JPH10305534A - Laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate useful for interior finish material utility with excellent stainproofness (stain removability) and chemical resistance. SOLUTION: The laminate is obtained by laminating a saponified ethylene- vinyl acetate copolymer layer having 20 to 60 mol.% of ethylene content and 90 mol.% or more of degree of saponification and a resin composition layer made of carboxyl group-containing ethylene-vinyl acetate copolymer and thermoplastic resin having 8.5 to 11 of SP value (calculated from Small formula).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminate using a saponified ethylene-vinyl acetate copolymer (hereinafter abbreviated as EVOH), and more particularly to stain resistance (stain removal property) and chemical resistance. The present invention relates to a laminate having excellent properties.

[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. However, such a vinyl chloride resin contains a large amount of a plasticizer,
Wallpaper in which EVOH is laminated on a vinyl chloride resin layer in order to prevent the plasticizer in the vinyl chloride resin from being adversely affected.
No. 015) and a polyvinyl chloride film containing a plasticizer in an amount of 25 to 55% by weight.
(Japanese Patent Application Laid-Open No. 60-224542)
Has been proposed.

[0003]

However, although any of the above laminates (wallpaper) has a short-term plasticizer suppression effect, it is left for a long time at a high humidity and at a temperature of about 30 to 40 ° C. In such a case, it is presumed that the suppression effect is also reduced, and a new improvement is desired.

[0004]

The inventor of the present invention has conducted intensive studies to solve the above-mentioned problems. As a result, the present inventors have found that an E content of 20 to 60 mol% and a saponification degree of 90 mol% or more are E.
VOH (A) layer and carboxyl group-containing ethylene-vinyl acetate copolymer (B1) and SP value (calculated from Small's formula)
A laminate obtained by laminating a resin composition (B) layer composed of a thermoplastic resin (B2) having a particle size of 8.5 to 11 can solve the above-mentioned problems, and further has a resin composition (B) layer In the carboxyl group-containing ethylene-vinyl acetate copolymer (B1)
When the thermoplastic resin (B2) having a P value (calculated from the Small formula) of 8.5 to 11 is dispersed, it has been found that the effects of the present invention can be remarkably obtained, and the present invention has been completed. .

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described specifically. The EVOH (A) of the present invention has an ethylene content of 20.
-60 mol% (furthermore, 25-50 mol%), and the degree of saponification of the vinyl acetate component is 90 mol% or more (furthermore, 95 mol%).
When the ethylene content is less than 20 mol%, the effect of suppressing the plasticizer under high humidity becomes insufficient. On the other hand, when it exceeds 60 mol%, the barrier property of EVOH decreases, and The object cannot be achieved, and even if the saponification degree is less than 90 mol%, the effect of suppressing the plasticizer under high humidity becomes insufficient, and the object of the present invention cannot be achieved.

The EVOH further comprises a small amount of an α-olefin such as propylene, isobutene, α-octene, α-dodecene, α-octadecene, an unsaturated carboxylic acid or a salt thereof, a partial alkyl ester, a complete alkyl ester, a nitrile. Comonomers such as amides / anhydrides, unsaturated sulfonic acids or salts thereof may be included. Also,
The melt index (MI) of EVOH (A) is 0.
5 to 50 g / 10 min (210 ° C., 2160 g load) is preferred, and more preferably 1 to 35 g / 10 min (same as above). If the MI is less than 0.5 g / 10 min (same as above), the processability in solution or extrusion coating becomes poor, and if it exceeds 50 g / 10 min (same as above), the stain removal property becomes insufficient, which is not preferable. .

The resin composition (B) layer laminated with the EVOH (A) layer has a carboxyl group-containing ethylene-vinyl acetate copolymer (B1) and an SP value (calculated from the Small's formula).
Is composed of 8.5 to 11 thermoplastic resin (B2),
As such a carboxyl group-containing ethylene-vinyl acetate copolymer (B1), the vinyl acetate content is preferably from 1 to 40% by weight, more preferably from 2 to 35% by weight, and if the content is less than 1% by weight. Insufficient adhesion, conversely 40
If the content is more than 0.5% by weight, the appearance of the laminate becomes poor, which is not preferable.
When the content is less than 0.5 mol%, the adhesion is insufficient, and when the content exceeds 20 mol%, the appearance of the laminate becomes poor. Not preferred.

In introducing such a carboxyl group, an unsaturated carboxylic acid-containing monomer such as acrylic acid, methacrylic acid, maleic acid, crotonic acid, fumaric acid, itaconic acid, or an anhydride thereof is converted to EVA or ethylene. And vinyl acetate. Also, SP
If the thermoplastic resin (B2) has a value (calculated from the Small formula) of 8.5 to 11, the SP value is less than 8.5, the effect of suppressing the plasticizer becomes insufficient. The object of the present invention cannot be achieved because the effect of suppressing the plasticizer under humidity is insufficient, and furthermore, a small number (G) containing at least 30% by weight of a substituent having 250 or more in one molecule. It is also not preferable that when a substituent having a Small number (G) of 250 or more is not contained in an amount of 30% by weight or more in one molecule, the effect of suppressing the plasticizer becomes insufficient.

The substituent having a Small number (G) of 250 or more specifically includes a carbonyl group (G = 275), a carboxyl group (G = 390), and a phenyl group (G = 73).
5), (o, m, p-) phenylene group (G = 658),
Naphthyl group (G = 1146), nitro group (G = 44)
0), a cyano group (G = 410) and the like. Among them, a carbonyl group (G = 275) and a carboxyl group (G = 39)
0), a phenyl group (G = 735), and an (o, m, p-) phenylene group (G = 658) can be suitably used. Specific examples of the thermoplastic resin (B2) include polystyrene. (SP value = 9.1), ethylene-vinyl acetate copolymer (vinyl acetate content 35-70% by weight) (SP
Value = 8.5-9.0), NBR (nitrile rubber) (SP
Value = 9.3), SBS (styrene / butadiene / styrene copolymer) (SP value = 8.6), ABS (acrylonitrile / butadiene / styrene copolymer) (SP value =
9.0), amorphous polyester (SP value = 10.5-1)
1.0) and the like, and preferably, polystyrene (SP value = 9.1) or ethylene-vinyl acetate copolymer (vinyl acetate content 35 to 70% by weight) (SP value = 8.5 to 9.5).
0) and their derivatives.

The compounding weight ratio (B1) / (B2) of the carboxyl group-containing ethylene-vinyl acetate copolymer (B1) and the thermoplastic resin (B2) is preferably from 95/5 to 50/50, more preferably from 90/50. When the compounding weight ratio exceeds 95/5, the effect of suppressing the plasticizer becomes insufficient, and when it is less than 50/50, the adhesiveness becomes insufficient, which is not preferable.

The mixing and blending of the carboxyl group-containing ethylene-vinyl acetate copolymer (B1) and the thermoplastic resin (B2) are not particularly limited. However, the mixing and blending are performed so that (B2) is dispersed in (B1). By doing so, the effects of the present invention can be remarkably exhibited, and specifically, it is sufficient to melt-mix (B2) in the molten state with (B1) in the molten state,
In order to bring (B1) into a molten state, it is not particularly limited, but it may be melted at a temperature 20 to 80 ° C. higher than its melting point by a multi-screw extruder such as a single-screw extruder or a twin-screw extruder. In melting (B2), similarly to (B1), using a multi-screw extruder such as a single-screw extruder or a twin-screw extruder,
What is necessary is just to melt at the temperature 20-80 degreeC higher than the melting point.

In order to mix (B1) and (B2) in such a molten state, a method of melt-mixing while extruding from (B2) extruder to (B1) extruder while melt-feeding, (B1) extruder (B2) is weighed, solid-side-fed and melt-mixed, (B1) extruder is melt-mixed while being melt-side-fed to (B2) extruder, (B2) is extruder (B2) A method in which B1) is solid-side-fed while being measured and melt-mixed, and the like are not particularly limited, but the method is preferably carried out in view of the compatibility of (B2) in (B1). By such a method, it is sufficient that (B2) is compatible with or dispersed in the form of islands, particles, rods or the like in (B1).

In laminating the above-mentioned EVOH (A) layer and the resin composition (B) layer, the EVOH (A) layer previously formed into a film or a sheet is added to the EVOH (A) layer.
(A) may be laminated.
Lamination methods such as solution coating, melt extrusion coating, film lamination (dry lamination), and co-extrusion are exemplified. In the solution coating, EVOH (A) is coated on the surface of the resin composition (B) layer formed in advance. Such coatings include EVOH (A)
A solution or dispersion of is used, and a mixed solvent of water and alcohol is used as a solvent at that time, and the amount of water is 30 to
70% by weight (the amount of alcohol is 70-30% by weight), preferably 40-60% by weight (the amount of alcohol is 60-4%)
0% by weight), and if it is less than 30% by weight or more than 70% by weight, a uniform solution is difficult to obtain and the coating film becomes opaque. Also, alcohol is methanol,
Ethanol, n-propyl alcohol, iso-propyl alcohol, n-butyl alcohol, iso-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, and the like, and n-propyl alcohol and iso-propyl alcohol are preferably used. You. Such EVOH (A)
The concentration of EVOH (A) in the solution or dispersion is not particularly limited and can be applied in an arbitrary range, and is usually 0.5 to 25% by weight.
Although the degree is preferable, it is most preferably 10 to 20% by weight in order to exhibit the effect of the present invention efficiently.

For coating, known methods can be employed, and examples thereof include a gravure coater, a reverse roll coater, an air knife coater, a rotor screen coater, a flat screen coater, a spray, a brush coating, and a bar coater. A gravure coater or reverse roll coater is used. After that, it is heated and dried to form a coating layer of EVOH (A). An ideal EVOH (A) solution or dispersion is applied when the EVOH (A) solution or dispersion is applied and dried. The solution viscosity at the time and the subsequent drying temperature are such that the solution viscosity at the time of applying the EVOH (A) solution is 50 to 10
00 cps, and the subsequent drying temperature may be arbitrarily selected from the range of about 70 to 100 ° C. The time for drying is not particularly limited, but is usually appropriately selected from the range of 10 seconds to 10 minutes (more preferably, 30 seconds to 5 minutes). The thickness (after drying) of the EVOH (A) coating layer is not particularly limited, but is preferably 1 to 50 μm, and particularly preferably 2 to 10 μm.
it is preferable that the [mu] m, (attached amount after drying) Chakuryou of the EVOH (A) preferably is 1 to 50 g / m ^2, more preferably from 2 to 10 g / m ^2. (The deposition amount of EVOH (A) is also the same for the following.) In applying such an EVOH (A) solution or dispersion,
Usually, an adhesive (anchor coat) layer is provided on the surface of the resin composition (B) layer. Examples of such an adhesive include an organic titanium-based adhesive, a two-component reactive polyurethane-based adhesive, and a polyester / isocyanate-based adhesive. A two-component reactive polyurethane-based adhesive is preferably used.

In the melt extrusion coating, it is preferable that the surface of the resin composition (B) layer is subjected to a primer treatment as necessary, and the primer treatment agent may be the above-mentioned organic titanium-based adhesive, Two-component reactive polyurethane adhesives, polyester / isocyanate-based adhesives, and the like are preferably used. Two-component reactive polyurethane adhesives are preferably used, and the amount of the primer treatment agent is 0.1 to 10 g / m. ² , preferably 0.3 to 5 g / m ²
It is. The surface is subjected to melt extrusion coating of EVOH (A) using a known melt extruder. In addition, in the case of melt extrusion coating, a support layer such as a polyolefin resin may be added as necessary to perform stable coating of EVOH (A), and two or more types of melt extrusion coating may be performed. Good.

In the film lamination (dry lamination), the surface of the resin composition (B) layer formed in advance is subjected to the above-mentioned primer treatment as required, and then the EVOH (A) layer (film or sheet) is coated. Lamination is performed. In this case, the EVOH (A) layer may be stretched or unstretched. In the case of stretching, the heat of fusion described later can be increased by the effect of short-time heat treatment and orientation. If a treatment or the like is performed, there is a possibility of shrinkage. In this case, a non-stretched film is preferable. The thickness of the EVOH (A) film at this time is preferably 5 to 50 μm, and more preferably 10 to 20 μm.

In co-extrusion, co-extrusion is performed through two types of two-layer dies. In the present invention, such EVOH
A layer of a thermoplastic resin (C) can be further provided outside the layer (B) of the laminate (layer (A) / resin composition (B)). In
Vinyl chloride resin, polyolefin resin, polyester resin, acrylic resin, polystyrene resin, polyamide resin and the like, among which vinyl chloride resin,
Polyolefin resins, polyester resins, and polyamide resins are preferably used.

Examples of such polyolefin resins include high-density polyethylene, medium-density polyethylene, (linear) low-density polyethylene, ultra-low-density polyethylene, vinyl acetate and acrylate, butene, hexene,
Polyethylene, polypropylene homopolymer copolymerized with α-olefins such as 4-methyl-1-pentene,
Polypropylene graft copolymerized with ethylene, polypropylene copolymerized with α-olefins such as 4-methyl-1-pentene, poly-1-butene, poly-4-methyl-1-pentene, and unsaturated carboxylic acid And modified polyolefin resins obtained by copolymerization or graft polymerization of acid anhydrides, vinyl silane compounds, epoxy group-containing compounds, etc., such as high-density polyethylene, medium-density polyethylene, (linear) low-density polyethylene, Polyethylene such as ultra-low density polyethylene, polypropylene homopolymer, polypropylene obtained by graft copolymerization of ethylene, polypropylene such as polypropylene obtained by copolymerizing α-olefins, and ethylene-vinyl acetate copolymer are preferably used.

In producing a laminate having the layer structure of (A) layer / (B) layer / (C) layer, the (C) layer is added to the laminate composed of (A) layer / (B) layer. A method of laminating, a method of performing film lamination, solution coating, and solution extrusion coating of (A) on the laminate comprising the (B) layer / (C) layer as described above, and adding (B) and (A) to the (C) layer Method of film lamination, solution coating, solution extrusion coating as described above, (A) to (C)
The layers can be formed by a method of co-extruding each layer.

Thus, a laminate having a layer structure of EVOH (A) layer / resin composition (B) layer or EVOH (A) layer / resin composition (B) layer / thermoplastic resin (C) layer can be obtained. However, in the present invention, E
Assuming that the VOH (A) layer is a, the resin composition (B) layer is b, and the thermoplastic resin (C) layer is c, c (polyolefin resin) / b / a, c (vinyl chloride resin) / b / a, c (polyolefin resin) / a / b / c (polyolefin resin), a / b / c (polyolefin resin) / c (vinyl chloride resin), a / b / c (polyester resin) /
c (vinyl chloride resin), c (acrylic resin) / a / b
/ C (vinyl chloride resin) and the like, in particular, (front side) a / b / c (vinyl chloride resin) (back side), (front side) a / b / c (polyolefin resin) /
Those having a laminated structure of c (vinyl chloride resin) (back side) are useful for interior material applications such as wallpaper and decorative sheets, and the back of the thermoplastic resin (C) layer of these laminates is paper or Japanese paper , Nonwoven fabric, asbestos, paper, glass, fiber, cloth, etc. for wallpaper can be applied with adhesive (adhesive) and then laminated by calendering method, laminating method, etc. A vinyl chloride resin (C) may be applied using a coater, a roll coater, or a flat screen coater, and then a laminate composed of the EVOH (A) and the resin composition (B) may be laminated.

When such a wallpaper is to be stuck to a wall, a well-known adhesive such as a commonly used aqueous starch paste may be applied to the base material and pressed against the wall, and the wall paper may be added with an added value such as design. It is also useful to form an uneven pattern by embossing at least one surface of these laminates in order to increase the roughness, as the uneven pattern is a wood grain conduit pattern, a pattern imitating the surface of a painted plate, an abstract pattern, Stone pattern, cloth pattern, line pattern, wood texture and a combination thereof can be used, and the depth of the concavo-convex pattern formed by such embossing varies depending on the pattern, but for wallpaper use,
Usually, it is preferable that the thickness is about 1 to 200 μm, because it gives a good three-dimensional effect. It is also useful to foam a layer of a vinyl chloride resin (C) or the like in order to impart a design property such as a wallpaper. In this case, a step of laminating a laminate comprising the EVOH (A) and the resin composition (B) May be before or after the foaming treatment, but it is preferable to perform the foaming treatment after laminating the laminate composed of the EVOH (A) and the resin composition (B) during the solution coating. In the case of the method, it is preferable that the EVOH (A) and the resin composition (B) are sequentially melt-coated after the foaming treatment, or the EVOH (A) and the resin composition (B) are laminated and laminated.

As a method of forming a concavo-convex pattern by embossing, a method of performing embossing using a normal heat embossing machine on which a desired concavo-convex pattern is formed, or a method of forming a desired concavo-convex pattern on a cooling roll of an extrusion coater or the like. Using a given embossing roll, a so-called mechanical embossing method such as a so-called doubling embossing method in which a laminate comprising the EVOH (A) and the resin composition (B) is formed and embossing at the same time, or a foaming inhibitor or a foaming accelerator is used. A chemical embossing method or the like is used in which an ink containing ink is printed and an uneven pattern is formed in a foaming process. A / b / c (vinyl chloride resin), a / b / c (polyolefin resin),
a / b / c (polyolefin resin) / c (polyolefin resin), a / b / c (polyolefin resin) /
c (polyolefin resin) / c (polyolefin resin) ..., a / b / c (vinyl chloride resin) / a, a /
b / c (polyolefin resin) / a, a / b / c (polyolefin resin) / c (polyolefin resin)
Those having a laminated structure such as ../a are useful as agricultural films (sheets).

In the present invention, a plasticizer (naturally contained in the soft vinyl chloride resin layer), a stabilizer, a surfactant, a crosslinkable substance (epoxy compound, polyvalent metal, inorganic Or organic polybasic acids or salts thereof), fillers, coloring agents, fibers (glass fibers, carbon fibers, etc.) as reinforcing materials, matting agents (talc, silica-based powder, resin fine powder such as polyethylene, polyurethane, etc.) ), A foaming agent and the like can be blended within a range that does not impair the effects of the present invention. In addition, a / b, a / b / c,.
The thicknesses of a, b, and c in the laminate such as... Cannot be unconditionally defined depending on the use or the like.
50 μm, b is 0.1 to 10 μm, c is 50 to 1000
It is arbitrarily selected from a range of about 0 μm.

The laminate of the present invention thus obtained can be used as a decorative sheet for finishing wallpaper such as wallpaper and furniture for office interiors, office supplies such as desk mats, notebooks and files using a cover made of PVC leather, and the like. It can be used for stationery, interior materials for automobiles, agricultural materials such as agricultural films, and daily necessities (vinyl mats, umbrellas, etc.), among which, as described in detail above, such as wallpaper and decorative sheets. It is very useful for interior materials and agricultural films (sheets), and especially useful for wallpaper with excellent stain resistance (stain removal properties).

[0025]

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 Vinyl acetate content 15%, carboxyl group content 1.5
90 parts by mole of maleic anhydride-modified ethylene-vinyl acetate copolymer (B1) and 10 parts of polystyrene (B2) having an SP value of 9.1 and MI of 1 g / 10 minutes (200 ° C., 5 kg load) were added to the mixture of (B1) The resin composition (B) is melt-mixed from the single screw extruder (B2) to the screw extruder by melt side feed method.
(Pellet) was obtained. (The blending ratio of (B1) and (B2) was adjusted by the discharge amount.) When the cross section of the pellet of the resin composition (B) was observed with a scanning electron microscope, it was found to be about 3 μm.
About (B2) particles were dispersed in (B1). Next, the resin composition (B) was formed into a film having a thickness of 20 μm by a single screw extruder. After applying 1.5 g / m ² of an isocyanate-reactive polyurethane adhesive on the surface of the film and drying, an ethylene content of 44 mol% and a saponification degree of 9 were obtained.
9.7 mol%, MI 12 g / 10 min (210 ° C., 216
A 12% solution of EVOH (A) (water / n-propanol = 40/60 (weight ratio)) having a weight of 0 g was prepared and coated (dry thickness: 5 μm). The following evaluation was performed using the obtained laminated body.

(Contamination removal property) Hot coffee at about 70 ° C. is applied or dropped to a size of about 2 cm in diameter on the surface of the EVOH (A) layer of the laminate, and exposed to water after leaving at 20 ° C. for 24 hours. The surface state of the laminate after wiping with cotton was visually evaluated as follows. In addition, it performed similarly about the soft polyvinyl chloride resin sheet single layer.
Separately, the obtained laminate was left to stand at 40 ° C. for 1 day, and the same evaluation was performed. In addition, shoe ink (wiped with a neutral detergent), softening, and water-based magic (wiped with a commercially available detergent (Magic Lin)) were similarly evaluated. ○ −−− Completely wiped off and no trace of contamination is observed. △ −−−− Although traces of contamination are observed, traces are smaller than in the case of the soft polyvinyl chloride resin sheet alone layer. C: Traces equivalent to those of a single layer of the soft polyvinyl chloride resin sheet are observed.

(Plasticizer migration) Laminate (10 cm × 10
cm) on a flat place with the EVOH (A) layer on top and a thickness of 3 m so as to be in contact with the surface of the EVOH (A) layer.
After placing a plasticizer-free vinyl chloride resin plate having a diameter of 5 cm and a diameter of 5 cm, a load of 50 g / cm ² was applied uniformly to 70
The weight change (plasticizer transfer amount) (g / m ² ) of the vinyl chloride resin plate after standing at 90 ° C. and 90% RH for 10 days was measured and evaluated as follows. ○ −−− Weight change is less than 2 g / m ² × −−− Weight change is 2 g / m ² or more

(Chemical resistance) About 1 cc of ethanol was dropped on the surface of the EVOH (A) layer of the laminate, and the surface state after standing for 1 hour in a normal state was visually observed and evaluated as follows. ○ −−− No abnormality × −−− Swelling is observed

Example 2 In the laminate of Example 1, an isocyanate-reactive polyurethane-based adhesive (AD-335A / cat-1 manufactured by Toyo Morton Co., Ltd.) was further provided on one surface of the resin composition (B) layer.
0) was laminated in the same manner as above except that a 400 μm thick vinyl chloride resin (C) sheet (plasticizer content: 50%) coated with 1.5 g / m ² was dry-laminated.
Evaluation was performed similarly.

Example 3 The same procedure as in Example 2 was carried out except that in place of the polystyrene (B2), an ethylene-vinyl acetate copolymer (B2) having a vinyl acetate content of 33% (SP value = 9.0) was used. To obtain a resin composition (B), a laminate was obtained in the same manner, and evaluation was performed in the same manner.

Example 4 Example 2 was repeated except that the polystyrene (B2) was replaced by a 1.5% maleic anhydride-modified ethylene-vinyl acetate copolymer (B2) (SP value = 8.7). Was performed in the same manner to obtain a resin composition (B), and then a laminate was obtained in the same manner, and evaluation was similarly performed.

Example 5 A laminate was obtained in the same manner as in Example 2 except that the mixing weight ratio of (B1) and (B2) was changed to (B1) / (B2) = 80 parts / 20 parts. Evaluation was performed similarly.

Example 6 In Example 3, EVOH (A) was replaced with ethylene having an ethylene content of 3.
2 mol%, saponification degree 99.8 mol%, MI 12 g / 10
A laminate was obtained in the same manner as above except that the EVOH was the same (same as above) to obtain a laminate, which was similarly evaluated.

Example 7 In Example 4, SB was used instead of polystyrene (B2).
A laminate was obtained in the same manner except that S (B2) (SP value = 8.6) was used, and was similarly evaluated.

Example 8 In Example 1, (B1) was replaced with a vinyl acetate content of 7
%, A maleic anhydride-modified ethylene-vinyl acetate copolymer (B1) having a carboxyl group content of 3 mol% was used and evaluated in the same manner.

Example 9 In Example 1, L was used instead of the vinyl chloride resin (C).
A laminate was obtained in the same manner except that LDPE (linear low-density polyethylene) (C) was used, and the laminate was similarly evaluated.

Comparative Example 1 A laminate was obtained in the same manner as in Example 1 except that the resin composition (B) was changed to the carboxyl group-containing ethylene-vinyl acetate copolymer (B1) alone. went.

Comparative Example 2 In Example 1, an unmodified ethylene-vinyl acetate copolymer having an ethylene content of 33% was used in place of the carboxyl group-containing (maleic acid-modified) ethylene-vinyl acetate copolymer (B1). A laminate was obtained in the same manner as above except that the test was performed, and the same evaluation was performed.

Comparative Example 3 A laminate was obtained in the same manner as in Example 1 except that polyisoprene (SP value = 8.0) was used instead of polystyrene (B2), and the same evaluation was performed. .

Comparative Example 4 A laminate was obtained in the same manner as in Example 1 except that polyacrylonitrile (SP value = 12) was used instead of polystyrene (B2), and the same evaluation was performed. Table 1 shows the evaluation results of the examples and the comparative examples.

[0041]

[Table 1] Stain removal plasticizer transferability Chemical resistance No treatment Example 1 after standing treatment ○ ○ ○ ○ 〃 2 ○ ○ ○ ○ 〃 3 ○ ○ ○ ○ ○ ４ 4 ○ ○ ○ ○ 〃 5 ○ ○ ○ ○ ６6 ○ ○ ○ 〃 ７7 ○ ○ ○ 〃 ８8 ○ ○ ○ 〃9 ○ ○ ○ ○ Comparative example 1 １ × × ○ 〃2 × × × 〃 ○ 3 × × × × ○ 4 × × × ×

[0042]

The laminate of the present invention is obtained by laminating a resin composition layer in which a specific thermoplastic resin is blended with a carboxyl group-containing ethylene-vinyl acetate copolymer and an EVOH layer. Excellent in decontamination properties, chemical resistance, etc., office supplies such as desk mats, office supplies such as desk mats, notebooks and files using PVC leather covers, as well as wallpaper for building interiors and decorative sheets for furniture etc. It is also very useful for laminated materials such as interior materials for automobiles, agricultural materials such as agricultural films, and daily goods (vinyl mats, umbrellas, etc.).

Claims (12)

[Claims] 1. A saponified ethylene-vinyl acetate copolymer (A) layer having an ethylene content of 20 to 60 mol% and a degree of saponification of 90 mol% or more, a carboxyl group-containing ethylene-vinyl acetate copolymer (B1) and SP value (calculated from Small's formula)
Wherein a resin composition (B) layer composed of a thermoplastic resin (B2) having a particle size of 8.5 to 11 is laminated. 2. An SP value (calculated from Small's formula) of 8.5.
The thermoplastic resin (B2) of ~ 11 has a Small number (G) of 250
2. The laminate according to claim 1, wherein the substituent is contained in an amount of 30% by weight or more in one molecule. 3. The laminate according to claim 2, wherein the substituent having a Small number (G) of 250 or more is any of a carbonyl group, a carboxyl group, a phenyl group, and a phenylene group. 4. An SP value (calculated from the Small formula) of 8.5.
The laminate according to any one of claims 1 to 3, wherein the thermoplastic resin (B2) is a polystyrene compound, an ethylene-vinyl acetate copolymer, or a derivative thereof. 5. A resin composition (B) having an SP value (Sm) in a carboxyl group-containing ethylene-vinyl acetate copolymer (B1).
thermoplastic resin (B calculated from the formula of all) 8.5 to 11
The laminate according to any one of claims 1 to 4, wherein 2) is dispersed. 6. A compounding weight ratio (B1) of a carboxyl group-containing ethylene-vinyl acetate copolymer (B1) and a thermoplastic resin (B2) having an SP value (calculated from the Small formula) of 8.5 to 11.
The laminate according to any one of claims 1 to 5, wherein / (B2) is 95/5 to 50/50. 7. The carboxyl group-containing ethylene-vinyl acetate copolymer (B1) has a carboxyl group content of 0.5 to 2.
The laminate according to any one of claims 1 to 6, wherein the amount is 0 mol%. 8. The method according to claim 1, wherein a thermoplastic resin (C) is further laminated outside the resin composition (B) layer.
A laminate according to any one of claims 1 to 7. 9. The thermoplastic resin (C) is a vinyl chloride resin,
The laminate according to claim 8, wherein the laminate is any one of a polyolefin resin, a polyester resin, and a polyamide resin. 10. The laminate according to claim 1, wherein the laminate is formed by any one of a solution coating method, a melt extrusion coating method, a dry laminating method, and a co-extrusion method. 11. The laminate according to claim 1, which is used for an interior material or an agricultural film. 12. The laminate according to claim 11, wherein the interior material is used for wallpaper.