WO2022032836A1 - Zipper tooth, method for preparing zipper tooth, and zipper having zipper tooth - Google Patents

Zipper tooth, method for preparing zipper tooth, and zipper having zipper tooth Download PDF

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Publication number
WO2022032836A1
WO2022032836A1 PCT/CN2020/119905 CN2020119905W WO2022032836A1 WO 2022032836 A1 WO2022032836 A1 WO 2022032836A1 CN 2020119905 W CN2020119905 W CN 2020119905W WO 2022032836 A1 WO2022032836 A1 WO 2022032836A1
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Prior art keywords
tooth
homopolyoxymethylene
zipper
fastener element
fastener
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PCT/CN2020/119905
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French (fr)
Chinese (zh)
Inventor
陈凌剑
朱松峰
张田
余培
武刚
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福建浔兴拉链科技股份有限公司
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Publication of WO2022032836A1 publication Critical patent/WO2022032836A1/en

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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
    • 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

Definitions

  • the present application relates to a fastener element, a method for preparing the fastener element, and a zipper having the fastener element, belonging to the field of fasteners.
  • Zippers are widely used in clothing, bags, shoes and other daily necessities. With the development of the clothing and luggage industry and the continuous improvement of people's living standards, people's requirements for the performance of zipper products are also getting higher and higher.
  • the zipper is generally exposed on the surface of clothing and bags, directly contacting external harmful bacteria and microorganisms, which brings health risks to those who use the zipper.
  • the antibacterial properties of the zippers used in medical surgical gowns and protective clothing are also getting higher and higher.
  • silver ions are used to coat the surface of zipper components to achieve bacteriostatic effect, but silver is easily oxidized and easily lost when the slider slides, so the antibacterial/bacteriostatic effect of zippers containing silver ion materials Not ideal.
  • the present application provides a fastener element, a method for preparing the fastener element, a slide fastener having the fastener element, and a product.
  • the fastener element includes a tooth head, a tooth neck and a tooth tail, and the tooth head, tooth neck and tooth tail are made of homopolyoxymethylene.
  • the molecular formula of the homopolyoxymethylene is in the molecular weight range of 10,000 to 20,000.
  • the melt flow rate of the homopolyoxymethylene used to make the fastener elements is in the range of 9-32 g/10min.
  • the surface roughness of the fastener element does not exceed 1.6um.
  • the antibacterial activity value of the fastener element is greater than 2.
  • the present application proposes a method for preparing the above-mentioned fastener elements, which includes the steps of melting, injection molding and pressure holding; in the melting step, the homopolyoxymethylene is heated so that the melt flow rate of the homopolyoxymethylene is 9-32 g. Within the range of /10min; in the injection molding step, the homopolyoxymethylene is injected from the injection molding machine into the injection mold; in the pressure maintaining step, the homopolyoxymethylene is injected into the injection mold compaction.
  • the temperature range of the injection molding machine is set to 180-215°C.
  • the water content of the homopolyoxymethylene prior to the melting step is lower than 0.1%.
  • the injection speed is in the range of 0.3-3 mm/min, and the injection pressure is in the range of 60-120 Mpa.
  • the present application also proposes a zipper including fastener elements, sliders and cloth tapes, wherein the fastener elements include a tooth head, a tooth neck and a tooth tail, and the tooth head, the tooth neck and the tooth tail are made of polyoxymethylene.
  • the fastener elements include a tooth head, a tooth neck and a tooth tail, and the tooth head, the tooth neck and the tooth tail are made of polyoxymethylene.
  • the slider is made of the homopolyoxymethylene.
  • the zipper further includes a top stop and a bottom stop, and the top stop and/or the bottom stop are made of the homopolyoxymethylene.
  • the cloth tape is made of the homopolyacetal fiber filaments.
  • the present application also provides an article comprising the above-mentioned zipper.
  • Figure 1 shows the structure of the intermeshing elements.
  • Figure 2 shows a single element structure
  • FIG. 3 shows the general structure of a slide fastener.
  • a fastener element 1 comprising a tooth head 11 , a tooth neck 12 and a tooth tail 13 , and the tooth head 11 , the tooth neck 12 and the tooth tail 13 are made of homopolyacetal .
  • the molecular formula of homopolyoxymethylene is Molecular weights range from 10,000 to 20,000.
  • the production process of homopolyoxymethylene usually includes: using formaldehyde solution as a raw material, generating ethyl hemi-aqueous formaldehyde solution with isooctyl alcohol, and then obtaining pure formaldehyde through dehydration refining and thermal cracking.
  • the pure formaldehyde is passed into an inert solution containing a cationic catalyst (such as boron trifluoride diethyl ether complex) to polymerize into homopolyformaldehyde.
  • a cationic catalyst such as boron trifluoride diethyl ether complex
  • the polymer material is separated by filtration and dried, it is end-capped by hydroxyl esterification with acetic anhydride to obtain thermally stable polyoxymethylene; then additives such as antioxidants are added, and the finished product is obtained by extrusion and granulation.
  • the molecular structure of polyoxymethylene Compared with other polymer materials, the molecular structure of polyoxymethylene has its particularity and excellent self-lubricating properties.
  • the homopolyoxymethylene used in this application has a more regular and normal molecular arrangement than the copolymerized polyoxymethylene of two monomers because of its single monomer molecular unit. Therefore, the crystallinity of homopolyoxymethylene is higher, for example, more than 50%, and its material structure is more dense and uniform. This makes it difficult for bacteria and microorganisms to attach and absorb the nutrients they need to reproduce.
  • the chain elements made of homopolyacetal material also have excellent antibacterial properties, and the antibacterial effect is lasting.
  • the surface roughness of the fastener element does not exceed 1.6um.
  • the surface roughness of fastener elements generally refers to the arithmetic mean deviation of the surface roughness profile from the peak to the trough, that is, the arithmetic mean of the absolute value of the profile deviation within the sampling length.
  • the antibacterial activity value of the fastener elements is greater than 2.
  • the melt flow rate of the homopolyoxymethylene used in the fastener element proposed in the present application is in the range of 9-32 g/10min. Further preferably, the melt flow rate of the homopolyoxymethylene is in the range of 15-32 g/10min.
  • injection molding refers to a process in which 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 fastener element proposed in the present application can be made by the following injection molding process, and the process mainly includes the steps of melting, injection molding and pressure holding.
  • the processing temperature and the corresponding allowable residence time of POM in the screw barrel of the injection molding machine can be: when the temperature is 200°C, the time is within 60 minutes; or, when the temperature is 210°C , the time is within 30 minutes; or, when the temperature is 220°C, the time is within 15 minutes; or, when the temperature is 230°C, the time is within 10 minutes.
  • the homopolyoxymethylene material has a moisture content below 0.1% prior to initiation of the melting step.
  • the moisture content is higher than 0.1%, the material can be dried, and the drying conditions are 80-90°C/3-4 hours.
  • the homopolyoxymethylene is injected from an injection molding machine into an injection mold.
  • the temperature of the injection machine can be set to 180-215°C.
  • the temperature settings from the side of the hopper seat of the injection molding machine to the side of the nozzle are: 180-195°C, 195-205°C, 205-215°C, and 195-210°C.
  • the rotational speed of the screw in the injection machine is in the range of 100-150 rpm, 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 60-120Mpa.
  • the homopolyoxymethylene is compacted in the injection mold.
  • the range of the holding pressure is 60-100 Mpa, and the range of the holding time is 1-3s.
  • the temperature range of the injection mold can be set to 35-85°C.
  • the switching point from the injection process to the packing process is when the cavity is 80-95% full.
  • the fastener element it is preferable to process homopolyoxymethylene to make fastener elements, and develop a matching fastener element forming process for this material, so as to obtain fastener elements with dense and uniform molecular structure and dense and smooth texture.
  • Microorganisms and bacteria are difficult to adhere to the surface of the fastener element, and cannot absorb the nutrients required for their own reproduction on the surface of the fastener element, so the fastener element has an excellent antibacterial effect.
  • the homopolyoxymethylene itself is relatively stable in nature, and it is not easy to react with other substances, that is, it is not easy to lose itself, so the antibacterial effect of the fastener elements can be exerted for a long time.
  • the present application also proposes a slide fastener, which includes a slider 2, a cloth tape 3 and a fastener element 1 made of homopolyacetal.
  • a slide fastener which includes a slider 2, a cloth tape 3 and a fastener element 1 made of homopolyacetal.
  • at least a portion of the zipper puller is made of homopolyacetal.
  • the zipper further includes a top stop 4 and a bottom stop 5, and the top stop 4 and/or the bottom stop 5 are made of polyoxymethylene.
  • the cloth tape 3 is made of homopolyacetal fiber filaments.
  • the present application also provides an article comprising the above-mentioned zipper.
  • the testing method is strictly in accordance with the relevant testing standards, such as the conditions and testing requirements specified in ISO: 22196-2011 or GB/T31402-2015 (the standard name is "Test Method for Antibacterial Properties of Plastic Surfaces”), including:
  • strains are inoculated on appropriate medium, stored at 5-10°C, and transferred once a month;
  • a sterile inoculating loop transfer a loop of pre-cultured bacteria to a small amount of 1/500NB. Make sure that the bacteria are evenly dispersed, and measure the number of bacteria using microscope observation and counting plates or by other suitable methods (eg, spectrophotometry). Dilute the bacterial suspension with 1/500NB to make the bacterial concentration between 2.5 ⁇ 10 5 CFU/mL ⁇ 10 ⁇ 10 5 CFU/mL, and the optimal concentration is 6.0 ⁇ 10 5 CFU/mL, which is used as the inoculum. If the inoculum is not to be used immediately, place it on ice (0°C) and use within 2 hours.
  • the outer surface of the article is used as the test surface, and the cross-section of the article does not need to be tested.
  • the culture dish containing the inoculated samples (including 3 inoculated samples without antibacterial treatment products) was incubated at (35 ⁇ 1) °C and the relative humidity was not less than 90% for (24 ⁇ 1) h.
  • the antibacterial effect of the product is determined according to the antibacterial performance value obtained by testing at the incubation temperature.
  • control sample is a plastic film without antibacterial properties.
  • Sample pretreatment Wipe the surface of the sample with 70% alcohol, rinse with sterile water, and dry naturally.
  • the antibacterial activity values of the fastener elements proposed in this application are 3.8 and 2.8 respectively, which are obviously better than those of materials without antibacterial properties (ie, the control sample).

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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

A zipper tooth (1), a method for preparing the zipper tooth (1), and a zipper having the zipper tooth (1). The zipper tooth (1) comprises a tooth head (11), a tooth neck (12) and a tooth tail (13). The tooth head (11), the tooth neck (12) and the tooth tail (13) are made of a polyoxymethylene homopolymer. The method for preparing the zipper tooth (1) comprises a melting step, an injection molding step and a compaction step. In the melting step, a polyoxymethylene homopolymer is heated, such that a flow rate of the melted polyoxymethylene homopolymer is within a range of 9-32 g/10 min. In the injection molding step, the polyoxymethylene homopolymer is injected from an injection molding machine into an injection mold. In the compaction step, the polyoxymethylene homopolymer is compacted in the injection mold. The zipper tooth (1) prepared using the polyoxymethylene homopolymer has a dense and uniform molecular structure and improved antimicrobial effects.

Description

一种链牙、链牙制备方法及具有该链牙的拉链A kind of fastener element, method for preparing fastener element and slide fastener with the fastener element 技术领域technical field
本申请涉及一种链牙、链牙制备方法及具有该链牙的拉链，属于拉链领域。The present application relates to a fastener element, a method for preparing the fastener element, and a zipper having the fastener element, belonging to the field of fasteners.
背景技术Background technique
拉链广泛应用于服装、箱包、鞋等日用品中。随着服装、箱包行业的发展和人们生活水平不断提高，人们对于拉链产品性能的要求也越来越高。拉链一般暴露在服装、箱包表面，直接接触外部有害细菌和微生物，从而给使用拉链的人带来健康隐患。另外，医用手术服和防护服对其使用的拉链的抗菌性能要求也越来越高。目前，银离子被用于涂覆在拉链部件的表面以实现抑菌效果，但是银极易发生氧化，在拉头滑动时也容易发生损耗，因此含有银离子材料的拉链的抗菌/抑菌效果并不理想。Zippers are widely used in clothing, bags, shoes and other daily necessities. With the development of the clothing and luggage industry and the continuous improvement of people's living standards, people's requirements for the performance of zipper products are also getting higher and higher. The zipper is generally exposed on the surface of clothing and bags, directly contacting external harmful bacteria and microorganisms, which brings health risks to those who use the zipper. In addition, the antibacterial properties of the zippers used in medical surgical gowns and protective clothing are also getting higher and higher. At present, silver ions are used to coat the surface of zipper components to achieve bacteriostatic effect, but silver is easily oxidized and easily lost when the slider slides, so the antibacterial/bacteriostatic effect of zippers containing silver ion materials Not ideal.
发明内容SUMMARY OF THE INVENTION
本申请提出一种链牙、链牙制备方法、具有该链牙的拉链以及制品。该链牙包括牙头、牙颈和牙尾，所述牙头、牙颈和牙尾由均聚聚甲醛制成。优选地，所述均聚聚甲醛分子式为，分子量范围为10000至20000。或者优选地，用于制作链牙的所述均聚聚甲醛的熔流速率处于9-32g/10min范围内。或者优选地，所述链牙的表面粗糙度不超过1.6um。或者优选地，所述链牙的抗菌活性值大于2。The present application provides a fastener element, a method for preparing the fastener element, a slide fastener having the fastener element, and a product. The fastener element includes a tooth head, a tooth neck and a tooth tail, and the tooth head, tooth neck and tooth tail are made of homopolyoxymethylene. Preferably, the molecular formula of the homopolyoxymethylene is in the molecular weight range of 10,000 to 20,000. Or preferably, the melt flow rate of the homopolyoxymethylene used to make the fastener elements is in the range of 9-32 g/10min. Or preferably, the surface roughness of the fastener element does not exceed 1.6um. Or preferably, the antibacterial activity value of the fastener element is greater than 2.
本申请提出上述链牙的制备方法，包括熔融、注射成型和保压步骤；在所述熔融步骤中，加热所述均聚聚甲醛，使所述均聚聚甲醛的熔流速率处于9-32g/10min范围内；在所述注射成型步骤中，将所述均聚聚甲醛从注塑机注射到注塑模具中；在所述保压步骤中，将所述均聚聚甲醛在所述注塑模具中压实。优选地，在所述注射成型步骤中，所述注塑机的温度范围设置为180-215℃。 或者优选地，所述均聚聚甲醛在所述熔融步骤之前的含水率低于0.1％。或者优选地，在所述注射成型步骤中，注射速度范围为0.3-3mm/min，注射压力范围为60-120Mpa。The present application proposes a method for preparing the above-mentioned fastener elements, which includes the steps of melting, injection molding and pressure holding; in the melting step, the homopolyoxymethylene is heated so that the melt flow rate of the homopolyoxymethylene is 9-32 g. Within the range of /10min; in the injection molding step, the homopolyoxymethylene is injected from the injection molding machine into the injection mold; in the pressure maintaining step, the homopolyoxymethylene is injected into the injection mold compaction. Preferably, in the injection molding step, the temperature range of the injection molding machine is set to 180-215°C. Or preferably, the water content of the homopolyoxymethylene prior to the melting step is lower than 0.1%. Or preferably, in the injection molding step, the injection speed is in the range of 0.3-3 mm/min, and the injection pressure is in the range of 60-120 Mpa.
本申请还提出一种拉链，包括链牙、拉头和布带，所述链牙包括牙头、牙颈和牙尾，所述牙头、牙颈和牙尾由均聚聚甲醛制成。优选地，所述拉头的至少一部分由所述均聚聚甲醛制成。或者优选地，该拉链还包括上止和下止，所述上止和/或下止由所述均聚聚甲醛制成。或者优选地，所述布带由所述均聚聚甲醛纤维丝制成。The present application also proposes a zipper including fastener elements, sliders and cloth tapes, wherein the fastener elements include a tooth head, a tooth neck and a tooth tail, and the tooth head, the tooth neck and the tooth tail are made of polyoxymethylene. Preferably, at least a portion of the slider is made of the homopolyoxymethylene. Or preferably, the zipper further includes a top stop and a bottom stop, and the top stop and/or the bottom stop are made of the homopolyoxymethylene. Or preferably, the cloth tape is made of the homopolyacetal fiber filaments.
本申请还提出一种制品，包括上述拉链。The present application also provides an article comprising the above-mentioned zipper.
附图说明Description of drawings
此处所说明的附图用来提供对本申请的进一步理解，构成本申请的一部分，本申请的示意性实施例及其说明用于解释本申请，并不构成对本申请的不当限定。在附图中：The drawings described herein are used to provide further understanding of the present application and constitute a part of the present application. The schematic embodiments and descriptions of the present application are used to explain the present application and do not constitute an improper limitation of the present application. In the attached image:
图1示出相互啮合的链牙结构。Figure 1 shows the structure of the intermeshing elements.
图2示出单个链牙结构。Figure 2 shows a single element structure.
图3示出拉链的一般结构。FIG. 3 shows the general structure of a slide fastener.
附图中，各附图标记所代表的部件名称如下所示：In the accompanying drawings, the names of the components represented by the reference numerals are as follows:
1、链牙，11、牙头，12、牙颈，13、牙尾，2、布带，3、拉头，4、上止，5、下止。1. Chain element, 11, tooth head, 12, tooth neck, 13, tooth tail, 2, cloth belt, 3, slider, 4, top stop, 5, bottom stop.
具体实施方式detailed description
为了使本申请实施例中的技术方案及优点更加清楚明白，以下结合附图对本申请的示例性实施例进行进一步详细的说明，显然，所描述的实施例仅是本申请的一部分实施例，而不是所有实施例的穷举。需要说明的是，在不冲突的情况下，本申请中的实施例及实施例中的特征可以相互组合。In order to make the technical solutions and advantages of the embodiments of the present application clearer, the exemplary embodiments of the present application will be described in further detail below with reference to the accompanying drawings. Obviously, the described embodiments are only a part of the embodiments of the present application, and Not all embodiments are exhaustive. It should be noted that the embodiments in the present application and the features of the embodiments may be combined with each other in the case of no conflict.
如图1至3所示，本申请提出一种链牙1，包括牙头11、牙颈12和牙尾 13，所述牙头11、牙颈12和牙尾13由均聚聚甲醛制成。As shown in FIGS. 1 to 3 , the present application proposes a fastener element 1 , comprising a tooth head 11 , a tooth neck 12 and a tooth tail 13 , and the tooth head 11 , the tooth neck 12 and the tooth tail 13 are made of homopolyacetal .
在一个实施例中，均聚聚甲醛分子式为
Figure PCTCN2020119905-appb-000001
分子量范围为10000至20000。 In one embodiment, the molecular formula of homopolyoxymethylene is
Figure PCTCN2020119905-appb-000001
Molecular weights range from 10,000 to 20,000.
在所属技术领域中，均聚聚甲醛的生产流程通常包括：以甲醛溶液为原料，经与异辛醇生成乙基半水甲醛溶液，再经脱水精制、热裂解得到纯甲醛。将纯甲醛通入含有阳离子型催化剂(如三氟化硼***络合物)的惰性溶液中聚合成均聚甲醛。聚合料经过滤分离、干燥后，用醋酐进行羟基酯化封端，得到热稳定的聚甲醛；然后加入抗氧剂等助剂，通过挤出造粒制得成品。In the technical field, the production process of homopolyoxymethylene usually includes: using formaldehyde solution as a raw material, generating ethyl hemi-aqueous formaldehyde solution with isooctyl alcohol, and then obtaining pure formaldehyde through dehydration refining and thermal cracking. The pure formaldehyde is passed into an inert solution containing a cationic catalyst (such as boron trifluoride diethyl ether complex) to polymerize into homopolyformaldehyde. After the polymer material is separated by filtration and dried, it is end-capped by hydroxyl esterification with acetic anhydride to obtain thermally stable polyoxymethylene; then additives such as antioxidants are added, and the finished product is obtained by extrusion and granulation.
聚甲醛分子结构与其他高分子材料相比具有其特殊性，自润滑性能优良。本申请利用的均聚聚甲醛因其单一的单体分子单元，比双单体的共聚聚甲醛分子排布更为规整和归一。因此，均聚聚甲醛的结晶度更高，例如超过50％，其材料组织更为致密和均匀。细菌和微生物因而难以附着，也无法吸取其自身繁殖所需的营养。采用均聚聚甲醛材料制成的链牙也因此具有优良的抗菌性能，且抗菌效果持久。Compared with other polymer materials, the molecular structure of polyoxymethylene has its particularity and excellent self-lubricating properties. The homopolyoxymethylene used in this application has a more regular and normal molecular arrangement than the copolymerized polyoxymethylene of two monomers because of its single monomer molecular unit. Therefore, the crystallinity of homopolyoxymethylene is higher, for example, more than 50%, and its material structure is more dense and uniform. This makes it difficult for bacteria and microorganisms to attach and absorb the nutrients they need to reproduce. The chain elements made of homopolyacetal material also have excellent antibacterial properties, and the antibacterial effect is lasting.
在另一个实施例中，所述链牙的表面粗糙度不超过1.6um。在拉链技术领域中，链牙的表面粗糙度一般是指表面粗糙度轮廓波峰到波谷的算术平均偏差，即在取样长度内轮廓偏距绝对值的算术平均值。In another embodiment, the surface roughness of the fastener element does not exceed 1.6um. In the field of zipper technology, the surface roughness of fastener elements generally refers to the arithmetic mean deviation of the surface roughness profile from the peak to the trough, that is, the arithmetic mean of the absolute value of the profile deviation within the sampling length.
在又一个实施例中，链牙的抗菌活性值大于2。In yet another embodiment, the antibacterial activity value of the fastener elements is greater than 2.
在一个优选的实施例中，本申请提出的链牙所采用的均聚聚甲醛的熔流速率在9-32g/10min范围内。进一步优选的，均聚聚甲醛的熔流速率在15-32g/10min范围内。利用熔流速率处于上述范围内的均聚聚甲醛材料，能够制成分子结构致密且均匀、抗菌性能优良且稳定的链牙。In a preferred embodiment, the melt flow rate of the homopolyoxymethylene used in the fastener element proposed in the present application is in the range of 9-32 g/10min. Further preferably, the melt flow rate of the homopolyoxymethylene is in the range of 15-32 g/10min. Using the homopolyacetal material with the melt flow rate in the above range, the fastener element with dense and uniform molecular structure, excellent antibacterial performance and stability can be made.
本申请提出的链牙是通过注塑加工成型工艺来制成。注塑加工成型是指在一定温度下，熔融的塑料材料被高压射入模腔，经冷却固化后得到成型品的工艺。The fastener elements proposed in the present application are made by injection molding. Injection molding refers to a process in which 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.
本申请提出的链牙可以通过以下注塑加工成型工艺制成，工艺主要包括熔 融、注射成型和保压步骤。The fastener element proposed in the present application can be made by the following injection molding process, and the process mainly includes the steps of melting, injection molding and pressure holding.
在熔融步骤中，加热均聚聚甲醛，使其熔流速率处于9-32g/10min范围内。在一个优选的实施例中，均聚聚甲醛在注塑机螺杆料筒内的处理温度及对应的允许滞留时间可以为：温度为200℃时，时间在60分钟以内；或者，温度为210℃时，时间在30分钟以内；或者，温度为220℃时，时间在15分钟以内；或者，温度为230℃时，时间在10分钟以内。In the melting step, the homopolyoxymethylene is heated so that its melt flow rate is in the range of 9-32 g/10min. In a preferred embodiment, the processing temperature and the corresponding allowable residence time of POM in the screw barrel of the injection molding machine can be: when the temperature is 200°C, the time is within 60 minutes; or, when the temperature is 210°C , the time is within 30 minutes; or, when the temperature is 220°C, the time is within 15 minutes; or, when the temperature is 230°C, the time is within 10 minutes.
优选地，在熔融步骤启动之前，均聚聚甲醛材料的含水率低于0.1％。当含水率高于0.1％时，可对材料进行干燥处理，干燥条件为80-90℃/3-4小时。Preferably, the homopolyoxymethylene material has a moisture content below 0.1% prior to initiation of the melting step. When the moisture content is higher than 0.1%, the material can be dried, and the drying conditions are 80-90°C/3-4 hours.
在注射成型步骤中，将所述均聚聚甲醛从注塑机注射到注塑模具中。优选地，注射机的温度可设置为180-215℃。进一步优选地，从注塑机料斗座侧到射嘴侧的温度设置依次为：180-195℃，195-205℃，205-215℃，195-210℃。In the injection molding step, the homopolyoxymethylene is injected from an injection molding machine into an injection mold. Preferably, the temperature of the injection machine can be set to 180-215°C. Further preferably, the temperature settings from the side of the hopper seat of the injection molding machine to the side of the nozzle are: 180-195°C, 195-205°C, 205-215°C, and 195-210°C.
在另一个优选的实施例中，注射机内螺杆的转速范围为100-150rpm，背压范围为0.5-3Mpa。进一步地，注射速度范围为0.3-3mm/min，注射压力范围为60-120Mpa。In another preferred embodiment, the rotational speed of the screw in the injection machine is in the range of 100-150 rpm, 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 60-120Mpa.
在所述保压步骤中，将所述均聚聚甲醛在所述注塑模具中压实。在一个实施例中，保压压力范围为60-100Mpa，保压时间范围为1-3s。注塑模具的温度范围可以设置为35-85℃。由注射过程切换到保压过程的切换点为当模腔的80-95％被填充满时。In the pressure-holding step, the homopolyoxymethylene is compacted in the injection mold. In one embodiment, the range of the holding pressure is 60-100 Mpa, and the range of the holding time is 1-3s. The temperature range of the injection mold can be set to 35-85°C. The switching point from the injection process to the packing process is when the cavity is 80-95% full.
本申请优选均聚聚甲醛加工制作链牙，并针对该材料开发配套的链牙成型加工工艺，得到分子结构致密且均匀、自身质地密实且光滑的链牙。微生物与细菌难以附着在该链牙表面，也无法在链牙表面吸取其自身繁殖所需的营养，因此该链牙具有优良的抗菌效果。另外，均聚聚甲醛本身性质较为稳定，不易与其他物质发生反应，即自身不易发生损耗，链牙的抗菌效果因而得以持久发挥。In the present application, it is preferable to process homopolyoxymethylene to make fastener elements, and develop a matching fastener element forming process for this material, so as to obtain fastener elements with dense and uniform molecular structure and dense and smooth texture. Microorganisms and bacteria are difficult to adhere to the surface of the fastener element, and cannot absorb the nutrients required for their own reproduction on the surface of the fastener element, so the fastener element has an excellent antibacterial effect. In addition, the homopolyoxymethylene itself is relatively stable in nature, and it is not easy to react with other substances, that is, it is not easy to lose itself, so the antibacterial effect of the fastener elements can be exerted for a long time.
本申请还提出一种拉链，包括拉头2、布带3以及由均聚聚甲醛制成的链牙1。在一个实施例中，拉链拉头的至少一部分由均聚聚甲醛制成。在另一个 实施例中，拉链还包括上止4和下止5，上止4和/或下止5由均聚聚甲醛制成。进一步优选的，布带3由均聚聚甲醛纤维丝制成。The present application also proposes a slide fastener, which includes a slider 2, a cloth tape 3 and a fastener element 1 made of homopolyacetal. In one embodiment, at least a portion of the zipper puller is made of homopolyacetal. In another embodiment, the zipper further includes a top stop 4 and a bottom stop 5, and the top stop 4 and/or the bottom stop 5 are made of polyoxymethylene. Further preferably, the cloth tape 3 is made of homopolyacetal fiber filaments.
本申请还提出一种制品，包括上述拉链。The present application also provides an article comprising the above-mentioned zipper.
下面就本申请提出的链牙抗菌效果的检测方法和检测结果进行说明。The detection method and detection result of the antibacterial effect of the fastener element proposed in the present application will be described below.
检测方法严格按照相关检测标准，如ISO：22196-2011或GB/T31402-2015(标准名称为《塑料表面抗菌性能试验方法》)中规定的条件与检测要求，具体包括：The testing method is strictly in accordance with the relevant testing standards, such as the conditions and testing requirements specified in ISO: 22196-2011 or GB/T31402-2015 (the standard name is "Test Method for Antibacterial Properties of Plastic Surfaces"), including:
(1)相关材料——一定浓度的金黄色葡萄球菌与大肠杆菌，试剂、培养基与溶液，仪器(干热灭菌箱、培养箱、移液器、搅拌器、超音波清洗器、接种环、覆盖膜、培养皿、纱布、脱脂棉、容量瓶等等)；(1) Related materials - Staphylococcus aureus and Escherichia coli with a certain concentration, reagents, culture medium and solution, instruments (dry heat sterilization box, incubator, pipette, stirrer, ultrasonic cleaner, inoculation loop , cover film, petri dish, gauze, absorbent cotton, volumetric flask, etc.);
(2)干热灭菌条件：180℃，30分钟；(2) Dry heat sterilization conditions: 180°C, 30 minutes;
(3)菌种的接种与保藏条件：菌种接种于适当的培养基上，存放在5-10℃的条件下，每月转种一次；(3) Inoculation and storage conditions of strains: strains are inoculated on appropriate medium, stored at 5-10°C, and transferred once a month;
(4)细菌预培养(4) Bacterial pre-culture
用无菌接种环将细菌从保藏菌种的培养基上转移到斜面培养基上并在(35±1)℃培养16h～24h。再用无菌接种环将此细菌转移至新鲜的斜面培养基上，在(35±1)℃培养16h～20h。Use a sterile inoculating loop to transfer bacteria from the culture medium to the slant medium and culture at (35±1)°C for 16h to 24h. Then transfer the bacteria to fresh slant medium with a sterile inoculating loop, and cultivate at (35±1)℃ for 16h～20h.
(5)试样的制备(5) Preparation of samples
经过抗菌处理的材料至少准备3片试样，未经抗菌处理的材料至少准备6片试样。3片未经抗菌处理试样用于接种后立即测量活的细菌数，另3片用于测量接种后24h的活细菌数。Prepare at least 3 samples for materials that have undergone antibacterial treatment, and prepare at least 6 samples for materials without antibacterial treatment. Three samples without antibacterial treatment were used to measure the number of live bacteria immediately after inoculation, and the other three samples were used to measure the number of live bacteria 24h after inoculation.
(6)接种液的制备(6) Preparation of inoculum
使用无菌的接种环，转移一环预培养好的细菌到少量的1/500NB中。确保细菌分散均匀，并采用显微镜观测及计数板或利用其他合适的方法(如分光光度计法)测定细菌数量。用1/500NB稀释菌悬液，使细菌的浓度在2.5×10 5CFU/mL～10×10 5CFU/mL之间，最佳浓度为6.0X10 5CFU/mL，用作接种液。 如果接种液不立即使用，将其放置于冰块上(0℃)并在2小时内使用。 Using a sterile inoculating loop, transfer a loop of pre-cultured bacteria to a small amount of 1/500NB. Make sure that the bacteria are evenly dispersed, and measure the number of bacteria using microscope observation and counting plates or by other suitable methods (eg, spectrophotometry). Dilute the bacterial suspension with 1/500NB to make the bacterial concentration between 2.5×10 5 CFU/mL～10×10 5 CFU/mL, and the optimal concentration is 6.0×10 5 CFU/mL, which is used as the inoculum. If the inoculum is not to be used immediately, place it on ice (0°C) and use within 2 hours.
(7)试样接种(7) Sample inoculation
制品的外表面作为测试表面，制品的横切面不需要测试。将试样分别放入无菌的培养皿中，测试面朝上。用移液管吸取0.4mL接种液，滴到每个试样表面。并将制备好的40mmX40mm的薄膜覆盖于接种好的菌液上，并向下轻轻按压薄膜，使菌液向四周扩散，确保菌液不会从薄膜边缘溢出，在试样接种完并盖上薄膜后，盖上培养皿盖。The outer surface of the article is used as the test surface, and the cross-section of the article does not need to be tested. Place the specimens individually into sterile petri dishes with the test side facing up. Pipette 0.4mL of the inoculum and drop it onto the surface of each sample. Cover the prepared 40mmX40mm film on the inoculated bacterial liquid, and gently press the film downward to spread the bacterial liquid around to ensure that the bacterial liquid does not overflow from the edge of the film. After the sample is inoculated and covered After filming, cover the petri dish.
(8)接种试样的培养条件(8) Culture conditions for inoculated samples
含有接种试样(包括3片未经抗菌处理制品的接种试样)的培养皿，在(35±1)℃、相对湿度不小于90％的条件下培养(24±1)h。根据在培养温度下检测所得到的抗菌性能值来确定制品的抗菌效果。The culture dish containing the inoculated samples (including 3 inoculated samples without antibacterial treatment products) was incubated at (35 ± 1) ℃ and the relative humidity was not less than 90% for (24 ± 1) h. The antibacterial effect of the product is determined according to the antibacterial performance value obtained by testing at the incubation temperature.
本申请提出的链牙经检测，得出以下检测结果：The fasteners proposed in this application have been tested, and the following test results have been obtained:
检测菌种Detection of bacteria 大肠杆菌ATCC 8739Escherichia coli ATCC 8739 金黄色葡萄球菌ATCC 6538Staphylococcus aureus ATCC 6538
接种菌液浓度(CFU/mL)Inoculum concentration (CFU/mL) 1.2x10＾61.2x10＾6 6.4x10＾56.4x10＾5
接种菌液量(mL)Inoculum volume (mL) 0.20.2 0.20.2
U0U0 4.144.14 3.893.89
UtUt 4.694.69 5.515.51
AtAt 0.910.91 2.762.76
抗菌活性值RAntibacterial activity value R 3.83.8 2.82.8
备注：1.对照样为无抗菌性能塑料膜。Remarks: 1. The control sample is a plastic film without antibacterial properties.
2.U0：对照样在0h接触时间洗脱后获得的细菌数(CFU/cm 2)的对数值。 2. U0: the logarithmic value of the bacterial count (CFU/cm 2 ) obtained after the control sample was eluted at a contact time of 0 h.
3.Ut：对照样在24h接触时间洗脱后获得的细菌数(CFU/cm 2)的对数值。 3. Ut: the logarithm of the number of bacteria (CFU/cm 2 ) obtained after elution of the control sample at a contact time of 24 h.
4.At：样品在24h接触时间洗脱后获得的细菌数(CFU/cm 2)的对数值。 4. At: logarithm of the number of bacteria (CFU/cm 2 ) obtained for the sample after elution at a 24h contact time.
5.R：抗菌活性值，R＝Ut-At。5. R: Antibacterial activity value, R=Ut-At.
6.样品前处理：用70％酒精擦拭样品表面，无菌水冲洗，自然晾干。6. Sample pretreatment: Wipe the surface of the sample with 70% alcohol, rinse with sterile water, and dry naturally.
根据检测结果发现，本申请提出的链牙的抗菌活性值分别为3.8和2.8，明显优于无抗菌性能材料(即对照样)。According to the test results, it is found that the antibacterial activity values of the fastener elements proposed in this application are 3.8 and 2.8 respectively, which are obviously better than those of materials without antibacterial properties (ie, the control sample).
尽管已描述了本申请一些可选的实施例，但本领域内的技术人员一旦得知了基本创造性概念，则可对这些实施例作出另外的变更和修改。所以，所附权利要求意欲解释为包括一些可选的实施例以及落入本申请范围的所有变更和修改。While a few alternative embodiments of the present application have been described, additional changes and modifications to these embodiments may occur to those skilled in the art once the basic inventive concepts are known. Therefore, the appended claims are intended to be construed to include alternative embodiments and all changes and modifications that fall within the scope of the present application.
显然，本领域的技术人员可以对本申请进行各种改动和变型而不脱离本申请的精神和范围。这样，倘若本申请的这些修改和变型属于本申请权利要求及其等同技术的范围之内，则本申请也意图包含这些改动和变型在内。Obviously, those skilled in the art can make various changes and modifications to the present application without departing from the spirit and scope of the present application. Thus, if these modifications and variations of the present application fall within the scope of the claims of the present application and their equivalents, the present application is also intended to include these modifications and variations.

Claims (14)

  1. 一种链牙，其特征在于，包括牙头、牙颈和牙尾，所述牙头、牙颈和牙尾由均聚聚甲醛制成。A fastener is characterized in that it comprises a tooth head, a tooth neck and a tooth tail, and the tooth head, tooth neck and tooth tail are made of homopolyoxymethylene.
  2. 根据权利要求1所述的链牙，其特征在于，所述均聚聚甲醛分子式为
    Figure PCTCN2020119905-appb-100001
    分子量范围为10000至20000。     The fastener element according to claim 1, wherein the molecular formula of the homopolyoxymethylene is:
    Figure PCTCN2020119905-appb-100001
    Molecular weights range from 10,000 to 20,000.
  3. 根据权利要求1所述的链牙，其特征在于，用于制作链牙的所述均聚聚甲醛的熔流速率处于9-32g/10min范围内。The fastener element according to claim 1, characterized in that, the melt flow rate of the homopolyoxymethylene used to make the fastener element is in the range of 9-32 g/10min.
  4. 根据权利要求1所述的链牙，其特征在于，所述链牙的表面粗糙度不超过1.6um。The fastener element according to claim 1, wherein the surface roughness of the fastener element is not more than 1.6um.
  5. 根据权利要求1所述的链牙，其特征在于，所述链牙的抗菌活性值大于2。The fastener element according to claim 1, wherein the antibacterial activity value of the fastener element is greater than 2.
  6. 一种如权利要求1至5任一项所述链牙的制备方法，包括熔融、注射成型和保压步骤；A method for preparing a fastener element as claimed in any one of claims 1 to 5, comprising the steps of melting, injection molding and pressure-holding;
    在所述熔融步骤中，加热所述均聚聚甲醛，使所述均聚聚甲醛的熔流速率处于9-32g/10min范围内；In the melting step, heating the homopolyoxymethylene, so that the melt flow rate of the homopolyoxymethylene is in the range of 9-32g/10min;
    在所述注射成型步骤中，将所述均聚聚甲醛从注塑机注射到注塑模具中；In the injection molding step, the homopolyoxymethylene is injected from an injection molding machine into an injection mold;
    在所述保压步骤中，将所述均聚聚甲醛在所述注塑模具中压实。In the pressure-holding step, the homopolyoxymethylene is compacted in the injection mold.
  7. 根据权利要求6所述链牙的制备方法，其特征在于，在所述注射成型步骤中，所述注塑机的温度范围设置为180-215℃。The method for preparing a fastener element according to claim 6, wherein in the injection molding step, the temperature range of the injection molding machine is set to 180-215°C.
  8. 根据权利要求6所述链牙的制备方法，其特征在于，所述均聚聚甲醛在所述熔融步骤之前的含水率低于0.1％。The method for preparing a fastener element according to claim 6, wherein the water content of the homopolyoxymethylene before the melting step is lower than 0.1%.
  9. 根据权利要求6所述链牙的制备方法，其特征在于，在所述注射成型步 骤中，注射速度范围为0.3-3mm/min，注射压力范围为60-120Mpa。The method for preparing a fastener element according to claim 6, characterized in that, in the injection molding step, the injection speed is in the range of 0.3-3mm/min, and the injection pressure is in the range of 60-120Mpa.
  10. 一种拉链，包括链牙、拉头和布带，所述链牙为权利要求1-5任一项所述的链牙。A zipper includes fastener elements, sliders and cloth tapes, wherein the fastener elements are the fastener elements described in any one of claims 1-5.
  11. 根据权利要求10所述的拉链，其特征在于，所述拉头的至少一部分由所述均聚聚甲醛制成。The slide fastener of claim 10, wherein at least a portion of the slider is made of the homopolyoxymethylene.
  12. 根据权利要求10所述的拉链，还包括上止和下止，所述上止和/或下止由所述均聚聚甲醛制成。The zipper according to claim 10, further comprising a top stop and a bottom stop, the top stop and/or the bottom stop being made of the homopolyoxymethylene.
  13. 根据权利要求10所述的拉链，所述布带由所述均聚聚甲醛纤维丝制成。The zipper according to claim 10, wherein the cloth tape is made of the homopolyacetal fiber filaments.
  14. 一种制品，包括如权利要求10-13任一项所述的拉链。An article comprising the zipper of any one of claims 10-13.
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