CN104817880B - A kind of anti-anode masking protection ink of ultraviolet light polymerization - Google Patents
A kind of anti-anode masking protection ink of ultraviolet light polymerization Download PDFInfo
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- CN104817880B CN104817880B CN201510167209.1A CN201510167209A CN104817880B CN 104817880 B CN104817880 B CN 104817880B CN 201510167209 A CN201510167209 A CN 201510167209A CN 104817880 B CN104817880 B CN 104817880B
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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
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
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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
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
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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
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
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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
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C09D11/107—Printing 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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Abstract
The present invention provides a kind of ultraviolet light polymerization anti-anode masking protection ink, and on the basis of the gross weight of ink composite, the ink includes following components in percentage by weight：Oligomer 55 80%；Activated monomer 5 15%；Initiator 3 8%；Filler 15 25%；Wherein, the oligomer is aliphatic urethane acrylate, the mixture of anhydride modified epoxy acrylate.The ultraviolet light polymerization anti-anode masking that the present invention is provided protects that ink solidification speed is fast, adhesive force is good, resistance to CNC, scratch resistance, the immersion of resistance to various cutting fluids, anti-anodic oxidation, easy demoulding, the high-performance moving back noresidue after film, do not corrode base material; suitable for aluminium or aluminum alloy base material, plastic rubber substrate, the preparation base material of aluminium and plastic cement is particularly well-suited to.
Description
Technical field
The present invention relates to surface protection ink product technical field, and in particular to a kind of anti-anode masking of ultraviolet light polymerization is protected
Shield ink, is particularly well-suited to the composite base material that aluminium is inlayed with plastic cement.
Background technology
UV curable ink, also known as UV ink, is a kind of environmental protection ink for developing rapidly, the oil with traditional type
Ink is compared, with instantaneous solidification, without volatile organic solvent, production efficiency it is high, into film hardness it is strong, solvent resistance is good, right
Environmental pollution is small, the features such as save energy, because it has the incomparable advantage of traditional solvent-borne ink, widely should
For the multi-party field such as Yan Bao, Jiu Bao, cosmetic package, Key works Drug packing and pressure-sensitive adhesive trade mark.
Now, increasing product (such as phone housing, panel computer etc.) is entered using multiple materials such as metal, plastic cement
Row appearance design, metal and the plastic cement of formation inlay substrate surface also to be needed to use CNC to process to meet the demand of more complicated design,
And metal is easily scratched in CNC process, cause product bad, this is required in CNC process to product
Surface is protected, and as the change of material and products C NC processing more become more meticulous, this is just in products C NC process
Surface protection proposes requirement higher.Wherein, aluminium or aluminium alloy be because of characteristics such as its cheap and easy to get, soft easy processings, often quilt
For in the processing of such product.It is existing in order to strengthen the aesthetic property of the corrosion resistance of aluminium or aluminium alloy, product appearance
The product casing prepared by aluminium or aluminium alloy in technology is carried out multiple anodized more, will first time own anodic oxygen
The figure for changing part is protected, and then carries out the anodized of secondary or more time, then inoxidizability is strong, resistance to CNC
Protection ink turns into very powerful and exceedingly arrogant product.
As Chinese patent literature CN103045015 discloses a kind of anti-anodic oxidation ink of liquid photosensitive imaging and developing with alkali,
The ink includes according to parts by weight:Photosensitive resin 30-50 parts, 5-15 parts of propylene oxide vinegar resin, reactive diluent 10-20
Part, solvent 5-15 parts, light trigger 1-10 parts, auxiliary agent 1-3 parts, filler 20-40 parts and pigment 0.5-0.8 parts, the alkali solubility
Photosensitive resin is made up of following raw material:35-50 parts of epoxy resin, 20-40 parts of DBE, 15-20 parts of acrylic acid, 8-15 parts of maleic acid
Match somebody with somebody, 0.5-1 parts of hydroquinones, 0.5-1 parts of tetraethyl Australia presses.The anti-anti- spray of anodic oxidation ink of the liquid photosensitive imaging and developing with alkali
Sand, resistance to highly basic, resistance to strong acid, anti-anodic oxidation.But, for the composite base material that aluminium and plastic cement are inlayed, oil is protected using this kind
Ink has that plastic surface upper protective film demoulding is difficult, if using traditional plastic cement protect ink exist again diaphragm intolerant to
The problem of CNC so that traditional protection ink is difficult to the surface protection demand of competent aluminium and plastic cement preparation base material, and then
Have that product yield is low, it is competent to be difficult in having a case that the design of curved surface and complex profile, it is impossible to which adequately protect product.
The content of the invention
When what the present invention was solved is that ink is applied to aluminium with plastic cement inlaid material in the prior art, it is impossible to while meeting aluminium
The resistance to CNC of material base protection ink, resistance to anodic oxidation, plastic rubber substrate protect the technical need of the easy demoulding of ink, pad pasting protection technique
Efficiency is low, product yield is low and the technical problem such as competent is difficult in the design with curved surface and complex profile, and then provides one
Kind of simple to operate, efficiency high, curing rate is fast, adhesive force is good, resistance to CNC, scratch resistance, resistance to various cutting fluids immersions, anti-anodic oxygen
Change, easy demoulding, the high-performance ultraviolet cured anti-anode masking protection ink for moving back noresidue after film, not corroding base material.
A kind of anti-anode masking protection ink of ultraviolet light polymerization, on the basis of the gross weight of ink composite, the ink
Including following components in percentage by weight：
Wherein, the oligomer is aliphatic urethane acrylate, the mixture of anhydride modified epoxy acrylate.
The aliphatic urethane acrylate is 2 derived from esters and/or ethers long-chain polyhydric alcohol, degree of functionality, molecule
It is 960-5000 to measure.
The caprolactone-derived long-chain polyhydric alcohol of aliphatic urethane acrylate and tetrahydrofuran long-chain polyhydric alcohol.
On the basis of the gross weight of ink composite, the oligomer includes that percentage by weight is the aliphatic of 50-60%
Urethane acrylate, percentage by weight is the anhydride modified epoxy acrylate of 20-30%.
The anhydride modified epoxy acrylate molecular weight is 3000-5000, and acid number is 70-100.
The oligomer also includes one or more in aromatic urethane acrylate, polyester acrylate.
The degree of functionality of the aromatic urethane acrylate is 2, and molecular weight is 6000-8000；And/or
The degree of functionality of the polyester acrylate is 2-3, and molecular weight is 1000-2000.
The activated monomer is trimethylolpropane trimethacrylate, tripropylene glycol diacrylate, the acrylic acid of glycerine three
Ester, glycol diacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, isobutyl acrylate, acrylic acid borneol
In ester, isobornyl acrylate, isobornyl methacrylate, hydroxy-ethyl acrylate, hydroxypropyl acrylate, acrylated phosphate
One or more；And/or
The initiator is the methylphenyl acetone of 2- hydroxyls -2,1- hydroxy-cyciohexyls Benzophenone, 2,4,6- trimethylbenzenes
Formoxyl-diphenyl phosphine oxide, benzophenone, 2,4,4- trimethylpentylphosphine oxides, benzil, 4- phenyl benzophenones
In one or more.
Described filler is one or more in barium sulfate, silica, bentonite, talcum powder, kaolin.
On the basis of the gross weight of ink composite, the ink also includes following components in percentage by weight：
Pigment 0.5-1%；And/or
Auxiliary agent 0.3-2%.
And/or
The pigment is one or more in carbon black, phthalocyanine blue, dark green；And/or
The auxiliary agent is polyether-modified dimethyl silicone polymer, polyacrylate, 2,6- DI-tert-butylphenol compounds, amino methoxy
One or more in base silane.
The anti-anode masking protection ink of ultraviolet light polymerization is applied to the composite base material that aluminium is inlayed with plastic cement.
The anti-anode masking protection ink of ultraviolet light polymerization that the present invention is provided, on the basis of the gross weight of ink composite,
The ink includes following components in percentage by weight：Oligomer 55-80%；Activated monomer 5-15%；Initiator 3-8%；Filler
15-25%；Wherein, the oligomer is aliphatic urethane acrylate, the mixture of anhydride modified epoxy acrylate.Third
Alkene acid ester resin constitutes the basic framework of cured article, and inventor is formulated herein by discovery pleasantly surprised after many experiments
The surface tension that lower oligomer is collectively forming the macromolecule net-structured film of crosslinking when being acted on activated monomer is less than aluminium base
Material and plastic rubber substrate surface tension, good tack is respectively provided with two kinds of base materials.The present invention uses aliphatic polyurethane third
The mixing of olefin(e) acid ester and anhydride modified epoxy acrylate, the structural membrane that the lower oligomer of ratio mixing is crosslinked with activated monomer
With prominent film forming extensibility, pliability and inoxidizability.The plastic cement for being coated with present invention offer ink inlays base with aluminium
When material is with remover phase separation, ink shows easily to move back the characteristic of film, noresidue.The ink that i.e. present invention is provided is particularly well-suited to
Aluminium and plastic cement inlay base material, can meet simultaneously resistance to CNC on aluminium, on anti-oxidant, plastic material easy demoulding technical need,
Go for the design structure with curved surface and complex profile.
In the ultraviolet light polymerization anti-anode masking protection ink that the present invention is provided oligomer can be derived from esters and/or
Ethers long-chain polyhydric alcohol, degree of functionality are the aliphatic urethane acrylate that 2, molecular weight is 960-5000, low degree of functionality it is poly-
Urethane acrylate has the film forming speed with high-ranking official's degree material equity, and its low functional structure causes that shrinkage factor during film forming becomes again
Obtain smaller, therefore the ink has good adhesive force while effective acquisition toughness film on base material.Polyurethane
The material of acrylate structural is the molecular configuration combined with soft and hard segments, and excellent abrasion resistance properties can be provided in film,
The ink embodies excellent resistance to CNC, anti-zoned Flaw characterization.
Aliphatic urethane acrylate is described in the anti-anode masking protection ink of ultraviolet light polymerization that the present invention is provided
Caprolactone long-chain polyhydric alcohol and the lipid structure urethane acrylate of tetrahydrofuran long-chain polyhydric alcohol synthesis, caprolactone long-chain are more
First alcohol assigns ink excellent pliability and demoulding performance, and tetrahydrofuran long-chain polyhydric alcohol assigns ink splendid tack.
The molecule of anhydride modified epoxy acrylate in the anti-anode masking protection ink of ultraviolet light polymerization that the present invention is provided
It is 3000-5000 to measure, and acid number is 70-100.Contain substantial amounts of hydroxyl in Epocryl, be esterified with acid anhydrides
Reaction can introduce carboxyl improve molecular polarity so that improve the hydrophily of Epocryl, the adhesive force to base material and
The alkali solubility of resin, for ink provides good resistance to cutting fluid performance, assigns ink splendid anti-anodic oxidation performance.Work as base material
For aluminium and during plastic cement combination, in anhydride modified epoxy acrylate-COOH group can react with alkali, so ought select
During alkaline depainting water, demoulding is better.And Epocryl carboxylated degree is higher, it is better that aqueous resin dissipates property；
When the timing of carboxylated degree one, degree of neutralization are higher, it is better that aqueous resin dissipates property.Inventor is by pleasantly surprised after many experiments
It was found that, the film that molecular weight is 3000-5000 and acid number to be formed for the anhydride modified epoxy acrylate of 70-100 is to base material
Adhesive force, anti-anode performance are optimal, and acid number is too high, the hydraulic performance decline of resistance to CNC；Acid number is too low, resistance to anodic oxidation performance reduction.
In the anti-anode masking protection ink of ultraviolet light polymerization that the present invention is provided, the oligomer is including percentage by weight
The aliphatic urethane acrylate of 50%-60%, percentage by weight is the anhydride modified epoxy acrylate of 20%-30%.
Aliphatic urethane acrylate addition is bigger, and demoulding is easier, and anti-sandblasting performance is better, and resistance to CNC performances are poorer, resistance to anode
Oxidation susceptibility is also poorer；Anhydride modified epoxy acrylate addition is bigger, and resistance to CNC performances are better, and resistance to anodic oxidation performance is got over
It is good, but demoulding performance is poorer.Determined through experiment, be 50%-60% in aliphatic urethane acrylate addition, it is anhydride modified
When epoxy acrylate addition is 20%-30%, can balance the property retentions such as the resistance to CNC of ink, resistance to anodic oxidation, demoulding.
It is 2- that oligomer can also add degree of functionality in the anti-anode masking protection ink of ultraviolet light polymerization that the present invention is provided
3rd, molecular weight is the polyester acrylate of 1000-2000, strengthens the toughness of film.
The anti-anode masking protection ink of ultraviolet light polymerization that the present invention is provided, can be prepared using method commonly used in the art,
Step is simple, easy to operate, and because its curing rate is fast, adhesive force is good, it is resistance to CNC, scratch resistance, the immersion of resistance to various cutting fluids, anti-
Anodic oxidation, easy demoulding, the high-performance moved back noresidue after film, do not corrode base material, it is adaptable to aluminium or aluminum alloy base material, plastic cement base
Material, is particularly well-suited to the preparation base material of aluminium and plastic cement.
Specific embodiment：
In order that the object, technical solutions and advantages of the present invention are clearer, below in conjunction with embodiment to of the invention
Implementation method is described in further detail.
The invention provides a kind of anti-anode masking protection ink of ultraviolet light polymerization, the gross weight with ink composite is as base
Standard, the ink includes oligomer, activated monomer, initiator and filler.
Wherein, oligomer constitutes the basic framework of cured article as the matrix resin of product, after determining solidification
The key property (hardness, pliability, adhesive force, optical property, ageing-resistant etc.) of product.The oligomer is a kind of molecular weight phase
The polymer of 2 to tens times is repeated to relatively low, monomeric unit, oligomer selection molecular weight of the present invention is 1000-8000, excellent
The acrylic compounds photosensitive resin of 2000-7000 or 2500-5000 is selected, if relative molecular mass is excessive, viscosity is too high, is unfavorable for
Allotment and construction, coating performance are not easy to control.
Oligomer is aliphatic urethane acrylate, the mixture of anhydride modified epoxy acrylate in the present invention, is somebody's turn to do
Mixing oligomer has prominent inoxidizability and excellent adhesive force with the structural membrane of activated monomer crosslinking.
Used as selectable embodiment, oligomer includes that percentage by weight is the aliphatic polyurethane third of 50%-60%
Olefin(e) acid ester, percentage by weight is the anhydride modified epoxy acrylate of 20%-30%.Aliphatic urethane acrylate addition
Bigger, demoulding is easier, and anti-sandblasting performance is better, and resistance to CNC performances are poorer, and resistance to anodic oxidation performance is also poorer；Anhydride modified ring
Oxypropylene acid esters addition is bigger, and resistance to CNC performances are better, and resistance to anodic oxidation performance is better, but demoulding performance is poorer.Surveyed through experiment
It is fixed, it is 50%-60% in aliphatic urethane acrylate addition, anhydride modified epoxy acrylate addition is 20%-
When 30%, can balance the property retentions such as the resistance to CNC of ink, resistance to anodic oxidation, demoulding.
Used as selectable embodiment, aliphatic urethane acrylate is long derived from esters or ethers in the present invention
The lipid structure urethane acrylate of chain polyalcohol, its basic structure includes soft chain segment (polyurethane portion) and hard segment (third
Olefin(e) acid ester moiety), the oligomer is collectively forming cross-linked polymer network structure with activated monomer, forms and aluminium material, plastic cement
Base material has a soft and tough film of high adhesion, and this layer of tough diaphragm have in the presence of remover it is excellent
Demoulding.Wherein, the carbochain in the esters of acrylic acid synthesizing ester oligomer or ethers long-chain polyhydric alcohol is C12~C30.It is preferred that official
Energy degree is 2, and molecular weight is the aliphatic urethane acrylate of 960-5000 or 1000-4000 or 2000-3000.Preferably
It is, the caprolactone-derived long-chain polyhydric alcohol of aliphatic urethane acrylate and/or tetrahydrofuran long-chain polyhydric alcohol that caprolactone is long
Chain polyalcohol assigns ink excellent pliability and demoulding performance, and tetrahydrofuran long-chain polyhydric alcohol assigns ink splendid attachment
Property.
Aromatic urethane acrylate, polyester acrylic are may also include as selectable embodiment, in oligomer
One or more in ester.Aromatic urethane acrylate can improve the endurance of ink.Polyester acrylate can be carried
High solidification speed, improves cured film mechanical mechanics property, strengthens the toughness and solvent resistance of film, and preferably degree of functionality is 2-3, point
Son amount is 1000-2000, or 1200-1800, or 1300-1700, or 1400-1600 polyester acrylate.
As selectable embodiment, oligomer selection aliphatic urethane acrylate, anhydride modified propylene oxide
Acid esters, aromatic urethane acrylate, the mixture of polyester acrylate, its ratio are (50%-60%)：(20%-
30%)：(5%-10%)：(5%-10%).
Used as selectable embodiment, on the basis of ink composite gross weight, the consumption 55-80% of oligomer is excellent
Select 60-75%, more preferably 65-70%, more preferably 68%.
Activated monomer is a kind of functional form monomer, has solidification concurrently in the compositional system of UV curable ink and is crosslinked and molten
The dual-use function of agent, its effect is the viscosity for adjusting UV curable ink, and the oligomer larger to viscosity is diluted, and it can
To control solidification crosslink density, improve physics, the mechanical performance of film, participate in film-forming.The degree of functionality of activated monomer is to solid
Change speed to have an impact, degree of functionality is bigger, and curing rate is faster.Activated monomer can be selected from the acrylic acid of single functionality in the present invention
One or more in esters, the esters of acrylic acid of bifunctionality, the esters of acrylic acid of three-functionality-degree.
The acrylic ester monomer of three-functionality-degree, can be enumerated as trimethylolpropane trimethacrylate, the acrylic acid of glycerine three
Ester.The acrylic ester monomer of bifunctionality, can enumerate glycol diacrylate.The acrylic ester monomer of single functionality,
Methyl acrylate, ethyl acrylate, propyl acrylate, isobutyl acrylate, acrylic acid norbornene ester, the different ice of acrylic acid can be enumerated
Piece ester, isobornyl methacrylate, hydroxypropyl acrylate, acrylated phosphate.Above acrylic ester monomer both can be single
Solely use, it is also possible to which two or more is applied in combination.
Used as selectable embodiment, on the basis of ink composite gross weight, the consumption of activated monomer is 5-15%,
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 activity
The material of unsaturated group polymerization in ion radical, and then initiation ink, it is produced vivaciously certainly after caning absorb the luminous energy of certain wavelength
By base or cation, trigger or be catalyzed the polymerization of corresponding monomer or prepolymer.The performance of initiator determines ultraviolet light polymerization
The state of cure and curing rate of ink.Selection can trigger the initiator of radical polymerization by ultraviolet excitation in the present invention.
Used as selectable embodiment, initiator can be selected from following material：The methylphenyl acetone of 2- hydroxyls -2,1- hydroxyls
Phenylcyclohexyl ketone, 2,4,6- trimethylbenzoy-diphenies phosphine oxide, benzophenone, the oxidation of 2,4,4- tri-methyl-amyls
One or more in phosphine, benzil, 4- phenyl benzophenones.
As selectable embodiment, on the basis of ink composite gross weight, the consumption 3-8% of initiator, preferably
4-7%, more preferably 5-6%.
In the present invention, described filler, to its important function of the rheological characteristic and physical and mechanical property of ink, can be various normal
One or more in the filler of rule, for example, barium sulfate, silica, bentonite, talcum powder, kaolin；With ink combination
On the basis of thing gross weight, the consumption of filler is 15-25%, preferably 18-22%, such as 20%；
To make ink of the present invention have more preferable implementation result in implementation process, pigment can also be included in ink,
Also dependent on needing appropriate other auxiliary agents of addition, such as one or more in defoamer, stabilizer, levelling agent.
Used as selectable embodiment, on the basis of the gross weight of ink composite, the ink also includes following heavy
Measure the component of part：
Pigment 0.5-1%, preferably 0.8%；And/or
Auxiliary agent 0.3-2%, preferably 0.5-1.5%, more preferably 0.8-1.2%, such as 1.0%.
The pigment can be various conventional pigment, make ink that certain color, for example, carbon black, titanium dioxide, phthalein is presented
One or more in blue or green pigment (such as phthalocyanine blue, dark green), can be selected as needed；
The auxiliary agent is preferably polyether-modified dimethyl silicone polymer, polyacrylate, 2,6- DI-tert-butylphenol compounds, amino
One or more in methoxy silane.
The anti-anode masking protection ink of ultraviolet light polymerization of the present invention can be prepared using following methods, and the method includes
Following steps：
Step 1：Material oligomer, activated monomer and initiator are weighed in proportion, raw material is transferred in dispersion machine and is stirred
Mixing, such as mixing time are 1-1.5 hours, and initiator fully dissolves, material dispersion is uniform；
Step 2：The mixture of finely dispersed, the suitable viscosity of step 1 gained is filtered, required finished product is obtained final product.
The anti-anode masking protection ink of ultraviolet light polymerization of the present invention is applied to aluminium or aluminum alloy base material, plastic cement base
Material, is particularly well-suited to the composite base material that aluminium is inlayed with plastic cement.
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate the present invention
Rather than limitation the scope of the present invention.The experimental technique of unreceipted actual conditions in the following example, generally marks according to country
Standard is determined.If without corresponding national standard, being built according to general international standard, normal condition or according to manufacturer
The condition of view is carried out.Unless otherwise indicated, otherwise all of metering is the weight portion with ink composite as gross weight meter, described
Polymer molecular weight be number-average molecular weight, the raw material for not illustrating polymeric composition can be commercially available.
Embodiment 1：
Raw material：In terms of total weight, anhydride modified epoxy acrylate 15%；Aliphatic urethane acrylate
30%；Aromatic urethane acrylate 25%；Hydroxy-ethyl acrylate 10%；1- hydroxy-cyciohexyls Benzophenone 3%；2,4,6-
Trimethylbenzoy-dipheny phosphine oxide 1.5%；Talcum powder 15%；Phthalocyanine blue 0.5%；Polyether-modified polydimethylsiloxanes
Alkane 0.3%.
Preparation method：Step 1：The raw material of said ratio amount is stirred 1.5 hours with dispersion machine, initiator is dissolved and is made
Material is well mixed；Step 2：By the filtering of step 1 gains, get product.
Product hardness HB is measured, adhesive force 5B, test performance is as shown in table 1.
Embodiment 2：
Raw material：In terms of total weight, anhydride modified epoxy acrylate 20%；Caprolactone-derived long-chain polyhydric alcohol
Aliphatic urethane acrylate 50%；Aromatic urethane acrylate 5%；Isobornyl acrylate 5%；Acrylate phosphorus
Acid esters 0.5%；1- hydroxy-cyciohexyls Benzophenone 3%；2,4,6- trimethylbenzoy-diphenies phosphine oxide 1%；Talcum powder
15%；Phthalocyanine blue 0.5%；Polyether-modified dimethyl silicone polymer 0.3%.
Step 1：The raw material of said ratio amount is stirred 1.5 hours with dispersion machine, initiator is dissolved and is mixed material
Uniformly；Step 2：By the filtering of step 1 gains, get product.
Product hardness HB is measured, adhesive force 5B, test performance is as shown in table 1.
Embodiment 3：
Raw material：In terms of total weight, the aliphatic urethane acrylate derived from tetrahydrofuran long-chain polyhydric alcohol
40%；Anhydride modified epoxy acrylate 20%；Isobornyl acrylate 15%；1- hydroxy-cyciohexyls Benzophenone 2%；2,4,
6- trimethylbenzoy-diphenies phosphine oxide 1.5%；Talcum powder 20%；Phthalocyanine blue 0.5%；Aminomethoxy silane 1%；
Polyether-modified dimethyl silicone polymer 0.3%.
Step 1：The raw material of said ratio amount is stirred 1.5 hours with dispersion machine, initiator is dissolved and is mixed material
Uniformly；Step 2：By the filtering of step 1 gains, get product.
Product hardness HB is measured, adhesive force 5B, test performance is as shown in table 1.
Embodiment 4：
Raw material：In terms of total weight, anhydride modified epoxy acrylate 25%；Caprolactone-derived long-chain polyhydric alcohol and
The aliphatic urethane acrylate 50% of tetrahydrofuran long-chain polyhydric alcohol；Trimethylolpropane trimethacrylate 5%；1- hydroxyls
Base-phenylcyclohexyl ketone 3%；2,4,6- trimethylbenzoy-diphenies phosphine oxide 1.5%；Talcum powder 15%；Phthalocyanine blue
0.5%；Polyether-modified dimethyl silicone polymer 0.3%.
Step 1：The raw material of said ratio amount is stirred 1.5 hours with dispersion machine, initiator is dissolved and is mixed material
Uniformly；Step 2：By the filtering of step 1 gains, get product.
Product hardness HB is measured, adhesive force 5B, test performance is as shown in table 1.
Embodiment 5：
Raw material：In terms of total weight, aliphatic urethane acrylate 50%；Anhydride modified epoxy acrylate
15%；Hydroxy-ethyl acrylate 10%；Trimethylolpropane trimethacrylate 5%；Acrylate phosphate 1%；Talcum powder 15%；
1- hydroxy-cyciohexyls Benzophenone 3%；Phthalocyanine blue 0.5%；Polyether-modified dimethyl silicone polymer 0.5%.
Step 1：The raw material of said ratio amount is stirred 1.5 hours with dispersion machine, initiator is dissolved and is mixed material
Uniformly；Step 2：By the filtering of step 1 gains, get product.
Product hardness HB is measured, adhesive force 5B, test performance is as shown in table 1.
Comparative example 1：
Raw material：In terms of total weight, aliphatic urethane acrylate 40%；Hydroxy-ethyl acrylate 5%；Trihydroxy methyl
Propane triacrylate 10%；Acrylate phosphate 1%；Talcum powder 40%；1- hydroxy-cyciohexyls Benzophenone 3%；Phthalocyanine blue
0.5%；Polyether-modified dimethyl silicone polymer 0.5%.
Step 1：The raw material of said ratio amount is stirred 1.5 hours with dispersion machine, initiator is dissolved and is mixed material
Uniformly；Step 2：By the filtering of step 1 gains, get product.
Product hardness HB is measured, adhesive force 5B, test performance is as shown in table 1.
Comparative example 2：
Raw material：In terms of total weight, anhydride modified epoxy acrylate 40%；Isobornyl acrylate 15%；1- hydroxyls
Base-phenylcyclohexyl ketone 2%；2,4,6- trimethylbenzoy-diphenies phosphine oxide 1.5%；Talcum powder 40%；Phthalocyanine blue
0.5%；Aminomethoxy silane 1%；Polyether-modified dimethyl silicone polymer 0.3%.
Step 1：The raw material of said ratio amount is stirred 1.5 hours with dispersion machine, initiator is dissolved and is mixed material
Uniformly；Step 2：By the filtering of step 1 gains, get product.
Product hardness HB is measured, adhesive force 5B, test performance is as shown in table 1.
The anti-anode masking protection ink of above-mentioned ultraviolet light polymerization is applied and is inlayed on base material in metal and plastic cement, construction technology
It is:
1. pre-treatment：The metal of product and plastic cement are inlayed into substrate surface cleaning；
2. oil is opened：Using preceding uniform stirring, 5-10 minutes is stood, with diluent with weight ratio about 1:0.5 (viscosity 12-
15 seconds) Mixed adjustment viscosity；
3. spray：Ink is sprayed on into aluminium, plastic cement to inlay on substrate surface, thickness of dry film is in 30-45um；
4. condition of cure：A. first the product surface after spraying is toasted 5 minutes at 80 DEG C；
B. the product surface after baking is carried out into UV solidifications, energy:1400-1600mj/cm2；
5. process：CNC cuttings, anodic oxidation etc. are carried out to surface through the product of photocuring to process；
6. film is moved back：Product after processing is placed in 70-80 degree is heated up in depainting water, in ultrasonic oscillation 5 minutes completely
Demoulding.
Ink test performance described in the embodiment of table 1
Be can be seen that by above example, comparative example, the anti-anode masking protection ink adhesion of ultraviolet light polymerization of the invention
Excellent, resistance to CNC, resistance to cutting fluid, resistance to cleaning, resistance to anodic oxidation, easy demoulding, protective capability are extremely strong.
Obviously, above-described embodiment is only intended to clearly illustrate example, and not to the restriction of implementation method.It is right
For those of ordinary skill in the art, can also make on the basis of the above description other multi-forms change or
Change.There is no need and unable to be exhaustive to all of implementation method.And the obvious change thus extended out or
Among changing still in protection scope of the present invention.
Claims (22)
1. ink is protected in the anti-anode masking of a kind of ultraviolet light polymerization, it is characterised in that：On the basis of the gross weight of ink composite,
The ink includes following components in percentage by weight：
Wherein, the oligomer is aliphatic urethane acrylate, the mixture of anhydride modified epoxy acrylate；
On the basis of the gross weight of ink composite, the oligomer includes that percentage by weight is the aliphatic poly ammonia of 50-60%
Ester acrylate, percentage by weight is the anhydride modified epoxy acrylate of 20-30%.
2. ink is protected in the anti-anode masking of ultraviolet light polymerization according to claim 1, it is characterised in that：The aliphatic poly
Urethane acrylate is 2 derived from esters and/or ethers long-chain polyhydric alcohol, degree of functionality, and molecular weight is 960-5000.
3. ink is protected in the anti-anode masking of ultraviolet light polymerization according to claim 1 and 2, it is characterised in that：The fat
The caprolactone-derived long-chain polyhydric alcohol of adoption urethane acrylate and tetrahydrofuran long-chain polyhydric alcohol.
4. ink is protected in the anti-anode masking of ultraviolet light polymerization according to claim 1 and 2, it is characterised in that：The acid anhydrides
Modified epoxy acrylic ester molecular weight is 3000-5000, and acid number is 70-100.
5. ink is protected in the anti-anode masking of ultraviolet light polymerization according to claim 3, it is characterised in that：It is described anhydride modified
Epoxy acrylate molecular weight is 3000-5000, and acid number is 70-100.
6. the anti-anode masking protection ink of ultraviolet light polymerization according to claim 1 or 2 or 5, it is characterised in that：It is described low
Polymers also includes one or more in aromatic urethane acrylate, polyester acrylate.
7. ink is protected in the anti-anode masking of ultraviolet light polymerization according to claim 3, it is characterised in that：The oligomer is also
Including one or more in aromatic urethane acrylate, polyester acrylate.
8. ink is protected in the anti-anode masking of ultraviolet light polymerization according to claim 4, it is characterised in that：The oligomer is also
Including one or more in aromatic urethane acrylate, polyester acrylate.
9. ink is protected in the anti-anode masking of ultraviolet light polymerization according to claim 6, it is characterised in that：The fragrant adoption
The degree of functionality of urethane acrylate is 2, and molecular weight is 6000-8000；And/or
The degree of functionality of the polyester acrylate is 2-3, and molecular weight is 1000-2000.
10. the anti-anode masking protection ink of ultraviolet light polymerization according to claim 7 or 8, it is characterised in that：The fragrance
The degree of functionality of adoption urethane acrylate is 2, and molecular weight is 6000-8000；And/or
The degree of functionality of the polyester acrylate is 2-3, and molecular weight is 1000-2000.
11. according to claim 1-2, or 5, or the anti-anode masking protection ink of ultraviolet light polymerization described in 7-9 any one, its
It is characterised by：The activated monomer is trimethylolpropane trimethacrylate, tripropylene glycol diacrylate, the acrylic acid of glycerine three
Ester, glycol diacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, isobutyl acrylate, acrylic acid borneol
In ester, isobornyl acrylate, isobornyl methacrylate, hydroxy-ethyl acrylate, hydroxypropyl acrylate, acrylated phosphate
One or more；And/or
The initiator is the methylphenyl acetone of 2- hydroxyls -2,1- hydroxy-cyciohexyls Benzophenone, 2,4,6- trimethylbenzoyls
In base-diphenyl phosphine oxide, benzophenone, 2,4,4- trimethylpentylphosphine oxides, benzil, 4- phenyl benzophenones
One or more；And/or
Described filler is one or more in barium sulfate, silica, bentonite, talcum powder, kaolin.
The 12. anti-anode masking protection ink of ultraviolet light polymerization according to claim 3, it is characterised in that：The activity is single
Body is trimethylolpropane trimethacrylate, tripropylene glycol diacrylate, glycerol tri-acrylate, ethylene glycol diacrylate
Ester, methyl acrylate, ethyl acrylate, propyl acrylate, isobutyl acrylate, acrylic acid norbornene ester, isobornyl acrylate,
One or more in isobornyl methacrylate, hydroxy-ethyl acrylate, hydroxypropyl acrylate, acrylated phosphate；And/or
The initiator is the methylphenyl acetone of 2- hydroxyls -2,1- hydroxy-cyciohexyls Benzophenone, 2,4,6- trimethylbenzoyls
In base-diphenyl phosphine oxide, benzophenone, 2,4,4- trimethylpentylphosphine oxides, benzil, 4- phenyl benzophenones
One or more；And/or
Described filler is one or more in barium sulfate, silica, bentonite, talcum powder, kaolin.
The 13. anti-anode masking protection ink of ultraviolet light polymerization according to claim 4, it is characterised in that：The activity is single
Body is trimethylolpropane trimethacrylate, tripropylene glycol diacrylate, glycerol tri-acrylate, ethylene glycol diacrylate
Ester, methyl acrylate, ethyl acrylate, propyl acrylate, isobutyl acrylate, acrylic acid norbornene ester, isobornyl acrylate,
One or more in isobornyl methacrylate, hydroxy-ethyl acrylate, hydroxypropyl acrylate, acrylated phosphate；And/or
The initiator is the methylphenyl acetone of 2- hydroxyls -2,1- hydroxy-cyciohexyls Benzophenone, 2,4,6- trimethylbenzoyls
In base-diphenyl phosphine oxide, benzophenone, 2,4,4- trimethylpentylphosphine oxides, benzil, 4- phenyl benzophenones
One or more；And/or
Described filler is one or more in barium sulfate, silica, bentonite, talcum powder, kaolin.
The 14. anti-anode masking protection ink of ultraviolet light polymerization according to claim 6, it is characterised in that：The activity is single
Body is trimethylolpropane trimethacrylate, tripropylene glycol diacrylate, glycerol tri-acrylate, ethylene glycol diacrylate
Ester, methyl acrylate, ethyl acrylate, propyl acrylate, isobutyl acrylate, acrylic acid norbornene ester, isobornyl acrylate,
One or more in isobornyl methacrylate, hydroxy-ethyl acrylate, hydroxypropyl acrylate, acrylated phosphate；And/or
The initiator is the methylphenyl acetone of 2- hydroxyls -2,1- hydroxy-cyciohexyls Benzophenone, 2,4,6- trimethylbenzoyls
In base-diphenyl phosphine oxide, benzophenone, 2,4,4- trimethylpentylphosphine oxides, benzil, 4- phenyl benzophenones
One or more；And/or
Described filler is one or more in barium sulfate, silica, bentonite, talcum powder, kaolin.
The 15. anti-anode masking protection ink of ultraviolet light polymerization according to claim 10, it is characterised in that：The activity is single
Body is trimethylolpropane trimethacrylate, tripropylene glycol diacrylate, glycerol tri-acrylate, ethylene glycol diacrylate
Ester, methyl acrylate, ethyl acrylate, propyl acrylate, isobutyl acrylate, acrylic acid norbornene ester, isobornyl acrylate,
One or more in isobornyl methacrylate, hydroxy-ethyl acrylate, hydroxypropyl acrylate, acrylated phosphate；And/or
The initiator is the methylphenyl acetone of 2- hydroxyls -2,1- hydroxy-cyciohexyls Benzophenone, 2,4,6- trimethylbenzoyls
In base-diphenyl phosphine oxide, benzophenone, 2,4,4- trimethylpentylphosphine oxides, benzil, 4- phenyl benzophenones
One or more；And/or
Described filler is one or more in barium sulfate, silica, bentonite, talcum powder, kaolin.
16. according to claim 1-2, or 5, or 7-9, or the anti-anode masking guarantor of ultraviolet light polymerization described in 12-15 any one
Shield ink, it is characterised in that：On the basis of the gross weight of ink composite, the ink also group including following percentage by weight
Point：
Pigment 0.5-1%；With/
Or auxiliary agent 0.3-2%,
Wherein, the pigment is one or more in carbon black, phthalocyanine blue, dark green；And/or
The auxiliary agent is polyether-modified dimethyl silicone polymer, polyacrylate, 2,6- DI-tert-butylphenol compounds, aminomethoxy silicon
One or more in alkane.
The 17. anti-anode masking protection ink of ultraviolet light polymerization according to claim 3, it is characterised in that：With ink combination
On the basis of the gross weight of thing, the ink also includes following components in percentage by weight：
Pigment 0.5-1%；With/
Or auxiliary agent 0.3-2%,
Wherein, the pigment is one or more in carbon black, phthalocyanine blue, dark green；And/or
The auxiliary agent is polyether-modified dimethyl silicone polymer, polyacrylate, 2,6- DI-tert-butylphenol compounds, aminomethoxy silicon
One or more in alkane.
The 18. anti-anode masking protection ink of ultraviolet light polymerization according to claim 4, it is characterised in that：With ink combination
On the basis of the gross weight of thing, the ink also includes following components in percentage by weight：
Pigment 0.5-1%；With/
Or auxiliary agent 0.3-2%,
Wherein, the pigment is one or more in carbon black, phthalocyanine blue, dark green；And/or
The auxiliary agent is polyether-modified dimethyl silicone polymer, polyacrylate, 2,6- DI-tert-butylphenol compounds, aminomethoxy silicon
One or more in alkane.
The 19. anti-anode masking protection ink of ultraviolet light polymerization according to claim 6, it is characterised in that：With ink combination
On the basis of the gross weight of thing, the ink also includes following components in percentage by weight：
Pigment 0.5-1%；With/
Or auxiliary agent 0.3-2%,
Wherein, the pigment is one or more in carbon black, phthalocyanine blue, dark green；And/or
The auxiliary agent is polyether-modified dimethyl silicone polymer, polyacrylate, 2,6- DI-tert-butylphenol compounds, aminomethoxy silicon
One or more in alkane.
The 20. anti-anode masking protection ink of ultraviolet light polymerization according to claim 10, it is characterised in that：With ink combination
On the basis of the gross weight of thing, the ink also includes following components in percentage by weight：
Pigment 0.5-1%；With/
Or auxiliary agent 0.3-2%,
Wherein, the pigment is one or more in carbon black, phthalocyanine blue, dark green；And/or
The auxiliary agent is polyether-modified dimethyl silicone polymer, polyacrylate, 2,6- DI-tert-butylphenol compounds, aminomethoxy silicon
One or more in alkane.
The 21. anti-anode masking protection ink of ultraviolet light polymerization according to claim 11, it is characterised in that：With ink combination
On the basis of the gross weight of thing, the ink also includes following components in percentage by weight：
Pigment 0.5-1%；With/
Or auxiliary agent 0.3-2%,
Wherein, the pigment is one or more in carbon black, phthalocyanine blue, dark green；And/or
The auxiliary agent is polyether-modified dimethyl silicone polymer, polyacrylate, 2,6- DI-tert-butylphenol compounds, aminomethoxy silicon
One or more in alkane.
The anti-anode masking protection ink of one of the 22. claim 1-21 ultraviolet light polymerization is in being combined that aluminium and plastic cement are inlayed
Application in base material.
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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 light solidification 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 | Anodic oxidation resistant protective ink and preparation method and application thereof |
| 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 |
| CN112165819B (en) * | 2020-10-29 | 2022-03-22 | Oppo广东移动通信有限公司 | Electronic equipment shell, manufacturing method thereof and electronic equipment |
| CN113150604B (en) * | 2021-03-16 | 2023-02-10 | 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 |
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| CN103045013B (en) * | 2013-01-25 | 2015-05-20 | 深圳市万佳原丝印器材有限公司 | Ultraviolet full-shielding printing ink and preparation method thereof |
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