CN115785729B - A multi-purpose UV-LED light-curing high-hiding screen printing ink and preparation method thereof - Google Patents
A multi-purpose UV-LED light-curing high-hiding screen printing ink and preparation method thereof Download PDFInfo
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Landscapes
- Inks, Pencil-Leads, Or Crayons (AREA)
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Abstract
本发明公开了一种多用途UV‑LED光固化高遮盖网印油墨，包括光油组分、色浆组分；光油组分为A组分和/或B组分；色浆组分为彩色系色浆或者白色系色浆。市面上常见的UV固化体系的油墨，种类繁多，性能不一，且都局限于较小的应用领域，适用性差，用户实际生产中为满足不同的需求就得采购不同种类或特性的产品，带来较大的库存压力，且UV光固化类的产品保质期短，造成不必要的资源浪费，和环保压力。为了解决现有技术问题，本发明公开了一种多用途UV‑LED光固化高遮盖网印油墨；具体的，本发明开创性的配方设计和其独特的应用模式，很好的解决了上述问题，同时给用户一种全新的应用体验。
The present invention discloses a multi-purpose UV-LED light-curing high-hiding screen printing ink, including a varnish component and a color paste component; the varnish component is component A and/or component B; the color paste component is a color paste or a white color paste. The common UV-curing system inks on the market are of various types and different performances, and are all limited to a small application field and have poor applicability. In actual production, users have to purchase products of different types or characteristics to meet different needs, which brings great inventory pressure, and UV-curing products have a short shelf life, resulting in unnecessary waste of resources and environmental pressure. In order to solve the problems of the prior art, the present invention discloses a multi-purpose UV-LED light-curing high-hiding screen printing ink; specifically, the groundbreaking formula design and its unique application mode of the present invention well solve the above problems and provide users with a brand new application experience.
Description
Technical Field
The invention relates to the technical field of screen printing ink, in particular to multipurpose UV-LED photo-curing high-coverage screen printing ink.
Background
At present, UV light-cured printing ink is mainly used in two modes of medium-high pressure UV mercury lamp curing and UV-LED lamp curing, and has the common characteristics that a single formula design is adopted, the UV light-cured printing ink is suitable for a certain material or a certain material, the applicability is narrow, the UV light-cured printing ink is generally only applied to a certain field to solve a specific problem or requirement, the application of the UV light-cured printing ink on plastic workpieces such as PC, ABS or PC/ABS can be solved by a certain product technology from the dimension of a certain application industry, the common printing of fonts such as computer keyboard surfaces, LOGO printing on the surfaces of plastic shells of electric appliances and the like, but the formula design of the product is fixed and printed on materials with other properties such as PET, PP or PMMA, the product design cannot meet the requirement, and the product design is also suitable for the PMMA material with good adhesion and high hardness, but the product cannot meet the application on PET films. In short, the existing ink has single formula design, relatively fixed product performance characteristics, and can only solve a specific requirement, and has poor adaptability and narrow application range.
Disclosure of Invention
In summary, the common UV curing system inks in the market have various types, different performances, limited to smaller application fields, poor applicability, and large stock pressure caused by purchasing different types or characteristics of products to meet different demands in actual production of users, short shelf life of UV light curing products, unnecessary resource waste, and environmental protection pressure. In order to solve the problems in the prior art, the invention discloses multipurpose UV-LED photo-curing high-coverage screen printing ink, in particular to an original formula design and a unique application mode thereof, which well solves the problems and provides a brand-new application experience for users.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a multipurpose UV-LED photo-curing high-coverage screen printing ink comprises a gloss oil component and a color paste component, wherein the gloss oil component is a component A and/or a component B, and the color paste component is color paste or white color paste.
The multipurpose UV-LED photo-curing high-coverage screen printing ink comprises a gloss oil component and a color paste component, wherein the gloss oil component is an A component and/or a B component, and the color paste component is color paste or white color paste.
The component A comprises the following components in parts by mass:
the component B comprises the following components in parts by mass:
The color system color paste comprises the following components in parts by mass:
the white color paste comprises the following components in parts by mass:
In the invention, the raw materials of all the components are mixed to obtain the complete component. The preparation method of the multipurpose UV-LED photo-curing high-coverage screen printing ink comprises the steps of mixing gloss oil components and color paste components, wherein the gloss oil components are A components and/or B components, and the color paste components are color paste or white color paste.
The preparation method of the gloss oil component (A component and B component) comprises the following steps:
(1) Adding a photoinitiator into the mixing barrel, stirring until the photoinitiator is completely dissolved and no particles exist, and filtering out impurities to obtain a mixed solution;
(2) Adding the full-acrylic ester prepolymer, the polyurethane acrylic ester 1 and the polyurethane acrylic ester 2 into a batching bucket, stirring to uniformly mix the full-acrylic ester prepolymer, the polyurethane acrylic ester 1 and the polyurethane acrylic ester 2, adding a filler, stirring, sequentially adding a thickening agent and a defoaming agent, and stirring to obtain slurry;
(3) Grinding the slurry by using a nano grinder, adding the mixed solution, the auxiliary initiator and the oxygen polymerization inhibitor, uniformly stirring, and filtering to obtain a component A or a component B.
The preparation method of the color paste component (color paste C1 component and white color paste C2 component) comprises the following steps:
(1) Putting the monomer into a batching bucket, then putting the full-acrylic ester prepolymer and the modified epoxy acrylic ester resin into the batching bucket in sequence, stirring to uniformly mix the full-acrylic ester prepolymer and the modified epoxy acrylic ester resin, then adding the dispersing agent, stirring uniformly, then adding the pigment, stirring, then adding the defoaming agent, and stirring to obtain slurry;
(2) Grinding the slurry by a grinder, and filtering to obtain C1 component (color paste) and C2 component (white color paste).
In the invention, the stirring, grinding and filtering are conventional technologies, for example, a stirring device in the step is specifically a dispersing machine, the rotating speed of the dispersing machine is 800-1200r/min, a grinding machine is specifically a nano bead grinding machine, the grinding fineness is less than or equal to 1 mu m, and the mesh number of filtered filter cloth is 300 meshes.
The multipurpose UV-LED photo-curing screen printing ink has wide application range, is suitable for various base materials commonly used in the market, can be used for surface screen printing processes of PC, PMMA, ABS, PC +ABS, PC+ PMMA, PET, PP, PVC and other materials, has excellent adhesiveness and good sun resistance, can meet the requirements of hard material surfaces on providing hardness, wear resistance and other functionalities, can realize the field of flexible film sheets with stamping and stretching requirements, and has the effects of decorating, beautifying and protecting materials.
The invention takes various UV resin oligomers and prepolymers as the connecting materials, and polymerizes under the photo-curing condition to form high molecular polymers, thereby playing excellent physical properties and reactivity, having good adhesive force to various plastic materials, PET and PI films, having toughness, high hardness, wear resistance, solvent resistance, low shrinkage, good sun-proof performance and good compatibility.
Preferably, the photoinitiator is one or more of TPO (2, 4, 6-trimethylbenzoyl-diphenyl phosphine oxide), 184 (1-hydroxy-cyclohexyl-phenyl ketone), 819 (phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide), pasteur Irgacure784, pasteur Irgacure 261 and ITX (2 (2, 4 isomer mixture)). The preferred photoinitiator or the compound mixture has an absorption effect on ultraviolet light at the wavelength of 250-440nm, has a wide absorption wave spectrum range, has a plurality of effective absorption peaks at 231nm,258nm,307nm,370nm, 292 nm,400 and 405nm, and can be used together with different photoinitiators to enable part of the photoinitiators to be excited under the irradiation of an LED ultraviolet lamp with the wavelength of 365nm or 395nm to generate high-energy free radicals, on one hand, the high-energy free radicals directly trigger the polymerization reaction of the UV resin, and on the other hand, part of the high-energy free radicals further trigger other synergistic photosensitizers to release more free radicals to trigger further polymerization reaction, so that deep curing is promoted. The (2, 4, 6-trimethyl benzoyl-diphenyl phosphine oxide) is a high-efficiency general ultraviolet light initiator, has an effective absorption peak value of 350-400nm and is absorbed to about 420nm, is a high-efficiency free radical (I) photoinitiator, has high photocuring speed and excellent absorption performance, and is particularly suitable for the curing fields of white, colored systems and film layers. The Pasteur Irgacure 261 is a novel cationic photoinitiator, is yellow powder, has strong absorption at the positions of 240-250nm of far ultraviolet and 390-400nm of near ultraviolet, is creatively applied to a UV-LED photocuring system, has high ultraviolet utilization rate, is efficient in initiating polymerization reaction, can still continuously initiate polymerization crosslinking reaction after illumination is stopped, and performs post-curing, and particularly, for the photocuring of a colored coating with the thickness of more than 4 microns, the relevant physical properties of the coating are improved by 10% -20% after ultraviolet radiation is finished and the photocuring is kept stand for 12 hours in the dark. The invention relates to a black system, which is added with 1% -2% of common photoinitiator and compounded with TPO and ITX, wherein the curing effect is good when the UV energy value is 400mj/cm < 2> (1-hydroxy-cyclohexyl-phenyl ketone) at the film thickness of 4 micrometers, white crystalline powder with the effective absorption peak value of 246nm, 278nm is a high-efficiency free radical (I) type solid photoinitiator without yellowing, has good non-yellowing property, and is particularly suitable for transparent gloss oil and white systems. The application of the modified TPO resin is good in the matching use effect of the modified TPO resin and the modified TPO resin is optimal in the compatibility curing efficiency of the transparent system according to the mass ratio of 2:1. The photoinitiator 819 (phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide) is a high-efficiency photoinitiator, the wavelength absorption peak is at 370nm and 405nm, the maximum absorption wavelength can reach 450nm, the initiator has higher initiation activity than TPO, the 819 produced by the IGM company is preferential, the effective component is more than 98%, the color is lighter, 0.5% -1% is added in a dark color system, and the problems of lower film gloss, surface orange peel and the like caused by inconsistent surface drying and deep curing speeds are effectively solved. The photoinitiator ITX (2 (2, 4 isomer mixture)) is a high-efficiency free radical II type photoinitiator with the absorption wavelength of 258,3832 nm, is matched with tertiary amine synergistic resin for UV polymerization curing, and has ideal curing effect when 2-4% of the photoinitiator is added into a color system.
Preferably, the co-initiator is ethyl p-dimethylaminobenzoate (EDB), the tertiary amine sensitizer has absorption at 228-308nm in the ultraviolet region, has no photo-curing effect per se, can be used together with a free radical photoinitiator to increase the photo-sensitivity, and is mainly matched with ITX for photo-curing a colored system.
Preferably, the oxygen polymerization inhibitor is double bond chemical DOUBLEMER L,234, is a special UV-LED curing polymerization auxiliary initiator, effectively reduces oxygen polymerization inhibition phenomenon, promotes surface curing, and promotes curing efficiency in a low energy state, wherein 0.5% -1% of the oxygen polymerization inhibitor is added in the formula, and the curing efficiency is improved by more than 10%.
Preferably, the polyurethane modified acrylic ester 1 can be double bond chemical 6915, changxing chemical DR-U052, and has viscosity of 18000-28000cps at 25 ℃, belongs to 4-functionality aliphatic polyurethane acrylic ester, is favorable for reducing the viscosity of a formula, has high reactivity and high crosslinking density, has excellent flexibility, and has good adhesiveness to plastic substrates such as PET/PI;
The polyurethane modified acrylic ester 2 can be long-standing chemical DR-U591, five-element material science and technology LED9500, has the viscosity of 25000-50000cps at 25 ℃, belongs to 6-10-functional high-functionality aliphatic polyurethane acrylic ester, has high reactivity, high crosslinking density, high hardness, toughness and wear resistance, and is used as a main body connecting material in a matched manner, and the resin with the two characteristics is cured together with a monomer and other acrylic esters to endow the ink system with basic physical properties, excellent wear resistance and flexibility, good hardness and chemical resistance and the like.
Preferably, the full acrylate prepolymer is double bond chemical 6MX75 and Changxing chemical 6533B-40, and has obvious effects of reducing shrinkage, promoting and improving the adhesiveness of the ink on a plastic substrate.
Preferably, the modified epoxy acrylate resin is DOUBLEMER TF-5, is modified bisphenol A epoxy acrylate, has the viscosity of 45000-65000cps at the temperature of 2 and 25 ℃, has the advantages of 9.6 percent of elongation, good flexibility, high curing speed, promotion effect on adhesiveness of plastic substrates such as PET/PP/PE and the like, good wettability effect on pigments, contribution to wetting and coating of main resin on the pigments and fillers, unexpected covering effect under the condition of low pigment addition amount, compatibility of fluidity of ink, improvement of wettability of the ink on the substrates, and effective avoidance of light transmission and light leakage phenomena such as pinholes, trachoma and the like. DOUBLEMER 176TF-5 is the main resin for preparing the nano color paste, and is combined with the full acrylic prepolymer, the dispersing agent and the pigment, and the nano color paste is prepared by grinding and dispersing.
Preferably, the monomer is one or more of HDDA (1, 6-hexanediol diacrylate), IBOA (isobornyl acrylate), DPHA (dipentaerythritol hexaacrylate), TPGDA (tripropylene glycol diacrylate) and PET3A (pentaerythritol triacrylate), so that the viscosity of the ink system can be adjusted to adapt to the requirements of a printing process, and the ink system can be adhered to a resin, the reaction speed can be adjusted, the crosslinking density can be adjusted, and the like, such as compatibility, dilutability, high reactivity and high crosslinking density can be realized.
Preferably, the dispersing agent is one or more of the Pick chemical BYK-110, BYK-163, BYK-168, lu Borun SOLSPERSE (TM) 20000, in the invention, the dispersing agent is a high molecular weight block copolymer containing pigment affinity groups, which is favorable for dispersing solid particles and can prevent sedimentation and agglomeration of the solid particles, and preferably, the defoaming agent is BYK-054, china HX-2085 and Michaelis-A-750S defoaming agent.
Preferably, the pigment is titanium dioxide, F3RK yellow light red, permanent red F5RK is one or more of blue light red, hansha yellow R, hansha yellow H4G, permanent yellow, phthalocyanine blue BGS, ultramarine, quinacridone purple and carbon black, the titanium dioxide is specifically one or two of Kemu rutile type titanium dioxide R706, R900 and stone original PFR209, wherein the Kemu rutile type titanium dioxide R706 or R900 has extremely high glossiness, supernormal hiding power and tinting strength and is easy to disperse and is used for a bright white system, and the stone original PFR209 is a medium-grain-diameter rutile type titanium dioxide pigment prepared by a vulcanization process and through silicon-aluminum surface treatment and is suitable for a matte white system. The carbon black is specifically one or two of medium-high pigment carbon black with the particle size of 20-40 nanometers, mitsubishi MA285, columbia ADITYA BIRLA Raven carbon black and cabot R400R, and is characterized by having an oil absorption value of 60-100 (cm 3/100 g), a coloring strength of 110-150 and a PH value of 3-5;
The filler is specifically one or more of light calcium carbonate (nano-scale), nano barium sulfate, lithopone, poly (tetrafluoro) ethylene wax and PE wax, the nano filler has good compatibility with organic components, the comprehensive performance of a paint film is not impaired, and the refraction of the filler can enable a light source to penetrate into the inside of a film layer to play a role in promoting solidification. In addition, poly (tetrafluoro) ethylene wax, PE wax and the like also play a role in blocking oxygen and polymerization on the surface of the ink, and promote UV curing.
The thickener is one or more of fumed silica, polyamide wax and organic bentonite, and is used for adjusting the viscosity and printing adaptability of the ink system and assisting the dispersion and storage stability of pigment.
On one hand, ultraviolet light emitted by UV-LED light curing equipment has a wave band from 260nm to 410nm, but the current commonly used lamp group generally selects 365+/-5 nm and 395+/-5 nm in consideration of curing efficiency and use cost, has single wave band, and spectrum release is concentrated in a narrow band, belongs to a cold light source, compared with a medium-high pressure mercury lamp, has no thermal radiation, generally increases the surface temperature of a printing stock by about 1-3 degrees in the ultraviolet radiation curing process, increases the surface temperature of an object to be illuminated, is not easy to deform, and particularly solves the long-term heat injury problem in the production of heat sensitive materials such as optical communication, liquid crystal screens and the like. Meanwhile, the multipurpose UV-LED photo-curing high-coverage screen printing ink can be applied to fields with low added value such as application and packaging materials, and the like, and can be applied to fields such as instruments and meters, electronic communication, liquid crystal display screens, and the like, so that market application scenes are greatly widened, and the multipurpose UV-LED photo-curing high-coverage screen printing ink has important significance for sustainable development of UV curing system ink and further improvement of market share.
Compared with the prior art, the invention provides the multipurpose UV-LED photo-curing high-coverage screen printing ink, which has the following beneficial effects:
1. the ink prepared by the invention adopts a unique formula design thought, has wide universality, is suitable for the surface screen printing requirements of various common materials in the market, has good adhesiveness, toughness, wear resistance, sun resistance and chemical resistance, can be used independently or can be mixed with other components for use, and the addition amount of the component C determines the color concentration and the covering effect of the ink.
2. The UV ink has the advantages of multipurpose and multifunctional creative formula design and unique application modes, well solves the problems that the traditional UV ink is single in formula design, relatively fixed in performance characteristics, poor in adaptability, narrow in application range and the like, can only solve a specific requirement, avoids large stock pressure caused by purchasing products of different types or characteristics for meeting different requirements at a client application end, and is short in shelf life, easy to cause unnecessary resource waste and environment-friendly pressure.
3. The invention has good adhesiveness of the related ink and strong universality, solves the adhesiveness problem of the ink on the surfaces of various materials, and can be simultaneously applied to the screen printing process requirements of PET, PVC, PC, PMMA, PP, ABS, PC +ABS, PC+PMMA and other materials.
4. The ink related to the invention has rich color system, can meet most of color requirements, can be prepared by self to meet the color requirements of diversity and individuation of users, and has the color concentration improved by 30-40% compared with common photo-cured products.
5. The UV-LED cold light source is adopted for solidification, the surface temperature of the irradiated object is low, the workpiece is not easy to deform, the UV-LED cold light source is suitable for the fields with shading requirements such as electronic equipment, liquid crystal touch screens, instrument panels and the like, and thermal damage similar to that generated in the traditional UV mercury lamp solidification process is not required to be worried.
6. The photoinitiator and the formula are designed, the curing system is efficient, the film forming effect is good under the condition of lower ultraviolet energy radiation, and the curing system is suitable for curing the LED lamps with 365nm wavelength and 395nm wavelength. The UV energy value is 250-300mj/cm < 2 > when the thickness of the printing film layer is smaller than 4 microns, the UV energy value is 400-450mj/cm < 2 > when the thickness of the printing film layer is 4-6 microns, the printing film layer can be printed twice when the thickness of the printing film layer exceeds 8 microns, the first film thickness is 4-5 microns, the UV energy value is 400-450mj/cm < 2 > and the second film thickness is 2-3 microns, the UV energy value is 400-450mj/cm < 2 > and the curing is finished.
7. The ink prepared by the method has good wettability to a base material, good leveling property and high smoothness of an ink layer, the cured ink layer is resistant to solvent erosion and has good weather resistance and no yellowing for a long time, the cured ink layer has excellent hiding power, wherein the OD value reaches 4 when the black film thickness is 4-5 microns, and the adverse phenomena such as orange peel, pinholes and the like are avoided. The ink has good curing effect, excellent physical properties of the ink layer, alcohol resistance (500 gf is more than or equal to 500 times and 99.5 percent of ethanol), cosmetic resistance test (500 gf is more than or equal to 300 times and certain brand of hand cream), wear resistance (512 rubber and 500gf is more than or equal to 300 times), and good ductility, and is suitable for the requirement of a stretching process.
Drawings
FIG. 1 shows the effect of silk screen printing of the white ink on PC sheet (bright white) according to example I;
FIG. 2 is a graph showing the effect of silk-screen printing of black ink (blue-phase bright black) on PC sheets;
fig. 3 shows the effect of silk screen printing of the blue ink on PC sheet (BGS phthalocyanine blue) produced in example three.
Detailed Description
The raw materials adopted by the invention are all existing products, are conventional raw materials in the field of printing ink, and the specific preparation operation and the testing method are conventional technologies, so that the conventional requirements of the printing ink are met. The grinding machine is specifically a nano bead grinding machine, the grinding fineness is required to be less than or equal to 1 mu m, the mesh number of filtering cloth for filtering is 300 meshes, the stirring device is specifically a dispersing machine, the rotating speed is 1000r/min, and each mass part is 1Kg.
The invention provides a formula composed of resin, auxiliary agent, pigment and filler, which solves the problem of narrow applicability of the existing ink as a whole, and the technical scheme in the embodiment of the invention is clearly and completely described below by combining the embodiment of the invention, and obviously, the described embodiment is only a part of embodiments of the invention, but not all embodiments.
Example 1
A multipurpose UV-LED photo-curing high-coverage screen printing ink is white and consists of an A component and a C2 component.
The monomer is a mixture of HDDA, IBOA, PET A, and the weight ratio is 6:1:3;
The photoinitiator is TPO (2, 4, 6-trimethylbenzoyl-diphenyl phosphine oxide), 184 (1-hydroxy-cyclohexyl-phenyl ketone) and 819 (phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide) which are mixed and matched for use, and the weight ratio is 6:3:0.3;
the co-initiator is ethyl p-dimethylaminobenzoate (EDB);
the oxygen polymerization inhibitor is double bond chemical DOUBLEMER L,234;
The full-acrylate prepolymer is double bond chemical 6MX75;
The polyurethane modified acrylic ester 1 is the Changxing chemical DR-U052, and the polyurethane modified acrylic ester 2 is the Changxing chemical DR-U591;
the thickener is specifically fumed silica;
The defoamer is specifically HX-2085;
the filler is nano light calcium carbonate and poly (tetrafluoro) ethylene wax, and the weight ratio is 8:2;
The modified epoxy acrylate is DOUBLEMER to 176TF-5;
The dispersant is Pick chemical BYK-110;
The pigment is titanium dioxide, and specifically is Kemu R706.
The component A comprises the following components in parts by mass:
The C2 component (white color paste) comprises the following components in parts by mass:
the preparation method of the component A comprises the following steps:
(1) Adding a photoinitiator into the mixing barrel, stirring until the photoinitiator is completely dissolved and no particles exist, and filtering out impurities to obtain a mixed solution;
(2) Adding the full-acrylic ester prepolymer, the polyurethane acrylic ester 1 and the polyurethane acrylic ester 2 into a batching bucket, stirring to uniformly mix the full-acrylic ester prepolymer, the polyurethane acrylic ester 1 and the polyurethane acrylic ester 2, adding a filler, stirring, sequentially adding a thickening agent and a defoaming agent, and stirring to obtain slurry;
(3) Grinding the slurry by using a nano grinder, adding the mixed solution, the auxiliary initiator and the oxygen polymerization inhibitor, uniformly stirring, and filtering to obtain the main gloss oil of the component A.
The preparation method of the color paste component comprises the following steps:
(1) Putting the monomer into a batching bucket, then putting the full-acrylic ester prepolymer and the modified epoxy acrylic ester resin into the batching bucket in sequence, stirring to uniformly mix the full-acrylic ester prepolymer and the modified epoxy acrylic ester resin, then adding the dispersing agent, stirring uniformly, then adding the pigment, stirring, then adding the defoaming agent, and stirring to obtain slurry;
(2) Grinding the slurry by a grinder, and then filtering to obtain a C2 component (white color paste).
The component A and the component C2 (white color paste) are mixed to form the multipurpose UV-LED photo-curing high-coverage screen printing white ink, and the multipurpose UV-LED photo-curing high-coverage screen printing white ink is prepared by uniformly stirring the components A (main gloss oil) and C2 (white color paste) =50:50 according to the mass parts.
The ink can be cured by using an LED lamp with the specification of 365nm or 395nm, does not yellow, has the characteristics of low viscosity, high functionality, rapid curing of the ink by matching with a high-reactivity monomer, low odor, low irritation and good wettability and low shrinkage due to the fact that the preferable polyurethane acrylate is used for curing the ink by using the LED lamp with the specification of 365nm or 395nm, can be matched with other components to improve the adhesiveness of the ink to a substrate, and can be prepared into fine and uniform ink dispersoid through dispersion grinding, so that the excellent printability is provided, and the extremely high glossiness, the extraordinary hiding power and the excellent whiteness are provided.
Example two
The monomer is a mixture of HDDA, TPGDA, PET A, and the weight ratio is 6:2:2;
The photoinitiator is TPO (2, 4, 6-trimethylbenzoyl-diphenyl phosphine oxide), ITX (2 (2, 4 isomer mixture)), and Basf Irgacure 784 (bis (1- (2, 4-difluorophenyl) -3-pyrrolyl) titanocene), wherein the Basf Irgacure 261 is mixed and matched for use, and the weight ratio is 4:2:2:2;
the co-initiator is ethyl p-dimethylaminobenzoate (EDB);
the oxygen polymerization inhibitor is double bond chemical DOUBLEMER L,234;
the full acrylic ester prepolymer is Changxing chemical 6533B-40;
the polyurethane modified acrylic ester 1 is double bond chemical 6915, and the polyurethane modified acrylic ester 2 is five-element material science and technology LED9500;
the thickener is specifically fumed silica;
the defoamer is specifically China HX-2085;
The filler is specifically light calcium carbonate (nano-scale) and poly (tetrafluoro) ethylene wax, and the weight ratio is 8:2;
The modified epoxy acrylate is DOUBLEMER to 176TF-5;
the dispersing agent is specifically Lubo nuciferase (TM) 20000;
the pigment is carbon black, and particularly comprises ADITYA BIRLA Raven 1255 carbon black;
The multipurpose UV-LED photo-curing high-coverage screen printing ink is black, wherein the component A (main body gloss oil) and the component C1 (color system color paste) are mixed, and the finished black ink can be obtained by uniformly stirring the components A (main body gloss oil)/C1 (color system color paste) =70/30 in parts by mass;
The component A (main body gloss oil) comprises the following components in parts by mass:
the C1 component (color system color paste) is black, and comprises the following components in parts by mass:
the preparation method of the component A comprises the following steps:
(1) Adding a photoinitiator into the mixing barrel, stirring until the photoinitiator is completely dissolved and no particles exist, and filtering out impurities to obtain a mixed solution;
(2) Adding the full-acrylic ester prepolymer, the polyurethane acrylic ester 1 and the polyurethane acrylic ester 2 into a batching bucket, stirring to uniformly mix the full-acrylic ester prepolymer, the polyurethane acrylic ester 1 and the polyurethane acrylic ester 2, adding a filler, stirring, sequentially adding a thickening agent and a defoaming agent, and stirring to obtain slurry;
(3) Grinding the slurry by using a nano grinder, adding the mixed solution, the auxiliary initiator and the oxygen polymerization inhibitor, uniformly stirring, and filtering to obtain the main gloss oil of the component A.
The preparation method of the color paste component comprises the following steps:
(1) Putting the monomer into a batching bucket, then putting the full-acrylic ester prepolymer and the modified epoxy acrylic ester resin into the batching bucket in sequence, stirring to uniformly mix the full-acrylic ester prepolymer and the modified epoxy acrylic ester resin, then adding the dispersing agent, stirring uniformly, then adding the pigment, stirring, then adding the defoaming agent, and stirring to obtain slurry;
(2) Grinding the slurry by a grinder, and then filtering to obtain a C1 component (black color paste).
The ultraviolet light absorbing and curing ink has the absorption effect on ultraviolet light at the wavelength of 250-400nm, the synergistic effect of the auxiliary initiator on the Ethyl Dimethylaminobenzoate (EDB) enables the ink prepared by the ultraviolet light absorbing and curing ink to meet the curing requirements of the LED lamps with the two specifications of 365nm or 395nm, the used polyurethane acrylic ester has the characteristics of low viscosity, high functionality, high reactivity, low irritation and low shrinkage, the whole acrylic ester has the characteristics of low odor and low shrinkage, the adhesion of the ink to a substrate can be improved when the ultraviolet light absorbing and curing ink is used in color ink, the modified epoxy acrylic ester has good pigment wettability and fine and uniform black paste dispersion is finally prepared through dispersion grinding, and the prepared ink has the advantages of extremely high glossiness, extraordinary hiding power, excellent physical properties, alcohol resistance, wear resistance and sun resistance.
Example III
The multipurpose UV-LED photo-curing high-coverage screen printing ink is formed by mixing a component A (main body gloss oil), a component B (blended gloss oil) and a component C1 (color system color paste) in blue, wherein the blue of the component A (main body gloss oil)/the component B (blended gloss oil)/the component C1 (color system color paste) is=50/20/30, and the finished blue ink can be obtained by uniformly stirring.
The monomer is a mixture of HDDA, TPGDA, PET A, and the weight ratio is 6:2:2;
The photoinitiator is TPO (2, 4, 6-trimethylbenzoyl-diphenyl phosphine oxide), ITX (2 (2, 4 isomer mixture)), and Pasteur Irgacure 261,819 (phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide) which are mixed and matched for use, wherein the weight ratio is 4:2:2:2;
the co-initiator is ethyl p-dimethylaminobenzoate (EDB);
the oxygen polymerization inhibitor is double bond chemical DOUBLEMER L,234;
the full acrylic ester prepolymer is Changxing chemical 6533B-40;
The polyurethane modified acrylic ester 1 is double bond chemical 6915, and the polyurethane modified acrylic ester 2 is DR-U591 of Changxing chemical;
the thickener is specifically fumed silica;
the defoamer is specifically a Michaemap 750S defoamer;
the filler is specifically poly (tetrafluoro) ethylene wax;
The modified epoxy acrylate is DOUBLEMER to 176TF-5;
The dispersant is BYK-168;
the pigment is the BGS of the Craien pigment phthalocyanine blue.
The component A (main body gloss oil) comprises the following components in parts by mass:
Component B (blending gloss oil):
The C1 component (color system color paste) is blue, and comprises the following components in parts by mass:
the preparation method of the component A comprises the following steps:
(1) Adding a photoinitiator into the mixing barrel, stirring until the photoinitiator is completely dissolved and no particles exist, and filtering out impurities to obtain a mixed solution;
(2) Adding the full-acrylic ester prepolymer, the polyurethane acrylic ester 1 and the polyurethane acrylic ester 2 into a batching bucket, stirring to uniformly mix the full-acrylic ester prepolymer, the polyurethane acrylic ester 1 and the polyurethane acrylic ester 2, adding a filler, stirring, sequentially adding a thickening agent and a defoaming agent, and stirring to obtain slurry;
(3) Grinding the slurry by using a nano grinder, adding the mixed solution, the auxiliary initiator and the oxygen polymerization inhibitor, uniformly stirring, and filtering to obtain the main gloss oil of the component A.
The preparation method of the component B comprises the following steps:
(1) Adding a photoinitiator into the mixing barrel, stirring until the photoinitiator is completely dissolved and no particles exist, and filtering out impurities to obtain a mixed solution;
(2) Adding the full-acrylic ester prepolymer, the polyurethane acrylic ester 1 and the polyurethane acrylic ester 2 into a batching bucket, stirring to uniformly mix the full-acrylic ester prepolymer, the polyurethane acrylic ester 1 and the polyurethane acrylic ester 2, adding a filler, stirring, sequentially adding a thickening agent and a defoaming agent, and stirring to obtain slurry;
(3) Grinding the slurry by using a nano grinder, adding the mixed solution, the auxiliary initiator and the oxygen polymerization inhibitor, uniformly stirring, and filtering to obtain the component B modified light oil.
The preparation method of the C1 component (color system color paste) blue color paste comprises the following steps:
(1) Putting the monomer into a batching bucket, then putting the full-acrylic ester prepolymer and the modified epoxy acrylic ester resin into the batching bucket in sequence, stirring to uniformly mix the full-acrylic ester prepolymer and the modified epoxy acrylic ester resin, then adding the dispersing agent, stirring uniformly, then adding the pigment, stirring, then adding the defoaming agent, and stirring to obtain slurry;
(2) Grinding the slurry by a grinder, and then filtering to obtain a C1 component (blue color paste).
The ultraviolet light absorbing and curing ink has an absorbing effect on ultraviolet light at the wavelength of 250-400nm, the synergistic effect of the initiator on the Ethyl Dimethylaminobenzoate (EDB) enables the ink prepared by the ultraviolet light absorbing and curing ink to meet the curing requirements of the LED lamps with the two specifications of 365nm or 395nm, the used polyurethane acrylate has low viscosity, high functionality and high reactivity, the ink can be quickly cured by being matched with a high-reactivity monomer, the full acrylate has the characteristics of low odor and low irritation and low shrinkage, the adhesion of the ink to a substrate can be improved when the full acrylate is used in color ink, the modified epoxy acrylate has good pigment wettability and fine and uniform blue color paste dispersion is finally prepared through dispersion grinding, and excellent printability is provided.
Performance test:
The UV-LED photo-curing high-coverage screen printing ink is screen printed on the surface of a substrate through a 300-mesh screen printing plate, and then a UV-LED cold light source (wavelength 365nm, UV energy value 300-400mj/cm 2) is adopted for radiation curing, so that a high-coverage UV resin film with the film thickness of 4-6 microns is obtained. The high-coverage UV resin film has bright and full color, higher color concentration than that of common UV ink by 30% -40%, high black coverage, OD (optical density) value of 4-6 microns when the film thickness is 4, white bright light type and matte type, good whiteness, L value of more than 89, sun resistance of 6-7 grades, excellent film forming property, no adverse phenomena such as orange peel, pinholes and the like, good curing effect, alcohol resistance (500 gf is more than or equal to 500 times and 99.5% of ethanol), cosmetic resistance test (500 gf is more than or equal to 300 times and for certain brand of hand cream), wear resistance (512 rubber and 500gf is more than or equal to 300 times), good adhesion (3M adhesive tape and 5B), good toughness, bending resistance, good recoating property, multicolor overprinting and good interlayer adhesion.
The substrates were tested as 12.5 micron thick PC sheet, 35 micron green sheet PMMA sheet, 4.5 micron transparent PET film material, respectively. The thickness of the prepared film layer is 5 micrometers, the curing condition is a UV-LED cold light source with the wavelength of 365nm and the UV energy value of 400mj/cm 2. Fig. 1 shows the effect of the white ink silk-screen on the PC sheet (bright white) according to the first embodiment, fig. 2 shows the effect of the black ink silk-screen on the PC sheet (blue-phase bright black) according to the second embodiment, and fig. 3 shows the effect of the blue ink silk-screen on the PC sheet (BGS phthalocyanine blue) according to the third embodiment.
Table 1A multipurpose UV-LED light curable high coverage Screen printing ink performance Standard (example two, black ink)
The competitive product ink is two types with the best effect on a single base material in the like products sold in the market at present, and the number of times of table values is the limit value of the abrasion resistance test of the competitive product.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
The existing UV curing system ink has several disadvantages:
① The UV light curing ink prepared by the prior art has the common characteristics of single formula design, narrow applicability and capability of being applied to a certain material or a certain class of material in a targeted manner, and can be applied to a certain field only to solve a specific problem or requirement;
② The existing UV curing system ink has various types, different performances and poor applicability, is limited in smaller application fields, and can be used for purchasing products with different types or characteristics to meet different requirements in actual production of users, so that the UV curing system ink has larger stock pressure, and the UV curing system ink has short quality guarantee period, so that the resource waste and environmental protection pressure are brought;
③ The traditional medium-pressure UV mercury lamp is also called a medium-high pressure gas discharge lamp, high-intensity ultraviolet light is generated through metal vapor in the UV lamp tube, the spectrum range is wider, besides the ultraviolet light wave band can simultaneously generate infrared wave band, the surface of the irradiated UV material can be damaged by heat radiation, meanwhile, the temperature in a mercury lamp workshop can be quickly increased, and the operation environment is poorer;
④ The traditional UV system ink solidified by the medium-pressure mercury lamp cannot be applied to the fields of electronic equipment, liquid crystal screens, fine instruments and the like due to thermal injury, is generally applied to the decoration fields of packaging materials and the like, has lower added value, is higher in cost than solvent type ink, is weak in market application intention, and is not beneficial to sustainable development of the UV system ink, and further improves the market share.
The common UV-LED cured UV system ink cannot overcome the oxygen polymerization inhibition effect of oxygen on the surface of a coating, and the energy output of each UV-LED lamp bead is 100-300mW at present and is far lower than that of a traditional UV light source, so that the curing efficiency is lower, the deep curing effect is poor and the like, so that the related product cannot achieve a good covering effect, and the application of the product in large-area printing or with certain covering power requirements is limited, such as a touch screen frame, a 5G mobile phone back cover plate and the like.
At present, UV-LED cured ink has various types, but has simple design, single function and narrow application range, and is mostly used for printing fine fonts, lines, frames and products with lower covering power requirements, such as semitransparent color ink, gloss oil, frosted oil and the like;
The common UV curing system ink has poor applicability, generally has adhesive force fastness on the surfaces of plastic materials such as PC, ABS, PC+ABS, and the like, has poor surface adhesion on some materials such as PET, PP, PMMA, PC +PMMA, which are difficult to adhere, and can only solve the adhesion problem of transparent color systems such as gloss oil, frosted oil, and the like, but the adhesion problem of colored system, especially dark color system ink, is not solved, so that a complete color system is not available to meet the requirements of users on color diversity and individuation.
The invention aims and technical effects that:
The photo-curing resin materials and the monomers are introduced and the photoinitiator, the auxiliary initiator and the oxygen polymerization inhibitor are used, so that the oxygen polymerization inhibition effect of oxygen on the surface of the coating, which is difficult to overcome in the UV-LED curing process, is effectively solved, the photo-curing efficiency is improved, and the curing effect is improved; the proper preparation process and pigment optimization greatly improve the UV-LED photo-curing efficiency and deep curing effect compared with the common products, so that the preparation of the UV-LED photo-curing system ink with high hiding power effect is realized;
The UV-LED photo-curing efficiency is higher, so that the product related by the invention is suitable for the printing requirement of a thicker film layer with larger area, higher hiding power effect and higher color concentration to meet the color requirement of a printed matter with high concentration;
The high covering power, namely has high shielding effect under the condition of low film thickness, is suitable for the fields with light shielding requirements such as electronic equipment, liquid crystal touch screens, instrument panels and the like, and does not need to worry about thermal injury similar to that generated in the curing process of the traditional UV mercury lamp.
The invention has the advantages that the creative formula design and the unique application mode thereof achieve multiple purposes, multiple functions, relatively fixed performance characteristics, only one specific requirement can be met, the adaptability is poor, the application area is narrow, and the client application end can purchase products with different types or characteristics to meet different requirements, so that the invention brings larger stock pressure, and the quality guarantee period of the UV light curing products is short, and the problems of unnecessary resource waste, environmental protection pressure and the like are easily caused;
The multipurpose UV-LED photo-curing screen printing ink is wide in application range, is suitable for various base materials commonly used in the market, can be used for surface screen printing processes of PC, PMMA, ABS, PC +ABS, PC+ PMMA, PET, PP, PVC and other materials, is excellent in adhesiveness, good in sun resistance and good in chemical resistance, can meet the requirements of hard material surfaces on providing hardness, wear resistance and other functionalities, can realize the field of flexible film sheets with stamping and stretching requirements, and has the effects of decorating and beautifying materials and protecting the materials.
Claims (8)
1. A multipurpose UV-LED photo-curing high-coverage screen printing ink consists of a component A and a component C2;
the component A comprises the following components in parts by mass:
The C2 component white color paste comprises the following components in parts by mass:
wherein the monomer is a mixture of HDDA, IBOA, PET A with a weight ratio of 6:1:3, the photoinitiator is formed by mixing TPO, 184 and 819, and the weight ratio is 6:3:0.3;
the auxiliary initiator is ethyl p-dimethylaminobenzoate;
the oxygen polymerization inhibitor is double bond chemical DOUBLEMER L,234;
The full-acrylate prepolymer is double bond chemical 6MX75;
The polyurethane modified acrylic ester 1 is the Changxing chemical DR-U052, and the polyurethane modified acrylic ester 2 is the Changxing chemical DR-U591;
the thickener is fumed silica;
The defoamer is HX-2085;
the filler is nano light calcium carbonate and poly (tetrafluoro) ethylene wax, and the weight ratio is 8:2;
The modified epoxy acrylate is DOUBLEMER to 176TF-5;
The dispersant is Pick chemical BYK-110;
the pigment is titanium dioxide.
2. A multipurpose UV-LED photo-curing high-coverage screen printing ink consists of a component A and a component C1;
The component A comprises the following components in parts by mass:
the C1 component color paste comprises the following components in parts by mass:
The photo initiator is TPO and ITX, and the mixture of the monomer and the photo initiator is Pasteur Irgacure 784, wherein the monomer is HDDA, TPGDA, PET A, the weight ratio is 6:2:2, and the photo initiator is used by mixing and collocating the Pasteur Irgacure261, and the weight ratio is 4:2:2:2;
the auxiliary initiator is ethyl p-dimethylaminobenzoate;
the oxygen polymerization inhibitor is double bond chemical DOUBLEMER L,234;
the full acrylic ester prepolymer is Changxing chemical 6533B-40;
the polyurethane modified acrylic ester 1 is double bond chemical 6915, and the polyurethane modified acrylic ester 2 is five-element material science and technology LED9500;
the thickener is fumed silica;
the defoaming agent is China HX-2085;
the filler is nano-scale light calcium carbonate and poly (tetrafluoro) ethylene wax, and the weight ratio is 8:2;
The modified epoxy acrylate is DOUBLEMER to 176TF-5;
The dispersing agent is Lubo run SOLSPERSE20000;
The pigment is carbon black.
3. The method for preparing the multipurpose UV-LED photo-curing high-coverage screen printing ink according to claim 1 or 2, which is characterized in that the multipurpose UV-LED photo-curing high-coverage screen printing ink is obtained by mixing the raw materials of the components.
4. The method for preparing the multipurpose UV-LED photo-curing high-coverage screen printing ink according to claim 3, wherein the preparation method of the component A comprises the following steps:
(1) Adding a photoinitiator into the mixing barrel, stirring until the photoinitiator is completely dissolved and no particles exist, and filtering out impurities to obtain a mixed solution;
(2) Adding the full-acrylic ester prepolymer, the polyurethane acrylic ester 1 and the polyurethane acrylic ester 2 into a batching bucket, stirring to uniformly mix the full-acrylic ester prepolymer, the polyurethane acrylic ester 1 and the polyurethane acrylic ester 2, adding a filler, stirring, sequentially adding a thickening agent and a defoaming agent, and stirring to obtain slurry;
(3) Grinding the slurry by using a nano grinder, adding the mixed solution, the auxiliary initiator and the oxygen polymerization inhibitor, uniformly stirring, and filtering to obtain the component A.
5. The method for preparing the multipurpose UV-LED photo-curing high-coverage screen printing ink according to claim 3, wherein the preparation method of the color paste component comprises the following steps:
(1) Putting the monomer into a batching bucket, then putting the full-acrylic ester prepolymer and the modified epoxy acrylic ester into the batching bucket in sequence, stirring to uniformly mix the full-acrylic ester prepolymer and the modified epoxy acrylic ester, then adding the dispersing agent, stirring uniformly, then adding the pigment, stirring, and then adding the defoaming agent, stirring to obtain slurry;
(2) Grinding the slurry by using a grinder, and then filtering to obtain a color paste component.
6. A high hiding coating layer obtained by curing the multi-purpose UV-LED photo-curable high hiding screen printing ink as claimed in claim 1 or 2.
7. Use of the multi-purpose UV-LED photo-curable high hiding screen printing ink as claimed in claim 1 or 2 as multi-purpose UV-LED photo-curable screen printing ink.
8. The use according to claim 7, wherein the substrate of the use comprises PC, PMMA, ABS, PET, PP, PVC and pc+abs, pc+pmma composites.
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