High ultra-soft, high-transparency and high-deformation-resistance TPE (thermoplastic elastomer) particles as well as preparation method and application thereof

Abstract

The invention discloses a highly ultra-soft, highly transparent and highly deformation-resistant TPE (thermoplastic elastomer) particle, and belongs to the technical field of high polymer materials. Comprising the following materials: matrix rubber, triple hydrogenated white oil, a release agent, a main antioxidant, an auxiliary antioxidant and a light stabilizer. The water-based surface modifier A is used for preventing the surface of the TPE particles from sticking and is used during pelletizing, and the surface modifier B is used during drying. The TPE particles provided by the invention have the characteristics of high super-softness, high transparency and high deformation resistance.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer materials, and in particular to a super-soft, highly transparent, and highly deformation-resistant TPE particle, and a preparation method and application thereof. Background Art

[0002] Existing ultra-soft TPE materials (hardness 0V-15V) have the following technical bottlenecks in achieving high transparency, high oil filling rate and deformation resistance: Extraction problem: In highly oil-filled systems (white oil content >80%), the SEBS / SEPS molecular chain's insufficient oil-binding capacity leads to plasticizer migration and precipitation ("oil exudation"), resulting in oil stains on the surface ("The molecular weight of the (hard segment) base rubber in special-grade ultra-soft, ultra-transparent TPE determines the addition ratio of hydrogenated white oil in the (soft segment) and the material's oil absorption (binding) properties"); Transparency flaws: The refractive index of ordinary mineral oil (1.46-1.48) does not match the rubber matrix (SEBS refractive index 1.51), and insufficient multiple hydrogenation results in residual fluorescent impurities and a transmittance of less than 85% ("Using high-quality oils that have been hydrogenated multiple times can achieve better transparency"); Processing disorders: Ultra-soft TPE (die head temperature needs to be ≤90°C) will experience severe die blocking in traditional underwater pelletizers (die head temperature 130-170°C) ("die hole blocking or clogging at low temperatures"); Highly sticky particles stick together and clump together during dehydration ("capacity clumping and blade connection, dehydrator has difficulty in dehydration"); Storage of agglomerates: The oil-filled particles agglomerate into clumps during transportation due to oil migration ("the greater the proportion of oil, the greater the possibility of precipitation (oil spitting), which causes the transparent particles to agglomerate").

[0003] Limitations of existing solutions: Increasing the molecular weight of SEBS can improve oil lock, but at the expense of transparency (increase in crystalline phase); Although adding silicone oil additives can prevent sticking, it will cause the transmittance to drop by more than 10% ("improper use of additives will aggravate surface oiling"). Summary of the Invention

[0004] In view of the above-mentioned technical deficiencies, the purpose of the present invention is to provide a super-soft, highly transparent and highly deformation-resistant TPE particle and a preparation method thereof to solve the problems mentioned in the background technology.

[0005] To solve the above technical problems, the present invention adopts the following technical solution: The present invention provides a highly soft, highly transparent, and highly deformation-resistant TPE particle, comprising the following materials: a base rubber, tertiary hydrogenated white oil, a release agent, a primary antioxidant, a secondary antioxidant, and a light stabilizer; and also comprising an aqueous surface modifier A for preventing the surface of the TPE particles from sticking and used during pelletizing, and a surface modifier B for use during drying.

[0006] Preferably, the weight ratio of the materials is: base rubber 7-9%, tertiary hydrogenated white oil 80-91.5%, release agent 0.05-0.1%, primary antioxidant 0.3-0.4%, auxiliary antioxidant 0.2-0.3%, light stabilizer 0.1-0.2%; the weight ratio of surface modifier A to water is 1:20, and 1-2 kg of surface modifier B is added to every 100 g of TPE particles.

[0007] Preferably, the weight ratio of the materials is: base rubber 9-10%, tertiary hydrogenated white oil 80-90%, release agent 0.05-0.1%, primary antioxidant 0.2-0.4%, auxiliary antioxidant 0.3-0.4%, light stabilizer 0.1-0.2%; the weight ratio of surface modifier A to water is 1:20, and 1-2 kg of surface modifier B is added to every 100 g of TPE particles.

[0008] Preferably, the weight ratio of the materials is: base rubber 10-12%, tertiary hydrogenated white oil 80-88%, release agent 0.05-0.1%, primary antioxidant 0.2-0.4%, auxiliary antioxidant 0.2-0.4%, light stabilizer 0.1-0.2%; the weight ratio of surface modifier A to water is 1:20, and 1-2 kg of surface modifier B is added to every 100 g of TPE particles.

[0009] Preferably, the base rubber is a mixture of SEPTOP and SEPTON, and the weight ratio of SEPTOP to SEPTON is 7:3; the tertiary hydrogenated white oil is prepared by hydrogenating two or three of hydrogenated mineral oil, vegetable butter, and cosmetic-grade white mineral oil; the release agent is synthetic polyester wax, the primary antioxidant is a hindered phenol antioxidant, the secondary antioxidant is a liquid aromatic amine antioxidant, and the light stabilizer is a hindered amine light stabilizer; the surface modifier A is prepared by emulsifying and dispersing 95% of a polysiloxane-polyalkoxy ether copolymer emulsion with 5% of a nano-degreasing emulsifier; and the surface modifier B is a modified silicone oil containing a high phenyl functional group.

[0010] Preferably, the base rubber is a mixture of SEPTOP and SEPTON, and the weight ratio of SEPTOP to SEPTON is 8:2; the tertiary hydrogenated white oil is prepared by hydrogenating two or three of hydrogenated mineral oil, vegetable butter, and cosmetic-grade white mineral oil; the release agent is synthetic polyester wax, the primary antioxidant is a liquid hindered phenol antioxidant, the secondary antioxidant is a liquid aromatic amine antioxidant, and the light stabilizer is a hindered amine light stabilizer; the surface modifier A is prepared by emulsifying and dispersing 95% of a polysiloxane-polyalkoxy ether copolymer emulsion with 5% of a nano-degreasing emulsifier; and the surface modifier B is a modified silicone oil containing a high phenyl functional group.

[0011] Preferably, the base rubber is KRATONG; the tertiary hydrogenated white oil includes two or three of hydrogenated mineral oil, vegetable butter, and cosmetic-grade white mineral oil, which are prepared by hydrogenation treatment; the release agent is polyester wax; the primary antioxidant is a hindered phenol-type antioxidant; the auxiliary antioxidant is antioxidant 1330; the light stabilizer is a hindered amine light stabilizer; the surface modifier A is 95% polysiloxane-polyalkoxy ether copolymer emulsion, which is emulsified and dispersed with 5% of a nano-oil removal emulsifier; and the surface modifier B is a modified silicone oil containing a high phenyl functional group.

[0012] The present invention provides a method for preparing ultra-soft, highly transparent, and highly deformation-resistant TPE particles, comprising the following steps: (1) Mixing: Mix the base rubber and tertiary hydrogenated white oil at 160°C for 20-40 minutes; (2) Adding additives: Add release agent, primary antioxidant, auxiliary antioxidant and light stabilizer in sequence and continue mixing for 10-15 minutes; (3) Low temperature underwater pelletizing: The melt was extruded through a GTE-65B parallel co-rotating twin-screw extruder with a screw length-diameter ratio of 48:1; Barrel temperature zone control: Zone 1: 150-160℃, Zone 2: 155-165℃, Zone 3: 160-170℃, Zone 4: 160-170℃, Zone 5: 160-170℃, Zone 6: 155-165℃, Zone 7: 150-160℃, Zone 8: 140-150℃, Zone 9: 130-140℃, Zone 10: 120-130℃, Zone 11: 110-120℃, Zone 12: 100-110℃; When pelletizing, the die temperature is 90-100℃ and the cutter temperature is 70-80℃; When pelletizing, pour the surface modifier A diluted at 1:20 into the water tank, and the water temperature should be ≤5℃; (4) Dehydration and surface treatment: The wet granules were processed in a centrifugal dehydrator (speed 800-1200 rpm); Spray surface modifier B (2kg / 100kg particles) at ≤5°C; After spraying, let it stand for 20-30 minutes.

[0013] The present invention provides a super-soft, highly transparent, and highly deformation-resistant TPE particle, which is used in the preparation of environmentally friendly, super-soft, and highly transparent toys, floating simulated fishing bait, and simulated green plants.

[0014] The beneficial effects of the present invention are: 1. Ultra-soft and highly transparent collaboration: By synergistically controlling the refractive index of SEEPS (SEPTOP / SEPTON) and triple hydrogenated white oil (1.48±0.01), a transmittance of >90% is achieved at 0V hardness, overcoming the dilemma of achieving both ultra-softness and high transparency. 2. Long-term anti-precipitation: High molecular weight SEEPS (300,000) compounded with SEBS (220,000) forms a dense network, with an oil migration rate of <0.1% at a 10-fold oil filling ratio ("better oil locking"); 3. Processing adaptability: Low-temperature pelletizing + double-surface modifier solves the adhesion problem of ultra-soft TPE from pelletizing to packaging, and the yield rate is increased to 99%. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0016] Figure 1 This is a TPE tensile test data table provided in Example 1 of the present invention.

[0017] Figure 2 This is a TPE tensile test data table provided in Example 2 of the present invention.

[0018] Figure 3 This is a TPE tensile test data table provided in Example 3 of the present invention. DETAILED DESCRIPTION

[0019] The following will clearly and completely describe the technical solutions in the embodiments of the present invention in conjunction with the accompanying drawings. Obviously, the described embodiments 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 creative efforts are within the scope of protection of the present invention.

[0020] Example: The present invention provides a highly soft, highly transparent, and highly deformation-resistant TPE particle, comprising a base rubber, tertiary hydrogenated white oil, a release agent, a primary antioxidant, an auxiliary antioxidant, and a light stabilizer; and further comprising an aqueous surface modifier A for preventing the surface of the TPE particles from sticking and used during pelletizing, and a surface modifier B for use during drying.

[0021] Example 1 This embodiment provides a highly soft, highly transparent, and highly deformation-resistant TPE particle, comprising the following materials in parts by weight: 7-9% base rubber, 80-91.5% tertiary hydrogenated white oil, 0.05-0.1% release agent, 0.3-0.4% primary antioxidant, 0.2-0.3% auxiliary antioxidant, and 0.1-0.2% light stabilizer.

[0022] In this embodiment, the VLRH hardness (hereinafter referred to as V) of the TPE particles is 0V.

[0023] Specifically, ① Selection of base rubber (SEBS, SEPS, SEEPS) (SEEPS) is a hydrogenated styrene block copolymer (HSBC) obtained by selective hydrogenation of polystyrene-b-polybutadiene / polyisoprene-b-polystyrene-propylene)-styrene block copolymer synthesized from SBIS by hydrogenation. SEEPS and SEBS both have good weather resistance and heat resistance, but SEEPS has higher strength and oil filling capacity. The oil-filled SEEPS blend has excellent flexibility, high tensile strength and low permanent deformation.

[0024] The base rubber used in this embodiment is a mixture of SEPTOP and SEPTON: (1) SEPTOP is a selective hydrogenation product of styrene-butadiene / isoprene-styrene block copolymer (SBIS), with a styrene content of 30% (molecular weight of 220,000). SEPTON has extremely high transparency while ensuring the mechanical properties of the product.

[0025] (2) SEPTON ultra-high molecular weight SEEPS, with a molecular weight of approximately 300,000, is a special structure SEEPS developed using unique ultra-high molecular weight technology. Compared with SEBS, it has the following performance advantages: higher tensile strength; better oil lock; high transparency and smoother surface; and better low-temperature performance.

[0026] ② Base rubber SEPTOP / SEPTON ratio Special grade of ultra-soft, ultra-transparent TPE with a VLRH hardness of 0V. To balance the molecular weight of SEEPS, high molecular weight SEPTOP rubber is selected as the main component and ultra-high molecular weight SEPTON rubber as the auxiliary component for blending. While meeting the requirements of high-rate oil filling, the performance indicators of ultra-soft, ultra-transparent TPE particles meet the requirements of the formula design.

[0027] In this embodiment, the ratio of SEPTOP / SEPTON is 70:30%.

[0028] 3. This embodiment uses tertiary hydrogenated white oil (including hydrogenated mineral oil, vegetable butter, and cosmetic grade white mineral oil).

[0029] Select two or more tertiary hydrogenated white oils, which are colorless, odorless, non-fluorescent, transparent, oily liquids. This balances the white oil's quality indicators (molecular weight 450-500), kinematic viscosity (14-16 at 40°C), flash point (170-180°C), and refractive index 1.48). Triple hydrogenated white oil is a key component in ensuring the high transparency of ultra-soft, ultra-transparent TPE.

[0030] ④ In this embodiment, the selection of release agent (also wetting agent, leveling agent, dispersant): CERALENE 691 is a modified synthetic polyester wax with a density (23°C) of 0.96-0.98 g / cm³, a dropping point of 73°C, a viscosity (120°C) of 130 mPa·s, and an acid value of 10 mg KOH / g. CERALENE 691 is used as a wetting agent, leveling agent, dispersant, and release agent for various plastics. Its excellent temperature stability, extremely low volatility, and improved surface gloss are prevented from precipitation.

[0031] ⑤⑥⑦ In this embodiment, the selection of auxiliary materials, main and auxiliary antioxidants, and light stabilizers: (1) IRGANOX 1135 is a 100% active liquid hindered phenol antioxidant (i.e., antioxidant) with a flash point molecular weight of 390; a flash point of 52°C; and a refractive index (20°C) of 1.493 to 1.499. IRGANOX 1135 is easily emulsified and can be dissolved, dispersed, or maintained in a pure liquid state during processing. Its effectiveness is enhanced when used in combination with other antioxidants such as IRGANOX 5057 and light stabilizers (e.g., UV absorbers and hindered amines).

[0032] (2) IRGANOX5057 ODP | Benzenamine, N-phenyl, reaction products with 2,4,4-trimethylpentene Antioxidant MIANOX5057 is a liquid aromatic amine antioxidant with a melting point of 95, a molecular weight of 361.563, a flash point of 238.9, and a refractive index of 1.552. (3) Hindered Amine 770; Bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate; Light Stabilizer GW-480; Light Stabilizer HA-10; Bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, 98%; Bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate; Light Stabilizer UV-770; Bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate (T770) sebacate is a low molecular weight UV hindered amine light stabilizer (HALS) composed of nitrooxy groups. Molecular weight: 480.73, transmittance: 425nm ≥97% 500nm ≥98%, can improve heat resistance when used with antioxidants, and has a synergistic effect with light stabilizers to improve light stabilization effect.

[0033] ⑧ Selection of surface modifier A Surface Anti-Stick Treatment: Add 1:20 Surface Modifier A (water-based) to the water tank to prevent sticking during pelletizing and ensure smooth dehumidification and drying of the material. (Homemade Surface Modifier A is composed of 95% polysiloxane-polyalkoxy ether copolymer emulsion and 5% nano-oil removal emulsifier, emulsified and dispersed).

[0034] Surface modifier A is used to ensure the anti-adhesion and smoothness of special grade super soft and super transparent TPE particles during the early pelletizing and dehydration process.

[0035] ⑨Selection of surface modifier B This modified silicone oil, SIC 64※※, contains high phenyl functionality and is domestically produced. Its refractive index (RI) at 25°C is 1.5340 ± 0.0050, and its viscosity at 25°C ranges from 800 to 1400 CPS. It offers excellent scratch resistance, a smooth feel, high transparency, excellent compatibility, and smooth and release properties. It provides both external and internal lubrication. External lubrication improves material processing, enhances fluidity, and reduces equipment wear. It forms a uniform lubricating layer on the plastic surface, significantly reducing the coefficient of friction and improving wear resistance. Surface Modifier B in this formulation acts as an anti-blocking agent for special-grade, ultra-soft, and ultra-transparent TPE during pellet drying, packaging, and transportation. It also acts as a release agent in subsequent injection molded products, imparting a smooth feel. Surface Modifiers A and B complement each other and are essential.

[0036] Add 1-2 kg of surface modifier B to every 100 kg of TPE pellets.

[0037] Example 2 This embodiment provides a highly soft, highly transparent, and highly deformation-resistant TPE particle, comprising the following materials in parts by weight: 9-10% base rubber, 80-90% tertiary hydrogenated white oil, 0.05-0.1% release agent, 0.2-0.4% primary antioxidant, 0.3-0.4% auxiliary antioxidant, and 0.1-0.2% light stabilizer.

[0038] In this embodiment, the VLRH hardness (hereinafter referred to as V) of the TPE particles is 5V.

[0039] Compared with the first embodiment, in this embodiment, The ratio of base rubber SEPTOP / SEPTON is 80:20%, accounting for 7~9% in this formula system.

[0040] ③Three times hydrogenated white oil (hydrogenated mineral oil, vegetable butter, cosmetic grade white mineral oil) selection Select two or more tertiary hydrogenated white oils, which are colorless, odorless, non-fluorescent, transparent, oily liquids. This balances the white oil's quality indicators (molecular weight 400-450), kinematic viscosity (13-15 at 40°C), flash point (160-170°C), and refractive index 1.48). Triple hydrogenated white oil is a key component in ensuring the high transparency of ultra-soft, ultra-transparent TPE.

[0041] ④ In this embodiment, the choice of release agent (also wetting agent, leveling agent, dispersant) Croda Incromax 100 release agent has a long-lasting lubricating effect. Even when added in amounts as low as 1000PPM, it can still achieve good lubrication and demoulding effects, with good transparency and high brightness.

[0042] ⑤⑥⑦ Selection of main and auxiliary antioxidants and light stabilizers for auxiliary materials (1) Basf additive: Chemical name: 6-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate octadecyl ester is a highly effective hindered phenol antioxidant with a flash point of 273°C and a molecular weight of 530. Transmittance: 425nm ≥96%, 500nm ≥98%. It has good compatibility with most polymers. It has a good effect in preventing discoloration caused by light and heat, and also has a certain light stabilization effect. When used in combination with auxiliary antioxidants such as AT-168 and DLTDP, it can produce a synergistic effect and achieve a better antioxidant effect.

[0043] (2) Tris (2,4-di-tert-butylphenyl) phosphite (AT-168), appearance is white crystalline powder, melting point 182℃-186.5℃, flash point 257℃, transmittance: 425nm ≥97%, 500nm ≥98%, generally not used alone, often used in combination with phenolic primary antioxidants, can improve the thermal stability of polymer processing. (3) Poly-{[6-[(1,1,3,3,-tetramethylbutyl)-amino]1,3,5,-triazine-2,4-diyl][(2,2,6,6-tetramethyl-*-yl)-imino]-1,6-hexanediyl-[(2,2,6,6-tetramethyl-*-yl)-imino]}CHIMASSORB944FD: molecular weight: 2000~3000, flash point 257℃, transmittance: 425nm ≥90%, 500nm ≥95%,

[0044] ⑧ Selection of surface modifier A Surface Anti-Stick Treatment: Add 1:20 Surface Modifier A (water-based) to the water tank to prevent sticking during pelletizing and dehydration, ensuring smooth dehumidification and drying of the material. (Homemade Surface Modifier A is composed of 95% polysiloxane-polyalkoxy ether copolymer emulsion and 5% nano-degreasing emulsifier.) Surface Modifier A prevents sticking and maintains smoothness during pelletizing and dehydration in the dehydrator for the special grade, ultra-soft, ultra-transparent TPE pellets.

[0045] ⑨Selection of surface modifier B Modified silicone oil with high phenyl functionality, SIC 64※※, domestically produced: refractive index / 25℃ 1.5340±0.0050, viscosity / 25℃ CPS 800-1400, excellent scratch resistance, smooth feel, high transparency, excellent compatibility, smoothness, and mold release properties. It provides both external and internal lubrication. External lubrication improves material processing performance, enhances flowability, and reduces equipment wear. It forms a uniform lubricating layer on the plastic surface, significantly reducing surface friction and improving wear resistance. Surface Modifier B in this formulation acts as an anti-blocking agent during pellet drying, packaging, and transportation for special-grade, ultra-soft, and ultra-transparent TPE. It also acts as a release agent in subsequent injection molding processes, imparting a smooth feel to the product. Surface Modifiers A and B complement each other and are essential. Add 1-2 kg of Surface Modifier B to every 100 kg of TPE pellets.

[0046] Example 3 This embodiment provides a highly soft, highly transparent, and highly deformation-resistant TPE particle, comprising the following materials in parts by weight: 10-12% base rubber, 80-88% tertiary hydrogenated white oil, 0.05-0.1% release agent, 0.2-0.4% primary antioxidant, 0.2-0.4% auxiliary antioxidant, and 0.1-0.2% light stabilizer.

[0047] In this embodiment, the VLRH hardness (hereinafter referred to as V) is 15V.

[0048] ① Selection of base rubber (SEBS, SEPS, SEEPS) KRATONG is a high-molecular-weight SEBS with a molecular weight of 220,000, a styrene content of 33, and a 5wt% mPa S of 50,000. SEBS is a linear triblock copolymer with polystyrene as the terminal segments and an ethylene-butylene copolymer derived from hydrogenated polybutadiene as the middle elastic block. Compared to SEBS, it offers higher tensile strength, transparency, and oil retention, as well as superior anti-leakage and deformation properties.

[0049] (2) The proportion of base rubber SEBS in this formula system Special grade ultra-soft and ultra-transparent TPE15V formula uses KRATONG and 220,000 molecular weight SEBS as the main material. This SEBS has high tensile strength, high transparency, high oil lock, and strong anti-precipitation and anti-deformation capabilities.

[0050] Triple hydrogenated white oil (hydrogenated mineral oil, vegetable butter, cosmetic grade white mineral oil) selection Select two or more tertiary hydrogenated white oils, which are colorless, odorless, non-fluorescent, transparent, oily liquids. This balances the white oil's quality indicators (molecular weight 300-400), kinematic viscosity (12-14 at 40°C), flash point (150-160°C), and refractive index 1.48). Triple hydrogenated white oil is a key component in ensuring the high transparency of ultra-soft, ultra-transparent TPE.

[0051] ④ Selection of wetting agent, leveling agent and dispersant Honeywell Rheochem® HPL-6901 is a high-performance lubricant for plastics applications. Its primary function in plastics is to provide excellent internal and external lubrication, improving surface quality without affecting mechanical properties. It is particularly suitable for TPU, PC, PA, and coatings requiring a low melting point.

[0052] Honeywell RHEOCHEM@HPL-6901 is a new specialty polyester wax product, montan wax, with excellent lubricity and heat resistance. It helps improve mold release while minimally affecting product transparency and mechanical properties. Transparency: 89.84 at 550nm, Viscosity: 12 cps @ 100°C, Acid Value: 13 KOH mg / g. It has excellent lubricity and heat resistance, making it particularly suitable for modifying transparent products such as TPU, PA, PC, TPE, and PMMA.

[0053] (1) Basf additive: Chemical name: 6-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate octadecyl ester is a highly effective hindered phenol antioxidant with a flash point of 273°C and a molecular weight of 530. Transmittance: 425nm ≥96%, 500nm ≥98%. It has good compatibility with most polymers. It has a good effect in preventing discoloration caused by light and heat, and also has a certain light stabilization effect. When used in combination with auxiliary antioxidants such as AT-168 and DLTDP, it can produce a synergistic effect and achieve a better antioxidant effect.

[0054] (2) Antioxidant 1330 is a secondary antioxidant used in synthetic materials. Its chemical name is tris(2,4-di-tert-butylphenyl)phosphite (CAS No.: 31570-04-4). It appears as a white crystalline powder with a melting point of 182°C-186.5°C, a flash point of 257°C, and a transmittance of ≥97% at 425nm and ≥98% at 500nm. It is generally not used alone and is often used in combination with a phenolic primary antioxidant to improve the thermal stability of polymer processing.

[0055] (3) Polymeric high molecular weight hindered amine light stabilizer, selected light stabilizer UV944, poly-{[6-[(1,1,3,3,-tetramethylbutyl)-amino]1,3,5,-triazine-2,4-diyl][(2,2,6,6-tetramethyl*)-imino]-1,6-hexanediyl-[(2,2,6,6-tetramethyl*)-subunit]}CHIMASSORB944FD: molecular weight: 2000~3000, flash point 257℃, transmittance: 425nm ≥90%, 500nm ≥95%, ⑧ Selection of surface modifier A Surface Anti-Stick Treatment: Add 1:20 Surface Modifier A (water-based) to the water tank to prevent sticking during pelletizing and dehydration, ensuring smooth dehumidification and drying of the material. (Homemade Surface Modifier A is composed of 95% polysiloxane-polyalkoxy ether copolymer emulsion and 5% nano-degreasing emulsifier.) Surface Modifier A prevents sticking and maintains smoothness during pelletizing and dehydration in the dehydrator for the special grade, ultra-soft, ultra-transparent TPE pellets.

[0056] ⑨Selection of surface modifier B This modified silicone oil, SIC 64※※, contains high phenyl functionality and is domestically produced. Its refractive index (RI) at 25°C is 1.5340 ± 0.0050, and its viscosity at 25°C ranges from 800 to 1400 CPS. It offers excellent scratch resistance, a smooth feel, high transparency, excellent compatibility, and smooth and release properties. It provides both external and internal lubrication. External lubrication improves material processing, enhances fluidity, and reduces equipment wear. It forms a uniform lubricating layer on the plastic surface, significantly reducing the coefficient of friction and improving wear resistance. Surface Modifier B in this formulation acts as an anti-blocking agent for special-grade, ultra-soft, and ultra-transparent TPE during pellet drying, packaging, and transportation. It also acts as a release agent in subsequent injection molded products, imparting a smooth feel. Surface Modifiers A and B complement each other and are essential.

[0057] SIC 64※※Refractive index 1.534 (Add 1-2 kg of surface modifier B to every 100 kg of TPE pellets).

[0058] See Table 1, which is a table showing the tensile performance test data of three embodiments of the present invention. Table 1 Mechanical properties test: Tensile properties: National standard for tensile properties GB / T 528-2009. ISO37:2005 complies with ASTM 412-1998.

[0059] Physical and chemical performance test: 1. Melt index: GB / T 3682-2000 national standard test, in line with ASTM, ISO, JIS, CNS standards, carried out on HD-R803 melt index instrument, 2. Hardness test: GB / T531-99 national standard, in line with DIN53505, ASTM D 2240, carried out on a MODEL-X hardness tester. 3. Density: GB / T / 1033.2-2010 national standard, in compliance with ASTM D792 and ASTM D297, measured on an MH-300A plastics densitometer.

[0060] The above performance tests all meet the standards.

[0061] like Figure 1 Table 2 shows the tensile test report of Example 1 of the present invention: Table 2 like Figure 2 Table 3 shows the tensile test report of Example 2 of the present invention: Table 3 like Figure 3 Table 4 shows the tensile test report of Example 3 of the present invention: Table 4 Because special-grade ultra-soft TPE is filled with a large amount of plasticizer (white oil) and is viscous, the aspect ratio of ordinary TPE equipment is insufficient. The screw structure needs to be reorganized and adjusted, and the homogenizing section needs to be lengthened to better reduce the temperature and ensure smooth pelletizing.

[0062] To this end, the present invention also provides a method for preparing super-soft, highly transparent, and highly deformation-resistant TPE particles, specifically: The following steps are involved: (1) Mixing: Mix the base rubber and tertiary hydrogenated white oil at 160°C for 20-40 minutes; (2) Adding additives: Add release agent, primary antioxidant, auxiliary antioxidant and light stabilizer in sequence and continue mixing for 10-15 minutes; (3) Low temperature underwater pelletizing: ① Extrusion equipment for special grade super soft TPE granules; GTE-65B parallel twin-screw extruder; The parallel co-rotating twin-screw extruder is used with its excellent mixing and plasticizing performance, good screw self-cleaning function, and the "building block combination" function of the screw barrel, and the screw structure combination is easy to adjust.

[0063] Screw diameter: 62.4mm, aspect ratio L / D: 48, screw speed: ≥600rpm, motor power: 90KW, Adopt low temperature underwater pelletizing system The low-temperature underwater pelletizing system features die head insulation technology, low-pressure production without blockage, and an exposed, integral mold plate that is removable and easy to operate. The system also features a pioneering pneumatic start valve, which is simple, reliable, and pollution-free. The 45-degree water inlet and discharge pipe ensures smooth pellet flow. The water chamber features a quick-release mechanism with no bypass. The system also features removable automatic blade adjustment technology to prevent blade entanglement and blockage. Auxiliary underwater pelletizing equipment also includes a water tank, a chiller, a dehydrator, a secondary blower, and a dryer.

[0064] TPE granule molding process: Because the special grade super soft TPE is filled with a large amount of plasticizer and is viscous, the entire process needs to be completed from viscosity - conveying - compression - melting - vacuum - homogenization and cooling - die head - pelletizing - dehydration - drying. Screw structure: A twin-screw structure is required, and the aspect ratio is required to be 1:48. The screw structure consists of five sections: conveying section, compression section, melting section, exhaust section, and homogenization section, with a total of twelve sections.

[0065] Temperature Control: Zone 1: 150-160°C, Zone 2: 155-165°C, Zone 3: 160-170°C, Zone 4: 160-170°C, Zone 5: 160-170°C, Zone 6: 155-165°C, Zone 7: 150-160°C, Zone 8: 140-150°C, Zone 9: 130-140°C, Zone 10: 120-130°C, Zone 11: 110-120°C, Zone 12: 100-110°C, Die Head: 90-100°C, Cutter: 70-80°C. Equipment modification and temperature control are key to resolving the issues of difficulty or inability to pelletize ultra-soft TPE.

[0066] Adopt high and low mixing - 500 / 1000 hot and cold mixing unit, Model: SRL-Z500 / 1000, total volume: 500 / 1000L, stirring paddle speed: 130r / min, high speed 860r / min, heating and cooling method: self-friction / water cooling, mixing time: 8-12min, drive motor power: 75 / 15KW, speed regulation method: variable frequency speed regulation.

[0067] The main mixing process is as follows: base rubber unpacking inspection → screening → formulation → high-speed mixing → cooling and mixing.

[0068] The super-soft, highly transparent, and highly deformation-resistant TPE particles provided by the present invention are used in the preparation of environmentally friendly, super-soft, and highly transparent toys, floating simulated fishing baits, and simulated green plants.

[0069] Obviously, those skilled in the art may make various changes and modifications to the present invention without departing from the spirit and scope of the present invention. Thus, if such changes and modifications fall within the scope of the claims and their equivalents, the present invention is intended to include such changes and modifications.

Claims

1. A super soft, highly transparent and highly deformation resistant TPE particle, characterized in that: The invention includes the following materials: base rubber, tertiary hydrogenated white oil, release agent, primary antioxidant, auxiliary antioxidant, light stabilizer; it also includes water-based surface modifier A used for anti-sticking on the surface of TPE particles and used during pelletizing, as well as surface modifier B used during drying.

2. The ultra-soft, highly transparent, and highly deformation-resistant TPE particles according to claim 1, characterized in that: The weight ratio of the materials is: base rubber 7-9%, tertiary hydrogenated white oil 80-91.5%, release agent 0.05-0.1%, primary antioxidant 0.3-0.4%, auxiliary antioxidant 0.2-0.3%, light stabilizer 0.1-0.2%; the weight ratio of surface modifier A to water is 1:20, and 1-2 kg of surface modifier B is added to every 100 g of TPE particles.

3. The ultra-soft, highly transparent, and highly deformation-resistant TPE particles according to claim 1, characterized in that: The weight ratio of the materials is: base rubber 9-10%, tertiary hydrogenated white oil 80-90%, release agent 0.05-0.1%, primary antioxidant 0.2-0.4%, auxiliary antioxidant 0.3-0.4%, light stabilizer 0.1-0.2%; the weight ratio of surface modifier A to water is 1:20, and 1-2 kg of surface modifier B is added to every 100 g of TPE particles.

4. The ultra-soft, highly transparent, and highly deformation-resistant TPE particles according to claim 1 are characterized in that: The weight ratio of the materials is: base rubber 10-12%, tertiary hydrogenated white oil 80-88%, release agent 0.05-0.1%, primary antioxidant 0.2-0.4%, auxiliary antioxidant 0.2-0.4%, light stabilizer 0.1-0.2%; the weight ratio of surface modifier A to water is 1:20, and 1-2 kg of surface modifier B is added to every 100 g of TPE particles.

5. The ultra-soft, highly transparent, and highly deformation-resistant TPE particles according to claim 2, characterized in that: The base rubber is a mixture of SEPTOP and SEPTON, with the weight ratio of SEPTOP to SEPTON being 7:

3. The tertiary hydrogenated white oil is prepared by hydrogenating two or three of hydrogenated mineral oil, vegetable butter, and cosmetic-grade white mineral oil. The release agent is synthetic polyester wax, the primary antioxidant is a hindered phenol antioxidant, the secondary antioxidant is a liquid aromatic amine antioxidant, and the light stabilizer is a hindered amine light stabilizer. The surface modifier A is prepared by emulsifying and dispersing 95% of a polysiloxane-polyalkoxy ether copolymer emulsion with 5% of a nano-degreasing emulsifier. The surface modifier B is a modified silicone oil containing a high phenyl functional group.

6. The ultra-soft, highly transparent, and highly deformation-resistant TPE particles according to claim 3, characterized in that: The base rubber is a mixture of SEPTOP and SEPTON, with the weight ratio of SEPTOP to SEPTON being 8:

2. The tertiary hydrogenated white oil is prepared by hydrogenating two or three of hydrogenated mineral oil, vegetable butter, and cosmetic-grade white mineral oil. The release agent is synthetic polyester wax, the primary antioxidant is a liquid hindered phenol antioxidant, the secondary antioxidant is a liquid aromatic amine antioxidant, and the light stabilizer is a hindered amine light stabilizer. The surface modifier A is prepared by emulsifying and dispersing 95% of a polysiloxane-polyalkoxy ether copolymer emulsion with 5% of a nano-degreasing emulsifier. The surface modifier B is a modified silicone oil containing a high phenyl functional group.

7. The ultra-soft, highly transparent, and highly deformation-resistant TPE particles according to claim 4, characterized in that: The base rubber is KRATONG; the tertiary hydrogenated white oil is prepared by hydrogenating two or three of hydrogenated mineral oil, vegetable butter, and cosmetic-grade white mineral oil; the release agent is polyester wax; the primary antioxidant is a hindered phenol-type antioxidant; the auxiliary antioxidant is antioxidant 1330; the light stabilizer is a hindered amine light stabilizer; the surface modifier A is prepared by emulsifying and dispersing 95% of a polysiloxane-polyalkoxy ether copolymer emulsion with 5% of a nano-oil removal emulsifier; and the surface modifier B is a modified silicone oil containing a high phenyl functional group.

8. The method for preparing super-soft, highly transparent, and highly deformation-resistant TPE particles according to claim 1, characterized in that: The following steps are involved: (1) Mixing: Mix the base rubber and tertiary hydrogenated white oil at 160°C for 20-40 minutes; (2) Adding additives: Add release agent, primary antioxidant, auxiliary antioxidant and light stabilizer in sequence and continue mixing for 10-15 minutes; (3) Low temperature underwater pelletizing: The melt was extruded through a GTE-65B parallel co-rotating twin-screw extruder with a screw length-diameter ratio of 48:1; Barrel temperature zone control: Zone 1: 150-160℃, Zone 2: 155-165℃, Zone 3: 160-170℃, Zone 4: 160-170℃, Zone 5: 160-170℃, Zone 6: 155-165℃, Zone 7: 150-160℃, Zone 8: 140-150℃, Zone 9: 130-140℃, Zone 10: 120-130℃, Zone 11: 110-120℃, Zone 12: 100-110℃; When pelletizing, the die temperature is 90-100℃ and the cutter temperature is 70-80℃; When pelletizing, pour the surface modifier A diluted at 1:20 into the water tank, and the water temperature should be ≤5℃; (4) Dehydration and surface treatment: The wet granules were processed in a centrifugal dehydrator (speed 800-1200 rpm); Spray surface modifier B (2kg / 100kg particles) at ≤5°C; After spraying, let it sit for 20-30 minutes.

9. The ultra-soft, highly transparent, and highly deformation-resistant TPE particles according to claim 1, characterized in that: It is used in the preparation of environmentally friendly, ultra-soft, highly transparent toys, floating simulated fishing baits, and simulated green plants.

Images