JPH09201917A - Manufacturing method of laminate - Google Patents

Abstract

(57) Abstract: [PROBLEMS] To provide a method for producing a laminate having excellent appearance characteristics without surging. SOLUTION: In producing a laminate comprising a thermoplastic resin layer (/ adhesive resin layer) / a polyolefin resin layer (/ adhesive resin layer) / a saponified ethylene-vinyl acetate copolymer layer, a thermoplastic resin layer is used. A laminate obtained by melt extrusion coating a polyolefin resin or a polyolefin resin and an adhesive resin, and then melt extrusion coating the saponified product of ethylene-vinyl acetate copolymer or the saponified product of ethylene-vinyl acetate copolymer and the adhesive resin thereon. Manufacturing method.

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 the above problems, and as a result, the thermoplastic resin layer / polyolefin resin layer / ethylene-vinyl acetate copolymer saponified layer is formed. In producing a laminate, after melt extrusion coating a polyolefin-based resin to the thermoplastic resin layer, then melt-extrusion coating of ethylene-vinyl acetate copolymer saponification on it to solve the above problems. Heading The present invention has been completed. In the present invention, in particular, the thermoplastic resin layer is melt-extrusion coated by co-extrusion with the adhesive resin and the polyolefin resin, and then the adhesive resin and the saponified ethylene-vinyl acetate copolymer are melt-extruded by co-extrusion. Preferably. In the present invention, the use of the adhesive resin layer is optional, and both of the adhesive resin layers may be adopted or only one of the adhesive resin layers 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. Once the layer has been melt-extruded with a polyolefin resin or melt-extruded with an adhesive resin and a polyolefin resin by co-extrusion, EVOH is then melt-extruded with the resin or co-extruded with the adhesive resin and the EVOH. The greatest feature is stacking in two stages such as.

First, the polyolefin resin layer is laminated on the thermoplastic resin layer, and the lamination is performed by melt extrusion coating using a known melt extruder. In particular, it is preferable to perform melt extrusion coating by melt coextrusion of two kinds and two layers using a modified polyolefin resin such as carboxylic acid modified as an adhesive resin layer. Further, if necessary, it is preferable from the viewpoint of adhesiveness that the surface on which the thermoplastic resin layer is laminated is subjected to a primer treatment in advance. As the primer treatment agent,
Two-component reactive polyurethane adhesives, organic titanium adhesives, polyester / isocyanate adhesives and the like can be mentioned, but two-component reactive polyurethane adhesives are preferably used, and the thickness of the primer treatment layer is 0. .1 to 10 μ
m, preferably 0.3 to 5 μm.

Next, the EVO is formed on the laminate of the thermoplastic resin layer (/ adhesive resin layer) / polyolefin resin layer obtained above, that is, on the surface of the polyolefin resin layer.
H layers are stacked. Also during the lamination, melt extrusion coating is performed using a known melt extruder in the same manner as above. Here, as in the above case, a modified polyolefin resin such as a carboxylic acid-modified resin is used as an adhesive resin for melt coextrusion of EVOH and two kinds of two layers, and the surface of the polyolefin resin layer (EV
It is preferable to apply a primer treatment to the surface on which the OH layer is laminated).

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, a laminate comprising a thermoplastic resin layer / polyolefin resin layer / EVOH layer obtained by the method of the present invention or a thermoplastic resin layer / adhesive resin layer / polyolefin resin layer / adhesive resin layer / EVOH layer Consists of office supplies such as desk mats, wallpaper for interior decoration and decorative sheets for finishing furniture, stationery such as notebooks and files using a cover of PVC leather, interior materials for automobiles, It can be used for agricultural materials such as agricultural films, daily sundries (vinyl mats, umbrellas, etc.), and is particularly 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), a linear low-density polyethylene and a carboxylic acid-modified polyethylene as an adhesive resin were co-extruded and melt-coated with a 2-kind 2-layer melt extruder. After that, the surface of the polyethylene layer was treated with a primer (0.5 μm) with a two-component reactive polyurethane adhesive (AD-335A / cat-10, manufactured by Toyo Morton Co., Ltd.), and then two kinds of two layers were melted. In the extruder, carboxylic acid-modified polyethylene as an adhesive resin and EVOH (ethylene content: 44 mol%,
Degree of saponification: 99.7 mol%, MI (melt index): 12 g / 10 minutes (210 ° C, load 2160 g))
Was coextruded and melt-coated. The thickness of each layer of the obtained laminate is vinyl chloride resin film / carboxylic acid-modified polyethylene / polyethylene / carboxylic acid-modified polyethylene / E.
VOH = 80 μm / 5 μm / 25 μm / 5 μm / 10 μ
m. 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]

INDUSTRIAL APPLICABILITY In the present invention, a thermoplastic resin layer is melt-extrusion coated with a polyolefin resin, or an adhesive resin and a polyolefin resin are melt-extrusion coated by co-extrusion, and then EVOH is melt-extrusion coated onto the thermoplastic resin layer. Since EVOH and adhesive resin are melt-extrusion coated by co-extrusion, it is possible to obtain a laminate with excellent appearance characteristics that does not cause surging. For office supplies such as desk mats, stationery such as notebooks and files using PVC leather covers, interior materials for automobiles, agricultural materials such as agricultural films, daily sundries (vinyl mats, umbrellas, etc.) It is very useful.

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Claims (4)

[Claims] 1. In producing a laminate comprising a thermoplastic resin layer / a polyolefin resin layer / a saponified ethylene-vinyl acetate copolymer layer, a thermoplastic resin layer is melt-extruded with a polyolefin resin and then coated. A method for producing a laminate, comprising melt-extrusion coating a saponified ethylene-vinyl acetate copolymer thereon. 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,
The thermoplastic resin layer is characterized in that the adhesive resin and the polyolefin resin are melt-extrusion coated by co-extrusion, and then the adhesive resin and the saponified ethylene-vinyl acetate copolymer are melt-extrusion coated by co-extrusion. Method for manufacturing laminated body. 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.