WO2021103062A1 - 一种复合高分子层压织物及其制法 - Google Patents

一种复合高分子层压织物及其制法 Download PDF

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Publication number
WO2021103062A1
WO2021103062A1 PCT/CN2019/122835 CN2019122835W WO2021103062A1 WO 2021103062 A1 WO2021103062 A1 WO 2021103062A1 CN 2019122835 W CN2019122835 W CN 2019122835W WO 2021103062 A1 WO2021103062 A1 WO 2021103062A1
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Prior art keywords
fabric
composite polymer
layer
base material
coating
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PCT/CN2019/122835
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English (en)
French (fr)
Inventor
封利苹
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杭州盛得新材料有限公司
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Priority claimed from CN201911171784.3A external-priority patent/CN110725135B/zh
Priority claimed from CN201911171788.1A external-priority patent/CN110922670B/zh
Application filed by 杭州盛得新材料有限公司 filed Critical 杭州盛得新材料有限公司
Publication of WO2021103062A1 publication Critical patent/WO2021103062A1/zh

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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/06Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04Homopolymers or copolymers of ethene
    • C08L23/08Copolymers of ethene
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06NWALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/04Layered products comprising a layer of synthetic resin as impregnant, bonding, or embedding substance

Definitions

  • the invention relates to a laminated fabric or a coated fabric, in particular to a composite polymer laminated fabric and a coated fabric and their preparation method.
  • Fabric coating generally refers to the process of uniformly coating polymer compounds on the surface of the fabric. It can not only improve the appearance and feel of the fabric, but also improve the functions of the fabric, such as making the fabric waterproof, breathable, and flame retardant. Special functions such as anti-fouling and shading and reflection.
  • Laminated fabrics also known as bonded fabrics, laminated fabrics. It refers to the bonding of fabric and other soft sheet materials to form a composite material with multiple functions, which is used in raincoats, tents, etc.
  • the newly formed plastic film and fabric can be laminated and laminated into artificial leather products.
  • PVC polyvinyl styrene
  • 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 it is degraded.
  • EVA material does not contain halogen and meets environmental protection standards.
  • EVA is usually used to manufacture polymer sheets and can be used as an intermediate layer of laminated glass.
  • a large number of discarded building laminated glass, automobile windshield and other garbage contain recyclable EVA film.
  • EVA recycled materials are weaker in all aspects.
  • various properties such as flexibility, strength, and abrasion resistance need to be strengthened.
  • the reuse of EVA to manufacture polymer coated fabrics is still an urgent problem in this field.
  • the present invention aims to solve the above-mentioned problems, thereby providing a composite polymer coated fabric.
  • a composite polymer coated fabric comprising a fabric substrate layer and a composite polymer coating attached to at least one side of the fabric substrate layer;
  • the fabric substrate layer is selected from polyester, acrylic, nylon, vinylon, and spandex , Polypropylene, plant fiber, or a blended yarn of any ratio made by weaving or knitting process;
  • the yarn denier of the fabric base material is 20-4800D;
  • the composite polymer The coated fabric also includes a base material melt layer of 5 to 50 ⁇ m;
  • the base material melt layer is a composite structure formed by a part of the composite polymer coating embedded in the fabric base material layer during the production process;
  • the fabric The fabric structure of the base material layer and the base material sizing layer are integrated, and the composite polymer coating and the base material sizing layer are integrated;
  • the thickness of the composite polymer coating is 10 to 500 ⁇ m;
  • the composite polymer The coating contains a composite polymer component and a filler; the composite polymer component takes EVA as an essential component and is added with other components,
  • the auxiliary materials include a type of auxiliary material and a type of auxiliary material.
  • the first type of auxiliary material includes but is not limited to acrylic resin, epoxy resin, and cellulose ether.
  • the second type of auxiliary material is silane coupling agent or titanate coupling agent.
  • Another object of the present invention is to provide the above-mentioned composite polymer coating fabric method, which comprises the following steps:
  • the sizing slurry contains the following components by mass:
  • the solvent is selected from a mixture of ethanol and ethyl acetate, wherein the volume ratio of ethanol is 30-70 vol%.
  • the thermal drying is specifically that the heating tunnel is provided with a temperature gradient, and the temperature gradient from the entrance to the exit of the drying tunnel is: 80-90°C, 90-100°C, 100-110 °C, 110 ⁇ 120°C; stay for 2 ⁇ 25S in each temperature section.
  • the base material melt slurry layer is composed of part of the fabric structure of the textile base material and the composite polymer coating; specifically, a part of the coating is embedded in the textile base material. Therefore, the fabric weave in the fabric substrate layer and the fabric weave in the substrate melt layer are integrated; the coating that is not embedded in the fabric substrate and the substrate melt layer are also integrated; and they are not embedded in the fabric.
  • the coating in the substrate also forms a composite polymer coating by itself.
  • the coated fabric in the prior art does not form a base material melt slurry layer, or the formed base material melt slurry layer is very thin, usually below 5 ⁇ m or even lower, so the interlayer composite strength is not high.
  • the appearance of the base material melted layer is closely related to the choice of the fabric base material of the present invention, the choice of coating formula, and the process parameters.
  • woven fabric In the choice of fabric base material, choose woven fabric instead of non-woven fabric; among woven fabrics, woven fabric is especially preferred.
  • the microstructure of the woven fabric is relatively stiff. When applying slurry, it is easier to embed the coating by applying pressure, whether it is a knife coating method or a roll coating method.
  • thermoplastic components such as PP, LDPE, etc.
  • thermoplastic elastomer components such as TPU, SBS, EPDM, etc.
  • One level of toughness is mainly manifested in the resistance to tensile fracture, which increases the tensile strength of the product. For example, a greater external force is required to change the shape of the product, and it is not easy to be broken, which can improve the stress resistance of the product; A level of toughness is reflected in the restoration of the original shape of the product, that is, the elastic deformation of the product, which significantly increases the elongation at break of the product, even if the effect of external force makes the shape of the product greatly changed, after the external force is removed, The product can still quickly return to its original form without becoming longer or slack.
  • the thermal drying is specifically that the heating tunnel is provided with a temperature gradient, and the temperature gradient from the entrance to the exit of the drying tunnel is: 80-90°C, 90-100°C, 100-110 °C, 110 ⁇ 120°C; stay for 2 ⁇ 25S in each temperature section.
  • Another object of the present invention is to provide the above-mentioned coated fabric in raincoats, umbrellas, tents, covers, handbags, bags, tool bags, shoes, clothes, furniture, shopping bags, ice bags, water bags, chairs, sofa fabrics, and seat cushions. , Pillows, sporting goods, car supplies, writing instruments, toys, baby products, horse clothes, pet supplies, etc. or similar items.
  • Another object of the present invention is to provide a composite polymer laminated fabric.
  • a composite polymer laminated fabric comprising a fabric base material layer, a base material melting layer with a thickness of 40-150 ⁇ m, an adhesive layer, and a composite polymer calendering layer of 0.02-2 mm.
  • the base material is melted
  • the adhesive layer is composed of a partial thickness of the fabric substrate layer, the adhesive layer and a partial thickness of the composite polymer calendering layer;
  • the fabric substrate is selected from polyester, acrylic, nylon, vinylon, spandex, polypropylene, plant fibers
  • a yarn or a blended yarn of any ratio in the fabric is made by weaving or knitting;
  • the yarn denier of the fabric substrate is 20-4800D;
  • the fabric structure in the fabric substrate layer is The fabric structure in the base material melt layer is derived from one body; part of the adhesive layer penetrates into the fabric base material to make the adhesive layer and the fabric base material glue together; the composite polymer calendered layer and the The adhesive layer is glued into one body, and part of the adhesive layer together with a part of the thickness
  • the graft-modified copolymer is selected from PE-g-MAH, PE-g-GMA, PE-g-AA, PE-g- One or more of MMA; the filler is selected from one or any combination of calcium carbonate, talc, attapulgite clay, wollastonite, etc.; the composite polymer coating contains the following parts by mass Component: EVA 10 ⁇ 35, other components 15 ⁇ 30, filler 5 ⁇ 30.
  • EVA is used as one of the polymer components, and other resins are combined to form a composite polymer component.
  • EVA has good feel, wear resistance, film-forming properties, and water repellency, but its comprehensive performance needs to be improved.
  • PE, PP or other thermoplastic materials have good scratch resistance and surface strength, but they are not soft enough. Therefore, the inventor proposed to blend the two types of materials to form a composite material with good flexibility and scratch resistance.
  • the thermoplastic component can significantly improve the surface strength and scratch resistance of the product.
  • the addition amount of the thermoplastic component is not particularly large, for example, it can be controlled at 5wt% to 15wt%, it will not significantly change the product. With its own soft properties, it is suitable for pressing after film formation.
  • EVA is used as one of the polymer components, and other resins are combined to form a composite polymer component.
  • TPU or other thermoplastic elastomers have good toughness and elasticity, and can also improve better tensile strength. Therefore, the inventor proposed to combine the two types of substances to form a composite material with better flexibility and better hand feeling.
  • the elastomer component can significantly improve the tensile strength, toughness, elongation at break and better hand feeling of the product.
  • the addition amount of the thermoplastic elastomer component is not particularly large, for example, it can be controlled at 5 wt% to 10 wt%, the softness of the product will not be significantly increased, and the product will not be too soft and unsuitable for pressing after film formation.
  • EVA is used as one of the polymer components, combined with a thermoplastic component and a thermoplastic elastomer component, so that the quality of the product is comprehensively improved.
  • the comprehensive use of thermoplastic components and thermoplastic elastomers can give EVA products better toughness, and their toughness manifests in different levels.
  • One level of toughness is mainly manifested in the resistance to tensile fracture, which makes the product improve the tensile strength.
  • the base material melt adhesive layer is composed of a partial thickness of the fabric base material layer, the adhesive layer and a partial thickness of the composite polymer calendering layer, and the fabric in the fabric base material layer
  • the fabric structure in the melted layer of tissue and substrate is derived from one body; part of the adhesive layer penetrates into the fabric substrate to make the adhesive layer and the fabric substrate glue into one body; the composite polymer calendering layer and The adhesive layer is glued into one body, and part of the adhesive layer together with part of the thickness of the composite polymer calendering layer is embedded in the fabric tissue gap of the fabric base material, thereby forming the base material melted glue Floor.
  • the above structure because the adhesive layer and the composite polymer calendering layer are not only attached to the surface of the fabric tissue, they are also embedded in the fabric base material.
  • the above structure enables the present invention to have the advantage of high bonding strength compared with the laminated fabric in the prior art.
  • Laminated fabrics in the prior art do not form a base material melt layer, or the formed base material melt layer is very thin, usually below 20 ⁇ m or even lower, so the bonding strength between layers is not high, because cracking often occurs Between the adhesive layer and the fabric. Between the adhesive layer and the composite polymer layer, cracks rarely occur due to the close physical properties.
  • the appearance of the base material melt layer is closely related to the choice of the fabric base material of the present invention, the choice of adhesive, and the process parameters.
  • woven fabric In the choice of fabric base material, choose woven fabric instead of non-woven fabric; among woven fabrics, woven fabric is especially preferred.
  • the microstructure of the woven fabric is relatively stiff, and uniform and stable interstitials are formed. It is easier to evenly embed the adhesive and the composite polymer calendered layer by applying pressure during gluing and calendering.
  • Glue with a slightly higher viscosity is relatively unlikely to be embedded in the fabric substrate, but this is not absolute.
  • it is also related to the factors during the bonding. For example, it is related to the rolling pressure and the temperature during bonding.
  • the lamination of the present invention can be carried out immediately after the calendering process, and the residual temperature of the calendering layer can heat the dried adhesive so that no secondary heating is required; or the laminating machine is used through the secondary heating of the laminating machine.
  • the adhesive on the calendered layer and/or the fabric substrate layer is heated; then roll-composite is performed.
  • Another object of the present invention is to provide a method for composite polymer laminated fabric, which includes the following steps:
  • the materials of the calendering formula include the following components by mass:
  • a filtering step is further provided, and the filtering step is to extrude the rubber or virgin material from a machine equipped with a filter screen; or step e includes two times Open refining, the filtering step is set between two refining.
  • Another object of the present invention is to provide the laminated fabric in raincoats, umbrellas, tents, covers, handbags, luggage, tool bags, shoes, clothes, furniture, shopping bags, coolers, water bags, chairs, sofa fabrics, and cushions. , Pillows, sporting goods, car supplies, writing instruments, toys, baby products, horse clothes, pet supplies, etc. or similar items.
  • the present invention has the following beneficial effects:
  • the present invention takes the replacement of the existing PVC materials as the starting point and provides a complete set of composite technologies of composite polymers and fabric substrates.
  • the quality of the coated fabric is mainly reflected in the surface strength of the coating, hand feel, wrinkle recovery after buckling, and fastness to tie yarns, etc.; the surface strength is mainly reflected in scratch resistance; the hand feeling is mainly reflected in changing the original softer characteristics of the fabric. Make it hard and affect the feel; the fastness of the tie yarn is mainly reflected in the ability to fix the fabric structure, after coating the fabric, it can change the fragile edge characteristics of the original fabric.
  • the composite polymer coating provided by the invention has good scratch resistance, flexibility and resistance to stress, and because the material does not contain halogen, no toxic substances are generated during the degradation process.
  • the quality of laminated fabric is mainly reflected in the surface strength of the polymer layer, hand feel, wrinkle recovery after buckling, etc.; surface strength is mainly reflected in scratch resistance; hand feeling is mainly reflected in changing the original softer characteristics of the fabric to make it harder And affect the feel.
  • the composite polymer laminated fabric provided by the invention has good scratch resistance, flexibility and stress resistance, and because the material does not contain halogen, no toxic substances are generated during the degradation process.
  • ethyl acetate is a low-toxic solvent, but the solubility of ethyl acetate is relatively low, and the mixture does not simply reflect the characteristics of dissolution, but swells, and the result of swelling is for the slurry
  • the preparation is difficult to control, and it will seriously affect the coating properties of the slurry, such as adhesion.
  • Ethanol is also a low-toxic solvent, but its polarity is strong, and the dispersibility of other raw materials in ethanol is not good, while the polarity of ethyl acetate is significantly less than that of ethanol, and the dispersibility of other raw materials in ethyl acetate is better.
  • the present invention determines a scheme for preparing a mixed solvent from ethyl acetate and ethanol, and ethanol accounts for 30 to 70 vol%, preferably 40 to 60 vol%, and more preferably 1:1. This combination not only solves the swelling characteristics of the mixture in ethyl acetate, but also improves the dispersibility of other raw materials to a certain extent.
  • other resins are compounded to enhance adhesion, such as epoxy resin or acrylic resin used in the formulation; resin modifiers are used to strengthen the adhesion fastness, so that the fabric structure and polymer material layer can be formed after molding. As a whole, it is difficult to peel off the composite polymer coating even with high-pressure steam.
  • the basic principle of adding this type of material is that this type of material can have a certain degree of curing effect, which is equivalent to the effect of a crosslinking agent, which significantly improves the adhesion and the reinforcing strength of the fabric substrate.
  • fillers can be used to properly enhance the scratch resistance of the product while appropriately reducing the amount of resin.
  • Coupling agents can improve the adhesion of the slurry to fabric substrates of different materials.
  • the choice of coupling agents can be titanate coupling agents and silane coupling agents such as HK-550, HK-551, etc.
  • the titanate coupling agent is preferred.
  • the titanate coupling agent has better dispersibility to other components than the silane coupling agent and better adhesion to various fabric substrates.
  • the use of the above coupling agent can also improve the dispersion effect of fillers, colorants, etc. in the slurry.
  • the present invention uses EVA, PP, TPU and other substances as the main components, and the EVA, PP, TPU and other raw materials of the present invention can be waste materials in other industries; therefore, the present invention can solve the problem by recycling The disposal of EVA, PP, TPU and other waste materials, and turning waste into treasure, produces great economic benefits.
  • Figure 1 is a schematic diagram of the roller coating equipment of the preferred embodiment
  • Figure 2 is a schematic diagram of the rubber mixing equipment of the preferred embodiment
  • Figure 3 is a schematic diagram of the calendering equipment of the preferred embodiment
  • Figure 4 is a schematic diagram of the knife coating equipment of the second embodiment
  • a composite polymer laminated fabric includes a fabric base material layer, a 100 ⁇ m base melt adhesive layer, an adhesive layer and a 0.2 mm composite polymer layer.
  • the base material melt adhesive layer is composed of part of the fabric structure of the textile base material and the adhesive cross composition, the textile structure in the textile base material layer and the textile structure in the base material melt layer form an integrated body; the adhesive layer and the base material
  • the melting glue layer constitutes a whole; the composite polymer layer is attached to the fabric substrate layer through the adhesive layer.
  • the fabric base material is made of polyester yarn selected through a plain weave process.
  • the composite polymer layer includes the following components by mass:
  • the pressure of the rolling is 0.1 MPa, and the vehicle speed is 25 m/min.
  • the coating amount of the adhesive is 50 g/m2.
  • the yarn denier of the fabric substrate is 500D.
  • the adhesive layer adopts a roller coating process, the adhesive viscosity is 2500cps, the coating temperature is room temperature, through multiple coatings, the total coating volume is controlled to 30g/m2, and the coating is completed at 80°C. Heat for 30s in the drying tunnel.
  • the equipment includes unwinding roller 1, guide roller 3, glue box 4, gravure roller 5, rubber roller 6, hot air oven 7.
  • Winding roller 8. The unwinding roll 1 continuously provides a PET fabric substrate, which is calendered in advance.
  • the adhesive is placed in the adhesive box 4, and the gravure roller 5 is partially immersed in the adhesive box. Through rotation, the adhesive is continuously sent to the fabric substrate by the gravure roller 5, and then passes through the pressure roller group. (Rubber roller 6 and gravure roller 5), the adhesive is evenly coated on the surface of the tensioned fabric substrate; the press roller set can further roll the un-dried coating layer by layer The pressure can drive away the air mixed into it and effectively improve the quality of the adhesive layer.
  • the adhesive can be partially or completely pressed into the interior of the fabric substrate through the action of mechanical force, thereby reducing the overall Thickness, and strengthen the overall fastness.
  • the solvent inside the rubber compound is evaporated, so that the adhesive is not sticky.
  • the semi-finished product is obtained by rewinding, which is ready for use (transferred to as shown in Figure 3). Put it on the reel).
  • the composite polymer calendering equipment combination includes twin-screw mixer 10, first conveyor 11, pulverizer 12, shut-off fan 13, internal mixer 14, conveyor 15, second conveyor 16, filter Device 17, open mixing mill 19.
  • the materials in the calendering formula such as EVA, PP, PE-g-MAH, TPU, ultra-fine CaCO3 used as fillers, pigments such as pigment carbon black, and zinc stearate as a mold release agent should be used first.
  • the twin-screw mixer 10 is stirred to make it evenly mixed, and then the mixed solid powder is sent to the pulverizer 12 through the first conveyor 11, so that the material is pulverized, sieved, and the sieve residue is returned to the pulverizer 12 or
  • the twin-screw mixer 10 continues to operate; the under-sieve is sent into the mixing chamber of the internal mixer 14 through the shut-off fan 13, and then the temperature is increased and the pressure is increased to perform the internal mixing operation.
  • the titanate coupling agent TTS is selected.
  • the internal mixer 14 includes a mixing chamber, a rotor, a rotor sealing component, a feeding component, a heating component, a hydraulic component, a discharge device, a transmission device, and a base.
  • a mixing chamber After the material is loaded into the mixing chamber, the material The door is closed, the top bolt of the pressing device is pressed down, the two rotors in the mixing chamber rotate towards each other, and the rubber is continuously stirred, folded and kneaded between the rotors and between the rotor and the wall of the mixing chamber. Function; At the same time, the materials are dispersed and mixed evenly due to shearing action to achieve the purpose of rubber mixing.
  • the temperature rise is achieved by electric heating, and the boost is achieved by hydraulic components.
  • the unloading device which is the rotary discharge hopper 14-1 in Figure 2, opens the mixing chamber by turning, and the rubber is discharged from the rotary discharge hopper 14-1 and falls into In the transfer frame 15-1 of the conveyor 15, it is then transported along the slope track and enters the arc top track. When it crosses the highest point and continues to the limit position, as shown in 15-1 ⁇ in the figure, the glue The material falls from the transfer frame 15-1 and enters the second conveyor 16. Then through the filter device 17 installed on the second conveyor 16, the substance 18 is finally obtained.
  • Substance 18 is suitable for smelting, it is in a semi-hot melt state, semi-solidified state, and has a certain fluidity.
  • the solid powder can be kneaded to form a hot melt state, semi-solidified state, and a certain fluidity material, making it suitable for the open mill 19 to form a thin layer.
  • the substance is shown as number 18 in Figure 2 or Figure 3.
  • the body of the filter device 17 is a metal filter screen with a certain strength.
  • the material 18 is processed by the filter device 17 by forcibly squeezing the material through the filter device 17 by the second conveyor 16.
  • FIG. 3 is a combination of calendering equipment, including an open mill 19, a calender 20, a hot-pressing compound machine 22, a water-cooled roll group 23, and a second unwinding roll 21 and a second winding roll 24.
  • the semi-finished product on the winding roller 8 in FIG. 1 is transferred to the position indicated by the reference number 21 in FIG. 3.
  • the second unwinding roller 21 we call it the second unwinding roller 21.
  • the operation of the open mill 19 on the substance 18 is shown in detail.
  • the substance 18 becomes a continuous thin layer with a certain width.
  • the continuous thin layer is fed into the calender 20, and through the function of the calender 20, a stable composite high molecular polymer laminated film is formed.
  • the fabric substrate 2 that has been coated with the adhesive and cured is unrolled at the position of the second unwinding roller 21, and the above-mentioned stable composite polymer laminate film passes through the action of the guide roller. It is fed into the laminating machine 22 in two ways to form an appropriate angle.
  • the laminating machine 22 has a roller set consisting of two rollers, one roller is a rubber roller, and the other roller is a mirror roller or a pattern roller.
  • the roller set can provide strong pressure, so that the adhesive on the fabric substrate 2 is heated by the residual heat of the calendering layer and starts to melt and exhibit viscosity, so that the fabric substrate 2 and the stable composite polymer laminate film are in contact with each other. Under the action of strong pressure, an integrated composite is formed; then, the composite is guided and wound into the cooling roller set 23 in a continuous S-shaped manner at an appropriate angle, and then is cooled. Finally, the winding is performed at the position of the second winding roller 24 to complete the manufacturing of the finished product.
  • the laminated fabric of this embodiment is basically the same as the best embodiment, except that their fabric substrates are slightly different, their calendering layer formulations are slightly different, and their adhesive formulations are slightly different.
  • the fabric substrate layer is a blended fabric of PET and nylon composite fibers, and the structure is a plain weave.
  • the thickness of a part of the adhesive layer that is hot pressed into the fabric structure of the fabric substrate layer is 50 ⁇ m.
  • the pressure of the roller is 0.5MPa, and the vehicle speed is 35m/min.
  • the coating amount of the adhesive is 100 g/m2.
  • the yarn denier of the fabric substrate is 600D.
  • the adhesive layer adopts a roller coating process, the viscosity of the adhesive is 5000 cps, the gluing temperature is room temperature, and the gluing amount is controlled to 100 g/m2. After gluing is completed, it is heated in a drying tunnel at 120° C. for 15 seconds.
  • the calendering formula contains the following components by mass:
  • a composite polymer coating fabric includes a fabric base material layer, a 100 ⁇ m thick base melt slurry layer, and a composite polymer coating.
  • the slurry viscosity is 5000 cps
  • the coating temperature is room temperature
  • the coating amount is 100 g/m2.
  • the fabric base material is made of PET yarn through plain weaving process.
  • the fabric base material has been calendered in advance, the calendering speed is 50m/min, and the calendering temperature is 90°C.
  • the composite polymer coating fabric is formed by uniformly coating the composite polymer slurry on a calendered surface of the fabric substrate layer by a knife coater, and then drying the coating by heat drying. In the process of knife coating, due to the application of pressure and the certain hardness of the fabric substrate layer itself, the composite polymer slurry is partially embedded in the fabric substrate layer, thereby forming a composite of 100 ⁇ m thick substrate melt slurry layer. structure.
  • the process of thermal drying is not only a process of solvent evaporation, but also a process of solidification of the slurry.
  • the thermal drying parameters are controlled as follows: the heating tunnel is a tunnel type and is equipped with a temperature gradient. The temperature gradients from the entrance to the exit of the drying tunnel are: 80 ⁇ 90°C, 90 ⁇ 100°C, 100 ⁇ 110°C, 110 ⁇ 120°C; drying time is 80s.
  • the formula of the composite polymer slurry includes the following components by mass:
  • FIG. 4 shows the equipment for making the above-mentioned composite polymer coated fabric, which includes an unwinding roller 100, a supporting plate 300, a slurry box 400, a coating knife 500, a pressing roller set 600, a hot air oven 700, and a winding roller 800.
  • the unwinding roll 100 continuously provides a PET fabric substrate, which is calendered in advance.
  • the above-mentioned slurry is placed in the slurry box 400, and the bottom of the slurry box 400 has an opening, which can continuously provide the slurry of the above formula, and the slurry is coated on the tensioned fabric by the coating knife 400 Above the substrate; the fabric substrate has been squeezed by the coating knife to form a relatively uniform coating that has not yet dried.
  • the present invention also sets a pressure roller set here.
  • the roller set can further roll the un-dried coating one after another, which can drive away the air mixed into it, and effectively improve the quality of the coating; at the same time, it can also reduce the coating part through the action of mechanical force. Or it is completely pressed into the interior of the fabric base material, thereby reducing the overall thickness and strengthening the overall fastness.
  • After rolling through the heating effect of the tunnel-type hot-air oven 700, the solvent inside the slurry is evaporated, the coating is cured and formed, and finally the composite polymer coated fabric is obtained by winding.
  • the present invention reverses the orientation of the coating knife in the prior art.
  • the purpose of this is to increase the amount of coating. Press into the fabric base material to reduce the overall thickness, so that a composite polymer coated fabric with a thickness up to the standard and strengthened can be obtained.
  • the coated fabric has better strength and better bonding fastness than the existing ones, and the flexural feel is also improved due to the optimization of the formula, and has good resilience.
  • a composite polymer coated fabric is different from the second embodiment only in the formulation of the paste.
  • the formulation of the slurry includes the following components by mass:
  • a composite polymer coated fabric is different from the second embodiment only in the formulation of the paste.
  • the slurry coating of this embodiment includes the following components by mass:
  • a composite polymer coated fabric is different from the second embodiment only in the formulation of the paste.
  • the slurry coating of this embodiment includes the following components by mass:
  • a composite polymer coated fabric is different from the second embodiment only in the formulation of the paste.
  • the slurry coating of this embodiment includes the following components by mass:

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)

Abstract

一种复合高分子涂层织物、层压织物及它们的制备方法、用途。复合高分子涂层织物包括织物基材层、复合高分子涂层以及由部分的复合高分子涂层嵌入织物基材层组织内部形成的基材融浆层。复合高分子层压织物包括织物基材层、胶黏剂层、复合高分子压延层以及部分的胶黏剂层连同部分厚度的复合高分子压延层嵌入到所述的织物基材的织物组织空隙内形成的基材融胶层。复合高分子组分以EVA为必要组分,并添加有其他组分。复合高分子涂层织物和层压织物具有良好的耐刮擦、柔韧性和抗应力作用的能力,并且由于不含卤素,降解过程中不产生毒性物质。

Description

一种复合高分子层压织物及其制法 技术领域
本发明涉及一种层压织物或涂层织物,尤其涉及一种复合高分子层压织物和涂层织物及它们的制备方法。
背景技术
织物涂层,泛指将高分子类化合物均匀涂布在织物表面的工艺技术,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。
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。
它们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。
它们现有技术中,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。
EVA材料不含卤素,符合环保标准,现有技术中,EVA通常用于制造聚合物片材,可用作夹胶玻璃的中间层。而现阶段,大量废弃的建筑物夹胶玻璃、汽车挡风玻璃等垃圾中含有可回收利用的EVA胶片。但EVA回用料相比新料在各方面性能上都有所弱化,尤其是添加一些助剂用于生产涂层织物时,在柔韧性,强度,耐磨度等各种性能都有待加强。而回用EVA来制造高分子涂层织物,仍然是本领域亟需解决的问题。
发明概述
技术问题
问题的解决方案
技术解决方案
本发明要解决上述问题,从而提供一种复合高分子涂层织物。
本发明解决上述问题的技术方案如下:
一种复合高分子涂层织物,包括织物基材层和附着在所述织物基材层至少一面的复合高分子涂层;所述织物基材层采用选自涤纶、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;所述复合高分子涂层织物还包括5~50μm的基材融浆层;所述基材融浆层是在生产过程中由部分的复合高分子涂层嵌入织物基材层组织内部形成的复合结构;所述织物基材层与基材融浆层的织物组织构成一体,所述复合高分子涂层与基材融浆层构成一体;所述复合高分子涂层的厚度为10~500μm;所述复合高分子涂层包含复合高分子组分和填料;所述的复合高分子组分以EVA为必要组分,并添加有其他组分,所述其他组分包含但不限于(a)LDPE、LLDPE、PP的一种或多种和/或(b)TPU、SBS、TPR、EPDM中的一种或多种;当其他组分包含(a)和(b)时,所述其他组分中还包含有用于提高相容性的接枝改性共聚物,所述接枝改性共聚物选自PE-g-MAH、PE-g-GMA、PE-g-AA、PE-g-MMA中的一种或多种;所述填料选自碳酸钙、滑石粉、凹凸棒黏土、硅灰石等中的一种或其任意种类的组合;所述复合高分子涂层包含以下质量份的组分:EVA 10~35、其他组分15~30、填料1~30。
作为上述技术方案的优选,当所述复合高分子涂层还包含辅料时,所述辅料包括一类辅料和二类辅料,一类辅料包含但不限于丙烯酸树脂、环氧树脂、纤维素醚中的一种或多种;二类辅料为硅烷偶联剂或钛酸酯偶联剂。
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:
A、选择一织物基材,进行前处理,烘干,备用;
B、在所述织物基材上进行涂浆,涂浆完成后烘干,使浆料固化不发粘,并与织物基材形成一体,得涂浆织物基材;浆料粘度为900~150000cps,总涂胶量控制在5~200g/m2;
C、涂浆完成后热烘;
所述涂浆的浆料包含以下质量份的组分:
Figure PCTCN2019122835-appb-000001
所述溶剂选自乙醇和乙酸乙酯的混合液,其中乙醇的体积比为30~70vol%。
作为上述技术方案的优选,所述热烘具体为,热烘的烘道设有温度梯度,所述温度梯度从烘道入口至出口依次为:80~90℃,90~100℃,100~110℃,110~120℃;每个温度段停留2~25S。
本发明上述技术方案中,基材融浆层由织物基材的部分织物组织和所述复合高分子涂层交叉组成;具体是部分涂层嵌入到织物基材中形成的。因此,织物基材层中的织物组织与基材融浆层中的织物组织是一体的;未嵌入到织物基材中的涂层和基材融浆层也形成了一体;并且未嵌入到织物基材中的涂层还独自形成了复合高分子涂层。上述结构,由于复合高分子涂层并非仅仅附着在织物组织的表面,它还通过形成织物融浆层的形式嵌入到织物基材中;使得本发明相对于现有技术中的涂层织物具有涂层附着强度高的优点。
现有技术中的涂层织物由于没有形成基材融浆层,或者形成的基材融浆层非常薄,通常在5μm以下甚至更低,因此层间复合强度不高。
本发明上述技术方案中,基材融浆层的出现,是跟本发明织物基材的选择,跟涂层配方的选择,以及工艺参数都是密切相关的。
在织物基材的选择上,选择织造布,而非无纺布;在织造布中,尤以梭织布为佳。梭织布的微观组织结构相对硬挺,在进行涂浆时,无论是刀涂刮浆法还是辊涂法都更加容易通过施压把涂层嵌入。
在涂层配方的选择以及工艺的搭配上,尤以稍高粘度浆料一次涂胶并达到规定的涂浆量的方案为好。粘度低的浆料,相对来说需要蒸发更多的溶剂,溶剂蒸发地越多越容易发生表面变化,使得产品表面收缩,影响产品质量。除了浆料的粘度外,还跟涂浆时的压力有关,通常设置的压力要超过0.5MPa,以使形成更厚的基材融浆层,从而提高涂层的附着强度。
当其他组分中含有LDPE、LLDPE、TPE、PVA中的一种或多种时,可以显著 增强复合涂层的耐摩擦强度、表面硬度、防水能力以及材料的整体强度。但会使得复合涂层在手感上变硬,质感下降;而当添加一定比例的热塑性弹性体后,可以改变这种情况,可使复合涂层变得柔韧,从而提高产品的柔韧性。
研究显示,在增加了热塑性组分后,如PP、LDPE等,能够显著提高其耐磨度和强度;但过多的添加量会使产品变硬;通常增加5%~15%的热塑性组分就能够起到良好的增强作用,且并不显著提高成膜后的表面硬度;表面硬度的提高还可以通过添加热塑性弹性体组分,如TPU、SBS、EPDM等,予以解决。虽然单独的EVA也有一定的柔韧性,强度,耐磨度,但总体上,其各种性能都有待加强,从而制得一种综合性能更佳的产品。相对单独的EVA而言,热塑性组分和热塑性弹性体的综合使用可赋予EVA产品更好的韧性,并且他们的韧性表现在不同的层次。一个层次的韧性主要表现在抗拉伸断裂,使得产品提高了拉伸强度,如使产品发生形态改变需要更大的外力作用,并且不容易被拉断,它可以提高产品的抗应力能力;另一个层次的韧性体现在恢复产品的原有形态,也即产品的弹性形变上,显著提高产品的断裂伸长率,即使外力的作用使得产品的形态发生了较大改变,在撤销该外力后,产品仍能迅速恢复到原有形态而没有变得更长或松弛。
作为上述技术方案的优选,所述热烘具体为,热烘的烘道设有温度梯度,所述温度梯度从烘道入口至出口依次为:80~90℃,90~100℃,100~110℃,110~120℃;每个温度段停留2~25S。
本发明的再一个目的是提供上述的涂层织物在雨衣、雨伞、帐篷、罩子、手袋、箱包、工具袋、鞋、衣服、家具、购物袋、冰袋、水袋、椅、沙发面料、座垫、抱枕、体育用品、汽车用品、书写工具、玩具、婴童用品马衣、宠物用品等或类似物品方面的用途。
本发明的再一个目的是,提供一种复合高分子层压织物。
一种复合高分子层压织物,包括依次布置的织物基材层、厚度为40~150μm的基材融胶层、胶黏剂层和0.02~2mm的复合高分子压延层,所述基材融胶层由部分厚度的织物基材层、所述胶黏剂层以及部分厚度的复合高分子压延层共同组成;织物基材采用选自涤纶、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;所述织物基材层中的织物组织与基材融胶层中的织物组织源自一体;部分所述的胶黏剂层渗入到织物基材中使胶黏剂层与织物基材胶合成一体;所述复合高分子压延层与所述的胶黏剂层胶合成一体,并且部分的胶黏剂层连同部分厚度的复合高分子压延层嵌入到所述的织物基材的织物组织空隙内,从而形成所述的基材融胶层;所述复合高分子压延层包含复合高分子组分和填料;所述的复合高分子组分以EVA为必要组分,并添加有其他组分,所述其他组分包含但不限于(a)LDPE、LLDPE、PP的一种或多种和/或(b)TPU、SBS、TPR、EPDM中的一种或多种;当其他组分包含(a)和(b)时,所述其他组分中还包含有用于提高相容性的接枝改性共聚物,所述接枝改性共聚物选自PE-g-MAH、PE-g-GMA、PE-g-AA、PE-g-MMA中的一种或多种;所述填料选自碳酸钙、滑石粉、凹凸棒黏土、硅灰石等中的一种或其任意种类的组合;所述复合高分子涂层包含以下质量份的组分:EVA 10~35、其他组分15~30、填料5~30。
本发明以EVA为高分子组分之一,并配合其他树脂形成了一种复合的高分子组分。EVA具有良好的手感、耐磨、成膜性、拒水性,但其综合性能还有待提高。PE、PP或其他热塑性材料具有良好的耐刮擦性能和表面强度,但不够柔软。故本发明人提出了将两类物质共混复合,形成一种柔韧性好、耐刮擦的复合材料。
本发明上述技术方案中,热塑性组分能够显著提高产品的表面强度和耐刮擦能力,只要热塑性组分的添加量不是特别大,比如可以控制在5wt%~15wt%,就不显著改变产品的本身较柔的属性,适于成膜后压贴。
本发明以EVA为高分子组分之一,并配合其他树脂形成了一种复合的高分子组分。TPU或其他热塑性弹性体具有良好的韧性和弹性,也能提高更好的拉伸强度。故本发明人提出了将两类物质复合,形成一种柔韧性更好、手感更佳的复合材料。
本发明上述技术方案中,弹性体组分能够显著提高产品的拉伸强度、韧性、断裂拉伸率以及更好的手感。只要热塑性弹性体组分的添加量不是特别大,比如 可以控制在5wt%~10wt%,就不显著增加产品的柔软性,不会使产品过于柔软而不适合成膜后的压贴。
更为优选的,本发明以EVA为高分子组分之一,并配合热塑性组分和热塑性弹性体组分,从而使得产品的品质全面提升。相对单独的EVA而言,热塑性组分和热塑性弹性体的综合使用可赋予EVA产品更好的韧性,并且他们的韧性表现在不同的层次。一个层次的韧性主要表现在抗拉伸断裂,使得产品提高了拉伸强度,如使产品发生形态改变需要更大的外力作用,并且使产品难以被拉断,它可以提高产品的抗应力能力;另一个层次的韧性体现在恢复产品的原有形态,也即产品的弹性形变上,显著提高产品的断裂伸长率,即使外力的作用使得产品的形态发生了较大改变,在撤销该外力后,产品仍能迅速恢复到原有形态而没有变得更长或松弛。
本发明上述技术方案中,所述基材融胶层由部分厚度的织物基材层、所述胶黏剂层以及部分厚度的复合高分子压延层共同组成,所述织物基材层中的织物组织与基材融胶层中的织物组织源自一体;部分所述的胶黏剂层渗入到织物基材中使胶黏剂层与织物基材胶合成一体;所述复合高分子压延层与所述的胶黏剂层胶合成一体,并且部分的胶黏剂层连同部分厚度的复合高分子压延层嵌入到所述的织物基材的织物组织空隙内,从而形成所述的基材融胶层。上述结构,由于胶黏剂层和复合高分子压延层并非仅仅附着在织物组织的表面,它还嵌入到织物基材中。上述结构,使得本发明相对于现有技术中的层压织物具有贴合强度高的优点。
现有技术中的层压织物由于没有形成基材融胶层,或者形成的基材融胶层非常薄,通常在20μm以下甚至更低,因此层间贴合强度不高,因为开裂往往是出现在胶黏剂层与织物组织之间。胶黏剂层与复合高分子层之间,由于物性的接近很少发生开裂的情况。
本发明上述技术方案中,基材融胶层的出现,是跟本发明织物基材的选择,跟胶黏剂的选择,跟工艺参数都是密切相关的。
在织物基材的选择上,选择织造布,而非无纺布;在织造布中,尤以梭织布为佳。梭织布的微观组织结构相对硬挺,并且形成有均匀稳定的组织间隙,在进 行涂胶和压延时,更加容易通过施压把胶黏剂和复合高分子压延层均匀地嵌入。
在胶黏剂的选择以及工艺的搭配上,尤以稍低粘度胶水多次涂胶并达到规定的涂胶量的方案为好。稍高粘度的胶水,相对来说不太容易被嵌入到织物基材中,但这不是绝对的。因为除了涂胶时的因素外,还跟贴合时的因素有关。比如跟辊压压力有关,还跟贴合时的温度有关。本发明的贴合可以是在压延工序后即刻进行,压延层的余温可将烘干的胶黏剂热化故而不需要二次加热;或者采用贴合机,通过贴合机的二次加热使压延层和/或者织物基材层上的胶黏剂热化;然后进行辊压复合。
本发明的再一个目的是提供一种复合高分子层压织物的方法,该法包括以下步骤:
a、选择一织物基材,对其进行预处理,烘干;
b、在所述织物基材上进行涂胶黏剂,烘干,使胶黏剂固化不发粘,并与织物基材形成一体,得涂胶织物基材,备用;胶黏剂粘度为900~150000cps,总涂胶量控制在5~200g/m2;
c、将压延配方量的物料,放入搅拌机搅拌,得固态混料;
d、将固态混料输入密炼机,进行炼胶,得胶料;
e、将胶料转至开炼机进行开炼,得到初生料;
f、将初生料输入压延机进行压延,得到复合高分子压延膜;
g、将复合高分子压延膜和涂胶织物基材进行辊压复合,成型;
h、通过冷却辊组,收卷;
所述压延配方量的物料包括以下质量份的组分:
EVA         10~35
其他组分    15~30
填料        5~30。
作为上述技术方案的优选,在步骤e之前或者之后,还设置有过滤步骤,所述过滤步骤是把胶料或者初生料从加装有过滤网筛的机器中挤出;或者步骤e包括两次开炼,所述过滤步骤设置在两次开炼之间。
本发明的再一个目的是提供所述层压织物在雨衣、雨伞、帐篷、罩子、手袋、箱包、工具袋、鞋、衣服、家具、购物袋、冰袋、水袋、椅、沙发面料、座垫、抱枕、体育用品、汽车用品、书写工具、玩具、婴童用品马衣、宠物用品等或类似物品方面的用途。
发明的有益效果
有益效果
综上所述,本发明具有以下有益效果:
1、因PVC材料在降解过程中极易产生戴奥辛类剧毒物质,故本发明以代替现有PVC材料为出发点,提供一整套完整的复合高分子与织物基材的复合技术。涂层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、绑纱牢度等;表面强度主要体现在耐刮擦;手感主要体现在改变织物本来较柔软的特性,使之变硬而影响手感;绑纱牢度主要是体现在固定织物组织的能力,在对织物进行涂层后,可改变原织物易散边的特性。本发明提供的复合高分子涂层,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。层压织物的质量主要体现在高分子层的表面强度、手感、屈曲后的褶皱恢复性等;表面强度主要体现在耐刮擦;手感主要体现在改变织物本来较柔软的特性,使之变硬而影响手感。本发明提供的复合高分子层压织物,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。
2、溶剂的选择上,乙酸乙酯是低毒溶剂,但乙酸乙酯溶解度相对略低,而且混合料在其中并不单纯地体现出溶解的特性,而是溶胀,溶胀的结果对于浆料的制备较难把控,并且也会严重影响浆料的涂层性能,如粘结性等。乙醇也是低毒溶剂,但其极性较强,其他原料在乙醇中的分散性能不佳,而乙酸乙酯的极性明显小于乙醇,其他原料在乙酸乙酯中的分散性较好。但乙酸乙酯与乙醇显然需要一个最佳的配比,乙醇偏多则其他物料的分散性不好,乙醇偏少则物料的溶解度会下降并且更容易发生溶胀。本发明最终确定了乙酸乙酯和乙醇来制备混合溶剂的方案,并且乙醇占30~70vol%,优选40~60vol%,进一步优选1∶1。这种搭配,既解决了混合物料在乙酸乙酯中的溶胀特性,也一定程度上提升 了其他原料的分散性。
3、本发明通过复配其他树脂来增强粘结性,比如配方中使用了环氧树脂或丙烯酸树脂;通过树脂改性剂来强化粘接牢度,使得织物组织和高分子材料层在成型后成为一个整体,即使通过高压蒸汽也难以将复合高分子涂层剥离。添加这类物质的基本原理是,这类物质能够起到一定程度的固化作用,也就是相当于交联剂的作用,显著提高粘结性,也提高了对织物基材的补强强度。另外,本发明人发现通过填料来适当增强产品的耐刮擦性能,同时适当降低树脂的用量,但填料用量过多在提升耐刮擦的同时也容易影响产品手感,使产品变硬,一般控制在5wt%以内。偶联剂能提高浆料对于不同材质织物基材的附着性,偶联剂的选择可使用钛酸酯偶联剂和硅烷偶联剂如HK-550,HK-551等。优选钛酸酯偶联剂,钛酸酯偶联剂比硅烷偶联剂在对其他组分的分散性上更好,对各种织物基材的附着性能也更佳。上述偶联剂的使用,还能提高填料、着色剂等在浆料中的分散效果。
4、本发明采用EVA、PP、TPU等物质为主要成分,而作为本发明的EVA、PP、TPU等原料,可以是其他工业中的废料;因此,本发明可以通过回收再利用的方式,解决EVA、PP、TPU等废料的处置,并且变废为宝,产生极大的经济效益。
对附图的简要说明
附图说明
图1是最佳实施例的辊涂设备示意图;
图2是最佳实施例的炼胶设备示意图;
图3是最佳实施例的压延设备示意图;
图4是实施例二的刀涂设备示意图;
图中,1-放卷辊,2-织物基材,3-导辊,4-黏胶箱,5-凹纹辊,6-橡胶辊,7-热风烘箱,8-收卷辊;10-双螺杆搅拌机、11-第一输送机、12-粉碎机、13-关风机、14-密炼机、15-传送机、16-第二输送机、17-过滤装置、18-物质、19-开炼机;20-压延机、21-第二放卷辊、22-贴合机、23-水冷辊组、24-第二收卷辊24;14-1-旋转式出料斗,15-1-转运框,15-1`-同一转运框在不同时间下的位置信息;10 0-放卷辊,200-织物基材,300-支撑板,400-浆料箱,500-涂刀,600-压辊组,700-热风烘箱,800-收卷辊,900-导辊。
发明实施例
本发明的实施方式
以下结合附图对本发明进行进一步的解释说明。
本具体实施方式仅仅是对本发明的解释,并不是对本发明的限制,本领域技术人员在阅读了本发明的说明书之后,所做的任何改变,只要在权利要求书的范围内,都将受到专利法的保护。
一种复合高分子层压织物,包括织物基材层、100μm的基材融胶层、胶黏剂层和0.2mm的复合高分子层。基材融胶层由织物基材的部分织物组织和所述胶黏剂交叉组成,织物基材层中的织物组织与基材融胶层中的织物组织构成一体;胶黏剂层与基材融胶层构成一体;复合高分子层通过胶黏剂层贴合在所述的织物基材层上。
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。
所述复合高分子层包括以下质量份的组分:
Figure PCTCN2019122835-appb-000002
所述辊压复合工艺中,辊压的压力为0.1MPa,车速为25m/min。所述胶黏剂的涂胶量为50g/m2。所述织物基材的纱线旦数为500D。
所述胶黏剂层采用辊涂工艺,胶黏剂粘度为2500cps,涂胶温度为室温,通过多道次的涂覆,总涂浆量控制为30g/m2,涂浆完成后在80℃的烘道内热烘30s。
如图1所示,为制备将胶黏剂涂覆到织物基材上的设备,该设备包括放卷辊1,导辊3,黏胶箱4,凹纹辊5,橡胶辊6,热风烘箱7,收卷辊8。放卷辊1源源不断 地提供PET织物基材,该基材是预先轧光过的。胶黏剂被放置在黏胶箱4内,凹纹辊5部分浸渍在黏胶箱内,通过转动,胶黏剂被凹纹辊5源源不断地送到织物基材上,再经过压辊组(橡胶辊6和凹纹辊5)的作用,该胶黏剂被均匀涂布在张紧的织物基材的表面;该压辊组可进一步地把尚未干化的涂层进行一道次地辊压,可以把混入其内的空气赶跑,有效地提高胶黏剂层的质量;同时还可以通过机械力的作用,把胶黏剂部分或者全部地压入织物基材内部,从而降低整体的厚度,并强化整体的牢度。在辊压后,经过隧道式的热风烘箱7的加热作用,使胶料内部的溶剂蒸发,使胶黏剂不发粘,最后经过收卷,得到半成品,待用(转运到图3所示的放卷轴上)。
如图2所示,复合高分子的压延设备组合,包括双螺杆搅拌机10、第一输送机11、粉碎机12、关风机13、密炼机14、传送机15、第二输送机16、过滤装置17、开炼机19。
使用上述设备组合时,先把压延配方中物料如EVA、PP、PE-g-MAH、TPU、用作填料的超细CaCO3、颜料如色素炭黑以及脱模剂硬脂酸锌等物质,在双螺杆搅拌机10中进行搅拌使之混匀,然后通过第一输送机11把混合的固体粉料送入到粉碎机中12中,使物料被粉碎,过筛,筛余物返回粉碎机12或者双螺杆搅拌机10继续操作;筛下物通过关风机13被送入到密炼机14的密炼室中,然后升温升压,进行密炼操作。本实施例中选用钛酸酯偶联剂TTS。
更具体地,密炼机14包括密炼室、转子、转子密封部件、加料部件、加热部件、液压部件、卸料装置、传动装置以及基座等部分,物料装入到密炼室后,料门关闭,压料装置的上顶栓压下,密炼室内两个转子相向回转,胶料在转子之间、在转子与密炼室壁之间受到不断的搅拌、折卷和强烈的捏炼作用;同时物料由于受到剪切作用而分散并混合均匀,达到炼胶目的。升温是通过电加热实现的,升压是通过液压部件实现的。在胶料炼制完成后,通过卸料装置,也就是图2中的旋转式出料斗14-1,通过转动使密炼室打开,胶料从旋转式出料斗14-1排出,落入到传送机15的转运框15-1中,然后沿着坡面轨道进行输送,进入弧顶轨道,当越过最高点并继续前进至限位位置,如图中15-1`所示处时,胶料从转运框15-1掉落,进入第二输送机16。接着通过安装在第二输送机16上的过滤装 置17,最终得到物质18。物质18是适于开炼的,它处于半热熔状态的,半固化态的,并具有一定的流动性。
通过密炼机14,可把固态粉料经过捏炼作用,形成热熔状态的、半固化态的、有一定流动性的物质,使之适用于开炼机19进行形成薄层的加工,该物质如图2或图3中标号18所示。
当然,为了确保物质18的质量,再进入开炼机19操作之前,还需要通过过滤装置17的处理,把该物质内颗粒较大的成分给截留下来,从而保证物质18中不含颗粒物。过滤装置17的本体是一个具有一定强度的金属过滤网,物质18通过过滤装置17的处理,具体是通过第二输送机16强行将物料挤过过滤装置17实现的。
图3是压延设备组合,包括开炼机19、压延机20、热压复合机22、水冷辊组23以及第二放卷辊21和第二收卷辊24。
图1中收卷辊8上的半成品,在图3中被转运到了标号21所示的位置,为了便于区分,我们称之为第二放卷辊21。
如图3所示,具体展示了开炼机19对于物质18的操作,通过开炼机19,物质18变成了连续的、具有一定宽幅的薄层状物。然后经过导向辊,连续的薄层状物被喂入压延机20,经过压延机20的作用,形成了稳定的复合高分子聚合物层压薄膜。另一方面,已经涂好胶黏剂并且固化了的织物基材2在第二放卷辊21的位置,被放卷出来,与上述稳定的复合高分子聚合物层压薄膜通过导向辊的作用分两路以形成合适角度的方式被喂入贴合机22。贴合机22的由两个辊子构成的辊组,一个辊子为橡胶辊,另一个辊子为镜面辊或者花纹辊。辊组能够提供强大的压力,使得织物基材2上的胶黏剂受到压延层的余热作用开始热熔并展现黏性,从而使得织物基材2与稳定的复合高分子聚合物层压薄膜在强大压力的作用下,形成一体复合物;然后该复合物经过导向以合适的角度以连续的S型方式绕设进入冷却辊组23,之后被冷却。最后于第二收卷辊24位置进行收卷,完成成品的制造。
实施例一
本实施例的层压织物与最佳实施例基本一致,不同在于,它们的织物基材略有 不同,它们的压延层的配方略有不同,它们的胶黏剂的配方略有不同。
具体的,织物基材层,是PET和锦纶复合纤维的混织布,组织为平纹组织。
本实施例中,被热压入所述的织物基材层的织物组织内的部分胶黏剂层的厚度为50μm。在贴合工艺中,辊压的压力为0.5MPa,车速为35m/min。所述胶黏剂的涂胶量为100g/m2。所述织物基材的纱线旦数为600D。
所述胶黏剂层采用辊涂工艺,胶黏剂粘度为5000cps,涂胶温度为室温,控制涂胶量为100g/m2,涂胶完成后在120℃的烘道内热烘15s。
本实施例中,压延配方包含如下质量份的组分:
Figure PCTCN2019122835-appb-000003
实施例二
一种复合高分子涂层织物,包括织物基材层、100μm厚的基材融浆层、以及复合高分子涂层。本实施例中,浆料粘度为5000cps,涂胶温度为室温,涂浆量为100g/m2。织物基材为PET纱线经平纹织造工艺制成。所述织物基材预先经过轧光处理,轧光车速为50m/min,轧光温度为90℃。复合高分子涂层织物是通过刀涂机将复合高分子浆料均匀涂覆在织物基材层的一个轧光处理过的表面上,然后经热烘,使涂层干化而成。在刀涂的过程中,由于压力的施加,以及织物基材层本身一定的硬度,使得复合高分子浆料部分嵌入到织物基材层中,从而形成了100μm厚的基材融浆层的复合结构。
热烘的过程既是溶剂蒸发的过程,也是浆料固化的过程。热烘参数控制如下:热烘的烘道为隧道式,并设有温度梯度,所述温度梯度从烘道入口至出口依次为:80~90℃,90~100℃,100~110℃,110~120℃;热烘时间为80s。
本实施例中,复合高分子浆料的配方包括如下质量份的组分:
Figure PCTCN2019122835-appb-000004
图4所示为制作上述复合高分子涂层织物的设备,它包括放卷辊100,支撑板300,浆料箱400,涂刀500,压辊组600,热风烘箱700,收卷辊800。放卷辊100源源不断地提供PET织物基材,该基材是预先轧光过的。于支撑板处,上述浆料被放置在浆料箱400内,浆料箱400底部有开口,可以源源不断地提供上述配方的浆料,该浆料被涂刀400涂布在张紧的织物基材的上面;织物基材经过涂刀的刮浆处理,已经形成了较为均匀的尚未干化的涂层,考虑到涂层质量,本发明还在此处设置了一个压辊组,该压辊组可进一步地把尚未干化的涂层进行一道次地辊压,可以把混入其内的空气赶跑,有效地提高涂层的质量;同时还可以通过机械力的作用,把涂层部分或者全部地压入织物基材内部,从而降低整体的厚度,并强化整体的牢度。在辊压后,经过隧道式的热风烘箱700的加热作用,使浆料内部的溶剂蒸发,使涂层固化成型,最后经过收卷,得到成品的复合高分子涂层织物。需要注意的是,为了提高涂浆质量,本发明把现有技术中的涂刀的朝向进行反向设置,这样做的目的是可以提高涂浆量,然后通过压辊组的作用,把浆料压入织物基材内,降低整体厚度,这样就可以获得厚度达标,并且强化的复合高分子涂层织物。该涂层织物相比现有的具有更好的强度以及更好地结合牢度,并且在屈曲手感上也因为配方的优化而获得提升,具有良好的回弹性。
实施例三
一种复合高分子涂层织物,与实施例二不同之处仅在于涂浆的配方不同。
本实施例中,浆料的配方包括如下质量份的组分:
Figure PCTCN2019122835-appb-000005
实施例四
一种复合高分子涂层织物,与实施例二不同之处仅在于涂浆的配方不同。
具体的,本实施例的浆料涂层包括如下质量份的组分:
Figure PCTCN2019122835-appb-000006
实施例五
一种复合高分子涂层织物,与实施例二不同之处仅在于涂浆的配方不同。
具体的,本实施例的浆料涂层包括如下质量份的组分:
Figure PCTCN2019122835-appb-000007
Figure PCTCN2019122835-appb-000008
由于结构相同,浆料涂层在配方选择上没有本质的区别,因此,可以采用如实施例一所述的设备。
实施例六
一种复合高分子涂层织物,与实施例二不同之处仅在于涂浆的配方不同。
具体的,本实施例的浆料涂层包括如下质量份的组分:
Figure PCTCN2019122835-appb-000009

Claims (9)

  1. 一种复合高分子涂层织物,包括织物基材层和附着在所述织物基材层至少一面的复合高分子涂层;所述织物基材层采用选自涤纶、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;其特征在于:所述复合高分子涂层织物还包括5~50μm的基材融浆层;所述基材融浆层是在生产过程中由部分的复合高分子涂层嵌入织物基材层组织内部形成的复合结构;所述织物基材层与基材融浆层的织物组织构成一体,所述复合高分子涂层与基材融浆层构成一体;所述复合高分子涂层的厚度为10~500μm;所述复合高分子涂层包含复合高分子组分和填料;所述的复合高分子组分以EVA为必要组分,并添加有其他组分,所述其他组分包含但不限于(a)LDPE、LLDPE、PP的一种或多种和/或(b)TPU、SBS、TPR、EPDM中的一种或多种;当其他组分包含(a)和(b)时,所述其他组分中还包含有用于提高相容性的接枝改性共聚物,所述接枝改性共聚物选自PE-g-MAH、PE-g-GMA、PE-g-AA、PE-g-MMA中的一种或多种;所述填料选自碳酸钙、滑石粉、凹凸棒黏土、硅灰石等中的一种或其任意种类的组合;所述复合高分子涂层包含以下质量份的组分:EVA 10~35、其他组分15~30、填料1~30。
  2. 根据权利要求1所述的一种复合高分子涂层织物,其特征在于:当所述复合高分子涂层还包含辅料时,所述辅料包括一类辅料和二类辅料,一类辅料包含但不限于丙烯酸树脂、环氧树脂、纤维素醚中的一种或多种;二类辅料为硅烷偶联剂或钛酸酯偶联剂。
  3. 制造如权利要求1所述复合高分子涂层织物的方法,包括以下步骤:
    a、选择一织物基材,进行前处理,烘干,备用;
    b、在所述织物基材上进行涂浆,涂浆完成后烘干,使浆料固化不 发粘,并与织物基材形成一体,得涂浆织物基材;浆料粘度为900~150000cps,总涂胶量控制在5~200g/m 2
    c、涂浆完成后热烘;
    所述涂浆的浆料包含以下质量份的组分:
    Figure PCTCN2019122835-appb-100001
    所述溶剂选自乙醇和乙酸乙酯的混合液,其中乙醇的体积比为30~70vol%。
  4. 根据权利要求3所述的方法,其特征在于:所述热烘具体为,热烘的烘道设有温度梯度,所述温度梯度从烘道入口至出口依次为:80~90℃,90~100℃,100~110℃,110~120℃;每个温度段停留2~25S。
  5. 根据权利要求1所述的涂层织物在雨衣、雨伞、帐篷、罩子、手袋、箱包、工具袋、鞋、衣服、家具、购物袋、冰袋、水袋、椅、沙发面料、座垫、抱枕、体育用品、汽车用品、书写工具、玩具、婴童用品马衣、宠物用品等或类似物品方面的用途。
  6. 一种复合高分子层压织物,包括依次布置的织物基材层、厚度为40~150μm的基材融胶层、胶黏剂层和0.02~2mm的复合高分子压延层,所述基材融胶层由部分厚度的织物基材层、所述胶黏剂层以及部分厚度的复合高分子压延层共同组成;织物基材采用选自涤纶、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;其特征在于:所述织物基材层中的织物组织与基材融胶层中的织物组织源自一体;部分所述的胶黏剂层渗入到织物基材中使胶黏剂层与织物基材胶合成一体;所述复合高分子压延层与所述的胶黏剂层胶合成一体,并且部分的胶黏剂 层连同部分厚度的复合高分子压延层嵌入到所述的织物基材的织物组织空隙内,从而形成所述的基材融胶层;所述复合高分子压延层包含复合高分子组分和填料;所述的复合高分子组分以EVA为必要组分,并添加有其他组分,所述其他组分包含但不限于(a)LDPE、LLDPE、PP的一种或多种和/或(b)TPU、SBS、TPR、EPDM中的一种或多种;当其他组分包含(a)和(b)时,所述其他组分中还包含有用于提高相容性的接枝改性共聚物,所述接枝改性共聚物选自PE-g-MAH、PE-g-GMA、PE-g-AA、PE-g-MMA中的一种或多种;所述填料选自碳酸钙、滑石粉、凹凸棒黏土、硅灰石等中的一种或其任意种类的组合;所述复合高分子涂层包含以下质量份的组分:EVA 10~35、其他组分15~30、填料5~30。
  7. 制造如权利要求6所述的一种复合高分子层压织物的方法,包括以下步骤:
    a、选择一织物基材,对其进行预处理,烘干;
    b、在所述织物基材上进行涂胶黏剂,烘干,使胶黏剂固化不发粘,并与织物基材形成一体,得涂胶织物基材,备用;胶黏剂粘度为900~150000cps,总涂胶量控制在5~200g/m 2
    c、将压延配方量的物料,放入搅拌机搅拌,得固态混料;
    d、将固态混料输入密炼机,进行炼胶,得胶料;
    e、将胶料转至开炼机进行开炼,得到初生料;
    f、将初生料输入压延机进行压延,得到复合高分子压延膜;
    g、将复合高分子压延膜和涂胶织物基材进行辊压复合,成型;
    h、通过冷却辊组,收卷;
    所述压延配方量的物料包括以下质量份的组分:
    EVA       10~35
    其他组分    15~30
    填料     5~30。
  8. 根据权利要求7所述的制造复合高分子层压织物的方法,其特征在 于:在步骤e之前或者之后,还设置有过滤步骤,所述过滤步骤是把胶料或者初生料从加装有过滤网筛的机器中挤出;或者步骤e包括两次开炼,所述过滤步骤设置在两次开炼之间。
  9. 权利要求6所述的一种复合高分子层压织物的用途,其特征在于:所述层压织物在雨衣、雨伞、帐篷、罩子、手袋、箱包、工具袋、鞋、衣服、家具、购物袋、冰袋、水袋、椅、沙发面料、座垫、抱枕、体育用品、汽车用品、书写工具、玩具、婴童用品马衣、宠物用品等或类似物品方面的用途。
PCT/CN2019/122835 2019-11-26 2019-12-04 一种复合高分子层压织物及其制法 WO2021103062A1 (zh)

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DE4416356C2 (de) * 1994-05-09 1997-10-02 Contitech Elastomer Besch Gmbh Transparentes, gasdichtes Verbundmaterial und dessen Verwendung
CN1078917C (zh) * 1995-02-28 2002-02-06 南亚塑胶工业股份有限公司 以乙烯-醋酸乙烯酯共聚合树脂为主要成分的塑胶皮、布及其制备方法
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