WO2020085440A1 - Moisture-absorbing resin composition, moisture-absorbing film, and production method for moisture-absorbing film - Google Patents

Moisture-absorbing resin composition, moisture-absorbing film, and production method for moisture-absorbing film Download PDF

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Publication number
WO2020085440A1
WO2020085440A1 PCT/JP2019/041748 JP2019041748W WO2020085440A1 WO 2020085440 A1 WO2020085440 A1 WO 2020085440A1 JP 2019041748 W JP2019041748 W JP 2019041748W WO 2020085440 A1 WO2020085440 A1 WO 2020085440A1
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film
moisture
zeolite
mass
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PCT/JP2019/041748
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French (fr)
Japanese (ja)
Inventor
周 加藤
直美 関谷
香織 角田
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共同印刷株式会社
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Priority to JP2020552594A priority Critical patent/JPWO2020085440A1/en
Publication of WO2020085440A1 publication Critical patent/WO2020085440A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment

Definitions

  • hygroscopic films containing zeolite as a hygroscopic agent may be used.
  • a film described in Patent Document 1 is known.
  • Patent Document 2 includes a zeolite having an average particle diameter D50 of 100 nm or less, a specific oxide (excluding zeolite) having an average particle diameter D50 of 100 nm or less, a specific ester compound, and a thermoplastic resin, and a light transmittance.
  • a hygroscopic film is disclosed.
  • Patent Document 2 has extremely high transparency and is useful as a sealing film for organic EL or the like.
  • Patent Documents 3 and 4 describe methods for producing nano-sized zeolite.
  • An object of the present invention is to provide a hygroscopic resin composition useful as a packaging material, a film containing the same, and a method for producing the same.
  • ⁇ Mode 1 Zeolite having an average particle diameter D50 of 300 nm or less, The haze, which contains an ester compound and a thermoplastic resin, and is measured in a film having a thickness of 100 ⁇ m before moisture absorption according to JIS K7105 is 25% or more and 80% or less, Hygroscopic resin composition.
  • ⁇ Mode 2 The composition according to aspect 1, wherein the haze measured after moisture absorption is 10% or more lower than the haze.
  • ⁇ Mode 3 The composition according to aspect 1 or 2, wherein the average particle diameter D50 of the zeolite is more than 100 nm.
  • ⁇ Mode 4 >> 4.
  • Composition. ⁇ Mode 5 The composition according to any one of aspects 1 to 4, wherein the thermoplastic resin is a polyolefin resin.
  • ⁇ Mode 6 >> 6.
  • the melt flow rate measured according to JIS K7210 under the conditions of a temperature of 190 ° C. and a load of 21.18 N is 0.3 g / 10 min or more and 30 g / 10 min or less, and the melt flow rate is any one of Aspects 1 to 5.
  • the composition according to. ⁇ Mode 7 >> 7.
  • ⁇ Mode 8 >> 8.
  • ⁇ Aspect 9 >> A hygroscopic film comprising the composition according to any one of aspects 1 to 8.
  • ⁇ Mode 10 >> A hygroscopic laminate having the film according to Aspect 8 or 9 between an outer skin layer and an inner skin layer.
  • ⁇ Mode 11 A method for producing a moisture absorbent film, which comprises molding the composition according to any one of aspects 1 to 8 by a T-die method or an inflation method.
  • the moisture absorbent resin composition of the present invention has a mean particle size D50 of 300 nm or less of zeolite, an ester compound and a thermoplastic resin, and the haze when measured in a film having a thickness of 100 ⁇ m before moisture absorption according to JIS K7105. , 25% or more and 80% or less.
  • a conventional hygroscopic film containing zeolite as a hygroscopic agent as described in Patent Document 1 becomes transparent after moisture absorption, but is white before moisture absorption, and when used in a packaging container or the like, check the inside. Was difficult.
  • the film described in Patent Document 2 has extremely high transparency because it is used as a sealing film for organic EL or the like. Therefore, when the film described in Patent Document 2 is used in a packaging container, the contents can be confirmed due to its high transparency.
  • Patent Document 1 when the film described in Patent Document 2 is used in a packaging container or the like, it is not possible to visually determine whether or not the film has absorbed moisture.
  • the moisture-absorbing film of Patent Document 1 has a property of becoming transparent after moisture absorption, and thus it is possible to easily determine whether or not moisture has been absorbed.
  • the present inventors formed a film of the specific composition of the present invention, it is possible to confirm the inside when used for a packaging container and the like, and to determine whether or not it has absorbed moisture. I found it easy to do.
  • the resin composition of the present invention has a haze of 25% or more, 30% or more, 40% or more when measured as a film having a thickness of 100 ⁇ m before moisture absorption according to JIS K7105. It may be 50% or more, or 60% or more.
  • the haze is 80% or less, and may be 70% or less, 60% or less, or 50% or less.
  • the haze may be 25% or more and 70% or less, or 30% or more and 60% or less.
  • the film can be provided with transparency to the extent that the inside can be confirmed when used as a packaging container and the like, and opacity to the extent that the change in transparency can be seen after absorbing moisture. In particular, if the change in haze before and after moisture absorption is 10% or more, 20% or more, or 30% or more, the change in color is easily visible.
  • the resin composition of the present invention has a melt flow rate of 0.3 g / 10 min or more and 30 g / 10 min or less when measured according to JIS K7210 under the conditions of a temperature of 190 ° C. and a load of 21.18 N. preferable.
  • the melt flow rate may be 0.5 g / 10 min or more, 0.8 g / 10 min or more, 1.0 g / 10 min or more, 3.0 g / 10 min or more, or 5.0 g / 10 min or more, 20 g / 10 min Or less, or 15 g / 10 min or less, 10 g / 10 min or less, 8.0 g / 10 min or less, or 5.0 g / 10 min or less.
  • the melt flow rate may be 0.5 g / 10 min or more and 10 g / 10 min or less.
  • the resin composition of the present invention can be relatively easily formed into a film by the T-die method or the inflation method.
  • T A film cannot be formed by a die method or an inflation method, and a specific composition of a resin composition having preferable thermal characteristics for forming the film is not disclosed.
  • the zeolite contained in the resin composition of the present invention is zeolite particles having an average particle diameter D50 of 300 nm or less.
  • the pore (absorption port) diameter of zeolite may be 0.3 nm or more and 1 nm or less, and may be 0.3 nm or more and 0.5 nm or less.
  • the average particle diameter D50 of zeolite is 300 nm or less from the viewpoint of giving appropriate haze to the composition.
  • the average particle size D50 of the zeolite may be 250 nm or less, 200 nm or less, 150 nm or less, or 100 nm or less.
  • the average particle diameter D50 of the zeolite may be 10 nm or more, 30 nm or more, 50 nm or more, or 100 nm or more.
  • the average particle diameter D50 of zeolite may be 10 nm or more and 300 nm or less, or more than 100 nm and 250 nm or less.
  • the value of the atomic ratio of Si to Al in the zeolite (Si / Al) is arbitrary, and may be, for example, 1 or more, 2 or more, 3 or more, 5 or more, 10 or more, or 15 or more, and for example, 80 Hereafter, it may be 60 or less, 50 or less, 40 or less, or 30 or less.
  • the zeolite used in the present invention is preferably hydrophilic, and Na-A type zeolite is particularly preferably used.
  • the zeolite used in the present invention can be produced, for example, by the methods described in Patent Documents 3 and 4. Such a zeolite may be used by adjusting the bulk density as described in Patent Document 2.
  • Zeolite can be obtained, for example, by dispersing a raw material zeolite represented by the following formula (1) in an aqueous solution containing a silicate or aluminosilicate represented by the following formula (2) and recrystallizing the raw material zeolite.
  • B in the above formula (1) may be, for example, 2 to 60 or 20 to 80.
  • c may be, for example, 0.01 to 1.
  • the ratio d / g in the above formula (2) may be, for example, 0.003 to 0.010.
  • the ratio e / g may be, for example, 0 or 0.000003 to 0.000250.
  • the ratio f / g may be, for example, 0.0001 to 0.0160 or 0.006 to 0.025.
  • the raw material zeolite of the above formula (1) for example, NaSiAlO 4 , NaSi 12 AlO 26 , NH 4 Si 19 AlO 40, etc. can be used.
  • the zeolite obtained as described above may be subjected to ion exchange, pulverization, or both, and then used.
  • the content of zeolite in the resin composition of the present invention is not particularly limited as long as the advantageous effects of the present invention can be provided.
  • the content of zeolite may be 5 mass% or more, 10 mass% or more, 20 mass% or more, 30 mass% or more, 40 mass% or more, or 50 mass% or more, 70 mass% or less, 60 It may be less than or equal to 50% by weight, less than or equal to 50% by weight, or less than or equal to 40% by weight.
  • the content of zeolite may be 20% by mass or more and 60% by mass or less, or 30% by mass or more and 50% by mass or less.
  • the resin composition of the present invention comprises one or more elements selected from Al, Si, Ti, and Zr having an average particle diameter D50 of 100 nm or less as used in the invention described in Patent Document 2. It is not necessary to include oxides (excluding zeolite).
  • the resin composition of the present invention does not contain such an oxide, it is not necessary to consider the mixed state of the zeolite and the oxide, the dispersed state of the oxide, etc., so that it can be easily produced, The cost can also be reduced.
  • the resin composition of the present invention contains an ester compound.
  • an ester compound a compound used as an emulsifying agent or the like can be used, and the zeolite used in the present invention and the thermoplastic resin can be mixed.
  • an ester compound having an HLB value of 5 or less may be used.
  • the HLB value is an index indicating hydrophilicity or lipophilicity.
  • the HLB value of the ester compound being 5 or less means that the ester compound has a high lipophilicity, and is, for example, a numerical value in a range used as an antifoaming agent or an emulsifier of an emulsion.
  • the HLB value of the ester compound may be 5 or more as long as the advantageous effects of the present invention are obtained, and for example, the HLB value of the ester compound is 8.0 or less, 6.0 or less, 5. It may be 0 or less, 4.5 or less, 4.0 or less, or 3.5 or less, and may be 2.0 or more, 2.5 or more, or 3.0 or more.
  • the HLB value of the ester compound may be 2.0 or more and 5.0 or less, or 2.5 or more and 4.5 or less.
  • the ester compound is, for example, a monoester compound of a polyhydric alcohol and a fatty acid.
  • the polyhydric alcohol may be, for example, glycerin, alkylene glycol or the like.
  • the fatty acid may be, for example, a saturated or unsaturated fatty acid having 12 to 24 carbon atoms.
  • the ester compound may be a monoester of an alkylene glycol having 2 to 6 carbon atoms and a fatty acid having 15 to 24 carbon atoms.
  • the alkylene glycol may be, for example, ethylene glycol, propylene glycol, diethylene glycol or the like.
  • the above-mentioned fatty acids having 15 to 24 carbon atoms may be saturated or unsaturated, and may be, for example, stearic acid, behenic acid and the like.
  • the ester compound may be, for example, propylene glycol monostearate, propylene glycol monobehenate, or the like.
  • the content of the ester compound in the resin composition of the present invention is not particularly limited as long as the advantageous effects of the present invention can be provided.
  • the content of the ester compound is 2.0% by mass or more and 15% by mass or less, and may be 2.5% by mass or more, 3.0% by mass or more, or 5.0% by mass or more. It may be less than or equal to 10% by weight, less than or equal to 10% by weight, less than or equal to 8.0% by weight, or less than or equal to 6.0% by weight.
  • the content of the ester compound may be 2.5% by mass or more and 12% by mass or less, or 3.0% by mass or more and 10% by mass or less.
  • the resin composition of the present invention contains a thermoplastic resin, particularly a thermoplastic resin containing ethylene units.
  • the resin composition of the present invention is preferably a thermoplastic resin containing a polar group such as a carboxylic acid group or a carboxylic acid ester group and an ethylene unit.
  • thermoplastic resin examples include a polyolefin resin
  • examples of the polyolefin resin include a polyethylene resin, a polypropylene resin, and a copolymer of ethylene and an oxygen-containing ethylenically unsaturated monomer.
  • examples of the copolymer of ethylene and an oxygen-containing ethylenically unsaturated monomer include EVOH (ethylene-vinyl alcohol copolymer) and the like.
  • the polyethylene-based resin includes a repeating unit of an ethylene group in a main chain of a polymer, including 30 mol% or more, 40 mol% or more, 50 mol% or more, 60 mol% or more, 70 mol% or more, or 80 mol% or more.
  • Resins such as low density polyethylene (LDPE), linear low density polyethylene (LLDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), ethylene-acrylic acid copolymer (EAA), ethylene- Methacrylic acid copolymer (EMAA), ethylene-methyl methacrylate copolymer (EMMA), ethylene-ethyl acrylate copolymer (EEA), ethylene-methyl acrylate copolymer (EMA), ethylene-vinyl acetate copolymer ( EVA), carboxylic acid modified polyethylene, cal Phosphate-modified ethylene vinyl acetate copolymer, ionomer, and their derivatives, and selected from the group consisting of mixtures.
  • LDPE low density polyethylene
  • LLDPE linear low density polyethylene
  • MDPE medium density polyethylene
  • HDPE high density polyethylene
  • EAA ethylene-acrylic acid copolymer
  • EMMA ethylene-methyl methacrylate copolymer
  • EMMA
  • a polypropylene-based resin is a resin containing a repeating unit of a propylene group in the main chain of a polymer, which is 30 mol% or more, 40 mol% or more, 50 mol% or more, 60 mol% or more, 70 mol% or more, or 80 mol% or more.
  • PP polypropylene
  • random PP random polypropylene
  • block PP block polypropylene
  • chlorinated polypropylene carboxylic acid modified polypropylene, and derivatives thereof, and mixtures thereof.
  • ethylene-vinyl acetate copolymer can be mentioned among these.
  • the vinyl acetate content in the ethylene-vinyl acetate copolymer may be 10% by mass or more, 15% by mass or more, 20% by mass or more, 25% by mass or more, or 30% by mass or more, and 60% by mass or less, 55% by mass. % Or less, 50% by mass or less, 45% by mass or less, or 40% by mass or less.
  • the vinyl acetate content in the ethylene-vinyl acetate copolymer may be, for example, 5% by mass or more and 50% by mass or less, or 20% by mass or more and 40% by mass or less.
  • the content of the thermoplastic resin in the resin composition of the present invention may be 30% by mass or more, 40% by mass or more, 50% by mass or more, 60% by mass or more, or 70% by mass or more, and 80% by mass or less. , 70 mass% or less, 60 mass% or less, or 50 mass% or less.
  • the content of the thermoplastic resin may be 30% by mass or more and 80% by mass or less, or 40% by mass or more and 70% by mass or less.
  • the resin composition of the present invention contains, in addition to the above-mentioned components, if necessary, a lubricant, an antistatic agent, a release agent, a plasticizer, an antioxidant, an antibacterial agent, an antifungal agent, an ultraviolet absorber. Can further contain optional additives such as.
  • the moisture absorbent film of the present invention contains or consists of the above moisture absorbent resin composition.
  • the thickness of the film of the present invention may be 10 ⁇ m or more, 20 ⁇ m or more, 30 ⁇ m or more, or 40 ⁇ m or more, and may be 300 ⁇ m or less, 200 ⁇ m or less, 100 ⁇ m or less, 90 ⁇ m or less, 80 ⁇ m or less, 70 ⁇ m or less, or 60 ⁇ m or less.
  • the film of the present invention may have a thickness of 10 ⁇ m or more and 300 ⁇ m or less, or 20 ⁇ m or more and 100 ⁇ m or less.
  • the moisture absorbent laminate of the present invention can be obtained by laminating the above moisture absorbent film with another film, for example, a skin layer.
  • the laminate of the present invention may be a laminate of the above-mentioned film and a normal film used as a packaging material.
  • the moisture absorbent laminate of the present invention may include the moisture absorbent film described above and a transparent barrier film (for example, a PET film obtained by vapor deposition of silica, alumina, or the like, a polyamide film, or the like).
  • a transparent barrier film for example, a PET film obtained by vapor deposition of silica, alumina, or the like, a polyamide film, or the like.
  • the laminate of the present invention may have a skin layer on at least one surface of the film, for example, an outer skin layer and an inner skin layer on both surfaces thereof.
  • the skin layer improves the film formation stability of the film of the present invention, imparts surface smoothness, prevents the zeolite in the film from falling off, prevents the zeolite from being directly exposed to the outside, and mechanically when used as a packaging container. It has at least one function of improving strength (for example, tensile strength) and improving heat seal strength with other films or laminates.
  • the resin forming the skin layer a resin generally used for films can be used.
  • the resins constituting the respective skin layers may be the same or different.
  • resin constituting the skin layer for example, polystyrene resin, polyester resin, acrylic resin, polyamide resin, polyvinyl alcohol resin, polyurethane resin, polyolefin resin, polycarbonate resin, polysulfone resin, and derivatives thereof, And mixtures thereof.
  • the thickness of the skin layer can be 1 ⁇ m or more, 3 ⁇ m or more, 5 ⁇ m or more, or 7 ⁇ m or more, and can be 50 ⁇ m or less, 40 ⁇ m or less, 30 ⁇ m or less, 20 ⁇ m or less, or 15 ⁇ m or less per one surface.
  • the thickness of these skin layers may be the same or different.
  • the method for forming the moisture-absorbing film or the laminate is not particularly limited, and examples thereof include a single-layer or multi-layer inflation method, a T-die method, a casting method, etc., and the T-die method or the inflation method is particularly preferable.
  • a pellet-shaped moisture-absorbent resin composition (masterbatch) should be prepared by extruding a mixture of the materials contained in the moisture-absorbent resin composition in a pellet form and cooling the mixture. You can Alternatively, the materials contained in the hygroscopic resin composition may be kneaded to form a film as it is.
  • the kneading can be performed using, for example, a batch kneader such as a kneader, a Banbury mixer, a Henschel mixer, a mixing roll, or a continuous kneader such as a twin-screw kneader.
  • a kneading temperature of 60 ° C. or higher, 80 ° C. or higher, 100 ° C. or higher, or 120 ° C. or higher and 170 ° C. or lower, 150 ° C. or lower, or 130 ° C. or lower, 0.5. Kneading can be performed for a kneading time of not less than 30 minutes and not more than 30 minutes.
  • the moisture-absorbing film of the present invention is obtained by kneading the materials contained in the moisture-absorbent resin composition described above, for example, with a biaxial kneading extruder or the like, and as it is, 100 ° C or higher, 120 ° C or higher, 130 ° C or higher, 135 ° C or higher, 140 ° C or higher. Or 150 ° C. or more, 250 ° C. or less, 220 ° C. or less, or less than 200 ° C., to form moisture absorption by molding by an inflation molding method or a T-die method.
  • the masterbatch can be prepared as described above, reheated, and manufactured by an inflation molding method, a T-die method, or the like.
  • a skin layer made of, for example, an olefin resin may be coextruded on both sides of the moisture absorption film, or a film to be the skin layer may be laminated by thermocompression bonding to form a moisture absorption laminate.
  • thermoplastic resin Na-A type zeolite, and ester compound (propylene glycol monobehenate, HLB value 3.4) were melt-kneaded at 160 ° C. for 10 minutes using a Banbury mixer with the composition shown in Table 1, The resin composition of each example was obtained.
  • ⁇ Haze> The resin composition was cut into a predetermined weight, and a film having a thickness of 100 ⁇ m was produced by hot press molding.
  • the press conditions were a temperature of 160 ° C. and a pressure of 40 to 60 MPa for 2 minutes.
  • the film thus obtained was cut into a 50 mm square, and the haze was measured according to JIS K7105 using a haze measuring instrument (Murakami Color Research Laboratory, HR-100).
  • the film was left to stand in an environment of 23 ° C. and 50%, allowed to absorb moisture until the weight change after moisture absorption became constant, and then measured by the same method as above.
  • Table 1 shows the constitution and evaluation result of each example.

Abstract

This moisture-absorbing resin composition includes a zeolite that has an average particle size D50 of no more than 300 nm, an ester compound, and a thermoplastic resin. The haze of the moisture-absorbing resin composition as measured for a film that is 100 µm thick in accordance with JIS K7105 pre-moisture-absorption is 25%–80%.

Description

吸湿樹脂組成物、並びに吸湿フィルム及びその製造方法Hygroscopic resin composition, hygroscopic film and method for producing the same
　包装材料の分野においては、ゼオライトを吸湿剤として含む吸湿フィルムが用いられることがある。このようなフィルムとしては、例えば特許文献１に記載のようなフィルムが知られている。 In the field of packaging materials, hygroscopic films containing zeolite as a hygroscopic agent may be used. As such a film, for example, a film described in Patent Document 1 is known.
　また、医薬品、電子部品、精密機械等の分野に使用されるフィルムとして、透明性と吸湿性とを有するフィルムが用いられることがある。例えば特許文献２には、平均粒子径Ｄ５０が１００ｎｍ以下のゼオライト、平均粒子径Ｄ５０が１００ｎｍ以下の特定の酸化物（ゼオライトを除く）、特定のエステル化合物、及び熱可塑性樹脂を含む、光透過性吸湿フィルムが開示されている。 Also, a film having transparency and hygroscopicity may be used as a film used in fields such as pharmaceuticals, electronic parts, and precision machinery. For example, Patent Document 2 includes a zeolite having an average particle diameter D50 of 100 nm or less, a specific oxide (excluding zeolite) having an average particle diameter D50 of 100 nm or less, a specific ester compound, and a thermoplastic resin, and a light transmittance. A hygroscopic film is disclosed.
　特許文献２に記載のフィルムは、極めて高い透明性を有しており、有機ＥＬの封止用フィルム等に有用である。 The film described in Patent Document 2 has extremely high transparency and is useful as a sealing film for organic EL or the like.
　なお、ナノ粒径のゼオライトの製造方法が特許文献３及び４に記載されている。 Note that Patent Documents 3 and 4 describe methods for producing nano-sized zeolite.
特開２００３－１９２９０８号公報JP, 2003-192908, A 特開２０１８－１００３９０号公報Japanese Patent Laid-Open No. 2018-100390 特開２０１１－２４６２９２号公報JP, 2011-246292, A 特開２０１３－４９６０２号公報JP, 2013-49602, A
　本発明は、包装材料等として有用な吸湿樹脂組成物、並びにそれを含むフィルム及びその製造方法を提供することを目的とする。 An object of the present invention is to provide a hygroscopic resin composition useful as a packaging material, a film containing the same, and a method for producing the same.
　本発明者らは、以下の態様を有する本発明により、上記課題を解決できることを見出した。
《態様１》
　平均粒子径Ｄ５０が３００ｎｍ以下のゼオライト、
　エステル化合物、及び
　熱可塑性樹脂を含み、かつ
　ＪＩＳ　Ｋ７１０５に準拠して吸湿前の１００μｍの厚みのフィルムにいて測定したときのヘイズが、２５％以上８０％以下である、
吸湿樹脂組成物。
《態様２》
　吸湿後に測定したときのヘイズが、前記ヘイズより、１０％以上低い、態様１に記載の組成物。
《態様３》
　前記ゼオライトの平均粒子径Ｄ５０が１００ｎｍ超である、態様１又は２に記載の組成物。
《態様４》
　平均粒子径Ｄ５０が１００ｎｍ以下の、Ａｌ、Ｓｉ、Ｔｉ、及びＺｒから選択される１種以上の元素の酸化物（ゼオライトを除く）を含んでいない、態様１～３のいずれか一項に記載の組成物。
《態様５》
　前記熱可塑性樹脂が、ポリオレフィン系樹脂である、態様１～４のいずれか一項に記載の組成物。
《態様６》
　温度１９０℃かつ荷重２１．１８Ｎの条件の下でＪＩＳ　Ｋ７２１０に準拠して測定した場合のメルトフローレートが、０．３ｇ／１０ｍｉｎ以上３０ｇ／１０ｍｉｎ以下である、態様１～５のいずれか一項に記載の組成物。
《態様７》
　前記ゼオライトを、２０重量％以上６０重量％以下で含む、態様１～６のいずれか一項に記載の組成物。
《態様８》
　前記エステル化合物のＨＬＢ値が５以下である、態様１～７のいずれか一項に記載の組成物。
《態様９》
　態様１～８のいずれか一項に記載の組成物を含む、吸湿フィルム。
《態様１０》
　態様８又は９に記載のフィルムを、外スキン層と内スキン層との間に有する、吸湿積層体。
《態様１１》
　態様１～８のいずれか一項に記載の組成物をＴダイ法又はインフレーション法によって成形することを含む、吸湿フィルムの製造方法。 The present inventors have found that the above problems can be solved by the present invention having the following aspects.
<< Mode 1 >>
Zeolite having an average particle diameter D50 of 300 nm or less,
The haze, which contains an ester compound and a thermoplastic resin, and is measured in a film having a thickness of 100 μm before moisture absorption according to JIS K7105 is 25% or more and 80% or less,
Hygroscopic resin composition.
<< Mode 2 >>
The composition according to aspect 1, wherein the haze measured after moisture absorption is 10% or more lower than the haze.
<< Mode 3 >>
The composition according to aspect 1 or 2, wherein the average particle diameter D50 of the zeolite is more than 100 nm.
<< Mode 4 >>
4. The method according to any one of aspects 1 to 3, which does not include an oxide (excluding zeolite) of one or more elements selected from Al, Si, Ti, and Zr, having an average particle diameter D50 of 100 nm or less. Composition.
<< Mode 5 >>
The composition according to any one of aspects 1 to 4, wherein the thermoplastic resin is a polyolefin resin.
<< Mode 6 >>
6. The melt flow rate measured according to JIS K7210 under the conditions of a temperature of 190 ° C. and a load of 21.18 N is 0.3 g / 10 min or more and 30 g / 10 min or less, and the melt flow rate is any one of Aspects 1 to 5. The composition according to.
<< Mode 7 >>
7. The composition according to any one of aspects 1 to 6, which contains the zeolite in an amount of 20% by weight or more and 60% by weight or less.
<< Mode 8 >>
8. The composition according to any one of aspects 1 to 7, wherein the ester compound has an HLB value of 5 or less.
<< Aspect 9 >>
A hygroscopic film comprising the composition according to any one of aspects 1 to 8.
<< Mode 10 >>
A hygroscopic laminate having the film according to Aspect 8 or 9 between an outer skin layer and an inner skin layer.
<< Mode 11 >>
A method for producing a moisture absorbent film, which comprises molding the composition according to any one of aspects 1 to 8 by a T-die method or an inflation method.
《吸湿樹脂組成物》
　本発明の吸湿樹脂組成物は、平均粒子径Ｄ５０が３００ｎｍ以下のゼオライト、エステル化合物及び熱可塑性樹脂を含み、ＪＩＳ　Ｋ７１０５に準拠して吸湿前の１００μｍの厚みのフィルムにいて測定したときのヘイズが、２５％以上８０％以下である。 <Hygroscopic resin composition>
The moisture absorbent resin composition of the present invention has a mean particle size D50 of 300 nm or less of zeolite, an ester compound and a thermoplastic resin, and the haze when measured in a film having a thickness of 100 μm before moisture absorption according to JIS K7105. , 25% or more and 80% or less.
　特許文献１に記載のようなゼオライトを吸湿剤として含む従来の吸湿フィルムは、吸湿後には透明になるが、吸湿前は白色であり、包装容器等に用いた場合には、内部を確認することが困難であった。 A conventional hygroscopic film containing zeolite as a hygroscopic agent as described in Patent Document 1 becomes transparent after moisture absorption, but is white before moisture absorption, and when used in a packaging container or the like, check the inside. Was difficult.
　特許文献２に記載のフィルムは、有機ＥＬの封止用フィルム等に用いるために、極めて高い透明性を有している。したがって、特許文献２に記載のフィルムを包装容器に使用すると、その高い透明性から内容物を確認することができる。 The film described in Patent Document 2 has extremely high transparency because it is used as a sealing film for organic EL or the like. Therefore, when the film described in Patent Document 2 is used in a packaging container, the contents can be confirmed due to its high transparency.
　しかしながら、特許文献２に記載のフィルムを包装容器等に使用した場合、フィルムが吸湿したかどうかの判断を目視で行うことができない。これに関して、特許文献１の吸湿フィルムは、吸湿後には透明になるという性質があるため、吸湿したかどうかの判断を容易にすることができる。 However, when the film described in Patent Document 2 is used in a packaging container or the like, it is not possible to visually determine whether or not the film has absorbed moisture. In this regard, the moisture-absorbing film of Patent Document 1 has a property of becoming transparent after moisture absorption, and thus it is possible to easily determine whether or not moisture has been absorbed.
　それに対して、本発明者らは、本発明の特定の組成物をフィルム化した場合には、包装容器等に使用した場合に内部の確認をすることができ、かつ吸湿したかどうかの判断を容易にできることを見出した。 On the other hand, when the present inventors formed a film of the specific composition of the present invention, it is possible to confirm the inside when used for a packaging container and the like, and to determine whether or not it has absorbed moisture. I found it easy to do.
　具体的には、本発明の樹脂組成物は、ＪＩＳ　Ｋ７１０５に準拠して吸湿前の１００μｍの厚みのフィルムにして測定したときのヘイズが、２５％以上であり、３０％以上、４０％以上、５０％以上、又は６０％以上であってもよい。また、ヘイズは、８０％以下であり、７０％以下、６０％以下、又は５０％以下であってもよい。例えば、ヘイズは、２５％以上７０％以下、又は３０％以上６０％以下であってもよい。このような範囲であれば、包装容器等として用いた場合に内部を確認できる程度の透明性と、吸湿後にその透明性の変化がわかる程度の不透明性をフィルムに与えることができる。特に、吸湿前と吸湿後でのヘイズの変化が１０％以上、２０％以上、又は３０％以上であると、その色の変化が視認しやすい。 Specifically, the resin composition of the present invention has a haze of 25% or more, 30% or more, 40% or more when measured as a film having a thickness of 100 μm before moisture absorption according to JIS K7105. It may be 50% or more, or 60% or more. The haze is 80% or less, and may be 70% or less, 60% or less, or 50% or less. For example, the haze may be 25% or more and 70% or less, or 30% or more and 60% or less. Within such a range, the film can be provided with transparency to the extent that the inside can be confirmed when used as a packaging container and the like, and opacity to the extent that the change in transparency can be seen after absorbing moisture. In particular, if the change in haze before and after moisture absorption is 10% or more, 20% or more, or 30% or more, the change in color is easily visible.
　本発明の樹脂組成物は、温度１９０℃かつ荷重２１．１８Ｎの条件の下でＪＩＳ　Ｋ７２１０に準拠して測定した場合のメルトフローレートが、０．３ｇ／１０ｍｉｎ以上３０ｇ／１０ｍｉｎ以下であることが好ましい。このメルトフローレートは、０．５ｇ／１０ｍｉｎ以上、０．８ｇ／１０ｍｉｎ以上、１．０ｇ／１０ｍｉｎ以上、３．０ｇ／１０ｍｉｎ以上、又は５．０ｇ／１０ｍｉｎ以上であってもよく、２０ｇ／１０ｍｉｎ以下、又は１５ｇ／１０ｍｉｎ以下、１０ｇ／１０ｍｉｎ以下、８．０ｇ／１０ｍｉｎ以下、又は５．０ｇ／１０ｍｉｎ以下であってもよい。例えば、このメルトフローレートは、０．５ｇ／１０ｍｉｎ以上１０ｇ／１０ｍｉｎ以下であってもよい。このような範囲であれば、本発明の樹脂組成物は、Ｔダイ法又はインフレーション法によってフィルムへの成形が比較的容易となる。これに関して、本発明者らが検討したところ、特許文献２では、熱プレスによってフィルムを製造することを具体的に開示しているものの、特許文献２に具体的に開示されている組成では、Ｔダイ法又はインフレーション法によってフィルムを成形することができず、そのフィルム成形のために好ましい熱特性を有する樹脂組成物の具体的な組成も開示されていなかった。 The resin composition of the present invention has a melt flow rate of 0.3 g / 10 min or more and 30 g / 10 min or less when measured according to JIS K7210 under the conditions of a temperature of 190 ° C. and a load of 21.18 N. preferable. The melt flow rate may be 0.5 g / 10 min or more, 0.8 g / 10 min or more, 1.0 g / 10 min or more, 3.0 g / 10 min or more, or 5.0 g / 10 min or more, 20 g / 10 min Or less, or 15 g / 10 min or less, 10 g / 10 min or less, 8.0 g / 10 min or less, or 5.0 g / 10 min or less. For example, the melt flow rate may be 0.5 g / 10 min or more and 10 g / 10 min or less. Within such a range, the resin composition of the present invention can be relatively easily formed into a film by the T-die method or the inflation method. Regarding this, when the present inventors examined, in Patent Document 2, although specifically disclosing that a film is produced by hot pressing, in the composition specifically disclosed in Patent Document 2, T A film cannot be formed by a die method or an inflation method, and a specific composition of a resin composition having preferable thermal characteristics for forming the film is not disclosed.
〈ゼオライト〉
　本発明の樹脂組成物に含有されるゼオライトは、平均粒子径Ｄ５０が３００ｎｍ以下のゼオライト粒子である。ゼオライトの細孔（吸収口）径は、０．３ｎｍ以上１ｎｍ以下であってよく、０．３ｎｍ以上０．５ｎｍ以下であってよい。 <Zeolite>
The zeolite contained in the resin composition of the present invention is zeolite particles having an average particle diameter D50 of 300 nm or less. The pore (absorption port) diameter of zeolite may be 0.3 nm or more and 1 nm or less, and may be 0.3 nm or more and 0.5 nm or less.
　ゼオライトの平均粒子径Ｄ５０とは、走査型電子顕微鏡(SEM)を用いて、無作為に選択した100個の粒子の長軸を測定し、その個数基準の粒度分布における積算値５０％での粒径を意味する。ゼオライトの平均粒子径Ｄ５０は、組成物に適度なヘイズを与える観点から、３００ｎｍ以下である。ゼオライトの平均粒子径Ｄ５０は、２５０ｎｍ以下、２００ｎｍ以下、１５０ｎｍ以下、又は１００ｎｍ以下であってよい。ゼオライトの平均粒子径Ｄ５０は、１０ｎｍ以上、３０ｎｍ以上、５０ｎｍ以上、又は１００ｎｍ以上であってよい。例えば、ゼオライトの平均粒子径Ｄ５０は、１０ｎｍ以上３００ｎｍ以下、又は１００ｎｍ超２５０ｎｍ以下であってもよい。 What is the average particle diameter D50 of zeolite? The long axis of 100 randomly selected particles is measured using a scanning electron microscope (SEM), and the particles with an integrated value of 50% in the particle size distribution based on the number are measured. Means diameter. The average particle diameter D50 of the zeolite is 300 nm or less from the viewpoint of giving appropriate haze to the composition. The average particle size D50 of the zeolite may be 250 nm or less, 200 nm or less, 150 nm or less, or 100 nm or less. The average particle diameter D50 of the zeolite may be 10 nm or more, 30 nm or more, 50 nm or more, or 100 nm or more. For example, the average particle diameter D50 of zeolite may be 10 nm or more and 300 nm or less, or more than 100 nm and 250 nm or less.
　ゼオライト中のＳｉとＡｌとの原子比（Ｓｉ／Ａｌ）の値は任意であり、例えば、１以上、２以上、３以上、５以上、１０以上、又は１５以上であってよく、例えば、８０以下、６０以下、５０以下、４０以下、又は３０以下であってよい。 The value of the atomic ratio of Si to Al in the zeolite (Si / Al) is arbitrary, and may be, for example, 1 or more, 2 or more, 3 or more, 5 or more, 10 or more, or 15 or more, and for example, 80 Hereafter, it may be 60 or less, 50 or less, 40 or less, or 30 or less.
　本発明で用いられるゼオライトとしては、吸湿性の観点から、親水性であることが好ましく、特にＮａ－Ａ型ゼオライトを使用することが好ましい。 From the viewpoint of hygroscopicity, the zeolite used in the present invention is preferably hydrophilic, and Na-A type zeolite is particularly preferably used.
　本発明で用いられるゼオライトは、例えば、特許文献３及び４に記載のような方法によって製造することができる。そのようなゼオライトを、特許文献２に記載のように、かさ密度を調整して用いてもよい。 The zeolite used in the present invention can be produced, for example, by the methods described in Patent Documents 3 and 4. Such a zeolite may be used by adjusting the bulk density as described in Patent Document 2.
　ゼオライトは、例えば、下記式（１）で表される原料ゼオライトを、下記式（２）で表されるシリケート又はアルミノシリケートを含有する水溶液に分散させ、再結晶させることにより、得ることができる。
　　ａＭ１ ２Ｏ・ｂＳｉＯ２・Ａｌ２Ｏ３・ｃＭｅＯ　　　（１）
｛式（１）中、Ｍ１はアルカリ金属原子、水素原子、又はアンモニウムイオンであり、Ｍｅはアルカリ土類金属イオン原子、ａは０．０１～１であり、ｂは１～８０であり、ｃは０～１である。｝
　　ｄＭ２ ２Ｏ・ｅＡｌ２Ｏ３・ｆＳｉＯ２・ｇＨ２Ｏ　　　（２）
｛式（２）中、比ｄ／ｇは０．０００３５～０．０２０００であり、比ｅ／ｇは０～０．０００２５であり、ｆ／ｇは０．０００１～０．０２５である。｝ Zeolite can be obtained, for example, by dispersing a raw material zeolite represented by the following formula (1) in an aqueous solution containing a silicate or aluminosilicate represented by the following formula (2) and recrystallizing the raw material zeolite.
aM 1 2 O ・ bSiO 2・ Al 2 O 3・ cMeO (1)
{In the formula (1), M 1 is an alkali metal atom, a hydrogen atom, or an ammonium ion, Me is an alkaline earth metal ion atom, a is 0.01 to 1, b is 1 to 80, c is 0 to 1. }
dM 2 2 O · eAl 2 O 3 · fSiO 2 · gH 2 O (2)
{In the formula (2), the ratio d / g is 0.00035 to 0.02000, the ratio e / g is 0 to 0.00025, and the f / g is 0.0001 to 0.025. }
　上記式（１）中のｂは、例えば、２～６０又は２０～８０であってよい。ｃは、例えば、０．０１～１であってよい。上記式（２）における比ｄ／ｇは、例えば、０．００３～０．０１０であってよい。比ｅ／ｇは、例えば、０又は０．０００００３～０．０００２５０であってよい。比ｆ／ｇは、例えば、０．０００１～０．０１６０又は０．００６～０．０２５であってよい。 B in the above formula (1) may be, for example, 2 to 60 or 20 to 80. c may be, for example, 0.01 to 1. The ratio d / g in the above formula (2) may be, for example, 0.003 to 0.010. The ratio e / g may be, for example, 0 or 0.000003 to 0.000250. The ratio f / g may be, for example, 0.0001 to 0.0160 or 0.006 to 0.025.
　上記式（１）の原料ゼオライトとしては、例えば、ＮａＳｉＡｌＯ４、ＮａＳｉ１２ＡｌＯ２６、ＮＨ４Ｓｉ１９ＡｌＯ４０等を用いることができる。上記式（２）のシリケートとしては、例えば、０．２９２Ｎａ２Ｏ・ｈＳｉＯ２・５５．５Ｈ２Ｏ（ｈ＝０．４００、０．６５０、０．８００、又は１．００）、ｉＮａ２Ｏ・０．６５０ＳｉＯ２・５５．５Ｈ２Ｏ（ｉ＝０．１６５又は０．５５）等を用いることができる。上記式（２）のアルミノシリケートとしては、例えば、４０５Ｎａ２Ｏ・ｊＡｌ２Ｏ３・ｋＳｉＯ２・２９，９００Ｈ２Ｏ（（ｊ，ｋ）＝（１，２３）、（１，５１）、（２，２３）、又は（２，５１））等を用いることができる。 As the raw material zeolite of the above formula (1), for example, NaSiAlO 4 , NaSi 12 AlO 26 , NH 4 Si 19 AlO 40, etc. can be used. Examples of the silicate of the above formula (2) include 0.292Na 2 O.hSiO 2 55.5H 2 O (h = 0.400, 0.650, 0.800, or 1.00), iNa 2 O. · 0.650SiO 2 · 55.5H 2 O ( i = 0.165 or 0.55), or the like can be used. As the aluminosilicate of the above formula (2), for example, 405Na 2 O · jAl 2 O 3 · kSiO 2 · 29,900H 2 O ((j, k) = (1,23), (1,51), ( 2, 23), (2, 51)) or the like can be used.
　ゼオライトとしては、上記のようにして得られたものに、イオン交換若しくは粉砕又はこれらの双方を施した後に使用に供してもよい。 As the zeolite, the zeolite obtained as described above may be subjected to ion exchange, pulverization, or both, and then used.
　本発明の樹脂組成物におけるゼオライトの含有量は、本発明の有利な効果を与えられる範囲であれば特に限定されない。例えば、ゼオライトの含有量は、５質量％以上、１０質量％以上、２０質量％以上、３０質量％以上、４０質量％以上、又は５０質量％以上であってもよく、７０質量％以下、６０質量％以下、５０質量％以下、又は４０質量％以下であってもよい。例えば、ゼオライトの含有量は、２０質量％以上６０質量％以下、又は３０質量％以上５０質量％以下であってもよい。 The content of zeolite in the resin composition of the present invention is not particularly limited as long as the advantageous effects of the present invention can be provided. For example, the content of zeolite may be 5 mass% or more, 10 mass% or more, 20 mass% or more, 30 mass% or more, 40 mass% or more, or 50 mass% or more, 70 mass% or less, 60 It may be less than or equal to 50% by weight, less than or equal to 50% by weight, or less than or equal to 40% by weight. For example, the content of zeolite may be 20% by mass or more and 60% by mass or less, or 30% by mass or more and 50% by mass or less.
〈酸化物〉
　本発明の樹脂組成物は、特許文献２に記載の発明で用いられているような、平均粒子径Ｄ５０が１００ｎｍ以下の、Ａｌ、Ｓｉ、Ｔｉ、及びＺｒから選択される１種以上の元素の酸化物（ただし、ゼオライトを除く。）を含まなくてもよい。 <Oxide>
The resin composition of the present invention comprises one or more elements selected from Al, Si, Ti, and Zr having an average particle diameter D50 of 100 nm or less as used in the invention described in Patent Document 2. It is not necessary to include oxides (excluding zeolite).
　本発明の樹脂組成物が、このような酸化物を含有しない場合、ゼオライトと酸化物との混合状態、酸化物の分散状態等について配慮する必要がないため、容易に製造することができ、またコストも低減できる。 If the resin composition of the present invention does not contain such an oxide, it is not necessary to consider the mixed state of the zeolite and the oxide, the dispersed state of the oxide, etc., so that it can be easily produced, The cost can also be reduced.
〈エステル化合物〉
　本発明の樹脂組成物は、エステル化合物を含む。エステル化合物は、乳化剤等として用いられるような化合物を用いることができ、本発明で用いられるゼオライトと熱可塑性樹脂との混合を可能にする。 <Ester compound>
The resin composition of the present invention contains an ester compound. As the ester compound, a compound used as an emulsifying agent or the like can be used, and the zeolite used in the present invention and the thermoplastic resin can be mixed.
　エステル化合物としては、例えばＨＬＢ値５以下のエステル化合物を用いてもよい。ＨＬＢ値は、親水性か親油性かを示す指標である。エステル化合物のＨＬＢ値が５以下であるということは、該エステル化合物の親油性が高いことを意味し、例えば、消泡剤、又はエマルジョンの乳化剤として使用される領域の数値である。 As the ester compound, for example, an ester compound having an HLB value of 5 or less may be used. The HLB value is an index indicating hydrophilicity or lipophilicity. The HLB value of the ester compound being 5 or less means that the ester compound has a high lipophilicity, and is, for example, a numerical value in a range used as an antifoaming agent or an emulsifier of an emulsion.
　しかし、本発明の有利な効果が得られる範囲であればエステル化合物のＨＬＢ値は、５以上であってもよく、例えばエステル化合物のＨＬＢ値は、８．０以下、６．０以下、５．０以下、４．５以下、４．０以下、又は３．５以下であってよく、２．０以上、２．５以上、又は３．０以上であってよい。例えば、エステル化合物のＨＬＢ値は、２．０以上５．０以下、又は２．５以上４．５以下であってもよい。 However, the HLB value of the ester compound may be 5 or more as long as the advantageous effects of the present invention are obtained, and for example, the HLB value of the ester compound is 8.0 or less, 6.0 or less, 5. It may be 0 or less, 4.5 or less, 4.0 or less, or 3.5 or less, and may be 2.0 or more, 2.5 or more, or 3.0 or more. For example, the HLB value of the ester compound may be 2.0 or more and 5.0 or less, or 2.5 or more and 4.5 or less.
　エステル化合物としては、例えば、多価アルコールと脂肪酸とのモノエステル化合物である。多価アルコールは、例えば、グリセリン、アルキレングリコール等であってよい。脂肪酸は、例えば、炭素数１２以上２４以下の、飽和又は不飽和の脂肪酸であってよい。 The ester compound is, for example, a monoester compound of a polyhydric alcohol and a fatty acid. The polyhydric alcohol may be, for example, glycerin, alkylene glycol or the like. The fatty acid may be, for example, a saturated or unsaturated fatty acid having 12 to 24 carbon atoms.
　エステル化合物としては、特に、炭素数２以上６以下のアルキレングリコールと炭素数１５以上２４以下の脂肪酸とのモノエステルであってよい。上記アルキレングリコールは、例えば、エチレングリコール、プロピレングリコール、ジエチレングリコール等であってよい。上記と炭素数１５以上２４以下の脂肪酸は、飽和又は不飽和であってよく、例えば、ステアリン酸、ベヘン酸等であってよい。 The ester compound may be a monoester of an alkylene glycol having 2 to 6 carbon atoms and a fatty acid having 15 to 24 carbon atoms. The alkylene glycol may be, for example, ethylene glycol, propylene glycol, diethylene glycol or the like. The above-mentioned fatty acids having 15 to 24 carbon atoms may be saturated or unsaturated, and may be, for example, stearic acid, behenic acid and the like.
　エステル化合物は、具体的には例えば、プロピレングリコールモノステアレート、プロピレングリコールモノベヘネート等であってよい。 The ester compound may be, for example, propylene glycol monostearate, propylene glycol monobehenate, or the like.
　本発明の樹脂組成物におけるエステル化合物の含有量は、本発明の有利な効果を与えられる範囲であれば特に限定されない。例えば、エステル化合物の含有量は、２．０質量％以上１５質量％以下であり、２．５質量％以上、３．０質量％以上、又は５．０質量％以上であってもよく、１２質量％以下、１０質量％以下、８．０質量％以下、又は６．０質量％以下であってもよい。例えば、エステル化合物の含有量は、２．５質量％以上１２質量％以下、又は３．０質量％以上１０質量％以下であってもよい。 The content of the ester compound in the resin composition of the present invention is not particularly limited as long as the advantageous effects of the present invention can be provided. For example, the content of the ester compound is 2.0% by mass or more and 15% by mass or less, and may be 2.5% by mass or more, 3.0% by mass or more, or 5.0% by mass or more. It may be less than or equal to 10% by weight, less than or equal to 10% by weight, less than or equal to 8.0% by weight, or less than or equal to 6.0% by weight. For example, the content of the ester compound may be 2.5% by mass or more and 12% by mass or less, or 3.0% by mass or more and 10% by mass or less.
〈熱可塑性樹脂〉
　本発明の樹脂組成物は、熱可塑性樹脂、特にエチレン単位を含む熱可塑性樹脂を含む。特に、本発明の樹脂組成物は、カルボン酸基、カルボン酸エステル基等の極性基とエチレン単位とを含む熱可塑性樹脂であることが好ましい。 <Thermoplastic resin>
The resin composition of the present invention contains a thermoplastic resin, particularly a thermoplastic resin containing ethylene units. In particular, the resin composition of the present invention is preferably a thermoplastic resin containing a polar group such as a carboxylic acid group or a carboxylic acid ester group and an ethylene unit.
　熱可塑性樹脂としては、ポリオレフィン系樹脂を挙げることができポリオレフィン系樹脂としては、ポリエチレン系樹脂、ポリプロピレン系樹脂、エチレンと酸素含有エチレン性不飽和単量体との共重合体等が挙げられる。エチレンと酸素含有エチレン性不飽和単量体との共重合体としては、例えばＥＶＯＨ（エチレン－ビニルアルコール共重合体）等が挙げられる。 Examples of the thermoplastic resin include a polyolefin resin, and examples of the polyolefin resin include a polyethylene resin, a polypropylene resin, and a copolymer of ethylene and an oxygen-containing ethylenically unsaturated monomer. Examples of the copolymer of ethylene and an oxygen-containing ethylenically unsaturated monomer include EVOH (ethylene-vinyl alcohol copolymer) and the like.
　なお、本明細書において、ポリエチレン系樹脂とは、ポリマーの主鎖にエチレン基の繰返し単位を、３０ｍｏｌ％以上、４０ｍｏｌ％以上、５０ｍｏｌ％以上、６０ｍｏｌ％以上、７０ｍｏｌ％以上、又は８０ｍｏｌ％以上含む樹脂であり、例えば、低密度ポリエチレン（ＬＤＰＥ）、直鎖状低密度ポリエチレン（ＬＬＤＰＥ）、中密度ポリエチレン（ＭＤＰＥ）、高密度ポリエチレン（ＨＤＰＥ）、エチレン－アクリル酸共重合体（ＥＡＡ）、エチレン－メタクリル酸共重合体（ＥＭＡＡ）、エチレン－メチルメタクリレート共重合体（ＥＭＭＡ）、エチレン－エチルアクリレート共重合体（ＥＥＡ）、エチレン－メチルアクリレート共重合体（ＥＭＡ）、エチレン－酢酸ビニル共重合体（ＥＶＡ）、カルボン酸変性ポリエチレン、カルボン酸変性エチレンビニルアセテート共重合体、アイオノマー、及びこれらの誘導体、並びにこれらの混合物からなる群より選択される。 In addition, in the present specification, the polyethylene-based resin includes a repeating unit of an ethylene group in a main chain of a polymer, including 30 mol% or more, 40 mol% or more, 50 mol% or more, 60 mol% or more, 70 mol% or more, or 80 mol% or more. Resins such as low density polyethylene (LDPE), linear low density polyethylene (LLDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), ethylene-acrylic acid copolymer (EAA), ethylene- Methacrylic acid copolymer (EMAA), ethylene-methyl methacrylate copolymer (EMMA), ethylene-ethyl acrylate copolymer (EEA), ethylene-methyl acrylate copolymer (EMA), ethylene-vinyl acetate copolymer ( EVA), carboxylic acid modified polyethylene, cal Phosphate-modified ethylene vinyl acetate copolymer, ionomer, and their derivatives, and selected from the group consisting of mixtures.
　本明細書において、ポリプロピレン系樹脂とは、ポリマーの主鎖にプロピレン基の繰返し単位を、３０ｍｏｌ％以上、４０ｍｏｌ％以上、５０ｍｏｌ％以上、６０ｍｏｌ％以上、７０ｍｏｌ％以上、又は８０ｍｏｌ％以上含む樹脂であり、例えば、ポリプロピレン（ＰＰ）ホモポリマー、ランダムポリプロピレン（ランダムＰＰ）、ブロックポリプロピレン（ブロックＰＰ）、塩素化ポリプロピレン、カルボン酸変性ポリプロピレン、及びこれらの誘導体、並びにこれらの混合物が挙げられる。 In the present specification, a polypropylene-based resin is a resin containing a repeating unit of a propylene group in the main chain of a polymer, which is 30 mol% or more, 40 mol% or more, 50 mol% or more, 60 mol% or more, 70 mol% or more, or 80 mol% or more. There are, for example, polypropylene (PP) homopolymer, random polypropylene (random PP), block polypropylene (block PP), chlorinated polypropylene, carboxylic acid modified polypropylene, and derivatives thereof, and mixtures thereof.
　ゼオライト及びエステル化合物との親和性との観点から、これらの中でも特に、エチレン－酢酸ビニル共重合体を挙げることができる。エチレン－酢酸ビニル共重合体における酢酸ビニル含量は、１０質量％以上、１５質量％以上、２０質量％以上、２５質量％以上、又は３０質量％以上であってよく、６０質量％以下、５５質量％以下、５０質量％以下、４５質量％以下、又は４０質量％以下であってよい。エチレン－酢酸ビニル共重合体における酢酸ビニル含量は、例えば５質量％以上５０質量％以下、又は２０質量％以上４０質量％以下であってよい。 From the viewpoint of affinity with zeolite and ester compounds, ethylene-vinyl acetate copolymer can be mentioned among these. The vinyl acetate content in the ethylene-vinyl acetate copolymer may be 10% by mass or more, 15% by mass or more, 20% by mass or more, 25% by mass or more, or 30% by mass or more, and 60% by mass or less, 55% by mass. % Or less, 50% by mass or less, 45% by mass or less, or 40% by mass or less. The vinyl acetate content in the ethylene-vinyl acetate copolymer may be, for example, 5% by mass or more and 50% by mass or less, or 20% by mass or more and 40% by mass or less.
　本発明の樹脂組成物における熱可塑性樹脂の含有量は、３０質量％以上、４０質量％以上、５０質量％以上、６０質量％以上、又は７０質量％以上であってもよく、８０質量％以下、７０質量％以下、６０質量％以下、又は５０質量％以下であってもよい。例えば、熱可塑性樹脂の含有量は、３０質量％以上８０質量％以下、又は４０質量％以上７０質量％以下であってもよい。 The content of the thermoplastic resin in the resin composition of the present invention may be 30% by mass or more, 40% by mass or more, 50% by mass or more, 60% by mass or more, or 70% by mass or more, and 80% by mass or less. , 70 mass% or less, 60 mass% or less, or 50 mass% or less. For example, the content of the thermoplastic resin may be 30% by mass or more and 80% by mass or less, or 40% by mass or more and 70% by mass or less.
〈任意的添加剤〉
　本発明の樹脂組成物は、上記の各成分の他に、必要に応じて、滑材、帯電防止剤、離型剤、可塑剤、酸化防止剤、防菌剤、防かび剤、紫外線吸収剤等の任意的添加剤を更に含有することができる。 <Optional additives>
The resin composition of the present invention contains, in addition to the above-mentioned components, if necessary, a lubricant, an antistatic agent, a release agent, a plasticizer, an antioxidant, an antibacterial agent, an antifungal agent, an ultraviolet absorber. Can further contain optional additives such as.
《吸湿フィルム》
　本発明の吸湿フィルムは、上記の吸湿樹脂組成物を含み、又はこの組成物からなる。 <Hygroscopic film>
The moisture absorbent film of the present invention contains or consists of the above moisture absorbent resin composition.
　本発明のフィルムの厚みは、１０μｍ以上、２０μｍ以上、３０μｍ以上、又は４０μｍ以上であってよく、３００μｍ以下、２００μｍ以下、１００μｍ以下、９０μｍ以下、８０μｍ以下、７０μｍ以下、又は６０μｍ以下であってよい。例えば、本発明のフィルムの厚みは、１０μｍ以上３００μｍ以下、又は２０μｍ以上１００μｍ以下であってもよい。 The thickness of the film of the present invention may be 10 μm or more, 20 μm or more, 30 μm or more, or 40 μm or more, and may be 300 μm or less, 200 μm or less, 100 μm or less, 90 μm or less, 80 μm or less, 70 μm or less, or 60 μm or less. . For example, the film of the present invention may have a thickness of 10 μm or more and 300 μm or less, or 20 μm or more and 100 μm or less.
《吸湿積層体》
　本発明の吸湿積層体は、上記の吸湿フィルムを他のフィルム、例えばスキン層と積層して得られる。また、本発明の積層体は、包装材料として用いられる通常のフィルムと、上記のフィルムとが積層されているものであってもよい。例えば、本発明の吸湿積層体は、上記の吸湿フィルムと、透明バリアフィルム（例えば、シリカ、アルミナ等を蒸着したＰＥＴフィルム、ポリアミドフィルム等）とを含んでいてもよい。このような積層体は、内部の確認をすることができ、かつ吸湿したかどうかの判断を容易にでき、また外部からのバリア性を有している点で、包装用のパウチ等として非常に有用である。 <Hygroscopic laminate>
The moisture absorbent laminate of the present invention can be obtained by laminating the above moisture absorbent film with another film, for example, a skin layer. Further, the laminate of the present invention may be a laminate of the above-mentioned film and a normal film used as a packaging material. For example, the moisture absorbent laminate of the present invention may include the moisture absorbent film described above and a transparent barrier film (for example, a PET film obtained by vapor deposition of silica, alumina, or the like, a polyamide film, or the like). Such a laminated body can be checked for the inside, it can be easily judged whether or not it has absorbed moisture, and it has a barrier property from the outside, so that it is very useful as a pouch for packaging or the like. It is useful.
〈スキン層〉
　本発明の積層体は、上記フィルムの少なくとも一方の面にスキン層を有していてもよく、例えばその両面に外スキン層と内スキン層とを有していてもよい。スキン層は、本発明のフィルムの成膜安定性の向上、表面平滑性の付与、フィルム中のゼオライトの脱落防止、ゼオライトが外部に直接露出することの防止、包装容器として使用する場合の機械的強度（例えば引張強度）の向上、及び他のフィルム又は積層体とのヒートシール強度の向上のうちの少なくとも１つの機能を有する。 <Skin layer>
The laminate of the present invention may have a skin layer on at least one surface of the film, for example, an outer skin layer and an inner skin layer on both surfaces thereof. The skin layer improves the film formation stability of the film of the present invention, imparts surface smoothness, prevents the zeolite in the film from falling off, prevents the zeolite from being directly exposed to the outside, and mechanically when used as a packaging container. It has at least one function of improving strength (for example, tensile strength) and improving heat seal strength with other films or laminates.
　スキン層を構成する樹脂としては、フィルムに一般的に用いられている樹脂を用いることができる。吸湿フィルムが外スキン層と内スキン層とを有する場合、それぞれのスキン層を構成する樹脂は、同一であっても異なっていてもよい。 As the resin forming the skin layer, a resin generally used for films can be used. When the moisture absorption film has an outer skin layer and an inner skin layer, the resins constituting the respective skin layers may be the same or different.
　スキン層を構成する樹脂としては、例えばポリスチレン系樹脂、ポリエステル系樹脂、アクリル系樹脂、ポリアミド系樹脂、ポリビニルアルコール系樹脂、ポリウレタン系樹脂、ポリオレフィン系樹脂、ポリカーボネート樹脂、ポリスルホン樹脂、及びこれらの誘導体、並びにこれらの混合物等が挙げられる。 As the resin constituting the skin layer, for example, polystyrene resin, polyester resin, acrylic resin, polyamide resin, polyvinyl alcohol resin, polyurethane resin, polyolefin resin, polycarbonate resin, polysulfone resin, and derivatives thereof, And mixtures thereof.
　スキン層の厚さは、片面当たり、１μｍ以上、３μｍ以上、５μｍ以上、又は７μｍ以上であることができ、５０μｍ以下、４０μｍ以下、３０μｍ以下、２０μｍ以下、又は１５μｍ以下であることができる。吸湿フィルムが外スキン層と内スキン層とを有する場合、これらのスキン層の厚さは同一であっても異なっていてもよい。 The thickness of the skin layer can be 1 μm or more, 3 μm or more, 5 μm or more, or 7 μm or more, and can be 50 μm or less, 40 μm or less, 30 μm or less, 20 μm or less, or 15 μm or less per one surface. When the moisture absorbent film has the outer skin layer and the inner skin layer, the thickness of these skin layers may be the same or different.
《吸湿フィルム又は積層体の製造方法》
　吸湿フィルム又は積層体の成形法は特に限定されないが、単層又は多層インフレーション法、Ｔダイ法、キャスト法等が挙げられ、特にＴダイ法又はインフレーション法が好ましい。 << Method of manufacturing moisture absorption film or laminate >>
The method for forming the moisture-absorbing film or the laminate is not particularly limited, and examples thereof include a single-layer or multi-layer inflation method, a T-die method, a casting method, etc., and the T-die method or the inflation method is particularly preferable.
　吸湿フィルムを成形する前に、上記の吸湿樹脂組成物に含まれる材料を混練したものをペレット状に押し出して冷却することで、ペレット状の吸湿樹脂組成物（マスターバッチ）を作製しておくことができる。また、上記の吸湿樹脂組成物に含まれる材料を混練し、そのままフィルムを成形してもよい。 Before molding the moisture-absorbing film, a pellet-shaped moisture-absorbent resin composition (masterbatch) should be prepared by extruding a mixture of the materials contained in the moisture-absorbent resin composition in a pellet form and cooling the mixture. You can Alternatively, the materials contained in the hygroscopic resin composition may be kneaded to form a film as it is.
　混練は、例えば、ニーダー、バンバリーミキサー、ヘンシェルミキサー、ミキシングロールなどのバッチ式混練機、２軸混練機などの連続混練機などを用いて行うことができる。この際には、使用する材料に応じて、６０℃以上、８０℃以上、１００℃以上、又は１２０℃以上で、かつ１７０℃以下、１５０℃以下、又は１３０℃以下の混練温度、０．５分以上３０分以下の混練時間で混練することができる。 The kneading can be performed using, for example, a batch kneader such as a kneader, a Banbury mixer, a Henschel mixer, a mixing roll, or a continuous kneader such as a twin-screw kneader. At this time, depending on the material used, a kneading temperature of 60 ° C. or higher, 80 ° C. or higher, 100 ° C. or higher, or 120 ° C. or higher and 170 ° C. or lower, 150 ° C. or lower, or 130 ° C. or lower, 0.5. Kneading can be performed for a kneading time of not less than 30 minutes and not more than 30 minutes.
　本発明の吸湿フィルムは、例えば上記の吸湿樹脂組成物に含まれる材料を２軸混練押出機などで混練し、そのまま、１００℃以上、１２０℃以上、１３０℃以上、１３５℃以上、１４０℃以上、又は１５０℃以上、２５０℃以下、２２０℃以下、又は２００℃未満で、インフレーション成形法又はＴダイ法等により成形して吸湿を製造することができる。また、好ましくは、上記のようにマスターバッチを作製し、それを再加熱して、インフレーション成形法又はＴダイ法等により製造することができる。このとき、吸湿フィルムの両面には、例えばオレフィン系樹脂からなるスキン層を共押出して、又はスキン層となるフィルムを熱圧着等によってラミネートして、吸湿積層体としてもよい。 The moisture-absorbing film of the present invention is obtained by kneading the materials contained in the moisture-absorbent resin composition described above, for example, with a biaxial kneading extruder or the like, and as it is, 100 ° C or higher, 120 ° C or higher, 130 ° C or higher, 135 ° C or higher, 140 ° C or higher. Or 150 ° C. or more, 250 ° C. or less, 220 ° C. or less, or less than 200 ° C., to form moisture absorption by molding by an inflation molding method or a T-die method. In addition, preferably, the masterbatch can be prepared as described above, reheated, and manufactured by an inflation molding method, a T-die method, or the like. At this time, a skin layer made of, for example, an olefin resin may be coextruded on both sides of the moisture absorption film, or a film to be the skin layer may be laminated by thermocompression bonding to form a moisture absorption laminate.
　本発明を以下の実施例でさらに具体的に説明をするが、本発明はこれによって限定されるものではない。 The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.
《製造例》
　熱可塑性樹脂、Ｎａ－Ａ型ゼオライト、及びエステル化合物（プロピレングリコールモノベヘネート、ＨＬＢ値３．４）を、表１に記載の配合でバンバリーミキサーを用いて１６０℃で１０分間溶融混練して、各例の樹脂組成物を得た。 <Production example>
The thermoplastic resin, Na-A type zeolite, and ester compound (propylene glycol monobehenate, HLB value 3.4) were melt-kneaded at 160 ° C. for 10 minutes using a Banbury mixer with the composition shown in Table 1, The resin composition of each example was obtained.
《評価》
〈メルトフローレート〉
　各例の樹脂組成物を測定可能なサイズにカットした。カットした樹脂組成物について、メルトインデクサ（株式会社テクノ・セブン）を用いて、温度１９０℃かつ荷重２１．１８Ｎの条件の下で、ＪＩＳ Ｋ７２１０に準拠して、メルトフローレート（ＭＦＲ）を測定した。 << Evaluation >>
<Melt flow rate>
The resin composition of each example was cut into a measurable size. The melt flow rate (MFR) of the cut resin composition was measured using a melt indexer (Techno Seven Co., Ltd.) under the conditions of a temperature of 190 ° C. and a load of 21.18 N in accordance with JIS K7210. .
〈ヘイズ〉
　樹脂組成物を所定の重量にカットして、熱プレス成型によって１００μｍの厚みのフィルムを作製した。ここで、プレスの条件は、温度１６０℃、圧力４０～６０ＭＰａ、２分間とした。このようにして得られたフィルムを、５０ｍｍ四方にカットして、ヘイズ測定器（株式会社村上色彩研究所、ＨＲ－１００）を用いて、ＪＩＳ Ｋ７１０５に準拠してヘイズを測定した。なお、吸湿後のヘイズについては、上記フィルムを２３℃５０％の環境下に静置し、吸湿後の重量変化が一定になるまで吸湿させ、その後上記と同じ方法で測定した。 <Haze>
The resin composition was cut into a predetermined weight, and a film having a thickness of 100 μm was produced by hot press molding. Here, the press conditions were a temperature of 160 ° C. and a pressure of 40 to 60 MPa for 2 minutes. The film thus obtained was cut into a 50 mm square, and the haze was measured according to JIS K7105 using a haze measuring instrument (Murakami Color Research Laboratory, HR-100). Regarding the haze after moisture absorption, the film was left to stand in an environment of 23 ° C. and 50%, allowed to absorb moisture until the weight change after moisture absorption became constant, and then measured by the same method as above.
《結果》
　各例の構成及び評価結果を表１に示す。 "result"
Table 1 shows the constitution and evaluation result of each example.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001

Claims (11)

  1. 　平均粒子径Ｄ５０が３００ｎｍ以下のゼオライト、
    　エステル化合物、及び
    　熱可塑性樹脂を含み、かつ
    　ＪＩＳ　Ｋ７１０５に準拠して吸湿前の１００μｍの厚みのフィルムにいて測定したときのヘイズが、２５％以上８０％以下である、
    吸湿樹脂組成物。     Zeolite having an average particle diameter D50 of 300 nm or less,
    The haze, which contains an ester compound and a thermoplastic resin, and is measured in a film having a thickness of 100 μm before moisture absorption according to JIS K7105 is 25% or more and 80% or less,
    Hygroscopic resin composition.
  2. 　吸湿後に測定したときのヘイズが、前記ヘイズより、１０％以上低い、請求項１に記載の組成物。 The composition according to claim 1, wherein the haze when measured after moisture absorption is 10% or more lower than the haze.
  3. 　前記ゼオライトの平均粒子径Ｄ５０が１００ｎｍ超である、請求項１又は２に記載の組成物。 The composition according to claim 1 or 2, wherein the average particle diameter D50 of the zeolite is more than 100 nm.
  4. 　平均粒子径Ｄ５０が１００ｎｍ以下の、Ａｌ、Ｓｉ、Ｔｉ、及びＺｒから選択される１種以上の元素の酸化物（ゼオライトを除く）を含んでいない、請求項１～３のいずれか一項に記載の組成物。 The oxide particles of one or more elements selected from Al, Si, Ti, and Zr (excluding zeolite) having an average particle diameter D50 of 100 nm or less are not included, and any one of claims 1 to 3 is included. The composition as described.
  5. 　前記熱可塑性樹脂が、ポリオレフィン系樹脂である、請求項１～４のいずれか一項に記載の組成物。 The composition according to any one of claims 1 to 4, wherein the thermoplastic resin is a polyolefin resin.
  6. 　温度１９０℃かつ荷重２１．１８Ｎの条件の下でＪＩＳ　Ｋ７２１０に準拠して測定した場合のメルトフローレートが、０．３ｇ／１０ｍｉｎ以上３０ｇ／１０ｍｉｎ以下である、請求項１～５のいずれか一項に記載の組成物。 6. The melt flow rate measured according to JIS K7210 under conditions of a temperature of 190 ° C. and a load of 21.18 N is 0.3 g / 10 min or more and 30 g / 10 min or less, and the melt flow rate is any one of claims 1 to 5. The composition according to the item.
  7. 　前記ゼオライトを、２０重量％以上６０重量％以下で含む、請求項１～６のいずれか一項に記載の組成物。 The composition according to any one of claims 1 to 6, which contains the zeolite in an amount of 20% by weight or more and 60% by weight or less.
  8. 　前記エステル化合物のＨＬＢ値が５以下である、請求項１～７のいずれか一項に記載の組成物。 The composition according to any one of claims 1 to 7, wherein the ester compound has an HLB value of 5 or less.
  9. 　請求項１～８のいずれか一項に記載の組成物を含む、吸湿フィルム。 A hygroscopic film containing the composition according to any one of claims 1 to 8.
  10. 　請求項８又は９に記載のフィルムを、外スキン層と内スキン層との間に有する、吸湿積層体。 A hygroscopic laminate having the film according to claim 8 or 9 between an outer skin layer and an inner skin layer.
  11. 　請求項１～８のいずれか一項に記載の組成物をＴダイ法又はインフレーション法によって成形することを含む、吸湿フィルムの製造方法。 A method for producing a moisture absorbent film, which comprises molding the composition according to any one of claims 1 to 8 by a T-die method or an inflation method.
PCT/JP2019/041748 2018-10-26 2019-10-24 Moisture-absorbing resin composition, moisture-absorbing film, and production method for moisture-absorbing film WO2020085440A1 (en)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0333162A (en) * 1989-06-30 1991-02-13 Mizusawa Ind Chem Ltd Resin compounding ingredient composition
JP2009029964A (en) * 2007-07-27 2009-02-12 Riken Technos Corp Water absorptive film
JP2010116436A (en) * 2008-11-11 2010-05-27 Toyo Seikan Kaisha Ltd Water-absorbing resin composition
WO2015022896A1 (en) * 2013-08-12 2015-02-19 共同印刷株式会社 Adsorbent composition, adsorbent-containing film and method for producing same
JP2018100390A (en) * 2016-12-20 2018-06-28 共同印刷株式会社 Light transmissive moisture absorption film and method for producing the same
WO2019151142A1 (en) * 2018-01-31 2019-08-08 日本ゼオン株式会社 Resin composition, resin film and organic electroluminescent device

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0333162A (en) * 1989-06-30 1991-02-13 Mizusawa Ind Chem Ltd Resin compounding ingredient composition
JP2009029964A (en) * 2007-07-27 2009-02-12 Riken Technos Corp Water absorptive film
JP2010116436A (en) * 2008-11-11 2010-05-27 Toyo Seikan Kaisha Ltd Water-absorbing resin composition
WO2015022896A1 (en) * 2013-08-12 2015-02-19 共同印刷株式会社 Adsorbent composition, adsorbent-containing film and method for producing same
JP2018100390A (en) * 2016-12-20 2018-06-28 共同印刷株式会社 Light transmissive moisture absorption film and method for producing the same
WO2019151142A1 (en) * 2018-01-31 2019-08-08 日本ゼオン株式会社 Resin composition, resin film and organic electroluminescent device

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