CN115926613A - Coating for laser film transfer and preparation method thereof - Google Patents
Coating for laser film transfer and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a coating for laser film transfer and a preparation method thereof, and relates to the technical field of coating coatings. When preparing the coating for laser film transfer, firstly, reacting calcium lignosulphonate with aniline to prepare doped polyaniline; reacting imidazole with 1-bromodecane to prepare N-decyl imidazole, and reacting the N-decyl imidazole with dibromoneopentyl glycol to prepare a bisimidazolium salt chain extender; reacting isophorone diisocyanate, a bisimidazolium salt chain extender and polyether polyol, and capping with hydroxyethyl acrylate to obtain a bisimidazolium salt polyurethane oligomer; the paint for laser film transfer is prepared by mixing the bisimidazolium salt polyurethane acrylate oligomer, the doped polyaniline, the reactive diluent and the photoinitiator. The coating for laser film transfer prepared by the invention has good corrosion resistance, antibacterial performance and laser film transfer effect after laser film transfer.
Description
Technical Field
The invention relates to the technical field of coating paint, in particular to a paint for laser film transfer and a preparation method thereof.
Background
With the development of modern science and technology, various packaging materials are emerging continuously. The laser transfer paper is popular in various fields since the world as a high-end packaging material, is more and more widely applied to the field of packaging, and the using amount of the laser transfer paper is greatly increased year by year. However, the glass transition temperature of the traditional laser transfer paper coating is relatively high, which requires that the temperature of a plate roller during mould pressing is high, but the stretching deformation of a base film is easily generated due to the high temperature of the plate roller during mould pressing. Therefore, research and development on the laser film cold transfer process are gradually rising.
In the cold transfer process of the laser film, a plurality of problems still remain to be solved, such as wrinkling, pinholes, white spots, bubbles and the like, which cause unstable performance. The key of the laser film cold transfer process is the coating, so that improvement of the laser film cold transfer process is essential to improvement and research of the coating for laser film transfer.
Disclosure of Invention
The invention aims to provide a coating for laser film transfer and a preparation method thereof, which are used for solving the problems in the prior art.
In order to solve the technical problems, the invention provides the following technical scheme:
a preparation method of a coating for laser film transfer comprises the following preparation steps:
(1) Reacting calcium lignosulphonate with aniline to prepare doped polyaniline;
(2) Reacting imidazole with 1-bromodecane to prepare N-decyl imidazole, and reacting the N-decyl imidazole with dibromoneopentyl glycol to prepare a bisimidazolium salt chain extender;
(3) Reacting isophorone diisocyanate, a bis-imidazolium salt chain extender and polyether polyol, and capping with hydroxyethyl acrylate to obtain a bis-imidazolium salt polyurethane oligomer;
(4) The paint for laser film transfer is prepared by mixing the bisimidazolium salt polyurethane acrylate oligomer, the doped polyaniline, the reactive diluent and the photoinitiator.
As optimization, the preparation method of the coating for laser film transfer comprises the following preparation steps:
(1) Preparing doped polyaniline: ammonium persulfate and 18-22% of hydrochloric acid solution in mass percentage are mixed according to the mass ratio of 1:3 to 1:4, uniformly mixing, adding aniline solution with the mass 2.7-3.1 times of that of the ammonium persulfate at a constant speed within 30-40 min under the stirring condition of 300-500 r/min at the temperature of 0-5 ℃, continuously stirring and reacting for 20-24 h after the dropwise addition is finished, filtering, washing for 3-5 times by using pure water and absolute ethyl alcohol, and drying for 6-8 h at the temperature of-1-10 ℃ under 1-10 Pa to prepare doped polyaniline;
(2) Preparation of the bisimidazolium salt chain extender: n-decyl imidazole, dibromo neopentyl glycol and dimethyl sulfoxide are mixed according to the mass ratio of 2:1: 15-2: 1:25, uniformly mixing, stirring and reacting for 14-18 h at 110-120 ℃ and 300-500 r/min in a nitrogen atmosphere, standing for 3-4 h at 20-30 ℃ and 1-2 kPa after the reaction is finished, washing for 3-5 times by using tetrahydrofuran, filtering, and drying for 6-8 h at 60-70 ℃ to obtain the bisimidazolium salt chain extender;
(3) Preparation of bisimidazolium salt polyurethane oligomer: isophorone diisocyanate and a bis-imidazolium salt chain extender are added according to the mass ratio of 2.8:1 to 3.2:1, uniformly mixing, adding polyether polyol 4-5 times of the mass of isophorone diisocyanate and dibutyltin dilaurate 0.08-0.12 time of the mass of isophorone diisocyanate, stirring and reacting for 3-4 h at 45-55 ℃ at 300-500 r/min, adding hydroxyethyl acrylate 0.3-0.4 time of the mass of isophorone diisocyanate, continuously stirring and reacting for 3-4 h, and standing for 6-8 h at 20-30 ℃ under 50-100 Pa to obtain a bis-imidazolium salt polyurethane oligomer;
(4) Mixing materials: the method comprises the following steps of mixing bisimidazolium salt polyurethane acrylate oligomer, doped polyaniline, an active diluent and a photoinitiator according to a mass ratio of 60:4:25:1 to 70:6:30:1, blending, stirring at the temperature of 20-30 ℃ at the speed of 800-1000 r/min for 20-30 min, and obtaining the coating for laser film transfer.
Preferably, the aniline solution obtained in the step (1) is prepared by mixing calcium lignin benzene sulfonate and pure water according to a mass ratio of 1:20 to 1:25, then adding aniline with the mass 3-5 times of that of the calcium lignosulphonate, and stirring for 4-6 h at the temperature of 20-30 ℃ at the speed of 500-800 r/min.
As optimization, the preparation method of the N-decyl imidazole in the step (2) comprises the following steps: imidazole, potassium hydroxide and dimethyl sulfoxide are mixed according to the mass ratio of 1.2:1: 3-1.4: 1:4, uniformly mixing, stirring and reacting for 3-4 h at 85-95 ℃ at 500-800 r/min, cooling to 10-20 ℃, adding 1-bromodecane 2.8-3 times the mass of the imidazole, stirring and reacting for 14-18 h at 60-70 ℃ at 500-800 r/min, adding pure water 14-18 times the mass of the imidazole, continuously stirring for 20-30 min, extracting for 3-5 times by using anhydrous ether, and removing the solvent by using a rotary evaporator to prepare the catalyst.
Preferably, the polyether polyol in the step (3) is HSH330.
Preferably, the reactive diluent in the step (4) is one or more of 1, 6-hexanediol diacrylate, isobornyl acrylate and trimethylolpropane trimethacrylate.
Preferably, the photoinitiator in the step (4) is 2-hydroxy-2-methyl-1-propiophenone.
As optimization, the application method of the coating for laser film transfer comprises the following steps: 5.5 to 6g/m of coating for transferring the laser film 3 Coating the coating weight on a PET base film, rolling and pressing the PET base film and the surface of the laser film with the laser micro grooves, irradiating for 3-4 min by using an ultraviolet lamp, stripping the laser film from the coated PET base film, and standing for 10-12 h at room temperature to obtain the laser film transfer coating.
Compared with the prior art, the invention has the following beneficial effects:
when the coating for laser film transfer is prepared, firstly, isophorone diisocyanate, a bisimidazolium salt chain extender and polyether polyol react, hydroxyethyl acrylate is used for blocking, a bisimidazolium salt polyurethane oligomer is prepared, and the bisimidazolium salt polyurethane acrylate oligomer, doped polyaniline, an active diluent and a photoinitiator are mixed to prepare the coating for laser film transfer.
Firstly, calcium lignosulphonate reacts with aniline to prepare doped polyaniline, a large number of active groups exist in the calcium lignosulphonate, the doped polyaniline is promoted to be fused with a main body, double bonds contained in lignin can participate in polymerization of free radicals, a curing structure is more compact, corrosion resistance is improved, the compact curing structure enables the whole body not to be separated easily, and therefore the laser film transfer effect is good.
Secondly, imidazole and 1-bromodecane react to prepare N-decyl imidazole, the N-decyl imidazole and dibromoneopentyl glycol react to prepare a bisimidazolium salt chain extender, an imidazole ring in the bisimidazolium salt chain extender is of a five-membered heterocyclic conjugated structure, has an antibacterial effect and is provided with a long alkyl chain, and after the electrostatic attraction of imidazole cations and bacterial cell membranes, the long alkyl chain can pierce the bacterial cell membranes to accelerate the outflow of bacterial cell contents and kill bacteria, so that the antibacterial performance is improved, and after the bisimidazolium salt chain extender participates in chain extension, the long alkyl chain outside enables the whole to be hydrophobic, so that the corrosion resistance is improved; the hydroxyethyl acrylate is used for end capping, so that carbon-carbon double bonds are contained on two sides of the double imidazolium salt polyurethane oligomer and can participate in polymerization of double bonds initiated by a photoinitiator, and a polymer network structure is formed overall, so that the corrosion resistance and the laser film transfer effect are improved.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In order to more clearly illustrate the method provided by the present invention, the following examples are used to describe the method for testing the indexes of the coating for laser film transfer, which is prepared in the following examples, as follows:
the application method comprises the following steps: the coating for transferring the laser film is 5.8g/m 3 Coating the coating weight on a PET base film, rolling and pressing the PET base film and the surface of the laser film with the laser micro grooves, irradiating for 3.5min by using an ultraviolet lamp, stripping the laser film from the coated PET base film, and standing for 11h at room temperature to obtain the laser film transfer coating.
Corrosion resistance: the coating for laser film transfer obtained in each example and the comparative example material are coated and cured into a coating with the same size, shape and thickness, soaked in 10% hydrochloric acid solution for 4h, taken out, washed, dried and weighed, and the corrosion amount is recorded.
Antibacterial property: the coating for laser film transfer obtained in each example and the comparative example material were applied and cured to form a coating layer having the same size and shape thickness, and the antibacterial ratio was measured and recorded according to ISO 22196.
The laser film transfer effect is as follows: the coating for transferring the laser film obtained in each example and the comparative example material are applied in the same mass, and the surface after application is observed to have the phenomena of wrinkle, pinholes, white spots, bubbles and the like.
Example 1
A preparation method of a coating for laser film transfer mainly comprises the following preparation steps:
(1) Preparing doped polyaniline: mixing calcium lignosulphonate and pure water according to a mass ratio of 1:20, uniformly mixing, adding aniline with the mass of 3 times that of the calcium lignosulphonate, and stirring at the temperature of 20 ℃ and at the speed of 500r/min for 6 hours to prepare aniline solution; ammonium persulfate and 18% hydrochloric acid solution in mass fraction are mixed according to the mass ratio of 1:3, uniformly mixing, adding aniline solution with the mass 2.7 times that of the ammonium persulfate within 40min at a constant speed under the stirring condition of 300r/min at 0 ℃, continuing stirring and reacting for 24h after finishing dripping, filtering, washing for 3 times by using pure water and absolute ethyl alcohol, and drying for 8h at-1 ℃ under 1Pa to prepare doped polyaniline;
(2) Preparation of the bisimidazolium salt chain extender: imidazole, potassium hydroxide and dimethyl sulfoxide are mixed according to the mass ratio of 1.2:1:3, uniformly mixing, stirring and reacting at 85 ℃ and 500r/min for 4h, cooling to 10 ℃, adding 1-bromodecane 2.8 times the mass of imidazole, stirring and reacting at 60 ℃ and 500r/min for 18h, adding pure water 14 times the mass of imidazole, continuously stirring for 30min, extracting with anhydrous ether for 3 times, and removing the solvent through a rotary evaporator to obtain a yellow oily product N-decylimidazole; n-decyl imidazole, dibromo neopentyl glycol and dimethyl sulfoxide are mixed according to the mass ratio of 2:1:15, uniformly mixing, stirring and reacting at 110 ℃ and 300r/min for 18h in a nitrogen atmosphere, standing for 4h at 20 ℃ and 1kPa after the reaction is finished, washing for 3 times by using tetrahydrofuran, filtering, and drying for 8h at 60 ℃ to obtain the bisimidazolium salt chain extender;
(3) Preparation of bis-imidazolium salt polyurethane oligomer: isophorone diisocyanate and a bis-imidazolium salt chain extender are added according to the mass ratio of 2.8:1, uniformly mixing, adding polyether polyol HSH330 with the mass being 4 times that of isophorone diisocyanate and dibutyltin dilaurate with the mass being 0.08 time that of isophorone diisocyanate, stirring and reacting for 4 hours at 45 ℃ at 300r/min, adding hydroxyethyl acrylate with the mass being 0.3 time that of isophorone diisocyanate, continuing stirring and reacting for 4 hours, and standing for 8 hours at 20 ℃ under 50Pa to obtain a bis-imidazolium salt polyurethane oligomer;
(4) Mixing materials: mixing bis-imidazolium salt polyurethane acrylate oligomer, doped polyaniline, 1, 6-hexanediol diacrylate and 2-hydroxy-2-methyl-1-propiophenone according to a mass ratio of 60:4:25:1, blending, stirring at 20 ℃ and 800r/min for 30min to prepare the coating for laser film transfer.
Example 2
A preparation method of a coating for laser film transfer mainly comprises the following preparation steps:
(1) Preparing doped polyaniline: mixing calcium lignosulphonate and pure water according to a mass ratio of 1:22, adding aniline with the mass 4 times that of the calcium lignosulphonate, and stirring at the temperature of 25 ℃ and the speed of 600r/min for 5 hours to prepare aniline solution; ammonium persulfate and 20% hydrochloric acid solution in mass fraction are mixed according to the mass ratio of 1:3.5, uniformly mixing, adding an aniline solution with the mass 2.9 times that of the ammonium persulfate within 35min at a constant speed under the stirring condition of 400r/min at the temperature of 3 ℃, continuing to stir and react for 22h after finishing dropping, filtering, washing for 4 times by using pure water and absolute ethyl alcohol, and drying for 7h at the temperature of-5 ℃ under 5Pa to prepare doped polyaniline;
(2) Preparation of the bisimidazolium salt chain extender: imidazole, potassium hydroxide and dimethyl sulfoxide are mixed according to the mass ratio of 1.3:1:
3.5, uniformly mixing, stirring and reacting at 90 ℃ and 650r/min for 3.5h, cooling to 15 ℃, adding 1-bromodecane 2.9 times the mass of the imidazole, stirring and reacting at 65 ℃ and 650r/min for 16h, adding pure water 16 times the mass of the imidazole, continuously stirring for 25min, extracting with anhydrous ether for 4 times, and removing the solvent by a rotary evaporator to obtain a yellow oily product N-decylimidazole; n-decyl imidazole, dibromo neopentyl glycol and dimethyl sulfoxide are mixed according to the mass ratio of 2:1:20, uniformly mixing, stirring and reacting at 115 ℃ and 400r/min for 16h in a nitrogen atmosphere, standing for 3.5h at 25 ℃ and 1.5kPa after the reaction is finished, washing for 4 times by using tetrahydrofuran, filtering, and drying for 7h at 65 ℃ to obtain the bisimidazolium salt chain extender;
(3) Preparation of bisimidazolium salt polyurethane oligomer: isophorone diisocyanate and a bis-imidazolium salt chain extender are added according to the mass ratio of 3:1, uniformly mixing, adding polyether glycol HSH330 with the mass being 4.5 times that of isophorone diisocyanate and dibutyltin dilaurate with the mass being 0.1 time that of isophorone diisocyanate, stirring and reacting for 3.5h at 50 ℃ at 400r/min, adding hydroxyethyl acrylate with the mass being 0.35 time that of isophorone diisocyanate, continuing to stir and react for 3.5h, and standing for 7h at 20-30 ℃ under 80Pa to prepare a bis-imidazolium salt polyurethane oligomer;
(4) Mixing materials: the method comprises the following steps of mixing bis-imidazolium salt polyurethane acrylate oligomer, doped polyaniline, isobornyl acrylate and 2-hydroxy-2-methyl-1-propiophenone according to a mass ratio of 65:5:28:1, blending, and stirring at 25 ℃ and 900r/min for 25min to obtain the coating for laser film transfer.
Example 3
A preparation method of a coating for laser film transfer mainly comprises the following preparation steps:
(1) Preparing doped polyaniline: mixing calcium lignosulphonate and pure water according to a mass ratio of 1:25, uniformly mixing, adding aniline with the mass 5 times that of the calcium lignosulphonate, and stirring at 30 ℃ at 800r/min for 4-6 h to prepare an aniline solution; ammonium persulfate and a hydrochloric acid solution with the mass fraction of 22% are mixed according to the mass ratio of 1:4, uniformly mixing, adding aniline solution with the mass of 3.1 times of that of ammonium persulfate at a constant speed within 30min under the stirring condition of 500r/min at the temperature of 5 ℃, continuing stirring and reacting for 24h after finishing dropping, filtering, washing for 5 times by using pure water and absolute ethyl alcohol, and drying for 6h at the temperature of-10 ℃ and 10Pa to prepare doped polyaniline;
(2) Preparation of the bisimidazolium salt chain extender: imidazole, potassium hydroxide and dimethyl sulfoxide are mixed according to the mass ratio of 1.4:1:4, uniformly mixing, stirring and reacting at 95 ℃ and 800r/min for 3 hours, cooling to 20 ℃, adding 1-bromodecane accounting for 3 times of the mass of the imidazole, stirring and reacting at 70 ℃ and 800r/min for 14 hours, adding pure water accounting for 18 times of the imidazole, continuously stirring for 30 minutes, extracting for 3 times by using anhydrous ether, and removing the solvent by using a rotary evaporator to obtain a yellow oily product N-decyl imidazole; n-decyl imidazole, dibromo neopentyl glycol and dimethyl sulfoxide are mixed according to the mass ratio of 2:1:25, uniformly mixing, stirring and reacting for 14 hours at 120 ℃ and 500r/min in a nitrogen atmosphere, standing for 3 hours at 30 ℃ and 2kPa after the reaction is finished, washing for 3 times by using tetrahydrofuran, filtering, and drying for 6 hours at 70 ℃ to obtain the bisimidazolium salt chain extender;
(3) Preparation of bisimidazolium salt polyurethane oligomer: isophorone diisocyanate and a bis-imidazolium salt chain extender are added according to the mass ratio of 3.2:1, uniformly mixing, adding polyether polyol HSH330 accounting for 5 times of the mass of isophorone diisocyanate and dibutyltin dilaurate accounting for 0.12 time of the mass of isophorone diisocyanate, stirring and reacting for 3 hours at 55 ℃ and 500r/min, adding hydroxyethyl acrylate accounting for 0.4 time of the mass of isophorone diisocyanate, continuously stirring and reacting for 3 hours, and standing for 6 hours at 30 ℃ and 100Pa to obtain a bis-imidazolium salt polyurethane oligomer;
(4) Mixing materials: mixing bis-imidazolium salt polyurethane acrylate oligomer, doped polyaniline, trimethylolpropane trimethacrylate and 2-hydroxy-2-methyl-1-propiophenone according to the mass ratio of 60:4:25:1 to 70:6:30:1, blending, stirring at the temperature of between 20 and 30 ℃ at the speed of between 800 and 1000r/min for 20 to 30min, and preparing the coating for laser film transfer.
Comparative example 1
A preparation method of a coating for laser film transfer mainly comprises the following preparation steps:
(1) Preparation of the bis-imidazolium salt chain extender: imidazole, potassium hydroxide and dimethyl sulfoxide are mixed according to the mass ratio of 1.3:1:3.5, uniformly mixing, stirring and reacting at 90 ℃ and 650r/min for 3.5h, cooling to 15 ℃, adding 1-bromodecane 2.9 times the mass of the imidazole, stirring and reacting at 65 ℃ and 650r/min for 16h, adding pure water 16 times the mass of the imidazole, continuously stirring for 25min, extracting with anhydrous ether for 4 times, and removing the solvent by a rotary evaporator to obtain a yellow oily product N-decylimidazole; n-decyl imidazole, dibromo neopentyl glycol and dimethyl sulfoxide are mixed according to the mass ratio of 2:1:20, uniformly mixing, stirring and reacting at 115 ℃ and 400r/min for 16h in a nitrogen atmosphere, standing for 3.5h at 25 ℃ and 1.5kPa after the reaction is finished, washing for 4 times by using tetrahydrofuran, filtering, and drying for 7h at 65 ℃ to obtain the bisimidazolium salt chain extender;
(2) Preparation of bisimidazolium salt polyurethane oligomer: isophorone diisocyanate and a bisimidazolium salt chain extender are mixed according to a mass ratio of 3:1, uniformly mixing, adding polyether glycol HSH330 with the mass of 4.5 times that of isophorone diisocyanate and dibutyltin dilaurate with the mass of 0.1 time that of isophorone diisocyanate, stirring and reacting for 3.5h at 50 ℃ at 400r/min, adding hydroxyethyl acrylate with the mass of 0.35 time that of isophorone diisocyanate, continuing stirring and reacting for 3.5h, and standing for 7h at 20-30 ℃ under 80Pa to obtain a bis-imidazolium salt polyurethane oligomer;
(3) Mixing materials: mixing bis-imidazolium salt polyurethane acrylate oligomer, polyaniline, isobornyl acrylate and 2-hydroxy-2-methyl-1-propiophenone according to a mass ratio of 65:5:28:1, blending, stirring at the temperature of 25 ℃ and 900r/min for 25min to prepare the coating for laser film transfer.
Comparative example 2
A preparation method of a coating for laser film transfer mainly comprises the following preparation steps:
(1) Preparing doped polyaniline: mixing calcium lignosulphonate and pure water according to a mass ratio of 1:22, adding aniline with the mass 4 times that of the calcium lignosulphonate, and stirring at the temperature of 25 ℃ and the speed of 600r/min for 5 hours to prepare aniline solution; ammonium persulfate and 20% hydrochloric acid solution in mass fraction are mixed according to the mass ratio of 1:3.5, uniformly mixing, adding an aniline solution with the mass 2.9 times that of the ammonium persulfate within 35min at a constant speed under the stirring condition of 400r/min at the temperature of 3 ℃, continuing to stir and react for 22h after finishing dropping, filtering, washing for 4 times by using pure water and absolute ethyl alcohol, and drying for 7h at the temperature of-5 ℃ under 5Pa to prepare doped polyaniline;
(2) Preparation of urethane oligomer: mixing isophorone diisocyanate and a polyurethane chain extender HER according to a mass ratio of 3:1, uniformly mixing, adding polyether glycol HSH330 with the mass of 4.5 times that of isophorone diisocyanate and dibutyltin dilaurate with the mass of 0.1 time that of isophorone diisocyanate, stirring and reacting for 3.5h at 50 ℃ at 400r/min, adding hydroxyethyl acrylate with the mass of 0.35 time that of isophorone diisocyanate, continuing stirring and reacting for 3.5h, and standing for 7h at 20-30 ℃ under 80Pa to obtain a polyurethane oligomer;
(4) Mixing materials: polyurethane acrylate oligomer, doped polyaniline, isobornyl acrylate and 2-hydroxy-2-methyl-1-propiophenone are mixed according to the mass ratio of 65:5:28:1, blending, stirring at the temperature of 25 ℃ and 900r/min for 25min to prepare the coating for laser film transfer.
Comparative example 3
The preparation method of the coating for laser film transfer mainly comprises the following preparation steps:
(1) Preparing doped polyaniline: mixing calcium lignosulphonate and pure water according to a mass ratio of 1:22, uniformly mixing, adding aniline with the mass of 4 times that of the calcium lignosulphonate, and stirring at the temperature of 25 ℃ and the speed of 600r/min for 5 hours to prepare aniline solution; ammonium persulfate and 20% hydrochloric acid solution in mass fraction are mixed according to the mass ratio of 1:3.5, uniformly mixing, adding aniline solution with the mass 2.9 times that of the ammonium persulfate within 35min under the stirring condition of 400r/min at the temperature of 3 ℃, continuing to stir and react for 22h after finishing dripping, filtering, washing for 4 times by using pure water and absolute ethyl alcohol, and drying for 7h at the temperature of-5 ℃ under the pressure of 5Pa to prepare doped polyaniline;
(2) Preparation of the bisimidazolium salt chain extender: imidazole, potassium hydroxide and dimethyl sulfoxide are mixed according to the mass ratio of 1.3:1:3.5, uniformly mixing, stirring and reacting at 90 ℃ and 650r/min for 3.5h, cooling to 15 ℃, adding 1-bromodecane 2.9 times the mass of the imidazole, stirring and reacting at 65 ℃ and 650r/min for 16h, adding pure water 16 times the mass of the imidazole, continuously stirring for 25min, extracting with anhydrous ether for 4 times, and removing the solvent by a rotary evaporator to obtain a yellow oily product N-decylimidazole; n-decyl imidazole, dibromo neopentyl glycol and dimethyl sulfoxide are mixed according to the mass ratio of 2:1:20, uniformly mixing, stirring and reacting at 115 ℃ and 400r/min for 16h in a nitrogen atmosphere, standing for 3.5h at 25 ℃ and 1.5kPa after the reaction is finished, washing for 4 times by using tetrahydrofuran, filtering, and drying for 7h at 65 ℃ to obtain the bisimidazolium salt chain extender;
(3) Preparation of bisimidazolium salt polyurethane oligomer: isophorone diisocyanate and a bis-imidazolium salt chain extender are added according to the mass ratio of 3:1, uniformly mixing, adding polyether glycol HSH330 with the mass of 4.5 times that of isophorone diisocyanate and dibutyltin dilaurate with the mass of 0.1 time that of isophorone diisocyanate, stirring and reacting for 3.5h at 50 ℃ at 400r/min, adding hydroxyethyl propionate with the mass of 0.35 time that of isophorone diisocyanate, continuing stirring and reacting for 3.5h, and standing for 7h at 20-30 ℃ under 80Pa to obtain a bis-imidazolium salt polyurethane oligomer;
(4) Mixing materials: mixing a bisimidazolium salt polyurethane acrylate oligomer, doped polyaniline, isobornyl acrylate and 2-hydroxy-2-methyl-1-propiophenone according to a mass ratio of 65:5:28:1, blending, stirring at the temperature of 25 ℃ and 900r/min for 25min to prepare the coating for laser film transfer.
Examples of effects
The following table 1 shows the results of performance analysis of the corrosion resistance, the antibacterial property and the laser film transfer effect after the application of the coatings for laser film transfer of examples 1 to 3 of the present invention and comparative examples 1 to 3.
TABLE 1
| Amount of corrosion | Antibacterial rate | Surface condition of the surface | Amount of corrosion | Antibacterial rate | Surface condition of | ||
| Example 1 | 32mg | 99.4％ | Intact | Comparative example 1 | 153mg | 99.3％ | In general terms |
| Example 2 | 27mg | 99.5％ | Intact | Comparative example 2 | 96mg | 68.5％ | Intact |
| Example 3 | 28mg | 99.5％ | Intact | Comparative example 3 | 682mg | 99.3％ | Poor quality |
As can be seen from the comparison of the experimental data of examples 1 to 3 and comparative examples 1 to 3 in Table 1, the coating for laser film transfer prepared by the invention has good anticorrosion performance, antibacterial performance and laser film transfer effect after being applied.
The experimental data comparison of the examples 1, 2 and 3 and the comparative example 1 shows that the corrosion amount of the examples 1, 2 and 3 is low and the surface condition is intact compared with the comparative example 1, which indicates that the doped polyaniline prepared by adding the calcium lignosulphonate has a large amount of active groups, the doped polyaniline is promoted to be fused with the main body, and double bonds contained in the lignin can participate in the polymerization of free radicals, so that the curing structure is more compact, the corrosion resistance is improved, and the compact curing structure enables the whole body not to be easily separated, so that the laser film transfer effect is good; from the comparison of experimental data of examples 1, 2 and 3 and comparative example 2, it can be found that the corrosion amount of examples 1, 2 and 3 is low and the antibacterial rate is high compared with comparative example 2, which indicates that the use of the bisimidazolium salt chain extender indicates that the imidazole ring in the bisimidazolium salt chain extender is a five-membered heterocyclic conjugated structure, has an antibacterial effect and is provided with a long alkyl chain, after the electrostatic attraction of imidazole cations and bacterial cell membranes, the long alkyl chain pierces the bacterial cell membranes to accelerate the outflow of bacterial cell contents and kill bacteria, so that the antibacterial performance is improved, and after the bisimidazolium salt chain extender participates in the chain extension, the long alkyl chain makes the whole body hydrophobic on the outer side, so that the anti-corrosion performance is improved; from the comparison of experimental data of examples 1, 2 and 3 and comparative example 3, it can be seen that the corrosion amount of examples 1, 2 and 3 is low and the surface condition is good compared with comparative example 3, and the comparison of hydroxyethyl acrylate and hydroxyethyl propionate shows that the capping with hydroxyethyl acrylate makes the double imidazolium salt polyurethane oligomer contain carbon-carbon double bonds on both sides and participate in the polymerization of double bonds initiated by the photoinitiator, so that the polymer network structure is formed overall, and the corrosion resistance and the laser film transfer effect are improved.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Claims (8)
1. A preparation method of a coating for laser film transfer is characterized by mainly comprising the following preparation steps:
(1) Reacting calcium lignosulphonate with aniline to prepare doped polyaniline;
(2) Reacting imidazole with 1-bromodecane to obtain N-decyl imidazole, and reacting the N-decyl imidazole with dibromo neopentyl glycol to obtain a bis-imidazolium salt chain extender;
(3) Reacting isophorone diisocyanate, a bisimidazolium salt chain extender and polyether polyol, and capping with hydroxyethyl acrylate to obtain a bisimidazolium salt polyurethane oligomer;
(4) The paint for laser film transfer is prepared by mixing the bisimidazolium salt polyurethane acrylate oligomer, the doped polyaniline, the active diluent and the photoinitiator.
2. The preparation method of the coating for laser film transfer according to claim 1, wherein the preparation method of the coating for laser film transfer mainly comprises the following preparation steps:
(1) Preparing doped polyaniline: ammonium persulfate and 18-22% of hydrochloric acid solution in mass percentage are mixed according to the mass ratio of 1:3 to 1:4, uniformly mixing, adding aniline solution with the mass 2.7-3.1 times of that of the ammonium persulfate at a constant speed within 30-40 min under the stirring condition of 300-500 r/min at the temperature of 0-5 ℃, continuously stirring and reacting for 20-24 h after the dropwise addition is finished, filtering, washing for 3-5 times by using pure water and absolute ethyl alcohol, and drying for 6-8 h at the temperature of-1-10 ℃ under 1-10 Pa to prepare doped polyaniline;
(2) Preparation of the bisimidazolium salt chain extender: n-decyl imidazole, dibromo neopentyl glycol and dimethyl sulfoxide are mixed according to the mass ratio of 2:1: 15-2: 1:25, uniformly mixing, stirring and reacting for 14-18 h at 110-120 ℃ and 300-500 r/min in a nitrogen atmosphere, standing for 3-4 h at 20-30 ℃ and 1-2 kPa after the reaction is finished, washing for 3-5 times by using tetrahydrofuran, filtering, and drying for 6-8 h at 60-70 ℃ to obtain the bisimidazolium salt chain extender;
(3) Preparation of bisimidazolium salt polyurethane oligomer: isophorone diisocyanate and a bisimidazolium salt chain extender are mixed according to a mass ratio of 2.8:1 to 3.2:1, adding polyether polyol 4-5 times of the mass of isophorone diisocyanate and dibutyltin dilaurate 0.08-0.12 times of the mass of isophorone diisocyanate, reacting at 45-55 ℃,
stirring and reacting for 3-4 h at the speed of 300-500 r/min, adding hydroxyethyl acrylate with the mass of 0.3-0.4 time of that of isophorone diisocyanate, continuously stirring and reacting for 3-4 h, and standing for 6-8 h at the temperature of 20-30 ℃ and the pressure of 50-100 Pa to obtain a bis-imidazolium salt polyurethane oligomer;
(4) Mixing materials: the method comprises the following steps of mixing bisimidazolium salt polyurethane acrylate oligomer, doped polyaniline, an active diluent and a photoinitiator according to a mass ratio of 60:4:25:1 to 70:6:30:1, blending, stirring at the temperature of 20-30 ℃ at the speed of 800-1000 r/min for 20-30 min, and obtaining the coating for laser film transfer.
3. The method for preparing the coating for laser film transfer according to claim 2, wherein the aniline solution in the step (1) is prepared by mixing calcium lignosulphonate and pure water in a mass ratio of 1:20 to 1:25, then adding aniline with the mass 3-5 times of that of the calcium lignosulphonate, and stirring for 4-6 h at the temperature of 20-30 ℃ at the speed of 500-800 r/min.
4. The preparation method of the coating for laser film transfer according to claim 2, wherein the preparation method of the N-decyl imidazole in the step (2) comprises the following steps: imidazole, potassium hydroxide and dimethyl sulfoxide are mixed according to the mass ratio of 1.2:1:3 to 1.4:1:4, uniformly mixing, stirring and reacting for 3-4 h at 85-95 ℃ at 500-800 r/min, cooling to 10-20 ℃, adding 1-bromodecane 2.8-3 times the mass of the imidazole, stirring and reacting for 14-18 h at 60-70 ℃ at 500-800 r/min, adding pure water 14-18 times the mass of the imidazole, continuously stirring for 20-30 min, extracting for 3-5 times by using anhydrous ether, and removing the solvent by using a rotary evaporator to prepare the catalyst.
5. The method for preparing the coating for laser film transfer according to claim 2, wherein the polyether polyol in the step (3) is HSH330.
6. The method for preparing a coating for laser film transfer according to claim 2, wherein the reactive diluent in step (4) is one or more of 1, 6-hexanediol diacrylate, isobornyl acrylate, and trimethylolpropane trimethacrylate.
7. The method for preparing a coating for laser film transfer according to claim 2, wherein the photoinitiator in step (4) is 2-hydroxy-2-methyl-1-propiophenone.
8. The preparation method of the laser film transfer paint according to claim 2, wherein the application method of the laser film transfer paint comprises the following steps: 5.5 to 6g/m of coating for transferring the laser film 3 Coating the coating weight on a PET base film, rolling and pressing the PET base film and the surface of the laser film with the laser micro grooves, irradiating for 3-4 min by using an ultraviolet lamp, stripping the laser film from the coated PET base film, and standing for 10-12 h at room temperature to obtain the laser film transfer coating.
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| CN116587760A (en) * | 2023-07-19 | 2023-08-15 | 无锡臻创包装新材料科技有限公司 | Environment-friendly BOPP laser transfer film |
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