JP5501868B2 - Matte film, interior material using the same, and method for producing matte film - Google Patents

Description

  The present invention relates to a matte film containing an ethylene-vinyl alcohol copolymer, an interior material using the same, and a method for producing the matte film.

  Utilizing the fact that ethylene-vinyl alcohol copolymer (hereinafter also referred to as “EVOH”) is excellent in chemical resistance, stain resistance, anti-bleeding property of plasticizer, etc., the surface of vinyl chloride wallpaper, etc. An EVOH film is attached to the plate. Thus, when using an EVOH film on the surface of a wallpaper, since the glossiness of an EVOH film is high, the matte (lower glossiness) of the EVOH film surface is requested | required. As a method for matting the EVOH film surface, a sandblasting method, a surface treatment method using chemicals, a method of blending powdered inorganic substances, and the like are known. However, these methods are costly or have poor film-forming properties. Has inconvenience. In addition, since EVOH itself is not very flexible, wallpaper using this EVOH film on its surface is not particularly workable in low-temperature environments such as in winter. For example, when the surface folds when folded In addition, there is a risk of causing a case where a floating portion is generated without being in close contact with the wall in pasting to the corner of the wall.

  Therefore, as a matte film with reduced gloss, a film containing a carboxylic acid-modified polyethylene resin in EVOH has been developed (see, for example, JP-A Nos. 64-74252 and 1-166951). . In the EVOH film containing the carboxylic acid-modified polyethylene resin, since the carboxylic acid-modified polyethylene resin is dispersed and present in the EVOH matrix, unevenness is formed on the surface and the gloss is suppressed.

  However, although the wallpaper using the EVOH film containing the carboxylic acid-modified polyethylene resin on the surface has realized low glossiness, it has not led to the improvement of the above inconvenience of workability. Therefore, in order to improve this low workability, it is conceivable to increase the content of the carboxylic acid-modified polyethylene resin with respect to EVOH in order to reduce the content of EVOH with low flexibility. However, when the content of the carboxylic acid-modified polyethylene resin is increased, the film formability of the film is significantly lowered. In other words, according to the EVOH resin composition having a high content of the carboxylic acid-modified polyethylene resin, when the film is formed at a high take-off speed so as to obtain a film having the required thinness, the film often has holes, and the resin The film forming property of the composition is lowered, and the productivity of the film is lowered.

  On the other hand, in order to improve the flexibility of a molded article containing EVOH, a composite resin in which a thermoplastic elastomer is contained in EVOH as a flexible resin has been developed (see Japanese Patent Application Laid-Open No. 2007-9171). However, when a film is formed from this thermoplastic elastomer-containing EVOH resin, the surface unevenness is not sufficiently formed. Further, when the film is heat laminated on the substrate surface when producing wallpaper, the film surface unevenness is further increased. There is a disadvantage that the wallpaper is smoothed and the glossiness of the resulting wallpaper is increased.

  Further, when a film is formed from a thermoplastic elastomer-containing EVOH resin, a residue of the resin composition (hereinafter referred to as “Meani”) tends to adhere to a tip portion such as a die lip portion of an extruder over time. Become. The occurrence of this may reduce the formability of the film and may reduce the productivity due to the removal operation of this mean.

JP-A 64-74252 JP-A-1-166951 JP 2007-9171 A

  The present invention has been made in view of these circumstances, and maintains the film-formability of the resin composition and the low glossiness of the obtained film, and is applied to interior materials such as wallpaper using this film. It is intended to provide a matte film that can improve the properties of the matte, and in addition, a matte film in which the occurrence of a scum is suppressed during melt molding, an interior material using the matte film, and a method for producing such a matte film .

The invention made to solve the above problems is
Molded from a resin composition containing an ethylene-vinyl alcohol copolymer (A), an acid-modified polyolefin (B) and a thermoplastic elastomer (C);
The total content of the acid-modified polyolefin (B) and the thermoplastic elastomer (C) with respect to 100 parts by mass of the ethylene-vinyl alcohol copolymer (A) is 5 parts by mass or more and 100 parts by mass or less.
A matte film in which the thermoplastic elastomer (C) has a melt index of 2 g / 10 min to 18 g / 10 min and the thermoplastic elastomer (C) has a mass average acid value of 2.5 mgKOH / g to 20 mgKOH / g It is.

  In the matte film, the resin composition, which is a molding material, is a thermoplastic elastomer having a specific fluidity and acid value in addition to the acid-modified polyolefin (B) with respect to the ethylene-vinyl alcohol copolymer (A). Even if the content of the resin other than the ethylene-vinyl alcohol copolymer (A) is increased by containing the above-mentioned amount of C), the film-forming property of the resin composition on the film and thus the productivity is maintained. Can do. In addition, the matte film can improve flexibility by containing the thermoplastic elastomer (C) as described above, and as a result, improve the workability when the film is used for wallpaper or the like. be able to. Further, the matte film contains an acid-modified polyolefin (B) and a thermoplastic elastomer (C), and these two types of resins are dispersed in the ethylene-vinyl alcohol copolymer (A) and exist in an island shape. Therefore, the two types of resin present in the island shape facilitate the formation of surface irregularities, and can further suppress the smoothing of the irregularities during the heat laminating process.

  Further, the matte film has a predetermined range of acid value and contains a thermoplastic elastomer having a moderate compatibility with the ethylene-vinyl alcohol copolymer (A) as the component (C). Therefore, the matte film suppresses the occurrence of scumming that occurs when the component (C) dispersed in the form of particles separates from the component (A) during melt molding and adheres to the die slip portion. can do. Therefore, according to the matte film, it is possible to reduce the removal work of the spears generated in the die lip portion or the like and improve the productivity.

  That is, according to the matte film, the film-forming property of the resin composition and the low gloss of the film can be maintained, and in addition, the occurrence of scumming during melt molding can be suppressed. Workability such as wallpaper can be improved.

  The mass ratio [(C) / (B)] of the thermoplastic elastomer (C) to the acid-modified polyolefin (B) is preferably 1.5 or more and 10 or less. The matte film can improve both flexibility and concavo-convex formability by adjusting the mass ratio of the acid-modified polyolefin (B) and the thermoplastic elastomer (C) within the above range. It is possible to further improve the film forming property, the workability of wallpaper using the film, and the low glossiness of the film.

  The thermoplastic elastomer (C) is preferably an acid-modified ethylene-α-olefin copolymer. According to the matte film, since the thermoplastic elastomer (C) is an acid-modified ethylene-α-olefin copolymer, the uniform dispersibility of the thermoplastic elastomer (C) can be easily and effectively increased. As a result, the film-forming property and the unevenness-forming property of the resin composition can be further enhanced, and the ability to suppress the occurrence of scum can be further enhanced.

  The acid-modified ethylene-α-olefin copolymer is preferably a carboxylic acid-modified ethylene-butene copolymer. According to the matte film, the thermoplastic elastomer (C) is a carboxylic acid-modified ethylene-butene copolymer, thereby further improving the uniform dispersibility of the thermoplastic elastomer (C) in the resin composition. As a result, the film-forming property and the unevenness-forming property of the resin composition can be further enhanced, and the ability to suppress the occurrence of scum can be further enhanced.

  The acid-modified polyolefin (B) preferably has a melt index of 0.01 g / 10 min to 10 g / 10 min. According to the matte film, the acid-modified polyolefin (B) dispersed in the resin composition at the time of film formation by setting the melt index of the acid-modified polyolefin (B) to a relatively small value within the above range. As a result, unevenness can be effectively formed on the surface, and smoothing of the unevenness during the heat laminating process can be further suppressed.

  The acid-modified polyolefin (B) is preferably acid-modified polyethylene. According to the matte film, the dispersibility of the acid-modified polyolefin in the resin composition can be increased by using the acid-modified polyolefin as the acid-modified polyethylene. The sex can be further enhanced.

  The acid-modified polyethylene may be a carboxylic acid-modified high density polyethylene. According to the matte film, when the acid-modified polyolefin (B) is a carboxylic acid-modified high-density polyethylene, the film-forming property and the unevenness-forming property of the resin composition can be further maintained or improved.

  The ethylene-vinyl alcohol copolymer (A) preferably has a melt index of 0.1 g / 10 min to 30 g / 10 min. According to the matte film, in addition to being able to maintain the film-forming property of the resin composition by setting the melt index of the ethylene-vinyl alcohol copolymer (A) to a relatively large value in the above range, During film formation, the surface can be more effectively formed with unevenness by the acid-modified polyethylene (B) and the thermoplastic elastomer (C) dispersed in the resin composition.

  The value obtained by subtracting the melt index of the thermoplastic elastomer (C) from the melt index of the ethylene-vinyl alcohol copolymer (A) is preferably 5 g / 10 min or more. According to the matte film, the melt index difference between the thermoplastic elastomer (C) and the ethylene-vinyl alcohol copolymer (A) is increased as described above, so that the matte film is dispersed during film formation. With the thermoplastic elastomer (C), irregularities large enough to reduce gloss can be easily formed on the surface.

  The ethylene unit content of the ethylene-vinyl alcohol copolymer (A) is preferably 35 mol% or more and 60 mol% or less. According to the matte film, by increasing the ethylene unit content of the ethylene-vinyl alcohol copolymer (A) as described above, the flexibility is enhanced, and the workability when this film is used for wallpaper or the like. Can be further increased.

  The saponification degree of the ethylene-vinyl alcohol copolymer (A) is preferably 90 mol% or more. According to the matte film, by making the saponification degree of the ethylene-vinyl alcohol copolymer (A) 90 mol% or more, the film forming property of the resin composition and the film were used on the surface of wallpaper or the like. The workability at the time can be further enhanced.

  The mass average acid value of the entire resin composition is preferably from 0.1 mgKOH / g to 5.0 mgKOH / g. According to the matte film, by making the average acid value of the resin composition in the above range, the film-forming property of the resin composition can be further improved and the uniform dispersibility of each component can be improved. The unevenness forming property can be further improved, and as a result, the glossiness of the matte film can be further reduced. In addition, according to the matte film, by setting the average acid value of the resin composition in the above range, the components (A) to (C) are in an intermediate state between a dispersed state and a compatible state, It is possible to simultaneously achieve formation and suppression of occurrence of scum.

  The storage elastic modulus at 5 ° C. of the matte film is preferably 1.6 GPa or less. According to the matte film, it is possible to suppress a decrease in flexibility particularly in a low-temperature environment such as winter, and the workability when used for wallpaper or the like can be further enhanced.

  The unevenness degree of the matte film is preferably 8 μm or more. According to the matte film, the glossiness can be effectively suppressed by providing the degree of unevenness.

  Another invention made in order to solve the above-mentioned subject is an interior material provided with a substrate and the above-mentioned matte film laminated on the surface of this substrate by heat lamination. According to the interior material, glossiness can be suppressed and the workability can be improved because the flexibility of the film is high.

  The glossiness of the surface of the interior material is preferably 20% or less. Thus, since the said interior material is provided with the matte film on the surface, it can use suitably as interior material with low surface glossiness by suppressing the glossiness of a surface to 20% or less.

  The method for producing a matte film of the present invention comprises the steps of obtaining a resin composition by mixing an ethylene-vinyl alcohol copolymer (A), an acid-modified polyolefin (B) and a thermoplastic elastomer (C), and the resin composition A total content of the acid-modified polyolefin (B) and the thermoplastic elastomer (C) with respect to 100 parts by mass of the ethylene-vinyl alcohol copolymer (A) of the resin composition is 5 parts by mass. The thermoplastic elastomer (C) has a melt index of 2 g / 10 min or more and 18 g / 10 min or less, and the thermoplastic elastomer (C) has a mass average acid value of 2.5 mgKOH / g. It is the manufacturing method of the matte film which is 20 mgKOH / g or less above. The production method can provide a matte film having excellent film-forming properties such as suppression of the occurrence of cracks during melt molding, and having low gloss and excellent workability.

  Here, the “melt index” is a value measured at a temperature of 210 ° C. and a load of 2160 g in accordance with JIS-K7210. “Roughness” is the difference between the maximum thickness measured and the theoretical thickness calculated from the mass and density. “Storage modulus” is a value measured according to JIS-K7244-4. “Glossiness” is a value measured at an angle of 60 degrees in accordance with JIS-Z8741. The “acid value” is a value measured by the method described in Examples described later.

  As described above, according to the matte film, the resin composition, which is a film-forming material, has high film-formability, and is excellent in productivity because the occurrence of scouring during melt molding is also suppressed. Moreover, low glossiness can be exhibited by having moderate unevenness on the surface. Furthermore, since the matte film is highly flexible even in a low temperature environment, it is possible to improve the workability of wallpaper and the like using this film. According to the interior material, the gloss of the surface can be suppressed, and the workability can be improved. Moreover, according to the manufacturing method of the said matte film, the matte film which has the above-mentioned performance can be obtained.

  Hereinafter, embodiments of the present invention will be described in detail in the order of a matte film, a method for producing the matte film, and an interior material.

  The matte film of the present invention is molded from a resin composition containing an ethylene-vinyl alcohol copolymer (A), an acid-modified polyolefin (B), and a thermoplastic elastomer (C).

  The matte film is molded from a resin composition containing a thermoplastic elastomer (C) in addition to the acid-modified polyolefin (B) with respect to EVOH (A), thereby containing a resin other than EVOH (A). Even if the rate is increased, the film-forming property of the resin composition on the film can be maintained, and as a result, productivity can be maintained. Moreover, since the said matte film can improve a softness | flexibility by containing a thermoplastic elastomer (C) in this way, it can improve the workability at the time of using this film for wallpaper etc. it can. Furthermore, the matte film contains an acid-modified polyolefin (B) and a thermoplastic elastomer (C), so that these two types of resins are dispersed in islands in EVOH (A) and exist as sea-island structures. Therefore, the surface unevenness can be easily formed by these two kinds of resins, and further, the smoothing of the unevenness can be suppressed during the heat laminating process. Therefore, according to the matte film, the film-forming property of the resin composition and the low glossiness of the film can be maintained, and the workability of wallpaper and the like using this film can be improved.

  In the resin composition, the lower limit of the total content of the acid-modified polyolefin (B) and the thermoplastic elastomer (C) with respect to 100 parts by mass of the ethylene-vinyl alcohol copolymer (A) is 5 parts by mass. Mass parts are preferred, 30 parts by mass are more preferred, 40 parts by mass are particularly preferred, and 45 parts by mass are even more preferred. On the other hand, the upper limit of the total content of the acid-modified polyolefin (B) and the thermoplastic elastomer (C) with respect to 100 parts by mass of the ethylene-vinyl alcohol copolymer (A) is 100 parts by mass, and 80 parts by mass. Is preferable, 60 parts by mass is more preferable, and 55 parts by mass is particularly preferable. According to the resin composition, by including the acid-modified polyolefin (B) other than EVOH (A) and the thermoplastic elastomer (C) in the above range, the low flexibility of EVOH can be improved. it can. That is, according to the matte film formed from the resin composition, the flexibility is improved, and the workability of a wallpaper or the like using the matte film can be improved. When the total content of the components (B) and (C) is smaller than the lower limit, this flexibility is not sufficiently improved. Conversely, if the total content of the components (B) and (C) exceeds the above upper limit, the components (B) and (C) may be uniformly dispersed in the EVOH of the component (A) and exist in an island shape. It becomes difficult and it becomes difficult to form uniform unevenness on the surface, or the film forming property is lowered.

<Ethylene-vinyl alcohol copolymer (A)>
The ethylene-vinyl alcohol copolymer (A) has an ethylene unit and a vinyl alcohol unit 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 preferably 35 mol%, more preferably 40 mol%. 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%. If 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 matte film may be lowered, and the workability when used for wallpaper or the like may be lowered. In addition, the performance of the film such as water resistance and hot water resistance may be deteriorated. Conversely, if the ethylene unit content of EVOH exceeds the above upper limit, the strength of the matte film may be reduced, or the plasticizer is prevented from bleeding when it is laminated on a resin containing a plasticizer and used for wallpaper. Performance may be reduced.

  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%. 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, unevenness forming property, flexibility and the like cannot be expected so much.

  The lower limit of the EVOH melt index is preferably 0.1 g / 10 min, more preferably 0.5 g / 10 min, particularly preferably 1 g / 10 min, further particularly preferably 5 g / 10 min, and 6 g / 10 min. More preferably, 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 the matte film, by setting the EVOH melt index to a relatively large value within the above range, the film-forming property of the resin composition can be maintained, and during the film formation, Unevenness can be formed on the surface more effectively by the acid-modified polyethylene (B) and the thermoplastic elastomer (C) dispersed in. If the EVOH melt index is smaller than the above lower limit, it becomes difficult to form a thin film, the film-forming property of the resin composition is lowered, and it is difficult to make a difference in melt viscosity from the components (B) and (C). , The formation of irregularities on the surface is reduced. On the other hand, if the EVOH melt index exceeds the above upper limit, the chemical resistance of the film, the bleed prevention of the plasticizer when used as wallpaper, etc. may be reduced.

  Next, a method for producing EVOH will be specifically described. 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, a monomer that can be copolymerized in addition to the above components, for example, alkenes other than those described above; unsaturated acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, or anhydrides thereof Products, 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; Vinyl ethers, vinyl ketone, N-vinyl pyrrolidone, vinyl chloride, vinylidene chloride and the like can be copolymerized in a small amount. 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, diisopropylperoxycarbonate, di-n- Organic peroxide initiators such as propyl peroxydicarbonate, t-butyl peroxyneodecanoate, lauroyl peroxide, benzoyl peroxide, t-butyl hydroperoxide, and the like 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.

<Acid-modified polyolefin (B)>
The acid-modified polyolefin (B) refers to a polyolefin having an acidic group such as a carboxyl group or its anhydride group or sulfonic acid group. The acid-modified polyolefin (B) is a carboxylic acid-modified polyolefin obtained by graft polymerization or addition of an α, β-unsaturated carboxylic acid such as (anhydrous) itaconic acid or (anhydrous) maleic acid and / or an anhydride thereof to the polyolefin. Examples thereof include polyolefins. 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 amount component, unless the objective and effect of this invention are prevented.

  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 as the component (B), it becomes easy to take a sea-island structure in the resin composition, and in addition, it becomes easy to adjust to a desired melt index described below. Therefore, according to the matte film containing carboxylic acid-modified high-density polyethylene as the component (B), the film forming property of the resin composition can be improved, and the unevenness forming property can be improved. Furthermore, the matte film can improve chemical resistance and plasticizer bleed prevention.

  The acid-modified polyolefin (B) is preferably a plastomer that does not have elastic properties, that is, does not have rubbery elasticity at room temperature. Thus, by using an acid-modified polyolefin having no elastic property as the component (B), it is possible to efficiently form a sufficiently large unevenness on the surface during film formation, The smoothing of the unevenness can be further suppressed during the heat laminating process.

  The lower limit of the acid value of the acid-modified polyolefin is preferably 0.5 mgKOH / g, more preferably 1 mgKOH / g, and particularly preferably 1.5 mgKOH / g. On the other hand, the upper limit of the acid value is preferably 5 mgKOH / g, more preferably 4 mgKOH / g, and particularly preferably 3 mgKOH / g. If the acid value of the acid-modified polyolefin is smaller than the above lower limit, the dispersibility deteriorates upon mixing with EVOH, and the matte function of the film is not sufficiently exhibited. On the other hand, when the acid value exceeds the above upper limit, the melt viscosity of the resin composition increases, and the film forming property may be deteriorated.

  The lower limit of the melt index of the acid-modified polyolefin (B) is preferably 0.01 g / 10 minutes, more preferably 0.1 g / 10 minutes, and particularly preferably 0.3 g / 10 minutes. On the other hand, the upper limit of the melt index of the acid-modified polyolefin (B) is preferably 10 g / 10 minutes, more preferably 5 g / 10 minutes, and particularly preferably 2 g / 10 minutes. By setting the melt index of the acid-modified polyolefin (B) to a relatively small value within the above range, the surface is effectively made uneven by the acid-modified polystyrene (B) dispersed in the resin composition during film formation. It can form, and the smoothing of the unevenness | corrugation in the case of a heat laminating process can further be suppressed. If the melt index of the acid-modified polyolefin (B) is smaller than the above lower limit, the acid-modified polyolefin (B) is difficult to be uniformly dispersed in the resin composition, and the film forming property may be deteriorated. Conversely, if the melt index exceeds the above upper limit, the film surface unevenness forming property is lowered, and the effect of suppressing unevenness flattening during the heat laminating process is lowered, and as a result, the glossiness is not reduced. There is a fear.

  It does not specifically limit as a manufacturing method of the said acid-modified polyolefin (B), A well-known method can be used. For example, an acid-modified polyolefin (B) can be obtained by copolymerizing an olefin and an unsaturated carboxylic acid as a monomer by a known method, or introducing an α, β-unsaturated carboxylic acid into a side chain by a known method. Can be obtained.

<Thermoplastic elastomer (C)>
The thermoplastic elastomer is a resin that has fluidity when heated and has rubber-like elasticity at room temperature. In the present invention, the acid-modified polyolefin (B) is not included in the thermoplastic elastomer even when the above conditions are satisfied.

  The mass average acid value of the thermoplastic elastomer (C) is 2.5 mgKOH / g or more and 20 mgKOH / g or less. According to the matte film of the present invention, by setting the acid value of the thermoplastic elastomer (C) in such a range, EVOH (A) and the thermoplastic elastomer (C) have appropriate dispersibility and compatibility. Can be kept in good balance. Therefore, according to the matte film, the component (C) dispersed and present in the particle form is in a state compatible with EVOH to some extent. Therefore, the component (C) is separated from EVOH (A) during melt molding. As a result, it is possible to suppress the occurrence of a sag generated by adhering to a die slip portion or the like. Therefore, according to the matte film, it is possible to reduce the removal work of the spears generated in the die slip portion or the like and improve the productivity.

  The lower limit of the acid value of this thermoplastic elastomer is 2.5 mgKOH / g, preferably 3 mgKOH / g, particularly preferably 4 mgKOH / g. On the other hand, the upper limit of the acid value is 20 mgKOH / g, preferably 15 mgKOH / g, more preferably 10 mgKOH / g, and particularly preferably 8 mgKOH / g.

  When the acid value of the thermoplastic elastomer (C) is smaller than the lower limit, the dispersibility is deteriorated upon mixing with EVOH, and the matte function of the film is not sufficiently exhibited. Further, when the acid value of the thermoplastic elastomer (C) is smaller than the lower limit, the compatibility with EVOH is reduced, and the thermoplastic elastomer (C) is separated during melt molding and easily adheres to the die lip part or the like. As a result, it becomes easy to generate sag. On the other hand, when the acid value exceeds the above upper limit, the melt viscosity of the resin composition becomes high and the film-forming property is lowered, or the compatibility with EVOH is too high, so that the irregularity forming ability is lowered.

  The lower limit of the melt index of the thermoplastic elastomer (C) is 2 g / 10 minutes, preferably 2.3 g / 10 minutes, and more preferably 2.5 g / 10 minutes. On the other hand, the upper limit of the melt index of the thermoplastic elastomer (C) is 18 g / 10 min, preferably 10 g / 10 min, more preferably 6 g / 10 min, particularly preferably 5 g / 10 min. 10 minutes is even more particularly preferred. The matte film contains the thermoplastic elastomer (C) having a melt index in the above range, so that the flexibility is improved, and as a result, the workability when this film is used for wallpaper or the like is improved. Can do. If the melt index of the thermoplastic elastomer (C) is smaller than the above lower limit, the film forming property of the resin composition becomes insufficient, and it becomes difficult to form a thin film. On the other hand, when the melt index exceeds the above upper limit, the unevenness-forming property is lowered and low glossiness may not be achieved.

  The value obtained by subtracting the melt index of the thermoplastic elastomer (C) from the melt index of the ethylene-vinyl alcohol copolymer (A) is preferably 5 g / 10 min or more, more preferably 7 g / 10 min or more, 7.5 g / 10 minutes or more is particularly preferable. In addition, the melt index of the ethylene-vinyl alcohol copolymer (A) at this time is 5 g / 10 minutes or more. As described above, in the resin composition, the thermoplastic elastomer (C) having a melt index value lower than a certain value with respect to the melt index of EVOH (A) is contained, so that the heat can be increased during film formation. By the plastic elastomer (C), it is possible to easily form unevenness of a sufficiently large size, and to further reduce the glossiness of the matte film obtained. On the other hand, the upper limit of the value obtained by subtracting the melt index of the thermoplastic elastomer (C) from the melt index of the ethylene-vinyl alcohol copolymer (A) is not particularly limited, but productivity, availability of materials, etc. In consideration of the above, 20 g / 10 min is preferable. When the thermoplastic elastomer (C) is a mixture of a plurality of thermoplastic elastomers, the melt index of the thermoplastic elastomer (C) is the mass average of the melt indexes of the respective thermoplastic elastomers.

  As the thermoplastic elastomer (C), an acid-modified thermoplastic elastomer is used at least partially in order to have an acid value in the above range. 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.

  The acid-modified thermoplastic elastomer is not particularly limited as long as it satisfies the definition of the above-mentioned acid-modified thermoplastic elastomer, and examples thereof include urethane-based, polyamide-based, polyester-based, and polyolefin-based acid-modified thermoplastic elastomers. Polyolefin acid-modified thermoplastic elastomers are preferred from the standpoints of film-forming properties and unevenness-forming properties.

  Examples of polyolefin acid-modified 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. Examples thereof include acid-modified products such as a copolymer of a monomer and a modified product of a copolymer of an olefin monomer and another monomer. 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 acid-modified thermoplastic elastomers can be used alone or in admixture of two or more.

  As this acid-modified thermoplastic elastomer, an acid-modified ethylene-α-olefin copolymer is preferable, and specifically, a carboxylic acid-modified ethylene-butene copolymer is preferable. As the carboxylic acid-modified ethylene-butene copolymer, a maleic anhydride-modified ethylene-butene copolymer is particularly preferable. By using such an acid-modified thermoplastic elastomer, the melt index of the acid-modified thermoplastic elastomer (C) and the average acid value of the entire resin composition can be easily and suitably adjusted. It is possible to improve the film-formability (meani suppression, etc.), the unevenness-forming property, and the workability when used as wallpaper. Here, the α-olefin refers to an α-olefin having 3 or more carbon atoms.

  It does not specifically limit as a manufacturing method of the said acid-modified thermoplastic elastomer, A well-known method can be used. For example, a carboxylic acid-modified ethylene-butene copolymer is copolymerized by a known method using ethylene, butene, and an unsaturated carboxylic acid as monomers, or an unsaturated carboxylic acid such as maleic anhydride is added to the ethylene-butene copolymer. It can be obtained by introducing it into the side chain by a known method.

  The thermoplastic elastomer (C) is composed only of an acid-modified thermoplastic elastomer that does not contain an acid-unmodified thermoplastic elastomer, even if it is a mixture of an acid-modified thermoplastic elastomer and an acid-unmodified thermoplastic elastomer. There may be. In order to enhance the ability to suppress the occurrence of cracks during melt molding, it is preferable that the thermoplastic elastomer (C) contains substantially no acid-unmodified thermoplastic elastomer. Examples of the acid-unmodified thermoplastic elastomer include urethane-based, polyamide-based, polyester-based, and polyolefin-based thermoplastic elastomers that are not acid-modified.

  The lower limit of the mass ratio [(C) / (B)] of the thermoplastic elastomer (C) to the acid-modified polyolefin (B) is preferably 1.5 and more preferably 2. On the other hand, the upper limit of the mass ratio [(C) / (B)] is preferably 10, more preferably 8, and particularly preferably 7. If this mass ratio [(C) / (B)] is smaller than the above lower limit, the improvement of the flexibility of the matte film is difficult to appear, and the workability of the wallpaper or the like using this film may not be improved. On the contrary, if this mass ratio [(C) / (B)] exceeds the above upper limit, the film surface is not sufficiently uneven, and the surface in the heat laminate when the wallpaper is produced using this film. As a result, the glossiness of the obtained wallpaper or the like may not be reduced.

<Other additives>
In addition to the above three components, the resin composition forming the matte film of the present invention may contain other additives as long as the object of the present invention is not impaired. Examples of such additives include a lubricant (D), an antibacterial agent, an antioxidant, and an ultraviolet absorber.

  By containing the lubricant (D) in the resin composition, friction in the extruder of the resin composition such as the acid-modified thermoplastic elastomer (C) during melt molding can be reduced. Therefore, according to the resin composition containing the lubricant, it is possible to further suppress the occurrence of scum (residue of the resin composition) in the die lip portion during molding, and the productivity can be increased.

  Although it does not specifically limit as content of a lubricant (D), 0.001 mass part or more with respect to 100 mass parts of total amounts of EVOH (A), acid-modified polyolefin (B), and acid-modified thermoplastic elastomer (C) 5 mass parts or less are preferable, 0.01 mass part or more and 1 mass part or less are more preferable, 0.03 mass part or more and 0.3 mass part or less are further more preferable. When the content of the lubricant is smaller than the lower limit, the resin composition such as the acid-modified thermoplastic elastomer (C) cannot sufficiently exhibit the friction reducing ability, and there is a possibility that the suppression of the occurrence of the scum is not achieved. On the contrary, when the content of the lubricant exceeds the above upper limit, the friction of the resin composition is excessively decreased, and the workability of melt molding may be decreased.

  The lubricant (D) is not particularly limited as long as it is generally used as a lubricant. For example, higher fatty acid amide, higher fatty acid metal salt, higher fatty acid ester, low molecular weight polyolefin (for example, molecular weight 500) And low molecular weight polyethylene of about 10,000 to low molecular weight polypropylene).

  Examples of higher fatty acid amides include higher saturated fatty acid amides such as stearic acid amide, palmitic acid amide, lauric acid amide, ethylene bis stearic acid amide, and methylene bis stearic acid amide, and higher unsaturated fatty acid amides such as oleic acid amide and erucic acid amide. And so on.

  Examples of higher fatty acid metal salts include higher saturated fatty acids such as stearic acid, palmitic acid, lauric acid, montanic acid and behenic acid, and calcium and zinc salts of higher unsaturated fatty acids such as oleic acid and erucic acid. .

  Examples of higher fatty acid esters include higher unsaturated fatty acid esters such as ethyl laurate and isopropyl myristate, and higher unsaturated fatty acid esters such as ethyl oleate and ethyl erucate.

  Among these lubricants (D), higher saturated fatty acid derivatives (higher saturated fatty acid amides, higher saturated fatty acid metal salts, higher saturated fatty acid esters, etc.) are preferable. The lubricant (D) having such a higher saturated fatty acid skeleton can reduce the friction between the resin composition and the die lip portion or the like during extrusion molding within a suitable range. Therefore, according to the matte film, it is possible to more efficiently suppress the occurrence of the mains. The reason why the lubricant (D) having a higher saturated fatty acid skeleton exhibits the above-mentioned action is not clear, but such a lubricant is unlikely to be modified by heat, EVOH (A) and thermoplastic elastomer (C). It is considered that the compatibility with the both is excellent, and as a result, the solubility of the thermoplastic elastomer (C) in the resin composition is enhanced, and there is an effect of preventing complete separation of the component (C).

  Here, the “higher saturated fatty acid derivative” refers to a saturated fatty acid derivative having 6 or more carbon atoms, but a saturated fatty acid derivative having 10 or more carbon atoms is more preferable. On the other hand, as the upper limit of the carbon number, a higher saturated fatty acid derivative having 30 or less carbon atoms is preferable, and a higher saturated fatty acid derivative having 25 or less carbon atoms is more preferable. By setting the carbon number within the above range, it is considered that the dispersibility and solubility of the component (C) can be compatible within a preferable range.

  Among the above-mentioned higher saturated fatty acid derivatives, ethylenebisstearic acid amide and calcium salts and zinc salts of higher saturated fatty acids having 17 to 28 carbon atoms are particularly used as the lubricant (D) from the viewpoint of the effect of suppressing the occurrence of scallops and ease of handling. Preferably used.

  In addition, it does not specifically limit as a form in the case of addition of a lubricant (D), For example, any, such as a powder form, a solution form, and a dispersion liquid, may be sufficient.

  The antibacterial agent protects the matte film surface from contamination by microorganisms and improves the stain resistance. As the antibacterial agent, known ones can be used, but when a matte film is used for wallpaper or the like, a silver atom, a copper atom and a zinc atom are used in order to maintain a certain antibacterial performance during the period of use. An inorganic antibacterial agent having any of these as an antibacterial component is preferred. Among these, an antibacterial agent having silver ions as an antibacterial component is most preferable from the viewpoint of antibacterial strength and safety. Examples of such antibacterial agents include those in which silver ions are supported on hydroxyapatite, potassium titanate, water-soluble glass, titanium oxide, zeolite, and the like. Among these, silver-supported titanium oxide and silver-supported zeolite are particularly preferable because they are excellent in compatibility with EVOH (A) and exhibit excellent antibacterial properties. Although it does not specifically limit as content of the said antibacterial agent, The range of 0.01 mass% or more and 10 mass% or less is suitable with respect to the gross mass of a matte film.

<Resin composition>
The resin composition for forming the matte film of the present invention is prepared by adjusting the mass average acid value of the entire resin composition, and uniforming the acid-modified polyolefin (B) and the thermoplastic elastomer (C) in EVOH (A). By improving the dispersibility, the unevenness forming property can be further improved, and as a result, the glossiness of the matte film can be further reduced. The lower limit of the mass average acid value is preferably 0.1 mgKOH / g, more preferably 0.5 mgKOH / g, and particularly preferably 0.8 mgKOH / g. On the other hand, the upper limit of the average acid value is preferably 5.0 mgKOH / g, more preferably 3.0 mgKOH / g, and particularly preferably 2.0 mgKOH / g.

  When the average acid value is smaller than the above lower limit, the uniform dispersibility of the acid-modified polyolefin (B) and the thermoplastic elastomer (C) is insufficient, and the unevenness forming property is lowered, and as a result, it is difficult to reduce the glossiness. . On the other hand, if the average acid value is smaller than the above lower limit, the compatibility of the acid-modified polyolefin (B) and the thermoplastic elastomer (C) with the EVOH (A) is lowered, and it becomes easy to separate, so that during the melt molding, the Is likely to occur. On the other hand, when the average acid value exceeds the above upper limit, the unevenness may be roughened during film formation or the film forming property may be deteriorated.

<Matte film>
The matte film of the present invention may have either a single layer or a multilayer structure. The thickness (maximum thickness) of the matte film is not particularly limited, but the lower limit is preferably 10 μm, and more preferably 12 μm. 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.

  In addition, the thickness (maximum thickness: L1) of this matte film is a value obtained by sampling a 20 cm × 20 cm film and measuring the maximum thickness with a thickness measuring instrument at a total of 9 locations of 3 × 3 at intervals of 5 cm. Average value.

  The lower limit of the unevenness of the matte film of the present invention is preferably 8 μm, and more preferably 8.5 μm. On the other hand, the upper limit of the unevenness is not particularly limited, but is preferably 20 μm, more preferably 15 μm, and particularly preferably 12 μm. When the unevenness degree of the matte film is smaller than the above lower limit, the glossiness becomes high and the function as the matte film becomes insufficient. On the other hand, when the unevenness degree exceeds the above upper limit, holes are easily formed in the film, the film forming property is lowered, and the workability is also lowered.

  The unevenness degree is a difference between the measured maximum thickness (L1) and the theoretical thickness (L2) calculated from the mass and density, and can be obtained by the following method. The mass of the 20 cm × 20 cm sampling film is measured, and the density of the sampling film is measured by a buoyancy method using a toluene / carbon tetrachloride mixed solution. The theoretical thickness (L2) of the film is calculated from this mass and density. The degree of unevenness is a value calculated as this difference ((L1)-(L2)).

  The storage elastic modulus at 5 ° C. of the matte film of the present invention is preferably 1.6 GPa or less, more preferably 1.4 GPa or less, and particularly preferably 1.35 GPa or less. Since the matte film has such a low storage elastic modulus at 5 ° C., it can suppress a decrease in flexibility particularly in a low-temperature environment such as winter, and further improve the workability when used for wallpaper or the like. be able to. On the other hand, the lower limit of the storage elastic modulus at 5 ° C. is preferably 0.6 GPa or more, more preferably 1 GPa or more from the viewpoint of productivity such as film forming property.

  The haze (total haze) of the matte film of the present invention is preferably 60% or more, more preferably 65% or more, and particularly preferably 70% or more. The matte film can achieve effective low glossiness by having such a high haze value. The upper limit of the haze is not particularly limited, but is preferably 90% or less from the viewpoint of realistic productivity, for example.

  The internal haze of the matte film of the present invention is preferably 15% or more, more preferably 18% or more, and particularly preferably 20% or more. The haze derived from the internal structure of the matte film (internal haze) is hardly affected by the heat laminating process. Therefore, according to the matte film having such a high internal haze, the glossiness can be reduced even when used on the surface of wallpaper or the like by heat lamination. On the other hand, the upper limit of the internal haze is not particularly limited, but is preferably, for example, 50% or less from the viewpoint of realistic productivity. The “internal haze” value is a haze value measured after applying a silicone oil thickness of about 2 μm on both sides of the matte film and filling the surface with fine irregularities to make it smooth.

  The glossiness of the matte film of the present invention is preferably 15% or less, more preferably 10% or less, and particularly preferably 8% or less. Since the matte film has such a low glossiness, it can be suitably used as an interior material such as wallpaper. On the other hand, the lower limit of the glossiness of the matte film of the present invention is not particularly limited, but is preferably 3% or more from the standpoint of practical productivity.

<Method for producing matte film>
The matte film can be obtained by a production method comprising a step of mixing the above components to obtain a resin composition and a step of forming (forming a film) the resin composition.

  As a method for mixing (blending) the components such as each resin, a known method can be used, and examples thereof include a method such as melt blending using a single screw or twin screw extruder. Although this blended resin composition may be formed into a film as it is, it is preferable to form a film after pelletizing it once. When forming into a film as it is without pelletizing, the dispersibility of the (B) and (C) component in a resin composition is bad, and there exists a possibility that the target matte film may not be obtained.

  The matte film of the present invention can be obtained by forming the blended resin composition by a melt extrusion molding method such as a normal T-die method. When the molten resin is extruded, the matte film is dispersed due to the difference in melt index of each resin component, and the components (B) and (C) having a relatively small melt index are raised on the surface. Fine irregularities can be formed on the surface. In forming the film, the film may be stretched or unstretched. Normally, a matte film is formed without stretching, but even when it is not stretched, fine unevenness is formed on the film surface as described above due to the difference in fluidity of each resin component when extruded. The In addition, according to the matte film, since the component (C) has a certain degree of compatibility with EVOH (A), it is difficult to completely separate in the extruder, and the component (C) or the like is not easily separated into the die lip part. This prevents the occurrence of the sticking caused by sticking.

  In addition, when obtaining the said film by a T-die method, it is preferable to quench the extruded molten resin. When it is slowly cooled, the surface unevenness is not sufficiently formed, and the glossiness may increase. Here, the rapid cooling means that the air gap of the die is made as small as possible and is rapidly cooled by a cast roll by air slit or electrostatic application.

<Interior material>
The interior material of the present invention comprises a base material and the matte film laminated on the surface of the base material by heat lamination. 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 that can effectively utilize the high flexibility of the matte film of the present invention.

  A typical example of the base material in the wallpaper is a plasticizer-containing soft polyvinyl chloride film or sheet. 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 phosphate-based plasticizers such as phosphate, tributyl phosphate, 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 to 75% by mass, and more preferably 25% by mass to 55% by mass with respect to the total mass of the base material. 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 addition amount of the plasticizer exceeds 75% by mass, physical properties such as strength of the base material are deteriorated, which is not preferable.

  Since the interior material includes a matte film having irregularities formed on the surface as described above, the interior material has a high matte function even when formed by heat lamination. The glossiness of the interior material is preferably 25% or less, and more preferably 20% or less. Since the interior material has such a low glossiness, it can be suitably used as an interior material for each application. On the other hand, the lower limit of the glossiness of the interior material is not particularly limited, but is preferably 5% or more in consideration of realistic productivity and the like.

  In addition, the interior material, especially wallpaper, is equipped with a matte film that is highly flexible even in low-temperature environments. Has a high workability such that it is difficult to produce a floating part without being in close contact with the wall.

  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]
As component (A), 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 are 100 masses. And
As the component (B), 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,
As component (C), a maleic anhydride-modified ethylene-butene copolymer (C1-a) pellet having a melt index (210 ° C., load 2160 g) of 2.9 g / 10 minutes and an acid value of 5.6 mg KOH / g is 17 masses. The parts were 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 acid value of each resin is calculated by the following method. This blended pellet was subjected to a T-die extruder (20 mm extruder D2020 manufactured by Toyo Seiki Seisakusho Co., Ltd. (D (mm) = 20, L / D = 20, compression ratio = 2.0, screw: full flight shallow groove type, die: Coat hanger 300 mm wide die, screen: 50/100/50 Mesh)), extrusion temperature: supply part / compression part / metering part / die = 170/210/225/215 ° C., screw rotation speed 75 rpm, discharge amount 1.9 kg A film was formed under the conditions of / hr. At this time, the take-off speed was adjusted, and the thinnest film capable of being formed was formed at the maximum take-off speed at which film formation was possible to obtain a matte film having a thickness (maximum thickness) of 13.0 μm.

(Acid value)
80 mL of xylene was added to 400 mg of a precisely weighed sample, heated and stirred at 130 ° C. to obtain a uniform solution, and neutralized with 0.05 M potassium hydroxide ethanol solution. The acid value A (mgKOH / g) of each resin was calculated from the amount of 0.05 M potassium hydroxide ethanol solution required until neutralization according to the following formula (1).
A = 56.1 × 0.05 × B × C / D (1)
A: Acid value (KOHmg / g)
B: Amount of use of 0.05M potassium hydroxide ethanol solution (mL)
C: Concentration correction value of 0.05M potassium hydroxide ethanol solution D: Sample mass (g)

[Examples 2 to 4, Comparative Examples 1 to 11]
A matte film according to these examples and comparative examples was obtained in the same manner as in Example 1 except that the pellets were blended in the types and amounts as described in Table 1. In Example 2, 0.15 parts by mass of ethylenebisstearic acid amide was blended as a lubricant. In addition, each (C) component in Table 1 has the following melt index and acid value.
-Maleic anhydride modified ethylene-butene copolymer (C1-b)
Melt index (210 ° C., load 2160 g): 0.3 g / 10 min Acid value: 9.2 mg KOH / g
・ Ethylene-butene copolymer (C2-a)
Melt index (210 ° C., load 2160 g): 5.1 g / 10 min Acid value: 0 mgKOH / g
・ Ethylene-butene copolymer (C2-b)
Melt index (210 ° C., load 2160 g): 23.7 g / 10 min Acid value: 0 mgKOH / g

<Characteristic evaluation>
Each characteristic of the matte film obtained in Examples 1-4 and Comparative Examples 1-8 was evaluated according to the method described below. In Comparative Examples 9 to 11, no film could be formed. These evaluation results are shown in Table 1 together with the component ratio and physical properties of the resin composition.

(1) Thickness of the thinnest film that can be formed Film is sampled at a size of 20 cm x 20 cm when the film is formed at the maximum take-off speed that can be formed as the thinnest film that can be formed by adjusting the take-off speed. did. An average value (L1) of values obtained by measuring the thickness (maximum thickness) of the sampling film at nine places with a thickness measuring instrument (DIAL INDICATOR MODERU LCM-0101 manufactured by Saginomiya) was calculated.

(2) Degree of unevenness The density of the sampling film was measured by a buoyancy method using a toluene carbon tetrachloride mixed solution, and the theoretical thickness (L2) of the film was calculated from the mass and the density. A difference ((L1)-(L2)) between the actually measured thickness and the theoretical thickness was calculated and used as the degree of unevenness.

(3) Gloss after heat lamination Mixture of Dick Seal LA-100Z and KP-90 (curing agent) manufactured by Dainippon Ink & Chemicals, Inc., which is an organic solvent, at a mass ratio of 100 parts to 0.6 parts 80 20 parts by mass of methyl ethyl ketone as a solvent was added to parts by mass to obtain an adhesive. This was coated on each thinnest film using a No. 10 bar coater and dried for 1 minute in a dryer at 80 ° C. The adhesive-coated surface of the above film is aligned on the vinyl chloride surface of the non-foamed vinyl chloride wallpaper base material manufactured by Nankai Technate Co., Ltd., and further, a biaxially stretched polyester film (trade name Lumirror S105, thickness 50 μm, manufactured by Toray Industries, Inc.) ). Next, using a laminator DX-350 manufactured by Tokyo Lamix Co., Ltd., heat lamination was performed under the conditions of a temperature of 120 ° C. and a speed of 2 m / min to obtain an interior material of a film / vinyl chloride wallpaper. The glossiness of the film surface of this interior material was measured at an angle of 60 degrees with a gloss meter VGS-300A manufactured by Nippon Denshoku Industries Co., Ltd. according to JIS-Z8741.

(4) Storage elastic modulus Each thinnest matte film was cut into 20 mm in the MD direction (flow direction) and 5 mm in the TD direction (vertical direction). The cut film was attached to a tensile chuck of a viscoelasticity measurement / analysis apparatus “DVE-4 Rheospectr” manufactured by Rheology Co., Ltd. According to JIS-K7244-4, measurement mode tension (t = 1 mm or less), −120 ° C. to 120 ° C., heating rate 3 ° C./min, fundamental frequency 10 Hz, strain waveform sine wave, dynamic viscoelasticity of film against temperature A graph showing the change was prepared, and the storage elastic modulus (E ′) at 5 ° C. was read.

(5) Average acid value The mass average of the acid value of each resin calculated by the above method was defined as the average acid value of the resin composition.

(6) Glossiness Each thinnest matte film described above was measured at an angle of 60 degrees with a gloss meter VGS-300A manufactured by Nippon Denshoku Industries Co., Ltd. in accordance with JIS-Z8741.

(7) Internal haze / total haze Measurement was performed according to JIS-D8741 using an HR-100 type haze meter manufactured by Murakami Color Research Laboratory. The total haze is the value of each of the thinnest films, and the internal haze is a value measured by applying silicon oil with a thickness of about 2 μm on both surfaces of each of the thinnest films.

(8) Amount of generated scum In Examples 1 to 4 and Comparative Examples 1 to 5, in order to confirm the generated amount of sag in extrusion molding, at the time point 30 minutes after the start of extrusion when obtaining a strand (blend pellet). The resin composition (Meani) adhered to the extrusion port was taken out and the mass was measured. In addition, in order to confirm the amount of generation of the mains, it was decided to compare the amount of the mains generated in the extrusion molding of the strands that are easy to generate the mains rather than the film forming.

  As shown in Table 1, the matte films of Examples 1 to 4 can be formed into a thickness of 16 μm or less, have a low glossiness of 10% or less, and after heat lamination The glossiness is also suppressed to 20% or less. Furthermore, the storage elastic modulus at 5 ° C. is 1.5 GPa or less, and the flexibility in a low temperature environment is also excellent.

  Furthermore, although the matte film of Examples 1-4 contains (C) component, the amount of generation | occurrence | production of the mean at the time of obtaining a strand is reduced. In Examples 1 to 4, the occurrence of cracks during film formation was not visually confirmed.

  On the other hand, although the matte films of Comparative Examples 1 to 4 have sufficient performance as a matte film, the content of the unmodified thermoplastic elastomer is large and the acid value of the component (C) is low. There was a lot of spear generation. In addition, the matte film of Comparative Example 5 that does not contain the thermoplastic elastomer (C) has insufficient flexibility at low temperatures. The matte films of Comparative Example 6 containing no acid-modified polyolefin (B) and Comparative Examples 7 and 8 containing a thermoplastic elastomer (C) having a large melt index value have low irregularity and high gloss. Conversely, Comparative Example 9 containing a thermoplastic elastomer (C) having a low melt index value, Comparative Example 10 containing a high content of acid-modified polyolefin (B), and a high content of (B) and (C) Each matte film of Example 11 could not be formed.

  As described above, the matte film of the present invention suppresses the occurrence of scouring during melt molding, has excellent film-forming properties of the resin composition, has low gloss, and has high flexibility in a low-temperature environment. It is suitably used for interior materials such as wallpaper.

Claims (17)

Molded from a resin composition containing an ethylene-vinyl alcohol copolymer (A), an acid-modified polyolefin (B) and a thermoplastic elastomer (C);
The total content of the acid-modified polyolefin (B) and the thermoplastic elastomer (C) with respect to 100 parts by mass of the ethylene-vinyl alcohol copolymer (A) is 5 parts by mass or more and 100 parts by mass or less.
A gloss index wherein the thermoplastic elastomer (C) has a melt index of 2 g / 10 min to 18 g / 10 min, and the thermoplastic elastomer (C) has a mass average acid value of 2.5 mgKOH / g to 20 mgKOH / g Eraser film.   The matte film according to claim 1, wherein a mass ratio [(C) / (B)] of the thermoplastic elastomer (C) to the acid-modified polyolefin (B) is 1.5 or more and 10 or less.   The matte film according to claim 1 or 2, wherein the thermoplastic elastomer (C) is an acid-modified ethylene-α-olefin copolymer.   The matte film according to claim 3, wherein the acid-modified ethylene-α-olefin copolymer is a carboxylic acid-modified ethylene-butene copolymer.   The matte film according to any one of claims 1 to 4, wherein the acid-modified polyolefin (B) has a melt index of 0.01 g / 10 min to 10 g / 10 min.   The matte film according to any one of claims 1 to 5, wherein the acid-modified polyolefin (B) is acid-modified polyethylene.   The matte film according to claim 6, wherein the acid-modified polyethylene is a carboxylic acid-modified high-density polyethylene.   The matte film according to any one of claims 1 to 7, wherein the ethylene-vinyl alcohol copolymer (A) has a melt index of 0.1 g / 10 min to 30 g / 10 min.   The value obtained by subtracting the melt index of the thermoplastic elastomer (C) from the melt index of the ethylene-vinyl alcohol copolymer (A) is 5 g / 10 min or more. The matte film described.   The matte film according to any one of claims 1 to 9, wherein the ethylene unit content of the ethylene-vinyl alcohol copolymer (A) is 35 mol% or more and 60 mol% or less.   The matte film according to any one of claims 1 to 10, wherein the saponification degree of the ethylene-vinyl alcohol copolymer (A) is 90 mol% or more.   The matte film according to any one of claims 1 to 11, wherein a mass average acid value of the entire resin composition is 0.1 mgKOH / g or more and 5.0 mgKOH / g or less.   The matte film according to any one of claims 1 to 12, wherein a storage elastic modulus at 5 ° C is 1.6 GPa or less.   The matte film according to any one of claims 1 to 13, wherein the unevenness degree is 8 µm or more.   The interior material provided with a base material and the matte film of any one of Claims 1-14 laminated | stacked on the surface of this base material by thermal lamination.   The interior material according to claim 15, wherein the glossiness of the surface is 20% or less. A process of obtaining a resin composition by mixing an ethylene-vinyl alcohol copolymer (A), an acid-modified polyolefin (B) and a thermoplastic elastomer (C), and a process of molding the resin composition,
The total content of the acid-modified polyolefin (B) and the thermoplastic elastomer (C) with respect to 100 parts by mass of the ethylene-vinyl alcohol copolymer (A) of the resin composition is 5 parts by mass or more and 100 parts by mass or less,
A gloss index wherein the thermoplastic elastomer (C) has a melt index of 2 g / 10 min to 18 g / 10 min, and the thermoplastic elastomer (C) has a mass average acid value of 2.5 mgKOH / g to 20 mgKOH / g A method for producing an eraser film.