Fluororesin color master batch, preparation method thereof and fluororesin composition

Abstract

The invention discloses a fluororesin color master batch which is characterized in that the number of lumps on the surface of the fluororesin color master batch is observed to be less than 20 under the conditions that a BA200 microscope of Motic is adopted and the amplification factor is 100; measuring the fluororesin color master batch delta Elt by adopting a ball colorimeter Color i5 of the Eixian Co., Ltd; and 1.0. The fluororesin color master batch provided by the invention is smooth in surface and relatively good in coloring property and chromaticity uniformity.

Description

Technical Field

[0001] This invention relates to the field of resin coloring, specifically to a fluororesin masterbatch and its preparation method, and a fluororesin composition. Background Technology

[0002] Masterbatch technology is the most commonly used method for coloring plastics. Masterbatch involves pre-dispersing pigments in a carrier resin, offering several advantages: firstly, it improves pigment dispersibility, prevents pigment agglomeration within the matrix, and thus extends the shelf life of the masterbatch. Secondly, compared to traditional coloring methods, masterbatch technology is less environmentally polluting, has a simpler process, and is easier to clean.

[0003] Due to the strong carbon-fluorine bond structure of fluororesins, they have excellent stability and are difficult to modify. On the other hand, the dispersion performance of pigment particles in fluororesins is poor, which affects the coloring quality of fluororesin masterbatches. Summary of the Invention

[0004] In view of the shortcomings of the prior art, the present invention provides a fluoropolymer masterbatch, which aims to improve the appearance, coloring performance and color uniformity of the fluoropolymer masterbatch.

[0005] The above-mentioned objective of this invention is achieved through the following technical solution:

[0006] In a first aspect, the present invention provides a fluoropolymer masterbatch, wherein the number of bumps on the surface of the fluoropolymer masterbatch is less than 20 when observed using a Motic BA200 microscope at a magnification of 100; and the ΔE of the fluoropolymer masterbatch is measured to be less than 1.0 using a Colori5 spherical colorimeter from X-Rite Ltd.

[0007] In some embodiments of the present invention, the fluororesin masterbatch raw material comprises, by weight, 20-100 parts of irradiated fluororesin and 10-20 parts of color powder modified by coupling agent.

[0008] In some embodiments of the present invention, the fluoropolymer masterbatch raw material comprises, by weight: 30-50 parts of irradiated fluoropolymer, 10-20 parts of color powder modified with coupling agent, and 50-70 parts of unirradiated fluoropolymer, wherein the total mass of the unirradiated fluoropolymer and the irradiated fluoropolymer is 100 parts.

[0009] In some embodiments of the present invention, the fluororesin includes at least one of fluorinated ethylene propylene copolymer (FEP), meltable polytetrafluoroethylene (PFA), polytetrafluoroethylene (PTFE), and ethylene-tetrafluoroethylene copolymer (ETFE).

[0010] In some embodiments of the present invention, the pigment includes at least one of phthalocyanine blue, phthalocyanine green, iron oxide red, iron oxide yellow, pigment red, pigment yellow, pigment purple, carbon black, and titanium dioxide;

[0011] And / or, the coupling agent is a silane coupling agent.

[0012] In some embodiments of the present invention, the mass ratio of the coupling agent to the color powder modified with the coupling agent is (0.25-2):100.

[0013] In some embodiments of the present invention, the irradiation dose of the irradiated fluoropolymer is 5-10 MRad.

[0014] In a second aspect, the present invention provides a method for preparing the above-mentioned fluororesin masterbatch, the method comprising the following steps:

[0015] The irradiated fluororesin and the color powder modified with coupling agent are mixed in an internal mixer to prepare a mixture. The mixture is then extruded, drawn into strips, and granulated by an extrusion device to obtain the fluororesin masterbatch.

[0016] In some embodiments of the present invention, the mixing temperature of the internal mixer is 220-260°C and the mixing time is 5-10 min;

[0017] And / or, during extrusion using an extrusion device, the unirradiated fluoropolymer is added to the mixture;

[0018] And / or, the extrusion temperature of the extrusion equipment is 260-300℃.

[0019] In a third aspect, the present invention provides a fluororesin composition comprising the fluororesin masterbatch as described above. Using a Motic BA200 microscope at a magnification of 100, the number of bumps on the surface of the fluororesin composition is observed to be less than 20. Using a Color i5 spherical colorimeter from X-Rite Ltd., the ΔE of the fluororesin masterbatch is measured to be less than 2.0.

[0020] The fluororesin masterbatch of this invention, observed using a Motic BA200 microscope at 100x magnification, showed a surface nodules of less than 30; the ΔE of the fluororesin masterbatch was measured to be ≤1.2 using a Colori5 spherical colorimeter from X-Rite Co., Ltd. The fluororesin masterbatch provided by this invention has a smooth surface, good coloring performance, and good color uniformity. Detailed Implementation

[0021] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. It should be understood that the following embodiments are only used to explain the present invention and are not intended to limit the present invention.

[0022] Unless otherwise specified, all technical and scientific terms used herein have their usual meaning within the field to which the subject matter is claimed.

[0023] Masterbatch technology is the most commonly used method for coloring plastics. Masterbatch involves pre-dispersing pigments in a carrier resin, offering several advantages: firstly, it improves pigment dispersibility, prevents pigment agglomeration within the matrix, and thus extends the shelf life of the masterbatch. Secondly, compared to traditional coloring methods, masterbatch technology is less environmentally polluting, has a simpler process, and is easier to clean.

[0024] Due to the strong carbon-fluorine bond structure of fluororesins, they have excellent stability and are difficult to modify. On the other hand, the dispersion performance of pigment particles in fluororesins is poor, which affects the coloring quality of fluororesin masterbatches.

[0025] To address the aforementioned problems, the first aspect of this invention provides a fluoropolymer masterbatch. Using a Motic BA200 microscope at 100x magnification, the number of bumps on the surface of the fluoropolymer masterbatch is observed to be less than 20. The ΔE of the fluoropolymer masterbatch is measured to be less than 1.0 using a Colori5 spherical colorimeter from X-Rite Ltd.

[0026] The fluororesin masterbatch provided by this invention has a smooth surface, good coloring performance, and good color uniformity.

[0027] In some embodiments of the present invention, the fluororesin masterbatch raw material comprises, by weight, 20-100 parts of irradiated fluororesin and 10-20 parts of color powder modified by coupling agent.

[0028] In some embodiments of the present invention, the irradiated fluoropolymer can be any number of parts by weight from 20 to 100, such as 20 parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight, 45 parts by weight, 50 parts by weight, 55 parts by weight, 60 parts by weight, 65 parts by weight, 70 parts by weight, 75 parts by weight, 80 parts by weight, 85 parts by weight, 90 parts by weight, 95 parts by weight, and 100 parts by weight.

[0029] In some embodiments of the present invention, the color powder modified by the coupling agent can be any number of parts from 10 to 20 parts by weight, such as 10 parts by weight, 11 parts by weight, 12 parts by weight, 13 parts by weight, 14 parts by weight, 15 parts by weight, 16 parts by weight, 17 parts by weight, 18 parts by weight, 19 parts by weight, and 20 parts by weight.

[0030] Fluoropolymer masterbatch prepared using the above-mentioned parts by weight of irradiated fluoropolymer and color powder modified with coupling agent has a smooth surface, good coloring performance, and good color uniformity.

[0031] After irradiation pretreatment, fluororesin undergoes slight oxidative degradation, forming active free radicals. On the one hand, the slight degradation of fluororesin reduces its melt viscosity, which is more conducive to the shear dispersion of pigments in fluororesin. On the other hand, coupling agents can be used to bridge fluororesin and pigment particles, forming chemical bonds, which improves the dispersion of pigment particles in fluororesin, making the surface of fluororesin masterbatch smooth and improving the coloring performance, color uniformity, and mechanical properties of fluororesin masterbatch.

[0032] The fluoropolymer resin is irradiated using an irradiation device with an irradiation dose of 5-10 MRad. Too low an irradiation dose will result in incomplete degradation of the fluoropolymer resin and a reduced number of active sites; too high an irradiation dose will lead to a severe decline in the mechanical and other properties of the fluoropolymer resin. This invention does not limit the type of irradiation device; it can be a gamma-ray irradiation device or an electron accelerator irradiation device.

[0033] After grinding the pigment powder, a small amount of water is added to make a slurry. The coupling agent is dissolved in anhydrous ethanol and then added dropwise to the slurry. The mixture is stirred for 5-10 minutes. After the reaction is complete, the mixture is dried to obtain the pigment powder modified with the coupling agent.

[0034] In some embodiments of the present invention, the fluoropolymer masterbatch raw material, calculated by weight, includes: 30-50 parts of irradiated fluoropolymer, 10-20 parts of color powder modified by coupling agent, and 50-70 parts of unirradiated fluoropolymer, wherein the total mass of the unirradiated fluoropolymer and the irradiated fluoropolymer is 100 parts.

[0035] In some embodiments of the present invention, the irradiated fluoropolymer can be any number of parts from 30 to 50 parts by weight, such as 30 parts by weight, 32 parts by weight, 34 parts by weight, 36 parts by weight, 38 parts by weight, 40 parts by weight, 42 parts by weight, 44 parts by weight, 46 parts by weight, 48 parts by weight, and 50 parts by weight.

[0036] In some embodiments of the present invention, the color powder modified by the coupling agent can be any number of parts from 10 to 20 parts by weight, such as 10 parts by weight, 11 parts by weight, 12 parts by weight, 13 parts by weight, 14 parts by weight, 15 parts by weight, 16 parts by weight, 17 parts by weight, 18 parts by weight, 19 parts by weight, and 20 parts by weight.

[0037] In some embodiments of the present invention, the unirradiated fluoropolymer can be any number of parts from 50 to 70 parts by weight, such as 50 parts by weight, 52 parts by weight, 54 parts by weight, 56 parts by weight, 58 parts by weight, 60 parts by weight, 62 parts by weight, 64 parts by weight, 66 parts by weight, 68 parts by weight, and 70 parts by weight.

[0038] Understandably, adding unirradiated fluoropolymer can improve the mechanical properties of fluoropolymer masterbatches.

[0039] In some embodiments of the present invention, the fluororesin includes at least one of fluorinated ethylene propylene copolymer (FEP), meltable polytetrafluoroethylene (PFA), polytetrafluoroethylene (PTFE), and ethylene-tetrafluoroethylene copolymer (ETFE).

[0040] In some embodiments of the present invention, the fluororesin is fluorinated ethylene propylene copolymer (FEP), meltable polytetrafluoroethylene (PFA), polytetrafluoroethylene (PTFE), or ethylene-tetrafluoroethylene copolymer (ETFE); the fluororesin is fluorinated ethylene propylene copolymer (FEP) and meltable polytetrafluoroethylene (PFA); the fluororesin is fluorinated ethylene propylene copolymer (FEP) and polytetrafluoroethylene (PTFE); the fluororesin is fluorinated ethylene propylene copolymer (FEP) and ethylene-tetrafluoroethylene copolymer (ETFE); the fluororesin is meltable polytetrafluoroethylene (PFA) and polytetrafluoroethylene (PTFE); the fluororesin is meltable polytetrafluoroethylene (PFA) and ethylene-tetrafluoroethylene copolymer (ETFE); the fluororesin is polytetrafluoroethylene (PTFE) and ethylene-tetrafluoroethylene copolymer (ETFE). The fluororesin is an ethylene-propylene copolymer (ETFE); the fluororesin is a fluorinated ethylene-propylene copolymer (FEP), fusible polytetrafluoroethylene (PFA), and polytetrafluoroethylene (PTFE); the fluororesin is a fluorinated ethylene-propylene copolymer (FEP), fusible polytetrafluoroethylene (PFA), and ethylene-tetrafluoroethylene copolymer (ETFE); the fluororesin is a fluorinated ethylene-propylene copolymer (FEP), fusible polytetrafluoroethylene (PTFE), and ethylene-tetrafluoroethylene copolymer (ETFE); the fluororesin is a fusible polytetrafluoroethylene (PFA), fusible polytetrafluoroethylene (PTFE), and ethylene-tetrafluoroethylene copolymer (ETFE); the fluororesin is a fluorinated ethylene-propylene copolymer (FEP), fusible polytetrafluoroethylene (PFA), polytetrafluoroethylene (PTFE), and ethylene-tetrafluoroethylene copolymer (ETFE).

[0041] Understandable, fluorinated ethylene propylene copolymer (FEP) Propylene, also known as perfluoroethylene propylene, commonly called F46, is a melt-processable fluoropolymer copolymerized from tetrafluoroethylene (TFE) and hexafluoropropylene (HFP). Melt-processable polytetrafluoroethylene (PFA) is a high-performance fluoroplastic copolymerized from tetrafluoroethylene (TFE) and a small amount of perfluoroalkoxy vinyl ether (such as PPVE), combining the excellent properties of PTFE with the easy processability of thermoplastics. Polytetrafluoroethylene (PTFE), also known as Teflon, is a high-molecular polymer polymerized from tetrafluoroethylene as a monomer, exhibiting excellent heat and cold resistance and long-term use at -180~260℃. Ethylene-tetrafluoroethylene copolymer (ETFE), commonly known as polyvinyl fluoride, also called F-40, is a copolymerized from ethylene and tetrafluoroethylene.

[0042] In some embodiments of the present invention, the pigment includes at least one selected from phthalocyanine blue, phthalocyanine green, iron oxide red, iron oxide yellow, pigment red, pigment yellow, pigment purple, carbon black, and titanium dioxide.

[0043] The pigment is phthalocyanine blue, phthalocyanine green, iron oxide red, iron oxide yellow, pigment red, pigment yellow, pigment purple, carbon black, or titanium dioxide; the pigment is any two, three, four, or even more of phthalocyanine blue, phthalocyanine green, iron oxide red, iron oxide yellow, pigment red, pigment yellow, pigment purple, carbon black, and titanium dioxide.

[0044] In some embodiments of the present invention, the particle size of the pigment is 20-500 nm; more preferably, the particle size of the pigment is 20-200 nm.

[0045] In some embodiments of the present invention, the coupling agent is a silane coupling agent.

[0046] The silane coupling agent is one or more of γ-aminopropyltriethoxysilane (KH550), γ-glycidoxypropyltrimethoxysilane (KH560), and γ-methacryloyloxypropyltrimethoxysilane (KH570).

[0047] Adding coupling agents can improve the dispersibility of pigments in fluoropolymers and their compatibility with fluoropolymers.

[0048] In some embodiments of the present invention, the mass ratio of the coupling agent to the color powder modified with the coupling agent is (0.25-2):100.

[0049] Insufficient coupling agent content will affect the interfacial bonding ability between pigment and fluororesin, resulting in poor dispersion of pigment in fluororesin and poor coloring performance and color uniformity. Excessive coupling agent content will cause the coupling agent molecules to condense, which will promote the agglomeration of pigment particles and increase the number of bumps on the surface of the masterbatch.

[0050] In a second aspect, the present invention provides a method for preparing the above-mentioned fluororesin masterbatch, the method comprising the following steps:

[0051] The irradiated fluororesin and the color powder modified with coupling agent are mixed in an internal mixer to prepare a mixture. The mixture is then extruded, drawn into strips, and granulated by an extrusion device to obtain the fluororesin masterbatch.

[0052] In some embodiments of the present invention, the mixing temperature of the internal mixer is 220-260°C and the mixing time is 5-10 min;

[0053] And / or, during extrusion using an extrusion device, the unirradiated fluoropolymer is added to the mixture;

[0054] And / or, the extrusion temperature of the extrusion equipment is 260-300℃.

[0055] In a third aspect, the present invention provides a fluororesin composition comprising the fluororesin masterbatch as described above. Using a Motic BA200 microscope at a magnification of 100, the number of bumps on the surface of the fluororesin composition is observed to be less than 10. Using a Color i5 spherical colorimeter from X-Rite Ltd., the ΔE of the fluororesin masterbatch is measured to be less than 1.0.

[0056] The following specific embodiments and data explain the content of the present invention.

[0057] Example 1

[0058] The fluororesin masterbatch of this embodiment comprises the following components by weight, as shown in Table 1:

[0059] ① Irradiated FEP resin: 20 parts, wherein the FEP was obtained from commercially available (Zhejiang Juhua FJP810);

[0060] ② Iron oxide red modified with coupling agent: 20 parts, with a coupling agent to iron oxide red mass ratio of 2:100. Among them, the iron oxide red was obtained commercially (Lanxess Pigment Co., Ltd. 180M), and the coupling agent was KH550 (Jiangsu Nanjing Shuguang Chemical Plant).

[0061] The preparation process of fluoropolymer masterbatch is as follows:

[0062] 1) The FEP resin was irradiated using an irradiation device (ELV-8 type) with an irradiation dose of 5MRad to obtain 20 parts of irradiated FEP resin.

[0063] 2) After grinding the iron oxide red through a three-roll mill, a small amount of water was added to make a slurry. The coupling agent KH550 was dissolved in anhydrous ethanol and then added dropwise to the slurry. The mixture was stirred for 5-10 minutes to react with the pigment. After the reaction was completed, the mixture was dried to obtain 20 parts of iron oxide red modified with the coupling agent. The mass ratio of the coupling agent to the iron oxide red was 2:100.

[0064] 3) Place 20 parts of the above-mentioned irradiated FEP resin and 20 parts of the above-mentioned iron oxide modified by coupling agent into a mixer for mixing reaction. The mixing temperature is 220-260℃ and the mixing time is 5-10 min. After preparing the mixture, put the mixture into a twin-screw extruder for extrusion. The extrusion temperature is 260-300℃. After extrusion molding, pelletize the mixture into FEP masterbatch by pelletizing.

[0065] Preparation of fluoropolymer compositions:

[0066] The fluoropolymer masterbatch and FEP resin (Zhejiang Juhua FJP810) prepared above were put into a high-speed mixer at a mass ratio of 3:100 and stirred evenly for 5 minutes. Then, the mixture was extruded and blended using a single screw extruder to prepare a fluoropolymer composition.

[0067] Example 2

[0068] Please refer to Table 1. This embodiment includes the following parts by weight of raw materials:

[0069] ① Irradiated FEP resin: 50 parts, wherein the FEP was obtained from commercially available (Zhejiang Juhua FJP810);

[0070] ② Iron oxide red modified with coupling agent: 15 parts, with a coupling agent to iron oxide red mass ratio of 1:100. Among them, the iron oxide red was obtained commercially (Lanxess Pigment Co., Ltd. 180M), and the coupling agent was KH550 (Jiangsu Nanjing Shuguang Chemical Plant).

[0071] The preparation methods of fluororesin masterbatch and fluororesin composition are basically the same as those in Example 1, except that the proportions of each raw material component and the irradiation dose are different.

[0072] Example 3

[0073] Please refer to Table 1. This embodiment includes the following parts by weight of raw materials:

[0074] ① Irradiated FEP resin: 100 parts, wherein the FEP was obtained from commercially available (Zhejiang Juhua FJP810);

[0075] ② Iron oxide red modified with coupling agent: 10 parts, with a coupling agent to iron oxide red mass ratio of 0.25:100. Among them, the iron oxide red was obtained from commercially available (Lanxess Pigment Co., Ltd. 180M), and the coupling agent was KH550 (Jiangsu Nanjing Shuguang Chemical Plant).

[0076] The preparation methods of fluororesin masterbatch and fluororesin composition are basically the same as those in Example 1, except that the proportions of each raw material component and the irradiation dose are different.

[0077] Example 4

[0078] Please refer to Table 1. This embodiment includes the following parts by weight of raw materials:

[0079] ① Irradiated FEP resin: 30 parts, wherein the FEP was obtained from commercially available (Zhejiang Juhua FJP810);

[0080] ② Iron oxide red modified with coupling agent: 15 parts, with a coupling agent to iron oxide red mass ratio of 1:100. Among them, the iron oxide red was obtained commercially (Lanxess Pigment Co., Ltd. 180M), and the coupling agent was KH550 (Jiangsu Nanjing Shuguang Chemical Plant);

[0081] ③ Unirradiated FEP resin: 70 parts, of which the FEP was obtained from commercially available (Zhejiang Juhua FJP810).

[0082] The preparation process of fluoropolymer masterbatch is as follows:

[0083] 1) The FEP resin was irradiated using an irradiation device (ELV-8 type) with an irradiation dose of 8MRad to obtain 30 parts of irradiated FEP resin.

[0084] 2) After grinding the iron oxide red through a three-roll mill, a small amount of water was added to make a slurry. The coupling agent KH550 was dissolved in anhydrous ethanol and then added dropwise to the slurry to react with the pigment. The stirring time was 5-10 minutes. After the reaction was completed, the mixture was dried to obtain 15 parts of iron oxide red modified with the coupling agent. The mass ratio of the coupling agent to the iron oxide red was 1:100.

[0085] 3) Place 30 parts of the above-mentioned irradiated FEP resin and 15 parts of the above-mentioned iron oxide modified by coupling agent into a mixer for mixing reaction. The mixing temperature is 220-260℃ and the mixing time is 5-10 minutes. After preparing the mixture, put the mixture and 70 parts of the above-mentioned unirradiated fluororesin into a twin-screw extruder for extrusion. The extrusion temperature is 260-300℃. After extrusion molding, pelletize the mixture into FEP masterbatch by pelletizing.

[0086] Preparation of fluoropolymer compositions:

[0087] The fluoropolymer masterbatch and FEP resin (Zhejiang Juhua FJP810) prepared above were put into a high-speed mixer at a mass ratio of 3:100 and stirred evenly for 5 minutes. Then, the mixture was extruded and blended using a single screw extruder to prepare a fluoropolymer composition.

[0088] Example 5

[0089] Please refer to Table 1. This embodiment includes the following parts by weight of raw materials:

[0090] ① Irradiated FEP resin: 40 parts, wherein the FEP was obtained from commercially available (Zhejiang Juhua FJP810);

[0091] ② Iron oxide red modified with coupling agent: 15 parts, with a coupling agent to iron oxide red mass ratio of 1:100. Among them, the iron oxide red was obtained commercially (Lanxess Pigment Co., Ltd. 180M), and the coupling agent was KH550 (Jiangsu Nanjing Shuguang Chemical Plant);

[0092] ③ Unirradiated FEP resin: 60 parts, wherein the FEP was obtained from commercially available (Zhejiang Juhua FJP810).

[0093] The preparation methods of fluoropolymer masterbatch and fluoropolymer composition are basically the same as those in Example 4, except that the proportions of each raw material component are different.

[0094] Example 6

[0095] Please refer to Table 1. This embodiment includes the following parts by weight of raw materials:

[0096] ① Irradiated FEP resin: 50 parts, wherein the FEP was obtained from commercially available (Zhejiang Juhua FJP810);

[0097] ② Iron oxide red modified with coupling agent: 15 parts, with a coupling agent to iron oxide red mass ratio of 1:100. Among them, the iron oxide red was obtained commercially (Lanxess Pigment Co., Ltd. 180M), and the coupling agent was KH550 (Jiangsu Nanjing Shuguang Chemical Plant);

[0098] ③ Unirradiated FEP resin: 50 parts, wherein the FEP was obtained from commercially available (Zhejiang Juhua FJP810).

[0099] The preparation methods of fluoropolymer masterbatch and fluoropolymer composition are basically the same as those in Example 4, except that the proportions of each raw material component are different.

[0100] Example 7

[0101] Please refer to Table 1. This embodiment includes the following parts by weight of raw materials:

[0102] ① Irradiated FEP resin: 30 parts, wherein the FEP was obtained from commercially available (Zhejiang Juhua FJP810);

[0103] ② Iron oxide yellow modified with coupling agent: 15 parts, with a coupling agent to iron oxide yellow mass ratio of 1:100. Among them, the iron oxide yellow was obtained commercially (BAYFERROX 3905), and the coupling agent was KH550 (Jiangsu Nanjing Shuguang Chemical Plant);

[0104] ③ Unirradiated FEP resin: 70 parts, of which the FEP was obtained from commercially available (Zhejiang Juhua FJP810).

[0105] The preparation methods of fluoropolymer masterbatch and fluoropolymer composition are basically the same as those in Example 4, except that the composition and proportion of each raw material component are different.

[0106] Example 8

[0107] Please refer to Table 1. This embodiment includes the following parts by weight of raw materials:

[0108] ① Irradiated PFA resin: 30 parts, wherein the PFA was obtained commercially available (Zhejiang Juhua FJY-A06);

[0109] ② Iron oxide red modified with coupling agent: 15 parts, with a coupling agent to iron oxide red mass ratio of 1:100. Among them, the iron oxide red was obtained commercially (Lanxess Pigment Co., Ltd. 180M), and the coupling agent was KH550 (Jiangsu Nanjing Shuguang Chemical Plant);

[0110] ③ Unirradiated PFA resin: 70 parts, of which the PFA was obtained commercially available (Zhejiang Juhua FJY-A06).

[0111] The preparation methods of fluoropolymer masterbatch and fluoropolymer composition are basically the same as those in Example 4, except that the composition and proportion of each raw material component are different.

[0112] Comparative Example 1

[0113] Please refer to Table 1. This comparative example includes the following parts by mass of raw materials:

[0114] ① Irradiated FEP resin: 10 parts, wherein the FEP was obtained from commercially available sources (Zhejiang Juhua FJP810);

[0115] ② Iron oxide red modified with coupling agent: 15 parts, with a coupling agent to iron oxide red mass ratio of 1:100. Among them, the iron oxide red was obtained commercially (Lanxess Pigment Co., Ltd. 180M), and the coupling agent was KH550 (Jiangsu Nanjing Shuguang Chemical Plant);

[0116] ③ Unirradiated FEP resin: 90 parts, of which the FEP was obtained from commercially available (Zhejiang Juhua FJP810).

[0117] The preparation methods of fluoropolymer masterbatch and fluoropolymer composition are basically the same as those in Example 4, except that the proportions of each raw material component are different.

[0118] Comparative Example 2

[0119] Please refer to Table 1. This comparative example includes the following parts by mass of raw materials:

[0120] ① Irradiated FEP resin: 70 parts, wherein the FEP was obtained from commercially available (Zhejiang Juhua FJP810);

[0121] ② Iron oxide red modified with coupling agent: 15 parts, with a coupling agent to iron oxide red mass ratio of 1:100. Among them, the iron oxide red was obtained commercially (Lanxess Pigment Co., Ltd. 180M), and the coupling agent was KH550 (Jiangsu Nanjing Shuguang Chemical Plant);

[0122] ③ Unirradiated FEP resin: 30 parts, wherein the FEP was obtained from commercially available sources (Zhejiang Juhua FJP810).

[0123] The preparation methods of fluoropolymer masterbatch and fluoropolymer composition are basically the same as those in Example 4, except that the proportions of each raw material component are different.

[0124] Comparative Example 3

[0125] Please refer to Table 1. This comparative example includes the following parts by mass of raw materials:

[0126] ① Irradiated FEP resin: 30 parts, wherein the FEP was obtained from commercially available (Zhejiang Juhua FJP810);

[0127] ② Iron oxide red modified with coupling agent: 5 parts, with a coupling agent to iron oxide red mass ratio of 1:100. Among them, the iron oxide red was obtained commercially (Lanxess Pigment Co., Ltd. 180M), and the coupling agent was KH550 (Jiangsu Nanjing Shuguang Chemical Plant);

[0128] ③ Unirradiated FEP resin: 70 parts, of which the FEP was obtained from commercially available (Zhejiang Juhua FJP810).

[0129] The preparation methods of fluoropolymer masterbatch and fluoropolymer composition are basically the same as those in Example 4, except that the proportions of each raw material component are different.

[0130] Comparative Example 4

[0131] Please refer to Table 1. This comparative example includes the following parts by mass of raw materials:

[0132] ① Irradiated FEP resin: 30 parts, wherein the FEP was obtained from commercially available (Zhejiang Juhua FJP810);

[0133] ② Iron oxide red modified with coupling agent: 25 parts, with a coupling agent to iron oxide red mass ratio of 1:100. Among them, the iron oxide red was obtained commercially (Lanxess Pigment Co., Ltd. 180M), and the coupling agent was KH550 (Jiangsu Nanjing Shuguang Chemical Plant);

[0134] ③ Unirradiated FEP resin: 70 parts, of which the FEP was obtained from commercially available (Zhejiang Juhua FJP810).

[0135] The preparation methods of fluoropolymer masterbatch and fluoropolymer composition are basically the same as those in Example 4, except that the proportions of each raw material component are different.

[0136] Comparative Example 5

[0137] Please refer to Table 1. This comparative example includes the following parts by mass of raw materials:

[0138] ① Irradiated FEP resin: 30 parts, wherein the FEP was obtained from commercially available (Zhejiang Juhua FJP810);

[0139] ② Iron oxide red: 15 parts, iron oxide red was obtained commercially (Lanxess Pigment Ltd. 180M);

[0140] ③ Unirradiated FEP resin: 70 parts, of which the FEP was obtained from commercially available (Zhejiang Juhua FJP810).

[0141] The preparation methods of fluoropolymer masterbatch and fluoropolymer composition are basically the same as those in Example 4, except that the proportions of each raw material component are different.

[0142] Comparative Example 6

[0143] Please refer to Table 1. This comparative example includes the following parts by mass of raw materials:

[0144] ① Irradiated FEP resin: 30 parts, wherein the FEP was obtained from commercially available (Zhejiang Juhua FJP810);

[0145] ② Iron oxide red modified with coupling agent: 15 parts, with a coupling agent to iron oxide red mass ratio of 0.134:100. Among them, the iron oxide red was obtained from commercially available (Lanxess Pigment Co., Ltd. 180M), and the coupling agent was KH550 (Jiangsu Nanjing Shuguang Chemical Plant);

[0146] ③ Unirradiated FEP resin: 70 parts, of which the FEP was obtained from commercially available (Zhejiang Juhua FJP810).

[0147] The preparation methods of fluoropolymer masterbatch and fluoropolymer composition are basically the same as those in Example 4, except that the proportions of each raw material component are different.

[0148] Comparative Example 7

[0149] Please refer to Table 1. This comparative example includes the following parts by mass of raw materials:

[0150] ① Irradiated FEP resin: 30 parts, wherein the FEP was obtained from commercially available (Zhejiang Juhua FJP810);

[0151] ② Iron oxide red modified with coupling agent: 15 parts, with a coupling agent to iron oxide red mass ratio of 4.895:100. Among them, the iron oxide red was obtained from commercially available (Lanxess Pigment Co., Ltd. 180M), and the coupling agent was KH550 (Jiangsu Nanjing Shuguang Chemical Plant);

[0152] ③ Unirradiated FEP resin: 70 parts, of which the FEP was obtained from commercially available (Zhejiang Juhua FJP810).

[0153] The preparation methods of fluoropolymer masterbatch and fluoropolymer composition are basically the same as those in Example 4, except that the proportions of each raw material component are different.

[0154] Comparative Example 8

[0155] Please refer to Table 1. This comparative example includes the following parts by mass of raw materials:

[0156] ① Unirradiated FEP resin: 100 parts, wherein the FEP was obtained from commercially available (Zhejiang Juhua FJP810);

[0157] ② Iron oxide red modified with coupling agent: 15 parts, with a coupling agent to iron oxide red mass ratio of 1:100. Among them, the iron oxide red was obtained commercially (Lanxess Pigment Co., Ltd. 180M), and the coupling agent was KH550 (Jiangsu Nanjing Shuguang Chemical Plant);

[0158] The preparation process of fluoropolymer masterbatch is as follows:

[0159] 1) After grinding iron oxide red through a three-roll mill, a small amount of water was added to make a slurry; the coupling agent KH550 was dissolved in anhydrous ethanol, and then added dropwise to the slurry to react with the pigment, stirring for 5-10 minutes; after the reaction was completed, the mixture was dried to obtain 15 parts of iron oxide red modified with the coupling agent. The mass ratio of coupling agent to iron oxide red was 1:100.

[0160] 3) 100 parts of the above-mentioned unirradiated FEP resin and 15 parts of the above-mentioned iron oxide modified with coupling agent are placed in a mixer for mixing reaction. The mixing temperature is 220-260℃ and the mixing time is 5-10 min. After preparing the mixture, the mixture is placed in a twin-screw extruder for extrusion. The extrusion temperature is 260-300℃. After extrusion molding, the mixture is pelletized by a pelletizer to prepare FEP masterbatch.

[0161] Preparation of fluoropolymer compositions:

[0162] The fluoropolymer masterbatch and FEP resin (Zhejiang Juhua FJP810) prepared above were put into a high-speed mixer at a mass ratio of 3:100 and stirred evenly for 5 minutes. Then, the mixture was extruded and blended using a single screw extruder to prepare a fluoropolymer composition.

[0163] The preparation methods of fluoropolymer masterbatch and fluoropolymer composition are basically the same as those in Example 4, except that the proportions of each raw material component are different.

[0164] Comparative Example 9

[0165] Please refer to Table 1. This comparative example includes the following parts by mass of raw materials:

[0166] ① Irradiated FEP resin: 30 parts, wherein the FEP was obtained from commercially available (Zhejiang Juhua FJP810);

[0167] ② Iron oxide red modified with coupling agent: 15 parts, with a coupling agent to iron oxide red mass ratio of 1:100. Among them, the iron oxide red was obtained commercially (Lanxess Pigment Co., Ltd. 180M), and the coupling agent was KH550 (Jiangsu Nanjing Shuguang Chemical Plant);

[0168] ③ Unirradiated FEP resin: 70 parts, of which the FEP was obtained from commercially available (Zhejiang Juhua FJP810).

[0169] The preparation process of fluoropolymer masterbatch is as follows:

[0170] 1) The FEP resin was irradiated using an irradiation device (ELV-8 type) with an irradiation dose of 3MRad to obtain 30 parts of irradiated FEP resin.

[0171] 2) After grinding the iron oxide red through a three-roll mill, a small amount of water was added to make a slurry. The coupling agent KH550 was dissolved in anhydrous ethanol and then added dropwise to the slurry to react with the pigment. The stirring time was 5-10 minutes. After the reaction was completed, the mixture was dried to obtain 15 parts of iron oxide red modified with the coupling agent. The mass ratio of the coupling agent to the iron oxide red was 1:100.

[0172] 3) Place 30 parts of the above-mentioned irradiated FEP resin and 15 parts of the above-mentioned iron oxide modified by coupling agent into a mixer for mixing reaction. The mixing temperature is 220-260℃ and the mixing time is 5-10 minutes. After preparing the mixture, put the mixture and 70 parts of the above-mentioned unirradiated fluororesin into a twin-screw extruder for extrusion. The extrusion temperature is 260-300℃. After extrusion molding, pelletize the mixture into FEP masterbatch by pelletizing.

[0173] Preparation of fluoropolymer compositions:

[0174] The fluoropolymer masterbatch and FEP resin (Zhejiang Juhua FJP810) prepared above were put into a high-speed mixer at a mass ratio of 3:100 and stirred evenly for 5 minutes. Then, the mixture was extruded and blended using a single screw extruder to prepare a fluoropolymer composition.

[0175] Comparative Example 10

[0176] Please refer to Table 1. This comparative example is similar to Comparative Example 9, except that the irradiation dose is 15MRad.

[0177] The fluororesin masterbatches and fluororesin compositions prepared in the above examples and comparative examples were pressed into films using a flatbed hot press, and their elongation at break, tensile strength, nodule count, and ΔE were measured according to the following standards:

[0178] (1) Elongation at break and tensile strength

[0179] The test was conducted according to Clause 9 of GB 1040—2008, with a test temperature of 23±2℃. The tensile test used a standard dumbbell-shaped specimen with a tensile speed of 250 mm / min. The tensile strength and elongation at break of five specimens were tested using a micro-controlled electronic universal tensile testing machine from Dongguan High-Speed ​​Railway Testing Co., Ltd., and the average value of the results was taken.

[0180] (2) Number of bumps

[0181] The dispersion of fluoropolymer masterbatch and fluoropolymer composition on the surface of a 2mm thick plastic sheet with an area of ​​120cm*120cm was observed using an optical microscope (Motic, microscope BA200). The microscope magnification was 100x.

[0182] (3)ΔE

[0183] A colorimeter (Color i5 spherical colorimeter from X-Rite Inc.) was used to measure the prepared 2mm thick plastic plate sample. The CIELAB color space, D65 light source, and 10° observer viewing angle were selected. Multiple measurements were taken in SCE mode, and the average value was calculated. According to the CIE color system L*a*b* color space, L* represents lightness, +a* represents redness, -a* represents greenness, +b* represents yellowness, and -b* represents blueness. The color performance is evaluated by assessing the magnitude of the color difference ΔE. ΔE is a mathematical formula for calculating the total difference between two colors (usually a standard color / target color) in the L*a*b* color space: ΔE = √(ΔL*b ... 2 +Δa 2 +Δb 2 The smaller the value, the closer the two colors are, and the better the color performance.

[0184] The test results are detailed in Table 2.

[0185] Table 1. Preparation conditions of fluororesin masterbatch for embodiments and comparative examples of the present invention.

[0186]

[0187] Table 2 Performance parameters of embodiments and comparative examples of the present invention

[0188]

[0189]

[0190] As shown in Tables 1 and 2, in Examples 1-8, the number of bumps on the surface of the fluororesin masterbatch was less than 20 when observed using a Motic BA200 microscope at 100x magnification. The ΔE of the fluororesin masterbatch was measured to be less than 1.0 using a Colori5 spherical colorimeter from X-Rite Ltd. This indicates that when 20-100 parts of irradiated fluororesin and 10-20 parts of color powder modified with a coupling agent are used, the fluororesin masterbatch of this invention has a smooth surface and good coloring performance and color uniformity.

[0191] As shown in Tables 1 and 2, Examples 1-8 show that the ratio of fluororesin masterbatch to fluororesin in the fluororesin composition is 3:100, meaning that a very small amount of fluororesin masterbatch is added. Using a Motic BA200 microscope at 100x magnification, the number of bumps on the surface of the fluororesin composition is less than 10. Using a Color i5 spherical colorimeter from X-Rite Co., Ltd., the ΔE of the fluororesin composition is measured to be <1.0, indicating that the fluororesin composition of the present invention has a smooth surface and good coloring performance and color uniformity. This also indicates that the fluororesin masterbatch of the present invention has a smooth surface and good coloring performance and color uniformity.

[0192] Examples 1-3 show that the elongation at break of Example 1 was 157% and the tensile strength was 45.1 MPa, the elongation at break of Example 2 was 163% and the tensile strength was 44.8 MPa, and the elongation at break of Example 3 was 188% and the tensile strength was 43.4 MPa. Without adding unirradiated fluoropolymer, when the irradiation dose was 5-10 MRad, the elongation at break of the fluoropolymer masterbatch increased and the tensile strength decreased with the increase of the irradiation dose.

[0193] Compared with Example 2, Example 6 did not include unirradiated fluororesin. The elongation at break of Example 2 was 163% and the tensile strength was 44.8 MPa. With the addition of unirradiated fluororesin, the elongation at break of Example 6 was 199% and the tensile strength was 52.7 MPa. The mechanical properties of Example 6 were significantly better than those of Example 2, indicating that adding unirradiated fluororesin can simultaneously improve the elongation at break and tensile strength of fluororesin masterbatch, thereby improving the mechanical properties of fluororesin masterbatch.

[0194] Compared with Example 4, Comparative Examples 1 and 2 showed that the amount of irradiated FEP fluororesin was too small. Comparative Example 1 had 32 nodules, ΔE of 1.4, elongation at break of 122%, and tensile strength of 39.1 MPa. Comparative Examples 2 showed too much irradiated FEP fluororesin. Comparative Example 2 had 20 nodules, ΔE of 0.7, elongation at break of 147%, and tensile strength of 38.4 MPa. Example 4 had 19 nodules, ΔE of 0.7, elongation at break of 166%, and tensile strength of 46.9 MPa. The surface smoothness, color, and mechanical properties of Comparative Example 1 were all worse. The surface smoothness and color of Comparative Example 2 were similar to those of Example 4, but the mechanical properties were significantly worse. Therefore, irradiated fluororesin in the range of 30-50 parts can simultaneously improve surface smoothness, color, and mechanical properties compared to less than 30 parts; and compared to more than 50 parts, it can improve mechanical properties.

[0195] Compared with Example 4, Comparative Examples 3 and 4 showed that the amount of pigment modified with coupling agent was too small. Comparative Example 3 had 23 nodules, ΔE of 1.1, elongation at break of 142%, and tensile strength of 40.2 MPa. Comparative Examples 4 showed too much pigment modified with coupling agent. Comparative Example 4 had 30 nodules, ΔE of 0.7, elongation at break of 134%, and tensile strength of 45.9 MPa. Example 4 had 19 nodules, ΔE of 0.7, elongation at break of 166%, and tensile strength of 46.9 MPa. The surface smoothness, color, and mechanical properties of Comparative Example 3 all deteriorated. The color of Comparative Example 4 was similar to that of Example 4, but its surface smoothness and mechanical properties deteriorated. Insufficient pigment modified with coupling agent resulted in poor dispersibility in the fluoropolymer, leading to poor appearance, color, and mechanical properties. Excessive pigment modified with coupling agent increased the number of nodules and also reduced mechanical properties to some extent. Therefore, it can be seen that, compared with less than 10 parts of the color powder modified by coupling agent, the color powder modified by coupling agent in the range of 10-20 parts can simultaneously improve the surface smoothness, color and mechanical properties; compared with more than 20 parts of the color powder modified by coupling agent, it can improve the mechanical properties.

[0196] Compared with Example 4, Comparative Examples 5, 6, and 7 showed the following results: Comparative Example 5, without coupling agent modification, had 35 nodules, ΔE of 1.3, elongation at break of 144%, and tensile strength of 39.7 MPa; Comparative Example 6, with an excessively low ratio of coupling agent to pigment, had 32 nodules, ΔE of 1.0, elongation at break of 149%, and tensile strength of 41.1 MPa; Comparative Example 7, with an excessively high ratio of coupling agent to pigment, had 28 nodules, ΔE of 0.9, elongation at break of 162%, and tensile strength of 45.2 MPa; and Example 4 had 19 nodules, ΔE of 0.7, elongation at break of 166%, and tensile strength of 46.9 MPa. The surface smoothness, color, and mechanical properties of Comparative Examples 5 and 6 deteriorated. The color and mechanical properties of Comparative Example 7 were similar to those of Example 4, but the surface smoothness deteriorated. If the ratio of coupling agent to pigment is too small, its dispersibility in fluoropolymers is poor, resulting in deterioration of appearance, color, and mechanical properties. Conversely, if the ratio is too large, it leads to condensation of coupling agent molecules, which in turn promotes pigment particle agglomeration, increasing the number of lumps and reducing mechanical properties. Therefore, a coupling agent to pigment mass ratio of (0.25-2):100, compared to a ratio less than 0.25:100, can simultaneously improve surface smoothness, color, and mechanical properties; and compared to a ratio greater than 2:100, it can improve appearance.

[0197] Compared with Example 4, Comparative Examples 8, 9, and 10 used completely unirradiated fluoropolymers. Comparative Example 8 had 34 nodules, ΔE of 1.5, elongation at break of 156%, and tensile strength of 44.3 MPa. The irradiation dose was too low, resulting in 27 nodules, 1.2 ΔE, 160% elongation at break, and 44.9 MPa for Comparative Example 9. The irradiation dose was too high, resulting in 18 nodules, 0.7 ΔE, 172% elongation at break, and 38.4 MPa for Comparative Example 4. The nodules were 19, ΔE was 0.7, elongation at break was 166%, and tensile strength was 46.9 MPa. The surface smoothness, color, and mechanical properties of Comparative Examples 8 and 9 deteriorated. The color and appearance properties of Comparative Example 10 were similar to those of Example 4, but the tensile properties were significantly worse. Too low an irradiation dose will lead to incomplete degradation of fluoropolymers and fewer active sites; too high an irradiation dose will cause a severe decline in various properties of fluoropolymers, such as tensile strength. Therefore, compared to an irradiation dose of less than 5 MRad, an irradiation dose of 5-10 MRad can simultaneously improve surface smoothness, color, and mechanical properties; and compared to an irradiation dose of more than 10 MRad, it can improve tensile strength.

[0198] As can be seen from Examples 4-8, Comparative Examples 1-2, and Comparative Examples 8-10 above, 30-50 parts of irradiated fluororesin, 10-20 parts of color powder modified with coupling agent, and 50-70 parts of unirradiated fluororesin, with an irradiation dose of 5-10 MRad, form a synergistic effect. The resulting fluororesin masterbatch has good appearance, color, and mechanical properties. This is because after the fluororesin of the present invention undergoes irradiation pretreatment, it will undergo slight oxidative degradation, forming active free radicals. On the one hand, after slight degradation of the fluororesin, the melt viscosity decreases, which is more conducive to the shear dispersion of color powder in the fluororesin. On the other hand, the fluororesin and color powder particles can be bridged by the coupling agent to form chemical bonds, improving the dispersion of color powder particles in the fluororesin. This makes the surface of the fluororesin masterbatch smooth, improving the coloring performance, color uniformity, and mechanical properties of the fluororesin masterbatch, and simultaneously improving the elongation at break and tensile strength.

[0199] The above are merely preferred embodiments of the present invention and do not limit the patent scope of the present invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the patent protection scope of the present invention.

Claims

1. A fluororesin masterbatch, characterized in that, Using a Motic BA200 microscope at 100x magnification, the number of bumps on the surface of the fluororesin masterbatch was found to be less than 20; the ΔE of the fluororesin masterbatch was measured to be less than 1.0 using a Colori5 spherical colorimeter from X-Rite Ltd.

2. The fluoropolymer masterbatch as described in claim 1, characterized in that, The fluororesin masterbatch raw material, by weight, includes: 20-100 parts of irradiated fluororesin and 10-20 parts of color powder modified by coupling agent.

3. The fluoropolymer masterbatch as described in claim 2, characterized in that, The fluororesin masterbatch raw material, by weight, includes: 30-50 parts of irradiated fluororesin, 10-20 parts of color powder modified with coupling agent, and 50-70 parts of unirradiated fluororesin, wherein the total mass of the unirradiated fluororesin and the irradiated fluororesin is 100 parts.

4. The fluoropolymer masterbatch as described in claim 2, characterized in that, The fluororesin includes at least one of fluorinated ethylene propylene copolymer (FEP), meltable polytetrafluoroethylene (PFA), polytetrafluoroethylene (PTFE), and ethylene-tetrafluoroethylene copolymer (ETFE).

5. The fluoropolymer masterbatch as described in claim 2, characterized in that, The pigment includes at least one of phthalocyanine blue, phthalocyanine green, iron oxide red, iron oxide yellow, pigment red, pigment yellow, pigment purple, carbon black, and titanium dioxide; And / or, the coupling agent is a silane coupling agent.

6. The fluoropolymer masterbatch as described in claim 2, characterized in that, In the color powder modified with coupling agent, the mass ratio of the coupling agent to the color powder is (0.25-2):

100.

7. The fluoropolymer masterbatch as described in claim 2, characterized in that, The irradiation dose of the irradiated fluoropolymer is 5-10 MRad.

8. A method for preparing fluoropolymer masterbatch as described in claim 2, characterized in that, Includes the following steps: The irradiated fluororesin and the color powder modified with coupling agent are mixed in an internal mixer to prepare a mixture. The mixture is then extruded, drawn into strips, and granulated by an extrusion device to obtain the fluororesin masterbatch.

9. A method for preparing fluororesin masterbatch as described in claim 8, characterized in that, The mixing temperature of the internal mixer is 220-260℃, and the mixing time is 5-10 minutes. And / or, during extrusion using an extrusion device, the unirradiated fluoropolymer is added to the mixture; And / or, the extrusion temperature of the extrusion equipment is 260-300℃.

10. A fluoropolymer composition, characterized in that, The fluororesin masterbatch as described in claim 1 was observed to have less than 10 bumps on the surface of the fluororesin composition under a Motic BA200 microscope at a magnification of 100; and the ΔE of the fluororesin masterbatch was measured to be less than 1.0 using a Color i5 spherical colorimeter from X-Rite Ltd.

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