CN103173185A - 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 has obtained rapid raising as an emerging independent educational project.Due to card use 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 are all take solvent borne polyurethane as main, but organic solvent is inflammable, explosive, smell is large, volatile, easily cause atmospheric pollution when using, and have certain toxicity.Constantly strengthen due to the pressure from public opinion of protection of the environment and people's environmental consciousness in recent years, many countries have formulated the laws and regulations of restriction volatile organic compound (VOC), and these factors have promoted the development of aqueous polyurethane.Except with solvent borne polyurethane has some identical character, 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 and do not contain or the advantages such as few solvent-laden coating and tackiness agent, is 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 that obtains of coating, it is explored with research and still remains to be developed.The wetting ability of the hydrophobic card matrix material of aqueous polyurethane effects on surface is relatively poor, and after having introduced hydrophilic group, its water resistance can descend again to some extent; Other some performances still are necessary to improve as functions such as resistance to settling, tear-resistant intensity, tensile strength, wear resistancies.The card series products of institute's overlay film after the card matrix material coating, its surface has the ink color pigment of more complicated, and this is very high to the requirement with the laminate product quality.Universal aqueous polyurethane is applied to this coating and has many deficiencies, as water-fast, heat-resisting, ageing-resistant performance is relatively poor.Especially product to CMYK class colour atla hot pressing pass through again stripping strength after hydrothermal aging, enjoy the producer and user's concern.
The 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 keep hydrothermal aging numerical value, for the anti-fake mark of colour atla printing, mostly shows as the 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 technique rarely has report.
Summary of the invention
The objective 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 present 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 to a certain extent in the colour atla overlay film.
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 ℃ with 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 the mixing vulcabond, form raw mix, the amount of described mixing vulcabond is 55～60% of melting mixing amount, mixing vulcabond is isophorone diisocyanate and dicyclohexyl methyl hydride-4, the 4-vulcabond, its mass ratio is 1:0.1～0.2, then progressively be 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 mix quality, progressively be warming up to 60～65 ℃, then add the acetone that accounts for raw mix quality 25～35%, reacted 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 mix quality; Linking agent is BDO and TriMethylolPropane(TMP), both accounts for respectively 2.0～4.0% and 0.8～1.0% of raw mix quality; Acrylate with hydroxyl is methacrylic acid-beta-hydroxy ethyl ester, accounts for 2.0～4.0% of raw mix 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 that adds in neutralizing agent and step (1) be 1:2.0～2.5, reacted 15～20 minutes, make in carboxyl structure wherein and salify, neutralizing agent is triethylamine.
(3) preparation 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 mix and deionized water is 1.1～1.3, obtains aqueous polyurethane dispersion.
(4) preparation aqueous polyurethane
Speed dropping diamine compound with 0.055～0.133g/min in the above-mentioned aqueous polyurethane dispersion that makes carries out chain extending reaction, add diamine compound quality and raw material in mix vulcabond mass ratio be 1:24～35, reaction times continues 15～20 minutes, makes aqueous polyurethane.Diamine compound is quadrol, carries out chain extending reaction under 20～25 ℃.
(5) preparation of waterborne polyurethane adhesive
Above-mentioned aqueous polyurethane and 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, are namely made 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 space field chemical industry company limited
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
The BDO: (analytical pure of Isosorbide-5-Nitrae-BG) Chemical Reagent Co., Ltd., Sinopharm Group
TriMethylolPropane(TMP): (TMP) rich Dihua, analytical pure Tianjin work company limited
Methacrylic acid-beta-hydroxy ethyl ester: (HEMA) analytical pure Tianjin City Chemical Agent Research Institute
Acetone: ammonia ester level Shanghai chemical reagent company limited of enterprise of shaking
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: technical grade Hubei Xinyi combination work company limited
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: the technical grade Shandong prompt green technology of letter 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 industry company limited.
The present invention compared with prior art has following beneficial effect:
1, adopt two kinds of different alicyclic diisocyanates to mix synergy, have more the advantages such as hydrolysis, anti-xanthochromia, excellent performance, product stock be stable than aromatic diisocyanate, and symmetrical vulcabond can produce the orderly block copolymer of compound with regular structure, thereby make product have higher modulus and tear strength, be more suitable for the band glued membrane coating of card matrix material.
2, two kinds of polyester glycol and polytetrahydrofuran diols that contain poly-hexanodioic acid mix use, brought into play not only 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 tack, bonding comprehensive and chemical-resistant preferably.
4, hydrophilic chain extender changes dimethylolpropionic acid into by the dimethylol propionic acid of routine, has reduced fusing point, has avoided the use of n-formyl sarcolysine base pyrrolidone noxious solvent.The organo-bismuth that catalyzer uses, 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
Further explain the present invention below in conjunction with embodiment, but embodiment does not do any type of restriction 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 dewatered 1 hour, then be cooled to 50 ℃ and shift out loft drier.Under the drying nitrogen protection, with 35g isophorone diisocyanate and 3.5g dicyclohexyl methyl hydride-4, the mixture of 4-vulcabond joins in above-mentioned four-hole boiling flask, then progressively is 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 progressively is 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, add deionized water 119.35g in dispersion machine, stir 15min and evenly spread in deionized water to polyurethane prepolymer.Slowly add at last 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, namely obtaining aqueous polyurethane emulsion 261.5g.Add 2.615g polyoxyethylene pentaerythritol ether, 2.615g Vltra tears, 1.3075g polydimethylsiloxane, 1.3075g BYK-300 and 0.523g 2 in resulting aqueous polyurethane emulsion, 2-dihydroxyl-4-methoxy benzophenone mixes, and namely 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 (%) | The 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 the PVC facial mask, and resulting band glued membrane carries out coverlay film lamination to the CMYK colour atla, and it is 130 ℃ that laminating temperature is set, and lamination pressure is 3MPa, and the lamination time is 18min.The peel strength test that the coverlay film lamination colour atla carries out aging front and back compares, 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 the UV test.Result is relatively as table 2:
The salient features of table 2 coverlay film lamination CMYK colour atla
| The coverlay film lamination colour atla | Aging front stripping strength | Aging rear stripping strength | The UV test |
| Red card | 9.9N/CM | 8.3N/CM | Clear |
| The cyan card | 9.2N/CM | 8.0N/CM | Clear |
| Yellow card | 11.3N/CM | 10.1N/CM | Clear |
| The 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 dewatered 2 hours, then be cooled to 60 ℃ and shift out loft drier.Under the drying nitrogen protection, with 40g isophorone diisocyanate and 8g dicyclohexyl methyl hydride-4, the mixture of 4-vulcabond joins in above-mentioned four-hole boiling flask, then progressively is 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 progressively is 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, add deionized water 166.4g in dispersion machine, stir 15min and evenly spread in deionized water to polyurethane prepolymer.Slowly add at last 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, namely obtaining aqueous polyurethane emulsion 350.8g.Add 5.262g polypropylene glycerol aether, 10.524 Natvosols, 3.508g polydimethylsiloxane, 3.508g BYK-306 and 1.754g 2 in resulting aqueous polyurethane emulsion, 2-dihydroxyl-4-methoxy benzophenone mixes, and namely 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 (%) | The 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
| The coverlay film lamination colour atla | Aging front stripping strength | Aging rear stripping strength | The UV test |
| Red card | 9.6N/CM | 8.0N/CM | Clear |
| The cyan card | 9.8N/CM | 9.1N/CM | Clear |
| Yellow card | 10.2N/CM | 9.9N/CM | Clear |
| The 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 dewatered 1 hour, then be cooled to 60 ℃ and shift out loft drier.Under the drying nitrogen protection, with 37.5g isophorone diisocyanate and 7.5g dicyclohexyl methyl hydride-4, the mixture of 4-vulcabond joins in above-mentioned four-hole boiling flask, then progressively is 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 progressively is 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, add deionized water 132g in dispersion machine, stir 15min and evenly spread in deionized water to polyurethane prepolymer.Slowly add at last 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, namely obtaining aqueous polyurethane emulsion 293.8g.Add 2.938g polyoxyethylene pentaerythritol ether, 8.814g Vltra tears, 2.938g polydimethylsiloxane, 1.469g BYK-300 and 1.469g 2 in resulting aqueous polyurethane emulsion, 2-dihydroxyl-4-methoxy benzophenone mixes, and namely 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 (%) | The 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
| The coverlay film lamination colour atla | Aging front stripping strength | Aging rear stripping strength | The UV test |
| Red card | 9.2N/CM | 8.1N/CM | Clear |
| The cyan card | 9.5N/CM | 8.9N/CM | Clear |
| Yellow card | 9.7N/CM | 8.3N/CM | Clear |
| The 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 dewatered 2 hours, then be cooled to 60 ℃ and shift out loft drier.Under the drying nitrogen protection, with 37.5g isophorone diisocyanate and 3.75g dicyclohexyl methyl hydride-4, the mixture of 4-vulcabond joins in above-mentioned four-hole boiling flask, then progressively is 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 progressively is 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, add deionized water 127.875g in dispersion machine, stir 15min and evenly spread in deionized water to polyurethane prepolymer.Slowly add at last 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, namely obtaining aqueous polyurethane emulsion 283.2g.Add 4.248g polypropylene glycerol aether, 2.832 Natvosols, 1.416g polydimethylsiloxane, 2.832g BYK-306 and 0.5664g 2 in resulting aqueous polyurethane emulsion, 2-dihydroxyl-4-methoxy benzophenone mixes, and namely 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 (%) | The 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
| The coverlay film lamination colour atla | Aging front stripping strength | Aging rear stripping strength | The UV test |
| Red card | 9.7N/CM | 8.2N/CM | Clear |
| The cyan card | 9.6N/CM | 8.8N/CM | Clear |
| Yellow card | 11.1N/CM | 9.8N/CM | Clear |
| The 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 dewatered 1.5 hours, then be cooled to 55 ℃ and shift out loft drier.Under the drying nitrogen protection, with 36g isophorone diisocyanate and 6g dicyclohexyl methyl hydride-4, the mixture of 4-vulcabond joins in above-mentioned four-hole boiling flask, then progressively is 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 progressively is 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, add deionized water 130g in dispersion machine, stir 15min and evenly spread in deionized water to polyurethane prepolymer.Slowly add at last 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, namely obtaining aqueous polyurethane emulsion 290.8g.Add 3.49g polypropylene glycerol aether, 5.8 Xylo-Mucines, 2.1g polydimethylsiloxane, 2.2g BYK-306 and 0.89g 2 in resulting aqueous polyurethane emulsion, 2-dihydroxyl-4-methoxy benzophenone mixes, and namely 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 (%) | The 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
| The coverlay film lamination colour atla | Aging front stripping strength | Aging rear stripping strength | The UV test |
| Red card | 9.0N/CM | 7.9N/CM | Clear |
| The cyan card | 9.7N/CM | 8.5N/CM | Clear |
| Yellow card | 10.8N/CM | 9.2N/CM | Clear |
| The black card | 8.6N/CM | 7.2N/CM | Clear |
Claims (8)
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 ℃ with 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 the mixing vulcabond, form raw mix, the amount of described mixing vulcabond is 55～60% of melting mixing amount, mixing vulcabond is isophorone diisocyanate and dicyclohexyl methyl hydride-4, the 4-vulcabond, its mass ratio is 1:0.1～0.2, then progressively be 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 mix quality, progressively be warming up to 60～65 ℃, then add the acetone that accounts for raw mix quality 25～35%, reacted 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 that adds in the neutralizing agent that adds and step (1) is 1:2.0～2.5, reacts 15～20 minutes;
(3) preparation 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 mix and deionized water is 1.1～1.3, obtains aqueous polyurethane dispersion;
(4) preparation aqueous polyurethane
Speed dropping diamine compound with 0.055～0.133g/min in the above-mentioned aqueous polyurethane dispersion that makes 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;
(5) preparation of waterborne polyurethane adhesive
The aqueous polyurethane that makes and 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, are namely made waterborne polyurethane adhesive.
2. preparation method as claimed in claim 1, it is characterized in that: in step (1), organic bismuth catalyst is bismuth zinc composite catalyst.
3. preparation method as claimed in claim 1, it is characterized in that: in step (1), hydrophilic chain extender is dimethylolpropionic acid, accounts for 4.0～5.0% of raw mix quality.
4. preparation method as claimed in claim 1, it is characterized in that: in step (1), linking agent is BDO and TriMethylolPropane(TMP), both accounts for respectively 2.0～4.0% and 0.8～1.0% of raw mix quality.
5. preparation method as claimed in claim 1 is characterized in that: in step (1), be methacrylic acid-beta-hydroxy ethyl ester with the acrylate of hydroxyl, account for 2.0～4.0% of raw mix quality.
6. preparation method as claimed in claim 1, it is characterized in that: in step (2), neutralizing agent is triethylamine, carries out neutralization reaction under 20～25 ℃.
7. preparation method as claimed in claim 1, it is characterized in that: in step (4), diamine compound is quadrol, carries out chain extending reaction under 20～25 ℃.
8. preparation method as claimed in claim 1, it 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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| CN103396753A (en) * | 2013-08-15 | 2013-11-20 | 西安大天新材料有限公司 | Preparation method of hot-melt polyurethane resin for bonding material |
| CN104193946A (en) * | 2014-09-15 | 2014-12-10 | 山东天庆科技发展有限公司 | Self-extinction polyurethane resin and preparation method thereof |
| CN105693987A (en) * | 2014-11-25 | 2016-06-22 | 江苏华信新材料股份有限公司 | Degradable waterborne polyurethane, and preparation method and applications thereof |
| CN105860010A (en) * | 2016-06-08 | 2016-08-17 | 江苏华大新材料有限公司 | Preparing method for solvent-free polyurethane adhesive for fabric-fabric combination |
| CN105860011A (en) * | 2016-06-08 | 2016-08-17 | 江苏华大新材料有限公司 | Cloth compositing method based on solvent-free polyurethane adhesive |
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| CN106589310A (en) * | 2017-02-14 | 2017-04-26 | 中山市博海精细化工有限公司 | Temperature-resisting waterborne polyurethane emulsion for transfer coating and preparing method of temperature-resisting waterborne polyurethane emulsion |
| CN109762508A (en) * | 2018-12-26 | 2019-05-17 | 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 |
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| 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 |
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