JPH10305533A - Laminate - Google Patents

Abstract

(57) [Problem] To provide a laminate excellent in antifouling resistance (contamination removal property), chemical resistance and the like, and also useful for interior material use. SOLUTION: A saponified ethylene-vinyl acetate copolymer (A1) having an ethylene content of 20 to 60 mol% and a saponification degree of 90 mol% or more and an SP value (calculated from the Small formula) of 8.
A resin composition (A) layer composed of 5 to 11 thermoplastic resins (A2) and a thermoplastic resin (B) layer are laminated.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

[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 inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that ethylene-vinyl acetate having an ethylene content of 20 to 60 mol% and a saponification degree of 90 mol% or more. A resin composition (A) layer consisting of a polymer saponified product (A1) and a thermoplastic resin (A2) having an SP value (calculated from the Small formula) of 8.5 to 11 and a thermoplastic resin (B) layer are laminated. The inventors have found that the above-mentioned laminate solves the above-mentioned problems, and have completed the present invention.

[0005]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the production method of the present invention will be specifically described. The EVOH (A1) of the present invention has an ethylene content of 20 to 60 mol% (further 25 to 50 mol%),
The degree of saponification of the vinyl acetate component is 90 mol% or more (further 9
5% by mole or more) and has an ethylene content of 20
If the amount is less than 50 mol%, the effect of suppressing the plasticizer under high humidity becomes insufficient. On the other hand, if the amount exceeds 60 mol%, the barrier property of EVOH decreases, and the object of the present invention cannot be achieved. Even if the degree of conversion 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 (A1) 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 thermoplastic resin (A2) of the present invention must have an SP value (calculated from the Small formula) of 8.5 to 11, and further have a substituent having a Small number (G) of 250 or more. 1
It is preferable to contain 30% by weight or more in the molecule. If the SP value is less than 8.5, the resulting molded article has poor appearance and the effect of suppressing the plasticizer becomes insufficient. If the SP value exceeds 11, the effect of suppressing the plasticizer under high humidity is insufficient. As a result, the object of the present invention cannot be achieved. Also, when the substituent having a Small number (G) of not less than 250 is not contained in an amount of not less than 30% by weight in one molecule, the effect of suppressing the plasticizer becomes insufficient, which is not preferable.

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 (A2) include polystyrene. (SP value = 9.1), ethylene-vinyl acetate copolymer (vinyl acetate content 30-70% 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 30 to 70% by weight) (SP value = 8.5 to 9.5).
0) and their derivatives.

The blending weight ratio of the above (A1) and (A2) is not particularly limited, but the blending weight ratio is (A1) / (A2) = 9.
It is preferably 5 to 50/5 to 50, and more preferably (A
It is preferred that 1) / (A2) = 90-70 / 10-30. If the ratio (A1) is too large, the effect of suppressing the plasticizer under high humidity will be insufficient. On the other hand, if the ratio (A1) is too low, the decontamination property will be insufficient, which is not preferable. The method of mixing (A1) and (A2) is not particularly limited, but in the present invention, it is preferable that (A2) is melt-mixed with (A1) in a molten state or purified after dispersing in a solution. Thermoplastic resin (B) laminated with the resin composition (A) comprising (A1) and (A2) obtained above
Examples thereof include a vinyl chloride resin, a polyolefin resin, a polyester resin, an acrylic resin, a polystyrene resin, and a polyamide resin. Among them, a vinyl chloride resin, a polyolefin resin, a polyester resin, and a polyamide resin are preferable. Used for

The polyolefin resins include high-density polyethylene, medium-density polyethylene, (linear) low-density polyethylene, ultra-low-density polyethylene, vinyl acetate and acrylate, butene, hexene, and the like.
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.

The formation (lamination) of the laminate of the resin composition (A) layer and the thermoplastic resin (B) layer is not particularly limited, but may be a solution coating, a melt extrusion coating, a film lamination (dry lamination). ,
Lamination methods such as co-extrusion are mentioned. In the solution coating, a solution or dispersion of the resin composition (A) is used, and a mixed solvent of water and an 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 to 30% by weight), preferably 40 to 60% by weight (the amount of alcohol is 60 to 40% by weight). There is a problem that the coating is difficult to obtain and the coating becomes opaque. Examples of the alcohol include methanol, ethanol, n-propyl alcohol, iso-propyl alcohol, n-butyl alcohol, iso-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, etc., and n-propyl alcohol, iso-propyl Alcohol is preferably used.

The concentration of the resin composition (A) in the resin composition (A) solution or dispersion is not particularly limited and can be applied in an arbitrary range, and is usually preferably about 0.5 to 25% by weight. In order to exhibit the effect of the present invention efficiently, 10 to 2
0% by weight is most preferred. The solution or dispersion of the resin composition (A) is coated on the surface of the thermoplastic resin (B) layer. For such coating, a known method can be employed, for example, a gravure coater or a reverse roll coater. , Air knife coater,
Examples thereof include a rotor screen coater, a flat screen coater, a spray, a brush coating, and a bar coater. A gravure coater or a reverse roll coater is preferably used. Thereafter, the resin composition is heated and dried to form a coating layer of EVOH on the surface of the thermoplastic resin (B) layer. An ideal solution for applying and drying such a resin composition (A) solution or dispersion is used. The solution viscosity at the time of applying the resin composition (A) solution or dispersion and the subsequent drying temperature are such that the solution viscosity at the time of applying the resin composition (A) solution is 50 to 1000 cp.
s, and the subsequent drying temperature may be arbitrarily selected from the range of about 80 to 120 ° C. The drying time is not particularly limited, but is usually 10 seconds to 10 minutes (further 3 hours).
0 seconds to 5 minutes).

The thickness (after drying) of the coating layer of the resin composition (A) is not particularly limited, but is preferably 1 to 50 μm, particularly preferably 2 to 10 μm. The amount of coating (the amount of coating after drying) is 1 to 50 g / m
² is preferable, and ² to 10 g / m ² is more preferable. (The coating amount of the resin composition (A) is the same for the following.) When applying the resin composition (A) solution or dispersion, an adhesive (anchor) is usually attached to the surface of the base material. Coat) layer is provided. 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 thermoplastic resin (B) layer is subjected to a primer treatment, if necessary. As the primer treatment agent, the organic titanium-based adhesive described above, 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 . When the resin composition (A) is melt-extruded, a known melt extruder can be used, and it is preferable to perform melt extrusion coating on the surface of the base material (primed as necessary). In addition, at the time of melt extrusion coating, a support layer such as a polyolefin resin is inserted as necessary in order to perform stable coating of the resin composition (A), and two or more types of melt extrusion coating are performed. You may.

In the film lamination (dry lamination), the surface of the thermoplastic resin (B) layer is subjected to the above-mentioned primer treatment as required, and then an organic titanium-based adhesive, a two-part reactive polyurethane-based adhesive is used. In this case, the film of the resin composition (A) may be stretched or non-stretched. In the case of stretching, a short time heat treatment and an orientation The heat of fusion described below can be increased by the effect, but if an embossing treatment or the like is performed later, the film may shrink, and in this case, a non-stretched film is preferable. The thickness of the resin composition (A) film at this time is preferably 5 to 50 μm, more preferably 10 to 20 μm.
Is preferred.

In the co-extrusion, the layers (A) and (B) may be co-extruded through two or two or three or three dies through an adhesive resin layer as necessary. Thus, the resin composition (A) (layer) / thermoplastic resin (B) of the present invention
Although a laminate of (layer) is obtained, in the present invention, besides this, the resin composition (A) layer of the present invention may be a,
Assuming that the thermoplastic resin (B) layer is b, b (polyolefin resin) / a / b (vinyl chloride resin), b (polyolefin resin) / a / (polyolefin resin), a /
b (polyolefin resin) / b (vinyl chloride resin),
A laminated structure such as a / b (polyester resin) / b (vinyl chloride resin) and b (acrylic resin) / a / b (vinyl chloride resin) can be given.
/ B (vinyl chloride resin) (back side), (front side) a / b (polyolefin resin) / b (vinyl chloride resin) (back side)
Are useful for interior materials such as wallpaper and decorative sheets, and the back side of the thermoplastic resin (b) layer of these laminates is paper, Japanese paper, non-woven fabric, asbestos,
It is also possible to apply a sticking agent to paper, glass, fiber, cloth and other wallpaper materials and apply them by a method such as a calendar method or a laminating method. The vinyl chloride resin (B) can be applied by a flat screen coater, and then the resin composition (A) can be laminated.

When such a wallpaper is to be stuck to a wall, a known adhesive such as a water-based starch paste, which is generally used, 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 the laminate in order to increase the roughness, and the uneven pattern may be a wood grain conduit pattern, a pattern imitating the surface of a painted plate, an abstract pattern, a stone Eye pattern, cloth pattern, line pattern,
Wood patterns and combinations thereof can be used, and the depth of the concavo-convex pattern formed by such embossing varies depending on the pattern.
The thickness of about 200 μm is preferable because it gives a good three-dimensional effect. It is also useful to foam a base material such as a vinyl chloride resin in order to impart design properties such as wallpaper. In this case, the laminating step of the resin composition (A) may be performed before or after the foaming treatment. Specifically, at the time of solution coating, it is preferable to perform foaming treatment after laminating the resin composition (A), and at the time of melt coating or film laminating method, it is preferable to laminate the resin composition (A) after foaming treatment.

As a method of forming a concavo-convex pattern by embossing, a method of performing embossing using a normal heat embossing machine having a desired concavo-convex pattern, or a method of forming a desired concavo-convex pattern on a cooling roll of an extrusion coater or the like. Using an applied embossing roll, printing a so-called mechanical embossing method such as a so-called doubling embossing method or embossing simultaneously with forming a resin composition layer or an ink containing a foaming inhibitor or a foaming accelerator, and forming an uneven pattern in the foaming step. For example, a chemical embossing method is used. Also, a
/ B (polyvinyl chloride resin), a / b (polyolefin resin), a / b (polyolefin resin), a / b (polyolefin resin) / b (polyolefin resin), a
/ B (polyolefin resin) / b (polyolefin resin) / b (polyolefin resin) ..., a / b
Those having a laminated structure of (vinyl chloride resin) / a, a / b (polyolefin resin) / a, a / b (polyolefin resin) / b (polyolefin resin). Useful as a film (sheet).

In the present invention, a plasticizer (naturally contained in the soft vinyl chloride resin layer), a stabilizer, a surfactant and 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.) ) And the like can be blended as long as the effects of the present invention are not inhibited. Note that a / b, b / a / b,...
Although the thicknesses of a and b in the laminate such as cannot be unconditionally determined depending on the use or the like, usually, a is 1 to 50 μm, b
Is arbitrarily selected from the range of about 50 to 10000 μm, and when an adhesive is used between layers, the thickness of the adhesive layer is about 0.1 to 10 μm.

The thus obtained laminate of the present invention can be used as a decorative sheet for finishing wallpaper such as wallpaper for interior decoration or furniture, office supplies such as desk mats, notebooks and files using a cover made of PVC leather. 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).

[0021]

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 Ethylene content: 44 mol%, degree of saponification: 99.7 mol%,
MI 12g / 10min (210 ° C, 2160g load) E
80 parts of VOH (A1) and SP value 9.1, MI1g / 10
(200 ° C, 5kg load) polystyrene (A2) 20
The parts were melt-mixed to obtain a resin composition (A). Next, the resin composition (A) was formed into a film having a thickness of 20 μm by a single screw extruder. Further, an isocyanate reaction type polyurethane adhesive (AD-33, manufactured by Toyo Morton Co., Ltd.)
Dry lamination of the above film on the adhesive surface of a soft polyvinyl chloride (B) sheet (plasticizer content: about 50% by weight) having a thickness of 400 μm coated with 5A / cat-10) of 1.5 g / m ^2. Thus, a laminate was produced. The following evaluation was performed using the obtained laminated body.

(Stain Removal Property) Resin Composition (A) of Laminate
Hot coffee at about 70 ° C. is applied or dropped on the layer surface to a size of about 2 cm in diameter, left standing at 20 ° C. for 24 hours, and then wiped off with a bleached cotton soaked in water. The evaluation was 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) is placed on a flat surface with the resin composition (A) layer facing upward, and a plasticizer-free vinyl chloride resin plate having a thickness of 3 mm and a diameter of 5 cm is in contact with the surface of the resin composition (A) layer. Is placed, a uniform load of 50 g / cm ² is applied to
The weight change (plasticizer transfer amount) (g / m ² ) of the vinyl chloride resin plate after standing at 0 ° C. and 90% RH for 10 days was measured.
The evaluation was 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 resin composition (A) layer of the laminate, and the surface condition after standing for 1 hour in a normal state was visually observed and evaluated as follows. ○ −−− No abnormality × −−− Swelling is observed

Example 2 The procedure of Example 1 was repeated, except that the polystyrene (A2) was replaced by an ethylene-vinyl acetate copolymer (A2) having a vinyl acetate content of 33% (SP value = 9.0). To obtain the resin composition (A), water / n-propanol = 1
/ 1 (weight ratio), after dissolving and dispersing so that the resin content becomes 15%, and then coating on the sheet of the soft polyvinyl chloride (B) pretreated in Example 1, Drying was performed at 100 ° C. for 5 minutes to obtain a laminate having a / b = 5 μm / 400 μm, which was similarly evaluated.

Example 3 Example 1 was repeated except that the polystyrene (A2) was replaced by a 1.5% maleic anhydride-modified ethylene-vinyl acetate copolymer (A2) (SP value = 8.7). Was carried out in the same manner to obtain a resin composition (A), and then an ethylene-vinyl acetate copolymer-based adhesive (manufactured by Mitsubishi Chemical Corporation) was placed on the sheet of flexible polyvinyl chloride (B) pretreated in Example 1. , "Modic-AP E-300S") and the resin composition (A) were melt-extruded in this order, and a / adhesive layer / b =
A laminate of 5 μm / 10 μm / 400 μm was obtained and evaluated in the same manner.

Example 4 A laminate was obtained in the same manner as in Example 2, except that the mixing weight ratio of EVOH (A1) and polystyrene (A2) was changed to (A1) / (A2) = 70 parts / 30 parts. And evaluated similarly.

Example 5 In Example 3, EVOH (A1) was converted to 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 amount was the same (as above), and the evaluation was performed in the same manner.

Example 6 In Example 4, SB was used instead of polystyrene (A2).
A laminate was obtained in the same manner except that S (A2) (SP value = 8.6) was used, and was similarly evaluated.

Example 7 The procedure of Example 5 was repeated, except that the maleic anhydride-modified ethylene-vinyl acetate copolymer (A2) was replaced by an amorphous polyester (A2) (SP value = 10.5). To obtain a laminate, which was similarly evaluated.

Comparative Example 1 A laminate was obtained in the same manner as in Example 1 except that polyisoprene (SP value = 8.0) was used instead of polystyrene (A2), and a similar evaluation was performed. .

Comparative Example 2 A laminate was obtained in the same manner as in Example 1 except that polyacrylonitrile (SP value = 12) was used instead of polystyrene (A2), and a laminate was similarly evaluated. Table 1 shows the evaluation results of the examples and the comparative examples.

[0033]

[Table 1] Stain removal plasticizer transferability Chemical resistance No treatment Example 1 after standing treatment ○ ○ ○ ○ 〃 2 ○ ○ ○ ○ 〃 3 ○ ○ ○ ○ ○ ４ 4 ○ ○ ○ ○ 〃 5 ○ ○ ○ ○ ６ 6 ○ ○ ○ ○ 〃 7 ○ ○ ○ ○ Comparative Example 1 ○ × × × 〃 2 ○ × × ×

[0034]

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

Claims (9)

[Claims] 1. A saponified ethylene-vinyl acetate copolymer (A1) having an ethylene content of 20 to 60 mol% and a saponification degree of 90 mol% or more and an SP value (calculated from the Small formula) of 8.
A laminate comprising: a resin composition (A) layer composed of 5 to 11 thermoplastic resins (A2); and a thermoplastic resin (B) layer. 2. An SP value (calculated from Small's formula) of 8.5.
Thermoplastic resin (A2) having 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 (A2) is a polystyrene-based compound, an ethylene-vinyl acetate copolymer, or a derivative thereof. 5. A saponified ethylene-vinyl acetate copolymer (A1) having an ethylene content of 20 to 60 mol% and a saponification degree of 90 mol% or more and an SP value of 8.5 to 11 (calculated from Small's formula). Of thermoplastic resin (A2)
The laminate according to any one of claims 1 to 4, wherein 1) / (A2) = 95 to 50/5 to 50. 6. The thermoplastic resin (B) is a vinyl chloride resin,
It is any one of a polyolefin resin, a polyester resin, and a polyamide resin.
5. The laminate according to any one of 5. 7. 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 film laminating method, and a co-extrusion method. 8. The laminate according to claim 1, wherein the laminate is used for interior materials or agricultural films. 9. The laminate according to claim 8, wherein the interior material is used for wallpaper.