Odor-absorbing film for vehicle interiors

Abstract

To provide an odor adsorptive film for vehicle interior which has an excellent balance among manufacture suitability such as film formation properties, filling machine suitability, and a high odor adsorption effect for adsorbing VOC component odor, tobacco odor, body odor, life odor or pet odor over a long period of time.SOLUTION: An odor adsorptive film for vehicle interior for adsorbing VOC component odor, tobacco odor, body odor, life odor or pet odor has at least an odor adsorptive layer, in which the odor adsorptive layer contains a binder resin and an odor adsorbent, and the odor adsorbent contains hydrophobic zeolite and / or a metal-carried inorganic porous body.SELECTED DRAWING: Figure 3

Description

[Technical Field]

[0001] The present invention particularly relates to an absorbent film for vehicle interiors that has excellent absorbency for odorous substances such as VOC components, cigarette odor, body odor, household odors, and pet odors. [Background technology]

[0002] In recent years, there has been a strong demand for materials that can improve odors in the interior spaces of vehicles that are shared by various people and used for long periods of time, such as shared cars, rental cars, Shinkansen bullet trains, and airplanes. Packaging materials incorporating odor adsorbents have been proposed. In these packaging materials, odor adsorbents such as synthetic zeolite and activated carbon are kneaded into the resin material (Patent Document 1). However, these materials have the problem of adsorbing not only odors but also moisture in the air, and once adsorbed, the odors are released, so sufficient odor adsorption effects are not achieved. Packaging materials containing odor adsorbents made by supporting a chemical adsorbent on an inorganic porous material are also known (Patent Document 2), but the main substances to be adsorbed are only odor components with specific functional groups, and unless the resin material is selected appropriately, they are unable to adequately adsorb odor components of organic substances that do not have functional groups. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Patent No. 2538487 [Patent Document 2] Japanese Patent Application Laid-Open No. 2014-233408 Summary of the Invention [Problem to be solved by the invention]

[0004] The present invention aims to solve the above-mentioned problems and to provide an adsorbent film for vehicle interiors that has an excellent balance of manufacturing suitability such as film-forming properties, suitability for filling machines, and a high odor adsorption effect over a long period of time against odorous substances such as VOC components, cigarette odor, body odor, household odors, and pet odors. [Means for solving the problem]

[0005] As a result of extensive investigations, the present inventors have found that an absorbent film for vehicle interiors having a specific odor-absorbing layer can achieve the above-mentioned object. The present invention is characterized by the following points. 1. An absorbent film for vehicle interiors to absorb VOC component odors, cigarette odors, body odors, household odors, or pet odors, The adsorbent film for vehicle interiors has at least an odor adsorption layer, the odor absorbing layer contains a binder resin and an odor absorbing agent; The odor adsorbent contains hydrophobic zeolite and / or a metal-supported inorganic porous material, The absorbent film for vehicle interiors. 2. The adsorbent film for vehicle interiors according to the above item 1, wherein the odor adsorbent further contains an amino group-supported inorganic porous material and / or a hydroxyl group-supported inorganic porous material. 3. The binder resin has a density of 0.90 g / cm 3 More than 0.94g / cm 3 3. The adsorbent film for vehicle interiors according to 1 or 2 above, which is one or more types selected from the group consisting of C4-LLDPE, C6-LLDPE and C8-LLDPE. 4. An adsorbent film for vehicle interiors, as described in any one of 1 to 3 above, wherein the odor adsorbent is melt-kneaded in advance with a thermoplastic resin in a mass ratio of odor adsorbent / thermoplastic resin of 0.5 / 99.5 to 40 / 60. 5. The layer structure of the adsorbent film for vehicle interiors is: a layer structure consisting of only the odor adsorption layer; a layer structure having the odor adsorption layer and a thermoplastic resin layer on one surface thereof; a layer structure having the odor adsorption layer and thermoplastic resin layers on both surfaces thereof; Any layer structure selected from the group consisting of: the thermoplastic resin layer contains a thermoplastic resin but does not contain the odor adsorbent; 5. An adsorbent film for vehicle interior use according to any one of 1 to 4 above. 6. The binder resin and / or the thermoplastic resin is a heat-sealable resin, The adsorbent film for vehicle interiors has heat sealability. 6. An adsorbent film for vehicle interior use according to any one of 1 to 5 above. [Effects of the Invention]

[0006] According to the present invention, it is possible to provide an adsorbent film for vehicle interiors that has an excellent balance of manufacturing suitability such as film-forming properties, suitability for filling machines, and a high odor adsorption effect over a long period of time against odorous substances such as VOC components, cigarette odor, body odor, household odors, and pet odors. Furthermore, when an interior material made using the adsorbent film for vehicle interiors of the present invention is used in the interior of a vehicle, the concentration of odorous substances such as VOC components, cigarette odor, body odor, household odor, or pet odor in the air inside the vehicle is reduced, thereby reducing discomfort to passengers and maintaining their health. [Brief explanation of the drawings]

[0007] [Figure 1] 1 is a schematic cross-sectional view showing an example of the layer structure of an adsorbent film for vehicle interiors of the present invention. [Figure 2] FIG. 2 is a schematic cross-sectional view showing another example of the layer structure of the adsorbent film for vehicle interior use of the present invention. [Figure 3] FIG. 2 is a schematic cross-sectional view showing another example of the layer structure of the adsorbent film for vehicle interior use according to the present invention. [Figure 4] FIG. 1 is a diagram showing the adsorption mechanism of odorous substances by a chemical adsorbent-supporting inorganic porous material. DETAILED DESCRIPTION OF THE INVENTION

[0008] The adsorbent film for vehicle interiors of the present invention will be described in detail below. Specific examples will be given, but the present invention is not limited thereto.

[0009] <<Odor-absorbent film for vehicle interiors>> The odor-absorbing film for vehicle interiors of the present invention is a film having odor-absorbing properties, and is particularly excellent in absorbing VOC component odors, cigarette odors, body odors, household odors, and pet odors. In the interior spaces of vehicles such as automobiles, trains, and airplanes, odors such as cigarette smoke, body odor, household odors, and pet odors are generated, and in new vehicles, the odor of VOC components is strong. However, by using the absorbent film for vehicle interiors of the present invention as an interior material, these odors can be reduced. The layer structure of the odor-absorbing film for vehicle interiors includes at least an odor-absorbing layer. The adsorbent film for vehicle interiors may be a single layer structure as shown in FIG. 1, which is composed only of an odor adsorption layer, or may be a laminate structure having a multi-layer structure. In the case of a multi-layer structure, it may further contain various layers other than the odor adsorption layer, such as a substrate layer, various intermediate layers, and printed layers, as necessary. Additionally, for vehicle interior applications, the absorbent film can be subjected to lamination (dry lamination or extrusion lamination), bag making, and other post-processing processes.

[0010] The odor absorbing layer contains an odor adsorbent and a binder resin, and may contain other components. If the binder resin is a heat-sealable resin, the odor absorbing layer can have heat-sealability. The odor adsorption layer may be composed of a single layer containing a binder resin and an odor adsorbent, or may be composed of two or more layers with the same and / or different compositions, for example, two or more layers with different types or amounts of odor adsorbents. Furthermore, for example, one or both surfaces of the adsorbent film for vehicle interiors may be a thermoplastic resin layer containing a thermoplastic resin but not containing an odor adsorbent, as shown in Figures 2 and 3. If the thermoplastic resin in this thermoplastic resin layer is a heat-sealable resin, this layer can function as a heat-sealable layer with excellent heat-sealability. By providing a heat seal layer or an odor absorbing layer with a low odor absorbing agent content on the outer surface of the absorbent film for vehicle interiors, the absorbent film for vehicle interiors can have high heat sealability. The absorbent film for vehicle interiors may contain other components in addition to the binder resin, thermoplastic resin, and odor absorbent, such as slip agents, antiblocking agents, antioxidants, solvents, and other additives in small amounts as needed. Furthermore, in the case of vehicle interiors, the layers constituting the adsorbent film may be laminated via an adhesive layer.

[0011] Specific examples of layer configurations of absorbent films for vehicle interiors include a single-layer configuration consisting of an odor-absorbing layer, a two-layer configuration consisting of a thermoplastic resin layer / odor-absorbing layer, and a three-layer configuration consisting of a thermoplastic resin layer / odor-absorbing layer / thermoplastic resin layer.

[0012] The content of the odor adsorbent in the odor adsorption layer is preferably 0.3% by mass or more and 15% by mass or less, and more preferably 0.5% by mass or more and 14% by mass or less. If the content is less than this range, the odor adsorption effect is difficult to achieve, and if the content is more than this range, film formability may be impaired.

[0013] The thickness of the adsorbent film for vehicle interiors of the present invention is preferably 20 μm or more and 150 μm or less, and more preferably 25 μm or more and 130 μm or less, in order to achieve a good balance between odor adsorption properties and rigidity, heat sealability, etc. If it is thinner than the above range, it is prone to tearing, and if it is thicker than the above range, it is too rigid and is likely to be inferior in suitability for vehicle interior applications. The thickness of the odor adsorption layer is preferably 10 μm or more and 100 μm or less. If it is thinner than this range, the heat sealability and / or odor adsorption properties may be insufficient, and if it is thicker than this range, the laminate may be too rigid.

[0014] [Odor absorption] In the present invention, odor adsorption ability refers to the ability to physically adsorb odorous substances, the ability to chemically adsorb odorous substances, or the ability to decompose and deodorize them by oxidation-reduction reaction. In the present invention, the odors to be adsorbed are VOC component odors, cigarette odors, body odors, household odors, and pet odors. Details of these odors include, for example, VOC component odors such as formaldehyde odor, acetaldehyde odor, and organic solvent odor, tobacco odors such as acetaldehyde odor and organic solvent odor, body odors such as sebum odors such as diacetyl odor, aging odors such as nonenal odor and diacetyl odor, everyday odors such as hydrogen sulfide odor and acetic acid odor, and pet odors such as amine-based odors and sulfur-based odors. Specific examples of amine compounds that emit amine-based odors include ammonia, dimethylamine, pyridine, and trimethylamine. Specific examples of sulfur compounds that emit sulfur-based odors include hydrogen sulfide, methanethiol, dimethyl sulfide, propanethiol, and dimethyl disulfide.

[0015] (Suitable for filling machines) Filling machine suitability refers to the manufacturing suitability that does not cause defects such as poor heat sealing or pinholes in a process using a filling machine that continuously produces a sterilization-generated odor-absorbing package and fills it with the contents.

[0016] [Odor absorbent] In the present invention, the odor adsorbent may be a physical odor adsorbent and / or a chemical odor adsorbent. The physical odor adsorbent is an odor adsorbent that physically adsorbs odorous substances, preferably exhibiting a neutralizing effect, and specific compounds include hydrophobic zeolite and inorganic porous materials. Chemical odor adsorbents are odor adsorbents that chemically adsorb odorous substances and preferably decompose the odorous substances through an oxidation-reduction reaction. Examples of such adsorbents include deodorizing glass with oxidation-reduction properties, mixtures of metal salts and metal oxides, and inorganic porous bodies carrying chemical adsorbents. Examples of the inorganic porous material carrying a chemical adsorbent include an amino group-carrying inorganic porous material, a hydroxyl group-carrying inorganic porous material, and a metal-carrying inorganic porous material. The odor adsorption layer of the present invention can contain one or more odor adsorbents selected from the above group, and preferably contains a hydrophobic zeolite and / or a metal salt-supported inorganic porous material. It is even more preferable that the layer further contains an amino group-supported inorganic porous material and / or a hydroxyl group-supported inorganic porous material, if necessary.

[0017] (hydrophobic zeolite) In the present invention, the hydrophobic zeolite has a function of mainly physically adsorbing odorous substances. Hydrophobic zeolites have excellent adsorption performance for aldehydes, ketones, sulfur-based compounds, and amines, and are particularly excellent in adsorption performance for aldehydes, ketones, and sulfur-based compounds. In the present invention, the hydrophobic zeolite used as the odor adsorbent preferably has a SiO2 / Al2O3 molar ratio of 400 / 1 to 10000 / 1. When the molar ratio is within the above range, the hydrophobicity and pore size are well balanced, and good odor adsorption properties can be achieved. The hydrophobic zeolite maintains its effect of adsorbing odorous components even when the laminate of the present invention is exposed to temperatures of 230°C or higher. The hydrophobic zeolite may have any external shape such as a sphere, a rod, an ellipse, or the like, and may be in any form such as a powder, a lump, or a granule. However, from the viewpoints of uniform dispersibility, kneading properties, film-forming properties, and the like when dispersed in a resin, a powder form is preferred.

[0018] In the present invention, the average particle size of the hydrophobic zeolite can be selected appropriately depending on the application, but the average particle size is preferably 0.01 μm to 15 μm. Here, the average particle size is a value measured by dynamic light scattering. If the average particle size is smaller than the above range, the hydrophobic zeolite tends to aggregate and the dispersibility tends to decrease, whereas if the average particle size is larger than the above range, the film-forming properties of the layer containing the hydrophobic zeolite tend to be poor, making it difficult to add a large amount of hydrophobic zeolite, and furthermore, the surface area is reduced, which may result in insufficient deodorizing effect.

[0019] Unlike non-hydrophobic (hydrophilic) zeolites, in which odorous substances and water vapor are adsorbed at the same adsorption sites, hydrophobic zeolites are hydrophobic and therefore have difficulty adsorbing highly polar water molecules, but have a high affinity for less polar odorous molecules, hydrophobic gases, and lipophilic gases (including solvent-based gases), which are easily adsorbed. Furthermore, due to the effect of alkali metals and alkaline earth metals such as Ca, Na, and K present on the zeolite surface, the zeolite surface exhibits basicity, making it easy to adsorb acidic gases through a neutralization reaction.

[0020] (Inorganic porous material) Examples of inorganic porous materials used in physical odor adsorbents include activated clay and activated bentonite. Activated clay is a type of clay that is porous, has a large specific surface area, and has excellent adsorption properties. It is obtained by heat treating acid clay, whose main component is naturally occurring montmorillonite, with inorganic acids such as sulfuric acid or hydrochloric acid. Activated clay with a large specific surface area is preferred. There is no particular limit to the specific surface area, but a specific surface area of ​​50 to 400 m is preferred. 2 The pH (5% suspension) is preferably 2.5 to 9, more preferably 3 to 7. Activated bentonite is made by artificially converting Ca-type bentonite into Na-type bentonite by adding a few wt% of sodium carbonate, and exhibits properties similar to those of Na-type bentonite. Here, bentonite is a substance whose main component is the clay mineral montmorillonite and contains minerals such as quartz and feldspar as impurities. + Na-type bentonite containing a lot of ions and Ca-type bentonite 2+ Basic bentonite is preferred, with a pH of preferably 8 to 13, more preferably 9 to 12, and even more preferably 10 to 11.

[0021] (Deodorizing glass) Deodorizing glass is a glassy inorganic material with deodorizing effects, and contains compounds in which phosphorus, copper, silicon, and other metal salts are supported on inorganic materials. Trace amounts of the contained metal elements are ionized to exert a deodorizing effect. The metal components in the deodorizing glass are ionized and act as a catalyst to accelerate the decomposition reaction of odorous substances.

[0022] (Metal salt / metal oxide mixture) The metal salt-metal oxide mixture is a mixture of a salt consisting of a metal cation and an inorganic acid anion mixed with a metal oxide, such as alum (AlK(SO4)2) mixed with CaO and ZnO. The metal components in the metal salt / metal oxide mixture are ionized, and act as a catalyst to accelerate the decomposition of odorous sulfur compounds.

[0023] (Chemical adsorbent-supported inorganic porous material) In the present invention, the chemical adsorbent-supported inorganic porous material is an inorganic porous material that supports an organic compound or a metal compound and has the function of mainly chemically adsorbing odorous substances, and examples thereof include amino group-supported inorganic porous materials, hydroxyl group-supported inorganic porous materials, and metal-supported inorganic porous materials. In the present invention, the organic compound used in the chemical adsorbent-supported inorganic porous material is a compound that has a reactive functional group that chemically reacts with and bonds to odorous substances and that can be supported on the inorganic porous material. More specifically, it is a compound having a functional group that is reactive to bond with aldehydes, ketones, sulfur-based compounds, or amines, and examples of such compounds include compounds having an amino group, compounds having a hydroxyl group, and metal compounds.

[0024] As a method for supporting the chemical adsorbent, a known or commonly used supporting method can be applied. For example, the chemical adsorbent can be supported by impregnating the inorganic porous body with a solution containing the chemical adsorbent described below and drying the resultant. In the present invention, by using a chemical adsorbent-supported inorganic porous material, the adsorption capacity per unit mass of the odor adsorbent can be significantly increased, the content of the odor adsorbent in the anticorrosive layer can be reduced, and physical adsorption properties in the pores of the inorganic porous material can also be expected. These properties make it possible to maintain excellent film-forming properties, and in some cases to maintain a balance with coatability, heat-sealability, and the like.

[0025] The chemical adsorbent-supporting inorganic porous material may have any external shape, such as a spherical, rod-like, or elliptical shape, and may be in any form, such as a powder, a lump, or a granule. However, from the viewpoints of the above-mentioned film-forming properties, uniform dispersibility, kneading properties, etc., a powder form is preferred.

[0026] The average particle size of the chemical adsorbent-supporting inorganic porous material can be selected appropriately depending on the application, but in the present invention, the average particle size is preferably 0.01 μm to 15 μm, more preferably 0.1 μm to 13 μm, and even more preferably 1 μm to 12 μm. Here, the average particle size is a value measured by dynamic light scattering. If the average particle size is smaller than the above range, the chemical adsorbent-supporting inorganic porous material is likely to aggregate, and dispersibility tends to decrease. Furthermore, if the average particle size is larger than the above range, the film-forming properties will be poor, making it difficult to incorporate a large amount of the chemical adsorbent-supporting inorganic porous material, and there is a possibility that a sufficient adsorption effect will not be obtained.

[0027] The mechanism by which the chemical adsorbent-carrying inorganic porous material adsorbs odorous substances will be explained in more detail using specific examples shown in FIGS. 4(a) and 4(b), but the present invention is not limited to these. Figure 4(a) shows the case where carboxylic acid odorants are chemically adsorbed onto a hydroxyl group-supported inorganic porous material. The carboxylic acid groups of the carboxylic acid odorants and the hydroxyl groups of the hydroxyl group-supported inorganic porous material undergo a chemical reaction to bond, resulting in the adsorption of the carboxylic acid odorants. Figure 4(b) shows the case where aldehyde odorants are chemically adsorbed onto an inorganic porous material carrying amino groups. The aldehyde groups of the aldehyde odorants and the amino groups of the inorganic porous material undergo a chemical reaction to bond, resulting in the adsorption of the aldehyde odorants.

[0028] The chemical adsorbent-carrying inorganic porous material is chemically adsorbed, so that once adsorbed odorous substances are difficult to desorb, and odor adsorption can be carried out efficiently. Furthermore, since odorants bind to specific functional groups of the chemical adsorbent, it is less susceptible to the effects of various substances that reduce odor adsorption capacity, such as water vapor.

[0029] (Amino group-supported inorganic porous material) The amino group-supported inorganic porous material is an inorganic porous material that supports amino groups on the surface, and is capable of chemically adsorbing odorous substances that chemically react with the amino groups. The amino group-supporting inorganic porous material can be prepared, for example, by using a compound having an amino group. Examples of compounds containing an amino group include alkylamines, cyclic amines, polyamines, and alcoholamines, such as ethylenediamine, tetramethylenediamine, metaphenylenediamine, diethylenetriamine, triethylenetriamine, tetraethylenepentamine, ethanolamine, piperazine, and piperidine. The amino group-supported inorganic porous material has excellent adsorption performance for aldehydes and ketones. Aldehydes and ketones react chemically with amino groups via the Schiff reaction and are adsorbed.

[0030] (Hydroxyl group-supported inorganic porous material) The hydroxyl group-supporting inorganic porous material is an inorganic porous material that supports hydroxyl groups on the surface, and is capable of chemically adsorbing odorous substances that chemically react with hydroxyl groups. The hydroxyl group-supporting inorganic porous material can be prepared, for example, by using a compound having a hydroxyl group. Examples of compounds having a hydroxyl group include metal hydroxides, such as sodium hydroxide, potassium hydroxide, magnesium hydroxide, and iron hydroxide. The hydroxyl group-supported inorganic porous material has excellent adsorption performance for carboxylic acids and amines.

[0031] (Metal salt-supported inorganic porous material) The metal-supported inorganic porous material is an inorganic porous material that supports a metal element in the state of metal, metal ion, or metal oxide. Metal-supported inorganic porous materials have excellent adsorption performance for sulfur-based compounds, ketones, and amines. The metal species to be supported preferably contains one or more metals selected from the group consisting of copper, zinc, silver, platinum, iron and cobalt. In the present invention, by using a metal-supported inorganic porous material, the adsorption capacity per unit mass of the odor adsorbent can be significantly increased, the content in the laminate can be reduced, and physical adsorption properties in the pores of the inorganic porous material can also be expected. Furthermore, the metal-supported inorganic porous material may have any external shape, such as a spherical, rod-like, or elliptical shape, and may be in any form, such as a powder, a lump, or a granule. However, from the viewpoints of the above-mentioned film-forming properties, uniform dispersibility, kneading properties, etc., a powder form is preferred.

[0032] The metal-supported inorganic porous material can be selected from those with any average particle size depending on the application, but in the present invention, those with an average particle size of 0.01 μm to 15 μm are particularly preferred, those with an average particle size of 0.1 μm to 13 μm are more preferred, and those with an average particle size of 1 μm to 12 μm are even more preferred. Here, the average particle size is a value measured by dynamic light scattering. If the average particle size is smaller than the above range, the metal-supported inorganic porous material is likely to aggregate, and dispersibility tends to decrease. If the average particle size is larger than the above range, the film-forming properties will be poor, making it difficult to incorporate a large amount of the metal-supported inorganic porous material, and there is a possibility that a sufficient adsorption effect will not be obtained.

[0033] (Inorganic porous material used for chemical adsorbent-supporting inorganic porous material) In the present invention, the inorganic porous material used in the chemical adsorbent-supporting inorganic porous material can be any inorganic compound having a large number of pores on its surface. Examples include zeolite, silicon dioxide, silicates, activated carbon, titania, inorganic phosphates such as calcium phosphate, alumina, aluminum hydroxide, magnesium hydroxide, and mixtures thereof. In particular, aluminum hydroxide, zeolites, and silicates are preferably used in view of the pore state having pore sizes effective for the molecular size or cluster size of the substance to be adsorbed, and from the viewpoint of safety. In the above, the zeolite is preferably hydrophobic, and more preferably has an SiO2 / Al2O3 molar ratio of 400 / 1 to 10,000 / 1. In particular, aluminum hydroxide, zeolite, and silicates are preferably used from the viewpoint of safety and having a porous state with pores of an effective size relative to the molecular size or cluster size of the substance to be adsorbed. The inorganic porous body may have any external shape, such as a spherical shape, a rod shape, an elliptical shape, or the like, and may be in any form, such as a powder shape, a lump shape, or a granular shape. However, a powder shape is preferred from the viewpoints of the film-forming properties, uniform dispersion, kneading properties, and the like, after the inorganic porous body is made by supporting the chemical adsorbent.

[0034] The inorganic porous material can be selected from those with any average particle size depending on the application, but in order to achieve the average particle size of the above-mentioned chemical adsorbent-supported inorganic porous material, the average particle size is preferably 0.01 μm to 15 μm, more preferably 0.1 μm to 13 μm, and even more preferably 1 μm to 12 μm.

[0035] (Improved dispersion by making odor adsorbents into master batches) The odor adsorbent may be directly mixed with the other components of the odor adsorption layer and melt-kneaded, but it is preferable to increase the dispersibility of the odor adsorbent in the odor adsorption layer by using the so-called masterbatch method, in which the odor adsorbent is mixed at a high concentration with a thermoplastic resin and then melt-kneaded (melt-blended) to prepare a masterbatch, and this is then mixed with the other components of the odor adsorption layer in a ratio corresponding to the target content and melt-kneaded. By employing the masterbatch method, even when an odor adsorbent that is prone to aggregation is used, the odor adsorbent can be dispersed efficiently and uniformly in the odor adsorption layer. Here, the thermoplastic resin that is a constituent component of the odor adsorption layer and the thermoplastic resin contained in the masterbatch may be the same or different.

[0036] The mass ratio of gas adsorbent to thermoplastic resin in the masterbatch is not particularly limited, but is preferably 0.5 / 99.5 to 40 / 60, and more preferably 1 / 99 to 35 / 65. As a method for kneading the odor adsorbent and the thermoplastic resin, a known or commonly used kneading method can be applied. The thermoplastic resin used in the masterbatch can be of a type and content within a range that does not significantly adversely affect the heat sealability, film formability, or odor adsorption properties of the entire odor adsorption layer.

[0037] The MFR (melt flow rate) of the thermoplastic resin is preferably 0.2 g / 10 min or more and 10 g / 10 min or less. An MFR in this range facilitates melt-kneading with the odor adsorbent, facilitating dispersion of the odor adsorbent in the odor adsorption layer, and maintaining the film-forming properties of the odor adsorption layer.

[0038] Specific examples of thermoplastic resins include general-purpose polyethylene, polypropylene, methylpentene polymer, polyolefin resins such as acid-modified polyolefin resins, and mixtures of these resins, but are not limited to these resins, and the type of thermoplastic resin can be selected depending on the purpose. Furthermore, it is possible and preferable to use the thermoplastic resin contained in the odor adsorption layer as the thermoplastic resin.

[0039] [Binder resin] The binder resin contained in the odor adsorption layer is preferably a thermoplastic resin that can disperse the odor adsorbent and form the odor adsorption layer. When the odor adsorption layer has heat-sealing properties, it is preferable to use a heat-sealing resin as the binder resin. Examples of binder resins include polyolefins, olefin copolymers, copolymers of olefins and vinyl compounds, copolymers of olefins and various (meth)acrylic compounds, copolymers of olefins and unsaturated carboxylic acids, ionomer resins, terpolymer resins of olefins, various (meth)acrylic compounds, and various unsaturated carboxylic acids, polyethylene terephthalate (PET), polyacrylonitrile (PAN), etc. These may be used alone or in combination of two or more. Among the above, polyolefins and olefin copolymers are preferred, olefin copolymers are more preferred, and among olefin copolymers, polyethylene resins are even more preferred. These resins also have excellent heat-sealing properties. Specific examples of polyethylene-based resins include low-density polyethylene (LDPE), medium-density polyethylene (MDPE), high-density polyethylene (HDPE), linear low-density polyethylene (LLDPE), ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-methyl methacrylic acid copolymer, ethylene-propylene copolymer, and mixtures of these resins, but are not limited to these resins. Among the above polyethylene resins, LLDPE is more preferable, and the density is 0.90 g / cm 3 More than 0.94g / cm 3 More preferred is one or more selected from the group consisting of C4-LLDPE, C6-LLDPE, and C8-LLDPE. These resins also have excellent heat-sealing properties. By setting the density within the above range, good stretchability due to good softness can be obtained. If the density is below the above range, the softening point may be too low, making it difficult to maintain the layer structure, and if the density is above the above range, there is a risk that the stretchability will decrease. The MFR (melt flow rate) of the binder resin is preferably 1 g / 10 min or more and 10 g / 10 min or less, and more preferably 1.5 g / 10 min or more and 7 g / 10 min or less. If the MFR is within the above range, even when mixed with the odor adsorbent, the binder resin can maintain a good MFR and exhibit good film-forming properties and adhesive properties.

[0040] <Heat seal layer> The heat-sealable layer is a layer having excellent heat-sealability that is laminated on one or both surfaces of the odor-adsorbing stretched film of the present invention. The heat seal layer is a layer containing a heat sealable resin and no or a low content of an odor adsorbent.

[0041] (Heat sealable resin) Examples of heat-sealable resins include polyolefins, olefin copolymers, copolymers of olefins and vinyl compounds, copolymers of olefins and various (meth)acrylic compounds, copolymers of olefins and unsaturated carboxylic acids, ionomer resins, terpolymer resins of olefins, various (meth)acrylic compounds, and various unsaturated carboxylic acids, polyethylene terephthalate (PET), polyacrylonitrile (PAN), etc. These may be used alone or in combination of two or more. Among the above, polyolefins and olefin copolymers are preferred, olefin copolymers are more preferred, and among olefin copolymers, polyethylene resins are even more preferred. Specific examples of polyethylene-based resins include low-density polyethylene (LDPE), medium-density polyethylene (MDPE), high-density polyethylene (HDPE), linear low-density polyethylene (LLDPE), ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-methyl methacrylic acid copolymer, ethylene-propylene copolymer, and mixtures of these resins, but are not limited to these resins. Among the above polyethylene resins, LLDPE is more preferable, and the density is 0.90 g / cm 3 More than 0.94g / cm 3 More preferred is one or more selected from the group consisting of C4-LLDPE, C6-LLDPE, and C8-LLDPE. By setting the density within the above range, good stretchability due to good softness can be obtained. If the density is below the above range, the softening point may be too low, making it difficult to maintain the layer structure, and if the density is above the above range, there is a risk that the stretchability will decrease. The MFR (melt flow rate) of the heat-sealable resin is preferably 1 g / 10 min or more and 10 g / 10 min or less, and more preferably 1.5 g / 10 min or more and 7 g / 10 min or less. If the MFR is within the above range, even when mixed with an odor adsorbent, the resin can maintain a good MFR and exhibit good film-forming properties and adhesive properties.

[0042] Details of LLDPE, polyolefin, vinyl compound, and unsaturated carboxylic acid in binder resin and heat-sealable resin are given below.

[0043] (LLDPE) LLDPE is a copolymer of repeating units of ethylene and some amount of alpha-olefin. In detail, C4-LLDPE is a linear low-density polyethylene made from a copolymer of ethylene and 1-butene as an α-olefin, C6-LLDPE is a linear low-density polyethylene made from a copolymer of ethylene and 1-hexene and / or 4-methyl-1-pentene, and C8-LLDPE is a linear low-density polyethylene made from a copolymer of ethylene and 1-octene. Each of these molecular structures has an ethylene-derived LLDPE main chain with side chains of 4, 6, and 8 carbon atoms derived from 1-butene, 1-hexene and / or 4-methyl-1-pentene, and 1-octene, respectively. Common polyethylene has a density of 0.90 g / cm 3 There are also those with a lower limit of 0.96 g / cm 3 Although JIS K6899-1:2000 defines the density of LLDPE as 0.910 to 0.925, in the present invention, densities outside this range are also treated as LLDPE.

[0044] (Polyolefin) In the present invention, polyolefin refers to a resin whose main chain is composed of repeating units derived from one or more types of monomers. Examples of the polyethylene include polyethylene, polypropylene, methylpentene polymer, cyclic polyolefin resin, etc. Examples of the polyethylene include low-density polyethylene (LDPE), medium-density polyethylene (MDPE), high-density polyethylene (MDPE), linear low-density polyethylene (LLDPE), metallocene polyethylene, etc. These may be used alone or in combination of two or more.

[0045] (vinyl compounds) The vinyl compound is a compound having a vinyl group, and specific examples thereof include vinyl acetate, vinyl alcohol, etc., and various (meth)acrylic compounds include (meth)acrylic acid, (meth)acrylic acid esters, etc. These may be used alone or in combination of two or more.

[0046] (unsaturated carboxylic acid) The unsaturated carboxylic acid is a carboxylic acid having an unsaturated carbon-carbon bond, and specific examples thereof include maleic acid, fumaric acid, and anhydrides thereof. These may be used alone or in combination of two or more.

[0047] <Adhesive layer> In the present invention, it is also possible to provide adhesive layers between the layers constituting the laminate and between layers within each layer. Furthermore, before forming the adhesive layer, an anchor coat layer may be formed in advance on the surface of the layer to be adhered in order to improve adhesiveness.

[0048] The adhesive (adhesive composition) forming the adhesive layer may be a thermosetting type, an ultraviolet-curing type, an electron beam-curing type, or the like, and may be in any form such as an aqueous type, a solution type, an emulsion type, or a dispersion type. In addition, the adhesive may be in any form such as a film / sheet type, a powder type, or a solid type. Furthermore, the adhesive mechanism may be in any form such as a chemical reaction type, a solvent evaporation type, a thermal melting type, or a thermal pressure type. Examples of such adhesives include polyvinyl acetate adhesives such as polyvinyl acetate and vinyl acetate-ethylene copolymers, polyacrylic acid adhesives made from copolymers of polyacrylic acid and polystyrene, polyester, polyvinyl acetate, etc., cyanoacrylate adhesives, ethylene copolymer adhesives made from copolymers of ethylene and monomers such as vinyl acetate, ethyl acrylate, acrylic acid, and methacrylic acid, cellulose adhesives, polyurethane adhesives, polyester adhesives, polyamide adhesives, polyimide adhesives, polyolefin adhesives, amino resin adhesives made from urea resin or melamine resin, phenolic resin adhesives, epoxy adhesives, reactive (meth)acrylic adhesives, elastomer adhesives made from chloroprene rubber, nitrile rubber, styrene-butadiene rubber, etc., silicone adhesives, and inorganic adhesives made from alkali metal silicates, low-melting point glass, etc.

[0049] In one embodiment of the present invention, the adhesive layer may be a layer made of any of an adhesive for EC (extrusion coating), an adhesive for dry lamination, an adhesive for non-solvent lamination, and the like. When an EC adhesive is used, there are no particular limitations, but for example, the adhesive is first heated and melted, expanded and stretched in the required width direction using a T-die or the like, and extruded in a curtain shape, allowed to flow down onto the layer to be adhered, and then sandwiched between a rubber roll and a cooled metal roll, thereby simultaneously forming an adhesive layer and adhering and laminating to the layer to be adhered.

[0050] In another embodiment, the adhesive layer may be formed by sand lamination. In this case, any resin that can be applied by heating and melting in an extruder can be used for the adhesive layer. Specifically, the resins listed above as thermoplastic resins having heat sealability can be preferably used.

[0051] When using a dry laminating adhesive, the adhesive dispersed or dissolved in a solvent is applied to one film and dried, and then the other film is placed on top of it and laminated.Then, the adhesive is cured by aging at 30 to 120°C for several hours to several days, thereby adhering and laminating the films.

[0052] When using a non-solvent laminating adhesive, the adhesive itself is applied to the layer to be adhered without being dispersed or dissolved in a solvent, and then dried. The film that will form the other layer is then laminated on top of the adhesive, and the adhesive is then cured and laminated by aging at 30 to 120°C for several hours to several days.

[0053] The adhesive for dry lamination or the adhesive for non-solvent lamination can be used by coating, for example, by roll coating, gravure roll coating, kiss coating, etc., and the coating amount is 0.1 to 10 g / m 2 By setting the coating amount within the above range, good adhesion can be obtained.

[0054] (Anchor coat layer) The anchor coat layer can be formed from any anchor coat agent. Examples of anchor coating agents that can be used include organic titanium-based, isocyanate (urethane-based), polyethyleneimine-based, acid-modified polyethylene-based, polybutadiene-based, polyacrylic-based, polyester-based, epoxy-based, polyvinyl acetate-based, cellulose-based, and other anchor coating agents.

[0055] [Method for producing an absorbent film for vehicle interiors] For example, an example of the production of an adsorbent film for vehicle interiors having a layer structure of heat seal layer / odor adsorption layer / heat seal layer will be described. The production method shown below is an example and does not limit the present invention. As long as the layers are laminated in this order, the order in which the layers are formed and laminated may be arbitrary. First, a heat-sealable resin and a resin composition for an odor-adsorbing layer are laminated by inflation film formation to obtain an odor-adsorbing sealant film having a layer structure of heat-sealing layer / odor-adsorbing layer / heat-sealing layer.

[0056] The lamination of each layer described above can be carried out by any lamination method used in the production of ordinary packaging materials, such as wet lamination, dry lamination, solventless dry lamination, extrusion lamination, T-die coextrusion molding, coextrusion lamination, inflation molding, or the like. Next, the odor-absorbing sealant film obtained above is placed in a roll stretching machine at 50 to 100°C and stretched longitudinally 2 to 4 times in the film-forming direction, to obtain a uniaxially stretched absorbent film for vehicle interiors. The biaxial stretching treatment can be carried out, for example, by longitudinally stretching the film 2 to 4 times using a roll stretching machine at 50 to 100° C., then further transversely stretching it 3 to 5 times using a tenter stretching machine in an atmosphere of 90 to 150° C., and subsequently heat-treating it using the same tenter in an atmosphere of 100 to 240° C. The stretching treatment may be simultaneous biaxial stretching or sequential biaxial stretching. Next, an aging treatment may be carried out as necessary. In this manner, an absorbent film can be prepared for vehicle interiors.

[0057] The adsorbent film for vehicle interior use obtained above can also be subjected to secondary processing in order to impart surface functions such as chemical functions, electrical functions, magnetic functions, mechanical functions, friction / wear / lubrication functions, optical functions, thermal functions, and biocompatibility. Examples of secondary processing include embossing, painting, adhesive, printing, metallizing (plating, etc.), machining, and surface treatment (antistatic treatment, corona discharge treatment, plasma treatment, photochromic treatment, physical vapor deposition, chemical vapor deposition, coating, etc.).

[0058] <<Vehicle interior materials>> Vehicle interior materials prepared using the adsorbent film of the present invention for vehicle interiors include wall materials, floor materials, and ceiling materials that form the passenger space, and covers for components installed in the passenger space. [Example]

[0059] Details of the raw materials used in the examples are as follows.

[0060] [Thermoplastic resin] Heat-sealable resin 1: Ultzex ​​1520L, manufactured by Prime Polymer Co., Ltd. C6-LLDPE, density 0.916 g / cm 3 , MFR2.3g / 10min. Heat-sealable resin 2: Ube Maruzen Polyethylene Co., Ltd., Yumerit 720FT, C4-LLDPE, density 0.918 g / cm 3 , MFR4g / 10min. Heat-sealable resin 3: Ube Maruzen Polyethylene Co., Ltd., Yumerit 125NF, HAO-LLDPE (copolymerized LLDPE with higher alpha olefins of 6 or more carbon atoms, such as C6 and C8, as comonomers), density 0.924 g / cm 3 , MFR2.2g / 10min.

[0061] [Odor absorbent] Hydrophobic zeolite 1: Silton MT400, a hydrophobic zeolite manufactured by Mizusawa Industrial Chemicals, Ltd. SiO2 / Al2O3 molar ratio = 400 / 1, average particle size = 5 to 7 μm. Hydrophobic zeolite 2: Silton MT-8000, a hydrophobic zeolite manufactured by Mizusawa Industrial Chemicals, Ltd. SiO2 / Al2O3 molar ratio = 8000 / 1, average particle size = 0.8 μm. General-purpose zeolite 1: Mizusawa Sieves 5AP, a zeolite manufactured by Mizusawa Industrial Chemicals, Inc. SiO2 / Al2O3 molar ratio = 2 / 1, average particle size 5 μm. Amino group-supported inorganic porous material 1: Kesmon NS-241 manufactured by Toagosei Co., Ltd. Average particle size: 3.5 μm. Amino group-supported silica dioxide. · Hydroxyl group-supporting inorganic porous material 1: Kesmon NS-80E, manufactured by Toagosei Co., Ltd. Average particle size 2μm. Metal salt-supported inorganic porous material: Dashlight CZU, manufactured by Sinanen Zeomic Co., Ltd. CuO, ZnO-supported zeolite, average particle size = 3 to 5 μm.

[0062] [Masterbatch preparation] The masterbatch used in the odor adsorption layer was prepared as follows. (Preparation of Masterbatch 1) Heat-sealable resin 1 and hydrophobic zeolite 1 were melt-blended in the following ratio to obtain masterbatch 1 (MB1). Heat-sealable resin 1 70 parts by mass Hydrophobic zeolite 1 30 parts by mass

[0063] [Preparation of Masterbatches 2 to 6] According to the formulations in Table 1, melt blending was carried out in the same manner as for Masterbatch 1, to obtain Masterbatches 2 to 6 (MB2 to 6).

[0064] [Table 1]

[0065] [Preparation of Odor Adsorption Layer Resin Composition] By dry blending the raw materials according to the compositions shown in Tables 2 and 3, resin compositions 1 to 15 for the odor absorbing layer were obtained.

[0066] [Table 2]

[0067] [Table 3]

[0068] <Preparation and evaluation of absorbent films for vehicle interiors> [Example 1] The odor absorbing layer resin composition 1 and heat sealable resin 1 obtained above were laminated by inflation film formation at 160°C to obtain the following three-layered absorbent film 1 for vehicle interior use. Layer structure of film 1: thermoplastic resin layer 1 / odor absorbing layer / thermoplastic resin layer 2=heat sealable resin 1 (10 μm) / odor absorbing layer resin composition 1 (30 μm) / heat sealable resin 1 (10 μm).

[0069] [Examples 2 to 9, 13 to 15] Using the raw materials of each example shown in Tables 4 to 6, the same procedure as in Example 1 was carried out to obtain an adsorbent film for vehicle interior use, which was then similarly evaluated.

[0070] [Examples 10 to 14, Comparative Examples 1 to 3] Using the raw materials of each example shown in Tables 5 and 6, an absorbent film for vehicle interior use was obtained in the same manner as in Example 1, except that thermoplastic resin layer 1 and / or thermoplastic resin layer 2 were not provided, according to the layer structure of the film shown in Tables 5 and 6, and was evaluated in the same manner.

[0071] [Table 4]

[0072] [Table 5]

[0073] [Table 6]

[0074] <Summary of results> All of the odor-adsorbent films for vehicle interiors according to the present invention exhibited a good balance of film-forming properties, stretchability, water vapor permeability, odor adsorption effect, and odor diffusion suppression effect. Comparative Example 1, which contained general-purpose zeolite instead of hydrophobic zeolite, showed poor odor adsorption performance. The laminates of Comparative Examples 2 and 3, which did not have an odor adsorption layer, showed poor results in terms of odor adsorption effect and odor sensory evaluation. Furthermore, the laminate of Comparative Example 3, in which the concentration of the odor adsorbent was too high, showed results that were inferior in film-forming properties, heat-sealing properties, and stretchability.

[0075] <Evaluation method> [Film forming property] The appearance of the absorbent film for vehicle interior use was observed and evaluated sensorily according to the following criteria: ○: Adsorbent film for vehicle interiors can be produced without wrinkles or bumps. ×: When used for vehicle interiors, the adsorbent film had many wrinkles and bumps, making film formation difficult.

[0076] [Odor component concentration] An adsorbent film (20 cm x 20 cm) for vehicle interior use was placed in a gas sampling bag (GL Sciences Inc., SMART BAG PA AKK-10, pouch area A4 size), and the gas sampling bag was filled with 1000 ml of test odor gas (acetaldehyde: 100 ppm, diacetyl: 400 ppm, hydrogen sulfide: 25 ppm, acetic acid: 30 ppm, concentrated ammonia: 30 ppm) and sealed. After leaving the container at room temperature for 48 hours, the concentration of each gas component was measured using the following measuring device. Acetaldehyde concentration: Detector tube (Gastec Corporation, No. 92M) Diacetyl concentration: detector tube (Gastec Corporation, No. 92) Hydrogen sulfide concentration: Detector tube (Gastec Corporation, No. 4LK) Acetic acid concentration: detector tube (Gastec Corporation, No. 81) Ammonia concentration: detector tube (Gastec Corporation, No. 3L)

[0077] [Heat sealability] For vehicle interior use, the adsorbent film was cut into 10 cm x 10 cm pieces, and if there was a heat seal layer, the heat seal layers were overlapped facing each other. If there was no heat seal layer, the thermoplastic resin layers were overlapped facing each other, the thermoplastic resin layer and the odor adsorption layer, or the odor adsorption layers were overlapped facing each other in that order of priority. Using a heat seal tester (TP-701-A manufactured by Tester Sangyo Co., Ltd.), a 1 cm x 10 cm area was heat sealed under the following conditions, and a test piece for peel strength was prepared in which the edges were not heat sealed and were divided into two. This test piece was cut into a 15 mm wide strip, and each bifurcated end was attached to a tensile tester to measure the peel strength (N / 15 mm) under the conditions below, and the result was judged as pass / fail according to the pass / fail criteria below. Heat sealing conditions Temperature: 160℃ Pressure: 1kgf / cm 2 Time: 1 second Test conditions Test speed: 300 mm / min Load range: 50N Pass / fail criteria ○: 30N / 15mm or more, passed. ×: Less than 30N / 15mm, failed. [Explanation of symbols]

[0078] 1. Odor-absorbing films for vehicle interiors, odor-absorbing packaging materials 2. Odor absorption layer 3 Thermoplastic resin layer 10 Chemical adsorbent-supported inorganic porous material

Claims

1. An adsorbent film for vehicle interiors that adsorbs VOC component odors, cigarette odors, body odors, household odors, or pet odors, The adsorbent film for vehicle interiors has heat sealability, The adsorbent film for vehicle interiors does not contain an aliphatic polyamine compound, an aromatic polyamine compound, or a hydrazide compound, The adsorbent film for vehicle interiors has at least an odor adsorption layer, the odor absorbing layer contains a binder resin and an odor absorbing agent; the binder resin is a heat-sealable resin, The odor adsorbent contains a hydrophobic zeolite, or contains a hydrophobic zeolite and a metal-supported inorganic porous material, SiO of the hydrophobic zeolite 2 / Al 2 O 3 The molar ratio is 400 / 1 to 10000 / 1; The absorbent film for vehicle interiors.

2. 2. The adsorbent film for vehicle interiors according to claim 1, wherein the odor adsorbent further comprises an inorganic porous material carrying an amino group-containing compound and / or an inorganic porous material carrying a hydroxyl group.

3. The binder resin has a density of 0.90 g / cm 3 Above, 0.94g / cm 3 3. The adsorbent film for vehicle interiors according to claim 1, wherein the film is one or more selected from the group consisting of C4-LLDPE, C6-LLDPE, and C8-LLDPE.

4. 4. The adsorbent film for vehicle interiors according to claim 1, wherein the odor adsorbent is used as a masterbatch that is melt-kneaded in advance with a thermoplastic resin capable of forming an odor adsorption layer as the binder resin in a mass ratio of odor adsorbent / thermoplastic resin of 0.5 / 99.5 to 40 / 60.

5. The layer structure of the adsorbent film for vehicle interiors is: a layer structure consisting of only the odor adsorption layer; a layer structure having the odor adsorption layer and a thermoplastic resin layer on one surface thereof; a layer structure having the odor adsorption layer and thermoplastic resin layers on both surfaces thereof; Any layer structure selected from the group consisting of:

5. The adsorbent film for vehicle interiors according to claim 1, wherein the thermoplastic resin layer contains a thermoplastic resin but does not contain the odor adsorbent.

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