A high-speed coated electrochromic aluminum color coating and a preparation method thereof

Abstract

The application relates to a high-speed coated electrochemical aluminum color coating and relates to the field of electrochemical aluminum. The high-speed coated electrochemical aluminum color coating comprises the following raw materials in mass parts: 12-18 parts of silicone-modified acrylic emulsion; 24-30 parts of water-based acrylic resin; 12-24 parts of maleate-modified acrylic resin; 1-3 parts of defoaming agent; 2-5 parts of wet dispersing agent; 1-2 parts of leveling agent; 60-90 parts of water; and 0.5-1 part of ammonia water; wherein the glass transition temperature of the silicone-modified acrylic emulsion is 150-180 DEG C, the glass transition temperature of the water-based acrylic resin is 60-90 DEG C, and the glass transition temperature of the maleic anhydride-modified acrylic resin is 80-100 DEG C. The application can accelerate the complete curing speed of the color coating and improve the coating speed.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of electrochemical aluminum, in particular to a high-speed coated electrochemical aluminum color layer paint and a preparation method thereof. BACKGROUND

[0002] Electrochemical aluminum refers to a gilding material made of a paint and a vacuum metal layer on a film substrate. Through electrochemical aluminum, various colors, patterns and texts can be printed on paper, cigarette boxes, plastics, leathers, wood and other printing materials to make the surface of the printing material more beautiful. Among them, the laser electrochemical aluminum has beautiful holographic rainbow colors and various colors, and is one of the widely used anti-counterfeiting means.

[0003] Laser electrochemical aluminum includes a base film, a release layer, a color layer, an aluminum plating layer and an adhesive layer. The base film serves as a carrier, the release layer has good peeling performance and is used to separate the color layer from the base film and transfer and bond on the surface of the object to be printed. The color layer and the aluminum plating layer can be used to display patterns or present marks, and the adhesive layer is used to bond the electrochemical aluminum film to the printing material. Laser electrochemical aluminum needs to use a mold pressing device to press a laser pattern on the color layer.

[0004] At present, laser color layer paint is usually composed of acrylic resin, curing agent and solvent. After the paint is coated on the release layer, it is dried and cured to form a color layer. After the paint is coated, the acrylic resin and the curing agent react, and it takes about 5 seconds to completely cure in the oven. However, the length of the oven of the current coating equipment is 15-18 meters, which leads to the problem of slow coating speed. The current coating speed is 75-100 m / min, and the production efficiency is low. SUMMARY

[0005] In order to speed up the complete curing speed of the color layer paint and improve the coating speed, the present application provides a high-speed coated electrochemical aluminum color layer paint and a preparation method thereof.

[0006] The high-speed coated electrochemical aluminum color layer paint and the preparation method thereof provided by the present application adopt the following technical scheme:

[0007] A high-speed coated electrochemical aluminum color layer paint comprises the following raw materials by mass:

[0008] Silicone-modified acrylic emulsion 12-18 parts;

[0009] Water-based acrylic resin 24-30 parts;

[0010] Maleate-modified acrylic resin 12-24 parts;

[0011] Defoaming agent 1-3 parts;

[0012] Wetting dispersant 2-5 parts;

[0013] Leveling agent 1-2 parts;

[0014] Water 60-90 parts;

[0015] Ammonia 0.5-1 part;

[0016] The glass transition temperature of the organic silicon modified acrylic emulsion is 150-180℃, the glass transition temperature of the water-based acrylic resin is 60-90℃, and the glass transition temperature of the maleate modified acrylic resin is 80-100℃.

[0017] By the above technical scheme, the organic silicon modified acrylic emulsion with high glass transition temperature and the water-based acrylic resin and the maleate modified acrylic resin with low glass transition temperature are combined, without using a curing agent, the color layer paint can be cured at low temperature and the curing speed is fast, so that the coating speed can be increased to 250 m / min, and the production efficiency is improved.

[0018] By complementation, the temperature resistance and slitting resistance of the organic silicon modified acrylic resin are utilized, so that the electroplated aluminum does not discolor at 145℃ stamping and does not adhere to the stamping plate during mold pressing; the water-based acrylic resin and the maleate modified acrylic resin make the coating soft during mold pressing, and the laser graphics are clear and obvious at 175℃ mold pressing. By combination, the adhesion between the color layer paint and the base film layer and the plated aluminum layer is good, the slitting resistance is good, and the laser effect is good.

[0019] Preferably, the organic silicon modified acrylic emulsion is made of the following raw materials by weight:

[0020] Acrylic acid 5-15 parts;

[0021] Methyl methacrylate 10-18 parts;

[0022] Isobornyl methacrylate 5-8 parts;

[0023] Silicone monomer 3-7 parts;

[0024] Emulsifier 2-5 parts;

[0025] Initiator 1-3 parts;

[0026] Deionized water 50-75 parts.

[0027] By the above technical scheme, acrylic acid is selected as a soft monomer, methyl methacrylate and isobornyl methacrylate are selected as hard monomers, the glass transition temperature of the monomers is high, the organic silicon monomer with temperature resistance is used for modification, the toughness of the emulsion is improved, the prepared organic silicon modified acrylic emulsion is easy to form a film, and the temperature resistance and slitting resistance are good, the color does not change during stamping, and the plate does not adhere during mold pressing.

[0028] Preferably, the organic silicon monomer is selected from one or more of vinyl trimethoxysilane, methacryloxypropyl trimethoxysilane, and 4-vinylbenzylamine modified (3-glycidoxypropyl) trimethoxysilane.

[0029] By the above technical solution, the cross-linking of the organic silicon monomer and the acrylic monomer is realized by using vinyl silane, so that the coating structure has strong stability.

[0030] Preferably, the 4-vinylbenzylamine modified (3-glycidoxypropyl) trimethoxysilane is composed of the following raw materials by weight:

[0031] (3-glycidoxypropyl) trimethoxysilane 40-55 parts;

[0032] 4-vinylbenzylamine 13-20 parts;

[0033] Catalyst 1-3 parts.

[0034] By the above technical solution, the ring-opening of the epoxy group and the amine group is promoted by the catalyst, so that a benzene ring is introduced into the organic silicon monomer, the toughness of the organic silicon modified acrylic emulsion is enhanced, the slitting property is improved, and the mold pressing is facilitated.

[0035] Preferably, the maleate modified acrylic resin is made from the following raw materials by weight:

[0036] Maleate monomer 5-7 parts;

[0037] Butyl methacrylate 35-40 parts;

[0038] Acrylic acid 18-22 parts;

[0039] Styrene 45-55 parts;

[0040] Initiator 2-4 parts;

[0041] Solvent 23-28 parts.

[0042] By the above technical solution, the maleate monomer is used to modify the acrylic resin, the maleate monomer acts as a mobile phase, and is mixed with styrene, acrylic acid, and butyl methacrylate, so that the toughness of the resin is improved, clear lines are formed in the mold pressing, and the brightness of the mold pressing is improved.

[0043] Preferably, the maleate modified acrylic resin is prepared by the following steps:

[0044] The maleate monomer, butyl methacrylate, acrylic acid, styrene, initiator and solvent are uniformly mixed, and then polymerized at 65-75 DEG C, 0.8-2.2 MPa for 5-8 h, and then the solvent is removed by distillation under reduced pressure to obtain a maleate modified acrylic resin.

[0045] Preferably, the maleate monomer includes one or more of dibutyl maleate, ethylene glycol maleate, dimethyl maleate.

[0046] Preferably, the aqueous acrylic resin has a molecular weight of 6500-8000 and an acid value of 82-88 mgKOH / g.

[0047] By the above technical solution, the molecular weight and acid value of the aqueous acrylic resin are controlled, the viscosity and flowability of the aqueous acrylic resin are controlled, which is conducive to improving the compatibility of the color coating system, and facilitating the film-forming property and color development of the coating.

[0048] The application provides a preparation method of a high-speed coated electrochemical aluminum color coating, including the following steps:

[0049] Water is put into a reaction kettle, and the aqueous acrylic resin and the maleate modified acrylic resin are put into the reaction kettle under stirring, heated to 75-95 DEG C, until the aqueous acrylic resin and the maleate modified acrylic resin are completely dissolved, ammonia water is added to adjust the pH value to 7.5-8.5, and an aqueous solution is obtained for standby;

[0050] An organic silicon modified acrylic emulsion is added into another reaction kettle, the aqueous solution is added under stirring, stirred for 20-30 min, a defoaming agent, a wet dispersing agent and a leveling agent are added, and stirring is continued for 1-1.5 h until mixing, ammonia water is added to adjust the pH value to 7.5-8.5, and an electrochemical aluminum color coating is obtained.

[0051] By the above technical solution, the aqueous solution of the aqueous acrylic resin and the maleate modified acrylic resin is prepared first, and then mixed with the organic silicon modified acrylic emulsion, so that the compatibility and stability of the coating system are strong, and the preparation process is simple.

[0052] Preferably, the organic silicon modified acrylic emulsion is prepared by the following steps:

[0053] After the acrylic acid, methyl methacrylate, isobornyl methacrylate and organic silicon monomer are uniformly mixed at room temperature, they are added to a solution composed of part of deionized water and part of emulsifier, and stirred and emulsified to obtain a pre-emulsion; the remaining deionized water and emulsifier are heated to 70-80 DEG C, part of the pre-emulsion and part of the initiator are added, and the reaction is maintained for 20-30 min; the remaining pre-emulsion and initiator are added dropwise at 80-84 DEG C, and the addition is completed within 2 h, and the reaction is maintained for 1-2 h, and then the temperature is lowered and filtered to obtain the organic silicon modified acrylic emulsion.

[0054] By the above technical scheme, the silicone-modified acrylic emulsion with excellent temperature resistance is obtained by seed polymerization.

[0055] In summary, the present application has the following beneficial effects:

[0056] The present application selects the silicone-modified acrylic emulsion with high glass transition temperature and the water-based acrylic resin and the maleate-modified acrylic resin with low glass transition temperature, does not need to use a curing agent, and the color layer paint can be cured at low temperature and has fast curing speed, so that the coating speed can be increased to 250 m / min, and the production efficiency is improved.

[0057] By complementation of the two, the temperature resistance and slitting resistance of the silicone-modified acrylic resin are utilized, so that the electrochemical aluminum can not discolor at 145°C stamping, and does not adhere to the mold pressing plate during mold pressing; the water-based acrylic resin and the maleate-modified acrylic resin are utilized, so that the coating can become soft during mold pressing, and the laser graphics are clear and obvious at 175°C mold pressing. By combination, the color layer paint has good adhesion to the base film layer and the aluminum plating layer, and has good slitting resistance. DETAILED DESCRIPTION

[0058] The present application is further described below in combination with Examples 1-6 and Comparative Examples 1-3.

[0059] Preparation Example

[0060] Preparation Example 1

[0061] The silicone-modified acrylic emulsion comprises the following raw materials:

[0062] Acrylic acid 5 kg;

[0063] Methyl methacrylate 10 kg;

[0064] Isobornyl methacrylate 5 kg;

[0065] Silicone monomer 3 kg, in the present preparation example, the silicone monomer is specifically vinyl trimethoxysilane;

[0066] Emulsifier 2 kg, in the present preparation example, the emulsifier is specifically selected as 1 kg of reactive emulsifier ER-10 and 1 kg of non-ionic emulsifier CO-430;

[0067] Initiator 1 kg, in the present preparation example, the initiator is specifically selected as potassium persulfate;

[0068] Deionized water 50 kg.

[0069] The silicone-modified acrylic emulsion is prepared by the following steps:

[0070] Take acrylic acid, methyl methacrylate, isobornyl methacrylate, silicone monomer at room temperature after mixing evenly, added to the solution of 35 kg deionized water and 1 kg emulsifier, stirring emulsification, get pre-emulsion; the remaining deionized water and emulsifier heated to 70 ℃, add 1 / 3 pre-emulsion and 0.4 kg initiator, incubation reaction 20 min; at 80 ℃ drop the remaining pre-emulsion and initiator in 2 h drop is completed, incubation reaction 1 h, drop to room temperature, adjust pH to 6.5 with ammonia, with 200 mesh sieve filter to get acrylic resin emulsion, get silicone modified acrylic emulsion.

[0071] The glass transition temperature of the silicone modified acrylic emulsion is 150 ℃.

[0072] Preparation Example 2

[0073] The silicone modified acrylic emulsion comprises the following raw materials:

[0074] Acrylic acid 15 kg;

[0075] Methyl methacrylate 18 kg;

[0076] Isobornyl methacrylate 8 kg;

[0077] Silicone monomer 7 kg, in this preparation example, the silicone monomer is specifically selected from methacryloxypropyl trimethoxysilane;

[0078] Emulsifier 5 kg, in this preparation example, the emulsifier is specifically selected from 3 kg of n-octyl sodium sulfate and 2 kg of nonylphenol polyoxyethylene ether; initiator 3 kg, in this preparation example, the initiator is specifically selected from ammonium persulfate;

[0079] Deionized water 75 kg.

[0080] The silicone modified acrylic emulsion is prepared by the following steps:

[0081] Take acrylic acid, methyl methacrylate, isobornyl methacrylate, silicone monomer at room temperature after mixing evenly, added to the solution of 35 kg deionized water and 1 kg emulsifier, stirring emulsification, get pre-emulsion; the remaining deionized water and emulsifier heated to 70 ℃, add 1 / 3 pre-emulsion and 0.4 kg initiator, incubation reaction 20 min; at 80 ℃ drop the remaining pre-emulsion and initiator in 2 h drop is completed, incubation reaction 1 h, drop to room temperature, adjust pH to 6.5 with ammonia, with 200 mesh sieve filter to get acrylic resin emulsion, get silicone modified acrylic emulsion.

[0082] The glass transition temperature of the silicone modified acrylic emulsion is 150 ℃.

[0083] Preparation Example 3

[0084] The silicone-modified acrylic emulsion comprises the following raw materials:

[0085] Acrylic acid 10 kg;

[0086] Methyl methacrylate 14 kg;

[0087] Isobornyl methacrylate 7 kg;

[0088] Silicone monomer 5 kg, in this preparation example, the silicone monomer is specifically selected from 2 kg of vinyl trimethoxysilane and 3 kg of methacryloyloxypropyl trimethoxysilane;

[0089] Emulsifier 3 kg, in this preparation example, the emulsifier is specifically selected from 1.8 kg of sodium sulfosuccinate dibutyl and 1.2 kg of sodium sulfosuccinate monooctadecylamide;

[0090] Initiator 2 kg, in this preparation example, the initiator is specifically selected from potassium persulfate;

[0091] Deionized water 60 kg.

[0092] The silicone-modified acrylic emulsion is prepared by the following steps:

[0093] After the acrylic acid, methyl methacrylate, isobornyl methacrylate, and silicone monomer are uniformly mixed at room temperature, they are added to a solution composed of 45 kg of deionized water and 2.2 kg of emulsifier, and stirred and emulsified to obtain a pre-emulsion. The remaining deionized water and emulsifier are heated to 75°C, 2 / 5 of the pre-emulsion and 1.5 kg of initiator are added, and the reaction is maintained for 25 min. The remaining pre-emulsion and initiator are added dropwise at 82°C, and the addition is completed within 2 h. The reaction is maintained for 1.5 h, and then the temperature is lowered to room temperature. The pH is adjusted to 6.5 with ammonia water, and the acrylic resin emulsion is filtered with a 200-mesh sieve to obtain the silicone-modified acrylic emulsion.

[0094] The glass transition temperature of the silicone-modified acrylic emulsion is measured to be 160°C.

[0095] Preparation Example 4

[0096] The difference between this preparation example and Preparation Example 1 is that the silicone monomer is 4-vinylbenzylamine-modified (3-epoxypropoxypropyl) trimethoxysilane.

[0097] The 4-vinylbenzylamine-modified (3-epoxypropoxypropyl) trimethoxysilane is prepared from the following raw materials:

[0098] (3-epoxypropoxypropyl) trimethoxysilane 3.5 kg;

[0099] 4-vinylbenzylamine 1.4 kg;

[0100] Catalyst 0.1 kg, the catalyst is selected from stannous octoate.

[0101] The preparation method is as follows: 8 kg of dimethyl sulfoxide is added to a reaction kettle, stirring is started, (3-glycidoxypropyl) trimethoxysilane, 4-vinylbenzylamine and a catalyst are added, heating is started to 75 °C, and reaction is carried out for 2 h. Dimethyl sulfoxide is removed by vacuum distillation, and 4-vinylbenzylamine modified (3-glycidoxypropyl) trimethoxysilane is obtained by cleaning and drying.

[0102] The glass transition temperature of the silicone-modified acrylic emulsion is measured to be 180 °C.

[0103] Preparation Example 5

[0104] The difference between the present preparation example and Preparation Example 1 is that the silicone monomer is selected to be 4-vinylbenzylamine modified (3-glycidoxypropyl) trimethoxysilane.

[0105] 4-vinylbenzylamine modified (3-glycidoxypropyl) trimethoxysilane is prepared from the following raw materials:

[0106] (3-glycidoxypropyl) trimethoxysilane 5 kg;

[0107] 4-vinylbenzylamine 1.8 kg;

[0108] Catalyst 0.3 kg, the catalyst is selected from stannous octoate.

[0109] The preparation method is as follows: 10 kg of dimethyl sulfoxide is added to a reaction kettle, stirring is started, (3-glycidoxypropyl) trimethoxysilane, 4-vinylbenzylamine and a catalyst are added, heating is started to 80 °C, and reaction is carried out for 3 h. Dimethyl sulfoxide is removed by vacuum distillation, and 4-vinylbenzylamine modified (3-glycidoxypropyl) trimethoxysilane is obtained by cleaning and drying.

[0110] The glass transition temperature of the silicone-modified acrylic emulsion is measured to be 172 °C.

[0111] Preparation Example 6

[0112] The maleate-modified acrylic resin comprises the following raw materials:

[0113] Maleate monomer 0.5 kg, in the present preparation example, the maleate monomer is selected to be dibutyl maleate;

[0114] Butyl methacrylate 3.5 kg;

[0115] Acrylic acid 1.8 kg;

[0116] Styrene 4.5 kg;

[0117] 0.2 kg, in the present preparation example, the initiator is selected from di-tert-butyl peroxide;

[0118] 2.3 kg, in the present preparation example, the solvent is selected from toluene.

[0119] The preparation method of the maleate-modified acrylic resin is as follows:

[0120] The maleate monomer, butyl methacrylate, acrylic acid, styrene, initiator and solvent are uniformly mixed, and then polymerized at 65 DEG C and 0.8 MPa for 5 h, and then the solvent is removed by distillation under reduced pressure, and the discharge is cooled to room temperature to obtain the maleate-modified acrylic resin.

[0121] The glass transition temperature of the maleate-modified acrylic resin is measured to be 80 DEG C.

[0122] Preparation Example 7

[0123] The maleate-modified acrylic resin comprises the following raw materials:

[0124] 0.7 kg, in the present preparation example, the maleate monomer is selected from maleic acid glycol ester;

[0125] 4 kg of butyl methacrylate;

[0126] 2.2 kg of acrylic acid;

[0127] 5.5 kg of styrene;

[0128] 0.4 kg, in the present preparation example, the initiator is selected from azobisisobutyronitrile;

[0129] 2.8 kg, in the present preparation example, the solvent is selected from ethyl acetate.

[0130] The preparation method of the maleate-modified acrylic resin is as follows:

[0131] The maleate monomer, butyl methacrylate, acrylic acid, styrene, initiator and solvent are uniformly mixed, and then polymerized at 75 DEG C and 2.2 MPa for 8 h, and then the solvent is removed by distillation under reduced pressure, and the discharge is cooled to room temperature to obtain the maleate-modified acrylic resin.

[0132] The glass transition temperature of the maleate-modified acrylic resin is measured to be 98 DEG C.

[0133] Preparation Example 8

[0134] The maleate-modified acrylic resin comprises the following raw materials:

[0135] 0.6 kg, in the present preparation example, the maleate monomer is selected from dimethyl maleate;

[0136] butyl methacrylate 3.8 kg;

[0137] acrylic acid 2 kg;

[0138] styrene 5 kg;

[0139] initiator 0.3 kg, in this preparation example, the initiator is selected as di-t-butyl peroxide;

[0140] solvent 2.5 kg, in this preparation example, the solvent is selected as ethyl acetate.

[0141] The preparation method of the maleate-modified acrylic resin is as follows:

[0142] The maleate monomer, butyl methacrylate, acrylic acid, styrene, initiator and solvent are uniformly mixed, and then polymerized at 70°C and 1.5 MPa for 6 h, and then the solvent is removed by distillation under reduced pressure, and the discharge is cooled to room temperature to obtain the maleate-modified acrylic resin.

[0143] The glass transition temperature of the maleate-modified acrylic resin is measured to be 87°C.

[0144] Example

[0145] Example 1

[0146] The anodized aluminum color coating includes the following raw materials:

[0147] silicone-modified acrylic emulsion 12 kg, selected as the silicone-modified acrylic emulsion prepared in Preparation Example 1;

[0148] water-based acrylic resin 24 kg, selected as a water-based acrylic resin with a glass transition temperature of 70°C, a molecular weight of 6500, an acid value of 85 mgKOH / g, and a model number of HANWA S-60L;

[0149] maleate-modified acrylic resin 12 kg, selected as the maleate-modified acrylic resin prepared in Preparation Example 6;

[0150] defoamer 1 kg, selected as a water-based mineral oil defoamer of WINCREATION Surfynol DF220;

[0151] wetting dispersant 2 kg, selected as a water-based alkyne diol dispersant of DEGOS Dispers 740W;

[0152] leveling agent 1 kg, selected as a water-based silicone leveling agent of DEGOS Glide B 1484;

[0153] water 60 kg;

[0154] ammonia 0.5 kg.

[0155] The preparation method of the electrochemical aluminum color coating is as follows:

[0156] Water is put into a reaction kettle, and the water-based acrylic resin and the maleate-modified acrylic resin are put into the reaction kettle under stirring, heated to 75°C, until the water-based acrylic resin and the maleate-modified acrylic resin are completely dissolved, ammonia water is added to adjust the pH value to 7.5, and a water solution is obtained for standby;

[0157] The silicone-modified acrylic emulsion is added into another reaction kettle, and the water solution is added under stirring, stirred for 20 min, and then the defoaming agent, the wet dispersant and the leveling agent are added, and stirring is continued for 1 h until mixing, ammonia water is added to adjust the pH value to 7.5, and the high-speed coating electrochemical aluminum color coating is obtained.

[0158] Example 2

[0159] The electrochemical aluminum color coating comprises the following raw materials:

[0160] The silicone-modified acrylic emulsion 18 kg is selected from the silicone-modified acrylic emulsion prepared in Preparation Example 1;

[0161] The water-based acrylic resin 30 kg is selected from the water-based acrylic resin with a glass transition temperature of 70°C, a molecular weight of 6500, an acid value of 85 mgKOH / g, and a model number of HANWA S-60L;

[0162] The maleate-modified acrylic resin 24 kg is selected from the maleate-modified acrylic resin prepared in Preparation Example 6;

[0163] The defoaming agent 3 kg is selected from the water-based molecular level defoaming agent of WIN CRE Surfynol DF-110L;

[0164] The wet dispersant 5 kg is selected from the water-based polycarboxylate dispersant of SINOPEC SN-DISPERSANT 5040;

[0165] The leveling agent 2 kg is selected from the acetylenic glycol leveling agent of WIN CRE Dynol 604;

[0166] Water 90 kg;

[0167] Ammonia water 1 kg.

[0168] The preparation method of the electrochemical aluminum color coating is as follows:

[0169] Water is put into a reaction kettle, and the water-based acrylic resin and the maleate-modified acrylic resin are put into the reaction kettle under stirring, heated to 95°C, until the water-based acrylic resin and the maleate-modified acrylic resin are completely dissolved, ammonia water is added to adjust the pH value to 8.5, and a water solution is obtained for standby;

[0170] Into another reaction kettle, add silicone modified acrylic emulsion, add aqueous solution under stirring, stir for 30 min, then add defoaming agent, wetting dispersant and leveling agent, continue to stir for 1.5 h to mix, add ammonia water to adjust pH value to 8.5, to obtain high-speed coating anodized aluminum color layer paint.

[0171] Examples 3-6

[0172] Examples 3-6 are different from Example 1 in that the silicone modified acrylic emulsion and the maleate modified acrylic resin used in the raw materials are different, as shown in Table 1.

[0173] Table 1

[0174] Comparative Example

[0175] Comparative Example 1

[0176] The difference between this comparative example and Example 1 is that no maleate modified acrylic resin is added in the preparation of the color layer paint of this comparative example.

[0177] Comparative Example 2

[0178] The difference between this comparative example and Example 1 is that no silicone modified acrylic emulsion is added in the preparation of the color layer paint of this comparative example.

[0179] Comparative Example 3

[0180] The difference between this comparative example and Example 1 is that the color layer paint in this comparative example is prepared from a water-based acrylic resin with a glass transition temperature of 105℃, a molecular weight of 7000, an acid value of 220 mgKOH / g, and a model number of Hwaseung S-70.

[0181] Performance Test

[0182] The anodized aluminum color layer paint prepared in each example and comparative example of the present application is mixed with dye to prepare different color layer slurries. The color layer paint accounts for 90% and the dye accounts for 10%.

[0183] Preparation of anodized aluminum:

[0184] 1. Preparation for each example:

[0185] The color layer paint of each example is coated onto a PET base film with a release coating using a coater, the release coating is prepared from water-based wax (20% solid content) 1.1 kg, pure water 12 kg, ethanol 15 kg, the coating weight is 0.088 g / m 2 , the coating speed is 100 m / min;

[0186] The coating amount of the color layer paint is 1.1 g / m2 The laser color layer was obtained by coating at a speed of 250 m / min, drying in an oven with the following drying parameters: 80℃ for zone 1, 120℃ for zone 2, 160℃ for zone 3, 155℃ for zone 4, and 140℃ for zone 5.

[0187] The laser color layer was embossed with the following process: starting temperature of 140℃, gradually increasing to 175℃, and gradually increasing the machine speed from 5 m / min to 50 m / min.

[0188] After embossing, aluminum was plated on the laser color layer to form an aluminum plating layer with an OD value of 1.2. Finally, an adhesive layer was formed by coating an adhesive and drying to obtain the electrochemical aluminum.

[0189] 2. Preparation of each comparative example: The difference from the examples is that the coating speed of the color layer paint is 80 m / min.

[0190] The electrochemical aluminum mold was tested for slitting property, temperature resistance, and laser effect.

[0191] Slitting property: The prepared electrochemical aluminum film was hot stamped onto the surface of the printing material at 125℃, and the film was torn off. The printing material was packaging paper, and the hot stamping pattern was a continuous tiled square. After hot stamping, the appearance of the square boundary was observed and recorded in Table 2. The clearer the boundary, the better the slitting property.

[0192] Temperature resistance: 145℃ hot stamping was observed for discoloration, and the hot stamping delay was 0.4s.

[0193] Laser effect: After separating the paint layer and release layer of the electrochemical aluminum from the substrate film, the pattern clarity of the unattached part of the paint layer was observed and evaluated, where 1st grade was clear pattern without speckles, 2nd grade was clear pattern with slight speckles, 3rd grade was slightly blurred pattern, and 4th grade was obviously blurred pattern.

[0194] Hot stamping quality: The prepared electrochemical aluminum film was hot stamped onto the surface of the printing material at 125℃, and the hot stamping pattern area was a square pattern of 50mm x 50mm. The pattern clarity and integrity were observed.

[0195] Table 2

[0196] Sample Slitting Temperature resistance Laser effect Hot stamping quality Example 1 Clear border No discoloration 1st grade Pattern clear and complete Example 2 Clear border No discoloration 1st grade Pattern clear and complete Example 3 Clear border No discoloration 1st grade Pattern clear and complete Example 4 Clear border No discoloration 1st grade Pattern clear and complete Example 5 Clear border No discoloration 1st grade Pattern clear and complete Example 6 Clear border No discoloration 1st grade Pattern clear and complete Comparative Example 1 Fuzzy border No discoloration 4th grade Pattern fuzzy Comparative Example 2 Fuzzy border Discoloration 2nd grade Pattern fuzzy Comparative Example 3 Clear border No discoloration 3rd grade Pattern fuzzy

[0197] According to Table 2, the combination of the high glass transition temperature organic silicone modified acrylic emulsion and the low glass transition temperature water-based acrylic resin of the present application can accelerate the curing speed of the color layer paint, increase the coating speed to 250 m / min, and improve the production efficiency of the electrochemical aluminum. Moreover, the color layer paint has good temperature resistance, does not discolor at 145℃ hot stamping, has good laser effect, good slitting property, and good hot stamping quality, meeting the needs of high-speed hot stamping.

[0198] Compared with Comparative Examples 1-3 and Example 1, the silicone-modified acrylic emulsion and the water-based acrylic resin, the combination of the water-based acrylic resin are changed, which shows that the silicone-modified acrylic emulsion provides good slitting property and high temperature resistance, the water-based acrylic resin, the water-based acrylic resin provides appropriate mold temperature and good laser effect, so that the laser pattern is clear, and the three synergistically realize good hot stamping effect.

[0199] The specific embodiment is only an explanation of the present application, which is not a limitation of the present application, and those skilled in the art can make modifications to the specific embodiment without creative contribution after reading the specification, but as long as it is within the scope of the claims of the present application, it is protected by the patent law.

Claims

1. A high speed coated electrochromic color band coating characterized by: The raw materials include the following quality parts: Silicone modified acrylic emulsion 12-18 parts; Water-based acrylic resin 24-30 parts; Maleate modified acrylic resin 12-24 parts; Defoaming agent 1-3 parts; Wetting dispersant 2-5 parts; Leveling agent 1-2 parts; Water 60-90 parts; Ammonia 0.5-1 part; The glass transition temperature of the silicone modified acrylic emulsion is 150-180℃, the glass transition temperature of the water-based acrylic resin is 60-90℃, the molecular weight is 6500-8000, the acid value is 82-88mgKOH / g, and the glass transition temperature of the maleate modified acrylic resin is 80-100℃.

2. A high speed coated electrochromic color band coating according to claim 1, characterized in that: The silicone modified acrylic emulsion is made from the following raw materials by weight: Acrylic acid 5-15 parts; Methyl methacrylate 10-18 parts; Isobornyl methacrylate 5-8 parts; Silicone monomer 3-7 parts; Emulsifier 2-5 parts; Initiator 1-3 parts; Deionized water 50-75 parts.

3. A high speed coated electrochromic pigment according to claim 2, characterized in that: The silicone monomer is selected from one or more of vinyltrimethoxysilane, methacryloyloxypropyltrimethoxysilane, and 4-vinylbenzylamine modified (3-glycidoxypropyl) trimethoxysilane.

4. A high speed coated electrochromic coating according to claim 3, characterized in that: The 4-vinylbenzylamine modified (3-glycidoxypropyl) trimethoxysilane is composed of the following raw materials by weight: (3-Glycidoxypropyl) trimethoxysilane 35-50 parts; 4-Vinylbenzylamine 14-18 parts; Catalyst 1-3 parts.

5. A high speed coated electrochromic color band coating according to claim 1, characterized in that: The maleate modified acrylic resin is made from the following raw materials by weight: Maleate monomer 5-7 parts; Butyl methacrylate 35-40 parts; Acrylic acid 18-22 parts; Styrene 45-55 parts; Initiator 2-4 parts; Solvent 23-28 parts.

6. A high speed coated electrochromic coating according to claim 5, wherein, The maleate modified acrylic resin is prepared by the following steps: Mix the maleate monomer, butyl methacrylate, acrylic acid, styrene, initiator, and solvent uniformly, then polymerize at 65-75℃ and 0.8-2.2MPa for 5-8h, then remove the solvent by distillation under reduced pressure to obtain the maleate modified acrylic resin.

7. A high speed coated electrochromic coating according to claim 5, characterized in that: The maleate monomer includes one or more of dibutyl maleate, maleic acid glycol ester, and dimethyl maleate.

8. A process for the preparation of a high speed coated electrochromic colour coating according to any one of claims 1 to 7, characterised in that, The steps include: Put water into the reaction kettle, add water-based acrylic resin and maleate modified acrylic resin under stirring, heat to 75-95℃, until the water-based acrylic resin and maleate modified acrylic resin are completely dissolved, add ammonia to adjust the pH value to 7.5-8.5, obtain an aqueous solution for standby; Add silicone modified acrylic emulsion to another reaction kettle, add the aqueous solution under stirring, stir for 20-30min, then add defoaming agent, wetting dispersant, and leveling agent, continue to stir for 1-1.5h to mix, add ammonia to adjust the pH value to 7.5-8.5, obtain the aluminum color coating.

9. A method of preparing a high speed coated electrochromic pigment according to claim 8, characterized in that, The silicone modified acrylic emulsion is prepared by the following steps: The acrylic acid, methyl methacrylate, isobornyl methacrylate and silicone monomer are mixed uniformly at room temperature, and then added into a solution of part of deionized water and part of emulsifier to be stirred and emulsified to obtain a pre-emulsion; the remaining deionized water and emulsifier are heated to 70-80℃, part of the pre-emulsion and part of the initiator are added, and the reaction is preserved for 20-30 min; the remaining pre-emulsion and initiator are added dropwise at 80-84℃, and the dropping is completed within 2 h, and the reaction is preserved for 1-2 h, and then cooled and filtered to obtain a silicone-modified acrylic emulsion.

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