CN109367176A - A kind of anti-scratch transparent membrane, scratch resistant surface article and composite sheet - Google Patents

A kind of anti-scratch transparent membrane, scratch resistant surface article and composite sheet Download PDF

Info

Publication number
CN109367176A
CN109367176A CN201811288673.6A CN201811288673A CN109367176A CN 109367176 A CN109367176 A CN 109367176A CN 201811288673 A CN201811288673 A CN 201811288673A CN 109367176 A CN109367176 A CN 109367176A
Authority
CN
China
Prior art keywords
pmma
layer
scratch
layers
pet
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201811288673.6A
Other languages
Chinese (zh)
Inventor
廖洪传
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Suzhou Zhongrun New Materials Co.,Ltd.
Original Assignee
Individual
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Publication of CN109367176A publication Critical patent/CN109367176A/en
Pending legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • B65D65/40—Applications of laminates for particular packaging purposes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/07—Flat, e.g. panels
    • B29C48/08—Flat, e.g. panels flexible, e.g. films
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
    • B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
    • B29C48/21—Articles comprising two or more components, e.g. co-extruded layers the components being layers the layers being joined at their surfaces
    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • 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
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2033/00—Use of polymers of unsaturated acids or derivatives thereof as moulding material
    • B29K2033/04—Polymers of esters
    • B29K2033/12—Polymers of methacrylic acid esters, e.g. PMMA, i.e. polymethylmethacrylate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
    • B29K2067/003—PET, i.e. poylethylene terephthalate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2007/00—Flat articles, e.g. films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2009/00—Layered products
    • 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
    • B32B2250/244—All polymers belonging to those covered by group B32B27/36
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/40—Symmetrical or sandwich layers, e.g. ABA, ABCBA, ABCCBA
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • 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
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/412—Transparent
    • 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
    • B32B2307/554—Wear resistance
    • 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
    • B32B2307/558—Impact strength, toughness
    • 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
    • B32B2307/584—Scratch resistance
    • 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
    • B32B2307/712—Weather resistant
    • 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
    • B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion

Abstract

The invention discloses a kind of anti-scratch transparent membrane, scratch resistant surface article and composite sheets, pet layer including being located at the PMMA layer on upper layer and set on the PMMA layer lower surface, the pet layer is selected from PETG (non-crystalline type is copolymerized PET) or APET (amorphous PET) or CPET (crystal type PET) layer, the thickness of the PMMA layer accounts for the 5~40% of overall thickness, and the thickness of the pet layer accounts for the 20~95% of overall thickness；Further, also PMMA layers or PC layers or PC layers and PMMA layers can be set in the lower surface of the pet layer.The present invention is surface article or the extexine of packaging material with PMMA layers, provide good scratch-resistant performance, more preferably weather resistance, better temperature tolerance, meanwhile using pet layer and PMMA direct combination also overcome PMMA layers itself fragility and defect at high cost.

Description

A kind of anti-scratch transparent membrane, scratch resistant surface article and composite sheet
Technical field
The present invention relates to a kind of anti-scratch transparent membrane and scratch resistant surface article, the surface article can for film, Shell, protective case, window panel, touch screen panel, other panels, form, eyeglass, label etc., the transparent membrane can be used for Packaging material and label, panel etc..
Background technique
The surface article of current numerous products is the piece film or moulding that the resins such as PMMA, PC, PET, PP are substrate.So And the performance of homogenous material tends not to meet simultaneously that shock resistance, scratch resistant, low cost of some surface articles etc. are a variety of to be wanted It asks.For example, the impact resistance of PC is fine, but hardness is insufficient, easily scratches, scoring resistance can be still not good enough after doing stiffened processing；And Although PMMA hardness is very high, the embrittlement vulnerable to impact.
Wherein, plastic, transparent film has been widely used in packaging field, mainly have PET, PC, PMMA, PVC, PP, PE and The materials such as PS, wherein PVC does not meet environmentally friendly trend, disabled in many countries, enterprise；The transparency of PP, PE are poor；PS compared with It is easy embrittlement, processability is general, and not can be carried out solvent adhesive and connect；PMMA light transmittance and hardness are all higher than other different materials, Lip river Family name's hardness (R scale) is not easy to scratch up to 118, can carry out the processing such as solvent splicing, heat-sealing, ultrasonic bonding, weatherability is all It is best in thermoplastic, heatproof ratio PETG high, about 84 DEG C of heat distortion temperature, but higher cost, it is close with PETG, PC, add Also it is easy embrittlement in work, and is easy stress cracking；The transparency of PC is also higher, and intensity is also very high, but cost is very high, and cannot use Solvent is glued, and manufacture field (such as handmade box) use being quickly engaged is being needed to be restricted；PET points are common amorphous PET (being commonly called as APET) and PETG, the feature of environmental protection are good, wherein and APET film cost is far below PC and PMMA, but whitens because it is easy crystallization, It cannot be processed with techniques such as solvent splicing, heat-sealings；PETG is formed not because joined 1,4 cyclohexane dimethanol in the course of the polymerization process The copolymer of crystallization, so the processing technologys such as dissolvable agents splicing, heat-sealing, ultrasonic bonding, but cost is suitable with PC, and hardness is too Low, Rockwell hardness (R scale) only has 105 or so, and heatproof is also poor, and heat distortion temperature only has 70 DEG C or so.To sum up, existing modeling The defect of transparent membrane mainly at high cost, easy scratch, easy embrittlement, easy stress cracking are expected, therefore, without a kind of thin-film material energy Enough while realizing low cost, scratch resistant, be not easy embrittlement, be not easy stress cracking.
In addition, for surface article, the performance of homogenous material, which tends not to meet a variety of of some surface articles, to be wanted It asks.With the mature of new technology decoration technique inside mold (IMD), a current New Technological Trends are, with composite sheet knot It closes IMD technique and makes product casing, impose printing, high-pressure molding, punching on the membrane surface, and stiffened is handled, then through IMD work Skill and other materials connecting shaping.The representative of this kind of composite sheet is exactly two layers of composite material of PMMA/PC, and the superficial layer of material is It is PMMA layers, wear-resisting, it is the outer surface of product casing, another layer is PC layers, good toughness, is the inner surface of product casing.At present PMMA/PC composite material just obtains Rapid Popularization.But the shortcomings that this material is that the easy stress cracking of PC leads to product globality Can be bad, and product overall cost is higher inside general-purpose thermoplastic plastic.
Summary of the invention
The present invention provides a kind of anti-scratch transparent membrane, scratch resistant surface article and composite sheet and their systems Preparation Method.
Technical scheme is as follows:
A kind of anti-scratch transparent membrane is used for packaging material, including being located at the PMMA layer on the film upper layer and being set to PETG or APET layers of the PMMA layer lower surface, the thickness of the PMMA layer account for the 5~40% of overall thickness, described PETG or APET layers of thickness accounts for the 20~95% of overall thickness, and further preferably, the PETG or APET layers of thickness account for always The 60~95% of thickness.The overall thickness refers to PMMA layers described, described PETG or APET layers and may be PC layers, PMMA layers additional It etc. the overall thickness of all structure sheafs, but does not include the thickness for the extra play that surface treatment obtains.
In a preferred embodiment of the invention, the PMMA thickness degree is less than the PETG or APET layers of thickness.
In one of embodiment of the invention, PMMA layers are additionally provided in PETG or APET layers of the lower surface, it should PMMA layers of thickness accounts for the 5~40% of overall thickness, at this time the preferably described PETG or APET layers of thickness account for overall thickness 20~ 90%.
Preferably, the overall thickness of the film be 0.1~6mm, further preferably 0.1~3mm, more preferably 0.15~0.95mm.
When the overall thickness of transparent membrane is 0.5mm or less, the ratio that the thickness of the PMMA layers of single layer accounts for overall thickness is excellent 10~15% are selected as, the ratio that the PETG or APET layers of thickness account for overall thickness is preferably 70~90%；Work as transparent membrane Overall thickness be greater than 0.5mm when, the ratio that the thickness of the PMMA layers of single layer accounts for overall thickness is preferably 5~10%, described The ratio that PETG or APET layers of thickness accounts for overall thickness is preferably 80~95%.It is real while such thickness proportion is arranged more preferable Effect that is at low cost, anti-scratch, being not easy embrittlement and stress cracking is showed.
Preferably, the hardness of ratio PETG or APET layers of the hardness of the film is high, and the Rockwell of the specific film is hard It spends R scale and is not less than 110.
Preferably, the light transmittance of the film is greater than 86%, and the light transmittance of the further preferably film is greater than 90%.
Preferably, PMMA layer, which can be free of, has PET or containing a small amount of PET, the content range of PET is 0~50%, Preferably 0~40%, more preferably 0~30%；Described PETG or APET layers, which can be free of, has PMMA or containing a small amount of PMMA, The content range of PMMA is 0~50%, preferably 0~40%, more preferably 0~30%.
In a preferred embodiment of the invention, described PMMA layers with the PETG or APET layers by coextrusion process it is direct It links together.
The invention also discloses a kind of preparation methods of above-mentioned anti-scratch transparent membrane, including squeeze out PMMA from one Machine extrusion plasticizing, fused materials flow to distributor, and make PETG or APET from another extruder extrusion plasticizing, fused materials Flow to distributor, wherein PMMA is divided into one or two layers melting stream in distributor, in distributor and the one of PETG or APET layers Side or two sides are superimposed together, and form two layers or three-decker, are cooled and shaped after flowing out die head as solid film.
The invention also discloses the preparation methods of another above-mentioned anti-scratch transparent membrane, including make PMMA from First Extruder extrusion plasticizing, fused materials flow to distributor, and make PETG or APET from second extruder extrusion plasticizing, fusant Material also flows to distributor, also makes PMMA from third platform extruder extrusion plasticizing, and fused materials flow to distributor, from First, the The PMMA fused materials of three extruder extrusion plasticizings are superimposed together in distributor and PETG or APET layers of two sides, form three Layer structure is cooled and shaped after flowing out die head as solid film.
In above-mentioned preparation method, each fused materials can also be overlapped into multilayered structure at die head.
Anti-scratch transparent membrane of the invention is combined as main structural with PMMA and PETG or APET layers of structure, together When realize effect that is at low cost, anti-scratch, being not easy embrittlement and stress cracking.In addition, various functions layers can also be added thereon, Such as hardened layer, antiglare layer, anti-fingerprint layer.
The present invention also provides a kind of scratch resistant surface article, the scratch resistant surface article is with anti-scratch composite sheet system Make, the anti-scratch composite sheet includes one layer of pet layer, and the upper layer of the pet layer is equipped with PMMA layers, the PMMA on upper layer Layer is used as the outer surface of the anti-scratch composite sheet, and the thickness of the PMMA layer accounts for the 5~40% of overall thickness, described The thickness of pet layer accounts for the 20~95% of overall thickness.It is further preferred that the thickness of the pet layer account for overall thickness 60~ 95%.
Anti-scratch composite sheet of the invention is combined as main structural with PMMA and pet layer structure, realizes simultaneously Effect that is at low cost, anti-scratch, being not easy embrittlement and stress cracking.In addition, various functions layers can also be added thereon, such as harden Layer, antiglare layer, anti-fingerprint layer etc., so that scratch resistant surface article be made.
Preferably, the overall thickness of the anti-scratch composite sheet be 0.1~6mm, further preferably 0.1~0.95mm, More preferably 0.1~0.49mm.
In a preferred embodiment of the invention, the PMMA thickness degree is less than the PETG or APET layers of thickness.
The pet layer of the anti-scratch composite sheet can not have lower layer, and lower layer also can be set, the feelings of lower layer are arranged Under condition, the lower layer are as follows:
PMMA layers, the anti-scratch composite sheet described at this time is three-decker, abbreviation PMMA/PET/PMMA composite sheet；Or
PC layers, the anti-scratch composite sheet described at this time is three-decker, abbreviation PMMA/PET/PC composite sheet；Or
PC layers, PMMA layers are additionally provided under PC layers described, the anti-scratch composite sheet described at this time is four-layer structure, referred to as PMMA/PET/PC/PMMA composite sheet.
The thickness of above-mentioned possible additional lower layer is not associated with pet layer and the PMMA on upper layer layer, can be to appoint if PC layers Meaning thickness, if PMMA layers, range is 0.01mm~2mm.
When the overall thickness of the anti-scratch composite sheet is 0.5mm or less, the PMMA layer or PMMA layers described of the lower layer Thickness proportion with PC layers is 10~15%；The overall thickness of the composite sheet be greater than 0.5mm when, the PMMA layer of the lower layer or Described PMMA layers is 5%~10% with PC layers of thickness proportion.
Preferably, the PMMA layer of the anti-scratch composite sheet is together with pet layer is by co-extrusion direct combination.
The preparation method of the anti-scratch composite sheet includes making PMMA from an extruder extrusion plasticizing, flow of molten materials To distributor, and make PET from another extruder extrusion plasticizing, fused materials also flow to distributor, wherein PMMA is in distributor It is divided into one or two layers melting stream, is superimposed together in the one or both sides of distributor and pet layer, forms two layers or three-layered node Structure is cooled and shaped after flowing out die head as solid sheet material.
The preparation method of the anti-scratch composite sheet, which may also is that, makes PMMA from First extruder extrusion plasticizing, melts Melt flow direction of material distributor, and make PET from second extruder extrusion plasticizing, fused materials also flow to distributor, also make PMMA From third platform extruder extrusion plasticizing, fused materials flow to distributor, from First, the PMMA of third platform extruder extrusion plasticizing Fused materials are superimposed together in the two sides of distributor and pet layer, form three-decker, are cooled and shaped after flowing out die head as solid Sheet material.
The invention also discloses the preparation methods of another above-mentioned coextru-lamination sheet material, in above two preparation method, An extruder is added again squeezes out PC, melting PC flows to distributor, overlaps on the outside of PMMA/PET layers of basic structure of pet layer, PMMA/PET/PC three-decker or PMMA/PET/PC/PMMA four-layer structure are formed, is cooled and shaped after flowing out die head as solid piece Material.In addition to the above methods, PC layers can also after the completion of pet layer is with PMMA layers of co-extrusion by IMD it is compound.
In above-mentioned preparation method, each fused materials can also be overlapped into multilayered structure at die head.
Preferably, the pet layer of composite sheet used is amorphous PET (APET), or the crystal type PET added with nucleating agent (CPET) or non crystallized modified PET (PETG) both, or in which appoint or three's mixing in any proportion.Wherein, added at The heat resistance of the crystallinity PET (CPET) of core agent improves, and then improves the temperature tolerance of the composite sheet；The cost of APET It is substantially reduced compared with PC in the prior art；And APET layers or CPET layers without PC layers of stress cracking problem, (stress is opened Split finger have it is slight scratch or notch after again stress when easy stress concentrate and be broken), while composite sheet also taken into account it is good Toughness, and there is good scoring resistance energy.
Preferably, the PET content of the pet layer of the composite sheet is 10%~100%, preferably 50%~100%, More preferably 60%~100%, further preferably 70%~100%, it is still more preferably 90%~100%.The PET The other compositions that layer may include can such as be based on leftover pieces reuse process for PMMA, will contain the leftover pieces of all components as The pet layer of subsequent handling is added in raw material, PMMA can be introduced in pet layer, leads to the content of PET in pet layer not always 100%. Alternatively, the other polymers for not significantly affecting its toughness are added in pet layer based on any other reason.
Preferably, form the composite sheet wherein one layer or it is several layers of can add lubricant, the lubricant adds In the matrix for entering each layer.Lubricant is added can be in order to squeeze out processing, and increase the smooth degree of superficial layer, and then to anti- Only scratching has certain help.
In addition, the composition composite sheet wherein one layer or several layers of can also add one or more functional additions Agent, for example, antioxidant, ultraviolet absorbing agent, coupling agent and compatilizer (such as some ternarys for increasing PC layers with pet layer binding force Copolymer), nucleating agent etc. and the fillers and toner, color masterbatch etc. such as glass fibre, calcium carbonate, barium sulfate.
Preferably, the Rockwell hardness R scale of the composite sheet is not less than 110.
Preferably, the PMMA layer of the composite sheet can be free of and have or containing a small amount of PET, the content range of PET is 0 ~50%, preferably 0~40%, more preferably 0~30%；The pet layer, which can be free of, or contains a small amount of PMMA, PMMA's Content range is 0~50%, preferably 0~40%, more preferably 0~30%.
The preparation method of the scratch resistant surface article is: by the anti-scratch composite sheet case hardened, cold stamping, Hot-forming (containing the moulding process by all kinds of heating pressuring methods, such as hot bending folding, plastic uptake), IMD (including IML, IMF, IMR), anti-fingerprint processing, anti-dazzle light processing, hydrophobic oleophobic processing, vacuum vapour deposition, in-mold labels method, printing, one in plating Kind or kinds of processes processing, are made all kinds of scratch resistant surface articles, including but not limited to following a few class surface articles: instrument board, Automotive upholstery, shell, protective case, panel, touch screen panel, form, label, key, eyeglass, cell phone rear cover, MP3/MP4/ The products such as the panel of DVD/ Digital Frame/GPS navigator/instrument etc..
It specifically, for example can be following by the method that the anti-scratch composite sheet prepares the scratch resistant surface article One kind:
(1) by above-mentioned double-layer structure composite sheet PMMA/PET or three-decker composite sheet PMMA/PET/PC, PMMA/ PET/PMMA or four-layer structure composite sheet PMMA/PET/PC/PMMA is through all kinds of protectors of IML injection moulding and attaching, or can use hot pressing Or high-pressure molding, or can be also directly molded with additional increased PC or pet layer with IMD technology, and then do not need using any viscous Agent is tied, the surface articles such as instrument board and automotive upholstery are obtained.
(2) anti-dazzle light processing can be done on above-mentioned anti-scratch composite sheet, the tables such as form class panel, eyeglass, label is made Flour product.The method of anti-dazzle light processing can be the antiglare layer mode that applies and (anti-dazzle particle be added in masking liquid, keeps coating dry solid On surface, formation dimple is convex apparent after change, is diffusely reflected incident light to reach antiglare effect)；Can also be evaporated in vacuo, The methods of vapor deposition, sputtering, embossing, sandblasting, chemical etching realize that dimple is convex apparent, reach antiglare effect.
(3) anti-fingerprint processing can be done on above-mentioned anti-scratch composite sheet (by applying hydrophobic oleophobic layer in product surface Mode realize that the coating is usually fluorine material, such as perfluoropolyether, following anti-fingerprint for mentioning are handled with described herein), system Obtain the surface articles such as all kinds of panels, protective film, label of anti-fingerprint.
(4) Surface hardening treatment is done on above-mentioned anti-scratch composite sheet surface and (such as applies stiffening layer, stiffening layer is, for example, to contain One of machine silicon, titanium oxide, dicyandiamide, cobalt compound and organic polycarboxylic acid or a variety of coatings, following stiffeneds mentioned Layer is with described herein), UV cure process, in combination with printing technology, be made each electron-like, touch screen panel or display window, The surface articles such as label, key.The PMMA surface layer of composite plate can all carry out cure process, in addition, superficial layer can also be AF The processing of the specific functions such as (anti-fingerprint), AG (anti-dazzle), antifog.
(5) by above-mentioned anti-scratch composite sheet through printing, UV connection with production of structures, plating, priming operation, cut, cold stamping shaped Or it is hot-forming, Surface hardening treatment, CNC finishing impression, IMD (in-mold decoration processes contain IML, IMF, IMR, similarly hereinafter) or fitting, anti- One or more process in the techniques such as dizzy, anti-fingerprint are made and can be used for anti-scratch product casing or panel, such as mobile phone The panel of rear cover, protective case and MP3/MP4/DVD/ Digital Frame/GPS navigator/instrument etc..
(6) by the methods of above-mentioned anti-scratch composite sheet vacuum vapour deposition, in-mold labels method, silk-screen and plating on surface In addition one layer of reflecting layer, is made eyeglass.Lens surface can make the surface treatment such as stiffened, anti-dazzle, anti-fingerprint.
The present invention also provides a kind of anti-scratch composite sheets, for any of the above-described anti-scratch composite sheet or compound Sheet material.
Compared with prior art, beneficial effects of the present invention are as follows:
One, currently used packaging material film and scratch resistant surface article be mainly made of PMMA and PC, and this The cost of two kinds of raw materials is relatively high；And the present invention is in most cases, can be used APET layers as films and described The main body materials of composite sheet, thus significantly reduce the cost of product；
Two, a kind of anti-scratch transparent membrane and scratch resistant surface article for packaging material of the invention, by PETG or APET layers of upper surface is arranged a PMMA layers, with the PMMA layers of extexine for packaging material, can provide good resistance to Performance is scratched, avoids being scratched because slightly rubbing, maintains beautiful and light transmission effect；And for a long time in outdoor exposure in sunshine Appearance varies less in wind and rain, has more preferably weather resistance；
Three, a kind of anti-scratch transparent membrane and scratch resistant surface article for packaging material of the invention, is cleverly selected With two kinds of materials of PET and PMMA and bound directly that (such as by coextrusion processes, when extrusion can add compatilizer increase Binding force), adhesive is not added, and then the shortcomings that PMMA layers of easy embrittlement and stress embrittlement is overcome well by pet layer, pet layer It is not easy embrittlement, the processing such as quarter pressure, punching, folding can be carried out without rupturing, meanwhile, the performance of pet layer not scratch-resistant is by PMMA Layer it is complementary and be improved significantly；
Four, in a kind of anti-scratch transparent membrane and scratch resistant surface article for packaging material of the invention, PMMA's Heat distortion temperature is 84 DEG C, 14 DEG C higher than PETG heat distortion temperature (about 70 DEG C), therefore the anti-scratch transparent membrane and scratch resistant Surface article can preferably be resistant to storage, transport, the hot environment in use process without softening transform, tacky；
Five, a kind of anti-scratch transparent membrane and scratch resistant surface article for packaging material of the invention also makes full use of The high transparency of PMMA, improves the light transmittance of product entirety；
Six, for there is the product of more high-temperature resistant requirement and shock resistance requirement, the present invention can be using the composite sheet for having PC layers Material, such as PMMA/PET/PC composite sheet and PMMA/PET/PC/PMMA composite sheet, therefore, the scope of application of the invention is more Extensively.
Certainly, it implements any of the products of the present invention and does not necessarily require achieving all the advantages described above at the same time.
Detailed description of the invention
Fig. 1 is a kind of structural schematic diagram of anti-scratch transparent membrane for packaging material of one embodiment of the invention；
Fig. 2 is a kind of another structural representation of anti-scratch transparent membrane for packaging material of one embodiment of the invention Figure；
Fig. 3 is the structural representation of anti-scratch composite sheet used in the scratch resistant surface article of one embodiment of the invention Figure；
In figure, 1-PMMA layers；2-PET layers；3-PC layers；4-PMMA layers.
Specific embodiment
It is commonly in the market PET film, it is not high that there are surface hardnesses for Wrapping films product, it is easy to It is scratched because slightly rubbing, influences the effect that beautiful and light transmission uses, and heat distortion temperature is low, the defect of weatherability difference.
Normally, although PMMA in terms of hardness, light transmittance and the weatherability on show advantageous, it is easy to there is processing The defect of embrittlement, and because easy embrittlement can not be made < thin slice of 0.5mm, it is furthermore at high cost to also limit it on packaging material It uses.
In addition, the basic material optical thin film of touch screen is mainly made in PMMA by the prior art, it is coated hardening accelerator and is made Anti-scratch optical thin film.Therefore, the personnel in housing material field can't be readily apparent that using the hardness of PMMA itself come auxiliary The hardness for improving other materials is helped, especially because cost factor will not be applied on packaging field.
Therefore, researching and developing one kind not only has PET film property but also has PMMA property, and the housing material of advantage of lower cost Film seems particularly important.
The trade mark range of choice of transparent PET G is narrow, Rockwell hardness substantially in 105~108 (R scales), transparent PMMA and PC has the material of various hardness, and some PMMA hardness ratio PETG are low, the PC hardness ratio PMMA high also having, such as Yi Siman chemistry The Rockwell hardness (R scale) of PETG GN120 is 107, Rockwell hardness (the R mark of the PMMA ShinkoLite-P UT-300 of Mitsubishi Ruler) it is 100, the PC 300-6 Rockwell hardness (R scale) for containing auspiciousness Austria is then 118.
The PMMA of present invention selection hardness ratio PETG high makees the superficial layer of scratch-resistant, and PMMA is thin as basic materials optical Then its hardness is not required when film.
Anti-scratch transparent membrane of the invention is arranged one layer PMMA layers by the upper surface at least at PETG or APET layers, i.e., With the PMMA layers of upper surface layer or upper and lower surface layer for packaging material, PETG or the APET layers of undersurface layer or folder for packaging material The advantageous characteristics such as PMMA is upper in terms of hardness, light transmittance and weatherability and the upper dissolvable agents of processing are glued, but also benefit be not only utilized in central layer The advantages that with the flexibility and APET low in cost of PETG or APET, i.e., using advantage of the side in a certain performance to solve Another party and takes into account cost factor in the disadvantage of the performance so that film of the invention have scratch-resistant performance, weather resistance, The high grade of transparency and the process such as quarter pressure, punching, folding are being carried out without rupturing, and the advantages that advantage of lower cost.Usually Reduction cost consideration, mostly uses APET layers, and can mix a small amount of PETG wherein, or do not add PETG.
Scratch resistant surface article of the invention provides good scratch-resistant with the PMMA layers of extexine for surface article Can, it avoids being scratched because slightly rubbing；More preferably weather resistance is provided simultaneously, even if being exposed to sunshine wind and rain China and foreign countries for a long time See variation also very little；Better temperature tolerance, the also not softening transform, tacky in storage, transport, use process；And APET layers or PETG layers then provide the mechanical performance of sufficient intensity for surface article product, and greatly reduce the cost of product casing.
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate this hair It is bright, rather than limit the scope of protection of the present invention.What those skilled in the art made according to the present invention in practical applications changes Into and adjustment, still fall within protection scope of the present invention.
In order to better illustrate the present invention, the present invention is described in detail below with attached drawing.
As shown in Figure 1, a kind of anti-scratch transparent membrane or composite sheet for packaging material of the invention, including be located at The PMMA layer 1 on the film upper layer and PETG or APET layer 2 (i.e. pet layer) set on 1 lower surface of PMMA layer, it is described The thickness of PMMA layer 1 account for the 5~40% of overall thickness, the thickness of the PETG or APET layer 2 accounts for the 20~95% of overall thickness, It is preferred that PETG or APET layers of the thickness accounts for the 60~95% of overall thickness.
In another specific embodiment of the invention, as shown in Fig. 2, the lower surface of PETG or the APET layer 2 also Equipped with PMMA layer 3, the thickness of PMMA layer 3 accounts for the 5~40% of overall thickness.Preferably described PETG or APET layers of thickness are accounted at this time The 20~90% of overall thickness.
Wherein, when using PMMA as the upper surface layer of film packing material or upper and lower surface layer, it is excellent that thickness accounts for overall thickness It is selected as 7~20%, the thickness of the PETG or APET layer 2 accounts for the 30~90% of overall thickness.
In addition, can also add all kinds of additions for not appreciably affecting film light transmittance in the layers of material of the film Agent, such as antioxidant, ultraviolet absorbing agent, lubricant and the coupling agent for increasing PMMA layers with pet layer binding force.
The invention also discloses a kind of preparation methods of above-mentioned anti-scratch transparent membrane for packaging material, including For PMMA from an extruder extrusion plasticizing, fused materials flow to distributor, PETG or APET from another extruder extrusion plasticizing, Fused materials also flow to distributor, wherein PMMA is divided into one or two layers melting stream in distributor, in distributor and PETG or APET layers of one or both sides are superimposed together, and form the film of two layers or three-decker.
That is: PMMA is divided into two layers of melting stream in distributor, is superimposed together in distributor and pet layer two sides, forms three The film of layer structure；Or, PMMA need not be divided into two layers at distributor, is directly overlapped with pet layer, form the thin of double-layer structure Film.Two layers after overlapping or three layers of fused materials continue to flow to die head, and three roller fast cooling shapings, warp are entered after die head outflow Deburring winding, can be prepared by the film.
In addition, coextrusion process compound in mould, which also can be used, produces the transparent membrane, i.e., two layers or three layers of fused materials It does not overlap in distributor, but is superimposed together after entering die head；And those skilled in the art is also known that described three layers of production When co-extrusion transparent membrane, PMMA can also use two extruders extrusion plasticizing, form two strands of melting charges and squeeze with another extruder The PET melting charge for being plasticized output out is overlapped.
The present invention also provides a kind of scratch resistant surface article, the scratch resistant surface article is with anti-scratch composite sheet system Make, the anti-scratch composite sheet includes one layer of pet layer, and the upper layer of the pet layer is equipped with PMMA layers, described in upper layer The PMMA layers of outer surface for being used as the anti-scratch composite sheet, the thickness of the PMMA layer accounts for the 5~40% of overall thickness, described The thickness of pet layer account for the 20~95% of overall thickness.
The pet layer of the anti-scratch composite sheet is not provided with lower layer or setting lower layer, in the case where lower layer is arranged, The lower layer are as follows:
PMMA layers, the scratch resistant surface article is three-decker, abbreviation PMMA/PET/PMMA composite sheet at this time；Or
PC layers, the scratch resistant surface article is three-decker, abbreviation PMMA/PET/PC composite sheet at this time；Or
PC layers, PMMA layers are additionally provided under PC layers described, the scratch resistant surface article is four-layer structure at this time, referred to as PMMA/PET/PC/PMMA composite sheet.
Fig. 3 is referred to, in some embodiments of the invention, the structure of composite sheet includes: the PMMA as outer surface Layer 1, is arranged in the pet layer 2 of 1 lower layer of PMMA layer, and the PC layer 3 under pet layer 2 is arranged in and is arranged under PC layer 3 PMMA layer 4.
In the preferred embodiment of the present invention, composite sheet used in the scratch resistant surface article is coextru-lamination piece Material.In addition to coextrusion process, lower layer is PMMA layers additional, PC layers or PC+PMMA layers, can also be incorporated in pet layer by IMD technique On.
The pet layer of composite sheet used in the present invention is amorphous PET (APET), or the crystal type PET added with nucleating agent (CPET) or non crystallized copolymerization PET (PETG) both, or in which appoint or three's mixing in any proportion.
The overall thickness of the composite sheet be 0.1~6mm, preferably 0.1~0.95mm, more preferably 0.1~ 0.49mm.The overall thickness of the composite sheet be 0.5mm or less when, the PMMA layer of the lower layer or it is described PMMA layers with PC layers Thickness proportion is 10~15%；When the overall thickness of the composite sheet is greater than 0.5mm, the PMMA layer of the lower layer or the PMMA Layer is 5%~10% with PC layers of thickness proportion.
The PET content of the pet layer of the composite sheet is 10%~100%, preferably 50%~100%, more preferably It is 60%~100%, further preferably 70%~100%, is still more preferably 90%~100%.
The PMMA layer of the composite sheet does not contain or containing a small amount of PET, the content range of PET is 0~50%, excellent It is selected as 0~40%, more preferably 0~30%；The pet layer does not contain or containing a small amount of PMMA, and the content range of PMMA is 0 ~50%, preferably 0~40%, more preferably 0~30%.
The preparation method of the composite sheet includes making PMMA from an extruder extrusion plasticizing, fused materials flow direction distribution Device, and make PET from another extruder extrusion plasticizing, fused materials also flow to distributor, wherein PMMA is divided into one in distributor Layer or two layers of melting stream, are superimposed together in the one or both sides of distributor and pet layer, form two layers or three-decker, stream Be cooled and shaped after die head out is solid sheet material.
The preparation method of the composite sheet, which may also is that, makes PMMA from First extruder extrusion plasticizing, fused materials Distributor is flowed to, and makes PET from second extruder extrusion plasticizing, fused materials also flow to distributor, and there are also PMMA from third Platform extruder extrusion plasticizing, fused materials flow to distributor, from First, the PMMA fusant of third platform extruder extrusion plasticizing Material is superimposed together in the two sides of distributor and pet layer, forms three-decker, is cooled and shaped after flowing out die head as solid sheet material.
The invention also discloses the preparation methods of another above-mentioned coextru-lamination sheet material, in above two preparation method, An extruder is added again squeezes out PC, melting PC flows to distributor, overlaps on the outside of PMMA/PET layers of basic structure of pet layer, PMMA/PET/PC three-decker or PMMA/PET/PC/PMMA four-layer structure are formed, cooling and shaping are that solid is thin after flowing out die head Film.
In above-mentioned preparation method, each fused materials can also be overlapped into multilayered structure at die head.
The preparation method of the scratch resistant surface article is: by the anti-scratch composite sheet case hardened, cold stamping, One of hot-forming, IMD, anti-dazzle light processing, hydrophobic oleophobic processing, vacuum vapour deposition, in-mold labels method, printing, plating Or kinds of processes processing, all kinds of scratch resistant surface articles are made.
In some embodiments, form the composite sheet wherein one layer or it is several layers of can added with lubricant, The lubricant is added in the matrix of each layer.
In some embodiments, form the composite sheet wherein one layer or it is several layers of can also add it is a kind of or more Kind functional additive.For example, antioxidant, ultraviolet absorbing agent, the coupling agent and compatilizer for increasing PC layers with pet layer binding force Fillers and the toner, color masterbatch such as (such as some terpolymers), nucleating agent and glass fibre, calcium carbonate, barium sulfate Deng.
In a preferred embodiment, the Rockwell hardness R scale of the composite sheet is not less than 110.
The present invention also provides a kind of anti-scratch composite sheet, the anti-scratch composite sheet is above-mentioned anti-scratch composite sheet Material or composite sheet.
Embodiment 1
A kind of anti-scratch transparent membrane for packaging material of the present embodiment 1, including being located at the film upper layer PMMA layer 1, the APET layer 2 set on 1 lower surface of PMMA layer and the PMMA that is additionally provided in the lower surface of the APET layer 2 Layer 3, the thickness of the PMMA layer 1 account for the 10% of overall thickness, and the thickness of the APET layer 2 accounts for the 80% of overall thickness, described The thickness of PMMA layer 3 account for the 10% of overall thickness, the overall thickness of the film is 0.3mm.Preparation method are as follows: by PMMA Material, APET pellet are dried respectively, are delivered to coextrusion sheet unit extrusion molding；The performance test results, such as one institute of table Show, and using the PETG/APET/PETG thin-film material of condition of equivalent thickness as control, performance is as shown in Table 2.
Table one
Table two
PMMA raw material and PETG cost of material are essentially identical.The above comparative illustration, with PETG/APET/ currently on the market PETG three-layer tablet material is compared, and in the case where cost is constant, the present invention significantly improves the hardness of film, to significantly improve The anti-scratch performance of film.In addition light transmittance also has a degree of improvement.
Embodiment 2
A kind of anti-scratch transparent membrane for packaging material of the present embodiment 2, including being located at the film upper layer PMMA layer 1 and APET layer 2 set on 1 lower surface of PMMA layer, the thickness of the PMMA layer 1 account for the 20% of overall thickness, The thickness of the APET layer 2 accounts for the 80% of overall thickness, and the overall thickness of the film is 0.25mm.Preparation method are as follows: PMMA pellet and PET pellet are dried, and are then sent to coextrusion sheet unit extrusion molding；Performance test, such as table three It is shown, and using the PETG/APET thin-film material of condition of equivalent thickness as control, performance is as shown in Table 4.
Table three
Table four
The above comparative illustration, compared with PETG/APET two sheets currently on the market, in the case where cost is constant, The present invention significantly improves the hardness of film, to significantly improve the anti-scratch performance of film.In addition light transmittance also has centainly The improvement of degree.
Embodiment 3
A kind of anti-scratch transparent membrane for packaging material of the present embodiment 3, including being located at the film upper layer PMMA layer 1, the APET layer 2 set on 1 lower surface of PMMA layer and the PMMA that is additionally provided in the lower surface of the APET layer 2 Layer 3, the thickness of the PMMA layer 1 account for the 7% of overall thickness, and the thickness of the APET layer 2 accounts for the 86% of overall thickness, described The thickness of PMMA layer 3 accounts for the 7% of overall thickness, and the overall thickness of the film is 3mm.Preparation method are as follows: by PMMA pellet, APET pellet is dried respectively, is delivered to coextrusion sheet unit extrusion molding；Performance test as shown in Table 5, and is adopted Use the PETG thin-film material of condition of equivalent thickness as control, performance is as shown in Table 6.Further, since the PETG/ of condition of equivalent thickness APET/PETG sheet material APET when thickness is greater than 1mm is easy to crystallize and whiten because cooling velocity is too slow, seriously affects transparency, Herein not as comparative example.
Table five
Table six
The above comparative illustration, compared with PETG/APET/PETG sheet material currently on the market, in the case where cost is constant, Other than the hardness and anti-scratch performance that significantly improve film, the heat distortion temperature of sheet material also improves the present invention.
Embodiment 4
With two layers of composite sheet (thickness proportion 10:90) of 0.5mm thickness PMMA/APET through printing, UV connection with production of structures, plating, Priming operation, hot-forming, painting UV stiffening layer, CNC finishing impression, are made anti-scratch phone housing.
Compared with the PMMA product of same thickness, the phone housing surface hardness of the present embodiment is identical, but material cost section 40% is saved, shock strength improves 2 times.With the phone housing phase of two layers of composite sheet (thickness proportion 10:90) of PMMA/PC production Than material cost also saves 40%, but not stress cracking.
Embodiment 5
With tri- layers of composite sheet sheet material (thickness proportion 10:80:10) of 0.5mm thickness PMMA/CPET/PMMA through printing, hot pressing Molding applies UV stiffening layer, and anti-scratch phone housing is made.
Compared with the PMMA product of same thickness, the phone housing surface hardness of the present embodiment is identical, but material cost section 36% is saved, shock strength improves 1.8 times.
For the present embodiment because middle layer is the CPET layer of crystallization, heat distortion temperature is the implementation of APET than article inner surface layer Example 4 improves 30 degree.
Compared with the phone housing of tri- layers of composite sheet (thickness proportion 10:80:10) of PMMA/PC/PMMA production, this implementation The material cost of example also saves 36%, but not stress cracking.
Embodiment 6
With transparent tri- layers of composite sheet (thickness proportion 12.5:75:12.5) of 0.2mm thickness PMMA/APET/PMMA in two tables Surface layer applies UV stiffening layer, and window panel is made.
PMMA is because shock resistance is poor, easily embrittlement, the film of 0.2mm can not be made, but the structure of the present embodiment then can The film face-plate of enough obtained thickness 0.2mm, and obtained panel is harder than the surface of other visible PET, PC panels in the market Du Gaoyue 10 (R scale), anti-scratch performance is more preferable.
Embodiment 7
UV is applied in two superficial layers with transparent two layers of composite sheet (thickness proportion 20:80) of 0.15mm thickness PMMA/APET to add Hard formation, in a face gluing and is covered with release film, can make non-glare treated in another side, add oleophobic hydrophobic coating, the electricity such as mobile phone are made The surfacecti proteon film of sub- product.
For PMMA because shock resistance is poor, the film of 0.15mm can not be made in easily embrittlement.The surfacecti proteon film of the present embodiment More than the surface hardness high by about 10 (R scale) of other visible PET, PC, PP, PVC protective films in the market, anti-scratch performance is more It is good.
Embodiment 8
UV stiffening layer, true is applied with tri- layers of composite sheet (thickness proportion 10:80:10) of 0.5mm thickness PMMA/APET/PMMA Sky, which is aluminized, is made eyeglass.
Compared with the PMMA product of same thickness, the surface hardness of the eyeglass of the present embodiment is identical, but material cost is saved 36%, shock strength improves 1.8 times.
The structure of the present embodiment can also make thinner eyeglass, but PMMA in the prior art is not then because embrittlement problem can Production.
The eyeglass of the present embodiment is higher by about 10 (R scale) than the surface hardness of other visible PET, PC panels in the market, prevents It is more preferable to scratch performance.
Embodiment 9
UV stiffening layer is applied with two layers of composite sheet (thickness proportion 10:90) of 0.5mm thickness PMMA/APET, electricity is made in printing Sub- product or instrument and equipment panel, label.
Compared with the PMMA product of same thickness, the panel of the present embodiment, sign surface hardness are identical, but material cost section 40% is saved, shock strength improves 2 times, and about 10 (R higher than the surface hardness of other visible plastics PET, PC panels in the market Scale), anti-scratch performance is more preferable.
Present invention disclosed above preferred embodiment is only intended to help to illustrate the present invention.There is no detailed for preferred embodiment All details are described, are not limited the invention to the specific embodiments described.Obviously, according to the content of this specification, It can make many modifications and variations.These embodiments are chosen and specifically described to this specification, is in order to better explain the present invention Principle and practical application, so that skilled artisan be enable to better understand and utilize the present invention.The present invention is only It is limited by claims and its full scope and equivalent.

Claims (24)

1. a kind of anti-scratch transparent membrane is used for packaging material, which is characterized in that the PMMA including being located at the film upper layer Layer and set on PETG or APET layers of the PMMA layer lower surface, the thickness of the PMMA layer accounts for the 5~40% of overall thickness, PETG or APET layers of the thickness accounts for the 20~95% of overall thickness.
2. anti-scratch transparent membrane according to claim 1, which is characterized in that in PETG or APET layers of the following table Face is additionally provided with PMMA layers, and thickness accounts for the 5~40% of overall thickness.
3. anti-scratch transparent membrane according to claim 1 or 2, which is characterized in that the overall thickness of the film is 0.1 ~6mm, preferably 0.1~3mm, more preferably 0.15~0.95mm.
4. anti-scratch transparent membrane according to claim 1 or 2, which is characterized in that when the overall thickness of the film is When 0.5mm or less, the ratio that the thickness of the PMMA layers of single layer accounts for overall thickness is 10~15%, the PETG or APET layers The ratio that thickness accounts for overall thickness is 70~90%；When the overall thickness of film is greater than 0.5mm, the thickness of the PMMA layers of single layer is accounted for The ratio of overall thickness is 5~10%, and the ratio that the PETG or APET layers of thickness account for overall thickness is 80~95%.
5. anti-scratch transparent membrane according to claim 1 or 2, which is characterized in that the Rockwell hardness R of the film is marked Ruler is not less than 110.
6. anti-scratch transparent membrane according to claim 1 or 2, which is characterized in that the light transmittance of the film is greater than 86%.
7. anti-scratch transparent membrane according to claim 1 or 2, which is characterized in that the PMMA layer without or with The content range of a small amount of PET, PET are 0~50%, preferably 0~40%, more preferably 0~30%；The PETG or APET layers without or with a small amount of PMMA, the content range of PMMA is 0~50%, preferably 0~40%, more preferably 0~ 30%.
8. anti-scratch transparent membrane according to claim 1 or 2, which is characterized in that described PMMA layers with the PETG or APET layers are directly linked together by coextrusion process.
9. a kind of preparation method of the anti-scratch transparent membrane as described in any in claim 1~8, which is characterized in that including By PMMA from an extruder extrusion plasticizing, and fused materials is made to flow to distributor, by PETG or APET from another extruder Extrusion plasticizing, and fused materials is made also to flow to distributor, wherein PMMA is divided into one or two layers melting stream in distributor, Distributor is superimposed together with PETG or APET layers of one or both sides, forms two layers or three-decker, flows out cooling after die head It is shaped to solid film.
10. a kind of preparation method of the anti-scratch transparent membrane as described in any in claim 1~8, which is characterized in that including Make PMMA from First extruder extrusion plasticizing, fused materials flow to distributor, and make PETG or APET from second extruder Extrusion plasticizing, fused materials also flow to distributor, also make PMMA from third platform extruder extrusion plasticizing, fused materials flow direction distribution Device is folded from the PMMA fused materials of First, third platform extruder extrusion plasticizing in distributor and PETG or APET layers of two sides It is combined, forms three-decker, be cooled and shaped after flowing out die head as solid film.
11. the preparation method of anti-scratch transparent membrane according to claim 9 or 10, which is characterized in that each fused materials Not at distributor, but multilayered structure is overlapped at die head.
12. a kind of scratch resistant surface article, which is characterized in that the scratch resistant surface article is made of anti-scratch composite sheet , the anti-scratch composite sheet includes one layer of pet layer, and the upper layer of the pet layer is equipped with PMMA layers, described in upper layer The PMMA layers of outer surface for being used as the anti-scratch composite sheet, the thickness of the PMMA layer accounts for the 5~40% of overall thickness, described The thickness of pet layer account for the 20~95% of overall thickness.
13. scratch resistant surface article according to claim 12, which is characterized in that the anti-scratch composite sheet it is described Pet layer is not provided with lower layer or setting lower layer, in the case where lower layer is arranged, the lower layer are as follows:
PMMA layers, the anti-scratch composite sheet described at this time is three-decker, abbreviation PMMA/PET/PMMA composite sheet；Or
PC layers, the anti-scratch composite sheet described at this time is three-decker, abbreviation PMMA/PET/PC composite sheet；Or
PC layers, PMMA layers are additionally provided under PC layers described, the anti-scratch composite sheet described at this time is four-layer structure, abbreviation PMMA/ PET/PC/PMMA composite sheet.
14. scratch resistant surface article according to claim 12, which is characterized in that the PET of the anti-scratch composite sheet Layer is together with PMMA layers by co-extrusion direct combination.
15. scratch resistant surface article according to claim 12 or 13, which is characterized in that the anti-scratch composite sheet Pet layer is amorphous PET, or added with the crystal type PET or non crystallized copolymerization PET of nucleating agent, or in which appoints the two or three Mixing in any proportion.
16. scratch resistant surface article according to claim 12 or 13, which is characterized in that the total thickness of the composite sheet Degree is 0.1~6mm, preferably 0.1~0.95mm, more preferably 0.1~0.49mm.
17. scratch resistant surface article according to claim 12 or 13, which is characterized in that the overall thickness of the composite sheet When for 0.5mm or less, the PMMA layer of the lower layer or described PMMA layers with PC layers of thickness proportion are 10~15%；It is described compound When the overall thickness of sheet material is greater than 0.5mm, the PMMA layer of the lower layer or it is described PMMA layers with PC layers of thickness proportion for 5%~ 10%.
18. scratch resistant surface article according to claim 12 or 13, which is characterized in that the PET of the composite sheet The PET content of layer is 10%~100%, preferably 50%~100%, more preferably 60%~100%, further preferably 70%~100%, it is still more preferably 90%~100%.
19. scratch resistant surface article according to claim 12 or 13, which is characterized in that the PMMA of the composite sheet Layer does not contain or containing a small amount of PET, and the content range of PET is 0~50%, preferably 0~40%, more preferably 0~30%； The pet layer does not contain or containing a small amount of PMMA, and the content range of PMMA is 0~50%, preferably 0~40%, more preferably It is 0~30%.
20. scratch resistant surface article according to claim 12 or 13, which is characterized in that the scratch resistant surface article Preparation method is: the case hardened, cold stamping, hot-forming, IMD, anti-dazzle light processing, hydrophobic by the anti-scratch composite sheet One of oleophobic processing, vacuum vapour deposition, in-mold labels method, printing, plating or kinds of processes processing, are made all kinds of scratch resistants Surface article.
21. scratch resistant surface article according to claim 12 or 13, which is characterized in that form the composite sheet Wherein one layer or several layers of added with lubricant, the lubricant is added in the matrix of each layer.
22. scratch resistant surface article according to claim 12 or 13, which is characterized in that form the composite sheet Wherein one layer or several layers of also add one or more functional additives.
23. scratch resistant surface article according to claim 12 or 13, which is characterized in that the Rockwell of the composite sheet Hardness R scale is not less than 110.
24. a kind of anti-scratch composite sheet, which is characterized in that the anti-scratch composite sheet is any in claim 12-23 The anti-scratch composite sheet or composite sheet.
CN201811288673.6A 2017-11-08 2018-10-31 A kind of anti-scratch transparent membrane, scratch resistant surface article and composite sheet Pending CN109367176A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN2017110915829 2017-11-08
CN201711091582.9A CN107719943A (en) 2017-11-08 2017-11-08 A kind of anti-scratch transparent membrane for packaging material and preparation method thereof

Publications (1)

Publication Number Publication Date
CN109367176A true CN109367176A (en) 2019-02-22

Family

ID=61223131

Family Applications (3)

Application Number Title Priority Date Filing Date
CN201711091582.9A Pending CN107719943A (en) 2017-11-08 2017-11-08 A kind of anti-scratch transparent membrane for packaging material and preparation method thereof
CN201811288673.6A Pending CN109367176A (en) 2017-11-08 2018-10-31 A kind of anti-scratch transparent membrane, scratch resistant surface article and composite sheet
CN201821783323.2U Active CN210174337U (en) 2017-11-08 2018-10-31 Scratch-proof transparent film, scratch-proof surface product and scratch-proof composite sheet

Family Applications Before (1)

Application Number Title Priority Date Filing Date
CN201711091582.9A Pending CN107719943A (en) 2017-11-08 2017-11-08 A kind of anti-scratch transparent membrane for packaging material and preparation method thereof

Family Applications After (1)

Application Number Title Priority Date Filing Date
CN201821783323.2U Active CN210174337U (en) 2017-11-08 2018-10-31 Scratch-proof transparent film, scratch-proof surface product and scratch-proof composite sheet

Country Status (1)

Country Link
CN (3) CN107719943A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112109407A (en) * 2019-06-20 2020-12-22 四川大学 Scratch-resistant polymethyl methacrylate material
CN114590011A (en) * 2022-04-01 2022-06-07 苏州奥美材料科技有限公司 Composite film with high needle flame test tolerance time and high CTI value as well as preparation method and application thereof

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019091305A1 (en) * 2017-11-08 2019-05-16 廖洪传 Anti-scratch transparent thin film, scratch-resistant surface article and composite sheet
CN107719943A (en) * 2017-11-08 2018-02-23 廖洪传 A kind of anti-scratch transparent membrane for packaging material and preparation method thereof
CN109177405B (en) * 2018-09-06 2020-07-28 东莞市大盛丰电子科技有限公司 Method for manufacturing mobile phone screen protective film
CN111941973A (en) * 2019-05-17 2020-11-17 洛阳尖端技术研究院 Tear-resistant light-transmitting composite film, light-reflecting film, preparation method and application thereof

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006082442A (en) * 2004-09-16 2006-03-30 Mitsubishi Plastics Ind Ltd Extrusion film for deep drawing, bottom material using it and deep drawing container
CN202088598U (en) * 2011-06-16 2011-12-28 深圳市天常科技有限公司 PC/PMMA (polycarbonate/polymethyl methacrylate) composite sheet material
CN102303438A (en) * 2011-07-01 2012-01-04 广州市白云信达反光材料有限公司 PMMA (Polymethyl Methacrylate)/PC(Polycarbonate)/PMMA (Polymethyl Methacrylate) double-sided scratch-proof optical film and preparation method thereof
CN102681053A (en) * 2012-04-16 2012-09-19 浙江元泰特种膜有限公司 Photoelectric diffusion film and process for manufacturing same
CN103116426A (en) * 2012-11-20 2013-05-22 漳州宝发光电科技有限公司 Composite material type touch screen and production technology thereof
WO2017073987A1 (en) * 2015-10-29 2017-05-04 (주)엘지하우시스 Decorative sheet having excellent scratch resistance
CN210174337U (en) * 2017-11-08 2020-03-24 廖洪传 Scratch-proof transparent film, scratch-proof surface product and scratch-proof composite sheet

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006082442A (en) * 2004-09-16 2006-03-30 Mitsubishi Plastics Ind Ltd Extrusion film for deep drawing, bottom material using it and deep drawing container
CN202088598U (en) * 2011-06-16 2011-12-28 深圳市天常科技有限公司 PC/PMMA (polycarbonate/polymethyl methacrylate) composite sheet material
CN102303438A (en) * 2011-07-01 2012-01-04 广州市白云信达反光材料有限公司 PMMA (Polymethyl Methacrylate)/PC(Polycarbonate)/PMMA (Polymethyl Methacrylate) double-sided scratch-proof optical film and preparation method thereof
CN102681053A (en) * 2012-04-16 2012-09-19 浙江元泰特种膜有限公司 Photoelectric diffusion film and process for manufacturing same
CN103116426A (en) * 2012-11-20 2013-05-22 漳州宝发光电科技有限公司 Composite material type touch screen and production technology thereof
WO2017073987A1 (en) * 2015-10-29 2017-05-04 (주)엘지하우시스 Decorative sheet having excellent scratch resistance
CN210174337U (en) * 2017-11-08 2020-03-24 廖洪传 Scratch-proof transparent film, scratch-proof surface product and scratch-proof composite sheet

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
杜彦飞;: "薄膜表面硬化涂层的研究和应用", 信息记录材料, no. 06, pages 153 - 31 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112109407A (en) * 2019-06-20 2020-12-22 四川大学 Scratch-resistant polymethyl methacrylate material
CN112109407B (en) * 2019-06-20 2022-05-13 四川大学 Scratch-resistant polymethyl methacrylate material
CN114590011A (en) * 2022-04-01 2022-06-07 苏州奥美材料科技有限公司 Composite film with high needle flame test tolerance time and high CTI value as well as preparation method and application thereof
CN114590011B (en) * 2022-04-01 2023-03-14 苏州奥美材料科技有限公司 Composite film with high needle flame test tolerance time and high CTI value, and preparation method and application thereof

Also Published As

Publication number Publication date
CN107719943A (en) 2018-02-23
CN210174337U (en) 2020-03-24

Similar Documents

Publication Publication Date Title
CN109367176A (en) A kind of anti-scratch transparent membrane, scratch resistant surface article and composite sheet
US6455138B1 (en) Metallized sheeting, composites, and methods for their formation
CN102171277B (en) Optical film and method of preparing same
TWI810332B (en) Light-transmissive plastic plate structure with curved surface
JP5235557B2 (en) Transparent multilayer sheet for display faceplate
CN112644132A (en) High-hardness and high-weather-resistance polycarbonate composite board with excellent impact resistance and preparation method thereof
JP3802041B1 (en) Laminate for producing nameplates that can prevent fluctuations in reflected light
KR20170031154A (en) Synthetic resin laminate
CN207417537U (en) A kind of anti-scratch transparent membrane for packaging material
WO2019091305A1 (en) Anti-scratch transparent thin film, scratch-resistant surface article and composite sheet
CN201233450Y (en) Photochromic polarization sunglass
JP7065633B2 (en) Resin laminate and resin molded product using it
JPH10305453A (en) Lighting instrument lens
JP2946573B2 (en) Method for producing synthetic resin molded article having surface protective film and surface protective layer
JP2014012366A (en) Method of manufacturing highly elastic transparent resin laminate
KR20140009114A (en) Synthetic resin laminate
JP6818104B1 (en) Light-transmitting plastic plate structure with curved surface and its manufacturing method
JP3790265B1 (en) A laminate for producing nameplates that can prevent fluctuations in reflected light
JP2021101221A (en) Optical function resin panel and method for manufacturing the same
JP2016022616A (en) Multilayer film, film for decorative molding, and decorative molding
CN211814241U (en) Protection sticker structure for mobile phone
JPS61120102A (en) Reflector and its production
KR101950380B1 (en) Environment-friendly decoration film having metallic luster and manufacturing method thereof
JPH0421588B2 (en)
CN116003862A (en) Fingerprint-resistant scratch-resistant composite PET protective film and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
TA01 Transfer of patent application right

Effective date of registration: 20230712

Address after: 215345 Room 3, No. 888, Xinxing Road, Dianshanhu Town, Kunshan, Suzhou, Jiangsu Province

Applicant after: Suzhou Zhongrun New Materials Co.,Ltd.

Address before: 201100 Room 801, No. 70, Lane 1288, Lianhua South Road, Minhang District, Shanghai

Applicant before: Liao Hongchuan

TA01 Transfer of patent application right