JP4865707B2 - ガスバリア性積層体およびその製造方法ならびにそれを用いた包装体 - Google Patents
ガスバリア性積層体およびその製造方法ならびにそれを用いた包装体 Download PDFInfo
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- JP4865707B2 JP4865707B2 JP2007518979A JP2007518979A JP4865707B2 JP 4865707 B2 JP4865707 B2 JP 4865707B2 JP 2007518979 A JP2007518979 A JP 2007518979A JP 2007518979 A JP2007518979 A JP 2007518979A JP 4865707 B2 JP4865707 B2 JP 4865707B2
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- 238000011160 research Methods 0.000 description 1
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- 238000007790 scraping Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- AIFMYMZGQVTROK-UHFFFAOYSA-N silicon tetrabromide Chemical compound Br[Si](Br)(Br)Br AIFMYMZGQVTROK-UHFFFAOYSA-N 0.000 description 1
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- HDUMBHAAKGUHAR-UHFFFAOYSA-J titanium(4+);disulfate Chemical compound [Ti+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O HDUMBHAAKGUHAR-UHFFFAOYSA-J 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- MYWQGROTKMBNKN-UHFFFAOYSA-N tributoxyalumane Chemical compound [Al+3].CCCC[O-].CCCC[O-].CCCC[O-] MYWQGROTKMBNKN-UHFFFAOYSA-N 0.000 description 1
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 description 1
- CPYKRKMVWIPNFZ-UHFFFAOYSA-N trichloro-(3-chloro-2-phenylpropyl)silane Chemical compound Cl[Si](Cl)(Cl)CC(CCl)C1=CC=CC=C1 CPYKRKMVWIPNFZ-UHFFFAOYSA-N 0.000 description 1
- CDNLYCKVRAKJMX-UHFFFAOYSA-N trichloro-[2-(chloromethyl)phenyl]silane Chemical compound ClCC1=CC=CC=C1[Si](Cl)(Cl)Cl CDNLYCKVRAKJMX-UHFFFAOYSA-N 0.000 description 1
- OEBWMIHWFIEUFN-UHFFFAOYSA-N trichloromethoxysilane Chemical compound [SiH3]OC(Cl)(Cl)Cl OEBWMIHWFIEUFN-UHFFFAOYSA-N 0.000 description 1
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 1
- 239000005052 trichlorosilane Substances 0.000 description 1
- NMEPHPOFYLLFTK-UHFFFAOYSA-N trimethoxy(octyl)silane Chemical compound CCCCCCCC[Si](OC)(OC)OC NMEPHPOFYLLFTK-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- LFRDHGNFBLIJIY-UHFFFAOYSA-N trimethoxy(prop-2-enyl)silane Chemical compound CO[Si](OC)(OC)CC=C LFRDHGNFBLIJIY-UHFFFAOYSA-N 0.000 description 1
- UAEJRRZPRZCUBE-UHFFFAOYSA-N trimethoxyalumane Chemical compound [Al+3].[O-]C.[O-]C.[O-]C UAEJRRZPRZCUBE-UHFFFAOYSA-N 0.000 description 1
- SPHALHRGAQVBKI-UHFFFAOYSA-N trimethoxysilylmethanol Chemical compound CO[Si](CO)(OC)OC SPHALHRGAQVBKI-UHFFFAOYSA-N 0.000 description 1
- 125000002221 trityl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C([*])(C1=C(C(=C(C(=C1[H])[H])[H])[H])[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 239000005050 vinyl trichlorosilane Substances 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229960000314 zinc acetate Drugs 0.000 description 1
- 235000013904 zinc acetate Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
- GBNDTYKAOXLLID-UHFFFAOYSA-N zirconium(4+) ion Chemical compound [Zr+4] GBNDTYKAOXLLID-UHFFFAOYSA-N 0.000 description 1
- LJQSESUEJXAKBR-UHFFFAOYSA-J zirconium(4+) tetrachloride octahydrate Chemical compound O.O.O.O.O.O.O.O.[Cl-].[Cl-].[Cl-].[Cl-].[Zr+4] LJQSESUEJXAKBR-UHFFFAOYSA-J 0.000 description 1
Classifications
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- B32B27/00—Layered products comprising a layer of synthetic resin
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- B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
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- B65D65/40—Applications of laminates for particular packaging purposes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/10—Block or graft copolymers containing polysiloxane sequences
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/724—Permeability to gases, adsorption
- B32B2307/7242—Non-permeable
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- B32B2553/00—Packaging equipment or accessories not otherwise provided for
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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
- C08K2201/00—Specific properties of additives
- C08K2201/008—Additives improving gas barrier properties
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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
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- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K5/04—Oxygen-containing compounds
- C08K5/05—Alcohols; Metal alcoholates
- C08K5/057—Metal alcoholates
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
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- Y10T428/1334—Nonself-supporting tubular film or bag [e.g., pouch, envelope, packet, etc.]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
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Description
本発明のガスバリア性積層体は、基材と、基材の少なくとも一方の面に積層された層(以下、「ガスバリア層」という場合がある)とを含むガスバリア性積層体(多層構造体)である。そのガスバリア層は、ハロゲン原子およびアルコキシ基から選ばれる少なくとも1つの基が結合した金属原子を含む少なくとも1種の化合物(L)の加水分解縮合物と、カルボキシル基およびカルボン酸無水物基から選ばれる少なくとも1つの官能基を含有する重合体の中和物と、化合物(D)と、を含む組成物からなる。該少なくとも1つの官能基に含まれる−COO−基の少なくとも一部は2価以上の金属イオンで中和されている。化合物(L)は、上記金属原子に、ハロゲン原子、メルカプト基および水酸基から選ばれる少なくとも1つの特性基を有する有機基がさらに結合した少なくとも1種の化合物(A)を含む。化合物(D)は、上記加水分解縮合物の表面の基、および、上記少なくとも1つの官能基に含まれる−COO−基の両方と結合する化合物である。なお、組成物は、1種類の化合物(D)を含んでもよいし、複数種の化合物(D)を含んでもよい。
Si(OR1)mR2 nX1 kZ4-m-n-k・・・(I)
[化学式(I)中、R1およびR2はそれぞれ独立にアルキル基を表す。X1はハロゲン原子を表す。Zはハロゲン原子、メルカプト基および水酸基から選ばれる少なくとも1つの特性基を有する有機基を表す。mは0〜3の整数を表す。nは0〜2の整数を表す。kは0〜3の整数を表す。1≦m+k≦3である。1≦m+n+k≦3である。]
M(OR3)qR4 p-q-rX2 r・・・(II)
以下、ガスバリア性積層体を製造するための本発明の方法について説明する。この方法によれば、本発明のガスバリア性積層体を容易に製造できる。本発明の製造方法に用いられる材料、および積層体の構成は、上述したものと同様であるので、重複する部分については説明を省略する場合がある。
ガスバリア層/AC/OPETという構造を有する積層体について、酸素透過量測定装置(モダンコントロール社製「MOCON OX−TRAN10/50」)を用いて酸素透過度を測定した。具体的には、酸素供給側にガスバリア層が向き、キャリアガス側にOPETが向くように積層体をセットし、温度20℃、酸素圧1気圧、キャリアガス圧力1気圧の条件下で、酸素透過度(単位:cc/m2・day・atm)を測定した。このとき、湿度を85%RHとし、酸素供給側とキャリアガス側とを同一の湿度とした。
ガスバリア層/AC/OPET/接着剤/ONy/接着剤/PPという構造を有する積層体(サイズ:12cm×12cm)を2枚作製した。そして、その2枚をガスバリア層が外側になるように重ねあわせたのち、積層体の3辺をその端から5mmまでヒートシールした。ヒートシールされた2枚の積層体の間に蒸留水80gを注入したのち、残された第4辺を同様にヒートシールした。このようにして、蒸留水が中に入ったパウチを作製した。
上記の(1)酸素バリア性の評価用に作製した積層体について、ヘイズメータ(株式会社村上色彩技術研究所、HR−100)を用いてJIS K 7105の方法に基づいてヘイズ値を測定した。
上記の(1)酸素バリア性の評価用に作製した積層体について、フーリエ変換赤外分光光度計(株式会社島津製作所製、8200PC)を用いて、ATR(全反射測定)のモードで、ガスバリア層に含まれるC=O伸縮振動のピークを観察した。イオン化前のカルボン酸含有重合体のカルボキシル基のC=O伸縮振動に帰属されるピークは1600cm-1〜1850cm-1の範囲に観察され、イオン化された後のカルボキシル基のC=O伸縮振動は1500cm-1〜1600cm-1の範囲に観察された。そして、それぞれの範囲における最大の吸光度からその比を算出し、その比と予め下記の方法で作成した検量線とを用いてイオン化度を求めた。
数平均分子量150,000のポリアクリル酸を蒸留水に溶解し、所定量の水酸化ナトリウムでカルボキシル基を中和した。得られたポリアクリル酸の中和物の水溶液を、基材上に、イオン化度の測定の対象となる積層体のガスバリア層と同じ厚さになるようにコートし、乾燥させた。基材には、2液型のアンカーコート剤(三井武田ケミカル株式会社製、タケラック3210(商品名)およびタケネートA3072(商品名)、以下ACと略記することがある)を表面にコートした延伸PETフィルム(東レ株式会社製、ルミラー(商品名)。厚さ12μm。以下、「OPET」と略記することがある)を用いた。このようにして、カルボキシル基の中和度が、0〜100モル%間で10モル%ずつ異なる11種類の標準サンプル[積層体(ポリアクリル酸の中和物からなる層/AC/OPET)]を作製した。これらのサンプルについて、フーリエ変換赤外分光光度計(島津製作所製、8200PC)を用いて、ATR(全反射測定)のモードで、赤外吸収スペクトルを測定した。そして、ポリアクリル酸の中和物からなる層に含まれるC=O伸縮振動に対応する2つのピーク、すなわち、1600cm-1〜1850cm-1の範囲に観察されるピークと1500cm-1〜1600cm-1の範囲に観察されるピークとについて、吸光度の最大値の比を算出した。そして、算出した比と、各標準サンプルのイオン化度とを用いて検量線を作成した。
イオン化処理前のガスバリア層の無機成分含有率を、上述した方法、すなわち仕込み原料の重量から算出する方法で算出した。
ガスバリア層/AC/OPETという構造を有する積層体を、23℃50%RHに調整した部屋に1週間以上置いて調湿した。この積層体から、スリップ板(SUS製、23.6×10.5×0.2cm)を包み込める大きさの積層体1枚と、スレッド(SUS製、4×3×1cm、重さ91.9281g)を包み込める大きさの積層体5枚とを切り出した。
(7−1)レトルト処理前の剥離強度
OPET/AC/ガスバリア層/接着剤(1)/ONy/接着剤(2)/PPの構成の積層体を作製し、この積層体を幅15mmに切断した。ガスバリア層と接着剤(1)との間を剥離面として、T型剥離強度を引張速度250mm/分で測定した。
OPET/AC/ガスバリア層/接着剤(1)/ONy/接着剤(2)/PPの構成の積層体を作製し、該積層体を25mm×150mmに切断した。別途、2枚ポリプロピレン層(40mm×200mm)を重ねあわせたのち、その3辺をその端から5mmまでヒートシールしたパウチを作製した。該パウチの中に、上述した積層体を入れ、更に蒸留水を注入して積層体が水で完全に浸っている状態にした後、パウチ内のエアーを抜きながら、第4辺を同様にヒートシールした。このようにして、蒸留水に浸漬した積層体が中に入ったパウチを作製した。
上記(1)酸素バリア性の評価用に作製した積層体について、目視によって、透明性や、ガスバリア層の表面状態(凹凸、クラック等の有無)を観察した。凹凸、クラック等が発生していない場合については、「良好(A)」と判定し、発生している場合については、「不良(B)」と判定した。
数平均分子量150,000のポリアクリル酸(PAA)を蒸留水で溶解し、水溶液中の固形分濃度が10重量%であるポリアクリル酸水溶液を得た。
数平均分子量150,000のポリアクリル酸(PAA)を蒸留水で溶解し、水溶液中の固形分濃度が10重量%であるポリアクリル酸水溶液を得た。
数平均分子量150,000のポリアクリル酸(PAA)を蒸留水で溶解し、水溶液中の固形分濃度が10重量%であるポリアクリル酸水溶液を得た。
数平均分子量150,000のポリアクリル酸(PAA)を蒸留水で溶解し、水溶液中の固形分濃度が10重量%であるポリアクリル酸水溶液を得た。
数平均分子量150,000のポリアクリル酸(PAA)を蒸留水で溶解し、水溶液中の固形分濃度が10重量%であるポリアクリル酸水溶液を得た。
数平均分子量150,000のポリアクリル酸(PAA)を蒸留水で溶解し、水溶液中の固形分濃度が10重量%であるポリアクリル酸水溶液を得た。
数平均分子量150,000のポリアクリル酸(PAA)を蒸留水で溶解し、水溶液中の固形分濃度が10重量%であるポリアクリル酸水溶液を得た。
数平均分子量150,000のポリアクリル酸(PAA)を蒸留水で溶解し、水溶液中の固形分濃度が10重量%であるポリアクリル酸水溶液を得た。
数平均分子量150,000のポリアクリル酸(PAA)を蒸留水で溶解し、水溶液中の固形分濃度が10重量%であるポリアクリル酸水溶液を得た。
数平均分子量150,000のポリアクリル酸(PAA)を蒸留水で溶解し、水溶液中の固形分濃度が10重量%であるポリアクリル酸水溶液を得た。
数平均分子量150,000のポリアクリル酸(PAA)を蒸留水で溶解し、水溶液中の固形分濃度が10重量%であるポリアクリル酸水溶液を得た。
数平均分子量150,000のポリアクリル酸(PAA)を蒸留水で溶解し、水溶液中の固形分濃度が10重量%であるポリアクリル酸水溶液を得た。
Claims (18)
- 基材と、前記基材の少なくとも一方の面に積層された層とを含み、
前記層は、ハロゲン原子およびアルコキシ基から選ばれる少なくとも1つの基が結合した金属原子を含む少なくとも1種の化合物(L)の加水分解縮合物と、カルボキシル基およびカルボン酸無水物基から選ばれる少なくとも1つの官能基を含有する重合体の中和物と、化合物(D)と、を含む組成物からなり、
前記少なくとも1つの官能基に含まれる−COO−基の少なくとも一部が2価以上の金属イオンで中和されており、
前記化合物(L)は、前記金属原子に、ハロゲン原子、メルカプト基および水酸基から選ばれる少なくとも1つの特性基を有する有機基がさらに結合した少なくとも1種の化合物(A)を含み、
前記加水分解縮合物の表面には、水酸基、アルコキシ基およびハロゲン原子からなる群より選ばれる少なくとも1つの基が存在し、
前記化合物(D)は、前記加水分解縮合物の表面の水酸基、アルコキシ基またはハロゲン原子と結合可能な第1の原子団と、前記少なくとも1つの官能基に含まれる−COO−基と結合可能な第2の原子団とを備える、チタン化合物および/またはジルコニウム化合物であり、
前記少なくとも1つの官能基に含まれる−COO−基の量に対する前記化合物(D)の量の割合が、0.01〜50モル%の範囲にある、ガスバリア性積層体。 - 前記金属原子がケイ素原子である請求項1に記載のガスバリア性積層体。
- 前記化合物(A)が、以下の化学式(I)で示される請求項1に記載のガスバリア性積層体。
Si(OR1)mR2 nX1 kZ4-m-n-k・・・(I)
[化学式(I)中、R1およびR2はそれぞれ独立にアルキル基を表す。X1はハロゲン原子を表す。Zはハロゲン原子、メルカプト基および水酸基から選ばれる少なくとも1つの特性基を有する有機基を表す。mは0〜3の整数を表す。nは0〜2の整数を表す。kは0〜3の整数を表す。1≦m+k≦3である。1≦m+n+k≦3である。] - 前記化合物(A)が、クロロメチルトリアルコキシシラン、クロロメチルトリクロロシラン、2−クロロエチルトリアルコキシシラン、2−クロロエチルトリクロロシラン、3−クロロプロピルトリアルコキシシラン、3−クロロプロピルトリクロロシラン、メルカプトメチルトリアルコキシシラン、メルカプトメチルトリクロロシラン、2−メルカプトエチルトリアルコキシシラン、2−メルカプトエチルトリクロロシラン、3−メルカプトプロピルトリアルコキシシラン、3−メルカプトプロピルトリクロロシラン、N−(3−トリアルコキシシリルプロピル)グルコンアミド、N−(3−トリアルコキシシリルプロピル)−4−ヒドロキシブチルアミドから選ばれる少なくとも1種の化合物を含む請求項1に記載のガスバリア性積層体。
- 20℃85%RH雰囲気における酸素透過速度が1.0cc/m2・day・atm以下である請求項1に記載のガスバリア性積層体。
- ヘイズ値が3%以下である請求項1に記載のガスバリア性積層体。
- 前記化合物(L)が、以下の化学式(II)で表される少なくとも1種の化合物(B)をさらに含む請求項1に記載のガスバリア性積層体。
M(OR3)qR4 p-q-rX2 r・・・(II)
[化学式(II)中、MはSi、Al、Ti、Zr、Cu、Ca、Sr、Ba、Zn、B、Ga、Y、Ge、Pb、P、Sb、V、Ta、W、LaまたはNdを表す。R3はアルキル基を表す。R4はアルキル基、アラルキル基、アリール基またはアルケニル基を表す。X2はハロゲン原子を表す。pは金属元素Mの原子価と等しい。qは0〜pの整数を表す。rは0〜pの整数を表す。また、1≦q+r≦pである。] - 前記化合物(L)に含まれる前記化合物(A)と前記化合物(B)とのモル比が、前記化合物(A)/前記化合物(B)=0.1/99.9〜40/60である請求項7に記載のガスバリア性積層体。
- 前記組成物中における前記化合物(L)由来の無機成分の含有率が、5〜50重量%の範囲である請求項7に記載のガスバリア性積層体。
- 前記少なくとも1つの官能基に含まれる−COO−基の10モル%以上が、前記金属イオンによって中和されている請求項1に記載のガスバリア性積層体。
- 前記少なくとも1つの官能基に含まれる−COO−基の0.1〜10モル%が、1価のイオンによって中和されている請求項1に記載のガスバリア性積層体。
- 前記重合体が、ポリアクリル酸およびポリメタクリル酸から選ばれる少なくとも1種の重合体である請求項1に記載のガスバリア性積層体。
- 前記化合物(D)がテトラアルコキシチタンである請求項1に記載のガスバリア性積層体。
- 請求項1に記載のガスバリア性積層体を用いた包装体。
- (i)ハロゲン原子およびアルコキシ基から選ばれる少なくとも1つの基が結合した金属原子を含む少なくとも1種の化合物(L)の加水分解縮合物と、カルボキシル基およびカルボン酸無水物基から選ばれる少なくとも1つの官能基を含有する重合体と、化合物(D)とが混合された混合液を調製する工程と、
(ii)前記混合液を基材上に塗布して乾燥させることによって前記基材上に層を形成する工程と、
(iii)前記層を、2価以上の金属イオンを含む溶液に接触させる工程と、を含み、
前記化合物(L)は、前記金属原子に、ハロゲン原子、メルカプト基および水酸基から選ばれる少なくとも1つの特性基を有する有機基がさらに結合した少なくとも1種の化合物(A)を含み、
前記加水分解縮合物の表面には、水酸基、アルコキシ基およびハロゲン原子からなる群より選ばれる少なくとも1つの基が存在し、
前記化合物(D)は、前記加水分解縮合物の表面の水酸基、アルコキシ基またはハロゲン原子と結合可能な第1の原子団と、前記少なくとも1つの官能基に含まれる−COO−基と結合可能な第2の原子団とを備える、チタン化合物および/またはジルコニウム化合物であり、
前記少なくとも1つの官能基に含まれる−COO−基の量に対する前記化合物(D)の量の割合が、0.01〜50モル%の範囲にある、ガスバリア性積層体の製造方法。 - 前記(iii)の工程において、前記少なくとも1つの官能基に含まれる−COO−基の10モル%以上を前記2価以上の金属イオンで中和する、請求項15に記載のガスバリア性積層体の製造方法。
- 前記(i)の工程において、前記加水分解縮合物と前記化合物(D)とを混合したのち、さらに前記重合体を混合して前記混合液を得る、請求項15に記載のガスバリア性積層体の製造方法。
- 前記化合物(D)がテトラアルコキシチタンである請求項15に記載のガスバリア性積層体の製造方法。
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JP2004314563A (ja) | 2003-04-21 | 2004-11-11 | Toppan Printing Co Ltd | ガスバリアフィルム積層体 |
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2006
- 2006-05-29 WO PCT/JP2006/310696 patent/WO2006129619A1/ja active Application Filing
- 2006-05-29 JP JP2007518979A patent/JP4865707B2/ja active Active
- 2006-05-29 KR KR1020087000068A patent/KR101245541B1/ko active IP Right Grant
- 2006-05-29 AU AU2006253520A patent/AU2006253520B2/en active Active
- 2006-05-29 CN CN200680019547XA patent/CN101189125B/zh active Active
- 2006-05-29 EP EP06746974.2A patent/EP1892089B1/en active Active
- 2006-05-29 US US11/916,371 patent/US7799396B2/en active Active
- 2006-05-29 CA CA 2610461 patent/CA2610461A1/en not_active Abandoned
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JP2002326303A (ja) * | 2001-04-27 | 2002-11-12 | Nippon Shokubai Co Ltd | 気体バリア性積層フィルム |
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JP2003292713A (ja) * | 2002-04-01 | 2003-10-15 | Rengo Co Ltd | ガスバリア性樹脂組成物及びこれから成形されるガスバリア性フィルム |
WO2003091317A1 (en) * | 2002-04-23 | 2003-11-06 | Kureha Chemical Industry Company, Limited | Film and process for producing the same |
WO2005053954A1 (ja) * | 2003-12-03 | 2005-06-16 | Kuraray Co., Ltd. | ガスバリア性積層体および包装体ならびにガスバリア性積層体の製造方法 |
JP4365826B2 (ja) * | 2003-12-03 | 2009-11-18 | 株式会社クラレ | ガスバリア性積層体および包装体ならびにガスバリア性積層体の製造方法 |
Also Published As
Publication number | Publication date |
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JPWO2006129619A1 (ja) | 2009-01-08 |
CN101189125B (zh) | 2012-04-04 |
CA2610461A1 (en) | 2006-12-07 |
WO2006129619A1 (ja) | 2006-12-07 |
AU2006253520A1 (en) | 2006-12-07 |
CN101189125A (zh) | 2008-05-28 |
AU2006253520B2 (en) | 2010-09-23 |
KR101245541B1 (ko) | 2013-03-21 |
EP1892089A4 (en) | 2011-10-19 |
EP1892089B1 (en) | 2019-05-29 |
US20090030126A1 (en) | 2009-01-29 |
US7799396B2 (en) | 2010-09-21 |
KR20080020667A (ko) | 2008-03-05 |
EP1892089A1 (en) | 2008-02-27 |
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