Synthetic resin tile with high impact resistance and preparation method thereof

Abstract

The invention discloses a synthetic resin tile with high impact resistance and a preparation method thereof, and relates to the technical field of tiles. The synthetic resin tile with the high impact resistance comprises an ASA surface layer, a modified PVC resin filling layer and a PVC resin layer which are sequentially arranged from top to bottom, and the ASA surface layer is made of ASA resin; the modified PVC resin filling layer is prepared from regenerated PVC resin, dicyclopentadiene diformate, alkenyl-terminated polysiloxane, modified nano calcium carbonate, a heat stabilizer, an initiator and the balance of new PVC resin, and preparation raw materials of the modified nano calcium carbonate comprise a silane coupling agent and nano calcium carbonate; and the PVC resin layer is prepared from a new material PVC resin. According to the synthetic resin tile, the regenerated PVC resin is used as a main material of the modified PVC resin filling layer, and the regenerated PVC resin is modified, so that the synthetic resin tile with excellent impact resistance, tensile property and heat resistance is obtained.

Description

Technical Field

[0001] The present application relates to the technical field of tiles, and in particular to a synthetic resin tile with strong impact resistance and a preparation method thereof. Background Art

[0002] As a new type of building material, synthetic resin tiles have been widely used in the construction field in recent years. It has many excellent properties such as light weight, high strength, waterproof, moisture-proof, anti-corrosion, flame-retardant, sound insulation and heat insulation. However, with the continuous increase of market demand and the increasing diversification of application scenarios, higher requirements are put forward for the performance of synthetic resin tiles, especially the impact resistance.

[0003] Among them, at present, some synthetic resin tiles on the market use a large amount of recycled PVC resin in order to reduce costs. Although the utilization rate of resources is improved, the impact resistance of recycled PVC resin is lower than that of new PVC resin. Directly using recycled PVC resin to prepare synthetic resin tiles will cause a significant decrease in its impact resistance.

[0004] At present, in order to improve the problem of poor impact resistance of recycled PVC resin, relevant technologies try to add glass fiber for modification. However, due to compatibility problems, the improvement effect of glass fiber on the impact resistance of recycled PVC resin is relatively poor.

[0005] Therefore, it has important research significance to improve the impact resistance and other properties of synthetic resin tiles while increasing the utilization rate of recycled PVC resin. Summary of the Invention

[0006] In order to improve the utilization rate of recycled PVC resin and improve the performance of synthetic resin tiles, the present application provides a synthetic resin tile with strong impact resistance and a preparation method thereof.

[0007] In the first aspect, a synthetic resin tile with strong impact resistance provided by the present application adopts the following technical solution: A synthetic resin tile with strong impact resistance, comprising an ASA surface layer, a modified PVC resin filling layer and a PVC resin layer arranged in sequence from top to bottom, and the thickness ratio of the ASA surface layer, the modified PVC resin filling layer and the PVC resin layer is (1-1.5):(7-8):(1-1.5); wherein: The ASA surface layer is made of ASA resin; The modified PVC resin filling layer is made of 50-55wt% recycled PVC resin, 3.5-4.4wt% dicyclopentadiene dimethylate, 8.5-9.8wt% vinyl-terminated polysiloxane, 15-20wt% modified nano calcium carbonate, 4-6wt% heat stabilizer, 0.1-0.2wt% initiator and the balance of new PVC resin. The preparation raw materials of the modified nano calcium carbonate include silane coupling agent and nano calcium carbonate; The PVC resin layer is made of virgin PVC resin.

[0008] In this application, the synthetic resin tile includes an ASA surface layer, a modified PVC resin filling layer, and a PVC resin layer. In the modified PVC resin filling layer, the main raw materials are recycled PVC resin and modified nano calcium carbonate, which can improve the utilization rate of recycled PVC resin and reduce waste of resources. However, the impact resistance of recycled PVC resin is lower than that of virgin PVC resin. Directly using recycled PVC resin to prepare the modified PVC resin filling layer will cause a significant decrease in the impact resistance of the synthetic resin tile. Therefore, in this application, an initiator is added to the raw materials for preparing the modified PVC resin filling layer. Under the initiation of the initiator, dicyclopentadiene dimethacrylate and vinyl-terminated polysiloxane are used together to crosslink and modify the recycled PVC resin, so as to improve the impact resistance, tensile properties, and heat resistance of the modified PVC resin filling layer. At the same time, an appropriate amount of modified nano calcium carbonate obtained by modifying nano calcium carbonate with a silane coupling agent is also added. The addition of the modified nano calcium carbonate can further improve the heat resistance of the synthetic resin tile and is beneficial to improving the dimensional stability of the synthetic resin tile.

[0009] In some specific embodiments, the modified nano calcium carbonate is nano calcium carbonate modified with a vinyl silane coupling agent.

[0010] Among them, the vinyl silane coupling agent is at least one of vinyltriethoxysilane, vinyltrimethoxysilane, and vinyltris(β-methoxyethoxy)silane.

[0011] In some preferred embodiments, the raw materials for preparing the modified nano calcium carbonate include allyl-terminated epoxy polyether, amino silane coupling agent, and nano calcium carbonate, and the weight ratio of the allyl-terminated epoxy polyether, amino silane coupling agent, and nano calcium carbonate is (20 - 25):(2.5 - 3.5):1.

[0012] In this application, the modified nano calcium carbonate is a product obtained by jointly modifying nano calcium carbonate with allyl-terminated epoxy polyether and amino silane coupling agent, which can further improve the impact resistance and tensile properties of the modified PVC resin filling layer, that is, it is beneficial to further improve the impact resistance and tensile strength of the synthetic resin tile.

[0013] In some specific embodiments, the allyl-terminated epoxy polyether is any one of allyl-terminated epoxy polyoxyethylene ether, allyl-terminated epoxy polyoxypropylene ether, and allyl-terminated epoxy polyoxyethylene polyoxypropylene ether.

[0014] In some preferred embodiments, the allyl-terminated epoxy polyether is allyl-terminated epoxy polyoxyethylene ether, and in the allyl-terminated epoxy polyoxyethylene ether, the degree of polymerization of the ethoxy chain segment is 40-50.

[0015] In the present application, the allyl epoxy polyether is further preferably allyl-terminated epoxy polyoxyethylene ether with the degree of polymerization of the polyoxyethylene chain segment being 40-50, which is beneficial to further improving the impact resistance of the synthetic resin tile.

[0016] In some specific embodiments, the alkenyl-terminated polysiloxane is at least one of vinyl-terminated polysiloxane and allyl-terminated polysiloxane.

[0017] In some preferred embodiments, in the alkenyl-terminated polysiloxane, the degree of polymerization of the polysiloxane chain segment is 20-25.

[0018] In the present application, the alkenyl-terminated polysiloxane is preferably alkenyl-terminated polysiloxane with the degree of polymerization of the polysiloxane chain segment being 20-25, which can further improve the impact resistance of the synthetic resin tile and at the same time can play a role in assisting the rapid and uniform dispersion of the modified nano calcium carbonate.

[0019] In some specific embodiments, the melt index of the ASA resin is 18-22 g / 10 min (220 °C / 10 kg).

[0020] In some preferred embodiments, the heat stabilizer includes (C 12 H 12 N2S)(C5H6O4)Zn, stearate, and organic stabilizer, and the weight ratio of (C 12 H 12 N2S)(C5H6O4)Zn, stearate, and organic stabilizer is (1-2):(1-2):1.

[0021] In the present application, the heat stabilizer is preferably a composition of (C 12 H 12 N2S)(C5H6O4)Zn, stearate, and organic stabilizer with a weight ratio of (1-2):(1-2):1. Through the synergistic cooperation of the three, it can effectively reduce the thermal degradation problem of the resin raw material in the processing of the modified PVC resin filling layer, further improve the impact resistance, tensile property, and thermal stability of the modified PVC resin filling layer, and thus improve the impact resistance, tensile strength, and dimensional thermal stability of the synthetic resin tile.

[0022] In some specific embodiments, the organic stabilizer is at least one of stearyl β-aminocrotonate and 1,4-butanediol bis(β-aminocrotonate).

[0023] In some specific embodiments, the initiator is a peroxide initiator.

[0024] Second, a preparation method of a synthetic resin tile with strong impact resistance provided by this application adopts the following technical solution: A preparation method of a synthetic resin tile with strong impact resistance includes the following steps: Put ASA resin into extruder A and melt it evenly at 190 - 220 °C to obtain ASA surface layer melt; Put recycled PVC resin, dicyclopentadiene dimethylate, vinyl-terminated polysiloxane, modified nano calcium carbonate, heat stabilizer, initiator and virgin PVC resin into extruder B according to the ratio and melt them evenly at 160 - 180 °C to obtain modified PVC resin filling layer melt; Put virgin PVC resin into extruder C and melt it evenly at 160 - 180 °C to obtain PVC resin layer melt; Distribute the ASA surface layer melt, modified PVC resin filling layer melt and PVC resin layer melt to the co-extrusion die head for co-extrusion according to the ratio, then hot press at 190 - 220 °C, and finally cool to obtain the synthetic resin tile.

[0025] This application uses the above method to prepare the synthetic resin tile, which is beneficial to promoting the full mixing and reaction of each raw material in the modified PVC resin filling layer and improving the finished product stability of the synthetic resin tile.

[0026] In summary, this application includes at least the following beneficial technical effects: (1) In this application, an initiator is added to the preparation raw materials of the modified PVC resin filling layer. Under the initiation of the initiator, the recycled PVC resin is crosslinked and modified by using dicyclopentadiene dimethylate and vinyl-terminated polysiloxane together to improve the impact resistance, tensile property and heat resistance of the modified PVC resin filling layer. At the same time, this application also adds an appropriate amount of modified nano calcium carbonate obtained by modifying nano calcium carbonate with a silane coupling agent. The addition of the modified nano calcium carbonate can further improve the heat resistance of the synthetic resin tile and is beneficial to enhancing the dimensional stability of the synthetic resin tile.

[0027] (2) In this application, the modified nano calcium carbonate is a product obtained by modifying nano calcium carbonate with allyl-terminated epoxy polyether and amino silane coupling agent together, which can further improve the impact resistance and tensile property of the modified PVC resin filling layer, that is, it is beneficial to further improve the impact resistance and tensile strength of the synthetic resin tile.

[0028] (3) In this application, the heat stabilizer is preferably (C 12 H 12A composition of N2S)(C5H6O4)Zn, stearate and organic stabilizer with a weight ratio of (1-2):(1-2):1 can effectively reduce the thermal degradation problem of resin raw materials in the processing of the modified PVC resin filling layer through the synergistic cooperation of the three. It can further improve the impact resistance, tensile properties and thermal stability of the modified PVC resin filling layer, and then improve the impact resistance, tensile strength and dimensional thermal stability of the synthetic resin tile. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 It is a longitudinal sectional schematic view of a synthetic resin tile with strong impact resistance in this application.

[0030] Description of the reference numerals: 1. ASA surface layer; 2. Modified PVC resin filling layer; 3. PVC resin layer. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0031] The following further illustrates this application in combination with specific experiments. Among them, the recycled PVC resin in each embodiment of this application uses SG5 type PVC resin recycled material, and the ash content in this recycled material is 5.5%, and the viscosity is 93.6 mL / g.

[0032] PREPARATION EXAMPLE

Preparation Example 1

[0033] In this preparation example, the preparation method of the modified nano calcium carbonate is as follows: Add vinyltriethoxysilane to ethanol, stir evenly, then add nano calcium carbonate and disperse evenly, then heat up to 45 °C, stir and reflux for 2 h, and finally separate the solid and dry to obtain the modified nano calcium carbonate.

[0034]

Preparation Example 2

[0035] In this preparation example, the preparation method of the modified nano calcium carbonate is as follows: Add amino-silane coupling agent KH550 into water. After stirring evenly, add nano-calcium carbonate and disperse it evenly. Then raise the temperature to 45 °C, stir and reflux for 2 h. Next, add allyl-terminated epoxy polyoxyethylene ether and continue to react for 1 h. Finally, separate the solid and dry it to obtain modified nano-calcium carbonate.

[0036]

Preparation Example 3

[0037] In this preparation example, the preparation method of the modified nano-calcium carbonate is as follows: Add epoxy-silane coupling agent KH560 into water. After stirring evenly, add nano-calcium carbonate and disperse it evenly. Then raise the temperature to 45 °C, stir and reflux for 2 h. Next, add allyl-terminated epoxy polyoxyethylene ether and continue to react for 1 h. Finally, separate the solid and dry it to obtain modified nano-calcium carbonate. Examples

[0038]

Example 1

[0039] In this example, the ASA surface layer 1 is made of ASA resin (LG LI-918 from South Korea); the modified PVC resin filling layer 2 is made of 50 wt% recycled PVC resin, 3.5 wt% dicyclopentadiene dimethylsodium, 8.5 wt% divinyl-terminated polydimethylsiloxane (the polymerization degree of the dimethylsiloxane segment is 25), 20 wt% of the modified nano-calcium carbonate prepared in

Preparation Example 1

[0040] In this embodiment, the preparation method of the synthetic resin tile with strong impact resistance includes the following steps: Put the ASA resin into extruder A and melt it evenly at 190 °C to obtain the ASA surface layer melt; Put the recycled PVC resin, sodium dicyclopentadiene dicarboxylate, divinyl - terminated polydimethylsiloxane, modified nano - calcium carbonate, heat stabilizer, diisopropylbenzene peroxide, and virgin PVC resin into extruder B according to the ratio and melt them evenly at 160 °C to obtain the modified PVC resin filling layer melt; Put the virgin PVC resin into extruder C and melt it evenly at 160 °C to obtain the PVC resin layer melt; Distribute the ASA surface layer melt, modified PVC resin filling layer melt, and PVC resin layer melt to the co - extrusion die head for co - extrusion, then hot - press at 190 °C, and finally cool to obtain the synthetic resin tile.

[0041]

Example 2

[0042] In this embodiment, the ASA surface layer 1 is made of ASA resin (South Korea LG LI - 918); the modified PVC resin filling layer 2 is made of 55 wt% recycled PVC resin, 4.4 wt% sodium dicyclopentadiene dicarboxylate, 9.8 wt% divinyl - terminated polydimethylsiloxane (the degree of polymerization of the dimethylsiloxane chain segment is 25), 15 wt% modified nano - calcium carbonate prepared in

Preparation Example 1

[0043] In this embodiment, the preparation method of the synthetic resin tile with strong impact resistance includes the following steps: Put the ASA resin into extruder A and melt it evenly at 220°C to obtain the ASA surface layer melt; Put the recycled PVC resin, sodium dicyclopentadiene dicarboxylate, divinyl-terminated polydimethylsiloxane, modified nano calcium carbonate, heat stabilizer, diisopropylbenzene peroxide, and new PVC resin into extruder B according to the ratio and melt them evenly at 180°C to obtain the modified PVC resin filling layer melt; Put the new PVC resin into extruder C and melt it evenly at 180°C to obtain the PVC resin layer melt; Distribute the ASA surface layer melt, modified PVC resin filling layer melt, and PVC resin layer melt to the co-extrusion die head according to the ratio for co-extrusion, then hot press at 220°C, and finally cool to obtain the synthetic resin tile.

[0044]

Example 3

Example 1

Preparation Example 2

[0045]

Example 4

Example 1

Preparation Example 3

[0046]

Example 5

Example 3

[0047]

Example 6

Example 3

[0048]

Example 7

Example 3

[0049]

Example 8

Example 3

[0050] Comparative Example

Comparative Example 1

Example 1

[0051]

Comparative Example 2

Example 1

[0052]

Comparative Example 3

Example 1

[0053] In this comparative example, the modified PVC resin filling layer 2 is prepared from 60 wt% recycled PVC resin, 8.5 wt% sodium dicyclopentadiene dimethylate, 3.5 wt% divinyl-terminated polydimethylsiloxane (the degree of polymerization of the dimethylsiloxane segment is 25), 10 wt% modified nano calcium carbonate prepared in

Preparation Example 1

[0054]

Comparative Example 4

Example 1

[0055] Performance Detection Test 1. Drop hammer impact: Refer to JG / T 346-2011 to detect the number of specimens that are cracked or separated at different drop hammer heights. The number of specimens in each group of tests is 10. Among them, when the drop hammer falls from a height of 1000 mm, if the number of specimens with cracks or separations does not exceed 1, it is considered qualified.

[0056] 2. Tensile strength: Detect according to JG / T 346-2011. Among them, if the tensile strength is greater than 25 MPa, it is considered qualified.

[0057] 3. Dimensional change rate after heating: Detect according to JG / T 346-2011. The test temperature is 100 °C and the heating time is 120 min. Among them, if the dimensional change rate after heating is not greater than 2%, it is considered qualified.

[0058] Table 1 Table 2 Specimen Tensile strength / MPa Dimensional change rate after heating / % Example 1 28.4 1.01 Example 2 28.9 1.11 Example 3 30.2 0.94 Example 4 28.7 1.02 Example 5 28.1 1.27 Example 6 27.4 1.36 Example 7 27.8 1.31 Example 8 28.9 1.18 Comparative Example 1 30.5 0.71 Comparative Example 2 24.8 1.26 Comparative Example 3 22.1 2.58 Comparative Example 4 18.6 5.94 Combining the detection data in Comparative Examples 1-4, Example 1, and Tables 1-2 above, it can be seen that crosslinking and modifying recycled PVC resin with dicyclopentadiene dimethylate and alkenyl-terminated polysiloxane in a specific ratio is beneficial to obtaining synthetic resin tiles with good impact resistance, tensile properties, and heat resistance.

[0059] Combining the detection data in Examples 3-4, Example 1, and Tables 1-2, it can be seen that the product obtained by modifying nano calcium carbonate with allyl-terminated epoxy polyether and amino silane coupling agent can further improve the impact resistance and tensile properties of the modified PVC resin filling layer, that is, it is beneficial to further improve the impact resistance and tensile strength of the synthetic resin tile.

[0060] Combining the detection data in Example 3, Examples 5-8, and Tables 1-2, it can be seen that the heat stabilizer is preferably a composition of (C 12 H 12 N2S)(C5H6O4)Zn, stearate, and organic stabilizer with a weight ratio of (1-2):(1-2):1, which is beneficial to further improving the impact resistance, tensile properties, and heat stability of the modified PVC resin filling layer, and thus improving the impact resistance, tensile strength, and dimensional thermal stability of the synthetic resin tile.

[0061] This specific embodiment is only an interpretation of the present application and does not limit the present application. After reading this specification, those skilled in the art can make modifications to this specific embodiment without creative contributions as needed, but as long as it is within the scope of the claims of the present application, it is protected by the patent law.

Claims

1. A synthetic resin tile with strong impact resistance, characterized in that: It includes an ASA surface layer (1), a modified PVC resin filling layer (2), and a PVC resin layer (3) which are arranged in sequence from top to bottom. The thickness ratio of the ASA surface layer (1), the modified PVC resin filling layer (2), and the PVC resin layer (3) is (1 - 1.5):(7 - 8):(1 - 1.5); where: The ASA surface layer (1) is made of ASA resin; The modified PVC resin filling layer (2) is made of 50 - 55wt% recycled PVC resin, 3.5 - 4.4wt% dicyclopentadiene dimethylate, 8.5 - 9.8wt% vinyl-terminated polysiloxane, 15 - 20wt% modified nano calcium carbonate, 4 - 6wt% heat stabilizer, 0.1 - 0.2wt% initiator, and the balance of virgin PVC resin. The preparation raw materials of the modified nano calcium carbonate include silane coupling agent and nano calcium carbonate; The PVC resin layer (3) is made of virgin PVC resin.

2. The synthetic resin tile with strong impact resistance according to claim 1, characterized in that: The preparation raw materials of the modified nano calcium carbonate include allyl-terminated epoxy polyether, amino silane coupling agent, and nano calcium carbonate. The weight ratio of the allyl-terminated epoxy polyether, the amino silane coupling agent, and the nano calcium carbonate is (20 - 25):(2.5 - 3.5):

1.

3. The synthetic resin tile with strong impact resistance according to claim 2, characterized in that: The allyl-terminated epoxy polyether adopts any one of allyl-terminated epoxy polyoxyethylene ether, allyl-terminated epoxy polyoxypropylene ether, and allyl-terminated epoxy polyoxyethylene polyoxypropylene ether.

4. The synthetic resin tile with strong impact resistance according to claim 3, characterized in that: The allyl-terminated epoxy polyether adopts allyl-terminated epoxy polyoxyethylene ether, and in the allyl-terminated epoxy polyoxyethylene ether, the polymerization degree of the ethoxy chain segment is 40 - 50.

5. The synthetic resin tile with strong impact resistance according to claim 1, characterized in that: The vinyl-terminated polysiloxane adopts at least one of vinyl-terminated polysiloxane and allyl-terminated polysiloxane.

6. The synthetic resin tile with strong impact resistance according to claim 1, wherein: In the vinyl-terminated polysiloxane, the polymerization degree of the polysiloxane chain segment is 20 - 25.

7. The synthetic resin tile with strong impact resistance according to claim 1, characterized in that: The heat stabilizer includes (C 12 H 12 N2S)(C5H6O4)Zn, stearate, and an organic stabilizer. The weight ratio of (C 12 H 12 N2S)(C5H6O4)Zn, stearate, and the organic stabilizer is (1 - 2):(1 - 2):

1.

8. The synthetic resin tile with strong impact resistance according to claim 7, wherein: The organic stabilizer adopts at least one of stearyl β-aminocrotonate and 1,4-butanediol bis(β-aminocrotonate).

9. The synthetic resin tile with strong impact resistance according to claim 1, wherein: The initiator adopts a peroxide initiator.

10. A preparation method of a synthetic resin tile with strong impact resistance as described in any one of claims 1-9, characterized in that, It includes the following steps: Put the ASA resin into extruder A and melt it evenly at 190 - 220°C to obtain the ASA surface layer melt; Put the recycled PVC resin, dicyclopentadiene dimethylate, vinyl-terminated polysiloxane, modified nano calcium carbonate, heat stabilizer, initiator, and virgin PVC resin into extruder B according to the ratio and melt them evenly at 160 - 180°C to obtain the modified PVC resin filling layer melt; Put the virgin PVC resin into extruder C and melt it evenly at 160 - 180°C to obtain the PVC resin layer melt; Distribute the ASA surface layer melt, the modified PVC resin filling layer melt, and the PVC resin layer melt to the coextrusion die head according to the ratio for coextrusion, then hot press at 190 - 220°C, and finally cool to obtain the synthetic resin tile.

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