Soft Transparent MABS Material for Beauty Industry Ornaments and Preparation Method

Abstract

The present invention discloses a soft transparent MABS material for beauty industry ornaments and a preparation method thereof. The material comprises 80-100 parts of MABS resin, 5-10 parts of ABS resin, 4-10 parts of phthalic acid diester, 10-40 parts of polyethylene glycol fatty acid ester, 3-7 parts of thermoplastic elastomer POE, 1-5 parts of tris(2,4-di-tert-butylphenyl) phosphite, 5-10 parts of nano calcium carbonate powder, and 10-30 parts of nano titanium dioxide powder. Using MABS and ABS resin as the main components, through the research on plasticizers, stabilizers and fillers, a soft transparent MABS material meeting the performance requirements is finally obtained, expanding the application of the material; the compounding of small molecular weight and large molecular weight plasticizers is adopted, so that the material has excellent low temperature resistance and durability, and still maintains stable softness during long-term use. It can be widely applied to beauty industry ornaments and has good economic value.

Description

Technical Field

[0001] The present invention belongs to the field of polymer materials, and particularly relates to a soft transparent MABS material for beauty industry ornaments and a preparation method thereof. Background Art

[0002] With the demands of people for the quality of life and the environment, the beauty industry has seen a large market demand. Due to the particularity of beauty industry ornaments, the requirements for their materials in terms of aesthetics and performance are getting higher and higher. Among them, transparent and soft materials have received increasing attention and demand, which has also given rise to a large number of related materials. Commonly used materials are mainly PVC-based materials and ABS-based materials. However, soft transparent PVC materials are sensitive to temperature, easily become hard at low temperatures and lose elasticity; while their durability deteriorates at higher temperatures, which limits the application of PVC materials. There has also been increasing research on ABS materials, but there are still many drawbacks. Transparent MABS is a type of special resin developed on the basis of general ABS resin, which can meet the light transmission requirements while having excellent mechanical properties.

[0003] Chinese Patent CN106188980A discloses a clear and soft PVC film, which is prepared from the following raw materials in parts by mass: 100 parts of PVC resin, 1 - 7 parts of plasticizer, 10 - 20 parts of filler, 1.5 - 3 parts of heat stabilizer, 0.5 - 2 parts of lubricant, 1 - 2 parts of softening agent, 1 - 2 parts of vinyl methacrylate resin, and 0.5 - 1.5 parts of surface modifier, and the surface modifier is a borate ester.

[0004] Chinese Patent CN 105936732 A discloses a high-transparency, high-hardness flame-retardant ABS composite material and a preparation method thereof; it is made from the following raw materials in parts by weight: 60 - 85 parts of resin A, 10 - 30 parts of PMMA, 10 - 20 parts of flame-retardant masterbatch, and 5 - 25 parts of toughening agent; wherein, the resin A is MABS. Although this scheme can obtain a material with excellent transparency, its hardness is still relatively high and cannot meet the softness requirement.

[0005] How to seek to prepare a composite material with high transparency and softness is still a demand in the field of composite materials. Summary of the Invention

[0006] Based on the defects and demands existing in the prior art, the present invention provides a soft transparent MABS material for beauty industry ornaments and a preparation method thereof. Through the present invention, a high-light-transmission and soft ABS material is prepared, which has excellent low-temperature resistance and durability.

[0007] According to one of the purposes of the present invention, the following technical solutions are provided:

[0008] A soft transparent MABS material applied to beauty industry ornaments, and the soft transparent MABS material comprises the following raw materials by weight:

[0009] 80 - 100 parts of MABS resin,

[0010] 5 - 10 parts of ABS resin,

[0011] 4 - 10 parts of phthalic acid diester,

[0012] 10 - 40 parts of polyethylene glycol fatty acid ester,

[0013] 3 - 7 parts of thermoplastic elastomer POE,

[0014] 1 - 5 parts of tris(2,4 - di - tert - butylphenyl) phosphite,

[0015] 5 - 10 parts of nano calcium carbonate powder,

[0016] 10 - 30 parts of nano titanium dioxide powder.

[0017] Further, the soft transparent MABS material comprises the following raw materials by weight:

[0018] 85 - 95 parts of MABS resin,

[0019] 7 - 8 parts of ABS resin,

[0020] 5 - 7 parts of phthalic acid diester,

[0021] 15 - 28 parts of polyethylene glycol fatty acid ester,

[0022] 5 - 6 parts of thermoplastic elastomer POE,

[0023] 2 - 4 parts of tris(2,4 - di - tert - butylphenyl) phosphite,

[0024] 7 - 8 parts of nano calcium carbonate powder,

[0025] 14 - 24 parts of nano titanium dioxide powder.

[0026] Adding plasticizers to MABS materials can effectively reduce the glass transition temperature of the materials and improve their low-temperature resistance. However, to a large extent, small-molecular-weight plasticizers are prone to migration, which also makes the molecular migration of MABS materials easier. As the service life extends, it will lead to a bleeding phenomenon, so the hardness of MABS materials increases and they lose their soft properties. Although large-molecular-weight plasticizers can limit and inhibit migration, they have the defect of poor compatibility and also make the low-temperature resistance of the materials worse. In the prior art, different types of plasticizers are usually compounded to overcome the above deficiencies. However, there are few studies on MABS materials, and there is no exact theoretical guidance on how to select. Through repeated experiments and verification, the applicant finally selects the compound of dibutyl phthalate and polyethylene glycol fatty acid ester to improve the low-temperature and durability performance of soft and transparent MABS materials. After long-term use, the materials can still maintain good flexibility.

[0027] Furthermore, the dosage of dibutyl phthalate and polyethylene glycol fatty acid ester also has a great impact on the performance. The applicant found in the experiment that the deviation in the ratio of dibutyl phthalate and polyethylene glycol fatty acid ester brings many uncertain factors; specifically, the mass ratio of dibutyl phthalate and polyethylene glycol fatty acid ester is controlled to be 1:(3-4).

[0028] In the application document, tris(2,4-di-tert-butylphenyl) phosphite is an antioxidant heat stabilizer; it can effectively improve the thermal stability and antioxidant properties of soft and transparent MABS materials. Preferably, in this application, the weight portion of tris(2,4-di-tert-butylphenyl) phosphite is controlled to be 1-5 parts.

[0029] Furthermore, nano calcium carbonate powder and nano titanium dioxide powder are used as inorganic fillers. Preferably, the particle size of the nano calcium carbonate powder is 300-500 nm, and the particle size of the nano titanium dioxide powder is 100-200 nm; more preferably, the mass ratio of the nano calcium carbonate powder to the nano titanium dioxide powder is 1:(2-3).

[0030] In the application document, thermoplastic elastomer POE is used to improve the flexibility of soft and transparent MABS materials, making the materials more bendable.

[0031] Furthermore, the light transmittance of the soft and transparent MABS material is ≥91%; the Shore hardness is 50-60 HA.

[0032] Furthermore, in the case of low requirements for transparency, the soft and transparent MABS material of this application can also include masterbatch. Appropriate masterbatch can be added according to the color requirements.

[0033] The present invention also provides a preparation method of a soft transparent ABS material for beauty industry ornaments, which specifically includes the following steps:

[0034] (1) Mix MABS resin, ABS resin, dioctyl phthalate, polyethylene glycol fatty acid ester, thermoplastic elastomer POE, and tris(2,4-di-tert-butylphenyl) phosphite evenly according to the weight ratio.

[0035] (2) Feed the mixture obtained in step (1) through the main feeder, and feed nano calcium carbonate powder and nano titanium dioxide powder through the side feeder, and then melt, mix, extrude and pelletize through a twin-screw extruder; thus, the soft transparent ABS material is obtained.

[0036] Further, the ratio of the length to the diameter of the twin-screw extruder is (45-50):1, and the screw rotation speed is controlled at 300-400 r / min.

[0037] Further, the set temperature of the twin-screw extruder is as follows: the first section: 180-200 °C, the second section: 185-205 °C, the third section: 190-210 °C, the fourth section: 195-215 °C, the fifth section: 200-220 °C, the sixth section: 190-210 °C, the seventh section: 190-210 °C, the eighth section: 190-210 °C, the ninth section: 195-215 °C, the 10th section: 200-220 °C, and the head: 240-260 °C.

[0038] Compared with the prior art, the present invention has the following beneficial effects: (1) Using MABS resin as the main component, through the research on plasticizers, stabilizers and fillers, a soft transparent MABS material that meets the performance requirements is finally obtained, expanding the application of the material. (2) The compounding of small molecular weight and large molecular weight plasticizers is adopted, so that the material has excellent low temperature resistance and durability, and still maintains stable softness during long-term use. Specific Embodiments

[0039] The following combines specific embodiments to further describe the present invention in detail with examples, so that the advantages of the present invention are more easily understood by those skilled in the art, but it is not used to limit the protection scope of the present invention.

[0040] Example 1

[0041] A soft transparent MABS material for beauty industry ornaments, calculated by weight, the soft transparent MABS material includes the following raw materials: 80 parts of MABS resin, 5 parts of ABS resin, 4 parts of dioctyl phthalate, 12 parts of polyethylene glycol fatty acid ester, 3 parts of thermoplastic elastomer POE, 1 part of tris(2,4-di-tert-butylphenyl) phosphite, 5 parts of nano calcium carbonate powder, and 10 parts of nano titanium dioxide powder.

[0042] Among them: the particle size of the nano calcium carbonate powder is 300 nm, and the particle size of the nano titanium dioxide powder is 100 nm.

[0043] The preparation method of the soft transparent MABS material specifically includes the following steps: (1) Mix MABS resin, ABS resin, dioctyl phthalate, polyethylene glycol fatty acid ester, thermoplastic elastomer POE, tris(2,4-di-tert-butylphenyl) phosphite evenly according to the weight ratio; (2) Feed the mixture obtained in step (1) through the main feeder, and feed the nano calcium carbonate powder and nano titanium dioxide powder through the side feeder, and melt, mix, extrude and pelletize through a twin-screw extruder; thus obtaining the soft transparent ABS material.

[0044] Among them, the length-diameter ratio of the twin-screw extruder is 45:1, and the screw speed control is set at 350 r / min; the set temperature of the twin-screw extruder is: section 1: 180 °C, section 2: 185 °C, section 3: 190 °C, section 4: 195 °C, section 5: 200 °C, section 6: 190 °C, section 7: 190 °C, section 8: 190 °C, section 9: 195 °C, section 10: 200 °C, head: 240 °C.

[0045] Example 2

[0046] A soft transparent MABS material applied to beauty industry ornaments, the soft transparent MABS material includes the following raw materials by weight: 100 parts of MABS resin, 10 parts of ABS resin, 10 parts of dioctyl phthalate, 40 parts of polyethylene glycol fatty acid ester, 7 parts of thermoplastic elastomer POE, 5 parts of tris(2,4-di-tert-butylphenyl) phosphite, 10 parts of nano calcium carbonate powder, and 30 parts of nano titanium dioxide powder.

[0047] Among them: the particle size of the nano calcium carbonate powder is 500 nm, and the particle size of the nano titanium dioxide powder is 200 nm.

[0048] The preparation method of the soft transparent MABS material specifically includes the following steps: (1) Mix MABS resin, ABS resin, dioctyl phthalate, polyethylene glycol fatty acid ester, thermoplastic elastomer POE, tris(2,4-di-tert-butylphenyl) phosphite evenly according to the weight ratio; (2) Feed the mixture obtained in step (1) through the main feeder, and feed the nano calcium carbonate powder and nano titanium dioxide powder through the side feeder, and melt, mix, extrude and pelletize through a twin-screw extruder; thus obtaining the soft transparent ABS material.

[0049] Among them, the length-diameter ratio of the twin-screw extruder is 50:1, and the screw rotation speed is controlled at 350 r / min; the set temperature of the twin-screw extruder is as follows: the first section: 200 °C, the second section: 205 °C, the third section: 210 °C, the fourth section: 215 °C, the fifth section: 220 °C, the sixth section: 210 °C, the seventh section: 210 °C, the eighth section: 210 °C, the ninth section: 215 °C, the 10th section: 220 °C, and the head: 260 °C.

[0050] Example 3

[0051] A soft transparent MABS material applied to beauty industry ornaments. The soft transparent MABS material, by weight, comprises the following raw materials: 90 parts of MABS resin, 7 parts of ABS resin, 6 parts of phthalic acid diester, 24 parts of polyethylene glycol fatty acid ester, 6 parts of thermoplastic elastomer POE, 4 parts of tris(2,4-di-tert-butylphenyl) phosphite, 8 parts of nano calcium carbonate powder, and 16 parts of nano titanium dioxide powder.

[0052] Among them: the particle size of the nano calcium carbonate powder is 400 nm, and the particle size of the nano titanium dioxide powder is 150 nm.

[0053] The preparation method of the soft transparent MABS material specifically comprises the following steps: (1) Mix 90 parts of MABS resin, 7 parts of ABS resin, 6 parts of phthalic acid diester, 24 parts of polyethylene glycol fatty acid ester, 6 parts of thermoplastic elastomer POE, and 4 parts of tris(2,4-di-tert-butylphenyl) phosphite evenly according to the weight ratio; (2) Feed the mixture obtained in step (1) through the main feeder, and feed the nano calcium carbonate powder and the nano titanium dioxide powder through the side feeder, and melt, mix, extrude, and pelletize through a twin-screw extruder; thus, the soft transparent ABS material is obtained.

[0054] Among them, the length-diameter ratio of the twin-screw extruder is 50:1, and the screw rotation speed is controlled at 350 r / min; the set temperature of the twin-screw extruder is as follows: the first section: 190 °C, the second section: 200 °C, the third section: 195 °C, the fourth section: 200 °C, the fifth section: 210 °C, the sixth section: 195 °C, the seventh section: 200 °C, the eighth section: 200 °C, the ninth section: 210 °C, the 10th section: 210 °C, and the head: 250 °C.

[0055] In order to better elaborate the functions and impacts of the raw materials in this application, the applicant takes the raw materials and weight parts of Example 3 as the benchmark and focuses on investigating the impacts of the plasticizer and the thermoplastic elastomer POE.

[0056] Comparative Example 1

[0057] A soft transparent MABS material applied to beauty industry ornaments. The soft transparent MABS material, by weight, comprises the following raw materials: 90 parts of MABS resin, 7 parts of ABS resin, 24 parts of polyethylene glycol fatty acid ester, 6 parts of thermoplastic elastomer POE, 4 parts of tris(2,4-di-tert-butylphenyl) phosphite, 8 parts of nano calcium carbonate powder, and 16 parts of nano titanium dioxide powder.

[0058] Among them: The particle size of the nano calcium carbonate powder is 400 nm, and the particle size of the nano titanium dioxide powder is 150 nm.

[0059] The preparation method of the soft transparent MABS material specifically comprises the following steps: (1) Mix 90 parts of MABS resin, 7 parts of ABS resin, 24 parts of polyethylene glycol fatty acid ester, 6 parts of thermoplastic elastomer POE, and 4 parts of tris(2,4-di-tert-butylphenyl) phosphite evenly according to the weight ratio; (2) Feed the mixture obtained in step (1) through the main feeder, and feed the nano calcium carbonate powder and the nano titanium dioxide powder through the side feeder, and melt, mix, extrude, and pelletize through a twin-screw extruder; thus, the soft transparent ABS material is obtained.

[0060] Among them, the length-diameter ratio of the twin-screw extruder is 50:1, and the screw speed control is set at 350 r / min; the set temperature of the twin-screw extruder is as follows: the first section: 190 °C, the second section: 200 °C, the third section: 195 °C, the fourth section: 200 °C, the fifth section: 210 °C, the sixth section: 195 °C, the seventh section: 200 °C, the eighth section: 200 °C, the ninth section: 210 °C, the 10th section: 210 °C, and the head: 250 °C.

[0061] Comparative Example 2

[0062] A soft transparent MABS material applied to beauty industry ornaments. The soft transparent MABS material, by weight, comprises the following raw materials: 90 parts of MABS resin, 7 parts of ABS resin, 6 parts of phthalic acid diester, 6 parts of thermoplastic elastomer POE, 4 parts of tris(2,4-di-tert-butylphenyl) phosphite, 8 parts of nano calcium carbonate powder, and 16 parts of nano titanium dioxide powder.

[0063] Among them: The particle size of the nano calcium carbonate powder is 400 nm, and the particle size of the nano titanium dioxide powder is 150 nm.

[0064] The preparation method of the soft transparent MABS material specifically includes the following steps: (1) Mix MABS resin, ABS resin, dioctyl phthalate, thermoplastic elastomer POE, and tris(2,4-di-tert-butylphenyl) phosphite evenly according to the weight ratio; (2) Feed the mixture obtained in step (1) through the main feeder, and feed nano calcium carbonate powder and nano titanium dioxide powder through the side feeder, and melt, mix, extrude, and pelletize through a twin-screw extruder; thus obtaining the soft transparent ABS material.

[0065] Among them, the length-diameter ratio of the twin-screw extruder is 50:1, and the screw rotation speed control is set at 350 r / min; the set temperature of the twin-screw extruder is: the first section: 190 °C, the second section: 200 °C, the third section: 195 °C, the fourth section: 200 °C, the fifth section: 210 °C, the sixth section: 195 °C, the seventh section: 200 °C, the eighth section: 200 °C, the ninth section: 210 °C, the 10th section: 210 °C, the head: 250 °C.

[0066] Comparative Example 3

[0067] A soft transparent MABS material applied to beauty industry ornaments, the soft transparent MABS material includes the following raw materials by weight: 90 parts of MABS resin, 7 parts of ABS resin, 6 parts of dioctyl phthalate, 24 parts of polyethylene glycol fatty acid ester, 4 parts of tris(2,4-di-tert-butylphenyl) phosphite, 8 parts of nano calcium carbonate powder, and 16 parts of nano titanium dioxide powder.

[0068] Among them: the particle size of the nano calcium carbonate powder is 400 nm, and the particle size of the nano titanium dioxide powder is 150 nm.

[0069] The preparation method of the soft transparent MABS material specifically includes the following steps: (1) Mix MABS resin, ABS resin, dioctyl phthalate, polyethylene glycol fatty acid ester, and tris(2,4-di-tert-butylphenyl) phosphite evenly according to the weight ratio; (2) Feed the mixture obtained in step (1) through the main feeder, and feed nano calcium carbonate powder and nano titanium dioxide powder through the side feeder, and melt, mix, extrude, and pelletize through a twin-screw extruder; thus obtaining the soft transparent ABS material.

[0070] Among them, the length-diameter ratio of the twin-screw extruder is 50:1, and the screw rotation speed control is set at 350 r / min; the set temperature of the twin-screw extruder is: the first section: 190 °C, the second section: 200 °C, the third section: 195 °C, the fourth section: 200 °C, the fifth section: 210 °C, the sixth section: 195 °C, the seventh section: 200 °C, the eighth section: 200 °C, the ninth section: 210 °C, the 10th section: 210 °C, the head: 250 °C.

[0071] The light transmittance was tested according to the standard of GB / T 2410—2008 "Determination of Transmittance and Haze of Transparent Plastics". For each sample, three points on the surface were selected for measurement respectively, and the results were averaged.

[0072] The hardness was tested according to the standard of GB / T 2411—2008 "Determination of Indentation Hardness (Shore Hardness) of Plastics and Hard Rubber by Means of a Durometer". The test specimen was composed of two layers of 4-mm-thick sample pieces laminated together. The A-type Shore durometer was used to test for 20 s. For each sample, measurements were taken 3 times at different positions, and the results were averaged.

[0073] According to the standard of GB 5470-85, the embrittlement temperature of the materials in the examples and comparative examples was tested under low-temperature conditions.

[0074] The results of the above tests are recorded in Table 1 below:

[0075] Table 1

[0076]

[0077] (1) According to the experimental data in Table 1, it can be seen that the soft transparent MABS material provided by the present invention has good light transmittance and moderate softness, which can meet the requirements of beauty industry ornaments; and it has excellent low-temperature resistance.

[0078] (2) From the data of Example 3 and Comparative Examples 1-3, it can be seen that phthalic acid diester, polyethylene glycol fatty acid ester, and thermoplastic elastomer POE have little influence on the light transmittance performance of the soft transparent MABS material; however, their influence on the hardness and low-temperature resistance performance is significant.

[0079] The hardness of Comparative Examples 1-3 is much higher than that of Example 3 of the present application; this shows that the technical solution of the present application obtains a soft and moderate transparent material; while the hardness of Comparative Examples 1-3 increases significantly; it is not suitable for application environments that require softness characteristics.

[0080] In the case of the absence of phthalic acid diester, the embrittlement temperature of Example 1 increased, but the increase amplitude was not large; however, in the case of the absence of polyethylene glycol fatty acid ester, the embrittlement temperature increased to -25°C, which was significantly increased compared with that; this shows that polyethylene glycol fatty acid ester has a very obvious influence on the low-temperature resistance performance of the material.

[0081] In summary, the present application uses MABS and ABS as the main components, and cooperates with other plasticizers, stabilizers, and inorganic fillers to prepare a material with high light transmittance and moderate softness for beauty industry ornaments; it greatly improves the application scenario requirements of the material and has high economic value.

[0082] The technical means disclosed in the technical solution of this application are not limited to the technical means described above, but also include technical solutions composed of any combination of the above technical features. The above is the specific implementation manner of the present invention. It should be noted that for those skilled in the art of this technology, without departing from the principle of the present invention, several improvements and modifications can be made, and these improvements and modifications are also regarded as the protection scope of the present invention.

Claims

1. A soft and transparent MABS material applied to beauty industry ornaments, characterized in that, The soft transparent MABS material comprises the following raw materials by weight parts: 80-100 parts of MABS resin, 5-10 parts of ABS resin, 4-10 parts of phthalic acid diester, 10-40 parts of polyethylene glycol fatty acid ester, 3-7 parts of thermoplastic elastomer POE, 1-5 parts of tris(2,4-di-tert-butylphenyl) phosphite, 5-10 parts of nano calcium carbonate powder, 10-30 parts of nano titanium dioxide powder.

2. The soft and transparent MABS material for beauty industry ornaments according to claim 1, characterized in that, The soft transparent MABS material comprises the following raw materials by weight parts: 85-95 parts of MABS resin, 7-8 parts of ABS resin, 5-7 parts of phthalic acid diester, 15-28 parts of polyethylene glycol fatty acid ester, 5-6 parts of thermoplastic elastomer POE, 2-4 parts of tris(2,4-di-tert-butylphenyl) phosphite, 7-8 parts of nano calcium carbonate powder, 14-24 parts of nano titanium dioxide powder.

3. The soft transparent MABS material applied to beauty industry ornaments according to claim 1 or 2, characterized in that, The mass ratio of phthalic acid diester to polyethylene glycol fatty acid ester is 1:(3-4).

4. A soft transparent MABS material for beauty industry ornaments according to any one of claims 1 to 3, characterized in that, The particle size of the nano calcium carbonate powder is 300-500 nm, and the particle size of the nano titanium dioxide powder is 100-200 nm.

5. The soft transparent MABS material for beauty industry ornaments according to claim 4, characterized in that, The mass ratio of the nano calcium carbonate powder to the nano titanium dioxide powder is 1:(2-3).

6. A soft transparent MABS material for beauty industry ornaments according to any one of claims 1 to 5, characterized in that, The light transmittance of the soft transparent MABS material is ≥91%; the Shore hardness is 50-60 HA.

7. A soft transparent MABS material for beauty industry ornaments according to any one of claims 1 to 6, characterized in that, The soft transparent MABS material may further include color masterbatch.

8. A preparation method of the soft transparent ABS material applied to beauty industry ornaments as described in any one of claims 1-7, specifically comprising the following steps: (1) Mix the MABS resin, ABS resin, phthalic acid diester, polyethylene glycol fatty acid ester, thermoplastic elastomer POE, and tris(2,4-di-tert-butylphenyl) phosphite evenly according to the weight part ratio; (2) Feed the mixture obtained in step (1) through the main feeder, and feed the nano calcium carbonate powder and nano titanium dioxide powder through the side feeder, and melt, mix, extrude, and pelletize through a twin-screw extruder; thus obtaining the soft transparent ABS material.

9. The preparation method of a soft and transparent MABS material applied to beauty industry ornaments according to claim 8, characterized in that, The length-diameter ratio of the twin-screw extruder is (45-50):1, and the screw rotation speed control is set at 300-400 r / min.

10. The preparation method of a soft and transparent MABS material applied to beauty industry ornaments according to claim 8 or 9, characterized in that, The set temperature of the twin-screw extruder is: the first section: 180-200 °C, the second section: 185-205 °C, the third section: 190-210 °C, the fourth section: 195-215 °C, the fifth section: 200-220 °C, the sixth section: 190-210 °C, the seventh section: 190-210 °C, the eighth section: 190-210 °C, the ninth section: 195-215 °C, the 10th section: 200-220 °C, the head: 240-260 °C.

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