Antiskid resin type artificial stone material and preparation method thereof

Abstract

The invention discloses an anti-skid resin type artificial stone material which comprises the following raw materials in parts by weight: 10 parts of composite resin, 55-70 parts of modified stone aggregate, 10-25 parts of needle-like wollastonite, 0.4-0.8 part of a curing agent, 0.05-0.2 part of a catalyst and 0.05-0.2 part of a light stabilizer, the composite resin comprises unsaturated polyester resin and an anti-skid filler in a mass ratio of 9: 1-7: 3, and the anti-skid resin type artificial stone material is prepared from the following raw materials in parts by weight: 10 parts of modified stone aggregate, 10-25 parts of needle-like wollastonite, 0.4-0.8 part of a curing agent, 0.05-0.2 part of a catalyst and 0.05-0.2 part of a light stabilizer. The anti-skid filler is one of ethylene glycol acrylate, glyceryl acrylate and acrylic acid modified sorbitol, the modified stone aggregate is formed by modifying stone aggregate through a stone aggregate modifier, and the catalyst is one of cobalt naphthenate, cobalt iso-octoate and manganese iso-octoate. The invention further discloses a preparation method of the anti-skid resin type artificial stone material, optimization balance of the anti-skid performance and other key performance of the artificial stone material is achieved, the application value of the artificial stone material in building decoration can be improved, and the safety and attractiveness of building space can be remarkably improved.

Description

Technical Field

[0001] The invention relates to the technical field of stone materials, and in particular to an anti-slip resin-type artificial stone material and a preparation method thereof. Background Art

[0002] Artificial stone materials are widely used in architectural decoration applications such as floors, countertops, walls, and staircases due to their excellent physical properties, rich color and texture options, and easy processability. However, traditional resin-based artificial stone materials have a relatively smooth surface, which can easily cause slipping in humid or oily environments, posing a significant safety hazard. This is especially true in high-humidity environments such as public places, bathrooms, and kitchens, where insufficient anti-slip properties can pose a potential safety hazard. Therefore, developing an artificial stone material with excellent anti-slip properties is particularly important.

[0003] Currently, most anti-slip materials on the market utilize mechanical surface treatments (such as sandblasting and etching) or the addition of anti-slip particles. However, these methods often result in increased surface roughness, which affects aesthetics, harbors dirt, and makes cleaning and maintenance difficult. Furthermore, these anti-slip measures often lack durability, with their effectiveness gradually diminishing over time. Therefore, finding a solution that can create an anti-slip structure within the material while maintaining a smooth, easily cleanable surface remains a major technical challenge.

[0004] Despite the potential advantages of unsaturated polyols in the anti-slip field, existing research on their application is relatively limited. In particular, optimizing the balance between anti-slip performance and other material properties (such as wear resistance, strength, and decorative effects) remains a major technical challenge. For example, controlling the dosage and distribution of unsaturated polyols to ensure anti-slip properties without compromising the overall mechanical properties and aesthetics remains a key challenge for researchers. Summary of the Invention

[0005] The purpose of the present invention is to provide an anti-slip resin-type artificial stone material. By rationally utilizing the anti-slip properties of unsaturated polyhydroxy compounds in anti-slip fillers and combining them with the addition of anti-slip additives with needle-like structures, a new anti-slip artificial stone material with a synergistically enhanced anti-slip effect is developed. In addition, an optimized balance between anti-slip performance and other key properties is achieved in the preparation process. This can not only enhance the application value of artificial stone materials in architectural decoration, but also significantly improve the safety and aesthetics of architectural spaces.

[0006] In order to achieve the above object, the solution of the present invention is: A non-slip resin-type artificial stone material comprises the following raw materials in parts by weight: 10 parts of a composite resin, 55-70 parts of a modified stone aggregate, 10-25 parts of needle-shaped wollastonite, 0.4-0.8 parts of a curing agent, 0.05-0.2 parts of a catalyst, and 0.05-0.2 parts of a light stabilizer. The composite resin comprises an unsaturated polyester resin and an anti-slip filler in a mass ratio of 9:1-7:3, the anti-slip filler is one of ethylene glycol acrylate, glycerol acrylate, and acrylic acid-modified sorbitol, the modified stone aggregate is stone aggregate modified by a stone aggregate modifier, and the catalyst is one of cobalt naphthenate, cobalt isooctanoate, and manganese isooctanoate.

[0007] The stone aggregate is one or more of calcium carbonate, marble fragments or quartz sand, the particle size of the stone aggregate is 10 mesh to 400 mesh, and the stone aggregate modifier is one of polyvinyl pyrrolidone, polyvinyl alcohol and epoxy resin.

[0008] The unsaturated polyester resin is one of unsaturated polyester resin 191 , unsaturated polyester resin 196 and unsaturated polyester resin 198 .

[0009] The curing agent is one of methyl ethyl ketone peroxide, benzoyl peroxide and cyclohexanone peroxide.

[0010] The light stabilizer is one of UV-9, UV-31 and 2,2,6,6-tetramethylpiperidinol.

[0011] A method for preparing an anti-slip resin-type artificial stone material comprises the following steps: Step 1: Pre-mix 10 parts of composite resin, 0.05-0.2 parts of catalyst and 0.05-0.2 parts of light stabilizer under stirring according to the formula ratio at a stirring speed of 300-500 rpm for 5-15 minutes to obtain a mixed resin; Step 2: then completely immerse the stone aggregate in the stone aggregate modifier for 10 to 30 minutes, remove it from the stone aggregate and dry it to obtain modified stone aggregate; Step 3: The mixed resin, 55-70 parts of modified stone aggregate and 10-25 parts of needle-shaped wollastonite are then mixed under stirring at a stirring speed of 100-200 rpm for 5-15 minutes, 0.4-0.8 parts of a curing agent are added, and stirring is continued for 5-30 minutes to obtain a uniformly mixed material; Step 4: Pour the evenly mixed material into a mold, vibrate and degas under vacuum, and then pressurize and cure at room temperature for 24 to 48 hours, then cure at room temperature for 1 week, demold the obtained cured sample, and perform coarse and fine grinding on the surface of the cured sample using a grinder to obtain the anti-slip resin-type artificial stone material.

[0012] In step 2, the drying temperature is 80-120° C., and the drying time is 2-4 hours.

[0013] In step 4, the vacuum degree under the vacuum state is 0.09 MPa, and the vibration degassing time is 5 to 10 minutes.

[0014] In step 4, the pressure applied during the pressurized curing process is 0.1-0.2 MPa.

[0015] In step 4, the particle sizes of the abrasives used in the coarse grinding process are 150 mesh, 200 mesh, and 500 mesh, respectively, and scratches, bumps and other defects on the surface of the cured sample are removed from deep to shallow by gradient grinding. The particle sizes of the abrasives used in the fine grinding process are 2000 mesh, 6000 mesh, and 10000 mesh, respectively, for the purpose of polishing and removing some fine scratches on the surface of the cured sample to achieve the effect of increasing the gloss.

[0016] After adopting the above technical solution, the anti-slip resin-type artificial stone material and the preparation method thereof of the present invention have the following beneficial effects: 1. Excellent anti-slip performance: The anti-slip filler is made of one of ethylene glycol acrylate, glycerol acrylate and acrylic acid-modified sorbitol. The molecule contains multiple hydroxyl groups (-OH) and unsaturated double bonds (C=C). The unsaturated double bonds can copolymerize with the unsaturated bonds in the unsaturated polyester resin to form a polymer network with anti-slip properties. The polyhydroxy structure in the anti-slip filler and the fine protrusions and grooves of the needle-shaped wollastonite can synergistically destroy the complete water film on the material surface, increase the actual contact area, and significantly increase the adhesion and friction of the material surface, thereby improving the material's anti-slip performance. 2. Good mechanical properties: The hydroxyl groups in the anti-slip filler can undergo physical adsorption or chemical reaction with the surface of stone aggregate and needle-shaped wollastonite, enhancing the interfacial bonding between the additive and the resin matrix. This not only improves the dispersibility of the anti-slip filler, but also further enhances the mechanical properties and wear resistance of the material. 2. Green and environmentally friendly products: The selected unsaturated polyhydroxy compounds are derived from natural resources or can be synthesized through environmentally friendly chemical pathways, reducing the negative impact on the environment. The use of these compounds helps to reduce the volatile organic compound (VOC) emissions of materials, meeting the environmental protection requirements of modern building materials.

[0017] Furthermore, the modified stone aggregate is a stone aggregate modified by a stone aggregate modifier, thereby improving the interface compatibility between the resin matrix and the inorganic stone aggregate. DETAILED DESCRIPTION

[0018] In order to further explain the technical solution of the present invention, the present invention is described in detail below through specific embodiments.

[0019] 1. Material preparation Example 1 A method for preparing an anti-slip resin-type artificial stone material comprises the following steps: Step 1: Premix 9 kg of unsaturated polyester resin 196, 1 kg of anti-slip filler acrylic acid-modified sorbitol, 0.2 kg of catalyst cobalt isooctanoate, and 0.05 kg of light stabilizer UV-9 under stirring according to the formula ratio. The stirring speed is controlled at 500 rpm for 15 minutes to obtain a mixed resin. Step 2: 55 kg of 400-mesh calcium carbonate was completely immersed in 550 kg of epoxy resin E51 for 10 minutes, and then removed from the mixture and dried at 120° C. for 2 hours to obtain a modified stone aggregate; Step 3: The mixed resin, 55 kg of modified stone aggregate and 25 kg of needle-shaped wollastonite were then mixed under stirring at a stirring speed of 200 rpm for 15 minutes, 0.4 kg of curing agent methyl ethyl ketone peroxide was added, and stirring was continued for 30 minutes to obtain a uniformly mixed material; Step 4: Pour the evenly mixed material into a mold, perform vibration degassing for 5 minutes under a vacuum state of 0.09 MPa, and then apply 0.2 MPa pressure to cure at room temperature for 24 hours, and then cure at room temperature for 1 week. Demold the obtained cured sample, and perform coarse and fine grinding on the surface of the cured sample using a grinder to obtain a non-slip resin-type artificial stone material.

[0020] Furthermore, the particle sizes of the abrasives used in the coarse grinding process are 150 mesh, 200 mesh, and 500 mesh, respectively, and the particle sizes of the abrasives used in the fine grinding process are 2000 mesh, 6000 mesh, and 10000 mesh, respectively. The abrasives are abrasives known in the art, such as a mixture of quartz sand, corundum, and resin.

[0021] Example 2 A method for preparing an anti-slip resin-type artificial stone material comprises the following steps: Step 1: Premix 7 kg of unsaturated polyester resin 191, 3 kg of anti-slip filler ethylene glycol acrylate, 0.05 kg of catalyst manganese isooctanoate, and 0.1 kg of light stabilizer UV-31 under stirring according to the formula ratio. The stirring speed is controlled at 300 rpm for 5 minutes to obtain a mixed resin. Step 2: 70 kg of 300-mesh marble fragments were completely immersed in 350 kg of polyvinyl alcohol 1788 for 10 minutes, and then removed from the mixture and dried at 80° C. for 4 hours to obtain modified stone aggregate; Step 3: The mixed resin, 70 kg of modified stone aggregate and 10 kg of needle-shaped wollastonite were then mixed under stirring at a stirring speed of 100 rpm for 5 minutes, 0.8 kg of curing agent benzoyl peroxide was added, and stirring was continued for 5 minutes to obtain a uniformly mixed material; Step 4: Pour the evenly mixed material into a mold, perform vibration degassing for 10 minutes under a vacuum state of 0.09 MPa, and then apply 0.1 MPa pressure to cure at room temperature for 30 hours, and then cure at room temperature for 1 week. Demold the obtained cured sample, and perform coarse and fine grinding on the surface of the cured sample using a grinder to obtain a non-slip resin-type artificial stone material.

[0022] Furthermore, the particle sizes of the abrasives used in the coarse grinding process are 150 mesh, 200 mesh, and 500 mesh, respectively, and the particle sizes of the abrasives used in the fine grinding process are 2000 mesh, 6000 mesh, and 10000 mesh, respectively. The abrasives are abrasives known in the art, such as a mixture of quartz sand, corundum, and resin.

[0023] Example 3 A method for preparing an anti-slip resin-type artificial stone material comprises the following steps: Step 1: Premix 8 kg of unsaturated polyester resin 198, 2 kg of anti-slip filler glycerol acrylate, 0.1 kg of catalyst cobalt naphthenate, and 0.2 kg of light stabilizer 2,2,6,6-tetramethylpiperidinol according to the formula ratio under stirring at a stirring speed of 350 rpm for 5 minutes to obtain a mixed resin; Step 2: 65 kg of 100-mesh quartz sand was completely immersed in 520 kg of polyvinylpyrrolidone K30 for 10 minutes, and then the sand was removed from the quartz sand and dried at 100° C. for 2.5 hours to obtain a modified stone aggregate; Step 3: The mixed resin, 65 kg of modified stone aggregate and 15 kg of needle-shaped wollastonite were then mixed under stirring at a stirring speed of 200 rpm for 5 minutes, 0.7 kg of curing agent cyclohexanone peroxide was added, and stirring was continued for 5 minutes to obtain a uniformly mixed material; Step 4: Pour the evenly mixed material into a mold, perform vibration degassing for 7 minutes under a vacuum state of 0.09 MPa, and then apply 0.15 MPa pressure to cure at room temperature for 48 hours, and then cure at room temperature for 1 week. Demold the obtained cured sample, and perform coarse and fine grinding on the surface of the cured sample using a grinder to obtain a non-slip resin-type artificial stone material.

[0024] Furthermore, the particle sizes of the abrasives used in the coarse grinding process are 150 mesh, 200 mesh, and 500 mesh, respectively, and the particle sizes of the abrasives used in the fine grinding process are 2000 mesh, 6000 mesh, and 10000 mesh, respectively. The abrasives are abrasives known in the art, such as a mixture of quartz sand, corundum, and resin.

[0025] Comparative Example 1 The preparation method of the anti-slip resin artificial stone material is substantially the same as that of Example 2, except that: 3 kg of diethylene glycol is added in step 1 to replace the anti-slip filler ethylene glycol acrylate.

[0026] Comparative Example 2 The preparation method of the anti-slip resin artificial stone material is substantially the same as that of Example 2, except that: 3 kg of methyl methacrylate is added in step 1 instead of the anti-slip filler ethylene glycol acrylate.

[0027] Comparative Example 3 The preparation method of the anti-slip resin artificial stone material is substantially the same as that of Example 2, except that: in step 3, 10 kg of 300-mesh calcium carbonate is added to replace the needle-shaped wollastonite.

[0028] Comparative Example 4 The preparation method of the anti-slip resin artificial stone material is substantially the same as that of Example 2, except that: 3 kg of diethylene glycol is added in step 1 instead of the anti-slip filler ethylene glycol acrylate, and 10 kg of 300-mesh calcium carbonate is added in step 3 instead of the needle-shaped wollastonite.

[0029] Comparative Example 5 The preparation method of the anti-slip resin artificial stone material is substantially the same as that of Example 2, except that the amount of the anti-slip filler ethylene glycol acrylate added in step 1 is changed to 1 kg.

[0030] Comparative Example 6 The preparation method of the anti-slip resin artificial stone material is substantially the same as that of Example 2, except that: in step 3, 2 kg of paraffin wax is first heated to 70°C until it is molten, and then 70 kg of modified stone aggregate and 10 kg of needle-shaped wollastonite are added. The temperature is maintained at 70°C and stirred at 200 rpm for 15 minutes. After cooling, the mixture is sieved to obtain the paraffin-coated modified aggregate and needle-shaped wollastonite, which are then mixed with the mixed resin.

[0031] In the above examples and comparative examples, unsaturated polyester resin 191 was purchased from Jiangsu Bosite Chemical Technology Co., Ltd., unsaturated polyester resin 196 was purchased from Jinan Qingtian Chemical Technology Co., Ltd., unsaturated polyester resin 198 was purchased from Xinyang Technology Group Co., Ltd., ethylene glycol acrylate was purchased from Shandong Yingsheng Chemical Co., Ltd., glycerol acrylate was purchased from Guangzhou Shanghe Chemical Technology Co., Ltd., acrylic acid modified sorbitol was prepared by the method disclosed in the invention patent with publication number CN115772080B, a preparation method and application of acrylic acid modified sorbitol water tree inhibitor, cycloalkane Cobalt octanoate was purchased from Jinan Yunuo Chemical Co., Ltd., cobalt 2-ethylhexanoate was purchased from Qilu New Materials Co., Ltd., manganese 2-ethylhexanoate was purchased from Xinghai Chemical Co., Ltd., polyvinyl pyrrolidone K30 was purchased from Jinan Zhengkang Chemical Co., Ltd., polyvinyl alcohol 1788 was purchased from Jining Fangyu Chemical Co., Ltd., epoxy resin E51 was purchased from Shandong Chuangying Chemical Co., Ltd., light stabilizer UV-9 was purchased from Smike Technology Co., Ltd., light stabilizer UV-31 was purchased from Tianjin Lianlong New Materials Co., Ltd., and light stabilizer 2,2,6,6-tetramethylpiperidinol was purchased from Zhongshan Dixin Chemical Co., Ltd.

[0032] 2. Performance Testing The following performance evaluations were performed on the anti-slip resin-based artificial stone materials prepared in each embodiment and comparative example: (1) Anti-slip performance Tested according to EN 14231:2003.

[0033] (2) Compressive strength Tested according to EN 14617-15:2005.

[0034] (3) Flexural strength Tested according to EN 14617-2:2016.

[0035] (4) Wear resistance Tested according to EN 14617-4:2012.

[0036] Table 1 Performance evaluation of anti-slip resin artificial stone materials

[0037] The performance evaluation results of the anti-slip resin-type artificial stone materials prepared in each embodiment and comparative example are shown in Table 1. The results show that compared with Examples 1 and 3, the anti-slip artificial stone material prepared in Example 2 has the best comprehensive mechanical properties of anti-slip performance, wear resistance and strength.

[0038] In Comparative Example 1, diethylene glycol was used in place of the anti-slip filler ethylene glycol acrylate in step 1. Although both contain hydroxyl groups, diethylene glycol does not have unsaturated bonds and therefore cannot copolymerize with the unsaturated polyester resin. Diethylene glycol is dissolved and removed by water during the coarse and fine grinding processes in step 4, resulting in a decrease in the anti-slip, compressive strength, and flexural strength of Comparative Example 1. In Comparative Example 2, methyl methacrylate is used in place of the anti-slip filler ethylene glycol acrylate in step 1. Both contain unsaturated double bonds, but methyl methacrylate does not have a hydroxyl functional group. Therefore, it can copolymerize with the unsaturated polyester resin during the curing process, but it does not have an anti-slip effect, resulting in a significant decrease in the anti-slip effect of Comparative Example 2. In Comparative Example 3, 300-mesh calcium carbonate was used to replace the needle-shaped wollastonite in step 3. Unlike the needle-shaped structure, calcium carbonate usually exists in the form of fine particles or spherical particles. Fine particles or spherical particles make the surface smoother, which reduces the anti-slip performance. At the same time, because spherical particles have a smaller contact area and fewer contact points than needle-shaped particles, the filling effect of the resin is reduced, resulting in a significant decrease in the anti-slip effect and flexural strength of Comparative Example 3. Comparative Example 4 used diethylene glycol to replace the anti-slip filler ethylene glycol acrylate in step 1, and 300 mesh calcium carbonate to replace the acicular wollastonite in step 3. This completely replaced the anti-slip filler ethylene glycol acrylate and the acicular wollastonite with a synergistic anti-slip effect. The anti-slip effect of this sample was significantly reduced, and the strength and wear resistance also decreased. In Comparative Example 5, only 1 kg of anti-slip filler ethylene glycol acrylate was added in step 1. The reduction in the amount of anti-slip filler added directly affected the anti-slip properties of the sample, and the strength and wear resistance of the sample also decreased. In Comparative Example 6, paraffin wax is used to coat the modified stone aggregate and needle-shaped wollastonite in step 3. Paraffin wax itself is a relatively slippery material. Coating it on the surface of stone aggregate or anti-slip filler may make the brick surface smoother, reduce the surface roughness, and reduce the anti-slip property of the sample. In addition, a paraffin film exists on the surface of the coated aggregate and needle-shaped wollastonite, and the interfacial effect between the aggregate and the resin is reduced, resulting in a weakened bonding force between the filler and the resin, thereby reducing the overall strength of the brick.

[0039] The above embodiments do not limit the product form and style of the present invention. Any appropriate changes or modifications made by ordinary technicians in the relevant technical field should be deemed to be within the patent scope of the present invention.

Claims

1. A non-slip resin-type artificial stone material, characterized by: The invention comprises the following raw materials in parts by weight: 10 parts of composite resin, 55-70 parts of modified stone aggregate, 10-25 parts of needle-shaped wollastonite, 0.4-0.8 parts of curing agent, 0.05-0.2 parts of catalyst and 0.05-0.2 parts of light stabilizer, wherein the composite resin comprises unsaturated polyester resin and anti-slip filler in a mass ratio of 9:1-7:3, the anti-slip filler is one of ethylene glycol acrylate, glycerol acrylate and acrylic acid-modified sorbitol, the modified stone aggregate is stone aggregate modified by a stone aggregate modifier, and the catalyst is one of cobalt naphthenate, cobalt isooctanoate and manganese isooctanoate.

2. The anti-slip resin-type artificial stone material according to claim 1, characterized in that: The stone aggregate is one or more of calcium carbonate, marble fragments or quartz sand, the particle size of the stone aggregate is 10 mesh to 400 mesh, and the stone aggregate modifier is one of polyvinyl pyrrolidone K30, polyvinyl alcohol 1788 and epoxy resin E51.

3. The anti-slip resin artificial stone material according to claim 1, characterized in that: The unsaturated polyester resin is one of unsaturated polyester resin 191 , unsaturated polyester resin 196 and unsaturated polyester resin 198 .

4. The anti-slip resin-type artificial stone material according to claim 1, characterized in that: The curing agent is one of methyl ethyl ketone peroxide, benzoyl peroxide and cyclohexanone peroxide.

5. The anti-slip resin-type artificial stone material according to claim 1, characterized in that: The light stabilizer is one of UV-9, UV-31 and 2,2,6,6-tetramethylpiperidinol.

6. A method for preparing the anti-slip resin-based artificial stone material according to claim 1, characterized in that: The following steps are involved: Step 1: Pre-mix 10 parts of composite resin, 0.05-0.2 parts of catalyst and 0.05-0.2 parts of light stabilizer under stirring according to the formula ratio at a stirring speed of 300-500 rpm for 5-15 minutes to obtain a mixed resin; Step 2: then completely immerse the stone aggregate in the stone aggregate modifier for 10 to 30 minutes, remove it from the stone aggregate and dry it to obtain modified stone aggregate; Step 3: The mixed resin, 55-70 parts of modified stone aggregate and 10-25 parts of needle-shaped wollastonite are then mixed under stirring at a stirring speed of 100-200 rpm for 5-15 minutes, 0.4-0.8 parts of a curing agent are added, and stirring is continued for 5-30 minutes to obtain a uniformly mixed material; Step 4: Pour the evenly mixed material into a mold, vibrate and degas under vacuum, and then pressurize and cure at room temperature for 24 to 48 hours, then cure at room temperature for 1 week, demold the obtained cured sample, and perform coarse and fine grinding on the surface of the cured sample using a grinder to obtain the anti-slip resin-type artificial stone material.

7. The method for preparing a non-slip resin-based artificial stone material according to claim 6, characterized in that: In step 2, the drying temperature is 80-120° C., and the drying time is 2-4 hours.

8. The method for preparing a non-slip resin-based artificial stone material according to claim 6, characterized in that: In step 4, the vacuum degree under the vacuum state is 0.09 MPa, and the vibration degassing time is 5 to 10 minutes.

9. The method for preparing a non-slip resin-based artificial stone material according to claim 6, characterized in that: In step 4, the pressure applied during the pressurized curing process is 0.1-0.2 MPa.

10. The method for preparing a non-slip resin-based artificial stone material according to claim 6, characterized in that: In step 4, the particle sizes of the abrasives used in the coarse grinding process are 150 mesh, 200 mesh, and 500 mesh, respectively, and the particle sizes of the abrasives used in the fine grinding process are 2000 mesh, 6000 mesh, and 10000 mesh, respectively.

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