CN103012724B - Preparation method of polyurethane resin for gravure composite ink - Google Patents
Preparation method of polyurethane resin for gravure composite ink Download PDFInfo
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Abstract
The invention discloses a preparation method of polyurethane resin for gravure composite ink, wherein the polyurethane resin is alcohol ester-soluble polyurethane resin not containing free cyanate ester radicals. Large amounts of allophanate radicals are introduced into the resin so that the ink prepared from the resin has excellent adhesion fastness to substrates such as PET (Polyethylene Glycol Terephthalate), NY (Nylon) and PP (Polypropylene) and the like. The preparation method is characterized in that diisocyanate is reacted with high-molecular polyol to generate NCO-terminated prepolymers, and then the prepolymers are added into a solvent containing an amine chain extender to achieve the polyurethane resin for the ink. The soft and hard segment of the resin has the advantages of wide adjustable range, large cohesive energy, good anti-aftertack property and good heat resistance; and the prepared ink has high binding strength to various printing substrates and has high composite strength. The preparation method provided by the invention has obvious characteristics of stable reaction in the synthesis process of the resin, easiness in control of the preparation process, narrow distribution of the molecular weight and good dissolubility of the resin.
Description
Technical field
The present invention relates to adhesive for printing ink, particularly relate to and a kind ofly to plastics film, there is excellent attachment fastness, color developing, the anti-preparation method returning sticky polyurethane resin for gravure composite ink.
Background technology
The gravure ink that current press uses generally is made up of Chlorinated Polypropylene III.In Printing ink producing process, Chlorinated Polypropylene III needs to use strong solvent (as aromatic solvents such as toluene) to dissolve, and also needs the viscosity regulating ink with toluene in printing process.Now, Chlorinated Polypropylene III ink system is considered to non-environmentfriendly products.Because the Chlorofluorocarbons (CFCs) that it volatilizes aborning can destroy atmospheric ozone layer; In Printing ink producing and printing process, the use of the aromatic solvents such as toluene can produce injury to the health and safety of workman.In addition, the aromatic solvents such as toluene are slow drying solvent, very easily remain in dried layer of ink, can pollute pack content and produce peculiar smell.Polyurethanes ink, compared with Chlorinated Polypropylene III, has the following advantages: 1. polyurethane ink adopts alcohol, esters solvent, without the need to relying on benzene kind solvent; 2. the stripping strength of polyurethane ink and base material is far above Chlorinated Polypropylene III class, as the stripping strength of Chlorinated Polypropylene III on NY only have 1-2N/15mm, and polyurethane ink can reach 2-5/15mm; 3. polyurethane ink can regulate ink performance as drying property, sticking power, viscosity etc. by adjustment material combination, proportion of composing, reaches good balance, realizes excellent printability; 4. relative to chlorinated polymer, urethane application base material is extensive, and the former generally can only be used for the gravure of BOPP, and the latter can be common to the base materials such as PET, NY, BOPP, PE.
CN1696217A mentions a kind of urethane resin obtained by the following method: first prepare through isocyanate-terminated prepolymer, then diamines is added in the diluent of prepolymer and carry out chain extension, finally carry out end-blocking with monoamine, described urethane resin is for the preparation of printing ink composition.CN101168633A discloses a kind of urethane resin dissolving in ethanol, first preparation end NCO base performed polymer, then is added in performed polymer by butyleneglycol and carry out chain extension, and the course of processing, without hazardous solvent, meets environmental requirement.CN1972977A discloses the preparation method of Polyurethane Resins for Inks, and wherein said urethane resin adopts polycaprolactone and isocyanate reaction, then adds diamines chain extension and be prepared.
The shortcoming of above-mentioned urethane is, their preparation method adopts " one still process " to be prepared, namely in performed polymer, NCO is excessive, then in same reactor, diamines is added in the performed polymer containing NCO and carry out chain extension, due to NCO and amino speed of response very fast, after adding diamine chain stretching agent, diamines partial concn is too high, cause local molecular amount in system very large, molecular weight distribution is irregular, resin viscosity is wayward, simultaneously, chain extension process is owing in system being the excessive state of NCO all the time, the urethane resin finally obtained is very easily containing unreacted NCO group completely, can slowly react after these NCO group are long placed in, molecular resin amount is caused to continue to increase, viscosity changes, potential safety hazard is brought to use, and the molecular resin chain end group that aforesaid method synthesizes is NCO base or alkyl, be low-pole group, the ink adhesion causing this resin-made to obtain is generally poor, easily return sticky, color developing is poor, combined strength bination is little.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of preparation method of polyurethane resin for gravure composite ink, and solving tackiness agent that current method obtains, to be used in the sticking power existed in ink poor, the problems such as easily return sticky, color developing is poor, and combined strength bination is little.
The technical scheme solved the problems of the technologies described above is as follows:
The invention provides a kind of preparation method of polyurethane resin for gravure composite ink, comprising:
Preparation polyester diol:
The dibasic alcohol of the diprotic acid of 48 ~ 56 mass parts, 44 ~ 52 mass parts is added in polyester synthesis reactor, is warming up to 200 ~ 240 DEG C, react and complete esterification in 5 ~ 6 hours; 160 DEG C are cooled to after esterification completes, start vacuum pump, polyester synthesis reactor is vacuumized, keeps vacuum tightness at-0.094Mpa, take out 1 ~ 2 hour, maintain vacuum tightness afterwards constant, with 5 ~ 8 hours by the still temperature rise to 210 of polyester synthesis reactor DEG C ~ 230 DEG C, after cut total amount to theoretical value, release overhead product, complete polycondensation, the product obtained is polyester diol;
Preparation end NCO base performed polymer:
After the mixing of the vulcabond of the catalyzer of the polyether Glycols of the above-mentioned obtained polyester diol of 36 ~ 76 mass parts, 10 ~ 36 mass parts, 0.05 ~ 0.2 mass parts, 16 ~ 28 mass parts, react under 50 ~ 120 DEG C of conditions after 2 ~ 4 hours and obtain that there is following structure end NCO base performed polymer: OCN-B-(-NH-CO-O-R
1-O-CO-NH-)
m-B-NCO; Wherein, R
1for methyl, methylene radical, ester group or aryl radical group, B is methyl, methylene radical, aryl radical or alicyclic hydrocarbon radical group;
Chain extension synthesizes:
In another container, add the amine chain extender (c) of 0.7 ~ 1.4 mass parts, ester class (d) of 46 ~ 56 mass parts, the alcoholic solvent (e) of 14 ~ 24 mass parts form mixing solutions, the above-mentioned obtained described end NCO base performed polymer of 28 ~ 30 mass parts was put in described mixing solutions with 5 ~ 50 minutes and carries out chain extending reaction, temperature of reaction is 30 ~ 50 DEG C, react the urethane resin namely obtaining having following structure after 2 ~ 4 hours and be polyurethane resin for gravure composite ink, the structure of this urethane resin is: NH
2-R
2-NH-(-CO-NH-R
1-NH-CO-)
n-NH-R
2-NH
2; Wherein, R
2for methyl, methylene radical, aryl radical or alicyclic hydrocarbon radical group.
In aforesaid method, described preparation polyester diol also comprises: after completing esterification, confirms the step whether esterification is qualified, if the Suan Zhi≤20mgKOH/g of reactant, confirm that esterification is qualified by the acid number measuring reactant.
In aforesaid method, described preparation polyester diol also comprises: after polycondensation completes, the step whether polycondensation is qualified is confirmed by test polycondensation product, if measure the hydroxyl value obtaining sample from described polycondensation product to reach 53 ± 3mgKOH/g and acid number < 1.0mgKOH/g, then confirm that the polycondensation product as polyester diol is qualified.
In aforesaid method, the diprotic acid that described preparation polyester diol adopts is selected from: any one or any two kinds in the ester formative derivative of aliphatic dicarboxylic acid, aromatic dicarboxylic acid, aliphatic dicarboxylic acid, the ester formative derivative of aromatic dicarboxylic acid;
The dibasic alcohol that described preparation polyester diol adopts is selected from: ethylene glycol, glycol ether, 1,2-propylene glycol, 1, ammediol, 1,4-butyleneglycol, 1,3-butyleneglycol, neopentyl glycol, 1,6-hexylene glycol, 3-methyl isophthalic acid, 5 pentanediols, 2-methyl isophthalic acid, the mixture of ammediol, any one and any two kinds had in the low-molecular-weight diol class of ring structure.
In aforesaid method, described aliphatic dicarboxylic acid is selected from: any one in succinic acid, sebacic acid, hexanodioic acid, nonane diacid, pentanedioic acid;
Described aromatic dicarboxylic acid is selected from: any one in terephthalic acid, m-phthalic acid, phthalic acid;
The described low-molecular-weight diol class with ring structure is selected from the ethylene oxide adduct of cyclohexane dimethanol or dihydroxyphenyl propane.
In aforesaid method, described preparation end NCO base performed polymer also comprises: after reaction, the mass content measuring the-NCO in reaction product confirms the step whether reaction product is qualified, if the mass percentage measuring the-NCO in the reaction product obtained is 1.0 ~ 4.5%, then confirm that the obtained reaction product as end NCO base performed polymer is qualified.
In aforesaid method, the polyether Glycols that described preparation end NCO base performed polymer adopts is selected from: the polytetramethylene ether diol that the polyoxypropyleneglycol that the polyoxypropyleneglycol that the polyoxypropyleneglycol that number-average molecular weight is 1000, number-average molecular weight are M2000, number-average molecular weight are 3000, number-average molecular weight are 1000, number-average molecular weight be 2000 polytetramethylene ether diol, number-average molecular weight be any one in the polytetramethylene ether diol of 3000;
The isocyanate-monomer that described preparation end NCO base performed polymer adopts is selected from: isoflurane chalcone diisocyanate, tolylene diisocyanate, dicyclohexyl methane diisocyanate, ditan-4,4 vulcabond, in 1,6 hexamethylene diisocyanates, tetramethylxylylene diisocyanate any one or several arbitrarily;
The catalyzer that described preparation end NCO base performed polymer adopts is selected from: dibutyl tin dilaurate, stannous octoate, tin protochloride, any one in tetrabutyl titanate.
In aforesaid method, described chain extension synthesis also comprises: the step of testing the polyurethane resin for gravure composite ink obtained, if the rotary viscosity testing the polyurethane resin for gravure composite ink 25 DEG C obtained is 800 ± 400mPa.s, solid content is 28 ~ 32%, and it is qualified to be;
In aforesaid method, the amine chain extender adopted in the synthesis of described chain extension is selected from: have in the aliphatics of primary amine groups or secondary amino group, alicyclic, aromatic series or heterocyclic diamine any one or several arbitrarily;
The esters solvent adopted in the synthesis of described chain extension is selected from: any one or mixtures several arbitrarily in vinyl acetic monomer, n-propyl acetate, n-butyl acetate;
The alcoholic solvent adopted in the synthesis of described chain extension is selected from: in ethanol, n-propyl alcohol, Virahol, propyl carbinol, methyl alcohol any one or several arbitrarily.
In aforesaid method, the amine chain extender adopted in described chain extension synthesis is selected from: different fluorine that ketone diamines, quadrol, 1,6-hexanediamine, Putriscine, new pentamethylene diamine, 4, in 4'-diamino-dicyclohexyl methane, Isosorbide-5-Nitrae-tetrahydrobenzene diamines, m-xylene diamine any one or several arbitrarily.
Beneficial effect of the present invention is as follows:
(1) by adopt " two still methods " chain extension technological design afterwards, reaction temperature and, chain extension process is steadily controlled; With traditional " one still process " directly in performed polymer compared with chain extension, and adopt and in amidebased solvents, carry out chain extension, narrow molecular weight distribution, viscosity is easy to control, and prepares workable;
(2) obtained molecular resin chain two ends are amino, not containing free NCO, and resin viscosity good stability;
(3) obtained urethane resin is Amino End Group end-blocking, and polarity is strong, and the ink obtained by this resin-made is strong to various substrate surface reactive force, and attachment fastness is good, and combined strength bination is high, anti-ly returns sticky, and resistance to elevated temperatures is good;
(4) obtained urethane resin solvability is good, and have good wettability to various pigment, the ink stability made is good;
(5) obtained urethane resin soft or hard section variable range is wide, and hard segment content can control in the scope of 15% to 30%;
(6) obtained urethane resin is the molten type polyurethane of a kind of environment-friendly type single-component alcohol ester, is solvent by alcohols and ester class, not containing the noxious solvent such as arene, ketone, meets ecological requirements.
Embodiment
Be clearly and completely described the technical scheme in the embodiment of the present invention below, obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiments.Based on embodiments of the invention, those of ordinary skill in the art, not making the every other embodiment obtained under creative work prerequisite, belong to protection scope of the present invention.
Below the embodiment of the present invention is described in further detail.
Embodiment 1:
The present embodiment provides a kind of preparation method of polyurethane resin for gravure composite ink, specifically comprises the following steps:
(1) preparation of polyester polyol
The hexanodioic acid of the phthalic acid of 24 mass parts, 32 mass parts, the butyleneglycol of 44 mass parts are added in polyester synthesis reactor, be warming up to 200 ~ 240 DEG C, reaction 5 is little after acid number is less than 20, completes esterification; Be cooled to 160 DEG C after esterification completes, start vacuum pump, vacuumize, keep vacuum tightness at-0.094Mpa, take out 2 hours, afterwards, maintain vacuum tightness constant, with 5 hours, still temperature is slowly risen to 210 DEG C, after after cut total amount to theoretical value 15 mass parts, release overhead product, obtain polyester diol, acid number is 0.6, and hydroxyl value is 55;
(2) preparation end NCO base performed polymer:
By the polyether Glycols of polyester diol obtained in 36 mass parts (1), 36 mass parts, after the catalyzer of 0.07 mass parts, 28 mass parts MDI mix, the NCO obtained react 3h under 80 DEG C of conditions after is the performed polymer of 6.4;
(3) chain extension synthesis:
Another preparation one flask; add 1.3 quality quadrols, 56 mass parts n-propyl acetates, 14 mass parts ethanol; stir; chain extending reaction is carried out by dropping in above-mentioned mixing solutions in performed polymer 5min obtained in 28.7 mass parts (2); temperature of reaction controls at 30 DEG C; react and namely obtain urethane resin after 2.5 hours, viscosity is 1100mpa.s, and solid content is 29.7%;
Embodiment 2
The present embodiment provides a kind of preparation method of polyurethane resin for gravure composite ink, specifically comprises the following steps:
(1) preparation of polyester polyol
The hexanodioic acid of the m-phthalic acid of 27 mass parts, 23 mass parts, the neopentyl glycol of 50 mass parts are added in polyester synthesis reactor, is warming up to 200 ~ 240 DEG C, react and complete esterification in 5 hours; Be cooled to 160 DEG C after esterification completes, start vacuum pump, vacuumize, keep vacuum tightness at-0.094Mpa, take out 2 hours, afterwards, maintain vacuum tightness constant, with 5 hours, still temperature is slowly risen to 210 DEG C, after cut total amount to 20 mass parts, release overhead product, obtain polyester polyol, acid number is 0.3, and hydroxyl value is 57;
(2) preparation end NCO base performed polymer:
By the PPG2000 of polyester diol obtained in 56 mass parts (1), 28 mass parts, after the catalyzer of 0.07 mass parts, 16 mass parts TDI mix, the nco value obtained react 2h under 80 DEG C of conditions after is the performed polymer of 4.2;
(3) chain extension synthesis:
Another preparation one flask; add 1.4 mass parts 1; 6 hexanediamines, 46 mass parts N-BUTYL ACETATEs, 24 mass parts Virahols; stir; carry out chain extending reaction by dropping in above-mentioned mixing solutions in performed polymer 30min obtained in 28.6 mass parts (2), temperature of reaction controls at 40 DEG C, reacts and namely obtains urethane resin after 2 hours; viscosity is 820mpa.s, and solid content is 30.2%;
Embodiment 3
The present embodiment provides a kind of preparation method of polyurethane resin for gravure composite ink, specifically comprises the following steps:
(1) preparation of polyester polyol
The glycol ether of the hexanodioic acid of 48 mass parts, 52 mass parts is added in polyester synthesis reactor, is warming up to 200 ~ 240 DEG C, react and complete esterification in 5.5 hours; 160 DEG C are cooled to after esterification completes, start vacuum pump, vacuumize, keep vacuum tightness at-0.094Mpa, take out 2 hours, afterwards, maintain vacuum tightness constant, with 5 hours, still temperature is slowly risen to 210 DEG C, after cut total amount to 25 mass parts, release overhead product, obtaining polyester diol acid number is 0.9, and hydroxyl value is 54;
(2) preparation end NCO base performed polymer:
By the PPG1000 of polyester diol obtained in 76 mass parts (1), 10 mass parts, after the catalyzer of 0.07 mass parts, 24 mass parts IPDI mix, the nco value obtained react 3h under 90 DEG C of conditions after is the performed polymer of 5.0;
(3) chain extension synthesis:
Another preparation one flask; add 0.7 mass parts different fluorine that ketone diamines, 46 mass parts n-propyl acetates, 24 mass parts ethanol; stir; chain extending reaction is carried out by dropping in above-mentioned mixing solutions in performed polymer 50min obtained in 29.3 mass parts (2); temperature of reaction controls at 50 DEG C; react and namely obtain urethane resin after 2 hours, viscosity is 1600, and solid content is 30.1;
Compound experiment result is as shown in table 2:
Table 2. compound experiment result
As can be seen from Table 2, resin prepared by " two still methods ", soft or hard section variable range is wide, and evenly, viscosity is easy to control, and molecular weight distribution is narrower, and obtained resin transparent is good in preparation process reaction.
Application examples
Polyurethane resin solution embodiment 1 ~ 3 obtained makes printing-ink according to the formula of table 3.Inner capacities 250cm is loaded by following raw material
3sealed plastic bottle in, with the mixing 2-3 hour of quick worker, obtain printing ink composition.Following performance test is carried out to the ink obtained.
Table 3 intaglio compound plastic film ink is filled a prescription
| Raw material | Chalk mass parts | Red black mass parts | Yellow black mass parts | Blue black mass parts | Tusche mass parts |
| Urethane resin | 66 | 54 | 54 | 54 | 54 |
| 20% chlorine vinegar solution | 10 | 20 | 20 | 20 | 20 |
| Titanium dioxide | 60 | ||||
| 146 is red | 18 | ||||
| Diarylide yellow | 18 | ||||
| Phthalocyanine blue | 18 | ||||
| Carbon black | 18 | ||||
| Polyethylene wax | 1 | 1 | 1 | 1 | 1 |
| Vinyl acetic monomer | 39 | 51 | 51 | 36 | 34 |
| N-propyl acetate | 16 | 44 | 44 | 44 | 44 |
| Virahol | 8 | 12 | 12 | 12 | 12 |
| Amount to | 200 | 200 | 200 | 200 | 200 |
Remarks: chlorine vinegar used is Japanese SHIN-ETSU HANTOTAI chlorine vinegar A resin are 20% solid content with vinyl acetic monomer dilution
(1) the ink attachment fastness method of inspection:
Use silk rod at the upper dope ink composition of surface treated polyester film (PET), make solids component be the thickness of 2-3um.After drying up with blower, paste 3M adhesive tape at coated face, adhesive tape and painting face direction at a right angle is peeled off rapidly, observe coated face state.
Judgement criteria is: O: ink residue more than 90%.
△: ink residue 50 ~ 90%
×: ink residue discontented 50%
(2) the ink colors method of inspection:
Label taking sample ink is a small amount of, drips in OPP film upper left side, then it is a small amount of in upper right side to materials, and both are adjacent and be not connected.Exert oneself from top to bottom with silk rod, ink is scraped lamellar on OPP film.Observe sample whether consistent with the complexion of standard specimen.
Judgement criteria: O: approximate standard specimen
×: differ larger with standard specimen
(3) the ink viscosity method of inspection:
By ink temperature adjustment to room temperature (about 25 DEG C).Ink of materialsing is poured 3# into and is examined in grace cup, until ink with examine till grace cup edge flushes, scrape off bubble with glass stick.Test sample, from starting to flow out to required time when sample stream silk interrupts and presents first, is the viscosity of this ink.
(4) the ink combined strength bination method of inspection:
Use silk rod at the upper dope ink composition of surface treated polyester film (PET), make solids component be the thickness of 2-3um.After drying up with blower, with silk rod coating polyurethane binder, spread is 2-2.5g/m3.(tackiness agent adopts the YH2000S/YH10 of Beijing Gao Meng limited-liability company) then carries out compound with the OPP film through surface treatment process, slaking 48h at 50 DEG C.Composite membrane is made the sample of wide 15mm, measure T stripping strength with universal electronic drawing machine, and in this, as combined strength bination.Numerical value is larger, and combined strength bination is higher.
(5) the ink antiblocking method of inspection:
Use silk rod at the upper dope ink composition of surface treated polyester film (PET), make solids component be the thickness of 2-3um, fully dry up with blower.Coated face is overlapped with uncoated, under temperature 50 C, applies the load of 2.0kgf/cm2.Peel off after 2 hours, observe its condition of surface.
Judgement criteria O: do not have adhesion during stripping
△: have adhesion during stripping
×: ink shifts
(6) the ink solubility method of inspection:
By Ink Application on a glass, make solids component reach the thickness of 2 ~ 3um, deposit 30 seconds under room temperature (about 25 DEG C) after, the weight ratio being immersed in vinyl acetic monomer/n-propyl acetate/Virahol is in the solvent of 1:1:1, observes the solvability again of ink film.
Judgement criteria O: film dissolves again
×: film does not dissolve and residues in sheet glass
(7) the ink stability method of inspection:
After the ink configured is deposited 30 days under room temperature (about 25 DEG C), observe ink layering and precipitation status.
Judgement criteria O: ink is without layering, without precipitation
△: ink, without layering, has a small amount of precipitation
×: ink layering, or have a large amount of precipitation
The performance test results is as shown in table 4:
Table 4 application performance test result
Combined strength bination test result is as shown in table 5:
Table 5. combined strength bination test result
The above-mentioned method of inspection to utilizing the embodiment of the present invention to obtain the standby polyurethane ink of resin-made, be measure its quality index according to National Standard of the People's Republic of China, concrete reference standard is as follows:
As can be seen from table 4, table 5 application testing result, the urethane resin that " the two still methods " that adopt in the present invention is obtained, have attachment fastness with the ink that this resin-made obtains good, color developing is good, combined strength bination is high, solubility, good stability, anti-returns the plurality of advantages such as sticky.
In sum, the preparation method of the embodiment of the present invention with ester class and alcohols for the obtained binder resin of primary solvent, can be used for gravure composite printing ink to use, there is the various features such as safe, nontoxic, environmental protection, health, the ink fastness made with this resin is good, and color development is good, and combined strength bination is high, solubility, good stability, anti-return sticky, can as a without benzene without ketone ink binder.The method overcome many shortcomings of above-mentioned " one still process " polyurethane system, have employed unique " two still methods " technological design, namely first in the first reactor, performed polymer is synthesized, separately prepare a reactor again, amine chain extender and diluting solvent is added in this reactor, then performed polymer obtained in the first reactor is slowly added drop-wise in the second reactor and carries out rear chain extension, by this processing method, ensure that chain extension process is slowly gentle, resin viscosity slowly increases, the molecular resin amount narrow distribution finally obtained.The molecular resin amount chain two ends of this method synthesis are all amino, because amino is strong polar group, can significantly improve the sticking power between resin and base material, improve the wettability between resin and pigment.Therefore, the ink fastness made with the resin that this technique obtains is good, and combined strength bination is high, and anti-after tack is good, is applicable to the gravure printing technique applied on the base material of wide region.
The above; be only the present invention's preferably embodiment, but protection scope of the present invention is not limited thereto, is anyly familiar with those skilled in the art in the technical scope that the present invention discloses; the change that can expect easily or replacement, all should be encompassed within protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection domain of claims.
Claims (9)
1. a preparation method for polyurethane resin for gravure composite ink, is characterized in that, comprising:
Preparation polyester diol:
The dibasic alcohol of the diprotic acid of 48 ~ 56 mass parts, 44 ~ 52 mass parts is added in polyester synthesis reactor, is warming up to 200 ~ 240 DEG C, react and complete esterification in 5 ~ 6 hours; 160 DEG C are cooled to after esterification completes, start vacuum pump, polyester synthesis reactor is vacuumized, keeps vacuum tightness at-0.094Mpa, take out 1 ~ 2 hour, maintain vacuum tightness afterwards constant, with 5 ~ 8 hours by the still temperature rise to 210 of polyester synthesis reactor DEG C ~ 230 DEG C, after cut total amount to theoretical value, release overhead product, complete polycondensation, the product obtained is polyester diol;
Preparation end NCO base performed polymer:
After the mixing of the vulcabond of the catalyzer of the polyether Glycols of the above-mentioned obtained polyester diol of 36 ~ 76 mass parts, 10 ~ 36 mass parts, 0.05 ~ 0.2 mass parts, 16 ~ 28 mass parts, react under 50 ~ 120 DEG C of conditions after 2 ~ 4 hours and obtain end NCO base performed polymer;
Described polyether Glycols is selected from: the polytetramethylene ether diol that the polyoxypropyleneglycol that the polyoxypropyleneglycol that the polyoxypropyleneglycol that number-average molecular weight is 1000, number-average molecular weight are 2000, number-average molecular weight are 3000, number-average molecular weight are 1000, number-average molecular weight be 2000 polytetramethylene ether diol, number-average molecular weight be any one in the polytetramethylene ether diol of 3000; Described isocyanate-monomer is selected from: isophorone diisocyanate, tolylene diisocyanate, dicyclohexyl methane diisocyanate, ditan-4,4 vulcabond, in hexamethylene diisocyanate, tetramethylxylylene diisocyanate any one or several arbitrarily; Described catalyzer is selected from: dibutyl tin laurate, stannous octoate, tin protochloride, any one in tetrabutyl titanate;
Chain extension synthesizes:
In another container, add the amine chain extender (c) of 0.7 ~ 1.4 mass parts, ester class (d) of 46 ~ 56 mass parts, the alcoholic solvent (e) of 14 ~ 24 mass parts form mixing solutions, the above-mentioned obtained described end NCO base performed polymer of 28 ~ 30 mass parts was put in described mixing solutions with 5 ~ 50 minutes and carries out chain extending reaction, temperature of reaction is 30 ~ 50 DEG C, reacts namely to obtain urethane resin after 2 ~ 4 hours and be polyurethane resin for gravure composite ink.
2. method according to claim 1, it is characterized in that, described preparation polyester diol also comprises: after completing esterification, confirms the step whether esterification is qualified, if the Suan Zhi≤20mgKOH/g of reactant, confirm that esterification is qualified by the acid number measuring reactant.
3. method according to claim 1, it is characterized in that, described preparation polyester diol also comprises: after polycondensation completes, the step whether polycondensation is qualified is confirmed by test polycondensation product, if measure the hydroxyl value obtaining sample from described polycondensation product to reach 53 ± 3mgKOH/g and acid number < 1.0mgKOH/g, then confirm that the polycondensation product as polyester diol is qualified.
4. the method according to any one of claims 1 to 3, is characterized in that, the diprotic acid that described preparation polyester diol adopts is selected from: any one or any two kinds in aliphatic dicarboxylic acid, aromatic dicarboxylic acid;
The dibasic alcohol that described preparation polyester diol adopts is selected from: ethylene glycol, glycol ether, 1,2-propylene glycol, 1, ammediol, 1,4-butyleneglycol, 1,3-butyleneglycol, neopentyl glycol, 1,6-hexylene glycol, 3-methyl isophthalic acid, 5-pentanediol, 2-methyl isophthalic acid, the mixture of ammediol, any one and any two kinds had in the low-molecular-weight diol class of ring structure.
5. method according to claim 4, is characterized in that, described aliphatic dicarboxylic acid is selected from: any one in succinic acid, sebacic acid, hexanodioic acid, nonane diacid, pentanedioic acid;
Described aromatic dicarboxylic acid is selected from: any one in terephthalic acid, m-phthalic acid, phthalic acid;
The described low-molecular-weight diol class with ring structure is selected from the ethylene oxide adduct of cyclohexane dimethanol or dihydroxyphenyl propane.
6. method according to claim 1, it is characterized in that, described preparation end NCO base performed polymer also comprises: after reaction, the mass content measuring the-NCO in reaction product confirms the step whether reaction product is qualified, if the mass percentage measuring the-NCO in the reaction product obtained is 1.0 ~ 4.5%, then confirm that the obtained reaction product as end NCO base performed polymer is qualified.
7. method according to claim 1, it is characterized in that, described chain extension synthesis also comprises: the step of testing the polyurethane resin for gravure composite ink obtained, if the 25 DEG C of rotary viscosities testing the polyurethane resin for gravure composite ink obtained are 800 ± 400mpa.s, solid content is 28 ~ 32%, and it is qualified to be.
8. method according to claim 1, is characterized in that, the amine chain extender adopted in the synthesis of described chain extension is selected from: have in the aliphatics of primary amine groups or secondary amino group, alicyclic, aromatic series or heterocyclic diamine any one or several arbitrarily;
The esters solvent adopted in the synthesis of described chain extension is selected from: any one or mixtures several arbitrarily in vinyl acetic monomer, n-propyl acetate, n-butyl acetate;
The alcoholic solvent adopted in the synthesis of described chain extension is selected from: in ethanol, n-propyl alcohol, Virahol, propyl carbinol, methyl alcohol any one or several arbitrarily.
9. method according to claim 8, it is characterized in that, the amine chain extender adopted in described chain extension synthesis is selected from: isophorone diamine, quadrol, 1,6-hexanediamine, 1,4-butanediamine, new pentamethylene diamine, 4, in 4'-diamino-dicyclohexyl methane, Isosorbide-5-Nitrae-tetrahydrobenzene diamines, m-xylene diamine any one or several arbitrarily.
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| JP6299765B2 (en) * | 2013-11-11 | 2018-03-28 | 日立化成株式会社 | Binder for printing ink, laminate ink composition for soft packaging, and printed matter |
| CN103613736A (en) * | 2013-11-19 | 2014-03-05 | 张家港威迪森化学有限公司 | Preparation method of polyurethane adhesive |
| TWI586751B (en) | 2014-11-10 | 2017-06-11 | 財團法人工業技術研究院 | Thermoplastic polyester elastomer and method for manufacturing the same |
| CN104448216A (en) * | 2014-11-27 | 2015-03-25 | 成都锦汇科技有限公司 | Ethanol-soluble polyurethane resin for printing ink and preparation method of ethanol-soluble polyurethane resin |
| CN106554476A (en) * | 2016-07-15 | 2017-04-05 | 新东方油墨有限公司 | A kind of preparation method of the polyurethane resin for flexible package intaglio plate table printing ink |
| CN106519162A (en) * | 2016-11-18 | 2017-03-22 | 北京高盟新材料股份有限公司 | Single ester-soluble polyurethane resin for printing ink, and preparation method thereof |
| WO2018199085A1 (en) * | 2017-04-26 | 2018-11-01 | 大日精化工業株式会社 | Bio-based polyurethane resin, bio-based polyurethane resin solution, and printing ink |
| CN110818881B (en) * | 2019-11-22 | 2021-10-22 | 万华化学（北京）有限公司 | Preparation method of polyurethane ink resin, polyurethane ink resin prepared by preparation method and ink |
| CN110698638A (en) * | 2019-11-26 | 2020-01-17 | 南通高盟新材料有限公司 | Single-solvent polyurethane ink binder and preparation method thereof |
| CN114920902A (en) * | 2022-06-10 | 2022-08-19 | 东莞市宏达聚氨酯有限公司 | Environment-friendly low-temperature-resistant polyurethane resin for table printing ink and application thereof |
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| CN102432808A (en) * | 2011-08-04 | 2012-05-02 | 北京高盟新材料股份有限公司 | Preparation method of low-cost resin for printing ink |
| CN102775576A (en) * | 2012-07-05 | 2012-11-14 | 新东方油墨有限公司 | Connecting material for printing composite ink in polyurethane by using high-speed printer and preparation method for connecting material |
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| WO2009060838A1 (en) * | 2007-11-05 | 2009-05-14 | Asahi Glass Company, Limited | Polyurethane for printing ink binder, method for producing the same and printing ink |
| CN102432808A (en) * | 2011-08-04 | 2012-05-02 | 北京高盟新材料股份有限公司 | Preparation method of low-cost resin for printing ink |
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