CN112590341A - Recyclable high-barrier composite sheet with high composite strength and preparation method thereof - Google Patents
Recyclable high-barrier composite sheet with high composite strength and preparation method thereof Download PDFInfo
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- CN112590341A CN112590341A CN202011471019.6A CN202011471019A CN112590341A CN 112590341 A CN112590341 A CN 112590341A CN 202011471019 A CN202011471019 A CN 202011471019A CN 112590341 A CN112590341 A CN 112590341A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D7/00—Producing flat articles, e.g. films or sheets
- B29D7/01—Films or sheets
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
-
- 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
- B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/54—Yield strength; Tensile strength
Abstract
The invention discloses a recyclable high-barrier composite sheet with high composite strength, which consists of an inner layer, an intermediate layer and an outer layer, wherein the inner layer is POP (post office purchase protocol), the POP is a PP-EVOH (polypropylene-ethylene-vinyl alcohol) multilayer co-extrusion high-barrier film, EVOH accounts for 7-10% of the layer thickness ratio, and the balance is PP; the middle layer is a PP sheet, and the outer layer is cast polypropylene; according to the invention, through related process innovation and equipment reformation, the composite strength of the prepared recyclable high-barrier composite sheet with high composite strength can reach 7N/15mm, and the requirement of the peel strength index of the composite forming sheet is completely met.
Description
Technical Field
The invention belongs to the technical field of films, and particularly relates to a recyclable high-barrier composite sheet with high composite strength and a preparation method thereof.
Background
Most of high-barrier composite sheets adopted in the current market adopt aluminum foil or EVOH as a high barrier layer, but the recovery of sheet waste materials adopting the aluminum foil as the high barrier layer is difficult and the cost is high; the use of EVOH is expensive due to its excessive addition amount, and the range of use is limited.
The patent application with publication number CN202388877U discloses a high-barrier composite sheet material, which consists of a high-barrier layer and a film lamination layer, wherein the film lamination mode is to perform double-sided film lamination on the high-barrier layer to form the film lamination layer; the high barrier layer consists of a coating substrate layer and a polyvinyl alcohol coating, and the polyvinyl alcohol coating is coated on the corona treatment surface of the coating substrate layer in advance; replace aluminium foil and PVDC coating with PVA as high oxygen resistant layer, this coating is degradable material, makes things convenient for whole composite sheet recovery processing, and polyolefin and middle high barrier layer take the non-adhesive to drench the membrane complex simultaneously, and green adopts this coating cost simultaneously and is lower than aluminium foil and PVDC, and more traditional sheet has bigger advantage.
Patent application with publication number CN205705609U discloses a high-barrier composite sheet, which comprises an inner film layer, a core material layer and a surface layer, wherein the inner film layer is a barrier film layer, the barrier film layer is a single-layer film or at least two layers of co-extruded barrier films, the barrier film layer is made of at least one selected from ethylene vinyl alcohol copolymer, polyamide and polyvinylidene chloride, and the surface layer is made of polyethylene terephthalate. The high-barrier composite sheet is reasonable in structure, the inner layer film and the surface layer are directly laminated with the core material layer, the use of an adhesive in the sheet is reduced, the use of a box body made of the sheet under a long-time low-temperature refrigeration condition is facilitated, the polyethylene terephthalate film is used as the outer layer film, the surface of the box body can be guaranteed to be smooth, the mechanical strength is good, and the sheet is suitable for packaging food such as bean curd. The utility model also discloses a packing box body of making with above-mentioned high separation composite sheet.
In the above two prior art documents, there are problems that the peel strength of the prepared high-barrier composite sheet is low, and the prepared high-barrier composite sheet has a low content of a single component and is difficult to recover, so that it is necessary to develop a sheet which uses a single component as a raw material and is easy to recover.
Disclosure of Invention
It is a first object of the present invention to provide a recyclable high barrier composite sheet having high composite strength.
The second purpose of the invention is to provide a preparation method of the recyclable high-barrier composite sheet with high composite strength.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the invention provides a recyclable high-barrier composite sheet with high composite strength, which consists of an inner layer, a middle layer and an outer layer, wherein the inner layer is POP (post office purchase protocol), the POP is a PP-EVOH (polypropylene-ethylene-vinyl alcohol) multilayer co-extrusion high-barrier film, EVOH accounts for 7-10% of the layer thickness ratio, and the balance is PP; the middle layer is a PP sheet, and the outer layer is cast polypropylene;
the preparation method of the recyclable high-barrier composite sheet with high composite strength comprises the following steps:
performing gravure inner printing on cast polypropylene, and then performing solvent-free compounding, curing and subsequent slitting treatment to obtain the recyclable high-barrier composite sheet with high composite strength;
the cast polypropylene gravure inner printing is to machine a cast polypropylene film, perform gravure printing by a plurality of color groups, and finally roll the cast polypropylene film to obtain a printing film with a complete printing pattern;
the solvent-free compounding comprises the following steps: coating a polyurethane adhesive (the coating amount is 1-3g) on a PP sheet with the surface subjected to corona treatment, and then compounding the PP sheet with the printing film with the printing pattern;
the curing is performed for 1-120 h at the temperature of 60-70 ℃.
The POP is prepared by an up-blowing method, is heated, melted and extruded to form a film, and does not contain an adhesive.
The outer layer is a printing layer.
The PP content in the recyclable high-barrier composite sheet with high composite strength is more than 95%.
In the recoverable high resistant composite sheet that separates that has high combined strength, outer thickness is 50um, and the intermediate layer thickness is 250um, and inlayer thickness is 50 um.
The second aspect of the invention provides a preparation method of the recyclable high-barrier composite sheet with high composite strength, which comprises the following steps:
performing gravure inner printing on cast polypropylene, and then performing solvent-free compounding, curing and subsequent slitting treatment to obtain the recyclable high-barrier composite sheet with high composite strength;
the cast polypropylene gravure inner printing is to machine a cast polypropylene film, perform gravure printing by a plurality of color groups, and finally roll the cast polypropylene film to obtain a printing film with a complete printing pattern;
the solvent-free compounding comprises the following steps: coating a polyurethane adhesive (the coating amount is 1-3g) on a PP sheet with the surface subjected to corona treatment, and then compounding the PP sheet with the printing film with the printing pattern;
the curing is performed for 1-120 h at the temperature of 60-70 ℃.
And performing corona treatment on the surface of the PP sheet at the speed of 50-100m/min (preferably 85-100 m/min).
Due to the adoption of the technical scheme, the invention has the following advantages and beneficial effects:
the recyclable high-barrier composite sheet with high composite strength, disclosed by the invention, has the advantages that the outer layer is a cast polypropylene film, the middle layer is a PP sheet, the inner layer is a high-barrier PP multi-layer co-extrusion film, only EVOH high-barrier resin is contained in the inner layer high-barrier PP multi-layer co-extrusion film, in the integral structure, the material consumption of polypropylene PP reaches more than 95%, and the standard requirement of a single recyclable material is met.
The invention relates to a multilayer sheet product which is obtained by compounding a PP sheet serving as a main body structure with a cast polypropylene film and a high-barrier PP multilayer co-extruded film. 95% is the polypropylene material in this composite sheet product, accords with single recoverable material requirement completely, and simultaneously, outer curtain coating polypropylene film can regard as the printing layer, and inlayer high resistant separates PP multilayer co-extrusion membrane and provides involution and high resistant characteristic, and current composite sheet demand can be satisfied completely to whole composite construction.
The composite strength of the traditional PP material structure is low, the related peeling strength is basically below 1.2N/15mm, and the composite strength of the recyclable high-barrier composite sheet with high composite strength can reach 7N/15mm through related process innovation and equipment reformation, so that the requirement of the peeling strength index of the composite forming sheet is completely met.
The preparation method of the recyclable high-barrier composite sheet with high composite strength is a solvent-free production process, adopts the high-viscosity polyurethane adhesive, improves the initial adhesion force of the lower machine, and reduces the number of defective outer rings in the traditional solvent-free production scheme.
The high-barrier PP multilayer co-extruded film of the inner layer is prepared by adopting an up-blowing method, most of the traditional PP resin is used for production by a tape casting method, and the high-barrier PP multilayer co-extruded film obtained by the up-blowing method has better orientation, and the mechanical property and the stiffness are enhanced to a certain extent after transverse and longitudinal blowing stretching.
The invention improves the existing curing chamber, the curing temperature reaches 60-70 ℃, the temperature requirement of the traditional soft package curing chamber can meet the requirement below 50 ℃, and the size stability and the heat resistance of the sheet are considered to be better, so the curing temperature is greatly improved, and the peel strength between the composite layers is greatly improved.
The power of the surface treatment device on the conventional compound equipment is improved along with the improvement of the production speed, and the production speed of sheet products is low (not more than 80m/min), so that in order to achieve the optimal treatment effect, the surface treatment control program is redesigned, and the treatment power is set manually to meet the low-speed production condition.
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below in connection with preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
Both CPP and PP used in the examples of the present invention are commercially available products.
Example 1
The CPP (casting polypropylene) used in the embodiment of the invention is a temperature-resistant type, the stretching change of the printing drying channel is small, and the overprinting is accurate.
The POP used in the embodiment of the invention is a PP-EVOH multilayer co-extruded high-barrier film, and corresponding functions can be added according to needs: antifogging, easy uncovering, etc.
The preparation method of the recyclable high-barrier composite sheet with high composite strength comprises the following steps:
CPP gravure inner printing → solvent-free compounding → curing → back cut processing.
CPP gravure inner printing: and (3) the CPP film is arranged on a machine, and is subjected to gravure printing by a plurality of color groups and finally is rolled to obtain the printing film with a complete printing pattern.
Solvent-free compounding: the solvent-free production process adopts the high-viscosity polyurethane adhesive, improves the initial adhesion force of the machine, and reduces the number of defective outer rings in the traditional solvent-free production scheme.
And gluing the PP sheet (the glue coating amount is 1-3g), and then compounding with the CPP printing film.
POP is a PP-EVOH multilayer co-extrusion high-barrier film and is prepared by an up-blowing method, and the method comprises the following specific steps: EVOH accounts for 10 percent of the layer thickness ratio, and the balance is PP, and the EVOH is made into a film by heating, melting and extruding without adhesive.
The curing process comprises the following steps: aging at 65 ℃ for 72 hours.
And (3) subsequent slitting treatment: and (3) producing by using a conventional splitting machine, and cleaning the environment.
Redesigning a surface treatment control program: the surface of the PP sheet is processed by corona treatment, and the speed of the special equipment is 85 m/min.
The prepared recyclable high-barrier composite sheet with high composite strength has the structure of an outer layer CPP 50/a middle layer PP sheet 250/an inner layer POP50 (the inner 50 or 250 is the thickness value of 50um or 250 um); the inner layer POP50 contained EVOH 10%,
the content of PP in the recyclable high-barrier composite sheet with high composite strength is 95.9%, and the international certification standard of single material is over 95%.
The properties of the prepared recyclable high barrier composite sheet with high composite strength are as follows:
the peel strength test method is carried out according to the peel test method of GB/T8808 soft composite plastic materials, the peel strength of the embodiment is 5N/15mm, and various tray containers can be blow-molded.
The recyclable high-barrier composite sheet with high composite strength can be recycled and granulated after being used, and then is processed into other plastic parts.
Example 2
The preparation method of the recyclable high-barrier composite sheet with high composite strength comprises the following steps:
CPP gravure inner printing → solvent-free compounding → curing → back cut processing.
CPP gravure inner printing: and (3) the CPP film is arranged on a machine, and is subjected to gravure printing by a plurality of color groups and finally is rolled to obtain the printing film with a complete printing pattern.
Solvent-free compounding: the solvent-free production process adopts the high-viscosity polyurethane adhesive, improves the initial adhesion force of the machine, and reduces the number of defective outer rings in the traditional solvent-free production scheme.
And gluing the PP sheet (the glue coating amount is 1-3g), and then compounding with the CPP printing film.
POP is a PP-EVOH multilayer co-extrusion high-barrier film and is prepared by an up-blowing method, and the method comprises the following specific steps: EVOH accounts for 9 percent of the layer thickness ratio, and the balance is PP, and the EVOH is made into a film by heating, melting and extruding without adhesive.
The curing process comprises the following steps: aging at 60 deg.C for 84 hr.
And (3) subsequent slitting treatment: and (3) producing by using a conventional splitting machine, and cleaning the environment.
Redesigning a surface treatment control program: the surface of the PP sheet is processed by corona treatment, and the speed of the special equipment is 90 m/min.
The prepared recyclable high-barrier composite sheet with high composite strength has the structure of an outer layer CPP 50/a middle layer PP sheet 250/an inner layer POP50 (the inner 50 or 250 is the thickness value of 50um or 250 um); the inner layer POP50 contained EVOH 9%,
the content of PP in the recyclable high-barrier composite sheet with high composite strength is 96.3%, and the international certification standard of single material is over 95%.
The properties of the prepared recyclable high barrier composite sheet with high composite strength are as follows:
the peel strength test method is carried out according to the peel test method of GB/T8808 soft composite plastic materials, the peel strength of the embodiment is 7N/15mm, and various tray containers can be blow-molded.
The recyclable high-barrier composite sheet with high composite strength can be recycled and granulated after being used, and then is processed into other plastic parts.
Example 3
The preparation method of the recyclable high-barrier composite sheet with high composite strength comprises the following steps:
CPP gravure inner printing → solvent-free compounding → curing → back cut processing.
CPP gravure inner printing: and (3) the CPP film is arranged on a machine, and is subjected to gravure printing by a plurality of color groups and finally is rolled to obtain the printing film with a complete printing pattern.
Solvent-free compounding: the solvent-free production process adopts the high-viscosity polyurethane adhesive, improves the initial adhesion force of the machine, and reduces the number of defective outer rings in the traditional solvent-free production scheme.
And gluing the PP sheet (the glue coating amount is 1-3g), and then compounding with the CPP printing film.
POP is a PP-EVOH multilayer co-extrusion high-barrier film and is prepared by an up-blowing method, and the method comprises the following specific steps: EVOH accounts for 8 percent of the layer thickness ratio, and the balance is PP, and the EVOH is made into a film by heating, melting and extruding without adhesive.
The curing process comprises the following steps: aging at 70 deg.C for 60 hr.
And (3) subsequent slitting treatment: and (3) producing by using a conventional splitting machine, and cleaning the environment.
Redesigning a surface treatment control program: the surface of the PP sheet is processed by corona treatment with a special device at the speed of 100 m/min.
The prepared recyclable high-barrier composite sheet with high composite strength has the structure of an outer layer CPP 50/a middle layer PP sheet 250/an inner layer POP50 (the inner 50 or 250 is the thickness value of 50um or 250 um); the inner layer POP50 contained EVOH 8%,
the content of PP in the recyclable high-barrier composite sheet with high composite strength is 96.4%, and the international certification standard of single material is over 95%.
The properties of the prepared recyclable high barrier composite sheet with high composite strength are as follows:
the peel strength test method is carried out according to the peel test method of GB/T8808 soft composite plastic materials, the peel strength of the embodiment is 6N/15mm, and various tray containers can be blow-molded.
The recyclable high-barrier composite sheet with high composite strength can be recycled and granulated after being used, and then is processed into other plastic parts.
Example 4
The preparation method of the recyclable high-barrier composite sheet with high composite strength comprises the following steps:
CPP gravure inner printing → solvent-free compounding → curing → back cut processing.
CPP gravure inner printing: and (3) the CPP film is arranged on a machine, and is subjected to gravure printing by a plurality of color groups and finally is rolled to obtain the printing film with a complete printing pattern.
Solvent-free compounding: the solvent-free production process adopts the high-viscosity polyurethane adhesive, improves the initial adhesion force of the machine, and reduces the number of defective outer rings in the traditional solvent-free production scheme.
And gluing the PP sheet (the glue coating amount is 1-3g), and then compounding with the CPP printing film.
POP is a PP-EVOH multilayer co-extrusion high-barrier film and is prepared by an up-blowing method, and the method comprises the following specific steps: EVOH accounts for 7 percent of the layer thickness ratio, and the balance is PP, and the EVOH is made into a film by heating, melting and extruding without adhesive.
The curing process comprises the following steps: aging at 65 ℃ for 72 hours.
And (3) subsequent slitting treatment: and (3) producing by using a conventional splitting machine, and cleaning the environment.
Redesigning a surface treatment control program: and performing corona treatment on the surface of the PP sheet by using special equipment at the speed of 95 m/min.
The prepared recyclable high-barrier composite sheet with high composite strength has the structure of an outer layer CPP 50/a middle layer PP sheet 250/an inner layer POP50 (the inner 50 or 250 is the thickness value of 50um or 250 um); the inner layer POP50 contained EVOH 7%,
the content of PP in the recyclable high-barrier composite sheet with high composite strength is 96.5%, and the international certification standard of single material is over 95%.
The properties of the prepared recyclable high barrier composite sheet with high composite strength are as follows:
the peel strength test method is carried out according to the peel test method of GB/T8808 soft composite plastic materials, the peel strength of the embodiment is 5.5N/15mm, and various tray containers can be blow-molded.
The recyclable high-barrier composite sheet with high composite strength can be recycled and granulated after being used, and then is processed into other plastic parts.
Comparative example 1
The product prepared by the preparation method with the solvent is CPP gravure inner printing → dry compounding → curing → back cutting treatment.
The peel strength of the product is 4.5N/15mm, and the solvent residue is more than or equal to 5 mg.
Compared with the method of the invention, the method has the advantages that the peel strength of the prepared product is not as good as that of the product prepared by the method of the invention, and simultaneously, the solvent residue is generated, but the method of the invention has no solvent residue.
Comparative example 2
The product prepared by the traditional solvent-free preparation method does not adopt a sheet surface corona treatment process, and the peel strength of the product is only 1-2N/15 mm.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (7)
1. The recyclable high-barrier composite sheet with high composite strength is characterized by comprising an inner layer, a middle layer and an outer layer, wherein the inner layer is POP (post office purchase) which is a PP-EVOH (polypropylene-ethylene-vinyl alcohol copolymer) multilayer co-extrusion high-barrier film, EVOH accounts for 7-10% of the layer thickness ratio, and the balance is PP; the middle layer is a PP sheet, and the outer layer is cast polypropylene;
the preparation method of the recyclable high-barrier composite sheet with high composite strength comprises the following steps:
performing gravure inner printing on cast polypropylene, and then performing solvent-free compounding, curing and subsequent slitting treatment to obtain the recyclable high-barrier composite sheet with high composite strength;
the cast polypropylene gravure inner printing is to machine a cast polypropylene film, perform gravure printing by a plurality of color groups, and finally roll the cast polypropylene film to obtain a printing film with a complete printing pattern;
the solvent-free compounding comprises the following steps: coating a polyurethane adhesive on a PP sheet with the surface subjected to corona treatment, and then compounding the PP sheet with the printing film with the printing pattern;
the curing is performed for 1-120 h at the temperature of 60-70 ℃.
2. The recyclable high barrier composite sheet with high composite strength according to claim 1, wherein the POP is prepared by an up-blowing method, is formed into a film by heating and melt extrusion, and is free of adhesives.
3. The recyclable high barrier composite sheet with high composite strength of claim 1, wherein the outer layer is a printed layer.
4. The recyclable high barrier composite sheet with high composite strength of claim 1, wherein the PP content of the recyclable high barrier composite sheet with high composite strength is 95% or more.
5. The recyclable high barrier composite sheet with high composite strength of claim 1, wherein the recyclable high barrier composite sheet with high composite strength has an outer layer thickness of 50um, an intermediate layer thickness of 250um and an inner layer thickness of 50 um.
6. A method for preparing the recyclable high barrier composite sheet with high composite strength as claimed in any one of claims 1 to 5, comprising the steps of:
performing gravure inner printing on cast polypropylene, and then performing solvent-free compounding, curing and subsequent slitting treatment to obtain the recyclable high-barrier composite sheet with high composite strength;
the cast polypropylene gravure inner printing is to machine a cast polypropylene film, perform gravure printing by a plurality of color groups, and finally roll the cast polypropylene film to obtain a printing film with a complete printing pattern;
the solvent-free compounding comprises the following steps: coating a polyurethane adhesive on a PP sheet with the surface subjected to corona treatment, and then compounding the PP sheet with the printing film with the printing pattern;
the curing is performed for 1-120 h at the temperature of 60-70 ℃.
7. The method for preparing recyclable high barrier composite sheet with high composite strength as claimed in claim 6, wherein the PP sheet is corona treated at a speed of 50-100 m/min.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113561597A (en) * | 2021-06-08 | 2021-10-29 | 升辉新材料股份有限公司 | Recyclable exquisite printing composite molding sheet and preparation method thereof |
| CN113844069A (en) * | 2021-08-11 | 2021-12-28 | 东南大学 | Preparation method of recyclable high-barrier high-strength composite film |
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