CN107304318A - 3D ink composition for ink-jet printing, ink group and preparation method thereof - Google Patents
3D ink composition for ink-jet printing, ink group and preparation method thereof Download PDFInfo
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- CN107304318A CN107304318A CN201610263448.1A CN201610263448A CN107304318A CN 107304318 A CN107304318 A CN 107304318A CN 201610263448 A CN201610263448 A CN 201610263448A CN 107304318 A CN107304318 A CN 107304318A
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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
- C09D11/40—Ink-sets specially adapted for multi-colour inkjet printing
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/32—Inkjet printing inks characterised by colouring agents
- C09D11/322—Pigment inks
Abstract
The present invention provides a kind of 3D ink composition for ink-jet printing, ink group and preparation method thereof, and composition for ink includes the composition of following parts by weight：45~75 parts of acrylic acid oligomer, 20~45 parts of acrylic monomers, 1~9 part of ultraviolet initiator, 0.2~10 part of auxiliary agent, 0~4 part of colouring agent；One or more of the acrylic acid oligomer in urethane acrylate, polyester acrylate and polyether acrylate；At 25 DEG C, the viscosity of the composition for ink is 25~70cps；At 40~60 DEG C, the surface tension of the composition for ink is 20~35dyn；During at least one temperature in 40~60 DEG C, the viscosity of the composition for ink is 9~14.5cps.The composition for ink composition of the present invention is simple, can extend the service life of printhead, and solidification process is simple, VOC free discharge, and pollution-free, product is without buckling deformation.
Description
Technical field
The present invention relates to printing technique, more particularly to a kind of 3D ink composition for ink-jet printing, ink group and its preparation
Method.
Background technology
3D inkjet technologies are the operation principles according to ink-jet printer, make nozzle chamber under the excitation of data signal
In liquid (moulding material) form drop in moment, and sprayed with certain speed and frequency from nozzle, by specified path
Successively curing molding, finally gives 3D objects.
The moulding material that existing 3D ink-jet printers are carried out used in inkjet printing can be divided into temperature-curable material and UV light is solid
Change the major class of material two, wherein temperature-curable material is mainly the material containing wax, and solid or semisolid wax-like materials are by adding
Heat fusing is changed into fluid-like material and carries out inkjet printing into print-head nozzle, before wax liquor drop sprays from print-head nozzle and fallen on
When on one supporting body, it is solid on intended trajectory that temperature control device drops in wax liquor process of the wax liquor drop with a cooling just sprayed
Change, be superimposed and be solidificated in preceding layer in the same way according to the model data later layer of 3D objects, ultimately form target 3D
Object, but it is larger to be due to that wax is affected by temperature, and especially easily melts in the case of a high temperature, thus cause its application
It is affected.
UV photo-curing materials at least contain photosensitive resin and initiator, and such as European patent EP 1458825B1 discloses one
Kind of radiation-curable composition, wherein comprising it is at least one can UV radiation curings urethane methacrylic resin, at least one wax,
At least one methacrylic acid diluent, at least one light trigger and at least one polymerization initiator, said composition are used to spray
The temperature of composition need to be increased to 70-90 DEG C, composition provides a cooling environment after printhead ejection will during ink printing
The composition material of distribution is changed into solid, carries out the layer that radiation forms 3D objects with UV light afterwards, foregoing step is repeated afterwards
It is rapid to form 3D objects.High temperature is needed it is melted the printing that therefore it is installed in printer Design when being used due to said composition
Head must be able to high temperature resistant, and thus one side high temperature is impacted to the service life of printhead, and another aspect energy consumption is higher, and group
Contain wax and resin material in compound, this is the entirely different material of two class properties, be carried out in two steps in solidification process is carried out,
First passing through cooling makes composition not fully cured, then is further solidified by UV light, and the former is physical process being of the latter
Process, it is complicated that this causes composition to use.
The content of the invention
For above-mentioned technological deficiency, the present invention provides a kind of 3D ink composition for ink-jet printing, ink group and its preparation
Method, the good stability of the 3D objects of composition for ink manufacture, will not be deformed upon, and can drop due to temperature factor
The operating temperature of low printhead, solidification process is simple.
The present invention provides a kind of 3D ink composition for ink-jet printing, includes the composition of following parts by weight：Acrylic acid is oligomeric
45~75 parts of thing, 20~45 parts of acrylic monomers, 1~9 part of ultraviolet initiator, 0.2~10 part of auxiliary agent, 0~4 part of colouring agent；
One or more of the acrylic acid oligomer in urethane acrylate, polyester acrylate and polyether acrylate；
At 25 DEG C, the viscosity of the composition for ink is 25~70cps；At 40~60 DEG C, the composition for ink
Surface tension be 20~35dyn；During at least one temperature in 40~60 DEG C the viscosity of the composition for ink for 9~
14.5cps。
The composition for ink of the present invention is during inkjet printing is carried out, and ultraviolet is radiated at established 3D objects piece
On layer, the ultraviolet initiator induced in composition for ink produces free radical, so as to promote acrylic acid oligomer and acrylic acid list
Polymerisation occurs for body.Wherein, acrylic acid oligomer can strengthen the wearability and pliability of 3D objects, and acrylic monomers can
Quick to occur polymerisation, ultraviolet initiator can induce composition for ink and polymerize under ultraviolet light, work as coloring
Agent consumption is transparent ink composition when being zero.And appropriate auxiliary agent and colouring agent can optimize the printing effect of 3D objects
Really, because increase colorant concentration can reduce volume contraction when composition for ink is used to print 3D objects, but colouring agent is again
Composition for ink can be hindered to occur polymerisation, so as to cause the 3D object mechanical properties decreases of printing, therefore, the weight of colouring agent
4 can not be more than by measuring part, wherein, it is transparent ink composition when colouring agent is 0.
Wherein, acrylic acid oligomer in urethane acrylate, polyester acrylate and polyether acrylate one
Plant or a variety of.When acrylic acid oligomer is the mixture of above-mentioned three kinds of compounds, ratio of the present invention to above-mentioned three kinds of compounds
Example is not limited.
Specifically, the urethane acrylate that the present invention is selected is primarily referred to as the oligomer containing ammonia ester bond (- NHCOO-),
It can form a variety of hydrogen bonds between macromolecular chain, cured film is had excellent wearability and pliability, and elongation at break is high, tool
There is preferably combination property.Can voluntarily prepare, can also be commercially available, the CN9110NS of such as Sartomer, CN963B80,
CN966J75NS, CN985B88, CN991NS, CN9167, CN970A60NS, CN975NS etc., the polyurethane of Taiwan Changxing company
Acrylic acid oligomer 6101,6103,6153-1,6155W, 6185,5104D, DR-U011, DR-U012, DR-U250, DR-U381
Deng, moisten Unicryl R-7162 difficult to understand, sharp high Genomer 1122, Genomer 4297, Greatech GT8010,
Greatech GT8440, Greatech GT-8220, Greatech GT-8270 etc..
The polyester acrylate of the present invention is to be made by low molecular weight polyester glycol through acroleic acid esterification, with low gas
Taste, low irritant, preferable pliability and pigment wettability, can select commercial products such as Sartomer CN2262,
CN2283NS, CN8200, CN8201NS etc., Taiwan Changxing company 6320,6325-100,6327-100,6328,6333-
100th, 6351,6364-1,6372,6382, DR-E850 etc., EB81, EB810 of Qing Te companies etc..
The present invention is it is also an option that the polyether acrylate with good pliability and yellowing resistance, such material is also optional
Select commercially available, amine modified polyether acrylate CN550, CN551 of such as Sartomer, the low viscosity polyethers propylene of Rui Ang companies
Acid esters Genomer 3364, Genomer 3414, Genomer 3497, EBECRYL 81, the EBECRYL 810 of Qing Te companies,
PPG triacrylate M3130 of Gu Di companies etc..
The composition for ink composition of the present invention is simple, does not contain any wax material, can be directly under ultraviolet light
Photocuring is carried out, solidification process is simple.Make the composition for ink to be formed that there is more excellent answer by the selection to composition material
With performance and printing effect, for example, viscosity is 25~70cps at 25 DEG C；Viscosity is 9 during at least one temperature in 40~60 DEG C
~14.5cps, surface tension is 20~35dyn at 40~60 DEG C, so that the composition for ink of the present invention provides more excellent
Printing effect and operation adaptive, especially at 40~60 DEG C, its viscosity can just be reduced to the viscosity for suitably carrying out printing injection,
Therefore the composition for ink requires control at 40~60 DEG C to the temperature tolerance of printhead, the printhead strong without temperature tolerance,
Energy consumption, which can not only be saved, can also effectively extend the service life of printhead.And when being printed for 40~60 DEG C, the ink
The surface tension of water composition as little as 20~35dyn, therefore contribute to the fast shaping of composition for ink, the 3D compositions of generation
Good stability.
Further, viscosity is less than 500cps hyperbranched ball-type propylene when 25 DEG C are included in the acrylic acid oligomer
Acid esters oligomer.For example, hyperbranched ball-type acrylate oligomer can select at least one dendroid as shown in Equation 1 to overspend
Change oligomer, wherein, the A in formula 1 can be acryloxy, methacryloxy, hydroxyl, carboxyl, epoxy radicals, nitrine
At least containing a kind of acryloyl for carrying out photocuring in base, amino, phenyl, ester group, or the higher carbochain of the degree of branching and carbochain
Epoxide or methacryloxy.
[formula 1]
Using the hyperbranched ball-type acrylate oligomer of low viscosity, its globular molecule profile is produced in polymerisation
Steric effect can effectively reduce contraction, therefore, global formation part shrinkage factor is low, and its cubical contraction be less than 5.0%,
Product is without buckling deformation.Meanwhile, hyperbranched ball-type acrylate oligomer can control composition for ink occurring polymerisation
When shrinkage factor, it is to avoid the existing contraction produced when being polymerize using a large amount of monomers, enhance the stability of 3D objects.In this hair
In bright embodiment, 45~75 parts of acrylic acid oligomers, the hyperbranched ball-type acrylic ester compound can be controlled
Parts by weight are 30~60 parts.The presently commercially available viscosity at 25 DEG C is less than 500cps hyperbranched ball-type acrylate oligomer
Product is a lot, the feature ball-type acrylate SPC-1495 of such as Shenzhen Sa Bisi companies, and the polyfunctionality of Sartomer gathers
Esters hyperbranched oligomer CN2302, CN2303 etc., the 6361-100 of Taiwan Changxing company etc..
Further, the acrylic monomers be more preferably selected from monofunctional acrylates' ester, it is bifunctional acrylate, many
One or more in functional group propenoic acid ester and vinyl ethers monomer.
Specifically, monofunctional acrylates' ester of the invention can be alkyl acrylate, with cyclic structure or phenyl ring
(methyl) acrylate of structure etc..Alkyl acrylate can be isodecyl acrylate, commercially available prod such as Taiwan Changxing company
EM219, EM2191, EM309 etc.；Can be lauryl acrylate, commercially available prod such as EM215 in Taiwan Changxing etc.；Can be
Ethoxyethoxy ethyl acrylate, EOEOEA, the EM211 in Changxing of commercially available prod such as DSM N. V. etc..With cyclic structure or
(methyl) acrylate of benzene ring structure can be isobornyl acrylate IBOA, the SR506NS of commercially available prod such as Sartomer, length
Emerging EM70, the IBXA of Osaka chemistry etc.；Can be tetrahydrofuran (methyl) acrylate, the EM214 in commercially available prod such as Changxing,
EM314, SR285, SR203 of Sartomer etc.；Can be phenoxy group acrylate, the 2- Phenoxyethyls in commercially available prod such as Changxing
Acrylate EM210, ethoxyquin phenoxy group acrylate EM2103 etc..
The bifunctional acrylate of the present invention can be propandiols diacrylate, such as propylene glycol diacrylate
(DPGDA), the SR508NS of commercially available prod such as Sartomer, the EM222 in Changxing etc.；Such as tri (propylene glycol) diacrylate
(TPGDA), the SR306NS of commercially available prod such as Sartomer, the EM223 in Changxing etc.；Can be other glycols diacrylates
Ester, such as 1,6- hexanediyl esters (HDDA), the SR238NS of commercially available prod such as Sartomer, the EM221 in Changxing, DSM N. V.
HDDA etc.；Can be the methanol acrylate with heterocycle, such as Tricyclodecane Dimethanol diacrylate, commercially available prod such as sand
SR833S of many agates, the EM2204 in Changxing etc..
The multi-functional acrylate of the present invention includes three-functionality-degree monomer and polyfunctional monomer, wherein three-functionality-degree list
Body can be ethoxyquin trimethylolpropane trimethacrylate (TMPTA), the EM2382 in commercially available prod such as Changxing etc.；Can be third
Aoxidize glycerol tri-acrylate, the EM8327 in commercially available prod such as Changxing etc.；Polyfunctional monomer can be dipentaerythritol 5 third
Olefin(e) acid ester, the SR399LV NS of commercially available prod such as Sartomer；It is worth noting that, polyfunctional monomer is no more than in the present invention
Five degrees of functionality, the 3D object volumes shrinkage factor otherwise printed can be very big, will be more than 20%.
The vinyl ethers monomer of the present invention refers to contain-O-CH=CH2Or-O-CH2- CH=CH2The monomer of structure, can
To be n-butyl glycidyl ether, triethyleneglycol divinylether (DVE-3) etc..
In addition, acrylic monomers of the invention also includes monofunctional acrylates' ester containing special construction, for example
Can be acryloyl morpholine ACMO, 3,3,5- trimethyl-cyclohexane acrylate, the SR420 of commercially available prod such as Sartomer, Changxing
EM2104 etc.；Trimethylolpropane formal acrylate, the Viscoat#200 of commercially available prod such as Osaka chemistry；Can be
Caprolactone grafted propylene acid hydroxyl ester, commercially available prod such as Guangzhou Boxing B-30 etc..
Further, when the acrylic monomers is monofunctional acrylates' ester, bifunctional acrylate, many officials
When can roll into a ball at least two compound in acrylate and vinyl ethers monomer, the change of content at most in the acrylic monomers
The parts by weight of compound are 20~30 parts, and viscosity of the most compound of the content at 25 DEG C is less than 15cps.Pass through control
The content and viscosity of various compounds in acrylic monomers processed, can further control the shrinkage factor of 3D objects.
Further, the colouring agent is selected from the self-dispersion nano-level pigment of white, red, yellow, blueness and black
One kind in mill base.The present invention uses self-dispersion nano-level dispersible pigment color paste to be as colouring agent reason, self-dispersion type nanometer
The surface of level dispersible pigment color paste have passed through chemical modification, therefore, it is possible to prevent pigment from occurring flocculation coagulation, so as to ensure that ink group
The stability of compound.
Colouring agent is selected from self-dispersion nano-level dispersible pigment color paste, specially self-dispersion nano-level inorganic pigment in the present invention
Mill base or self-dispersion nano-level organic pigment mill base, wherein self-dispersion nano-level inorganic pigment color paste can be Chinese whites
Mill base specifically has titanium dioxide, zinc oxide, lithopone, white lead etc., can be that black pigment mill base specifically has carbon black, graphite, oxygen
Change iron black, nigrosine, carbon black etc.；Self-dispersion nano-level organic pigment mill base can be that color pigment mill base specifically has bronze red
(PR21), Lithol Red (PR49：1), paratonere G (PR37), paratonere 171 (PR171), Fast Yellow G (PY1), Chinese husky of common dye R
(PY10), permanent yellow GR (PY13), pigment Yellow 12 9 (PY129), pigment yellow 150 (PY150), pigment yellow 185 (PY185), phthalocyanine
Blue (PB15), indanthrone (PB60) etc..It should be noted that each composition for ink is monochromatic, that is to say, that an ink
A kind of colouring agent of color is comprised only in composition.
Further, the granules of pigments diameter in the self-dispersion nano-level dispersible pigment color paste is less than 500nm, so as to
Effectively reduce the chance that the nozzle of printhead is blocked.
Further, the ultraviolet initiator is that hydrogen-abstraction free radical photo-initiation and/or cracking type free radical light draw
Send out agent；The one kind or many of the hydrogen-abstraction free radical photo-initiation in benzophenone/tertiary amines and thioxanthone/tertiary amines
Kind；The cracking type free radical photo-initiation is in Alpha-hydroxy ketone, α-amido ketone, acylphosphine oxide and oxime esters
One or more.
Ultraviolet initiator can be any compound in the present invention, as long as it can be produced freely under ultraviolet light
Base, induces composition for ink and occurs polymerisation.Wherein, hydrogen-abstraction radical initiator such as benzophenone/tertiary amine, thia
Anthrone/tertiary amines, the preferred ITX of thioxanthone (isopropyl thioxanthone), tertiary amines are aided initiating, are at least contained in structure
One a-H tertiary amine, is the hydrogen donor of hydrogen-abstraction free radical photo-initiation, preferred tertiary amine benzoic ether of the present invention, reactive amines
Deng tertiary amine benzoic ether has N, N- mesitylenic acids ethyl ester, N, N- mesitylenic acid -2- ethylhexyls, benzoic acid two
Methylamino ethyl ester etc.；Reactive amines are the tertiary amine with acryloxy, may participate in cross-linking reaction, there is the reaction in Changxing commercially available prod
Special EBECRYL7100 of type tertiary amine aided initiating 6420, sharp high Genomer 5142, cyanogen etc..In addition, cracking type free radical
Light trigger can be Alpha-hydroxy ketone such as trade name 1173 (2- hydroxy-2-methyl -1- phenylacetones), 184 (1- hydroxyls
Base-phenylcyclohexyl ketone), the product such as 2959 (2- hydroxy-2-methyl -1- are to ethoxy ether phenylacetones)；Can be α-amine
Base ketone such as 907 (2- methyl isophthalic acids-[4- methyl mercaptos phenyl] -2- morpholinyl -1- acetone), 369 (2- benzyl -2- dimethylaminos -
1- (4- morpholinyl phenyls) -1- butanone) etc. product；Can be acylphosphine oxide such as trade name TEPO (2,4,6- trimethyls
Benzoyl-ethyoxyl-phenyl phosphine oxide), TPO (2,4,6- trimethylbenzoy-dipheny phosphine oxide), 819 (it is double (2,
4,6- trimethylbenzoyls) phenyl phosphine oxide) etc. product；The Irgacure OXE 01 of oxime esters such as BASF and
Irgacure OXE 02, its structural formula is respectively
Deng.
Further, one or more of the auxiliary agent in toughener, defoamer, levelling agent and stabilizer.
Wherein, toughener can be 305T, 205N of polycaprolactone trihydroxylic alcohol and polyalcohols product, such as Yi Sheng companies,
Greatech GT8003 of Gu Di companies etc.；Defoamer species is unrestricted, as long as it can eliminate institute in filtering and print procedure
The bubble of generation, it is to avoid the aeration printing fluency of generation, such as selectable defoamer is organic for BYK companies
Silicon and polymer defoamer BYK-088 etc., modified polyorganosiloxane copolymer solution BYK-1798 etc., enlightening is high to disappear without organosilicon
Infusion TEGO Airex 920, TEGO Airex 921 etc.；Levelling agent main function be in order to promote marking ink surface levelling,
The disadvantages such as shrinkage cavity, trace road are reduced, so as to obtain smooth surface；The levelling agent that the present invention is used can be Bi Ke companies
BYK-333, BYK-371, BYK-377 etc.；Stabilizer is that polymerization inhibitor can prevent ink from depositing, it is ensured that during ink storage
Stability, conventional stabilizer can be GENORAD 16, GENORAD 18, GENORAD 20, the GENORAD of Rui Ang companies
22 etc..
The present invention also provides a kind of ink group, and the ink group is at least two in any of the above-described composition for ink
The combination of composition for ink, wherein, the colouring agent containing different colours at least two composition for ink, and it is described not
With color toner, the content of colouring agent meets following relation at least two composition for ink：
White color agents ＞ red stain ＞ blue colorant ＞ yellow colorants ＞ black colorants.
Due to when being printed, it is necessary to composition for ink is put into the ink cartridge of printer, if will beat
The object of print is polychrome, then needs to be respectively put into the composition for ink of multiple different colours into several ink cartridges of printer
In, the composition for ink of multiple different colours now just constitutes ink group.Thus, ink group is at least two different face
The combination of the composition for ink of color.
When carrying out print job using ink group, because the pigment of different colours differs to the degree of absorption of ultraviolet light
Sample, it is black that it, which absorbs UV energy power,>Yellow>Blueness>It is red>White, i.e. black absorption are most strong, and reaction is least filled
Point, so volume contraction is minimum when black ink composition is used to print 3D objects.Ink group while pigment concentration is increased
The color burn of compound, and higher color depth can cause the 3D objects of printing to successively decrease rapidly along direction of illumination light energy,
3D objects top layer shrinks fast, and internal layer shrinks slow, produces larger internal stress, thereby results in the defects such as 3D objects cracking.In order to overcome
Drawbacks described above, when carrying out ink set combinations using the composition for ink of different colours, the white ink composition in ink group
It is black at it that parts by weight of the middle white color agents in its composition for ink need to be more than red stain in red ink composition
Parts by weight of the red stain in its composition for ink need to be more than in parts by weight in water composition, red ink composition
Blue colorant in parts by weight of the blue colorant in its composition for ink in blue ink composition, blue ink composition
Parts by weight in its composition for ink are needed more than yellow colorants in yellow ink composition in its composition for ink
Parts by weight of the yellow colorants in its composition for ink need to be more than black ink combination in parts by weight, yellow ink composition
Parts by weight of the black colorant in its composition for ink in thing.Only meet the ink of the composition for ink of above-mentioned parts by weight
Group, just can guarantee that the 3D object mechanical properties of the polychrome printed are good, be not susceptible to the phenomenons such as fracture layering.
The present invention also provides a kind of preparation method of any of the above-described 3D ink composition for ink-jet printing, including as follows
Step：
1) 45~75 parts of acrylic acid oligomers, 20~45 parts of acrylic monomers and 0.2~10 part of auxiliary agent are well mixed, it is raw
Into the first mixture；Then to 1~9 part of ultraviolet initiator of addition in first mixture until the ultraviolet initiator
Dissolving is complete, generates the second mixture；0~4 part of colouring agent is added into second mixture and is well mixed, generation the 3rd
Mixture；
2) the 3rd mixture is filtered, filtrate is collected, obtains the composition for ink.
After adding a colorant into the second mixture, high speed shear dispersion machine can be used to make to be well mixed, so that
Obtain the 3rd mixture.The preparation method of the present invention just can only be completed by mixing, filtering, simple to operation, be not only contributed to
Stable composition for ink is formed, the liquefaction and injection of composition for ink is also helped, thereby using more facilitating, especially fitted
Share in the printing of 3D objects.
Further, described be filtered into carries out secondary filtration using miillpore filter to the 3rd mixture；Wherein, first
Level filtering use aperture for 0.6 μm of glass fibre membrane, and the second level, which is filtered, uses aperture for 0.2 μm of polypropylene screen (abbreviation PP
Film).
Further, in addition to collected filtrate it is de-gassed processing.The time of control degassing process is not higher than 5h.
The one kind of the mode of operation of degassing process in decompression degassing, atmospheric degasification and heat de-airing, it is preferred that by degassing time control
System is in 1~3h.By being de-gassed processing to composition for ink, making composition for ink, fluency is good in use, will not
Printing is caused to be broken because of the interference of bubble in composition for ink, the formed precision of final influence 3D objects.
The implementation of the present invention, at least has the advantage that：
1st, composition for ink of the invention composition is simple, easy to use, its viscosity at a temperature of at least one in 40~60 DEG C
Just the viscosity of suitable for printing head injection, which can be reduced to, therefore not only save energy consumption can also effectively extend the service life of printhead.
2nd, composition for ink of the invention has a wide range of application, and because of temperature reason shape will not occur for the 3D objects of generation
Become, and volatile organic solvent is not contained in composition for ink, VOC free discharge is pollution-free.Composition for ink is through overspray
Afterwards, only just need to can all it solidify by ultraviolet light, solidification process is simple.
3rd, composition for ink of the invention can be prevented effectively from pigment generation flocculation coagulation, not only ensure that composition for ink
Stability, it also avoid the blocked risk of print-head nozzle.
4th, the 3D body contracts rates using composition for ink and ink the group generation of the present invention are low, and cubical contraction is less than
5%, product is without buckling deformation.
5th, the preparation method of composition for ink of the present invention is simple, it is easy to control, and is assisted without large scale equipment, production cost
It is low.
Embodiment
To make the purpose, technical scheme and advantage of the embodiment of the present invention clearer, below in conjunction with the implementation of the present invention
Example, the technical scheme in the embodiment of the present invention is clearly and completely described, it is clear that described embodiment is the present invention
A part of embodiment, rather than whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art are not having
The every other embodiment obtained under the premise of creative work is made, the scope of protection of the invention is belonged to.
Embodiment 1
The composition for ink of the present embodiment, includes following component according to parts by weight：
Preparation method：
(1) weigh 30 parts of polyesters hyperbranched oligomer CN2302,23.8 parts of simple function urethane acrylate CN975S,
15 parts of 1,6 hexanediol diacrylate SR238NS, 25 parts of 3,3,5- trimethyl-cyclohexane acrylate SR420 and 0.3 part
GENORAD16,0.5g BYK-333 are stirred to each material after being well mixed, generation in glass container using agitator
First mixture；Weigh 1.6 parts of light trigger TPO, 184 2 parts proceed stirring into the first mixture, afterwards to ultraviolet
Light trigger, which is completely dissolved, obtains the second mixture, and the red face of 1.8 parts of bronze reds (PR21) is added in most backward second mixture
High speed shear is carried out in being transferred to after material in the intelligent scattered sand mills of VFF-230 to disperse, and to well mixed, obtains the 3rd mixing
Thing；
(2) the 3rd mixture is carried out after by-pass filtration with 0.6 μm of glass fibre membrane, then carried out with 0.2 μm of PP films
Secondary filtration, obtains filtrate；Then under 0.1MPa vacuums, to filtrate decompression suction filtration 1 hour, the bubble in filtrate is removed,
Finally obtain the red ink composition applied to 3D inkjet printings.
Performance test is carried out to the composition for ink in the present embodiment 1：
1st, the composition for ink in the present embodiment is existed using DV-I digital displays viscosimeter and BZY-1 full-automatic surface tension instruments
Room temperature and viscosity and surface tension at 40 DEG C -60 DEG C of injection temperation are tested.
2nd, using the particle diameter distribution of American-European gram LS900 laser particle size analyzer tested inks compositions；
3rd, the composition for ink of the present embodiment is applied on the 3D photo-curing ink-jet printers of industrial nozzle, and will be ultraviolet
Radiant wavelength is set to 395nm, carries out the test of ink fluency and shaping at 40 DEG C, 50 DEG C and 60 DEG C of injection temperation respectively
The accuracy test of part, the accuracy test mainly reflects that method of testing is by cubical contraction：
Using bottle method, using water as reference, the density p 1 before photosensitive resin solidification is determined at 25 DEG C and its completely solid
Density p 2 after change, is calculated as follows cubical contraction：
Each test result see the table below 1.
Embodiment 2
Preparation method：
The preparation method and embodiment one of the present embodiment ink inside composition are essentially identical, will simply depressurize the time of degassing
It is adjusted to 2 hours, finally obtains the yellow ink composition applied to 3D inkjet printings.
According to method of testing same as Example 1, performance test, test are carried out to the composition for ink in the present embodiment
It the results are shown in Table 1.
Embodiment 3
Preparation method：
The preparation method and embodiment one of the present embodiment ink inside composition are essentially identical, will simply depressurize the time of degassing
It is adjusted to 3 hours, finally obtains the blue ink composition applied to 3D inkjet printings.
According to method of testing same as Example 1, performance test, test are carried out to the composition for ink in the present embodiment
It the results are shown in Table 1.
Embodiment 4
Preparation method：
The preparation method and embodiment one of the present embodiment ink inside composition are essentially identical, simply stand degassing using normal pressure
Processing is de-gassed, the white ink composition applied to 3D inkjet printings is finally obtained.
According to method of testing same as Example 1, performance test, test are carried out to the composition for ink in the present embodiment
It the results are shown in Table 1.
Embodiment 5
Preparation method：
The preparation method and embodiment one of the present embodiment ink inside composition are essentially identical, simply using the side of heat de-airing
Composition for ink temperature is heated to 40-60 DEG C and is de-gassed processing by formula, finally obtains the black ink applied to 3D inkjet printings
Water composition.
According to method of testing same as Example 1, performance test, test are carried out to the composition for ink in the present embodiment
It the results are shown in Table 1.
Embodiment 6
Preparation method：
The preparation method and embodiment one of the present embodiment ink inside composition are essentially identical, simply stand degassing using normal pressure
Processing is de-gassed, the transparent ink composition applied to 3D inkjet printings is finally obtained.
According to method of testing same as Example 1, performance test, test are carried out to the composition for ink in the present embodiment
It the results are shown in Table 1.
Embodiment 7
Preparation method：
The preparation method and embodiment one of the present embodiment ink inside composition are essentially identical, will simply depressurize the time of degassing
It is adjusted to 3 hours, finally obtains the white ink composition applied to 3D inkjet printings.
According to method of testing same as Example 1, performance test, test are carried out to the composition for ink in the present embodiment
It the results are shown in Table 1.
Embodiment 8
Preparation method：
The preparation method and embodiment one of the present embodiment ink inside composition are essentially identical, will simply depressurize the time of degassing
It is adjusted to 2 hours, finally obtains the yellow ink composition applied to 3D inkjet printings.
According to method of testing same as Example 1, performance test, test are carried out to the composition for ink in the present embodiment
It the results are shown in Table 1.
Embodiment 9
Preparation method：
The preparation method and embodiment one of the present embodiment ink inside composition are essentially identical, simply stand degassing using normal pressure
Processing is de-gassed, the transparent ink composition applied to 3D inkjet printings is finally obtained.
According to method of testing same as Example 1, performance test, test are carried out to the composition for ink in the present embodiment
It the results are shown in Table 1.
The performance parameter of each embodiment ink inside composition of table 1
"-" represents that composition for ink is not applied under corresponding temperature and do not tested
As seen from the results in Table 1:
1st, viscosity is respectively less than 70cps to composition for ink of the invention at room temperature, and with its viscosity of the rise of temperature
Significantly reduce, the viscosity of suitable for printing head injection just can be reached during at least one temperature in 40~60 DEG C, therefore need not make
High temperature resistant printhead is used, and can effectively extend the service life of printhead.
2nd, composition for ink surface tension of the invention is moderate, therefore the 3D objects deformation formed in print procedure may
It is relatively low.
3rd, composition for ink shrinkage factor of the invention is low, therefore the 3D object global formation part shrinkage factors being made are low, will not
Generation buckling deformation.
4th, composition for ink fluency of the invention is good, and grain diameter therein is small, therefore, it is possible to ensure composition for ink
Stability, and avoid the generation of print-head nozzle blockage problem in print procedure.
Composition for ink in various embodiments above can constitute the condition that ink set combinations are used, and be first combination of inks
Thing normal injection temperature is identical, next to that in ink group the amount of colouring agent contained by each composition for ink to meet white color agents ＞ red
Chromatic colorant agent ＞ blue colorant ＞ yellow colorants ＞ black colorants；
What the composition for ink in the various embodiments described above may be constructed ink group has embodiment one, embodiment five, embodiment
Seven and embodiment eight in any two or more composition for ink combination；And embodiment two, embodiment three, example IV and reality
Apply any two or more composition for ink combination in example five.
Finally it should be noted that：Various embodiments above is merely illustrative of the technical solution of the present invention, rather than its limitations；To the greatest extent
The present invention is described in detail with reference to foregoing embodiments for pipe, it will be understood by those within the art that：Its according to
The technical scheme described in foregoing embodiments can so be modified, or which part or all technical characteristic are entered
Row equivalent substitution；And these modifications or replacement, the essence of appropriate technical solution is departed from various embodiments of the present invention technology
The scope of scheme.
Claims (14)
1. a kind of 3D ink composition for ink-jet printing, it is characterised in that include the composition of following parts by weight：Acrylic acid oligomer
45~75 parts, 20~45 parts of acrylic monomers, 1~9 part of ultraviolet initiator, 0.2~10 part of auxiliary agent, 0~4 part of colouring agent；Institute
State one or more of the acrylic acid oligomer in urethane acrylate, polyester acrylate and polyether acrylate；
At 25 DEG C, the viscosity of the composition for ink is 25~70cps；At 40~60 DEG C, the table of the composition for ink
Face tension force is 20~35dyn；During at least one temperature in 40~60 DEG C the viscosity of the composition for ink for 9~
14.5cps。
2. composition for ink according to claim 1, it is characterised in that when being included in 25 DEG C in the acrylic acid oligomer
Viscosity is less than 500cps hyperbranched ball-type acrylate oligomer.
3. composition for ink according to claim 2, it is characterised in that the hyperbranched ball-type acrylate oligomer
Parts by weight are 30~60 parts.
4. composition for ink according to claim 1, it is characterised in that the acrylic monomers is selected from simple function group propylene
One or more in acid esters, bifunctional acrylate, multi-functional acrylate and vinyl ethers monomer.
5. composition for ink according to claim 4, it is characterised in that in the multi-functional acrylate, functional group
Degree≤5.
6. composition for ink according to claim 4, it is characterised in that the acrylic monomers is the simple function group third
At least two compounds in olefin(e) acid ester, bifunctional acrylate, multi-functional acrylate and vinyl ethers monomer, institute
The parts by weight for stating the most compound of content in acrylic monomers are 20~30 parts, and the most compound of the content is 25
DEG C when viscosity be less than 15cps.
7. composition for ink according to claim 1, it is characterised in that the colouring agent be selected from white, red, yellow,
One kind in the self-dispersion nano-level dispersible pigment color paste of blueness and black.
8. composition for ink according to claim 7, it is characterised in that in the self-dispersion nano-level dispersible pigment color paste
Granules of pigments diameter is less than 500nm.
9. composition for ink according to claim 1, it is characterised in that the ultraviolet initiator is hydrogen-abstraction free radical
Light trigger and/or cracking type free radical photo-initiation；
The one kind or many of the hydrogen-abstraction free radical photo-initiation in benzophenone/tertiary amines and thioxanthone/tertiary amines
Kind；The cracking type free radical photo-initiation is in Alpha-hydroxy ketone, α-amido ketone, acylphosphine oxide and oxime esters
One or more.
10. composition for ink according to claim 1, it is characterised in that the auxiliary agent be selected from toughener, defoamer,
One or more in levelling agent and stabilizer.
11. a kind of ink group, it is characterised in that the ink group is any described composition for ink in claim 1~10
In at least two composition for ink combination, wherein, the colouring agent containing different colours at least two composition for ink,
And different colours colouring agent content of colouring agent at least two composition for ink meets following relation：
White color agents ＞ red stain ＞ blue colorant ＞ yellow colorants ＞ black colorants.
12. the preparation method of any 3D ink composition for ink-jet printing of claim 1 to 10, it is characterised in that including
Following steps：
1) 45~75 parts of acrylic acid oligomers, 20~45 parts of acrylic monomers and 0.2~10 part of auxiliary agent are well mixed, generation the
One mixture；Then to 1~9 part of ultraviolet initiator of addition in first mixture until the ultraviolet initiator dissolves
Completely, the second mixture is generated；0~4 part of colouring agent is added into second mixture and is well mixed, generation the 3rd is mixed
Thing；
2) the 3rd mixture is filtered, filtrate is collected, obtains the composition for ink.
13. preparation method according to claim 12, it is characterised in that described to be filtered into using miillpore filter to described the
Three mixtures carry out secondary filtration；Wherein, first order filtering uses aperture for 0.6 μm of glass fibre membrane, and the second level is filtered and adopted
With the polypropylene screen that aperture is 0.2 μm.
14. preparation method according to claim 12, it is characterised in that also including being de-gassed place to collected filtrate
Reason.
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| CN201610263448.1A CN107304318B (en) | 2016-04-25 | 2016-04-25 | 3D ink composition for ink-jet printing, ink group and preparation method thereof |
| PCT/CN2016/087019 WO2017185508A1 (en) | 2016-04-25 | 2016-06-24 | 3d ink-jet printing ink composition and ink set, and method for fabrication thereof |
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| CN201610263448.1A CN107304318B (en) | 2016-04-25 | 2016-04-25 | 3D ink composition for ink-jet printing, ink group and preparation method thereof |
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| WO2017185508A1 (en) | 2017-11-02 |
| CN107304318B (en) | 2018-11-20 |
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