Anti-warping and anti-aging plastic floor substrate, floor and preparation method thereof

Abstract

The present invention belongs to the technical field of high molecular polymer floor materials, and specifically relates to a warping and aging-resistant plastic floor substrate, a floor, and a preparation method. The floor substrate of the present invention is made of a certain ratio of PETG resin, ABS resin, compatibilizer, activated halloysite / calcium carbonate composite powder, chain extender, lubricant, coupling agent, antioxidant, and light stabilizer. The floor substrate of the present invention can be coated with a color film, a transparent film, and a sound-proof layer to produce a floor product. The floor made from the floor substrate of the present invention has the advantages of low warping, cracking and arching resistance, halogen-free and environmentally friendly, and is a green, low-carbon, PVC-free and environmentally friendly floor.

Description

Technical Field

[0001] The present invention belongs to the technical field of high molecular polymer floor materials, and in particular relates to an anti-warping and anti-aging plastic floor substrate, a floor and a preparation method thereof. Background Art

[0002] PVC flooring, the most widely used plastic flooring, faces challenges such as high recycling costs and dioxin generation from direct incineration. With the recent rise of environmentally friendly concepts like "Non-PVC" and "PVC-Free," the use of non-PVC materials like PP and PE in the home building materials industry is expanding. Research and development of safe, environmentally friendly, and durable non-PVC flooring is a key trend in future technological development.

[0003] PET (polyethylene terephthalate), also known as polyethylene terephthalate, offers advantages such as being non-toxic, odorless, safe, environmentally friendly, and recyclable. However, as a semi-crystalline polymer with strong macromolecular aggregation, PET exhibits poor impact resistance, making it unsuitable for elastic plastic flooring. Limited research on PET flooring is currently available, such as in patents CN110029796A and CN114571821A. PETG (polyethylene terephthalate-1,4-cyclohexanedimethylene terephthalate), also known as polyethylene terephthalate-1,4-cyclohexanedimethylene terephthalate, is a transparent, non-crystalline copolyester. However, compared to existing PVC elastic plastic flooring, PETG's light and thermal expansion properties fall short of practical requirements. Parameters such as dimensional stability still need improvement. There are currently a small number of documents that use PETG for flooring, such as patent document CN115139616A (PETG as an anti-scratch layer and a glass fiber layer), CN219706385U (PETG only as a film layer), CN214329733U (PETG is made together with a carbon fiber sheet layer and a polyphosphate sheet), CN212453480U (PETG only as a wear-resistant layer), CN112064977A (PETG only as a wear-resistant layer and a decorative layer, the base material layer is an MDI flame-retardant fiberboard), and CN112009060A (PETG as a wear-resistant layer, a decorative layer, and a base material layer).

[0004] ABS resin (Acrylonitrile Butadiene Styrene) is a thermoplastic polymer material with high strength, good toughness, and easy processing and molding. Due to its high strength, corrosion resistance, and high temperature resistance, it is often used in the manufacture of plastic casings for instruments. However, ABS also has the problem of being prone to warping, as shown in CN109206832A.

[0005] There are reports on the use of PETG / ABS alloys in the production of rubber for ship fenders and computer monitor housings, such as in CN105482274A and CN109535634A. However, the complex nature of the materials makes them unsuitable for use as flooring substrates. Currently, there are no reports on the research and performance of PETG / ABS alloys for flooring. Summary of the Invention

[0006] In view of the above problems, the purpose of the present invention is to provide a warping and aging-resistant plastic floor substrate and a floor and a preparation method. The floor has low warping and other properties that are difficult to achieve with ordinary floors, thereby improving the overall performance of the floor.

[0007] The technical solution of the present invention includes:

[0008] First, the present invention provides an anti-warping and anti-aging plastic floor substrate, which is made of the following materials, in parts by weight: 40-60 parts of PETG resin, 10-30 parts of ABS resin, 2-10 parts of compatibilizer, 150-200 parts of activated halloysite / calcium carbonate composite powder, 0.4-2 parts of chain extender, 0.4-1.5 parts of coupling agent, 1-3 parts of lubricant, 0.5-1.5 parts of antioxidant, and 0.1-2 parts of light stabilizer. The activated halloysite / calcium carbonate composite powder is obtained by heating and activating acidified halloysite, then blending it with calcium carbonate in water, and then filtering and drying it after ultrasonic treatment.

[0009] Preferably, when preparing the activated halloysite / calcium carbonate composite powder, the mass ratio of halloysite to calcium carbonate is 1:(1-4).

[0010] Preferably, the compatibilizer is one or more of AS-g-MAH, SEBS-g-GMA, POE-g-GMA, and ABS-g-MAH, more preferably POE-g-GMA.

[0011] Preferably, the chain extender is one or more of epoxies, oxazolines, isocyanates, and acid anhydrides; more preferably, it is one or more of 2,2-(1,3-phenylene)-bis(2-oxazoline) (PBO, oxazolines), triglycidyl isocyanurate (TGIC, isocyanates), and pyromellitic dianhydride (PMDA, anhydrides).

[0012] Preferably, the coupling agent is one or more of aluminate, phosphate, and titanate, and more preferably one or two of aluminate and titanate.

[0013] Preferably, the lubricant is one or more of zinc stearate, erucamide, ethylene bisstearamide (EBS), and mineral white oil, and more preferably EBS.

[0014] Preferably, the antioxidant is one or more of hindered phenols, aromatic amines, phosphites, and sulfur-containing esters. More preferably, the antioxidant is one or more of Antioxidant 1010 (hindered phenols), Antioxidant 5057 (aromatic amines), Antioxidant 626 (phosphites), and ditridecyl thiodipropionate (DTDTP, sulfur-containing esters).

[0015] Preferably, the light stabilizer is one or more of carbon black, benzophenones (e.g., BASF Chimassorb 81), acetanilides (e.g., Sanduvor VSU), benzotriazoles (e.g., UV-320), or triazines (e.g., UV-1164). Carbon black is more preferred.

[0016] Secondly, the present invention provides a method for preparing the aforementioned plastic floor substrate, comprising the following steps:

[0017] S1: The halloysite is acidified with hydrochloric acid, and then heated and activated at 60° C. for 8 h. The acidified halloysite and calcium carbonate are then added to pure water, mixed, and ultrasonically treated for 2 h. The activated halloysite / calcium carbonate composite powder is obtained by filtering and drying.

[0018] S2: Activated halloysite / calcium carbonate composite powder, PETG resin, ABS resin, compatibilizer, chain extender, lubricant, coupling agent, antioxidant and light stabilizer are placed in a high-speed mixer and stirred at a speed of 300-350 r / min for 10-20 minutes. The resulting mixture is twin-screw extruded, with the temperatures of the twin-screw zones being 200-190°C, 195-190°C, 190-180°C, 185-175°C, and 180-170°C, respectively, and the confluence core temperature being 170-160°C. The plastic floor substrate is then shaped and fixed in thickness to obtain the plastic floor substrate.

[0019] Again, the present invention provides a floor prepared using the aforementioned plastic floor substrate, which is made of six layers of materials, and the layering order of the six layers of materials is: a first coating layer, a transparent film layer, a color film layer, an anti-warping and anti-aging plastic floor substrate layer, a second coating layer, and a sound-absorbing layer.

[0020] Preferably, the color film layer and the transparent film layer are both made of PETG;

[0021] Preferably, the thickness of the plastic floor substrate layer is 4.1-4.2 mm;

[0022] Preferably, the color film layer has a thickness of 1 mm;

[0023] Preferably, the transparent film layer has a thickness of 2 to 3 mm.

[0024] Preferably, the first coating layer and the second coating layer are made of polyurethane-acrylic resin coating;

[0025] Preferably, the sound absorbing layer is selected from radiation cross-linked polyethylene (IXPE) sound-absorbing pad or radiation cross-linked polypropylene (IXPP) sound-absorbing pad.

[0026] The beneficial effects of the present invention include:

[0027] In the plastic flooring substrate of the present invention, PETG has good structural regularity and high flatness; ABS has good toughness, but ABS is prone to shrinkage and warping due to thermal stress during the molding process. Blending PETG and ABS to form an alloy can achieve both material flatness and toughness. Furthermore, the activated halloysite / calcium carbonate filler, obtained by potentiometric adsorption of acid-activated halloysite onto the surface hydroxyl groups of calcium carbonate, can improve the strength of the PETG / ABS flooring substrate, reduce warping, and mitigate defects such as cracking in the flooring. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 This is a schematic cross-sectional view of a low-warping, anti-aging PETG / ABS plastic floor product of the present invention;

[0029] In the figure, 1 is the first coating layer, 2 is the transparent film layer, 3 is the color film layer, 4 is the anti-warping and anti-aging plastic floor base material layer, 5 is the second coating layer, and 6 is the sound-absorbing layer. DETAILED DESCRIPTION

[0030] In order to better illustrate the purpose, technical solutions and effects of the present invention, the present invention will be further described below in conjunction with specific embodiments. It should be understood that specific embodiments are only used to explain the present invention and are not intended to limit the scope of protection of the present invention. The materials used in the following examples are all conventional materials sold on the market. Unless otherwise specified, the same name material sources, specifications, etc. in the following examples are all the same. Wherein PETG resin, ABS resin, POE-g-GMA and other compatibilizers, PMDA and other chain extenders, EBS and other lubricants are purchased from Henan Yinjinda New Materials Co., Ltd., China Taiwan Chi Mei Industrial Co., Ltd., Jiayirong Polymer (Shanghai) Co., Ltd., Jiangsu Hualun Chemical Co., Ltd., and Xingbeida Chemical Materials Co., Ltd.

[0031] The following experimental samples and comparative samples were prepared by the following method. The plastic flooring substrate was prepared according to the ingredients shown in Tables 1 and 2. The specific steps are as follows:

[0032] S1: The halloysite is acidified with hydrochloric acid, and then heated and activated at 60° C. for 8 h. The acidified halloysite and calcium carbonate are then added to pure water, mixed, and ultrasonically treated for 2 h. The activated halloysite / calcium carbonate composite powder is obtained by filtering and drying.

[0033] S2: Activated halloysite / calcium carbonate composite powder, PETG resin, ABS resin, compatibilizer, chain extender, lubricant, coupling agent, antioxidant and light stabilizer are placed in a high-speed mixer and stirred at a speed of 300-350 r / min for 10-20 minutes. The resulting mixture is twin-screw extruded, with the temperatures of the twin-screw zones being 200-190°C, 195-190°C, 190-180°C, 185-175°C, and 180-170°C, respectively, and the confluence core temperature being 170-160°C. The plastic floor substrate is then shaped and fixed in thickness to obtain the plastic floor substrate.

[0034] S3: Follow Figure 1 The structure of the plastic flooring is conventionally coated online with PETG color film and PETG transparent film, coated and tempered, punched and grooved, and then covered with IXPE silent pad to produce the flooring product. The first coating layer 1 and the second coating layer 5 are polyurethane-acrylic resin coatings.

[0035] As test samples, the floorings of the following embodiments and comparative examples have the same size and thickness of each layer (the thickness of the anti-warping and anti-aging plastic flooring substrate layer is 4.1 mm; the thickness of the PETG color film layer is 1 mm; and the thickness of the PETG transparent film layer is 2 mm).

[0036] Example 1 Preparation of floor substrate and floor

[0037] Table 1 Ingredients of experimental sample floor substrate (parts by weight)

[0038]

[0039] Table 2 Comparative sample floor base material ingredients (parts by weight)

[0040]

[0041] Table Notes: Comparative Sample A, 5, did not use halloysite or activated halloysite (replaced with an equal amount of calcium carbonate), and step S1 was not required in the preparation. Comparative Sample B, 6, activated halloysite was replaced with an equal amount of unactivated halloysite, and step S1 did not include the halloysite acidification and heat activation steps.

[0042] Example 2 Performance testing and comparison of floor samples

[0043] The experimental samples and comparative samples prepared in Example 1 were subjected to the following performance tests, and the test standards and methods were as follows:

[0044] Warpage test: Tested in accordance with ISO 24342. Cut the sample into a 250mm x 250mm square and place it on a flat surface. Use a feeler gauge to test each of the four corners. The maximum value among the four corners is used as the test result. Warpage must be ≤ 1.2mm.

[0045] Thermal Shrinkage Test: Tested in accordance with ISO 24342. Cut the sample into a 250mm x 250mm square. Measure and record the length and width of the sample (all four sides must be measured and recorded; length is L10 and L20, and width is W10 and W20). Place the sample in an 80°C oven for 6 hours. After 6 hours, remove it from the oven and allow it to rest in the laboratory for 3 hours. After resting, measure the length and width of the sample (length is L11 and L21, and width is W11 and W21). Calculate the length as {[(L10 + L20) / 2 - (L11 + L21) / 2] / [(L10 + L20) / 2]} × 100%; the width as {[(W10 + W20) / 2 - (W11 + W21) / 2] / [(W10 + W20) / 2]} × 100%. The maximum value is used. The thermal shrinkage requirement is ≤ 0.12%.

[0046] Wheelchair testing: Tested in accordance with EN425. Samples are slotted to create U-shaped or vertical buckles, cut into specific shapes, and then spliced. The spliced samples are fixed to the wheelchair tester and tested at different rotation speeds. The wheelchair must be tested at ≥25,000 rotations.

[0047] Thermal Expansion Test: Cut a 180mm x 1220mm sample and place it in a drying oven at 20°C. After the oven reaches the set temperature, hold it for 3 hours. Measure the length and width, recording L10 and L20 for the lengths and W10 and W20 for the widths. Next, set the oven temperature to 70°C and hold it for 3 hours. Measure the length and width, recording L11 and L21 for the lengths and W11 and W21 for the widths. Calculate the experimental data: the coefficient of thermal expansion for length is: {[(L11+L21) / 2-(L10+L20) / 2] / [(L10+L20) / 2] / 50}×100,000; the coefficient of thermal expansion for width is: {[(W11+W21) / 2-(W10+W20) / 2] / [(W10+W20) / 2] / 50}×100,000. The maximum value is selected as the test result. The thermal expansion coefficient is required to be ≤6.

[0048] Cracking test: Tested in accordance with EN13329. A 300mm x 250mm sample is placed on the base of a drop ball impact tester and secured with screws. A 2280g ball is dropped from a height of 1500mm for impact testing. No cracking is required.

[0049] Lighting test: Cut a sample of 180mm x 1220mm and place it in a lighting laboratory at a temperature of 70°C for 3 hours. No arching is required after exposure.

[0050] Elastic modulus and static flexural strength test: Tested in accordance with GB17657. Cut a 50mm x 150mm sample, measure the sample thickness, place the sample on the support roller of a universal mechanical testing machine, input the sample thickness, and then test. Requires an elastic modulus ≥ 3500MPa and a static flexural strength ≥ 18MPa.

[0051] Table 3 Performance test data of experimental samples 1 to 6

[0052]

[0053] Table 4 Performance test data of comparative samples 1 to 6

[0054]

[0055] The test results of the above samples (Tables 3 and 4) show that the flooring samples 1-6 outperformed the control samples in terms of warping resistance, wheelchair test results, thermal expansion coefficient, cracking test results, and arching. Their thermal shrinkage was lower than that of control samples 1 to 4, and their elastic modulus and static bending strength were higher than those of control sample 1 and control samples 3 to 6. The flooring samples of the present invention exhibited superior overall performance to the control samples.

[0056] Experimental analysis reveals complex factors influencing floor warping, cracking, and arching. While adjusting the compounding ratio of PETG and ABS can improve warping resistance, cracking still exists. Comparative Examples 1 and 2, while free of cracking, exhibit arching and other issues. The use of activated halloysite combined with compounding adjustments significantly contributes to addressing cracking.

[0057] The above embodiments are only some of the preferred solutions of the present invention and do not limit the present invention in any form. Without exceeding the description of the specification, based on the overall concept of the present invention, simple replacement / transformation solutions that can be obtained by those skilled in the art without creative work should still be considered within the scope of protection of the present invention.

Claims

1. A warping and aging resistant plastic floor substrate, characterized in that: The plastic floor substrate is made of the following materials in parts by weight: 40-60 parts of PETG resin, 10-30 parts of ABS resin, 2-10 parts of compatibilizer, 150-200 parts of activated halloysite / calcium carbonate composite powder, 0.4-2 parts of chain extender, 0.4-1.5 parts of coupling agent, 1-3 parts of lubricant, 0.5-1.5 parts of antioxidant, and 0.1-2 parts of light stabilizer. The activated halloysite / calcium carbonate composite powder is obtained by heating and activating acidified halloysite, then blending it with calcium carbonate in water, and then filtering and drying it after ultrasonic treatment.

2. The anti-warping and anti-aging plastic floor substrate according to claim 1, characterized in that: When preparing the activated halloysite / calcium carbonate composite powder, the mass ratio of halloysite to calcium carbonate is 1:(1-4).

3. The anti-warping and anti-aging plastic floor substrate according to claim 1, characterized in that: The compatibilizer is one or more of AS-g-MAH, SEBS-g-GMA, POE-g-GMA, and ABS-g-MAH.

4. The anti-warping and anti-aging plastic floor substrate according to claim 1, characterized in that: The chain extender is one or more of epoxies, oxazolines, isocyanates and acid anhydrides.

5. The anti-warping and anti-aging plastic floor substrate according to claim 1, characterized in that: The coupling agent is one or more of aluminate, phosphate and titanate.

6. The anti-warping and anti-aging plastic floor substrate according to claim 1, characterized in that: The lubricant is one or more of zinc stearate, erucamide, ethylene bisstearamide, and mineral white oil.

7. The anti-warping and anti-aging plastic floor substrate according to claim 1, characterized in that: The antioxidant is one or more of hindered phenols, aromatic amines, phosphites, and sulfur-containing esters.

8. The anti-warping and anti-aging plastic floor substrate according to claim 1, characterized in that: The light stabilizer is one or more of carbon black, benzophenones, acetanilides, benzotriazoles or triazines.

9. The method for preparing a warping and aging-resistant plastic floor substrate according to claim 1, characterized in that: The steps include: S1: acidifying the halloysite with hydrochloric acid, then heating and activating it at 60° C. for 8 h, then adding the acidified halloysite and calcium carbonate into pure water, mixing them, ultrasonically treating them for 2 h, filtering, and drying to obtain an activated halloysite / calcium carbonate composite powder; S2: Activated halloysite / calcium carbonate composite powder, PETG resin, ABS resin, compatibilizer, chain extender, lubricant, coupling agent, antioxidant and light stabilizer are placed in a high-speed mixer and stirred at a speed of 300-350 r / min for 10-20 minutes. The resulting mixture is twin-screw extruded, with the temperatures of the twin-screw zones being 200-190°C, 195-190°C, 190-180°C, 185-175°C, and 180-170°C, respectively, and the confluence core temperature being 170-160°C. The plastic floor substrate is then shaped and fixed in thickness to obtain the plastic floor substrate.

10. A composite flooring made from the anti-warping and anti-aging plastic flooring substrate according to any one of claims 1 to 8 or the anti-warping and anti-aging plastic flooring substrate prepared by the preparation method according to claim 9, characterized in that: The composite floor is made of six layers of materials, and the six layers are arranged in the following order: a first coating layer, a transparent film layer, a color film layer, an anti-warping and anti-aging plastic floor base material layer, a second coating layer, and a sound-absorbing layer.

11. The composite flooring according to claim 10, characterized in that The color film layer and the transparent film layer are both made of PETG.

12. The composite flooring according to claim 10, wherein: The thickness of the anti-warping and anti-aging plastic floor substrate layer is 4.1-4.2 mm.

13. The composite flooring according to claim 10, wherein: The color film layer has a thickness of 1 mm.

14. The composite flooring according to claim 10, wherein: The thickness of the transparent film layer is 2-3 mm.

15. The composite flooring according to claim 10, wherein: The first coating layer and the second coating layer are made of polyurethane-acrylic resin coating; the sound-absorbing layer is selected from radiation cross-linked polyethylene sound-absorbing pad or radiation cross-linked polypropylene sound-absorbing pad.

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