JP2010260346A - Defogging propylene based resin sheet - Google Patents
Defogging propylene based resin sheet Download PDFInfo
- Publication number
- JP2010260346A JP2010260346A JP2010087464A JP2010087464A JP2010260346A JP 2010260346 A JP2010260346 A JP 2010260346A JP 2010087464 A JP2010087464 A JP 2010087464A JP 2010087464 A JP2010087464 A JP 2010087464A JP 2010260346 A JP2010260346 A JP 2010260346A
- Authority
- JP
- Japan
- Prior art keywords
- propylene
- based resin
- resin sheet
- sheet
- antifogging
- 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.)
- Granted
Links
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- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims abstract description 83
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- 239000011347 resin Substances 0.000 title claims abstract description 78
- -1 aromatic carboxylate Chemical class 0.000 claims abstract description 42
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 39
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- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims abstract description 17
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- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 13
- 239000011342 resin composition Substances 0.000 claims abstract description 12
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- 229910052744 lithium Inorganic materials 0.000 description 1
- 229940031993 lithium benzoate Drugs 0.000 description 1
- 229910001386 lithium phosphate Inorganic materials 0.000 description 1
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 1
- LDJNSLOKTFFLSL-UHFFFAOYSA-M lithium;benzoate Chemical compound [Li+].[O-]C(=O)C1=CC=CC=C1 LDJNSLOKTFFLSL-UHFFFAOYSA-M 0.000 description 1
- LLUXWTMBMUHPJN-UHFFFAOYSA-M lithium;bis(4-tert-butylphenyl) phosphate Chemical compound [Li+].C1=CC(C(C)(C)C)=CC=C1OP([O-])(=O)OC1=CC=C(C(C)(C)C)C=C1 LLUXWTMBMUHPJN-UHFFFAOYSA-M 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910001463 metal phosphate Inorganic materials 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- CPEULHAPWXMDDV-UHFFFAOYSA-N n-[3,5-bis(2,2-dimethylpropanoylamino)phenyl]-2,2-dimethylpropanamide Chemical compound CC(C)(C)C(=O)NC1=CC(NC(=O)C(C)(C)C)=CC(NC(=O)C(C)(C)C)=C1 CPEULHAPWXMDDV-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- KUVXJBSVPBXHEK-UHFFFAOYSA-N octylaluminum Chemical compound CCCCCCCC[Al] KUVXJBSVPBXHEK-UHFFFAOYSA-N 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 229940103091 potassium benzoate Drugs 0.000 description 1
- 235000010235 potassium benzoate Nutrition 0.000 description 1
- 239000004300 potassium benzoate Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000007613 slurry method Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 1
- 235000010234 sodium benzoate Nutrition 0.000 description 1
- 239000004299 sodium benzoate Substances 0.000 description 1
- 229960003885 sodium benzoate Drugs 0.000 description 1
- IEFYQJPRHOKDLM-UHFFFAOYSA-M sodium;1,3,7,9-tetratert-butyl-5-methyl-11-oxido-5h-benzo[d][1,3,2]benzodioxaphosphocine 11-oxide Chemical compound [Na+].CC1C2=CC(C(C)(C)C)=CC(C(C)(C)C)=C2OP([O-])(=O)OC2=C1C=C(C(C)(C)C)C=C2C(C)(C)C IEFYQJPRHOKDLM-UHFFFAOYSA-M 0.000 description 1
- SNAQARSCIHDMGI-UHFFFAOYSA-M sodium;bis(4-tert-butylphenyl) phosphate Chemical compound [Na+].C1=CC(C(C)(C)C)=CC=C1OP([O-])(=O)OC1=CC=C(C(C)(C)C)C=C1 SNAQARSCIHDMGI-UHFFFAOYSA-M 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 1
- 238000007666 vacuum forming Methods 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
Landscapes
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Laminated Bodies (AREA)
Abstract
Description
本発明は、防曇性、透明性に優れたプロピレン系樹脂シートに関し、さらに詳しくは、透明性と防曇性に優れ、かつ再生使用しても変色の少ない防曇性プロピレン系樹脂シートに関する。 The present invention relates to a propylene resin sheet excellent in antifogging property and transparency, and more particularly relates to an antifogging propylene resin sheet excellent in transparency and antifogging property and having little discoloration even when recycled.
透明性に優れている非結晶性の熱可塑性樹脂であるポリスチレン、ポリ塩化ビニール、ポリエチレンテレフタレート等は、内容物を見分けることが可能であるため、シート状に加工され、さらに熱成形によって食品の容器や蓋材として広く活用されている。
しかし、これらの非結晶性樹脂は、近年電子レンジ加熱食品の増加に伴い、耐熱不良や耐衝撃不良等で容器や蓋が変形したり、割れたりして問題があり、容器や蓋製造業者からは透明で防曇性が有り、しかも耐熱性や耐衝撃性のある材料が望まれていた。
一方、結晶性のポリプロピレン系樹脂シートは、耐熱性や耐衝撃性には強いが透明性が劣り、その表面が極めて疎水性であるため、容器や蓋材として使用した場合、内容物の水蒸気が表面に微小水滴として付着し、内容物を見分けることが困難であるという防曇性の問題があった。
Polystyrene, polyvinyl chloride, polyethylene terephthalate, etc., which are non-crystalline thermoplastic resins with excellent transparency, can be distinguished from each other, so they are processed into sheets, and food containers are formed by thermoforming. It is widely used as a cover material.
However, these non-crystalline resins have a problem in that the containers and lids are deformed or cracked due to poor heat resistance and shock resistance, etc. in recent years due to the increase in foods heated in microwave ovens. The material has been desired to be transparent, antifogging, heat resistant and impact resistant.
On the other hand, a crystalline polypropylene resin sheet is strong in heat resistance and impact resistance but poor in transparency, and its surface is extremely hydrophobic. There was a problem of anti-fogging property that it adhered to the surface as fine water droplets and it was difficult to distinguish the contents.
ポリプロピレン系樹脂シートの透明性は、シート加工時に鏡面加工を施された金属ロールや金属ベルトで急速に冷却固化させるといった方法、さらにプロピレンとα−オレフィンとの共重合を行って結晶性を低下させたポリプロピレン系樹脂を用いる方法、さらにポリプロピレン系樹脂に核剤を添加する方法等（特許文献１）で、実用レベルの透明性まで改良がされてきた。 The transparency of the polypropylene resin sheet reduces crystallinity by rapidly cooling and solidifying with a metal roll or metal belt that has been mirror-finished during sheet processing, and by copolymerizing propylene and α-olefin. In addition, a method using a polypropylene resin, a method of adding a nucleating agent to a polypropylene resin, etc. (Patent Document 1) have been improved to a practical level of transparency.
一方、ポリプロピレン系樹脂シートの防曇性は、シート加工時にそのライン上でポリプロピレン系樹脂を冷却固化した後、コロナ処理、プラズマ処理、フレーム処理等を施すことによって疎水性を改良し、液体状の防曇剤を塗布しながら乾燥してシートを巻き取る方法（特許文献２、特許文献３、特許文献４等）で、防曇性を付与できるようになってきた。 On the other hand, the antifogging property of the polypropylene resin sheet improves the hydrophobicity by cooling and solidifying the polypropylene resin on the line at the time of sheet processing, and then applying corona treatment, plasma treatment, flame treatment, etc. It has become possible to impart antifogging properties by a method (Patent Document 2, Patent Document 3, Patent Document 4, etc.) of winding and drying a sheet while applying an antifogging agent.
ところが、近年、経済性や環境保護の観点から、資源の再利用が積極的に進められるようになってきた。食品の容器や蓋材等も例外ではなく、防曇剤を塗布したシートや製品であっても再生使用が求められるようになってきた。
特に、シートから熱成形で容器や蓋材を生産すると、どうしても容器や蓋材製品を打ち抜いた後のシートロス部分が発生する。さらに、容器や蓋材製品を回収して再生使用することも求められることになる。
シートや製品の再生使用にあたっては、シートや製品を粉砕してバージン原料と混合し、シート成形機にかける方法や、シートや製品を粉砕したあと、押出機にて溶融混練してペレット（粒）状に加工してバージン原料と混合し、シート成形機にかける方法が行われる。
この場合、再生使用の割合にもよるが、押出機にて溶融混練してペレット（粒）状に加工した方が、原料の嵩密度が安定するために、シート成形加工が安定する。
However, in recent years, the reuse of resources has been actively promoted from the viewpoint of economic efficiency and environmental protection. Food containers and lids are no exception, and sheets and products coated with an antifogging agent have been required to be recycled.
In particular, when a container or a lid material is produced from a sheet by thermoforming, a sheet loss portion is inevitably generated after the container or lid material is punched out. Furthermore, it is also required to collect and recycle containers and lid products.
When reusing sheets and products, the sheets and products are pulverized and mixed with virgin raw materials, and then applied to a sheet molding machine. After pulverizing the sheets and products, they are melt-kneaded in an extruder and pellets (grains) The sheet is processed into a shape, mixed with the virgin raw material, and applied to a sheet forming machine.
In this case, although depending on the ratio of recycle use, the sheet forming process is more stable when the raw material is melt kneaded and processed into pellets (grains) because the bulk density of the raw material is more stable.
この際、防曇剤が塗布されたポリプロピレン系樹脂シートやそれを用いて得た製品を粉砕してシート成形すると著しい茶褐色に変色することが判明した。特に、嵩密度の安定のために、シートや製品の粉砕品を押出機にて溶融混練してペレット（粒）状に加工すると、さらに激しい変色が発生することが明らかになってきた。 At this time, it was found that when a polypropylene resin sheet coated with an antifogging agent or a product obtained using the same was pulverized and formed into a sheet, the color changed to marked brown. In particular, in order to stabilize the bulk density, it has become clear that more severe discoloration occurs when a crushed product of a sheet or product is melt-kneaded with an extruder and processed into a pellet.
このように、非結晶性樹脂の有する欠点である耐熱不良や耐衝撃不良等で容器や蓋が変形したり、割れたりするという問題を解決するために用いるポリプロピレン系樹脂シートを、防曇性の要求される容器や蓋材として効率よく使用するためには、この欠点を改良する必要があったが、未だ実現されず、その開発が希求されている。 Thus, the polypropylene resin sheet used for solving the problem that the container and the lid are deformed or cracked due to the heat resistance failure and the impact resistance failure which are the disadvantages of the amorphous resin, In order to use it efficiently as a required container or lid, it was necessary to improve this drawback, but it has not been realized yet and its development is desired.
本発明の目的は、上記従来技術の問題点に鑑み、透明性と防曇性に優れ、かつ再生使用しても変色の少ない防曇性プロピレン系樹脂シートを提供することにある。 An object of the present invention is to provide an anti-fogging propylene-based resin sheet that is excellent in transparency and anti-fogging properties and has little discoloration even when recycled.
本発明者らは、上記課題を解決すべく鋭意検討した結果、特定のプロピレン系樹脂に特定の造核剤を特定の割合で配合してなるプロピレン系樹脂組成物を用いて形成された特定のプロピレン系樹脂シートの少なくとも片面に、特定の防曇剤を特定の塗布量で塗布したところ、透明性と防曇性を維持しながら再生使用しても変色の少ない防曇性プロピレン系樹脂シートが得られることを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a specific propylene resin composition is formed by using a specific propylene resin and a specific nucleating agent blended in a specific ratio. When a specific anti-fogging agent is applied to at least one side of the propylene-based resin sheet at a specific application amount, an anti-fogging propylene-based resin sheet that is less discolored even when recycled is used while maintaining transparency and anti-fogging properties. As a result, the present invention was completed.
すなわち、本発明の第１の発明によれば、厚みが０．１〜２ｍｍのプロピレン系樹脂シートの少なくとも片面に、固形分量で０．０２〜２ｇ／ｍ２の防曇剤を塗布してなるプロピレン系樹脂シートであって、上記プロピレン系樹脂シートは、ＭＦＲが０．２〜３０ｇ／１０分のプロピレン系樹脂１００重量部に対し、芳香族カルボン酸金属塩系、芳香族リン酸金属塩系、ソルビトール系およびアミン系造核剤からなる群から選ばれる少なくとも１種の造核剤を０．００１〜１重量部の割合で配合してなるプロピレン系樹脂組成物から形成され、かつ炭素数６〜２２の遊離脂肪酸の含有量が５０ｐｐｍ以下であり、一方、上記防曇剤は、炭素数６〜２２の脂肪酸の蔗糖脂肪酸エステルからなることを特徴とする防曇性プロピレン系樹脂シートが提供される。 That is, according to the first invention of the present invention, an antifogging agent having a solid content of 0.02 to 2 g / m 2 is applied to at least one surface of a propylene-based resin sheet having a thickness of 0.1 to 2 mm. A propylene-based resin sheet, wherein the propylene-based resin sheet is based on 100 parts by weight of a propylene-based resin having an MFR of 0.2 to 30 g / 10 min. And a propylene resin composition comprising at least one nucleating agent selected from the group consisting of sorbitol and amine nucleating agents in a proportion of 0.001 to 1 part by weight, and having 6 carbon atoms. An antifogging propylene-based resin sheet characterized in that the content of ˜22 free fatty acids is 50 ppm or less, while the antifogging agent comprises a sucrose fatty acid ester of a fatty acid having 6 to 22 carbon atoms. Provided.
また、本発明の第２の発明によれば、第１の発明において、前記プロピレン系樹脂が、プロピレン含量１００〜９０重量％とα−オレフィン含量０〜１０重量％とのランダム共重合体であることを特徴とする防曇性プロピレン系樹脂シートが提供される。 According to the second invention of the present invention, in the first invention, the propylene-based resin is a random copolymer having a propylene content of 100 to 90% by weight and an α-olefin content of 0 to 10% by weight. An antifogging propylene-based resin sheet is provided.
また、本発明の第３の発明によれば、第２の発明において、α−オレフィンが、エチレンであることを特徴とする防曇性プロピレン系樹脂シートが提供される。 According to a third aspect of the present invention, there is provided an antifogging propylene-based resin sheet characterized in that in the second aspect, the α-olefin is ethylene.
さらに、本発明の第４の発明によれば、第１〜３のいずれかの発明において、０．３５ｍｍ厚シートのヘイズ値（ＨＡＺＥ値）が１０以下であることを特徴とする防曇性プロピレン系樹脂シートが提供される。 Furthermore, according to the fourth invention of the present invention, in any one of the first to third inventions, the haze value (HAZE value) of the 0.35 mm-thick sheet is 10 or less. A resin sheet is provided.
本発明によれば、透明性と防曇性に優れ、かつ再生使用しても変色の少ない防曇性プロピレン系樹脂シートを提供することができる。そしてこれらのシートは、経済性、環境性に優れ、食品日用品の包装や医療部品、電子部品の分野に好適に使用することができる。 According to the present invention, it is possible to provide an anti-fogging propylene-based resin sheet that is excellent in transparency and anti-fogging property and has little discoloration even when recycled. These sheets are excellent in economic efficiency and environmental friendliness, and can be suitably used in the fields of food daily necessities packaging, medical parts, and electronic parts.
本発明は、上記したように、特定のプロピレン系樹脂シートの少なくとも片面に、特定の防曇剤を塗布してなる再生使用しても変色の少ない防曇性プロピレン系樹脂シートである。
以下、本発明の防曇性プロピレン系樹脂シートを形成する組成物の構成成分やその製造方法、防曇剤、さらにはそれらを用いた防曇性プロピレン系樹脂シートの製造方法等について詳細に説明する。
As described above, the present invention is an anti-fogging propylene resin sheet that is less discolored even when recycled by coating a specific anti-fogging agent on at least one surface of the specific propylene resin sheet.
Hereinafter, the constituents of the composition forming the antifogging propylene resin sheet of the present invention, the production method thereof, the antifogging agent, and the production method of the antifogging propylene resin sheet using them will be described in detail. To do.
［１］［構成成分］
１．プロピレン系樹脂
本発明で用いられるプロピレン系樹脂のＭＦＲは、０．２〜３０ｇ／１０分、好ましくは、０．３〜１５ｇ／１０分、さらに好ましくは、０．４〜１０／１０分である。ＭＦＲが上記の数値範囲を下回ると成形加工時の表面が荒れて製品の外観が損なわれ、一方、ＭＦＲが上記の数値範囲を上回ると製品の衝撃強度が低下する。
[1] [Components]
1. Propylene-based resin The MFR of the propylene-based resin used in the present invention is 0.2 to 30 g / 10 minutes, preferably 0.3 to 15 g / 10 minutes, and more preferably 0.4 to 10/10 minutes. . When the MFR is below the above numerical range, the surface during molding is roughened and the appearance of the product is impaired. On the other hand, when the MFR exceeds the above numerical range, the impact strength of the product is reduced.
本発明で用いられるプロピレン系樹脂は、プロピレン単独重合体でも良いが、プロピレンとα−オレフィンとのランダム或いはブロック共重合体が好ましい。これらは、それぞれ単独で用いてもよく、混合して使用しても差し支えない。
α−オレフィンとしては、エチレン、ブテン−１、ペンテン−１、ヘキセン−１、４−メチル−ペンテン−１等を用いることができる。中でもプロピレンとエチレンとのランダム共重合体が好ましい。プロピレンとエチレンとのランダム共重合体では、エチレン含量は、０．１〜１０重量％が好ましく、０．２〜５重量％がさらに好ましく、０．４〜３．５重量％が特に好ましい。エチレン含量が０．１重量％を下回ると製品の衝撃強度が損なわれ、一方、エチレン含量が１０重量％を上回ると製品の剛性が低下しやすい。
The propylene resin used in the present invention may be a propylene homopolymer, but is preferably a random or block copolymer of propylene and an α-olefin. These may be used alone or in combination.
As the α-olefin, ethylene, butene-1, pentene-1, hexene-1, 4-methyl-pentene-1, or the like can be used. Among these, a random copolymer of propylene and ethylene is preferable. In the random copolymer of propylene and ethylene, the ethylene content is preferably 0.1 to 10% by weight, more preferably 0.2 to 5% by weight, and particularly preferably 0.4 to 3.5% by weight. When the ethylene content is less than 0.1% by weight, the impact strength of the product is impaired. On the other hand, when the ethylene content is more than 10% by weight, the rigidity of the product tends to decrease.
本発明に用いられるプロピレン系樹脂は、任意の重合法で製造することができ、スラリー法、気相法、バルク法等が使用できる。
プロピレン系樹脂は、後述の方法によって得られるもののほか、市販品を使用することができる。市販品としては、例えば、チーグラー系触媒を使用した製品例として日本ポリプロ社製「ノバテックＰＰ」（商品名）シリーズ、メタロセン系触媒を使用した製品例として日本ポリプロ社製「ウインテック」（商品名）シリーズのなかから本発明の範囲に適合するものを使用することができる。
The propylene-based resin used in the present invention can be produced by any polymerization method, and a slurry method, a gas phase method, a bulk method, or the like can be used.
As the propylene-based resin, commercially available products can be used in addition to those obtained by the method described below. Examples of commercially available products include “NOVATEC PP” (trade name) series manufactured by Nippon Polypro as a product example using a Ziegler catalyst, and “WINTEC” (trade name) manufactured by Nippon Polypro as a product example using a metallocene catalyst. ) From the series, those that meet the scope of the present invention can be used.
２．造核剤
本発明では、芳香族カルボン酸金属塩系、芳香族リン酸金属塩系、ソルビトール系およびアミン系造核剤から選ばれる少なくとも１種の造核剤が用いられる。
2. Nucleating Agent In the present invention, at least one nucleating agent selected from aromatic carboxylic acid metal salt-based, aromatic phosphate metal salt-based, sorbitol-based and amine-based nucleating agents is used.
芳香族カルボン酸金属塩系の造核剤としては、例えば安息香酸アルミニウム、安息香酸カリウム、安息香酸ナトリウム、安息香酸リチウム、ジ−パラ−ｔ−ブチル安息香酸アルミニウム、ジ−パラ−ｔ−ブチル安息香酸チタン、ジ−パラ−ｔ−ブチル安息香酸クロム、ヒドロキシ−ジ−ｔ−ブチル安息香酸アルミニウム、アルミニウム−ｐ−ブチルベンゾエート、β−ナフトエ酸ナトリウムなどが挙げられる。 Examples of the aromatic carboxylic acid metal salt nucleating agent include aluminum benzoate, potassium benzoate, sodium benzoate, lithium benzoate, aluminum di-para-t-butylbenzoate, and di-para-t-butylbenzoic acid. Examples thereof include titanium oxide, chromium di-para-t-butylbenzoate, aluminum hydroxy-di-t-butylbenzoate, aluminum-p-butylbenzoate, and sodium β-naphthoate.
芳香族リン酸金属塩系造核剤としては、例えばビス（４−ｔ−ブチルフェニル）リン酸ナトリウム塩、ビス（４−ｔ−ブチルフェニル）リン酸リチウム塩、ビス（４−ｔ−ブチルフェニル）リン酸アルミニウム塩、２，２’−メチレン−ビス（４，６−ジ−ｔ−ブチルフェニル）リン酸ナトリウム塩、２，２’−メチレン−ビス（４，６−ジ−ｔ−ブチルフェニル）リン酸リチウム塩、２，２’−メチレン−ビス（４，６−ジ−ｔ−ブチルフェニル）リン酸アルミニウム塩、２，２’−メチリデン−ビス（４，６−ジ−ｔ−ブチルフェニル）リン酸カルシウム塩、２，２’−エチリデン−ビス（４，６−ジ−ｔ−ブチルフェニル）リン酸ナトリウム塩、２，２’−エチリデン−ビス（４，６−ジ−ｔ−ブチルフェニル）リン酸塩リチウム、２，２’−エチリデン−ビス（４，６−ジ−ｔ−ブチルフェニル）リン酸アルミニウム塩、ビス−（４−ｔ−ブチルフェニル）リン酸カルシウム塩などが挙げられ、市販されているものとしては、例えばＡＤＥＫＡ社から販売されている「アデカスタブＮＡ−１１」、「アデカスタブＮＡ−２１」、「アデカスタブＮＡ−７１」などが、好ましく挙げられる。 Examples of the aromatic metal phosphate nucleating agent include sodium bis (4-t-butylphenyl) phosphate, lithium bis (4-t-butylphenyl) phosphate, and bis (4-t-butylphenyl). ) Aluminum phosphate, 2,2'-methylene-bis (4,6-di-t-butylphenyl) sodium phosphate, 2,2'-methylene-bis (4,6-di-t-butylphenyl) ) Lithium phosphate, 2,2′-methylene-bis (4,6-di-t-butylphenyl) aluminum phosphate, 2,2′-methylidene-bis (4,6-di-t-butylphenyl) ) Calcium phosphate, 2,2′-ethylidene-bis (4,6-di-t-butylphenyl) phosphate sodium salt, 2,2′-ethylidene-bis (4,6-di-t-butylphenyl) phosphorus Lithium salt, 2 2'-ethylidene-bis (4,6-di-t-butylphenyl) aluminum phosphate, bis- (4-tert-butylphenyl) calcium phosphate, and the like are commercially available. “Adeka Stub NA-11”, “Adeka Stub NA-21”, “Adeka Stub NA-71” and the like sold by the company are preferably mentioned.
ソルビトール系造核剤としては、例えば、ジベンジリデンソルビトール、１，３−ジ（メチルベンジリデン）ソルビトール、２，４−ジ（メチルベンジリデン）ソルビトール、１，３−ジ（エチルベンジリデン）ソルビトール、２，４−ジ（エチルベンジリデン）ソルビトール、１，３−ジ（ブチルベンジリデン）ソルビトール、２，４−ジ（ブチルベンジリデン）ソルビトール、１，３−ジ（メトキシベンジリデン）ソルビトール、２，４−ジ（メトキシベンジリデン）ソルビトール、１，３−ジ（エトキシベンジリデン）ソルビトール、２，４−ジ（エトキシベンジリデン）ソルビトール、１．３−クロルベンジリデン，２．４−メチルベンジリデンソルビトール、モノ（メチル）ジベンジリデンソルビトール等が挙げられる。 Examples of the sorbitol nucleating agent include dibenzylidene sorbitol, 1,3-di (methylbenzylidene) sorbitol, 2,4-di (methylbenzylidene) sorbitol, 1,3-di (ethylbenzylidene) sorbitol, 2,4 -Di (ethylbenzylidene) sorbitol, 1,3-di (butylbenzylidene) sorbitol, 2,4-di (butylbenzylidene) sorbitol, 1,3-di (methoxybenzylidene) sorbitol, 2,4-di (methoxybenzylidene) Examples include sorbitol, 1,3-di (ethoxybenzylidene) sorbitol, 2,4-di (ethoxybenzylidene) sorbitol, 1.3-chlorobenzylidene, 2.4-methylbenzylidene sorbitol, mono (methyl) dibenzylidene sorbitol, and the like. .
これらの造核剤の中では、ｐ−ｔ−ブチル安息香酸アルミニウム、リン酸２，２’−メチレンビス（４，６−ジ−ｔ−ブチルフェニル）ナトリウム、リン酸２，２’−メチレンビス（４，６−ジ−ｔ−ブチルフェニル）アルミニウム、ｐ−メチル−ベンジリデンソルビトール、ｐ−エチル−ベンジリデンソルビトール、１，３：２，４−ジベンジリデンソルビトール、１，３：２，４−ビス（ｐ−メチルベンジリデン）ソルビトール、１，３−ｐ−クロルベンジリデン−２，４−ｐ−メチルべンジリデンソルビトール、１，３：２，４−ビス（ｐ−エチルベンジリデン）ソルビトール、１，３：２，４−ビス（３，４−ジメチルベンジリデン）ソルビトール、トリアミノベンゼン誘導体等が好適である。これらは、２種以上の混合物として用いても良い。 Among these nucleating agents, p-t-butylbenzoate aluminum, 2,2′-methylenebis (4,6-di-t-butylphenyl) sodium phosphate, 2,2′-methylenebisphosphate (4 , 6-Di-t-butylphenyl) aluminum, p-methyl-benzylidene sorbitol, p-ethyl-benzylidene sorbitol, 1,3: 2,4-dibenzylidene sorbitol, 1,3: 2,4-bis (p- Methylbenzylidene) sorbitol, 1,3-p-chlorobenzylidene-2,4-p-methylbenzylidenesorbitol, 1,3: 2,4-bis (p-ethylbenzylidene) sorbitol, 1,3: 2,4 -Bis (3,4-dimethylbenzylidene) sorbitol, triaminobenzene derivatives and the like are preferred. These may be used as a mixture of two or more.
また、上記造核剤を添加する場合の配合割合は、プロピレン系樹脂１００重量部に対して、０．００１〜１重量部、好ましくは０．００５〜０．８重量部、特に好ましくは０．０１〜０．６重量部の割合である。造核剤の配合量が上記範囲未満では、透明性が不足することがあり、一方、配合量が上記範囲を越えると、透明性付与効果が頭打ちとなり単なるコストアップにつながるので好ましくない。 The blending ratio when the nucleating agent is added is 0.001 to 1 part by weight, preferably 0.005 to 0.8 part by weight, particularly preferably 0.001 part by weight based on 100 parts by weight of the propylene resin. The ratio is from 01 to 0.6 parts by weight. If the blending amount of the nucleating agent is less than the above range, the transparency may be insufficient. On the other hand, if the blending amount exceeds the above range, the effect of imparting transparency will reach its peak, leading to a mere increase in cost.
３．その他の添加剤
本発明では、これらの必須成分の他に付加的成分を本発明の効果を損なわない範囲で添加することができる。それらの付加的成分としては、通常のポリプロピレンに用いられる酸化防止剤、光安定剤、紫外線吸収剤、滑剤、帯電防止剤、防曇剤、分子量調整剤（過酸化物）、着色剤、中和剤、ハイドロタルサイト類、各種フィラー等の各種助剤、他のプロピレン単独あるいは他のα−オレフィンとの共重合体、低密度ポリエチレン、高密度ポリエチレン等の他の重合体、各種熱可塑性エラストマー等を挙げることができる。
3. Other Additives In the present invention, in addition to these essential components, additional components can be added as long as the effects of the present invention are not impaired. These additional components include antioxidants, light stabilizers, UV absorbers, lubricants, antistatic agents, antifogging agents, molecular weight modifiers (peroxides), colorants, neutralizing agents used in ordinary polypropylene. Agents, hydrotalcites, various auxiliary agents such as various fillers, other propylene homopolymers or copolymers with other α-olefins, other polymers such as low density polyethylene and high density polyethylene, various thermoplastic elastomers, etc. Can be mentioned.
［２］［プロピレン系樹脂組成物の調製］
本発明に用いられるプロピレン系樹脂組成物の製造方法は、上記成分の添加順序や用いる装置に特に限定されないが、一般に使用されるヘンシェルミキサー、Ｖブレンター、リボンブレンダー、バンバリーミキサー、ニーダーブレンダー又は押出機の如き通常の混合機または混錬機を用いて所定時間混合し、通常の押出機にて粒状とする方法が好ましい。
又、本発明で用いられるプロピレン系樹脂組成物は、造核剤を目的とする配合量よりあらかじめ多く配合しておき、シートの製造前にプロピレン系樹脂で目的量に希釈する所謂マスターバッチの方式を取ることもできる。
また、本発明においては、本発明により製造された防曇性シートを再生使用するために、使用済みの防曇性シートを粉砕機等により粉砕した後、あるいはその粉砕品を溶融混錬して再生ペレットとした後、バージン原料に混合し、新しいプロピレン系樹脂組成物とすることができる。
しかし、その際、再生ペレットの配合には、その中の遊離脂肪酸により生じると思われる変色の面からおのずと限度があり、組成物全体で、遊離脂肪酸の含有量が５０ｐｐｍ以下となるように新しい樹脂組成物を調製する必要がある。遊離脂肪酸の含有量が５０ｐｐｍを上回ると、変色が激しくなる。このように調製することで、再生使用しても変色の少ないプロピレン系樹脂シートとすることができる。
[2] [Preparation of propylene-based resin composition]
The production method of the propylene-based resin composition used in the present invention is not particularly limited to the order of addition of the above components and the apparatus to be used. A method of mixing for a predetermined time using an ordinary mixer or kneader as described above and granulating with an ordinary extruder is preferred.
In addition, the propylene resin composition used in the present invention is a so-called masterbatch method in which a nucleating agent is compounded in advance in a larger amount than the target compounding amount, and diluted to the target amount with the propylene resin before the production of the sheet. You can also take.
In the present invention, in order to recycle and use the antifogging sheet produced according to the present invention, the used antifogging sheet is pulverized by a pulverizer or the like, or the pulverized product is melt-kneaded. After making a regenerated pellet, it can be mixed with a virgin raw material to obtain a new propylene-based resin composition.
However, in that case, there is a natural limit to the blending of the regenerated pellets in terms of discoloration that appears to be caused by the free fatty acids therein, and a new resin is used so that the content of free fatty acids in the entire composition is 50 ppm or less. A composition needs to be prepared. When the content of free fatty acid exceeds 50 ppm, discoloration becomes severe. By preparing in this way, it can be set as the propylene-type resin sheet with little discoloration even if it recycles.
［３］［シートとその製造方法］
１．プロピレン系樹脂シート
本発明に用いられるプロピレン系樹脂シートの厚みは、０．１〜２ｍｍであり、０．１５〜１．５ｍｍが好ましく、０．２〜１ｍｍが特に好ましい。
厚みが０．１ｍｍを大きく下回る場合は、製品の剛性が損なわれ、厚みが２ｍｍを大きく上回る場合は、シートの透明性が充分ではなくなる。
[3] [Sheet and its manufacturing method]
1. Propylene-based resin sheet The thickness of the propylene-based resin sheet used in the present invention is 0.1 to 2 mm, preferably 0.15 to 1.5 mm, and particularly preferably 0.2 to 1 mm.
When the thickness is much less than 0.1 mm, the rigidity of the product is impaired, and when the thickness is much more than 2 mm, the transparency of the sheet is not sufficient.
また、本発明に用いられるプロピレン系樹脂シートは、０．３５ｍｍ厚シートのヘイズ（ＨＡＺＥ）値が１０以下であることが望ましい。ＨＡＺＥ値がこの範囲であると、透明性の必要とする食品の包装に好適に利用できる。 Moreover, as for the propylene-type resin sheet used for this invention, it is desirable for the haze (HAZE) value of a 0.35 mm thickness sheet to be 10 or less. When the HAZE value is within this range, it can be suitably used for packaging foods that require transparency.
一方、本発明に用いられるプロピレン系樹脂シートは、再生・再使用の観点から、遊離脂肪酸の含有量が５０ｐｐｍ以下であることが必要であり、好ましくは４０ｐｐｍ以下である。遊離脂肪酸の含有量が本発明の範囲を上回ると、本発明により防曇剤を塗付したシートを再生使用した時に変色が激しくなるため、望ましくない。
なお、ここでの脂肪酸とは、炭素数６〜２２の脂肪酸であり、ステアリン酸、パルチミン酸、ミチスチン酸、オレイン酸、ベヘニン酸、ラウリン酸、エリカ酸等の１種以上の混合物をいう。
On the other hand, the propylene-based resin sheet used in the present invention needs to have a free fatty acid content of 50 ppm or less, preferably 40 ppm or less, from the viewpoint of regeneration and reuse. If the content of the free fatty acid exceeds the range of the present invention, it is not desirable because discoloration becomes severe when the sheet coated with the antifogging agent according to the present invention is recycled.
In addition, a fatty acid here is a C6-C22 fatty acid, and means 1 or more types of mixtures, such as a stearic acid, a palmitic acid, a myristic acid, an oleic acid, a behenic acid, a lauric acid, an ericic acid.
２．シートの成形
本発明に用いられるプロピレン系樹脂シートは、押出しシート成形、カレンダー成形等によって製造することができる。
押出しシート成形としては、単軸又は二軸のスクリュー押出機を通してコートハンガーダイからシート状に押出される。押出されたシートは、内部で冷却水や油が循環している金属ロール表面に、エアーナイフ、エアーチャンバー、硬質ゴムロール、スチールベルト、金属ロール等にて押さえつけ冷却固化されてシートに製造される。又、シート両面をスチールベルトで挟んで冷却固化することもできる。押出しシート成形は、単層の他に多層シートも使用できる。多層シートとしては、本発明のプロピレン系樹脂組成物の押出機に加え、複数の押出機を用い、フィードブロックやマルチマニホールドを用いてガスバリア樹脂層、接着性樹脂層、再生樹脂層、加飾樹脂層、等を重ねた多層シートとすることが出来る。
さらに、押出しシート成形、カレンダー成形されたシートは、真空成形、真空圧空成形、熱盤圧空成形等の熱成形により各種容器や蓋材に加工することができる。
2. Sheet Forming The propylene-based resin sheet used in the present invention can be produced by extrusion sheet forming, calendar forming, or the like.
As extrusion sheet forming, the sheet is extruded from a coat hanger die through a single-screw or twin-screw extruder. The extruded sheet is pressed and solidified by cooling with an air knife, an air chamber, a hard rubber roll, a steel belt, a metal roll or the like on the surface of a metal roll through which cooling water or oil circulates, and is manufactured into a sheet. It is also possible to cool and solidify both sides of the sheet with a steel belt. Extrusion sheet molding can use a multilayer sheet in addition to a single layer. As a multilayer sheet, in addition to the propylene-based resin composition extruder of the present invention, a plurality of extruders are used, and a gas barrier resin layer, an adhesive resin layer, a recycled resin layer, and a decorative resin are used using a feed block and a multi-manifold. A multilayer sheet in which layers and the like are stacked can be obtained.
Further, extruded sheet molding and calendered sheet can be processed into various containers and lid materials by thermoforming such as vacuum forming, vacuum pressure forming, hot platen pressure forming and the like.
［４］［防曇性シートとその製造方法］
１．防曇剤
本発明で使用される防曇剤は、炭素数６〜２２の脂肪酸の蔗糖脂肪酸エステルであり、この化合物は、食品用添加物として認められており、安全性の点で最も好ましい。
この中では、ステアリン酸、パルチミン酸、ミチスチン酸、オレイン酸、ベヘニン酸、ラウリン酸、エリカ酸の蔗糖脂肪酸エステルが特に好適である。
本発明で使用される蔗糖脂肪酸エステルは、市販品を使用できる。市販品としては、三菱化学フーズ社製の「リョートーシュガーエステル」（商品名）を挙げる事ができる。
[4] [Anti-fogging sheet and manufacturing method thereof]
1. Antifogging agent The antifogging agent used in the present invention is a sucrose fatty acid ester of a fatty acid having 6 to 22 carbon atoms, and this compound is recognized as an additive for foods and is most preferable from the viewpoint of safety.
Of these, sucrose fatty acid esters of stearic acid, palmitic acid, myristic acid, oleic acid, behenic acid, lauric acid and ericic acid are particularly preferred.
A commercial item can be used for the sucrose fatty acid ester used in the present invention. Commercially available products include “Ryoto Sugar Ester” (trade name) manufactured by Mitsubishi Chemical Foods Corporation.
本発明で使用される防曇剤の塗付量は、０．０２〜２ｇ／ｍ２である。塗付量がこの範囲を下回るとシートの防曇性が不足し、塗付量がこの範囲を上回るとそれ以上の効果が期待できないばかりか、シート表面がべた付いて透明性が損なわれる。 The coating amount of the antifogging agent used in the present invention is 0.02 to 2 g / m 2 . If the coating amount is less than this range, the antifogging property of the sheet is insufficient. If the coating amount is more than this range, not only a further effect cannot be expected, but the sheet surface becomes sticky and the transparency is impaired.
２．防曇剤の塗布方法
本発明に用いられるプロピレン系樹脂シートに防曇剤を塗布する際には、あらかじめシートをコロナ処理、プラズマ処理、フレーム処理等の酸化処理を施すことが、防曇剤の安定に有効である。この中ではコロナ処理によって、シート表面の濡れ張力を３５〜５５ダイン、好ましくは３６〜４５ダインの範囲となるよう処理されるのが好ましい。濡れ張力がこの範囲を上回るとシートの酸化臭が発生して好ましくない。濡れ張力がこの範囲を下回ると防曇剤のシートへの接着性が損なわれる。
2. Application method of anti-fogging agent When applying the anti-fogging agent to the propylene-based resin sheet used in the present invention, the sheet is subjected to oxidation treatment such as corona treatment, plasma treatment, flame treatment, etc. in advance. It is effective for stability. Among these, the sheet surface is preferably treated by corona treatment so that the wetting tension of the sheet surface is in the range of 35 to 55 dynes, preferably 36 to 45 dynes. If the wetting tension exceeds this range, an oxidized odor of the sheet is generated, which is not preferable. If the wetting tension is below this range, the adhesion of the antifogging agent to the sheet is impaired.
酸化処理されたシートへの防曇剤の塗付は、防曇剤を０．０１〜１０重量％の防曇剤溶液として塗付後、乾燥する方法を用いることが好ましい。防曇剤溶液に用いる溶媒としては、例えば、水、アルコール等で防曇剤を溶解し、且つポリプロピレン系樹脂シートを溶解しない溶液で、しかも適用分野によっては安全性を充たす溶媒を適宜選択して用いるのが良い。前記該シートへの防曇剤固形分としては、０．０２〜２．０ｇ／ｍ２塗布する。防曇剤の塗付量がこの範囲を下回ると防曇性能が不足し、防曇剤の塗付量がこの範囲を上回るとべた付きによる該シート間のブロッキングが発生して好ましくない。
上記の防曇剤の塗付法は、各種のロール印刷法やどぶ漬け法や吹き付け法等、いずれの方法でも使用できる。前記塗布法は、シート成形後に引き続いて行うインラインコートやシート成形・巻取り後に巻き戻し工程で行うアウトラインコートする方法等で実施できる。
防曇剤塗布後の乾燥方法としては、蒸気や電気で熱した乾燥炉（溶媒が水の場合は、１００℃以上が好ましい。）にシートを通して、溶媒を蒸発させる方法等が挙げられるが、特に制限はない。
Application of the antifogging agent to the oxidized sheet is preferably performed by applying the antifogging agent as an antifogging agent solution of 0.01 to 10% by weight and then drying. As the solvent used in the antifogging agent solution, for example, a solution that dissolves the antifogging agent with water, alcohol, etc. and that does not dissolve the polypropylene resin sheet, and depending on the application field, appropriately select a solvent that satisfies safety. It is good to use. As an antifogging agent solid content to the said sheet | seat, 0.02-2.0 g / m < 2 > is apply | coated. When the coating amount of the antifogging agent is below this range, the antifogging performance is insufficient, and when the coating amount of the antifogging agent exceeds this range, blocking between the sheets due to stickiness is not preferable.
The above antifogging agent can be applied by any method such as various roll printing methods, soaking methods, and spraying methods. The coating method can be carried out by in-line coating performed after sheet forming or outline coating performed in a rewinding step after sheet forming / winding.
Examples of the drying method after applying the antifogging agent include a method of evaporating the solvent through a sheet through a drying furnace heated by steam or electricity (when the solvent is water, 100 ° C. or higher is preferable). There is no limit.
３．防曇性シート等
本発明の防曇性ポリプロピレン系樹脂シートは、防曇性、透明性および再生使用に極めて優れているので、食品、化粧品、日用品の包装製品や、ＩＣチップや液晶パネルなど電子部品の梱包トレー、ディスプレー用の箱などの産業部材に最適である。
シートや製品の再生使用にあたっては、シートや製品を粉砕してバージン原料と混合し、シート成形機にかける方法や、シートや製品を粉砕したあと、押出機にて溶融混練してペレット（粒）状に加工してバージン原料と混合し、シート成形機にかける方法が行われる。
この場合、再生使用の割合にもよるが、押出機にて溶融混練してペレット（粒）状に加工した方が、原料の嵩密度が安定するために、シート成形加工が安定する。
3. Anti-fogging sheet, etc. The anti-fogging polypropylene resin sheet of the present invention is extremely excellent in anti-fogging property, transparency and reusable use, so that it can be used for packaging products for food, cosmetics, daily necessities, IC chips, liquid crystal panels, etc. Most suitable for industrial parts such as parts packing trays and display boxes.
When reusing sheets and products, the sheets and products are pulverized and mixed with virgin raw materials, and then applied to a sheet molding machine. After pulverizing the sheets and products, they are melt-kneaded in an extruder and pellets (grains) The sheet is processed into a shape, mixed with the virgin raw material, and applied to a sheet forming machine.
In this case, although depending on the ratio of recycle use, the sheet forming process is more stable when the raw material is melt kneaded and processed into pellets (grains) because the bulk density of the raw material is more stable.
以下に実施例を挙げて、本発明をさらに具体的に説明するが、本発明は、その要旨を超えない限り、これら実施例に制約されるものではない。なお、各実施例および比較例で用いた物性値の測定方法、評価法は、以下のとおりである。 EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples unless it exceeds the gist. In addition, the measuring method and evaluation method of the physical property values used in each example and comparative example are as follows.
Ｉ．測定方法、評価方法
１）ＭＦＲ
ＭＦＲは、ＪＩＳ Ｋ７２１０（２３０℃、２．１６ｋｇ荷重）に準拠して測定した。
I. Measurement method and evaluation method 1) MFR
MFR was measured based on JIS K7210 (230 degreeC, 2.16kg load).
２）引張弾性率
引張弾性率は、厚み０．３５ｍｍのシートに対して成形１日後にＪＩＳ Ｋ７１２７に準拠して測定した。
2) Tensile elastic modulus Tensile elastic modulus was measured based on JIS K7127 after 1 day for a sheet having a thickness of 0.35 mm.
３）ヘイズ値（ＨＡＺＥ値）
ＨＡＺＥは、厚み０．３５ｍｍのシートに対して成形１日後にＪＩＳ Ｋ７１３６に準拠して測定した。
3) Haze value (HAZE value)
HAZE was measured on a sheet having a thickness of 0.35 mm in accordance with JIS K7136 one day after molding.
４）エチレンの含量
エチレンの含量は、下記の条件の１３Ｃ−ＮＭＲ法によって計測された値である。
装置：日本電子社製 ＪＥＯＬ−ＧＳＸ２７０
濃度：３００ｍｇ／２ｍＬ
溶媒：オルソジクロロベンゼン
4) Ethylene content The ethylene content is a value measured by the 13 C-NMR method under the following conditions.
Apparatus: JEOL-GSX270 manufactured by JEOL Ltd.
Concentration: 300 mg / 2 mL
Solvent: Orthodichlorobenzene
５）防曇性
８０℃の湯にシートの防曇材塗布面をかざし、水滴の付着状況を観察した。
○：水滴が全く付着せず、良く透視できる。
△：大きな水滴が付き、７０％以上透視できる。
×：細かい水滴が付き、３０％以下しか透視できない。
5) Antifogging property The antifogging material application surface of the sheet was held over 80 ° C. hot water, and the state of water droplet adhesion was observed.
○: Water droplets do not adhere at all and can be seen well.
(Triangle | delta): A big water droplet is attached and 70% or more can be seen through.
X: A fine water droplet is attached and only 30% or less can be seen through.
６）遊離脂肪酸量
シートをアルミ箔で挟み、２１０℃で熱プレス加工して３℃に冷却し１００μｍ以下のフィルムに成形した。
次いで、このフィルム１．２５ｇを１ｃｍ×１ｃｍの大きさに裁断してフラスコに入れ、クロロホルム３０ｍＬを用いて２回抽出した。クロロホルム３０ｍＬを加え、還流冷却下、６０℃の湯浴中で１時間、超音波照射した。湯浴から取り出して室温まで静置冷却した後、ろ紙を用いてろ過して１度目のろ液を回収する。残ったフィルムにさらにクロロホルム３０ｍＬを加えて還流冷却下、６０℃の湯浴中で１５分間、超音波照射した。湯浴から取り出して室温まで静置冷却した後、先ほどと同じろ紙を用いてろ過して２度目のろ液を回収する。残ったフィルムとフラスコをさらに１５ｍＬのクロロホルムで洗い、洗液を先ほどと同じろ紙を用いてろ過して回収した。全てのろ液（洗液も含む）を合わせてナスフラスコに入れ、溶媒を減圧留去して抽出物を得た。
得られた抽出物にクロロホルム２ｍＬを（ホールピペット等を用いて）正確に加え、よく混合して得られた溶液をフィルターでろ過してガスクロマトグラフ測定用試料溶液を得た。
得られたガスクロマトグラフ測定用試料溶液を以下の条件で測定し、標準溶液の保持時間と一致するピークから、ミリスチン酸、パルミチン酸、ステアリン酸のピーク面積をそれぞれ求めた。
6) Amount of free fatty acid The sheet was sandwiched between aluminum foils, hot pressed at 210 ° C., cooled to 3 ° C., and formed into a film of 100 μm or less.
Next, 1.25 g of this film was cut into a size of 1 cm × 1 cm, put into a flask, and extracted twice using 30 mL of chloroform. 30 mL of chloroform was added, and ultrasonic irradiation was performed for 1 hour in a 60 ° C. hot water bath under reflux cooling. After taking out from a hot water bath and standing and cooling to room temperature, it filters using a filter paper and collects the 1st filtrate. 30 mL of chloroform was further added to the remaining film, and ultrasonic irradiation was performed for 15 minutes in a 60 ° C. hot water bath under reflux cooling. After removing from the hot water bath and allowing to cool to room temperature, it is filtered using the same filter paper as before, and the second filtrate is recovered. The remaining film and flask were further washed with 15 mL of chloroform, and the washing was collected by filtration using the same filter paper as before. All the filtrates (including the washings) were combined and placed in an eggplant flask, and the solvent was distilled off under reduced pressure to obtain an extract.
To the obtained extract, 2 mL of chloroform was accurately added (using a whole pipette or the like), and the solution obtained by mixing well was filtered through a filter to obtain a sample solution for gas chromatograph measurement.
The obtained sample solution for gas chromatograph measurement was measured under the following conditions, and the peak areas of myristic acid, palmitic acid, and stearic acid were determined from peaks that coincided with the retention time of the standard solution.
装置：島津製作所社製ガスクロマトグラフ「ＧＣ−２０１０」
装置条件
検出器：ＦＩＤ検出器
気化室温度：３２０℃
検出器温度：３５０℃
圧力制御：８０ｋＰａで１５分間置き、５０ｋＰａ／ｍｉｎの速度で５８０ｋＰａまで昇圧する。
カラム温度：１１０℃から１５℃／ｍｉｎの速度で３４１℃まで昇温し、９．６分間保つ。
カラム：Ｊ＆Ｗ Ｓｃｉｅｎｔｉｆｉｃ， ＤＢ−５ＭＳ （膜厚０．２５μｍ，φ０．２５ｍｍ×５ｍ）
注入量：１．０μＬ
標準溶液：１００ｍＬメスフラスコにミリスチン酸、パルミチン酸、ステアリン酸をそれぞれ１２．５ｍｇ量りとり、クロロホルムを加えて正確に１００ｍＬにした溶液。
以下の計算式によりそれぞれの遊離脂肪酸量を定量した。
シート中の遊離ミリスチン酸濃度（ｐｐｍ）
＝（測定試料溶液のミリスチン酸ピーク面積）÷（標準溶液のミリスチン酸ピーク面積）
×０．１２５（ｍｇ／ｍＬ）×２（ｍＬ）÷１２５０（ｍｇ）×１００００００
以下同様にして遊離パルミチン酸、遊離ステアリン酸のトータル濃度を求め、遊離脂肪酸含有量（ｗｔｐｐｍ）とした。
Apparatus: Gas chromatograph “GC-2010” manufactured by Shimadzu Corporation
Equipment conditions Detector: FID detector Vaporization chamber temperature: 320 ° C
Detector temperature: 350 ° C
Pressure control: Place at 80 kPa for 15 minutes, and increase the pressure to 580 kPa at a rate of 50 kPa / min.
Column temperature: The temperature is raised from 110 ° C. to 341 ° C. at a rate of 15 ° C./min, and maintained for 9.6 minutes.
Column: J & W Scientific, DB-5MS (film thickness 0.25 μm, φ0.25 mm × 5 m)
Injection volume: 1.0 μL
Standard solution: A solution in which 12.5 mg each of myristic acid, palmitic acid, and stearic acid was weighed into a 100 mL volumetric flask, and chloroform was added to make exactly 100 mL.
The amount of each free fatty acid was quantified by the following calculation formula.
Free myristic acid concentration in the sheet (ppm)
= (Myristic acid peak area of measurement sample solution) ÷ (Myristic acid peak area of standard solution)
× 0.125 (mg / mL) × 2 (mL) ÷ 1250 (mg) × 1000000
In the same manner, the total concentration of free palmitic acid and free stearic acid was determined and used as the free fatty acid content (wtppm).
ＩＩ．材料
１）プロピレン系樹脂
プロピレン系樹脂として、以下のプロピレン系樹脂（Ａ）、プロピレン系樹脂（Ｂ）を用いた。
（１）プロピレン系樹脂（Ａ）の製造
［触媒の製造］
攪拌翼と還流装置を取り付けた５Ｌセパラブルフラスコに、純水１，７００ｇを投入し、９８％硫酸５００ｇを滴下した。そこへ、平均粒径１８μｍに造粒したモンモリロナイト（原料として水澤化学工業社製商品名「ベンクレイＳＬ」を用いた）を３００ｇ添加後、攪拌した。その後９０℃で２時間反応させた。このスラリーをろ過、洗浄した。回収したケーキに２７％硫酸リチウム水溶液１，２３０ｇを加え、９０℃で２時間反応させた。このスラリーをろ過し、さらに、ろ液のｐＨが４以上となるまで洗浄した。回収したケーキを１００℃で予備乾燥した後に２００℃で２時間乾燥した。その結果、２７５ｇの化学処理モンモリロナイトを得た。
１Ｌフラスコに、化学処理モンモリロナイト２０ｇを加え、ヘプタン１２９ｍｌとトリイソブチルアルミニウムのヘプタン溶液７１ｍｌ（５０ｍｍｏｌ）を加え、室温で１時間攪拌した。その後、ヘプタンで残液率１／１００まで洗浄し、最後にスラリー量を１００ｍｌに調製した。さらに、トリノルマルオクチルアルミニウムのヘプタン溶液３ｍｌ（１ｍｍｏｌ）を加えて、１０分間室温で攪拌した。
２００ｍｌフラスコ中で、（ｒ）−ジメチルシリレンビス［１，１’−｛２−メチル−４−（４−クロロフェニル）−４Ｈ−アズレニル｝］ハフニウム（３００μｍｏｌ）にヘプタン（５０ｍｌ）を加えてスラリーとした後、上記１Ｌフラスコに加えて室温で６０分間攪拌した。その後、ヘプタン１８１ｍｌを加えて触媒スラリーを調製した。
II. Material 1) Propylene resin As propylene resin, the following propylene resin (A) and propylene resin (B) were used.
(1) Production of propylene resin (A) [Production of catalyst]
Into a 5 L separable flask equipped with a stirring blade and a reflux apparatus, 1,700 g of pure water was added, and 500 g of 98% sulfuric acid was added dropwise. Thereto, 300 g of montmorillonite granulated to an average particle size of 18 μm (product name “Benclay SL” manufactured by Mizusawa Chemical Industry Co., Ltd. was used as a raw material) was added and stirred. Thereafter, the mixture was reacted at 90 ° C. for 2 hours. This slurry was filtered and washed. To the collected cake, 1,230 g of a 27% lithium sulfate aqueous solution was added and reacted at 90 ° C. for 2 hours. This slurry was filtered and further washed until the pH of the filtrate reached 4 or higher. The recovered cake was pre-dried at 100 ° C. and then dried at 200 ° C. for 2 hours. As a result, 275 g of chemically treated montmorillonite was obtained.
To a 1 L flask, 20 g of chemically treated montmorillonite was added, 129 ml of heptane and 71 ml (50 mmol) of a heptane solution of triisobutylaluminum were added, and the mixture was stirred at room temperature for 1 hour. Thereafter, the residue was washed with heptane to a residual liquid ratio of 1/100, and finally the amount of slurry was adjusted to 100 ml. Furthermore, 3 ml (1 mmol) of a heptane solution of trinormal octyl aluminum was added and stirred at room temperature for 10 minutes.
In a 200 ml flask, heptane (50 ml) was added to (r) -dimethylsilylenebis [1,1 ′-{2-methyl-4- (4-chlorophenyl) -4H-azurenyl}] hafnium (300 μmol) to form a slurry. Then, in addition to the 1 L flask, the mixture was stirred at room temperature for 60 minutes. Thereafter, 181 ml of heptane was added to prepare a catalyst slurry.
［予備重合］
窒素で十分置換を行った内容積１．０Ｌの撹拌式オートクレーブに、上記触媒スラリーを全量導入した。温度が４０℃に安定したところでプロピレンを１０ｇ／時間の速度で供給し、温度を維持した。４時間後プロプレンの供給を停止し、さらに１時間維持した。予備重合終了後、残モノマーをパージし、撹拌を停止させ、十分窒素置換を行った１Ｌフラスコにスラリーを抜き出した。このスラリーを減圧乾燥して予備重合触媒を６３．４ｇ回収した。
［重合］
内容積２００Ｌの誘導撹拌機付オートクレーブ内をプロピレンで十分置換した後に、十分に脱水処理した液化プロピレン４５ｋｇを導入し３０℃に保持した。これに、トリイソブチルアルミニウムのヘプタン溶液４７０ｍｌ（５０ｇ／ｌ）を加えた。水素２．０ＮＬ、エチレンを０．９ｋｇ導入し、上記予備重合触媒１．７ｇをアルゴンで圧入した。温度６５℃まで４０分かけて昇温し、６５℃で２時間反応させた。また、この間水素を０．１２ｇ／ｈｒの定速で導入した。その後、エタノール１００ｍｌを圧入して、反応を停止させ、残ガスをパージした。その結果、１８．４ｋｇのプロピレン系樹脂（Ａ）が得られた。該樹脂のＭＦＲは、１．４ｇ／１０ｍｉｎ、エチレン含量１．３重量％であった。
[Preliminary polymerization]
The entire amount of the catalyst slurry was introduced into a stirring autoclave having an internal volume of 1.0 L that had been sufficiently replaced with nitrogen. When the temperature was stabilized at 40 ° C., propylene was supplied at a rate of 10 g / hour to maintain the temperature. After 4 hours, the supply of proprene was stopped and maintained for another hour. After completion of the prepolymerization, the residual monomer was purged, the stirring was stopped, and the slurry was extracted into a 1 L flask that had been sufficiently purged with nitrogen. This slurry was dried under reduced pressure to recover 63.4 g of a prepolymerized catalyst.
[polymerization]
After sufficiently replacing the interior of the autoclave with an induction stirrer with an internal volume of 200 L with propylene, 45 kg of sufficiently dehydrated liquefied propylene was introduced and maintained at 30 ° C. To this, 470 ml (50 g / l) of a heptane solution of triisobutylaluminum was added. Hydrogen 2.0NL and ethylene 0.9kg were introduced, and 1.7g of the prepolymerized catalyst was injected with argon. The temperature was raised to 65 ° C. over 40 minutes, and the reaction was carried out at 65 ° C. for 2 hours. During this time, hydrogen was introduced at a constant speed of 0.12 g / hr. Thereafter, 100 ml of ethanol was injected to stop the reaction, and the remaining gas was purged. As a result, 18.4 kg of propylene resin (A) was obtained. The resin had an MFR of 1.4 g / 10 min and an ethylene content of 1.3% by weight.
（２）プロピレン系樹脂（Ｂ）の製造
内容積２００リットルの攪拌式重合槽により、プロピレン−エチレンランダム共重合体の製造を実施した。重合槽内をプロピレンで充分置換した後、脱水・脱酸素したｎ−ヘプタン６０リットルを導入し、ジエチルアルミニウムクロライド３０．０ｇ、ソルベー社タイプ三塩化チタン触媒１０ｇをプロピレン雰囲気下、６０℃で導入した。
重合槽内の温度を６０℃に昇温した後、プロピレンを５．９ｋｇ／時間、エチレンを０．１８ｋｇ／時間のフィード速度で導入し、併用する水素は、気相部の水素濃度１．１ｖｏｌ．％で制御した。６時間重合を継続した後、プロピレンとエチレンの導入を止め、さらに重合槽内の温度を６０℃で６０分間継続させた。
このようにして得られたスラリーを、濾過、乾燥して３２．０ｋｇのパウダー状のプロピレン−エチレンランダム共重合体であるプロピレン系樹脂（Ｂ）を得た。得られたプロピレン系樹脂（Ｂ）は、ＭＦＲ＝１．０ｇ／１０分、エチレン含有量＝２．５重量％であった。
(2) Production of propylene-based resin (B) Propylene-ethylene random copolymer was produced in a stirring polymerization tank having an internal volume of 200 liters. After sufficiently replacing the inside of the polymerization tank with propylene, 60 liters of dehydrated and deoxygenated n-heptane was introduced, and 30.0 g of diethylaluminum chloride and 10 g of Solvay type titanium trichloride catalyst were introduced at 60 ° C. in a propylene atmosphere. .
After raising the temperature in the polymerization tank to 60 ° C., propylene is introduced at a feed rate of 5.9 kg / hour and ethylene is introduced at a feed rate of 0.18 kg / hour. . %. After the polymerization was continued for 6 hours, the introduction of propylene and ethylene was stopped, and the temperature in the polymerization tank was further continued at 60 ° C. for 60 minutes.
The slurry thus obtained was filtered and dried to obtain 32.0 kg of a propylene-based resin (B) which is a powdery propylene-ethylene random copolymer. The obtained propylene-based resin (B) had MFR = 1.0 g / 10 min and ethylene content = 2.5% by weight.
２）造核剤
造核剤として、以下の造核剤を用いた。
（１）ＡＤＥＫＡ社製商品名「アデカスタブＮＡ−１１」：
リン酸２，２’−メチレンビス（４，６−ジ−ｔ−ブチルフェニル）ナトリウム
（２）ＡＤＥＫＡ社製商品名「アデカスタブＮＡ−７１」：
リン酸２，２’−メチレンビス（４，６−ジ−ｔ−ブチルフェニル）リチウム系造核剤
（３）チバ・スペシャリティ・ケミカルズ社製商品名「イルガクリアＸＴ３８６」：
トリアミノベンゼン系造核剤
（４）新日本理化社製商品名「ゲルオールＭＤ」：
１，３：２，４−ジ（ｐ−メチルベンジリデン）ソルビトール
（５）ＡＤＥＫＡ社製商品名「アデカスタブＮＡ−２１」：
ビス（２，４，８，１０−テトラ−ｔｅｒｔ−ブチル−６−ヒドロキシ−１２Ｈ−ジベンゾ［ｄ，ｇ］［１，２，３］ジオキサホスホシン−６−オキシド）水酸化アルミニウム塩
2) Nucleating agent The following nucleating agents were used as nucleating agents.
(1) Product name “ADEKA STAB NA-11” manufactured by ADEKA:
2,2′-Methylenebis (4,6-di-t-butylphenyl) sodium phosphate (2) Trade name “ADEKA STAB NA-71” manufactured by ADEKA Corporation:
Phosphoric acid 2,2′-methylenebis (4,6-di-t-butylphenyl) lithium nucleating agent (3) trade name “Irga Clear XT386” manufactured by Ciba Specialty Chemicals, Inc .:
Triaminobenzene nucleating agent (4) Brand name “Gelall MD” manufactured by Shin Nippon Rika Co., Ltd .:
1,3: 2,4-di (p-methylbenzylidene) sorbitol (5) Trade name “ADEKA STAB NA-21” manufactured by ADEKA Corporation:
Bis (2,4,8,10-tetra-tert-butyl-6-hydroxy-12H-dibenzo [d, g] [1,2,3] dioxaphosphocin-6-oxide) aluminum hydroxide salt
３）防曇剤
防曇剤として、以下の化合物を用いた。
（１）三菱化学フーズ社製商品名「リョートーシュガーエステルＬＷＡ−１５７０」：
蔗糖ラウリン酸エステル
3) Antifogging agent The following compounds were used as an antifogging agent.
(1) Trade name “Ryoto Sugar Ester LWA-1570” manufactured by Mitsubishi Chemical Foods Corporation:
Sucrose laurate
［実施例１］
１−１）組成物の調製
プロピレン系系樹脂（Ａ）１００重量部に対し、造核剤としてリン酸２，２’−メチレンビス（４，６−ジ−ｔ−ブチルフェニル）ナトリウム（商品名：ＡＤＥＫＡ社製「アデカスタブＮＡ−１１」）０．１重量部、さらに酸化防止剤として〔テトラキス（３，５−ジ−ｔ−ブチルフェニルプロピオネート）〕メタン０．０３重量部（商品名：チバスペシャリティケミカル（株）製「イルガノックスＲＡ１０１０」）とトリス（ジブチルフェニル）フォスファイト（商品名：チバスペシャリティケミカル（株）製「イルガフォス１６８」）０．１重量部を添加してヘンシェルミキサーにて混合しプロピレン系樹脂組成物を得た後、２６０℃に加熱されたスクリュー径が５０ｍｍの押出機にて押出し、粒状物とした。
[Example 1]
1-1) Preparation of composition With respect to 100 parts by weight of the propylene-based resin (A), 2,2′-methylenebis (4,6-di-t-butylphenyl) sodium phosphate (trade name: trade name: 0.1 part by weight of “ADEKA STAB NA-11” manufactured by ADEKA, and 0.03 part by weight of [tetrakis (3,5-di-t-butylphenylpropionate)] methane as an antioxidant (trade name: Ciba Specialty) "Irganox RA1010" manufactured by Chemical Co., Ltd.) and 0.1 parts by weight of Tris (dibutylphenyl) phosphite (trade name: "Irgaphos 168" manufactured by Ciba Specialty Chemicals Co., Ltd.) are added and mixed using a Henschel mixer. After obtaining a propylene-based resin composition, it was extruded with an extruder heated at 260 ° C. and having a screw diameter of 50 mm to obtain a granular material.
１−２）押出シートの作製
得られた粒状物を２３０℃に加熱されたスクリュー径４０ｍｍの押出シート成形機にて幅７５０ｍｍ、ダイリップ間隔０．８ｍｍのコートハンガーダイから水平方向に押出し、３０℃の水が内部で循環している鏡面加工された硬質クロムメッキの金属ロールで挟んで冷却固化し、片面にコロナ処理をかけて４０ダインとしながら厚み０．３５ｍｍのシートを製造した。得られたシートの物性の測定結果を第１表に示す。
１−３）防曇剤の塗布
次いで、上記シートのコロナ処理面に、三菱化学フーズ社製「リョートーシュガーエステルＬＷＡ−１５７０」（蔗糖ラウリン酸エステル）の４０倍水溶液をグラビアコーターにて４ｇ／ｍ２を塗付し、１２０℃の空気が循環している乾燥機にて乾燥後巻取り機にて巻き取って防曇シートを作成した。防曇剤固形分は０．０４ｇ／ｍ２の塗付量である。この防曇シートを５枚重ねて日本電色社製のカラーマシンにてＹＩ値を測定した。結果を第１表に示す。
1-2) Production of Extruded Sheet The obtained granular material was extruded in a horizontal direction from a coat hanger die having a width of 750 mm and a die lip interval of 0.8 mm in an extrusion sheet molding machine heated to 230 ° C. and having a screw diameter of 40 mm, and 30 ° C. The sheet was cooled and solidified with a mirror-finished hard chrome-plated metal roll in which water was circulated, and a sheet having a thickness of 0.35 mm was manufactured while corona treatment was applied to one side to make 40 dynes. The measurement results of the physical properties of the obtained sheet are shown in Table 1.
1-3) Application of antifogging agent Next, a 40 times aqueous solution of “Ryoto Sugar Ester LWA-1570” (sucrose lauric acid ester) manufactured by Mitsubishi Chemical Foods Co., Ltd. was applied to the corona-treated surface of the above sheet with a gravure coater. m 2 was applied, dried in a dryer in which air at 120 ° C. was circulated, and wound up with a winder to prepare an antifogging sheet. The antifogging agent solid content is a coating amount of 0.04 g / m 2 . Five of these anti-fogging sheets were stacked and the YI value was measured with a color machine manufactured by Nippon Denshoku. The results are shown in Table 1.
１−４）再生ペレットの作製
その後、上記防曇シートを、株式会社ホーライ製の粉砕機ＵＩ０３−３０１２０ＭＲＦＳ型で、φ９ｍｍのスクリーンにかけて粉砕品を得た。この粉砕品を２３０℃に加熱されたスクリュー径が４０ｍｍの押出機にて溶融混錬して再生ペレットを製造した。
１−５）再生シートの製造
１−１）の粒状物５０重量部に対し、１−４）の再生ペレット５０重量部を混合して１−１）〜１−３）の方法で再生防曇シートを作成した。この防曇シートを５枚重ねて日本電色社製のカラーマシンにてＹＩ値を測定した。結果を第１表に示す。
1-4) Production of Recycled Pellet Then, the above antifogging sheet was applied to a φ9 mm screen with a crusher UI03-30120MRFS manufactured by Horai Co., Ltd. to obtain a pulverized product. This pulverized product was melt-kneaded with an extruder having a screw diameter of 40 mm heated to 230 ° C. to produce recycled pellets.
1-5) Production of Recycled Sheet 50 parts by weight of the granulated material of 1-1) is mixed with 50 parts by weight of the regenerated pellets of 1-4), and regenerated antifog by the method of 1-1) to 1-3) Created a sheet. Five of these anti-fogging sheets were stacked and the YI value was measured with a color machine manufactured by Nippon Denshoku. The results are shown in Table 1.
［実施例２］
実施例１において、配合物を表２に示す如く変化させた以外は、実施例１と同様に実施した。その結果を表１に示す。
[Example 2]
Example 1 was carried out in the same manner as Example 1 except that the formulation was changed as shown in Table 2. The results are shown in Table 1.
［実施例３］
実施例１において、配合物を表２に示す如く変化させた以外は、実施例１と同様に実施した。その結果を表１に示す。
[Example 3]
Example 1 was carried out in the same manner as Example 1 except that the formulation was changed as shown in Table 2. The results are shown in Table 1.
［実施例４］
実施例１において、配合物を表２に示す如く変化させた以外は、実施例１と同様に実施した。その結果を表１に示す。
[Example 4]
Example 1 was carried out in the same manner as Example 1 except that the formulation was changed as shown in Table 2. The results are shown in Table 1.
［実施例５］
プロピレン系樹脂（Ｂ）１００重量部に対し、造核剤としてリン酸２，２’−メチレンビス（４，６−ジ−ｔ−ブチルフェニル）ナトリウム（「アデカスタブＮＡ１１」）０．１重量部、さらに酸化防止剤として〔テトラキス（３，５−ジ−ｔ−ブチルフェニルプロピオネート）〕メタン０．０３重量部（「イルガノックスＲＡ１０１０」）とトリス（ジブチルフェニル）フォスファイト（「イルガフォス１６８」）０．１重量部を添加してヘンシェルミキサーにて混合し、プロピレン系樹脂組成物を得た後、２６０℃に加熱されたスクリュー径が５０ｍｍの押出機にて押出し粒状物とした。
その後、この粒状物に実施例１の１−３）〜１−５）と同様の方法を適用し、再生防曇シートを作成した。その結果を第１表に示す。
[Example 5]
0.1 part by weight of 2,2′-methylenebis (4,6-di-t-butylphenyl) sodium phosphate (“ADK STAB NA11”) as a nucleating agent with respect to 100 parts by weight of the propylene-based resin (B), [Tetrakis (3,5-di-t-butylphenylpropionate)] methane 0.03 part by weight ("Irganox RA1010") and tris (dibutylphenyl) phosphite ("Irgaphos 168") 0. 1 part by weight was added and mixed with a Henschel mixer to obtain a propylene-based resin composition, which was then extruded into a granulated product by an extruder having a screw diameter of 50 mm heated to 260 ° C.
Thereafter, the same method as in 1-3) to 1-5) of Example 1 was applied to the granular material to prepare a recycled antifogging sheet. The results are shown in Table 1.
［比較例１、２］
プロピレン系樹脂組成物の配合物を第２表に示す如く変えた以外は、実施例１と同様にして評価した。その結果を第２表に示す。
[Comparative Examples 1 and 2]
Evaluation was performed in the same manner as in Example 1 except that the composition of the propylene-based resin composition was changed as shown in Table 2. The results are shown in Table 2.
［比較例３］
組成物を下記のノバテックＰＰ「ＥＡ７Ａ」に造核剤としてリン酸２，２’−メチレンビス（４，６−ジ−ｔ−ブチルフェニル）ナトリウム（「アデカスタブＮＡ−１１」）を添加した組成物に変えた以外は、実施例１と同様にして評価した。その結果を第２表に示す。
「ノバテックＰＰ ＥＡ７Ａ」（日本ポリプロ社製 ＭＦＲ＝１．４ｇ／１０分のプロピレン単独重合体）１００重量部に対して、「イルガノックスＲＡ１０１０」が０．０５重量部と「イルガフォス１６８」が０．１重量部と、ステアリン酸カルシウムが０．０５重量部を含有している。
[Comparative Example 3]
The composition was added to the following Novatec PP “EA7A” with 2,2′-methylenebis (4,6-di-t-butylphenyl) sodium phosphate (“ADK STAB NA-11”) added as a nucleating agent. The evaluation was performed in the same manner as in Example 1 except that the change was made. The results are shown in Table 2.
With respect to 100 parts by weight of “Novatech PP EA7A” (Propylene homopolymer made by Nippon Polypro Co., Ltd. MFR = 1.4 g / 10 min), 0.05 parts by weight of “Irganox RA1010” and 0. 1 part by weight and 0.05 parts by weight of calcium stearate.
［比較例４］
比較例１で防曇剤を塗付しなかった以外は、実施例３と同様にして評価した。その結果を第２表に示す。
[Comparative Example 4]
Evaluation was performed in the same manner as in Example 3 except that the antifogging agent was not applied in Comparative Example 1. The results are shown in Table 2.
［実施例６〜８］
実施例１において、配合物を表３に示す如く変えた以外は、実施例１と同様に実施した。なお、ステアリン酸アルミニウムとして、日東化成工業株式会社製商品名「Ａｌ−ＳＴ（１０３）」を使用した。その結果を表３に示す。
[Examples 6 to 8]
Example 1 was carried out in the same manner as in Example 1 except that the formulation was changed as shown in Table 3. In addition, the product name "Al-ST (103)" by Nitto Kasei Kogyo Co., Ltd. was used as aluminum stearate. The results are shown in Table 3.
これらの結果より明らかなように、実施例１〜８では、本発明の防曇性プロピレン系樹脂シートは、ＨＡＺＥ値が小さく（透明性に優れ）、防曇性に優れ、再生しても色相変化が少ない事が解る。
これに対し、比較例１〜３では、本発明で特定する遊離脂肪酸の量が上回る為に、再生シートの色相が極めて悪いものであった。また、比較例４では、本発明で特定する脂肪酸金属塩の量が上回るが、防曇剤を塗付していないために、再生シートの色相変化が少ないものの、防曇性能が全く無いものであった。
以上の各実施例のデータ、及び各比較例との対照結果より、本発明の防曇性プロピレン系樹脂シートが、従来の材料より、透明性や防曇性が優れ、かつ再生しても色相変化が少ないことが明白であり、本発明を構成する要件の合理性と有意性が実証され、従来技術への卓越性も明らかにされている。
As is clear from these results, in Examples 1 to 8, the antifogging propylene resin sheet of the present invention has a small HAZE value (excellent transparency), excellent antifogging properties, and hue even when regenerated. I understand that there is little change.
On the other hand, in Comparative Examples 1-3, since the amount of the free fatty acid specified by the present invention exceeded, the hue of the recycled sheet was extremely bad. Further, in Comparative Example 4, the amount of the fatty acid metal salt specified in the present invention exceeds, but since no antifogging agent is applied, the hue of the recycled sheet is small, but there is no antifogging performance at all. there were.
From the data of each of the above examples and the comparison result with each comparative example, the antifogging propylene-based resin sheet of the present invention has better transparency and antifogging properties than conventional materials, and even when reproduced, the hue. It is clear that there is little change, the rationality and significance of the requirements that make up the present invention are demonstrated, and the superiority to the prior art is also revealed.
以上、説明したように、本発明によれば、透明性と防曇性に優れ、かつ再生使用しても変色の少ない防曇性プロピレン系樹脂シートが得られるため、経済性、環境性に優れ、食品日用品の包装や医療電子部品の分野に好適に使用することができ、その産業上の有用性は非常に高い。 As described above, according to the present invention, an antifogging propylene-based resin sheet that is excellent in transparency and antifogging properties and has little discoloration even after being recycled can be obtained. It can be suitably used in the field of food daily necessities packaging and medical electronic parts, and its industrial utility is very high.
Claims (4)
上記プロピレン系樹脂シートは、ＭＦＲが０．２〜３０ｇ／１０分のプロピレン系樹脂１００重量部に対し、芳香族カルボン酸金属塩系、芳香族リン酸金属塩系、ソルビトール系およびアミン系造核剤からなる群から選ばれる少なくとも１種の造核剤を０．００１〜１重量部の割合で配合してなるプロピレン系樹脂組成物から形成され、かつ炭素数６〜２２の遊離脂肪酸の含有量が５０ｐｐｍ以下であり、
一方、上記防曇剤は、炭素数６〜２２の脂肪酸の蔗糖脂肪酸エステルからなることを特徴とする防曇性プロピレン系樹脂シート。 A propylene resin sheet obtained by applying 0.02 to 2 g / m 2 of an antifogging agent in a solid content to at least one surface of a propylene resin sheet having a thickness of 0.1 to 2 mm,
The propylene-based resin sheet has an aromatic carboxylic acid metal salt-based, aromatic phosphate metal salt-based, sorbitol-based, and amine-based nucleating with respect to 100 parts by weight of a propylene-based resin having an MFR of 0.2 to 30 g / 10 min. Of a free fatty acid having 6 to 22 carbon atoms, which is formed from a propylene-based resin composition obtained by blending at least one nucleating agent selected from the group consisting of agents in a proportion of 0.001 to 1 part by weight. Is 50 ppm or less,
On the other hand, the said antifogging agent consists of sucrose fatty acid ester of a C6-C22 fatty acid, The antifogging propylene-type resin sheet characterized by the above-mentioned.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011084613A (en) * | 2009-10-14 | 2011-04-28 | Japan Polypropylene Corp | Antifogging propylene-based resin sheet |
| JP2012102246A (en) * | 2010-11-10 | 2012-05-31 | Adeka Corp | Polypropylene-based resin composition |
| JP2013233694A (en) * | 2012-05-08 | 2013-11-21 | Japan Polypropylene Corp | Molding |
| JP2016221760A (en) * | 2015-05-28 | 2016-12-28 | 住友ベークライト株式会社 | Multilayer film and package |
| JP2019209694A (en) * | 2019-09-10 | 2019-12-12 | 住友ベークライト株式会社 | Multilayer film and package |
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| JPS5499180A (en) * | 1978-01-20 | 1979-08-04 | Toyobo Co Ltd | Anti-fogging transparent film |
| JPH10158419A (en) * | 1996-11-27 | 1998-06-16 | Mitsubishi Chem Corp | Production of thermoformed propylene resin item, and thermoformed item |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2011084613A (en) * | 2009-10-14 | 2011-04-28 | Japan Polypropylene Corp | Antifogging propylene-based resin sheet |
| JP2012102246A (en) * | 2010-11-10 | 2012-05-31 | Adeka Corp | Polypropylene-based resin composition |
| JP2013233694A (en) * | 2012-05-08 | 2013-11-21 | Japan Polypropylene Corp | Molding |
| JP2016221760A (en) * | 2015-05-28 | 2016-12-28 | 住友ベークライト株式会社 | Multilayer film and package |
| JP2019209694A (en) * | 2019-09-10 | 2019-12-12 | 住友ベークライト株式会社 | Multilayer film and package |
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