CN107745561A - A kind of scissile nylon EVOH high-resistant diaphragms and its production method - Google Patents
A kind of scissile nylon EVOH high-resistant diaphragms and its production method Download PDFInfo
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- CN107745561A CN107745561A CN201710917111.2A CN201710917111A CN107745561A CN 107745561 A CN107745561 A CN 107745561A CN 201710917111 A CN201710917111 A CN 201710917111A CN 107745561 A CN107745561 A CN 107745561A
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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
- B32B27/327—Layered products comprising a layer of synthetic resin comprising polyolefins comprising polyolefins obtained by a metallocene or single-site catalyst
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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
-
- 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
- B32B27/08—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 of synthetic resin
-
- 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
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
-
- 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
- B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
-
- 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
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
- B32B37/15—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state
- B32B37/153—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state at least one layer is extruded and immediately laminated while in semi-molten state
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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
-
- 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
- B32B2250/00—Layers arrangement
- B32B2250/40—Symmetrical or sandwich layers, e.g. ABA, ABCBA, ABCCBA
-
- 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
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/31—Heat sealable
-
- 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
-
- 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
- B32B2307/70—Other properties
- B32B2307/724—Permeability to gases, adsorption
- B32B2307/7242—Non-permeable
- B32B2307/7244—Oxygen barrier
-
- 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
- B32B2307/70—Other properties
- B32B2307/724—Permeability to gases, adsorption
- B32B2307/7242—Non-permeable
- B32B2307/7246—Water vapor barrier
-
- 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
- B32B2439/00—Containers; Receptacles
- B32B2439/70—Food packaging
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
- Laminated Bodies (AREA)
Abstract
The present invention relates to a kind of scissile nylon EVOH high-resistant diaphragms and its production method.The first PE film layers, the first bonding film layer, the first PA film layers, middle EVOH film layers, the 2nd PA film layers, the second bonding film layer and the 2nd PE film layers that nylon EVOH high-resistant diaphragms include contact successively and are molded by being coextruded mode；First, second PE film layers are made up of metallocene PE, linear polyethylene and polyethylene from high pressure process；First, second bonding film layer is made up of binder resin；First, second PA film layers are made up of polyamide；Middle EVOH film layers are made up of ethylene-vinyl alcohol copolymer.Nylon EVOH high-resistant diaphragms are melted by the way that the material of each film layer is added in seven-layer co-extrusion film blowing machine barrel, blown film cooling and shaping after coextrusion and obtain.Nylon EVOH high-resistant diaphragm barrier properties of the present invention are high, and heat sealability is excellent.Nylon EVOH high-resistant diaphragm coefficient of friction of the present invention is moderate, and adhesion will not be produced during cut-out, is skidded, is adapted to high-speed packaging production line.
Description
Technical field
The invention belongs to thin film materials art, is specifically related to a kind of scissile nylon EVOH high-resistant diaphragms and its production
Method.
Background technology
The 1990s mid-term rise, researcher starts primary study transparency high separation composite membrane, i.e., with PET, PA,
The single thin films such as PP, PE, EVOH, PVDC are raw material, compound by the way that dry type is compound, the extrusion technique such as compound carries out transparency high separation
The production of film, such as will coating PVDC films, evaporation oxidation film, EVOH resin co-extrusion films film by it is one or many it is compound i.e.
It can obtain transparency high separation composite membrane.But remained in the obtained high-barrier transparency film of the techniques such as dry type is compound, extrusion is compound
A large amount of double solvents, environmental pollution is not only resulted in, and production cost is higher.Patent CN102700210A discloses one kind seven
Layer co-extrusion high-barrier transparency film and preparation method thereof, although the preparation method is more environmentally friendly, and obtained high-barrier transparency film is saturating
Bright property and barrier property are preferable, but the heat seal strength of the film is weaker, and are not easy to be cut off on packaging production line, easily
In generation adhesion.
The content of the invention
In order to solve the above-mentioned technical problem, the present invention provides a kind of scissile nylon EVOH high-resistant diaphragms and its producer
Method.The film not only has high barrier property, and has extraordinary heat seal strength, while holds on packaging production line
Easily it is cut off, adhesion will not be produced, be especially suitable for high-speed packaging production line.
In order to realize the purpose of the present invention, present invention employs following technical scheme：
A kind of scissile nylon EVOH high-resistant diaphragms, including the first PE for contacting and being molded by coextrusion mode successively
Film layer, the first bonding film layer, the first PA film layers, middle EVOH film layers, the 2nd PA film layers, the second bonding film layer and the 2nd PE films
Layer；
The first PE film layers, the 2nd PE film layers are made up of metallocene PE, linear polyethylene and polyethylene from high pressure process,
The metallocene PE, linear polyethylene and polyethylene from high pressure process mass ratio are (45~55):(20~30):(20~30)；
The first bonding film layer, the second bonding film layer are made up of binder resin；
The first PA film layers, the 2nd PA film layers are made up of polyamide；
The middle EVOH film layers are made up of ethylene-vinyl alcohol copolymer.
Further, the first PE film layers, the first bonding film layer, the first PA film layers, middle EVOH film layers, the 2nd PA films
The thickness of layer, the second bonding film layer and the 2nd PE film layers is respectively 16 μm, 9 μm, 6 μm, 18 μm, 6 μm, 9 μm, 16 μm.
Further, the density of nylon EVOH high-resistant diaphragms is 1.12g/cm3, the density of the middle EVOH film layers
1.17g/cm3。
Further, the metallocene PE, linear polyethylene and polyethylene from high pressure process mass ratio are 50:25:25.
A kind of production method of described nylon EVOH high-resistant diaphragms, seven-layer co-extrusion is added to by the material of above-mentioned each film layer
Melted in film blowing machine barrel, blown film cooling and shaping obtains the nylon EVOH high-resistant diaphragms after coextrusion；The first PE film layers,
The melt temperature of 2nd PE film layer materials is 200 DEG C, and the first bonding film layer, the melt temperature of the second bonding film layer material are
225 DEG C, the first PA film layers, the melt temperature of the 2nd PA film layer materials are 255 DEG C, and the middle EVOH film layers material melts
Temperature is 225 DEG C.
Further, the material co-extrusion output is 500kg/h.
The beneficial effects of the present invention are：
(1) metallocene PE contamination resistance of the present invention is strong, and sealing effect is good, used in film the first PE film layers and
In 2nd PE film layers, heat seal effect is mainly played, ensures that packaging does not reveal liquid；The linear polyethylene, play enhancing institute
State the effect of the heat seal effect of metallocene PE；Because metallocene PE and the linear polyethylene blown film that mixes are endured
Degree is inadequate, after adding the polyethylene from high pressure process, serves the function of auxiliary production, film bubble is stablized and blows out, improves mouldability.
The first bonding film layer, the first bonding film layer are made up of binder resin, and its bonding effect is good, can be by PE film layers
It is bonded together well with PA film layers.
The first PA film layers, the density of polyamide in the 2nd PA film layers are 1.15g/cm3, use temperature range is wide,
It can be resistant to from -60 DEG C~200 DEG C, the higher sterilising temp of liquid milk can be resistant to, also can tolerate relatively low refrigeration temperature
Degree；Meanwhile polyamide has preferable tensile strength, puncture resistance, oxygen resistance is preferable, the utilization of two PA film layers, makes Buddhist nun
Imperial EVOH high-resistant diaphragms have more preferable oxygen barrier property.
The middle EVOH film layers are made up of ethylene-vinyl alcohol copolymer, and ethylene-vinyl alcohol copolymer is always using most
More high barrier materials.Its distinguishing feature is that have fabulous barrier to gas, and processability is fabulous.But ethene-
Vinyl alcohol copolymer resin is very poor to most polymers adhesive force, need to use special adhering resin, but ethylene-vinyl alcohol is total to
Homopolymer film can be adhered well on nylon membrane, i.e., ethylene-vinyl alcohol copolymer and polyamide have fairly good affine
Power.The glass transition temperature of ethylene-vinyl alcohol copolymer is high, adapts to processing and forming, and this performance can change the heating of PA film layers
When the shortcomings that being also easy to produce modification, so in inventive formulation, EVOH film layers are placed between two PA film layers.
The present invention has high resistance by being formulated the change formed, co-extrusion except the nylon EVOH high-resistant diaphragms that shaping obtains
Separating performance, wherein steam penetrating capacity≤5.0g/ (㎡ 24h), oxygen transit dose≤5.0cm3/ (㎡ 24h0.1MPa),
Effectively extend the shelf-life of pack content；Secondly heat sealability is excellent, and contamination resistance is strong, has extraordinary heat-sealing strong
Degree；Besides nylon EVOH high-resistant diaphragm coefficient of friction of the present invention is moderate, adhesion will not be produced during cut-out and is not in skid,
It is especially suitable for high-speed packaging production line.
(2) nylon EVOH high-resistant diaphragms of the present invention can only produce on seven-layer co-extrusion blown film machine equipment, and equipment mould
Each layer must have good effect of heat insulation.Production method of the present invention may insure processing temperature and material performance corresponding to each layer
Match, for example polyamide melt temperature is at 255 DEG C or so, and ethylene-vinyl alcohol copolymer melt temperature is at 225 DEG C or so,
Polyethylene melt temperature can not conduct heat between 255 DEG C or so, each layer, to prevent phase between each layer of different processing temperatures
Mutually pass and replace heat, so as to cause the problem of resin degraded can not be produced normally occur because heating is uncontrolled.
Embodiment
More specific detail is made to technical solution of the present invention with reference to embodiment：
Table 1 below is material source in embodiment：
Embodiment 1
By above-mentioned first PE film layers, the first bonding film layer, the first PA film layers, middle EVOH film layers, the 2nd PA film layers, second
The material of bonding film layer and the 2nd PE film layers, which is added in seven-layer co-extrusion film blowing machine barrel, to be melted, and blown film cooling is fixed after coextrusion
Type obtains the nylon EVOH high-resistant diaphragms；
Metallocene PE, linear polyethylene and polyethylene from high pressure process described in wherein the first PE film layers, the 2nd PE film layers
Mass ratio be 45:30:30；
The first PE film layers, the melt temperature of the 2nd PE film layer materials are 200 DEG C, the first bonding film layer, second
The melt temperature for bonding film layer material is 225 DEG C, and the first PA film layers, the melt temperature of the 2nd PA film layer materials are 255 DEG C,
The melt temperature of the middle EVOH film layers material is 225 DEG C.The material co-extrusion output is 500kg/h.
First PE film layers of the nylon EVOH high-resistant diaphragms obtained by above method production, the first bonding film layer, first
PA film layers, middle EVOH film layers, the 2nd PA film layers, the second bonding film layer and the thickness of the 2nd PE film layers are respectively 16 μm, 9 μ
m、6μm、18μm、6μm、9μm、16μm.The density of nylon EVOH high-resistant diaphragms is 1.12g/cm3。
Embodiment 2
By above-mentioned first PE film layers, the first bonding film layer, the first PA film layers, middle EVOH film layers, the 2nd PA film layers, second
The material of bonding film layer and the 2nd PE film layers, which is added in seven-layer co-extrusion film blowing machine barrel, to be melted, and blown film cooling is fixed after coextrusion
Type obtains the nylon EVOH high-resistant diaphragms；
Metallocene PE, linear polyethylene and polyethylene from high pressure process described in wherein the first PE film layers, the 2nd PE film layers
Mass ratio be 55:20:25；
The first PE film layers, the melt temperature of the 2nd PE film layer materials are 200 DEG C, the first bonding film layer, second
The melt temperature for bonding film layer material is 225 DEG C, and the first PA film layers, the melt temperature of the 2nd PA film layer materials are 255 DEG C,
The melt temperature of the middle EVOH film layers material is 225 DEG C.The material co-extrusion output is 500Kg/H.
First PE film layers of the nylon EVOH high-resistant diaphragms obtained by above method production, the first bonding film layer, first
PA film layers, middle EVOH film layers, the 2nd PA film layers, the second bonding film layer and the thickness of the 2nd PE film layers are respectively 16 μm, 9 μ
m、6μm、18μm、6μm、9μm、16μm.The density of nylon EVOH high-resistant diaphragms is 1.12g/cm3。
Embodiment 3
By above-mentioned first PE film layers, the first bonding film layer, the first PA film layers, middle EVOH film layers, the 2nd PA film layers, second
The material of bonding film layer and the 2nd PE film layers, which is added in seven-layer co-extrusion film blowing machine barrel, to be melted, and blown film cooling is fixed after coextrusion
Type obtains the nylon EVOH high-resistant diaphragms；
Metallocene PE, linear polyethylene and polyethylene from high pressure process described in wherein the first PE film layers, the 2nd PE film layers
Mass ratio be 50:25:20；
The first PE film layers, the melt temperature of the 2nd PE film layer materials are 200 DEG C, the first bonding film layer, second
The melt temperature for bonding film layer material is 225 DEG C, and the first PA film layers, the melt temperature of the 2nd PA film layer materials are 255 DEG C,
The melt temperature of the middle EVOH film layers material is 225 DEG C.The material co-extrusion output is 500kg/h.
First PE film layers of the nylon EVOH high-resistant diaphragms obtained by above method production, the first bonding film layer, first
PA film layers, middle EVOH film layers, the 2nd PA film layers, the second bonding film layer and the thickness of the 2nd PE film layers are respectively 16 μm, 9 μ
m、6μm、18μm、6μm、9μm、16μm.The density of nylon EVOH high-resistant diaphragms is 1.12g/cm3
Table 2 below is the performance test results of nylon EVOH high-resistant diaphragms in above-described embodiment：
The scissile nylon EVOH high-resistant diaphragms of the present invention carry out compound, its barrier by way of hot pressing with paper film
Can be more excellent and with the characteristics of being more easy to cutting off processing.
Claims (6)
- A kind of 1. scissile nylon EVOH high-resistant diaphragms, it is characterised in that：Including contact successively and by coextrusion mode into First PE film layers of type, first bonding film layer, the first PA film layers, middle EVOH film layers, the 2nd PA film layers, second bonding film layer with And the 2nd PE film layers；The first PE film layers, the 2nd PE film layers are made up of metallocene PE, linear polyethylene and polyethylene from high pressure process, described Metallocene PE, linear polyethylene and polyethylene from high pressure process mass ratio are (45~55):(20~30):(20~30)；The first bonding film layer, the second bonding film layer are made up of binder resin；The first PA film layers, the 2nd PA film layers are made up of polyamide；The middle EVOH film layers are made up of ethylene-vinyl alcohol copolymer.
- 2. nylon EVOH high-resistant diaphragms as claimed in claim 1, it is characterised in that：The first PE film layers, the first bonding film Layer, the first PA film layers, middle EVOH film layers, the 2nd PA film layers, the second bonding film layer and the thickness of the 2nd PE film layers are respectively 16μm、9μm、6μm、18μm、6μm、9μm、16μm。
- 3. nylon EVOH high-resistant diaphragms as claimed in claim 1, it is characterised in that：The density of nylon EVOH high-resistant diaphragms is 1.12g/cm3, the density 1.17g/cm of the middle EVOH film layers3。
- 4. nylon EVOH high-resistant diaphragms as claimed in claim 1, it is characterised in that：The metallocene PE, linear poly- second Alkene and polyethylene from high pressure process mass ratio are 50:25:25.
- A kind of 5. production method of nylon EVOH high-resistant diaphragms as described in any one of Claims 1 to 4, it is characterised in that：Will The material of above-mentioned each film layer, which is added in seven-layer co-extrusion film blowing machine barrel, to be melted, and blown film cooling and shaping obtains the Buddhist nun after coextrusion Imperial EVOH high-resistant diaphragms；The first PE film layers, the melt temperature of the 2nd PE film layer materials are 200 DEG C, first bonding film Layer, the melt temperature of the second bonding film layer material are 225 DEG C, the first PA film layers, the melt temperature of the 2nd PA film layer materials For 255 DEG C, the melt temperature of the middle EVOH film layers material is 225 DEG C.
- 6. the production method of nylon EVOH high-resistant diaphragms as claimed in claim 5, it is characterised in that：The material co-extrusion output For 500kg/h.
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| CN201710917111.2A CN107745561A (en) | 2017-09-30 | 2017-09-30 | A kind of scissile nylon EVOH high-resistant diaphragms and its production method |
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| CN201710917111.2A CN107745561A (en) | 2017-09-30 | 2017-09-30 | A kind of scissile nylon EVOH high-resistant diaphragms and its production method |
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Cited By (8)
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|---|---|---|---|---|
| CN109397779A (en) * | 2018-11-22 | 2019-03-01 | 江阴升辉包装材料有限公司 | A kind of high resistant oxygen film and the preparation method and application thereof |
| CN111251683A (en) * | 2020-02-27 | 2020-06-09 | 上海迈高新材料科技有限公司 | High-barrier seven-layer co-extruded film and preparation method thereof |
| CN113580703A (en) * | 2021-06-09 | 2021-11-02 | 浙江金仪盛世生物工程有限公司 | Film material for multilayer co-extrusion disposable biological process bag |
| CN113665210A (en) * | 2021-08-30 | 2021-11-19 | 广东丹青印务有限公司 | Degradable high-barrier food packaging bag, preparation device and method |
| CN115179628A (en) * | 2022-05-31 | 2022-10-14 | 江阴宝柏新型包装材料有限公司 | High-strength corrosion-resistant aluminum-plastic sheet and preparation method thereof |
| WO2022257252A1 (en) * | 2021-06-09 | 2022-12-15 | 浙江金仪盛世生物工程有限公司 | Film for single-use bioprocess bag and preparation method therefor |
| CN115847972A (en) * | 2022-11-10 | 2023-03-28 | 黄山永新股份有限公司 | Self-sealing and easy-to-uncover nine-layer co-extrusion barrier film and preparation process thereof |
| CN115847972B (en) * | 2022-11-10 | 2024-11-15 | 黄山永新股份有限公司 | Nine-layer co-extrusion barrier film with self-sealing and easy uncovering functions and preparation process thereof |
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