A method for preparing a permanent antibacterial acrylic bathroom panel

Abstract

This invention discloses a method for preparing a permanent antibacterial acrylic bathroom panel, comprising the following steps: Step 1: Prepolymerizing materials including methyl methacrylate, hydroxyl-terminated acrylate, phosphate-terminated monomers, and a high-temperature initiator to obtain an acrylic prepolymer; Step 2: Predispersing an antibacterial agent to obtain an antibacterial agent slurry; Step 3: Uniformly mixing materials including the acrylic prepolymer, the antibacterial agent slurry, a polyfunctional acrylate crosslinking agent, and a low-temperature initiator; Step 4: Pouring the mixture into a glass mold, heating it in a 60°C water bath until the edges harden, and then baking it at 120°C for 2-3 hours; Step 5: Cooling to room temperature, demolding, and obtaining a permanent antibacterial acrylic panel suitable for bathroom products; Effects: By copolymerizing methyl methacrylate, hydroxyl-terminated acrylate monomers, and phosphate-terminated acrylate monomers, the dispersibility, firmness, mechanical properties, and water resistance of the antibacterial agent are improved; and an antibacterial agent slurry is obtained through a specific predispersion formula and process.

Description

Technical Field

[0001] This invention relates to the field of bathroom panel manufacturing technology, and in particular to a method for preparing a permanent antibacterial acrylic bathroom panel. Background Technology

[0002] With the frequent emergence of COVID-19, influenza virus, and various infectious bacteria, the public's attention to hygiene and epidemic prevention has been increasing, and the demand for various antibacterial and antiviral products has also increased rapidly. Acrylic products are widely used in construction, furniture, bathroom products, interior decoration, medical devices, automotive instruments, industrial control instruments and other applications that may come into contact with the skin, and the demand for antibacterial acrylic is also increasing.

[0003] Currently, many technical solutions for permanent antibacterial acrylic sheets have been published, most of which use silver ion antibacterial agents, added to acrylic materials through physical blending. However, when used in bathroom materials, the sheets undergo high temperatures and stretching during post-processing. If the antibacterial agent is not evenly dispersed in the sheet, defects such as bumps, bubbles, and discoloration may appear on the stretched surface, or processing problems such as cracking and breakage may occur. At the same time, the addition of antibacterial agents affects the mechanical properties, water resistance, and heat resistance of acrylic sheets. The acrylic sheet formula needs to be modified when adding antibacterial agents to reduce the loss of other properties. Existing acrylic sheets are not performing well and cannot meet people's needs.

[0004] In view of the above, it is necessary to improve the existing acrylic sheets to meet the current needs of acrylic sheet use. Summary of the Invention

[0005] The technical solution of the present invention to achieve the above objectives is a method for preparing a permanent antibacterial acrylic bathroom panel, comprising the following steps:

[0006] Step 1: Acrylic prepolymer is obtained by prepolymerizing materials including methyl methacrylate, hydroxyl-terminated acrylate, phosphate-terminated monomers, and high-temperature initiator;

[0007] Step 2: Obtain antibacterial agent slurry by pre-dispersing the antibacterial agent;

[0008] Step 3: Mix the materials, including acrylic prepolymer, antibacterial slurry, polyfunctional acrylate crosslinking agent, and low-temperature initiator, evenly.

[0009] Step 4: Pour into a glass mold, heat in a 60℃ water bath until the edges harden, then bake at 120℃ for 2-3 hours;

[0010] Step 5: Cool to room temperature, demold, and obtain a permanent antibacterial acrylic sheet that can be used in bathroom products.

[0011] As a further supplement to this technical solution, the acrylic prepolymer is added in the following proportions: 100 parts methyl methacrylate, 1-3 parts hydroxyl-terminated acrylate, 0.1-0.5 parts phosphate-terminated monomer, and 0.001-0.003 parts high-temperature initiator. The prepolymer is prepolymerized at 80-105℃ for 30-60 minutes, and the room temperature viscosity of the prepolymer is 300-1000 CPS.

[0012] To further supplement this technical solution, the preparation method of the antibacterial agent slurry is as follows: the ratio of antibacterial agent to dispersant is 1:0.03 to 1:0.10, and the feeding sequence is as follows: first, add the acrylic prepolymer to the mixing tank, and stir at a speed of 1000-2000 rpm; then add the dispersant and stir evenly; then slowly add the antibacterial agent powder while stirring; after the feeding is completed, continue stirring for 3 hours; and obtain the antibacterial agent slurry after filtering through a 1000-mesh filter.

[0013] As a further supplement to this technical solution, the addition ratio of acrylic prepolymer, antibacterial agent slurry, polyfunctional acrylate crosslinking agent, and low-temperature initiator in step three is as follows: 100 parts of total acrylic prepolymer (including acrylic prepolymer in the preparation of antibacterial agent slurry), 0.3-0.6 parts of antibacterial agent, 0.01-0.05 parts of polyfunctional acrylate crosslinking agent, and 0.01-0.05 parts of low-temperature initiator. Mix and stir evenly, and remove air bubbles by vacuuming. If the viscosity of the prepolymer is too high, it is difficult to remove air bubbles; if the viscosity is too low, it is easy to precipitate.

[0014] As a further supplement to this technical solution, the hydroxyl-terminated acrylate is any one of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxymethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, and hydroxymethyl methacrylate.

[0015] As a further supplement to this technical solution, the terminal phosphate ester monomer is one or more of the following: methacryloyloxyethyl ester, methacryloyloxyethyl ester, methacryloyloxyethyl ester, acryloyloxyethyl ester, acryloyloxyethyl ester, acryloyloxyethyl ester, diethyl methacryloyloxyethyl ester, and diethyl acryloyloxyethyl ester.

[0016] As a further supplement to this technical solution, the high-temperature initiator is any one of azobisisobutyronitrile, benzoyl peroxide, di(4-methylbenzoyl peroxide), tert-amyl peroxide-2-ethylhexanoate, and tert-butyl peroxide-2-ethylhexanoate.

[0017] As a further supplement to this technical solution, the antibacterial agent is a silver ion antibacterial agent.

[0018] As a further supplement to this technical solution, the polyfunctional acrylate crosslinking agent is any one of pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, triisocyanurate triacrylate, and trimethylolpropane triacrylate.

[0019] As a further supplement to this technical solution, the low-temperature initiator is any one of azobisisoheptanenitrile, diisobutyryl peroxide, cumyl peroxyneodecanate, and bis(3-methoxybutyl peroxydicarbonate).

[0020] Its beneficial effects are as follows: This invention provides a method for preparing a permanent antibacterial acrylic bathroom panel. By copolymerizing methyl methacrylate, hydroxyl-terminated acrylate monomers, and phosphate-terminated acrylate monomers, the dispersibility and stability of the antibacterial agent are improved. Through a specific pre-dispersion formula and process, an antibacterial agent slurry is obtained. Before casting the panel, a polyfunctional acrylate crosslinking agent is added to improve the mechanical properties and water resistance. A permanent antibacterial acrylic panel for use in bathroom products is obtained. Detailed Implementation

[0021] To facilitate a clearer understanding of this technical solution by those skilled in the art, the technical solution of the present invention will be described in detail below:

[0022] A method for preparing a permanent antibacterial acrylic bathroom panel includes the following steps:

[0023] Step 1: Acrylic prepolymer is obtained by prepolymerizing materials including methyl methacrylate, hydroxyl-terminated acrylate, phosphate-terminated monomers, and high-temperature initiator;

[0024] Step 2: Obtain antibacterial agent slurry by pre-dispersing the antibacterial agent;

[0025] Step 3: Mix the materials, including acrylic prepolymer, antibacterial slurry, polyfunctional acrylate crosslinking agent, and low-temperature initiator, evenly.

[0026] Step 4: Pour into a glass mold, heat in a 60℃ water bath until the edges harden, then bake at 120℃ for 2-3 hours;

[0027] Step 5: Cool to room temperature, demold, and obtain a permanent antibacterial acrylic sheet that can be used in bathroom products.

[0028] The acrylic prepolymer is prepared by adding 100 parts of methyl methacrylate, 1-3 parts of hydroxyl-terminated acrylate, 0.1-0.5 parts of phosphate-terminated monomer, and 0.001-0.003 parts of high-temperature initiator, and prepolymerizing at 80-105℃ for 30-60 minutes. The room temperature viscosity of the prepolymer is 300-1000 CPS.

[0029] The preparation method of the antibacterial agent slurry is as follows: the ratio of antibacterial agent to dispersant is 1:0.03 to 1:0.10, and the feeding sequence is as follows: first, add acrylic prepolymer to the mixing tank, and stir at a speed of 1000-2000 rpm. Then, add the dispersant and stir evenly. Then, slowly add the antibacterial agent powder while stirring. After the feeding is completed, continue stirring for 3 hours. After filtering through a 1000-mesh filter, the antibacterial agent slurry is obtained.

[0030] In step three, the addition ratios of acrylic prepolymer, antibacterial agent slurry, polyfunctional acrylate crosslinking agent, and low-temperature initiator are as follows: 100 parts of total acrylic prepolymer (including acrylic prepolymer in the preparation of antibacterial agent slurry), 0.3-0.6 parts of antibacterial agent, 0.01-0.05 parts of polyfunctional acrylate crosslinking agent, and 0.01-0.05 parts of low-temperature initiator. Mix and stir evenly, and remove air bubbles by vacuuming. If the viscosity of the prepolymer is too high, it will be difficult to remove air bubbles; if the viscosity is too low, it will easily settle.

[0031] The hydroxyl-terminated acrylate is any one of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxymethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, and hydroxymethyl methacrylate.

[0032] The terminal phosphate ester monomer is one or more of the following: mono(methacryloyloxyethyl) phosphate, di(methacryloyloxyethyl) phosphate, tri(methacryloyloxyethyl) phosphate, mono(acryloyloxyethyl) phosphate, di(acryloyloxyethyl) phosphate, tri(acryloyloxyethyl) phosphate, diethyl phosphate, and diethyl phosphate.

[0033] The high-temperature initiator is any one of azobisisobutyronitrile (AIBN), benzoyl peroxide (BPO), bis(4-methylbenzoyl peroxide), tert-amyl peroxide-2-ethylhexanoate, and tert-butyl peroxide-2-ethylhexanoate.

[0034] Among them, the antibacterial agent is a silver ion antibacterial agent.

[0035] Among them, the polyfunctional acrylate crosslinking agent is any one of pentaerythritol tetraacrylate (Changxing EM241), dipentaerythritol hexaacrylate (Changxing EM263), tri(2-hydroxyethyl) isocyanurate triacrylate (Changxing EM2308), and trimethylolpropane triacrylate (Changxing EM231).

[0036] The low-temperature initiator is any one of azobisisoheptanenitrile (ADVN), diisobutyryl peroxide (DIPB), cumyl peroxyneodecanate (CPND), or bis(3-methoxybutyl peroxy)dicarbonate.

[0037] In this embodiment of the invention, methyl methacrylate (MMA) is referred to as CAS Registry No. 80-62-6.

[0038] In this embodiment of the invention, the terminal hydroxy acrylate is hydroxyethyl methacrylate, abbreviated as HEMA, CAS Registry No. 868-77-9;

[0039] In the embodiments of this invention, the terminal phosphate monomers, Sartoma SR9050, is mono(methacryloyloxyethyl) phosphate, and Changxing EM39 is a mixture of mono(methacryloyloxyethyl) phosphate and di(methacryloyloxyethyl) phosphate.

[0040] In this invention, the antibacterial agent is a silver ion antibacterial agent, and the agent selected in the examples is silver ion antibacterial agent. BC 11-01 BCA 21-61; Antibacterial agents are expensive, and excessive addition increases costs and reduces the performance of the board.

[0041] In this embodiment of the invention, the dispersant is Lubrizol 24000;

[0042] In this embodiment of the invention, an ultraviolet absorber, Suqian Liansheng UV329, was added during the preparation of materials before plate making, with an addition amount of 0.1-0.5 parts;

[0043] In this embodiment of the invention, an antioxidant, specifically the high-temperature resistant antioxidant Revonox 608, was added during the pre-processing of the board material, at a dosage of 0.1-0.5 parts.

[0044] Example

[0045] The following table lists the formulations of five acrylic prepolymers:

[0046]

[0047]

[0048] The processing conditions and room temperature viscosity of the five acrylic prepolymers are detailed in the table below:

[0049] project Prepolymer 1 Prepolymer 2 Prepolymer 3 Prepolymer 4 Prepolymer 5 reaction temperature 80℃ 95℃ 105℃ 95℃ 95℃ Pre-gathering time 30min 60min 45min 60min 60min viscosity at room temperature 331cps 986cps 662cps 708cps 826cps

[0050] The following lists the mixing ratios of five antibacterial agent slurries and the phenomena observed after standing:

[0051]

[0052] Note: In the antibacterial slurry, the antibacterial agent accounts for approximately 50%;

[0053] The formula for making antibacterial bathroom panels using the above five types of acrylic prepolymer materials and antibacterial agent slurry is as follows:

[0054]

[0055]

[0056] Note: In the antibacterial slurry, the antibacterial agent accounts for approximately 50%;

[0057] After the antibacterial acrylic slurry from Examples 1-5 is stirred evenly, 2 kg is placed in a beaker and left to stand for 48 hours to observe whether sedimentation occurs. The remaining material is poured into a 3 mm glass mold. The mold is heated in a 60°C water bath for 3 hours, then removed and heated in a 120°C water bath for 2 hours. After cooling, it is demolded to obtain an antibacterial acrylic bathroom panel.

[0058] The performance data and sedimentation phenomena of the antibacterial acrylic bathroom panels in Examples 1-5 are shown in the table below:

[0059]

[0060] Five comparative antibacterial bathroom panels were prepared using the above five types of acrylic prepolymer materials and antibacterial agent slurry. The formulas are as follows:

[0061]

[0062]

[0063] Note: In the antibacterial slurry, the antibacterial agent accounts for approximately 50%;

[0064] After mixing the materials in the above comparative ratios 1-5 evenly, take 2 kg of the antibacterial acrylic slurry and put it in a beaker. Let it stand for 48 hours to observe whether there is sedimentation. Pour the remaining material into a 3mm glass mold. After heating the mold in a 60℃ water bath for 3 hours, take it out and heat it in a 120℃ water bath for 2 hours. After cooling, demold to obtain the antibacterial acrylic bathroom panel.

[0065] The performance data and sedimentation phenomena of the antibacterial acrylic bathroom panels in Comparative Examples 1-5 are shown in the table below:

[0066] Observation Projects Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 The mixed slurry was left to stand for 48 hours. Layering Unlayered Rockwell hardness / HRM / 86 <![CDATA[Izod impact strength / KJ / m 2 > / 18.1 Tensile strength / MPa / 61 Elongation at break / % / 4.3 Tensile modulus of elasticity / MPa / 2606 Vicat softening point / °C / 91 Hot water resistance / Gray mark level 2 crosslinking degree / qualified Water absorption / mg / 67 Vacuum forming test / No abnormalities Surface appearance after vacuum forming / No abnormalities Escherichia coli antibacterial rate / 99.6％ Staphylococcus aureus antibacterial rate / 99.7％

[0067] As can be seen from the comparison between Example 2 and Comparative Example 1: when hydroxyl-terminated acrylate and phosphate-terminated acrylate are not added to the acrylic prepolymer, the dispersion effect of the antibacterial agent becomes worse, and precipitation occurs after standing for 48 hours after preparation.

[0068] As can be seen from the comparison between Example 2 and Comparative Example 2, when preparing antibacterial agent slurry, adding too much dispersant will lead to a decrease in the mechanical properties, water resistance, and heat resistance of the final board.

[0069] Among them, the performance testing method for antibacterial bathroom panels is as follows:

[0070] 1. Rockwell hardness, GB / T 3398.2;

[0071] 2. Unnotched impact strength, GB / T 1043.1;

[0072] 3. Tensile strength, GB / T 1040;

[0073] 4. Elongation at break, GB / T 1040;

[0074] 5. Tensile modulus of elasticity, GB / T 1040;

[0075] 6. Vicat softening point, GB / T 1633;

[0076] 7. Hot water resistance, EN263:2008, Section 3.6.2, gray scale grade ≥3 is acceptable;

[0077] 8. Crosslinking degree, EN263:2008, Section 4.6, the standard sample is qualified if there is no dissolution or adhesion after soaking in MMA for 16 hours;

[0078] 9. Water absorption, EN263:2008, Section 4.7, according to common industry requirements, for a 50mm×50mm sample block, the water absorption ≤40mg;

[0079] 10. Vacuum forming test: Take a 1m x 1m sample, heat it at 200℃ for 15 minutes, and then place it in a mold with an inner cavity size of 0.8m x 0.8m x 0.8m. Vacuum form it and observe whether there are any cracks, and whether there are any defects such as bumps, dents or bubbles on the surface.

[0080] 11. Antibacterial test, standard ISO 22196, test species: Escherichia coli (ATCC 8739) and Staphylococcus aureus (ATCC 6538P), antibacterial rate (%) calculation formula: (BC) / B×100%.

[0081] B: Average bacterial count (cells / cm²) 24 hours after inoculation of blank sample (untreated control sample) 2 )

[0082] C: Average bacterial count (cells / cm²) 24 hours after inoculation of the test sample 2 ).

[0083] The above technical solutions only embody the preferred technical solutions of the present invention. Any modifications that may be made by those skilled in the art to certain parts thereof embody the principles of the present invention and fall within the protection scope of the present invention.

Claims

1. A method for preparing a permanent antibacterial acrylic bathroom panel, characterized in that, Includes the following steps: Step 1: Acrylic prepolymer is obtained by prepolymerizing materials including methyl methacrylate, hydroxyl-terminated acrylate, phosphate-terminated monomers, and high-temperature initiator; Step 2: Obtain antibacterial agent slurry by pre-dispersing the antibacterial agent; Step 3: Mix the materials, including acrylic prepolymer, antibacterial slurry, polyfunctional acrylate crosslinking agent, and low-temperature initiator, evenly. Step 4: Pour into a glass mold, heat in a 60℃ water bath until the edges harden, then bake at 120℃ for 2-3 hours; Step 5: Cool to room temperature, demold, and obtain a permanent antibacterial acrylic sheet that can be used in bathroom products; The acrylic prepolymer is added in the following proportions: 100 parts methyl methacrylate, 1-3 parts hydroxyl-terminated acrylate, 0.1-0.5 parts phosphate-terminated monomer, and 0.001-0.003 parts high-temperature initiator. It is prepolymerized at 80-105℃ for 30-60 minutes. The room temperature viscosity of the prepolymer is 300-1000 CPS. The method for preparing the antibacterial agent slurry is as follows: the ratio of antibacterial agent to dispersant is 1:0.03 to 1:0.10, and the feeding sequence is as follows: first, add a portion of acrylic prepolymer to the mixing tank, and stir at a speed of 1000-2000 rpm; then add the dispersant and stir evenly; then slowly add the antibacterial agent powder while stirring; after the feeding is completed, continue stirring for 3 hours; and obtain the antibacterial agent slurry after filtering through a 1000-mesh filter. In step three, the addition ratios of the total amount of acrylic prepolymer, antibacterial agent, polyfunctional acrylate crosslinking agent, and low-temperature initiator are as follows: 100 parts of total acrylic prepolymer, 0.3-0.6 parts of antibacterial agent, 0.01-0.05 parts of polyfunctional acrylate crosslinking agent, and 0.01-0.05 parts of low-temperature initiator. Mix and stir evenly, and then vacuum to remove air bubbles. The antibacterial agent is a silver ion antibacterial agent.

2. The method for preparing a permanent antibacterial acrylic bathroom panel according to claim 1, characterized in that, The hydroxyl-terminated acrylate is any one of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxymethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, and hydroxymethyl methacrylate.

3. The method for preparing a permanent antibacterial acrylic bathroom panel according to claim 1, characterized in that, The terminal phosphate ester monomer is one or more of the following: mono(methacryloyloxyethyl) phosphate, di(methacryloyloxyethyl) phosphate, tri(methacryloyloxyethyl) phosphate, mono(acryloyloxyethyl) phosphate, di(acryloyloxyethyl) phosphate, tri(acryloyloxyethyl) phosphate, diethyl (methacryloyloxyethyl) phosphate, and diethyl (acryloyloxyethyl) phosphate.

4. The method for preparing a permanent antibacterial acrylic bathroom panel according to claim 1, characterized in that, The high-temperature initiator is any one of azobisisobutyronitrile (AIBN), benzoyl peroxide (BPO), bis(4-methylbenzoyl peroxide), tert-amyl peroxide-2-ethylhexanoate, and tert-butyl peroxide-2-ethylhexanoate.

5. The method for preparing a permanent antibacterial acrylic bathroom panel according to claim 1, characterized in that, The polyfunctional acrylate crosslinking agent is any one of pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, triisocyanurate triacrylate, and trimethylolpropane triacrylate.

6. The method for preparing a permanent antibacterial acrylic bathroom panel according to claim 1, characterized in that, The low-temperature initiator is any one of azobisisoheptanenitrile, diisobutyryl peroxide, cumyl peroxyneodecanate, and bis(3-methoxybutyl peroxydicarbonate).

Images