CN103173185B - Preparation method of waterborne polyurethane adhesive for card matrix material - Google Patents
Preparation method of waterborne polyurethane adhesive for card matrix material Download PDFInfo
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Abstract
The invention provides a preparation method of waterborne polyurethane adhesive for a card matrix material, and belongs to the technical field of high polymer materials. The method comprises the following preparation steps of: carrying out polymerization reaction on mixed binary isocyanate formed by isophorone diisocyanate and dicyclohexyl methane-4,4-diisocyanate and polyhydric alcohol of taking polyester diol as a primary material and polyether glycol as an auxiliary material; adding proper hydroxyl acrylate to a reaction system, and preparing a polyurethane prepolymer by virtue of a chain extender; neutralizing by use of triethylamine, and adding water to emulsify in a high-speed disperser, so as to obtain a waterborne polyurethane dispersing body; adding ethanediamine to carry out chain extension again, and finally mixing with assistants such as a defoamer, a thickener, anti-adhesive and an ultraviolet light absorber to obtain the waterborne polyurethane adhesive for the card matrix material. The preparation method has the characteristics of being low in preparation cost, strong in adhesion and the like, is simple in production technology and can be used for easily coating products; the solid content can achieve 40%; and the coated film with glue is especially suitable for coating various color cards.
Description
Technical field
The present invention relates to a kind of preparation method who blocks base material coating use polyurethane adhesives, belong to technical field of polymer materials.
Background technology
Along with advancing by leaps and bounds of expanding economy and computer technology and digital printing technology, modern card manufacturing technology, as an emerging independent educational project, has obtained rapid raising.Because card application is extremely extensive, and of a great variety, quantity is surprising, has driven the development of card base material coating with tamanori.The initial all kinds of tamanoris that use all be take solvent borne polyurethane as main, but organic solvent is inflammable, explosive, smell is large, volatile, easily cause atmospheric pollution while using, and there is certain toxicity.Because the pressure from public opinion of protection of the environment and people's environmental consciousness constantly strengthen, many countries have formulated the laws and regulations of restriction volatile organic compound (VOC) in recent years, and these factors have promoted the development of aqueous polyurethane.Except thering are some identical character with solvent borne polyurethane, that aqueous polyurethane also has is nonflammable, smell is little, processing free from environmental pollution, energy-conservation, easy to operate and modification, VOC content are low, can be deployed into not containing or the advantage such as few solvent-laden coating and tackiness agent, be subject to people's attention.
Although card base material coating aqueous polyurethane has been obtained a large amount of achievements, for the rear functional derived product obtaining of coating, it is explored with research and still needs to be developed.The wetting ability of the hydrophobic card matrix material of aqueous polyurethane effects on surface is poor, has introduced after hydrophilic group, and its water resistance can decline again to some extent; Other some performances, as the functions such as resistance to settling, tear-resistant intensity, tensile strength, wear resistance are still necessary to improve.The card series products of institute's overlay film after card matrix material coating, its surface has the ink color pigment of more complicated, and this is very high to the requirement with laminate product quality.Universal aqueous polyurethane is applied to this coating and has many deficiencies, as water-fast, heat-resisting, ageing-resistant performance is poor.Especially product, to the CMYK class colour atla hot pressing stripping strength after hydrothermal aging again, enjoys the producer and user's concern.
Card base material is coated with the waterborne polyurethane adhesive product of use at present, and after overlay film, the stripping strength of colour atla is difficult to maintain hydrothermal aging numerical value, for the anti-fake mark of colour atla printing, mostly shows as UV test fuzzy, can not realize the re-set target that product will reach.And adopt multiple isocyanic ester, polyvalent alcohol and appropriate hydroxy acrylate coordinate system Preparation Method, and can improve the multinomial technical indicator of card base material band glued membrane overlay film colour atla, this kind of technique rarely has report.
Summary of the invention
The object of the invention is in order to overcome the shortcomings such as the existing hydrothermal aging of overlay film colour atla after the coating of current card base material aqueous polyurethane, UV test are fuzzy, a kind of new aqueous polyurethane preparation method is provided, and this method can be improved the deficiency that card base material band glued membrane faces in colour atla overlay film to a certain extent.
The present invention realizes by following technical solution: a kind of preparation method who blocks base material coating use polyurethane adhesives, comprises the steps:
(1) polyurethane preformed polymer
The melting mixing in 80～85 ℃ by polyester glycol and polyether glycol, form molten mixture, described polyester glycol is poly adipate succinic acid ester and poly-hexanodioic acid hexylene glycol ester, polyether glycol is polytetrahydrofuran diol, three's mass ratio is followed successively by 1:0.2～0.3: 0.2～0.3, and the mixed molecular-weight average of three is 2000～3000, then vacuum-drying is 1～2 hour, be cooled to 50～60 ℃, add mixing vulcabond, form raw mixture, the amount of described mixing vulcabond is 55～60% of melting mixing amount, mixing vulcabond is isophorone diisocyanate and dicyclohexyl methyl hydride-4, 4-vulcabond, its mass ratio is 1:0.1～0.2, then be progressively warming up to 80～90 ℃, react after 1.5～2 hours, be cooled to 40～50 ℃, add organic bismuth catalyst, hydrophilic chain extender, linking agent and with the acrylate of hydroxyl, the amount of described organic bismuth catalyst is 0.02～0.04% of raw mixture quality, progressively be warming up to 60～65 ℃, then add the acetone that accounts for raw mixture quality 25～35%, react 4～5 hours, make polyurethane prepolymer,
Organic bismuth catalyst is bismuth zinc composite catalyst; Hydrophilic chain extender is dimethylolpropionic acid, accounts for 4.0～5.0% of raw mixture quality; Linking agent is BDO and TriMethylolPropane(TMP), and the two accounts for respectively 2.0～4.0% and 0.8～1.0% of raw mixture quality; Acrylate with hydroxyl is methacrylic acid-beta-hydroxy ethyl ester, accounts for 2.0～4.0% of raw mixture quality.
(2) neutralization reaction
Above-mentioned polyurethane prepolymer is cooled to 20～25 ℃, add neutralizing agent to carry out neutralization reaction, to add the hydrophilic chain extender mass ratio adding in neutralizing agent and step (1) be 1:2.0～2.5, react 15～20 minutes, make in carboxyl structure wherein and salify, neutralizing agent is triethylamine.
(3) prepare aqueous polyurethane dispersion
Polyurethane prepolymer after above-mentioned neutralization is transferred in high speed dispersor, and the shearing rotating speed that dispersion machine is set is 3500～4000r/min, evenly spread in deionized water to polyurethane prepolymer, the mass ratio of raw mixture and deionized water is 1.1～1.3, obtains aqueous polyurethane dispersion.
(4) prepare aqueous polyurethane
Speed dropping diamine compound with 0.055～0.133g/min in the above-mentioned aqueous polyurethane dispersion making carries out chain extending reaction, to add the quality of diamine compound be 1:24～35 with the mass ratio that mixes vulcabond in raw material, reaction times continues 15～20 minutes, makes aqueous polyurethane.Diamine compound is quadrol, carries out chain extending reaction at 20～25 ℃.
(5) preparation of waterborne polyurethane adhesive
By above-mentioned aqueous polyurethane with defoamer, thickening material, anti-stick, flow agent and ultraviolet radiation absorption agent aid in mass ratio for the ratio of 100:1.0～1.5:1～3:0.5～1:0.5～1:0.2～0.5 mixes, make waterborne polyurethane adhesive.
Described defoamer is polyoxyethylene pentaerythritol ether or polypropylene glycerol aether;
Described thickening material is any one of Vltra tears, Xylo-Mucine and Natvosol;
Described anti-stick is polydimethylsiloxane;
Described flow agent is BYK-300 or BYK-306;
Described UV light absorber is 2,2-dihydroxyl-4-methoxy benzophenone.
The raw material sources that the present invention selects are as follows:
Poly adipate succinic acid ester: (PBA3000) technical grade Qingdao Yu Tian Chemical Co., Ltd.
Poly-hexanodioic acid hexylene glycol ester: (PHA2000) technical grade Anhui Amway synthetic leather company limited
Polytetrahydrofuran diol: (PTMG2000) technical grade Mitsubishi KCC
Isophorone diisocyanate: (IPDI) technical grade Beyer Co., Ltd
Dicyclohexyl methyl hydride-4,4-vulcabond: (HMDI) technical grade Yantai Wanhua Polyurethane Co., Ltd
Bismuth zinc composite catalyst: the leading chemical company of the analytical pure U.S.
Dimethylolpropionic acid: (DMBA) technical grade NCM
BDO: (Isosorbide-5-Nitrae-BG) analytical pure Chemical Reagent Co., Ltd., Sinopharm Group
TriMethylolPropane(TMP): (TMP) analytical pure Tianjin Bo Di Chemical Co., Ltd.
Methacrylic acid-beta-hydroxy ethyl ester: (HEMA) analytical pure Tianjin City Chemical Agent Research Institute
Acetone: ammonia ester level Shanghai Zhen Qi chemical reagent company limited
Triethylamine: (TEA) analytical pure Shanghai traditional Chinese medicines group
Quadrol: (EDA) analytical pure Shanghai traditional Chinese medicines group
Polyoxyethylene pentaerythritol ether: technical grade Wuhan large magnificent great achievement medication chemistry company limited
Polypropylene glycerol aether: Chemical Co., Ltd. is closed in Xinyi, technical grade Hubei
Vltra tears: technical grade Hebei Xingtai Mierocrystalline cellulose company limited
Natvosol: technical grade Hebei Xingtai Mierocrystalline cellulose company limited
Xylo-Mucine: technical grade Shanghai Nai Jin Industrial Co., Ltd.
Polydimethylsiloxane: technical grade Shandong Xin Jie green technology company limited
BYK-300: technical grade Germany Bi Ke chemical company
BYK-306: technical grade Germany Bi Ke chemical company
2,2-dihydroxyl-4-methoxy benzophenone: Xinda, Dezhou, technical grade Shandong Chemical Co., Ltd..
the present invention compared with prior art, has following beneficial effect:
1, adopt two kinds of different alicyclic diisocyanates to mix synergy, than aromatic diisocyanate, have more the advantages such as hydrolysis, resistance to xanthochromia, excellent performance, product stock be stable, and symmetrical vulcabond can produce the orderly block copolymer of compound with regular structure, thereby make product there is higher modulus and tear strength, be more suitable for the band glued membrane coating of card matrix material.
2, two kinds contain polyester glycol and the polytetrahydrofuran diol mixing use that gathers hexanodioic acid, not only brought into play that polyether glycol intensity is large, good toughness, have outside higher good solubility-resistence effect, also embody poly-hexanodioic acid kind polyester glycol and prepare water-base polyurethane material good elasticity and bond performance.
3, appropriate Hydroxylated acrylic resin has been given prominence to the mechanical property of aqueous polyurethane product, has strengthened the sticking power of overlay film, has improved the solid content of product, makes product have good tack, bonding comprehensive and chemical-resistant.
4, hydrophilic chain extender changes dimethylolpropionic acid into by conventional dimethylol propionic acid, has reduced fusing point, has avoided the use of nitrogen methyl-2-pyrrolidone noxious solvent.The organo-bismuth that catalyzer is used, not only, than traditional organic tin catalyzer environmental protection more, its induction time is shorter, and the finished product mechanical property of making is better.
Embodiment
Below in conjunction with embodiment, further explain the present invention, but embodiment does not limit in any form to the present invention.
embodiment 1
50g poly adipate succinic acid ester, the poly-hexanodioic acid hexylene glycol ester of 10g and 10g polytetrahydrofuran diol are joined in the four-hole boiling flask of 500ml, be placed on the interior melting mixing of vacuum drying oven of 80 ℃, and dewater 1 hour, be then cooled to 50 ℃ and shift out loft drier.Under drying nitrogen protection, by 35g isophorone diisocyanate and 3.5g dicyclohexyl methyl hydride-4, the mixture of 4-vulcabond joins in above-mentioned four-hole boiling flask, is then progressively warming up to 80 ℃.React after 1.5 hours, be cooled to 40 ℃, add bismuth zinc composite catalyst 0.0217g, hydrophilic chain extender dimethylolpropionic acid 4.34g, linking agent 1,4-butyleneglycol 2.17g, TriMethylolPropane(TMP) 0.868g, methacrylic acid-beta-hydroxy ethyl ester 2.17g, is progressively warming up to 60 ℃, then add 27.125g acetone, sustained reaction 4 hours.Be cooled to 20 ℃, add triethylamine 1.736g to neutralize, reaction continues 15min, polyurethane prepolymer after neutralization is transferred in high speed dispersor, and the shearing rotating speed that dispersion machine is set is 3500r/min, in dispersion machine, add deionized water 119.35g, stir 15min and evenly spread in deionized water to polyurethane prepolymer.Finally slowly add chainextender quadrol 1.1g to carry out secondary chain extension and continue 15min, dripping the rate-controlling of diamine between 0.055～0.133g/min, obtaining aqueous polyurethane emulsion 261.5g.In resulting aqueous polyurethane emulsion, add 2.615g polyoxyethylene pentaerythritol ether, 2.615g Vltra tears, 1.3075g polydimethylsiloxane, 1.3075g BYK-300 and 0.523g 2,2-dihydroxyl-4-methoxy benzophenone mixes, and makes card base material coating use polyurethane adhesives.
the evaluation of embodiment 1 product and the detection of the impact of performance
The tamanori analytical test leading indicator that table 1 makes for this embodiment
| Product | Probe temperature (℃) | Testing humidity (%) | Viscosity (mpa.s) | Solid content (%) | PH value |
| Index | 22 | 30 | 16.9 | 40 | 7.5 |
The prepared card base material coating of embodiment use polyurethane adhesives carries out hardened coating to PVC facial mask, and resulting band glued membrane carries out coverlay film lamination to CMYK colour atla, and it is 130 ℃ that laminating temperature is set, and lamination pressure is 3MPa, and the lamination time is 18min.Coverlay film lamination colour atla carries out the peel strength test comparison of aging front and back, and it is 95% that ageing oven humidity is set, and temperature is 50 ℃, and the time is 72 hours.Stripping strength (T-shaped) testing method: measure according to GB/T 14916-2006 adopting by equation ISO/IEC 7810:2003.The anti-fake mark of coverlay film lamination colour atla adopts ultraviolet ray to carry out UV test.Result is relatively as table 2:
The salient features of table 2 coverlay film lamination CMYK colour atla
| Coverlay film lamination colour atla | Aging front stripping strength | Aging rear stripping strength | UV test |
| Red card | 9.9N/CM | 8.3N/CM | Clear |
| Cyan card | 9.2N/CM | 8.0N/CM | Clear |
| Yellow card | 11.3N/CM | 10.1N/CM | Clear |
| Black card | 8.7N/CM | 7.5N/CM | Clear |
embodiment 2
50g poly adipate succinic acid ester, the poly-hexanodioic acid hexylene glycol ester of 15g and 15g polytetrahydrofuran diol are joined in the four-hole boiling flask of 500ml, be placed on the interior melting mixing of vacuum drying oven of 85 ℃, and dewater 2 hours, be then cooled to 60 ℃ and shift out loft drier.Under drying nitrogen protection, by 40g isophorone diisocyanate and 8g dicyclohexyl methyl hydride-4, the mixture of 4-vulcabond joins in above-mentioned four-hole boiling flask, is then progressively warming up to 90 ℃.React after 2 hours, be cooled to 50 ℃, add bismuth zinc composite catalyst 0.0512g, hydrophilic chain extender dimethylolpropionic acid 6.4g, linking agent 1,4-butyleneglycol 5.12g, TriMethylolPropane(TMP) 1.28g, methacrylic acid-beta-hydroxy ethyl ester 5.12g, is progressively warming up to 65 ℃, then add 44.8g acetone, sustained reaction 5 hours.Be cooled to 25 ℃, add triethylamine 3.2g to neutralize, reaction continues 20min, polyurethane prepolymer after neutralization is transferred in high speed dispersor, and the shearing rotating speed that dispersion machine is set is 4000r/min, in dispersion machine, add deionized water 166.4g, stir 15min and evenly spread in deionized water to polyurethane prepolymer.Finally slowly add chainextender quadrol 2.0g to carry out secondary chain extension and continue 20min, dripping the rate-controlling of diamine between 0.055～0.133g/min, obtaining aqueous polyurethane emulsion 350.8g.In resulting aqueous polyurethane emulsion, add 5.262g polypropylene glycerol aether, 10.524 Natvosols, 3.508g polydimethylsiloxane, 3.508g BYK-306 and 1.754g 2,2-dihydroxyl-4-methoxy benzophenone mixes, and makes card base material coating use polyurethane adhesives.
the evaluation of embodiment 2 products and the detection of the impact of performance
The tamanori analytical test leading indicator that table 3 makes for this embodiment
| Product | Probe temperature (℃) | Testing humidity (%) | Viscosity (mpa.s) | Solid content (%) | PH value |
| Index | 21 | 33 | 18.2 | 42 | 7.4 |
The coverlay film lamination colour atla salient features testing method of embodiment 2 is with embodiment 1, and result is relatively as table 4:
The salient features of table 4 coverlay film lamination CMYK colour atla
| Coverlay film lamination colour atla | Aging front stripping strength | Aging rear stripping strength | UV test |
| Red card | 9.6N/CM | 8.0N/CM | Clear |
| Cyan card | 9.8N/CM | 9.1N/CM | Clear |
| Yellow card | 10.2N/CM | 9.9N/CM | Clear |
| Black card | 8.1N/CM | 7.7N/CM | Clear |
embodiment 3
50g poly adipate succinic acid ester, the poly-hexanodioic acid hexylene glycol ester of 10g and 15g polytetrahydrofuran diol are joined in the four-hole boiling flask of 500ml, be placed on the interior melting mixing of vacuum drying oven of 85 ℃, and dewater 1 hour, be then cooled to 60 ℃ and shift out loft drier.Under drying nitrogen protection, by 37.5g isophorone diisocyanate and 7.5g dicyclohexyl methyl hydride-4, the mixture of 4-vulcabond joins in above-mentioned four-hole boiling flask, is then progressively warming up to 80 ℃.React after 1.5 hours, be cooled to 40 ℃, add bismuth zinc composite catalyst 0.048g, hydrophilic chain extender dimethylolpropionic acid 6.0g, linking agent 1,4-butyleneglycol 4.8g, TriMethylolPropane(TMP) 1.2g, methacrylic acid-beta-hydroxy ethyl ester 4.8g, is progressively warming up to 60 ℃, then add 31.25 acetone, sustained reaction 5 hours.Be cooled to 20 ℃, add triethylamine 2.4g to neutralize, reaction continues 20min, polyurethane prepolymer after neutralization is transferred in high speed dispersor, and the shearing rotating speed that dispersion machine is set is 3500r/min, in dispersion machine, add deionized water 132g, stir 15min and evenly spread in deionized water to polyurethane prepolymer.Finally slowly add chainextender quadrol 1.875g to carry out secondary chain extension and continue 15min, dripping the rate-controlling of diamine between 0.055～0.133g/min, obtaining aqueous polyurethane emulsion 293.8g.In resulting aqueous polyurethane emulsion, add 2.938g polyoxyethylene pentaerythritol ether, 8.814g Vltra tears, 2.938g polydimethylsiloxane, 1.469g BYK-300 and 1.469g 2,2-dihydroxyl-4-methoxy benzophenone mixes, and makes card base material coating use polyurethane adhesives.
the evaluation of embodiment 3 products and the detection of the impact of performance
The tamanori analytical test leading indicator that table 5 makes for this embodiment
| Product | Probe temperature (℃) | Testing humidity (%) | Viscosity (mpa.s) | Solid content (%) | PH value |
| Index | 23 | 32 | 17.6 | 41 | 7.6 |
The coverlay film lamination colour atla salient features testing method of embodiment 3 is with embodiment 1, and result is relatively as table 6:
The salient features of table 6 coverlay film lamination CMYK colour atla
| Coverlay film lamination colour atla | Aging front stripping strength | Aging rear stripping strength | UV test |
| Red card | 9.2N/CM | 8.1N/CM | Clear |
| Cyan card | 9.5N/CM | 8.9N/CM | Clear |
| Yellow card | 9.7N/CM | 8.3N/CM | Clear |
| Black card | 8.5N/CM | 7.2N/CM | Clear |
embodiment 4
50g poly adipate succinic acid ester, the poly-hexanodioic acid hexylene glycol ester of 15g and 10g polytetrahydrofuran diol are joined in the four-hole boiling flask of 500ml, be placed on the interior melting mixing of vacuum drying oven of 80 ℃, and dewater 2 hours, be then cooled to 60 ℃ and shift out loft drier.Under drying nitrogen protection, by 37.5g isophorone diisocyanate and 3.75g dicyclohexyl methyl hydride-4, the mixture of 4-vulcabond joins in above-mentioned four-hole boiling flask, is then progressively warming up to 90 ℃.React after 2 hours, be cooled to 50 ℃, add bismuth zinc composite catalyst 0.02325g, hydrophilic chain extender dimethylolpropionic acid 4.65g, linking agent 1,4-butyleneglycol 4.65g, TriMethylolPropane(TMP) 1.1625g, methacrylic acid-beta-hydroxy ethyl ester 2.325g, is progressively warming up to 60 ℃, then add 29.0625g acetone, sustained reaction 4 hours.Be cooled to 25 ℃, add triethylamine 1.86g to neutralize, reaction continues 15min, polyurethane prepolymer after neutralization is transferred in high speed dispersor, and the shearing rotating speed that dispersion machine is set is 4000r/min, in dispersion machine, add deionized water 127.875g, stir 15min and evenly spread in deionized water to polyurethane prepolymer.Finally slowly add chainextender quadrol 1.71g to carry out secondary chain extension and continue 20min, dripping the rate-controlling of diamine between 0.055～0.133g/min, obtaining aqueous polyurethane emulsion 283.2g.In resulting aqueous polyurethane emulsion, add 4.248g polypropylene glycerol aether, 2.832 Natvosols, 1.416g polydimethylsiloxane, 2.832g BYK-306 and 0.5664g 2,2-dihydroxyl-4-methoxy benzophenone mixes, and makes card base material coating use polyurethane adhesives.
the evaluation of embodiment 4 products and the detection of the impact of performance
The tamanori analytical test leading indicator that table 7 makes for this embodiment
| Product | Probe temperature (℃) | Testing humidity (%) | Viscosity (mpa.s) | Solid content (%) | PH value |
| Index | 22 | 32 | 17.1 | 40 | 7.4 |
The coverlay film lamination colour atla salient features testing method of embodiment 4 is with embodiment 1, and result is relatively as table 8:
The salient features of table 8 coverlay film lamination CMYK colour atla
| Coverlay film lamination colour atla | Aging front stripping strength | Aging rear stripping strength | UV test |
| Red card | 9.7N/CM | 8.2N/CM | Clear |
| Cyan card | 9.6N/CM | 8.8N/CM | Clear |
| Yellow card | 11.1N/CM | 9.8N/CM | Clear |
| Black card | 8.3N/CM | 7.8N/CM | Clear |
embodiment 5
50g poly adipate succinic acid ester, the poly-hexanodioic acid hexylene glycol ester of 12g and 13g polytetrahydrofuran diol are joined in the four-hole boiling flask of 500ml, be placed on the interior melting mixing of vacuum drying oven of 82 ℃, and dewater 1.5 hours, be then cooled to 55 ℃ and shift out loft drier.Under drying nitrogen protection, by 36g isophorone diisocyanate and 6g dicyclohexyl methyl hydride-4, the mixture of 4-vulcabond joins in above-mentioned four-hole boiling flask, is then progressively warming up to 85 ℃.React after 2 hours, be cooled to 45 ℃, add bismuth zinc composite catalyst 0.035g, hydrophilic chain extender dimethylolpropionic acid 4.7g, linking agent 1,4-butyleneglycol 3.8g, TriMethylolPropane(TMP) 1.0g, methacrylic acid-beta-hydroxy ethyl ester 3.6g, is progressively warming up to 60 ℃, then add 35g acetone, sustained reaction 4.5 hours.Be cooled to 20 ℃, add triethylamine 2.0g to neutralize, reaction continues 15min, polyurethane prepolymer after neutralization is transferred in high speed dispersor, and the shearing rotating speed that dispersion machine is set is 3800r/min, in dispersion machine, add deionized water 130g, stir 15min and evenly spread in deionized water to polyurethane prepolymer.Finally slowly add chainextender quadrol 1.5g to carry out secondary chain extension and continue 18min, dripping the rate-controlling of diamine between 0.055～0.133g/min, obtaining aqueous polyurethane emulsion 290.8g.In resulting aqueous polyurethane emulsion, add 3.49g polypropylene glycerol aether, 5.8 Xylo-Mucines, 2.1g polydimethylsiloxane, 2.2g BYK-306 and 0.89g 2,2-dihydroxyl-4-methoxy benzophenone mixes, and makes card base material coating use polyurethane adhesives.
the evaluation of embodiment 5 products and the detection of the impact of performance
The tamanori analytical test leading indicator that table 9 makes for this embodiment
| Product | Probe temperature (℃) | Testing humidity (%) | Viscosity (mpa.s) | Solid content (%) | PH value |
| Index | 22 | 31 | 17.9 | 41 | 7.5 |
The coverlay film lamination colour atla salient features testing method of embodiment 5 is with embodiment 1, and result is relatively as table 10:
The salient features of table 10 coverlay film lamination CMYK colour atla
| Coverlay film lamination colour atla | Aging front stripping strength | Aging rear stripping strength | UV test |
| Red card | 9.0N/CM | 7.9N/CM | Clear |
| Cyan card | 9.7N/CM | 8.5N/CM | Clear |
| Yellow card | 10.8N/CM | 9.2N/CM | Clear |
| Black card | 8.6N/CM | 7.2N/CM | Clear |
Claims (7)
1. a preparation method who blocks base material coating use polyurethane adhesives, is characterized in that comprising the steps:
(1) polyurethane preformed polymer
The melting mixing in 80～85 ℃ by polyester glycol and polyether glycol, form molten mixture, described polyester glycol is poly adipate succinic acid ester and poly-hexanodioic acid hexylene glycol ester, polyether glycol is polytetrahydrofuran diol, three's mass ratio is followed successively by 1:0.2～0.3: 0.2～0.3, and the mixed molecular-weight average of three is 2000～3000, then vacuum-drying is 1～2 hour, be cooled to 50～60 ℃, add mixing vulcabond, form raw mixture, the amount of described mixing vulcabond is 55～60% of melting mixing amount, mixing vulcabond is isophorone diisocyanate and dicyclohexyl methyl hydride-4, 4-vulcabond, its mass ratio is 1:0.1～0.2, then be progressively warming up to 80～90 ℃, react after 1.5～2 hours, be cooled to 40～50 ℃, add organic bismuth catalyst, hydrophilic chain extender, linking agent and with the acrylate of hydroxyl, the amount of described organic bismuth catalyst is 0.02～0.04% of raw mixture quality, progressively be warming up to 60～65 ℃, then add the acetone that accounts for raw mixture quality 25～35%, react 4～5 hours, make polyurethane prepolymer,
(2) neutralization reaction
Above-mentioned polyurethane prepolymer is cooled to 20～25 ℃, adds neutralizing agent to carry out neutralization reaction, the mass ratio of the hydrophilic chain extender adding in the neutralizing agent adding and step (1) is 1:2.0～2.5, reacts 15～20 minutes;
(3) prepare aqueous polyurethane dispersion
Polyurethane prepolymer after neutralization is transferred in high speed dispersor, and the shearing rotating speed that dispersion machine is set is 3500～4000r/min, evenly spread in deionized water to polyurethane prepolymer, the mass ratio of raw mixture and deionized water is 1.1～1.3, obtains aqueous polyurethane dispersion;
(4) prepare aqueous polyurethane
Speed dropping diamine compound with 0.055～0.133g/min in the above-mentioned aqueous polyurethane dispersion making carries out chain extending reaction, to add diamine compound be 1:24～35 with the mass ratio that mixes vulcabond in step (1), reaction times continues 15～20 minutes, makes aqueous polyurethane; Described diamine compound is quadrol, carries out chain extending reaction at 20～25 ℃;
(5) preparation of waterborne polyurethane adhesive
By the aqueous polyurethane making with defoamer, thickening material, anti-stick, flow agent and UV light absorber in mass ratio for the ratio of 100:1.0～1.5:1～3:0.5～1:0.5～1:0.2～0.5 mixes, make waterborne polyurethane adhesive.
2. preparation method as claimed in claim 1, is characterized in that: in step (1), organic bismuth catalyst is bismuth zinc composite catalyst.
3. preparation method as claimed in claim 1, is characterized in that: in step (1), hydrophilic chain extender is dimethylolpropionic acid, accounts for 4.0～5.0% of raw mixture quality.
4. preparation method as claimed in claim 1, is characterized in that: in step (1), linking agent is BDO and TriMethylolPropane(TMP), and the two accounts for respectively 2.0～4.0% and 0.8～1.0% of raw mixture quality.
5. preparation method as claimed in claim 1, is characterized in that: in step (1), with the acrylate of hydroxyl, be methacrylic acid-beta-hydroxy ethyl ester, account for 2.0～4.0% of raw mixture quality.
6. preparation method as claimed in claim 1, is characterized in that: in step (2), neutralizing agent is triethylamine, carries out neutralization reaction at 20～25 ℃.
7. preparation method as claimed in claim 1, is characterized in that: in step (5), described defoamer is polyoxyethylene pentaerythritol ether or polypropylene glycerol aether;
Described thickening material is any one of Vltra tears, Xylo-Mucine and Natvosol;
Described anti-stick is polydimethylsiloxane;
Described flow agent is BYK-300 or BYK-306;
Described UV light absorber is 2,2-dihydroxyl-4-methoxy benzophenone.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103396753B (en) * | 2013-08-15 | 2015-02-25 | 西安大天新材料有限公司 | Preparation method of hot-melt polyurethane resin for bonding material |
| CN104193946B (en) * | 2014-09-15 | 2017-04-26 | 山东天庆科技发展有限公司 | self-extinction polyurethane resin and preparation method thereof |
| CN105693987B (en) * | 2014-11-25 | 2019-03-05 | 江苏华信新材料股份有限公司 | Degradable aqueous polyurethane and its preparation method and application |
| CN106167640A (en) * | 2015-10-30 | 2016-11-30 | 丹阳市日月漆业有限公司 | A kind of interfacial adhesion promoting agent and its preparation method and application |
| CN105860010B (en) * | 2016-06-08 | 2018-06-05 | 江苏华大新材料有限公司 | A kind of preparation method of the solvent-free polyurethane adhesive compound for cloth cloth |
| CN105860011B (en) * | 2016-06-08 | 2018-06-05 | 江苏华大新材料有限公司 | A kind of cloth cloth complex method based on solvent-free polyurethane adhesive |
| CN106117486B (en) * | 2016-06-27 | 2019-02-15 | 青岛科技大学 | The dihydric alcohol of the key containing acylhydrazone, the dihydric alcohol of key containing acylhydrazone and cystine linkage, selfreparing polyurethane elastomer and preparation method thereof |
| CN110358047B (en) * | 2017-02-14 | 2021-08-10 | 广东博海化工科技有限公司 | Waterborne polyurethane coating for environment-friendly temperature-resistant transfer coating and preparation method thereof |
| CN109762508B (en) * | 2018-12-26 | 2021-12-14 | 襄阳精信汇明科技股份有限公司 | Water-based hot melt adhesive with adjustable melting point and preparation method thereof |
| CN111117550A (en) * | 2019-12-31 | 2020-05-08 | 江苏华信新材料股份有限公司 | Preparation method of adhesive for mirror substrate compounding |
| CN111876097A (en) * | 2020-07-03 | 2020-11-03 | 江门市长河化工实业集团有限公司 | Prefabricated polyurethane sports floor glue and preparation method thereof |
| CN112029341B (en) * | 2020-09-15 | 2021-06-25 | 浙江华宝油墨有限公司 | Environment-friendly acrylate modified waterborne polyurethane printing ink and preparation method thereof |
| CN112172366A (en) * | 2020-09-30 | 2021-01-05 | 襄阳和顺发彩色印刷有限公司 | Printing process of green environment-friendly color box |
| CN112778963B (en) * | 2021-02-09 | 2023-03-17 | 河南银金达新材料股份有限公司 | Transparent adhesive for PETG (polyethylene terephthalate glycol) film and preparation method thereof |
| CN117069989B (en) * | 2023-08-18 | 2024-04-05 | 广东中鼎科技发展有限公司 | Anti-counterfeiting TPU high-low temperature film and preparation method thereof |
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| CN102993401A (en) * | 2012-12-05 | 2013-03-27 | 中国科学院山西煤炭化学研究所 | Method for synthesizing room-temperature cured polyurethane composite material for coating solid medicine |
| CN102977838B (en) * | 2012-12-22 | 2016-03-16 | 昆山天洋热熔胶有限公司 | A kind of lining cloth moisture-curable polyurethane hot melt adhesive and preparation method thereof |
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