A process for producing a bio-based waterproof and moisture-permeable glove liner material

Abstract

The application discloses a production process of a bio-based waterproof and moisture-permeable glove lining material, and belongs to the technical field of glove lining material production. The production process comprises the following steps: PP non-woven fabric and bio-based fiber film are high-temperature hot-pressed through a film laminating machine, and then cooling, shaping, cutting and sewing are carried out to obtain the bio-based waterproof and moisture-permeable glove lining material. The bio-based waterproof and moisture-permeable glove lining material prepared by the application is hot-pressed from PP non-woven fabric and bio-based fiber film. In the double-layer composite structure, the bio-based fiber film of the outer layer is obtained after bio-based PA11 material is subjected to melt spinning, hydrophobic modification and weaving. The bio-based fiber film of the outer layer has a fine and uniform microporous structure with uniform pore size and distribution. Meanwhile, the prepared bio-based glove lining material has excellent waterproof, moisture-permeable and antibacterial properties.

Description

Technical Field

[0001] This invention belongs to the field of glove lining material production technology, specifically relating to a production process for a bio-based waterproof and breathable glove lining material. Background Technology

[0002] In the research and development of bio-based polyamide materials (bio-based PA), commonly used renewable raw material resources include castor oil, oleic acid and linoleic acid, and glucose. Among them, castor seeds, as a raw material for castor oil, are a fast-growing crop with a quarterly stem height of up to 2 meters. They can be planted in poor soil without competing with food crops for land. The yield of castor beans can reach about 10 tons per hectare, making them an excellent renewable raw material.

[0003] The technology for developing bio-based polyamide materials using castor oil is already quite mature. For example, BASF's bio-based PA610 uses 60% sebacic acid derived from castor oil; Arkema's bio-based PA11 uses castor seeds as raw material to obtain 11-aminoundecanoic acid, which is then polymerized in three stages to obtain poly11-aminoundecanoic acid. According to research results from the French Institute of Textile and Clothing (IFTH), PA11 fibers and their fabrics have many characteristics, including high abrasion resistance, good chlorine resistance, good flame retardancy, and quick-drying properties.

[0004] This invention aims to apply bio-based PA11 material to the field of waterproof and breathable glove lining materials. Waterproof and breathable glove lining materials refer to glove lining materials where water cannot penetrate under certain pressure, while sweat emitted by the human body can be conducted to the outside as water vapor through the lining material. These materials prevent sweat from accumulating and condensing between the skin and the lining, thus maintaining clothing comfort. It is a high-tech, unique, and functional glove lining material. The application of bio-based PA11 material in the field of textile glove lining materials has promising prospects. Summary of the Invention

[0005] The purpose of this invention is to provide a method for applying bio-based PA11 material in the field of waterproof and breathable glove lining materials. At the same time, through improvements in process methods and process parameters, as well as directional modification of the material, a production process for bio-based waterproof and breathable glove lining materials is ultimately formed.

[0006] The objective of this invention can be achieved through the following technical solutions:

[0007] A manufacturing process for a bio-based waterproof and breathable glove lining material includes the following steps:

[0008] The PP nonwoven fabric and bio-based fiber membrane are hot-pressed together at high temperature using a laminating machine, and then cooled, shaped, cut and sewn to obtain the bio-based waterproof and breathable glove lining material.

[0009] The bio-based fiber membrane is obtained by melt spinning of bio-based polyamide material to obtain bio-based fibers; the bio-based fibers are sized and modified with hydrophobic modified slurry and then plain woven to obtain the bio-based fiber membrane.

[0010] Furthermore, the inner lining material of the bio-based waterproof and breathable gloves is a two-layer composite structure or a three-layer composite structure; the two-layer composite structure is PP non-woven fabric + bio-based fiber membrane; the three-layer composite structure is PP non-woven fabric + bio-based fiber membrane + PP non-woven fabric.

[0011] Furthermore, the basis weight of the PP nonwoven fabric is 15-25 g / m². 2 The basis weight of the bio-based fiber membrane is 15-25 g / m³. 2 .

[0012] Furthermore, the bio-based fiber membrane is prepared by the following steps:

[0013] Step S1: The pre-treated bio-based polyamide is fed into a spinning machine for melt spinning. The temperature range of the melt spinning machine is as follows: Zone 1 is the preheating temperature of 100-105℃, Zone 2 is the compression temperature of 125-130℃, Zone 3 is the compression temperature of 150-155℃, and Zone 4 is the extrusion temperature of 185℃. The screw speed of the spinning machine is controlled at 50 rpm, the drawing speed is 10 m / min, and the extrusion pressure is 2 MPa. After extrusion, bio-based fibers are obtained.

[0014] Step S2: Bio-based fibers are sized using a hydrophobically modified sizing agent under high pressure. The feed tension of the bio-based fibers is controlled at 60-65 mN, and the take-up tension is controlled at 65-70 mN. After sizing, the fibers are dried in stages: the first stage temperature is 136-138℃, the second stage temperature is 130-132℃, the third stage temperature is 98-110℃, and the fourth stage temperature is 90-92℃. The sizing rate is controlled to ensure a sizing rate of 4.8-5.2%. After sizing, plain weaving is performed at a speed of 520-550 rpm / min. After weaving, the fibers are set at 70-80℃. After the set-up process, the bio-based fiber membrane is obtained.

[0015] Furthermore, the preprocessing procedure in step S1 includes the following steps:

[0016] The bio-based polyamide material was placed in a vacuum oven at 60°C for 6 hours for drying and pretreatment, then removed and cooled to room temperature for later use.

[0017] Furthermore, in step S1, the outlet diameter of the melt spinning machine during the melt spinning process is 0.30 mm.

[0018] Furthermore, the bio-based polyamide material is bio-based PA11.

[0019] Furthermore, the hydrophobic modified slurry for high-pressure sizing is prepared by the following steps:

[0020] 5-Difluoromethoxy-2-mercapto-1H-benzimidazole was added to anhydrous ethanol and stirred until dissolved. Then, dichloromethane and vinyltrimethoxysilane were added and stirred until mixed. An initiator and a catalyst were added, and the mixture was reacted under 30W ultraviolet light for 20 minutes to obtain a fluorinated silane solution. Polypropylene resin was added to the fluorinated silane solution and stirred at high speed to obtain a hydrophobic modified slurry.

[0021] Further, the ratio of anhydrous ethanol, 5-difluoromethoxy-2-mercapto-1H-benzimidazole, dichloromethane, vinyltrimethoxysilane, initiator, catalyst and polypropylene resin is 40mL:0.22-0.23g:60mL:11.5-12.0mL:0.02g:0.01g:3.1-3.2g.

[0022] Furthermore, the initiator is 2,2-dimethoxyphenylacetophenone; the catalyst is triethylenetetramine.

[0023] The beneficial effects of this invention are:

[0024] (1) The bio-based waterproof and breathable glove lining material prepared by the present invention is made of PP non-woven fabric and bio-based fiber membrane by hot pressing. In the double-layer composite structure, the bio-based fiber membrane is the outer layer and the PP non-woven fabric is the inner layer. The bio-based fiber membrane of the outer layer is obtained by melt spinning, hydrophobic modification and weaving of bio-based PA11 material. It has a fine and uniform microporous structure with uniform pore size and distribution. At the same time, the prepared bio-based glove lining material has excellent waterproof, breathable and antibacterial properties.

[0025] (2) The bio-based fiber membrane prepared by this invention is modified with a hydrophobic modified slurry. The fluorinated silane solution in the hydrophobic modified slurry has good hydrophobicity. At the same time, the imidazole ring structure of the silane side chain in the fluorinated silane solution has excellent antibacterial properties, which helps to improve the antibacterial effect of the glove lining material. Then, the PP nonwoven fabric of the inner layer of the bio-based fiber membrane has water absorption. After being made into glove lining material, the outer bio-based fiber membrane has excellent waterproof performance. The inner PP nonwoven fabric can absorb the heat and sweat generated by the human body and then diffuse through the outer layer to remove the excess heat and sweat generated by the human body during activities in time, maintaining a more comfortable and suitable internal condition. It has excellent waterproof and breathable performance. In addition, the bio-based PA11 material is made from 100% bio-based castor oil. This invention provides a direction for the modification and application of bio-based PA11 material. Attached Figure Description

[0026] The invention will now be further described with reference to the accompanying drawings.

[0027] Figure 1 This is a schematic diagram of the finished glove structure produced by applying the lining material prepared in Example 7 of the present invention to the production of bio-based waterproof and breathable gloves. Detailed Implementation

[0028] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0029] Example 1

[0030] Preparation of hydrophobically modified slurry:

[0031] 0.22 g of 5-difluoromethoxy-2-mercapto-1H-benzimidazole was added to 40 mL of anhydrous ethanol and stirred until dissolved. Then, 60 mL of dichloromethane and 11.5 mL of vinyltrimethoxysilane were added and stirred until mixed. 0.02 mL of initiator 2,2-dimethoxyphenylacetophenone (99% purity) and 0.01 mL of catalyst triethylenetetramine were added and reacted under 30 W UV light for 20 min to obtain a fluorinated silane solution. 3.1 g of polypropylene resin (purchased from ExxonMobil) was added to the fluorinated silane solution and stirred at high speed to obtain a hydrophobically modified slurry.

[0032] Example 2

[0033] Preparation of hydrophobically modified slurry:

[0034] 0.23 g of 5-difluoromethoxy-2-mercapto-1H-benzimidazole was added to 40 mL of anhydrous ethanol and stirred until dissolved. Then, 60 mL of dichloromethane and 11.8 mL of vinyltrimethoxysilane were added and stirred until mixed. 0.02 mL of initiator 2,2-dimethoxyphenylacetophenone (99% purity) and 0.01 mL of catalyst triethylenetetramine were added and reacted under 30 W UV light for 20 min to obtain a fluorinated silane solution. 3.2 g of polypropylene resin (purchased from ExxonMobil) was added to the fluorinated silane solution and stirred at high speed to obtain a hydrophobically modified slurry.

[0035] Example 3

[0036] Preparation of hydrophobically modified slurry:

[0037] 0.23 g of 5-difluoromethoxy-2-mercapto-1H-benzimidazole was added to 40 mL of anhydrous ethanol and stirred until dissolved. Then, 60 mL of dichloromethane and 12.0 mL of vinyltrimethoxysilane were added and stirred until mixed. 0.02 mL of initiator 2,2-dimethoxyphenylacetophenone (99% purity) and 0.01 mL of catalyst triethylenetetramine were added and reacted under 30 W UV light for 20 min to obtain a fluorinated silane solution. 3.2 g of polypropylene resin (purchased from ExxonMobil) was added to the fluorinated silane solution and stirred at high speed to obtain a hydrophobically modified slurry.

[0038] Example 4

[0039] Preparation of bio-based fiber membranes:

[0040] Step S1: Place the bio-based polyamide material in a vacuum oven at 60℃ for drying and pretreatment for 6 hours. After removing it and cooling it to room temperature, put the dried and pretreated bio-based polyamide into a spinning machine for melt spinning. The outlet diameter of the melt spinning machine is 0.30 mm. The temperature range of the melt spinning machine is as follows: Zone 1 is the preheating temperature of 100℃, Zone 2 is the compression temperature of 125℃, Zone 3 is the compression temperature of 150℃, and Zone 4 is the extrusion temperature of 185℃. Control the screw speed of the spinning machine to be 50 rpm, the drawing speed to be 10 m / min, and the extrusion pressure to be 2 MPa. After extrusion, bio-based fibers are obtained.

[0041] Step S2: Using the hydrophobic modified sizing material prepared in Example 1, bio-based fibers were sized using a high-pressure sizing method. The feed tension of the bio-based fibers was controlled at 60 mN, and the take-up tension at 65 mN. After sizing, the fibers were dried in stages: the first stage temperature was 136℃, the second stage temperature was 130℃, the third stage temperature was 98℃, and the fourth stage temperature was 90℃. The sizing rate was controlled to ensure a sizing rate of 5.2%. After sizing, plain weaving was performed at a weaving speed of 520 rpm / min. After weaving, the fibers were placed at 70℃ for setting treatment. After the setting treatment, a bio-based fiber membrane was obtained. The basis weight of the bio-based fiber membrane was measured to be 15 g / m³. 2 .

[0042] Example 5

[0043] Preparation of bio-based fiber membranes:

[0044] Step S1: The bio-based polyamide material is placed in a vacuum oven at 60°C for drying and pretreatment for 6 hours. After being removed and cooled to room temperature, the dried and pretreated bio-based polyamide is fed into a spinning machine for melt spinning. The outlet diameter of the melt spinning machine is 0.30 mm. The temperature range of the melt spinning machine is as follows: Zone 1 is the preheating temperature of 102°C, Zone 2 is the compression temperature of 128°C, Zone 3 is the compression temperature of 154°C, and Zone 4 is the extrusion temperature of 185°C. The screw speed of the spinning machine is controlled at 50 rpm, the drawing speed is 10 m / min, and the extrusion pressure is 2 MPa. After extrusion, bio-based fibers are obtained.

[0045] Step S2: Using the hydrophobic modified sizing material prepared in Example 2, bio-based fibers were sized using a high-pressure sizing method. The feed tension of the bio-based fibers was controlled at 64 mN, and the take-up tension at 67 mN. After sizing, the fibers were dried in stages: the first stage at 137°C, the second at 131°C, the third at 105°C, and the fourth at 91°C. The sizing rate was controlled to ensure a sizing rate of 4.9%. After sizing, plain weaving was performed at a speed of 540 rpm / min. After weaving, the fibers were set at 75°C. After the set-up treatment, a bio-based fiber membrane was obtained. The basis weight of the bio-based fiber membrane was measured to be 20 g / m³. 2 .

[0046] Example 6

[0047] Preparation of bio-based fiber membranes:

[0048] Step S1: Place the bio-based polyamide material in a vacuum oven at 60℃ for drying and pretreatment for 6 hours. After removing it and cooling it to room temperature, put the dried and pretreated bio-based polyamide into a spinning machine for melt spinning. The outlet diameter of the melt spinning machine is 0.30 mm. The temperature range of the melt spinning machine is as follows: Zone 1 is a preheating temperature of 105℃, Zone 2 is a compression temperature of 130℃, Zone 3 is a compression temperature of 155℃, and Zone 4 is an extrusion temperature of 185℃. Control the screw speed of the spinning machine to be 50 rpm, the drawing speed to be 10 m / min, and the extrusion pressure to be 2 MPa. After extrusion, bio-based fibers are obtained.

[0049] Step S2: Using the hydrophobic modified sizing material prepared in Example 3, bio-based fibers were sized using a high-pressure sizing method. The feed tension of the bio-based fibers was controlled at 65 mN, and the take-up tension at 70 mN. After sizing, the fibers were dried in stages: the first stage temperature was 138℃, the second stage temperature was 132℃, the third stage temperature was 110℃, and the fourth stage temperature was 92℃. The sizing rate was controlled to ensure a sizing rate of 5.2%. After sizing, plain weaving was performed at a weaving speed of 520 rpm / min. After weaving, the fibers were set at 80℃. After the set-up treatment, a bio-based fiber membrane was obtained. The basis weight of the bio-based fiber membrane was measured to be 25 g / m³. 2 .

[0050] Example 7

[0051] A manufacturing process for a bio-based waterproof and breathable glove lining material includes the following steps:

[0052] PP nonwoven fabric (15g / m²) is laminated using a laminating machine. 2 The nonwoven fabric side is hot-pressed onto one side of the bio-based fiber membrane prepared in Example 4, and then cooled, shaped, cut, and sewn to obtain the lining material of the bio-based waterproof and breathable glove. The nonwoven fabric side is the inner side, and the bio-based fiber membrane side is the outer side. Finally, bio-based waterproof and breathable gloves can be produced. The glove structure is shown in the attached figure. Figure 1 As shown in the image.

[0053] Example 8

[0054] A manufacturing process for a bio-based waterproof and breathable glove lining material includes the following steps:

[0055] PP nonwoven fabric (20g / m²) is laminated using a laminating machine. 2 The nonwoven fabric side is hot-pressed with one side of the bio-based fiber membrane prepared in Example 5, and then cooled, shaped, cut and sewn to obtain a bio-based waterproof and breathable glove lining material, wherein the nonwoven fabric side is the inner side and the bio-based fiber membrane side is the outer side.

[0056] Example 9

[0057] A manufacturing process for a bio-based waterproof and breathable glove lining material includes the following steps:

[0058] PP nonwoven fabric (25g / m²) is laminated using a laminating machine. 2 The nonwoven fabric side is hot-pressed with one side of the bio-based fiber membrane prepared in Example 6, and then cooled, shaped, cut and sewn to obtain a bio-based waterproof and breathable glove lining material, wherein the nonwoven fabric side is the inner side and the bio-based fiber membrane side is the outer side.

[0059] Example 10

[0060] A manufacturing process for a bio-based waterproof and breathable glove lining material includes the following steps:

[0061] Two layers of PP nonwoven fabric (15g / m²) are laminated using a laminating machine. 2 The bio-based fiber membrane prepared in Example 4 is hot-pressed and laminated with both sides at high temperature, and then cooled, shaped, cut and sewn to obtain the bio-based waterproof and breathable glove lining material.

[0062] Example 11

[0063] A manufacturing process for a bio-based waterproof and breathable glove lining material includes the following steps:

[0064] Two layers of PP nonwoven fabric (20g / m²) are laminated using a laminating machine. 2 The bio-based fiber membrane prepared in Example 5 is hot-pressed and laminated to both sides at high temperature. After cooling, shaping, cutting and sewing, a bio-based waterproof and breathable glove lining material is obtained.

[0065] Example 12

[0066] A manufacturing process for a bio-based waterproof and breathable glove lining material includes the following steps:

[0067] Two layers of PP nonwoven fabric (25g / m²) are laminated using a laminating machine. 2 The bio-based fiber membrane prepared in Example 6 is hot-pressed and laminated with both sides at high temperature, and then cooled, shaped, cut and sewn to obtain the bio-based waterproof and breathable glove lining material.

[0068] Comparative Example 1

[0069] Comparative Example 1 served as the control group for Example 8.

[0070] First, prepare a bio-based fiber membrane: replace the hydrophobic modified slurry prepared in Example 2 in step S2 of Example 5 with polyvinyl alcohol (PVA; viscosity: 45.0-55.0 mPa*s; Mw approximately 45000), while keeping the other raw materials and preparation methods unchanged. Finally, a bio-based fiber membrane is obtained.

[0071] Then, a manufacturing process for a bio-based waterproof and breathable glove lining material includes the following steps:

[0072] The PP nonwoven fabric is hot-pressed with one side of the above-prepared bio-based fiber membrane using a laminating machine. After cooling, shaping, cutting and sewing, a bio-based waterproof and breathable glove lining material is obtained, wherein the nonwoven fabric side is the inner side and the bio-based fiber membrane side is the outer side.

[0073] Example 13

[0074] The pore size of the bio-based fiber membranes in Examples 7-9 and Comparative Example 1 was measured. Then, the moisture permeability, air permeability, and antibacterial properties of the bio-based waterproof and breathable glove lining materials prepared in Examples 7-9 and Comparative Example 1 were tested. The test results are shown in Table 1. Specifically:

[0075] Pore ​​size determination: The pore size and distribution of the bio-based fiber membrane were tested using the gas permeation bubble point method;

[0076] The moisture permeability was tested according to GB / T 12704-2009 "Textiles - Test Method for Moisture Permeability of Fabrics";

[0077] The air permeability performance was determined according to GB / T 5453-1997 "Textiles - Determination of Air Permeability of Fabrics";

[0078] The surface water repellency performance was determined according to GB / T 4745-2012 "Test and Evaluation of Water Repellency of Textiles - Water-Soaking Method";

[0079] The antibacterial properties were evaluated according to GB / T 20944.1-2007 "Evaluation of antibacterial properties of textiles - Part 1: Agar plate diffusion method".

[0080] Table 1

[0081]

[0082]

[0083] As can be seen from Table 1, the bio-based fiber membrane prepared by the present invention has a fine and uniform microporous structure with uniform pore size and distribution. At the same time, the prepared bio-based glove lining material has excellent waterproof, breathable and antibacterial properties.

[0084] It should be noted that, in this document, terms such as “comprising,” “including,” or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such process, method, article, or apparatus.

[0085] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A manufacturing process for a bio-based waterproof and breathable glove lining material, characterized in that, Includes the following steps: The PP nonwoven fabric and bio-based fiber membrane are hot-pressed together at high temperature using a laminating machine, and then cooled, shaped, cut and sewn to obtain the bio-based waterproof and breathable glove lining material. The bio-based fiber membrane is obtained by melt spinning bio-based polyamide material to obtain bio-based fibers; The bio-based fiber is modified by sizing with a hydrophobic modified slurry and then woven in plain weave to obtain a bio-based fiber membrane. The bio-based fiber membrane is prepared by the following steps: Step S1: The pre-treated bio-based polyamide is fed into a spinning machine for melt spinning. The temperature range of the melt spinning machine is as follows: Zone 1 is the preheating temperature of 100-105℃, Zone 2 is the compression temperature of 125-130℃, Zone 3 is the compression temperature of 150-155℃, and Zone 4 is the extrusion temperature of 185℃. The screw speed of the spinning machine is controlled at 50 rpm, the drawing speed is 10 m / min, and the extrusion pressure is 2 MPa. After extrusion, bio-based fibers are obtained. Step S2: Bio-based fibers are sized using a high-pressure sizing method with a hydrophobic modified sizing agent. The feed tension of the bio-based fibers is controlled at 60-65mN and the take-up tension at 65-70mN. After sizing, the fibers are dried in stages: the first stage temperature is 136-138℃, the second stage temperature is 130-132℃, the third stage temperature is 98-110℃, and the fourth stage temperature is 90-92℃. The sizing rate is controlled to ensure a sizing rate of 4.8-5.2%. After sizing, plain weaving is performed at a speed of 520-550rpm / min. After weaving, the fibers are set at 70-80℃. After the set-up process, a bio-based fiber membrane is obtained. The hydrophobic modified slurry for high-pressure sizing is prepared by the following steps: 5-Difluoromethoxy-2-mercapto-1H-benzimidazole was added to anhydrous ethanol and stirred until dissolved. Then, dichloromethane and vinyltrimethoxysilane were added and stirred until mixed. An initiator and catalyst were added and reacted under 30W ultraviolet light for 20 minutes to obtain a fluorinated silane solution. Polypropylene resin was added to the fluorinated silane solution and stirred at high speed to obtain a hydrophobic modified slurry. The ratio of anhydrous ethanol, 5-difluoromethoxy-2-mercapto-1H-benzimidazole, dichloromethane, vinyltrimethoxysilane, initiator, catalyst, and polypropylene resin is 40 mL: 0.22-0.23 g: 60 mL: 11.5-12.0 mL: 0.02 mL: 0.01 mL: 3.1-3.2 g; The initiator is 2,2-dimethoxyphenylacetophenone; the catalyst is triethylenetetramine.

2. The production process of a bio-based waterproof and breathable glove lining material according to claim 1, characterized in that, The inner lining material of the bio-based waterproof and breathable gloves is a two-layer composite structure or a three-layer composite structure; the two-layer composite structure is PP non-woven fabric + bio-based fiber membrane; the three-layer composite structure is PP non-woven fabric + bio-based fiber membrane + PP non-woven fabric.

3. The production process of a bio-based waterproof and breathable glove lining material according to claim 1, characterized in that, The basis weight of the PP nonwoven fabric is 15-25 g / m². 2 The basis weight of the bio-based fiber membrane is 15-25 g / m³. 2 .

4. The production process of a bio-based waterproof and breathable glove lining material according to claim 1, characterized in that, The preprocessing process described in step S1 includes the following steps: The bio-based polyamide material was placed in a vacuum oven at 60°C for 6 hours for drying and pretreatment, then removed and cooled to room temperature for later use.

5. The production process of a bio-based waterproof and breathable glove lining material according to claim 1, characterized in that, In step S1, the outlet diameter of the melt spinning machine during the melt spinning process is 0.30 mm.

6. The production process of a bio-based waterproof and breathable glove lining material according to claim 1, characterized in that, The bio-based polyamide material is bio-based PA11.

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