KR102547535B1 - Laminated sheet - Google Patents

Abstract

TPO (thermoplastic polyolefin elastomer) base layer; a first primer layer laminated on the TPO base layer; a printed layer laminated on the first primer layer; and a TPO surface layer laminated on the printed layer; Including, a laminated sheet is disclosed.

Description

Laminated sheet {LAMINATED SHEET}

It relates to a laminated sheet, more specifically a TPO base layer; a first primer layer laminated on the TPO base layer; a printed layer laminated on the first primer layer; and a TPO surface layer laminated on the printed layer; It relates to a laminated sheet including.

In general, natural leather is widely used in products such as shoes, bags, wallets, various pouches, sofas, and clothing, but its resources are limited and it is not able to fully meet the demand, as well as various environmental problems and animal protection movements that began in Europe. The supply and demand tend to gradually decrease due to the spread of Therefore, as an alternative, artificial leather having various patterns formed on the surface is widely used.

Synthetic leather is usually manufactured by coating thin fabrics, knitted fabrics or non-woven fabrics with synthetic resins such as polyurethane (PU) and polyvinyl chloride (PVC). It is widely used as a material for making bags, clothes, etc.

However, PVC is always exposed to halogen gas, phthalate, and dioxin, and PU is also not free from hydrogen cyanide, DMF, formaldehyde, and MEK. In particular, PVC artificial leather generates hydrogen chloride gas in case of fire, which is harmful to the human body, and also generates a lot of volatile organic compounds (VOCs), which is not environmentally friendly.

An object of the present invention is to provide an eco-friendly and recyclable laminated sheet.

Another object of the present invention is to provide a useful laminated sheet as a lightweight material.

Another object of the present invention is to provide a laminated sheet excellent in abrasion resistance, scratch resistance, bending resistance, recovery and stain resistance.

1. According to one aspect, a laminated sheet is provided. The laminated sheet may include a TPO (thermoplastic polyolefin elastomer) base layer; a first primer layer laminated on the TPO base layer; a printed layer laminated on the first primer layer; and a TPO surface layer laminated on the printed layer; can include

2. In the above 1, the TPO surface layer may have an abrasion strength of 40,000 times or more measured under a load condition of 800 gr according to the Martindale method in accordance with KS K ISO 12947-2.

3. In the above 1 or 2, the TPO base layer and the first primer layer may be in direct contact, and the first primer layer and the printed layer may be in direct contact.

4. In any one of 1 to 3, a second primer layer or adhesive layer may be further included between the printing layer and the TPO surface layer.

5. In the above 4, the printing layer and the second primer layer or the adhesive layer may be in direct contact, and the second primer layer or the adhesive layer and the TPO surface layer may be in direct contact.

6. In any one of 1 to 5 above, an acrylic or urethane-based surface protection layer may be further included on the TPO surface layer.

7. In any one of 1 to 6, embossing may be formed on the surface of the TPO surface layer.

8. In any one of 1 to 7 above, the TPO base layer may be a TPO foam layer.

9. In any one of 1 to 8, at least one of the TPO base layer and the TPO surface layer is a hot melt adhesive resin, a filler, a reinforcing agent, a lubricant, a heat stabilizer, an antioxidant, a slip agent, a UV stabilizer, a colorant, and One or more of processing aids may be further included.

10. In any one of 1 to 9, the laminated sheet may have a bending resistance of 50,000 times or more as measured in accordance with KS M ISO 17694.

The present invention has the effect of providing a laminated sheet that is environmentally friendly, recyclable, useful as a lightweight material, and has excellent abrasion resistance, scratch resistance, bending resistance, restoration and stain resistance.

1 schematically illustrates a laminated sheet according to one embodiment of the present invention.
2 schematically shows a laminated sheet according to another embodiment of the present invention.

In this specification, expressions in the singular number include plural expressions unless the context clearly dictates otherwise.

Like reference numbers designate like elements throughout the specification. In addition, in describing the present invention, if it is determined that a detailed description of related known technologies may unnecessarily obscure the subject matter of the present invention, the detailed description will be omitted.

When the positional relationship of two parts is described by 'over', 'over', 'under', 'beside', etc., between the two parts unless 'immediately' or 'directly' is used. One or more other parts may be located in

In describing the drawings, positional relationships such as 'top', 'top', 'bottom', and 'bottom' are only described based on the drawings, and do not represent absolute positional relationships. That is, the positions of 'upper' and 'lower' or 'upper surface' and 'lower surface' may be changed depending on the observation position.

In this specification, terms such as include or have mean that the features or elements described in the specification exist, and do not preclude the possibility that one or more other features or elements may be added.

Terms such as first and second used in this specification may be used to describe various components, but the components should not be limited by the terms. Terms are only used to distinguish one component from another.

In interpreting the components, even if there is no separate explicit description, it is interpreted as including the error range.

In the present specification, "a to b" representing a numerical range, "to" is defined as ≥a and ≤b.

Hereinafter, a laminated sheet according to an embodiment of the present invention will be described with reference to the drawings.

1 schematically illustrates a laminated sheet according to one embodiment of the present invention.

Referring to Figure 1, the laminated sheet 100 according to one embodiment of the present invention is a TPO base layer 110; a first primer layer 120 laminated on the TPO base layer 110; a printed layer 130 laminated on the first primer layer 120; and a TPO surface layer 140 laminated on the printed layer 130; can include

The TPO base layer 110 may be a film including thermoplastic polyolefin (TPO). TPO is an eco-friendly material that has both the elasticity of rubber and the thermoplasticity of plastic, and is advantageous in manufacturing laminated sheets because of its excellent recovery, shock absorption, processability, workability, flexibility, stain resistance, light weight, and recyclability. TPO may include olefinic resins and olefinic rubbers, examples of olefinic resins include polyethylene (PE) and polypropylene (PP), and examples of olefinic rubbers include ethylene-propylene monomer (EPM) rubber, ethylene-propylene-diene monomer (EPDM) rubber, and the like, but are not limited thereto. TPO can be divided into C-TPO (compound thermoplastic polyolefin) and R-TPO (reactor thermoplastic polyolefin) depending on the manufacturing method. It is prepared through a polymerization reaction using a metallocene catalyst or the like, and the TPO base layer 110 may include C-TPO, R-TPO, or both. For example, the TPO base layer 110 may include C-TPO and/or R-TPO including PE and/or PP and EPM and/or EPDM.

According to one embodiment, the TPO base layer 110 may be a TPO foam layer. In this case, the texture of the laminated sheet may be more soft. The TPO foam layer may be prepared by incorporating a foaming agent into a composition for forming a TPO base layer and foaming, but is not limited thereto.

According to one embodiment, the TPO base layer 110 may have a multilayer structure in which two or more TPO layers are stacked. In this case, it may be easier to control the physical properties of the laminated sheet.

According to one embodiment, the TPO base layer 110 includes, in addition to TPO, a hot melt adhesive resin, a filler, a reinforcing agent, a lubricant, a heat stabilizer, an antioxidant, a slip agent, and UV as necessary within a range not impairing the object of the present invention. Stabilizers, colorants, processing aids and the like may be further included alone or in combination of two or more. These may be included in 0.1 to 30% by weight, for example, 0.1 to 15% by weight of the total weight of the TPO base layer 110, but the content may be changed as needed.

The thickness of the TPO base layer 110 is not particularly limited and may vary depending on required physical properties. For example, when high softness is required, the thickness needs to be thin and the hardness low, and on the contrary, when high hardness is required, the thickness needs to be thick and the hardness high. . According to one embodiment, the thickness of the TPO base layer 110 may be 10 to 900 μm, and softness and hardness of the laminated sheet may be easily controlled in the above range, but is not limited thereto.

The manufacturing method of the TPO base layer 110 is not particularly limited, but may be manufactured in the form of a film through, for example, a calendering process or a T-die extrusion process.

A first primer layer 120 may be stacked on the TPO base layer 110 . The first primer layer 120 may improve adhesion between the TPO base layer 110 and the printed layer 130 . In general, since TPO is non-polar, it is difficult to attach a print on the TPO base layer 110, and even if the print is attached, there may be a problem in that it is easily removed by external factors. However, this problem can be solved when the first primer layer 120 is formed between the TPO base layer 110 and the printed layer 130 like the laminated sheet according to one embodiment of the present invention.

The first primer layer 120 may include a compound having polarity as a primer. For example, the first primer layer 120 may include a chlorinated polyolefin-based primer or a polyurethane-based primer (eg, a one-component or two-component polyurethane-based primer). Examples of the chlorinated polyolefin-based primer include, but are not limited to, chlorinated polypropylene (CPP) primers.

According to one embodiment, the TPO base layer 110 and the first primer layer 120 may be in direct contact. Here, 'direct contact' may mean that no other layer is interposed between the TPO base layer 110 and the first primer layer 120 .

The thickness of the first primer layer 120 is not particularly limited, but may be, for example, 3 to 100 μm, and sufficient adhesion may be provided between the TPO base layer 110 and the printed layer 130 within the above range. .

A method of forming the first primer layer 120 is not particularly limited, but may be formed by coating a primer on the TPO base layer 110 , for example. As the coating method, various methods such as gravure coating, spray coating, and micro gravure coating may be used without limitation.

A printing layer 130 may be stacked on the first primer layer 120 . The printed layer 130 may play an important role in determining the final appearance of the laminated sheet by imparting a pattern to the laminated sheet 100 .

According to one embodiment, the printing layer 130 may include acrylic or urethane-based ink. In this case, due to the polarity of the acrylic or urethane-based ink, adhesion to the first primer layer 120 including the chlorinated polyolefin-based primer or polyurethane-based primer may be excellent.

According to one embodiment, the first primer layer 120 and the printed layer 130 may be in direct contact.

The method of forming the printing layer 130 is not particularly limited, but, for example, a printed material may be printed on the first primer layer 120 using a gravure method, a photocopy (digital print) method, a transfer method, or the like, and A printing method may be appropriately selected according to the desired resolution, printing quality, and the like.

A TPO surface layer 140 may be stacked on the printed layer 130 . The TPO surface layer 140 can protect printed matter, maintain transparency to improve visual quality, and impart surface durability to the laminated sheet 100. In addition, if necessary, the TPO surface layer 140 may be given a color.

The TPO surface layer 140 may be a film containing TPO. For a description of TPO, refer to the description of TPO in the TPO base layer 110.

According to one embodiment, the TPO surface layer 140 may have a multilayer structure in which two or more TPO layers are stacked. In this case, by laminating TPO layers with different physical properties (for example, by providing a foam layer to a specific layer), it is possible to design a laminated sheet with new physical properties, making it easier to control the physical properties of the laminated sheet.

According to one embodiment, the TPO surface layer 140 includes, in addition to TPO, a hot-melt adhesive resin, a filler, a reinforcing agent, a lubricant, a heat stabilizer, an antioxidant, a UV stabilizer, and a colorant as needed within a range not impairing the object of the present invention. , Processing aids, etc. may be included singly or in combination of two or more. These may be included in 0.1 to 30% by weight, for example, 0.1 to 15% by weight of the total weight of the TPO surface layer 140, but the content may be changed as needed.

The thickness of the TPO surface layer 140 is not particularly limited and may vary depending on required physical properties. For example, when high softness is required, the thickness needs to be thin and the hardness low, and conversely, when high hardness is required, the thickness needs to be thick and the hardness high. According to one embodiment, the thickness of the TPO surface layer 140 may be 10 to 900 μm, and softness and hardness of the laminated sheet may be easily controlled within the above range, but is not limited thereto.

The manufacturing method of the TPO surface layer 140 is not particularly limited, but may be manufactured in the form of a film through, for example, a calendering process or a T-die extrusion process.

According to one embodiment, the TPO surface layer 140 may have an abrasion strength of 40,000 times or more measured under a load condition of 800 gr according to the Martindale method in accordance with KS K ISO 12947-2. The abrasion strength of the TPO surface layer 140 may be, for example, 50,000 times or more, 60,000 times or more for another example, 70,000 times or more for another example, and 80,000 times or more for another example, but is not limited thereto. .

2 schematically shows a laminated sheet according to another embodiment of the present invention.

Referring to FIG. 2 , a second primer layer or an adhesive layer 250 may be further included between the printing layer 230 and the TPO surface layer 240 . For a description of the second primer layer 250 , refer to the description of the first primer layer 220 .

As the adhesive used in forming the adhesive layer, known adhesives may be used without limitation within a range that does not impair the object of the present invention. According to one embodiment, the adhesive may be a water-based adhesive or a solvent-free adhesive in consideration of VOC, odor, etc. Examples of the water-based adhesive may include a water-dispersed two-component urethane-based adhesive, but are not limited thereto.

The thickness of the second primer layer or adhesive layer 250 is not particularly limited, but may be, for example, 1 to 100 μm, and sufficient adhesion between the printed layer 230 and the TPO surface layer 240 can be provided within the above range. can

A method of forming the second primer layer or adhesive layer 250 is not particularly limited, but may be formed by coating a primer or an adhesive on the print layer 230 and/or the TPO surface layer 240, for example. As the coating method, various methods such as gravure coating, spray coating, and micro gravure coating may be used without limitation.

According to one embodiment, the printed layer 230 and the second primer layer or adhesive layer 250 may be in direct contact, and the second primer layer or adhesive layer 250 and the TPO surface layer 240 may be in direct contact.

According to one embodiment, an acrylic or urethane-based surface protection layer (not shown) may be further included on the TPO surface layers 140 and 240 . In this case, scratch resistance improvement, matte effect, etc. may be expressed by the surface protective layer.

According to one embodiment, embossing may be formed on the surfaces of the TPO surface layers 140 and 240 (not shown). In this case, a visual effect of texture may be expressed.

According to one embodiment, the laminated sheets 100 and 200 may have a bending resistance of 50,000 times or more as measured in accordance with KS M ISO 17694. The bending resistance of the laminated sheets 100 and 200 may be, for example, 60,000 times or more, another example of 70,000 times or more, and another example of 80,000 times or more, but is not limited thereto.

The above-described laminated sheet includes a TPO base layer / first primer layer / printed layer / TPO surface layer structure, so it is eco-friendly, effective in reducing VOC, useful as a lightweight material due to its low specific gravity, wear resistance, bending resistance, stain resistance, etc. this can be great

The above-described laminated sheet is prepared by, for example, forming a first primer layer on a TPO base layer, forming a printed layer on the first primer layer, and adhering a TPO surface layer on the printed layer. It can be. For example, forming a first primer layer by coating a primer on the TPO base layer in the form of a film; forming a printed layer by attaching a printed material on the first primer layer using a gravure method, a photocopy (digital print) method, a transfer method, or the like; In addition, after laminating a TPO surface layer in the form of a film on the printed layer, compression or thermal compression may be applied, or a primer or adhesive may be applied on the printed layer and/or the TPO surface layer, and then the printed layer and the TPO surface layer may be laminated and bonded. Optionally, a step of forming a surface protective layer by coating a coating agent for a surface protective layer, for example, an acrylic or urethane-based coating agent on the TPO surface layer may be further included. In addition, optionally, a step of forming embossing on the surface of the TPO surface layer may be further included, for example, the above-described TPO base layer / first primer layer / printed layer / (second primer layer or adhesive layer) / TPO surface layer Embossing can be formed on the surface of the TPO surface layer by passing the laminated sheet including / (surface protective layer) through an embossing roll.

The above-described laminated sheet may be used to manufacture artificial leather, for example. For example, the TPO base layer of the laminated sheet is laminated on the artificial leather fiber layer (backing cloth layer) giving the texture of artificial leather so that the TPO base layer is in contact with each other, and then compressed or heat-compressed, or between the artificial leather fiber layer and the TPO base layer. Artificial leather may be manufactured by applying an adhesive. Artificial leather manufactured using the above-described laminated sheet is eco-friendly and may have excellent moldability, stain resistance, abrasion resistance, bending resistance, etc., and may have bags, shoe skins, sofas, tables, exterior finishing materials for furniture, flooring materials, and automobile interior materials. etc. can be useful. However, the use of the laminated sheet is not limited thereto, and for example, the above-described laminated sheet may also be used for manufacturing decorative sheets and the like.

Hereinafter, the present invention will be described in more detail by way of examples. However, this is presented as a preferred example of the present invention, and cannot be construed as limiting the present invention by this in any sense.

Example

Example 1

First, the melt-flow index (MI) measured according to ASTM D1238 is 1g / 10min (190 ℃, 2.16kg), the Shore A hardness measured according to ASTM D2240 is 76, and the thickness is 180㎛ A primer (JR-650, Jinkwang Co.) was coated on a TPO film (Hanwha Solutions Co.) for a substrate layer by a gravure method (chamber temperature: about 80° C., speed: about 15 m/min) and dried to form a first primer layer. Thereafter, a printing layer was formed on the first primer layer by a gravure method (chamber temperature: about 100° C., speed: about 15 m/min). Then, MI measured according to ASTM D1238 is 3g / 10min (190 ℃, 2.16kg), Shore A hardness measured according to ASTM D2240 is 75, and thickness is 100㎛ TPO film for surface layer (Hanwha Solution Co., Ltd.) On top of the gravure method (chamber temperature: about 80 ℃, speed: about 10 m / min), the adhesive (KW-100, Heungin Chemical Co.) is coated and adhered to the printed layer, after aging at about 60 ℃ for 24 hours, embossing process (Temperature: about 180 ° C., pressure: about 50 kgf) to prepare a laminated sheet.

Example 2

As a TPO film for the surface layer, the MI measured according to ASTM D1238 is 1g / 10min (190 ℃, 2.16kg), the Shore A hardness measured according to ASTM D2240 is 75, and the TPO film has a thickness of 100㎛ (Hanwha Solutions Co., Ltd. A laminated sheet was prepared in the same manner as in Example 1, except that ) was used.

Comparative Example 1

Instead of attaching a TPO film for the surface layer on the printed layer, a urethane-based surface layer is formed using a gravure method (chamber temperature: about 100 ° C, speed: about 15 m / min) using a liquid urethane-based coating agent (KU-904, Heungin Chemical Co.) Except for one, a laminated sheet was prepared using the same method as in Example 1.

Comparative Example 2

Instead of attaching a TPO film for the surface layer on the printed layer, an acrylic surface layer is formed using a gravure method (chamber temperature: about 100 ° C, speed: about 15 m / min) using a liquid acrylic coating agent (KA-160, Heungin Chemical Co.) Except for one, a laminated sheet was prepared using the same method as in Example 1.

Comparative Example 3

Instead of attaching the TPO film for the surface layer on the printed layer, the gravure method ( Chamber temperature: about 100 ° C., speed: about 15 m / min), except that the urethane-based / acrylic surface layer was formed, using the same method as in Example 1 to prepare a laminated sheet.

Comparative Example 4

Instead of attaching the TPO film for the surface layer on the printed layer, a liquid two-component type urethane-based coating agent (KW-328, Heungin Chemical Co., Ltd.) is used and the gravure method (chamber temperature: about 150 ℃, speed: about 10 m/min) A laminated sheet was prepared in the same manner as in Example 1, except that the urethane-based surface layer was formed.

Comparative Example 5

A laminated sheet was prepared in the same manner as in Example 1, except that a TPU film (T-MAX, SKFC) was attached instead of attaching the TPO film for the surface layer on the printed layer.

The physical properties of the prepared laminated sheet were evaluated as follows, and the results are shown in Table 1 below.

Property evaluation method

(1) Abrasion resistance (unit: times): According to the KS K ISO 12947-2 standard, the abrasion strength of the surface of the laminated sheet was measured according to the Martindale method under a load condition of 800 gr.

(2) Flexural resistance (unit: times): The number of reciprocal bending (bending resistance) until lifting or surface cracking of the laminated sheet occurs at room temperature using a flexural strength test apparatus in accordance with KS M ISO 17694: 2004 standards was measured.

(3) Touch Feel: Through a tactile feel test, it was marked as O if the laminated sheet was soft and excellent in elasticity, X if not, and △ if it was unsatisfactory but usable.

Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Abrasion resistance (times) Over 80,000 Over 80,000 8,200 7,500 15,900 19,800 35,000 Flexibility (time) Over 80,000 Over 80,000 35,000 20,500 18,000 8,200 45,000 Touch Feel O O O X X X △

As can be seen from Table 1, the laminated sheet of Example 1-2 in which the TPO base layer, the first primer layer, the print layer, and the TPO surface layer are sequentially laminated is the laminated sheet of Comparative Example 1-4, which is not the case. It can be seen that the abrasion resistance, bending resistance, and touch feel are all excellent compared to this product.

So far, the present invention has been looked at mainly through embodiments. Those skilled in the art to which the present invention pertains will be able to understand that the present invention may be implemented in a modified form without departing from the essential characteristics of the present invention. Therefore, the disclosed embodiments should be considered from an illustrative rather than a limiting point of view. The scope of the present invention is shown in the claims rather than the foregoing description, and all differences within the equivalent scope will be construed as being included in the present invention.

100, 200: laminated sheet
110, 210: TPO base layer
120, 220: first primer layer
130, 230: printing layer
140, 240: TPO surface layer
250: second primer layer or adhesive layer

Claims (10)

A laminated sheet formed on a fiber layer for artificial leather, wherein the laminated sheet comprises
TPO (thermoplastic polyolefin elastomer) base layer;
a first primer layer laminated on the TPO base layer;
a printed layer laminated on the first primer layer; and
a TPO surface layer laminated on the printed layer; including,
In accordance with KS K ISO 12947-2, the abrasion strength measured under the 800gr load condition according to the Martindale method is more than 80,000 times,
In accordance with the KS M ISO 17694: 2004 standard, the number of reciprocal bending until lifting or surface cracking of the laminated sheet at room temperature using a flexural strength test device is 80,000 or more,
The first primer layer and the printing layer are in direct contact,
laminated sheet.
delete According to claim 1,
The laminated sheet in which the TPO base layer and the first primer layer are in direct contact.
According to claim 1,
Further comprising a second primer layer or an adhesive layer between the printed layer and the TPO surface layer, laminated sheet.
According to claim 4,
The printing layer and the second primer layer or the adhesive layer are in direct contact,
Wherein the second primer layer or the adhesive layer and the TPO surface layer are in direct contact.
According to claim 1,
Laminated sheet further comprising an acrylic or urethane surface protective layer on the TPO surface layer.
According to claim 1,
Laminated sheet in which embossing is formed on the surface of the TPO surface layer.
According to claim 1,
Wherein the TPO base layer is a TPO foam layer, laminated sheet.
According to claim 1,
At least one of the TPO base layer and the TPO surface layer contains at least one of a hot melt adhesive resin, a filler, a reinforcing agent, a lubricant, a heat stabilizer, an antioxidant, a slip agent, a UV stabilizer, a colorant, and processing aids. Further comprising a laminated sheet.
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