WO2018205326A1 - 一种免粘合剂的瓶盖垫片和/或衬垫及其制备方法 - Google Patents

一种免粘合剂的瓶盖垫片和/或衬垫及其制备方法 Download PDF

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WO2018205326A1
WO2018205326A1 PCT/CN2017/087230 CN2017087230W WO2018205326A1 WO 2018205326 A1 WO2018205326 A1 WO 2018205326A1 CN 2017087230 W CN2017087230 W CN 2017087230W WO 2018205326 A1 WO2018205326 A1 WO 2018205326A1
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Prior art keywords
gasket
styrene
oil
block copolymer
adhesive
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PCT/CN2017/087230
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English (en)
French (fr)
Inventor
车俊峥
祝方明
简静姬
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佛山市同骏环保科技有限公司
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Publication of WO2018205326A1 publication Critical patent/WO2018205326A1/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
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • 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
    • C08L2207/04—Thermoplastic elastomer
    • 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
    • C08L2207/06—Properties of polyethylene
    • C08L2207/066—LDPE (radical process)

Definitions

  • the invention belongs to the technical field of materials, and in particular to an adhesive-free cap gasket and/or pad and a preparation method thereof.
  • cap gaskets and liners are widely used in the food industry such as alcohol, food, health care products, pharmaceuticals, cosmetics.
  • Food bottle cap gaskets and liners are made of various structural materials, including polyethylene (PE), ethylene/vinyl acetate copolymer (EVA), polyvinyl chloride (PVC), thermoplastic elastomer (TPE), vulcanized rubber, Polymer materials such as epoxy resin coatings and copper sheets or papers, among which PVC, PE, TPE and other polymers and blends thereof are mainly used for reinforcing the seal between the two planes. Prevent fluid leakage.
  • Chinese invention patent CN102408603A discloses a pellet for producing beer and beverage crown cap polyolefin gasket, which has a low density polyethylene of 58.1-72.5 parts by weight, a thermoplastic elastomer of 18.2-39.4 parts, 2.5 ⁇ 8.5 parts of antioxidant masterbatch and 0-0.8 parts of coloring masterbatch are mixed, extruded, pelletized, water cooled, sieved, dried and then cooled to form a material for producing food bottle cap gaskets and liners.
  • the technical problem to be solved by the present invention is to overcome the defects and deficiencies of the prior art cap gasket and/or liner which need to use the adhesive technology, and to provide an adhesive-free cap gasket particle and preparation method thereof
  • the gasket and/or the gasket prepared by the gasket pellet are non-toxic and tasteless, sealed, and have good resilience and good Sealing and adhesion; strong bonding strength and strong pressure resistance; the gasket pellets make the production process of the cap easier and reduce energy consumption, and have broad application prospects.
  • Another object of the present invention is to provide a method of preparing the above-described cap gasket pellets.
  • An adhesive-free cap gasket pellet prepared from the following parts by weight:
  • the rosin resin is creatively introduced into the preparation process of the gasket pellet, and optimized.
  • the ratio between the components is prepared in the above ratio range to obtain the binder-free cap gasket pellets, and the prepared cap gasket and/or gasket is non-toxic and tasteless, and the bond strength is Large, high pressure resistance.
  • cap gasket pellets are prepared from the following parts by weight of raw materials:
  • cap gasket and/or liner is prepared from the following parts by weight of raw materials:
  • thermoplastic elastomer is a block copolymer constructed of at least one soft block and at least two hard blocks, the hard block comprises a polystyrene, and the soft block comprises a polyconjugated diene or Hydride.
  • the block copolymer is a styrene-isoprene-styrene block copolymer, a styrene-butadiene-styrene triblock copolymer, a hydrogenated styrene-butadiene-styrene Triblock copolymer or hydrogenated benzene One of ethylene-isoprene-styrene block copolymers.
  • the styrene-isoprene-styrene block copolymer has a polystyrene and polyisoprene block mass content of 15 to 50%, respectively; the styrene-butadiene- The polystyrene and polybutadiene block mass content in the styrene triblock copolymer is 20-50%, respectively; the hydrogenated styrene-butadiene-styrene triblock copolymer is polystyrene and hydrogenated The polyisoprene block mass content is 20-50%, respectively; the hydrogenated styrene-isoprene-styrene block copolymer has a mass content of polystyrene and hydrogenated polybutadiene block of 20, respectively. ⁇ 50%.
  • the block copolymer has a melt index of from 3 to 10.
  • the block copolymer is an oil-extended block copolymer having an oil charge of from 0 to 20% by mass of the block copolymer.
  • the polyolefin is in low density polyethylene or linear low density polyethylene or a mixture thereof. More preferably, the low density polyethylene or linear low density polyethylene has a molecular weight of 10 4 to 10 5 , a melt index of 20 to 40, and a density of 0.918 to 0.935 g/cm 3 .
  • the hot melt adhesiveness is not strong; the wettability is poor; the drying property, water resistance and hardness of the coating film are not ideal; the viscosity and physical and mechanical properties are not good; thermal stability, oxidation resistance, hardness Poor, brittle, easy to oxidize, etc.
  • the present invention obtains a gasket or lining which is excellent in adhesion performance by modifying the rosin resin.
  • the rosin resin is a modified rosin resin.
  • the modified rosin resin is one of rosin soap, rosin polyol ester, rosin modified phenol resin, rosin maleic anhydride polyol ester, disproportionated rosin, polymerized rosin or hydrogenated rosin.
  • the oil-filled oil is one of an environmentally friendly aromatic hydrocarbon oil, a paraffin oil, a naphthenic oil or an aromatic hydrocarbon oil.
  • the oil-filled oil is a naphthenic oil having a relative density of 0.89 to 0.95, a flash point of >160 ° C, an acid value of ⁇ 0.1 mg KOH/g, an aniline point of 66 to 82 ° C, a freezing point of ⁇ 18 ° C, and a refractive index of 1.4860 ⁇ . 1.4963.
  • the method for preparing the above-mentioned binder-free cap gasket pellets wherein the raw material thermoplastic elastomer, polyethylene, rosin resin and mold release agent are uniformly mixed in a weight ratio, and then added to an injection molding machine hopper. Extrusion granulation was carried out; the granulation temperature was 85 to 170 ° C, and the rotation speed was 350 to 550 r/min to obtain a gasket pellet.
  • thermoplastic elastomer is subjected to an oil-filling treatment prior to mixing.
  • the cap gasket and/or the gasket are prepared by placing the gasket pellets into a molding machine, extruding the droplets in the cap at 100-150 ° C, and press-forming to obtain a non-stick. Cap gasket and/or lining of the mixture pad.
  • the invention has the following beneficial effects:
  • the adhesive-free cap gasket pellet of the invention can meet the corresponding food safety requirements, and is particularly suitable for the production of food caps, and the gasket and the gasket and the cap have a pressure-sensitive adhesive strength. No adhesive, and low cost, suitable for pipeline production with fast mass processing.
  • cap gasket and/or the gasket prepared by the invention are non-toxic and tasteless, have good sealing, good resilience, good sealing property and adhesion, strong strength and strong pressure resistance.
  • the adhesive-free cap gasket and/or liner of the present invention does not involve adhesiveness due to the production process, does not use an adhesive, and therefore does not cause chemical pollution, meets environmental protection requirements, and has broad application prospects.
  • the number average molecular weight of the styrene-butadiene-styrene block copolymer is 5.25.2 ⁇ 10 5 , and the mass contents of the polystyrene and polybutadiene blocks are 15% and 45%, respectively;
  • the polyethylene is a linear low density polyethylene (LLDPE) and a low density polyethylene (LDPE) and a mixture thereof, wherein the LLDPE content is 60%, the LDPE content is 40%, and the melt index MFI of LLDPE and LDPE is 3.2/10 min, respectively. 230 ° C, 2.16 kg) and 0.8/10 min (230 ° C, 2.16 kg).
  • Step 1 mixing the above raw materials uniformly, and then adding them to the hopper of the injection molding machine for extrusion granulation; granulation temperature 150 ° C, twin screw rotation speed 360 r / min, to obtain gasket pellets;
  • Step 2 The gasket pellet obtained in the first step is placed in a molding machine, and the droplets are extruded into a bottle cap at 100 ° C, and press-molded to obtain a gasket or a liner.
  • the number average molecular weight of the styrene-butadiene-styrene block copolymer (SBS) is 3.8 ⁇ 10 5
  • the mass contents of the polystyrene and polybutadiene blocks are 20% and 35%, respectively;
  • the polyethylene is a linear low density polyethylene (LLDPE) and a low density polyethylene (LDPE) and a mixture thereof, wherein the LLDPE content is 50%, the LDPE content is 50%, and the melt index MFI of LLDPE and LDPE is 4.4/10 min, respectively. 230 ° C, 2.16 kg) and 0.8/10 min (230 ° C, 2.16 kg).
  • Step 1 mixing the above raw materials uniformly, and then adding them to the hopper of the injection molding machine for extrusion granulation; granulation temperature 85 ° C, twin screw rotation speed 350 r / min, to obtain gasket pellets;
  • Step 2 The gasket pellet obtained in the first step is placed in a molding machine, and the droplets are extruded into a bottle cap at 150 ° C, and press-molded to obtain a gasket or a liner.
  • the number average molecular weight of the styrene-isoprene-styrene block copolymer (SIS) is 1.8 ⁇ 10 5 , and the mass contents of the polystyrene and polyisoprene blocks are 15% and 45%, respectively;
  • the polyethylene is a linear low density polyethylene (LLDPE) and a low density polyethylene (LDPE) and a mixture thereof, wherein the LLDPE content is 40%, the LDPE content is 60%, and the melt index MFI of LLDPE and LDPE is 5.2/10 min, respectively. 230 ° C, 2.16 kg) and 0.8/10 min (230 ° C, 2.16 kg).
  • Step 1 mixing the above raw materials uniformly, and then adding them to the hopper of the injection molding machine for extrusion granulation; granulation temperature 170 ° C, twin screw rotation speed 500 r / min, to obtain gasket pellets;
  • Step 2 The gasket pellet obtained in the first step is placed in a molding machine, and the droplets are extruded into a cap at 120 ° C, and press-molded to obtain a gasket or a liner.
  • the number average molecular weight of the hydrogenated styrene-isoprene monostyrene block copolymer is 2.1 ⁇ 10 5 , and the mass contents of the polystyrene and polyisoprene blocks are 20% and 45%, respectively. ;
  • the polyethylene is a linear low density polyethylene (LLDPE) and a low density polyethylene (LDPE) and a mixture thereof, wherein the LLDPE content is 30%, the LDPE content is 70%, and the melt index MFI of LLDPE and LDPE is 2.5/10 min, respectively. 230 ° C, 2.16 kg) and 4.5/10 min (230 ° C, 2.16 kg).
  • LLDPE linear low density polyethylene
  • LDPE low density polyethylene
  • Step 1 mixing the above raw materials uniformly, and then adding them to the hopper of the injection molding machine for extrusion granulation; granulation temperature 150 ° C, twin screw rotation speed 550 r / min, to obtain gasket pellets;
  • Step 2 The gasket pellet obtained in the first step is placed in a molding machine, and the droplets are extruded into a bottle cap at 100 ° C, and press-molded to obtain a gasket or a liner.
  • the number average molecular weight of the hydrogenated styrene-isoprene monostyrene block copolymer is 4.5 ⁇ 10 5 , and the mass contents of the polystyrene and polybutadiene blocks are 25 and 45%, respectively;
  • the polyethylene is a linear low density polyethylene (LLDPE) and a low density polyethylene (LDPE) and a mixture thereof, wherein the LLDPE content is 40%, the LDPE content is 60%, and the melt index MFI of LLDPE and LDPE is 2.8/10 min, respectively. 230 ° C, 2.16 kg) and 4.5/10 min (230 ° C, 2.16 kg).
  • Step 2 mixing the above raw materials uniformly, and then adding them to the hopper of the injection molding machine for extrusion granulation; granulation temperature 160 ° C, twin screw rotation speed 400 r / min, to obtain gasket pellets;
  • Step 3 The gasket pellet obtained in the first step is placed in a molding machine, and the droplets are extruded in a bottle cap at 130 ° C, and press-molded to obtain a gasket or a liner.
  • the number average molecular weight of the styrene-isoprene monostyrene block copolymer (SIS) is 8.6 ⁇ 10 5 , and the mass contents of the polystyrene and polyisoprene blocks are 20% and 40%, respectively;
  • the oil content of the naphthenic oil is 10% of the mass of the block copolymer;
  • the polyethylene is a linear low density polyethylene (LLDPE) and a low density polyethylene (LDPE) and a mixture thereof, wherein the LLDPE content is 40%, the LDPE content is 60%, and the melt index MFI of LLDPE and LDPE is 5.2/10 min, respectively. 230 ° C, 2.16 kg) and 0.8/10 min (230 ° C, 2.16 kg).
  • Step 1 The TPE naphthenic oil is oil-filled to make the oil-filling amount 10% of the mass of the block copolymer.
  • Step 2 mixing the above raw materials uniformly, and then adding them to the hopper of the injection molding machine for extrusion granulation; the granulation temperature is 170 ° C, the twin screw rotation speed is 300 r / min, and the gasket pellets are obtained;
  • Step 3 The gasket pellet obtained in the first step is placed in a molding machine, and the droplets are extruded into a bottle cap at 140 ° C, and press-molded to obtain a gasket or a liner.
  • the number average molecular weight of the styrene-isoprene monostyrene block copolymer (SIS) is 7.8 ⁇ 10 4 , and the mass contents of the polystyrene and polyisoprene blocks are 15 and 45%, respectively;
  • the aromatic oil is oil-filled to 15% by mass of the block copolymer;
  • the polyethylene is a linear low density polyethylene (LLDPE) and a low density polyethylene (LDPE) and a mixture thereof, wherein the LLDPE content is 60%, the LDPE content is 40%, and the melt index MFI of LLDPE and LDPE is 7.0/10 min (230 °C, 2.16kg).
  • LLDPE linear low density polyethylene
  • LDPE low density polyethylene
  • Step 1 TPE environmentally friendly aromatic oil is oil-filled to make the oil-filling amount 15% of the mass of the block copolymer.
  • Step 2 mixing the above raw materials uniformly, and then adding them to the hopper of the injection molding machine for extrusion granulation;
  • the granulation temperature is 150 ° C, the twin screw speed is 400 r / min, and the gasket pellets are obtained;
  • Step 3 The gasket pellet obtained in the first step is placed in a molding machine, and the droplets are extruded into a bottle cap at 100 ° C, and press-molded to obtain a gasket or a liner.
  • the number average molecular weight of the styrene-butadiene-styrene block copolymer is 8.2 ⁇ 10 5 , and the mass contents of the polystyrene and polybutadiene blocks are 15 and 45%, respectively;
  • the amount of oil is 15% of the mass of the block copolymer;
  • the low density polyethylene had a melt index MFI of 3.6/10 min (230 ° C, 2.16 kg).
  • Step 1 The TPE paraffin oil is oil-filled to make the oil-filling amount 15% of the mass of the block copolymer.
  • Step 2 mixing the above raw materials uniformly, and then adding them to the hopper of the injection molding machine for extrusion granulation; granulation temperature 130 ° C, twin screw rotation speed 450 r / min, to obtain gasket pellets;
  • Step 3 The gasket pellet obtained in the first step is placed in a molding machine, and the droplets are extruded in a bottle cap at 130 ° C, and press-molded to obtain a gasket or a liner.
  • the number average molecular weight of the hydrogenated styrene-isoprene monostyrene block copolymer is 2.1 ⁇ 10 5 , and the mass contents of the polystyrene and polyisoprene blocks are 15 and 45%, respectively;
  • the oil content of the aromatic hydrocarbon oil is 10% by mass of the mass of the block copolymer;
  • the polyethylene is a linear low density polyethylene (LLDPE) and a low density polyethylene (LDPE) and a mixture thereof, wherein the LLDPE content is 60%, the LDPE content is 40%, and the melt index MFI of LLDPE and LDPE is 2.5/10 min, respectively. 230 ° C, 2.16 kg) and 4.5/10 min (230 ° C, 2.16 kg).
  • LLDPE linear low density polyethylene
  • LDPE low density polyethylene
  • Step 1 The TPE aromatic oil is oil-filled to make the oil-filling amount 15% of the mass of the block copolymer.
  • Step 2 mixing the above raw materials uniformly, and then adding them to the hopper of the injection molding machine for extrusion granulation; granulation temperature 160 ° C, twin screw rotation speed 500 r / min, to obtain gasket pellets;
  • Step 3 The gasket pellet obtained in the first step is placed in a molding machine, and the droplets are extruded into a bottle cap at 100 ° C, and press-molded to obtain a gasket or a liner.
  • the number average molecular weight of the hydrogenated styrene-isoprene monostyrene block copolymer is 4.5 ⁇ 10 5 , and the mass contents of the polystyrene and polybutadiene blocks are 15 and 45%, respectively;
  • the oil content of the alkane oil is 10% of the mass of the block copolymer;
  • LLDPE linear low density polyethylene
  • Step 1 The TPE naphthenic oil is oil-filled to make the oil-filling amount 10% of the mass of the block copolymer.
  • Step 2 mixing the above raw materials uniformly, and then adding them to an injection molding machine hopper for extrusion granulation; granulation temperature of 180 ° C, twin screw rotation speed of 400 r / min, to obtain gasket pellets;
  • Step 3 The gasket pellet obtained in the first step is placed in a molding machine, and the droplets are extruded into a cap at 120 ° C, and press-molded to obtain a gasket or a liner.
  • the number average molecular weight of the styrene-isoprene monostyrene block copolymer (SIS) is 8.6 ⁇ 10 5 , and the mass contents of the polystyrene and polyisoprene blocks are 20% and 40%, respectively;
  • the oil content of the naphthenic oil is 10% of the mass of the block copolymer;
  • the low density polyethylene (LDPE) melt index MFI is 3.8/10 min (230 ° C, 2.16 kg)
  • Step 1 The TPE naphthenic oil is oil-filled to make the oil-filling amount 10% of the mass of the block copolymer.
  • Step two the above raw materials are uniformly mixed, and then added to the hopper of the injection molding machine for extrusion granulation; the granulation temperature is 170 ° C, the twin screw rotation speed is 300 r / min, and the gasket pellets are obtained;
  • Step 3 The gasket pellet obtained in the first step is placed in a molding machine, and the droplets are extruded into a bottle cap at 140 ° C, and press-molded to obtain a gasket or a liner.
  • the number average molecular weight of the styrene-isoprene monostyrene block copolymer (SIS) is 8.6 ⁇ 10 5 , and the mass contents of the polystyrene and polyisoprene blocks are 20% and 40%, respectively;
  • the oil content of the naphthenic oil is 10% of the mass of the block copolymer;
  • the polyethylene is a linear low density polyethylene (LLDPE) and a low density polyethylene (LDPE) and a mixture thereof, wherein the LLDPE content is 40%, the LDPE content is 60%, and the melt index MFI of LLDPE and LDPE is 5.2/10 min, respectively. 230 ° C, 2.16 kg) and 0.8/10 min (230 ° C, 2.16 kg).
  • Step 1 The TPE naphthenic oil is oil-filled to make the oil-filling amount 10% of the mass of the block copolymer.
  • Step two the above raw materials are uniformly mixed, and then added to the hopper of the injection molding machine for extrusion granulation; the granulation temperature is 170 ° C, the twin screw rotation speed is 300 r / min, and the gasket pellets are obtained;
  • Step 3 The gasket pellet obtained in the first step is placed in a molding machine, and the droplets are extruded into a bottle cap at 140 ° C, and press-molded to obtain a gasket or a liner.
  • the number average molecular weight of the styrene-isoprene monostyrene block copolymer (SIS) is 8.6 ⁇ 10 5 , and the mass contents of the polystyrene and polyisoprene blocks are 20% and 40%, respectively;
  • the oil content of the naphthenic oil is 10% of the mass of the block copolymer;
  • the polyethylene is a linear low density polyethylene (LLDPE) and a low density polyethylene (LDPE) and a mixture thereof, wherein the LLDPE content is 40%, the LDPE content is 60%, and the melt index MFI of LLDPE and LDPE is 5.2/10 min, respectively. 230 ° C, 2.16 kg) and 0.8/10 min (230 ° C, 2.16 kg).
  • Step 1 The TPE naphthenic oil is oil-filled to make the oil-filling amount 10% of the mass of the block copolymer.
  • Step two the above raw materials are uniformly mixed, and then added to the hopper of the injection molding machine for extrusion granulation; the granulation temperature is 170 ° C, the twin screw rotation speed is 300 r / min, and the gasket pellets are obtained;
  • Step 3 The gasket pellet obtained in the first step is placed in a molding machine, and the droplets are extruded into a bottle cap at 140 ° C, and press-molded to obtain a gasket or a liner.
  • the number average molecular weight of the styrene-isoprene monostyrene block copolymer (SIS) is 8.6 ⁇ 10 5 , and the mass contents of the polystyrene and polyisoprene blocks are 20% and 40%, respectively;
  • the oil content of the naphthenic oil is 10% of the mass of the block copolymer;
  • the polyethylene is a linear low density polyethylene (LLDPE) and a low density polyethylene (LDPE) and a mixture thereof, wherein the LLDPE content is 40%, the LDPE content is 60%, and the melt index MFI of LLDPE and LDPE is 5.2/10 min, respectively. 230 ° C, 2.16 kg) and 0.8/10 min (230 ° C, 2.16 kg).
  • Step 1 The TPE naphthenic oil is oil-filled to make the oil-filling amount 10% of the mass of the block copolymer.
  • Step two the above raw materials are uniformly mixed, and then added to the hopper of the injection molding machine for extrusion granulation; the granulation temperature is 170 ° C, the twin screw rotation speed is 300 r / min, and the gasket pellets are obtained;
  • Step 3 The gasket pellet obtained in the first step is placed in a molding machine, and the droplets are extruded into a bottle cap at 140 ° C, and press-molded to obtain a gasket or a liner.
  • a cap gasket/or lining prepared from the following weight fractions of raw materials:
  • the number average molecular weight of the styrene-isoprene monostyrene block copolymer (SIS) is 8.6 ⁇ 10 5 , and the mass contents of the polystyrene and polyisoprene blocks are 20% and 40%, respectively;
  • the oil content of the naphthenic oil is 10% of the mass of the block copolymer;
  • the polyethylene is a linear low density polyethylene (LLDPE) and a low density polyethylene (LDPE) and a mixture thereof, wherein the LLDPE content is 40%, the LDPE content is 60%, and the melt index MFI of LLDPE and LDPE is 5.2/10 min, respectively. 230 ° C, 2.16 kg) and 0.8/10 min (230 ° C, 2.16 kg).
  • Step 1 The TPE naphthenic oil is oil-filled to make the oil-filling amount 10% of the mass of the block copolymer.
  • Step two the above raw materials are uniformly mixed, and then added to the hopper of the injection molding machine for extrusion granulation; the granulation temperature is 170 ° C, the twin screw rotation speed is 300 r / min, and the gasket pellets are obtained;
  • Step 3 The gasket pellet obtained in the first step is placed in a molding machine, and the droplets are extruded into a bottle cap at 140 ° C, and press-molded to obtain a gasket or a liner.
  • a cap gasket/or lining prepared from the following weight fractions of raw materials:
  • the number average molecular weight of the styrene-isoprene monostyrene block copolymer (SIS) is 8.6 ⁇ 10 5 , and the mass contents of the polystyrene and polyisoprene blocks are 20% and 40%, respectively;
  • the oil content of the naphthenic oil is 10% of the mass of the block copolymer;
  • the polyethylene is a linear low density polyethylene (LLDPE) and a low density polyethylene (LDPE) and a mixture thereof, wherein the LLDPE content is 40%, the LDPE content is 60%, and the melt index MFI of LLDPE and LDPE is 5.2/10 min, respectively. 230 ° C, 2.16 kg) and 0.8/10 min (230 ° C, 2.16 kg).
  • Step 1 The TPE naphthenic oil is oil-filled to make the oil-filling amount 10% of the mass of the block copolymer.
  • Step 2 mixing the above raw materials uniformly, and then adding them to the hopper of the injection molding machine for extrusion granulation; the granulation temperature is 170 ° C, the twin screw rotation speed is 300 r / min, and the gasket pellets are obtained;
  • Step 3 The gasket pellet obtained in the first step is placed in a molding machine, and the droplets are extruded at a cap at 140 ° C. Medium, press forming to obtain a gasket or liner.
  • a cap gasket/rubber is prepared from the following raw materials by weight: except that the raw material does not contain the rosin resin, the other raw materials and the preparation method are the same as in the sixth embodiment.
  • a bottle cap gasket or lining material is prepared from the following raw materials by weight fraction: the rosin resin is replaced with a terpene phenol resin, and other materials and preparation methods are the same as in the sixth embodiment.
  • a cap gasket/rubber is prepared from the following raw materials by weight: the rosin resin is replaced by an epoxy resin, and the other materials and preparation methods are the same as in the sixth embodiment.
  • the gasket or the lining material prepared in the scope of the invention does not need the adhesive while ensuring the application function of the gasket, so that the production process of the cap is simpler, the energy consumption is reduced, and the application prospect is greater. .

Abstract

一种免粘合剂的瓶盖垫片粒料，由以下重量分数的原料制备而成：热塑性弹性体50～80份；聚乙烯15～40份；松香树脂5～15份；硬脂酸酰胺5～10份；将上述原料按重量份数充分混匀，挤塑、切粒、水冷却、干燥后形成瓶盖垫片及衬垫专用粒料，将粒料放入模塑机中，100～150℃下挤出液滴于瓶盖中，压制成型，即得到免粘合剂的垫片和/或衬垫。所述垫片粒料可直接注塑成型形成与瓶盖粘结强度大垫片和/或衬垫，无需任何粘合剂；使瓶盖生产过程更加简便、降低了能耗；所述垫片粒料通过了严格的食品安全检测，尤其适用于食品瓶盖生产，且避免了粘合剂对瓶中食品的不良影响，极大地提升国内瓶盖生产厂家的竞争力。

Description

一种免粘合剂的瓶盖垫片和/或衬垫及其制备方法 技术领域
本发明属于材料技术领域，具体地，涉及一种免粘合剂的瓶盖垫片和/或衬垫及其制备方法。
背景技术
随着经济的不断发展，瓶盖垫片及衬垫被广泛应用在酒类、食品、保健品、药品、化妆品等食品行业中。食品瓶盖垫片及衬垫由各种结构材料制成，包括聚乙烯(PE)、乙烯/乙酸乙烯酯共聚物(EVA)、聚氯乙烯(PVC)、热塑性弹性体(TPE)、硫化橡胶、环氧树脂涂层等聚合物材料及铜片或纸张，其中以PVC、PE、TPE等聚合物及其共混物材质为主，用来放到两平面之间用以加强密封的材料，具有防止流体泄漏的作用。
目前，国内食品瓶盖垫片及衬垫的材料大多使用聚氯乙烯材质，由于其成分中含有增塑剂、稳定剂以及聚氯乙烯中的氯乙烯单体残留量等，存在食用安全性的问题。中国发明专利CN102408603A公开了一种用于生产啤酒、饮料皇冠盖聚烯烃垫片的粒料，由重量份数为58.1～72.5份的低密度聚乙烯、18.2～39.4份的热塑性弹性体、2.5～8.5份的抗氧剂母料和0～0.8份的着色母料，经混合、挤塑、切粒、水冷却、过筛、干燥后再冷却形成生产食品瓶盖垫片及衬垫的材料。一般相关文献的研究内容大致为：使用聚氯乙烯制作生产食品瓶盖垫片及衬垫，使用茂金属聚乙烯和助剂(增塑剂、增容剂、增韧剂、加工助剂、抗氧剂)制备无卤高阻隔聚烯烃瓶盖垫片及衬垫用料粒及其它使用聚乙烯、无纺布破碎料、苯乙烯-丁二烯嵌段共聚物、二硼化钒、甲基三丁酮肟基硅烷、亚麻籽胶、四氯间苯二甲腈、陶瓷粉、膨胀珍珠岩、烷基苯磺酸钠、聚环氧琥珀酸、钙沸石、泡花碱、防腐助剂、聚乙二醇为原料制作瓶盖用垫片材料。这些材料制成的垫片及衬垫都需要使用粘合剂技术，这就无形中增大了工艺的复杂性，加大了能耗和VOC排放量。
发明内容
本发明要解决的技术问题是克服现有技术中瓶盖垫片和/或衬垫需要使用粘合剂技术的缺陷和不足，提供一种免粘合剂的瓶盖垫片粒料及其制备方法，所述垫片粒料制备得到的垫片和/或衬垫无毒无味，密封，回弹性好，具有良好的 密封性和粘附性；粘结强度大，耐压性强；该垫片粒料使瓶盖生产过程更加简便、降低了能耗，具有广阔的应用前景。
本发明的目的是提供一种免粘合剂的瓶盖垫片粒料。
本发明另一目的是提供上述瓶盖垫片粒料的制备方法。
本发明的再一目的是提供一种由上述垫片粒料制备得到的免粘合剂的垫片和/或衬垫。
本发明上述目的通过以下技术方案实现：
一种免粘合剂的瓶盖垫片粒料，由以下重量份数的原料制备而成：
Figure PCTCN2017087230-appb-000001
本发明为了使生产的垫片和/或衬垫在具备垫片应有的功能之外还具有免粘合剂的功能，创造性的将松香树脂引入到垫片粒料的制备过程中，通过优化各组分之间的配比，在上述配比范围内制备得到了免粘合剂的瓶盖垫片粒料，其制备得到的瓶盖垫片和/或衬垫无毒无味，粘结强度大，耐压性强。
优选地，所述瓶盖垫片粒料由以下重量份数的原料制备而成：
Figure PCTCN2017087230-appb-000002
再优选地，所述瓶盖垫片和/或衬垫由以下重量份数的原料制备而成：
Figure PCTCN2017087230-appb-000003
优选地，所述热塑性弹性体为至少一软嵌段和至少二硬嵌段构建的嵌段共聚物，硬嵌段包含一种聚苯乙烯，软嵌段包含一种聚共轭二烯烃或其氢化物。
优选地，所述嵌段共聚物为苯乙烯-异戊二烯-苯乙烯嵌段共聚物、苯乙烯-丁二烯-苯乙烯三嵌段共聚物、氢化苯乙烯-丁二烯-苯乙烯三嵌段共聚物或氢化苯 乙烯-异戊二烯-苯乙烯嵌段共聚物中的一种。
更优选地，所述苯乙烯-异戊二烯-苯乙烯嵌段共聚物中聚苯乙烯和聚异戊二烯嵌段质量含量分别为15～50％；所述苯乙烯-丁二烯-苯乙烯三嵌段共聚物中聚苯乙烯和聚丁二烯嵌段质量含量分别为20～50％；所述氢化苯乙烯-丁二烯-苯乙烯三嵌段共聚物中聚苯乙烯和氢化聚异戊二烯嵌段质量含量分别为20～50％；所述氢化苯乙烯-异戊二烯-苯乙烯嵌段共聚物中聚苯乙烯和氢化聚丁二烯嵌段质量含量分别为20～50％。
优选地，所述嵌段共聚物的熔融指数为3～10。
优选地，所述嵌段共聚物为充油处理的嵌段共聚物，其充油量为嵌段共聚物质量的0～20％。
优选地，所述聚烯烃为低密度聚乙烯或线性低密度聚乙烯中或其混合物。更优选地，所述低密度聚乙烯或线性低密度聚乙烯分子量为104～105，熔融指数为20～40，密度为0.918～0.935g/cm3。
由于未改性的松香树脂存在着：热熔黏合性不强；润湿性差；涂膜干燥性、耐水性和硬度不理想；粘性和物理机械性能不好；热稳定性、抗氧化性、硬度较差；脆性高，易氧化等缺陷，为了进一步提高垫片或衬料的粘合性，本发明通过对松香树脂进行改性，获得了粘合性能优良更加优良的垫片或衬料。
优选地，所述松香树脂为改性松香树脂。
更优选地，所述改性松香树脂为松香皂，松香多元醇酯，松香改性酚醛树脂，松香顺酐多元醇酯，歧化松香，聚合松香或氢化松香中的一种。
优选地，所述充油为环保芳烃油、石蜡油、环烷油或芳烃油中的一种。
更优选地，所述充油为环烷油，其相对密度0.89～0.95，闪点>160℃，酸值<0.1mgKOH/g，苯胺点66～82℃，凝固点≤18℃，折射率1.4860～1.4963。
上述免粘合剂的瓶盖垫片粒料的制备方法，所述方法为将上述原料热塑性弹性体、聚乙烯、松香树脂、脱模剂按重量比混合均匀，然后加入到注塑机料斗中，进行挤出造粒；造粒温度85～170℃，转速350～550r/min，得到垫片粒料。
优选地，所述热塑性弹性体在混匀前进行充油处理。
一种由上述垫片粒料制备得到的免粘合剂的瓶盖垫片和/或衬垫。
优选地，所述瓶盖垫片和/或衬垫的制备方法为将垫片粒料放入模塑机中，100～150℃下挤出液滴于瓶盖中，压制成型，得到免粘合剂的瓶盖垫片和/或衬 垫。
本发明与现有技术相比，具有以下有益效果：
(1)本发明所述免粘合剂的瓶盖垫片粒料，能满足相应的食品安全要求，特别适用于食品瓶盖生产，其垫片及衬垫与瓶盖压敏粘结强度大，无需粘合剂，且成本较低，适合于快速大量加工的流水线生产。
(2)本发明制备得到的瓶盖垫片和/或衬垫无毒无味，密封，回弹性好，具有良好的密封性和粘附性；强度大，耐压性强。
(3)本发明所述免粘合剂的瓶盖垫片和/或衬垫由于生产工艺不涉及胶粘，不使用胶粘剂，因此不会产生化学污染，符合环保要求，具有广阔的应用前景。
具体实施方式
以下结合说明书附图和具体实施例来进一步说明本发明，但实施例并不对本发明做任何形式的限定。除非特别说明，本发明采用的试剂、方法和设备为本技术领域常规试剂、方法和设备。
除非特别说明，以下实施例所用试剂和材料均为市购。
实施例1
一种免粘合剂的瓶盖垫片/或衬料，由以下重量分数的原料制备而成：
Figure PCTCN2017087230-appb-000004
其中，苯乙烯一丁二烯一苯乙烯嵌段共聚物(SBS)的数均分子量为5.25.2×105，聚苯乙烯和聚丁二烯嵌段质量含量分别为15％和45％；
所述聚乙烯为线性低密度聚乙烯(LLDPE)与低密度聚乙烯(LDPE)和混合物，其中LLDPE含量为60％，LDPE含量为40％，LLDPE和LDPE的熔融指数MFI分别为3.2/10min(230℃，2.16kg)和0.8/10min(230℃，2.16kg)。
步骤一：将上述原料混合均匀，然后加入到注塑机料斗中，进行挤出造粒；造粒温度150℃，双螺杆转速360r/min，得到垫片粒料；
步骤二：将步骤一得到的垫片粒料放入模塑机中，100℃下挤出液滴于瓶盖中，压制成型，得到垫片或衬垫。
实施例2
一种免粘合剂的瓶盖垫片/或衬料，由以下重量分数的原料制备而成：
Figure PCTCN2017087230-appb-000005
其中，苯乙烯一丁二烯一苯乙烯嵌段共聚物(SBS)的数均分子量为3.8×105，聚苯乙烯和聚丁二烯嵌段质量含量分别为20％和35％；
所述聚乙烯为线性低密度聚乙烯(LLDPE)与低密度聚乙烯(LDPE)和混合物，其中LLDPE含量为50％，LDPE含量为50％，LLDPE和LDPE的熔融指数MFI分别为4.4/10min(230℃，2.16kg)和0.8/10min(230℃，2.16kg)。
步骤一：将上述原料混合均匀，然后加入到注塑机料斗中，进行挤出造粒；造粒温度85℃，双螺杆转速350r/min，得到垫片粒料；
步骤二：将步骤一得到的垫片粒料放入模塑机中，150℃下挤出液滴于瓶盖中，压制成型，得到垫片或衬垫。
实施例3
一种免粘合剂的瓶盖垫片/或衬料，由以下重量分数的原料制备而成：
Figure PCTCN2017087230-appb-000006
其中，苯乙烯一异戊二烯一苯乙烯嵌段共聚物(SIS)的数均分子量为1.8×105，聚苯乙烯和聚异戊二烯嵌段质量含量分别为15％和45％；
所述聚乙烯为线性低密度聚乙烯(LLDPE)与低密度聚乙烯(LDPE)和混合物，其中LLDPE含量为40％，LDPE含量为60％，LLDPE和LDPE的熔融指数MFI分别为5.2/10min(230℃，2.16kg)和0.8/10min(230℃，2.16kg)。
步骤一：将上述原料混合均匀，然后加入到注塑机料斗中，进行挤出造粒；造粒温度170℃，双螺杆转速500r/min，得到垫片粒料；
步骤二：将步骤一得到的垫片粒料放入模塑机中，120℃下挤出液滴于瓶盖中，压制成型，得到垫片或衬垫。
实施例4
一种免粘合剂的瓶盖垫片/或衬料，由以下重量分数的原料制备而成：
Figure PCTCN2017087230-appb-000007
其中，氢化苯乙烯一异戊二烯一苯乙烯嵌段共聚物(SEPS)的数均分子量为2.1×105，聚苯乙烯和聚异戊二烯嵌段质量含量分别为20％和45％；
所述聚乙烯为线性低密度聚乙烯(LLDPE)与低密度聚乙烯(LDPE)和混合物，其中LLDPE含量为30％，LDPE含量为70％，LLDPE和LDPE的熔融指数MFI分别为2.5/10min(230℃，2.16kg)和4.5/10min(230℃，2.16kg)。
步骤一：将上述原料混合均匀，然后加入到注塑机料斗中，进行挤出造粒；造粒温度150℃，双螺杆转速550r/min，得到垫片粒料；
步骤二：将步骤一得到的垫片粒料放入模塑机中，100℃下挤出液滴于瓶盖中，压制成型，得到垫片或衬垫。
实施例5
一种免粘合剂的瓶盖垫片/或衬料，由以下重量分数的原料制备而成：
Figure PCTCN2017087230-appb-000008
其中，氢化苯乙烯一异戊二烯一苯乙烯嵌段共聚物(SEPS)的数均分子量为4.5×105，聚苯乙烯和聚丁二烯嵌段质量含量分别为25和45％；
所述聚乙烯为线性低密度聚乙烯(LLDPE)与低密度聚乙烯(LDPE)和混合物，其中LLDPE含量为40％，LDPE含量为60％，LLDPE和LDPE的熔融指数MFI分别为2.8/10min(230℃，2.16kg)和4.5/10min(230℃，2.16kg)。
步骤二：将上述原料混合均匀，然后加入到注塑机料斗中，进行挤出造粒；造粒温度160℃，双螺杆转速400r/min，得到垫片粒料；
步骤三：将步骤一得到的垫片粒料放入模塑机中，130℃下挤出液滴于瓶盖中，压制成型，得到垫片或衬垫。
实施例6
一种免粘合剂的瓶盖垫片/或衬料，由以下重量分数的原料制备而成：
Figure PCTCN2017087230-appb-000009
其中，苯乙烯一异戊二烯一苯乙烯嵌段共聚物(SIS)的数均分子量为8.6×105，聚苯乙烯和聚异戊二烯嵌段质量含量分别为20％和40％；环烷油充油量为嵌段共聚物质量的10％；
所述聚乙烯为线性低密度聚乙烯(LLDPE)与低密度聚乙烯(LDPE)和混合物，其中LLDPE含量为40％，LDPE含量为60％，LLDPE和LDPE的熔融指数MFI分别为5.2/10min(230℃，2.16kg)和0.8/10min(230℃，2.16kg)。
步骤一：TPE环烷油充油，使其充油量为嵌段共聚物质量的10％。
步骤二：将上述原料混合均匀，然后加入到注塑机料斗中，进行挤出造粒；造粒温度170℃，双螺杆转速300r/min，得到垫片粒料；
步骤三：将步骤一得到的垫片粒料放入模塑机中，140℃下挤出液滴于瓶盖中，压制成型，得到垫片或衬垫。
实施例7
一种免粘合剂的瓶盖垫片/或衬料，由以下重量分数的原料制备而成：
Figure PCTCN2017087230-appb-000010
其中，苯乙烯一异戊二烯一苯乙烯嵌段共聚物(SIS)的数均分子量为7.8×104，聚苯乙烯和聚异戊二烯嵌段质量含量分别为15和45％；环保芳烃油充油为嵌段共聚物质量的15％；
所述聚乙烯为线性低密度聚乙烯(LLDPE)与低密度聚乙烯(LDPE)和混合物，其中LLDPE含量为60％，LDPE含量为40％，LLDPE和LDPE的熔融指数MFI为7.0/10min(230℃，2.16kg)。
步骤一：TPE环保芳烃油充油，使其充油量为嵌段共聚物质量的15％。
步骤二：将上述原料混合均匀，然后加入到注塑机料斗中，进行挤出造粒； 造粒温度150℃，双螺杆转速400r/min，得到垫片粒料；
步骤三：将步骤一得到的垫片粒料放入模塑机中，100℃下挤出液滴于瓶盖中，压制成型，得到垫片或衬垫。
实施例8
一种免粘合剂的瓶盖垫片/或衬料，由以下重量分数的原料制备而成：
Figure PCTCN2017087230-appb-000011
其中，苯乙烯一丁二烯一苯乙烯嵌段共聚物(SBS)的数均分子量为8.2×105，聚苯乙烯和聚丁二烯嵌段质量含量分别为15和45％；石蜡油充油量量为嵌段共聚物质量的15％；
所述低密度聚乙烯的熔融指数MFI为3.6/10min(230℃，2.16kg)。
步骤一：TPE石蜡油充油，使其充油量为嵌段共聚物质量的15％。
步骤二：将上述原料混合均匀，然后加入到注塑机料斗中，进行挤出造粒；造粒温度130℃，双螺杆转速450r/min，得到垫片粒料；
步骤三：将步骤一得到的垫片粒料放入模塑机中，130℃下挤出液滴于瓶盖中，压制成型，得到垫片或衬垫。
实施例9
一种免粘合剂的瓶盖垫片/或衬料，由以下重量分数的原料制备而成：
Figure PCTCN2017087230-appb-000012
其中，氢化苯乙烯一异戊二烯一苯乙烯嵌段共聚物(SEPS)的数均分子量为2.1×105，聚苯乙烯和聚异戊二烯嵌段质量含量分别为15和45％；芳烃油充油量为嵌段共聚物质量的10％％；
所述聚乙烯为线性低密度聚乙烯(LLDPE)与低密度聚乙烯(LDPE)和混合物，其中LLDPE含量为60％，LDPE含量为40％，LLDPE和LDPE的熔融指数MFI分别为2.5/10min(230℃，2.16kg)和4.5/10min(230℃，2.16kg)。
步骤一：TPE芳烃油充油，使其充油量为嵌段共聚物质量的15％。
步骤二：将上述原料混合均匀，然后加入到注塑机料斗中，进行挤出造粒；造粒温度160℃，双螺杆转速500r/min，得到垫片粒料；
步骤三：将步骤一得到的垫片粒料放入模塑机中，100℃下挤出液滴于瓶盖中，压制成型，得到垫片或衬垫。
实施例10
一种免粘合剂的瓶盖垫片/或衬料，由以下重量分数的原料制备而成：
Figure PCTCN2017087230-appb-000013
其中，氢化苯乙烯一异戊二烯一苯乙烯嵌段共聚物(SEPS)的数均分子量为4.5×105，聚苯乙烯和聚丁二烯嵌段质量含量分别为15和45％；环烷油充油量为嵌段共聚物质量的10％；
所述线性低密度聚乙烯(LLDPE)，LLDPE的熔融指数MFI为2.8/10min(230℃，2.16kg)。
步骤一：TPE环烷油充油，使其充油量为嵌段共聚物质量的10％。
步骤二：将上述原料混合均匀，然后加入到注塑机料斗中，进行挤出造粒；造粒温度180℃，双螺杆转速400r/min，得到垫片粒料；
步骤三：将步骤一得到的垫片粒料放入模塑机中，120℃下挤出液滴于瓶盖中，压制成型，得到垫片或衬垫。
实施11
一种免粘合剂的瓶盖垫片/或衬料，由以下重量分数的原料制备而成：
Figure PCTCN2017087230-appb-000014
其中，苯乙烯一异戊二烯一苯乙烯嵌段共聚物(SIS)的数均分子量为8.6×105，聚苯乙烯和聚异戊二烯嵌段质量含量分别为20％和40％；环烷油充油量为嵌段共聚物质量的10％；
所述低密度聚乙烯(LDPE)熔融指数MFI分别为3.8/10min(230℃，2.16kg)
步骤一：TPE环烷油充油，使其充油量为嵌段共聚物质量的10％。
步骤二：将上述原料混合均匀，然后加入到注塑机料斗中，进行挤出造粒；造粒温度170℃，双螺杆转速300r/min，得到垫片粒料；
步骤三：将步骤一得到的垫片粒料放入模塑机中，140℃下挤出液滴于瓶盖中，压制成型，得到垫片或衬垫。
实施12
一种免粘合剂的瓶盖垫片/或衬料，由以下重量分数的原料制备而成：
Figure PCTCN2017087230-appb-000015
其中，苯乙烯一异戊二烯一苯乙烯嵌段共聚物(SIS)的数均分子量为8.6×105，聚苯乙烯和聚异戊二烯嵌段质量含量分别为20％和40％；环烷油充油量为嵌段共聚物质量的10％；
所述聚乙烯为线性低密度聚乙烯(LLDPE)与低密度聚乙烯(LDPE)和混合物，其中LLDPE含量为40％，LDPE含量为60％，LLDPE和LDPE的熔融指数MFI分别为5.2/10min(230℃，2.16kg)和0.8/10min(230℃，2.16kg)。
步骤一：TPE环烷油充油，使其充油量为嵌段共聚物质量的10％。
步骤二：将上述原料混合均匀，然后加入到注塑机料斗中，进行挤出造粒；造粒温度170℃，双螺杆转速300r/min，得到垫片粒料；
步骤三：将步骤一得到的垫片粒料放入模塑机中，140℃下挤出液滴于瓶盖中，压制成型，得到垫片或衬垫。
实施例13
一种免粘合剂的瓶盖垫片/或衬料，由以下重量分数的原料制备而成：
Figure PCTCN2017087230-appb-000016
其中，苯乙烯一异戊二烯一苯乙烯嵌段共聚物(SIS)的数均分子量为 8.6×105，聚苯乙烯和聚异戊二烯嵌段质量含量分别为20％和40％；环烷油充油量为嵌段共聚物质量的10％；
所述聚乙烯为线性低密度聚乙烯(LLDPE)与低密度聚乙烯(LDPE)和混合物，其中LLDPE含量为40％，LDPE含量为60％，LLDPE和LDPE的熔融指数MFI分别为5.2/10min(230℃，2.16kg)和0.8/10min(230℃，2.16kg)。
步骤一：TPE环烷油充油，使其充油量为嵌段共聚物质量的10％。
步骤二：将上述原料混合均匀，然后加入到注塑机料斗中，进行挤出造粒；造粒温度170℃，双螺杆转速300r/min，得到垫片粒料；
步骤三：将步骤一得到的垫片粒料放入模塑机中，140℃下挤出液滴于瓶盖中，压制成型，得到垫片或衬垫。
实施例14
一种免粘合剂的瓶盖垫片/或衬料，由以下重量分数的原料制备而成：
Figure PCTCN2017087230-appb-000017
其中，苯乙烯一异戊二烯一苯乙烯嵌段共聚物(SIS)的数均分子量为8.6×105，聚苯乙烯和聚异戊二烯嵌段质量含量分别为20％和40％；环烷油充油量为嵌段共聚物质量的10％；
所述聚乙烯为线性低密度聚乙烯(LLDPE)与低密度聚乙烯(LDPE)和混合物，其中LLDPE含量为40％，LDPE含量为60％，LLDPE和LDPE的熔融指数MFI分别为5.2/10min(230℃，2.16kg)和0.8/10min(230℃，2.16kg)。
步骤一：TPE环烷油充油，使其充油量为嵌段共聚物质量的10％。
步骤二：将上述原料混合均匀，然后加入到注塑机料斗中，进行挤出造粒；造粒温度170℃，双螺杆转速300r/min，得到垫片粒料；
步骤三：将步骤一得到的垫片粒料放入模塑机中，140℃下挤出液滴于瓶盖中，压制成型，得到垫片或衬垫。
对比例1
一种瓶盖垫片/或衬料，由以下重量分数的原料制备而成：
Figure PCTCN2017087230-appb-000018
Figure PCTCN2017087230-appb-000019
其中，苯乙烯一异戊二烯一苯乙烯嵌段共聚物(SIS)的数均分子量为8.6×105，聚苯乙烯和聚异戊二烯嵌段质量含量分别为20％和40％；环烷油充油量为嵌段共聚物质量的10％；
所述聚乙烯为线性低密度聚乙烯(LLDPE)与低密度聚乙烯(LDPE)和混合物，其中LLDPE含量为40％，LDPE含量为60％，LLDPE和LDPE的熔融指数MFI分别为5.2/10min(230℃，2.16kg)和0.8/10min(230℃，2.16kg)。
步骤一：TPE环烷油充油，使其充油量为嵌段共聚物质量的10％。
步骤二：将上述原料混合均匀，然后加入到注塑机料斗中，进行挤出造粒；造粒温度170℃，双螺杆转速300r/min，得到垫片粒料；
步骤三：将步骤一得到的垫片粒料放入模塑机中，140℃下挤出液滴于瓶盖中，压制成型，得到垫片或衬垫。
对比例2
一种瓶盖垫片/或衬料，由以下重量分数的原料制备而成：
Figure PCTCN2017087230-appb-000020
其中，苯乙烯一异戊二烯一苯乙烯嵌段共聚物(SIS)的数均分子量为8.6×105，聚苯乙烯和聚异戊二烯嵌段质量含量分别为20％和40％；环烷油充油量为嵌段共聚物质量的10％；
所述聚乙烯为线性低密度聚乙烯(LLDPE)与低密度聚乙烯(LDPE)和混合物，其中LLDPE含量为40％，LDPE含量为60％，LLDPE和LDPE的熔融指数MFI分别为5.2/10min(230℃，2.16kg)和0.8/10min(230℃，2.16kg)。
步骤一：TPE环烷油充油，使其充油量为嵌段共聚物质量的10％。
步骤二：将上述原料混合均匀，然后加入到注塑机料斗中，进行挤出造粒；造粒温度170℃，双螺杆转速300r/min，得到垫片粒料；
步骤三：将步骤一得到的垫片粒料放入模塑机中，140℃下挤出液滴于瓶盖 中，压制成型，得到垫片或衬垫。
对比例3
一种瓶盖垫片/或衬料，由以下重量分数的原料制备而成：除了原料中不含有松香树脂外，其他原料及制备方法均与实施例6相同。
对比例4
一种瓶盖垫片/或衬料，由以下重量分数的原料制备而成：将松香树脂换成萜烯酚树脂，其他原料及制备方法均与实施例6相同。
对比例5
一种瓶盖垫片/或衬料，由以下重量分数的原料制备而成：将松香树脂换成环氧树脂，其他原料及制备方法均与实施例6相同。
实施例15
1、垫片或衬料的密封、耐压性测试
(1)将上述实施例1～14与对比例1～5所得垫片或衬垫成品应用于瓶盖上，然后将带有垫片或衬垫的瓶盖进行瞬间耐压试验：每组取50个带有垫片或衬垫瓶盖，用封盖机压在装有单向阀和压力表耐压装置瓶口上，瓶口应符合GB10809规定；检查封口合格后放入水箱中，对瓶内充注二氧化碳，从0MPa开始，升压至1.05～1.10MPa停lmin，观察有无漏气现象，并作记录。
(2)结果显示，本发明实施例1～14所述垫片或衬垫的瓶盖在1.10MPa压力下仍无漏气，对比例1～5均由不同程度的漏气。试验结束后检查瓶盖内的密封垫，均完整无缺，无变形。其中，实施例6制备得到的垫片或衬料在1.05～1.10MPa停2min时依然不漏气，表现出了很好的密闭性与耐压性。
2、垫片或衬料的粘结强度测试
(1)将上述实施例1～14与对比例1～5所得垫片或衬垫成品应用于瓶盖上，然后将带有垫片或衬垫的瓶盖进行巴氏灭菌后，看其密封垫是否脱落；
(2)结果显示，实施例1～14的密封垫均不脱落，而对比例1～5所述垫片均已脱落。
由此可见，本发明所述范围内制备出的垫片或衬料在保证垫片应用功能的同时无需粘合剂，使瓶盖生产过程更加简便、降低了能耗，具有较大的应用前景。

Claims (10)

  1. 一种免粘合剂的瓶盖垫片粒料，其特征在于，由以下重量份数的原料制备而成：
    Figure PCTCN2017087230-appb-100001
  2. 根据权利要求1所述的垫片粒料，其特征在于，由以下重量份数的原料制备而成：
    Figure PCTCN2017087230-appb-100002
  3. 根据权利要求1或2所述的垫片粒料，其特征在于，所述热塑性弹性体为至少一软嵌段和至少二硬嵌段构建的嵌段共聚物，硬嵌段包含一种聚苯乙烯，软嵌段包含一种聚共轭二烯烃或其氢化物。
  4. 根据权利要求3所述的垫片粒料，其特征在于，所述嵌段共聚物为苯乙烯-异戊二烯-苯乙烯嵌段共聚物、苯乙烯-丁二烯-苯乙烯三嵌段共聚物、氢化苯乙烯-丁二烯-苯乙烯三嵌段共聚物或氢化苯乙烯-异戊二烯-苯乙烯嵌段共聚物中的一种。
  5. 根据权利要求4所述的垫片粒料，其特征在于，所述嵌段共聚物的熔融指数为3～10；所述苯乙烯-异戊二烯-苯乙烯嵌段共聚物中聚苯乙烯和聚异戊二烯嵌段质量含量分别为15～50％；所述苯乙烯-丁二烯-苯乙烯三嵌段共聚物中聚苯乙烯和聚丁二烯嵌段质量含量分别为20～50％；所述氢化苯乙烯-丁二烯-苯乙烯三嵌段共聚物中聚苯乙烯和氢化聚异戊二烯嵌段质量含量分别为20～50％；所述氢化苯乙烯-异戊二烯-苯乙烯嵌段共聚物中聚苯乙烯和氢化聚丁二烯嵌段质量含量分别为20～50％。
  6. 根据权利要求3～5任一所述的垫片粒料，其特征在于，所述嵌段共聚物为充油处理的嵌段共聚物，其充油量为嵌段共聚物质量的0～20％。
  7. 根据权利要求1或2所述的垫片粒料，其特征在于，所述充油为环保芳烃油、石蜡油、环烷油或芳烃油中的一种。
  8. 根据权利要求1或2所述的垫片粒料，其特征在于，所述聚烯烃为低密度聚乙烯或线性低密度聚乙烯中或其混合物。
  9. 根据权利要求1或2所述的垫片粒料，其特征在于，所述松香树脂为改性松香树脂。
  10. 权利要求1～9任一所述的垫片粒料制备得到的免粘合剂的垫片和/或衬垫。
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