TPEE synthetic brush wire and preparation method thereof

Abstract

The invention relates to the field of thermoplastic elastomer materials, in particular to a TPEE synthetic brush wire and a preparation method thereof.The TPEE synthetic brush wire is prepared from, by weight, 55-75 parts of TPEE resin, 25-45 parts of polyester resin, 5-10 parts of compatilizer, 8-16 parts of modified polysiloxane, 12-24 parts of plasticizer, 1-3 parts of lubricant, 0.3-1 part of antioxidant and 0.6-1.2 parts of stabilizer. The TPEE resin and the polyester resin are used as main raw materials, the compatilizer, the modified polysiloxane and the plasticizer are added as auxiliary raw materials, and the lubricant, the antioxidant and the stabilizer are added as additives, so that the prepared brush wire not only has the advantages of proper hardness and rigidity and high strength, but also has better antibacterial performance.

Description

Technical Field

[0001] The invention relates to the field of thermoplastic elastomer materials, and in particular to TPEE synthetic brush filaments and a preparation method thereof. Background Art

[0002] Thermoplastic polyester elastomer (TPEE), also known as polyester rubber, is a type of linear block copolymer containing PBT (polybutylene terephthalate) polyester hard segment and aliphatic polyester or polyether soft segment. TPEE combines the excellent elasticity of rubber with the easy processing of thermoplastic plastics, with adjustable hardness and design freedom. It is a new type of thermoplastic elastomer that has attracted much attention. Polyester elastomer materials are usually used to make toothbrushes. This material has excellent elasticity, wear resistance and aging resistance, and can adapt to the impact and pressure that toothbrushes are subjected to during use.

[0003] Conventional PA (polyamide) or polyester (PBT) brush filaments are basically made of hard materials. The harder the material, the poorer the bending modulus performance after being made into brush filaments. When repeatedly rubbed against teeth for cleaning, long-term fatigue bending deformation will cause hair frying. Although TPEE's elastic modulus and resilience are slightly better than traditional brush filament materials such as nylon (PA) and polyester (PBT), and it can recover to its original state more quickly under low strain conditions (such as repeated bending when brushing teeth), the hardness and rigidity of TPEE brush filaments currently on the market are still not flexible enough in adjustment, and they have poor skin-friendliness and insufficient strength. They are easily curled after being bent and twisted under pressure. When used on toothbrush filaments, if the rigidity is slightly larger, the elasticity is insufficient, which not only hurts the gums but also makes it difficult to clean the gaps between teeth. It is easy to deform and damage during long-term use. Therefore, there is a need in the market for a TPEE brush filament with appropriate hardness and rigidity, high strength and not easy to damage. Summary of the invention

[0004] In view of the problems existing in the prior art, the purpose of the present invention is to provide a TPEE synthetic brush filament and a preparation method thereof.

[0005] The purpose of the present invention is achieved by adopting the following technical solutions:

[0006] In a first aspect, the present invention provides a TPEE synthetic brush filament, calculated by weight, comprising:

[0007] 55-75 parts of TPEE resin, 25-45 parts of polyester resin, 5-10 parts of compatibilizer, 8-16 parts of modified polysiloxane, 12-24 parts of plasticizer, 1-3 parts of lubricant, 0.3-1 parts of antioxidant and 0.6-1.2 parts of stabilizer.

[0008] Preferably, the density of the TPEE resin is 1.1-1.3 g / cm 3, the melt flow rate is 6-12 g / 10 min (220°C, 2.16 kg), and the polyether mass content is 30%-60%.

[0009] Preferably, the polyester resin is PET or PBT; more preferably PBT, with a density of 1.32-1.40 g / cm 3 , the melt flow rate is 8.2-16.4 g / 10 min (250°C, 2.16 kg).

[0010] Preferably, the preparation method of the modified polysiloxane comprises:

[0011] S1. Weigh mercaptopolysiloxane and limonene respectively, add them to toluene solvent, introduce nitrogen as protective gas, and stir thoroughly to obtain a mixed solution;

[0012] S2. After adding a photosensitizer to the mixed solution, the solution is irradiated under ultraviolet light while being stirred at a speed of 100-200 rpm. After reacting for 0.8-2.4 hours, the solvent is removed by rotary evaporation. The solution is washed with water three times and then dried in a vacuum to obtain a modified polysiloxane.

[0013] More preferably, in S1, the mass volume ratio of mercaptopolysiloxane, limonene and toluene is 1 g:(0.14-0.28) g:(10-20) mL.

[0014] More preferably, in S2, the photosensitizer is benzoin dimethyl ether, and the added amount is 1%-6% of the mass of mercaptopolysiloxane.

[0015] Preferably, the plasticizer is a bio-based plasticizer, specifically at least one of epoxidized soybean oil, epoxidized linseed oil, epoxidized castor oil, epoxidized sunflower oil, triethyl citrate, tributyl citrate, and acetyl tributyl citrate, more preferably acetyl tributyl citrate.

[0016] Preferably, the lubricant is at least one of stearic acid, calcium stearate, zinc stearate and paraffin, and more preferably a mixture of calcium stearate and paraffin in a mass ratio of 1.2-1.8:1.

[0017] Preferably, the compatibilizer is one of EVA, POE-g-GMA, and PP-g-GMA; more preferably PP-g-GMA, with a grafting rate of 1%-1.5% and a density of 0.90-0.92 g / cm 3 , the melt flow rate is 35-45g / 10min (190℃ / 2.16kg).

[0018] Preferably, the antioxidant is a phenolic antioxidant, specifically at least one of antioxidant 1010, antioxidant 1076, and antioxidant 2246. More preferably, antioxidant 1076 is used.

[0019] Preferably, the stabilizer is a phosphate stabilizer, specifically at least one of triphenyl phosphite, tris(2,4-di-tert-butylphenyl)phosphite, and bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, more preferably tris(2,4-di-tert-butylphenyl)phosphite.

[0020] Preferably, the preparation process of the mercaptopolysiloxane comprises:

[0021] Weigh 3-mercaptopropyltriethoxysilane and hydroxy silicone oil and mix them in deionized water. After fully stirring, add hydrochloric acid solution dropwise. After stirring at room temperature for 1-3 hours, heat to 60-80°C and keep warm for 3-6 hours. After the reaction is completed, add saturated sodium bicarbonate solution dropwise until the reaction system is neutral, then wash with alcohol for at least three times and dry in vacuo to obtain mercaptopolysiloxane.

[0022] More preferably, the hydroxyl content of the hydroxyl silicone oil is 3.2% and the weight average molecular weight is 1000.

[0023] More preferably, the mass volume ratio of 3-mercaptopropyltriethoxysilane, hydroxy silicone oil and deionized water is 1 g: (0.2-0.6) g: (10-20) mL.

[0024] More preferably, the concentration of the hydrochloric acid solution is 0.1-1 mol / L, and the amount added is 0.2%-0.8% of the mass of the deionized water.

[0025] In a second aspect, the present invention provides a method for preparing TPEE synthetic brush filaments, comprising the following steps:

[0026] Step 1, weighing TPEE resin, polyester resin, compatibilizer, modified polysiloxane, plasticizer, lubricant, antioxidant and stabilizer respectively, and drying them in a forced air drying oven until the water content is less than 0.1%;

[0027] Step 2, blending the raw materials into an extruder, heating to 240-260° C. until they are melted, mixing them evenly, and extruding them into filaments;

[0028] Step 3, stretching and shaping the filaments, with the stretching ratio being 3-8 times and the shaping temperature being 160-180°C, and then winding up after cooling to obtain TPEE synthetic brush filaments.

[0029] The beneficial effects of the present invention are:

[0030] 1. The present invention prepares a TPEE synthetic brush filament, which uses TPEE resin and polyester resin as main raw materials, adds a compatibilizer, modified polysiloxane, and a plasticizer as auxiliary raw materials, and further adds a lubricant, an antioxidant, and a stabilizer as additives. The prepared brush filament not only has the advantages of suitable hardness and rigidity and high strength, but also has good antibacterial performance.

[0031] 2. The TPEE resin and polyester resin in the present invention are designed according to a unique mixing ratio, which can have certain rigidity and toughness at the same time. With the introduction of modified polysiloxane and plasticizer, the toughness performance can be significantly improved on the basis of ensuring high rigidity, so that the brush wire made of it not only has a better curvature but also is not easy to fry.

[0032] 3. Modified polysiloxane is prepared by using mercapto polysiloxane and limonene as reactants through the ClickChemistry reaction of mercapto-double bonds. The obtained product contains thioether groups and siloxane groups, which have good performance in adjusting the strength and toughness of brush filament materials, and can also improve its antibacterial performance. DETAILED DESCRIPTION

[0033] The technical solution of the present invention is described below through specific examples. It should be understood that the one or more method steps mentioned in the present invention do not exclude the existence of other method steps before and after the combination step or the insertion of other method steps between these explicitly mentioned steps; it should also be understood that these embodiments are only used to illustrate the present invention and are not used to limit the scope of the present invention. Moreover, unless otherwise specified, the numbering of each method step is only a convenient tool for identifying each method step, and is not intended to limit the order of arrangement of each method step or to limit the scope of the present invention. The change or adjustment of the relative relationship thereof shall also be regarded as the scope of the present invention without substantially changing the technical content.

[0034] In order to better understand the above technical scheme, the exemplary embodiments of the present invention are described in more detail below. Although exemplary embodiments of the present invention are shown, it should be understood that the present invention can be implemented in various forms and should not be limited by the embodiments set forth herein. On the contrary, these embodiments are provided in order to enable a more thorough understanding of the present invention and to enable the scope of the present invention to be fully communicated to those skilled in the art.

[0035] The present invention will be further described below in conjunction with the following examples.

[0036] Example 1

[0037] A TPEE synthetic brush filament, calculated by weight, comprising:

[0038] 65 parts of TPEE resin, 35 parts of polyester resin, 8 parts of compatibilizer, 12 parts of modified polysiloxane, 18 parts of plasticizer, 2 parts of lubricant, 0.6 parts of antioxidant and 1 part of stabilizer.

[0039] Wherein, the density of the TPEE resin is 1.2g / cm 3 The melt flow rate is 8g / 10min (220℃, 2.16kg), and the polyether mass content is 40%. The polyester resin is PBT, with a density of 1.36g / cm 3 The melt flow rate is 12.3 g / 10 min (250°C, 2.16 kg). The lubricant is a mixture of calcium stearate and paraffin in a mass ratio of 1.5:1. The compatibilizer is PP-g-GMA, with a grafting rate of 1.2% and a density of 0.91 g / cm 3 , the melt flow rate is 40g / 10min (190℃ / 2.16kg). The plasticizer is tributyl acetyl citrate. The antioxidant is antioxidant 1076. The stabilizer is tris(2,4-di-tert-butylphenyl)phosphite.

[0040] Wherein, the preparation method of the modified polysiloxane comprises:

[0041] S1. Weigh 1 g of 3-mercaptopropyltriethoxysilane and 0.4 g of hydroxy silicone oil (hydroxyl mass content of 3.2%, weight average molecular weight of 1000) and mix them in 15 mL of deionized water. After fully stirring, add 0.5 mol / L hydrochloric acid solution in an amount of 0.4% of the mass of deionized water. Stir at room temperature for 2 h, heat to 70°C, and keep warm for 4 h. After the reaction is completed, add saturated sodium bicarbonate solution until the reaction system is neutral, then wash with alcohol at least three times, and dry in vacuo to obtain mercaptopolysiloxane.

[0042] S2, weighing 1 g of mercaptopolysiloxane and 0.21 g of limonene respectively, adding them to 15 mL of toluene solvent, introducing nitrogen as a protective gas, and stirring thoroughly to obtain a mixed solution;

[0043] S3. Add photosensitizer benzoin dimethyl ether to the mixed solution in an amount of 3% of the mass of the mercaptopolysiloxane, and then place it under ultraviolet light for irradiation while stirring at a speed of 150 rpm. After the reaction treatment for 1.6 hours, remove the solvent by rotary evaporation, wash with water three times, and vacuum dry to obtain modified polysiloxane.

[0044] The preparation method of the above-mentioned TPEE synthetic brush filaments comprises the following steps:

[0045] Step 1, weighing TPEE resin, polyester resin, compatibilizer, modified polysiloxane, plasticizer, lubricant, antioxidant and stabilizer respectively, and drying them in a forced air drying oven until the water content is less than 0.1%;

[0046] Step 2, blending the raw materials into an extruder, heating to 250° C. until they are melted, mixing them evenly, and extruding them into filaments;

[0047] Step 3, stretching and shaping the filament with a stretching ratio of 5 times and a shaping temperature of 170°C, and then winding it after cooling to obtain TPEE synthetic brush filaments.

[0048] Example 2

[0049] A TPEE synthetic brush filament, calculated by weight, comprising:

[0050] 55 parts of TPEE resin, 25 parts of polyester resin, 5 parts of compatibilizer, 8 parts of modified polysiloxane, 12 parts of plasticizer, 1 part of lubricant, 0.3 parts of antioxidant and 0.6 parts of stabilizer.

[0051] Wherein, the density of the TPEE resin is 1.2g / cm 3 The melt flow rate is 8g / 10min (220℃, 2.16kg), and the polyether mass content is 40%. The polyester resin is PBT, with a density of 1.36g / cm 3 , the melt flow rate is 12.3 g / 10 min (250° C., 2.16 kg). The lubricant is stearic acid. The compatibilizer is EVA. The plasticizer is epoxidized soybean oil. The antioxidant is antioxidant 1010. The stabilizer is triphenyl phosphite. The preparation method of the modified polysiloxane is the same as that of Example 1.

[0052] The preparation method of the above-mentioned TPEE synthetic brush filaments comprises the following steps:

[0053] Step 1, weighing TPEE resin, polyester resin, compatibilizer, modified polysiloxane, plasticizer, lubricant, antioxidant and stabilizer respectively, and drying them in a forced air drying oven until the water content is less than 0.1%;

[0054] Step 2, blending the raw materials into an extruder, heating to 240° C. until they are melted, mixing them evenly, and extruding them into filaments;

[0055] Step 3, stretching and shaping the filament with a stretching ratio of 3 times and a shaping temperature of 160°C, and then winding it after cooling to obtain TPEE synthetic brush filaments.

[0056] Example 3

[0057] A TPEE synthetic brush filament, calculated by weight, comprising:

[0058] 75 parts of TPEE resin, 45 parts of polyester resin, 10 parts of compatibilizer, 16 parts of modified polysiloxane, 24 parts of plasticizer, 3 parts of lubricant, 1 part of antioxidant and 1.2 parts of stabilizer.

[0059] Wherein, the density of the TPEE resin is 1.2g / cm 3 The melt flow rate is 8g / 10min (220℃, 2.16kg), and the polyether mass content is 40%. The polyester resin is PBT, with a density of 1.36g / cm 3 , the melt flow rate is 12.3g / 10min (250℃, 2.16kg). The lubricant is zinc stearate. The compatibilizer is POE-g-GMA. The plasticizer is triethyl citrate. The antioxidant is antioxidant 2246. The stabilizer is bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite. The preparation method of the modified polysiloxane is the same as that of Example 1.

[0060] The preparation method of the above-mentioned TPEE synthetic brush filaments comprises the following steps:

[0061] Step 1, weighing TPEE resin, polyester resin, compatibilizer, modified polysiloxane, plasticizer, lubricant, antioxidant and stabilizer respectively, and drying them in a forced air drying oven until the water content is less than 0.1%;

[0062] Step 2, blending the raw materials into an extruder, heating to 260° C. until they are melted, mixing them evenly, and extruding them into filaments;

[0063] Step 3, stretching and shaping the filament with a stretching ratio of 8 times and a shaping temperature of 180°C, and then winding it after cooling to obtain TPEE synthetic brush filaments.

[0064] Example 4

[0065] A TPEE synthetic brush filament, which is different from Example 1 only in that the preparation method of the modified polysiloxane is different.

[0066] Wherein, the preparation method of the modified polysiloxane comprises:

[0067] S1. Weigh 1 g of 3-mercaptopropyltriethoxysilane and 0.2 g of hydroxy silicone oil (hydroxyl mass content of 3.2%, weight average molecular weight of 1000) and mix them into 10 mL of deionized water. After fully stirring, add 0.1 mol / L hydrochloric acid solution in an amount of 0.2% of the mass of deionized water. Stir at room temperature for 1 h, heat to 60° C., and keep warm for 3 h. After the reaction is completed, add saturated sodium bicarbonate solution until the reaction system is neutral, then wash with alcohol at least three times, and dry in vacuo to obtain mercaptopolysiloxane.

[0068] S2, weighing 1 g of mercaptopolysiloxane and 0.14 g of limonene respectively, adding them to 10 mL of toluene solvent, introducing nitrogen as a protective gas, stirring thoroughly to obtain a mixed solution;

[0069] S3. Add photosensitizer benzoin dimethyl ether to the mixed solution in an amount of 1% of the mass of the mercaptopolysiloxane, and then place it under ultraviolet light for irradiation treatment while stirring at a speed of 100 rpm. After the reaction treatment for 0.8 h, remove the solvent by rotary evaporation, wash with water three times, and vacuum dry to obtain modified polysiloxane.

[0070] Example 5

[0071] A TPEE synthetic brush filament, which is different from Example 1 only in that the preparation method of the modified polysiloxane is different.

[0072] Wherein, the preparation method of the modified polysiloxane comprises:

[0073] S1. Weigh 1 g of 3-mercaptopropyltriethoxysilane and 0.6 g of hydroxy silicone oil (the mass content of hydroxyl group is 3.2% and the weight average molecular weight is 1000) and mix them into 20 mL of deionized water. After fully stirring, add 1 mol / L hydrochloric acid solution dropwise in an amount of 0.8% of the mass of deionized water. Stir at room temperature for 3 h, heat to 80° C., and keep warm for 6 h. After the reaction is completed, add saturated sodium bicarbonate solution dropwise until the reaction system is neutral, then wash with alcohol for at least three times, and dry in vacuo to obtain mercaptopolysiloxane.

[0074] S2, weighing 1 g of mercaptopolysiloxane and 0.28 g of limonene respectively, adding them to 20 mL of toluene solvent, introducing nitrogen as a protective gas, and stirring thoroughly to obtain a mixed solution;

[0075] S3. Add photosensitizer benzoin dimethyl ether to the mixed solution in an amount of 6% of the mass of the mercaptopolysiloxane, and then place it under ultraviolet light for irradiation treatment while stirring at a speed of 200 rpm. After the reaction treatment for 2.4 hours, remove the solvent by rotary evaporation, wash with water three times, and vacuum dry to obtain modified polysiloxane.

[0076] Comparative Example 1

[0077] A TPEE synthetic brush filament, which is different from Example 1 only in that the modified polysiloxane is replaced by hydroxy silicone oil.

[0078] Comparative Example 2

[0079] A TPEE synthetic brush filament, which differs from Example 1 only in that the modified polysiloxane is replaced by mercaptopolysiloxane, and the preparation process is the same as that of Example 1.

[0080] Comparative Example 3

[0081] A TPEE synthetic brush filament, which differs from Example 1 only in that the modified polysiloxane is replaced by a mixture of mercaptopolysiloxane and limonene, the mass ratio of mercaptopolysiloxane to limonene is 1:0.21, and the preparation process of mercaptopolysiloxane is the same as that of Example 1.

[0082] The properties of the brush filament materials prepared in Example 1 and Comparative Examples 1-3 were tested. The tensile strength test reference standard was GB / T 1040.1-2018, the flexural modulus test reference standard was GB / T 9341-2008, the hardness test reference standard was GB / T 531-1999, and the antibacterial rate test reference standard was ISO 22196-2011. The test results are shown in Table 1:

[0083] Table 1 Performance test results of different brush materials

[0084]

[0085] It can be seen from Table 1 that the brush filament material prepared in Example 1 of the present invention not only has high strength and hardness, but also can maintain good toughness, has the advantages of suitable hardness and softness and high strength, and can also have good antibacterial performance.

[0086] In the description of this specification, the description with reference to the terms "one embodiment", "some embodiments", "example", "specific example", or "some examples" etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representation of the above terms should not be understood as necessarily being directed to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described may be combined in any one or more embodiments or examples in a suitable manner. In addition, those skilled in the art may combine and combine different embodiments or examples described in this specification.

[0087] Although the embodiments of the present invention have been shown and described above, it is to be understood that the above embodiments are exemplary and are not to be construed as limitations of the present invention. A person skilled in the art may change, modify, replace and vary the above embodiments within the scope of the present invention.

Claims

1. A TPEE synthetic brush filament, characterized in that: Calculated by weight, including: 55-75 parts of TPEE resin, 25-45 parts of polyester resin, 5-10 parts of compatibilizer, 8-16 parts of modified polysiloxane, 12-24 parts of plasticizer, 1-3 parts of lubricant, 0.3-1 parts of antioxidant and 0.6-1.2 parts of stabilizer.

2. A TPEE synthetic brush filament according to claim 1, characterized in that: The density of the TPEE resin is 1.1-1.3 g / cm 3 , the melt flow rate is 6-12 g / 10 min at 220° C. and 2.16 kg, the mass content of the polyether is 30%-60%; and the polyester resin is PET or PBT.

3. A TPEE synthetic brush filament according to claim 1, characterized in that: The preparation method of the modified polysiloxane comprises: S1. Weigh mercaptopolysiloxane and limonene respectively, add them to toluene solvent, introduce nitrogen as protective gas, and stir thoroughly to obtain a mixed solution; S2. After adding a photosensitizer to the mixed solution, the solution is irradiated under ultraviolet light while being stirred at a speed of 100-200 rpm. After reacting for 0.8-2.4 hours, the solvent is removed by rotary evaporation. The solution is washed with water three times and then dried in a vacuum to obtain a modified polysiloxane.

4. A TPEE synthetic brush filament according to claim 3, characterized in that: In the S1, the mass volume ratio of mercaptopolysiloxane, limonene and toluene is 1 g: (0.14-0.28) g: (10-20) mL.

5. A TPEE synthetic brush filament according to claim 3, characterized in that: In the S2, the photosensitizer is benzoin dimethyl ether, and the added amount is 1%-6% of the mass of mercaptopolysiloxane.

6. The TPEE synthetic brush filament according to claim 1, characterized in that: The plasticizer is a bio-based plasticizer, specifically at least one of epoxidized soybean oil, epoxidized linseed oil, epoxidized castor oil, epoxidized sunflower oil, triethyl citrate, tributyl citrate, and acetyl tributyl citrate.

7. The TPEE synthetic brush filament according to claim 1, characterized in that: The lubricant is at least one of stearic acid, calcium stearate, zinc stearate and paraffin.

8. The TPEE synthetic brush filament according to claim 1, characterized in that: The compatibilizer is one of EVA, POE-g-GMA and PP-g-GMA.

9. The TPEE synthetic brush filament according to claim 1, characterized in that: The antioxidant is a phenolic antioxidant, specifically at least one of antioxidant 1010, antioxidant 1076, and antioxidant 2246; the stabilizer is a phosphate stabilizer, specifically at least one of triphenyl phosphite, tris(2,4-di-tert-butylphenyl)phosphite, and bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite.

10. A method for preparing the TPEE synthetic brush filament according to claim 1, characterized in that: The following steps are involved: Step 1, weighing TPEE resin, polyester resin, compatibilizer, modified polysiloxane, plasticizer, lubricant, antioxidant and stabilizer respectively, and drying them in a forced air drying oven until the water content is less than 0.1%; Step 2, blending the raw materials into an extruder, heating to 240-260° C. until they are melted, mixing them evenly, and extruding them into filaments; Step 3, stretching and shaping the filaments, with the stretching ratio being 3-8 times and the shaping temperature being 160-180°C, and then winding up after cooling to obtain TPEE synthetic brush filaments.

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