diameter of water-based UV resin emulsion is 60nm, and the number-average molecular weight of water-based thermosetting resin is 3000, weight average moleculeAmount is 10000, and vitrification point is 50 DEG C, and the number-average molecular weight of water-based UV resin is 3000, and vitrification point is 6 DEG C, waterDescribed in solid resin emulsion hot in nature, the content of water-based thermosetting resin is 40%, and now the acid number of described water-based thermosetting resin emulsion is6.2mgKOH/g, described in described water-based UV resin emulsion, the content of water-based UV resin is 40%, now described water-based UVThe acid number of resin emulsion is 15mgKOH/g;
2, pre-coating composition is diluted to 5% solid content, is applied on untreated pet layer, through excess temperature with 200 order steel ridersSpend 70 DEG C, time 45s continuous drying, obtains lamination layer structure, and wherein pre-coating composition forms precoated shet;
3, under the condition of 10 times of 100 DEG C of preliminary drying temperature, preliminary drying time 30s, stretching ratio, what step 2 was obtained is compoundLayer structure carried out stretch processing;
4, under the condition of 180 DEG C of temperature, time 20s, the lamination layer structure after the stretching that step 3 is obtained is shapedProcess, then coating UV coating, UV coating formed, then through energy 500mJ/cm2UV solidifies, solid to form respectively UVChange bottom and UV cured skin.
Embodiment 7
In the pre-coating composition of the present embodiment, the percentage by weight of each component is in table 1, the preparation method of UV cured article comprise withLower step:
1, provide component and percentage by weight pre-coating composition as shown in table 1, wherein, the particle diameter of water-based thermosetting resin emulsionFor 30nm, the particle diameter of water-based UV resin emulsion is 60nm, and the number-average molecular weight of water-based thermosetting resin is 3000, weight average moleculeAmount is 18000, and vitrification point is 50 DEG C, and the number-average molecular weight of water-based UV resin is 5000, and vitrification point is 6 DEG C, waterDescribed in solid resin emulsion hot in nature, the content of water-based thermosetting resin is 40%, and now the acid number of described water-based thermosetting resin emulsion is6.2mgKOH/g, described in described water-based UV resin emulsion, the content of water-based UV resin is 40%, now described water-based UVThe acid number of resin emulsion is 15mgKOH/g;
2, pre-coating composition is diluted to 5% solid content, is applied on untreated pet layer, through excess temperature with 200 order steel ridersSpend 70 DEG C, time 45s continuous drying, obtains lamination layer structure, and wherein pre-coating composition forms precoated shet;
3, under the condition of 10 times of 100 DEG C of preliminary drying temperature, preliminary drying time 30s, stretching ratio, what step 2 was obtained is compoundLayer structure carried out stretch processing;
4, under the condition of 180 DEG C of temperature, time 20s, the lamination layer structure after the stretching that step 3 is obtained is shapedProcess, then coating UV coating, UV coating formed, then through energy 500mJ/cm2UV solidifies, solid to form respectively UVChange bottom and UV cured skin.
Comparative example 1
In this comparative example, the preparation method of UV cured article comprises the following steps:
1, on untreated pet layer, be coated with and UV coating identical in above-described embodiment 1 to 7, form UV coating, thenThrough energy 500mJ/cm2UV solidifies, to form lamination layer structure;
2, under the condition of 15 times of 110 DEG C of preliminary drying temperature, preliminary drying time 40s, stretching ratio, what step 2 was obtained is compoundLayer structure carried out stretch processing.
Comparative example 2
The pre-coating composition of this comparative example is water-based off-line coated product, adopts water-borne acrylic resin (model: AC-7505)With the composite gained of isocyanates (model: DNW-5500), the preparation method of UV cured article comprises the following steps:
1, deionized water and water-borne acrylic resin are dropped in reactor, control 800 revs/min of rotating speeds and stir 20min, make to mixClose evenly, and the particle diameter of water-borne acrylic resin is 60nm;
2, in reactor, add isocyanate curing agent, 800 revs/min of stirring 15min of rotating speed, make to mix to obtain waterProperty off-line coated product, wherein, the percentage by weight of water-borne acrylic resin is 90%, the percentage by weight of isocyanates is 10%.
3, pre-coating composition is diluted to 5% solid content, is applied on untreated pet layer, through temperature with 200 order steel riders110 DEG C～120 DEG C, time 30s～50s continuous drying, solidify to form precoated shet, then coating UV coating, forms UV coating,Then through energy 500mJ/cm2UV solidifies, and solidifies bottom and UV cured skin to form respectively UV.
By above-mentioned comparative example 1 and 2 and embodiment 1 to 7 in preparation UV cured article poach 30min after, utilize hundred lattice cuttvesMethod is tested the performance of UV cured article, and test result is as follows:
1, for the uncoated UV cured article that has pre-coating composition in comparative example 1, it is directly formed on pet layerUV cured skin can pull for 1 time with 3M adhesive tape;
2, for the UV cured article in comparative example 2, utilize 3M adhesive tape to pull UV cured skin 1 time, its UV solidifiesTop layer just comes off;
3, for the UV cured article in embodiment 1,2,4 to 7, utilize 3M adhesive tape to pull UV cured skin 3 times,Its UV cured skin also can not come off;
4,, for the UV cured article in embodiment 3, owing to not adding curing agent, utilize 3M adhesive tape to pull UV and solidify tableLayer 1 time, its UV cured skin just comes off.
Can be found out by above-mentioned test result, adopt the application's pre-coating composition on plastic basis material layer, to form the curing bottom of UVAfter form again UV cured skin, and by increase curing agent, effectively improved between UV cured skin and plastic basis material layerAdhesive force.
As can be seen from the above description, the above embodiments of the present invention have realized following technique effect:
1, functional pair of key in the enough and precoating UV coating of functional pair of bond energy of the water-based UV resin of above-mentioned particle size range is in advanceBe coated with under the effect of initator in UV coating and react, by improving the density of precoated shet when the film forming, improved precoated shet withAdhesive force between UV coating;
2, the water-based thermosetting resin emulsion of above-mentioned particle size range can, with curing agent by reacting to each other, improve this pre-coating compositionCohesive force and the density of precoated shet when resistance to water and film forming, adhere to thereby further improved between precoated shet and UV coatingPower;
3, the precoated shet being formed by pre-coating composition in online coating process can not rupture, and then makes above-mentioned pre-coatingComposition is in use without carrying out the processing such as corona, and can be applicable in online coating process;
4, utilize the UV cured article that above-mentioned preparation method is prepared to there is high surface tension value, at least can reach 40More than dyne, thereby can not cause the contraction of recoat material face, but also can increase the adherence effect of recoat material, and thenBe applicable to the application such as photocuring and thermosetting material recoat;
5, above-mentioned UV cured article can be prepared by online coating process, thereby has simplified operation, has improved UV and has solidified productThe overall yield of product.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for those skilled in the art, the present invention can have various modifications and variations. Within the spirit and principles in the present invention all, any amendment of doing, etc.With replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (10)
1. a pre-coating composition, is characterized in that, comprises that percentage by weight is 60%～80% water-based thermosetting resin emulsion, weightThe curing agent that the water-based UV resin emulsion that amount percentage is 10%～25% and percentage by weight are 1%～15%, described water-basedThermosetting resin emulsion comprises water-based thermosetting resin, and described water-based UV resin emulsion comprises water-based UV resin, and described water-basedThe particle diameter of thermosetting resin emulsion is less than 100nm, and the particle diameter of described water-based UV resin emulsion is less than 150nm.
2. pre-coating composition according to claim 1, is characterized in that, described water-based thermosetting resin is anionic resin,And the number-average molecular weight of described water-based thermosetting resin is 1000～20000, be preferably 1000～5000, described water-based thermosetting treeThe weight average molecular weight of fat is 5000～50000, is preferably 10000～30000, the vitrification point of described water-based thermosetting resinBe 20～120 DEG C, be preferably 20～70 DEG C.
3. pre-coating composition according to claim 1, is characterized in that, water-based described in described water-based thermosetting resin emulsionThe content of thermosetting resin is 30%～60%, and now the acid number of described water-based thermosetting resin emulsion is 5～10mgKOH/g.
4. according to the pre-coating composition described in any one in claims 1 to 3, it is characterized in that described water-based thermosetting resin choosingAny one or more in water-borne acrylic resin, waterborne polyurethane resin and waterborne, polycarbonate resin.
5. pre-coating composition according to claim 1, is characterized in that, the number-average molecular weight of described water-based UV resin is1000～20000, be preferably 3000～10000, the vitrification point of described water-based UV resin is less than 20 DEG C.
6. pre-coating composition according to claim 1, is characterized in that, water-based described in described water-based UV resin emulsionThe content of UV resin is 30%～60%, and now the acid number of described water-based UV resin emulsion is 10～20mgKOH/g.
7. according to the pre-coating composition described in any one in claim 1,5 and 6, it is characterized in that described water-based UV resinBe selected from water-based unsaturated polyester resin and/or waterborne epoxy acrylate.
8. a preparation method for UV cured article, is characterized in that, comprises the following steps:
Pre-coating composition described in any one in claim 1 to 7 is arranged on plastic basis material layer;
Pre-coating composition is dried to processing, obtains lamination layer structure, wherein said pre-coating composition forms precoatingLayer;
UV coating is arranged on the surface of described precoated shet, forms UV coating;
Described precoated shet and described UV coating are carried out to the curing processing of UV, and described precoated shet forms UV and solidifies bottom, instituteState UV coating formation UV cured skin.
9. preparation method according to claim 8, is characterized in that, described plastic basis material layer is pet layer, by described UVBefore coating is arranged at the step on described plastic basis material layer surface, described preparation method also comprises described lamination layer structure is complied withInferior step of carrying out stretch processing and heat treatment;
The preliminary drying temperature of preferred described stretch processing is 90 DEG C～110 DEG C, and the preliminary drying time is 20s～40s, and stretching ratio is 4～15Doubly;
The setting temperature of preferred described heat treatment is 160 DEG C～200 DEG C, and shaping time is 10s～30s.
10. a UV cured article, is characterized in that, described UV cured article is by the preparation method's system described in claim 8 or 9Standby forming.
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| CN108047434A (en) * | 2017-11-13 | 2018-05-18 | 广州擎天材料科技有限公司 | A kind of water solubility unsaturated polyester (UP) and Photocurable composition |
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