JP2004034390A - Process for producing resin composition for food packaging and laminate for packaging - Google Patents
Process for producing resin composition for food packaging and laminate for packaging Download PDFInfo
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- JP2004034390A JP2004034390A JP2002191924A JP2002191924A JP2004034390A JP 2004034390 A JP2004034390 A JP 2004034390A JP 2002191924 A JP2002191924 A JP 2002191924A JP 2002191924 A JP2002191924 A JP 2002191924A JP 2004034390 A JP2004034390 A JP 2004034390A
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- kneading
- layered silicate
- resin composition
- polyolefin
- raw material
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- 239000011342 resin composition Substances 0.000 title claims abstract description 20
- 238000004806 packaging method and process Methods 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title claims description 12
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000004898 kneading Methods 0.000 claims abstract description 26
- 229920000098 polyolefin Polymers 0.000 claims abstract description 24
- 239000002994 raw material Substances 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 230000004888 barrier function Effects 0.000 claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 claims abstract description 10
- 150000004760 silicates Chemical class 0.000 claims abstract description 10
- 238000005187 foaming Methods 0.000 claims abstract description 8
- 230000008961 swelling Effects 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 238000004299 exfoliation Methods 0.000 claims description 3
- 230000014759 maintenance of location Effects 0.000 abstract description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 3
- 239000003205 fragrance Substances 0.000 abstract description 3
- 239000001301 oxygen Substances 0.000 abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 abstract description 3
- 238000010586 diagram Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 15
- 229920000642 polymer Polymers 0.000 description 8
- -1 polyethylene Polymers 0.000 description 7
- 239000004698 Polyethylene Substances 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- 239000004927 clay Substances 0.000 description 4
- 229910000271 hectorite Inorganic materials 0.000 description 4
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 230000032798 delamination Effects 0.000 description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 229920001684 low density polyethylene Polymers 0.000 description 2
- 239000004702 low-density polyethylene Substances 0.000 description 2
- 229920001179 medium density polyethylene Polymers 0.000 description 2
- 239000004701 medium-density polyethylene Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229910052901 montmorillonite Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229910052615 phyllosilicate Inorganic materials 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 241000588724 Escherichia coli Species 0.000 description 1
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 description 1
- 241001595840 Margarites Species 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 241000589517 Pseudomonas aeruginosa Species 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- RJDOZRNNYVAULJ-UHFFFAOYSA-L [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[F-].[F-].[Mg++].[Mg++].[Mg++].[Al+3].[Si+4].[Si+4].[Si+4].[K+] Chemical compound [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[F-].[F-].[Mg++].[Mg++].[Mg++].[Al+3].[Si+4].[Si+4].[Si+4].[K+] RJDOZRNNYVAULJ-UHFFFAOYSA-L 0.000 description 1
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- VNSBYDPZHCQWNB-UHFFFAOYSA-N calcium;aluminum;dioxido(oxo)silane;sodium;hydrate Chemical compound O.[Na].[Al].[Ca+2].[O-][Si]([O-])=O VNSBYDPZHCQWNB-UHFFFAOYSA-N 0.000 description 1
- 229910001919 chlorite Inorganic materials 0.000 description 1
- 229910052619 chlorite group Inorganic materials 0.000 description 1
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 1
- 229910052620 chrysotile Inorganic materials 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 229910001649 dickite Inorganic materials 0.000 description 1
- YGANSGVIUGARFR-UHFFFAOYSA-N dipotassium dioxosilane oxo(oxoalumanyloxy)alumane oxygen(2-) Chemical compound [O--].[K+].[K+].O=[Si]=O.O=[Al]O[Al]=O YGANSGVIUGARFR-UHFFFAOYSA-N 0.000 description 1
- 229910052621 halloysite Inorganic materials 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- CYPPCCJJKNISFK-UHFFFAOYSA-J kaolinite Chemical compound [OH-].[OH-].[OH-].[OH-].[Al+3].[Al+3].[O-][Si](=O)O[Si]([O-])=O CYPPCCJJKNISFK-UHFFFAOYSA-J 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 229910052630 margarite Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229920001526 metallocene linear low density polyethylene Polymers 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052627 muscovite Inorganic materials 0.000 description 1
- 150000004010 onium ions Chemical class 0.000 description 1
- 229910052628 phlogopite Inorganic materials 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229910052903 pyrophyllite Inorganic materials 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910000275 saponite Inorganic materials 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- WSNJABVSHLCCOX-UHFFFAOYSA-J trilithium;trimagnesium;trisodium;dioxido(oxo)silane;tetrafluoride Chemical compound [Li+].[Li+].[Li+].[F-].[F-].[F-].[F-].[Na+].[Na+].[Na+].[Mg+2].[Mg+2].[Mg+2].[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O WSNJABVSHLCCOX-UHFFFAOYSA-J 0.000 description 1
- CWBIFDGMOSWLRQ-UHFFFAOYSA-N trimagnesium;hydroxy(trioxido)silane;hydrate Chemical compound O.[Mg+2].[Mg+2].[Mg+2].O[Si]([O-])([O-])[O-].O[Si]([O-])([O-])[O-] CWBIFDGMOSWLRQ-UHFFFAOYSA-N 0.000 description 1
- 229910052902 vermiculite Inorganic materials 0.000 description 1
- 239000010455 vermiculite Substances 0.000 description 1
- 235000019354 vermiculite Nutrition 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Wrappers (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
【目的】食品衛生上、安全であり、廉価に製造でき、優れた酸素バリア性、保香及び品質保持性を有する樹脂組成物の製造法及び食品用包装積層体を提供することを目的とする。
【構成】ポリオレフィン中に実質的に均一に分散している微小な層状珪酸塩を含有する樹脂組成物の製造法であって、天然若しくは合成の層状珪酸塩原料を調製し、その層状珪酸塩原料を、後工程の混練工程での層状剥離を容易にする程度に最少の水分で膨潤化し、水膨潤化した原料をポリオレフィンと共に、２軸押出機に充填し、水分の発泡を防ぐ混練条件下で、層状珪酸塩を微小に層状に剥離しながら混練することを特徴とする。
【選択図】 なし[Object] It is an object of the present invention to provide a method for producing a resin composition which is safe in terms of food hygiene, can be produced at a low cost, has excellent oxygen barrier properties, fragrance retention and quality retention, and a packaging laminate for food. .
A method for producing a resin composition containing fine layered silicates substantially uniformly dispersed in a polyolefin, comprising preparing a natural or synthetic layered silicate raw material, Is swollen with a minimum amount of moisture to the extent that laminar peeling in the subsequent kneading step is facilitated, and the water-swelled raw material is charged together with the polyolefin into a twin-screw extruder under kneading conditions to prevent water foaming. It is characterized in that kneading is performed while the layered silicate is finely separated into layers.
[Selection diagram] None
Description
【０００１】
本発明は、食品包装用樹脂組成物の製造法及び包装用積層体に関する。
【０００２】
【従来の技術】
樹脂組成物、例えば、ポリオレフィン、ポリアミド等のポリマーのガスバリヤー性を改良する方法として、層状珪酸塩（いわゆる、クレイ、粘土類）または層間イオンを有機オニウムイオンでイオン交換した層状珪酸塩をポリアミド樹脂中に分散し複合化する方法がある。
【０００３】
複合化の手法としては大きく二種類に分けられる。ポリマーに層状珪酸塩を均一に分散させる方法は、膨潤化剤と接触させて、予め層間を拡げて層間にモノマーを取り込みやすくしたのち、モノマーと混合し、重合する方法（特開昭４８−１０３６５３号公報、特公昭５８−３５５４２号公報、特開昭６２−７４９５７号公報参照）、膨潤化剤に高分子化合物を用い、予め層間を１００Å以上に拡げて、ポリマーと層状珪酸塩をポリマーの溶融温度以上の温度条件下で、二軸押出機等を使用して機械的剪断力により層状珪酸塩を分散させる方法（溶融混合法）（特公昭５８−３５５４２号公報、特開昭４７−３６６８６号公報参照）である。ポリオレフィンなどの無極性の樹脂では、特に、膨潤化していない粘土類は、微小に層状に剥離するすることが難しい。得られた樹脂組成物は、食品包装用バリア性積層体として用いられる。
【０００４】
しかし、重合する上記方法では、重合装置自体の改造が必要になり、大規模かつ高価になる。上記溶融混合法で製造した層状珪酸塩／ポリマー複合化フィルムでは、層状珪酸塩の分散自体も充分でなく、フィルム表面に凹凸等が現れ、フィルム外観や透明性を著しく損なうという他にも、機械的性質が低下するという欠点も有していた。
しかも、食品用包装に用いる場合、食品衛生上、添加する膨潤化剤が問題になることもある。
【０００５】
【発明が解決しようとする課題】
解決しようとする課題は、上記問題点であり、
本発明は、食品衛生上問題になる添加剤の膨潤化剤を用いず安全であり、小規模の生産であっても廉価に製造でき、簡易に層状珪酸塩の均一分散ができ、成形フィルム表面が平滑で、機械的性質が低下しない食品包装用樹脂組成物の製造法及び包装用積層体を提供することを目的とする。
【０００６】
【課題を解決するための手段】
この課題を解決するために本発明は、層状珪酸塩原料を、層状剥離を容易にする程度に最少の水分で膨潤化し、水膨潤化した原料をポリオレフィンと共に、２軸押出機内で、水分の発泡を防ぐ混練条件下で、層状珪酸塩を微小に層状に剥離しながら混練して、ポリオレフィン中に実質的に均一に分散している微小な層状珪酸塩を含有する樹脂組成物を得ることを特徴とする。
このように構成したことにより、上記目的を実現する。
【０００７】
【発明の実施の形態】
本発明の請求項１に記載の発明は、ポリオレフィン中に実質的に均一に分散している微小な層状珪酸塩を含有する樹脂組成物の製造法であって、
天然若しくは合成の層状珪酸塩原料を調製し、
層状珪酸塩の該原料を、後工程の混練工程での層状剥離を容易にする程度に最少の水分で膨潤化し、
水分で膨潤化した該原料をポリオレフィンと共に、２軸押出機に充填し、
水分の発泡を防ぐ混練条件で、層状珪酸塩を微小に層状に剥離しながら混練することを特徴とする食品包装用樹脂組成物の製造法である。
微小な層状化及び分散が容易であるように、水による膨潤化が容易な天然若しくは合成の層状珪酸塩原料を選択し調製する。層状珪酸塩の該原料を最少の水分で膨潤化し、その水分量は後工程の混練工程での層状剥離を容易にする。水分で膨潤化した原料をポリオレフィンと共に、押出機（好ましくは、２軸押出機）に充填し、水分の発泡を防ぐ混練条件で、層状珪酸塩を微小に層状に剥離しながら混練して、ポリオレフィン中に実質的に均一に分散している微小な層状珪酸塩を含有する樹脂組成物を得ることできるという作用を有する。
【０００８】
請求項２に記載の発明は、ポリオレフィン中に実質的に均一に分散している微小な層状珪酸塩を含有するバリア層を含む積層体であって、
該バリア層が、膨潤化剤を用いず水分により膨潤した天然若しくは合成の層状珪酸塩原料をポリオレフィンと共に、押出機（好ましくは、２軸押出機）で、水分の発泡を防ぐ混練条件で、層状珪酸塩を微小に層状に剥離しながら混練して得た樹脂組成物であることを特徴とする食品包装用積層体である。
ポリオレフィン中に実質的に均一に分散している微小な層状珪酸塩を含有するバリア層を含む積層体であって、添加剤の膨潤化剤を含んでおらず食品衛生的に安全であり、水分による発泡が無いので、機械的強度を保ち、均一に分散している微小な層状珪酸塩がバリア性を付与することできるという作用を有する。
以下、本発明の実施の形態について、説明する。
【０００９】
本発明で使用されるポリオレフィンは、ポリエチレン及びポリプロピレンなどの単独重合のポリオレフィン、そのポリオレフィンとのコポリマー、ポリオレフィンとのブンレンドポリマーなどである。
【００１０】
ポリエチレンを用いた場合は、ポリエチレンとしては、包装としてヒートシール性が要求されることから、低密度ポリエチレン（ＬＤＰＥ）や直鎖状低密度ポリエチレン（ＬＬＤＰＥ）、メタロセンＰＥを用いる。また、中密度ポリエチレン（ＭＤＰＥ）や高密度ポリエチレン（ＨＤＰＥ）を用いても良い。
【００１１】
本発明における好ましい態様において、ポリエチレン中に実質的に均一に分散している、微小な層状珪酸塩を含有するにポリオレフィンである。好ましくは、ポリエチレン中に、平均粒径が１〜８０ミクロンの範囲内にあり、かつ３００ミクロン以上の粒径を含まない層状珪酸塩を０．１〜１０重量％含有し、層状珪酸塩は、層間距離が５０オングストローム以上に実質的に均一に分散する。
【００１２】
層状珪酸塩の原料としては、珪酸マグネシウムまたは珪酸アルミニウムの層から構成される層状フィロ珪酸鉱物を例示することができる。具体的には、１：１型層状珪酸塩、即ち、カオリナイト、ディッカイト、ハロイサイト、アンチゴナイト、クリソタイル等や、２：１型層状珪酸塩、即ち、モンモリロナイト、ヘクトライト、フッ素ヘクトライト、サポナイト、バイデライト、スブチンサイト、バーミキュライト等のスメクタイト類、白雲母、金雲母等の雲母類、フッ素金雲母、フッ素白雲母、Ｋ型フッ素テニオライト、Ｋ型四珪素雲母等の膨潤性合成雲母等、Ｌｉ型フッ素テニオライト、Ｎａ型フッ素テニオライト、Ｎａ型四珪素フッ素雲母等の膨潤性合成フッ素雲母、マーガライト、パイロフィライト、タルク、緑泥石等などが挙げられる。表面外観、製品着色、ガスバリヤー性の観点から、中でもモンモリロナイト、ヘクトライト、フッ素ヘクトライト、膨潤性合成フッ素雲母等が好ましい。
【００１３】
本発明の好ましい態様において、Ｎａ、Ｋ、Ｌｉ及びＣａを除く金属イオン（例えば、Ａｇ、Ｚｎ、Ｃｏ、Ｃｄ、Ｃｕから選ばれた金属イオン）又はその金属化合物を層間に有する層状珪酸塩（粘土鉱物）を用いることができる。この層状珪酸塩自体が、緑膿菌、大腸菌、黄色ブドウ球菌などの種々の微生物に対して優れた抗菌性を備える。従って、この層状珪酸塩を含有するバリア層にもこの抗菌性が、更に本発明による包装積層体にも、抗菌性が付与される。
【００１４】
層状珪酸塩の配合量は、ポリオレフィンに対して、酸素バリア性、ストレスに対する耐久性、保香及び品質保持性などの改良効果などを考慮して、適宜、選択・変更できる。
【００１５】
この発明において、ポリオレフィンに層状珪酸塩を均一に分散させる方法は、まず、微小な層状化及び分散が容易であるように、水による膨潤化が容易な天然若しくは合成の層状珪酸塩原料を選択し調製する。その層状珪酸塩原料を最少の水分で膨潤化する。その水分量は、後工程の混練工程での層状剥離を容易にする程度である。水分で膨潤化した原料をポリオレフィンと共に、押出機（好ましくは、２軸押出機）に充填し、水分の発泡を防ぐ混練条件（温度、真空度など）で、層状珪酸塩を微小に層状に剥離しながら混練する。この混練工程により、ポリオレフィン中に実質的に均一に分散している微小な層状珪酸塩を含有する樹脂組成物を得る。
【００１６】
【発明の効果】
以上説明したように本発明の樹脂組成物の製造法及び食品用包装積層体によって、食品衛生上問題になる添加剤の膨潤化剤を用いず安全である。
本発明における食品包装用樹脂組成物及び包装用積層体は、ポリマー中に層状珪酸塩が均一に分された状態で存在することから、優れた酸素バリア性を備え、しかも、保香及び品質保持性に優れている。
【００１７】
この発明の膨潤条件及び混練条件さえ満足すれば、廉価な天然若しくは合成の層状珪酸塩原料を用いることができる。
この発明において、小規模の生産であっても廉価に製造でき、簡易に層状珪酸塩の均一分散ができる。
得られた食品包装用樹脂組成物の成形フィルムは、その表面が平滑で、機械的性質が低下しない。[0001]
The present invention relates to a method for producing a resin composition for food packaging and a laminate for packaging.
[0002]
[Prior art]
As a method of improving the gas barrier properties of a resin composition, for example, a polymer such as polyolefin or polyamide, a layered silicate (so-called clay or clay) or a layered silicate obtained by ion-exchanging interlayer ions with organic onium ions is used as a polyamide resin. There is a method of dispersing and compounding inside.
[0003]
There are roughly two types of compounding methods. A method of uniformly dispersing a layered silicate in a polymer is a method of contacting with a swelling agent, expanding the layers in advance to make it easier to take in monomers between the layers, and then mixing with the monomers and polymerizing (Japanese Patent Laid-Open No. 48-103653). JP-B-58-35542, JP-A-62-74957), using a polymer compound as a swelling agent, expanding the interlayer between layers to 100 mm or more in advance, and melting the polymer and the layered silicate into a polymer. Method of dispersing layered silicate by mechanical shearing force using a twin-screw extruder or the like under a temperature condition not lower than the temperature (melt mixing method) (JP-B-58-35542, JP-A-47-36686) Gazette). In the case of non-polar resins such as polyolefins, it is particularly difficult to exfoliate clay, which is not swelled, in a minute layer. The obtained resin composition is used as a barrier laminate for food packaging.
[0004]
However, the above-mentioned method of polymerizing requires modification of the polymerization apparatus itself, which is large and expensive. In the layered silicate / polymer composite film produced by the above-described melt mixing method, the dispersion of the layered silicate itself is not sufficient, and irregularities and the like appear on the film surface, and the film appearance and transparency are significantly impaired. Also had the disadvantage that the mechanical properties deteriorated.
In addition, when used for food packaging, the added swelling agent may be problematic in food hygiene.
[0005]
[Problems to be solved by the invention]
The problem to be solved is the above problem,
The present invention is safe without using an additive swelling agent which is a problem in food hygiene, can be manufactured at low cost even in small-scale production, can easily uniformly disperse the layered silicate, and can easily form a molded film surface. It is an object of the present invention to provide a method for producing a resin composition for food packaging and a packaging laminate, wherein the resin composition is smooth and the mechanical properties are not reduced.
[0006]
[Means for Solving the Problems]
In order to solve this problem, the present invention swells a layered silicate raw material with a minimum amount of water to the extent that delamination is facilitated, and expands the water-swelled raw material together with a polyolefin in a twin-screw extruder. Under the kneading conditions for preventing the kneading, the layered silicate is kneaded while exfoliating finely in layers to obtain a resin composition containing fine layered silicate substantially uniformly dispersed in the polyolefin. And
With this configuration, the above object is achieved.
[0007]
BEST MODE FOR CARRYING OUT THE INVENTION
The invention according to claim 1 of the present invention is a method for producing a resin composition containing fine layered silicates substantially uniformly dispersed in a polyolefin,
Prepare natural or synthetic layered silicate raw material,
The raw material of the layered silicate, swelling with a minimum amount of water to the extent that the layered exfoliation in the subsequent kneading step is facilitated,
The raw material swelled with water is filled into a twin screw extruder together with a polyolefin,
A method for producing a resin composition for food packaging, characterized in that kneading is performed while kneading the layered silicate in a minute layer under kneading conditions for preventing foaming of water.
A natural or synthetic layered silicate raw material that is easily swelled with water is selected and prepared so that minute layering and dispersion are easy. The raw material of the layered silicate is swelled with a minimum amount of water, and the amount of water facilitates the delamination in the subsequent kneading step. The extruder (preferably a twin-screw extruder) is charged with the raw material swollen with water and mixed with an extruder (preferably a twin-screw extruder), and kneaded under kneading conditions for preventing foaming of water while exfoliating the layered silicate minutely into layers. This has the function of obtaining a resin composition containing fine layered silicates substantially uniformly dispersed therein.
[0008]
The invention according to claim 2 is a laminate including a barrier layer containing fine layered silicate dispersed substantially uniformly in polyolefin,
The barrier layer is formed by laminating a natural or synthetic layered silicate raw material swollen by moisture without using a swelling agent together with polyolefin in an extruder (preferably a twin screw extruder) under kneading conditions for preventing foaming of moisture. A food packaging laminate characterized by being a resin composition obtained by kneading a silicate while exfoliating it finely in layers.
A laminate comprising a barrier layer containing fine layered silicates substantially uniformly dispersed in a polyolefin, which does not contain an additive swelling agent, is safe for food hygiene, and has a high moisture content. Since there is no foaming due to the above, there is an effect that the mechanical strength is maintained, and the finely dispersed fine layered silicate can impart a barrier property.
Hereinafter, embodiments of the present invention will be described.
[0009]
The polyolefin used in the present invention is a homopolymerized polyolefin such as polyethylene and polypropylene, a copolymer with the polyolefin, a bunlend polymer with the polyolefin, and the like.
[0010]
When polyethylene is used, low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), and metallocene PE are used because polyethylene is required to have heat-sealing properties for packaging. Further, medium density polyethylene (MDPE) or high density polyethylene (HDPE) may be used.
[0011]
In a preferred embodiment of the present invention, it is a polyolefin containing fine layered silicates substantially uniformly dispersed in polyethylene. Preferably, the polyethylene contains 0.1 to 10% by weight of a layered silicate having an average particle diameter in a range of 1 to 80 microns and not containing a particle diameter of 300 microns or more. It is substantially uniformly dispersed when the interlayer distance is 50 Å or more.
[0012]
Examples of the raw material of the layered silicate include a layered phyllosilicate mineral composed of a layer of magnesium silicate or aluminum silicate. Specifically, 1: 1 type layered silicates, ie, kaolinite, dickite, halloysite, antigonite, chrysotile, etc., and 2: 1 type layered silicates, ie, montmorillonite, hectorite, fluorine hectorite, saponite , Swelling synthetic mica such as smectites such as beidellite, subbutinsite and vermiculite, mica such as muscovite and phlogopite, fluorophlogopite, fluorphlogopite, K-type fluoroteniolite and K-type tetrasilicic mica; Li Swellable synthetic fluoromica such as fluorinated teniolite, Na-fluorinated teniolite and Na-tetrasilicon fluormica, margarite, pyrophyllite, talc, chlorite and the like. From the viewpoint of surface appearance, product coloring, and gas barrier properties, montmorillonite, hectorite, fluorine hectorite, and swellable synthetic fluorine mica are preferred.
[0013]
In a preferred embodiment of the present invention, a layered silicate (clay) having a metal ion other than Na, K, Li and Ca (for example, a metal ion selected from Ag, Zn, Co, Cd and Cu) or a metal compound thereof between layers. Mineral) can be used. The layered silicate itself has excellent antibacterial properties against various microorganisms such as Pseudomonas aeruginosa, Escherichia coli, and Staphylococcus aureus. Accordingly, the antibacterial property is imparted to the barrier layer containing the layered silicate, and also to the packaging laminate according to the present invention.
[0014]
The blending amount of the layered silicate can be appropriately selected and changed with respect to the polyolefin in consideration of the oxygen barrier property, the durability against stress, the effect of improving fragrance retention and quality retention, and the like.
[0015]
In the present invention, a method of uniformly dispersing a layered silicate in a polyolefin is as follows: first, a natural or synthetic layered silicate raw material that is easily swelled with water is selected so as to facilitate fine layering and dispersion. Prepare. The phyllosilicate material is swelled with a minimum of water. The water content is such that the laminar exfoliation in the subsequent kneading step is facilitated. Fill the extruder (preferably a twin-screw extruder) with the raw material swelled with moisture together with the polyolefin, and exfoliate the layered silicate into small layers under kneading conditions (temperature, degree of vacuum, etc.) to prevent foaming of moisture. While kneading. By this kneading step, a resin composition containing fine layered silicates substantially uniformly dispersed in the polyolefin is obtained.
[0016]
【The invention's effect】
As described above, the method for producing the resin composition and the food packaging laminate of the present invention are safe without using an additive swelling agent which poses a problem in food hygiene.
The food packaging resin composition and the packaging laminate according to the present invention have excellent oxygen barrier properties because the layered silicate is present in the polymer in a uniformly divided state, and furthermore, have a fragrance retention and quality retention. Excellent in nature.
[0017]
As long as the swelling conditions and kneading conditions of the present invention are satisfied, inexpensive natural or synthetic layered silicate raw materials can be used.
In the present invention, even a small-scale production can be manufactured at low cost, and the layered silicate can be easily and uniformly dispersed.
The resulting molded film of the resin composition for food packaging has a smooth surface and does not deteriorate in mechanical properties.
Claims (2)
天然若しくは合成の層状珪酸塩原料を調製し、
層状珪酸塩の該原料を、後工程の混練工程での層状剥離を容易にする程度に最少の水分で膨潤化し、
水分で膨潤化した該原料をポリオレフィンと共に、押出機に充填し、
水分の発泡を防ぐ混練条件で、層状珪酸塩を微小に層状に剥離しながら混練することを特徴とする食品包装用樹脂組成物の製造法。A method for producing a resin composition containing fine layered silicates substantially uniformly dispersed in a polyolefin,
Prepare natural or synthetic layered silicate raw material,
The raw material of the layered silicate, swelling with a minimum amount of water to the extent that the layered exfoliation in the subsequent kneading step is facilitated,
The raw material swelled with water is filled into an extruder together with a polyolefin,
A process for producing a resin composition for food packaging, characterized in that kneading is carried out while kneading the layered silicate in a finely layered manner under kneading conditions for preventing foaming of water.
該バリア層が、膨潤化剤を用いず水分により膨潤した天然若しくは合成の層状珪酸塩原料をポリオレフィンと共に、押出機で、水分の発泡を防ぐ混練条件で、層状珪酸塩を微小に層状に剥離しながら混練して得た樹脂組成物であることを特徴とする食品包装用積層体。A laminate comprising a barrier layer containing fine layered silicates substantially uniformly dispersed in a polyolefin,
The barrier layer is formed by extruding a natural or synthetic layered silicate raw material swollen by water without using a swelling agent together with a polyolefin, and extruding the layered silicate into a fine layer by kneading under a kneading condition for preventing foaming of water. A laminate for food packaging, which is a resin composition obtained by kneading while kneading.
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| JP2002191924A JP2004034390A (en) | 2002-07-01 | 2002-07-01 | Process for producing resin composition for food packaging and laminate for packaging |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7208039B2 (en) | 2001-09-07 | 2007-04-24 | Imerys Pigments, Inc. | Hyperplaty clays and their use in paper coating and filling, methods for making same, and paper products having improved brightness |
| US7413601B2 (en) | 2000-08-17 | 2008-08-19 | Imerys Pigments, Inc. | Kaolin products and their use |
| US7442281B2 (en) | 2000-08-17 | 2008-10-28 | Imerys Minerals Limited | Kaolin products and their production |
| JP2020063430A (en) * | 2019-09-10 | 2020-04-23 | 孝 大野 | Resin composite material |
-
2002
- 2002-07-01 JP JP2002191924A patent/JP2004034390A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7413601B2 (en) | 2000-08-17 | 2008-08-19 | Imerys Pigments, Inc. | Kaolin products and their use |
| US7442281B2 (en) | 2000-08-17 | 2008-10-28 | Imerys Minerals Limited | Kaolin products and their production |
| US7875151B2 (en) | 2000-08-17 | 2011-01-25 | Imerys Minerals Ltd. | Kaolin products and their production |
| US7208039B2 (en) | 2001-09-07 | 2007-04-24 | Imerys Pigments, Inc. | Hyperplaty clays and their use in paper coating and filling, methods for making same, and paper products having improved brightness |
| US7214264B2 (en) | 2001-09-07 | 2007-05-08 | Imerys Pigments, Inc. | Hyperplaty clays and their use in paper coating and filling, methods for making same, and paper products having improved brightness |
| US7226005B2 (en) | 2001-09-07 | 2007-06-05 | Imerys Pigments, Inc. | Hyperplaty clays and their use in paper coating and filling, methods for making same, and paper products having improved brightness |
| JP2020063430A (en) * | 2019-09-10 | 2020-04-23 | 孝 大野 | Resin composite material |
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