CN108070299A - For the functional ink and preparation method and application of inkjet printing - Google Patents
For the functional ink and preparation method and application of inkjet printing Download PDFInfo
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- CN108070299A CN108070299A CN201710526185.3A CN201710526185A CN108070299A CN 108070299 A CN108070299 A CN 108070299A CN 201710526185 A CN201710526185 A CN 201710526185A CN 108070299 A CN108070299 A CN 108070299A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/0011—Pre-treatment or treatment during printing of the recording material, e.g. heating, irradiating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/0023—Digital printing methods characterised by the inks used
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/36—Inkjet printing inks based on non-aqueous solvents
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes
Abstract
The present invention relates to one kind to be used for special base material（Glass, ceramics, metal）The functional ink and preparation method and application of surface inkjet printing.The functional ink of the present invention contains the component of following parts by weight：Epoxy resin 1# is 5 20 parts, and epoxy resin 2# is 10 30 parts, 1 10 parts of curing agent, 0.5 5 parts of accelerating agent, and solvent 1# is 25 50 parts, and solvent 2# is 1 15 parts, 0.05 2 parts of auxiliary agent.The invention further relates to the preparation methods, performance parameter and application method of the functional ink.The functional ink of the present invention contains epoxy resin, curing agent, accelerating agent, solvent and other auxiliary agents of approrpiate wts proportioning, there is excellent stability and high temperature rapid curing, cured glued membrane has splendid adhesive force, water resistance, toughness and hardness.The functional ink of the present invention plays the role of the transition zone between such substrate surface and UV layer of ink particularly suitable for particular substrate surfaces such as glass, ceramics, metals, thus by UV（Ultra-violet curing）Ink-jet technology be broadly generalized to printing packaging, decoration field industrialized production in.
Description
Technical field
The present invention relates to a kind of functional inks for inkjet printing, are suitble to the special base material tables such as glass, ceramics, metal
The transition zone between such substrate surface and UV layer of ink is played the role of in face, so as to which UV ink-jet technologies be broadly generalized to
Printing packaging, decoration field industrialized production in.
Background technology
Various bills start to show increasingly stronger personalized tendency, telecommunications, postal in China, digital printing market
The potentiality in the personal printings such as political affairs, bank, security, insurance market are very huge.On Beijing, Shanghai, Guangzhou, Shenzhen and other places, arrive
Locate the big and small fast print shop in visible curbside, it is sufficient to prove that digital printing has been enter into our daily life.
At abroad, digital printing is commonly used to printing report, customer directory, enterprise's picture album, commercial affairs printing and a small amount of books and periodicals,
Such as postcard, business card, front cover, brochure and CD sets；For the small-sized packaging of packages printing such as drug, healthy articles for use and gift；
For drawing a design, promoting, testing and sell；It is additionally operable to printing wallpaper, stringcourse and lace paper etc..
Digital printing device becomes indispensable in an office with its distinctive characteristic such as convenient and efficient all the time
Auxiliary tool.However, sides such as " breadth are small, speed is low, color image reproducibility is poor, requires height to stock " can not be broken through by suffering from
The factor limitation in face, the technology are limited by always between the narrow and small building that write, and can not be played and be made in the more wide industrial world
With.It reviews in industrial circle, although CTP（Computer Direct Plate Making）、ERP（Enterprise digital management）Etc. digital technologies just rich
Rich the various applications of printing industry, if however inkjet printing etc. " light printing " technology can be introduced, just can be to a certain extent
The situation of current " traditional printing is weak, digital printing is powerless " this gap between generations of taking on a new look.
Ink jet printing
Ink jet printing（Ink-jet Printing）It is a kind of important digital printing mode in addition to laser printing, it is a kind of
Contactless, no pressure, the print reproduction technology without printing plate, the common trait with no version digital printing, and can realize variable letter
Breath printing.Study carefully its principle, actually play the same tune on different musical instruments wonderful, the figure for first storing computer with many digital technologies such as CTP
Literary information inputs ink-jet apparatus, then by special device, under computer control, is sprayed from nozzle to stock surface vaporific
Ink droplet, according to charge effect in the direct imaging of stock surface, become final printed matter.It is divided into and is sprayed for continous way among these
Ink print（CIJ）With on-demand ink jet printing（DOD）Two classes.Continuous ink jet printing, no matter picture and text or non-graphic, be all with
The mode of flowing continuously generates ink droplet, then deflects to form image by electric field, finally by the recycling of the ink droplet of unnecessary appearance or
It is scattered.On-demand ink jet printing only just generates ink droplet in plating part, is exclusively used in the image of printing one's best quality, is suitable for
The printing of coloured picture, textile and large format billboard is packed, is the ideal chose of full color, high accuracy prints, press quality is
This most important Consideration of mode.
Ultra-violet curing ink jet printing
UV ink jet printings are with ultraviolet light in ink jet printing（UV）Rapid curing is a kind of extensive use decoration of characteristic
Industrial mode of production, it conform to the main flow direction of packages printing technology in the world to digitlization, networking, high-speed low-consumption,
More environmentally-friendly and personalized trend.West Europe UV ink jet printing market scales are about 2,400,000,000 dollars within 2013, and will be not
Come in 5 years to keep 13.6% annual average compound growth rate.UV ink jet printings also show scene of flourishing life, future in North America
5 years, speedup was up to 16.2%.Smithers Pai Nuo companies（The global well-known survey institute of printing packaging industry）Portion is issued
《UV ink jet printing market predictions in 2018》Report, report show UV ink jet printings will rapidly develop in the world,
Market scale will increase by 18.3% in the five-year, and will reach 15,900,000,000 dollars in 2018.Domestic UV ink jet printings market belongs to
In the starting stage, but the market share is also progressively expanding, with the introduction of equipment, the improvement of UV ink-jet inks, UV ink jet printings
Perfect, ink-jetting process the exploitation of system, ink-jet printing technology applying on glass, ceramics, metal are progressively showing.
UV ink-jets are suitble to the bill of materials of printing as follows：
| Material type | Material category |
| Flexible material | Printing paper, specialties, leather, canvas, vinyl film or piece, magnetic sticker |
| Hard material | Corrugated paper, original screen panel, PET/PC/PP, iPad/iPhone shell, marble, plank, KT plates, PVC expansion sheet, X-Board, acrylic |
| Need the rigid special materials being coated with | Glass, ceramics, metal |
Traditional specialty printing technique
It is printed for special substance（Glass, ceramics, metal）Traditional handicraft is highly developed, and silk-screen printing is wherein using non-
Normal extensive traditional handicraft, occupation rate of market is up to more than 90%.By way of silk-screen printing, we can be easily in wine
The surfaces such as bottle, glass, glass panel, ceramic bottle, canister directly print various patterns, but silk-screen printing there is also
It needs to change plate when picture and text precision is low, not overprintable tone variations are few, printing needs contact, different pattern printings need to individually make a plate, change the line of production
Roll change the defects of time-consuming.
Ceramic ink jet prints
Ceramic field is that ink jet printing enters at first in three big special substance printings, the global large-scale promotion number early in 2013
Word production method, global ceramic tile inkjet printing equipment is grown rapidly with technology within 2014.In December, 2010, number was installed in the whole world
Printing equipment about 538, the end of the year 2011 increased to 1054, rose to 1537 to 12 months 2012 bottoms, increased every year on average
Length is more than 500.
Only one-year age in 2013, digital printing apparatus just increase 1367 newly.According to statistics, to sum on January 31st, 2014
Reach 2904（Increase+89% within 13 months）.Some countries are more early using this technology and equipment, therefore development is also faster, example
Such as：There are about 300 equipment now to use for Spain, and there are also 240 equipment to use for Italy（It was installed including 2013
43）, some statistics may be higher, and some possibility are relatively low, in non-european countries, is increased using digital printing apparatus most fast
Be Asian countries.
Inkjet printing technology in 2011 starts to apply in China's ceramic tile industry, and the whole nation has more than 1/3rd pottery so far
Ceramic tile production line is equipped with ink jet printing device.Manufacturing enterprise is mainly used for ceramic tile, Antique Imitation Tiles, full throwing using inkjet printing technology
The ink-jet printer quantity that the glaze decorating of the products such as glazed brick, exterior wall tile, wherein tile class enterprise use is most, tile class product
One production line needs to configure 3 or more ink-jet printers, and the ink-jet printer of the large-scale ceramic tile manufacturing enterprise equipment in part surpasses
Cross 10, for inkjet printing product proportion 50%~60%, some enterprises have begun the complete ink-jet printed product of production.Except
Tile, Antique Imitation Tiles and Full-glazed tile are also the two major class products using ink-jet printer, especially from 2013, in some porcelain
The Antique Imitation Tiles in area and Full-glazed tile manufacturing enterprise start to promote inkjet printing technology, also have many Antique Imitation Tiles enterprises to prepare to increase spray
Black printer, for relatively common Antique Imitation Tiles, inkjet printing pattern effect is more preferable, and client is easier to receive.
By in April, 2014, the ceramic ink jet equipment of China's on-line operation is more than 2000, domestic ceramic ink jet printing
The market share of equipment at home has accounted for 60% or so, occupies leading position.To the end of the year in 2014, domestic ceramic tile production enterprise
The ink jet printing device that industry is equipped with has reached 3000.
The success of ink-jet ceramic printing is that inkjet printing breaches the limitation of silk screen at many aspects, such as：Precision is up to
More than 360dpi, hanging non-contacting printing type can prevent damaged, male and fomale(M＆F) printing from can realize various textures, complicated face
Color prints to realize gradual transition.
Ink jet coatings technology
Another factor that can not ignore of ink-jet ceramic printing success is industrial advantages, as Development of Real Estate continued in recent years
In a high position, ceramic tile is in great demand, and ceramic tile belongs to high value added product, and the slightly promotion of decoration technology cost will not be to product
Overall price generates much influences.
And for packages printing industry（Glass, ceramics, canister）, since individual price is relatively low, decoration technology cost
Promotion will be a greater impact to product price, therefore the inferior position of ink-jet ceramic printing process costs will display.Ink-jet ceramics print
It is insufficient existing for brush equipment：1. resolution ratio only 360dpi（UV industrial printer resolution ratio is up to 600dpi）2. ink cannot be instant
Dry and hard, glaze paint pattern can obscure, 3. printing grain effect difference needs high temperature sintering（600℃）4. nozzle and ink need import cost
It is high.
The ink of UV ink-jets is very good in the adaptability of flexible material and hard material surface, the sample fineness to gush out
Height, durability is strong, therefore UV ink-jets are widely used in terms of above two material is drawn a design for silk-screen with short slab printing.But for
Need the rigid material being coated with ceramics, glass, the adhesive force of surface of steel plate UV marking inks and water resistance aspect not fully up to expectations
（Through investigation, obtained including consulting U.S. DCS embossment printer technologies assistant director）.
In terms of packages printing（Glass wine bottle, ceramic bottle, canister, tin graphed sheet tank）And in terms of decoration（Shower
Room, toilet, the glassware in kitchen, outdoor decoration glass, glass, disk, furred ceiling etc.）If can solve adhesive force and
Water resistance, UV ink-jets will trigger packages printing, the technological revolution of decoration industry surface finish.
Be useful for currently on the market improve UV ink-jets glass, ceramics, metal surface adhesive force, water resistance coating
Product, such as：The UV-603F-A/B types of Chemical Co., Ltd. of Shenzhen Donggang City（Suitable for glass surface）, UV-6125D hand wiping types（It is suitable
For metal surface）, this two treatment fluid has certain help, but UV-603F- to the raising of glass ceramics metal surface adhesive force
A/B types belong to AB liquid using preceding needing to mix, and there are timeliness, while two belongs to hand wiping type and be not suitable for industrialized big life
Production.
Conclusion
In summary, it is necessary to develop it is a kind of have the function of transition zone effect, one-component stability it is excellent and be suitble to ink jet printing
UV ink-jet technologies could be successfully generalized to packages printing, the decoration field of large-scale industrial production by ink.
The content of the invention
In order to achieve the above object, the present invention provides a kind of single component, simple production process, for special substance（Glass
Glass, ceramics, metal）Surface has high adhesion strength, high temperature resistance, scoring resistance, water resistance, resistance to boiling, chemical-resistant
The functional ink of the features such as energy, versatility, excellent weather resistance and hard.
The functional ink of the present invention, the component containing parts by weight once：Epoxy resin 1# is 5-20 parts, and epoxy resin 2# is
10-30 parts, 1-10 parts of curing agent, 0.5-5 parts of accelerating agent, solvent 1# is 25-50 parts, and solvent 2# is 1-15 parts, auxiliary agent 0.05-2
Part.
The functional ink of the present invention, wherein the preferably described epoxy resin 1# is bisphenol A type epoxy resin, selected from E03,
One or more kinds of combinations in E06, E10, E12, E14, E20, E31, E35, E39, E42, E44, E51, E55 etc.,
The epoxy resin market is on sale.
The functional ink of the present invention, wherein the preferably described epoxy resin 2# is phenol aldehyde type epoxy resin, selected from F51,
One or more kinds of combinations in F48, F44, F47, F43 etc., the epoxy resin market are on sale.
The functional ink of the present invention, wherein it is preferred that the curing agent is selected from dicyandiamide, biguanides, organic acid hydrazides, trifluoro
Change boron-amine complex, boron triflouride-mono aminoethane complex compound, boron trifluoride-benzylamine complex compound, aminimide（AI）, super coordination
Silicate（ECSS）, m-phenylene diamine (MPD), alkane diamines, diaminodiphenyl-methane, diaminodiphenylsulfone, hexahydrophthalic acid anhydride,
Methyl hexahydrophthalic acid anhydride, carbic anhydride（NA）, methylnadic anhydride（MNA）, glutaric anhydride, hydrogenating methyl nadik
One or more kinds of combinations in acid anhydrides, methylcyclohexene tetracarboxylic dianhydride, the curing agent are commercially available.
The functional ink of the present invention, wherein it is preferred that the accelerating agent is selected from DMP-30（2,4,6- tri-（Dimethylamino first
Base）Phenol）、BDMA（Benzyl dimethylamine）、DMP-10（Adjacent hydroxybenzyl dimethylamine）, chromium acetylacetonate, zinc acetylacetonate, acetyl
Acetone nickel, acetylacetone cobalt, benzyltrimethylammonium chloride, triethanolamine borate, triethanol amine titanate, tin octoate, quaternary phosphines
Salt, diazabicylo, benzoyl peroxide, thiocarbamide, 2E4MZ（2-ethyl-4-methylimidazole）, 2- benzylimidazolines, 2- mercaptan
One or more kinds of combinations in base benzothiazole, the accelerating agent are commercially available.
The functional ink of the present invention, wherein the preferably described solvent 1# selected from acetone, butanone, methyl iso-butyl ketone (MIBK), pentanone,
One or more kinds of combinations in benzene,toluene,xylene, ether, chloroform, hexamethylene.
The functional ink of the present invention, wherein it is preferred that the solvent 2# is selected from methanol, ethyl alcohol, ethylene glycol, isopropanol, fourth
Alcohol, ethylene glycol monomethyl ether, butyl glycol ether, propylene glycol monomethyl ether, propylene-glycol ethyl ether, propandiol butyl ether, methyl acetate, ethyl acetate,
Butyl acetate, dimethyl carbonate, DBE（Dimethyl succinate, dimethyl glutarate, the mixed solvent of dimethyl adipate）In
One or more kinds of mixtures.
The invention further relates to the methods for preparing functional ink, and epoxy resin 1# is crushed into powder last solvent 1# dissolvings,
Sticky liquid is obtained, then is stirred evenly with curing agent, it is homogeneous always then to add in solvent 2# guarantee systems while stirring
Clarified solution, by above-mentioned 50 DEG C of architecture heat preservation and mix slowly 5-24 it is small when, add in epoxy resin 2# thereafter to being completely dissolved, then add
Enter accelerating agent to being completely dissolved, be eventually adding auxiliary agent.
The invention further relates to the functional ink performance parameter of inkjet printable, viscosity number 5-30mPa.s（25℃）, surface
Tension is 25-50dyn/cm（25℃）.
The invention further relates to a kind of ultra-violet curing inkjet printing methods, comprise the following steps：
1) cleaning：Oil removing, dedusting, drying process are carried out to stock surface；
2) step is activated：Use silane coupling agent（Weight percent 0.1-0.5%）Aqueous solution the stock surface is carried out
Activation；
3) step is sprayed in advance：Functional ink described in claim 9 is passed through into UV（Ultra-violet curing）Printer is in the stock table
Face printing picture and text and infra-red drying；
4) ink-jet step：UV inks are cured by UV printers in the stock printout surface picture and text and UV；
5) curing schedule：The stock that printing finishes is put into 120 DEG C -180 DEG C of baking oven to toast 10-30 minutes.
The present invention utilizes epoxy resin（It is commonly called as all-purpose adhesive）The characteristics of distinctive hydroxyl and excellent epoxy group caking property, in addition idol
Join the organic and inorganic reaction of agent, make its solidified glue film and UV inks and solidified glue film and special substance（Glass, ceramics,
Metal）Firm chemical bond is all formed between surface, splendid adhesive force and water resistance are reached by chaining.
The present invention obtains splendid toughness using the Long carbon chain of bisphenol-A epoxy and the phenyl ring rigid structure of epoxy novolac
And hardness.
The present invention forms stable addition structure using the pre-reaction of bisphenol-A epoxy and curing agent and alcohol ester solvent, makes
System after its addition accelerating agent has the characteristics that excellent stability and high temperature rapid curing.
The present invention is improved solvability, is reduced harm of the solvent to environment using the cooperation of conventional strong solvent and Weak solvent
Property.
The present invention utilizes solvent combination, to OK range, to be allowed to be suitble to piezoelectric type by the viscosity of system and surface tension adjustment
The nozzle characteristic of ink-jet printer.
The advantage that the present invention is compared with the prior art is：
1) meet the parameter request of printing head, can directly go up machine printing and meet industrial automation mass production；
2) plug and play, without now matching somebody with somebody, stability is excellent, and Storage period reaches more than half a year, meets inkjet printing requirement；
3) low-temperature bake（120℃-180℃）Energy-saving environmental protection；
4) without free radical, monomer residue after toasting, product use is safer；
5) cured layer clear, colorless on printing picture and text quality almost without influence thereon；
6) cured layer toughness is excellent, hardness is big, can play the role of good transition zone between material surface and UV inks, and have
There is very excellent water boiling resistance performance；
7) it can coordinate with most of UV inks on the market, reach very excellent scratch-resistant lattice, scratch resistance, wear-resisting, water-fast.
Description of the drawings
Fig. 1 shows the ultra-violet curing InkJet printing processes flow of functional ink.
Specific embodiment：
Make in more detail with test effect, the technical characteristic above-mentioned and other to the present invention and advantage with reference to embodiments
It is bright.
Embodiment：The preparation of functional ink
Functional ink（1）Preparation
Weigh epoxy resin 1#（E03：E14=3：2）Mixed composition 100g grinds the burning for into powder, pouring into 1000ml using mortar
In cup, solvent 1# is then added in（Toluene：Acetone=1:4）400g, which fully dissolves, obtains homogeneous thick liquid；Add in curing agent（Two
Aminodiphenylmethane）For 60g, it is to be mixed uniformly after, add in solvent 2# while stirring（Ethylene glycol monomethyl ether）80g, guarantee system
Always be homogeneous clarified solution, by above-mentioned 50 DEG C of architecture heat preservation and mix slowly 12 it is small when, add in epoxy resin 2# thereafter（F44）
180g adds accelerating agent to being completely dissolved（2E4MZ）9g is eventually adding auxiliary agent to being completely dissolved（Levelling agent enlightening high 100 is
0.2g, antioxidant Chemtura 1076 are 0.3g, and the high LTW of adhesion promoter enlightening is 0.1g）.
Embodiment 2：The preparation of UV printouts
Printout（a）
Glass sheet surface is subjected to oil removing, dedusting, drying process, with coupling agent DOW CORNING 6121（0.1-0.5%）Aqueous solution pair
Glass sheet surface carries out spraying moisture film, strikes off and dry（Activation）, by functional ink（1）Pour into DCS companies of U.S. 3D printer
The transparent ink passage of 1024UVHS（Other channels inks are original-pack UV inks）, transparent ink is used on sheet glass upon activation
Printing picture and text and drying ensure that solvent volatilizees completely, colored picture and text and UV curings are printed in transparent layer of ink, by printed material
Matter is put into baking oven and toasts 30 minutes for 160 DEG C.
Fig. 1 shows the functional ink ultra-violet curing inkjet printing methods of the present invention in a manner of technological process.Completion removes
Sheet glass 12 after oil, dedusting, drying process enters production line 13：Sheet glass 12 initially enters active module, battle array of spraying
Row 1 are to 12 surface spraying coupling agent aqueous solution 2 of sheet glass；It subsequently enters and scrapes film module, blade insert or air knife 3 are by sheet glass
12 excess surface moistures strike off, only remaining very thin moisture film；Into drying module, infrared dryer 4 dries rapidly moisture film；Into
Enter functional ink print module, functional ink printing head 5 in the transparent picture and text effect of 12 printout surface of sheet glass as shown at 14,
And it carries out infra-red drying rapidly and dries the solvent in functional ink；Into tetra- color print modules of UV, yellow print nozzle 6 is in glass
The yellow ink of 12 surface double exposure of glass piece, in printing, UV cures 7, and printing effect is as shown in 15；So repeatedly, successively by pinkish red printing
Nozzle 8, cyan print nozzle 9, the ink printed of black print nozzle 10 and curing, double exposure effect is respectively such as 16,17,18 institutes
Show；Finally enter hot setting room 11,160 DEG C of baking completes glass ornamenting processing after 30 minutes.
Printout（b）
Potsherd surface is subjected to oil removing, dedusting, drying process, with coupling agent DOW CORNING 6121（0.1-0.5%）Aqueous solution pair
Potsherd surface carries out spraying moisture film, strikes off and dry（Activation）, functional ink is poured into DCS companies of U.S. 3D printer
The transparent ink passage of 1024UVHS（Other channels inks are original-pack UV inks）, transparent ink is used on potsherd upon activation
Printing picture and text and drying ensure that solvent volatilizees completely, colored picture and text and UV curings are printed in transparent layer of ink, by printed material
Matter is put into baking oven and toasts 30 minutes for 160 DEG C.
Printout（c）
Sheet metal surface is subjected to oil removing, dedusting, drying process, with coupling agent DOW CORNING 6040（0.1-0.5%）Aqueous solution pair
Sheet metal surface carries out spraying moisture film, strikes off and dry（Activation）, functional ink is poured into DCS companies of U.S. 3D printer
The transparent ink passage of 1024UVHS（Other channels inks are original-pack UV inks）, with transparent on dried sheet metal is activated
Ink printed picture and text and drying ensure that solvent volatilizees completely, and colored picture and text and UV curings are printed in transparent layer of ink, will be printed
Material be put into baking oven 160 DEG C and toast 30 minutes.
Ink case of comparative examples（2）
Weigh epoxy resin 1#（E03：E14=3：2）Mixed composition 100g grinds the burning for into powder, pouring into 1000ml using mortar
In cup, solvent 1# is then added in（Toluene：Acetone=1:4）400g, which fully dissolves, obtains homogeneous thick liquid；Add in curing agent（Two
Aminodiphenylmethane）For 60g, it is to be mixed uniformly after, add in solvent 2# while stirring（Ethylene glycol monomethyl ether）80g, guarantee system
Always be homogeneous clarified solution, by above-mentioned 50 DEG C of architecture heat preservation and mix slowly 12 it is small when, add in accelerating agent（2E4MZ）9g is to complete
Fully dissolved adds in auxiliary agent（Levelling agent enlightening high 100 is 0.2g, and antioxidant Chemtura 1076 is 0.3g, and adhesion promoter enlightening is high
LTW is 0.1g）.
Ink case of comparative examples（3）
Weigh epoxy resin 2#（F44）180g is ground using mortar into powder, is poured into the beaker of 1000ml, is then added in solvent
1#（Toluene：Acetone=1:4）400g, which fully dissolves, obtains homogeneous thick liquid；Add in curing agent（Diaminodiphenyl-methane）For
60g, it is to be mixed uniformly after, add in solvent 2# while stirring（Ethylene glycol monomethyl ether）80g, guarantee system are homogeneous clarification always
Liquid, by above-mentioned 50 DEG C of architecture heat preservation and mix slowly 12 it is small when, add in accelerating agent（2E4MZ）9g is eventually adding to being completely dissolved
Auxiliary agent（Levelling agent enlightening high 100 is 0.2g, and antioxidant Chemtura 1076 is 0.3g, and the high LTW of adhesion promoter enlightening is 0.1g）.
Ink case of comparative examples（4）
Weigh epoxy resin 1#（E03：E14=3：2）Mixed composition 100g grinds the burning for into powder, pouring into 1000ml using mortar
In cup, solvent 1# is then added in（Toluene：Acetone=1:4）400g, which fully dissolves, obtains homogeneous thick liquid；Add in curing agent（Two
Aminodiphenylmethane）For 60g, it is to be mixed uniformly after, add in solvent 2# while stirring（Ethylene glycol monomethyl ether）80g, guarantee system
Always be homogeneous clarified solution, by above-mentioned 50 DEG C of architecture heat preservation and mix slowly 12 it is small when, add in epoxy resin 2# thereafter（F44）
180g is eventually adding auxiliary agent to being completely dissolved（Levelling agent enlightening high 100 is 0.2g, and antioxidant Chemtura 1076 is 0.3g, is adhered to
The high LTW of power accelerating agent enlightening is 0.1g）.
Ink case of comparative examples（5）
Weigh epoxy resin 1#（E03：E14=3：2）Mixed composition 100g grinds the burning for into powder, pouring into 1000ml using mortar
In cup, solvent 1# is then added in（Toluene：Acetone=1:4）400g, which fully dissolves, obtains homogeneous thick liquid；Add in curing agent（Two
Aminodiphenylmethane）For 60g, it is to be mixed uniformly after, add in epoxy resin 2#（F44）180g is added in being completely dissolved
Accelerating agent（2E4MZ）2g is eventually adding auxiliary agent to being completely dissolved（Levelling agent enlightening high 100 be 0.2g, antioxidant Chemtura 1076
For 0.3g, the high LTW of adhesion promoter enlightening is 0.1g）.
Print case of comparative examples（d）
Glass sheet surface is subjected to oil removing, dedusting, drying process, with coupling agent DOW CORNING 6121（0.1-0.5%）Aqueous solution pair
Glass sheet surface carries out spraying moisture film, strikes off and dry（Activation）, colored picture and text are directly printed in the sheet glass for activating dried
And UV cures, and printed material is put into baking oven and is toasted 30 minutes for 160 DEG C.
Print case of comparative examples（e）
Glass sheet surface is subjected to oil removing, dedusting, drying process, functional ink is poured into DCS companies of U.S. 3D printer
The transparent ink passage of 1024UVHS（Other channels inks are original-pack UV inks）, transparent ink is used on dried sheet glass
Printing picture and text and drying ensure that solvent volatilizees completely, colored picture and text and UV curings are printed in transparent layer of ink, by printed material
Matter is put into baking oven and toasts 30 minutes for 160 DEG C.
Print case of comparative examples（f）
Glass sheet surface is subjected to oil removing, dedusting, drying process, with coupling agent DOW CORNING 6121（0.1-0.5%）Aqueous solution pair
Glass sheet surface carries out spraying moisture film, strikes off and dry（Activation）, functional ink is poured into DCS companies of U.S. 3D printer
The transparent ink passage of 1024UVHS（Other channels inks are original-pack UV inks）, with transparent on dried sheet glass is activated
Ink printed picture and text and drying ensure that solvent volatilizees completely, and colored picture and text and UV curings are printed in transparent layer of ink.
Test example：Performance evaluation
To functional ink（1）With ink case of comparative examples（2）-（5）It is film-made and cures 160 DEG C 30 minutes, to the cut appearance of glued membrane
（Cross-hatching）, hardness（Pencil hardness method）, stability（Working life：The time that storage medium viscosity value doubles）It is tested,
It the results are shown in Table 1.
1 functional ink of table（1）With ink case of comparative examples（2）-（5）Performance test
| Sample | Cut appearance | Hardness | Working life | Remarks |
| Functional ink（1） | Nothing is burst apart | 3H | It is more than half a year | |
| Case of comparative examples（2） | Nothing is burst apart | B | —— | Without epoxy 2# |
| Case of comparative examples（3） | It bursts apart | 3H | —— | Without epoxy 1# |
| Case of comparative examples（4） | Nothing is burst apart | B | It is more than half a year | Without accelerating agent |
| Case of comparative examples（5） | Nothing is burst apart | 3H | 5 days | No alcohol ester heat preservation |
As it can be seen from table 1 case of comparative examples（2）Because system lacks epoxy 2#（The rigid phenyl ring of band）The low glued membrane difference of hardness of the degree of cross linking；
Case of comparative examples（3）Because system lacks epoxy 1#（Backbone）Glued membrane degree of cross linking high rigidity is high but poor toughness, therefore tool marks when drawing lattice
It easily bursts apart at edge；Case of comparative examples（4）The excellent storage time of system stability is long, but because lacking accelerating agent glued membrane in short-term baking
Curing degree is low under environment, therefore difference of hardness；Case of comparative examples（5）Because no alcohol ester is kept the temperature, curing agent does not have addition reaction, epoxy segment
There is no space steric effects therefore system to be easy to be cured reaction at normal temperatures, and system storage time is short.
To printout（a）-（c）With printing case of comparative examples（d）-（f）Sample be compared, to the adhesive force of picture and text on sample
（3M adhesive tape methods）, water boiling resistance（Boiling is impregnated）It is tested, the results are shown in Table 2.
Table 2 is to printout（a）-（c）With printing case of comparative examples（d）-（f）Properties of sample test
| Sample | Adhesive force | Water boiling resistance | Remarks |
| Printout（a） | 100% nothing comes off | 24 it is small when more than | Glass |
| Printout（b） | 100% nothing comes off | 24 it is small when more than | Ceramics |
| Printout（c） | 100% nothing comes off | 24 it is small when more than | Metal |
| Print case of comparative examples（d） | More than 90% comes off | —— | Nonfunctional ink |
| Print case of comparative examples（e） | 100% nothing comes off | 1 comes off when small | Without activation |
| Print case of comparative examples（f） | 100% nothing comes off | 1 comes off when small | Without high-temperature baking |
From table 2 it can be seen that functional ink is suitable for glass, ceramics, the special substance of metal, picture and text adhesive force is excellent after printing
And water boiling resistance 24 it is small when more than；Print case of comparative examples（d）Because of nonfunctional ink pre-print, printing picture and text are in material surface adhesive force
It is very poor；Print case of comparative examples（e）Because no coupling agent activates, picture and text water boiling resistance poor-performing is printed；Print case of comparative examples（f）Because of nothing
High-temperature baking, functional ink layer do not crosslink, cannot play linkage effects therefore print picture and text water boiling resistance poor-performing.
The weight proportion of each component is inventor by long-term production experience and tests many times in functional ink of the present invention
The preferable value range that optimal screening obtains, i.e., when epoxy resin 1# is 5-20 parts, epoxy resin 2# is 10-30 parts, curing agent
1-10 parts, 0.5-5 parts of accelerating agent, solvent 1# is 25-50 parts, and solvent 2# is 1-15 parts, 0.05-2 parts of auxiliary agent, has preferable effect
Fruit（As shown in table 1）.When each component weight ratio is not within the scope of the invention or when lacking certain component, the physics of functional ink
Hydraulic performance decline, obtained glued membrane toughness, hardness are all undesirable.
In other implementations, epoxy resin 1# can also be E06, E10, E12, E20, E31, E35, E39, E42,
One or more kinds of combinations in the bisphenol A epoxide resins such as E44, E51, E55；Epoxy resin 2# can also be F51,
One or more kinds of combinations in the novolac epoxy resins such as F48, F47, F43；Curing agent can also be dicyandiamide, double
Guanidine, organic acid hydrazides, boron trifluoride-amine complex, boron triflouride-mono aminoethane complex compound, boron trifluoride-benzylamine complex compound, amine
Aminimide（AI）, super coordination silicate（ECSS）, m-phenylene diamine (MPD), alkane diamines, diaminodiphenylsulfone, hexahydro phthalic acid
Acid anhydride, methyl hexahydrophthalic acid anhydride, sodium Dick acid anhydrides（NA）, methylnadic anhydride（MNA）, glutaric anhydride, hydrogenating methyl receive
One or more kinds of combinations in Dick acid anhydrides, methylcyclohexene tetracarboxylic dianhydride；Accelerating agent can also be DMP-30
（2,4,6- tri-（Dimethylamino methyl）Phenol）、BDMA（Benzyl dimethylamine）、DMP-10（Adjacent hydroxybenzyl dimethylamine）, levulinic
Ketone chromium, zinc acetylacetonate, nickel acetylacetonate, acetylacetone cobalt, benzyltrimethylammonium chloride, triethanolamine borate, three ethyl alcohol
Amine titanate esters, tin octoate, quaternary alkylphosphonium salts, diazabicylo, benzoyl peroxide, thiocarbamide, 2- benzylimidazolines, two-mercapto benzene
And one or more kinds of combinations in thiazole；Solvent 1# can also be butanone, methyl iso-butyl ketone (MIBK), pentanone, benzene, diformazan
One or more kinds of combinations in benzene, ether, chloroform, hexamethylene；Solvent 2# can also be methanol, ethyl alcohol, ethylene glycol,
Isopropanol, butanol, butyl glycol ether, propylene glycol monomethyl ether, propylene-glycol ethyl ether, propandiol butyl ether, methyl acetate, ethyl acetate, vinegar
Acid butyl ester, dimethyl carbonate, DBE（Dimethyl succinate, dimethyl glutarate, the mixed solvent of dimethyl adipate）In one
Kind or two or more combinations, the citing being not limited in above-described embodiment.
In the present invention to material surface into the coupling agent of line activating, can also be DOW CORNING Z-6020, Z-6026, Z-
6032nd, one or more kinds of groups in Z-6030, Z-6075, Z-6076 and other brand organo silane coupling agents
It closes, the citing being not limited in above-described embodiment.
Embodiment described above is only that the preferred embodiment of the present invention is described, not to the model of the present invention
It encloses and is defined, on the premise of design spirit of the present invention is not departed from, those of ordinary skill in the art are to the technical side of the present invention
The various modifications and improvement that case is made should all be fallen into the protection domain that claims of the present invention determines.
Attached drawing Major Symbol explanation：
1. 2. coupling agent aqueous solution of spray array, 3. blade insert or 4. infrared dryer of air knife
5. the yellow black printing head 7.UV solidification devices of functional ink printing head 6.UV
The blue or green black printing head 10.UV tusche printing heads of 8.UV magenta ink printing heads 9.UV
11. 12. sheet glass, 13. production line 14. functional ink in hot setting room prints picture and text effect（Clear, colorless）
15. the blue or green black 18. tusche double exposure of double exposure picture and text effect of 16. magenta ink double exposure picture and text effect of yellow ink double exposure picture and text effect 17.
Picture and text effect
Claims (10)
1. a kind of functional ink, which is characterized in that be made of the component of following parts by weight：Epoxy resin 1# is 5-20 parts, epoxy
Resin 2# is 10-30 parts, 1-10 parts of curing agent, 0.5-5 parts of accelerating agent, and solvent 1# is 25-50 parts, and solvent 2# is 1-15 parts, is helped
0.05-2 parts of agent.
2. functional ink as described in claim 1, it is characterised in that：The epoxy resin 1# is bisphenol A type epoxy resin,
It is more than one or two kinds of in E03, E06, E10, E12, E14, E20, E31, E35, E39, E42, E44, E51, E55 etc.
Mixture.
3. functional ink as described in claim 1, it is characterised in that：The epoxy resin 2# is phenol aldehyde type epoxy resin,
One or more kinds of mixtures in F51, F48, F44, F47, F43 etc..
4. functional ink as described in claim 1, it is characterised in that：The curing agent is selected from dicyandiamide, biguanides, organic acid
Hydrazides, boron trifluoride-amine complex, boron triflouride-mono aminoethane complex compound, boron trifluoride-benzylamine complex compound, aminimide
（AI）, super coordination silicate（ECSS）, m-phenylene diamine (MPD), alkane diamines, diaminodiphenyl-methane, diaminodiphenylsulfone, hexahydro
Phthalate anhydride, methyl hexahydrophthalic acid anhydride, carbic anhydride（NA）, methylnadic anhydride（MNA）, glutaric anhydride, hydrogen
Change one or more kinds of mixtures in methylnadic anhydride, methylcyclohexene tetracarboxylic dianhydride.
5. functional ink as described in claim 1, it is characterised in that：The accelerating agent is selected from DMP-30（2,4,6- tri-（Two
Methyaminomethyl）Phenol）、BDMA（Benzyl dimethylamine）、DMP-10（Adjacent hydroxybenzyl dimethylamine）, chromium acetylacetonate, levulinic
It is ketone zinc, nickel acetylacetonate, acetylacetone cobalt, benzyltrimethylammonium chloride, triethanolamine borate, triethanol amine titanate, pungent
Sour tin, quaternary alkylphosphonium salts, diazabicylo, benzoyl peroxide, thiocarbamide, 2E4MZ（2-ethyl-4-methylimidazole）, 2- phenylimidazoles
One or more kinds of mixtures in quinoline, 2- benzothiazolyl mercaptans.
6. functional ink as described in claim 1, it is characterised in that：The solvent 1# is selected from acetone, butanone, methyl tert-butyl
One or more kinds of mixtures in base ketone, pentanone, benzene,toluene,xylene, ether, chloroform, hexamethylene.
7. functional ink as described in claim 1, it is characterised in that：The solvent 2# be selected from methanol, ethyl alcohol, ethylene glycol,
Isopropanol, butanol, ethylene glycol monomethyl ether, butyl glycol ether, propylene glycol monomethyl ether, propylene-glycol ethyl ether, propandiol butyl ether, methyl acetate,
Ethyl acetate, butyl acetate, dimethyl carbonate, DBE（The mixing of dimethyl succinate, dimethyl glutarate, dimethyl adipate
Solvent）In one or more kinds of mixtures.
8. prepare the method for functional ink described in claim 1, it is characterised in that：Epoxy resin 1# is crushed into powder last use
Solvent 1# dissolves, and obtains sticky liquid, then is stirred evenly with curing agent, then adds in solvent 2# guarantee systems while stirring and begins
Homogeneous clarified solution eventually, by above-mentioned 50 DEG C of architecture heat preservation and mix slowly 5-24 it is small when, add in epoxy resin 2# thereafter to complete
Fully dissolved adds accelerating agent to being completely dissolved, is eventually adding auxiliary agent.
9. a kind of functional ink of inkjet printable, it is characterised in that：The viscosity number of functional ink is as described in claim 1
5-30mPa.s（25℃）And surface tension is 25-50dyn/cm（25℃）.
10. a kind of ultra-violet curing inkjet printing methods, comprise the following steps：
1）Cleaning：Oil removing, dedusting, drying process are carried out to stock surface；
2）Activate step：Use silane coupling agent（Weight percent 0.1-0.5%）Aqueous solution the stock surface is swashed
It is living；
3）Pre- spray step：Functional ink described in claim 9 is passed through into UV（Ultra-violet curing）Printer is in the stock table
Face printing picture and text and infra-red drying；
4）Ink-jet step：UV inks are cured by UV printers in the stock printout surface picture and text and UV；
5）Curing schedule：The stock that printing finishes is put into 120 DEG C -180 DEG C of baking oven to toast 10-30 minutes.
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| CN201710526185.3A CN108070299A (en) | 2017-06-30 | 2017-06-30 | For the functional ink and preparation method and application of inkjet printing |
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| CN201710526185.3A CN108070299A (en) | 2017-06-30 | 2017-06-30 | For the functional ink and preparation method and application of inkjet printing |
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Cited By (2)
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| CN110183937A (en) * | 2019-06-13 | 2019-08-30 | 四川渝邻汽车零部件有限公司 | A kind of printed liquid of printed coating and the method for preparing printed coating |
| US11787733B2 (en) | 2019-03-06 | 2023-10-17 | Owens-Brockway Glass Container Inc. | Three-dimensional printing of a porous matrix on a container |
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Address after: Room 302, unit 1, building 1, Yuxiang building, Baiyang street, Wuyi County, Jinhua City, Zhejiang Province 321200 Applicant after: Shi Yingying Address before: 321200 11 Lane four lane, Wuyi house, Wuyi, Jinhua, Zhejiang Applicant before: Shi Yingying |
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