WO2022057145A1 - 一种桌垫用环保型tpu薄膜及其制备方法 - Google Patents

一种桌垫用环保型tpu薄膜及其制备方法 Download PDF

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Publication number
WO2022057145A1
WO2022057145A1 PCT/CN2020/140454 CN2020140454W WO2022057145A1 WO 2022057145 A1 WO2022057145 A1 WO 2022057145A1 CN 2020140454 W CN2020140454 W CN 2020140454W WO 2022057145 A1 WO2022057145 A1 WO 2022057145A1
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Prior art keywords
parts
polyol
diisocyanate
temperature
tpu film
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PCT/CN2020/140454
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English (en)
French (fr)
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何建雄
杨博
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何建雄
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Publication of WO2022057145A1 publication Critical patent/WO2022057145A1/zh

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    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
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    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
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    • C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
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    • C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
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    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6275—Polymers of halogen containing compounds having carbon-to-carbon double bonds; halogenated polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6279—Polymers of halogen containing compounds having carbon-to-carbon double bonds; halogenated polymers of compounds having carbon-to-carbon double bonds containing fluorine atoms
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    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/6505—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6511—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38 compounds of group C08G18/3203
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Definitions

  • Thermoplastic polyurethane elastomer is a linear or a small amount of branched and cross-linked polymer material with hard segment and soft segment block structure. It is one of the six promising synthetic materials in the world.
  • the hardness range of TPU is quite wide (Shore A60-Shore D80), and it has high elasticity in the whole hardness range, good flexibility in a wide temperature range (-40 ⁇ 120), and it also has tensile strength High elongation, low compression set, wear resistance and tear resistance.
  • TPU materials have been widely used in conveyor belts, hoses, auto parts, shoe soles, synthetic leather, coatings, wires and cables and other fields.
  • the properties of TPU materials are often very large, and it is usually necessary to design specific molecular structures according to the application.
  • Desk pads are one of the application fields of TPU materials.
  • Traditional table mat materials include cloth, PVC (polyvinyl chloride), soft glass, and the like.
  • the cloth table mat has the advantage of cleaning, but it has no buffering effect, nor is it waterproof and oil-proof. Difficult to remove; soft glass table mats have similar disadvantages as PVC table mats.
  • TPU material is soft in texture and high in strength. Table pads using TPU have good cushioning properties, which can improve the comfort of human arms, and have been widely used in various pad products.
  • TPU also has the disadvantage of poor stain resistance.
  • slip resistance is also one of the indicators that table mat materials need to pay attention to, but it is often the opposite of stain resistance. Therefore, there is a need to study a table mat material with good stain resistance and adhesion.
  • the purpose of the present invention is to provide an environment-friendly TPU film for table pads and a preparation method thereof.
  • the TPU film has good stain resistance and adhesion, does not contain volatile organic substances, is safe and environmentally friendly, and is suitable for use in table mat products.
  • the present invention provides a kind of environment-friendly TPU film for table mat, and the TPU film includes the following raw material components in parts by weight:
  • thermosetting fluorocarbon resin and polyvinyl butyral can react with diisocyanate to form the main part of the molecular chain of the polyurethane material together with the oligomer polyol.
  • the thermosetting fluorocarbon resin contains a large amount of fluorine, which can significantly reduce the surface tension of the TPU film and improve the anti-fouling property of the TPU film, but at the same time, it will also lead to a low coefficient of friction of the TPU film, which is not easy to be attached to the desktop;
  • Polyvinyl butyral contains a large number of polar groups, which has good adhesion to wood fibers, metals and polymers, and helps to improve the friction between TPU films and desktops made of various materials.
  • the present invention obtains a TPU film that is soft in texture, anti-staining, firmly attached to the desktop, and not easy to slip through the coordination of the above-mentioned components.
  • the amount of thermosetting fluorocarbon resin and polyvinyl butyral needs to be kept within the above-mentioned range. If the amount of thermosetting fluorocarbon resin is too large, due to its poor compatibility with the polyurethane matrix, it is easy to cause the TPU film. The strength is low and the adhesion is poor; if the amount of polyvinyl butyral is too much, the surface of the TPU film is likely to be sticky, and it is easy to absorb solid particles and oil stains, and it is not easy to clean.
  • the weight parts of the diisocyanate can be 20 parts, 21 parts, 22 parts, 23 parts, 24 parts, 25 parts, 26 parts, 27 parts, 28 parts, 29 parts or 30 parts, etc.
  • the weight parts of the oligomer polyol can be 80 parts, 82 parts, 83 parts, 85 parts, 87 parts, 88 parts, 90 parts, 92 parts, 94 parts, 95 parts, 96 parts, 98 parts or 100 parts. copies etc.
  • the weight part of the thermosetting fluorocarbon resin can be 5 parts, 5.5 parts, 6 parts, 6.5 parts, 7 parts, 7.5 parts, 8 parts, 8.5 parts, 9 parts, 9.5 parts or 10 parts, etc.
  • the weight parts of the polyvinyl butyral can be 20 parts, 21 parts, 22 parts, 23 parts, 24 parts, 25 parts, 26 parts, 27 parts, 28 parts, 29 parts or 30 parts, etc.
  • the weight part of the chain extender can be 4 parts, 4.5 parts, 5 parts, 5.5 parts, 6 parts, 6.5 parts, 7 parts, 7.5 parts or 8 parts, etc.
  • the weight part of the catalyst can be 0.1 part, 0.2 part, 0.3 part, 0.4 part, 0.5 part, 0.6 part, 0.7 part, 0.8 part, 0.9 part or 1 part, etc.
  • the diisocyanates are aliphatic diisocyanates and/or aromatic diisocyanates.
  • the content of aliphatic diisocyanate in the diisocyanate is above 80wt%; for example, it may be 80wt%, 82wt%, 85wt%, 88wt%, 90wt%, 93wt%, 95wt%, 97wt% or 100wt%, etc.
  • the aliphatic diisocyanate is selected from one or a combination of at least two of hexamethylene diisocyanate, cyclohexane dimethylene diisocyanate and isophorone diisocyanate.
  • the aromatic diisocyanate is selected from one or a combination of at least two of the diisocyanates selected from toluene diisocyanate, diphenylmethane diisocyanate, p-phenylene diisocyanate or naphthalene diisocyanate.
  • the oligomer polyol is a polyether polyol and/or a polyester polyol.
  • the hydroxyl value of the polyether polyol is 75-80 mg KOH/g (for example, it may be 75 mg KOH/g, 76 mg KOH/g, 77 mg KOH/g, 78 mg KOH/g, 79 mg KOH/g or 80 mg KOH /g, etc.), the number average molecular weight is 1000-2000 (for example, it can be 1000, 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, 1900 or 2000, etc.).
  • the hydroxyl value of the polyester polyol is 50-60 mg KOH/g (for example, it can be 50 mg KOH/g, 51 mg KOH/g, 52 mg KOH/g, 53 mg KOH/g, 54 mg KOH/g, 55 mg KOH/g /g, 56mg KOH/g, 57mg KOH/g, 58mg KOH/g, 59mg KOH/g or 60mg KOH/g, etc.), the number average molecular weight is 2000-4000 (for example, it can be 2000, 2200, 2400, 2600, 2800 , 3000, 3200, 3400, 3600, 3800 or 4000, etc.).
  • the polyether polyol is selected from one or a combination of at least two of polyoxyethylene polyol, polyoxypropylene polyol, and polytetrahydrofuran polyol.
  • the polyester polyol is selected from one of polycaprolactone polyol, polyethylene adipate polyol, polyethylene adipate polyol, polycarbonate polyol or A combination of at least two.
  • thermosetting fluorocarbon resin is a trifluoroethylene-vinyl ether-vinyl ester copolymer.
  • the chain extender is selected from 1,4-butanediol, 1,6-hexanediol, diethylene glycol, diethylaminoethanol, N,N-dihydroxy (diisopropyl alcohol) base) one or a combination of at least two of aniline, ethylenediamine, 3,3'-dichloro-4,4'diamino-diphenylmethane.
  • the catalyst is selected from triethanolamine, N-methylmorphine, N,N'-bismorpholinyl diethyl ether, tetra-n-butyltin, stannous chloride, stannous octoate, One or a combination of at least two of hydroxytrimethyltin or dibutyltin dilaurate.
  • the TPU film further includes 8-15 parts of flame retardant
  • the flame retardant is selected from melamine, melamine cyanuric acid, melamine phosphate, triphenyl phosphate, tris( ⁇ -chloroethyl) phosphate (TCEP), tris( ⁇ -chloropropyl) phosphate ( One or a combination of at least two of TCPP), tris(2,3-dichloropropyl) phosphate (TDCPP), polyphosphate.
  • TCEP tris( ⁇ -chloroethyl) phosphate
  • TDCPP tris(2,3-dichloropropyl) phosphate
  • the present invention provides a TPU film preparation method as described in the first aspect, the preparation method comprising the following steps:
  • step (2) adding the mixed solution obtained in step (1) and other raw material components into the twin-screw extruder, and extruding while reacting to form TPU particles;
  • step (3) refining the TPU particles obtained in step (2) by an internal mixer, and then rolling to form a film to obtain the TPU film.
  • the dehydration in the step (1) is carried out under vacuum conditions.
  • the temperature of the feeding section of the twin-screw extruder in step (2) is 100-130°C (for example, it can be 100°C, 102°C, 105°C, 108°C, 112°C, 116°C, 119°C, 121°C, 124°C, 127°C or 130°C, etc.), the temperature of the mixing section is 130-160°C (for example, it can be 130°C, 134°C, 138°C, 141°C, 145°C, 149°C, 152°C, 155°C, 157°C or 160°C, etc.), the extrusion temperature is 160-200°C (for example, it can be 160°C, 163°C, 167°C, 170°C, 175°C, 180°C, 185°C, 190°C, 193°C, 196°C or 200°C, etc.), the head temperature is 150-200°C (for example, it can be 150°C,
  • the temperature of the banburying in step (3) is 180-220°C (for example, it can be 180°C, 184°C, 188°C, 191°C, 195°C, 200°C, 204°C, 208°C, 212°C, 216°C or 220°C, etc.), the time is 20-40min (for example, it can be 20min, 22min, 24min, 26min, 28min, 30min, 32min, 34min, 36min, 38min or 40min, etc.).
  • the temperature of the rolling in step (3) is 150-180°C, such as 150°C, 155°C, 160°C, 165°C, 170°C, 175°C or 180°C, etc.
  • the preparation method comprises the following steps:
  • step (2) adding the mixed solution obtained in step (1) and other raw material components into the twin-screw extruder, and controlling the temperature of the feeding section of the twin-screw extruder to be 100-130° C. and the temperature of the mixing section to be 130-130° C. 160°C, the extrusion temperature is 160-200°C, the die temperature is 150-200°C, extrude while reacting to form TPU particles;
  • step (3) adding the TPU particles obtained in step (2) into the internal mixer, banburying at 180-220° C. for 20-40 min, and then rolling at 150-180° C. to form a film to obtain the TPU film.
  • the present invention has the following beneficial effects:
  • the invention obtains a TPU film with good anti-contamination and adhesion properties by cooperating each component in a specific ratio, the anti-contamination of the TPU film reaches level 1, and the dry friction static friction coefficient reaches 1-1.2, and does not contain volatile organic substances, safe and environmentally friendly, suitable for use in table mat products.
  • Trifluoroethylene-vinyl ether-vinyl ester copolymer Asahi Glass Co., Ltd. Lumiflon LF710;
  • Polyvinyl butyral Japan Kuraray B20H.
  • the present embodiment provides an environment-friendly TPU film for table pads, comprising the following raw material components in parts by weight:
  • the diisocyanate is composed of hexamethylene diisocyanate and diphenylmethane diisocyanate in a weight ratio of 90:10, the hydroxyl value of the polyoxyethylene polyol is 78KOH/g, and the number average molecular weight is 1600.
  • the preparation method of above-mentioned environment-friendly TPU film is as follows:
  • step (2) adding the mixed solution obtained in step (1) and other raw material components into the twin-screw extruder, and controlling the temperature of the feeding section of the twin-screw extruder to be 110° C. and the temperature of the mixing section to be 140° C.
  • the temperature of the exit section is 180°C, and the temperature of the die head is 170°C, extruding while reacting to form TPU particles;
  • step (3) adding the TPU particles obtained in step (2) into an internal mixer, banburying at 200° C. for 30 minutes, and then rolling at 160° C. to form a film to obtain the above-mentioned environmentally friendly TPU film.
  • the present embodiment provides an environment-friendly TPU film for table pads, comprising the following raw material components in parts by weight:
  • the diisocyanate is composed of cyclohexane dimethylene diisocyanate and toluene diisocyanate in a weight ratio of 82:18
  • the oligomer polyol is composed of polytetrahydrofuran polyol and polycaprolactone polyol in a weight ratio of 50:50
  • the hydroxyl value of polytetrahydrofuran polyol is 75KOH/g
  • the number average molecular weight is 1000
  • the hydroxyl value of polycaprolactone polyol is 60KOH/g
  • the number average molecular weight is 4000.
  • the preparation method of above-mentioned environment-friendly TPU film is as follows:
  • step (2) adding the mixed solution obtained in step (1) and other raw material components into the twin-screw extruder, controlling the temperature of the feeding section of the twin-screw extruder to be 110°C, the temperature of the mixing section to be 130°C, and the extrusion
  • the temperature of the exit section is 170°C
  • the temperature of the die head is 180°C, extruding while reacting to form TPU particles;
  • step (3) adding the TPU particles obtained in step (2) into an internal mixer, banburying at 190° C. for 40 min, and then rolling at 150° C. to form a film to obtain the above-mentioned environmentally friendly TPU film.
  • This embodiment provides an environment-friendly TPU film for a desk pad. Including the following raw material components in parts by weight:
  • the oligomer polyol is composed of polytetrahydrofuran polyol and polycarbonate polyol in a weight ratio of 63:37, the hydroxyl value of the polytetrahydrofuran polyol is 75KOH/g, the number average molecular weight is 1000, and the hydroxyl value of the polycarbonate polyol is 75KOH/g. The value was 55 KOH/g, and the number average molecular weight was 3000.
  • the preparation method of above-mentioned environment-friendly TPU film is as follows:
  • step (2) adding the mixed solution obtained in step (1) and other raw material components into the twin-screw extruder, controlling the temperature of the feeding section of the twin-screw extruder to be 100°C, the temperature of the mixing section to be 145°C, and the extrusion
  • the temperature of the exit section is 160°C
  • the temperature of the die head is 160°C, extruding while reacting to form TPU particles;
  • step (3) adding the TPU particles obtained in step (2) into the Banbury mixer, banburying at 210° C. for 20 minutes, and then rolling at 170° C. to form a film to obtain the above-mentioned environmentally friendly TPU film.
  • the present embodiment provides an environment-friendly TPU film for table pads, comprising the following raw material components in parts by weight:
  • the diisocyanate is composed of isophorone diisocyanate and p-phenylene diisocyanate in a weight ratio of 85:15, the hydroxyl value of polyethylene adipate polyol is 50KOH/g, and the number average molecular weight is 2000.
  • the preparation method of above-mentioned environment-friendly TPU film is as follows:
  • step (2) adding the mixed solution obtained in step (1) and other raw material components into the twin-screw extruder, controlling the temperature of the feeding section of the twin-screw extruder to be 130°C, the temperature of the mixing section to be 150°C, and the extrusion
  • the temperature of the exit section is 200°C
  • the temperature of the die head is 150°C, extruding while reacting to form TPU particles
  • step (3) adding the TPU particles obtained in step (2) into the Banbury mixer, banburying at 180° C. for 25 minutes, and then rolling at 165° C. to form a film to obtain the above-mentioned environmentally friendly TPU film.
  • the present embodiment provides an environment-friendly TPU film for table pads, comprising the following raw material components in parts by weight:
  • the hydroxyl value of the polyoxypropylene polyol was 80 KOH/g, and the number average molecular weight was 2000.
  • the preparation method of above-mentioned environment-friendly TPU film is as follows:
  • step (2) adding the mixed solution obtained in step (1) and other raw material components into the twin-screw extruder, and controlling the temperature of the feeding section of the twin-screw extruder to be 120° C. and the temperature of the mixing section to be 160° C.
  • the temperature of the exit section is 190°C, and the temperature of the die head is 200°C, extruding while reacting to form TPU particles;
  • step (3) adding the TPU particles obtained in step (2) into the Banbury mixer, banburying at 220° C. for 35 minutes, and then rolling at 180° C. to form a film to obtain the above-mentioned environmentally friendly TPU film.
  • the present embodiment provides an environment-friendly TPU film for table pads, comprising the following raw material components in parts by weight:
  • the hydroxyl value of polyethylene adipate polyol was 57KOH/g, and the number average molecular weight was 3400.
  • the preparation method of above-mentioned environment-friendly TPU film is as follows:
  • step (2) adding the mixed solution obtained in step (1) and other raw material components into the twin-screw extruder, controlling the temperature of the feeding section of the twin-screw extruder to be 115°C, the temperature of the mixing section to be 155°C, and the extrusion
  • the temperature of the exit section is 175°C, and the temperature of the die head is 190°C, extruding while reacting to form TPU particles;
  • step (3) adding the TPU particles obtained in step (2) into an internal mixer, banburying at 195° C. for 20 min, and then rolling at 175° C. to form a film to obtain the above-mentioned environmentally friendly TPU film.
  • Example 2 The difference from Example 2 is that the weight fraction of the trifluoroethylene-vinyl ether-vinyl ester copolymer is 2 parts, and other parts are the same as those in Example 2.
  • Example 3 The difference from Example 3 is that the weight fraction of trifluoroethylene-vinyl ether-vinyl ester copolymer is 15 parts, and other parts are the same as those of Example 3.
  • Example 4 The difference from Example 4 is that the weight portion of polyvinyl butyral is 15 parts, and other parts are the same as those of Example 4.
  • Example 5 The difference from Example 5 is that the weight portion of polyvinyl butyral is 35 parts, and other parts are the same as those of Example 5.
  • Stain resistance According to the provisions of JGT 304-2011 standard, test the stain resistance of TPU film to oily markers; level 1 means it can be removed with dry lint-free cotton cloth, level 2 means weak cleaning with 1% neutral water Level 3 means that it can be removed with citrus-based cleaning agent, level 4 means it can be removed with anhydrous ethanol, and "non-removable” means that none of the above four cleaning materials can be removed or the material has lost its gloss, discolored or damaged after cleaning;
  • Dry friction static friction coefficient test according to the method of GB/T 3903.6-2005.
  • Example 3 1 1..02 Example 4 1 1.05 Example 5 1 1.12 Example 6 1 1.17 Comparative Example 1 3 1.21 Comparative Example 2 1 0.67 Comparative Example 3 1 0.85 Comparative Example 4 2 1.16
  • thermosetting fluorocarbon resin in Comparative Example 1 Compared with Example 2, the amount of thermosetting fluorocarbon resin in Comparative Example 1 is too small, and although the obtained TPU film has an improved coefficient of friction and better adhesion, its anti-fouling property is significantly reduced. Compared with Example 3, the amount of thermosetting fluorocarbon resin used in Comparative Example 2 is too much, resulting in lower surface tension of the TPU film, a significant decrease in friction coefficient, and poor adhesion.
  • Example 4 Compared with Example 4, the addition amount of polyvinyl butyral in Comparative Example 3 is too small, resulting in lower friction coefficient and poor adhesion of the TPU film. Compared with Example 5, the amount of polyvinyl butyral added in Comparative Example 4 was too large, resulting in a sticky surface of the TPU film, easy to absorb oil stains, and poor stain resistance.

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Abstract

一种桌垫用环保型TPU薄膜，包括如下重量份数的原料组分：二异氰酸酯20-30份、低聚物多元醇80-100份、热固性氟碳树脂5-10份、聚乙烯醇缩丁醛20-30份、扩链剂4-8份和催化剂0.1-1份。所述的TPU薄膜是通过将低聚物多元醇、热固性氟碳树脂和聚乙烯醇缩醛先脱水混合得到混合液，然后将混合液和其他原料组分通过挤出机挤出造粒，最后经密炼机密炼，辊压成膜制备得到。上述桌垫用环保型TPU薄膜具有良好的抗沾污性和贴附性、较高的柔性和强度，不含挥发性有机物质，安全环保，适用于桌垫产品中。

Description

一种桌垫用环保型TPU薄膜及其制备方法 技术领域
本公开基于申请号为202010988945.4，申请日为2020年09月18日的中国专利申请提出，并要求该中国专利申请的优先权，该中国专利申请的全部内容在此引入本申请作为参考。
背景技术
热塑性聚氨酯弹性体(TPU)是一种具有硬段和软段嵌段结构的线性或含有少量支化、交联的高分子材料，是当前世界六大具有发展前途的合成材料之一。TPU的硬度范围相当宽(邵氏A60-邵氏D80)，并且在整个硬度范围内具有高弹性，在很宽的温度范围内(-40～120)具有良好的柔性，其还具有拉伸强度高、伸长率大、压缩永久变形率低、耐磨和抗撕裂等优点。
随着技术的发展，TPU材料已广泛应用于传送带、软管、汽车零部件、鞋底、合成皮革、涂料、电线电缆等领域。根据应用领域的不同，TPU材料的性质往往有很大，通常需要根据用途设计特定的分子结构。
桌垫是TPU材料的应用领域之一。传统的桌垫材料包括布、PVC(聚氯乙烯)、软玻璃等。其中布质桌垫的优点是方面清洗，但其没有缓冲作用，也没有防水防油作用；PVC桌垫具有防水能力，但质地较硬，容易开裂，且使用一段时间后容易覆盖一层油污，难以清除；软玻璃桌垫同样具有与PVC桌垫类似的缺点。
TPU材料质地柔软，强度高，采用TPU的桌垫具有良好的缓冲性能，能够提高人手臂的舒适度，在各类垫产品中已广泛使用。但TPU作为有机聚合物材料，同样存在抗沾污性较差的缺点。此外，防滑性也是桌垫材料需要关注的指标之一，但其往往与抗沾污性相悖。因此，有待于研究一种兼具良好抗沾污性 和贴附性的桌垫材料。
发明内容
针对现有技术存在的不足，本发明的目的在于提供一种桌垫用环保型TPU薄膜及其制备方法。该TPU薄膜具有良好的抗沾污性和贴附性，不含挥发性有机物质，安全环保，适合用于桌垫产品中。
为达此目的，本发明采用以下技术方案：
第一方面，本发明提供一种桌垫用环保型TPU薄膜，所述TPU薄膜包括如下重量份数的原料组分：
二异氰酸酯20-30份、低聚物多元醇80-100份、热固性氟碳树脂5-10份、聚乙烯醇缩丁醛20-30份、扩链剂4-8份和催化剂0.1-1份。
本发明中，热固性氟碳树脂、聚乙烯醇缩丁醛能够与二异氰酸酯反应，与低聚物多元醇一起构成聚氨酯材料分子链的主要部分。其中，热固性氟碳树脂含有大量氟元素，能够显著降低TPU薄膜的表面张力，提高TPU薄膜的抗沾污性，但同时也会导致TPU薄膜的摩擦系数较低，不易于贴附在桌面上；聚乙烯醇缩丁醛含有大量极性基团，对木质纤维、金属、聚合物具有良好的粘附性，有助于提高TPU薄膜与各类材质的桌面之间的摩擦力。本发明通过上述组分之间的配合，从而得到了一种质地柔软，抗沾污，且能牢固贴附在桌面上，不易打滑的TPU薄膜。
本发明中，热固性氟碳树脂和聚乙烯醇缩丁醛的用量需要保持在上述范围内，若热固性氟碳树脂用量过多，由于其与聚氨酯基体的相容性不好，容易导致TPU薄膜的强度较低，贴附性较差；若聚乙烯醇缩丁醛的用量过多，则容易导致TPU薄膜表面较粘，容易吸附固体颗粒和油污，不易清洁。
本发明中，所述二异氰酸酯的重量份数可以是20份、21份、22份、23份、 24份、25份、26份、27份、28份、29份或30份等。
所述低聚物多元醇的重量份数可以是80份、82份、83份、85份、87份、88份、90份、92份、94份、95份、96份、98份或100份等。
所述热固性氟碳树脂的重量份数可以是5份、5.5份、6份、6.5份、7份、7.5份、8份、8.5份、9份、9.5份或10份等。
所述聚乙烯醇缩丁醛的重量份数可以是20份、21份、22份、23份、24份、25份、26份、27份、28份、29份或30份等。
所述扩链剂的重量份数可以是4份、4.5份、5份、5.5份、6份、6.5份、7份、7.5份或8份等。
所述催化剂的重量份数可以是0.1份、0.2份、0.3份、0.4份、0.5份、0.6份、0.7份、0.8份、0.9份或1份等。
以下作为本发明的优选技术方案，但不作为对本发明提供的技术方案的限制，通过以下优选地技术方案，可以更好地达到和实现本发明的目的和有益效果。
作为本发明的优选技术方案，所述二异氰酸酯为脂族二异氰酸酯和/或芳族二异氰酸酯。
优选地，所述二异氰酸酯中脂族二异氰酸酯的含量在80wt％以上；例如可以是80wt％、82wt％、85wt％、88wt％、90wt％、93wt％、95wt％、97wt％或100wt％等。
优选地，所述脂族二异氰酸酯选自六亚甲基二异氰酸酯、环己烷二亚甲基二异氰酸酯和异佛尔酮二异氰酸酯中的一种或至少两种的组合。
优选地，所述芳族二异氰酸酯选自二异氰酸酯选自甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、对苯二异氰酸酯或萘二异氰酸酯中的一种或至少两种的组 合。
作为本发明的优选技术方案，所述低聚物多元醇为聚醚多元醇和/或聚酯多元醇。
优选地，所述聚醚多元醇的羟值为75-80mg KOH/g(例如可以是75mg KOH/g、76mg KOH/g、77mg KOH/g、78mg KOH/g、79mg KOH/g或80mg KOH/g等)，数均分子量为1000-2000(例如可以是1000、1100、1200、1300、1400、1500、1600、1700、1800、1900或2000等)。
优选地，所述聚酯多元醇的羟值为50-60mg KOH/g(例如可以是50mg KOH/g、51mg KOH/g、52mg KOH/g、53mg KOH/g、54mg KOH/g、55mg KOH/g、56mg KOH/g、57mg KOH/g、58mg KOH/g、59mg KOH/g或60mg KOH/g等)，数均分子量为2000-4000(例如可以是2000、2200、2400、2600、2800、3000、3200、3400、3600、3800或4000等)。
优选地，所述聚醚多元醇选自聚氧化乙烯多元醇、聚氧化丙烯多元醇、聚四氢呋喃多元醇中的一种或至少两种的组合。
优选地，所述聚酯多元醇选自聚己内酯多元醇、聚己二酸己二醇酯多元醇、聚己二酸乙二醇酯多元醇、聚碳酸酯多元醇中的一种或至少两种的组合。
作为本发明的优选技术方案，所述热固性氟碳树脂为三氟乙烯-乙烯基醚-乙烯基酯共聚物。
作为本发明的优选技术方案，所述扩链剂选自1，4-丁二醇、1，6-己二醇、二甘醇、二乙氨基乙醇、N，N-二羟基(二异丙基)苯胺、乙二胺、3，3′-二氯-4，4′二氨基-二苯基甲烷中的一种或至少两种的组合。
作为本发明的优选技术方案，所述催化剂选自三乙醇胺、N-甲基吗琳、N，N′-双吗琳基二乙基醚、四正丁基锡、氯化亚锡、辛酸亚锡、羟基三甲基锡或二丁 基二月桂酸锡中的一种或至少两种的组合。
作为本发明的优选技术方案，所述TPU薄膜还包括8-15份阻燃剂；例如可以是8份、9份、10份、11份、12份、13份、14份或15份等。
优选地，所述阻燃剂选自三聚氰胺、三聚氰胺氰尿酸、三聚氰胺磷酸酯、磷酸三苯酯、磷酸三(β-氯乙基)酯(TCEP)、磷酸三(β-氯丙基)酯(TCPP)、磷酸三(2，3-二氯丙基)酯(TDCPP)、多磷酸酯中的一种或至少两种的组合。
第二方面，本发明提供一种如第一方面所述的TPU薄膜制备方法，所述的制备方法包括如下步骤：
(1)将低聚物多元醇、热固性氟碳树脂和聚乙烯醇缩醛脱水并混合；
(2)将步骤(1)得到的混合液和其他原料组分加入双螺杆挤出机中，边反应边挤出，形成TPU颗粒；
(3)将步骤(2)得到的TPU颗粒经密炼机密炼，然后辊压成膜，得到所述TPU薄膜。
作为本发明的优选技术方案，所述步骤(1)中所述脱水是在真空条件下进行。
优选地，步骤(2)中所述双螺杆挤出机的喂料段温度为100-130℃(例如可以是100℃、102℃、105℃、108℃、112℃、116℃、119℃、121℃、124℃、127℃或130℃等)，混合段温度为130-160℃(例如可以是130℃、134℃、138℃、141℃、145℃、149℃、152℃、155℃、157℃或160℃等)，挤出段温度为160-200℃(例如可以是160℃、163℃、167℃、170℃、175℃、180℃、185℃、190℃、193℃、196℃或200℃等)，机头温度为150-200℃(例如可以是150℃、155℃、160℃、165℃、170℃、175℃、180℃、185℃、190℃、195℃或200℃等)。
优选地，步骤(3)中所述密炼的温度为180-220℃(例如可以是180℃、184℃、188℃、191℃、195℃、200℃、204℃、208℃、212℃、216℃或220℃等)，时间为20-40min(例如可以是20min、22min、24min、26min、28min、30min、32min、34min、36min、38min或40min等)。
优选地，步骤(3)中所述辊压的温度为150-180℃，例如可以是150℃、155℃、160℃、165℃、170℃、175℃或180℃等。
作为本发明的优选技术方案，所述制备方法包括如下步骤：
(1)将低聚物多元醇、热固性氟碳树脂和聚乙烯醇缩醛混合，在-0.085～-0.095MPa的真空条件下脱水1-2h；
(2)将步骤(1)得到的混合液和其他原料组分加入双螺杆挤出机中，控制所述双螺杆挤出机的喂料段温度为100-130℃，混合段温度为130-160℃，挤出段温度为160-200℃，机头温度为150-200℃，边反应边挤出，形成TPU颗粒；
(3)将步骤(2)得到的TPU颗粒加入密炼机中，在180-220℃下密炼20-40min，然后在150-180℃下辊压成膜，得到所述TPU薄膜。
与现有技术相比，本发明具有以下有益效果：
本发明通过各组分在特定的比例下相互配合，得到了一种兼具良好抗沾污性和贴附性的TPU薄膜，该TPU薄膜的抗沾污性达到1级，干摩擦静摩擦系数达到1-1.2，且不含挥发性有机物质，安全环保，适合用于桌垫产品中。
具体实施方式
下面通过具体实施例来进一步说明本发明的技术方案。本领域技术人员应该明了，所述实施例仅仅是帮助理解本发明，不应视为对本发明的具体限制。
本发明实施例中采用的部分原料来源如下：
三氟乙烯-乙烯基醚-乙烯基酯共聚物：旭硝子株式会社Lumiflon LF710；
聚乙烯醇缩丁醛：日本可乐丽B20H。
实施例1：
本实施例提供一种桌垫用环保型TPU薄膜，包括如下重量份数的原料组分：
Figure PCTCN2020140454-appb-000001
其中，二异氰酸酯由六亚甲基二异氰酸酯和二苯基甲烷二异氰酸酯按重量比90∶10组成，聚氧化乙烯多元醇的羟基值为78KOH/g，数均分子量为1600。
上述环保型TPU薄膜的制备方法如下：
(1)将聚氧化乙烯多元醇、三氟乙烯-乙烯基醚-乙烯基酯共聚物和聚乙烯醇缩醛混合，在-0.085MPa的真空条件下脱水1h；
(2)将步骤(1)得到的混合液和其他原料组分加入双螺杆挤出机中，控制所述双螺杆挤出机的喂料段温度为110℃，混合段温度为140℃，挤出段温度为180℃，机头温度为170℃，边反应边挤出，形成TPU颗粒；
(3)将步骤(2)得到的TPU颗粒加入密炼机中，在200℃下密炼30min，然后在160℃下辊压成膜，得到上述环保型TPU薄膜。
实施例2：
本实施例提供一种桌垫用环保型TPU薄膜，包括如下重量份数的原料组分：
Figure PCTCN2020140454-appb-000002
Figure PCTCN2020140454-appb-000003
其中，二异氰酸酯由环己烷二亚甲基二异氰酸酯和甲苯二异氰酸酯按重量比82∶18组成，低聚物多元醇由聚四氢呋喃多元醇和聚己内酯多元醇按重量比50∶50组成，聚四氢呋喃多元醇的羟基值为75KOH/g，数均分子量为1000，聚己内酯多元醇的羟基值为60KOH/g，数均分子量为4000。
上述环保型TPU薄膜的制备方法如下：
(1)将聚四氢呋喃多元醇、聚己内酯多元醇、三氟乙烯-乙烯基醚-乙烯基酯共聚物和聚乙烯醇缩醛混合，在-0.05MPa的真空条件下脱水1.5h；
(2)将步骤(1)得到的混合液和其他原料组分加入双螺杆挤出机中，控制所述双螺杆挤出机的喂料段温度为110℃，混合段温度为130℃，挤出段温度为170℃，机头温度为180℃，边反应边挤出，形成TPU颗粒；
(3)将步骤(2)得到的TPU颗粒加入密炼机中，在190℃下密炼40min，然后在150℃下辊压成膜，得到上述环保型TPU薄膜。
实施例3：
本实施例提供一种桌垫用环保型TPU薄膜。包括如下重量份数的原料组分：
Figure PCTCN2020140454-appb-000004
Figure PCTCN2020140454-appb-000005
其中，低聚物多元醇由聚四氢呋喃多元醇和聚碳酸酯多元醇按重量比63∶37组成，聚四氢呋喃多元醇的羟基值为75KOH/g，数均分子量为1000，聚碳酸酯多元醇的羟基值为55KOH/g，数均分子量为3000。
上述环保型TPU薄膜的制备方法如下：
(1)将聚四氢呋喃多元醇、聚碳酸酯多元醇、三氟乙烯-乙烯基醚-乙烯基酯共聚物和聚乙烯醇缩醛混合，在0.015MPa的真空条件下脱水1.2h；
(2)将步骤(1)得到的混合液和其他原料组分加入双螺杆挤出机中，控制所述双螺杆挤出机的喂料段温度为100℃，混合段温度为145℃，挤出段温度为160℃，机头温度为160℃，边反应边挤出，形成TPU颗粒；
(3)将步骤(2)得到的TPU颗粒加入密炼机中，在210℃下密炼20min，然后在170℃下辊压成膜，得到上述环保型TPU薄膜。
实施例4：
本实施例提供一种桌垫用环保型TPU薄膜，包括如下重量份数的原料组分：
Figure PCTCN2020140454-appb-000006
Figure PCTCN2020140454-appb-000007
其中，二异氰酸酯由异佛尔酮二异氰酸酯和对苯二异氰酸酯按重量比85∶15组成，聚己二酸乙二醇酯多元醇的羟基值为50KOH/g，数均分子量为2000。
上述环保型TPU薄膜的制备方法如下：
(1)将聚己二酸己二醇酯多元醇、三氟乙烯-乙烯基醚-乙烯基酯共聚物和聚乙烯醇缩醛混合，在0.04MPa的真空条件下脱水2h；
(2)将步骤(1)得到的混合液和其他原料组分加入双螺杆挤出机中，控制所述双螺杆挤出机的喂料段温度为130℃，混合段温度为150℃，挤出段温度为200℃，机头温度为150℃，边反应边挤出，形成TPU颗粒；
(3)将步骤(2)得到的TPU颗粒加入密炼机中，在180℃下密炼25min，然后在165℃下辊压成膜，得到上述环保型TPU薄膜。
实施例5：
本实施例提供一种桌垫用环保型TPU薄膜，包括如下重量份数的原料组分：
Figure PCTCN2020140454-appb-000008
其中，聚氧化丙烯多元醇的羟基值为80KOH/g，数均分子量为2000。
上述环保型TPU薄膜的制备方法如下：
(1)将聚氧化丙烯多元醇、三氟乙烯-乙烯基醚-乙烯基酯共聚物和聚乙烯 醇缩醛混合，在0.065MPa的真空条件下脱水1.8h；
(2)将步骤(1)得到的混合液和其他原料组分加入双螺杆挤出机中，控制所述双螺杆挤出机的喂料段温度为120℃，混合段温度为160℃，挤出段温度为190℃，机头温度为200℃，边反应边挤出，形成TPU颗粒；
(3)将步骤(2)得到的TPU颗粒加入密炼机中，在220℃下密炼35min，然后在180℃下辊压成膜，得到上述环保型TPU薄膜。
实施例6：
本实施例提供一种桌垫用环保型TPU薄膜，包括如下重量份数的原料组分：
Figure PCTCN2020140454-appb-000009
其中，聚己二酸乙二醇酯多元醇的羟基值为57KOH/g，数均分子量为3400。
上述环保型TPU薄膜的制备方法如下：
(1)将聚氧化丙烯多元醇、三氟乙烯-乙烯基醚-乙烯基酯共聚物和聚乙烯醇缩醛混合，在0.095MPa的真空条件下脱水1.6h；
(2)将步骤(1)得到的混合液和其他原料组分加入双螺杆挤出机中，控制所述双螺杆挤出机的喂料段温度为115℃，混合段温度为155℃，挤出段温度为175℃，机头温度为190℃，边反应边挤出，形成TPU颗粒；
(3)将步骤(2)得到的TPU颗粒加入密炼机中，在195℃下密炼20min， 然后在175℃下辊压成膜，得到上述环保型TPU薄膜。
对比例1
与实施例2的区别在于，三氟乙烯-乙烯基醚-乙烯基酯共聚物的重量份数为2份，其他与实施例2相同。
对比例2
与实施例3的区别在于，三氟乙烯-乙烯基醚-乙烯基酯共聚物的重量份数为15份，其他与实施例3相同。
对比例3
与实施例4的区别在于，聚乙烯醇缩丁醛的重量份数为15份，其他与实施例4相同。
对比例4
与实施例5的区别在于，聚乙烯醇缩丁醛的重量份数为35份，其他与实施例5相同。
对上述实施例和对比例提供的TPU薄膜的性能进行测试，测试标准如下：
抗沾污性：按照JGT 304-2011标准的规定，测试TPU薄膜对于油性记号笔以的抗沾污性；1级表示用干无绒棉布可清除，2级表示用1％中性水性弱清洗剂可清除，3级表示用柑橘基清洗剂可清除，4级表示用无水乙醇可清除，“不可清除”表示上述四种清洗材料均不能清除或清洗后材料失光变色或损伤；
干摩擦静摩擦系数：按照GB/T 3903.6-2005的方法测试。
上述性能的测试结果如下表1所示：
表1
测试项目 抗沾污性 干摩擦静摩擦系数
实施例1 1 1.08
实施例2 1 1.13
实施例3 1 1..02
实施例4 1 1.05
实施例5 1 1.12
实施例6 1 1.17
对比例1 3 1.21
对比例2 1 0.67
对比例3 1 0.85
对比例4 2 1.16
由表1的结果可以看出，本发明提供的TPU薄膜的抗沾污性达到1级，干摩擦静摩擦系数达到1-1.2，具有良好的抗沾污性和贴附性，不含挥发性有机物质，安全环保，适合用于桌垫产品中。
其中，与实施例2相比，对比例1中热固性氟碳树脂的用量过少，得到的TPU薄膜虽然摩擦系数提高，贴附性更好，但抗沾污性明显下降。与实施例3相比，对比例2中热固性氟碳树脂的用量过多，导致TPU薄膜的表面张力较低，摩擦系数明显下降，贴附性变差。
与实施例4相比，对比例3中聚乙烯醇缩丁醛的添加量过少，导致TPU薄膜的摩擦系数较低，贴附性变差。与实施例5相比，对比例4中聚乙烯醇缩丁醛的添加量过多，导致TPU薄膜表面较粘，容易吸附油污，抗沾污性较差。
申请人声明，以上所述仅为本发明的具体实施方式，但本发明的保护范围并不局限于此，所属技术领域的技术人员应该明了，任何属于本技术领域的技术人员在本发明揭露的技术范围内，可轻易想到的变化或替换，均落在本发明的保护范围和公开范围之内。

Claims (10)

  1. 一种桌垫用环保型TPU薄膜，其特征在于，所述TPU薄膜包括如下重量份数的原料组分：
    二异氰酸酯20-30份、低聚物多元醇80-100份、热固性氟碳树脂5-10份、聚乙烯醇缩丁醛20-30份、扩链剂4-8份和催化剂0.1-1份。
  2. 根据权利要求1所述的TPU薄膜，其特征在于，所述二异氰酸酯为脂族二异氰酸酯和/或芳族二异氰酸酯；
    优选地，所述二异氰酸酯中脂族二异氰酸酯的含量在80wt％以上；
    优选地，所述脂族二异氰酸酯选自六亚甲基二异氰酸酯、环己烷二亚甲基二异氰酸酯和异佛尔酮二异氰酸酯中的一种或至少两种的组合；
    优选地，所述芳族二异氰酸酯选自甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、对苯二异氰酸酯或萘二异氰酸酯中的一种或至少两种的组合。
  3. 根据权利要求1或2所述的TPU薄膜，其特征在于，所述低聚物多元醇为聚醚多元醇和/或聚酯多元醇；
    优选地，所述聚醚多元醇的羟值为75-80mg KOH/g，数均分子量为1000-2000；
    优选地，所述聚酯多元醇的羟值为50-60mg KOH/g，数均分子量为2000-4000；
    优选地，所述聚醚多元醇选自聚氧化乙烯多元醇、聚氧化丙烯多元醇、聚四氢呋喃多元醇中的一种或至少两种的组合；
    优选地，所述聚酯多元醇选自聚己内酯多元醇、聚己二酸己二醇酯多元醇、聚己二酸乙二醇酯多元醇、聚碳酸酯多元醇中的一种或至少两种的组合。
  4. 根据权利要求1-3任一项所述的TPU薄膜，其特征在于，所述热固性氟碳树脂为三氟乙烯-乙烯基醚-乙烯基酯共聚物。
  5. 根据权利要求1-4任一项所述的TPU薄膜，其特征在于，所述扩链剂选自1，4-丁二醇、1，6-己二醇、二甘醇、二乙氨基乙醇、N，N-二羟基(二异丙基)苯胺、乙二胺、3，3′-二氯-4，4′二氨基-二苯基甲烷中的一种或至少两种的组合。
  6. 根据权利要求1-5任一项所述的TPU薄膜，其特征在于，所述催化剂选自三乙醇胺、N-甲基吗琳、N，N′-双吗琳基二乙基醚、四正丁基锡、氯化亚锡、辛酸亚锡、羟基三甲基锡或二丁基二月桂酸锡中的一种或至少两种的组合。
  7. 根据权利要求1-6任一项所述的TPU薄膜，其特征在于，所述TPU薄膜还包括8-15份阻燃剂；
    优选地，所述阻燃剂选自三聚氰胺、三聚氰胺氰尿酸、三聚氰胺磷酸酯、磷酸三苯酯、磷酸三(β-氯乙基)酯、磷酸三(β-氯丙基)酯、磷酸三(2，3-二氯丙基)酯、多磷酸酯中的一种或至少两种的组合。
  8. 一种如权利要求1-7任一项所述的TPU薄膜的制备方法，其特征在于，所述制备方法包括如下步骤：
    (1)将低聚物多元醇、热固性氟碳树脂和聚乙烯醇缩醛脱水并混合；
    (2)将步骤(1)得到的混合液和其他原料组分加入双螺杆挤出机中，边反应边挤出，形成TPU颗粒；
    (3)将步骤(2)得到的TPU颗粒经密炼机密炼，然后辊压成膜，得到所述TPU薄膜。
  9. 根据权利要求8所述的制备方法，其特征在于，步骤(1)中所述脱水是在真空条件下进行；
    优选地，步骤(2)中所述双螺杆挤出机的喂料段温度为100-130℃，混合段温度为130-160℃，挤出段温度为160-200℃，机头温度为150-200℃；
    优选地，步骤(3)中所述密炼的温度为180-220℃，时间为20-40min；
    优选地，步骤(3)中所述辊压的温度为150-180℃。
  10. 根据权利要求8或9所述的制备方法，其特征在于，所述制备方法包括如下步骤：
    (1)将低聚物多元醇、热固性氟碳树脂和聚乙烯醇缩醛混合，在-0.085～-0.095MPa的真空条件下脱水1-2h；
    (2)将步骤(1)得到的混合液和其他原料组分加入双螺杆挤出机中，控制所述双螺杆挤出机的喂料段温度为100-130℃，混合段温度为130-160℃，挤出段温度为160-200℃，机头温度为150-200℃，边反应边挤出，形成TPU颗粒；
    (3)将步骤(2)得到的TPU颗粒加入密炼机中，在180-220℃下密炼20-40min，然后在150-180℃下辊压成膜，得到所述TPU薄膜。
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