CN106554476A - A kind of preparation method of the polyurethane resin for flexible package intaglio plate table printing ink - Google Patents
A kind of preparation method of the polyurethane resin for flexible package intaglio plate table printing ink Download PDFInfo
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- CN106554476A CN106554476A CN201610557157.3A CN201610557157A CN106554476A CN 106554476 A CN106554476 A CN 106554476A CN 201610557157 A CN201610557157 A CN 201610557157A CN 106554476 A CN106554476 A CN 106554476A
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- polyurethane resin
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6607—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
Abstract
The invention discloses a kind of preparation method of the polyurethane resin for flexible package intaglio plate table printing ink, belongs to ink material preparation field.The invention in turn includes the following steps：Heating in polyacid and dihydroxylic alcohols input reaction vessel, according to the mol ratio, is vacuumized prepared PEPA by the synthesis of PEPA；The synthesis of performed polymer；Chain extending reaction, is slowly added to small molecule polyol chain extender in performed polymer and polyurethane resin is obtained；Obtained polyurethane resin is slowly added to ethyl acetate, absolute ethyl alcohol, modified resin and auxiliary agent by product configuration, and the polyurethane resin for flexible package intaglio plate table printing ink is obtained.Stable processing technique of the present invention, by the use of polyurethane resin as the link stuff resin for preparing ink, improve pigment-dispersing, transparency and the rate of drying of ink, improve the printing adaptability of ink, glossiness, shallow net metastatic, to base material adhesive force and freeze proof cold resistance, and environmental protection, meets the needs of production and application.
Description
Technical field
The invention belongs to ink material preparation field, and in particular to a kind of polyurethane for flexible package intaglio plate table printing ink
The preparation method of resin.
Background technology
In current country flexible package plastic film printing field, intaglio plate ink used for plastic technology and market are constantly developed, and which should
All of packaging field is included almost with scope, such as in all types of plastic film substrate bag of the industries such as food, medicine, commodity
Dress.As developing rapidly for press, the number to be printed of various flexible package plastics improve constantly, product packaging class is required also to get over
Come higher.
Ink is mainly made up of binder resin, solvent, pigment and four part of auxiliary agent, wherein playing key to ink performance
Effect is ink adhesive resin.China is molten with the molten type polyamide of benzene and alcohol currently used for flexible package intaglio plate table printing ink resin
Based on property polyamide.The ink that the molten type polyamide of benzene is prepared will use substantial amounts of benzene class in production and printing process
Solvent, has very big harm to the health of operating personnel, while its volatilization also result in environmental pollution.In addition, due to benzene
Class belongs to slow drying solvent, easily remains in dry ink film layer, can corrode the food in packaging, produces noxious odor, gives
The health of consumer brings harm.Although the polyamide-based ink of ethanol-soluble type does not use benzene kind solvent, such ink is at low temperature
Easily separate out, shallow net metastatic it is poor, winter printing need to return jellys, the phenomenon such as summer printing easily sticks together, peels off, using being subject to greatly
Restriction.
Polyurethanes ink is attached with its excellent printing adaptability, splendid glossiness, good shallow net metastatic, base material
The characteristics such as the property, freeze proof cold resistance gradually instead of traditional benzene it is molten/ethanol-soluble type polyamide ink, become the master of environment-friendly ink
Angle.Because of the pliability of polyurethane resin, caking property, the dispersiveness excellent to pigment, more suitable for intaglio plate ink used for plastic especially
Table prints resin, is beneficial to the demand for meeting that improving product packs class.
Polyurethane resin is affecting and is determining the adhesive strength of ink, curing rate, rate of drying simultaneously, gives ink again
The physical properties such as certain glossiness, rub resistance, yellowing resistance and resistance to impact, and ink is decide to a great extent
Viscosity, viscosity, yield value and mobility, so, the ink of high-quality comes from the link stuff resin of high-quality.With regard to polyurethane oil
Inkwood fat, foreign countries realize industrialization in 20 century 70s, such as company of Japanese Japan, big Japanese ink chemical industry and force
Field medicine company etc..The polyurethane ink resin used by the country is usually from external import polyurethane micelle, then carries out dissolving processing
Use, demand is larger.In recent years, domestic existing many producing scientific research units were engaged in the research of polyurethane ink resin, and
Preferable effect is achieved, but the combination property of product has a certain distance compared with imported product.It is reported that, it is domestic for oil
30% or so, high accomplishes 45% or so to the polyurethane resin of ink solid content most absolutely, but its performance is general, market competition
Advantage is not obvious, and technical merit still needs further improvement, and have in product quite a few using benzene, ketone such as toluene,
, used as solvent, the toxicity of toluene is stronger, and Long Term Contact has carcinogenic possibility for butanone, cyclohexanone etc.；And the smell of butanone residual
It is dense, and have certain toxicity, do not meet the requirement of environmental protection yet.For the resin of water-based polyurethane ink, comparing oiliness has
Machine solvent borne polyurethane ink resin, water-based polyurethane ink resin do not result in the volatilization of a large amount of organic solvents, and toxicity is low, right
The healthy impact of direct labor is little, in the today for increasingly paying attention to environmental protection and health of human body, waterborne polyurethane resin
There is huge development prospect, but the development of water-based polyurethane ink resin does not have solvent type ink developer resin ripe, permitted
Shortcomings in many performances, are particularly useful for its glossiness in flexible package intaglio plate table printing ink, heat endurance, rate of drying, water-fast
The performances such as property still do not reach solvent type standard, and technology is relatively difficult to break through in a short time.
The content of the invention
The technical problem to be solved is to overcome the above-mentioned deficiency in the presence of prior art, and provides a kind of raw
Production. art is stable, improves pigment-dispersing, transparency and the rate of drying of ink, improve the printing adaptability of ink, glossiness,
Shallow net metastatic, to base material adhesive force, resistance to water, heat resistanceheat resistant adhesive and freeze proof cold resistance for flexible package intaglio plate table printing ink
Polyurethane resin preparation method.
In order to solve above-mentioned technical problem, the technical solution adopted in the present invention is：It is a kind of to print for flexible package intaglio plate table
The preparation method of the polyurethane resin of ink, it is characterised in that：The polyurethane resin for flexible package intaglio plate table printing ink
Preparation method in turn include the following steps：
（1）The synthesis of PEPA, according to hydroxyl：Carboxyl mol ratio is nOH : nCOOH =（1.2-3.0）:1 ratio, will
The polyacid for measuring and the dihydroxylic alcohols for measuring put into reaction vessel successively, and heat temperature raising, the material in question response container melt
Stirring is started after melting, 10-300ppm catalyst is added, is passed through nitrogen, temperature reaches 150 DEG C of beginning water outlets, control in reaction vessel
100 DEG C -102 DEG C of fractionation tower temperature processed, continues to have gone out theoretical water when heating, 220 DEG C of reaction vessel Nei Wenduda, and control is anti-
In 4-5 hours between seasonable, when fractionation tower temperature is below 70 DEG C, sampling detecting acid number, acid number are opened in 20-30mgKOH/g
Beginning vacuumizes, and 1-2 hours, the 30 minutes sampling detecting acid numbers in interval and hydroxyl value are first slowly vacuumized under the conditions of 0.02-0.08MPa,
Then continue to vacuumize at 220 DEG C -230 DEG C with temperature under the conditions of high vacuum 0.099-0.1MPa, taken out according to molecular weight requirement
Vacuum polycondensation 4-9 hour, midway are spaced 30 minutes sampling detecting acid numbers and hydroxyl value, and final control acid number is in 0.3-
0.5mgKOH/g, control hydroxyl value are obtained PEPA of the molecular weight in 1000-3000 in 36mgKOH/g-117mgKOH/g；
（2）The synthesis of performed polymer, by step（1）Obtained PEPA and PPG in molar ratio 5:（0.5-2）'s
Ratio puts into reaction vessel, is vacuum dried 1-2 hours, is cooled to 60 DEG C -80 DEG C, according to hydroxyl under conditions of 100 DEG C -120 DEG C
Base：Mol ratio n of isocyanoOH : nNCO=1：（1.2-2.0）Ratio be slowly added dropwise isocyanates, rate of addition presses temperature
Situation control less than 90 DEG C, after isocyanates is dripped under the conditions of 70 DEG C -90 DEG C reacts 2-4 hours, is cooled to 60
DEG C, 10% ethyl acetate is added, is stirred evenly standby；
（3）Chain extending reaction, in step（2）Small molecule polyol chain extender is slowly added in obtained performed polymer, according to hydroxyl with
Isocyano mol ratio n in performed polymerOH : nNCO=(0.3-0.8)：1 ratio is added, after polyol chain extender is added,
Control temperature adds isocyanate blocking agents to continue reaction in 60 DEG C of -80 DEG C of scopes reaction 2-4 hours, until reaction stops, system
Obtain polyurethane resin；
（4）Product configuration, by step（3）Obtained polyurethane resin be slowly added to ethyl acetate, absolute ethyl alcohol, modified resin and
Auxiliary agent, is obtained the polyurethane resin for flexible package intaglio plate table printing ink, adds acetic acid per 100 parts of polyurethane resin domestic demands
Ethyl ester 10.0-15.0 parts, absolute ethyl alcohol 10.0-15.0 parts, modified resin 2.0-8.0 part and auxiliary agent 0.1-5.0 parts are described to change
Property resin be at least one in terpene resin and rosin derivative resin, the auxiliary agent includes scratch resistance agent and coupling agent.
Further, the step（1）In the synthesis of PEPA, polyacid be azelaic acid, decanedioic acid, adipic acid,
One or more in M-phthalic acid and maleic acid, dihydroxylic alcohols are methyl propanediol, 1,6- hexylene glycols, diethyleneglycol bisphenol
One or more in A, ethylene glycol and BDO, catalyst are butyl titanate, tetraisopropyl titanate, zinc acetate and three
One or more in antimony oxide.
Further, the step（2）In the synthesis of performed polymer, isocyanates is Carbodiimide-Modified MDI, many methylenes
Quito polyphenyl polyisocyanate（PAPI）, hexamethylene diisocyanate（HDI）, isoflurane chalcone diisocyanate（IPDI）, benzene two
Methyl diisocyanate（XDI）, Methylcyclohexyl diisocyanate（HTDI）And dicyclohexyl methyl hydride diisocyanate（HMDI）
In one or more.
Further, the step（3）In chain extending reaction, polyol chain extender is ethylene glycol, diethylene glycol (DEG), Isosorbide-5-Nitrae-fourth two
One or more in alcohol, 1,6- hexylene glycols, sorbierite, glycerine and trimethylolpropane.
Further, the physical and chemical index of the polyurethane resin for flexible package intaglio plate table printing ink is：Solid content
68.0%-72.0%, viscosity 1000-3000mPa.s (25 DEG C).
The present invention compared with prior art, has the following advantages that and effect：Stable processing technique of the present invention is controllable, utilizes
Polyurethane resin improves pigment-dispersing, transparency and the rate of drying of ink, changes as the link stuff resin for preparing ink
Be apt to the printing adaptability of ink, glossiness, shallow net metastatic, to base material adhesive force, resistance to water, heat resistanceheat resistant adhesive and freeze proof resistance to
It is cold, and environmental protection, meet the needs of production and application.
The solvent type polyurethane resin of the present invention is compared to traditional molten type polyamide of employing benzene and alcohol-soluble polyamides
Link stuff resin of the polyimide resin as ink, as the ink that the molten type polyamide of benzene is prepared will in production and printing process
Using substantial amounts of benzene kind solvent, readily volatilized to cause environmental pollution and injury is also resulted in human body, due to benzene class, to belong to slow curing molten
Agent, easily remains in dry ink film layer, can corrode the food in packaging, produces noxious odor, to the health of consumer
Harm is brought, the ink that ethanol-soluble type polyamide is configured easily is separated out at low temperature and shallow net metastatic is poor, and winter printing need to be returned
Freeze, summer printing easily sticks together, peels off, and printing quality is poor, the more environmentally friendly safety of solvent type polyurethane resin of the present invention, and
And printing adaptability is strong；Compared to waterborne polyurethane resin, as the production technology of waterborne polyurethane resin does not have solvent-borne type to gather
Urethane developer resin is ripe, the Shortcomings in many performances, and the solvent type polyurethane resin production technology of the present invention is more stable
It is controllable, and there is preferable glossiness, heat endurance, rate of drying and resistance to water.
Specific embodiment
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment, and the embodiment can be made further to the present invention
Supplement and explanation, but the present invention is not limited to these embodiments.
Embodiment 1
A kind of preparation method of the polyurethane resin for flexible package intaglio plate table printing ink of the present invention comprises the steps：
（1）The synthesis of PEPA, according to hydroxyl：Carboxyl mol ratio is nOH : nCOOH =1.5:1 ratio, will measure
Maleic acid and the methyl propanediol that measures put into reaction vessel, heat temperature raising, the material in question response container successively
Stirring is started after melting, 150ppm catalyst is added, is passed through nitrogen, temperature reaches 150 DEG C of beginning water outlets, control in reaction vessel
100 DEG C -102 DEG C of fractionation tower temperature, continues to have gone out theoretical water when heating, 220 DEG C of reaction vessel Nei Wenduda, control reaction
Time, when fractionation tower temperature is below 70 DEG C, sampling detecting acid number, acid number started to take out true in 25mgKOH/g in 4-5 hours
Sky, first slowly vacuumizes 1-2 hours, the 30 minutes sampling detecting acid numbers in interval and hydroxyl value, under the conditions of 0.04MPa then in high vacuum
Continue to vacuumize at 225 DEG C with temperature under the conditions of 0.1MPa, vacuumize polycondensation reaction 6 hours, the sampling in 30 minutes of midway interval is surveyed
Acid number and hydroxyl value, in 0.42mgKOH/g, control hydroxyl value is obtained molecular weight in 1900- in 56mgKOH/g to final control acid number
2100 PEPA；
（2）The synthesis of performed polymer, by step（1）Obtained PEPA and PPG in molar ratio 5:1.5 ratio
Input reaction vessel, is vacuum dried 1-2 hours under conditions of 110 DEG C, is cooled to 65 DEG C, according to hydroxyl：Isocyano rubs
You compare nOH : nNCO=1：1.8 ratio is slowly added dropwise Carbodiimide-Modified MDI, and rate of addition is less than 90 DEG C by temperature
Situation is controlled, and is reacted 2-4 hours, is cooled to 60 DEG C, add after Carbodiimide-Modified MDI is dripped under the conditions of 75 DEG C
10% ethyl acetate, stirs evenly standby；
（3）Chain extending reaction, in step（2）Ethylene glycol is slowly added in obtained performed polymer, according to different in hydroxyl and performed polymer
Cyanate radical mol ratio nOH : nNCO=0.5：1 ratio is added, and after ethylene glycol is added, control temperature is in 70 DEG C of scope reaction 2-4
Hour, add isocyanate blocking agents to continue reaction, until reaction stops, polyurethane resin is obtained；
（4）Product configuration, by step（3）Obtained polyurethane resin be slowly added to ethyl acetate, absolute ethyl alcohol, terpene resin and
Auxiliary agent, is obtained the polyurethane resin for flexible package intaglio plate table printing ink, adds acetic acid per 100 parts of polyurethane resin domestic demands
3.0 parts of 12.0 parts of ethyl ester, 13.0 parts of absolute ethyl alcohol, 5.0 parts of terpene resin and auxiliary agent, auxiliary agent includes scratch resistance agent and coupling agent.
The physical and chemical index of the polyurethane resin for flexible package intaglio plate table printing ink of the invention obtained is：Solid content
70.0%, viscosity 1500mPa.s (25 DEG C).
Embodiment 2
A kind of preparation method of the polyurethane resin for flexible package intaglio plate table printing ink of the present invention comprises the steps：
（1）The synthesis of PEPA, according to hydroxyl：Carboxyl mol ratio is nOH : nCOOH =1.8:1 ratio, will measure
Maleic acid and the methyl propanediol that measures put into reaction vessel, heat temperature raising, the material in question response container successively
Stirring is started after melting, 120ppm catalyst is added, is passed through nitrogen, temperature reaches 150 DEG C of beginning water outlets, control in reaction vessel
100 DEG C -102 DEG C of fractionation tower temperature, continues to have gone out theoretical water when heating, 220 DEG C of reaction vessel Nei Wenduda, control reaction
Time, when fractionation tower temperature is below 70 DEG C, sampling detecting acid number, acid number started to take out true in 20mgKOH/g in 4-5 hours
Sky, first slowly vacuumizes 1-2 hours, the 30 minutes sampling detecting acid numbers in interval and hydroxyl value, under the conditions of 0.08MPa then in high vacuum
Continue to vacuumize at 230 DEG C with temperature under the conditions of 0.1MPa, polycondensation reaction is vacuumized 4 hours according to molecular weight requirement, between midway
Every 30 minutes sampling detecting acid numbers and hydroxyl value, final control acid number is obtained and is divided in 110mgKOH/g in 0.5mgKOH/g, control hydroxyl value
PEPA of the son amount in 1000-1200；
（2）The synthesis of performed polymer, by step（1）Obtained PEPA and PPG in molar ratio 5:1.8 ratio
Input reaction vessel, is vacuum dried 1-2 hours under conditions of 100 DEG C, is cooled to 70 DEG C, according to hydroxyl：Isocyano rubs
You compare nOH : nNCO=1：1.5 ratio is slowly added dropwise Carbodiimide-Modified MDI, and rate of addition is less than 90 DEG C by temperature
Situation is controlled, and is reacted 2-4 hours, is cooled to 60 DEG C, add 10% acetic acid second after isocyanates is dripped under the conditions of 80 DEG C
Ester, stirs evenly standby；
（3）Chain extending reaction, in step（2）Ethylene glycol is slowly added in obtained performed polymer, according to different in hydroxyl and performed polymer
Cyanate radical mol ratio nOH : nNCO=0.8：1 ratio is added, and after ethylene glycol is added, control temperature is in 80 DEG C of scope reaction 2-4
Hour, add isocyanate blocking agents to continue reaction, until reaction stops, polyurethane resin is obtained；
（4）Product configuration, by step（3）Obtained polyurethane resin be slowly added to ethyl acetate, absolute ethyl alcohol, modified resin and
Auxiliary agent, is obtained the polyurethane resin for flexible package intaglio plate table printing ink, adds acetic acid per 100 parts of polyurethane resin domestic demands
4.0 parts of 15.0 parts of ethyl ester, 15.0 parts of absolute ethyl alcohol, 8.0 parts of terpene resin and auxiliary agent, auxiliary agent includes scratch resistance agent and coupling agent.
In the embodiment of the present invention, the physical and chemical index of the obtained polyurethane resin for flexible package intaglio plate table printing ink is：
Solid content 72.0%, viscosity 2100mPa.s (25 DEG C).
Embodiments of the invention 1 and polyurethane resin obtained in embodiment 2 are configured to table printing ink for flexible package intaglio plate
In printing, printing performance index is as follows：
Although the present invention is disclosed as above with embodiment, which is not limited to protection scope of the present invention, any to be familiar with being somebody's turn to do
The technical staff of item technology, in the change made without departing from the spirit and scope of the invention and retouching, all should belong to the present invention
Protection domain.
Claims (5)
1. a kind of preparation method of the polyurethane resin for flexible package intaglio plate table printing ink, it is characterised in that：It is described for soft
The preparation method of the polyurethane resin of packaging intaglio plate table printing ink in turn includes the following steps：
（1）The synthesis of PEPA, according to hydroxyl：Carboxyl mol ratio is nOH: nCOOH=（1.2-3.0）:1 ratio, will meter
Measured polyacid and the dihydroxylic alcohols for measuring put into reaction vessel, heat temperature raising, the material melts in question response container successively
After start stirring, add 10-300ppm catalyst, be passed through nitrogen, in reaction vessel, temperature reaches 150 DEG C of beginning water outlets, control
100 DEG C -102 DEG C of fractionation tower temperature, continues to have gone out theoretical water when heating, 220 DEG C of reaction vessel Nei Wenduda, control reaction
Time, when fractionation tower temperature is below 70 DEG C, sampling detecting acid number, acid number started in 20-30mgKOH/g in 4-5 hours
Vacuumize, 1-2 hours, the 30 minutes sampling detecting acid numbers in interval and hydroxyl value are first slowly vacuumized under the conditions of 0.02-0.08MPa, so
Continue to vacuumize at 220 DEG C -230 DEG C with temperature afterwards under the conditions of high vacuum 0.099-0.1MPa, taken out very according to molecular weight requirement
Empty polycondensation reaction 4-9 hours, midway are spaced 30 minutes sampling detecting acid numbers and hydroxyl value, and final control acid number is in 0.3-0.5mgKOH/
G, control hydroxyl value are obtained PEPA of the molecular weight in 1000-3000 in 36mgKOH/g-117mgKOH/g；
（2）The synthesis of performed polymer, by step（1）Obtained PEPA and PPG in molar ratio 5:（0.5-2）'s
Ratio puts into reaction vessel, is vacuum dried 1-2 hours, is cooled to 60 DEG C -80 DEG C, according to hydroxyl under conditions of 100 DEG C -120 DEG C
Base：Mol ratio n of isocyanoOH: nNCO=1：（1.2-2.0）Ratio be slowly added dropwise isocyanates, rate of addition by temperature not
Situation control more than 90 DEG C, after isocyanates is dripped under the conditions of 70 DEG C -90 DEG C reacts 2-4 hours, is cooled to 60 DEG C,
10% ethyl acetate is added, is stirred evenly standby；
（3）Chain extending reaction, in step（2）Small molecule polyol chain extender is slowly added in obtained performed polymer, according to hydroxyl with
Isocyano mol ratio n in performed polymerOH: nNCO=(0.3-0.8)：1 ratio is added, after polyol chain extender is added, control
Temperature processed is added isocyanate blocking agents to continue reaction, until reaction stops, being obtained in 60 DEG C of -80 DEG C of scopes reaction 2-4 hours
Polyurethane resin；
（4）Product configuration, by step（3）Obtained polyurethane resin be slowly added to ethyl acetate, absolute ethyl alcohol, modified resin and
Auxiliary agent, is obtained the polyurethane resin for flexible package intaglio plate table printing ink, adds acetic acid per 100 parts of polyurethane resin domestic demands
Ethyl ester 10.0-15.0 parts, absolute ethyl alcohol 10.0-15.0 parts, modified resin 2.0-8.0 part and auxiliary agent 0.1-5.0 parts are described to change
Property resin be at least one in terpene resin and rosin derivative resin, the auxiliary agent includes scratch resistance agent and coupling agent.
2. the preparation method of a kind of polyurethane resin for flexible package intaglio plate table printing ink according to claim 1, its
It is characterised by：The step（1）In the synthesis of PEPA, polyacid is azelaic acid, decanedioic acid, adipic acid, isophthalic diformazan
One or more in acid and maleic acid, dihydroxylic alcohols are methyl propanediol, 1,6- hexylene glycols, diethyleneglycol bisphenol A, ethylene glycol
With one or more in BDO, catalyst is in butyl titanate, tetraisopropyl titanate, zinc acetate and antimony trioxide
One or more.
3. the preparation method of a kind of polyurethane resin for flexible package intaglio plate table printing ink according to claim 1, its
It is characterised by：The step（2）In the synthesis of performed polymer, isocyanates is Carbodiimide-Modified MDI, polymethylene polyphenyl
Polyisocyanates（PAPI）, hexamethylene diisocyanate（HDI）, isoflurane chalcone diisocyanate（IPDI）, xyxylene two it is different
Cyanate（XDI）, Methylcyclohexyl diisocyanate（HTDI）And dicyclohexyl methyl hydride diisocyanate（HMDI）In one kind
Or it is several.
4. the preparation method of a kind of polyurethane resin for flexible package intaglio plate table printing ink according to claim 1, its
It is characterised by：The step（3）In chain extending reaction, polyol chain extender be ethylene glycol, diethylene glycol (DEG), BDO, 1,6- oneself
One or more in glycol, sorbierite, glycerine and trimethylolpropane.
5. the preparation method of a kind of polyurethane resin for flexible package intaglio plate table printing ink according to claim 1, its
It is characterised by：The physical and chemical index of the polyurethane resin for flexible package intaglio plate table printing ink is：Solid content 68.0%-
72.0%, viscosity 1000-3000mPa.s (25 DEG C).
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| CN114773558A (en) * | 2022-04-28 | 2022-07-22 | 清远市美佳乐环保新材股份有限公司 | High-solid printing resin for flexible material and preparation method thereof |
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