KR102404831B1 - Laminated film having the heterogeneous resin layer, and decorative sheet containing the same - Google Patents

Abstract

The present invention relates to a laminated film having a heterogeneous resin layer and a cosmetic sheet comprising the same, wherein the laminated film contains glycol-modified polyethylene terephthalate (PETG) and has excellent printing visibility and ink wettability as a printed layer on a heterogeneous resin layer. Since it is manufactured by thermal bonding of the substrate layer on the printing layer after forming, it not only has excellent printability, but also has excellent structural stability by including a plate-shaped inorganic filler in the heterogeneous resin layer, and shows appropriate gloss with low eye fatigue. Therefore, it can be usefully used for decorative sheets for building interior materials used for flooring.

Description

Laminated film having the heterogeneous resin layer, and a decorative sheet containing the same

The present invention is provided with a heterogeneous resin layer comprising a heterogeneous resin, specifically polyethylene terephthalate (PET) and glycol-modified polyethylene terephthalate (PETG), to provide excellent printing processability and structural stability, and a laminate film having low gloss and It relates to a cosmetic sheet including the same.

In general, residential flooring is mainly used for finishing the floors of living rooms and rooms of single-family houses or apartments. It provides a hygienic space by blocking dust and cold air from the cement floor. It also has a decorative effect, such as changing the interior atmosphere to a cozy place according to your taste.

Recently, with the improvement of the income level, the demand of consumers to pursue a pleasant and convenient quality of life is increasing. Currently, decorative sheets such as high pressure laminate (HPL), low pressure laminate (LPL), low pressure melamine (LPM), polyvinylchloride (PVC), and polycarbonate (PC) are used as flooring materials.

Among the cosmetic sheets, polyvinyl chloride (PVC) sheets are mainly used for mass production, and in particular, they have high hardness and light properties that can replace metal, glass, wood, paper, cloth, etc. have. However, the sheet including polyvinyl chloride (PVC) has poor heat resistance, so there is a problem in that yellowing occurs due to micro thermal deformation during processing or curling occurs when contacting a heat source due to a low softening point. In addition, since a plasticizer is used in manufacturing the sheet, when the printing layer is formed on the surface of the sheet, ink wetting is low, so that the printing effect cannot be sufficiently realized.

In recent years, studies to replace polyvinyl chloride (PVC) sheets with polyester films such as polyethylene terephthalate (PET) sheets have been actively conducted. However, since polyester films such as polyethylene terephthalate (PET) films have very high gloss, when laminating them on an adherend, it is difficult to accurately distinguish the color or designed patterns or patterns of the adherend due to light reflection, and users There is a problem that increases the fatigue of the eyes.

Therefore, there is an urgent need for the development of a flooring material with improved resistance to heat, excellent structural stability even at high temperatures, excellent ink wettability, etc. to improve printing processability and reduce user's eye fatigue.

Republic of Korea Patent Publication No. 2018-0026827

An object of the present invention is to provide a decorative sheet for flooring with improved resistance to heat, excellent structural stability even at high temperatures, excellent ink wettability, etc., so that print processability is improved and the user's eye fatigue is low.

Another object of the present invention is to provide a method for manufacturing the decorative sheet for flooring.

Accordingly, in order to solve the above problem,

The present invention in one embodiment,

base layer;

a printed layer provided on the base layer; and

It is provided on the printing layer and includes a heterogeneous resin layer comprising glycol-modified polyethylene terephthalate (PETG), polyester, and a plate-shaped inorganic filler,

When evaluating structural stability, it provides a laminated film that exhibits curling of 1T or less under cooling conditions of 22±2°C after 7 days at 80±2°C.

The present invention in one embodiment,

Forming a printing layer on the heterogeneous resin layer comprising glycol-modified polyethylene terephthalate (PETG), polyester, and a plate-shaped inorganic filler; and

Including bonding the substrate layer on the printed layer,

It provides a method for producing a laminated film, characterized in that the surface glossiness is 15 to 60 under 60 ° gloss conditions.

The present invention in one embodiment,

It provides a cosmetic sheet including the laminated film.

The laminated film according to the present invention contains glycol-modified polyethylene terephthalate (PETG) to form a printed layer on a heterogeneous resin layer having excellent print visibility and ink wettability, and then thermally bonding the substrate layer on the printed layer. In addition to excellent workability, since the heterogeneous resin layer contains a plate-shaped inorganic filler, it has excellent structural stability and exhibits appropriate gloss with low user's eye fatigue.

BRIEF DESCRIPTION OF THE DRAWINGS It is sectional drawing which shows the structure of the laminated|multilayer film of this invention.
2 is a cross-sectional view showing the structure of a laminated film provided with a heterogeneous resin layer containing a plate-shaped inorganic filler.

Since the present invention can have various changes and can have various embodiments, specific embodiments are illustrated in the drawings and described in detail in the detailed description.

However, this is not intended to limit the present invention to specific embodiments, and it should be understood to include all modifications, equivalents and substitutes included in the spirit and scope of the present invention.

In the present invention, terms such as "comprises" or "have" are intended to designate that the features, numbers, steps, operations, components, parts, or combinations thereof described in the specification exist, but one or more other features It should be understood that this does not preclude the existence or addition of numbers, steps, operations, components, parts, or combinations thereof.

In the present invention, the unit “T” is a unit indicating the thickness of a layer constituting the film, sheet or laminated film, and may be the same as the unit “mm”.

In the present invention, "total volatile organic carbon (TVOC)" is a hydrocarbon compound that volatilizes in the atmosphere to generate odor or ozone, and when measured by GC/MS, hexane (C ₆ ) to hexadecane (C ₁₆ ) It means the sum of the substances detected in the range.

The present invention relates to a laminated film and a cosmetic sheet comprising the same.

Recently, as the level of income increases, the demand of consumers to pursue a comfortable and convenient quality of life is increasing. , PVC (polyvinylchloride), PC (polycarbonate), such as cosmetic sheets are used.

Among the cosmetic sheets, polyvinyl chloride (PVC) sheets are mainly used for mass production, and in particular, they have high hardness and light properties that can replace metal, glass, wood, paper, cloth, etc. have. However, the sheet including polyvinyl chloride (PVC) has poor heat resistance, so there is a problem in that yellowing occurs due to micro thermal deformation during processing or curling occurs when contacting a heat source due to a low softening point. In addition, since a plasticizer is used in manufacturing the sheet, when the printing layer is formed on the surface of the sheet, ink wetting is low, so that the printing effect cannot be sufficiently realized.

In recent years, studies to replace polyvinyl chloride (PVC) sheets with polyester films such as polyethylene terephthalate (PET) sheets have been actively conducted. However, since polyester films such as polyethylene terephthalate (PET) films have very high gloss, when laminating them on an adherend, it is difficult to accurately distinguish the colors or designed patterns or patterns of the adherend due to the reflection of light, and users There is a problem that increases the fatigue of the eyes.

Accordingly, the present invention provides a laminated film having a heterogeneous resin layer and a cosmetic sheet including the same.

The laminated film according to the present invention contains glycol-modified polyethylene terephthalate (PETG) to form a printed layer on a heterogeneous resin layer having excellent print visibility and ink wettability, and then thermally bonding the substrate layer on the printed layer. In addition to excellent workability, since the heterogeneous resin layer contains a plate-shaped inorganic filler, it has excellent structural stability and exhibits appropriate gloss with low user eye fatigue, so it can be usefully used for decorative sheets used for flooring and the like.

Hereinafter, the present invention will be described in more detail.

laminated film

The present invention in one embodiment,

base layer;

a printed layer provided on the base layer; and

It is provided on the printing layer and includes a heterogeneous resin layer comprising glycol-modified polyethylene terephthalate (PETG), polyester, and a plate-shaped inorganic filler,

When evaluating structural stability, it provides a laminated film that exhibits curling of 1T or less under cooling conditions of 22±2°C after 7 days at 80±2°C.

The laminated film according to the present invention has a structure in which a base layer, a printing layer, and a heterogeneous resin layer are sequentially laminated, wherein the heterogeneous resin layer is a plate-shaped inorganic resin together with glycol-modified polyethylene terephthalate (PETG) and a polyester heterogeneous resin. It can be laminated on the base layer without a separate adhesive layer including fillers, and the wettability and haze of the ink are excellent, so the printing visibility is excellent, and the surface gloss is not high, so the user's eye fatigue is low, and the resistance to heat is improved It has excellent structural stability.

As an example, the laminated film may exhibit curling of 1T or less at 22±2°C cooling conditions after 7 days at 80±2°C when structural stability is evaluated. In general, resins exhibit intrinsic thermal shrinkage according to the type, but in the case of a film in which layers including different resins are laminated, there is a problem in that curling occurs even at low temperature changes due to different thermal shrinkage. However, since the laminated film according to the present invention contains a plate-shaped inorganic filler of a certain size in the heterogeneous resin layer and has excellent resistance to high temperatures of 80°C or higher, the structural stability of the laminated film is improved, and after 7 days at 80±2°C Under the cooling conditions of 22±2℃, curling of 1T or less may occur, and specifically, curling of 0.9T or less, 0.9T or less, 0.8T or less, 0.7T or less, 0.6T or less, or 0.5T or less may occur. In some cases, culling does not occur at all, indicating 0T culling.

As another example, the multilayer film may be 15 to 60 under a Gloss 60° condition when evaluating surface glossiness. Specifically, the laminate film has a surface gloss of 15 to 50, 15 to 40, 15 to 30, 20 to 60, 20 to 40, 30 to 50, 40 to 50, 15 to 25, 18 to 22, 20 to 35 , 22-32, 25-35, 24-31, 24-28, 24-26, 28-31, 29-32, 29-35, 26-32, 27-31, 28-32, 29-46, 42 to 47, 44 to 46, or 28 to 47.

In the laminated film according to the present invention, a printed layer 20 and a heterogeneous resin layer 30 are sequentially laminated on the base layer 10 as shown in FIG. As shown in b), it may have a structure in which the coating layer 40 is further laminated on the heterogeneous resin layer 30 .

Hereinafter, each configuration of the laminated film according to the present invention will be described in more detail with reference to FIG. 1 .

First, the base layer 10 is a layer serving as a base of the laminated film, and may include at least one selected from the group consisting of polyvinyl chloride (PVC) and polyethylene terephthalate (PET).

In addition, the base layer 10 is not particularly limited as long as it includes a film or sheet containing at least one of polyvinyl chloride (PVC) and polyethylene terephthalate (PET), and specifically, an easy layer, A calendered polyvinyl chloride (PVC) sheet and a white layer may be sequentially stacked. Here, the white layer may be located on the surface on which the printing layer 20 is formed so as to conceal the color of the base layer 10 in order to assist the clarity and realism of the printed pattern of the printing layer 20 . In addition, the white layer may include polyvinyl chloride (PVC) as a main component, but is not limited thereto, and when a barium-zinc stabilizer is included as an additive, heat resistance stability may be improved, and inorganic materials such as calcium carbonate When the filler is included, the hardness of the laminated film may be improved, and heat may be dispersed when heat is applied to the surface of the laminated film.

In addition, the average thickness of the base layer 10 is 150㎛ to 300㎛, or 150㎛ to 200㎛, 200㎛ to 250㎛, 250㎛ to 300㎛, 180㎛ to 220㎛, 240㎛ to 260㎛, 280 μm to 300 μm or 150 μm to 180 μm.

Next, the printing layer 20 is a layer formed of ink, and performs a function of imparting an aesthetic effect to the surface of the laminated film. The printing layer 20 may be formed by various printing methods used in the art, for example, offset, gravure, screen printing, roll-to-roll printing, etc., and since 2 to 4 patterns are printed by ink, the average thickness is several nm or less, and in some cases, thickness measurement may not be possible.

Next, the heterogeneous resin layer 30 is a transparent film layer having the same shrinkage in MD and TD directions extruded without stretching, and functions to improve print processability and structural stability of the laminated film.

Specifically, the heterogeneous resin layer 30 includes glycol-modified polyethylene terephthalate (PETG), polyester, and a plate-shaped inorganic filler, wherein the glycol-modified polyethylene terephthalate (PETG) is printed on the heterogeneous resin layer 30 . It serves to improve visibility and ink wettability.

As an example, the heterogeneous resin layer 30 may have a haze indicating print visibility of 80% or less based on ISO 7105, specifically 40 to 80%, 40 to 70%, 45 to 65%, 45 to 60 %, 45-55%, 48-53%, 45-53%, 48-58%, 55-68%, 55-65%, 40-50%, 55-75%, 58-72%, 62-77 %, 65 to 78% or 49 to 61%.

In addition, since the heterogeneous resin layer 30 has high surface energy, it has excellent wettability with respect to ink. Specifically, the heterogeneous resin layer 30 may have a surface energy of 40 mN/m or more, and more specifically, 40 mN/m or more, 45 mN/m or more, 50 mN/m or more, 40 mN/m to 70 mN/m, 40 mN/m to 60 mN/m, 40 mN/m to 55 mN/m, 40 mN/m to 50 mN/m, 40 mN/m to 45 mN/m, 42 mN/m to 46 mN/m, 43 mN/m to 48 mN/m, 43 mN/m to 45 mN/m, 45 mN/m to 60 mN/m, 45 mN/m to 55 mN/m, 48 mN/m to 53 mN/m, 50 mN/m to 55 mN/m, 52 mN/m to 58 mN/m, 53 mN/m to 55 mN/m, 51 mN/m to 58 mN/m, 55 mN/m to 65 mN/m, or from 58 mN/m to 62 mN/m.

In addition, the heterogeneous resin layer 30 may include polyester, but may include glycol-modified polyethylene terephthalate (PETG) together with polyester, and may be laminated on the base layer without a separate adhesive layer. The glycol-modified polyethylene terephthalate (PETG) is modified by partially using 1.4-cyclohexanedimethanol (CHDM) as a diol compound during polymerization of polyethylene terephthalate (PET), and has a crystallinity compared to polyethylene terephthalate (PET). Due to this low, molding is possible without whitening, and it has a relatively low melting point. Therefore, when a certain amount of glycol-modified polyethylene terephthalate (PETG) is included in the heterogeneous resin layer 30 together with polyester, thermal adhesiveness can be imparted, so that it can be laminated on the base layer without a separate adhesive layer.

Here, the heterogeneous resin layer 30 may include 10 to 40 parts by weight of polyester based on 100 parts by weight of glycol-modified polyethylene terephthalate (PETG), more specifically, 10 to 35 parts by weight of polyester; 10 to 30 parts by weight; 10 to 25 parts by weight; 15 to 40 parts by weight; 20 to 35 parts by weight; 20 to 30 parts by weight; 30 to 40 parts by weight; 22 to 32 parts by weight; 18 to 27 parts by weight; 17 to 23 parts by weight; 27 to 34 parts by weight; 22 to 28 parts by weight; Or 24 to 26 parts by weight may be included.

In the present invention, by adjusting the content ratio of glycol-modified polyethylene terephthalate (PETG) and polyester included in the heterogeneous resin layer 30 to the above range, the hardness of the surface of the laminated film is maintained constant while the printing visibility of the heterogeneous resin layer and the ink Wettability can be effectively improved, and the substrate layer 10 can be laminated on the surface of the heterogeneous resin layer 30 on which the printing layer 20 is formed without a separate adhesive layer by implementing appropriate adhesion.

In addition, the polyester included in the heterogeneous resin layer 30 is not particularly limited as long as it has high crystallinity and excellent surface hardness when cured. As an example, the polyester may be polyethylene terephthalate (PET). Unlike polybutylene terephthalate (PBT), which is polyester, the polyethylene terephthalate (PET) has high crystallinity and low elasticity, so that when applied to the heterogeneous resin layer 30 , excellent surface hardness can be realized.

In addition, the heterogeneous resin layer 30 is selected from the group consisting of ceramic particles such as kaolinite containing calcium carbonate, talc, wollastonite, silica, glass particles, silicon (Si) particles and aluminosilicate. One or more inorganic fillers 31 may be included.

Here, the inorganic filler 31 may be plate-shaped particles having a specific size. Specifically, the inorganic filler 31 may be plate-shaped particles having an average size of 0.1 to 100 μm and an average thickness of 5 μm or less, and more specifically, an average size of 0.1 to 90 μm, 0.1 to 80 μm, 0.1 to 70 μm, 0.1 to 60 μm, 0.1 to 50 μm, 0.1 to 40 μm, 0.1 to 30 μm, 0.1 to 20 μm, 0.1 to 10 μm, 10 to 90 μm, 20 to 80 μm, 30 to 70 μm, 40 to 60 μm, 45 to 55 μm, 30 to 55 μm, 42 to 53 μm, 47 to 61 μm, 0.1 to 15 μm 0.1 to 8 μm, 0.1 to 6 μm, 0.1 to 5 μm, 0.1 to 4 μm, 0.5 to 3 μm or 1 to 2.5 μm; average thickness of 5 μm or less, 4 μm or less, 3 μm or less, 2 μm or less, 1 μm or less, 0.1 to 5 μm, 0.1 to 4 μm, 0.1 to 3 μm, 0.1 to 2 μm, 0.1 to 1 μm, 0.5 to 5 μm, 0.5 to 3 μm, 0.5 to 2 μm, 0.5 to 1.5 μm, or 0.5 to 1 μm.

The present invention includes the plate-shaped inorganic filler 31 in the heterogeneous resin layer to not only improve the structural stability of the base layer 10 according to external temperature changes, but also to set the average size and thickness of the inorganic filler 31 within the above range By controlling as , it is possible to prevent an increase in user eye fatigue due to the high gloss of the laminated film and to prevent an excessive increase in haze of the heterogeneous resin layer 30 .

Furthermore, the inorganic filler is a total volatile organic compound generated in the base material layer 10, etc. located below the heterogeneous resin layer 30 as the inorganic filler 31 is positioned parallel to the heterogeneous resin layer 30 as shown in FIG. 2 . (TVOC) can be suppressed from being emitted to the outside of a laminated|multilayer film.

As an example, the laminated film contains the inorganic filler 31 in the heterogeneous resin layer 30 to measure the amount of total volatile organic compounds (TVOC) generated according to ASTM D5116 at 23±2° C. and 50±5% humidity may be an average of 0.055 mg/m 2 h or less, specifically 0.010 to 0.055 mg/m 2 h; 0.020 to 0.055 mg/m 2 h; 0.030 to 0.055 mg/m 2 h; 0.040 to 0.055 mg/m 2 h; 0.045 to 0.055 mg/m 2 h; 0.046 to 0.052 mg/m 2 h; 0.047 to 0.050 mg/m 2 h; 0.048 to 0.050 mg/m 2 h; 0.050 to 0.052 mg/m 2 h; 0.048 to 0.051 mg/m 2 h; 0.049 to 0.053 mg/m 2 h; or 0.050 to 0.052 mg/m 2 h.

In addition, the content of the inorganic filler 31 may be 5 to 30 parts by weight based on 100 parts by weight of glycol-modified polyethylene terephthalate (PETG) contained in the heterogeneous resin layer 30, specifically 5 to 25 parts by weight, 5 to 20 parts by weight, 5 to 15 parts by weight, 5 to 10 parts by weight, 10 to 20 parts by weight, 15 to 20 parts by weight, 10 to 15 parts by weight, 6 to 18 parts by weight, 7 to 15 parts by weight, 9 to 13 parts by weight, 15 to 27 parts by weight, 18 to 29 parts by weight, 22 to 26 parts by weight, 24 to 30 parts by weight, or 24 to 26 parts by weight.

In the present invention, by including the inorganic filler 31 in the above range in the heterogeneous resin layer 30 , it is possible to effectively control the surface gloss of the laminated film and the haze of the heterogeneous resin layer 30 . Specifically, the heterogeneous resin layer 30 includes the inorganic filler 31 in an amount of 11 to 13 parts by weight based on 100 parts by weight of glycol-modified polyethylene terephthalate (PETG), so that the haze according to ISO 7105 is 48 to 62, including it The laminated film may have a surface glossiness of 28 to 32 under 60° gloss conditions.

Meanwhile, the heterogeneous resin layer 30 may have a single-layer structure, and in some cases may have a multi-layer structure of two, three, or four or more layers. In addition, the average thickness of the heterogeneous resin layer 30 may be 20 to 80 μm, specifically, 30 to 70 μm, 35 to 65 μm, 40 to 60 μm, 45 to 55 μm, 30 to 60 μm, 45 to 80 μm, 45 to 75 μm or 48 to 52 μm.

Finally, the coating layer 40 may be selectively provided on the outermost surface of the laminated film to protect the heterogeneous resin layer 30 while controlling the gloss of the laminated film.

In addition, the type of the coating layer 40 is not particularly limited, but may be formed using a polyurethane dispersion (PUD), etc., and the polyurethane water dispersion (PUD) includes reactive particles. Contamination resistance of the coating layer 40 may be imparted. In this case, the form or size of the reactive particles is not particularly limited, but specifically, metal particles such as silicon (Si), aluminum (Al), and magnesium (Mg) may be included.

On the other hand, the average thickness of the laminated film according to the present invention may be 200㎛ to 350㎛, specifically 200㎛ to 250㎛, 250㎛ to 300㎛, 300㎛ to 350㎛, 230㎛ to 270㎛, 280㎛ to 330 μm, 240 μm to 260 μm, 290 μm to 310 μm, or 320 μm to 350 μm. The present invention can control the average thickness of the decorative sheet including the same by adjusting the average thickness of the laminated film in the above range.

Manufacturing method of laminated film

In addition, in one embodiment of the present invention,

Forming a printing layer on the heterogeneous resin layer comprising glycol-modified polyethylene terephthalate (PETG), polyester, and a plate-shaped inorganic filler; and

It provides a method of manufacturing a laminated film comprising the step of bonding a substrate layer on a printed layer.

The method for manufacturing a laminated film according to the present invention forms a printed layer by printing a desired pattern or pattern with ink on a heterogeneous resin layer, placing the substrate layer on one side of the heterogeneous resin layer on which the printing layer is formed, and applying heat to contact It can be done by

In general, when a plasticizer is included in the base layer, there is a problem in that the ink wettability of the surface is weak, so that the printing processability is remarkably low when the printing layer is formed. However, the manufacturing method of the laminated film according to the present invention preferentially comprises glycol-modified polyethylene terephthalate (PETG), polyester, and plate-shaped inorganic filler to form a printing layer on a heterogeneous resin layer having excellent ink wettability. By carrying out, the print processability of a laminated|multilayer film can be improved.

Here, the heterogeneous resin layer may be subjected to a corona or plasma treatment step before forming the printing layer in order to further improve the ink wettability. The heterogeneous resin layer according to the present invention exhibits a high surface energy of 40 to 50 mN/m, but is higher than the original 55 when the surface is corona or plasma treated. Since it exhibits a surface energy of to 70 mN/m, wettability with respect to the ink can be further improved.

In addition, since the heterogeneous resin layer according to the present invention contains glycol-modified polyethylene terephthalate (PETG) and can implement thermal adhesion at a certain temperature, a printing layer without a separate adhesive layer is formed on one side of the heterogeneous resin layer under constant temperature conditions. The step of bonding the base layer may be performed.

In this case, the step of bonding the base layer may be performed at 80 to 120° C. where the heterogeneous resin layer can implement thermal adhesion, and specifically 85 to 120° C., 90 to 120° C., 95 to 120° C., 80 to 110 °C, 80 to 105 °C, 85 to 110 °C, 95 to 105 °C, 98 to 110 °C, 85 to 103 °C or 97 to 104 °C.

In addition, the manufacturing method of the laminated film according to the present invention comprises the steps of corona or plasma treatment of the surface of the heterogeneous resin layer after bonding the base layer; and/or may further include forming a coating layer on the heterogeneous resin layer.

In the present invention, the gloss of the laminated film can be easily controlled by additionally forming a coating layer on the heterogeneous resin layer.

In this case, the coating layer may be formed on a heterogeneous resin layer having improved adhesion by increasing surface energy through corona or plasma treatment. In addition, the coating layer is formed by applying a polyurethane water dispersion (PUD) on the heterogeneous resin layer and drying it at a temperature of 80° C. or higher to prevent the occurrence of a characteristic odor due to the unreacted and residual initiator or monomer after curing. In this case, the coating method of the polyurethane water dispersion (PUD) may be used in a gravure or roll-to-roll method commonly used in the art. In addition, the polyurethane water dispersion (PUD) is reactive particles, for example, metal particles such as silicon (Si), aluminum (Al), magnesium (Mg), based on 100 parts by weight of polyurethane water dispersion (PUD) 5 to By including 15 parts by weight, it is possible to improve the stain resistance of the coating layer.

makeup sheet

Further, in one embodiment, the present invention provides a cosmetic sheet comprising the above-described laminated film.

The cosmetic sheet according to the present invention is lightweight by laminating a heterogeneous resin layer on a base layer without a separate adhesive layer, including the laminated film according to the present invention, as described above, and has a simple manufacturing process, as well as a low surface gloss, so that the user's eyesight It has features of low fatigue, excellent printing processability, excellent heat resistance, and high structural stability.

Hereinafter, the present invention will be described in more detail by way of Examples and Experimental Examples.

However, the following Examples and Experimental Examples are merely illustrative of the present invention, and the content of the present invention is not limited to the following Examples and Experimental Examples.

Preparation Examples 1 to 9.

Glycol-modified polyethylene terephthalate (PETG), polyester polyethylene terephthalate (PET and inorganic filler, kaolinite) were compounded as shown in Table 1 below, and extruded without a stretching process to prepare a heterogeneous resin layer. At this time, the average thickness of the heterogeneous resin layer was 50±1㎛, and the surface energy and haze according to ISO 7105 of each prepared heterogeneous resin layer were measured.

unit:
parts by weight Preparation Example 1 Preparation 2 Preparation 3 Preparation 4 Preparation 5 Preparation 6 Preparation 7 Preparation 8 Preparation 9 PETG 100 100 100 100 100 100 100 50 150 PET 25 25 25 25 25 25 25 25 25 weapon
filler content 12.5 10 25 6.25 12.5 12.5 12.5 12.5 12.5 shape plate type plate type plate type plate type rectangle plate type rectangle plate type plate type size 2㎛ 50㎛ 2㎛ 2㎛ 3㎛ 50㎛ >10㎛ 2㎛ 2㎛ thickness <2㎛ <5 μm <2㎛ <2㎛ - >5㎛ - <2㎛ <2㎛ haze 50 75 65 40 50 70 60 50 50 surface energy 44 mN/m 44mN/m 48 mN/m 44 mN/m 46 mN/m 44 mN/m 44 mN/m 50 mN/m 50 mN/m

Examples 1 to 3.

On the heterogeneous resin layer prepared in Preparation Examples 1 to 3, a three-degree pattern printing was performed by a gravure method to form a printed layer. Then, prepare a polyvinyl chloride (PVC, average thickness: 200±10㎛) film, place it on the side where the printed layer is formed, cut it to 15cm in width and 15cm in length, and then roll it with a heating roll at 95~105℃ ( Heating-roll) to prepare a laminated film.

The heterogeneous resin layer used Example 1 Film of Preparation Example 1 Example 2 Film of Preparation Example 2 Example 3 Film of Preparation Example 3

Example 4.

Corona treatment (surface energy: 54 mN / m) of the heterogeneous resin layer side of the laminated film prepared in Example 1, coating polyurethane water dispersion (PUD) by gravure coating method, and then drying in an oven at 80 ℃ to the outermost A laminated film in which a coating layer was formed on each layer was prepared. In this case, the polyurethane water dispersion (PUD) was used as reactive particles containing silicon (Si) particles (shape: spherical, average size: 5 μm) in an amount of 10% by weight.

Comparative Examples 1 to 6.

As shown in Table 3 below, a laminated film was prepared in the same manner as in Example 1, except that those prepared in Preparation Examples 4 to 9 were used as the heterogeneous resin layer on which the printing layer was formed.

The heterogeneous resin layer used Comparative Example 1 Film of Preparation Example 4 Comparative Example 2 Film of Preparation Example 5 Comparative Example 3 Film of Preparation Example 6 Comparative Example 4 Film of Preparation Example 7 Comparative Example 5 Film of Preparation Example 8 Comparative Example 6 Film of Preparation Example 9

experimental example.

In order to evaluate the physical properties of the laminated film according to the present invention, the laminated films prepared in Examples 1 to 3 and Comparative Examples 1 to 6 were subjected to surface glossiness, structural stability, print visibility, adhesion, and total volatile organic compounds (TVOC). ) was evaluated. The specific evaluation method is as follows, and the results are shown in Table 4 below:

A) Glossiness evaluation

A gloss meter (Gloss Meter) was used to measure 60° gloss (gloss 60° condition).

B) Structural stability evaluation

After each laminated film was left in an oven at 80±2° C. for 7 days, it was taken out of the oven and cooled at room temperature (22±2° C.), and the degree of warpage of the laminated film was measured in “T” unit using a vernier caliper.

C) Evaluation of print visibility

Each laminated film was observed with the naked eye, but the laminated film was positioned at a distance of 30 cm from the eye, and the printed pattern or pattern on the laminated film was visually observed to evaluate the print state. The evaluation criteria are as follows:

Good: Patterns or patterns are clearly observed.

Normal: The shape of the pattern or pattern is seen as blurry

Defect: Difficult to check the shape of the pattern or pattern

D) Adhesion

According to the evaluation method A of ASTM D3359, the surface of the laminated film was cut in an X shape having an angle of 30 to 45° and a length of about 40 mm (1.5 inch) with a knife. After that, a tape (length about 75 mm (3 inch)) was firmly attached to the cut surface along the letter X, and the peeling state of the cut X was confirmed by quickly peeling it off. It was assigned according to the confirmed peeling state, and the criteria were as follows:

Grade 0: X area completely peeled off;

Grade 1: Exfoliation of about 50% or more of the total area was confirmed;

Grade 2: Delamination of up to 3.2 mm (1/8 inch) on both sides of the cut X-shaped straight part is confirmed in a zigzag manner;

Grade 3: Delamination of about 1.6 mm (1/6 inch) on both sides of the cut X-shaped straight part is confirmed in a zigzag manner;

Grade 4: Traces of delamination or removal of less than about 5% of the total area along the straight line or intersection of the cut X are confirmed;

Grade 5: No delamination of the cut surface was observed.

E) Total amount of volatile organic compounds (TVOC) generated

The amount of total volatile organic compounds (TVOC) generated per unit area (m2) of the laminated film per hour at 23±2° C. and 50±5% humidity using a GC/MS analyzer according to ASTM D5116 was measured. At this time, total volatile organic compounds (TVOC) were limited to substances detected in the range of hexane (C ₆ ) to hexadecane (C ₁₆ ) when measured by GC/MS.

surface gloss structural stability print visibility adherence
[Rating] TVOC average
[mg/m2h] Example 1 30 0T Good 5 0.048 Example 2 30 0T Good 5 0.055 Example 3 20 0T usually 5 0.042 Comparative Example 1 50 2T Good 5 0.053 Comparative Example 2 60 5T Good 5 0.102 Comparative Example 3 35 0T error 5 0.059 Comparative Example 4 40 5T error 5 0.128 Comparative Example 5 40 10T error 5 0.064 Comparative Example 6 50 15T error 5 0.071

The laminated film according to the present invention can be laminated on a base layer without a separate adhesive layer, including a heterogeneous resin layer containing glycol-modified polyethylene terephthalate (PETG) and polyester, and has low surface gloss and print processability and It can be seen that the structural stability is excellent.

Specifically, the laminated films of Examples 1 to 3 containing glycol-modified polyethylene terephthalate (PETG) and polyester in a certain ratio in the heterogeneous resin layer showed low surface glossiness of about 30 or less, and resistance to heat was It was confirmed that warpage did not occur even after heat treatment at 80°C. In addition, in the laminated films of Examples 1 to 3, the shape of the printed pattern or pattern could be checked, and the adhesion between the base layer and the different resin layer was high, so that peeling did not occur even when the tape was attached to or detached from the X-cut part. It was found that the amount of TVOC generation was significantly lower.

On the other hand, the laminated film of Comparative Example 1 not including the inorganic filler had a surface glossiness of more than 30, and it was difficult to confirm the shape of the printed pattern or pattern, or was warped by heat. In addition, it was confirmed that the laminated films of Comparative Examples have a high amount of TVOC generation.

It is possible to improve the gloss of the laminated film as well as print processability and structural stability by providing a heterogeneous resin layer including glycol-modified polyethylene terephthalate (PETG), polyester, and plate-shaped inorganic fillers in the laminated film, and total volatile organic compounds This indicates that the amount of (TVOC) generation can be significantly reduced.

From these results, the laminated film according to the present invention is provided with a heterogeneous resin layer containing glycol-modified polyethylene terephthalate (PETG) and polyester in a certain ratio along with a plate-shaped inorganic filler to be laminated on the base layer without a separate adhesive layer. It can be seen that not only the surface glossiness is low, but also the print processability and structural stability of the laminated film are excellent.

10: base layer
20: printed layer
30: heterogeneous resin layer
31: inorganic filler
40: coating layer

Claims (15)

base layer;
a printed layer provided on the base layer; and
It is provided on the printing layer and includes a heterogeneous resin layer comprising glycol-modified polyethylene terephthalate (PETG), polyester, and a plate-shaped inorganic filler,
The surface energy of the heterogeneous resin layer is 40 mN/m or more,
When evaluating structural stability, a laminated film exhibiting curling of 1T or less under cooling conditions of 22±2℃ after 7 days at 80±2℃.
According to claim 1,
The laminated film, characterized in that the surface glossiness of the laminated film is 15 to 60 under 60° gloss conditions.
delete base layer;
a printed layer provided on the base layer; and
It is provided on the printing layer and includes a heterogeneous resin layer comprising glycol-modified polyethylene terephthalate (PETG), polyester, and a plate-shaped inorganic filler,
When evaluating structural stability, it exhibits curling of less than 1T at 22±2℃ cooling condition after 7 days at 80±2℃,
The heterogeneous resin layer has a haze according to ISO 7105 of 80% or less.
5. The method of claim 1 or 4,
The heterogeneous resin layer,
100 parts by weight of glycol-modified polyethylene terephthalate (PETG);
10 to 40 parts by weight of polyester, and
5 to 30 parts by weight of the inorganic filler.
5. The method of claim 1 or 4,
The inorganic filler is a laminated film comprising at least one selected from the group consisting of calcium carbonate, talc, wollastonite, silica, glass particles, silicon (Si) particles, and ceramic particles.
5. The method of claim 1 or 4,
The inorganic filler is a laminated film, characterized in that the particles having an average size of 0.1 to 100 μm and an average thickness of 5 μm or less.
5. The method of claim 1 or 4,
The base layer is a laminated film comprising at least one selected from the group consisting of polyvinyl chloride (PVC) and polyethylene terephthalate (PET).
5. The method of claim 1 or 4,
The laminated film is a laminated film further comprising a coating layer on the heterogeneous resin layer.
Forming a printed layer on a heterogeneous resin layer comprising glycol-modified polyethylene terephthalate (PETG), polyester, and a plate-shaped inorganic filler; and
Including bonding the substrate layer on the printed layer,
Bonding the substrate layer on the printed layer is performed at a temperature of 80 to 120 ℃,
The surface glossiness is 15 to 60 under the condition of Gloss 60°,
The heterogeneous resin layer is a method of manufacturing a laminated film, characterized in that the surface is corona-treated.
delete delete Forming a printed layer on a heterogeneous resin layer comprising glycol-modified polyethylene terephthalate (PETG), polyester, and a plate-shaped inorganic filler;
bonding the substrate layer on the printed layer; and
Comprising the step of forming a coating layer on the heterogeneous resin layer,
Bonding the substrate layer on the printed layer is performed at a temperature of 80 to 120 ℃,
The surface glossiness is 15 to 60 under the condition of Gloss 60°,
The coating layer is a method of manufacturing a laminated film formed by drying a polyurethane dispersion (PUD) containing reactive particles.
delete A cosmetic sheet comprising the laminated film according to claim 1 or 4.

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