JP5455679B2 - wallpaper - Google Patents

Description

  The present invention relates to a wallpaper to be applied to a wall or the like in order to adjust indoor decoration and environment, and in particular, ethylene-vinyl ester having a 1,2-diol structural unit represented by the following general formula (1) The present invention relates to a wallpaper having a saponified copolymer layer.

  Conventionally, a wallpaper or a decorative board made of a thermoplastic resin such as polyvinyl chloride is known. However, these wallpaper and decorative boards made of thermoplastic resin are easily contaminated with cigarette smoke, dirt, graffiti, pigments in various foods, and the plasticizer that the thermoplastic resin normally contains is used for wallpaper and decorative boards. There was a problem that the surface bleeds, and dust easily adheres to the surface, which makes it easy to get dirty.

Therefore, even if the base material bleeds out the plasticizer, the base material has a saponified ethylene-vinyl ester copolymer (hereinafter referred to as EVOH) in order to prevent the base material from seeping out. There is known a wallpaper in which layers are laminated (for example, see Non-Patent Document 1).
Further, according to such a technique, EVOH has a specific resistance of being strong against an organic solvent and an aqueous solvent, respectively, and therefore has an advantage that each of oily and aqueous stains is difficult to be attached.

Japanese Utility Model Publication No.59-172797

  However, although the above technology is excellent in antifouling properties, there is room for improvement in moisture absorption performance and moisture release performance, and it is not possible to alleviate indoor humidity fluctuations, which may cause discomfort due to fluctuations in the indoor environment. . In order to reduce such discomfort due to humidity, the ability to absorb and release moisture in the air has been demanded.

In view of the above circumstances, as a result of intensive studies, the inventors of the present invention have an EVOH layer in which the content of an ethylene structural unit is 20 to 60 mol% and a 1,2-diol structural unit is present in a side chain. It has been found that by using a wallpaper made by laminating layers, the conventional EVOH has the basic performance of antifouling properties and exhibits high affinity for moisture in the air.
This is because, by having a 1,2-diol structural unit, the number of hydroxyl groups per molecule of the polymer is increased, so that the hydrophilicity of EVOH is improved and the water absorption and release performance is improved. -It is considered that the performance of the main chain is maintained by the presence of the diol structural unit in the side chain, and the antifouling performance inherent to EVOH can be maintained.

That is, the gist of the present invention is ethylene having a 1,2-diol structural unit represented by the following general formula (1) having a content of ethylene structural units of 20 to 60 mol% on a substrate. -It exists in the wallpaper which provides the saponified material layer of a vinyl ester copolymer.
[In General Formula (1), R1, R2, and R3 each independently represent a hydrogen atom or an organic group, X represents a single bond or a bond chain, and R4, R5, and R6 each independently represent a hydrogen atom. Or an organic group is shown. ]

A conventional EVOH has a base material using a wallpaper in which an EVOH layer having an ethylene structural unit content of 20 to 60 mol% and having a 1,2-diol structural unit in the side chain is used. The performance of the improvement point is improved while maintaining the basic performance. Specifically, it not only has good contamination resistance and solvent resistance, but also has an environmental adjustment function by the ability to absorb and release moisture in the air (hereinafter sometimes referred to as moisture absorption / release performance). Newly granted.

Hereinafter, although it demonstrates in detail about the structure of this invention, these show an example of a desirable embodiment. The present invention resides in a wallpaper in which an ethylene-vinyl ester copolymer saponified layer having a 1,2-diol structural unit represented by the following general formula (1) is provided on a base material.

[In General Formula (1), R ¹ , R ² , and R ³ each independently represent a hydrogen atom or an organic group, X represents a single bond or a bonded chain, and R ⁴ , R ⁵ , and R ⁶ represent Each independently represents a hydrogen atom or an organic group. ]

(Explanation of EVOH)
The saponified ethylene-vinyl ester copolymer having a 1,2-diol structural unit represented by the general formula (1) will be described.
The modified EVOH having a structural unit represented by the general formula (1) used in the present invention is known.

  Examples of the vinyl ester monomers include vinyl formate, vinyl acetate, vinyl propionate, vinyl valelate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caprate, vinyl laurate, vinyl stearate, vinyl versatate, etc. Aliphatic vinyl esters, aromatic vinyl esters such as vinyl benzoate, and the like. Usually, aliphatic vinyl esters having 3 to 20 carbon atoms, preferably 4 to 10 carbon atoms, and particularly preferably 4 to 7 carbon atoms. . From the economical viewpoint, vinyl acetate is particularly preferably used. These are usually used alone, but a plurality of them may be used simultaneously as necessary.

  The content of the structural unit (1) in EVOH is usually 0.1 to 30 mol%, preferably 0.5 to 10 mol%, particularly preferably 0.3 to 3 mol%, particularly preferably 1 to 2. Mol%. If the content is too small, the moisture absorption / release performance tends to decrease, and if the content is too large, resistance to hot water contamination (for example, a warm beverage such as coffee) tends to be low.

  Further, in order to adjust the content of the structural unit, it is also possible to adjust by blending at least two types of EVOH having different contents of the structural unit (1), and at least one of them is a structural unit ( EVOH resin not containing 1) may be used.

With regard to EVOH in which the side chain 1,2-diol bond amount is adjusted in this way, the side chain 1,2-diol bond amount can be calculated by weight average, and exactly ¹ H-NMR measurement is possible. From the results, the amount of side chain 1,2-diol bonded can be calculated.

In addition, EVOH used in the present invention has an ethylene structural unit content of 20 to 60 mol%, preferably 20 to 55 mol%, particularly preferably 25 to 50 mol%, measured based on ISO14663. If the ethylene content is too low, the resistance to hot water contamination (for example, a warm beverage such as coffee) tends to be low, and if it is too high, the moisture absorption / release performance tends to be low.

  Furthermore, the saponification degree of the EVOH component is a value measured by a titration method (JIS K6726) (however, EVOH is a solution uniformly dissolved in water / methanol solvent) and is usually 90 to 100 mol%, preferably 95 to 100%. It is mol%, particularly preferably 98 to 100%. When the degree of saponification is too low, the heat resistance of EVOH is lowered, and the workability tends to be lowered.

  The melt flow rate (hereinafter sometimes referred to as MFR) of the EVOH component is usually 0.1 to 100 g / 10 minutes, preferably 1 to 50 g / 10 minutes, particularly preferably measured at 210 ° C. and a load of 2160 g. 2 to 40 g / 10 min. If this value is too low, the processability tends to decrease, and if it is too high, the strength of the film tends to decrease.

The organic group in the 1,2-diol structural unit represented by the general formula (1) is not particularly limited, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and an isobutyl group. And saturated hydrocarbon groups such as tert-butyl group, aromatic hydrocarbon groups such as phenyl group and benzyl group, halogen atom, hydroxyl group, acyloxy group, alkoxycarbonyl group, carboxyl group and sulfonic acid group.
R ^{1 to} R ³ are usually preferably a saturated hydrocarbon group or a hydrogen atom having 1 to 30 carbon atoms, particularly 1 to 15 carbon atoms, and more preferably 1 to 4 carbon atoms. R ^{4 to} R ⁵ are preferably an aliphatic hydrocarbon group or a hydrogen atom having 1 to 30 carbon atoms, particularly 1 to 15 carbon atoms, more preferably 1 to 4 carbon atoms, and most preferably a hydrogen atom. In particular, it is preferable that R ^{1 to} R ⁶ are all hydrogen and X is a single bond.

Further, X in the structural unit represented by the general formula (1) is typically a single bond from the viewpoint of heat resistance during processing.
In addition, a bond chain may be used as long as the effect of the present invention is not inhibited. Such a bonding chain is not particularly limited, but other than hydrocarbon chains such as alkylene, alkenylene, alkynylene, phenylene, naphthylene (these hydrocarbons may be substituted with halogen such as fluorine, chlorine, bromine, etc.), _{-O -, - (CH 2 O} ) m -, - (OCH 2) m -, - (CH 2 O) m CH 2 - structure containing an ether binding site, such as, -CO -, - COCO -, - CO _{(CH 2) m CO -,} - CO (C 6 H 4) CO- structure containing a carbonyl group such as, -S -, - CS -, - SO -, - SO 2 - structure containing a sulfur atom, such as, -NR -, - CONR -, - NRCO -, - CSNR -, - NRCS -, - structure comprising NRNR- such as nitrogen atoms, -HPO ₄ - structure containing a hetero atom such as structure containing a phosphorus atom, such as, -Si _{(OR) 2} - _{-OSi (OR) 2 -, -} OSi (OR) structure containing 2 O- such as silicon _{atoms, -Ti (OR) 2 -,} - OTi (OR) 2 -, - OTi (OR) 2 O- , etc. Examples include a structure containing a titanium atom, a structure containing a metal atom such as a structure containing an aluminum atom such as -Al (OR)-, -OAl (OR)-, and -OAl (OR) O-. And a hydrogen atom or an alkyl group is preferred, and m is a natural number, usually 1 to 30, preferably 1 to 15, and more preferably 1 to 10. Among them, —CH ₂ OCH ₂ — and a hydrocarbon chain having 1 to 10 carbon atoms are preferable from the viewpoint of stability at the time of production or use, and further, a hydrocarbon chain having 1 to 6 carbon atoms, particularly 1 carbon atom. It is preferable that

The most preferred EVOH structure in the present invention is one in which R ¹ and R ^{2 to} R ⁴ in the structural unit (1) are all hydrogen atoms and X is a single bond. That is, those containing a structural unit represented by the following structural formula (1a) are preferable.

The most preferred constitution of EVOH is that the structural unit (1a) is 1 to 2 mol%, the ethylene content is 25 to 50 mol%, a structural unit derived from vinyl alcohol, and the remainder is a vinyl acetoxy structure derived from vinyl acetate. It consists of units and has a saponification degree of 98 to 100 mol% and MFR of 2 to 40 g / 10 min (210 ° C., load 2160 g).

  The method for producing EVOH used in the present invention is not particularly limited. When EVOH containing structural unit (1a) which is the most preferable structure is taken as an example, [1] 3,4-diol-1-butene as a comonomer, 3,4-diacyloxy-1-butene, 3-acyloxy-4-ol-1-butene, 4-acyloxy-3-ol-1-butene, 3,4-diacyloxy-2-methyl-1-butene, etc. are used. These are copolymerized with vinyl ester monomers to obtain copolymers, and then saponified, or [2] vinyl ethylene carbonate or the like is used as a comonomer to copolymerize these with vinyl ester monomers. To obtain a copolymer and then saponify and decarboxylate it, or [3] 2,2-dialkyl-4-vinyl as a comonomer Using 1,3-dioxolane, etc., copolymerized with these with a vinyl ester monomer to obtain a copolymer, then saponification, and a method of deacetalization thereof.

  Among them, the polymerization proceeds well, and it is easy to uniformly introduce 1,2-diol structural units into EVOH, and there are few problems when melt-molding the obtained EVOH, and further, In view of the final film characteristics, the production method [1] is preferably used, and particularly preferably, 3,4-diacyloxy-1-butene and a vinyl ester monomer are used in view of excellent copolymerization reactivity. This is a method for saponifying a copolymer obtained by copolymerization. Furthermore, it is preferable to use 3,4-diacetoxy-1-butene as 3,4-diacyloxy-1-butene. Moreover, you may use the mixture of these said monomers.

In addition, the reactive ratio of each monomer when vinyl acetate is used as the vinyl ester monomer and 3,4-diacetoxy-1-butene is copolymerized is r (vinyl acetate) = 0.710, r ( 3,4-diacetoxy-1-butene) = 0.701, and in the case of vinyl ethylene carbonate described later, r (vinyl acetate) = 0.85, r (vinyl ethylene carbonate) = 5.4, 3,4-diacetoxy-1-butene is superior in copolymerization reactivity with vinyl acetate.
The chain transfer constant of 3,4-diacetoxy-1-butene is Cx (3,4-diacetoxy-1-butene) = 0.003 (65 ° C.). In the case of vinyl ethylene carbonate, Cx (vinyl Ethylene carbonate) = 0.005 (65 [deg.] C.) and Cx (2,2-dimethyl-4-vinyl-1,3-dioxolane) in the case of 2,2-dimethyl-4-vinyl-1,3-dioxolane = Compared with 0.023 (65 ° C.), it is a hindrance to polymerization and does not easily increase the degree of polymerization or cause a decrease in polymerization rate.

  In addition, such 3,4-diacetoxy-1-butene is the same as that derived from the vinyl acetate structural unit, which is a main structural unit, as a by-product generated when the copolymer is saponified. The fact that there is no need to provide a special device or process is also a great industrial advantage. Further, 3,4-diacetoxy-1-butane, 1,4-diacetoxy-1-butene, 1,4-diacetoxy-1-butane and the like may be contained as a small amount of impurities.

  3,4-diol-1-butene is available from Eastman Chemical Co., and 3,4-diacetoxy-1-butene is commercially available from Eastman Chemical Co. be able to. Further, 3,4-diacetoxy-1-butene obtained as a by-product during the production process of 1,4-butanediol can also be used.

  EVOH having a 1,2-diol structural unit produced by the production method of [2] and [3] described above has a carbonate ring and a side chain in the case where the degree of saponification is low or decarboxylation is insufficient. Since the dioxolane ring remains and the resulting EVOH structure lacks denseness and is inferior in gas barrier properties, it must be used with this in mind.

  In addition, what is necessary is just to determine the weight ratio of the 1, 2-diol structural unit monomer represented by the said General formula (1) at the time of copolymerizing according to the desired introduction amount mentioned above. Moreover, depending on the case, you may copolymerize the ethylenically unsaturated monomer which can be copolymerized in the range which does not inhibit the effect of this invention at the time of copolymerization (for example, 50 mol% or less).

  Moreover, it is preferable to add a known polymerization inhibitor used in radical polymerization to the reaction system at the end of the polymerization. Examples of such polymerization inhibitors include m-dinitrobenzene, ascorbic acid, sorbic acid, benzoquinone, α-methyl. Examples include dimers of styrene and p-methoxyphenol.

  The copolymer thus obtained is then saponified, and the resin obtained by solid-liquid separation is dried, whereby the 1,2-diol structural unit represented by the above general formula (1) is obtained. EVOH having is obtained.

Therefore, EVOH in the present invention can have a structure derived from a partially unsaponified comonomer.
The other part is a vinyl alcohol structural unit and a remaining vinyl ester-derived acyloxy group-containing structural unit (and a small amount of a copolymerizable ethylenically unsaturated monomer structural unit).
The saponification degree in the present invention is a value measured by a titration method (JIS K6726). The ester part of the vinyl ester monomer and the acyloxy part or carbonate of the comonomer corresponding to the 1,2-diol structural unit are used. This means the rate of change (mol%) of the total amount of parts and acetal parts to hydroxyl groups.

  The EVOH used in the present invention may be a blend of EVOH containing the structural unit (1) and other EVOH different from the EVOH. Other EVOH resins include those having different structural units, Examples thereof include those having different ethylene contents, those having different saponification degrees, and those having different melt flow rates.

Other thermoplastic resins can be blended with the above-mentioned EVOH within a range not inhibiting the effects of the present invention (for example, 30% by weight or less with respect to EVOH).
In addition, the EVOH used in the present invention includes a thermal stabilizer (for example, acetic acid, phosphoric acid, boric acid and salts thereof, hinders, if necessary (for example, 10% by weight or less based on a resin component such as EVOH). Dophenol compounds, hindered amine compounds) antioxidants, lubricants, plasticizers, surfactants, light stabilizers, UV absorbers, colorants, antistatic agents, antibacterial agents, inorganic fillers, oxygen absorbers, gel generation prevention An agent (for example, a hydrotalcite-based compound or the like can be added within a range that does not impair the effects of the present invention.

(Description of wallpaper)
The wallpaper in the present invention is formed by providing an EVOH layer having a base material layer and containing the structural unit (1) on the surface layer. As such a base material, a base material used for general wallpaper is used.
Examples of such a substrate include flame retardant paper, inorganic paper, high quality paper, thin paper and the like; cloth such as woven fabric and nonwoven fabric; glass fiber; wood; and thermoplastic resin. From the viewpoint of wallpaper versatility, paper and thermoplastic resin are preferred. As the substrate, at least one of these may be used, and two or more of these may be used at the same time, for example.
Among them, it is particularly preferable to use paper and a thermoplastic resin in combination as a base material from the viewpoint of strength, handleability, and the like.

  Examples of the thermoplastic resin used for the base material include polyethylene such as linear low density polyethylene, low density polyethylene, ultra low density polyethylene, medium density polyethylene, and high density polyethylene, polypropylene, and ethylene-propylene (block and random). Copolymer, propylene-α-olefin (α-olefin having 4 to 20 carbon atoms) copolymer, polybutene, polypentene, cyclic polyolefin, or those obtained by graft-modifying these polyolefin resins with unsaturated carboxylic acid or ester thereof Polyolefin resins such as polyethylene terephthalate resins, polybutylene terephthalate resins, polyethylene naphthalate resins and other polyester resins; nylon 6, nylon 66, nylon 6/12, nylon 6/66, MXD6 na Polyamide resins such as Iron; Chlorine resins such as polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene; polystyrene, ionomers, ethylene-vinyl acetate copolymers, ethylene-acrylic acid copolymers, ethylene -Acrylic acid ester copolymers, acrylic resins, vinyl ester resins, polyester elastomers, polyurethane elastomers, aromatic or aliphatic polyketones, and polyalcohols obtained by reducing them, polycarbonates, etc. From the standpoint of performance and production cost, it is preferably at least one selected from a chlorine-based resin, a polyolefin-based resin, and an ethylene-vinyl acetate-based copolymer, and particularly preferably polyvinyl chloride, polyethylene, ethylene-vinyl acetate-based Is it a copolymer? It is at least one selected. Particularly preferred are polyvinyl chloride and ethylene-vinyl acetate copolymers.

  The above thermoplastic resins are generally used plasticizers, lubricants, heat stabilizers, light stabilizers, ultraviolet absorbers, antioxidants, colorants, antistatic agents, surfactants, antibacterial agents, and inorganic fillers. It is also possible to blend additives such as oxygen absorbers or blend other resins (for example, polyolefin resins, polyamide resins, etc.). In particular, as a gel generation inhibitor, a hydrotalcite compound, a hindered phenol compound, a hindered amine heat stabilizer, or a metal salt of a higher aliphatic carboxylic acid may be included.

  Further, the thermoplastic resin may be foamed if necessary, or may be foamed after being laminated with EVOH.

(Wallpaper manufacturing method)
The wallpaper of the present invention can be manufactured by a generally known method. For example, (1) a method of preparing the EVOH film, and laminating the substrate and the film (dry laminating method); (2) applying the EVOH solution or dispersion to the substrate and drying (3) a method of melt laminating the above EVOH on a base material, and a method of melt laminating a base resin on EVOH when the base material is a thermoplastic resin, (4) a base material is heated In the case of a plastic resin, a coextrusion molding method may be mentioned. Among them, (1) dry laminating method and (3) melt laminating method (4) coextrusion molding method are preferably selected.

  When producing an EVOH film in the above (1), a known general production method can be adopted as the production method.

The base material may be subjected to a known printing process. Furthermore, it is also preferable that the interlayer between the base material and the EVOH is bonded via a known adhesive or adhesive resin.
Among these, (4) the co-extrusion molding method is most preferable from the viewpoint of cost and environment.

The wallpaper of the present invention may be subjected to post-processing such as surface matting or three-dimensional molding.
Since the EVOH used in the present invention is excellent in molding processability, the wallpaper of the present invention is easy to have uneven patterns even when subjected to three-dimensional molding processing such as drawing and embossing, and it is difficult to generate extra wrinkles. There are advantages.

In the wallpaper of the present invention, the total thickness is usually 25 to 1200 μm. When the thickness is too thick, handling tends to be difficult due to an increase in weight, and when it is too thin, the strength tends to decrease.
When using paper as a base material layer, the basic weight is 50-300 g / m <2> normally. When using a thermoplastic resin as a base material layer, the thickness is 10-1000 micrometers normally, Preferably it is 30-700 micrometers, Most preferably, it is 50-500 micrometers.
In addition, when using together paper and a thermoplastic resin as a base material layer, and when using multiple layers of paper and a thermoplastic resin, respectively, it is preferable that the thickness of each single layer is said range.

The thickness of the EVOH layer is usually 1 to 100 μm, preferably 3 to 50 μm, particularly preferably 5 to 30 μm. If the thickness is too thick, the handleability tends to be low when the wallpaper is applied, and if it is too thin, the antifouling property tends to be low.
Furthermore, the thickness ratio in the case of using a thermoplastic resin as a base material is usually 1/10 to 6/10 as thermoplastic resin / EVOH in a state where the respective layers are added together.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist. In the examples, “parts” and “%” are based on weight unless otherwise specified.

Example 1
Saponified ethylene-vinyl acetate copolymer having the structural unit (1a) as EVOH (ethylene composition 38 mol%, saponification degree 99.6 mol%, structural unit (1a) content 1.5 mol%, MFR 4 g / 10 min (210 ° C., load 2160 g), density 1.17 g / cm ³ ) was used.

The EVOH was formed under the following conditions using a single screw extruder to obtain a single layer film having a thickness of 60 μm.
Extruder: Diameter (D) = 40mm, L / D = 28
Screen pack: 90/120/90 mesh Screw rotation speed: 80 rpm
Set temperature: C1 / C2 / C3 / C4 / C5 / C6-D = 150/200/220/220/220/220
-℃
Discharge rate: 16kg / hr
Take-off speed: 10 m / min
Cooling temperature: 50 ° C

Further, the EVOH was formed under the following conditions using a single screw extruder to obtain a single layer film having a thickness of 200 μm.

Extruder: Diameter (D) = 40mm, L / D = 28
Screen pack: 90/120/90 mesh Screw rotation speed: 80 rpm
Set temperature: C1 / C2 / C3 / C4 / C5 / C6-D = 150/200/220/220/220/220
-℃
Discharge rate: 16kg / hr
Take-off speed: 3m / min
Cooling temperature: 50 ° C
Using these films, antifouling tests and moisture absorption / release tests were performed as follows.

[Evaluation]
<Water resistance stain test>
Draw a circle with a diameter of 25mm with oil-based alcohol ink (JOINTEX oil-based twin marker H027J black) on the film surface of 60μm in thickness, and about 140ml of coffee with a temperature of 80 ℃ (KEURIG coffee extractor KFE B40J with basic roast) Extraction) was applied uniformly. The film was naturally dried at 23 ° C. and 50% RH for 1 hour, and then half of the circle was masked with a transparent adhesive tape.
The circle marked with a cloth dampened with water was wiped off, and the state of the film was observed.
○: Dirt is almost completely removed and there is no coloring. △ ... Dirt is removed, but some coloring remains. × ... Dirt and coloring are the same as the masked part. Remaining

<Oil resistance stain test 1>
A circle with a diameter of 25 mm was drawn on the surface of a film having a thickness of 60 μm with oil-based ink (Pentel pen oil-based medium red), and the circle was uniformly painted with the same ink. The film was allowed to stand for 10 minutes at 23 ° C. and 50% RH, and then half of the circle was masked with a transparent adhesive tape.
The circle marked with a cloth moistened with xylene was wiped off and the state of the film was observed.
○: Dirt is almost completely removed and there is no coloring. △ ... Dirt is removed, but some coloring remains. × ... Dirt and coloring are the same as the masked part. Remaining

<Oil resistance stain test 2>
A circle with a diameter of 25 mm was drawn on the surface of a 60 μm-thick film with oil-based alcohol ink (JOINTEX oil-based twin marker H027J fine black), and the circle was uniformly painted with the same ink. The film was allowed to stand for 10 minutes at 23 ° C. and 50% RH, and then half of the circle was masked with a transparent adhesive tape.
The circle marked with a cloth moistened with xylene was wiped off and the state of the film was observed.
○: Dirt is almost completely removed and there is no coloring. △ ... Dirt is removed, but some coloring remains. × ... Dirt and coloring are the same as the masked part. Remaining

<Moisture absorption / release test>
A film having a thickness of 200 μm was cut into a size of 100 mm × 100 mm, the sample was immersed in ion-exchanged water placed in a 500 ml beaker, and the water absorption rate was determined from the amount of water absorbed one day later.
Further, after 6 days, the film was taken out and the saturated water absorption was determined. Furthermore, the water discharge rate when naturally dried for 1 day under conditions of 23 ° C. and 50% RH was determined.

Comparative Example 1
Unmodified ethylene-vinyl acetate copolymer saponified product (ethylene composition 38 mol%, saponification degree 99.6 mol%, MFR 4 g / 10 min (210 ° C., load 2160 g), density 1.17 g / cm ³ ) A film was prepared in the same manner as in Example 1 except that it was used, and evaluated in the same manner.
The results are shown in Tables 1 and 2

[Table 1]

[Table 2]

In the antifouling test, it has been clarified that the wallpaper having the EVOH of the present invention does not deteriorate the excellent antifouling property that has been conventionally obtained by containing the structural unit (1).
Moreover, in the moisture absorption / release test, it was shown that the modified EVOH included in the wallpaper of the present invention has a high hydrophilic ability and an excellent environment adjusting ability.

  The wallpaper of the present invention is particularly useful for wallpaper that is capable of preventing condensation in the walls and controlling the humidity in the room, and an inner wall structure (such as an inner wall board, inner wall panel, and inner wall structure) using the wallpaper. It can also be used for interiors of furniture in which moisture is desired, close-ups, interiors of automobiles, linings of storage devices such as musical instruments and artworks, and the like.

Claims (4)

An ethylene-vinyl ester copolymer having a base layer, an ethylene structural unit content of 20 to 60 mol%, and a 1,2-diol structural unit represented by the following general formula (1) A wallpaper in which a combined saponification layer is provided on the surface layer.
[In General Formula (1), R1, R2, and R3 each independently represent a hydrogen atom or an organic group, X represents a single bond or a bond chain, and R4, R5, and R6 each independently represent a hydrogen atom. Or an organic group is shown. ]   2. The wallpaper according to claim 1, wherein paper is used as a base material.   The wallpaper according to claim 1 or 2, wherein a thermoplastic resin is used as a base material. 4. The wallpaper according to claim 3, wherein at least one selected from a polyvinyl chloride resin, a polyolefin resin, and an ethylene-vinyl acetate copolymer is used as a base material.