An anti-flying aluminum transfer coating and its preparation method

Abstract

The present invention discloses an anti-flying aluminum transfer coating and a preparation method thereof. The anti-flying aluminum transfer coating comprises 10-18 parts of polyacrylate resin, 3-8 parts of modified polyacrylate resin, 1-3 parts of blocked curing agent, 1-8 parts of cellulose ester resin, 0-0.3 parts of auxiliary agent, and 70-85 parts of solvent. The modified polyacrylate resin is a copolymer formed by polymerization of one or more of hydroxyacrylate or aminoacrylate and acrylate, and the blocked curing agent is an isocyanate curing agent. The preparation method is as follows: The solvent is put into a reaction kettle, and after heating and stirring evenly, the powder materials are put into the reaction kettle and stirred evenly, and then the auxiliary agent is added and stirred evenly, and the product can be obtained by cooling and filtering. The present invention introduces a modified polyacrylate resin and an isocyanate curing agent, and undergoes deblocking crosslinking during the application process, increasing the overall polarity of the system and improving the aluminum flying performance.

Description

Technical Field

[0001] The present invention belongs to the field of coatings, and particularly relates to an anti-flying aluminum transfer coating and a preparation method thereof. Background Art

[0002] With the development of technology, the current packaging boxes mostly adopt the transfer process. That is, a transfer coating is coated on a plastic base film, dried, and then vacuum aluminized to make an aluminized film. A transfer glue is coated, the base film is peeled off, and the coating is transferred to the packaging cardboard. Finally, the finished packaging box does not contain non-degradable aluminum foil and plastic film, and the finished product is green and environmentally friendly. Due to the differences in the performance of the coating itself in terms of strength, ductility, and the adhesion of the coating to aluminum, as well as those of the plastic base film and aluminum foil, the phenomenon of flying aluminum will occur during use. Patent CN109294377A discloses a laser transfer coating with excellent flexibility, which mentions the anti-flying aluminum performance, but it will reduce the temperature resistance of the system and affect its scope of use. Patent CN103031027A discloses an environmentally friendly laser aluminized transfer coating with high aluminum layer adhesion, which also mentions the problem of preventing the aluminum layer from detaching, but its design concept is completely different from that of the present invention, and the cost is relatively high. Summary of the Invention

[0003] An object of the present invention is to solve at least the above problems and / or defects and provide at least the advantages described hereinafter.

[0004] To achieve these objects and other advantages of the present invention, there is provided an anti-flying aluminum transfer coating, which is characterized in that the anti-flying aluminum transfer coating comprises the following components in percentage by weight: 10-18 parts of polyacrylate resin, 3-8 parts of modified polyacrylate resin, 1-3 parts of blocked curing agent, 1-8 parts of cellulose ester resin, 0-0.3 parts of auxiliary agent, and 70-85 parts of solvent. The modified polyacrylate resin is a copolymer formed by polymerization of one or more of hydroxyacrylate or aminoacrylate and acrylate, and the blocked curing agent is an isocyanate curing agent.

[0005] Preferably, the polyacrylate resin is a polymer of one or more monomers selected from methyl methacrylate, ethyl methacrylate, butyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, isobornyl acrylate, and acrylic acid. The glass transition temperature of the polyacrylate resin is 50-110°C, and the molecular weight is 30,000-140,000.

[0006] Preferably, the cellulose ester resin is one or more of cellulose acetate, cellulose acetate butyrate, and cellulose acetate propionate with a molecular weight of 30,000-140,000.

[0007] Preferably, the solvent is one or more of ethyl acetate, n-propyl acetate, n-butyl acetate, ethanol, n-propanol, isopropanol, acetone, methyl ethyl ketone, propylene glycol methyl ether, and propylene glycol ethyl ether.

[0008] Preferably, the auxiliary agent is one or more of a leveling agent, an antifoaming agent, and an anti-scratch agent.

[0009] Preferably, the leveling agent is one or more of Flow300, Glide410, Glide435, Glide450, Glide432, BYK-306, BYK-333, BYK-323, BYK-358N, BYK-354, DC11, DC67, DC57, DC56, DC54, DC5211.

[0010] Preferably, the antifoaming agent is one or more of BYK-141, BYK-052, BYK-051, BYK-066N, BYK-0234, Airex900, Airex910, Airex920, Airex9313, DC163, DC62, DC65.

[0011] Preferably, the anti-scratch agent is one or more of DC51, DC52, DC29, DC27, DC18.

[0012] Preferably, the hydroxyacrylate is one or more of 2-hydroxyethyl methacrylate, hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, hydroxypropyl acrylate, the aminoacrylate is 2-aminoethyl methacrylate, the acrylate is one or more of methyl methacrylate, ethyl methacrylate, butyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, isobornyl acrylate, and acrylic acid, and the blocked curing agent is an isocyanate curing agent with a deblocking temperature range of 90-150°C.

[0013] A preparation method of an anti-flying aluminum transfer coating includes the following steps:

[0014] Step 1: Put the solvent into a reaction kettle, then heat it to 45-55°C and maintain the stirring speed at 60-100 rpm;

[0015] Step 2: Add polyacrylate resin, modified polyacrylate resin, blocked curing agent, and cellulose ester resin into the reaction kettle and continue stirring for 1.5-3 h;

[0016] Step 3: Add the auxiliary agent into the reaction kettle, stop stirring after stirring for 0.5-1 h, cool the product and then filter it, and then carry out packaging to obtain the anti-flying aluminum transfer coating product.

[0017] The present invention has at least the following beneficial effects:

[0018] (1) Simple production process: The production process and use process of the system provided by the present invention are consistent with the production and use process of existing products, and there is no need to modify the existing equipment and process. It is simple and easy to operate in terms of practicality;

[0019] (2) The present invention introduces a latent curing agent into the coating system while introducing a modified polyacrylate resin to participate in the system reaction. The latent curing agent is sensitive to temperature and can be unblocked within the range of 90 to 150°C. At room temperature, the system is stable and will not react. When the system is dried and molded, the unblocking reaction crosslinks to form a crosslinking network, which increases the polarity of the system, improves the aluminum-free performance of the system, and does not affect the temperature resistance of the system. Although there is a curing agent in the system, its sensitive temperature range is set, so it can be made into a single component, which does not increase the difficulty of using the coating;

[0020] (3) Cross-linking will occur during the use of the system, thereby improving the strength of the system and the coating has excellent embossing resistance;

[0021] (4) When the coating system is cut, the cut is smooth and there is no adhesion.

[0022] Other advantages, objectives and features of the present invention will be embodied in part through the following description, and in part will be understood by those skilled in the art through study and practice of the present invention. DETAILED DESCRIPTION

[0023] The present invention is described in further detail below so that those skilled in the art can implement it according to the description.

[0024] Example 1

[0025] A method for preparing an anti-flying aluminum transfer coating, comprising:

[0026] Step 1: 20 kg of ethyl acetate, 20 kg of butanone, 20 kg of n-propyl acetate and 10 kg of propylene glycol methyl ether were placed in a reaction kettle as solvents by weight, the reaction kettle was heated to 50° C., a stirring device was turned on, and the stirring speed was maintained at 100 rpm for uniform stirring;

[0027] Step 2: Add 10 kg of polyacrylate resin (glass transition temperature 100°C, molecular weight 70,000), 1 kg of cellulose acetate resin, 3 kg of modified polyacrylate resin (polymerized from hydroxyethyl acrylate, methyl methacrylate, and butyl acrylate), and 1 kg of isocyanate curing agent into the reactor by weight, and continue stirring for 2 hours;

[0028] Step 3: Add 0.01 kg of leveling agent BYK-333 into the reaction kettle, stir for 1 h until it is uniform, then stop stirring. Cool the product to 20 °C, filter it, and then package it to obtain the anti-flying aluminum transfer coating product.

[0029] Among them, the synthesis method of the modified polyacrylate resin in Step 2 is as follows:

[0030] S1. In an intermittent reaction vessel, add zinc chloride and 0.1 kg of polyethylene glycol into water to form an aqueous phase with a zinc chloride concentration of 5 ppm, stir and heat up to 50 °C;

[0031] S2. Mix 25 kg of hydroxyethyl acrylate, 40 kg of methyl methacrylate, 30 kg of butyl acrylate, 0.4 kg of tert-butyl peroxy-2-ethylhexanoate, and 3 kg of isooctyl mercaptoacetate evenly to obtain an oil phase;

[0032] S3. Add the oil phase to the aqueous phase according to the volume ratio of oil phase to aqueous phase of 1:3, then stir at 50 °C for 30 min, then heat up to 85 °C, continue to stir and react for 3 h, and then heat up to 95 °C and keep stirring for 2 h;

[0033] S4. After the reaction is completed, collect the solid product by static settlement and filtration. The obtained solid product is washed and then dried at 45 °C for 10 h to obtain the modified polyacrylate resin.

[0034] Example 2

[0035] A preparation method of an anti-flying aluminum transfer coating, comprising:

[0036] Step 1: Place 30 kg of ethyl acetate, 15 kg of butyl acetate, 25 kg of acetone, 15 kg of n-propanol, and 5 kg of propylene glycol ethyl ether as solvents in the reaction kettle, heat the reaction kettle to 60 °C, turn on the stirring device, and maintain the stirring speed at 100 rpm, and stir evenly;

[0037] Step 2: Add 18 kg of polyacrylate resin (glass transition temperature 70 °C, molecular weight 70000), 8 kg of cellulose acetate propionate resin, 8 kg of modified polyacrylate resin (polymerized from ethyl methacrylate, butyl methacrylate, and 2-aminoethyl methacrylate), and 3 kg of isocyanate curing agent into the reaction kettle, and continue to stir for 2 h;

[0038] Step 3: Add 0.25 kg of leveling agent Flow300 and 0.05 kg of defoaming agent Airex900 into the reaction kettle, stir for 1 h until it is uniform, then stop stirring. Cool the product to 20 °C, filter it, and then package it to obtain the anti-flying aluminum transfer coating product.

[0039] Among them, the synthesis method of the modified polyacrylate resin in step two is as follows:

[0040] S1. In a batch reactor, zinc chloride and 0.1 kg of polyethylene glycol are added to water to form an aqueous phase with a zinc chloride concentration of 5 ppm, stirred and heated to 50 °C.

[0041] S2. 25 kg of 2-aminoethyl methacrylate, 40 kg of ethyl methacrylate, 30 kg of butyl methacrylate, 0.4 kg of tert-butyl peroxy-2-ethylhexanoate and 3 kg of isooctyl mercaptoacetate are mixed evenly to obtain an oil phase.

[0042] S3. The oil phase is added to the aqueous phase according to the volume ratio of oil phase to aqueous phase of 1:3, then stirred at 50 °C for 30 min, then heated to 85 °C, and continuously stirred and reacted for 3 h, and then heated to 95 °C and kept stirring for 2 h.

[0043] S4. After the reaction is completed, the solid product is collected by static sedimentation and filtration. The obtained solid product is washed and dried at 45 °C for 10 h to obtain the modified polyacrylate resin.

[0044] Example 3

[0045] A preparation method of an anti-flying aluminum transfer coating, comprising:

[0046] Step one. 6 kg of ethanol, 15 kg of ethyl acetate, 25 kg of methyl ethyl ketone, 16 kg of n-propanol, and 20 kg of dimethyl carbonate are used as solvents and placed in a reaction kettle. The reaction kettle is heated to 60 °C and the stirring device is started, and the stirring speed is maintained at 100 rpm and stirred evenly.

[0047] Step two. 14 kg of polyacrylate resin (glass transition temperature 80 °C, molecular weight 85,000), 4.5 kg of cellulose acetate butyrate resin, 5.5 kg of modified polyacrylate resin (polymerized from hydroxypropyl acrylate, methyl acrylate, and butyl acrylate), and 2 kg of isocyanate curing agent are added to the reaction kettle and continuously stirred for 2 h.

[0048] Step three. 0.15 kg of leveling agent Glide450, 0.1 kg of anti-scratch agent DC51, and 0.01 kg of defoaming agent BYK-052 are added to the reaction kettle, stirred for 1 h until uniform, then the stirring is stopped, the product is cooled to 20 °C and filtered, and then packaged to obtain the anti-flying aluminum transfer coating product.

[0049] Among them, the synthesis method of the modified polyacrylate resin in step two is as follows:

[0050] S1. In an intermittent reaction vessel, zinc chloride and 0.1 kg of polyethylene glycol are added to water to form an aqueous phase with a zinc chloride concentration of 5 ppm, and the mixture is stirred and heated to 50 °C.

[0051] S2. 25 kg of hydroxypropyl acrylate, 40 kg of methyl acrylate, 30 kg of butyl acrylate, 0.4 kg of tert-butyl peroxy-2-ethylhexanoate, and 3 kg of isooctyl mercaptoacetate are mixed uniformly to obtain an oil phase.

[0052] S3. The oil phase is added to the aqueous phase at a volume ratio of oil phase:aqueous phase of 1:3, then stirred at 50 °C for 30 min, heated to 85 °C, and continuously stirred for 3 h, and then heated to 95 °C and kept stirring for 2 h.

[0053] S4. After the reaction is completed, the solid product is collected by static sedimentation and filtration. The obtained solid product is washed and dried at 45 °C for 10 h to obtain the modified polyacrylate resin.

[0054] Comparative Example 1

[0055] The difference between this comparative example and Example 1 is that in Step 2: 10 kg of polyacrylate resin (glass transition temperature 100 °C, molecular weight 70000), 4 kg of cellulose acetate resin, and 1 kg of isocyanate curing agent are added to the reaction kettle by weight, and stirring is continued for 2 h.

[0056] The remaining steps are the same as the preparation method of Example 1.

[0057] Comparative Example 2

[0058] The difference between this comparative example and Example 1 is that in Step 2: 10 kg of polyacrylate resin (glass transition temperature 100 °C, molecular weight 70000), 2 kg of cellulose acetate resin, and 3 kg of modified polyacrylate resin (polymerized from hydroxyethyl acrylate, methyl methacrylate, and butyl acrylate) are added to the reaction kettle by weight, and stirring is continued for 2 h.

[0059] The remaining steps are the same as the preparation method of Example 1.

[0060] Comparative Example 3

[0061] The difference between this comparative example and Example 1 is that in Step 2: 10 kg of polyacrylate resin (glass transition temperature 100 °C, molecular weight 70000) and 5 kg of cellulose acetate resin are added to the reaction kettle by weight, and stirring is continued for 2 h.

[0062] The remaining steps are the same as the preparation method of Example 1.

[0063] Comparative Example 4

[0064] The difference between this comparative example and Example 1 lies in that in Step 2: 10 kg of polyacrylate resin (glass transition temperature 100 °C, molecular weight 70,000), 1 kg of cellulose acetate resin, 3 kg of hydroxyethyl acrylate, and 1 kg of isocyanate curing agent were added to the reaction kettle by weight, and stirring was continued for 2 h;

[0065] The remaining steps were the same as the preparation method of Example 1.

[0066] Comparative Example 5

[0067] The difference between this comparative example and Example 1 lies in that in Step 2: 10 kg of polyacrylate resin (glass transition temperature 100 °C, molecular weight 70,000), 1 kg of cellulose acetate resin, 3 kg of methyl methacrylate, and 1 kg of isocyanate curing agent were added to the reaction kettle by weight, and stirring was continued for 2 h;

[0068] The remaining steps were the same as the preparation method of Example 1.

[0069] Comparative Example 6

[0070] The difference between this comparative example and Example 1 lies in that in Step 2: 10 kg of polyacrylate resin (glass transition temperature 100 °C, molecular weight 70,000), 1 kg of cellulose acetate resin, 3 kg of butyl acrylate, and 1 kg of isocyanate curing agent were added to the reaction kettle by weight, and stirring was continued for 2 h;

[0071] The remaining steps were the same as the preparation method of Example 1.

[0072] The printing performance of Examples 1 to 3 and Comparative Examples 1 to 6 was tested, and the results are shown in Table 1 below.

[0073] Sample preparation: The coatings obtained in the examples and the comparative examples were coated on the surface of a PET film, dried at 90 - 130 °C, the coating dry weight was 1.2 - 1.4 g, the coating was embossed at a temperature of 180 - 185 °C, then vacuum aluminized, the coating was transferred to cardboard using glue, and relevant performance tests were carried out on the transferred cardboard. For the heat resistance performance test, a heat sealer was used, with a pressure of 2 kg, and the surface of the heat-pressed coating was 2S, and the color change of the coating was observed; for the pressure resistance and flower resistance performance test: the surface of the coating was pressed at a pressure of 25 kg at room temperature for one week, and the change of the coating was observed.

[0074] Table 1

[0075] Performance Test Cutting without Aluminum Spatter Flatness of Cut Temperature Resistance Performance Pressure Resistance Flowering Example 1 Cutting without Aluminum Spatter Flat 140℃ No Obvious Change Example 2 Cutting without Aluminum Spatter Flat 150℃ No Obvious Change Example 3 Cutting without Aluminum Spatter Flat 150℃ No Obvious Change Comparative Example 1 Cutting without Aluminum Spatter Slightly Adhesive 120℃ Partial Flowering Comparative Example 2 Cutting with Aluminum Spatter Adhesive 110℃ Severe Surface Flowering Comparative Example 3 Cutting with Aluminum Spatter Slightly Adhesive 130℃ Slightly Flowering Comparative Example 4 Unable to Test Unable to Test Unable to Test Unable to Test Comparative Example 5 Unable to Test Unable to Test Unable to Test Unable to Test Comparative Example 6 Unable to Test Unable to Test Unable to Test Unable to Test

[0076] As can be seen from Table 1, the anti-flying aluminum transfer coatings prepared in Examples 1 to 3, due to the addition of modified polyacrylate resin and isocyanate curing agent, can be quickly unblocked to form crosslinks during coating, drying and molding, which increases the polarity of the system, has higher temperature resistance, can effectively prevent the flying aluminum phenomenon during cutting, and at the same time, the incision is smooth and has excellent embossing resistance. However, in Comparative Example 1, no modified polyacrylate resin is added, only isocyanate curing agent is added, which cannot form unblocking crosslinks, and the obtained coating has poor performance, and there will be slight adhesion of the incision, local embossing and other phenomena; in Comparative Example 2, no isocyanate curing agent is added, only modified polyacrylate resin is added, and there is no isocyanate curing agent in the system, which will cause the modified polyacrylate resin to have a counter-effect in the system, affecting the entire system, and the obtained coating has very poor performance, which will There are phenomena such as flying aluminum during cutting, adhesion of the incision, and severe flowery surface; in comparative example 3, no modified polyacrylate resin and isocyanate curing agent are added, and the performance of the obtained coating is general, and there are phenomena such as flying aluminum during cutting, slight adhesion of the incision, and slight flowery surface; it can be seen that the anti-flying aluminum transfer coatings prepared in Examples 1 to 3 of the present invention are better than the coatings of comparative examples 1 to 3 in terms of incision flatness and embossing resistance. The incisions during cutting are smoother and will not stick, and there will be no flowery surface during mold embossing. In the preparation of the coatings of comparative examples 4 to 6, the raw materials of synthetic modified polyacrylate resin are added. Since the small molecule raw materials that have not been polymerized are added, they are unstable in the system, resulting in abnormalities such as flowery and cracking on the coating surface after coating and drying, and it is impossible to prepare a complete product, and then it is impossible to carry out subsequent tests normally.

[0077] Although the embodiments of the present invention have been disclosed as above, they are not limited to the applications listed in the specification and the implementation modes. They can be fully applied to various fields suitable for the present invention. For those familiar with the art, additional modifications can be easily implemented. Therefore, without departing from the general concept defined by the claims and the scope of equivalents, the present invention is not limited to specific details.

Claims

1. A preparation method of an anti-flying aluminum transfer coating, characterized in that The anti-flying aluminum transfer coating comprises the following components in weight percentage: 10-18 parts of polyacrylate resin, 3-8 parts of modified polyacrylate resin, 1-3 parts of isocyanate curing agent with an unblocking temperature range of 90-150° C., 1-8 parts of cellulose ester resin, 0-0.3 parts of auxiliary agent, and 70-85 parts of solvent; The cellulose ester resin is one or more of cellulose acetate, cellulose acetate butyrate, and cellulose acetate propionate with a molecular weight of 30,000 to 140,000; The preparation method of the anti-flying aluminum transfer coating comprises the following steps: Step 1: Add the solvent into the reaction kettle, then heat it to 45-55°C and maintain the stirring speed at 60-100 rpm; Step 2: Add polyacrylate resin, modified polyacrylate resin, isocyanate curing agent and cellulose ester resin into the reaction kettle and continue stirring for 1.5 to 3 hours; Step 3: Add the additive to the reactor, stir for 0.5 to 1 hour, then stop stirring, cool the product, filter it, and then package it to obtain an anti-flying aluminum transfer coating product; Wherein, the synthesis method of the modified polyacrylate resin in step 2 is: S1. In a batch reaction vessel, zinc chloride and 0.1 kg of polyethylene glycol are added to water to form an aqueous phase with a zinc chloride concentration of 5 ppm, and the mixture is stirred and heated to 50°C; S2, 25kg of 2-aminoethyl methacrylate, 40kg of ethyl methacrylate, 30kg of butyl methacrylate, 0.4kg of tert-butyl peroxy-2-ethylhexanoate and 3kg of isooctyl thioglycolate were mixed to obtain an oil phase; S3, adding the oil phase to the water phase at a volume ratio of 1:3, stirring at 50°C for 30 min, heating to 85°C, stirring and reacting for 3 h, heating to 95°C and stirring for 2 h; S4. After the reaction is completed, the solid product is collected by static sedimentation and filtration. The obtained solid product is washed and dried at 45° C. for 10 hours to obtain a modified polyacrylate resin.

2. The preparation method of the anti-flying aluminum transfer coating according to claim 1, characterized in that, The polyacrylate resin is a polymer of one or more monomers selected from methyl methacrylate, ethyl methacrylate, butyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, and isobornyl acrylate. The polyacrylate resin has a glass transition temperature of 50-110° C. and a molecular weight of 30,000-140,000.

3. The preparation method of the anti-flying aluminum transfer coating according to claim 1, wherein, The solvent is one or more of ethyl acetate, n-propyl acetate, n-butyl acetate, ethanol, n-propanol, isopropanol, acetone, butanone, propylene glycol methyl ether, and propylene glycol ethyl ether.

4. The preparation method of the anti-flying aluminum transfer coating according to claim 1, characterized in that, The auxiliary agent is one or more of a leveling agent, a defoaming agent, and an anti-scratch agent.

5. The preparation method of the anti-flying aluminum transfer coating according to claim 4, characterized in that, The leveling agent is one or more of Flow300, Glide410, Glide435, Glide450, Glide432, BYK-306, BYK-333, BYK-323, BYK-358N, BYK-354, DC11, DC67, DC57, DC56, DC54, and DC5211.

6. The preparation method of the anti-flying aluminum transfer coating according to claim 4, characterized in that The defoamer is one or more of BYK-141, BYK-052, BYK-051, BYK-066N, BYK-0234, Airex900, Airex910, Airex920, Airex9313, DC163, DC62, and DC65.

7. The preparation method of the anti-flying aluminum transfer coating according to claim 4, wherein The scratch-resistant agent is one or more of DC51, DC52, DC29, DC27, and DC18.