CN115197577B - Antistatic silicone rubber composite material, flexible electrostatic shielding bag and preparation method thereof - Google Patents

Antistatic silicone rubber composite material, flexible electrostatic shielding bag and preparation method thereof Download PDF

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CN115197577B
CN115197577B CN202210934338.9A CN202210934338A CN115197577B CN 115197577 B CN115197577 B CN 115197577B CN 202210934338 A CN202210934338 A CN 202210934338A CN 115197577 B CN115197577 B CN 115197577B
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silica gel
parts
shielding bag
mixing
silicone rubber
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CN115197577A (en
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王超
陆磊
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Zhenjiang Gaomei New Material Co ltd
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Zhenjiang Gaomei New Material Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/10—Layered products comprising a layer of natural or synthetic rubber next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/20—Layered products comprising a layer of natural or synthetic rubber comprising silicone rubber
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/08—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer the fibres or filaments of a layer being of different substances, e.g. conjugate fibres, mixture of different fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D31/00—Bags or like containers made of paper and having structural provision for thickness of contents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D81/00—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents
    • B65D81/18—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents providing specific environment for contents, e.g. temperature above or below ambient
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/103—Metal fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/106—Carbon fibres, e.g. graphite fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/14—Mixture of at least two fibres made of different materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/21—Anti-static
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/552—Fatigue strength
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/558—Impact strength, toughness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles
    • B32B2439/02—Open containers
    • B32B2439/06—Bags, sacks, sachets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0862—Nickel
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/001—Conductive additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/017—Additives being an antistatic agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/04—Antistatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets

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  • Polymers & Plastics (AREA)
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Abstract

The invention discloses an antistatic silicon rubber composite material, a flexible electrostatic shielding bag and a preparation method thereof, wherein the antistatic silicon rubber composite material comprises the following components in parts by weight: 100 parts of methyl vinyl silicone rubber, 35-45 parts of gas phase white carbon black, 3-8 parts of hydroxyl silicone oil, 0.6-2 parts of zinc stearate, 0.2-0.5 part of vulcanizing agent, 0-3 parts of nonionic antistatic agent, 2-5 parts of high molecular antistatic agent and 2-10 parts of conductive filler; wherein the nonionic antistatic agent is fatty alkanolamide nonionic antistatic agent; the high molecular antistatic agent is one or a combination of more of quaternary ammonium salt type, polyether type, sulfonic acid type or betaine type; the conductive filler is a composite use of a metal conductive filler and a carbon conductive filler. The anti-static shielding bag is prepared, has good anti-static effect, can provide omnibearing shape-following support protection, has good shockproof function, effectively prevents the risk of collision or falling collision, and has good practical value.

Description

Antistatic silicone rubber composite material, flexible electrostatic shielding bag and preparation method thereof
Technical Field
The invention relates to an antistatic silicon rubber composite material, a flexible electrostatic shielding bag and a preparation method thereof.
Background
With the increasing roles played by multimedia applications in people's daily lives and the increasing intimate relationship between computers and consumer electronics, the demands of people on portability and functionality of electronic products have also increased continuously, which puts higher demands on electrostatic protection of electronic products. Static electricity is an objectively existing natural phenomenon, and is generated in a plurality of modes, such as contact, friction, induction between electric appliances and the like. Friction electrification and human static electricity are two major hazards in the electronic industry, and often cause unstable operation and even damage of electronic and electric products. The main reason is that: 1) Dust is adsorbed by static electricity, so that the insulation resistance of the element is reduced, and the service lives of electronic products and components are shortened; 2) Electrostatic discharge damage elements, rendering them potentially damaged or directly damaged inoperable; 3) The electromagnetic field generated by electrostatic discharge has a large amplitude (up to hundreds of volts/meter), and the frequency spectrum is extremely wide (from tens of megameters to several gigabytes), which causes serious electromagnetic interference and even damage to an electronic generator. For example, the problems of frequent dead halt, automatic shutdown, poor voice quality, high noise, good time difference in signal, key error and the like of the mobile phone are mostly related to electrostatic damage. Therefore, electrostatic protection is important for normal use of electronic products and for ensuring the service life thereof.
Silicone rubber is one of the preferred elastomers in many extreme environments because of its excellent resistance to extreme temperatures; and the composite material has excellent dielectric strength, heat conductivity and fireproof performance, and is widely applied to various fields of aviation, aerospace, communication, electric power, electronics, electric appliances and the like. However, silicone rubber is a good electrical insulator, and has been conventionally used as an insulator in the fields of electric power, electronics, electric appliances, etc., but is very disadvantageous in terms of antistatic properties, and is unsuitable for use particularly when electrostatic discharge protection is required.
Electrostatic discharge (ESD) protection, hereinafter referred to as ESD protection, is of great importance for high-density, miniaturized and complex-function electronic devices such as mobile phones. Electrostatic discharge is a process of discharging electrostatic charges charged on an object, and the most common method of ESD protection is to protect with an electrostatic shielding bag. The anti-static shielding bag is a flexible packaging bag with static shielding performance and static leakage performance on the inner surface of the product which is directly contacted with static sensitivity, and is widely used for packaging various pc boards, computer main boards, sound cards, display cards, network cards and static sensitivity high-tech electronic products.
At present, an aluminum foil material is mostly adopted for the electrostatic shielding bag to achieve an antistatic effect, or an antistatic agent is coated to achieve an electrostatic shielding effect. However, the shielding bag prepared from aluminum foil has stiff texture, and the bag body is more likely to be broken when being bent and collided in the packaging and transportation processes; on the one hand, the product coated with the antistatic agent has complex coating process and is easy to have the problem of missing coating or uneven coating, on the other hand, the antistatic agent is a surface treatment agent, the duration of antistatic effect is shorter, and the problem of expiration of antistatic is existed for the storage and use of the product. In addition, the existing shielding bag is single in bag type, and for different products, the packaging bag is used, so that not only is packaging bag materials and space wasted, but also the products cannot be protected along with the shape; and under the conditions of collision, drop or vibration, the electronic device or the element loaded in the electronic device cannot be effectively protected, and the protection requirement of some high-end fine sensitive devices which are sensitive to static electricity and are easy to damage by the static electricity cannot be met.
Therefore, it would be a new idea to modify silicone rubber to make it antistatic and apply to electrostatic discharge protection.
Disclosure of Invention
Aiming at the problems of the conventional electrostatic shielding bag and in order to achieve the purposes, the invention provides an antistatic silicon rubber composite material, a flexible electrostatic shielding bag and a preparation method thereof. The specific technical scheme is as follows:
firstly, the invention provides an antistatic silicone rubber composite material, which comprises the following components in parts by weight: 100 parts of methyl vinyl silicone rubber, 35-45 parts of gas phase white carbon black, 3-8 parts of hydroxyl silicone oil, 0.6-2 parts of zinc stearate, 0.2-0.5 part of vulcanizing agent, 0-3 parts of nonionic antistatic agent, 2-5 parts of high molecular antistatic agent and 2-10 parts of conductive filler; wherein the nonionic antistatic agent is fatty alkanolamide nonionic antistatic agent; the high molecular antistatic agent is one or a combination of more of quaternary ammonium salt type, polyether type, sulfonic acid type or betaine type; the conductive filler is a composite use of a metal conductive filler and a carbon conductive filler.
The antistatic silicone rubber composite material comprises the following components in parts by weight: 100 parts of methyl vinyl silicone rubber, 35-45 parts of gas-phase white carbon black, 3-8 parts of hydroxyl silicone oil, 0.6-2 parts of zinc stearate, 0.2-0.5 part of vulcanizing agent, 0-3 parts of coconut diethanolamide, 2-5 parts of sulfonic acid, 1-5 parts of oriented carbon nano tube and 1-5 parts of conductive nickel powder.
Secondly, the invention provides an antistatic silicon rubber composite flexible electrostatic shielding bag, which comprises the following components in parts by weight: comprises a shielding bag body and a sealing strip; the shielding bag body comprises an internal silica gel supporting layer, an external silica gel protecting layer and a fiber reinforced protecting layer which is arranged between the internal silica gel supporting layer and the external silica gel protecting layer; the built-in silica gel supporting layer and the external silica gel protecting layer are prepared from the antistatic silica gel composite material; the fiber reinforced protective layer is formed by interweaving metal wires and carbon fibers.
Preferably, the antistatic silicone rubber composite flexible electrostatic shielding bag comprises the components of the built-in silica gel supporting layer in parts by weight: 100 parts of methyl vinyl silicone rubber, 35 parts of gas phase white carbon black, 2 parts of hydroxyl silicone oil, 0.5 part of zinc stearate, 0.3 part of vulcanizing agent, 2 parts of sulfonic acid, 5 parts of oriented carbon nano tube and 5 parts of conductive nickel powder; the external silica gel supporting layer comprises the following components in parts by weight: 100 parts of methyl vinyl silicone rubber, 45 parts of gas phase white carbon black, 5 parts of hydroxyl silicone oil, 2 parts of zinc stearate, 0.5 part of vulcanizing agent, 3 parts of coconut diethanolamide, 5 parts of sulfonic acid, 5 parts of oriented carbon nano tube and 2 parts of conductive nickel powder; in the fiber reinforced protective layer, the mass ratio of the metal wires to the carbon fibers is 1:2.
Preferably, the thickness of the built-in silica gel supporting layer of the flexible electrostatic shielding bag made of the antistatic silicone rubber composite material is 1-10 mm or is set according to the specific shape and specification of the product; the thickness of the external silica gel protective layer is 1-5 mm; the thickness of the fiber reinforced protective layer is 0.1-0.2 mm; the built-in silica gel supporting layer and the external silica gel protecting layer are respectively formed integrally; the metal wires and the carbon fibers are crisscrossed after being stranded, the warp and weft density is 100 pieces per 1 square inch, wherein the warp direction is 55 pieces, and the weft direction is 45 pieces; the sealing strip is arranged on the fiber reinforced protective layer, and the edge of the opening of the built-in silica gel supporting layer is stopped at the inner side of the sealing strip.
In addition, the invention also provides a preparation method of the antistatic silicone rubber composite flexible electrostatic shielding bag, which comprises the following steps:
1) Preparing materials: preparing materials according to the components of the antistatic silicone rubber composite material to prepare an internal silica gel supporting layer and an external silica gel protecting layer; simultaneously preparing metal wires and carbon fibers for interweaving according to the fiber reinforced protective layer component of any one of claims 3-5;
2) Mixing: respectively adding the components for preparing the internal silica gel supporting layer and the external silica gel protecting layer into a banburying device for respectively mixing to form a mixed rubber material for later use;
3) Interleaving: after the metal wires and the carbon fibers are stranded, the metal wires are crisscrossed according to the appointed warp and weft density to form a fiber reinforced net sheet for standby;
4) Injection molding: the mixed rubber material of the mixed built-in silica gel supporting layer and the mixed rubber material of the external silica gel protective layer are reworked, the reworked mixed rubber material of the built-in silica gel supporting layer is paved in a flat plate die or a prefabricated molded surface die, a fiber reinforced net sheet is placed after prepressing, and then the reworked mixed rubber material of the external silica gel protective layer is paved, and a flat plate die is adopted;
5) Presulfiding: pre-vulcanizing the injection molded mixed rubber and the fiber reinforced net sheet under a certain vulcanization condition, and processing the sealing strips to be adhered;
6) Folding and shaping: folding the pre-vulcanized mixed rubber and the fiber reinforced net sheet by a forming die, removing the residual area of the inner die and shaping to form a shielding bag body;
7) Secondary vulcanization: and vulcanizing the folded and molded mixed rubber and the fiber reinforced net together with the mold again, and demoulding after vulcanization is finished to obtain the antistatic silicone rubber composite material flexible electrostatic shielding bag.
The flexible electrostatic shielding bag of the antistatic silicone rubber composite material is prepared by mixing the components in the step 2) for preparing the internal silica gel supporting layer and the external silica gel protecting layer, wherein the feeding sequence and mixing time are as follows: preheating an internal mixer to 80 ℃, stabilizing for a period of time, adding methyl vinyl silicone rubber, mixing for 1min, adding hydroxyl silicone oil, mixing for 1.5min, adding gas phase white carbon black, mixing for 3min, adding zinc stearate, mixing for 1.5min, adding sulfonic acid, mixing for 2min, adding oriented carbon nano tube, mixing for 1.5min, adding conductive nickel powder, mixing for 5min, adding coconut oil diethanolamide, and mixing for 1min; and then the temperature is raised to 150-180 ℃ to fully mix for 2-3 hours, then vacuum heat treatment is carried out for 20-40 minutes, the rotation direction of the internal mixer is controlled to be unchanged, and the mixed rubber material for preparing the internal silica gel supporting layer and the external silica gel protecting layer is obtained after cooling and discharging.
Preferably, in the step 4), the back-mixing is to put the mixed rubber material of the internal silica gel supporting layer or the mixed rubber material of the external silica gel protecting layer into an open mill, and adding a vulcanizing agent, and carrying out thin-pass for 15-20 times for vulcanization; the die structure for vulcanization molding of the electrostatic shielding bag is as follows: comprises an inner mold and an outer mold, both of which are provided with folding areas; the cavity type of the inner die cavity is designed according to the requirements of users and is provided with a detachable allowance zone; the outer mould tool is in the form of a foldable plate.
Preferably, the conditions of the prevulcanisation in step 5) are: and (3) die pressing and vulcanizing for 10-15 min under the pressure of 12-15 MPa and the temperature of 175-185 ℃.
Preferably, the secondary vulcanization conditions in step 7) are: the process is carried out in a constant temperature oven, the temperature is controlled to be 190-200 ℃, and the time is controlled to be 4-6 h.
The invention has the beneficial effects that:
1) The antistatic silicone rubber composite material improves the conductivity of the silicone rubber material through the composite modification of the oriented carbon nano tube and the conductive nickel powder and the unique preparation method, so that the antistatic silicone rubber composite material is suitable for packaging and protecting electronic products, can release redundant static electricity of the electronic products and elements, avoids damage of electronic circuits or electronic components caused by static electricity, and improves the safety of product storage and transportation.
2) The invention provides an anti-static shielding bag prepared from a modified silicon rubber material for the first time, which not only has a good shielding function and plays a good anti-static role, but also can provide omnibearing shape-following support protection for electronic products and components, and simultaneously has a good shockproof function, thereby effectively preventing the risk of collision or falling impact on content electronic products or components and meeting the packaging requirement of high-end electronic products.
3) The anti-static shielding bag realizes the shape-dependent change of electronic products and components and provides omnibearing support protection by the built-in silica gel supporting layer; the fiber reinforced protective layer arranged in the middle not only provides good puncture resistance for the shielding bag, but also isolates the objects in the shielding bag from an electrostatic field to prevent static accumulation and prevent static damage; and the external silica gel protective layer with excellent conductivity can lead out static electricity in the bag.
4) The invention relates to a modified conductive nickel powder and a preparation method thereof, which comprises the following steps: the carboxyl residue of the sulfonic acid excites the activity of the conductive nickel powder, the good ferromagnetic property of the conductive nickel powder can form a good conductive network, the directional mixing in the preparation process is combined to guide the directional carbon nano tube to be directionally dispersed in the nickel powder network to form a compact shielding structure, and the non-ionic antistatic agent and the high molecular antistatic agent are added to fully improve the conductive property of the silica gel material to release redundant static electricity of electronic products and elements, avoid damage of electronic circuits or electronic components caused by static electricity and improve the safety in the transportation and transfer process of products.
5) The invention sets the internal silica gel supporting layer and the external silica gel protecting layer to shield, so that the resistance of the inner surface and the outer surface of the shielding bag and the smaller internal induction energy are realized; the middle fiber reinforced protective layer is formed by interweaving metal wires and carbon fibers, the metal wires can ensure electric conduction, a Faraday cage induction cover effect is well formed, and an electrostatic isolation effect is ensured; the carbon fiber has good toughness, so that the puncture resistance of the shielding bag is improved; and the metal wires are interwoven with the carbon fibers, the warp and weft density is 100/1 square inch, the warp direction is 55, the weft direction is 45, the adhesion of the inner silica gel supporting layer and the outer silica gel protecting layer in the later stage vulcanization is ensured, the inner silica gel supporting layer and the outer silica gel protecting layer form a whole, and the electrostatic shielding effect is ensured.
6) The shielding bag can be processed into any shape according to the requirements of users, has stable performance, good ageing-resistant tensile strength and impact strength, is soft and flexible, can be recycled for multiple times, and has good practical value.
Drawings
FIG. 1 is a schematic view of a mold structure for vulcanization molding of an electrostatic shielding bag according to the present invention;
fig. 2 is a schematic cross-sectional view of the electrostatic shielding bag of the present invention after being folded after a silicone material is applied to a mold for vulcanization molding.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described below with reference to the embodiments.
Wherein, example 1 is antistatic liquid silicone rubber and preparation method thereof, and examples 2-6 are verification analysis of the formulation of antistatic liquid silicone rubber and improvement points and improvement effects of preparation process described in example 1.
Example 1
The embodiment is to prepare an antistatic silicon rubber composite material. The antistatic silicone rubber composite material comprises the following components in parts by weight: 100 parts of methyl vinyl silicone rubber, 35 parts of gas phase white carbon black, 2 parts of hydroxyl silicone oil, 0.5 part of zinc stearate, 0.3 part of vulcanizing agent, 2 parts of sulfonic acid, 5 parts of oriented carbon nano tube and 5 parts of conductive nickel powder; the preparation method comprises the following steps:
preheating an internal mixer to 80 ℃, stabilizing for a period of time, adding methyl vinyl silicone rubber, mixing for 1min, adding hydroxyl silicone oil, mixing for 1.5min, adding gas phase white carbon black, mixing for 3min, adding zinc stearate, mixing for 1.5min, mixing for 2min, adding oriented carbon nano tube, mixing for 1.5min, adding conductive nickel powder, and mixing for 5min; and then the temperature is raised to 150 ℃ for fully mixing for 3 hours, then vacuum heat treatment is carried out for 30 minutes, the rotation direction of the internal mixer is controlled unchanged during the period, and the mixed rubber material is obtained after cooling and discharging.
Then adding a vulcanizing agent into an open mill, carrying out thin-pass 15 times, and then vulcanizing to obtain the antistatic silicone rubber composite material.
Example 2
The embodiment also prepares an antistatic silicone rubber composite material. The components of the composition comprise the following components in parts by weight: 100 parts of methyl vinyl silicone rubber, 45 parts of gas phase white carbon black, 5 parts of hydroxyl silicone oil, 2 parts of zinc stearate, 0.5 part of vulcanizing agent, 3 parts of coconut diethanolamide, 5 parts of sulfonic acid, 5 parts of oriented carbon nano tubes and 2 parts of conductive nickel powder. The preparation method comprises the following steps:
preheating an internal mixer to 80 ℃, stabilizing for a period of time, adding methyl vinyl silicone rubber, mixing for 1min, adding hydroxyl silicone oil, mixing for 1.5min, adding gas phase white carbon black, mixing for 3min, adding zinc stearate, mixing for 1.5min, adding sulfonic acid, mixing for 2min, adding oriented carbon nano tube, mixing for 1.5min, adding conductive nickel powder, mixing for 5min, adding coconut oil diethanolamide, and mixing for 1min; and then the temperature is increased to 180 ℃ for fully mixing for 2 hours, then vacuum heat treatment is carried out for 40 minutes, the rotation direction of the internal mixer is controlled unchanged during the period, and the mixed rubber material is obtained after cooling and discharging.
Then adding a vulcanizing agent into an open mill, carrying out thin-pass for 20 times, and then vulcanizing to obtain the antistatic silicone rubber composite material.
Example 3
The embodiment is to prepare the antistatic silicon rubber composite material flexible electrostatic shielding bag. The electrostatic shielding bag comprises a shielding bag body and a sealing strip; the shielding bag body comprises an internal silica gel supporting layer, an external silica gel protecting layer and a fiber reinforced protecting layer between the internal silica gel supporting layer and the external silica gel protecting layer. The composition of the built-in silica gel supporting layer is the same as that of example 1; the composition of the external silica gel protective layer is the same as that of example 2. The preparation method comprises the following steps:
1) Preparing materials: preparing the components according to the formula of the example 1 to prepare a built-in silica gel supporting layer; preparing the components according to the formula of the example 2 to prepare an external silica gel protective layer; and preparing the metal wires and the carbon fibers at the same time to prepare the fiber reinforced protective layer.
2) Mixing: mixing the material of the built-in silica gel supporting layer in an internal mixer according to the method of the embodiment 1 to obtain a mixed rubber material of the built-in silica gel supporting layer for later use; the components of the external silica gel protective layer were mixed in an internal mixer as described in example 2 to obtain an external silica gel support layer mixed rubber material for further use. The external silica gel protective layer comprises a non-ionic antistatic agent of coconut oil diethanolamide, so that the antistatic effect is enhanced.
3) Interleaving: and (3) the prepared metal wires and the carbon fibers are crisscrossed after being stranded, so that fiber reinforced meshes are formed for standby. The metal wire is preferably a copper wire or a silver-copper alloy or other alloys with good electric conductivity; the ratio of the metal wires to the carbon fibers is 1:2, namely, one metal wire and two carbon fibers are interwoven in a stranding mode. The interweaving mode adopts longitudinal and transverse tiling interweaving; preferably, the warp and weft densities are 100 per 1 square inch, wherein the warp direction is 55 and the weft direction is 45; the thickness of the woven fiber reinforced net sheet is about 0.1-0.2 mm. Ensure that milk pierces through the new laminating that can guarantee built-in silica gel supporting layer and external silica gel protective layer of later stage vulcanization simultaneously, make it form wholly, guarantee electrostatic shielding effect.
4) Injection molding: mixing the mixed rubber material of the internal silica gel supporting layer and the mixed rubber material of the external silica gel protecting layer for remilling; placing the mixed rubber material with the silica gel supporting layer inside an open mill, adding a vulcanizing agent, and carrying out thin-pass 15 times; mixing rubber materials with an external silica gel protective layer in an open mill, adding a vulcanizing agent, and carrying out thin-pass for 20 times; and then paving the mixed rubber material of the back-refined internal silica gel supporting layer in a flat plate die or a prefabricated molded surface die, pre-pressing and flattening, placing a fiber reinforced net sheet, paving the mixed rubber material of the back-refined external silica gel protective layer, and adopting a flat plate die. The die structure for vulcanization molding of the electrostatic shielding bag is as follows: comprises an inner mold and an outer mold, both of which are provided with folding areas; the cavity type of the inner die cavity is designed according to the requirements of users and is provided with a detachable allowance zone; the outer mould tool is in the form of a foldable plate. As shown in fig. 1 and 2, the inner mold is provided with a film cavity with a certain thickness, the cavity can be a flat plate type, the thickness can be designed according to the molded surface of a product to be packaged, and the thickness can be controlled to be 1-10 mm according to the product and the requirement of a customer; the edge of the glass fiber reinforced plastic composite material is provided with a detachable surplus board so as to be beneficial to paving fiber reinforced meshes and an external silica gel protective layer. The surplus board is set to a certain depth to control the thickness of the external silica gel protective layer, and the thickness of the external silica gel protective layer is controlled to be 1-5 mm. After the mixed rubber material of the internal silica gel supporting layer is paved on the internal mold to be flattened, the fiber reinforced net sheet is placed, the fibers of the net sheet are symmetrically arranged, then the mixed rubber material of the external silica gel protecting layer is additionally paved, finally the external mold is covered on the mixed rubber material of the external silica gel protecting layer to be flattened, and the rubber layer of the folding area can be thicker. The folding area of the inner mold and the outer mold is arranged in the middle, and the width of the folding area is determined according to the thickness of the inner silica gel and the outer silica gel and the products to be packaged. In addition, the inner die and the outer die can be provided with positioning devices for positioning the silica gel layer and positioning after folding, and the folded silica gel layer can be fixed by positioning pins or other suitable modes in the field, so that the two sides of the prepared shielding bag are bonded neatly and reach the specification standard of the electrostatic shielding bag.
5) Presulfiding: the injection molded mixed rubber and the fiber reinforced net sheet are subjected to first vulcanization molding under the presulfiding condition, and the specific conditions are as follows: and (3) die pressing and vulcanizing for 10-15 min under the pressure of 12-15 MPa and the temperature of 175-185 ℃. After pre-vulcanization molding, removing the residual plates at the two ends of the inner mold, and adhering the sealing strips on the fiber reinforced net sheet for folding molding.
6) Folding and shaping: and folding the pre-vulcanized mixed rubber and the fiber reinforced net sheet through a forming die, removing the residual plate of the die, attaching the mixed rubber material with the external silica gel protective layer, brushing a layer of vulcanizing agent for ensuring the adhesiveness, supplementing a certain amount of the mixed rubber material with the external silica gel protective layer, and forming the shielding bag body after molding.
7) Secondary vulcanization: and vulcanizing the folded and molded mixed rubber and the fiber reinforced net together with the mold again, wherein the secondary vulcanization conditions are as follows: the process is carried out in a constant temperature oven, the temperature is controlled to be 190-200 ℃, and the time is controlled to be about 4-6 h. And after the vulcanization is finished, demoulding to obtain the antistatic silicone rubber composite material flexible electrostatic shielding bag.
Comparative example 1 contains no conductive Nickel powder
The embodiment is to prepare the antistatic silicon rubber composite material flexible electrostatic shielding bag. The electrostatic shielding bag structure was the same as in example 3. But the components of the built-in silica gel supporting layer comprise the following components in parts by weight: 100 parts of methyl vinyl silicone rubber, 35 parts of gas phase white carbon black, 2 parts of hydroxyl silicone oil, 0.5 part of zinc stearate, 0.3 part of vulcanizing agent, 2 parts of sulfonic acid and 5 parts of oriented carbon nano tube; the external silica gel supporting layer comprises the following components in parts by weight: 100 parts of methyl vinyl silicone rubber, 45 parts of gas phase white carbon black, 5 parts of hydroxyl silicone oil, 2 parts of zinc stearate, 0.5 part of vulcanizing agent, 3 parts of coconut diethanolamide, 5 parts of sulfonic acid and 5 parts of oriented carbon nanotubes; the preparation method is the same as in example 3.
Comparative example 2 contains no aligned carbon nanotubes
This example also provides a flexible electrostatic shielding bag of antistatic silicone rubber composite material. The electrostatic shielding bag structure was the same as in example 3. But the components of the built-in silica gel supporting layer comprise the following components in parts by weight: 100 parts of methyl vinyl silicone rubber, 35 parts of gas phase white carbon black, 2 parts of hydroxyl silicone oil, 0.5 part of zinc stearate, 0.3 part of vulcanizing agent, 2 parts of sulfonic acid and 5 parts of conductive nickel powder; the external silica gel supporting layer comprises the following components in parts by weight: 100 parts of methyl vinyl silicone rubber, 45 parts of gas phase white carbon black, 5 parts of hydroxyl silicone oil, 2 parts of zinc stearate, 0.5 part of vulcanizing agent, 3 parts of coconut diethanolamide, 5 parts of sulfonic acid and 2 parts of conductive nickel powder; the preparation method is the same as in example 3.
Comparative example 3 contains no conductive nickel powder and oriented carbon nanotubes
This example also provides a flexible electrostatic shielding bag of antistatic silicone rubber composite material. The electrostatic shielding bag structure was the same as in example 3. But the components of the built-in silica gel supporting layer comprise the following components in parts by weight: 100 parts of methyl vinyl silicone rubber, 35 parts of gas phase white carbon black, 2 parts of hydroxyl silicone oil, 0.5 part of zinc stearate, 0.3 part of vulcanizing agent and 2 parts of sulfonic acid; the external silica gel supporting layer comprises the following components in parts by weight: 100 parts of methyl vinyl silicone rubber, 45 parts of gas phase white carbon black, 5 parts of hydroxyl silicone oil, 2 parts of zinc stearate, 0.5 part of vulcanizing agent, 3 parts of coconut diethanolamide and 5 parts of sulfonic acid; the preparation method is the same as in example 3.
Comparative example 4 containing no conductive nickel powder, aligned carbon nanotubes and antistatic agent
This example also provides a flexible electrostatic shielding bag of antistatic silicone rubber composite material. The electrostatic shielding bag structure was the same as in example 3. But the components of the built-in silica gel supporting layer comprise the following components in parts by weight: 100 parts of methyl vinyl silicone rubber, 35 parts of gas phase white carbon black, 2 parts of hydroxyl silicone oil, 0.5 part of zinc stearate and 0.3 part of vulcanizing agent; the external silica gel supporting layer comprises the following components in parts by weight: 100 parts of methyl vinyl silicone rubber, 45 parts of gas phase white carbon black, 5 parts of hydroxyl silicone oil, 2 parts of zinc stearate and 0.5 part of vulcanizing agent; the preparation method is the same as in example 3.
Comparative example 5 without a fiber reinforced mesh
This example also provides a flexible electrostatic shielding bag of antistatic silicone rubber composite material. The electrostatic shielding bag structure was not provided with a fiber reinforced mesh sheet as compared with example 3. The internal silica gel support layer component and the external silica gel support layer component thereof were the same as in example 3; the preparation method is the same as in example 3.
Effect example
In this example, the performance of the electrostatic shielding bags prepared in example 3 and comparative examples 1 to 5 was measured, and each index was measured according to GB/T39588-2020, and the specific results are shown in Table 1.
TABLE 1 electrostatic shielding bag Performance test results
Figure SMS_1
From the above table, the seal strength of the electrostatic shielding bag of each embodiment meets the requirements, but the puncture resistance strength of the electrostatic shielding bag does not meet the requirements without the fiber-reinforced mesh; in terms of surface resistance, the fiber-reinforced mesh sheet containing the metal wires also contributes to the conductivity of the bag body; and the surface resistance of the oriented carbon nano tube and the conductive nickel powder can meet the specified standard of the shielding bag only when the oriented carbon nano tube and the conductive nickel powder are used simultaneously. The activity of the conductive nickel powder is excited by carboxyl residues of sulfonic acid to form a conductive network, the combination of the conductive network and the directional carbon nano tube enables the shielding structure to be compact, the surface resistivity to be reduced, and the metal wires in the fiber reinforced net sheet to further reduce the surface resistivity to form a good Faraday cage, so that static electricity is shielded, and the inductive electric energy in the conductive nickel powder is at a lower level, thereby enabling the prepared electrostatic shielding bag to meet the production standard and meeting the use requirement.
According to the invention, the non-ionic antistatic agent (coconut diethanolamide used for an external protective layer), the high molecular antistatic agent (sulfonic acid) and the conductive nickel powder and the directional carbon nanotube double-component conductive filler are added, so that the conductive performance of the silica gel material is fully improved, redundant static electricity of electronic products and components is discharged, the damage of electronic circuits or electronic components caused by static electricity is avoided, and the safety of the products in the transportation and transfer process is improved. The invention provides an anti-static shielding bag prepared from the modified silicon rubber material for the first time, which not only has a good shielding function and plays a good anti-static role, but also can provide omnibearing shape-following support protection for electronic products and components, and simultaneously has a good shockproof function, thereby effectively preventing the risk of collision or falling impact on the content electronic products or components and meeting the packaging requirement of high-end electronic products. The anti-static shielding bag realizes the shape-dependent change of electronic products and components and provides omnibearing support protection by the built-in silica gel supporting layer; the fiber reinforced protective layer arranged in the middle not only provides good puncture resistance for the shielding bag, but also isolates the objects in the shielding bag from an electrostatic field to prevent static accumulation and prevent static damage; the external silica gel protective layer with excellent conductivity can lead out static electricity in the bag, provides new ideas and concepts for developing and applying the static shielding bag, and has good use value and important economic value
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. Accordingly, the embodiments are to be considered in all respects as illustrative and not restrictive. Furthermore, it should be understood that, although the present disclosure describes embodiments, this description is not intended to include only one embodiment, and those skilled in the art should understand that the present disclosure is not limited to the embodiments described herein, and that the embodiments described in the examples may be combined appropriately to form other embodiments that will be understood by those skilled in the art.

Claims (7)

1. An antistatic silicone rubber composite flexible electrostatic shielding bag, which is characterized in that: comprises a shielding bag body and a sealing strip; the shielding bag body comprises an internal silica gel supporting layer, an external silica gel protecting layer and a fiber reinforced protecting layer which is arranged between the internal silica gel supporting layer and the external silica gel protecting layer;
the components of the internal silica gel supporting layer and the external silica gel protecting layer comprise the following components in parts by weight:
100 parts of methyl vinyl silicone rubber, and the mixture,
35-45 parts of gas-phase white carbon black,
3-8 parts of hydroxyl silicone oil,
0.6 to 2 parts of zinc stearate,
0.2 to 0.5 part of vulcanizing agent,
0 to 3 parts of coconut diethanolamide,
2-5 parts of sulfonic acid,
1 to 5 parts of directional carbon nano tube,
1-5 parts of conductive nickel powder;
the fiber reinforced protective layer is formed by interweaving metal wires and carbon fibers.
2. The antistatic silicone rubber composite flexible electrostatic shielding bag of claim 1, wherein:
the thickness of the built-in silica gel supporting layer is 1-10 mm or is set according to the specific shape and specification of the product;
the thickness of the external silica gel protective layer is 1-5 mm;
the thickness of the fiber reinforced protective layer is 0.1-0.2 mm;
the built-in silica gel supporting layer and the external silica gel protecting layer are respectively formed integrally;
the metal wires and the carbon fibers are crisscrossed after being stranded, the warp and weft density is 100 pieces per 1 square inch, wherein the warp direction is 55 pieces, and the weft direction is 45 pieces;
the sealing strip is arranged on the fiber reinforced protective layer, and the edge of the opening of the built-in silica gel supporting layer is stopped at the inner side of the sealing strip.
3. A preparation method of an antistatic silicon rubber composite flexible electrostatic shielding bag is characterized by comprising the following steps: the method comprises the following steps:
1) Preparing materials: the component preparation materials of the built-in silica gel supporting layer and the external silica gel protecting layer of the antistatic silicone rubber composite material flexible electrostatic shielding bag according to claim 1 or 2, so as to prepare the built-in silica gel supporting layer and the external silica gel protecting layer; simultaneously preparing metal wires and carbon fibers for interweaving according to the fiber reinforced protective layer component;
2) Mixing: respectively adding the components for preparing the internal silica gel supporting layer and the external silica gel protecting layer into a banburying device for respectively mixing to form a mixed rubber material for later use;
3) Interleaving: after the metal wires and the carbon fibers are stranded, the metal wires are crisscrossed according to the appointed warp and weft density to form a fiber reinforced net sheet for standby;
4) Injection molding: the mixed rubber material of the mixed built-in silica gel supporting layer and the mixed rubber material of the external silica gel protective layer are reworked, the reworked mixed rubber material of the built-in silica gel supporting layer is paved in a flat plate die or a prefabricated molded surface die, a fiber reinforced net sheet is placed after prepressing, and then the reworked mixed rubber material of the external silica gel protective layer is paved, and a flat plate die is adopted;
5) Presulfiding: pre-vulcanizing the injection molded mixed rubber and the fiber reinforced net sheet under a certain vulcanization condition, and processing the sealing strips to be adhered;
6) Folding and shaping: folding the pre-vulcanized mixed rubber and the fiber reinforced net sheet by a forming die, removing the residual area of the inner die and shaping to form a shielding bag body;
7) Secondary vulcanization: and vulcanizing the folded and molded mixed rubber and the fiber reinforced net together with the mold again, and demoulding after vulcanization is finished to obtain the antistatic silicone rubber composite material flexible electrostatic shielding bag.
4. The method for manufacturing the antistatic silicone rubber composite flexible electrostatic shielding bag according to claim 3, wherein: the mixing in the step 2) is used for preparing the materials of the internal silica gel supporting layer and the external silica gel protecting layer, and the feeding sequence and mixing time are as follows:
preheating an internal mixer to 80 ℃, stabilizing for a period of time, adding methyl vinyl silicone rubber, mixing for 1min, adding hydroxyl silicone oil, mixing for 1.5min, adding gas phase white carbon black, mixing for 3min, adding zinc stearate, mixing for 1.5min, adding sulfonic acid, mixing for 2min, adding oriented carbon nano tube, mixing for 1.5min, adding conductive nickel powder, mixing for 5min, adding coconut oil diethanolamide, and mixing for 1min;
and then the temperature is raised to 150-180 ℃ to fully mix for 2-3 hours, then vacuum heat treatment is carried out for 20-40 minutes, the rotation direction of the internal mixer is controlled to be unchanged, and the mixed rubber material for preparing the internal silica gel supporting layer and the external silica gel protecting layer is obtained after cooling and discharging.
5. The method for manufacturing the antistatic silicone rubber composite flexible electrostatic shielding bag according to claim 3, wherein: the injection molding in the step 4) is carried out, wherein the remixing is that mixed rubber materials of an internal silica gel supporting layer or mixed rubber materials of an external silica gel protective layer are placed in an open mill, vulcanizing agents are added, and the thin pass is carried out for 15-20 times for vulcanization;
the die structure for vulcanization molding of the electrostatic shielding bag is as follows: comprises an inner mold and an outer mold, both of which are provided with folding areas; the cavity type of the inner die cavity is designed according to the requirements of users and is provided with a detachable allowance zone; the outer mould tool is in the form of a foldable plate.
6. The method for manufacturing the antistatic silicone rubber composite flexible electrostatic shielding bag according to claim 3, wherein: the conditions of the prevulcanization in step 5) are: and (3) die pressing and vulcanizing for 10-15 min under the pressure of 12-15 MPa and the temperature of 175-185 ℃.
7. The method for manufacturing the antistatic silicone rubber composite flexible electrostatic shielding bag according to claim 3, wherein: the secondary vulcanization conditions in step 7) are: the process is carried out in a constant temperature oven, the temperature is controlled to be 190-200 ℃, and the time is controlled to be 4-6 h.
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