Wear-resistant and waterproof high-gloss polish and preparation method thereof

Abstract

This invention discloses a wear-resistant and waterproof high-gloss varnish and its preparation method. The raw materials of the high-gloss varnish include: 18-25% water-based acrylic resin, 20-25% acrylic film-forming emulsion, 25-30% acrylic non-film-forming emulsion, 15-20% acrylic-polyurethane emulsion, 13-4% wax emulsion, 20.5-1% wax emulsion, 0.05-0.15% wear-resistant additive, 0.5-0.8% leveling agent, 0.5-0.8% wetting agent, 0.04-0.8% defoamer, 0-2% thickener, and the balance being deionized water; the wax emulsion 1 is an emulsifier-free modified paraffin emulsion; the wax emulsion 2 is a polyethylene / paraffin emulsion. The synergistic effect of the acrylic-modified polyurethane and the wear-resistant additive greatly improves the wear resistance of the varnish; the synergistic effect of wax emulsion 1, wax emulsion 2, and the wear-resistant additive not only blocks moisture diffusion, thus providing water resistance, but also prevents re-sticking.

Description

Technical Field

[0001] This invention relates to the field of varnishes, and more specifically to a wear-resistant and waterproof high-gloss varnish. Background Technology

[0002] Lamination is a common post-printing processing technique used to protect and enhance the surface of printed materials. Lamination not only enhances the aesthetic appeal of printed materials but also makes their surfaces smoother, more resistant to stains, water, oil, abrasion, and folding, protecting them from damage during storage, transportation, distribution, and use, thus extending their lifespan. However, the use of plastic film poses environmental problems. Replacing lamination with water-based varnishes can reduce "white pollution" (plastic waste), facilitate its disposal and recycling, conserve resources, and reduce energy waste.

[0003] Water-based plastic varnish is a high-gloss water-based varnish. The components of water-based varnish, such as polyacrylate, contain hydrophilic functional groups, and polyacrylate emulsions and wax emulsions contain emulsifiers, which are highly hydrophilic. After the varnish dries and forms a film, it is easy to stick together in a high temperature and high humidity environment, which will cause loss of protective function and damage. At the same time, for packaging boxes, because the protected objects are heavy, the frictional resistance is greater, and the requirements for the wear resistance of the varnish are higher. Summary of the Invention

[0004] The purpose of this invention is to provide a wear-resistant and waterproof high-gloss varnish and its preparation method.

[0005] To achieve the above objectives, the present invention adopts the following technical solution:

[0006] This invention provides a wear-resistant and waterproof high-gloss varnish, the raw materials of which include the following components by weight percentage:

[0007] Water-based acrylic resin ·················18%-25%

[0008] Acrylic film-forming emulsions ··················20%-25%

[0009] Acrylic non-film-forming emulsion... 25%-30%

[0010] Acrylic-polyurethane emulsion ················15%-20%

[0011] Wax emulsion 1·····················3%-4%

[0012] Wax emulsion 2·····················0.5%-1%

[0013] Wear-resistant additives·····················0.05%-0.15%

[0014] Leveling agent ······················0.5%-0.8%

[0015] Wetting agent ······················0.5%-0.8%

[0016] Defoamer ······················0.04%-0.8%

[0017] Thickener ·····················0-2%

[0018] Deionized water... remaining balance.

[0019] The wax emulsion 1 is a modified paraffin emulsion without emulsifier, which has the effects of waterproofing, anti-sticking, alcohol resistance, improving surface smoothness, anti-caking, and anti-scratch.

[0020] The wax emulsion 2 is a polyethylene / paraffin emulsion with excellent water-repellent properties.

[0021] Preferably, the solid content of the wax emulsion 1 is 25%, and the particle size is 0.01μm to 0.5μm. More preferably, the wax emulsion 1 is CT3360 type wax emulsion (Weng Kai'er).

[0022] Preferably, the solid content of the wax emulsion 2 is 33%-35%, and the average particle size is 0.08 μm. More preferably, the wax emulsion 2 is a Joncryl Wax 120 type wax emulsion (BASF).

[0023] In a preferred embodiment of the present invention, the raw materials of the high-gloss varnish comprise the following components by weight percentage:

[0024] Water-based acrylic resin... 19%-22%

[0025] Acrylic film-forming emulsions... 20%-24%

[0026] Acrylic non-film-forming emulsion... 25%-28%

[0027] Acrylic-polyurethane emulsion... 18%-20%

[0028] Wax emulsion 1········3%-4%

[0029] Wax emulsion 2········0.6%-1%

[0030] Wear-resistant additives... 0.08%-0.12%

[0031] Leveling agent ········0.6%-0.8%

[0032] Wetting agent: 0.6%-0.7%

[0033] Defoamer ········0.06%-0.7%

[0034] Thickener ········0.5-1.5%

[0035] Deionized water... remaining balance.

[0036] Preferably, the waterborne acrylic resin is a styrene-acrylic resin solution used to adjust the viscosity of the varnish, allowing it to be transferred smoothly. More preferably, the styrene-acrylic resin solution has a solid content of 32%, a molecular weight of 8500, and a viscosity (25°C) of 2800 cPs. Even more preferably, the styrene-acrylic resin solution is Joncryl 354 type styrene-acrylic resin solution (BASF).

[0037] Preferably, the acrylic film-forming emulsion is a styrene-acrylic film-forming emulsion, which has excellent water and oil resistance and a high coefficient of friction. It has a low glass transition temperature (Tg), preferably -16°C, and can dry to form a film at room temperature. It possesses a certain degree of flexibility, and when used alone, the film has high viscosity, functioning similarly to an adhesive, with poor anti-re-sticking properties. However, due to the softness of the film, its wear resistance is also insufficient. Furthermore, its solid content is preferably 48.5%, and its viscosity (at 25°C) is preferably 700 cPs. More preferably, the styrene-acrylic film-forming emulsion is Joncryl 74-A type styrene-acrylic film-forming emulsion (BASF).

[0038] Preferably, the acrylic non-film-forming emulsion is a styrene-acrylic non-film-forming emulsion, which has high gloss and fast-drying properties. Preferably, the acrylic non-film-forming emulsion has a glass transition temperature (Tg) of 110°C. Its high glass transition temperature means it does not form a film after drying at room temperature, resulting in high resin hardness, good wear resistance, and good anti-re-tack properties. Therefore, this invention uses both acrylic film-forming and acrylic non-film-forming emulsions simultaneously. Furthermore, its solid content is preferably 44%, and its viscosity (25°C) is preferably 200 cPs. More preferably, the styrene-acrylic non-film-forming emulsion is JONCRYL 90 type styrene-acrylic non-film-forming emulsion (BASF).

[0039] The acrylic-polyurethane emulsion is a high-gloss, medium-hardness acrylic-modified polyurethane, which is heat-resistant, low-temperature resistant, forms a clear and full film, and has good water and solvent resistance. Preferably, the acrylic-polyurethane emulsion is HD4 type acrylic-modified polyurethane (Weng Kai'er).

[0040] Preferably, the wear-resistant additive is a water-dispersible, ultra-high molecular weight polydimethylsiloxane dispersion, which can improve wear resistance and scratch resistance. More preferably, the wear-resistant additive is DC-51 type wear-resistant additive (Dow Corning).

[0041] Preferably, the leveling agent is polyether-modified dimethylsiloxane, used to reduce the surface tension of the varnish and promote the formation of a smooth, uniform film during the drying process. More preferably, the leveling agent is BYK333 type leveling agent (BYK Chemicals).

[0042] Preferably, the wetting agent is a nonionic organic surfactant used to reduce the surface tension of the varnish, allowing it to better wet and spread on the substrate. More preferably, the wetting agent is WET D-500 type wetting agent (Weng Kai'er).

[0043] Preferably, the defoamer is a polyether siloxane copolymer emulsion used for defoaming and foam suppression. More preferably, the defoamer is FA-025 type defoamer (Weng Kai'er).

[0044] Preferably, the thickener is a polyurethane-modified polyether used to adjust viscosity. More preferably, the thickener is a 612NC type thickener (Synopco).

[0045] Another aspect of the present invention provides a method for preparing the above-mentioned high-gloss varnishes, the method comprising the following steps:

[0046] Add some deionized water and water-based acrylic resin to a container and stir until homogeneous. Then, add defoamer, leveling agent, wetting agent, and abrasion-resistant additive in sequence, and stir until homogeneous. Finally, add acrylic film-forming emulsion, acrylic non-film-forming emulsion, acrylic-polyurethane emulsion, wax emulsion 1, and wax emulsion 2 in sequence.

[0047] Stir until homogeneous (preferably at 800 rpm to 1200 rpm for 0.3 to 1 hour); then add the thickener while stirring and stir until homogeneous.

[0048] After cooling to room temperature, add ammonia or an organic ammonia neutralizer (such as AMP-95) to adjust the pH to 8-9, and add water to adjust the viscosity to obtain the high-gloss varnish.

[0049] Preferably, water is added to adjust the viscosity to 40-60 s / 25℃.

[0050] Preferably, the mixture is filtered and bottled after adding water to adjust the viscosity.

[0051] The addition of acrylic-polyurethane emulsion increases the elasticity of the varnish film. During the varnish film formation process, the wear-resistant additive migrates to the surface of the varnish film, forming a very thin silicone layer. When subjected to external force, the silicone layer on the surface is relatively hard and can resist external friction, while the underlying resin layer is elastic and can store some force. After the external force disappears, the stored force is released. The synergistic effect of acrylic-modified polyurethane and wear-resistant additive can greatly improve the wear resistance of the varnish.

[0052] During the varnish film formation process, the wax emulsion and wear-resistant additive float to the surface of the varnish film. In addition to excellent wear resistance, the wear-resistant additive of this invention also exhibits strong hydrophobicity. Due to their extremely low surface energy, water droplets cannot spread on the surface of the wax emulsion 2 and the wear-resistant additive, resulting in a water-repellent property with a "lotus leaf effect." The wax emulsion 1 is a modified paraffin emulsion without emulsifiers and has no polar functional groups. The wax emulsion 2 and the wear-resistant additive repel water, and the wax emulsion 1 does not absorb water. The wax emulsion 1, wax emulsion 2, and wear-resistant additive float to the varnish surface, forming a dense insulating layer with weak adhesion, reducing tackiness during contact. The three components work synergistically to both prevent water diffusion and prevent re-adhesion. Detailed Implementation

[0053] To more clearly illustrate the present invention, the following description, in conjunction with preferred embodiments, further clarifies the invention. Those skilled in the art should understand that the specific descriptions below are illustrative rather than restrictive, and should not be construed as limiting the scope of protection of the present invention.

[0054] The high-gloss varnishes used in the following examples and comparative examples were prepared using the following steps:

[0055] 1) Pour some deionized water and water-based acrylic resin into a container in sequence, stir at 400 rpm, stir evenly, then add some defoamer, leveling agent, wetting agent, defoamer and wear-resistant additive in sequence, and stir evenly.

[0056] 2) While stirring, add the acrylic film-forming emulsion, acrylic non-film-forming emulsion, acrylic-polyurethane emulsion, and wax emulsion in sequence, stirring at 1000 rpm for 1 hour;

[0057] 3) Add the thickener while stirring and stir until well combined;

[0058] 4) Cool to room temperature, add ammonia to adjust the pH to 8-9, add water to adjust the viscosity, filter and bottle.

[0059] The raw materials involved are specifically:

[0060] Waterborne acrylic resin: Joncryl 354, BASF;

[0061] Acrylic film-forming emulsion: Joncryl 74-A, BASF;

[0062] Acrylic non-film-forming emulsion: JONCRYL 90, BASF;

[0063] Acrylic-polyurethane emulsion: HD4, Weng Kai'er;

[0064] Wax emulsion 1: CT3360, Weng Kai'er;

[0065] Wax emulsion 2: Joncryl Wax 120, BASF;

[0066] Wear-resistant additives: DC-51, Dow Corning;

[0067] Leveling agent: BYK333, BYK Chemicals;

[0068] Wetting agent: WET D-500, Onkel;

[0069] Defoamer: FA-025, Weng Kai'er;

[0070] Thickener: 612NC thickener, Sanopco.

[0071] The performance tests involved include:

[0072] 1) Viscosity / 25℃:

[0073] To test the viscosity, use a DIN 4# cup. Block the outlet with your finger and slowly pour the water-based varnish into the cup until the liquid level rises above the upper edge. If there are air bubbles, wait for them to float to the surface. Then, use a clean, flat glass plate to push along the edge once to remove the protruding liquid level and air bubbles, ensuring that the liquid level is level with the upper edge. Release your finger, and the water-based varnish will flow out vertically. Simultaneously, start a stopwatch. The water-based varnish will flow out in a line. Stop the stopwatch when you stop the stopwatch. The measured time is the viscosity of the water-based varnish, in seconds.

[0074] 2) Gloss:

[0075] Gloss refers to the ability of a printed sample to reflect light at a certain angle. Gloss is tested using a BYK gloss meter at a 60° angle.

[0076] 3) Abrasion resistance:

[0077] The test was conducted according to the test conditions for ink layer abrasion resistance in GB / T 7706-2008 "Relief Printing of Decorative Materials" 6.8. The abrasion resistance of the environmentally friendly water-based varnish was judged by whether the ink layer color was rubbed off. The number of rubbings when the ink layer color first started to be rubbed off was also recorded.

[0078] 4) Smoothness:

[0079] Using a slip angle device, one of the oiled samples (oiled side up) is fixed flat on a horizontal test platform with the sample parallel to the length of the test platform. The other oiled sample, with the smooth side down, is attached to a 1kg slider. The slider with the sample fixed is then placed in the center of the first sample to start the test. The test is stopped when the slider slides down, and the angle of the test platform is recorded.

[0080] 5) Water resistance and anti-sticking performance:

[0081] Apply varnish to white cardstock using a No. 0 wire rod. After drying, cut the sample into a 12×12cm square. Place one of the cut squares on a glass plate in an oven with the varnish side facing up. Add 0.2mL of water to the varnish side. Place the other sample on top of the water-dripping sample with the varnish side facing down. Place another glass plate on top of the other sample, and then place a 1kg weight on the glass plate. Incubate at 60℃ for 60 minutes and observe the adhesion.

[0082] The raw material formulations for each embodiment and comparative example are as follows (containing the following ingredients per 1000 grams of product):

[0083] Example 1

[0084] Water-based acrylic resin (styrene-acrylic resin solution) ······· 200g

[0085] Acrylic film-forming emulsion··············230g

[0086] Acrylic non-film-forming emulsion·············270g

[0087] Acrylic-polyurethane emulsion············200g

[0088] Wax emulsion 1················36g

[0089] Wax emulsion 2·······················8g

[0090] Wear-resistant additive·······················1g

[0091] Leveling agent·······················7g

[0092] Wetting agent························6g

[0093] Defoamer·······················6g

[0094] Thickener·······················1g

[0095] Deionized water· ...

[0096] Example 2

[0097] Water-based acrylic resin (styrene-acrylic resin solution) ············ 200g

[0098] Acrylic film-forming emulsion···················230g

[0099] Acrylic non-film-forming emulsion··················270g

[0100] Acrylic-polyurethane emulsion··················200g

[0101] Wax emulsion 1······················30g

[0102] Wax emulsion 2······················8g

[0103] Wear-resistant additive·····················1g

[0104] Leveling agent·····················7g

[0105] Wetting agent······················6g

[0106] Defoamer·····················6g

[0107] Thickener·····················1g

[0108] Deionized water· ...

[0109] Example 3

[0110] Water-based acrylic resin (styrene-acrylic resin solution) ··········· 200g

[0111] Acrylic film-forming emulsion··················230g

[0112] Acrylic non-film-forming emulsion·················270g

[0113] Acrylic-polyurethane emulsion················200g

[0114] Wax emulsion 1····················40g

[0115] Wax emulsion 2····················8g

[0116] Wear-resistant additive····················1g

[0117] Leveling agent····················7g

[0118] Wetting agent·····················6g

[0119] Defoamer·····················6g

[0120] Thickener····················1g

[0121] Deionized water· ...

[0122] Comparative Example 1

[0123] Water-based acrylic resin (styrene-acrylic resin solution) ·········· 200g

[0124] Acrylic film-forming emulsion·················230

[0125] Acrylic non-film-forming emulsion················270g

[0126] Acrylic-polyurethane emulsion················0g

[0127] Wax emulsion 1···················36g

[0128] Wax emulsion 2·······················8g

[0129] Wear-resistant additive······················1g

[0130] Leveling agent······················7g

[0131] Wetting agent·······················6g

[0132] Defoamer·······················6g

[0133] Thickener·······················1g

[0134] Deionized water· ...

[0135] Comparative Example 2

[0136] Water-based acrylic resin (styrene-acrylic resin solution) ············ 200g

[0137] Acrylic film-forming emulsion···················230g

[0138] Acrylic non-film-forming emulsion··················270g

[0139] Acrylic-polyurethane emulsion·················200g

[0140] Wax emulsion 1·····················36g

[0141] Wax emulsion 2·····················8g

[0142] Wear-resistant additives·····················0g

[0143] Leveling agent·····················7g

[0144] Wetting agent······················6g

[0145] Defoamer·····················6g

[0146] Thickener·····················1g

[0147] Deionized water· ...

[0148] Comparative Example 3

[0149] Water-based acrylic resin (styrene-acrylic resin solution) ············ 200g

[0150] Acrylic film-forming emulsion···················230g

[0151] Acrylic non-film-forming emulsion··················270g

[0152] Acrylic-polyurethane emulsion·················200g

[0153] Wax emulsion 1·····················0g

[0154] Wax emulsion 2·····················0g

[0155] Wear-resistant additive·····················1g

[0156] Leveling agent·····················7g

[0157] Wetting agent······················6g

[0158] Defoamer·····················6g

[0159] Thickener·····················1g

[0160] Deionized water· ...

[0161] Comparative Example 4

[0162] Water-based acrylic resin (styrene-acrylic resin solution) ··········· 200g

[0163] Acrylic film-forming emulsion··················230g

[0164] Acrylic non-film-forming emulsion·················270g

[0165] Acrylic-polyurethane emulsion················200g

[0166] Wax emulsion 1····················0g

[0167] Wax emulsion 2······················8g

[0168] Wear-resistant additive······················1g

[0169] Leveling agent······················7g

[0170] Wetting agent·······················6g

[0171] Defoamer·······················6g

[0172] Thickener······················1g

[0173] Deionized water· ...

[0174] Comparative Example 5

[0175] Water-based acrylic resin (styrene-acrylic resin solution) ··········· 200g

[0176] Acrylic film-forming emulsion··················230g

[0177] Acrylic non-film-forming emulsion·················270g

[0178] Acrylic-polyurethane emulsion················200g

[0179] Wax emulsion 1····················36g

[0180] Wax emulsion 2·····················0g

[0181] Wear-resistant additive····················1g

[0182] Leveling agent····················7g

[0183] Wetting agent·····················6g

[0184] Defoamer·····················6g

[0185] Thickener····················1g

[0186] Deionized water· ...

[0187] The varnishes obtained in the above examples and comparative examples were subjected to film formation tests, and the performance test results are shown in Table 1 below.

[0188] Table 1. Performance test results of the varnish films obtained in the examples and comparative examples.

[0189]

[0190] In the formulation of this invention, the addition of acrylic-modified polyurethane increases the elasticity of the varnish film. During the varnish film formation process, the wear-resistant additive migrates to the surface of the varnish film, forming a very thin silicone layer on its surface. When subjected to external force, the silicone layer on the surface is relatively hard, resisting external friction, while the underlying resin layer is elastic and can store some force. After the external force disappears, the stored force is released. The synergistic effect of acrylic-modified polyurethane and wear-resistant additive can greatly improve the wear resistance of the varnish.

[0191] During the varnish film formation process, the wax emulsion and abrasion-resistant additive float to the surface of the varnish film. In addition to its excellent abrasion resistance, the abrasion-resistant additive also has extremely strong hydrophobicity. Due to their extremely low surface energy, water droplets cannot spread on the surface of wax emulsion 2 and the abrasion-resistant additive, resulting in a water-repellent property with a "lotus leaf effect." Wax emulsion 1 is a modified paraffin emulsion without emulsifiers and has no polar functional groups. Wax emulsion 2 and the abrasion-resistant additive repel water, and wax emulsion 1 does not absorb water. Wax emulsion 1, wax emulsion 2, and the abrasion-resistant additive float to the varnish surface, forming a dense isolation layer with weak adhesion, reducing tackiness upon contact. The three work synergistically to both block water diffusion and prevent re-adhesion.

[0192] Obviously, the above embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the implementation of the present invention. For those skilled in the art, other variations or modifications can be made based on the above description. It is impossible to exhaustively list all the implementation methods here. All obvious variations or modifications derived from the technical solutions of the present invention are still within the protection scope of the present invention.

Claims

1. A wear-resistant and waterproof high-gloss varnish, characterized in that, The raw materials for the high-gloss varnish include the following components by weight percentage: Water-based acrylic resin... 18%-25% Acrylic film-forming emulsions... 20%-25% Acrylic non-film-forming emulsion... 25%-30% Acrylic-polyurethane emulsion... 15%-20% Wax emulsion 1············3%-4% Wax emulsion 2············0.5%-1% Wear-resistant additives ···········0.05%-0.15% Leveling agent ···········0.5%-0.8% Wetting agent: 0.5%-0.8% Defoamer ···········0.04%-0.8% Thickener ············0-2% Deionized water... Remaining amount The aqueous acrylic resin is a styrene-acrylic resin solution with a solid content of 32%, a molecular weight of 8500, and a viscosity of 2800 cPs at 25°C. The acrylic film-forming emulsion is a styrene-acrylic film-forming emulsion with a glass transition temperature of -16°C, a solid content of 48.5%, and a viscosity of 700 cPs at 25°C. The acrylic non-film-forming emulsion is a styrene-acrylic non-film-forming emulsion with a glass transition temperature of 110°C, a solid content of 44%, and a viscosity of 200 cPs at 25°C. The acrylic-polyurethane emulsion used is HD4 type acrylic-modified polyurethane; The wax emulsion 1 is an emulsifier-free modified paraffin emulsion; the solid content of the wax emulsion 1 is 25%, and the particle size is 0.01 μm ~ 0.5 μm; The wax emulsion 2 is a polyethylene / paraffin emulsion; the solid content of the wax emulsion 2 is 33%-35%, and the average particle size is 0.08μm; The wear-resistant additive is a polydimethylsiloxane dispersion.

2. The high-gloss varnish according to claim 1, characterized in that, The leveling agent is polyether-modified dimethylsiloxane.

3. The high-gloss varnish according to claim 1, characterized in that, The wetting agent is a nonionic organic surfactant.

4. The high-gloss varnish according to claim 1, characterized in that, The defoamer is a polyether siloxane copolymer emulsion.

5. The high-gloss varnish according to claim 1, characterized in that, The thickener is a polyurethane-modified polyether.

6. A method for preparing a high-gloss varnish according to any one of claims 1-5, characterized in that, The preparation method includes the following steps: Add some deionized water and water-based acrylic resin to a container and stir until homogeneous. Then add defoamer, leveling agent, wetting agent, defoamer and wear-resistant additive in sequence and stir until homogeneous. Then add acrylic film-forming emulsion, acrylic non-film-forming emulsion, acrylic-polyurethane emulsion, wax emulsion 1 and wax emulsion 2 in sequence and stir until homogeneous. Then add thickener while stirring and stir until homogeneous. After cooling to room temperature, add ammonia or an organic ammonia neutralizer to adjust the pH to 8-9, and add water to adjust the viscosity to obtain the high-gloss varnish.

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