CN101993628B - Method for preparing alcohol-soluble bi-component thermophilic digestion-resistant plastic composite gravure printing ink - Google Patents
Method for preparing alcohol-soluble bi-component thermophilic digestion-resistant plastic composite gravure printing ink Download PDFInfo
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- CN101993628B CN101993628B CN200910060332.8A CN200910060332A CN101993628B CN 101993628 B CN101993628 B CN 101993628B CN 200910060332 A CN200910060332 A CN 200910060332A CN 101993628 B CN101993628 B CN 101993628B
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- 239000002131 composite material Substances 0.000 title claims abstract description 44
- 229920003023 plastic Polymers 0.000 title claims abstract description 37
- 239000004033 plastic Substances 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 35
- 230000029087 digestion Effects 0.000 title abstract 4
- 238000007646 gravure printing Methods 0.000 title abstract 3
- 238000007639 printing Methods 0.000 claims abstract description 71
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 230000008569 process Effects 0.000 claims abstract description 28
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000000203 mixture Substances 0.000 claims abstract description 17
- 239000000049 pigment Substances 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 15
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 10
- 229920005906 polyester polyol Polymers 0.000 claims abstract description 10
- 229920000570 polyether Polymers 0.000 claims abstract description 10
- -1 polypropylene Polymers 0.000 claims abstract description 3
- 238000002360 preparation method Methods 0.000 claims description 34
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical class CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 31
- 238000009835 boiling Methods 0.000 claims description 17
- 150000001412 amines Chemical class 0.000 claims description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- 239000012046 mixed solvent Substances 0.000 claims description 12
- 229920005989 resin Polymers 0.000 claims description 12
- 239000011347 resin Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- 239000004576 sand Substances 0.000 claims description 10
- 239000006185 dispersion Substances 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 238000010792 warming Methods 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 238000004821 distillation Methods 0.000 claims description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 5
- 238000003556 assay Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000009413 insulation Methods 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 238000003801 milling Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000012856 packing Methods 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 5
- 238000009472 formulation Methods 0.000 claims description 4
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical group CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 claims description 2
- 239000012752 auxiliary agent Substances 0.000 claims description 2
- SYECJBOWSGTPLU-UHFFFAOYSA-N hexane-1,1-diamine Chemical compound CCCCCC(N)N SYECJBOWSGTPLU-UHFFFAOYSA-N 0.000 claims description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 2
- 229920000768 polyamine Polymers 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims description 2
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 abstract description 11
- 239000003822 epoxy resin Substances 0.000 abstract description 10
- 229920000647 polyepoxide Polymers 0.000 abstract description 10
- 239000007822 coupling agent Substances 0.000 abstract description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052782 aluminium Inorganic materials 0.000 abstract description 3
- 238000004132 cross linking Methods 0.000 abstract description 3
- 239000011888 foil Substances 0.000 abstract description 3
- 229920000728 polyester Polymers 0.000 abstract 2
- 229920005862 polyol Polymers 0.000 abstract 2
- 150000003077 polyols Chemical class 0.000 abstract 2
- 239000004743 Polypropylene Substances 0.000 abstract 1
- 238000005266 casting Methods 0.000 abstract 1
- 125000005442 diisocyanate group Chemical group 0.000 abstract 1
- 239000012948 isocyanate Substances 0.000 abstract 1
- 150000002513 isocyanates Chemical class 0.000 abstract 1
- 229920001155 polypropylene Polymers 0.000 abstract 1
- 231100000331 toxic Toxicity 0.000 abstract 1
- 230000002588 toxic effect Effects 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- 238000005187 foaming Methods 0.000 description 9
- 230000007613 environmental effect Effects 0.000 description 6
- 239000004814 polyurethane Substances 0.000 description 6
- 229920002635 polyurethane Polymers 0.000 description 6
- 238000010025 steaming Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000010411 cooking Methods 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- 150000002148 esters Chemical group 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 239000002390 adhesive tape Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000002939 deleterious effect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 238000004659 sterilization and disinfection Methods 0.000 description 3
- 230000001988 toxicity Effects 0.000 description 3
- 231100000419 toxicity Toxicity 0.000 description 3
- OSNILPMOSNGHLC-UHFFFAOYSA-N 1-[4-methoxy-3-(piperidin-1-ylmethyl)phenyl]ethanone Chemical compound COC1=CC=C(C(C)=O)C=C1CN1CCCCC1 OSNILPMOSNGHLC-UHFFFAOYSA-N 0.000 description 2
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 2
- 235000017491 Bambusa tulda Nutrition 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 2
- 239000004705 High-molecular-weight polyethylene Substances 0.000 description 2
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 2
- 125000005594 diketone group Chemical group 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 235000010215 titanium dioxide Nutrition 0.000 description 2
- 241000209128 Bambusa Species 0.000 description 1
- 241001330002 Bambuseae Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- OWIKHYCFFJSOEH-UHFFFAOYSA-N Isocyanic acid Chemical compound N=C=O OWIKHYCFFJSOEH-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-N anhydrous cyanic acid Natural products OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- RFAFBXGYHBOUMV-UHFFFAOYSA-N calcium chromate Chemical compound [Ca+2].[O-][Cr]([O-])(=O)=O RFAFBXGYHBOUMV-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002070 germicidal effect Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000012463 white pigment Substances 0.000 description 1
Landscapes
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
The invention discloses a method for preparing alcohol and water-soluble bi-component thermophilic digestion-resistant plastic composite gravure printing ink. The alcohol and water-soluble bi-component thermophilic digestion-resistant plastic composite gravure printing ink consists of component A printing ink and component B curing agent with a mass ratio of 18 to 50:1, wherein the component A printing ink is prepared from diisocyanate, polyether polyol (or polyester polyol or a mixture of the polyether polyol and the polyester polyol), a solvent, a pigment and an auxiliary according to a specific process; and the component B curing agent is mainly prepared from an epoxy resin or a coupling agent or a mixture of the epoxy resin and the coupling agent. Both the printing ink and the curing agent prepared by the method of the invention are alcohol and water soluble, do not contain toxic isocyanate (-NCO) groups, do not pollute environment and products, are economic and environmentally friendly, have high adaptability to a printing environment, and can be used in a damp environment; and by a cross linking reaction between the components A and B, high thermophilic digestion resistance can be guaranteed, and the printing ink is mainly used for the printing of polyester (PET) films, NY films and the like which require high-temperature resistance, the adhesion of the printing ink is high, the printing ink can be compounded with aluminum foils, casting polypropylene (CPP) films and the like, and after being sterilized by digesting at the temperature of between 100 and 135 DEG C for 30 minutes, a printed product is not discolored and foamed, and a compound layer is not separated.
Description
Technical field
The present invention relates to plastic rotogravure composite ink, particularly alcohol-soluble bicomponent high-temperature boiling resistant plastic rotogravure composite ink and preparation method thereof.
Technical background
In recent years,, not only driven the growth at full speed of packaging industry, also promoted the continuous development in plastics base gravure ink technology and market along with the continuous lifting of living standards of the people.The plastics base gravure ink has obtained to use very widely in plastic wrapping at present, and like all types of plastic film substrate packing in industries such as food, medicine, agricultural byproducts, daily necessities, its range of application has almost been included all packaging fields.For adapting to the pursuit of social development to " green and environmental protection "; Plastics base gravure ink enterprise and correlative study mechanism are devoted to the research and development of " environmental protection " printing ink in recent years always; Substitute traditional benzene soluble ink in the hope of dissolving printing ink, thereby alleviate to the pollution of environment with to the threat of HUMAN HEALTH with cleanliness without any pollution/oligosaprobic alcohol-soluble and water-soluble or alcohol.The pure water-based compound oil ink that is used for intaglio plate is disclosed like number of patent application CN200610022514.2; Number of patent application CN200510044632.9 discloses a kind of environment protection plastic printing ink and preparation method thereof, and intaglio plate carton Preprinted ink and paper that number of patent application CN200410012541.2 and CN200610020124.1 then disclose pure dissolubility respectively stamp gloss oil.These printing ink are compared with traditional benzene dissolubility plastics base gravure ink, have good environment-friendly advantage.
As one of important kind of plastic food packing, high-temperature retort bag can carry out germicidal treatment under the condition of high temperature, and it is fresh-keeping that packed article more is prone to, and therefore the quality guaranteed period also becomes longer.The above advantage that high-temperature retort bag has is taken the course of its own it in plastic wrapping industry, obtained wide development space.According to the pertinent data statistics, the consumption of high temperature steaming packing bag in recent years increases sharply with the speed in every year nearly 20%.The high temperature steaming packing has higher requirement to employed printing-ink on it.The plastic rotogravure composite ink of high-temperature boiling resistant also must can be at 30 minutes cooking disinfection of 100～130 ℃ of high temperature tolerances and nondiscoloration, non-foaming except that possessing good printing adaptability and attachment fastness, and composite bed does not separate.
It is main with the two component polyurethane compound oil ink mainly that present high temperature steaming is packed used high-temperature boiling resistant plastic rotogravure composite ink.Host A component is the polyurethane ink of hydroxyl, and solidifying agent B component is the polyurethane oligomer that contains isocyanate groups.Since the A component need through its polyurethane molecular chain institute hydroxyl with the B component reaction, contain hydroxyl solvent (alcohols or water) like system, then can obviously influence solidification effect, so A component printing ink normally used be higher benzene class and ketones solvent of toxicity; Because the existence of isocyanate groups makes the B component have very big toxicity; Isocyanic acid acid esters group is very active group in addition, and the compound that is prone to contain with water and other reactive hydrogen at normal temperatures reacts, so this component is stable very poor, difficult storage, and to environmental factors (like humidity etc.) sensitivity.Above factor directly causes the toxicity of traditional double part polyurethane compound oil ink high, big to the pollution of environment, and printing adaptability is poor.For avoiding the weak point of above-mentioned prior art, the present invention provides a kind of preparation method of alcohol-soluble bicomponent high-temperature boiling resistant plastic rotogravure composite ink, and its A, B component are alcohol-soluble and water-soluble; (NCO) group is to environment, goods are pollution-free, economic environmental protection not contain deleterious isocyanic ester; And the flexibility to printing environment is better; Can use in a humid environment, can satisfy packaging industry, can obtain ideal printing and composite effect the plastics packed print request of high-temperature boiling resistant.
Summary of the invention
The object of the present invention is to provide a kind of alcohol-soluble and water-soluble two-pack plastic rotogravure composite ink and preparation worker method thereof.This alcohol-soluble and water-soluble two-pack high-temperature boiling resistant plastic rotogravure composite ink is made up of A component printing ink and B component solidifying agent; Be alcohol-soluble and water-soluble; (NCO) group is to environment, goods are pollution-free, economic environmental protection not contain deleterious isocyanic ester; And the flexibility to printing environment is better, can use in a humid environment; Through the crosslinking reaction between the two-pack; The good heat-resistance cooking characteristic can be provided, be mainly used in the printing of the PET film, NY film etc. of high temperature resistant needs, the printing ink attachment fastness is good; But clad aluminum foil, CPP film etc.; Cooking disinfection is 30 minutes under high temperature (100～135 ℃) condition, printing nondiscoloration, non-foaming, and composite bed does not separate.
The objective of the invention is to realize through following technical scheme:
Alcohol-soluble and water-soluble two-pack plastic rotogravure composite ink according to the invention is made up of A component printing ink and B component solidifying agent, and both mass ratioes are 18～50: 1.Said A component printing ink is prepared from by the special process process by vulcabond, polyether glycol or polyester polyol or both mixtures, solvent, pigment, auxiliary agent.Wherein each raw material composition weight ratio is following:
10～30 parts of vulcabond
70～90 parts in polyether glycol or polyester polyol or both mixtures
8～16 parts of hexanes
4～9 parts of Virahols
5～10 parts in acetone
3～9 parts of amine
115～250 parts of ethanol
80～100 parts of pigment
2～5 parts of dispersion agents
0～1 part in wax powder
Preparation process in the such scheme specific technological process below being:
(1) preparation performed polymer: vulcabond, polyether glycol or polyester polyol or both mixtures, hexane are added reaction kettle in proportion, slowly be warming up to 75 ℃, insulation reaction is 1.0～1.5 hours then; In 0.5 hour, temperature is risen to 100 ℃ subsequently, after 3.0～6.0 hours, be cooled to 50 ℃ in this thermotonus;
(2) preparation Schiff's base: in another reaction kettle, add hexane, Virahol, acetone, amine in proportion successively, while stirring the cooling, make its after 3 hours temperature less than 25 ℃;
(3) polyreaction: the prepolymer of technological process (1) preparation was joined in 4～6 minutes in the reaction kettle of technological process (2) preparation Schiff's base, and stir fast, make its uniform mixing, the cooling of water flowing simultaneously kept room temperature reaction 5～30 minutes;
(4) distillation: reaction mass heated to 70～130 in the technological process (3) ℃ with solvent distillation, after recovered solvent amount to be distilled reaches requirement, are stopped heating, cool off after 5 minutes, adding ethanol is mixed with the resin solution that solid content is 50wt%;
(5) ink formulation: the ethanol and the water that water cut are not higher than 5wt% are processed mixed solvent in 9: 1～2: 1 ratio; Resin solution and pigment, dispersion agent, wax powder and the mixed solvent of technological process (4) preparation are added blender loader, stirred 20～30 minutes, it is mixed with high speed dispersor; The material that mixes is taken out, send into sand mill and carry out sand milling, treat to take out after fineness is lower than 10 microns, filter; Through after the assay was approved, pack, promptly make the A component printing ink of alcohol-soluble bicomponent high-temperature resistance plastice gravure composite printing ink.Wherein during A component ink formulation each raw material to form weight ratio following:
30～35 parts of resin solutions
30～35 parts of mixed solvents
30～35 parts of pigment
1～3 part of dispersion agent
0～1 part in wax powder
Wherein: vulcabond is different Buddhist diketone vulcabond (IPDI) or tolylene diisocyanate (TDI); Amine is organic amine, like quadrol, hexanediamine, triethylamine, polyethylene polyamine etc., and the amine of above organic amine for recommending to use, but be not limited only to above-mentioned organic amine in actual the use; Pigment is resistant to elevated temperatures pigment; Select Rutile type Titanium Dioxide for use like white pigment, black pigment is selected carbon black for use, and yellow ultramarine is selected for use benzidine yellow G and benzidine yellow 10G to piece together and used; Redness is selected lithol that dark red 243 for use; Blueness selects for use the phthalein mountain valley with clumps of trees and bamboo blue, with the paint is to recommend to use pigment, but is not limited only to above-mentioned pigment in actual the use; The wax powder is a ultra high molecular weight polyethylene wax.
Said B component solidifying agent is dissolved in Virahol by epoxy resin or coupling agent or both mixtures and makes.Wherein each raw material composition weight ratio of B component solidifying agent is following:
0～75 part of epoxy resin
0～75 part of coupling agent
0～75 part of Virahol
Corresponding process for preparation is: with epoxy resin or coupling agent or both mixtures adding reaction kettle, add Virahol then earlier, stir and be warming up to 30～40 ℃, the system dissolving is mixed; After being cooled to room temperature, promptly making solid content is the B component solidifying agent of 75wt%.Wherein: epoxy resin is EP828 type epoxy resin; Coupling agent is a KH560 type organo-silicon coupling agent.
Before the printing by mass ratio be 18～50: 1 A component printing ink and B component solidifying agent directly mixed after, filtration promptly makes the plastic rotogravure composite ink that can satisfy the high-temperature boiling resistant requirement.
Alcohol-soluble and water-soluble two-pack high-temperature boiling resistant plastic rotogravure composite ink of the present invention is compared with traditional two component polyurethane printing ink; Biggest advantage is that component A, B are alcohol-soluble and water-soluble; (NCO) group is to environment, goods are pollution-free, have green environmental protection not contain deleterious isocyanic ester; And the flexibility to printing environment is better, can use in a humid environment; The preparation method is simple, through the crosslinking reaction between the two-pack, the good heat-resistance cooking characteristic can be provided.Can be used for that the PET film of high temperature resistant needs is arranged, the printing of NY film; The printing ink attachment fastness is good; Ability clad aluminum foil, CPP film, cooking disinfection is 30 minutes under high temperature (100～135 ℃) condition, printing nondiscoloration, non-foaming; Composite bed does not separate, and has broad application prospects in high-temperature boiling resistant plastic rotogravure composite ink field.
Embodiment:
Embodiment one
(1) with 80 parts of (weight ratio, as follows) polyether Glycols, 20 parts tolylene diisocyanate, 10 parts hexane add reaction kettle, slowly are warming up to 75 ℃, and insulation reaction is 1.0 hours then; In 0.5 hour, temperature is risen to 100 ℃ subsequently, after 3.0 hours, be cooled to 50 ℃ in this thermotonus;
(2) in another reaction kettle, add 5 parts of hexanes, 5 parts of Virahols, 6 parts of amine, while stirring the cooling, make its after 3 hours temperature less than 25 ℃.
(3) prepolymer with technological process (1) preparation joined in 4 minutes in the reaction kettle of technological process (2) preparation Schiff's base, and stirred fast, made its uniform mixing, and the cooling of water flowing simultaneously kept room temperature reaction 20 minutes;
(4) with reaction mass heated to 70～130 in the technological process (3) ℃ with solvent distillation, after recovered solvent amount to be distilled reaches requirement, stop heating, cool off after 5 minutes, adding ethanol is mixed with the resin solution that solid content is 50wt%;
(5) ethanol and the water that water cut are not higher than 5wt% are processed mixed solvent in 9: 1 ratio; 35 parts of resin solutions and 35 parts of Rutile type Titanium Dioxides, 2 parts of BYK-191 dispersion agents, 1 part of High molecular weight polyethylene wax powder and 35 parts of mixed solvents of technological process (4) preparation are added blender loaders, stirred 30 minutes, it is mixed with high speed dispersor; The material that mixes is taken out, send into sand mill and carry out sand milling, treat to take out after fineness is lower than 10 microns, filter; Through after the assay was approved, pack, promptly make the A component printing ink of alcohol-soluble bicomponent high-temperature resistance plastice gravure composite printing ink.
(6) 75 parts of EP828 type epoxy resin are added reaction kettle, add 75 parts of Virahols then, stirring is warming up to 30 ℃ mixes the system dissolving; After being cooled to room temperature, promptly making solid content is 75wt%B component solidifying agent.
(7) before the printing by ratio of quality and the number of copies be A component printing ink and B component solidifying agent directly mixed in 30: 1 after, filtration promptly makes the plastic rotogravure composite ink that can satisfy the high-temperature boiling resistant requirement.
The key technical indexes of the plastic rotogravure composite ink that prepared high-temperature boiling resistant requires is as shown in the table:
| Test item | National standard | Detected value | The result |
| Fineness (μ m) (scraper plate appearance) | ≤25 | ≤10 | Qualified |
| Tinting strength (%) | 95～110 | 98～105 | Qualified |
| Viscosity (s) (4# cup/25 ℃) | 25～70 | 28～50 | Qualified |
| Just do (mm) (30s/25 ℃) | 25～50 | 28～38 | Qualified |
| Attachment fastness (%) (adhesive tape method) | ≥85 | 93～98 | Qualified |
| Benzene content (ppm) | / | Do not have | Qualified |
Above detected result is according to the QB/T2024-1994 standard testing.
After the printed plastics film of printing ink was compound, through 100 ℃ of high temperature poach 30 minutes, printing ink nondiscoloration, non-foaming, composite bed did not separate; After the printed plastics film of printing ink was compound, through 135 ℃ of high temperature steamings 30 minutes, printing ink nondiscoloration, non-foaming, composite bed did not separate.
Embodiment two
(1) with 80 parts (weight ratios, down with) part polyester polyols, 25 parts tolylene diisocyanate, 10 parts hexane add reaction kettle, slowly are warming up to 75 ℃, and insulation reaction is 1.0 hours then; In 0.5 hour, temperature is risen to 100 ℃ subsequently, after 3.0 hours, be cooled to 50 ℃ in this thermotonus;
(2) in another reaction kettle, add 6 parts of hexanes, 6 parts of Virahols, 7 parts of amine, while stirring the cooling, make its after 3 hours temperature less than 25 ℃.
(3) prepolymer with technological process (1) preparation joined in 5 minutes in the reaction kettle of technological process (2) preparation Schiff's base, and stirred fast, made its uniform mixing, and the cooling of water flowing simultaneously kept room temperature reaction 15 minutes;
(4) with reaction mass heated to 70～130 in the technological process (3) ℃ with solvent distillation, after recovered solvent amount to be distilled reaches requirement, stop heating, cool off after 5 minutes, adding ethanol is mixed with the resin solution that solid content is 50wt%;
(5) ethanol and the water that water cut are not higher than 5wt% are processed mixed solvent in 9: 1 ratio; 35 parts of resin solutions of technological process (4) preparation and 35 parts of phthalein mountain valley with clumps of trees and bamboos is blue, 3 parts of BYK-191 dispersion agents and 35 parts of mixed solvents add blender loaders, stir 30 minutes with high speed dispersor, and it is mixed; The material that mixes is taken out, send into sand mill and carry out sand milling, treat to take out after fineness is lower than 10 microns, filter; Through after the assay was approved, pack, promptly make the A component printing ink of alcohol-soluble bicomponent high-temperature resistance plastice gravure composite printing ink.
(6) 25 parts of EP828 type epoxy resin, 50 parts of KH560 type organo-silicon coupling agents are added reaction kettle, add 75 parts of Virahols then, stirring is warming up to 30 ℃ mixes the system dissolving; After being cooled to room temperature, promptly making solid content is 75wt%B component solidifying agent.
(7) before the printing by ratio of quality and the number of copies be A component printing ink and B component solidifying agent directly mixed in 20: 1 after, filtration promptly makes the plastic rotogravure composite ink that can satisfy the high-temperature boiling resistant requirement.
The key technical indexes of the plastic rotogravure composite ink that prepared high-temperature boiling resistant requires is as shown in the table:
| Test item | National standard | Detected value | The result |
| Fineness (μ m) (scraper plate appearance) | ≤25 | ≤10 | Qualified |
| Tinting strength (%) | 95～110 | 98～105 | Qualified |
| Viscosity (s) (4# cup/25 ℃) | 25～70 | 28～50 | Qualified |
| Just do (mm) (30s/25 ℃) | 25～50 | 28～38 | Qualified |
| Attachment fastness (%) (adhesive tape method) | ≥85 | 93～98 | Qualified |
| Benzene content (ppm) | / | Do not have | Qualified |
Above detected result is according to the QB/T2024-1994 standard testing.
After the printed plastics film of printing ink was compound, through 100 ℃ of high temperature poach 30 minutes, printing ink nondiscoloration, non-foaming, composite bed did not separate; After the printed plastics film of printing ink was compound, through 135 ℃ of high temperature steamings 30 minutes, printing ink nondiscoloration, non-foaming, composite bed did not separate.
Embodiment three
(1) with 50 parts of (weight ratio, down together) polyether Glycols, 20 parts of polyester polyols, 18 parts different Buddhist diketone vulcabond, 10 parts hexane add reaction kettle, slowly are warming up to 75 ℃, and insulation reaction is 1.5 hours then; In 0.5 hour, temperature is risen to 100 ℃ subsequently, after 6.0 hours, be cooled to 50 ℃ in this thermotonus;
(2) in another reaction kettle, add 5 parts of hexanes, 6 parts of Virahols, 5 parts of amine, while stirring the cooling, make its after 3 hours temperature less than 25 ℃.
(3) prepolymer with technological process (1) preparation joined in 6 minutes in the reaction kettle of technological process (2) preparation Schiff's base, and stirred fast, made its uniform mixing, and the cooling of water flowing simultaneously kept room temperature reaction 30 minutes;
(4) with reaction mass heated to 70～130 in the technological process (3) ℃ with solvent distillation, after recovered solvent amount to be distilled reaches requirement, stop heating, cool off after 5 minutes, adding ethanol is mixed with the resin solution that solid content is 50wt%;
(5) ethanol and the water that water cut are not higher than 5wt% are processed mixed solvent in 8: 1 ratio; Your dark red 243,3 parts of BYK-191 dispersion agents of 30 parts of resin solutions of technological process (4) preparation and 30 parts of lithols, 1 part of High molecular weight polyethylene wax powder and 30 parts of mixed solvents are added blender loaders, stirred 30 minutes, it is mixed with high speed dispersor; The material that mixes is taken out, send into sand mill and carry out sand milling, treat to take out after fineness is lower than 10 microns, filter; Through after the assay was approved, pack, promptly make the A component printing ink of alcohol-soluble bicomponent high-temperature resistance plastice gravure composite printing ink.
(6) 50 parts of EP828 type epoxy resin, 25 parts of KH560 type organo-silicon coupling agents are added reaction kettle, add 75 parts of Virahols then, stirring is warming up to 40 ℃ mixes the system dissolving; After being cooled to room temperature, promptly making solid content is 75wt%B component solidifying agent.
(7) before the printing by ratio of quality and the number of copies be A component printing ink and B component solidifying agent directly mixed in 25: 1 after, filtration promptly makes the plastic rotogravure composite ink that can satisfy the high-temperature boiling resistant requirement.
The key technical indexes of the plastic rotogravure composite ink that prepared high-temperature boiling resistant requires is as shown in the table:
| Test item | National standard | Detected value | The result |
| Fineness (μ m) (scraper plate appearance) | ≤25 | ≤10 | Qualified |
| Tinting strength (%) | 95～110 | 98～105 | Qualified |
| Viscosity (s) (4# cup/25 ℃) | 25～70 | 28～50 | Qualified |
| Just do (mm) (30s/25 ℃) | 25～50 | 28～38 | Qualified |
| Attachment fastness (%) (adhesive tape method) | ≥85 | 93～98 | Qualified |
| Benzene content (ppm) | / | Do not have | Qualified |
Above detected result is according to the QB/T2024-1994 standard testing.
After the printed plastics film of printing ink was compound, through 100 ℃ of high temperature poach 30 minutes, printing ink nondiscoloration, non-foaming, composite bed did not separate; After the printed plastics film of printing ink was compound, through 135 ℃ of high temperature steamings 30 minutes, printing ink nondiscoloration, non-foaming, composite bed did not separate.
Claims (6)
1. the preparation method of an alcohol-soluble and water-soluble two-pack high-temperature resistance plastice gravure composite printing ink is characterized in that this alcohol-soluble and water-soluble two-pack high-temperature resistance plastice gravure composite printing ink is made up of A component printing ink and B component solidifying agent, and both mass ratioes are 18 ~ 50:1;
Said A component printing ink is prepared from by the special process process by vulcabond, polyether glycol or polyester polyol or both mixtures, solvent, pigment, auxiliary agent, and wherein to form weight following for each raw material:
10 ~ 30 parts of vulcabond
70 ~ 90 parts in polyether glycol or polyester polyol or both mixtures
8～16 parts of hexanes
4～9 parts of Virahols
5～10 parts in acetone
3～9 parts of amine
115 ~ 250 parts of ethanol
80 ~ 100 parts of pigment
2～5 parts of dispersion agents
Wax powder 0～l part;
The preparation process of described A component printing ink is following specific technological process:
(1) preparation performed polymer: vulcabond, polyether glycol or polyester polyol or both mixtures, hexane are added reaction kettle in proportion, slowly be warming up to 75 ℃, insulation reaction is 1.0～1.5 hours then; Subsequently in 0.5 hour, with temperature
Degree rises to 100 ℃, after 3.0～6.0 hours, is cooled to 50 ℃ in this thermotonus;
(2) preparation Schiff's base: in another reaction kettle, add hexane, Virahol, acetone, amine in proportion successively, while stirring the cooling, make its after 3 hours temperature less than 25 ℃;
(3) polyreaction: the prepolymer of technological process (1) preparation was joined in 4～6 minutes in the reaction kettle of technological process (2) preparation Schiff's base, and stir fast, make its uniform mixing, the cooling of water flowing simultaneously kept room temperature reaction 5～30 minutes
Clock;
(4) distillation: reaction mass heated to 70 ~ 130 in the technological process (3) ℃ with solvent distillation, after recovered solvent amount to be distilled reaches requirement, are stopped heating, cool off after 5 minutes, adding ethanol is mixed with the resin solution that solid content is 50wt%;
(5) ink formulation: the ethanol and the water that water cut are not higher than 5wt% are processed mixed solvent in the ratio of 9:1 ~ 2:1; Resin solution and pigment, dispersion agent, wax powder and the mixed solvent of technological process (4) preparation are added blender loader,
Stirred 20 ~ 30 minutes with high speed dispersor, it is mixed; The material that mixes is taken out, send into sand mill and carry out sand milling, treat to take out after fineness is lower than 10 microns, filter; Through after the assay was approved, packing promptly makes the A component printing ink of alcohol-soluble and water-soluble two-pack high-temperature resistance plastice gravure composite printing ink, wherein during A component ink formulation each raw material to form weight following:
30～35 parts of resin solutions
30 ~ 35 parts of mixed solvents
30 ~ 35 parts of pigment
Dispersion agent l～3 part
Wax powder 0～l part.
2. the preparation method of a kind of alcohol-soluble and water-soluble two-pack high-temperature resistance plastice gravure composite printing ink according to claim 1 is characterized in that: vulcabond is isophorone diisocyanate or tolylene diisocyanate.
3. the preparation method of a kind of alcohol-soluble and water-soluble two-pack high-temperature resistance plastice gravure composite printing ink according to claim 1 is characterized in that: amine is quadrol, hexanediamine, triethylamine, polyethylene polyamine.
4. the preparation method of a kind of alcohol-soluble and water-soluble two-pack high-temperature resistance plastice gravure composite printing ink according to claim 1 is characterized in that: pigment is resistant to elevated temperatures pigment.
5. the preparation method of a kind of alcohol-soluble and water-soluble two-pack high-temperature resistance plastice gravure composite printing ink according to claim 1 is characterized in that: the wax powder is a ultra high molecular weight polyethylene wax.
6. according to the preparation method of the described a kind of alcohol-soluble and water-soluble two-pack high-temperature resistance plastice gravure composite printing ink of claim l; It is characterized in that: before the printing by mass ratio after to be 18～50:l with A component printing ink and B component solidifying agent directly mix; Filter, promptly make the plastic rotogravure composite ink that can satisfy the high-temperature boiling resistant requirement.
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| CN200910060332.8A CN101993628B (en) | 2009-08-12 | 2009-08-12 | Method for preparing alcohol-soluble bi-component thermophilic digestion-resistant plastic composite gravure printing ink |
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| CN102746735B (en) * | 2011-04-18 | 2014-03-12 | 中国科学院化学研究所 | Alcohol soluble polyurethane ink binder |
| CN102746736B (en) * | 2011-04-18 | 2014-03-12 | 中国科学院化学研究所 | Alcohol soluble bi-component polyurethane ink binder |
| CN102604478A (en) * | 2012-03-25 | 2012-07-25 | 重庆宏图油墨有限公司 | Alcohol-aqueous general composite printing ink and preparation method thereof |
| CN102618118A (en) * | 2012-04-09 | 2012-08-01 | 广东国望精细化学品有限公司 | Bi-component high-temperature resistant alcohol-soluble ink binder, preparation method and application thereof |
| CN102796242B (en) * | 2012-08-28 | 2014-02-12 | 山西省应用化学研究所 | Preparation method of polyurethane resin for single-component steaming and boiling resistant composite ink |
| CN103589229B (en) * | 2013-11-20 | 2014-11-19 | 苏州安洁科技股份有限公司 | Brilliant black environment-friendly printing ink and preparation method thereof |
| CN104788665B (en) * | 2015-04-21 | 2016-08-24 | 中国科学院化学研究所 | A kind of alcohol water-soluble modified poly ester ink resin and preparation method thereof |
| CN111087571A (en) * | 2019-12-27 | 2020-05-01 | 黄山中泽新材料有限公司 | Solvent-resistant diluted polyurethane ink binder and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1201057A (en) * | 1997-05-21 | 1998-12-09 | 莱克斯马克国际公司 | Ink composition |
| CN1542066A (en) * | 2003-11-07 | 2004-11-03 | 中山大学 | Water-based plastic composite ink |
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2009
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1201057A (en) * | 1997-05-21 | 1998-12-09 | 莱克斯马克国际公司 | Ink composition |
| CN1542066A (en) * | 2003-11-07 | 2004-11-03 | 中山大学 | Water-based plastic composite ink |
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