JP6613405B2 - Flame-retardant resin composition and method for producing flame-retardant resin composition - Google Patents
Flame-retardant resin composition and method for producing flame-retardant resin composition Download PDFInfo
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Description
本発明は、難燃性樹脂組成物、及び難燃性樹脂組成物の製造方法に関する。 The present invention relates to a flame retardant resin composition and a method for producing the flame retardant resin composition.
合成樹脂に難燃剤を添加した難燃性樹脂組成物が知られている。この種の難燃性樹脂組成物では、有機系難燃剤、無機系難燃剤等の様々な種類の難燃剤が利用されている。また、特許文献１に示されるように、環境負荷低減等を目的として、植物由来物質（例えば、トマトの茎の粉砕物）からなる難燃剤が用いられる場合もある。
A flame retardant resin composition in which a flame retardant is added to a synthetic resin is known. In this type of flame retardant resin composition, various types of flame retardants such as organic flame retardants and inorganic flame retardants are used. In addition, as shown in
難燃剤を合成樹脂に添加する際、難燃剤の溶解性が問題となることがある。難燃剤の溶解性が低いと、難燃剤が合成樹脂中に均一に分散されず、難燃剤が合成樹脂表面から浮き出る等の不具合が生じることがあった。そのため、この種の難燃剤としては、合成樹脂の種類毎に、溶解性が高く相溶性に優れるものが適宜、選択されている。したがって、溶解性（相溶性）の観点より、特定の合成樹脂に対して使用可能な難燃剤は、ある程度限られてしまうのが実情であった。 When adding a flame retardant to a synthetic resin, the solubility of the flame retardant may be a problem. If the solubility of the flame retardant is low, the flame retardant is not uniformly dispersed in the synthetic resin, and there may be a problem that the flame retardant floats from the surface of the synthetic resin. Therefore, as this kind of flame retardant, those having high solubility and excellent compatibility are appropriately selected for each type of synthetic resin. Therefore, from the viewpoint of solubility (compatibility), the actual situation is that the flame retardant usable for a specific synthetic resin is limited to some extent.
また、合成樹脂に対して難燃剤を添加し過ぎると、合成樹脂が増粘等することで成形不良等の問題が発生することがあった。つまり、難燃剤は、合成樹脂に対して無制限に添加できるものではなく、限られた添加量の範囲で、合成樹脂に難燃性を付与する必要がある。そのため、難燃剤によっては、合成樹脂に対して最大限に添加しても、得られる難燃性の効果に限界があった。 Moreover, when a flame retardant is added too much with respect to a synthetic resin, problems, such as a molding defect, may generate | occur | produce by the synthetic resin becoming thickened. That is, the flame retardant can not be added to the synthetic resin without limitation, and it is necessary to impart flame retardancy to the synthetic resin within a limited amount of addition. Therefore, depending on the flame retardant, even if it is added to the synthetic resin to the maximum extent, the flame retardant effect obtained has a limit.
例えば、合成樹脂に添加する難燃剤として、上記植物由来物質を使用した場合、最終的に得られる樹脂組成物の難燃性は、ＵＬ９４規格でＨＢ程度（遅燃性）であり、更なる難燃性の向上が求められていた。 For example, when the above plant-derived substance is used as a flame retardant added to a synthetic resin, the flame resistance of the resin composition finally obtained is about HB (slow flame retardancy) in the UL94 standard, which is further difficult There was a need for improved flammability.
本発明の目的は、植物性廃棄物を利用した難燃性に優れた樹脂組成物（難燃性樹脂組成物）、及び前記樹脂組成物（難燃性樹脂組成物）の製造方法を提供することである。 The objective of this invention provides the resin composition (flame retardant resin composition) excellent in the flame retardance using vegetable waste, and the manufacturing method of the said resin composition (flame retardant resin composition). That is.
本発明者らは、前記目的を達成すべく鋭意検討を行った結果、難燃剤を、ナス科の植物の茎等を粉砕して得た粉砕物に予め付着させた状態で合成樹脂に添加すると、難燃剤を効率的に合成樹脂中に分散配合できると共に、合成樹脂に難燃性を付与できることを見出し、本発明の完成に至った。 As a result of intensive studies to achieve the above object, the present inventors have added a flame retardant to a synthetic resin in a state in which the flame retardant is previously attached to a pulverized product obtained by pulverizing a stem of a solanaceous plant. The inventors have found that a flame retardant can be efficiently dispersed and blended in a synthetic resin, and that flame retardancy can be imparted to the synthetic resin, and the present invention has been completed.
前記課題を解決するための手段は、以下の通りである。即ち、
＜１＞ 合成樹脂と、ナス科植物の茎及び／又は葉を粉砕した粉砕物からなる担体に難燃剤を担持させてなる担持型難燃剤とを含有する難燃性樹脂組成物。
Means for solving the above problems are as follows. That is,
<1> A flame retardant resin composition comprising a synthetic resin and a supported flame retardant obtained by supporting a flame retardant on a carrier made of a pulverized product obtained by pulverizing a stem and / or leaf of a solanaceous plant.
＜２＞ 前記担持型難燃剤を、前記合成樹脂１００質量部に対して、５〜４０質量部の割合で含有する前記＜１＞に記載の難燃性樹脂組成物。 <2> The flame retardant resin composition according to <1>, wherein the supported flame retardant is contained in an amount of 5 to 40 parts by mass with respect to 100 parts by mass of the synthetic resin.
＜３＞ 前記担持型難燃剤は、前記難燃剤を、前記担体１００質量部に対して、１０〜２５０質量部の割合で含有する前記＜１＞又は＜２＞に記載の難燃性樹脂組成物。 <3> The flame retardant resin composition according to <1> or <2>, wherein the supported flame retardant contains the flame retardant at a ratio of 10 to 250 parts by mass with respect to 100 parts by mass of the carrier. Stuff.
＜４＞ 前記担体の大きさは、１０００μｍ以下である前記＜１＞〜＜３＞の何れか１つに記載の難燃性樹脂組成物。 <4> The flame-retardant resin composition according to any one of <1> to <3>, wherein the carrier has a size of 1000 μm or less.
＜５＞ 前記合成樹脂１００質量部に対して、５質量部以下の範囲で相溶化剤を含有する前記＜１＞〜＜４＞の何れか１つに記載の難燃性樹脂組成物。 <5> The flame-retardant resin composition according to any one of <1> to <4>, which contains a compatibilizer in a range of 5 parts by mass or less with respect to 100 parts by mass of the synthetic resin.
＜６＞ 前記合成樹脂は、ポリオレフィン系樹脂からなり、前記ナス科植物は、トマトからなり、前記難燃剤は、リン酸塩からなる前記＜１＞〜＜５＞の何れか１つに記載の難燃性樹脂組成物。 <6> The synthetic resin is made of a polyolefin-based resin, the solanaceous plant is made of tomato, and the flame retardant is phosphate, according to any one of <1> to <5>. Flame retardant resin composition.
＜７＞ 合成樹脂を軟化させる軟化工程と、軟化した合成樹脂に、ナス科植物の茎及び／又は葉を粉砕した粉砕物からなる担体に難燃剤を担持させてなる担持型難燃剤を添加して、前記合成樹脂と前記担持型難燃剤とを混練する混練工程とを有する難燃性樹脂組成物の製造方法。 <7> A softening step for softening a synthetic resin, and a supported flame retardant obtained by supporting a flame retardant on a softened synthetic resin, a carrier made of a pulverized product obtained by pulverizing a stem and / or leaf of a solanaceous plant. And a kneading step for kneading the synthetic resin and the supported flame retardant.
＜８＞ 前記担体に前記難燃剤を溶媒に分散又は溶解させてなる難燃剤溶液を含浸させて、前記担体に前記難燃剤を担持させる担持工程を有する前記＜７＞に記載の難燃性樹脂組成物の製造方法。 <8> The flame retardant resin according to <7>, further including a supporting step of impregnating the carrier with a flame retardant solution obtained by dispersing or dissolving the flame retardant in a solvent, and supporting the flame retardant on the carrier. A method for producing the composition.
本願発明によれば、植物性廃棄物を利用した難燃性に優れた樹脂組成物（難燃性樹脂組成物）、及び前記樹脂組成物（難燃性樹脂組成物）の製造方法を提供することができる。 According to the present invention, there are provided a resin composition (flame retardant resin composition) excellent in flame retardancy using plant waste and a method for producing the resin composition (flame retardant resin composition). be able to.
〔難燃性樹脂組成物〕
本発明の難燃性樹脂組成物は、合成樹脂と、担持型難燃剤とを含有するものからなる。図１は、本発明の難燃性樹脂組成物１を模式的に表した説明図である。図１には、担持型難燃剤５が、合成樹脂２中に分散されている状態の難燃性樹脂組成物１が模式的に示されている。
[Flame-retardant resin composition]
The flame retardant resin composition of the present invention comprises a synthetic resin and a supported flame retardant. FIG. 1 is an explanatory view schematically showing the flame
（担持型難燃剤）
担持型難燃剤は、担体に難燃剤を担持させたものからなる。担体は、ナス科植物に由来する茎及び／葉を粉砕した粉砕物からなる。
(Supported flame retardant)
The supported flame retardant is made by supporting a flame retardant on a carrier. The carrier consists of a pulverized product obtained by pulverizing stems and / or leaves derived from solanaceous plants.
（担体）
担体は、難燃剤を担持する部材であり、担体の表面や内部に難燃剤が固定される。
(Carrier)
The carrier is a member that carries a flame retardant, and the flame retardant is fixed to the surface or inside of the carrier.
担体として利用されるナス科植物は、果実等の有用な部分が収穫された後に残された状態のものであり、主として、茎、葉、根等からなる。そのような状態のナス科植物から、植物材料として、茎、葉が利用される。なお、担体に利用されるナス科植物の部位としては、茎のみでも良いし、葉のみでも良いし、茎と葉の双方であっても良い。担体に利用されるナス科植物の部位としては、難燃剤を担持させ易い等の理由により、特に茎が好ましい。 The solanaceous plant used as a carrier is in a state in which useful parts such as fruits are left after being harvested, and mainly consists of stems, leaves, roots and the like. From such a solanaceous plant, stems and leaves are used as plant materials. The part of the solanaceous plant used as a carrier may be a stem alone, a leaf alone, or both a stem and a leaf. As a part of the solanaceous plant used as a carrier, a stem is particularly preferable because it easily supports a flame retardant.
ナス科植物に由来する茎等の植物材料（以下、単に「植物材料」と称する場合がある）としては、植物中に含まれる水溶性成分が除去されたものが好ましい。植物中には、糖類（単糖類、二糖類、多糖類等）、植物酵素、アミノ酸等の有機成分、カリウム等の無機成分等の各種水溶性成分が含まれている。このような水溶性成分は、担持型難燃剤が添加されている製品の変色等の原因となる場合があるため、植物材料から、除去することが好ましい。 As a plant material such as a stem derived from a solanaceous plant (hereinafter sometimes simply referred to as “plant material”), a material from which water-soluble components contained in the plant have been removed is preferable. Plants contain various water-soluble components such as saccharides (monosaccharides, disaccharides, polysaccharides, etc.), plant enzymes, organic components such as amino acids, and inorganic components such as potassium. Since such a water-soluble component may cause discoloration of a product to which the supported flame retardant is added, it is preferably removed from the plant material.
植物材料から水溶性成分を除去する方法としては、例えば、水、アルコール等の水系溶媒に植物材料を浸漬又は植物材料を前記水系溶媒で洗浄して、植物材料から水溶性成分を抽出除去する方法、凍結乾燥（フリーズドライ）法等が挙げられる。なお、水溶性成分を除去した後の植物材料は、適宜、乾燥される。 As a method for removing water-soluble components from plant materials, for example, a method for extracting and removing water-soluble components from plant materials by immersing the plant materials in an aqueous solvent such as water or alcohol or washing the plant materials with the aqueous solvent. And freeze-drying method. In addition, the plant material after removing the water-soluble component is appropriately dried.
後述するように、植物材料を水系溶媒中に浸漬した状態で解砕（粉砕）することで、解砕と同時に水溶性成分の抽出除去を行ってもよい。 As will be described later, the water-soluble component may be extracted and removed simultaneously with the pulverization by pulverizing (pulverizing) the plant material in a state of being immersed in an aqueous solvent.
また、ナス科植物としては、本発明の目的を損なわない限り、特に制限はないが、例えば、ナス科ナス属の植物が好ましく、ナス、トマトがより好ましく、トマトが特に好ましい。 The solanaceous plant is not particularly limited as long as the object of the present invention is not impaired. For example, a plant belonging to the genus Solanum is preferable, eggplant and tomato are more preferable, and tomato is particularly preferable.
担体は、ナス科植物由来の茎等の植物材料が、粉末状に粉砕されたものからなる。植物材料の粉砕方法としては、本発明の目的を損なわない限り、特に制限はないが、例えば、機械的な方法で、圧縮力、せん断力、摩擦力、衝撃力等を加えて、植物材料を粉砕する方法（機械的粉砕方法）、爆砕等が挙げられる。 The carrier is formed by pulverizing a plant material such as a stem derived from a solanaceous plant into a powder form. The plant material is not particularly limited as long as it does not impair the object of the present invention. For example, the plant material may be compressed by mechanical methods such as compressive force, shear force, friction force, impact force, etc. Examples thereof include a pulverization method (mechanical pulverization method) and explosion.
なお、機械的粉砕方法では、例えば、高速回転ミル、各種ボールミル（転動ボールミル，振動ミル、遊星ミル）、媒体撹拌式ミル、気流式粉砕機等が利用される。 In the mechanical pulverization method, for example, a high-speed rotary mill, various ball mills (rolling ball mill, vibration mill, planetary mill), a medium stirring mill, an airflow pulverizer, or the like is used.
また、植物材料を、水等の水系溶媒中に浸漬した状態で、水中解砕装置（例えば、ホモジナイザー）を利用して、粉砕（解砕）してもよい。 Moreover, you may grind | pulverize (pulverize) a plant material using the submerged crushing apparatus (for example, homogenizer) in the state immersed in aqueous solvents, such as water.
植物材料の粉砕は、徐々に粒径が小さくなるように、複数の段階に分けて行ってもよい。例えば、茎等の植物材料を、数センチ程度の大きさに粗粉砕し、その粗粉砕物を更に、数百ミクロン程度まで粉砕（微粉砕）してもよい。 You may grind | pulverize plant material in several steps so that a particle size may become small gradually. For example, a plant material such as a stem may be roughly pulverized to a size of about several centimeters, and the coarsely pulverized product may be further pulverized (pulverized) to about several hundred microns.
また、植物材料の粉砕により得られた粉砕物は、篩等を利用して、適宜、分級されてもよい。 Moreover, the pulverized material obtained by pulverizing the plant material may be classified appropriately using a sieve or the like.
担体の形状、粒径等は、本発明の目的を損なわない限り、特に制限はないが、例えば、担体の粒径（最大直径）は、１０００μｍ以下が好ましく、６００μｍ以下がより好ましい。 The shape, particle size and the like of the carrier are not particularly limited as long as the object of the present invention is not impaired. For example, the particle size (maximum diameter) of the carrier is preferably 1000 μm or less, more preferably 600 μm or less.
なお、植物材料及びその粉砕物に対して、電磁波、温度、圧力及び薬品を利用した殺菌処理を施してもよい。 In addition, you may perform the sterilization process using electromagnetic waves, temperature, a pressure, and a chemical | medical agent with respect to plant material and its ground material.
ここで、担体の製造方法の一例を、図２を参照しつつ説明する。図２は、担体の製造方法の手順の一例を示すフロー図である。 Here, an example of the manufacturing method of the carrier will be described with reference to FIG. FIG. 2 is a flowchart showing an example of the procedure of the carrier manufacturing method.
図２のＳ１に示されるように、植物材料の茎の粗粉砕が行われる。その後、図２のＳ２に示されるように、得られた粗粉砕物が水中解砕される。水中解砕後に得られた解砕物は、図２のＳ３に示されるように、ろ過装置を利用してろ過され、残渣が回収される。回収された残渣は、図２のＳ４に示されるように、乾燥される。なお、図２のＳ２〜Ｓ４の工程は、複数回繰り返して行ってもよい。乾燥されたろ過残渣は、図２のＳ５に示されるように、更に細かく粉砕（微粉砕）される。その後、得られた粉砕物を、図２のＳ６に示されるように、篩い分け（分級）して、目的の粒径範囲の粉砕物を回収することで、担体が得られる（図２のＳ７参照）。 As shown in S1 of FIG. 2, the stalk of the plant material is roughly pulverized. Thereafter, as shown in S2 of FIG. 2, the obtained coarsely pulverized product is crushed in water. As shown in S3 of FIG. 2, the crushed material obtained after the crushing in water is filtered using a filtration device, and the residue is recovered. The collected residue is dried as shown in S4 of FIG. In addition, you may repeat the process of S2-S4 of FIG. 2 several times. The dried filtration residue is further finely pulverized (fine pulverized) as shown in S5 of FIG. Thereafter, the obtained pulverized product is sieved (classified) as shown in S6 of FIG. 2, and a pulverized product having a target particle size range is collected to obtain a carrier (S7 of FIG. 2). reference).
（難燃剤）
難燃剤は、担体に担持可能な物質であれば、特に制限はないが、担体に担持させ易い等の理由により、所定の溶媒に分散又は溶解されて難燃剤溶液を調製できるものが好ましい。後述するように、難燃剤溶液を、担体に含浸させ、その後、適宜、乾燥することで、担体に難燃剤を担持させることができる。
(Flame retardants)
The flame retardant is not particularly limited as long as it is a substance that can be supported on a carrier. However, a material that can be dispersed or dissolved in a predetermined solvent to prepare a flame retardant solution is preferable because it can be easily supported on a carrier. As will be described later, the flame retardant solution can be supported on the carrier by impregnating the carrier with a flame retardant solution and then drying appropriately.
難燃剤溶液に利用される溶媒としては、水、アルコール等の水系溶媒、有機溶媒等が挙げられ、特に、水系溶媒が好ましい。前記溶媒が、水系溶媒の場合、難燃剤としては、水溶性難燃剤が好ましく、特に、リン酸アンモニウム等のリン酸塩が好ましい。難燃剤は、１種類のものを単独で用いても良いし、２種以上のものを用いてもよい。 Examples of the solvent used in the flame retardant solution include water-based solvents such as water and alcohol, organic solvents, and the like, and water-based solvents are particularly preferable. When the solvent is an aqueous solvent, the flame retardant is preferably a water-soluble flame retardant, and particularly preferably a phosphate such as ammonium phosphate. One type of flame retardant may be used alone, or two or more types may be used.
難燃剤溶液中の難燃剤の濃度は、担体に担持させる難燃剤の量を考慮して、適宜、設定される。 The concentration of the flame retardant in the flame retardant solution is appropriately set in consideration of the amount of the flame retardant carried on the carrier.
担体に、難燃剤溶液を含浸させる方法としては、特に制限されないが、例えば、後述するドリップ装置を用いて含浸させてもよい。 The method for impregnating the carrier with the flame retardant solution is not particularly limited. For example, the carrier may be impregnated by using a drip device described later.
担持型難燃剤は、難燃剤を、担体１００質量部に対して、１０〜２５０質量部の割合で含有することが好ましく、５０〜２５０質量部の割合で含有することがより好ましく、１００〜２００質量部の割合で含有することが更に好ましい。担持型難燃剤における難燃剤の含有割合がこのような範囲であると、合成樹脂に対して、効果的に難燃性を付与することができる。 The supported flame retardant preferably contains the flame retardant in a proportion of 10 to 250 parts by mass, more preferably 50 to 250 parts by mass, with respect to 100 parts by mass of the carrier. More preferably, it is contained in a proportion by mass. When the content ratio of the flame retardant in the supported flame retardant is within such a range, flame retardancy can be effectively imparted to the synthetic resin.
ここで、担持型難燃剤の製造方法の一例を、図３を参照しつつ説明する。図３は、担持型難燃剤の製造方法の手順の一例を示すフロー図である。 Here, an example of a method for producing a supported flame retardant will be described with reference to FIG. FIG. 3 is a flowchart showing an example of a procedure of a method for producing a supported flame retardant.
図３のＳ１１に示されるように、難燃剤を溶媒に溶解等させて難燃剤溶液が作製される。次いで、図３のＳ１２に示されるように、別途、作製した担体（例えば、図２参照）を、難燃剤溶液に含浸させる。含浸後の担体は、図３のＳ１３に示されるように、所定の水分率となるまで乾燥され、溶媒が除去される。乾燥後、担体に難燃剤が担持された担持型難燃剤が得られる（図３のＳ１４参照）。 As shown in S11 of FIG. 3, the flame retardant solution is prepared by dissolving the flame retardant in a solvent. Next, as shown in S12 of FIG. 3, a separately prepared carrier (for example, see FIG. 2) is impregnated with a flame retardant solution. As shown in S13 of FIG. 3, the impregnated carrier is dried until a predetermined moisture content is obtained, and the solvent is removed. After drying, a supported flame retardant having a flame retardant supported on a carrier is obtained (see S14 in FIG. 3).
なお、他の担持型難燃剤の製造方法においては、粗粉砕の状態で、難燃剤溶液を用いた含浸処理、乾燥処理を行い、その後、粉砕処理を施して、担持型難燃剤を得ても良い。 In another method for producing a supported flame retardant, an impregnation process using a flame retardant solution and a drying process may be performed in a coarsely pulverized state, and then a pulverization process may be performed to obtain a supported flame retardant. good.
（合成樹脂）
難燃性樹脂組成物に含まれる合成樹脂としては、担持型難燃剤が配合されることで、難燃性が向上するものであれば、特に制限はないが、担持型難燃剤と混合し易い等の観点より、熱可塑性樹脂が好ましい。
(Synthetic resin)
The synthetic resin contained in the flame retardant resin composition is not particularly limited as long as the flame retardant improves by adding a supported flame retardant, but is easy to mix with the supported flame retardant. From such viewpoints, a thermoplastic resin is preferable.
熱可塑性樹脂としては、例えば、ポリエチレン（ＰＥ）、ポリプロピレン（ＰＰ）、エチレン−プロピレン共重合体等のポリオレフィン系樹脂、アクリル系樹脂、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）等のポリエステル系樹脂、ポリスチレン系樹脂、アクリロニトリル・ブタジエン・スチレン（ＡＢＳ）樹脂、変性ポニフェニレンエーテル等が挙げられる。熱可塑性樹脂は、単独で、又は２種以上を組み合わせて用いてもよい。これらの熱可塑性樹脂のうち、ポリオレフィン系樹脂が好ましい。 Examples of the thermoplastic resin include polyolefin resins such as polyethylene (PE), polypropylene (PP), and ethylene-propylene copolymer, polyester resins such as acrylic resin, polyethylene terephthalate (PET), and polybutylene terephthalate (PBT). Examples thereof include resins, polystyrene resins, acrylonitrile / butadiene / styrene (ABS) resins, and modified poniphenylene ether. You may use a thermoplastic resin individually or in combination of 2 or more types. Of these thermoplastic resins, polyolefin resins are preferred.
難燃性樹脂組成物は、合成樹脂１００質量部に対して、担持型難燃剤を、５〜４０質量部の割合で含有することが好ましい。担持型難燃剤の含有割合がこのような範囲であると、難燃性樹脂組成物の難燃性が確保され易い。 The flame retardant resin composition preferably contains a supported flame retardant in a proportion of 5 to 40 parts by mass with respect to 100 parts by mass of the synthetic resin. When the content ratio of the supported flame retardant is in such a range, the flame retardancy of the flame retardant resin composition is easily ensured.
（その他の成分）
難燃性樹脂組成物は、本発明の目的を損なわない限り、必要に応じて、相溶化剤、熱安定剤、可塑剤、紫外線吸収剤、酸化防止剤、顔料、染料、離型剤、抗菌剤、防カビ剤、発泡剤等の各種成分が添加されてもよい。
(Other ingredients)
The flame retardant resin composition may be used as necessary as a compatibilizer, a heat stabilizer, a plasticizer, an ultraviolet absorber, an antioxidant, a pigment, a dye, a mold release agent, and an antibacterial, as long as the object of the present invention is not impaired. Various components such as an agent, a fungicide, and a foaming agent may be added.
相溶化剤としては、例えば、無水マレイン酸変性ポリオレフィン（例えば、無水マレイン酸変性ポリプロピレン（「カヤブリッド」、化薬アクゾ株式会社製））が挙げられる。本発明の場合、相溶化剤の含有量は、合成樹脂１００質量部に対して、５質量部以下の範囲とすることが可能であり、好ましくは３質量部以下の範囲とすることが可能である。 Examples of the compatibilizing agent include maleic anhydride-modified polyolefin (for example, maleic anhydride-modified polypropylene (“Kayabrid”, manufactured by Kayaku Akzo Corporation)). In the case of the present invention, the content of the compatibilizer can be 5 parts by mass or less, preferably 3 parts by mass or less, with respect to 100 parts by mass of the synthetic resin. is there.
（難燃性樹脂組成物の製造方法）
難燃性樹脂組成物は、合成樹脂に、担持型難燃剤を添加し、それらを互いに混練することで得られる。なお、担持型難燃剤に起因する変色を抑制等するために、予め加熱により軟化させた状態の合成樹脂に、担持型難燃剤を添加して混合（混練）することが好ましい。
(Method for producing flame retardant resin composition)
The flame retardant resin composition is obtained by adding a supported flame retardant to a synthetic resin and kneading them together. In order to suppress discoloration caused by the supported flame retardant, it is preferable to add the supported flame retardant and mix (knead) the synthetic resin that has been softened by heating in advance.
ここで、難燃性樹脂組成物の製造方法の一例を、図４を参照しつつ説明する。図４は、難燃性樹脂組成物のペレットの製造方法の手順の一例を示すフロー図である。 Here, an example of the manufacturing method of a flame-retardant resin composition is demonstrated, referring FIG. FIG. 4 is a flowchart showing an example of the procedure of the method for producing a flame retardant resin composition pellet.
先ず、図４のＳ２１に示されるように、混練押出機を用いて、合成樹脂（熱可塑性樹脂）を軟化させる。続いて、図４のＳ２２に示されるように、加熱軟化した合成樹脂に、担持型難燃剤が添加される。なお、相溶化剤等の他の成分を添加する場合、Ｓ２２において、担持型難燃剤と共に、添加される。その後、図４のＳ２３に示されるように、合成樹脂、担持型難燃剤等が加熱されながら混練され、難燃性樹脂組成物が得られる。そして、図４のＳ２４に示されるように、難燃性樹脂組成物は混練押出機から押し出されてストランド化される。ストランド化された難燃性樹脂組成物は、冷却された後、ストランドカッターにより、所定長さに切断されて、ペレット状の難燃性樹脂組成物が得られる（図４のＳ２５参照）。 First, as shown in S21 of FIG. 4, the synthetic resin (thermoplastic resin) is softened using a kneading extruder. Subsequently, as shown in S22 of FIG. 4, a supported flame retardant is added to the heat-softened synthetic resin. In addition, when adding other components, such as a compatibilizing agent, it adds with a support type flame retardant in S22. Thereafter, as shown in S23 of FIG. 4, a synthetic resin, a supported flame retardant, and the like are kneaded while being heated to obtain a flame retardant resin composition. And as shown by S24 of FIG. 4, a flame-retardant resin composition is extruded from a kneading extruder, and is made into a strand. The flame-retardant resin composition formed into a strand is cooled and then cut into a predetermined length by a strand cutter to obtain a pellet-like flame-retardant resin composition (see S25 in FIG. 4).
なお、合成樹脂等を混練する装置としては、特に制限はなく、例えば、押出機（一軸、二軸等）、ラボプラストミル等の公知の混練装置が利用される。 In addition, there is no restriction | limiting in particular as an apparatus which knead | mixes synthetic resin etc. For example, well-known kneading apparatuses, such as an extruder (uniaxial, biaxial), a lab plast mill, are utilized.
以下、実施例に基づいて本発明を更に詳細に説明する。なお、本発明はこれらの実施例により何ら限定されるものではない。 Hereinafter, the present invention will be described in more detail based on examples. In addition, this invention is not limited at all by these Examples.
〔実施例１〕
（担体の作製）
実の収穫を終えたトマト（ナス科植物の一例）の茎を、粗粉砕装置（リョービ株式会社製）を利用して、１ｃｍ程度の大きさに切断及び粉砕し、茎の粗粉砕物を得た。次いで、得られた粗粉砕物（５００ｇ）を、水（２リットル）中に入れ、ホモジナイザーを利用して２分間水中解砕した後、ろ過した。ろ過したもの（ろ過残渣）に対し再び同様に水中解砕処理を２回繰り返し、計３回の水中解砕を行った。
[Example 1]
(Production of carrier)
Using a coarse crusher (made by Ryobi Co., Ltd.), the stems of tomatoes (an example of solanaceous plants) that have been harvested are cut and crushed to a size of about 1 cm to obtain a coarsely pulverized product of stems. It was. Next, the obtained coarsely pulverized product (500 g) was placed in water (2 liters), crushed in water for 2 minutes using a homogenizer, and then filtered. In the same way, the water disintegration treatment was repeated twice again on the filtered product (filtration residue), and the water disintegration was performed 3 times in total.
その後、最終的に得られた残渣に対して、乾燥処理を行った。なお、乾燥処理は、二段階で行った。先ず一段階目の乾燥処理は、温度を１３０℃、時間を８時間に設定して、殺菌も目的として行った。二段階目の乾燥処理は、温度を１０５℃、時間を１２時間に設定して行った。 Thereafter, the residue finally obtained was subjected to a drying treatment. The drying process was performed in two stages. First, the drying process at the first stage was performed for the purpose of sterilization by setting the temperature to 130 ° C. and the time to 8 hours. The second drying process was performed by setting the temperature to 105 ° C. and the time to 12 hours.
乾燥処理後のろ過残渣を、微粉砕装置（大阪ケミカル株式会社製）を利用して、５００μｍ程度に粉砕し、微粉砕物を得た。その後、微粉砕物を篩い分け装置により、篩い分けして、５００μｍ以下の微粉砕物からなるトマト由来の担体を得た。 The filtration residue after the drying treatment was pulverized to about 500 μm using a pulverizer (Osaka Chemical Co., Ltd.) to obtain a pulverized product. Thereafter, the finely pulverized product was sieved using a sieving device to obtain a tomato-derived carrier comprising a finely pulverized product of 500 μm or less.
（リン酸アンモニウム溶液の作製）
リン酸アンモニウムに水を加えて、リン酸アンモニウム水溶液（リン酸アンモニウム濃度：３０質量％）を作製した。
(Preparation of ammonium phosphate solution)
Water was added to ammonium phosphate to prepare an aqueous ammonium phosphate solution (ammonium phosphate concentration: 30% by mass).
（担持型難燃剤の作製）
図５に示されるドリップ装置１０を利用して、トマト残渣の粉砕物からなる担体に、リン酸アンモニウム水溶液（３０質量％）を含浸させた。ここで、先ずドリップ装置１０について説明する。
(Production of supported flame retardant)
Using a
ドリップ装置１０は、所謂コーヒードリッパーとして市販されているものであり、主として、ホルダ部１１、ドリップ部１２、フィルタ１３、及びろ液回収容器１４より構成されている。ホルダ部１１は、フィルタ１３が設置される部分であり、円錐を逆さにしたような上方に開口した漏斗のような形をなしている。なお、フィルタ１３は、円錐を逆さにしたような上方に開口したろ紙からなる。ドリップ部１２は、ホルダ部１１の下部に配置し、ホルダ部１１内の液体を下方へ滴下させるための貫通孔（不図示）を備えている。ろ液回収容器１４は、ドリップ部１２より滴下する液体を下方から受ける形で回収する容器である。なお、ホルダ部１１は、ろ液回収容器１４の上部に図示されない固定部材を利用して固定される。
The
続いて、ドリップ装置１０を利用して、担体にリン酸アンモニウム水溶液を含浸させる方法を説明する。先ず、ホルダ部１１内にフィルタ１３を設置し、そのフィルタ１３内に、担体３（３０ｇ）を入れた。次いで、リン酸アンモニウム水溶液（３０質量％）１５（１５０ｍｌ）を、フィルタ１３内に注ぎ入れて、担体３をリン酸アンモニウム水溶液１５に浸漬させた。その後、リン酸アンモニウム水溶液１５の滴下が終わるまで約１分間放置した。
Next, a method for impregnating a carrier with an aqueous ammonium phosphate solution using the
滴下が終了した後、フィルタ１３内の担体３を回収し、水分率が約６質量％程度となるまで、担体３を乾燥させた。このようにして、担体にリン酸アンモニウム水溶液を含浸させることで、担体にリン酸アンモニウムを担持させて、担持型難燃剤を得た。
After the dropping was completed, the
（難燃性樹脂組成物の作製）
溶融混練機としてラボブラストミルを使用して、ポリプロピレン（商品名「ＰＭＡ２０Ｖ」、サンアロマー社製）７０質量部と、上記担持型難燃剤３０質量部の割合で混練した。具体的には、先ずポリプロピレンのみを１８０℃で約２分間加熱して、ポリプロピレンを軟化させた。その後、軟化した状態のポリプロピレンに、上記担持型難燃剤を添加し、１８０℃で１０分間、３０ｒｐｍの条件で、ポリプロピレンと担持型難燃剤（リン酸アンモニウム付き粉砕物）とを混練した。
(Production of flame retardant resin composition)
Using a lab blast mill as a melt kneader, 70 parts by mass of polypropylene (trade name “PMA20V”, manufactured by Sun Allomer Co., Ltd.) and 30 parts by mass of the supported flame retardant were kneaded. Specifically, only the polypropylene was first heated at 180 ° C. for about 2 minutes to soften the polypropylene. Thereafter, the supported flame retardant was added to the softened polypropylene, and the polypropylene and the supported flame retardant (pulverized product with ammonium phosphate) were kneaded at 180 ° C. for 10 minutes at 30 rpm.
なお、相溶化剤として、無水マレイン酸変性ポリプロピレン（「カヤブリッド００６ＰＰ−Ｎ」）を１質量部、上記担持型難燃剤と共にポリプロピレンに添加した。 As a compatibilizer, 1 part by mass of maleic anhydride-modified polypropylene (“Kayabrid 006PP-N”) was added to the polypropylene together with the supported flame retardant.
その後、得られた混練物をプレス成形（加熱温度：１８０℃、プレス時間：約８分間）して、難燃性樹脂組成物からなシート状の成形品（厚み：１ｍｍ）を得た。 Thereafter, the obtained kneaded product was press-molded (heating temperature: 180 ° C., pressing time: about 8 minutes) to obtain a sheet-like molded product (thickness: 1 mm) from the flame-retardant resin composition.
そして、更に上記成形品を所定の大きさに切り出して、試験片（長さ１２５ｍｍ、幅１３ｍｍ、厚み１ｍｍ）を得た。
Further, the molded product was cut into a predetermined size to obtain a test piece (length 125 mm, width 13 mm,
〔実施例２〕
ポリプロピレンと担持型難燃剤との配合割合を、ポリプロピレン９０質量部、担持型難燃剤１０質量部に変更したこと以外は、基本的に、実施例１と同様にして、難燃性樹脂組成物からなるシート状の成形品、及び試験片を得た。
[Example 2]
Basically, in the same manner as in Example 1, except that the blending ratio of polypropylene and the supported flame retardant was changed to 90 parts by mass of polypropylene and 10 parts by mass of the supported flame retardant, from the flame retardant resin composition. A sheet-like molded product and a test piece were obtained.
〔比較例１〕
担持型難燃剤を配合せず、ポリプロピレンのみを用いること以外は、基本的に、実施例１と同様にして、ポリプロピレンからなるシート状の成形品、及び試験片を得た。
[Comparative Example 1]
A sheet-like molded article made of polypropylene and a test piece were obtained basically in the same manner as in Example 1 except that no supported flame retardant was blended and only polypropylene was used.
〔比較例２〕
担持型難燃剤に代えて、リン酸アンモニウムを担持させていない担体（トマト残渣の粉砕物）を用いつつ、ポリプロピレンと担体との配合割合を、ポリプロピレン７０質量部、担体３０質量部に変更したこと以外は、基本的に、実施例１と同様にして、シート状の成形品、及び試験片を得た。
[Comparative Example 2]
The blending ratio of polypropylene and carrier was changed to 70 parts by mass of polypropylene and 30 parts by mass of the carrier while using a carrier that did not carry ammonium phosphate (ground tomato residue) instead of the supported flame retardant. Except for the above, a sheet-like molded product and a test piece were obtained basically in the same manner as in Example 1.
〔比較例３〕
ポリプロピレンと担体との配合割合を、ポリプロピレン９０質量部、担体１０質量部に変更したこと以外は、基本的に、比較例２と同様にして、シート状の成形品、及び試験片を得た。
[Comparative Example 3]
A sheet-like molded product and a test piece were obtained basically in the same manner as in Comparative Example 2 except that the blending ratio of the polypropylene and the carrier was changed to 90 parts by mass of polypropylene and 10 parts by mass of the carrier.
〔燃焼試験による難燃性評価〕
実施例１，２及び比較例１〜３の各試験片について、ＵＬ９４規格に基づいて、燃焼試験を行い、難燃性を評価した。結果は、表１にまとめた。
[Flame resistance evaluation by combustion test]
About each test piece of Examples 1, 2 and Comparative Examples 1-3, the combustion test was done based on UL94 specification and the flame retardance was evaluated. The results are summarized in Table 1.
表１に示されるように、実施例１については、ＵＬ９４の垂直燃焼試験を行い、Ｖ０等級という高い難燃性を示すことが確かめられた。 As shown in Table 1, the vertical combustion test of UL94 was conducted for Example 1, and it was confirmed that the flame retardancy as high as V0 was shown.
これに対し、実施例２及び比較例１〜３については、Ｖ０等級の難燃性は得られなかった。そのため、表１に示されるように、ＵＬ９４ＨＢの水平燃焼試験を行った。その結果、実施例２及び比較例１〜３では、何れの場合も、１分当たりの燃焼速度が、７６．２ｍｍ／ｍｉｎ以下であり、ＨＢ等級の難燃性を備えることが確かめられた。 On the other hand, about Example 2 and Comparative Examples 1-3, the flame retardance of V0 grade was not obtained. Therefore, as shown in Table 1, a horizontal combustion test of UL94HB was performed. As a result, in Example 2 and Comparative Examples 1 to 3, the burning rate per minute was 76.2 mm / min or less, and it was confirmed that the flame retardancy of HB grade was provided.
ただし、表１に示されるように、担持型燃焼剤を含む実施例２の試験片では、燃焼速度が５６．８ｍｍ／ｍｉｎであり、各比較例の燃焼速度と比べて、燃焼速度が遅く、難燃性に優れることが確かめられた。また、難燃性試験中のドリップ数についても、実施例２の場合が最も少なく、ドリップ防止性にも優れることが確かめられた。なお、比較例１のドリップ数については、試験片から絶えずドリップが発生する状態であり、約３００回という結果となった。 However, as shown in Table 1, in the test piece of Example 2 including the supported combustion agent, the combustion speed is 56.8 mm / min, and the combustion speed is slower than the combustion speed of each comparative example. It was confirmed that it was excellent in flame retardancy. In addition, the number of drip during the flame retardancy test was the smallest in Example 2, and it was confirmed that the drip prevention was excellent. In addition, about the drip number of the comparative example 1, it was in the state which a drip generate | occur | produces continuously from a test piece, and resulted in about 300 times.
〔実施例３〕
リン酸アンモニウム水溶液のリン酸アンモニウム濃度を、２０質量％に変更したこと以外は、実施例１と同様にして、トマト残渣の粉砕物からなる担体に、リン酸アンモニウム水溶液を含浸させることで、担体にリン酸アンモニウムを担持させて、担持型難燃剤（２０質量％）を得た。
Example 3
Except that the ammonium phosphate concentration of the aqueous ammonium phosphate solution was changed to 20% by mass, the carrier made of a pulverized tomato residue was impregnated with the aqueous ammonium phosphate solution in the same manner as in Example 1. Was supported with ammonium phosphate to obtain a supported flame retardant (20% by mass).
担持型難燃剤（３０質量％）に代えて、担持型難燃剤（２０質量％）を用いつつ、ポリプロピレンと担持型難燃剤（２０質量％）との配合割合を、ポリプロピレン９０質量部、担持型難燃剤（２０質量％）１０質量部に変更したこと以外は、基本的に、実施例１と同様にして、シート状の成形品、及び試験片を得た。 In place of the supported flame retardant (30% by mass), the blending ratio of polypropylene and the supported flame retardant (20% by mass) is changed to 90 parts by mass of polypropylene, supported type while using the supported flame retardant (20% by mass). A sheet-like molded product and a test piece were obtained basically in the same manner as in Example 1 except that the flame retardant (20% by mass) was changed to 10 parts by mass.
〔実施例４〕
リン酸アンモニウム水溶液のリン酸アンモニウム濃度を、４０質量％に変更したこと以外は、実施例１と同様にして、トマト残渣の粉砕物からなる担体に、リン酸アンモニウム水溶液を含浸させることで、担体にリン酸アンモニウムを担持させて、担持型難燃剤（４０質量％）を得た。
Example 4
Except that the ammonium phosphate concentration of the aqueous ammonium phosphate solution was changed to 40% by mass, the carrier made of a pulverized tomato residue was impregnated with the aqueous ammonium phosphate solution in the same manner as in Example 1. Was supported with ammonium phosphate to obtain a supported flame retardant (40% by mass).
担持型難燃剤（３０質量％）に代えて、担持型難燃剤（４０質量％）を用いつつ、ポリプロピレンと担持型難燃剤（４０質量％）との配合割合を、ポリプロピレン９０質量部、担持型難燃剤（４０質量％）１０質量部に変更したこと以外は、基本的に、実施例１と同様にして、シート状の成形品、及び試験片を得た。 Instead of the supported flame retardant (30% by mass), the blending ratio of polypropylene and the supported flame retardant (40% by mass) was changed to 90 parts by mass of polypropylene, supported type while using the supported flame retardant (40% by mass). A sheet-like molded product and a test piece were obtained basically in the same manner as in Example 1 except that the flame retardant (40% by mass) was changed to 10 parts by mass.
〔強度評価〕
実施例２〜４、及び比較例１，３の各試験片について、引張圧縮試験機を用いて、応力σとひずみεとの関係（ｓ−ｓ曲線）を求めた。結果（グラフ）は、図６に示した。そして、得られた結果（ｓ−ｓ曲線）より、各試験片について、曲げ弾性率（ＭＰａ）及び曲げ強さ（ＭＰａ）を求めた。求めた曲げ弾性率（ＭＰａ）及び曲げ強さ（ＭＰａ）は、表２にまとめた。
[Strength evaluation]
About each test piece of Examples 2-4 and Comparative Examples 1 and 3, the relationship (s-s curve) of stress (sigma) and distortion (epsilon) was calculated | required using the tension compression testing machine. The results (graph) are shown in FIG. And the bending elastic modulus (MPa) and bending strength (MPa) were calculated | required about each test piece from the obtained result (ss curve). The obtained bending elastic modulus (MPa) and bending strength (MPa) are summarized in Table 2.
図６及び表２に示されるように、実施例３，２，４の各試験片では、担体に含浸させるリン酸アンモニウムの濃度が高くなるにつれて、曲げ弾性率が向上することが確かめられた。また、実施例３，２，４の各試験片の曲げ強さについては、殆ど差が見られなかった。 As shown in FIG. 6 and Table 2, it was confirmed that in each of the test pieces of Examples 3, 2, and 4, the flexural modulus improved as the concentration of ammonium phosphate impregnated in the carrier increased. Moreover, about the bending strength of each test piece of Example 3,2,4, the difference was hardly seen.
〔トマト残渣に担持されるリン酸アンモニウムの検証〕
トマトの茎（フリーズドライ済み）を、１センチ程度の長さで切断したものを試験片Ｔとした。この試験片Ｔに、リン酸アンモニウム水溶液（リン酸アンモニウム濃度：４０質量％）に、５分間浸漬した。その後、水分率が約６％となるまで試験片Ｔを乾燥させた。乾燥後の試験片Ｔを、ＥＤＸ（エネルギー分散型Ｘ線分光法、装置名「電界放出型操作電子顕微鏡（ＦＥ−ＳＥＭ）」、日本電子株式会社製）を用いて、試験片の各部位に含まれる各成分を検出した。試験片の各検出部位は、図７の符号１〜５で示される部分である。図７には、試験片（茎）の断面写真が示されている。図７の検出部位Ｉは表皮であり、検出部位ＩＩは表皮と維管束の境界付近であり、検出部位ＩＩＩは維管束であり、検出部位ＩＶは維管束と髄との境界付近であり、検出部位Ｖは髄である。
[Verification of ammonium phosphate supported on tomato residue]
A test piece T was prepared by cutting a tomato stem (freeze-dried) to a length of about 1 cm. This test piece T was immersed in an aqueous ammonium phosphate solution (ammonium phosphate concentration: 40% by mass) for 5 minutes. Thereafter, the test piece T was dried until the moisture content was about 6%. The test piece T after drying is applied to each part of the test piece using EDX (energy dispersive X-ray spectroscopy, apparatus name “field emission type operation electron microscope (FE-SEM)”, manufactured by JEOL Ltd.). Each component contained was detected. Each detection part of a test piece is a part shown by numerals 1-5 of Drawing 7. FIG. 7 shows a cross-sectional photograph of the test piece (stem). The detection site I in FIG. 7 is the epidermis, the detection site II is near the boundary between the epidermis and the vascular bundle, the detection site III is the vascular bundle, and the detection site IV is near the boundary between the vascular bundle and the medulla. Site V is the medulla.
各検出部位における各成分の検出スペクトルの結果は、それぞれ図８〜図１２に示した。図８〜図１２に示されるように、検出部位ＩＩＩ（維管束）を除くすべての部位において、リン（Ｐ）成分が検出された。このことから、各検出部位に、リン酸アンモニウムが存在していることが確認された。リン酸アンモニウムは、茎の表皮のみならず、表皮（外皮）と維管束との境界部分や、維管束と髄との境界部分でも確認され、リン酸アンモニウムが茎の内部にも浸透していることが確かめられた。 The results of the detection spectrum of each component at each detection site are shown in FIGS. As shown in FIGS. 8 to 12, the phosphorus (P) component was detected at all sites except the detection site III (vascular bundle). From this, it was confirmed that ammonium phosphate was present at each detection site. Ammonium phosphate is found not only at the epidermis of the stem, but also at the boundary between the epidermis (outer skin) and the vascular bundle, and at the boundary between the vascular bundle and the medulla, and ammonium phosphate penetrates into the stem. It was confirmed.
１…難燃性樹脂組成物、２…合成樹脂（母材）、３…担体、４…難燃剤、５…担持型難燃剤、１０…ドリップ装置、１１…ホルダ部、１２…ドリップ部、１３…フィルタ、１４…ろ液回収容器、１５…リン酸アンモニウム水溶液（難燃剤溶液）
DESCRIPTION OF
Claims (8)
前記難燃剤は、リン酸塩を含み、かつ
前記難燃剤は、前記粉砕物に含まれる表皮と維管束との境界部分、及び維管束と髄との境界部分に担持される難燃性樹脂組成物。 Containing a synthetic resin and a supported flame retardant obtained by supporting a flame retardant on a carrier containing a pulverized product obtained by pulverizing tomato stems ;
The flame retardant comprises phosphate, and
The flame retardant is a flame retardant resin composition supported on a boundary portion between an epidermis and a vascular bundle and a boundary portion between a vascular bundle and a medulla contained in the pulverized product.
軟化した合成樹脂に、トマトの茎を粉砕した粉砕物であって、表皮と維管束との境界部分、及び維管束と髄との境界部分を含む粉砕物を含む担体に、リン酸塩を含む難燃剤を前記表皮と前記維管束との前記境界部分、及び前記維管束と前記髄との前記境界部分に担持させてなる担持型難燃剤を添加して、前記合成樹脂と前記担持型難燃剤とを混練する混練工程とを有する難燃性樹脂組成物の製造方法。 A softening process for softening the synthetic resin;
The softened synthetic resin, a pulverized product obtained by pulverizing tomato stem, the boundary portion between the skin and the vascular and the carrier containing a pulverized product containing the boundary portion of the vascular bundles and marrow, including phosphate A flame retardant is added to the boundary portion between the epidermis and the vascular bundle, and a supported flame retardant that is supported on the boundary portion between the vascular bundle and the medulla, and the synthetic resin and the supported flame retardant are added. And a kneading step for kneading the flame retardant resin composition.
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