JP6377579B2 - Polyethylene terephthalate laminated paper - Google Patents
Polyethylene terephthalate laminated paper Download PDFInfo
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- JP6377579B2 JP6377579B2 JP2015141820A JP2015141820A JP6377579B2 JP 6377579 B2 JP6377579 B2 JP 6377579B2 JP 2015141820 A JP2015141820 A JP 2015141820A JP 2015141820 A JP2015141820 A JP 2015141820A JP 6377579 B2 JP6377579 B2 JP 6377579B2
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- 229920000139 polyethylene terephthalate Polymers 0.000 title claims description 81
- 239000005020 polyethylene terephthalate Substances 0.000 title claims description 81
- -1 Polyethylene terephthalate Polymers 0.000 title claims description 32
- 229920005989 resin Polymers 0.000 claims description 96
- 239000011347 resin Substances 0.000 claims description 96
- 239000011342 resin composition Substances 0.000 claims description 37
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 32
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 31
- 150000002894 organic compounds Chemical class 0.000 claims description 25
- 125000003700 epoxy group Chemical group 0.000 claims description 23
- 238000004519 manufacturing process Methods 0.000 claims description 20
- 238000001125 extrusion Methods 0.000 claims description 18
- 239000000758 substrate Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 15
- 238000002844 melting Methods 0.000 claims description 14
- 230000008018 melting Effects 0.000 claims description 14
- 238000002425 crystallisation Methods 0.000 claims description 11
- 230000008025 crystallization Effects 0.000 claims description 11
- 238000010030 laminating Methods 0.000 claims description 11
- 238000003475 lamination Methods 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- 238000004898 kneading Methods 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 claims description 4
- 239000000155 melt Substances 0.000 claims description 4
- 238000004458 analytical method Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims 1
- 238000000113 differential scanning calorimetry Methods 0.000 claims 1
- 230000004927 fusion Effects 0.000 claims 1
- 239000000123 paper Substances 0.000 description 50
- 230000000052 comparative effect Effects 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- 235000013305 food Nutrition 0.000 description 7
- 239000002655 kraft paper Substances 0.000 description 7
- 230000000903 blocking effect Effects 0.000 description 6
- 239000003549 soybean oil Substances 0.000 description 6
- 235000012424 soybean oil Nutrition 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 235000019198 oils Nutrition 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000004970 Chain extender Substances 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 229920002873 Polyethylenimine Polymers 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003205 fragrance Substances 0.000 description 3
- 229920005672 polyolefin resin Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 238000009966 trimming Methods 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 238000010411 cooking Methods 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 235000013312 flour Nutrition 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 229920001684 low density polyethylene Polymers 0.000 description 2
- 239000004702 low-density polyethylene Substances 0.000 description 2
- NMHTWXYFOWTMJH-UHFFFAOYSA-N oxiran-2-ylmethyl 2-methylprop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.CC(=C)C(=O)OCC1CO1 NMHTWXYFOWTMJH-UHFFFAOYSA-N 0.000 description 2
- 229920002215 polytrimethylene terephthalate Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 229920003355 Novatec® Polymers 0.000 description 1
- 244000046052 Phaseolus vulgaris Species 0.000 description 1
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 235000013353 coffee beverage Nutrition 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 235000021539 instant coffee Nutrition 0.000 description 1
- 239000005001 laminate film Substances 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- RLAWWYSOJDYHDC-BZSNNMDCSA-N lisinopril Chemical compound C([C@H](N[C@@H](CCCCN)C(=O)N1[C@@H](CCC1)C(O)=O)C(O)=O)CC1=CC=CC=C1 RLAWWYSOJDYHDC-BZSNNMDCSA-N 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000001953 sensory effect Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
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- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
Images
Landscapes
- Laminated Bodies (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、ポリエチレンテレフタレートを主成分とする樹脂組成物を紙基材上に溶融押出ラミネートする積層紙の製造方法に関するものである。 The present invention relates to a method for producing a laminated paper in which a resin composition containing polyethylene terephthalate as a main component is melt-extruded laminated on a paper substrate.
紙容器は食品の直接容器として、多種多様に亘って常用されている。これらの紙容器の内面には、耐水性の付与やヒートシールによる製函ができるようにポリオレフィン樹脂層、とりわけポリエチレン樹脂層を配した積層体が多用されている。 Paper containers are widely used as direct food containers. On the inner surface of these paper containers, a laminate in which a polyolefin resin layer, particularly a polyethylene resin layer is provided, is often used so that water resistance can be imparted and heat-sealing can be performed.
しかしながら、ポリオレフィン樹脂は、食品中に含まれる芳香性の高い成分や脂溶性の成分を吸着、収着し易く、味や香りの一部が失われるという性質があるため、保香性が必要な食品容器には用いることはできなかった。さらにポリオレフィン樹脂は、融点が最も高いポリプロピレン樹脂においても１６０℃近傍であり、これを越える高温域での使用（たとえば２００℃前後のオーブン加熱）はできなかった。 However, since polyolefin resin has the property of easily adsorbing and sorbing highly aromatic components and fat-soluble components contained in foods and losing a part of the taste and fragrance, it needs aroma retention. It could not be used for food containers. Further, the polyolefin resin has a temperature of around 160 ° C. even in the polypropylene resin having the highest melting point, and cannot be used in a high temperature range exceeding this (for example, oven heating at around 200 ° C.).
保香性、耐熱性および耐油性に優れ、且つ廉価な材料の１つとしてポリエチレンテレフタレート（以下、ＰＥＴと記す。）樹脂が挙げられ、内面にＰＥＴ樹脂が積層された紙容器も上市されている。 Polyethylene terephthalate (hereinafter referred to as PET) resin is listed as one of inexpensive materials with excellent fragrance retention, heat resistance and oil resistance, and paper containers having PET resin laminated on the inner surface are also on the market. .
しかし溶融状態になると著しく粘度が低下する性状をもつＰＥＴ樹脂を紙基材と溶融積層する場合、下記の問題点があった。
（１）ネックインやドローダウンと呼ばれる製品フィルム幅がダイ出口幅より狭くなる現象が生じ、採取製品収率が低下していた。
（２）また商業生産を考えた場合、積層工程の高速化が必要となるが、高速化は前述のネックインやドローダウンがより顕著となるため、低速で加工せざるを得なかった。
However, when a PET resin having a property that the viscosity is remarkably lowered when it is in a molten state is melt-laminated with a paper substrate, there are the following problems.
(1) The phenomenon that the product film width called neck-in or drawdown becomes narrower than the die exit width occurred, and the yield of collected products was reduced.
(2) When considering commercial production, it is necessary to increase the speed of the laminating process. However, since the above-mentioned neck-in and draw-down become more conspicuous, it is necessary to process at a low speed.
本発明者らは、このネックインやドローダウンを解決する手段として、ＰＥＴ樹脂に、（メタ）アクリル酸グリシジル、スチレン−（メタ）アクリル酸メチル−メタクリル酸グリシジル、エポキシ化大豆油等の鎖延長剤を添加して紙層上に押し出してＰＥＴ樹脂積層紙を製造する方法を開発した（特許文献１）。 As a means for solving this neck-in and drawdown, the present inventors have added chain extension of PET resin, glycidyl (meth) acrylate, styrene-methyl (meth) acrylate-glycidyl methacrylate, epoxidized soybean oil, etc. A method for producing a PET resin laminated paper by adding an agent and extruding it onto a paper layer was developed (Patent Document 1).
また、ＰＥＴ樹脂と同様にネックインやドローダウンの問題があるポリブチレンテレフタレート（以下、ＰＢＴと記す。）樹脂についてもエポキシ化大豆油やエチレン−（メタ）アクリル酸グリシジル共重合体などの１分子内に２個以上のエポキシ基をもつ有機化合物を配合して紙基材上に押し出してＰＢＴ樹脂積層紙を製造する方法も開発した（特許文献２）。 Similarly to PET resin, polybutylene terephthalate (hereinafter referred to as PBT) resin, which has neck-in and draw-down problems, is also one molecule such as epoxidized soybean oil or ethylene- (meth) acrylate glycidyl copolymer. A method has also been developed in which an organic compound having two or more epoxy groups is blended therein and extruded onto a paper substrate to produce a PBT resin laminated paper (Patent Document 2).
特許文献１の方法では、積層体のＰＥＴ樹脂は結晶化度が１５％未満でＰＥＴ樹脂層間のヒートシールが可能である。しかし、鎖延長剤は一般に液状や粉状をしており、その均一分散性を高めるためにＰＥＴ樹脂を用いてマスターバッチを作製すると、鎖延長剤は、ＰＥＴ樹脂との反応性にとんでいてその間にも反応が進行してしまうため、使用量が増加して経済的に好ましくないという問題があった。また、積層体を積み重ねて長時間放置すると、それが原反状である場合も容器に形成されている場合もブロッキングを起こして個々に分離しにくくなるという問題もあった。 In the method of Patent Document 1, the PET resin of the laminate has a crystallinity of less than 15% and can be heat-sealed between the PET resin layers. However, the chain extender is generally in the form of liquid or powder, and when a masterbatch is prepared using PET resin in order to increase its uniform dispersibility, the chain extender is very reactive with the PET resin. In the meantime, since the reaction proceeds, there is a problem that the amount used is increased, which is not preferable economically. In addition, when the laminates are stacked and left for a long time, there is a problem in that they are difficult to separate individually due to blocking even when they are in a raw fabric state or formed in a container.
特許文献２の方法では、ＰＢＴ樹脂は、元来ヒートシール性がないため、その積層紙は密封が要求される用途には使えないという問題があった。 In the method of Patent Document 2, since the PBT resin originally has no heat sealability, the laminated paper cannot be used for applications requiring sealing.
本発明の目的は、ＰＥＴ樹脂積層時のネックインやドローダウンを解決し、樹脂層間でヒートシールでき、保香性、耐熱性、耐油性に優れ、ブロッキングの問題のない紙容器にすることができるＰＥＴ樹脂積層紙を安価に製造できる方法を提供することにある。 The object of the present invention is to solve the neck-in and drawdown when laminating the PET resin, heat seal between the resin layers, and to make a paper container excellent in aroma retaining property, heat resistance, oil resistance and free from blocking problems. Another object of the present invention is to provide a method capable of producing a PET resin laminated paper that can be produced at low cost.
本発明者らは、これらの問題を解決するべく鋭意検討の結果、鎖延長剤として機能させる１分子内に少なくとも２個のエポキシ基をもつ有機化合物をマスターバッチにする樹脂にＰＢＴを用いると反応性がＰＥＴ程高くないため有機化合物の消費を抑えて使用量を削減できることを見出した。そして、マスターバッチ用の樹脂にＰＢＴを用いるとブロッキングの問題も解消できることを見出した。これは、ＰＢＴ樹脂の結晶化温度がＰＥＴ樹脂よりも高いため、積層後の冷却において、まずＰＢＴ樹脂の結晶化が始まることによると考えられる。 As a result of intensive studies to solve these problems, the present inventors have reacted when PBT is used as a resin for making a master batch of an organic compound having at least two epoxy groups in one molecule that functions as a chain extender. It was found that the amount of the organic compound consumed can be reduced by suppressing the consumption of the organic compound because the property is not as high as that of PET. And when PBT was used for resin for master batches, it discovered that the problem of blocking could also be eliminated. This is presumably because the crystallization temperature of the PBT resin is higher than that of the PET resin, and thus the crystallization of the PBT resin starts first in the cooling after the lamination.
本発明は、これらの知見に基づいてなされたものであり、ポリブチレンテレフタレート樹脂に１分子内に少なくとも２個のエポキシ基をもつ有機化合物を溶融混練してマスターバッチを作製し、これをポリエチレンテレフタレート樹脂に加えて溶融混練し、紙基材上に押し出し積層することを特徴とする、ポリエチレンテレフタレート樹脂積層紙の製造方法を提供するものである。 The present invention has been made on the basis of these findings. A master batch was prepared by melt-kneading an organic compound having at least two epoxy groups in one molecule in a polybutylene terephthalate resin. The present invention provides a method for producing a polyethylene terephthalate resin laminated paper, which is melt-kneaded in addition to a resin and extruded and laminated on a paper substrate.
本発明においては、マスターバッチを製造する樹脂にＰＢＴを用いたことにより、マスターバッチ製造時の１分子内に少なくとも２個のエポキシ基をもつ有機化合物の反応を抑制して使用量を節減することができ、さらに、このマスターバッチを用いて積層したＰＥＴ樹脂層のブロッキング問題も解消させることができた。 In the present invention, by using PBT as a resin for producing a masterbatch, the reaction of an organic compound having at least two epoxy groups in one molecule during the production of the masterbatch is suppressed, thereby reducing the amount used. Furthermore, the blocking problem of the PET resin layer laminated using this master batch could be solved.
本発明で製造されるＰＥＴ樹脂積層紙の基本構成は、紙基材上にＰＥＴ樹脂層が溶融積層されてなっている。 The basic structure of the PET resin laminated paper produced by the present invention is such that a PET resin layer is melt laminated on a paper substrate.
基材に用いられる紙は、紙容器の種類等に応じて任意のものを選択できるが、典型的には、クラフト紙、晒クラフト紙等で、坪量が２０〜４００ｇ／ｍ２のものが用いられる。 The paper used for the substrate can be selected arbitrarily depending on the type of paper container, etc., but is typically kraft paper, bleached kraft paper, etc., with a basis weight of 20 to 400 g / m 2 . Used.
この紙基材の少なくとも一面にポリエチレンテレフタレート（ＰＥＴ）樹脂を主成分とする樹脂組成物層を設ける。ポリエチレンテレフタレート樹脂は、テレフタル酸とエチレングリコールを縮合反応させて得られるものであるが、本発明の機能を損なわない範囲で第三成分を含む共重合体であってもよい。この第三成分には、アジピン酸、イソフタル酸等のジカルボン酸、ネオペンチルグリコール等のジオール化合物などが含まれる。ＰＥＴ樹脂には固有粘度が０．５５〜０．９０ｄｌ／ｇ、好ましくは０．６５〜０．８８ｄｌ／ｇのものを用いる。 A resin composition layer mainly composed of polyethylene terephthalate (PET) resin is provided on at least one surface of the paper substrate. The polyethylene terephthalate resin is obtained by condensation reaction of terephthalic acid and ethylene glycol, but may be a copolymer containing a third component as long as the function of the present invention is not impaired. This third component includes dicarboxylic acids such as adipic acid and isophthalic acid, and diol compounds such as neopentyl glycol. A PET resin having an intrinsic viscosity of 0.55 to 0.90 dl / g, preferably 0.65 to 0.88 dl / g is used.
この固有粘度はフェノール：テトラクロロエタンが容積比で１：１の混合溶媒を用い、ＪＩＳK7367−5に従って測定したものである。ＰＥＴ樹脂の固有粘度が０．５５ｄｌ／ｇ未満になると、基材上へ溶融積層する際に、ドローダウンやネックインと呼ばれる膜の拡がりが不十分となり、一方、０．９０ｄｌ／ｇを越えると、ＰＢＴ樹脂の粘度が著しく増加して積層厚みが不必要に厚くなるとともに、柔軟性や屈曲性が乏しくなるので好ましくない。 This intrinsic viscosity is measured according to JIS K7367-5 using a mixed solvent of phenol: tetrachloroethane in a volume ratio of 1: 1. When the intrinsic viscosity of the PET resin is less than 0.55 dl / g, the film spreading called drawdown or neck-in becomes insufficient during melt lamination on the base material, while when the viscosity exceeds 0.90 dl / g. In addition, the viscosity of the PBT resin is remarkably increased and the laminated thickness becomes unnecessarily thick, and the flexibility and flexibility are poor.
ＰＥＴ樹脂層は、ＰＥＴ樹脂１００重量部に対し１分子内に２個以上のエポキシ基を持つ有機化合物を０．１〜１．０重量部、特に０．４〜０．７重量部を配合することが好ましい。この化合物を配合することによって、ＰＥＴ樹脂の溶融粘度と溶融張力を適正に保ち、積層時のドローダウンやネックインを抑制する効果がある。０．１重量部未満であると、この効果の発現が期待できず好ましくない。一方、１．０重量部を越えると、ＰＥＴ樹脂の溶融粘度が過剰に増大して積層厚みを薄くすることができず、柔軟性や屈曲性が乏しくなるので好ましくない。 The PET resin layer contains 0.1 to 1.0 part by weight, particularly 0.4 to 0.7 part by weight of an organic compound having two or more epoxy groups in one molecule with respect to 100 parts by weight of the PET resin. It is preferable. By blending this compound, the melt viscosity and melt tension of the PET resin are properly maintained, and there is an effect of suppressing drawdown and neck-in during lamination. If the amount is less than 0.1 parts by weight, this effect cannot be expected, which is not preferable. On the other hand, if it exceeds 1.0 part by weight, it can not be melt viscosity of P E T resin is thin excessively increased by laminating thickness, since the flexibility and bending property becomes poor undesirably.
２個以上のエポキシ基を持つ有機化合物（以下、エポキシ基含有有機化合物と記す。）の例としては、（メタ）アクリル酸グリシジル、スチレン−（メタ）アクリル酸メチル−メタクリル酸グリシジル、エポキシ化大豆油、エポキシ化亜麻仁油、エチレン−（メタ）アクリル酸グリシジル共重合体、エポキシ化ポリブタジエン等が挙げられるが、多官能エポキシ基を有する有機化合物であれば特に限定されない。 Examples of organic compounds having two or more epoxy groups (hereinafter referred to as epoxy group-containing organic compounds) include glycidyl (meth) acrylate, styrene-methyl (meth) acrylate-glycidyl methacrylate, and large epoxidation. Examples include bean oil, epoxidized linseed oil, ethylene- (meth) acrylate glycidyl copolymer, epoxidized polybutadiene, and the like, but are not particularly limited as long as they are organic compounds having a polyfunctional epoxy group.
ＰＥＴ樹脂層を形成する樹脂組成物には、その性質を損わない範囲で第三成分を含有させることができる。その例としてはポリエチレンナフタレート（ＰＥＮ）、ポリトリメチレンテレフタレート（ＰＴＴ）等の他のポリエステル、ポリオレフィンなどの樹脂成分や、ステアリン酸カルシウムやオレイン酸アミド等の滑剤、炭酸カルシウムやタルク等の充填材を挙げることができる。 The resin composition forming the PET resin layer can contain a third component as long as the properties are not impaired. Examples include resin components such as polyethylene naphthalate (PEN) and polytrimethylene terephthalate (PTT), polyolefins, lubricants such as calcium stearate and oleic amide, and fillers such as calcium carbonate and talc. Can be mentioned.
該ＰＥＴ樹脂層の厚みは、５μｍ以上４０μｍ未満であることが好ましく、より好ましくは１２〜２０μｍである。５μｍ未満であると膜に欠陥性を生じやすくなり、一方４０μｍ以上になると柔軟性や屈曲性が悪くなり、後工程のハンドリングに支障を生じ、欠陥製品も生じやすくなるとともに、不必要に製造原価の上昇原因となるため好ましくない。 The thickness of the PET resin layer is preferably 5 μm or more and less than 40 μm, more preferably 12 to 20 μm. If the thickness is less than 5 μm, the film tends to be defective. On the other hand, if the thickness is 40 μm or more, the flexibility and the flexibility are deteriorated, the handling of the subsequent process is hindered, and a defective product is likely to be generated. This is not preferable because it causes a rise in
本発明で、ＰＥＴ樹脂層を溶融積層する際に、まずエポキシ基含有有機化合物のマスターバッチを作製するが、その際にマスターバッチ用の樹脂としてＰＢＴを用いるところに特徴がある。 In the present invention, when a PET resin layer is melt-laminated, a master batch of an epoxy group-containing organic compound is first prepared. In that case, PBT is used as a resin for the master batch.
マスターバッチは、ＰＥＴ樹脂層の主体であるＰＥＴ樹脂にエポキシ基含有有機化合物を混練することも考えられるが、該化合物はＰＥＴ樹脂との反応性に富み、高温溶融によるマスターバッチの作製工程において後述の積層工程で期待する反応以外にあずかる消費量が多く、経済的に好ましくない。 The masterbatch can be considered to knead an epoxy group-containing organic compound with the PET resin, which is the main component of the PET resin layer, but the compound is rich in reactivity with the PET resin and will be described later in the masterbatch production process by high-temperature melting. The amount of consumption other than the reaction expected in the laminating process is large, which is economically undesirable.
一方、ＰＢＴ樹脂はＰＥＴに比べて融点が低く、且つ該エポキシ化合物との反応性が緩慢であるためマスターバッチに配合する有効量が少なく経済的にも好ましい。 On the other hand, the PBT resin has a lower melting point than PET and is slow in reactivity with the epoxy compound, so that an effective amount to be blended into the master batch is small and economically preferable.
ＰＢＴ樹脂は、テレフタル酸とし、４−ブタンジオールを縮合反応させて得られるものであるが、本発明の機能を損なわない範囲で第三成分を含んでよいことはＰＥＴ樹脂と同様である。固有粘度も０．５５〜０．９０ｄｌ／ｇ、好ましくは０．６５〜０．８８ｄｌ／ｇのものを用いる。マスターバッチにおけるエポキシ基含有有機化合物の濃度は２〜３５重量％、好ましくは１０〜３０重量％、更に好ましくは１５〜２５重量％、ＰＢＴ樹脂濃度は６５〜９８重量％、好ましくは７０〜９０重量％、更に好ましくは７５〜８５重量％程度とするのがよい。 P B T resin, and terephthalic acid, 4-but-butanediol is obtained by condensation reaction are the same as the PET resin functions to the extent that does not impair that may include a third component of the present invention . The intrinsic viscosity is 0.55 to 0.90 dl / g, preferably 0.65 to 0.88 dl / g. The concentration of the epoxy group-containing organic compound in the master batch is 2 to 35% by weight, preferably 10 to 30% by weight, more preferably 15 to 25% by weight, and the PBT resin concentration is 65 to 98% by weight, preferably 70 to 90% by weight. %, More preferably about 75 to 85% by weight.
エポキシ基含有有機化合物濃度が２重量％未満では、溶融押出時のマスターバッチ比率が大きくなり、このマスター作製に係るコストが過剰に上乗せとなるため好ましくない。一方、有機化合物濃度が３５重量％を越えると、溶融押出時のマスターバッチ比率が少なくなり、樹脂組成物層の均一性が低下するため好ましくない。 If the concentration of the epoxy group-containing organic compound is less than 2% by weight, the ratio of the master batch at the time of melt-extrusion is increased, and the cost for producing the master is excessively increased. On the other hand, if the concentration of the organic compound exceeds 35% by weight, the ratio of the master batch at the time of melt extrusion decreases, and the uniformity of the resin composition layer decreases, which is not preferable.
マスターバッチ比率は、形成されるＰＥＴ樹脂層におけるＰＥＴ樹脂とＰＢＴ樹脂の比率も考慮して定めるのがよい。ＰＥＴ／ＰＢＴの比率が重量比で９０／１０以下になるとヒートシール性が不十分となり好ましくない。９９．９／０．１以上になると過剰に反応するため好ましくない。好ましい比率は９０／１０〜９９．９／０．１程度、特に９５／５〜９５．５／４．５程度である。 The master batch ratio is preferably determined in consideration of the ratio of the PET resin and the PBT resin in the formed PET resin layer. When the PET / PBT ratio is 90/10 or less by weight , the heat sealability is insufficient, which is not preferable. Since it will react excessively when it becomes 99.9 / 0.1 or more, it is not preferable. A preferred ratio is about 90/10 to 99.9 / 0.1, particularly about 95/5 to 95.5 / 4.5.
マスターバッチの作製は、ＰＢＴ樹脂とエポキシ基含有有機化合物を１０〜１００ｓｅｃ―１の高剪断速度の下に、ＰＢＴ融点（２２８℃前後）＋１０℃未満の温度で均一に溶融混練することが好ましい。 In producing the master batch, it is preferable to melt and knead the PBT resin and the epoxy group-containing organic compound uniformly at a temperature of less than 10 ° C. at a PBT melting point (around 228 ° C.) under a high shear rate of 10 to 100 sec- 1 .
マスターバッチ作製時の混練温度がＰＢＴ樹脂融点より10℃を越えると、両者（ＰＢＴと有機化合物）の反応性が著しく高まり、溶融押出時に必要な増粘性が失活し所望の効果を得ることができず好ましくない。一方、ＰＢＴ融点未満では溶融混練ができない。 If the kneading temperature at the time of masterbatch production exceeds 10 ° C from the melting point of the PBT resin, the reactivity between the two (PBT and organic compound) is significantly increased, and the thickening required during melt extrusion is deactivated, and the desired effect can be obtained. This is not preferable. On the other hand, melt kneading is not possible if the melting point is lower than the PBT melting point.
マスターバッチを製造するその他の条件は周知の方法に従えばよい。 Other conditions for producing the master batch may be in accordance with known methods.
樹脂組成物が溶融積層される紙基材の表面あるいは印刷面にはラミネートアンカー剤を予め塗布しておくことが好ましい。使用するラミネートアンカー剤としては、ポリイミン系のものが好ましい。ポリイミンの分子鎖末端に存在する第二級アミンが、溶融したＰＥＴ樹脂の分子鎖末端に存在する水酸基やカルボキシル基と共有結合するため、紙基材との積層接着強度が強化される。樹脂組成物にエポキシ基含有有機化合物が配合されており、該エポキシ基が未反応のまま存在している場合は、第二級アミンがエポキシ基との共有結合により積層接着強度はさらに強化される。最も好ましいポリイミンとしてポリエチレンイミンが挙げられる。これを主成分とするラミネートアンカー剤が市販されている。 A laminate anchor agent is preferably applied in advance to the surface or printed surface of the paper substrate on which the resin composition is melt-laminated. The laminate anchor agent used is preferably a polyimine-based agent. Since the secondary amine present at the molecular chain end of the polyimine is covalently bonded to the hydroxyl group or carboxyl group present at the molecular chain end of the molten PET resin, the lamination adhesive strength with the paper substrate is enhanced. When an epoxy group-containing organic compound is blended in the resin composition and the epoxy group is left unreacted, the laminate adhesive strength is further strengthened by the covalent bond between the secondary amine and the epoxy group. . The most preferred polyimine is polyethyleneimine. Laminate anchor agents containing this as a main component are commercially available.
ＰＥＴ樹脂は、樹脂組成物を溶融積層する際に予備乾燥してから他成分との混合を行い、乾燥させたＰＥＴ樹脂とＰＢＴマスターバッチをブレンダーで混合して、押出ラミネート加工用の押出機に投入して溶融押出する。予備乾燥は含水率が５０ｐｐｍ程度以下になるようにするのがよい。溶融押出温度は広範囲で、２３０〜３４０℃程度が通常であり、２７０〜３００℃程度が好ましい。２３０℃未満ではＰＥＴ樹脂の融点以下となって溶融押出ができず、一方、３４０℃を越えるとＰＥＴ樹脂の熱劣化や著しい溶融粘度低下が起こるので好ましくない。 The PET resin is pre-dried when the resin composition is melt-laminated, and then mixed with other components, and the dried PET resin and PBT master batch are mixed with a blender, and the resulting mixture is fed into an extruder for extrusion laminating. Add and melt extrude. The preliminary drying is preferably performed so that the water content is about 50 ppm or less. The melt extrusion temperature is a wide range, usually about 230 to 340 ° C, and preferably about 270 to 300 ° C. If it is less than 230 ° C., it becomes less than the melting point of the PET resin and cannot be melt-extruded. On the other hand, if it exceeds 340 ° C., it is not preferable because thermal degradation or significant decrease in melt viscosity occurs.
押出機のＴダイスから溶融押出しされた樹脂組成物は紙基材上に積層される。この工程においてＴダイスから基材表面までのエアーギャップはなるべく短くし、積層後のニップロールは冷却ロールであることが好ましい。ＰＥＴ樹脂の結晶化速度は速いので、可能な限り急冷することが好ましい。これにより、ＰＥＴ樹脂の結晶化度を小さくして、柔軟性および屈曲性を良好に保つことができる。ＰＥＴ層の結晶化度を１５％未満、好ましくは１０％未満、より好ましくは８％未満にすることができる。最低は特に制限されず、０％であってもよい。 The resin composition melt extruded from the T die of the extruder is laminated on the paper substrate. In this step, it is preferable that the air gap from the T die to the substrate surface is as short as possible, and the nip roll after lamination is a cooling roll. Since the crystallization speed of the PET resin is fast, it is preferable to cool it as quickly as possible. Thereby, the crystallinity degree of PET resin can be made small and a softness | flexibility and a flexibility can be kept favorable. The crystallinity of the PET layer can be less than 15%, preferably less than 10%, more preferably less than 8%. The minimum is not particularly limited, and may be 0%.
本明細書における結晶化度とは、示差走査熱量計（ＤＳＣ）分析において検出される融解エンタルピーΔＨｍ、結晶化エンタルピーΔＨＣＬから式（ａ）でχＣとして求められる値である。 The crystallinity in this specification is a value obtained as χ C in the equation (a) from the melting enthalpy ΔH m and the crystallization enthalpy ΔH CL detected in the differential scanning calorimeter (DSC) analysis.
χＣ＝１００×（ΔＨｍ−ΔＨＣＬ）／１４０．０・・・（ａ）
このＰＥＴ樹脂積層紙を用いた紙容器の用途は特に限定されないが、食品容器として好ましく用いることができる。箱形の容器の例を図１に示す。同図において右側面はフラッグ部分に糊付して貼合している。
χ C = 100 × (ΔH m −ΔH CL ) /140.0 (a)
Although the use of the paper container using this PET resin laminated paper is not particularly limited, it can be preferably used as a food container. An example of a box-shaped container is shown in FIG. In the figure, the right side surface is glued to the flag portion.
その場合、ＰＥＴを主成分とする樹脂組成物層のある面を内面として所望する紙容器のブランクに打ち抜き、カートン、カップ類等のそれぞれ専用の製函機で製函する。 In that case, the surface having the resin composition layer containing PET as a main component is used as the inner surface, punched out into a blank of a desired paper container, and boxed with a dedicated boxing machine such as a carton or cup.
紙容器が耐熱性を必要としない用途であれば、製函した紙容器をそのまま使用できる。容器内面が保香性に優れるＰＥＴ樹脂で形成されているので多種多様の食品を収容することができる。 If the paper container is an application that does not require heat resistance, the boxed paper container can be used as it is. Since the inner surface of the container is made of PET resin having excellent fragrance retention properties, a wide variety of foods can be accommodated.
耐熱性を必要とする用途では、予め加熱して結晶化度を高めておいてもよく、加熱調理時の熱で結晶化が促進され耐熱性が高まるのを利用してもよい。例えば、食品が収容された容器をオーブン加熱調理時に、１３０〜２００℃で３０分以上加熱すると、ＰＥＴ樹脂の結晶化度が高まって２００℃以上の耐熱性が発現する。結晶化度（χＣ）は１５％以上とすることができる。上限は特に制限されないが実用的に７０％程度までである。 In applications that require heat resistance, the degree of crystallization may be increased by heating in advance, or it may be utilized that crystallization is promoted by heat during cooking to increase heat resistance. For example, when a container containing food is heated at 130 to 200 ° C. for 30 minutes or longer during cooking in the oven, the crystallinity of the PET resin increases and heat resistance of 200 ° C. or higher is developed. The crystallinity (χ C ) can be 15% or more. Although the upper limit is not particularly limited, it is practically up to about 70%.
天面が開口形態の紙容器の封緘（ヒートシール）は、ヒートシール性を有するＰＥＴ層等を内面に配したアルミ箔ラミネートフィルム等を天面に置き、カップであればフランジ部分のリング状の熱シール板で押さえ、２３０〜２４０℃程度でヒートシールする。ＰＥＴとヒートシールできオーブン加熱に耐えられる材料はＰＥＴ、ＰＥＴ共重合体などが挙げられる。 Sealing (heat-sealing) a paper container with an opening on the top surface is an aluminum foil laminate film or the like with a heat-sealable PET layer on the inner surface. Hold with a heat seal plate and heat seal at about 230-240 ° C. Materials that can be heat sealed with PET and can withstand oven heating include PET and PET copolymers.
溶融押出による積層工程では、積層前に押出条件を整えるために、Ｔダイスから樹脂組成物の垂れ流しを行い、その結果、塊状の工程ロスが生じる。本発明では、該塊状のロス材料を回収・粉砕し、樹脂組成物の６５〜８０重量％に対して、１分子内に少なくとも2個のエポキシ基をもつ前記の有機化合物２０〜３５重量％を再配合して高剪断下にて、ＰＥＴ融点（２６０℃前後）＋１０℃未満の温度で均一に溶融混練したマスターバッチとして再生利用できる。 In the laminating process by melt extrusion, the resin composition is allowed to flow from the T die in order to adjust the extruding conditions before the laminating, resulting in a lump process loss. In the present invention, the massive loss material is recovered and pulverized, and the organic compound having 20 to 35 % by weight of at least two epoxy groups in one molecule is contained with respect to 65 to 80% by weight of the resin composition. It can be reused as a master batch that is re-blended and uniformly melt-kneaded at a temperature below PET melting point (around 260 ° C.) + 10 ° C. under high shear.
同様にＰＥＴ樹脂積層紙から正製品を採取するために、両端部をスリットして除外するときにも樹脂組成物のロスが生じる。積層紙端部から除外したロス、前記の塊状ロスである樹脂組成物を回収・粉砕したもの１００重量部に対して、１分子内に少なくとも2個のエポキシ基をもつ前記の有機化合物０．１〜０．７重量部を配合し、多層式の溶融押出機を用いて、紙基材積層面に該再生樹脂組成物、他面に本発明で述べたバージン原料からなる樹脂組成物が積層されてもよい。 Similarly, a loss of the resin composition occurs when removing both ends by slitting in order to collect a regular product from the PET resin laminated paper. The organic compound having at least two epoxy groups in one molecule with respect to 100 parts by weight of the loss excluded from the end of the laminated paper and 100 parts by weight of the resin composition which is the lump loss collected and pulverized ~ 0.7 part by weight, and using a multilayer melt extruder, the recycled resin composition is laminated on the paper substrate lamination surface, and the resin composition comprising the virgin raw material described in the present invention is laminated on the other surface. May be.
本発明の樹脂組成物は、溶融押出工程でのネックイン抑制性に優れるが、ネックイン率はゼロではない。製造時の両端部ロスを最小限とするため、Ｔダイスの内部にディッケルを設け（インナーディッケル）、ネックイン幅に相当する吐出を制限し、溶融樹脂成分の端部ロスを最小限として積層することも有用である。 Although the resin composition of the present invention is excellent in neck-in inhibiting property in the melt extrusion process, the neck-in rate is not zero. In order to minimize the loss at both ends at the time of manufacture, a deck is provided inside the T die (inner deck), and the discharge corresponding to the neck-in width is limited, and the end loss of the molten resin component is minimized. It is also useful to do.
本発明の樹脂組成物を用いた積層体は、溶融押出時のネックインが著しく解消されるため、積層工程速度を最高２００ｍ／分まで高めることが可能となる。 In the laminate using the resin composition of the present invention, the neck-in at the time of melt extrusion is remarkably eliminated, so that the lamination process speed can be increased up to 200 m / min.
本発明で得られた積層紙は、ヒートシール性がなく、且つＰＥＴ樹脂に比べて結晶化温度が高いＰＢＴ樹脂が配合されているため、積層工程の冷却時において最初にＰＢＴ（副材）の結晶化が起こり、次いで結晶化温度が低いＰＥＴ（主材）の結晶化が起こる。このため、ヒートシール性は維持されるが、ブロッキングしにくい積層体となる。 The laminated paper obtained in the present invention is not heat-sealable and is blended with a PBT resin having a higher crystallization temperature than PET resin. Crystallization occurs, followed by crystallization of PET (main material) having a low crystallization temperature. For this reason, the heat sealability is maintained, but a laminated body that is difficult to block is obtained.
本発明について実施例を挙げて更に具体的に説明する。
＜検体の作製＞
The present invention will be described more specifically with reference to examples.
<Preparation of specimen>
ＰＢＴ樹脂「５００ＦＰ」（ポリプラスチックス（株）製、固有粘度＝０．８７５ｄｌ／ｇ）７０重量％とエポキシ化大豆油「Ｏ−１３０Ｐ」（旭電化（株）製）３０重量％を攪拌混合した樹脂組成物を、直径＝４０ｍｍ、Ｌ／Ｄ＝３２のスクリューを備えた同方向回転の二軸押出機を用いて押出温度２３５℃、剪断速度＝２１ｓｅｃ−１なる条件で溶融混練して「マスターバッチＶ」を造粒作製した。 70% by weight of PBT resin “500FP” (manufactured by Polyplastics Co., Ltd., intrinsic viscosity = 0.875 dl / g) and 30% by weight of epoxidized soybean oil “O-130P” (manufactured by Asahi Denka Co., Ltd.) The obtained resin composition was melt-kneaded under the conditions of an extrusion temperature of 235 ° C. and a shear rate of 21 sec −1 using a co-rotating twin screw extruder equipped with a screw having a diameter = 40 mm and L / D = 32. A master batch V "was prepared by granulation.
ＰＥＴ樹脂「ＣＲ８８１６」（華潤製、固有粘度＝０．８１０ｄｌ／ｇ）１００重量部と前記「マスターバッチＶ」１．７重量部を攪拌混合した樹脂組成物を、日立造船（株）製の同方向回転の二軸押出機「ＨＭＴ１００」（Ｌ／Ｄ＝３８、Ｔダイス幅＝１６００ｍｍ）に投入し、押出温度＝２８０℃で溶融混練させながら、ポリエチレンイミン系アンカーコート剤（日本触媒製「エポミン」）を予め紙基材上に０．１ｇ／ｍ２（乾燥後の固形分換算量）で塗布した。７０ｇ／ｍ２の晒クラフト紙の上にＰＥＴ樹脂層の厚みが２０μｍになるように溶融積層した後、速やかに２５℃に調温した冷却ロールで挟持しながら急冷して積層紙を得た。この積層紙の樹脂組成物層の結晶化度は１０．８％であった。 PET resin "CR8816" (the China Resources Ltd., intrinsic viscosity = 0.810dl / g) 100 by weight parts as the "masterbatch V" 1.7 parts by weight of the resin composition was mixed with stirring, Hitachi Zosen Co., Ltd. A polyethyleneimine anchor coating agent (manufactured by Nippon Shokubai Co., Ltd.) was introduced into a twin screw extruder “HMT100” (L / D = 38, T die width = 1600 mm) rotated in the same direction and melt kneaded at an extrusion temperature = 280 ° C. Epomin ") was previously applied on a paper substrate at 0.1 g / m 2 (in terms of solid content after drying). After melt lamination so that the thickness of the PET resin layer was 20 μm on 70 g / m 2 bleached kraft paper, it was rapidly cooled while being sandwiched by a cooling roll adjusted to 25 ° C. to obtain a laminated paper. The crystallinity of the resin composition layer of this laminated paper was 10.8%.
実施例１検体を作製する際の条件出しに垂れ流した塊状ロス７０重量％とエポキシ化大豆油「Ｏ−１３０Ｐ」（旭電化（株）製）３０重量％を攪拌混合した樹脂組成物を、直径＝４０ｍｍ、Ｌ／Ｄ＝３２のスクリューを備えた同方向回転の二軸押出機を用いて押出温度２３５℃、剪断速度＝２１ｓｅｃ−１なる条件で溶融混練して「マスターバッチＲ」を造粒作製した。 Example 1 A resin composition obtained by stirring and mixing 70% by weight of a lump loss lump spilled to prepare conditions for preparing a specimen and 30% by weight of epoxidized soybean oil “O-130P” (Asahi Denka Co., Ltd.) "Masterbatch R" is granulated by melt-kneading under the conditions of extrusion temperature of 235 ° C and shear rate of 21 sec -1 using a co-rotating twin screw extruder equipped with a screw of = 40 mm and L / D = 32 Produced.
ＰＥＴ樹脂「ＣＲ８８１６」（華潤製、固有粘度＝０．８１０dl／g）１００重量部と前記「マスターバッチＲ」１．７重量部を撹拌混合した樹脂組成物を、ポリエチレンイミン系アンカーコート剤（日本触媒製「エポミン」）を予め紙基材上に０．１ｇ／ｍ２（乾燥後の固形分換算量）で塗布した以外は、実施例１と同様の操作を経て積層紙を得た。この積層紙の樹脂組成物層の結晶化度は９．３％であった。 A resin composition obtained by stirring and mixing 100 parts by weight of PET resin “CR8816” (manufactured by Huajun, intrinsic viscosity = 0.810 dl / g) and 1.7 parts by weight of “Masterbatch R” was added to a polyethyleneimine anchor coating agent (Japan) A laminated paper was obtained through the same operation as in Example 1 except that “Epomin” (catalyst) was previously applied on a paper substrate at 0.1 g / m 2 (in terms of solid content after drying). The crystallinity of the resin composition layer of this laminated paper was 9.3%.
ＰＥＴ樹脂「ＣＲ８８１６」（華潤製、固有粘度＝０．８１０dl／g）１００重量部とエポキシ化大豆油「Ｏ−１３０Ｐ」（旭電化（株）製）０．５重量部を撹拌混合した樹脂組成物を、日立造船（株）製の同方向回転の二軸押出機「ＨＭＴ１００」（Ｌ／Ｄ＝３８、Ｔダイス幅＝１６００mm）に投入し、押出温度＝２８０℃で溶融混練させながら、７０ｇ／ｍ２の晒クラフト紙の上に樹脂組成物層の厚みが２０μｍになるように溶融積層した後、速やかに２５℃に調温した冷却ロールで挟持しながら急冷して積層紙を得た。この積層紙の樹脂組成物層の結晶化度は８．４％であった。 Resin composition obtained by stirring and mixing 100 parts by weight of PET resin “CR8816” (manufactured by Huajun, intrinsic viscosity = 0.810 dl / g) and 0.5 parts by weight of epoxidized soybean oil “O-130P” (manufactured by Asahi Denka Co., Ltd.) The product is put into a twin screw extruder “HMT100” (L / D = 38, T die width = 1600 mm) manufactured by Hitachi Zosen Co., Ltd. and melt-kneaded at an extrusion temperature of 280 ° C. After being melt-laminated so that the thickness of the resin composition layer becomes 20 μm on / m 2 bleached kraft paper, it was rapidly cooled while being sandwiched by a cooling roll adjusted to 25 ° C. to obtain a laminated paper. The crystallinity of the resin composition layer of this laminated paper was 8.4%.
ＰＥＴ樹脂「ＣＲ８８１６」（華潤製、固有粘度＝０．８１０dl／g）を、日立造船（株）製の同方向回転の二軸押出機「ＨＭＴ１００」（Ｌ／Ｄ＝３８、Ｔダイス幅＝１６００ｍｍ）に投入し、押出温度＝２８０℃で溶融混練させながら、７０ｇ／ｍ２の晒クラフト紙の上に樹脂組成物層の厚みが２０μｍになるように溶融積層した後、速やかに２０℃に調温した冷却ロールで挟持しながら急冷して積層紙を得た。この積層紙の樹脂組成物層の結晶化度は８．２％であった。 PET resin “CR8816” (manufactured by Huajun, intrinsic viscosity = 0.810 dl / g), a twin-screw extruder “HMT100” (L / D = 38, T die width = 1600 mm) manufactured by Hitachi Zosen Corporation ), Melt-kneaded on a 70 g / m 2 bleached kraft paper so that the thickness of the resin composition layer is 20 μm while melt-kneading at an extrusion temperature of 280 ° C., and then quickly adjusting to 20 ° C. Laminated paper was obtained by quenching while being sandwiched by a heated cooling roll. The crystallinity of the resin composition layer of this laminated paper was 8.2%.
ＰＥＴ樹脂「ＣＲ８８１６」（華潤製、固有粘度＝０．８１０dl／g）１００重量部とエポキシ化大豆油「Ｏ−１３０Ｐ」（旭電化（株）製）１．０重量部を撹拌混合した樹脂組成物を、日立造船（株）製の同方向回転の二軸押出機「ＨＭＴ１００」（Ｌ／Ｄ＝３８、Ｔダイス幅＝１６００ｍｍ）に投入し、押出温度＝２８０℃で溶融混練させながら、７０ｇ／ｍ２の晒クラフト紙の上に樹脂組成物層の厚みが２０μｍになるように溶融積層した後、速やかに２０℃に調温した冷却ロールで挟持しながら急冷して積層紙を得た。この積層紙の樹脂組成物層の結晶化度は８．４％であった。 Resin composition obtained by stirring and mixing 100 parts by weight of PET resin “CR8816” (manufactured by Huajun, intrinsic viscosity = 0.810 dl / g) and 1.0 part by weight of epoxidized soybean oil “O-130P” (manufactured by Asahi Denka Co., Ltd.) The product is put into a twin screw extruder “HMT100” (L / D = 38, T die width = 1600 mm) manufactured by Hitachi Zosen Co., Ltd. and melt-kneaded at an extrusion temperature of 280 ° C. After being melt-laminated so that the thickness of the resin composition layer becomes 20 μm on / m 2 bleached kraft paper, it was rapidly cooled while being sandwiched by a cooling roll adjusted to 20 ° C. to obtain a laminated paper. The crystallinity of the resin composition layer of this laminated paper was 8.4%.
７０ｇ／ｍ２の晒クラフト紙の上に低密度ポリエチレン（日本ポリエチレン製「ノバテックＬＣ６０４」を押出温度＝３３０℃とした以外は、実施例１と同様の操作を経て、厚み２０μｍの積層紙を得た。 A laminated paper having a thickness of 20 μm is obtained through the same operation as in Example 1 except that low-density polyethylene (“NOVATEC LC604” manufactured by Nippon Polyethylene is set at an extrusion temperature = 330 ° C.) on a bleached kraft paper of 70 g / m 2. It was.
＜ネックイン指標としてのトリミングロス量の評価＞
積層厚み２０±４（μｍ）の範囲内にある積層紙を製品幅１０００ｍｍで採取できるよう、インナーディッケルを用いてＴダイス吐出幅をＸ0（ｍ）に制限する。このとき紙基材に溶融積層された１ｍ相当分の吐出樹脂量Ｗ0（ｇ）を、
Ｗ0＝20 × Ｘ0 ×１×1.4(PET密度)と近似する。
製品幅1×1（m）の積層樹脂量Ｗ1(g)は、
Ｗ1＝20×１×１×1.4＝28.0(g)となる。
したがってトリミングロス量をＷ0−Ｗ1(g/ｍ２)で表わすこととした。
但し前述の比較例４は、
Ｗ0＝20×Ｘ0×１×0.92(LDPE密度)と近似し、
Ｗ1＝20×１×１×0.92＝18.4(g)としてトリミングロス量を計算した。
<Evaluation of trimming loss as a neck-in index>
An inner deckle is used to limit the T dice discharge width to X 0 (m) so that laminated paper having a laminated thickness of 20 ± 4 (μm) can be collected at a product width of 1000 mm. At this time, the discharge resin amount W 0 (g) corresponding to 1 m melt-laminated on the paper base material is
Approximate to W 0 = 20 × X 0 × 1 × 1.4 (PET density).
The amount of laminated resin W 1 (g) with a product width of 1 x 1 (m) is
W 1 = 20 × 1 × 1 × 1.4 = 28.0 (g).
Therefore, the trimming loss amount is expressed by W 0 −W 1 (g / m 2 ).
However, the above Comparative Example 4 is
Approximate with W 0 = 20 × X 0 × 1 × 0.92 (LDPE density)
The trimming loss amount was calculated as W 1 = 20 × 1 × 1 × 0.92 = 18.4 (g).
＜芳香成分の吸着耐性評価＞
実施例および比較例で得られた検体を１００×１００ｍｍに裁断した試験片の積層面に市販インスタントコーヒー２０ｇを散布し、６０℃に調整したオーブン内に２４時間静置する。これを取出し、コーヒー粉末を除去して常温に冷却した後、試験片に残る臭気を官能評価した。
判定基準は、下記３段階とした。
Ｓ…何もにおわない
Ａ…かすかなにおいがある
Ｂ…かなり強くにおう
<Adsorption resistance evaluation of aromatic components>
20 g of commercially available instant coffee is sprayed on the laminated surface of the test pieces obtained by cutting the specimens obtained in Examples and Comparative Examples to 100 × 100 mm, and left in an oven adjusted to 60 ° C. for 24 hours. This was taken out, the coffee powder was removed, and after cooling to room temperature, the odor remaining on the test piece was subjected to sensory evaluation.
The judgment criteria were the following three stages.
S ... No smell A ... Small smell B ... Smell very strong
＜耐熱性の評価＞
実施例１，２および比較例２，３で得られた検体を１００×１００ｍｍに裁断した試験片の積層面に水でペースト状に溶いた小麦粉を塗り、２００℃に調温した家電用ホットプレート上で５分間加熱した。加熱後は小麦粉ペーストへの焦げ目の有無を確認するとともに、試験片の積層樹脂を剥離洗浄し、ＤＳＣにより結晶化度を測定した。
結果一覧を表１に記す。
<Evaluation of heat resistance>
Hot plate for home appliances in which the specimens obtained in Examples 1 and 2 and Comparative Examples 2 and 3 were cut to 100 × 100 mm and coated with flour dissolved in water in the form of paste with water and adjusted to 200 ° C. Heated for 5 minutes above. After heating, the presence or absence of burns on the flour paste was confirmed, the laminated resin of the test piece was peeled and washed, and the crystallinity was measured by DSC.
The result list is shown in Table 1.
＜ブロッキング評価＞
積層体（１０×１０ｃｍに裁断）を２枚重ね、１０×１０ｃｍ×１ｋｇの荷重を２３℃×５０％ＲＨ×２４ｈｒ載せた後、重ねた２枚を剥がす抵抗を指標にします。
〇：抵抗もなく剥がれる
△：少し抵抗がある
×：容易に剥がれない
<Blocking evaluation>
After stacking two laminates (cut to 10 x 10 cm) and placing a 10 x 10 cm x 1 kg load at 23 ° C x 50% RH x 24 hr, use the resistance to peel off the two piles as an index.
◯: Peels without resistance Δ: Slight resistance ×: Does not peel easily
本発明は、ポリエチレンテレフタレートを主成分とする樹脂組成物を紙基材に効率よく積層することができ、この積層体は、保香性、耐熱性、耐油性等に優れているので、各種容器、特に食品容器でそのまま加熱調理もできる容器に広く利用できる。 The present invention can efficiently laminate a resin composition containing polyethylene terephthalate as a main component on a paper substrate, and since this laminate is excellent in aroma retention, heat resistance, oil resistance, etc., various containers In particular, it can be widely used in food containers that can be cooked as they are.
Claims (9)
χＣ＝１００×（△Ｈｍ−△ＨＣＬ）／１４０．０・・・（ａ）
註）ポリエチレンテレフタレートの結晶の平衡融解熱（△ＨＭ＝１４０．０Ｊ／ｇ） The degree of crystallinity of the melt-laminated polyethylene terephthalate resin layer is obtained by the following formula (a) from the melting enthalpy ΔH m and the crystallization enthalpy ΔH CL detected in the differential scanning calorimeter (DSC) analysis. 4. The production method according to claim 1, wherein C is less than 15% .
χ C = 100 × (ΔH m −ΔH CL ) /140.0 (a)
Ii) Equilibrium heat of fusion of polyethylene terephthalate crystals (Δ HM = 140.0 J / g)
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| JPS55166247A (en) * | 1979-06-11 | 1980-12-25 | Dainippon Printing Co Ltd | Polyester coated laminated film or sheet and its preparation |
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