CN114525086A - Polyolefin release film, preparation method thereof and preparation method of roughened surface layer - Google Patents

Polyolefin release film, preparation method thereof and preparation method of roughened surface layer Download PDF

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Publication number
CN114525086A
CN114525086A CN202210096457.1A CN202210096457A CN114525086A CN 114525086 A CN114525086 A CN 114525086A CN 202210096457 A CN202210096457 A CN 202210096457A CN 114525086 A CN114525086 A CN 114525086A
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China
Prior art keywords
polyolefin
layer
release film
coating
polymer
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Inventor
韩忠强
朱元华
段艳全
曹雪
陈永初
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Jinsinan Film Shanghai Technology Co ltd
Nantong Jinsinan Membrane Material Co ltd
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Jinsinan Film Shanghai Technology Co ltd
Nantong Jinsinan Membrane Material Co ltd
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Priority to CN202210096457.1A priority Critical patent/CN114525086A/en
Publication of CN114525086A publication Critical patent/CN114525086A/en
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/40—Adhesives in the form of films or foils characterised by release liners
    • C09J7/403—Adhesives in the form of films or foils characterised by release liners characterised by the structure of the release feature
    • 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
    • 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
    • B32B27/32—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
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/40—Adhesives in the form of films or foils characterised by release liners
    • C09J7/401—Adhesives in the form of films or foils characterised by release liners characterised by the release coating composition
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/24—Organic non-macromolecular coating
    • 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
    • B32B2307/538—Roughness
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/04—Homopolymers or copolymers of ethene
    • C08J2423/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/10—Homopolymers or copolymers of propene
    • C08J2423/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2483/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica

Abstract

The invention belongs to the technical field of waterproof materials, and relates to a polyolefin release film, a preparation method thereof and a preparation method of a roughened surface layer. The release film includes: a polyolefin polymer matte finish and an organic polymer hardened barrier coating; the organic polymer hardening isolation coating is coated on at least one side of the roughening surface layer; the matte surface layer comprises a polyolefin polymer and a micropowder material embedded therein, at least a portion of the micropowder material protruding from the base film of the matte surface layer, the micropowder material being free of a change in state below 240 ℃. The rough surface of the polyolefin release film does not contain any foaming substance, coarse particle substance or sharp raised structure, and does not damage the structure and performance of the substrate film; simultaneously, this structure has still been solved from the homogeneity of type coating for this polyolefin is from the even stability of type force and incomplete the connecing lower of type membrane, from the type membrane more easily with the coiled material separation and peel off the back and be difficult for having pitch to remain, has promoted the efficiency of construction.

Description

Polyolefin release film, preparation method thereof and preparation method of roughened surface layer
Technical Field
The invention belongs to the technical field of waterproof materials, and particularly relates to a polyolefin release film, a preparation method thereof and a preparation method of a roughened surface layer.
Background
The release film is an important anti-sticking and isolating functional material of the self-adhesive modified asphalt waterproof coiled material. CN204020090U discloses a release film with an embossed structure, which selects a series of semi-destructive protruding points in the film, and buffers the residual local stress during the curling and storage of the asphalt coiled material, so as to improve the wrinkle state of the surface layer of the coiled material. However, the embossing is of a sharp and soft protruding structure, and is very easy to inlay in the asphalt self-adhesive layer under the action of pressure, so that an anchoring structure is formed between the release film and the self-adhesive layer, and the embossing is difficult to tear in the construction process. CN102666094A discloses a release film formed on a base film and containing more than one protrusions containing cured products of a photo-curable resin composition, the protrusions of this structure are also easily embedded inside an asphalt self-adhesive layer, thereby causing difficulty in tearing off the film during construction, and simultaneously, due to the lack of a barrier layer, it is not possible to reduce the migration of small molecules in asphalt and glue, which greatly shortens the service life of the waterproof roll.
Through investigation, at present, there is another technique of adding hollow microspheres having an expansion effect at a certain temperature to a base film and roughening a surface structure by using at least one volatile organic compound in the hollow microspheres. However, this process is difficult to control during the process, and the "destructive" roughening is very likely to destroy the structure of the release film itself.
In summary, the current release film roughening treatment methods include the following three methods:
1) the method adopts a compression roller with a certain grain structure to press under certain temperature and pressure to realize roughening treatment of the surface of the base film.
2) The surface of the base film is roughened by forming uneven spots on the surface of the base film using a composition containing a photocurable resin.
3) Hollow microspheres with expansion function at a certain temperature are added, and roughening treatment of the surface structure is realized by utilizing at least one volatile organic compound in the hollow microspheres.
Through the analysis, the three roughening treatment modes of the release film cannot effectively solve the problem that the release film is effectively separated from the coiled material, and the structure of the substrate film can be damaged.
In order to solve the above problems, the present invention achieves roughening of the surface of a substrate by adding a high-melting organic-inorganic solid particulate material to a polymer carrier, utilizing the thermodynamic difference between the polymer carrier and the organic-inorganic solid particulate material. The rough surface of the invention does not contain sharp raised structures in the embossing release film, but is in a flat plate grain shape, and does not damage any structure and performance of the substrate film; meanwhile, the structure also better solves the problem of uniformity of release coating, and the release force is uniform and stable. The polyolefin release film disclosed by the invention is uniform and stable in release force and low in residual connection, and the fluctuation of the release force is less than 10% after long-term storage, so that the release film is easier to separate from a coiled material, asphalt residue is not easy to occur after stripping, and the construction efficiency is improved. Furthermore, the waterproof coiled material with the polyolefin release film has excellent self-adhesion retention rate, and the adhesion retention rate is over 85 percent after the waterproof coiled material is aged at 70 ℃ for 7 days.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the polyolefin release film, the rough surface of the polyolefin release film does not contain any foaming substance, rough particle substance and sharp raised structure, and does not damage any structure and performance of the substrate film; simultaneously, this structure has still been solved from the homogeneity of type coating for this polyolefin is from type membrane from type force even stability and incomplete connecing lower, through long-term storage after the fluctuation of type force < 10%, make from type membrane easier with the coiled material separation and be difficult for after peeling off have pitch to remain, promoted the efficiency of construction.
In order to achieve the above object, a first aspect of the present invention provides a polyolefin release film comprising: a polyolefin polymer matte finish and an organic polymer hardened barrier coating; the organic polymer hardening isolation coating is coated on at least one surface of the roughened surface layer; the matte finish comprises a polyolefin polymer and a micropowder material embedded therein, at least a portion of the micropowder material protruding from the base film of the matte finish, the micropowder material being free of a change in state below 240 ℃.
The second aspect of the present invention provides a method for preparing a polyolefin release film, which is characterized in that the method comprises: laminating other layers except the organic polymer hardening isolation coating layer in a mould to prepare a film in one step, and coating slurry of the organic polymer hardening isolation coating layer on at least one surface of the film and then thermally curing to form the polyolefin release film;
the die is preferably any one of a circular die and a flat die;
the preparation mode of the film is preferably selected from any one of a casting mode, a co-extrusion film blowing mode and a co-extrusion film blowing-extrusion mode;
the coating mode is preferably any one of extrusion coating and transfer coating;
the thermal curing is preferably ultraviolet light high-pressure mercury lamp thermal curing; the power of the high-pressure mercury lamp is preferably 10-50 kilowatts, and the heat curing temperature is preferably 100-140 ℃;
the film is preferably subjected to surface roughening and/or corona treatment before coating; the surface roughening is preferably formed by embossing treatment through a roller with lines on the surface; the temperature of the embossing treatment is preferably not more than 130 ℃ and the pressure is not more than 10 kgf; the depth of the roller grain is preferably 0.5 to 10% of the thickness of the base film of the roughened surface layer (R).
In a third aspect, the present invention provides a process for preparing a matte finish, comprising: blending the micro powder particles and the polyolefin polymer, melting and extruding, and carrying out casting cooling to form the roughened surface layer;
the temperature of the melt extrusion is preferably 150-250 ℃;
the addition amount of the fine powder particles is preferably 3 to 20% and the addition amount of the polyolefin polymer is preferably 80 to 97%, based on the total weight of the fine powder particles and the polyolefin polymer.
The invention has the following beneficial effects:
1) the rough surface adopts special pattern design, the coverage of the release agent can be ensured under the condition of lower coating gram weight of the release agent, and the raw material cost is saved.
2) The waterproof coiled material can effectively improve the wrinkles in the storage and use processes of the waterproof coiled material, and the waterproof performance is improved.
3) The release force is stable and the residual connection is low, the fluctuation of the release force is less than 10 percent after long-term storage, so that the release film is easier to separate from the coiled material and is not easy to have asphalt residue after being stripped, and the construction efficiency is improved.
4) The rough surface does not contain any foaming substance and coarse particle substance, is prepared by mould pressing, and is simple, convenient and practical.
5) Compared with the existing embossing release film, the rough surface of the invention does not contain sharp raised structures in the embossing release film, but is in a flat plate grain shape, and does not damage any structure and performance of the substrate film; meanwhile, the structure also better solves the problem of uniformity of release coating, and the release force is uniform and stable.
6) Compared with the existing PE and PP release films, the release film has a multilayer structure with a rough structure functional layer on the surface, fully plays the functional role of each structure by the function superposition of a plurality of functional layers, effectively improves the wrinkles of the waterproof roll in the storage and use processes, and improves the waterproof performance.
7) Compared with the existing release film, the release film can also reduce the migration of small molecules in asphalt and glue water, reduce the oxygen communication between air and the self-adhesive layer, improve the durability of the self-adhesive layer and prolong the service life of the waterproof coiled material.
8) Compared with the existing release film, the release film has small change range of the peeling force when being attached to the coiled material and stable film tearing performance. The adhesive tape is stored for 50 days under natural conditions, when the white adhesive tape is used as an anti-yellowing test method, the yellowing color difference of the adhesive tape is less than 5, and the conventional release film has serious color difference.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The above and other objects, features and advantages of the present invention will become more apparent by describing in more detail exemplary embodiments thereof with reference to the attached drawings, in which like reference numerals generally represent like parts throughout.
Fig. 1 is a schematic cross-sectional view of a polyolefin release film in example 1 of the present invention.
Fig. 2 is a schematic cross-sectional view of a polyolefin release film in example 2 of the present invention.
Fig. 3 is a schematic cross-sectional view of a polyolefin release film in example 3 of the present invention.
FIG. 4 is a schematic view of the surface embossing pattern of the polyolefin release film in the embodiment of the invention.
R-polyolefin polymer matte finish, Si-organic polymer hardened barrier coating, P-barrier layer, a-polyolefin polymer layer, d-modified binder layer
Detailed Description
Preferred embodiments of the present invention will be described in more detail below. While the following describes preferred embodiments of the present invention, it should be understood that the present invention may be embodied in various forms and should not be limited by the embodiments set forth herein.
The present invention provides a polyolefin release film, comprising: a polyolefin polymer matte finish R and an organic polymer hardened release coating Si; the organic polymer hardening isolation coating Si is coated on at least one surface of the roughening surface layer R; the matte surface layer R comprises a polyolefin polymer and a micropowder material embedded therein, at least part of the micropowder material protrudes from the base film of the matte surface layer R, and the micropowder material has no physical change below 240 ℃.
The solid state-free change means that the physical state changes such as melting, expansion and the like do not occur.
In the release film, the roughened surface layer is formed by organic and/or inorganic micro powder with a certain size, the micro powder material is preferably organic and/or inorganic filler with a non-hollow structure, most preferably silica micro powder and acrylic resin microspheres, and the micro powder or the microspheres are distributed in the roughened layer R and still keep a complete structural shape and interlayer positions in the high-temperature high-speed processing process, so that the roughened surface layer has a stable roughened structure after the whole release film is formed. Because the device is integrally formed and does not have a chemical expansion process in the process, the quality control is convenient and the equipment investment is low.
The roughened surface layer does not contain any foaming substance and coarse particle substance, is prepared by mould pressing, and is simple, convenient and practical.
Preferably, the release film further comprises: a barrier layer P and at least one modified adhesive layer.
The modified adhesive layer is positioned between the barrier layer P and the roughened surface layer R.
The organic polymer hardened release coating Si is coated on the outer surface of at least one of the matte finish layers R.
Preferably, the release film further comprises at least one polyolefin polymer layer.
The polyolefin polymer layer is in contact with the matte finish R and/or the modified adhesive layer.
Compared with the existing PE and PP release films, the release film has a multilayer structure with a rough structure functional layer on the surface, fully plays the functional role of each structure by the function superposition of a plurality of functional layers, effectively improves the wrinkles of the waterproof roll in the storage and use processes, and improves the waterproof performance.
Compared with the existing release film, the release film can also reduce the migration of small molecules in asphalt and glue water, reduce the oxygen communication between air and the self-adhesive layer, improve the durability of the self-adhesive layer and prolong the service life of the waterproof coiled material.
According to the invention, the polyolefin polymer in the polyolefin polymer roughening surface layer R is at least one selected from the group consisting of homo-polypropylene, co-polypropylene, high density polyethylene, linear low density polyethylene, metallocene polyethylene, thermoplastic polyolefin elastomer.
The micro powder material is organic or inorganic filler with a solid structure, and is preferably selected from at least one of polyacrylic resin microspheres and silica micro powder.
The particle size of the micro powder material is 0.1-280 microns, and preferably 0.5-180 microns.
The size of the base film of the micro-powder material protruding the roughening surface layer R is not more than 4 microns.
The mass fraction of the fine powder particles is preferably 3 to 20% and the mass fraction of the polyolefin polymer is preferably 80 to 97% based on the total mass of the matte surface layer R.
The thickness of the matte surface layer R is 1 to 10 micrometers, preferably 3 to 7 micrometers.
Specifically, at least one surface of the roughened surface layer R is provided with grains.
The organic polymer hardening isolation coating Si is coated on the surface with the grain of the roughened surface layer R.
The texture is preferably embossing roller texture, and the shape of the texture is preferably any one of curve shape, reticulate line shape, dendritic shape, rectangle shape, diamond shape and polygon shape.
The depth of the grain is preferably 0.5 to 10% of the thickness of the base film of the matte layer R.
The roughened surface layer adopts special pattern design, the coverage of the release agent can be ensured under the condition of lower coating gram weight of the release agent, and raw materials are saved.
The non-continuous grain pattern is used for improving the wrinkle problem generated during the storage of the coiled material, is easier to peel and does not remain after peeling.
Compared with the existing embossing release film, the roughening surface layer does not contain sharp raised structures in the embossing release film, but is in a flat plate grain shape, and does not damage any structure and performance of the substrate film; simultaneously, the structure also better solves the problem of uniformity of release coating, and the release force is uniform and stable.
According to the invention, the slurry of the organic polymer hardening isolation coating Si is any one of epoxy modified organic siloxane compound, organic acrylate modified organic siloxane compound, vinyl organic siloxane compound and fluorine-silicon polymer.
The thickness of the organic polymer hardening isolation coating Si is 0.2-1.5 micrometers.
According to the invention, the raw material of the barrier layer P is any one of polyamide and ethylene-vinyl alcohol copolymer, and the thickness of the barrier layer P is 1-10 microns, preferably 2-5 microns.
The ethylene content in the ethylene-vinyl alcohol copolymer is preferably 21 mol% to 38 mol%.
The raw material of the modified bonding layer is at least one of maleic anhydride modified polyethylene and maleic anhydride modified polypropylene.
The modified tie layer has a thickness of 1 to 7 microns, preferably 3 to 5 microns.
Specifically, the polyolefin polymer in the polyolefin polymer layer is the same as or different from the polyolefin polymer in the roughened surface layer R, and is selected from at least one of homo-polypropylene, co-polypropylene, high density polyethylene, linear low density polyethylene, metallocene polyethylene and thermoplastic polyolefin elastomer;
the thickness of the polyolefin polymer layer is 1 to 10 microns, preferably 3 to 7 microns.
The invention also provides a preparation method of the polyolefin release film, which comprises the following steps: laminating other layers except the organic polymer hardening isolation coating Si in a mould in one step to prepare a film, and coating the slurry of the organic polymer hardening isolation coating Si on at least one surface of the film and then thermally curing to form the polyolefin release film;
the die is preferably any one of a circular die and a flat die;
the preparation mode of the film is preferably selected from any one of a casting mode, a co-extrusion film blowing mode and a co-extrusion film blowing-extrusion mode;
the coating mode is preferably any one of extrusion coating and transfer coating;
the thermal curing is preferably ultraviolet light high-pressure mercury lamp thermal curing; the power of the high-pressure mercury lamp is preferably 10-50 kilowatts, and the heat curing temperature is preferably 100-140 ℃;
the film is preferably subjected to surface roughening and/or corona treatment before coating; the surface roughening is preferably formed by embossing treatment through a roller with lines on the surface; the temperature of the embossing treatment is preferably not more than 130 ℃ and the pressure is not more than 10 kgf; the depth of the roller grain is preferably 0.5 to 10% of the thickness of the base film of the roughened surface layer R.
The invention also provides a method for preparing a roughened surface layer, which comprises the following steps: and blending the micro powder particles and the polyolefin polymer, melting and extruding, and performing casting cooling to form the roughened surface layer.
The temperature of the melt extrusion is preferably 150-250 ℃.
The addition amount of the fine powder particles is preferably 3 to 20% and the addition amount of the polyolefin polymer is preferably 80 to 97%, based on the total weight of the fine powder particles and the polyolefin polymer.
The polyolefin release film has at least one of the following characteristics: the fluctuation of the release force is less than 20 percent, preferably less than 10 percent; the peeling force range of the release film/asphalt coiled material is 5-30 g/25 mm; the 50-day yellowing resistance color difference is less than 15, preferably less than 10.
The fluctuation test of the release force is carried out according to GB/T25256, and the method comprises the following steps: after 50 days of storage period, the self-adhesive asphalt with the release film is tested for the standard release force of the release film.
The release force range test is carried out according to GB/T25256, and the method comprises the following steps: the self-adhesive asphalt with the release film was stored for a long period of time and tested for the range of variation in peel force during the process.
The non-yellowing 50-day test is carried out according to an internal test method of an enterprise, and the method comprises the following steps: and (3) attaching the white film adhesive tape to the non-silicon surface of the release film, and testing the color difference of the surface of the adhesive tape before and after long-time storage.
The present invention is explained in more detail by examples, comparative examples and test examples.
Comparative example 1
The polyolefin release film consists of an embossed convex structure layer and a hardened isolation coating, and the total thickness is 20 micrometers; the thickness of the embossed convex structure layer R is 19.5 micrometers, the embossed convex structure layer R is composed of 100% homopolymerized polypropylene, the thickness of the hardening isolation coating Si is 0.5 micrometer, and the hard polysiloxane silicone oil layer is formed after UV light curing. Blowing the homopolymerized polypropylene into a film with the thickness of 19.5 microns by a screw extruder at 220-250 ℃, and passing through an extrusion roller with sharp protrusions on the surface on line to form an embossing protrusion structure layer; and then transferring to a coating roller to uniformly coat the rough surface, and curing and molding through a UV light curing device.
Example 1
This example is for illustrating the method of preparing the polyolefin release film of the present invention.
The polyolefin release film consists of a polyolefin polymer roughened surface layer R and an organic polymer hardening isolation coating Si, and the total thickness is 20 mu m; the R thickness of the polyolefin polymer roughened surface layer is 19.5 micrometers, the R thickness is composed of 100% of homopolymerized polypropylene and 15% of silicon dioxide micropowder by mass, and the Si thickness of the organic polymer hardened isolation coating is 0.5 micrometer and is a hard polysiloxane silicone oil layer formed after UV light curing. Blending silicon dioxide micro powder and homopolymerized polypropylene, blowing a film by a screw extruder at 220-250 ℃ to form a film with the thickness of 19.5 microns, and performing extrusion roller with the surface formed by points and curves to form a polyolefin polymer roughened surface layer R; and then transferring the substrate to a coating roller to uniformly coat the organic polymer hardening isolation coating Si slurry on the rough surface, and curing and molding the substrate by UV light curing equipment.
Example 2
This example is for illustrating the method of preparing the polyolefin release film of the present invention.
The thickness of the polyolefin release film is 40 microns, and the polyolefin release film consists of a polyolefin polymer roughened surface layer R, a polyolefin polymer layer a, a modified adhesive layer d, a barrier layer P and an organic polymer hardening isolation coating Si. Wherein, the thickness of the polyolefin polymer roughened surface layer R is 3.9 microns, and the roughened surface layer R consists of 55 percent of High Density Polyethylene (HDPE), 40 percent of Linear Low Density Polyethylene (LLDPE), 5 percent of homopolymerized polypropylene (MPP) and 10 percent of silicon dioxide micropowder by mass; the polyolefin polymer layer a has a thickness of 5 μm and consists of 55% Linear Low Density Polyethylene (LLDPE) and 45% High Density Polyethylene (HDPE); the thickness of the modified adhesive layer d is 4 micrometers, and the modified adhesive layer d is composed of 100% maleic anhydride modified polyethylene; the barrier layer P was 4 microns thick and comprised of 100% nylon 6. Blending the silicon dioxide micro powder with High Density Polyethylene (HDPE), Linear Low Density Polyethylene (LLDPE) and homopolymerized polypropylene (MPP), and blowing the mixture by a screw extruder at 220-250 ℃ to form a polyolefin polymer roughened surface layer R with the thickness of 3.9 microns; superposing the polyolefin polymer roughened surface layer R and other layers in sequence and then co-extruding and blowing a film; then coating slurry of an organic polymer hardening isolation coating Si after passing through an extrusion roller with a surface prefabricated into points and curves, and finally performing thermosetting molding; wherein the organic polymer hardened release coating Si has a thickness of 0.2 microns.
Example 3
This example is for illustrating the method of preparing the polyolefin release film of the present invention.
The polyolefin release film has the thickness of 20 microns and consists of a polyolefin polymer roughened surface layer R, a modified binder layer d, a barrier layer P and an organic polymer hardened isolation coating Si. Wherein the thickness of the polyolefin polymer roughened surface layer R is 3.8 microns, and the polyolefin polymer roughened surface layer R consists of 40 percent of homopolymerized polypropylene, 60 percent of copolymerized polypropylene and 15 percent of polyacrylic resin microspheres by mass; the thickness of the modified adhesive layer is 4 microns, and the modified adhesive layer is composed of 100% maleic anhydride modified polypropylene; the barrier layer P was 4 microns thick and was 100% EVOH. Blending polyacrylic resin microspheres with homo-polypropylene and co-polypropylene, and blowing a film by a screw extruder at 220-250 ℃ to form a polyolefin polymer roughened surface layer R with the thickness of 3.8 microns; superposing the polyolefin polymer roughened surface layer R and other layers in sequence and carrying out coextrusion casting; then coating organic polymer hardening isolation coating Si slurry after passing through an extrusion roller with a surface prefabricated into points and curves, and finally carrying out UV curing molding; wherein the organic polymer hardened release coating Si has a thickness of 0.4 microns.
Test example 1
The release film prepared in the comparative example and the examples 1 to 3 is applied to the performance of the self-adhesive asphalt coiled material for carrying out the silicone oil coating gram weight test, and the test method comprises the following steps: the test was carried out using an Oxford Lab-X3500 silicon coating tester, and the test results are shown in Table 1.
Test example 2
The release film prepared in the comparative example and the examples 1 to 3 is applied to the performance of the self-adhesive asphalt coiled material for carrying out a release force test, and the test method comprises the following steps: the test was carried out using a Texas 7475 tape having a width of 25mm, and the test results are shown in Table 1.
Test example 3
The release film prepared in the comparative example and the examples 1 to 3 is applied to the performance of the self-adhesive asphalt coiled material for carrying out release film/asphalt stripping force test, and the test method comprises the following steps: a release film with the thickness of 25mm is attached to the surface of the asphalt self-adhesive layer, the asphalt self-adhesive layer is uniformly reciprocated for 3 times by a compression roller, the asphalt self-adhesive layer is parked for 24 hours, after debugging is completed, testing is carried out at the speed of 300mm/min, and the testing results are shown in table 1.
Test example 4
The release film prepared in the comparative example and the examples 1 to 3 is applied to the performance of self-adhesive asphalt coiled materials to carry out asphalt self-adhesive layer/aluminum plate peeling force test according to GB/T23441, and the method comprises the following steps: the asphalt self-adhesive layer with the width of 50mm is stuck on an aluminum plate, and is rolled back and forth for 3 times by a compression roller, the rolling roller is parked for 24 hours, and then the test is carried out at the speed of 100mm/min, and the test results are shown in table 1.
Test example 5
The release film prepared in the comparative example and the examples 1 to 3 is applied to the asphalt self-adhesive layer/aluminum plate bonding peeling force retention rate after the performance of the self-adhesive asphalt coiled material is subjected to heat aging, and the test is carried out according to GB/T23441, and the method comprises the following steps: the self-adhesive asphalt with the release film was placed in an oven at 70 ℃ for heat treatment for 7 days and then tested, and the test results are shown in table 1.
Test example 6
The release film prepared in the comparative example and the examples 1 to 3 is applied to the performance of self-adhesive asphalt coiled materials to carry out the fluctuation test of release force, and the test is carried out according to GB/T25256, and the method is as follows: the release film was tested for its standard release force after 50 days storage period for self-adhesive asphalt with release film, the test results are shown in table 1.
Test example 7
The release film prepared in the comparative example and the examples 1 to 3 is applied to the performance of the self-adhesive asphalt coiled material to carry out a release force range test, and the test is carried out according to GB/T25256, and the method comprises the following steps: the self-adhesive asphalt with the release film was stored for a long period of time and tested for the range of variation in peel force during the test, the results of which are shown in table 1.
Test example 8
The release film prepared in the comparative example and the examples 1 to 3 is applied to the performance of the self-adhesive asphalt coiled material for a 50-day non-yellowing test, and the test is carried out according to an internal test method of an enterprise, wherein the method comprises the following steps: the white film adhesive tape was attached to the non-silicon surface of the release film, and the color difference of the surface of the adhesive tape before and after long-term storage was measured, with the test results shown in table 1.
TABLE 1
Figure BDA0003490969740000121
As can be seen from the comparative data in table 1, the properties of example 3 are the most excellent. Example 3 is 0.4g/m in terms of silicone oil coating grammage2The coated grammage of the release agents of the embodiment 1, the embodiment 2 and the comparative example 1 is also very low, which shows that the covering performance of the release agent can be ensured under the condition of lower coated grammage of the release agent by adopting special pattern design on the rough surface. Examples 1-3 were all lower in release film/asphalt peel force, indicating that the matte finish R embedded with the micropowder material had excellent peel force. In terms of the appearance of the asphalt coiled material, the examples 1 to 3 have no wrinkles, and the functional superposition of a plurality of functional layers in the release film improves the wrinkle resistance of the release film. Examples 1-3 performed well in terms of retention of the peel strength of the asphalt self-adhesive layer/aluminum panel bond after heat aging, indicating that the embedded micro-powder material roughened surface layer R was not readily heat-bondable to the asphalt self-adhesive layer. In the test of the fluctuation of the release force, the fluctuation of the release force of the examples 1 to 3 is small along with the change of time, which shows that the release film coated with silicon after adopting the rough structure has stable performance. In terms of the range of the release force, the change range of the examples 1 to 3 is very small in the long-term storage process of the asphalt coiled material, which shows that the release film coated with silicon by adopting a rough structure and a UV curing mode has stable performance and excellent release force with the asphalt coiled material. In a test of 50 days of yellowing resistance, the color difference change of the examples 1-3 is obviously better than that of a comparative example, which shows that the structural design of the roughening layer improves the yellowing resistance to a certain extent, and the yellowing resistance is effectively improved by the structure of a plurality of functional layers.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.

Claims (10)

1. A polyolefin release film, comprising: a polyolefin polymer matte finish (R) and an organic polymer hardened release coating (Si);
said organic polymer hardening barrier coating (Si) is applied to at least one side of said roughened surface layer (R);
the matte surface (R) comprises a polyolefin polymer and a micropowder material embedded therein, at least part of the micropowder material protruding from the base film of the matte surface (R), the micropowder material being free of a change in state below 240 ℃.
2. The polyolefin release film according to claim 1, further comprising: a barrier layer (P) and at least one modified adhesive layer;
the modified adhesive layer is positioned between the barrier layer (P) and the roughened surface layer (R);
the organic polymer hardening barrier coating (Si) is coated on the outer surface of at least one of the matte finish layers (R).
3. The polyolefin release film of claim 1, further comprising at least one polyolefin polymer layer; the polyolefin polymer layer is in contact with the matte finish (R).
4. The polyolefin release film of claim 2, further comprising at least one polyolefin polymer layer; the polyolefin polymer layer is in contact with the matte layer (R) and/or the modified adhesive layer.
5. The polyolefin release film according to any of claims 1 to 4, wherein the polyolefin polymer in the polyolefin polymer matte surface layer (R) is selected from at least one of homo polypropylene, co polypropylene, high density polyethylene, linear low density polyethylene, metallocene polyethylene, thermoplastic polyolefin elastomer;
the micro powder material is organic or inorganic filler with a solid structure, and is preferably selected from at least one of polyacrylic resin microspheres and silica micro powder;
the particle size of the micro powder material is 0.1-280 microns, preferably 0.5-180 microns;
the size of the base film of the micro powder material protruding out of the roughened surface layer (R) is not more than 4 micrometers;
the mass fraction of the fine powder particles is preferably 3 to 20% and the mass fraction of the polyolefin polymer is preferably 80 to 97%, based on the total mass of the roughened surface layer (R);
the thickness of the matte layer (R) is 1 to 22 microns, preferably 3 to 20 microns.
6. The polyolefin release film according to any one of claims 1 to 4, wherein the roughened surface layer (R) has a texture on at least one side;
the organic polymer hardening isolation coating (Si) is coated on the textured surface of the roughened surface layer (R);
the texture is preferably embossing roller texture, and the shape of the texture is preferably any one of curve, reticulate pattern, tree-like shape, rectangle, rhombus and polygon;
the depth of the grain is preferably 0.5 to 10% of the thickness of the base film of the roughened surface layer (R);
the slurry of the organic polymer hardening isolation coating (Si) is any one of an epoxy modified organic siloxane compound, an organic acrylate modified organic siloxane compound, a vinyl organic siloxane compound and a fluorine-silicon polymer;
the thickness of the organic polymer hardening isolation coating (Si) is 0.2-1.5 microns.
7. The polyolefin release film according to any one of claims 2 or 4, wherein the barrier layer (P) is made of any one of polyamide and ethylene-vinyl alcohol copolymer, and has a thickness of 1-10 microns, preferably 2-5 microns;
the ethylene content in the ethylene-vinyl alcohol copolymer is preferably 21 mol% to 38 mol%;
the raw material of the modified bonding layer is at least one of maleic anhydride modified polyethylene and maleic anhydride modified polypropylene;
the modified tie layer has a thickness of 1 to 7 microns, preferably 3 to 5 microns.
8. The polyolefin release film according to any of claims 3 to 4, wherein the polyolefin polymer in the polyolefin polymer layer is the same or different from the polyolefin polymer in the matte finish (R) and is selected from at least one of homo polypropylene, co-polypropylene, high density polyethylene, linear low density polyethylene, metallocene polyethylene, thermoplastic polyolefin elastomer;
the thickness of the polyolefin polymer layer is 1 to 10 microns, preferably 3 to 7 microns.
9. The method for preparing the polyolefin release film according to any one of claims 1 to 8, wherein the method comprises the following steps: laminating other layers except the organic polymer hardening isolation coating (Si) in a mould in one step to prepare a film, and thermally curing at least one surface of the film after coating slurry of the organic polymer hardening isolation coating (Si) to form the polyolefin release film;
the die is preferably any one of a circular die and a flat die;
the preparation mode of the film is preferably selected from any one of a casting mode, a co-extrusion film blowing mode and a co-extrusion film blowing-extrusion mode;
the coating mode is preferably any one of extrusion coating and transfer coating;
the thermal curing is preferably ultraviolet light high-pressure mercury lamp thermal curing; the power of the high-pressure mercury lamp is preferably 10-50 kilowatts, and the heat curing temperature is preferably 100-140 ℃;
the film is preferably subjected to surface roughening and/or corona treatment before coating; the surface roughening is preferably formed by embossing treatment through a roller with lines on the surface; the temperature of the embossing treatment is preferably not more than 130 ℃ and the pressure is not more than 10 kgf; the depth of the roller grain is preferably 0.5-10% of the thickness of the base film of the roughened surface layer (R);
the matte finish (R) is preferably prepared by: blending the micro powder particles and the polyolefin polymer, melting and extruding, and performing casting cooling to form the roughened surface layer (R);
the temperature of the melt extrusion is preferably 150-250 ℃;
the addition amount of the fine powder particles is preferably 3 to 20% and the addition amount of the polyolefin polymer is preferably 80 to 97%, based on the total weight of the fine powder particles and the polyolefin polymer.
10. The polyolefin release film of any one of claims 1-8, characterized in that it has at least one of the following characteristics:
the fluctuation of the release force is less than 20 percent, preferably less than 10 percent;
the peeling force range of the release film/asphalt coiled material is 5-30 g/25 mm;
the 50-day yellowing resistance color difference is less than 15, preferably less than 10.
CN202210096457.1A 2022-01-26 2022-01-26 Polyolefin release film, preparation method thereof and preparation method of roughened surface layer Pending CN114525086A (en)

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Publication number Priority date Publication date Assignee Title
CN115403849A (en) * 2022-09-23 2022-11-29 广州鹿山新材料股份有限公司 Uncoiling master batch and preparation method and application thereof

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Publication number Priority date Publication date Assignee Title
US20130316113A1 (en) * 2011-02-15 2013-11-28 Huhtamaki Films Germany Gmbh & Co. Kg Release film having a rough surface structure

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130316113A1 (en) * 2011-02-15 2013-11-28 Huhtamaki Films Germany Gmbh & Co. Kg Release film having a rough surface structure

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115403849A (en) * 2022-09-23 2022-11-29 广州鹿山新材料股份有限公司 Uncoiling master batch and preparation method and application thereof
CN115403849B (en) * 2022-09-23 2023-09-26 广州鹿山新材料股份有限公司 Uncoiling master batch and preparation method and application thereof

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