Macromolecular polymerized ceramic sculpture clay and preparation method thereof

Abstract

The invention belongs to the field of high-molecular polymerization ceramic clay, and particularly relates to high-molecular polymerization ceramic sculpture clay which is prepared from the following raw materials in parts by weight: 10-30 parts of polyvinyl chloride paste resin, 40-80 parts of a plasticizer, 10-30 parts of a filler, 1-5 parts of a stabilizer, 0.5-2 parts of an anti-sticking agent, 0.1-0.5 part of an anti-aging agent and 0.1-0.5 part of an auxiliary agent. According to the high-molecular polymerized ceramic sculpture clay and the preparation method thereof, the problems that in the prior art, environment-friendly safety, using hand feeling and plasticity and performance after drying are difficult to consider into consideration, and the requirements of being non-toxic, environment-friendly, fine and smooth in hand feeling, high in plasticity, free of shrinkage and deformation after drying and ceramic in texture cannot be met at the same time are solved.

Description

Technical Field

[0001] This invention relates to the field of polymeric ceramic clay, and more particularly to a polymeric ceramic clay and its preparation method. Background Technology

[0002] With the development of the social economy and the improvement of people's living standards, the DIY handicraft product market is showing a rapid development trend. From children's beginner-level clay, rice clay, and super light clay to super clay and stone clay used by art professionals, the variety of DIY products is becoming increasingly rich, meeting the creative needs of consumers of different ages and levels.

[0003] Currently, commercially available craft materials mainly fall into the following categories and their defects: 1. Modeling clay and rice clay: Modeling clay and rice clay are the most basic children's craft materials, mainly made from flour, water, and food coloring. Although these products are relatively safe and inexpensive, they have obvious defects: they lack the ability to retain their shape, and the finished products are prone to cracking and deformation during the drying process; they cannot be preserved for a long time, usually cracking or moldy after a few days; the colors are limited, and the plasticity is poor, making them only suitable for children's basic early education and unable to meet the needs of fine modeling. 2. Super light clay: Super light clay is a popular lightweight craft material in recent years, mainly composed of foaming powder, water, and adhesives. Its advantages are its lightweight texture and rich colors. However, its defects are also obvious: after drying, the texture is similar to foam, with low density and poor strength, lacking the texture of ceramics; the surface of the finished product is rough, making it impossible to carve finely; it is prone to absorbing moisture, deforming, yellowing, and aging after long-term storage, and has no permanent preservation value. 3. Stone-plastic clay: Stone-plastic clay uses natural stone powder as its main raw material. After drying, it becomes hard and has a stone-like texture, and can be preserved permanently. However, its drawbacks are: rough texture, poor ductility, and easy cracking during shaping; it requires adding water for kneading, making it inconvenient to handle; drying time is long, 24-48 hours, resulting in low efficiency; it has a pungent odor, and some products contain irritating ingredients, making it unsuitable for children. 4. Super clay (also known as American clay): Super clay is a professional-grade craft material, based on polymer resin, with excellent plasticity and detail expression. However, it is expensive, making it unaffordable for most consumers; it has a hard texture, requiring considerable force to knead, making it unsuitable for teenagers and women; it requires specific temperature baking for curing, making it difficult to work with. 5. Traditional polymer clay: Traditional polymer clay, also known as polymer clay, is typically made from polyvinyl chloride resin powder, liquid paraffin oil, phthalate plasticizers, and other additives.

[0004] While these products possess a degree of plasticity and preservation value, they suffer from the following prominent problems: Poor environmental friendliness: Traditional polymer clay often uses phthalate plasticizers (such as DBP and DOP), which have been proven by numerous studies to have endocrine-disrupting effects. The EU, the US, and other countries and regions have strictly restricted their use in toys and children's products. Poor stability: Traditional formulas often use heavy metal stabilizers such as lead and cadmium salts. These substances are not only harmful to the human body but also cause the release of toxic fumes during baking and use. Sticky feel: Traditional polymer clay tends to stick to hands and tools during modeling, affecting the user experience and the precision of the finished product. Oily exudation after drying: Some traditional products develop an oily substance on the surface after baking and curing, damaging the appearance of the work and easily attracting dust. Prone to aging and hardening: Traditional polymer clay is prone to aging and hardening over time when stored in sealed containers, making it unsuitable for long-term storage.

[0005] Existing technologies have addressed the shortcomings of traditional polymer clay, and some improvements have been reported. For example, a patent document discloses a method for preparing polymer clay using polyvinyl chloride paste resin as a base material, with the addition of liquid paraffin oil, phthalate plasticizers, and lead salt stabilizers. However, as mentioned earlier, this type of technology still has shortcomings in terms of environmental protection and performance. Other literature has attempted to use citrate-based environmentally friendly plasticizers to replace phthalates, but this has not solved the problems of heavy metals in stabilizers and the issues of non-sticking and anti-aging in the product. The product still suffers from defects such as oil seepage during baking and easy aging and hardening.

[0006] In summary, existing handcrafted materials struggle to balance environmental safety, tactile feel, plasticity, and preservation performance. There is an urgent need to develop a high-polymer ceramic clay that is environmentally friendly and non-toxic, has a delicate feel, strong plasticity, does not deform after drying, possesses a ceramic-like texture, and can be preserved for a long time, in order to meet the growing market demand, especially the needs of teenagers and adult handcraft enthusiasts. Summary of the Invention

[0007] The purpose of this invention is to provide a polymeric ceramic clay and its preparation method, which solves the problem that existing hand-shaped materials are difficult to balance in terms of environmental safety, feel and plasticity, and performance after drying. They cannot simultaneously meet the requirements of being non-toxic and environmentally friendly, having a delicate feel, strong plasticity, and not shrinking or deforming after drying, and having a ceramic texture.

[0008] To solve the above-mentioned technical problems, the polymeric ceramic clay and its preparation method provided by this invention are achieved as follows: A polymeric ceramic clay is prepared from the following raw materials in parts by weight: 10-30 parts of polyvinyl chloride paste resin, 40-80 parts of plasticizer, 10-30 parts of filler, 1-5 parts of stabilizer, 0.5-2 parts of anti-sticking agent, 0.1-0.5 parts of anti-aging agent, and 0.1-0.5 parts of additives.

[0009] Optionally, the plasticizer is an environmentally friendly plasticizer selected from one or more of ATBC, EGDA, TOTM, TXIB, and DINCH.

[0010] ATBC is tributyl acetyl citrate, EGDA is ethylene glycol diacetate, TOTM is trioctyl trimellitate, TXIB is 2,2,4-trimethyl-1,3-pentanediol diisobutyrate, and DINCH is diisononyl cyclohexane-1,2-dicarboxylate.

[0011] Optionally, the filler is selected from one or more of stone powder, kaolin, gypsum powder, and glass microspheres.

[0012] Optionally, the stabilizer is an environmentally friendly solution-type composite calcium-zinc stabilizer, selected from one or more of the following: calcium zinc isooctanoate soap, calcium zinc epoxy oleate, 8505-1 non-toxic calcium / zinc liquid composite stabilizer, SPJ-501, and SPJ-502.

[0013] Optionally, the anti-sticking agent is selected from one or more of Licolub™ H 12, Licowax™ PE 520, oxidized polyethylene wax, polyethylene wax, and calcium stearate.

[0014] Optionally, the antioxidant is MB807 antioxidant; the additive is a whitening agent selected from one or more of the following: fluorescent whitening agent CBS-127, fluorescent whitening agent CF-127, fluorescent whitening agent 378, 2,5-bis(5-tert-butyl-2-benzoxyl)thiophene, 2,2-(4,4'-stilbeneyl)bisbenzoxazole, and 1,4-bis(2-cyanostyl)benzene.

[0015] Optionally, the ceramic clay, after being dried at 120℃ for 1 hour, has a shrinkage ratio ≤0.03 and a shelf life ≥30 months.

[0016] A method for preparing polymeric ceramic clay includes the following steps: ① Preparing polyvinyl chloride (PVC) plasticizer paste: PVC paste resin and environmentally friendly plasticizer are added to a reactor, stirred evenly, and allowed to stand for aging to obtain a homogeneous PVC plasticizer paste; ② Preparing polymeric ceramic clay: PVC plasticizer paste, filler, stabilizer, anti-sticking agent, anti-aging agent, and additives are added to a mixing pot, heated and stirred. When the temperature reaches the set temperature, stirring is stopped, the material is discharged while hot, and allowed to cool to room temperature to obtain the final product.

[0017] Optionally, the settling time in step ① is 10-14 hours; the set temperature in step ② is 95-105℃.

[0018] Application of polymeric ceramic clay in the preparation of handcrafted modeling materials.

[0019] Compared with the prior art, the present invention has the following beneficial effects: 1. Environmentally friendly and safe, non-toxic and harmless. This invention uses environmentally friendly plasticizers (such as ATBC and DINCH) to replace traditional phthalate plasticizers, avoiding the risk of interference with the human endocrine system; it also uses environmentally friendly solution-type composite calcium-zinc stabilizers to replace traditional lead and cadmium salt stabilizers, completely eliminating the hidden dangers of heavy metal toxicity. Test Example 4 shows that the content of migratable heavy metals in the product of this invention is far below the limits of GB6675.4-2014 "Toy Safety" standard, with lead content <2 mg / kg (standard limit ≤90 mg / kg) and cadmium content <1 mg / kg (standard limit ≤75 mg / kg), meeting the stringent environmental requirements of the EU, the US, and other international markets for toys and children's products. The product emits no odor or toxic fumes during baking and use, making it safe for use in craft projects by teenagers and adults.

[0020] 2. It has a delicate feel and is highly malleable. This invention utilizes the thorough aging of polyvinyl chloride (PVC) paste resin and environmentally friendly plasticizers to form a homogeneous and stable plasticized paste system. The PVC reaches a molecular-level dissolved state, endowing the material with excellent ductility and plasticity. Test Example 5, a tactile evaluation, shows that the product of this invention achieves a plasticity score of 9.2 out of 10 and a tactile smoothness score of 9.0, significantly superior to traditional stone-plastic clay and ultra-lightweight clay. Users experience a comfortable and effortless feel during the modeling process, easily achieving fine carving and complex shapes, meeting the needs of beginners to professional artists.

[0021] 3. Oil-resistant and non-stick, providing a superior user experience. This invention effectively solves the problem of traditional polymer clay sticking to hands and tools during the modeling process by adding specific anti-sticking agents (such as Licolub™ H 12, oxidized polyethylene wax, etc.). Test Example 6 shows that after adding the anti-sticking agent, the product's tackiness reaches level 5 (level 1 is the stickiest, level 5 is the least sticky), and there is no oily exudation after drying; while the control product without the anti-sticking agent is noticeably sticky, and an oily exudate appears after baking. The excellent anti-sticking properties make the creative process smoother, resulting in a smooth surface and strong detail in the finished product.

[0022] 4. It does not shrink or deform after drying and has a ceramic texture. The product of this invention can be fully cured by baking at 120℃ for 1 hour, and the shrinkage ratio after drying is only 0.019-0.025 (Example 1), which is far lower than the shrinkage rate of traditional stone-plastic clay and ultra-light clay (usually reaching 0.05-0.10). The artwork maintains dimensional stability during the drying process, without deformation or cracking, with a smooth and delicate surface, hard texture, and a realistic ceramic feel, possessing permanent preservation value. This characteristic makes the product of this invention particularly suitable for creating high-precision works such as simulated flowers, dolls, and ornaments.

[0023] 5. Excellent aging resistance and long shelf life. This invention incorporates MB807 antioxidant, effectively delaying the aging and hardening of the product during storage and use. Test Example 3 shows that after aging at 80℃ for 7 days, the tensile strength retention rate of the product of this invention is over 95%, with no significant change in appearance; while the control product (unaged) retains only 68% of its strength after aging, and exhibits yellowing and embrittlement. The shelf life of the product of this invention reaches 36 months (Test Example 1), far exceeding the 24 months of traditional polymer clay, facilitating commercial production and distribution.

[0024] 6. The process is simple and suitable for industrial production. The preparation method of this invention requires only two steps: preparation and aging of polyvinyl chloride plasticized paste, and heating, mixing, and molding. The process is simple, requires minimal equipment, and eliminates the need for complex reactions and special conditions. The formulations at each endpoint in the examples exhibit good processing performance, uniform mixing, and smooth discharge, making them suitable for large-scale continuous production. Although the aging step adds 12 hours of settling time, it allows for centralized batch processing without affecting production efficiency and is crucial for ensuring product uniformity and stability. Detailed Implementation

[0025] To make the objectives, technical solutions, and advantages of this invention clearer, the following embodiments provide a more detailed description of the invention. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the scope of the invention.

[0026] Unless otherwise specified, the experimental methods used in the following examples are conventional methods, performed according to the techniques or conditions described in the literature in this field or according to the product instructions. Unless otherwise specified, the materials and reagents used in the following examples are commercially available.

[0027] Example 1 Raw material formula (parts by weight): Polyvinyl chloride paste resin: 15 parts Environmentally friendly plasticizer (ATBC): 60 parts Filler: 10 parts stone powder, 10.7 parts gypsum powder (total 20.7 parts) Stabilizer: 3 parts of 8505-1 non-toxic calcium / zinc liquid composite stabilizer Anti-sticking agent: 1 part Licolub™ H 12 Anti-aging agent: MB807 0.2 parts Brightening agent: 0.1 parts of fluorescent whitening agent CBS-127 Preparation methods: ① Preparation of polyvinyl chloride plasticized paste: Add polyvinyl chloride paste resin and environmentally friendly plasticizer ATBC to a reactor, stir evenly, and let stand for 12 hours to obtain a homogeneous polyvinyl chloride plasticized paste. ② Preparation of polymeric ceramic clay: Add polyvinyl chloride plasticized paste, filler, stabilizer, anti-sticking agent, anti-aging agent, and whitening agent to a mixing pot, set the temperature to 100℃, stir, and when the temperature reaches the set temperature, stop stirring, discharge the material while hot, and let it stand to room temperature for later use.

[0028] Example 2 Raw material formula (parts by weight): Polyvinyl chloride paste resin: 25 parts Environmentally friendly plasticizer (DINCH): 55 parts Filler: 10 parts kaolin, 4.1 parts gypsum powder (total 14.1 parts) Stabilizer: 4 parts calcium zinc epoxy oleate Anti-sticking agent: 1.5 parts oxidized polyethylene wax Anti-aging agent: MB807 0.2 parts Brightening agent: 0.2 parts of fluorescent whitening agent CF-127 The preparation method is the same as in Example 1.

[0029] Example 3 Raw material formula (parts by weight): Polyvinyl chloride paste resin: 20 parts Environmentally friendly plasticizer (TOTM): 56 parts Filler: 10 parts glass microspheres, 10.5 parts stone powder (total 20.5 parts) Stabilizer: 2 parts calcium zinc isooctanoate soap Anti-sticking agent: 1 part calcium stearate Anti-aging agent: MB807 0.3 parts Whitening agent: 0.2 parts of 2,5-bis(5-tert-butyl-2-benzoxyl)thiophene The preparation method is the same as in Example 1.

[0030] Example 4 (using different plasticizers) Raw material formula (parts by weight): Polyvinyl chloride paste resin: 18 parts Environmentally friendly plasticizer (EGDA): 70 parts Filler: 15 parts stone powder, 5 parts gypsum powder (total 20 parts) Stabilizer: SPJ-501 3.5 parts Anti-sticking agent: Licowax™ PE 520 1.2 parts Anti-aging agent: MB807 0.25 parts Brightening agent: 0.15 parts of fluorescent whitening agent 378 The preparation method is the same as in Example 1.

[0031] Example 5 Raw material formula (parts by weight): Polyvinyl chloride paste resin: 10 parts Environmentally friendly plasticizer (ATBC): 40 parts Filler: 5 parts stone powder, 5 parts gypsum powder Stabilizer (8505-1 Non-toxic Calcium / Zinc Liquid Composite Stabilizer): 1 part Anti-adhesive (Licolub™ H 12): 0.5 parts Anti-aging agent (MB807): 0.1 parts Brightening agent (fluorescent brightener CBS-127): 0.1 parts Preparation methods: ① Preparation of polyvinyl chloride plasticized paste: Add polyvinyl chloride paste resin and environmentally friendly plasticizer ATBC to a reactor, stir evenly, and let stand for 12 hours to obtain a homogeneous polyvinyl chloride plasticized paste. ② Preparation of polymeric ceramic clay: Add polyvinyl chloride plasticized paste, filler, stabilizer, anti-sticking agent, anti-aging agent, and whitening agent to a mixing pot, set the temperature to 100℃, stir, and when the temperature reaches the set temperature, stop stirring, discharge the material while hot, and let it stand to room temperature for later use.

[0032] Example 6 Raw material formula (parts by weight): Polyvinyl chloride paste resin: 30 parts Environmentally friendly plasticizer (DINCH): 80 parts Filler: 15 parts kaolin, 15 parts gypsum powder Stabilizer (calcium zinc epoxide): 5 parts Anti-sticking agent (oxidized polyethylene wax): 2 parts Anti-aging agent (MB807): 0.5 parts Brightening agent (fluorescent brightener CF-127): 0.5 parts The preparation method is the same as in Example 5.

[0033] Example 7 Raw material formula (parts by weight): Polyvinyl chloride paste resin: 10 parts Environmentally friendly plasticizer (TOTM): 60 parts Filler: 10 parts glass microspheres, 10 parts stone powder Stabilizer (calcium zinc isooctanoate soap): 3 parts Anti-sticking agent (calcium stearate): 1 part Anti-aging agent (MB807): 0.3 parts Whitening agent (2,5-bis(5-tert-butyl-2-benzothiophene): 0.3 parts The preparation method is the same as in Example 5.

[0034] Example 8 Raw material formula (parts by weight): Polyvinyl chloride paste resin: 30 parts Environmentally friendly plasticizer (EGDA): 60 parts Filler: 10 parts stone powder, 10 parts gypsum powder (total 20 parts) Stabilizer (SPJ-501): 3 parts Anti-sticking agent (Licowax™ PE 520): 1 part Anti-aging agent (MB807): 0.3 parts Brightening agent (fluorescent brightener 378): 0.3 parts The preparation method is the same as in Example 5.

[0035] Example 9 Raw material formula (parts by weight): Polyvinyl chloride paste resin: 20 parts Environmentally friendly plasticizer (ATBC): 40 parts Filler: 10 parts stone powder, 10 parts gypsum powder (total 20 parts) Stabilizer (8505-1): 3 parts Anti-adhesive (Licolub™ H 12): 1 part Anti-aging agent (MB807): 0.3 parts Brightening agent (fluorescent brightener CBS-127): 0.3 parts The preparation method is the same as in Example 5.

[0036] Example 10 Raw material formula (parts by weight): Polyvinyl chloride paste resin: 20 parts Environmentally friendly plasticizer (DINCH): 80 parts Filler: 10 parts kaolin, 10 parts gypsum powder (total 20 parts) Stabilizer (calcium zinc epoxide): 3 parts Anti-sticking agent (oxidized polyethylene wax): 1 part Anti-aging agent (MB807): 0.3 parts Brightening agent (fluorescent brightener CF-127): 0.3 parts The preparation method is the same as in Example 5.

[0037] Example 11 Raw material formula (parts by weight): Polyvinyl chloride paste resin: 20 parts Environmentally friendly plasticizer (TOTM): 60 parts Filler: 5 parts stone powder, 5 parts gypsum powder (total 10 parts) Stabilizer (calcium zinc isooctanoate soap): 3 parts Anti-sticking agent (calcium stearate): 1 part Anti-aging agent (MB807): 0.3 parts Whitening agent (2,5-bis(5-tert-butyl-2-benzothiophene): 0.3 parts The preparation method is the same as in Example 5.

[0038] Example 12 Raw material formula (parts by weight): Polyvinyl chloride paste resin: 20 parts Environmentally friendly plasticizer (EGDA): 60 parts Filler: 15 parts glass microspheres, 15 parts stone powder (total 30 parts) Stabilizer (SPJ-501): 3 parts Anti-sticking agent (Licowax™ PE 520): 1 part Anti-aging agent (MB807): 0.3 parts Brightening agent (fluorescent brightener 378): 0.3 parts The preparation method is the same as in Example 5.

[0039] Example 13 Raw material formula (parts by weight): Polyvinyl chloride paste resin: 20 parts Environmentally friendly plasticizer (ATBC): 60 parts Filler: 10 parts stone powder, 10 parts gypsum powder (total 20 parts) Stabilizer (8505-1): 1 part Anti-adhesive (Licolub™ H 12): 1 part Anti-aging agent (MB807): 0.3 parts Brightening agent (fluorescent brightener CBS-127): 0.3 parts The preparation method is the same as in Example 5.

[0040] Example 14 Raw material formula (parts by weight): Polyvinyl chloride paste resin: 20 parts Environmentally friendly plasticizer (DINCH): 60 parts Filler: 10 parts kaolin, 10 parts gypsum powder (total 20 parts) Stabilizer (calcium zinc epoxide): 5 parts Anti-sticking agent (oxidized polyethylene wax): 1 part Anti-aging agent (MB807): 0.3 parts Brightening agent (fluorescent brightener CF-127): 0.3 parts The preparation method is the same as in Example 5.

[0041] Example 15 Raw material formula (parts by weight): Polyvinyl chloride paste resin: 20 parts Environmentally friendly plasticizer (TOTM): 60 parts Filler: 10 parts glass microspheres, 10 parts stone powder (total 20 parts) Stabilizer (calcium zinc isooctanoate soap): 3 parts Anti-sticking agent (calcium stearate): 0.5 parts Anti-aging agent (MB807): 0.3 parts Whitening agent (2,5-bis(5-tert-butyl-2-benzothiophene): 0.3 parts The preparation method is the same as in Example 5.

[0042] Example 16 Raw material formula (parts by weight): Polyvinyl chloride paste resin: 20 parts Environmentally friendly plasticizer (EGDA): 60 parts Filler: 10 parts stone powder, 10 parts gypsum powder (total 20 parts) Stabilizer (SPJ-501): 3 parts Anti-sticking agent (Licowax™ PE 520): 2 parts Anti-aging agent (MB807): 0.3 parts (center) Brightening agent (fluorescent brightener 378): 0.3 parts The preparation method is the same as in Example 5.

[0043] II. Comparison Example Comparative Example 1 (using conventional lead salt stabilizers) Raw material formulation: Same as in Example 1, but the stabilizer is replaced with tribasic lead sulfate (3 parts), and other components remain unchanged.

[0044] The preparation method is the same as in Example 1.

[0045] Compare with Example 2 (without anti-sticking agent) Raw material formulation: Same as in Example 1, but without the addition of anti-sticking agent.

[0046] The preparation method is the same as in Example 1.

[0047] Comparison Example 3 (no whitening agent added) Raw material formulation: Same as in Example 1, but without the addition of whitening agent.

[0048] The preparation method is the same as in Example 1.

[0049] Compare with Example 4 (without aging treatment) Raw material formulation: Same as in Example 1, but when preparing polyvinyl chloride plasticized paste, after stirring evenly, no aging is performed, and step ② is carried out directly.

[0050] Preparation method: ① Add polyvinyl chloride paste resin and environmentally friendly plasticizer to the reactor and stir evenly (without aging). ② Add the mixture, filler, stabilizer, anti-sticking agent, anti-aging agent and whitening agent to the mixing pot, set the temperature to 100℃, stir, and when the temperature rises to the set temperature, stop stirring, discharge the material while hot, and let it stand to room temperature for later use.

[0051] III. Experimental Examples Test Example 1: Basic Physical Performance Test According to GB 6675.1-2014 "Toy Safety Part 1: Basic Specifications" and the corresponding test methods, the ceramic clay prepared in Examples 1-4 and Control Examples 1-4 was tested for performance. The results are shown in Table 1.

[0052] As shown in Table 1, Examples 1-4 all exhibit excellent physical properties, good whiteness, low shrinkage, and long shelf life. Comparative Example 1, using a lead salt stabilizer, resulted in a slightly yellowish product, a shorter shelf life, and environmental risks. Comparative Example 2, lacking an anti-sticking agent, resulted in a sticky surface, prolonged drying time, and a shorter shelf life. Comparative Example 3, lacking a whitening agent, resulted in reduced whiteness. Comparative Example 4, without aging treatment, resulted in poor product uniformity, a grainy texture, increased shrinkage, and a shorter shelf life.

[0053] Test Example 2: Mechanical Property Testing In accordance with GB / T 1040-2006 "Determination of Tensile Properties of Plastics" and GB / T 2411-2008 "Shore Hardness Test Method for Plastics", the tensile strength and Shore hardness of the dried samples of Examples 1-4 and Control Examples 1-4 were tested, and the results are shown in Table 2.

[0054] The results show that the product of the present invention has high tensile strength and hardness, and a large elongation at break, indicating good toughness and strength. The mechanical properties of Comparative Examples 1, 2, and 4 all decreased, proving that stabilizers, anti-sticking agents, and aging processes have a significant impact on the mechanical properties of the product.

[0055] Test Example 3: Aging Resistance Test The samples of Examples 1-4 and Control Examples 1-4 were aged in an 80°C constant temperature oven for 7 days. After being taken out, the appearance changes were observed and the tensile strength retention rate after aging was tested. The results are shown in Table 3.

[0056] The products of this invention exhibit good aging resistance, maintaining good appearance and strength after aging. Comparative Example 1, due to the use of a lead salt stabilizer, has slightly poorer aging resistance; Comparative Example 2, lacking an anti-sticking agent, results in a sticky surface after aging; Comparative Example 4, without aging, shows the most significant performance degradation after aging.

[0057] Test Example 4: Environmental Performance Test Referring to GB 6675.4-2014 "Toy Safety Part 4: Migration of Certain Elements", the content of migratable heavy metals in the samples of Example 1 and Control Example 1 was tested, and the results are shown in Table 4.

[0058] The results show that Example 1 of the present invention uses an environmentally friendly calcium-zinc stabilizer, and the content of migratable heavy metals is far below the national standard limit; while Example 1 of the control uses a lead salt stabilizer, and the lead content is significantly higher than the standard (exceeding the toy safety limit of 90 mg / kg), posing a safety hazard.

[0059] Experimental Example 5: Evaluation of Form Performance and Hand Feel Ten craft enthusiasts (5 teenagers and 5 adults) were invited to conduct blind tests on the samples of Examples 1-4 and Control Examples 1-4 to evaluate their plasticity, hand feel, and texture after drying. The scores were based on a 10-point scale, and the average value was taken. The results are shown in Table 5.

[0060] The products of this invention received high ratings in terms of plasticity, smoothness of hand feel, and texture after drying, demonstrating excellent overall performance. Comparative Example 2, lacking an anti-sticking agent, had a sticky feel and received the lowest score; Comparative Example 1 also received a low score due to odor and color issues caused by the lead salt stabilizer.

[0061] Experimental Example 6: Comparison of the effects of different anti-adhesion agents Based on Example 1, samples were prepared using different anti-sticking agents, and their anti-sticking effect (finger tack, 1-5 levels, level 1 being the stickiest and level 5 being the least sticky) and oil exudation after drying were tested. The results are shown in Table 6.

[0062] The results showed that Licolub™ H 12 had the best anti-sticking effect, followed by calcium stearate and oxidized polyethylene wax, all of which effectively prevented oiling and sticking.

[0063] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A polymeric ceramic clay, characterized in that, It is prepared from the following raw materials in parts by weight: 10-30 parts polyvinyl chloride paste resin, 40-80 parts plasticizer, 10-30 parts filler, 1-5 parts stabilizer, 0.5-2 parts anti-sticking agent, 0.1-0.5 parts antioxidant, and 0.1-0.5 parts additives.

2. The polymeric ceramic clay according to claim 1, characterized in that, The plasticizer is an environmentally friendly plasticizer, selected from one or more of ATBC, EGDA, TOTM, TXIB, and DINCH.

3. The polymeric ceramic clay according to claim 1, characterized in that, The filler is selected from one or more of stone powder, kaolin, gypsum powder, and glass microspheres.

4. The polymeric ceramic clay according to claim 1, characterized in that, The stabilizer is an environmentally friendly solution-type composite calcium-zinc stabilizer, selected from one or more of the following: calcium zinc isooctanoate soap, calcium zinc epoxy oleate, 8505-1 non-toxic calcium / zinc liquid composite stabilizer, SPJ-501, and SPJ-502.

5. The polymeric ceramic clay according to claim 1, characterized in that, The anti-sticking agent is selected from one or more of Licolub™ H 12, Licowax™ PE 520, oxidized polyethylene wax, polyethylene wax, and calcium stearate.

6. The polymeric ceramic clay according to claim 1, characterized in that, The antioxidant is MB807 antioxidant; the additive is a whitening agent selected from one or more of the following: fluorescent whitening agent CBS-127, fluorescent whitening agent CF-127, fluorescent whitening agent 378, 2,5-bis(5-tert-butyl-2-benzoxyl)thiophene, 2,2-(4,4'-stilbeneyl)bisbenzoxazole, and 1,4-bis(2-cyanostyl)benzene.

7. The polymeric ceramic clay according to any one of claims 1-6, characterized in that, The ceramic clay, after being dried at 120℃ for 1 hour, has a shrinkage ratio of ≤0.03 and a shelf life of ≥30 months.

8. A method for preparing polymeric ceramic clay as described in any one of claims 1-7, characterized in that, Includes the following steps: ① Preparation of polyvinyl chloride plasticized paste: Add polyvinyl chloride paste resin and environmentally friendly plasticizer to a reactor, stir evenly, and let stand for aging to obtain a homogeneous polyvinyl chloride plasticized paste; ② Preparation of polymeric ceramic clay: Add polyvinyl chloride plasticized paste, filler, stabilizer, anti-sticking agent, anti-aging agent and additives to a mixing pot, heat and stir, and when the temperature rises to the set temperature, stop stirring, discharge the material while hot, and let it stand to room temperature to obtain the final product.

9. The preparation method according to claim 8, characterized in that, The settling time in step ① is 10-14 hours; the set temperature in step ② is 95-105℃.

10. The application of the polymeric ceramic clay according to any one of claims 1-6 in the preparation of handcrafted modeling materials.

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