CN112107084B - Zipper tooth, preparation method of zipper tooth and zipper with zipper tooth - Google Patents
Zipper tooth, preparation method of zipper tooth and zipper with zipper tooth Download PDFInfo
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- CN112107084B CN112107084B CN202010795299.XA CN202010795299A CN112107084B CN 112107084 B CN112107084 B CN 112107084B CN 202010795299 A CN202010795299 A CN 202010795299A CN 112107084 B CN112107084 B CN 112107084B
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- tooth
- zipper
- polyformaldehyde
- injection molding
- polyoxymethylene
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- A—HUMAN NECESSITIES
- A44—HABERDASHERY; JEWELLERY
- A44B—BUTTONS, PINS, BUCKLES, SLIDE FASTENERS, OR THE LIKE
- A44B19/00—Slide fasteners
- A44B19/24—Details
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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
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/0001—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor characterised by the choice of material
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L59/00—Compositions of polyacetals; Compositions of derivatives of polyacetals
- C08L59/02—Polyacetals containing polyoxymethylene sequences only
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2059/00—Use of polyacetals, e.g. POM, i.e. polyoxymethylene or derivatives thereof, as moulding material
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Slide Fasteners (AREA)
Abstract
The invention provides a zipper tooth, which comprises a tooth head, a tooth neck and a tooth tail, wherein the tooth head, the tooth neck and the tooth tail are made of homopolymerized polyformaldehyde. The invention also provides a preparation method of the zipper teeth and a zipper with the zipper teeth. The preparation method of the zipper teeth comprises the steps of melting, injection molding and pressure maintaining, wherein in the melting step, the homopolymerized polyformaldehyde is heated, so that the melt flow rate of the homopolymerized polyformaldehyde is in the range of 9-32g/10 min; in the injection molding step, the homopolyformaldehyde is injected from an injection molding machine into an injection mold; in the pressure-holding step, the homo-polyoxymethylene is compacted in the injection mold. The chain teeth prepared from the homopolymerized polyformaldehyde have compact and uniform molecular structure, so that microorganisms and bacteria are difficult to attach, and nutrients required by the propagation of the chain teeth cannot be absorbed, so that the chain teeth have a good antibacterial effect.
Description
Technical Field
The invention relates to a zipper tooth, a preparation method of the zipper tooth and a zipper with the zipper tooth, and belongs to the field of zippers.
Background
The zipper is widely applied to daily necessities such as clothes, bags, shoes and the like. With the development of the clothing and case industry and the continuous improvement of the living standard of people, the requirements of people on the performance of zipper products are higher and higher. The zipper is generally exposed on the surfaces of clothes and bags and directly contacts with external harmful bacteria and microorganisms, thereby bringing health hidden troubles to people using the zipper. In addition, medical surgical gowns and protective clothing are also increasingly demanding on the antimicrobial properties of the zippers they use. Currently, silver ions are used to coat the surface of a zipper part to achieve a bacteriostatic effect, but silver is very easily oxidized and easily lost when a slider slides, so that the antibacterial/bacteriostatic effect of a zipper containing a silver ion material is not ideal.
Disclosure of Invention
The invention provides a zipper tooth, a preparation method of the zipper tooth, a zipper with the zipper tooth and a product. The tooth comprises a tooth head, a tooth neck and a tooth tail, wherein the tooth head, the tooth neck and the tooth tail are made of homopolymerized polyformaldehyde. Preferably, the homopolymeric polyoxymethylene is of the formula
The molecular weight range is 10000 to 20000. Or preferably, the melt flow rate of the homopolymeric polyoxymethylene used to make the element is in the range of 9 to 32g/10 min. Or preferably, the surface roughness of the coupling element is not more than 1.6 um. Or preferably, the antibacterial activity value of the tooth element is greater than 2.
The invention provides a preparation method of the zipper teeth, which comprises the steps of melting, injection molding and pressure maintaining; in the melting step, the homopolymerized polyformaldehyde is heated, so that the melt flow rate of the homopolymerized polyformaldehyde is in the range of 9-32g/10 min; in the injection molding step, the homopolyformaldehyde is injected from an injection molding machine into an injection mold; in the pressure-holding step, the homo-polyoxymethylene is compacted in the injection mold. Preferably, in the injection molding step, the temperature range of the injection molding machine is set to 180-. Or preferably, the water content of the homopolymethylenes prior to the melting step is less than 0.1%. Or preferably, in the injection molding step, the injection speed ranges from 0.3 to 3mm/min and the injection pressure ranges from 60 to 120 Mpa.
The invention also provides a zipper, which comprises zipper teeth, a pull head and a cloth belt, wherein the zipper teeth comprise tooth heads, tooth necks and tooth tails, and the tooth heads, the tooth necks and the tooth tails are made of homopolymerized polyformaldehyde. Preferably, at least a portion of the slider is made of the homopolymeric polyoxymethylene. Or preferably, the zipper further comprises an upper stop and a lower stop, wherein the upper stop and/or the lower stop are made of the homopolymerized polyformaldehyde. Or preferably, the cloth belt is made of the homopolymerized polyformaldehyde fiber yarns.
The invention also provides an article comprising the zipper.
Drawings
FIG. 1 shows an interlocking element configuration.
FIG. 2 is a single element construction.
Figure 3 is the general structure of a zipper.
In the drawings, the names of the components represented by the respective reference numerals are as follows:
1. the zipper teeth comprise a zipper tooth body 11, a tooth head 12, a tooth neck 13, a tooth tail 2, a cloth belt 3, a zipper head 4, an upper stop 5 and a lower stop.
Detailed Description
The principles and features of this invention are described below in conjunction with the following drawings, which are set forth by way of illustration only and are not intended to limit the scope of the invention.
As shown in FIGS. 1 to 3, the present invention provides an element 1 comprising a head 11, a neck 12 and a tail 13, the head 11, neck 12 and tail 13 being made of a homopolymeric polyoxymethylene.
In one embodiment, the homopolymeric polyoxymethylene is of the formula
The molecular weight range is 10000 to 20000.
In the art, the production flow of homopolymethylenes generally comprises: the formaldehyde solution is used as a raw material, and is reacted with isooctanol to generate an ethyl hemihydrated formaldehyde solution, and then the ethyl hemihydrated formaldehyde solution is dehydrated, refined and thermally cracked to obtain pure formaldehyde. Introducing pure formaldehyde into an inert solution containing a cationic catalyst (such as boron trifluoride diethyl etherate complex) to polymerize into the homopolymerized formaldehyde. Filtering, separating and drying the polymer material, and then carrying out hydroxyl esterification end capping by using acetic anhydride to obtain thermostable polyformaldehyde; then adding an antioxidant and other auxiliary agents, and preparing a finished product through extrusion granulation.
Compared with other high polymer materials, the molecular structure of the polyformaldehyde has the particularity and excellent self-lubricating property. The homopolymerized polyformaldehyde utilized by the invention is more regular and unified in molecular arrangement than the copolymerized polyformaldehyde of a double monomer due to a single monomer molecular unit. Thus, homopolymethylenes have a higher degree of crystallinity, for example, more than 50%, and a more dense and homogeneous material structure. Bacteria and microorganisms are thus difficult to attach and cannot take up the nutrients required for their own reproduction. The zipper teeth made of the homopolymerized polyformaldehyde material also have excellent antibacterial performance and durable antibacterial effect.
In another embodiment, the surface roughness of the tooth element is not more than 1.6 um. In the field of zipper technology, the surface roughness of a fastener element generally refers to the arithmetic mean deviation of peaks to valleys of a surface roughness profile, i.e. the arithmetic mean of absolute values of profile offsets within a sampling length.
In yet another embodiment, the zipper element has an antimicrobial activity value greater than 2.
In a preferred embodiment, the polyoxymethylene homopolymer used in the fastener elements of the present invention has a melt flow rate in the range of 9 to 32g/10 min. It is further preferred that the melt flow rate of the homopolymethylenes is in the range from 15 to 32g/10 min. The chain teeth with compact and uniform molecular structure, excellent antibacterial performance and stability can be prepared by utilizing the homopolymerized polyformaldehyde material with the melt flow rate within the range.
The zipper tooth provided by the invention is manufactured by an injection molding process. Injection molding refers to a process in which a molten plastic material is injected into a mold cavity under high pressure at a certain temperature, and a molded product is obtained after cooling and solidification.
The zipper tooth provided by the invention can be manufactured by the following injection molding process, and the process mainly comprises the steps of melting, injection molding and pressure maintaining.
In the melting step, the homopolyformaldehyde is heated to a melt flow rate in the range of 9 to 32g/10 min. In a preferred embodiment, the processing temperature and corresponding allowable residence time of the homopolyformaldehyde in the screw barrel of the injection molding machine may be: the temperature is 200 ℃, and the time is within 60 minutes; or the temperature is 210 ℃ and the time is within 30 minutes; or the time is within 15 minutes when the temperature is 220 ℃; alternatively, the temperature is 230 ℃ and the time is within 10 minutes.
Preferably, the water content of the homopolymeric polyoxymethylene material is below 0.1% before the melting step is initiated. When the water content is higher than 0.1%, the material can be dried under the condition of 80-90 ℃/3-4 hours.
In the injection molding step, the homopolyformaldehyde is injected from an injection molding machine into an injection mold. Preferably, the temperature of the injector may be set at 180-. Further preferably, the temperature setting from the hopper seat side to the nozzle side of the injection molding machine is, in order: 195 ℃ at 180 ℃ and 205 ℃ at 205 ℃ and 215 ℃ at 195 ℃ and 210 ℃.
In another preferred embodiment, the screw speed in the injection machine is in the range of 100-150rpm and the back pressure is in the range of 0.5-3 MPa. Further, the injection speed range is 0.3-3mm/min, and the injection pressure range is 60-120 MPa.
In the pressure-holding step, the homo-polyoxymethylene is compacted in the injection mold. In one embodiment, the dwell pressure is in the range of 60-100Mpa and the dwell time is in the range of 1-3 s. The temperature range of the injection mold may be set to 35-85 deg.c. The switching point from the injection process to the dwell process is when the mold cavity is 80-95% full.
According to the invention, the chain teeth are manufactured by preferably processing homopolymerized polyformaldehyde, and a matched chain tooth forming processing technology is developed aiming at the material, so that the chain teeth with compact and uniform molecular structures and compact and smooth self texture are obtained. Microorganisms and bacteria are difficult to attach to the surface of the fastener elements, and nutrients required for the propagation of the fastener elements cannot be absorbed by the surfaces of the fastener elements, so that the fastener elements have an excellent antibacterial effect. In addition, the homopolymerized polyformaldehyde is stable in property and not easy to react with other substances, namely, the homopolymerized polyformaldehyde is not easy to lose, and the antibacterial effect of the zipper teeth is exerted for a long time.
The invention also provides a zipper, which comprises a pull head 2, a cloth belt 3 and a zipper tooth 1 made of homopolymerized polyformaldehyde. In one embodiment, at least a portion of the zipper pull is made of homopoly-polyoxymethylene. In another embodiment, the zipper further comprises an upper stop 4 and a lower stop 5, the upper stop 4 and/or the lower stop 5 being made of homopolymeric polyoxymethylene. Further preferably, the cloth belt 3 is made of homopolymerized polyformaldehyde fiber yarns.
The invention also provides an article comprising the zipper.
The method for detecting the antibacterial effect of the fastener element and the detection result of the method are described below.
The detection method is strictly in accordance with relevant detection standards, such as ISO: 22196-2011 or GB/T31402-2015 (standard name of test method for antibacterial property of plastic surface) stipulated conditions and detection requirements specifically comprise:
(1) related materials-Staphylococcus aureus and Escherichia coli at a certain concentration, reagents, media and solutions, instruments (dry heat sterilization chamber, incubator, pipetter, stirrer, ultrasonic cleaner, inoculating loop, cover film, petri dish, gauze, absorbent cotton, volumetric flask, etc.);
(2) dry heat sterilization conditions: 30 minutes at 180 ℃;
(3) inoculating and preserving conditions of strains: inoculating the strain on proper culture medium, storing at 5-10 deg.C, and inoculating once a month;
(4) bacterial preculture
Bacteria are transferred from the culture medium of the preserved strain to a slant culture medium by using a sterile inoculating loop and cultured for 16 to 24 hours at the temperature of (35 +/-1). Then transferring the bacteria to a fresh slant culture medium by using an aseptic inoculating loop, and culturing for 16-20 h at the temperature of (35 +/-1).
(5) Preparation of the samples
At least 3 samples of the material subjected to the antibacterial treatment were prepared, and at least 6 samples of the material not subjected to the antibacterial treatment were prepared. 3 samples without antimicrobial treatment were used to measure the number of live bacteria immediately after inoculation, and another 3 samples were used to measure the number of live bacteria 24 hours after inoculation.
(6) Preparation of inoculum
Using a sterile inoculating loop, one loop of the pre-cultured bacteria was transferred to a small amount of 1/500 NB. Ensure that the bacteria are evenly dispersed and determine the bacterial count using a microscope observation and counting plate or by other suitable means, such as spectrophotometry. The bacterial suspension was diluted with 1/500NB to a bacterial concentration of 2.5X 105CFU/mL～10×105The optimal concentration is 6.0X10 between CFU/mL5CFU/mL, used as a seed inoculum. If the inoculum is not used immediately, it is placed on ice (0 ℃) and used within 2 hours.
(7) Inoculation of the sample
The outer surface of the article serves as a test surface and the cross-section of the article does not require testing. The samples were placed individually in sterile petri dishes with the test side facing up. 0.4mL of the inoculum was pipetted and dropped onto the surface of each sample. And covering the prepared film of 40mmX40mm on the inoculated bacterial liquid, slightly pressing the film downwards to diffuse the bacterial liquid to the periphery to ensure that the bacterial liquid does not overflow from the edge of the film, and covering a culture dish cover after the sample is inoculated and the film is covered.
(8) Culture conditions for inoculated samples
The petri dish containing the inoculated sample (including 3 inoculated samples without the antibacterial-treated product) was incubated at (35 + -1) deg.C with a relative humidity of not less than 90% for (24 + -1) h. The antibacterial effect of the product is determined according to the antibacterial property value obtained by detecting at the culture temperature.
The chain tooth provided by the invention is detected to obtain the following detection results:
| detection of bacterial species | Escherichia coli ATCC 8739 | Staphylococcus aureus ATCC 6538 |
| Concentration of inoculum (CFU/mL) | 1.2x10＾6 | 6.4x10＾5 |
| Inoculum size (mL) | 0.2 | 0.2 |
| U0 | 4.14 | 3.89 |
| Ut | 4.69 | 5.51 |
| At | 0.91 | 2.76 |
| Antibacterial activity value R | 3.8 | 2.8 |
Remarking: 1. the control was a plastic film without antimicrobial properties.
2, U0: number of bacteria (CFU/cm) obtained after elution of the control sample at 0h contact time2) The logarithmic value of (c).
3. Ut: number of bacteria (CFU/cm) obtained after elution of the control sample at 24h contact time2) The logarithmic value of (c).
At: number of bacteria (CFU/cm) obtained after the sample was eluted at 24h contact time2) The logarithmic value of (c).
5, R: the antibacterial activity value, R ═ Ut-At.
6. Sample pretreatment: wiping the surface of the sample with 70% alcohol, washing with sterile water, and naturally drying.
According to the detection result, the antibacterial activity values of the zipper tooth provided by the invention are respectively 3.8 and 2.8, and the antibacterial activity values are obviously superior to those of a material without antibacterial performance (namely a control sample).
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (13)
1. The zipper tooth is characterized by comprising a tooth head, a tooth neck and a tooth tail, wherein the tooth head, the tooth neck and the tooth tail are made of homopolymerized polyformaldehyde; the molecular weight range of the homopolymerized polyformaldehyde is 10000-20000, and the surface roughness of the zipper teeth is not more than 1.6 um.
2. The fastener of claim 1, wherein said homopolymeric polyoxymethylene is of the formula
。
3. The fastener element of claim 1, wherein the melt flow rate of the homopolymeric polyoxymethylene used to make the fastener element is in the range of 9-32g/10 min.
4. The tooth element of claim 1, wherein said tooth element has an antimicrobial activity value greater than 2.
5. A method of making the fastener element of any one of claims 1 to 4, comprising the steps of melting, injection molding and holding pressure;
in the melting step, the homo-polyformaldehyde is heated, so that the melt flow rate of the homo-polyformaldehyde is in the range of 9-32g/10 min;
in the injection molding step, the homopolyformaldehyde is injected from an injection molding machine into an injection mold;
in the pressure-holding step, the homo-polyoxymethylene is compacted in the injection mold.
6. The method for preparing the fastener element according to claim 5, wherein the temperature range of the injection molding machine is set to 180-215 ℃ in the injection molding step.
7. The method for producing the fastener element according to claim 5, wherein the water content of the polyoxymethylene homopolymer before the melting step is less than 0.1%.
8. The method for manufacturing a coupling element according to claim 5, wherein in the injection molding step, the injection speed is in a range of 0.3 to 3mm/min and the injection pressure is in a range of 60 to 120 Mpa.
9. A slide fastener comprising an element, a slider and a tape, the element being the element defined in any one of claims 1 to 4.
10. The zipper of claim 9, wherein at least a portion of the slider is made of the homopolymeric polyoxymethylene.
11. The zipper of claim 9, further comprising an upper stop and a lower stop, the upper and/or lower stops being made of the homopolymeric polyoxymethylene.
12. A zipper according to claim 9, said tapes being made of said homopolymeric polyoxymethylene fiber filaments.
13. An article comprising the zipper of any one of claims 9-12.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010795299.XA CN112107084B (en) | 2020-08-10 | 2020-08-10 | Zipper tooth, preparation method of zipper tooth and zipper with zipper tooth |
| PCT/CN2020/119905 WO2022032836A1 (en) | 2020-08-10 | 2020-10-09 | Zipper tooth, method for preparing zipper tooth, and zipper having zipper tooth |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010795299.XA CN112107084B (en) | 2020-08-10 | 2020-08-10 | Zipper tooth, preparation method of zipper tooth and zipper with zipper tooth |
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| Publication Number | Publication Date |
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| CN112107084A CN112107084A (en) | 2020-12-22 |
| CN112107084B true CN112107084B (en) | 2022-05-17 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN202010795299.XA Active CN112107084B (en) | 2020-08-10 | 2020-08-10 | Zipper tooth, preparation method of zipper tooth and zipper with zipper tooth |
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| Country | Link |
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| CN (1) | CN112107084B (en) |
| WO (1) | WO2022032836A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113170956A (en) * | 2021-04-23 | 2021-07-27 | 福建浔兴拉链科技股份有限公司 | Zipper cloth belt, zipper and article using zipper |
| CN114532672B (en) * | 2022-04-02 | 2023-06-23 | 温州日成拉链有限公司 | Degradable injection molding zipper and preparation method thereof |
Family Cites Families (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1174007A (en) * | 1997-03-28 | 1998-02-25 | 福建省石狮市华联服装配件企业有限公司 | Zipper head of engineering plastics and its production process |
| AUPP176898A0 (en) * | 1998-02-12 | 1998-03-05 | Moldflow Pty Ltd | Automated machine technology for thermoplastic injection molding |
| KR20040003515A (en) * | 2002-07-03 | 2004-01-13 | 한국엔지니어링플라스틱 주식회사 | Polyoxymethylene composition for colored zipper, colored zipper using polyoxymethylene composition and method for preparing colored zipper |
| US7056417B2 (en) * | 2003-05-16 | 2006-06-06 | Illinois Tool Works Inc. | Method and apparatus for sealing flanges and deforming profiles of plastic zipper |
| CN102051020B (en) * | 2009-10-30 | 2013-02-06 | 中国石油化工股份有限公司 | Antibacterial polyoxymethylene composition and preparation method and application thereof |
| CN103169205B (en) * | 2012-06-27 | 2016-01-20 | 福建浔兴拉链科技股份有限公司 | A kind of zipper tooth and adopt the slide fastener of this zipper tooth |
| CN103859708B (en) * | 2012-12-10 | 2016-02-03 | 浙江伟星实业发展股份有限公司 | A kind of injection molding zipper and production technology thereof |
| CN103059502B (en) * | 2013-01-06 | 2015-03-18 | 上海秋橙新材料科技有限公司 | Antibacterial POM plastic |
| WO2016067400A1 (en) * | 2014-10-29 | 2016-05-06 | Ykk株式会社 | Fastener element and fastener element manufacturing method |
| CN106317759A (en) * | 2016-08-30 | 2017-01-11 | 道晟拉链科技（太仓）有限公司 | Antibacterial resin zipper |
| CN106360888A (en) * | 2016-08-30 | 2017-02-01 | 道晟拉链科技（太仓）有限公司 | Zipper having health care function |
| JP6846196B2 (en) * | 2016-12-27 | 2021-03-24 | Ykk株式会社 | Fastener tape and fastener stringer |
| CN107337896B (en) * | 2017-08-14 | 2019-10-18 | 浙江伟星实业发展股份有限公司 | A kind of modified injection molding zipper and its production technology |
| CN108912589A (en) * | 2018-05-31 | 2018-11-30 | 苏州乔纳森新材料科技有限公司 | A kind of preparation method of medical impact resistant plastics |
| CN210672308U (en) * | 2019-09-27 | 2020-06-05 | 福建浔兴拉链科技股份有限公司 | Zipper tooth and zipper using same |
| CN110819063B (en) * | 2019-10-22 | 2022-09-23 | 华合新材料科技股份有限公司 | High-performance antibacterial spraying-free POM composite material and preparation method thereof |
| CN111070733A (en) * | 2019-12-17 | 2020-04-28 | 安徽奇艺新材塑胶有限公司 | Processing method for weaving fiber tows into ultrathin braided fabric |
| CN111134423A (en) * | 2020-01-13 | 2020-05-12 | 东莞市瑞翔新型材料科技有限公司 | Waterproof zipper with three-dimensional effect and manufacturing method thereof |
-
2020
- 2020-08-10 CN CN202010795299.XA patent/CN112107084B/en active Active
- 2020-10-09 WO PCT/CN2020/119905 patent/WO2022032836A1/en active Application Filing
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| CN112107084A (en) | 2020-12-22 |
| WO2022032836A1 (en) | 2022-02-17 |
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