CN210174337U

CN210174337U - Scratch-proof transparent film, scratch-proof surface product and scratch-proof composite sheet

Info

Publication number: CN210174337U
Application number: CN201821783323.2U
Authority: CN
Inventors: Hongchuan Liao; 廖洪传
Original assignee: Individual
Current assignee: Suzhou Zhongrun New Materials Co ltd
Priority date: 2017-11-08
Filing date: 2018-10-31
Publication date: 2020-03-24
Anticipated expiration: 2028-10-31
Also published as: CN107719943A; CN109367176A

Abstract

The utility model discloses an anti-scratch transparent film, anti-scratch surface product and anti-scratch composite sheet, including the PMMA layer that is located the upper strata and locating the PET layer of PMMA layer lower surface, the PET layer is selected from PETG (amorphous copolymerization PET) or APET (amorphous PET) or CPET (crystalline PET) layer, the thickness on PMMA layer account for 5~40% of gross thickness, the thickness on PET layer account for 20~95% of gross thickness; furthermore, a PMMA layer or a PC layer and a PMMA layer can be arranged on the lower surface of the PET layer. The utility model discloses use the PMMA layer as surface goods or packaging material's extexine, provide good resistant flower performance, more excellent weather resistance, better temperature toleration, simultaneously, use PET layer and PMMA direct complex still to overcome the fragility and the defect with high costs of PMMA layer itself.

Description

Scratch-proof transparent film, scratch-proof surface product and scratch-proof composite sheet

Technical Field

The utility model relates to an anti-scratch transparent film and scratch-resistant surface goods, surface goods can be film, shell, protective sheath, window panel, touch-sensitive screen panel, other panels, window, lens, sign etc. transparent film can be used to packaging material and sign, panel etc.

Background

At present, surface products of various products are sheet films or injection molding parts which take PMMA, PC, PET, PP and other resins as base materials. However, the properties of a single material often do not satisfy the requirements of some surface articles for impact resistance, scratch resistance, low cost, and the like. For example, PC has good impact resistance, but insufficient hardness and easy scratching, and the scratch resistance is still insufficient after hardening treatment; PMMA, while very hard, is susceptible to brittle fracture upon impact.

The plastic transparent film has wide application in the field of packaging, and is mainly made of materials such as PET, PC, PMMA, PVC, PP, PE, PS and the like, wherein the PVC does not accord with the environmental protection trend and is forbidden in many countries and enterprises; the transparency of PP and PE is poor; PS is easy to crack and has general processability, and solvent bonding cannot be carried out; the PMMA has higher light transmittance and hardness than other materials, the Rockwell hardness (R scale) reaches 118, the PMMA is not easy to scratch, the PMMA can be processed by solvent adhesive bonding, heat sealing, ultrasonic welding and the like, the weather resistance is the best of all thermoplastic plastics, the temperature resistance is higher than that of PETG, the thermal deformation temperature is about 84 ℃, but the cost is higher, the PMMA is close to that of PETG and PC, and the PMMA is easy to crack during processing and stress cracking; PC is also high in transparency and strength, but high in cost, cannot be glued by using a solvent, and is limited to be used in processing fields (such as manual boxes) which need quick bonding; PET is divided into common amorphous PET (commonly called APET) and PETG, and has good environmental protection, wherein the cost of the APET film is far lower than that of PC and PMMA, but the APET film is easy to crystallize and whiten and cannot be processed by processes such as solvent bonding, heat sealing and the like; because 1, 4-cyclohexanedimethanol is added in the polymerization process of PETG to form a non-crystallized copolymer, the PETG can be processed by a solvent adhesive bonding, heat sealing, ultrasonic welding and the like, but the cost is equivalent to PC, the hardness is too low, the Rockwell hardness (R scale) is only about 105, the temperature resistance is also poor, and the heat deformation temperature is only about 70 ℃. In summary, the existing plastic transparent film has the defects of high cost, easy scratch, brittle fracture and stress crack, so that no film material can simultaneously realize low cost, scratch resistance, brittle fracture resistance and stress crack resistance.

In addition, for surface articles, the properties of a single material often do not meet the multiple requirements of some surface articles. With the development of the in-mold decoration (IMD) technology, a new technology trend is to manufacture the product housing by combining the IMD process with the composite sheet, apply printing, high-pressure forming, punching and hardening treatment on the surface of the film, and then combine the film with other materials for forming through the IMD process. The composite sheet material is represented by a PMMA/PC two-layer composite material, wherein the surface layer of the material is a PMMA layer which is wear-resistant and is the outer surface of a product shell, and the other layer of the material is a PC layer which is good in toughness and is the inner surface of the product shell. At present, PMMA/PC composite materials are rapidly popularized. However, this material has the disadvantage that PC is prone to stress cracking resulting in poor overall product performance and the overall cost of the product is high within the general purpose thermoplastics.

SUMMERY OF THE UTILITY MODEL

The utility model provides an anti-scratch transparent film, a scratch-resistant surface product and a composite sheet, and preparation methods thereof.

The technical scheme of the utility model as follows:

the anti-scratch transparent film is used for packaging materials and comprises a PMMA layer positioned on the upper layer of the film and a PETG or APET layer arranged on the lower surface of the PMMA layer, wherein the thickness of the PMMA layer accounts for 5-40% of the total thickness, the thickness of the PETG or APET layer accounts for 20-95% of the total thickness, and further preferably, the thickness of the PETG or APET layer accounts for 60-95% of the total thickness. The total thickness refers to the total thickness of the PMMA layer, the PETG or APET layer, and possibly all structural layers of additional PC layers, PMMA layers, etc., but not to the thickness of additional layers obtained by surface treatment.

In a preferred embodiment of the invention, the thickness of the PMMA layer is less than the thickness of the PETG or APET layer.

The utility model discloses a one of them embodiment the lower surface on PETG or APET layer still be equipped with the PMMA layer, the thickness on this PMMA layer accounts for 5~40% of gross thickness, preferredly this moment the thickness on PETG or APET layer account for 20~ 90% of gross thickness.

Preferably, the total thickness of the film is 0.1-6 mm, more preferably 0.1-3 mm, and even more preferably 0.15-0.95 mm.

When the total thickness of the transparent film is less than 0.5mm, the proportion of the thickness of the PMMA layer in the total thickness is preferably 10-15%, and the proportion of the thickness of the PETG or APET layer in the total thickness is preferably 70-90%; when the total thickness of the transparent film is larger than 0.5mm, the proportion of the thickness of the PMMA layer in the total thickness is preferably 5-10%, and the proportion of the thickness of the PETG or APET layer in the total thickness is preferably 80-95%. The thickness proportion is better, and the effects of low cost, scratch resistance, difficult brittle fracture and stress cracking are realized.

Preferably, the hardness of the film is higher than that of the PETG or APET layer, and particularly the Rockwell hardness R scale of the film is not less than 110.

Preferably, the light transmittance of the film is greater than 86%, and more preferably, the light transmittance of the film is greater than 90%.

Preferably, the PMMA layer does not contain PET or contains a small amount of PET, and the content range of the PET is 0-50%, preferably 0-40%, and more preferably 0-30%; the PETG or APET layer does not contain PMMA or contains a small amount of PMMA, and the content range of PMMA is 0-50%, preferably 0-40%, and more preferably 0-30%.

In a preferred embodiment of the invention, the PMMA layer and the PETG or APET layer are directly connected together by a co-extrusion process.

The utility model also discloses a preparation method of foretell anti-scratch transparent film, including making PMMA extrude the plastify from an extruder, the melting material flow direction distributor to make PETG or APET extrude the plastify from another extruder, the melting material also flows to the distributor, wherein, PMMA falls into one deck or two-layer melting material stream at the distributor, superposes together in one side or both sides on distributor and PETG or APET layer, forms two-layer or three layer construction, flows out the cooling shaping behind the die head and is solid film.

The utility model also discloses another kind of foretell anti-scratch transparent film's preparation method, including making PMMA extrude the plastify from first extruder, melting material flow direction distributor, and make PETG or APET extrude the plastify from second extruder, melting material also flows to the distributor, still make PMMA extrude the plastify from third extruder, melting material flow direction distributor, from first, the plasticized PMMA melting material of third extruder extrusion is in the both sides superpose on distributor and PETG or APET layer together, form three layer construction, the cooling shaping is solid film behind the outflow die head.

In the above production method, the respective molten materials may be stacked at the die to form a multilayer structure.

The utility model discloses an anti-scratch transparent film to PMMA and PETG or APET layer structure's combination is as the major structure layer, has realized with low costs, anti-scratch simultaneously, is difficult for the brittle failure and the effect of stress cracking. In addition, various functional layers such as a hardened layer, an antiglare layer, an anti-fingerprint layer, and the like may be added thereto.

The utility model provides a resistant surperficial goods of scraping, resistant surperficial goods of scraping is with the preparation of scratch-proof composite sheet, scratch-proof composite sheet includes one deck PET layer, the upper strata on PET layer is equipped with the PMMA layer, the upper strata the PMMA layer is used as scratch-proof composite sheet's surface, the thickness on PMMA layer account for 5~40% of gross thickness, the thickness on PET layer account for 20~95% of gross thickness. Further preferably, the thickness of the PET layer accounts for 60-95% of the total thickness.

The utility model discloses an anti-scratch composite sheet to PMMA and PET layer structure's combination is as the major structure layer, has realized with low costs, anti-scratch, difficult brittle failure and stress cracking's effect simultaneously. In addition, various functional layers such as a hardening layer, an antiglare layer, an anti-fingerprint layer, and the like may be added thereto to produce a scratch-resistant surface article.

Preferably, the total thickness of the anti-scratch composite sheet is 0.1-6 mm, more preferably 0.1-0.95 mm, and even more preferably 0.1-0.49 mm.

The anti-scratch composite sheet material the PET layer can not have the lower floor, also can set up the lower floor, under the condition of setting the lower floor, the lower floor is:

the anti-scratch composite sheet is a three-layer structure, namely a PMMA/PET/PMMA composite sheet for short; or

The PC layer, the scratch-proof composite sheet material is a three-layer structure, called PMMA/PET/PC composite sheet material for short; or

And the scratching-resistant composite sheet material is of a four-layer structure, namely a PMMA/PET/PC/PMMA composite sheet material for short.

The thickness of the possible additional lower layers mentioned above is not linked to the PET layer and the PMMA layer of the upper layer, and can be of any thickness in case of a PC layer, and in case of a PMMA layer, in the range of 0.01mm to 2 mm.

When the total thickness of the scratch-resistant composite sheet is less than 0.5mm, the thickness ratio of the PMMA layer of the lower layer or the PMMA layer to the PC layer is 10-15%; when the total thickness of the composite sheet is larger than 0.5mm, the thickness ratio of the PMMA layer of the lower layer or the PMMA layer and the PC layer is 5-10%.

Preferably, the PMMA layer and the PET layer of the scratch-resistant composite sheet are directly compounded together by co-extrusion.

The preparation method of the anti-scratch composite sheet comprises the steps of extruding and plasticizing PMMA from one extruder, enabling molten materials to flow to a distributor, extruding and plasticizing PET from the other extruder, enabling the molten materials to flow to the distributor, dividing PMMA into one layer or two layers of molten material flow in the distributor, overlapping the PMMA and the PET layer at one side or two sides of the distributor to form a two-layer or three-layer structure, and cooling and forming the PMMA into a solid sheet after flowing out of a die head.

The preparation method of the anti-scratch composite sheet can also comprise the following steps: and extruding and plasticizing PMMA from the first extruder, allowing the molten material to flow to the distributor, extruding and plasticizing PET from the second extruder, allowing the molten material to flow to the distributor, extruding and plasticizing PMMA from the third extruder, allowing the molten material to flow to the distributor, overlapping the plasticized PMMA molten material extruded from the first extruder and the third extruder with two sides of a PET layer to form a three-layer structure, and cooling and molding the PMMA molten material after flowing out of the die head to form a solid sheet.

The utility model also discloses another kind of above-mentioned preparation method of crowded composite sheet altogether, in above-mentioned two kinds of preparation methods, add an extruder again and extrude PC, melting PC flow direction distributor, in the PET layer outside coincide on basic structure PMMA/PET layer, form PMMA/PET/PC three layer construction or PMMA/PET/PC/PMMA four layer construction, the cooling shaping is solid sheet behind the outflow die head. In addition to the above method, the PC layer may also be compounded by IMD after the co-extrusion of the PET layer and PMMA layer is completed.

Preferably, the PET layer of the composite sheet used is Amorphous PET (APET), or Crystalline PET (CPET) with nucleating agent, or non-crystalline modified PET (PETG), or a mixture of any two or three thereof in any proportion. The temperature resistance of the Crystalline PET (CPET) added with the nucleating agent is improved, so that the temperature resistance of the composite sheet is improved; the cost of APET is greatly reduced compared with PC used in the prior art; the APET layer or the CPET layer does not have the stress cracking problem of the PC layer (stress cracking means that the APET layer or the CPET layer is easy to break due to stress concentration after slight scratch or gap is formed and then stressed), and meanwhile, the composite sheet also has good toughness and good scratch resistance.

Preferably, the PET content of the PET layer of the composite sheet is 10% to 100%, preferably 50% to 100%, more preferably 60% to 100%, still more preferably 70% to 100%, and still more preferably 90% to 100%. The PET layer may contain PMMA as an additional component, for example, based on a scrap recycling process, adding scrap containing all components as a raw material to a PET layer of a subsequent process introduces PMMA into the PET layer, resulting in a PET layer having a PET content of not always 100%. Alternatively, other polymers that do not significantly affect the toughness of the PET layer are added for any other reason.

Preferably, one or more of the layers making up the composite sheet may be supplemented with a lubricant incorporated into the matrix of the respective layer. The lubricant is added to facilitate extrusion processing, and the smoothness of the surface layer is increased, thereby helping to prevent scratching.

In addition, one or more functional additives, such as an antioxidant, an ultraviolet absorber, a coupling agent and a compatilizer (such as a terpolymer) for increasing the bonding force between the PC layer and the PET layer, a nucleating agent and the like, a filler such as glass fiber, calcium carbonate, barium sulfate and the like, a toner, a color master and the like, can be added into one or more layers of the composite sheet.

Preferably, the rockwell hardness R scale of the composite sheet is not less than 110.

Preferably, the PMMA layer of the composite sheet material does not contain or contains a small amount of PET, and the content range of the PET is 0-50%, preferably 0-40%, and more preferably 0-30%; the PET layer does not contain or contains a small amount of PMMA, and the content range of PMMA is 0-50%, preferably 0-40%, and more preferably 0-30%.

The preparation method of the scratch-resistant surface product comprises the following steps: the scratch-resistant composite sheet is processed by one or more of surface hardening, cold stamping, hot press molding (including molding processes in various heating and pressurizing modes, such as hot bending, plastic suction and the like), IMD (including IML, IMF and IMR), fingerprint resistance treatment, anti-glare treatment, hydrophobic and oleophobic treatment, vacuum evaporation, in-mold labeling, printing and electroplating to prepare various scratch-resistant surface products, including but not limited to the following surface products: instrument panels, automotive upholstery, housings, protective covers, panels, touch screen panels, windows, signs, buttons, lenses, cell phone back covers, panels for MP3/MP 4/DVD/digital photo frame/GPS navigator/instruments, and the like.

Specifically, the method for producing the scratch-resistant surface article from the scratch-resistant composite sheet may be, for example, one of:

(1) and (2) performing injection molding on the two-layer structure composite sheet PMMA/PET or the three-layer structure composite sheet PMMA/PET/PC, PMMA/PET/PMMA or the four-layer structure composite sheet PMMA/PET/PC/PMMA by IML to be attached to various protective stickers, or performing hot pressing or high-pressure molding, or performing injection molding on the additionally added PC or PET layer directly by using an IMD technology, so that surface products such as instrument panels, automobile interior trim parts and the like can be prepared without using any binder.

(2) The anti-scratching composite sheet can be subjected to anti-glare treatment to be made into surface products such as window panels, lenses, labels and the like. The anti-dazzle treatment method can be an anti-dazzle layer coating mode (namely, anti-dazzle particles are added into coating liquid, and a micro concavo-convex appearance is formed on the surface of the coating after the coating is dried and cured, so that incident light is diffusely reflected to achieve the anti-dazzle effect); the micro concave-convex appearance can also be realized by methods such as vacuum evaporation, vapor deposition, sputtering, embossing, sand blasting, chemical etching and the like, so that the anti-dazzle effect is achieved.

(3) The anti-fingerprint treatment (which is realized by coating a hydrophobic and oleophobic layer on the surface of the product, wherein the coating is usually a fluorine-containing material such as perfluoropolyether, and the anti-fingerprint treatment mentioned below is the same as that described herein) can be carried out on the anti-scratch composite sheet to prepare various anti-fingerprint surface products such as panels, protective films, labels and the like.

(4) The surface of the anti-scratch composite sheet is subjected to surface hardening treatment (such as coating a hardened layer, wherein the hardened layer is a coating containing one or more of organic silicon, titanium oxide, dicyandiamide, a cobalt compound and organic polycarboxylic acid, the hardened layer is described in the specification), UV hardening treatment and printing process, and various electronic and touch screen panels or surface products such as display windows, signs, keys and the like can be prepared. The PMMA surface layer of the composite board can be hardened, and in addition, the surface layer can be processed with special functions such as AF (anti-fingerprint), AG (anti-dazzle), anti-fog and the like.

(5) The anti-scratch composite sheet is subjected to one or more processes of printing, UV texture manufacturing, electroplating, priming coating, cutting, cold stamping forming or hot press forming, surface hardening treatment, CNC engraving, IMD (in-mold decoration process including IML, IMF and IMR, the same below) or laminating, anti-dazzle, anti-fingerprint and the like to manufacture a product shell or panel capable of being used for anti-scratch, such as a mobile phone rear cover, a protective sleeve, a panel of MP3/MP 4/DVD/digital photo frame/GPS navigator/instrument and the like.

(6) And (3) adding a reflecting layer on the surface of the anti-scratch composite sheet by using a vacuum evaporation method, an in-mold labeling method, a silk-screen printing method, an electroplating method and the like to prepare the lens. The surface of the lens can be subjected to surface treatment such as hardening, anti-dazzle, fingerprint prevention and the like.

The utility model also provides an anti-scratch composite sheet, it is above-mentioned arbitrary anti-scratch composite sheet or composite sheet.

Compared with the prior art, the beneficial effects of the utility model are as follows:

firstly, the film of the packaging material and the scratch-resistant surface product which are commonly used at present are mainly made of PMMA and PC, and the cost of the two raw materials is higher; in most cases, the APET layer can be used as the main material of the film and the composite sheet, thereby effectively reducing the cost of the product;

secondly, the utility model discloses a scratch-proof transparent film and scratch-resistant surface goods for packaging material, through set up a PMMA layer on the upper surface of PETG or APET layer, regard PMMA layer as the extexine of packaging material, can provide good scratch-resistant colored performance, avoid being scratched because of slight friction, have kept pleasing to the eye and photic effect; and the appearance change is very small when the film is exposed to sunshine, wind and rain for a long time, and the film has better weather resistance;

thirdly, the utility model discloses a scratch-resistant transparent film and scratch-resistant surface goods for packaging material, two kinds of materials of PET and PMMA have been selected for use ingeniously and have been combined it directly (for example through coextrusion technology, can add the compatilizer and increase the cohesion when extruding), do not add the adhesive, and then the easy brittle rupture of PMMA layer and the fragile defect of stress are overcome by the PET layer is fine, the PET layer is difficult fragile rupture, can carve and press, die-cut, folding etc. and not break, simultaneously, the performance that the PET layer does not scrape is complemented by the PMMA layer and is obviously improved;

fourth, in the utility model, the thermal deformation temperature of PMMA is 84 ℃ which is 14 ℃ higher than the thermal deformation temperature (about 70 ℃) of PETG, therefore, the scratch-proof transparent film and the scratch-proof surface product can better endure the high temperature environment in the process of storage, transportation and use without softening, deformation and stickiness;

fifthly, the anti-scratch transparent film and the anti-scratch surface product for the packaging material fully utilize the high light transmittance of PMMA, and improve the light transmittance of the whole product;

sixthly, to having the goods that higher temperature resistant required and the requirement of shocking resistance, the utility model discloses can adopt the composite sheet that has the PC layer, like PMMA/PET/PC composite sheet and PMMA/PET/PC/PMMA composite sheet, consequently, the utility model discloses an application scope is more extensive.

Of course, it is not necessary for any particular product to achieve all of the above-described advantages at the same time.

Drawings

Fig. 1 is a schematic structural view of an anti-scratch transparent film for packaging material according to an embodiment of the present invention;

fig. 2 is another schematic structural view of an anti-scratch transparent film for packaging material according to an embodiment of the present invention;

FIG. 3 is a schematic view of the construction of a scratch resistant composite sheet for use in a scratch resistant surface article according to an embodiment of the present invention;

in the figure, 1-PMMA layer; 2-a PET layer; 3-PC layer; 4-PMMA layer.

Detailed Description

For the outer packaging film products, the PET film is commonly used in the market, and has the defects of low surface hardness, easy scratching due to slight friction, influence on the appearance and the effect of light transmission, low heat deformation temperature and poor weather resistance.

Generally, PMMA, although superior in hardness, light transmittance and weather resistance, has a drawback of being brittle during processing, and cannot be made into a sheet of <0.5mm due to brittle fracture, and its use in packaging materials is limited due to its high cost.

In addition, in the prior art, PMMA is mainly made into a base material optical film of the touch screen, and then a hardening agent is coated to make the scratch-resistant optical film. Thus, one skilled in the art of outer packaging materials would not readily appreciate the use of the stiffness of PMMA itself to assist in improving the stiffness of other materials, particularly for reasons of cost.

Therefore, it is very important to develop an outer packaging material film having both properties of PET film and PMMA film and relatively low cost.

The trade mark selection range of the transparent PETG is narrow, the Rockwell hardness is basically 105-108 (R scale), the transparent PMMA and PC are made of materials with various hardness, the hardness of some PMMA is lower than that of PETG, the hardness of some PC is higher than that of PMMA, for example, the Rockwell hardness (R scale) of PETG GN120 of Islam chemistry is 107, the Rockwell hardness (R scale) of PMMAShinkoLite-P UT-300 of Mitsubishi is 100, and the Rockwell hardness (R scale) of PC 300-6 of Sheng is 118.

The utility model selects PMMA with hardness higher than PETG as the scratch-resistant surface layer, and PMMA does not have requirements on the hardness when being used as the optical film of the base material.

The utility model discloses an anti-scratch transparent film sets up one deck PMMA layer through the upper surface at PETG or APET layer at least, use the PMMA layer to be packaging material's upper surface layer or upper and lower superficial layer promptly, PETG or APET layer are packaging material's lower surface layer or sandwich layer, both utilized PMMA on hardness, luminousness and weatherability and processed on the soluble agent superior characteristic such as splice, utilized PETG or APET's pliability and APET advantage such as low cost again, utilize the advantage of one side on certain performance in order to solve the disadvantage of another side at this performance promptly, and compromise the cost factor, make the utility model discloses a film has resistant scratch flower performance, weather resistance, high transparency and is carving pressure, die-cut, processes such as folding and not split, and advantage such as the cost is lower relatively. In general, to reduce cost, an APET layer is often used, and a small amount of PETG may be mixed therein, or PETG may not be added.

The scratch-resistant surface product of the utility model takes the PMMA layer as the outer surface layer of the surface product, thereby providing good scratch-resistant performance and avoiding being scratched due to slight friction; simultaneously provides better weather resistance, and has little change of appearance even if exposed to sunshine, wind and rain for a long time; better temperature resistance, and no softening, deformation or stickiness during storage, transportation and use; and the APET layer or the PETG layer provides mechanical properties with enough strength for surface product products, and greatly reduces the cost of product shells.

The present invention will be further described with reference to the following specific examples. It should be understood that these examples are only for illustrating the present invention, and are not intended to limit the scope of the present invention. In practical applications, the improvement and adjustment made by those skilled in the art according to the present invention still belong to the protection scope of the present invention.

For better illustration of the present invention, the following detailed description of the present invention is provided in conjunction with the accompanying drawings.

As shown in figure 1, the utility model discloses an anti-scratch transparent film or composite sheet for packaging material, including being located PMMA layer 1 on film upper strata and locating PETG or APET layer 2 (PET layer) of PMMA layer 1 lower surface, PMMA layer 1's thickness account for 5~40% of gross thickness, PETG or APET layer 2's thickness account for 20~95% of gross thickness, preferably, PETG or APET layer's thickness account for 60 ~95% of gross thickness.

In another embodiment of the present invention, as shown in fig. 2, the lower surface of the PETG or APET layer 2 is further provided with a PMMA layer 3, and the thickness of the PMMA layer 3 accounts for 5-40% of the total thickness. In this case, the thickness of the PETG or APET layer is preferably 20-90% of the total thickness.

When PMMA is used as the upper surface layer or the upper surface layer and the lower surface layer of the film packaging material, the thickness of PMMA accounts for 7-20% of the total thickness, and the thickness of the PETG or APET layer 2 accounts for 30-90% of the total thickness.

In addition, various additives which do not obviously affect the light transmittance of the film, such as an antioxidant, an ultraviolet absorber, a lubricant, a coupling agent for increasing the bonding force between the PMMA layer and the PET layer and the like can be added into each layer of material of the film.

The utility model also discloses a foretell a preparation method for scratch-proof transparent film for packaging material, including PMMA extrudees the plastify from an extruder, and the melting material flows to the distributor, and PETG or APET extrude the plastify from another extruder, and the melting material also flows to the distributor, and wherein, PMMA falls into one deck or two-layer melting material stream at the distributor, superposes together in one side or both sides on distributor and PETG or APET layer, forms two-layer or three layer construction's film.

Namely: the PMMA is divided into two layers of molten material flow at a distributor, and the two layers of molten material flow are overlapped together at the distributor and two sides of a PET layer to form a film with a three-layer structure; or, PMMA is directly laminated with the PET layer without being divided into two layers at the distributor to form a film with a two-layer structure. And continuously flowing the superposed two-layer or three-layer molten materials to a die head, flowing out of the die head, entering a three-roller for rapid cooling and forming, and trimming and rolling to obtain the film.

In addition, the transparent film can also be produced by adopting an in-mold compounding co-extrusion process, namely two layers or three layers of melting materials are not overlapped at a distributor but are overlapped together after entering a die head; and those skilled in the art also know that when the three-layer co-extruded transparent film is produced, PMMA can also be extruded and plasticized by two extruders to form two molten materials which are overlapped with PET molten materials extruded and plasticized by the other extruder.

The utility model provides a resistant surperficial goods of scraping, resistant surperficial goods of scraping is with the preparation of scratch-proof composite sheet, scratch-proof composite sheet includes one deck PET layer, the upper strata on PET layer is equipped with the PMMA layer, locates the upper strata the PMMA layer is used as scratch-proof composite sheet's surface, the thickness on PMMA layer account for 5~40% of gross thickness, the thickness on PET layer account for 20~95% of gross thickness.

Anti-scratch composite sheet the PET layer does not set up the lower floor or sets up the lower floor, under the condition that sets up the lower floor, the lower floor is:

a PMMA layer, wherein the scratch-resistant surface product is a three-layer structure, namely a PMMA/PET/PMMA composite sheet for short; or

The PC layer is a three-layer structure, namely a PMMA/PET/PC composite sheet for short; or

And a PMMA layer is also arranged below the PC layer, and the scratch-resistant surface product has a four-layer structure, namely a PMMA/PET/PC/PMMA composite sheet for short.

Referring to fig. 3, in some embodiments of the present invention, the structure of the composite sheet includes: a PMMA layer 1 serving as an outer surface, a PET layer 2 disposed under the PMMA layer 1, and a PC layer 3 disposed under the PET layer 2 and a PMMA layer 4 disposed under the PC layer 3.

In a preferred embodiment of the present invention, the composite sheet used in the scratch resistant surface article is a co-extruded composite sheet. In addition to the coextrusion process, the lower additional PMMA layer, PC layer or PC + PMMA layer can also be combined on the PET layer by the IMD process.

The PET layer of the composite sheet material used in the utility model is Amorphous PET (APET), or Crystalline PET (CPET) added with nucleating agent, or non-crystalline copolymerized PET (PETG), or the mixture of any two or three of the Amorphous PET (APET) and the non-crystalline copolymerized PET (PETG) according to any proportion.

The total thickness of the composite sheet is 0.1-6 mm, preferably 0.1-0.95 mm, and more preferably 0.1-0.49 mm. When the total thickness of the composite sheet is less than 0.5mm, the thickness ratio of the PMMA layer of the lower layer or the PMMA layer to the PC layer is 10-15%; when the total thickness of the composite sheet is larger than 0.5mm, the thickness ratio of the PMMA layer of the lower layer or the PMMA layer and the PC layer is 5-10%.

The PET content of the PET layer of the composite sheet is 10% to 100%, preferably 50% to 100%, more preferably 60% to 100%, still more preferably 70% to 100%, and still more preferably 90% to 100%.

The PMMA layer of the composite sheet does not contain or contains a small amount of PET, and the content range of the PET is 0-50%, preferably 0-40%, and more preferably 0-30%; the PET layer does not contain or contains a small amount of PMMA, and the content range of PMMA is 0-50%, preferably 0-40%, and more preferably 0-30%.

The preparation method of the composite sheet comprises the steps of extruding and plasticizing PMMA from one extruder, enabling molten materials to flow to a distributor, extruding and plasticizing PET from the other extruder, enabling the molten materials to flow to the distributor, dividing PMMA into one layer or two layers of molten material flow in the distributor, overlapping the PMMA and the PET layer at one side or two sides of the distributor to form a two-layer or three-layer structure, and cooling and forming the PMMA into a solid sheet after flowing out of a die head.

The preparation method of the composite sheet can also comprise the following steps: and extruding and plasticizing PMMA from a first extruder, allowing the molten material to flow to a distributor, extruding and plasticizing PET from a second extruder, allowing the molten material to flow to the distributor, extruding and plasticizing PMMA from a third extruder, allowing the molten material to flow to the distributor, overlapping the plasticized PMMA molten material extruded from the first extruder and the third extruder with two sides of a PET layer to form a three-layer structure, and cooling and molding the PMMA sheet after flowing out of a die head to form a solid sheet.

The utility model also discloses another kind of above-mentioned preparation method of crowded composite sheet altogether, in above-mentioned two kinds of preparation methods, add an extruder again and extrude PC, melting PC flow direction distributor, in the PET layer outside coincide on basic structure PMMA/PET layer, form PMMA/PET/PC three layer construction or PMMA/PET/PC/PMMA four layer construction, the cooling shaping is solid film behind the outflow die head.

The preparation method of the scratch-resistant surface product comprises the following steps: and carrying out one or more processes of surface hardening, cold stamping, hot press molding, IMD (in-mold decoration), anti-dazzle treatment, hydrophobic and oleophobic treatment, vacuum evaporation method, in-mold labeling method, printing and electroplating on the anti-scratch composite sheet to prepare various scratch-resistant surface products.

In some embodiments, one or more of the layers making up the composite sheet may be added with a lubricant that is incorporated into the matrix of each layer.

In some embodiments, one or more of the layers comprising the composite sheet may further comprise one or more functional additives. For example, antioxidants, ultraviolet absorbers, coupling agents and compatibilizers (such as some terpolymers), nucleating agents and the like for increasing the bonding force between the PC layer and the PET layer, fillers such as glass fibers, calcium carbonate, barium sulfate and the like, and toners, color concentrates and the like.

In a preferred embodiment, the composite sheet has a rockwell hardness R scale of not less than 110.

The utility model also provides an anti-scratch composite sheet, anti-scratch composite sheet is foretell anti-scratch composite sheet or composite sheet.

Example 1

The scratch-resistant transparent film for the packaging material in the embodiment 1 comprises a PMMA layer 1 located on the upper layer of the film, an APET layer 2 located on the lower surface of the PMMA layer 1, and a PMMA layer 3 further located on the lower surface of the APET layer 2, wherein the thickness of the PMMA layer 1 accounts for 10% of the total thickness, the thickness of the APET layer 2 accounts for 80% of the total thickness, the thickness of the PMMA layer 3 accounts for 10% of the total thickness, and the total thickness of the film is 0.3 mm. The preparation method comprises the following steps: respectively drying PMMA granules and APET granules, and conveying the PMMA granules and APET granules to a co-extrusion sheet machine set for extrusion molding; the results of the performance tests are shown in the table one, and the properties of the PETG/APET/PETG film material with the same thickness are shown in the table two as a comparison.

Watch 1

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The cost of the PMMA raw material is basically the same as that of the PETG raw material. The comparison above shows, compare with PETG/APET/PETG three-layer sheet on the existing market, under the unchangeable condition of cost, the utility model discloses the hardness of film has obviously been improved to show the anti-scratch performance who has improved the film. In addition, the light transmittance is improved to a certain extent.

Example 2

The scratch-resistant transparent film for the packaging material in this embodiment 2 includes a PMMA layer 1 located on the upper layer of the film and an APET layer 2 located on the lower surface of the PMMA layer 1, wherein the thickness of the PMMA layer 1 accounts for 20% of the total thickness, the thickness of the APET layer 2 accounts for 80% of the total thickness, and the total thickness of the film is 0.25 mm. The preparation method comprises the following steps: drying the PMMA granules and the PET granules, and then conveying the PMMA granules and the PET granules to a co-extrusion sheet machine set for extrusion molding; the performance test is shown in table three, and the performance of the PETG/APET film material with the same thickness is used as a comparison, and the performance is shown in table four.

Watch III

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The comparison above shows, compare with the two-layer sheet of PETG APET on the existing market, under the unchangeable condition of cost, the utility model discloses the hardness of film has obviously been improved to the anti-scratch performance of film has been showing and has been improved. In addition, the light transmittance is improved to a certain extent.

Example 3

The scratch-resistant transparent film for the packaging material in this embodiment 3 includes a PMMA layer 1 located on the upper layer of the film, an APET layer 2 located on the lower surface of the PMMA layer 1, and a PMMA layer 3 further located on the lower surface of the APET layer 2, wherein the thickness of the PMMA layer 1 accounts for 7% of the total thickness, the thickness of the APET layer 2 accounts for 86% of the total thickness, the thickness of the PMMA layer 3 accounts for 7% of the total thickness, and the total thickness of the film is 3 mm. The preparation method comprises the following steps: respectively drying PMMA granules and APET granules, and conveying the PMMA granules and APET granules to a co-extrusion sheet machine set for extrusion molding; the performance test is shown in table five, and the performance of the PETG film material with the same thickness is used as a comparison, and the performance is shown in table six. In addition, the PETG/APET/PETG sheet with the same thickness is not taken as a comparative example, because APET is easy to crystallize and whiten due to too slow cooling speed when the thickness is more than 1mm, and the transparency is seriously influenced.

Watch five

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The comparison above shows that, compared with the PETG/APET/PETG sheet material on the current market, under the condition of unchanged cost, the utility model discloses except that the hardness and the anti-scratch performance of film have obviously been improved, the heat distortion temperature of sheet material has also been improved.

Example 4

Printing a PMMA/APET two-layer composite sheet (thickness ratio is 10: 90) with the thickness of 0.5mm, manufacturing UV textures, electroplating, coating a bottom layer, hot-press molding, coating a UV hardening layer, and CNC engraving to manufacture the scratch-resistant mobile phone shell.

Compared with PMMA products with the same thickness, the surface hardness of the mobile phone shell of the embodiment is the same, but the material cost is saved by 40%, and the impact strength is improved by 2 times. Compared with the mobile phone shell made of a PMMA/PC two-layer composite sheet (thickness ratio is 10: 90), the material cost is saved by 40%, and stress cracking is avoided.

Example 5

Printing, hot-press forming and coating a UV (ultraviolet) hardening layer on a PMMA/CPET/PMMA three-layer composite sheet material (thickness ratio is 10: 80:10) with the thickness of 0.5mm to prepare the scratch-proof mobile phone shell.

Compared with PMMA products with the same thickness, the surface hardness of the mobile phone shell of the embodiment is the same, but the material cost is saved by 36 percent, and the impact strength is improved by 1.8 times.

This example shows that the heat distortion temperature is 30 degrees higher than example 4 where the inner surface layer of the article is APET because the intermediate layer is a crystalline CPET layer.

Compared with the mobile phone shell made of a PMMA/PC/PMMA three-layer composite sheet (thickness ratio is 10: 80:10), the material cost of the mobile phone shell is saved by 36%, and stress cracking is avoided.

Example 6

A transparent 0.2mm thick PMMA/APET/PMMA three-layer composite sheet (thickness ratio 12.5: 75: 12.5) was coated with a UV-hardened layer on both surface layers to produce a glazing panel.

PMMA is very easy to crack due to poor impact resistance and cannot be made into a 0.2mm thin film, but the structure of the embodiment can be used for manufacturing a 0.2mm thick thin film panel, the surface hardness of the manufactured panel is about 10(R scale) higher than that of other PET and PC panels visible in the market, and the scratch resistance is better.

Example 7

Coating a UV hardening layer on two surface layers by using a transparent PMMA/APET two-layer composite sheet (thickness ratio is 20: 80) with the thickness of 0.15mm, coating adhesive on one surface and covering a release film, performing anti-dazzle treatment on the other surface, and adding an oleophobic and hydrophobic coating to prepare the surface protective film of electronic products such as mobile phones and the like.

PMMA is very easy to crack due to poor impact resistance, and cannot be made into a 0.15mm thin film. The surface protection film of the embodiment has the surface hardness higher than that of other PET, PC, PP and PVC protection films on the market by more than about 10(R scale), and has better scratch resistance.

Example 8

A PMMA/APET/PMMA three-layer composite sheet (thickness ratio is 10: 80:10) with the thickness of 0.5mm is coated with a UV hardening layer and is subjected to vacuum aluminum plating to prepare the lens.

The lens of this example has the same surface hardness but a 36% material cost savings and 1.8 times improved impact strength compared to a PMMA article of the same thickness.

The structure of the present embodiment can also be used to make thinner lenses, but PMMA in the prior art cannot be made due to brittle fracture.

The surface hardness of the lens of the embodiment is higher than that of other PET and PC panels on the market by about 10(R scale), and the scratch resistance is better.

Example 9

A PMMA/APET two-layer composite sheet with the thickness of 0.5mm (the thickness ratio is 10: 90) is coated with a UV hardening layer and printed to be made into a panel and a label of an electronic product or instrument.

Compared with PMMA products with the same thickness, the surface hardness of the panel and the sign of the embodiment is the same, but the material cost is saved by 40 percent, the impact strength is improved by 2 times, and the surface hardness is about 10(R scale) higher than that of other plastic PET and PC panels on the market, and the scratch resistance is better.

The preferred embodiments of the present invention disclosed above are intended only to help illustrate the present invention. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and its practical applications, to thereby enable others skilled in the art to best understand the invention for and utilize the invention. The present invention is limited only by the claims and their full scope and equivalents.

Claims

1. The anti-scratch transparent film is used for a packaging material and is characterized by comprising a PMMA layer positioned on the upper layer of the film and a PETG or APET layer arranged on the lower surface of the PMMA layer, wherein the thickness of the PMMA layer accounts for 5-40% of the total thickness, and the thickness of the PETG or APET layer accounts for 20-95% of the total thickness.

2. The anti-scratch transparent film as claimed in claim 1, wherein a PMMA layer is further arranged on the lower surface of the PETG or APET layer, and the thickness of the PMMA layer accounts for 5-40% of the total thickness.

3. The scratch-resistant transparent film according to claim 1 or 2, wherein the total thickness of the film is 0.1-6 mm.

4. The scratch-resistant transparent film according to claim 1 or 2, wherein the total thickness of the film is 0.1-3 mm.

5. The scratch-resistant transparent film according to claim 1 or 2, wherein the total thickness of the film is 0.15-0.95 mm.

6. The scratch-resistant transparent film as claimed in claim 1 or 2, wherein when the total thickness of the film is less than 0.5mm, the thickness of the PMMA layer accounts for 10-15% of the total thickness, and the thickness of the PETG or APET layer accounts for 70-90% of the total thickness; when the total thickness of the film is larger than 0.5mm, the thickness of the PMMA layer accounts for 5-10% of the total thickness, and the thickness of the PETG or APET layer accounts for 80-95% of the total thickness.

7. The scratch-resistant transparent film according to claim 1 or 2, wherein the film has a rockwell hardness R scale of not less than 110.

8. The scratch-resistant transparent film according to claim 1 or 2, wherein the light transmittance of the film is greater than 86%.

9. The scratch-resistant transparent film according to claim 1 or 2, wherein the PMMA layer and the PETG or APET layer are directly connected together by a co-extrusion process.

10. The scratch-resistant surface product is characterized by being made of a scratch-resistant composite sheet, wherein the scratch-resistant composite sheet comprises a PET layer, a PMMA layer is arranged on the upper layer of the PET layer, the PMMA layer arranged on the upper layer is used as the outer surface of the scratch-resistant composite sheet, the thickness of the PMMA layer accounts for 5-40% of the total thickness, and the thickness of the PET layer accounts for 20-95% of the total thickness.

11. The scratch resistant surface article of claim 10 wherein the PET layer of the scratch resistant composite sheet is provided without an underlayer or with an underlayer, where provided, the underlayer is:

12. The scratch resistant surface article of claim 10 wherein the PET layer and the PMMA layer of the scratch resistant composite sheet are directly compounded together by co-extrusion.

13. The scratch resistant surface article of claim 10 or 11, wherein the total thickness of the composite sheet is 0.1 to 6 mm.

14. The scratch resistant surface article of claim 10 or 11, wherein the total thickness of the composite sheet is 0.1 to 0.95 mm.

15. The scratch resistant surface article of claim 10 or 11, wherein the total thickness of the composite sheet is 0.1 to 0.49 mm.

16. The scratch-resistant surface article of claim 11, wherein when the total thickness of the composite sheet is 0.5mm or less, the thickness ratio of the PMMA layer of the lower layer or the PMMA layer to the PC layer is 10 to 15%; when the total thickness of the composite sheet is larger than 0.5mm, the thickness ratio of the PMMA layer of the lower layer or the PMMA layer and the PC layer is 5% -10%.

17. The anti-scratch composite sheet is characterized by comprising a PET layer, wherein a PMMA layer is arranged on the upper layer of the PET layer, the PMMA layer arranged on the upper layer is used as the outer surface of the anti-scratch composite sheet, the thickness of the PMMA layer accounts for 5-40% of the total thickness, and the thickness of the PET layer accounts for 20-95% of the total thickness.