CN106349432A - Polyurethane modified silicone-acrylic emulsion and preparation method and application thereof - Google Patents
Polyurethane modified silicone-acrylic emulsion and preparation method and application thereof Download PDFInfo
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- CN106349432A CN106349432A CN201610804966.XA CN201610804966A CN106349432A CN 106349432 A CN106349432 A CN 106349432A CN 201610804966 A CN201610804966 A CN 201610804966A CN 106349432 A CN106349432 A CN 106349432A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
- C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers
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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
- C08G18/28—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
- C08G18/34—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
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
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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
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C09D11/107—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof
Abstract
The invention belongs to the technical field of water-based polyurethane ink, and discloses polyurethane modified silicone-acrylic emulsion and preparation method and application thereof. The preparation method comprises the following steps: dissolving a dyhydroxyl compound with a long carbon chain in polyol; then adding diisocyanate to react; after the content of -NCO group reaches a certain value, adding a hydrophilic chain extender to react; then adding acrylate monomers containing hydroxyl groups to react; adding the acrylate monomers and organosilicone monomers to reduce viscosity of a reactant to obtain polyurethane prepolymers; adding a neutralizer to ionize the polyurethane prepolymers, and then carrying out aqueous dispersion emulsification; and adding an initiator to initiate unsaturated monomers to carry out free radical polymerization so as to obtain the polyurethane modified silicone-acrylic emulsion. The obtained polyurethane modified silicone-acrylic emulsion has good adhesion strength on polyolefin plastic (OPP, PE) films, and is good in water resistance and steaming and boiling resistance.
Description
Technical field
The invention belongs to water-based polyurethane ink technical field is and in particular to a kind of polyurethane-modified silicone acrylic emulsion and its system
Preparation Method and application.
Background technology
Water color ink is current one of printing-ink of environmental protection the most, is also currently the only to be recommended and approved by U.S. fda
, the printing-ink kind that can be used for direct food contact.With respect to solvent type ink, water color ink has not atmosphere pollution
Environment, low toxicity, low-resource energy consumption and working environment safe the features such as.In China, paper printing is market-oriented with water color ink,
But the not absorption characteristics due to plastic sheeting and low-surface-energy characteristic, package plastics of food film printing water color ink also in
The research starting stage.At present, polyolefin plasticss film packaging printing substantially uses solvent-borne type ink used for plastic, this is because
Polyolefin plasticss film surface energy is low, hydrophobicity is strong, be not available for the active group of reaction, and general waterborne polymeric is difficult to moistening
Its surface simultaneously obtains good adhesion strength.According to the adhesion mechanism on polyolefin plasticss surface, the polarity of ink adhesive with poly-
Olefin plastics surface polarity is closer to ink is better in polyolefin plasticss wettability of the surface, adhesion strength；Ink adhesive
Molecular structure is more similar to polyolefin plasticss molecular structure, and molecular force is bigger between the two.Application No.
201310338763.2 patent report is a kind of to be suitable for printing the water solublity self-crosslinking acrylic tree of compound oil ink in opp
Fat, primary raw material is acrylic acid and its derivant, non-acrylic compounds carboxylic monomer, using the relatively low polarity of acrylate polymer
And carboxylic group obtains good adhesive strength on opp, pet base material, but acrylate polymer is heated and easily returns viscous, and gloss is relatively
Low and scrub performance is poor.
Aqueous polyurethane as new environment-friendly material, has fabulous wearability, marresistance and good low
Warm nature energy, Gloss Retention etc., have broad application prospects in water color ink field.But aqueous polyurethane contains a large amount of polar groups
Group, the poor adhesive force to non-polar polyolefinic plastic sheeting.At present, improve water color ink polyurethane binder in polyolefin plasticss
On thin film, the method for adhesive force is mainly by two kinds.One is to add chloridized polyolefin adhesion promoter.But the master of chloridized polyolefin
Want solvent to be toluene, not only environment and workmen endangered big, and easily remain in ink layer, endanger food safety,
Meanwhile, in chloridized polyolefin, chlorine atom is reactive group, meets high temperature or is easily come off by illumination chlorine atom for a long time, ink layer is tough
Property and poor durability.Two is introducing acrylate polymer in aqueous polyurethane.Using the relatively low table of acrylate polymer
Face polarity adjusts the surface property of aqueous polyurethane, and similar to the molecular structure of polyolefin plasticss using acrylate polymer
Property is so as to have good adhesion strength on polyolefin plasticss.The patent report of Application No. 201010190353.4 one
There is kind to all types of plastic film substrate the integrated plastic gravure alcohol-soluble water aqueous composite ink resin of good adhesion, be with can
Polymerizable polyurethane polymeric monomer, (methyl) acrylate, vinylacetate and active function monomer are raw material, by Solution Free Radical
Copolymerization is obtained.But the preparation technology of this resin is complex, is unfavorable for industrialized production.
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 poly- ammonia
The preparation method of ester modified silicone acrylic emulsion.
Another object of the present invention is to providing a kind of polyurethane-modified silicone acrylic emulsion preparing by said method.
It is still another object of the present invention to provide above-mentioned polyurethane-modified silicone acrylic emulsion is in polyolefin plasticss film ink
Application.
The object of the invention is achieved through the following technical solutions:
A kind of preparation method of polyurethane-modified silicone acrylic emulsion, including following preparation process:
(1) c will be carried12～18The dihydroxy compounds of Long carbon chain are dissolved in polyvalent alcohol at 60～80 DEG C, add two
Isocyanates, prepolymerization reaction 60～90min at 70～85 DEG C, end-nco base performed polymer with double bond is obtained；
(2) add hydrophilic chain extender in the end-nco base performed polymer of step (1) resulting tape double bond, anti-at 70～85 DEG C
Answer 60～90min, add hydroxyl acrylic ester monomer, react 15～30min, be then cooled to 40～60 DEG C, add
Acrylic ester monomer and organic silicon monomer adjust viscosity, prepared base polyurethane prepolymer for use as；
(3) add nertralizer to carry out ionizing 3～5min in step (2) gained performed polymer, then pass through to shear moisture
Scattered emulsifying 5～10min, obtains aqueous polyurethane emulsion；
(4) in step (3) gained aqueous polyurethane emulsion add initiator, at 75～85 DEG C reaction 60～
120min, obtains described polyurethane-modified silicone acrylic emulsion.
Described band c12～18The dihydroxy compounds of Long carbon chain are preferably dihydroxypropyl octadecane acid esters, 1,2- hexadecane
At least one in glycol, 2,3- dihydroxy propanol dodecanoate；Band c12～18The addition of the dihydroxy compounds of Long carbon chain accounts for
The 2%～8% of solidss quality in the final polyurethane-modified silicone acrylic emulsion of gained.
Described polyvalent alcohol be preferably poly-epsilon-caprolactone glycol, dimer (fatty acid) yl esterdiol, in polypropylene glycol at least one
Kind；The addition of polyvalent alcohol accounts for 29%～33% of solidss quality in the polyurethane-modified silicone acrylic emulsion of final gained.
Described diisocyanate is preferably isophorone diisocyanate, hexamethylene diisocyanate, 4,4 '-two hexamethylenes
At least one in dicyclohexylmethane diisocyanate；The addition of diisocyanate accounts in the polyurethane-modified silicone acrylic emulsion of final gained
The 9%～16% of solidss quality.
Hydrophilic chain extender described in step (2) be preferably 2,2- dihydromethyl propionic acid, in dimethylolpropionic acid at least
A kind of；The addition of hydrophilic chain extender accounts for 2%～4% of solidss quality in the polyurethane-modified silicone acrylic emulsion of final gained.
Described hydroxyl acrylic ester monomer is preferably Hydroxypropyl acrylate, at least one in 2-(Acryloyloxy)ethanol；
The addition of hydroxyl acrylic ester monomer account for solidss quality in the polyurethane-modified silicone acrylic emulsion of final gained 0.3%～
1%.
Described acrylic ester monomer is preferably butyl acrylate, butyl methacrylate, acrylic acid methyl ester., metering system
At least one in sour methyl ester；The addition of acrylic ester monomer accounts for solidss in the polyurethane-modified silicone acrylic emulsion of final gained
The 45%～48% of quality.
Described organic silicon monomer is preferably γ-methacryloxypropyl trimethoxy silane, vinyl trimethoxy
At least one in silane, vinyl silane triisopropoxide；Preferentially adopt vinyl silane triisopropoxide；Organic silicon monomer
The addition accounting for accounts for 2%～4% of solidss quality in the polyurethane-modified silicone acrylic emulsion of final gained.
Nertralizer described in step (3) is preferably triethylamine, ammonia, at least one in sodium hydroxide, with degree of neutralization
100% amount is added.
Initiator described in step (4) is preferably Ammonium persulfate., at least one in potassium peroxydisulfate；The addition of initiator
Amount accounts for the 0.5%～0.7% of acrylic ester monomer and organic silicon monomer gross mass.
A kind of polyurethane-modified silicone acrylic emulsion, is prepared by said method.
Application in polyolefin plasticss film ink for the above-mentioned polyurethane-modified silicone acrylic emulsion.
The principle of the present invention is using band Long carbon chain (c12～18) dihydroxy compounds modified polyurethane, then with modified
Polyurethane-modified siloxane-acrylate copolymer.- the oh of the dihydroxy compounds with Long carbon chain (12～18c) and-nco of polyisocyanates
Group reacts, the aqueous polyurethane emulsion of prepared belt length carbon chain branches, then with its modified siloxane-acrylate copolymer.On the one hand, long
Carbon chain branches can reduce the polarity of polyurethane, by it and have the organosilicon of low-surface-energy and share and can further improve polymer and exist
Wettability on non-polar polyolefinic plastic sheeting, meanwhile, the structure of Long carbon chain side chain is similar to polyolefin plasticss molecular structure,
When both intermolecular distances are sufficiently small, stronger intermolecular force can provide good adhesion strength between the two, and organic
Silicon has raising polymer wettability on low surface energy substrates, shortens the work of the distance between polymer molecule and substrate molecule
With.On the other hand, the hydrophobicity of Long carbon chain side chain and organosilicon can improve polyurethane-modified polyacrylate emulsion resistance to water and
Boiling resistance.
The preparation method of the present invention and obtained product have the advantage that and beneficial effect:
(1) present invention will carry Long carbon chain (c12～18) dihydroxy compounds modified polyurethane and organosilicon-modified acrylic
Two systems of ester combine, common raising wettability on non-polar polyolefinic plastic sheeting for the waterborne polymeric, contracting
Distance between short polymer molecule and substrate molecule；
(2) the polyurethane-modified silicone acrylic emulsion of present invention preparation due in its molecule the structure of some segments and polyolefin gather
Adduct molecule structure is similar, and intermolecular dispersion force is stronger, so that polymer molecule is had on non-polar polyolefinic plastic film substrate
There is good adhesion strength, can need not add adhesion promoter as water color ink binder；
(3), during the present invention prepares polyurethane-modified silicone acrylic emulsion, not using any catalyst, and carry Long carbon chain
(c12～18) dihydroxy compounds mostly be non-toxic and safe compound, therefore this polyurethane-modified silicone acrylic emulsion is applied to packaging for foodstuff
Ink adhesive.
Brief description
Fig. 1 is contact angle test result figure on opp thin film for the polyurethane-modified silicone acrylic emulsion of embodiment of the present invention gained.
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) add 40g polypropylene glycol in equipped with agitator, thermometer, the 500ml four-hole boiling flask of reflux condensing tube
(ppg, molecular weight is 2000), 2.7g dihydroxypropyl octadecane acid esters stir 10min at 65 DEG C.Then heat to 78.5
DEG C, add 18.7g isophorone diisocyanate (ipdi), react 70min, end-nco base performed polymer is obtained.
(2) 2.7g dihydromethyl propionic acid (dmpa) is dissolved in 5g acetone, is added in-nco base the performed polymer of above-mentioned end, in
React 70min at 78.5 DEG C, be subsequently adding 0.7g 2-(Acryloyloxy)ethanol, react 20min；React and be cooled to 40 DEG C, added
65.5g unsaturated monomer (27g butyl acrylate, 34.5g methyl methacrylate, 4g vinyl silane triisopropoxide) is adjusted
Viscosity, prepared base polyurethane prepolymer for use as.
(3) above-mentioned base polyurethane prepolymer for use as is moved in dispersion tank, add 2.1g triethylamine (tea), 5g water, in 1000r/
Ionizing 5min under min mixing speed；Another edge height mixing speed, to 7000r/min, adds 140g water to be disperseed
Emulsifying, obtains aqueous polyurethane emulsion after emulsifying 10min.
(4) it is added to after 0.4g potassium peroxydisulfate being dissolved in 10g water in aqueous polyurethane emulsion, carry out freedom at 80 DEG C
Base is polymerized, and the response time is 90min, and reaction is cooled to 40 DEG C after terminating, and discharging obtains final product polyurethane-modified silicone acrylic emulsion.
Embodiment 2
(1) add 40g polypropylene glycol in equipped with agitator, thermometer, the 500ml four-hole boiling flask of reflux condensing tube
(ppg, molecular weight is 2000), 5.3g 1,2- hexadecane diol, stirs 10min at 65 DEG C.Then heat to 78.5 DEG C, plus
Enter 15.7g isophorone diisocyanate (ipdi), react 70min, end-nco base performed polymer is obtained.
(2) 3g dihydromethyl propionic acid (dmpa) is dissolved in 5g acetone, is added in-nco base the performed polymer of above-mentioned end, in
React 70min at 78.5 DEG C, be subsequently adding 0.7g 2-(Acryloyloxy)ethanol, react 20min；React and be cooled to 55 DEG C, added
65.5g is unsaturated to be adjusted to monomer (27g butyl acrylate, 34.5g methyl methacrylate, 4g vinyl silane triisopropoxide)
Section viscosity, prepared base polyurethane prepolymer for use as.
(3) above-mentioned base polyurethane prepolymer for use as is moved in dispersion tank, add 2.2g triethylamine (tea), 5g water, in 1000r/
Ionizing 5min under min mixing speed；Another edge height mixing speed, to 7000r/min, adds 140g water to be disperseed
Emulsifying, obtains aqueous polyurethane emulsion after emulsifying 10min.
(4) it is added to after 0.4g potassium peroxydisulfate being dissolved in 10g water in aqueous polyurethane emulsion, carry out freedom at 80 DEG C
Base is polymerized, and the response time is 90min, and reaction is cooled to 40 DEG C after terminating, and discharging obtains final product polyurethane-modified silicone acrylic emulsion.
Embodiment 3
(1) add 40g polypropylene glycol in equipped with agitator, thermometer, the 500ml four-hole boiling flask of reflux condensing tube
(ppg, molecular weight is 2000), 7.9g 2,3- dihydroxy propanol dodecanoate, stirs 10min at 65 DEG C.Then heat to
78.5 DEG C, add 12.9g isophorone diisocyanate (ipdi), react 70min, end-nco base performed polymer is obtained.
(2) 3.1g dihydromethyl propionic acid (dmpa) is dissolved in 5g acetone, is added in-nco base the performed polymer of above-mentioned end, in
React 70min at 78.5 DEG C, be subsequently adding 0.7g 2-(Acryloyloxy)ethanol, react 20min；React and be cooled to 60 DEG C, added
65.5g is unsaturated to be adjusted to monomer (27g butyl acrylate, 34.5g methyl methacrylate, 4g vinyl silane triisopropoxide)
Section viscosity, prepared base polyurethane prepolymer for use as.
(3) above-mentioned base polyurethane prepolymer for use as is moved in dispersion tank, add 2.3g triethylamine (tea), 5g water, in 1000r/
Ionizing 5min under min mixing speed；Another edge height mixing speed, to 7000r/min, adds 140g water to be disperseed
Emulsifying, obtains aqueous polyurethane emulsion after emulsifying 10min.
(4) it is added to after 0.4g potassium peroxydisulfate being dissolved in 10g water in aqueous polyurethane emulsion, carry out freedom at 80 DEG C
Base is polymerized, and the response time is 90min, and reaction is cooled to 40 DEG C after terminating, and discharging obtains final product polyurethane-modified silicone acrylic emulsion.
Properties of product are tested:
1. surface tension and contact angle:
Using the jc2000 type surface tension tester test of upper marine morning Numerical Technologies Inc be obtained polyurethane-modified
The surface tension of silicone acrylic emulsion and the contact angle on opp thin film, result such as Fig. 1 (is respectively embodiment 1, is implemented by left-to-right
Example 2 and embodiment 3) and table 1 shown in.
The table tension force of polyurethane-modified silicone acrylic emulsion of table 1 embodiment 1～3 preparation and the contact angle on opp thin film
From Fig. 1 and Biao 1, carry c12～18The addition of the dihydroxy compounds of Long carbon chain and organosilicon composition reduces poly-
The urethane modification surface tension of silicone acrylic emulsion and the contact angle on opp thin film.The introducing of Long carbon chain side chain provides aqueouss and gathers
The hydrophobicity of urethane molecule so that polyurethane molecular amphipathic property becomes apparent from, and all on side chain, freedom of movement,
During water surface absorption, lipophilic group is more easy to towards air.With the increase of Long carbon chain content, water surface saturated extent of adsorption by
Cumulative big, surface tension is gradually lowered therewith.The capillary reduction of polyurethane-modified silicone acrylic emulsion improves it in opp thin film
On wettability so that its contact angle on opp thin film tapers into.
2. peel strength test:
Using printing ink intaglio printing proof press by be obtained polyurethane-modified silicone acrylic emulsion film on opp, pe thin film, dry
Carry out gluing (the solvent-borne type glue of resistance to steaming and decocting) thereon after dry, after the volatilization of its surface solvent, then be combined with cpp film,
Measure its 90 ° of peel strengths after ripening 48h, rate of extension is 300mm/min, test result is as shown in table 2:
The peel strength of the polyurethane-modified silicone acrylic emulsion of table 2 embodiment 1～3 preparation
From table 2, the peel strength of all embodiments is all higher.This is because the molecule of polyurethane-modified silicone acrylic emulsion
The Long carbon chain side chain of middle introducing and organosilicon chain link reduce the surface tension of aqueous polyurethane so as to thin in opp and pe plastics
Good wettability is had on film, meanwhile, the structure of Long carbon chain side chain is similar to opp and pe molecular structure, stronger point between the two
Sub- intermolecular forces provide good adhesion strength.
3. decocting in water and steaming and decocting test:
Taking embodiment 2 as a example, by the polyurethane-modified silicone acrylic emulsion film of synthesis on opp, pe thin film, at it after drying
On carry out gluing (the solvent-borne type glue of resistance to steaming and decocting), after the volatilization of its surface solvent, then be combined with cpp film, then according to
People's Republic of China's light industry standard " water-base gravure plastic sheeting table printing ink " (qbt 4103-2010), is carried out respectively
100 DEG C of decocting in water and 121 DEG C of steaming and decocting tests, whether observation test sample product are wrinkling, rupture.
After decocting in water, steaming and decocting, sample is not wrinkling, do not rupture, and shows the water boiling resistance of prepared polyurethane-modified silicone acrylic emulsion
Good with boiling resistance.
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 polyurethane-modified silicone acrylic emulsion is it is characterised in that include following preparation process:
(1) c will be carried12～18The dihydroxy compounds of Long carbon chain are dissolved in polyvalent alcohol at 60～80 DEG C, add two isocyanides
Acid esters, prepolymerization reaction 60～90min at 70～85 DEG C, end-nco base performed polymer with double bond is obtained；
(2) add hydrophilic chain extender in the end-nco base performed polymer of step (1) resulting tape double bond, at 70～85 DEG C, react 60
～90min, adds hydroxyl acrylic ester monomer, reacts 15～30min, is then cooled to 40～60 DEG C, adds propylene
Esters of gallic acid monomer and organic silicon monomer adjust viscosity, prepared base polyurethane prepolymer for use as；
(3) add nertralizer to carry out ionizing 3～5min in step (2) gained performed polymer, then pass through to shear the scattered breast of moisture
Change 5～10min, obtain aqueous polyurethane emulsion；
(4) add initiator in step (3) gained aqueous polyurethane emulsion, react 60～120min at 75～85 DEG C, obtain
To described polyurethane-modified silicone acrylic emulsion.
2. a kind of polyurethane-modified silicone acrylic emulsion according to claim 1 preparation method it is characterised in that: described band
c12～18The dihydroxy compounds of Long carbon chain are dihydroxypropyl octadecane acid esters, 1,2- hexadecane diol, 2,3- dihydroxy propanol
At least one in dodecanoate；Band c12～18It is polyurethane-modified that the addition of the dihydroxy compounds of Long carbon chain accounts for final gained
The 2%～8% of solidss quality in silicone acrylic emulsion.
3. a kind of polyurethane-modified silicone acrylic emulsion according to claim 1 preparation method it is characterised in that: described poly- many
First alcohol is poly-epsilon-caprolactone glycol, dimer (fatty acid) yl esterdiol, at least one in polypropylene glycol；The addition of polyvalent alcohol accounts for
The 29%～33% of solidss quality in the final polyurethane-modified silicone acrylic emulsion of gained.
4. a kind of polyurethane-modified silicone acrylic emulsion according to claim 1 preparation method it is characterised in that: described two is different
Cyanate is isophorone diisocyanate, hexamethylene diisocyanate, in 4,4 '-dicyclohexyl methyl hydride diisocyanate
At least one；The addition of diisocyanate account for solidss quality in the polyurethane-modified silicone acrylic emulsion of final gained 9%～
16%.
5. a kind of polyurethane-modified silicone acrylic emulsion according to claim 1 preparation method it is characterised in that: step (2)
Described in hydrophilic chain extender be 2,2- dihydromethyl propionic acid, at least one in dimethylolpropionic acid；Hydrophilic chain extender
Addition accounts for 2%～4% of solidss quality in the polyurethane-modified silicone acrylic emulsion of final gained.
6. a kind of polyurethane-modified silicone acrylic emulsion according to claim 1 preparation method it is characterised in that: described band hydroxyl
Base acrylic ester monomer is Hydroxypropyl acrylate, at least one in 2-(Acryloyloxy)ethanol；Hydroxyl acrylic ester monomer
Addition account for 0.3%～1% of solidss quality in the polyurethane-modified silicone acrylic emulsion of final gained.
7. a kind of polyurethane-modified silicone acrylic emulsion according to claim 1 preparation method it is characterised in that: described propylene
Esters of gallic acid monomer is butyl acrylate, butyl methacrylate, acrylic acid methyl ester., at least one in methyl methacrylate；
The addition of acrylic ester monomer accounts for 45%～48% of solidss quality in the polyurethane-modified silicone acrylic emulsion of final gained；Institute
State organic silicon monomer be γ-methacryloxypropyl trimethoxy silane, vinyltrimethoxy silane, vinyl three different
At least one in npropoxysilane；Preferentially adopt vinyl silane triisopropoxide；The addition that organic silicon monomer accounts for accounts for
The 2%～4% of solidss quality in the polyurethane-modified silicone acrylic emulsion of whole gained.
8. a kind of polyurethane-modified silicone acrylic emulsion according to claim 1 preparation method it is characterised in that: step (3)
Described in nertralizer be triethylamine, ammonia, at least one in sodium hydroxide, added with the amount of degree of neutralization 100%；Step
(4) initiator described in is Ammonium persulfate., at least one in potassium peroxydisulfate；The addition of initiator accounts for esters of acrylic acid list
Body and the 0.5%～0.7% of organic silicon monomer gross mass.
9. a kind of polyurethane-modified silicone acrylic emulsion it is characterised in that: by the preparation of method described in any one of claim 1～8
Obtain.
10. application in polyolefin plasticss film ink for the polyurethane-modified silicone acrylic emulsion described in claim 9.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111647306A (en) * | 2020-07-14 | 2020-09-11 | 南通贝得彩色印刷有限公司 | In situ generation of organized SiO2Environment-friendly enhanced waterborne polyurethane ink and preparation method 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 |
| CN112646391A (en) * | 2020-12-22 | 2021-04-13 | 无锡米科思新材料科技有限公司 | Dye dispersant and preparation method thereof |
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| CN102433052A (en) * | 2011-09-10 | 2012-05-02 | 中国十七冶集团有限公司 | Aqueous polyurethane modified silicon-acrylate multifunctional waterproof heat-insulation elastic paint and preparation method thereof |
| CN104804492A (en) * | 2015-04-08 | 2015-07-29 | 牛无畏 | Scraping-resistant high-performance waterborne wood coating |
| CN105566607A (en) * | 2016-02-29 | 2016-05-11 | 深圳市姿彩科技有限公司 | Modified polyurethane acrylate and preparation method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102433052A (en) * | 2011-09-10 | 2012-05-02 | 中国十七冶集团有限公司 | Aqueous polyurethane modified silicon-acrylate multifunctional waterproof heat-insulation elastic paint and preparation method thereof |
| CN104804492A (en) * | 2015-04-08 | 2015-07-29 | 牛无畏 | Scraping-resistant high-performance waterborne wood coating |
| CN105566607A (en) * | 2016-02-29 | 2016-05-11 | 深圳市姿彩科技有限公司 | Modified polyurethane acrylate and preparation method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| CN111647306A (en) * | 2020-07-14 | 2020-09-11 | 南通贝得彩色印刷有限公司 | In situ generation of organized SiO2Environment-friendly enhanced waterborne polyurethane ink and preparation method thereof |
| CN112646391A (en) * | 2020-12-22 | 2021-04-13 | 无锡米科思新材料科技有限公司 | Dye dispersant and preparation method thereof |
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