JP4077526B2 - Manufacturing method of laminate - Google Patents

Description

[0001]
[Industrial application fields]
The present invention relates to a thermoplastic resin layer / adhesive resin layer / polyolefin resin layer / adhesive resin layer / ethylene-vinyl acetate copolymer saponified product (hereinafter abbreviated as EVOH) based on a thermoplastic resin such as vinyl chloride resin. More specifically, the present invention relates to a method for manufacturing a laminate having excellent appearance characteristics.
[0002]
[Prior art]
Conventionally, vinyl chloride resin sheets and films have been used for decorative interior sheets for furniture and furniture for architectural interiors, agricultural materials, automotive interior materials, daily goods (vinyl mats, umbrellas, etc.) It is also widely used for office supplies such as desk mats, file covers, notebook covers, and stationery.
In order to prevent the adverse effect of the plasticizer in the vinyl chloride resin, a method of laminating EVOH has been proposed (Japanese Utility Model Publication No. 2-47015), and in order to apply such a laminate to a decorative sheet, JP-A-6-328635 is proposed. The publication describes a laminate comprising a thermoplastic resin layer / adhesive resin layer / polyolefin-based resin layer / adhesive resin layer / EVOH layer by multilayer coextrusion.
[0003]
[Problems to be solved by the invention]
However, the present inventors have studied in detail such a laminate composed of vinyl chloride resin / EVOH and a laminate composed of thermoplastic resin layer / adhesive resin layer / polyolefin-based resin layer / adhesive resin layer / EVOH layer by multilayer coextrusion. However, considering the recent advancement of technology, the physical properties of the appearance are still not satisfactory, and the technology disclosed in Japanese Patent Laid-Open No. 6-328635 has a good appearance such as surging. A laminate is difficult to obtain. Then, this invention provides the manufacturing method of the laminated body which consists of a thermoplastic resin layer / adhesive resin layer / polyolefin-type resin layer / adhesive resin layer / EVOH layer which was excellent in the external appearance property in such a background. Objective.
[0004]
[Means for Solving the Problems]
Therefore, the present inventor has conducted extensive research to solve such problems, and as a result, a laminate comprising a thermoplastic resin layer / adhesive resin layer / polyolefin-based resin layer / adhesive resin layer / ethylene-vinyl acetate copolymer saponified layer. In manufacturing the body, the present inventors have found that the above-mentioned problems can be solved by subjecting a thermoplastic resin layer to melt extrusion coating of a polyolefin resin, a saponified ethylene-vinyl acetate copolymer and an adhesive resin by coextrusion. It came to be completed.
[0005]
DETAILED DESCRIPTION OF THE INVENTION
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. Then, a vinyl chloride resin is preferably used.
[0006]
Examples of the polyolefin resin used for the polyolefin resin layer include high-density polyethylene, medium-density polyethylene, (linear) low-density polyethylene, ultra-low-density polyethylene, vinyl acetate, acrylate ester, butene, hexene, 4- Polyethylene copolymerized with α-olefins such as 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 polyolefin resin obtained by copolymerizing or graft polymerization of unsaturated carboxylic acid, its anhydride, vinylsilane compound, epoxy group-containing compound, etc. to the above polyolefin High density polyester Polyethylene and ethylene such as polyethylene, polypropylene homopolymer, polypropylene grafted with ethylene, polypropylene copolymerized with α-olefins, such as polyethylene, medium density polyethylene, (linear) low density polyethylene, and ultra low density polyethylene -Vinyl acetate copolymer etc. are used suitably.
[0007]
Further, the EVOH used in the EVOH layer preferably has an ethylene content of 25 to 55 mol%, more preferably 28 to 48 mol%, and a vinyl acetate component having a saponification degree of 90 mol% or more, more preferably 95 mol% or more. If the ethylene content is less than 25 mol%, the water resistance is insufficient. On the other hand, if the ethylene content exceeds 55 mol%, the barrier properties are deteriorated and the physical properties are insufficient. On the other hand, if the degree of saponification is less than 90 mol%, the water resistance and thermal stability are insufficient, which is not preferable. The melt index (MI) is 1 to 40 g / 10 min (210 ° C., load 2160 g), preferably 2 to 15 g / 10 min.
The EVOH is a small amount of propylene, isobutene, α-octene, α-dodecene, α-olefins such as α-octadecene, unsaturated carboxylic acids or salts thereof, partial alkyl esters, complete alkyl esters, nitriles, amides and anhydrides. Further, it may contain a comonomer such as unsaturated sulfonic acid or a salt thereof.
[0008]
In the present invention, in producing a laminate composed of a thermoplastic resin layer / adhesive resin layer / polyolefin resin layer / adhesive resin layer / EVOH layer using these resins, the thermoplastic resin layer includes a polyolefin resin and The greatest feature is that EVOH is melt-extruded by coextrusion or adhesive resin, polyolefin resin and EVOH are melt-extruded by coextrusion, and this method will be specifically described.
[0009]
The polyolefin resin layer and the EVOH layer are laminated on the thermoplastic resin layer. In the lamination, the polyolefin resin and EVOH are melt-extruded by coextrusion using a known melt extruder. In the present invention, in particular, a modified polyolefin resin such as carboxylic acid modified is used as an adhesive resin layer in three types and three layers (polyolefin resin layer / adhesive resin layer / EVOH layer), or three types in four layers (adhesive resin layer / polyolefin type). Resin layer / adhesive resin layer / EVOH layer) is melt extrusion co-extruded onto the thermoplastic resin layer.
[0010]
If necessary, it is preferable from the viewpoint of adhesion that the surface on which the thermoplastic resin layer is laminated is previously subjected to primer treatment. Examples of the primer treatment agent include a two-component reactive polyurethane adhesive, an organic titanium-based adhesive, a polyester / isocyanate-based adhesive, and the like, and preferably a two-component reactive polyurethane adhesive is used. The primer treatment layer has a thickness of 0.1 to 10 μm, preferably 0.3 to 5 μm.
[0011]
The thickness of each layer of the obtained laminate of the present invention is not particularly limited, but thermoplastic resin layer / adhesive resin layer / polyolefin-based resin layer / adhesive resin layer / EVOH layer = 10 to 5000 μm / 3 to 10 μm / 10 to 100 μm It is arbitrarily selected from the range of / 3 to 10 μm / 3 to 20 μm .
[0012]
Thus, the laminate of the present invention can be obtained. In the present invention, each layer of the laminate has a plasticizer (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 their salts, etc.), fillers, colorants, fibers as reinforcing materials (glass fibers, carbon fibers, etc.), matting agents (talc, silica-based powders) , Resin fine particle powders such as polyethylene and polyurethane) and the like can be blended within a range that does not impair the effects of the present invention.
[0013]
In addition, the laminate obtained by the method of the present invention 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. As the pattern, a wood grain conduit pattern, a pattern imitating the surface of a painted plate, an abstract pattern, a stone pattern, a cloth pattern, a line pattern, a bark pattern, and a combination thereof can be used.
Moreover, although the depth of the uneven | corrugated pattern formed by embossing changes with patterns, in the case of a wallpaper use, forming in about 20-100 micrometers normally gives a favorable three-dimensional effect, and is preferable.
[0014]
As a method of forming a concavo-convex pattern by embossing, a method of embossing using a normal hot embossing machine in which a desired concavo-convex pattern is formed after forming an EVOH layer, a cooling roll of an extrusion coating apparatus, etc. are desired. Using an embossing roll with a concavo-convex pattern, printing an ink containing a so-called mechanical embossing method such as a so-called doubling embossing method or embossing at the same time as forming an EVOH layer, or a foaming inhibitor or foaming accelerator. The chemical embossing method etc. which give an uneven pattern are used.
[0015]
Thus, the laminate comprising the thermoplastic resin layer / adhesive resin layer / polyolefin resin layer / adhesive resin layer / EVOH layer obtained by the method of the present invention is a wallpaper for architectural interiors, a decorative sheet for finishing furniture, etc. Office supplies such as desk mats, stationery such as notebooks and files using the cover of PVC leather, interior materials for automobiles, agricultural materials such as agricultural films, daily miscellaneous goods (vinyl mats, umbrellas, etc.) It is particularly useful for interior materials such as wallpaper and decorative sheets.
It is also very useful for chemical punches (chemical anchor / punch type).
[0016]
When the laminate of the present invention is used as wallpaper, the surface of the thermoplastic resin layer of the laminate of the present invention is sticky (contacted) to a substrate such as paper, Japanese paper, non-woven fabric, asbestos, paper, glass, fiber, or cloth. It is also possible to apply an adhesive and laminate it by a method such as a calendar method or a laminate method. When pasting such wallpaper on a wall, apply a commonly used adhesive to the base material and apply it to the wall surface. What is necessary is just to make it crimp.
[0017]
【Example】
Hereinafter, the method of the present invention will be specifically described with reference to examples.
Note that “%” and “parts” are based on weight unless otherwise specified.
Example 1
Three layers and four layers are melted on a vinyl chloride resin film (80 μm) that has been primed (0.5 μm) with a two-component reactive polyurethane adhesive (AD-335A / cat-10, manufactured by Toyo Morton Co., Ltd.) on one side In an extruder, linear low density polyethylene, EVOH (ethylene content: 44 mol%, saponification degree: 99.7 mol%, MI (melt index): 12 g / 10 min (210 ° C., load 2160 g)) Then, carboxylic acid-modified polyethylene as an adhesive resin was coextruded and melt extrusion coated (3 types, 4 layers: adhesive resin layer / polyethylene layer / adhesive resin layer / EVOH layer). The thickness of each layer of the obtained laminate was vinyl chloride resin film / carboxylic acid modified polyethylene layer / polyethylene layer / carboxylic acid modified polyethylene layer / EVOH layer = 80 μm / 5 μm / 25 μm / 5 μm / 10 μm.
The obtained laminate did not generate surging and had a good appearance.
[0018]
Comparative Example 1
4 types and 5 layers of melt coextrusion using vinyl chloride resin, polypropylene, EVOH, and ethylene-vinyl acetate copolymer adhesive (Mitsubishi Chemical Co., Ltd., MODEC-AP E-300S). A laminate of resin / polypropylene / adhesive resin / EVOH = 1000 μm / 5 μm / 10 μm / 5 μm / 10 μm (thickness) was obtained.
The obtained laminate was significantly surging and had poor appearance.
[0019]
【The invention's effect】
In the present invention, the thermoplastic resin layer is melt-extruded by coextrusion with a polyolefin resin and an ethylene-vinyl acetate copolymer saponified product, or melt-extruded with an adhesive resin, a polyolefin resin and EVOH by coextrusion. As a result, it is possible to obtain a laminate that does not generate surging and has excellent appearance characteristics, such as wallpaper for architectural interiors and decorative sheets for finishing furniture etc., office supplies such as desk mats, and cover of PVC leather. It is very useful for stationery items such as notebooks and files used, interior materials for automobiles, agricultural materials such as agricultural films, and household goods (vinyl mats, umbrellas, etc.).

Claims (2)

Vinyl resin film / adhesive resin layer / polyolefin resin layer / adhesive resin layer / ethylene chloride - in manufacturing a laminate consisting of vinyl acetate copolymer saponified layer, the vinyl chloride resin film, adhesive resin, a polyolefin resin and A method for producing a laminate, comprising melt-extrusion coating a saponified ethylene-vinyl acetate copolymer by coextrusion.   The method for producing a laminate according to claim 1, wherein the polyolefin resin is any one of polyethylene, polypropylene, and ethylene-vinyl acetate copolymer.