A high-toughness and scratch-resistant glasses frame and preparation method thereof

Abstract

The present application relates to the field of thermoplastic elastomer processing, and more specifically, it relates to a high-toughness and scratch-resistant eyeglass frame and a preparation method thereof. It is prepared from the following raw materials in weight percentage: polytetramethylene ether glycol, terephthalic acid, 1,4-butanediol, processing aid, catalyst, modifier; the modifier is composed of silicone masterbatch, hydroxyl toughening agent, inorganic filler, and hexamethylene diisocyanate trimer; the hydroxyl toughening agent is hydroxyl-modified ternary chloroacetic acid resin and / or branched hydroxyl polyester. By using silicone masterbatch, hydroxyl toughening agent, inorganic filler, and hexamethylene diisocyanate trimer as modifiers, TPEE is modified together to further enhance its toughness, scratch resistance, and chemical resistance. Therefore, the obtained eyeglass frame is not prone to breakage, scratching, wear, creep, etc. during use, and is not easily eroded by sweat, chemicals, etc., thereby improving the beauty and durability of the eyeglass frame.

Description

Technical Field

[0001] The present application relates to the field of thermoplastic elastomer processing, and more specifically, to a high-toughness and scratch-resistant eyeglass frame and a preparation method thereof. Background Art

[0002] The main structure of the spectacle frame includes temples, lens rings, nose bridge, nose pads, and stumps. The spectacle lenses are installed in the lens rings of the spectacle frame to form the glasses. The spectacle frame mainly supports the spectacle lenses. The spectacle frame with beautiful appearance can also play a role in aesthetics. The materials of the spectacle frame are mainly metal, plastic or resin, natural materials, etc. Although the current metal spectacle frames have good strength, they are easy to rust. There are electroplating processes for coating, but when used for a long time, human sweat and chemicals are easy to corrode the spectacle frames, causing the coating on the metal spectacle frames to fall off easily, affecting the beauty of the spectacle frames.

[0003] Plastic or resin has the advantages of good corrosion resistance, easy processing, light weight, etc., so it is widely used in the production of eyeglass frames. However, plastic eyeglass frames are easy to break, especially for children. Children are prone to drop their glasses during use, resulting in cracks, scratches, breaks, wear and tear on the frames, thus reducing the beauty and durability of the frames.

[0004] Based on the above problems, thermoplastic polyester elastomer (TPEE) is currently used to produce eyeglass frames. 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 has both the excellent elasticity of rubber and the easy processing of thermoplastics, and its hardness is adjustable. Therefore, the eyeglass frames produced have better drop resistance, which reduces the possibility of breakage, scratches, and wear during use. When TPEE materials are used to produce eyeglass frames, they are usually formed into a one-piece frame and temples, and the frame and temples are hinged to form the frame, and the frame includes a lens ring, nose bridge, nose pads, and studs.

[0005] However, with the advancement of technology, more and more people have higher requirements for the quality of eyeglass frames, especially for high-end eyeglass frames, such as the current half-frame, frameless and other types of eyeglass frames. Usually, one eyeglass frame can be adapted to multiple lenses. For myopic people, different lenses need to be replaced every once in a while, but the frames do not need to be replaced. Therefore, the appearance and durability of the eyeglass frames are required to be high. Although the eyeglass frames currently produced with TPEE can have better anti-fall performance, they are still prone to scratching, creep, corrosion and other phenomena during long-term use, which affects the appearance and durability of the glasses. Therefore, further research is needed. Summary of the invention

[0006] In order to improve the drop resistance of eyeglass frames, reduce the occurrence of scratching, creep corrosion and other phenomena after long-term use, and maintain better aesthetics and durability, the present application provides a high-toughness and scratch-resistant eyeglass frame and a preparation method thereof.

[0007] In a first aspect, a high-toughness and scratch-resistant eyeglass frame comprises a frame and two temples hinged to two sides of the frame, wherein the frame and the temples are made of the following raw materials in the following weight percentages:

[0008] Polytetramethylene glycol 22-38%

[0009] 1,4-Butanediol 18-30%

[0010] Terephthalic acid 22.5-3.49%

[0011] Catalyst 0.1-0.5%

[0012] Modifier 10-15%

[0013] The balance is processing aids;

[0014] The modifier consists of silicone masterbatch, hydroxy toughening agent, inorganic filler and hexamethylene diisocyanate trimer.

[0015] The hydroxy toughening agent is a hydroxy-modified ternary chloroacetic acid resin and / or a branched hydroxy polyester.

[0016] In the above technical solution, polytetramethylene ether glycol and terephthalic acid are used as polymerization monomers, and polymerization is carried out through the action of a catalyst. The generated TPEE has better flexibility, the added processing aid plays a role in assisting processing, and the modifier can further toughen and modify TPEE, so that the prepared eyeglass frame has better toughness and scratch resistance. Scratch resistance refers to both scratch resistance and wear resistance.

[0017] Specifically, in the modifier, hydroxyl-modified ternary chloroacetic acid resin and / or branched hydroxyl polyester are used as hydroxyl toughening agents, both of which contain hydroxyl functional groups and can react with the ester group in TPEE or form hydrogen bonds, thereby improving the compatibility of the raw material system, making the silicone masterbatch and the raw material system of TPEE fully mixed and uniform, and further increasing the crosslinking density of TPEE or forming an interpenetrating network structure, further improving the mechanical strength, toughness and chemical resistance of TPEE. The obtained eyeglass frame has better scratch resistance, wear resistance, drop resistance, sweat resistance and chemical corrosion resistance, and also has better creep resistance, reducing the creep of the eyeglass frame during use, which affects the stability of wearing glasses.

[0018] Hexamethylene diisocyanate trimer contains three isocyanate groups, which can react with the active hydrogen atoms in TPEE to increase the cross-linking density of TPEE, thereby improving its mechanical strength, toughness, chemical resistance and scratch resistance.

[0019] Silicone masterbatch has the characteristics of toughening, reducing friction coefficient, reducing internal stress, and improving processing efficiency. It can improve the wetting effect between resin and inorganic matter and increase the affinity of its surface. Therefore, silicone masterbatch is added to improve the compatibility of inorganic filler and TPEE raw material system, and cooperate with hydroxyl toughening agent and hexamethylene diisocyanate trimer to play a synergistic effect and have a better modification effect on TPEE, so that the obtained eyeglass frames have better toughness, scratch resistance and chemical resistance.

[0020] In summary, the present application uses silicone masterbatch, hydroxyl toughening agent, inorganic filler, and hexamethylene diisocyanate trimer as modifiers to jointly modify TPEE, thereby achieving better toughening, scratch resistance, and chemical resistance. Therefore, the resulting eyeglass frames are not prone to breakage, scratching, wear, creep, etc. during use, and are not easily eroded or corroded by sweat, chemicals, etc., thereby improving the appearance and durability of the eyeglass frames.

[0021] The high toughness in the present application refers to obtaining a higher elongation at break and tensile strength after adding a modifier, making it more tough, and obtaining better wear resistance, scratch resistance, drop resistance, and creep resistance.

[0022] When wearing glasses, the frames are constantly subjected to stress from the head, nose bridge and ears. Although these stresses are usually lower than the yield strength of the material, they may still cause creep if they continue for a long time. Creep can cause the shape and size of the frames to change, which in turn affects the wearing comfort. For example, the temples may become loose or tight, and the nose pads may no longer fit the bridge of the nose. Therefore, creep resistance is an important feature of glasses frames.

[0023] Preferably, the weight ratio of the silicone masterbatch, hydroxyl toughening agent, inorganic filler and hexamethylene diisocyanate trimer is (1-3): (1-2): (5-6): 1.

[0024] When the silicone masterbatch, hydroxyl toughening agent, inorganic filler and hexamethylene diisocyanate trimer in the above ratio are used to modify TPEE together, the obtained eyeglass frames have higher toughness, scratch resistance and chemical resistance, which can reduce the wear, breakage, scratches and creep of the eyeglass frames during use, and at the same time improve the tolerance of the eyeglass frames to sweat and chemicals, reducing the possibility of aging and wear of the eyeglass frames.

[0025] Preferably, the weight ratio of the hydroxy-modified ternary vinyl chloride resin to the branched hydroxy polyester is 1:(1-4).

[0026] When hydroxy-modified ternary chloroacetic acid resin and branched hydroxy polyester are compounded, they play a synergistic role in toughening and chemical resistance, making the eyeglass frames more tolerant to sweat and chemicals, and reducing the possibility of aging, wear, breakage, scratches, creep, etc. during use.

[0027] Preferably, the inorganic filler is one or more of single crystal corundum powder, hexagonal boron nitride, single crystal zircon powder, and quartz powder.

[0028] Single crystal corundum powder, hexagonal boron nitride, single crystal zircon powder, and quartz powder all have good wear resistance, corrosion resistance, and chemical stability. Therefore, they are not easily corroded by oils, chemicals, etc., and after TPEE is modified with silicone masterbatch, hydroxyl toughening agent, and hexamethylene diisocyanate trimer, the obtained eyeglass frames have high toughness, scratch resistance, and chemical resistance, which reduces the breakage, wear, scratches, etc. of the eyeglass frames during use, and reduces the possibility of aging and discoloration caused by sweat and chemicals corroding the eyeglass frames.

[0029] Preferably, the weight ratio of the single crystal corundum powder, hexagonal boron nitride, single crystal zircon powder and quartz powder is 1:(1-2):(1-3):(1-4).

[0030] When the above raw materials are used in combination, they play a synergistic role, thereby making the wear resistance and scratch resistance of the eyeglass frames better.

[0031] Preferably, the particle sizes of the single crystal corundum powder, hexagonal boron nitride, single crystal zircon powder and quartz powder are all 30-50 nm.

[0032] The above-mentioned single crystal corundum powder, hexagonal boron nitride, single crystal zircon powder and quartz powder in the nanometer range are selected to play a better dispersing role and are easy to be filled in the raw material system of TPEE. In addition, after the TPEE is modified by combining with silicone masterbatch, hydroxyl toughening agent and hexamethylene diisocyanate trimer, the obtained eyeglass frames have higher toughness, scratch resistance and chemical resistance.

[0033] Preferably, the inorganic filler is a modified inorganic filler, and the modified inorganic filler is prepared from the following raw materials in parts by weight:

[0034] 8-15 parts of 60-80% ethanol solution

[0035] 1-3 parts of ethylene-maleic anhydride-vinyl acetate terpolymer emulsion

[0036] Carboxyl modified vinyl chloride-vinyl acetate-maleic anhydride terpolymer resin 0.1-1 part

[0037] Methacryloyloxypropyl tris(trimethylsiloxy)silane 1-5 parts

[0038] Acrylate Polyethylene Glycol Silane 0.1-0.5 parts

[0039] Initiator 0.05-0.1 parts

[0040] 20-50 parts of inorganic filler.

[0041] In the above scheme, the ternary copolymer emulsion of ethylene-maleic anhydride-vinyl acetate and the carboxyl-modified vinyl chloride-vinyl acetate-maleic anhydride ternary copolymer resin have good film-forming properties, adhesion and flexibility after film formation, while methacryloxypropyl tris(trimethylsiloxy)silane and acrylate polyethylene glycol silane can self-polymerize and have good compatibility with polymers and inorganic substances.

[0042] Therefore, under the dilution effect of the ethanol solution, the ternary copolymer emulsion of ethylene-maleic anhydride-vinyl acetate, the carboxyl-modified vinyl chloride-vinyl acetate-maleic anhydride ternary copolymer resin, methacryloxypropyl tris(trimethylsiloxy)silane, and acrylate polyethylene glycol silane are mixed and compounded, and the inorganic filler can be surface-modified, so that the prepared modified inorganic filler can be uniformly dispersed in the raw material system of TPEE.

[0043] In combination with other modifiers, the obtained eyeglass frames are less likely to be worn, broken, scratched, or creeping, while reducing the erosion of sweat and chemicals, thereby improving the appearance and durability of the eyeglass frames.

[0044] Preferably, the modified inorganic filler is prepared by the following method:

[0045] According to weight parts, methacryloxypropyl tri(trimethylsiloxy)silane, acrylate polyethylene glycol silane, 60-80% ethanol solution and initiator are weighed and stirred evenly, heated to 63-78°C, reacted for 50-80 minutes, and then ethylene-maleic anhydride-vinyl acetate ternary copolymer latex and carboxyl-modified vinyl chloride-vinyl acetate-maleic anhydride ternary copolymer resin are added and stirred for 30-60 minutes to obtain a modified liquid; inorganic filler is weighed, and then the modified liquid is sprayed on the surface of the inorganic filler to fully mix the modified liquid and the inorganic filler, and dried to obtain a modified inorganic filler.

[0046] In the above process, methacryloxypropyl tri(trimethylsiloxy)silane and acrylate polyethylene glycol silane both contain siloxy groups. After compounding and copolymerizing, they are further compounded with ethylene-maleic anhydride-vinyl acetate ternary copolymer emulsion and carboxyl-modified vinyl chloride-vinyl acetate-maleic anhydride ternary copolymer resin, so that the obtained modified liquid has better film-forming properties, adhesion and film-forming flexibility.

[0047] It is sprayed on the surface of the inorganic filler, and after curing, a coating film with good flexibility and compatibility is formed on the surface of the inorganic filler, so that the modified inorganic filler can play the role of toughening and increasing scratch resistance. In addition, TPEE is modified together with silicone masterbatch, hydroxyl toughening agent and hexamethylene diisocyanate trimer, so that the obtained eyeglass frames have higher scratch resistance, toughness and chemical resistance.

[0048] At the same time, it reduces scratches, breakages, wear and tear on the frames during use, improves the frames' tolerance to sweat and chemicals, reduces aging, discoloration and wear on the frames, and improves the frames' appearance and durability.

[0049] Preferably, the processing aid is one or more of an anti-aging agent, a plasticizer, a colorant, and a lubricant.

[0050] Adding anti-aging agent can improve the aging resistance of the eyeglass frame, while plasticizer plays a plasticizing role to improve the convenience of processing. Colorant plays a coloring role to make the eyeglass frame colorful, and lubricant facilitates the demoulding of the eyeglass frame.

[0051] Preferably, the anti-aging agent is one or more of 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, 2,6-di-tert-butyl-p-cresol, N-phenyl-N'-isopropyl-p-phenylenediamine, and UV-770.

[0052] The above 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, 2,6-di-tert-butyl-p-cresol, N-phenyl-N'-isopropyl-p-phenylenediamine and UV-770 as anti-aging agents all play an anti-aging role and reduce the possibility of aging of eyeglass frames.

[0053] In a second aspect, the present application provides a method for preparing a high-toughness and scratch-resistant eyeglass frame, comprising the following steps:

[0054] According to weight parts, polytetrahydrofuran ether glycol, terephthalic acid, and 1,4-butanediol are weighed, heated to 150-165°C, reacted for 2-3 hours to obtain TPEE prepolymer, heated to 220-235°C, added with catalyst, and polycondensed for 2-3 hours to obtain TPEE polycondensate.

[0055] The temperature is lowered to 175-185°C, a processing aid is added to mix it evenly with the TPEE polycondensate, silicone masterbatch, hydroxyl toughening agent and inorganic filler are added, the reaction is carried out for 1-3 hours, hexamethylene diisocyanate trimer is added, the reaction is continued for 3-5 hours, the material is discharged, cooled, granulated and dried to obtain a modified TPEE material, and the modified TPEE material is processed and formed to obtain a spectacle frame.

[0056] In the above process, polytetramethylene ether glycol and terephthalic acid are used as polymerization monomers, 1,4-butanediol is used to further extend the chain, and under the action of the catalyst, further polycondensation reaction is carried out to obtain TPEE polycondensate in a semi-polycondensation state. After adding the processing aid, it is convenient to mix with the silicone masterbatch, hydroxyl toughening agent, and inorganic filler. Under the action of the remaining catalyst, the TPEE polycondensate further extends the chain or cross-links with the hydroxyl toughening agent. At the same time, under the action of the hydroxyl toughening agent, the silicone masterbatch and the TPEE polycondensate are fully and evenly mixed.

[0057] The silicone masterbatch promotes the uniform mixing of the inorganic filler and the TPEE polycondensate, and then hexamethylene diisocyanate trimer is further added. Under the remaining catalyst, the TPEE polycondensate is further reacted to further improve the toughness, scratch resistance, and chemical resistance, and reduce the possibility of wear, scratches, breakage, creep, etc. on the resulting eyeglass frames.

[0058] At the same time, the tolerance of the glasses frame to sweat and chemicals is improved. Therefore, the glasses frame obtained in the present application is not easily corroded by sweat and chemicals on the human face during long-term use and contact with human skin, thereby improving the appearance and durability of the glasses frame.

[0059] In summary, this application has the following beneficial effects:

[0060] 1. The present application uses silicone masterbatch, hydroxyl toughening agent, inorganic filler and hexamethylene diisocyanate trimer as modifiers to jointly modify TPEE, thereby achieving better toughness enhancement, scratch resistance, creep resistance and chemical resistance.

[0061] The glasses frame thus obtained is not prone to breakage, scratching, abrasion and the like during use, and is also not easily corroded by sweat, grease and the like, thereby improving the appearance and durability of the glasses frame.

[0062] 2. By using modified inorganic fillers and combining with other modifiers, the obtained eyeglass frames are less susceptible to wear, breakage, scratching, and creep, while reducing the erosion of sweat and grease, thereby improving the appearance and durability of the eyeglass frames.

[0063] 3. Through the preparation process of the present application, the TPEE polycondensate is in a semi-condensation state, and under the joint modification of silicone masterbatch, hydroxyl toughening agent, inorganic filler and hydroxyl toughening agent, the toughness, scratch resistance and chemical resistance of TPEE are further improved, and the possibility of wear, scratching, fracture and creep of the obtained eyeglass frames is reduced.

[0064] At the same time, the tolerance of the glasses frame to sweat and chemicals is improved. Therefore, the glasses frame obtained in the present application is not easily corroded by sweat and chemicals on the human face during long-term use and contact with human skin, thereby improving the appearance and durability of the glasses frame. DETAILED DESCRIPTION

[0065] The present application is further described in detail below in conjunction with embodiments.

[0066] Introduction table of some raw materials;

[0067] Table 1 Introduction of some raw materials

[0068]

[0069]

[0070] Example

[0071] Example 1

[0072] A high-toughness, scratch-resistant eyeglass frame is prepared by the following method:

[0073] 2.2 kg of polytetrahydrofuran ether glycol, 3.49 kg of terephthalic acid and 3.0 kg of 1,4-butanediol were weighed and put into a reactor, heated to 150° C., reacted for 3 h to obtain a TPEE prepolymer, and then heated to 235° C., 0.01 kg of a catalyst was added, and the polycondensation reaction was carried out for 2 h to obtain a TPEE polycondensate.

[0074] The temperature was lowered to 175°C, 0.25kg of plasticizer and 0.05kg of anti-aging agent were added to mix them with the TPEE polycondensate, 0.3kg of silicone masterbatch, 0.1kg of hydroxyl toughening agent and 0.5kg of inorganic filler were added, mixed evenly and reacted for 1h, 0.1kg of hexamethylene diisocyanate trimer was added, and the reaction was continued for 5h, the material was discharged, and cooled to 40°C, and placed in a granulator for granulation, and then placed in an oven at 80°C for drying for 2h to obtain modified TPEE material. After processing the modified TPEE material, a frame and temples were obtained, and the frame and temples were hinged to obtain a glasses frame.

[0075] The processing temperature of the modified TPEE material is 180-240° C., and in this embodiment, it is preferably 220° C. The processing technology can be mold forming or injection molding.

[0076] The hydroxy toughening agent is a hydroxy modified ternary chloroacetic acid resin; the anti-aging agent is an antioxidant 1010; the inorganic filler is a single crystal corundum powder, and the average particle size of the single crystal corundum powder is 30 nm.

[0077] Example 2

[0078] The difference between Example 2 and Example 1 is that the amount of some raw materials and process parameters are different, as follows:

[0079] The spectacle frame is made by the following method:

[0080] 3.8 kg of polytetrahydrofuran ether glycol, 2.47 kg of terephthalic acid and 2.5 kg of 1,4-butanediol were weighed and put into a reactor, heated to 165° C., reacted for 2 h to obtain a TPEE prepolymer, and then heated to 235° C., 0.03 kg of catalyst was added, and polycondensation reaction was carried out for 3 h to obtain a TPEE polycondensate.

[0081] The temperature was lowered to 180°C, 0.18kg plasticizer and 0.02kg anti-aging agent were added to mix them with the TPEE polycondensate, 0.3kg silicone masterbatch, 0.1kg hydroxyl toughening agent and 0.5kg inorganic filler were mixed evenly and reacted for 1h, and 0.1kg hexamethylene diisocyanate trimer was added to continue the reaction for 4h. The material was discharged and cooled to 40°C, placed in a granulator for granulation, and then placed in an 80°C oven for drying for 2h to obtain modified TPEE material. The modified TPEE material was processed and shaped to obtain a frame and temples, and the frame and temples were hinged to obtain a glasses frame.

[0082] Example 3

[0083] The difference between Example 3 and Example 2 is that the amount of some raw materials and process parameters are different, as follows:

[0084] 3.8 kg of polytetrahydrofuran ether glycol, 2.25 kg of terephthalic acid and 2.3 kg of 1,4-butanediol were weighed and put into a reactor, heated to 165° C., reacted for 2 h to obtain a TPEE prepolymer, then heated to 220° C., added with 0.05 kg of catalyst, and subjected to polycondensation reaction for 3 h to obtain a TPEE polycondensate.

[0085] The temperature was lowered to 185°C, 0.09kg plasticizer and 0.01kg anti-aging agent were added to mix them with the TPEE polycondensate, 0.45kg silicone masterbatch, 0.15kg hydroxy toughening agent and 0.75kg inorganic filler were added, mixed evenly and reacted for 3h, 0.15kg hexamethylene diisocyanate trimer was added, the reaction was continued for 3h, the material was discharged, and cooled to 40°C, placed in a granulator for granulation, and then placed in an 80°C oven for drying for 2h to obtain modified TPEE material, the modified TPEE material was processed and formed to obtain a frame and temples, and the frame and temples were hinged to obtain a glasses frame.

[0086] Example 4

[0087] The difference between Example 4 and Example 3 is that the amounts of silicone masterbatch, hydroxyl toughening agent, inorganic filler, and hexamethylene diisocyanate trimer are different, specifically as follows: 0.15 kg silicone masterbatch, 0.3 kg hydroxyl toughening agent, 0.9 kg inorganic filler, and 0.15 kg hexamethylene diisocyanate trimer.

[0088] Example 5

[0089] The difference between Example 5 and Example 4 is that the hydroxy toughening agent is composed of hydroxy-modified ternary chloroacetic acid resin and branched hydroxy polyester in a weight ratio of 1:1.

[0090] Example 6

[0091] The difference between Example 6 and Example 4 is that the hydroxy toughening agent is composed of hydroxy-modified ternary chloroacetic acid resin and branched hydroxy polyester in a weight ratio of 1:4.

[0092] Example 7

[0093] The difference between Example 7 and Example 6 is that the inorganic filler is composed of single crystal corundum powder, hexagonal boron nitride, single crystal zircon powder, and quartz powder in a weight ratio of 2:1:1:1, and the average particle size of single crystal corundum powder, hexagonal boron nitride, single crystal zircon powder, and quartz powder is 30 nm.

[0094] Example 8

[0095] The difference between Example 8 and Example 6 is that the inorganic filler is composed of single crystal corundum powder, hexagonal boron nitride, single crystal zircon powder, and quartz powder in a weight ratio of 5:3:2:1, and the average particle size of single crystal corundum powder, hexagonal boron nitride, single crystal zircon powder, and quartz powder is 50 nm.

[0096] Example 9

[0097] The difference between Example 9 and Example 8 is that the inorganic filler is a modified inorganic filler, and the modified inorganic filler is prepared by the following method:

[0098] Weigh 1kg of methacryloxypropyl tris(trimethylsiloxy)silane, 0.5kg of acrylate polyethylene glycol silane, 8kg of 80% ethanol solution and 0.05kg of initiator BPO into a reactor, stir for 5min at a speed of 50r / min, heat to 63°C, react for 80min, then add 3kg of ethylene-maleic anhydride-vinyl acetate ternary copolymer emulsion and 0.1kg of carboxyl-modified vinyl chloride-vinyl acetate-maleic anhydride ternary copolymer resin and continue stirring for 60min to obtain a modified liquid.

[0099] Weigh 20 kg of inorganic filler (composed of single crystal corundum powder, hexagonal boron nitride, single crystal zircon powder, and quartz powder in a weight ratio of 5:3:2:1) and put it into a stirring device, then spray the modified liquid on the surface of the inorganic filler through a spraying device to fully mix the modified liquid and the inorganic filler, put it into an oven at 120°C for drying for 2 hours to obtain a modified inorganic filler.

[0100] Example 10

[0101] The difference between Example 10 and Example 9 is that the amount of raw materials and process parameters of the modified inorganic filler are different, as follows:

[0102] Weigh 3kg of methacryloyloxypropyl tris(trimethylsiloxy)silane, 0.3kg of acrylate polyethylene glycol silane, 12kg of 70% ethanol solution and 0.08kg of initiator BPO into a reactor, stir for 5min at a speed of 50r / min, heat to 70°C, react for 65min, add 2kg of ethylene-maleic anhydride-vinyl acetate ternary copolymer emulsion and 0.5kg of carboxyl-modified vinyl chloride-vinyl acetate-maleic anhydride ternary copolymer resin and continue stirring for 60min to obtain a modified liquid.

[0103] Weigh 38 kg of inorganic filler (composed of single crystal corundum powder, hexagonal boron nitride, single crystal zircon powder, and quartz powder in a weight ratio of 5:3:2:1) and put it into a stirring device. Then spray the modified liquid on the surface of the inorganic filler through a spraying device to fully mix the modified liquid and the inorganic filler. Put it in an oven at 120°C for drying for 2 hours to obtain a modified inorganic filler.

[0104] Embodiment 11

[0105] The difference between Example 11 and Example 9 is that the amount of raw materials and process parameters of the modified inorganic filler are different, as follows:

[0106] Weigh 5kg of methacryloxypropyl tris(trimethylsiloxy)silane, 0.1kg of acrylate polyethylene glycol silane, 15kg of 70% ethanol solution and 0.1kg of initiator BPO into a reactor, stir for 5min at a speed of 50r / min, heat to 78°C, react for 50min, then add 3kg of ethylene-maleic anhydride-vinyl acetate ternary copolymer emulsion and 1kg of carboxyl-modified vinyl chloride-vinyl acetate-maleic anhydride ternary copolymer resin and continue stirring for 30min to obtain a modified liquid.

[0107] Weigh 50 kg of inorganic filler (composed of single crystal corundum powder, hexagonal boron nitride, single crystal zircon powder, and quartz powder in a weight ratio of 5:3:2:1) and put it into a stirring device, then spray the modified liquid on the surface of the inorganic filler through a spraying device to fully mix the modified liquid and the inorganic filler, put it into an oven at 120°C for drying for 2 hours to obtain a modified inorganic filler.

[0108] Example 12

[0109] The difference between Example 12 and Example 9 is that the carboxyl-modified vinyl chloride-vinyl acetate-maleic anhydride ternary copolymer resin is replaced by an equal amount of ethylene-maleic anhydride-vinyl acetate ternary copolymer emulsion.

[0110] Embodiment 13

[0111] The difference between Example 13 and Example 9 is that the acrylate polyethylene glycol silane is replaced by an equal amount of methacryloxypropyl tris(trimethylsiloxy)silane.

[0112] Comparative Example

[0113] Comparative Example 1

[0114] The difference between Comparative Example 1 and Example 1 is that the hydroxyl toughening agent is replaced by hexamethylene diisocyanate trimer in equal amount.

[0115] Comparative Example 2

[0116] The difference between Comparative Example 2 and Example 1 is that an equal amount of inorganic filler replaces the silicone masterbatch.

[0117] Comparative Example 3

[0118] The difference between Comparative Example 3 and Example 1 is that the hexamethylene diisocyanate trimer and the hydroxyl toughening agent are replaced by an inorganic filler.

[0119] Performance testing

[0120] Detection method / test method

[0121] The modified TPEE materials obtained in Examples 1-13 and Comparative Examples 1-3 were subjected to injection molding at an injection temperature of 220° C. to obtain test samples for the following tests:

[0122] 1) Physical properties Tensile strength: refer to ASTM D638, the test condition is 50mm / min, and the thickness of the test sample is 2mm.

[0123] Elongation at break: refer to ASTM D638, the test condition is 50mm / min, and the thickness of the test sample is 2mm.

[0124] 2) Wear test The test sample was cut into long strips according to the national standard GB / T 1689-2014, and then the wear resistance of the test sample was tested using an Akron abrasion machine. The standard HG / T2073-91 "Akron Abrasion Machine Technical Conditions" was implemented, and the Akron wear was recorded as A.

[0125] Aging treatment: The aging solution is prepared by mixing artificial sweat with a pH value of 4.7, squalane, glycerol, and butanediol in a weight ratio of 20:1:1:3; the test sample is placed in the aging solution at 45°C, and after soaking for 7 days, the test sample is taken out and placed in an oven at 50°C for drying for 2 hours, and then the wear resistance test is carried out. The test method is the same as 1), and the obtained Akron wear is recorded as B. The calculation of the growth rate of Akron wear = [(BA) / A]*100%.

[0126] The setting of experiment 2) is based on the fact that when wearing glasses, the frames will come into contact with human skin, and human skin is usually protected by cosmetics. Squalane (CAS No. 111-01-3), glycerol, and butylene glycol are the main raw materials of most cosmetics. Therefore, the aging liquid obtained by compounding artificial sweat, squalane, glycerol, and butylene glycol is closer to the substance that the frames are in contact with during actual use, and the test is carried out at 37°C, which is close to human body temperature. Therefore, it can better highlight the tolerance of the frames in the actual application process.

[0127] 3) Scratch resistance test

[0128] The glasses frames obtained in Examples 1-13 and Comparative Examples 1-3 were subjected to the aging treatment in 2), and then completely fixed. Then, a copper brush with a copper wire diameter of 0.1 mm was used to scratch back and forth on the plane of the wider plane of the temple of the glasses frame (the scratching force was 3N and the scratch length was 2 cm). The test was repeated 3 times, and whether scratches appeared after 30 seconds. The ambient temperature was 25°C and the humidity was 60%.

[0129] 4) Creep resistance test

[0130] The temples obtained in Examples 1-13 and Comparative Examples 1-3 are right-angle temples, and their specifications are preferably 130 mm in length, 5 mm in width, and 3 mm in thickness; one temple is fixed close to the end of the frame and recorded as the fixed point, and the endpoint of the temple away from the fixed point is marked and recorded as the initial point.

[0131] Move the temple outward to the fixed point at an angle of 45 degrees. At this time, the end point of the temple away from the fixed point is recorded as the moving point, and the distance from the initial point to the moving point is measured and recorded as L1. Maintain this state for 14 days. The test environment temperature is 45°C and the humidity is 60%. Remove the force. After leaving it for 2 hours, mark the end point of the temple away from the fixed point as the creep point, and measure the distance from the moving point to the creep point, which is recorded as L2. The creep rate is 1-(L2 divided by L1 multiplied by 100%). The larger the creep rate, the worse the anti-creep effect.

[0132] The above experiments were tested 3 times and the average value was taken. The specific data are shown in Table 2;

[0133] Table 2 Experimental data of Examples 1-13 and Comparative Examples 1-3

[0134]

[0135]

[0136] Combining Example 1 and Comparative Examples 1-3 and Table 2, it can be seen that the elongation at break and the tensile strength of Comparative Examples 1-3 are lower than those of Example 1, while the Akron wear, the growth rate of Akron wear and the creep rate are higher than those of Example 1, and no scratches occur in Example 1, indicating that the silicone masterbatch, hydroxyl toughening agent, inorganic filler and hexamethylene diisocyanate trimer combination of the present application and the modification of TPEE have a better synergistic effect, thereby reducing the possibility of fracture, scratching, corrosion, creep, etc., and improving the durability of the prepared eyeglass frames.

[0137] Combining Example 4 and Example 5-6 with Table 2, it can be seen that the elongation at break and the tensile strength of Example 5-6 are higher than those of Example 4, and the Akron wear, the growth rate of Akron wear and the creep rate are lower than those of Example 4, indicating that the compounding of the hydroxyl-modified ternary chloroacetic acid resin and the branched hydroxyl polyester has a synergistic effect, further improving the toughness, scratch resistance and chemical resistance of the modified TPEE material, and reducing the possibility of wear, fracture, corrosion, creep, etc. on the eyeglass frame.

[0138] Combining Example 6 and Example 7-8 and Table 2, it can be seen that the elongation at break and the tensile strength of Example 7-8 are higher than those of Example 6, and the Akron wear, the growth rate of Akron wear and the creep rate are lower than those of Example 6, indicating that the compounding of single crystal corundum powder, hexagonal boron nitride, single crystal zircon powder and quartz powder, and the combination of silicone masterbatch, hydroxyl toughening agent and hexamethylene diisocyanate trimer, has a better modification effect on TPEE, further improving the toughness, scratch resistance, wear resistance and chemical resistance of the prepared eyeglass frames, and reducing the possibility of wear, fracture, scratches, creep and the like.

[0139] Combining Example 8 with Examples 9-11 and Table 2, it can be seen that the elongation at break and the tensile strength of Examples 9-11 are higher than those of Example 8, and the Akron wear, the growth rate of Akron wear, and the creep rate are lower than those of Example 8, indicating that the modified inorganic filler obtained by the preparation method of the present application has better toughening and wear resistance, and is combined with silicone masterbatch, hydroxyl toughening agent, and hexamethylene diisocyanate trimer to make the modified TPEE material used in the production of eyeglass frames less prone to wear, breakage, scratching, and creep, and has better tolerance to sweat and chemicals.

[0140] Combining Example 9 and Example 12-13 and Table 2, it can be seen that the elongation at break and tensile strength of Example 12-13 are higher than those of Example 9, and the Akron wear and Akron wear growth rate are lower than those of Example 9, indicating that the modified liquid prepared by compounding the ternary copolymer emulsion of ethylene-maleic anhydride-vinyl acetate, carboxyl-modified vinyl chloride-vinyl acetate-maleic anhydride ternary copolymer resin, and methacryloxypropyl tris(trimethylsiloxy)silane has a better modification effect on the inorganic filler, and it is combined with silicone masterbatch, hydroxyl toughening agent, and hexamethylene diisocyanate trimer to modify TPEE, which has a synergistic effect, and the obtained eyeglass frame has better toughness, wear resistance, creep resistance and chemical resistance, thereby improving the durability of the eyeglass frame.

[0141] This specific embodiment is merely an explanation of the present application and is not a limitation of the present application. After reading this specification, those skilled in the art may make modifications to the present embodiment without any creative contribution as needed, but such modifications are protected by the patent law as long as they are within the scope of the claims of the present application.

Claims

1. A high-toughness and scratch-resistant eyeglass frame, comprising a frame and two temples hinged to both sides of the frame, characterized in that: The frame and temples are made of the following raw materials in percentage by weight: Polytetramethylene glycol 22-38% 1,4-Butanediol 18-30% Terephthalic acid 22.5-3.49% Catalyst 0.1-0.5% Modifier 10-15% The balance is processing aids; The modifier is composed of silicone masterbatch, hydroxyl toughening agent, inorganic filler and hexamethylene diisocyanate trimer in a weight ratio of (1-3): (1-2): (5-6): 1; The hydroxy toughening agent is a hydroxy-modified ternary chloroacetic acid resin and / or a branched hydroxy polyester; The processing aid is one or more of an anti-aging agent, a plasticizer, a colorant, and a lubricant; The inorganic filler is composed of single crystal corundum powder, hexagonal boron nitride, single crystal zircon powder and quartz powder in a weight ratio of (2-6): (1-3): (1-4): 1; The hydroxy toughening agent is composed of hydroxy-modified ternary chloroacetic acid resin and branched hydroxy polyester in a weight ratio of 1: (1-4); The preparation of a high-toughness, scratch-resistant eyeglass frame comprises the following steps: According to weight parts, polytetrahydrofuran ether glycol, terephthalic acid, and 1,4-butanediol are weighed, heated to 150-165°C, reacted for 2-3h to obtain TPEE prepolymer, heated to 225-235°C, added with catalyst, polycondensed for 2-3h to obtain TPEE polycondensate; and cooled to 175-185°C, added with processing aid, and mixed evenly with TPEE polycondensate, and then silicone masterbatch, hydroxyl toughening agent, and inorganic filler are added, reacted for 1-3h, and then hexamethylene diisocyanate trimer is added, and the reaction is continued for 3-5h, the material is discharged, cooled, granulated, and dried to obtain modified TPEE material, and the modified TPEE material is processed and formed to obtain eyeglass frames.

2. The high-toughness and scratch-resistant eyeglass frame according to claim 1, characterized in that: The particle sizes of the single crystal corundum powder, hexagonal boron nitride, single crystal zircon powder and quartz powder are all 30-50 nm.

3. A high-toughness and scratch-resistant eyeglass frame according to any one of claim 1, characterized in that: The inorganic filler is a modified inorganic filler, and the modified inorganic filler is prepared from the following raw materials in parts by weight: 8-15 parts of 60-80% ethanol solution 1-3 parts of ethylene-maleic anhydride-vinyl acetate terpolymer emulsion Carboxyl modified vinyl chloride-vinyl acetate-maleic anhydride terpolymer resin 0.1-1 part Methacryloyloxypropyl tris(trimethylsiloxy)silane 1-5 parts Acrylate Polyethylene Glycol Silane 0.1-0.5 parts Initiator 0.05-0.1 parts 20-50 parts of inorganic filler.

4. The high-toughness and scratch-resistant eyeglass frame according to claim 3, characterized in that: The modified inorganic filler is prepared by the following method: According to weight parts, methacryloxypropyl tris(trimethylsiloxy)silane, acrylate polyethylene glycol silane, 60-80% ethanol solution and initiator are weighed and stirred evenly, heated to 63-78°C, reacted for 50-80 minutes, and then added with ethylene-maleic anhydride-vinyl acetate ternary copolymer latex and carboxyl-modified vinyl chloride-vinyl acetate-maleic anhydride ternary copolymer resin and stirred for 30-60 minutes to obtain a modified liquid; The inorganic filler is weighed, and the modified liquid is sprayed on the surface of the inorganic filler to fully and evenly mix the modified liquid and the inorganic filler, and then dried to obtain the modified inorganic filler.

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