Modified TPU (thermoplastic polyurethane) waterproof and moisture-permeable formula granule, modified TPU waterproof and moisture-permeable film as well as preparation method and application thereof

Abstract

The invention provides modified TPU (thermoplastic polyurethane) waterproof and moisture-permeable formula granules, a TPU waterproof and moisture-permeable film as well as a preparation method and application thereof, and belongs to the technical field of composite materials. The preparation method comprises the following steps: reacting polyether polyol, isocyanate, a chain extender and an auxiliary agent to generate moisture-permeable TPU, then adding TPEE particles, diatomite master batch and a lubricant to blend and modify the TPU to obtain a modified TPU waterproof and moisture-permeable material, and then melting the modified TPU waterproof and moisture-permeable material and PE particles to perform two-layer film blowing to obtain the TPU waterproof and moisture-permeable film. The TPU waterproof moisture-permeable film has good waterproofness and moisture permeability, the maximum moisture permeability reaches 4620g / m < 2 >. 24h when a drying agent positive cup moisture absorption method is adopted for detection, and the maximum moisture permeability reaches 10400g / m < 2 >. 24h when a water inverted cup evaporation method is adopted for detection.

Description

Technical Field

[0001] The present invention relates to the technical field of composite materials, and in particular to a modified TPU waterproof and breathable formula particle, a TPU waterproof and breathable film, and a preparation method and application thereof. Background Art

[0002] Waterproof and breathable membrane is a special material that can prevent moisture from penetrating from the outside into the inside of clothing, while allowing the sweat generated by the human body to be discharged in the form of water vapor. This membrane is usually made of high molecular polymers, such as polyurethane (PU), polyacrylonitrile (PAN), cellulose, etc., and is processed into a film with waterproof and breathable functions through a specific process. The application of waterproof and breathable membrane in clothing is mainly through combining it with textile materials to form waterproof and breathable fabrics. This fabric is widely used in outdoor clothing, protective clothing and other fields.

[0003] As an emerging environmentally friendly material, TPU has ideal comprehensive properties. It is produced by cast or blown film through an extruder, and has the inherent advantages of environmental protection, energy saving, and high efficiency. In the traditional clothing field, waterproof and breathable films mainly use PU glue coating and drying production process. During the synthesis and application of glue, a large amount of organic solvents need to be used and contacted, causing environmental and physical damage.

[0004] The new environmentally friendly TPU waterproof and breathable membrane is used as the waterproof layer of the jacket, and no organic solvent is added during the synthesis of TPU particles. When the film is produced, the blow molding or cast film process is adopted to avoid the use of solvents, which has a good environmental protection effect and reduces environmental pollution and body damage. However, the main reason why the TPU waterproof and breathable membrane has a breathable effect is that TPU contains hydrophilic groups. Under the action of temperature, water molecules combine with hydrophilic groups and diffuse to the side with low water molecule concentration to achieve a breathable effect. However, the breathability of the TPU waterproof and breathable membrane is subject to the influence of the back-end jacket processing technology (film temperature resistance and strength), and the breathability of the TPU waterproof and breathable membrane cannot be improved, which makes the wearing experience of the finished garment worse. Therefore, there is an urgent need for a waterproof and breathable membrane with good waterproof effect and large breathability. Summary of the invention

[0005] The purpose of the present invention is to provide a modified TPU waterproof and breathable formula particle, a TPU waterproof and breathable film and a preparation method and application thereof. The TPU waterproof and breathable film has a good waterproof effect and a large breathability.

[0006] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0007] The present invention provides a waterproof and breathable TPU particle, wherein the waterproof and breathable TPU particle is composed of the following raw materials in parts by weight:

[0008] 35-45 parts of polyether polyol, 35-45 parts of MDI, 8-10 parts of chain extender, 0-1 part of anti-hydrolysis agent, 0-1 part of antioxidant, 0-1 part of light stabilizer, and 0-1 part of ultraviolet absorber.

[0009] Preferably, the polyether polyol includes one or more of PEG with a molecular weight of 1000, 2000, 3000 or PBA with a molecular weight of 1000, 2000, 3000.

[0010] Preferably, the chain extender includes one or more of ethylene glycol, butanediol, and hexanediol; the anti-hydrolysis agent is polycarbodiimide; the antioxidant is one or more of antioxidant 1010, antioxidant 168, and antioxidant 1076; the light stabilizer is BasfB75; and the ultraviolet absorber is one or more of UV328, UV326, and UV234.

[0011] The present invention also provides a modified TPU waterproof and breathable formula particle prepared based on the waterproof and breathable TPU particle, which is composed of the following raw materials in parts by weight:

[0012] 80-90 parts of waterproof and breathable TPU particles, 0-10 parts of TPEE particles, 5-10 parts of diatomaceous earth masterbatch, and 0-5 parts of lubricant.

[0013] Preferably, the TPEE particles have a softening point of 185°C to 195°C, a melt index of 10 to 20 g / 10 min (220°C, 2160 g), and a moisture permeability of 6000 to 10000 g / m 2 ·24h; the lubricant is a particle made by blending TPU with oleamide or erucamide.

[0014] The present invention also provides a method for preparing modified TPU waterproof and breathable formula particles, comprising the following steps:

[0015] (1) After the polyether polyol, anti-hydrolysis agent, antioxidant, light stabilizer, and ultraviolet absorber are heated and mixed uniformly, the mixture is pumped into a polyurethane extruder in proportion with MDI and a chain extender through a metering pump for reaction and granulation to obtain waterproof and breathable TPU particles;

[0016] (2) Preparation of diatomaceous earth masterbatch: kneading and granulating the waterproof and breathable TPU particles prepared in step (1) with diatomaceous earth powder to obtain a diatomaceous earth masterbatch with a diatomaceous earth content of 50 to 70%;

[0017] (3) Preparation of modified TPU waterproof and breathable formula particles: The waterproof and breathable TPU particles prepared in step (1) are evenly mixed with TPEE particles, diatomaceous earth masterbatch, and lubricant, and then dried to obtain modified TPU waterproof and breathable formula particles.

[0018] Preferably, the polyether polyol, anti-hydrolysis agent, antioxidant, light stabilizer and ultraviolet absorber in step (1) are heated to a temperature of 100°C-110°C, and are pumped into an extruder in proportion with the molten MDI and chain extender through a metering pump for reaction at a temperature of 195°C for reaction granulation; and the drying conditions in step (3) are 90-110°C for 8-12 hours.

[0019] The present invention also provides a method for preparing a TPU waterproof and breathable membrane based on the modified TPU waterproof and breathable formula particles, comprising the following steps:

[0020] The modified TPU waterproof and breathable formula particles and PE particles are added to the A and B extruders respectively, heated and melted and extruded to the inner layer and outer layer of the die head, and then compounded in the die at the die lip and blown into a modified TPU / PE composite film with a thickness of 0.025mm-0.045mm, with the modified TPU waterproof and breathable film on the outside. After cooling, the modified TPU waterproof and breathable film is trimmed and rolled up, wherein the thickness of the modified TPU waterproof and breathable film is 0.015mm-0.025mm.

[0021] The present invention also provides a TPU waterproof and breathable membrane prepared by the method for preparing the TPU waterproof and breathable membrane.

[0022] The present invention also provides an application of a TPU waterproof and breathable membrane in preparing a waterproof and breathable material.

[0023] The beneficial effects of the present invention compared with the prior art are:

[0024] The present invention utilizes polyether polyol, isocyanate, chain extender reaction, and auxiliary agent to generate moisture permeable TPU particles, uses TPEE particles, diatomite masterbatch and lubricant to modify TPU to obtain modified TPU waterproof and moisture permeable material, and then melts and blows PE particles to obtain modified TPU waterproof and moisture permeable film. The TPU waterproof and moisture permeable film has good waterproofness and moisture permeability. When the desiccant positive cup moisture absorption method is used for detection, the maximum moisture permeability reaches 4620g / m 2 ·24h, the maximum moisture permeability reached 10400g / m when the water inverted cup evaporation method was adopted 2 ·24h. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative labor.

[0026] Figure 1The TPU waterproof and breathable membrane prepared in Example 1 of the present invention, wherein 1 is a modified TPU waterproof and breathable membrane, and 2 is a PE membrane;

[0027] Figure 2 This is the process flow for preparing TPU waterproof and breathable membrane in Example 1 of the present invention, wherein 1 is extruder A, 2 is air ring, 3 is herringbone, 4 is die head, 5 is extruder B, 6 is trimming, and 7 is winding. DETAILED DESCRIPTION

[0028] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as limiting the present invention, but should be understood as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0029] It should be understood that the terms described in the present invention are only for describing special embodiments and are not intended to limit the present invention. In addition, for the numerical range in the present invention, it should be understood that each intermediate value between the upper and lower limits of the scope is also specifically disclosed. Each smaller range between the intermediate value in any stated value or stated range and any other stated value or intermediate value in the described range is also included in the present invention. The upper and lower limits of these smaller ranges can be independently included or excluded in the scope.

[0030] Unless otherwise indicated, all technical and scientific terms used herein have the same meanings as those generally understood by those skilled in the art. Although the present invention describes only preferred methods and materials, any methods and materials similar or equivalent to those described herein may also be used in the implementation or testing of the present invention. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and / or materials associated with the documents. In the event of a conflict with any incorporated document, the content of this specification shall prevail.

[0031] It will be apparent to those skilled in the art that various modifications and variations may be made to the specific embodiments of the present invention description without departing from the scope or spirit of the present invention. Other embodiments derived from the present invention description will be apparent to those skilled in the art. The present invention description and examples are exemplary only.

[0032] The words “include,” “including,” “have,” “contain,” etc. used in this document are open-ended terms, meaning including but not limited to.

[0033] On the one hand, the present invention provides a method for preparing modified TPU waterproof and breathable formula particles, comprising the following steps:

[0034] (1) After the polyether polyol, anti-hydrolysis agent, antioxidant, light stabilizer, and ultraviolet absorber are heated and mixed uniformly, molten MDI and chain extender are added in proportion, extruded and granulated to obtain waterproof and breathable TPU particles;

[0035] (2) Preparation of diatomite masterbatch: kneading and granulating the waterproof and breathable TPU particles prepared in step (1) with diatomite powder to obtain a diatomite masterbatch with a diatomite content of 50 to 70%;

[0036] (3) Preparation of modified TPU waterproof and breathable formula particles: The waterproof and breathable TPU particles prepared in step (1) are evenly mixed with TPEE particles, diatomaceous earth masterbatch, and lubricant to obtain modified TPU waterproof and breathable formula particles.

[0037] Another aspect of the present invention provides a method for preparing a modified TPU waterproof and breathable membrane based on the modified TPU waterproof and breathable formula particles, comprising the following steps:

[0038] The modified TPU waterproof and breathable formula particles and PE particles are added to the extruder respectively, heated and melted and extruded to the inner layer and outer layer of the die head, and then compounded in the die at the die lip and blown into a modified TPU / PE composite film with a thickness of 0.025mm-0.045mm, with the modified TPU waterproof and breathable film on the outside. After cooling, the modified TPU waterproof and breathable film is trimmed and rolled up, wherein the thickness of the modified TPU waterproof and breathable film is 0.015mm-0.025mm.

[0039] Example 1

[0040] In Example 1 of the present invention, a modified TPU waterproof and breathable membrane is prepared, and the specific steps are as follows:

[0041] (1) 45 parts of polyether polyol, 0.5 parts of polycarbodiimide, 0.5 parts of antioxidant 1010, 0.5 parts of UV328, and 0.5 parts of BasfB75 were heated to 100° C. and mixed evenly, and then pumped into a polyurethane extruder through a metering pump with 45 parts of MDI and 8 parts of ethylene glycol in a molten state for granulation at an extruder temperature of 195° C. to obtain waterproof and breathable TPU particles;

[0042] (2) Preparation of diatomite masterbatch: The waterproof and breathable TPU particles prepared in step (1) are kneaded and granulated with diatomite powder to obtain a diatomite masterbatch with a diatomite content of 60%;

[0043] (3) Preparation of modified TPU waterproof and breathable formula particles: 80 parts of the waterproof and breathable TPU particles prepared in step (1) were mixed evenly with 8 parts of TPEE particles, 7 parts of diatomaceous earth masterbatch, and 5 parts of lubricant, and then dried at 100° C. for 8 hours to obtain modified TPU waterproof and breathable formula particles.

[0044] (4) Add the modified TPU waterproof and breathable formula particles and PE particles into the TPU film blowing machine (see Figure 2 ) extruder A and extruder B, heat and melt extrude to the inner layer and outer layer of the die head, through the die lip in-mold compound, according to the process of Table 1, blow molded into a modified TPU / PE composite film with a thickness of 0.025mm-0.045mm, wherein the thickness of the modified TPU film is 0.015mm-0.025mm, and the modified TPU waterproof and breathable membrane is on the outside (see Figure 1 ), and then trimmed and rolled after cooling. The properties of the modified TPU composite film were tested, and the results are shown in Table 2.

[0045] Table 1 Production process

[0046]

[0047]

[0048] Table 2 Performance

[0049]

[0050] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A waterproof and breathable TPU particle, characterized in that: The waterproof and breathable TPU particles are composed of the following raw materials in parts by weight: 35-45 parts of polyether polyol, 35-45 parts of MDI, 8-10 parts of chain extender, 0-1 part of anti-hydrolysis agent, 0-1 part of antioxidant, 0-1 part of light stabilizer, and 0-1 part of ultraviolet absorber.

2. The waterproof and breathable TPU particles according to claim 1, characterized in that: The polyether polyol includes one or more of PEG with a molecular weight of 1000, 2000, 3000 or PBA with a molecular weight of 1000, 2000, 3000.

3. The waterproof and breathable TPU particles according to claim 1, characterized in that: The chain extender includes one or more of ethylene glycol, butanediol, and hexanediol; the anti-hydrolysis agent is polycarbodiimide; the antioxidant is one or more of antioxidant 1010, antioxidant 168, and antioxidant 1076; the light stabilizer is BasfB75; and the ultraviolet absorber is one or more of UV328, UV326, and UV234.

4. A modified TPU waterproof and breathable formula particle prepared based on the waterproof and breathable TPU particle according to any one of claims 1 to 3, characterized in that: It is composed of the following raw materials in parts by weight: 80-90 parts of waterproof and breathable TPU particles, 0-10 parts of TPEE particles, 5-10 parts of diatomaceous earth masterbatch, and 0-5 parts of lubricant.

5. The modified TPU waterproof and breathable formula particles according to claim 4, characterized in that: The TPEE particles have a softening point of 185°C to 195°C, a melt index of 10 to 20 g / 10 min (220°C, 2160 g), and a moisture permeability of 6000 to 10000 g / m 2 ·24h; the lubricant is a particle made by blending TPU with oleamide or erucamide.

6. A method for preparing the modified TPU waterproof and breathable formula particles according to any one of claims 4 to 5, characterized in that: The steps include: (1) After the polyether polyol, anti-hydrolysis agent, antioxidant, light stabilizer, and ultraviolet absorber are heated and mixed uniformly, the mixture is pumped into a polyurethane extruder in proportion with MDI and a chain extender through a metering pump for reaction and granulation to obtain waterproof and breathable TPU particles; (2) Preparation of diatomaceous earth masterbatch: kneading and granulating the waterproof and breathable TPU particles prepared in step (1) with diatomaceous earth powder to obtain a diatomaceous earth masterbatch with a diatomaceous earth content of 50 to 70%; (3) Preparation of modified TPU waterproof and breathable formula particles: The waterproof and breathable TPU particles prepared in step (1) are evenly mixed with TPEE particles, diatomaceous earth masterbatch, and lubricant, and then dried to obtain modified TPU waterproof and breathable formula particles.

7. The method for preparing the modified TPU waterproof and breathable formula particles according to claim 6, characterized in that: The polyether polyol, anti-hydrolysis agent, antioxidant, light stabilizer and ultraviolet absorber in step (1) are heated to a temperature of 100° C.-110° C., and are pumped into an extruder in proportion with molten MDI and chain extender through a metering pump for reaction at a temperature of 195° C. for reaction granulation; the drying conditions in step (3) are 90-110° C. for 8-12 hours.

8. A method for preparing a modified TPU waterproof and breathable membrane based on the modified TPU waterproof and breathable formula particles according to any one of claims 1 to 5 or the modified TPU waterproof and breathable formula particles prepared by the preparation method according to any one of claims 6 to 7, characterized in that: The steps include: The modified TPU waterproof and breathable formula particles and PE particles are added to the A and B extruders respectively, heated and melted and extruded to the inner layer and outer layer of the die head, and then compounded in the die at the die lip and blown into a modified TPU / PE composite film with a thickness of 0.025mm-0.045mm, with the modified TPU waterproof and breathable film on the outside. After cooling, the modified TPU waterproof and breathable film is trimmed and rolled up, wherein the thickness of the modified TPU waterproof and breathable film is 0.015mm-0.025mm.

9. A TPU waterproof and breathable membrane prepared by the method for preparing a TPU waterproof and breathable membrane according to claim 8.

10. Use of the TPU waterproof and breathable membrane according to claim 9 in preparing waterproof and breathable materials.

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