CN106432679A - Waterborne polyurethane printing ink connecting material and preparation method thereof - Google Patents
Waterborne polyurethane printing ink connecting material and preparation method thereof Download PDFInfo
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- CN106432679A CN106432679A CN201610803026.9A CN201610803026A CN106432679A CN 106432679 A CN106432679 A CN 106432679A CN 201610803026 A CN201610803026 A CN 201610803026A CN 106432679 A CN106432679 A CN 106432679A
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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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- 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
- C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
- C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
- C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
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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
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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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
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3225—Polyamines
- C08G18/3228—Polyamines acyclic
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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
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3893—Low-molecular-weight compounds having heteroatoms other than oxygen containing silicon
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- C—CHEMISTRY; METALLURGY
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- 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
- C08G18/65—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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- 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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- Life Sciences & Earth Sciences (AREA)
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- Polyurethanes Or Polyureas (AREA)
Abstract
The invention belongs to the technical field of waterborne printing ink and discloses a waterborne polyurethane printing ink connecting material and a preparation method thereof. The preparation method includes the steps that oligomer polyhydric alcohol and polyisocyanate react, then a hydrophilic chain extender and an alcohol micromolecular chain extender are sequentially added for a chain extending reaction, and after a reaction product is diluted and neutralized, an NCO-base-terminated polyurethane prepolymer is obtained; the polyurethane prepolymer is subjected to phase inversion emulsion dispersion in water, then an amine chain extender and a silane coupling agent are added for a rear chain extending and cross-linking reaction, and the waterborne polyurethane printing ink connecting material is obtained. The obtained product has excellent water resistance, heat stability and adhesion firmness, and is safe, free of toxins and suitable for printing thin films for food packaging.
Description
Technical field
The invention belongs to water color ink technical field is and in particular to a kind of water-based polyurethane ink binder and its preparation side
Method.
Background technology
Water color ink abbreviation ink, is formed through abrasive machining by link stuff, colorant, water and auxiliary agent, because having
VOC content is low, nonflammable, nontoxic and becomes unique environment-friendly type oil through the accreditation of food and medicine association of the U.S. the features such as free from extraneous odour
Ink.Water color ink is mainly used in intaglio printing and flexible version printing, and product mostly is plastic film for wrapping etc., is mainly used in food
The fields such as packaging, tobacco and wine packaging, toy for children packaging, the therefore requirement to the safety of ink, resistance to water and adhesiveness is very high.
Binder is the key factor determining water color ink performance.In recent years, aqueous polyurethane is safe and environment-friendly and excellent because of it
Good application performance, is used for food flexible packing print field as water color ink binder in a large number.For avoiding two component inks
Operate the shortcomings of inconvenience, the limited time, wish researcher to obtain a kind of monocomponent waterborne polyurethane ink of excellent performance more.
But monocomponent waterborne polyurethane resin ink in the market, due to the restriction of the aspects such as material choice, production technology, exists
Problems, as not good in stability, resistance to water is poor, adhesion property is bad etc..Therefore, improve monocomponent waterborne polyurethane
Application performance is particularly important.
For improving the performances such as resistance to water and the tack of water-based polyurethane ink, numerous research workers have done substantial amounts of grinding
Study carefully.As patent CN103980461 discloses a kind of preparation method of hydrolysis-resistant waterborne polyurethane dispersion, by synthesis of polyurethane
Performed polymer carry out cross-linking modified, be subsequently adding end-capping reagent 1- aminopropyl -2-methylimidazole carry out block emulsifying, the poly- ammonia of gained aqueouss
Ester resistance to water is good, but the method easily causes in performed polymer stage crosslinked chain extension that crosslink density is excessive, and molecular weight is too high, emulsifying
Difficulty, haves such problems as that stability of emulsion is poor；Patent CN103910851 discloses a kind of preparation of aqueous polyurethane binder
Method, the binder that the method is obtained has good attachment fastness to plastic sheeting, and has good resistance to water and resistance to steaming
Boil performance, high comprehensive performance, but the method carries out multiple batch charging, complex technical process.
Content of the invention
In place of solving the shortcoming and defect of above prior art, the primary and foremost purpose of the present invention is to provide a kind of aqueouss
The preparation method of polyurethane oil ink connecting material.
Another object of the present invention is to providing a kind of water-based polyurethane ink preparing by said method connection
Material.
The object of the invention is achieved through the following technical solutions：
A kind of preparation method of water-based polyurethane ink binder, including following preparation process：
(1) preparation of base polyurethane prepolymer for use as：Oligomer polyol and polyisocyanates are added in reactor, 75～80
React 1.5～2h at DEG C, be subsequently adding the hydrophilic chain extender being dissolved in solvent at 70～75 DEG C to reaction 1～1.5h, add
Alcohols small molecule chain extender carries out chain extending reaction 1～1.5h with the mixture of solvent at 65～70 DEG C；System is cooled to 30～
Add solvent to reduce viscosity after 50 DEG C, add nertralizer neutralization, obtain holding the base polyurethane prepolymer for use as of NCO base；
(2) emulsifying of base polyurethane prepolymer for use as：The base polyurethane prepolymer for use as of step (1) is cooled to 30～40 DEG C, adds deionization
Water dispersed with stirring, makes base polyurethane prepolymer for use as disperse through Phase Inversion Emulsification in water；
(3) chain extension and crosslinking after emulsion：Amine chain extender is added to carry out rear chain extension, Ran Houjia in the emulsion of step (2)
Silane coupler carries out post-crosslinking reaction, obtains described water-based polyurethane ink binder.
Described oligomer polyol for molecular weight be 1000～2000 polyether polyol or polyester polyol, excellent
Select at least one in poly-epsilon-caprolactone glycol (PCL), polyoxypropyleneglycol (PPG), PTMG (PTMG)
Or it is several, to obtain excellent resistance to water.The addition of oligomer polyol accounts for final gained water-based polyurethane ink binder
The 52%～60% of middle solidss quality.Oligomer polyol is before use first in 110～120 DEG C, 0.8～1MPa vacuum condition
Lower dehydration 1-2h is to almost completely free water.
Described polyisocyanates is aromatic diisocyanate or aliphatic diisocyanate, and more preferably, such as six is sub- for the latter
Methyl diisocyanate (HDI), isophorone diisocyanate (IPDI), dicyclohexyl methyl hydride diisocyanate (H12MDI in)
At least one or more of, more preferably isophorone diisocyanate, the color inhibition of prepared water-based polyurethane ink binder
Excellent performance, resistance to water and thermostability are preferable.The addition of polyisocyanates accounts for final gained water-based polyurethane ink binder
The 30%～35% of middle solidss quality.
Described hydrophilic chain extender is carboxyl type chain extender or sulfonate type chain extender, from the former water resistance more
Good.Preferably dihydromethyl propionic acid (DMPA), dimethylolpropionic acid (DMBA) one or two, hydrophilic chain extender give polyurethane
Polymer self-emulsifying properties, can obtain good stability, resistance to water preferably aqueous polyurethane emulsion.The addition of hydrophilic chain extender
Amount accounts for 2.5%～4% of solidss quality in final gained water-based polyurethane ink binder.
Described alcohols small molecule chain extender is ethylene glycol, BDO (BDO), hexanediol, in diglycol
At least one；Preferably BDO (BDO), after the small-molecule substance of this symmetrical structure is reacted with isocyanates, Ke Yiyou
Effect increases the hard segment content in segment and promotes to crystallize, and makes the good hardness of acquisition and resistance to water.Alcohols small molecule chain extender
Addition accounts for 3%～6% of solidss quality in final gained water-based polyurethane ink binder.
The preferred triethylamine of described nertralizer, is conducive to preferable, the uniform and stable emulsion system of acquisition outward appearance, nertralizer
The degree of neutralization that addition presses 95%～100% adds.
The mol ratio of the NCO/OH of Waterborne Polyurethane Prepolymer of step (1) presses 1.2～1.5 Proportionality design.
The condition of the described dispersed with stirring of step (2) is 6000～6500r/min.
Described amine chain extender is selected in ethylenediamine, diethylenetriamine, triethylene tetramine, diethylenetriamines at least
A kind of；Preferably ethylenediamine, improves molecular weight, heat stability and the resistance to water of polyurethane to a certain extent as rear chain extender.
The addition of amine chain extender accounts for 2%～4% of solidss quality in final gained water-based polyurethane ink binder.
Described silane coupler selects aminopropyl triethoxysilane, N- aminoethyl -3- aminopropyl triethoxysilane
One or two；Amino and NCO base react relatively acutely more difficult control, select the rear chain extension stage after performed polymer dispersion to add
Enter, effective control reaction avoids gel implode, makes steadily to carry out chain extension and cross-linking reaction.Preferably N- aminoethyl -3- aminopropyl three
Ethoxysilane, this coupling agent can play chain extension effect, and can play crosslinked action, improves polyurethane molecular quality, Ke Yiming
Aobvious improve water-based polyurethane ink binder attachment fastness on a plastic film and resistance to water.The addition of silane coupler
Amount accounts for 1%～4% of solidss quality in final gained water-based polyurethane ink binder.
The preferred acetone of described solvent and two kinds of N-Methyl pyrrolidone；On the one hand a small amount of low boiling point solvent can play fall
The effect of low system viscosity, and easily distill out；On the other hand, high boiling solvent is conducive to film forming plasticising uniform.
The addition of described deionized water control the solid content of final gained water-based polyurethane ink binder be 40～
44%；Make one viscosity of System forming and the more homogeneous emulsion of particles size and distribution, meanwhile, relatively low viscosity is beneficial to binder
Dispersion flows, higher solid content contributes to the drying of ink, shortens drying time.
A kind of water-based polyurethane ink binder, is prepared by said method.
The preparation method of the present invention and obtained product have the advantage that and beneficial effect：
(1) the water-based polyurethane ink binder of the present invention adopts water as main dispersing medium, and does not have in building-up process
Have using organic tin poisoned catalyst, therefore obtained binder and water color ink safety non-toxic it is adaptable to packaging for foodstuff
Printing with thin film.
(2) to carry out polyurethane using the N- aminoethyl -3- aminopropyl triethoxysilane containing two amino pre- for the present invention
The rear chain extension of polymers and cross-linking modified, improves mean molecule quantity and the crosslink density of aqueous polyurethane.This reaction process is simple,
Easily controllable, a large amount of organic solvents need not be used, it is to avoid after amino chain extender adds in common process, system viscosity drastically rises
The high danger even producing gel.
(3) organic moiety of coupling agent is incorporated into polyurethane backbone by rear chain extension by the present invention, simultaneously in main chain both sides
Regularly it is dispersed with the crosslinked siloxy group of hydrolyzable.The surface tension of obtained product is lower, thus in non-polar substrate
On adhesion property strengthen.Additionally, the hydroxyl being formed after organosilicon side-chain hydrolysis and moulding after processing (as sided corona treatment)
Easily there is condensation reaction in the hydroxyl on material film substrate or carboxyl.Therefore, the method significantly improves the water-fast of aqueous polyurethane
Property and the adhesion property in Plastic film for food.
(4) the water-based polyurethane ink binder of the present invention is to have the monocomponent waterborne polyurethane of good storage stability
Emulsion system, possesses excellent water resistance, heat stability and attachment fastness.Compared to double-component waterborne polyurethane system, it is to avoid
Packaging, transport, use time be limited and the shortcomings of operation inconvenience it is easier to construction.
Specific embodiment
With reference to embodiment, the present invention is described in further detail, but embodiments of the present invention not limited to this.
Embodiment 1
(1) synthesis of base polyurethane prepolymer for use as：Equipped with agitator, thermometer, the 500ml four-hole boiling flask of condensing reflux pipe
After adding poly-epsilon-caprolactone dihydroxylic alcohols and 80 DEG C of insulation reaction 2h of 29.8g isoflurane chalcone diisocyanate after 60g dehydration, cooling
React 1.5h to 75 DEG C of dihydromethyl propionic acid (DMPA) mix and blends adding 3.98g to be dissolved in 2gN- methyl pyrrolidone, so
It is slowly added dropwise the 4.68g1 mixing with 4g acetone afterwards under the conditions of 70 DEG C, 4- butanediol, about 15min drip off, insulation reaction 1.5h,
Finally being cooled to 50 DEG C adds a small amount of acetone to reduce viscosity, adds 3g triethylamine neutralization reaction 15min after 5min, and end NCO is obtained
The base polyurethane prepolymer for use as of base.
(2) emulsifying of Waterborne Polyurethane Prepolymer, rear chain extension and crosslinking：The base polyurethane prepolymer for use as that step (1) is synthesized drops
40 DEG C of Wen Zhiyue, while pouring 120g deionization waterside lifting mixing speed into 6500r/min, makes performed polymer disperse breast through phase reversal
After changing 5min, add chain extension after 0.88g ethylenediamine, after stirring reaction 5min, add 1.02g N- aminoethyl -3- aminopropyl three second
After TMOS, chain extension and hydrolytic crosslinking react 20min, mixing speed is down to discharging after 2000r/min stirring 30min, will lack
Amount acetone vacuum removal, prepared solid content is 44% water-based polyurethane ink binder.
The water-based polyurethane ink binder that the present embodiment is obtained can stably be stored more than 6 months at normal temperatures, is obtained
Polyurethane laminate 24h water absorption rate be 6.5%, in PET film, attachment fastness is preferable.
Embodiment 2
(1) synthesis of base polyurethane prepolymer for use as：Equipped with agitator, thermometer, the 500ml four-hole boiling flask of condensing reflux pipe
After adding poly-epsilon-caprolactone dihydroxylic alcohols and 80 DEG C of insulation reaction 2h of 36.8g isoflurane chalcone diisocyanate after 60g dehydration, cooling
React 1.5h to 75 DEG C of dihydromethyl propionic acid (DMPA) mix and blends adding 2.8g to be dissolved in 1.5gN- methyl pyrrolidone, so
It is slowly added dropwise the 5.32g1 mixing with 4g acetone afterwards under the conditions of 70 DEG C, 4- butanediol, about 15min drip off, insulation reaction 1.5h,
Finally being cooled to 30～50 DEG C adds a small amount of acetone to reduce viscosity, adds 2.11g triethylamine neutralization reaction 15min, system after 5min
The base polyurethane prepolymer for use as of NCO base must be held.
(2) emulsifying of Waterborne Polyurethane Prepolymer, rear chain extension and crosslinking：The base polyurethane prepolymer for use as that step (1) is synthesized drops
40 DEG C of Wen Zhiyue, while pouring 140g deionization waterside lifting mixing speed into 6500r/min, makes performed polymer disperse breast through phase reversal
After changing 5min, add chain extension after 2.3g ethylenediamine, after stirring 5min, add 4.5g N- aminoethyl -3- aminopropyl-triethoxy silicon
Alkane chain extension and hydrolytic crosslinking react after 20min, and mixing speed is down to discharging after 2000r/min stirring 30min, and prepared consolidating contains
Measure the water-based polyurethane ink binder for 40%.
The water-based polyurethane ink binder that the present embodiment is obtained can stably be stored more than 6 months at normal temperatures, is obtained
Polyurethane laminate 24h water absorption rate be 4.6%, in PET film, attachment fastness is fine.
Embodiment 3
(1) synthesis of base polyurethane prepolymer for use as：Equipped with agitator, thermometer, the 500ml four-hole boiling flask of condensing reflux pipe
After adding poly-epsilon-caprolactone dihydroxylic alcohols and 80 DEG C of insulation reaction 2h of 36.8g isoflurane chalcone diisocyanate after 60g dehydration, cooling
React 1.5h to 75 DEG C of dihydromethyl propionic acid (DMPA) mix and blends adding 3.8g to be dissolved in 2gN- methyl pyrrolidone, then
It is slowly added dropwise the 4.62g1 mixing with 4g acetone under the conditions of 70 DEG C, 4- butanediol, about 15min drip off, insulation reaction 1.5h,
After be cooled to 50 DEG C about and add a small amount of acetone to reduce viscosity, add 2.86g triethylamine neutralization reaction 15min after 5min, be obtained
The base polyurethane prepolymer for use as of end NCO base.
(2) emulsifying of Waterborne Polyurethane Prepolymer, rear chain extension and crosslinking：The base polyurethane prepolymer for use as that step (1) is synthesized drops
40 DEG C of Wen Zhiyue, while pouring 140g deionization waterside lifting mixing speed into 6500r/min, makes performed polymer disperse breast through phase reversal
After changing 5min, add chain extension after 1.24g ethylenediamine and 1.38g diethylenetriamine, after stirring 5min, addition 2.2g N- aminoethyl-
After 3- aminopropyl triethoxysilane chain extension hydrolytic crosslinking reaction 20min, mixing speed is down to 2000r/min stirring 30min
Discharging afterwards, prepared solid content is 42% water-based polyurethane ink binder.
By the water-based polyurethane ink binder that above-mentioned formula and technique are obtained can stably store at normal temperatures 6 months with
On, the 24h water absorption rate of prepared polyurethane laminate is 5.5%, and the attachment fastness in PET film is good.
The performance test methods of above example products therefrom：
1. glued membrane water absorption rate
The preparation of glued membrane：By evenly laid out for appropriate prepared water-based polyurethane ink binder in polyfluortetraethylene plate
On, horizontal positioned, spontaneously dry 3d under room temperature, after coating film forming, put into 50 DEG C of oven drying 24h, be then dried under vacuum to
Constant weight, puts into standby in exsiccator.
Water absorption rate measures：Glued membrane is cut into the print of 2cm × 2cm size, and weigh on analytical balance M0Afterwards, it is immersed in
Take out after 24h in water, blot surface moisture with filter paper and weigh again M1, it is calculated as follows the water absorption rate of latex film：
Water absorption rate W/%=(M1-M0)/M0× 100%.
2. the attachment fastness on plastic sheeting
Tested according to GB/T 13217.7-1991, criterion remains 90% on a plastic film for printed coating
More than, attachment fastness is fine；Printed coating remains 80-90% on a plastic film, and attachment fastness is good；Printed coating is thin in plastics
70-80% is remained on film, attachment fastness is preferable；Printed coating remains 60-70% on a plastic film, and attachment fastness is general；Print
Brush applied coating remains less than 60% on a plastic film, and attachment fastness is poor.
From the point of view of test result, the monocomponent waterborne polyurethane ink adhesive of present invention preparation has to be stablized well
Property, resistance to water and good adhesion property is had on PET thin film, and non-toxic and safe environmental protection, process is simple, stable easily grasp
Make, Product transport, easy to use, do not limited by use time.
Above-described embodiment is the present invention preferably embodiment, but embodiments of the present invention are not subject to above-described embodiment
Limit, other any spirit without departing from the present invention and the change made under principle, modification, replacement, combine, simplify,
All should be equivalent substitute mode, be included within protection scope of the present invention.
Claims (10)
1. a kind of preparation method of water-based polyurethane ink binder is it is characterised in that include following preparation process：
(1) preparation of base polyurethane prepolymer for use as：Oligomer polyol and polyisocyanates are added in reactor, at 75～80 DEG C
Reaction 1.5～2h, is subsequently adding the hydrophilic chain extender being dissolved in solvent at 70～75 DEG C to reaction 1～1.5h, adds alcohols
Small molecule chain extender carries out chain extending reaction 1～1.5h with the mixture of solvent at 65～70 DEG C；System is cooled to 30～50 DEG C
Add solvent to reduce viscosity afterwards, add nertralizer neutralization, obtain holding the base polyurethane prepolymer for use as of NCO base；
(2) emulsifying of base polyurethane prepolymer for use as：The base polyurethane prepolymer for use as of step (1) is cooled to 30～40 DEG C, adds deionized water to stir
Mix dispersion, so that base polyurethane prepolymer for use as is disperseed through Phase Inversion Emulsification in water；
(3) chain extension and crosslinking after emulsion：Then plus silane amine chain extender is added to carry out rear chain extension, in the emulsion of step (2)
Coupling agent carries out post-crosslinking reaction, obtains described water-based polyurethane ink binder.
2. a kind of water-based polyurethane ink binder according to claim 1 preparation method it is characterised in that：Described
Oligomer polyol for molecular weight be 1000～2000 polyether polyol or polyester polyol；Oligomer polyol plus
Enter that amount accounts for solidss quality in final gained water-based polyurethane ink binder 52%～60%.
3. a kind of water-based polyurethane ink binder according to claim 1 preparation method it is characterised in that：Described
Polyisocyanates is aromatic diisocyanate or aliphatic diisocyanate；The addition of polyisocyanates accounts for final gained water
The 30%～35% of solidss quality in property polyurethane oil ink connecting material.
4. a kind of water-based polyurethane ink binder according to claim 1 preparation method it is characterised in that：Described
Hydrophilic chain extender is carboxyl type chain extender or sulfonate type chain extender；The addition of hydrophilic chain extender accounts for final gained aqueouss
The 2.5%～4% of solidss quality in polyurethane oil ink connecting material.
5. a kind of water-based polyurethane ink binder according to claim 1 preparation method it is characterised in that：Described
Alcohols small molecule chain extender is ethylene glycol, BDO, hexanediol, at least one in diglycol；Little point of alcohols
The addition of sub- chain extender accounts for 3%～6% of solidss quality in final gained water-based polyurethane ink binder.
6. a kind of water-based polyurethane ink binder according to claim 1 preparation method it is characterised in that：Described
Nertralizer is triethylamine；The degree of neutralization that the addition of nertralizer presses 95%～100% adds.
7. a kind of water-based polyurethane ink binder according to claim 1 preparation method it is characterised in that：Described
Amine chain extender selects at least one in ethylenediamine, diethylenetriamine, triethylene tetramine, diethylenetriamines；Amine chain extension
The addition of agent accounts for 2%～4% of solidss quality in final gained water-based polyurethane ink binder.
8. a kind of water-based polyurethane ink binder according to claim 1 preparation method it is characterised in that：Described
Silane coupler selects one of aminopropyl triethoxysilane, N- aminoethyl -3- aminopropyl triethoxysilane or two kinds；
The addition of silane coupler accounts for 1%～4% of solidss quality in final gained water-based polyurethane ink binder.
9. a kind of water-based polyurethane ink binder according to claim 1 preparation method it is characterised in that：Described go
It is 40～44% that the addition of ionized water controls the solid content of final gained water-based polyurethane ink binder.
10. a kind of water-based polyurethane ink binder it is characterised in that：By the method system described in any one of claim 1～9
Standby obtain.
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| CN106986979A (en) * | 2017-04-13 | 2017-07-28 | 合肥科天水性科技有限责任公司 | A kind of synchronous chain extension preparation technology of cationic aromatic aqueous polyurethane |
| CN107141882A (en) * | 2017-03-20 | 2017-09-08 | 江苏百瑞特新材料有限公司 | A kind of synthetic method of aqueous polyurethane resin used for water color ink |
| CN107778990A (en) * | 2017-11-28 | 2018-03-09 | 佛山市高明区海帝陶瓷原料有限公司 | A kind of preparation method of the slurry of the ink-jet on packaging material |
| CN107916027A (en) * | 2017-11-28 | 2018-04-17 | 佛山市高明区海帝陶瓷原料有限公司 | A kind of slurry of the ink-jet on packaging material |
| CN107936219A (en) * | 2017-12-18 | 2018-04-20 | 广州聚碳合成材料有限公司 | Modified aqueous polyurethane emulsion and preparation method thereof and water-based ink resin |
| CN108084785A (en) * | 2017-12-18 | 2018-05-29 | 广州聚碳合成材料有限公司 | Modified aqueous polyurethane dispersoid and preparation method thereof and water-based ink resin |
| CN109021200A (en) * | 2018-08-15 | 2018-12-18 | 芜湖扬展新材料科技服务有限公司 | A kind of modified aqueous polyurethane ink adhesive and preparation method thereof |
| CN109180899A (en) * | 2018-07-20 | 2019-01-11 | 张家港市东方高新聚氨酯有限公司 | aqueous polyurethane and preparation method thereof |
| CN109651582A (en) * | 2018-11-27 | 2019-04-19 | 上海华峰新材料研发科技有限公司 | Water-based polyurethane ink binder and preparation method thereof |
| CN111471157A (en) * | 2020-05-06 | 2020-07-31 | 江门东洋油墨有限公司 | Water-based polyurethane ink binder and preparation method and application thereof |
| CN111732704A (en) * | 2020-06-02 | 2020-10-02 | 旭川化学（苏州）有限公司 | Polyurethane adhesive for 121 ℃ high-temperature-cooking-resistant water-based gravure printing ink and preparation method thereof |
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| CN107778990A (en) * | 2017-11-28 | 2018-03-09 | 佛山市高明区海帝陶瓷原料有限公司 | A kind of preparation method of the slurry of the ink-jet on packaging material |
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| CN109021200A (en) * | 2018-08-15 | 2018-12-18 | 芜湖扬展新材料科技服务有限公司 | A kind of modified aqueous polyurethane ink adhesive and preparation method thereof |
| CN109651582A (en) * | 2018-11-27 | 2019-04-19 | 上海华峰新材料研发科技有限公司 | Water-based polyurethane ink binder and preparation method thereof |
| CN109651582B (en) * | 2018-11-27 | 2022-02-01 | 上海华峰新材料研发科技有限公司 | Waterborne polyurethane ink binder and preparation method thereof |
| CN111471157A (en) * | 2020-05-06 | 2020-07-31 | 江门东洋油墨有限公司 | Water-based polyurethane ink binder and preparation method and application thereof |
| CN111732704A (en) * | 2020-06-02 | 2020-10-02 | 旭川化学（苏州）有限公司 | Polyurethane adhesive for 121 ℃ high-temperature-cooking-resistant water-based gravure printing ink and preparation method thereof |
| CN111732704B (en) * | 2020-06-02 | 2022-04-26 | 旭川化学（苏州）有限公司 | Polyurethane adhesive for 121 ℃ high-temperature-cooking-resistant water-based gravure printing ink and preparation method thereof |
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| CN114773567A (en) * | 2022-04-27 | 2022-07-22 | 江苏中金玛泰医药包装有限公司 | Preparation method of high-humidity-heat-resistance water-based polyurethane adhesive |
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Application publication date: 20170222 |