CN109504168A - Ink and preparation method thereof - Google Patents

Ink and preparation method thereof Download PDF

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Publication number
CN109504168A
CN109504168A CN201811386769.6A CN201811386769A CN109504168A CN 109504168 A CN109504168 A CN 109504168A CN 201811386769 A CN201811386769 A CN 201811386769A CN 109504168 A CN109504168 A CN 109504168A
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CN
China
Prior art keywords
ink
resin
revolving speed
link stuff
sheet metal
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Granted
Application number
CN201811386769.6A
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Chinese (zh)
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CN109504168B (en
Inventor
邹文格
杜文力
曾德祥
陈章荣
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HUIZHOU FORYOU OPTICAL TECHNOLOGY Co Ltd
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HUIZHOU FORYOU OPTICAL TECHNOLOGY Co Ltd
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Priority to CN201811386769.6A priority Critical patent/CN109504168B/en
Publication of CN109504168A publication Critical patent/CN109504168A/en
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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
    • C09D11/02Printing inks
    • C09D11/10Printing inks based on artificial resins
    • C09D11/102Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
    • C09D11/103Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds of aldehydes, e.g. phenol-formaldehyde resins
    • 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
    • C09D11/02Printing inks
    • C09D11/03Printing inks characterised by features other than the chemical nature of the binder
    • 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
    • C09D11/02Printing inks
    • C09D11/03Printing inks characterised by features other than the chemical nature of the binder
    • C09D11/037Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
    • 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
    • C09D11/02Printing inks
    • C09D11/10Printing inks based on artificial resins
    • C09D11/101Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
    • 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
    • C09D11/02Printing inks
    • C09D11/10Printing inks based on artificial resins
    • C09D11/106Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C09D11/107Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)

Abstract

This application discloses a kind of ink and preparation method thereof, which includes link stuff and sheet metal pigment;The link stuff includes resin compound, and the resin compound includes thermoplastic resin.By the above-mentioned means, the application can enhance the metal effect after ink printing and improve ink stability, reduces and fail due to causing viscosity to increase or solidify agglomeration there is a situation where dark curing self-crosslinking reaction, it is user-friendly.

Description

Ink and preparation method thereof
Technical field
This application involves chemical technology fields, more particularly to a kind of ink and preparation method thereof.
Background technique
Ink with mirror effect is a kind of ink with special-effect, and the printed matter of the ink can obtain mirror effect.It is common Ink with mirror effect classified according to curing mode, there are mainly of two types.One is solvent volatile dry type ink (or for from dry Type), by solvent volatile dry, another kind is ultraviolet light (also known as UV) curing type ink with mirror effect, that is, passes through ultraviolet light Curing and drying.
Relative to self-drying type ink with mirror effect, UV curing type ink with mirror effect is fast with curing rate, is free of solvent or containing only few The advantages of measuring solvent can be improved printing efficiency and reduce volatile organic compounds (VOC) discharge.
However, and resin in current UV curing type ink with mirror effect in link stuff have and carry out ultraviolet light curing reaction Unsaturated group has biggish volume contraction when receiving UV irradiation instantaneous solidification, to influence pigment orientation;On the other hand, Under the action of sheet metal living radical particle, it is anti-to be easy to happen dark curing self-crosslinking chemistry in pigment for resin in link stuff It answers, makes ink in storage and transportational process, be easy to cause viscosity to increase or solidify the failure of agglomeration, so that ink with mirror effect Link stuff and pigment need separately packaging, or need to refrigerate in storage and transportational process, to reduce reactivity, avoid sending out Raw dark curing reaction, causes client inconvenient for use, and increase packed and transported cost.
Summary of the invention
The application is mainly solving the technical problems that provide a kind of ink and preparation method thereof, after capable of enhancing ink printing Metal effect and improve ink stability, reduce due to occur dark curing self-crosslinking reaction and cause viscosity increase or solidification knot Block and the case where fail, it is user-friendly.
In order to solve the above technical problems, the technical solution that the application uses is: providing a kind of ink, the ink packet Containing link stuff and sheet metal pigment;The link stuff includes resin compound, and the resin compound includes thermoplastic resin.
In order to solve the above technical problems, another technical solution that the application uses is: providing a kind of preparation side of ink Method, which comprises link stuff and sheet metal pigment are provided, wherein the link stuff includes resin compound, the resin Mixture includes thermoplastic resin;The sheet metal pigment is mixed with the link stuff, to obtain the ink.
The beneficial effect of the application is: being in contrast to the prior art, the link stuff of the application ink includes thermoplasticity Resin, and thermoplastic resin does not participate in curing reaction, the volume contraction of ink when so as to reduce curing reaction, is conducive to gold Belong to the orientation of sheet metal in piece pigment, to enhance the metal effect after ink printing;Moreover, thermoplastic resin can reduce oil The reactivity of black system is allowed to that the chemical reaction of dark curing self-crosslinking does not occur in storage and transportational process, to reduce oil Ink storage and transportational process in, due to occur dark curing self-crosslinking reaction and cause viscosity increase or solidify agglomeration and failure Situation improves ink stability, and then can be packaged together link stuff and sheet metal pigment, and user is facilitated directly to use.
Detailed description of the invention
In order to more clearly explain the technical solutions in the embodiments of the present application, make required in being described below to embodiment Attached drawing is briefly described, it should be apparent that, the drawings in the following description are only some examples of the present application, for For those of ordinary skill in the art, without creative efforts, it can also be obtained according to these attached drawings other Attached drawing.Wherein:
Fig. 1 is the flow diagram of one embodiment of preparation method of the application ink;
Fig. 2 is the flow diagram of another embodiment of preparation method of the application ink.
Specific embodiment
Below in conjunction with the attached drawing in the embodiment of the present application, technical solutions in the embodiments of the present application carries out clear, complete Site preparation description, it is clear that described embodiments are only a part of embodiments of the present application, rather than whole embodiments.Based on this Embodiment in application, those of ordinary skill in the art are obtained every other under the premise of not making creative labor Embodiment shall fall in the protection scope of this application.
In one embodiment of the application ink, ink includes link stuff and sheet metal pigment.
Ink in present embodiment can be ultraviolet curing type ink with mirror effect, and sheet metal is contained in pigment, thus It can be after being printed using the ink, printed article can be presented mirror effect and have metal sense.
Specifically, the sheet metal in sheet metal pigment can be nanometer aluminum piece, silver strip, nickel sheet, chromium piece etc., can be used true High purity metal aluminium or silver, nickel, chromium etc., i.e., be vaporized on the flexible substrates for being pre-coated with abscission layer, then by empty coating method production It is obtained by processes such as demoulding, cleaning, crushing, surface treatments.
In an application scenarios, sheet metal is micro- aluminium flake, with a thickness of 10nm-50nm, specific such as 10nm, 20nm, 30nm, 40nm, 50nm etc., D50 partial size are 3 μm -50 μm, specific such as 3 μm, 5 μm, 10 μm, 30 μm, 50 μm.
Further, link stuff includes resin compound, and resin compound may include having thermoplastic resin.
In present embodiment, when being solidified using ultraviolet light to ink, the thermoplastic resin in link stuff is not participated in Curing reaction, the volume contraction of ink when so as to reduce curing reaction, is conducive to the orientation of sheet metal, to enhance ink Metal effect after printing.Moreover, thermoplastic resin can reduce the reactivity of ink system, it is allowed to storing and transporting The chemical reaction of dark curing self-crosslinking does not occur in journey, so that ink is reduced in storage and transportational process, since dark curing occurs Self-crosslinking reaction and cause viscosity increase or solidification agglomeration and the case where fail, improve ink stability, and then link stuff and gold Belonging to piece pigment can be packaged together, and user is facilitated directly to use.
Further, in one embodiment, thermoplastic resin has hydroxyl group.
It should be pointed out that with micro- aluminium flake in above-mentioned sheet metal pigment key can occur for the hydroxyl in thermoplastic resin It closes, to promote the orientation of micro- aluminium flake, is conducive to the printing effect for improving ink.
Specifically, in one embodiment, thermoplastic resin can be aldehyde ketone resin, aldehyde resin and thermoplastic acrylic At least one of resin.
Wherein, aldehyde ketone resin (also known as polyketone resin) refers to the thermoplastic resin being polymerized by ketone and aldehydes.This In embodiment, it can be used and obtained by cyclohexanone and formaldehyde through polycondensation reaction.Specifically, the softening point of used aldehyde ketone resin Can be 55 DEG C -130 DEG C, more specifically can be 85 DEG C -115 DEG C, such as 55 DEG C, 65 DEG C, 75 DEG C, 85 DEG C, 95 DEG C, 105 DEG C, 115 DEG C, 125 DEG C, 130 DEG C etc..
Aldehyde resin (also known as urea formaldehyde) refers to based on the polymer resin based on fatty aldehydes.In present embodiment, The softening point of used aldehyde resin is 80 DEG C -110 DEG C, such as 80 DEG C, 90 DEG C, 100 DEG C, 110 DEG C etc..
Thermoplastic acrylic resin refers to the thermoplastic acrylic resin made of acrylic acid, methacrylic polymeric.Tool Body, the glass transition temperature of used thermoplastic acrylic resin can be 40 DEG C -60 DEG C, such as 40 DEG C, 50 DEG C, 60 DEG C.
Thermoplastic resin employed in present embodiment, in addition to that can be bonded with micro- aluminium flake with hydroxyl group Except, also there is appropriate glass transition temperature or softening point, so as to dissolubility, the dispersibility etc. for increasing ink system, thus Further be conducive to showing for the metal effect of ink.
Wherein, in one embodiment, resin compound also includes the first monomer, for molten during preparing ink Thermoplastic resin is solved, so that resin compound becomes flowing, transparent, clear liquid.
Specifically, the first monomer can be 1,6- hexylene glycol double methacrylate (HDDA), tripropylene glycol double methacrylate (TPGDA), two contracting propylene glycol double methacrylates (DPGDA), trimethylolpropane trimethacrylate (TMPTA), dipentaerythritol Five or six acrylate (DPHA), isobornyl acrylate (IBOA), hydroxyethyl methacrylate (HEMA), ethoxy ethoxy second At least one of base acrylate (EOEOEA), pentaerythritol tetraacrylate.
In an application scenarios, in resin compound, the mass percentage of the first monomer is 30%-95%, Such as can be 30%, 45%, 60%, 75%, 95% etc., the mass percentage of thermoplastic resin is 5%-70%, such as It can be 5%, 20%, 35%, 50%, 65%, 70% etc..
Further, in one embodiment, link stuff also includes initiator, second comonomer, solvent, auxiliary agent.
Wherein, initiator is specially photoinitiator, can absorb the energy of certain wavelength in ultraviolet region, generate free radicals, Cation etc., to cause the solidification of ink system polymerization crosslinking.Specifically, initiator can be 2- methyl-1-(4- methylthio phenyl Base) -2- morpholinyl -1- acetone (907), 1- hydroxy-cyclohexyl phenyl ketone (184), 2- hydroxy-methyl phenyl-propane -1- acetone (1173), 2- benzyl -2- dimethylamino -1- (4- morpholinyl phenyl) butanone (369), 2,4,6- trimethylbenzoyl-hexichol Base phosphine oxide (TPO), 2,4,6- trimethylbenzoyl phenyl phosphinic acid ethyl ester (TPO-L), benzoin dimethylether (651), it is bis- (2, 4,6- trimethylbenzoyl) phenyl phosphine oxide (819), benzophenone analog derivative, at least one in tertiary amines aided initiating Kind.
Second comonomer can be HDDA, TPGDA, DPGDA, TMPTA, DPHA, IBOA, HEMA, EOEOEA, pentaerythrite four At least one of acrylate.
Wherein, second comonomer can be the same or different with the first monomer.
Solvent can be at least one of esters, alcohol ethers solvent.
Auxiliary agent may include defoaming agent, levelling agent, in-can stabilizer.
Wherein, defoaming agent can for polysiloxanes, dimethyl silicone polymer, tributyl phosphate, in poly- modified silicon oil extremely Few one kind.
Levelling agent can change for polyether-modified dimethyl silicone polymer, fluorine-carbon modified polyacrylate solution, alkylbenzene At least one of property dimethyl silicone polymer, alkyl-modified poly- methyl alkyl siloxane, silicone diacrylate.
In-can stabilizer can for p-hydroxyanisole, ST-1 (8% 3 (N- nitroso-N-Phenylhydroxylamine) aluminium salt and 92%2- phenolic group ethoxy acrylate), ST-2 (4% 3 (N- nitroso-N-Phenylhydroxylamine) aluminium salt and 96% ethyoxyl list oil Triacrylate), in 701 (2,2,6,6- tetramethyl -4- hydroxy piperidine NO free radicals, 2,6- di-tert-butyl methyl phenol) At least one.
Further, in ink, the mass percentage of resin compound can be 25%-60%, specific such as 25%, 35%, 45%, 55%, 60% etc., the mass percentage of initiator can be 2%-10%, it is specific such as 2%, 4%, 6%, 8%, 10% etc., the mass percentage of second comonomer can be 18%-40%, specifically such as 18%, 28%, 38%, 40%, The mass percentage of solvent can be 0-5%, and specifically such as 0,1%, 2%, 3%, 4%, 5%, the quality percentage of auxiliary agent contain Amount can be 0-6%, and specific such as 0,2%, 4%, 6%, the mass percentage of sheet metal pigment can be 5%-40%, tool Body such as 5%, 15%, 25%, 35%, 40% etc..
Wherein, the specific mass percentage of above-mentioned each substance depending on actual needs, is not specifically limited herein.
In addition, sheet metal pigment employed in present embodiment is aluminium paste, specifically float type mirror surface aluminum paste, can adopt The METALURE Mirrorshine 1006 blocked with love, 1801/1802 etc. of Huizhou City Huayang Optics Technological Co., Ltd, it can To use at least one therein according to specific requirement.
Referring to Fig. 1, Fig. 1 is the flow diagram of one embodiment of preparation method of the application ink, the embodiment Include:
Step S11: link stuff and sheet metal pigment are provided.
Step S12: sheet metal pigment is mixed with link stuff, to obtain ink.
Wherein, link stuff and sheet metal pigment directly can enough be bought, or voluntarily be prepared.
It should be pointed out that ink and link stuff and sheet metal pigment and above-mentioned the application oil in present embodiment Identical in black embodiment, related detailed content please refers to above embodiment, and details are not described herein again.
Similarly, thermoplastic resin is used in the link stuff of present embodiment.Ink is solidified using ultraviolet light When, the thermoplastic resin in link stuff does not participate in curing reaction, so as to reduce the volume contraction of ink, is conducive to sheet metal Orientation, thus enhance ink printing after metal effect.Moreover, the reaction that thermoplastic resin can reduce ink system is living Property, it is allowed to that the chemical reaction of dark curing self-crosslinking does not occur in storage and transportational process, is storing and transporting to reduce ink In the process, it fails due to causing viscosity to increase or solidify agglomeration there is a situation where dark curing self-crosslinking reaction, improves ink Stability, and then link stuff and sheet metal pigment can be packaged together, and user is facilitated directly to use.
Further, referring to Fig. 2, in one embodiment, link stuff can be prepared by the following method:
Step S101: the first monomer is stirred with 200r/min-400r/min revolving speed, thermoplastic resin is added in whipping process Rouge, and 40 DEG C -55 DEG C are heated to, maintain temperature to stablize, it is single to be then stirred first with 700r/min-1500r/min revolving speed The mixture of body and thermoplastic resin is not less than 1.5 hours, after filtering, is cooled to room temperature, obtains resin compound.
Wherein, the additive amount of the first monomer and thermoplastic resin can be mixed according to resin in the above-mentioned ink embodiment of the application Close mass percentage and first monomer and thermoplastic resin quality percentage in the resin mixture of the object in ink Content determines.
In the step, it can be added before thermoplastic resin is added into the first monomer or during or after Heat, wherein heating temperature is specifically as follows 40 DEG C, 45 DEG C, 50 DEG C, 55 DEG C etc.;It is specific to stir revolving speed used by the first monomer It can be 200r/min, 250r/min, 300r/min, 350r/min, 400r/min etc.;It is stirred after thermoplastic resin is added The revolving speed mixed is specifically as follows 700r/min, 900r/min, 1100r/min, 1300r/min, 1500r/min etc.;Thermoplastic is added The time being stirred after property resin is specifically as follows 1.5 hours, 2 hours, 2.5 hours, 3 hours etc., herein without limitation.
Wherein, mixing time after thermoplastic resin is added can as the case may be depending on, for example, by thermoplastic resin It is dissolved completely in the first monomer, and can stop stirring after transparent, clarification, uniform liquid.Further, it can be used Grenadine is filtered 80-300 mesh (being specifically as follows 80 mesh, 100 mesh, 150 mesh, 200 mesh, 250 mesh, 300 mesh etc.), and is being filtered It is cooled to room temperature after the completion, it is spare.
Step S102: stirring second comonomer with 200r/min-400r/min revolving speed, initiator be added in whipping process, And 40 DEG C -55 DEG C are heated to, it maintains temperature constant, is then not less than 1.5 hours with the stirring of 700r/min-1500r/min revolving speed, And be cooled to room temperature, obtain initiator mixture.
Wherein, second comonomer can be according to corresponding in ink in the above-mentioned ink embodiment of the application with the additive amount of initiator Mass percentage in the middle is determined.
In the step, it can be heated before initiator is added into second comonomer or during or after, Wherein, heating temperature is specifically as follows 40 DEG C, 45 DEG C, 50 DEG C, 55 DEG C etc.;Stirring revolving speed used by second comonomer specifically can be with For 200r/min, 250r/min, 300r/min, 350r/min, 400r/min etc.;The revolving speed being stirred after initiator is added It is specifically as follows 700r/min, 900r/min, 1100r/min, 1300r/min, 1500r/min etc.;It is carried out after initiator is added The time of stirring is specifically as follows 1.5 hours, 2 hours, 2.5 hours, 3 hours etc., herein without limitation.
Wherein, be added initiator after mixing time can as the case may be depending on, for example, being completely dissolved by initiator It can stop stirring in the first monomer, and after transparent, clarification, uniform liquid, and further be cooled to room temperature, it is spare.
Step S103: resin compound is added, and in initiator mixture with the progress of 200r/min-400r/min revolving speed Stirring, and solvent and auxiliary agent are added in whipping process, it is then small with 400r/min-700r/min revolving speed progress 0.5 hour -1 When, and maintain temperature not higher than 50 DEG C, it then is cooled to room temperature, obtains link stuff.
Wherein, the additive amount of solvent and auxiliary agent can correspond in ink according in the above-mentioned ink embodiment of the application Mass percentage is determined.
The revolving speed being stirred after resin compound mixing is added in the step, in initiator mixture to be specifically as follows 200r/min, 250r/min, 300r/min, 350r/min, 400r/min etc.;What is be stirred after solvent and auxiliary agent is added turns Speed is to be specifically as follows 400r/min, 500r/min, 600r/min, 700r/min etc.;What addition solvent and auxiliary agent were stirred Time is specifically as follows 0.5 hour, 0.6 hour, 0.7 hour, 0.8 hour, 0.9 hour, 1 hour etc., herein without limitation, can Temperature is maintained 20 DEG C -40 DEG C or 10 DEG C, 20 DEG C, 30 DEG C, 40 DEG C, 50 DEG C etc..
It should be pointed out that it is above-mentioned solvent and auxiliary agent is added during preparing link stuff after be stirred so that Link stuff is obtained to be uniformly dispersed.
Further, step S12 includes:
Step S104: link stuff is stirred with 200-400r/min revolving speed, and sheet metal pigment is added in whipping process, so Afterwards with 400-700r/min revolving speed stirring -1 hour 0.2 hour, maintains temperature to be not higher than 45 DEG C, after filtering, is cooled to room temperature, Obtain ink.
Wherein, when stirring link stuff, revolving speed is specifically as follows 200r/min, 250r/min, 300r/min, 350r/ Min, 400r/min etc.;Be added sheet metal pigment after, revolving speed be specifically as follows 400r/min, 500r/min, 600r/min, 700r/min etc.;Be added after sheet metal pigment time for being stirred can for 0.2 hour, 0.4 hour, 0.6 hour, it is 0.8 small When, 1 hour etc., be not specifically limited herein;After sheet metal pigment is added, temperature specifically can be maintained into 10 DEG C -30 DEG C or 10 DEG C, 20 DEG C, 30 DEG C, 40 DEG C, 45 DEG C etc..
Wherein, sheet metal pigment is added and further (80 can be specifically as follows using 80-200 mesh after stirring, being uniformly dispersed Mesh, 100 mesh, 150 mesh, 200 mesh etc.) grenadine filtering, and be cooled to room temperature after the completion of filtering, to obtain ink.
Wherein, the first monomer, thermoplastic resin, second comonomer, initiator, molten in present embodiment ink preparation method The specific ingredient of agent, auxiliary agent etc. can be identical as in the above-mentioned ink embodiment of the application, and related detailed content please refers to above-mentioned Embodiment, details are not described herein again.
It is further noted that preparing resin compound, initiator mixture and connection in present embodiment When material, it is cooled to room temperature finally, meanwhile, temperature, which is controlled, during preparing link stuff and being dispersed is not higher than 50 DEG C, And when then controlling temperature during preparing ink and being dispersed not higher than 45 DEG C, so as to reduce prepared ink knot Block improves the stability of ink to the probability of failure.
The application above scheme is specifically described below by specific embodiment and comparative example.
Embodiment 1
1) it prepares resin compound: under normal temperature and pressure, by weight, sequentially adding 15 part of three contracting the third two in a stirring kettle Alcohol double methacrylate (TPGDA) and 20 parts of 1,6- hexylene glycol double methacrylates (HDDA), in the stirring bar that revolving speed is 300r/min It is slowly uniformly added into 65 parts of polyketone resins under part, is heated uniformly to 50 DEG C, and maintains temperature constant.Then it is with 1000r/min Revolving speed is dispersed with stirring 2.5 hours, until resin is completely dissolved transparent, clarification, uniform liquid, then using the net of 200 mesh Yarn filtering, is cooled to room temperature spare.
2) initiator mixture: under normal temperature and pressure, by weight, 15 parts of trimethylolpropane tris are added in a stirring kettle Acrylate (TMPTA) and 15 parts of double-five or six acrylate of pentaerythrite (DPHA), while with the stirring of 300r/min revolving speed successively 3.2 parts of 2- methyl-1s-(4- methyl mercapto phenyl) -2- morpholinyl -1- acetone (907) and 1 part 2,4,6- trimethylbenzoyls are added Base-diphenyl phosphine oxide (TPO), is heated to 50 DEG C, and maintains temperature constant, and stirring is then dispersed under 800r/min revolving speed 2.5 hours, until initiator is completely dissolved, transparent, clarification, uniform liquid were cooled to room temperature spare.
3) link stuff is prepared: in above-mentioned steps 2) in obtained initiator mixture, under the revolving speed stirring of 300r/min, 35 parts of resin compound, 0.2 part of in-can stabilizer ST-1,0.6 part of the 4019 (Guangzhou Silok that step 1) obtains is added The defoaming agent of Si Luoke high molecular polymer Co., Ltd), maintain temperature in 35 DEG C, and stir 40 points with 550r/min revolving speed Clock, until being cooled to room temperature after being uniformly dispersed.
4) it prepares ink with mirror effect: being obtained in link stuff in step 3), is added in the case where revolving speed is the stirring condition of 300r/min 30 parts of float type mirror surface aluminum paste 1801, and maintain temperature in 25 DEG C, with 500r/min revolving speed stirring 30 minutes, until being uniformly dispersed Afterwards, 100 mesh filter, and obtain UV curing type ink with mirror effect.
Embodiment 2
1) it prepares resin compound: under normal temperature and pressure, by weight, sequentially adding 30 parts of 1,6- two in a stirring kettle Alcohol double methacrylate (HDDA) and 20 parts of tripropylene glycol double methacrylates (TPGDA), in the stirring bar that revolving speed is 300r/min It is slowly uniformly added into 30 parts of polyketone resins and 20 parts of acrylic resins under part, is heated uniformly to 50 DEG C, and maintains temperature constant.So Be dispersed with stirring 2.5 hours by revolving speed of 1000r/min afterwards, until resin be completely dissolved it is transparent, clarification, uniform liquid, so It is filtered, is cooled to room temperature spare using the grenadine of 200 mesh afterwards.
2) initiator mixture: under normal temperature and pressure, by weight, 15 parts of trimethylolpropane tris are added in a stirring kettle Acrylate (TMPTA), 14 parts of double-five or six acrylate of pentaerythrite (DPHA), while with the stirring of 300r/min revolving speed successively 2 parts of 2- methyl-1s-(4- methyl mercapto phenyl) -2- morpholinyl -1- acetone (907), 0.7 part 2,4,6- trimethylbenzoyls are added Base-diphenyl phosphine oxide (TPO), 2 parts of 1- hydroxy-cyclohexyl phenyl ketones (184) and 0.5 part 2,4,6- trimethylbenzoyls Phenyl-phosphonic acid ethyl ester (TPO-L), is heated to 50 DEG C, and maintains temperature constant, the then dispersion stirring 2.5 under 800r/min revolving speed Hour, until initiator is completely dissolved, transparent, clarification, uniform liquid are cooled to room temperature spare.
3) link stuff is prepared: in above-mentioned steps 2) in obtained initiator mixture, under the revolving speed stirring of 300r/min, 35 parts of resin compound that step 1) obtains are added, 0.3 part of in-can stabilizer ST-1 is added, 0.5 part of Defom is added 6800 [defoaming agents of modest (Shanghai) Chemical Co., Ltd. of moral] maintain temperature in 35 DEG C, and stir 40 points with 550r/min revolving speed Clock, until being cooled to room temperature after being uniformly dispersed.
4) it prepares ink with mirror effect: being obtained in link stuff in step 3), is added in the case where revolving speed is the stirring condition of 300r/min 25 part 1801,5 parts 1802, and maintain temperature in 25 DEG C, with 550r/min revolving speed stirring 30 minutes, until after being uniformly dispersed, 100 Mesh filtering, obtains UV curing type ink with mirror effect.
Embodiment 3
1) it prepares resin compound: under normal temperature and pressure, by weight, sequentially adding 50 parts of 1,6- two in a stirring kettle Alcohol double methacrylate (HDDA) is slowly uniformly added into 50 parts of aldehyde resin in the case where revolving speed is the stirring condition of 300r/min, uniformly 50 DEG C are heated to, and maintains temperature constant.Then it is dispersed with stirring 2.5 hours by revolving speed of 1000r/min, until resin is completely molten Transparent, clarification, uniform liquid are solved, is then filtered, is cooled to room temperature spare using the grenadine of 200 mesh.
2) initiator mixture: under normal temperature and pressure, by weight, 15 parts of trimethylolpropane tris are added in a stirring kettle Acrylate (TMPTA), 13 parts of double-five or six acrylate of pentaerythrite (DPHA), 3 part of two contracting propylene glycol double methacrylate (DPGDA), 2 parts of 2- methyl-1s-(4- methyl mercapto phenyl) -2- morpholinyl -1- is sequentially added while with the stirring of 300r/min revolving speed Acetone (907), 1 part 2,4,6- trimethylbenzoy-dipheny phosphine oxides (TPO) and 2.5 parts of 1- hydroxy-cyclohexyl phenyl first Ketone (184), is heated to 50 DEG C, and maintains temperature constant, then dispersion stirring 2.5 hours, Zhi Daoyin under 800r/min revolving speed Hair agent is completely dissolved, and transparent, clarification, uniform liquid are cooled to room temperature spare.
3) link stuff is prepared: in above-mentioned steps 2) in obtained initiator mixture, under the revolving speed stirring of 300r/min, Be added obtain 34 parts of resin compound of step 1), 0.2 part 701,1 portions of n-propyl acetates of in-can stabilizer, maintain temperature in 35 DEG C, and with 550r/min revolving speed stirring 40 minutes, until being cooled to room temperature after being uniformly dispersed.
4) it prepares ink with mirror effect: being obtained in link stuff in step 3), is added in the case where revolving speed is the stirring condition of 300r/min The float type mirror surface aluminum paste 1006 of 30 parts Eckart GmbH & Co. KG, and maintain temperature in 25 DEG C, it is stirred 30 minutes with 550r/min revolving speed, To after being uniformly dispersed, the filtering of 100 mesh obtains UV curing type ink with mirror effect.
Comparative example 1
1) it prepares resin compound: under normal temperature and pressure, by weight, sequentially adding 18 parts of polyurethane third in a stirring kettle Olefin(e) acid and 10 parts of epoxy acrylic resins are heated uniformly to 50 DEG C under 300r/min stirring condition, and maintain temperature constant. After persistently stirring 0.4 hour, it is cooled to room temperature spare.
2) initiator mixture: under normal temperature and pressure, by weight, it is double that 12.1 parts of 1,6- hexylene glycols are added in a stirring kettle Acrylate (HDDA), 10 parts of five or six acrylate of dipentaerythritol (DPHA) and 13.9 parts of trimethylolpropane trimethacrylates (TMPTA), 2 parts of 2- methyl-1s-(4- methyl mercapto phenyl) -2- morpholinyl -1- is sequentially added while with the stirring of 300r/min revolving speed Acetone (907), 0.7 part 2,4,6- trimethylbenzoy-dipheny phosphine oxides (TPO), 2 parts of 1- hydroxy-cyclohexyl phenyl ketones (184) and 0.5 part 2,4,6- trimethylbenzoyl phenyl phosphinic acid ethyl esters (TPO-L) are heated to 50 DEG C, and maintain temperature permanent Fixed, then dispersion stirring 2.5 hours under 800r/min revolving speed, are completely dissolved initiator, transparent, clarification, uniform liquid After body, it is cooled to room temperature spare.
3) link stuff is prepared: in above-mentioned steps 2) in obtained initiator mixture, under the revolving speed stirring of 300r/min, Resin compound, 0.3 part of in-can stabilizer ST-1,0.5 part of the BYK-307 that step 1) obtains is added, and (German Bi Ke BYK is public The surface modifier of department), maintain temperature at 35 DEG C, and with 550r/min revolving speed stirring 40 minutes, until being cooled to often after being uniformly dispersed Temperature.
4) it prepares ink with mirror effect: being obtained in link stuff in step 3), is added in the case where revolving speed is the stirring condition of 300r/min 25 part 1801,5 parts 1802, and maintain temperature in 25 DEG C, with 550r/min revolving speed stirring 30 minutes, until after being uniformly dispersed, 100 Mesh filtering, obtains UV curing type ink with mirror effect.
Comparative example 2
1) it prepares resin compound: under normal temperature and pressure, by weight, sequentially adding 30 parts of 1,6- two in a stirring kettle Alcohol double methacrylate (HDDA) and 20 parts of tripropylene glycol double methacrylates (TPGDA), in the stirring bar that revolving speed is 300r/min Slow uniform 30 parts of polyketone resins and 20 parts of acrylic resins, are heated to 60 DEG C, and maintain temperature constant under part.Then with 1000r/min be revolving speed be dispersed with stirring 2.5 hours, until resin be completely dissolved it is transparent, clarification, uniform liquid, then adopt It is filtered with the grenadine of 200 mesh.
2) initiator mixture: under normal temperature and pressure, by weight, 15 parts of trimethylolpropane tris are added in a stirring kettle Acrylate (TMPTA) and 14 parts are double-five or six acrylate of pentaerythrite (DPHA), in the revolving speed stirring with 300r/min according to Secondary addition 2 parts of 2- methyl-1s-(4- methyl mercapto phenyl) -2- morpholinyl -1- acetone (907), 0.7 part 2,4,6- trimethylbenzoyls Base-diphenyl phosphine oxide (TPO), 2 parts of 1- hydroxy-cyclohexyl phenyl ketones (184) and 0.5 part 2,4,6- trimethylbenzoyls Phenyl-phosphonic acid ethyl ester (TPO-L), is heated to 60 DEG C, and maintains temperature constant, the then dispersion stirring 2.5 under 800r/min revolving speed Hour, until initiator is completely dissolved, transparent, clarification, uniform liquid.
3) link stuff is prepared: in above-mentioned steps 2) in obtained initiator mixture, under the revolving speed stirring of 300r/min, Be added step 1) obtain 35 parts of resin compound, 0.3 part of in-can stabilizer ST-1, [moral is modest by 0.5 part of Defom 6800 The defoaming agent of (Shanghai) Chemical Co., Ltd.], temperature 60 C is maintained, and with 550r/min revolving speed stirring 40 minutes, until dispersion is equal It is even.
4) it prepares ink with mirror effect: being obtained in link stuff in step 3), is added in the case where revolving speed is the stirring condition of 300r/min The 1802 of 25 parts 1801 and 5 parts, and maintaining temperature is 60 DEG C, with 550r/min revolving speed stirring 30 minutes, until after being uniformly dispersed, The filtering of 100 mesh, obtains UV curing type ink with mirror effect.
Wherein, the mass parts of ink raw materials employed in each embodiment and comparative example are as shown in table 1 below:
Table 1
By UV curing type ink with mirror effect made from the embodiment of the present invention 1-3 and comparative example 1-2, storage stability is carried out respectively The detection of energy, color effects, UV solidification energy and printing performance.
Wherein, the test method of storability are as follows: under normal pressure, ink is put into 60 DEG C of baking oven, baking 8 is small daily When, during which stopping when the viscosity or pull metal effect of ink have significant change takes out and has seen whether viscosity change or agglomeration, And sample preparation monitoring metallic luster effect variation.
The test method of color effects are as follows: ink 350 mesh silk-screen printings, embodiment 2-3 and comparative example in embodiment 1 The KPP proof press sample preparation of 1-2 RK PRINTCOAT INSTRUMENTS company, Britain, by its metal sense of visual observations, i.e., Observe the power for the silvery white brilliant metallic texture that it shows.Wherein, pull metal effect is by strong to weak sequence: 1 grade -2 - 3 grades -4 grades of grade.
The test method of UV solidification energy are as follows: the speed of UV curing is adjusted to 30r/min, is stablized to UV irradiation energy Afterwards, required irradiation energy is fully cured with UV energy meter detection pull.
The test method of printing performance are as follows: under normal temperature and pressure, the ink in embodiment 1 is carried out quickly with Semi-automatic printer Continuous printing, ground are art paper, and pattern is the colored and real block of group, and mesh is 350 mesh, testing of printed sample situation.Embodiment 2-3 The KPP proof press sample preparation that RK PRINTCOAT INSTRUMENTS company is used with the ink in comparative example 1-2, prints 10 respectively It is secondary, observe pull situation.
Specific testing result is as shown in table 2:
Table 2
In above-mentioned temperature tolerance test, by the way of baking oven high-temperature baking accelerated ageing, simulate in practical application for a long time The stability of storage.Comparative example 1 does not use non-reacted inert plastic, and heat resistance is substantially reduced, and comparative example 2 uses high temperature work Skill production, heat resistance and metal effect are substantially reduced.And embodiment 1-3 is all made of thermoplastic resin, ink heat resistance is big Width improves, and metal effect is stablized, and has preferable performance during production and application with formula of the invention, has obtained mutually testing Card.
The foregoing is merely presently filed embodiments, are not intended to limit the scope of the patents of the application, all to utilize this Equivalent structure or equivalent flow shift made by application specification and accompanying drawing content, it is relevant to be applied directly or indirectly in other Technical field similarly includes in the scope of patent protection of the application.

Claims (10)

1. a kind of ink, which is characterized in that the ink includes link stuff and sheet metal pigment;
The link stuff includes resin compound, and the resin compound includes thermoplastic resin.
2. ink according to claim 1, which is characterized in that
The thermoplastic resin has hydroxyl group.
3. ink according to claim 2, which is characterized in that
The thermoplastic resin is at least one of aldehyde ketone resin, aldehyde resin and thermoplastic acrylic resin.
4. ink according to claim 3, which is characterized in that
The softening point of the aldehyde ketone resin is 55 DEG C -130 DEG C;
The softening point of the aldehyde resin is 80 DEG C -110 DEG C;
The glass transition temperature of the thermoplastic acrylic resin is 40 DEG C -60 DEG C.
5. ink according to claim 1, which is characterized in that
The sheet metal pigment includes micro- aluminium flake, micro- aluminium flake with a thickness of 10nm-50nm, D50 partial size is 3 μm -50 μm.
6. ink according to claim 1, which is characterized in that
The resin compound also includes the first monomer;
The mass percentage of first monomer is 30%-95%, and the mass percentage of the thermoplastic resin is 5%- 70%.
7. ink according to claim 6, which is characterized in that
The link stuff also includes initiator, second comonomer, solvent, auxiliary agent;
The mass percentage of resin compound described in the ink is 25%-60%, and the quality percentage of the initiator contains Amount is 2%-10%, and the mass percentage of the second comonomer is 18%-40%, and the mass percentage of the solvent is 0- 5%, the mass percentage of the auxiliary agent is 0-6%, and the mass percentage of the sheet metal pigment is 5%-40%.
8. ink according to claim 6, which is characterized in that
First monomer is 1,6- hexylene glycol double methacrylate, tripropylene glycol double methacrylate, the double propylene of two contracting propylene glycol Acid esters, trimethylolpropane trimethacrylate, five or six acrylate of dipentaerythritol, isobornyl acrylate, methacrylic acid At least one of hydroxyl ethyl ester, ethoxyethoxyethyl acrylate, pentaerythritol tetraacrylate;
The second comonomer is 1,6- hexylene glycol double methacrylate, tripropylene glycol double methacrylate, the double propylene of two contracting propylene glycol Acid esters, trimethylolpropane trimethacrylate, five or six acrylate of dipentaerythritol, isobornyl acrylate, methacrylic acid At least one of hydroxyl ethyl ester, ethoxyethoxyethyl acrylate, pentaerythritol tetraacrylate;
The initiator be 2- methyl-1-(4- methyl mercapto phenyl)-2- morpholinyl-1- acetone, 1- hydroxy-cyclohexyl phenyl ketone, 2- hydroxy-methyl phenyl-propane -1- acetone, 2- benzyl -2- dimethylamino -1- (4- morpholinyl phenyl) butanone, 2,4,6- front three Base benzoyl-diphenyl phosphine oxide, 2,4,6- trimethylbenzoyl phenyl phosphinic acid ethyl ester, benzoin dimethylether, it is bis- (2,4, 6- trimethylbenzoyl) phenyl phosphine oxide, benzophenone analog derivative, at least one of tertiary amines aided initiating;
The solvent is at least one of esters, alcohol ethers solvent;
The auxiliary agent includes defoaming agent, levelling agent, in-can stabilizer;
The defoaming agent is at least one of polysiloxanes, dimethyl silicone polymer, tributyl phosphate, poly- modified silicon oil;
The levelling agent is polyether-modified dimethyl silicone polymer, fluorine-carbon modified polyacrylate solution, alkylbenzene are modified poly- At least one of dimethyl siloxane, alkyl-modified poly- methyl alkyl siloxane, silicone diacrylate;
The in-can stabilizer is p-hydroxyanisole, 8% 3 (N- nitroso-N-Phenylhydroxylamine) aluminium salt and 92%2- phenolic group second Oxygroup acrylate, 4% 3 (N- nitroso-N-Phenylhydroxylamine) aluminium salt and 96% ethyoxyl list oil triacrylate, 2,2,6, At least one of 6- tetramethyl -4- hydroxy piperidine NO free radical, 2,6- di-tert-butyl methyl phenol;
The sheet metal pigment is aluminium paste.
9. a kind of preparation method of ink, which is characterized in that the described method includes:
There is provided link stuff and sheet metal pigment, wherein the link stuff includes resin compound, and the resin compound includes heat Plastic resin;
The sheet metal pigment is mixed with the link stuff, to obtain the ink.
10. preparation method according to claim 9, which is characterized in that the offer link stuff includes:
The first monomer is stirred with 200r/min-400r/min revolving speed, the thermoplastic resin is added in whipping process, and heat To 40 DEG C -55 DEG C, maintains temperature to stablize, first monomer and institute are then stirred with 700r/min-1500r/min revolving speed The mixture of thermoplastic resin is stated not less than 1.5 hours, after filtering, is cooled to room temperature, obtains the resin compound;
With 200r/min-400r/min revolving speed stir second comonomer, initiator is added in whipping process, and be heated to 40 DEG C- It 55 DEG C, maintains temperature constant, is then not less than 1.5 hours with the stirring of 700r/min-1500r/min revolving speed, and be cooled to room temperature, Obtain initiator mixture;
The resin compound is added in the initiator mixture, and is stirred with 200r/min-400r/min revolving speed, And solvent and auxiliary agent are added in whipping process, then with 400r/min-700r/min revolving speed progress -1 hour 0.5 hour, and It maintains temperature to be not higher than 50 DEG C, then is cooled to room temperature, obtains the link stuff;
The sheet metal pigment is mixed with the link stuff, to obtain the ink, comprising:
Stir the link stuff with 200r/min-400r/min revolving speed, and sheet metal pigment be added in whipping process, then with 400r/min-700r/min revolving speed stirs -1 hour 0.2 hour, and temperature is maintained to be not higher than 45 DEG C, after filtering, is cooled to often Temperature obtains the ink.
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