A fluorine resin fluorine rubber composite material with high breaking work and a preparation method thereof

Abstract

The application provides a fluororesin fluororubber composite material with high breaking work and a preparation method thereof, raw materials of the fluororesin fluororubber composite material include the following components in parts by weight: 100-120 parts of fluororubber; 20-40 parts of fluororesin micro powder; 1-8 parts of a crosslinking agent; and 0.1-6 parts of an auxiliary crosslinking agent. The fluororesin fluororubber composite material can improve breaking work, cleanliness and etching gas resistance.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of fluororubber composites, in particular to a fluororesin fluororubber composite with high breaking work and a preparation method thereof. BACKGROUND

[0002] Fluororubber refers to a synthetic high polymer rubber (elastomer) containing fluorine atoms on the carbon atoms of the main chain or side chain. Due to the strong electronegativity of fluorine atoms and the high bond energy of fluorine-carbon bonds, fluororubber has outstanding chemical resistance, weather resistance, heat resistance and other characteristics, and is therefore widely used as a sealing material in semiconductor processing equipment with harsh working conditions.

[0003] Fluororubber generally requires a certain amount of filler for reinforcement. In addition to traditional fillers such as carbon black and white carbon black, fluororesin as a new type of filler has also received increasing attention. Common fluororesins have good plasma resistance and cleanliness compared to traditional fillers, but their reinforcing properties are generally inferior to those of traditional fillers.

[0004] In the prior art, patent application file with authorization number CN 113681740 B discloses a method for modifying ternary fluororubber with fluororesin. The fluororesin powder has excellent comprehensive performance, good dispersibility, and easy mixing with other materials, which can improve the processing performance and physical properties of F246 ternary fluororubber. Patent application file with authorization number CN 113943467 B discloses a fluororubber composition, its preparation method and application. The use of fluororesin reduces the friction coefficient of fluororubber dynamic seals, thereby prolonging their service life.

[0005] In summary, the fluororubber compositions in the prior art cannot simultaneously have high plasma resistance and high breaking work and breaking toughness. In theory, the higher the fluorine content of the resin, the better the performance of resisting fluorine-containing etching gas. However, most PTFE micropowder is only used as a filler in the rubber formulation system, and there is no good mutual interaction force between this crystalline resin and the rubber system, i.e. no chemical or polar physical bond interaction force, so the breaking energy of the entire system is very low. SUMMARY

[0006] In view of the above-mentioned shortcomings of the prior art, the purpose of the present application is to provide a fluororesin fluororubber composite with high breaking work and a preparation method thereof, which can improve the breaking energy, cleanliness and etching gas resistance, thereby solving the problems in the prior art.

[0007] To achieve the above-mentioned purposes and other related purposes, one aspect of the present application provides a fluororesin fluororubber composite. The raw materials of the fluororesin fluororubber composite include the following components by weight:

[0008]

[0009]

[0010] The fluororesin micro powder is selected from one or more of tetrafluoroethylene hexafluoropropylene copolymer, polyvinylidene fluoride, polytetrafluoroethylene and melt polytetrafluoroethylene.

[0011] The second aspect of the present application provides a preparation method of the fluororesin fluororubber composite material according to the first aspect of the present application, and the preparation method comprises:

[0012] 1) uniformly plasticize the fluororubber on a two-roll open mill, then add the fluororesin micro powder, crosslinking agent and co-crosslinking agent into the open mill to mix uniformly to obtain a wrapped roll rubber mixture;

[0013] 2) cut the wrapped roll rubber mixture left and right, adjust the roll gap of the open mill to the minimum, wrap a triangle, uniformly mix and knead, and then sheet out to obtain a rubber mixture;

[0014] 3) stop the rubber mixture, re-mix and sheet out for use.

[0015] The third aspect of the present application provides the use of the fluororesin fluororubber composite material according to the first aspect of the present application in the fields of semiconductors, photovoltaics, aerospace.

[0016] Compared with the prior art, the present application has the following beneficial effects:

[0017] The present application provides a fluororesin fluororubber composite material and a preparation method thereof, by adding specific fluororesin micro powder to the fluorine-containing rubber to prepare a composite material, not only the breaking work and mechanical properties of the fluorine-containing rubber can be improved, but also the fluororubber can still maintain a relatively high cleanliness after being subjected to high ion working environment, thereby expanding the use range of the fluororubber. Thus, the sealing material can meet the higher working environment requirements of the semiconductor, photovoltaic, aerospace and other fields in terms of breaking resistance and plasma resistance. Specifically, the Shore A hardness is > 56, preferably > 60; the tensile strength is > 9 MPa, preferably > 11 MPa; the elongation at break is > 240%, preferably > 250%; the 100% modulus is > 5 MPa, preferably > 9 MPa; the breaking work is > 0.35 N / m, preferably > 0.4 MN / m; and the plasma mass loss is less than 1.6%, preferably less than 1.5%. DETAILED DESCRIPTION

[0018] Hereinafter, an embodiment of a fluororesin fluororubber composite material with high breaking work and a preparation method thereof are specifically disclosed.

[0019] The ranges disclosed herein are defined by the endpoints as modified by "about" to allow for variations that are minor alterations of a given range. Such ranges are inclusive of the endpoints and are also inclusive of any point or sub-range derivable by any combination of the endpoints. For example, if a range is stated as 60-120 and 80-110, it is understood that a range of 60-110 and 80-120 is also contemplated. Furthermore, if a minimum range value of 1 and 2 is stated, and a maximum range value of 3, 4, and 5 is stated, then the following ranges are all contemplated: 1-3, 1-4, 1-5, 2-3, 2-4, and 2-5. In this application, unless otherwise indicated, a numerical range "a-b" means a range of any combination of the numbers a and b, wherein a and b are both real numbers. For example, the numerical range "0-5" means that all real numbers between "0-5" have been listed herein, and "0-5" is merely a shorthand for listing all of those numbers. Also, when a parameter is stated to be an integer > 2, it is equivalent to stating that the parameter is, for example, an integer 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.

[0020] Unless otherwise specified, all embodiments and optional embodiments of the present application can be combined with each other to form new technical solutions.

[0021] The present application can not only improve the fracture work and mechanical properties of fluorine-containing rubber, but also maintain relatively high cleanliness of fluorine-containing rubber after being subjected to high ion working environment, thereby expanding the use range of fluorine-containing rubber, by optimizing the formula, specifically, by comprehensively selecting a specific kind of fluororesin micro powder and adding it to the fluorine-containing rubber to prepare a composite material. Thus, the sealing material can meet the higher working environment of the semiconductor, photovoltaic, aerospace and other fields in terms of fracture resistance and plasma resistance. On this basis, the present application is completed.

[0022]

Fluororesin fluororubber composite material

[0023] One aspect of the present application provides a fluororesin fluororubber composite material, which raw materials include fluororubber, fluororesin micro powder, crosslinking agent, and crosslinking aid.

[0024] The fluororesin fluororubber composite material provided by the present application can include 100-120 parts of fluororubber by weight. Alternatively, the weight of fluororubber is 100-110 parts, 110-120 parts, or 100 parts.

[0025] Further, the fluorine rubber is selected from one or more of FKM 26, FKM 246, perfluoroalkoxy alkoxy (PFA), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), perfluoroalkoxy alkoxy (PFA), perfluoroelastomer (FFKM), fluorinated phosphazene rubber.

[0026] The fluororesin fluorine rubber composite provided by the present application can include 20-40 parts of fluororesin powder by weight. Alternatively, the fluororesin powder can be 20-30 parts, 30-40 parts, 20-35 parts, or 35-40 parts by weight. Preferably, the amount is 30-40 parts, and more preferably 35-40 parts. Too much will make the plastic too strong and the elasticity will decrease, and too little will not be strong enough and the plasma resistance will be weak.

[0027] Further, the fluororesin powder is selected from one or more of tetrafluoroethylene-hexafluoropropylene copolymer (FEP), polyvinylidene fluoride (PVDF), polytetrafluoroethylene, and melt-processable polytetrafluoroethylene. Alternatively, the melt-processable polytetrafluoroethylene can be EA2000 produced by AGC.

[0028] The fluororesin powder has a melting peak, and the fluororesin powder includes C, F, and other elements, which are one or more of oxygen, sulfur, and nitrogen, and the molar ratio of other elements to total elements is 3-10 parts per million. Alternatively, the molar ratio of other elements to total elements is 3-5 parts per million, 5-10 parts per million, 5-8 parts per million, or 8-10 parts per million. When the ratio of other elements exceeds 10 parts per million, the crystallization of the resin is destroyed, the polymerization difficulty is increased, and the etching resistance of the formed powder is decreased. When the ratio of other elements is less than 3%, the formed resin powder has poor effect on improving the breaking energy.

[0029] The molar ratio of elements is obtained by standard XPS element analysis, and the following Table 1 is used as an example:

[0030] Table 1

[0031]

[0032] The fluororesin fluorine rubber composite provided by the present application can include 1-8 parts of a crosslinking agent by weight. Alternatively, the crosslinking agent can be 1-3 parts, 3-8 parts, 3-5 parts, or 5-8 parts by weight.

[0033] Further, the crosslinking agent is selected from one or more of 2,5-dimethyl-2,5-bis(tert-butyl peroxy)hexane (such as DBPH), 2,2-bis(3-amino-4-hydroxyphenyl)-hexafluoropropane (such as BOAP), and fluorinated aralkyl phosphonium salt. Preferably, the crosslinking agent is 2,5-dimethyl-2,5-bis(tert-butyl peroxy)hexane.

[0034] The fluororesin fluororubber composite provided by the present application can include 0.1-6 parts of a co-crosslinking agent by weight. Alternatively, the co-crosslinking agent can be 3-6 parts, 3-4 parts, 4-5 parts or 5-6 parts by weight.

[0035] Further, the co-crosslinking agent is triallyl isocyanurate (TAIC) or trimethallyl isocyanurate (TMAIC). Preferably, the co-crosslinking agent is triallyl isocyanurate.

[0036] The fluororesin fluororubber composite provided by the present application has a Shore A hardness of >56, preferably >60, such as 60-70, 60-65, etc., and more preferably >65.

[0037] The fluororesin fluororubber composite provided by the present application has a tensile strength of >9 MPa, preferably >11 MPa, such as 11-14, and more preferably >13 MPa.

[0038] The fluororesin fluororubber composite provided by the present application has an elongation at break of >240%, preferably >250%, such as 250-270%, and more preferably >260%.

[0039] The fluororesin fluororubber composite provided by the present application has a 100% modulus of >5 MPa, preferably >9 MPa, such as 9.2-12 MPa, and more preferably >11 MPa.

[0040] The fluororesin fluororubber composite provided by the present application has a work of rupture of >0.35 N / m, preferably >0.4 MN / m, and more preferably >0.45 MN / m.

[0041] The fluororesin fluororubber composite provided by the present application has a plasma mass loss of <1.6%, preferably <1.5%, such as 1.1-1.4, and more preferably <1.2%.

[0042] Method for preparing the fluororesin fluororubber composite

[0043] The second aspect of the present application provides a method for preparing the fluororesin fluororubber composite of the first aspect of the present application, which comprises:

[0044] 1) uniformly plasticize the fluororubber on a two-roll mill, then add the fluororesin powder, crosslinking agent and co-crosslinking agent into the mill to mix uniformly to obtain a wrapped roll rubber mixture;

[0045] 2) The rubber mixture of the roll is cut left and right, the roll gap of the mill is adjusted to the minimum, the triangle bag is punched, and the rubber is mixed evenly to obtain the rubber sheet;

[0046] 3) The rubber is parked, re-mixed and sheeted for use.

[0047] In the preparation method of the fluororesin fluororubber composite material provided by the application, in step 2), the left and right knives are each cut 3-10 times.

[0048] In the preparation method of the fluororesin fluororubber composite material provided by the application, in step 2), the triangle bag is punched 10-30 times.

[0049] In the preparation method of the fluororesin fluororubber composite material provided by the application, in step 2), the roll cylinder temperature of the mill is controlled within 60 DEG C.

[0050] In the preparation method of the fluororesin fluororubber composite material provided by the application, in step 3), the rubber is parked for 16 h or more.

[0051] In the preparation method of the fluororesin fluororubber composite material provided by the application, in step 3), the rubber is re-mixed for 10 min and sheeted for use.

[0052]

Application

[0053] The third aspect of the application provides the use of the fluororesin fluororubber composite material according to the first aspect of the application in the fields of semiconductors, photovoltaics, aerospace.

[0054] The beneficial effects of the application are further illustrated by the following examples.

[0055] In order to make the invention purposes, technical solutions and beneficial technical effects of the application clearer, the application is further described in detail in combination with the following examples. However, it should be understood that the examples of the application are only for the purpose of explaining the application, and are not intended to limit the application, and the examples of the application are not limited to the examples given in the specification. The specific experimental conditions or operation conditions in the examples are not specified, and are made according to the conventional conditions or the conditions recommended by the material suppliers.

[0056] Furthermore, it should be understood that the recitations of one or more method steps in the present application do not, unless otherwise specified, preclude the presence of additional method steps before and / or after the combined steps, nor do they preclude the insertion of additional method steps between the explicitly recited steps; it should also be understood that the recitations of a combined connection between one or more devices / apparatuses in the present application do not, unless otherwise specified, preclude the presence of additional devices / apparatuses before and / or after the combined devices / apparatuses, nor do they preclude the insertion of additional devices / apparatuses between the explicitly recited two devices / apparatuses. Moreover, unless otherwise specified, the numbering of the method steps is merely a convenient tool to identify individual method steps and does not serve as a limitation on the arrangement of the method steps or as a definition of the scope of the application, and a change in the relative positions of the method steps, or a modification of the method steps, without substantial alteration of the technical content, is also deemed to be within the scope of the application.

[0057] In the following examples, the reagents, materials and instruments used are commercially available unless otherwise specified.

[0058] The molar ratio of elements is obtained by standard XPS elemental analysis.

[0059] The fluororubber is purchased from AGC with model 600X.

[0060] The fluororesin fine powder 1 is purchased from AGC with model EA2000. The content of other elements is 8.1 parts per thousand.

[0061] The fluororesin fine powder 2 is purchased from Solvay with model F5AR. The content of other elements is 0.5 parts per thousand.

[0062] The fluororesin fine powder 3 is purchased from Zhejiang GeRu with model GR-C547. The content of other elements is 0.2 parts per thousand.

[0063] The crosslinking agent is 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane.

[0064] The co-crosslinking agent is triallyl isocyanurate.

[0065] The test methods or standards involved are as follows

[0066] 1. Shore A hardness: GB / T 531.1;

[0067] 2. Tensile strength: GB / T 528;

[0068] 3. Elongation at break: GB / T 528;

[0069] 4. 100% modulus: GB / T 528;

[0070] 5. Work of rupture: GB / T 528 tensile test stress-strain curve integral;

[0071] 6. Plasma mass loss: ICP etching, room temperature, 10 Pa, 60 min, CF4.

[0072] Example 1

[0073] A method for preparing a fluororesin fluororubber composite material, comprising the following steps:

[0074] (1) uniformly plasticize and roll 100 parts of fluororubber on a two-roll open mill, then gradually add 20 parts of fluororesin powder 1, 3 parts of 2,5-dimethyl-2,5-di(tert-butyl peroxy) hexane, and 3 parts of triallyl isocyanurate into the open mill and mix uniformly;

[0075] (2) cut the rolled rubber mixture left and right for 10 times respectively, adjust the roll gap of the open mill to the minimum, punch the triangular package for 30 times, control the roll cylinder temperature of the open mill within 60°C, and then out of the sheet after mixing uniformly;

[0076] (3) stop the mixing rubber for 16h, re-mix for 10min, and out of the sheet for standby.

[0077] Example 2

[0078] A method for preparing a fluororesin fluororubber composite material, comprising the following steps:

[0079] (1) uniformly plasticize and roll 100 parts of fluororubber on a two-roll open mill, then gradually add 30 parts of fluororesin powder 1, 3 parts of 2,5-dimethyl-2,5-di(tert-butyl peroxy) hexane, and 3 parts of triallyl isocyanurate into the open mill and mix uniformly;

[0080] (2) cut the rolled rubber mixture left and right for 10 times respectively, adjust the roll gap of the open mill to the minimum, punch the triangular package for 30 times, control the roll cylinder temperature of the open mill within 60°C, and then out of the sheet after mixing uniformly;

[0081] (3) stop the mixing rubber for 16h, re-mix for 10min, and out of the sheet for standby.

[0082] Example 3

[0083] A method for preparing a fluororesin fluororubber composite material, comprising the following steps:

[0084] (1) uniformly plasticize and roll 100 parts of fluororubber on a two-roll open mill, then gradually add 40 parts of fluororesin powder 1, 3 parts of 2,5-dimethyl-2,5-di(tert-butyl peroxy) hexane, and 3 parts of triallyl isocyanurate into the open mill and mix uniformly;

[0085] (2) The rubber mixture on the roll is cut left and right for 10 times each, the roll gap of the open mill is adjusted to the minimum, and the triangular bag is punched for 30 times. The roll temperature of the open mill is controlled within 60°C, and the mixing is uniform after which the sheet is discharged;

[0086] (3) The mixed rubber is parked for 16h, and then re-mixed for 10min before discharging the sheet.

[0087] Comparative Example 1

[0088] The preparation method of the fluororesin fluororubber composite material comprises the following steps:

[0089] (1) 100 parts of fluororubber are uniformly plasticized on a double-roll open mill and wrapped on the roll, and then 3 parts of 2,5-dimethyl-2,5-di(tert-butyl peroxy) hexane and 3 parts of triallyl isocyanurate are gradually added to the open mill for mixing;

[0090] (2) The rubber mixture on the roll is cut left and right for 10 times each, the roll gap of the open mill is adjusted to the minimum, and the triangular bag is punched for 30 times. The roll temperature of the open mill is controlled within 60°C, and the mixing is uniform after which the sheet is discharged;

[0091] (3) The mixed rubber is parked for 16h, and then re-mixed for 10min before discharging the sheet.

[0092] Comparative Example 2

[0093] The preparation method of the fluororesin fluororubber composite material comprises the following steps:

[0094] (1) 100 parts of fluororubber are uniformly plasticized on a double-roll open mill and wrapped on the roll, and then 20 parts of fluororesin powder 2, 3 parts of 2,5-dimethyl-2,5-di(tert-butyl peroxy) hexane, and 3 parts of triallyl isocyanurate are gradually added to the open mill for mixing;

[0095] (2) The rubber mixture on the roll is cut left and right for 10 times each, the roll gap of the open mill is adjusted to the minimum, and the triangular bag is punched for 30 times. The roll temperature of the open mill is controlled within 60°C, and the mixing is uniform after which the sheet is discharged;

[0096] (3) The mixed rubber is parked for 16h, and then re-mixed for 10min before discharging the sheet.

[0097] Comparative Example 3

[0098] The preparation method of the fluororesin fluororubber composite material comprises the following steps:

[0099] (1) 100 parts of fluororubber are uniformly plasticized on a double-roll open mill and wrapped on the roll, and then 20 parts of fluororesin powder 3, 3 parts of 2,5-dimethyl-2,5-di(tert-butyl peroxy) hexane, and 3 parts of triallyl isocyanurate are gradually added to the open mill for mixing;

[0100] (2) The rubber mixture of the wrapped roller is cut left and right for 10 times each, the roller gap of the open mill is adjusted to the minimum, and the triangular bag is punched for 30 times. The roller temperature of the open mill is controlled within 60°C, and the mixing is uniform after which the sheet is discharged;

[0101] (3) The mixed rubber is parked for 16h, and the sheet is discharged after being returned to the mill for 10min.

[0102] Comparative Example 4

[0103] The preparation method of the fluororesin fluororubber composite material comprises the following steps:

[0104] (1) 100 parts of fluororubber are uniformly plasticized on a double roller open mill and wrapped, and then 20 parts of white carbon black R972, 3 parts of 2,5-dimethyl-2,5-di(tert-butyl peroxy) hexane, and 3 parts of triallyl isocyanurate are gradually added to the open mill and uniformly mixed;

[0105] (2) The rubber mixture of the wrapped roller is cut left and right for 10 times each, the roller gap of the open mill is adjusted to the minimum, and the triangular bag is punched for 30 times. The roller temperature of the open mill is controlled within 60°C, and the mixing is uniform after which the sheet is discharged;

[0106] (3) The mixed rubber is parked for 16h, and the sheet is discharged after being returned to the mill for 10min.

[0107] Comparative Example 5

[0108] The preparation method of the fluororesin fluororubber composite material comprises the following steps:

[0109] (1) 100 parts of fluororubber are uniformly plasticized on a double roller open mill and wrapped, and then 20 parts of white carbon black R972, 3 parts of 2,5-dimethyl-2,5-di(tert-butyl peroxy) hexane, and 3 parts of triallyl isocyanurate are gradually added to the open mill and uniformly mixed;

[0110] (2) The rubber mixture of the wrapped roller is cut left and right for 10 times each, the roller gap of the open mill is adjusted to the minimum, and the triangular bag is punched for 30 times. The roller temperature of the open mill is controlled within 60°C, and the mixing is uniform after which the sheet is discharged;

[0111] (3) The mixed rubber is parked for 16h, and the sheet is discharged after being returned to the mill for 10min.

[0112] Comparative Example 6

[0113] The preparation method of the fluororesin fluororubber composite material comprises the following steps:

[0114] (1) 100 parts of fluororubber are uniformly plasticized on a double roller open mill and wrapped, and then 10 parts of fluororesin powder 1, 3 parts of 2,5-dimethyl-2,5-di(tert-butyl peroxy) hexane, and 3 parts of triallyl isocyanurate are gradually added to the open mill and uniformly mixed;

[0115] (2) The rubber mixture of the wrapped roll is cut left and right for 10 times each, the roll gap of the open mill is adjusted to the minimum, and a triangular bag is punched for 30 times. The roll temperature of the open mill is controlled within 60°C, and the mixing is uniform, and then the sheet is discharged;

[0116] (3) The mixed rubber is parked for 16h, and then re-mixed for 10min, and the sheet is discharged for use.

[0117] Comparative Example 7

[0118] The preparation method of the fluororesin fluororubber composite material comprises the following steps:

[0119] (1) 100 parts of fluororubber is uniformly plasticized on a double-roll open mill and wrapped, and then 50 parts of fluororesin powder 1, 3 parts of 2,5-dimethyl-2,5-di(tert-butyl peroxy) hexane, and 3 parts of triallyl isocyanurate are gradually added to the open mill for mixing;

[0120] (2) The rubber mixture of the wrapped roll is cut left and right for 10 times each, the roll gap of the open mill is adjusted to the minimum, and a triangular bag is punched for 30 times. The roll temperature of the open mill is controlled within 60°C, and the mixing is uniform, and then the sheet is discharged;

[0121] (3) The mixed rubber is parked for 16h, and then re-mixed for 10min, and the sheet is discharged for use.

[0122] The raw materials and amounts of each example and comparative example are shown in Table 2.

[0123] Table 2

[0124]

[0125]

[0126] The performance test results are shown in Table 3.

[0127] Table 3

[0128]

[0129] In combination with Table 2 and Table 3, it can be known from Examples 1-3 and Comparative Examples 6 and 7 that as the amount of fluororesin powder increases, the Shore A hardness, tensile strength, 100% modulus, and breaking work all increase, and the plasma mass loss decreases. In Comparative Example 7, when the amount exceeds 40 parts, the material formability becomes poor, the breaking work decreases, and the elongation at break becomes poor.

[0130] In combination with Table 2 and Table 3, it can be known from the comparison between Example 1 and Comparative Example 1 that, other than the fluororesin powder of the present application is removed in Comparative Example 1, the Shore A hardness, tensile strength, 100% modulus, and especially the breaking work all decrease significantly. In addition, the plasma mass loss increases significantly.

[0131] From Table 2 and Table 3, it can be known from the comparison of Example 1 and Comparative Examples 2, 3 that, with other conditions unchanged, only the fluororesin micro powder of the application is replaced by other fluororesin micro powder, the Shore A hardness, tensile strength, 100% modulus and breaking work are all decreased, and in addition, the plasma mass loss is increased.

[0132] From Table 2 and Table 3, it can be known from the comparison of Example 1 and Comparative Example 4 that, with other conditions unchanged, only the fluororesin micro powder of the application is replaced by white carbon black R972, the breaking work is increased, and the plasma mass loss is significantly increased.

[0133] From Table 2 and Table 3, it can be known from the comparison of Example 1 and Comparative Example 5 that, with other conditions unchanged, only the fluororesin micro powder of the application is replaced by carbon black N990, the Shore A hardness, tensile strength, 100% modulus and breaking work are all decreased, especially the breaking work is significantly decreased, and the plasma mass loss is significantly increased.

[0134] In summary, the application uses a screened fluororesin micro powder, which is added to the fluororubber, and the mechanical properties of the fluororubber are more significantly improved compared with other fillers. The fluororesin / fluororubber composite material prepared by the application has better plasma resistance and high cleanliness, and is very suitable for the semiconductor, photovoltaic, aerospace and other industries with high cleanliness and plasma resistance requirements.

[0135] In summary, the application effectively overcomes the shortcomings in the prior art and has high industrial utilization value.

[0136] The above is only a preferred embodiment of the application, and is not a limitation on the form and substance of the application. It should be noted that, for those skilled in the art, without departing from the method of the application, some improvements and supplements can be made, and these improvements and supplements should also be considered as the protection scope of the application. For those skilled in the art, without departing from the spirit and scope of the application, some changes, modifications and equivalent changes made by using the disclosed technical content are equivalent embodiments of the application; at the same time, any equivalent changes, modifications and evolution of the above-mentioned embodiments according to the essential technology of the application are still within the scope of the technical solutions of the application.

Claims

1. A fluororesin fluororubber composite material, characterized by, The raw materials of the fluororesin fluororubber composite include the following components by weight: Fluororubber 100-120 parts; Fluororesin micro powder 20-40 parts; Crosslinking agent 1-8 parts; Co-crosslinking agent 0.1-6 parts; The fluororesin micro powder is selected from one or more of tetrafluoroethylene-hexafluoropropylene copolymer, polyvinylidene fluoride, and polytetrafluoroethylene; The fluororesin micro powder has a melting peak, and the fluororesin micro powder includes C, F, and other elements, the other elements are one or more of oxygen, sulfur, and nitrogen, and the molar ratio of the other elements to the total elements is 3-10 parts per million.

2. The fluororesin fluororubber composite material according to claim 1, wherein The fluororubber is selected from one or more of type 26 fluororubber, type 246 fluororubber, perfluoroether rubber, tetrapropyl fluororubber, perfluoroether rubber, and fluorinated phosphine nitride rubber.

3. The fluororesin fluororubber composite material according to claim 1, wherein The particle size of the fluororesin micro powder is 1-500 μm; And / or, the weight of the fluororesin micro powder is 30-40 parts.

4. The fluororesin fluororubber composite material according to claim 3, wherein The weight of the fluororesin micro powder is 35-40 parts.

5. The fluororesin fluororubber composite material according to claim 1, wherein The crosslinking agent is selected from one or more of 2,5-dimethyl-2,5-bis(tert-butyl peroxy) hexane, 2,2-bis(3-amino-4-hydroxyphenyl)-hexafluoropropane, and fluorine aralkyl phosphonium salt; And / or, the co-crosslinking agent is triallyl isocyanurate or trimethallyl isocyanurate.

6. The fluororesin fluororubber composite material according to claim 5, wherein The crosslinking agent is 2,5-dimethyl-2,5-bis(tert-butyl peroxy) hexane; And / or, the co-crosslinking agent is triallyl isocyanurate.

7. The fluororesin fluororubber composite material according to claim 1, wherein The fluororesin fluororubber composite includes any one or more of the following features: A1) the Shore A hardness is greater than 56 according to GB / T 531.1; A2) the tensile strength is greater than 9 MPa according to GB / T 528; A3) the elongation at break is greater than 240% according to GB / T 528; A4) the 100% modulus is greater than 5 MPa according to GB / T 528; A5) the fracture work is greater than or equal to 0.35 N / m according to the stress-strain curve integral test obtained by tensile test according to GB / T 528; A6) the plasma mass loss is less than 1.6% according to ICP etching, room temperature, 10 Pa, 60 min, and CF4.

8. The method for producing a fluororesin fluororubber composite material according to any one of claims 1 to 7, characterized by, The preparation method includes: 1) uniformly plasticize the fluororubber on a two-roll open mill, then add the fluororesin micro powder, crosslinking agent, and co-crosslinking agent into the open mill to mix uniformly to obtain a wrapped roll rubber mixture; 2) cut the wrapped roll rubber mixture left and right, adjust the open mill roll gap to the minimum, punch a triangular package, mix uniformly, and then discharge the sheet to obtain a mixed rubber; 3) stop the mixed rubber, re-mix, and discharge the sheet for use.

9. The method for producing a fluororesin fluororubber composite material according to claim 8, characterized by, In step 2), each left and right cut is 3-10 times; And / or, in step 2), punch the triangular package 10-30 times; And / or, in step 2), the open mill roller temperature is controlled within 60°C; And / or, in step 3), the mixed rubber is stopped for 16 h or more.

10. Use of the fluororesin fluororubber composite according to any one of claims 1-8 in the fields of semiconductors, photovoltaics, and aerospace.

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