CN105925056B - A kind of cork paper intaglio printing water color ink and preparation method thereof - Google Patents
A kind of cork paper intaglio printing water color ink and preparation method thereof Download PDFInfo
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- CN105925056B CN105925056B CN201610331534.1A CN201610331534A CN105925056B CN 105925056 B CN105925056 B CN 105925056B CN 201610331534 A CN201610331534 A CN 201610331534A CN 105925056 B CN105925056 B CN 105925056B
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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
- C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
- C08G18/6415—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63 having nitrogen
- C08G18/6423—Polyalkylene polyamines; polyethylenimines; Derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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Abstract
The invention belongs to polymer chemistry and technical field of fine, specifically related to a kind of cork paper intaglio printing water color ink and preparation method thereof, the cork paper intaglio printing water color ink is made up of modified polyurethane emulsion, color stuffing, auxiliary agent, cosolvent and water, modified polyurethane emulsion is dihydroxylic alcohols using polyethylene glycol caprolactone copolymer, the pliability of the moisture retention, moisture dispersibility to pigment and polycaprolactone of polyethylene glycol is not only had concurrently, and degradable, environmental pollution is little.The present invention introduces the quaternised polyvinyl amine of tool anti-microbial property in polyurethane, had both improve ink moisture retention, and had improved the curling resistance of printing paper, and had increased paper wet strength, the Retention that improve color stuffing, ink adhesion and antibiotic property again.Water color ink prepared by the present invention, nonpoisonous and tasteless, rate of drying is very fast, and dispersion stabilization is good, and print product is indeformable, not crimping, and bright-colored, antibiotic property is excellent.
Description
Technical field
The invention belongs to polymer chemistry and technical field of fine, and in particular to a kind of cork paper intaglio printing water
Property ink and preparation method thereof.
Background technology
Cork paper is " cigarette tipping paper ", is the dedicated paper that cigarette is got up with filter tip tipping.The printing of cork paper with
Based on intaglio printing, at present, cork paper printing house is mostly using the ink printing cork paper of alcohol-soluble and ester dissolubility, printing process
In dissolvent residual in a large amount of volatile organic solvents for being related to and printed matter can bring one to the physical and mental health of environment and people
Fixed impact.With growing to even greater heights for environmental protection cry, cork paper printing Environmental-protection water-based ink becomes the direction of industry development.
At present, cork paper printing water base gravure ink is primarily present problems with：1）As water color ink is using a large amount of
Water as solvent, and cork paper papery is relatively thin, hole big, absorption is fast, causes cork paper excessive to moisture absorption, and paper goes out
The problems such as now serious contraction distortion, tensile strength decline, paper becomes fragile；2）The slow drying speed of water color ink, impact printing
Speed and following process, it is also possible to cause intaglio plate the phenomenons such as photographic fog and scumming occur.Exactly these factors, hinder water color ink
Application on cork paper.Chinese patent CN105269997A discloses a kind of preparation method of green cigarette paper, main
Will be by controlling the ink performances such as water color ink pigment fineness of dispersion, viscosity, and the typography such as intaglio plate groove depth, dry regulation
To realize application of the water color ink on cork paper.Chinese patent CN102952431A adopts water-borne acrylic resin, iron oxide
Pigment is primary raw material, and adding aziridine increases ink adhesion, and adjusts ink performance by auxiliary agent so that ink dried
Energy, printing performance make moderate progress.
In addition, when smoker's smoking, cork paper directly can be contacted with mouth, and therefore hygienic requirements is higher, national cigarette
Careless monopoly bureau has formulated the mandatory sanitary index of cigarette cork paper, standard etc. come specification tobacco business.The aqueous oil of cork paper
In addition to requiring that volatile organic solvent and harmful heavy metal content reach standard requirement in ink, its antibiotic property is also people pass to ink
One emphasis of note.Due to being suitable for vegetative condition containing suitable starch, moisture etc. in cork paper, so cigarette filter
There is the presence of certain bacterium on mouth unavoidably；Plus people transmission and using cigarette during inevitably connect with bacterium
Touch, therefore, it is necessary to improve sterilization and the antibacterial ability of cork paper.It is to realize sterilizing function most directly and effectively to add antiseptic
Method, but it is small organic molecule to commonly use antiseptic, has that heat resistance is poor, easily separate out and the defect such as migrate, for
For the cork paper ink product of human body intimate contact, there is the risk of impact health.
Content of the invention
It is an object of the invention to overcoming above-mentioned the deficiencies in the prior art, a kind of aqueous oil of cork paper intaglio printing is provided
Ink and preparation method thereof, the water color ink have the advantages that nonpoisonous and tasteless, rate of drying is fast, dispersion stabilization is good, print product
Indeformable when drying, not crimping, antibiotic property are excellent.
The technical scheme of present disclosure is, a kind of cork paper intaglio printing water color ink, it is characterised in that：By following
The raw material composition of percentage by weight：
Modified polyurethane emulsion 35 ~ 60%
Color stuffing 15 ~ 25%
Wetting dispersing agent 1 ~ 5%
Thickener 0.5 ~ 2%
Defoamer 0.2 ~ 2%
Deionized water 10 ~ 18%
Cosolvent 8 ~ 16%
Wherein, the modified polyurethane emulsion is prepared from by the raw material of following weight portion：
Polyvinylamine 5.3 ~ 18
Quarternary ammonium salt compound 4.8 ~ 9.2
Polyethylene glycol 11.6 ~ 57
Polycaprolactone 32.5 ~ 66
Ferric acetyl acetonade 0.5 ~ 1
Diisocyanate 8.8 ~ 17.5
Carboxylic acid type hydrophilic monomer 2 ~ 5
Salt-forming reagent 0.5 ~ 3.5
Catalyst 0.01 ~ 0.03
Deionized water 180 ~ 285
Appropriate aqueous sodium carbonate.
Further improvement of the present invention, the polyvinylamine molecular weight for constituting modified polyurethane emulsion are 600 ~ 1800.Poly- second
Enamine is the water-soluble polymer that a kind of amino is connected directly between on hydrocarbon backbone, and its a large amount of high reaction activity amino having can
React with compounds such as isocyanates, epoxies, aldehydes, anhydrides, carboxylic acids, carboxylic acid halides, so as to realize the grafting of polymer
And functional modification.Amino of the present invention using polyvinylamine and the reaction of NCO, connect in polyurethane used for water color ink
Polyvinylamine is introduced in splicing, its hydrophilic amino can both improve ink moisture retention, it is to avoid cork paper is because absorbing ink too much
In moisture and there is gross distortion, paper wet strength, the Retention of color stuffing and ink adhesion can be promoted again.
Further improvement of the present invention, the quarternary ammonium salt compound for constituting modified polyurethane emulsion are the quaternary ammonium salt containing epoxy radicals
Compound, concrete structure are as follows：
, wherein, it is 12 ~ 16 that R1, R2 are respectively-CH3 or-CH2CH3, R3 for-(CH2) nCH3, N.The present invention utilizes poly- second
The amino of enamine and epoxy reaction, introduce the quarternary ammonium salt compound with bactericidal action, improve water color ink and its printing
Antibiotic property, while avoiding the migration problem being likely to occur using small molecule antiseptic.In addition, though existing many researchs are closed
Polymer antibacterial agent is become, but which has affected ink printing glossiness using there is a problem of and system binder poor compatibility
Etc. performance, the present invention is directly grafted to antiseptic on binder strand, successfully solves the problems referred to above.Experiment shows, contains
The quaternary ammonium salt of long alkyl chain is than the similar small toxicity containing short alkyl chain, and when alkyl chain carbon atomicity is 12 ~ 16, anti-microbial property is most
Good, therefore it is preferred that n is 12 ~ 16.
Further improvement of the present invention, the molecular weight polyethylene glycol for constituting modified polyurethane emulsion are 400 ~ 1000.Poly- second
Glycol has good moisture dispersibility to pigment, is conducive to improving the dispersion stabilization of ink, and its hydrophily makes it have excellent
Different moisture retention, can improve the curling resistance of printing paper.Copolymer using polyethylene glycol and caprolactone is had concurrently as dihydroxylic alcohols
The hydrophily of polyethylene glycol and the pliability of caprolactone, both copolymer good biocompatibilities, degradable, alleviate to environment
The pressure for causing.In synthesis of dibasic alcohol, shared by caprolactone, molar ratio is too little, then the polyurethane resin hydrophily which synthesizes is too
By force, poor water resistance；Shared by caprolactone, molar ratio is too big, then which is reduced with the percent grafting of polyethylene glycol, is fallen flat.
It is preferred that the mol ratio of polyethylene glycol and caprolactone is 1:5~1:20.
Further improvement of the present invention, the diisocyanate for constituting modified polyurethane emulsion are isophorone diisocyanate
One or more in ester, hexamethylene diisocyanate, toluene di-isocyanate(TDI), -4,4 ＇ of diphenyl methane-diisocyanate
Mixture.
Further improvement of the present invention, constitute modified polyurethane emulsion carboxylic acid type hydrophilic monomer be dihydromethyl propionic acid,
The mixture of one or more in dimethylolpropionic acid, diaminobenzoic acid.
Further improvement of the present invention, the catalyst for constituting modified polyurethane emulsion are laurate bismuth, stannous octoate, February
One or more mixture in dilaurylate, preferably laurate bismuth.
In the present invention, salt-forming reagent is triethylamine, ammoniacal liquor, NaOH or potassium hydroxide.
Invention further discloses a kind of preparation method of cork paper intaglio printing water color ink, comprises the following steps：
S1, polyvinylamine and quantitative deionized water are added in reactor, with aqueous sodium carbonate adjust pH value be 10 ±
0.5,60 ~ 80 DEG C are warming up to, the quarternary ammonium salt compound aqueous solution are dripped, is dripped off in 0.5 ~ 1h, continue 3 ~ 5h of reaction, obtain quaternized
Polyvinylamine；
S2, in another reactor, polyethylene glycol and caprolactone monomer is added, lead to nitrogen, 130 ~ 150 DEG C are warmed up to, add
Ferric acetyl acetonade, reacts 20 ~ 24h.Cooling, product is dissolved in dichloromethane, plus methanol extraction, and vacuum drying obtains poly- second two
Alcohol-caprolactone dihydroxylic alcohols；
S3, polyethylene glycol-caprolactone dihydroxylic alcohols that step S2 is synthesized and carboxylic acid type hydrophilic monomer, diisocyanate are mixed
Close, 70 ~ 90 DEG C are warming up to, catalyst is added, 3 ~ 4h of reaction generates polyurethane prepolymer；
S4, in the prepolymer of step S3 synthesis, add salt-forming reagent, stir 10 ~ 15min, add quantitative deionized water and
The quaternised polyvinyl amine of step S1 synthesis, under ice-water bath, emulsified in 800 ~ 1500r/min mixing speed and react 1 ~ 2h,
Obtain modified polyurethane emulsion；
S5, in proportion modified polyurethane emulsion, deionized water and cosolvent are put in reactor and mix, then put into
Color stuffing, wetting dispersing agent, thickener, defoamer, are disperseed with the mixing speed of 800 ~ 1500r/min at a high speed, eventually pass sand
Grinding machine is ground to fineness≤20 μm, obtains final product cork paper intaglio printing water color ink.
In above step, color stuffing includes inorganic pigment, organic pigment and inserts.Cigarette is required with cork paper printed matter
Assume specific yellow form and aspect, at present, the form and aspect can only rely on inorganic pigment realize, inorganic pigment than great, free settling, and
Printed matter vividness and gloss are less than organic pigment, and the present invention is meeting form and aspect by compounding inorganic pigment and organic pigment
Printing color and luster is improved while requirement.Cosolvent is ethanol, isopropanol, normal propyl alcohol, one or two the mixing in isobutanol
Thing.In water color ink, the evaporation rate of water is slower, adds the drying property that organic solvent can adjust ink as cosolvent, institute
From organic solvent should property compatible with water good, there is to resin preferable solvability again, and require that evaporation rate is moderate,
If volatilization easily causes very much the printing troubles such as heap version soon.
Compared with prior art, the present invention has the advantages that：
（1）The invention discloses a kind of cork paper intaglio printing water color ink, modified polyurethane emulsion is using poly- second two
Alcohol-caprolactone copolymer is dihydroxylic alcohols, and, to pigment wetting good dispersion, pliability is high, and performance of keeping humidity is excellent for the emulsion of its synthesis,
It is prevented effectively from printing paper excessive and Texturized because absorbing water.
（2）The present invention introduces polyvinylamine in polyurethane, can improve ink moisture retention, promote paper wet strength, raising
The Retention of color stuffing and ink adhesion, and the amino using polyvinylamine and epoxy reaction, introduce tool bactericidal action
Quarternary ammonium salt compound, improve the antibiotic property of water color ink and its printing, it is to avoid be likely to occur using small molecule antiseptic
Migration problem, and the resin compatible sex chromosome mosaicism existed using polymer antibacterial agent.
（3）The cork paper intaglio printing water color ink of present disclosure, nonpoisonous and tasteless, rate of drying are very fast, dispersion is steady
Qualitative good, print product is indeformable, not crimping, and bright-colored, antibiotic property is excellent.
Specific embodiment
In order to deepen the understanding of the present invention, the present invention is described in further detail below in conjunction with embodiment, the reality
Apply example to be only used for the present invention is explained, protection scope of the present invention is not constituted and limit.Unless stated otherwise, involved in embodiment
And reagent, method be reagent commonly used in the art and method.
The performance of water-base gravure ink is according to GB/T 26395-2011《Aqueous cigarette bag base gravure ink》Tested.
Curling resistance is tested：Ink is printed on cork paper, after drying, observes its Texturized phenomenon.
Ink anti-microbial property is according to GB/T 21866-2008《Antibiotic paint（Paint film）Antibiotic property determination method and antibacterial effect
Really》, carried out from the staphylococcus aureus nutrient solution that the E. coli broth that concentration is 1/500, concentration are 1/100 respectively
Test.
Embodiment 1：
First, the preparation of modified polyurethane emulsion
S1. polyvinylamine that 18.0g molecular weight is 1800 and 35.0g deionized water are added in reactor, with concentration 15%
Aqueous sodium carbonate adjust pH value be about 10, be warming up to 60 DEG C, by 9.2g 2,3- glycidyl dimethyl dodecyl base chlorination
Ammonium is dissolved in 20.0g deionized water and drips, and drips off in 1h, continues reaction 5h, obtains quaternised polyvinyl amine；
S2. polyethylene glycol and the 66.0g caprolactone monomer that 11.6g molecular weight is 400 is added in another reactor（Poly- second
Glycol：The mol ratio of caprolactone is 1:20）, lead to nitrogen, 140 DEG C be warmed up to, 0.8g ferric acetyl acetonade is added, react 24h.Drop
Temperature, product is dissolved in dichloromethane, plus methanol extraction, and vacuum drying obtains polyethylene glycol-caprolactone dihydroxylic alcohols；
S3. polyethylene glycol-caprolactone the dihydroxylic alcohols for step S2 being synthesized and 5.0g dihydromethyl propionic acid, the different fluorine that of 17.5g
Ketone diisocyanate mixes, and is warming up to 90 DEG C, adds 0.02g laurate bismuth, and reaction 4h generates polyurethane prepolymer；
S4. add 3.5g triethylamine in the prepolymer of step S3 synthesis, stir 15min, add 230g deionized water and
The quaternised polyvinyl amine of step S1 synthesis, under ice-water bath, emulsified in 800r/min mixing speed and react 2h, obtain modification
Polyaminoester emulsion.
Gained emulsion is pale yellow half penetrating, and solid content is 31.0%, and at 25 DEG C, viscosity is 85mpa.s.
2nd, cork paper intaglio printing water color ink is prepared according to following formula compositions：
1 cork paper intaglio printing water-soluble printing ink formula of table
| Material title | Quality/g |
| Above-mentioned modified polyurethane emulsion | 52 |
| Iron oxide yellow | 6.5 |
| Iron oxide red | 3 |
| Benzidine yellow | 1 |
| Calcium carbonate | 4.5 |
| Deionized water | 15 |
| Isopropanol | 16 |
| Wetting dispersing agent（BYK-193） | 1 |
| Thickener（ASE-60） | 0.8 |
| Defoamer（CF268） | 0.2 |
Weigh and mix in quantitative modified polyurethane emulsion, water, isopropanol input reactor, add color stuffing, wetting
Dispersant, thickener, defoamer, are disperseed with the mixing speed of 1100r/min at a high speed, eventually pass sand mill be ground to fineness≤
20 μm, cork paper printing water base gravure ink is obtained, ink Ju Ti Pei Fang is shown in Table 1.
Embodiment 2：
First, the preparation of modified polyurethane emulsion
S1. polyvinylamine that 5.3g molecular weight is 600 and 20.0g deionized water are added in reactor, with concentration 15%
Aqueous sodium carbonate adjusts pH value and is about 10, is warming up to 80 DEG C, by 4.8g 2,3- glycidyl dimethyl hexadecyl ammonium chloride
It is dissolved in 10.0g deionized water and drips, drip off in 1h, continues reaction 3h, obtain quaternised polyvinyl amine；
S2. polyethylene glycol and 32.5 caprolactone monomers that 57.0g molecular weight is 1000 are added in another reactor（Poly- second
Glycol：The mol ratio of caprolactone is 1:5）, lead to nitrogen, 130 DEG C be warmed up to, 1.0g ferric acetyl acetonade is added, react 22h.Cooling,
Product is dissolved in dichloromethane, plus methanol extraction, vacuum drying obtains polyethylene glycol-caprolactone dihydroxylic alcohols；
S3. polyethylene glycol-caprolactone the dihydroxylic alcohols for synthesizing step S2 is different with 2.0g dimethylolpropionic acid, 8.8g toluene two
Cyanate mixes, and is warming up to 70 DEG C, adds 0.01g laurate bismuth, and reaction 3h generates polyurethane prepolymer；
S4. 1.0g ammoniacal liquor is added in the prepolymer of step S3 synthesis, stir 10min, add 150g deionized water and step
The quaternised polyvinyl amine of rapid S1 synthesis, under ice-water bath, emulsified in 1500r/min mixing speed and react 1h, obtain modification
Polyaminoester emulsion.
Gained emulsion is pale yellow half penetrating, and solid content is 37.8%, and at 25 DEG C, viscosity is 105mpa.s.
2nd, cork paper intaglio printing water color ink is prepared according to following formula compositions：
2 cork paper intaglio printing water-soluble printing ink formula of table
| Material title | Quality/g |
| Above-mentioned modified polyurethane emulsion | 35 |
| Iron oxide yellow | 10 |
| Iron oxide red | 4 |
| Benzidine yellow | 3 |
| Titanium dioxide | 8 |
| Deionized water | 18 |
| Ethanol | 13 |
| Wetting dispersing agent（BYK-185） | 5 |
| Thickener（RJ-945） | 2 |
| Defoamer（F-111） | 2 |
Weigh and mix in quantitative modified polyurethane emulsion, water, ethanol input reactor, add color stuffing, wetting point
Powder, thickener, defoamer, are disperseed with the mixing speed of 1500r/min at a high speed, eventually pass sand mill and be ground to fineness≤20
μm, cork paper printing water base gravure ink is obtained, ink Ju Ti Pei Fang is shown in Table 2.
Embodiment 3
First, the preparation of modified polyurethane emulsion
S1. polyvinylamine that 12.0g molecular weight is 1200 and 25.0g deionized water are added in reactor, with concentration is
15% aqueous sodium carbonate adjusts pH value and is about 10, is warming up to 70 DEG C, by 6.7g 2,3- glycidyl diethyldodecane base
Ammonium chloride is dissolved in 15.0g deionized water and drips, and drips off in 0.5h, continues reaction 5h, obtains quaternised polyvinyl amine；
S2. polyethylene glycol and the 55.2g caprolactone monomer that 29.0g molecular weight is 600 is added in another reactor（Poly- second
Glycol：The mol ratio of caprolactone is 1:10）, lead to nitrogen, 150 DEG C be warmed up to, 0.5g ferric acetyl acetonade is added, react 20h.Drop
Temperature, product is dissolved in dichloromethane, plus methanol extraction, and vacuum drying obtains polyethylene glycol-caprolactone dihydroxylic alcohols；
S3. polyethylene glycol-caprolactone the dihydroxylic alcohols for step S2 being synthesized and 3.0g diaminobenzoic acid, 14.3g hexichol first
Alkane diisocyanate mixes, and is warming up to 80 DEG C, adds 0.03g laurate bismuth, and reaction 3.5h generates polyurethane prepolymer；
S4. 5% sodium hydrate aqueous solution of 10g is added in the prepolymer of step S3 synthesis, stir 10min, add 200g
Deionized water and the quaternised polyvinyl amine of step S1 synthesis, under ice-water bath, emulsified in 1300r/min mixing speed and react
1.5h, obtains modified polyurethane emulsion.
Gained emulsion is pale yellow half penetrating, and solid content is 33.1%, and at 25 DEG C, viscosity is 80mpa.s.
3rd, cork paper intaglio printing water color ink is prepared according to following formula compositions：
3 cork paper intaglio printing water-soluble printing ink formula of table
| Material title | Quality/g |
| Above-mentioned modified polyurethane emulsion | 60 |
| Iron oxide yellow | 9 |
| Iron oxide red | 2 |
| Lithol Red | 1 |
| Calcium carbonate | 6 |
| Deionized water | 10 |
| Ethanol | 8 |
| Wetting dispersing agent（BYK-185） | 2.5 |
| Thickener（ASE-60） | 0.5 |
| Defoamer（Extra large river 334） | 1 |
Weigh and mix in quantitative modified polyurethane emulsion, water, ethanol input reactor, add color stuffing, wetting point
Powder, thickener, defoamer, are disperseed with the mixing speed of 800r/min at a high speed, eventually pass sand mill and be ground to fineness≤20 μ
M, is obtained cork paper printing water base gravure ink, and ink Ju Ti Pei Fang is shown in Table 3.
The water color ink prepared by each embodiment, outsourcing water-base gravure ink carry out dependence test, are as a result summarized in
In table 4 below.
Water color ink prepared by 4 embodiment of table is contrasted with outsourcing ink performance
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Outsourcing ink | |
| Viscosity/s | 23 | 26 | 25 | 25 |
| Fineness/μm | ≤20 | ≤20 | ≤20 | ≤25 |
| Tinting strength, tinting power/% | 98 | 101 | 99 | 93 |
| Curling resistance | No Texturized | No Texturized | No Texturized | Obvious crimping |
| Anti- Escherichia coli rate/% | 99.9 | 99.6 | 99.7 | 91.5 |
| Anti-Staphylococcus aureus rate/% | 99.9 | 99.5 | 99.5 | 91.1 |
| Bin stability | >1 year | >1 year | >1 year | >6 months |
From table 4, it can be seen that the cork paper intaglio printing water color ink prepared by the embodiment of the present invention is aqueous with outsourcing
Base gravure ink is compared, and tinting strength, tinting power, antibiotic property and bin stability are all significantly improved, in addition the cork paper intaglio plate prepared by embodiment
Printing water ink, its printing cork paper dry after be not in Texturized, and outsourcing water color ink printing yew
Then there is obvious edge-curl phenomenon in paper.
General principle, principal character and the advantage of the present invention has been shown and described above.The technical staff of the industry should
Understand, the present invention is not restricted to the described embodiments, the original that the present invention is simply described described in above-described embodiment and specification
Reason, without departing from the spirit and scope of the present invention, the present invention also has various changes and modifications, these changes and improvements
Both fall within scope of the claimed invention.The claimed scope of the invention is by appending claims and its equivalent circle.
Fixed.
Claims (8)
1. a kind of cork paper intaglio printing water color ink, it is characterised in that：Comprise the following raw materials by weight percent：
Modified polyurethane emulsion 35 ~ 60%
Color stuffing 15 ~ 25%
Wetting dispersing agent 1 ~ 5%
Thickener 0.5 ~ 2%
Defoamer 0.2 ~ 2%
Deionized water 10 ~ 18%
Cosolvent 8 ~ 16%
Wherein, the modified polyurethane emulsion is prepared from by the raw material of following weight portion：
Polyvinylamine 5.3 ~ 18
Quarternary ammonium salt compound 4.8 ~ 9.2
Polyethylene glycol 11.6 ~ 57
Caprolactone 32.5 ~ 66
Ferric acetyl acetonade 0.5 ~ 1
Diisocyanate 8.8 ~ 17.5
Carboxylic acid type hydrophilic monomer 2 ~ 5
Salt-forming reagent 0.5 ~ 3.5
Catalyst 0.01 ~ 0.03
Deionized water 180 ~ 285
Appropriate aqueous sodium carbonate；
Wherein, the quarternary ammonium salt compound of the composition modified polyurethane emulsion is the quarternary ammonium salt compound containing epoxy radicals, and structure is such as
Under：
, wherein, R1、R2Respectively-CH3Or-CH2CH3, R3For-(CH2)nCH3, n is 12 ~ 16.
2. cork paper intaglio printing water color ink according to claim 1, it is characterised in that：The modified poly- ammonia of the composition
The polyvinylamine molecular weight of ester emulsion is 600 ~ 1800.
3. cork paper intaglio printing water color ink according to claim 1, it is characterised in that：The modified poly- ammonia of the composition
The molecular weight polyethylene glycol of ester emulsion is 400 ~ 1000.
4. cork paper intaglio printing water color ink according to claim 1, it is characterised in that：The modified poly- ammonia of the composition
The mol ratio of the polyethylene glycol of ester emulsion and caprolactone is 1:5~1:20.
5. cork paper intaglio printing water color ink according to claim 1, it is characterised in that：The modified poly- ammonia of the composition
The diisocyanate of ester emulsion is IPDI, hexamethylene diisocyanate, toluene di-isocyanate(TDI), hexichol
The mixture of one or more in -4,4 ＇ of methylmethane-diisocyanate.
6. cork paper intaglio printing water color ink according to claim 1, it is characterised in that：The modified poly- ammonia of the composition
The carboxylic acid type hydrophilic monomer of ester emulsion is dihydromethyl propionic acid, dimethylolpropionic acid, one or more in diaminobenzoic acid
Mixture.
7. cork paper intaglio printing water color ink according to claim 1, it is characterised in that：The modified poly- ammonia of the composition
The catalyst of ester emulsion is laurate bismuth, stannous octoate, one or more mixture in dibutyl tin laurate.
8. a kind of preparation method of cork paper intaglio printing water color ink as claimed in claim 1, it is characterised in that：Including
Following steps：
S1, polyvinylamine and quantitative deionized water are added in reactor, it is 10 ± 0.5 to adjust pH value with aqueous sodium carbonate,
60 ~ 80 DEG C are warming up to, the quarternary ammonium salt compound aqueous solution are dripped, is dripped off in 0.5 ~ 1h, continue 3 ~ 5h of reaction, obtain quaternized poly- second
Enamine；
S2, in another reactor, polyethylene glycol and caprolactone monomer is added, lead to nitrogen, 130 ~ 150 DEG C are warmed up to, add acetyl
Acetone iron, react 20 ~ 24h, cooling, product is dissolved in dichloromethane, plus methanol extraction, vacuum drying obtain polyethylene glycol-
Caprolactone dihydroxylic alcohols；
S3, the polyethylene glycol-caprolactone dihydroxylic alcohols for synthesizing step S2 are mixed with carboxylic acid type hydrophilic monomer, diisocyanate, are risen
Temperature adds catalyst to 70 ~ 90 DEG C, and 3 ~ 4h of reaction generates polyurethane prepolymer；
S4, in the prepolymer of step S3 synthesis, salt-forming reagent is added, 10 ~ 15min is stirred, adds quantitative deionized water and step
The quaternised polyvinyl amine of S1 synthesis, under ice-water bath, emulsified in 800 ~ 1500r/min mixing speed and react 1 ~ 2h, obtain
Modified polyurethane emulsion；
S5, in proportion modified polyurethane emulsion, deionized water and cosolvent are put in reactor and mix, then put into face and fill out
Material, wetting dispersing agent, thickener, defoamer, are disperseed with the mixing speed of 800 ~ 1500r/min at a high speed, eventually pass sand mill
Fineness≤20 μm are ground to, obtain final product cork paper intaglio printing water color ink.
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| CN107266969A (en) * | 2017-06-27 | 2017-10-20 | 常州西夏墅东方工具有限公司 | A kind of antibacterial aqueous ink and preparation method thereof |
| CN108912820A (en) * | 2018-07-17 | 2018-11-30 | 芜湖倍思科创园有限公司 | A kind of water-based ink and preparation method thereof |
| CN111004540B (en) * | 2019-12-24 | 2022-01-25 | 南京金升华包装材料有限公司 | Water-based tipping paper |
| CN112646419A (en) * | 2020-09-24 | 2021-04-13 | 东莞市万润涂料有限公司 | MY-C paper gravure ink with gradually changed colors and preparation method thereof |
| CN112457707A (en) * | 2020-11-27 | 2021-03-09 | 江苏唐彩新材料科技股份有限公司 | Tipping paper water-based ink containing composite antibacterial material and preparation method thereof |
| CN113861378A (en) * | 2021-09-27 | 2021-12-31 | 武汉淡雅香生物科技有限公司 | Thermal adhesion resistant waterborne polyurethane based on cigarette tipping paper and preparation method thereof |
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