CN103242618B - Novel antibacterial plastic for household appliances and preparation method thereof - Google Patents
Novel antibacterial plastic for household appliances and preparation method thereof Download PDFInfo
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- CN103242618B CN103242618B CN201310185440.4A CN201310185440A CN103242618B CN 103242618 B CN103242618 B CN 103242618B CN 201310185440 A CN201310185440 A CN 201310185440A CN 103242618 B CN103242618 B CN 103242618B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92561—Time, e.g. start, termination, duration or interruption
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/9258—Velocity
- B29C2948/9259—Angular velocity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92885—Screw or gear
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92904—Die; Nozzle zone
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides novel antibacterial plastic for household appliances. The novel antibacterial plastic for the household appliances is characterized by being prepared by mixing the following raw materials in parts by weight: 60 to 80 parts of resin, 8 to 20 parts of macromolecular antibacterial agent, 5 to 15 parts of toughening agent and 0.1 to 0.5 part of antioxidant. The novel antibacterial plastic for the household appliances has low cost; the ageing resistance of plastic products is enhanced; the household appliances are not blackened and yellowed after being used for a long term; and the novel antibacterial plastic has long-term antibacterial effect, so the service life of the plastic pieces of the household appliances is prolonged.
Description
Technical field
The invention belongs to macromolecule engineering plastics technology field, particularly antibiotic plastic and preparation method thereof for a kind of household electrical appliances.
Background technology
In daily life, quite a few unwanted bacteria is exist and breed on the surface of plastics, the position frequently contacting with human body, object in household electrical appliance, if refrigerator rack, gasket, door handle, agitation wheel for washing machine, control knob, Telephone handset, microphone etc. surface is vegetative place.The auxiliary agent using in plastics processing is the nutrition source of microorganism, and at surface contamination greasy dirt, bacterium, mould more easily grow in a humid environment.Human body contacts with plastics and causes various diseases.Along with the continuous enhancing of people to healthy and environmental consciousness, the demand of " antibacterial, sterilization " is proposed to contacting household electrical appliance plastic components frequently in daily life.
The development and research of antibiotic plastic starts from the 80's of 20th century, makes great progress and be widely used in household electric appliances take developed countries such as Japan, the U.S. and West Europe as main research.The research of the antibacterial household electrical appliances plastics of China just grew up in recent years, and research starting point is lower, and achievement in research and world level gap are larger, especially weak foundation aspect the industrial applications of antiseptic-germicide.Household electrical appliances have a good application prospect with antibiotic plastic, along with the formal appearance of relative national standards GB21551.2-2010 " antibacterial, the degerming of family expenses and similar applications electrical equipment, the particular requirement of purification function anti-biotic material ", antibiotic plastic also will be more wide in the prospect of household electrical appliances market.
The core composition of antibiotic plastic is antiseptic-germicide, and plastic antimicrobial agent is a class novel plastic additive, is mainly divided into inorganic, organic and natural three large series.
Organic antiseptic-germicide is owing to having limited its application at aspect Shortcomings such as security, thermotolerance, Durability of antimicrobial effect and broad-spectrum antibacterial property; The shortcomings such as natural antimicrobial agent toxicity is low, uses safety, but exists poor heat resistance, and range of application is narrow, Durability of antimicrobial effect is poor.
Chinese patent CN102675817 has recorded a kind of household electrical appliances antibiotic plastic and preparation method thereof, adopt the oxide carried heavy metal nanoparticle of photocatalytic metal subtype complex antimicrobials mineral-type antiseptic-germicide mostly to be metal ion class antiseptic-germicide, formed by carrier and antimicrobial component.This antiseptic-germicide utilizes the methods such as ion-exchange, absorption, precipitation that metal ion is attached on the carriers such as zeolite, titanium dioxide, pottery, phosphatic rock.Antimicrobial component is silver ions, zine ion, cupric ion etc., and wherein the application of silver ions salt is more.The antibacterial ability of silver ions is the strongest, but its chemical property is active, easily changes brown silver suboxide into or is reduced to the simple substance silver of black through ultraviolet catalytic.In addition, use in a large number silver-colored cost high, so solving the discoloration problem of inorganic antiseptic and reducing costs these two problems is global problems.
Summary of the invention
The present invention seeks to, in order to overcome the deficiencies in the prior art, provides a kind of novel household appliance antibiotic plastic, it is characterized in that mainly being made through blend by following mass fraction raw material:
Resin 60-80 part
Polymer antibacterial agent 8-20 part
Toughner 5-15 part
Antioxidant 0.1-0.5 part
Preferably, made through blend by following parts by weight raw material,
Resin 75-85 part
Polymer antibacterial agent 13-15 part
Toughner 10-12 part
Antioxidant 0.2-0.4 part
Preferably, made through blend by following parts by weight raw material,
80 parts of resins
14 parts of polymer antibacterial agents
11 parts of toughner
0.3 part of antioxidant.
Preferably, described polymer antibacterial agent be matrix resin on molecular chain, assemble antibacterial group, described functional group be quaternary, season phosphonium salt type, guanidinesalt type or pyridine, be preferably quaternary polymer antibacterial agent.The features such as compare micromolecular inorganic and organic antibacterial agent, polymer antibacterial agent has higher electric density, and antibacterial ability is stronger, in addition, also has chemical stability high, and residual toxicity is low, easy processing.
The preparation method of quaternary polymer antibacterial agent mainly contains two kinds, and one is first to prepare antiseptic monomer, then prepares the dangle polymkeric substance of quaternary ammonium salt group of side chain by polyreaction; Another kind method is first to prepare the polymkeric substance of needs, then react with the active function groups on polymer chain by chemical reaction carry out antibacterial functionalized.
The preparation method of quaternary polymer antibacterial agent master batch: other auxiliary agents such as matrix resin, dispersion agent, oxidation inhibitor are mixed in high-speed mixer with the powder of the antiseptic-germicide of above-mentioned preparation.
Wherein, above-mentioned antiseptic-germicide is composite granule or the antibacterial matrices that is a granulated into by composite granule and matrix resin.The particle diameter of described antimicrobial powder is 70-90nm.
Preferably, described polymer antibacterial agent be selected from antibacterial functionalized polypropylene masterbatch (PPNH) and antibacterial functionalized polyethylene masterbatch (PENH) wherein one or both.
Further preferably, described resin is ABS, GPPS, HIPS or PP resin.
ABS resin refers to vinyl cyanide-divinyl-styrol copolymer, and ABS is the acronym of Acrylonitrile Butadiene Styrene, is that a kind of intensity is high, good toughness, is easy to thermoplastics type's macromolecular material of machine-shaping.
GPPS resin is commonly called as benzene, is that polymerizable raw material forms by styrene monomer, is that a kind of tint permanence is good, dimensional stabilizing, thermoplastic resin that goods are transparent.
HIPS resin is commonly called as and changes benzene, is rubber modified polystyrene, and its outstanding feature is that easy processing, dimensional stabilizing, shock strength are high.
PP resin is acrylic resin, is crystalline high polymer, has the features such as good fluidity, Heat stability is good, erosion resistance.
Described toughner is methyl acrylate-butadiene-styrene terpolymer, and wherein the weight percentage of divinyl is 20-30%, and the weight percentage of methyl acrylate is 5-25%, and cinnamic weight percentage is 20-70%.
Wherein, above-mentioned household electrical appliances, with in antibiotic plastic, also comprise the color master-batch of 2～10 parts.
Described color master-batch is at least one in mineral dye, pigment dyestuff or dyestuff.
Further, described color master-batch is pigment dyestuff.
Wherein, above-mentioned household electrical appliances are with in antibiotic plastic, and described resin is ABS, GPPS, HIPS or PP resin.
Wherein, above-mentioned household electrical appliances are with in antibiotic plastic, described toughner is methyl acrylate-divinyl-styrene copolymer, wherein the weight percentage of divinyl is 10～40%, the weight percentage of methyl acrylate is 5～45%, and cinnamic weight percentage is 15～60%.
Wherein, above-mentioned household electrical appliances are with in antibiotic plastic, and described antioxidant comprises main anti-oxidant and auxiliary antioxidant, and the weight ratio of main anti-oxidant and auxiliary antioxidant is 1 ︰ 5-8.
Further, the weight ratio of main anti-oxidant and auxiliary antioxidant is 1 ︰ 6.
Wherein, main anti-oxidant is 1010 type hindered phenol antioxidant, and auxiliary antioxidant is 168 type hindered phenol antioxidant.
The method of antibiotic plastic for described household electrical appliances is, after various raw materials are mixed, to carry out blend and can make household electrical appliances antibiotic plastic in the temperature range of 180-250 ℃.
Preferably, adopt forcing machine to carry out blend when blend, Heating temperature is 180-250 ℃, and head extrusion temperature is 200-235 ℃.
Preferably, when blend, forcing machine main frame screw speed 12r/min, reinforced rotating speed 15-20r/min; The blend time is 5 minutes.
The invention has the beneficial effects as follows: high for solving existing antiseptic-germicide application negatively charged ion cost, oxidizable blackening, the problem that causes plastics smooth finish to reduce, the present invention adopts novel polymer antibacterial agent and resin and other plastics auxiliary agent reasonable formula, a kind of novel household appliance antibiotic plastic and its preparation method are developed, novel household appliance antibiotic plastic of the present invention, not only cost is low, the ageing-resistant ability of plastics strengthens, the not blackening of household electrical appliances life-time service is non-yellowing, and durable antibiotic, has extended work-ing life of household electrical appliances plastic component.
Prepared antibiotic plastic can be applicable in refrigerator, washing machine, air-conditioning, televisor, mobile phone, computer product.
Embodiment
Below by embodiment, the present invention is further described.
embodiment mono-
80 parts of ABS resin (content of vinyl cyanide is 20%, and Vicat softening point is 103 ℃, and under 200 ℃, the condition of 10Kg, its melting index is 23g/10min)
14 parts of antibacterial functionalized polypropylene
11 parts of toughner (methyl acrylate-butadiene-styrene terpolymer, wherein the weight percent content of methyl acrylate is 25%, butadiene content is 15%, styrene content is 60%)
Antioxidant 264(2,6-di-tert-butyl-4-methy phenol or
twobutylhydroxy toluene) 0.3 part.
(1) above-mentioned raw materials is mixed 5 minutes to reinforced rotating speed 20r/min; Discharging again.
(2) melt pelletization obtains antibiotic plastic, reinforced rotating speed 15r/min, and Heating temperature section: 1 section/180 ℃, 2 sections/190 ℃, 3 sections/200 ℃, 4 sections/210 ℃, 5 sections/210 ℃, 6 sections/215 ℃, 7 sections/215 ℃, 8 sections/215 ℃, 9 sections/205 ℃, head temperature: 215 ℃.
embodiment bis-
60 parts of ABS resin (content of vinyl cyanide is 20%, and Vicat softening point is 103 ℃, and under 200 ℃, the condition of 10Kg, its melting index is 23g/10min)
8 parts of antibacterial functionalized polyethylene
5 parts of toughner (methyl acrylate-butadiene-styrene terpolymer, wherein the weight percent content of methyl acrylate is 25%, butadiene content is 15%, styrene content is 60%)
Antioxidant 264(2,6-di-tert-butyl-4-methy phenol or
twobutylhydroxy toluene) 0.1 part.
(1) above-mentioned raw materials is mixed 5 minutes to reinforced rotating speed 20r/min; Discharging again.
(2) melt pelletization obtains antibiotic plastic, reinforced rotating speed 15r/min, and Heating temperature section: 1 section/180 ℃, 2 sections/190 ℃, 3 sections/200 ℃, 4 sections/210 ℃, 5 sections/210 ℃, 6 sections/215 ℃, 7 sections/215 ℃, 8 sections/215 ℃, 9 sections/205 ℃, head temperature: 215 ℃.
embodiment tri-
80 parts of ABS resin (content of vinyl cyanide is 20%, and Vicat softening point is 103 ℃, and under 200 ℃, the condition of 10Kg, its melting index is 23g/10min)
20 parts of antibacterial functionalized polyethylene
15 parts of toughner (methyl acrylate-butadiene-styrene terpolymer, wherein the weight percent content of methyl acrylate is 25%, butadiene content is 15%, styrene content is 60%)
Antioxidant 264(2,6-di-tert-butyl-4-methy phenol or
twobutylhydroxy toluene) 0.5 part.
(1) above-mentioned raw materials is mixed 5 minutes to reinforced rotating speed 20r/min; Discharging again.
(2) melt pelletization obtains antibiotic plastic, reinforced rotating speed 20r/min, and Heating temperature section: 1 section/180 ℃, 2 sections/190 ℃, 3 sections/200 ℃, 4 sections/210 ℃, 5 sections/210 ℃, 6 sections/215 ℃, 7 sections/215 ℃, 8 sections/215 ℃, 9 sections/205 ℃, head temperature: 215 ℃.
Performance test example one
Sample: embodiment 1-3,
Comparative example: prepare with reference to Chinese patent CN102675817
The above-mentioned antibacterial sample of moulding is placed 12 months, got 10g and be dissolved in 10ml chloroform, be heated to dissolve, proportional diluted, obtains the solution to be measured of a series of concentration gradients, and concrete concentration and experimental result are as shown in table 1.
Note: "+" represents obvious colony growth, "-" represents to have no colony growth.
It can be seen from the table, the sample of the embodiment of the present invention is still just brought into play anti-microbial property in 1 year through placing under very low concentration, and prescription of the present invention is described, antiseptic-germicide stability is strong, and the plastics of making also have strong more lasting antibacterial effect.
Claims (1)
1. a novel household appliance antibiotic plastic, is characterized in that, is made through blend by following parts by weight raw material:
80 parts of resins
14 parts of polymer antibacterial agents
11 parts of toughner
0.3 part of antioxidant;
Described polymer antibacterial agent be matrix resin on molecular chain, assemble antibacterial group, described functional group be quaternary, season phosphonium salt type or guanidinesalt type;
Described polymer antibacterial agent be selected from antibacterial functionalized polypropylene masterbatch, antibacterial functionalized polypropylene and antibacterial functionalized polyethylene wherein one or both;
Described resin is ABS, GPPS, HIPS or PP resin;
Described toughner is methyl acrylate-butadiene-styrene terpolymer, and wherein the weight percentage of divinyl is 20-30%, and the weight percentage of methyl acrylate is 5-25%, and cinnamic weight percentage is 20-70%;
After various raw materials are mixed, in the temperature range of 180-250 ℃, carry out blend and can make household electrical appliances antibiotic plastic;
When blend, adopt forcing machine to carry out blend, Heating temperature is 180-250 ℃, and head extrusion temperature is 200-235 ℃;
When blend, forcing machine main frame screw speed 12r/min, reinforced rotating speed 15-20r/min; The blend time is 5 minutes.
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| CN201310185440.4A CN103242618B (en) | 2013-05-20 | 2013-05-20 | Novel antibacterial plastic for household appliances and preparation method thereof |
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| CN201310185440.4A CN103242618B (en) | 2013-05-20 | 2013-05-20 | Novel antibacterial plastic for household appliances and preparation method thereof |
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| CN103242618B true CN103242618B (en) | 2014-05-14 |
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| CN105524355B (en) * | 2016-01-05 | 2018-01-23 | 江家城 | A kind of self-cleaning kitchen and bath's tubing of PP R and preparation method thereof |
| CN105936734A (en) * | 2016-06-07 | 2016-09-14 | 天津金发新材料有限公司 | Transparent flame-retardant antibacterial ABS material and preparation method thereof |
| CN107746533A (en) * | 2017-09-30 | 2018-03-02 | 河南科航环保科技有限公司 | A kind of ABS composite material of antibacterial and preparation method thereof |
| CN107964204A (en) * | 2017-12-20 | 2018-04-27 | 何志方 | The anti-aging HIPs plastics of bacteria mildew-proof and its processing technology |
| CN113150439A (en) * | 2021-04-09 | 2021-07-23 | 佛山市顺德区美的饮水机制造有限公司 | Plastic composition and application thereof, plastic part and preparation method and application thereof |
| CN116285053B (en) * | 2022-11-23 | 2024-09-27 | 宁波金雨科技实业有限公司 | Antibacterial packaging material for daily necessities replacement and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP0606762B1 (en) * | 1992-12-25 | 1998-08-05 | Japan Synthetic Rubber Co., Ltd. | Antibacterial resin composition |
| CN1294144A (en) * | 2000-11-14 | 2001-05-09 | 上海博纳科技发展有限公司 | Mother particles of antibacterial plastics and its application in preparing antibacterial plastic products |
| CN102040771B (en) * | 2009-10-16 | 2013-02-27 | 中国石油化工股份有限公司 | Antibacterial thermoplastic plastic composition and preparation method thereof |
| CN102321350A (en) * | 2011-08-24 | 2012-01-18 | 昆山埃登新材料有限公司 | Preparation method of PET antibacterial high-molecular material |
| CN102653617B (en) * | 2012-05-03 | 2014-08-27 | 光大环保科技发展（北京）有限公司 | Environment-friendly antibacterial ABS (Acrylonitrile Butadiene StyreneAcrylonitrile Butadiene Styrene) plastic and preparation method thereof |
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