WO2022095149A1 - Fabric laminate of recycled modified pvb and preparation method therefor - Google Patents

Fabric laminate of recycled modified pvb and preparation method therefor Download PDF

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Publication number
WO2022095149A1
WO2022095149A1 PCT/CN2020/131046 CN2020131046W WO2022095149A1 WO 2022095149 A1 WO2022095149 A1 WO 2022095149A1 CN 2020131046 W CN2020131046 W CN 2020131046W WO 2022095149 A1 WO2022095149 A1 WO 2022095149A1
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Prior art keywords
pvb
layer
fabric
modified pvb
modified
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PCT/CN2020/131046
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French (fr)
Chinese (zh)
Inventor
封利苹
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杭州盛得新材料有限公司
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Publication of WO2022095149A1 publication Critical patent/WO2022095149A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/42—Layered products comprising a layer of synthetic resin comprising condensation resins of aldehydes, e.g. with phenols, ureas or melamines
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/08—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the cooling method
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
    • C08J2329/14—Homopolymers or copolymers of acetals or ketals obtained by polymerisation of unsaturated acetals or ketals or by after-treatment of polymers of unsaturated alcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/101—Esters; Ether-esters of monocarboxylic acids
    • C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/11—Esters; Ether-esters of acyclic polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds

Definitions

  • the invention relates to a laminated fabric, in particular to a laminated fabric of recycled modified PVB and a preparation method thereof.
  • Laminated fabrics also known as bonded fabrics, laminated fabrics. It refers to the bonding of fabrics and other soft sheet materials to form composite materials with multiple functions, which are used in raincoats, tents, etc.
  • the newly formed plastic film and fabric can be laminated to form artificial leather products. It can not only improve the appearance and feel of the fabric, but also improve the function of the fabric, such as making the fabric have special functions such as waterproof, breathable and moisture-permeable, flame-retardant and anti-fouling, and light-shielding reflection.
  • US Patent US8486848 also introduces a PVB fabric composite material, the fabric is directly composited with PVB or is also composited with PVB through an adhesive layer.
  • the direct compounding of the fabric with PVB has the disadvantage of low adhesive strength, and the compounding through the adhesive layer will have the above-mentioned disadvantages such as complicated production process, harsh production environment and high cost.
  • the present invention aims to solve the above-mentioned problems, thereby providing a fabric laminate for recycling modified PVB.
  • the present invention uses PVB material recovered from automobile front windshield or building laminated glass as raw material, and is obtained by mixing with inorganic filler, plasticizer, isocyanate, etc., and then calendering into film and directly compounding with fabric.
  • the present invention improves the adhesion performance between the PVB layer and the fabric layer by modifying the recovered PVB.
  • a fabric laminate for recycling modified PVB comprising a fabric layer and a modified PVB layer compounded on at least one surface of the fabric layer, the thickness of the modified PVB layer is 0.02-2 mm, and the
  • the raw material of the modified PVB layer includes the following components by mass:
  • the utilization ratio of recycled PVB is 40% to 100%.
  • the recovered PVB can be PVB films recovered from automobile front windshields or laminated glass used in buildings, or these films are subjected to preliminary treatment, such as removing impurities, cleaning, drying, and breaking.
  • the recycled PVB can also be the leftovers of PVB films produced in the production process of automobile front windshields and building laminated glass.
  • the preparation method of the modified PVB layer comprises the following steps:
  • the inorganic filler is first treated with a silane coupling agent, specifically, the inorganic filler and the silane coupling agent are mixed and dispersed in a high-speed mixer for 5 to 20 minutes;
  • the isocyanate is selected from one of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, lysine diisocyanate or multiple, or one or more of the prepolymers of the aforementioned isocyanates.
  • the plasticizer is selected from triethylene glycol diisocaprylate, tetraethylene glycol diheptanoate, dibutyl sebacate, dioctyl sebacate, dioctyl adipate, para One or more of dioctyl phthalate.
  • the antioxidant includes a main antioxidant and an auxiliary antioxidant;
  • the main antioxidant is a hindered phenolic antioxidant, selected from one of BASF antioxidants IRGANOX1010, IRGANOX1076, IRGANOX1098 or Multiple
  • the auxiliary antioxidant is selected from BASF IRGAFOS 168, IRGAFOS 126, IRGAFOS One or more of P-EPQ.
  • the fabric layer is made of a kind of yarn selected from polyester, acrylic, nylon, vinylon, spandex, polypropylene, and vegetable fibers or a blended yarn in any proportion by weaving or knitting;
  • the yarn denier of the fabric substrate is 20-4800D.
  • the formula raw materials are refined into rubber material through the rubber mixing process, and then the rubber material is pressed into a continuous sheet by a calender, and then the above-mentioned rolled fabric layer is re-unrolled, and the modified material is re-rolled.
  • the continuous flakes are compounded together by a laminating machine. During the lamination process, if the continuous flakes have cooled, they need to be heated.
  • the laminated fabric is passed through a set of cooling rolls, and the finished product is obtained after cooling.
  • the present invention adopts the scheme of modifying PVB, using isocyanate and/or its prepolymer to modify PVB, so that it can produce sufficient adhesion to the fabric substrate. This avoids a pre-operation of glue curing on the fabric layer.
  • the modified PVB layer can be directly and firmly adhered to the fabric substrate layer without using the adhesive and its supporting process.
  • the modified PVB layer increases the bonding ability with the fabric fibers, which is mainly achieved by adding an isocyanate-based co-binder.
  • Adding isocyanate through the reaction between isocyanate and the hydroxyl group in PVB, can improve the bonding force with the fabric fiber, and make a certain degree of cross-linking between PVB, improve the mechanical properties of PVB layer.
  • the addition amount of isocyanate should not be too much, too much addition will make the PVB cross-linking reaction excessive, causing processing difficulties, and will also make the PVB layer tend to hard plasticize.
  • the addition amount of the isocyanate is 0.1-10%, preferably 0.2-2%.
  • the timing of adding isocyanate should be carried out after the addition of other additives and a certain degree of refining.
  • inorganic fillers can increase the density of the PVB layer, which improves the overall texture, and on the other hand, can improve the mechanical properties of the product, such as scratch resistance and tensile strength.
  • the addition amount of inorganic fillers should not be too much. Too much addition will not only make the PVB layer too heavy, but also make the PVB layer tend to be petrochemical.
  • the amount of plasticizer can generally be determined according to needs. The increase in the proportion of plasticizer will soften the hand of the PVB layer, thereby improving the touch. Usually, it is more appropriate to set the amount of plasticizer to be 0.1 to 10.0 parts by mass; more preferably 0.5 to 8.0 parts by mass.
  • Another object of the present invention is to provide a method for the above-mentioned composite polymer coated fabric, the method comprising the following steps:
  • the fabric layer is first treated with corona equipment, so that the surface energy of the fabric layer is reduced and the adhesion with the PVB layer is enhanced;
  • the inorganic filler is firstly surface-treated with a silane coupling agent, specifically, the inorganic filler and the silane coupling agent are mixed and dispersed in a high-speed mixer for 5-20 minutes;
  • step S3 the inorganic filler obtained through the treatment of step S2 and the recovered PVB, isocyanate, plasticizer, antioxidant and lubricant are mixed with an internal mixer and an open mixer, and then extruded through a screw extruder,
  • the modified PVB film is obtained by calendering;
  • step S4 make the fabric layer obtained by the treatment of step S1 and the modified PVB film obtained by the treatment of step S3 heat-compressed and bonded by a hot-press laminating machine, and then cool down by a cooling roller group to obtain the fabric laminate.
  • step S2 is specifically:
  • the inorganic filler is first treated with a silane coupling agent, specifically, the inorganic filler and the silane coupling agent are mixed and dispersed in a high-speed mixer for 5 to 20 minutes;
  • Another object of the present invention is to provide the above-mentioned recycled modified PVB fabric laminate in raincoats, umbrellas, tents, covers, bags, luggage, shoes, clothes, chairs, sofas, cushions, pillows, sporting goods, writing implements, toys , baby products, horse clothing, pets.
  • the present invention has the following beneficial effects:
  • the quality of the laminated fabric is mainly reflected in the surface strength, hand feel, and wrinkle recovery after buckling of the coating; the surface strength is mainly reflected in the scratch resistance; the fabric laminate of recycled modified PVB provided by the present invention has good properties. Scratch, flexibility and resistance to stress, and because the material is halogen-free, no toxic substances are produced during degradation.
  • the modified PVB layer prepared by the invention has high mechanical strength, good weather resistance and soft hand feeling.
  • the present invention modifies the recycled PVB by using isocyanate and/or isocyanate prepolymer, so that sufficient self-adhesion between the PVB layer and the fabric layer can be produced, so that gluing on the fabric layer can be avoided. It solves a series of problems caused by gluing, such as workshop environmental pollution, complex process, and high production cost. It has a good promotion for the reuse of recovered PVB in laminated glass.
  • the preparation method of the fabric laminate of above-mentioned recycled modified PVB is as follows:
  • the fabric layer is first treated with corona equipment, so that the surface energy of the fabric layer is reduced and the adhesion with the PVB layer is enhanced;
  • step S4 make the fabric layer obtained through the treatment of step S1 and the modified PVB layer obtained by the treatment of step S3 through the hot-pressing laminating machine, and then pass the cooling roller set to cool down to obtain the fabric laminate.
  • a fabric laminate for recycling modified PVB comprising a fabric layer and a modified PVB layer compounded on one surface of the fabric layer, and the thickness of the modified PVB layer is 1.0 mm.
  • the fabric base material is made of polyester yarn selected from the plain weave process.
  • the preparation method of the fabric laminate of above-mentioned recycled modified PVB is as follows:
  • the fabric layer is first treated with corona equipment, so that the surface energy of the fabric layer is reduced and the adhesion with the PVB layer is enhanced;
  • step S4 make the fabric layer obtained through the treatment of step S1 and the modified PVB layer obtained by the treatment of step S3 through the hot-pressing laminating machine, and then pass the cooling roller set to cool down to obtain the fabric laminate.
  • a fabric laminate for recycling modified PVB the laminate comprises a fabric layer and a modified PVB layer compounded on one surface of the fabric layer, and the thickness of the modified PVB layer is 0.8 mm.
  • the fabric base material is made of polyester yarn selected from the plain weave process.
  • the preparation method of the fabric laminate of above-mentioned recycled modified PVB is as follows:
  • the fabric layer is first treated with corona equipment, so that the surface energy of the fabric layer is reduced and the adhesion with the PVB layer is enhanced;
  • step S4 make the fabric layer obtained through the treatment of step S1 and the modified PVB layer obtained by the treatment of step S3 through the hot-pressing laminating machine, and then pass the cooling roller set to cool down to obtain the fabric laminate.
  • a fabric laminate for recycling modified PVB the laminate comprises a fabric layer and a modified PVB layer compounded on one surface of the fabric layer, and the thickness of the modified PVB layer is 0.6 mm.
  • the fabric base material is made of polyester yarn selected from the plain weave process.
  • the preparation method of the fabric laminate of above-mentioned recycled modified PVB is as follows:
  • the fabric layer is first treated with corona equipment, so that the surface energy of the fabric layer is reduced and the adhesion with the PVB layer is enhanced;
  • step S4 make the fabric layer obtained through the treatment of step S1 and the modified PVB layer obtained by the treatment of step S3 through the hot-pressing laminating machine, and then pass the cooling roller set to cool down to obtain the fabric laminate.
  • a fabric laminate for recycling modified PVB the laminate comprises a fabric layer and a modified PVB layer compounded on one surface of the fabric layer, and the thickness of the modified PVB layer is 0.6 mm.
  • the fabric base material is made of polyester yarn selected from the plain weave process.
  • the preparation method of the fabric laminate of above-mentioned recycled modified PVB is as follows:
  • the fabric layer is first treated with corona equipment, so that the surface energy of the fabric layer is reduced and the adhesion with the PVB layer is enhanced;
  • step S4 make the fabric layer obtained through the treatment of step S1 and the modified PVB layer obtained by the treatment of step S3 through the hot-pressing laminating machine, and then pass the cooling roller set to cool down to obtain the fabric laminate.
  • the samples prepared in Examples 1, 2, 3, 4, and 5 were taken as samples, which were recorded as Sample 1, Sample 2, Sample 3, Sample 4, and Sample 5, respectively.
  • the sample width is 10cm.
  • the test is carried out on a common strength machine.
  • the two layers of the sample are subjected to opposite tensile forces in two directions to peel off; during the peeling process of the sample, with the increase of the tensile force, the automatic recorder can continue to A rising curve is drawn, and when the tensile force is loaded to a certain magnitude, the adhesion between the fabric layer and the PVB layer on the force line is destroyed, and the two are separated. At this time, the tensile force decreases rapidly, recording The instrument draws a descending curve, and the intersection of the ascending curve and the descending curve forms a "peak".
  • the peaks represent the tensile force required to separate the PVB layer and the fabric layer at different positions of the sample. Obviously, the larger the peaks, the stronger the bond is, while the peaks and valleys represent different positions. The value of the tensile force reduction during the separation of the upper PVB from the fabric layer, therefore, the test of bond firmness mainly focuses on the peak value.
  • the first is the number of peaks on the force curve.
  • the force curve must produce a "peak” at the breaking point, but if the specimen is very uniformly bonded, the magnitude of the peaks produced by each peel line will be nearly equal. Then the force curve will be a curve close to the horizontal line without peaks. "Peaks" appear only when the breaking strengths of the individual peel lines are unequal in size. Therefore, whether there is a peak in the stress curve, and the number of peaks depends on the adhesion of the sample.
  • the fabric layer is non-uniform, it is a woven plain weave, and the PVB layer is intercalated with it to a certain extent. There are gaps. At the same time, the protruding parts of the fabric layer are closely bonded to the PVB layer, while the protruding parts of the fabric layer are loosely bonded to the PVB layer. Therefore, a large number of peaks and valleys must appear in the sample during the peeling process.
  • the peeling test of samples 1, 2, 3, 4, and 5 is carried out, and the results are shown in the following table.
  • the test method is to record all the peaks on the stress curve during the peeling process of the sample, and then calculate the average value of these peaks and the discrete relationship between the peaks.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Fluid Mechanics (AREA)
  • Laminated Bodies (AREA)

Abstract

A fabric laminate of recycled modified PVB and a preparation method therefor. The fabric laminate comprises a fabric layer and a modified PVB layer composited on a surface of the fabric layer, wherein the thickness of the modified PVB layer is 0.02-2 mm; and the raw materials for the modified PVB layer include: 20-99 parts of PVB, 0.1-10 parts of an isocyanate, 0.4-60 parts of an inorganic filler, 0.1-2.0 parts of a silane coupling agent, 0.1-10.0 parts of a plasticizer, 0.1-2.0 parts of an antioxidant, and 0.5-3.0 parts of a lubricant, wherein the usage proportion of the recycled PVB is 0.1-100%. By modifying the recycled PVB with an isocyanate and/or an isocyanate prepolymer, sufficient self-adhesion is generated between the PVB layer and the fabric layer, thereby avoiding performing gluing on the fabric layer. A series of problems such as a polluted workshop environment, a complex process, and a high production cost caused by gluing are thus solved.

Description

一种回收改性PVB的织物层压体及其制备方法A fabric laminate of recycled modified PVB and preparation method thereof 技术领域technical field
本发明涉及一种层压织物，尤其涉及一种回收改性PVB的层压织物及其制备方法。The invention relates to a laminated fabric, in particular to a laminated fabric of recycled modified PVB and a preparation method thereof.
背景技术Background technique
层压织物，又称粘合织物、叠层织物。是指将织物与其他软片材料黏结在一起，形成兼有多种功能的复合材料，应用于雨衣、帐篷等。可在压延机上，把刚形成的塑料薄膜和织物贴合，层压成人造革类产品。它不仅能改善织物的外观和手感，还能改善织物的功能，诸如使织物具有防水、通气透湿、阻燃防污以及遮光反射等特殊功能。Laminated fabrics, also known as bonded fabrics, laminated fabrics. It refers to the bonding of fabrics and other soft sheet materials to form composite materials with multiple functions, which are used in raincoats, tents, etc. On the calender, the newly formed plastic film and fabric can be laminated to form artificial leather products. It can not only improve the appearance and feel of the fabric, but also improve the function of the fabric, such as making the fabric have special functions such as waterproof, breathable and moisture-permeable, flame-retardant and anti-fouling, and light-shielding reflection.
技术问题technical problem
现有技术中，常用PVC来进行层压织物或者涂层织物的制造。该产品的优点是，价格便宜，柔软性好，弹性佳，并具有一定的耐腐蚀性；但其低温柔软性差，并且有毒性，降解时易产生戴奥辛类剧毒物质。In the prior art, PVC is commonly used for the manufacture of laminated fabrics or coated fabrics. The product has the advantages of low price, good flexibility, good elasticity, and certain corrosion resistance; but its low temperature flexibility is poor, and it is toxic, and it is easy to produce dioxin-like highly toxic substances when degraded.
聚乙烯醇缩丁醛（PVB）夹胶玻璃因其优异的光学性能、耐老化性能和安全性能在汽车、建筑安全玻璃领域得到了广泛的应用。然而夹胶玻璃作为损耗品，汽车挡风玻璃和建筑夹胶安全玻璃每年的报废量是巨大的。如何将这些报废的夹胶玻璃回收再利用成为了工业界和环保领域的重要研究课题。Polyvinyl butyral (PVB) laminated glass has been widely used in the fields of automotive and architectural safety glass due to its excellent optical properties, aging resistance and safety performance. However, laminated glass is a consumable product, and the annual scrap of automobile windshield and architectural laminated safety glass is huge. How to recycle these scrapped laminated glass has become an important research topic in the field of industry and environmental protection.
中国专利CN104441886，介绍了一种回收利用夹胶玻璃的方法。它主要是将回收的PVB膜干燥造粒后流延或者压延成膜与纺织物复合做成水面料。然而其在做纺织物与PVB膜中间还有一层聚氨酯的粘结层来增加PVB膜与聚氨酯层的粘结力。聚氨酯层的存在使得生产过程复杂，聚氨酯在涂布过程中使用的溶剂也使得生产环境恶劣，成本也大幅增加。Chinese patent CN104441886 introduces a method for recycling laminated glass. It mainly uses the recycled PVB film after drying and granulation, casting or calendering to form film and compounding with textile to make water fabric. However, it also has a polyurethane adhesive layer between the textile and the PVB film to increase the adhesion between the PVB film and the polyurethane layer. The existence of the polyurethane layer complicates the production process, and the solvent used in the coating process of the polyurethane also makes the production environment harsh and the cost increases significantly.
美国专利US8486848也介绍了一种PVB织物复合材料，织物与PVB直接复合或者也是也通过粘结层与PVB复合。织物直接与PVB复合存在接着强度不高的缺点，而通过粘结层来复合又会有上述的生产过程复杂，生产环境恶劣，成本较高等缺点。US Patent US8486848 also introduces a PVB fabric composite material, the fabric is directly composited with PVB or is also composited with PVB through an adhesive layer. The direct compounding of the fabric with PVB has the disadvantage of low adhesive strength, and the compounding through the adhesive layer will have the above-mentioned disadvantages such as complicated production process, harsh production environment and high cost.
技术解决方案technical solutions
本发明要解决上述问题，从而提供一种回收改性PVB的织物层压体。本发明使用从汽车前风挡或者是建筑夹层玻璃中回收得到的PVB材料为原料，通过与无机填料、增塑剂、异氰酸酯等混炼后，再经压延成膜与织物直接复合得到。本发明通过改性回收的PVB来提升PVB层与织物层的粘接性能。The present invention aims to solve the above-mentioned problems, thereby providing a fabric laminate for recycling modified PVB. The present invention uses PVB material recovered from automobile front windshield or building laminated glass as raw material, and is obtained by mixing with inorganic filler, plasticizer, isocyanate, etc., and then calendering into film and directly compounding with fabric. The present invention improves the adhesion performance between the PVB layer and the fabric layer by modifying the recovered PVB.
本发明解决上述问题的技术方案如下：The technical scheme that the present invention solves the above-mentioned problem is as follows:
一种回收改性PVB的织物层压体，所述层压体包括织物层和复合在所述织物层至少一个表面的改性PVB层，所述改性PVB层的厚度为0.02~2mm，所述改性PVB层的原料包括以下质量份的组分：A fabric laminate for recycling modified PVB, the laminate comprising a fabric layer and a modified PVB layer compounded on at least one surface of the fabric layer, the thickness of the modified PVB layer is 0.02-2 mm, and the The raw material of the modified PVB layer includes the following components by mass:
PVB          30~80PVB 30~80
异氰酸酯     0.1~10Isocyanate 0.1~10
无机填料     0.4~60Inorganic filler 0.4~60
硅烷偶联剂   0.1~2.0Silane coupling agent 0.1~2.0
增塑剂       0.1~10.0Plasticizer 0.1~10.0
抗氧剂       0.1~2.0Antioxidant 0.1~2.0
润滑剂       0.5~3.0；Lubricant 0.5~3.0;
所述的PVB中，回收PVB的使用比例为40%~100%。In the described PVB, the utilization ratio of recycled PVB is 40% to 100%.
所述的回收PVB可以是从汽车前挡风玻璃或者用于建筑物的夹胶玻璃中回收得到的PVB胶片，或再将这些胶片进行初步的处理，如去杂、清洗、干燥、破碎等。所述的回收PVB也可以是，汽车前挡风玻璃和建筑物夹胶玻璃生产过程中产生的PVB胶片的下脚料。The recovered PVB can be PVB films recovered from automobile front windshields or laminated glass used in buildings, or these films are subjected to preliminary treatment, such as removing impurities, cleaning, drying, and breaking. The recycled PVB can also be the leftovers of PVB films produced in the production process of automobile front windshields and building laminated glass.
作为优选，所述改性PVB层的制备方法包括以下步骤：Preferably, the preparation method of the modified PVB layer comprises the following steps:
a、将无机填料先用硅烷偶联剂进行表面处理，具体为将无机填料与硅烷偶联剂在高速混合机中混合分散5~20分钟；a. The inorganic filler is first treated with a silane coupling agent, specifically, the inorganic filler and the silane coupling agent are mixed and dispersed in a high-speed mixer for 5 to 20 minutes;
b、开动密炼机，待温度上升后将PVB从加料口投入，炼胶1~5min；然后将增塑剂、抗氧剂和润滑剂从加料口投入，混炼1~5min；然后将上一步骤处理得到的无机填料从加料口投入，混炼5~10min；最后将异氰酸酯从加料口投入，混炼2~5min，得到胶料；再将从密炼机排出的胶料投到开炼机上进行包辊，待胶料温度降到120℃以下，取下胶料，投入螺杆挤出机，经螺杆挤出机挤出，再经压延得到改性PVB层。b. Start the mixer, after the temperature rises, put the PVB into the feed port, and mix the rubber for 1~5min; then put the plasticizer, antioxidant and lubricant from the feed port, and mix for 1~5min; The inorganic filler obtained by the one-step treatment is put in from the feeding port and mixed for 5~10 minutes; finally, the isocyanate is put in from the feeding port and mixed for 2~5 minutes to obtain a rubber compound; then the rubber material discharged from the internal mixer is put into the open mixing Rolling is carried out on the machine, and when the temperature of the rubber material drops below 120°C, the rubber material is removed, put into the screw extruder, extruded through the screw extruder, and then calendered to obtain the modified PVB layer.
  作为优选，所述硅烷偶联剂选自乙烯基三乙氧基硅烷、甲基丙烯酰氧基三甲氧基硅烷、氨丙基三甲氧基硅烷中的一种或多种。Preferably, the silane coupling agent is selected from one or more of vinyltriethoxysilane, methacryloxytrimethoxysilane, and aminopropyltrimethoxysilane.
  作为优选，所述异氰酸酯选自甲苯二异氰酸酯、异佛尔酮二异氰酸酯、二苯基甲烷二异氰酸酯、二环己基甲烷二异氰酸酯、六亚甲基二异氰酸酯、赖氨酸二异氰酸酯中的一种或多种，或者是上述异氰酸酯的预聚体中的一种或多种。Preferably, the isocyanate is selected from one of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, lysine diisocyanate or multiple, or one or more of the prepolymers of the aforementioned isocyanates.
  作为优选，所述的增塑剂选自三甘醇二异辛酸酯、四甘醇二庚酸酯、癸二酸二丁酯、癸二酸二辛酯、己二酸二辛脂、对苯二甲酸二辛酯中的一种或多种。Preferably, the plasticizer is selected from triethylene glycol diisocaprylate, tetraethylene glycol diheptanoate, dibutyl sebacate, dioctyl sebacate, dioctyl adipate, para One or more of dioctyl phthalate.
作为优选，所述的抗氧剂包括主抗氧剂和辅助抗氧剂；所述主抗氧剂为受阻酚类抗氧剂，选自巴斯夫抗氧剂IRGANOX1010、IRGANOX1076、IRGANOX1098中的一种或多种，所述辅助抗氧剂选自巴斯夫IRGAFOS 168、IRGAFOS 126、IRGAFOS P-EPQ中的一种或多种。Preferably, the antioxidant includes a main antioxidant and an auxiliary antioxidant; the main antioxidant is a hindered phenolic antioxidant, selected from one of BASF antioxidants IRGANOX1010, IRGANOX1076, IRGANOX1098 or Multiple, the auxiliary antioxidant is selected from BASF IRGAFOS 168, IRGAFOS 126, IRGAFOS One or more of P-EPQ.
作为优选，所述硅烷偶联剂选自乙烯基三乙氧基硅烷、甲基丙烯酰氧基三甲氧基硅烷、氨丙基三甲氧基硅烷中的一种或多种。Preferably, the silane coupling agent is selected from one or more of vinyltriethoxysilane, methacryloxytrimethoxysilane and aminopropyltrimethoxysilane.
作为优选，所述织物层采用选自涤纶、腈纶、锦纶、维纶、氨纶、聚丙烯、植物纤维中的一种纱线或其任意配比的混纺纱线经梭织或针织工艺制成；所述织物基材的纱线旦数为20~4800D。Preferably, the fabric layer is made of a kind of yarn selected from polyester, acrylic, nylon, vinylon, spandex, polypropylene, and vegetable fibers or a blended yarn in any proportion by weaving or knitting; The yarn denier of the fabric substrate is 20-4800D.
现有技术中的层压织物在制作过程中，需要在一生产线上先将胶水涂覆在织物层上，然后通过热烘设备将该胶水临时固化，使之暂时性失去粘性，收卷；然后在另一生产线上，通过炼胶工艺将配方原料炼制成胶料，然后通过压延机把胶料压制成连续性的薄片状物，接着把上述的收卷的织物层重新放卷，与改连续性的薄片状物通过贴合机复合在一起，贴合过程中，若连续性的薄片状物已经冷却则需要对其进行加热，若连续性的薄片状物余温尚足，则可利用余温将织物层表面固化的胶水热化，使之恢复粘性，再利用贴合机的物理辊压贴合作用，使得织物层和连续性的薄片状物贴合在一起形成层压织物；后续再将层压织物通过冷却辊组，冷却后得到成品。这种方法不仅操作繁琐，涂覆胶水时还容易影响车间环境，生产成本也较高。In the production process of the laminated fabric in the prior art, it is necessary to first coat the glue on the fabric layer in a production line, and then temporarily cure the glue through a heat drying device to temporarily lose its viscosity and wind it up; then In another production line, the formula raw materials are refined into rubber material through the rubber mixing process, and then the rubber material is pressed into a continuous sheet by a calender, and then the above-mentioned rolled fabric layer is re-unrolled, and the modified material is re-rolled. The continuous flakes are compounded together by a laminating machine. During the lamination process, if the continuous flakes have cooled, they need to be heated. If the residual temperature of the continuous flakes is still sufficient, the residual Warmly heat the glue cured on the surface of the fabric layer to restore its viscosity, and then use the physical rolling and laminating action of the laminating machine to make the fabric layer and the continuous sheet-like object stick together to form a laminated fabric; The laminated fabric is passed through a set of cooling rolls, and the finished product is obtained after cooling. This method is not only cumbersome to operate, but also easily affects the workshop environment when applying glue, and the production cost is also high.
本发明采用了改性PVB的方案，利用异氰酸酯和/或其预聚体，对PVB进行改性，使之本身对织物基材产生足够的粘结性。这样就可避免在织物层上进行涂胶固化的预操作。可在不使用胶粘剂及其配套工艺的情况下，直接将改性PVB层牢牢地粘附在织物基材层上。The present invention adopts the scheme of modifying PVB, using isocyanate and/or its prepolymer to modify PVB, so that it can produce sufficient adhesion to the fabric substrate. This avoids a pre-operation of glue curing on the fabric layer. The modified PVB layer can be directly and firmly adhered to the fabric substrate layer without using the adhesive and its supporting process.
本发明上述技术方案中，改性PVB层增加了与织物纤维的粘结能力，主要是通过添加异氰酸酯类助粘结剂实现的。添加异氰酸酯，通过异氰酸酯与PVB中的羟基反应，可以提高其与织物纤维的粘结力，并且使得PVB之间产生一定程度的交联，提高PVB层的力学性能。但是异氰酸酯的添加量不能太多，过多的添加量会使得PVB交联反应过度，造成加工困难，也会使得PVB层趋向于硬塑化。所述异氰酸酯的添加量为0.1~10%，优选为0.2~2%。并且，异氰酸酯的添加时机应该是在其他助剂添加完成并且经过一定程度的炼化后进行的。In the above technical solutions of the present invention, the modified PVB layer increases the bonding ability with the fabric fibers, which is mainly achieved by adding an isocyanate-based co-binder. Adding isocyanate, through the reaction between isocyanate and the hydroxyl group in PVB, can improve the bonding force with the fabric fiber, and make a certain degree of cross-linking between PVB, improve the mechanical properties of PVB layer. However, the addition amount of isocyanate should not be too much, too much addition will make the PVB cross-linking reaction excessive, causing processing difficulties, and will also make the PVB layer tend to hard plasticize. The addition amount of the isocyanate is 0.1-10%, preferably 0.2-2%. In addition, the timing of adding isocyanate should be carried out after the addition of other additives and a certain degree of refining.
为了提高层压织物的质感，需要加入适量的无机填料。无机填料一方面可以提高PVB层的密度，使得整体质感得到提升，另一方面可以提高产品的力学性能，如耐刮擦、抗拉强度等。但是无机填料的添加量不能太多，过多的添加量不仅会使得PVB层过重，也使得PVB层趋向于石化。In order to improve the texture of laminated fabrics, it is necessary to add an appropriate amount of inorganic fillers. On the one hand, inorganic fillers can increase the density of the PVB layer, which improves the overall texture, and on the other hand, can improve the mechanical properties of the product, such as scratch resistance and tensile strength. However, the addition amount of inorganic fillers should not be too much. Too much addition will not only make the PVB layer too heavy, but also make the PVB layer tend to be petrochemical.
为了提高层压织物的质感，需要加入适量的增塑剂，增塑剂的添加量一般可以根据需要来定，增塑剂的比例增加会使PVB层的手感变软，从而提高触感。通常将增塑剂的添加量设定为0.1~10.0质量份是较为合适的；更为优选的是0.5~8.0质量份。In order to improve the texture of the laminated fabric, it is necessary to add an appropriate amount of plasticizer. The amount of plasticizer can generally be determined according to needs. The increase in the proportion of plasticizer will soften the hand of the PVB layer, thereby improving the touch. Usually, it is more appropriate to set the amount of plasticizer to be 0.1 to 10.0 parts by mass; more preferably 0.5 to 8.0 parts by mass.
本发明上述技术方案中，润滑剂通常选自硬脂酸钙、硬脂酸锌、硬脂酸单双甘油酯、芥酸酰胺、油酸酰胺等。其中，硬脂酸钙、硬脂酸锌为优选。In the above technical solution of the present invention, the lubricant is usually selected from calcium stearate, zinc stearate, mono- and diglycerides of stearate, erucamide, oleic acid amide and the like. Among them, calcium stearate and zinc stearate are preferable.
本发明的另一个目的是提供上述复合高分子涂层织物的方法，该法包括以下步骤：Another object of the present invention is to provide a method for the above-mentioned composite polymer coated fabric, the method comprising the following steps:
S1、将织物层先用电晕设备进行处理，使得织物层表面能下降，与PVB层的粘结性增强；S1. The fabric layer is first treated with corona equipment, so that the surface energy of the fabric layer is reduced and the adhesion with the PVB layer is enhanced;
S2、将无机填料先用硅烷偶联剂进行表面处理，具体为将无机填料与硅烷偶联剂在高速混合机中混合分散5~20分钟；S2. The inorganic filler is firstly surface-treated with a silane coupling agent, specifically, the inorganic filler and the silane coupling agent are mixed and dispersed in a high-speed mixer for 5-20 minutes;
    S3、将经过步骤S2处理得到的无机填料与回收PVB、异氰酸酯、增塑剂、抗氧剂、润滑剂，通过密炼机和开炼机进行混炼处理，然后通过螺杆挤出机挤出，经压延得到改性PVB膜；  S3, the inorganic filler obtained through the treatment of step S2 and the recovered PVB, isocyanate, plasticizer, antioxidant and lubricant are mixed with an internal mixer and an open mixer, and then extruded through a screw extruder, The modified PVB film is obtained by calendering;
  S4、通过热压贴合机，使经过步骤S1处理得到的织物层与步骤S3处理得到的改性PVB膜热压贴合，再通过冷却辊组降温，得到所述的织物层压体。S4, make the fabric layer obtained by the treatment of step S1 and the modified PVB film obtained by the treatment of step S3 heat-compressed and bonded by a hot-press laminating machine, and then cool down by a cooling roller group to obtain the fabric laminate.
作为优选，步骤S2具体为：Preferably, step S2 is specifically:
a、将无机填料先用硅烷偶联剂进行表面处理，具体为将无机填料与硅烷偶联剂在高速混合机中混合分散5~20分钟；a. The inorganic filler is first treated with a silane coupling agent, specifically, the inorganic filler and the silane coupling agent are mixed and dispersed in a high-speed mixer for 5 to 20 minutes;
b、开动密炼机，待温度上升后将PVB从加料口投入，炼胶1~5min；然后将增塑剂、抗氧剂和润滑剂从加料口投入，混炼1~5min；然后将上一步骤处理得到的无机填料从加料口投入，混炼5~10min；最后将异氰酸酯从加料口投入，混炼2~5min，得到胶料；再将从密炼机排出的胶料投到开炼机上进行包辊，待胶料温度降到120℃以下，取下胶料，投入螺杆挤出机，经螺杆挤出机挤出，再经压延得到改性PVB层。b. Start the mixer, after the temperature rises, put the PVB into the feed port, and mix the rubber for 1~5min; then put the plasticizer, antioxidant and lubricant from the feed port, and mix for 1~5min; The inorganic filler obtained by the one-step treatment is put in from the feeding port and mixed for 5~10 minutes; finally, the isocyanate is put in from the feeding port and mixed for 2~5 minutes to obtain a rubber compound; then the rubber material discharged from the internal mixer is put into the open mixing Rolling is carried out on the machine, and when the temperature of the rubber material drops below 120°C, the rubber material is removed, put into the screw extruder, extruded through the screw extruder, and then calendered to obtain the modified PVB layer.
本发明的再一个目的是提供上述回收改性PVB的织物层压体在雨衣、雨伞、帐篷、罩子、袋、箱包、鞋、衣服、椅、沙发、垫、枕、体育用品、书写工具、玩具、婴童用品、马衣、宠物方面的用途。Another object of the present invention is to provide the above-mentioned recycled modified PVB fabric laminate in raincoats, umbrellas, tents, covers, bags, luggage, shoes, clothes, chairs, sofas, cushions, pillows, sporting goods, writing implements, toys , baby products, horse clothing, pets.
有益效果beneficial effect
综上所述，本发明具有以下有益效果：To sum up, the present invention has the following beneficial effects:
1、层压织物的质量主要体现在涂层的表面强度、手感、屈曲后的褶皱恢复性；表面强度主要体现在耐刮擦；本发明提供的回收改性PVB的织物层压体具有良好的耐刮擦、柔韧性和抗应力作用的能力，并且由于材料不含卤素，降解过程中不产生毒性物质。1. The quality of the laminated fabric is mainly reflected in the surface strength, hand feel, and wrinkle recovery after buckling of the coating; the surface strength is mainly reflected in the scratch resistance; the fabric laminate of recycled modified PVB provided by the present invention has good properties. Scratch, flexibility and resistance to stress, and because the material is halogen-free, no toxic substances are produced during degradation.
2、本发明制得的改性PVB层力学强度高，耐候性好，手感柔和。2. The modified PVB layer prepared by the invention has high mechanical strength, good weather resistance and soft hand feeling.
3、本发明通过利用异氰酸酯和/或异氰酸酯的预聚体来对回用PVB进行改性，使得PVB层与织物层之间产生足够的自粘贴性，从而可以避免在织物层上进行涂胶。解决了因涂胶而产生的一系列问题，如车间环境污染、工艺复杂、生产生本高等问题。对于夹层玻璃中的回收PVB的再利用有较好的促进。3. The present invention modifies the recycled PVB by using isocyanate and/or isocyanate prepolymer, so that sufficient self-adhesion between the PVB layer and the fabric layer can be produced, so that gluing on the fabric layer can be avoided. It solves a series of problems caused by gluing, such as workshop environmental pollution, complex process, and high production cost. It has a good promotion for the reuse of recovered PVB in laminated glass.
本发明的最佳实施方式BEST MODE FOR CARRYING OUT THE INVENTION
实施例一Example 1
一种回收改性PVB的织物层压体，该层压体包括织物层和复合在所述织物层一个表面的改性PVB层，改性PVB层的厚度为1.2mm。本实施例中，织物基材采用选自涤纶纱线，经平纹织造工艺制成。A fabric laminate for recycling modified PVB, the laminate comprises a fabric layer and a modified PVB layer compounded on one surface of the fabric layer, and the thickness of the modified PVB layer is 1.2 mm. In this embodiment, the fabric base material is made of polyester yarn selected from the plain weave process.
上述回收改性PVB的织物层压体的制备方法如下：The preparation method of the fabric laminate of above-mentioned recycled modified PVB is as follows:
S1、将织物层先用电晕设备进行处理，使得织物层表面能下降，与PVB层的粘结性增强；S1. The fabric layer is first treated with corona equipment, so that the surface energy of the fabric layer is reduced and the adhesion with the PVB layer is enhanced;
S2、将50kg碳酸钙用1.8kg乙烯基三乙氧基硅烷进行表面处理，具体为将碳酸钙与乙烯基三乙氧基硅烷在高速混合机中混合分散5分钟；S2, 50kg calcium carbonate is surface-treated with 1.8kg vinyltriethoxysilane, specifically, calcium carbonate and vinyltriethoxysilane are mixed and dispersed in a high-speed mixer for 5 minutes;
S3、开动密炼机，待温度上升到50℃后将60kg 回用PVB从加料口投入，炼胶3分钟；然后将4.5kg三甘醇二异辛酸酯、0.6kg巴斯夫IRGANOX1010、0.2kg巴斯夫IRGAFOS 168和1.5kg硬脂酸锌从加料口投入，混炼5分钟；然后将上一步骤处理得到的碳酸钙从加料口投入，混炼8min；最后将5.6kg异佛尔酮二异氰酸酯从加料口投入，混炼5min，得到胶料；再将从密炼机排出的胶料投到开炼机上进行包辊，待胶料温度降到120℃以下，取下胶料，投入螺杆挤出机，经螺杆挤出机挤出，再经压延得到改性PVB层；S3. Start the mixer, and after the temperature rises to 50°C, put 60kg of recycled PVB into the feeding port, and mix the rubber for 3 minutes; IRGAFOS 168 and 1.5kg of zinc stearate were put in from the feeding port, and mixed for 5 minutes; then the calcium carbonate obtained in the previous step was put in from the feeding port, and mixed for 8 minutes; finally, 5.6 kg of isophorone diisocyanate was added from the feeding port Put it into the mouth, mix it for 5 minutes to get the rubber material; then put the rubber material discharged from the internal mixer into the open mixer for roll wrapping, when the temperature of the rubber material drops below 120 ℃, remove the rubber material and put it into the screw extruder , extruded by a screw extruder, and then calendered to obtain a modified PVB layer;
  S4、通过热压贴合机，使经过步骤S1处理得到的织物层与步骤S3处理得到的改性PVB层热压贴合，再通过冷却辊组降温，得到所述的织物层压体。S4, make the fabric layer obtained through the treatment of step S1 and the modified PVB layer obtained by the treatment of step S3 through the hot-pressing laminating machine, and then pass the cooling roller set to cool down to obtain the fabric laminate.
本发明的实施方式Embodiments of the present invention
实施例二Embodiment 2
一种回收改性PVB的织物层压体，该层压体包括织物层和复合在所述织物层一个表面的改性PVB层，改性PVB层的厚度为1.0mm。本实施例中，织物基材采用选自涤纶纱线，经平纹织造工艺制成。A fabric laminate for recycling modified PVB, the laminate comprising a fabric layer and a modified PVB layer compounded on one surface of the fabric layer, and the thickness of the modified PVB layer is 1.0 mm. In this embodiment, the fabric base material is made of polyester yarn selected from the plain weave process.
上述回收改性PVB的织物层压体的制备方法如下：The preparation method of the fabric laminate of above-mentioned recycled modified PVB is as follows:
S1、将织物层先用电晕设备进行处理，使得织物层表面能下降，与PVB层的粘结性增强；S1. The fabric layer is first treated with corona equipment, so that the surface energy of the fabric layer is reduced and the adhesion with the PVB layer is enhanced;
S2、将50kg碳酸钙用1.6kg甲基丙烯酰氧基三甲氧基硅烷进行表面处理，具体为将碳酸钙与甲基丙烯酰氧基三甲氧基硅烷在高速混合机中混合分散5分钟；S2, 50kg calcium carbonate is surface-treated with 1.6kg methacryloyloxytrimethoxysilane, specifically, calcium carbonate and methacryloyloxytrimethoxysilane are mixed and dispersed in a high-speed mixer for 5 minutes;
S3、开动密炼机，待温度上升到50℃后将50kg 回用PVB从加料口投入，炼胶5分钟；然后将2.5kg四甘醇二庚酸酯、0.5kg巴斯夫IRGANOX1076、0.2kg巴斯夫IRGAFOS 126和1.5kg硬脂酸锌从加料口投入，混炼5分钟；然后将上一步骤处理得到的碳酸钙从加料口投入，混炼8min；最后将6.2kg六亚甲基二异氰酸酯从加料口投入，混炼5min，得到胶料；再将从密炼机排出的胶料投到开炼机上进行包辊，待胶料温度降到120℃以下，取下胶料，投入螺杆挤出机，经螺杆挤出机挤出，再经压延得到改性PVB层；S3. Start the mixer, and after the temperature rises to 50°C, put 50kg of recycled PVB into the feeding port, and mix the rubber for 5 minutes; 126 and 1.5kg of zinc stearate were dropped in from the feeding port, and mixed for 5 minutes; then the calcium carbonate that was processed in the previous step was dropped in from the feeding port, and mixed for 8min; 6.2kg of hexamethylene diisocyanate was added from the feeding port Put in, mix for 5 minutes to get the rubber material; then put the rubber material discharged from the internal mixer into the open mixer for roll wrapping, when the temperature of the rubber material drops below 120 ℃, remove the rubber material, put it into the screw extruder, Extruded by a screw extruder, and then calendered to obtain a modified PVB layer;
  S4、通过热压贴合机，使经过步骤S1处理得到的织物层与步骤S3处理得到的改性PVB层热压贴合，再通过冷却辊组降温，得到所述的织物层压体。S4, make the fabric layer obtained through the treatment of step S1 and the modified PVB layer obtained by the treatment of step S3 through the hot-pressing laminating machine, and then pass the cooling roller set to cool down to obtain the fabric laminate.
实施例三Embodiment 3
一种回收改性PVB的织物层压体，该层压体包括织物层和复合在所述织物层一个表面的改性PVB层，改性PVB层的厚度为0.8mm。本实施例中，织物基材采用选自涤纶纱线，经平纹织造工艺制成。A fabric laminate for recycling modified PVB, the laminate comprises a fabric layer and a modified PVB layer compounded on one surface of the fabric layer, and the thickness of the modified PVB layer is 0.8 mm. In this embodiment, the fabric base material is made of polyester yarn selected from the plain weave process.
上述回收改性PVB的织物层压体的制备方法如下：The preparation method of the fabric laminate of above-mentioned recycled modified PVB is as follows:
S1、将织物层先用电晕设备进行处理，使得织物层表面能下降，与PVB层的粘结性增强；S1. The fabric layer is first treated with corona equipment, so that the surface energy of the fabric layer is reduced and the adhesion with the PVB layer is enhanced;
S2、将50kg碳酸钙用1.2kg氨丙基三甲氧基硅烷进行表面处理，具体为将碳酸钙与氨丙基三甲氧基硅烷在高速混合机中混合分散5分钟；S2, 50kg calcium carbonate is surface-treated with 1.2kg aminopropyltrimethoxysilane, specifically, calcium carbonate and aminopropyltrimethoxysilane are mixed and dispersed in a high-speed mixer for 5 minutes;
S3、开动密炼机，待温度上升到50℃后将70kg 回用PVB从加料口投入，炼胶5分钟；然后将3.6kg对苯二甲酸二辛酯、0.5kg巴斯夫IRGANOX1098、0.5kg巴斯夫IRGAFOS P-EPQ和2.0kg硬脂酸锌从加料口投入，混炼5分钟；然后将上一步骤处理得到的碳酸钙从加料口投入，混炼10min；最后将8.3kg二苯基甲烷二异氰酸酯从加料口投入，混炼5min，得到胶料；再将从密炼机排出的胶料投到开炼机上进行包辊，待胶料温度降到120℃以下，取下胶料，投入螺杆挤出机，经螺杆挤出机挤出，再经压延得到改性PVB层；S3. Start the mixer, and after the temperature rises to 50°C, put 70kg of recycled PVB into the feeding port, and mix the rubber for 5 minutes; P-EPQ and 2.0kg of zinc stearate were put in from the feeding port and mixed for 5 minutes; then the calcium carbonate obtained from the previous step was put in from the feeding port and mixed for 10min; Put in the feeding port and mix for 5 minutes to get the rubber compound; then put the rubber material discharged from the internal mixer into the open mixer for roll wrapping, and when the rubber material temperature drops below 120 °C, remove the rubber material and put it into the screw for extrusion machine, extruded by screw extruder, and then calendered to obtain modified PVB layer;
  S4、通过热压贴合机，使经过步骤S1处理得到的织物层与步骤S3处理得到的改性PVB层热压贴合，再通过冷却辊组降温，得到所述的织物层压体。S4, make the fabric layer obtained through the treatment of step S1 and the modified PVB layer obtained by the treatment of step S3 through the hot-pressing laminating machine, and then pass the cooling roller set to cool down to obtain the fabric laminate.
实施例四Embodiment 4
一种回收改性PVB的织物层压体，该层压体包括织物层和复合在所述织物层一个表面的改性PVB层，改性PVB层的厚度为0.6mm。本实施例中，织物基材采用选自涤纶纱线，经平纹织造工艺制成。A fabric laminate for recycling modified PVB, the laminate comprises a fabric layer and a modified PVB layer compounded on one surface of the fabric layer, and the thickness of the modified PVB layer is 0.6 mm. In this embodiment, the fabric base material is made of polyester yarn selected from the plain weave process.
上述回收改性PVB的织物层压体的制备方法如下：The preparation method of the fabric laminate of above-mentioned recycled modified PVB is as follows:
S1、将织物层先用电晕设备进行处理，使得织物层表面能下降，与PVB层的粘结性增强；S1. The fabric layer is first treated with corona equipment, so that the surface energy of the fabric layer is reduced and the adhesion with the PVB layer is enhanced;
S2、将50kg碳酸钙用2.0kg氨丙基三甲氧基硅烷进行表面处理，具体为将碳酸钙与氨丙基三甲氧基硅烷在高速混合机中混合分散5分钟；S2, 50kg calcium carbonate is surface-treated with 2.0kg aminopropyltrimethoxysilane, specifically, calcium carbonate and aminopropyltrimethoxysilane are mixed and dispersed in a high-speed mixer for 5 minutes;
S3、开动密炼机，待温度上升到50℃后将65kg 回用PVB从加料口投入，炼胶5分钟；然后将5.8kg对己二酸二辛脂、0.5kg巴斯夫IRGANOX1010、0.5kg巴斯夫IRGAFOS 168和2.6kg硬脂酸锌从加料口投入，混炼5分钟；然后将上一步骤处理得到的碳酸钙从加料口投入，混炼10min；最后将7.6kg甲苯二异氰酸酯从加料口投入，混炼5min，得到胶料；再将从密炼机排出的胶料投到开炼机上进行包辊，待胶料温度降到120℃以下，取下胶料，投入螺杆挤出机，经螺杆挤出机挤出，再经压延得到改性PVB层；S3. Start the mixer, and after the temperature rises to 50°C, put 65kg of recycled PVB into the feeding port, and mix the rubber for 5 minutes; 168 and 2.6kg of zinc stearate were dropped in from the feeding port, and mixed for 5 minutes; then the calcium carbonate obtained in the previous step was dropped in from the feeding port, and mixed for 10min; Knead for 5 minutes to obtain rubber material; then put the rubber material discharged from the internal mixer into the open mixer for roll wrapping, when the temperature of the rubber material drops below 120 ° C, remove the rubber material, put it into the screw extruder, and extrude it through the screw Extruded out of the machine, and then calendered to obtain a modified PVB layer;
  S4、通过热压贴合机，使经过步骤S1处理得到的织物层与步骤S3处理得到的改性PVB层热压贴合，再通过冷却辊组降温，得到所述的织物层压体。S4, make the fabric layer obtained through the treatment of step S1 and the modified PVB layer obtained by the treatment of step S3 through the hot-pressing laminating machine, and then pass the cooling roller set to cool down to obtain the fabric laminate.
实施例五Embodiment 5
一种回收改性PVB的织物层压体，该层压体包括织物层和复合在所述织物层一个表面的改性PVB层，改性PVB层的厚度为0.6mm。本实施例中，织物基材采用选自涤纶纱线，经平纹织造工艺制成。A fabric laminate for recycling modified PVB, the laminate comprises a fabric layer and a modified PVB layer compounded on one surface of the fabric layer, and the thickness of the modified PVB layer is 0.6 mm. In this embodiment, the fabric base material is made of polyester yarn selected from the plain weave process.
上述回收改性PVB的织物层压体的制备方法如下：The preparation method of the fabric laminate of above-mentioned recycled modified PVB is as follows:
S1、将织物层先用电晕设备进行处理，使得织物层表面能下降，与PVB层的粘结性增强；S1. The fabric layer is first treated with corona equipment, so that the surface energy of the fabric layer is reduced and the adhesion with the PVB layer is enhanced;
S2、将50kg碳酸钙用1.2kg乙烯基三乙氧基硅烷进行表面处理，具体为将碳酸钙与乙烯基三乙氧基硅烷在高速混合机中混合分散5分钟；S2, 50kg calcium carbonate is surface-treated with 1.2kg vinyltriethoxysilane, specifically, calcium carbonate and vinyltriethoxysilane are mixed and dispersed in a high-speed mixer for 5 minutes;
S3、开动密炼机，待温度上升到50℃后将75kg 回用PVB从加料口投入，炼胶5分钟；然后将8.6kg癸二酸二辛酯、0.5kg巴斯夫IRGANOX1076、0.5kg巴斯夫IRGAFOS 168和2.3kg硬脂酸锌从加料口投入，混炼5分钟；然后将上一步骤处理得到的碳酸钙从加料口投入，混炼10min；最后将6.9kg二环己基甲烷二异氰酸酯从加料口投入，混炼5min，得到胶料；再将从密炼机排出的胶料投到开炼机上进行包辊，待胶料温度降到120℃以下，取下胶料，投入螺杆挤出机，经螺杆挤出机挤出，再经压延得到改性PVB层；S3. Start the mixer, and after the temperature rises to 50°C, put 75kg of recycled PVB into the feeding port, and mix for 5 minutes; And 2.3kg zinc stearate is dropped into from the feed port, and mixed for 5 minutes; then the calcium carbonate that the previous step is processed is dropped into from the feed port, and mixed for 10min; 6.9kg of dicyclohexylmethane diisocyanate is dropped into the feed port at last , knead for 5 minutes to obtain the rubber material; then put the rubber material discharged from the internal mixer into the open mixer for roll wrapping, when the temperature of the rubber material drops below 120 ℃, remove the rubber material, put it into the screw extruder, Extruded by a screw extruder, and then calendered to obtain a modified PVB layer;
  S4、通过热压贴合机，使经过步骤S1处理得到的织物层与步骤S3处理得到的改性PVB层热压贴合，再通过冷却辊组降温，得到所述的织物层压体。S4, make the fabric layer obtained through the treatment of step S1 and the modified PVB layer obtained by the treatment of step S3 through the hot-pressing laminating machine, and then pass the cooling roller set to cool down to obtain the fabric laminate.
胶合强度测试Bond Strength Test
取实施例一、二、三、四、五各自制得的样品作为试样，分别记为试样一、试样二、试样三、试样四和试样五。试样宽度10cm。The samples prepared in Examples 1, 2, 3, 4, and 5 were taken as samples, which were recorded as Sample 1, Sample 2, Sample 3, Sample 4, and Sample 5, respectively. The sample width is 10cm.
在普通的强力机上进行测试，在测试时，试样的两个层受两个方向相对的拉力作用，进行剥离；试样在被剥离过程中，随着拉力的加大，自动记录仪可持续绘出一条上升的曲线，而当拉力加载到一定大小时，处于该受力线上的织物层和PVB层之间的粘合被破坏，两者即发生分离，此时拉力迅速减小，记录仪便绘制出一条下降的曲线，而上升的曲线和下降的曲线的交点便形成一个“峰”，当试样分离至粘合较为牢固的下一条受力线时，又需要加大拉力才能使其剥离，记录仪又会给出一条上升的曲线。下降曲线和上升曲线的交点便形成一个“谷”，然后继续执行剥离的操作。如此，当试样用等速牵引强力机进行剥离的受力情况，可绘制出一个由许多“峰”和“谷”组成的受力曲线。The test is carried out on a common strength machine. During the test, the two layers of the sample are subjected to opposite tensile forces in two directions to peel off; during the peeling process of the sample, with the increase of the tensile force, the automatic recorder can continue to A rising curve is drawn, and when the tensile force is loaded to a certain magnitude, the adhesion between the fabric layer and the PVB layer on the force line is destroyed, and the two are separated. At this time, the tensile force decreases rapidly, recording The instrument draws a descending curve, and the intersection of the ascending curve and the descending curve forms a "peak". When the sample is separated to the next force line that is more firmly bonded, it needs to increase the pulling force to make the It peels off, and the recorder will give a rising curve again. The intersection of the descending and ascending curves forms a "valley", and the stripping operation continues. In this way, when the sample is peeled off with a constant velocity pulling force machine, a force curve consisting of many "peaks" and "valleys" can be drawn.
  在上述受力曲线上，峰值表示试样不同位置上PVB层与织物层被分离所需要施加的拉力的大小，显然，峰值越大，反映该处粘合越牢固，而峰谷则表示不同位置上PVB与织物层分离过程中拉力减小的数值，因此，测试粘合牢固主要注重峰值的情况。On the above stress curve, the peaks represent the tensile force required to separate the PVB layer and the fabric layer at different positions of the sample. Obviously, the larger the peaks, the stronger the bond is, while the peaks and valleys represent different positions. The value of the tensile force reduction during the separation of the upper PVB from the fabric layer, therefore, the test of bond firmness mainly focuses on the peak value.
首先是受力曲线上峰的数目，如前所述，在剥离测试过程中，试样是被一条线一条线地逐步剥离的，每一条线的粘合被破坏均可视为织物的断裂，如断裂强力试样那样，受力曲线在断裂点必然产生一个“峰”，但是试样如果粘合状态非常均匀，每条剥离线产生的峰值大小则几乎相等。那么受力曲线将是一条接近于水平线的曲线，而不会产生峰值。只有当各条剥离线上的断裂强度大小不等才会出现“峰”。因此，受力曲线是否有峰产生，峰的数目多少取决于试样的粘合情况。由于织物层是非均匀的，是一种梭织的平纹组织，PVB层与它之间产生一定程度的嵌合，PVB层嵌入平纹组织的部分形成一个个微小的胶粒，且胶粒之间必然存在间隔。同时，织物层织纹突出的地方与PVB层粘合较紧密，而织纹突出的地方与PVB层粘合较松。因而，试样在剥离过程中必然出现大量的峰和谷。经对试样一、二、三、四、五进行剥离检测，结果显示如下表。The first is the number of peaks on the force curve. As mentioned above, during the peel test, the sample is gradually peeled off line by line, and the failure of the bond of each line can be regarded as the break of the fabric. As with breaking strength specimens, the force curve must produce a "peak" at the breaking point, but if the specimen is very uniformly bonded, the magnitude of the peaks produced by each peel line will be nearly equal. Then the force curve will be a curve close to the horizontal line without peaks. "Peaks" appear only when the breaking strengths of the individual peel lines are unequal in size. Therefore, whether there is a peak in the stress curve, and the number of peaks depends on the adhesion of the sample. Since the fabric layer is non-uniform, it is a woven plain weave, and the PVB layer is intercalated with it to a certain extent. There are gaps. At the same time, the protruding parts of the fabric layer are closely bonded to the PVB layer, while the protruding parts of the fabric layer are loosely bonded to the PVB layer. Therefore, a large number of peaks and valleys must appear in the sample during the peeling process. The peeling test of samples 1, 2, 3, 4, and 5 is carried out, and the results are shown in the following table.
Figure 316414dest_path_image001
Figure 316414dest_path_image001
为了测出织物层与PVB层之间的粘合强度，测试方法是记录试样剥离过程中受力曲线上全部峰值，然后计算这些峰值的平均值和峰值之间的离散关系。In order to measure the adhesive strength between the fabric layer and the PVB layer, the test method is to record all the peaks on the stress curve during the peeling process of the sample, and then calculate the average value of these peaks and the discrete relationship between the peaks.
    结合上述表格，可以看出，在对10cm宽度试样进行粘合强度的测试时，计算得到的平均值都在85N以上，完全符合层压织物的正常要求。  Combining the above table, it can be seen that when testing the adhesive strength of the 10cm width sample, the calculated average values are all above 85N, which fully meets the normal requirements of laminated fabrics.

Claims (8)

  1. 一种回收改性PVB的织物层压体，所述层压体包括织物层和复合在所述织物层至少一个表面的改性PVB层，所述改性PVB层的厚度为0.02~2mm，所述改性PVB层包括以下质量份的组分：A fabric laminate for recycling modified PVB, the laminate comprising a fabric layer and a modified PVB layer compounded on at least one surface of the fabric layer, the thickness of the modified PVB layer is 0.02-2 mm, and the The modified PVB layer includes the following components by mass:
    PVB          20~99PVB 20~99
    异氰酸酯     0.1~10Isocyanate 0.1~10
    无机填料     0.4~60Inorganic filler 0.4~60
    硅烷偶联剂   0.1~2.0A silane coupling agent 0.1~2.0
    增塑剂       0.1~10.0Plasticizer 0.1~10.0
    抗氧剂       0.1~2.0Antioxidant 0.1~2.0
    润滑剂       0.5~3.0；Lubricant 0.5~3.0;
    所述PVB中，回用PVB的使用比例为0.1%~100%。In the PVB, the usage ratio of recycled PVB is 0.1% to 100%.
  2. 根据权利要求1所述的一种回收改性PVB的织物层压体，其特征在于：所述硅烷偶联剂选自乙烯基三乙氧基硅烷、甲基丙烯酰氧基三甲氧基硅烷、氨丙基三甲氧基硅烷中的一种或多种。A fabric laminate for recycling modified PVB according to claim 1, wherein the silane coupling agent is selected from the group consisting of vinyl triethoxy silane, methacryloxy trimethoxy silane, One or more of aminopropyltrimethoxysilane.
  3. 根据权利要求1所述的一种回收改性PVB的织物层压体，其特征在于：所述异氰酸酯选自甲苯二异氰酸酯、异佛尔酮二异氰酸酯、二苯基甲烷二异氰酸酯、二环己基甲烷二异氰酸酯、六亚甲基二异氰酸酯、赖氨酸二异氰酸酯中的一种或多种，或者是上述异氰酸酯的预聚体中的一种或多种。A fabric laminate for recycling modified PVB according to claim 1, wherein the isocyanate is selected from the group consisting of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane One or more of diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, or one or more of the prepolymers of the above-mentioned isocyanates.
  4. 根据权利要求1所述的一种回收改性PVB的织物层压体，其特征在于：所述的抗氧剂包括主抗氧剂和辅助抗氧剂；所述主抗氧剂为受阻酚类抗氧剂，选自巴斯夫抗氧剂IRGANOX1010、IRGANOX1076、IRGANOX1098中的一种或多种，所述辅助抗氧剂选自巴斯夫IRGAFOS 168、IRGAFOS 126、IRGAFOS P-EPQ中的一种或多种。A fabric laminate for recycling modified PVB according to claim 1, characterized in that: the antioxidant comprises a primary antioxidant and an auxiliary antioxidant; the primary antioxidant is hindered phenols Antioxidant, selected from one or more of BASF antioxidants IRGANOX1010, IRGANOX1076, IRGANOX1098, the auxiliary antioxidant is selected from one or more of BASF IRGAFOS 168, IRGAFOS 126, IRGAFOS P-EPQ.
  5. 根据权利要求1所述的一种回收改性PVB的织物层压体，其特征在于：所述织物层采用选自涤纶、腈纶、锦纶、维纶、氨纶、聚丙烯、植物纤维中的一种纱线或其任意配比的混纺纱线经梭织或针织工艺制成；所述织物层的纱线旦数为20~4800D。A fabric laminate for recycling modified PVB according to claim 1, wherein the fabric layer is a yarn selected from the group consisting of polyester, acrylic, nylon, vinylon, spandex, polypropylene, and plant fibers. The thread or its blended yarn in any proportion is made by weaving or knitting process; the yarn denier of the fabric layer is 20-4800D.
  6. 根据权利要求1所述的一种回收改性PVB的织物层压体，其特征在于：所述增塑剂选自三甘醇二异辛酸酯、四甘醇二庚酸酯、癸二酸二丁酯、癸二酸二辛酯、己二酸二辛脂、对苯二甲酸二辛酯中的一种或多种。A fabric laminate for recycling modified PVB according to claim 1, wherein the plasticizer is selected from the group consisting of triethylene glycol diisocaprylate, tetraethylene glycol diheptanoate, sebacic acid One or more of dibutyl ester, dioctyl sebacate, dioctyl adipate, and dioctyl terephthalate.
  7. 根据权利要求1所述的一种回收改性PVB的织物层压体的制备方法，包括以下步骤：A kind of preparation method of the fabric laminate of recycling modified PVB according to claim 1, comprises the following steps:
    S1、将织物层先用电晕设备进行处理，使得织物层表面能下降，与PVB层的粘结性增强；S1. The fabric layer is first treated with corona equipment, so that the surface energy of the fabric layer is reduced and the adhesion with the PVB layer is enhanced;
    S2、将无机填料先用硅烷偶联剂进行表面处理，具体为将无机填料与硅烷偶联剂在高速混合机中混合分散5~20分钟； S2. The inorganic filler is firstly surface-treated with a silane coupling agent, specifically, the inorganic filler and the silane coupling agent are mixed and dispersed in a high-speed mixer for 5-20 minutes;
      S3、将经过步骤S2处理得到的无机填料与回收PVB、异氰酸酯、增塑剂、抗氧剂、润滑剂，通过密炼机或开炼机进行混炼处理，再经过压延成膜得到改性PVB层；或者将混合好的物料通过螺杆挤出机挤出，经流延得到改性PVB层；S3. The inorganic filler obtained through the treatment of step S2 and the recovered PVB, isocyanate, plasticizer, antioxidant, and lubricant are mixed with an internal mixer or an open mixer, and then rolled into a film to obtain modified PVB. layer; or extrude the mixed material through a screw extruder, and obtain a modified PVB layer by casting;
      S4、通过热压贴合机，使经过步骤S1处理得到的织物层与步骤S3处理得到的改性PVB层热压贴合，再通过冷却辊组降温，得到所述的织物层压体。S4, make the fabric layer obtained through the treatment of step S1 and the modified PVB layer obtained by the treatment of step S3 through the hot-pressing laminating machine, and then pass the cooling roller set to cool down to obtain the fabric laminate.
  8.   根据权利要求7所述的一种回收改性PVB的织物层压体的制备方法，其特征在于：步骤S3具体为，开动密炼机，待温度上升后将PVB从加料口投入，炼胶1~5min；然后将增塑剂、抗氧剂和润滑剂从加料口投入，混炼1~5min；然后将上一步骤处理得到的无机填料从加料口投入，混炼5~10min；最后将异氰酸酯从加料口投入，混炼2~5min，得到胶料；再将从密炼机排出的胶料投到开炼机上进行包辊，待胶料温度降到120℃以下，取下胶料，再经压延得到改性PVB层；或者将混合好的物料投到螺杆挤出机，经螺杆挤出机挤出后，再经流延成膜，得到改性PVB层。The method for preparing a fabric laminate for recycling modified PVB according to claim 7, characterized in that: step S3 is specifically: starting the internal mixer, after the temperature rises, putting PVB into the feeding port, mixing 1 ~5min; then put the plasticizer, antioxidant and lubricant from the feeding port, and mix for 1~5min; then put the inorganic filler obtained in the previous step from the feeding port, and mix for 5~10min; finally, the isocyanate Input from the feeding port and mix for 2~5min to obtain the rubber compound; then the rubber material discharged from the internal mixer is thrown into the open mixer for roll wrapping. The modified PVB layer is obtained by calendering; or the mixed material is put into the screw extruder, and after being extruded by the screw extruder, the modified PVB layer is obtained by casting into a film.
PCT/CN2020/131046 2020-11-05 2020-11-24 Fabric laminate of recycled modified pvb and preparation method therefor WO2022095149A1 (en)

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