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CN104817880A - Ultraviolet curing anti-anodic oxidation shielding protection printing ink - Google Patents

Ultraviolet curing anti-anodic oxidation shielding protection printing ink Download PDF

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Publication number
CN104817880A
CN104817880A CN201510167209.1A CN201510167209A CN104817880A CN 104817880 A CN104817880 A CN 104817880A CN 201510167209 A CN201510167209 A CN 201510167209A CN 104817880 A CN104817880 A CN 104817880A
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acrylate
ink
anode
ultraviolet light
light polymerization
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CN104817880B (en
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朱婉平
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Good Former Science And Technology Co Ltd That Refines In Shenzhen Ten Thousand
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Good Former Science And Technology Co Ltd That Refines In Shenzhen Ten Thousand
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D11/00Inks
    • C09D11/02Printing inks
    • C09D11/10Printing inks based on artificial resins
    • C09D11/101Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D11/00Inks
    • C09D11/02Printing inks
    • C09D11/03Printing inks characterised by features other than the chemical nature of the binder
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D11/00Inks
    • C09D11/02Printing inks
    • C09D11/10Printing inks based on artificial resins
    • C09D11/102Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D11/00Inks
    • C09D11/02Printing inks
    • C09D11/10Printing inks based on artificial resins
    • C09D11/106Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C09D11/107Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)

Abstract

The invention provides an ultraviolet curing anti-anodic oxidation shielding protection printing ink, by taking total weight of a printing ink composition as a reference, the ultraviolet curing anti-anodic oxidation shielding protection printing ink comprises the following components by weight percentage: 55-80% of low polymer, 5-15% of active monomer, 3-8 parts of initiator and 15-25% of filling material; wherein the low polymer is one or two selected from aliphatic polyurethane acrylate and acid anhydride-modified epoxy acrylate. The ultraviolet curing anti-anodic oxidation shielding protection printing ink has the advantages of fast solidification speed, better adhesive force, CNC resistance, scratch resistance, immersion resistance by various cutting fluids, anodic oxidation resistance, easy stripping, no residues after film-stripping, and no base material corrosion; is suitable for aluminum material or aluminum alloy base material and plastic cement base material, and is especially suitable for an aluminum material and plastic cement-embedded composite base material.

Description

The anti-anode of a kind of ultraviolet light polymerization covers protection ink
Technical field
The present invention relates to surface protection ink product technical field, be specifically related to the anti-anode of a kind of ultraviolet light polymerization and cover protection ink, be specially adapted to the composite base material that aluminium and plastic cement are inlayed.
Background technology
UV curable ink is also known as UV ink, a kind of environmental protection ink developed rapidly, compared with the ink of traditional type, there is instantaneous solidification, not containing volatile organic solvent, production efficiency is high, one-tenth film hardness is strong, solvent resistance is good, environmental pollution is little, save the features such as the energy, because it has the incomparable advantage of traditional solvent-borne ink, be widely applied to the field in many ways such as tobacco bale, Jiu Bao, cosmetic package, drug packaging and pressure-sensitive adhesive trade mark.
Now; increasing product (such as phone housing, panel computer etc.) adopts the multiple material such as metal, plastic cement to carry out appearance design; substrate surface inlayed by the metal formed and plastic cement also needs to adopt CNC to process with the demand of satisfied more somewhat complex design; and metal is easily scratched in the CNC course of processing; cause product bad; this protects the surface of product in the CNC course of processing with regard to requiring; along with the change of material and products C NC processing become more meticulous more, this just has higher requirement to the surface protection in the products C NC course of processing.Wherein, aluminium or aluminium alloy, because of characteristics such as it is cheap and easy to get, soft easily processing, are often used in the processing of this series products.In order to strengthen the erosion resistance of aluminium or aluminium alloy, the aesthetic property of product appearance; by aluminium or the standby product casing of aluminum alloy is carried out repeatedly anodic oxidation treatment in prior art; the figure being about to first time own anodic oxidation part is protected; then carry out the anodic oxidation treatment that secondary or more is secondary, then the protection ink of strong, the resistance to CNC of oxidation-resistance becomes very powerful and exceedingly arrogant product.
As Chinese patent literature CN103045015 discloses the anti-anodic oxidation ink of a kind of liquid photosensitive imaging and developing with alkali, this ink comprises according to parts by weight: photosensitive resin 30-50 part, propylene oxide vinegar resin 5-15 part, reactive thinner 10-20 part, solvent 5-15 part, light trigger 1-10 part, auxiliary agent 1-3 part, filler 20-40 part and pigment 0.5-0.8 part, described alkaline soluble photosensitive resin is made up of following raw material: 35-50 part epoxy resin, 20-40 part DBE, 15-20 part vinylformic acid, 8-15 part toxilic acid is joined, 0.5-1 part Resorcinol, 0.5-1 part tetraethyl-Australia presses.The anti-sandblasting of this liquid photosensitive imaging and developing with alkali anti-anodic oxidation ink, resistance to highly basic, resistance to strong acid, anti-anodic oxidation.But; for the composite base material that aluminium and plastic cement are inlayed; this kind of protection ink is used to there is the problem of plastic surface upper protective film demoulding difficulty; if use traditional plastic cement protection ink to there is again the problem of the not resistance to CNC of protective membrane; traditional protection ink is made to be difficult to the surface protection demand of competent aluminium and plastic cement preparation base material; and then exist product yield low, in the design with curved surface and complex profile, be difficult to the situation of being competent at, can not adequately protect product.
Summary of the invention
What the present invention solved is when in prior art, ink is applicable to aluminium and plastic cement inlaid material, the resistance to CNC of aluminium base protection ink can not be met simultaneously, resistance to anodic oxidation, the technical need of the easy demoulding of plastic rubber substrate protection ink, pad pasting protection process efficiency is low, product yield is low and be difficult to technical problems such as being competent in the design with curved surface and complex profile, and then provide a kind of simple to operate, efficiency is high, curing speed is fast, sticking power is good, resistance to CNC, scratch resistance, resistance to various cutting fluid is soaked, anti-anodic oxidation, easy demoulding, move back noresidue after film, the high-performance ultraviolet cured anti-anode not corroding base material covers protection ink.
The anti-anode of a kind of ultraviolet light polymerization covers protection ink, and with the gross weight of ink composite for benchmark, described ink comprises the component of following weight percent:
Wherein, described oligopolymer is the mixture of aliphatic urethane acrylate, anhydride modified epoxy acrylate.
Described aliphatic urethane acrylate is derived from ester class and/or ethers long-chain polyhydric alcohol, and functionality is 2, and molecular weight is 960-5000.
The caprolactone-derived long-chain polyhydric alcohol of described aliphatic urethane acrylate and tetrahydrofuran (THF) long-chain polyhydric alcohol.
With the gross weight of ink composite for benchmark, described oligopolymer comprises the aliphatic urethane acrylate that weight percent is 50-60%, and weight percent is the anhydride modified epoxy acrylate of 20-30%.
Described anhydride modified epoxy acrylate molecular weight is 3000-5000, and acid number is 70-100.
Described oligopolymer also comprise in aromatic urethane acrylate, polyester acrylate one or more.
The functionality of described aromatic urethane acrylate is 2, and molecular weight is 6000-8000; And/or
The functionality of described polyester acrylate is 2-3, and molecular weight is 1000-2000.
Described reactive monomer is one or more in Viscoat 295, tripropylene glycol diacrylate, glycerol tri-acrylate, glycol diacrylate, methyl acrylate, ethyl propenoate, propyl acrylate, isobutyl acrylate, vinylformic acid norbornene ester, isobornyl acrylate, isobornyl methacrylate, Hydroxyethyl acrylate, Propylene glycol monoacrylate, acrylated phosphate; And/or
Described initiator is 2-hydroxyl-2 methylphenyl acetone, 1-hydroxy-cyciohexyl benzophenone, 2; 4; one or more in 6-trimethylbenzoy-dipheny phosphine oxide, benzophenone, 2,4,4-trimethylpentylphosphine oxide, benzil, 4-phenyl benzophenone.
Described filler is one or more in barium sulfate, silicon-dioxide, wilkinite, talcum powder, kaolin.
With the gross weight of ink composite for benchmark, described ink also comprises the component of following weight percent:
Pigment 0.5-1%; And/or
Auxiliary agent 0.3-2%.
And/or
Described pigment is one or more in carbon black, phthalocyanine blue, phthalein viridescent; And/or
Described auxiliary agent is polyether-modified polydimethylsiloxane, polyacrylic ester, 2,6 di t butyl phenol, one or more in aminomethoxy silane.
The anti-anode of described ultraviolet light polymerization covers protection ink and is applicable to the composite base material that aluminium and plastic cement inlay.
The anti-anode of ultraviolet light polymerization provided by the invention covers protection ink, and with the gross weight of ink composite for benchmark, this ink comprises the component of following weight percent: oligopolymer 55-80%; Reactive monomer 5-15%; Initiator 3-8%; Filler 15-25%; Wherein, described oligopolymer is the mixture of aliphatic urethane acrylate, anhydride modified epoxy acrylate.Acrylate resin constitutes the basic framework of solidifying product, contriver is in discovery pleasantly surprised after great many of experiments, this formula under oligopolymer with jointly form the surface tension of crosslinked polymer net-structured film during reactive monomer effect lower than aluminium base material and plastic rubber substrate surface tension, two kinds of base materials all have good tack.The present invention adopts mixing of aliphatic urethane acrylate and anhydride modified epoxy acrylate, and the structural membrane that the oligopolymer under the mixing of this ratio and reactive monomer are cross-linked has outstanding film forming extensibility, snappiness and oxidation-resistance.Be coated with the plastic cement that the invention provides ink and aluminium and inlay base material and remover when acting on mutually, ink shows the characteristic of easily moving back film, noresidue.Namely ink provided by the invention is specially adapted to aluminium and base material inlayed by plastic cement, can meet the technical need of easily demoulding on resistance to CNC on aluminium, anti-oxidant, plastic material simultaneously, go for the project organization with curved surface and complex profile.
The anti-anode of ultraviolet light polymerization provided by the invention to cover in protection ink oligopolymer can for be 2 derived from ester class and/or ethers long-chain polyhydric alcohol, functionality, molecular weight is the aliphatic urethane acrylate of 960-5000; the urethane acrylate of low functionality has the film forming speed with high-ranking official's degree material equity; its low functional structure makes again shrinking percentage during film forming become less, and therefore this ink has good sticking power while effective acquisition tenacity film on base material.The material of urethane acrylate structure is the molecular configuration with the combination of soft or hard section, can provide excellent abrasion resistance properties in film, and this ink body reveals excellent resistance to CNC, scratch resistance characteristic.
It is the lipid structure urethane acrylate of caprolactone long-chain polyhydric alcohol and the synthesis of tetrahydrofuran (THF) long-chain polyhydric alcohol that the anti-anode of ultraviolet light polymerization provided by the invention covers aliphatic urethane acrylate described in protection ink; caprolactone long-chain polyhydric alcohol gives snappiness and the demoulding performance of ink excellence, and tetrahydrofuran (THF) long-chain polyhydric alcohol gives ink splendid tack.
The molecular weight that the anti-anode of ultraviolet light polymerization provided by the invention covers anhydride modified epoxy acrylate in protection ink is 3000-5000, and acid number is 70-100.Containing a large amount of hydroxyls in Epocryl, carboxyl can be introduced with acid anhydrides generation esterification and improve molecular polarity, thus improve Epocryl wetting ability, to the sticking power of base material and the caustic solubility of resin, for ink provides good resistance to cutting fluid performance, give the anti-anodic oxidation performance that ink is splendid.When base material be aluminium and plastic cement combination time ,-COOH the group in anhydride modified epoxy acrylate can with alkali reaction, so when selecting alkaline depainting water, demoulding effect is better.And the carboxylated degree of Epocryl is higher, faling apart property of aqueous resin is better; When carboxylated degree one timing, degree of neutralization is higher, and faling apart property of aqueous resin is better.Contriver is in discovery pleasantly surprised after great many of experiments, and molecular weight is 3000-5000 and the film that formed of the anhydride modified epoxy acrylate that acid number is 70-100 is optimum to the sticking power of base material, anti-anode performance, and acid number is too high, resistance to CNC degradation; Acid number is too low, and resistance to anodic oxidation performance reduces.
The anti-anode of ultraviolet light polymerization provided by the invention covers in protection ink, and described oligopolymer comprises the aliphatic urethane acrylate that weight percent is 50%-60%, and weight percent is the anhydride modified epoxy acrylate of 20%-30%.Aliphatic urethane acrylate addition is larger, and demoulding is easier, and anti-sandblasting performance is better, and resistance to CNC performance is poorer, and resistance to anodic oxidation performance is also poorer; Anhydride modified epoxy acrylate addition is larger, and resistance to CNC performance is better, and resistance to anodic oxidation performance is better, but demoulding performance is poorer.Through test determination, be 50%-60% at aliphatic urethane acrylate addition, when anhydride modified epoxy acrylate addition is 20%-30%, the property retention balances such as the resistance to CNC of ink, resistance to anodic oxidation, demoulding can be made.
The anti-anode of ultraviolet light polymerization provided by the invention covers oligopolymer in protection ink can also add that functionality is 2-3, molecular weight is the polyester acrylate of 1000-2000, strengthens the toughness of film.
The anti-anode of ultraviolet light polymerization provided by the invention covers protection ink; this area common method preparation can be adopted; step is simple; easy to operate; and because its curing speed is fast, sticking power is good, resistance to CNC, scratch resistance, the immersion of resistance to various cutting fluid, anti-anodic oxidation, easily demoulding, move back film after noresidue, do not corrode the high-performance of base material; be applicable to aluminium or aluminum alloy base material, plastic rubber substrate, be specially adapted to the preparation base material of aluminium and plastic cement.
Embodiment:
In order to make the object, technical solutions and advantages of the present invention clearly, below in conjunction with embodiment, embodiments of the present invention are described in further detail.
The invention provides the anti-anode of a kind of ultraviolet light polymerization and cover protection ink, with the gross weight of ink composite for benchmark, described ink comprises oligopolymer, reactive monomer, initiator and filler.
Wherein, oligopolymer as product matrix resin, constitute the basic framework of solidifying product, determine the fundamental property (hardness, snappiness, sticking power, optical property, ageing-resistant etc.) of product after solidification.Described oligopolymer is that a kind of molecular weight is relatively low, monomeric unit repeats the polymkeric substance of 2 to tens times, oligopolymer of the present invention selects molecular weight to be 1000-8000, the acrylic acid or the like photosensitive resin of preferred 2000-7000 or 2500-5000, if relative molecular mass is excessive, viscosity is too high, be unfavorable for allotment and construction, coating performance is also wayward.
In the present invention, oligopolymer is the mixture of aliphatic urethane acrylate, anhydride modified epoxy acrylate, and the structural membrane that this mixing oligopolymer and reactive monomer are cross-linked has outstanding oxidation-resistance and excellent sticking power.
As selectable embodiment, oligopolymer comprises the aliphatic urethane acrylate that weight percent is 50%-60%, and weight percent is the anhydride modified epoxy acrylate of 20%-30%.Aliphatic urethane acrylate addition is larger, and demoulding is easier, and anti-sandblasting performance is better, and resistance to CNC performance is poorer, and resistance to anodic oxidation performance is also poorer; Anhydride modified epoxy acrylate addition is larger, and resistance to CNC performance is better, and resistance to anodic oxidation performance is better, but demoulding performance is poorer.Through test determination, be 50%-60% at aliphatic urethane acrylate addition, when anhydride modified epoxy acrylate addition is 20%-30%, the property retention balances such as the resistance to CNC of ink, resistance to anodic oxidation, demoulding can be made.
As selectable embodiment; in the present invention, aliphatic urethane acrylate is the lipid structure urethane acrylate derived from ester class or ethers long-chain polyhydric alcohol; its basic structure comprises soft chain segment (polyurethane portion) and hard segment (acrylate part); this oligopolymer and reactive monomer form cross-linked polymer reticulated structure jointly; define the softness and tough film with aluminium material, plastic rubber substrate with high adhesion, and this layer of tough protective membrane has excellent demoulding under the effect of remover.Wherein, the carbochain in the ester class of acrylic acid synthesizing ester oligomer or ethers long-chain polyhydric alcohol is C12 ~ C30.Preferred functionality is 2, and molecular weight is the aliphatic urethane acrylate of 960-5000 or 1000-4000 or 2000-3000.Preferably, the caprolactone-derived long-chain polyhydric alcohol of aliphatic urethane acrylate and/or tetrahydrofuran (THF) long-chain polyhydric alcohol, caprolactone long-chain polyhydric alcohol gives snappiness and the demoulding performance of ink excellence, and tetrahydrofuran (THF) long-chain polyhydric alcohol gives ink splendid tack.
As selectable embodiment, one or more in aromatic urethane acrylate, polyester acrylate in oligopolymer, also can be comprised.Aromatic urethane acrylate can improve the endurance of ink.Polyester acrylate can improve solidification rate, improves cured film mechanical mechanics property, strengthens toughness and the solvent resistance of film, preferred functionality is 2-3, and molecular weight is 1000-2000, or 1200-1800, or 1300-1700, or the polyester acrylate of 1400-1600.
As selectable embodiment, oligopolymer selects the mixture of aliphatic urethane acrylate, anhydride modified epoxy acrylate, aromatic urethane acrylate, polyester acrylate, and its ratio is (50%-60%): (20%-30%): (5%-10%): (5%-10%).
As selectable embodiment, with ink composite gross weight for benchmark, the consumption 55-80% of oligopolymer, preferred 60-75%, more preferably 65-70%, be more preferably 68%.
Reactive monomer is a kind of functional type monomer, the dual-use function of curing cross-linked and solvent is had concurrently in the compositional system of UV curable ink, its effect is the viscosity regulating UV curable ink, the oligopolymer larger to viscosity dilutes, it can control curing cross-linked density, improve the physics of film, mechanical property, participate in film-forming.The functionality of reactive monomer has impact to curing speed, and functionality is larger, and curing speed is faster.In the present invention, reactive monomer can be selected from one or more in the esters of acrylic acid of the esters of acrylic acid of single functionality, the esters of acrylic acid of difunctionality, three-functionality-degree.
The acrylic ester monomer of three-functionality-degree, can be enumerated as Viscoat 295, glycerol tri-acrylate.The acrylic ester monomer of difunctionality, can enumerate glycol diacrylate.The acrylic ester monomer of single functionality, can enumerate methyl acrylate, ethyl propenoate, propyl acrylate, isobutyl acrylate, vinylformic acid norbornene ester, isobornyl acrylate, isobornyl methacrylate, Propylene glycol monoacrylate, acrylated phosphate.Above acrylic ester monomer both may be used alone, two or more kinds can also be used in combination.
As selectable embodiment, with ink composite gross weight for benchmark, the consumption of reactive monomer is 5-15%, is preferably 7-12%, more preferably 8-10%, such as 9%.
Initiator in UV curable ink is that a class easily absorbs UV energy generation living radical or active ion base, and then the material of unsaturated group polymerization in initiation ink, Active Radicals Produced or positively charged ion is produced, the polymerization of initiation or the corresponding monomer of catalysis or prepolymer after the luminous energy of the certain wavelength of its Absorbable rod.The performance of initiator determines state of cure and the curing speed of UV curable ink.The initiator that can be caused radical polymerization by ultraviolet excitation is selected in the present invention.As selectable embodiment; initiator can be selected from following material: 2-hydroxyl-2 methylphenyl acetone, 1-hydroxy cyclohexyl phenylketone, 2; 4; 6-trimethylbenzoy-dipheny phosphine oxide, benzophenone, 2; one or more in 4,4-trimethylpentylphosphine oxide, benzil, 4-phenyl benzophenone.
As selectable embodiment, with ink composite gross weight for benchmark, the consumption 3-8% of initiator, preferred 4-7%, is more preferably 5-6%.
In the present invention, described filler, to the rheological of ink and its vital role of physical and mechanical property, can be the filler of various routine, such as, be one or more in barium sulfate, silicon-dioxide, wilkinite, talcum powder, kaolin; With ink composite gross weight for benchmark, the consumption of filler is 15-25%, preferred 18-22%, such as 20%;
For making ink of the present invention have better implementation result in implementation process, can also comprise pigment in ink, other auxiliary agents of interpolation that also can be suitable as required, as one or more in defoamer, stablizer, flow agent etc.
As selectable embodiment, with the gross weight of ink composite for benchmark, described ink also comprises the component of following weight part:
Pigment 0.5-1%, preferably 0.8%; And/or
Auxiliary agent 0.3-2%, preferred 0.5-1.5%, more preferably 0.8-1.2%, such as 1.0%.
Described pigment can be the pigment of various routine, makes ink present certain color, such as, be one or more in carbon black, titanium dioxide, the blue or green pigment of phthalein (as phthalocyanine blue, phthalein viridescent), can select as required;
Described auxiliary agent is preferably polyether-modified polydimethylsiloxane, polyacrylic ester, 2,6 di t butyl phenol, one or more in aminomethoxy silane.
The anti-anode of ultraviolet light polymerization of the present invention covers protection ink and following methods can be adopted to prepare, and the method comprises the following steps:
Step 1: take material oligomer, reactive monomer and initiator in proportion, transfers to raw material in dispersion machine and is uniformly mixed, and such as churning time is 1-1.5 hour, and initiator fully dissolves, material dispersion is even;
Step 2: mixture that is finely dispersed for step 1 gained, that be applicable to viscosity is filtered, obtains required finished product.
The anti-anode of ultraviolet light polymerization of the present invention covers protection ink and is applicable to aluminium or aluminum alloy base material, plastic rubber substrate, is specially adapted to the composite base material that aluminium and plastic cement are inlayed.
Below in conjunction with specific embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.The experimental technique of unreceipted actual conditions in the following example, measures according to national standard usually.If there is no corresponding national standard, then according to general international standard, normal condition or carry out according to the condition that manufacturer advises.Unless otherwise indicated, otherwise all meterings take ink composite as the weight part of total weight, and described polymericular weight is number-average molecular weight, does not illustrate the raw material of polymeric composition by being commercially available.
Embodiment 1:
Raw material: in total weight, anhydride modified epoxy acrylate 15%; Aliphatic urethane acrylate 30%; Aromatic urethane acrylate 25%; Hydroxyethyl acrylate 10%; 1-hydroxy-cyciohexyl benzophenone 3%; 2,4,6-trimethylbenzoy-dipheny phosphine oxide 1.5%; Talcum powder 15%; Phthalocyanine blue 0.5%; Polyether-modified polydimethylsiloxane 0.3%.
Preparation method: step 1: the raw material dispersion machine of said ratio amount is stirred 1.5 hours, makes initiator dissolve and makes mixing of materials even; Step 2: step 1 gains are filtered, gets product.
Record product hardness HB, sticking power 5B, test performance is as shown in table 1.
Embodiment 2:
Raw material: in total weight, anhydride modified epoxy acrylate 20%; The aliphatic urethane acrylate 50% of caprolactone-derived long-chain polyhydric alcohol; Aromatic urethane acrylate 5%; Isobornyl acrylate 5%; Acrylate phosphate 0.5%; 1-hydroxy-cyciohexyl benzophenone 3%; 2,4,6-trimethylbenzoy-dipheny phosphine oxide 1%; Talcum powder 15%; Phthalocyanine blue 0.5%; Polyether-modified polydimethylsiloxane 0.3%.
Step 1: the raw material dispersion machine of said ratio amount is stirred 1.5 hours, makes initiator dissolve and makes mixing of materials even; Step 2: step 1 gains are filtered, gets product.
Record product hardness HB, sticking power 5B, test performance is as shown in table 1.
Embodiment 3:
Raw material: in total weight, derived from the aliphatic urethane acrylate 40% of tetrahydrofuran (THF) long-chain polyhydric alcohol; Anhydride modified epoxy acrylate 20%; Isobornyl acrylate 15%; 1-hydroxy-cyciohexyl benzophenone 2%; 2,4,6-trimethylbenzoy-dipheny phosphine oxide 1.5%; Talcum powder 20%; Phthalocyanine blue 0.5%; Aminomethoxy silane 1%; Polyether-modified polydimethylsiloxane 0.3%.
Step 1: the raw material dispersion machine of said ratio amount is stirred 1.5 hours, makes initiator dissolve and makes mixing of materials even; Step 2: step 1 gains are filtered, gets product.
Record product hardness HB, sticking power 5B, test performance is as shown in table 1.
Embodiment 4:
Raw material: in total weight, anhydride modified epoxy acrylate 25%; The aliphatic urethane acrylate 50% of caprolactone-derived long-chain polyhydric alcohol and tetrahydrofuran (THF) long-chain polyhydric alcohol; Viscoat 295 5%; 1-hydroxy-cyciohexyl benzophenone 3%; 2,4,6-trimethylbenzoy-dipheny phosphine oxide 1.5%; Talcum powder 15%; Phthalocyanine blue 0.5%; Polyether-modified polydimethylsiloxane 0.3%.
Step 1: the raw material dispersion machine of said ratio amount is stirred 1.5 hours, makes initiator dissolve and makes mixing of materials even; Step 2: step 1 gains are filtered, gets product.
Record product hardness HB, sticking power 5B, test performance is as shown in table 1.
Embodiment 5:
Raw material: in total weight, aliphatic urethane acrylate 50%; Anhydride modified epoxy acrylate 15%; Hydroxyethyl acrylate 10%; Viscoat 295 5%; Acrylate phosphate 1%; Talcum powder 15%; 1-hydroxy-cyciohexyl benzophenone 3%; Phthalocyanine blue 0.5%; Polyether-modified polydimethylsiloxane 0.5%.
Step 1: the raw material dispersion machine of said ratio amount is stirred 1.5 hours, makes initiator dissolve and makes mixing of materials even; Step 2: step 1 gains are filtered, gets product.
Record product hardness HB, sticking power 5B, test performance is as shown in table 1.
Comparative example 1:
Raw material: in total weight, aliphatic urethane acrylate 40%; Hydroxyethyl acrylate 5%; Viscoat 295 10%; Acrylate phosphate 1%; Talcum powder 40%; 1-hydroxy-cyciohexyl benzophenone 3%; Phthalocyanine blue 0.5%; Polyether-modified polydimethylsiloxane 0.5%.
Step 1: the raw material dispersion machine of said ratio amount is stirred 1.5 hours, makes initiator dissolve and makes mixing of materials even; Step 2: step 1 gains are filtered, gets product.
Record product hardness HB, sticking power 5B, test performance is as shown in table 1.
Comparative example 2:
Raw material: in total weight, anhydride modified epoxy acrylate 40%; Isobornyl acrylate 15%; 1-hydroxy-cyciohexyl benzophenone 2%; 2,4,6-trimethylbenzoy-dipheny phosphine oxide 1.5%; Talcum powder 40%; Phthalocyanine blue 0.5%; Aminomethoxy silane 1%; Polyether-modified polydimethylsiloxane 0.3%.
Step 1: the raw material dispersion machine of said ratio amount is stirred 1.5 hours, makes initiator dissolve and makes mixing of materials even; Step 2: step 1 gains are filtered, gets product.
Record product hardness HB, sticking power 5B, test performance is as shown in table 1.
Anti-for above-mentioned ultraviolet light polymerization anode is covered protection ink and be applied in metal and plastic cement is inlayed on base material, construction technology is:
1. pre-treatment: the metal of product and plastic cement are inlayed substrate surface and cleans;
2. open oil: uniform stirring before using, leave standstill 5-10 minute, be about 1:0.5 (viscosity 12-15 second) Mixed adjustment viscosity with thinner with weight ratio;
3. spray: ink is sprayed on aluminium, plastic cement inlays on substrate surface, build is at 30-45um;
4. the product surface after spraying first toasts 5 minutes by condition of cure: a. at 80 DEG C;
B. the product surface after baking is carried out UV solidification, energy: 1400-1600mj/cm 2;
5. process: effects on surface carries out the processing such as CNC cutting, anodic oxidation through the product of photocuring;
6. move back film: the product after processing is placed in depainting water and heats to 70-80 degree, demoulding completely in ultrasonic oscillation 5 minutes.
Ink test performance described in table 1 embodiment
Can be found out by above embodiment, comparative example, the anti-anode of ultraviolet light polymerization of the present invention covers protection ink adhesion excellent, resistance to CNC, resistance to cutting fluid, resistance to cleaning, resistance to anodic oxidation, easily demoulding, protective capability are extremely strong.
Obviously, above-described embodiment is only for clearly example being described, and the restriction not to embodiment.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here exhaustive without the need to also giving all embodiments.And thus the apparent change of extending out or variation be still among protection scope of the present invention.

Claims (10)

1. the anti-anode of ultraviolet light polymerization covers a protection ink, it is characterized in that: with the gross weight of ink composite for benchmark, and described ink comprises the component of following weight percent:
Wherein, described oligopolymer is the mixture of aliphatic urethane acrylate, anhydride modified epoxy acrylate.
2. the anti-anode of ultraviolet light polymerization according to claim 1 covers protection ink, it is characterized in that: described aliphatic urethane acrylate is derived from ester class and/or ethers long-chain polyhydric alcohol, and functionality is 2, and molecular weight is 960-5000.
3. the anti-anode of ultraviolet light polymerization according to claim 1 and 2 covers protection ink, it is characterized in that: the caprolactone-derived long-chain polyhydric alcohol of described aliphatic urethane acrylate and tetrahydrofuran (THF) long-chain polyhydric alcohol.
4. the anti-anode of the ultraviolet light polymerization according to claim 1-3 any one covers protection ink; it is characterized in that: with the gross weight of ink composite for benchmark; described oligopolymer comprises the aliphatic urethane acrylate that weight percent is 50-60%, and weight percent is the anhydride modified epoxy acrylate of 20-30%.
5. the anti-anode of the ultraviolet light polymerization according to claim 1-4 any one covers protection ink, it is characterized in that: described anhydride modified epoxy acrylate molecular weight is 3000-5000, and acid number is 70-100.
6. the anti-anode of the ultraviolet light polymerization according to claim 1-5 any one covers protection ink, it is characterized in that: described oligopolymer also comprise in aromatic urethane acrylate, polyester acrylate one or more.
7. the anti-anode of ultraviolet light polymerization according to claim 6 covers protection ink, it is characterized in that: the functionality of described aromatic urethane acrylate is 2, and molecular weight is 6000-8000; And/or
The functionality of described polyester acrylate is 2-3, and molecular weight is 1000-2000.
8. the anti-anode of the ultraviolet light polymerization according to claim 1-7 any one covers protection ink, it is characterized in that: described reactive monomer is one or more in Viscoat 295, tripropylene glycol diacrylate, glycerol tri-acrylate, glycol diacrylate, methyl acrylate, ethyl propenoate, propyl acrylate, isobutyl acrylate, vinylformic acid norbornene ester, isobornyl acrylate, isobornyl methacrylate, Hydroxyethyl acrylate, Propylene glycol monoacrylate, acrylated phosphate; And/or
Described initiator is 2-hydroxyl-2 methylphenyl acetone, 1-hydroxy-cyciohexyl benzophenone, 2,4, one or more in 6-trimethylbenzoy-dipheny phosphine oxide, benzophenone, 2,4,4-trimethylpentylphosphine oxide, benzil, 4-phenyl benzophenone; And/or
Described filler is one or more in barium sulfate, silicon-dioxide, wilkinite, talcum powder, kaolin.
9. the anti-anode of the ultraviolet light polymerization according to claim 1-8 any one covers protection ink, it is characterized in that: with the gross weight of ink composite for benchmark, and described ink also comprises the component of following weight percent:
Pigment 0.5-1%; And/or
Auxiliary agent 0.3-2%,
Wherein, described pigment is one or more in carbon black, phthalocyanine blue, phthalein viridescent; And/or
Described auxiliary agent is polyether-modified polydimethylsiloxane, polyacrylic ester, 2,6 di t butyl phenol, one or more in aminomethoxy silane.
10. the anti-anode of ultraviolet light polymerization described in claim 1-9 covers protection ink and is applicable to the composite base material that aluminium and plastic cement inlay.
CN201510167209.1A 2015-04-09 2015-04-09 A kind of anti-anode masking protection ink of ultraviolet light polymerization Expired - Fee Related CN104817880B (en)

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105968938A (en) * 2016-05-27 2016-09-28 广州亦盛环保科技有限公司 Ultraviolet-curable acid-resistant glass protection ink and preparation method thereof
CN108165087A (en) * 2017-12-28 2018-06-15 中科院广州化学有限公司 A kind of anti-anodic oxidation protection ink and preparation method and application
WO2019226645A1 (en) * 2018-05-25 2019-11-28 Corning Incorporated Hybrid inks including uv monomers, oligomers, and resins
CN112165819A (en) * 2020-10-29 2021-01-01 Oppo广东移动通信有限公司 Electronic equipment shell, manufacturing method thereof and electronic equipment
CN112759976A (en) * 2019-11-04 2021-05-07 北京氦舶科技有限责任公司 Touch screen conductive circuit protection ink and preparation method and construction process thereof
CN113150604A (en) * 2021-03-16 2021-07-23 上海抚佳精细化工有限公司 Printing ink and preparation method and application thereof
CN113913088A (en) * 2021-10-18 2022-01-11 深圳市金达盛化工有限公司 Preparation and application method of circuit board backing board protective coating
CN114231082A (en) * 2021-12-10 2022-03-25 浙江亚欣包装材料有限公司 Nano ink capable of increasing binding force with aluminum layer
CN115895403A (en) * 2022-12-28 2023-04-04 江阴通利光电科技有限公司 Hardening liquid for PETG (polyethylene terephthalate glycol) membrane, PETG composite membrane and preparation method
CN116180186A (en) * 2023-02-16 2023-05-30 广州亦盛环保科技有限公司 A local anti-anodizing process for the metal middle frame of a mobile phone

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103045015A (en) * 2013-01-25 2013-04-17 深圳市万佳原丝印器材有限公司 Liquid photo-imageable alkali developable and anodizing resistant ink and preparation method thereof
CN103045013A (en) * 2013-01-25 2013-04-17 深圳市万佳原丝印器材有限公司 Ultraviolet full-shielding printing ink and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103045015A (en) * 2013-01-25 2013-04-17 深圳市万佳原丝印器材有限公司 Liquid photo-imageable alkali developable and anodizing resistant ink and preparation method thereof
CN103045013A (en) * 2013-01-25 2013-04-17 深圳市万佳原丝印器材有限公司 Ultraviolet full-shielding printing ink and preparation method thereof

Cited By (14)

* Cited by examiner, † Cited by third party
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CN105968938B (en) * 2016-05-27 2019-06-14 广州亦盛环保科技有限公司 A kind of ultraviolet curing acid-resistant glass protective ink and preparation method thereof
CN105968938A (en) * 2016-05-27 2016-09-28 广州亦盛环保科技有限公司 Ultraviolet-curable acid-resistant glass protection ink and preparation method thereof
CN108165087B (en) * 2017-12-28 2021-07-23 中科院广州化学有限公司 A kind of anti-anodizing protective ink and preparation method and application
CN108165087A (en) * 2017-12-28 2018-06-15 中科院广州化学有限公司 A kind of anti-anodic oxidation protection ink and preparation method and application
WO2019226645A1 (en) * 2018-05-25 2019-11-28 Corning Incorporated Hybrid inks including uv monomers, oligomers, and resins
CN112759976A (en) * 2019-11-04 2021-05-07 北京氦舶科技有限责任公司 Touch screen conductive circuit protection ink and preparation method and construction process thereof
CN112165819A (en) * 2020-10-29 2021-01-01 Oppo广东移动通信有限公司 Electronic equipment shell, manufacturing method thereof and electronic equipment
CN112165819B (en) * 2020-10-29 2022-03-22 Oppo广东移动通信有限公司 Housing for electronic equipment, method of manufacturing the same, and electronic equipment
CN113150604A (en) * 2021-03-16 2021-07-23 上海抚佳精细化工有限公司 Printing ink and preparation method and application thereof
CN113913088A (en) * 2021-10-18 2022-01-11 深圳市金达盛化工有限公司 Preparation and application method of circuit board backing board protective coating
CN114231082A (en) * 2021-12-10 2022-03-25 浙江亚欣包装材料有限公司 Nano ink capable of increasing binding force with aluminum layer
CN115895403A (en) * 2022-12-28 2023-04-04 江阴通利光电科技有限公司 Hardening liquid for PETG (polyethylene terephthalate glycol) membrane, PETG composite membrane and preparation method
CN116180186A (en) * 2023-02-16 2023-05-30 广州亦盛环保科技有限公司 A local anti-anodizing process for the metal middle frame of a mobile phone
CN116180186B (en) * 2023-02-16 2025-10-10 广州亦盛环保科技有限公司 A local anti-anodization process for the metal middle frame of a mobile phone

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