CN113211917A - Polypropylene-based composite film and preparation method thereof - Google Patents
Polypropylene-based composite film and preparation method thereof Download PDFInfo
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- CN113211917A CN113211917A CN202110465023.XA CN202110465023A CN113211917A CN 113211917 A CN113211917 A CN 113211917A CN 202110465023 A CN202110465023 A CN 202110465023A CN 113211917 A CN113211917 A CN 113211917A
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- polypropylene
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- 125000000524 functional group Chemical group 0.000 claims abstract description 15
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- 238000000034 method Methods 0.000 claims description 21
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- RESSOZOGQXKCKT-UHFFFAOYSA-N ethene;propane-1,2-diol Chemical compound C=C.CC(O)CO RESSOZOGQXKCKT-UHFFFAOYSA-N 0.000 description 1
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- 239000002245 particle Substances 0.000 description 1
- VFNSMNYXBSDMNK-UHFFFAOYSA-N penta-1,3-diene styrene Chemical class C=CC1=CC=CC=C1.C=CC=CC.C=CC1=CC=CC=C1 VFNSMNYXBSDMNK-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
-
- 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
-
- 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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
-
- 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
-
- 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
- B32B2250/24—All layers being polymeric
-
- 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
- B32B2307/75—Printability
Landscapes
- Laminated Bodies (AREA)
Abstract
The invention discloses a polypropylene-based composite film and a preparation method thereof, wherein the polypropylene-based composite film comprises the following components: the material of the polypropylene base layer comprises polypropylene; a tie layer attached to the polypropylene base layer, the material of the tie layer comprising polar functional group modified polypropylene; a printed layer attached to the tie layer, the printed layer being of a material selected from one or more of the group consisting of: (i) any one of ethylene-vinyl alcohol copolymer, thermoplastic polyurethane and polyamide or a blend of at least two of the two; (ii) copolymers of at least two of ethylene-vinyl alcohol copolymers, thermoplastic polyurethanes, polyamides; (iii) a blend of at least two of said copolymers. According to the invention, the connecting layer is introduced between the polypropylene base layer and the printing layer, so that materials between the layers are tightly bonded, the raised edge layering is not easy to occur, and the printing effect of the printing layer is ensured.
Description
Technical Field
The invention relates to the technical field of plastic films, in particular to a polypropylene-based composite film and a preparation method thereof.
Background
With the popularization of whole house customization, the demand of people for decorative home is gradually increased. The whole house customized furniture mostly adopts artificial boards such as particle boards, density boards, splice boards and the like as main bodies, and because the wood sources are different in color, and in addition, in order to take care of the preference of different groups of people to different color styles, customized furniture manufacturers often stick decorative film materials on artificial boards to form various decorative styles, so that the door/cabinet boards are more attractive and durable and have bright and uniform color.
The materials used by the current decorative film are mainly divided into two types: one type of decorative paper is the paper which comprises impregnated bond paper, pre-painted paper, melamine paper and the like, and is adhered to the surface of furniture after pattern printing and surface treatment are carried out on the paper. However, the decorative paper has poor water resistance and wear resistance, is easy to mildew, cannot avoid the release of formaldehyde, and is difficult to meet the high-end application requirements. The other decorative film material is polyvinyl chloride (PVC), which has the series advantages of good printing property, bright color, capability of impressing simulated wood grains, soft touch, good conformability and the like, and is widely applied to high-end panel furniture. However, PVC also has some disadvantages, such as poor heat resistance and aging resistance, is easy to yellow and discolor after long-time illumination, generates toxic hydrogen chloride gas during combustion, can cause certain fire safety hidden dangers, and is not beneficial to recovery and treatment.
In order to overcome the above-mentioned performance defects of PVC, decorative films based on polypropylene (PP) have been produced. The PP has good wear resistance, heat resistance, water resistance, aging resistance, chemical solvent resistance and good mechanical property, integrates the advantages of decorative paper and PVC films, and in addition, the PP does not contain chlorine element and heavy metal, and the waste can be recycled, thereby being an ideal raw material for a new generation of environment-friendly decorative films. Compared with the PVC material which is widely used at present, the PP material has the greatest difference that the polarity of the material is different, the PP material belongs to a non-polar material, and the PVC material is a polar material. The nonpolar PP surface has poor compatibility with the existing water-based ink, is difficult to print, and has poor adhesion on the surface of the ink.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art. Therefore, the invention provides the polypropylene-based composite film and the preparation method thereof, and the water-based ink has strong adhesive force on the polypropylene-based composite film and better printing effect.
In a first aspect of the present invention, there is provided a polypropylene-based composite film comprising:
the material of the polypropylene base layer comprises polypropylene;
a tie layer attached to the polypropylene base layer, the material of the tie layer comprising polar functional group modified polypropylene;
a printed layer attached to the tie layer, the printed layer being of a material selected from the group consisting of: (i) any one of ethylene-vinyl alcohol copolymer, thermoplastic polyurethane and polyamide or a blend of at least two of the two; (ii) copolymers of at least two of ethylene-vinyl alcohol copolymers, thermoplastic polyurethanes, polyamides; (iii) a blend of at least two of said copolymers.
The polypropylene-based composite film according to the embodiment of the invention has at least the following beneficial effects:
the invention provides a polypropylene-based composite film, wherein a selected specific printing layer material has high ink printing adhesion, and can meet the subsequent requirement for co-extrusion processing, in order to solve the problem of large polarity difference between a polypropylene base layer and a printing layer, a connecting layer is introduced between the polypropylene base layer and the printing layer, on one hand, the used connecting layer contains a polypropylene skeleton, and can have good compatibility with the polypropylene base layer, and can be fused with the polypropylene base layer in the subsequent melting and compounding process in a molecular diffusion and winding way, on the other hand, the material skeleton of the connecting layer contains a polar functional group, and the polar group can easily react with amino or hydroxyl at high temperature to form a chemical bond, so that the connecting layer and the printing layer are bonded together macroscopically. Therefore, the materials between the layers in the formed polypropylene-based composite film are tightly bonded, edge warping and layering are not easy to occur, and the printing effect of the printing layer is ensured.
The polypropylene used in the invention can be homopolymerized polypropylene, block copolymerization polypropylene, random copolymerization polypropylene or ternary copolymerization polypropylene, the product form of the polypropylene can be granules or powder, and the synthesis method can be Ziegler-Natta catalytic synthesis, metallocene catalytic synthesis or other conventional production preparation methods in the industry. Combinations of one or more of the above may be used in preparing the polypropylene-based layer.
In some embodiments of the present invention, the polypropylene-based layer material comprises 35 to 100% polypropylene, 0 to 30% filler and auxiliary agent by mass of the polypropylene-based layer. The filling material can be added when the polypropylene base layer is prepared, the used filling material is used for improving the dimensional stability and the thermal deformation temperature of the polypropylene base layer and reducing the cost, and the filling material can be one or more of wood powder, straw powder, calcium carbonate, mica, talcum powder, halloysite, barium sulfate, wollastonite, silicon dioxide and toner; one or more of calcium carbonate, talc and toner are preferred. The fillers mentioned above are fillers used in conventional plastics processing and are available by conventional means or commercially. Commercially available plastic masterbatches containing the above-mentioned fillers should also be regarded as a category of such fillers.
In some embodiments of the present invention, the auxiliary agent comprises 0 to 35% of a toughening agent and 0 to 5% of a compatibilizer based on the mass of the polypropylene-based layer.
The above toughening agent is used for improving the flexibility of the polypropylene base layer, and the toughening agent used may be one or more of polyethylene, ethylene-alpha-olefin copolymer (POE), ethylene-propylene copolymer (EPR), ethylene-propylene-diene monomer rubber (EPDM), ethylene-vinyl acetate copolymer (EVA), styrene-butadiene-styrene block copolymer (SBS), hydrogenated styrene-butadiene-styrene block copolymer (SEBS), hydrogenated styrene-pentadiene-styrene block copolymer (SEPS). Wherein the alpha-olefin in the POE refers to aliphatic olefin with 4-20 carbon atoms. The above toughening agents are all available by conventional means or commercially.
The compatilizer is used for improving the compatibility among the filler, the polypropylene and the toughening agent, and further is used for improving the mechanical property of the polypropylene base layer. The compatilizer can be selected from maleic anhydride or acrylic acid modified polyethylene, polypropylene, POE, EPR, EPDM, EVA, SEBS and SEPS, can also be binary or multicomponent copolymer containing carboxyl or anhydride groups, such as ethylene-maleic anhydride binary copolymer, ethylene-acrylic acid-acrylate ternary copolymer, ethylene-methacrylic acid-acrylate ternary copolymer and ethylene-acrylate-maleic anhydride ternary copolymer, and can also be silane coupling agent, titanate coupling agent or aluminate coupling agent. Partial compatilizers, such as maleic anhydride modified POE, maleic anhydride modified EPR, maleic anhydride modified EPDM, maleic anhydride modified EVA and maleic anhydride modified SEBS can be simultaneously used as the compatilizer and the toughening agent. The compatibilizing agent may be obtained by conventional means or commercially available, and may be used by selecting one or a combination of plural types of products.
In some embodiments of the present invention, the adjuvant further comprises at least one of an antioxidant, an ultraviolet absorber, a thermal stabilizer, a lubricant, a nucleating agent, and an anti-yellowing agent. The polypropylene base material can be used for improving the processing performance, the aging resistance and the like of polypropylene base layer materials by selecting auxiliary agents such as an antioxidant, an ultraviolet absorbent, a heat stabilizer, a lubricant, a nucleating agent, an anti-yellowing agent and the like.
In some embodiments of the present invention, the polar functional group-modified polypropylene comprises at least one of maleic anhydride-modified polypropylene, acrylic acid-modified polypropylene. The printing layer material such as polyamide, polyurethane or ethylene-vinyl alcohol copolymer has more amino and hydroxyl groups on the molecular structure, has strong hydrophilicity, is beneficial to printing by using water-based ink and has better environmental protection property. The polypropylene is modified by polar functional groups such as maleic anhydride groups and acrylic acid groups, so that the polar functional groups are introduced into the material of the connecting layer, and the connecting layer and the printing layer can be tightly bonded together by utilizing the chemical bonding of the polar functional groups and amino groups or hydroxyl groups in the printing layer.
In some embodiments of the present invention, the content of the polar functional group in the polar functional group-modified polypropylene is greater than or equal to 0.03% by mass of the tie layer. The introduced polar functional group is used for bonding with a group in the printing layer, and the bonding capability of the connecting layer and the printing layer is regulated and controlled by controlling the content of the polar functional group.
In some embodiments of the invention, the tie layer has a melt index of 1 to 15g/10min at a load of 2.16Kg at 230 ℃; preferably, the polypropylene-based layer has a melt index of 1-15g/10min under a load of 2.16Kg at 230 ℃. The melt index of the connecting layer is controlled, so that the subsequent co-extrusion with the polypropylene base layer and the printing layer is facilitated to prepare the composite film.
In some embodiments of the invention, the ethylene-vinyl alcohol copolymer has a melting point of 140 to 220 ℃; preferably, the melting point of the thermoplastic polyurethane is 150-250 ℃; preferably, the melting point of the polyamide is 180-260 ℃, and processing and molding are facilitated.
In some embodiments of the present invention, the polypropylene-based layer has a thickness of 50 to 95% of the thickness of the polypropylene-based composite film. The polypropylene base layer is too thin, the mechanical property of the formed composite film is insufficient, and burrs, depressions or other flaws on the surface of the decorated wood board cannot be effectively covered.
In some embodiments of the present invention, the tie layer has a thickness of 2 to 25% of the thickness of the polypropylene-based composite film. Because the polypropylene base layer is nonpolar polypropylene based material, and the printing layer is the polar layer, the two compatibility is poor, unable direct complex, the articulamentum that sets up is used for bonding polypropylene base layer and printing layer, make the polypropylene based composite film that forms become unified whole, when the thickness of articulamentum is too thin, the adhesion stress is too weak, the complex film is easy to delaminate, the thickness of articulamentum is too thick can make the holistic cost of complex film too high, the thickness that sets up the articulamentum accounts for 2 ~ 25% of whole complex film thickness can be in the balanced preparation cost when guaranteeing the adhesion stress.
The printing layer in the polypropylene-based composite film is arranged on the outer layer when in use and is made of polar materials. The print layer is generally used for decorative pattern printing. In some embodiments, the thickness of the printing layer is 3 to 25% of the thickness of the polypropylene-based composite film. The printing layer is too thin, the coloring property of the printing ink is poor, and the ink is easy to deink; too thick will affect the stiffness of the decorative film and cause excessive costs.
The material of the printing layer can be selected from ethylene vinyl alcohol copolymer (EVOH). In some embodiments, the ethylene content in the EVOH is 15-55 mol.%, preferably 20-45 mol.%. The ethylene content is too high, the polarity of the material is reduced, and the printing performance is insufficient; the ethylene content is too low, the brittleness of the material is increased, and the flexibility of the film is influenced. In some embodiments, the melting point of the EVOH is 140-220 ℃, preferably 160-200 ℃, which is beneficial for processing and molding.
The material of the printed layer may be selected from Thermoplastic Polyurethane (TPU). In some embodiments, the TPU may be a polyester TPU having a soft segment polymerized from a polyester, a polyether TPU having a soft segment polymerized from a polyether, or a copolymer TPU having a soft segment copolymerized from a polyester and a polyether. The melting point of the TPU is 150 ℃ to 250 ℃, preferably 170 ℃ to 220 ℃, and the processing and molding are facilitated. The Shore A hardness of the TPU is 50-95, preferably 70-95, and the mechanical property is favorably maintained.
The material of the printed layer may be selected from Polyamide (PA). The polymerization monomer of the PA is preferably aliphatic or alicyclic amine or acid, and can be PA6, PA12, PA610, PA1010 or special long-carbon-chain polyamide. In some embodiments, the melting point of PA is 180-260 ℃, preferably 200-250 ℃, which is beneficial for processing and molding. In some embodiments, the relative viscosity of the PA is greater than or equal to 3.0, preferably greater than or equal to 3.3, and PA with a relative viscosity in this range has a higher melt strength, which is beneficial for ensuring the strength and flatness of the film during the forming process.
It will be appreciated that the material of the print layer may also be a blend of at least two of the above-mentioned ethylene vinyl alcohol copolymers, thermoplastic polyurethanes, polyamides, copolymers or a blend of at least two of the copolymers.
In a second aspect of the present invention, a method for preparing the polypropylene-based composite film is provided, which comprises the following steps:
and (3) taking the material of the polypropylene base layer, the material of the connecting layer and the material of the printing layer, and preparing the polypropylene-based composite film by using a co-extrusion process.
The preparation method of the polypropylene-based composite film according to the embodiment of the invention has at least the following beneficial effects:
according to the invention, the polypropylene-based composite film is prepared by adopting a co-extrusion process, the polypropylene base layer and the connecting layer can be physically fused in the co-extrusion preparation process, and the connecting layer and the printing layer can be chemically bonded, so that the prepared polypropylene-based composite film is tightly bonded, edge warping and layering are not easy to occur, and the polypropylene-based composite film has better peel strength. The preparation method provided by the invention can be formed in one step through a co-extrusion process, the process is simple, and large-scale production can be carried out.
In some embodiments of the invention, the method comprises the following steps:
uniformly mixing the materials of the polypropylene base layer, and then extruding and granulating at 150-220 ℃ to prepare a polypropylene base layer material;
drying the material of the printing layer to obtain a printing layer material;
taking the material of the connecting layer as the material of the connecting layer for direct use;
and (3) preparing the polypropylene-based layer material, the connecting layer material and the printing layer material by a co-extrusion process to obtain the polypropylene-based composite film.
Before utilizing coextrusion technology preparation polypropylene composite film, to the polypropylene basic unit, adopt the material mixture of polypropylene basic unit and extrude the mode of granulation and handle, carry out drying process to the material of printing layer, the material of articulamentum directly uses, adopts different processing methods to different layer materials, closely bonds between each layer when doing benefit to the coextrusion preparation to do benefit to and promote the peel strength of the polypropylene based composite film who forms.
In some embodiments of the invention, the coextrusion process is coextrusion blown film or coextrusion cast film. In some embodiments of the present invention, specifically, the material of the polypropylene base layer, the material of the connection layer, and the material of the printing layer are respectively added into different extrusion runners of a three-layer melt co-extrusion processing apparatus or a multi-layer melt co-extrusion processing apparatus, and the polypropylene-based composite film is prepared by cooling, slitting, and winding in a co-extrusion film blowing or co-extrusion casting film forming manner.
In some embodiments of the invention, the co-extrusion process has a processing temperature of 170 to 250 ℃. In some embodiments of the present invention, specifically, if a co-extrusion film blowing manner is adopted, the temperature of the screw is controlled to be 170-250 ℃; cooling by air cooling at 5-20 deg.C and blow-up ratio of 2-3. If a co-extrusion casting film forming mode is adopted, the temperature of the screw is 170-250 ℃, the speed of the casting roller is 10-60m/min, and the temperature of the casting roller is 20-40 ℃; the roller cooling mode is adopted, the speed of the cooling roller is 10-60m/min, and the temperature is 20-40 ℃.
Drawings
The invention is further described with reference to the following figures and examples, in which:
FIG. 1 is a schematic view of the structure of a polypropylene-based composite film according to some embodiments of the present invention;
FIG. 2 is a cross-sectional view under an optical microscope of a polypropylene-based composite film prepared in example 1 of the present invention.
Detailed Description
The concept and technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments to fully understand the objects, features and effects of the present invention. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and those skilled in the art can obtain other embodiments without inventive effort based on the embodiments of the present invention, and all embodiments are within the protection scope of the present invention.
Referring to fig. 1, the present application provides a polypropylene-based composite film including a polypropylene-based layer 1, a tie layer 2 attached to the polypropylene-based layer 1, and a printed layer 3 attached to the tie layer 2. The following schemes may be used:
the total thickness of the polypropylene-based composite film is 0.05 to 0.60mm, preferably 0.20 to 0.50 mm. The film thickness is too thin, the mechanical property of the multilayer film is insufficient, and the multilayer film is easy to damage; the film thickness is too thick, the performance of attaching to a non-planar plate surface (such as a cabinet door panel with a part of engraved patterns) is not good, and the cost is too high. In some embodiments, the polypropylene base layer has a thickness of 50 to 95% of the entire thickness of the polypropylene-based composite film, the tie layer has a thickness of 2 to 25% of the entire thickness of the polypropylene-based composite film, and the print layer has a thickness of 3 to 25% of the entire thickness of the polypropylene-based composite film.
The polypropylene base layer is mainly made of polypropylene, the polypropylene can be homopolymerized polypropylene, block copolymerization polypropylene, random copolymerization polypropylene or ternary copolymerization polypropylene, the product form of the polypropylene can be granules or powder, and the synthesis method can be Ziegler-Natta catalytic synthesis or metallocene catalytic synthesis or other conventional industrial conventional production preparation methods. Combinations of one or more of the above may be used in preparing the polypropylene-based layer. The polypropylene base layer is an important component of the composite film, and the thickness of the polypropylene base layer accounts for 50-95% of the thickness of the composite film in some embodiments. In some embodiments, the polypropylene-based layer material has a melt index of 1 to 15g/10min, preferably 2 to 10g/10min (230 ℃, 2.16Kg), under a load of 2.16Kg at 230 ℃. The tensile strength of the polypropylene base layer is more than or equal to 15MPa, preferably more than or equal to 20 MPa; elongation at break of 200% or more, preferably 300% or more; the right angle tear strength is more than or equal to 100kN/m, preferably more than or equal to 120 kN/m; the dimensional shrinkage is 1.0% or less, preferably 0.5% or less. The Vicat softening point of the polypropylene base layer is equal to or greater than 100 ℃, preferably equal to or greater than 120 ℃.
In order to improve the performance of the polypropylene base layer, fillers, auxiliary agents and the like can be added, and the used auxiliary agents include but are not limited to toughening agents, compatilizers, antioxidants, ultraviolet absorbers, heat stabilizers, lubricants, nucleating agents, anti-yellowing agents and the like.
When the polypropylene-based layered material is prepared, the raw materials of the polypropylene-based layer are weighed according to the composition proportion and put into a high-speed mixer for uniform mixing. The rotating speed of the material mixer is 800-; mixing for 0.5-1 min. Then the raw material mixture is put into a double-screw extruder for melt mixing extrusion, and the extrusion temperature is 150-220 ℃. And cooling and dicing the extruded sample for later use.
In order to meet the printing effect of polar ink on the printing layer, the printing layer material generally needs to have stronger polarity, other polymer materials such as Polyethylene (PE), polyethylene-vinyl acetate (EVA) and the like have too low polarity, the ink adhesion is low, the PE adhesion grade is 5, the EVA adhesion grade is 4-5, the printing effect is poor, and the polymethyl methacrylate (PMMA) and Polycarbonate (PC) which have stronger polarity are brittle and cannot be bent, so that the printing layer material is not suitable for being made into a film by a co-extrusion processing method. Although polyethylene terephthalate (PET) and polyvinylidene chloride (PVDC) have strong polarity, the PET and the PVDC can also be melted and processed into a film, the adhesive property of the adhesive to the two materials is poor, delamination and separation can occur in co-extrusion, an integrally formed composite film cannot be obtained, and the composite film can be obtained only by respectively preparing a polypropylene film and a PET/PVDC film, then coating glue, and finally bonding the two films. The printing layer material selected by the application is selected from: (i) any one of ethylene-vinyl alcohol copolymer, thermoplastic polyurethane and polyamide or a blend of at least two of the two; (ii) copolymers of at least two of ethylene-vinyl alcohol copolymers, thermoplastic polyurethanes, polyamides; (iii) a blend of at least two of said copolymers. The selected printing layer material has higher polarity, the ink has large adhesive force on the surface thereof and good printing effect, and a connecting layer is introduced between the polypropylene base layer and the printing layer in order to solve the problem of large polarity difference between the polypropylene base layer and the printing layer.
The tie layer material in the present application comprises polar functional group modified polypropylene. In some embodiments, the polar functional group-modified polypropylene comprises at least one of maleic anhydride-modified polypropylene, acrylic acid-modified polypropylene. The content of the polar functional groups in the polar functional group modified polypropylene accounts for more than or equal to 0.03 percent of the mass fraction of the connecting layer. The 180-degree peel strength of the polypropylene base layer and the printing layer which are bonded through the connecting layer is more than or equal to 5N/cm. The melt index of the connecting layer is 1-15g/10min when the load is 2.16Kg at 230 ℃.
The polypropylene-based composite film disclosed by the application is in contact with the substrates such as wood in a laminating manner when in use, so that sufficient mechanical strength can be provided, the printing layer is mainly used as a printing stock, patterns and the like can be printed on the printing layer, and the polypropylene-based composite film can cover defects of the substrates and decorate the surface layer.
Example 1
The implementation provides a polypropylene-based composite film, which comprises a polypropylene base layer, a connecting layer attached to the polypropylene base layer and a printing layer attached to the connecting layer, and the polypropylene-based composite film is prepared by the following steps:
(1) preparation of polypropylene-based layer material: the raw materials of each component are weighed according to the composition proportion in the table 1 and put into a high-speed mixer for uniform mixing. The rotating speed of the mixer is 800-. Then the raw material mixture is put into a double-screw extruder for melt mixing extrusion, and the extrusion temperature is 190 ℃. And cooling and dicing the extruded sample for later use.
Preparing a connecting layer material: the raw materials were prepared as shown in Table 1 and used as a tie layer material.
Preparing a printing layer material: the raw materials were prepared as shown in Table 1, dried at 100 ℃ for 2-4 hours and used as printing layer.
Wherein, the polypropylene in Table 1 is purchased from petrochemical group of China, Inc.; the toughener is POE (polyolefin elastomer) available from dow chemical, usa; maleic anhydride modified polypropylene was purchased from mitsui chemicals; TPU is available from Vanhua chemical group, Inc.
(2) Preparing a polypropylene-based composite film: and adding the materials of each layer into three-layer co-extrusion casting equipment, adjusting the temperature of a screw rod to be 210 ℃, the speed of a casting roller to be 30m/min, the temperature of the casting roller to be 20 ℃, adjusting the thicknesses of the polypropylene base layer, the connecting layer and the printing layer, adopting a roller cooling mode, adjusting the speed of a cooling roller to be 30m/min and the temperature to be 20 ℃, and slitting and rolling to obtain the polypropylene-based composite film of the embodiment.
The total thickness of the polypropylene-based composite film prepared in this example is about 0.25mm, wherein the thicknesses of the polypropylene-based layer, the tie layer and the printing layer respectively account for 65%, 21% and 14% of the total film thickness of the composite film. The cross-sectional view of the polypropylene-based composite film prepared by the embodiment under an optical microscope is shown in fig. 2, the label 1 is a polypropylene base layer, the label 2 is a connecting layer, the label 3 is a printing layer, the connection between the layers can be seen from the figure to be tight, the non-polar polypropylene base layer with large surface energy difference and the polar printing layer are unified into a whole by arranging the connecting layer, so that materials with different functions can be integrated into a whole, and respective functions can be realized in different areas without mutual interference, and the polypropylene-based composite film can have the effect of each layer.
Table 1 example 1 composition and arrangement of materials of respective layers in polypropylene-based composite film
Example 2
The embodiment provides a polypropylene-based composite film, which comprises a polypropylene base layer, a connecting layer attached to the polypropylene base layer and a printing layer attached to the connecting layer, and is prepared by the following steps:
(1) preparation of polypropylene-based layer material: the raw materials of each component were weighed according to the composition ratios in table 2 and put into a high-speed mixer for uniform mixing. The rotating speed of the mixer is 800-. Then the raw material mixture is put into a double-screw extruder for melt mixing extrusion, and the extrusion temperature is 210 ℃. And cooling and dicing the extruded sample for later use.
Preparing a connecting layer material: the raw materials were prepared as shown in Table 2 and used as binders.
Preparing a printing layer material: the raw materials were prepared as shown in Table 2, and dried at 100 ℃ for 2-4 hours to be used as a printing layer.
Wherein, the polypropylene in Table 2 is purchased from petrochemical group of China, Inc.; the compatibilizer was maleic anhydride modified SEBS (hydrogenated styrene-butadiene block copolymer) available from kraton corporation, usa; maleic anhydride modified polypropylene was purchased from liard basel, netherlands; EVOH is available from the company Coli, Japan.
(2) Preparing a polypropylene-based composite film: and adding the materials of each layer into three-layer co-extrusion casting equipment, adjusting the temperature of a screw rod to be 200 ℃, the speed of a casting roller to be 30m/min, the temperature of the casting roller to be 20 ℃, adjusting the thicknesses of the polypropylene base layer, the connecting layer and the printing layer, adopting a roller cooling mode, adjusting the speed of a cooling roller to be 30m/min and the temperature to be 20 ℃, and slitting and rolling to obtain the polypropylene-based composite film of the embodiment.
The total thickness of the polypropylene-based composite film prepared in this example is about 0.35mm, wherein the thicknesses of the polypropylene-based layer, the tie layer and the printing layer respectively account for 70%, 10% and 20% of the total film thickness of the composite film.
Table 2 example 2 composition and arrangement of materials of respective layers in polypropylene-based composite film
Example 3
The embodiment provides a polypropylene-based composite film, which comprises a polypropylene base layer, a connecting layer attached to the polypropylene base layer and a printing layer attached to the connecting layer, and is prepared by the following steps:
(1) preparation of polypropylene-based layer material: the raw materials of each component were weighed according to the composition ratios in table 3 and put into a high-speed mixer for uniform mixing. The rotating speed of the mixer is 800-. Then the raw material mixture is put into a double-screw extruder for melt mixing extrusion, and the extrusion temperature is 170 ℃. And cooling and dicing the extruded sample for later use.
Preparing a connecting layer material: the raw materials were prepared as shown in Table 3 and used as a tie layer material.
Preparing a printing layer material: the raw materials were prepared as shown in Table 3, and dried at 100 ℃ for 2-4 hours to be used as a printing layer.
Wherein the polypropylene in Table 3 is purchased from petrochemical group, Inc., China; the toughening agent was EPR (ethylene propylene glycol) available from Exxon Mobil; the color master batch is blue color master batch which is purchased from Ningbo color master batch GmbH; nucleating agents were purchased from Milliken & company, USA; maleic anhydride modified polypropylene was purchased from liard basel, netherlands; PA (Polyamide) was PA6, available from BASF corporation.
(2) Preparing a polypropylene-based composite film: adding the materials into three-layer co-extrusion casting equipment, adjusting the temperature of screws of the polypropylene base layer, the connecting layer and the printing layer to be 200 ℃, 220 ℃ and 250 ℃, the speed of a casting roller to be 60m/min, the temperature of the casting roller to be 20 ℃, adjusting the thickness of the polypropylene base layer, the connecting layer and the printing layer, adopting a roller cooling mode, the speed of a cooling roller to be 60m/min and the temperature to be 20 ℃, and slitting and rolling to obtain the polypropylene-based composite film of the embodiment.
The total thickness of the polypropylene-based composite film prepared in this example is about 0.50mm, wherein the thicknesses of the polypropylene-based layer, the tie layer and the printing layer respectively account for 85%, 5% and 10% of the total film thickness of the composite film.
Table 3 example 3 composition and arrangement of materials of respective layers in polypropylene-based composite film
Comparative example of Effect
Comparative example 1: comparative example 1 a polypropylene-based film was provided, which was prepared in the same manner as in example 1 except that the tie layer and the printed layer were not included.
Comparative example 2: comparative example 2 provides a polypropylene-based composite film, which was prepared in the same manner as in example 1, except that the tie layer was not included.
Comparative example 3: comparative example 3 provides a polypropylene-based film subjected to surface corona treatment, which was prepared by the following method: the polypropylene-based film obtained in comparative example 1 was subjected to a surface polarization treatment by high-voltage corona so that the surface tension coefficient of the film was 50dyn/cm or more.
The polypropylene-based composite films of examples 1 to 3 and the samples of comparative examples 1 to 3 were subjected to evaluations of printing properties and compounding properties, and the evaluation results are shown in table 4, as follows:
printing performance was used to evaluate the adhesion of printing inks on films by the test method: the sample film was cut out and the film size was fixed at 30cm by 30 cm. The film samples were coated centrally with a commercially available water-based ink, with a coating area of 20cm by 20cm and an ink layer thickness of 0.02mm, placed in an oven at 100 ℃ for 1h, removed and placed at ambient temperature for 24h before testing. The ink adhesion is tested by adopting a grid cutting method according to the method of the national standard GB/T9286, and the adhesion grade is divided into six grades from good to bad, namely 0-5. And randomly selecting at least 5 areas of the same sample for testing, and recording the maximum value of the adhesive force grade as a test result.
The composite performance is used for evaluating the bonding performance between layers of the multilayer film, and the test method comprises the following steps: film samples were cut 20cm by 1cm, softened by heating the port using a heat gun, and the multilayer film was separated with a sharp-pointed forceps while hot. After the sample is completely cooled, the two separated films are respectively placed at two ends of a universal mechanical testing machine, and the peel strength of the films is tested. The same sample was tested 5 times on average and the average was recorded as the test result.
As can be seen from Table 4, the surface printing performance of the polypropylene-based composite films prepared in examples 1 to 3 is significantly improved, the adhesion to conventional water-based inks reaches the highest level, and the actual application requirements can be met, compared with the samples of comparative examples 1 to 3. The printing layer is a polar material, the surface performance of the printing layer cannot be attenuated along with time, the printing layer can still keep good printability after being placed for six months, and the printing adhesion grade reaches the highest grade. In addition, the polypropylene-based composite film prepared by the method can connect the polar printing layer material and the nonpolar PP base material into a unified whole after the connecting layer is introduced, does not warp and delaminate, and has good composite performance.
TABLE 4 printability and Complexity Properties of film samples of examples 1-3 and comparative examples 1-3
Reprint adhesion rating: the samples were allowed to stand at room temperature for six months, and then were printed with the same ink to evaluate adhesion.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention.
Claims (10)
1. A polypropylene-based composite film comprising:
the material of the polypropylene base layer comprises polypropylene;
a tie layer attached to the polypropylene base layer, the material of the tie layer comprising polar functional group modified polypropylene;
a printed layer attached to the tie layer, the printed layer being of a material selected from one or more of the group consisting of: (i) any one of ethylene-vinyl alcohol copolymer, thermoplastic polyurethane and polyamide or a blend of at least two of the two; (ii) copolymers of at least two of ethylene-vinyl alcohol copolymers, thermoplastic polyurethanes, polyamides; (iii) a blend of at least two of said copolymers.
2. The polypropylene-based composite film according to claim 1, wherein the polypropylene-based layer comprises an auxiliary, 35 to 100% polypropylene and 0 to 30% filler, based on the mass of the polypropylene-based layer.
3. The polypropylene-based composite film according to claim 2, wherein the auxiliary comprises 0-35% of a toughening agent and 0-5% of a compatilizer by mass of the polypropylene-based layer.
4. The polypropylene-based composite film according to claim 3, wherein the auxiliary agent further comprises at least one of an antioxidant, an ultraviolet absorber, a thermal stabilizer, a lubricant, a nucleating agent and an anti-yellowing agent.
5. The polypropylene-based composite film according to any one of claims 1 to 4, wherein the polar functional group-modified polypropylene comprises at least one of maleic anhydride-modified polypropylene, acrylic acid-modified polypropylene; preferably, the content of the polar functional group in the polar functional group modified polypropylene accounts for more than or equal to 0.03 percent of the mass fraction of the connecting layer.
6. The polypropylene-based composite film according to any one of claims 1 to 4, wherein the tie layer has a melt index of 1 to 15g/10min under a load of 2.16Kg at 230 ℃; preferably, the polypropylene-based layer has a melt index of 1-15g/10min under a load of 2.16Kg at 230 ℃.
7. The polypropylene-based composite film according to any one of claims 1 to 4, wherein the ethylene-vinyl alcohol copolymer has a melting point of 140 to 220 ℃; preferably, the melting point of the thermoplastic polyurethane is 150-250 ℃; preferably, the melting point of the polyamide is 180-260 ℃.
8. The polypropylene-based composite film according to any one of claims 1 to 4, wherein the polypropylene-based layer has a thickness of 50 to 95% of the thickness of the polypropylene-based composite film; preferably, the thickness of the connection layer accounts for 2-25% of the thickness of the polypropylene-based composite film.
9. The method for preparing a polypropylene-based composite film according to any one of claims 1 to 8, comprising the steps of: and (3) taking the material of the polypropylene base layer, the material of the connecting layer and the material of the printing layer, and preparing the polypropylene-based composite film by using a co-extrusion process.
10. The method of preparing a polypropylene-based composite film according to claim 9, comprising the steps of:
uniformly mixing the materials of the polypropylene base layer, extruding and granulating at 150-220 ℃ to prepare a polypropylene base layer material,
drying the material of the printing layer to obtain a printing layer material,
the material of the connecting layer is taken as the material of the connecting layer for direct use,
preparing the polypropylene-based layer material, the connecting layer material and the printing layer material by a co-extrusion process to obtain a polypropylene-based composite film; preferably, the co-extrusion process is co-extrusion film blowing or co-extrusion film casting; preferably, the processing temperature of the co-extrusion process is 170-250 ℃.
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| CN114196054A (en) * | 2021-12-29 | 2022-03-18 | 清远爱奇制造有限公司 | Polyolefin seat and preparation method and application thereof |
| CN115873523A (en) * | 2021-09-26 | 2023-03-31 | 大正新型材料(肇庆)有限公司 | Polypropylene decorative film with adhesive film layer and preparation method and application thereof |
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| CN102873950A (en) * | 2012-09-21 | 2013-01-16 | 海南赛诺实业有限公司 | High-surface-energy double-direction stretching polypropylene thin film and manufacturing method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102873950A (en) * | 2012-09-21 | 2013-01-16 | 海南赛诺实业有限公司 | High-surface-energy double-direction stretching polypropylene thin film and manufacturing method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115873523A (en) * | 2021-09-26 | 2023-03-31 | 大正新型材料(肇庆)有限公司 | Polypropylene decorative film with adhesive film layer and preparation method and application thereof |
| CN114196054A (en) * | 2021-12-29 | 2022-03-18 | 清远爱奇制造有限公司 | Polyolefin seat and preparation method and application thereof |
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