CN101747685A - Composite alcohol water plastic printing ink and preparation method thereof - Google Patents
Composite alcohol water plastic printing ink and preparation method thereof Download PDFInfo
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- CN101747685A CN101747685A CN 200910312353 CN200910312353A CN101747685A CN 101747685 A CN101747685 A CN 101747685A CN 200910312353 CN200910312353 CN 200910312353 CN 200910312353 A CN200910312353 A CN 200910312353A CN 101747685 A CN101747685 A CN 101747685A
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Abstract
The invention discloses composite alcohol water plastic printing ink which comprises the following components in parts by weight: 15 to 45 parts of modified acroleic acid copolymerization resin, 2 to 10 parts of modified aldehyde ketone resin, 2 to 5 parts of dispersants, 8 to 35 parts of pigment, 6 to 10 parts of modified vibrin, 1 to 4 parts of adhesion accelerants and 20 to 40 parts of ethanol. The composite alcohol water plastic printing ink has good safety and printing suitability, and is suitable for different high speed or low speed printing. The printing ink can be directly diluted by water or ethanol in the using process, has no harm to environment and human bodies, is an ideal environmental protection product, and has very considerable market potential.
Description
Technical field
The present invention relates to a kind of printing packaging already the intaglio plate composite inks for plastics, particularly a kind of composite alcohol water plastic printing ink and preparation method thereof of usefulness.
Background technology
In recent years, along with the packaging industry develop rapidly, plastic gravure printing ink market also constantly increases, current China is in the printing of plastics film, gravure has the incomparable distinctive feature in other printshop, particularly should have on food and medicine packing, gorgeous in the color that the food shelf in each emporium, supermarket are being put, packing is novel, a feast for the eyes various food all adopt is plastics intaglio printing packing, the packages printing of these plastics is inseparable with people's life.Simultaneously, because the raising of human consumer's environmental consciousness, they are to the security of packages printing, the feature of environmental protection is extremely paid close attention to, traditional plastic printing ink is oiliness and pure dissolubility, although dissolvent residual has been done strict demand, but also there are injury and the influence of seal back dissolvent residual peculiar smell and the security problems of food that HUMAN HEALTH is produced, receive the concern of country, country put into effect a GB/T10004-2008 standard and the food safety method disabled to the aromatic solvent of similar toluene in the food product pack printing, other developed countries also have relevant environmental protection law to control the release of volatile organic compounds; At present, abroad agricultural byproducts, the food pack printing ink to China's outlet has clear and definite regulation, directly requiring employed printing ink must be water-soluble printing ink, therefore, improve the packages printing quality and become the important channel that commodity improve the market competitiveness and improve added value, along with society more and more pays close attention to the security of food, agricultural-food and daily necessities packing, will be more and more higher also to the requirement of packing.For adapting to the social development demand,, will inevitably require to use " Green Packaging and green printing ink " to manage to reduce pollution and destruction to environment.
Summary of the invention
The objective of the invention is to provide a kind of and can reduce environmental pollution for the deficiency that solves above-mentioned technology, security is good, printability is good, composite alcohol water plastic printing ink of environmental protection and preparation method thereof.
In order to achieve the above object, a kind of composite alcohol water plastic printing ink provided by the invention, it comprises modified acroleic acid copolymer resins, modification aldehyde ketone resin, dispersion agent, pigment, modified polyester resin, adhesion promoter and ethanol, the weight part content that it is characterized in that each component is respectively 15 parts~45 parts of modified acroleic acid copolymer resinses, 2 parts~10 parts of modification aldehyde ketone resins, 2 parts~5 parts of dispersion agents, 8 parts~35 parts of pigment, 6 parts~10 parts of modified polyester resins, 1 part~4 parts of adhesion promoters, 20 parts~40 parts of ethanol.The molecular-weight average of described modified acroleic acid copolymer resins is 8000~100000, and described modified acroleic acid copolymer resins is the polyurethane-modified acrylic acid copolymer resins.Described modified polyester resin is an acrylic ester modified polyester resin.Described ethanol is the ethanol of content 95%; Described dispersion agent is BYK-220S; Described adhesion promoter is the high connection of titanic acid ester agent HW-801.
Selection of pigment of the present invention is an example with the Wuyuan of printing usefulness, white pigment can be selected the titanium dioxide of rutile-type for use, as C.I.Pigment White 6, black pigment can be selected carbon black for use, as C.I.Pigment Black 7, yellow ultramarine can be selected diarylide yellow for use, as C.I.Pigment Yellow 14, red pigment can select for use azo lake red, as C.I.PigmentRed 57:1, blue pigments can be selected phthalocyanine blue for use, as C.I.Pigment Blue 15:4.
A kind of preparation method according to above-mentioned described composite alcohol water plastic printing ink provided by the invention is characterized in that adopting following step:
A), pre-dispersed, modified acroleic acid copolymer resins, modification aldehyde ketone resin, modified polyester resin, dispersion agent, ethanol are joined respectively in the pre-mixing dispersion cylinder by the 1/3-2/3 of formula rate, starting dispersion machine stirs it, the pigment, the adhesion promoter that in whipping process, add formula ratio then gradually, the reinforced back that finishes is opened dispersion machine and is stirred, high speed dispersion is wetting fully so that pigment is carried out, and makes pre-dispersed mill base to be ground;
B), grind to disperse, pre-dispersed mill base is undertaken finely divided by grinding plant, the aggregate that separates pigment with external force makes it to become the fineness≤15 μ m that meet ink technique and require, thereby obtains dispersible pigment color paste;
C), allotment, modified acroleic acid copolymer resins liquid, modification aldehyde ketone resin liquid, modified polyester resin liquid, dispersion agent, the ethanol of remainder are joined in the dispersible pigment color paste, starting high speed dispersor stirs even with abundant dispersing and mixing, and then viscosity, the form and aspect of printing ink are adjusted, thereby reach predetermined specification of quality, make finished product printing ink;
D), purify packing, remove mechanical impurity and coarse grain by filter plant, then packing.
At this, described modified acroleic acid copolymer resins can be the polyurethane-modified acrylic acid copolymer resins, the production method of described polyurethane-modified acrylic acid copolymer resins is to utilize at first that polyether Glycols and vulcabond are synthetic to be had-base polyurethane prepolymer for use as of NCO group, its reaction process as the formula (1):
(n+1) OCN-R-NCO+nHO-R ’ Period H → OCN-(RNHCOOR ' OCONH) nR Tun CO
Utilize decompression that polyether Glycols is distilled, the base polyurethane prepolymer for use as that obtains further reacts with hydroxyl acrylic and generates two ends the end capped polyurethane acroleic acid performed polymer of vinylformic acid is all arranged, its reaction process as the formula (2):
OCN~NCO+2CH
2=CHCOOCH
2CH(CH
3)OH→CH
2=
CHCOOH
2CH(CH
3)OCONH~NHOCOCH(CH
3)CH
2COOCH=CH
2
By above-mentioned reaction formula (2) as can be known, add Propylene glycol monoacrylate and not only play the effect of sealing active-NCO group, but also introduced unsaturated double-stranded key at polyurethane acroleic acid macromolecular chain two ends, thereby under the initiator effect, in 50~100 ℃ scope, the polyurethane acroleic acid performed polymer that obtains again with the monomer acroleic acid polymerization, the polymeric solution that polymerization makes in water medium is the polyurethane-modified acrylic acid copolymer resins.
The polyurethane-modified acrylic acid copolymer resins that the present invention obtains can be used for the production of above-mentioned composite alcohol water plastic printing ink directly as the connection material of printing ink as the modified acroleic acid copolymer resins of selecting.This polyurethane-modified acrylic acid copolymer resins has the good thickening energy, and dispersion suspension performance, flocculating property, adhesive property and film forming properties combine the pure water color ink of formation with pigment, and the printing transfer effect is good, and print speed is fast, lovely luster.
Modified polyester resin of the present invention can be an acrylic ester modified polyester resin, the production method of described acrylic ester modified polyester resin is to be raw material with vinylformic acid, methyl acrylic ester monomer, acrylic ester monomer and vinylbenzene, acrylic ester synthesizing performed polymer under the effect of the two thioesters of the warm and fine chain-transfer agent of initiator azo two isobutyls; Then, select acrylate performed polymer, polyvalent alcohol and polyprotonic acid acrylic ester synthesizing modified polyester resin under the effect of catalyzer Mono-n-butyltin for use; Then, select for use acrylate performed polymer, polyvalent alcohol and polyprotonic acid in 80~100 ℃ scope, to add the catalyzer Mono-n-butyltin and stirred acrylic ester synthesizing modified polyester resin under the effect of catalyzer Mono-n-butyltin 2-5 hour; Zhi Bei acrylic ester modified polyester resin has the advantage of acrylic resin and vibrin concurrently thus, and acrylic ester modified polyester resin that obtains thus and modified acroleic acid copolymer resins have good consistency.
The present invention is owing to adopted above technical scheme, the product of being produced has solved the disadvantage of conventional plastic printing-ink, its quality product reaches external like product quality advanced level, product remove have nontoxic, have no irritating odor, non-corrosiveness, do not fire, outside not quick-fried, the characteristics such as safety in utilization good, concentration is high, viscosity is low, printing adaptability is good, especially have following characteristics:
Tinting strength is good, printing is bright in colour, glossiness is high;
Strong adhesion, China ink layer do not come off, wear resisting property is good;
No blocking under warming phenomenon, clear patterns, full;
Anti-chemical is strong, chance is sour, grease is constant;
Water repelling property is good, heat-resisting water, anti-frozen water;
Nontoxic, tasteless, meet the requirement of current food, agricultural byproducts transition packing.
Applied range of the present invention, thermostability is good, and BOPP, PET, BOPA and K coating (PVDC) film etc. are had good sticking power, all can provide good stripping strength to various composite packaging structures, adapt to the post-treatment requirement of varieties of food items packing, as freezing, boil and boil and high temperature steaming etc.Can also be applicable to various complex methods in addition, compound as dry type, to extrude compound and solvent-free compoundly etc., range of application is very extensive.
Printing ink of the present invention not only security is good, and printability is good, is fit to different high speed or low speed printings.Printing ink is directly water or alcohol dilution in use, there are not harm in the environment and the person, absolute be Green Product, and as solvent or thinner, this ethanol is to use the renewable resources that ferments through farm crop to printing ink provided by the invention with 95% ethanol or edible ethanol; At this, substitute the pure water-base gravure ink used for plastic of Nonrenewable resources with renewable resources; Its market potential is very considerable.
Embodiment
The present invention is further described by the following embodiment.
Embodiment 1:
A kind of composite alcohol water plastic printing ink that present embodiment provides, it comprises modified acroleic acid copolymer resins, modification aldehyde ketone resin, dispersion agent, pigment, modified polyester resin, adhesion promoter and ethanol, the weight part content of each component is respectively 15 parts of modified acroleic acid copolymer resinses, 2 parts of modification aldehyde ketone resins, 2 parts of dispersion agents, 8 parts of pigment, 6 parts of modified polyester resins, 1 part of adhesion promoter, 20 parts of ethanol.The molecular-weight average of described modified acroleic acid copolymer resins is 8000, and described modified acroleic acid copolymer resins is the polyurethane-modified acrylic acid copolymer resins; Described modified polyester resin is an acrylic ester modified polyester resin.Described ethanol is the ethanol of content 95%; Described dispersion agent is BYK-220S; Described adhesion promoter is the high connection of titanic acid ester agent HW-801; Described pigment is selected carbon black for use.
The preparation method of the composite alcohol water plastic printing ink that present embodiment provides, adopt following step:
A), pre-dispersed, modified acroleic acid copolymer resins, modification aldehyde ketone resin, modified polyester resin, dispersion agent, ethanol are joined respectively in the pre-mixing dispersion cylinder by the 1/3-2/3 of formula rate, starting dispersion machine stirs it, the pigment, the adhesion promoter that in whipping process, add formula ratio then gradually, the reinforced back that finishes is opened dispersion machine and is stirred, dispersion is wetting fully so that pigment is carried out, and makes pre-dispersed mill base to be ground;
B), grind to disperse, pre-dispersed mill base is undertaken finely divided by grinding plant, the aggregate that separates pigment with external force makes it to become the fineness≤15 μ m that meet ink technique and require, thereby obtains dispersible pigment color paste;
C), allotment, modified acroleic acid copolymer resins liquid, modification aldehyde ketone resin liquid, modified polyester resin liquid, dispersion agent, the ethanol of remainder are joined in the dispersible pigment color paste, starting high speed dispersor stirs even with abundant dispersing and mixing, and then viscosity, the form and aspect of printing ink are adjusted, thereby reach predetermined specification of quality, make finished product printing ink;
D), purify packing, remove mechanical impurity and coarse grain by filter plant, then packing.
Embodiment 2:
A kind of composite alcohol water plastic printing ink that present embodiment provides, the weight part content of its each component are respectively 45 parts of modified acroleic acid copolymer resinses, 10 parts of modification aldehyde ketone resins, 5 parts of dispersion agents, 35 parts of pigment, 10 parts of modified polyester resins, 4 parts of adhesion promoters, 40 parts of ethanol; Described pigment is selected diarylide yellow for use; The molecular-weight average of described modified acroleic acid copolymer resins is 100000.
Embodiment 3:
The composite alcohol water plastic printing ink that present embodiment provides (redness) comprises the component of the proportioning of following weight part:
30 parts of modified acroleic acid copolymer resinses; 3 parts of modification aldehyde ketone resins; 2 parts of dispersion agents; Select 20 parts of the red red pigments of azo lake for use; 7 parts of modified polyester resins; 1 part of adhesion promoter; 35 parts of ethanol.
The preparation technology of above-mentioned composite alcohol water plastic printing ink is as follows:
(1), the second alcohol and water in will filling a prescription is made mixed solvent in 8: 4 ratio;
(2), the modified acroleic acid copolymer resins is made into resin liquid, modification aldehyde ketone resin, modified polyester resin, adds above-mentioned (1) mixed solvent by weight, is stirred to whole dissolvings with high speed dispersor;
(3), by prescription accurate weighing pigment, dispersion agent, resin liquid, ethanol, adhesion promoter, and pour into respectively successively and disperse in the cylinder, with high speed dispersor blending dispersion 30 minutes;
(4), mixed scuffing of cylinder bore material, grind 3~6 times with sand mill, fineness stops when reaching 15 μ m grinding;
(5), to ground material, completely examine according to country and the every quality and technical index of industry standard;
(6), filter and package the finished product warehouse-in after the assay was approved.
Embodiment 4:
The composite alcohol water plastic printing ink that present embodiment provides (white) comprises the component of the proportioning of following weight part:
30 parts of modified acroleic acid copolymer resinses; 4 parts of modification aldehyde ketone resins; 2 parts of dispersion agents; The titanium dioxide of selecting rutile-type for use is 26 parts of white pigments; 6.5 parts of modified polyester resins; 1.5 parts of adhesion promoters; 30 parts of ethanol
The preparation technology of above-mentioned composite alcohol water plastic printing ink is as follows:
(1), the second alcohol and water in will filling a prescription is made mixed solvent in 3: 5 ratio;
(2), the modified acroleic acid copolymer resins is made into resin liquid, modification aldehyde ketone resin, modified polyester resin, adds above-mentioned (1) mixed solvent by weight percentage, is stirred to whole dissolvings with high speed dispersor;
(3), by prescription accurate weighing pigment, dispersion agent, resin liquid, ethanol, adhesion promoter, and pour into respectively successively in the scuffing of cylinder bore, with high speed dispersor blending dispersion 30 minutes;
(4), mixed scuffing of cylinder bore material, grind 3~6 times with sand mill, fineness stops when reaching 15 μ m grinding;
(5), to ground material, completely examine according to country and the every quality and technical index of industry standard;
(6), filter and package the finished product warehouse-in after the assay was approved.
Embodiment 5:
What present embodiment was described is that described modified acroleic acid copolymer resins is the polyurethane-modified acrylic acid copolymer resins, the production method of described polyurethane-modified acrylic acid copolymer resins is to utilize at first that polyether Glycols and vulcabond are synthetic to be had-base polyurethane prepolymer for use as of NCO group, its reaction process as the formula (1):
(n+1) OCN-R-NCO+nHO-R ’ Period H → OCN-(RNHCOOR ' OCONH) nR Tun CO
Utilize decompression that polyether Glycols is distilled, the base polyurethane prepolymer for use as that obtains further reacts with hydroxyl acrylic and generates two ends the end capped polyurethane acroleic acid performed polymer of vinylformic acid is all arranged, its reaction process as the formula (2):
OCN~NCO+2CH
2=CHCOOCH
2CH(CH
3)OH→CH
2=
CHCOOH
2CH(CH
3)OCONH~NHOCOCH(CH
3)CH
2COOCH=CH
2
Under the fine effect of initiator azo two isobutyls, in 50~100 ℃ scope, the polyurethane acroleic acid performed polymer that obtains again with the monomer acroleic acid polymerization, the polymeric solution that polymerization makes in water medium is the polyurethane-modified acrylic acid copolymer resins.
Embodiment 6:
What present embodiment was described is that described modified polyester resin is an acrylic ester modified polyester resin, the production method of described acrylic ester modified polyester resin is to be raw material with vinylformic acid, methyl acrylic ester monomer, acrylic ester monomer and vinylbenzene, acrylic ester synthesizing performed polymer under the effect of the two thioesters of the warm and fine chain-transfer agent of initiator azo two isobutyls; Then, select for use acrylate performed polymer, polyvalent alcohol and polyprotonic acid in 80~100 ℃ scope, to add the catalyzer Mono-n-butyltin and stirred acrylic ester synthesizing modified polyester resin under the effect of catalyzer Mono-n-butyltin 2-5 hour.
Claims (8)
1. composite alcohol water plastic printing ink, it comprises modified acroleic acid copolymer resins, modification aldehyde ketone resin, dispersion agent, pigment, modified polyester resin, adhesion promoter and ethanol, the weight part content that it is characterized in that each component is respectively 15 parts~45 parts of modified acroleic acid copolymer resinses, 2 parts~10 parts of modification aldehyde ketone resins, 2 parts~5 parts of dispersion agents, 8 parts~35 parts of pigment, 6 parts~10 parts of modified polyester resins, 1 part~4 parts of adhesion promoters, 20 parts~40 parts of ethanol.
2. composite alcohol water plastic printing ink according to claim 1, the molecular-weight average that it is characterized in that described modified acroleic acid copolymer resins is 8000~100000, the modified acroleic acid copolymer resins is the polyurethane-modified acrylic acid copolymer resins.
3. composite alcohol water plastic printing ink according to claim 1 and 2 is characterized in that described modified polyester resin is an acrylic ester modified polyester resin.
4. composite alcohol water plastic printing ink according to claim 1 and 2 is characterized in that described ethanol is the ethanol of content 95%; Described dispersion agent is BYK-220S; Described adhesion promoter is the high connection of titanic acid ester agent HW-801.
5. composite alcohol water plastic printing ink according to claim 3 is characterized in that described ethanol is the ethanol of content 95%; Described dispersion agent is BYK-220S; Described adhesion promoter is the high connection of titanic acid ester agent HW-801.
6. one kind requires the preparation method of described composite alcohol water plastic printing ink according to aforesaid right, it is characterized in that adopting following step:
A), pre-dispersed, modified acroleic acid copolymer resins, modification aldehyde ketone resin, modified polyester resin, dispersion agent, ethanol are joined respectively in the pre-mixing dispersion cylinder by the 1/3-2/3 of formula rate, starting dispersion machine stirs it, the pigment, the adhesion promoter that in whipping process, add formula ratio then gradually, the reinforced back that finishes is opened dispersion machine and is stirred, dispersion is wetting fully so that pigment is carried out, and makes pre-dispersed mill base to be ground;
B), grind to disperse, pre-dispersed mill base is undertaken finely divided by grinding plant, the aggregate that separates pigment with external force makes it to become the fineness≤15 μ m that meet ink technique and require, thereby obtains dispersible pigment color paste;
C), allotment, modified acroleic acid copolymer resins liquid, modification aldehyde ketone resin liquid, modified polyester resin liquid, dispersion agent, the ethanol of remainder are joined in the dispersible pigment color paste, starting high speed dispersor stirs even with abundant dispersing and mixing, and then viscosity, the form and aspect of printing ink are adjusted, thereby reach predetermined specification of quality, make finished product printing ink;
D), purify packing, remove mechanical impurity and coarse grain by filter plant, then packing.
7. the preparation method of composite alcohol water plastic printing ink according to claim 6, it is characterized in that described modified acroleic acid copolymer resins is the polyurethane-modified acrylic acid copolymer resins, the production method of described polyurethane-modified acrylic acid copolymer resins is to utilize at first that polyether Glycols and vulcabond are synthetic to be had-base polyurethane prepolymer for use as of NCO group, its reaction process as the formula (1):
(n+1) OCN-R-NCO+nHO-R ’ Period H → OCN-(RNHCOOR ' OCONH) nR Tun CO
Utilize decompression that polyether Glycols is distilled, the base polyurethane prepolymer for use as that obtains further reacts with hydroxyl acrylic and generates two ends the end capped polyurethane acroleic acid performed polymer of vinylformic acid is all arranged, its reaction process as the formula (2):
OCN-(RNHCOOR ' OCONH) nR Tun CO+2CH2=CHCOOCH2CH (CH3) OH → CH2=
CHCOOH2CH (CH3) OCONH-(RNHCOOR ' OCONH) nR Tun HOCOCH (CH3) CH2COOCH=CH2
Under the fine effect of initiator azo two isobutyls, in 50~100 ℃ scope, the polyurethane acroleic acid performed polymer that obtains again with the monomer acroleic acid polymerization, the polymeric solution that polymerization makes in water medium is the polyurethane-modified acrylic acid copolymer resins.
8. according to the preparation method of claim 6 or 7 described composite alcohol water plastic printing inks, it is characterized in that described acrylic ester modified polyester resin, described production method is to be raw material with vinylformic acid, methyl acrylic ester monomer, acrylic ester monomer and vinylbenzene, acrylic ester synthesizing performed polymer under the effect of the two thioesters of the warm and fine chain-transfer agent of initiator azo two isobutyls; Then, select acrylate performed polymer, polyvalent alcohol and polyprotonic acid acrylic ester synthesizing modified polyester resin under the effect of catalyzer Mono-n-butyltin for use.
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CN114835925A (en) * | 2022-03-22 | 2022-08-02 | 广东宏开新材料科技有限公司 | Aldehyde ketone resin pre-dispersed sand and preparation method thereof |
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Application publication date: 20100623 |