CN107502040A - A kind of visible-light curing solvent-free type environment-friendly ink composite - Google Patents
A kind of visible-light curing solvent-free type environment-friendly ink composite Download PDFInfo
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- CN107502040A CN107502040A CN201610422827.0A CN201610422827A CN107502040A CN 107502040 A CN107502040 A CN 107502040A CN 201610422827 A CN201610422827 A CN 201610422827A CN 107502040 A CN107502040 A CN 107502040A
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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
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the 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
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
- C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
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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
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C09D11/107—Printing 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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- 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
The invention discloses a kind of light-curable ink composition, the ink composite includes the component of following parts by weight：Polymerisable monomer, it is oligomer and/or dilution the property parts by weight of monomer 100, the parts by weight of light trigger 0.01 5, the parts by weight of light trigger auxiliary agent 05, the parts by weight of pigment 1 20 and other parts by weight of function additive 0.5 5；Wherein, the light trigger is the one or more in following active compounds under visible light wave range 415nm 780nm laser or monochromatic visible light radiation：Quinones, titanocene complex, iodine salt compounds, sulphur salt compounds and iron arene complexes class compound.The more common uv radiation source of visible light source used in ink composite solidification in the present invention has the advantages that safe, inexpensive.The ink composite of the present invention is free of any volatile organic solvent, and pollutant emission is few, and the bright-coloured light of mass colour, water-fast, chemical-resistance, adhesion performance are excellent.
Description
Technical field
The present invention relates to a kind of light-curable ink composition, and in particular to a kind of visible-light curing solvent-free type environment-friendly ink
Composition.
Background technology
With the continuous enhancing of popular environmental consciousness, many conventionally manufactured fields with certain environment harmfulness are gradually opened
Begin to make the transition to environmentally friendly production mode reform.The chemical raw material essential as printing industry, the safe handling of ink receive more next
More concerns.It is in traditional printing to use solvent-based ink more, wherein containing substantial amounts of volatile organic component, as benzene, toluene,
Dimethylbenzene etc., there is suitable harmfulness to environment, have great threat to the health of producer and user.Therefore, energetically
Develop environmental type ink, eliminate traditional solvent-based ink, become trend of the times and the market demand of industry development
Inevitable outcome.
To adapt to both at home and abroad to the demand of environment-friendly ink, a variety of environment-friendlyink inks, such as the molten ink of alcohol, water-based ink, offset printing
Soybean Oil Ink etc. is developed in succession, and achieves good expection.Wherein, light-curable ink is as a kind of particularly important
One of environment-friendlyink ink, its great advantage be free from solvent, eliminate pollution of the volatile organic components to environment significantly.This
Outside, light-curable ink also have it is safe, system viscosity is small, rheological characteristic is good and the excellent feature of stability, can be widely applied to
The print field that food, medicine, fabric and tableware etc. are in contact with human body.And at present in light-curable ink technology, use solid
Change light source is ultraviolet light (UV), still not fully up to expectations in security and cost of manufacture, limits its application.Therefore, open
The light-curable ink under new type light source is sent out, is applied in actual printing technology, and the printing performance for increasing ink becomes
One urgent problem to be solved.
The content of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of new ink combination for being used to print
Thing, the ink composite solve the existing safety issue using ultraviolet light in the prior art, together by visible-light curing
The laser curing velocity of Shi Suoshu ink composites, wearability, hardness and adhesive force etc. can meet that most of printing types will
Ask.
To achieve the above object, the present invention adopts the following technical scheme that：
A kind of light-curable ink composition, the ink composite include the component of following parts by weight：
Wherein, the light trigger radiates for following laser or monochromatic visible light in visible light wave range 415nm-780nm
Under one or more in active compound：Quinones, titanocene complex, iodine salt compounds, sulphur
Salt compounds and iron arene complexes class compound.
According to the present invention, volatile organic solvent is free of in the composition.
According to the present invention, the quinones is, for example, camphorquinone (CQ).
According to the present invention, the titanocene complex is, for example, fluorinated diphenyl titanocenes (Irgacure 784), double (five
Fluorinated phenyl) titanocenes etc..
According to the present invention, the iodine salt compounds are, for example, triaryl salt compounded of iodine, diaryl group iodized salt, alkyl iodide
Salt etc., preferably diaryl group iodized salt, more preferably 4,4'- dimethyl diphenyl iodine hexafluorophosphate, diphenyl iodine hexafluoro
Phosphate etc.；The sulphur salt compounds are, for example, triaryl sulfonium salts, diaryl sulfosalt, alkyl sulfosalt etc., preferably
Triaryl sulfonium salts, more preferably 3- nitrobenzophenones diphenyl sulphur hexafluorophosphate, 4- chlorphenyl diphenyl sulphur hexafluorophosphates.
According to the present invention, the iron arene complexes class compound is, for example, η 6- isopropylbenzene cyclopentadienyl iron hexafluorophosphates (Irgacure
261)。
According to the present invention, the light trigger is following laser in visible light wave range 415nm-780nm or monochromatic visible
One kind under light radiation in active compound：Quinones, titanocene complex；Or it is the quinones
With the mixture of one or more arbitrary proportions in a kind of and following compounds in the titanocene complex：The iodine
Salt compounds, the sulphur salt compounds and the iron arene complexes class compound.
According to the present invention, the content of the light trigger is preferably 0.05-2 parts by weight, and more preferably 0.1-0.5 is heavy
Measure part.
According to the present invention, the ink composite is mixed to get by the component.Preferably, the ink composite
It is mixed to get by the component.
In the present invention, the ink composite can pass through visible light wave range 415nm-780nm laser or monochromatic visible
Light carries out efficient photocuring.Specifically, the ink composite can in visible light wave range 415nm-780nm laser or monochrome
See that light irradiation lower hardening time is preferably smaller than 5 seconds, be further preferably no larger than equal to 2 seconds.
According to the present invention, the oligomer is unsaturated polyester (UP), epoxy acrylate, urethane acrylate, polyester third
One or more in olefin(e) acid ester, polyether acrylate, pure acrylate, epoxy resin, silicone oligomer.It is highly preferred that
The oligomer is the one or more in unsaturated polyester (UP), epoxy acrylate, urethane acrylate or epoxy resin；Enter
Preferably, the unsaturated polyester (UP) is, for example, GMA (GMA) to one step, and the epoxy acrylate is for example
It is bisphenol-a epoxy acrylate (such as E-51), the epoxy resin is, for example, phenol aldehyde type epoxy resin (such as F-51).
According to the present invention, it is described dilution property monomer be (methyl) acrylic ester compound (such as MMA, BA, IDA, LA,
EHA, TMPTA, TMPTMA, PETA, tetraethylene glycol diacrylate TEGDA, polyethyleneglycol diacrylate PEGDA etc.), vinyl
One kind or more in class compound (such as St, VA, NVP), vinyl ethers compound, epoxy compounds (such as EPOX)
Kind.It is highly preferred that the dilution property monomer is one kind or more in MMA, LA, TMPTA, TMPTMA, TEGDA, PEGDA, EPOX
Kind.
It is further preferred that when the polymerisable monomer only includes oligomer, the oligomer is epoxy acrylate,
E.g. bisphenol-a epoxy acrylate；It is described low when the polymerisable monomer is simultaneously including oligomer with dilution property monomer
Polymers is selected from unsaturated polyester (UP) (such as GMA), epoxy acrylate (such as bisphenol type epoxy acrylic acid
Ester), the one or more in urethane acrylate and epoxy resin (such as phenol aldehyde type epoxy resin), the dilution property monomer choosing
From (methyl) acrylic ester compound (such as MMA, BA, IDA, LA, EHA, TMPTA, TMPTMA, PETA, TEGDA, PEGDA)
With the one or more in epoxy compounds (such as EPOX)；When the polymerisable monomer only includes dilution property monomer, institute
State dilution property monomer be at least one (methyl) acrylic ester compound (such as MMA, BA, IDA, LA, EHA, TMPTA,
TMPTMA, PETA etc.) or at least one (methyl) acrylic ester compound (such as MMA, BA, IDA, LA, EHA, TMPTA,
TMPTMA, PETA etc.) with the mixtures of at least one epoxy compounds (such as EPOX), for example, TMPTMA or EPOX with
TMPTA mixture.
According to the present invention, the light trigger auxiliary agent be secondary-amine compound (such as diethylamine), tertiary amine compounds (such as
Triethylamine, N, N- dimethyl ethyl aminobenzoates etc.), secondary alcohol compounds, one kind in tertiary alcohols compound.Preferably, institute
It is tertiary amine compounds (such as triethylamine, N, N- dimethyl ethyl aminobenzoates etc.) to state light trigger auxiliary agent.Preferably, when described
When light trigger includes camphorquinone, the content of the light trigger auxiliary agent is more than 0 parts by weight and is less than or equal to 5 parts by weight, preferably
0.05-1 parts by weight, more preferably 0.1-0.5 parts by weight；It is described light-initiated when the light trigger does not include quinones
The content of agent aid is 0-5 parts by weight, preferably 0-1 parts by weight, more preferably 0-0.5 parts by weight.
According to the present invention, the pigment can be organic pigment, inorganic pigment and the mixing with two kinds of paint and the above
Thing.The organic pigment is selected from phthalocyanine green, phthalocyanine blue, AZOpigments, diazo pigment, nitroso pigments etc., specific such as paratonere
53 (Pigment Red 53), pigment blue 15 (Pigment Blue 15) or pigment yellow 13 (Pigment Yellow 13) etc..
The inorganic pigment is selected from cadmium yellow, cadmium red, chrome green, barba hispanica etc..The pigment can be any color, including but not limited to red
Color, orange, yellow, green, blueness, purple, and their secondary colour.Preferably, the content of the pigment is 5-15 weight
Part.
According to the present invention, other described function additives include inorganic filler (such as calcium carbonate (preferably nano-calcium carbonate), sulfuric acid
Barium, titanium dioxide, montmorillonite, talcum powder etc.), antioxidant, defoamer (such as ethanol, n-butanol, organo-silicon ester, mineral oil
Deng), wetting agent (such as lecithin, polyamino salt, polyvalent carboxylic acid's salt), in polymerization inhibitor (such as hydroxyanisol, hydroquinones)
One or more.Preferably, other function additives are inorganic filler (such as calcium carbonate (preferably nano-calcium carbonate), barium sulfate, two
Titanium oxide, montmorillonite, talcum powder etc.).
Beneficial effects of the present invention：
1st, the present invention is creatively provided and a kind of can solidified by 415nm-780nm laser or monochromatic visible light first
Ink composite, by selecting specific light trigger so that the material solidification is fast, excellent performance, is completely suitable for more
The requirement of kind printing type, existing ink solidification is avoided using problems such as the securities of ultraviolet light.
2nd, ink composite of the invention is free of any volatile organic solvent, and pollutant emission is few, the bright-coloured light of mass colour,
Water-fast, chemical-resistance, adhesion performance are excellent.
Embodiment
Illustrate embodiments of the present invention below by way of specific instantiation, those skilled in the art can be by this specification
Disclosed content understands other advantages and effect of the present invention easily.The present invention can also pass through different specific embodiment parties
Formula is embodied or practiced, the various details in this specification can also the application based on different aspect, without departing from this hair
Various modifications or alterations are carried out under bright spirit.
Embodiment 1
By the bisphenol-a epoxy acrylate (E-51) of 30 parts by weight, the methyl methacrylate (MMA) of 70 parts by weight,
The camphorquinone (CQ) of 0.1 parts by weight, the triethylamine of 0.1 parts by weight, the paratonere 53 (Pigment Red 53) of 10 parts by weight, 1
The nano-calcium carbonate of parts by weight is uniformly mixed in normal temperature environment, obtains red light cured printing ink composition；The ink group
Compound can solidify under 440nm blueness visible lasers；And the ink composite is free of volatile organic solvent, pollutant emission
Few, the bright-coloured light of mass colour, water-fast, chemical-resistance, adhesion performance are excellent.
Embodiment 2
By the trimethylol-propane trimethacrylate (TMPTMA) of 100 parts by weight, the fluorinated diphenyl of 0.1 parts by weight
Titanocenes, the pigment blue 15 (Pigment Blue 15) of 15 parts by weight, the montmorillonite of 1 parts by weight is stirred in normal temperature environment to be mixed
Close uniformly, obtain blue light cured printing ink composition；The ink composite can solidify under 415nm blueness visible lasers；And institute
State ink composite and be free of volatile organic solvent, pollutant emission is few, the bright-coloured light of mass colour, water-fast, chemical-resistance, attachment
Power excellent performance.
Embodiment 3
The trimethylolpropane trimethacrylate (TMPTA) of 50 parts by weight, the Glycidyl methacrylate of 50 parts by weight is sweet
Grease (GMA), the camphorquinone of 0.1 parts by weight, 4, the 4'- dimethyl diphenyl iodine hexafluorophosphates of 0.25 parts by weight, 5 weight
The pigment yellow 13 (Pigment Yellow 13) of part, the titanium dioxide of 3 parts by weight is uniformly mixed in normal temperature environment, is obtained
To sodium yellow cured printing ink composition；The ink composite can solidify under 475nm blueness visible lasers；And the ink combination
Thing is free of volatile organic solvent, and pollutant emission is few, and the bright-coloured light of mass colour, water-fast, chemical-resistance, adhesion performance are excellent
It is different.
Embodiment 4-9
The ink composite of the present invention is prepared using the method similar with embodiment 1-3, concrete composition and proportioning are shown in Table 1.
The composition and content of the embodiment 4-9 of table 1 ink composite
Embodiment 4-9 ink composite has the performance close with embodiment 1-3 ink.
Claims (10)
1. a kind of light-curable ink composition, it is characterised in that the ink composite includes the component of following parts by weight：
Wherein, the light trigger has to be following under visible light wave range 415nm-780nm laser or monochromatic visible light radiation
One or more in active compound：Quinones, titanocene complex, iodine salt compounds, sulfosalt class
Compound and iron arene complexes class compound.
2. light-curable ink composition according to claim 1, it is characterised in that have in the composition without volatility
Solvent.
3. light-curable ink composition according to claim 1 or 2, it is characterised in that the quinones is, for example,
Camphorquinone (CQ).
Preferably, the titanocene complex is, for example, fluorinated diphenyl titanocenes (Irgacure 784), double (five fluorination benzene
Base) titanocenes etc..
Preferably, the iodine salt compounds are, for example, triaryl salt compounded of iodine, diaryl group iodized salt, alkyl salt compounded of iodine etc., excellent
Select diaryl group iodized salt, more preferably 4,4'- dimethyl diphenyl iodine hexafluorophosphate, diphenyl iodine hexafluorophosphate
Deng；The sulphur salt compounds are, for example, triaryl sulfonium salts, diaryl sulfosalt, alkyl sulfosalt etc., preferably triaryl
Sulfosalt, more preferably 3- nitrobenzophenones diphenyl sulphur hexafluorophosphate, 4- chlorphenyl diphenyl sulphur hexafluorophosphates.
Preferably, the iron arene complexes class compound is, for example, η 6- isopropylbenzene cyclopentadienyl iron hexafluorophosphates (Irgacure261).
4. according to the light-curable ink composition described in claim any one of 1-3, it is characterised in that under the light trigger is
State one kind in active compound under visible light wave range 415nm-780nm laser or monochromatic visible light radiation：Quinone
Class compound, titanocene complex；Or it is a kind of and followingization in the quinones and the titanocene complex
The mixture of one or more arbitrary proportions in compound：The iodine salt compounds, the sulphur salt compounds and
The iron arene complexes class compound.
5. according to the light-curable ink composition described in claim any one of 1-4, it is characterised in that the light trigger contains
Amount is preferably 0.05-2 parts by weight, more preferably 0.1-0.5 parts by weight.
6. according to the light-curable ink composition described in claim any one of 1-5, it is characterised in that the oligomer is insatiable hunger
With polyester, epoxy acrylate, urethane acrylate, polyester acrylate, polyether acrylate, pure acrylate, epoxy
One or more in resin, silicone oligomer.It is highly preferred that the oligomer be unsaturated polyester (UP), epoxy acrylate,
One or more in urethane acrylate or epoxy resin；It is further preferred that the unsaturated polyester (UP) is, for example, methyl
Glycidyl acrylate (GMA), the epoxy acrylate is, for example, bisphenol-a epoxy acrylate (such as E-51), described
Epoxy resin is, for example, phenol aldehyde type epoxy resin (such as F-51).
7. according to the light-curable ink composition described in claim any one of 1-6, it is characterised in that it is described dilution property monomer be
(methyl) acrylic ester compound (such as MMA, BA, IDA, LA, EHA, TMPTA, TMPTMA, PETA, TEGDA, PEGDA),
One kind in vinylic chemical compound (such as St, VA, NVP), vinyl ethers compound, epoxy compounds (such as EPOX)
It is or a variety of.It is highly preferred that the dilution property monomer is one kind in MMA, LA, TMPTA, TMPTMA, TEGDA, PEGDA, EPOX
It is or a variety of.
It is further preferred that when the polymerisable monomer only includes oligomer, the oligomer is epoxy acrylate, such as
It is bisphenol-a epoxy acrylate；When the polymerisable monomer is simultaneously including oligomer with dilution property monomer, the oligomer
Selected from unsaturated polyester (UP) (such as GMA), epoxy acrylate (such as bisphenol-a epoxy acrylate), gather
One or more in urethane acrylate and epoxy resin (such as phenol aldehyde type epoxy resin), the dilution property monomer are selected from (first
Base) acrylic ester compound (such as MMA, BA, IDA, LA, EHA, TMPTA, TMPTMA, PETA, TEGDA, PEGDA) and ring
One or more in oxygen class compound (such as EPOX)；It is described dilute when the polymerisable monomer only includes dilution property monomer
The property released monomer be at least one (methyl) acrylic ester compound (such as MMA, BA, IDA, LA, EHA, TMPTA, TMPTMA,
PETA etc.) or at least one (methyl) acrylic ester compound (such as MMA, BA, IDA, LA, EHA, TMPTA, TMPTMA,
PETA etc.) with the mixtures of at least one epoxy compounds (such as EPOX), for example, TMPTMA or EPOX's and TMPTA
Mixture.
8. according to the light-curable ink composition described in claim any one of 1-7, it is characterised in that the light trigger auxiliary agent
For secondary-amine compound (such as diethylamine), tertiary amine compounds (such as triethylamine, N, N- dimethyl ethyl aminobenzoates etc.), secondary
One kind in alcohol compound, tertiary alcohols compound.Preferably, the light trigger auxiliary agent is tertiary amine compounds (such as three second
Amine, N, N- dimethyl ethyl aminobenzoates etc.).Preferably, when the light trigger includes camphorquinone, the light trigger helps
The content of agent is more than 0 parts by weight and is less than or equal to 5 parts by weight, preferably 0.05-1 parts by weight, more preferably 0.1-0.5 parts by weight；When
When the light trigger does not include quinones, the content of the light trigger auxiliary agent is 0-5 parts by weight, preferably 0-1 weight
Part, more preferably 0-0.5 parts by weight.
9. according to the light-curable ink composition described in claim any one of 1-8, it is characterised in that the pigment can be organic
Pigment (such as phthalocyanine green, phthalocyanine blue, AZOpigments, diazo pigment, nitroso pigments, it is specific such as the (Pigment of paratonere 53
Red 53), pigment blue 15 (Pigment Blue 15) or pigment yellow 13 (Pigment Yellow 13) etc.) or inorganic pigment
(such as cadmium yellow, cadmium red, chrome green, barba hispanica), and with two kinds of paint and the mixture of the above.Pigment can be any color,
Including but not limited to red, orange, yellow, green, blueness, purple, and their secondary colour.
10. according to the light-curable ink composition described in claim any one of 1-9, it is characterised in that other described functions help
Agent includes inorganic filler (such as calcium carbonate (preferably nano-calcium carbonate), barium sulfate, titanium dioxide, montmorillonite, talcum powder), antioxygen
Agent, defoamer (such as ethanol, n-butanol, organo-silicon ester, mineral oil), wetting agent (such as lecithin, polyamino salt, multivalence carboxylic
Hydrochlorate etc.), the one or more in polymerization inhibitor (such as hydroxyanisol, hydroquinones).Preferably, other function additives are nothing
Machine filler (such as calcium carbonate (preferably nano-calcium carbonate), barium sulfate, titanium dioxide, montmorillonite, talcum powder).
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610422827.0A CN107502040A (en) | 2016-06-14 | 2016-06-14 | A kind of visible-light curing solvent-free type environment-friendly ink composite |
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| CN201610422827.0A CN107502040A (en) | 2016-06-14 | 2016-06-14 | A kind of visible-light curing solvent-free type environment-friendly ink composite |
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| CN109181383A (en) * | 2018-09-06 | 2019-01-11 | 左晓玲 | A kind of visible-light curing water paint and preparation method thereof |
| CN110205015A (en) * | 2019-07-09 | 2019-09-06 | 河源轩朗光电科技有限公司 | Reflective coating and its preparation method and application |
| CN110951004A (en) * | 2019-12-04 | 2020-04-03 | 中国科学院化学研究所 | Water-based ink emulsion, water-based ink, and preparation method and application thereof |
| CN111117367A (en) * | 2018-10-30 | 2020-05-08 | 中国科学院化学研究所 | Photosensitive silver-based conductive ink, method for preparing silver conductive structure by using photosensitive silver-based conductive ink and flexible conductive material |
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| CN110951004B (en) * | 2019-12-04 | 2021-12-17 | 中国科学院化学研究所 | Water-based ink emulsion, water-based ink, and preparation method and application thereof |
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Application publication date: 20171222 |
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