CN107987611A - A kind of hyperbranched resin base UV cures jetted ink and its preparation method and application - Google Patents

A kind of hyperbranched resin base UV cures jetted ink and its preparation method and application Download PDF

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CN107987611A
CN107987611A CN201711429157.6A CN201711429157A CN107987611A CN 107987611 A CN107987611 A CN 107987611A CN 201711429157 A CN201711429157 A CN 201711429157A CN 107987611 A CN107987611 A CN 107987611A
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CN107987611B (en
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袁腾
梁斌
苏宇沛
杨卓鸿
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South China Agricultural University
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    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D11/00Inks
    • C09D11/30Inkjet printing inks
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D11/00Inks
    • C09D11/02Printing inks
    • C09D11/10Printing inks based on artificial resins
    • C09D11/101Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing

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Abstract

The invention belongs to UV cured printing ink preparing technical fields, disclose a kind of hyperbranched resin base UV and cure jetted ink and its preparation method and application.Natural reproducible resource vegetable oil is introduced the preparation of ink by the present invention, synthesize a vegetable oil base UV and cure ultra-branched polyurethane acrylate, it instead of the UV curing monomers of the polyfunctionality of traditional petrochemical origin, new application field is opened for natural material, its use value is improved, alleviates the pressure of petrochemical industry.Six-membered ring structure is introduced in the hyperbranched UV cured polyurethane acrylates of plant oil base prepared by the present invention, so that after its UV film-forming, cured film has more preferable hardness and heat resistance.Hyper-branched prepolymers are introduced in UV cured printing inks, so that ink has lower viscosity, it is possible to reduce the usage amount of reactive diluent.The hyperbranched resin base UV of the present invention cures jetted ink and can be widely used in UV ink jet printing industrial systems.

Description

A kind of hyperbranched resin base UV cures jetted ink and its preparation method and application
Technical field
The invention belongs to UV cured printing ink preparing technical fields, more particularly to a kind of hyperbranched resin base UV cures ink-jet oil Ink and its preparation method and application.
Background technology
UV ink jet printings are a kind of new technologies to grow up at the end of the 20th century, it combines ink-jet printing technology and UV cures The respective advantage of technology, existing ink-jet printing technology using and operational facility, also have UV curing technologies economically, skill Advantage in art and in environmental protection:First, UV jetted inks will not dry up face on the print head, avoid ink setting and be bonded in spray Cause serious problems in mouth, it is not required that the insoluble substance in cleaning sprayer, and cleaning sprayer is in other ink-jet technologies The problem of common;Secondly, ink-jet products have prominent light resistance and product resistance, and curing rate of drying is quick, and spray Organic volatile is free of in the component of black ink.Therefore it is that one kind that ink develops becomes that UV jetted inks, which substitute solvent-based ink, Gesture, China is every year because of the VOC up to hundreds of thousands tons being discharged into using solvent-borne type ink used for plastic in air, if using UV ink-jets oil Ink substitutes solvent-borne type ink used for plastic, and tremendous contribution will be made to reducing China's VOC emission.
The main reason for influencing the development of UV jetted inks, its existing ink-jet apparatus derived from a few external producer, price Costliness, and restricted be subject to its main raw material(s) resin property and price, it is mainly few by foreign countries to result in current UV jetted inks Several several chemical industry giants are monopolized.Wherein design it is low it is viscous, surface tension is suitable, high curing reactivity, strong mechanical performance UV resins And realize that its industrialization is to develop the key of UV jetted inks, it is its hardness to cured film, pliability, intensity, adhesion, wear-resisting Property, corrosion resistance etc. and decisive influence is suffered to the cured sensitivity of UV.The more UV of research cures pure third at present Appearance of film, hardness and the chemical-resistance of alkene acid ester resin are often not satisfactory, its reason is exactly matrix resin chain structure list One, viscosity is high, and solid content is low, and functional group's degree of unsaturation and UV activity of curing reaction are low, and curing performance, which is not enough to reach, is expected to want Ask.Hyperbranched resin because of its unique three-dimensional spherical multiple-branching construction, and with peripheral degree of functionality is high, reactivity by force, viscosity it is low Etc. numerous characteristics, UV inkjet ink systems can be applied to, to alleviate the contradiction between linear systems large arch dam and low viscosity, carried The performance of whole UV curing systems is risen, but since the structure design of hyperbranched resin has certain difficulty, at present can be really real The hyperbranched resin of existing industrialization is also seldom.
The content of the invention
In order to overcome the shortcomings and deficiencies of the prior art described above, primary and foremost purpose of the invention is to provide a kind of hyperbranched tree Aliphatic radical UV cures the preparation method of jetted ink.
Hyperbranched resin base UV another object of the present invention is to provide above method preparation cures jetted ink.
It is still another object of the present invention to provide the application that above-mentioned hyperbranched resin base UV cures jetted ink.
The purpose of the present invention is realized by following proposal:
A kind of hyperbranched resin base UV cures the preparation method of jetted ink, mainly includes the following steps that:
(1) preparation of plant oil base tricarboxylic acid:30% sodium hydroxide solution is added in reaction vessel, whisks and is heated to 75~85 DEG C, vegetable oil D-A reaction products are added, stirring 2.5~3h of reaction, is acidified to pH by gained reaction solution after reaction Repurity is up to plant oil base tricarboxylic acid after=2.0~2.5;
(2) synthesis of vegetable oil-based polyols:Plant oil base tricarboxylic acid prepared by step (1) and diethanol amine is molten Solution carries out neutralization reaction, that is, obtains vegetable oil base hexahydroxylic alcohols in solvent;Dihydromethyl propionic acid is added, in catalyst action Lower carry out esterification, obtains nine yuan of alcohol of plant oil base;
(3) acroleic acid esterification of isophorone diisocyanate (IPDI):Weigh crylic acid hydroxy ester, by the use of dichloromethane as Solvent, be sufficiently stirred dissolve crylic acid hydroxy ester dichloromethane solution;Weigh IPDI, add dichloromethane as solvent with Dibutyl tin laurate installs condensation reflux unit, crylic acid hydroxy ester is slowly added dropwise at 30~40 DEG C as catalyst Dichloromethane solution, 10~15min are dripped off, and stirring 3~4h of reaction, gained reaction solution is rotated remove solvent two after completion of the reaction Chloromethanes, that is, obtain the acrylic acid-esterified product of IPDI;
(4) plant oil base UV cures the preparation of ultra-branched polyurethane acrylate:By the obtained plant oil base of step (2) Hexahydroxylic alcohols is dissolved in methylene chloride with the obtained IPDI acrylic acid-esterified products of step (3), adds tin dilaurate two Butyl tin is placed in 3~4h of reaction in 60~80 DEG C of thermostat water bath, that is, obtains vegetable oil base UV and cure over-expense as catalyst Change urethane acrylate (PUA);
(5) hyperbranched resin base UV cures the preparation of jetted ink:By reactive diluent, basic film-forming resin, step (4) Obtained plant oil base UV cures hyperbranched PUA, photoinitiator mixes in proportion, is dispersed with stirring and uniformly obtains hyperbranched resin Base UV cures jetted ink.
The vegetable oil in vegetable oil D-A reaction products described in step (1) is preferably tung oil, castor oil, linseed oil, waist At least one of shell oil, corn oil, rapeseed oil, peanut oil, sesame oil, soybean oil;The vegetable oil D-A reaction products Preparation method and structural formula see the Chinese invention patent of Publication No. CN106565651A;
The dosage of 30% sodium hydroxide solution and vegetable oil D-A reaction products described in step (1) meets every 100~ 30% sodium hydroxide solution of 120mL, which corresponds to, adds 19.5~22g vegetable oil D-A reaction products;
Acidifying described in step (1) refers to be acidified with the hydrochloric acid of 1mol/L;The purifying refers to three separated out after being acidified Acid is extracted with ethyl acetate, and after organic layer is washed with hot water, adds anhydrous Na2SO4Dry 12h, vegetable oil base is obtained after filtering Tricarboxylic acid.
In step (2), the solvent is ethanol, normal propyl alcohol, isopropanol, n-butanol, dichloromethane, acetone, acetic acid second At least one of ester;The catalyst is sulfuric acid, one kind in hydrochloric acid, nitric acid, phosphoric acid.
The molar ratio of plant oil base tricarboxylic acid and diethanol amine described in step (2) is 1:3~1:3.5, it is described The dosage of dihydromethyl propionic acid meets that the molar ratio of dihydromethyl propionic acid and ethylene glycol amine is 2:1~2.1:1.
In step (2), the neutralization reaction refers to react 1~2h at 20~30 DEG C;The esterification refers to 50~80 DEG C of 2~4h of reaction.
Crylic acid hydroxy ester described in step (3) is hydroxy-ethyl acrylate (HEA), hydroxyethyl methacrylate (HEMA), one kind in hydroxypropyl acrylate (HPA), hydroxy propyl methacrylate (HPMA).
In step (3), the amount of the catalyst is catalytic amount, the crylic acid hydroxy ester and phorone diisocyanate The molar ratio of ester (IPDI) is (1~1.1):1;The dichloromethane solution of the crylic acid hydroxy ester refers to the two of 50~60mL The crylic acid hydroxy ester of 20~30g is added in chloromethanes.The amount and crylic acid hydroxy ester of the methylene chloride added in IPDI Dichloromethane solution in dichloromethane volume ratio be 50~60:50~60;
Mixing speed is 200~300r/min in stirring reaction described in step (3), whole reaction process must every Carried out under conditions of exhausted air and moisture.
The step of described in step (4) (2) obtained plant oil base hexahydroxylic alcohols with the obtained IPDI propylene of step (3) The molar ratio of Esterification product is 1:9~1:9.5;The amount of the catalyst is catalytic amount.
Reactive diluent described in step (5) is reactive diluent commonly used in the art, is preferably propylene Sour hydroxyl ethyl ester, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxy propyl methacrylate, lauryl acrylate, metering system At least one in acid glycidyl ester, isobornyl acrylate, isobornyl methacrylate and acrylic acid tetrahydrofuran methyl esters Kind.
Basic film-forming resin described in step (5) is UV cured polyurethane acrylate prepolymers, its molecular weight is 1000~3000.
Photoinitiator described in step (5) is free radical photo-initiation 1- hydroxycyclohexyl phenyl ketones (Irgacure- 184), 2- hydroxy-2-methyls -1- phenylacetones (Irgacure-1173), 2- methyl -2- (4- morpholinyls) -1- [4- (first sulphur Base) phenyl] -1- acetone (Irgacure-907), 2,4,6- trimethylbenzoy-diphenies phosphine oxide (TPO), 2,4,6- tri- At least one of methyl benzoyl phenyl-phosphonic acid ethyl ester (TPO-L).
Reactive diluent, basic film-forming resin, plant oil base UV described in step (5) cure hyperbranched PUA and light The mass ratio of initiator is (30~40):(10~30):(10~20):(1~10).
Being dispersed with stirring described in step (5) is preferably uniformly to disperse 10~20min under 1000~2000r/min;
A kind of hyperbranched resin base UV being prepared by the above method cures jetted ink.
Above-mentioned hyperbranched resin base UV cures application of the jetted ink in UV ink jet printing industrial systems.
The time that the hyperbranched resin base UV cures jetted ink ultra-violet curing is preferably 3~5min;Ultra-violet curing The a length of 245~405nm of UV light waves.
The present invention is had the following advantages and beneficial effect relative to the prior art:
(1) natural reproducible resource tung oil is introduced the preparation of ink by the present invention, has synthesized vegetable oil base UV curings Ultra-branched polyurethane acrylate, instead of the UV curing monomers of the polyfunctionality of traditional petrochemical origin, is opened for natural material New application field has been warded off, has improved its use value, has alleviated the pressure of petrochemical industry.
(2) hexatomic ring knot is introduced in the hyperbranched UV cured polyurethane acrylates of plant oil base prepared by the present invention Structure, so that after its UV film-forming, cured film has more preferable hardness and heat resistance.The present invention draws in UV cured printing inks Hyper-branched prepolymers are entered, so that ink has lower viscosity, it is possible to reduce the usage amount of reactive diluent.
Embodiment
With reference to embodiment, the present invention is described in further detail, but the implementation of the present invention is not limited to this.
Agents useful for same can routinely be bought from market unless otherwise specified in embodiment.
Embodiment 1
(1) preparation of plant oil base tricarboxylic acid:The 30wt% sodium hydroxide solutions for weighing 120mL add reaction vessel In, whisk and be heated to 85 DEG C;22g tung oil D-A reaction products are added (in the Chinese invention patent of Publication No. CN106565651A Embodiment 1 product), stirring reaction 3h, then be acidified to 1mol/L hydrochloric acid three acid of pH=2.5 precipitations and extracted with ethyl acetate Take, after organic layer is washed with hot water, add anhydrous Na2SO4Dry 12h, vegetable oil base tricarboxylic acid is obtained after filtering;
(2) synthesis of vegetable oil-based polyols:Plant oil base tricarboxylic acid prepared by step (1) is pressed with diethanol amine According to molar ratio 1:3.5 ratio is dissolved in solvent, is carried out neutralization reaction, that is, is obtained vegetable oil base hexahydroxylic alcohols;Then dihydroxy is pressed Methylpropanoic acid is 2.1 with ethylene glycol amine molar ratio:1 adds above-mentioned reactor carries out esterification under catalyst action, to obtain the final product To nine yuan of alcohol of plant oil base;
(3) acroleic acid esterification of IPDI:22.23gIPDI is weighed in three-necked flask, then adds the dichloro of 50~60mL Methane, as catalyst, installs condensation reflux unit, is placed in 40 DEG C of thermostat water bath as solvent and 4 DBTDL dripped; 11.61g hydroxy-ethyl acrylates are weighed in beaker, 60mL dichloromethane is added as solvent, dissolving is sufficiently stirred, then by it It is slowly dropped into the three-necked flask equipped with IPDI, 15min is dripped off, and is reacted 4h, after completion of the reaction, is transferred them to round-bottomed flask In, methylene chloride is removed using Rotary Evaporators, that is, obtains the acrylic acid-esterified product of IPDI;
(4) plant oil base UV cures the preparation of ultra-branched polyurethane acrylate:By the obtained plant oil base of step (2) Hexahydroxylic alcohols is with the obtained IPDI acrylic acid-esterified products of step (3) according to molar ratio 1:9.5 ratio is dissolved in solvent dichloro In methane, 3 drop dibutyl tin laurates are added as catalyst, is placed in 80 DEG C of thermostat water bath and reacts 4h, that is, obtain Plant oil base UV cures ultra-branched polyurethane acrylate (PUA);
(5) hyperbranched resin base UV cures the preparation of jetted ink:By reactive diluent hydroxy-ethyl acrylate, basis film forming Resin (Bao Jun Chemical Co., Ltd.s 2668), plant oil base UV cure hyperbranched PUA, photoinitiator Irgacure-184 presses quality Than for 40:30:10:5 are mixed, and are dispersed with stirring and are uniformly obtained hyperbranched resin base UV curing jetted inks.
Embodiment 2
(1) preparation of plant oil base tricarboxylic acid:The 30wt% sodium hydroxide solutions for weighing 100mL add reaction vessel In, whisk and be heated to 75 DEG C;Adding 19.5g castor oil D-A reaction products, (Chinese invention of Publication No. CN106565651A is special The product of embodiment 7 in profit), 2.5h is reacted in stirring, then three acid acetic acid of pH=2.0 precipitations are acidified to 1mol/L hydrochloric acid Ethyl ester extracts, and after organic layer is washed with hot water, adds anhydrous Na2SO4Dry 12h, vegetable oil base ternary carboxylic is obtained after filtering Acid;
(2) synthesis of vegetable oil-based polyols:Plant oil base tricarboxylic acid prepared by step (1) is pressed with diethanol amine According to molar ratio 1:3 ratio is dissolved in solvent, is carried out neutralization reaction, that is, is obtained vegetable oil base hexahydroxylic alcohols;Then dihydroxy first is pressed Base propionic acid is 2 with ethylene glycol amine molar ratio:1 adds above-mentioned reactor carries out esterification under catalyst action, that is, is planted Nine yuan of alcohol of thing oil base;
(3) acroleic acid esterification of IPDI:22.23g IPDI are weighed in three-necked flask, then add the dichloromethane of 60mL Alkane, as catalyst, installs condensation reflux unit, is placed in 30 DEG C of thermostat water bath as solvent and 4 DBTDL dripped;Claim 14.32g hydroxyethyl methacrylates are taken in beaker, 50mL dichloromethane is added as solvent, is sufficiently stirred dissolving, then will It is slowly dropped into the three-necked flask equipped with IPDI, and 10min is dripped off, and reacts 3h, after completion of the reaction, transfers them to round bottom burning In bottle, methylene chloride is removed using Rotary Evaporators, that is, obtains the acrylic acid-esterified product of IPDI;
(4) tung oil base UV cures the preparation of ultra-branched polyurethane acrylate:By the obtained plant oil base six of step (2) First alcohol is with the obtained IPDI acrylic acid-esterified products of step (3) according to molar ratio 1:9 ratio is dissolved in methylene chloride In, 3 drop dibutyl tin laurates are added as catalyst, are placed in 60 DEG C of thermostat water bath and are reacted 3h, that is, obtain plant Oil base UV cures ultra-branched polyurethane acrylate (PUA);
(5) hyperbranched resin base UV cures the preparation of jetted ink:By reactive diluent hydroxypropyl acrylate, basis film forming Resin (Bao Jun Chemical Co., Ltd.s 2665), plant oil base UV cure hyperbranched PUA, photoinitiator Irgacure-1173 presses matter Amount is than being 35:30:20:10 are mixed, and are dispersed with stirring and are uniformly obtained hyperbranched resin base UV curing jetted inks.
Embodiment 3
(1) preparation of plant oil base tricarboxylic acid:30% sodium hydroxide solution for weighing 110mL is added in reaction vessel, Whisk and be heated to 80 DEG C;20g rapeseed oil D-A reaction products are added (in the Chinese invention patent of Publication No. CN106565651A Embodiment 1 in tung oil replaced with rapeseed oil after product), stirring reaction 3h, then with 1mol/L hydrochloric acid be acidified to pH=2.5 analysis Three acid gone out are extracted with ethyl acetate, and after organic layer is washed with hot water, add anhydrous Na2SO4Dry 12h, is planted after filtering Thing oil base ternary carboxylic acid;
(2) synthesis of vegetable oil-based polyols:Plant oil base tricarboxylic acid prepared by step (1) is pressed with diethanol amine According to molar ratio 1:3 ratio is dissolved in solvent, is carried out neutralization reaction, that is, is obtained vegetable oil base hexahydroxylic alcohols;Then dihydroxy first is pressed Base propionic acid is 2 with ethylene glycol amine molar ratio:1 adds above-mentioned reactor carries out esterification under catalyst action, that is, is planted Nine yuan of alcohol of thing oil base;
(3) acroleic acid esterification of IPDI:22.23g IPDI are weighed in three-necked flask, then add the dichloromethane of 55mL Alkane, as catalyst, installs condensation reflux unit, is placed in 35 DEG C of thermostat water bath as solvent and 4 DBTDL dripped;Claim 13.01g hydroxypropyl acrylates are taken in beaker, 50mL dichloromethane is added as solvent, is sufficiently stirred dissolving, is then delayed Slowly it is added dropwise in the three-necked flask equipped with IPDI, 10min is dripped off, and is reacted 3h, after completion of the reaction, is transferred them to round-bottomed flask In, methylene chloride is removed using Rotary Evaporators, that is, obtains the acrylic acid-esterified product of IPDI;
(4) tung oil base UV cures the preparation of ultra-branched polyurethane acrylate:By the obtained plant oil base six of step (2) First alcohol is with the obtained IPDI acrylic acid-esterified products of step (3) according to molar ratio 1:9 ratio is dissolved in methylene chloride In, 3 drop dibutyl tin laurates are added as catalyst, are placed in 70 DEG C of thermostat water bath and are reacted 4h, that is, obtain plant Oil base UV cures ultra-branched polyurethane acrylate (PUA);
(5) hyperbranched resin base UV cures the preparation of jetted ink:By reactive diluent lauryl acrylate, basis film forming Resin (Bao Jun Chemical Co., Ltd.s 2668), plant oil base UV cure hyperbranched PUA, photoinitiator Irgacure-907 presses quality Than for 30:30:20:1 is mixed, and is dispersed with stirring and is uniformly obtained hyperbranched resin base UV curing jetted inks.
Embodiment 4
(1) preparation of plant oil base tricarboxylic acid:30% sodium hydroxide solution for weighing 100mL is added in reaction vessel, Whisk and be heated to 75 DEG C;22g linseed oil D-A reaction products are added (in the Chinese invention patent of Publication No. CN106565651A Embodiment 2 product), stirring reaction 3h, then be acidified to 1mol/L hydrochloric acid three acid of pH=2.5 precipitations and extracted with ethyl acetate Take, after organic layer is washed with hot water, add anhydrous Na2SO4Dry 12h, vegetable oil base tricarboxylic acid is obtained after filtering;
(2) synthesis of vegetable oil-based polyols:Plant oil base tricarboxylic acid prepared by step (1) is pressed with diethanol amine According to molar ratio 1:3 ratio is dissolved in solvent, is carried out neutralization reaction, that is, is obtained vegetable oil base hexahydroxylic alcohols;Then dihydroxy first is pressed Base propionic acid is 2 with ethylene glycol amine molar ratio:1 adds above-mentioned reactor carries out esterification under catalyst action, that is, is planted Nine yuan of alcohol of thing oil base;
(3) acroleic acid esterification of IPDI:22.23g IPDI are weighed in three-necked flask, then add the two of 50~60mL Chloromethanes, as catalyst, installs condensation reflux unit, is placed in 30 DEG C of thermostat water bath as solvent and 4 DBTDL dripped In;15.86g hydroxy propyl methacrylates are weighed in beaker, 50mL dichloromethane is added as solvent, is sufficiently stirred dissolving, Then it is slowly dropped into the three-necked flask equipped with IPDI, 10min is dripped off, and is reacted 3h, after completion of the reaction, is transferred them to In round-bottomed flask, methylene chloride is removed using Rotary Evaporators, that is, obtains the acrylic acid-esterified product of IPDI;
(4) tung oil base UV cures the preparation of ultra-branched polyurethane acrylate:By the obtained plant oil base six of step (2) First alcohol is with the obtained IPDI acrylic acid-esterified products of step (3) according to molar ratio 1:9 ratio is dissolved in methylene chloride In, 3 drop dibutyl tin laurates are added as catalyst, are placed in 70 DEG C of thermostat water bath and are reacted 3h, that is, obtain plant Oil base UV cures ultra-branched polyurethane acrylate (PUA);
(5) hyperbranched resin base UV cures the preparation of jetted ink:By reactive diluent glycidyl methacrylate, Basic film-forming resin (Bao Jun Chemical Co., Ltd.s 2665), plant oil base UV cure hyperbranched PUA, photoinitiator TPO presses quality Than for 30:20:20:5 are mixed, and are dispersed with stirring and are uniformly obtained hyperbranched resin base UV curing jetted inks.
Embodiment 5
(1) preparation of plant oil base tricarboxylic acid:30% sodium hydroxide solution for weighing 110mL is added in reaction vessel, Whisk and be heated to 80 DEG C;Add the 21g cashew nut shell oil D-A reaction product (Chinese invention patents of Publication No. CN106565651A In embodiment 1 in tung oil replaced by cashew nut shell oil after product), stirring reaction 3h, then is acidified to pH=with 1mol/L hydrochloric acid 2.5 three acid separated out are extracted with ethyl acetate, and after organic layer is washed with hot water, add anhydrous Na2SO4Dry 12h, after filtering i.e. Obtain plant oil base tricarboxylic acid;
(2) synthesis of vegetable oil-based polyols:Plant oil base tricarboxylic acid prepared by step (1) is pressed with diethanol amine According to molar ratio 1:3 ratio is dissolved in solvent, is carried out neutralization reaction, that is, is obtained vegetable oil base hexahydroxylic alcohols;Then dihydroxy first is pressed Base propionic acid is 2 with ethylene glycol amine molar ratio:1 adds above-mentioned reactor carries out esterification under catalyst action, that is, is planted Nine yuan of alcohol of thing oil base;
(3) acroleic acid esterification of IPDI:22.23g IPDI are weighed in three-necked flask, then add the two of 50~60mL Chloromethanes, as catalyst, installs condensation reflux unit, is placed in 35 DEG C of thermostat water bath as solvent and 4 DBTDL dripped In;14.32g hydroxyethyl methacrylates are weighed in beaker, 50mL dichloromethane is added as solvent, is sufficiently stirred dissolving, Then it is slowly dropped into the three-necked flask equipped with IPDI, 10min is dripped off, and is reacted 3h, after completion of the reaction, is transferred them to In round-bottomed flask, methylene chloride is removed using Rotary Evaporators, that is, obtains the acrylic acid-esterified product of IPDI;
(4) tung oil base UV cures the preparation of ultra-branched polyurethane acrylate:By the obtained plant oil base six of step (2) First alcohol is with the obtained IPDI acrylic acid-esterified products of step (3) according to molar ratio 1:9.5 ratio is dissolved in solvent dichloromethane In alkane, 3 drop dibutyl tin laurates are added as catalyst, is placed in 80 DEG C of thermostat water bath and reacts 4h, that is, planted Thing oil base UV cures ultra-branched polyurethane acrylate (PUA);
(5) hyperbranched resin base UV cures the preparation of jetted ink:By reactive diluent isobornyl acrylate, basis into Film resin (Bao Jun Chemical Co., Ltd.s 2668), plant oil base UV cure hyperbranched PUA, photoinitiator TPO-L is in mass ratio 40:10:20:10 are mixed, and are dispersed with stirring and are uniformly obtained hyperbranched resin base UV curing jetted inks.
Embodiment 6
(1) preparation of plant oil base tricarboxylic acid:30% sodium hydroxide solution for weighing 120mL is added in reaction vessel, Whisk and be heated to 85 DEG C;22g soybean oil D-A reaction products are added (in the Chinese invention patent of Publication No. CN106565651A Embodiment 3 product), stirring reaction 3h, then be acidified to 1mol/L hydrochloric acid three acid of pH=2.5 precipitations and extracted with ethyl acetate Take, after organic layer is washed with hot water, add anhydrous Na2SO4Dry 12h, vegetable oil base tricarboxylic acid is obtained after filtering;
(2) synthesis of vegetable oil-based polyols:Plant oil base tricarboxylic acid prepared by step (1) is pressed with diethanol amine According to molar ratio 1:3.5 ratio is dissolved in solvent, is carried out neutralization reaction, that is, is obtained vegetable oil base hexahydroxylic alcohols;Then dihydroxy is pressed Methylpropanoic acid is 2.1 with ethylene glycol amine molar ratio:1 adds above-mentioned reactor carries out esterification under catalyst action, to obtain the final product To nine yuan of alcohol of plant oil base;
(3) acroleic acid esterification of IPDI:22.23g IPDI are weighed in three-necked flask, then add the dichloromethane of 60mL Alkane, as catalyst, installs condensation reflux unit, is placed in 40 DEG C of thermostat water bath as solvent and 4 DBTDL dripped;Claim 14.32g hydroxyethyl methacrylates are taken in beaker, 60mL dichloromethane is added as solvent, is sufficiently stirred dissolving, then will It is slowly dropped into the three-necked flask equipped with IPDI, and 10min is dripped off, and reacts 4h, after completion of the reaction, transfers them to round bottom burning In bottle, methylene chloride is removed using Rotary Evaporators, that is, obtains the acrylic acid-esterified product of IPDI;
(4) tung oil base UV cures the preparation of ultra-branched polyurethane acrylate:By the obtained plant oil base six of step (2) First alcohol is with the obtained IPDI acrylic acid-esterified products of step (3) according to molar ratio 1:9 ratio is dissolved in methylene chloride In, 3 drop dibutyl tin laurates are added as catalyst, are placed in 80 DEG C of thermostat water bath and are reacted 4h, that is, obtain plant Oil base UV cures ultra-branched polyurethane acrylate (PUA);
(5) hyperbranched resin base UV cures the preparation of jetted ink:By reactive diluent acrylic acid tetrahydrofuran methyl esters, base Plinth film-forming resin (Bao Jun Chemical Co., Ltd.s 2668), plant oil base UV cure hyperbranched PUA, photoinitiator Irgacure-184 It is 35 in mass ratio:30:20:10 are mixed, and are dispersed with stirring and are uniformly obtained hyperbranched resin base UV curing jetted inks.
Performance test embodiment
Surface drying time, polytetrafluoroethylene (PTFE) plate surface is uniformly applied to by UV ink, light source and time for exposure in setting It is lower to cure through UV.According to GB1728-79, by the cured film upper a piece of filter paper of 200g drying counterweight pressures, weight is removed after a certain period of time Code, overturns cured film, and filter paper can freely be fallen down, that is, thinks surface drying, measures ink solidification surface drying time;
Hardness analysis, according to the hardness of GB/T 6739-1996 measure paint films;Membrane body tensile strength and elongation at break point Analysis, the mechanical property according to GB13022-91 using UTM4204 type universal electricals testing machine measure photocured film;Water resistance by Water absorption rate characterizes, and is tested according to the method for GB/T1733-93;The measure of adhesive force is tested according to the method for GB/T9286-1998.
Thermal stability analysis, test table is carried out using Shimadzu, Japan DTG-60 types thermogravimetric analyzer to resin Sign, heating rate:20℃/min;Atmosphere:Nitrogen;Crucible material:Aluminium crucible.When recording each embodiment mass loss up to 5% Thermal degradation temperature.
Each embodiment product all-round property testing result of table 1
Good UV cured printing inks are generally fast with solidification rate, and hardness is moderate, right after film forming the features such as excellent in mechanical performance For polyurethane acroleic acid, this requires resin surface drying time is shorter, tensile strength is bigger, the better i.e. extension at break of pliability The more big then resin comprehensive performance of rate is better, from table 1 it follows that the UV prepared by the present invention cures jetted ink surface drying time Respectively less than 10 seconds, for hardness all in H to HB scopes, tensile strength was all higher than 34Mpa, and elongation at break is all higher than 7%.Embodiment sample UV cured printing inks its solidification rate that product prepare gained is very fast, excellent in mechanical performance, and heat endurance is good, thermal degradation temperature compared with The comprehensive performances such as height, the UV cured printing inks that the preparation method provided by invention is prepared into, excellent combination property, film dynamic performance Fully meet practical application needs.
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention and from above-described embodiment Limitation, other any Spirit Essences without departing from the present invention with made under principle change, modification, replacement, combine, simplification, Equivalent substitute mode is should be, is included within protection scope of the present invention.

Claims (10)

1. a kind of hyperbranched resin base UV cures the preparation method of jetted ink, it is characterised in that mainly includes the following steps that:
(1) preparation of plant oil base tricarboxylic acid:30% sodium hydroxide solution is added in reaction vessel, whisk and be heated to 75~ 85 DEG C, vegetable oil D-A reaction products are added, stirring 2.5~3h of reaction, is acidified to pH=by gained reaction solution after reaction Repurity is up to plant oil base tricarboxylic acid after 2.0~2.5;
(2) synthesis of vegetable oil-based polyols:Plant oil base tricarboxylic acid prepared by step (1) is dissolved in diethanol amine In solvent, neutralization reaction is carried out, that is, obtains vegetable oil base hexahydroxylic alcohols;Add dihydromethyl propionic acid, under catalyst action into Row esterification, obtains nine yuan of alcohol of plant oil base;
(3) acroleic acid esterification of isophorone diisocyanate:Crylic acid hydroxy ester is weighed, by the use of dichloromethane as solvent, fully Stirring and dissolving obtains the dichloromethane solution of crylic acid hydroxy ester;IPDI is weighed, adds dichloromethane as solvent and tin dilaurate Dibutyl tin installs condensation reflux unit, the dichloromethane of crylic acid hydroxy ester is slowly added dropwise at 30~40 DEG C as catalyst Solution, 10~15min are dripped off, and stirring 3~4h of reaction, gained reaction solution is rotated remove methylene chloride after completion of the reaction, Obtain the acrylic acid-esterified product of IPDI;
(4) plant oil base UV cures the preparation of ultra-branched polyurethane acrylate:The obtained plant oil base of step (2) is hexa-atomic Alcohol is dissolved in methylene chloride with the obtained IPDI acrylic acid-esterified products of step (3), adds di lauric dibutyl Tin is placed in 3~4h of reaction in 60~80 DEG C of thermostat water bath, that is, obtains vegetable oil base UV and cure hyperbranched poly as catalyst Urethane acrylate;
(5) hyperbranched resin base UV cures the preparation of jetted ink:Reactive diluent, basic film-forming resin, step (4) are obtained Plant oil base UV cure ultra-branched polyurethane acrylate, photoinitiator and mix in proportion, be dispersed with stirring and uniformly surpassed Branched resin base UV cures jetted ink.
2. hyperbranched resin base UV according to claim 1 cures the preparation method of jetted ink, it is characterised in that:
The vegetable oil in vegetable oil D-A reaction products described in step (1) is tung oil, castor oil, linseed oil, cashew nut shell oil, At least one of corn oil, rapeseed oil, peanut oil, sesame oil, soybean oil;
The dosage of 30% sodium hydroxide solution and vegetable oil D-A reaction products described in step (1) meets every 100~120mL 30% sodium hydroxide solution correspond to add 19.5~22g vegetable oil D-A reaction products;
Acidifying described in step (1) refers to be acidified with the hydrochloric acid of 1mol/L;Three acid that the purifying refers to separate out after acidifying are used Ethyl acetate extracts, and after organic layer is washed with hot water, adds anhydrous Na2SO4Dry 12h, vegetable oil base ternary is obtained after filtering Carboxylic acid.
3. hyperbranched resin base UV according to claim 1 cures the preparation method of jetted ink, it is characterised in that:
In step (2), the solvent is ethanol, in normal propyl alcohol, isopropanol, n-butanol, dichloromethane, acetone, ethyl acetate At least one;The catalyst is sulfuric acid, one kind in hydrochloric acid, nitric acid, phosphoric acid;
The molar ratio of plant oil base tricarboxylic acid and diethanol amine described in step (2) is 1:3~1:3.5, the dihydroxy The dosage of methylpropanoic acid meets that the molar ratio of dihydromethyl propionic acid and ethylene glycol amine is 2:1~2.1:1;
In step (2), the neutralization reaction refers to react 1~2h at 20~30 DEG C;The esterification refers to 50~ 80 DEG C of 2~4h of reaction.
4. hyperbranched resin base UV according to claim 1 cures the preparation method of jetted ink, it is characterised in that:
Crylic acid hydroxy ester described in step (3) is hydroxy-ethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, One kind in hydroxy propyl methacrylate;
In step (3), the amount of the catalyst is catalytic amount, the crylic acid hydroxy ester and isophorone diisocyanate Molar ratio is (1~1.1):1;The dichloromethane solution of the crylic acid hydroxy ester refers to add in the dichloromethane of 50~60mL Enter the crylic acid hydroxy ester of 20~30g;The amount of the methylene chloride added in IPDI and the dichloromethane of crylic acid hydroxy ester The volume ratio of dichloromethane is 50~60 in solution:50~60;
Mixing speed is 200~300r/min in stirring reaction described in step (3), and whole reaction process must be empty in isolation Carried out under conditions of gas and moisture.
5. hyperbranched resin base UV according to claim 1 cures the preparation method of jetted ink, it is characterised in that:
The step of described in step (4) (2) obtained plant oil base hexahydroxylic alcohols with the obtained IPDI acrylate of step (3) The molar ratio for changing product is 1:9~1:9.5;The amount of the catalyst is catalytic amount.
6. hyperbranched resin base UV according to claim 1 cures the preparation method of jetted ink, it is characterised in that:
Reactive diluent described in step (5) is hydroxy-ethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, first Base hydroxypropyl acrylate, lauryl acrylate, glycidyl methacrylate, isobornyl acrylate, methacrylic acid are different At least one of norbornene ester and acrylic acid tetrahydrofuran methyl esters;
Basic film-forming resin described in step (5) is UV cured polyurethane acrylate prepolymers, its molecular weight for 1000~ 3000;
Photoinitiator described in step (5) is free radical photo-initiation 1- hydroxycyclohexyl phenyl ketones, 2- hydroxyl -2- first Base -1- phenylacetones, 2- methyl -2- (4- morpholinyls) -1- [4- (methyl mercapto) phenyl] -1- acetone, 2,4,6- trimethylbenzene first At least one of acyl group-diphenyl phosphine oxide, 2,4,6- trimethylbenzoyl phenyl phosphinic acid ethyl esters.
7. hyperbranched resin base UV according to claim 1 cures the preparation method of jetted ink, it is characterised in that:
Reactive diluent described in step (5), basic film-forming resin, plant oil base UV cure hyperbranched PUA and light-initiated The mass ratio of agent is (30~40):(10~30):(10~20):(1~10);
Being dispersed with stirring described in step (5) uniformly refers to disperses 10~20min under 1000~2000r/min.
8. a kind of be prepared hyperbranched resin base UV curing jetted inks according to claim 1~7 any one of them method.
9. hyperbranched resin base UV according to claim 8 cures jetted ink answering in UV ink jet printing industrial systems With.
10. hyperbranched resin base UV according to claim 9 cures application of the jetted ink in UV inkjet ink systems, It is characterized in that:The time that the hyperbranched resin base UV cures jetted ink ultra-violet curing is 3~5min;Ultra-violet curing A length of 245~the 405nm of UV light waves.
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CN109438656A (en) * 2018-10-19 2019-03-08 中国林业科学研究院林产化学工业研究所 A kind of anacardol based polyurethanes acrylic resin and preparation method and application
CN111647120A (en) * 2020-05-19 2020-09-11 广东职业技术学院 Preparation method of hyperbranched polyurethane oligomer
CN112250854A (en) * 2020-10-13 2021-01-22 河南科技大学 UV ink oligomer resin for heat transfer film and preparation method and application thereof
CN115368578A (en) * 2021-05-19 2022-11-22 黄建发 Preparation method of nano silicon dioxide with core-shell structure
CN115537063A (en) * 2022-11-03 2022-12-30 西华师范大学 Preparation method of branched vegetable oil-based photosensitive resin and UV (ultraviolet) curing glass printing ink
CN115746249A (en) * 2022-11-16 2023-03-07 华南农业大学 Castor oil-based waterborne UV-cured polyurethane acrylate as well as preparation method and application thereof

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CN109438656A (en) * 2018-10-19 2019-03-08 中国林业科学研究院林产化学工业研究所 A kind of anacardol based polyurethanes acrylic resin and preparation method and application
CN111647120A (en) * 2020-05-19 2020-09-11 广东职业技术学院 Preparation method of hyperbranched polyurethane oligomer
CN111647120B (en) * 2020-05-19 2022-05-20 广东职业技术学院 Preparation method of hyperbranched polyurethane oligomer
CN112250854A (en) * 2020-10-13 2021-01-22 河南科技大学 UV ink oligomer resin for heat transfer film and preparation method and application thereof
CN115368578A (en) * 2021-05-19 2022-11-22 黄建发 Preparation method of nano silicon dioxide with core-shell structure
CN115537063A (en) * 2022-11-03 2022-12-30 西华师范大学 Preparation method of branched vegetable oil-based photosensitive resin and UV (ultraviolet) curing glass printing ink
CN115537063B (en) * 2022-11-03 2023-09-12 西华师范大学 Branched vegetable oil-based photosensitive resin and preparation method of UV (ultraviolet) cured glass ink
CN115746249A (en) * 2022-11-16 2023-03-07 华南农业大学 Castor oil-based waterborne UV-cured polyurethane acrylate as well as preparation method and application thereof

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