JP5452310B2 - Deodorizing functional layer, multilayer structure, interior material and method for producing multilayer structure - Google Patents

Description

  The present invention relates to a deodorizing functional layer containing an ethylene-vinyl alcohol copolymer, a multilayer structure provided with this layer, an interior material, and a method for producing the multilayer structure.

  In a semi-enclosed space such as a house, it is important in order to maintain a comfortable living environment to suppress odors derived from various volatile substances. In recent years, it has been important not only to improve the comfort of consumers but also to prevent various symptoms represented by sick house syndrome, to maintain a comfortable living environment by suppressing odors in the space. ing.

  Under such circumstances, as a technique capable of exhibiting a deodorizing function in an interior material such as a house, for example, (1) a composition containing a deodorant in a binder resin such as an acrylic resin is applied to the surface of a substrate. A deodorizing wallpaper formed by processing has been proposed (see, for example, JP-A-2006-348430). In addition, a wallpaper having a layer containing (2) an ethylene-vinyl alcohol copolymer having an excellent antifouling function and a deodorant component such as a photocatalyst has also been proposed (for example, JP-A No. 2003-305810). Gazette, JP-A-2-139484, etc.).

  However, the wallpaper using the acrylic resin or the like of (1) as a binder resin is liable to crack when embossing, and does not have a function of preventing dirt. In addition, wallpaper having a layer containing the ethylene-vinyl alcohol copolymer (2) and a deodorant component such as a photocatalyst may also have a deodorant performance because the contained deodorant component does not function sufficiently. Is not enough.

JP 2006-348430 A JP 2003-305810 A Japanese Patent Laid-Open No. 2-139484

  The present invention has been made based on these circumstances, and aims to provide a deodorizing functional layer having a high deodorizing function in addition to an excellent antifouling function, a multilayer structure including this layer, and an interior material. To do.

The invention made to solve the above problems is
An ethylene-vinyl alcohol copolymer having an ethylene unit content of 10 mol% or more, and a deodorizing functional layer containing deodorizing particles,
The deodorant particles as a core, and having a plurality of convex portions formed on the surface by covering at least most of the surface of the core with the ethylene-vinyl alcohol copolymer,
The mass ratio of the ethylene-vinyl alcohol copolymer to the deodorant particles is 1 or more and 3 or less,
The content of the deodorant particles is 0.3 g / m ² or more and 1.2 g / m ² or less.

  The deodorant functional layer contains deodorant particles, and since a plurality of convex portions having the deodorant particles as a core are formed on the surface, the surface area is increased due to the convex portions. ing. Therefore, according to the deodorizing functional layer, the deodorizing function can be efficiently exhibited especially by the deodorizing particles located near the surface of the layer. In addition, the deodorizing functional layer uses an ethylene-vinyl alcohol copolymer having a dirt prevention function as a binder resin, and the deodorizing property in which the ethylene-vinyl alcohol copolymer is the core of the convex portion. Since at least most of the surface of the layer is covered so as to cover the particles, an excellent antifouling function and crack resistance can be exhibited.

  The ratio of the average particle diameter of the deodorant particles to the average thickness of the deodorant functional layer is preferably 1 or more and 10 or less. By setting the average particle size of the deodorant particles to be equal to or greater than the average thickness of the layer itself, the surface of the deodorant functional layer can surely form a convex portion with the deodorant particles as the core, and high deodorization. The function can be demonstrated.

  The average particle size of the deodorant particles is preferably 1 μm or more and 10 μm or less. By using deodorant particles having a relatively large particle diameter in this manner, the surface area can be easily increased, and the deodorizing function can be further enhanced.

  The average thickness of the deodorant functional layer is preferably 1 μm or more and 3 μm or less. By setting the average thickness within the above range, the deodorizing function and the antifouling function can be sufficiently exhibited while satisfying the layer formability and the handleability.

  The mass ratio of the ethylene-vinyl alcohol copolymer to the deodorant particles is 1 or more and 3 or less. By setting the mass ratio of the ethylene-vinyl alcohol copolymer and the deodorant particles in the above range, the antifouling function and the deodorizing function can be achieved at a high level.

The content of the deodorant particles is 0.3 g / m ² or more and 1.2 g / m ² or less. By setting the content per unit area of the deodorant particles in the above range, the surface coverage of the deodorant particles is adjusted to the optimum range, and both the antifouling function and the deodorant function are achieved at a higher level. be able to.

  The deodorant particles are preferably inorganic porous particles. As described above, by using inorganic porous particles having a large surface area as the deodorant particles, the deodorization function can be further enhanced by the adsorption ability of the particles.

  It is preferable that the inorganic porous particles carry a photocatalyst. When the inorganic porous particles carry the photocatalyst, the adsorbed odor component can be decomposed, and the re-release of the odor component can be suppressed, so that the deodorizing function can be further enhanced.

  The ethylene content of the ethylene-vinyl alcohol copolymer is preferably 20 mol% or more and 60 mol% or less, and the saponification degree is preferably 90% or more. By using an ethylene-vinyl alcohol copolymer having an ethylene content and a saponification degree within the above ranges, water resistance, oil resistance, and antifouling properties can be further improved.

  The said deodorizing functional layer is good to be formed by application | coating of the resin composition containing an ethylene-vinyl alcohol copolymer, a deodorizing particle, and a solvent. By forming by coating in this way, a plurality of convex parts coated with an ethylene-vinyl alcohol copolymer can be easily and reliably formed with deodorant particles as the core, and the resulting deodorizing function The layer can exhibit an excellent deodorizing function and antifouling function.

  The multilayer structure of this invention has a base material layer and the said deodorizing functional layer laminated | stacked so that a convex part may be located in the outer surface on the one surface side of this base material layer. According to the multilayer structure, by having the deodorizing functional layer on the outer surface, it is possible to provide a high level of antifouling properties and deodorizing properties on the outer surface.

  The base material layer preferably contains an ethylene-vinyl alcohol copolymer. By including the ethylene-vinyl alcohol copolymer in the base material layer, the deodorizing functional layer can be firmly bonded without performing surface treatment of the base material layer. In addition, the multilayer structure in which the base material layer is made of an ethylene-vinyl alcohol copolymer also exhibits the ability to suppress bleed-out of the vinyl chloride plasticizer when used on the surface of vinyl chloride wallpaper. Can do.

  The interior material of the present invention includes the multilayer structure on the surface. According to the interior material, the deodorizing functional layer on the surface can exhibit high deodorizing properties and antifouling properties in a well-balanced manner, and can be suitably used as wallpaper.

  The glossiness of the surface of the interior material is preferably 2% or more and 20% or less. The interior material surface has such a low glossiness so that it has high matteness and can be suitably used as a wallpaper, etc., and the surface has a plurality of convex portions with deodorant particles as the core. Therefore, an excellent deodorizing function can be exhibited.

  The multilayer structure includes a step of applying a resin composition containing an ethylene-vinyl alcohol copolymer having an ethylene unit content of 10 mol% or more and deodorant particles on one surface side of the base material layer, and the application The obtained resin composition is dried, and can be produced by a method including a convex portion forming step of forming a plurality of convex portions having the deodorant particles as nuclei on the outer surface. According to such a manufacturing method, a plurality of convex portions having deodorant particles as a core can be easily and reliably formed on the surface by applying the above-described composition, and both the antifouling property and the deodorizing property can be obtained. An excellent multilayer structure can be obtained.

  Here, the “average thickness” is a value measured in accordance with JIS-K7130 “Test Method B1 for Thickness by Mass Method of Sample”. The “average particle size” is a value measured by a laser diffraction method. “Glossiness” is a value measured at an angle of 60 degrees in accordance with JIS-Z8741.

  As described above, according to the deodorant functional layer, since an ethylene-vinyl alcohol copolymer is used as a binder, a plurality of convex portions having deodorant particles as a core are formed on the surface. In addition, an excellent deodorizing function can be exhibited while providing antifouling properties and crack resistance. Therefore, the multilayer structure provided with the deodorant functional layer on the outer surface can be suitably used as an interior material such as wallpaper having both excellent antifouling function and deodorant function.

It is a typical sectional view showing a deodorant functional layer concerning one embodiment of the present invention. It is typical sectional drawing which shows a multilayer structure provided with the deodorizing functional layer of FIG. 3 is an electron micrograph of the surface of an interior material of Example 1. FIG.

Hereinafter, embodiments of the present invention will be described in detail in the order of a deodorizing functional layer, a multilayer structure, and an interior material with reference to the drawings.
(Deodorizing functional layer)
The deodorant functional layer 1 in FIG. 1 contains an ethylene-vinyl alcohol copolymer (hereinafter also referred to as “EVOH”) 2 and a deodorant particle 3 as a binder, and the deodorant particle 3 is provided on the surface. It has the some convex part 4 formed as a nucleus.

  Since the deodorizing functional layer 1 has a plurality of convex portions 4 with the deodorizing particles 3 as nuclei on the surface, the surface area is expanded due to the convex portions 4. Therefore, according to the deodorizing functional layer 1, the deodorizing function can be efficiently exhibited by the deodorizing particles 3 particularly located near the surface. Moreover, since the said deodorizing functional layer 1 uses EVOH2 as a binder resin, it can exhibit an excellent antifouling function. Moreover, since the deodorizing functional layer 1 uses EVOH having a Tg lower than a general processing temperature at the time of embossing as a binder resin, even when embossed on the surface using the surface of wallpaper, Generation of cracks can be prevented.

  Note that most of the deodorant particles 3 are not completely exposed on the surface and are thinly coated with EVOH2. Even in such a state, since a certain amount of odor components permeate through EVOH2, an excellent deodorizing function can be exhibited. On the other hand, since EVOH covers most of the layer surface, excellent dirt is obtained. The prevention function can be exhibited. However, at least a part of the deodorizing particles 3 may be exposed on the surface of the deodorizing functional layer 1. If the deodorant particles 3 are not even partially covered with EVOH2 and are exposed on the surface, the deodorant particles 3 can directly act on the odor components, thus exhibiting an extremely excellent deodorizing function. can do.

(EVOH)
EVOH2 is a polymer having ethylene units and vinyl alcohol units as main structural units. The EVOH may contain one or more other structural units in addition to the ethylene unit and the vinyl alcohol unit.

  This EVOH is usually obtained by polymerizing ethylene and a vinyl ester and saponifying the resulting ethylene-vinyl ester copolymer.

  The lower limit of the ethylene unit content of EVOH (that is, the ratio of the number of ethylene units to the total number of monomer units in EVOH) is 10 mol%, preferably 20 mol%, more preferably 30 mol%. preferable. On the other hand, the upper limit of the ethylene unit content of EVOH is preferably 60 mol%, more preferably 55 mol%, and particularly preferably 50 mol%. When the ethylene unit content of EVOH is smaller than the above lower limit, water resistance is lowered, and as a result, water-based dirt is likely to permeate, so that performance such as dirt prevention may be lowered. Conversely, if the ethylene unit content of EVOH exceeds the above upper limit, the oil resistance is lowered and oily dirt is likely to permeate.

  The lower limit of the saponification degree of EVOH (that is, the ratio of the number of vinyl alcohol units to the total number of vinyl alcohol units and vinyl ester units in EVOH) is preferably 90 mol%, more preferably 95 mol%, and 99 mol% Is particularly preferred. On the other hand, the upper limit of the saponification degree of EVOH is preferably 99.99 mol%. Even when the saponification degree of EVOH is smaller than the above lower limit, the oil resistance is lowered and oily dirt is likely to permeate. On the other hand, if the saponification degree of EVOH exceeds the above upper limit, the production cost of EVOH increases, but an increase in layer forming property, antifouling property, etc. cannot be expected so much.

  Next, the manufacturing method of EVOH2 is demonstrated. The copolymerization method of ethylene and vinyl ester is not particularly limited, and for example, any of solution polymerization, suspension polymerization, emulsion polymerization, and bulk polymerization may be used. Moreover, any of a continuous type and a batch type may be sufficient.

  As the vinyl ester used in the polymerization, a fatty acid vinyl such as vinyl acetate, vinyl propionate or vinyl pivalate can be suitably used.

  In the above polymerization, as a copolymerization component, a monomer that can be copolymerized in addition to the above components, for example, alkenes other than ethylene; unsaturated acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid or the like Anhydrides, salts, mono- or dialkyl esters, etc .; Nitriles such as acrylonitrile and methacrylonitrile; Amides such as acrylamide and methacrylamide; Olefin sulfonic acids such as vinyl sulfonic acid, allyl sulfonic acid and methallyl sulfonic acid; Alkyl vinyl ethers, vinyl ketones, N-vinyl pyrrolidone, vinyl chloride, vinylidene chloride and the like can also be copolymerized in small amounts. Moreover, a vinyl silane compound can be contained as 0.0002 mol% or more and 0.2 mol% or less as a copolymerization component. Here, examples of the vinylsilane compound include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri (β-methoxy-ethoxy) silane, and γ-methacryloyloxypropylmethoxysilane. Of these, vinyltrimethoxysilane and vinyltriethoxysilane are preferably used.

  The solvent used for the polymerization is not particularly limited as long as it is an organic solvent that can dissolve ethylene, vinyl ester, and ethylene-vinyl ester copolymer. As such a solvent, for example, alcohols such as methanol, ethanol, propanol, n-butanol and tert-butanol; dimethyl sulfoxide and the like can be used. Among them, methanol is particularly preferable in that removal and separation after the reaction is easy.

  Examples of the catalyst used for polymerization include 2,2-azobisisobutyronitrile, 2,2-azobis- (2,4-dimethylvaleronitrile), 2,2-azobis- (4-methoxy-2,4). -Dimethylvaleronitrile), 2,2-azobis- (2-cyclopropylpropionitrile) and other azonitrile initiators; isobutyryl peroxide, cumylperoxyneodecanoate, diisopropylperoxydicarbonate, di-n Organic peroxide initiators such as -propyl peroxydicarbonate, t-butyl peroxyneodecanoate, lauroyl peroxide, benzoyl peroxide, and t-butyl hydroperoxide can be used.

  The polymerization temperature is preferably 20 to 90 ° C, more preferably 40 to 70 ° C. The polymerization time is preferably 2 to 15 hours, more preferably 3 to 11 hours. The polymerization rate is preferably 10 to 90% by mass, more preferably 30 to 80%, based on the charged vinyl ester. The resin content in the solution after polymerization is preferably 5 to 85%, more preferably 20 to 70%.

  After polymerization for a predetermined time or after reaching a predetermined polymerization rate, a polymerization inhibitor is added as necessary, and after removing unreacted ethylene gas, unreacted vinyl ester is removed. As a method for removing the unreacted vinyl ester, for example, the above copolymer solution is continuously supplied from the upper part of the tower filled with Raschig rings at a constant rate, and an organic solvent vapor such as methanol is blown from the lower part of the tower. A method may be employed in which a mixed vapor of an organic solvent such as methanol and unreacted vinyl ester is distilled from the top, and a copolymer solution from which unreacted vinyl ester has been removed is removed from the bottom of the column.

  Next, an alkali catalyst is added to the copolymer solution to saponify the copolymer. The saponification method can be either a continuous type or a batch type. As this alkali catalyst, for example, sodium hydroxide, potassium hydroxide, alkali metal alcoholate and the like are used.

  As the saponification conditions, for example, in the case of a batch system, the copolymer solution concentration is 10 to 50%, the reaction temperature is 30 to 65 ° C., and the amount of catalyst used is 0.02 to 1.0 per mole of vinyl ester structural unit. Mole, saponification time is 1-6 hours.

  EVOH after the saponification reaction contains an alkali catalyst, by-product salts such as sodium acetate and potassium acetate, and other impurities. Therefore, it is preferable to remove these by neutralization and washing as necessary. Here, when EVOH after the saponification reaction is washed with water containing almost no metal ions such as ion-exchanged water, chloride ions, or the like, a part of sodium acetate, potassium acetate or the like may remain.

(Deodorant particles)
The deodorant particles 3 are not particularly limited as long as they have a deodorizing function, and include organic compound particles, inorganic compound particles, or composite particles of an organic compound and an inorganic compound. The deodorant particle 3 can use 1 type (s) or 2 or more types.

  Examples of the organic compound that can be used for the deodorant particles 3 include amine compounds such as aliphatic polyamine compounds, aromatic polyamine compounds, and hydrazine derivatives. Among these, hydrazine derivatives can be preferably used. . Examples of the hydrazine derivative include sebacic acid dihydrazide, dodecanedioic acid dihydrazide, and isophthalic acid dihydrazide. By using such an amine compound as the deodorizing particles 3, it is possible to exhibit a particularly high deodorizing function for aldehydes.

  Examples of the inorganic compound particles that can be used for the deodorant particles 3 include metal oxide particles and inorganic porous particles.

  Examples of the metal oxide particles include metal oxide particles such as zinc oxide, iron oxide, silver oxide, copper oxide, aluminum oxide, magnesium oxide, manganese oxide, nickel oxide, cobalt oxide, and titanium oxide. By using metal oxide particles as deodorant particles 3, chemical substances such as hydrogen sulfide, mercaptans, acetic acid, amines, and ammonia can be decomposed, and particularly have a high deodorizing function against acetic acid. It can be demonstrated.

  An inorganic porous particle means the inorganic particle which has many pores in particle | grains, and can use a natural mineral or an artificial thing. Since the inorganic porous particles have a large surface area of the deodorant particles and a high adsorbing ability of the deodorant component, they can exhibit an excellent deodorizing function when used as the deodorant particles 3, particularly ammonia and A high deodorizing function against acetic acid can be exhibited.

Examples of inorganic porous particles of natural minerals include, for example, andesite, quartz andesite, rhyolite, shale, sandstone, lephestone, and other porous rocks, pumice tuff, mudstone, gravel, Sand, silt, clay and volcanic ash, porous rock, scoria, scoria tuff, scoria-containing material, calcined perlite, calcined obsidian, calcined pumice, vermiculite, zeolite, diatomaceous earth, mica, coral sand, seashell, barley stone (main component: SiO ₂ about 70%, Al ₂ O ₃ about 14%, Fe ₂ O ₃ about 2-3%), and the like.

  Artificial inorganic porous particles include artificial pumice, artificial gravel, artificial sand, artificial aggregate, porous glass, hollow glass, porous block, ceramic, synthetic zeolite, expandable silica, silica gel, charcoal, activated carbon, Examples include coal, coke, fly ash, blast furnace slug, foamed concrete (ALC), lightweight concrete, etc., granulated and molded as necessary.

  The inorganic porous particles preferably carry a photocatalyst. When the inorganic porous particles carry the photocatalyst, the adsorbed odor component can be decomposed, and the re-release of the odor component can be suppressed, so that the deodorizing function can be further enhanced.

  The photocatalyst is a substance that exhibits a catalytic action against decomposition of odor components when irradiated with light, and examples thereof include titanium oxide, zinc oxide, tungsten oxide, iron oxide, molybdenum sulfide, cadmium sulfide, and strontium titanate. It is done. Among these, titanium oxide having a high photocatalytic function, chemically stable, and harmless is preferable. Titanium oxide includes, in addition to titanium oxide, what is generally called hydrous titanium oxide, hydrated titanium oxide, metatitanic acid, orthotitanic acid, titanium hydroxide, etc., and its crystal type (rutile type, anatase type, etc.) ) Does not matter. These titanium oxides can be obtained by known methods. For example, (1) a method of hydrolyzing a titanium compound such as titanyl sulfate, titanium chloride, or an organic titanium compound, (2) titanyl sulfate, titanium chloride, or an organic titanium compound. (3) Method of vapor phase oxidation of titanium chloride, organic titanium compound, etc. (4) Oxidation obtained by the methods (1) and (2) above The method of baking titanium is mentioned. In particular, titanium oxide obtained by the methods (1) and (2) is preferable because of its high photocatalytic function.

  These photocatalysts may be coated with a metal such as platinum, gold, silver, copper, palladium, rhodium or ruthenium, or a metal oxide such as ruthenium oxide or nickel oxide to improve the photocatalytic function. .

  The lower limit of the average particle size of the deodorant particles 3 is preferably 1 μm, more preferably 2 μm, and particularly preferably 3 μm. On the other hand, the upper limit of the average particle diameter is preferably 10 μm, more preferably 8 μm, and particularly preferably 6 μm. According to the deodorant functional layer 1, by using the deodorant particles 3 having a relatively large particle diameter as described above, the surface area can be easily enlarged and the particles can be easily exposed to the surface of the layer. The odor function can be further enhanced.

  When the average particle diameter of the deodorant particles 3 is less than the lower limit, sufficient convex portions cannot be formed on the surface of the layer, and even when convex portions are formed, the particles are exposed to the surface. Since it becomes difficult, there exists a possibility that a deodorizing function may not fully be exhibited. On the other hand, if the average particle diameter exceeds the upper limit, a convex portion is easily formed on the surface of the layer, but it is not sufficiently fixed to EVOH as a binder, and the handleability may be lowered.

  The lower limit of the average pore diameter of the deodorant particles 3 is preferably 2 nm, more preferably 5 nm, and particularly preferably 10 nm. On the other hand, the upper limit of the average pore diameter is preferably 80 nm, more preferably 40 nm, further preferably 20 nm, and particularly preferably 15 nm. By making the average pore diameter of the deodorant particles 3 within the above range, the adsorptivity of the odor component to the deodorant particles 3 can be improved, and the deodorization function can be further enhanced.

The lower limit of the BET specific surface area of the deodorant particles 3, preferably ^{50m 2 / g, 100m 2 /} g is more preferable. On the other hand, the upper limit of the BET specific surface area is preferably 2000 m ² / g, 1000 m and more preferably ² / g, 500m ² / g is particularly preferred. By making the BET specific surface area of the deodorant particles 3 within the above range, the adsorptivity of the odor component to the deodorant particles 3 can be improved, and the deodorization function can be further enhanced.

  The average pore diameter and the BET specific surface area of the deodorant particles 3 were measured by measuring the adsorption isotherm with nitrogen by the nitrogen adsorption method, calculating the BET specific surface area by the BET multipoint method, and obtaining the fine pore size obtained by the BJH method. It is a value calculated as an average pore diameter from the values of pore volume and specific surface area. However, for the case where the adsorption isotherm indicates type I, the average pore diameter is calculated from the pore volume and specific surface area values obtained by the MP method.

The lower limit of the content per unit area of the deodorant particles 3, preferably 0.3 g / ^{m 2,} more preferably ^{0.4g / m 2, 0.5g / m} 2 is particularly preferred. In contrast, the upper limit of the content per unit area is preferably 1.2 g / ^{m 2,} more preferably ^{1.0g / m 2, 0.8g / m} 2 is particularly preferred. By setting the content per unit area of the deodorant particles 3 in the above range, the surface coverage of the deodorant particles can be adjusted to an optimum range, and the antifouling function and the deodorization function are higher. Can be balanced at the level.

  When the content per unit area of the deodorant particles 3 is less than the lower limit, the surface coverage of the deodorant particles is low, and there is a possibility that a sufficient deodorizing function cannot be exhibited. On the contrary, if the content per unit area of the deodorant particles 3 exceeds the above upper limit, the surface coverage of the deodorant particles increases and the deodorizing function increases, but the area where EVOH is exposed on the surface decreases. As a result, the anti-smudge function may be reduced.

  In addition to the EVOH 2 and the deodorant particles 3, the deodorant functional layer 1 may contain other resins, color pigments, moisture-resistant pigments, dispersants, and the like as long as the effects of the present invention are not impaired. .

(Layer shape, etc.)
The lower limit of the average thickness of the deodorant functional layer 1 is preferably 1 μm, and more preferably 1.5 μm. On the other hand, the upper limit of the average thickness is preferably 3 μm, and more preferably 2.5 μm. By setting the average thickness within the above range, the deodorizing function and the antifouling function can be sufficiently exhibited while satisfying the layer formability and the handleability.

  The lower limit of the ratio of the average particle diameter of the deodorant particles 3 to the average thickness of the deodorant functional layer 1 is preferably 1, more preferably 1.2, and particularly preferably 1.5. On the other hand, the upper limit of this ratio is preferably 10, more preferably 8, and particularly preferably 6. By making the average particle diameter of the deodorant particles 3 with respect to the average thickness within the above range, that is, by setting the average particle diameter of the deodorant particles 3 to be equal to or greater than the average thickness of the layer 1 itself, the surface of the deodorant functional layer 1 It is possible to reliably form a convex portion having the deodorant particles 3 as a core, and to expose the deodorant particles 3 on the surface, thereby exhibiting a high deodorizing function.

  If the average particle diameter of the deodorant particles 3 with respect to the average thickness of the deodorant functional layer 1 is smaller than the above lower limit, the convex portion to the surface having the deodorant particles 3 as a core is not sufficiently formed, and particularly on the surface. Since it becomes difficult to expose the deodorizing particles 3, the deodorizing function may not be sufficiently exhibited. On the contrary, when the average particle diameter of the deodorant particles 3 with respect to the average thickness of the deodorant functional layer 1 exceeds the above upper limit, the thickness of EVOH as a binder becomes small with respect to the particle diameter of the deodorant particles 3. And the sticking property of the deodorant particle 3 will fall.

  The lower limit of the mass ratio of EVOH2 to deodorant particles 3 is preferably 1, and more preferably 1.4. Conversely, the upper limit of the mass ratio of EVOH2 to deodorant particles 3 is preferably 3, and more preferably 2.6. By setting the mass ratio of EVOH 2 and deodorant particles 3 in the above range, the antifouling function and the deodorizing function can be achieved at a high level.

  If the content of the EVOH 2 with respect to the deodorant particles 3 is smaller than the above lower limit, the portion where the EVOH 2 is exposed on the surface of the layer decreases, so that the antifouling function may not be sufficiently exhibited. On the contrary, if the content of EVOH 2 with respect to the deodorant particles 3 exceeds the above upper limit, the portion occupied by the deodorant particles 3 on the surface becomes small, so that the deodorization function may not be sufficiently exhibited.

(Multilayer structure)
The multilayer structure 5 in FIG. 2 has a base material layer 6 and a deodorizing functional layer 1 laminated on one surface side of the base material layer 6 so that the convex portion 4 is located on the outer surface. Since the deodorizing functional layer 1 is the same as that of FIG. 1, description is abbreviate | omitted. According to this multilayer structure 5, by having the deodorizing functional layer 1 on the outer surface, it is possible to provide the outer surface with antifouling properties and deodorizing properties at a high level.

  The substrate layer 6 is not particularly limited, and examples thereof include synthetic resins such as vinyl chloride resin, styrene resin, acrylic resin, and polyethylene resin, paper, nonwoven fabric, woven fabric, and the like. What is contained is good. Since the base material layer 6 includes EVOH in the same manner as the deodorizing functional layer, the deodorizing functional layer 1 can be firmly adhered to the surface without performing the surface treatment of the base material layer 6. In addition, the multilayer structure in which the base material layer 6 is made of EVOH as described above can also exhibit the ability to suppress bleed-out of the vinyl chloride plasticizer when used as a vinyl chloride wallpaper.

  The base material layer 6 is preferably formed from a resin composition containing an acid-modified polyolefin and / or a thermoplastic elastomer in addition to EVOH because of its excellent flexibility.

  Since the base material layer 6 is molded from a resin composition containing an acid-modified polyolefin and / or a thermoplastic elastomer with respect to EVOH, the content of a resin other than EVOH can be increased. The workability when the multilayer structure 5 including the base material layer 6 is used for wallpaper or the like can be improved.

  In addition, when forming the base material layer 6 from the resin composition containing acid-modified polyolefin with EVOH, a fine unevenness | corrugation can be easily provided in the base material layer surface. Since the fine irregularities increase the surface area of the base material layer 6, the surface area of the deodorizing functional layer 1 laminated on the surface of the base material layer 6 is also increased. Therefore, according to the multilayer structure 5 including the base material layer 6 formed from a resin composition containing EVOH and acid-modified polyolefin, the area where the deodorant particles 3 can exist is expanded. Deodorizing performance can be further enhanced.

  In the base material layer 6, the lower limit of the total content of the acid-modified polyolefin and the thermoplastic elastomer with respect to 100 parts by mass of EVOH is preferably 5 parts by mass, more preferably 20 parts by mass, further preferably 30 parts by mass, and 40 parts by mass. More preferred is 45 parts by mass, and still more preferred. On the other hand, the upper limit of the total content of the acid-modified polyolefin and the thermoplastic elastomer with respect to 100 parts by mass of EVOH is preferably 100 parts by mass, more preferably 80 parts by mass, further preferably 60 parts by mass, and particularly preferably 55 parts by mass. According to this resin composition, the low flexibility of EVOH can be improved by containing acid-modified polyolefin and thermoplastic elastomer other than EVOH in the above range. That is, according to the base material layer 6 molded from this resin composition, the flexibility is improved, and the workability of wallpaper and the like using the multilayer structure 5 can be improved. If the total content of the acid-modified polyolefin and the thermoplastic elastomer is smaller than the lower limit, the flexibility is not sufficiently improved. Conversely, if the total content of the acid-modified polyolefin and the thermoplastic elastomer exceeds the above upper limit, it becomes difficult for the acid-modified polyolefin and the thermoplastic elastomer to uniformly disperse in the EVOH and exist in an island shape, thereby forming a film. May decrease.

  As a minimum of ethylene unit content of EVOH used suitably for substrate layer 6, 35 mol% is preferred and 40 mol% is still more preferred. On the other hand, the upper limit of the ethylene unit content of EVOH is preferably 60 mol%, more preferably 55 mol%, and particularly preferably 50 mol%. When the ethylene unit content of EVOH is smaller than the above lower limit, the film forming property of the resin composition may be lowered, the flexibility of the base material layer may be lowered, and construction when the multilayer structure is used for wallpaper or the like. There is a concern that the performance of the base material layer may deteriorate, and further, performance such as water resistance and hot water resistance of the base material layer may decrease. Conversely, if the ethylene unit content of EVOH exceeds the above upper limit, the strength of the base material layer 6 may be reduced, or the plasticizer may be prevented from bleeding when used as a wallpaper by being laminated on a resin containing a plasticizer. Performance may be reduced.

  As a minimum of the saponification degree of EVOH used suitably for the base material layer 6, 90 mol% is preferable, 95 mol% is more preferable, 99 mol% is especially preferable. On the other hand, the upper limit of the saponification degree of EVOH is preferably 99.99 mol%. If the saponification degree of EVOH is smaller than the above lower limit, the film-forming property of the resin composition may be lowered, or the plasticizer bleed prevention performance is lowered when it is used for wallpaper etc. by being laminated on a resin containing a plasticizer. There is a risk. On the other hand, if the saponification degree of EVOH exceeds the above upper limit, the production cost of EVOH increases, but an increase in film forming property, flexibility and the like cannot be expected so much.

  The lower limit of the EVOH melt index suitably used for the substrate layer 6 is preferably 0.1 g / 10 minutes, more preferably 0.5 g / 10 minutes, particularly preferably 1 g / 10 minutes, and further 5 g / 10 minutes. Particularly preferable, 6 g / 10 min is more preferable, 8 g / 10 min is further particularly preferable, and 10 g / 10 min is further particularly preferable. On the other hand, the upper limit of the EVOH melt index is preferably 30 g / 10 min, more preferably 25 g / 10 min, particularly preferably 20 g / 10 min, and particularly preferably 15 g / 10 min. According to this base material layer 6, the film forming property of the resin composition can be maintained by setting the EVOH melt index to a value in the above-described range. If the EVOH melt index is smaller than the above lower limit, it becomes difficult to form a thin film and the film-forming property of the resin composition is lowered. On the other hand, if the EVOH melt index exceeds the above upper limit, the chemical resistance of the base material layer, the bleed prevention property of the plasticizer when used as wallpaper or the like may be lowered.

  The acid-modified polyolefin preferably used for the base material layer 6 refers to a polyolefin having an acidic group such as a carboxyl group or its anhydride group or sulfonic acid group. Examples of the acid-modified polyolefin include a carboxylic acid-modified polyolefin obtained by graft polymerization or addition of an α, β-unsaturated carboxylic acid such as itaconic acid and maleic acid and / or an anhydride thereof to the polyolefin. The polyolefin for obtaining the carboxylic acid-modified polyolefin is preferably a poly α-olefin which is a homopolymer obtained by polymerizing a monomer mainly composed of ethylene or an α-olefin having 3 or more carbon atoms. As this poly α-olefin, polyethylene, polypropylene, and poly 1-butene are preferable, and among them, polyethylene is most preferable. In addition, this poly alpha olefin may contain other monomers, such as an olefin type monomer, as a trace component.

  As described above, the acid-modified polyolefin is preferably acid-modified polyethylene, and more preferably carboxylic acid-modified high-density polyethylene obtained by modifying high-density polyethylene with carboxylic acid. By using carboxylic acid-modified high-density polyethylene, it becomes easy to take a sea-island structure in this resin composition, and in addition, it becomes easy to adjust to the desired melt index described below. Therefore, according to the base material layer containing the carboxylic acid-modified high-density polyethylene, the film forming property of the resin composition can be improved.

  The thermoplastic elastomer suitably used for the base material layer 6 is a resin that has fluidity when heated and has rubber-like elasticity at room temperature. In this base material layer 6, the acid-modified polyolefin is not included in the thermoplastic elastomer even when the above conditions are satisfied.

  The thermoplastic elastomer is not particularly limited as long as it satisfies the definition of the thermoplastic elastomer described above, and examples thereof include urethane-based, polyamide-based, polyester-based, polyolefin-based thermoplastic elastomers, and the like, film forming properties of resin compositions, etc. From this point, a polyolefin-based thermoplastic elastomer is preferable.

  Examples of polyolefin-based thermoplastic elastomers include polymers of olefin monomers such as ethylene, propylene, 1-butene, 2-butene, iso-butene, and 1,3-butadiene, or two or more olefin monomers. And copolymers of olefinic monomers with other monomers and modified products thereof. Examples of the polymer of these olefinic monomers include 1,2-polybutadiene, and examples of the copolymer include an ethylene-propylene copolymer, an ethylene-butene copolymer, and an ethylene-vinyl acetate copolymer. Etc. Examples of these modified products include ion-crosslinked ethylene-methacrylic acid copolymers, chlorinated polyethylene, and the like. These thermoplastic elastomers can be used alone or in admixture of two or more.

  The thermoplastic elastomer may include an acid-modified thermoplastic elastomer. The acid-modified thermoplastic elastomer refers to a thermoplastic elastomer having an acidic group such as a carboxyl group or its anhydride group or sulfonic acid group. Examples of the acid-modified thermoplastic elastomer include acid-modified thermoplastic elastomers modified with an α, β-unsaturated carboxylic acid such as (anhydrous) itaconic acid and (anhydrous) maleic acid. Thus, by using an acid-modified thermoplastic elastomer, the dispersibility of the thermoplastic elastomer in the resin composition can be enhanced, and it becomes easy to adjust to a desired suitable melt index. Therefore, the base material layer 6 having such a thermoplastic elastomer can further improve the film forming property of the resin composition.

  As the thermoplastic elastomer, a mixture of an acid-modified ethylene-α-olefin copolymer and an ethylene-α-olefin copolymer is preferable. Specifically, a carboxylic acid-modified ethylene-butene copolymer and ethylene are used. -A mixture with a butene copolymer is preferred. As the carboxylic acid-modified ethylene-butene copolymer, a maleic anhydride-modified ethylene-butene copolymer is particularly preferable. By using such a thermoplastic elastomer, the melt index of the thermoplastic elastomer and the average acid value of the entire resin composition can be easily and suitably adjusted. The workability at the time of using can be improved. Here, the α-olefin refers to an α-olefin having 3 or more carbon atoms.

  Although it does not specifically limit as thickness (maximum thickness) of this base material layer 6, As a minimum, 10 micrometers is preferable and 12 micrometers is more preferable. Moreover, as this upper limit, 50 micrometers is preferable, 40 micrometers is more preferable, and 30 micrometers is especially preferable. Film formation when the thickness is smaller than the above lower limit may be difficult. Conversely, if the thickness exceeds the above upper limit, the workability when used for wallpaper or the like may be reduced.

(Manufacturing method of multilayer structure and deodorant functional layer)
The multilayer structure includes, for example, a step of applying a resin composition containing EVOH having an ethylene unit content of 10 mol% or more and deodorant particles on one surface side of the base material layer, and the applied resin composition Can be produced by a method including a projecting portion forming step of forming a plurality of projecting portions having the deodorant particles as nuclei on the outer surface. According to such a manufacturing method, a plurality of convex portions having deodorant particles as a core as a deodorizing functional layer can be easily and reliably formed on the outer surface in a state where EVOH is coated, and the antifouling property and A deodorizing functional layer and a multilayer structure excellent in both deodorizing properties can be obtained.

  The method for applying the resin composition on one surface side of the base material layer is not particularly limited, and examples include gravure roll processing, spray processing, roll coater processing, jet print processing, transfer print processing, and screen print processing. it can. After applying the resin composition on one side of the base material layer and drying it, the deodorant particles are firmly fixed together with EVOH as a binder resin on one side of the base material layer as a deodorizing functional layer. Can be made.

  In the said resin composition, in order to improve applicability | paintability, it is preferable to contain a solvent in addition to EVOH and a deodorizing particle. The solvent is not particularly limited, and for example, n-propanol, a mixed solution of n-propanol and water (mass ratio 65:35), or the like can be used.

  After the application, as the convex portion forming step, the applied resin composition is dried, whereby the solvent is volatilized and a plurality of convex portions having the deodorant particles as nuclei on the surface can be formed. It does not specifically limit as this drying method, Natural drying may be sufficient and heat addition may be performed.

  In addition, as a manufacturing method of the said multilayered structure and a deodorizing functional layer, it is not limited to the above-mentioned method, For example, it manufactures by bonding what formed each layer of the multilayered structure into the film form by the melt extrusion molding method etc. May be.

(Interior material)
The interior material of the present invention includes a base body and, for example, the above-described multilayer structure laminated on the surface of the base body by heat lamination or the like so that the deodorizing functional layer side becomes an outer surface. The interior material is a material used for decoration inside a building, and examples thereof include wallpaper, a decorative board, and a decoration material. Among these interior materials, wallpaper is preferably used as a material capable of effectively utilizing the excellent deodorizing properties and antifouling properties of the deodorizing functional layer and multilayer structure of the present invention.

  As a substrate in wallpaper, a plasticizer-containing soft polyvinyl chloride film or sheet is typically mentioned. The plasticizers contained in the soft polyvinyl chloride can be broadly classified into plasticizers that are liquid at room temperature (20 ° C.) and plasticizers that are solid at room temperature. For the former, for example, phthalate plasticizers such as dibutyl phthalate, di (2-ethylhexyl) phthalate, diisooctyl phthalate, didecyl phthalate, dinonyl phthalate, dilauryl phthalate, butyl lauryl phthalate, butyl benzyl phthalate, tricresyl Examples thereof include phosphates such as phosphate, tributyl phosphate and tri- (2-ethylhexyl) phosphate, and chlorine-containing plasticizers such as chlorinated paraffin. On the other hand, examples of the latter include phthalate plasticizers such as dicyclohexyl phthalate and phthalic acid diester having 13 or more carbon atoms of alcohol.

  The addition amount of the plasticizer is preferably 20% by mass or more and 75% by mass or less, and more preferably 25% by mass or more and 55% by mass or less with respect to the total mass of the substrate. When the addition amount of the plasticizer is less than 20% by mass, the flexibility of the substrate is lowered, and as a result, the workability of the wallpaper is lowered. On the other hand, when the added amount of the plasticizer exceeds 75% by mass, the physical properties such as the strength of the substrate are lowered, which is not preferable.

  According to the interior material, the deodorizing functional layer on the surface can exhibit a high deodorizing property and antifouling property in a balanced manner, and can be suitably used as wallpaper or the like.

  The lower limit of the glossiness of the interior material surface is preferably 2%, more preferably 3%, and particularly preferably 4%. On the other hand, the upper limit of the glossiness is preferably 20%, more preferably 16%, and particularly preferably 12%. In addition to being excellent in matting performance by having such a low glossiness, the interior material is excellent because a plurality of convex portions having deodorant particles as the core are sufficiently formed on the surface. Deodorizing function can be demonstrated.

  When the glossiness is less than the above lower limit, high matteness and excellent deodorizing function can be exhibited, but in order to reduce the glossiness to such a value, the content of deodorant particles is increased. As a result, the antifouling property may be reduced. On the other hand, when the glossiness exceeds the above upper limit, the matte property is not sufficient, and the convex portion having the deodorant particles as the core is not sufficiently formed on the surface, or the surface of the deodorant particles is not formed. Since there is little exposure, there is a possibility that the deodorizing function may not be sufficiently exhibited.

  In addition, since the interior material has a highly deodorant functional layer made of EVOH on the surface, it can be used as wallpaper, and even when embossed on the surface, the occurrence of cracks can be prevented, Excellent workability.

  The deodorant functional layer, multilayer structure and interior material of the present invention are not limited to the above embodiment. For example, as a deodorizing functional layer, a deodorizing functional layer can be formed by directly applying a resin composition constituting the deodorizing functional layer to a wall or glass, and the wall or glass is a multilayer of the present invention. It can function as a structure or an interior material. In addition to the two-layer structure of the base material layer and the deodorizing functional layer, if the multilayer structure is laminated so that a plurality of convex portions of the deodorizing functional layer are located on the outer surface, a multilayer of three or more layers It may be a structure.

  EXAMPLES Hereinafter, although this invention is explained in full detail based on an Example, this invention is not interpreted limitedly based on description of this Example.

[Example 1]
(Preparation of resin composition)
EVOH having an ethylene content of 44 mol% and a saponification degree of 99% was stirred in a mixed solvent of n-propanol / water (mass ratio 65/35) for 3 hours at 75 ° C. under reflux, and 7.5% by mass of EVOH. A solution was obtained. To this EVOH solution, Lionite PC-301P was added as deodorant particles so that the mass ratio of EVOH to deodorant particles (in terms of solid content) was 2.0: 1.0. A functional resin composition was obtained.

(Manufacture of base material layer)
100 parts by mass of EVOH pellets having an ethylene unit content of 44 mol%, a saponification degree of 99.97%, a melt index (210 ° C., load of 2160 g) of 12 g / 10 min, and an acid value of 0 mg KOH / g,
6 parts by mass of maleic anhydride-modified high-density polyethylene pellets having a melt index (210 ° C., load 2160 g) of 0.5 g / 10 min and an acid value of 2.2 mgKOH / g;
17 parts by mass of maleic anhydride-modified ethylene-butene copolymer pellets having a melt index (210 ° C., load 2160 g) of 2.9 g / 10 min, an acid value of 5.6 mg KOH / g, and a melt index (210 ° C., load 2160 g) ) Is 5.1 g / 10 minutes, and 26 parts by mass of ethylene-butene copolymer pellets having an acid value of 0 mg KOH / g are weighed and mixed for 10 minutes using a tumbler (capacity 120 L).

  Batch-mixed raw material 40 mm in diameter, L / D = 22, single screw with full flight tip Maddock, strand die: 3 mmφ × 2 pieces, molding temperature 215 ° C., screw rotation speed 25 rpm, discharge rate 8 kg / hr The pellet was cut with a pelletizer while cooling the strand in a cooling water bath to obtain a cylindrical blend pellet. The blended pellets were formed into a T-die extruder (Toyo Seiki Seisakusho 20 mm extruder D2020 (D (mm) = 20, L / D = 20, compression ratio = 2.0, screw: full flight shallow groove type, die) : Coat hanger 300 mm width die, screen: 50/100/50 Mesh)), extrusion temperature: C1 / C2 / C3 / Die = 170/210/225/215 ° C., screw rotation speed 75 rpm, discharge rate 1.9 kg / hr Under the conditions, a substrate layer having a thickness (maximum thickness) of 20 μm was obtained.

(Formation of deodorant functional layer and multilayer structure)
The said resin composition was apply | coated to one side of said base material layer, and the multilayer structure was obtained with the deodorizing functional layer by making it dry. The average thickness of the deodorant functional layer of the obtained multilayer structure was 2 μm, and the content of the deodorant particles was 0.6 g / m ² .

  The average thickness of the deodorant functional layer is measured in accordance with JIS-K7130 “Test Method B1 of Thickness by Mass Method of Sample”, and the average thickness of the base material layer and the multilayer structure is measured. It is a value calculated as a difference.

(Manufacture of interior materials (wallpaper))
Methyl ethyl ketone 20 as a solvent was added to 80 parts by mass of Dicseal LA-100Z and KP-90 (curing agent) manufactured by Dainippon Ink & Chemicals, Inc., which is an organic solvent system, at a ratio of 100 parts by mass to 0.6 parts by mass. Mass parts were added to obtain an adhesive. This was applied to the back surface of the multilayer structure (external surface on the base material layer side) using a No. 10 bar coater and dried for 1 minute with a dryer at 80 ° C. The thickness of the adhesive layer after drying was 2 μm.

  A non-foamed vinyl chloride wallpaper manufactured by Nankai Technate Co., Ltd. was used as the substrate, and the adhesive-coated surface of the multilayer structure was aligned and superimposed on the vinyl chloride surface.

  Next, the laminate was heat laminated with a laminator DX-350 manufactured by Tokyo Lamix Co., Ltd. having an embossing roll under the conditions of a temperature of 120 ° C. and a speed of 2 m / min to obtain an interior material (wallpaper) of Example 1.

[Examples 2 to 4, 7 to 9, Reference Examples 5 and 6, and Comparative Examples 1 to 6]
The interior materials (wallpaper) according to these examples and comparative examples were the same as in Example 1 except that the base, the base material layer, the binder, and the deodorant particles as described in Table 1 were used. Obtained. In Example 4, a mixture of 10 parts by mass of Lionite PC and 3 parts by mass of dashlite was used as deodorant particles.

In addition, the abbreviations in Table 1 indicate the following.
(binder)
EVOH: EVOH having an ethylene unit content of 44 mol% and a saponification degree of 99%
EVOH (2): partially saponified EVOH having an ethylene unit content of 72 mol% and a saponification degree of 97%
-Ethylene-modified PVA: ethylene-modified PVA having an ethylene unit content of 8 mol% and a saponification degree of 99%
(Deodorant particles)
Lionite PC-301P: inorganic porous particles carrying a photocatalyst manufactured by Lion Corporation (particles containing porous silicate mineral synthesized from silica, alumina, metal oxide and titanium oxide as a photocatalyst)
・ Lionite SF: Inorganic porous particles manufactured by Lion Corporation (porous silicate mineral synthesized from silica, alumina, and metal oxide)
・ Mizukanite HP: Mizusawa Chemical Co., Ltd. inorganic porous particles (composite of silicon dioxide, zinc oxide, aluminum oxide)
Zeomic AV-10D: inorganic porous particles (composite of aluminum oxide, silicon dioxide, etc.) manufactured by Sinanen Co., Ltd.
・ Dashlight: A composite of an amine compound (hydrazine derivative) and a silicate inorganic compound manufactured by Sinanen Co., Ltd.

In addition, the particle diameter, BET specific surface area, and average pore diameter of each deodorant particle were calculated | required by the method of the following description.
(Particle size)
Using a laser diffraction particle size meter LA-950V2 manufactured by HORIBA, Ltd., 2.5 mL of a liquid in which 0.05 g of deodorant particles are dispersed in 20 mL of water is added to the apparatus, and then measured while irradiating with ultrasonic waves 5 times. The average median diameter determined in this manner was taken as the particle diameter. Measurement conditions: flow cell method (wet), refractive index 1.48, dispersion medium (water: 1.333).

(BET specific surface area and average pore diameter)
An adsorption isotherm by nitrogen was measured by a nitrogen gas adsorption method using 0.2 g of deodorant particles and using an automatic gas / vapor adsorption amount measuring device “BELSORP18PLUS-HT” manufactured by Nippon Bell Co., Ltd. As pretreatment conditions, vacuum degassing was performed at 150 ° C. for about 5 hours. The adsorbate _{N 2,} the dead volume measurement gas as He, relative pressure of about 0-1, the saturated vapor pressure 101.3 kPa, measured at a measuring temperature of 77K. The BET specific surface area was calculated by the BET method. Moreover, it calculated as an average pore diameter from the value of the pore volume and specific surface area obtained by BJH method, and it was set as the average pore diameter. Since Zeomic AV-10D showed an adsorption isotherm of type I, the average pore diameter was calculated from the pore volume and specific surface area values obtained by the MP method.

  In Comparative Example 2, the deodorant particles were obtained by kneading the resin composition for forming the base material layer, and the mass ratio of the binder and the deodorant particles in Table 1 is as follows. In Comparative Example 2, it is the mass ratio of the resin composition of the base material layer and the deodorant particles. Comparative Example 6 is only a non-foamed vinyl chloride wallpaper manufactured by Nankai Technate Co., Ltd., which does not have a multilayer structure.

  Moreover, the presence or absence of the convex part which made the deodorizing particle | grains on the surface of the obtained interior material (wallpaper) the nucleus was confirmed by observation of the surface with an electron microscope. In Table 1, “◯” indicates that the presence of a plurality of protrusions could be confirmed, and “X” indicates that the protrusion could not be confirmed. For example, as shown in the electron micrograph of FIG. 3, the wallpaper (interior material) of Example 1 has a plurality of convex portions with deodorant particles as the core formed on the surface.

<Characteristic evaluation>
Each characteristic of the interior material (wallpaper) obtained in Examples 1 to 4, 7 to 9, Reference Examples 5 and 6 and Comparative Examples 1 to 6 was evaluated according to the method described below. These evaluation results are shown in Table 2.

(1) Glossiness Based on JIS-Z8741, it measured with the gloss meter VGS-300A by Nippon Denshoku Industries Co., Ltd. at the angle of 60 degree | times.

(2) Crack resistance The surface after embossing was visually observed and evaluated as follows.
○ ・ ・ ・ No crack occurrence × ・ ・ ・ Crack occurrence

(3) Deodorizing performance The wallpaper was cut into 10 cm × 10 cm, and the back surface was closed with aluminum tape to obtain a wallpaper for evaluating deodorization. The wallpaper for evaluation of deodorization was put in a Tedlar bag, and 2 L of odor model gas (ammonia or acetic acid) adjusted so that the gas concentration was 100 ppm was injected. The gas concentration was measured with a gas detector manufactured by Gastec Co., Ltd., and the deodorization rate was determined from the following formula, and the following evaluation was made.
Deodorization rate = {(initial concentration−concentration after 24 hours) / initial concentration} × 100 (%)
A: Deodorization rate of 50% or more B ... Deodorization rate of 40% or more and less than 50% C: Deodorization rate of less than 40% Note that A and B are practically preferred levels as deodorization performance.

(4) Desorption property After the above (3) deodorization performance test, the inside of the Tedlar bag is replaced with fresh air, the gas concentration after heating at 50 ° C. for 1 hour is measured, and the release rate is obtained from the following formula. It was evaluated.
Release rate = (concentration after heating / concentration before heating) × 100%
○ ・ ・ ・ Release rate less than 50% △ ・ ・ ・ Release rate 50% or more and less than 100% × ・ ・ ・ Release rate 100% or more

(5) Antifouling performance In accordance with the wallpaper product standard (SV standard: Standard Value) established by the Wallpaper Industry Association, coffee, soy sauce, water-based magic, and crayons are applied to the surface of the wallpaper. After 24 hours, the coffee and soy sauce are water. Wiping, water-based magic and crayon were wiped off with a neutral detergent (Lion Mama Lemon). Oily magic was also wiped off with a light removal solution 24 hours after application. The remaining dirt was determined according to the SV standard, and the following evaluation was made.
○ ・ ・ ・ 4th grade or higher △ ・ ・ ・ 3rd grade × ・ ・ ・ 2nd grade or lower − ・ ・ ・ Deodorant functional layer disappeared.

(6) Water resistance and solvent resistance The deformation of the deodorant functional layer after the evaluation of the above (5) antifouling performance was evaluated. The water resistance was evaluated after wiping with a neutral detergent, and the solvent resistance was evaluated after wiping with a light removal liquid.
○ ・ ・ ・ Deformation of the deodorant functional layer was not observed. × ・ ・ ・ The surface of the deodorant functional layer was deformed by wiping.

  As shown in Table 2, the interior materials (wallpaper) of Examples 1 to 4, 7 to 9 and Reference Examples 5 and 6 are both excellent in deodorizing performance and antifouling performance. On the other hand, Comparative Example 1 in which the deodorant particles are not contained in the deodorant functional layer, although the deodorant particles are contained, it is kneaded in the base material layer and protrudes as a convex portion on the surface. The interior material (wallpaper) of Comparative Example 2 that has no deodorizing property is low. Moreover, the interior material (wallpaper) of Comparative Examples 3 to 5 using a binder other than EVOH has low crack resistance and stain resistance.

  As described above, the deodorizing functional layer and the multilayer structure of the present invention are excellent in both the deodorizing function and the antifouling function, and are suitably used for interior materials such as wallpaper.

DESCRIPTION OF SYMBOLS 1 Deodorizing functional layer 2 Ethylene-vinyl alcohol copolymer 3 Deodorizing particle 4 Convex part 5 Multilayer structure 6 Base material layer

Claims (14)

An ethylene-vinyl alcohol copolymer having an ethylene unit content of 10 mol% or more, and a deodorizing functional layer containing deodorizing particles,
The deodorant particles as a core, at least a majority of the surface of the nucleus of the ethylene - have a plurality of protrusions formed on the surface by coating with a vinyl alcohol copolymer,
The mass ratio of the ethylene-vinyl alcohol copolymer to the deodorant particles is 1 or more and 3 or less,
The deodorizing deodorizing functional layer content, characterized in der Rukoto 0.3 g / ^{m 2} or more 1.2 g / ^{m 2} or less of the particles.   The deodorant functional layer according to claim 1, wherein a ratio of an average particle diameter of the deodorant particles to an average thickness is 1 or more and 10 or less.   The deodorant functional layer according to claim 1 or 2, wherein the deodorant particles have an average particle diameter of 1 µm or more and 10 µm or less.   4. The deodorizing functional layer according to claim 1, wherein the average thickness is 1 μm or more and 3 μm or less. The deodorizing functional layer according to any one of claims 1 to 4 , wherein the deodorizing particles are inorganic porous particles. The deodorizing functional layer according to claim 5 , wherein the inorganic porous particles carry a photocatalyst. The deodorizing functional layer according to any one of claims 1 to 6 , wherein the ethylene-vinyl alcohol copolymer has an ethylene content of 20 mol% to 60 mol% and a saponification degree of 90% or more. . The deodorizing functional layer according to any one of claims 1 to 7 , wherein the deodorizing functional layer is formed by applying a resin composition containing the ethylene-vinyl alcohol copolymer, deodorant particles, and a solvent. A base material layer;
The multilayer structure which has the deodorizing functional layer of any one of Claim 1 to 8 laminated | stacked so that the said convex part may be located in the outer surface on the one surface side of this base material layer. The multilayer structure according to claim 9 , wherein the base material layer contains an ethylene-vinyl alcohol copolymer. Interior material comprising the multilayer structure according to claim 9 or claim 1 0 on the surface. Interior material according to claim 1 1 surface glossiness is 20% or less than 2%.   A wallpaper comprising the interior material according to claim 11 or 12. A step of applying a resin composition containing an ethylene-vinyl alcohol copolymer having an ethylene unit content of 10 mol% or more, deodorant particles and a solvent to one surface side of the base material layer, and the applied resin composition object is dried, a method for manufacturing a multilayer structure according to claim 9 or claim 1 comprising 0 convex portion forming step of forming a plurality of convex portions of the deodorant particles as nuclei to the outer surface.