CN103012724A - Preparation method of polyurethane resin for gravure composite ink - Google Patents
Preparation method of polyurethane resin for gravure composite ink Download PDFInfo
- Publication number
- CN103012724A CN103012724A CN2013100143918A CN201310014391A CN103012724A CN 103012724 A CN103012724 A CN 103012724A CN 2013100143918 A CN2013100143918 A CN 2013100143918A CN 201310014391 A CN201310014391 A CN 201310014391A CN 103012724 A CN103012724 A CN 103012724A
- Authority
- CN
- China
- Prior art keywords
- mass parts
- acid
- preparation
- resin
- performed polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Inks, Pencil-Leads, Or Crayons (AREA)
- Polyurethanes Or Polyureas (AREA)
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 of plastics film is had good attachment fastness, color developing, anti-ly returns sticking gravure composite printing ink with the preparation method of urethane resin.
Background technology
The gravure ink of at present press use is generally made by Chlorinated Polypropylene III.In the Printing ink producing process, Chlorinated Polypropylene III need to use strong solvent (such as aromatic solvents such as toluene) to dissolve, and also needs to regulate with toluene the viscosity of printing ink in printing process.Now, the Chlorinated Polypropylene III ink system is considered to non-environmentfriendly products.Because the Chlorofluorocarbons (CFCs) that it volatilizes aborning can be destroyed atmospheric ozone layer; In Printing ink producing and printing process, the use meeting of the aromatic solvents such as toluene produces injury to workman's health and safety.In addition, the aromatic solvents such as toluene are the slow curing solvents, very easily remain in the dried China ink layer, can pollute the packing content thing and produce peculiar smell.Polyurethanes printing ink is compared with Chlorinated Polypropylene III, has the following advantages: 1. polyurethane ink adopts alcohol, esters solvent, need not to rely on benzene kind solvent; 2. the stripping strength of polyurethane ink and base material is far above the 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 be regulated ink performance such as drying property, sticking power, viscosity etc. by regulating material combination, proportion of composing, reaches good balance, realizes excellent printability; 4. with respect to chlorinated polymer, it is extensive that urethane is used base material, 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 that obtains by the following method: at first prepare through isocyanate-terminated prepolymer, then diamines is added in the diluent of prepolymer and carry out chain extension, carry out end-blocking with monoamine at last, described urethane resin is for the preparation of printing ink composition.CN101168633A discloses a kind of urethane resin that dissolves in ethanol, and preparation end NCO base performed polymer adds butyleneglycol and carries out chain extension in the performed polymer first, and the course of processing meets environmental requirement without hazardous solvent.CN1972977A discloses the preparation method of Polyurethane Resins for Inks, and wherein said urethane resin adopts polycaprolactone and isocyanate reaction, adds the diamines chain extension again and is prepared.
The shortcoming of above-mentioned urethane is, their preparation method adopts " one still process " to be prepared, be that NCO is excessive in the performed polymer, then in same reactor, diamines added in the performed polymer contain NCO and carry out chain extension, because NCO and amino speed of response are very fast, after adding diamine chain stretching agent, the diamines partial concn is too high, causes the interior local molecular weight of system very large, and molecular weight distribution is irregular, resin viscosity is wayward, simultaneously, the chain extension process is owing to being the excessive state of NCO all the time in the system, and the urethane resin that finally obtains very easily contains completely NCO group of unreacted, after being long placed in, these NCO groups can slowly react, cause the molecular resin amount to continue to increase, viscosity changes, and brings potential safety hazard to use, and the molecular resin chain end group that aforesaid method synthesizes is NCO base or alkyl, be the low-pole group, the ink adhesion that causes this resin to get is generally relatively poor, easily returns sticking, color developing is poor, and combined strength bination is little.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of gravure composite printing ink with the preparation method of urethane resin, and solving tackiness agent that present method makes, to be used in the sticking power that exists in the printing ink relatively poor, easily return sticking, the problem such as color developing is poor, and combined strength bination is little.
The technical scheme that solves the problems of the technologies described above is as follows:
The invention provides a kind of gravure composite printing ink preparation method of urethane resin, comprising:
The preparation polyester diol:
The diprotic acid of 48～56 mass parts, the dibasic alcohol of 44～52 mass parts are added in the polyester synthesis reactor, be warming up to 200～240 ℃, react and finished esterification in 5～6 hours; After finishing, esterification is cooled to 160 ℃, start vacuum pump, the polyester synthesis reactor is vacuumized, keep vacuum tightness at-0.094Mpa, took out 1～2 hour, keep afterwards vacuum tightness constant, with 5～8 hours with the still temperature rise to 210 of polyester synthesis reactor ℃～230 ℃, the cut total amount is emitted overhead product after theoretical value, finish polycondensation, the product that obtains is polyester diol;
Preparation end NCO base performed polymer:
After the vulcabond of the catalyzer of the polyether Glycols of the above-mentioned polyester diol that makes of 36～76 mass parts, 10～36 mass parts, 0.05～0.2 mass parts, 16～28 mass parts mixed, after reacting 2～4 hours under 50～120 ℃ of conditions, obtain having following structure end NCO base performed polymer: OCN-B-(NH-CO-O-R
1-O-CO-NH-)
m-B-NCO; Wherein, R
1Be methyl, methylene radical, ester group or aryl radical group, B is methyl, methylene radical, aryl radical or alicyclic hydrocarbon radical group;
Chain extension is synthetic:
In another container, add the amine chain extender (c) of 0.7～1.4 mass parts, the ester class (d) of 46～56 mass parts, alcoholic solvent (e) the formation mixing solutions of 14～24 mass parts, the above-mentioned described end NCO base performed polymer that makes of 28～30 mass parts put into 5～50 minutes carry out chain extending reaction in the described mixing solutions, temperature of reaction is 30～50 ℃, react the urethane resin that namely obtains having following structure after 2～4 hours and be the gravure composite printing ink urethane resin, the structure of this urethane resin is: NH
2-R
2-NH-(CO-NH-R
1-NH-CO-)
n-NH-R
2-NH
2Wherein, R
2Be methyl, methylene radical, aryl radical or alicyclic hydrocarbon radical group.
In the aforesaid method, described preparation polyester diol also comprises: after finishing esterification, confirm whether qualified step of esterification by the acid number of measuring reactant, if the Suan Zhi＜=20mgKOH/g of reactant confirms that then esterification is qualified.
In the aforesaid method, described preparation polyester diol also comprises: after polycondensation is finished, confirm whether qualified step of polycondensation by the test polycondensation product, reach 53 ± 3mgKOH/g and acid number＜1.0mgKOH/g if measure the hydroxyl value that obtains sample from described polycondensation product, it is qualified then to confirm as the polycondensation product of polyester diol.
In the aforesaid method, the diprotic acid that described preparation polyester diol adopts is selected from: any in the ester formative derivative of aliphatic dicarboxylic acid, aromatic dicarboxylic acid, aliphatic dicarboxylic acid, the ester formative derivative of aromatic dicarboxylic acid or any two kinds;
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, have any and any two kinds mixture in the low-molecular-weight diol class of ring structure at ammediol.
In the aforesaid method, described aliphatic dicarboxylic acid is selected from: any in Succinic Acid, sebacic acid, hexanodioic acid, nonane diacid, the pentanedioic acid;
Described aromatic dicarboxylic acid is selected from: any in terephthalic acid, m-phthalic acid, the phthalic acid;
Described low-molecular-weight diol class with ring structure is selected from the ethylene oxide adduct of cyclohexyl dimethanol or dihydroxyphenyl propane.
In the aforesaid method, described preparation end NCO base performed polymer also comprises: after the reaction, measure in the reaction product-mass content of NCO confirms whether qualified step of reaction product, if in the reaction product that measures-the quality percentage composition of NCO is 1.0～4.5%, confirms that then the reaction product that makes as end NCO base performed polymer is qualified.
In the aforesaid method, the polyether Glycols that described preparation end NCO base performed polymer adopts is selected from: polyoxypropyleneglycol, the number-average molecular weight that number-average molecular weight is 1000 polyoxypropyleneglycol, number-average molecular weight is M2000 is that 3000 polyoxypropyleneglycol, number-average molecular weight are that 1000 polytetramethylene ether diol, number-average molecular weight are that 2000 polytetramethylene ether diol, number-average molecular weight are any in 3000 the polytetramethylene ether diol;
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 diisocyanate, the tetramethylxylylene diisocyanate any 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 in the tetrabutyl titanate.
In the aforesaid method, described chain extension is synthetic also to be comprised: the step that the gravure composite printing ink that obtains is tested with urethane resin, if the gravure composite printing ink that test obtains is 800 ± 400mPa.s with the rotary viscosity of 25 ℃ of urethane resins, solid content is 28～32%, and it is qualified to be;
In the aforesaid method, the amine chain extender that adopts during described chain extension is synthetic is selected from: have in the aliphatics of primary amine groups or secondary amino group, alicyclic, aromatic series or the heterocyclic diamine any or several arbitrarily;
The esters solvent that adopts during described chain extension is synthetic is selected from: any in vinyl acetic monomer, n-propyl acetate, the n-butyl acetate or any several mixture;
The alcoholic solvent that adopts during described chain extension is synthetic is selected from: any in ethanol, n-propyl alcohol, Virahol, propyl carbinol, the methyl alcohol or several arbitrarily.
In the aforesaid method, the amine chain extender that adopts during described chain extension is synthetic 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, the m-xylene diamine any or several arbitrarily.
Beneficial effect of the present invention is as follows:
(1) by adopting chain extension technological design after " two still methods ", reaction temperature and, the chain extension process is steadily controlled; Directly chain extension is compared in performed polymer with traditional " one still process ", and adopts and carry out chain extension in amino solvent, and narrow molecular weight distribution, viscosity are easy to control, prepare workable;
(2) the molecular resin chain two ends that make are amino, do not contain free NCO, the resin viscosity good stability;
(3) urethane resin that makes is amino-terminated for end, and polarity is strong, and the printing ink that gets with this resin is strong to various substrate surface reactive forces, and attachment fastness is good, and combined strength bination is high, resists to return stickingly, and resistance to elevated temperatures is good;
(4) the urethane resin solvability that makes is good, and various pigment are had good wettability, and the ink stability of making is good;
(5) the urethane resin soft or hard section variable range that makes is wide, and hard segment content can be controlled in 15% to 30% the scope;
(6) urethane resin that makes is the molten type polyurethane of a kind of environment-friendly type single-component alcohol ester, is solvent with alcohols and ester class, does not contain the noxious solvents such as arene, ketone, meets the environmental protection demand.
Embodiment
The below is clearly and completely described the technical scheme in the embodiment of the invention, and obviously, described embodiment only is the present invention's part embodiment, rather than whole embodiment.Based on embodiments of the invention, those of ordinary skills belong to protection scope of the present invention not making the every other embodiment that obtains under the creative work prerequisite.
The below is described in further detail the embodiment of the invention.
Embodiment 1:
The present embodiment provides the preparation method of a kind of gravure composite printing ink with urethane resin, specifically may further comprise the 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 the polyester synthesis reactor, are warming up to 200～240 ℃, react 5 hours to acid number less than after 20, finish esterification; Be cooled to 160 ℃ after esterification is finished, start vacuum pump, vacuumize, keep vacuum tightness at-0.094Mpa, took out 2 hours, and afterwards, kept vacuum tightness constant, with 5 hours the still temperature is slowly risen to 210 ℃, the cut total amount after theoretical value 15 mass parts after, emit overhead product, obtain polyester diol, acid number is 0.6, and hydroxyl value is 55;
(2) preparation end NCO base performed polymer:
With the polyester diol that makes in 36 mass parts (1), the polyether Glycols of 36 mass parts, behind the catalyzer of 0.07 mass parts, the 28 mass parts MDI mixings, the NCO that obtains behind reaction 3h under 80 ℃ of conditions is 6.4 performed polymer;
(3) chain extension is synthetic:
Other prepares a flask, add 1.3 quality quadrols, 56 mass parts n-propyl acetates, 14 mass parts ethanol, stir, the performed polymer that makes in 28.7 mass parts (2) is carried out chain extending reaction with dropping in the above-mentioned mixing solutions in the 5min, temperature of reaction is controlled at 30 ℃, 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 the preparation method of a kind of gravure composite printing ink with urethane resin, specifically may further comprise the steps:
(1) preparation of polyester polyol
The m-phthalic acid of 27 mass parts, the hexanodioic acid of 23 mass parts, the neopentyl glycol of 50 mass parts are added in the polyester synthesis reactor, be warming up to 200～240 ℃, react and finished esterification in 5 hours; Be cooled to 160 ℃ after esterification is finished, start vacuum pump, vacuumize, keep vacuum tightness at-0.094Mpa, took out 2 hours, and afterwards, kept vacuum tightness constant, with 5 hours the still temperature is slowly risen to 210 ℃, the cut total amount is emitted overhead product after 20 mass parts, obtain polyester polyol, acid number is 0.3, and hydroxyl value is 57;
(2) preparation end NCO base performed polymer:
With the polyester diol that makes in 56 mass parts (1), the PPG2000 of 28 mass parts, behind the catalyzer of 0.07 mass parts, the 16 mass parts TDI mixings, the nco value that obtains behind reaction 2h under 80 ℃ of conditions is 4.2 performed polymer;
(3) chain extension is synthetic:
Other prepares a flask, add 1.4 mass parts 1,6 hexanediamines, 46 mass parts N-BUTYL ACETATEs, 24 mass parts Virahols, stir, the performed polymer that makes in 28.6 mass parts (2) is carried out chain extending reaction with dropping in the above-mentioned mixing solutions in the 30min, and temperature of reaction is controlled at 40 ℃, reacts namely to obtain urethane resin after 2 hours, viscosity is 820mpa.s, and solid content is 30.2%;
Embodiment 3
The present embodiment provides the preparation method of a kind of gravure composite printing ink with urethane resin, specifically may further comprise the steps:
(1) preparation of polyester polyol
The hexanodioic acid of 48 mass parts, the glycol ether of 52 mass parts are added in the polyester synthesis reactor, be warming up to 200～240 ℃, react and finished esterification in 5.5 hours; After finishing, esterification is cooled to 160 ℃, start vacuum pump, vacuumize, keep vacuum tightness at-0.094Mpa, took out 2 hours, afterwards, keep vacuum tightness constant, with 5 hours the still temperature is slowly risen to 210 ℃, the cut total amount is after 25 mass parts, emit overhead product, obtaining the polyester diol acid number is 0.9, and hydroxyl value is 54;
(2) preparation end NCO base performed polymer:
With the polyester diol that makes in 76 mass parts (1), the PPG1000 of 10 mass parts, behind the catalyzer of 0.07 mass parts, the 24 mass parts IPDI mixings, the nco value that obtains behind reaction 3h under 90 ℃ of conditions is 5.0 performed polymer;
(3) chain extension is synthetic:
Other prepares a flask, add the different fluorine that of 0.7 mass parts ketone diamines, 46 mass parts n-propyl acetates, 24 mass parts ethanol, stir, the performed polymer that makes in 29.3 mass parts (2) is carried out chain extending reaction with dropping in the above-mentioned mixing solutions in the 50min, temperature of reaction is controlled at 50 ℃, react and namely obtain urethane resin after 2 hours, viscosity is 1600, and solid content is 30.1;
The compound experiment result is as shown in table 2:
Table 2. compound experiment result
As can be seen from Table 2, the resin of " two still methods " preparation, soft or hard section variable range is wide, and the preparation process reaction is even, and viscosity is easy to control, and molecular weight distribution is narrower, and the resin transparent that makes is good.
Application examples
Embodiment 1～3 resulting polyurethane resin solution is made printing-ink according to the prescription of table 3.Be about to the following raw material inner capacities 250cm that packs into
3Sealed plastic bottle in, with quick worker mixing 2-3 hour, obtain the printing ink composition.The printing ink that obtains is carried out following performance test.
Table 3 intaglio compound plastic film ink formulations
| Raw material | The chalk mass parts | Red black mass parts | Yellow black mass parts | Blue black mass parts | The tusche mass parts |
| Urethane resin | 66 | 54 | 54 | 54 | 54 |
[0082]?
| 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: used chlorine vinegar is the Japanese chlorine vinegar A of SHIN-ETSU HANTOTAI resin, is 20% solid content with the vinyl acetic monomer dilution
(1) the printing ink attachment fastness method of inspection:
Use the silk rod at the upper dope ink composition of surface treated polyester film (PET), making solids component is the thickness of 2-3um.After drying up with blower, paste the 3M adhesive tape at coated face, adhesive tape and the face that the is coated with direction that meets at right angles is peeled off rapidly, observe the coated face state.
Judgement criteria is: O: ink residue is more than 90%.
△: ink residue 50～90%
*: ink residue discontented 50%
(2) the ink colors method of inspection:
Label taking sample printing ink is a small amount of, drips in OPP film upper left side, materialses on a small quantity in the upper right side again, and both are adjacent and do not link to each other.China ink is scraped lamellar at the OPP film with the silk rod firmly from top to bottom.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:
With the printing ink temperature adjustment to room temperature (approximately 25 ℃).The printing ink of materialsing is poured 3# into and is examined in the grace cup, until printing ink with examine grace cup edge and flush till, scrape off bubble with glass stick.Test sample is required time when beginning to flow out to the interruption of sample stream silk and presenting first, is the viscosity of this printing ink.
(4) the printing ink combined strength bination method of inspection:
Use the silk rod at the upper dope ink composition of surface treated polyester film (PET), making solids component is the thickness of 2-3um.After drying up with blower, with silk rod coating polyurethane binder, spread is 2-2.5g/m3.It is compound that (tackiness agent adopts the YH2000S/YH10 of Beijing Gao Meng limited-liability company) then uses the OPP film of processing through surface treatment to carry out, in 50 ℃ of lower slaking 48h.Composite membrane is made the sample of wide 15mm, is measured the T stripping strength with the universal electronic drawing machine, and with this as combined strength bination.Numerical value is larger, and combined strength bination is higher.
(5) the printing ink antiblocking method of inspection:
Use the silk rod at the upper dope ink composition of surface treated polyester film (PET), making solids component is the thickness of 2-3um, fully dries up with blower.Coated face is overlapped with non-coated face, under temperature 50 C, apply the load of 2.0kgf/cm2.Peel off after 2 hours, observe its condition of surface.
Judgement criteria O: do not have adhesion when peeling off
△: adhesion is arranged when peeling off
*: printing ink shifts
(6) the printing ink solubility method of inspection:
Printing ink being coated on the sheet glass, making solids component reach the thickness of 2～3um, after depositing 30 seconds under the room temperature (approximately 25 ℃), is in the solvent of 1:1:1 with its weight ratio that is immersed in vinyl acetic monomer/n-propyl acetate/Virahol, observes the again solvability of ink film.
Judgement criteria O: the again dissolving of filming
*: film and do not dissolve and residue in sheet glass
(7) the ink stability method of inspection:
The printing ink that configures after depositing 30 days under the room temperature (approximately 25 ℃), is observed printing ink layering and precipitation situation.
Judgement criteria O: printing ink is without layering, without precipitation
△: printing ink has a small amount of precipitation without layering
*: the printing ink layering, or a large amount of precipitations are arranged
The performance test results is as shown in table 4:
Table 4 application performance test result
The combined strength bination test result is as shown in table 5:
Table 5. combined strength bination test result
Above-mentioned is to measure its quality index according to the State Standard of the People's Republic of China to utilizing the embodiment of the invention to make the method for inspection of the standby polyurethane ink of resin, and concrete reference standard is as follows:
Can find out from table 4, table 5 application testing result, it is good that the urethane resin that " the two still methods " that adopts among the present invention makes, the printing ink that gets with this resin have an attachment fastness, and color developing is good, combined strength bination is high, solubility, good stability, anti-ly returns the plurality of advantages such as sticking.
In sum, the binder resin that the preparation method of the embodiment of the invention makes as primary solvent take ester class and alcohols, can be used for gravure composite printing ink uses, have the various features such as safe, nontoxic, environmental protection, health, the printing ink fastness made from this resin is good, and color development is good, and combined strength bination is high, solubility, good stability, anti-return sticking, can be used as a without benzene without ketone printing ink binder.The method has overcome many shortcomings of above-mentioned " one still process " polyurethane system, adopted unique " two still methods " technological design, namely first in the first reactor, synthesize performed polymer, prepare in addition again a reactor, in this reactor, add amine chain extender and diluting solvent, then the performed polymer that makes in the first reactor slowly is added drop-wise to and carries out rear chain extension in the second reactor, by this processing method, guaranteed that the chain extension process is slowly gentle, resin viscosity slowly increases, the molecular resin amount narrow distribution that finally obtains.The synthetic molecular resin amount chain two ends of this method all are 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 printing ink fastness that the resin that obtains with this technique is made is good, and combined strength bination is high, and anti-after tack is good, is applicable to the gravure printing technique of using at the base material of wide region.
The above; only for the better embodiment of the present invention, but protection scope of the present invention is not limited to this, anyly is familiar with those skilled in the art in the technical scope that the present invention discloses; the variation 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 (10)
1. the preparation method of a gravure composite printing ink usefulness urethane resin is characterized in that, comprising:
The preparation polyester diol:
The diprotic acid of 48～56 mass parts, the dibasic alcohol of 44～52 mass parts are added in the polyester synthesis reactor, be warming up to 200～240 ℃, react and finished esterification in 5～6 hours; After finishing, esterification is cooled to 160 ℃, start vacuum pump, the polyester synthesis reactor is vacuumized, keep vacuum tightness at-0.094Mpa, took out 1～2 hour, keep afterwards vacuum tightness constant, with 5～8 hours with the still temperature rise to 210 of polyester synthesis reactor ℃～230 ℃, the cut total amount is emitted overhead product after theoretical value, finish polycondensation, the product that obtains is polyester diol;
Preparation end NCO base performed polymer:
After the vulcabond of the catalyzer of the polyether Glycols of the above-mentioned polyester diol that makes of 36～76 mass parts, 10～36 mass parts, 0.05～0.2 mass parts, 16～28 mass parts mixed, after reacting 2～4 hours under 50～120 ℃ of conditions, obtain having following structure end NCO base performed polymer: OCN-B-(NH-CO-O-R
1-O-CO-NH-)
m-B-NCO; Wherein, R
1Be methyl, methylene radical, ester group or aryl radical group, B is methyl, methylene radical, aryl radical or alicyclic hydrocarbon radical group;
Chain extension is synthetic:
In another container, add the amine chain extender (c) of 0.7～1.4 mass parts, the ester class (d) of 46～56 mass parts, alcoholic solvent (e) the formation mixing solutions of 14～24 mass parts, the above-mentioned described end NCO base performed polymer that makes of 28～30 mass parts put into 5～50 minutes carry out chain extending reaction in the described mixing solutions, temperature of reaction is 30～50 ℃, react the urethane resin that namely obtains having following structure after 2～4 hours and be the gravure composite printing ink urethane resin, the structure of this urethane resin is: NH
2-R
2-NH-(CO-NH-R
1-NH-CO-)
n-NH-R
2-NH
2Wherein, R
2Be methyl, methylene radical, aryl radical or alicyclic hydrocarbon radical group.
2. method according to claim 1, it is characterized in that, described preparation polyester diol also comprises: after finishing esterification, confirm whether qualified step of esterification by the acid number of measuring reactant, if the Suan Zhi＜=20mgKOH/g of reactant confirms that then esterification is qualified.
3. method according to claim 1, it is characterized in that, described preparation polyester diol also comprises: after polycondensation is finished, confirm whether qualified step of polycondensation by the test polycondensation product, reach 53 ± 3mgKOH/g and acid number＜1.0mgKOH/g if measure the hydroxyl value that obtains sample from described polycondensation product, it is qualified then to confirm as the polycondensation product of polyester diol.
4. according to claim 1 to 3 each described methods, it is characterized in that, the diprotic acid that described preparation polyester diol adopts is selected from: any in the ester formative derivative of aliphatic dicarboxylic acid, aromatic dicarboxylic acid, aliphatic dicarboxylic acid, the ester formative derivative of aromatic dicarboxylic acid or any two kinds;
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, have any and any two kinds mixture in the low-molecular-weight diol class of ring structure at 5 pentanediols, 2-methyl 1,3-PD.
5. each described method according to claim 4 is characterized in that, described aliphatic dicarboxylic acid is selected from: any in Succinic Acid, sebacic acid, hexanodioic acid, nonane diacid, the pentanedioic acid;
Described aromatic dicarboxylic acid is selected from: any in terephthalic acid, m-phthalic acid, the phthalic acid;
Described low-molecular-weight diol class with ring structure is selected from the ethylene oxide adduct of cyclohexyl 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 the reaction, measure in the reaction product-mass content of NCO confirms whether qualified step of reaction product, if in the reaction product that measures-the quality percentage composition of NCO is 1.0～4.5%, confirms that then the reaction product that makes as end NCO base performed polymer is qualified.
7. according to claim 1,6 or 7 described methods, it is characterized in that, the polyether Glycols that described preparation end NCO base performed polymer adopts is selected from: polyoxypropyleneglycol, the number-average molecular weight that number-average molecular weight is 1000 polyoxypropyleneglycol, number-average molecular weight is M2000 is that 3000 polyoxypropyleneglycol, number-average molecular weight are that 1000 polytetramethylene ether diol, number-average molecular weight are that 2000 polytetramethylene ether diol, number-average molecular weight are any in 3000 the polytetramethylene ether diol;
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 diisocyanate, the tetramethylxylylene diisocyanate any 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 in the tetrabutyl titanate.
8. method according to claim 1, it is characterized in that, described chain extension is synthetic also to be comprised: the step that the gravure composite printing ink that obtains is tested with urethane resin, if the gravure composite printing ink that test obtains is 800 ± 400mpa.s with 25 ℃ of rotary viscosities of urethane resin, solid content is 28～32%, and it is qualified to be.
9. method according to claim 1 is characterized in that, the amine chain extender that adopts during described chain extension is synthetic is selected from: have in the aliphatics of primary amine groups or secondary amino group, alicyclic, aromatic series or the heterocyclic diamine any or several arbitrarily;
The esters solvent that adopts during described chain extension is synthetic is selected from: any in vinyl acetic monomer, n-propyl acetate, the n-butyl acetate or any several mixture;
The alcoholic solvent that adopts during described chain extension is synthetic is selected from: any in ethanol, n-propyl alcohol, Virahol, propyl carbinol, the methyl alcohol or several arbitrarily.
10. method according to claim 9, it is characterized in that, the amine chain extender that adopts during described chain extension is synthetic is selected from: different fluorine that ketone diamines, quadrol, 1,6-hexanediamine, 1,4-butanediamine, new pentamethylene diamine, 4, in 4'-diamino-dicyclohexyl methane, Isosorbide-5-Nitrae-tetrahydrobenzene diamines, the m-xylene diamine any or several arbitrarily.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310014391.8A CN103012724B (en) | 2013-01-15 | 2013-01-15 | Preparation method of polyurethane resin for gravure composite ink |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310014391.8A CN103012724B (en) | 2013-01-15 | 2013-01-15 | Preparation method of polyurethane resin for gravure composite ink |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103012724A true CN103012724A (en) | 2013-04-03 |
| CN103012724B CN103012724B (en) | 2015-02-25 |
Family
ID=47961866
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310014391.8A Active CN103012724B (en) | 2013-01-15 | 2013-01-15 | Preparation method of polyurethane resin for gravure composite ink |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103012724B (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| CN105705595A (en) * | 2013-11-11 | 2016-06-22 | 日立化成株式会社 | Binder for printing ink, laminate ink composition for soft packaging, and printed article |
| 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 |
| 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 |
| US9688813B2 (en) | 2014-11-10 | 2017-06-27 | Industrial Technology Research Institute | Thermoplastic polyester elastomer and method for manufacturing the same |
| CN110546205A (en) * | 2017-04-26 | 2019-12-06 | 大日精化工业株式会社 | Bio-polyurethane resin, bio-polyurethane resin solution, and printing 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 |
| CN110818881A (en) * | 2019-11-22 | 2020-02-21 | 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 |
| 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 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 resin for low-cost 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 |
-
2013
- 2013-01-15 CN CN201310014391.8A patent/CN103012724B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 resin for low-cost 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 |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105705595B (en) * | 2013-11-11 | 2018-07-31 | 日立化成株式会社 | Adhesive for printing ink, flexible package laminating inks composition and printed article |
| CN105705595A (en) * | 2013-11-11 | 2016-06-22 | 日立化成株式会社 | Binder for printing ink, laminate ink composition for soft packaging, and printed article |
| 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 |
| US9688813B2 (en) | 2014-11-10 | 2017-06-27 | Industrial Technology Research Institute | 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 |
| CN110546205A (en) * | 2017-04-26 | 2019-12-06 | 大日精化工业株式会社 | Bio-polyurethane resin, bio-polyurethane resin solution, and printing ink |
| CN110546205B (en) * | 2017-04-26 | 2021-11-16 | 大日精化工业株式会社 | Bio-polyurethane resin, bio-polyurethane resin solution, and printing ink |
| CN110818881A (en) * | 2019-11-22 | 2020-02-21 | 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 |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103012724B (en) | 2015-02-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103012724B (en) | Preparation method of polyurethane resin for gravure composite ink | |
| CN105062403B (en) | Synthetic leather adhesive and preparation method | |
| US5300326A (en) | Method of coating a plastic substrate with an aqueous coating composition for plastic substrates | |
| CN108864807B (en) | Binder for printing ink, application thereof, and printed matter | |
| RU2256671C2 (en) | Polyurethane resin and a method for preparation thereof, coating composition containing polyurethane resin, and use of polyurethane resin for printing on plastic substances | |
| KR102231319B1 (en) | Lamination printing ink comprising an aqueous dispersion comprising polyurethane | |
| CN104861139A (en) | Preparation method of high-temperature steam endurance polyurethane resin for ink | |
| CN101238159A (en) | Solvent borne polyurethane composition | |
| CN101868507A (en) | Polyurethane resins for nitrocellulose inks | |
| CN103910849B (en) | The preparation method of adhesive for table printing ink | |
| CN108276761A (en) | Solvent-free leather polyurethane resin and preparation method and application | |
| CN110845685B (en) | Polyaspartic acid ester and polyurea-based repairing material for repairing polyurethane foam of automobile instrument panel, and preparation method and repairing method thereof | |
| AU2004275943B2 (en) | Two-component composition for producing polyurethane gel coats for epoxy-resin and vinyl-ester resin composite materials | |
| JP2013227465A (en) | Polyurethane resin composition for printing ink binder | |
| CN104592476A (en) | Method for preparing polyurethane binder for flexible printing composite ink | |
| CN109705304A (en) | A kind of preparation method of aqueous intaglio printing ink polyurethane binder | |
| CN110358047B (en) | Waterborne polyurethane coating for environment-friendly temperature-resistant transfer coating and preparation method thereof | |
| JP4074928B2 (en) | Printing ink composition for laminating and laminated product using the same. | |
| KR102374579B1 (en) | Ink composition for aqueous flexographic printing and process for preparing the same | |
| JP4061631B2 (en) | Non-aqueous primer composition | |
| JPH05171091A (en) | Aqueous polyurethane resin, its production, and its use | |
| AU2004255320A1 (en) | A polyurethane resin for color inks | |
| TW201910371A (en) | Sulfonic acid based aqueous polyurethane emulsion and process of producing the same | |
| JP3895035B2 (en) | Water-based printing ink composition | |
| CN108178977A (en) | A kind of aqueous OPP aluminizers back-coating and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |