JP6552959B2 - Textiles for palatable beverage extraction filter - Google Patents
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- JP6552959B2 JP6552959B2 JP2015257529A JP2015257529A JP6552959B2 JP 6552959 B2 JP6552959 B2 JP 6552959B2 JP 2015257529 A JP2015257529 A JP 2015257529A JP 2015257529 A JP2015257529 A JP 2015257529A JP 6552959 B2 JP6552959 B2 JP 6552959B2
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- 235000013361 beverage Nutrition 0.000 title claims description 41
- 238000000605 extraction Methods 0.000 title claims description 41
- 239000004753 textile Substances 0.000 title description 4
- 239000000306 component Substances 0.000 claims description 28
- 239000002131 composite material Substances 0.000 claims description 25
- 239000008358 core component Substances 0.000 claims description 25
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 24
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 22
- -1 poly ethylene terephthalate Polymers 0.000 claims description 21
- 238000002844 melting Methods 0.000 claims description 19
- 230000008018 melting Effects 0.000 claims description 19
- 239000004744 fabric Substances 0.000 claims description 17
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 16
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 16
- 239000002685 polymerization catalyst Substances 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 claims description 12
- 229910001385 heavy metal Inorganic materials 0.000 claims description 8
- 238000007654 immersion Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 235000019629 palatability Nutrition 0.000 claims description 7
- 229920001577 copolymer Polymers 0.000 claims description 6
- 150000002009 diols Chemical class 0.000 claims description 4
- 230000005484 gravity Effects 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 claims description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-L isophthalate(2-) Chemical group [O-]C(=O)C1=CC=CC(C([O-])=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-L 0.000 claims 1
- 229920000728 polyester Polymers 0.000 description 18
- 239000002759 woven fabric Substances 0.000 description 17
- 239000003054 catalyst Substances 0.000 description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 12
- 239000010936 titanium Substances 0.000 description 12
- 229910052719 titanium Inorganic materials 0.000 description 12
- 150000002681 magnesium compounds Chemical class 0.000 description 11
- 239000000835 fiber Substances 0.000 description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 9
- 239000011247 coating layer Substances 0.000 description 9
- 230000007613 environmental effect Effects 0.000 description 9
- 239000004952 Polyamide Substances 0.000 description 8
- 238000010828 elution Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 229920002647 polyamide Polymers 0.000 description 8
- 244000269722 Thea sinensis Species 0.000 description 6
- 229920001634 Copolyester Polymers 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000002074 melt spinning Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- 229920001225 polyester resin Polymers 0.000 description 4
- 239000004645 polyester resin Substances 0.000 description 4
- 235000013616 tea Nutrition 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 235000006468 Thea sinensis Nutrition 0.000 description 2
- INNSZZHSFSFSGS-UHFFFAOYSA-N acetic acid;titanium Chemical compound [Ti].CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O INNSZZHSFSFSGS-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920002215 polytrimethylene terephthalate Polymers 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- 150000003609 titanium compounds Chemical class 0.000 description 2
- 238000009941 weaving Methods 0.000 description 2
- 240000007154 Coffea arabica Species 0.000 description 1
- 235000007340 Hordeum vulgare Nutrition 0.000 description 1
- 240000005979 Hordeum vulgare Species 0.000 description 1
- 235000010254 Jasminum officinale Nutrition 0.000 description 1
- 240000005385 Jasminum sambac Species 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920001283 Polyalkylene terephthalate Polymers 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
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 235000020279 black tea Nutrition 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 235000016213 coffee Nutrition 0.000 description 1
- 235000013353 coffee beverage Nutrition 0.000 description 1
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 235000009569 green tea Nutrition 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 235000020333 oolong tea Nutrition 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
Landscapes
- Multicomponent Fibers (AREA)
- Apparatus For Making Beverages (AREA)
- Polyesters Or Polycarbonates (AREA)
Description
本発明は嗜好性飲料抽出フィルター用フィラメント及びそれからなる嗜好性飲料抽出フィルター用織物に関する。 The present invention relates to a filament for a palatability beverage extraction filter and a fabric for a palatability beverage extraction filter comprising the same.
従来から、嗜好性飲料抽出フィルターの素材としては、紙やポリプロピレンまたはポリエチレンの不織布が主流として用いられているが、透明性が悪く包装材中の茶葉が見えにくいこと、紙に至っては熱シール加工ができない等の問題がある。そこで、近年の傾向としては、嗜好性飲料抽出用バッグ中の茶葉が見える高級感のある織物製の嗜好性飲料抽出バッグが増えてきている。 Conventionally, paper, polypropylene or polyethylene non-woven fabric has been mainly used as a material for palatable beverage extraction filters, but it has poor transparency and the tea leaves in the packaging are difficult to see. There are problems such as being unable to. Therefore, as a trend in recent years, the preference beverage extraction bags made of textiles having a high-class feel with which tea leaves in the preference beverage extraction bags can be seen are increasing.
織物製の嗜好性飲料抽出用バッグに用いられる、嗜好性飲料抽出フィルターの素材繊維としてはポリアミド繊維が主流である。ポリアミド繊維を用いた織物製の抽出フィルターは、立体形状の形態保持性に優れ、また変形に対する弾性回復力にも富んでいることから、織物が柔らかく、風合いに優れている。しかし、ポリアミド繊維製の抽出用バッグは、空気中の酸素の影響による黄変、熱湯中でのポリアミド繊維の膨潤による抽出用バッグの寸法変化、抽出後のバッグを容器から取り出す際の液切れの悪さ、ポリアミドの比重が軽いことによる熱湯中での抽出用バッグの沈降性の悪さ、及び使用後の焼却による窒素酸化物の発生による環境汚染等の問題が以前から指摘されていた。 As a material fiber of a palatable beverage extraction filter to be used for a woven palatable beverage extraction bag, polyamide fiber is the mainstream. The extraction filter made of a woven fabric using a polyamide fiber is excellent in three-dimensional shape retention and also has an elastic recovery force against deformation, so that the woven fabric is soft and excellent in texture. However, the extraction bag made of polyamide fiber is yellowed due to the influence of oxygen in the air, the dimensional change of the extraction bag due to swelling of the polyamide fiber in hot water, and the liquid drainage when the bag after extraction is taken out from the container Problems such as badness, poor settling of extraction bags in hot water due to the low specific gravity of polyamide, and environmental pollution due to generation of nitrogen oxides by incineration after use have been pointed out.
このようなポリアミド繊維の問題点を改善する目的で、ポリエステル繊維による嗜好性飲料抽出フィルター等が研究されてきている。例えば、特許文献１では、芯と鞘に融点差を持たせた芯鞘構造を有するポリエステル系繊維を用いた織物からなる嗜好性飲料抽出フィルターの製造方法が提案されている。また、特許文献２では、イソフタル酸等を共重合成分とした共重合ポリエステルからなる嗜好性飲料抽出フィルター用ポリエステルモノフィラメントとなし得る分繊用マルチフィラメント及びそれから得られる嗜好性飲料抽出フィルターが提案されている。 For the purpose of improving such problems of polyamide fibers, a taste beverage extraction filter using polyester fibers has been studied. For example, in patent document 1, the manufacturing method of the palatable beverage extraction filter which consists of textiles using polyester type fiber which has a core sheath structure which gave melting | fusing point difference to the core and the sheath is proposed. Patent Document 2 proposes a polyester monofilament for a liquor beverage extraction filter comprising a copolyester containing isophthalic acid or the like as a copolymerization component, a multifilament for splitting that can be formed, and a palatability beverage extraction filter obtained therefrom. Yes.
しかしながら、特許文献１には、ポリエステル繊維中にポリエステル製造用触媒として用いられる重金属触媒については記載されておらず、またポリエステル繊維による嗜好性飲料抽出フィルターの環境安全性についても記載されていない。
また、特許文献２記載の共重合ポリエステルを用いた単成分のマルチフィラメントからなる織物は、熱処理した際に、溶着性が高く、剥離し難いものとなるが、織物をシールして、フィルターに成形しようとすると、シール時の熱処理により、生地強度が弱くなり、成形性に劣ったものとなる。
本発明は上記の背景に鑑みなされたものであり、その目的は、環境安全性に優れ、生地の強度が保持できる、成形性に優れた嗜好性飲料抽出フィルターを得るためのフィラメント及びそれからなる織物を提供することにある。
However, Patent Document 1 does not describe a heavy metal catalyst used as a polyester production catalyst in polyester fibers, nor does it describe the environmental safety of a palatable beverage extraction filter using polyester fibers.
In addition, a woven fabric composed of a single component multifilament using a copolyester described in Patent Document 2 has high weldability and is difficult to peel off when heat-treated, but the fabric is sealed and molded into a filter. If it is attempted, the heat treatment at the time of sealing weakens the fabric strength, resulting in poor formability.
The present invention has been made in view of the above background, and an object thereof is a filament for obtaining a palatable beverage extraction filter excellent in environmental safety and capable of maintaining the strength of a dough and excellent in moldability, and a woven fabric comprising the same Is to provide.
本発明は、上記の課題を解決するもので、以下の構成を要旨とする。
（１）芯成分は、固有粘度が０．５５以上、０．６５以下、融点が２２０℃以上のホモポリエチレンテレフタレート、鞘成分は、融点が芯成分より４０℃以上低いテレフタル酸及びジオールを主成分とするイソフタル酸共重合ポリエチレンテレフタレートであり、共重合ポリエチレンテレフタレートのテレフタル酸とイソフタル酸のモル比は９０／１０〜７０／３０の範囲であり、芯成分および鞘成分の重合触媒はチタン酸からなる被覆層が形成されたマグネシウム化合物であり、芯成分および鞘成分の樹脂の重合触媒含有量は５０〜２００ｐｐｍであり、１０質量％濃度のエタノール水溶液中で１００℃１時間浸漬後の質量変化率が４％以下、真比重５．０以上の重金属の金属元素の量が０．１ｐｐｍ未満であり、熱水収縮率が３％以上、８％以下であることを特徴とする嗜好性飲料抽出フィルター用芯鞘型複合フィラメントを用いてなる、引裂き強度が７Ｎ以上の嗜好性飲料抽出フィルター用織物。
The present invention solves the above-described problems, and has the following configuration as its gist.
(1) The core component is a homopolyethylene terephthalate having an intrinsic viscosity of 0.55 or more and 0.65 or less and a melting point of 220 ° C. or more, and the sheath component is mainly composed of terephthalic acid and a diol whose melting point is 40 ° C. or more lower than that of the core component isophthalic acid copolymerized polyethylene ethylene terephthalate and a molar ratio of polyethylene terephthalate copolymer of terephthalic acid and isophthalic acid is in the range of 90 / 10-70 / 30, the polymerization catalyst of the core component and sheath component are titanate The content of the polymerization catalyst of the resin of the core component and the sheath component is 50 to 200 ppm, and the mass change rate after immersion for 1 hour at 100 ° C. in an aqueous 10 mass% ethanol solution There 4% or less, Ri amount 0.1ppm less than der metal elements of the true specific gravity of 5.0 or more heavy metals, hot water shrinkage ratio of 3% or more Obtained by using the palatability brewing core-sheath type composite filament filter to 8% or less, wherein the der Rukoto, tear strength 7N more palatable beverage extraction filter fabrics.
本発明によれば、嗜好性飲料抽出フィルターに用いたときに、ポリアミドの問題点を改善し、環境安全性に優れ、フィルターを製造する際に、成形性に優れた嗜好性飲料抽出フィルター用フィラメント及びそれを用いた織物が提供される。 According to the present invention, when used in a palatability beverage extraction filter, the problem of polyamide is improved, the environmental safety is excellent, and the filament for palatability beverage extraction filter is excellent in moldability when manufacturing a filter. And the textile using it is provided.
本発明は、嗜好性飲料抽出フィルター用芯鞘型複合フィラメントである。
芯鞘型複合フィラメントの複合形態としては、マルチフィラメントでもモノフィラメントでもよいが、モノフィラメントであることが好ましい。
The present invention is a core-sheath composite filament for a palatable beverage extraction filter.
The composite form of the core-sheath composite filament may be a multifilament or a monofilament, but is preferably a monofilament.
本発明の嗜好性飲料抽出フィルター用芯鞘型複合フィラメントの芯成分は、融点が２２０℃以上のホモポリエステルである。ホモポリエステルとしては、例えば、ポリエチレンテレフタレート（ＰＥＴ）、ポリブチレンテレフタレート（ＰＢＴ）及びポリトリメチレンテレフタレート（ＰＴＴ）などのポリアルキレンテレフタレートを主体とするポリエステルが挙げられる。芯成分の融点が２２０℃未満となると、芯鞘型複合フィラメントを製織した織物は、乾熱処理後の強度保持率が低くなる傾向にある。フィルター用織物の強度保持率を保つ点からは、芯成分は、ポリエチレンテレフタレートであることが好ましい。 The core component of the core-sheath type composite filament for a palatable beverage extraction filter of the present invention is a homopolyester having a melting point of 220 ° C. or higher. Examples of the homopolyester include polyesters mainly composed of polyalkylene terephthalate such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polytrimethylene terephthalate (PTT). When the melting point of the core component is less than 220 ° C., the woven fabric of core / sheath composite filaments tends to have a low strength retention after dry heat treatment. From the viewpoint of maintaining the strength retention of the filter fabric, the core component is preferably polyethylene terephthalate.
芯成分のポリエステルの固有粘度は、０．４以上、０．８以下の範囲であることが好ましく、中でも０．５以上、０．７以下、特に０．５５以上、０．６５以下の範囲が好ましい。固有粘度が小さすぎると、製編織後の強度が不足する傾向があり、固有粘度が大きすぎると、原料ポリマーの固有粘度を過剰に引き上げる必要があり、コスト高となる傾向があるため、上記の範囲が好ましい。 The intrinsic viscosity of the core component polyester is preferably in the range of 0.4 to 0.8, and more preferably 0.5 to 0.7, particularly 0.55 to 0.65. preferable. If the intrinsic viscosity is too small, the strength after weaving tends to be insufficient, and if the intrinsic viscosity is too large, it is necessary to excessively increase the intrinsic viscosity of the raw material polymer, which tends to increase the cost. A range is preferred.
芯成分のホモポリエステルの重合触媒は、環境安全性の点から、チタン系触媒であることが好ましい。 The homopolyester polymerization catalyst of the core component is preferably a titanium-based catalyst from the viewpoint of environmental safety.
重合触媒として用いられるチタン系触媒としては、酢酸チタン、テトラアルコキサイドチタン、チタンハロゲン化物、チタン酸塩、チタンアルコキシド類等が好適に挙げられる。
これらは、触媒の活性をより高めるために、マグネシウムを用いた化合物との複合体を好適に用いることができる。特に好ましい例として、チタン酸からなる被覆層が形成されたマグネシウム化合物が挙げられる。本発明において、チタン酸からなる被覆層が形成されたマグネシウム化合物とは、５〜１００℃の範囲の温度、好ましくは、１５〜７０℃の範囲の温度で、マグネシウム化合物の存在下に、チタン化合物を加水分解して、その表面にチタン酸を析出させることによって、マグネシウム化合物の表面にチタン酸からなる被覆層を有せしめたものである。
上記チタン系触媒の含有量は、ポリエステル樹脂に対して１０〜５００ｐｐｍであることが好ましく、より好ましくは５０〜２００ｐｐｍである。
Preferred examples of the titanium-based catalyst used as the polymerization catalyst include titanium acetate, tetraalkoxytitanium, titanium halides, titanates and titanium alkoxides.
In order to further enhance the activity of the catalyst, a complex with a compound using magnesium can be suitably used. A particularly preferred example is a magnesium compound in which a coating layer made of titanic acid is formed. In the present invention, a magnesium compound having a coating layer of titanic acid formed is a titanium compound in the presence of a magnesium compound at a temperature of 5 to 100 ° C., preferably 15 to 70 ° C. Is hydrolyzed to deposit titanic acid on the surface thereof, thereby providing a coating layer made of titanic acid on the surface of the magnesium compound.
The content of the titanium-based catalyst is preferably 10 to 500 ppm, more preferably 50 to 200 ppm, based on the polyester resin.
本発明の芯鞘型複合フィラメントの鞘成分は、融点が芯成分に比べて４０℃以上低いテレフタル酸及びジオールを主成分とする共重合ポリエステルである。具体的には、テレフタル酸とエチレングリコール等のジオールを主成分とする共重合ポリエステルが好適に挙げられる。共重合成分としては、イソフタル酸、アジピン酸及びセバシン酸等が好適に挙げられる。中でも芯鞘構造の複合のし易さ、取り扱い性を考慮するとイソフタル酸が好ましい。尚、本発明において、融点ピークが生じない非晶性の成分の場合、軟化点を融点とする。 The sheath component of the core-sheath type composite filament of the present invention is a copolyester mainly composed of terephthalic acid and diol having a melting point lower by 40 ° C. or more than that of the core component. Specifically, a copolyester mainly composed of terephthalic acid and a diol such as ethylene glycol is preferably used. Preferable examples of the copolymer component include isophthalic acid, adipic acid, and sebacic acid. Of these, isophthalic acid is preferred in view of the ease with which the core-sheath structure can be combined and the handleability. In the present invention, in the case of an amorphous component that does not cause a melting point peak, the softening point is taken as the melting point.
また、共重合成分がイソフタル酸の場合、テレフタル酸とイソフタル酸の比率は、熱接着がし易く、取り扱い性に優れている点から、モル比（テレフタル酸／イソフタル酸）で、９０／１０〜７０／３０範囲であることが好ましい。
尚、鞘成分の融点については、共重合成分とその成分の量を調整する事でコントロールする事ができる。
When the copolymer component is isophthalic acid, the ratio of terephthalic acid to isophthalic acid is 90/10 to 10 in terms of molar ratio (terephthalic acid / isophthalic acid) because it is easy to thermally bond and has excellent handleability. The range is preferably 70/30.
The melting point of the sheath component can be controlled by adjusting the amount of the copolymerization component and its component.
上述したような共重合ポリエステルを鞘成分に用いると、適度に、芯成分より融点が低く、熱接着加工し易くなるため、成形性に優れたものとなる点からも好ましい。 When the above-described copolymer polyester is used for the sheath component, the melting point is appropriately lower than that of the core component, and it is easy to perform heat bonding processing, and therefore, it is preferable from the viewpoint of excellent moldability.
鞘成分の共重合ポリエステルの重合触媒は、環境安全性の点から、チタン系触媒であることが好ましい。 The polymerization catalyst of the copolyester of the sheath component is preferably a titanium catalyst from the viewpoint of environmental safety.
重合触媒として用いられるチタン系触媒としては、酢酸チタン、テトラアルコキサイドチタン、チタンハロゲン化物、チタン酸塩、チタンアルコキシド類等が好適に挙げられる。
これらは、触媒の活性をより高めるために、マグネシウムを用いた化合物との複合体を好適に用いることができる。特に好ましい例として、チタン酸からなる被覆層が形成されたマグネシウム化合物が挙げられる。本発明において、チタン酸からなる被覆層が形成されたマグネシウム化合物とは、５〜１００℃の範囲の温度、好ましくは、１５〜７０℃の範囲の温度で、マグネシウム化合物の存在下に、チタン化合物を加水分解して、その表面にチタン酸を析出させることによって、マグネシウム化合物の表面にチタン酸からなる被覆層を有せしめたものである。
上記チタン系触媒の含有量は、ポリエステル樹脂に対して１０〜５００ｐｐｍであることが好ましく、より好ましくは５０〜２００ｐｐｍである。
Preferred examples of the titanium-based catalyst used as the polymerization catalyst include titanium acetate, tetraalkoxytitanium, titanium halides, titanates and titanium alkoxides.
In order to further enhance the activity of the catalyst, a complex with a compound using magnesium can be suitably used. A particularly preferred example is a magnesium compound in which a coating layer made of titanic acid is formed. In the present invention, a magnesium compound having a coating layer of titanic acid formed is a titanium compound in the presence of a magnesium compound at a temperature of 5 to 100 ° C., preferably 15 to 70 ° C. Is hydrolyzed to deposit titanic acid on the surface thereof, thereby providing a coating layer made of titanic acid on the surface of the magnesium compound.
The content of the titanium-based catalyst is preferably 10 to 500 ppm, more preferably 50 to 200 ppm, based on the polyester resin.
本発明の芯鞘型フィラメントの芯鞘比率としては、２０／８０〜８０／２０（体積比）が好ましく、４０／６０〜６０／４０がより好ましい。この範囲であると、芯成分により適度な強度を保ち、嗜好性飲料抽出フィルター用芯鞘型複合フィラメントの熱収縮率を抑えることができる。このため、織物の目ずれを防ぎ易いものとなり、フィルターとしての成形性が良好である。 The core-sheath ratio of the core-sheath filament of the present invention is preferably 20/80 to 80/20 (volume ratio), more preferably 40/60 to 60/40. Within this range, it is possible to maintain an appropriate strength by the core component and to suppress the heat shrinkage rate of the core-sheath type composite filament for the palatable beverage extraction filter. For this reason, it becomes easy to prevent misalignment of the fabric, and the moldability as a filter is good.
本発明の芯鞘型複合フィラメントは、１０質量％濃度のエタノール水溶液中に１時間浸漬後の質量変化率が４％以下である。
このような質量変化率とすることにより、飲料抽出用フィルターとして、環境安全性や安全性により優れたものとなる。より好ましくは、質量変化率が２％以下であり、さらに好ましくは、質量変化率が１％以下である。
なお、質量変化率は、以下の式によって、求められる値である。
質量変化率（％）＝〔（浸漬前の質量−浸漬後の質量）／（浸漬前の質量）〕×１００
The core-sheath composite filament of the present invention has a mass change of 4% or less after being immersed in a 10% by mass aqueous ethanol solution for 1 hour.
By setting it as such a mass change rate, as a filter for beverage extraction, it becomes more excellent by environmental safety and safety. More preferably, the mass change rate is 2% or less, and more preferably, the mass change rate is 1% or less.
The mass change rate is a value obtained by the following equation.
Mass change rate (%) = [(mass before immersion−mass after immersion) / (mass before immersion)] × 100
本発明の芯鞘型複合フィラメントは、重金属の溶出量が０．１０ｐｐｍ未満である。ここで、溶出量は、フィラメントを１０質量％濃度のエタノール溶液に１００℃で１時間浸漬し溶出させ、真比重５．０以上の金属元素の量を溶出量とする。
このように重金属の溶出量が０．１０ｐｐｍ未満であると、飲料抽出用に好適に用いることができ、環境安全性にも優れたものとなる。
The core-sheath composite filament of the present invention has a heavy metal elution amount of less than 0.10 ppm. Here, the amount of elution is determined by immersing the filament in a 10% by weight ethanol solution at 100 ° C. for 1 hour for elution, and taking the amount of metal element having a true specific gravity of 5.0 or more as the elution amount.
Thus, when the elution amount of heavy metals is less than 0.10 ppm, it can be suitably used for beverage extraction, and is excellent in environmental safety.
本発明の芯鞘型複合フィラメントは、熱水処理後の収縮率が、１０％以下であることが好ましく、なかでも、８％以下であることが好ましい。この範囲とすることにより、織物の熱セット時に湾曲せず、成形時の加工性に優れる。接着性が良好で目ずれせずに取扱い易い点からは、熱水収縮率は、３％以上であることが好ましい。芯鞘型複合フィラメントの熱水処理後の収縮率は後述の方法で測定した値である。 The core-sheath composite filament of the present invention preferably has a shrinkage ratio of 10% or less after the hot water treatment, and more preferably 8% or less. By setting it as this range, it does not bend when the woven fabric is heat set, and is excellent in workability at the time of molding. The hot water shrinkage is preferably 3% or more from the viewpoint of good adhesiveness and easy handling without misalignment. The shrinkage ratio of the core-sheath composite filament after the hot water treatment is a value measured by the method described later.
本発明の芯鞘型複合フィラメントは、製織することにより、嗜好性飲料抽出フィルターに用いるのに好適な織物を製造することができる。 The core-sheath composite filament of the present invention can be woven to produce a woven fabric suitable for use in a palatable beverage extraction filter.
織物の組織としては、平織物等が好適である。
本発明において、嗜好性飲料抽出フィルター用織物としては、本発明の芯鞘型複合フィラメントを、１００％用いて製織してもよいし、一部に用いてもよい。好ましくは、４０％以上用いることである。
本発明の芯鞘型複合フィラメントを一部に用いる場合は、経糸にホモＰＥＴなどのレギュラーポリエステル、緯糸に本発明の芯鞘型複合フィラメントを用いると、織物の交点の熱融着性が良好であるため、好適である。
As the fabric structure, a plain fabric or the like is preferable.
In the present invention, as the fabric for a palatable beverage extraction filter, the core-sheath composite filament of the present invention may be woven using 100% or may be used in part. Preferably, 40% or more is used.
When the core-sheath type composite filament of the present invention is used in part, the heat fusion property of the cross point of the fabric is good when using regular polyester such as homoPET for the warp and the core-sheath type composite filament of the present invention for the weft Therefore, it is preferable.
本発明の芯鞘型複合フィラメントを用いた織物は、飲料抽出フィルターへ成形する際の加工性を良好にする点から、引裂き強度が、５Ｎ以上であることが好ましく、中でも、７Ｎ以上であることが好ましい。 The woven fabric using the core-sheath type composite filament of the present invention preferably has a tearing strength of 5 N or more, in particular 7 N or more, from the viewpoint of making the processability at the time of molding into a beverage extraction filter better. Is preferred.
本発明の芯鞘型複合フィラメントを用いた織物は、飲料抽出用フィルターとして用いたときに液切れがし易い点、フィルターの目ずれがしにくい点から、開口率は４０％〜７０％が好ましい。 The woven fabric using the core-sheath type composite filament of the present invention preferably has an aperture ratio of 40% to 70% from the viewpoint that liquid breakage easily occurs when used as a filter for beverage extraction and that the filter is not easily misaligned. .
本発明の芯鞘型複合フィラメントをからなる織物を用いて、熱処理し、超音波シール法等によりシールして成形することにより、嗜好性飲料用フィルターとして用いることができる。 By using a woven fabric comprising the core-sheath composite filament of the present invention, heat-treating, sealing by an ultrasonic sealing method or the like, and molding, it can be used as a filter for palatable beverages.
本発明の芯鞘型複合フィラメントをからなる織物は、シールしても生地強度を保持でき、成形性に優れているため、矩形で平面形状のもの、球形状のもの、テトラパック型のもの、四つ手網型のもの、その他、多面体形状のもなど、様々な立体形状の嗜好性飲料抽出用フィルターを容易に得ることができる。 The woven fabric comprising the core-sheath type composite filament of the present invention can maintain the fabric strength even when sealed and has excellent moldability, so that it is rectangular and planar, spherical, tetrapack type, It is possible to easily obtain filters for extracting a favorite beverage of various three-dimensional shapes, such as those of four-hand net type and others having a polyhedral shape.
本発明の芯鞘型複合フィラメントからなる織物を用いて得られる飲料抽出用フィルターは、紅茶、麦茶、烏龍茶、ジャスミン茶、緑茶、コーヒー等の種々の嗜好性飲料に好適に用いることができる。 The filter for beverage extraction obtained by using the woven fabric of core-sheath type composite filaments of the present invention can be suitably used for various palatable beverages such as black tea, barley tea, oolong tea, jasmine tea, green tea, coffee and the like.
本発明における嗜好性飲料抽出フィルターの好適な製造方法の例を以下に示す。
芯成分として、重合触媒をチタン系触媒としたポリエチレンテレフタレート、鞘成分として、チタン系触媒を重合触媒としたイソフタル酸共重合ポリエステルを用いて、芯鞘型複合型フィラメントを製造する。次に、得られた芯鞘型複合型フィラメントを、製織した後、織物の交点が目ずれしないように鞘成分を熱処理する。次いで、得られた織物を超音波シール法等によりシールし、テトラパック形状等適宜の形状に成形して、嗜好性飲料抽出用フィルターを得ることができる。
The example of the suitable manufacturing method of the favorite beverage extraction filter in this invention is shown below.
A core-sheath type composite filament is manufactured using, as a core component, polyethylene terephthalate having a titanium-based catalyst as a polymerization catalyst, and an isophthalic acid copolymer polyester having a titanium-based catalyst as a polymerization catalyst as a sheath component. Next, after weaving the obtained core-sheath composite filament, the sheath component is heat-treated so that the intersections of the fabrics are not misaligned. Subsequently, the obtained woven fabric is sealed by an ultrasonic sealing method or the like, and formed into an appropriate shape such as a tetrapack shape, whereby a palatable beverage extraction filter can be obtained.
物性の測定、評価は以下の通り、実施した。
１）固有粘度
フェノール／テトラクロロエタン＝６／４（重量比）混合液５０ｍｌに０．５ｇのポリマーを溶解して、温度２０℃においてオストワルド型粘度計を用いて測定した。
２）融点
パーキンエルマー社製ＤＳＣ−７型を用い、チップ１０ｍｇ、昇温速度１０℃／分の条件にて測定した。
３）強度、伸度
ＪＩＳ Ｌ １０１３に準じ、島津製作所（株）製、ＡＧＳ １ＫＮＧオートグラフ引張試験機を用い、試料糸長２００ｍｍ、引張速度２００ｍｍ／ｍｉｎの条件で試料が伸長破断したときの強度（ｃＮ／ｄｔｅｘ）、伸度（％）を求めた。
４）重金属の溶出量
糸試料を、１０質量％濃度のエタノール水溶液に１００℃で１時間浸漬し溶出させたエタノール溶液を、アジレントテクノロジー製のＩＣＰ質量分析装置（Ａｇｉｌｅｎｔ ７５００ｃｓ）と、アメテック製ＩＣＰ発光分析装置（ＣＩＲＯＳ ＣＣＤ）を用いて測定した。
５）質量変化率
糸試料の質量を測定し浸漬前の質量とした。次に、糸試料を、１０質量％濃度のエタノール水溶液に１００℃で１時間浸漬させ、乾燥させて、糸試料を測定し、浸漬後の質量とし、以下の式により、質量変化率を算出した。
質量変化率（％）＝〔（浸漬前の質量−浸漬後の質量）／（浸漬前の質量）〕×１００
６）収縮率
荷重２ｍｇ／ｄｔｅｘを掛けた試料長５００ｍｍの糸を沸騰水中に１５分間浸漬し、次いで風乾した後に次式により芯鞘型複合フィラメントの収縮率を求めた。
収縮率（％）＝［（初期試料長―収縮後の試料長）／初期試料長］×１００
７）引裂き強度
ＪＩＳ Ｌ１０９６ ８．１５．１ Ａ−１法（シングルタング法）に準じ、（株）オリエンティック製テンシロンＲＴＡ−５００引張試験機を用い、試料幅５０ｍｍ、試料長２５０ｍｍ、チャック間距離１００ｍｍ、引張速度１００ｍｍ／ｍｉｎの条件で試料を引き裂く時の最大荷重を測定した。
Measurement of physical properties and evaluation were carried out as follows.
1) Intrinsic viscosity 0.5 g of a polymer was dissolved in 50 ml of a mixture of phenol / tetrachloroethane = 6/4 (weight ratio) and measured using an Ostwald viscometer at a temperature of 20 ° C.
2) Melting point: It was measured under the conditions of a chip 10 mg and a temperature rising rate of 10 ° C./min using DSC-7 type manufactured by Perkin Elmer.
3) Strength, Elongation According to JIS L 1013, using an AGS 1KNG Autograph Tensile Tester manufactured by Shimadzu Corporation, the strength when the sample is elongationally fractured under the conditions of a sample yarn length of 200 mm and a tensile speed of 200 mm / min. (CN / dtex) and elongation (%) were determined.
4) Elution amount of heavy metal The ethanol solution obtained by immersing and eluting a yarn sample in a 10% by mass aqueous ethanol solution at 100 ° C. for 1 hour, and ICP mass spectrometer (Agilent 7500 cs manufactured by Agilent Technologies) and ICP emission manufactured by Ametec It measured using the analyzer (CIROS CCD).
5) Mass Change Rate The mass of the yarn sample was measured and taken as the mass before immersion. Next, the yarn sample was immersed in an ethanol aqueous solution having a concentration of 10% by mass at 100 ° C. for 1 hour, dried, the yarn sample was measured, and the mass after immersion was calculated. The mass change rate was calculated by the following equation. .
Mass change rate (%) = [(mass before immersion−mass after immersion) / (mass before immersion)] × 100
6) Shrinkage Rate A 500 mm sample length yarn loaded with 2 mg / dtex was immersed in boiling water for 15 minutes and then air-dried, and then the shrinkage rate of the core-sheath composite filament was determined by the following equation.
Shrinkage rate (%) = [(initial sample length−sample length after shrinkage) / initial sample length] × 100
7) Tear strength
Sample width 50 mm, sample length 250 mm, distance between chucks 100 mm, tensile speed according to JIS L1096 8.15.1 A-1 method (single tongue method) using Tensilon RTA-500 tensile tester manufactured by Orientic Co., Ltd. The maximum load when tearing the sample under the condition of 100 mm / min was measured.
（実施例１）
テレフタル酸とエチレングリコールを原料とし、ＰＥＴオリゴマーの重合触媒として、チタン酸からなる被覆層が形成されたマグネシウム化合物を１８０ｐｐｍ添加して重縮合し、芯成分に用いるポリエチレンテレフタレートを得た（固有粘度：０．６２９）。次に、テレフタル酸に対しイソフタル酸２５ｍｏｌ％を加えた酸成分とエチレングリコールを原料とし、重合触媒として、チタン酸からなる被覆層が形成されたマグネシウム化合物をポリエステルに対して１８０ｐｐｍ加え、重縮合し、鞘成分に用いるイソフタル酸２５ｍｏｌ共重合ポリエチレンテレフタレートを得た（固有粘度：０．６４３）。
上記で得られた２種のポリエステル樹脂を溶融紡糸装置に供給し、芯鞘体積比率１：１の割合でポリマーを吐出し、孔径０．４５ｍｍの紡糸口金を用いて、紡糸温度２９０℃、紡糸速度１５００ｍ／ｍｉｎの紡糸条件で溶融紡糸し未延伸ポリエステルモノフィラメント糸を得た。
さらに、この未延伸糸を、加熱ローラー温度９０℃で３．４倍に延伸し、加熱プレート温度１６０℃で弛緩熱処理を施し、ポリエステルモノフィラメントを得た（芯成分の融点：２５５℃、鞘成分の融点：１８５℃）。
得られたモノフィラメントを、経密度１００本／２．５４ｃｍ、緯密度１００本／２．５４ｃｍの条件で平織組織にて製織し織物を得た。得られた織物を精練し、２００℃で熱処理し、糸の交点の鞘成分を融着させて、フィルター用織物を得た。得られたフィルター用織物を、超音波シール法により、テトラパック形状に成形し、嗜好性飲料抽出用フィルター製造した。
Example 1
Using terephthalic acid and ethylene glycol as raw materials, 180 ppm of a magnesium compound with a coating layer made of titanic acid was added as a polymerization catalyst for PET oligomer and polycondensed to obtain polyethylene terephthalate used as a core component (inherent viscosity: 0.629). Next, an acid component obtained by adding 25 mol% of isophthalic acid to terephthalic acid and ethylene glycol are used as raw materials. As a polymerization catalyst, 180 ppm of a magnesium compound having a coating layer made of titanic acid is added to the polyester and subjected to polycondensation. And 25 mol of isophthalic acid copolymer polyethylene terephthalate used for the sheath component (inherent viscosity: 0.643).
The two types of polyester resins obtained above are supplied to a melt spinning apparatus, the polymer is discharged at a core-sheath volume ratio of 1: 1, and a spinning temperature of 290 ° C. using a spinneret with a pore diameter of 0.45 mm. Melt spinning was carried out at a spinning condition of 1500 m / min to obtain an undrawn polyester monofilament yarn.
Furthermore, this unstretched yarn was stretched 3.4 times at a heating roller temperature of 90 ° C. and subjected to relaxation heat treatment at a heating plate temperature of 160 ° C. to obtain a polyester monofilament (melting point of core component: 255 ° C., sheath component) Melting point: 185 ° C).
The obtained monofilament was woven in a plain weave structure under conditions of warp density 100 / 2.54 cm and weft density 100 / 2.54 cm to obtain a woven fabric. The obtained woven fabric was scoured and heat-treated at 200 ° C., and the sheath component at the intersection of the yarns was fused to obtain a filter woven fabric. The obtained filter woven fabric was formed into a tetra-pack shape by an ultrasonic sealing method, and a filter for palatable beverage extraction was manufactured.
（実施例２）
芯鞘体積比率７：３に変更する以外は、実施例１と同様に溶融紡糸し未延伸ポリエステルモノフィラメント糸を得た。さらに、この未延伸糸を加熱ローラー温度９０℃で３．３倍に延伸し、加熱プレート温度１４０℃で弛緩熱処理を施し、ポリエステルモノフィラメント（芯成分の融点：２５５℃、鞘成分の融点：１８５℃）を得て、実施例１と同様に、嗜好性飲料抽出用フィルターを製造した。
(Example 2)
The melt spinning was carried out in the same manner as in Example 1 except that the core-sheath volume ratio was changed to 7: 3, to obtain an undrawn polyester monofilament yarn. Further, this undrawn yarn was stretched 3.3 times at a heating roller temperature of 90 ° C., and subjected to a relaxation heat treatment at a heating plate temperature of 140 ° C. to obtain a polyester monofilament (melting point of core component: 255 ° C., melting point of sheath component: 185 ° C. In the same manner as in Example 1, a palatable beverage extraction filter was produced.
（実施例３）
テレフタル酸とエチレングリコールとを原料とし、ＰＥＴオリゴマーの重合触媒として、チタン酸からなる被覆層が形成されたマグネシウム化合物をＰＥＴオリゴマーに対して２００ｐｐｍ加え、重縮合し、芯成分に用いるポリエチレンテレフタレートを得た（固有粘度：０．６３）。
また、実施例１記載の方法で鞘成分に用いるイソフタル酸共重合ポリエチレンテレフタレートを得た。
この２種のポリエステル樹脂を、実施例１記載の方法で溶融紡糸、延伸を行いポリエステルモノフィラメントを得た（芯成分の融点：２５５℃、鞘成分の融点：１８５℃）。得られたポリエステルモノフィラメントを用いて実施例１と同様に、嗜好性飲料抽出用フィルターを製造した。
(Example 3)
Using terephthalic acid and ethylene glycol as raw materials, as a polymerization catalyst for PET oligomer, 200 ppm of magnesium compound with a coating layer made of titanic acid is added to the PET oligomer and polycondensed to obtain polyethylene terephthalate used as a core component. (Intrinsic viscosity: 0.63).
In addition, an isophthalic acid copolymerized polyethylene terephthalate used for the sheath component by the method described in Example 1 was obtained.
The two types of polyester resins were melt spun and stretched by the method described in Example 1 to obtain polyester monofilaments (melting point of core component: 255 ° C., melting point of sheath component: 185 ° C.). A filter for palatable beverage extraction was produced in the same manner as in Example 1 using the obtained polyester monofilament.
（比較例１）
芯成分及び鞘成分に用いるポリエチレンテレフタレートの重合触媒を、４００ｐｐｍの三酸化アンチモンとする以外は実施例１と同様に、重合、溶融紡糸、延伸を実施し、嗜好性飲料抽出用フィルターを製造した。
(Comparative example 1)
Polymerization, melt spinning and stretching were performed in the same manner as in Example 1 except that the polymerization catalyst of polyethylene terephthalate used for the core component and the sheath component was changed to 400 ppm of antimony trioxide, to produce a filter for extracting a palatable beverage.
（比較例２）
芯成分を、実施例１の鞘成分に用いる共重合ポリエチレンテレフタレートとする以外は実施例１と同様に、重合、溶融紡糸を実施し、嗜好性飲料抽出用フィルターを製造した。フィルター用織物の引裂き強度は５Ｎ未満であり、引裂き強度の低いものであった。
(Comparative example 2)
Polymerization and melt spinning were carried out in the same manner as in Example 1 except that the core component was changed to the copolymerized polyethylene terephthalate used for the sheath component of Example 1, to produce a palatable beverage extraction filter. The tear strength of the filter fabric was less than 5N, and the tear strength was low.
実施例１〜３、比較例１で用いる重合触媒、モノフィラメントの芯鞘比率、重金属溶出量、質量変化率、繊度、強度、伸度、収縮率、フィルター用織物の引裂き強度を、表１に示す。 Table 1 shows the polymerization catalysts used in Examples 1 to 3 and Comparative Example 1, the ratio of monofilament core-sheath, elution amount of heavy metal, mass change rate, fineness, strength, elongation, shrinkage rate, and tear strength of filter fabrics. .
実施例より得られたモノフィラメントからなるフィルター用織物は、ポリアミドの問題点を改善し、成形性に優れ、生地強度も十分で飲料抽出用バッグとして十分に使用でき、環境安全性に優れた飲料抽出用フィルターであった。また、芯成分にアンチモン触媒を用いた比較例１は、重金属の溶出量が多く、環境安全性に劣ったものであった。比較例２から得られたフィルター用織物は、生地強度が十分でなく、成形性に劣っており、嗜好性飲料抽出用フィルターとしては使用できないものであった。 The filter fabric made of monofilaments obtained from the examples improves the problems of polyamide, has excellent moldability, has sufficient dough strength, and can be used sufficiently as a bag for beverage extraction, and beverage extraction with excellent environmental safety It was a filter for. Moreover, the comparative example 1 which used the antimony catalyst for the core component had many elution amounts of heavy metals, and was inferior to environmental safety. The filter fabric obtained from Comparative Example 2 was insufficient in dough strength and inferior in moldability, and could not be used as a filter for extracting palatable beverages.
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| JP7018268B2 (en) * | 2017-07-05 | 2022-02-10 | Ｋｂセーレン株式会社 | Woven fabric for taste beverage extraction filter |
| JP7097594B2 (en) * | 2017-10-30 | 2022-07-08 | ユニチカ株式会社 | Beverage extraction filter that is transparent in air and water. |
| JP7279231B2 (en) * | 2018-03-30 | 2023-05-22 | Ｋｂセーレン株式会社 | Polylactic acid monofilament for palatability beverage extraction filter and its production method |
| JP7053346B2 (en) * | 2018-03-30 | 2022-04-12 | Ｋｂセーレン株式会社 | Polylactic acid monofilament for tasteful beverage extraction filter and its manufacturing method |
| KR20210108356A (en) * | 2019-01-09 | 2021-09-02 | 케이비 세렌 가부시키가이샤 | Multifilament for palatable beverage extraction filter fabric |
| KR102347498B1 (en) * | 2020-04-17 | 2022-01-05 | 도레이첨단소재 주식회사 | Spiral membrane module with low elution of heavy metal and preparing method of the same |
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