JP2750484B2 - Polypropylene laver cage - Google Patents
Polypropylene laver cageInfo
- Publication number
- JP2750484B2 JP2750484B2 JP4069592A JP6959292A JP2750484B2 JP 2750484 B2 JP2750484 B2 JP 2750484B2 JP 4069592 A JP4069592 A JP 4069592A JP 6959292 A JP6959292 A JP 6959292A JP 2750484 B2 JP2750484 B2 JP 2750484B2
- Authority
- JP
- Japan
- Prior art keywords
- polypropylene
- laver
- rod
- seaweed
- stretched
- 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.)
- Expired - Lifetime
Links
Landscapes
- Edible Seaweed (AREA)
Description
【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION
【０００１】[0001]
【産業上の利用分野】本発明は、ポリプロピレン製海苔
簀に関する。更に詳しくは、押出延伸加工方法により曲
げ剛性が著しく改善され、高強度・高弾性率を付与され
た管状または棒状構造のポリプロピレン製延伸棒状体を
編組してなるポリプロピレン製海苔簀に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laver made of polypropylene. More specifically, the present invention relates to a polypropylene seaweed cage which is formed by braiding a tubular or rod-shaped polypropylene stretched rod having a significantly improved bending rigidity and a high strength and a high elastic modulus by an extrusion stretching method.
【０００２】[0002]
【従来の技術とその問題点】現在、乾海苔製造のために
多用されている合成樹脂製海苔簀の素材としては、衛生
上の無害・無毒性や熱可塑性合成樹脂の中でも比較的高
温に耐えるという物性的特性と材料コスト等のバランス
上の観点から、ポリプロピレン樹脂を用いて一般的な押
出成形方法により製造された小口径のポリプロピレン製
棒状体が、その主流を占めている。しかしながら、前記
ポリプロピレン製海苔簀は、次の二つの大きな欠点を有
している。すなわち、海苔簀表面と生海苔との付着性
が弱いこと、海苔簀用として必要な剛性が不足してい
ること、の２点である。2. Description of the Related Art At present, synthetic resin seaweed cages which are widely used for the production of dried seaweed are harmless and nontoxic for hygiene and can withstand relatively high temperatures among thermoplastic synthetic resins. From the viewpoint of balance between physical properties and material costs, small-diameter polypropylene rods manufactured by a general extrusion molding method using a polypropylene resin occupy the mainstream. However, the polypropylene sea ladle has the following two major drawbacks. That is, there are two points: the adhesion between the surface of the laver and the raw laver is weak, and the rigidity required for laver is insufficient.
【０００３】前記の欠点による影響は、該海苔簀の使
用に当たって海苔との付着性が弱いので、乾燥工程にお
いて海苔が十分に乾燥されないうちに海苔簀から剥離し
易くなるため皺だらけの乾海苔が得られ、全く商品価値
のないものになる。この付着性の改良方法としては、該
海苔簀あるいは海苔簀用素材（ポリプロピレン製棒状
体）の表面に対して、コロナ放電や火炎放射等による酸
化処理、または該表面に塩素化ポリオレフィンを塗布す
る方法、あるいは不飽和カルボン酸またはその誘導体に
よって変性されたポリオレフィンを添加したポリプロピ
レン樹脂を成形して海苔簀を製造する方法等が採用され
ている。[0003] The effect of the above-mentioned drawbacks is that when the laver is used, the adhesiveness to the laver is weak, so that the laver is easily peeled off from the laver before the laver is not sufficiently dried in the drying step, so that wrinkled dry laver is obtained. And have no commercial value at all. As a method for improving the adhesiveness, a method of oxidizing a surface of the laver or a material for the laver (a rod-shaped body made of polypropylene) by corona discharge or flame radiation, or applying a chlorinated polyolefin to the surface is used. Alternatively, a method of molding a polypropylene resin to which a polyolefin modified with an unsaturated carboxylic acid or a derivative thereof is added to produce a seaweed cage is employed.
【０００４】他方、前記の欠点の具体的理由は、該海
苔簀を構成するポリプロピレン製棒状体の剛性が不十分
なため、該海苔簀上に負荷された未乾燥海苔の乾燥収縮
に伴って当初平面状の該海苔簀が湾曲し、機械乾燥装置
内における温風の流通を阻害することから派生する種々
の弊害によって、得られる乾海苔製品が著しく低品質の
ものとなるからである。このような従来のポリプロピレ
ン製海苔簀における棒状体の剛性不足を改善する方法と
しては、原料のポリプロピレン樹脂に各種の無機フィラ
ーや剛性の高い異種樹脂を適量混合した樹脂組成物を成
形原料に用いて該海苔簀を製造する方法もあるが、該樹
脂組成物を用いることにより剛性面以外に種々の問題点
が生じることから、本発明者等は、それらを克服する改
良方法として、特公昭６２−３９９９１（特許第１，５
２８，７９５号）に記載されている高剛性ポリプロピレ
ン製海苔簀を発明し、実用化に成功した。[0004] On the other hand, a specific reason for the above-mentioned disadvantage is that the rigidity of the polypropylene rods constituting the laver is insufficient, so that the dry laver loaded on the laver is initially shrunk with drying shrinkage. This is because the flat laver is curved, and the resulting dried laver product is extremely poor in quality due to various adverse effects derived from obstructing the flow of warm air in the mechanical drying device. As a method of improving the rigidity shortage of the rod-shaped body in such a conventional polypropylene sea ladle, a resin composition obtained by mixing a suitable amount of various inorganic fillers or a different kind of resin having high rigidity with a raw material polypropylene resin is used as a molding material. Although there is a method for producing the laver, various problems other than rigidity are caused by using the resin composition. Therefore, the present inventors have proposed, as an improved method for overcoming those problems, Japanese Patent Publication No. 39991 (Patent Nos. 1,5
No. 28,795) and invented a high rigidity polypropylene seaweed cage, and succeeded in putting it into practical use.
【０００５】[0005]
【発明が解決しようとする課題】前記高剛性ポリプロピ
レン製海苔簀の実用化によって、該海苔簀は海苔簀市場
において大きな地歩を築くに到ったが、海苔簀に要求さ
れる曲げ特性としては未だ１００％満足し得るものでは
なかった。即ち、海苔の性質は生殖する海域によって剛
質と軟質性とに大別され、特定海域で収穫される高剛質
の海苔に対してはその乾燥時の収縮力も大きくなるた
め、必然的により剛性の高い海苔簀を使用する必要性が
生じてくるが、それに対処するには前記高剛性ポリプロ
ピレン製海苔簀であってもなお剛性不十分であった。The practical use of the high-rigidity polypropylene laver has led to the establishment of a large foothold in the laver market, but the bending characteristics required for the laver still remain. It was not 100% satisfactory. In other words, the characteristics of laver are broadly classified into rigid and soft depending on the sea area in which they are reproductive, and the rigidity of high-rigid laver harvested in a specific sea area also increases because of its greater shrinkage during drying. However, in order to cope with this, even the aforementioned high-rigidity polypropylene laver is still insufficient in rigidity.
【０００６】棒状体の曲げ特性を定量的に示す一般的な
基準としては、材料力学上の曲げ弾性率と曲げ強度が用
いられる。曲げ弾性率とは、一定長さの棒状体を曲げて
一定量撓ませるのに必要な曲げ応力の度合いを示し、こ
の数値が大きければ、該棒状体は撓みにくくなり、剛性
が高いと言える。これを海苔簀の使用状態に即して言い
換えると、曲げ弾性率が大きい程、海苔の乾燥収縮力に
よる該海苔簀の曲がりが少なくなることを表している。
また、曲げ強度とは、一定長さの棒状体に曲げ荷重をか
けて、該棒状体が降伏点撓みに達した時の最大曲げ応力
の値を示し、この数値が大きい程、該棒状体を強い力で
曲げても折れにくくなり、剛性が高いと言える。As a general standard for quantitatively indicating the bending characteristics of a rod-shaped body, a bending elastic modulus and a bending strength in material mechanics are used. The flexural modulus indicates the degree of bending stress required to bend a given length of a rod-like body and bend it by a certain amount. If this value is larger, the rod-like body is less likely to bend and has higher rigidity. In other words, according to the use state of the laver, the larger the bending elastic modulus, the less the bend of the laver due to the drying shrinkage force of the laver.
The bending strength indicates the value of the maximum bending stress when a bending load is applied to a rod having a certain length and the rod reaches the yield point deflection. Even if it is bent with strong force, it will not break easily, and it can be said that it has high rigidity.
【０００７】本発明者等は、前記特定海域における高剛
質海苔からの乾海苔の製造実績に基づいて検討を重ねた
結果、該海苔の乾燥収縮力に充分に対応し得る海苔簀素
材の曲げ特性基準としては、次の数値が望ましいという
結論に到った。即ち、該海苔簀に供する棒状体の曲げ弾
性率は６００ｋｇｆ／ｍｍ2 以上であり、その曲げ強度
は１２ｋｇｆ／ｍｍ2 以上が望ましいとのデータを得
た。ここで、本発明における曲げ弾性率および曲げ強度
値とは、後述の実施例に記載する方法により測定される
値を示す。[0007] The inventors of the present invention have made repeated studies based on the production results of dry laver from high-rigid laver in the specific sea area. As a result, the bending characteristics of the laver material which can sufficiently cope with the drying shrinkage force of the laver. As a criterion, they came to the conclusion that the following figures are desirable. That is, the flexural modulus of the rod-like body to be subjected to the seaweed bamboo is a 600 kgf / mm 2 or more, the flexural strength data was obtained with 12 kgf / mm 2 or more. Here, the bending elastic modulus and the bending strength value in the present invention indicate values measured by a method described in Examples described later.
【０００８】現在、公知のポリプロピレン製海苔簀では
剛性的に対処できない上述の高剛質海苔を用いた乾海苔
の製造における乾燥収縮の対応手段としては、圧倒的に
剛性の高い天然素材の竹ひごを編組してなる海苔簀が採
用されている。しかしながら、該竹ひごは天然の素材で
あるがゆえに品質面のバラツキがあって管理が難しいう
えに、吸湿してカビが発生しやすい等の問題点があるこ
とから、海苔簀業界においては、前記高剛性ポリプロピ
レン製海苔簀の剛性レベルを凌駕して、竹ひご製海苔簀
に代替し得る高性能のポリプロピレン製海苔簀の出現を
強く望んでいる状況下にある。At present, as a means for coping with drying shrinkage in the production of dry laver using the above-mentioned high-rigid laver which cannot be rigidly dealt with by the known polypropylene laver, an overwhelmingly rigid natural bamboo string is used. A braided laver is used. However, since the bamboo straw is a natural material, there is a variation in quality due to its natural quality, it is difficult to manage, and there is a problem that mold is easily generated due to moisture absorption. There is a strong demand for the emergence of a high-performance polypropylene laver that exceeds the rigidity level of a high-rigidity polypropylene laver and can be substituted for a bamboo clam laver.
【０００９】本発明者等は、以上のような海苔簀業界の
開発要求に応えるべく、高性能のポリプロピレン製海苔
簀に関する製造技術について鋭意研究した。その結果、
汎用ポリプロピレン樹脂を用いて通常の押出成形方法に
より得られた管状または棒状構造体を、特定の条件下で
再加熱と延伸操作を連続処理することによって所定の形
状寸法に形成したポリプロピレン製延伸棒状体が、上述
の要求に応じ得ることを見い出し、本発明に到達した。
以上の記述から明らかなように、本発明の目的は、従来
のポリプロピレン系樹脂組成物や特公昭６２−３９９９
１に記載の高剛性ポリプロピレン樹脂を用いた無延伸の
押出成形品では達成できなかった高剛性・高強度を有す
るポリプロピレン製延伸棒状成形品を編組してなるポリ
プロピレン製海苔簀とを提供することにある。The present inventors have conducted intensive studies on the production technology for high-performance polypropylene laver cages in order to meet the development requirements of the laver industry described above. as a result,
A stretched rod made of polypropylene formed into a predetermined shape and size by subjecting a tubular or rod-like structure obtained by a usual extrusion molding method using a general-purpose polypropylene resin to continuous processing of reheating and stretching under specific conditions. However, the present inventors have found that the above-mentioned requirements can be met, and arrived at the present invention.
As is apparent from the above description, an object of the present invention is to provide a conventional polypropylene-based resin composition or JP-B-62-3999.
(1) To provide a polypropylene seaweed cage obtained by braiding a polypropylene stretched rod-shaped molded product having high rigidity and high strength, which cannot be achieved by a non-stretched extruded product using the high-rigidity polypropylene resin described in (1). is there.
【００１０】[0010]
【問題点を解決するための手段】本発明は、上記目的を
達成するためになされたもので、下記の構成を有する。 （１）軸方向に６倍以上に延伸処理した管状または棒状
構造体であって、その曲げ弾性率が６００ｋｇｆ／ｍｍ
2 以上で曲げ強度が１２ｋｇｆ／ｍｍ2 以上の曲げ剛性
を有するポリプロピレン製延伸棒状体を編組してなるこ
とを特徴とする高剛質海苔用ポリプロピレン製海苔簀。 （２）メルトフローレートが０．５〜２０ｇ／１０分の
範囲内にあるポリプロピレン樹脂を使用してなることを
特徴とする前記（１）記載の高剛質海苔用ポリプロピレ
ン製海苔簀。 （３）ポリプロピレン製延伸棒状体の表面を酸化処理し
てなることを特徴とする前記（１）記載の高剛質海苔用
ポリプロピレン製海苔簀。 （４）ポリプロピレン製延伸棒状体の表面に塩素化ポリ
オレフィンを被覆してなることを特徴とする前記（１）
記載の高剛質海苔用ポリプロピレン製海苔簀。 （５）ポリプロピレン製海苔簀を構成する延伸棒状体の
一部を無延伸ポリプロピレン製棒状体で置換してなるこ
とを特徴とする前記（１）記載の高剛質海苔用ポリプロ
ピレン製海苔簀。 （６）ポリプロピレン樹脂を溶融押出、賦形、冷
却、再加熱、延伸処理、再冷却、および表面処
理の７つの操作を連続的に実施する製造工程を経て延伸
棒状体を製造して得られる曲げ弾性率が６００ｋｇｆ／
ｍｍ 2 以上で曲げ強度が１２ｋｇｆ／ｍｍ 2 以上の曲げ
剛性を有する該棒状体を編組することを特徴とする高剛
質海苔用ポリプロピレン製海苔簀。SUMMARY OF THE INVENTION The present invention has been made to achieve the above object and has the following arrangement. (1) A tubular or rod-like structure that has been stretched 6 times or more in the axial direction, and has a flexural modulus of 600 kgf / mm.
High rigid seaweed for polypropylene laver bamboo bending in two or more strength characterized by being braided polypropylene stretched rod-shaped body having a 12 kgf / mm 2 or more bending stiffness. (2) The polypropylene seaweed cage for high-rigid seaweed according to the above (1), wherein a polypropylene resin having a melt flow rate in the range of 0.5 to 20 g / 10 minutes is used. (3) The polypropylene seaweed cage for high-rigid seaweed as described in (1) above, wherein the surface of the stretched rod-shaped body made of polypropylene is oxidized. (4) The above (1), wherein the surface of the drawn rod made of polypropylene is coated with a chlorinated polyolefin.
The high-rigidity laver for polypropylene according to the description. (5) The polypropylene laver for high-rigid laver according to the above (1), wherein a part of the stretched rod constituting the polypropylene laver is replaced with a non-stretched polypropylene rod. (6) Bending obtained by producing a stretched rod through a production process of continuously performing seven operations of melt extrusion, shaping, cooling, reheating, stretching, recooling, and surface treatment of a polypropylene resin. The elastic modulus is 600kgf /
mm 2 or more in bending strength 12 kgf / mm 2 or more bending
A high-rigidity laver made of polypropylene for laver, wherein the rod-shaped body having rigidity is braided.
【００１１】[0011]
【発明の構成と作用】本発明の構成とその作用につき、
以下に詳述する。本発明に使用する原料樹脂のポリプロ
ピレン樹脂は、一般的な押出成形機で連続的に成形可能
な結晶性ポリプロピレン樹脂であれば特別に限定される
ものではない。しかし、本発明における管状または棒状
構造体の押出成形性および延伸加工適性を考慮して、メ
ルトフロ−レ−ト（ＪＩＳ−Ｋ−６７５８準拠、樹脂温
２３０℃×荷重２．１６Ｋｇにより測定。以下、これを
ＭＦＲと略記する）が０．５〜２０ｇ／１０分の結晶性
プロピレン単独重合体、即ちホモポリプロピレン樹脂が
望ましい。該ＭＦＲが０．５ｇ／１０分未満のポリプロ
ピレン樹脂では、流動性が悪いため押出機からの吐出量
が低下し生産性が悪くなるので好ましくない。また、Ｍ
ＦＲが２０ｇ／１０分を超えるものは、溶融粘性が低い
ために管状または棒状構造体としての成形が困難になる
と共に、延伸配向の効果が発現しにくいので好ましくな
い。The structure and operation of the present invention will now be described.
Details will be described below. The polypropylene resin as a raw material resin used in the present invention is not particularly limited as long as it is a crystalline polypropylene resin that can be continuously molded by a general extruder. However, in consideration of the extrudability and stretchability of the tubular or rod-shaped structure in the present invention, a melt flow rate (measured by JIS-K-6758, resin temperature 230 ° C. × load 2.16 Kg. A crystalline propylene homopolymer having an MFR of 0.5 to 20 g / 10 min, that is, a homopolypropylene resin is desirable. The polypropylene resin having an MFR of less than 0.5 g / 10 minutes is not preferred because the flowability is poor and the discharge amount from the extruder is reduced, resulting in poor productivity. Also, M
A resin having an FR of more than 20 g / 10 minutes is not preferred because it has a low melt viscosity, which makes it difficult to form a tubular or rod-shaped structure and hardly exerts the effect of stretching orientation.
【００１２】なお、前記ホモポリプロピレン以外に、プ
ロピレンと他のα−オレフィン等との共重合体やこれら
を混合したポリプロピレン系樹脂を使用することができ
る。本発明においては、必要に応じて該ポリプロピレン
系樹脂に、他の合成樹脂や石油樹脂等の異種成分を適宜
添加することもできる。これらの異種成分としては例え
ば、ポリスチレン、ポリアミド等の熱可塑性樹脂や石油
樹脂が挙げられる。また、物性その他の品質性能を向上
させるために、酸化防止剤や紫外線吸収剤などの安定
剤、シリカやタルク、ジベリデンソルビト−ル系化合物
などの造核剤、炭酸カルシウムや珪酸カルシウム、硫酸
バリウム等の無機質充填剤、あるいは各種界面活性剤に
よる帯電防止剤やスリップ剤、難燃剤、分散剤、顔料な
どの各種添加剤等を適量添加したものを用いることがで
きる。In addition to the above-mentioned homopolypropylene, a copolymer of propylene with another α-olefin or the like, or a polypropylene resin obtained by mixing these may be used. In the present invention, a heterogeneous component such as another synthetic resin or a petroleum resin can be appropriately added to the polypropylene resin as required. Examples of these different components include thermoplastic resins such as polystyrene and polyamide, and petroleum resins. Further, in order to improve physical properties and other quality performance, stabilizers such as antioxidants and ultraviolet absorbers, nucleating agents such as silica, talc, diberiden sorbitol compounds, calcium carbonate and calcium silicate, and sulfuric acid. Inorganic fillers such as barium, or various additives such as antistatic agents by various surfactants, slip agents, flame retardants, dispersants, pigments and the like can be used.
【００１３】本発明におけるポリプロピレン製海苔簀
は、原料として前記ポリプロピレン樹脂を用い、該樹脂
に溶融押出、賦形、および冷却、ひきつづき再
加熱、延伸処理、再冷却、および表面処理の７つ
の操作を好ましくは連続的に付与する製造工程を経て製
造されたポリプロピレン製延伸棒状体を所定の長さに切
断した後、該棒状体を手編みもしくは機械的に編組する
ことによって得られる。前記〜の工程は、一般的に
知られている異形押出成形方法により管状または棒状構
造体を得る工程であり、本発明者等は延伸処理する前の
該棒状体を便宜的に原反と呼称している。該原反は、
溶融押出の工程で、原料樹脂であるホモポリプロピレン
とブロックまたはランダムポリプロピレンとの複層共押
出しでもよいし、あるいは該ポリプロピレン樹脂と他の
熱可塑性樹脂との多層共押出しで成形してもよい。The polypropylene laver in the present invention uses the above polypropylene resin as a raw material, and performs seven operations of melt extrusion, shaping, and cooling, followed by reheating, stretching, recooling, and surface treatment on the resin. Preferably, it is obtained by cutting a stretched rod-shaped rod made of polypropylene produced through a production step of continuously applying the rod to a predetermined length, and then manually knitting or mechanically braiding the rod. The above steps are steps for obtaining a tubular or rod-like structure by a generally known profile extrusion molding method, and the present inventors conveniently refer to the rod-like body before stretching as a raw material. doing. The web is
In the melt-extrusion step, a multi-layer co-extrusion of homopolypropylene and block or random polypropylene, which are raw material resins, or a multi-layer co-extrusion of the polypropylene resin and another thermoplastic resin may be used.
【００１４】ここで、該原反の形状寸法は、目的の海苔
簀用素材となる延伸棒状体の形状寸法に対応して、一定
の基準で拡大された形状寸法に賦形されなければならな
い。即ち、該原反の外径Ｄ1 は、該原反を延伸処理する
ことによって形成される延伸棒状体の外径Ｄ2 とその延
伸倍率λとの関係から、次式により算出した値を製造基
準として寸法管理する必要がある。 Ｄ1 ＝√λ×Ｄ2 なお、上式において該原反が管状構造の場合には、上式
の外径（Ｄ1 、Ｄ2 ）をそれぞれの内径（ｄ1 、ｄ2 ）
に、あるいはその厚み（ｔ1 、ｔ2 ）に置き換えても適
用できる。Here, the shape and size of the raw material must be formed into a shape and size which is enlarged on a predetermined basis in accordance with the shape and size of the stretched rod-shaped material to be used as the target material for laver. That is, the outer diameter D 1 of the raw material is a value calculated by the following equation from the relationship between the outer diameter D 2 of the drawn rod-shaped body formed by stretching the raw material and the draw ratio λ. It is necessary to control dimensions as a standard. D 1 = √λ × D 2 In the above equation, when the material has a tubular structure, the outer diameters (D 1 , D 2 ) of the above equation are replaced by the respective inner diameters (d 1 , d 2 ).
Or the thickness (t 1 , t 2 ).
【００１５】上記〜の工程で前記原反が形状固定さ
れる過程において、該原反は溶融押出の時点から数十秒
以内の間に７０℃以下の温度になるように急冷処理され
ることが望ましい。該原反をこのように急冷処理する本
質的な理由は、後述の延伸処理工程における前記棒状体
の延伸性を向上させることにある。すなわち、本発明に
使用するポリプロピレン樹脂のごとき結晶性を有する熱
可塑性樹脂を結晶構造維持下で延伸処理すると、該樹脂
組織中の結晶がずり変形を起こしてその分子鎖が延伸方
向に配向され、物理的特性の著しく向上した成形品が得
られるのであるが、この結晶のずり変形挙動をより一層
容易ならしめて該樹脂の延伸性を向上させるためには、
溶融樹脂が冷却再結晶化する際に、その結晶化度をでき
るだけ抑えて微細結晶核を多く作り、結晶を成長させな
いように該樹脂の再結晶化速度を速くする前記冷却条件
が必要である。ここで、該原反は、前記〜の工程に
おいて前記冷却条件が満たされずに著しく長い冷却時間
を要したり、あるいはまた冷却工程を出た後、時間を
置いて非連続的に次工程に供給した場合、結晶性熱可塑
性樹脂の再結晶化挙動の特性から、徐冷現象や経時変化
の影響で該樹脂中の球晶が大きく成長して結晶化度が高
くなるため、前述の理由により結晶のずり変形挙動が極
めて困難となり、延伸不適の状態に陥る。ここに、本発
明において前記〜の工程と後述の再加熱以後の工
程とを繋いで連続工程とする意義と目的がある。In the process of fixing the shape of the raw material in the above steps, the raw material may be rapidly cooled to a temperature of 70 ° C. or less within several tens of seconds from the time of melt extrusion. desirable. The essential reason for quenching the raw material in this way is to improve the stretchability of the rod-shaped body in the stretching process described below. That is, when a thermoplastic resin having crystallinity such as the polypropylene resin used in the present invention is stretched while maintaining the crystal structure, the crystals in the resin structure undergo shear deformation and the molecular chains thereof are oriented in the stretching direction, Although a molded article with significantly improved physical properties can be obtained, in order to further facilitate the shear deformation behavior of the crystal and improve the stretchability of the resin,
When the molten resin is cooled and recrystallized, the above-mentioned cooling conditions are required to suppress the crystallinity as much as possible to produce many fine crystal nuclei and to increase the recrystallization speed of the resin so as not to grow crystals. Here, the raw material is required to have a remarkably long cooling time because the cooling conditions are not satisfied in the above-mentioned steps, or the raw material is supplied to the next step discontinuously after a certain time after leaving the cooling step. In this case, since the recrystallization behavior of the crystalline thermoplastic resin is large, the spherulites in the resin grow large due to the effects of slow cooling and aging, and the degree of crystallinity increases. Shear deformation behavior becomes extremely difficult, resulting in an unsuitable stretching state. Here, in the present invention, there is the significance and purpose of connecting the above-mentioned steps to the steps after reheating described later to form a continuous step.
【００１６】かくして形状固定された前記原反は、次の
再加熱と延伸処理の工程において、適当な加熱装置
により延伸適正温度領域に再加熱された後、直ちにその
温度維持下で該原反の走行速度より大きい所定の速度で
その走行する方向に連続して引っ張ることによって延伸
処理が施され、所望の形状寸法に形成された延伸棒状体
へと形状が縮小変形する。ここで、再加熱による延伸適
正温度領域とは、結晶性熱可塑性樹脂の組織体が結晶構
造を形成している状態で物理的な引張り変形を付与され
ることにより、その変形方向に好適に分子鎖の配向を引
き起こし、配向方向の強度特性に優れた製品を得ること
ができる延伸処理温度の適正範囲を示す。本発明に用い
るポリプロピレン樹脂の場合は、１２０〜１５０℃、好
ましくは１３０〜１４５℃の範囲が延伸適正温度領域で
ある。The raw material thus fixed in shape is reheated to an appropriate stretching temperature range by a suitable heating device in the next reheating and stretching process, and immediately after maintaining the temperature, the raw material is heated. Stretching is performed by continuously pulling in a traveling direction at a predetermined speed higher than the traveling speed, and the shape is reduced and deformed into a stretched rod-like body having a desired shape and dimensions. Here, the appropriate temperature range for stretching by reheating means that the crystalline thermoplastic resin is subjected to physical tensile deformation in a state where the structure thereof has formed a crystal structure, so that the molecular structure can be suitably adjusted in the deformation direction. The drawing shows an appropriate range of a stretching treatment temperature at which chain orientation is caused and a product having excellent strength properties in the orientation direction can be obtained. In the case of the polypropylene resin used in the present invention, an appropriate stretching temperature range is 120 to 150 ° C, preferably 130 to 145 ° C.
【００１７】この再加熱による前記原反の延伸適正温度
は、本発明の目的とする曲げ剛性や形状精度を有するポ
リプロピレン製延伸棒状体を得る上で重要な管理項目で
あって、１２０℃より低い温度で延伸処理を行うと、当
該樹脂の分子配向が過度になるかまたは延伸ムラが発生
するため、ミクロボイドが生じて白化した状態になった
り、タテ割れが現出したりして、所望形状の延伸棒状体
が得られにくくなる。逆に、１５０℃以上の高い温度ま
で加熱すると、該原反が極度に軟化した状態となるため
見掛け上は延伸しやすくなるが、当該樹脂の分子配向が
起こりにくくなり、延伸処理による棒状体の高強度・高
剛性化の発現効果が大幅に低下して、所望の曲げ弾性率
や曲げ強度を有する延伸棒状体が得られにくくなる。The proper stretching temperature of the raw fabric by the reheating is an important control item in obtaining a polypropylene stretched rod having bending rigidity and shape accuracy which is the object of the present invention, and is lower than 120 ° C. If the stretching treatment is performed at a temperature, the molecular orientation of the resin becomes excessive or stretching unevenness occurs, so that microvoids are generated and the resin is whitened or warped cracks appear, and stretching of a desired shape is performed. It becomes difficult to obtain a rod-shaped body. Conversely, when heated to a high temperature of 150 ° C. or higher, the raw material is extremely softened and apparently easily stretched, but the molecular orientation of the resin is less likely to occur, and the rod-like body is stretched. The effect of exhibiting high strength and high rigidity is greatly reduced, and it becomes difficult to obtain a stretched rod having desired bending elastic modulus and bending strength.
【００１８】また、該延伸棒状体が、前記延伸処理の工
程において縮小変形するに際しての形態は、延伸処理前
の原反の外径をＤ1 、延伸処理後の延伸棒状体の外径を
Ｄ2とし、その延伸倍率をλとしたとき、実質的に次式
の条件を満足して前述の引張り変形が実行されたもので
なければならない。Further, when the stretched rod is reduced and deformed in the stretching process, the outer diameter of the raw material before stretching is D 1 and the outer diameter of the stretched rod after stretching is D 1 . Assuming that the stretching ratio is 2, and that the stretching ratio is λ, the above-described tensile deformation must be substantially performed while satisfying the following condition.
【００１９】[0019]
【式１】 (Equation 1)
【００２０】上式において、棒状体が管状構造である場
合には、上式の外径（Ｄ1 、Ｄ2 ）をそれぞれの内径
（ｄ1 、ｄ2 ）に、またはその厚み（ｔ1 、ｔ2 ）に置
き換えても適用できる。In the above formula, when the rod-like body has a tubular structure, the outer diameter (D 1 , D 2 ) of the above formula is replaced with the inner diameter (d 1 , d 2 ) or the thickness (t 1 , d 1 , d 2 ). It can be applied even if it is replaced with t 2 ).
【００２１】本発明におけるポリプロピレン製延伸棒状
体は、６倍以上の延伸倍率で延伸加工されていることが
好ましい。即ち、再加熱の工程において前述の延伸適
正温度範囲に再加熱された前記原反を、延伸処理の工
程において該原反の走行速度より６倍以上の大なる引張
速度を付加して延伸処理することによって、該樹脂中の
分子鎖が延伸方向に強く配向して、強度特性が著しく向
上し且つ上式の条件を満足する寸法精度および外観とも
に優れたポリプロピレン製延伸棒状体が得られる。延伸
倍率が６倍に満たない条件で延伸加工されたものは、前
記分子鎖の配向が不十分で強度特性が向上しないだけで
なく、延伸挙動が不安定となって著しい形状変化を引き
起こして、目的とする製品が得られなくなる。The stretched rod made of polypropylene in the present invention is preferably stretched at a stretch ratio of 6 times or more. That is, the raw material reheated to the above-described proper stretching temperature range in the reheating step is subjected to the stretching treatment by applying a tensile speed 6 times or more higher than the running speed of the raw fabric in the stretching treatment step. As a result, the molecular chain in the resin is strongly oriented in the stretching direction, and a stretched rod-shaped body made of polypropylene with excellent strength characteristics and excellent dimensional accuracy and appearance that satisfies the above-mentioned conditions is obtained. Stretched under conditions where the stretching ratio is less than 6 times, not only the orientation of the molecular chains is insufficient and strength properties are not improved, but also the stretching behavior becomes unstable and causes a significant change in shape, The desired product cannot be obtained.
【００２２】ここで、本発明におけるポリプロピレン製
延伸棒状体の延伸倍率の上限は特別に制限されるもので
はないが、次に示す理由により１２倍程度が限界と考え
られる。即ち、（１）該棒状体の延伸倍率と強度特性と
の関係は、延伸倍率が高くなるに伴って引張・曲げ強度
とも向上するが、１１〜１２倍の延伸倍率で該強度がほ
ぼピ−クに達すること、（２）過度の延伸配向は、当該
ポリプロピレン樹脂の分子鎖が破壊されたり、引張強度
の限界に達して該棒状体が延伸処理中に破断する、いわ
ゆる延伸破断の悪現象を生じたりすること、等である。Here, the upper limit of the stretching ratio of the stretched rod made of polypropylene in the present invention is not particularly limited, but is considered to be about 12 times for the following reason. That is, (1) the relationship between the stretching ratio and the strength characteristics of the rod-shaped body is such that both the tensile strength and the bending strength improve as the stretching ratio increases, but the strength is almost peaked at the stretching ratio of 11 to 12 times. (2) Excessive stretch orientation causes the so-called stretch-rupture phenomena, in which the molecular chain of the polypropylene resin is broken or the rod reaches the limit of tensile strength and breaks during the stretching process. And so on.
【００２３】かくして延伸倍率６倍以上に延伸され所望
する形状寸法に形成された延伸棒状体は、延伸処理の
工程に続く再冷却の工程において、直ちに適正温度以
下に降下するまで再冷却する。これは、延伸処理によっ
て強く配向した該樹脂中の分子構造を冷却固化すること
によりそのまま安定化させて、ここで得られた延伸棒状
体の強度特性や寸法精度、外観性等を確保するためであ
る。このようにして、ポリプロピレン樹脂から成る管状
または棒状構造体を特定の条件下でその軸方向に６倍以
上の延伸倍率で延伸処理した後、直ちに再冷却処理する
ことによって所望の形状寸法に形成され、後述の測定方
法により測定された曲げ弾性率が６００ｋｇｆ／ｍｍ2
以上で曲げ強度が１２ｋｇｆ／ｍｍ2 以上の曲げ剛性を
有していて、高剛性の海苔簀用素材として好適に使用で
きるポリプロピレン製延伸棒状体が得られる。The stretched rod thus stretched at a stretch ratio of 6 times or more and formed into a desired shape and size is immediately cooled again in the recooling process following the stretching process until the temperature drops to an appropriate temperature or lower. This is because the molecular structure in the resin, which is strongly oriented by the stretching treatment, is directly stabilized by cooling and solidifying, and the strength characteristics, dimensional accuracy, appearance, and the like of the obtained stretched rod-like body are obtained. is there. In this way, the tubular or rod-shaped structure made of the polypropylene resin is stretched in the axial direction at a stretch ratio of 6 times or more under specific conditions, and then immediately re-cooled to form the desired shape and dimensions. The flexural modulus measured by a measurement method described later is 600 kgf / mm 2
As described above, a stretched rod made of polypropylene, which has a bending strength of 12 kgf / mm 2 or more and can be suitably used as a high-rigid seaweed cage material, is obtained.
【００２４】本発明のポリプロピレン製海苔簀は、その
表面の一部または全面に各種海苔に対する適正な付着性
を付与しなければならないので、前記延伸棒状体は前記
再冷却の工程に続いて付設された表面処理の工程に
おいて、以下に述べるいずれかの方法により、表面処理
の操作を施す必要がある。すなわち、（１）該延伸棒状
体表面への各種の放電処理、例えばスパ−クまたはア−
クあるいはコロナ放電処理および（２）該延伸棒状体表
面へのプロパンガス等の燃焼ガス放射による火炎処理等
を行って酸化処理を施す、（３）該延伸棒状体の表面に
溶剤に溶解した塩素化ポリオレフィンを塗布または噴霧
等により被覆する、等の方法を挙げることができる。製
造に使用される海苔の種類に応じて付着性の強弱の程度
を適切に調整することも必要になる。これは前記（１）
の方法の場合、該延伸棒状体に対する放電強度や放電の
電極数を加減する、前記（２）では同じくガスバ−ナ−
の本数や燃焼ガスの放射熱量を増減する、また前記
（３）の方法であれば、塩素化ポリオレフィンの溶解濃
度あるいは該延伸棒状体への被覆厚み等によって調整す
ることができる。また、延伸棒状体を編組してなる本発
明の海苔簀の場合は、該海苔簀を構成する全部の延伸棒
状体でなく、その一部について前述（１）〜（３）の表
面処理を施したものを使用することによって、該海苔簀
の表面付着性を調整することもできる。Since the polypropylene laver cage of the present invention must impart proper adhesion to various types of laver to a part or the entire surface of the laver, the stretched rod is provided following the re-cooling step. In the surface treatment step, it is necessary to perform a surface treatment operation by any of the methods described below. That is, (1) various kinds of electric discharge treatments on the surface of the elongated rod, for example, spark or arc
Or a corona discharge treatment, and (2) a flame treatment or the like by irradiating a combustion gas such as propane gas to the surface of the elongated rod to perform an oxidation treatment. (3) Chlorine dissolved in a solvent on the surface of the elongated rod. For example, by coating or spraying a functionalized polyolefin. It is also necessary to appropriately adjust the degree of adhesiveness depending on the type of nori used in the production. This is the above (1)
In the case of the method (1), the discharge intensity and the number of discharge electrodes for the elongated rod are adjusted.
And the amount of radiant heat of the combustion gas can be increased or decreased. In the case of the above method (3), it can be adjusted by the dissolution concentration of the chlorinated polyolefin or the coating thickness of the stretched rod. Further, in the case of the seaweed cage of the present invention in which the stretched bar is braided, not the whole stretched bar which constitutes the seaweed but a part of the seaweed is subjected to the surface treatment described in (1) to (3) above. By using such a material, the surface adhesion of the laver can be adjusted.
【００２５】なお、該延伸棒状体の表面処理の操作は、
生産性を考慮して前述の如く再冷却〜表面処理と連
続したインライン工程で行うことが望ましいが、該延伸
棒状体が前記再冷却の工程に続いて所定の長さに切断さ
れた後、別に設けられたアウトライン工程で前述と同様
の表面処理操作を行ってもよいし、あるいは表面処理し
ていない延伸棒状体を所望の海苔簀に編組してから、該
海苔簀表面に前記表面処理を施してもよい。本発明にお
けるポリプロピレン製海苔簀としては、該海苔簀を構成
する延伸棒状体の一部を、従来の押出成形法で成形され
た無延伸の一般ポリプロピレン樹脂製棒状体、あるいは
特公昭６２−３９９９１記載の高剛性ポリプロピレン樹
脂製棒状体で置換して編組した海苔簀であってもよい。The operation of the surface treatment of the elongated rod is as follows.
In consideration of productivity, it is desirable to perform in an in-line process that is continuous with re-cooling to surface treatment as described above, but after the stretched rod is cut to a predetermined length following the re-cooling process, In the provided outline process, the same surface treatment operation as described above may be performed, or a stretched rod-shaped body that has not been subjected to surface treatment is braided into a desired laver, and then the surface treatment is performed on the laver surface. You may. As the polypropylene laver in the present invention, a part of the stretched rod constituting the laver is obtained by unstretching a general polypropylene resin rod formed by a conventional extrusion molding method, or described in JP-B-62-39991. The seaweed cage may be replaced with a high-rigidity polypropylene resin rod and braided.
【００２６】[0026]
【実施例】以下に本発明を、（ａ）海苔簀用素材の製
造、（ｂ）海苔簀実用試験とに区分し、それらの実施例
および比較例を示すことにより更に詳細に説明する。但
し、本発明はこの実施例によって限定されるものではな
い。なお、本実施例および比較例において海苔簀用素材
に用いる各種成形品（棒状体）の品質性能評価は、次の
試験方法によった。 海苔簀用素材の曲げ試験 ＪＩＳ−Ｋ−７２０３による硬質プラスチックの曲げ試
験方法を応用して、室温２３℃×湿度５０％の環境下で
３点曲げ試験を行い、海苔簀用素材に用いる各種成形品
（棒状体）の曲げ特性を評価した。試験要領は、当該成
形品を長さ６０ｍｍに切断したものを試験片とし、これ
を曲げ試験機の支点間距離４０ｍｍで２点支持に支える
ように置いた後、該試験片の２点支持の中央部に５００
ｍｍ／ｍｉｎの加重速度により荷重を加え、かくして該
試験片が曲げ降伏点に到るまでに要した荷重とその時の
該試験片の撓みを測定した。この試験による荷重−撓み
曲線から、当該成形品の曲げ弾性率および曲げ強度を以
下に示す計算式によって求めた。 （１）成形品曲げ弾性率 荷重−撓み曲線の最初の直線部分の傾斜より次式によっ
て算出した。The present invention will be described in more detail below by dividing the present invention into (a) production of a material for laver cages and (b) practical use of laver cages, and showing examples and comparative examples thereof. However, the present invention is not limited by this embodiment. In addition, in this example and the comparative example, the quality test evaluation of the various molded articles (rods) used for the material for laver was based on the following test method. Bending test of material for sea laver Applying the bending test method of hard plastic according to JIS-K-7203, a three-point bending test is performed in an environment of room temperature 23 ° C x 50% humidity, and various moldings used for sea laver material The bending characteristics of the product (rod) were evaluated. The test procedure is as follows. A test piece is obtained by cutting the molded product to a length of 60 mm, and is placed so as to be supported at two points at a distance between fulcrums of a bending tester of 40 mm. 500 in the center
A load was applied at a load speed of mm / min, and the load required for the test piece to reach the bending yield point and the deflection of the test piece at that time were measured. From the load-deflection curve obtained by this test, the bending elastic modulus and the bending strength of the molded product were obtained by the following calculation formulas. (1) Molded article flexural modulus It was calculated from the slope of the first straight line portion of the load-deflection curve by the following equation.
【００２７】[0027]
【式２】 (Equation 2)
【００２８】ここで、Ｌは該試験片の支点間距離（ｍ
ｍ）で、Ｉは該試験片の断面二次モーメント（ｍｍ
4 ）、Ｃは荷重−撓み曲線の最初の直線部分の勾配（ｋ
ｇｆ／ｍｍ）、即ちＣ＝Ｗ／δをそれぞれ表す。Ｗは該
試験片に掛かる荷重（ｋｇｆ）、δはその時の該試験片
の撓み（ｍｍ）を示すが、本実施例では、前記支点間距
離の２．５％撓み時のデータを採用した。なお、Ｉは金
属材料の梁の断面二次モーメントを求める機械工学上の
理論式を適用して計算した。 （２）成形品曲げ強度 該試験片が曲げ降伏点に達した点の荷重を最大曲げ荷重
として、次式により算出した。Here, L is the distance between the fulcrums of the test piece (m
m), I is the moment of inertia of area (mm
4 ), C is the slope (k) of the first straight line portion of the load-deflection curve
gf / mm), that is, C = W / δ. W indicates the load (kgf) applied to the test piece, and δ indicates the deflection (mm) of the test piece at that time. In the present embodiment, data when the distance between the fulcrums was 2.5% was adopted. In addition, I was calculated by applying a theoretical equation in mechanical engineering for obtaining a second moment of area of a beam made of a metal material. (2) Molded product bending strength The load at the point where the test piece reached the bending yield point was calculated as the maximum bending load by the following equation.
【００２９】[0029]
【式３】 (Equation 3)
【００３０】ここで、Ｗは該試験片の最大曲げ荷重（ｋ
ｇｆ）で、Ｌは該試験片の支点間距離（ｍｍ）、Ｚは該
試験片の断面係数（ｍｍ3 ）をされぞれ表す。なお、Ｚ
は金属材料の梁の断面係数を求める機械工学上の理論式
を適用して計算した。Here, W is the maximum bending load (k) of the test piece.
In gf), L represents the distance between the fulcrums of the test piece (mm), and Z represents the section modulus (mm 3 ) of the test piece. Note that Z
Was calculated by applying the theoretical formula in mechanical engineering to find the section modulus of a metal beam.
【００３１】（ａ）海苔簀用素材の製造 実施例１ 原料樹脂の曲げ弾性率（ＪＩＳ−Ｋ−６７５８に準拠、
以下同じ）が１３８ｋｇｆ／ｍｍ2 で、ＭＦＲ＝３．３
ｇ／１０分の汎用ポリプロピレン樹脂（商品名“ＵＰポ
リプロ”ＹＫ１２１−Ａ、チッソ石油化学（株）製、以
下これを“汎用ＰＰ”と略称する）を、一般的な押出機
で押出して、９ｍ／ｍｉｎの走行速度で六角形対辺の外
径４．７８ｍｍ、内円の直径２．５２ｍｍの中空断面構
造の六角形棒状体に賦形〜冷却処理して形状固定した
後、該棒状体（以下、これを原反と呼称する）を遠赤外
線ヒーター等を加熱源とする加熱装置内に導入して１３
５〜１４０℃の温度に再加熱し、該温度維持下に５４ｍ
／ｍｉｎの引張速度、即ち６倍の延伸倍率で延伸処理す
るとともに再冷却処理を施すことによって、六角形対辺
の外径１．９５ｍｍ、内円の直径１．０３ｍｍの中空断
面構造に形成されたポリプロピレン製延伸棒状体を製造
した。(A) Production of raw material for laver cage Example 1 Flexural modulus of raw material resin (based on JIS-K-6758;
138 kgf / mm 2 and MFR = 3.3.
g / 10 min. of a general-purpose polypropylene resin (trade name “UP Polypro” YK121-A, manufactured by Chisso Petrochemical Co., Ltd .; hereinafter, abbreviated as “general-purpose PP”) with a general extruder, 9 m The shape of the hexagonal rod having a hollow cross-sectional structure having an outer diameter of 4.78 mm on the opposite side of the hexagon and a diameter of 2.52 mm of the inner circle at a traveling speed of / min is fixed by performing a shape-cooling process, and then the rod-shaped body (hereinafter referred to as the , Which is referred to as a raw material) into a heating device using a far-infrared heater or the like as a heating source.
Reheat to a temperature of 5 to 140 ° C., and maintain 54 m
By performing a stretching treatment at a tensile speed of / min, that is, a stretching magnification of 6 times, and performing a re-cooling treatment, a hollow cross-sectional structure having an outer diameter of 1.95 mm on the opposite side of the hexagon and a diameter of 1.03 mm of the inner circle was formed. A stretched rod made of polypropylene was produced.
【００３２】実施例２ 原反の寸法を六角形対辺の外径５．５２ｍｍ、内円の直
径２．９１ｍｍ、再加熱後の引張速度を７２ｍ／ｍｉ
ｎ、延伸倍率を８倍とした以外は、実施例１と全く同様
にして同寸法のポリプロピレン製延伸棒状体を得た。Example 2 The dimensions of the raw material were an outer diameter of 5.52 mm on the opposite side of a hexagon, an inner circle diameter of 2.91 mm, and a tensile speed after reheating of 72 m / mi.
n, except that the draw ratio was set to 8, a stretched rod made of polypropylene of the same dimensions was obtained in exactly the same manner as in Example 1.
【００３３】実施例３ 原反の寸法を六角形対辺の外径６．１７ｍｍ、内円の直
径３．２６ｍｍ、再加熱後の引張速度を９０ｍ／ｍｉ
ｎ、延伸倍率を１０倍とした以外は、実施例１と全く同
様にして同寸法のポリプロピレン製延伸棒状体を得た。
以上の実施例１〜３で得たポリプロピレン製延伸棒状体
は、形状・寸法精度・外観ともに既存のポリプロピレン
製海苔簀用棒状体と比較して全く遜色がなく、海苔簀用
素材として好適に提供し得るものであった。以上の実施
例において製造した前記ポリプロピレン製延伸棒状体の
曲げ試験による曲げ特性の評価結果を表１に示す。Example 3 The dimensions of the raw material were the outer diameter of the opposite side of the hexagon 6.17 mm, the diameter of the inner circle 3.26 mm, and the tensile speed after reheating at 90 m / mi.
n, except that the draw ratio was set to 10 times, a polypropylene drawn rod having the same dimensions was obtained in exactly the same manner as in Example 1.
The stretched polypropylene rods obtained in the above Examples 1 to 3 are not inferior to the existing polypropylene laver rods in shape, dimensional accuracy, and appearance, and are suitably provided as a material for laver cages. Could be done. Table 1 shows the evaluation results of the bending characteristics of the polypropylene-made stretched rods manufactured in the above Examples by a bending test.
【００３４】比較例１および２ 本発明の実施例により製造したポリプロピレン製延伸棒
状体の曲げ特性レベルを確認するために、従来技術の押
出成形方法により現在量産されているポリプロピレン製
の海苔簀用素材であって、原料樹脂の曲げ弾性率が２０
５ｋｇｆ／ｍｍ2 で、ＭＦＲ＝６．５ｇ／１０分の高結
晶・高剛性ポリプロピレン樹脂（商品名“チッソＨＣＰ
Ｐ”ＸＦ１７９７、チッソ石油化学（株）製、以下これ
を“高剛性ＰＰ”と略称する）を用いて、実施例１〜３
と同じ断面構造で、六角形対辺の外径が１．９５〜２．
０５ｍｍ、内円の直径が１．０５〜１．１５ｍｍの中空
六角形体に形成された無延伸の“高剛性ＰＰ”製棒状体
を比較例１とし、外径１．６〜１．８ｍｍの中実構造の
竹ひごを比較例２として、これらの曲げ特性の評価結果
を表１に併記した。Comparative Examples 1 and 2 In order to confirm the bending characteristic level of the stretched rod made of polypropylene produced according to the example of the present invention, a polypropylene seaweed material mass-produced by a conventional extrusion molding method at present. And the bending elastic modulus of the raw material resin is 20
5 kgf / mm 2 , high crystallinity and high rigidity polypropylene resin with MFR = 6.5 g / 10 min (trade name “Chisso HCP
P "XF1797, manufactured by Chisso Petrochemical Co., Ltd .;
The outer diameter of the opposite side of the hexagon is 1.95 to 2.
A non-stretched “high-rigidity PP” rod-shaped body formed into a hollow hexagonal body having a diameter of 0.05 mm and an inner circle of 1.05 to 1.15 mm is referred to as Comparative Example 1 and has an outer diameter of 1.6 to 1.8 mm. Table 1 also shows the evaluation results of the bending properties of the actual structure bamboo higo as Comparative Example 2.
【００３５】[0035]
【表１】 [Table 1]
【００３６】表１より明らかなように、実施例１〜３で
用いた原料樹脂（汎用ＰＰ）の曲げ弾性率が比較例１の
それよりも小さいにも関わらず、該実施例で得られた本
発明のポリプロピレン製延伸棒状体は、成形品での曲げ
特性が従来品のポリプロピレン製海苔簀用素材の中で最
も剛性が高いと評価されている比較例１の“高剛性Ｐ
Ｐ”からなる棒状体に比べて格段に改良されていること
がわかる。曲げ特性レベルとしては、実施例１で得られ
た成形品（６倍延伸）の曲げ弾性率および曲げ強度以上
であれば、これを用いた海苔簀の実用試験において乾燥
収縮力の大きい高剛質海苔簀にも適応し得ることが実証
された。また、天然素材の竹ひご（比較例２）を凌駕す
るまでには到らないものの、実施例３で得られた延伸倍
率１０倍の“汎用ＰＰ”製延伸棒状体であれば、前記竹
ひごの剛性レベルにほぼ拮抗する曲げ特性を有している
ことから、該延伸棒状体を編組した本発明のポリプロピ
レン製海苔簀は、竹ひご製海苔簀にも充分に競合し得る
ことが実用試験の結果において実証された。As is clear from Table 1, although the flexural modulus of the raw material resin (general-purpose PP) used in Examples 1 to 3 was smaller than that of Comparative Example 1, it was obtained in this example. The stretched rod made of polypropylene according to the present invention has a bending property of a molded article which is evaluated to be the highest rigidity among the conventional polypropylene seaweed stock materials.
It can be seen that it is significantly improved as compared with the rod-shaped body made of P ". If the bending characteristic level is equal to or higher than the bending elastic modulus and bending strength of the molded product (6 times stretched) obtained in Example 1, In a practical test of a seaweed basin using this, it was proved that it could be applied to a high-rigid seaweed basin with a large drying shrinkage force. Although not achieved, the stretched rod made of “general-purpose PP” with a draw ratio of 10 obtained in Example 3 has a bending characteristic that almost antagonizes the rigidity level of the bamboo straw. Practical test results have demonstrated that the polypropylene laver cage of the present invention, in which the stretched rod-shaped body is braided, can sufficiently compete with the bamboo-higashi laver cage.
【００３７】（ｂ）海苔簀実用試験 実施例４ 前記（ａ）の実施例２におけるポリプロピレン製延伸棒
状体を製造する工程中の再冷却処理に続いて、該延伸棒
状体を塩素化ポリプロピレン（商品名”スーパークロ
ン”８０４Ｍ、塩素化度３４％、、山陽国策パルプ
（株）製）と塩素化ポリエチレン（商品名”スーパーク
ロン”５０７、塩素化度６８％、山陽国策パルプ（株）
製）の８０：２０（重量比）混合物１０％酢酸エステル
溶媒中に浸漬して通過させた後、熱風乾燥し、該延伸棒
状体表面に上記塩素化ポリオレフィンの皮膜を形成し
た。該皮膜形成後、所定の長さに切断した該延伸棒状体
を糸で編んで、本発明のポリプロピレン製海苔簀を得
た。(B) Practical sea laver test Example 4 Following the re-cooling treatment in the step of manufacturing the drawn polypropylene rod in Example 2 of (a), the drawn rod was treated with chlorinated polypropylene (commodity). Name "Supercron" 804M, chlorination degree 34%, manufactured by Sanyo Kokusaku Pulp Co., Ltd. and chlorinated polyethylene (trade name "Supercron" 507, chlorination degree 68%, Sanyo Kokusaku Pulp Co., Ltd.)
The mixture was immersed in an 80:20 (weight ratio) mixture of 10% acetate solvent and passed through, and then dried with hot air to form a film of the chlorinated polyolefin on the surface of the stretched rod. After forming the film, the drawn rod-shaped body cut to a predetermined length was knitted with a yarn to obtain a polypropylene seaweed cage of the present invention.
【００３８】比較例３ 前記（ａ）の比較例１で用いた”高剛性ＰＰ”製棒状体
の表面に、実施例４と同様に塩素化ポリオレフィンの皮
膜を形成後、該棒状体を糸で編んで海苔簀を得た。 比較例４ 前記（ａ）比較例２で用いた竹ひごと、比較例３の”高
剛性ＰＰ”製棒状体とを交互に糸で編んで海苔簀を得
た。以上の実施例４と比較例３および４で得た海苔簀を
各々３００枚ずつ用いて、海苔の中で最も硬いと言われ
ている兵庫県明石漁場の海苔を原料として乾海苔の製造
試験を行い、該試験における簀の曲がり、海苔の仕上が
り（特に表面光沢）および海苔の乾燥性について比較評
価した。なお、簀の曲がりは、使用前の海苔簀を基準に
して、該海苔簀を４５〜５０℃の温度に設定した温風乾
燥装置の中に１３０回循環させた後の該海苔簀素材の軸
方向における最大撓み量を実測した値である。それらの
結果を表２に示す。Comparative Example 3 A film of chlorinated polyolefin was formed on the surface of the "high-rigidity PP" rod-like body used in Comparative Example 1 of (a) in the same manner as in Example 4, and the rod-like body was then threaded. Weaved and obtained a laver cage. Comparative Example 4 A laver cage was obtained by alternately knitting (a) the bamboo string used in Comparative Example 2 and the "high-rigidity PP" rod-shaped body of Comparative Example 3 with yarn. Using 300 laver cages obtained in Example 4 and Comparative Examples 3 and 4 respectively, a dry laver production test was conducted using the laver of the Akashi fishing ground in Hyogo Prefecture, which is said to be the hardest of the laver, as a raw material. In this test, the bending of the cage, the finish of laver (particularly the surface gloss), and the drying property of laver were comparatively evaluated. In addition, the bend of the cage is based on the laver before use, and the shaft of the laver material after circulating the laver 130 times in a warm air drying device set at a temperature of 45 to 50 ° C. It is a value obtained by actually measuring the maximum deflection amount in the direction. Table 2 shows the results.
【００３９】[0039]
【表２】 [Table 2]
【００４０】表２から判るように、兵庫県明石漁場で収
穫されるような極めて硬い性質の海苔を乾燥する場合は
乾燥時に生じる海苔の収縮力が大きいため、これに使用
する海苔簀は高い剛性を有するものが必要となるが、本
発明のポリプロピレン製延伸棒状体を素材に用いた海苔
簀においては該海苔の乾燥収縮力に充分耐え得るので、
簀の曲がりも少なく竹ひごを用いた海苔簀とほぼ同等で
あり、乾海苔も光沢のあるものに仕上がって商品価値の
高い製品が得られる。一方、無延伸の高剛性ポリプロピ
レン製海苔簀は他地区の海苔製造には大きな実績を挙げ
ているが、本試験において製造した前記高剛質の海苔に
対しては剛性が劣るため、簀の曲がりが大きくなって乾
燥装置内の温風の流通を阻害し、その結果乾燥時間が長
く付着水分も多くなって、乾海苔の仕上がりが悪く商品
価値の低い製品となる。As can be seen from Table 2, when drying the very hard seaweed that is harvested at the Akashi fishing ground in Hyogo Prefecture, the seaweed shrinkage generated during drying is large, and the seaweed pens used for this purpose have high rigidity. Although it is necessary to have a, but in a laver cage using a polypropylene stretched rod-shaped body of the present invention as a material, since it can sufficiently withstand the drying shrinkage force of the laver,
There is little bending of the pond and it is almost the same as a nori pond using bamboo. The dried nori is finished to be glossy and a product with high commercial value can be obtained. On the other hand, unstretched high-rigidity polypropylene laver has a great track record in laver production in other areas, but the rigidity is inferior to the high-rigid laver produced in this test, so the bend of the laver Becomes large and hinders the circulation of warm air in the drying apparatus. As a result, the drying time is long and the amount of adhering water is increased, resulting in a product having poor dry laver finish and low commercial value.
【００４１】[0041]
【発明の効果】本発明のポリプロピレン製海苔簀は、既
存のポリプロピレン製海苔簀に特有の剛性不足や使用す
るポリプロピレン樹脂組成物中の剛性補強材に付随する
諸問題点が解消されると共に、天然素材であるがゆえに
品質管理の難しい竹ひご製海苔簀に代替し得る高剛性・
高品質の海苔簀として好適に提供することができ、海苔
産業の発展に寄与するところ極めて大なるものがある。EFFECT OF THE INVENTION The polypropylene seaweed of the present invention can solve the problems of rigidity inherent in existing polypropylene seaweeds and various problems associated with the rigid reinforcing material in the polypropylene resin composition to be used, as well as eliminating natural problems. High rigidity that can be used as a bamboo seaweed sea ladle that is difficult to control because of its material
There is an extremely large portion that can be suitably provided as a high quality laver cage and contributes to the development of the laver industry.
Claims (6)
たは棒状構造体であって、その曲げ弾性率が６００ｋｇ
ｆ／ｍｍ2 以上で曲げ強度が１２ｋｇｆ／ｍｍ2 以上の
曲げ剛性を有するポリプロピレン製延伸棒状体を編組し
てなることを特徴とする高剛質海苔用ポリプロピレン製
海苔簀。1. A tubular or rod-like structure stretched 6 times or more in an axial direction, and having a flexural modulus of 600 kg.
f / mm 2 or more in bending strength 12 kgf / mm 2 or more bending high rigid seaweed for polypropylene laver bamboo, characterized by comprising braided polypropylene stretched rod-shaped body having a rigidity.
１０分の範囲内にあるポリプロピレン樹脂を使用してな
ることを特徴とする請求項（１）記載の高剛質海苔用ポ
リプロピレン製海苔簀。2. A melt flow rate of 0.5 to 20 g /
The polypropylene seaweed cage for high-rigid seaweeds according to claim 1, wherein a polypropylene resin within a range of 10 minutes is used.
化処理してなることを特徴とする請求項（１）記載の高
剛質海苔用ポリプロピレン製海苔簀。3. The polypropylene seaweed cage for high-rigid seaweeds according to claim 1, wherein the surface of the stretched rod-shaped body made of polypropylene is oxidized.
素化ポリオレフィンを被覆してなることを特徴とする請
求項（１）記載の高剛質海苔用ポリプロピレン製海苔
簀。4. The polypropylene seaweed cage for highly rigid seaweed according to claim 1, wherein the surface of the stretched rod-like body made of polypropylene is coated with chlorinated polyolefin.
棒状体の一部を無延伸ポリプロピレン製棒状体で置換し
てなることを特徴とする請求項（１）記載の高剛質海苔
用ポリプロピレン製海苔簀。5. The polypropylene seaweed for high-rigid seaweed according to claim 1, wherein a part of the stretched seam constituting the polypropylene seaweed cage is replaced by a non-stretched polypropylene seaweed. Pens.
形、冷却、再加熱、延伸処理、再冷却、および
表面処理の７つの操作を連続的に実施する製造工程を
経て延伸棒状体を製造して得られる曲げ弾性率が６００
ｋｇｆ／ｍｍ 2 以上で曲げ強度が１２ｋｇｆ／ｍｍ 2 以
上の曲げ剛性を有する該棒状体を編組することを特徴と
する高剛質海苔用ポリプロピレン製海苔簀。6. The polypropylene resin melt extrusion, shaping, cooling, reheating, stretching treatment, resulting recooled, and seven operations of the surface treatment by producing oriented rod-like body via a continuously carry out the manufacturing process Bending modulus of elasticity is 600
kgf / mm 2 or more in bending strength 12 kgf / mm 2 or more
A high-rigidity laver made of polypropylene for laver, characterized by braiding the rod having the above bending rigidity .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4069592A JP2750484B2 (en) | 1992-02-19 | 1992-02-19 | Polypropylene laver cage |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4069592A JP2750484B2 (en) | 1992-02-19 | 1992-02-19 | Polypropylene laver cage |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0622733A JPH0622733A (en) | 1994-02-01 |
| JP2750484B2 true JP2750484B2 (en) | 1998-05-13 |
Family
ID=13407259
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4069592A Expired - Lifetime JP2750484B2 (en) | 1992-02-19 | 1992-02-19 | Polypropylene laver cage |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2750484B2 (en) |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61234761A (en) * | 1985-04-11 | 1986-10-20 | Chisso Corp | Laver screen made of high-rigidity polypropylene |
-
1992
- 1992-02-19 JP JP4069592A patent/JP2750484B2/en not_active Expired - Lifetime
Non-Patent Citations (1)
| Title |
|---|
| 総合化学研究所編、現場マニュアルＸ巻 延伸加工技術編（丸善）昭和４６年１１月発行 Ｐ．１０〜１３ |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0622733A (en) | 1994-02-01 |
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