JPH11198298A - Ethylene/vinyl alcohol copolymer film and laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a film excellent in antistaining properties and hardly receiving stain when used for the surface layer of a laminate, an interior material or the like. SOLUTION: An ethylene/vinyl alcohol copolymer film is obtained by applying a surfactant to the surface of a film comprising an ethylene/vinyl alcohol copolymer with ethylene content of 20-60 mol.% and a saponification value of 90% or more. The non-polar group of this surfactant is pref. a group comprising a polyalkylsiloxane or the polar group thereof is more pref. a group comprising polyalkylene glycol and the surfactant is optimally composed of a polyalkylsiloxane/polyalkylene glycol block copolymer. The ethylene/vinyl alcohol copolymer pref. contains 1-60 wt.% of a thermoplastic resin other than this copolymer or an org. or inorg. filler and the thermoplastic resin is more pref. carboxylic acid modified polyolefin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a film, a laminate, and an interior material having a high level of resistance to dirt and having excellent productivity and handleability.

[0002]

2. Description of the Related Art An ethylene-vinyl alcohol copolymer (E
VOH) is excellent in strength and chemical resistance, and does not substantially transmit various gases and organic compounds, and has excellent transparency such as being less likely to be charged with static electricity and dust, and has high transparency. Moreover, it has a high degree of aesthetics, such as being easy to adapt to human sensations without the cheapness inherent in plastics in appearance. Therefore, it is used alone or in combination with other materials, and is preferably used as a material for improving the durability, antifouling property, and aesthetics of various laminates. Particularly, as described in JP-B-4-56744, JP-B-6-49816, and JP-A-6-297654, when compounded with a polyvinyl chloride (PVC) sheet, an oily substance (oily magic, lipstick, vegetable oil) is used. , Tobacco, tartar, etc.) as well as preventing the exudation of the plasticizer contained in PVC, preventing the contamination of the indoor environment, the destruction of adjacent plastics, or the deterioration of appearance, which has occurred conventionally. It is often used because it can.

An EVOH film having such excellent properties has an exceptionally high affinity for only a part of a substance, for example, polyvinyl alcohol, starch paste, and the like.
Once attached, the removal requires a great deal of labor.
In addition, these substances themselves become nutrient sources such as microorganisms and may become discolored, or may adhere to dust and dirt around them, thereby significantly lowering the appearance.

Moreover, since the substance is a material excellent in cost performance, safety, and workability, it is widely used in daily office work, children's work, or building interior work. EVOH film contamination often occurs.

It is known that a certain degree of resistance to such film contamination can be imparted to ordinary plastic films by applying a release agent such as olefins or silicone oil.

However, the EVOH film does not allow the adhesion of a normal release agent due to its excellent stain resistance based on its high polarity, and is repelled on the surface by kneading or mechanical application. It has been considered impossible to use a release agent.

[0007] Further, no other improved method has been found, and the only possible countermeasure at present is a very passive method in which care is taken not to attach the substance.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems and to obtain an EVOH film having excellent resistance to all kinds of contamination, a laminate using the same, and an interior material. It is in.

[0009]

Means for Solving the Problems As a result of investigations to achieve the above object, the present inventors have found that when a surfactant is applied and used, it is not repelled on an EVOH film,
It was found that good adhesion could be obtained. In addition, this has revealed that the affinity between the EVOH film and polyvinyl alcohol, starch paste, etc. is significantly reduced, and the resistance to contamination is significantly improved, and at the same time, the resistance to oily stains is also significantly improved. Was. In addition, it has been found that the adhesiveness of the film, which has been regarded as a drawback of the conventional EVAL film, is remarkably reduced, and the productivity and handleability of the film are significantly improved. Thus, the present invention has been completed.

That is, an object of the present invention is to provide a film formed by coating a surface of a film made of an ethylene-vinyl alcohol copolymer having an ethylene content of 20 to 60 mol% and a saponification degree of 90% or more with a surfactant. Is achieved by doing

In this case, the surfactant has at least one group selected from the following group (A) as a non-polar group, and at least one group selected from the following group (B) as a polar group. It is preferable to have (A) group: a group comprising an aliphatic hydrocarbon group having 10 or more carbon atoms, an aromatic hydrocarbon group, and a polyalkylsiloxane. Group (B): a group consisting of polyalkylene glycol, a sulfonic acid group or a salt thereof, a carboxyl group or a salt thereof, a hydroxyl group, an amino group or a salt thereof.

More preferably, the non-polar group of the surfactant is a group comprising a polyalkylsiloxane, or the polar group is a group comprising a polyalkylene glycol.
Most preferably, it consists of a polyalkylene glycol block copolymer.

Preferably, the ethylene-vinyl alcohol copolymer contains 1 to 60% by weight of another thermoplastic resin or an inorganic or organic filler, and the thermoplastic resin is a carboxylic acid-modified polyolefin. Is more preferable.

A laminate formed by laminating a polyvinyl chloride film or sheet containing a plasticizer in an amount of 25 to 55% by weight and the above-mentioned EVOH film such that the surface coated with a surfactant is disposed on the outermost surface. This is a preferred mode of carrying out the invention. Further, the EVOH film or the laminate,
An interior material laminated so that the surface coated with the surfactant is disposed on the outermost surface is also a preferred embodiment of the present invention.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. The EVOH used in the present invention has an ethylene content of 20 to 60 mol%, preferably 25 to 50 mol%, and a saponification degree of 90% or more, preferably 95% or more. If the ethylene content is less than 20 mol%, the water resistance is reduced, the resistance to contamination by a water-soluble substance is reduced, the processability is reduced, and the design property when used as an interior material is limited. In addition, ethylene content is 60
If it exceeds mol%, or if the saponification degree is less than 90%, the oil resistance will be reduced, and contamination with oily substances will easily occur. In addition, the plasticizer will be allowed to pass through when laminated on PVC or elastomers. Therefore, it is not preferable.

As the fatty acid vinyl used as a raw material for the EVOH, any known one such as vinyl acetate can be used, but vinyl acetate is preferred. Further, comonomer components other than ethylene and fatty acid vinyl, such as propylene and N-vinylpyrrolidone, may be used as long as the effects of the present invention are not impaired.

The EVOH may be a blend of two or more EVOHs having different ethylene contents, saponification degrees and polymerization degrees. Boric acid, an antioxidant, a slip agent, Antibacterial agents, coloring agents, deodorants, ultraviolet absorbers, lubricants, and the like may be blended.

EVOH used in the film of the present invention
Preferably contains a thermoplastic resin other than EVOH or an inorganic or organic filler. Such a thermoplastic resin or an inorganic or organic filler other than EVOH is added to EVOH to reduce the adhesiveness of the film and to adjust the appearance (glossiness, transparency) of the film. The blending amount is arbitrarily adjusted according to the required gloss and transparency, but is preferably contained in an amount of 1 to 60% by weight based on the weight of the film. Especially for interior materials, 3
It is preferably contained in an amount of not less than 10% by weight, more preferably not less than 10% by weight, and more preferably not less than 15% by weight because glossiness (matte surface) having the most excellent sense of quality is obtained. When the compound to be compounded is a thermoplastic resin, the compounding amount is 60.
If the content is more than 10% by weight, the stain resistance and chemical resistance of the film will be reduced, and lamination may not be possible depending on the type. Further, when the compounding amount is an inorganic or organic filler, if the compounding amount exceeds 60% by weight, the film strength is remarkably reduced, which is not preferable.

The thermoplastic resin blended in the EVOH is not particularly limited, and may be polyolefin, PMMA,
Examples include polystyrene, polyacrylonitrile, polycarbonate, polyacetal, polyester, and polyamide. Above all, processing conditions such as lamination and embossing for imparting design properties are close to those of EVOH, and thus polyolefin resins are preferable because the workability of the compounded film is most excellent, and among them, polyethylene resins are most preferable. In addition, it shows stable dispersibility, and as a result, it is hard to cause a change in film performance due to production conditions, and since it is excellent in productivity, the polyolefin resin is maleic anhydride,
It is more preferable that the resin is modified with an unsaturated carboxylic acid such as (meth) acrylic acid.

The inorganic or organic filler to be incorporated in the EVOH is not particularly limited. Examples of the inorganic filler include talc, silica, kaolin, calcium carbonate, mica, glass flakes, glass beads, and various whiskers (titanic acid). Potassium, magnesium hydroxide, calcium carbonate, etc.), fly ash, aluminum hydroxide, zinc oxide, zinc sulfide, zeolites and the like. Examples of the organic filler include, for example, pulverized products of various thermosetting resins represented by thermosetting acrylic resins and epoxy resins, pulverized products of natural or synthetic rubber, various core-shell polymers, and low melting points of high melting points such as melamine. Molecular compound crystals and the like. Suitable average particle size of such organic or inorganic filler is 0.1 to 10 μm, more preferably 0.5 to 5 μm. If it is too fine, the effects of preventing sticking and improving the glossiness will be small, and if it is too large, the mechanical properties of the film may be reduced, or productivity may be reduced due to clogging during film formation.

In the present invention, EVOH and a thermoplastic resin or inorganic filler other than EVOH can be mixed by a known method to form a film. For example, simultaneously supplying both components to an extruder, forming a film by a cast or inflation method at the same time as blending, kneading and pelletizing both in advance, and then forming a film by another extruder, or extruding both at the same time After melt-kneading the mixture, the mixture is directly melt-extruded onto a target substrate and laminated.

The thickness of the EVOH film of the present invention is not particularly limited, and does not exclude a relatively thick sheet. However, in consideration of economy, design, productivity, and the like, a so-called thin film is preferable. Specific thickness is 3 to 300 μm
Is preferable, and a thickness of 5 to 200 μm is more preferable.

The EVOH in the film of the present invention is preferably highly crystallized and exhibits higher film properties. More specifically, 114 relative to 1090 cm ^-1 of the infrared absorption spectrum of the film, which is an index indicating crystallization.
It is preferable that the absorbance ratio at 0 cm ^-1 is 0.65 or more. As a method of performing such crystallization, for example, there is a method of performing a heat treatment at a temperature equal to or higher than the Tg of EVOH.

The surfactant used in the present invention is not particularly limited, but specifically has at least one group selected from the following group (A) as a nonpolar group,
Examples of the polar group include surfactants having at least one group selected from the following group (B).
(A) group: a group comprising an aliphatic hydrocarbon group having 10 or more carbon atoms, an aromatic hydrocarbon group, and a polyalkylsiloxane.
Group (B): a group consisting of polyalkylene glycol, a sulfonic acid group or a salt thereof, a carboxyl group or a salt thereof, a hydroxyl group, an amino group or a salt thereof. Examples of such a surfactant include a block copolymer of polyethylene glycol and polymethylsiloxane, sodium alkylbenzene sulfonate, partial stearic acid ester of polyglycerin, and sodium salt of linolenic acid sulfate.

Among them, the non-polar group is preferably a group composed of polyalkylsiloxane, more preferably a group composed of polyalkylsiloxane having an average silicon number of 5 or more. Further, the polar group is preferably a group composed of polyalkylene glycol, and more preferably a group composed of polyalkylene glycol having an average number of alkylene glycol units of 5 or more. Particularly preferred surfactants include those comprising a polyalkylsiloxane-polyalkylene glycol block copolymer, and a polyalkylsiloxane-polyethylene glycol block copolymer is most suitable. By using such a surfactant, it is possible to obtain an EVOH film excellent in stain prevention properties, handling properties and productivity. In addition, these surfactants can also be used in mixture of 2 or more types.

It is important that the surfactant in the present invention is used by coating. When kneaded with EVOH, even if embossing is observed on the surface, the effect of improving the resistance to contamination is not exhibited, probably because the molecular orientation is inappropriate.

The method for applying the surfactant in the present invention is not particularly limited, and a known method can be applied. For example, spray coating, coating with a gravure roll, or a method of applying using a brush or the like dissolved in various organic or inorganic solvents or in the form of a stock solution can be adopted. In addition to applying the film directly on the film and then laminating it, the film may be laminated and applied beforehand, or it may be applied in the form of an interior material and then applied to the surface. It is.

The film of the present invention contains 25 to 55 plasticizers.
It is preferable to laminate the polyvinyl chloride-based film or sheet containing the surfactant by weight so that the surface coated with the surfactant is disposed on the outermost surface. With the structure of such a laminate, bleeding of the plasticizer is suppressed, resistance to contamination of the polyvinyl chloride film, texture, etc. are significantly improved, interior materials such as wallpaper, synthetic leather on furniture surfaces, and the like. It is preferably used for applications.

Further, an interior material obtained by laminating the EVOH film of the present invention or a laminate laminated with the above-mentioned polyvinyl chloride film or sheet so that the surface coated with a surfactant is disposed on the outermost surface is also suitable. It is an embodiment.

[0030]

EXAMPLES The present invention will be described below in more detail with reference to examples, but the present invention is not limited to these examples. The evaluation performed in this example was performed in the following manner.

Glue peeling test A commercially available starch glue (Sangetsu Vest (TM) manufactured by Yazawa Chemical Co., Ltd.) was diluted with 50% by weight of water on the obtained EVOH film or the laminate obtained by heat lamination. It was applied, dried at room temperature, and the state of peeling of the paste was observed. Further, a polyvinyl alcohol paste (Arabic Yamato (TM) manufactured by Yamato Co., Ltd.) was applied, dried at room temperature, and the state of peeling of the paste was observed. The adhesive releasability was evaluated on the following four levels. ：: spontaneously peels off upon drying. ：: easily peeled off by rubbing after drying. Δ: Partially peelable by rubbing after drying. ×: Does not peel.

-Film adhesion test before adhesive application The unwound EVOH film was unwound by hand,
The adhesiveness of the film was sensory evaluated. Adhesiveness is the following 4
It was evaluated on a scale. ：: No sticking at all. ：: Slightly sticky feeling ：: There is sticky but rollable possible ×: Strong sticking and difficult to roll

Adhesive coated film adhesiveness test Vinyl chloride based on 100 parts by weight of a vinyl chloride copolymer containing 87 mol% of a vinyl chloride component and 13 mol% of a vinyl acetate component and 1.5 parts by weight of hexamethylene isocyanate The copolymer composition was prepared by adding methyl ethyl ketone: toluene = 1: 1.
Was dissolved in a mixed solvent having a solid content concentration of 20%, and applied to an EVOH film at a concentration of 2 g / m ² (based on solid content), dried and wound up to obtain an adhesive-coated film. This film was unwound by hand, and the adhesiveness of the adhesive-coated film was sensory tested. The evaluation method is the same as in the case of the film adhesiveness test before applying the adhesive.

Heat laminability test Adhesive coated film (wound up once in the above-mentioned adhesiveness test,
Unwound), PVC film 1, 2 and JI
Class 1 steel plate of SG3101 (0.1 × 15 × 200m
m) was subjected to thermal lamination at 130 ° C., and the adhesive strength of the film was measured by a T-type peel test.

An antifouling test An oil-based pen (Mitsubishi Marker (TM) manufactured by Mitsubishi Pencil Co., Ltd.) and a crayon (Sakura Crayon Futomaki (TM) manufactured by Sakura Crepas Co., Ltd.) were applied to the laminate obtained by heat lamination.
Red) and lipstick (Shiseido Resente Rouge Excellent (TM) Co., Ltd.), and 24 hours later, use a thinner (Nippon Paint Co., Ltd. lacquer thinner) for oil-based pens
(TM)), and for crayon and lipstick, a neutral detergent (Mama Lemon (TM) manufactured by Lion Corporation) was applied to a gauze and wiped off, and the remaining color strength was evaluated by JIS gray scale.

Reference Example 1 (Preparation of PVC sheet 1) 100 parts by weight of polyvinyl chloride resin, 50 parts by weight of plasticizer (di-2-ethylhexyl phthalate), 50 parts by weight of filler (calcium carbonate), pigment (TiO ₂₎ ) 20 parts by weight of the compound were extruded by an extruder to obtain a sheet having a thickness of 0.5 mm.

Reference Example 2 (Preparation of PVC Sheet 2) 100 parts by weight of polyvinyl chloride resin, 50 parts by weight of plasticizer (di-2-ethylhexyl phthalate), 50 parts by weight of filler (calcium carbonate), pigment (TiO ₂₎ ) A blend of 20 parts by weight and a foaming agent (azodicarbonamide) 2 parts was extruded by an extruder to form a sheet having a thickness of 0.5 mm, and then foamed to obtain a foamed PVC sheet.

Example 1 EVOH film (EVAL (TM) manufactured by Kuraray Co., Ltd.)
On the surface of EF-E), a polysiloxane-polyethylene glycol block copolymer (NUC Silicone (TM) L7
002) at a rate of 10 g / m ² (solution basis), dried and wound up to obtain a surfactant-coated film.

With respect to the obtained film and laminate,
An adhesive peel test, an adhesive test, an adhesive coated film adhesive test, a heat laminating test, and a stain prevention test were performed. Table 1 summarizes the obtained results.

Example 2 EVOH (EVAL ™ EC-E manufactured by Kuraray Co., Ltd.)
105) 75% by weight, and maleic anhydride modified polyethylene (MODIC-AP (TM) manufactured by Mitsubishi Kasei Corporation)
H511) was extruded using a twin-screw extruder to a thickness of 1
It was a 5 μm film. A test similar to that of Example 1 was performed using this film instead of the EVOH film of Example 1. Table 1 shows the results.

Example 3 A test was conducted in the same manner as in Example 2 except that polybutylene terephthalate (KS293F manufactured by Kuraray) was used instead of the maleic anhydride-modified polyethylene. Table 1 shows the results.

Example 4 The same test as in Example 2 was carried out except that kaolin (manufactured by Mori Kasei Kogyo Kogyo Kogyo Co., Ltd.) was used instead of the maleic anhydride-modified polyethylene. Table 1 shows the results.

Example 5 A test was conducted in the same manner as in Example 1 except that sodium alkyl sulfonate (Electrostripper (TM) PC manufactured by Kao) was used instead of the polysiloxane-polyethylene glycol block copolymer. Table 1 shows the results.

Example 6 A test was conducted in the same manner as in Example 1 except that polyoxyethylene lauryl ether (Nonion (TM) K-204, manufactured by NOF Corporation) was used in place of the polysiloxane-polyethylene glycol block copolymer. Was done. Table 1 shows the results.

Comparative Example 1 A test was conducted in the same manner as in Example 1 except that the polysiloxane-polyethylene glycol block copolymer was not applied. Table 2 shows the results.

Comparative Example 2 In place of the EVOH film used in Example 1, EVO
H98% by weight and 2% by weight of a polysiloxane-polyethylene glycol block copolymer were put into an extruder, and a polysiloxane-polyethylene glycol block copolymer was applied to the surface using a 15 μm thick film obtained by mixing and extruding. The test was performed in the same manner as in Example 1 except that the test was not performed. Table 2 shows the results.

Comparative Example 3 A test was performed in the same manner as in Example 1 except that a stearic acid bisamide emulsion (Alflow H50ES (TM) manufactured by NOF Corporation) was used instead of the polysiloxane-polyethylene glycol block copolymer. . Table 2 shows the results
Shown in

Comparative Example 4 Polysiloxane (NU manufactured by Nippon Unicar Co., Ltd.) was used instead of the polysiloxane-polyethylene glycol block copolymer.
The test was performed in the same manner as in Example 1 except that C silicone oil (TM) L45 (1000)) was used. Table 2 shows the results.

As described above, a film having a surface coated with a surfactant may be a conventional EVOH film, a film obtained by kneading a surfactant into this film, or a known release agent (eg, silicone oil, ethylene bisamide stearate, etc.). )
Not only does the resistance to starch glue, PVOH, etc. improve remarkably, but also the adhesiveness and the resistance to other contaminants are improved. It can be seen that the contact strength is remarkably excellent such that the contact strength to the substrate is not affected at all.

Example 7 A resin composition having the same composition as the PVC sheet 1 prepared in Reference Example 1, modified polyethylene (ADMERR VF500 manufactured by Mitsui Petrochemical Industries, Ltd.) and EVOH (EVAL ™ EC-E105 manufactured by Kuraray Co., Ltd.) ) Were subjected to co-extrusion using a co-extrusion extruder to form a PVC layer 0.5 mm, a denatured polyethylene layer 15 μm, and an EVOH layer 1
A laminated film is formed by laminating 5 μm in this order,
After a surfactant was coated on the EVOH surface in the same manner as in Example 1, a glue peeling test and a stain prevention test were performed. Table 3 shows the results.

COMPARATIVE EXAMPLE 5 The film prepared in Reference Example 1 was subjected to a glue peeling test and a stain prevention test. Table 3 shows the results.

From Example 7 and Comparative Example 5, it can be seen that the film layer of the present invention has excellent antifouling properties, and that its properties are exhibited regardless of the production method.

[0053]

[Table 1]

[0054]

[Table 2]

[0055]

[Table 3]

[0056]

The film of the present invention is excellent in stain resistance and agglutination resistance. By laminating the film of the present invention, an interior material having excellent stain resistance can be obtained.

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁶ Identification code FI // C08J 7/06 CES C08J 7/06 CESA

Claims (9)

[Claims] 1. A film comprising a film made of an ethylene-vinyl alcohol copolymer having an ethylene content of 20 to 60 mol% and a saponification degree of 90% or more, coated with a surfactant. 2. The surfactant has at least one group selected from the following group (A) as a non-polar group,
2. The film according to claim 1, wherein the polar group has at least one group selected from the following group (B). (A) group: a group comprising an aliphatic hydrocarbon group having 10 or more carbon atoms, an aromatic hydrocarbon group, and a polyalkylsiloxane. Group (B): a group consisting of polyalkylene glycol, a sulfonic acid group or a salt thereof, a carboxyl group or a salt thereof, a hydroxyl group, an amino group or a salt thereof. 3. The film according to claim 1, wherein the non-polar group is a group comprising a polyalkylsiloxane. 4. The film according to claim 1, wherein the polar group is a group comprising a polyalkylene glycol. 5. The method according to claim 1, wherein the surfactant is a polyalkylsiloxane.
The film according to any one of claims 1 to 4, comprising a polyalkylene glycol block copolymer. 6. The film according to claim 1, wherein the ethylene-vinyl alcohol copolymer contains 1 to 60% by weight of another thermoplastic resin or an inorganic or organic filler. 7. The film according to claim 6, wherein the thermoplastic resin is a carboxylic acid-modified polyolefin. 8. A polyvinyl chloride-based film or sheet containing 25 to 55% by weight of a plasticizer and the film according to any one of claims 1 to 7, wherein the surface coated with a surfactant is disposed on the outermost surface. A laminate that is laminated in such a manner. 9. An interior material obtained by laminating the film or the laminate according to any one of claims 1 to 8 such that the surface coated with the surfactant is disposed on the outermost surface.