Waterproof composite floor and preparation method thereof

Abstract

The present invention discloses a waterproof composite floor and a preparation method thereof, belonging to the technical field of flooring, comprising a substrate layer, a waterproof layer, a decorative layer and a balancing layer, wherein the upper surface of the substrate layer is provided with a waterproof layer, the upper surface of the waterproof layer is provided with a decorative layer, and the lower surface of the substrate layer is provided with a balancing layer; the material of the waterproof layer is a modified cement-based penetrating crystalline waterproof coating, the modified cement-based penetrating crystalline waterproof coating comprises a modified organic silicon waterproofing agent, the modified organic silicon waterproofing agent is prepared by using tannic acid and Fe 3+ The formation of a hydrophobic complex modifies the nano-calcium carbonate, increasing its lipophilic and hydrophobic properties, and thus increasing the hydrophobicity of the waterproofing agent, thereby significantly improving the waterproofing performance of the waterproof coating. The present invention utilizes a modified cement-based permeable crystalline waterproof coating as the waterproof layer, which is applied to the upper surface of the substrate layer. This effectively prevents moisture from penetrating the decorative layer, thus preventing the precipitation of verdigris through the decorative layer.

Description

Technical Field

[0001] The invention belongs to the technical field of flooring, and in particular relates to a waterproof composite flooring and a preparation method thereof. Background Art

[0002] Composite flooring is a type of flooring, but the natural structure of the composite flooring material is artificially changed to achieve certain physical properties that meet the expected requirements.

[0003] After recycling and crushing waste circuit boards and extracting metal, the remaining waste resin powder is used to make the base plate. After melamine hot-pressing, cutting and slotting, the composite flooring can be used in both wet and dry areas indoors and outdoors. The main components of waste electronic circuit board powder are epoxy resin and fiberglass as a skeleton material. The pressed board has waterproof properties and does not expand or deform even when soaked in water. However, the metal cannot be completely extracted and some residues remain. Although the decorative paper impregnated with melamine basically prevents moisture from penetrating the composite flooring, when exposed to water vapor or relative humidity for a long time (this often happens when water escapes from wet floors or concrete), the verdigris precipitates through the melamine decoration and is difficult to remove, affecting the appearance quality. Summary of the Invention

[0004] The purpose of the present invention is to provide a waterproof composite floor and a preparation method thereof to solve the following technical problems: the composite floor made by recycling waste circuit boards has poor waterproof performance, and verdigris precipitates when used in a humid environment for a long time, affecting the appearance quality.

[0005] The purpose of the present invention can be achieved through the following technical solutions:

[0006] A waterproof composite floor comprises a base material layer, a waterproof layer, a decorative layer and a balancing layer, wherein the waterproof layer is provided on the upper surface of the base material layer, the decorative layer is provided on the upper surface of the waterproof layer, and the balancing layer is provided on the lower surface of the base material layer;

[0007] The material of the waterproof layer is a modified cement-based penetrating crystalline waterproof coating, which is prepared by the following steps: by weight, 50-65 parts of Portland cement, 20-40 parts of quartz sand, 1-6 parts of sodium silicate, 0.5-7 parts of sodium sulfate, 0.3-1.5 parts of sodium hexametaphosphate, 0.05-0.2 parts of hydroxypropyl methylcellulose, 0-5 parts of sodium carbonate, 2-7 parts of modified organic silicon waterproofing agent, and 40-55 parts of water are mixed and stirred for 30-45 minutes to obtain the modified cement-based penetrating crystalline waterproof coating;

[0008] Sodium silicate, sodium sulfate, sodium hexametaphosphate, hydroxypropyl methylcellulose, and sodium carbonate can react with the Ca in cement. 2+ It reacts with the hydration product calcium hydroxide to form crystals or hydrated calcium silicate gel to plug cracks and pores, thus playing a waterproof role.

[0009] The modified organosilicon waterproofing agent comprises the following steps of preparation:

[0010] Step 1: Modification of nano-CaCO3: Add 2-8g of tannic acid and 1-2g of ferric chloride hexahydrate to 100mL of deionized water and stir to mix, then add 3-5g of nano-CaCO3 and disperse by ultrasonication. Adjust the pH to 8, let stand for 1-2h, filter, wash with water, and dry at 50-80℃ to constant weight to obtain modified nano-CaCO3.

[0011] Step 2, modification of silicone oil: 30-40g octamethylcyclotetrasiloxane, 1.8-2g N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane, 0.06-0.08g hexamethyldisiloxane and 1.5-2g hexadecanetrimethoxysilane are mixed, stirred and heated to 90°C, 0.048-0.064g KOH and 3-4g modified nano-CaCO3 are added, and the mixture is kept at a constant temperature of 110-120°C for 3-5h to obtain modified silicone oil;

[0012] Step 3: Evenly mix 2.5-3.5 g of modified silicone oil and 0.75-1 g of isomeric tridecanol polyoxyethylene ether, adjust the pH to 6, and add 8-15 mL of water to obtain a modified silicone waterproofing agent.

[0013] Furthermore, the substrate layer is prepared by the following steps:

[0014] 80-98 parts of waste resin powder and 2-20 parts of isocyanate adhesive are mixed evenly by weight, and transported to a multi-layer heated hydraulic press for hot pressing, plate production, cooling, cutting, and polishing to obtain a substrate layer.

[0015] Furthermore, the hot pressing temperature is 160-180° C., and the hot pressing pressure is 10-15 MPa.

[0016] Furthermore, the waste resin powder is prepared by the following steps:

[0017] Step 1: After removing the metal from the electronic components of the waste circuit boards, the waste circuit boards are sequentially subjected to detinning, crushing, magnetic separation to remove iron, and eddy current separation to remove aluminum to obtain pretreated powder;

[0018] Step 2: After adding grinding balls and ball milling media to the pretreated powder, ball mill it at a speed of 100-200 r / min for 15 min, then at a speed of 350 r / min for 1-2 h, pass it through a 40-100 mesh sieve, and dry it at 130°C-150°C to obtain waste resin powder.

[0019] Furthermore, the water content of the waste resin powder is 0-5%.

[0020] Furthermore, the grinding balls are prepared by mixing zirconium balls, agate balls and steel balls in a volume ratio of 2:2:1, and the diameter of the balls is 5-20 mm; the volume ratio of the pretreated powder, grinding balls and ball milling media is 1:1:1.

[0021] Furthermore, the ball milling medium is any one of water and ethanol.

[0022] The pretreated powder is an enriched mass of epoxy resin powder, glass fiber and copper. After being uniformly mixed with grinding balls and ball milling media at a low speed of 100-200 r / min, it is ball milled at a speed of 350 r / min to reduce the particle size of epoxy resin powder and glass fiber in the pretreated powder, while the copper particles are basically unaffected. The copper and ball milling media can be removed by passing through a 40-100 mesh sieve and drying.

[0023] Furthermore, the temperature of the detinning treatment is 180-230° C., and the particle size of the crushed particles is 20-30 mm.

[0024] Furthermore, the decorative layer is a combination of wear-resistant adhesive film paper and decorative adhesive film paper, or any one of wear-resistant decorative adhesive film paper.

[0025] Furthermore, the balancing layer is balancing film paper.

[0026] Furthermore, the method for preparing the waterproof composite floor comprises the following steps:

[0027] After the waterproof layer material is evenly applied on the upper surface of the base material layer, the balancing layer, base material layer and decorative layer are placed in sequence, and after hot pressing, the boards are separated and formed to obtain a waterproof composite floor.

[0028] Furthermore, the amount of the coating is 250-300 mL / m 2 .

[0029] Furthermore, the hot pressing temperature is 170-190°C, the hot pressing time is 32-35s, and the pressure is 2500-2800t / m 2 .

[0030] Beneficial effects of the present invention:

[0031] The present invention modifies the organosilicon waterproofing agent, and the silanol groups in the molecular structure of the organosilicon waterproofing agent react with the silanol groups in the silicate cement material to dehydrate and crosslink, thereby forming a hydrophobic layer, which plays a role of "water blocking". Tannic acid and Fe 3+The formation of hydrophobic complex modified nano calcium carbonate improves the lipophilicity and hydrophobicity of nano calcium carbonate, making it easier to combine with silicone oil and evenly disperse in the silicone waterproofing agent, and is not prone to agglomeration, thereby uniformly constructing a fine protrusion structure on the silicone surface. This structure can increase the hydrophobicity of the waterproofing agent, thereby significantly improving the waterproof performance of the cement-based penetrating crystalline waterproof coating.

[0032] The present invention adopts a modified cement-based penetrating crystallization waterproof coating as a waterproof layer and arranges it on the upper surface of the substrate layer, thereby effectively preventing moisture from penetrating the decorative layer, thereby avoiding the problem of patina precipitating through the decorative layer and affecting the appearance quality of the composite floor. DETAILED DESCRIPTION

[0033] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts shall fall within the scope of protection of the present invention.

[0034] Example 1

[0035] A modified cement-based penetrating crystalline waterproof coating is prepared by the following steps:

[0036] Step S1, preparation of modified silicone waterproofing agent:

[0037] Step 1: Modification of nano-CaCO3: Add 2g of tannic acid and 1g of ferric chloride hexahydrate to 100mL of deionized water and stir to mix, then add 3g of nano-CaCO3 and disperse by ultrasonication. Adjust the pH to 8, let stand for 1h, filter, wash with water, and dry at 50℃ to constant weight to obtain modified nano-CaCO3.

[0038] Step 2, modification of silicone oil: 30g octamethylcyclotetrasiloxane, 1.8g N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane, 0.06g hexamethyldisiloxane and 1.5g hexadecanetrimethoxysilane were mixed, stirred and heated to 90°C, 0.048g KOH and 3g modified nano-CaCO3 were added, and the mixture was kept at a constant temperature of 110°C for 3h to obtain modified silicone oil;

[0039] Step 3: Mix 2.5 g of modified silicone oil and 0.75 g of isomeric tridecanol polyoxyethylene ether, adjust the pH to 6, and add 8 mL of water to obtain a modified silicone waterproofing agent;

[0040] Step S2: By weight, 50 g of Portland cement, 20 g of quartz sand, 1 g of sodium silicate, 0.5 g of sodium sulfate, 0.3 g of sodium hexametaphosphate, 0.05 g of hydroxypropyl methylcellulose, 0 g of sodium carbonate, 2 g of modified organic silicone waterproofing agent, and 40 g of water are mixed and stirred for 30 min to obtain a modified cement-based penetrating crystalline waterproof coating.

[0041] Example 2

[0042] A modified cement-based penetrating crystalline waterproof coating is prepared by the following steps:

[0043] Step S1, preparation of modified silicone waterproofing agent:

[0044] Step 1: Modification of nano-CaCO3: Add 8g of tannic acid and 2g of ferric chloride hexahydrate to 100mL of deionized water and stir to mix, then add 5g of nano-CaCO3 and disperse by ultrasonication. Adjust the pH to 8, let stand for 2h, filter, wash with water, and dry at 80℃ to constant weight to obtain modified nano-CaCO3.

[0045] Step 2, modification of silicone oil: 40g of octamethylcyclotetrasiloxane, 2g of N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane, 0.08g of hexamethyldisiloxane and 2g of hexadecanetrimethoxysilane were mixed, stirred and heated to 90°C, 0.064g of KOH and 4g of modified nano-CaCO3 were added, and the mixture was kept at a constant temperature of 120°C for 5h to obtain modified silicone oil;

[0046] Step 3: Mix 3.5 g of modified silicone oil and 1 g of isomeric tridecanol polyoxyethylene ether, adjust the pH to 6, and add 15 mL of water to obtain a modified silicone waterproofing agent;

[0047] Step S2: By weight, 65 g of Portland cement, 40 g of quartz sand, 6 g of sodium silicate, 7 g of sodium sulfate, 1.5 g of sodium hexametaphosphate, 0.2 g of hydroxypropyl methylcellulose, 5 g of sodium carbonate, 7 g of modified organic silicone waterproofing agent, and 55 g of water are mixed and stirred for 45 minutes to obtain a modified cement-based penetrating crystalline waterproof coating.

[0048] Comparative Example 1

[0049] Compared with Example 1, this comparative example omitted step 1, and did not add "3-4g modified nano-CaCO3" in step 2. The remaining steps and parameters were the same.

[0050] Example 3

[0051] The preparation of the substrate layer includes the following preparation steps:

[0052] Step A1: Preparation of waste resin powder:

[0053] Step 1: After removing the metal from the electronic components of the waste circuit boards, the waste circuit boards are subjected to a 180°C detinning treatment, crushed (the crushed particles are 20-30 mm in size), magnetic separation to remove iron, and eddy current separation to remove aluminum to obtain pretreated powder;

[0054] Step 2: Add grinding balls (the grinding balls are zirconium balls, agate balls and steel balls mixed in a volume ratio of 2:2:1) and ball milling media (water, ethanol) (the volume ratio of pretreated powder, grinding balls and ball milling media is 1:1:1) to the pretreated powder, first ball milling at a speed of 100 r / min for 15 min, then ball milling at a speed of 350 r / min for 1 h, pass through a 40-mesh sieve, and dry at 130°C to obtain waste resin powder (water content of 0-5%).

[0055] Step A2: 80 g of waste resin powder and 2 g of isocyanate adhesive were mixed evenly by weight, and transported to a multi-layer heated hydraulic press for hot pressing at 160° C. and 10 MPa, sheeting, cooling, cutting, and polishing to obtain a substrate layer.

[0056] Example 4

[0057] The preparation of the substrate layer includes the following preparation steps:

[0058] Step A1: Preparation of waste resin powder:

[0059] Step 1: After removing the metal from the electronic components of the waste circuit boards, the waste circuit boards are subjected to a 230°C detinning treatment, crushed (the crushed particles are 20-30 mm in size), magnetic separation to remove iron, and eddy current separation to remove aluminum to obtain pretreated powder;

[0060] Step 2: Add grinding balls (the grinding balls are zirconium balls, agate balls and steel balls mixed in a volume ratio of 2:2:1) and ball milling media (water, ethanol) (the volume ratio of pretreated powder, grinding balls and ball milling media is 1:1:1) to the pretreated powder, first ball milling at a speed of 200 r / min for 15 min, then ball milling at a speed of 350 r / min for 2 h, sieve through a 100 mesh sieve, and dry at 150°C to obtain waste resin powder (water content of 0-5%).

[0061] Step A2: 98 g of waste resin powder and 20 g of isocyanate adhesive were mixed evenly by weight, and transported to a multi-layer heated hydraulic press for hot pressing at 180° C. and 15 MPa, sheeting, cooling, cutting, and polishing to obtain a substrate layer.

[0062] Example 5

[0063] A method for preparing a waterproof composite floor comprises the following steps:

[0064] The modified cement-based penetrating crystallization waterproof coating prepared in Example 1 was evenly applied on the upper surface of the substrate layer prepared in Example 3, and the amount of the coating was 250 mL / m 2 , place the balance film paper, base material layer, wear-resistant decorative film paper in turn, and perform hot pressing. The hot pressing temperature is 170℃, the hot pressing time is 32s, and the pressure is 2500t / m 2 , splitting the boards and forming the boards to obtain a waterproof composite floor.

[0065] Example 6

[0066] A method for preparing a waterproof composite floor comprises the following steps:

[0067] The modified cement-based penetrating crystallization waterproof coating prepared in Example 2 was evenly applied on the upper surface of the substrate layer prepared in Example 4, and the amount of the coating was 300 mL / m 2 , place the balance film paper, base material layer, wear-resistant decorative film paper in turn, and perform hot pressing. The hot pressing temperature is 190℃, the hot pressing time is 35s, and the pressure is 2800t / m 2 , splitting the boards and forming the boards to obtain a waterproof composite floor.

[0068] Comparative Example 2

[0069] A method for preparing a waterproof composite floor comprises the following steps:

[0070] Compared with Example 5, this comparative example only replaces the "modified cement-based penetrating crystallization waterproof coating prepared in Example 1" with the "modified cement-based penetrating crystallization waterproof coating prepared in Comparative Example 1", and the remaining steps and parameters are the same.

[0071] Comparative Example 3

[0072] A method for preparing a waterproof composite floor comprises the following steps:

[0073] Compared with Example 5, this comparative example only does not apply the modified cement-based penetrating crystallization waterproof coating on the upper surface of the substrate layer, and the remaining steps and parameters are the same.

[0074] The waterproof composite flooring prepared in Examples 5-6 and the waterproof composite flooring prepared in Comparative Examples 2-3 were tested for waterproof performance: the waterproof composite flooring to be tested was installed indoors, the indoor humidity was maintained at 65%-100%, and after 72 hours, the presence of verdigris was observed and recorded. The results are shown in Table 1:

[0075] Table 1

[0076]

[0077] It can be seen from Table 1 that the waterproof composite floor prepared in Examples 5-6 has better waterproof performance than the waterproof composite floor prepared in Comparative Examples 2-3, and can effectively prevent the precipitation of verdigris.

[0078] It should be noted that, in this document, relational terms such as first and second, etc., are used only to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any actual relationship or order between these entities or operations. Moreover, the terms "comprises," "comprising," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that includes a list of elements includes not only those elements but also other elements not explicitly listed, or elements inherent to such process, method, article, or apparatus.

[0079] While embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions, and variations may be made to these embodiments without departing from the principles and spirit of the invention, and that the scope of the invention is defined by the appended claims and their equivalents.

Claims

1. A waterproof composite floor, characterized in that: It includes a base material layer, a waterproof layer, a decorative layer and a balancing layer. The upper surface of the base material layer is provided with a waterproof layer, the upper surface of the waterproof layer is provided with a decorative layer, and the lower surface of the base material layer is provided with a balancing layer. The material of the waterproof layer is a modified cement-based penetrating crystalline waterproof coating, which is prepared by the following steps: by weight, 50-65 parts of Portland cement, 20-40 parts of quartz sand, 1-6 parts of sodium silicate, 0.5-7 parts of sodium sulfate, 0.3-1.5 parts of sodium hexametaphosphate, 0.05-0.2 parts of hydroxypropyl methylcellulose, 0-5 parts of sodium carbonate, 2-7 parts of modified organic silicon waterproofing agent, and 40-55 parts of water are mixed and stirred for 30-45 minutes to obtain the modified cement-based penetrating crystalline waterproof coating; The modified organosilicon waterproofing agent comprises the following steps of preparation: Step 1: Modification of nano-CaCO3: Add 2-8g of tannic acid and 1-2g of ferric chloride hexahydrate to 100mL of deionized water and stir to mix, then add 3-5g of nano-CaCO3 and disperse by ultrasonication. Adjust the pH to 8, let stand for 1-2h, filter, wash with water, and dry at 50-80℃ to constant weight to obtain modified nano-CaCO3. Step 2, modification of silicone oil: 30-40g octamethylcyclotetrasiloxane, 1.8-2g N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane, 0.06-0.08g hexamethyldisiloxane and 1.5-2g hexadecanetrimethoxysilane are mixed, stirred and heated to 90°C, 0.048-0.064g KOH and 3-4g modified nano-CaCO3 are added, and the mixture is kept at a constant temperature of 110-120°C for 3-5h to obtain modified silicone oil; Step 3: Evenly mix 2.5-3.5 g of modified silicone oil and 0.75-1 g of isomeric tridecanol polyoxyethylene ether, adjust the pH to 6, and add 8-15 mL of water to obtain a modified silicone waterproofing agent.

2. The waterproof composite floor according to claim 1, characterized in that: The substrate layer is prepared by the following steps: 80-98 parts of waste resin powder and 2-20 parts of isocyanate adhesive are mixed evenly by weight, and transported to a multi-layer heated hydraulic press for hot pressing, plate production, cooling, cutting, and polishing to obtain the substrate layer.

3. The waterproof composite floor according to claim 2, characterized in that: The temperature of the hot pressing is 160-180° C., and the pressure of the hot pressing is 10-15 MPa.

4. The waterproof composite floor according to claim 2, characterized in that: The waste resin powder comprises the following steps of preparing: Step 1: After removing the metal from the electronic components of the waste circuit boards, the waste circuit boards are sequentially subjected to detinning, crushing, magnetic separation to remove iron, and eddy current separation to remove aluminum to obtain pretreated powder; Step 2: Add grinding balls and ball milling media to the pretreated powder obtained in step 1, first ball mill at a speed of 100-200 r / min for 15 minutes, then ball mill at a speed of 350 r / min for 1-2 hours, pass through a 40-100 mesh sieve, and dry at 130°C-150°C to obtain waste resin powder.

5. The waterproof composite floor according to claim 2, characterized in that: The water content of the waste resin powder is 0-5%.

6. The method for preparing a waterproof composite floor according to claim 1, characterized in that: The method comprises the following preparation steps: evenly applying waterproof layer material on the upper surface of the substrate layer, sequentially placing a balancing layer, substrate layer and decorative layer, hot pressing, separating the panels and forming the panels to obtain a waterproof composite floor.

7. The method for preparing a waterproof composite floor according to claim 6, characterized in that: The amount of the coating is 250-300 mL / m 2 .

8. The method for preparing a waterproof composite floor according to claim 6, characterized in that: The hot pressing temperature is 170-190°C, the hot pressing time is 32-35s, and the pressure is 2500-2800t / m 2 .

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