CN111117550A - Preparation method of adhesive for mirror substrate compounding - Google Patents
Preparation method of adhesive for mirror substrate compounding Download PDFInfo
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- CN111117550A CN111117550A CN201911417656.2A CN201911417656A CN111117550A CN 111117550 A CN111117550 A CN 111117550A CN 201911417656 A CN201911417656 A CN 201911417656A CN 111117550 A CN111117550 A CN 111117550A
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- mirror substrate
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/08—Polyurethanes from polyethers
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/285—Nitrogen containing compounds
- C08G18/286—Oximes
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
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- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
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- C08G18/40—High-molecular-weight compounds
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
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- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
- C08G18/6677—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
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- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6685—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
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- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
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- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
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- C09J11/04—Non-macromolecular additives inorganic
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- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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- C08L2205/00—Polymer mixtures characterised by other features
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- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- Inorganic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention provides a preparation method of an adhesive for compounding mirror-like substrates. The preparation method comprises the following steps: dicyclohexylmethane diisocyanate and polytetramethylene ether glycol are subjected to polymerization reaction, a proper amount of epoxy resin is added into a reaction system for block modification to form a net structure, methyl ethyl ketoxime is selected as a blocking agent to block end-NCO, a modified polyurethane prepolymer is prepared by a hydrophilic chain extender, triethylamine is added for neutralization, hydrazine hydrate is added for chain extension again after emulsification, and finally defoaming, thickening, leveling, anti-sticking and other treatments are carried out to obtain the adhesive for compounding the mirror surface substrate. The adhesive obtained by the method has good initial adhesion when the mirror substrate is compounded at normal temperature, the obtained mirror substrate has good laser effect, and the peel strength is high after hot-pressing and card making.
Description
Technical Field
The invention belongs to the technical field of adhesives, and particularly relates to a preparation method of an adhesive for compounding a mirror substrate.
Background
The development of science and technology and social economy enables the information technology industry to flourish rapidly, and also brings new opportunity and platform for the smart card industry, and the application field of the intelligent card industry is more and more extensive. At present, the method is developed and applied in a large scale in multiple aspects of security documents, traffic, finance, communication, social security, medical health, education, electronic government affairs and the like, and the convenience degree of work and life of people is greatly improved. With the continuous development of the smart card industry, the card technology is promoted, the content of information is increased, the appearance is changed greatly, and the personalized card with a special appearance is popular in the market. At present, processes such as concave-convex code printing, gold stamping, front and back surface lithographic printing, laser engraving and the like are commonly adopted for manufacturing personalized cards, so that the personalized manufacture of the appearance of the smart card is realized, the development of the smart card from a conventional card to the personalized card is driven, but the processes cannot obtain the laser effect.
The mirror substrate is a new generation of personalized smart card substrate, the substrate transfers holographic images with rainbow dynamic and three-dimensional effects to a PET substrate through mould pressing by applying a computer dot matrix lithography technology, a 3D true color holographic technology, a multiple and dynamic imaging technology and the like, and then the PET substrate is compounded with PVC to obtain the mirror substrate, and the mirror substrate can enable the surface of the prepared smart card to obtain a laser effect.
In the lens substrate, because PVC is a polar material, PET is non-polar polyester, and the surface of PET has an extremely thin aluminized layer, the two materials cannot be directly attached, and an adhesive is required for compounding. The compounding process of the lens substrate comprises the following steps: coating the adhesive on a PVC film, drying, and compounding with a PET laser aluminizer, wherein the aluminized surface is inwards contacted with the adhesive. In order to ensure that the adhesive on the PVC film has certain initial adhesion during compounding, compounding needs to be carried out in a drying tunnel, but when the temperature in the drying tunnel exceeds 40 ℃, the mirror surface substrate obtained by compounding warps during rolling, and the warping is more obvious when the temperature is higher. Therefore, the adhesive is required to be capable of realizing compounding at normal temperature, and good bonding force is required between the two materials. Because the manufacturing process of the intelligent card needs to adopt 140 ℃ for hot pressing, the peeling strength between the PVC and the PET of the mirror substrate can meet the corresponding requirements of the intelligent card after the hot pressing.
The prior adhesive for compounding mirror substrates has good initial adhesion during normal-temperature compounding and can not reach the peeling strength after hot pressing; the peeling strength after hot pressing is good, the laser surface of the mirror surface substrate cannot be as smooth as a mirror surface, the laser effect of the formed card is influenced, and the expected target of the personalized smart card is difficult to achieve.
Disclosure of Invention
The invention aims to provide a preparation method of an adhesive for compounding a mirror substrate, the adhesive obtained by the method has better initial adhesion when the mirror substrate is compounded at normal temperature, the peel strength is high after hot pressing and card making, and the obtained mirror substrate has good laser effect.
In order to achieve the purpose, the invention adopts the following technical scheme:
the preparation method of the adhesive for mirror substrate compounding comprises the following steps:
(1) preparation of modified blocked-NCO polyurethane prepolymers
Drying polytetramethylene ether glycol at 80-90 ℃ for 1-2 hours in vacuum, cooling to 50-60 ℃, adding dicyclohexylmethane diisocyanate to form a raw material mixture, wherein the mass ratio of dicyclohexylmethane diisocyanate to polytetramethylene ether glycol in the mixture is 1: (1.5 to 2.0), then gradually heating to 80-85 ℃, reacting for 1.5-2 hours, cooling to 40-50 ℃, adding an organic bismuth catalyst, a hydrophilic chain extender, a cross-linking agent and epoxy resin, gradually heating to 60-65 ℃, then adding acetone accounting for 20-30% of the mass of the raw material mixture, reacting for 3-4 hours, cooling to 40-50 ℃, adding methyl ethyl ketoxime, and (3) keeping the temperature for reaction for 0.5-1 hour at the temperature, heating to 65-70 ℃, continuing to react for 1.5-2.5 hours, and adjusting the system viscosity by using acetone to prepare the modified end-capped-NCO polyurethane prepolymer.
The organic bismuth catalyst is a bismuth-zinc composite catalyst, and the addition amount of the organic bismuth catalyst is 0.2-0.4% of the mass of the raw material mixture; the hydrophilic chain extender is dimethylolbutyric acid which accounts for 4.0 to 5.0 percent of the mass of the raw material mixture; the cross-linking agent is 1, 4-butanediol and trimethylolpropane which respectively account for 2.0-4.0 percent and 0.8-1.0 percent of the mass of the raw material mixture; the epoxy value of the epoxy resin is 0.48-0.54, which accounts for 3.0-5.0% of the mass of the raw material mixture, and the methyl ethyl ketoxime accounts for 6.0-8.0% of the mass of the raw material mixture.
(2) Neutralization reaction
And (2) cooling the modified end-capped-NCO polyurethane prepolymer to 20-25 ℃, adding a neutralizing agent for neutralization reaction, wherein the mass ratio of the added neutralizing agent to the added hydrophilic chain extender is 1 (2.0-2.5), reacting for 15-20 minutes to neutralize the carboxyl structure in the polyurethane prepolymer into salt, and the neutralizing agent is triethylamine.
(3) Preparation of modified polyurethane
And transferring the neutralized modified end-capped-NCO polyurethane prepolymer into a high-speed dispersion machine, and setting the shearing speed of the dispersion machine to be 3500-4000 r/min until the modified end-capped-NCO polyurethane prepolymer is uniformly dispersed into deionized water, wherein the mass ratio of the raw material mixture to the deionized water is 1 (1.2-1.4), so as to obtain the aqueous dispersion. And (2) dropwise adding hydrazine hydrate into the aqueous dispersion at the speed of 0.05-0.1 g/min for post-chain extension reaction, wherein the mass ratio of the added hydrazine hydrate to dicyclohexylmethane diisocyanate in the raw material is 1 (25-30), and the reaction time lasts for 15-20 minutes, so that the modified polyurethane is prepared.
(4) Preparation of adhesive for mirror substrate lamination
And uniformly mixing the prepared modified polyurethane with a defoaming agent, a thickening agent, an anti-adhesive agent, a leveling agent and an ultraviolet absorbent according to the mass ratio of 100 (1.0-1.5) to (1-3) to (0.5-1) to (0.2-0.5) to obtain the adhesive for mirror substrate compounding.
The defoaming agent is polyoxyethylene pentaerythritol ether or polyoxypropylene glycerol ether;
the thickening agent is any one of hydroxypropyl methyl cellulose, sodium carboxymethyl cellulose and hydroxyethyl cellulose;
the anti-adhesive is micron-sized silicon oxide powder S620;
the leveling agent is polyether modified polydimethylsiloxane BYK-300 or BYK-306;
the ultraviolet absorbent is 2, 2-dihydroxy-4-methoxybenzophenone.
Compared with the prior art, the invention has the following advantages:
1. methyl ethyl ketoxime is adopted for blocking, when the PET laser aluminized film and the PVC film are compounded at normal temperature, because-NCO is blocked stably and does not participate in main reaction, free NCO in modified polyurethane, urethane bond and polar group in the film play a role in bonding; during the card-making hot-pressing period, the methyl ethyl ketoxime blocked-NCO is unblocked at the temperature of 110-125 ℃, the-NCO begins to participate in the reaction and is matched with other polar covalent bond bonding interfaces, when the highest card-making temperature is reached, the reaction is complete, and the bonding force is maximized. The bonding strength of different molecular chains is exerted at different temperatures and different time periods, so that the adhesive has certain initial adhesion at normal temperature, has higher peel strength after hot pressing, and is blocked by methyl ethyl ketoxime, so that the prepared adhesive has good storage stability.
2. Hydrazine hydrate carries out post chain extension on the polymerization reaction which takes dicyclohexyl diisocyanate and polytetramethylene ether glycol as main materials, the prepared waterborne polyurethane chain segment is softer, the cohesive energy is low, the glass transition temperature is low, the physical viscosity is high at normal temperature, the effect of initial adhesion with the surface of a substrate at normal temperature is good, the waterborne polyurethane chain segment is easily flattened when being rolled by a composite cold roll, the surface of a PET laser aluminizer is not damaged, therefore, the surface of the obtained mirror substrate is smooth, the curling and the warping can not occur when being rolled, and the subsequent slitting and pattern printing operation on the surface of the laser aluminizer are smooth.
3. The epoxy resin is adopted for modification, the crosslinking degree of the waterborne polyurethane is increased, and the water resistance of the coating is improved. Because the epoxy resin is a polyhydroxy compound, the epoxy resin participates in polycondensation in copolymerization modification, so that the synthesized modified polyurethane molecule is subjected to network crosslinking and block copolymerization, and the peel strength after hot-pressing card making can be further improved.
Detailed Description
The present invention will be described in detail below. The raw materials selected by the invention are as follows:
polytetramethylene ether glycol: (PTMEG2000) Industrial-grade Mitsubishi chemical corporation
Dicyclohexylmethane-4, 4-diisocyanate: (HMDI) Industrial grade Nitsche Wanhua polyurethane Ltd
Bismuth-zinc composite catalyst: analytical pure US leading Chemicals Co
Dimethylolbutyric acid: (DMBA) Industrial grade Shanghai and Debi chemical Co Ltd
1, 4-butanediol: (1,4-BG) analytical pure national drug group chemical reagent Co., Ltd
Epoxy resin: (E-51) institute of Industrial synthetic Material Industrial research institute of Industrial grade Tianjin
Trimethylolpropane: (TMP) analytical pure Tianjin Bodi chemical Co., Ltd
Methyl Ethyl Ketoxime (MEKO): industrial grade Zhejiang Jinhua New Material Ltd
Acetone: polyurethane grade Shanghai Shaqi chemical Agents Ltd
Triethylamine: (TEA) analytically pure Shanghai group of national drugs
Hydrazine hydrate: (80%) analytical pure Tianjin Damao chemical reagent plant
Polyoxyethylene pentaerythritol ether: industrial Wuhan Dahuawei pharmaceutical chemical Co Ltd
Polyoxypropylene glycerol ether: industrial Hubei letter and Yi chemical Co Ltd
Hydroxypropyl methylcellulose: cellulose of Hebei Xingtai, Inc. of Industrial grade
Hydroxyethyl cellulose: cellulose of Hebei Xingtai, Inc. of Industrial grade
Sodium carboxymethylcellulose: industrial grade Shanghai-resistant and today-resistant Industrial Co Ltd
Silicon powder S620: micron DuPont USA
Polyether modified polydimethylsiloxane BYK-300: technical grade German Bike chemical Co
Polyether modified polydimethylsiloxane BYK-306: technical grade German Bike chemical Co
2, 2-dihydroxy-4-methoxybenzophenone: industrial grade texas signal chemical ltd.
A preparation method of an adhesive for mirror substrate compounding comprises the following steps:
(1) preparation of modified blocked-NCO polyurethane prepolymers
Vacuum drying polytetramethylene ether glycol at 80-90 ℃ for 1-2 hours, cooling to 50-60 ℃, adding dicyclohexylmethane diisocyanate to form a raw material mixture, wherein the mass ratio of dicyclohexylmethane diisocyanate to polytetramethylene ether glycol in the mixture is 1: (1.5 to 2.0), then gradually heating to 80-85 ℃, reacting for 1.5-2 hours, cooling to 40-50 ℃, adding an organic bismuth catalyst, a hydrophilic chain extender, a cross-linking agent and epoxy resin, gradually heating to 60-65 ℃, then adding acetone accounting for 20-30% of the mass of the raw material mixture, reacting for 3-4 hours, cooling to 40-50 ℃, adding methyl ethyl ketoxime, and (3) keeping the temperature for reaction for 0.5-1 hour at the temperature, heating to 65-70 ℃, continuing to react for 1.5-2.5 hours, and adjusting the system viscosity by using acetone to prepare the modified end-capped-NCO polyurethane prepolymer.
The organic bismuth catalyst is a bismuth-zinc composite catalyst, and the addition amount of the organic bismuth catalyst is 0.2-0.4% of the mass of the raw material mixture; the hydrophilic chain extender is dimethylolbutyric acid which accounts for 4.0 to 5.0 percent of the mass of the raw material mixture; the cross-linking agent is 1, 4-butanediol and trimethylolpropane which respectively account for 2.0-4.0 percent and 0.8-1.0 percent of the mass of the raw material mixture; the epoxy value of the epoxy resin is 0.48-0.54, which accounts for 3.0-5.0% of the mass of the raw material mixture, and the methyl ethyl ketoxime accounts for 6.0-8.0% of the mass of the raw material mixture.
The ether group in the polyurethane prepared by adopting the polytetramethylene ether glycol is soft, and the rigidity is small after film forming and the smoothness is easy; polyurethane prepared from dicyclohexyl methane diisocyanate is resistant to yellowing and strong in binding power, and meets the industrial standard of subsequent card making; the epoxy resin is a polyhydroxy compound, participates in polycondensation in copolymerization modification, so that the synthesized modified polyurethane molecules are subjected to network crosslinking, and the bonding strength is improved; the methyl ethyl ketoxime is used for blocking-NCO, so that-NCO can participate in the reaction only when the-NCO reaches a certain temperature, and the bonding effect is generated.
(2) Neutralization reaction
And (2) cooling the modified end-capped-NCO polyurethane prepolymer to 20-25 ℃, adding a neutralizing agent for neutralization reaction, wherein the mass ratio of the added neutralizing agent to the added hydrophilic chain extender is 1 (2.0-2.5), reacting for 15-20 minutes to neutralize the carboxyl structure in the polyurethane prepolymer into salt, and the neutralizing agent is triethylamine.
(3) Preparation of modified polyurethane
And transferring the neutralized modified end-capped-NCO polyurethane prepolymer into a high-speed dispersion machine, and setting the shearing speed of the dispersion machine to be 3500-4000 r/min until the modified end-capped-NCO polyurethane prepolymer is uniformly dispersed into deionized water, wherein the mass ratio of the raw material mixture to the deionized water is 1 (1.2-1.4), so as to obtain the aqueous dispersion. And (2) dropwise adding hydrazine hydrate into the aqueous dispersion at the speed of 0.05-0.1 g/min for post-chain extension reaction, wherein the mass ratio of the added hydrazine hydrate to dicyclohexylmethane diisocyanate in the raw material is 1 (25-30), and the reaction time lasts for 15-20 minutes, so that the modified polyurethane is prepared.
In order to further reduce the glass transition temperature of the adhesive and improve the physical viscosity at normal temperature, hydrazine hydrate is adopted to carry out chain extension on the aqueous dispersion.
(4) Preparation of adhesive for mirror substrate lamination
And uniformly mixing the prepared modified polyurethane with a defoaming agent, a thickening agent, an anti-adhesive agent, a leveling agent and an ultraviolet absorbent according to the mass ratio of 100 (1.0-1.5) to (1-3) to (0.5-1) to (0.2-0.5) to obtain the adhesive for mirror substrate compounding.
The defoaming agent is polyoxyethylene pentaerythritol ether or polyoxypropylene glycerol ether;
the thickening agent is any one of hydroxypropyl methyl cellulose, sodium carboxymethyl cellulose and hydroxyethyl cellulose;
in order to facilitate the rolling of the coated product and avoid adhesion during storage, the anti-adhesive is micron-sized silicon oxide powder;
the leveling agent is polyether modified polydimethylsiloxane;
the ultraviolet absorbent is 2, 2-dihydroxy-4-methoxybenzophenone.
Example 1
120g of polytetramethylene ether glycol is added into a 500ml four-neck flask, placed in a vacuum drying oven at 90 ℃ for vacuum drying for 1 hour, cooled to 50 ℃ and removed from the drying oven. Under the protection of dry nitrogen, 80g of dicyclohexylmethane diisocyanate is added into the four-neck flask to form a raw material mixture, then the temperature is gradually increased to 80 ℃, after 1.5 hours of reaction, the temperature is decreased to 40 ℃, 0.4g of bismuth-zinc composite catalyst, 8.0g of hydrophilic chain extender dimethylolbutyric acid, 4.0g of cross-linking agent 1, 4-butanediol, 1.6g of trimethylolpropane and 6.0g of epoxy resin are added, the temperature is gradually increased to 60 ℃, and then 50.0g of acetone is added for continuous reaction for 3 hours. Cooling to 40 ℃, adding 12.0g of methyl ethyl ketoxime, keeping the temperature at the temperature for reaction for 0.5 hour, heating to 65 ℃, continuing to react for 1.5 hours, then cooling to 20 ℃, adding 4.0g of triethylamine for neutralization, continuing the reaction for 15 minutes, transferring the neutralized modified polyurethane prepolymer into a high-speed dispersion machine, setting the shearing speed of the dispersion machine to 3500r/min, adding 240.0g of deionized water into the dispersion machine, and stirring for 15 minutes until the modified polyurethane prepolymer is uniformly dispersed into the deionized water. And finally, slowly adding 3.2g of hydrazine hydrate serving as a chain extender to perform secondary chain extension for 15min, and controlling the dropping speed to be 0.05g/min to obtain 475.6g of modified polyurethane emulsion.
4.756g of polyoxyethylene pentaerythritol ether, 4.756g of hydroxypropyl methyl cellulose, 2.378g of polydimethylsiloxane, 2.378g of BYK-300 and 0.9512g of 2, 2-dihydroxy-4-methoxybenzophenone are added into the obtained modified polyurethane emulsion and uniformly mixed to obtain the adhesive for compounding the mirror substrate.
Example 1 major Performance test of the adhesive
Table 1 example 1 adhesive analysis test primary indices
| Product(s) | Test temperature (. degree. C.) | Viscosity (mpa.s) | Solid content (%) | pH value |
| Index (I) | 25 | 102.6 | 34 | 7.3 |
The adhesive for compounding the mirror-surface substrate prepared in the embodiment is coated on a PVC film, is compounded with a PET laser aluminizer after being dried by circulating air at normal temperature, the aluminized surface is inwards contacted with the adhesive, and a mirror-surface substrate product is obtained after being rolled. And carrying out hot pressing on the obtained mirror substrate, setting the hot pressing temperature to be 140 ℃, the hot pressing pressure to be 4MPa and the hot pressing time to be 20min, and carrying out film laminating peel strength test comparison before and after the cooling to the room temperature. Peel strength (T-type) test method: measured according to the same method as GB/T14916-2006 using ISO/IEC7810: 2003. The results of the various tests are shown in Table 2:
table 2 testing of the effectiveness of the application of the adhesive
| Item | Peel strength | Flatness of material | Laser effect |
| Before hot pressing | 2.9N/CM | No warp | Smooth surface and good laser effect |
| After hot pressing | 16.6N/CM | No warp | Smooth surface and good laser effect |
Example 2
160g of polytetramethylene ether glycol is added into a 500ml four-neck flask, placed in a vacuum drying oven at 80 ℃ for vacuum drying for 2 hours, cooled to 60 ℃ and removed from the drying oven. Under the protection of dry nitrogen, 80g of dicyclohexylmethane diisocyanate is added into the four-neck flask to form a raw material mixture, then the temperature is gradually increased to 85 ℃, after 2.0 hours of reaction, the temperature is decreased to 50 ℃, 0.96g of bismuth-zinc composite catalyst, 12.0g of hydrophilic chain extender dimethylolbutyric acid, 9.6g of cross-linking agent 1, 4-butanediol, 2.4g of trimethylolpropane and 12.0g of epoxy resin are added, the temperature is gradually increased to 65 ℃, then 72.0g of acetone is added, and the reaction is continued for 4 hours. Cooling to 50 ℃, adding 19.2g of methyl ethyl ketoxime, keeping the temperature at the temperature for reaction for 1.0 hour, heating to 70 ℃, continuing to react for 2.5 hours, then cooling to 25 ℃, adding 6.0g of triethylamine for neutralization, continuing the reaction for 20 minutes, transferring the neutralized modified polyurethane prepolymer into a high-speed dispersion machine, setting the shearing speed of the dispersion machine to be 4000r/min, adding 336.0g of deionized water into the dispersion machine, and stirring for 15 minutes until the modified polyurethane prepolymer is uniformly dispersed into the deionized water. And finally, slowly adding 2.66g of hydrazine hydrate serving as a chain extender to perform secondary chain extension for 20min, and controlling the dropping speed to be 0.1g/min to obtain 640.8g of modified polyurethane emulsion.
9.612g of polyoxyethylene pentaerythritol ether, 19.224g of hydroxypropyl methyl cellulose, 6.408g of polydimethylsiloxane, 6.408g of BYK-300 and 3.204g of 2, 2-dihydroxy-4-methoxybenzophenone are added into the obtained modified polyurethane emulsion and uniformly mixed to obtain the adhesive for compounding the mirror substrate.
Example 2 major performance tests of the adhesive:
table 3 example 2 adhesive analysis test key
| Product(s) | Test temperature (. degree. C.) | Viscosity (mpa.s) | Solid content (%) | pH value |
| Index (I) | 25 | 110.2 | 35 | 7.1 |
The adhesive for compounding the mirror-surface substrate prepared in the embodiment is coated on a PVC film, is compounded with a PET laser aluminizer after being dried by circulating air at normal temperature, the aluminized surface is inwards contacted with the adhesive, and a mirror-surface substrate product is obtained after being rolled. And carrying out hot pressing on the obtained mirror substrate, setting the hot pressing temperature to be 140 ℃, the hot pressing pressure to be 4MPa and the hot pressing time to be 20min, and carrying out film laminating peel strength test comparison before and after the cooling to the room temperature. Peel strength (T-type) test method: measured according to the same method as GB/T14916-2006 using ISO/IEC7810: 2003. The results of the various tests are shown in Table 4:
table 4 testing of the effectiveness of the application of the adhesive
| Item | Peel strength | Flatness of material | Laser effect |
| Before hot pressing | 2.7N/CM | No warp | Smooth surface and good laser effect |
| After hot pressing | 15.9N/CM | No warp | Smooth surface and good laser effect |
Example 3
Adding 130g of polytetramethylene ether glycol into a 500ml four-neck flask, placing the flask in a vacuum drying oven at 85 ℃ for vacuum drying for 1.5 hours, cooling to 55 ℃, and removing the flask. Under the protection of dry nitrogen, 80g of dicyclohexylmethane diisocyanate is added into the four-neck flask to form a raw material mixture, then the temperature is gradually increased to 83 ℃, after 1.6 hours of reaction, the temperature is decreased to 45 ℃, 0.7g of bismuth-zinc composite catalyst, 8.9g of hydrophilic chain extender dimethylolbutyric acid, 6.8g of cross-linking agent 1, 4-butanediol, 2.2g of trimethylolpropane and 7.5g of epoxy resin are added, the temperature is gradually increased to 65 ℃, then 60.0g of acetone is added, and the reaction is continued for 3.5 hours. Cooling to 45 ℃, adding 16.0g of methyl ethyl ketoxime, keeping the temperature at the temperature for reaction for 1.0 hour, heating to 70 ℃, continuing to react for 2.0 hours, then cooling to 25 ℃, adding 4.3g of triethylamine for neutralization, continuing the reaction for 15 minutes, transferring the neutralized modified polyurethane prepolymer into a high-speed dispersion machine, setting the shearing speed of the dispersion machine to 3800r/min, adding 280.0g of deionized water into the dispersion machine, and stirring for 18 minutes until the modified polyurethane prepolymer is uniformly dispersed into the deionized water. And finally, slowly adding 3.0g of hydrazine hydrate serving as a chain extender to perform secondary chain extension for 17min, and controlling the dropping speed to be 0.09g/min to obtain 539.4g of modified polyurethane emulsion.
6.472g of polyoxyethylene pentaerythritol ether, 6.536g of hydroxypropyl methyl cellulose, 4.315g of polydimethylsiloxane, 4.394g of BYK-300 and 1.618g of 2, 2-dihydroxy-4-methoxybenzophenone are added into the obtained modified polyurethane emulsion and uniformly mixed to obtain the adhesive for compounding the mirror substrate.
Example 3 major performance tests of the adhesive:
table 5 example 3 adhesive analysis test key
| Product(s) | Test temperature (. degree.C.)) | Viscosity (mpa.s) | Solid content (%) | pH value |
| Index (I) | 25 | 112.8 | 37 | 7.1 |
The prepared adhesive for compounding the mirror substrate is coated on a PVC film, is compounded with a PET laser aluminizer after being dried by circulating air at normal temperature, the aluminized surface is inwards contacted with the adhesive, and the mirror substrate product is obtained after being rolled. And carrying out hot pressing on the obtained mirror substrate, setting the hot pressing temperature to be 140 ℃, the hot pressing pressure to be 4MPa and the hot pressing time to be 20min, and carrying out film laminating peel strength test comparison before and after the cooling to the room temperature. Peel strength (T-type) test method: measured according to the same method as GB/T14916-2006 using ISO/IEC7810: 2003. The results of the various tests are shown in Table 6:
TABLE 6 examination of the effectiveness of the application of the adhesive
| Item | Peel strength | Flatness of material | Laser effect |
| Before hot pressing | 2.6N/CM | Without warpingMusical composition | Smooth surface and good laser effect |
| After hot pressing | 17.8N/CM | No warp | Smooth surface and good laser effect |
Example 4
140g of polytetramethylene ether glycol is added into a 500ml four-neck flask, placed in a vacuum drying oven at 85 ℃ for vacuum drying for 1 hour, cooled to 55 ℃, and removed from the drying oven. Under the protection of dry nitrogen, 80g of dicyclohexylmethane diisocyanate is added into the four-neck flask to form a raw material mixture, then the temperature is gradually increased to 85 ℃, after 1.5 hours of reaction, the temperature is decreased to 40 ℃, 0.7g of bismuth-zinc composite catalyst, 11.0g of hydrophilic chain extender dimethylolbutyric acid, 5.2g of cross-linking agent 1, 4-butanediol, 1.9g of trimethylolpropane and 10.0g of epoxy resin are added, the temperature is gradually increased to 63 ℃, and then 66.0g of acetone is added for continuous reaction for 3 hours. Cooling to 42 ℃, adding 15.0g of methyl ethyl ketoxime, keeping the temperature at the temperature for reaction for 0.5 hour, heating to 68 ℃, continuing to react for 1.5 hour, then cooling to 25 ℃, adding 4.4g of triethylamine for neutralization, continuing the reaction for 15min, transferring the neutralized modified polyurethane prepolymer into a high-speed dispersion machine, setting the shearing speed of the dispersion machine to 3600r/min, adding 265.0g of deionized water into the dispersion machine, and stirring for 17min until the modified polyurethane prepolymer is uniformly dispersed into the deionized water. And finally, slowly adding 3.0g of hydrazine hydrate serving as a chain extender to perform secondary chain extension for 15min, and controlling the dropping speed to be 0.06g/min to obtain 526.6g of modified polyurethane emulsion.
5.266g of polyoxyethylene pentaerythritol ether, 10.532g of hydroxypropyl methyl cellulose, 4.212g of polydimethylsiloxane, 4.463g of BYK-300 and 1.515g of 2, 2-dihydroxy-4-methoxybenzophenone are added into the obtained modified polyurethane emulsion and uniformly mixed to obtain the adhesive for compounding the mirror substrate.
Example 4 major performance tests of the adhesive:
table 7 example 4 adhesive analysis test key
| Product(s) | Test temperature (. degree. C.) | Viscosity (mpa.s) | Solid content (%) | pH value |
| Index (I) | 25 | 109.5 | 33 | 7.2 |
The adhesive for compounding the mirror-surface substrate prepared in the embodiment is coated on a PVC film, is compounded with a PET laser aluminizer after being dried by circulating air at normal temperature, the aluminized surface is inwards contacted with the adhesive, and a mirror-surface substrate product is obtained after being rolled. And carrying out hot pressing on the obtained mirror substrate, setting the hot pressing temperature to be 140 ℃, the hot pressing pressure to be 4MPa and the hot pressing time to be 20min, and carrying out film laminating peel strength test comparison before and after the cooling to the room temperature. Peel strength (T-type) test method: measured according to the same method as GB/T14916-2006 using ISO/IEC7810: 2003. The results of the various tests are shown in Table 8:
TABLE 8 examination of the effectiveness of the application of the adhesive
| Item | Peel strength | Flatness of material | Laser effect |
| Before hot pressing | 2.8N/CM | No warp | Smooth surface and good laser effect |
| After hot pressing | 17.1N/CM | No warp | Smooth surface and good laser effect |
Comparative example
And (3) carrying out hot pressing on the mirror substrate prepared by the two conventional adhesives, setting the hot pressing temperature to be 140 ℃, the hot pressing pressure to be 4MPa and the hot pressing time to be 20min, and cooling to room temperature, and then carrying out film laminating peel strength test comparison before and after hot pressing. Peel strength (T-type) test method: ISO/IEC7810:2003 was used in accordance with the same standard as GB/T14916-2006, and the measurement data are shown in Table 9:
TABLE 9 comparative example test results
As can be seen from the comparative example, the first one has better initial adhesion at normal temperature and better laser effect, but has poorer peel strength after hot pressing; the second type has better initial adhesion and peeling strength after hot pressing, but has rough surface and poor laser effect. The test results of the embodiment and the comparative example show that the adhesive for compounding the mirror substrate has better initial adhesion when being compounded at normal temperature, the obtained mirror substrate has good laser effect, and the peel strength is high after hot-pressing card making.
Claims (3)
1. A method for preparing an adhesive for mirror substrate lamination is characterized in that: the method comprises the following steps:
(1) preparation of modified blocked-NCO polyurethane prepolymers
Drying polytetramethylene ether glycol at 80-90 ℃ for 1-2 hours in vacuum, cooling to 50-60 ℃, adding dicyclohexylmethane diisocyanate to form a raw material mixture, wherein the mass ratio of dicyclohexylmethane diisocyanate to polytetramethylene ether glycol in the mixture is 1: (1.5 to 2.0), then gradually heating to 80-85 ℃, reacting for 1.5-2 hours, cooling to 40-50 ℃, adding an organic bismuth catalyst, a hydrophilic chain extender, a cross-linking agent and epoxy resin, gradually heating to 60-65 ℃, then adding acetone accounting for 20-30% of the mass of the raw material mixture, reacting for 3-4 hours, cooling to 40-50 ℃, adding methyl ethyl ketoxime, keeping the temperature at the temperature for reaction for 0.5-1 hour, heating to 65-70 ℃, continuing to react for 1.5-2.5 hours, and adjusting the system viscosity by using acetone to prepare a modified end-capped-NCO polyurethane prepolymer;
the organic bismuth catalyst is a bismuth-zinc composite catalyst, and the addition amount of the organic bismuth catalyst is 0.2-0.4% of the mass of the raw material mixture; the hydrophilic chain extender is dimethylolbutyric acid which accounts for 4.0 to 5.0 percent of the mass of the raw material mixture; the cross-linking agent is 1, 4-butanediol and trimethylolpropane which respectively account for 2.0-4.0 percent and 0.8-1.0 percent of the mass of the raw material mixture; the epoxy resin accounts for 3.0-5.0% of the mass of the raw material mixture, and the methyl ethyl ketoxime accounts for 6.0-8.0% of the mass of the raw material mixture;
(2) neutralization reaction
Cooling the modified end-capped-NCO polyurethane prepolymer to 20-25 ℃, adding a neutralizing agent for neutralization reaction, wherein the mass ratio of the added neutralizing agent to the added hydrophilic chain extender is 1 (2.0-2.5), reacting for 15-20 minutes to neutralize the carboxyl structure in the polyurethane prepolymer into salt, and the neutralizing agent is triethylamine;
(3) preparation of modified polyurethane
Transferring the neutralized modified end-capped-NCO polyurethane prepolymer into a high-speed dispersion machine, setting the shearing speed of the dispersion machine to be 3500-4000 r/min, and uniformly dispersing the modified end-capped-NCO polyurethane prepolymer into deionized water, wherein the mass ratio of the raw material mixture to the deionized water is 1 (1.2-1.4), so as to obtain an aqueous dispersion; dropwise adding hydrazine hydrate into the aqueous dispersion at the speed of 0.05-0.1 g/min for post-chain extension reaction, wherein the mass ratio of the added hydrazine hydrate to dicyclohexylmethane diisocyanate in the raw material is 1 (25-30), and the reaction time lasts for 15-20 minutes to prepare modified polyurethane;
(4) preparation of adhesive for mirror substrate lamination
And uniformly mixing the prepared modified polyurethane with a defoaming agent, a thickening agent, an anti-adhesive agent, a leveling agent and an ultraviolet absorbent according to the mass ratio of 100 (1.0-1.5) to (1-3) to (0.5-1) to (0.2-0.5) to obtain the adhesive for mirror substrate compounding.
2. The method for preparing an adhesive for mirror substrate lamination according to claim 1, wherein: the epoxy value of the epoxy resin is 0.48-0.54.
3. The method for preparing an adhesive for mirror substrate lamination according to claim 1, wherein: the defoaming agent is polyoxyethylene pentaerythritol ether or polyoxypropylene glycerol ether;
the thickening agent is any one of hydroxypropyl methyl cellulose, sodium carboxymethyl cellulose and hydroxyethyl cellulose;
the anti-adhesive is micron-sized silicon oxide powder;
the leveling agent is polyether modified polydimethylsiloxane;
the ultraviolet absorbent is 2, 2-dihydroxy-4-methoxybenzophenone.
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Application publication date: 20200508 |