CN117586695A - Preparation method of modified polyurethane-acrylic ester cold-stamping coating - Google Patents

Preparation method of modified polyurethane-acrylic ester cold-stamping coating Download PDF

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CN117586695A
CN117586695A CN202311643637.8A CN202311643637A CN117586695A CN 117586695 A CN117586695 A CN 117586695A CN 202311643637 A CN202311643637 A CN 202311643637A CN 117586695 A CN117586695 A CN 117586695A
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modified polyurethane
mol
solvent
acrylic acid
cold
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Inventor
张斯乔
唐丘
宋之太
李颂国
宋子轩
张晨曦
吴帅男
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Jiangsu Zhonglisheng Package Technology Co ltd
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Jiangsu Zhonglisheng Package Technology Co ltd
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Abstract

The invention belongs to the technical field of high polymer materials, and relates to a preparation method of a modified polyurethane-acrylic ester cold-stamping coating, which comprises the following steps: firstly preparing a bromomethylene compound, then adding inorganic base to hydrolyze to obtain a polyhydroxy compound containing a functional structure, then obtaining a modified polyurethane-acrylic acid prepolymer with polymeric polyol, polyisocyanate and fatty acid under the action of a catalyst, finally fully dispersing and stirring the modified polyurethane-acrylic acid prepolymer in a light-proof environment by using an acrylic acid active diluent, adding a photoinitiator and a flatting agent to obtain the modified polyurethane-acrylic acid ester cold-ironing coating, and sealing and preserving the modified polyurethane-acrylic acid ester cold-ironing coating. The cold-stamping coating prepared by the invention has good compatibility for fine strokes and large fields, can meet more complex transfer patterns, and greatly widens the application scene; the cured cold-stamping coating has good thermal stability, high adhesion fastness and excellent anti-fading performance, and can be applied to the fields of foods and medicines with higher requirements on packages.

Description

Preparation method of modified polyurethane-acrylic ester cold-stamping coating
Technical Field
The invention belongs to the technical field of high polymer materials, relates to free radical polymerization and preparation of a coating, and particularly relates to a preparation method of a modified polyurethane-acrylic ester cold-stamping coating.
Background
The copolymerization modification of two or more different kinds of high polymer prepolymers is a common operation in the field of high polymer polymerization.
The acrylic ester has excellent light resistance and weather resistance and low price, and can combine the excellent performances of the acrylic ester and the polyurethane when being used for modifying polyurethane, thereby obtaining polyurethane-acrylic ester with better comprehensive performance and further widening the application range of the polyurethane-acrylic ester. Because of the different preparation principles of the two, namely addition polymerization and free radical polymerization, the key to realize the success of the two copolymerization is to find a process which can combine the two different polymerization methods, and emulsion particles prepared by the process have a core-shell composite structure.
For example, hui Ye and team thereof, preparation and Properties of Methyl Methacrylate Modified Waterborne Polyurethane membrane. Polymer Materials Science & Engineering,2017,33 (7): 144-149, reported that an acrylic-polyurethane copolymer having stable properties was successfully prepared by modifying polyurethane with methyl methacrylate, and the effect of the amount of methyl methacrylate added on emulsion and film was studied, and as a result, it was revealed that the film water resistance was increased and the thermal stability of the film was also improved as the methyl methacrylate content was increased.
For another example, zhang X and team thereof, synthesis of acrylate modified polyurethane adhesive with better weatherability and yellowing resistance, adhesion,2017, reported that in order to improve weather resistance and yellowing resistance of polyurethane, polyurethane was modified with hydroxypropyl methacrylate as a modifier, a one-component polyurethane-acrylate adhesive having excellent properties was successfully prepared, and the influence of acrylate content on curing time and shear tensile strength of a coating film was studied. The result shows that the yellowing resistance and the weather resistance of the adhesive film are improved along with the addition of acrylic ester, and when the mass fraction of the acrylic ester in the total substance is increased, the curing time tends to be prolonged, and the shearing and the tensile strength of the film layer tend to be reduced.
From this, researchers are interested in the copolymerization modification of polyurethane and acrylic ester, and research results are young and young.
Disclosure of Invention
In order to overcome the defects that the glass transition temperature is generally low and the temperature resistance is poor after the traditional printing coating is cured, the applicability of high-temperature occasions is improved by adding the methods such as nitrocotton, rigid solid particles and the like, the potential safety hazard in the use process of raw materials is brought, the printing manufacturing cost is high, the improvement effect on the temperature resistance is not satisfactory, and the invention discloses a preparation method of a modified polyurethane-acrylic ester cold-stamping coating, which can remarkably improve the temperature resistance, the mechanical strength and the like of a printed matter.
Technical proposal
A preparation method of a modified polyurethane-acrylic ester cold-stamping coating comprises the following steps:
(1) Dissolving 0.95 to 1.35mol, preferably 0.98mol, of a polymethyl compound, 0.1 to 0.7mol, preferably 0.3mol, of peroxybenzoic acid in 50 to 160mL, preferably 140mL, of a solvent and stirring, adjusting the temperature to 40 to 140 ℃, preferably 107 ℃, adding 3.0 to 9.5mol, preferably 9.1mol, of N-bromosuccinimide (NBS), and refluxing for 2 to 50 hours, preferably 22 hours; removing the solvent to obtain a bromomethylene compound; wherein the polymethyl compound comprises a main structure such as aliphatic, ester ring type or aromatic type, preferably dimethylnaphthalene; the solvent is chloroform, benzene, petroleum ether, acetonitrile, cyclohexane, ethyl acetate, methyl acetate, acetone, dioxane, isopentane, isooctane, tert-butanol, butanone, methyl ethyl ketone, isophorone, isobutyl acetate, diethyl ether acetate of oxalic acid, propylene glycol methyl ether, tetrahydrofuran, etc., preferably dioxane;
(2) Dissolving 0.90 to 1.50mol, preferably 1.12mol of bromomethylene compound with 80 to 150mL, preferably 87mL, of solvent, stirring, adjusting the temperature to 35 to 120 ℃, preferably 64 ℃, adding 3.0 to 12.0mol, preferably 11.5mol of alkali, and then preserving the temperature for 30 to 120min, preferably 95min; removing the solvent to obtain polyhydroxy compound containing functional structure; wherein the solvent is cyclohexane, toluene, ethyl acetate, methyl acetate, dimethylformamide, isopentane, isooctane, paraxylene, tertiary butanol, butanone, methyl ethyl ketone, methyl isobutyl ketone, isophorone, isobutyl acetate, diethyl ether acetate of oxalate, propylene glycol methyl ether, tetrahydrofuran, preferably tetrahydrofuran; the base is NaOH or KOH, preferably NaOH;
(3) Dissolving 0.82 to 1.52mol, preferably 1.22mol, of polymeric polyol, 1.50 to 1.90mol, preferably 1.66mol, of polyisocyanate, 0.05 to 0.54mol, preferably 0.27mol, of polyhydroxy compound containing a functional structure with 70 to 250mL, preferably 210mL, of solvent and stirring, adjusting the temperature to 85 to 240 ℃, preferably 173 ℃, adding 0.01 to 0.09mol, preferably 0.07mol, 5 to 30mg, preferably 12mg of catalyst, refluxing for 3 to 15 hours, preferably 11 hours, adding 0.01 to 0.05mol, preferably 0.03mol of hydroxy acrylic acid, and refluxing for 1 to 7 hours, preferably 3.5 hours; removing the solvent to obtain a modified polyurethane-acrylic acid prepolymer; wherein the polymeric polyol is a polyether glycol (PPG-1000, PPG-2000, NJ210, NJ220, NJ 230), polytetrahydrofuran glycol (PTMG 1000, PTMG 2000), polyepsilon caprolactone glycol (PCL 1000, PCL 2000) or the like, preferably NJ220; the polyisocyanate is 4, 4-diphenyl (yl) methane diisocyanate, 1, 6-hexamethylene diisocyanate, cyclohexane diisocyanate, 4-dicyclohexylmethane diisocyanate, 3-dimethyl-4, 4-diphenyl diisocyanate, isophorone diisocyanate, 1, 5-naphthalene diisocyanate, terephthal-ylene diisocyanate, 3-dimethylbiphenyl-4, 4-diisocyanate, etc., preferably cyclohexane diisocyanate; the fatty acid is lauric acid, myristic acid, arachidonic acid, oleic acid, linoleic acid, linolenic acid, palmitoleic acid, rapeseed oleic acid, ricinoleic acid, etc., preferably palmitoleic acid; the catalyst is N-methylimidazole, dimorpholinodiethyl ether, potassium isooctanoate, dibutyl tin oxide and the like, preferably dibutyl tin oxide; the hydroxy acrylic acid is hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, 2-hydroxypropyl acrylate, diethylene glycol monoacrylate, etc., preferably hydroxyethyl methacrylate; the solvent is cyclohexane, toluene, ethyl acetate, methyl acetate, acetone, dioxane, dimethylformamide, isopentane, isooctane, paraxylene, butanone, methyl ethyl ketone, methyl isobutyl ketone, isophorone, isobutyl acetate, diethyl ether acetate, propylene glycol methyl ether, etc., preferably methyl isobutyl ketone;
(4) 50 to 100g, preferably 61g, of modified polyurethane-acrylic acid prepolymer is fully dispersed and stirred by 2.5 to 13.4g, preferably 10.7g, of acrylic acid reactive diluent in a light-shielding environment at room temperature, 2 to 10mg, preferably 3mg, of photoinitiator and 3 to 7mg, preferably 6mg, of flatting agent are added to obtain the modified polyurethane-acrylic ester cold-ironing coating, and the modified polyurethane-acrylic ester cold-ironing coating is stored in a sealing manner; wherein the photoinitiator is 2,4,6 (trimethylbenzoyl) diphenyl phosphine oxide (TPO), ethyl 2,4, 6-trimethylbenzoyl phosphonate (TPO-L), 2-methyl-1- [ 4-methylthiophenyl ] -2-morpholinyl-1-propanone (907), 2 isopropylthioxanthone (2, 4 isomer mixture) (ITX), ethyl 4-dimethylamino-benzoate (EDB), 1-hydroxy-cyclohexyl-phenyl methanone (184), 2-hydroxy-2-methyl-1-phenyl-1-propanone (1173), benzoin dimethyl ether and the like (BDK), preferably 1173; the acrylic acid reactive diluent is n-butyl acrylate-styrene (1 mol: 0.1-1.0 mol), n-butyl acrylate-trimethylolpropane triacrylate (1 mol: 0.1-0.9 mol), n-butyl acrylate-trimethylolpropane triacrylate (1 mol: 0.1-1.2 mol), n-propyl acrylate-styrene (1 mol: 0.1-1.1 mol), n-propyl acrylate-trimethylolpropane triacrylate (1 mol: 0.1-0.8 mol), 2-methyl-2-hexyl acrylate-trimethylolpropane triacrylate (1 mol: 0.1-1.2 mol), 2-methyl-2-trimethylolpropane triacrylate (1 mol: 0.1-1.4 mol), and the like, preferably n-propyl acrylate (1 mol: 0.9 mol); the leveling agent is H-810 (CAS No.: 128192-17-6), H-850 (CAS No.: 157479-55-5), polydimethylsiloxane (CAS No.: 9016-00-6), or the like, preferably polydimethylsiloxane.
In a preferred embodiment of the present invention, the polymethyl compound in the step (1) includes an aliphatic, ester ring-shaped or aromatic main structure, wherein the aliphatic polymethyl compound is 2,3, 4-trimethylpentane, 2, 3-dimethylhexane, 2, 4-dimethylheptane, isododecane, etc.; the ester ring type polymethyl compound is 1,3, 5-trimethyl cyclohexane, 1, 3-dimethyl cyclohexane, dimethyl pentane and the like; the aromatic polymethyl compound is 1, 2-dimethylbenzene, dimethylnaphthalene, 1, 2-dimethylanthracene, 4,6, 8-trimethyl chamomile blue and the like, and the table is below.
TABLE 1 type of polymethylene compound and its main structure
Experimental method
(1) Differential thermal (DSC) test
Solidifying the cold-stamping paint by ultraviolet light to form a film, taking the small amount of sample, and placing the sample in a differential scanning calorimeter (DSC-60 Plus, shimadzu corporation) at N 2 Atmosphere, heating rate of 10 ℃/min and temperature range-measuring the glass transition temperature of the sample at 80-100 ℃;
(2) Thermogravimetric (TGA) test
Solidifying cold wave paint into film by ultraviolet light, taking the small amount of sample, placing in thermal weightlessness instrument (DTG-60 AH, shimadzu corporation) at N 2 Measuring the heat resistance of the sample under the conditions of atmosphere, temperature rising rate of 10/min and temperature range of 20-600 ℃;
(3) Cold wave effect contrast experiment
The transfer effect of the comparative cold-ironing paint and the cold-ironing paint of example 1 was tested by a cold-ironing machine (HLZ-1050, shandong Huanan mechanical Co., ltd.) respectively, the machine running speed was 37m/min, and the ultraviolet power was 38kw;
(4) Friction resistance test of cold-stamping product
The cold wave product was tested for discoloration and coating hold after a 1 minute rub test using an ink tribometer (model 2000, sutherland, usa) set at a pressure of 4 lbs. and at 85 rpm.
Conventional cold-ironing paint on the market is adopted as a comparison material.
Advantageous effects
The cold-stamping coating can be prepared by the method provided by the invention, and the source of the polymethyl compound which is one of the main raw materials is wide and the price is low; the prepared cold-stamping coating has good compatibility for fine strokes and large fields, can meet more complex transfer patterns, and greatly widens the application scene; the cured cold-stamping coating has good thermal stability, high adhesion fastness and excellent anti-fading performance, and can be applied to the fields of foods and medicines with higher requirements on packages.
Drawings
FIG. 1 shows thermodynamic test results, wherein (1) is a DCS spectrum comparing cold-ironing paint with cold-ironing paint of example 1, and (2) is a TGA spectrum comparing cold-ironing paint with cold-ironing paint of example 1;
FIG. 2 shows a comparative graph of the cold wave effect, wherein (I) is a first comparative cold wave paint, (II) is a second comparative cold wave paint, and (III) is a cold wave paint of example 1;
FIG. 3 shows the friction-resistant graph, wherein (a) is a physical graph after friction of the comparative cold-wave paint, and (b) is a physical graph after friction of the cold-wave paint of example 1.
Detailed Description
The invention will now be described in detail with reference to specific examples which will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by those skilled in the art without departing from the spirit of the invention, which falls within the scope of the invention.
Example 1
A preparation method of a modified polyurethane-acrylic ester cold-stamping coating comprises the following steps:
dissolving 0.98mol of dimethylnaphthalene and 0.3mol of peroxybenzoic acid with 140mL of dioxane, stirring, adjusting the temperature to 107 ℃, adding 9.1mol of N-bromosuccinimide, and refluxing for 22 hours; removing the solvent to obtain a bromomethylene compound;
1.12mol of the bromomethylene compound is dissolved and stirred by 87mL of tetrahydrofuran, the temperature is regulated to be 64 ℃, and 11.5mol of NaOH is added and then the temperature is kept for 95min; removing the solvent to obtain polyhydroxy compound containing functional structure;
1.22mol of NJ220, 1.66mol of cyclohexane diisocyanate and 0.27mol of polyhydroxy compound containing the functional structure are dissolved and stirred by 210mL of methyl isobutyl ketone, the temperature is regulated to 173 ℃, 0.07mol of palmitoleic acid and 12mg of dibutyl tin oxide are added, the mixture is refluxed for 11 hours, and 0.03mol of hydroxyethyl methacrylate is added and the mixture is refluxed for 3.5 hours; removing the solvent to obtain a modified polyurethane-acrylic acid prepolymer;
61g of the modified polyurethane-acrylic acid prepolymer was fully dispersed and stirred with 10.7g of n-propyl acrylate-styrene (1 mol:0.5 mol) in a dark environment at room temperature, 3mg 1173 and 6mg polydimethylsiloxane were added to obtain a modified polyurethane-acrylic acid ester cold-stamping coating, and the coating was stored in a sealed state.
The synthetic route of this embodiment is:
example 2
A preparation method of a modified polyurethane-acrylic ester cold-stamping coating comprises the following steps:
dissolving 0.95mol of dimethylnaphthalene and 0.1mol of peroxybenzoic acid with 50mL of dioxane, stirring, adjusting the temperature to 40 ℃, adding 3.0mol of N-bromosuccinimide, and refluxing for 2 hours; removing the solvent to obtain a bromomethylene compound;
dissolving 0.901.12mol of the bromomethylene compound with 80mL of tetrahydrofuran, stirring, adjusting the temperature to 35 ℃, adding 3.0mol of NaOH, and preserving the temperature for 30min; removing the solvent to obtain polyhydroxy compound containing functional structure;
Dissolving 0.82mol of NJ220, 1.50mol of cyclohexane diisocyanate and 0.05mol of polyhydroxy compound containing the functional structure with 70mL of methyl isobutyl ketone, stirring, adjusting the temperature to 85 ℃, adding 0.01mol of palmitoleic acid and 5mg of dibutyl tin oxide, refluxing for 3 hours, adding 0.01mol of hydroxyethyl methacrylate, and refluxing for 1 hour; removing the solvent to obtain a modified polyurethane-acrylic acid prepolymer;
50g of the modified polyurethane-acrylic acid prepolymer is fully dispersed and stirred by 2.5g of n-propyl acrylate-styrene (1 mol:0.1 mol) in a light-shielding environment at room temperature, and 2mg of 1173 and 3mg of polydimethylsiloxane are added to obtain the modified polyurethane-acrylic ester cold-stamping coating, and the modified polyurethane-acrylic ester cold-stamping coating is stored in a sealing mode.
Example 3
A preparation method of a modified polyurethane-acrylic ester cold-stamping coating comprises the following steps:
1.35mol of dimethylnaphthalene and 0.7mol of peroxybenzoic acid are dissolved and stirred with 160mL of dioxane, the temperature is adjusted to 140 ℃, and after 9.5mol of N-bromosuccinimide is added, reflux is carried out for 50 hours; removing the solvent to obtain a bromomethylene compound;
1.50mol of the bromomethylene compound is dissolved and stirred by 150mL of tetrahydrofuran, the temperature is regulated to 120 ℃, 12.0mol of NaOH is added, and the temperature is kept for 120min; removing the solvent to obtain polyhydroxy compound containing functional structure;
1.52mol of NJ220, 1.90mol of cyclohexane diisocyanate and 0.54mol of polyhydroxy compound containing the functional structure are dissolved and stirred by 250mL of methyl isobutyl ketone, the temperature is regulated to 240 ℃, 0.09mol of palmitoleic acid and 30mg of dibutyl tin oxide are added, the mixture is refluxed for 15 hours, and 0.05mol of hydroxyethyl methacrylate is added, and the mixture is refluxed for 7 hours; removing the solvent to obtain a modified polyurethane-acrylic acid prepolymer;
100g of the modified polyurethane-acrylic acid prepolymer is fully dispersed and stirred by 13.4g of n-propyl acrylate-styrene (1 mol:1.1 mol) in a light-shielding environment at room temperature, 10mg 1173 and 7mg of polydimethylsiloxane are added to obtain the modified polyurethane-acrylic ester cold-stamping coating, and the modified polyurethane-acrylic ester cold-stamping coating is stored in a sealing mode.
Example 4
A preparation method of a modified polyurethane-acrylic ester cold-stamping coating comprises the following steps:
0.96mol of 2,3, 4-trimethylpentane and 0.2mol of peroxybenzoic acid are dissolved and stirred with 60mL of chloroform, the temperature is regulated to 50 ℃, and 4.0mol of N-bromosuccinimide is added and then refluxed for 3 hours; removing the solvent to obtain a bromomethylene compound;
1.0mol of the bromomethylene compound is dissolved and stirred by 90mL of cyclohexane, the temperature is regulated to 40 ℃, and the temperature is kept for 40min after 4.0mol of KOH is added; removing the solvent to obtain polyhydroxy compound containing functional structure;
0.90mol of PPG-1000, 1.6mol of 4, 4-diphenyl (yl) methane diisocyanate and 0.06mol of the polyhydroxy compound containing the functional structure are dissolved and stirred by 80mL of cyclohexane, the temperature is regulated to 90 ℃, 0.02mol of lauric acid and 4mg of N-methylimidazole are added, the mixture is refluxed for 4 hours, and 0.02mol of hydroxyethyl acrylate is added, and the mixture is refluxed for 2 hours; removing the solvent to obtain a modified polyurethane-acrylic acid prepolymer;
60g of the modified polyurethane-acrylic acid prepolymer is fully dispersed and stirred by 3.1g of n-butyl acrylate-styrene (1 mol:0.5 mol) in a light-shielding environment at room temperature, 4mg of TPO and 4mg of H-810 are added to obtain the modified polyurethane-acrylic acid ester cold-stamping coating, and the modified polyurethane-acrylic acid ester cold-stamping coating is stored in a sealing mode.
Example 5
A preparation method of a modified polyurethane-acrylic ester cold-stamping coating comprises the following steps:
0.97mol of 2, 3-dimethylhexane and 0.4mol of peroxybenzoic acid are dissolved with 70mL of benzene and stirred, the temperature is regulated to 60 ℃, and after 5.0mol of N-bromosuccinimide is added, reflux is carried out for 4 hours; removing the solvent to obtain a bromomethylene compound;
1.1mol of the bromomethylene compound is dissolved and stirred with 100mL of toluene, the temperature is regulated to 55 ℃, and 6.0mol of NaOH is added and then the temperature is kept for 42min; removing the solvent to obtain polyhydroxy compound containing functional structure;
1.03mol of PPG-2000, 1.71mol of 1, 6-hexamethylene diisocyanate and 0.26mol of the polyhydroxy compound containing the functional structure are dissolved and stirred by using 95mL of ethyl acetate, the temperature is regulated to 93 ℃, 0.04mol of myristic acid and 14mg of dimorpholinodiethyl ether are added, the mixture is refluxed for 5 hours, and 0.04mol of hydroxypropyl acrylate is added, and the mixture is refluxed for 2.5 hours; removing the solvent to obtain a modified polyurethane-acrylic acid prepolymer;
at room temperature in a dark environment, 62g of the modified polyurethane-acrylic acid prepolymer is fully dispersed and stirred by 7.8g of n-butyl acrylate-tripropylene glycol diacrylate (1 mol:0.2 mol), 4.4mg of ITX and 3.1mg of H-850 are added to obtain the modified polyurethane-acrylic acid ester cold wave paint, and the paint is stored in a sealing mode.
Example 6
A preparation method of a modified polyurethane-acrylic ester cold-stamping coating comprises the following steps:
0.99mol of isododecane and 0.6mol of peroxybenzoic acid are dissolved and stirred with 92mL of cyclohexane, the temperature is regulated to 112 ℃, and 4.7mol of N-bromosuccinimide is added and then refluxed for 41 hours; removing the solvent to obtain a bromomethylene compound;
1.47mol of the bromomethylene compound is dissolved and stirred with 121mL of dimethylformamide, the temperature is adjusted to 85 ℃, and 10.3mol of KOH is added and then the temperature is kept for 72min; removing the solvent to obtain polyhydroxy compound containing functional structure;
Dissolving 0.95mol of NJ230, 1.74mol of 3, 3-dimethyl-4, 4-diphenyl diisocyanate and 0.08mol of the polyhydroxy compound containing the functional structure by using 190mL of dioxane, stirring, adjusting the temperature to 164 ℃, adding 0.07mol of oleic acid and 12.5mg of potassium isooctanoate, refluxing for 7 hours, adding 0.03mol of 2-hydroxypropyl 2-acrylate, and refluxing for 5 hours; removing the solvent to obtain a modified polyurethane-acrylic acid prepolymer;
83g of the modified polyurethane-acrylic acid prepolymer is fully dispersed and stirred by 7.6g of n-butyl acrylate-trimethylolpropane triacrylate (1 mol:1.1 mol) in a light-shielding environment at room temperature, 9mg 184 and 6mg H-850 are added to obtain the modified polyurethane-acrylic acid ester cold-stamping coating, and the modified polyurethane-acrylic acid ester cold-stamping coating is stored in a sealed mode.
Example 7
A preparation method of a modified polyurethane-acrylic ester cold-stamping coating comprises the following steps:
0.96mol of isododecane and 0.3mol of peroxybenzoic acid are dissolved and stirred with 94mL of isopentane, the temperature is regulated to 70 ℃, and 4.3mol of N-bromosuccinimide is added and then refluxed for 40 hours; removing the solvent to obtain a bromomethylene compound;
1.22mol of the bromomethylene compound is dissolved and stirred with 86mL of paraxylene, the temperature is regulated to 59 ℃, and 10.6mol of NaOH is added and then the temperature is kept for 105min; removing the solvent to obtain polyhydroxy compound containing functional structure;
Dissolving 0.93mol of PTMG1000, 1.68mol of isophorone diisocyanate and 0.07mol of the polyhydroxy compound containing the functional structure with 103mL of dimethylformamide, stirring, adjusting the temperature to 182 ℃, adding 0.05mol of linoleic acid and 10.5mg of potassium isooctanoate, refluxing for 14h, adding 0.02mol of 2-hydroxypropyl 2-acrylate, and refluxing for 6.5h; removing the solvent to obtain a modified polyurethane-acrylic acid prepolymer;
54g of the modified polyurethane-acrylic acid prepolymer is fully dispersed and stirred by 11.3g of n-propyl acrylate-tripropylene glycol diacrylate (1 mol:0.4 mol) in a light-shielding environment at room temperature, 7mg of BDK and 5mg of H-810 are added to obtain the modified polyurethane-acrylic acid ester cold-stamping coating, and the modified polyurethane-acrylic acid ester cold-stamping coating is stored in a sealing mode.
Example 8
A preparation method of a modified polyurethane-acrylic ester cold-stamping coating comprises the following steps:
1.19mol of 1, 2-dimethylbenzene and 0.6mol of peroxybenzoic acid are dissolved and stirred with 80mL of tertiary butanol, the temperature is regulated to 55 ℃, and after 4.8mol of N-bromosuccinimide is added, reflux is carried out for 32h; removing the solvent to obtain a bromomethylene compound;
1.40mol of the bromomethylene compound is dissolved and stirred with 99mL of methyl ethyl ketone, the temperature is regulated to 74 ℃, and the mixture is kept for 50min after 4.6mol of KOH is added; removing the solvent to obtain polyhydroxy compound containing functional structure;
Dissolving 0.92mol of PTMG2000, 1.69mol of 1, 5-naphthalene diisocyanate and 0.19mol of the polyhydroxy compound containing the functional structure with 110mL of isooctane, stirring, adjusting the temperature to 233 ℃, adding 0.02mol of linolenic acid and 17mg of potassium isooctanoate, refluxing for 8 hours, adding 0.02mol of 2-hydroxy propyl 2-acrylate, and refluxing for 6 hours; removing the solvent to obtain a modified polyurethane-acrylic acid prepolymer;
at room temperature in a dark environment, 95g of the modified polyurethane-acrylic acid prepolymer is fully dispersed and stirred by 3.0g of n-propyl acrylate-trimethylolpropane triacrylate (1 mol:0.1 mol), 3mg of EDB and 4mg of H-810 are added to obtain the modified polyurethane-acrylic acid ester cold-stamping coating, and the modified polyurethane-acrylic acid ester cold-stamping coating is stored in a sealing mode.
Example 9
A preparation method of a modified polyurethane-acrylic ester cold-stamping coating comprises the following steps:
1.31mol of 1, 2-dimethyl anthracene and 0.5mol of peroxybenzoic acid are dissolved and stirred with 83mL of isophorone, the temperature is adjusted to 108 ℃, and after 5.3mol of N-bromosuccinimide is added, the mixture is refluxed for 32 hours; removing the solvent to obtain a bromomethylene compound;
1.45mol of the bromomethylene compound is dissolved and stirred with 99mL of isobutyl acetate, the temperature is regulated to 36 ℃, 8.7mol of NaOH is added, and the temperature is kept for 65min; removing the solvent to obtain polyhydroxy compound containing functional structure;
Dissolving 0.95mol of PCL2000, 1.74mol of p-phenylene diisocyanate and 0.38mol of polyhydroxy compound containing the functional structure with 110mL of isobutyl acetate, stirring, adjusting the temperature to 102 ℃, adding 0.07mol of rapeseed oleic acid and 4.3mg of N-methylimidazole, refluxing for 13h, adding 0.04mol of diethylene glycol monoacrylate, and refluxing for 5h; removing the solvent to obtain a modified polyurethane-acrylic acid prepolymer;
67g of the modified polyurethane-acrylic acid prepolymer is fully dispersed and stirred by 3.0g of n-propyl acrylate-trimethylolpropane triacrylate (1 mol:0.8 mol) in a light-shielding environment at room temperature, 9mg of BDK and 4mg of H-850 are added to obtain the modified polyurethane-acrylic acid ester cold-stamping coating, and the modified polyurethane-acrylic acid ester cold-stamping coating is stored in a sealing mode.
Example 10
A preparation method of a modified polyurethane-acrylic ester cold-stamping coating comprises the following steps:
1.12mol of 4,6, 8-trimethyl chamomile blue and 0.5mol of peroxybenzoic acid are dissolved and stirred with 150mL of propylene glycol methyl ether, the temperature is regulated to 88 ℃, and after 6.2mol of N-bromosuccinimide is added, the mixture is refluxed for 21 hours; removing the solvent to obtain a bromomethylene compound;
1.17mol of the bromomethylene compound is dissolved and stirred by 120mL of propylene glycol methyl ether, the temperature is regulated to 78 ℃, and the temperature is kept for 80min after 6.0mol of KOH is added; removing the solvent to obtain polyhydroxy compound containing functional structure;
Dissolving 1.08mol of NJ210, 1.54mol of 3, 3-dimethylbiphenyl-4, 4-diisocyanate and 0.38mol of the polyhydroxy compound containing the functional structure by using 230mL of propylene glycol methyl ether, stirring, adjusting the temperature to 155 ℃, adding 0.07mol of rapeseed oleic acid and 13mg of N-methylimidazole, refluxing for 14 hours, adding 0.03mol of 2-hydroxypropyl 2-acrylate, and refluxing for 2.5 hours; removing the solvent to obtain a modified polyurethane-acrylic acid prepolymer;
90g of the modified polyurethane-acrylic acid prepolymer is fully dispersed and stirred by 13.2g of 2-methyl-2-hexyl acrylate-styrene (1 mol:1.1 mol) in a light-shielding environment at room temperature, 6mg of BDK and 4.5mg of H-850 are added to obtain the modified polyurethane-acrylic acid ester cold wave coating, and the modified polyurethane-acrylic acid ester cold wave coating is stored in a sealing mode.
Example 11
A preparation method of a modified polyurethane-acrylic ester cold-stamping coating comprises the following steps:
1.21mol of 1, 2-dimethyl anthracene and 0.65mol of peroxybenzoic acid are dissolved and stirred with 85mL of diethyl oxalate acetate, the temperature is regulated to 64 ℃, 7.3mol of N-bromosuccinimide is added and then the mixture is refluxed for 45 hours; removing the solvent to obtain a bromomethylene compound;
0.94mol of the bromomethylene compound is dissolved and stirred with 141mL of methyl ethyl ketone, the temperature is regulated to 52 ℃, 3.6mol of NaOH is added, and the temperature is kept for 45min; removing the solvent to obtain polyhydroxy compound containing functional structure;
Dissolving 1.01mol of PTMG1000, 1.78mol of 3, 3-dimethylbiphenyl-4, 4-diisocyanate and 0.28mol of the polyhydroxy compound containing the functional structure with 210mL of paraxylene, stirring, adjusting the temperature to 160 ℃, adding 0.02mol of ricinoleic acid and 13mg of potassium isooctanoate, refluxing for 10 hours, adding 0.03mol of diethylene glycol monoacrylate, and refluxing for 5 hours; removing the solvent to obtain a modified polyurethane-acrylic acid prepolymer;
68g of the modified polyurethane-acrylic acid prepolymer is fully dispersed and stirred by 11.7g of 2-methyl-2-hexyl acrylate-trimethylolpropane triacrylate (1 mol:0.8 mol) in a light-shielding environment at room temperature, 4mg of TPO and 4mg of H-850 are added to obtain the modified polyurethane-acrylic acid ester cold-stamping coating, and the modified polyurethane-acrylic acid ester cold-stamping coating is stored in a sealing manner.
Example 12
A preparation method of a modified polyurethane-acrylic ester cold-stamping coating comprises the following steps:
1.06mol of dimethylpentane and 0.2mol of peroxybenzoic acid are dissolved and stirred with 60mL of isobutyl acetate, the temperature is adjusted to 67 ℃, and after 8.7mol of N-bromosuccinimide is added, the mixture is refluxed for 14 hours; removing the solvent to obtain a bromomethylene compound;
1.41mol of the bromomethylene compound is dissolved and stirred with 88mL of tertiary butanol, the temperature is regulated to 92 ℃, and after 4.2mol of NaOH is added, the temperature is kept for 97min; removing the solvent to obtain polyhydroxy compound containing functional structure;
1.06mol of PTMG2000, 1.51mol of 3, 3-dimethylbiphenyl-4, 4-diisocyanate and 0.09mol of the polyhydroxy compound containing the functional structure are dissolved and stirred by 208mL of dimethylformamide, the temperature is regulated to 91 ℃, 0.08mol of ricinoleic acid and 11mg of potassium isooctanoate are added, the mixture is refluxed for 11.5 hours, and 0.03mol of diethylene glycol monoacrylate is added, and the mixture is refluxed for 1.5 hours; removing the solvent to obtain a modified polyurethane-acrylic acid prepolymer;
90g of the modified polyurethane-acrylic acid prepolymer is fully dispersed and stirred by 10.7g of 2-methyl-2-hexyl acrylate-trimethylolpropane triacrylate (1 mol:0.1 mol) in a light-shielding environment at room temperature, 3mg of TPO and 3.5mg of H-850 are added to obtain the modified polyurethane-acrylic acid ester cold wave paint, and the modified polyurethane-acrylic acid ester cold wave paint is stored in a sealing mode.
Example 13
A preparation method of a modified polyurethane-acrylic ester cold-stamping coating comprises the following steps:
1.33mol of dimethylpentane and 0.15mol of peroxybenzoic acid are dissolved and stirred with 80mL of tetrahydrofuran, the temperature is adjusted to 43 ℃, and after 5.6mol of N-bromosuccinimide is added, the mixture is refluxed for 28 hours; removing the solvent to obtain a bromomethylene compound;
dissolving 0.93mol of bromomethylene compound with 128mL of paraxylene, stirring, adjusting the temperature to 83 ℃, adding 10.6mol of NaOH, and preserving the temperature for 30min; removing the solvent to obtain polyhydroxy compound containing functional structure;
1.05mol of PCL2000, 1.78mol of 3, 3-dimethylbiphenyl-4, 4-diisocyanate and 0.29mol of the polyhydroxy compound containing the functional structure are dissolved and stirred by 130mL of diethyl oxalate acetate, the temperature is regulated to 122 ℃, 0.06mol of linolenic acid and 24mg of N-methylimidazole are added, the mixture is refluxed for 12 hours, and 0.03mol of hydroxypropyl acrylate is added, and the mixture is refluxed for 6.5 hours; removing the solvent to obtain a modified polyurethane-acrylic acid prepolymer;
89g of the modified polyurethane-acrylic acid prepolymer is fully dispersed and stirred by 3.4g of 2-methyl-2-hexyl acrylate-tripropylene glycol diacrylate (1 mol: 0.1-1.3 mol) in a light-shielding environment at room temperature, 8.6mg 907 and 3.6mg H-850 are added to obtain the modified polyurethane-acrylic acid ester cold-ironing coating, and the modified polyurethane-acrylic acid ester cold-ironing coating is stored in a sealing mode.
Example 14
A preparation method of a modified polyurethane-acrylic ester cold-stamping coating comprises the following steps:
1.11mol of 1, 3-dimethylcyclohexane and 0.2mol of peroxybenzoic acid are dissolved and stirred with 58mL of isophorone, the temperature is adjusted to 42 ℃, and 3.1mol of N-bromosuccinimide is added and then refluxed for 28 hours; removing the solvent to obtain a bromomethylene compound;
1.48mol of the bromomethylene compound is dissolved and stirred by 93mL of propylene glycol methyl ether, the temperature is regulated to 39 ℃, and the mixture is kept for 110min after 11.2mol of NaOH is added; removing the solvent to obtain polyhydroxy compound containing functional structure;
1.50mol of PCL1000, 1.78mol of 4, 4-dicyclohexylmethane diisocyanate and 0.19mol of the polyhydroxy compound containing the functional structure are dissolved and stirred by 200mL of dimethylformamide, the temperature is regulated to 162 ℃, 0.03mol of ricinoleic acid and 17mg of dimorpholinyl diethyl ether are added, the mixture is refluxed for 10.5 hours, and 0.03mol of diethylene glycol monoacrylate is added, and the mixture is refluxed for 4.5 hours; removing the solvent to obtain a modified polyurethane-acrylic acid prepolymer;
at room temperature in a dark environment, 63g of the modified polyurethane-acrylic acid prepolymer is fully dispersed and stirred by 8.3g of n-propyl acrylate-tripropylene glycol diacrylate (1 mol: 0.1-0.7 mol), and 2.3mg184 and 7mg of polydimethylsiloxane are added to obtain the modified polyurethane-acrylic acid ester cold-stamping coating, and the modified polyurethane-acrylic acid ester cold-stamping coating is stored in a sealed mode.
Example 15
A preparation method of a modified polyurethane-acrylic ester cold-stamping coating comprises the following steps:
1.22mol of 1, 3-dimethylcyclohexane and 0.4mol of peroxybenzoic acid are dissolved and stirred with 51mL of acetone, the temperature is regulated to 75 ℃, and after 8.8mol of N-bromosuccinimide is added, the mixture is refluxed for 9 hours; removing the solvent to obtain a bromomethylene compound;
1.47mol of the bromomethylene compound is dissolved and stirred with 87mL of paraxylene, the temperature is regulated to 52 ℃, and 11.5mol of KOH is added and then the temperature is kept for 112min; removing the solvent to obtain polyhydroxy compound containing functional structure;
1.22mol of PCL2000, 1.65mol of 3, 3-dimethyl-4, 4-diphenyl diisocyanate and 0.09mol of the polyhydroxy compound containing the functional structure are dissolved and stirred by 73mL of dioxane, the temperature is regulated to 165 ℃, 0.07mol of ricinoleic acid and 10mg of dibutyl tin oxide are added, the mixture is refluxed for 14 hours, and 0.03mol of hydroxypropyl acrylate is added, and the mixture is refluxed for 2 hours; removing the solvent to obtain a modified polyurethane-acrylic acid prepolymer;
79g of the modified polyurethane-acrylic acid prepolymer is fully dispersed and stirred by 10.6g of n-butyl acrylate-tripropylene glycol diacrylate (1 mol:0.2 mol) in a light-shielding environment at room temperature, 9.2mg of EDB and 4mg of H-850 are added to obtain the modified polyurethane-acrylic acid ester cold-stamping coating, and the modified polyurethane-acrylic acid ester cold-stamping coating is stored in a sealing mode.
Example 16
A preparation method of a modified polyurethane-acrylic ester cold-stamping coating comprises the following steps:
0.99mol of 1, 2-dimethyl anthracene and 0.6mol of peroxybenzoic acid are dissolved and stirred by 155mL of butanone, the temperature is regulated to 59 ℃, and after 9.2mol of N-bromosuccinimide is added, the mixture is refluxed for 41 hours; removing the solvent to obtain a bromomethylene compound;
0.92mol of the bromomethylene compound is dissolved and stirred with 107mL of isobutyl acetate, the temperature is regulated to 88 ℃, 3.1mol of KOH is added, and the temperature is kept for 114min; removing the solvent to obtain polyhydroxy compound containing functional structure;
Dissolving 0.99mol of PCL1000, 1.75mol of 1, 5-naphthalene diisocyanate and 0.47mol of the polyhydroxy compound containing the functional structure with 180mL of isopentane, stirring, adjusting the temperature to 163 ℃, adding 0.07mol of ricinoleic acid and 25mg of potassium isooctanoate, refluxing for 10 hours, adding 0.02mol of hydroxyethyl acrylate, and refluxing for 4.5 hours; removing the solvent to obtain a modified polyurethane-acrylic acid prepolymer;
96g of the modified polyurethane-acrylic acid prepolymer is fully dispersed and stirred by 10.7g of 2-methyl-2-hexyl acrylate-trimethylolpropane triacrylate (1 mol:0.7 mol) in a light-shielding environment at room temperature, 4mg of TPO and 3.2mg of H-850 are added to obtain the modified polyurethane-acrylic acid ester cold wave paint, and the modified polyurethane-acrylic acid ester cold wave paint is stored in a sealing manner.
Example 17
A preparation method of a modified polyurethane-acrylic ester cold-stamping coating comprises the following steps:
1.24mol of 1, 2-dimethyl anthracene and 0.3mol of peroxybenzoic acid are dissolved and stirred with 150mL of isooctane, the temperature is regulated to 74 ℃, and after 9.3mol of N-bromosuccinimide is added, reflux is carried out for 42h; removing the solvent to obtain a bromomethylene compound;
1.29mol of the bromomethylene compound is dissolved and stirred with 82mL of dimethylformamide, the temperature is regulated to 68 ℃, and the mixture is kept for 77min after 11.5mol of KOH is added; removing the solvent to obtain polyhydroxy compound containing functional structure;
1.25mol of PCL1000, 1.81mol of terephthalylene diisocyanate and 0.09mol of polyhydroxy compound containing the functional structure are dissolved and stirred by 187mL of isooctane, the temperature is regulated to 86 ℃, 0.06mol of arachidonic acid and 29mg of dibutyltin oxide are added, the mixture is refluxed for 4 hours, and 0.04mol of diethylene glycol monoacrylate is added, and the mixture is refluxed for 2.5 hours; removing the solvent to obtain a modified polyurethane-acrylic acid prepolymer;
71g of the modified polyurethane-acrylic acid prepolymer is fully dispersed and stirred by 10.9g of n-butyl acrylate-trimethylolpropane triacrylate (1 mol:0.7 mol) in a light-shielding environment at room temperature, 3.8mg of BDK and 6.3mg of H-850 are added to obtain the modified polyurethane-acrylic acid ester cold wave coating, and the modified polyurethane-acrylic acid ester cold wave coating is stored in a sealing mode.
Example 18
A preparation method of a modified polyurethane-acrylic ester cold-stamping coating comprises the following steps:
1.34mol of 1, 3-dimethylcyclohexane and 0.6mol of peroxybenzoic acid are dissolved and stirred with 87mL of butanone, the temperature is regulated to 99 ℃, and after 8.1mol of N-bromosuccinimide is added, the mixture is refluxed for 13 hours; removing the solvent to obtain a bromomethylene compound;
0.94mol of the bromomethylene compound is dissolved and stirred with 86mL of isooctane, the temperature is regulated to 68 ℃, and 11.2mol of KOH is added and then the temperature is kept for 32min; removing the solvent to obtain polyhydroxy compound containing functional structure;
1.28mol of NJ230, 1.68mol of isophorone diisocyanate and 0.39mol of the polyhydroxy compound containing the functional structure are dissolved and stirred by 208mL of isooctane, the temperature is regulated to 89 ℃, 0.07mol of ricinoleic acid and 23mg of dimorpholinodiethyl ether are added, the mixture is refluxed for 10 hours, and 0.03mol of diethylene glycol monoacrylate is added, and the mixture is refluxed for 6 hours; removing the solvent to obtain a modified polyurethane-acrylic acid prepolymer;
71g of the modified polyurethane-acrylic acid prepolymer is fully dispersed and stirred by 10.9g of n-propyl acrylate-styrene (1 mol:0.3 mol) in a light-shielding environment at room temperature, 8mg of BDK and 5mg of H-850 are added to obtain the modified polyurethane-acrylic acid ester cold-stamping coating, and the modified polyurethane-acrylic acid ester cold-stamping coating is stored in a sealing mode.
Example 19
A preparation method of a modified polyurethane-acrylic ester cold-stamping coating comprises the following steps:
1.14mol of 1, 3-dimethylcyclohexane and 0.3mol of peroxybenzoic acid are dissolved and stirred with 70mL of propylene glycol methyl ether, the temperature is regulated to 128 ℃, and 9.4mol of N-bromosuccinimide is added and then refluxed for 43 hours; removing the solvent to obtain a bromomethylene compound;
1.47mol of the bromomethylene compound is dissolved and stirred with 86mL of dimethylformamide, the temperature is regulated to 55 ℃, and 3.2mol of NaOH is added and then the temperature is kept for 112min; removing the solvent to obtain polyhydroxy compound containing functional structure;
1.44mol of PTMG2000, 1.52mol of 3, 3-dimethyl-4, 4-diphenyl diisocyanate and 0.51mol of the polyhydroxy compound containing the functional structure are dissolved and stirred by 89mL of dimethylformamide, the temperature is regulated to 153 ℃, 0.07mol of lauric acid and 13mg of N-methylimidazole are added, the mixture is refluxed for 14 hours, and 0.02mol of 2-hydroxypropyl 2-acrylate is added and the mixture is refluxed for 2.5 hours; removing the solvent to obtain a modified polyurethane-acrylic acid prepolymer;
51g of the modified polyurethane-acrylic acid prepolymer is fully dispersed and stirred by 10.7g of n-butyl acrylate-tripropylene glycol diacrylate (1 mol:0.7 mol) in a light-shielding environment at room temperature, 8mg of EDB and 5mg of H-850 are added to obtain the modified polyurethane-acrylic acid ester cold-stamping coating, and the modified polyurethane-acrylic acid ester cold-stamping coating is stored in a sealing mode.
Example 20
A preparation method of a modified polyurethane-acrylic ester cold-stamping coating comprises the following steps:
1.06mol of 2,3, 4-trimethylpentane and 0.4mol of peroxybenzoic acid are dissolved and stirred with 133mL of cyclohexane, the temperature is adjusted to 77 ℃, and after 9.1mol of N-bromosuccinimide is added, the mixture is refluxed for 25 hours; removing the solvent to obtain a bromomethylene compound;
1.27mol of the bromomethylene compound is dissolved and stirred with 80mL of isobutyl acetate, the temperature is regulated to 36 ℃, and the mixture is kept for 58min after 11.6mol of KOH is added; removing the solvent to obtain polyhydroxy compound containing functional structure;
1.39mol of PTMG1000, 1.68mol of terephthalylene diisocyanate and 0.07mol of polyhydroxy compound containing the functional structure are dissolved and stirred by 240mL of toluene, the temperature is regulated to 162 ℃, 0.08mol of rapeseed oleic acid and 13mg of potassium isooctanoate are added, the mixture is refluxed for 10 hours, and 0.03mol of hydroxypropyl acrylate is added, and the mixture is refluxed for 2.5 hours; removing the solvent to obtain a modified polyurethane-acrylic acid prepolymer;
83g of the modified polyurethane-acrylic acid prepolymer is fully dispersed and stirred by 2.5g of n-propyl acrylate-trimethylolpropane triacrylate (1 mol:0.6 mol) in a light-shielding environment at room temperature, 7mg 184 and 6mg H-850 are added to obtain the modified polyurethane-acrylic acid ester cold-stamping coating, and the modified polyurethane-acrylic acid ester cold-stamping coating is stored in a sealing mode.
Experimental results and analysis
(1) The differential thermal (DSC) test was used to compare the DSC profile of the cold-ironing paint with that of example 1, as shown in fig. 1 (1). It can be seen that the Tg 27.09 ℃ of the cold-stamping coating of example 1 is lower than the Tg 29.54 ℃ of the comparative cold-stamping coating, mainly because the modified polyurethane-acrylic resin molecular chain prepared by taking the polyhydroxy compound with a functional structure as a chain extender has higher flexibility, and the Tg is obviously reduced, which indicates that the cold-stamping coating prepared by the technical scheme can form a film at a lower environmental temperature. Thermal stability of the comparative cold-iron coating was tested with the cold-iron coating of example 1 using Thermogravimetric (TGA) testing, as shown in fig. 1 (2). It can be seen that the mass loss of both samples is small when the temperature is below 200 ℃; the rate of weight loss of both resins is significantly faster at temperatures > 200 ℃, presumably because of the volatilization of the non-volatilized solvent and the unreacted, completely small monomers in the sample cured film; as the temperature increases above 350 ℃, the thermal decomposition rates of the two samples become significantly faster, the maximum thermal weight loss rate temperatures are 452.6 ℃ and 454.5 ℃ respectively, and the two samples begin to thermally decompose. As can be seen from comprehensive analysis, the cold-stamping coating of the embodiment 1 has heat resistance which is not inferior to that of the comparative cold-stamping coating, and the curing condition is milder.
(2) The transfer effect of two commercially available cold wave paints and the cold wave paint of example 1 were respectively tested, and the test results are shown in fig. 2. It can be seen that under the same transfer printing conditions (the machine running speed is 37m/min and the ultraviolet light power is 38 kw), the first cold-iron coating has obvious pen breakage phenomenon in the fine stroke area and obvious deletion in the large field area, the second cold-iron coating has clear lines in the fine stroke area and obvious deletion in the large field area, and the cold-iron coating in embodiment 1 has good transfer coverage effect in both the fine stroke area and the large field area. Comprehensive analysis can show that the cold-stamping paint of the embodiment 1 can simultaneously meet the working scene of combining fine strokes with large fields, and has excellent transfer printing effect and higher yield.
(3) The coatings of the cold wave paint purchased in the market and the finished product of the cold wave paint of the embodiment 1 are respectively tested. The test results are shown in FIG. 3. It can be seen that the coating is obviously damaged after the comparative cold-stamping coating is subjected to friction test, and a fading trace is left on the surface of the white paper, while the coating is hardly damaged after the coating is subjected to friction test in the example 1, and the fading trace on the surface of the white paper is negligible. Comprehensive analysis shows that the interlayer binding force of the cold-stamping coating of the embodiment 1 is higher, namely the adhesion fastness of the cold-stamping coating is better.
The foregoing description is only illustrative of the present invention and is not intended to limit the scope of the invention, and all equivalent structures or equivalent processes or direct or indirect application in other related technical fields are included in the scope of the present invention.

Claims (10)

1. The preparation method of the modified polyurethane-acrylic ester cold-stamping coating is characterized by comprising the following steps of:
(1) Dissolving 0.95-1.35 mol of a polymethyl compound and 0.1-0.7 mol of peroxybenzoic acid with 50-160 mL of solvent, stirring, adjusting the temperature to 40-140 ℃, adding 3.0-9.5 mol of N-bromosuccinimide, refluxing for 2-50 h, and removing the solvent to obtain a bromomethylene compound; wherein the polymethylene compound comprises an aliphatic, ester cyclic, or aromatic host structure; the solvent is chloroform, benzene, petroleum ether, acetonitrile, cyclohexane, ethyl acetate, methyl acetate, acetone, dioxane, isopentane, isooctane, tertiary butanol, butanone, methyl ethyl ketone, isophorone, isobutyl acetate, diethyl oxalate acetate, propylene glycol methyl ether and tetrahydrofuran;
(2) Dissolving 0.90-1.50 mol of bromomethylene compound with 80-150 mL of solvent, stirring, adjusting the temperature to 35-120 ℃, adding 3.0-12.0 mol of alkali, preserving the heat for 30-120 min, and removing the solvent to obtain polyhydroxy compound containing a functional structure; wherein the solvent is cyclohexane, toluene, ethyl acetate, methyl acetate, dimethylformamide, isopentane, isooctane, paraxylene, tertiary butanol, butanone, methyl ethyl ketone, methyl isobutyl ketone, isophorone, isobutyl acetate, diethyl ether acetate oxalate, propylene glycol methyl ether, tetrahydrofuran; the alkali is NaOH or KOH;
(3) Dissolving 0.82-1.52 mol of polymeric polyol, 1.50-1.90 mol of polyisocyanate and 0.05-0.54 mol of polyhydroxy compound containing a functional structure by using 70-250 mL of solvent, stirring, adjusting the temperature to 85-240 ℃, adding 0.01-0.09 mol of fatty acid and 5-30 mg of catalyst, refluxing for 3-15 h, adding 0.01-0.05 mol of hydroxy acrylic acid, refluxing for 1-7 h, and removing the solvent to obtain a modified polyurethane-acrylic acid prepolymer; wherein the polymeric polyol is polyether glycol PPG-1000, PPG-2000, NJ210, NJ220, NJ230, polytetrahydrofuran glycol PTMG1000, PTMG2000, polyepsilon caprolactone diol PCL1000, PCL2000; the polyisocyanate is 4, 4-diphenyl (yl) methane diisocyanate, 1, 6-hexamethylene diisocyanate, cyclohexane diisocyanate, 4-dicyclohexylmethane diisocyanate, 3-dimethyl-4, 4-diphenyl diisocyanate, isophorone diisocyanate, 1, 5-naphthalene diisocyanate, terephthal-ylene diisocyanate, terephthal-methylene diisocyanate, 3-dimethylbiphenyl-4, 4-diisocyanate; the fatty acid is lauric acid, myristic acid, arachidonic acid, oleic acid, linoleic acid, linolenic acid, palmitoleic acid, rapeseed oleic acid, and ricinoleic acid; the catalyst is N-methylimidazole, dimorpholinodiethyl ether, potassium isooctanoate and dibutyl tin oxide; the hydroxy acrylic acid is hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, 2-hydroxypropyl acrylate, diethylene glycol monoacrylate; the solvent is cyclohexane, toluene, ethyl acetate, methyl acetate, acetone, dioxane, dimethylformamide, isopentane, isooctane, paraxylene, butanone, methyl ethyl ketone, methyl isobutyl ketone, isophorone, isobutyl acetate, diethyl ether acetate, propylene glycol methyl ether;
(4) Dispersing and stirring 50-100 g of modified polyurethane-acrylic acid prepolymer with 2.5-13.4 g of acrylic acid reactive diluent, adding 2-10 mg of photoinitiator and 3-7 mg of flatting agent at room temperature in a dark place to obtain modified polyurethane-acrylic ester cold-ironing paint, and sealing and preserving; wherein the photoinitiator is 2,4,6 (trimethylbenzoyl) diphenyl phosphine oxide TPO, ethyl 2,4, 6-trimethylbenzoyl phosphonate TPO-L, 2-methyl-1- [ 4-methylthiophenyl ] -2-morpholino-1-propanone 907, 2 isopropylthioxanthone (2, 4 isomer mixture) ITX, 4-dimethylamino-ethyl benzoate EDB, 1-hydroxy-cyclohexyl-phenyl ketone 184, 2-hydroxy-2-methyl-1-phenyl-1-propanone 1173, benzoin dimethyl ether BDK; the acrylic acid reactive diluent is 1 mol:0.1-1.0 mol of n-butyl acrylate-styrene, 1 mol:0.1-0.9 mol of n-butyl acrylate-trimethylolpropane triacrylate, 1 mol:0.1-1.2 mol of n-butyl acrylate-trimethylolpropane triacrylate, 1 mol:0.1-1.1 mol of n-propyl acrylate-styrene, 1 mol:0.1-0.8 mol of n-propyl acrylate-trimethylolpropane triacrylate, 1 mol:0.1-1.2 mol of 2-methyl-2-hexyl acrylate:styrene, 1 mol:0.1-1.4 mol of 2-methyl-2-hexyl acrylate:trimethylolpropane triacrylate, 1:0.1-0.9 mol of 2-methyl-2-hexyl acrylate:trimethylolpropane triacrylate; the leveling agent is H-810, H-850 and polydimethylsiloxane.
2. The method for preparing the modified polyurethane-acrylate cold wave coating according to claim 1, which is characterized in that: in the step (1), 0.98mol of the polymethyl compound and 0.3mol of the peroxybenzoic acid are dissolved and stirred with 140mL of a solvent, the temperature is adjusted to 107 ℃, 9.1mol of N-bromosuccinimide is added, and then the mixture is refluxed for 22 hours, and the solvent is removed to obtain the bromomethylene compound.
3. The method for preparing the modified polyurethane-acrylate cold wave coating according to claim 1, which is characterized in that: the polymethyl compound in the step (1) is dimethylnaphthalene; the solvent is dioxane.
4. The method for preparing the modified polyurethane-acrylate cold wave coating according to claim 1, which is characterized in that: in the step (2), 1.12mol of bromomethylene compound is dissolved and stirred with 87mL of solvent, the temperature is regulated to 64 ℃, 11.5mol of alkali is added, the temperature is kept for 95min, and the solvent is removed to obtain the polyhydroxy compound containing the functional structure.
5. The method for preparing the modified polyurethane-acrylate cold wave coating according to claim 1, which is characterized in that: the solvent in step (2) is tetrahydrofuran; the base is NaOH.
6. The method for preparing the modified polyurethane-acrylate cold wave coating according to claim 1, which is characterized in that: in the step (3), 1.22mol of the polymeric polyol, 1.66mol of the polyisocyanate and 0.27mol of the polyhydroxy compound containing the functional structure are dissolved and stirred by using 210mL of a solvent, the temperature is regulated to 173 ℃, 0.07mol of fatty acid and 12mg of a catalyst are added, the mixture is refluxed for 11 hours, 0.03mol of hydroxy acrylic acid is added, the mixture is refluxed for 3.5 hours, and the solvent is removed to obtain the modified polyurethane-acrylic acid prepolymer.
7. The method for preparing the modified polyurethane-acrylate cold wave coating according to claim 1, which is characterized in that: the polymeric polyol in step (3) is a polyether glycol NJ220; the polyisocyanate is cyclohexane diisocyanate; the fatty acid is palmitoleic acid; the catalyst is dibutyl tin oxide; the hydroxy acrylic acid is hydroxyethyl methacrylate; the solvent is methyl isobutyl ketone.
8. The method for preparing the modified polyurethane-acrylate cold wave coating according to claim 1, which is characterized in that: and (4) dispersing and stirring 61g of modified polyurethane-acrylic acid prepolymer with 10.7g of acrylic acid reactive diluent at room temperature in a dark place, adding 3mg of photoinitiator and 6mg of flatting agent to obtain the modified polyurethane-acrylic ester cold-ironing coating, and sealing and preserving.
9. The method for preparing the modified polyurethane-acrylate cold wave coating according to claim 1, which is characterized in that: the photoinitiator in step (4) is 2-hydroxy-2-methyl-1-phenyl-1-propanone 1173; the acrylic acid reactive diluent is 1mol:0.5mol of n-propyl acrylate-styrene; the leveling agent is polydimethylsiloxane.
10. The modified polyurethane-acrylate cold wave coating prepared by the method according to any one of claims 1-9.
CN202311643637.8A 2023-12-01 2023-12-01 Preparation method of modified polyurethane-acrylic ester cold-stamping coating Pending CN117586695A (en)

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