JP3238123B2 - Olefin resin multilayer film or sheet - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a flexible multilayer film or sheet made of an olefin resin used for stationery, various cases, packaging, agricultural use, etc.
For details, refer to "Film / Sheet"). For more information, refer to Soft multilayer film made of olefin resin with excellent suitability for high frequency welder, scratch resistance, heat resistance, and cutting property.
It is about a sheet.

[0002]

2. Description of the Related Art Conventionally, flexible films and sheets made of synthetic resin have been used for stationery, various cases, packaging, agricultural use, and the like. Further, as this film / sheet, a single-layer film / sheet made of an ethylene-methyl methacrylate copolymer resin or an ethylene-vinyl acetate copolymer resin is known.

[0003]

The single-layer film / sheet composed of the above-mentioned ethylene-methyl methacrylate copolymer resin or ethylene-vinyl acetate copolymer resin has the advantages of flexibility and excellent suitability for high-frequency welding. In terms of point, it can be said that it is suitable for use in the above applications that often require secondary processing, but on the other hand, it has the disadvantage that the surface is easily scratched (poor in scratch resistance). Various proposals have been made to improve the above, specifically, such as adding a fatty acid amide or forming a coating film on the surface.

[0004] However, in order to improve the scratch resistance by the above-described method, it is difficult to use a high frequency welder which is inherently provided in a film or sheet made of an ethylene-methyl methacrylate copolymer resin or an ethylene-vinyl acetate copolymer resin. In many cases, such characteristics as being excellent in the properties are impaired.

Further, a single-layer film or sheet made of an ethylene-methyl methacrylate copolymer resin or an ethylene-vinyl acetate copolymer resin is inferior in heat resistance, and tends to be deformed even at a temperature of about 80 to 90 ° C. There is also a drawback or a defect that the cutting property is inferior and the blade is hard to enter at the time of cutting, so that the vicinity of the end (the end formed by cutting) is elongated and easily deformed.

On the other hand, in order to solve the above-mentioned problems, an ethylene-methyl methacrylate copolymer resin or ethylene-methyl methacrylate
We also considered forming an outer layer made of polypropylene on both sides of a film or sheet made of vinyl acetate copolymer resin.However, when using a commonly used polypropylene, ethylene was used without using an adhesive or the like. -It was practically impossible to directly laminate a film / sheet surface made of a methyl methacrylate copolymer resin or an ethylene-vinyl acetate copolymer resin. Further, even if the outer layer made of a generally used polypropylene is laminated on a film / sheet surface made of an ethylene-methyl methacrylate copolymer resin or an ethylene-vinyl acetate copolymer resin via a commonly used adhesive, The resulting film / sheet also has a problem that the high-frequency welder suitability is lower than that of a single-layer film / sheet made of an ethylene-methyl methacrylate copolymer resin or an ethylene-vinyl acetate copolymer resin.

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and impairs the inherent properties of a film / sheet made of an ethylene-methyl methacrylate copolymer resin or an ethylene-vinyl acetate copolymer resin, which is excellent in high-frequency welder suitability. In addition, the present invention provides a film / sheet having improved surface scratch resistance, heat resistance and cutability.

[0008]

According to the present invention, there is provided a film / sheet comprising an intermediate layer made of an olefin resin and an outer layer, wherein the olefin resin forming the intermediate layer is ethylene. An olefin resin mainly composed of one or more selected from (meth) acrylate copolymer resin and ethylene-vinyl acetate copolymer resin, and an olefin resin forming an outer layer having a low melting point (140 ° C. or less) propylene; Ethylene-butene ternary la
Olefin-based resin multilayer film sheets, characterized in that the olefin resin mainly composed of random copolymer.

The olefin resin forming the intermediate layer of the olefin resin multilayer film / sheet of the present invention is selected from ethylene- (meth) acrylate copolymer resins and ethylene-vinyl acetate copolymer resins as described above. Is an olefin resin mainly composed of a resin or a mixture of two or more selected from these.

The ethylene- (meth) acrylate copolymer resin is obtained by copolymerizing ethylene with an acrylate ester and / or a methacrylate ester. Specifically, the above-mentioned ethylene-methyl methacrylate copolymer resin is used. In addition to the resin, an ethylene-methyl acrylate copolymer resin, an ethylene-ethyl acrylate copolymer resin, and the like can be used.

The ethylene- (meth) acrylate copolymer resin has a (meth) acrylate component content of 5 to 30% by weight, particularly 15 to 30% by weight in view of suitability for a high frequency welder. Is preferred.

Of course, the ethylene- (meth) acrylate copolymer resin may be a mixture of different types of (meth) acrylate and its content, etc., copolymerized with ethylene. . In addition, as long as the properties of the obtained film / sheet are not impaired,
A copolymer of a monomer component other than ethylene and (meth) acrylate may be used.

As the ethylene-vinyl acetate copolymer resin, a resin having a vinyl acetate component of 5 to 30% by weight, particularly 15 to 30% by weight from the viewpoint of suitability for high frequency welding is preferred.

Of course, the ethylene-vinyl acetate copolymer resin may be a mixture of resins having different vinyl acetate contents. Further, as long as the properties of the obtained film / sheet are not impaired, a copolymer of monomer components other than ethylene and vinyl acetate may be used.

If necessary, one or more olefin resins selected from ethylene- (meth) acrylate copolymer resins and ethylene-vinyl acetate copolymer resins constituting the intermediate layer may contain an antistatic agent, an antioxidant, etc. Agents, light stabilizers such as hindered amine compounds, lubricants, ultraviolet absorbers,
Various additives such as an inorganic filler and a coloring agent such as a pigment may be added.

The intermediate layer of the olefin resin multilayer film / sheet of the present invention comprises an ethylene- (meth) acrylate copolymer resin and an ethylene-vinyl acetate copolymer resin to which various additives are added as required. It is formed of one or more selected olefin-based resins. The ethylene- (meth) acrylate copolymer resin and ethylene-vinyl acetate described above may be used as long as the properties of the resulting film or sheet are not impaired. For copolymer resin,
Other polymers, specifically, low density polyethylene,
Polyethylene such as linear low-density polyethylene, medium-density polyethylene, and high-density polyethylene; polypropylene (including random and block copolymers of propylene and ethylene, that is, random polypropylene, block polypropylene, etc.); polybutene; ethylene-based elastomer; ; Etc. may be mixed.

In the multilayer film / sheet made of olefin resin of the present invention, outer layers made of olefin resin are formed on both surfaces of the above-mentioned intermediate layer. As described above, the olefin resin forming the outer layer is mainly composed of a propylene-ethylene-butene ternary random copolymer having a low melting point (melting point of 140 ° C. or lower) (hereinafter sometimes referred to as a low-melting point random polypropylene). It is an olefin resin.

The melting point referred to herein is a differential scanning calorimeter (Differential scanning calorimeter).
second run (2n)
(drun). By using such a low-melting-point propylene-ethylene-butene ternary random copolymer, the interlayer adhesion with the intermediate layer is improved, and the outer layer can be formed without the use of an adhesive or the like. Become.

The olefin resin forming the outer layer may include, if necessary, a light stabilizer such as an antistatic agent, an antioxidant, a hindered amine compound, a lubricant, an ultraviolet ray, similarly to the olefin resin forming the intermediate layer. Various additives such as an absorbent, an inorganic filler, and a coloring agent such as a pigment may be added.

As long as the properties of the obtained film / sheet are not impaired, polymers other than the above-mentioned olefinic resins, specifically, low-density polyethylene, linear low-density polyethylene, medium-density polyethylene, Polyethylene such as high-density polyethylene; ethylene-based copolymers such as ethylene- (meth) acrylate copolymer and ethylene-vinyl acetate copolymer; polypropylenes other than the above-mentioned low melting point random polypropylene; polybutene; ethylene-based elastomer; A system rubber; a hydrogenated styrene-butadiene rubber; a hydrogenated styrene-isoprene rubber; and the like may be mixed.

The olefin resin multilayer film sheet of the present invention has outer layers formed on both surfaces of the intermediate layer. The multilayer film sheet of the present invention has excellent interlayer adhesion between the intermediate layer and the outer layer. Since there is no need to interpose an adhesive between the two layers, a co-extrusion method or a co-extrusion inflation method whose production process is simple is preferably used as a forming means. Of course, the intermediate layer and the outer layer are formed by a calender method, an extrusion method,
The multi-layer film of the present invention can also be formed separately by means such as inflation and then laminated by means such as heat lamination or bonding with an appropriate adhesive.
You can get a sheet.

The thickness of the olefin-based resin multilayer film / sheet of the present invention is not particularly limited, but is generally in the range of 0.03 to 2.0 m.
m.

The ratio of the thickness of the intermediate layer to the thickness of each outer layer in the olefin resin multilayer film sheet of the present invention is preferably in the range of 2: 1 to 40: 1. When the thickness ratio of the intermediate layer and the outer layer deviates significantly from the above range, a multilayer film that can solve the problem of the present invention.
I can't get a sheet. Note that the thickness of both outer layers does not necessarily have to be the same.

The olefin-based resin multilayer film / sheet of the present invention can form an embossed pattern such as satin or silk on one or both sides, or can form a printed pattern by ordinary printing. In addition, it is also possible to form a coating film of various paints such as water-based, solvent-based, and ultraviolet-curing types.However, the portion where the coating film is formed is significantly reduced in suitability for a high-frequency welder. Need to keep this in mind. Of course, the same applies to the case of forming a print pattern.

The multilayer film / sheet made of the olefin resin of the present invention having the above-mentioned constitution is soft, has excellent scratch resistance and heat resistance, and does not contain a coloring agent or has a small amount of coloring agent. (That is, in the case of a colored transparent film or sheet), it is also excellent in transparency. Further, since it is excellent in high frequency welder suitability and cutting property, it is suitable for use in applications requiring secondary processing.

[0026]

EXAMPLES Specific examples of the present invention will be described below, but the present invention is not limited to the following examples.

[Examples 1 to 3 and Comparative Examples 1 to 3] Using an olefin resin composition for an intermediate layer and an olefin resin composition for an outer layer having the composition shown in Table 1, the olefin resin composition was used in a three-layer T-die extruder. Extruded to a total thickness of 0.3 mm and a middle layer thickness of 0.3 mm.
An olefin resin multilayer film having a thickness of 25 mm and a thickness of each outer layer of 0.025 mm was obtained. However, in Comparative Examples 2 and 3, a single-layer film having a thickness of 0.3 mm was formed without forming an outer layer. The obtained film was evaluated for suitability for high-frequency welder, scratch resistance, transparency, interlayer adhesion, heat resistance, and cutability according to the following criteria.

(A) Suitability for high-frequency welding ◎: welding possible without heating the welder blade ○: welding possible by heating the welder blade to 40-60 ° C. △: heating the welder blade to 70 ° C. or more Can be welded ×: High-frequency welding is practically impossible (b) Scratch resistance Gakushin-type friction tester (Kanakin No.3, 50 rubbing times)
), The haze value (unit%) was measured based on JIS-K-6714, and compared with the haze value before rubbing. ：: increase in haze value is less than 20% ×: increase in haze value is 20% or more (c) transparency ○: haze value is less than 10% ×: haze value is 10% or more (d) interlayer adhesion ：: good (high frequency) ×: Poor (peeling occurs between layers of each layer during welding of high frequency welder) (e) Heat resistance ○: Deformation observed even after leaving at 100 ° C. for 1 hour Not possible ×: Deformation is observed when left at 100 ° C. for 1 hour. (F) Cutability ：: No deformation of film edge is observed when 50 films are stacked and cut ×: 50 films Deformation is seen at the edge of the film when cut and stacked

[0029]

[Table 1]

For reference, FIG. 1 shows a partially enlarged cross-sectional view of the olefin resin multilayer film of Example 1. In the drawing, reference numeral 1 denotes an olefin resin multilayer film, reference numeral 11 denotes an intermediate layer, reference numerals 12 (a) and (b) denote outer layers,
Each is shown.

[0031]

As described in detail above, the olefin resin multilayer film / sheet of the present invention is excellent in high-frequency welder suitability, scratch resistance, heat resistance and cutting properties, for stationery, for various cases, for packaging, It can be suitably used for agricultural purposes and the like.

When the amount of the coloring agent is small or when no coloring agent is added, there is an advantage that the transparency is excellent.

Furthermore, the olefin resin multilayer film / sheet of the present invention has excellent interlayer adhesion even without an adhesive between the intermediate layer and the outer layer. It can be manufactured.

[Brief description of the drawings]

FIG. 1 is a partially enlarged sectional view of one embodiment of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Multilayer film made of olefin resin 11 ... Intermediate layer 12 (a), (b) ... Outer layer

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int. Cl. ⁷ , DB name) B32B 1/00-35/00

Claims (1)

(57) [Claims] 1. An olefin-based resin multilayer film or sheet comprising an olefin-based resin intermediate layer and olefin-based resin outer layers formed on both surfaces thereof, wherein the olefin-based resin forms the intermediate layer. Is an olefin resin mainly composed of at least one selected from ethylene- (meth) acrylate copolymer resin and ethylene-vinyl acetate copolymer resin, and the olefin resin forming the outer layer has a melting point of 140 ° C. or lower ( The melting point referred to herein is a differential scanning calorimeter (Differ).
initial scanning calorimet
er) An olefin-based resin multilayer film or sheet, which is an olefin-based resin mainly composed of a propylene-ethylene-butene ternary random copolymer having a maximum peak temperature of 2nd run in the analysis.