1. A transparent elastomer sealing material with oxygen absorption function, which is used for sealing a liquid beverage bottle cap and is adapted to a container bottle cap, is characterized in that,

the transparent elastomer sealing material comprises a transparent elastomer substrate and, provided on its side which is to be directed towards the container inner, at least one activation layer with an active substance which can bind oxygen, wherein the active substance can be incorporated as a functional layer at least locally into the transparent elastomer substrate.

2. The transparent elastomeric sealing material according to claim 1, wherein said transparent elastomeric sealing material is prepared by the steps of:

melting and extruding the pre-prepared materials by using double-screw mixing and extruding equipment, and granulating after cooling to obtain particles;

the obtained particles are pressed by a cover pressing die press to form a gasket-shaped transparent elastomer sealing material.

3. The transparent elastomeric sealing material according to claim 2, wherein it is adapted to the inside of the bottle cap according to the following preparation steps:

placing the particles prepared by the double-screw mixing extrusion equipment in a cover pressing die press, and heating for the second time;

extruding liquid drops into a bottle cap at a preset temperature, and performing compression molding;

after cooling, a gasket-like transparent elastomer sealing material stably attached to the inside of the bottle cap is formed.

4. A transparent elastomeric sealing material according to claim 3, wherein said pre-formulation is prepared by the steps of:

weighing raw materials, stirring by using a high-speed stirrer, and stirring at a high speed for a preset time to obtain a mixture;

and putting the mixture into a ball mill with zirconia beads for ball milling and dispersion to prepare the pre-prepared material.

5. The transparent elastomer sealing material as claimed in claim 4, wherein the screw rotation speed of the twin-screw mixing extrusion device can be controlled within 170-360 rpm, and/or the extrusion temperature can be controlled within 160-260 ℃, and/or the feeding rotation speed can be controlled within 60-150 rpm.

6. The transparent elastomeric sealing material according to claim 5, wherein in a case where the bottle cap is unused, the transparent elastomeric sealing material which has been fitted on the bottle cap is in a first state; when the cap is used, the transparent elastomer sealing material placed on the cap is in the second state, and the inner wall of the cap body can be observed through the transparent elastomer sealing material in the first state or the second state.

7. The transparent elastomer sealing material as claimed in claim 6, wherein the rotation speed of a screw in the gland molding press can be controlled to 80 to 110 rpm, and/or the solution injection temperature can be controlled to 80 to 120 ℃.

8. The transparent elastomer sealing material as claimed in claim 7, wherein the transparent elastomer sealing material is prepared by mixing at least the following raw materials in percentage by mass: 10-97% of transparent elastomer base stock; 0.1-9% of active substance; and 0.1-10% of filling oil.

9. The transparent elastomeric sealant according to claim 8 wherein the sealant may comprise one or a combination of several of polyol type actives, catechol type actives, persulfate type actives, iron type actives, light sensitive dye actives, hydrocatalyst type actives, enzyme type actives.

10. The transparent elastomeric sealant material of claim 9 wherein the enzyme-based active comprises at least one of glucose oxidase-type active, 4-hexylresorcinol, catechol, or combinations thereof.

Background

The existing beer bottle cap mainly comprises a cap body punched by a metal sheet, and a sealing gasket is added on the inner surface of the cap body, and the bottle cap is pressed on a bottle mouth to seal the bottle mouth. The air circulation inside and outside the bottle is cut off, so that the beer liquid does not flow out. Its advantages are high sealing effect, simple manufacture and low cost. However, beer is a beverage very sensitive to oxygen, which is very likely to react with polyphenol substances in beer to produce other products, so that the beer has turbid liquid, dark color and loses the special flavor or delicacy of the beer. The main reason for the loss of freshness is that a certain amount of oxygen (generally 1300ppb or more) inevitably remains in the bottle during the filling of the beverage. This trace amount of oxygen is sufficient to cause a drastic reduction in the beer flavor, i.e., a significant reduction in its shelf life.

In order to effectively eliminate the trace oxygen inside the package, some prior arts have proposed to use a material with active oxygen absorption or oxygen barrier in the sealing gasket. An automatic oxygen-absorbing inner pad material suitable for a beer bottle cap as proposed in patent document with publication number CN104945719A, is characterized in that: the components of the composition by weight portion are as follows: the anti-oxidation coating comprises, by weight, 8-18 parts of SEBS, 10-20 parts of mineral oil, 60-70 parts of polyethylene, 5-15 parts of polyolefin elastomer, 3-7 parts of calcium carbonate, 1-3 parts of maleic anhydride grafted polyethylene, 0.1-0.5 part of C9 petroleum resin, 0.1-0.5 part of antioxidant and 1-2 parts of reduced iron powder. The influence of oxygen in the air on the flavor of the beer is avoided, so that the shelf life of the beer is prolonged.

The lid made of oxygen-consuming material has the phenomenon that the gasket turns white or changes from transparent to semitransparent or opaque in the using process after being packaged, and at least has the following defects: after the cover is opened, the transparency of the sealing gasket is poor, so that a consumer cannot directly observe or scan the two-dimensional code in the bottle cap; the seal gasket becomes translucent or opaque by transparent, easily makes the consumer feel the official poor, seriously reduces the consumer to the trust of food quality in the bottle.

Furthermore, on the one hand, due to the differences in understanding to the person skilled in the art; on the other hand, since the inventor has studied a lot of documents and patents when making the present invention, but the space is not limited to the details and contents listed in the above, however, the present invention is by no means free of the features of the prior art, but the present invention has been provided with all the features of the prior art, and the applicant reserves the right to increase the related prior art in the background.

Disclosure of Invention

In order to solve the defect that the oxygen consumption material in the prior art turns white or becomes opaque or semitransparent from transparent in the using process, the transparent elastomer sealing material provided by the invention has an oxygen absorption function, can be used for sealing the bottle cap of a liquid beverage, has a good removing effect on oxygen in the bottle, can prolong the shelf life of the beverage and improve the flavor. Meanwhile, the oxygen absorption sealing gasket prepared by the method has good transparency. For some packages needing two-dimensional codes to be sprayed, the scanning of the two-dimensional codes in the packaging materials is not influenced. The flavor preservation effect of the food in the container is good, the sense of the consumer is good, and the trust of the consumer on the quality of the food in the bottle is not influenced.

In view of the above-mentioned deficiencies of the prior art, the present invention provides a transparent elastomeric sealing material with oxygen-absorbing function for sealing liquid beverage bottle caps and adapted to container bottle caps, characterized in that said transparent elastomeric sealing material comprises a transparent elastomeric substrate and, provided on its side intended to face the inner packaging of the container, at least one activation layer with an active substance capable of binding oxygen, wherein said active substance is at least partially incorporated as a functional layer into the transparent elastomeric substrate.

According to a preferred embodiment, the transparent elastomeric sealing material can be prepared according to the following steps: melting and extruding the pre-prepared materials by using double-screw mixing and extruding equipment, and granulating after cooling to obtain particles; the obtained particles are pressed by a cover pressing die press to form a gasket-shaped transparent elastomer sealing material.

According to a preferred embodiment, the transparent elastomeric sealing material may be adapted to the inside of the cap according to the following preparation steps: placing the particles prepared by the double-screw mixing extrusion equipment in a cover pressing die press, and heating for the second time; extruding liquid drops into a bottle cap at a preset temperature, and performing compression molding; after cooling, a gasket-like transparent elastomer sealing material stably attached to the inside of the bottle cap is formed.

According to a preferred embodiment, the pre-formulation may be prepared according to the following steps: weighing raw materials, stirring by using a high-speed stirrer, and stirring at a high speed for a preset time to obtain a mixture; and putting the mixture into a ball mill with zirconia beads for ball milling and dispersion to prepare the pre-prepared material.

According to a preferred embodiment, the screw rotating speed of the double-screw mixing extrusion equipment can be controlled within 170-360 revolutions per minute, and/or the extrusion temperature can be controlled within 160-260 ℃, and/or the feeding rotating speed can be controlled within 60-150 revolutions per minute.

According to a preferred embodiment, the twin-screw mixing extrusion equipment at least comprises one or more of a conveying section, a melting section, a mixing section, an exhaust section and a homogenizing section, wherein the temperature of the conveying section can be controlled to be 170-185 ℃, and/or the temperature of the melting section can be controlled to be 175-195 ℃, and/or the temperature of the mixing section can be controlled to be 175-200 ℃, and/or the temperature of the exhaust section can be controlled to be 190-220 ℃, and/or the temperature of the homogenizing section can be controlled to be 220-240 ℃.

According to a preferred embodiment, in the case of an unused cap, the transparent elastomeric sealing material already fitted on the cap is in a first state; when the cap is used, the transparent elastomer sealing material placed on the cap is in the second state, and the inner wall of the cap body can be observed through the transparent elastomer sealing material in the first state or the second state.

According to a preferred embodiment, the rotation speed of the screw in the capping press may be controlled to be 80 to 110 rpm, and/or the solution injection temperature may be controlled to be 80 to 120 ℃.

According to a preferred embodiment, the transparent elastomer sealing material is prepared by mixing at least the following raw materials in percentage by mass: 10-97% of transparent elastomer base stock; 0.1-9% of active substance; and 0.1-10% of filling oil.

According to a preferred embodiment, the sealing material may comprise one or a combination of several of polyol type active substances, catechol type active substances, persulfate type active substances, iron type active substances, light sensitive dye active substances, hydrocatalyst type active substances, enzyme type active substances.

According to a preferred embodiment, the enzyme system active comprises at least one of glucose oxidase type active, 4-hexylresorcinol, catechol or a combination of several thereof.

Drawings

FIG. 1 is a graph showing the comparison of the transmittance of a gasket manufactured by the method of the present invention;

FIG. 2 is a graph showing the comparison of oxygen contents of the sealing gasket manufactured by the method of the present invention.

Detailed Description

In order that the present invention may be more clearly understood, the following description is given for the preparation of a gasket using a transparent elastomeric sealing material, which is provided in the present invention, and the description in this section is only exemplary and illustrative and should not be taken as limiting the scope of the present invention:

s1, weighing raw materials at least comprising one or more of transparent elastomer base materials, active substances and filling oil, stirring by using a high-speed stirrer, and stirring at a high speed for a preset time to obtain a mixture.

And S2, putting the mixture into a ball mill with zirconia beads for ball milling and dispersion to obtain the pre-prepared material with larger dispersity.

And S3, melting and extruding the added pre-ingredients by using a double-screw mixing and extruding device. The screw rotating speed of the double-screw mixing extrusion equipment can be controlled to be 170-360 revolutions per minute, and/or the extrusion temperature can be controlled to be 160-260 ℃, and/or the feeding rotating speed can be controlled to be 60-150 revolutions per minute. The screw rotating speed of the double-screw mixing extrusion equipment can be controlled to be 170-360 revolutions per minute, and/or the extrusion temperature can be controlled to be 160-260 ℃, and/or the feeding rotating speed can be controlled to be 60-150 revolutions per minute.

And S4, introducing inert gas at the discharge port of the screw of the double-screw mixing extrusion equipment. The gas flow rate can be controlled to be 40-120 mL/min.

And S5, melting and mixing the materials by a double-screw mixing extrusion device, cooling the materials by a cold water tank, and then cutting the materials into particles to prepare the particles.

And S6, placing the particles prepared by the double-screw mixing extrusion equipment into a gland molding press, and heating for the second time. The rotating speed of a screw in the gland molding press can be controlled to be 80-110 r/min, and/or the solution injection temperature can be controlled to be 80-120 ℃.

And S7, extruding the liquid drops into the bottle cap at a preset temperature, pressing and forming, and cooling to form the gasket-shaped transparent elastomer sealing material stably attached to the inside of the bottle cap.

Thus, the transparent elastomer sealing material with the oxygen absorption function can be prepared.

The following description will be made mainly with respect to the components and the compounding ratio of the transparent elastomer sealing material. The raw material of the transparent elastomer sealing material may include one or a combination of several of a transparent elastomer base, an extender oil, and an active material. The transparent elastomer base material accounts for 10-97% of the transparent elastomer sealing material by mass; the filling oil accounts for 0.1-9% of the transparent elastomer sealing material by mass percent; the active substance may be contained in the transparent elastomer sealing material in an amount of 0.1 to 10% by mass.

The transparent elastomeric base may comprise a homopolymer-based elastomeric base and/or a copolymer-based elastomeric base.

The homopolymer elastomer base material can comprise polyethylene and/or polypropylene, and the polyolefin elastomer base material at least comprises one or more copolymers of ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 4-methyl-1-pentene and other alpha-olefins and cycloolefins.

The copolymer elastomer base stock can comprise a polyolefin random copolymer base stock, a polyolefin alternating copolymer base stock, a polyolefin block copolymer base stock and a polyolefin graft copolymer base stock. The polyolefin component may include one or a combination of polypropylene, propylene-based elastomers, polyethylene, and ethylene-based elastomers. The polyethylene may be of molecular weight 10⁴～10⁵Linear low density polyethylene, low density polyethylene or a combination of several of them. The melt indices of the linear low density polyethylene and the low density polyethylene were 3.2/10min (230 ℃ C., 2.16kg) and 0.8/10min (230 ℃ C., 2.16kg), respectively.

The active substance may include one or a combination of iron-based active substances, persulfate-based active substances, hydrocatalyst-type active substances, enzyme-based active substances, photosensitive dye active substances, polyol-type active substances and catechol-type active substances.

The iron-based active material may include one or a combination of several of reduced iron powder, electrolytic iron powder, sponge iron powder, cast iron powder, and ferrous oxide.

The persulfate-based active may include one or a combination of potassium persulfate, oxone, sodium persulfate, and sodium persulfate.

The hydrogenation catalyst type active material may include a metal catalyst which may be one or a combination of several of platinum, palladium, ruthenium, rhenium, rhodium, osmium, iridium, nickel, cobalt, molybdenum, copper, tin. The hydrocatalytic active species further comprises a carrier, which may be a promoted zirconium material. The hydrogenation catalyst type active substance can be one or a combination of a plurality of supported transition metal sulfuration type catalysts, supported noble metal catalysts and supported transition metal reduction state catalysts.

The enzyme system active may comprise a combination of one or more of glucose oxidase type actives, 4-hexylresorcinol, catechol.

The photosensitive dye active may be an ethyl cellulose film. The inside of the ethyl cellulose membrane is dissolved with a photosensitive dye and a singlet oxygen acceptor. When the ethyl cellulose membrane is illuminated by light with a proper wavelength, the excited photosensitive dye molecules can sensitize oxygen molecules which permeate into the ethyl cellulose membrane from the environment into singlet oxygen, and the singlet oxygen molecules react with singlet oxygen acceptor molecules, so that the purpose of consuming oxygen is achieved.

The polyol-type active substance may include ascorbic acid and derivatives thereof and/or erythorbic acid and salts thereof. Ascorbic acid and its derivatives may include calcium polyol, sodium polyol, palmitate polyol. The erythorbic acid and its salts may include erythorbic acid and sodium erythorbate.

The extender oil may include one or a combination of mineral oil, liquid rubber, vegetable oil, food grade white oil, food grade paraffinic oil, naphthenic oil.

In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. That is, it should be understood that the following examples are illustrative only and should not be construed as limiting the scope of the practice of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1

This example mainly describes a method for manufacturing a gasket by using a transparent elastomer sealing material, which is proposed in the present application. The preparation method may comprise one or more of the following steps:

and S1, weighing the raw materials, stirring the raw materials by using a high-speed stirrer, and stirring the raw materials at a high speed for a preset time to obtain a mixed double-screw mixing extrusion material. The raw materials and the proportion (weight percentage) are as follows: 20% of linear low-density polyethylene, 6% of polypropylene, 20% of ethylene-1-butene copolymer, 30% of ethylene-4-methyl-1-pentene copolymer, 1.3% of reduced iron powder, 0.8% of potassium persulfate, 0.9% of 4-hexylresorcinol, 0.8% of vegetable oil and 0.2% of an auxiliary agent.

And S2, putting the mixture into a ball mill with zirconia beads for ball milling and dispersion to obtain the pre-prepared material with larger dispersity.

And S3, melting and extruding the added pre-ingredients by using a double-screw mixing and extruding device.

And S4, introducing nitrogen at the discharge port of the screw of the double-screw mixing extrusion equipment.

And S5, melting and mixing the materials by a double-screw mixing extrusion device, cooling the materials by a cold water tank, and then cutting the materials into particles to prepare the particles.

And S6, placing the particles prepared by the double-screw mixing extrusion equipment into a gland molding press, and heating for the second time.

And S7, extruding the liquid drops into the bottle cap at a preset temperature, pressing and forming, and cooling to form the gasket-shaped transparent elastomer sealing material stably attached to the inside of the bottle cap.

Thus, the transparent elastomer sealing material with the oxygen absorption function can be prepared.

Example 2

The embodiment provides a preparation method for manufacturing a sealing gasket by using a transparent elastomer sealing material with an oxygen absorption function. This embodiment may be a further improvement and/or a supplement to embodiment 1, and repeated contents are not described again. The preferred embodiments of the present invention are described in whole and/or in part in the context of other embodiments, which can supplement the present embodiment, without resulting in conflict or inconsistency.

And S1, weighing the raw materials, stirring the raw materials by using a high-speed stirrer, and stirring the raw materials at a high speed for a preset time to obtain a mixed double-screw mixing extrusion material. The raw materials and the proportion (weight percentage) are as follows: 40% of polypropylene, 10% of ethylene-propylene copolymer, 42% of ethylene-1-hexene copolymer, 1.9% of ferrous oxide, 2.1% of sodium erythorbate, 3% of catechol, 0.7% of vegetable oil and 0.3% of auxiliary agent.

And S2, putting the mixture into a ball mill with zirconia beads for ball milling and dispersion to obtain the pre-prepared material with larger dispersity.

And S3, melting and extruding the added pre-ingredients by using a double-screw mixing and extruding device.

And S4, introducing nitrogen at the discharge port of the screw of the double-screw mixing extrusion equipment.

And S5, melting and mixing the materials by a double-screw mixing extrusion device, cooling the materials by a cold water tank, and then cutting the materials into particles to prepare the particles.

And S6, placing the particles prepared by the double-screw mixing extrusion equipment into a gland molding press, and heating for the second time.

And S7, extruding the liquid drops into the bottle cap at a preset temperature, pressing and forming, and cooling to form the gasket-shaped transparent elastomer sealing material stably attached to the inside of the bottle cap.

Thus, the transparent elastomer sealing material with the oxygen absorption function can be prepared.

Application examples

Firstly, the application adopts GB/T2410-. The test instrument was selected from the HM-150 hazemeter available from the MCRL brand of Japan. The term "haze" as used herein means the ratio of the amount of scattered light flux which is transmitted through a sample and deviates from the incident light direction to the amount of transmitted light flux, and is expressed as a percentage (in the case of the present method, only the amount of scattered light flux which deviates from the incident light direction by 2.5 ° or more is used to calculate the haze). Here, "light transmittance" refers to the ratio of the light flux transmitted through a sample to the light flux incident on the sample, and is expressed as a percentage.

The specific method comprises the following steps: 10 vial cap gasket samples, which are circular disks 50mm in diameter, were prepared from the transparent elastomeric sealing material proposed by the present invention according to examples 1 and 2. After adjusting for not less than 40h according to the state of GB/T2918-. Then, 10 bottle cap sealing gasket samples are respectively added into water to be sealed and soaked for 30 days, then the bottle cap sealing gasket samples are taken out to be wiped dry, the steps are repeated again, and the light transmittance is detected.

For each sample, the light transmission, expressed as a percentage, is calculated as:

in the formula: t is_t-light transmittance; t is₂-total transmitted light flux through the sample; t is₁-the incident light flux. The results were averaged to obtain FIG. 1.

As can be seen from figure 1, the light transmittance of the oxygen inhalation bottle cap sealing gasket prepared by the invention is not changed greatly and is more than 83% after being soaked for 30 days, and the sealing gasket meets the scanning requirement, so that the sealing gasket prepared by the invention has good transparency.

And secondly, the transparency of the material is tested by adopting an ASTM F3136-15 Standard test method for measuring the oxygen permeability of the plastic film and the thin plate by adopting a dynamic accumulation method as a test method. The test instrument can be selected(GEN III 5250i, OxySense, Texas, USA) fluorescent residual oxygen analyzer. Wherein, the principle of oxygen absorption performance test is as follows: the blue light irradiates on the fluorescent substance to excite the fluorescent substance and emit red light, and because the oxygen molecules can take away energy, the time and the intensity of the excited red light are inversely proportional to the concentration of the oxygen molecules, and the concentration of the oxygen molecules can be calculated by measuring the phase difference between the excited red light and the reference light and comparing the phase difference with an internal calibration value.

The specific method comprises the following steps: the oxygen sensor sheet of the instrument is adhered to the inner side of the cover of a 500ml container in advance, 400ml of deionized water is poured into the container, 5 gasket samples with the weight of 1g prepared by the invention are respectively added into 5 containers and then sealed, and the change of the oxygen content in the containers is measured through the fluorescence signal of the oxygen sensor sheet. Placing the container in a constant temperature and humidity chamber, testing at 23 + -2 deg.C and relative humidity of 50 + -3%, detecting oxygen content again after 30 days, and finally converting to obtain oxygen absorption amount of the oxygen absorbing material, as shown in FIG. 2.

As can be seen from figure 2, the sealing gasket prepared by the invention has good oxygen absorption performance, and the oxygen absorption amount can reach 750ug/g, so that the oxygen absorption sealing gasket prepared by the invention is used for sealing the bottle cap of the liquid beverage, has good removal effect on oxygen in the bottle, prolongs the shelf life of the beverage and improves the flavor.

It should be noted that the above-mentioned embodiments are exemplary, and that those skilled in the art, having benefit of the present disclosure, may devise various arrangements that are within the scope of the present disclosure and that fall within the scope of the invention. It should be understood by those skilled in the art that the present specification and figures are illustrative only and are not limiting upon the claims. The scope of the invention is defined by the claims and their equivalents. The present description contains several inventive concepts, such as "preferably", "according to a preferred embodiment" or "optionally", each indicating that the respective paragraph discloses a separate concept, the applicant reserves the right to submit divisional applications according to each inventive concept.