CN104211904A - Environment-friendly vegetable oil-based polyurethane binder resin, corrugated board ink and preparation method of environment-friendly vegetable oil-based polyurethane binder resin - Google Patents
Environment-friendly vegetable oil-based polyurethane binder resin, corrugated board ink and preparation method of environment-friendly vegetable oil-based polyurethane binder resin Download PDFInfo
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- 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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- 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
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- 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
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- 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
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- 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
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
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- 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
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
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- 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
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6648—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6651—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
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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
- C08G18/65—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
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- 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
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Abstract
The invention relates to the field of corrugated board printing inks and particularly relates to environment-friendly vegetable oil-based polyurethane binder resin, a corrugated board ink and a preparation method of the environment-friendly vegetable oil-based polyurethane binder resin. The polyurethane binder resin is obtained by acting a vegetable oil-based polyurethane prepolymer, a hydrophilic chain extender, a micromolecule chain extender, a neutralizer and water, wherein the vegetable oil-based polyurethane prepolymer is obtained by reacting polyacrylate-modified vegetable oil, low polymer polyatomic alcohol and diisocyanate; and the vegetable oil-based polyurethane water-based ink is obtained by mixing pigments, a defoaming agent, water-based paraffin and water into the vegetable oil-based polyurethane binder resin. The water-based ink has good printability and has good biodegradability by using the vegetable oil to substitute most of organic polymers as synthetic raw materials of the binder resin; and the grain size of the ink is controlled within a micro-nano range, so that the ink is dried on the surface of the corrugated board very well to achieve film-forming and bonding effects.
Description
Technical field
The invention belongs to corrugated board printing ink area, relate to a kind of environmental-friendly plant oil base urethane low-melting ink vehicle resin, corrugated cardboard ink and method for making.
Background technology
China is packaging big country in the world, and Corrugated Box occupies critical role in China's packaging industry.Why corrugation package paper and derived product thereof obtain high speed development, that the features such as the lightweight that it possesses, eleganceization, repeatability, designability can meet the packaging demand of all trades and professions product greatly because the development of fluting board industry meets the requirement of Environmental Protection in China, Sustainable development and conservation-minded society.Because it is applied widely, the printing quality problem of Corrugated Box is following, because the printing quality of Corrugated Box is not only related to the visual appearance of Corrugated Box, also has certain influence to the prospect for sales of packaged product and the image of products production enterprise simultaneously.The Corrugated Box market constantly expanded along with China, result in the competition of Corrugated Box packages printing association area, and the producer possessing high quality printing often has more competitive edge in competition.
The key of giving Corrugated Box packaging aesthetic feeling and texture is the use of printing-ink, in high-speed printing process, requires to be energy rapid drying to the printing-ink of corruggted wrapping case.On the other hand, corrugated cardboard is the intertexture of fiber, loose porous, has stronger absorptivity, to permeate drying after corrugated board printing water color ink.So in corrugated board printing process, when ink permeates to carton interior, must ensure that it can not pollute inner package.The uniform liquid that water color ink is made up of binder, pigment, auxiliary agent etc.Because it is using water as solvent, so water color ink has significant Environmental Safety feature: nontoxic, do not fire not quick-fried, almost non-volatility organic compound (VOC) produce.Water color ink is particularly suitable for printing the strict packing of product of the health conditions requirings such as food, wine, cigarette, beverage, toy for children, medicine.Water color ink also possess good tinting strength, shelf-stable, to features such as machine and carton performance have no adverse effects.Therefore, the ink of printing corrugated cardboard substantially all selects water color ink.It is the current environment-friendlyink ink most with development potentiality, meets the requirement of China to the increasingly stringent of the safety and environmental protection of printing-ink industry.
Summary of the invention
But, the technical problem that prior art exists is that the water color ink ubiquity drying property in the market for corrugated box printing is not ideal enough, in water color ink, the decomposition of widely used polyacrylics departs from poor-performing, cause the printing-ink on the Corrugated Box discarded not easily to reclaim disengaging, and be difficult to the problems such as decomposition at occurring in nature.
So, in order to overcome the problems referred to above that current water color ink exists, the invention provides a kind of Corrugated Box water color ink preparing environment protection type easy degraded, drying property excellence.The present invention is intended to simplify the preparation technology of the Corrugated Box water color ink possessing excellent properties, solve drying property in Corrugated Box production process and the problem such as pollution of ink in discarded removal process, current non-existent a kind of environment-friendlyink ink on a kind of China's Corrugated Box water color ink market is provided, improve the competitive power in China's water color ink market, decrease the destruction of Printing industry to ecotope, accelerate " green engineering " paces of Corrugated Box packages printing industry, and " environmental protection " and industry are organically combined.That is, the invention provides a kind of safety non-toxic, the drying property vegetable oil based polyurethane water color ink for corrugated board printing that is excellent, that easily degrade, and the preparation method of this water color ink is provided.
The present invention adopts radical polymerization and the principle of being progressively polymerized to prepare vegetable oil based polyurethane low-melting ink vehicle resin, and adopts ball milled to prepare high performance water color ink.First by radical polymerization principle, adopt the monomer of butyl methacrylate and vinylformic acid two kinds of polyacrylic ester vegetables oil (Viscotrol C) to be carried out to the modification of double bond consumption, and on vegetables oil the more active group of keyed jointing (hydroxyl); Then the method by being progressively polymerized, modified vegetables oil is adopted to replace some oligomers polyvalent alcohol to carry out the preparation of aqueous polyurethane low-melting ink vehicle, reacted by the isocyanate groups on vulcabond and the active group on vegetables oil (being mainly hydroxyl), generate vegetable oil based polyurethane performed polymer, under the effect of hydrophilic chain extender, small molecule chain extender, neutralizing agent and water, then generate the aqueous polyurethane low-melting ink vehicle resin of excellent performance; Finally low-melting ink vehicle resin is mixed with coloured pigment such as Phthalocyanine Blue BGS, white pigment such as titanium white mill base, defoamer such as GPE type defoamer, water-based paraffin etc., use ball mill to carry out mixing and ball milling, preparation high-performance Corrugated Box water color ink.
Specifically, in order to solve the problems referred to above that prior art exists, the invention provides following technical scheme:
A kind of vegetable oil based polyurethane low-melting ink vehicle resin, it is obtained by vegetable oil based polyurethane performed polymer and hydrophilic chain extender, small molecule chain extender, neutralizing agent and water effect;
Wherein, vegetable oil based polyurethane performed polymer is prepared by following method: polyacrylate modified vegetables oil and oligomer polyol and di-isocyanate reaction obtain vegetable oil based polyurethane performed polymer.
Preferably, wherein, described vegetables oil is Viscotrol C, and described polyacrylate modified vegetables oil carries out emulsion free-radical polymerization by 2-6 weight part, preferably 3-5 weight part (methyl) acrylate, 3-8 weight part, preferably 5-7 parts by weight of acrylic acid and 25-35 weight part, preferably 28-32 weight part Viscotrol C and is obtained by reacting; Described oligomer polyol is selected from polyneopentyl glycol adipate, polyethylene glycol adipate or poly-hexanodioic acid hexylene glycol ester, be preferably polyneopentyl glycol adipate, described vulcabond is selected from tolylene diisocyanate, isophorone diisocyanate or diphenylmethanediisocyanate, is preferably isoflurane chalcone diisocyanate.
In the present invention, described oligomer polyol refers to the hexanodioic acid system aliphatic poly esterdiol that relative molecular weight is 1000 ~ 3000, functionality is 2 ~ 4.
Preferably, wherein, described hydrophilic chain extender is selected from dimethylol propionic acid or dimethylolpropionic acid; Described small molecule chain extender is selected from BDO, propylene glycol or glycol ether; When wherein preparing described vegetable oil based polyurethane performed polymer, polyacrylate modified vegetables oil is obtained relative to 25-35 weight part is castor oil modified, vulcabond consumption is 75-85 weight part, preferably 78-82 weight part, and oligomer polyol consumption is 43-50 weight part, preferably 44-48 weight part.
Preferably, wherein, described hydrophilic chain extender is 8-10 weight part, preferably 8.5-10 weight part, and small molecule chain extender is 10-15 weight part, preferably 11-14 weight part.
Preferably, wherein, (methyl) acrylate is selected from (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate and or (methyl) butyl acrylate); Hydrophilic chain extender is dimethylol propionic acid; Small molecule chain extender is BDO.
Preferably, wherein, vulcabond is isophorone diisocyanate, and (methyl) acrylate is (methyl) butyl acrylate.
The present invention also provides the preparation method of above-mentioned vegetable oil based polyurethane low-melting ink vehicle resin in addition, and it comprises the steps:
1) polyacrylate modified vegetables oil is prepared: by adopting hungry reinforced method to join in the mixed system of 25-35 weight part, preferably 28-32 weight part Viscotrol C and 0.5-1.5 parts by weight Emulsifier 2-6 weight part, preferably 3-5 weight part (methyl) acrylate and 3-8 weight part, preferably 5-7 parts by weight of acrylic acid, carrying out emulsion free-radical polymerization at 65-80 DEG C and being obtained by reacting;
2) vegetable oil based polyurethane performed polymer is prepared: by step 1) the polyacrylate modified vegetables oil that obtains and oligomer polyol and vulcabond be obtained by reacting vegetable oil based polyurethane performed polymer in 75-85 DEG C, wherein, polyacrylate modified vegetables oil is obtained relative to 25-35 weight part is castor oil modified, vulcabond consumption is 75-85 weight part, preferably 78-82 weight part, and oligomer polyol consumption is 43-50 weight part, preferably 44-48 weight part;
3) hydrophilic chain extender chain extension: in step 2) in the vegetable oil based polyurethane performed polymer that obtains, add hydrophilic chain extender 8-10 weight part, preferably 8.5-10 weight part and carry out chain extending reaction;
4) small molecule chain extender chain extending reaction: the small molecule chain extender of 10-15 weight part, preferably 11-14 weight part is dissolved in solvent and slowly adds step 3) in the reaction system that obtains, in 38-45 DEG C of reaction; And
5) neutralization reaction; In step 4) in the reaction system that obtains, slowly add amine aqueous solution; Then add mineral alkali, regulate pH value to 7.5-9, thus obtain vegetable oil based polyurethane low-melting ink vehicle resin.
Wherein, in the preparation process in accordance with the present invention, in step 2) in, the consumption controlling vulcabond when preparing base polyurethane prepolymer for use as is excessive, make obtained base polyurethane prepolymer for use as belong to end NCO fundamental mode performed polymer, thus add chainextender after being convenient to and carry out chain extending reaction.
Moreover the invention provides a kind of vegetable oil based polyurethane water color ink, it is obtained by hybrid pigment, defoamer, water-based paraffin and water in foregoing vegetable oil based polyurethane low-melting ink vehicle resin.
Wherein, described pigment optimization comprises conventional those colored tinting pigments such as phthalocyanine blue pigment and the white pigment such as titanium dioxide in this area, and those pigment that can be used in the present invention of every this area routine all can use in the present invention.Wherein, defoamer can adopt those defoamers well known in the art, and such as GP type defoamer, polyether-modified silicon etc. all may be used in the present invention.Wherein, GP type defoamer is initiator with glycerine, and by propylene oxide, or the mixture of oxyethane and propylene oxide carries out addition polymerization and makes.Wherein GPE type defoamer is the one in GP type defoamer, and namely GPE type defoamer steeps enemy, is the polypropylene glycol link ends addition of ethylene oxide again at GP type defoamer, becomes the polyoxyethylene oxypropylene glycerine that the end of the chain is hydrophilic group.The water-based paraffin that this area is commonly used all can be used in the present invention, and preferred paraffin active principle content is the water-based paraffin of 20-25%.
In addition, the invention provides the preparation method of described vegetable oil based polyurethane water color ink, it is characterized in that, comprise the steps:
1) polyacrylate modified vegetables oil is prepared: by adopting hungry reinforced method to join in the mixed system of 25-35 weight part, preferably 28-32 weight part Viscotrol C and 0.5-1.5 parts by weight Emulsifier 2-6 weight part, preferably 3-5 weight part (methyl) acrylate and 3-8 weight part, preferably 5-7 parts by weight of acrylic acid, carrying out emulsion free-radical polymerization at 65-80 DEG C and being obtained by reacting;
2) vegetable oil based polyurethane performed polymer is prepared: by step 1) the polyacrylate modified vegetables oil that obtains and oligomer polyol and vulcabond be obtained by reacting vegetable oil based polyurethane performed polymer in 75-85 DEG C, wherein, polyacrylate modified vegetables oil is obtained relative to 25-35 weight part is castor oil modified, vulcabond ester consumption is 75-85 weight part, preferably 78-82 weight part, and oligomer polyol consumption is 43-50 weight part, preferably 44-48 weight part;
3) hydrophilic chain extender chain extension: in step 2) in the vegetable oil based polyurethane performed polymer that obtains, add hydrophilic chain extender 8-10 weight part, preferably 8.5-10 weight part and carry out chain extending reaction;
4) small molecule chain extender chain extending reaction: the small molecule chain extender of 10-15 weight part, preferably 11-14 weight part is dissolved in solvent and slowly adds step 3) in the reaction system that obtains, in 38-45 DEG C of reaction; And
5) neutralization reaction; In step 4) in the reaction system that obtains, slowly add amine aqueous solution; Then add mineral alkali, regulate pH value to 7.5-9, thus obtain vegetable oil based polyurethane low-melting ink vehicle resin; And
6) hybrid pigment, defoamer, water-based paraffin and water: by step 4) the aqueous polyurethane low-melting ink vehicle resin that obtains and pigment, defoamer, water-based paraffin and water is mixed to get water color ink.
Wherein, step 5 above) in, amine used is preferably triethylamine.
Preferably, for the preparation method of the aforesaid vegetable oil based polyurethane water color ink of the present invention, wherein, also in step 4) after, in step 4) add a part of pigment in the reaction system that obtains after carry out step 5 again).Particularly when pigment be solid or pulverulence time, in step 4) in add be evenly fully in order to mix; When pigment is liquid state in step 6) in mix.
Preferably, for the preparation method of the aforesaid vegetable oil based polyurethane water color ink of the present invention, wherein, after step 4, in step 4) described a part of pigment of adding in the reaction system that obtains refers to the colored tinting pigment that this area such as phthalocyanine blue or phthalocyanine green is conventional, preferred Phthalocyanine Blue BGS 55-65 weight part; Wherein in step 6) in, described pigment is white pigment such as titanium dioxide or lithopone etc., preferred titanium white mill base 12-17 weight part, and described defoamer is GPE type defoamer 3-7 weight part, described water-based paraffin is 6-10 weight part, and described water is 180-250 weight part.
Preferably, for the preparation method of vegetable oil based polyurethane water color ink of the present invention, wherein, in step 6) described in pigment be Phthalocyanine Blue BGS 55-66 weight part and titanium white mill base 12-17 weight part, described defoamer is GPE type defoamer 3-7 weight part, described water-based paraffin is 6-10 weight part, and described water is 180-250 weight part.
Wherein, titanium white mill base is the mixing liquid that a kind of titanium dioxide of titanium dioxide content more than 65% and polyacrylic ester, ethyl acetate are formed.
Preferably, for the preparation method of aforesaid vegetable oil based polyurethane low-melting ink vehicle resin or water color ink, wherein, step 1) in, the described hunger method of feeding in raw material refers to 1.8-2.5 hour, preferably (methyl) acrylate and vinylformic acid is joined in the mixed system of Viscotrol C and emulsifying agent with 2 hours.
Preferably, for preparation method recited above, wherein, step 3) in, described chain extending reaction carries out chain extending reaction under 3-7 weight part ketone solvent exists, wherein, first 60 when carrying out chain extending reaction
-70 DEG C of reaction 8-12 minute; Again in 82-90 DEG C of reaction 1.8-2.5 hour.
In addition, the present invention's described application of vegetable oil based polyurethane water color ink in corrugated box printing of also providing described vegetable oil based polyurethane low-melting ink vehicle resin or described preparation method to obtain.
In addition, the present invention also provides a kind of corrugated cardboard ink, is obtained by the preparation method above described in any one.
Wherein, the Viscotrol C adopted in the present invention is a kind of natural polyhydroxy glycerin fatty acid ester, wherein containing about 70% glycerine three Viscotrol C oleic acid ester and 30% glycerine two Viscotrol C oleic acid ester list linoleate etc., average functionality is 2.7, namely, the chemical name of main component is 9-thiazolinyl-12-hydroxy octadecadienoic acid glyceryl ester, and its structural formula is as follows:
The Corrugated Box water color ink prepared in the present invention possesses good printability, can promote the popularization of environmentally friendly machine in Printing industry, is conducive to the reprocessing problem solving the discarded ink of printing.And use vegetables oil to replace most of organic polymer, as the synthesis material of low-melting ink vehicle resin, possess excellent biological degradability.The particle size range of the water color ink obtained, in micro-nano scope, can better carry out film forming cohesive action on the surface of corrugated cardboard by the drying mechanism that infiltration is dry.
Accompanying drawing explanation
Fig. 1 is the infrared comparison diagram in castor oil modified front and back in embodiment 1;
Fig. 2 is water color ink particle diameter and the grain size distribution of embodiment 1 preparation.
Embodiment
Have safety non-toxic, the drying property vegetable oil based polyurethane water color ink for corrugated board printing that is excellent, that easily degrade to prepare, preparation method of the present invention is as follows:
First, vegetable oil based polyurethane performed polymer is prepared by following method: polyacrylate modified vegetables oil and oligomer polyol and di-isocyanate reaction obtain vegetable oil based polyurethane performed polymer; Then, vegetable oil based polyurethane low-melting ink vehicle resin is obtained by vegetable oil based polyurethane performed polymer and hydrophilic chain extender, small molecule chain extender, neutralizing agent and water effect; Finally, hybrid pigment, defoamer, water-based paraffin and water obtain water color ink of the present invention then in vegetable oil based polyurethane low-melting ink vehicle resin.
In a preferred embodiment, the preparation method of vegetable oil based polyurethane corrugated cardboard water color ink of the present invention is as follows.
During preparation, adopt following raw material according to following component proportion: a kind of environmental-friendly plant oil base polyurethane corrugated carton ink, be prepared from by following raw material components and proportioning (according to parts by weight): butyl methacrylate (BMA): 2-6 weight part, vinylformic acid (AA): 3-8 weight part, Diisopropyl azodicarboxylate (AIBN): 0.1-0.5 weight part, emulsifier op-10: 0.5-1.2 weight part, vegetables oil (Viscotrol C): 25-35 weight part, polyneopentyl glycol adipate (PNA): 43-50 weight part, isophorone diisocyanate (IPDI): 75-85 weight part, dimethylol propionic acid (DMPA): 8-10 weight part, N-Methyl pyrrolidone (NMP): 14-18 weight part, 1, 4-butyleneglycol (BDO): 10-15 weight part, acetone: 4-6 weight part, deionized water: 600 weight parts, Phthalocyanine Blue BGS: 55-65 weight part, titanium white mill base 12-17 weight part, GPE type defoamer: 3-7 weight part, water-based paraffin: 6-10 weight part, di-n-butyltin dilaurate (DBTDL): 0.03-0.08 weight part, triethylamine (TEA): 8.8-12.8 weight part.Specifically, adopt above-mentioned raw materials preparation process as follows:
A, to be added by Viscotrol C clean with in the beaker of whipping appts, beaker is put into ultrasonic washing instrument, and setting ultrasonic temperature is 70 DEG C, and ultrasonic power is 600W, adds OP-10 in flask, is uniformly mixed; Get BMA, AA of metering and initiator A IBN to add in clean empty beaker and use glass stick to carry out mix and blend simultaneously, obtain mixture.Then, when ultrasonic cleaning instrument starts ultrasonic vibration, added to by mixture in the reaction system of Viscotrol C and OP-10, adding procedure adopts hungry reinforced method, has been added by mixture in 2 hours.Obtain the Viscotrol C that Polyacrylate monomer is modified;
B, by the modified castor oil in oligomer polyol and a respectively at 120 DEG C, dry 2 hours of the loft drier of 0.05Mpa vacuum tightness, after drying completes.IPDI, PNA of metering and Viscotrol C are added in the clean there-necked flask with reflux exchanger, thermometer and whipping appts, flask is put into 80 DEG C of thermostat water baths, stirring reaction is after 2 hours, add catalyzer DBTDL, react 1 hour again, make IPDI, sufficient reacting between oligomer polyol and Viscotrol C;
C, temperature of reaction system are reduced to 65 DEG C, pulverous hydrophilic chain extender DMPA is well-dispersed in a small amount of acetone, add reaction system, thus make hydrophilic chain extender under the effect of cosolvent acetone with system abundant contact reacts, better complete linking of hydrophilic radical and main chain, react 10 minutes between 60-70 DEG C, then continue to be warming up to 85 DEG C of reactions 2 hours;
D, be cooled to 40 DEG C, BDO be dissolved in N-Methyl pyrrolidone, slowly add reaction system, promote rotating speed simultaneously, high-speed stirring 1 hour.Load weighted Phthalocyanine Blue BGS is joined in reaction system, high-speed stirring mixes for 30 minutes, triethylamine is dissolved in quantitative deionized water after having reacted, slowly system is added dropwise under high-speed stirring and ultrasonic field, after being added dropwise to complete, add quantitative deionized water and carry out chain extension emulsification further, in high-speed stirring after 5 minutes, add the pH value of KOH solution regulation system to 7.5-9;
E, the low-melting ink vehicle resin in d to be mixed in beaker with titanium white mill base, GPE type defoamer, water-based paraffin, electric blender is used to be stirred by mixture, churning time is 30 minutes, then the mixture mixed is put into the discharging after 4 hours of planetary ball mill ball milling, obtain high performance vegetable oil based polyurethane corrugated cardboard water color ink.
In order to there be understanding clearly to technical characteristic of the present invention, object and effect, now describe the specific embodiment of the present invention in detail with embodiment.
Embodiment
Each raw material commercial source used in embodiment 1-3 is below as follows:
Isophorone diisocyanate (IPDI), industrial goods, Aladdin reagent;
Dimethylol propionic acid (DMPA), industrial goods, Shanghai Peng Teng Fine Chemical Co., Ltd product;
Butyl methacrylate (BMA), Tianjin good fortune chemical reagent factory in morning;
Viscotrol C (CO), chemical pure, Tianjin Tian Li chemical reagent company limited;
Vinylformic acid (AA), analytical pure, Tianjin Yong Sheng Fine Chemical Co., Ltd;
Emulsifier op-10, chemical pure, Tianjin Yong Sheng Fine Chemical Co., Ltd;
Diisopropyl azodicarboxylate (AIBN), analytical pure, Chengdu Ke Long chemical reagent factory;
Polyneopentyl glycol adipate (PNA) (molecular weight is 2000, and two ends are hydroxyl), analytical pure, Sigma-Aldrich;
Dimethylol propionic acid (DMPA), industrial goods, Shanghai Peng Teng Fine Chemical Co., Ltd product;
N-Methyl pyrrolidone (NMP), analytical pure, Tianjin recovery fine chemistry industry institute;
Acetone, analytical pure, Yantai City is Chemical Co., Ltd. in pairs;
BDO (BDO), analytical pure, Tianjin good fortune chemical reagent factory in morning;
Triethylamine (TEA), analytical pure, Tianjin Jin Yu Fine Chemical Co., Ltd;
Potassium hydroxide, analytical pure, Tianjin Chemical Co., Ltd.'s all generations;
Dibutyl tin dilaurate (DBTDL), chemical pure, Brassica rapa L analyses Chemical Industry Science Co., Ltd;
Phthalocyanine Blue BGS, titanium white mill base (titanium white mill base moiety: titanium dioxide: 65%, polyacrylate(s): 35%, ethyl acetate: 3%, polyoxyethyl propyl polyoxyethanyl glyceryl ether: 0.5%, paraffin: 0.5%, polydimethylsiloxane: 1%), industrial goods, Jiangsu Mei Kailun pigment chemical industry;
GPE type defoamer, analytical pure, the good industry chemical industry of the prosperous treasured in Xi'an;
Water-based paraffin (paraffin of 22%, the OP-10 of 3%, the sodium lauryl sulphate of 4.5%, water, the sodium hydroxide of 0.3%, the wilkinite of 0.2% of 70%), industrial goods, Guangzhou Guan Zhi Chemical Co., Ltd..
The preparation of embodiment 1 environmental-friendly plant oil base polyurethane corrugated carton ink
Preparation process is specific as follows:
A, to be added by the Viscotrol C of 30g clean with in the beaker of whipping appts, beaker is put into ultrasonic washing instrument, and design temperature is 70 DEG C, and ultrasonic power is 600W, and the OP-10 adding 1g, in flask, is uniformly mixed; The AIBN simultaneously getting AA and 0.3g of BMA, 6g of 4g adds in clean empty beaker and uses glass stick to carry out mix and blend, obtains mixture.Then, when ultrasonic cleaning instrument starts ultrasonic vibration, added to by mixture in the reaction system of Viscotrol C and OP-10, adding procedure adopts hungry reinforced method, has been added by mixture in 2 hours.Obtain the Viscotrol C that Polyacrylate monomer is modified;
B, by Viscotrol C modified in PNA and a of 46.4g at 120 DEG C, dry 2 hours of the loft drier of 0.05Mpa vacuum tightness, after drying completes.By the IPDI of 80g, add in the clean there-necked flask with reflux exchanger, thermometer and whipping appts with the modified Viscotrol C prepared in PNA and a, flask is put into 80 DEG C of thermostat water baths, stirring reaction is after 2 hours, add the catalyzer DBTDL of 0.05g, continue stirring reaction 1 hour, make IPDI, sufficient reacting between oligomer polyol and Viscotrol C;
C, reduction temperature of reaction system to 65 DEG C, the hydrophilic chain extender DMPA of pulverous 9.7g is well-dispersed in the acetone of 5g, add reaction system, thus make hydrophilic chain extender under the effect of cosolvent acetone with system abundant contact reacts, better complete linking of hydrophilic radical and main chain, react 10 minutes between 60-70 DEG C, then continue to be warming up to 85 DEG C of reactions 2 hours;
D, be cooled to 40 DEG C, by 1 of 12.4g, 4-butanediol is in the N-Methyl pyrrolidone of 16.5g, slowly add reaction system, promote rotating speed simultaneously, high-speed stirring reacts 1 hour, the Phthalocyanine Blue BGS of 60g is joined in reaction system, high-speed stirring mixes for 30 minutes, after having reacted, the triethylamine of 10.8g is dissolved in the deionized water of 100g, slowly system is added dropwise under high-speed stirring and ultrasonic field, after being added dropwise to complete, the deionized water adding 100g carries out chain extension emulsification further, in high-speed stirring after 15 minutes, KOH is dissolved in the deionized water of 50g, add the pH value to 7.5 of reaction system regulation system to,
E, the GPE type defoamer of the titanium white mill base of the low-melting ink vehicle resin in d and 15g, 5g, the water-based paraffin of 8g and the deionized water of 200g to be mixed in beaker, electric blender is used to be stirred by mixture, churning time is 30 minutes, then the mixture mixed is put into the discharging after 4 hours of planetary ball mill ball milling, obtain high performance vegetable oil based polyurethane corrugated cardboard water color ink.
Performance evaluation is carried out for the vegetable oil based polyurethane corrugated cardboard water color ink obtained:
Use the HADV-II+PRO type rotational viscosimeter of U.S. Brookfield to detect the viscosity of water color ink, the mean values of detection is 8570 mpaS, meets the viscosity requirement as corrugated cardboard printing water color ink; According to the solid content of the standard test water color ink of ISO 124:1997, the solid content obtaining water color ink is 56.5%, and possess higher amount of solid content, drying property is better.
SHIMADIU FTIR-8400S (CE) the type Fourier infrared spectrograph of Japanese Shimadzu is used to carry out structure detection to the Viscotrol C after modification money, as shown in Figure 1, as can be seen from Figure 1, the infrared spectrogram of the Viscotrol C is before modified at the peak of 3000 more than cm-1, narrow than before modified of the width of modified Viscotrol C, this region belongs to the stretching vibration region of the c h bond that unsaturated C=C key connects, so show that in the molecular chain chain of Viscotrol C, insatiable hunger degree is higher than modified Viscotrol C, show to consume the double bond in quantitative Viscotrol C, success has carried out modification to it.
LS-230 type laser granulometry is used to detect the particle diameter of the water color ink of preparation, its particle diameter and (volume) grain size distribution are as shown in Figure 2, as shown in Figure 2, the size distribution of the water color ink of preparation belongs to three peak distributions, particle size range is in micro-nano region, main median size is 162nm, 721nm and 2.208 μm, wherein distributing maximum is 721nm, particle diameter is less, for the Corrugated Box under infiltration drying mechanism, possess and permeate drying property fast, meet the high speed printing demand of corrugated cardboard.
The preparation of embodiment 2 environmental-friendly plant oil base polyurethane corrugated carton ink
Preparation process is specific as follows:
A, to be added by the Viscotrol C of 25g clean with in the beaker of whipping appts, beaker is put into ultrasonic washing instrument, and design temperature is 65 DEG C, and ultrasonic power is 600W, and the OP-10 adding 0.8g, in flask, is uniformly mixed; The AIBN simultaneously getting AA and 0.1g of BMA, 3g of 2g adds in clean empty beaker and uses glass stick to carry out mix and blend, obtains mixture.Then, when ultrasonic cleaning instrument starts ultrasonic vibration, added to by mixture in the reaction system of Viscotrol C and OP-10, adding procedure adopts hungry reinforced method, has been added by mixture in 1.5 hours.Obtain the Viscotrol C that Polyacrylate monomer is modified;
B, by Viscotrol C modified in PNA and a of 43g at 120 DEG C, dry 2 hours of the loft drier of 0.05Mpa vacuum tightness, after drying completes.By the IPDI of 75g, add in the clean there-necked flask with reflux exchanger, thermometer and whipping appts with the modified Viscotrol C prepared in PNA and a, flask is put into 75 DEG C of thermostat water baths, stirring reaction is after 2 hours, add the catalyzer DBTDL of 0.03g, continue stirring reaction 1 hour, make IPDI, sufficient reacting between oligomer polyol and Viscotrol C;
C, reduction temperature of reaction system to 60 DEG C, the hydrophilic chain extender DMPA of pulverous 8g is well-dispersed in the acetone of 4g, add reaction system, thus make hydrophilic chain extender under the effect of cosolvent acetone with system abundant contact reacts, the z better completing hydrophilic radical and main chain connects, react 10 minutes between 60 DEG C, then continue to be warming up to 82 DEG C of reactions 2 hours;
D, be cooled to 38 DEG C, by 1 of 10g, 4-butanediol is in the N-Methyl pyrrolidone of 14g, slowly add reaction system, promote rotating speed simultaneously, high-speed stirring reacts 1 hour, the Phthalocyanine Blue BGS of 55g is joined in reaction system, high-speed stirring mixes for 30 minutes, after having reacted, the triethylamine of 8.8g is dissolved in the deionized water of 100g, slowly system is added dropwise under high-speed stirring and ultrasonic field, after being added dropwise to complete, the deionized water adding 100g carries out chain extension emulsification further, in high-speed stirring after 15 minutes, KOH is dissolved in the deionized water of 50g, add the pH value to 8 of reaction system regulation system to,
E, the GPE type defoamer of the titanium white mill base of the low-melting ink vehicle resin in d and 12g, 3g, the water-based paraffin of 6g and the deionized water of 200g to be mixed in beaker, electric blender is used to be stirred by mixture, churning time is 30 minutes, then the mixture mixed is put into the discharging after 4 hours of planetary ball mill ball milling, obtain high performance vegetable oil based polyurethane corrugated cardboard water color ink.
Carry out performance evaluation for the vegetable oil based polyurethane corrugated cardboard water color ink obtained according to the method identical with embodiment 1, measurement result shows: the mean values of detection is 8600mPaS, meets the viscosity requirement as corrugated cardboard printing water color ink;
The solid content of water color ink is 62.5%, and possess higher amount of solid content, drying property is better.Fourier infrared spectrograph carries out structure detection to the Viscotrol C after modification money and shows that in the molecular chain chain of Viscotrol C, insatiable hunger degree is higher than modified Viscotrol C, shows to consume the double bond in quantitative Viscotrol C, has successfully carried out modification to it.
The size distribution of the water color ink of preparation belongs to three peak distributions, particle size range is in micro-nano region, main median size is 158nm, 718nm and 2.005 μm, wherein distributing maximum is 718nm, particle diameter is less, for the Corrugated Box under infiltration drying mechanism, possess and permeate drying property fast, meet the high speed printing demand of corrugated cardboard.
The preparation of embodiment 3 environmental-friendly plant oil base polyurethane corrugated carton ink
Preparation process is specific as follows:
B, to be added by the Viscotrol C of 35g clean with in the beaker of whipping appts, beaker is put into ultrasonic washing instrument, and design temperature is 80 DEG C, and ultrasonic power is 600W, and the OP-10 adding 1.2g, in flask, is uniformly mixed; The AIBN simultaneously getting AA and 0.5g of BMA, 8g of 6g adds in clean empty beaker and uses glass stick to carry out mix and blend, obtains mixture.Then, when ultrasonic cleaning instrument starts ultrasonic vibration, added to by mixture in the reaction system of Viscotrol C and OP-10, adding procedure adopts hungry reinforced method, has been added by mixture in 2.5 hours.Obtain the Viscotrol C that Polyacrylate monomer is modified;
B, by Viscotrol C modified in PNA and a of 50g at 120 DEG C, dry 2 hours of the loft drier of 0.05Mpa vacuum tightness, after drying completes.By the IPDI of 85g, add in the clean there-necked flask with reflux exchanger, thermometer and whipping appts with the modified Viscotrol C prepared in PNA and a, flask is put into 85 DEG C of thermostat water baths, stirring reaction is after 2 hours, add the catalyzer DBTDL of 0.08g, continue stirring reaction 1 hour, make IPDI, sufficient reacting between oligomer polyol and Viscotrol C;
C, reduction temperature of reaction system to 70 DEG C, the hydrophilic chain extender DMPA of pulverous 10g is well-dispersed in the acetone of 6g, add reaction system, thus make hydrophilic chain extender under the effect of cosolvent acetone with system abundant contact reacts, better complete linking of hydrophilic radical and main chain, react 10 minutes between 70 DEG C, then continue to be warming up to 90 DEG C of reactions 2 hours;
D, be cooled to 45 DEG C, by 1 of 15g, 4-butanediol is in the N-Methyl pyrrolidone of 18g, slowly add reaction system, promote rotating speed simultaneously, high-speed stirring reacts 1 hour, the Phthalocyanine Blue BGS of 65g is joined in reaction system, high-speed stirring mixes for 30 minutes, after having reacted, the triethylamine of 10.8g is dissolved in the deionized water of 100g, slowly system is added dropwise under high-speed stirring and ultrasonic field, after being added dropwise to complete, the deionized water adding 100g carries out chain extension emulsification further, in high-speed stirring after 15 minutes, KOH is dissolved in the deionized water of 50g, add the pH value to 9 of reaction system regulation system to,
E, the GPE type defoamer of the titanium white mill base of the low-melting ink vehicle resin in d and 17g, 7g, the water-based paraffin of 10g and the deionized water of 200g to be mixed in beaker, electric blender is used to be stirred by mixture, churning time is 30 minutes, then the mixture mixed is put into the discharging after 4 hours of planetary ball mill ball milling, obtain high performance vegetable oil based polyurethane corrugated cardboard water color ink.
Carry out performance evaluation for the vegetable oil based polyurethane corrugated cardboard water color ink obtained according to the method identical with embodiment 1, measurement result shows: the mean values of detection is 8340mPaS, meets the viscosity requirement as corrugated cardboard printing water color ink;
The solid content of water color ink is 60.5%, and possess higher amount of solid content, drying property is better.Fourier infrared spectrograph carries out structure detection to the Viscotrol C after modification money and shows that in the molecular chain chain of Viscotrol C, insatiable hunger degree is higher than modified Viscotrol C, shows to consume the double bond in quantitative Viscotrol C, has successfully carried out modification to it.
The size distribution of the water color ink of preparation belongs to three peak distributions, particle size range is in micro-nano region, main median size is 165nm, 730nm and 2.525 μm, wherein distributing maximum is 730nm, particle diameter is less, for the Corrugated Box under infiltration drying mechanism, possess and permeate drying property fast, meet the high speed printing demand of corrugated cardboard.
As can be seen from embodiment 1-3 above, the viscosity of water-based ink scope prepared by method of the present invention, in 8300-8600 mpaS, meets the viscosity requirement of corrugated cardboard printing water color ink; Its solid content is more than 55%, and possess higher solids content, drying property is better; Its particle diameter is less, and maximum particle diameter is within the scope of 710-730nm, and the less OA of water color ink particle diameter of the present invention, possesses and permeate drying property fast as can be seen here, meets the high speed printing demand of corrugated cardboard.
Claims (16)
1. a vegetable oil based polyurethane low-melting ink vehicle resin, it is obtained by vegetable oil based polyurethane performed polymer and hydrophilic chain extender, small molecule chain extender, neutralizing agent and water effect;
Wherein, vegetable oil based polyurethane performed polymer is prepared by following method: polyacrylate modified vegetables oil and oligomer polyol and di-isocyanate reaction obtain vegetable oil based polyurethane performed polymer.
2. vegetable oil based polyurethane low-melting ink vehicle resin according to claim 1, wherein, described vegetables oil is Viscotrol C, and described polyacrylate modified vegetables oil carries out emulsion free-radical polymerization by 2-6 weight part, preferably 3-5 weight part (methyl) acrylate, 3-8 weight part, preferably 5-7 parts by weight of acrylic acid and 25-35 weight part, preferably 28-32 weight part Viscotrol C and is obtained by reacting; Described oligomer polyol is selected from polyneopentyl glycol adipate, polyethylene glycol adipate or poly-hexanodioic acid hexylene glycol ester, be preferably polyneopentyl glycol adipate, described vulcabond is selected from tolylene diisocyanate, isophorone diisocyanate or diphenylmethanediisocyanate, is preferably isoflurane chalcone diisocyanate.
3. vegetable oil based polyurethane low-melting ink vehicle resin according to claim 1 and 2, wherein, described hydrophilic chain extender is selected from dimethylol propionic acid or dimethylolpropionic acid; Described small molecule chain extender is selected from BDO, propylene glycol or glycol ether;
When wherein preparing described vegetable oil based polyurethane performed polymer, polyacrylate modified vegetables oil is obtained relative to 25-35 weight part is castor oil modified, vulcabond consumption is 75-85 weight part, preferably 78-82 weight part, and oligomer polyol consumption is 43-50 weight part, preferably 44-48 weight part.
4. vegetable oil based polyurethane low-melting ink vehicle resin according to claim 3, wherein, described hydrophilic chain extender is 8-10 weight part, preferably 8.5-10 weight part, and small molecule chain extender is 10-15 weight part, preferably 11-14 weight part.
5. the vegetable oil based polyurethane low-melting ink vehicle resin according to any one of claim 1-3, wherein, (methyl) acrylate is selected from (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate and or (methyl) butyl acrylate); Hydrophilic chain extender is dimethylol propionic acid; Small molecule chain extender is BDO.
6. vegetable oil based polyurethane low-melting ink vehicle resin according to claim 5, wherein, vulcabond is isophorone diisocyanate, and (methyl) acrylate is (methyl) butyl acrylate.
7. the preparation method of the vegetable oil based polyurethane low-melting ink vehicle resin described in any one of claim 1-6, it comprises the steps:
1) polyacrylate modified vegetables oil is prepared: by adopting hungry reinforced method to join in the mixed system of 25-35 weight part, preferably 28-32 weight part Viscotrol C and 0.5-1.5 parts by weight Emulsifier 2-6 weight part, preferably 3-5 weight part (methyl) acrylate and 3-8 weight part, preferably 5-7 parts by weight of acrylic acid, carrying out emulsion free-radical polymerization at 65-80 DEG C and being obtained by reacting;
2) vegetable oil based polyurethane performed polymer is prepared: by step 1) the polyacrylate modified vegetables oil that obtains and oligomer polyol and vulcabond be obtained by reacting vegetable oil based polyurethane performed polymer in 75-85 DEG C, wherein, polyacrylate modified vegetables oil is obtained relative to 25-35 weight part is castor oil modified, vulcabond consumption is 75-85 weight part, preferably 78-82 weight part, and oligomer polyol consumption is 43-50 weight part, preferably 44-48 weight part;
3) hydrophilic chain extender chain extension: in step 2) in the vegetable oil based polyurethane performed polymer that obtains, add hydrophilic chain extender 8-10 weight part, preferably 8.5-10 weight part and carry out chain extending reaction;
4) small molecule chain extender chain extending reaction: the small molecule chain extender of 10-15 weight part, preferably 11-14 weight part is dissolved in solvent and slowly adds step 3) in the reaction system that obtains, in 38-45 DEG C of reaction; And
5) neutralization reaction; In step 4) in the reaction system that obtains, slowly add amine aqueous solution; Then add mineral alkali, regulate pH value to 7.5-9, thus obtain vegetable oil based polyurethane low-melting ink vehicle resin.
8. a vegetable oil based polyurethane water color ink, it is obtained by hybrid pigment, defoamer, water-based paraffin and water in the vegetable oil based polyurethane low-melting ink vehicle resin described in any one of claim 1-6.
9. the preparation method of vegetable oil based polyurethane water color ink according to claim 8, is characterized in that, comprise the steps:
1) polyacrylate modified vegetables oil is prepared: by adopting hungry reinforced method to join in the mixed system of 25-35 weight part, preferably 28-32 weight part Viscotrol C and 0.5-1.5 parts by weight Emulsifier 2-6 weight part, preferably 3-5 weight part (methyl) acrylate and 3-8 weight part, preferably 5-7 parts by weight of acrylic acid, carrying out emulsion free-radical polymerization at 65-80 DEG C and being obtained by reacting;
2) vegetable oil based polyurethane performed polymer is prepared: by step 1) the polyacrylate modified vegetables oil that obtains and oligomer polyol and vulcabond be obtained by reacting vegetable oil based polyurethane performed polymer in 75-85 DEG C, wherein, polyacrylate modified vegetables oil is obtained relative to 25-35 weight part is castor oil modified, vulcabond ester consumption is 75-85 weight part, preferably 78-82 weight part, and oligomer polyol consumption is 43-50 weight part, preferably 44-48 weight part;
3) hydrophilic chain extender chain extension: in step 2) in the vegetable oil based polyurethane performed polymer that obtains, add hydrophilic chain extender 8-10 weight part, preferably 8.5-10 weight part and carry out chain extending reaction;
4) small molecule chain extender chain extending reaction: the small molecule chain extender of 10-15 weight part, preferably 11-14 weight part is dissolved in solvent and slowly adds step 3) in the reaction system that obtains, in 38-45 DEG C of reaction; And
5) neutralization reaction; In step 4) in the reaction system that obtains, slowly add amine aqueous solution; Then add mineral alkali, regulate pH value to 7.5-9, thus obtain vegetable oil based polyurethane low-melting ink vehicle resin; And
6) hybrid pigment, defoamer, water-based paraffin and water: by step 4) the aqueous polyurethane low-melting ink vehicle resin that obtains and pigment, defoamer, water-based paraffin and water is mixed to get water color ink.
10. the preparation method of vegetable oil based polyurethane water color ink according to claim 9, wherein, also in step 4) after, in step 4) add a part of pigment in the reaction system that obtains after carry out step 5 again).
The preparation method of 11. vegetable oil based polyurethane water color inks according to claim 10, wherein, after step 4, in step 4) described a part of pigment of adding in the reaction system that obtains refers to colored tinting pigment 55-65 weight part; Wherein in step 6) in, described pigment is white pigment 12-17 weight part, and described defoamer is GPE type defoamer 3-7 weight part, and described water-based paraffin is 6-10 weight part, and described water is 180-250 weight part.
The preparation method of 12. vegetable oil based polyurethane water color inks according to claim 9, wherein, in step 6) described in pigment be Phthalocyanine Blue BGS 55-66 weight part and titanium white mill base 12-17 weight part, described defoamer is GPE type defoamer 3-7 weight part, described water-based paraffin is 6-10 weight part, and described water is 180-250 weight part.
13. preparation methods according to Claim 8 or described in any one of 9-12, wherein, step 1) in, the described hunger method of feeding in raw material refers to 1.8-2.5 hour, preferably (methyl) acrylate and vinylformic acid is joined in the mixed system of Viscotrol C and emulsifying agent with 2 hours.
14. preparation methods according to Claim 8 or described in any one of 9-12, wherein, step 3) in, described chain extending reaction carries out chain extending reaction under 3-7 weight part ketone solvent exists, wherein, first at 60-70 DEG C of reaction 8-12 minute when carrying out chain extending reaction; Again in 82-90 DEG C of reaction 1.8-2.5 hour.
The described application of vegetable oil based polyurethane water color ink in corrugated box printing that vegetable oil based polyurethane low-melting ink vehicle resin described in 15. any one of claim 1-6 or claim 8 or the preparation method described in any one of claim 9-14 obtain.
16. 1 kinds of corrugated cardboard ink, are obtained by the preparation method described in any one of claim 9-14.
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| CN116200073A (en) * | 2023-03-10 | 2023-06-02 | 广州市哲铭油墨涂料有限公司 | Water-based ink with quick-drying function and preparation method thereof |
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| CN103788328A (en) * | 2013-09-02 | 2014-05-14 | 上海涂料有限公司技术中心 | Oxidized self-cross-linked waterborne acrylic polyurethane dispersion and preparation method thereof |
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| CN106589291A (en) * | 2016-12-29 | 2017-04-26 | 合众（佛山）化工有限公司 | Castor oil terminated polyurethane water-based ink resin and preparation method thereof |
| CN107267049A (en) * | 2017-07-25 | 2017-10-20 | 安徽省禾健米业集团有限公司 | A kind of vegetable oil based polyurethane coating |
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| CN107814902A (en) * | 2017-11-06 | 2018-03-20 | 万华化学集团股份有限公司 | A kind of polyurethane aqueous dispersion body of hydroxyl and its production and use |
| 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 |
| CN116200073A (en) * | 2023-03-10 | 2023-06-02 | 广州市哲铭油墨涂料有限公司 | Water-based ink with quick-drying function and preparation method thereof |
| CN116200073B (en) * | 2023-03-10 | 2023-10-13 | 广州市哲铭油墨涂料有限公司 | Water-based ink with quick-drying function and preparation method thereof |
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