JPH09201863A - Production of laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a laminate free from surging and excellent in the appearance. SOLUTION: In producing a laminate composed of thermoplastic resin layer (/adhesive resin layer)/polyolefin resin layer (/adhesive resin layer)/saponified ethylene-vinyl acetate copolymer layer, a polyolefin resin and a saponified ethylene/vinyl acetate copolymer or an adhesive resin, a polyolefin resin and EVOH are subjected to co-extrusion to be laminated to the thermoplastic resin layer by melt extrusion coating.

Description

Detailed Description of the Invention

[0001]

The present invention relates to a thermoplastic resin layer (/ adhesive resin layer) / polyolefin resin layer (/ adhesive resin layer) / ethylene-vinyl acetate based on a thermoplastic resin such as vinyl chloride resin. The present invention relates to a method for producing a laminate comprising a saponified copolymer (hereinafter abbreviated as EVOH) layer, and more particularly to a method for producing a laminate having excellent appearance characteristics.

[0002]

2. Description of the Related Art Conventionally, vinyl chloride resin sheets and films have been used as decorative sheets for finishing wallpaper and furniture for architectural interiors, agricultural materials, automotive interior materials, and daily goods (vinyl mats, umbrellas). Etc.), as well as office supplies such as desk mats, file covers, notebook covers, stationery and the like. Then, a method of laminating EVOH in order to prevent the adverse effect of the plasticizer in the vinyl chloride resin has been proposed (Jpn. Pat. Appln. KOKAI Publication No. 2-47015), and in order to apply such a laminate to a decorative sheet, JP-A-6-328635. In the publication, a laminated body composed of a thermoplastic resin layer / adhesive resin layer / polyolefin resin layer / adhesive resin layer / EVOH layer by multi-layer coextrusion is described.

[0003]

However, such a laminate of vinyl chloride resin / EVOH and a laminate of thermoplastic resin layer / adhesive resin layer / polyolefin resin layer / adhesive resin layer / EVOH layer obtained by multi-layer coextrusion. When the present inventor studied in detail, considering the recent advancement of technology, the appearance physical properties are still unsatisfactory. Further, in the technology disclosed in JP-A-6-328635, the obtained laminate has It is difficult to obtain a laminate having a good appearance such as surging. Under the circumstances, the present invention provides a method for producing a laminate including a thermoplastic resin layer (/ adhesive resin layer) / polyolefin resin layer (/ adhesive resin layer) / EVOH layer having excellent appearance characteristics. The purpose is to provide.

[0004]

The inventors of the present invention have conducted extensive studies to solve such problems, and as a result, have found that the thermoplastic resin layer (/ adhesive resin layer) / polyolefin resin layer (/
Adhesive resin layer) / a saponified ethylene-vinyl acetate copolymer saponified layer is used to produce a thermoplastic resin layer containing a polyolefin resin and a saponified ethylene-vinyl acetate copolymer saponified resin (and an adhesive resin). The inventors have found that the above problems can be solved by melt-extrusion coating by extrusion, and have completed the present invention. In the present invention, in particular, the thermoplastic resin layer includes an adhesive resin, a polyolefin resin and an E resin.
Melt extrusion coating of VOH by coextrusion is preferred. In the present invention, the adoption of the adhesive resin layer is optional,
Both adhesive resin layers may be adopted, or only one adhesive resin layer may be adopted. Further, neither of them may be adopted, but preferably both adhesive resin layers are adopted.

[0005]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the production method of the present invention will be specifically described. Examples of the thermoplastic resin used in the thermoplastic resin layer of the present invention include vinyl chloride resin, polyester resin, acrylic resin, polystyrene resin, polyamide resin, and the like, but the effect of the present invention is most exerted. Then, vinyl chloride resin is preferably used.

As the polyolefin resin used for the polyolefin resin layer, high density polyethylene, medium density polyethylene, (linear) low density polyethylene, ultra low density polyethylene, vinyl acetate, acrylate ester or butene, and hexene are used. , Polyethylene copolymerized with α-olefins such as 4-methyl-1-pentene, polypropylene homopolymer, polypropylene grafted with ethylene, polypropylene copolymerized with α-olefins such as 4-methyl-1-pentene ,
Poly-1-butene, poly-4-methyl-1-pentene and modified polyolefins obtained by copolymerizing or graft-polymerizing unsaturated carboxylic acids or acid anhydrides thereof, vinylsilane compounds, epoxy group-containing compounds and the like with the above polyolefins. Examples of the resin include polyethylene such as high-density polyethylene, medium-density polyethylene, (linear) low-density polyethylene, ultra-low-density polyethylene, polypropylene homopolymer, polypropylene grafted with ethylene, and α-olefins. Polypropylene such as polymerized polypropylene and ethylene-vinyl acetate copolymer are preferably used.

Further, as EVOH used in the EVOH layer, ethylene content is 25 to 55 mol%, and further 28 to 4
A vinyl acetate component having a saponification degree of 8 mol% or more, 90 mol% or more, and further 95 mol% or more is preferably used. If the ethylene content is less than 25 mol%, the water resistance becomes insufficient, while 55 mol% If it exceeds, the barrier property will deteriorate, etc.
It is not preferable because the physical properties are insufficient. On the other hand, if the saponification degree is less than 90 mol%, the water resistance and the thermal stability become insufficient, which is not preferable. About melt index (MI)
40 g / 10 min (210 ° C., load 2160 g), preferably 2 to 15 g / 10 min is suitable. In addition, the EVOH is a small amount of propylene, isobutene, α-octene, α
Α-olefins such as dodecene and α-octadecene, unsaturated carboxylic acids or salts thereof, partial alkyl esters, complete alkyl esters, nitriles, amides, anhydrides, unsaturated sulfonic acids or comonomers such as salts thereof It doesn't matter.

In the present invention, a thermoplastic resin is used in producing a laminate comprising a thermoplastic resin layer (/ adhesive resin layer) / polyolefin resin layer (/ adhesive resin layer) / EVOH layer using these resins. The greatest feature of the layer is melt extrusion coating of a polyolefin resin and EVOH by coextrusion or melt extrusion coating of an adhesive resin, a polyolefin resin and EVOH by coextrusion, and such a method will be specifically described. .

The polyolefin resin layer and the EVOH layer are laminated on the thermoplastic resin layer. Upon lamination, the polyolefin resin and EVOH are melt extrusion coated by coextrusion using a known melt extruder. . In the present invention, a modified polyolefin resin such as a carboxylic acid modified resin is used as an adhesive resin layer in 3 types and 3 layers (polyolefin type resin layer / adhesive resin layer / EVOH layer) or 3 types 4
It is preferable to perform melt extrusion coating on the thermoplastic resin layer as melt coextrusion of the layer (adhesive resin layer / polyolefin resin layer / adhesive resin layer / EVOH layer).

If necessary, it is preferable from the viewpoint of adhesiveness that the surface on which the thermoplastic resin layer is laminated be subjected to a primer treatment in advance. The primer treatment agent is 2
Liquid-reactive polyurethane adhesive, organic titanium adhesive,
Polyester / isocyanate adhesives and the like can be mentioned, but a two-component reactive polyurethane adhesive is preferably used, and the thickness of the primer treatment layer is 0.1 to 10 μm, preferably 0.3 to 5 μm. is there.

The thickness of each layer of the obtained laminate of the present invention is not particularly limited, but a thermoplastic resin layer (/ adhesive resin layer)
/ Polyolefin resin layer (/ Adhesive resin layer) / EVOH
Layer = 10 to 5000 μm (/ 3 to 10 μm) / 10 to 1
It is arbitrarily selected from the range of 00 μm (/ 3 to 10 μm) / 3 to 20 μm.

Thus, the laminate of the present invention is obtained. In the present invention, each layer of the laminate has a plasticizer (which is naturally contained in the vinyl chloride resin layer), a stabilizer,
Surfactants, crosslinkable substances (epoxy compounds, polyvalent metals,
Inorganic or organic polybasic acids or salts thereof, etc.), fillers, colorants, fibers as reinforcing materials (glass fibers, carbon fibers, etc.),
A matting agent (talc, silica-based powder, resin fine particle powder such as polyethylene, polyurethane, etc.) and the like may be added within a range that does not impair the effects of the present invention.

The laminate obtained by the method of the present invention is
It is also useful to form an uneven pattern by embossing at least one surface of the laminate in order to increase added value such as designability, and as the uneven pattern, a wood grain conduit pattern,
What imitated the surface of the painted board, an abstract pattern, a stone pattern, a cloth pattern, a line pattern, a wood texture, a combination thereof, and the like can be used. Further, the depth of the uneven pattern formed by embossing varies depending on the pattern, but in the case of wallpaper use, it is preferable to form it to about 20 to 100 μ, because it gives a good three-dimensional effect.

As a method for forming an uneven pattern by embossing, a method of embossing using a normal hot embossing machine in which an EVOH layer is formed and then a desired uneven pattern is formed, or a cooling roll of an extrusion coater is used. Using an embossing roll imparted with a desired concavo-convex pattern to a so-called mechanical embossing method such as a so-called doubling embossing method or an ink containing a foaming inhibitor or a foaming accelerator that forms an EVOH layer at the same time as forming an EVOH layer, A chemical embossing method or the like that gives an uneven pattern in the foaming process is used.

Thus, the thermoplastic resin layer (/ adhesive resin layer) / polyolefin resin layer (/
Adhesive resin layer) / EVOH layer is a laminate that is used for office interiors such as wallpaper for interior decoration and decorative sheets for finishing furniture, desk mats, etc., stationery such as notebooks and files using PVC leather covers. It can be used for interior materials for automobiles, agricultural materials such as agricultural films, and sundries (vinyl mats, umbrellas, etc.), and is very useful as interior materials such as wallpaper and decorative sheets.

When the laminate of the present invention is used as a wallpaper, the surface of the thermoplastic resin layer of the laminate of the present invention is adhered to a base material such as foreign paper, Japanese paper, non-woven fabric, asbestos, paper, glass, fiber or cloth. It is also possible to apply a (adhesive) adhesive and then laminate it by a method such as a calendering method or a laminating method. When such a wallpaper is attached to a wall, a commonly used known adhesive is applied to a substrate. , It may be pressure-bonded to the wall surface.

[0017]

EXAMPLES The method of the present invention will be specifically described below with reference to examples. Unless otherwise specified, “%” and “parts” all mean on a weight basis. Example 1 A vinyl chloride resin film (8 μm) having one surface subjected to a primer treatment (0.5 μm) with a two-component reactive polyurethane-based adhesive (AD-335A / cat-10 manufactured by Toyo Morton Co., Ltd.)
0 μm) in a three-kind four-layer melt extruder, linear low-density polyethylene, EVOH (ethylene content: 44 mol%, saponification degree: 99.7 mol%, MI (melt index): 12 g / 10 minutes (210 ℃, load 2160
g)) and a carboxylic acid-modified polyethylene as an adhesive resin are co-extruded and melt-extrusion coated (constitution of 4 layers of 3 types: adhesive resin layer / polyethylene layer / adhesive resin layer / EVOH).
layer). The thickness of each layer of the obtained laminate is vinyl chloride resin film / carboxylic acid-modified polyethylene layer / polyethylene layer / carboxylic acid-modified polyethylene layer / EVOH layer = 80.
It was μm / 5 μm / 25 μm / 5 μm / 10 μm.
The obtained laminate had good appearance without surging.

Comparative Example 1 Vinyl chloride resin, polypropylene, EVOH and ethylene-vinyl acetate copolymer adhesive (Model DE-AP E-300S, manufactured by Mitsubishi Chemical Co., Ltd.) were used to perform melt coextrusion of 4 layers and 5 layers. , Vinyl chloride resin / adhesive resin / polypropylene / adhesive resin / EVOH = 1000 μm / 5 μm / 1
A laminated body of 0 μm / 5 μm / 10 μm (thickness) was obtained. The obtained laminate had a remarkable appearance due to remarkable surging.

[0019]

According to the present invention, the thermoplastic resin layer comprises
The polyolefin resin and saponified ethylene-vinyl acetate copolymer are melt-extrusion coated by co-extrusion, or the adhesive resin, polyolefin resin and EVOH are melt-extrusion coated by co-extrusion. An excellent laminate can be obtained, office supplies such as desk mats, wallpaper for interior decoration and decorative sheets for finishing furniture, stationery such as notebooks and files using PVC leather cover, automotive Interior materials,
It is very useful for agricultural materials such as agricultural films and daily sundries (vinyl mats, umbrellas, etc.).

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Claims (4)

[Claims] 1. When manufacturing a laminate comprising a thermoplastic resin layer / a polyolefin resin layer / a saponified ethylene-vinyl acetate copolymer layer, the thermoplastic resin layer is provided with a polyolefin resin and an ethylene-vinyl acetate copolymer. A method for producing a laminate, which comprises melt-extrusion coating a saponified product by coextrusion. 2. In producing a laminate comprising a thermoplastic resin layer / adhesive resin layer / polyolefin resin layer / adhesive resin layer / saponified ethylene-vinyl acetate copolymer layer,
A method for producing a laminate, comprising melt-extrusion coating an adhesive resin, a polyolefin-based resin, and a saponified ethylene-vinyl acetate copolymer on a thermoplastic resin layer by coextrusion. 3. The method for producing a laminate according to claim 1, wherein the thermoplastic resin is vinyl chloride resin. 4. The polyolefin resin is polyethylene,
It is either polypropylene or ethylene-vinyl acetate copolymer, The manufacturing method of the laminated body in any one of Claims 1-3 characterized by the above-mentioned.