KR20130113835A - Sheet having styrene co-polymer and olefin co-polymer, multilayer sheet and method of manufacturing the multilayer sheet using the same - Google Patents

Abstract

PURPOSE: A sheet has excellent polishing resistance, flame retardance, strength, and mechanical physical properties, has excellent embo-maintaining force, and is used for a vehicle interior. CONSTITUTION: A sheet includes an olefin-based copolymer and a styrene-based copolymer. The content of the styrene unit is 0.1-20 wt%. A multilayer sheet includes a display sheet laminated on the substrate sheet. A manufacturing method of the multilayer sheet comprises a step of arranging a substrate sheet and a cover sheet (S110); and a step of forming a multilayer sheet by synthesizing the cover sheet and the substrate sheet (S120). The cover sheet uses the sheet. [Reference numerals] (AA) Start; (BB) End; (S110) Arranging a substrate sheet and a cover sheet; (S120) Synthesizing the cover sheet and the substrate sheet; (S125) Forming embossing patterns; (S130) Crosslinking by irradiating electron beam

Description

SHEET HAVING STYRENE CO-POLYMER AND OLEFIN CO-POLYMER, MULTILAYER SHEET AND METHOD OF MANUFACTURING THE MULTILAYER SHEET USING THE SAME}

The present invention relates to a sheet manufacturing technology that can be utilized for automotive interior materials, and more particularly, by including the olefin copolymer and styrene copolymer together in the raw material for manufacturing the sheet, wear resistance, flame retardancy, strength and embossing retention An excellent sheet, a multilayer sheet using the same, and a method of manufacturing the same.

Typically, automotive interior materials are used polymer sheets. In the case of the polymer sheet, a single layer sheet or a multilayer sheet in which two or more sheets are laminated is used.

The polymer sheet used in the conventional automotive interior material mainly used polyvinyl chloride. However, with the recent suppression of the use of halogen-containing materials, polymer sheets using various polymers except polyvinyl chloride have been developed.

However, to date, most of the polymer sheet for automobile interior materials have problems such as insufficient wear resistance, flame retardancy, strength, or insufficient embossing force.

Background art related to the present invention is a flame-retardant olefin-based thermoplastic elastomer composition for the interior of the car interior disclosed in the Republic of Korea Patent Publication No. 10-0203220 (August 15, 1999.) and a laminate using the same.

SUMMARY OF THE INVENTION An object of the present invention is to provide a sheet having excellent mechanical properties such as wear resistance, flame retardancy, and strength, and having excellent emboss holding force.

Another object of the present invention is to provide a multi-layer sheet using a sheet having the above characteristics.

Still another object of the present invention is to provide a multi-layer sheet manufacturing method using the sheet having the above characteristics.

Sheet according to an embodiment of the present invention for achieving the above object comprises an olefin copolymer and a styrene copolymer, characterized in that the styrene unit content is 0.1 to 20% by weight.

In the sheet, the content of the olefinic unit may be 60 to 99% by weight, in which case, when the total amount of the styrene unit and the olefinic unit is less than 100% by weight, the remainder is one or more units except the styrene unit and the olefin unit. Can be done.

In this case, at least the olefin copolymer and the styrene copolymer may be crosslinked, or the styrene copolymer and the styrene copolymer may be crosslinked.

In addition, in the sheet, the olefin unit may include a propylene unit, an ethylene unit, at least one alkene having 3 to 8 carbon atoms, and an EPDM unit. In this case, 5 to 50 parts by weight of propylene units, 10 to 60 parts by weight of ethylene units, 1 to 50 parts by weight of one or more alkenes having 3 to 8 carbon atoms, and 0.1 to 50 parts by weight of EPDM units, based on 100 parts by weight of olefinic units. It may include.

In addition, the styrene-based copolymer in the sheet is polystyrene-block-poly (ethylene-ethylene / propylene) -block-hydroxyl-polystyrene (SEEPSOH), styrene- (ethylene / butylene) -styrene (SEBS) block copolymer, CEBC (crystalline block- (ethylene / butylene) -crystalline) block copolymer, HSBR (Hydrogenated styrene butadiene rubber), SEBC (Styrene- (ethylene / butylene) -crystalline) block copolymer, SEEPS (Polystyrene-block-poly (ethylene- ethylene / propylene) -block) polystyrene), SBS (Styrene-Butadiene-Styrene) copolymer, SEP (Polystyrene-block-poly (ethylene / propylene)) and SEPS (Polystyrene-block-poly (ethylene / propylene) -block- polystyrene) may include one or more.

Further, in the sheet, at least one additive selected from crosslinking agents, flame retardants, light stabilizers, ultraviolet absorbers, antioxidants, pigments, Talc, charcoal and lubricants based on 100 parts by weight of the olefin copolymer and the styrene copolymer combined The total amount may further include 20 parts by weight or less.

In addition, the sheet may be embossed pattern formed on the surface.

Multi-layered sheet according to an embodiment of the present invention for achieving the above another object includes a base sheet and a cover sheet laminated on the base sheet, the label sheet comprises an olefin copolymer and a styrene copolymer And, the styrene unit content is characterized by using a sheet of 0.1 to 20% by weight.

In this case, an embossed pattern may be formed on the surface of the cover sheet.

Multilayer sheet manufacturing method according to an embodiment of the present invention for achieving the above another object comprises the steps of preparing a cover sheet and a base sheet; And plywood the cover sheet and the base sheet to form a multilayer sheet, wherein the cover sheet includes an olefin copolymer and a styrene copolymer, and has a styrene unit content of 0.1 to 20% by weight. It characterized by using.

At this time, an embossed pattern may be formed on the surface of the cover sheet simultaneously with the plywood, or an embossed pattern may be formed on the surface of the cover sheet after the multilayer sheet is formed.

Further, at least the olefin copolymer and the styrene copolymer may be crosslinked or the styrene copolymer and the styrene copolymer may be crosslinked as the label sheet. Further, at least after the multilayer sheet is formed, The olefin copolymer and the styrene copolymer may be crosslinked, or the styrene copolymer and the styrene copolymer may be crosslinked.

The sheet according to the present invention is excellent in mechanical properties such as wear resistance, flame retardancy, strength, etc. by using polyolefin copolymer and polystyrene copolymer together, and optimally controlling the content of polystyrene units included in the sheet, and also has embossing retention There is an excellent advantage.

Accordingly, the seat according to the present invention can be usefully used for automobile interior materials and the like.

1 is a flow chart schematically showing a method for manufacturing a multilayer sheet according to the present invention.
Figure 2 shows the surface shape of the multilayer sheet prepared according to Examples 1 and 2 and Comparative Example 1.

Advantages and features of the present invention and methods of achieving them will become apparent with reference to the embodiments described in detail below. It should be understood, however, that the invention is not limited to the disclosed embodiments, but is capable of many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, To fully disclose the scope of the invention to those skilled in the art, and the invention is only defined by the scope of the claims.

Hereinafter, a sheet including a styrene copolymer and an olefin copolymer according to the present invention, a multilayer sheet using the same, and a method of manufacturing the same will be described in detail.

The sheet according to the present invention comprises an olefin copolymer and a styrene copolymer.

Polyolefin-based copolymers are excellent in strength and provide excellent emboss retention. In addition, the polyolefin-based copolymer has a particularly excellent moldability, thereby playing a role in facilitating sheet molding in the production of products such as automotive interior materials.

However, materials such as automotive interior materials are directly exposed to the user, and therefore, are required to have excellent wear resistance, flame retardancy, and strength. However, only the polyolefin copolymer itself has a limit in securing excellent wear resistance, flame retardancy, and strength.

Accordingly, the inventors of the present invention have conducted a lot of research, and as a result of using a polyolefin copolymer and a polystyrene copolymer as a sheet component, while excellent moldability, embossing retention, etc. of the polyolefin copolymer is maintained, wear resistance, flame retardancy, It was found that the intensity increased significantly.

In the case of the sheet according to the present invention, it may be composed of an olefin unit and a styrene unit or an olefin unit, a styrene unit and a third unit (for example, a siloxane unit). That is, the sheet component may be composed of only styrene units and olefin units, and if the total amount of styrene units and olefin units is less than 100% by weight, the remainder consists of third units.

In the sheet according to the invention, the styrene unit content is preferably 0.1 to 20% by weight. In the case of the styrene unit, it may be contained in the polystyrene-based copolymer, and some may be included in the polyolefin-based copolymer.

In the sheet according to the present invention, when the styrene unit content is less than 0.1% by weight, the effect of improving physical properties such as wear resistance, flame retardancy, strength and the like is insufficient. On the other hand, when the styrene unit content exceeds 20% by weight, the formability of the sheet may be lowered, making it difficult to manufacture a product having a desired shape.

In addition, the sheet according to the present invention may have an olefinic unit content of 60 to 99% by weight. When the content of the olefinic unit is less than 60% by weight, moldability and embossing retention may be lowered. On the contrary, when the content of the olefin unit exceeds 99% by weight, the styrene content is relatively decreased, so it is difficult to improve physical properties such as wear resistance, flame retardancy, and strength.

Olefinic units may include propylene units, ethylene units, one or more alkenes having 3 to 8 carbon atoms (eg, propene, butene, hexene, octene, etc.) and EPDM units.

The relative content of these units is not particularly limited, but with respect to 100 parts by weight of olefinic units, 5 to 50 parts by weight of propylene units, 10 to 60 parts by weight of ethylene units, 1 to 50 or more alkenes having 3 to 8 carbon atoms. When including the parts by weight and 0.1-50 parts by weight of the EPDM unit, it showed more excellent moldability and embossing retention, it is more preferable to include the olefin unit in the above range.

In the present invention, the styrene-based copolymer is polystyrene-block-poly (ethylene-ethylene / propylene) -block-hydroxyl-polystyrene (SEEPSOH), styrene- (ethylene / butylene) -styrene (SEBS) block copolymer, CEBC (crystalline) block- (ethylene / butylene) -crystalline) block copolymer, hydrogenated styrene butadiene rubber (HSBR), styrene- (ethylene / butylene) -crystalline block copolymer, polystyrene-block-poly (ethylene-ethylene / propylene) -block) polystyrene), SBS (Styrene-Butadiene-Styrene) copolymer, SEP (Polystyrene-block-poly (ethylene / propylene)) and SEPS (Polystyrene-block-poly (ethylene / propylene) -block-polystyrene) It may include one or more of them.

Meanwhile, in the sheet according to the present invention, the olefin copolymer and the styrene copolymer may be crosslinked. The crosslinking may be at least a crosslinked form of an olefin copolymer and a styrene copolymer, or a crosslinked form of a styrene copolymer and a styrene copolymer. In addition, a form in which the olefin copolymer and the olefin copolymer are crosslinked may also be included.

By crosslinking, tensile strength, abrasion resistance, flame retardancy, and the like can be further improved, and in particular, flame retardancy and embossing retention can be significantly increased. The degree of crosslinking may be about 5 to 60%, but is not necessarily limited thereto.

In addition, the sheet according to the present invention is one kind selected from crosslinking agents, flame retardants, light stabilizers, ultraviolet absorbers, antioxidants, pigments, Talc, coal stone and lubricants in order to improve the properties of crosslinking speed, antioxidant, flame retardancy, gloss, etc. It may further include the above additives. It is preferable that the sum total of such an additive is 20 weight part or less with respect to 100 weight part of sum total of an olefin type copolymer and a styrene type copolymer. When the content of the additive exceeds 20 parts by weight with respect to 100 parts by weight of the total amount of the olefin copolymer and the styrene copolymer, physical properties such as strength and moldability may be drastically lowered.

In addition, an embossed pattern may be formed on the sheet surface.

At this time, it is important that the embossed pattern is more precisely and uniformly formed, and in particular, the formed emboss is maintained. Referring to FIG. 2, in the case of the sheet according to the present invention, it can be seen that the formed fine emboss is maintained as it is.

The sheet according to the present invention can be used by itself, and can be used as a cover layer of a multilayer sheet.

The multilayer sheet to which the sheet according to the present invention is applied includes a base sheet and a cover sheet laminated on the base sheet. In this case, as described above, as described above, the sheet including the olefin copolymer and the styrene copolymer, the content of the styrene unit may be used a sheet of 0.1 to 20% by weight.

In addition, an embossed pattern may be formed on the surface of the cover sheet.

In the case of the base sheet, it may be a single layer structure, and may also be a multilayer structure in which two or more sheets are stacked. In addition, in the case of a base sheet, although there is no big limitation, it is more preferable to use what was formed from the composition containing the thermoplastic resin which is favorable for shaping | molding.

1 is a flow chart schematically showing a method for manufacturing a multilayer sheet according to an embodiment of the present invention.

Referring to FIG. 1, the illustrated multi-layer sheet manufacturing method includes a sheet preparing step S110 and a plywood step S120.

In the sheet preparing step (S110), a cover sheet and a base sheet are respectively provided. As described above, the cover sheet includes an olefin copolymer and a styrene copolymer, and a sheet having a content of styrene units of 0.1 to 20% by weight is used.

Next, in the plywood step (S120), the cover sheet and the base sheet are laminated to form a multilayer sheet.

Plywood of the cover sheet and the base sheet may be used in various ways such as a method using an adhesive, a thermocompression method.

In addition, in the method for manufacturing a multilayer sheet according to the present invention, an embossed pattern may be formed on the surface of the multilayer sheet. (S125) More specifically, when using a roll during plywood, a pattern opposite to the embossed pattern to be formed on the roll is formed. By forming, the embossed pattern can be formed by transferring the embossed pattern from the back surface of the cover sheet, more specifically from the back surface of the base sheet in contact with the roll, to the cover surface simultaneously with the plywood.

On the other hand, in the case of not using a roll, an embossed pattern may be formed on the surface of the cover sheet after the multilayer sheet is formed.

In addition, after the multilayer sheet is formed, crosslinking may be performed to at least crosslink the olefin copolymer and the styrene copolymer or to crosslink the styrene copolymer and the styrene copolymer. (S130) Of course, before plywood The cover sheet can be crosslinked in advance.

Example

Hereinafter, the configuration and operation of the present invention through the preferred embodiment of the present invention will be described in more detail. It is to be understood, however, that the same is by way of illustration and example only and is not to be construed in a limiting sense.

Details that are not described herein will be omitted since those skilled in the art can sufficiently infer technically.

1. Specimen Manufacturing

(1) Example 1

By weight%, consisting of 39.7% ethylene units, 9.5% propene units, 8.0% butene units, 2.6% hexene units, 11.7% octene units, 0.4% EPDM units, 4.0% styrene units, 0.1% siloxane units and the remaining propylene units A cover sheet was prepared.

As the base sheet, Keyflex TO1192A (manufactured by LG Chemical), which is a thermoplastic resin composition, was used.

Thereafter, the base sheet and the cover sheet were thermally pressed by passing through a roll having an embossed pattern while the base sheet and the cover sheet were heated to laminate the base sheet and the cover sheet. At this time, the embossed pattern was formed on the roll surface, and the multilayer sheet in which the embossed pattern was formed simultaneously with the plywood was manufactured.

(2) Example 2

Using the same cover sheet and base sheet as in Example 1, a multi-layer sheet was prepared in the same manner as in Example 1, and then crosslinked by irradiating an electron beam to the surface of the multi-layer sheet under an acceleration voltage of 800 kV and an electron beam irradiation current of 100 mA. After crosslinking, the degree of crosslinking was found to be 39.45%.

(3) Comparative Example 1

By weight%, a label sheet consisting of 35.5% ethylene units, 10.5% propene units, 2.5% butene units, 20.0% octene units, 1.0% EPDM units, 0.1% siloxane units, and remaining propylene units was prepared.

As the base sheet, Keyflex TO1192A (manufactured by LG Chemical), which is a thermoplastic resin composition, was used.

Thereafter, a multilayer sheet was prepared in the same manner as in Example 1.

2. Property evaluation result

Table 1 shows the physical property evaluation results of the multilayer sheets according to Examples 1 and 2 and Comparative Example 1.

[Table 1]

In Table 1, the tensile strength and elongation were measured according to the method of JIS K 6301. The abrasion resistance was evaluated by weight of before and after the test after scraping 2000 times using the method of SAE J365, to evaluate the weight loss rate (%). And flame retardance was performed horizontally by the MVSS 302 method, and the burning length was measured per minute.

Referring to Table 1, in Examples 1 to 2 in which the olefin copolymer and the styrene copolymer were applied together, the strength, wear resistance, and flame retardance were relative to those of Comparative Example 1, in which the label sheet made of the olefin copolymer was applied. Was excellent. In addition, compared to the multilayer sheet according to Example 1, which was not subjected to electron beam crosslinking, the multilayer sheet according to Example 2, which was subjected to electron beam crosslinking, was more excellent in strength, wear resistance, and flame resistance.

Figure 2 shows the surface shape of the multilayer sheet prepared according to Examples 1 and 2 and Comparative Example 1.

Referring to Figure 2, compared to the multilayer sheet according to Comparative Example 1, in the case of the multilayer sheet according to Examples 1 to 2, it can be seen that a finer and more uniform embossing pattern is formed.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims. . Accordingly, the true scope of the present invention should be determined by the following claims.

Claims (13)

An olefin copolymer and a styrene copolymer,
Styrene unit sheet, characterized in that 0.1 to 20% by weight.
The method of claim 1,
The sheet is
Olefin-based monomer content is 60 to 99% by weight,
When the total amount of the styrene unit and the olefin unit is less than 100% by weight, the sheet is characterized in that the remainder is composed of one or more units except for the styrene unit and the olefin unit.
The method of claim 1,
The sheet is
The olefin copolymer and the styrene copolymer are crosslinked,
A sheet characterized by crosslinking a styrene copolymer and a styrene copolymer.
The method of claim 1,
In the sheet,
Olefin-based monomers
A sheet comprising a propylene unit, an ethylene unit, at least one alkene unit having 3 to 8 carbon atoms, and an EPDM unit.
5. The method of claim 4,
5 to 50 parts by weight of propylene units, 10 to 60 parts by weight of ethylene units, 1 to 50 parts by weight of one or more alkenes having 3 to 8 carbon atoms, and 0.1 to 50 parts by weight of EPDM units, based on 100 parts by weight of the olefinic unit. Characterized in that the sheet.
The method of claim 1,
The styrenic copolymer
Polystyrene-block-poly (ethylene-ethylene / propylene) -block-hydroxyl-polystyrene (SEEPSOH), styrene- (ethylene / butylene) -styrene (SEBS) block copolymer, crystalline block- (ethylene / butylene) -crystalline ) Block copolymer, HSBR (Hydrogenated styrene butadiene rubber), SEBC (Styrene- (ethylene / butylene) -crystalline) block copolymer, SEEPS (Polystyrene-block-poly (ethylene-ethylene / propylene) -block) polystyrene, SBS (Styrene-Butadiene-Styrene) copolymer, SEP (Polystyrene-block-poly (ethylene / propylene)) and SEPS (Polystyrene-block-poly (ethylene / propylene) -block-polystyrene) Sheet made.
The method of claim 1,
In the sheet, at least one additive selected from a crosslinking agent, a flame retardant, a light stabilizer, an ultraviolet absorber, an antioxidant, a pigment, Talc, a coal and a lubricant, based on 100 parts by weight of the olefin copolymer and the styrene copolymer, is added 20 The sheet further comprises a weight part or less.
8. The method according to any one of claims 1 to 7,
An embossed pattern is formed on the surface of the sheet.
A base sheet and a cover sheet laminated on the base sheet,
The said cover sheet is a sheet | seat as described in any one of Claims 1-2, 4-7. The multilayer sheet characterized by the above-mentioned.
10. The method of claim 9,
An embossed pattern is formed on the surface of the cover sheet.
Preparing a cover sheet and a base sheet; And
Plywood the cover sheet and the base sheet to form a multilayer sheet; and
As said cover sheet, the sheet | seat of Claim 1 is used, The manufacturing method of the multilayer sheet characterized by the above-mentioned.
12. The method of claim 11,
Forming an embossed pattern on the surface of the cover sheet simultaneously with the plywood or forming an embossed pattern on the surface of the cover sheet after the multilayer sheet is formed.
12. The method of claim 11,
At least the olefin copolymer and the styrene copolymer are crosslinked, or the styrene copolymer and the styrene copolymer are crosslinked as the label sheet, or
After forming the multilayer sheet, at least, the olefin copolymer and the styrene copolymer crosslink, or the styrene copolymer and the styrene copolymer crosslink.

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