JPH09234834A - Manufacture of laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacture of a laminate which is excellent in external appearance without any surging. SOLUTION: When a laminate composed of a thermoplastic resin layer/an adhesive layer/a polyolefin resin layer (/an adhesive layer) an ethylenevinyl acetate copolymer saponified material layer is manufactured, a laminate wherein an ethylene/vinyl acetate copolymer saponified material is melted, extruded, and coated on the polyolefin resin layer, or a laminate wherein the polyolefin resin layer and the ethylene/vinyl acetate copolymer saponified material layer are dry laminated, and the thermoplastic resin layer are dry laminated.

Description

Detailed Description of the Invention

[0001]

The present invention relates to a thermoplastic resin layer / adhesive layer / polyolefin resin layer (/ adhesive layer) / ethylene-vinyl acetate copolymer based on a thermoplastic resin such as vinyl chloride resin. Combined saponification (hereinafter abbreviated as EVOH)
More particularly, the present invention relates 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 (/ adhesive layer) / EVOH layer. When manufacturing a laminate consisting of
A laminate (A) obtained by melt-extrusion coating a saponified ethylene-vinyl acetate copolymer on a polyolefin resin layer;
It has been found that the above problems can be solved by dry laminating a thermoplastic resin layer or a laminate (B) obtained by dry laminating a polyolefin resin layer and an EVOH layer, and a thermoplastic resin layer. The present invention has been completed. In the present invention, it is preferable to provide an adhesive layer between each layer, and in the case of melt extrusion coating, it is preferable to melt-extrude coat the polyolefin resin layer with the adhesive and EVOH by coextrusion. In the case of dry lamination, it is of course preferable to interpose an adhesive layer.

[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 polyolefin resin layer is prepared in advance in order to produce a laminate comprising a thermoplastic resin layer / adhesive layer / polyolefin resin layer (/ adhesive layer) / EVOH layer using these resins. A laminate (A) comprising a polyolefin-based resin layer (/ adhesive layer) / EVOH layer on which EVOH is laminated by melt extrusion.
A polyolefin resin layer in which a thermoplastic resin layer is dry laminated, or a polyolefin resin layer and EVOH are previously laminated by dry lamination.
The greatest feature is dry lamination of the laminate (B) composed of the adhesive layer / EVOH layer and the thermoplastic resin layer, and such a method will be specifically described.

Polyolefin resin layer (/ adhesive layer) /
In producing the laminate (A) including the EVOH layer,
Using a known melt extruder, E can be applied to the polyolefin resin layer.
VOH is melt extrusion coated. In particular, it is preferable that a modified polyolefin resin such as a carboxylic acid-modified is used as the adhesive layer to perform melt coextrusion of two layers of two types. The thickness of the laminate (A) comprising the polyolefin resin layer (/ adhesive layer) / EVOH layer is not particularly limited, but the polyolefin resin layer (/ adhesive layer) / EVOH layer = 5 to 50 μm
It is arbitrarily selected from the range of (/0.1 to 10 μm) / 3 to 20 μm. Further, in manufacturing the laminated body (B),
The polyolefin resin layer and the EVOH layer are dry laminated using an adhesive such as a two-component reactive polyurethane adhesive, an organic titanium adhesive, or a polyester / isocyanate adhesive. The adhesive may be applied to the polyolefin resin layer side or the EVOH layer side. A two-component reactive polyurethane-based adhesive is preferably used as the adhesive. The thickness of the laminate (B) composed of the polyolefin resin layer / adhesive layer / EVOH layer is not particularly limited, but the polyolefin resin layer / adhesive layer / EVOH layer = 5 to 50 μm / 0.1.
It is arbitrarily selected from the range of -10 μm / 3-20 μm.

Next, the obtained laminate (A) or laminate (B) and the thermoplastic resin are dry-laminated, but the dry-lamination is not particularly limited, and is adhered to, for example, one surface of the thermoplastic resin layer. After the primer treatment with the agent, the laminate (A) or the laminate (B) is dry-laminated, or conversely, the surface of the laminate (A) or the laminate (B) on the polyolefin resin layer side is treated with an adhesive. After that, there is a method such as dry laminating with the thermoplastic resin layer. Above all, the above method is preferably adopted from the viewpoint of workability and the like.

Here, as the adhesive used for the primer treatment, similar to the above, a two-component reactive polyurethane adhesive, an organic titanium adhesive, a polyester / isocyanate adhesive and the like can be mentioned, but preferably 2 A liquid reaction type polyurethane adhesive is used, and the thickness of the adhesive layer is 0.
It is 1 to 10 μm, preferably 0.3 to 5 μm. still,
In the present invention, the thickness of the thermoplastic resin layer is 10 to 5,000.
It is preferable that the thickness is 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 the concavo-convex pattern by embossing, a method for forming embossing by using a normal hot embossing machine in which a desired concavo-convex pattern is formed after forming the laminate (A) or the laminate (B) Alternatively, a so-called doubling embossing method, in which embossing is performed at the same time when the laminate (A) or the laminate (B) is formed by using an embossing roll having a desired concavo-convex pattern as a cooling roll of an extrusion coater Print the ink containing the mechanical embossing method or foam suppressor or foam promoter,
A chemical embossing method or the like that gives an uneven pattern in the foaming process is used.

Thus, the laminate comprising the thermoplastic resin layer / adhesive layer / polyolefin resin layer (/ adhesive layer) / EVOH layer obtained by the method of the present invention has a finish for wallpaper or furniture for interior construction. Office supplies such as decorative sheets for office use, desk mats, office supplies such as notebooks and files using vinyl leather cover, interior materials for automobiles, agricultural materials such as agricultural films, daily sundries (vinyl mats) , Umbrella, etc.)
It can be used for, for example, and is very useful for 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 On a linear low-density polyethylene layer, a carboxylic acid-modified polyethylene as an adhesive and EVOH (ethylene content: 44 mol%, saponification degree: 9) were applied in a 2-kind 2-layer melt extruder.
9.7 mol%, MI (melt index): 12 g /
Melt extrusion coating for 10 minutes (210 ° C, load 2160g) and laminate (A) (polyethylene layer / adhesive layer / EV)
OH layer = 25 μm / 5 μm / 10 μm) was obtained. Such a laminate (A) and a one-sided two-component reactive polyurethane adhesive (manufactured by Toyo Morton Co., AD-335A / cat-1)
A vinyl chloride resin film (80 μm) that had been subjected to the primer treatment (0.5 μm) in 0) was laminated by dry lamination so that the EVOH layer was on the surface. The obtained laminate had good appearance without surging.

Example 2 A two-component reactive polyurethane adhesive (AD-3 manufactured by Toyo Morton Co., Ltd.) was used as an adhesive layer on a linear low-density polyethylene layer.
35A / cat-10) is applied in advance, and then the EVOH layer (ethylene content: 44 mol%, saponification degree: 99.7 mol%, MI (melt index): 1 is applied to the applied surface.
2 g / 10 minutes (210 ° C., load 2160 g) was dry laminated to obtain a laminate (B) (polyethylene layer / adhesive layer / EVOH layer = 25 μm / 0.5 μm / 10 μm). This laminate (B) and a two-component reactive polyurethane adhesive on one side (manufactured by Toyo Morton, AD-335A /
A vinyl chloride resin film (80 μm) that had been subjected to a primer treatment (0.5 μm) with cat-10) was laminated by dry lamination so that the EVOH layer 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.

[0020]

According to the present invention, the thermoplastic resin layer comprises
Polyolefin resin layer (/ adhesive layer) / EVOH laminated by melt extrusion coating or dry lamination
Since the laminated body (A) or laminated body (B) consisting of layers is dry-laminated, a laminated body having excellent appearance characteristics without the occurrence of surging can be obtained, and finishing for wallpaper or furniture for interior construction Office supplies such as decorative sheets for office use, desk mats, office supplies such as notebooks and files using vinyl leather cover, interior materials for automobiles, agricultural materials such as agricultural films, daily sundries (vinyl mats) , Umbrellas, etc.) are very useful.

Claims (4)

[Claims] 1. When producing a laminate comprising a thermoplastic resin layer / adhesive layer / polyolefin resin layer / ethylene-vinyl acetate copolymer saponification layer, an ethylene-vinyl acetate copolymer is added to the polyolefin resin layer. A method for producing a laminate, which comprises dry laminating a thermoplastic resin layer with a laminate obtained by melt extrusion coating a saponified product. 2. A polyolefin resin layer and ethylene-acetic acid for producing a laminate comprising a thermoplastic resin layer / adhesive layer / polyolefin resin layer / adhesive layer / ethylene-vinyl acetate copolymer saponified layer. A method for producing a laminate, which comprises dry laminating a saponified vinyl copolymer layer and a thermoplastic resin 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.