CN112980244A - High-speed UV code-spraying ink and preparation method thereof - Google Patents

High-speed UV code-spraying ink and preparation method thereof Download PDF

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Publication number
CN112980244A
CN112980244A CN201911290517.8A CN201911290517A CN112980244A CN 112980244 A CN112980244 A CN 112980244A CN 201911290517 A CN201911290517 A CN 201911290517A CN 112980244 A CN112980244 A CN 112980244A
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speed
ink
printing
pigment
acrylate
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曹雷
姚群
李国栋
李永生
李栋
王静
王建阁
古筝
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Lucky Huaguang Graphics Co Ltd
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Lucky Huaguang Graphics Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00Inks
    • C09D11/30Inkjet printing inks
    • C09D11/32Inkjet printing inks characterised by colouring agents
    • C09D11/322Pigment inks

Abstract

The invention provides a high-speed UV code-spraying ink and a preparation method thereof, the high-speed UV code-spraying ink does not contain an organic solvent, and is cured by full UV; the coating can be cured instantly under the irradiation of a UV-LED light source; the curing speed is high, and the requirement of high vehicle speed is met; the content of the color paste is high, and the requirement of low-resolution printing quality is met; the continuity and the fluency are good, and the requirement of a high-speed ONEPASS printing mode is met; the hardness and the flexibility are moderate, and the coating is suitable for various base materials; good adhesion to paper and various film materials.

Description

High-speed UV code-spraying ink and preparation method thereof
Technical Field
The invention belongs to the technical field of ink-jet ink, and particularly relates to high-speed UV code-spraying ink and a preparation method thereof.
Background
With the development of society progress and science and technology, the printing technology is continuously advanced and developed, and the digital printing technology appears immediately, wherein the digital printing refers to that digital image-text information is directly recorded on a printing plate or a printing medium (paper, plastic and the like) by utilizing a certain technology or technological means, so that the digital page information manufactured by a computer can be directly output to the printing plate or a printed product after being processed by RIP (raster image processor), and the complicated steps of color separation and makeup, plate making, sample making and the like are eliminated, the full digital production is realized, and the process is simple.
The main characteristics of digital printing are: 1. short edition printing (single printing with the quantity less than 1000 minutes), the picture and text information edited by a computer directly records the information on a medium by a certain technical means, the process has the characteristics of short and precise, and the technical means comprises: the technologies of ink jet, laser, heat, magnetism and the like are more flexible and simpler compared with the traditional printing, so the traditional printing can be started up by more than 3000 minutes, but the digital printing can meet the requirement of one or more copies, along with the development of market economy, the types of commodities are more and more, the requirement on printed products is more and more complex, the printing is more and more exquisite, people cannot use the same base material and the same pattern invariably, short-plate printing becomes the development direction expected by people, the simplified digital printing system is suitable for the development trend of small batch, rapidity and individuation at present, in the short-plate printing, the price is invariable no matter one copy or 1000 copies are printed, the short-plate area for printing the traditional printing is made up, and the advantages of the system are obvious. 2. The printing on demand, digital printing can print the quantity, place, time, etc. of the printed matter flexibly in time according to the requirement of the customer, thus reach the zero stock, lower costs, include transmitting the electronic document to the printing company from the network, explain delivery place and time at the same time, the printing company carries out the fast transaction of ordering the goods next day of the same day according to the requirement of the customer, print on demand and can realize the requirement of the zero stock of the publishing agency. 3. The variable data printing and the digital printing have the characteristic of variable printing information, so that the change of the content and the format of the image-text information of a customer can be completed according to the requirement of the customer, in the real life, in order to attract the eyes of the customer, the merchant always pursues to seek new requests on an outer package, and the customer also hopes that the own packaging product is different from others, so that the variable data and the personalized printing appear, the digital printing can convert the idea of each composition into the electronic document printing and express the electronic document printing on an admission material, and the performances can not be met by the traditional printing.
In a word, the digital printing is mainly suitable for the printing on demand with the characteristics of personalized printing, variable information printing and instant printing, is a printing mode for providing relevant services for customers according to time requirements, place requirements, quantity requirements, cost requirements, specific requirements and the like of the users, is generally used for printing arbitrary reports, customer catalogues, enterprise albums, business printing, small books and periodicals and the like, also comprises postcards, business cards, front covers, booklets, personal images and the like, personalized packages, dairy products, medicines, small packages of health care products and gifts, can be used for the purposes of proofing, sales promotion, testing, distribution and the like, and can also be used for printing wallpaper, waist lines, flower weaves and the like; variable numbers, letters, patterns, and various bar codes, two-dimensional codes, etc. are printed, and thus, digital printing is complementary and perfected to conventional printing, and digital printing not only includes printing but also more value-added services.
Digital printing can be classified into the following three categories according to different imaging principles, 1, electrophotography is also called as electrostatic imaging technology, an electrostatic latent image is formed on a photoconductor in a laser scanning mode, and then the latent image is visualized by utilizing the charge effect between charged toner and the electrostatic latent image. Finally, transferring the toner image to a printing stock to finish printing, which is the most extensive digital printing technology; 2. in ink jet printing, droplets of ink are jetted from a fine nozzle to a substrate at a certain speed, and then an ink image is realized on line through interaction of ink droplets. 3. Other imaging techniques, magnetic particle imaging techniques, electron beam imaging techniques, magnetic particle ink jet techniques, and the like.
The variable data printing is the main advantage of digital printing, the digital printing technology of the ink jet mode is the important mode of the digital printing technology, that is, the ink jet mode is adopted in the printing field to carry out the variable data printing, the application is wider, and the trend of continuous rising is presented, and the jet printing content comprises the uniform printing such as one-dimensional bar codes, two-dimensional codes, dot codes, anti-counterfeiting codes, fixed pictures, variable pictures, characters, variable databases, serial numbers and the like. Along with the requirements of modern production, the product information is more and more important in the fields of intelligence, variability and identification, the product information is conveniently inquired and the authenticity is conveniently identified by customers, and the product information identification method can be applied to the aspects of counterfeit prevention, production flow control, automatic production, quality tracing, goods fleeing prevention, logistics two-dimensional code warehouse management and the like.
In the ink-jet printing and printing process, tiny ink fluid drops are directly sprayed on the surface of an ink receiver, the printing and printing equipment and the ink receiver are not in physical contact, the printing and printing equipment electronically stores printing data, a device (spray head) is controlled to spray the ink-jet ink drops onto the ink receiver in an image mode, the printing mode comprises a scanning mode and an ONEPASS printing mode, the scanning mode is mainly used for industries such as advertising and publishing and has high requirements on precision and color, the ONEPASS printing mode is mainly used for printing packaging materials such as labels, and an industrial ONEPASS printing method of multi-injection reprinting printing speed is a single-pass printing method and is a new printing mode, and the mode adopts a page-wide ink-jet printing head or a plurality of staggered ink-jet printing heads (which cover the width of the whole ink receiver surface) to print. In a single pass printing process, the inkjet print head is still stationary while the ink-receiver surface moves under the inkjet print head. The printing method is a production line type printing mode, has high printing speed, has high requirement on printing quality when the printed pattern is printed for one time, and meets the requirements of high-speed printing and less generation of printing tracks. In short, the ink jet digital printing has the advantages that 1, the speed is high, and the onepass ink jet mode can reach 200 meters and min or even higher vehicle speed. 2. The method is easy to edit and modify the contents of the jet printing data, changeable data such as date and time, serial numbers, batch numbers and the like can be added when the contents are edited without connecting a computer, and a U disk can be directly inserted when pictures are jet printed. 3. The applied surface material is wide, the ink-jet printer can be selected from various inks, and the ink-jet printing effect can be good on paper, plastic, metal, glass, hard surfaces or soft and fragile surfaces
With the national requirements for strengthening the supervision of industries such as medicine, cigarette, wine, food and the like, more and more new products need to code, particularly, a code-spraying module needs to be added to packaging materials adopting offset printing, gravure printing, flexo printing and other printing modes, so that the required vehicle speed can better meet the requirements of the vehicle speed of the original printing parties such as offset printing, gravure printing, flexo printing and the like and the vehicle speed requirements of 100 meters/min, even 200 meters and 300 meters, and thus, the requirements on equipment are higher and higher, and the requirements on ink are higher and higher.
Inkjet inks are an indispensable component of inkjet printing and printing, which is classified into water-based according to the drying mechanism involving absorption, permeation, and evaporation; oil-based, drying involving absorption and penetration; solvent-based, the drying mechanism of which involves mainly evaporation; thermal melting or phase change, where the ink is liquid at the jetting temperature and solid at room temperature, replaces drying by curing; UV curing, instead of drying, by polymerization. UV solidification is the photochemistry process, UV light energy is absorbed by photoinitiator in the UV printing ink binder, initiate the process that liquid active monomer or low polymerization form netted solid state macromolecule, UV photocuring inkjet ink has VOC zero release, low energy consumption, advantages such as green, be applicable to multiple stock, inkjet ink is not dry before UV light shines, can not produce the phenomenon of blockking up the shower nozzle because of ink solvent volatilizees, simultaneously UV inkjet prints owing to have and prints as required, high speed, high quality, low-cost advantage, more and more receive people's favor. The ultraviolet light source capable of causing UV curing was early mercury lamp, high-pressure or low-pressure mercury lamp, cold cathode tube, etc., and the emission wavelength was full band UVA, UVB, and UVC: UVA: 400nm to 320 nm; UV-B: 320nm to 290 nm; UVC: 290nm to 100nm, only a small part of the emitted light can be absorbed by a photoinitiator or a photoinitiator system in the irradiation curing process, the ineffective radiation of the light source accounts for 75 percent, most of the light is high-energy infrared light, a large amount of heat is generated to generate adverse effects on production control, meanwhile, the lamp contains heavy metals which are adverse to safety and environment protection, an ultraviolet light source UV-LED light source is gradually developed and matured in recent years, and an UVL-ED light source has multiple advantages compared with a mercury lamp, firstly, the radiation efficiency is greatly improved, and the effective utilization rate of light energy is improved by more than several times; the machine can be opened immediately without preheating; the service life is long. However, the method is different from the mercury lamp in that the wavelength peak emitted by the UV-LED light source is single, the wavelength of the common UV-LED light source is 395nm, the wavelength range is narrow, and the power and the irradiation are low compared with the mercury lamp, so that different requirements are imposed on the photoinitiation system of the matched ink. UVled light sources are mostly adopted in new equipment, and mercury lamp light sources are still used in only some old equipment.
Unlike water-based or solvent-based ink-jet inks that penetrate into a porous ink-receiver, UV-curable inks are typically jetted onto a substantially non-absorbing ink-receiver to form an image of a certain thickness. Such image thickness not only imparts a different look and feel, but may also suffer from deficiencies in physical properties. For example, when an ink-receiver having a cured image is bent, the image may crack or reduce adhesion, thereby requiring high flexibility and substrate adhesion of the ink, and reducing ink consumption may result in a thinner cured inkjet image, which is advantageous for achieving the desired flexibility and adhesion of the ink.
The UV curing high-speed code spraying process adopts an ONEPASS printing method, has high requirements on ink, and has the technical difficulties that: 1. the fluency and the continuity have higher requirements, and the high speed requirement; 2. the requirement for the blackness is higher and higher due to the limitation of the ignition frequency of the spray heads of the ink jet printing, the improvement of the vehicle speed needs to adopt different technologies, on one hand, the quantity of the spray heads is increased, the cost is increased, on the other hand, the resolution is reduced, the thickness of an ink layer is reduced, and the requirement for the blackness of the ink is higher than that of the ink with high resolution. 3. The curing speed is higher and higher, and the vehicle speed is higher, that is, the shorter the time of the ink under the irradiation of the light source, because the power of the light source is high, on one hand, the energy consumption is large, on the other hand, some substrates can be deformed and melted or burnt at high temperature, and therefore, the power of the light source cannot be too high, and the curing speed of the ink is required to be higher than that at low speed. 4. The ink has high pigment content, and the low-thickness coating meets the color requirement. 5. Meets the coating tolerance and simultaneously has good flexibility and substrate adhesion.
Disclosure of Invention
In order to meet the requirement of high-speed code spraying, the invention provides the high-speed UV code spraying ink and the preparation method thereof, the high-speed UV code spraying ink does not contain an organic solvent, and is cured by full UV; the coating can be cured instantly under the irradiation of a UV-LED light source; the curing speed is high, and the requirement of high vehicle speed is met; the content of the color paste is high, and the requirement of low-resolution printing quality is met; the continuity and the fluency are good, and the requirement of a high-speed ONEPASS printing mode is met; the hardness and the flexibility are moderate, and the coating is suitable for various base materials; good adhesion to paper and various film materials. The object of the invention is achieved by:
the ink-jet ink comprises the following components in percentage by weight:
the viscosity of the polyester acrylate is 150-.
The polyurethane acrylate at least contains one polyurethane acrylate with 1-2 functionality and at least one polyurethane acrylate with more than 4 functions.
The active monomer comprises low-viscosity monofunctional acrylate and/or acrylamide active monomer and contains- (CH) in molecular chain2)n-or- (OCH)2)nMono-or bi-functional acrylate monomer with structure (n is greater than or equal to 5), and the total adding amount of active monomer is 60-80%.
The pigment comprises at least one of titanium dioxide, phthalocyanine pigment, quinacridone pigment, azo pigment, benzimidazolone pigment or carbon black pigment.
Ink colors include CMYKW and spot colors.
The photoinitiator is a green environment-friendly photoinitiator. Including Norrish type I and Norrish type II photoinitiators.
The co-initiator is an active amine co-initiator.
The dispersant is at least one of modified acrylate block copolymer, olefine acid block copolymer, hyper-dispersant with anchor group and organic modified polysiloxane.
The auxiliary agent comprises at least one of a wetting and leveling agent, a thermal polymerization inhibitor, a deodorant, a defoaming agent or a foam inhibitor and an adhesion promoter.
The preparation method of the high-speed UV code-spraying ink is characterized by comprising the following steps: the method comprises the following specific steps: (1) dispersing and grinding a mixture of the pigment, the dispersing agent and part of the active monomer to prepare color paste; (2) stirring and dissolving a photoinitiator, an auxiliary initiator, an auxiliary agent, the rest part of active monomer, polyester acrylate and polyurethane acrylate to prepare a pre-solution; (3) dispersing the pre-solution in color paste at high speed; (4) and finally filtering the printing ink by using a microporous filter membrane to obtain the ink.
The invention has the beneficial effects that: the high-speed UV code-spraying ink does not contain an organic solvent, and is cured by full UV; the green environment-friendly photoinitiation system is adopted, so that the green environment-friendly photoinitiation system has the characteristic of being green and environment-friendly; the coating can be cured instantly under the irradiation of a UV-LED light source; the curing speed is high, and the requirement of high vehicle speed is met; the content of the color paste is high, and the requirement of low-resolution printing quality is met; the continuity and the fluency are good, and the requirement of a high-speed ONEPASS printing mode is met; the hardness and the flexibility are moderate, and the coating is suitable for various base materials; good adhesion to paper and various film materials.
Detailed Description
The high-speed UV code-spraying ink comprises the following components: the polyester acrylate, the polyurethane acrylate, the active monomer, the photoinitiator, the pigment, the dispersant, the wetting and leveling agent and the auxiliary agent are described in detail and the preparation method comprises the following steps:
1. polyester acrylate
The types of the prepolymers are more, different types of oligomers have different performances, and the performances of the oligomers with the same type and different structural units are different, so that the selection of the proper prepolymers has important significance for improving the performance of the ink, the requirements of a UV ink-jet ink system on the prepolymers include three important indexes of low viscosity, improvement of the film performance of the ink and maintenance of the stability of the system, and the polyester acrylate has good compatibility and affinity with the pigment, so that the system stability and the continuity of the ink-jet performance of the UV ink-jet ink can be improved, and meanwhile, the smoothness of high-speed code-spraying is met.
The functional group number of the polyester acrylate prepolymer applied to the UV ink-jet ink is generally 2-16, the viscosity is 150-8000cps (25 ℃), the consumption of the polyester acrylate is large, the viscosity of the ink is large, the consumption is small, the reactivity of the ink is low, the stability is poor, the hyperbranched polyester acrylate has higher activity and lower viscosity, the hyperbranched polyester acrylate is more preferably applied to the UV ink-jet ink, and in order to ensure that the low viscosity and the polyester acrylate with better activity, stability and high reactivity are ensured, the hyperbranched polyester acrylate with the viscosity of less than 8000 centipoises at 25 ℃ is preferred.
Examples of commercial products which may be mentioned are polyester acrylates: CN 2302, CN2301 and CN2303 produced by Saedoma; 6361-100 and 6362-100 from Changxing chemical industries, Inc.
The polyester acrylate in the invention can account for 3-15% of the total weight of the UV ink-jet ink.
2. Urethane acrylate
Because the macromolecular structure of the polyurethane acrylate is provided with the structural units of the urethane and the acrylate simultaneously, the excellent performances of the polyurethane and the acrylic resin are integrated, particularly the aliphatic polyurethane acrylate has higher photocuring speed, good adhesive force, flexibility, wear resistance, low temperature resistance and outstanding high elasticity and elongation. The functionality of the oligomer is important to the hardness and flexibility of the film layer, and the high functionality improves the crosslinking density, the curing speed and hardness, and the low functionality improves the flexibility and the substrate adhesion of the ink. The high-speed UV code-spraying ink at least contains one of 1-2 functionality polyurethane acrylate and at least one of polyurethane acrylate with more than 4 functionality.
Mention may be made, for example, of urethane acrylates with a functionality of 1 to 2: yangxing Chemicals 6112, 6113, 6115 and 6123. Shanxi Xilai dock UV6305, 6217. CN929, CN964, CN945 and CN9001 of SARTOMER company.
The addition weight accounts for 2-8% of the total weight of the UV ink-jet ink.
Examples of 4-functional urethane acrylates which may be mentioned are the following: changxing chemicals 6313, 6311, 6161, 6197. Shanxi Xilai dock UV6906, 6451, etc.
The addition weight accounts for 2-8% of the total weight of the UV ink-jet ink.
The adding weight of the urethane acrylate with the functionality of 1-2 and the urethane acrylate with the functionality of more than 4 accounts for 4-16% of the total weight of the UV ink-jet ink.
3. Pigment (I)
The two-dimensional code printed by the high-speed code spraying ink is mostly black, and the code spraying ink is mainly black ink, and carbon black is usually used as a coloring material in the black ink. Suitable Black Pigment materials include Carbon blacks such as Pigment Black 7 (e.g., Carbon Black MA8TM from MITSUISHI CHEMICAL), Regal 400R from CABOT Co., Mogul TML, Elftex 320, or Carbon Black FW18 from DEGUSSA, Special Black 250, Special Black 350, Special Black 550, Printex 25, Printex 35, Printex 55, Printex 90, Printex 150T, high Pigment Black C-311 Shanghai coking plant, and the like.
In a UV-curable black inkjet ink, which always has a warm-brown black hue, the hue can be corrected to a neutral hue by overprinting with cyan and magenta inks, hue adjustment is performed using a composition containing cyan and magenta pigments, the amount of addition is controlled in accordance with the amount of addition of + -3.0A and B values of CIELab color system, the amount of ink consumption can be reduced, and hue shift is not significant.
The total added weight of the black, cyan and magenta pigments is 1-10% of the total UV inkjet ink.
With the personalized requirements and anti-counterfeiting requirements, the requirements of code spraying on colors are more and more strong at present, different colors need different pigments, the colors adopt CMY basic colors and various spot colors, the colors generally adopt organic pigments, and the types include: phthalocyanine pigments, quinacridone pigments, azo pigments, benzimidazolone pigments.
Red or magenta pigment: pigment Red 3, 5, 19, 22, 31, 38, 48:1, 48:2, 48:3, 48:4, 48:5, 49:1, 53:1, 57:2, 58:4, 63:1, 81:1, 81:2, 81:3, 81:4, 88, 104, 108, 112, 122, 123, 144, 146, 149, 166, 168, 169, 170, 177, 178, 179, 184, 185, 208, 216, 226, 257, Pigment Violet 3, 19, 23, 29, 30, 37, 50, and 88;
blue or cyan pigment: pigment Blue 1, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17-1, 22, 27, 28, 29, 36 and 60;
green pigment: pigment Green 7, 26, 36 and 50;
yellow pigment: pigment Yellow 1, 3, 12, 13, 14, 17, 34, 35, 37, 55, 74, 81, 83, 93, 94, 95, 97, 108, 109, 110, 128, 137, 138, 139, 153, 154, 155, 157, 166, 167, 168, 177, 180, 185, and 193;
international and domestic suppliers include: DIC, Kelaien, Pasteur, Hangzhou lily, Shandong de pigment, Jiangsu Zhengxin pigment, etc.
The different colors are different pigments, a single pigment can be used, pigments with different color numbers can be selected according to requirements and mixed to obtain the required color, and the manufacturing method is similar.
The total weight of the color pigment ink is 1-10 wt%, preferably 1-5 wt%.
Pigment White was used as Pigment in Pigment White6, 18 and 21. The paint consists of one or more of nano titanium dioxide, fumed silica and fumed calcium carbonate, the main component is the nano titanium dioxide, the main molecular component is titanium dioxide, and white nano-scale pigment commodities which can be enumerated are as follows: japanese Shirai TIPAQUE R-9, Japanese Shirai titanium white R-980, Chunta (Yuanduo) titanium white R931 and U.S. Teno (Kemeji) titanium white TRONOX CR-828, etc.
The white pigment is required to be used for meeting the whiteness and the covering power of the UV ink-jet ink, and the adding amount of the white pigment accounts for 5-10% of the total weight of the ink.
In order to meet the requirement of high-speed code-spraying low-resolution printing, the addition amount of color paste is required to be large, and the color density of the radiation-curable ink-jet ink is between 1 and 3.
4. Photoinitiators and co-initiators
The activation energy required to cause the monomer and oligomer to undergo curing polymerization is relatively high, high energy is required to carry out polymerization, and the activation energy required by using a photoinitiator is relatively low, and the photoinitiator absorbs light and is responsible for generating free radicals or cations to initiate polymerization of the monomer and oligomer.
There are two main types of photoinitiators: norrish type I initiator, i.e. cleavage type radical photoinitiator, which is cleaved after activation to immediately obtain an initiating radical, typically mainly aryl alkyl ketone derivatives, including benzoin derivatives, benzil ketal derivatives, dialkoxy acetophenones, α -hydroxyalkyl phenones, α -aminoalkyl phenones, acylphosphine oxides, esterified oxime ketone compounds, aryl peroxy ester compounds, halogenated methyl aryl ketones, organic sulfur-containing compounds, benzoyl formate, etc.; representative hydrogen abstraction photoinitiators include benzophenone, thioxanthone, where this second compound is referred to as a polymerization synergist, co-initiator or co-initiator, such co-initiator is used in combination with the Norrish type II initiator, and the co-initiator is of the type including reactive tertiary amines, thiols, ketones, ethers, etc., and the co-initiator and the aryl ketone undergo a reduction reaction to generate reactive radicals to promote the radiation curing process while having the effect of a degree of resistance to oxygen inhibition, with tertiary amine co-initiators being the most common.
Examples of Norrish type I initiators include DEAP, BDMM, BAPO, TPO, 184, 1173, 819, 2959, LTM, etc.; norrish type II initiators include DETX, EHA, EMK, etc.; examples of tertiary amine co-initiators are: EDAB, changxing chemicals 641, 6412 and 6420, etc. In the green environment-friendly coating, the photoinitiators 907, ITX and BP are forbidden, so the invention does not use the three photoinitiators.
The photoinitiation system comprises a Norrish I type Norrish II system and a tertiary amine co-initiation system. The preferred amount of initiator is 3-15% by weight of the total ink, wherein Norrish type I is 1-14%, Norrish type II is 1-14%, and the tertiary amine co-initiator/co-initiator is 1-10% by weight of the total ink.
5. Reactive monomer
The reactive monomer is the main component of the UV ink-jet ink, and the types of the reactive monomers are various, and different types of the reactive monomers have different performances, including a monofunctional reactive monomer, a difunctional reactive monomer and a polyfunctional reactive monomer. Generally, the lower the functionality and the lower the viscosity, and in order to meet the low viscosity requirement of the ink, the invention uses monofunctional reactive monomers with relatively low viscosity.
Examples of monofunctional reactive monomers include styrene, N-ethylene-2-pyrrolidone, butyl acrylate, octyl acrylate, isooctyl acrylate, 2-phenoxyethyl-internal-acid ester, butyl acrylate, isobutyl acrylate, phea, la, ctfa, thfa, ethyl acrylate, oda, isoda, hexyl acrylate, hydroxypropyl acrylate, isobornyl acrylate, tetrahydrofurfuryl acrylate, nvc, acmo, dmaa, etc., and suppliers include Pasteur, Changxing Chemicals, and sandoma, etc., in a total amount of 15 to 65%.
Mono-or di-functional reactive monomers containing- (CH) in the molecular chain2)n- - (O- -O) - -or- - (OCH2)n-, n.gtoreq.5, such reactive monomer containing one or two reactive groups and at least 5-CH groups in the molecular chain2-or- (OCH)2)nChains, which, after photoinitiated polymerization, have at most two crosslinking points and are therefore capable of having multiple free-CH's in the molecule2- - (O- -O) - -or- - (OCH2)nLong chains, which ensure the flexibility of the ink.
Such commercial products that may be enumerated are: ISODA, PEGDA, ODA, IDMA, IDTMA, LMA, SMA and NDDA, etc., in a total amount of 15-65%.
The total adding amount of the adopted active monomers is 60-80%.
7. Dispersing agent
In order to disperse and stably exist in a composition system of active monomers or oligomers and the like, the pigment particles need to be subjected to super-dispersing, the super-dispersing agent is a special surfactant, the molecular structure of the super-dispersing agent contains two groups opposite in solubility and polarity, one of the groups is a shorter polar group called a hydrophilic group, the molecular structure characteristics of the super-dispersing agent enable the super-dispersing agent to easily move to be arranged on the surface of a substance or a two-phase interface and reduce the interfacial tension, and the other group is a lipophilic group which is a macromolecule and is easy to move and can rapidly move to the surface of particles to play a role in wetting protection, multi-point anchoring is formed on the surface of the particles, an effective space stabilizing effect can be achieved, and a lipophilic film cannot be introduced into the surface of the particles, so that the service performance of a product cannot be influenced, the adsorption fastness of ink is improved.
Examples of hyperdispersant commercial products that may be mentioned are SollsPERSE 39000, SOLSPERSE32000, SOLSPERSE5000, Solsperse325000, Solsperse36000, SOLSPERSE22000, Disperbyk-111, 162, 163, 168 of AFCONA 3580 Bikk chemistry; EFKA additives 4310, 4330, 4030 of EFKA; dispers710, 685, 655, etc. of degussa.
The dispersant accounts for 3-10% of the total weight of the ink.
8. Auxiliary agent
Wetting and leveling agent
A wetting and leveling agent is also a surfactant in an inkjet ink to reduce the surface tension of the ink, reduce the contact angle on the substrate, and improve the wetting of the ink on the substrate. On the other hand, jettable inks must meet stringent performance standards so that they can be jetted with increased accuracy and reliability for extended periods of time. To achieve both wetting of the ink to the substrate and high jetting performance, the surface tension of the ink, which is the reciprocal drag force per unit length between two adjacent portions of the liquid surface, is reduced by the addition of one or more surfactants, which is an expression of molecular forces. When the molecules on the liquid surface are attracted by the molecules in the liquid to make the liquid surface tend to shrink, the direction of the molecules is tangential to the liquid surface. The liquid surface always has a tendency to shrink as much as possible due to the effect of surface tension, so that the droplets are spherical. The inkjet ink must have a certain surface tension. Surface tension has a significant effect on the formation of ink droplets and the quality of the ink droplets during the ink jetting process. The presence or absence of spills around the nozzle, the length of break-off of the droplet, the circumference of the droplet and its stability, the speed at which the droplet is formed and whether it is travelling in a straight line, etc. are all affected by the surface tension of the ink. Too high a surface tension makes the ink less prone to fine droplet formation and may present long break lengths or "tail" like droplets when broken, directly affecting the image quality. In addition, excessive surface tension makes the nozzle surface difficult to be wetted, and the ink aggregation around the nozzle can affect the linear running of fine droplets and also affect the wetting and penetration of the droplets to the printing material and the drying performance of the ink. It is generally required that the surface tension of the inkjet ink must be lower than the surface free energy of the substrate. If the surface tension is too low, the liquid drops are unstable, star-shaped sputtering points are easy to form, the non-image-text part is dirty, and the image quality is affected. The surface tension is controlled to be such that it spreads smoothly over the substrate material and forms sufficiently small droplets during the ink jet process. Suitable surface tensions for the UV ink are 22-28 dynes/cm.
Examples of surfactants include TEGO GLIDE450, TEGO GLIDE432, TEGO GLIDE500, TEGORAD2100, TEGORAD2300, TEGO WET 270, etc., available from TEGO; BYK-161, BYK-163, BYK-190, BYK-2100, BYK-333, etc., from Pico.
The addition amount is preferably 0.1-1.5% of the total weight of the ink.
The auxiliary agent can also be added with thermal polymerization inhibitor, odor removing agent, defoaming or foam inhibitor, adhesion promoter, etc. as appropriate.
The adding amount of the thermal polymerization inhibitor accounts for 0.05-1% of the total weight of the ink.
The thermal polymerization inhibitor contains: phenol polymerization inhibitor, quinone polymerization inhibitor, aromatic nitro compound polymerization inhibitor, inorganic compound polymerization inhibitor, nitroxide radical piperidone polymerization inhibitor and the like. Specific examples include: p-hydroxyanisole hydroquinone, ZJ701, p-tert-butylcatechol, dinitro-p-cresol, dinitro-sec-butylphenol, benzoquinone, and the like, or combinations thereof.
Odor removing agent: the adding amount accounts for 0.05-2% of the total weight of the ink.
The odor-reducing agent comprises peptides, enzymes, masking agents, interfering agents, fragrances, or combinations thereof.
The addition amount of the defoaming agent or the foam inhibitor accounts for 0.05 to 2 percent of the total weight of the ink.
The defoaming agent or foam inhibitor can be selected from one or more of emulsified silicone oil, higher alcohol fatty acid ester complex, polyoxyethylene polyoxypropylene pentaerythritol ether, polyoxyethylene polyoxypropylene amine ether, polyoxypropylene glycerol ether, polyoxypropylene polyoxyethylene glycerol ether, polydimethylsiloxane, etc., and specific examples include EFKA defoamer, EFKA-2721, EFKA-E2038, and EFKA-E2028. TEGO Airex and TEGO Foamex series products: TEGO Airex922, TEGO Airex990, TEGO Airex945, TEGO Foamex1488, TEGO Foamex, 840TEGO and Foamex 3062, etc
The addition amount of the adhesion promoter accounts for 0.05-2% of the total weight of the ink.
The adhesion promoter is at least one of aminopropyltriethoxysilane, silane coupling agent Z-6040, silane coupling agent Z6020, silane coupling agent Z6030, silane coupling agent 570 and silane coupling agent 560.
The total addition amount of the auxiliary agent is 0.1-3%.
9. The manufacturing method comprises the following steps:
the manufacture of the UV inkjet ink comprises the following steps: (1) dispersing and grinding a mixture of the pigment, the dispersing agent and part of the active monomer by using grinding machine equipment to prepare color paste; (2) stirring and dissolving a photoinitiator, an auxiliary initiator, phosphate, an auxiliary agent, part of residual active monomers, a polyester acrylate prepolymer and a polyurethane acrylate prepolymer to prepare a pre-solution; (3) dispersing the pre-solution in color paste at high speed; (4) and finally, filtering the printing ink by using a microporous filter membrane.
The grinding and dispersing equipment is a colloid grinder, a high-speed disperser, a double-roller press, a bead mill, a three-roller press and the like; dispersion can also be carried out using ultrasonic energy, and many different types of materials can be used as milling media, such as glass, ceramic, metal, plastic, and the like.
Example (b):
1. the detection method comprises the following steps:
(1) particle size: the ink or color paste is diluted by 500-2000 times by using a solvent according to the pigment concentration, and the average particle size range D50 is measured by using a laser particle sizer.
(2) Viscosity: an NDJ-5S rotational viscometer of Shanghai Nirun Intelligent science and technology Limited is adopted;
(3) surface tension: the BZY-1 surface tension meter produced by Shanghai Hengping instrument and meter factories is adopted for testing;
(4) speed of curing
Power with UV-LED lamp: electric power 610W; irradiating 8W/cm2The distance between the lamps is about 6mm, and the energy of the lamp which goes on the conveyor belt once is as follows: 300-600mj/cm2. The determination that curing has occurred is made by rubbing with a finger on the printed surface thereby observing that the ink is not smeared or smeared on the surface.
(5) And (3) measuring the color density value, scraping the white coated paper by a wire rod scraper, forming a wet film with the thickness of 7 mu m, irradiating 8W/cm2 by a uv-led light source, ensuring that the lamp distance is about 6mm, curing for 5s, ensuring that the coating is completely cured, and testing the color density value by using an Aisenli 528 color densitometer.
(6) Pencil hardness test reference standard: GB/T9286-1998
Scraping the ink layer into a thin layer with a thickness of 12 μm by using a glass substrate, and irradiating by using a UV-LED curing machine at a speed of 8W/cm2And 5S is solidified to ensure complete solidification, and a pencil hardness meter is adopted for hardness detection.
(7) Adhesion force
Scraping the ink layer into a thin layer with a thickness of 7 μm on a paper or opp film material, curing with a UV-LED curing machine, and irradiating with 8W/cm2And (5) solidifying for 5S to ensure complete solidification, and forcibly kneading to ensure that the coating falls off by less than 5 percent to be qualified.
(8) Flexibility, adopting standard GB/T6742-2006
(9) Continuity and fluency
And continuously inspecting the continuous printing capability of the ink under a certain specific temperature-voltage, wherein the temperature of a set spray head on the ink to be tested is 36-45 ℃ and the voltage is 12-15V during detection, 5 plates are continuously printed under each condition, the spray head is printed for testing after the continuity of one plate is printed, the test is compared with a standard sample, and if the number of broken lines is less than 1% of the total number of spray holes of the spray head, the continuity of the ink at the temperature-voltage is qualified.
And (3) smoothness inspection of the adaptability of the ink to the spray nozzle (no damage to the spray nozzle), wherein the ink to be detected is loaded on a machine during detection, the spray nozzle test strips are printed every day, the quantity of the defects of the spray nozzle test strips, such as broken lines and broken line lines, is compared with a standard sample, and the smoothness of the ink in the time interval is qualified when the quantity of the defects of the spray nozzle test strips, such as broken line and broken line is less than 1%.
2. Detailed description of the preferred embodiments
The following are preparation examples of the present invention, and it should be understood that the present invention is not limited to the following examples, but is only for illustrating the scope of the present invention. In addition, various changes or modifications of the present invention by those skilled in the art are also within the scope of the claims of the present application, and the compounding ratio in the examples of the present invention is calculated by parts by weight.
Examples 1-4 black and white ink formulations are shown in table 1:
TABLE 1 Black and white ink formulations
The manufacturing steps are as follows:
(1) the mixture of the pigment, the dispersant and 30 percent of active monomer is dispersed and ground by a grinder device to prepare color paste, a ZETA experimental grinder of German Chiz-resistant company (CNETZSCH) is used for grinding and dispersing, and the dispersing and grinding time is 2 to 4 hours.
(2) Stirring and dissolving the photoinitiator, the auxiliary initiator, the auxiliary agent, 70 percent of residual active monomer, the polyester acrylate prepolymer and the polyurethane acrylate prepolymer to prepare a pre-solution. The stirring and dissolving process uses an experimental emulsifying machine of Shanghai Weiyu electromechanical manufacturing company Limited, and stirring and dissolving are carried out at the rotating speed of 1000 revolutions per minute for 2-4 hours.
(3) And dispersing the pre-solution in the color paste at a high speed. The high-speed dispersion process uses an experimental emulsifying machine of Shanghai Weiyu electromechanical manufacturing company, which is carried out at the rotating speed of 5000-.
(4) And finally, filtering the printing ink by using a microporous filter membrane, wherein the filtering precision is 1-3 mu m.
Examples 5-8 yellow and Red ink formulations are given in Table 2
TABLE 2 yellow and Red ink formulations
The manufacturing method comprises the following steps: the same procedure as in examples 1 to 4 was employed.
Examples 9-12 blue and violet ink formulations are shown in table 3:
TABLE 3 blue and Green ink formulations
The manufacturing method comprises the following steps: the same procedure as in examples 1 to 4 was employed.
3. The results of the performance measurements are shown in Table 4.
TABLE 4 Performance test results
And (4) conclusion:
the formula of the high-speed UV code-spraying ink does not contain an organic solvent, and the ink is cured by full UV. From the above test data it appears that: the high-speed UV code-spraying ink adopts a green environment-friendly photoinitiation system, and has the characteristic of green environment protection; the paint can be quickly cured under the irradiation of a UV-LED light source, and the requirement of high vehicle speed is met; the content of the color paste is high, and the requirement of low-resolution printing quality is met; the continuity and the fluency are good, and the requirement of a high-speed ONEPASS printing mode is met; the hardness and the flexibility are moderate, and the coating is suitable for various base materials; the adhesive has good adhesion on paper and film materials, and has wide development prospect.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various changes and modifications can be made without departing from the overall concept of the present invention, and these should also be considered as the protection scope of the present invention.

Claims (10)

1. A high-speed UV spouts a yard ink which characterized in that: the ink-jet ink comprises the following raw materials in percentage by weight:
3 to 15 percent of polyester acrylate
4-16% of polyurethane acrylate
60 to 80 percent of active monomer
1 to 10 percent of pigment
3 to 15 percent of photoinitiator
1 to 10 percent of auxiliary initiator
3 to 10 percent of dispersant
0.1 to 3 percent of auxiliary agent;
the auxiliary agent is at least one of a wetting and leveling agent, a thermal polymerization inhibitor, a deodorant, a defoaming agent or a foam inhibitor and an adhesion promoter.
2. The high-speed UV inkjet printing ink according to claim 1, wherein: the viscosity of the polyester acrylate is 150-.
3. The high-speed UV inkjet printing ink according to claim 1, wherein: the polyurethane acrylate is aliphatic polyurethane acrylate; the polyurethane acrylate at least contains one polyurethane acrylate with the functionality of 1-2 and at least one polyurethane acrylate with the functionality of more than 4; the 1-2 functionality polyurethane acrylate and the polyurethane acrylate with more than 4 functionalities respectively account for 2-8% of the total amount of the UV ink-jet ink.
4. The high-speed UV inkjet printing ink according to claim 1, wherein: the active monomer comprises low-viscosity monofunctional acrylate and acrylamide active monomer and contains- (CH) in molecular chain2)n-or- (OCH)2)nMono-or bi-functional acrylate monomers of the structure (n.gtoreq.5); the addition amount of the active monomer is 15-65%.
5. The high-speed UV inkjet printing ink according to claim 1, wherein: the pigment comprises at least one of titanium dioxide, phthalocyanine pigment, quinacridone pigment, azo pigment, benzimidazolone pigment or carbon black pigment; ink colors include CMYKW and spot colors.
6. The high-speed UV inkjet printing ink according to claim 1, wherein: the photoinitiators include Norrish type I and Norrish type II photoinitiators.
7. The high-speed UV inkjet printing ink according to claim 1, wherein: the co-initiator is an active amine co-initiator.
8. The high-speed UV inkjet printing ink according to claim 1, wherein: the photoinitiator is a green environment-friendly photoinitiator.
9. The high-speed UV inkjet printing ink according to claim 1, wherein: the dispersant is at least one of modified acrylate block copolymer, olefine acid block copolymer, hyper-dispersant with anchor group and organic modified polysiloxane.
10. A method of making a high speed UV inkjet printing ink according to any one of claims 1 to 9, wherein: the method comprises the following specific steps: (1) dispersing and grinding a mixture of the pigment, the dispersing agent and part of the active monomer to prepare color paste; (2) stirring and dissolving a photoinitiator, an auxiliary initiator, an auxiliary agent, the rest part of active monomer, polyester acrylate and polyurethane acrylate to prepare a pre-solution; (3) dispersing the pre-solution in color paste at high speed; (4) and finally, filtering the printing ink by using a microporous filter membrane.
CN201911290517.8A 2019-12-13 2019-12-13 High-speed UV code-spraying ink and preparation method thereof Pending CN112980244A (en)

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