WO2022241903A1 - 由废旧热塑性弹性体和回收聚酯形成的薄膜及层合物 - Google Patents

由废旧热塑性弹性体和回收聚酯形成的薄膜及层合物 Download PDF

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WO2022241903A1
WO2022241903A1 PCT/CN2021/101789 CN2021101789W WO2022241903A1 WO 2022241903 A1 WO2022241903 A1 WO 2022241903A1 CN 2021101789 W CN2021101789 W CN 2021101789W WO 2022241903 A1 WO2022241903 A1 WO 2022241903A1
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Prior art keywords
film
polyester
thermoplastic elastomer
elastomer
viscosity modifier
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PCT/CN2021/101789
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English (en)
French (fr)
Inventor
林裕卫
许颖博
曾东辉
颜志坚
格拉索·丹尼尔
黄慧卿
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佛山金万达科技股份有限公司
狼爪装备公司
卡拉威高尔夫公司
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Application filed by 佛山金万达科技股份有限公司, 狼爪装备公司, 卡拉威高尔夫公司 filed Critical 佛山金万达科技股份有限公司
Priority to EP21940352.4A priority Critical patent/EP4332164A1/en
Priority to KR1020237043795A priority patent/KR20240010025A/ko
Publication of WO2022241903A1 publication Critical patent/WO2022241903A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C08L67/025—Polyesters derived from dicarboxylic acids and dihydroxy compounds containing polyether sequences
    • 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
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • 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
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • 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
    • B32B5/022—Non-woven fabric
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/05—Alcohols; Metal alcoholates
    • C08K5/053—Polyhydroxylic 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1515—Three-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • 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
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • 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
    • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • 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
    • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • 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
    • C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/20—Recycled plastic
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/62—Plastics recycling; Rubber recycling

Definitions

  • the invention relates to the recycling of waste plastics, especially waste thermoplastic elastomers and recycled polyesters; more specifically, the invention relates to a film formed from waste thermoplastic elastomers and recycled polyesters and a laminate thereof.
  • PET Polyethylene terephthalate
  • the modification methods of recycled PET can be mainly divided into three categories: one is degradation modification, that is, by reducing the molecular weight, the recycled PET is depolymerized into low molecular weight substances such as terephthalic acid and its esters, and then resynthesized PET or made into other products
  • the second is solid-state polycondensation modification, which makes the recycled PET at a specific temperature and is assisted by other conditions, so that the molecular weight is increased, and it can be used as a high-viscosity polyester again
  • the third is chemical chain extension modification, so that the recycled PET and the chain extender occur The chemical reaction increases the molecular weight of recycled PET.
  • Chinese patent 99812803.1 discloses a method for preparing foam products, which includes: heating a mixture containing the following components to a temperature not lower than the melting point of polyester to prepare A low melt flow rate and 10-200% swollen polyester resin; the polyester resin is then thermally foamed with the help of a blowing agent, wherein the mixture comprises: (a) 100 parts by weight of linear saturated Polyester; (b) 0.1-10 parts by weight of a coupling agent mixture consisting of 0-100% by weight of a compound containing two epoxy groups in the molecule and 100-0% by weight of a compound containing two or more rings The compound composition of oxygen group; and (c) 0.01-5 parts by weight of carboxylate metal salt as a coupling reaction catalyst.
  • the patented technology turns recycled polyester into foam products for use as cushioning, insulation, packaging, food containers, dispensing and more.
  • Chinese patent 201110288666.8 discloses a method for toughening and tackifying waste PET, which includes the following steps: 1) preparing raw materials; 2) crushing and drying; 3) mixing; 4) feeding; 5) extrusion traction; grain. This patent also discloses a PET pellet made by this preparation method.
  • the prepared raw materials also include tougheners, antioxidants, heat stabilizers, chain extenders, talcum powder, etc., wherein: tougheners are maleic anhydride grafts or formazan Glycidyl acrylate graft; antioxidant is one or both of antioxidant 1010 and antioxidant 168; heat stabilizer is one of phosphoric acid, polyphosphoric acid and its derivative heat stabilizers , such as triphenyl phosphate (TPP), trimethyl phosphate (TMP), etc., whose function is to prevent or reduce the degradation or crosslinking of waste PET materials during processing and use, and prolong the service life of PET materials; chain extenders It is a combination of one or two of the carboxyl addition type chain extender and the hydroxyl addition type chain extender.
  • tougheners are maleic anhydride grafts or formazan Glycidyl acrylate graft
  • antioxidant is one or both of antioxidant 1010 and antioxidant 168
  • heat stabilizer is one of phosphoric acid, polyphosphoric acid and its derivative heat
  • the carboxyl addition type chain extender can use dioxirane compound, bicyclic imide ether compound, poly Imine compounds, lactam compounds, etc., and diisocyanate, bicyclic carboxylic acid anhydride, bicyclic imine ester, etc. can be used as hydroxyl addition type chain extenders.
  • Chinese patent 201410149632.4 discloses a method of using recycled PET bottles to manufacture textile filaments, including: crushing, washing and drying recycled PET bottles to obtain PET chips; adding PET chips to parallel co-rotating twin-screw extruders
  • the melt is obtained by melting, blending and filtering; the melt is sent into a closed reaction vessel, nitrogen is injected into the closed reaction vessel, dihydric alcohol is added under the agitation of the nitrogen flow, and then the aluminum-based catalyst is added, and the alcohol is mixed and stirred.
  • the processed melt is obtained; the processed melt is sent from the closed reaction vessel to the pressure-resistant reaction vessel through the closed pipeline, vacuumized after sealing, negative pressure stirring for polycondensation reaction, and the intrinsic viscosity of the melt reaches 0.65dl After /g-0.70dl/g, the filaments are discharged through the die, and the filaments for textile are obtained after high-speed spinning.
  • Chinese patent application 201410306245.7 discloses a high tensile strength ultra-thin polyester film and its preparation method.
  • the high tensile strength ultra-thin polyester film is made of the following components and weight percentages: Ester chips: 20-40, polyester masterbatch containing nano-scale SiO 2 additives: 20-40, recycled materials: 10-30, high-viscosity PET: 10-30; the intrinsic viscosity of high-viscosity PET is 0.72-0.76dl/ g;
  • the thickness of the ultra-thin polyester film with high tensile strength is 4-5 ⁇ m.
  • the patent application technology is relatively harsh on the selection of raw materials and is not suitable for recycling waste PET, so it has been rejected.
  • Chinese patent application 201910016689.X discloses a method of using a chain extender to increase the viscosity of recycled polyester bottle flakes and its application. The method is to use the recycled polyester bottle flakes as the base resin and add a chain extender to carry out a chemical chain extension reaction , to prepare high-viscosity polyester, the adopted chain extender is prepared from triphenyl phosphite and epoxy chain extender according to the ratio of 1.5:0.15-0.75 by weight.
  • Chinese patent application 202010232488.6 discloses a tackifier for recycling waste PET textiles.
  • the tackifier is a random copolymer of polystyrene and glycidyl methacrylate, wherein the mass percentage of polystyrene is 60-70%. %.
  • the technology of this application can recycle waste PET textiles, avoiding the pollution of the environment caused by the use of solvents.
  • the purpose of the present invention is to provide a film and laminate prepared by using waste thermoplastic elastomer and recycled polyester. It can be used for laminating fabrics for gloves, fabrics for laminating hats, equipment and food packaging, etc.
  • the present invention provides a film prepared from waste thermoplastic elastomers and recycled polyester, the thickness of the film is 3 ⁇ m-1000 ⁇ m; in weight percentage (the same below), the film includes :
  • thermoplastic elastomer 0%-98% fresh thermoplastic elastomer
  • thermoplastic elastomer is more than one selected from the following group: polyester elastomer, nylon elastomer, biologically derived nylon elastomer and biologically derived polyester elastomer;
  • the viscosity modifier is a reactive viscosity modifier and/or a non-reactive viscosity modifier, and the non-reactive viscosity modifier is selected from one or more of the following group of substances: paraffin wax, microcrystalline wax, polyethylene wax, oxidized polyethylene Waxes, polypropylene waxes, sasol waxes, hyperbranched polymers, APAO, ethylene bisstearamide, EVA, urea, hydroxylamine hydrochloride, hydroxylamine sulfate, and cyclohexanol; reactive viscosity modifiers are epoxy compounds or Low molecular weight, multifunctional esters or alcohols or amines containing hydroxyl or amino groups;
  • the slip agent is one or more selected from the following group: fatty acids and their esters, fatty acid amides, metal soaps, hydrocarbons, organosilicon compounds, stearic acid, butyl stearate and ethylene bisstearamide.
  • the used waste thermoplastic elastomer is scrap and/or head and tail (offcutting);
  • the recycled polyester used is more than one recyclate selected from the following group: polyester bottle, polyester fishing net , polyester packaging materials, polyester injection molded parts for electronics, polyester construction products and polyester home textiles, preferably recycled polyester bottles, polyester fishing nets, polyester packaging materials and polyester injection molded parts for electronics.
  • the intrinsic viscosity of recycled polyester is preferably 0.05-2.0, more preferably 0.05-1.5, which will affect the subsequent film bonding process.
  • the slip agent used is to prevent blocking during the film preparation process, especially during the winding process of the film. Therefore, slip agents are different from lubricants in plastic processing.
  • oleic acid amide In the general film-making process, there are three types of slip agents commonly used: oleic acid amide, erucic acid amide, and silicon dioxide (inorganic powder).
  • organic slippery agents such as oleic acid amide and erucic acid amide are not suitable for the film of the present invention, mainly because a relatively large amount of precipitates are gathered on the surface of the film, which is severe and affects the printability, heat sealability and The color also affects the subsequent bonding process.
  • the inorganic powder is an anti-blocking agent, which will affect the application and subsequent lamination of the film of the present invention. Therefore, one of the prerequisites for selecting a slip agent in the present invention is not to affect the subsequent lamination.
  • the slip agents of the present invention are fatty acids and their esters.
  • the viscosity modifier in the present invention is preferably a reactive viscosity modifier, such as a reactive viscosity modifier
  • the agent can be more than one alcohol chain extender selected from the following group: 1,4-butanediol (BDO), 1,6-hexanediol, glycerin, trimethylolpropane, diethylene glycol ( DEG), triethylene glycol, neopentyl glycol (NPG), sorbitol, and diethylaminoethanol (DEAE).
  • the reactive viscosity modifier is more than one amine and ester chain extender selected from the following group: MOCA, liquid MOCA modified with formaldehyde, ethylenediamine (DA), N,N- Dihydroxy(diisopropyl)aniline (HPA), hydroquinone-bis( ⁇ -hydroxyethyl)ether (HQEE), difunctional acid derivatives, isocyanates, anhydrides, epoxides and glycidyl esters and their polyfunctional groups derivative.
  • MOCA liquid MOCA modified with formaldehyde, ethylenediamine (DA), N,N- Dihydroxy(diisopropyl)aniline (HPA), hydroquinone-bis( ⁇ -hydroxyethyl)ether (HQEE), difunctional acid derivatives, isocyanates, anhydrides, epoxides and glycidyl esters and their polyfunctional groups derivative.
  • the viscosity modifier is epoxy compound and glycidyl ester and its multifunctional derivatives, because they are close to the structure of thermoplastic elastomer, similarly compatible, and will not affect the moisture permeability of thermoplastic elastomer film, elastic recovery Etc caused the drop and more importantly even helped.
  • More preferred are epoxy compounds with fewer functional groups, glycidyl esters and their multifunctional derivatives, which will not cause violent polymerization; for example, 2-4 functional groups, especially 3 functional groups.
  • the prepared film comprises:
  • thermoplastic elastomer 0% - 90% fresh thermoplastic elastomer.
  • the prepared film comprises:
  • thermoplastic elastomer 0% - 5% fresh thermoplastic elastomer.
  • the film of the present invention may also include some processing aids, such as antioxidants, UV agents, and the like.
  • the film of the present invention can be made into a film of any other color, and at this time, 0.1-45% toner needs to be added to the formula of the film.
  • some functional additives can be added to the formula of the film, such as inorganic and organic functional powders such as flame retardants, airgel, infrared powder, graphene, calcium carbonate, titanium dioxide, and phase change materials.
  • the ratio is 0-70%, but one of the prerequisites is still that it cannot affect the subsequent fitting. Therefore, the specific selection and dosage need to pay special attention.
  • the molding method of film (also can be referred to as sheet under the thicker situation) is: Carry out hot-melt molding extrusion with extruder: cast, blown film, spin into net, extrude to molding pumping Vacuum hole forming, calendering, biaxial stretching, uniaxial stretching; liquid forming: forming on the electrostatic spinning base belt, solution coating on the base material, casting forming; later mechanical drilling: laser, chemical corrosion, needle piercing, Flower rolling, ultrasonic drilling, etc.
  • microstructure of the film prepared by the present invention may have holes or no holes in the strict sense, and only molecular gaps exist, as shown in Figures 1-6.
  • the film prepared by the present invention (it can also be called a sheet when the thickness is large) can be washed 3-50 times with ISO6330, preferably 3-20 times.
  • the typical value of moisture permeability JIS L 1099 B1 is 100-60,000.
  • Pressure value JIS L 1092 typical value above 10000mm H 2 O, soft hand feeling (characterized by elastic modulus, ASTM D882), uniform appearance, no obvious glue spots, suitable for clothing, shoes, gloves, hats, bags, etc.
  • Applicable to special devices with moisture-permeable function (such as electronic products, electronic devices, etc.) for surface lamination or packaging, for food that requires moisture-permeable function, for surface lamination or packaging, etc., for various occasions and purposes, especially for clothing .
  • the purpose of the film prepared by the present invention is one of the following:
  • the thickness of the film can be 5 ⁇ m-50 ⁇ m;
  • the thickness of the film or sheet can be 10-500 ⁇ m
  • the thickness of the film can be 8-80 ⁇ m
  • the thickness of the film or sheet can be 50-1000 ⁇ m
  • the thickness of the film or sheet can be 50-1000 ⁇ m.
  • the prepared film or sheet of the present invention can carry out various surface treatments, and this surface treatment can be various functional treatment coatings or discontinuous coatings, especially printing, functional printing (suitable for UV curable ink , screen printing, thermal transfer printing, O-LED printing, roller printing, computer printing, etc., can be any pattern), hydrophobic treatment, hydrophilic treatment, UV or IR barrier treatment, color treatment, graphene coating, Inorganic or organic functional coatings such as airgel layer, phase change cold, heat, temperature sensitive, pressure sensitive, etc.; it can also be surface chemical burning treatment; it can also be various activations such as surface corona, plasma, oxidation, etc. deal with.
  • the thickness of the surface treatment layer is preferably 0.5 ⁇ m or more.
  • the present invention also provides a laminate comprising waste thermoplastic elastomer and recycled polyester, the laminate comprising:
  • the layer has a grammage of 7-1000 gsm
  • composition containing waste thermoplastic elastomer and recycled polyester comprises:
  • thermoplastic elastomer 0%-98% fresh thermoplastic elastomer
  • thermoplastic elastomer is more than one selected from the following group: polyester elastomer, nylon elastomer, biologically derived nylon elastomer and biologically derived polyester elastomer;
  • the viscosity regulator is a reactive viscosity regulator and/or Or non-reactive viscosity modifier, non-reactive viscosity modifier is selected from more than one of the following group of substances: paraffin wax, microcrystalline wax, polyethylene wax, oxidized polyethylene wax, polypropylene wax, sasol wax, overrun Polymers, APAO, ethylene bis stearic acid amide, EVA, urea, hydroxylamine hydrochloride, hydroxylamine sulfate and cyclohexanol; reactive viscosity modifiers are epoxy compounds, or low molecular weight polyfunctional groups containing hydroxyl or amino groups esters or alcohols or amine compounds;
  • the slip agent is more than one selected from the following group: fatty acids and their esters,
  • a glued layer is further included, and the glued layer It is formed by hot-melt glue, solvent glue or water-based glue, and its grammage is 3-80gsm.
  • the film or sheet prepared by the present invention can be laminated with non-woven fabrics and textile fabrics respectively to obtain a laminate, and can also be directly coated or laminated with a hot melt adhesive layer; it can also be laminated with non-woven fabrics or textile fabrics.
  • the hot melt adhesive layer is laminated on the film surface or the cloth surface; the latter two are preferably used for pre-coating glue, and then preferably used for water-stop strips at the seam position and composited with other laminates again, and finally realize the integrity of the entire product. It can be melted and fully recycled again; the hot melt adhesive layer can be continuous or discontinuous.
  • the film or sheet used can be made entirely of waste thermoplastic elastomers (except for viscosity modifiers, slip agents and possible functional additives), without or with little fresh thermoplastic elastomers.
  • the thickness of the film or sheet can be 5-1000 ⁇ m, preferably 5-50 ⁇ m for clothing, 10-500 ⁇ m for shoes, 50-1000 ⁇ m for bags, and 8-500 ⁇ m for adhesive strips.
  • the laminate of the present invention can be a 3-layer composite structure (the glued layer is regarded as one layer, the same below), that is, one layer of textile fabric is glued to one layer of film or sheet, or it can be a 5-layer composite structure, that is, two Layers of textile fabrics laminated with a layer of recycled film and sheet through glue; it can also be a composite structure with more layers.
  • the fabric structure of the selected textile fabric can be polar fleece, plain weave, knitted fabric (grid and plain, single and double knitting), woven fabric (plaid and plain, twill, Single and double-sided texture), foam, air layer, non-woven fabric, cotton (multi-layer interface, natural cotton, Thinsulate, etc.;
  • the material composition of the fabric is mainly PP, PE, PET, PLA, PBAT, PVA and other types alone Or a mixture, it can also be a natural fabric, the raw material of the whole combination of fabrics is recycled or recycled thermoplastic resin, the composition can be PET, nylon, polypropylene, ultra-high density polyethylene, polyethylene, polypropylene, polyvinyl chloride , polystyrene, polymethyl methacrylate, polyester, polyoxymethylene, polyamide, polyphenylene ether, polyurethane, polysulfone, rubber, polyether ether ketone (PEEK), PPS, polyimide (PI), Polyetherimide (PAI),
  • the glue can be pre-coated on the film (sheet) or fabric in advance, and then the fabric and film (sheet) can be compounded by heating; it can also be compounded while applying glue; it can also be pasted by burning Method
  • the surface of the fabric or film (sheet) is activated to have a glue effect and then pasted.
  • the formulation of the laminate of the present invention can be adjusted according to the occasion, so that it has suitable washing performance, moisture permeability, softness and the like.
  • Fig. 1 is a scanning electron microscope schematic diagram of a film structure without pores in strict physical meaning
  • Fig. 2 is a scanning electron microscope schematic diagram of a nano-wire mesh interlaced structure formed by electrospinning
  • Fig. 3 is the scanning electron microscope schematic diagram of the thin film structure that solution forms hole
  • Fig. 4 is the scanning electron microscope schematic diagram of the thin film structure of physical stretching
  • Fig. 5 is a scanning electron microscope schematic diagram of the structure formed by the direct laying non-woven method
  • Fig. 6 is the scanning electron microscope schematic diagram of the film structure of regular physical mechanical pore forming method
  • Fig. 7 is a curve diagram of elastic modulus test.
  • test methods for moisture permeability, hydrostatic pressure, modulus of elasticity, elongation at break, etc. are as follows:
  • Auxiliary membrane PTFE membrane with a pore size of 80% and a thickness of 25um. The auxiliary membrane is used to seal the mouth of the moisture-permeable cup filled with moisture absorbent;
  • Hygroscopic agent Add 100ml of deionized water to every 300g of potassium acetate and leave it for a day and night to form crystals;
  • the distance between the clamps is 250mm
  • the tensile speed is 25mm/min
  • the distance between the clamps is 50mm, and the tensile speed is 500mm/min, set the tensile machine and reset the force value;
  • the melt of the above formula can flow out through the gap at the front end of the die to form a film. After leaving the die, the melt passes through a short gap and reaches the surface of the casting roll at a low temperature to be rapidly cooled and shaped; the melt of the above formula can also be The melt is blown out through the high-pressure air of the rotating die to form a tubular film. After leaving the die, the melt passes through a short gap and reaches the low-temperature casting roll surface to be cooled and shaped rapidly; hole forming), the flat plastic hard sheet is heated and softened, then vacuum adsorbed on the surface of the mold, and formed after cooling;
  • the above formula can also be plasticized to close to the viscous flow temperature through a series of horizontal rollers rotating in opposite directions, so that the material can be squeezed and stretched to become a thin sheet product with a certain thickness, width and smooth surface;
  • the thick film or cast sheet is stretched longitudinally and transversely or uniaxially, and then properly cooled or heat-set in a tensioned state or Special processing (such as corona, coating, etc.);
  • the above-mentioned formula diaphragm can be mechanically drilled, and the mechanical shaft drives the high-strength drill to drill holes on the material with the cutting force generated by the high rotation; laser drilling can also be used, using a high-power density laser beam Irradiate the material to be processed, so that the material is quickly heated to the vaporization temperature, and evaporate to form holes; it can also be chemically etched, which refers to removing the protective film of the area to be etched after exposure to plate making and development, and contacting the chemical solution during etching to achieve dissolution and corrosion The effect of forming concave-convex or hollow-out molding; it is also possible to design needles to pierce holes.
  • This needle can be in the shape of a roll or a template.
  • the needle can be hot or it can be cold; it can also be formed by roll forming, using a smooth surface or a certain shape of the rotating roll to roll the raw material to obtain a certain shape of the product; it can also be punched with ultrasonic waves, and the output signal is sent to the piezoelectric ceramics.
  • the transducer converts ultrasonic electric energy into mechanical vibration energy, and the vibration head vibrates repeatedly under the cooperation of grinding powder (usually emery) and water, so that the processed part is worn through and a suitable small hole is punched.
  • the film prepared according to the above-mentioned film preparation method of this patent formula is compounded with various selected fabric structures and fabric components, which can be two-layer, three-layer sandwich structure, or more than three-layer structure;
  • the method can be liquid rubber roller coating or spraying, or hot melt adhesive melted and then rolled or sprayed, or hot melt adhesive net, mesh, and film are compounded after being melted by rolling, and can be bonded by burning and pasting. Lamination is carried out in different ways, and finally a laminate of patented products is formed.
  • Example 1 Effect of proportion of recycled PET bottle flakes
  • the film preparation process a series of 15 ⁇ m films were prepared, and the influence of the proportion of recycled PET bottle flakes on moisture permeability, hydrostatic pressure, washing times (hydrostatic pressure after how many times) and hand softness were investigated.
  • the results are shown in the table One, wherein, the film-forming composition does not contain fresh thermoplastic elastomers, except for recycled bottle flakes, viscosity regulators and slippery agents, all the others are waste thermoplastic elastomers (i.e. online leftovers);
  • Embodiment 2 the influence of the proportion of recycled PET bottle flakes and leftover material on product performance
  • Embodiment 3 The influence of film thickness on product performance
  • Embodiment 4 the influence of viscosity modifier on product performance
  • the experiment number 242-247 done by the applicant is the formula of recycled PET bottle flakes + waste thermoplastic elastomer accounting for 75%
  • the experiment number 248-253 is the formula of recycled PET bottle flakes + waste thermoplastic elastomer accounting for 50%
  • Experiment No. 254-259 is the formula of recycled PET bottle flakes + waste thermoplastic elastomer accounting for 25%
  • Experiment No. 260-264 is the formula of recycled PET bottle flakes + waste thermoplastic elastomer accounting for 10%.
  • 2 to the processing method of Fig. 6 is prepared, and the product obtained is also close to the performance of the product in Table 5.

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Abstract

公开了一种由废旧热塑性弹性体和回收聚酯制备的薄膜及其层合物，形成薄膜的组合物包括：0.5％－90％的废旧热塑性弹性体、0.5％－90％的特性粘度在0.5－2之间的回收聚酯、0.01％－3％的粘度调节剂、0.01％－10％的防止所制成薄膜收卷时粘合的爽滑剂以及0％－98％的新鲜热塑性弹性体；其中，回收聚酯为回收的聚酯瓶、聚酯渔网、聚酯包装材料、电子产品聚酯注塑件、聚酯建筑产品、聚酯家纺等；热塑性弹性体为涤纶弹性体、尼龙弹性体、生物来源的尼龙弹性体和/或生物来源的涤纶弹性体。制备的薄膜具有良好的透湿性能、洗涤性能、拉伸强度和所需要的手感柔软度。

Description

由废旧热塑性弹性体和回收聚酯形成的薄膜及层合物 技术领域
本发明涉及废旧塑料特别是废旧热塑性弹性体和回收聚酯的再生利用；更具体地讲，本发明涉及一种由废旧热塑性弹性体和回收聚酯形成的薄膜及其层合物。
背景技术
塑料制品自身良好的性能以及较低的成本，使得各种塑料制品在诸多领域中充当着重要的角色。但塑料制品在为人们生活带来便利的同时，废旧塑料对环境的污染导致地球不堪重负。事实证明，无论是填埋还是焚烧，都不是好的处理方法。能够进行低成本的回收处理，是一较佳的选择。
聚对苯二甲酸乙二醇酯(PET)是一种具有良好力学性能和加工性能的聚酯材料，可以用来生产饮料瓶、包装袋、薄膜、纤维等产品。消费者在使用PET包装后大多会直接丢弃，因此会产生大量的废弃PET。
目前回收PET的改性方法主要可分为三类：一是降解改性，即通过降低分子量使回收PET解聚成对苯二甲酸及其酯类等低分子量物质，然后重新合成PET或制成其他产品；二是固相缩聚改性，使回收PET在特定温度下并加以其他条件辅助，使分子量增加，重新作为高粘度聚酯使用；三是化学扩链改性，使回收PET与扩链剂发生化学反应，使得回收PET分子量增加。
现有技术中，中国专利99812803.1公开了一种制备泡沫制品的方法，其包括：将含有以下组分的混合物加热至不低于聚酯熔点的温度下，以制备具有50克/10分钟或更低的熔体流动速率和10－200％溶胀的聚酯树脂；然后在发泡剂的帮助下将该聚酯树脂进行热发泡，其中该混合物包含：(a)100重量份的线型饱和聚酯；(b)0.1－10重量份的偶联剂混合物，其由0－100重量％的在分子中含两个环氧基的化合物和100－0重量％的含两个或更多环氧基的化合物组成；以及(c)0.01－5重量份作为偶联反应催化剂的羧酸金属盐。该专利技术将回收的聚酯制成泡沫制品， 用作缓冲材料、绝热材料、包装材料、食品容器、分配材料等。
中国专利201110288666.8则公开了一种废旧PET增韧增粘方法，其包括以下步骤：1)预备原料；2)粉碎烘干；3)混合；4)加料；5)挤出牵引；6)冷却造粒。该专利还公开了一种利用这种制备方法所制得的PET粒料。在该专利中，其预备的原料除废旧PET外，还包括增韧剂、抗氧剂、热稳定剂、扩链剂、滑石粉等，其中：增韧剂为马来酸酐接枝物或甲基丙烯酸缩水甘油脂接枝物；抗氧剂为抗氧剂1010、抗氧剂168中的一种或两种；热稳定剂为磷酸、多磷酸及其衍生物类热稳定剂中的一种，如磷酸三苯酯(TPP)、磷酸三甲酯(TMP)等，其作用是防止或减少废旧PET料在加工使用过程中受热而发生降解或交联，延长PET材料使用寿命；扩链剂为羧基加成型扩链剂、羟基加成型扩链剂中的一种或两种的组合物，羧基加成型扩链剂可采用双环氧乙烷化合物、双环亚胺醚化合物、多聚碳化二亚胺化合物、内酰胺化合物等，羟基加成型扩链剂可采用二异氰酸脂、双环羧酸酐、双环亚胺脂等。
中国专利201410149632.4公开了一种利用回收的PET瓶制造纺织用长丝的方法，包括：将回收的PET瓶经破碎、洗涤和干燥，得到PET碎片；将PET碎片加入到平行同向双螺杆挤出机中，经熔融共混和过滤，得到熔体；将熔体送入密闭反应容器，向密闭反应容器中注入氮气，在氮气流鼓动下加入二元醇，再加入铝基催化剂，混合搅拌进行醇解反应，得到处理后的熔体；将处理后的熔体经密闭管道从密闭反应容器送入到耐压反应容器，密闭后抽真空，负压搅拌进行缩聚反应，熔体特性粘度达到0.65dl/g－0.70dl/g后，通过口模出丝，经高纺后得到纺织用长丝。
中国专利申请201410306245.7公开了一种高拉伸强度超薄型聚酯薄膜及其制备方法，该高拉伸强度超薄型聚酯薄膜由以下组分及重量百分比的原料制成：大有光聚酯切片：20～40、含纳米级SiO 2添加剂的聚酯母料：20～40、回收料：10～30、高粘PET：10～30；高粘PET的特性粘度为0.72～0.76dl/g；高拉伸强度超薄型聚酯薄膜的厚度为4～5μm。该专利申请技术对于原料的选择较为苛刻，并不适合回收废旧PET，已被驳回。
中国专利申请201910016689.X公开了一种利用扩链剂增粘回收聚酯瓶片的方法及其应用，该方法为以回收的聚酯瓶片为基体树脂，加入扩链剂进行化学扩链反应，制得高粘度聚酯，所采用的扩链剂是亚磷酸三苯酯和环氧扩链剂按照重量份为1.5：0.15～0.75的比例配制所得。
中国专利申请202010232488.6则公开了一种废旧PET纺织品回收的增粘剂，该增粘剂为聚苯乙烯与甲基丙烯酸缩水甘油酯的无规共聚物，其中聚苯乙烯的质量百分比为60～70％。该申请的技术可对废旧PET纺织品进行回收，避免了使用溶剂对环境造成的污染。
在人类的衣食住行中，衣服里面用到的树脂材料占据了能源很大的一块，其中日益崛起的代表服装的先进技术，集约了很多功能性服用产品。如何将废旧热塑性弹性体和回收聚酯同时应用于服用产品，同时如何把服用产品里面的不可重复利用的部分进行置换，是现有技术中需要解决的最主要问题。
发明内容
本发明的目的是提供一种利用废旧热塑性弹性体和回收聚酯制备的薄膜及其层合物，所得到的薄膜可以用于贴合服用面料、贴合鞋用面料、贴合箱包用面料、贴合手套用面料、贴合帽子用面料、器械及食品包装等用途。
为了实现上述的发明目的，一方面，本发明提供了一种由废旧热塑性弹性体和回收聚酯制备的薄膜，该薄膜的厚度为3μm－1000μm；以重量百分数计(下同)，该薄膜包括：
0.5％－90％的废旧热塑性弹性体；
0.5％－90％的、特性粘度在0.5－2之间的回收聚酯；
0.01％－3％的粘度调节剂；
0.01％－10％的防止所制成薄膜收卷时粘合的爽滑剂；以及
0％－98％的新鲜热塑性弹性体；
其中，热塑性弹性体为选自于如下一组的一种以上：涤纶弹性体、尼龙弹性体、生物来源的尼龙弹性体和生物来源的涤纶弹性体；
粘度调节剂为反应型粘度调节剂和/或非反应型粘度调节剂，非反应型粘度调节剂选自于如下一组物质的一种以上：石蜡、微晶蜡、聚乙烯蜡、氧化聚乙烯蜡、聚丙烯蜡、沙索蜡、超支化聚合物、APAO、亚乙基双硬脂酸酰胺、EVA、尿素、盐酸羟胺、硫酸羟胺和环己醇；反应型粘度调节剂为环氧化合物或者含羟基或氨基的低分子量的、多官能团的酯类或醇类或胺类化合物；
爽滑剂选自于如下一组的一种以上：脂肪酸及其酯类、脂肪酸酰胺、金属皂、烃类、有机硅化合物、硬脂酸、硬脂酸丁酯和乙撑双硬脂酰胺。
本发明中，所采用的废旧热塑性弹性体为边角料和/或头尾料(offcutting)；所采用的回收聚酯为选自于如下一组的一种以上回收物：聚酯瓶、聚酯渔网、聚酯包装材料、电子产品聚酯注塑件、聚酯建筑产品和聚酯家纺，优选为回收的聚酯瓶、聚酯渔网、聚酯包装材料和电子产品聚酯注塑件。
需要特别注意的是，回收聚酯的特性粘度优选为0.05－2.0、更优选为0.05－1.5，这会影响后续的薄膜贴合工艺。
本发明中，所使用的爽滑剂是防止薄膜制备过程中发生粘连，特别是在薄膜的收卷过程中。所以，爽滑剂不同于塑料加工过程中的润滑剂。
在一般的制膜过程中，常用的爽滑剂有三类：油酸酰胺、芥酸酰胺、二氧化硅(无机粉体)。然而，油酸酰胺、芥酸酰胺等有机爽滑剂不适合于本发明的薄膜，主要表现在有较大量的析出物聚集在薄膜表面，起爽严重，影响薄膜的印刷性、热封性及颜色，也影响了后续的贴合工艺。而无机粉体是一种开口剂，会影响本发明薄膜的使用用途和后续贴合等。所以，本发明选择爽滑剂的前提条件之一是不影响后续的贴合。
优选地，本发明的爽滑剂是脂肪酸及其酯类。
类似地，为了防止影响所制得的薄膜的印刷性、热封性及颜色，也为了防止影响后续的贴合工艺，本发明中粘度调节剂优选为反应型粘度调节剂，例如反应型粘度调节剂可以为选自于如下一组的一种以上的醇类扩链剂：1，4一丁二醇(BDO)、1，6一己二醇、甘油、三羟甲基丙烷、 二甘醇(DEG)、三甘醇、新戊二醇(NPG)、山梨醇和二乙氨基乙醇(DEAE)。
或者反应型粘度调节剂为选自于如下一组的一种以上的胺类及酯类扩链剂：MOCA、用甲醛改性制得的液体MOCA、乙二胺(DA)、N，N－二羟基(二异丙基)苯胺(HPA)、氢醌－二(β一羟乙基)醚(HQEE)、双官能团酸衍生物、异氰酸酯、酸酐、环氧化物和缩水甘油酯及其多官能团衍生物。
更优选地，粘度调节剂为环氧化合物和缩水甘油酯及其多官能团衍生物，因为他们与热塑性弹性体的结构接近，相似相容，且不会对热塑性弹性体薄膜的透湿性，弹性回复等造成下降，更重要的是甚至有帮助。更优选的是官能团较少环氧化合物和缩水甘油酯及其多官能团衍生物，其不会引起暴聚；例如，可以是2－4个官能团，特别是3个官能团。
在本发明的一具体实施方式中，所制备的薄膜包括：
2.5％－99.8％的废旧热塑性弹性体；
0.01％－2％的粘度调节剂；
0.01％－10％的不影响贴合的爽滑剂；以及
0％－90％的新鲜热塑性弹性体。
为了提高废旧热塑性弹性体的使用率，在本发明的另一具体实施方式中，所制备的薄膜包括：
80％－99.8％的废旧热塑性弹性体；
0.1％－2％的粘度调节剂；
0.1％－10％的不影响贴合的爽滑剂以及
0％－5％的新鲜热塑性弹性体。
一般情况下，本发明的薄膜中还可能包括一些加工助剂，如抗氧剂、UV剂等。
本发明的薄膜可以做成任意其他颜色的膜，此时需要在薄膜的配方中加入0.1－45％的色粉。
另外，在薄膜的配方中还可以加上一些功能化助剂，如阻燃剂、气凝胶、红外粉、石墨烯、碳酸钙、二氧化钛、相变材料等类型的无机、有机功能性粉末，比例为0－70％，但前提条件之一仍然是不能影响后续 的贴合。所以，具体的选择和用量需要格外注意。
本发明中，薄膜(较厚的情况下也可以称为片材)的成型方法为：用挤出机进行热熔融成型挤出：流延，吹膜，喷丝成网，挤出至成型抽真空孔洞成型，压延，双向拉伸，单向拉伸；液体成型：静电喷丝基带上成型，溶液涂布在基材上成型，浇注成型；后期机械打孔：激光，化学腐蚀，针扎，花辊压，超声波打孔等。
本发明所制备的薄膜的微观结构可以是有孔的，也可以是无严格意义上的孔，只有分子间隙存在，可参阅附图1－6。
本发明所制备的薄膜(厚度较大时也可称为片材)可用ISO6330洗涤3－50次，优选3－20次，透湿性能JIS L 1099 B1典型值是100－60，000，静水压值JIS L 1092典型值10000mm H 2O以上，手感柔软(用弹性模量表征，ASTM D882)，外观均匀，无明显胶点，适合服用、鞋用、手套用、帽子用、箱包用、需要透湿功能的特殊器械(如电子产品、电子器械等)面层贴合或包装用、需要透湿功能的食品的面层贴合或者包装用等多种场合、多种用途，特别是衣着用途。
更具体地，本发明所制备薄膜的用途为如下之一：
(1)用于贴合服用面料，其中，薄膜的厚度可为5μm－50μm；
(2)用于贴合鞋用面料，其中，薄膜或片材的厚度可为10－500μm；
(3)用于贴合手套、帽子用面料方面的用途，其中，薄膜的厚度可为8－80μm；
(4)用于贴合箱包面料，其中，薄膜或片材的厚度可为50－1000μm；
(5)用于需要透湿功能的器械的面层贴合或者包装，其中，薄膜或片材的厚度可为50－1000μm；
(6)用于需要透湿功能的食品的面层贴合或者包装，其中，薄膜或片材的厚度可为50－1000μm。
另外，本发明所制备的薄膜或片材可以进行各种表面处理，这种表面处理可以是各种功能处理涂层或者不连续涂层，尤其是印花、功能性印花(适用于紫外光固化油墨、丝网印花、热转移印花、O－LED印花， 辊印、电脑印花等等，可以是任意图案)、疏水处理、亲水化处理、UV或者IR阻隔处理、颜色处理、石墨烯涂层、气凝胶层、相变冷感、热感、温敏、压敏等无机或有机功能化涂层；也可以是表面化学烧花处理；还可以是表面电晕、等离子、氧化等各种活化处理。表面处理层的厚度优选为0.5μm以上。
另一方面，为了实现本发明的目的，本发明还提供了一种包含废旧热塑性弹性体和回收聚酯的层合物，该层合物包括：
至少一层由无纺布和/或纺织面料形成的层，该层的克重为7－1000gsm；以及
至少一层由含废旧热塑性弹性体的组合物形成的层，该层的厚度为5－1000μm；
其中，所述的含废旧热塑性弹性体和回收聚酯的组合物包括：
0.5％－90％的废旧热塑性弹性体；
0.5％－90％的、特性粘度在0.5－2之间的回收聚酯；
0.01％－3％的粘度调节剂；
0.01％－10％的防止所制成薄膜收卷时粘合的爽滑剂；以及
0％－98％的新鲜热塑性弹性体；
其中，热塑性弹性体为选自于如下一组的一种以上：涤纶弹性体、尼龙弹性体、生物来源的尼龙弹性体和生物来源的涤纶弹性体；粘度调节剂为反应型粘度调节剂和/或非反应型粘度调节剂，非反应型粘度调节剂选自于如下一组物质的一种以上：石蜡、微晶蜡、聚乙烯蜡、氧化聚乙烯蜡、聚丙烯蜡、沙索蜡、超支化聚合物、APAO、亚乙基双硬脂酸酰胺、EVA、尿素、盐酸羟胺、硫酸羟胺和环己醇；反应型粘度调节剂为环氧化合物、或者含羟基或氨基的低分子量的多官能团的酯类或醇类或胺类化合物；爽滑剂为选自于如下一组的一种以上：脂肪酸及其酯类、脂肪酸酰胺、金属皂、烃类、有机硅化合物、硬脂酸、硬脂酸丁酯和乙撑双硬脂酰胺。
优选地，在本发明的层合物中，在由无纺布和/或纺织面料形成的层和由含废旧热塑性弹性体的组合物形成的层之间，进一步包括一胶合层，该胶合层是由热熔胶、溶剂胶或水性胶形成的，其克重为3－80gsm。
例如，本发明制备的薄膜或片材可以分别与无纺和纺织面料层合得到层合物，也可以直接涂或者层合上热熔胶层；也可以是与无纺布或者纺织面料层合后，在膜面或者布面层合上热熔胶层；后两者优选为预涂胶用，再优选为缝合位置止水条用及再次与其它层合物复合用，最终实现整个制品的再次可熔融全回收；其中热熔胶层可以是连续的也可以是不连续的。
本发明层合物中，所采用的薄膜或片材可以是全部由废旧热塑性弹性体制得(除粘度调节剂、爽滑剂及可能的功能添加剂外)，不含或者少含新鲜的热塑性弹性体。薄膜或片材的厚度可为5－1000μm，其中服装用优选为5－50μm，鞋材用优选为10－500μm，箱包用优选为50－1000μm，胶条用的优选8－500μm。
本发明的层合物可以是3层复合结构(胶合层视为一层，下同)，即一层纺织面料通过胶贴合一层薄膜或片材，也可以是5层复合结构，即两层纺织面料通过胶中间贴合一层回收膜及片材；也可以是更多层数的复合结构。
本发明的层合物中，所选用的纺织面料的面料结构可以是摇粒绒、平织布、针织布(网格和平纹，单双针织)、梭织布(格子布和平纹，斜纹，单双面纹路)、泡棉、空气层、无纺布、棉(多层介面、天然棉、新雪丽等；面料的材料成分主要是PP、PE、PET、PLA、PBAT、PVA等类型单独的或混合物，也可以是天然织物，整个组合的面料的原料是可回收的或者回收了的热塑性树脂，成分可为PET，尼龙，丙纶，超高密度聚乙烯、聚乙烯、聚丙烯、聚氯乙烯、聚苯乙烯、聚甲基丙烯酸甲酯、聚酯、聚甲醛、聚酰胺、聚苯醚、聚氨酯、聚砜、橡胶、聚醚醚酮(PEEK)、PPS、聚酰亚胺(PI)、聚醚酰亚胺(PAI)、PVA等的单独的或者任意混合的)纺织而成。其中回收了的热塑性树脂里面的回收比例范围是0.5－100％，优选5％－100％的，优选与回收膜及片材同一类型的树脂。
贴合(或复合)时是要保证透湿率在100g/m2＊24h以上，水洗次数3次以上，可以选择胶是聚氨酯类、涤纶、APEO、尼龙等热熔胶、溶剂胶或水性胶，可以是点状、网格、喷丝、花纹等任意不连续胶点。也可 以选择不需要胶的方式，比如烧贴、淋复、规则状热贴等等。
贴合的方法：可以事先将胶预涂在薄膜(片材)或者面料上面，然后通过加热将面料和薄膜(片材)进行复合；也可以是涂胶的同时进行复合；也可以通过烧贴方法将面料或者薄膜(片材)的表面活化成具有胶合效果后进行贴合。
本发明的层合物可以根据场合，调整配方，使之具有相适合的洗涤性能、透湿性能、手感柔软度等。
下面，结合附图和具体实施方式对本发明作进一步的说明，但这些具体实施方式只是针对本发明某些特定的具体实施方式的说明而已，并非是对本发明的限定。
附图说明
图1是无严格物理意义孔隙的薄膜结构的扫描电镜示意图；
图2是利用静电纺丝形成的纳米丝网交错结构的扫描电镜示意图；
图3是溶液成孔的薄膜结构的扫描电镜示意图；
图4是物理拉伸成孔的薄膜结构的扫描电镜示意图；
图5是直铺无纺法所形成结构的扫描电镜示意图；
图6是规则物理机械成孔法的薄膜结构的扫描电镜示意图；
图7是弹性模量测试曲线图。
具体实施方式
在下面的各具体实施方式中，透湿率、静水压、弹性模量、断裂伸长率等测试方法如下：
(1)静水压检测：
A)检测标准：AATCC127；
B)采样标准：按斜对角取至少3块200mm*200mm的样，避免测试区域的折叠和污染；测试前样品在(21±2)℃，(65±2)％调湿至少4小时，测试需要区分面料正反面。
C)检测方法：在(21±2)℃条件下，擦干夹持装置表面的水， 夹持调湿后的样品使样品正面与水面接触。选择测试程序，升压速摄氏度(60mbar/min)，记录第三滴水珠出现时的水压值，三处水珠应是不同处且不是夹具边缘3mm内的水珠。
(2)透湿率:JIS L1099B1法醋酸钾法：
设备：恒温箱温度：30±2℃，恒温箱中的水槽温度：约23℃；天平内径56mm，高75mm的透湿杯
辅助膜：孔径80％，厚度25um的PTFE膜，辅助膜用于把装有吸湿剂的透湿杯的口密封好；
吸湿剂：每300g醋酸钾加100ml的去离子水，放置一昼夜后，形成的结晶体；
取样：约20cm x 20cm
测试步骤：
把样品用橡胶带固定在支撑框上，然后放入恒温箱的恒温水槽中，深度约10mm，放置15min，在透湿杯中放2/3的吸湿剂(约23℃)，拿辅助膜和橡胶带固定好透湿杯的杯口，把装好的透湿杯放在天平中称重a1，称完后把透湿杯倒立放置在固定好的测试样品上，15min后取出透湿杯，放在天平中称重a2计算透湿率。
(3)弹性模量：ASTM D882：
设备：具有稳定移动速度的拉力机；精确到0.0025mm的厚度计薄膜试样裁切机：裁切出来的样品不能有肉眼可见缺口，锯齿状等取样：按所需的测试方向进行裁切，试样宽度为15mm，长度300mm(裁切出来的样品如有明显得缺口或锯齿状，应丢弃，重新裁切)，每个方向至少准备5个样品，然后将裁切好的的试样放于23±1℃，相对湿度50±5％的条件下，不少于40h；
测试步骤：
按照约定好的负荷传感器，夹具间距250mm，拉伸速度25mm/min，将拉力机设定好，将力值清零
测量试样的厚度，宽度，输入拉力机的软件中，夹好试样，尽量让初始力值为0，点击开始，当图中出现最大斜率的拐点时(如图)，停止测试，读出并记录结果(Mpa)
(4)断裂伸长率：ASTM D882：
设备：具有稳定移动速度的拉力机；精确到0.0025mm的厚度计；薄膜试样裁切机：裁切出来的样品不能有肉眼可见缺口，锯齿状等取样：按所需的测试方向进行裁切，试样宽度为15mm，长度不小于150mm(裁切出来的样品如有明显得缺口或锯齿状，应重新裁切，)每个方向至少准备5个样品，然后将裁切好的的试样放于23±1℃，相对湿度50±5％的条件下，不少于40h；
测试步骤：
按照约定好的负荷传感器，夹具间距50mm，拉伸速度500mm/min，将拉力机设定好，将力值清零；
夹好试样，尽量让初始力值为0，点击开始，直至试样断裂，读出并记录试样断裂时的伸长率％(如测试过程中，试样有滑移，试样在缺陷处断裂等，均为无效结果)。
薄膜的制备：
可将上述配方的熔体通过模头前端的缝隙流出，形成薄膜，离开模头后，熔体经过一个短的间隙，到达低温的流延辊面而急剧冷却定型；也可将上述配方的熔体通过旋转模头高压空气吹出，形成管状薄膜，离开模头后，熔体经过一个短的间隙，到达低温的流延辊面而急剧冷却定型；还可将上述配方熔融挤出至成型抽真空孔洞成型)，将平展的塑料硬片材加热变软后，采用真空吸附于模具表面，冷却后成型；
也可将上述配方塑化到接近粘流温度通过一系列相向旋转着的水平辊筒间隙，使物料承受挤压和延展作用，成为具有一定厚度、宽度与表面光洁的薄片状制品；还可进一步将上述膜片在低于薄膜材料熔点、高于玻璃化转变温度时，对厚膜或铸片进行纵向和横向双向或者单向拉伸，然后在张紧状态下进行适当冷却或热定型处理或特殊的加工(如电晕、涂覆等)；
关于进步成孔，可将上述配方膜片进行机械打孔，用机械转轴带动高强度钻针以高度旋转产生的切削力在材料上钻出孔；也可以激光打孔，利用高功率密度激光束照射被加工材料，使材料很快被加热至汽化温度，蒸发形成孔洞；还可以化学蚀刻，指通过曝光制版、显影后，将 要蚀刻区域的保护膜去除，在蚀刻时接触化学溶液，达到溶解腐蚀的作用，形成凹凸或者镂空成型的效果；也还可以设计针状物扎出孔洞，这种针状物可以是辊状，也可以是模板状，同时这种针可以是热的，也可以是冷的；还可以通过辊压成型，利用表面光滑或加工有一定形状的旋转轧辊对原料进行压延，制得一定形状产品；也可以用超声波打孔，输出的信号送入以压电陶瓷构成的换能器，把超声波电能转换为机械震动能，震头在磨粉(一般为金钢砂)和水的配合下反复震动，使得加工部分磨穿，打出适合的小孔。
层合物的制备：
将本专利配方按照上述薄膜制备方法制备的薄膜，与选择的各种织物结构和织物成分进行复合，可以是两层，也可以是三明治三层结构，也可以是三层以上结构；采用的复合方式，可以是液体胶滚涂或者喷涂，也可以是热熔胶熔化后滚涂或者喷涂，还可以是热熔胶网，网格，膜通过辊压熔化后进行复合，更可以通过烧贴的方式进行贴合，最终形成专利产品的层合物。
实施例1：回收的PET瓶片比例的影响
按照上述的薄膜制备过程，制备一系列的15μm薄膜，考察回收PET瓶片的比例对于透湿度、静水压、水洗次数(多少次后的静水压)、手感柔软度的影响，结果见表一，其中，形成薄膜的组合物中，不含有新鲜的热塑性弹性体，除回收瓶片、粘度调节剂和爽滑剂外，其余均为废旧热塑性弹性体(即在线边角料)；
表一回收的PET瓶片比例对产品性能的影响
Figure PCTCN2021101789-appb-000001
表1中的数据表明，加入的回收PET瓶片的比例越高手感越硬，透湿度越低，静水压越高，越耐水洗；当回收PET瓶片的比例达到30％以上时，弹性模量快速增长，手感柔软度快速下降。
实施例2：回收的PET瓶片及边角料比例对产品性能的影响
按照上述的薄膜制备过程，制备一系列的15μm薄膜，考察回收的PET瓶片及边角料比例对产品性能的影响，结果见表二；
表二回收PET瓶片及边角料比例对产品性能的影响
Figure PCTCN2021101789-appb-000002
从表2中数据可以发现，当控制回收PET瓶片的比例超过30％，例如15％左右，即使形成薄膜的组合物中回收瓶片+废旧热塑性弹性体的比例相当高，例如基本、甚至完全不使用新鲜料(新的热塑性弹性体)时，所得到的薄膜在透湿度、静水压、洗涤次数、手感柔软度等性能方面，都是相当出色。
实施例3：薄膜厚度对产品性能影响
按照上述的薄膜制备过程，制备一系列厚度的薄膜，考察不同厚度对于透湿度、静水压、水洗次数(多少次后的静水压)的影响，结果见表三，其中，制备薄膜的组合物中，完全不使用新的热塑性弹性体，回收PET瓶片的比例在15％左右，其余为废旧热塑性弹性体、粘度调节剂和爽滑剂；
表三厚度对产品性能的影响
Figure PCTCN2021101789-appb-000003
从表3中数据可以发现，厚度越大，透湿度越小，但在5-30μm的厚度范围内，所有薄膜都具有相当高的透湿度；厚度越大，抗洗涤能力越高，在大于30μm后，薄膜几乎不受洗涤次数的影响。
实施例4：粘度调节剂对产品性能的影响
按照上述的薄膜制备过程，制备一系列具有不同粘度调节剂含量的薄膜，考察粘度调节剂的剂量对于成膜性能、透湿度、静水压、水洗次数(多少次后的静水压)、手感(弹性模量表征)的影响，结果见表四，其中所制备的薄膜不含有新鲜的热塑性弹性体，薄膜的厚度为15μm；
表四不同材质对产品性能的影响关系
Figure PCTCN2021101789-appb-000004
从表4中数据可以发现，对于一般的废旧热塑性弹性体和回收瓶片，不添加粘度调节剂或调节剂浓度过低，制膜时只能得到液态的物质，无 法成膜或无法形成稳定的膜。当然，如果废旧热塑性弹性体本身或者回收瓶片本身含有粘度调节剂，就另当别论了。
实施例5：薄膜结构的影响
按照上述的薄膜制备过程，制备一系列的薄膜，考察有孔膜和无孔膜的透湿度、静水压、水洗次数(多少次后的静水压)、手感(弹性模量表征)的影响，结果见表五，其中所制备的薄膜不含有新鲜的热塑性弹性体，薄膜的厚度为15μm；
表五有孔、无孔、孔型不同对产品性能的影响关系
Figure PCTCN2021101789-appb-000005
从表5中数据可以发现，采用不同的结构，各种薄膜的透湿性能相差不大，但强度、洗涤次数和弹性模量有一定差别；综合来看，无孔薄膜性能最优，溶液成孔的薄膜结构也表现不错。
实施例6
申请人所做的实验编号242－247为回收PET瓶片+废旧热塑性弹性体的比例占75％的配方、实验编号248－253为回收PET瓶片+废旧热塑性弹性体的比例占50％的配方、实验编号254－259为回收PET瓶片+废旧热塑性弹性体的比例占25％的配方、实验编号260－264为回收PET瓶片+废旧热塑性弹性体的比例占10％的配方，分别进行图2到图6的工艺方法进行制备，得到的产品也与表五产品性能接近。

Claims (10)

  1. 一种由废旧热塑性弹性体和回收的聚酯制备的薄膜，该薄膜的厚度为3μm－1000μm，其中，形成所述薄膜的组合物包括：
    0.5％－90％的废旧热塑性弹性体；
    0.5％－90％的、特性粘度在0.5－2之间的回收聚酯；
    0.01％－3％的粘度调节剂；
    0.01％－10％的防止所制成薄膜收卷时粘合的爽滑剂；以及
    0％－98％的新鲜热塑性弹性体；
    其中，所述的热塑性弹性体为选自于如下一组的一种以上：涤纶弹性体、尼龙弹性体、生物来源的尼龙弹性体和生物来源的涤纶弹性体；
    所述的粘度调节剂为反应型粘度调节剂和/或非反应型粘度调节剂及其混合物，所述的非反应型粘度调节剂选自于如下一组物质的一种以上：石蜡、微晶蜡、聚乙烯蜡、氧化聚乙烯蜡、聚丙烯蜡、沙索蜡、超支化聚合物、APAO、亚乙基双硬脂酸酰胺、EVA、尿素、盐酸羟胺、硫酸羟胺和环己醇；所述的反应型粘度调节剂为环氧化合物、或者含羟基或氨基的低分子量的多官能团的酯类或醇类或胺类化合物；
    所述的爽滑剂为选自于如下一组的一种以上：脂肪酸及其酯类、脂肪酸酰胺、金属皂、烃类、有机硅化合物、硬脂酸、硬脂酸丁酯和乙撑双硬脂酰胺。
  2. 如权利要求1所述的薄膜，其中，所述的薄膜包括：
    2.5％－80％的废旧热塑性弹性体；
    5％－80％的回收聚酯；
    0.01％－2％的粘度调节剂；
    0.01％－10％的不影响贴合的爽滑剂；以及
    0％－60％的新鲜热塑性弹性体。
  3. 如权利要求1所述的薄膜，其中，所述的废旧热塑性弹性体为边角料和/或头尾料。
  4. 如权利要求1所述的薄膜，其中，所述的回收聚酯为选自于如下一组的一种以上回收物：聚酯瓶、聚酯渔网、聚酯包装材料、电子产品聚酯注塑件、聚酯建筑产品和聚酯家纺。
  5. 如权利要求1所述的薄膜，其中，所述的反应型粘度调节剂为选自于如下一组的一种以上的醇类扩链剂：1，4一丁二醇(BDO)、1，6一己二醇、甘油、三羟甲基丙烷、二甘醇(DEG)、三甘醇、新戊二醇(NPG)、山梨醇和二乙氨基乙醇(DEAE)。
  6. 如权利要求1所述的薄膜，其中，所述的反应型粘度调节剂为选自于如下一组的一种以上的胺类及酯类扩链剂：MOCA、用甲醛改性制得的液体MOCA、乙二胺(DA)、N，N－二羟基(二异丙基)苯胺(HPA)、氢醌－二(β一羟乙基)醚(HQEE)、双官能团酸衍生物、异氰酸酯、酸酐、环氧化物和缩水甘油酯及其多官能团衍生物。
  7. 如权利要求1所述的薄膜，其中，所述的反应型粘度调节剂为环氧化合物。
  8. 如权利要求1－7之一所述的薄膜，其中，所述薄膜的用途为如下之一：
    (1)用于贴合服用面料，其中，所述的薄膜的厚度为5μm－50μm；
    (2)用于贴合鞋用面料，其中，所述的薄膜的厚度为10－500μm；
    (3)用于贴合手套、帽子用面料方面的用途，其中，所述的薄膜的厚度为8－80μm；
    (4)用于贴合箱包面料，其中，所述的薄膜的厚度为50－1000μm；
    (5)用于需要透湿功能的器械的面层贴合或者包装，其中，所述的薄膜的厚度为50－1000μm；
    (6)用于需要透湿功能的食品的面层贴合或者包装，其中，所述的薄膜的厚度为50－1000μm。
  9. 一种包含废旧热塑性弹性体和回收聚酯的层合物，该层合物包括：
    至少一层由无纺布和/或纺织面料形成的层，该层的克重为7－1000gsm；以及
    至少一层由含废旧热塑性弹性体的组合物形成的层，该层的厚度为5－1000μm；
    其中，所述的含废旧热塑性弹性体和回收聚酯的组合物包括：
    0.5％－90％的废旧热塑性弹性体；
    0.5％－90％的、特性粘度在0.5－2之间的回收聚酯；
    0.01％－3％的粘度调节剂；
    0.01％－10％的防止所制成薄膜收卷时粘合的爽滑剂；以及
    0％－98％的新鲜热塑性弹性体；
    其中，所述的热塑性弹性体为选自于如下一组的一种以上：涤纶弹性体、尼龙弹性体、生物来源的尼龙弹性体和生物来源的涤纶弹性体；
    所述的粘度调节剂为反应型粘度调节剂和/或非反应型粘度调节剂，所述的非反应型粘度调节剂选自于如下一组物质的一种以上：石蜡、微晶蜡、聚乙烯蜡、氧化聚乙烯蜡、聚丙烯蜡、沙索蜡、超支化聚合物、APAO、亚乙基双硬脂酸酰胺、EVA、尿素、盐酸羟胺、硫酸羟胺和环己醇；所述的反应型粘度调节剂为环氧化合物、或者含羟基或氨基的低分子量的多官能团的酯类或醇类或胺类化合物；
    所述的爽滑剂为选自于如下一组的一种以上：脂肪酸及其酯类、脂肪酸酰胺、金属皂、烃类、有机硅化合物、硬脂酸、硬脂酸丁酯和乙撑双硬脂酰胺。
  10. 如权利要求9所述的层合物，其中，该层合物在所述由无纺布和/或纺织面料形成的层和所述由含废旧热塑性弹性体的组合物形成的层之间，进一步包括一胶合层，该胶合层是由热熔胶、溶剂胶或水性胶形成的，其克重为3－80gsm。
PCT/CN2021/101789 2021-05-19 2021-06-23 由废旧热塑性弹性体和回收聚酯形成的薄膜及层合物 WO2022241903A1 (zh)

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