Resin-based material for zipper teeth, preparation method of resin-based material, zipper and preparation method of zipper

Abstract

The invention provides a resin-based material for zipper teeth, a preparation method of the resin-based material, a zipper and a preparation method of the zipper. The preparation method of the resin-based material for the zipper teeth, provided by the invention, comprises the following steps: mixing a main body raw material, an antioxidant and a lubricant to obtain a mixture; carrying out melt extrusion and granulation on the mixture to obtain a resin-based material; wherein the main raw material comprises the following components in percentage by mass: 45-70% of aromatic polyamide resin; and the balance of reinforced glass fiber filaments. Wherein the average diameter of the reinforced glass fiber filaments is 1-14 [mu] m; the use amount of the antioxidant is 0-1% of the mass of the main body raw material and is not 0%; the use amount of the lubricant is 0-1% of the mass of the main body raw material and is not 0%. The resin-based material provided by the invention can effectively improve the horizontal pulling strength of the zipper, and meets the fluoride-free requirement at the same time.

Description

Technical Field

[0001] The invention relates to the field of clothing accessories, and in particular to a resin-based material for zipper teeth and a preparation method thereof, a zipper and a preparation method thereof. Background Art

[0002] As a type of zipper, resin zipper is mainly made by installing polymer resin on a cloth belt woven from several polyester yarns through high-temperature melt injection molding, and then assembling upper and lower limiters and chain parts. It has the characteristics of light weight, good smoothness, and high longitudinal tensile strength. It is widely used in the placket and pocket areas of clothing, as well as light down jackets and skin clothing.

[0003] With the improvement of living standards, people pay more attention to the lightweight of clothing. The requirements for plastic-steel zippers for clothing, luggage and other products have increased significantly. Not only are plastic-steel zippers required to be more environmentally friendly and meet the requirements of environmentally friendly and non-toxic clothing, but they must also meet the requirements of higher lateral tensile strength and wear resistance on the basis of environmental protection.

[0004] At present, the load strength of existing plastic-steel zippers cannot meet the requirements of outdoor and military workwear, and the lateral tensile strength of the zipper teeth cannot meet the requirements, especially the plastic-steel zippers made by ordinary polyoxymethylene resin injection molding, which have low lateral tensile strength, resulting in the separation of the zipper teeth on both sides or even the zipper teeth on one side falling off during use. In addition, the total fluorine (PFAS) content of some zipper injection molding materials currently used cannot meet the requirements of international environmental protection standards, especially MXD6 (CN106061311B) in polyamide and its reinforcing fiber, whose total fluorine (PFAS) content exceeds the 50ppm required by international environmental protection standards. Summary of the invention

[0005] In view of this, the present invention provides a resin-based material for zipper teeth and a preparation method thereof, a zipper and a preparation method thereof. The resin-based material provided by the present invention can effectively improve the flat pulling strength of the zipper and meet the fluorine-free requirement at the same time.

[0006] The present invention provides a method for preparing a resin-based material for zipper teeth, comprising the following steps:

[0007] The main raw material, the antioxidant and the lubricant are mixed to obtain a mixture; the mixture is melt-extruded and granulated to obtain a resin-based material;

[0008] in,

[0009] In terms of mass percentage, the main raw materials include:

[0010] Aramid polyamide resin 45% to 70%;

[0011] Reinforcement glass fiber filament surplus;

[0012] Wherein, the average diameter of the reinforced glass fiber filaments is 1 to 14 μm;

[0013] The amount of the antioxidant is 0% to 1% of the mass of the main raw material, and is not 0%;

[0014] The amount of the lubricant is 0% to 1% of the mass of the main raw material, and is not 0%.

[0015] Preferably, the aromatic polyamide resin is a fluorine-free and environmentally friendly resin PARA;

[0016] The reinforcing glass fiber yarn is E glass fiber yarn.

[0017] Preferably, the aromatic polyamide resin is Solvay PARA-1622 and / or Solvay PARA-9048.

[0018] Preferably, the reinforcing glass fiber yarn is Boya Composites ECR high-performance glass fiber yarn.

[0019] Preferably, the antioxidant is preferably BASF1098 antioxidant;

[0020] The lubricant is Ceralene-CP45M lubricant.

[0021] Preferably, the melting temperature is 250-280°C.

[0022] The present invention also provides a resin-based material for zipper teeth obtained by the preparation method described in the above technical solution.

[0023] The present invention also provides a method for preparing a zipper, comprising: heating a raw material for injection molding on a zipper injection molding machine equipped with a resin zipper mold, and injection molding teeth on a corresponding resin zipper tape to obtain a zipper;

[0024] Wherein, the raw material is the resin-based material for zipper teeth described in the above technical solution.

[0025] Preferably, the temperature of the injection molding machine is set to 250-280° C., and the pressure of the injection molding machine is set to 45-50 MPa.

[0026] The present invention also provides a zipper made by the preparation method described in the above technical solution.

[0027] In order to achieve the high strength and low fluorine / fluorine-free requirements of resin zippers, the present invention provides a new fluorine-free high-strength resin zipper, which adopts a specific new high-performance aromatic polyamide, utilizes specific fluorine-free glass fiber filament reinforcement as the injection molding raw material of plastic-steel zipper teeth, and is matched with certain antioxidants and lubricants, adjusts the injection molding resin tooth raw material formula, and controls the zipper tooth injection molding parameters and zipper tape parameters, so as to achieve the improvement of the plastic-steel zipper in terms of high strength, fluorine and environmental protection, make up for the shortcomings of the plastic-steel zipper in special application scenarios, and meet the environmental protection requirements at the same time. DETAILED DESCRIPTION

[0028] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art to which this application belongs. The terms used herein in the specification of this application are only for the purpose of describing specific embodiments and are not intended to limit this application.

[0029] In this article, the technical features described in an open manner include closed technical solutions composed of the listed features, and also include open technical solutions containing the listed features.

[0030] As used herein, the term "and / or" includes any and all combinations of one or more of the associated listed items.

[0031] Herein, when it comes to numerical ranges, unless otherwise specified, the numerical ranges are deemed to be continuous and include the minimum and maximum values ​​of the range, as well as every value between such minimum and maximum values. Further, when a range refers to an integer, every integer between the minimum and maximum values ​​of the range is included. In addition, when multiple ranges are provided to describe features or characteristics, the ranges can be merged. In other words, unless otherwise specified, all ranges disclosed herein should be understood to include any and all subranges included therein.

[0032] In this article, when referring to the unit of a data range, if there is a unit only after the right endpoint, it means that the units of the left and right endpoints are the same. For example, 1-14 μm means that the units of the left endpoint "1" and the right endpoint "14" are both μm.

[0033] The present invention provides a method for preparing a resin-based material for zipper teeth, comprising the following steps:

[0034] The main raw material, the antioxidant and the lubricant are mixed to obtain a mixture; the mixture is melt-extruded and granulated to obtain a resin-based material;

[0035] in,

[0036] In terms of mass percentage, the main raw materials include:

[0037] Aramid polyamide resin 45% to 70%;

[0038] Reinforcement glass fiber filament surplus;

[0039] Wherein, the average diameter of the reinforced glass fiber filaments is 1 to 14 μm;

[0040] The amount of the antioxidant is 0% to 1% of the mass of the main raw material, and is not 0%;

[0041] The amount of the lubricant is 0% to 1% of the mass of the main raw material, and is not 0%.

[0042] At present, the existing plastic-steel zippers cannot meet the requirements of environmental protection, high load strength, etc. in some special scenarios, such as military equipment and popular assault jackets; moreover, in some extreme environments, such as severe longitudinal or transverse stretching, tearing, etc., the zipper teeth on both sides are easily separated from each other or the zipper teeth fall off, which seriously affects the performance and use effect. In addition, the total fluorine (PFAS) of some zipper injection molding materials currently used cannot meet the requirements of international environmental protection standards, especially MXD6 (CN106061311B) and its reinforcing fibers in polyamides, whose total fluorine (PFAS) content exceeds the 50ppm required by international environmental protection standards. In view of the above problems, the present invention provides a novel fluorine-free high-strength resin zipper, which can effectively improve the flat pull strength of the zipper, meet the application of special scenarios and extreme environments, and meet the fluorine-free requirements.

[0043] In the present invention, the main raw materials include, by mass percentage: 45% to 70% aromatic polyamide resin; and the remainder of reinforcing glass fiber.

[0044] in:

[0045] The aromatic polyamide resin is a high-performance aromatic polyamide resin, which is a thermoplastic polymer compound with repeating amide groups -(NHCO)- as the main constituent unit. In the present invention, the aromatic polyamide resin is preferably a fluorine-free environmentally friendly resin PARA, and more preferably Solvay PARA-1622 and / or Solvay PARA-9048. In the present invention, the amount of the aromatic polyamide resin in the main raw material is 45% to 70%, specifically 45%, 50%, 55%, 60%, 65%, 70%.

[0046] The reinforcing glass fiber yarn is preferably an inorganic glass fiber yarn, more preferably an E glass fiber yarn (i.e., an E-grade glass fiber yarn), further preferably an ECR reinforcing glass fiber yarn, and most preferably an ECR high-performance glass fiber of Boya Composite Materials Co., Ltd., abbreviated as Boya Composites ECR high-performance glass fiber yarn. In the present invention, the average diameter of the reinforcing glass fiber yarn is 1 to 14 μm, specifically 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm. In the present invention, the amount of the reinforcing glass fiber yarn in the main raw material is the remainder, that is, except for the aromatic polyamide resin, the rest is the reinforcing glass fiber yarn, which makes up 100%.

[0047] In the present invention, the antioxidant is preferably BASF 1098 antioxidant. In the present invention, the amount of the antioxidant is 0% to 1% of the mass of the main raw material, and is not 0%; specifically, it can be 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%.

[0048] In the present invention, the lubricant is preferably Ceralene-CP45M lubricant. In the present invention, the amount of the lubricant is 0% to 1% of the mass of the main raw material, and is not 0%; specifically, it can be 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%.

[0049] In one embodiment of the present invention, the materials used are as follows:

[0050] The main raw materials are:

[0051] Solvay PARA-1622 50%;

[0052] Boya Composites ECR high-performance glass fiber (average diameter 10μm) 50%;

[0053] The antioxidant is BASF1098 antioxidant, and the amount used is 1% of the total mass of the main raw material;

[0054] The lubricant is Ceralene-CP45M lubricant, and the amount used is 1% of the total mass of the main raw material.

[0055] In another embodiment of the present invention, the materials used are as follows:

[0056] The main raw materials are:

[0057] Solvay PARA-9048 70%;

[0058] Boya Composites ECR high-performance glass fiber (average diameter 10μm) 30%;

[0059] The antioxidant is BASF1098 antioxidant, and the amount used is 1% of the total mass of the main raw material;

[0060] The lubricant is Ceralene-CP45M lubricant, and the amount used is 1% of the total mass of the main raw material.

[0061] The present invention adopts certain aromatic polyamide resin and reinforced glass fiber filaments, wherein the reinforced glass fiber filaments are used to modify the reinforced resin material, and certain antioxidants and lubricants are added at the same time. The melting point of the obtained mixture is 250-280°C, and no fluorine-based substances appear under high-temperature injection molding conditions. No fluorine-based substances will be precipitated or released during processing and injection molding. Moreover, the above materials are matched with each other, which can effectively improve the flat pulling strength of the zipper teeth.

[0062] In the present invention, after the main raw material, antioxidant and lubricant are mixed to obtain a mixture, the mixture is melt-extruded. Specifically, the mixture is injection-molded by a horizontal screw molding machine, and the temperature condition is preferably 250-280° C., specifically 250° C., 260° C., 270° C., 280° C. After injection molding by the horizontal screw molding machine, extrusion, granulation, and preferably cooling are performed to obtain a mixture granular material, that is, a resin-based material.

[0063] The present invention also provides a resin-based material for zipper teeth obtained by the preparation method described in the above technical solution.

[0064] The present invention also provides a method for preparing a zipper, comprising: heating and injection molding a raw material on a zipper injection molding machine equipped with a resin zipper mold, and injection molding teeth on a corresponding resin zipper tape to obtain a zipper; wherein the raw material is the resin-based material for zipper teeth described in the above technical solution.

[0065] In the present invention, the above raw materials (i.e. the resin-based materials mentioned above) are preferably dried before use. The drying temperature is preferably 100-120°C, specifically 100°C, 110°C, 120°C. The drying time is preferably 2-4h, specifically 2h, 3h, 4h. After drying, the raw materials are fed into a zipper injection molding machine to prepare a zipper.

[0066] In the present invention, the resin zipper mold is a conventional mold in the art, such as a No. 5 resin zipper mold. The zipper injection molding machine is preferably a vertical zipper injection molding machine.

[0067] In the present invention, the temperature of the injection molding machine is set to 250-280°C (i.e., the injection molding temperature is 250-280°C), specifically 250°C, 260°C, 270°C, 280°C. The pressure of the injection molding machine is set to 45-50MPa, specifically 45MPa, 46MPa, 47MPa, 48MPa, 49MPa, 50MPa. After injection molding by the zipper injection molding machine, teeth are injection molded on the zipper tape to obtain a zipper product.

[0068] The present invention also provides a zipper made by the preparation method described in the above technical solution.

[0069] In order to achieve the high strength and low fluorine / fluorine-free requirements of resin zippers, the present invention provides a new fluorine-free high-strength resin zipper, which adopts a specific new high-performance aromatic polyamide, utilizes specific fluorine-free glass fiber filament reinforcement as the injection molding raw material of plastic-steel zipper teeth, and is matched with certain antioxidants and lubricants, adjusts the injection molding resin tooth raw material formula, and controls the zipper tooth injection molding parameters and zipper tape parameters, so as to achieve the improvement of the plastic-steel zipper in terms of high strength, fluorine and environmental protection, make up for the shortcomings of the plastic-steel zipper in special application scenarios, and meet the environmental protection requirements at the same time.

[0070] In order to further understand the present invention, preferred embodiments of the present invention are described below in conjunction with examples. However, it should be understood that these descriptions are only for further illustrating the features and advantages of the present invention, rather than limiting the claims of the present invention.

[0071] Example 1

[0072] 1. Preparation of resin-based materials:

[0073] The main raw material, BASF1098 antioxidant and Ceralene-CP45M lubricant are mixed to obtain a mixture; the mixture is injection molded by a horizontal screw molding machine at 280° C., and a resin-based granular material is obtained through extrusion, granulation and cooling.

[0074] Among them, the main raw materials are:

[0075] Solvay PARA-1622 50%;

[0076] Boya Composites ECR high-performance glass fiber (average diameter 10μm) 50%.

[0077] The amount of antioxidant used is 1% of the total mass of the main raw materials, and the amount of lubricant used is 1% of the total mass of the main raw materials.

[0078] 2. Preparation of zipper:

[0079] The resin-based granular material was dried in a drying machine at 120°C for 4 hours. Then, the zipper injection molding machine with the No. 5 resin zipper mold installed was used for temperature-injection molding. The injection molding temperature was set to 250°C, the injection molding pressure was set to 45 MPa, and the injection molding teeth were injection molded on the corresponding No. 5 resin zipper tape to obtain a zipper product.

[0080] Example 2

[0081] 1. Preparation of resin-based materials:

[0082] The main raw material, BASF1098 antioxidant and Ceralene-CP45M lubricant are mixed to obtain a mixture; the mixture is injection molded by a horizontal screw molding machine at 280° C., and a resin-based granular material is obtained through extrusion, granulation and cooling.

[0083] Among them, the main raw materials are:

[0084] Solvay PARA-9048 70%;

[0085] Boya Composites ECR high-performance glass fiber (average diameter 10μm) 30%.

[0086] The amount of antioxidant used is 1% of the total mass of the main raw materials, and the amount of lubricant used is 1% of the total mass of the main raw materials.

[0087] 2. Preparation of zipper:

[0088] The resin-based granular material was dried in a drying machine at 120°C for 4 hours. Then, the zipper injection molding machine with the No. 5 resin zipper mold installed was used for temperature-injection molding. The injection molding temperature was set to 270°C, the injection molding pressure was set to 50 MPa, and the injection molding teeth were injection molded on the corresponding No. 5 resin zipper tape to obtain a zipper product.

[0089] Comparative Example 1

[0090] The method is implemented in accordance with Example 1, except that the amount of aromatic polyamide resin in the main raw material is 30%, and the amount of reinforcing glass fiber is 70%.

[0091] As a result, during the zipper injection molding process, problems such as sticking of the mold, the inability to fully mold the zipper teeth, and the difficulty in feeding the zipper due to missing teeth occurred, making injection molding impossible.

[0092] Comparative Example 2

[0093] Taiwan Formosa Plastics FM207POM was dried in a drying machine at 120°C for 4 hours. Then, the temperature was raised and injection molding was performed on a zipper injection molding machine with a No. 5 resin zipper mold installed. The injection molding temperature was set to 180°C, the injection molding pressure was set to 45MPa, and the injection molding teeth were injection molded on the corresponding No. 5 resin zipper tape to obtain a zipper product.

[0094] Comparative Example 3

[0095] The method was implemented in accordance with Example 2, except that the Boya Composites ECR high-performance glass fiber yarn was replaced with E-glass chopped reinforcing fiber, model T435N, with a fiber diameter of 10 μm and a chopped length of 3.0 mm.

[0096] As a result, the total fluorine (PFAS) content of the resulting product was 894 ppm, far exceeding the requirements of international environmental protection standards and unable to meet actual application needs.

[0097] Product testing:

[0098] The zipper products obtained in each embodiment and comparative example were tested for maximum transverse strength load on a zipper fabric strength tester according to national standards, wherein 10 different points of each sample were tested; in addition, the total fluorine (PFAS) content of each sample was also tested (international environmental protection standards require ≤50ppm). The results are shown in Table 1.

[0099] Table 1: Test results

[0100]

[0101] It can be seen from the test results in Table 1 that the comparative example 1 cannot be injection molded due to the change in the raw material formula ratio. The comparative example 2 is a conventional material at present, and the comparative example 3 uses other reinforcing fiber yarns. As a result, the flat pull strength of the obtained product is low or the total fluorine exceeds the standard. The zippers obtained in Examples 1-2 of the present invention significantly improve the flat pull strength while ensuring low fluorine or no fluorine.

[0102] Specific examples are used herein to illustrate the principles and implementation methods of the present invention. The description of the above embodiments is only used to help understand the method of the present invention and its core ideas, including the best mode, and also enable any technician in the field to practice the present invention, including making and using any device or system, and implementing any combined method. It should be pointed out that for ordinary technicians in this technical field, without departing from the principle of the present invention, the present invention can also be improved and modified, and these improvements and modifications also fall within the scope of protection of the claims of the present invention. The scope of patent protection of the present invention is defined by the claims and may include other embodiments that can be thought of by those skilled in the art. If these other embodiments have structural elements similar to the literal expression of the claims, or if they include equivalent structural elements that are not substantially different from the literal expression of the claims, then these other embodiments should also be included in the scope of the claims.

Claims

1. A method for preparing a resin-based material for zipper teeth, characterized in that: The following steps are involved: The main raw material, the antioxidant and the lubricant are mixed to obtain a mixture; the mixture is melt-extruded and granulated to obtain a resin-based material; in, In terms of mass percentage, the main raw materials include: Aramid polyamide resin 45% to 70%; Reinforcement glass fiber filament surplus; Wherein, the average diameter of the reinforced glass fiber filaments is 1 to 14 μm; The amount of the antioxidant is 0% to 1% of the mass of the main raw material, and is not 0%; The amount of the lubricant is 0% to 1% of the mass of the main raw material, and is not 0%.

2. The preparation method according to claim 1, characterized in that: The aromatic polyamide resin is a fluorine-free and environmentally friendly resin PARA; The reinforcing glass fiber yarn is E glass fiber yarn.

3. The preparation method according to claim 1 or 2, characterized in that: The aromatic polyamide resin is Solvay PARA-1622 and / or Solvay PARA-9048.

4. The preparation method according to claim 1 or 2, characterized in that: The reinforcing glass fiber yarn is Boya Composites ECR high-performance glass fiber yarn.

5. The preparation method according to claim 1, characterized in that: The antioxidant is preferably BASF1098 antioxidant; The lubricant is Ceralene-CP45M lubricant.

6. The preparation method according to claim 1, characterized in that: The melting temperature is 250-280°C.

7. A resin-based material for zipper teeth obtained by the preparation method according to any one of claims 1 to 6.

8. A method for preparing a zipper, comprising: The raw material is heated and injection-molded on a zipper injection molding machine equipped with a resin zipper mold, and the injection-molded teeth are injection-molded on the corresponding resin zipper tape to obtain a zipper; Wherein, the raw material is the resin-based material for zipper teeth as described in claim 7.

9. The preparation method according to claim 8, characterized in that: The temperature of the injection molding machine is set to 250-280° C., and the pressure of the injection molding machine is set to 45-50 MPa.

10. A zipper made by the method according to any one of claims 8 to 9.

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