TPEE synthetic brush filaments and methods for making the same

Abstract

The present application relates to the field of thermoplastic elastomer material, in particular to a kind of TPEE synthetic brush wire and preparation method thereof, TPEE synthetic brush wire according to weight fraction, it includes: 55-75 parts TPEE resin, 25-45 parts polyester resin, 5-10 parts compatilizer, 8-16 parts modified polysiloxane, 12-24 parts plasticizer, 1-3 parts lubricant, 0.3-1 parts antioxidant and 0.6-1.2 parts stabilizer.The present application uses TPEE resin and polyester resin as main raw material, adds compatilizer, modified polysiloxane, plasticizer as auxiliary raw material, additionally still adds lubricant, antioxidant and stabilizer as additive, and the brush wire prepared has not only the advantages of suitable soft and hard rigidity and high strength, but also has good bacteriostatic performance.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of thermoplastic elastomer materials, in particular to a TPEE synthetic brush wire and a preparation method thereof. BACKGROUND

[0002] Thermoplastic polyester elastomer (TPEE) is also known as polyester rubber, which is a linear block copolymer containing PBT (polybutylene terephthalate) polyester hard segment and aliphatic polyester or polyether soft segment. TPEE has excellent elasticity of rubber and easy processability of thermoplastic plastic, and its hardness can be adjusted, so it is a new variety of thermoplastic elastomer that attracts much attention. Polyester elastomer material is usually used to make toothbrushes. This material has excellent elasticity, wear resistance and aging resistance, and can adapt to the impact force and pressure received by the toothbrush during use.

[0003] Conventional PA (polyamide) or polyester (PBT) brush wires are basically hard materials, and the harder the material, the poorer the bending modulus performance after being made into a brush wire. When repeatedly rubbed with teeth for cleaning, long-term fatigue bending deformation will cause the hair to burst. Although the elastic modulus and resilience of TPEE are slightly better than those of nylon (PA) and polyester (PBT) traditional brush wire materials, they can recover to the original state more quickly under low strain conditions (such as repeated bending during brushing), but the softness and rigidity of the TPEE brush wire on the market are still not flexible enough, and the skin friendliness is poor, the strength is insufficient, and the curling state is easily caused after bending and twisting under pressure. When used on toothbrush wires, if the rigidity is slightly large, the elasticity is insufficient, not only the gums are injured, but also the tooth gaps are difficult to clean, and they are easily deformed and damaged in the long-term use. Therefore, there is a need for a TPEE brush wire with appropriate softness, rigidity and high strength on the market. SUMMARY

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

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

[0006] In a first aspect, the present application provides a TPEE synthetic brush wire, which comprises, by weight:

[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 part 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℃, 2.16 kg), and the polyether mass content is 30%-60%.

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

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

[0011] S1, respectively, take the mercapto polysiloxane and limonene into the toluene solvent, and introduce nitrogen as the protective gas, and after fully stirring and uniform, a mixed solution is obtained;

[0012] S2, after adding a photosensitizer into the mixed solution, it is irradiated under ultraviolet light, and during the process, it is stirred at a speed of 100-200 rpm, and after reaction treatment for 0.8-2.4 h, the solvent is removed by rotary evaporation, and after washing with water for three times, vacuum drying is carried out, and the modified polysiloxane is obtained.

[0013] More preferably, in S1, the mass-volume ratio of mercapto polysiloxane, 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 addition amount is 1%-6% of the mass of the mercapto polysiloxane.

[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, acetyl tributyl citrate. More preferably, it is acetyl tributyl citrate.

[0016] Preferably, the lubricant is at least one of stearic acid, calcium stearate, zinc stearate, paraffin. More preferably, it is 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, PP-g-GMA; more preferably, it is PP-g-GMA, and the grafting rate is 1%-1.5%, and the density is 0.90-0.92 g / cm 3 , and the melt flow rate is 35-45 g / 10 min (190℃ / 2.16 kg).

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

[0019] Preferably, the stabilizer is a phosphite stabilizer, in particular at least one of triphenyl phosphite, tris(2,4-di-tert-butylphenyl) phosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite. More preferably, it is tris(2,4-di-tert-butylphenyl) phosphite.

[0020] Preferably, the preparation process of the mercapto polysiloxane comprises:

[0021] After the 3-mercaptopropyl triethoxysilane and the hydroxyl silicone oil are weighed into the deionized water and stirred uniformly, hydrochloric acid solution is added dropwise, and after stirring at room temperature for 1-3 h, the temperature is raised to 60-80 DEG C, and the reaction is kept for 3-6 h. After the reaction is completed, saturated sodium bicarbonate solution is added dropwise to the reaction system until it is neutral, and then it is washed with alcohol for at least three times, and vacuum dried to obtain the mercapto polysiloxane.

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

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

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

[0025] In the second aspect, the application provides a preparation method of TPEE synthetic brush filaments, comprising the following steps:

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

[0027] Step 2, blend the raw materials into an extruder, heat to 240-260 DEG C until melting, mix uniformly, and extrude into filamentous materials;

[0028] Step 3, stretch and shape the filamentous materials, the stretching multiple is 3-8 times, the shaping temperature is 160-180 DEG C, then cool and wind, to obtain the TPEE synthetic brush filaments.

[0029] The application has the following beneficial effects:

[0030] 1. This invention prepares a TPEE synthetic brush bristle, using TPEE resin and polyester resin as the main raw materials, and adding compatibilizer, modified polysiloxane, and plasticizer as auxiliary raw materials. In addition, lubricant, antioxidant and stabilizer are added as additives. The prepared brush bristle not only has the advantages of suitable softness and hardness and high strength, but also has good antibacterial properties.

[0031] 2. In this invention, TPEE resin and polyester resin are designed with a unique mixing ratio, which can simultaneously possess a certain degree of rigidity and toughness. With the introduction of modified polysiloxane and plasticizer, the toughness performance can be significantly improved while ensuring high rigidity. As a result, the bristles made from this material not only have a better bending rate, but are also less prone to fraying.

[0032] 3. Modified polysiloxane is prepared by using mercaptopolysiloxane and limonene as reactants through a ClickChemistry reaction of mercapto-double bonds. The resulting product contains groups such as thioether and siloxane, which have good performance in adjusting the strength and toughness of brush bristle materials, and can also improve their antibacterial performance. Detailed Implementation

[0033] The technical solution of the present invention is illustrated below through specific examples. It should be understood that the one or more method steps mentioned in the present invention do not preclude the existence of other method steps before or after the combined steps, or the insertion of other method steps between these explicitly mentioned steps; it should also be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the present invention. Furthermore, unless otherwise stated, the numbering of each method step is merely a convenient tool for identifying each method step, and not for limiting the order of the method steps or defining the scope of the present invention. Changes or adjustments to their relative relationships, without substantially altering the technical content, should also be considered within the scope of the present invention.

[0034] To better understand the above technical solutions, exemplary embodiments of the present invention are described in more detail below. While 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 to the embodiments set forth herein. Rather, these embodiments are provided to enable a more thorough understanding of the present invention and to fully convey the scope of the invention to those skilled in the art.

[0035] The present invention will be further described below with reference to the following embodiments.

[0036] Example 1

[0037] A type of TPEE synthetic brush bristles, by weight, comprises:

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

[0040] The preparation method of the modified polysiloxane comprises the following steps:

[0041] S1, 1g of 3-mercaptopropyl triethoxysilane and 0.4g of hydroxyl silicone oil (hydroxyl mass content is 3.2%, weight average molecular weight is 1000) are mixed into 15mL of deionized water, after being fully stirred and uniformly mixed, 0.5mol / L hydrochloric acid solution is added dropwise, the dropwise amount is 0.4% of the mass of deionized water, after being stirred at room temperature for 2h, the temperature is raised to 70℃, and the reaction is kept for 4h, after the reaction is completed, saturated sodium bicarbonate solution is added dropwise to the reaction system until it is neutral, then it is washed with alcohol at least three times, and vacuum dried to obtain mercapto polysiloxane;

[0042] S2, 1g of mercapto polysiloxane and 0.21g of limonene are respectively weighed into 15mL of toluene solvent, nitrogen gas is introduced as a protective gas, and after being fully stirred and uniformly mixed, a mixed solution is obtained;

[0043] S3, a photosensitizer benzoin dimethyl ether is added to the mixed solution, the addition amount is 3% of the mass of mercapto polysiloxane, and then it is placed under ultraviolet light for irradiation treatment, during which it is stirred at a speed of 150rpm, after being reacted for 1.6h, the solvent is removed by rotary evaporation, it is washed with water three times, and then vacuum dried to obtain modified polysiloxane.

[0044] The preparation method of the TPEE synthetic brush filament comprises the following steps:

[0045] Step 1, respectively, TPEE resin, polyester resin, compatibilizer, modified polysiloxane, plasticizer, lubricant, antioxidant and stabilizer, drying in the drying oven to moisture content less than 0.1%;

[0046] Step 2, the raw materials are blended into the extruder, heated to 250℃ to melt, mixed evenly, extruded into a filament;

[0047] Step 3, the filament is stretched and shaped, the stretching ratio is 5 times, the shaping temperature is 170℃, then cooled and wound, to obtain the TPEE synthetic brush filament.

[0048] Example 2

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

[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] 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, the density is 1.36g / cm 3 , and the melt flow rate is 12.3g / 10min (250℃, 2.16kg). The lubricant is stearic acid. The compatibilizer is EVA. The plasticizer is epoxy 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 TPEE synthetic brush filament, comprising the following steps:

[0053] Step 1, respectively, TPEE resin, polyester resin, compatibilizer, modified polysiloxane, plasticizer, lubricant, antioxidant and stabilizer, drying in the drying oven to moisture content less than 0.1%;

[0054] Step 2, the raw materials are blended into the extruder, heated to 240℃ to melt, mixed evenly, extruded into a filament;

[0055] Step 3, the filament is stretched and shaped, the stretching ratio is 3 times, the shaping temperature is 160℃, then cooled and wound, to obtain the TPEE synthetic brush filament.

[0056] Example 3

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

[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] The density of the TPEE resin is 1.2 g / cm 3 , the melt flow rate is 8 g / 10 min (220℃, 2.16 kg), and the polyether mass content is 40%. The polyester resin is PBT, the density is 1.36 g / cm 3 , and the melt flow rate is 12.3 g / 10 min (250℃, 2.16 kg). 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 TPEE synthetic brush filament comprises the following steps:

[0061] Step 1, respectively, TPEE resin, polyester resin, compatibilizer, modified polysiloxane, plasticizer, lubricant, antioxidant and stabilizer are weighed and dried in a forced air drying oven to a water content of less than 0.1%;

[0062] Step 2, the raw materials are blended into the extruder, heated to 260℃ to melt, then mixed uniformly, and extruded into a filament;

[0063] Step 3, the filament is stretched and shaped, the stretching ratio is 8 times, the shaping temperature is 180℃, then cooled and wound, to obtain the TPEE synthetic brush filament.

[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] The preparation method of the modified polysiloxane comprises:

[0067] S1, 1g of 3-mercaptopropyl triethoxysilane and 0.2g of hydroxyl silicone oil (hydroxyl mass content is 3.2%, weight average molecular weight is 1000) are mixed into 10mL of deionized water, stirred uniformly, then 0.1mol / L hydrochloric acid solution is added dropwise, the amount of deionized water is 0.2%, stirred at room temperature for 1h, then heated to 60℃, and reacted for 3h, after the reaction is completed, saturated sodium bicarbonate solution is added dropwise to the reaction system until it is neutral, then alcohol washed at least three times, and vacuum dried, to obtain mercapto polysiloxane.

[0068] S2, 1 g of mercaptan polysiloxane and 0.14 g of limonene were weighed respectively and added into 10 mL of toluene solvent, nitrogen was introduced as a protective gas, and after being fully stirred and uniformly mixed, a mixed solution was obtained;

[0069] S3, a photosensitizer, benzoin dimethyl ether, was added into the mixed solution, the amount of which was 1% of the mass of the mercaptan polysiloxane, and then the solution was treated under ultraviolet light, during which the solution was stirred at a speed of 100 rpm, after 0.8 h of reaction and treatment, the solvent was removed by rotary evaporation, the solution was washed with water for three times, and then vacuum drying was performed, thereby obtaining 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] The preparation method of the modified polysiloxane comprises the following steps:

[0073] S1, 1 g of 3-mercaptopropyl triethoxysilane and 0.6 g of hydroxyl silicone oil (the mass content of hydroxyl is 3.2%, and the weight average molecular weight is 1000) were weighed and mixed into 20 mL of deionized water, after being fully stirred and uniformly mixed, 1 mol / L hydrochloric acid solution was added dropwise, the amount of the dropwise addition was 0.8% of the mass of the deionized water, after being stirred at room temperature for 3 h, the temperature was increased to 80℃, and the reaction was kept for 6 h, after the reaction was completed, saturated sodium bicarbonate solution was added dropwise to the reaction system until the reaction system was neutral, then the reaction system was washed with alcohol for at least three times, and vacuum drying was performed, thereby obtaining mercaptan polysiloxane;

[0074] S2, 1 g of mercaptan polysiloxane and 0.28 g of limonene were weighed respectively and added into 20 mL of toluene solvent, nitrogen was introduced as a protective gas, and after being fully stirred and uniformly mixed, a mixed solution was obtained;

[0075] S3, a photosensitizer, benzoin dimethyl ether, was added into the mixed solution, the amount of which was 6% of the mass of the mercaptan polysiloxane, and then the solution was treated under ultraviolet light, during which the solution was stirred at a speed of 200 rpm, after 2.4 h of reaction and treatment, the solvent was removed by rotary evaporation, the solution was washed with water for three times, and then vacuum drying was performed, thereby obtaining 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 hydroxyl silicone oil.

[0078] Comparative example 2

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

[0080] Comparative Example 3

[0081] A TPEE synthetic brush filament, which is different from Example 1 only in that the modified polysiloxane is replaced by a mixture of mercaptosiloxane and limonene, the mass ratio of mercaptosiloxane and limonene is 1:0.21, and the preparation process of mercaptosiloxane 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 detected, the tensile strength detection referred to the standard GB / T 1040.1-2018, the bending modulus detection referred to the standard GB / T 9341-2008, the hardness detection referred to the standard GB / T 531-1999, and the antibacterial rate detection referred to the standard ISO 22196-2011, and the detection results are shown in Table 1:

[0083] Table 1 Performance detection results of different brush filament materials

[0084]

[0085] As can be seen from Table 1, the brush filament material prepared in Example 1 of the present application not only has high strength and hardness, but also can maintain good toughness, has the advantages of suitable soft and hard rigidity and high strength, and also has good antibacterial performance.

[0086] In the description of the present specification, the description of the terms "one embodiment", "some embodiments", "example", "specific example", or "some examples" and the like means that the specific features, structures, materials or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present application. In the present specification, the illustrative description of the above terms should not be understood as necessarily referring to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner. In addition, those skilled in the art can combine and combine different embodiments or examples described in the present specification.

[0087] Although the embodiments of the present application have been shown and described above, it should be understood that the above embodiments are exemplary and should not be construed as limiting the present application, and those skilled in the art can make changes, modifications, replacements and variations to the above embodiments within the scope of the present application.

Claims

1. A TPEE synthetic brush filament, characterized in that, According to the weight parts, comprising: 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 part of antioxidant and 0.6-1.2 parts of stabilizer; The preparation method of the modified polysiloxane comprises: S1, respectively, take the mercapto polysiloxane and limonene into the toluene solvent, and pass nitrogen as the protective gas, and after fully stirring and uniform, obtain the mixed solution; S2, after adding photosensitizer to the mixed solution, and then irradiating and treating under the ultraviolet light, and during the period, stirring at the speed of 100-200 rpm, and after reaction treatment of 0.8-2.4 h, removing the solvent by rotary evaporation, and after washing with water for three times, vacuum drying, obtain the modified polysiloxane.

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

3. The TPEE synthetic bristle of claim 1, wherein, In the S1, the mass-volume ratio of the mercapto polysiloxane, limonene and toluene is 1 g:(0.14-0.28) g:(10-20) mL.

4. The TPEE synthetic bristle of claim 1, wherein, In the S2, the photosensitizer is benzoin dimethyl ether, and the addition amount is 1%-6% of the mass of the mercapto polysiloxane.

5. The TPEE synthetic bristle of claim 1, wherein, The plasticizer is a bio-based plasticizer, specifically at least one of epoxy soybean oil, epoxy linseed oil, epoxy castor oil, epoxy sunflower oil, triethyl citrate, tributyl citrate, acetyl tributyl citrate.

6. The TPEE synthetic bristle of claim 1, wherein, The lubricant is at least one of stearic acid, calcium stearate, zinc stearate, paraffin.

7. The TPEE synthetic bristle of claim 1, wherein, The compatibilizer is one of EVA, POE-g-GMA, PP-g-GMA.

8. The TPEE synthetic bristle of claim 1, wherein, The antioxidant is a phenolic antioxidant, specifically at least one of antioxidant 1010, antioxidant 1076, antioxidant 2246; the stabilizer is a phosphate stabilizer, specifically at least one of triphenyl phosphite, tris(2,4-di-tert-butylphenyl) phosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite.

9. A process for the preparation of the TPEE synthetic bristle of claim 1, characterized in that, Comprising the following steps: Step 1, respectively, take the TPEE resin, polyester resin, compatibilizer, modified polysiloxane, plasticizer, lubricant, antioxidant and stabilizer, and dry in the air drying oven to the water content of less than 0.1%; Step 2, blend each raw material into the extruder, and after heating to 240-260℃ to melt, mix uniformly, and extrude into a filamentous material; Step 3, after stretching and setting the filamentous material, the stretching multiple is 3-8 times, and the setting temperature is 160-180℃, and then after cooling, wind up, and obtain the TPEE synthetic brush filament.

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