JP5937319B2 - Gas barrier film and production method - Google Patents
Gas barrier film and production method Download PDFInfo
- Publication number
- JP5937319B2 JP5937319B2 JP2011200233A JP2011200233A JP5937319B2 JP 5937319 B2 JP5937319 B2 JP 5937319B2 JP 2011200233 A JP2011200233 A JP 2011200233A JP 2011200233 A JP2011200233 A JP 2011200233A JP 5937319 B2 JP5937319 B2 JP 5937319B2
- Authority
- JP
- Japan
- Prior art keywords
- gas barrier
- film
- polyamine
- polycarboxylic acid
- swellable
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 230000004888 barrier function Effects 0.000 title claims description 80
- 238000004519 manufacturing process Methods 0.000 title 1
- 239000007789 gas Substances 0.000 claims description 71
- 239000002253 acid Substances 0.000 claims description 38
- 229920000768 polyamine Polymers 0.000 claims description 32
- 229910010272 inorganic material Inorganic materials 0.000 claims description 23
- 239000011147 inorganic material Substances 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 238000009835 boiling Methods 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 15
- 239000001301 oxygen Substances 0.000 claims description 15
- 229910052760 oxygen Inorganic materials 0.000 claims description 15
- 229920006255 plastic film Polymers 0.000 claims description 13
- 239000002985 plastic film Substances 0.000 claims description 13
- 230000035699 permeability Effects 0.000 claims description 12
- 239000000758 substrate Substances 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 9
- 229920002873 Polyethylenimine Polymers 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 229920002125 Sokalan® Polymers 0.000 claims description 7
- 239000004584 polyacrylic acid Substances 0.000 claims description 7
- 239000010445 mica Substances 0.000 claims description 6
- 229910052618 mica group Inorganic materials 0.000 claims description 6
- 229920000083 poly(allylamine) Polymers 0.000 claims description 6
- 239000004952 Polyamide Substances 0.000 claims description 5
- 229920002647 polyamide Polymers 0.000 claims description 5
- RLHGFJMGWQXPBW-UHFFFAOYSA-N 2-hydroxy-3-(1h-imidazol-5-ylmethyl)benzamide Chemical compound NC(=O)C1=CC=CC(CC=2NC=NC=2)=C1O RLHGFJMGWQXPBW-UHFFFAOYSA-N 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
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- 239000010408 film Substances 0.000 description 49
- 239000011248 coating agent Substances 0.000 description 30
- 238000000576 coating method Methods 0.000 description 18
- 239000007864 aqueous solution Substances 0.000 description 12
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- 238000001035 drying Methods 0.000 description 11
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- 125000003277 amino group Chemical group 0.000 description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 239000005022 packaging material Substances 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 239000012790 adhesive layer Substances 0.000 description 5
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
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- 238000004806 packaging method and process Methods 0.000 description 4
- 229920000058 polyacrylate Polymers 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 229910052814 silicon oxide Inorganic materials 0.000 description 4
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
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- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 2
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- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 2
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
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- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 2
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 2
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- WCRDXYSYPCEIAK-UHFFFAOYSA-N dibutylstannane Chemical compound CCCC[SnH2]CCCC WCRDXYSYPCEIAK-UHFFFAOYSA-N 0.000 description 2
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- 229940094522 laponite Drugs 0.000 description 2
- XCOBTUNSZUJCDH-UHFFFAOYSA-B lithium magnesium sodium silicate Chemical compound [Li+].[Li+].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Na+].[Na+].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3 XCOBTUNSZUJCDH-UHFFFAOYSA-B 0.000 description 2
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- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- AZJYLVAUMGUUBL-UHFFFAOYSA-A u1qj22mc8e Chemical compound [F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].O=[Si]=O.O=[Si]=O.O=[Si]=O.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3 AZJYLVAUMGUUBL-UHFFFAOYSA-A 0.000 description 2
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- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- IRXRGVFLQOSHOH-UHFFFAOYSA-L dipotassium;oxalate Chemical compound [K+].[K+].[O-]C(=O)C([O-])=O IRXRGVFLQOSHOH-UHFFFAOYSA-L 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- FLFJVPPJGJSHMF-UHFFFAOYSA-L manganese hypophosphite Chemical compound [Mn+2].[O-]P=O.[O-]P=O FLFJVPPJGJSHMF-UHFFFAOYSA-L 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 1
- 229940117841 methacrylic acid copolymer Drugs 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229910000273 nontronite Inorganic materials 0.000 description 1
- 229920006284 nylon film Polymers 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- HKOOXMFOFWEVGF-UHFFFAOYSA-N phenylhydrazine Chemical compound NNC1=CC=CC=C1 HKOOXMFOFWEVGF-UHFFFAOYSA-N 0.000 description 1
- 229940067157 phenylhydrazine Drugs 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229960005235 piperonyl butoxide Drugs 0.000 description 1
- 229920000724 poly(L-arginine) polymer Polymers 0.000 description 1
- 229920001652 poly(etherketoneketone) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 108010011110 polyarginine Proteins 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000656 polylysine Polymers 0.000 description 1
- 229920001444 polymaleic acid Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 229920000307 polymer substrate Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 150000004804 polysaccharides Chemical class 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229910001380 potassium hypophosphite Inorganic materials 0.000 description 1
- CRGPNLUFHHUKCM-UHFFFAOYSA-M potassium phosphinate Chemical compound [K+].[O-]P=O CRGPNLUFHHUKCM-UHFFFAOYSA-M 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- NONOKGVFTBWRLD-UHFFFAOYSA-N thioisocyanate group Chemical group S(N=C=O)N=C=O NONOKGVFTBWRLD-UHFFFAOYSA-N 0.000 description 1
- IUTCEZPPWBHGIX-UHFFFAOYSA-N tin(2+) Chemical compound [Sn+2] IUTCEZPPWBHGIX-UHFFFAOYSA-N 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Laminated Bodies (AREA)
Description
本発明は食品、医薬品、精密電子部品等の包装分野等に用いられる透明性を有するガスバリア性フィルムに関するものである。 The present invention relates to a gas barrier film having transparency used in the field of packaging foods, pharmaceuticals, precision electronic parts and the like.
近年、食品、医薬品、精密電子部品等の包装分野に用いられる包装材料は、内容物の変質、特に食品においては油脂の酸化や蛋白質の変質等を抑制して味や鮮度を保持するために、また医薬品においては有効成分の変質を抑制して効能を維持するために、さらに精密電子部品においては金属部分の腐食を抑制して絶縁不良等を防ぐために、包装材料を透過する酸素による影響を防止する必要があり、気体(ガス)を遮断するガスバリア性を備えることが求められている。 In recent years, packaging materials used in the packaging field of foods, pharmaceuticals, precision electronic components, etc. are used to maintain the taste and freshness by suppressing the alteration of contents, especially the oxidation of fats and oils and the alteration of proteins in foods. In addition, in pharmaceuticals, the effects of oxygen permeating through packaging materials are prevented in order to suppress the deterioration of active ingredients and maintain their efficacy, and in precision electronic parts, to suppress the corrosion of metal parts and prevent poor insulation. Therefore, it is required to have a gas barrier property to block gas (gas).
そのために、従来から塩化ビニリデン樹脂をコートしたポリプロピレン(KOP)やポリエチレンテレフタレート(KPET)或いはエチレンビニルアルコール共重合体(EVOH)など一般にガスバリア性が比較的高いと言われる高分子フィルムをガスバリア性フィルムとして用いた包装フィルム、あるいは酸化珪素(SiOx)などの珪素酸化物薄膜を透明高分子からなる基材上に真空蒸着などの手段によって設けた蒸着フィルムをガスバリア性フィルムとして用いた包装フィルムが一般的に使用されてきた。 For this purpose, polymer films that are generally said to have a relatively high gas barrier property such as polypropylene (KOP), polyethylene terephthalate (KPET), or ethylene vinyl alcohol copolymer (EVOH) coated with vinylidene chloride resin are used as gas barrier films. Generally used is a packaging film or a packaging film using, as a gas barrier film, a vapor deposition film in which a silicon oxide thin film such as silicon oxide (SiOx) is provided on a transparent polymer substrate by means of vacuum vapor deposition or the like. Have been used.
ところが、上述のEVOHを用いた包装フィルムは、温度や湿度の影響を受け易く、その変化によっては更にガスバリア性が低下することがあった。
さらにKOPやKPET等の塩化ビニリデン樹脂を用いた包装フィルムは、使用後の廃棄において焼却処理すると塩素ガスを発生するため、これが酸性雨の原因の一つになると言われ、最近では敬遠される傾向があった。
また、珪素酸化物薄膜を透明高分子からなる基材上に真空蒸着などの手段によって設けた蒸着フィルムは、屈曲等によって蒸着膜にクラックが入りやすく、結果としてガスバリア性が低下することがある。
However, the packaging film using the above-mentioned EVOH is easily influenced by temperature and humidity, and the gas barrier property may be further lowered depending on the change.
In addition, packaging films using vinylidene chloride resins such as KOP and KPET are said to be one of the causes of acid rain because they generate chlorine gas when incinerated after disposal. was there.
In addition, a deposited film in which a silicon oxide thin film is provided on a substrate made of a transparent polymer by means such as vacuum deposition may easily crack the deposited film due to bending or the like, and as a result, gas barrier properties may be lowered.
よってこれらの課題の解決を目的として、塗膜上にポリアクリル酸とポリアクリルアミド等の窒素含有官能基を有するポリマーの混合物を塗布後、2価以上の金属イオンのアルカリ性水溶液に浸漬することを特徴とするガスバリアフィルム(特許文献1)。塗膜上での有機高分子の架橋反応を利用するポリアクリル酸と、ポリアミンおよび/またはポリオールから製膜されたガスバリア層を有し、ポリカルボン酸の架橋度が40%以上であるガスバリアフィルム(特許文献2)。これらのガスバリア性フィルムが提案されている。しかし、前者は金属イオン水酸化物による2段目の架橋工程を必要とし、また前者後者ともに沸騰水によるボイル処理を30分行った後も十分にガスバリア性を発揮するガスバリア性フィルムではなかった。レトルト包装に用いられることの多いガスバリアフィルムにおいては、ボイル処理後もガスバリア性が低下しないことが望ましい。 Therefore, for the purpose of solving these problems, it is characterized in that after coating a coating of a polymer having a nitrogen-containing functional group such as polyacrylic acid and polyacrylamide on the coating film, it is immersed in an alkaline aqueous solution of divalent or higher metal ions. Gas barrier film (Patent Document 1). A gas barrier film having a gas barrier layer formed from polyacrylic acid using a cross-linking reaction of an organic polymer on a coating film and polyamine and / or polyol, and having a polycarboxylic acid crosslinking degree of 40% or more ( Patent Document 2). These gas barrier films have been proposed. However, the former requires a second step of crosslinking with a metal ion hydroxide, and neither of the former and the latter is a gas barrier film that exhibits sufficient gas barrier properties even after boiling for 30 minutes with boiling water. In a gas barrier film often used for retort packaging, it is desirable that the gas barrier property does not deteriorate even after the boil treatment.
本発明は、焼却時に塩素ガスを発生せず、温度湿度の変化や屈曲によるガスバリア性の低下がなく、かつボイル処理後も高いガスバリア性を保持するガスバリアフィルムを、複雑な工程を経ることなく取得することである。 The present invention obtains a gas barrier film that does not generate chlorine gas during incineration, does not deteriorate in gas barrier properties due to changes in temperature and humidity or bends, and retains a high gas barrier property even after boil processing without going through complicated steps. It is to be.
本願発明者らは上記課題を解決するために鋭意検討した結果、特定の組成のガスバリアコート剤を用いることで、目的とするガスバリアフィルムを得た。
すなわち本発明は、
(1)プラスチックフィルムからなる基材の少なくとも片面に、ポリアミンとポリカルボン酸と膨潤性薄片状無機物を重量比で、ポリアミン/ポリカルボン酸が12.5/87.5〜27.5/72.5、かつ、(ポリアミン+ポリカルボン酸)/膨潤性薄片状無機物が100/5〜100/50となるように混合してなる混合物が塗布されたフィルムであって、沸騰水によるボイル処理を30分行った直後の20℃×90%RHの酸素透過度が20cc/m2・atm・24h以下であることを特徴とするガスバリア性フィルム、
(2)前記ポリカルボン酸が、ポリアクリル酸、1,2,3,4−ブタンテトラカルボン酸から選ばれる少なくとも1種であることを特徴とする上記(1)記載のガスバリア性フィルム、
(3)前記ポリカルボン酸の重量平均分子量が10,000〜150,000であることを特徴とする、上記(1)または(2)に記載のガスバリア性フィルム、
(4)前記ポリアミンがポリアリルアミン、ポリエチレンイミンから選ばれる少なくとも1種であることを特徴とする上記(1)〜(3)のいずれか一つに記載のガスバリア性フィルム、
(5)前記膨潤性薄片状無機物が膨潤性スメクタイト、膨潤性マイカから選ばれる少なくとも1種であることを特徴とする、請求項1〜4のいずれか一項に記載のガスバリア性フィルム、
(6)前記プラスチックフィルムからなる基材が延伸ポリアミドフィルムもしくは、延伸ポリエステルフィルムであることを特徴とする上記(1)〜(5)のいずれか一つに記載のガスバリア性フィルム、
(7)前記混合物の塗布の後に、140℃以上、前記プラスチックフィルムの融点以下の温度で熱処理されて得られたものであることを特徴とする、上記(1)〜(6)のいずれか一つに記載のガスバリア性フィルム
に係るものである。
As a result of intensive investigations to solve the above problems, the present inventors have obtained a target gas barrier film by using a gas barrier coating agent having a specific composition.
That is, the present invention
(1) On at least one surface of a substrate made of a plastic film, polyamine / polycarboxylic acid and swellable flaky inorganic substance are in a weight ratio, and polyamine / polycarboxylic acid is 12.5 / 87.5 to 27.5 / 72. 5 and a film coated with a mixture of (polyamine + polycarboxylic acid) / swellable flaky inorganic material in a ratio of 100/5 to 100/50, and boiled with boiling water 30 A gas barrier film characterized by having an oxygen permeability of 20 cc × 90% RH immediately after the separation is 20 cc / m 2 · atm · 24 h or less,
(2) The gas barrier film according to (1), wherein the polycarboxylic acid is at least one selected from polyacrylic acid and 1,2,3,4-butanetetracarboxylic acid,
(3) The gas barrier film according to (1) or (2) above, wherein the polycarboxylic acid has a weight average molecular weight of 10,000 to 150,000.
(4) The gas barrier film according to any one of (1) to (3), wherein the polyamine is at least one selected from polyallylamine and polyethyleneimine,
(5) The gas barrier film according to any one of claims 1 to 4, wherein the swellable flaky inorganic material is at least one selected from swellable smectite and swellable mica,
(6) The gas barrier film according to any one of (1) to (5) above, wherein the base material comprising the plastic film is a stretched polyamide film or a stretched polyester film,
(7) Any one of the above (1) to (6), which is obtained by heat treatment at a temperature of 140 ° C. or higher and lower than the melting point of the plastic film after the application of the mixture. This relates to the gas barrier film described in 1. above.
本発明は、ボイル処理後もガスバリア性、特に酸素遮断性に優れ、かつ可撓性、透明性、耐湿性、耐薬品性等に優れたガスバリア層を有し、また環境負荷も小さい包装用材料を、複雑な工程を経ることなく提供することができた。本発明の包装用材料は、あらゆる分野の包装用材料として利用可能である。 The present invention provides a packaging material that has a gas barrier layer that is excellent in gas barrier properties, particularly oxygen barrier properties after boil treatment, and has excellent flexibility, transparency, moisture resistance, chemical resistance, and the like, and has a small environmental load. Can be provided without going through a complicated process. The packaging material of the present invention can be used as a packaging material in all fields.
本発明のガスバリア性フィルムは、プラスチックフィルムからなる基材の少なくとも片面に、ポリアミンとポリカルボン酸と膨潤性薄片状無機物との混合物からなるガスバリアコート剤が塗布されたフィルムであり、沸騰水によるボイル処理を行った後も高いガスバリア性を保持するものである。 The gas barrier film of the present invention is a film in which a gas barrier coating agent composed of a mixture of polyamine, polycarboxylic acid and swellable flaky inorganic material is applied to at least one surface of a substrate composed of a plastic film. High gas barrier properties are maintained even after the treatment.
本発明で使用されるポリアミンは、分子中にアミノ基として第一級、第二級から選ばれる少なくとも1種のアミノ基を2個以上有しており、その具体例としては、ポリアリルアミン、ポリビニルアミン、分岐状ポリエチレンイミン、線状ポリエチレンイミン、ポリリジン、キトサンのように側鎖にアミノ基を有する多糖類、ポリアルギニンのように側鎖にアミノ基を有するポリアミド類などを例示することができる。分子量に関しては、重量平均分子量で5000〜150000の範囲であることが好ましい。分子量が低すぎる場合は塗膜が脆弱になり、分子量が高すぎる場合はハンドリング性を損ない、場合によってはコート剤中で凝集しバリア性を損なう可能性がある。 The polyamine used in the present invention has at least two amino groups selected from primary and secondary as amino groups in the molecule. Specific examples thereof include polyallylamine, polyvinyl Examples thereof include polysaccharides having an amino group in the side chain such as amine, branched polyethyleneimine, linear polyethyleneimine, polylysine and chitosan, and polyamides having an amino group in the side chain such as polyarginine. Regarding the molecular weight, the weight average molecular weight is preferably in the range of 5,000 to 150,000. When the molecular weight is too low, the coating film becomes fragile, and when the molecular weight is too high, the handling property is impaired, and in some cases, the coating agent may aggregate to impair the barrier property.
本発明で使用されるポリカルボン酸は、分子中にカルボキシル基を2個以上有しており、これらのカルボキシル基が無水物を形成していても良く、その具体例としては、ポリアクリル酸、ポリメタクリル酸、アクリル酸−メタクリル酸共重合体、1,2,3,4−ブタンテトラカルボン酸、ポリマレイン酸、エチレン−無水マレイン酸共重合体、アルギン酸のように側鎖にカルボキシル基を有する多糖類、カルボキシル基含有のポリアミドもしくはポリエステルなどを例示することができる。ポリカルボン酸が重合体の場合、その分子量は、重量平均分子量で1,000〜1,000,000が好ましく、より好ましくは10,000〜150,000、さらに好ましくは15,000〜110,000の範囲である。分子量が低すぎる場合は塗膜が脆弱になり、分子量が高すぎる場合はハンドリング性を損ない、場合によってはコート剤中で凝集しバリア性を損なう可能性がある。
本発明で使用するポリカルボン酸は、金属水酸化物による部分中和処理を行わなくてよい。
The polycarboxylic acid used in the present invention has two or more carboxyl groups in the molecule, and these carboxyl groups may form an anhydride. Specific examples thereof include polyacrylic acid, Polymethacrylic acid, acrylic acid-methacrylic acid copolymer, 1,2,3,4-butanetetracarboxylic acid, polymaleic acid, ethylene-maleic anhydride copolymer, polyhydric acid having side chain carboxyl groups such as alginic acid Examples thereof include saccharides, carboxyl group-containing polyamides or polyesters. When the polycarboxylic acid is a polymer, its molecular weight is preferably 1,000 to 1,000,000, more preferably 10,000 to 150,000, and still more preferably 15,000 to 110,000 in terms of weight average molecular weight. Range. When the molecular weight is too low, the coating film becomes fragile, and when the molecular weight is too high, the handling property is impaired, and in some cases, the coating agent may aggregate to impair the barrier property.
The polycarboxylic acid used in the present invention does not need to be partially neutralized with a metal hydroxide.
本発明でポリアミンとポリカルボン酸を混合する際、混合物のゲル化が起こる可能性があるため、ゲル化の抑制を目的として、ポリカルボン酸に塩基を添加しておくことが望ましい。この時、使用する塩基としては、ガスバリア性を阻害しなければ何れでも良く、水酸化ナトリウム、水酸化カルシウムのような無機物、アンモニア、メチルアミン、ジエタノールアミン、ヒドロキシルアミン、ピリジン、p−フエネチジン、フェニルヒドラジン、p−トリイジン、ベンジジン、キノリン、m−トリイジン、アニリン、ο−フエネチジン、ο−トリイジン、m−フエネチジン、β−ナフチルアミン、α−ナフチルアミン、ベンジジン、尿素のような有機物の中から少なくとも1種を選ぶことができる。乾燥、熱処理で揮発する物が好ましく、具体例としては、アンモニアを例示することができる。使用する塩基の量としてはポリカルボン酸のカルボキシル基に対し0.6当量以上、好ましくは0.7当量以上、より好ましくは0.8当量以上である。添加するアンモニアが少なかった場合、コートの途中で混合物がゲル化し目的とするガスバリア性フィルムを造ることが困難となる。 When mixing polyamine and polycarboxylic acid in the present invention, gelation of the mixture may occur. Therefore, it is desirable to add a base to polycarboxylic acid for the purpose of suppressing gelation. At this time, any base may be used as long as it does not inhibit gas barrier properties, such as inorganic substances such as sodium hydroxide and calcium hydroxide, ammonia, methylamine, diethanolamine, hydroxylamine, pyridine, p-phenetidine, and phenylhydrazine. , P-triidine, benzidine, quinoline, m-triidine, aniline, ο-phenetidine, ο-triidine, m-phenetidine, β-naphthylamine, α-naphthylamine, benzidine, urea and at least one selected from organic materials be able to. Substances that volatilize by drying and heat treatment are preferred, and a specific example is ammonia. The amount of the base used is 0.6 equivalents or more, preferably 0.7 equivalents or more, more preferably 0.8 equivalents or more with respect to the carboxyl group of the polycarboxylic acid. When the amount of ammonia to be added is small, the mixture gels in the middle of the coating, making it difficult to produce the desired gas barrier film.
本発明におけるガスバリアコート剤の調製は、まずポリアミンとポリカルボン酸をそれぞれ重量比でポリアミン/ポリカルボン酸=12.5/87.5〜27.5/72.5となるように混合する。アミノ基の量がこれより少ないとカルボキシル基の架橋が不十分となり、逆に、アミノ基の量がこれより多いとアミノ基の架橋が不十分となり、沸騰水でボイル処理を30分行った直後の20℃×90%RHの酸素透過度が20cc/m2・atm・24h以下とならない。 In the preparation of the gas barrier coating agent in the present invention, first, polyamine and polycarboxylic acid are mixed so that the weight ratio of polyamine / polycarboxylic acid is 12.5 / 87.5 to 27.5 / 72.5. If the amount of amino groups is less than this, the crosslinking of carboxyl groups becomes insufficient. Conversely, if the amount of amino groups is more than this, crosslinking of amino groups becomes insufficient and immediately after boiling with boiling water for 30 minutes. The oxygen permeability of 20 ° C. × 90% RH is not less than 20 cc / m 2 · atm · 24 h.
前述のポリアミンとポリカルボン酸の反応を速やかに、もしくは穏和な条件で完了させるために、触媒や縮合剤を添加しても良い。触媒や縮合剤としては、オクチル酸スズ(II)、ジラウリン酸ジ−n−ブチルスズ(IV)などのスズを含有する化合物。三酸化アンチモン、シュウ酸チタン酸カリウム、酢酸カルシウム、酢酸マグネシウム、酢酸マンガン、次亜リン酸、次亜リン酸マンガン、次亜リン酸カリウム、次亜リン酸ナトリウム、酢酸亜鉛、チタンラクテート、チタンラクテートアンモニウム塩、チタンジイソプロポキシビス(トリエタノールアミネート)、チタンテトライソプロポキシド、チタンテトラノルマルブトキシド、チタンブトキシドダイマー、チタンテトラ−2−エチルヘキソキシド、チタンジイソプロポキシビス(アセチルアセトネート)、チタンテトラアセチルアセトネート、チタニウムジ−2−エチルヘキソキシビス(2−エチル−3−ヒドロキシヘキソキシド)、チタンジイソプロポキシビス(エチルアセトアセテート)、ポリヒドロキシチタンステアレート、2,4,6−トリクロロベンゾイルクロリド、ジフェニルリン酸アジド、ベンゾトリアゾール−1−イルオキシ−トリスジメチルアミノホスホニウム塩。N,N‘−ジシクロヘキシルカルボジイミド、1−ヒドロキシベンゾトリアゾール、N−ヒドロキシスクシンイミド、1−エチル−3−(3−ジメチルアミノプロピル)カルボジイミド塩酸塩などのカルボジイミド系化合物。4−(4,6−ジメトキシ−1,3,5−トリアジン−2−イル)−4−メチルモルホリニウムクロライド(DMT−MM)などを例示することができ、これらのうちから選ばれる、1種類以上を添加しても良い。 A catalyst or a condensing agent may be added in order to complete the reaction between the polyamine and the polycarboxylic acid promptly or under mild conditions. As a catalyst or a condensing agent, compounds containing tin such as tin (II) octylate and di-n-butyltin (IV) dilaurate. Antimony trioxide, potassium oxalate titanate, calcium acetate, magnesium acetate, manganese acetate, hypophosphorous acid, manganese hypophosphite, potassium hypophosphite, sodium hypophosphite, zinc acetate, titanium lactate, titanium lactate Ammonium salt, titanium diisopropoxybis (triethanolaminate), titanium tetraisopropoxide, titanium tetranormal butoxide, titanium butoxide dimer, titanium tetra-2-ethylhexoxide, titanium diisopropoxybis (acetylacetonate) Titanium tetraacetylacetonate, titanium di-2-ethylhexoxybis (2-ethyl-3-hydroxyhexoxide), titanium diisopropoxybis (ethylacetoacetate), polyhydroxytitanium stearate, 2 4,6-trichloro benzoyl chloride, diphenyl phosphoric acid azide, benzotriazol-1-yloxy - tris (dimethylamino) phosphonium salt. Carbodiimide compounds such as N, N'-dicyclohexylcarbodiimide, 1-hydroxybenzotriazole, N-hydroxysuccinimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride. 4- (4,6-dimethoxy-1,3,5-triazin-2-yl) -4-methylmorpholinium chloride (DMT-MM) and the like can be exemplified, and 1 selected from these More than one kind may be added.
本発明で使用される膨潤性薄片状無機物は、水に分散することで膨潤し、アスペクト比(薄片状無機物の直径/厚み)が25以上であることが好ましく、25未満であれば良好なバリア性が得られにくい。膨潤性薄片状無機物は、天然物もしくは合成物のいずれであっても良く、これらの混合物であっても良い。天然物としてはモンモリロナイト、バイデライト、ノントロナイト、サポナイト、ヘクトライト、ソーコナイト、スチーブンサイト等のスメクタイト系の粘土鉱物。モンモリロナイト含有量の高いベントナイト。純雲母、脆雲母等のマイカ系粘土鉱物。合成物としては、合成ヘクトライト(ケイ酸ナトリウム・マグネシウム)、合成ベントナイト、合成サポナイト、合成マイカなどを例示することができ、これらのうちから選ばれる少なくとも1種を添加することができる。 The swellable flaky inorganic material used in the present invention swells when dispersed in water, and the aspect ratio (diameter / thickness of the flaky inorganic material) is preferably 25 or more. It is difficult to obtain sex. The swellable flaky inorganic material may be a natural product or a synthetic product, or a mixture thereof. Natural products include smectite clay minerals such as montmorillonite, beidellite, nontronite, saponite, hectorite, soconite, and stevensite. Bentonite with high montmorillonite content. Mica clay minerals such as pure mica and brittle mica. Examples of the synthesized product include synthetic hectorite (sodium silicate / magnesium), synthetic bentonite, synthetic saponite, synthetic mica, and the like, and at least one selected from these can be added.
本発明で使用される膨潤性薄片状無機物の分散方法は、特に限定されるものではなく、分散後の膨潤性薄片状無機物のアスペクト比25以上になれば良く、ポリアミンとポリカルボン酸との混合物に添加後分散しても、膨潤性薄片状無機物を事前に分散してからポリアミンとポリカルボン酸との混合物に添加しても良い。また、必要に応じて膨潤性薄片状無機物の分散性を向上させる添加剤を添加しても良い。分散に用いる装置も特に限定されず、攪拌、ボールミル、ビーズミル、ジェットミル、ホモミキサー、ホモジナイザー、ナノマイザーなどを選ぶことができる。 The method for dispersing the swellable flaky inorganic material used in the present invention is not particularly limited, and it is sufficient that the aspect ratio of the swellable flaky inorganic material after dispersion is 25 or more, and a mixture of polyamine and polycarboxylic acid. Alternatively, the swellable flaky inorganic material may be dispersed in advance and then added to the mixture of polyamine and polycarboxylic acid. Moreover, you may add the additive which improves the dispersibility of a swellable flaky inorganic substance as needed. The apparatus used for dispersion is not particularly limited, and stirring, ball mill, bead mill, jet mill, homomixer, homogenizer, nanomizer, and the like can be selected.
膨潤性薄片状無機物は、ポリアミンとポリカルボン酸の混合物に、重量比で(ポリアミンとポリカルボン酸の合計の重量)/(膨潤性薄片状無機物)=100/5〜100/50となるように添加して混合し、ガスバリアコート剤とする。所定の量の膨潤性薄片状無機物を添加することにより、ガスバリア性が向上するため、添加しない場合に比べるとガスバリアコート膜の厚みを薄くすることができ、経済性、生産性の観点で非常に優れる。が、膨潤性薄片状無機物の量がこれより少ないと十分な迷路効果が得られず、膨潤性薄片状無機物によるガスバリア性の改善効果が不十分となる。逆に、膨潤性薄片状無機物の量がこれより多いと、ガスバリアコート膜中にボイドが形成されるためガスバリア性が低下する。 The swellable flaky inorganic substance is added to the mixture of polyamine and polycarboxylic acid so that the weight ratio is (total weight of polyamine and polycarboxylic acid) / (swellable flaky inorganic substance) = 100/5 to 100/50. Add and mix to make a gas barrier coating agent. By adding a predetermined amount of the swellable flaky inorganic material, the gas barrier property is improved, so that the thickness of the gas barrier coat film can be reduced compared with the case where it is not added. Excellent. However, if the amount of the swellable flaky inorganic material is smaller than this, a sufficient maze effect cannot be obtained, and the effect of improving the gas barrier property by the swellable flaky inorganic material becomes insufficient. On the contrary, if the amount of the swellable flaky inorganic material is larger than this, voids are formed in the gas barrier coat film, so that the gas barrier property is lowered.
本発明のガスバリアフィルムのガスバリア層には、前述したポリアミン、ポリカルボン酸、膨潤性薄片状無機物以外に、そのガスバリア性を損なわない範囲で、他の成分を含有させてもよい。 The gas barrier layer of the gas barrier film of the present invention may contain other components in addition to the aforementioned polyamine, polycarboxylic acid, and swellable flaky inorganic material as long as the gas barrier property is not impaired.
本発明において基材として用いられるプラスチックフィルムとは、ポリエチレン、ポリプロピレンなどのポリオレフィン系樹脂;ポリエチレンテレフタレート、ポリエチレンイソフタレート、ポリエチレン−2,6−ナフタレート、ポリブチレンテレフタレートなどのポリエステル系樹脂;ポリオキシメチレンなどのポリエーテル系樹脂;ポリアミド−6、ポリアミド−6,6、ポリメタキシレンアジパミドなどのポリアミド系樹脂;ポリスチレン、ポリ(メタ)アクリル酸エステル、ポリアクリロニトリル、ポリ酢酸ビニルなどのビニル系樹脂;ポリカーボネート系樹脂;セルロースアセテートなどのセルロース系樹脂;ポリイミド;ポリエーテルイミド;ポリフェニレンスルフィド;ポリエーテルスルフォン;ポリスルフォン;ポリエーテルエーテルケトン;ポリエーテルケトンケトンなどの熱可塑性樹脂を主成分とする。これらの熱可塑性樹脂は単独重合体であっても共重合体であってもよい。なお、本発明に用いられるプラスチックフィルムは、上記熱可塑性樹脂に限定されることなく、セロファンに代表される非熱可塑性フィルムも用いることが出来る。本発明の基材とはこれらの樹脂をフィルム状に成型したものが用いられる。未延伸フィルムや一軸または二軸に延伸したものいずれも使用できるが、バリア層をコートするときのコートしやすさ、バリア材の強度の観点から延伸ポリアミドフィルム、もしくは延伸ポリエステルフィルムが最も好ましい。 The plastic film used as a substrate in the present invention is a polyolefin resin such as polyethylene or polypropylene; a polyester resin such as polyethylene terephthalate, polyethylene isophthalate, polyethylene-2,6-naphthalate, or polybutylene terephthalate; Polyether resins such as polyamide-6, polyamide-6,6, polymethylene xylene adipamide and the like; vinyl resins such as polystyrene, poly (meth) acrylic acid ester, polyacrylonitrile and polyvinyl acetate; Polycarbonate resin; Cellulose resin such as cellulose acetate; Polyimide; Polyetherimide; Polyphenylene sulfide; Polyethersulfone; Polysulfone; Ether ketone; a thermoplastic resin such as polyether ketone ketone as a main component. These thermoplastic resins may be a homopolymer or a copolymer. In addition, the plastic film used for this invention is not limited to the said thermoplastic resin, The non-thermoplastic film represented by the cellophane can also be used. As the base material of the present invention, those obtained by molding these resins into a film shape are used. Either an unstretched film or a uniaxially or biaxially stretched film can be used, but a stretched polyamide film or a stretched polyester film is most preferable from the viewpoint of ease of coating when coating the barrier layer and the strength of the barrier material.
上述の方法で調製したガスバリアコート剤を用いて、プラスチックフィルムからなる基材に塗布するには、通常のコーティング法を用いることができる。例えば、リバースロールコーティング法、ディップコーティング法、メイヤーバーコーティング法、ナイフコート法、ノズルコーティング法、ダイコーティング法、スプレーコーティング法、カーテンコーティング法、スクリーン印刷、グラビアコート、などの各種印刷法などが挙げられる。これらを組み合わせてもよい。乾燥後のバリアコート層厚みは、0.01〜3.0μm、好ましくは0.05〜1.5μmがよい。乾燥後の厚さが0.01μm未満であると、充分なガスバリア性が発現しない。一方、乾燥後のコート層厚さが3.0μmを超えると、クラックの発生や不十分な密着強度によって、ガスバリア性が低下するし、コストアップともなるので好ましくない。 In order to apply the gas barrier coating agent prepared by the above-described method to a substrate made of a plastic film, a normal coating method can be used. Examples include reverse roll coating, dip coating, Mayer bar coating, knife coating, nozzle coating, die coating, spray coating, curtain coating, screen printing, gravure coating, and other printing methods. It is done. These may be combined. The barrier coat layer thickness after drying is 0.01 to 3.0 μm, preferably 0.05 to 1.5 μm. If the thickness after drying is less than 0.01 μm, sufficient gas barrier properties are not exhibited. On the other hand, if the coating layer thickness after drying exceeds 3.0 μm, the gas barrier property is lowered due to the occurrence of cracks and insufficient adhesion strength, and the cost is increased.
本発明において、プラスチックフィルムからなる基材とガスバリアコート剤塗布層との間に接着層を設けても良い。この接着層を形成する接着剤の具体例としてはカルボキシル基、酸無水物基、オキサゾリン基、チオイソシアネート基、エポキシ基を含む化合物を含有したものが挙げられる。接着剤中に無機フィラーを添加しても良く、添加する無機フィラーとしては、接着層中に均一に微分散し透明性を得る事が出来れば特に限定はされず、具体的にはシリカ、タルク、アルミナ、ウンモ、炭酸カルシウム等が挙げられる。無機フィラーは、表面未処理のもの、表面処理したものともに使用できる。 In the present invention, an adhesive layer may be provided between the substrate made of a plastic film and the gas barrier coating agent coating layer. Specific examples of the adhesive forming the adhesive layer include those containing a compound containing a carboxyl group, an acid anhydride group, an oxazoline group, a thioisocyanate group, and an epoxy group. An inorganic filler may be added to the adhesive, and the inorganic filler to be added is not particularly limited as long as it can be uniformly finely dispersed in the adhesive layer to obtain transparency. Specifically, silica, talc , Alumina, unmo, calcium carbonate and the like. The inorganic filler can be used both untreated and treated.
前述の接着剤を、プラスチックフィルムからなる基材に塗布するには、通常のコーティング法を用いることができる。例えば、リバースロールコーティング法、ディップコーティング法、メイヤーバーコーティング法、ナイフコート法、ノズルコーティング法、ダイコーティング法、スプレーコーティング法、カーテンコーティング法、スクリーン印刷、グラビアコート、などの各種印刷法などが挙げられる。これらを組み合わせてもよい。接着剤をコート後、乾燥することで、接着層が形成される。
乾燥後の接着層の厚みは、0.02〜0.40μm、好ましくは0.06〜0.20μmがよい。乾燥後の厚さが0.02μm未満であると、充分な接着力が発現しない。一方、乾燥後のコート層厚さが0.40μmを超えると、コストアップともなるので好ましくない。
In order to apply the above-mentioned adhesive to a substrate made of a plastic film, a normal coating method can be used. Examples include reverse roll coating, dip coating, Mayer bar coating, knife coating, nozzle coating, die coating, spray coating, curtain coating, screen printing, gravure coating, and other printing methods. It is done. These may be combined. The adhesive layer is formed by drying after coating the adhesive.
The thickness of the adhesive layer after drying is 0.02 to 0.40 μm, preferably 0.06 to 0.20 μm. When the thickness after drying is less than 0.02 μm, sufficient adhesive strength is not exhibited. On the other hand, if the thickness of the coating layer after drying exceeds 0.40 μm, the cost increases, which is not preferable.
ポリアミン、ポリカルボン酸、膨潤性薄片状無機物の混合物からなるガスバリアコート剤を塗布後は、バリアコート層の乾燥および熱処理を行い、高湿度下においても高いガスバリア性を有するバリアコート層を形成させる。具体的には、乾燥後、140以上260℃以下で1秒以上、好ましくは180以上215℃以下で45秒以上の熱処理を行う。140℃よりも低いと十分な熱処理効果が得られにくく、沸騰水によるボイル処理を30分行った直後の20℃×90%RHの酸素透過度が20cc/m2・atm・24h以下であるガスバリア性フィルムを得ることが困難となる。また、基材フィルムの融点付近であれば基材の強度が著しく低下するため好ましくない。 After applying the gas barrier coating agent comprising a mixture of polyamine, polycarboxylic acid, and swellable flaky inorganic material, the barrier coating layer is dried and heat-treated to form a barrier coating layer having high gas barrier properties even under high humidity. Specifically, after drying, heat treatment is performed at 140 to 260 ° C. for 1 second or longer, preferably 180 to 215 ° C. or lower for 45 seconds or longer. When the temperature is lower than 140 ° C., it is difficult to obtain a sufficient heat treatment effect, and a gas barrier whose oxygen permeability of 20 ° C. × 90% RH is 20 cc / m 2 · atm · 24 h or less immediately after boiling with boiling water for 30 minutes. It becomes difficult to obtain a conductive film. Moreover, if it is near melting | fusing point of a base film, since the intensity | strength of a base material will fall remarkably, it is unpreferable.
以上の工程により得られたガスバリア性フィルムは、沸騰水(98〜100℃)で30分以上ボイル後でも良好なガスバリア性を有している。
本発明のフィルムは、沸騰水で30分間ボイル処理を行い、水滴を拭き取った直後の20℃―90%RHでの酸素透過度が、20cc/m2・atm・24h以下となる。酸素透過度が、20cc/m2・atm・24h以下であれば、包装材料を透過する酸素による被包装物に対する酸化劣化等の影響を防止することができる。
The gas barrier film obtained by the above steps has good gas barrier properties even after boiling with boiling water (98 to 100 ° C.) for 30 minutes or more.
The film of the present invention is boiled with boiling water for 30 minutes, and has an oxygen permeability of 20 cc / m 2 · atm · 24 h or less immediately after wiping off water droplets at 20 ° C.-90% RH. If the oxygen permeability is 20 cc / m 2 · atm · 24 h or less, it is possible to prevent the influence of oxidative deterioration or the like on the object to be packaged by oxygen that permeates the packaging material.
実施例および比較例を用いて、本発明の有用性について具体的に説明する。なお、各物性の測定に用いた装置および条件は以下の通りである。 The usefulness of the present invention will be specifically described using examples and comparative examples. In addition, the apparatus and conditions used for the measurement of each physical property are as follows.
<酸素透過度測定>
イリノイ社製酸素透過度測定装置model8000を用いた。測定に際しては、前処理として沸騰水(98〜100℃)で30分間ボイル処理を行い、水滴を拭き取った後、直ちに20℃―90%RHでの酸素透過度の測定を行った
<Oxygen permeability measurement>
An oxygen permeability measuring apparatus model 8000 manufactured by Illinois was used. In the measurement, as a pretreatment, boiling treatment (98-100 ° C.) was performed for 30 minutes, and after wiping off water droplets, oxygen permeability was measured immediately at 20 ° C.-90% RH.
<コート剤調整に使用したポリマー>
(1) ポリアミン
・ポリアリルアミン:日東紡績株式会社製ポリアリルアミン10wt%水溶液「PAA−10C」。
・ポリエチレンイミン:純正化学株式会社製「ポリエチレンイミン 10000」1.25重量部に純水11.25重量部を加え、10wt%に希釈した水溶液。表1では「PEI」と表記。
(2) ポリカルボン酸
・ポリアクリル酸:重量平均分子量20000〜30000。東亜合成株式会社製ポリアクリル酸40wt%水溶液「ジュリマーAC−10L」10.0重量部に25wt%アンモニア水3.03重量部、純水7.00重量部を加えて20wt%に希釈した、カルボキシル基に対するアンモニアの添加量が0.8当量である水溶液。表1では「AC−10L」と表記。
・ポリアクリル酸アンモニウム:重量平均分子量100000。東亜合成株式会社製ポリアクリル酸アンモニウム30wt%水溶液「アロンA−30」10.0重量部に純水10.0重量部を加えて15wt%に希釈した水溶液。表1では「A−30」と表記。
・ポリアクリル酸アンモニウム:重量平均分子量100000。東亜合成株式会社製ポリアクリル酸アンモニウム30wt%水溶液「アロンA−30」10.0重量部に純水17.2重量部を加えて11wt%に希釈した水溶液。表1では「A−30−2」と表記。
(3) 膨潤性薄片状無機物
・合成ヘクトライト:アスペクト比25のROCKWOOD ADDITIVES LIMITED製Laponite RD3.0重量部に純水97.0重量部を加えて3.0wt%に希釈し、特殊機化工業株式会社製T.K. HOMOMIXER MARK II fmodelを使用して10000rpmで1時間攪拌した水溶液。表1では「Laponite RD」と表記。
・合成ヘクトライト:トピー工業株式会社製のナトリウムヘクトライト5wt%分散液「NHT−ゾルB2」60.0重量部に純水40.0重量部を加えて3.0wt%に希釈し、特殊機化工業株式会社製T.K. HOMOMIXER MARK II fmodelを使用して10000rpmで1時間攪拌した水溶液。表1では「NHT−ゾルB2」と表記。
・合成マイカ:アスペクト比が1000以上であるトピー工業株式会社製のナトリウム四ケイ素雲母6wt%分散液「NTS−5」50.0重量部に純水50.0重量部を加えて3.0wt%に希釈し、特殊機化工業株式会社製T.K. HOMOMIXER MARK II fmodelを使用して10000rpmで1時間攪拌した水溶液。表1では「NTS−5」と表記。
<Polymer used for coating agent adjustment>
(1) Polyamine / polyallylamine: a polyallylamine 10 wt% aqueous solution “PAA-10C” manufactured by Nitto Boseki Co., Ltd.
Polyethyleneimine: An aqueous solution obtained by adding 11.25 parts by weight of pure water to 1.25 parts by weight of “Polyethyleneimine 10000” manufactured by Junsei Chemical Co., Ltd. and diluting to 10 wt%. In Table 1, expressed as “PEI”.
(2) Polycarboxylic acid / polyacrylic acid: weight average molecular weight 20000-30000. Carboxyl carboxylate diluted to 20 wt% by adding 3.03 parts by weight of 25 wt% aqueous ammonia and 7.00 parts by weight of pure water to 10.0 parts by weight of polyacrylic acid 40 wt% aqueous solution “Durimer AC-10L” manufactured by Toa Gosei Co., Ltd. An aqueous solution in which the amount of ammonia added to the group is 0.8 equivalent. In Table 1, expressed as “AC-10L”.
-Ammonium polyacrylate: weight average molecular weight 100,000. An aqueous solution obtained by adding 10.0 parts by weight of pure water to 10.0 parts by weight of an aqueous solution of ammonium polyacrylate “Aron A-30” manufactured by Toa Gosei Co., Ltd. and then diluting to 15% by weight. In Table 1, expressed as “A-30”.
-Ammonium polyacrylate: weight average molecular weight 100,000. An aqueous solution prepared by adding 17.2 parts by weight of pure water to 10.0 parts by weight of an aqueous solution of ammonium polyacrylate “Aron A-30” manufactured by Toa Gosei Co., Ltd. and diluting to 11 wt%. In Table 1, expressed as “A-30-2”.
(3) Swellable flaky inorganic material / synthetic hectorite: Add 97.0 parts by weight of pure water to 3.0 parts by weight of Laponite RD made by ROCKWOOD ADDITIVES LIMITED with an aspect ratio of 25, and dilute to 3.0 wt%. T. K. Aqueous solution stirred for 1 hour at 10,000 rpm using a HOMOMIXER MARK II fmodel. In Table 1, expressed as “Laponite RD”.
-Synthetic hectorite: 40.0 parts by weight of pure water was added to 60.0 parts by weight of sodium hectorite dispersion "NHT-sol B2" manufactured by Topy Industries Co., Ltd. and diluted to 3.0% by weight. T.K. K. Aqueous solution stirred for 1 hour at 10,000 rpm using a HOMOMIXER MARK II fmodel. In Table 1, expressed as “NHT-sol B2”.
-Synthetic mica: 50.0 parts by weight of pure water 5% by weight of "NTS-5" dispersion 4% by weight of sodium tetrasilicon mica manufactured by Topy Industries Co., Ltd. having an aspect ratio of 1000 or more is added to 3.0 wt% And diluted to T. by Tokushu Kika Kogyo Co., Ltd. K. Aqueous solution stirred for 1 hour at 10,000 rpm using a HOMOMIXER MARK II fmodel. In Table 1, expressed as “NTS-5”.
<実施例1〜17、比較例1〜2、参考例1>
表1に示す、ポリアミンとポリカルボン酸と膨潤性薄片状無機物を、表1に示す重量比となるように混合して、表1に示す濃度のガスバリアコート剤を得た。この時、ガスバリアコート剤中にゲル状物や塊状物が見られた場合は、50℃の水浴で加温しながらゲル状物や塊状物が無くなるまで30分から1時間撹拌を行った。得られたガスバリアコート剤を「ボニール−HR」(株式会社興人製 耐熱性二軸延伸ナイロンフィルム。厚み15μm)上にメーヤーバーを用い塗布後、100℃で15秒乾燥した。乾燥後、熱処理中にフィルムが収縮しないように木枠に固定し、215℃で60秒間熱処理を行った。こうして得られたガスバリア性フィルムに関し、塗膜厚みの測定、酸素透過度の測定を行った。その結果を表1に示す。
<Examples 1-17, Comparative Examples 1-2, Reference Example 1>
Polyamine, polycarboxylic acid, and swellable flaky inorganic material shown in Table 1 were mixed so as to have a weight ratio shown in Table 1 to obtain a gas barrier coating agent having a concentration shown in Table 1. At this time, when a gel or a lump was found in the gas barrier coating agent, the mixture was stirred for 30 minutes to 1 hour until the gel or lump disappeared while heating in a 50 ° C. water bath. The obtained gas barrier coating agent was applied onto “Bonyl-HR” (a heat-resistant biaxially stretched nylon film manufactured by Kojin Co., Ltd., thickness: 15 μm) using a Mayer bar, and then dried at 100 ° C. for 15 seconds. After drying, the film was fixed to a wooden frame so that the film did not shrink during heat treatment, and heat treatment was performed at 215 ° C. for 60 seconds. The gas barrier film thus obtained was measured for coating film thickness and oxygen permeability. The results are shown in Table 1.
実施例、比較例、参考例の結果より、バリアコート剤であるポリアミン、ポリカルボン酸、膨潤性薄片状無機物の混合物において、ポリアミンとポリカルボン酸の重量比がポリアミン/ポリカルボン酸=12.5/87.5〜27.5/72.5、かつ、(ポリアミン+ポリカルボン酸)/膨潤性薄片状無機物が100/5〜100/50となるような範囲であれば、乾燥後の塗膜(バリアコート層)の厚みが1μm未満であっても、沸騰水によるボイル処理を30分行った直後の20℃×90%RHの酸素透過度が20cc/m2・atm・24h以下である良好なガスバリア性フィルムが得られることが分かる。 From the results of Examples, Comparative Examples, and Reference Examples, in the mixture of polyamine, polycarboxylic acid, and swellable flaky inorganic material that are barrier coating agents, the weight ratio of polyamine to polycarboxylic acid is polyamine / polycarboxylic acid = 12.5. /87.5 to 27.5 / 72.5, and (polyamine + polycarboxylic acid) / swellable flaky inorganic material in a range of 100/5 to 100/50, the coating film after drying Even if the thickness of the (barrier coat layer) is less than 1 μm, the oxygen permeability of 20 ° C. × 90% RH immediately after boiling for 30 minutes with boiling water is 20 cc / m 2 · atm · 24 h or less It can be seen that a gas barrier film can be obtained.
本願発明のガスバリアフィルムは、沸騰水中でボイルした後でも十分なガスバリア性を保持し、被包装物の酸化劣化を防止できるため、一般的なガスバリアフィルムの用途のほか、レトルト包装などにも好適に用いることができる。
The gas barrier film of the present invention retains sufficient gas barrier properties even after boiling in boiling water, and can prevent oxidative deterioration of the packaged object, so it is suitable for general gas barrier film applications, retort packaging, etc. Can be used.
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