CN113072780A - Antibacterial master batch, preparation method thereof and antibacterial ABS resin - Google Patents
Antibacterial master batch, preparation method thereof and antibacterial ABS resin Download PDFInfo
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
- C08L25/12—Copolymers of styrene with unsaturated nitriles
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- C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2325/02—Homopolymers or copolymers of hydrocarbons
- C08J2325/04—Homopolymers or copolymers of styrene
- C08J2325/08—Copolymers of styrene
- C08J2325/12—Copolymers of styrene with unsaturated nitriles
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- C08J2413/00—Characterised by the use of rubbers containing carboxyl groups
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- C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
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- C08J2455/00—Characterised by the use of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08J2423/00 - C08J2453/00
- C08J2455/02—Acrylonitrile-Butadiene-Styrene [ABS] polymers
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- C—CHEMISTRY; METALLURGY
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2497/00—Characterised by the use of lignin-containing materials
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- 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
- C08K2003/0806—Silver
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- 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
- C08K2003/085—Copper
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- 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
- C08K2003/0893—Zinc
Abstract
The invention discloses an antibacterial master batch, a preparation method thereof and antibacterial ABS resin. The antibacterial master batch comprises rubber powder and an inorganic antibacterial agent loaded on the rubber powder, and a carrier of the inorganic antibacterial agent is lignin. By applying the technical scheme of the invention, the carrier used by the inorganic antibacterial agent is lignin, so that the mechanical property reduction of the resin caused by the conventional inorganic carrier (such as phosphate, zeolite and the like) is avoided. The lignin is used as a high molecular polymer, the main components of the lignin are carbon, hydrogen and oxygen, so that the lignin is easily compatible with the ABS resin matrix, and in addition, the lignin contains various functional groups in the structure, and the lignin can possibly react with the resin matrix, so that the mechanical property of the resin matrix is improved, and the negative influence of the introduction of antibacterial components such as silver, zinc, copper and the like on the resin property is weakened.
Description
Technical Field
The invention relates to the technical field of antibacterial resin, and particularly relates to an antibacterial master batch, a preparation method of the antibacterial master batch and antibacterial ABS resin.
Background
ABS resin is a terpolymer of acrylonitrile, butadiene and styrene and is widely used for making liners for refrigerators, housings and interior parts for televisions, computers, air conditioners, dust collectors, telephones and other small appliances. As is well known, under the condition of appropriate objective conditions such as temperature and humidity, harmful microorganisms such as bacteria and mold can be bred on plastic products, and the daily life and the body health of people are seriously affected. Based on the increasing demand of ABS resin in the fields of home electric products, sanitary ware, interior decoration panels, etc., year by year, research related to antibacterial ABS resin is becoming one of the focus problems in the antibacterial field.
The antibacterial ABS resin is usually obtained by adding an antibacterial agent to the ABS resin, and among them, direct blending (direct blending) or masterbatch method of the antibacterial agent with the ABS resin is included. The direct mixing method is easy to ensure that the antibacterial agent is macroscopically uniformly dispersed in the ABS matrix and microscopically agglomerated, and is not generally adopted. The master batch method is to prepare the highly concentrated ABS antibacterial master batch firstly, and then mix the ABS antibacterial master batch with the ABS resin through the shearing action of a double-screw extruder, so that the antibacterial agent is dispersed in the ABS resin more uniformly, and the antibacterial performance of the resin is effectively improved. At present, most manufacturers adopt a master batch method to produce the antibacterial ABS resin.
The antibacterial agent mainly comprises two main classes of inorganic and organic antibacterial agents. The inorganic antibacterial agent is prepared by fixing metals (or ions thereof) such as silver, copper, titanium and the like in porous materials or layered crystal materials such as zeolite, silica gel, phosphonium salt and the like by mainly utilizing the antibacterial capacity of the metals such as silver, copper, zinc, titanium and the like through technical means such as physical adsorption, ion exchange, multilayer coating and the like, and then preparing the antibacterial agent through a certain processing technology. The organic antibacterial agent mainly comprises bactericide (ethanol, quaternary ammonium salt, etc.), antiseptic (organic halogen compound, etc.), and mildew-proof and algae-proof agent (pyridine, alkyl halide, etc.). The organic antibacterial agent has the main characteristics of high sterilization speed, wide antibacterial range and the like, but has the problems of poor heat resistance, easiness in exudation, toxicity of dissolved substances, washing fastness, short service life and the like, so the application of the organic antibacterial agent has great limitation.
The antibacterial master batch is usually prepared by a blending method in the market, and the method can not avoid partial inactivation (such as metal valence change) of the antibacterial active ingredients caused by high-temperature thermal experience of the antibacterial agent in the preparation process. In addition, the commonly used inorganic antibacterial agent improves the antibacterial performance of the matrix plastic and brings negative effects to the mechanical performance of the plastic product, such as great reduction of the mechanical performance, easy color change and the like. The novel antibacterial ABS master batch and the antibacterial ABS resin are developed by combining the current industrial standard requirements of China on plastic products (the antibacterial plastic with the antibacterial rate of more than 99 percent is strong antibacterial plastic, and the antibacterial rate of more than 90 percent is antibacterial plastic), so that the practical significance is realized.
Disclosure of Invention
The invention aims to provide an antibacterial master batch, a preparation method thereof and an antibacterial ABS resin, and provides a novel antibacterial master batch and an antibacterial ABS resin.
In order to achieve the above object, according to one aspect of the present invention, there is provided an antibacterial masterbatch. The antibacterial master batch comprises rubber powder and an inorganic antibacterial agent loaded on the rubber powder, and a carrier of the inorganic antibacterial agent is lignin.
Further, the rubber powder is a hydrophilic group-containing rubber powder.
Further, the rubber powder has a crosslinked structure, the rubber particles have a homogeneous structure, and the gel content is 60% or more.
Further, the rubber powder is at least one of carboxylic styrene-butadiene rubber, acrylate or ABS grafting powder.
Further, the inorganic antibacterial agent is a water-based antibacterial agent, and the bactericidal metal element is a bactericidal component, and the metal element is one or more of silver, copper and zinc.
Further, the content of the metal element accounts for 0.05 to 7 wt%, preferably 0.1 to 4 wt% of the inorganic antibacterial agent.
According to another aspect of the present invention, there is provided a method of preparing an antimicrobial masterbatch. The preparation method comprises the following steps: mixing lignin and water, and performing ultrasonic dispersion to prepare lignin hydrogel; adding a solution containing a bactericidal metal element into the lignin hydrogel, stirring and carrying out ultrasonic treatment to obtain a gel mixed solution; adding a sodium borohydride solution into the gel mixed solution, and stirring to obtain a water-based inorganic antibacterial agent; and mixing the water-based inorganic antibacterial agent with the powdered rubber, uniformly stirring and drying to obtain the antibacterial master batch.
Further, the weight ratio of the powdered rubber to the inorganic antibacterial agent is 100: 0.3-100: 30.
Further, the mixing of the water-based inorganic antibacterial agent with the powdered rubber is carried out at normal temperature; preferably, the drying is carried out in an oven at 90 ℃ to-110 ℃ for 24 hours.
According to still another aspect of the present invention, there is provided an antibacterial ABS resin. The raw materials of the antibacterial ABS resin comprise ABS resin and the antibacterial master batch.
Further, 100 parts by weight of ABS resin and 0.1-30 parts by weight of antibacterial master batch are included; preferably, 0.3-20 parts of antibacterial master batch.
Further, the antibacterial ABS resin also comprises one or more of flame retardant, plasticizer, reinforcing agent, flame retardant, antistatic agent, nucleating agent, moistening agent, pigment and dispersing agent.
By applying the technical scheme of the invention, the carrier used by the inorganic antibacterial agent is lignin, so that the mechanical property reduction of the resin caused by the conventional inorganic carrier (such as phosphate, zeolite and the like) is avoided. The lignin is used as a high molecular polymer, the main components of the lignin are carbon, hydrogen and oxygen, so that the lignin is easily compatible with the ABS resin matrix, and in addition, the lignin contains various functional groups in the structure, and the lignin can possibly react with the resin matrix, so that the mechanical property of the resin matrix is improved, and the negative influence of the introduction of antibacterial components such as silver, zinc, copper and the like on the resin property is weakened.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.
In view of the deficiencies of the prior art, according to an exemplary embodiment of the present invention, an antimicrobial masterbatch is provided. The antibacterial master batch comprises rubber powder and an inorganic antibacterial agent loaded on the rubber powder, and a carrier of the inorganic antibacterial agent is lignin.
The carrier used by the inorganic antibacterial agent is lignin, so that the reduction of the mechanical properties of the resin caused by the conventional inorganic carrier (such as phosphate, zeolite and the like) is avoided. The lignin is used as a high molecular polymer, the main components of the lignin are carbon, hydrogen and oxygen, so that the lignin is easily compatible with the ABS resin matrix, and in addition, the lignin contains various functional groups in the structure, and the lignin can possibly react with the resin matrix, so that the mechanical property of the resin matrix is improved, and the negative influence of the introduction of antibacterial components such as silver, zinc, copper and the like on the resin property is weakened.
Preferably, the rubber powder is a hydrophilic group-containing rubber powder, and the hydrophilic group-containing rubber powder can improve the dispersibility of the antibacterial agent in the rubber powder; the rubber powder has a cross-linked structure and can adsorb the inorganic antibacterial agent to the inside and the surface of the rubber under the action of concentration gradient; the rubber particles have a homogeneous structure, the gel content is more than or equal to 60 percent, and the free flowing micro powder can be formed without adding a separant after drying.
In a typical embodiment of the present invention, the rubber powder is at least one of carboxylated styrene-butadiene rubber, acrylate or ABS graft powder, and the rubber particles of the rubber powder have a homogeneous structure, which facilitates the uniform distribution of the antimicrobial agent in the rubber carrier.
Preferably, the inorganic antibacterial agent is a water-based antibacterial agent, and the bactericidal metal element is one or more of silver, copper and zinc. More preferably, the content of the metal element is 0.05 to 7 wt%, preferably 0.1 to 4 wt% of the antibacterial agent. The inorganic water-based antibacterial agent has good compatibility with the hydrophilic group-containing rubber powder, and can be rapidly distributed inside and outside the rubber. In addition, the inorganic water-based antibacterial agent is more environment-friendly, and pollution caused by volatilization of solvents or thermal decomposition is avoided in the subsequent processing stage. Meanwhile, the inorganic water-based antibacterial agent improves the water resistance of the antibacterial product.
According to an exemplary embodiment of the present invention, there is provided a method for preparing the above-described antibacterial masterbatch. The preparation method comprises the following steps: mixing lignin and water, and performing ultrasonic dispersion to prepare lignin hydrogel; adding a solution containing a bactericidal metal element into the lignin hydrogel, stirring and carrying out ultrasonic treatment to obtain a gel mixed solution; adding a sodium borohydride solution into the gel mixed solution, and stirring to obtain a water-based inorganic antibacterial agent; and (3) mixing the water-based inorganic antibacterial agent with the powdered rubber, uniformly stirring and drying to obtain the ABS antibacterial master batch. The preparation method of the antibacterial master batch provided by the invention has a simple process, and avoids partial metal ion inactivation caused by a high-temperature thermal process of preparing the antibacterial master batch by a traditional method.
Preferably, the weight ratio of the powder rubber to the inorganic antibacterial agent is 100: 0.3-100: 30. In the embodiment of the invention, the mixing of the water-based inorganic antibacterial agent and the powdered rubber is carried out at normal temperature; preferably, the drying is carried out in an oven at 90-110 ℃ for 24 hours.
According to an exemplary embodiment of the present invention, an antibacterial ABS resin is provided. The raw materials of the antibacterial ABS resin comprise ABS resin and any one of the antibacterial master batches. Preferably, the antibacterial ABS resin comprises 100 parts by weight of ABS resin and 0.1-30 parts by weight of ABS antibacterial master batch; more preferably, 0.3-20 parts of ABS antibacterial master batch. According to actual requirements, the antibacterial ABS resin also comprises one or more of a flame retardant, a plasticizer, a reinforcing agent, a flame retardant, an antistatic agent, a nucleating agent, a moistening agent, a pigment and a dispersing agent, and the addition amount can be adjusted according to actual conditions.
In a typical embodiment of the present invention, a method for preparing an antibacterial ABS resin comprises: mixing a proper amount of water-based lignin metal-loaded antibacterial agent with hydrophilic group-containing rubber powder, uniformly stirring, and drying at 100 ℃ for 24 hours to obtain the G-ABS antibacterial master batch. The antibacterial ABS resin obtained by adopting the blending method has the advantages of good antibacterial effect, good color, low cost, high impact strength and the like, and the preparation process is simple and is suitable for industrial application. The antibacterial ABS resin prepared by the invention has good antibacterial rate, good water resistance, discoloration resistance and higher impact strength
The following examples are provided to further illustrate the advantageous effects of the present invention.
The raw materials and equipment used in the following examples and comparative examples were as follows:
G-ABS powder (industrial product, PB rubber phase mass fraction is 60%), acrylonitrile-styrene copolymer (SAN, industrial product, bonded acrylonitrile mass fraction is 26.8%) and other auxiliary agents are all provided by Jilin petrochemical company; the carboxylated styrene-butadiene rubber powder and the acrylate powder are prepared by the applicant through conventional technical means in the field. In addition, silver-loaded lignin antimicrobials are available from the Jilin chemical industry institute.
Preparation of load type antibacterial master batch
Preparation of inorganic water-based antibacterial agent: putting a certain amount of lignin in a 500mL beaker, adding a proper amount of purified water, fully stirring and ultrasonically dispersing for 60 minutes to obtain lignin hydrogel, adding a certain amount of silver nitrate solution into the lignin hydrogel solution, stirring and ultrasonically oscillating for 5 minutes, then adding a certain amount of sodium borohydride solution into the solution, and magnetically stirring for 30 minutes at room temperature to obtain the water-based inorganic antibacterial agent.
Example 1
100G of G-ABS powder is put into a graduated cylinder, 300ml of lignin silver-loaded antibacterial agent aqueous solution (10G of antibacterial agent) is added, after being uniformly stirred, the mixture is put into a 100 ℃ oven and dried for 24 hours, and the G-ABS-lignin silver-loaded antibacterial master batch is obtained. The weight parts or weight ratios of the components are shown in Table 1.
Example 2
100G of G-ABS powder is put into a graduated cylinder, 300ml of lignin zinc-loaded antibacterial agent aqueous solution (20G of antibacterial agent) is added, after being uniformly stirred, the mixture is put into a 100 ℃ oven and dried for 24 hours, and the G-ABS-lignin zinc-loaded antibacterial master batch is obtained. The weight parts or weight ratios of the components are shown in Table 1.
Example 3
100G of G-ABS powder is put into a graduated cylinder, 300ml of lignin silver-zinc-loaded antibacterial agent aqueous solution (15G of antibacterial agent) is added, after being uniformly stirred, the mixture is put into a 100 ℃ oven and dried for 24 hours, and the G-ABS-lignin silver-zinc-loaded antibacterial master batch is obtained. The weight parts or weight ratios of the components are shown in Table 1.
Example 4
100G of G-ABS rubber powder is put into a graduated cylinder, 300ml of lignin silver-loaded antibacterial agent aqueous solution (0.3G of antibacterial agent) is added, after being uniformly stirred, the mixture is put into a 100 ℃ oven and dried for 24 hours, and the G-ABS-lignin silver-loaded antibacterial master batch is obtained. The weight parts or weight ratios of the components are shown in Table 1.
Example 5
100 g of carboxyl styrene butadiene rubber powder is put into a graduated cylinder, 300ml of aqueous solution of the lignin silver-loaded antibacterial agent (10 g of the antibacterial agent) is added, after being uniformly stirred, the mixture is put into a 100 ℃ oven and dried for 24 hours, and the carboxyl styrene butadiene rubber-lignin silver-loaded antibacterial master batch is obtained. The weight parts or weight ratios of the components are shown in Table 1.
Example 6
100 g of acrylate rubber powder is put into a graduated cylinder, 300ml of lignin silver-loaded antibacterial agent aqueous solution (10 g of antibacterial agent) is added, after being uniformly stirred, the mixture is put into a 100 ℃ oven and dried for 24 hours, and the acrylate-lignin silver-loaded antibacterial master batch is obtained. The weight parts or weight ratios of the components are shown in Table 1.
TABLE 1
| G-ABS powder | Antibacterial agent | The content of metal elements in the antibacterial agent is wt% | |
| Practice ofExample 1 | 100 | 10 | 2 |
| Example 2 | 100 | 20 | 3 |
| Example 3 | 100 | 15 | 2 |
| Example 4 | 100 | 0.3 | 2 |
| Example 5 | 100 | 10 | 2 |
| Example 6 | 100 | 10 | 2 |
Preparation of antibacterial ABS resin
Examples 1 to 1
Putting 25 parts of G-ABS powder, 5 parts of SAN75 parts of the G-ABS lignin silver-loaded antibacterial master batch prepared in the example 1 and 1.28 parts of other auxiliaries into a low-speed mixer, fully and uniformly stirring, then carrying out melt blending on the mixed materials through a double-screw extruder, carrying out extrusion granulation, and drying the granules for 2 hours at 80 ℃;
example 2-1
Putting 25 parts of G-ABS powder, 5 parts of SAN75 parts of the G-ABS lignin zinc-loaded antibacterial master batch prepared in the example 2 and 1.28 parts of other auxiliaries into a low-speed mixer, fully and uniformly stirring, then carrying out melt blending on the mixed materials through a double-screw extruder, carrying out extrusion granulation, and drying the granules for 2 hours at 80 ℃;
example 3-1
Putting 25 parts of G-ABS powder, 5 parts of SAN75 parts of the G-ABS lignin silver-zinc-loaded antibacterial master batch prepared in the example 3 and 1.28 parts of other additives into a low-speed mixer, fully and uniformly stirring, then carrying out melt blending on the mixed materials through a double-screw extruder, carrying out extrusion granulation, and drying the granules for 2 hours at 80 ℃;
example 4-1
Putting 25 parts of G-ABS powder, 5 parts of SAN75 parts of the silver-loaded lignin antibacterial master batch prepared in the embodiment 4 and 1.28 parts of other auxiliaries into a low-speed mixer, fully and uniformly stirring, then carrying out melt blending on the mixed materials through a double-screw extruder, carrying out extrusion granulation, and drying the granules for 2 hours at 80 ℃;
example 5-1
20 parts of G-ABS powder, 75 parts of SAN, 5 parts of the carboxylic styrene-butadiene rubber-lignin silver-loaded antibacterial master batch prepared in the example 5 and 1.28 parts of other additives are put into a low-speed mixer to be fully and uniformly stirred, then the mixed materials are melted and blended by a double-screw extruder, extruded and granulated, and then the granules are dried for 2 hours at 80 ℃;
example 6-1
Putting 25 parts of G-ABS powder, 0.3 part of SAN75 part of the acrylic ester-lignin silver-loaded antibacterial master batch prepared in the embodiment 6 and 1.28 parts of other additives into a low-speed mixer, fully and uniformly stirring, then carrying out melt blending on the mixed materials through a double-screw extruder, extruding and granulating, and drying the granules for 2 hours at 80 ℃;
comparative example 1
Putting 25 parts of G-ABS powder, 75 parts of SAN and 1.28 parts of other additives into a low-speed mixer, fully and uniformly stirring, then melting and blending the mixed materials through a double-screw extruder, extruding and granulating, and drying the granules for 2 hours at 80 ℃;
comparative example 2
Putting 25 parts of G-ABS powder, 75 parts of SAN, 0.6 part of inorganic silver antibacterial agent of Beijing Aisler company and 1.28 parts of other auxiliary agents into a low-speed mixer, fully and uniformly stirring, then melting and blending the mixed materials through a double-screw extruder, extruding and granulating, and drying the granules for 2 hours at 80 ℃;
the pellets obtained in examples 4 to 6 and comparative example 1-2 were molded into standard test specimens using an injection molding machine, Toshiba Is80, at 200 ℃ for mechanical properties, UV aging resistance and thermo-oxidative aging. And (3) injecting a sample of 50mm x 50mm at the injection temperature of 200-210 ℃ for antibacterial test.
The impact strength of the cantilever beam notch is tested according to ASTM D256; the antibacterial test was performed according to QB/T2591-. Further, the samples of the above examples and comparative examples were evaluated for ultraviolet aging resistance according to ASTM _ D _ 4587. Placing an ABS resin standard sample wafer for testing chromaticity in an ultraviolet aging box, and testing the comprehensive color difference delta E before and after aging after ultraviolet aging for 2 weeks; the evaluation method of the thermo-oxidative aging performance comprises the following steps: and (3) placing the ABS resin standard sample wafer for testing the chromaticity in a 70 ℃ oven, carrying out thermo-oxidative aging for 2 weeks in the air atmosphere, and testing the comprehensive color difference delta E before and after aging.
The results of the antibacterial tests and the impact strengths of the above examples 1-1 to 6-1 and comparative examples are shown in Table 2, and the results of UV aging and thermo-oxidative aging thereof are shown in Table 3.
As can be seen from the results in Table 2, compared with comparative example 1, the antibacterial ABS resin containing lignin carrying silver, zinc and silver zinc has good antibacterial performance, and meets the current domestic industrial standard of antibacterial plastics (the antibacterial rate is more than 90%); compared with the common inorganic antibacterial agent on the market (comparative example 2), the antibacterial ABS resin provided by the invention has higher impact strength, and is suitable for occasions requiring antibiosis and higher impact strength.
The data in Table 3 show that the Delta E after UV aging and thermal oxidative aging of examples 1-1 to 6-1 is significantly lower than that of comparative example, which shows that the anti-UV aging resistance and thermal oxidative aging resistance of the antibacterial ABS resin of the present invention are significantly improved, and the discoloration resistance of the antibacterial ABS resin containing lignins loaded with silver, zinc and silver zinc is superior to that of the antibacterial ABS resin commonly used in the market (comparative example 2).
TABLE 2
| Antibacterial ratio (%) | Sample bacterial species | Impact Strength (kJ/m)2) | |
| Examples 1 to 1 | 96.85 | Staphylococcus aureus | 22.5 |
| Example 2-1 | 92.13 | Staphylococcus aureus | 20.4 |
| Example 3-1 | 94.72 | Staphylococcus aureus | 21.2 |
| Example 4-1 | 90.14 | Staphylococcus aureus | 21.5 |
| Example 5-1 | 93.16 | Staphylococcus aureus | 20.9 |
| Example 6-1 | 91.18 | Staphylococcus aureus | 22.8 |
| Comparative example 1 | 50.10 | Staphylococcus aureus | 23.6 |
| Comparative example 2 | 94.6 | Staphylococcus aureus | 16.7 |
TABLE 3
| Delta E after UV aging | Delta E after thermo-oxidative aging | |
| Examples 1 to 1 | 5.53 | 1.02 |
| Example 2-1 | 6.01 | 1.24 |
| Example 3-1 | 4.92 | 0.89 |
| Example 4-1 | 6.36 | 1.29 |
| Example 5-1 | 5.78 | 1.10 |
| Example 6-1 | 5.87 | 1.19 |
| Comparative example 1 | 9.53 | 1.69 |
| Comparative example 2 | 8.51 | 1.44 |
From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects:
compared with the traditional preparation method of the antibacterial master batch, the preparation method of the load-type antibacterial master batch provided by the invention avoids partial metal ion inactivation caused by a high-temperature thermal process, ensures more sterilization active points, can provide higher sterilization rate under the condition of lower metal consumption, is simple and easy to operate, and is suitable for industrialization; in addition, the rubber powder-loaded antibacterial master batch has good compatibility with ABS resin, the lignin-loaded metal antibacterial agent fully utilizes the molecular structure characteristics and the metal ion passivation effect of the lignin-loaded metal antibacterial agent, the ABS resin is endowed with good antibacterial performance, the ABS resin is ensured to have higher impact strength, and the ABS resin shows excellent discoloration resistance under the UV aging condition.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (12)
1. The antibacterial master batch is characterized by comprising rubber powder and an inorganic antibacterial agent loaded on the rubber powder, wherein a carrier of the inorganic antibacterial agent is lignin.
2. The antimicrobial masterbatch according to claim 1, wherein the rubber powder is a hydrophilic group-containing rubber powder.
3. The antibacterial masterbatch according to claim 1, wherein the rubber powder has a crosslinked structure, the rubber particles have a homogeneous structure, and the gel content is 60% or more.
4. The antibacterial masterbatch according to claim 2 or 3, wherein the rubber powder is at least one of carboxylated styrene-butadiene rubber, acrylates or ABS graft powder.
5. The antibacterial masterbatch according to claim 1, wherein the inorganic antibacterial agent is a water-based antibacterial agent, and a bactericidal metal element is a bactericidal component, and the metal element is one or more of silver, copper and zinc.
6. The antimicrobial masterbatch according to claim 5, wherein the metal element content is 0.05 to 7 wt%, preferably 0.1 to 4 wt% of the inorganic antimicrobial agent.
7. A process for preparing an antimicrobial masterbatch according to any one of claims 1 to 6, comprising the steps of:
mixing lignin and water, and performing ultrasonic dispersion to prepare lignin hydrogel;
adding a solution containing a bactericidal metal element into the lignin hydrogel, stirring and carrying out ultrasonic treatment to obtain a gel mixed solution; adding a sodium borohydride solution into the gel mixed solution, and stirring to obtain a water-based inorganic antibacterial agent; and
and mixing the water-based inorganic antibacterial agent with powdered rubber, uniformly stirring and drying to obtain the antibacterial master batch.
8. The production method according to claim 7, wherein the weight ratio of the powder rubber to the inorganic antibacterial agent is 100:0.3 to 100: 30.
9. The production method according to claim 7, wherein the mixing of the water-based inorganic antibacterial agent with the powdered rubber is performed at normal temperature; preferably, the drying is carried out in an oven at 90 ℃ to-110 ℃ for 24 hours.
10. An antibacterial ABS resin characterized in that its raw materials comprise an ABS resin and the antibacterial masterbatch according to any one of claims 1 to 6.
11. The antibacterial ABS resin according to claim 10, wherein the antibacterial ABS resin comprises 100 parts by weight of the ABS resin, 0.1-30 parts by weight of the antibacterial master batch; preferably, 0.3-20 parts of the antibacterial master batch.
12. The antibacterial ABS resin of claim 10, wherein the antibacterial ABS resin further comprises one or more of a flame retardant, a plasticizer, a reinforcing agent, a flame retardant, an antistatic agent, a nucleating agent, a humectant, a pigment, a dispersant.
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