Preparation method of long-life non-slip mat for bathroom

Abstract

The invention discloses a preparation method of a long-life non-slip mat for a bathroom, and belongs to the field of high polymer materials. The method comprises the following steps: weighing a modified filler and a polymer base material, adding complexes such as a calcium-zinc stabilizer, an auxiliary agent and a lubricant, mixing, and preparing the non-slip mat through a plastic extrusion process. The non-slip mat has excellent anti-aging performance, anti-slip performance and mechanical strength, is suitable for being used in a humid and hot environment for a long time, can remarkably prolong the service life, and is suitable for the fields of home furnishing, public bathrooms and the like.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of high molecular materials, and particularly relates to a preparation method of a long-life anti-slip mat for bathroom. BACKGROUND

[0002] With the improvement of people's living standards, the bathroom as an important functional area of family and public places, the requirement of safety and comfort is increasing. The bathroom is in a humid state for a long time, and there are often water stains and soap residues on the ground, which can easily lead to the occurrence of slipping accidents. Therefore, the anti-slip mat as an effective safety protection product has been widely used.

[0003] Chinese patent ZL201710266137.5 discloses an anti-slip wear-resistant floor mat and a preparation method thereof. The anti-slip wear-resistant floor mat comprises a PVC substrate layer and a silk thread woven layer attached to the upper surface of the PVC substrate layer. The PVC substrate layer comprises the following raw materials by weight: PVC resin 80-100 parts, plasticizer 25-35 parts, filler 25-35 parts, calcium-zinc stabilizer 2-6 parts, impact modifier 5-9 parts, wear-resistant modifier 4-8 parts, anti-slip agent 3-5 parts, and lubricant 0.8-1.2 parts.

[0004] However, the current market anti-slip mats for bathroom mainly have the following problems:

[0005] Insufficient material performance: Traditional anti-slip mats are mostly made of ordinary PVC (polyvinyl chloride) or rubber materials. Although these materials have certain anti-slip properties, they can easily age, harden, crack, and discolor after long-term use in a humid environment, resulting in short service life and reduced safety performance. In addition, ordinary PVC materials may release harmful substances during processing and use, which does not meet modern environmental and health requirements.

[0006] Slip resistance performance decay: The surface of the anti-slip mat is easily worn due to friction or contamination during use, and the anti-slip texture gradually becomes smooth, resulting in a decrease in slip resistance performance. Especially under the action of lubricating media such as soap water, the anti-slip effect is greatly reduced, which cannot meet the high requirements of the bathroom environment.

[0007] Insufficient weather resistance: The bathroom environment is not only humid, but also often subjected to high temperature and cleaning agent erosion, which puts high requirements on the weather resistance of the anti-slip mat. The existing anti-slip mat has poor high temperature resistance, and long-term exposure to high temperature environment can cause the material to soften, deform, or even lose function. In addition, the chemical components in the cleaning agent can accelerate the degradation of the anti-slip mat, further shortening its service life.

[0008] Environmental and health problems: some cheap anti-skid mats add calcium zinc stabilizer or plasticizer containing heavy metals such as lead and cadmium, which may migrate into water or volatilize into the air during use, threatening the health of users, especially the elderly and children. At the same time, these anti-skid mats are difficult to degrade after being discarded, causing environmental pollution and not meeting the concept of sustainable development. SUMMARY

[0009] In order to overcome at least one of the technical problems in the above background art, the present method proposes a preparation method of long-life bathroom anti-skid mat, which optimizes the material formula and preparation process, effectively solves the above problems in the prior art, and significantly improves the comprehensive performance and service life of the anti-skid mat.

[0010] To achieve the above purpose, the technical scheme adopted by the present application is as follows:

[0011] A preparation method of long-life bathroom anti-skid mat, comprising the following steps:

[0012] Step one: weigh 10-18 parts of modified filler and 0.5-0.8 parts of epoxy succinic acid polymer / cerium complex, 0.5-2 parts of mercaptoacetic acid magnesium, 1.5-3.4 parts of sodium hydroxide, and put them into a high-speed mixer for mixing and stirring, the temperature is 80-90℃, the stirring speed is 500-1500 revolutions / minute, and the time is 3-5 minutes;

[0013] Step two: add 100-160 parts of polyvinyl chloride, 1-5 parts of acrylic resin, 1-3 parts of calcium zinc stabilizer, 0.1-0.5 parts of lubricant and auxiliary additives to the high-speed mixer, continue to stir, the temperature is 80-90℃, the speed is 800-1200 revolutions / minute, and the time is 5-10 minutes, to obtain a mixture;

[0014] Step three: place the mixture in a plastic extruder, control the screw rotation speed of the extruder at 50-80 revolutions / minute, control the temperature at 170-190℃, and extrude into a flat die, then cool to obtain the anti-skid mat.

[0015] The preparation method of the modified filler in step one is: add 100-120 parts of filler to 1000-1200 parts of deionized water solution containing 3-6 parts of triaminopropyl methyl dimethoxy silane, disperse and stir with a high-speed stirrer, continue to react for 2-4 hours, and finally centrifuge, wash and dry to obtain the desired modified filler; the filler is talc, calcium carbonate, wollastonite or a combination thereof, and the particle size range is 1-10μm.

[0016] The preparation method of the epoxy succinic acid polymer / cerium complex in step one is as follows: 20-30 parts of epoxy succinic acid polymer (CAS No. 51274-37-4), 15-25 parts of cerium nitrate, and 200-250 parts of deionized water are mixed, and reacted at 60-70℃ for 100-130 minutes, after which water is removed by evaporation, and vacuum drying is performed, to obtain the epoxy succinic acid polymer / cerium complex.

[0017] The lubricant is at least one of stearic acid, calcium stearate, or polyethylene wax.

[0018] The auxiliary agent in step two is an antioxidant and an ultraviolet absorber.

[0019] The antioxidant is antioxidant type 1010 or 168, and the addition amount is 0.1-0.5 parts.

[0020] The ultraviolet absorber is UV-531 or UV-326, and the addition amount is 0.1-0.3 parts.

[0021] The surface of the non-slip pad in step three can be subjected to embossing treatment using a pressurized embossing roller, with a pressure of 5-20 MPa, a temperature of 40-70℃, and a time of 2-5 seconds, to improve the non-slip performance.

[0022] The cooling process in step three uses water cooling or air cooling, with a cooling temperature controlled at 20-30℃, and a cooling time of 10-30 seconds.

[0023] Reaction mechanism:

[0024] Amino-epoxy ring-opening reaction mechanism: the amino group (-NH2) in the amino-modified filler has nucleophilicity, while the epoxy group in the epoxy succinic acid polymer / cerium complex is a highly polarized three-membered ring. During the reaction, the nitrogen atom on the amino group acts as a nucleophile, attacking the carbon atom with lower electron cloud density in the epoxy group, leading to the opening of the epoxy ring. Thus, the amino-modified filler and the epoxy succinic acid polymer / cerium complex are connected.

[0025] Mercapto-epoxy ring-opening reaction mechanism: the sulfur atom in the mercapto group acts as a nucleophilic center, attacking the carbon atom with partial positive charge in the epoxy group, triggering the opening of the epoxy ring. A product containing hydroxyl and thioether structures is generated, and a magnesium acetate complex is also produced, allowing the mercapto magnesium acetate and the epoxy succinic acid polymer / cerium complex to be connected to each other.

[0026] Technical effects:

[0027] Mechanical property improvement: Through these two kinds of ring-opening reactions, a more complex three-dimensional network structure is formed, greatly enhancing the intermolecular forces. This makes the modified filler used for PVC blending extrusion and other ingredients such as PVC more closely combined, thereby improving the overall strength, toughness, and wear resistance of the non-slip mat. In the long-term use process, the non-slip mat is less likely to crack, deform, and other problems, prolonging its service life.

[0028] Anti-slip performance improvement: By adding modified fillers and surface modifiers, the interfacial bonding force between the fillers and the PVC substrate is enhanced, and the depth of the anti-slip texture is formed through mold design.

[0029] Water resistance enhancement: The newly formed cross-linked structure and complex reduce the erosion of water molecules on the internal structure of the material. On the one hand, the complex molecular network hinders the penetration of water molecules; on the other hand, the newly generated chemical bonds and structures are more resistant to water, allowing the non-slip mat to maintain stable performance in a humid bathroom environment without performance degradation due to water absorption. DETAILED DESCRIPTION

[0030] The present application will be further described in conjunction with the following examples. The embodiments are implemented on the premise of the technical solutions of the present application, and detailed implementation methods and processes are given, but the protection scope of the present application is not limited to the following examples.

[0031] The experimental methods in the following examples without specific conditions are usually carried out under conventional conditions, and the raw materials and reagents used without special instructions are conventional commercially available products.

[0032] Example 1

[0033] Step 1:

[0034] Take 10 kg of modified filler, 0.5 kg of epoxy succinic acid polymer / cerium complex, 1 kg of mercaptoacetic acid magnesium, and 2.5 kg of sodium hydroxide, and put them into a high-speed mixer. The mixer is set to a temperature of 85°C, a stirring speed of 1000 revolutions per minute, and a stirring time of 4 minutes.

[0035] The preparation method of the modified filler is as follows: 100 kg of filler talc powder is added to 1000 kg of deionized water solution containing 3 kg of triaminopropyl methyl dimethoxy silane, and stirred and dispersed by a high-speed stirrer. Then, the reaction is continued for 2 hours under constant conditions, and finally the desired modified filler is obtained after centrifugal separation, washing, and drying.

[0036] The preparation method of the epoxy succinic acid polymer / cerium complex is as follows: 2 kg of epoxy succinic acid polymer (CAS No. 51274-37-4) is uniformly mixed with 1.5 kg of cerium nitrate and 20 kg of deionized water. Under constant temperature conditions at 60°C, the stirring reaction is carried out for 100 minutes to ensure that the epoxy succinic acid polymer and cerium nitrate fully react to form a complex. After the reaction is completed, the water in the reaction system is removed by evaporation equipment. Subsequently, the obtained mixture is placed in a vacuum drying box for further drying treatment until the dried epoxy succinic acid polymer / cerium complex is obtained.

[0037] Step two:

[0038] Into a high-speed mixer, 130 kg of polyvinyl chloride, 3 kg of acrylic resin, 2 kg of RR-80A calcium-zinc stabilizer, 0.3 kg of calcium stearate, 0.2 kg of 1010 antioxidant, and 0.2 kg of UV-531 ultraviolet absorber are added. The stirring is continued, the temperature is maintained at 85°C, the stirring speed is adjusted to 900 rpm, and the stirring time is 7 minutes to obtain a uniform mixture.

[0039] Step three:

[0040] The mixture is placed in a plastic extruder, the screw speed is set to 60 rpm, and the temperature is controlled at 180°C. Extrusion molding is performed through a flat die, and then embossing treatment is performed using a pressurized patterned roller (pressure 10 MPa, temperature 50°C, time 3 seconds) to enhance the slip resistance. Water cooling is used for cooling, the cooling temperature is controlled at 25°C, and the cooling time is 20 seconds to obtain the finished slip mat.

[0041] Example two

[0042] Step one:

[0043] 13 kg of modified filler, 0.6 kg of epoxy succinic acid polymer / cerium complex, 0.5 kg of magnesium mercaptoacetate, and 1.5 kg of sodium hydroxide are weighed and mixed under the conditions of temperature 80°C, stirring speed 500 rpm, and time 3 minutes.

[0044] The preparation method of the modified filler is as follows: 110 kg of filler calcium carbonate is weighed and added to a 1100 kg deionized water solution containing 4 kg of triaminopropylmethyldimethoxysilane. A high-speed stirrer is used for stirring and dispersion to uniformly disperse the filler in the solution. Then, the reaction is continuously carried out at a suitable temperature for 3 hours to ensure that the silane coupling agent fully reacts with the surface of the filler. After the reaction is completed, the modified filler is separated from the solution by centrifugal separation technology and is washed. Finally, the washed modified filler is dried to obtain the finished modified filler.

[0045] The preparation method of the epoxy succinic acid polymer / cerium complex: select 2.5 kg of epoxy succinic acid polymer and 2 kg of cerium nitrate, and an appropriate amount of 22.5 kg of deionized water, mix uniformly and then place in a reaction container. Stirring reaction at 65°C for 115 minutes to ensure that the epoxy succinic acid polymer and cerium nitrate can be fully combined. After the reaction is completed, remove the excess water by evaporation. Then, the reaction product is placed in a vacuum environment for drying, and the desired epoxy succinic acid polymer / cerium complex is finally obtained.

[0046] Step two:

[0047] Add 100 kg of polyvinyl chloride, 1 kg of acrylic resin, 1 kg of AW300M calcium-zinc stabilizer, 0.1 kg of stearic acid, 0.1 kg of 168 antioxidant and 0.1 kg of UV-326 ultraviolet absorber. The mixing conditions are temperature 80°C, stirring speed 800 rpm, and time 5 minutes.

[0048] Step three:

[0049] The screw speed of the extruder is 50 rpm, and the temperature is 170°C. After molding, embossing treatment (pressure 5 MPa, temperature 40°C, time 2 seconds), water cooling to 20°C, cooling time 10 seconds.

[0050] Example three

[0051] Step one:

[0052] Take 16 kg of modified filler, 0.7 kg of epoxy succinic acid polymer / cerium complex, 2 kg of mercaptoacetic acid magnesium, and 3.4 kg of sodium hydroxide. The mixing conditions are temperature 90°C, stirring speed 1500 rpm, and time 5 minutes.

[0053] The preparation method of the modified filler: add 120 kg of filler talc powder to 1200 kg of deionized water solution containing 5 kg of triaminopropyl methyl dimethoxy silane, and use a high-speed stirrer for efficient stirring and dispersion operation. During stirring, ensure that the filler and silane coupling agent are in full contact and reaction. After continuous reaction for 4 hours, separate the modified filler from the solution by centrifugal separation technology. Then, the modified filler is washed to remove excess silane coupling agent and other impurities. Finally, the washed modified filler is dried to obtain a modified filler product with stable quality.

[0054] The preparation method of the epoxy succinic acid polymer / cerium complex is as follows: 3 kg of epoxy succinic acid polymer is mixed with 2.5 kg of cerium nitrate, and 25 kg of deionized water is added and stirred uniformly. Under the condition of heating at 70 °C, the stirring reaction is carried out for 130 minutes to ensure the complete formation of the complex. After the reaction is completed, the water in the system is removed by evaporation technology. Then, the product is placed in a vacuum drying oven for drying treatment until the product reaches a constant weight, and the epoxy succinic acid polymer / cerium complex is obtained.

[0055] Step two:

[0056] 160 kg of polyvinyl chloride, 5 kg of acrylic resin, 3 kg of calcium-zinc stabilizer R-77A, 0.5 kg of polyethylene wax, 0.5 kg of antioxidant 1010, and 0.3 kg of UV-531 ultraviolet absorber are added. The mixing conditions are temperature 90 °C, stirring speed 1200 rpm, and time 10 minutes.

[0057] Step three:

[0058] The screw speed of the extruder is 80 rpm, and the temperature is 190 °C. After molding, embossing treatment is performed (pressure 20 MPa, temperature 70 °C, time 5 seconds), air cooling to 30 °C, and cooling time 30 seconds.

[0059] Example four

[0060] Step one:

[0061] 18 kg of modified filler, 0.8 kg of epoxy succinic acid polymer / cerium complex, 1.5 kg of magnesium mercaptoacetate, and 2 kg of sodium hydroxide are weighed. The mixing conditions are temperature 82 °C, stirring speed 800 rpm, and time 4 minutes.

[0062] The preparation method of the modified filler is as follows: 115 kg of filler wollastonite is weighed and placed in 1150 kg of deionized water solution containing 6 kg of triaminopropylmethyldimethoxysilane. A high-speed stirrer is used to stir and disperse the solution to ensure uniform distribution of the filler particles in the solution. The reaction is continued for 3.5 hours at a constant temperature and stirring speed to allow the silane coupling agent to fully bond to the surface of the filler. After the reaction is completed, the modified filler is separated from the solution by centrifugal separation. Then, the modified filler is thoroughly washed. Finally, the washed modified filler is placed in a drying device for drying treatment to obtain the desired modified filler product.

[0063] The preparation method of the epoxy succinic acid polymer / cerium complex: 2.75 kg of epoxy succinic acid polymer, 2.25 kg of cerium nitrate, and 23.75 kg of deionized water were mixed uniformly and then placed in a reaction kettle. Stirring reaction was carried out at a constant temperature of 67.5°C for 120 minutes to ensure that the reaction was fully carried out. After the reaction was completed, the water in the system was removed by evaporation. Subsequently, the obtained mixture was placed in a vacuum dryer for drying treatment until the product was completely dried, and finally the epoxy succinic acid polymer / cerium complex was obtained.

[0064] Step two:

[0065] 120 kg of polyvinyl chloride, 2 kg of acrylic resin, 2 kg of CZ9372 type calcium-zinc stabilizer, 0.2 kg of calcium stearate and stearic acid mixture (half and half), 0.3 kg of 168 type antioxidant, and 0.2 kg of UV-326 ultraviolet absorber were added. The mixing conditions were temperature 88°C, stirring speed 1000 rpm, and time 8 minutes.

[0066] Step three:

[0067] The screw speed of the extruder was 65 rpm, and the temperature was 185°C. After molding, embossing treatment was carried out (pressure 15 MPa, temperature 60°C, time 4 seconds), water cooling to 28°C, and cooling time 25 seconds.

[0068] Comparative Example 1

[0069] In this example, no modified filler was added, and the rest was consistent with Example 1.

[0070] Comparative Example 2

[0071] In this example, no epoxy succinic acid polymer / cerium complex was added, and the rest was consistent with Example 1.

[0072] Test method and results:

[0073] 1. Mechanical property test

[0074] Test method:

[0075] According to the standard GB / T 1040-2006 "Determination of tensile properties of plastics", a universal material testing machine (Instron 3369 type or similar equipment) was used to test the tensile strength and elongation at break of the sample. The specific steps are as follows:

[0076] 1) The anti-slip mat sample was cut into standard size (length 150 mm, width 20 mm, thickness 3 mm).

[0077] 2) Clamped in the upper and lower clamps of the testing machine, set the tensile rate to 50 mm / min.

[0078] 3) Record the force change during stretching until the sample breaks, calculate the tensile strength (MPa) and elongation at break (%).

[0079] Table 1: Mechanical property test results of examples and comparative examples

[0080] Tensile strength (MPa) Elongation at break (%) Example 1 18.5 222 Example 2 18.7 225 Example 3 19.0 228 Example 4 19.1 230 Comparative Example 1 18.0 215 Comparative Example 2 18.2 219

[0081] 2. Aging performance test

[0082] Test method:

[0083] According to ISO 188 standard, perform thermal oxidative aging test, specific steps as follows:

[0084] Place the anti-skid mat sample in the hot air aging oven, set the temperature to 150℃, and perform aging test.

[0085] Test for 10 days, detect its mechanical properties (tensile strength, elongation at break) and appearance (color change, crack) changes.

[0086] Table 2: Aging performance test results of examples and comparative examples

[0087]

[0088] 3. Anti-skid performance test

[0089] Test method:

[0090] According to GB / T 2423.50 standard, use friction coefficient tester to determine the friction coefficient of anti-skid mat in wet environment. Test steps as follows:

[0091] Lay the anti-skid mat sample on the test platform, and use the standard slider (the contact area between the slider and the surface is fixed) to slide on the sample surface.

[0092] Apply a certain load (1kg) and record the change of friction force during sliding.

[0093] Test under different wetness (including dry, wet, soap water wet), calculate its dynamic friction coefficient.

[0094] Table 3: Anti-skid performance test results of examples and comparative examples

[0095]

[0096]

[0097] To sum up, the anti-skid mat realizes the effects of high strength, good durability and excellent friction performance through optimizing the formula and the preparation process, can significantly prolong the service life of the bathroom anti-skid mat, and improve the safety and comfort of users.

[0098] The above embodiments are the preferred implementation of the present application, in addition to this, the present application can be implemented in other ways, without departing from the concept of the present application, any obvious replacement within the protection scope of the present application.

Claims

1. A method of making a long-life bath mat, characterized in that, The method comprises the following steps: Step 1: 10-18 parts of modified filler, 0.5-0.8 parts of epoxy succinic acid polymer / cerium complex, 0.5-2 parts of magnesium mercaptoacetate, and 1.5-3.4 parts of sodium hydroxide are weighed by weight parts, and then mixed and stirred in a high-speed mixer, the temperature is 80-90℃, the stirring speed is 500-1500 rpm, and the stirring time is 3-5 minutes; Step 2: 100-160 parts of polyvinyl chloride, 1-5 parts of acrylic resin, 1-3 parts of calcium-zinc stabilizer, 0.1-0.5 parts of lubricant and auxiliary additive are added into the high-speed mixer, and the mixture is continuously stirred, the temperature is 80-90℃, the speed is 800-1200 rpm, and the stirring time is 5-10 minutes to obtain a mixture; Step 3: The mixture is placed in a plastic extruder, the screw rotation speed of the extruder is controlled at 50-80 rpm, the temperature is controlled at 170-190℃, and the mixture is extruded into a non-slip mat through a flat die, and then the non-slip mat is cooled to obtain the non-slip mat.

2. A method of making a long life bath mat according to claim 1, characterised in that: In step 1, the modified filler is prepared by adding 100-120 parts of filler into 1000-1200 parts of deionized water solution containing 3-6 parts of triaminopropyl methyl dimethoxysilane, and then stirring and dispersing by using a high-speed stirrer, continuously reacting for 2-4 hours, and finally centrifuging, washing and drying to obtain the required modified filler; the filler is talc, calcium carbonate, wollastonite or a combination thereof, and the particle size range is 1-10 μm.

3. A method of making a long life bath mat according to claim 1, characterised in that: In step 1, the preparation method of the epoxy succinic acid polymer / cerium complex is as follows: 20-30 parts of epoxy succinic acid polymer, 15-25 parts of cerium nitrate and 200-250 parts of deionized water are mixed, and then reacted at 60-70℃ for 100-130 minutes, and then water is removed by evaporation, and then vacuum drying is performed to obtain the epoxy succinic acid polymer / cerium complex.

4. A method of making a long life bath mat according to claim 1, characterised in that: The lubricant is at least one of stearic acid, calcium stearate or polyethylene wax.

5. A method of making a long life bath mat according to claim 1, characterised in that: The auxiliary additive in step 2 is an antioxidant and an ultraviolet absorber: The antioxidant is a 1010 or 168 type antioxidant, and the addition amount is 0.1-0.5 parts; The ultraviolet absorber is UV-531 or UV-326, and the addition amount is 0.1-0.3 parts.

6. A method of making a long life bath mat according to claim 1, characterised in that: In step 3, the surface of the non-slip mat can be subjected to embossing treatment by using a pressure pattern roller, the pressure is 5-20 MPa, the temperature is 40-70℃, and the time is 2-5 seconds, so as to improve the anti-skid performance.

7. A method of making a long life bath mat according to claim 1, characterised in that: In step 3, water cooling or air cooling is adopted in the cooling process, the cooling temperature is controlled at 20-30℃, and the cooling time is 10-30 seconds.

Images