KR102091556B1 - Plastic laminate, preparation method thereof and plastic molded product obtained therefrom - Google Patents

Abstract

A plastic laminate according to the present invention is designed to have a symmetrical laminated structure of plastic films provided by hard coating layers, thereby significantly reducing curl generation in a high temperature environment. In addition, the plastic laminate has controlled process conditions, compositions and thickness of each layer, thereby improving not only dimensional stability, but also properties such as antifouling properties and printability. Accordingly, a plastic molded product molded from the plastic laminate has advantages of high durability and low cost, and thus can be applied as a front or rear cover of a mobile device by replacing conventional glass materials.

Description

Plastic laminate, manufacturing method and plastic molded body {PLASTIC LAMINATE, PREPARATION METHOD THEREOF AND PLASTIC MOLDED PRODUCT OBTAINED THEREFROM}

The present invention relates to a plastic laminate, a method for manufacturing the same, and a plastic molded body. Specifically, the present invention relates to a cover of a plastic material that can replace the glass material applied as a cover on the front or back of a mobile device.

Glass materials having advantages in terms of appearance, dimensional stability, and optical properties are generally used in front or rear covers of mobile devices. However, the front or rear cover of the glass material used in the mobile device is easily broken and scattered due to external impact. In addition, according to the recent trend of large-area mobile devices, when using a glass cover, it is difficult to reduce the weight and increase the cost.

Accordingly, attempts have been made to develop a cover using a plastic material to replace the glass material. In particular, the plastic material has the advantage of being lightweight, having excellent impact resistance, not being scattered even when broken, and having a low cost.

On the other hand, the front or rear cover is disposed on the outermost side is required to protect the mobile device from the external environment, for this purpose to form a hard coating layer on the outer exposed surface of the plastic substrate layer to improve the surface hardness and durability. In addition, since various designs are applied to the cover of the mobile device, it is required to give molded or printed advantageous properties to the hard coating layer disposed inside the device.

Korean Patent Publication No. 2017-5755

Despite the many advantages of the plastic material hard coating film for application to a mobile device, there is a problem in that curling occurs and dimensional stability is low due to a difference in heat shrinkage between layers in a high temperature environment.

Accordingly, as a result of research by the present inventors, the plastic film having a hard coating layer was designed in a symmetrical lamination structure, thereby significantly reducing curl generation in a high temperature environment. In addition, by controlling the thickness, component, and process conditions of each layer of the laminate, it was possible to further improve not only dimensional stability, but also properties such as antifouling properties and printability.

Accordingly, an object of the present invention is to provide a plastic laminate and a method for manufacturing the same, improving the low dimensional stability of the existing hard coating film and improving other properties. In addition, an object of the present invention is to provide a plastic molded article of high durability and low cost that can replace the glass material applied as a front or rear cover of a conventional mobile device by using the plastic laminate.

According to the above object, the present invention is a core substrate layer; A first sheet comprising a first substrate layer and a first hard coating layer sequentially disposed on one surface of the core substrate layer; And a second sheet sequentially disposed on the other surface of the core substrate layer, the second substrate layer and the second hard coating layer, wherein the first sheet and the second sheet are from 1: 0.9 to 1: 1.1. It provides a plastic laminate, having a thickness ratio of.

According to the other object, the present invention comprises the steps of obtaining a first sheet by forming a first hard coating layer on the first substrate layer; Forming a second hard coating layer on the second substrate layer to obtain a second sheet; Laminating the first sheet so that the first substrate layer faces on one surface of the core substrate layer; And laminating the second sheet so that the second substrate layer faces the other surface of the core substrate layer, wherein the first sheet and the second sheet have a thickness ratio of 1: 0.9 to 1: 1.1, Provided is a method of manufacturing a plastic laminate.

According to another object, the present invention provides a plastic molded body molded from the plastic laminate.

The plastic laminate according to the present invention includes a plastic film formed with a hard coating layer in a symmetrical structure, so that curl generation can be minimized even in a high temperature environment. In addition, the plastic laminate may be improved in properties such as anti-fouling property and printability, as well as dimensional stability by controlling the thickness, composition, and process conditions of each layer. Accordingly, the plastic molded body molded from the plastic laminate has advantages of high durability and low cost, and thus can be usefully applied as a front or rear cover of a mobile device by replacing a conventional glass material.

1 shows a cross-sectional view of a plastic laminate according to an embodiment of the present invention.

Hereinafter, the present invention will be described in more detail with reference to the accompanying drawings. In the accompanying drawings, a size or a gap may be exaggerated to help understanding, and a description that is obvious to a person skilled in the art may be omitted.

In the following description, when each component is described as being disposed above or below other components, it should be understood that all of the components with or without another component are included.

In this specification, "comprising" another component means that another component may be further included unless otherwise specified.

1 shows a cross-sectional view of a plastic laminate according to an embodiment of the present invention.

Plastic laminate according to the present invention, with reference to Figure 1, the core substrate layer 100; A first sheet 10 including a first base layer 210 and a first hard coating layer 310 sequentially disposed on one surface of the core base layer 100; And a second sheet 20 including the second base layer 220 and the second hard coating layer 320, which are sequentially disposed on the other surface of the core base layer 100, and the first sheet ( 10) and the second sheet 20 have a thickness ratio of 1: 0.9 to 1: 1.1.

In addition, the plastic laminate may include a first adhesive layer 410 disposed between the core base layer 100 and the first sheet 10; And a second adhesive layer 420 disposed between the core substrate layer 100 and the second sheet 20.

Hereinafter, each component layer will be described in more detail.

Core base layer

The core substrate layer is located at the center of the plastic laminate, serves as a support for the entire structure and serves to impart formability.

The core base layer may include a polymer resin, for example, a transparent polymer resin.

Specifically, the core substrate layer is polyethylene terephthalate (PET), polyimide (PI), cyclic olefin polymer (COP), polyethylene naphthalate (PEN), polyethersulfone (PES), polycarbonate (PC), polyether It may include one or more polymer resins selected from the group consisting of ether ketone (PEEK), polyphenylene sulfide (PPS), polyamide (PA) and polypropylene (PP).

As a specific example, it may be more advantageous for the core base layer to contain a polycarbonate resin to impart moldability and suppress curl.

The thickness of the core substrate layer may be 100 μm to 1000 μm, 100 μm to 600 μm, 150 μm to 500 μm, 200 μm to 450 μm, 200 μm to 300 μm, or 300 μm to 500 μm.

Specifically, the core substrate layer may have a thickness of 200 μm to 500 μm. When within the preferred thickness range, it may be more advantageous to suppress curl while having supportability and moldability for the entire structure.

First sheet and second sheet

The first sheet includes a first substrate layer and a first hard coating layer, which are sequentially arranged on one surface of the core substrate layer. In addition, the second sheet includes a second substrate layer and a second hard coating layer, which are sequentially arranged on the other surface of the core substrate layer.

The first base layer and the second base layer serve to support the first hard coating layer and the second hard coating layer, respectively.

The first sheet and the second sheet have a thickness ratio of 1: 0.9 to 1: 1. When within the above range, the first sheet and the second sheet have a symmetrical structure around the core substrate layer, and thus curl generation can be significantly suppressed. More specifically, the first sheet and the second sheet may have a thickness ratio of 1: 0.99 to 1: 1.01.

The first sheet and the second sheet can achieve a symmetrical structure in terms of detailed layer thickness.

Specifically, the first hard coating layer and the second hard coating layer have a thickness ratio of 1: 0.9 to 1: 1.1, and the first base layer and the second base layer have a thickness ratio of 1: 0.9 to 1: 1.1. You can.

More specifically, the first hard coating layer and the second hard coating layer have a thickness ratio of 1: 0.99 to 1: 1.01, and the first base layer and the second base layer have a thickness ratio of 1: 0.99 to 1: 1.01. Can have

The thickness of the first substrate layer and the second substrate layer may be 10 μm to 500 μm, 50 μm to 300 μm, 100 μm to 200 μm, 100 μm to 150 μm, or 150 μm to 200 μm, respectively.

The thickness of the first hard coating layer and the second hard coating layer is 1 μm to 50 μm, 1 μm to 30 μm, 1 μm to 20 μm, 1 μm to 10 μm, 3 μm to 10 μm, or 5 μm to 10 μm, respectively. Can be

Specifically, the first base layer and the second base layer may have a thickness of 100 μm to 200 μm, and the first hard coating layer and the second hard coating layer may have a thickness of 3 μm to 10 μm. When within the preferred thickness range, it can be more advantageous to suppress the curl while supporting the hard coating layer well.

The first base layer and the second base layer may include a polymer resin, and specifically, a transparent polymer resin.

For example, the first base layer and the second base layer are polyethylene terephthalate (PET), polyimide (PI), cyclic olefin polymer (COP), polyethylene naphthalate (PEN), polyethersulfone (PES), It may include at least one polymer resin selected from the group consisting of polycarbonate (PC), polyether ether ketone (PEEK), polyphenylene sulfide (PPS), polyamide (PA) and polypropylene (PP).

As a specific example, the first base layer and the second base layer may include polyethylene terephthalate resin, which may be more advantageous to impart stability after molding and suppress curl.

The first hard coating layer and the second hard coating layer are disposed on the outermost portion of the plastic laminate to improve surface hardness, antifouling properties, and printability.

The first hard coating layer and the second hard coating layer may include a thermoplastic resin, a thermosetting resin, a UV curable resin, and the like, and preferably may include a UV curable resin to exert high hard coating properties by increasing the surface hardness. have.

Specific examples of the thermoplastic resin and the thermosetting resin are acrylic resin, urethane resin, epoxy resin, urethane acrylate resin, epoxy acrylate resin, cellulose resin, acetal resin, melamine resin, phenol resin, silicone resin , Polyester resin, polycarbonate resin, polyethylene resin, polystyrene resin, polyamide resin, polyimide resin, and mixtures thereof.

As the UV curable resin, a photopolymerizable prepolymer that is crosslinked and cured by UV light irradiation may be used, and the photopolymerizable prepolymer may include a cationic polymerization type and a radical polymerization type photopolymerizable prepolymer. Examples of the cationic polymerization type photopolymerizable prepolymer include an epoxy-based resin, a vinyl ester-based resin, and the like, and the epoxy-based resins include bisphenol-based epoxy resins, no-blade-type epoxy resins, alicyclic epoxy resins, aliphatic epoxy resins, and these. And mixtures thereof. As the radical polymerization type photopolymerizable prepolymer, an acrylic prepolymer (hard prepolymer) having two or more acryloyl groups in one molecule and forming a three-dimensional network structure through crosslinking curing can be preferably used from the viewpoint of hard coating properties.

Examples of the acrylic prepolymer include urethane acrylate, polyester acrylate, epoxy acrylate, melamine acrylate, polyfluoroalkyl acrylate, silicone acrylate, and mixtures thereof. The urethane acrylate-based prepolymer can be obtained, for example, by esterifying a polyurethane oligomer obtained by reaction of polyether polyol or polyester polyol with polyisocyanate through reaction with (meth) acrylic acid. The polyester acrylate-based prepolymer is, for example, esterified with a (meth) acrylic acid hydroxyl group of a polyester oligomer having a receiver at both ends obtained by condensation of a polyhydric carboxylic acid with a polyhydric alcohol, or an alkylene oxide in a polyhydric carboxylic acid. It can be obtained by esterifying the hydroxyl group at the terminal of the oligomer obtained by adding a seed with (meth) acrylic acid. The epoxy acrylate-based prepolymer can be obtained, for example, by esterifying a relatively low molecular weight bisphenol-type epoxy resin or a noblock epoxy resin by reaction of an oxirane ring with (meth) acrylic acid.

Different additives may be added to the first hard coating layer and the second hard coating layer to provide additional functions required for each layer. For example, the first hard coating layer may include an antifouling agent, prevent fingerprints, stains, scratches, and the like and have excellent surface hardness. In addition, the second hard coating layer may include a leveling agent, which may facilitate mold formation or printing.

For example, the antifouling agent may be at least one selected from the group consisting of silicone polyether acrylate, polyether-modified acrylic functional siloxane, fluoropolyether and fluoroacrylic compound, and the leveling agent is a non-silicone acrylic compound And it may be one or more selected from the group consisting of a fluoroacrylic compound.

The antifouling agent and the leveling agent may be added in an amount of 0.001% to 3% by weight, or 0.01% to 1% by weight, respectively, based on the weight of the first hard coating layer and the second hard coating layer.

In addition, the first hard coating layer and the second hard coating layer may further include conventional additives such as an antioxidant, a light stabilizer, and a photoinitiator.

As a specific example, the first hard coating layer and the second hard coating layer may include a urethane acrylate oligomer resin having 4 to 10 functional groups or 4 to 8 functional groups or a resin derived therefrom, and organic for improving abrasion resistance. Silica and the like may be further included.

Also, both the first hard coating layer and the second hard coating layer may have excellent 3D formability.

First adhesive layer and second adhesive layer

The first adhesive layer is disposed between the core base layer and the first sheet to improve the bonding strength between them and impart formability. In addition, the second adhesive layer is disposed between the core substrate layer and the second sheet to improve the bonding force between them and impart formability.

The first adhesive layer and the second adhesive layer may have a thickness ratio of 1: 0.5 to 1: 1.5. When in the above range, the core substrate layer is centered, and has a more symmetrical structure up / down, so that curl generation can be suppressed. More specifically, the first adhesive layer and the second adhesive layer may have a thickness ratio of 1: 0.9 to 1: 1.1.

The thickness of the first adhesive layer and the second adhesive layer may be 1 μm to 50 μm, 3 μm to 30 μm, 5 μm to 20 μm, 5 μm to 15 μm, 7 μm to 12 μm, or 8 μm to 12 μm. have.

Specifically, the first adhesive layer and the second adhesive layer may have a thickness of 5 μm to 15 μm. When within the preferred thickness range, the interfacial adhesion is excellent and may be more advantageous for curl suppression.

The first adhesive layer and the second adhesive layer may include an adhesive resin and a curing agent.

The adhesive resin is not particularly limited, but may be, for example, a resin that can be cured by UV light irradiation, and accordingly, the first adhesive layer and the second adhesive layer may be prepared through UV curing. In addition, the adhesive resin may be a resin that is not yellowed by UV light and has good dispersibility in the UV absorber. For example, the adhesive resin includes polyester resin, acrylic resin, alkyd resin, amino resin, and the like. The adhesive resin may be used alone, or two or more copolymers or mixtures may be used. Among them, an acrylic resin excellent in optical properties, weather resistance, adhesion to a substrate, and the like is preferred. In addition, the adhesive resin may be an optically clear adhesive (OCA).

The curing agent is not particularly limited as long as it is a material capable of curing the adhesive resin. Specifically, one or more may be selected from the group consisting of isocyanate curing agents, epoxy curing agents, and aziridine curing agents that are not yellowed by UV light. In addition, the curing agent may be included in 0.2 to 0.5% by weight, 0.3 to 0.5% by weight, 0.3 to 0.45% by weight, or 0.35 to 0.45% by weight based on the weight of each of the first adhesive layer and the second adhesive layer.

Stacked structure example

According to a specific example, the plastic laminate may include a first adhesive layer disposed between the core substrate layer and the first sheet; And a second adhesive layer disposed between the core substrate layer and the second sheet, wherein the first hard coating layer and the second hard coating layer have a thickness ratio of 1: 0.9 to 1: 1.1, and the first substrate. The layer and the second base layer may have a thickness ratio of 1: 0.9 to 1: 1.1, and the first adhesive layer and the second adhesive layer may have a thickness ratio of 1: 0.5 to 1: 1.5.

Further, the core substrate layer has a thickness of 200 μm to 500 μm, the first substrate layer and the second substrate layer have a thickness of 100 μm to 200 μm, and the first hard coating layer and the second hard coating layer are It has a thickness of 3 μm to 10 μm, and the first adhesive layer and the second adhesive layer may have a thickness of 5 μm to 15 μm.

The total thickness of the plastic laminate may be 400 μm to 1000 μm, 500 μm to 900 μm, 500 μm to 750 μm, 700 μm to 900 μm, or 600 μm to 900 μm.

Curl change

The plastic laminate has very little curl change at high temperature.

For example, the plastic laminate may be left at 140 ° C. for 2 hours, and the edge curl change may be within 3.0 mm, within 2.0 mm, within 1.0 mm, within 0.5 mm, or within 0.3 mm. Specifically, the plastic laminate may have a curl change of height within 1.0 mm at the corner after leaving at 140 ° C for 2 hours.

In addition, the curl of the edge of the plastic laminate after standing at 100 ° C. for 72 hours may be within 3.0 mm, within 2.0 mm, within 1.0 mm, within 0.5 mm, or within 0.3 mm.

Manufacturing method of plastic laminate

The manufacturing method of the plastic laminate may include forming a first hard coating layer on the first substrate layer to obtain a first sheet; Forming a second hard coating layer on the second substrate layer to obtain a second sheet; Laminating the first sheet so that the first substrate layer faces on one surface of the core substrate layer; And laminating the second sheet so that the second substrate layer faces the other surface of the core substrate layer, wherein the first sheet and the second sheet have a thickness ratio of 1: 0.9 to 1: 1.1.

The step of stacking the first sheet on one surface of the core substrate layer and the step of stacking the second sheet on the other surface of the core substrate layer may be performed sequentially or simultaneously.

Preferably, the step of laminating the first sheet on one side of the core substrate layer and the step of laminating the second sheet on the other side of the core substrate layer are simultaneously performed, thereby forming a symmetrical structure to suppress curl generation. It can be more advantageous.

In addition, the method of manufacturing the plastic laminate, before the step of laminating the first sheet on one surface of the core substrate layer and the step of laminating the second sheet on the other surface of the core substrate layer, one surface of the core substrate layer And forming a first adhesive layer and a second adhesive layer on the other surface, respectively.

At this time, the first adhesive layer and the second adhesive layer may have a thickness ratio of 1: 0.5 to 1: 1.5.

Effects of plastic laminates

As described above, the plastic laminate according to the present invention includes a plastic film formed with a hard coating layer in a symmetrical structure, thereby minimizing curl generation even in a high temperature environment. In addition, the thickness and composition of each layer and the process conditions of the plastic laminate can be adjusted to improve dimensional stability as well as other properties such as antifouling properties and printability.

Molded body

The present invention also provides a plastic molded body molded from the plastic laminate.

The plastic molded body molded from the plastic laminate may have advantages of high durability and low cost.

Accordingly, the plastic molded body can be usefully applied as a front or rear cover of a mobile device by replacing a conventional glass material.

Such a plastic molded body may be manufactured by a process such as thermoforming from the plastic laminate, and during the molding process, curls are generated by layer-by-layer composition and composition of the plastic laminate, as well as curved portions of edges. In the crack generation can also be suppressed.

[Example]

The present invention will be described in more detail through the following examples. However, the following examples are only for illustrating the present invention, and the scope of the present invention is not limited thereto.

In the following examples, a V7610 product of SKC was used as a polyethylene terephthalate (PET) film, and a CCL series product of I-component was used as a polycarbonate (PC) film.

Example 1

1A. Film production

PET films or PC films were prepared in various thicknesses of a single layer (samples 1-1 to 1-7). In addition, a film in which two sheets of the PET film or the PC film were laminated was produced (samples 1-9 and 1-11).

In addition, a hard coating film was produced by coating a hard coating (HC) resin composition on the PET film to a thickness of about 15 μm (Sample 1-8). The hard coating resin composition was prepared by mixing 47.6 parts by weight of a urethane acrylate oligomer type resin (MIRAMER PU620NT, Miwon), 1.7 parts by weight of a curing agent (Irgacure 184, Ciba), and 50.7 parts by weight of a solvent (toluene). The hard coating resin composition was coated on the surface of the base layer using a Meyer bar coater, etc., and dried at 80 ° C. for 1 minute, followed by UV curing at 400 mJ / cm ² .

In addition, two sheets of the hard coating films prepared as described above were stacked so that their base layers contacted each other (sample 1-10). At the time of film lamination, an adhesive was applied to the abutting surface to a thickness of about 5 μm to adhere. As the adhesive, UV-type acrylate-based resin (TS-03, NCP Chem) was used. After applying the adhesive using a Meyer bar coater and laminating the films with a laminator, UV curing was performed under 400 mJ / cm ² conditions. Ordered.

1B. exam

To measure the initial curl of each film sample prepared, the maximum value of the excited heights of the four corners from the bottom of the film was measured. Then, the film was heat treated at 100 ° C for 72 hours, and curl was measured in the same manner. The curl change was calculated by subtracting the height of the initial curl from the measured curl height after the heat treatment.

The structures and evaluation results of the samples are shown in Table 1 below.

division Layer structure (without adhesive layer) Curl change Sample 1-1 PET (125㎛) 0 mm Sample 1-2 PET (188㎛) 0 mm Sample 1-3 PET (250㎛) 0.3mm Sample 1-4 PC (125㎛) 0 mm Sample 1-5 PC (200㎛) 0 mm Sample 1-6 PC (250㎛) 0 mm Sample 1-7 PC (380㎛) 0 mm Sample 1-8 HC (15㎛) / PET (188㎛) 34 mm Sample 1-9 PET (188㎛) / PET (188㎛) 2 mm Sample 1-10 HC (15㎛) / PET (188㎛) / PET (188㎛) / HC (15㎛) 3 mm Sample 1-11 PC (200㎛) / PC (200㎛) 0 mm

As shown in Table 1, the curl change of the hard coating film was larger than that of the PET or PC monolayer film. In addition, when two hard coating films were laminated in a symmetrical structure, the curl change was greater than when two PET or PC films were laminated, but the curl change was significantly less than that of a single hard coating film.

Example 2

2A. Film production

PET films or PC films were prepared in various thicknesses. A film in which the PET film and / or the PC film is laminated was produced (samples 2-2, 2-4, 2-6 to 2-10).

In addition, a hard coating (HC) resin composition on the PET film was coated to a thickness of about 15 μm to produce a hard coating film, which was laminated with a PET film and / or a PC film (Samples 2-1, 2-3, 2-5). At this time, the production, coating and curing conditions of the hard coating resin composition were the same as in Example 1.

At the time of lamination of the film, an adhesive was applied to the contact surface to a thickness of about 5 μm, and the adhesive type, application and curing conditions were the same as in Example 1.

2B. exam

For each prepared film sample, curl change was measured in the same manner as in Example 1, except that the heat treatment conditions were changed to 140 ° C and 2 hours.

The structures and evaluation results of the samples are shown in Table 2 below.

division Layer structure (without adhesive layer) Curl change Sample 2-1 HC (15㎛) / PET (250㎛) / PC (125㎛) / PET (250㎛) 13.0mm Sample 2-2 PET (250㎛) / PC (125㎛) / PET (250㎛) 11.5mm Sample 2-3 HC (15㎛) / PET (188㎛) / PC (250㎛) / PET (188㎛) 11.5mm Sample 2-4 PET (188㎛) / PC (250㎛) / PET (188㎛) 9.5mm Sample 2-5 HC (15㎛) / PET (125㎛) / PC (380㎛) / PET (125㎛) 7.5mm Sample 2-6 PET (125㎛) / PC (380㎛) / PET (125㎛) 7.0mm Sample 2-7 PET (250㎛) / PC (380㎛) 18.0mm Sample 2-8 PC (200㎛) / PET (250㎛) / PC (200㎛) 3.5mm Sample 2-9 PC (250㎛) / PC (300㎛) 2.5mm Sample 2-10 PET (250㎛) / PET (250㎛) 4.5mm

As shown in Table 2, when the upper and lower layers around the core layer are symmetrical structures, the curl change is less. In addition, when the thickness of the PC film (core layer) was 380 µm and the thickness of the PET film (base layer) was 125 µm, the curl change was the smallest.

Example 3

3A. Film production

A hard coating film was prepared by coating a hard coating (HC) resin composition on a PET film to a thickness of about 15 μm, and laminating it with a PC film and a PET film (Sample 3-1). At this time, the production, coating and curing conditions of the hard coating resin composition were the same as in Example 1.

In addition, a hard coating film was laminated on both sides of the PC film as a center (samples 3-2 to 3-5). At this time, the hard coating resin composition was diluted to change the hard coating thickness in the range of 9-15 μm.

At the time of lamination of the film, an adhesive was applied to the contact surface to a thickness of about 5 μm, and the adhesive type, application and curing conditions were the same as in Example 1.

3B. exam

For each prepared film sample, curl change was measured in the same manner as in Example 1, except that the heat treatment conditions were changed to 140 ° C and 2 hours.

The structures and evaluation results of the samples are shown in Table 3 below.

division Layer structure (without adhesive layer) Curl change Sample 3-1 HC (15㎛) / PET (125㎛) / PC (380㎛) / PET (125㎛) 7.5mm Sample 3-2 HC (15㎛) / PET (125㎛) / PC (380㎛) / PET (125㎛) / HC (15㎛) 5.5mm Sample 3-3 HC (13㎛) / PET (125㎛) / PC (380㎛) / PET (125㎛) / HC (13㎛) 5.5mm Sample 3-4 HC (11㎛) / PET (125㎛) / PC (380㎛) / PET (125㎛) / HC (11㎛) 4.5mm Sample 3-5 HC (9㎛) / PET (125㎛) / PC (380㎛) / PET (125㎛) / HC (9㎛) 3.5mm

As shown in Table 3, when the hard coating film was stacked on the top / bottom around the core layer (PC film), there was little curl change. In addition, the smaller the thickness of the hard coating layer, the less the curl change.

Example 4

4A. Film production

A hard coating film was prepared by coating a hard coating (HC) resin composition on a PET film to a thickness of about 9 μm. In this case, the following hard coating (HC) resin compositions were used in samples 4-1 to 4-3, respectively. Other coating and curing conditions of the hard coating resin composition were the same as in Example 1.

-Sample 4-1: 25.4 parts by weight of urethane acrylate oligomer type resin (100% by weight of solids, MIRAMER PU620NT, Miwon), 1.7 parts by weight of curing agent (Irgacure 184, Ciba), and 50.2 parts by weight of solvent (toluene)

-Sample 4-2: 47.6 parts by weight of urethane acrylate oligomer type resin (70% by weight of solids, D7, Miwon), 1.7 parts by weight of curing agent (Irgacure 184, Ciba), and 50.7 parts by weight of solvent (toluene)

-Sample 4-3: Urethane acrylate oligomer type resin (solid content 1000 wt%, D9, Miwon company) 25.4 parts by weight, curing agent (Irgacure 184, Ciba company) 1.7 parts by weight, and solvent (toluene) 50.2 parts by weight

Each of the hard coating films was laminated on both sides of the PC film. At the time of lamination of the film, an adhesive was applied to the contact surface to a thickness of about 5 μm, and the adhesive type, application and curing conditions were the same as in Example 1.

4B. exam

For each prepared film sample, curl change was measured in the same manner as in Example 1, except that the heat treatment conditions were changed to 140 ° C and 2 hours.

The structures and evaluation results of the samples are shown in Table 4 below.

division Layer structure (without adhesive layer) Curl change Sample 4-1 HC (9㎛) / PET (188㎛) / PC (380㎛) / PET (188㎛) / HC (9㎛) 3.5mm Sample 4-2 HC (9㎛) / PET (188㎛) / PC (380㎛) / PET (188㎛) / HC (9㎛) 2.0mm Sample 4-3 HC (9㎛) / PET (188㎛) / PC (380㎛) / PET (188㎛) / HC (9㎛) 2.5mm

As shown in Table 4, it was confirmed that the curl change was changed according to the composition of the hard coating layer. Specifically, the resin (MIRAMER PU620NT) used in the hard coating layer in Sample 4-1 is a high hardness hard coating oligomer having 6 functional groups, and the resin (D7) used in the hard coating layer in Sample 4-2 is flexible hard having 9 functional groups. As a coating oligomer, in general, when the hardness of the resin used in the hard coating layer is high, the wear resistance is high, but the occurrence of curls and cracks increases. On the contrary, when the resin hardness is low, the wear resistance is low, but the occurrence of curls and cracks tends to be small. . On the other hand, the resin (D9) used for the hard coating layer in Sample 4-3 was introduced as an organic silica as a flexible hard coating oligomer having 6 functional groups, and improved abrasion resistance while lowering the occurrence of curls and cracks.

Example 5

5A. Film production

A hard coating film was prepared by coating a hard coating (HC) resin composition on a PET film to a thickness of about 9 μm. At this time, the hard coating resin composition is a urethane acrylate oligomer type resin (solid content 70% by weight, D7, Miwon Co.) 47.6 parts by weight, curing agent (Irgacure 184, Ciba) 1.7 parts by weight, and solvent (toluene) 50.7 parts by weight It was prepared. The coating and curing conditions of the hard coating resin composition were the same as in Example 1 above.

Each of the hard coating films was laminated on both sides of the PC film. At the time of film lamination, the adhesive was applied to the contact surface with different thicknesses in the range of 5 to 10 μm, and other adhesive types, application and curing conditions were the same as in Example 1.

5B. exam

For each prepared film sample, curl change was measured in the same manner as in Example 1, except that the heat treatment conditions were changed to 140 ° C and 2 hours.

The structure and evaluation results of the samples are shown in Table 5 below.

division Layer structure (without adhesive layer) Adhesive thickness Curl change Sample 5-1 HC (9㎛) / PET (188㎛) / PC (380㎛) / PET (188㎛) / HC (9㎛) 5㎛ 2.0mm Sample 5-2 HC (9㎛) / PET (188㎛) / PC (380㎛) / PET (188㎛) / HC (9㎛) 7㎛ 1.0mm Sample 5-3 HC (9㎛) / PET (188㎛) / PC (380㎛) / PET (188㎛) / HC (9㎛) 10㎛ 0.5mm

As shown in Table 5, it was confirmed that the change in curl varies depending on the thickness of the adhesive layer.

Example 6

6A. Film production

On the PET film, a hard coating film was prepared by coating a hard coating (HC) resin composition with a different thickness within a range of 6 to 9 μm. In this case, the following hard coating (HC) resin compositions were used in samples 6-1 to 6-3, respectively. Other coating and curing conditions of the hard coating resin composition were the same as in Example 1.

-Sample 6-1: Urethane acrylate oligomer type resin (70% by weight of solids, D7, Miwon) 47.6 parts by weight, curing agent (Irgacure 184, Ciba) 1.7 parts by weight, and solvent (toluene) 50.7 parts by weight

-Sample 6-2: Urethane acrylate oligomer type resin (70% by weight of solids, D7, Miwon) 47.6 parts by weight, curing agent (Irgacure 184, Ciba) 1.7 parts by weight, and solvent (toluene) 56.8 parts by weight

-Sample 6-3: Urethane acrylate oligomer type resin (solid content 70% by weight, D7, Miwon) 47.6 parts by weight, curing agent (Irgacure 184, Ciba) 1.7 parts by weight, and solvent (toluene) 60.0 parts by weight

Each of the hard coating films was laminated on both sides of the PC film. At the time of lamination of the film, an adhesive was applied to the contact surface to a thickness of about 10 μm, and the adhesive type, application and curing conditions were the same as in Example 1.

6B. exam

For each prepared film sample, curl change was measured in the same manner as in Example 1, except that the heat treatment conditions were changed to 140 ° C and 2 hours.

The structures and evaluation results of the samples are shown in Table 6 below.

division Layer structure (without adhesive layer) Curl change Sample 6-1 HC (9㎛) / PET (188㎛) / PC (380㎛) / PET (188㎛) / HC (9㎛) 0.5mm Sample 6-2 HC (7㎛) / PET (188㎛) / PC (380㎛) / PET (188㎛) / HC (7㎛) 0.5mm Sample 6-3 HC (6㎛) / PET (188㎛) / PC (380㎛) / PET (188㎛) / HC (6㎛) 0.0mm

As shown in Table 6, it was confirmed that the curl change was changed according to the thickness of the hard coating layer.

Example 7

7A. Film production

A hard coating film was produced by coating a hard coating (HC) resin composition on a PET film to a thickness of 6 μm. At this time, the front / rear hard coating layers of Samples 7-1 and 7-2 were each of the following hard coating (HC) resin compositions. Other coating and curing conditions of the hard coating resin composition were the same as in Example 1.

-Sample 7-1 front / rear hard coating layer: urethane acrylate oligomer type resin (solid content 70% by weight, D7, Miwon) 47.6 parts by weight, curing agent (Irgacure 184, Ciba) 1.7 parts by weight, and solvent (toluene) 60.0 parts by weight

-Sample 7-2 front hard coating layer: urethane acrylate oligomer type resin (solid content 70% by weight, D7, Miwon) 47.6 parts by weight, curing agent (Irgacure 184, Ciba) 1.7 parts by weight, antifouling agent (KY-1203, ShinEtsu) 0.2 parts by weight and solvent (toluene) 50.7 parts by weight

-Back 7 hard coating layer of sample 7-2: urethane acrylate oligomer type resin (solid content 70 wt%, D7, Miwon company) 47.6 parts by weight, leveling agent (Flow-300; TEGO company) 1.7 parts by weight and solvent (toluene) 56.8 Parts by weight

Each of the hard coating films was laminated on both sides of the PC film. At the time of lamination of the film, an adhesive was applied to the contact surface to a thickness of about 10 μm, and the adhesive type, application and curing conditions were the same as in Example 1.

7B. exam

For each film sample prepared, the hard coating layer was evaluated as follows.

-Front hard coating layer: Measurement of contact angle with water

-Back hard coating layer: Measure surface tension using dyne pen (Acrotest)

The structures and evaluation results of the samples are shown in Table 7 below.

division Layer structure (without adhesive layer) Contact angle Surface tension Sample 7-1 HC (6㎛) / PET (188㎛) / PC (380㎛) / PET (188㎛) / HC (6㎛) 53˚ ≤26 dyne Sample 7-2 HC (6㎛) / PET (188㎛) / PC (380㎛) / PET (188㎛) / HC (6㎛) 110˚ 30 dyne

As shown in Table 7, the water contact angle was increased by adding an antifouling agent to the front hard coating layer, and accordingly, anti-pollution or anti-fingerprint properties could be exhibited on the front exposed to the outside. In addition, the surface tension was increased by adding a leveling agent to the back hard coating layer. In this case, it may be easy to form a mold for decoration or print the design.

Example 8

8A. Film production

Sample 4-1 prepared in Example 4 and Sample 7-1 prepared in Example 7 were prepared.

8B. exam

For the prepared samples, molding evaluation was performed through a thermoforming method. Specifically, it was tested under the following conditions using a heating molding apparatus (SHT-HTFC 001, Sungho Tech).

1) Molding temperature: 140 ℃

2) Molding time: preheating (10 seconds), molding (15 seconds), cooling (60 seconds)

3) Thermoforming jig: size (72.5mm x 155mm), edge curvature (4R)

The structure and evaluation results of the samples are shown in Table 8 below.

division Layer structure (without adhesive layer) Curl type Curl change Sample 4-1 HC (9㎛) / PET (188㎛) / PC (380㎛) / PET (188㎛) / HC (9㎛) torsion ≥5mm Sample 7-1 HC (6㎛) / PET (188㎛) / PC (380㎛) / PET (188㎛) / HC (6㎛) No curl 0 mm

As shown in Table 8, Sample 7-1 did not generate curl during heating molding.

In addition, in the case of Sample 7-1, no crack was found in the hard coating layer after heating molding, but in Sample 4-1, many cracks were found in the hard coating layer in the edge region.

Since the plastic molded article formed from the plastic laminate according to the present invention has advantages of high durability and low cost, it can be applied as a front or rear cover of a mobile device by replacing a conventional glass material.

10: first sheet, 20: second sheet,
100: core substrate layer,
210: first base layer, 220: second base layer,
310: first hard coating layer, 320: second hard coating layer,
410: first adhesive layer, 420: second adhesive layer.

Claims (15)

Core base layer;
A first sheet comprising a first substrate layer and a first hard coating layer sequentially disposed on one surface of the core substrate layer; And
A plastic laminate comprising a second sheet comprising a second substrate layer and a second hard coating layer, which are sequentially disposed on the other surface of the core substrate layer,
The first sheet and the second sheet have a thickness ratio of 1: 0.9 to 1: 1.1, the core substrate layer has a thickness of 300 μm to 500 μm, and the first substrate layer and the second substrate layer are 100 A urethane acrylate oligomer resin having a thickness of 3 to 6 μm and having a thickness of 3 to 6 μm and having a functional group of 6 to 10, and having a thickness of 200 μm to 200 μm and the first hard coating layer and a resin derived therefrom. And, after the plastic laminate is left at 140 ℃ for 2 hours, the plastic laminate having a curl (curl) change in height within 0.3 mm at the corners.
According to claim 1,
The first hard coating layer and the second hard coating layer further comprises an organic silica, plastic laminate.
According to claim 1,
The first hard coating layer and the second hard coating layer has a thickness ratio of 1: 0.9 to 1: 1.1,
The first substrate layer and the second substrate layer has a thickness ratio of 1: 0.9 to 1: 1.1, plastic laminate.
delete The method of claim 3,
The plastic laminate
A first adhesive layer disposed between the core substrate layer and the first sheet; And
Further comprising a second adhesive layer disposed between the core substrate layer and the second sheet,
The first adhesive layer and the second adhesive layer has a thickness ratio of 1: 0.5 to 1: 1.5, plastic laminate.
The method of claim 5,
The first adhesive layer and the second adhesive layer has a thickness of 5 ㎛ to 15 ㎛, plastic laminate.
According to claim 1,
The core substrate layer includes a polycarbonate resin,
The first base layer and the second base layer include a polyethylene terephthalate resin,
The first hard coating layer comprises an antifouling agent, the second hard coating layer comprises a leveling agent, a plastic laminate.
The method of claim 7,
The antifouling agent is at least one selected from the group consisting of silicone polyether acrylate, polyether-modified acrylic functional siloxane, fluoropolyether and fluoroacrylic compound,
The leveling agent is at least one selected from the group consisting of a non-silicone acrylic compound and a fluoroacrylic compound, a plastic laminate.
According to claim 1,
A first adhesive layer in which the plastic laminate is disposed between the core base layer and the first sheet; And a second adhesive layer disposed between the core substrate layer and the second sheet,
The first hard coating layer and the second hard coating layer has a thickness ratio of 1: 0.9 to 1: 1.1, and the first base layer and the second base layer have a thickness ratio of 1: 0.9 to 1: 1.1, and the first 1 adhesive layer and the second adhesive layer has a thickness ratio of 1: 0.5 to 1: 1.5,
The first adhesive layer and the second adhesive layer has a thickness of 5 ㎛ to 15 ㎛, plastic laminate.
According to claim 1,
The number of functional groups of the urethane acrylate-based oligomer resin is 9 to 10, a plastic laminate.
Forming a first hard coating layer on the first substrate layer to obtain a first sheet;
Forming a second hard coating layer on the second substrate layer to obtain a second sheet;
Laminating the first sheet so that the first substrate layer faces on one surface of the core substrate layer; And
A method of manufacturing a plastic laminate comprising the step of laminating the second sheet so that the second substrate layer faces the other surface of the core substrate layer,
The first sheet and the second sheet have a thickness ratio of 1: 0.9 to 1: 1.1, the core substrate layer has a thickness of 300 μm to 500 μm, and the first substrate layer and the second substrate layer are 100 A urethane acrylate oligomer resin having a thickness of 3 to 6 μm and having a thickness of 3 to 6 μm and having a functional group of 6 to 10, and having a thickness of 200 μm to 200 μm and the first hard coating layer and a resin derived therefrom. And, after the plastic laminate is left at 140 ℃ for 2 hours, having a curl (curl) change in height of less than 0.3 mm in the corner, the method of manufacturing a plastic laminate.
The method of claim 11,
A method of manufacturing a plastic laminate, simultaneously performing a step of laminating a first sheet on one surface of the core substrate layer and a step of laminating a second sheet on the other surface of the core substrate layer.
The method of claim 12,
Before the step of laminating a first sheet on one side of the core substrate layer and the step of laminating a second sheet on the other side of the core substrate layer,
The method further includes forming a first adhesive layer and a second adhesive layer on one surface and the other surface of the core substrate layer, respectively.
The first adhesive layer and the second adhesive layer has a thickness ratio of 1: 0.5 to 1: 1.5, the method of manufacturing a plastic laminate.
A plastic molded body molded from the plastic laminate of claim 1.
The method of claim 14,
The plastic molded body is applied to the front or rear cover of a mobile device, a plastic molded body.

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