JPH09201916A - Manufacturing method of laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To materialize a body, in which no surging develops and which is excellent in the appearance. SOLUTION: In order to manufacture a laminated body consisting of a thermoplastic resin layer/adhesive layer/polyolefin-based resin layer (/adhesive layer)/ saponified ethylene-vinyl acetate copolymer layer, a laminated body by coextrusion consisting of a polyolefin-based resin layer (/adhesive layer)/ saponified ethylene-vinyl acetate copolymer layer is dry-laminated to a thermoplastic resin layer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a thermoplastic resin layer (/ adhesive layer) based on a thermoplastic resin such as vinyl chloride resin.
/ Polyolefin resin layer (/ Adhesive layer) / Ethylene-
The present invention relates to a method for producing a laminate comprising a saponified vinyl acetate copolymer (hereinafter abbreviated as EVOH) layer, and more specifically 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 (Japanese Utility Model Publication No. 2-47015), and in order to apply such a laminated body to a decorative sheet, JP-A-6-328635. In the publication, a laminate composed of a thermoplastic resin layer / adhesive layer / polyolefin resin layer / adhesive layer / EVOH layer by multi-layer coextrusion is described.

[0003]

However, such a vinyl chloride resin / EVOH laminate and a multilayer coextrusion thermoplastic resin layer / adhesive layer / polyolefin resin layer / adhesive layer / EVOH layer laminate When the present inventor examined in detail, considering the recent sophistication of the technology, the appearance physical properties are still unsatisfactory, and in the technology disclosed in JP-A-6-328635,
It is difficult to obtain a laminate having a good appearance such as surging occurring in the obtained laminate. Under the circumstances, the present invention is directed to a thermoplastic resin layer / adhesive layer / polyolefin resin layer / (adhesive layer) / EV having excellent appearance characteristics.
It is an object of the present invention to provide a method for manufacturing a laminate including an OH layer.

[0004]

The inventors of the present invention have conducted extensive studies to solve the above problems, and as a result, have found that the thermoplastic resin layer / adhesive layer / polyolefin resin layer / ethylene-vinyl acetate copolymer ken. In producing a laminate comprising a compound layer, a thermoplastic resin layer is dry laminated with a laminate (A) comprising a polyolefin resin layer / ethylene-vinyl acetate copolymer saponified layer laminated by coextrusion. The inventors have found that the above problems can be solved and completed the present invention. In the present invention, it is particularly preferable that the coextrusion of the polyolefin resin and EVOH is a three-layer coextrusion through an adhesive.

[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 layer / adhesive layer / polyolefin resin layer (/ adhesive layer) / EVOH layer using these resins is preliminarily laminated by coextrusion before producing the laminate. The greatest feature is to dry-laminate the laminate (A) composed of the polyolefin resin layer (/ adhesive layer) / EVOH layer as described above, and the method will be specifically described. . Polyolefin resin layer (/ adhesive layer) / EV
The layered product (A) comprising the OH layer is produced by melt coextrusion of two layers of two types using a known melt extruder. In particular, it is preferable to use a modified polyolefin resin such as carboxylic acid-modified as an adhesive layer for melt coextrusion of 3 layers of 3 types.

The thickness of the laminate (A) comprising such a polyolefin resin layer (/ adhesive layer) / EVOH layer is not particularly limited, but the polyolefin resin layer (/ adhesive layer)
/ EVOH layer = 10 to 100 μm (/ 3 to 10 μm) /
It is arbitrarily selected from the range of 3 to 20 μm.

Next, the obtained laminate (A) is dry-laminated on a thermoplastic resin, but the dry-lamination is not particularly limited. For example, one surface of the thermoplastic resin layer is treated with an adhesive to obtain a primer. Dry lamination of the laminated body (A), or conversely, laminated body (A)
There is a method of subjecting the surface of the polyolefin resin layer side to a primer treatment with an adhesive and then dry laminating with the thermoplastic resin layer. Above all, the above method is preferably adopted from the viewpoint of workability and the like.

Here, examples of the adhesive used for the primer treatment include a two-component reaction type polyurethane adhesive, an organic titanium type adhesive, a polyester / isocyanate type adhesive and the like, but a two-component reaction type polyurethane is preferable. A system adhesive is used, and the thickness of the adhesive layer is 0.1 to 10 μm.
m, preferably 0.3 to 5 μm. In the present invention, the thickness of the thermoplastic resin layer is 10 to 5000 μm, preferably 50 to 1000 μm.

Thus, the laminate of the present invention can be obtained. Each layer of the laminate has a plasticizer (which is naturally contained in the vinyl chloride resin layer), a stabilizer, a surfactant, and a crosslinkable substance ( Epoxy compounds, polyvalent metals, inorganic or organic polybasic acids or salts thereof, fillers, coloring agents, fibers as reinforcing materials (glass fibers, carbon fibers, etc.), matting agents (talc,
Silica-based powder, resin fine particle powder such as polyethylene, polyurethane, etc.) may be blended 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 for performing embossing using an ordinary hot embossing machine in which a desired uneven pattern is formed after forming a laminate (A), or an extrusion coating apparatus A so-called mechanical embossing method such as a so-called doubling embossing method or a so-called doubling embossing method in which an embossing roll having a desired concavo-convex pattern is applied to a cooling roll of A chemical embossing method or the like is used in which an ink containing ink is printed and an uneven pattern is formed in the foaming process.

The thermoplastic resin layer / adhesive layer / polyolefin resin layer / EVOH thus obtained by the method of the present invention.
Layered product or thermoplastic resin layer / adhesive layer /
Laminates consisting of a polyolefin resin layer / adhesive layer / EVOH layer are used for office interiors such as wallpaper for interior decoration and decorative sheets for finishing furniture, desk mats, etc., notebooks using a cover of PVC leather, It can be used for stationery such as files, interior materials for automobiles, agricultural materials such as agricultural films, daily sundries (vinyl mats, umbrellas, etc.), and is particularly useful for interior materials such as wallpaper and decorative sheets. It is useful.

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 Using a three-kind three-layer melt extruder, linear low-density polyethylene, carboxylic acid-modified polyethylene as an adhesive and E
VOH (ethylene content: 44 mol%, degree of saponification: 9
9.7 mol%, MI (melt index): 12 g /
Laminate (A) consisting of 10 minutes (210 ° C., load 2160 g) (polyethylene layer / adhesive layer / EVOH layer = 25)
μm / 5 μm / 10 μm) was obtained. Such a laminate (A)
And a vinyl chloride resin film (80 μm) on one surface of which was 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.) by dry lamination into an EVOH layer Were laminated so that the surface was on the surface. 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
Since the laminate (A) composed of the polyolefin resin layer (/ adhesive layer) / EVOH layer laminated by co-extrusion is dry-laminated, it is possible to obtain a laminate excellent in appearance characteristics without causing surging. 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 covers, interior materials for automobiles, agricultural films, etc. Very useful for agricultural materials, daily sundries (vinyl mats, umbrellas, etc.).

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Claims (4)

[Claims] 1. When manufacturing a laminate comprising a thermoplastic resin layer / adhesive layer / polyolefin resin layer / ethylene-vinyl acetate copolymer saponification layer, a polyolefin laminated by coextrusion on the thermoplastic resin layer. A method for producing a laminate, which comprises dry laminating a laminate comprising a resin layer / saponified ethylene / vinyl acetate copolymer layer. 2. A polyolefin resin laminated by coextrusion in producing a laminate comprising a thermoplastic resin layer / adhesive layer / polyolefin resin layer / adhesive layer / ethylene-vinyl acetate copolymer saponified layer. Layer / adhesive layer /
A method for producing a laminate, which comprises dry laminating a laminate comprising a saponified ethylene-vinyl acetate copolymer layer. 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.