KR20220135756A - Inflation film - Google Patents

Abstract

An inflation film according to one aspect of the present invention has an inner layer comprising a silicone-based antifouling agent. An objective of the present invention according to one aspect is to provide an inflation film which is not easily creased and can be easily unfolded in a state where double films are in close contact with each other.

Description

INFLATION FILM

The present invention relates to an inflation film.

Conventionally, an inflation film in which a resin composition is formed by an inflation molding method is known. When the double-wound inflation film is deployed as one sheet, the inner layers of the inflation film may have too strong adhesion. In this case, it is easy to damage the inflation film if you try to peel it vigorously during deployment. In order to reduce the close_contact|adherence of inner layers, the inflation film containing an anti-blocking agent in an inner layer is known (for example, patent document 1 and patent document 2).

Japanese Patent Laid-Open No. 2016-068995 Japanese Patent Laid-Open No. 2011-042780

However, in the prior art as described above, the adhesion between the inner layers is too weak, and since the adhesion between the inner layers is peeled off before winding on a roll during manufacturing, wrinkles are likely to occur in the inflation film, and there is a problem that the production yield is deteriorated. When coating a coating liquid to the inflation film before winding up, it becomes a cause of coating unevenness.

One aspect of the present invention is not easily wrinkled in a state in which the double film is in close contact, and an object of the present invention is to provide an inflation film that can be easily deployed.

In order to solve the above problems, the inflation film according to an aspect of the present invention has an inner layer comprising a silicone-based antifouling agent.

According to one aspect of the present invention, it is possible to provide an inflation film that is not easily wrinkled in a state in which the double film is in close contact, and can be easily deployed.

1 is a graph showing infrared radiation (IR) measurement results of films obtained by press-molding SAB03390LD Anti-Dust and F200-0 to a thickness of 0.1 mm, respectively.

<Inflation film>

Inflation film according to an aspect of the present invention has an inner layer comprising a silicone-based antifouling agent. As used herein, the term “inflation film” refers to a film in which a resin composition is molded according to an inflation molding method. As the inflation film according to an aspect of the present invention has an inner layer containing a silicone-based antifouling agent, wrinkles do not easily occur in a state in which the double film is in close contact and can be easily deployed. The inflation film according to an aspect of the present invention may be a double film on a tube before being deployed, or a film after being deployed.

The inflation film according to an aspect of the present invention is a film having an inner layer. Inflation film according to an aspect of the present invention, for example, may be a single-layer film consisting of an inner layer, may be a multi-layer film having an inner layer. Examples of the multilayer film include a two-layer film composed of an inner layer and an outer layer; a three-layer film comprising an inner layer, an intermediate layer and an outer layer; a four-layer film consisting of an inner layer, two intermediate layers, and an outer layer; and a five-layer film comprising an inner layer, three intermediate layers, and an outer layer. In the three-layer film, the thickness of the inner layer and the outer layer is preferably 10 to 50 μm, respectively, and the thickness of the intermediate layer is preferably 30 to 150 μm. In the case of a three-layer film, the ratio of the thickness of each layer is preferably 1/1/1 to 1/4/1, more preferably 1/2/1 to 1/4/1, for inner layer/middle layer/outer layer. and 1/3/1 is more preferable.

[resin composition]

The resin composition is a material for forming an inflation film. The resin composition constituting the inner layer, the resin composition constituting the intermediate layer, and the resin composition constituting the outer layer contain a thermoplastic resin, preferably a polyolefin-based resin. The resin composition constituting the inner layer further contains a silicone antifouling agent. The resin composition constituting the intermediate layer and the resin composition constituting the outer layer do not necessarily contain the silicone antifouling agent. The resin composition constituting the intermediate layer may further include an inorganic filler. The resin composition constituting the inner layer, the resin composition constituting the intermediate layer, and the resin composition constituting the outer layer may have different compositions from each other.

(silicone antifouling agent)

The silicone-based antifouling agent may be an antifouling agent containing a silicone compound, and it is preferable to further include a resin material such as a polyolefin-based resin to be described later. As used herein, the silicone compound refers to a compound having a siloxane bond (Si-O-Si). Examples of the silicone-based antifouling agent include SAB03390LD Anti-Dust (manufactured by Kafrit) and GENIOPLAST pellet S (manufactured by Asahi Kasei Barker Silicone Co., Ltd.).

The content of the silicone-based antifouling agent relative to the total weight of the inner layer is preferably 0.2% by weight or more from the viewpoint that the double film can be easily developed. In addition, the content of the silicone antifouling agent relative to the total weight of the inner layer is preferably 2.0% by weight or less from the viewpoint of improving transparency and less wrinkling of the film.

(Polyolefin resin)

Examples of the polyolefin-based resin include a single aggregate of ethylene, a copolymer of ethylene and α-olefin, and a copolymer of ethylene and a monomer other than α-olefin. Among these, an ethylene-α-olefin copolymer (a copolymer of ethylene and α-olefin) is preferably used.

Examples of the ethylene-α-olefin copolymer include an ethylene-propylene copolymer, an ethylene-1-butene copolymer, an ethylene-1-pentene copolymer, an ethylene-1-hexene copolymer, and an ethylene-1-heptene copolymer. , an ethylene-1-octene copolymer, and the like. Among these, an ethylene-1-butene copolymer, an ethylene-1-hexene copolymer, and an ethylene-1-octene copolymer are particularly preferable. On the other hand, as the ethylene-α-olefin copolymer, a copolymer obtained by copolymerizing ethylene and two or more types of α-olefins may be used.

The ethylene-α-olefin copolymer contributes to the provision of a film having excellent strength. From the viewpoint of obtaining a film with high strength, the ethylene-α-olefin copolymer is preferably ethylene and α-olefin polymerized using a catalyst such as a metallocene catalyst, for example, a linear low-density polyolefin; Linear ultra-low-density polyolefin etc. are mentioned.

As the linear low-density polyolefin, those having a density of 910 kg/m 3 to 930 kg/m 3 are preferably used. Moreover, as a linear ultra-low-density polyolefin, the thing with a density of 865 kg/m<3> - 905 kg/m<3> is used preferably. The densities of the linear low-density polyolefin and the linear ultra-low-density polyolefin are values measured according to the method specified in Method A of JIS K7112:1999, and are the densities measured at 23°C.

As the resin material included in the resin composition, only one ethylene-α-olefin copolymer may be used, and two or more types of ethylene-α-olefin copolymer may be used in combination.

The melt flow rate (MFR) of the ethylene-α-olefin copolymer is preferably 0.05 g/10 min or more and 20 g/10 min or less, and more preferably 0.1 g/10 min or more and 15 g/10 min or less. The MFR is measured by method A according to JIS K 7120: 1995 under the conditions of a temperature of 190° C. and a load of 21.18 N.

Examples of commercially available ethylene-α-olefin copolymers include EXCELLEN (registered trademark) FX (manufactured by Sumitomo Chemical Corporation), TAFMER (registered trademark) (manufactured by Mitsui Chemicals Co., Ltd.), ENGAGE (registered trademark) (manufactured by Dow Chemical Co., Ltd.), AFFINITY (trademark) (made by Dow Chemical), EXACT (trademark) (made by ExxonMobil), KERNEL (trademark) (made by Nippon Polyethylene Corporation), etc. are mentioned.

A copolymer of ethylene and a monomer other than α-olefin, exemplified as a polyolefin-based resin, may also be referred to as an ethylene-based copolymer.

Examples of the ethylene-based copolymer include an ethylene-vinyl ester copolymer, a copolymer of ethylene and an unsaturated carboxylic acid and/or a derivative thereof (hereinafter also referred to as an ethylene-unsaturated carboxylic acid (derivative) copolymer.) have. An ethylene copolymer can be used independently and can also use two or more types of ethylene copolymers together.

The ethylene-vinyl ester copolymer refers to an ethylene-vinyl ester copolymer having, as main monomer units, a monomer unit derived from ethylene and a monomer unit derived from vinyl ester. The ethylene-vinyl ester copolymer may be a random copolymer of an ethylene monomer and a vinyl ester monomer, or may be a block copolymer.

As a vinyl ester used as a constituent material of an ethylene-vinyl ester copolymer, it is a vinyl ester of a fatty acid, for example, C2-C4 thing of the said fatty acid is mentioned, More specifically, vinyl acetate, vinyl propionate, etc. can be heard In one aspect of the present invention, the ethylene-based copolymer may include monomer units derived from two or more types of vinyl esters. Among them, the vinyl ester is preferably vinyl acetate.

Specific examples of the ethylene-vinyl ester copolymer having a monomer unit derived from ethylene and a monomer unit derived from a vinyl ester include an ethylene-vinyl acetate copolymer and an ethylene-vinyl propionate copolymer, and in particular, ethylene-acetic acid A vinyl copolymer (EVA) is preferably used. In addition, an ethylene-vinyl ester copolymer can be used independently, and two or more types of ethylene-vinyl ester copolymers can also be used together. In addition, the ethylene-vinyl ester copolymer may contain monomer units derived from monomers other than ethylene and vinyl ester.

On the other hand, the content of the monomer unit derived from ethylene in the ethylene-vinyl ester copolymer and the content of the monomer unit derived from the vinyl ester can be quantified by a saponification method, and more specifically, the ethylene-based copolymer is ethylene-derived. -In case of vinyl acetate copolymer, it can be quantified according to JIS　K　7192:1999.

The density of the ethylene-vinyl ester copolymer is 925 kg/m3 or more, more preferably 930 kg/m3 or more, more preferably 933 kg/m3 or more, 955 kg/m3 or less, 952 kg/m3 or less, more preferably 950 kg/m3 or less. It is more preferable that it is less than m3. The density of the ethylene-vinyl ester copolymer is in the range of 925 kg/m 3 or more and 955 kg/m 3 or less. On the other hand, the density of the ethylene-vinyl ester copolymer is a value measured according to the method A of JIS K7112: 1999, and is a density measured at 23°C.

The melt flow rate (MFR) of the ethylene-vinyl ester copolymer is preferably 0.05 g/10 min or more and 20 g/10 min or less, and more preferably 0.1 g/10 min or more and 15 g/10 min or less. The MFR is measured by method A according to JIS K 7210:1999 under conditions of a temperature of 190° C. and a load of 21.18 N.

As a commercial item usable as an ethylene-vinyl ester copolymer, for example, EVATATE (trademark) (made by Sumitomo Chemical Corporation), SUMITATE (trademark) (made by Sumitomo Chemical Corporation), NOVATEC (trademark) EVA (Nippon Polyethylene Co., Ltd.) ), ULTRATHENE (registered trademark) (manufactured by Tosoh Corporation), SUNTEC (registered trademark) EVA (manufactured by Asahi Kasei Corporation), and EVAFLEX (registered trademark) (manufactured by Mitsui DuPont Polychemical Corporation).

[additive]

The resin composition may contain additives such as a light stabilizer, an ultraviolet absorber, an antifogging agent, an antioxidant, an antifog agent, and a lubricant within the range that does not impair the effects of the present invention.

As a light stabilizer, the hindered amine compound which has the structure of Unexamined-Japanese-Patent No. 8-73667 is mentioned, for example. Specifically, brand names: Tinuvin 622, Chimassorb 944, Chimassorb 119 (above manufactured by BASF), HOSTAVIN N30, VP Sanduv　or PR-31 (above manufactured by Clariant), CYASORB UV3529, CYASORB UV3346 (above manufactured by Cytec), etc. have.

Moreover, the hindered amine compound which has the structure of Unexamined-Japanese-Patent No. 11-315067, Unexamined-Japanese-Patent No. 2001-139821, WO2005/082852, and Unexamined-Japanese-Patent No. 2009-530428 is mentioned. Specifically, a brand name: NOR371 (made by BASF), ADK STAB LA-900 (made by ADEKA Corporation), ADK STAB LA-81 (made by ADEKA Corporation), HOSTAVIN NOW (made by Clariant Corporation) is mentioned.

Moreover, the ethylene-cyclic aminovinyl compound copolymer which has a monomeric unit based on ethylene and a monomeric unit based on a cyclic aminovinyl compound as a light stabilizer is also mentioned. Examples of such an ethylene-cyclic aminovinyl compound copolymer include those having the structure described in Japanese Patent Application Laid-Open No. 2002-265693.

Examples of the ultraviolet absorber include 2-hydroxybenzophenones, 2-(2'-hydroxyphenyl)benzotriazoles, benzoates, substituted oxanilides, cyanoacrylates, and triazines. can

Examples of the 2-hydroxybenzophenones include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 5,5 '-methylenebis(2-hydroxy-4-methoxybenzophenone) etc. are mentioned.

Examples of 2-(2'-hydroxyphenyl)benzotriazoles include 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxyl-3',5'-dize-3 Butylphenyl)benzotriazole, 2-(2'-hydroxyl-3',5'-ditertiary butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxyl-3'-tertiary butyl -5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5'-tertiary octylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'- Dicumylphenyl)benzotriazole, 2-(2-hydroxy-3,5-di-tertylphenyl)benzotriazole, 2,2'-methylenebis(4-tert-octyl-6-benzotriazolyl)phenol , 2-(2'-hydroxy-3'-tertiary butyl-5-carboxyphenyl) benzotriazole, etc. are mentioned.

Examples of benzoates include phenyl salicylate, resorcinol monobenzoate, 2,4-ditertiary butylphenyl-3',5'-ditertiary butyl-4'-hydroxybenzoate, and 2,4-ditertiary benzoate. and amylphenyl-3',5'-ditertiary butyl-4'-hydroxybenzoate and hexadecyl-3,5-ditertiary butyl-4-hydroxybenzoate.

Examples of the substituted oxanilides include 2-ethyl-2'-ethoxyoxanilide and 2-ethoxy-4'-dodecyloxanilide.

Examples of the cyanoacrylates include ethyl-α-cyano-β,β-diphenyl acrylate and methyl-2-cyano-3-methyl-3-(p-methoxyphenyl)acrylate. .

Examples of the triazines include 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[(hexyl)oxy]-phenol, 2-[4,6-bis(2, 4-Dimethylphenyl)-1,3,5-triazin-2-yl]-5-(octyloxy)phenol, 2-(2-hydroxy-4-octoxyphenyl)-4,6-bis(2 ,4-ditertiarybutylphenyl)-s-triazine, 2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-s-triazine, 2-(2-hydroxy-4 -propoxy-5-methylphenyl)-4,6-bis(2,4-di tertiary butylphenyl)-s-triazine etc. are mentioned.

Preferably, they are 2-(2'-hydroxyphenyl) benzotriazoles, More preferably, 2-(2'-hydroxy-3'-tertbutyl-5'-methylphenyl)-5-chlorobenzo triazole and 2-(2-hydroxy-3,5-dizeterpentylphenyl)benzotriazole are mentioned.

Ultraviolet absorbers are used individually or in 2 or more types.

Examples of the antifogging agent include sorbitan fatty acid esters such as sorbitan monopalmitate, sorbitan monostearate, sorbitan monopalmitate, sorbitan monomontanate, sorbitan monooleate and sorbitan dioleate, and alkylene oxides thereof. Sorbitan surfactants such as adducts, glycerin monopalmitate, glycerin monostearate, diglycerin distearate, triglycerin monostearate, tetraglycerin dimontanate, glycerin monooleate, diglycerin monooleate, diglycerin monostearate Glycerin fatty acid esters and alkylenes thereof, such as glycerin sesquioleate, tetraglycerin monooleate, hexaglycerin monooleate, hexaglycerin trioleate, tetraglycerin trioleate, tetraglycerin monolaurate, and hexaglycerin monolaurate Glycerin-based surfactants such as oxide adducts, polyethylene glycol-based surfactants such as polyethylene glycol monopalmitate and polyethylene glycol monostearate, alkylene oxide adducts of alkylphenols, esters of sorbitan/glycerin condensates with organic acids, poly Oxyethylene (2 moles) stearylamine, polyoxyethylene (4 moles) stearylamine, polyoxyethylene (2 moles) stearylamine monostearate, polyoxyethylene (4 moles) laurylamine monostearate, etc. Nonionic surfactants, such as polyoxyethylene alkylamine and its fatty acid ester, are mentioned. These can be used independently and can also use 2 or more types together.

Examples of the antioxidant include so-called hindered phenol compounds such as 2,6-dialkylphenol derivatives and 2-alkylphenol derivatives, and trivalent phosphorus atoms such as phosphite compounds and phosphonite compounds. A phosphorus ester compound is mentioned. These antioxidants can be used independently and can also use 2 or more types together. In particular, from the viewpoint of color stabilization, it is preferable to use a hindered phenol-based compound and a phosphorus-based ester compound in combination.

Examples of the antifouling agent include a fluorine compound having a perfluoroalkyl group, an ω-hydrofluoroalkyl group, etc. (especially a fluorine-based surfactant), and a silicone-based compound having an alkylsiloxane group (particularly a silicone-based surfactant). . Specific examples of fluorine-based surfactants include Daikin Kogyo Co., Ltd. Unidyne DSN-403N, DS-403, DS-406, DS-401 (trade name), Surflon KC-40, AF-1000, AF manufactured by AGC Seimi Chemical Co., Ltd. -2000 (brand name) etc. are mentioned, As a silicone type surfactant, SH-3746 (trade name) by Toray Dow Corning Co., Ltd. is mentioned.

In addition, the inflation film according to an aspect of the present invention may further have an anti-fogging coating layer on the outer surface of the outer layer. Inflation film having an anti-fogging coating layer can reduce coating unevenness because the coating solution can be applied in a state where the double film is not easily wrinkled when the double film is in close contact. As the anti-fogging coating layer, an anti-fogging layer made of an inorganic colloid, an anti-fogging coating layer containing an inorganic colloid and a binder resin, an anti-fogging layer made of an inorganic colloid, and an anti-fogging coating layer containing an inorganic colloid and a binder resin are laminated. An antifogging coating film layer is mentioned.

The inorganic colloid imparts hydrophilicity to the surface of a hydrophobic polyolefin-based resin film, and is usually used in the form of a colloidal solution in which the inorganic colloid is dispersed in a liquid dispersion medium such as water. Specifically, a silica colloidal solution and an alumina colloidal solution are mentioned, A silica colloidal solution is preferable.

As binder resin, a polyurethane-type resin, an acrylic resin, an acrylic modified polyurethane-type resin, polyester-type resin, an epoxy resin etc. are mentioned, for example.

The binder resin is usually used as an aqueous emulsion in which the resin is dispersed in a mixed solvent of water or an aqueous solvent such as water and alcohol.

The anti-fogging coating layer is preferably an anti-fogging layer containing silica and binder resin. Moreover, as binder resin, a polyurethane-type resin, an acrylic resin, and an acrylic modified polyurethane-type resin are preferable.

As a preferable silica, the spherical thing whose average particle diameter is 5-100 nm is mentioned.

When the total of the silica and binder resin contained in the antifogging coating layer is 100 mass %, the content of silica is 30 to 70 mass %, it is preferable that the content of the binder resin is 30 to 70 mass %, and the content of silica It is this 50-65 mass %, and it is more preferable that content of binder resin is 35-50 mass %. When the content of silica is too small, a sufficient antifogging effect cannot be obtained. Conversely, when it is too large, the film becomes cloudy and the light transmittance under low temperature can be reduced.

<Method for Producing Inflation Film>

The method for manufacturing an inflation film according to an aspect of the present invention preferably includes a film forming step of forming a resin composition into a film according to an inflation molding method. The resin composition constituting the inner layer is as described above in <Inflation film>. In the inflation film according to an aspect of the present invention, since the inner layer includes a silicone-based antifouling agent, it is possible to prevent wrinkles from forming in a state in which the double film is in close contact during the film forming process.

An apparatus for manufacturing an inflation film used in the method for manufacturing an inflation film according to an aspect (first aspect) of the present invention includes a plurality of extruders and a mold, and the mold is provided with a plurality of flow passages therein. Here, the inflation film manufacturing apparatus is combined so that one extruder communicates with one flow path. The number of extruders may be set according to the number of flow paths provided in the mold, the fluidity of the melt of the resin composition, and the thickness of the resin composition to be formed, but may be at least two, preferably two to five, and two It is more preferable that it is a generation to 3 generations.

Each of the extruders may be appropriately selected according to the type of the resin composition to be melt-plasticized, and may be a single-stage extruder or a random two-stage extruder (two-stage extruder with different diameters).

In the process of obtaining the melt of the resin composition, the heating temperature for melt plasticizing the resin composition by the extruder is appropriately set with reference to the melt flow rate (MFR), melting point or glass transition temperature of the thermoplastic resin contained in the resin composition. do. For example, when using the resin composition containing the above-mentioned polyolefin resin, the heating temperature of the resin composition in the extruder is preferably 130°C or more and 200°C or less, and more preferably 140°C or more and 180°C or less.

The cylinder diameter of the extruder can be appropriately selected according to the fluidity of the melt of the resin composition to be melt-plasticized and extruded, or the amount of the melt required for production of the inflation film. In addition, the sum of the amount of supply of the melt of the resin composition to the mold from the plurality of extruders can be appropriately designed according to the type of the resin composition to be melt-plasticized, the type of the extruder, the diameter of the cylinder equipped with the extruder, etc. The amount of the melt supplied to the mold by a large extruder may be divided by the total amount of the melt to be supplied to the mold according to the number of extruders and flow passages provided in the inflation film manufacturing apparatus. Another advantage of the method for producing a film according to an embodiment is that a large amount of a melt with low fluidity can be supplied to the mold by using a plurality of extruders having a generally available cylinder diameter.

A plurality of flow paths provided in the mold are provided to join before reaching one annular slit (opening) in the inside of the mold (also referred to as a cavity). On the other hand, the temperature inside the mold for heating the melt of the resin composition supplied from the extruder may be appropriately set for the purpose of maintaining the temperature of the melted resin supplied, and a resin composition containing a polyolefin-based resin to be described later. When using, it is preferable that they are 130 degreeC or more and 200 degrees C or less, and it is more preferable that they are 140 degrees C or more and 180 degrees C or less.

In the step of merging the melts, each melt of the resin composition supplied from the extruder to the plurality of flow passages is extruded from one annular slit provided in the mold to the outside of the mold, the melt is merged into one layer inside the mold . On the other hand, the outer diameter of the annular slit may be designed according to the desired width of the film (circumferential length in a cylindrical shape, so-called film width in TD (Traverse Direction)). For example, in the case of producing a film having a film width (circumferential length in a cylindrical shape) of 10 m, a mold having an annular slit having an outer diameter in the range of 1,000 to 1,600 mm is preferably used. In addition, the width of the slit (also referred to as lip clearance) may be designed according to the type of resin to be used. For example, when using the resin composition containing the polyolefin resin mentioned later, the metal mold|die whose width|variety (lip clearance) of a slit is 1.0-5.0 mm is used preferably. The method of manufacturing a film according to an aspect may stabilize the manufacturing conditions of the film even when manufacturing a large film such as, for example, a width of 10 m to 12 m.

In the step of forming the layer of the resin composition, the melt of the resin composition joined inside the mold is extruded from the annular slit. Here, the annular slit is open toward the top of the mold and extrudes the melt upwards from the mold. The extruded melt forms a cylindrical film, and forms a film by cooling the cylindrical film and inflating while being drawn upwards. The take-up speed and blow-up ratio (BUR) of the melt in the inflation method may be appropriately designed according to the film thickness of the film to be inflation molded. The take-up speed of the melt is determined in accordance with the desired thickness and width of the film and is linked with the amount of melt supplied. On the other hand, the expansion ratio BUR is uniquely determined by the above-mentioned die size (outer diameter of the annular slit) and the desired width of the film. Since the expansion ratio (BUR) greatly affects the bubble stability at the time of film forming and the strength (balance of longitudinal/transverse directions) of the film obtained, assuming the maximum and minimum of the desired film width, the expansion ratio is in the range of 1.3 to 4.0. It is common to determine the mold size (outer diameter of the annular slit) to converge.

In the method for producing an inflation film according to an aspect, a plurality of extruders share the supply of a melt obtained by melt plasticizing a resin composition containing a silicone antifouling agent to a flow path in a mold by an extruder. Thereby, the pressure applied to the melt of the resin composition supplied to the mold by one extruder can be reduced without reducing the total amount of the melt to be supplied to the mold. For this reason, heat generation of the melt caused by excessive shear stress is applied to the melt, and the viscosity of the melt extruded from the mold can be stabilized. In addition, suppressing the heat generation of the melt in the extruder has the effect of stabilizing the temperature and fluidity of the melt in the mold and uniforming the film thickness of the melt in the circumferential direction of the annular slit.

That is, the method for producing an inflation film according to an aspect can stabilize the pressure when the extruder extrudes the melt, and thus, the temperature of the melt of the resin composition provided for the inflation film molding can be stabilized, so after When the inflation film is manufactured with the film of the melt in the process, it is possible to prevent shaking (rumble) of the film of the melt. Therefore, it can be prevented that the thickness of the inflation film to be produced becomes non-uniform or fails in the production of the inflation film due to the shaking of the film of the melt.

<Method for producing an inflation film according to another aspect>

The manufacturing method of the inflation film according to an aspect of the present invention is not limited to the above manufacturing method. For example, in the method for manufacturing an inflation film according to another aspect (second aspect) of the present invention, the melt is supplied to a mold having a plurality of flow paths respectively communicating with each other of a plurality of extruders and merged inside the mold In the step to be made, the layers of the melt of the other resin composition are joined to one or both surfaces of the layer formed from the joined melt. That is, the method for producing an inflation film according to the second aspect is a method for producing a multilayer film by co-extrusion inflation molding of a melt of a resin composition containing a silicone antifouling agent and a melt of a resin composition different from the resin composition. .

In the method for producing a multilayer film, the plurality of flow passages to which the melt is individually supplied from a plurality of extruders provided in the inflation film production apparatus are multilayered annular flow passages having the same center point as one annular slit, and the resin A melt of the composition is extruded from one annular slit through a multi-layered annular flow path. For example, when an inflation film manufacturing apparatus is equipped with three extruders, the three flow passages individually communicating with these extruders are joined sequentially or simultaneously in the mold to form a three-layer molten film (melt film). ) is provided as a flow path forming the Here, a melt of a resin composition different from the melt of a resin composition containing a silicone antifouling agent is supplied to a flow path forming the outermost layer of the three-layer molten film and a flow path forming an intermediate layer, and a flow path forming the innermost layer A melt of a resin composition containing a silicone antifouling agent is supplied. Accordingly, the melts supplied from the flow paths of the three lines are joined before being extruded from the annular slit to form a three-layer inflation film.

In addition, since the heating temperature of each resin composition in an extruder and the heating temperature of the molten body in a metal mold|die are the same as the 1st aspect mentioned above, the description is abbreviate|omitted. In addition, the supply amount of the melt of the resin composition containing the silicone antifouling agent and the supply amount of the melt of the resin composition different from the resin composition containing the silicone antifouling agent may be appropriately adjusted according to the fluidity of these resin compositions, and the description thereof is omitted. .

On the other hand, each of the extruders supplying the melt of the resin composition (that is, the resin composition for forming the inner layer) containing the silicone antifouling agent to the mold, the supply amount in each extruder is adjusted so as to distribute the total amount of the melt supplied to the mold, There may be, for example, the total amount of the melt supplied to the mold may be divided equally. The type of extruder for supplying the melt of the resin composition for forming the outer layer, and the melt of the resin composition for forming the intermediate layer to the mold, and the amount of the melt supplied in the extruder, the thickness of the outer layer and the intermediate layer in the inflation film to be produced It can be appropriately designed according to the thickness of the inner layer, and it is not necessary to be the same as the conditions for supplying the melt of the resin composition for forming the inner layer.

The method of manufacturing an inflation film according to an aspect of the present invention may further include a mixing process of mixing the resin composition before the film forming process.

As the resin composition, a resin material and another material (in the case of a resin composition for forming an inner layer, a silicone antifouling agent) are melt-kneaded in advance and molded into pellets, for example, can be used. By supplying the previously melt-kneaded resin composition to each of a plurality of extruders, the resin composition of the same composition is melt-plasticized in each extruder, and a film having one layer formed from one thermoplastic resin can be easily produced. can As a method of manufacturing a resin composition, the method of mixing a resin composition with mixers, such as a ribbon blender, a Bumberry mixer, a super mixer, or a twin-screw kneader, is mentioned, for example.

The method of manufacturing an inflation film according to an aspect of the present invention may further include a coating step of further forming an anti-fogging coating layer on the outside of the outer layer. In the inflation film according to an aspect of the present invention, since the inner layer contains a silicone-based antifouling agent, the coating solution can be applied in a state where the double film is in close contact with the wrinkle-resistant state in the film forming process, so that the coating stain can be reduced. have. The antifogging coating film layer containing silica and binder resin can be carried out as shown below, for example, and can be formed. An aqueous emulsion containing a binder resin, an aqueous silica colloidal solution containing silica, and water as a dispersion medium are mixed and stirred to obtain a coating solution. Next, an antifogging layer can be formed by apply|coating this coating liquid using a well-known means and drying. Specific examples of the application means include bar coating, gravure coating, reverse coating, brush coating, spray coating, kiss coating, die coating, and dipping. As a drying means, hot air drying is mentioned, for example.

In order to improve coatability, a silicone type surfactant and a fluorine type surfactant can be contained in a coating liquid. As a silicone type surfactant, polyether modified silicone oil is mentioned, for example.

In order to easily apply the coating solution to the surface of the film, the surface of the film may be subjected to a surface treatment such as corona treatment, frame treatment, plasma treatment and ozone treatment before applying the coating solution.

Moreover, a crosslinking agent, a light stabilizer, and a ultraviolet absorber can be added to the said coating liquid as needed.

The anti-fogging coating layer may be a monolayer film or a multilayer film of two or more layers.

The method of manufacturing an inflation film according to an aspect of the present invention may further include a developing process of deploying an inflation film on a tube after the film forming process or the coating process. Inflation film according to an aspect of the present invention, since the inner layer includes a silicone-based antifouling agent, it is possible to easily deploy the inflation film on a tube in the deployment process.

<Summary>

Inflation film according to an aspect of the present invention has an inner layer comprising a silicone-based antifouling agent.

The present invention is not limited to the above-described embodiments, and various modifications are possible within the scope shown in the claims, and the embodiments obtained by appropriately combining the technical means disclosed in other embodiments are also included in the technical scope of the present invention. Included. In addition, new technical features can be formed by combining the technical means disclosed in each embodiment.

Example

Hereinafter, the Example of this invention is shown.

<IR measurement of SAB03390LD　Anti　Dust>

In order to analyze the components contained in Kafrit's SAB03390LD Anti Dust, IR measurement was performed. 1 is a graph showing the IR measurement results of films obtained by press-molding SAB03390LD Anti Dust and F200-0 (LDPE: low-density polyethylene, manufactured by Sumitomo Chemical Co., Ltd.) to a thickness of 0.1 mm, respectively. As a result of IR measurement, it was recognized that SAB03390LD Anti Dust had a characteristic absorption characteristic of silicon-based compounds. Specifically, absorption was recognized at 790 cm ^-1 corresponding to characteristic absorption of Si-CH ₃ and 1070 cm ^-1 corresponding to characteristic absorption of Si-O-Si. Therefore, it was estimated that SAB03390LD Anti Dust contained a silicone-based compound. In addition, it was estimated that LDPE was included in SAB03390LD Anti Dust because the same absorption as F200-0 was also recognized in SAB03390LD Anti Dust as a result of IR measurement.

<Production of additive master batch pellets>

(1) Preparation of additive master batch pellets (MB1)

35% by weight of low-density polyethylene (trade name: SUMIKATHENE F200-0, manufactured by Sumitomo Chemical Co., Ltd.) (hereinafter referred to as PE-4) and a hydrotalcite compound (trade name: MAGCLEAR, manufactured by Toda Industries, Ltd.) (hereinafter referred to as B1) 65 % by weight (however, the sum of PE-4 and B1 is 100% by weight) was kneaded. Then, it granulated with a granulator, and produced the master batch pellet (henceforth MB1) which is an additive.

(2) Preparation of additive master batch pellets (MB2~4)

The additive master batch pellets (MB2-4) were prepared by changing the raw material of the additive master batch pellet as follows.

MB2: PE-4/C1=73/27 (wt%/wt%)

MB3: PE-4/C2=85/15 (wt%/wt%)

MB4: EVA-1/C3/C4=90/7.5/2.5 (wt%/wt%/wt%)

In addition, the meaning of abbreviation is as follows.

EVA-1: ethylene/vinyl acetate copolymer (trade name: EVATATE H2020, manufactured by Sumitomo Chemical Co., Ltd.)

EVA-2: ethylene/vinyl acetate copolymer (trade name: VF324G, manufactured by Ube Maruzen Polyethylene Co., Ltd.)

C1: hindered amine compound (trade name: Chimassorb 119, manufactured by BASF)

C2: hindered amine compound (trade name: Tinuvin 622, manufactured by BASF)

C3: 2-(3-t-Butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole

C4: 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole

<Production of polyethylene pellets>

Polyethylene pellets (PE-1 to PE-3) were produced by the method shown below.

<Adjustment of catalyst components>

(1) Preparation of promoter carrier

Silica (Davison's Sylopol 948; 50% volume average particle diameter = 55 µm; pore capacity = 1.67 ml/g; specific surface area = 325 m ² /g) 2.8 kg and 24 kg of toluene were added and stirred. Thereafter, after cooling to 5°C, a mixed solution of 0.9 kg of 1,1,1,3,3,3-hexamethyldisilazane and 1.4 kg of toluene was added dropwise over 30 minutes while maintaining the temperature of the reactor at 5°C. did. After completion of the dropwise addition, the mixture was stirred at 5°C for 1 hour, then heated to 95°C, stirred at 95°C for 3 hours, and filtered. The obtained solid product was washed 6 times with 20.8 kg of toluene. After that, 7.1 kg of toluene was added to form a slurry, and the mixture was left overnight.

3.46 kg of a hexane solution of diethyl zinc (diethyl zinc concentration: 50 wt %) and 2.05 kg of hexane were added to the obtained slurry and stirred. After cooling to 5°C, a mixed solution of 1.55 kg of 3,4,5-trifluorophenol and 2.88 kg of toluene was added dropwise over 60 minutes while maintaining the temperature of the reactor at 5°C. After completion of the dropwise addition, the mixture was stirred at 5°C for 1 hour, then heated to 40°C and stirred at 40°C for 1 hour. Then, it was cooled to 5 °C, and 0.221 kg of H ₂ O was added dropwise while maintaining the temperature of the reactor at 5 °C for 1.5 hours. After completion of the dropwise addition, the mixture was stirred at 5°C for 1.5 hours, then heated to 40°C and stirred at 40°C for 2 hours, then heated to 80°C and stirred at 80°C for 2 hours. After stirring, the supernatant was removed at room temperature to a residual amount of 16L, 11.6 kg of toluene was added, and then the temperature was raised to 95° C. and stirred for 4 hours. After stirring, the supernatant was removed at room temperature to obtain a solid product. The obtained solid product was washed 4 times with 20.8 kg of toluene and 3 times with 24 L of hexane. Thereafter, a solid component (hereinafter referred to as a cocatalyst carrier (a)) was obtained by drying.

(2) Preparation of prepolymerization catalyst component (1)

After putting 80 liters of butane into an autoclave with a stirrer with an internal volume of 210 L substituted with nitrogen in advance, 91.8 mmol of racemic-ethylenebis (1-indenyl) zirconium diphenoxide was added, and the autoclave was heated to 50 ° C. Stirred for 2 hours. Next, 0.7 kg of the co-catalyst carrier (a) is added, the autoclave is cooled to 31° C. to stabilize the system, and 0.1 kg of ethylene and 0.1 L of hydrogen (at room temperature and normal pressure volume) are added, followed by triisobutyl aluminum 267 mmol was added to initiate polymerization. After 30 minutes elapsed while continuously supplying ethylene and hydrogen at 0.6 kg/hour and 0.5 L (room temperature and normal pressure volume), the temperature was raised to 50°C, and ethylene and hydrogen were supplied at 3.6 kg/hour and 10.9 liters (room temperature and normal pressure volume), respectively. )/hour to carry out pre-polymerization for a total of 6 hours. After polymerization, ethylene, butane, hydrogen, etc. were purged, and the remaining solid was vacuum dried at room temperature to obtain a prepolymerization catalyst component (1) containing 37 g of polyethylene per 1 g of the promoter carrier (a).

(3) Preparation of powder of ethylene/1-hexene copolymer

Ethylene and 1-hexene were copolymerized in a continuous fluidized bed gas phase polymerization apparatus using the prepolymerization catalyst component (1). The polymerization conditions were a temperature of 85° C., a voltage of 2 MPa, a molar ratio of hydrogen to ethylene of 1.22%, and a molar ratio of 1-hexene to ethylene of 1.31%. In order to maintain a constant gas composition during polymerization, ethylene, 1-Hexene and hydrogen were continuously supplied. In addition, the total powder weight of the fluidized bed was maintained at 80 kg, and the prepolymerization catalyst component and triisobutylaluminum were continuously supplied at a constant ratio so that the average polymerization time was 4 hours. By polymerization, an ethylene/1-hexene copolymer powder was obtained with a polymerization efficiency of 20.5 kg/hour.

(4) granulation of ethylene/1-hexene copolymer powder

The ethylene/1-hexene copolymer powder obtained in (3) was fed by an extruder (LCM50 of Kobe Steel, Ltd.) at a feed rate of 50 kg/hr, a screw rotation speed of 450 rpm, a gate opening degree of 4.2 mm, a suction pressure of 0.2 MPa, By granulating under the conditions of a resin temperature of 200 to 230°C, pellets of an ethylene/1-hexene copolymer (hereinafter referred to as PE-1) were obtained. PE-1 had an MFR of 0.5 g/10 min and a density of 921 kg/m 3 .

<Production of polyethylene pellets (PE-2)>

(5) Preparation of ethylene/1-hexene copolymer powder

Ethylene and 1-hexene were copolymerized in a continuous fluidized bed gas phase polymerization apparatus using the prepolymerization catalyst component (1). The polymerization conditions were a temperature of 80° C., a voltage of 2 MPa, a molar ratio of hydrogen to ethylene of 1.48%, and a molar ratio of 1-hexene to ethylene of 1.70%, and during polymerization, ethylene, 1-hexene and hydrogen were used to keep the gas composition constant. was continuously supplied. In addition, the prepolymerization catalyst component and triisobutylaluminum were continuously supplied at a constant ratio so that the total powder weight of the fluidized bed was maintained at 80 kg and the average polymerization time was 4 hours. By polymerization, an ethylene/1-hexene copolymer powder was obtained with a polymerization efficiency of 20.3 kg/hour.

(6) granulation of ethylene/1-hexene copolymer powder

The ethylene/1-hexene copolymer powder obtained in (5) was fed by an extruder (LCM50 of Kobe Steel, Ltd.) at a feed rate of 50 kg/hour, a screw rotation speed of 450 rpm, a gate opening degree of 4.2 mm, a suction pressure of 0.2 MPa, By granulating under the conditions of a resin temperature of 200 to 230°C, pellets of an ethylene/1-hexene copolymer (hereinafter referred to as PE-2) were obtained. PE-2 had an MFR of 0.4 g/10 min and a density of 913 kg/m 3 .

<Production of polyethylene pellets (PE-3)>

PE-1 and PE-2 were mixed in a weight ratio of 1:1 to obtain PE-3.

[Example 1]

<Production of film>

A three-layer tubular film was molded at a processing temperature of 160° C. using a three-layer inflation film molding machine.

Specifically, 60% by weight of PE-2 and 36% by weight of ethylene/1-hexene copolymer (trade name: SUMIKATHENE E FV203, manufactured by Sumitomo Chemical Co., Ltd.) (hereinafter referred to as PE-5) and 4% by weight of MB6 (provided that PE-2, PE-5, and MB6 (total of 100% by weight) were mixed, and then put into the extruder for the outer layer. In addition, after mixing 70% by weight of EVA-2, 3% by weight of MB5, 12% by weight of MB1, and 15% by weight of reclaimed material (provided that the total of EVA-2, MB5, MB1 and reclaimed material is 100% by weight), It was put into the extruder for the intermediate layer. In addition, silicone-based PE master pellets (trade name: SAB03390LD, manufactured by Anti-Dust Kafrit) (hereinafter referred to as S-MB) 1.6% by weight, PE-3 45.2% by weight, PE-5 45% by weight, MB7　6.2% by weight and Eruka Acid amide PE master pellets (trade name: EMB-10, manufactured by Sumitomo Chemical Co., Ltd.) (hereinafter referred to as E-MB) 2% by weight (provided that S-MB, PE-3, PE-5, MB7, E-MB and After mixing the total of aminosilicate PE master pellets (trade name: CMB674SC2, manufactured by Sumika Color Co., Ltd.) (hereinafter referred to as SI-MB) as 100% by weight), it was put into an inner layer extruder. Melt-kneading was carried out in each extruder. After that, from the 1100 mm Φ die, the discharge amount is adjusted so that the inner layer becomes 30 μm, the middle layer becomes 90 μm, and the outer layer becomes 30 μm, and the molten resin composition of each layer is extruded and cooled to form a three-layer tubular film, cut and three layers of inflation film was obtained. On the other hand, the reclaimed material used as the intermediate layer is the raw material of the obtained inflation film (inflation film whose dimensions have changed until it is stabilized in mass production, and inflation film that has not been made into a product due to appearance problems such as wrinkles) by crushing and melting the material. It is pelletized. The raw materials used as the inner layer are shown in Table 1.

[Example 2]

As shown in Table 1, a three-layer inflation film was obtained in the same manner as in Example 1, except that 0.6 wt% of S-MB and 46.2 wt% of PE-3 among the raw materials used as the inner layer were changed.

[Example 3]

As shown in Table 1, a three-layer inflation film was obtained in the same manner as in Example 1, except that 0.2 wt% of S-MB and 46.6 wt% of PE-3 among the raw materials used as the inner layer were changed.

[Comparative Example 1]

As shown in Table 1, a three-layer inflation film was obtained in the same manner as in Example 1, except for changing to 2.5 wt% of S-MB and 44.3 wt% of PE-3 among the raw materials used as the inner layer.

[Comparative Example 2]

As shown in Table 1, a three-layer inflation film was obtained in the same manner as in Example 1, except that S-MB was not added among the raw materials used as the inner layer and changed to PE-3 46.8 wt%.

[Comparative Example 3]

As shown in Table 1, a three-layer inflation film was obtained in the same manner as in Comparative Example 1, except that 4% by weight of SI-MB and 42.8% by weight of PE-3 was added among the raw materials used as the inner layer.

[Comparative Example 4]

As shown in Table 1, a three-layer inflation film was obtained in the same manner as in Comparative Example 1, except that 0.5 wt% of SI-MB and 46.3 wt% of PE-3 was added among the raw materials used as the inner layer.

About the inflation of Examples 1-3 and Comparative Examples 1-4, transparency, openness, and fabric wrinkle were evaluated. Each evaluation criterion is shown below, and the result is shown in Table 2.

(Evaluation of transparency)

Sensory evaluation of the transparency was relatively performed on the basis of the inflation film of Comparative Example 2.

(circle): The deterioration of transparency was not recognized compared with the comparative example 2.

x: Transparency deteriorated compared with the comparative example 2.

(evaluation of individuality)

○: When one end of the double film was lifted with a finger, the film on the other side was naturally peeled off.

x: When one end of the double film was lifted with a finger, the film of the other side did not peel naturally.

(Evaluation of fabric wrinkles)

○: In the winding process of the double inflation film after 30 minutes or more after the replacement of the raw material, 10 or more wrinkles did not occur visually for 30 minutes.

×: In the winding process of the double inflation film after 30 minutes or more after the replacement of the raw material, 10 or more wrinkles were observed with the naked eye for 30 minutes.

The inflation film according to an aspect of the present invention can be preferably used as an agricultural film, such as a covering film for an agricultural or horticultural facility used in a greenhouse or tunnel for growing plants.

Claims (1)

An inflation film having an inner layer comprising a silicone-based antifouling agent.

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