CN103045038A - Curing transfer coating capable of embossing laser information layer and preparation method thereof - Google Patents
Curing transfer coating capable of embossing laser information layer and preparation method thereof Download PDFInfo
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- CN103045038A CN103045038A CN201210582737XA CN201210582737A CN103045038A CN 103045038 A CN103045038 A CN 103045038A CN 201210582737X A CN201210582737X A CN 201210582737XA CN 201210582737 A CN201210582737 A CN 201210582737A CN 103045038 A CN103045038 A CN 103045038A
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Abstract
The invention relates to a UV/EB (ultraviolet/electron beam) curing transfer coating capable of embossing a laser information layer and a preparation method thereof. The coating comprises the following raw materials: 10-50 of solid thermoplastic resin, 5-30 of acrylate prepolymer, 20-80 of reactive diluent, 2-4 or 0 of initiator and 0.5-3.0 of additive. The preparation method comprises the steps as follows: dissolving the smashed solid thermoplastic resin in the active diluent of 40-60 DEG C; mixing with the preheated acrylate prepolymer of 40-60 DEG C; uniformly dispersing; adding the additive and the initiator (adding the additive only when adopting the EB curing process); uniformly dispersing; and filtering a mixture at the temperature of 40-60 DEG C to obtain the UV/EB curing transfer coating capable of performing mould pressing on the laser information layer. The production process of the coating is safe, high in efficiency and low in energy consumption and has the characteristic of zero emission; the embossed holographic laser information is clear; the performance of stripping from a PET (polyester) film is good; the performance of adhesion between an aluminum layer and the transfer coating in the vacuum aluminum plating process is good; and the wear resistance, the solvent resistance, the temperature resistance, the flexibility and the printing adaptability are excellent.
Description
Technical field
The present invention relates to curing transfer coatings of moldable laser information layer and preparation method thereof, belong to radiation curable coating and preparation method thereof technical field.
Background technology
Vacuum aluminium-plated paper since its to the excellent barrier properties of water and air with and to the consumption of metallic material of aluminum the few and characteristics such as degradable, recoverable, become a kind of novel environment friendly material, be widely used in the packing box of cigarette, wine, sugar, tea, food, medicine and daily necessities product.In order to improve antifalse effect and aesthetic feeling, high-grade packing box adopts the transfer laser aluminizing cardboard more.
Transfer laser aluminizing paperboard production technology principle is: in high vacuum is aluminized system, be coated with the also aluminium lamination of plastic film deposition one deck 20～50 nanometers of molding laser information coating in advance, the aluminium lamination face of plastic film and paper utilize glue compound under certain pressure, peel off plastic film, paper is coated with processing through moisture regain or the back of the body in case of necessity, cuts or break to open by the product specification requirement to obtain transfer laser aluminizing paperboard finished product.Its basic production operation is: plastic film is filmed, and------aluminizing,---compound---peeling off---moisture regain or the back of the body are coated with---cuts/breaks and open in mold pressing.Wherein, it mainly is the wax shell that has good stripping performance in the plastic film coating that plastic film is coated with membrane process, is coated with the coating of the moldable holographic information of one deck at the wax shell again.At present up-to-date technology can be directly in plastic film coating one deck coating, and this coating has good stripping performance and stable moldable laser information function.
Because plastic film (being generally PET film or BOPP film) surface tension is low, wetting ability and the levelling property of coating on plastic film is poor, coating need to evenly be coated with on plastic film, generally use at present solvent based coating, in the production process, the solvent evaporates amount is larger, and production environment is comparatively abominable, processes bad environmental pollution larger.In addition, plastic film unreel with wrapup procedure in very easily gather static, solvent is too high in the production plant air, very easily produces fire even blast.The production safety risk is higher.In order to control the generation of static, be coated with the membrane process speed of a motor vehicle unsuitable too high, cause integral production efficient lower.
From formulation for coating material and Technology, solvent-borne type laser aluminized transfer coating technology is relatively ripe, has obtained at home generally using; Though the aqueous laser aluminizing transfer paint has the partial monopoly report, but because of coating relatively poor at the levelling property on organic film (PET film or BOPP film) surface, the vacuum aluminum-coated brightness of impact that film forming compactness is not enough, heat resistance is not enough, sticking version, stifled version and black print often appear in the embossed holographic laser information technological process, and because peeling off unclear caused small particles quality problems etc., the promotion and application of aqueous laser aluminizing transfer paint have been badly influenced; And UV/EB solidification laser aluminizing transfer paint has no bibliographical information.
Traditional UV(ultraviolet ray)/the EB(electron beam) coating material solidified prescription form in because the functionality of the acrylic ester prepolymer of selecting and reactive thinner component is high, cross-linking density behind the coating curing is high, coating is fine and close, molecular weight is very high, substantially there is not fixing range of molecular weight distributions, coated material does not have thermoplasticity, only has thermolysis under the high temperature, thereby can't make coating produce stable holographic laser information by mould pressing process.
Summary of the invention
The object of the invention is to overcome the technical barrier that existing UV/EB solidified coating material can not molding laser information, a kind of safe, efficient, energy-conservation and environmental protection is provided, the curing transfer coatings of the moldable stable formation holographic laser information of coating, the production method of this coating also is provided simultaneously, the radiation curing transfer coatings that uses the method to obtain can replace conventional solvent-borne type transfer laser coating to be used in respectively in UV or the EB curing process, is coated with process safety and the environmental-protecting performance of membrane process to promote existing transfer laser vacuum aluminizing paperboard.
For achieving the above object, the present invention has adopted following technical scheme:
The present invention is by introduce the solid thermoplastic resin of 80 ℃～150 ℃ of an amount of softening point ranges in formulation for coating material, strengthen the plasticization effect of the coating after solidifying, introduce an amount of simple function reactive thinner and adjust the cross-linking density of coating, introduce an amount of molecular weight regulator component adjust with the balance coating curing after molecular weight, thereby reach the purpose that coating can satisfy the mold pressing requirement.
The curing transfer coatings of moldable laser information layer, special character is to comprise the raw material of following mass parts:
Solid thermoplastic resin 10～50;
Acrylic ester prepolymer 5～30;
Reactive thinner 20～80;
Auxiliary agent 0.5～3.0.
The preparation method of the curing transfer coatings of moldable laser information layer, its special character is to comprise following process:
(1), prepares starting material by the formula rate requirement;
(2), the reactive thinner component is dropped in the reactor, stir and be preheated to 40～60 ℃;
(3), the solid thermoplastic resin components after will pulverizing slowly drops in the reactor of stirring, high-speed stirring dissolved it in 2～5 hours fully;
(4), the acrylic ester prepolymer component is preheated to 40～60 ℃, slowly join in the reactor, be stirred to and be uniformly dispersed;
(5), adjuvant component is added in the reactor, be stirred to and be uniformly dispersed;
(6), under 40～60 ℃ of temperature, filter, the EB that obtains moldable laser information solidifies transfer coatings.
When the curing transfer coatings of the moldable laser information layer of the above-mentioned EB of being applicable to curing system is applied to the UV curing system, also should comprise the initiator of 2～4 mass parts in its raw material; Its preparation method is corresponding being adjusted into also:
(1), prepares starting material by the formula rate requirement;
(2), the reactive thinner component is dropped in the reactor, stir and be preheated to 40～60 ℃;
(3), the solid thermoplastic resin components after will pulverizing drops in the reactor stage by stage, high-speed stirring dissolved it in 2～5 hours fully;
(4), the acrylic ester prepolymer component is preheated to 40～60 ℃, slowly join in the reactor, be stirred to and be uniformly dispersed;
(5), adjuvant component and initiator component are added respectively in the reactor, be stirred to and be uniformly dispersed;
(6), under 40～60 ℃ of temperature, filter, the UV that obtains moldable laser information solidifies transfer coatings.
Solid thermoplastic resin of the present invention comprises one or more in acrylic resin, Resins, epoxy, vibrin, resol, ketone resin, modified rosin resin, vinyl chloride-vinyl acetate resin and the celluosic resin of solid form, accounts for 10～50% of coating total amount.
Wherein:
The acrylic resin of solid form adopts one or more in pure the third resin, the styrene-acrylic resin, and its molecular weight is 8000～100000;
The softening temperature of Resins, epoxy, vibrin, resol, ketone resin, modified rosin resin is 80～150 ℃;
Vinyl chloride-vinyl acetate resin adopts one or more in binary vinylchlorid one vinyl acetate resin, trihydroxylic vinylchlorid one vinyl acetate resin or ternary carboxyl vinylchlorid one vinyl acetate resin, and its molecular weight is 10000～100000;
Celluosic resin adopts one or more of cellulose acetate resin, cellulose acetate butyrate resin, acetate-cellulose propionate resin, and its softening temperature is 100～140 ℃;
Acrylic ester prepolymer of the present invention comprises one or more in urethane acrylate, epoxy acrylate, polyester acrylate, polyether acrylate and the organic silicon acrylic ester, accounts for 5～30% of coating total amount.
Wherein:
The molecular weight of urethane acrylate is 1000～5200, functionality 1～3;
The molecular weight of epoxy acrylate is 500～2000, functionality 1～3;
The molecular weight of polyester acrylate is 500～3000, functionality 1～4;
The molecular weight of polyether acrylate is 500～2000, functionality 1～3;
The molecular weight of organic silicon acrylic ester is 200～1000, functionality 1～3;
Reactive thinner of the present invention comprises methyl methacrylate, butyl acrylate, Isooctyl acrylate monomer, isobornyl acrylate, ethoxylation vinylformic acid oxygen phenyl ester, the ethoxyethyl group acrylate, the tetrahydrofuran (THF) acrylate, the vinylformic acid caprolactone, TriMethylolPropane(TMP) methylal〔Su〕 mono acrylic ester, vinylbenzene, 1, the 6-hexanediyl ester, neopentyl glycol dipropoxy diacrylate, tripropylene glycol diacrylate, Viscoat 295, the ethoxyquin Viscoat 295, the propoxylated glycerol triacrylate, in alkoxylate tetramethylol methane tetraacrylate and the two contracting trimethylolpropane tetra-acrylate one or more account for 20～80% of coating total amount.
Initiator component of the present invention comprises one or more among Irgacure 184, Irgacure 907, Irgacure369, Darocur 1173, BP, ITX and the TPO, if adopt the UV curing process, accounts for 2～4% of coating total amount; If adopt the EB curing process, described initiator amount is 0.
Wherein: Irgacure 184, Irgacure 907, Irgacure369, Darocur 1173, BP, ITX and TPO are the commercial goods.
Auxiliary agent of the present invention comprises molecular weight regulator, wetting agent, flow agent and defoamer etc., and the auxiliary agent total amount accounts for 0.5～3.0% of coating total amount.
Wherein:
Molecular weight regulator is selected from a kind of in n-dodecyl mercaptan, uncle's lauryl mercaptan, the different monooctyl ester of 3-thiohydracrylic acid and 2, the 4-phenylbenzene-4-methyl-1-pentene;
Wetting agent is selected from a kind of in polyether-modified polydimethylsiloxane, aralkyl modification polymethyl siloxane, polyester modification polydimethylsiloxane and the organosilicon silicon modified polyacrylate;
Flow agent is selected from a kind of in modified polyorganosiloxane, silicone-modified polyacrylate and the fluorine modified polyacrylate;
Defoamer is selected from a kind of in polysiloxane, mineral oil and the hydrophobic particle defoaming agent;
The solid thermoplastic resin Composition that the present invention selects has suitable softening point temperature scope, and good resin compatible has the internal plasticization effect, guarantees the characteristic of the moldable performance of coating;
The acrylic ester prepolymer content that the present invention selects is suitable, guarantees that coating has moderate cross-linking density, good snappiness and the removability of coating;
The reactive thinner component that the present invention selects more is conducive to reduce the viscosity of coating take the simple function group monomer as main body, helps construction, but simultaneously balance the cross-linking density of coating, improve the thermoplasticity of coating after solidifying, promote the sticking power of coating and aluminium coated.
Compared with prior art, the present invention has the following advantages:
(1) substitute conventional solvent type coating with radiation curable coating, production process safety, efficient is high, less energy consumption, zero release, pollution-free;
(2) excellent combination property of coating: the brightness of aluminizing is high, metal-like is strong, the embossed holographic laser information is clear, good with PET film removability, and good with the attachment fastness of aluminium lamination, wear resistance, scratch resistance, anti-solvent, heatproof, snappiness and printing adaptability are excellent.
Embodiment
Below provide the specific embodiment of the present invention, by embodiment technical scheme of the present invention is described in further detail, but embodiment is not limitation of the invention.
Embodiment 1
A kind of UV of moldable laser information solidifies the preparation method of transfer coatings, and the method comprises following processing step:
(1), get the raw materials ready according to following component and content:
Solid styrene-acrylic resin 25;
Urethane acrylate 15;
Isobornyl acrylate 50;
Ethoxyquin Viscoat 295 5;
Irgacure 907 3；
Auxiliary agent 2.
The molecular weight 20000～40000 of solid styrene-acrylic resin; The molecular weight 2600 of urethane acrylate, functionality are 1.5.
(2), reactive thinner component (isobornyl acrylate ester, ethoxyquin Viscoat 295) is dropped in the reactor, stir and be preheated to 40～60 ℃;
(3), the solid thermoplastic resin resin components (solid propenoic acid resin) after will pulverizing drops in the reactor stage by stage, high-speed stirring dissolved it in 2～5 hours fully;
(4), acrylic ester prepolymer component (urethane acrylate) is preheated to 40～60 ℃, slowly join in the reactor, be stirred to and be uniformly dispersed;
(5), initiator component (Irgacure 907) and adjuvant component are added in the reactor, be stirred to and be uniformly dispersed;
(6), under 40～60 ℃ of temperature, filter, the UV that obtains moldable laser information solidifies transfer coatings.
Solid styrene-acrylic resin among the embodiment 1 is thermoplastic resin, does not participate in crosslinking reaction in solidification process, but can promote the thermoplasticity of coating behind coating curing; The urethane acrylate of higher molecular weight can strengthen the toughness of coating; The isobornyl acrylate of simple function is main reactive thinner, balance the cross-linking density of coating.Coating is preheating to 50 ℃ ± 5 ℃, viscosity (Cai En-3 glass, 50 ℃) 15～20 seconds, roller coat coating on the PET film that rubber roll is 18um at thickness with three-roller type, glue spread is controlled at 1.4～1.6g/ ㎡, and machine speed is for being controlled at 50m/min, and UV lamp power setting is 120W/ ㎝.After being coated with coating is carried out mold pressing, the moulding press temperature setting is set to 175 ℃, and machine speed is 40m/min, is prepared into the moulding film with laser effect.After aluminum-spraying machine was vacuum aluminum-coated, use glue was compound with aluminium plating film and paperboard with moulding film, and the PET film is stripped down from the paperboard surface, namely obtained having the transition card paper material of holographic laser information.The brightness of aluminizing on this paperboard surface is high, and laser information is clear, and the attachment fastness of UV solidified coating and aluminium lamination is good, and surface gloss is high, and rub resistance is good.
Embodiment 2
Preparation technology fills a prescription as follows with embodiment 1:
Ketone resin 20;
Modified rosin resin 15;
Polyether acrylate 12;
Organic silicon acrylic ester 3;
Neopentyl glycol dipropoxy diacrylate 5;
TriMethylolPropane(TMP) methylal〔Su〕 mono acrylic ester 30;
Vinylbenzene 10;
Irgacure 184 1.0；
BP 2.0；
Auxiliary agent 2.0.
The ketone resin softening temperature is 100～110 ℃; The softening temperature of modified rosin resin is 120～150 ℃; The polyether acrylate molecular weight is 600, functionality 3; The molecular weight of described organic silicon acrylic ester is 480～600.
Select the solubility properties of thermoplastic resin in thinner such as ketone resin and modified rosin resin better among the embodiment 2, consumption is relatively large, molding temperature can be reduced to below 150 ℃ on the basis of embodiment 1.
Embodiment 3
(1), get the raw materials ready according to following component and content:
Vinyl chloride-vinyl acetate resin 20;
Celluosic resin 8;
Epoxy acrylate 8;
1,6 hexanediol diacrylate 12;
Methyl methacrylate 10;
Isobornyl acrylate 20
Isooctyl acrylate monomer 20;
Auxiliary agent 2.0.
The molecular weight 30000 of vinyl chloride-vinyl acetate resin; The softening temperature of celluosic resin is 120 ℃; The molecular weight 650 of epoxy acrylate, functionality are 2.0.
(2), reactive thinner component (1,6 hexanediol diacrylate, methacrylic ester, isobornyl acrylate ester, Isooctyl acrylate monomer) is dropped in the reactor, stir and be preheated to 40～60 ℃;
(3), thermoplastic resin resin components (celluosic resin) is dropped in the reactor stage by stage, high-speed stirring dissolved it in 2～5 hours fully;
(4), acrylic ester prepolymer component (epoxy acrylate) is preheated to 40～60 ℃, slowly join in the reactor, be stirred to and be uniformly dispersed;
(5), adjuvant component is added in the reactor, be stirred to and be uniformly dispersed;
(6), under 40～60 ℃ of temperature, filter, the EB that obtains moldable laser information solidifies transfer coatings.
Do not contain initiator component in embodiment 3 coating, be applicable to the EB curing process.This coating is preheating to 30 ℃ ± 5 ℃, (Cai En-3 glass of viscosity, 30 ℃) 18～25 seconds, roller coat coating on the PET film that rubber roll is 18um at thickness with five roll-types, glue spread is controlled at 1.3～1.7g/ ㎡, and machine speed is for being set as 200m/min, and EB voltage is set as 110KV, radiation dose is 230000～27000kGy m/min, ambient oxygen content≤100ppm.After being coated with coating is carried out mold pressing, the moulding press temperature setting is set to 180 ℃, and machine speed is set as 40m/min, is prepared into the moulding film with laser effect.Carry out afterwards compoundly and peel off, namely obtain having the transition card paper material of holographic laser information.The characteristics of this technique are that high efficiency, production cost are low.
Embodiment 4
Preparation technology fills a prescription as follows with embodiment 3:
Resins, epoxy 30;
Resol 10;
Polyester acrylate 7;
Tripropylene glycol diacrylate 5;
Ethoxylation vinylformic acid oxygen phenyl ester 10;
Vinylbenzene 15;
Butyl acrylate 20;
Auxiliary agent 3;
The softening temperature of Resins, epoxy and resol is 120 ℃; The molecular weight 900 of polyester acrylate, functionality are 1.8.
Selecting Resins, epoxy and resol than high softening-point among the embodiment 4 is to improve thermoplastic functional resin, is coated with construction according to embodiment 3 techniques, and resulting materials has excellent gravure and offset printing adaptability.
Embodiment 5
Preparation technology fills a prescription as follows with embodiment 3:
Pure the third resin 24 of solid;
Celluosic resin 6;
Polyester acrylate 10;
Two contracting trimethylolpropane tetra-acrylate 7;
Tetrahydrofuran (THF) acrylate 30;
Vinylformic acid caprolactone 20;
Auxiliary agent 3.
The molecular weight of pure the third resin of solid is 60000; The softening temperature of celluosic resin is 120 ℃; The molecular weight 900 of polyester acrylate, functionality are 1.8.
Resulting materials has excellent snappiness among the embodiment 5.
Claims (10)
1. the curing transfer coatings of moldable laser information layer is characterised in that the raw material that comprises following mass parts:
Solid thermoplastic resin 10～50;
Acrylic ester prepolymer 5～30;
Reactive thinner 20～80;
Auxiliary agent 0.5～3.0.
2. the curing transfer coatings of moldable laser information layer as claimed in claim 1 is characterized in that
The initiator that also comprises 2～4 mass parts.
3. the curing transfer coatings of moldable laser information layer as claimed in claim 1 or 2 is characterized in that
Described solid thermoplastic resin comprises one or more in acrylic resin, Resins, epoxy, vibrin, resol, ketone resin, modified rosin resin, vinyl chloride-vinyl acetate resin and the celluosic resin of solid form.
4. the curing transfer coatings of moldable laser information layer as claimed in claim 3 is characterized in that
Described acrylic resin adopts one or more in pure the third resin, the styrene-acrylic resin, and its molecular weight is 8000～100000.
5. the curing transfer coatings of moldable laser information layer as claimed in claim 3 is characterized in that
The softening temperature of described Resins, epoxy, vibrin, resol, ketone resin, modified rosin resin is 80～150 ℃.
6. the curing transfer coatings of moldable laser information layer as claimed in claim 3 is characterized in that
Described vinyl chloride-vinyl acetate resin adopts one or more in binary vinylchlorid one vinyl acetate resin, trihydroxylic vinylchlorid one vinyl acetate resin or ternary carboxyl vinylchlorid one vinyl acetate resin, and its molecular weight is 10000～100000.
7. the curing transfer coatings of moldable laser information layer as claimed in claim 3 is characterized in that
Described celluosic resin adopts one or more of cellulose acetate resin, cellulose acetate butyrate resin, acetate-cellulose propionate resin, and its softening temperature is 100～140 ℃.
8. the curing transfer coatings of moldable laser information layer as claimed in claim 1 or 2 is characterized in that
Described acrylic ester prepolymer comprises one or more in urethane acrylate, epoxy acrylate, polyester acrylate, polyether acrylate and the organic silicon acrylic ester;
The molecular weight of described urethane acrylate is 1000～5200, functionality 1～3;
The molecular weight of described epoxy acrylate is 500～2000, functionality 1～3;
The molecular weight of described polyester acrylate is 500～3000, functionality 1～4;
The molecular weight of described polyether acrylate is 500～2000, functionality 1～3;
The molecular weight of described organic silicon acrylic ester is 200～1000.
9. the curing transfer coatings of moldable laser information layer as claimed in claim 1 or 2 is characterized in that
Described reactive thinner comprises methyl methacrylate, butyl acrylate, Isooctyl acrylate monomer, isobornyl acrylate, ethoxylation vinylformic acid oxygen phenyl ester, ethoxy ethoxy ethyl propylene acid esters, the tetrahydrofuran (THF) acrylate, the vinylformic acid caprolactone, TriMethylolPropane(TMP) methylal〔Su〕 mono acrylic ester, vinylbenzene, 1,6 hexanediol diacrylate, neopentyl glycol dipropoxy diacrylate, tripropylene glycol diacrylate, Viscoat 295, the ethoxyquin Viscoat 295, the propoxylated glycerol triacrylate, in alkoxylate tetramethylol methane tetraacrylate and the two contracting trimethylolpropane tetra-acrylate one or more.
10. the preparation method of the curing transfer coatings of moldable laser information layer is characterized in that preparation process comprises:
(1), by the starting material of formula rate requirement preparation in mass parts:
Solid thermoplastic resin 10～50;
Acrylic ester prepolymer 5～30;
Reactive thinner 20～80;
Initiator 0 or 2～4
Auxiliary agent 0.5～3.0;
(2), the reactive thinner component is dropped in the reactor, stir and be preheated to 40～60 ℃;
(3), the solid thermoplastic resin resin components after will pulverizing slowly drops in the reactor of stirring, high-speed stirring dissolved it in 2～5 hours fully;
(4), the acrylic ester prepolymer component is preheated to 40～60 ℃, slowly join in the reactor, be stirred to and be uniformly dispersed;
(5), adjuvant component is added in the reactor, add in case of necessity initiator component, be stirred to and be uniformly dispersed;
(6), under 40～60 ℃ of temperature, filter, the EB/UV that obtains moldable laser information solidifies transfer coatings.
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