JP2001164031A - Moldings comprising porous foam resin having heat- resistant and flame-retardant resin mixture layer and molding production thereof - Google Patents
Moldings comprising porous foam resin having heat- resistant and flame-retardant resin mixture layer and molding production thereofInfo
- Publication number
- JP2001164031A JP2001164031A JP35261899A JP35261899A JP2001164031A JP 2001164031 A JP2001164031 A JP 2001164031A JP 35261899 A JP35261899 A JP 35261899A JP 35261899 A JP35261899 A JP 35261899A JP 2001164031 A JP2001164031 A JP 2001164031A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- boron
- thermosetting resin
- inorganic compound
- based inorganic
- 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.)
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- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
Description
【0001】[0001]
【産業上の利用分野】本発明は、耐熱・難燃性が要求さ
れる建材などに用いられるボード、構造部材としてのプ
レートや成形品及び軽量成形部材に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a board used for a building material requiring heat resistance and flame retardancy, a plate as a structural member, a molded product, and a lightweight molded member.
【0002】[0002]
【従来の技術】建材などに用いられる断熱ボードは、断
熱性を持たせるためにポリスチレンなどの樹脂を発泡さ
せていわゆる発泡成形体としてボード状などの所定の形
状に成形して、これらの独立気泡により断熱性を持たせ
ている。これらの部材は、軽量・安価でしかも断熱性に
優れた特性を有するが、火災などに遇うとこれらの樹脂
素材は低融点であるため速やかに溶解して、気泡がつぶ
れるために構造体全体が速やかに収縮してしまい、同時
にこれらの樹脂は火災の熱で気化・燃焼し始めるために
黒煙を発し、建物内の視界を遮って内部の居住者の脱出
を妨げるばかりでなく、燃焼に伴って有害なガスをも発
生するため、火災の際に犠牲者が出る原因ともなってい
る。2. Description of the Related Art Insulating boards used for building materials are formed by foaming a resin such as polystyrene into a predetermined shape such as a board as a so-called foamed molded article so as to have heat insulating properties. To provide heat insulation. These members are lightweight, inexpensive, and have excellent heat insulation properties. However, in the event of fire, these resin materials have a low melting point and dissolve quickly, causing bubbles to collapse and the entire structure to collapse. These resins shrink quickly, and at the same time, these resins emit black smoke as they begin to vaporize and burn due to the heat of the fire, not only blocking the view inside the building and preventing the occupants inside from escaping, but also accompanying the burning. It also emits harmful gases, causing casualties in the event of a fire.
【0003】これに対して、この様な断熱性のボードな
どに耐熱性を付与したり、難燃性化する試みも行われて
いるが、このために添加した材料のために本来の断熱性
などの特性を損なったり、コストが上昇するなどのため
満足の行く成果を得られていない。[0003] On the other hand, attempts have been made to impart heat resistance to such a heat-insulating board or to make it flame-retardant. Satisfactory results have not been obtained due to impaired characteristics and increased costs.
【0004】たとえば、実開昭53‐2463号公報に
は、珪素又はホウ素を含有する無機物質によって気泡の
壁とし、この壁に水酸化アルミニウムを含有する合成樹
脂を一体とし、かつこれらの間に不燃無機質の粒子を配
してなるを有する合成樹脂発泡体が記載され、また、特
開昭51−67625号公報には、無機質泡状粒子とそ
の隙間に充填されて泡状粒子を互いに結合した発泡膨張
性の無機質粉粒物を混入した合成樹脂発泡体とからな
り、無機質粉粒物は発泡したとき前記泡状粒子の隙間以
上の容積となる量が合成樹脂発泡体に混入されている耐
火断熱材であり、これらの発泡により無機質泡状体と無
機質粉粒物及び樹脂発泡体をからなるの発泡成形体が得
られることが記載されている。For example, Japanese Utility Model Laid-Open Publication No. 53-2463 discloses that an inorganic substance containing silicon or boron is used to form a bubble wall, and a synthetic resin containing aluminum hydroxide is integrally formed on the wall, and between these walls. A synthetic resin foam having non-combustible inorganic particles disposed therein is described, and JP-A-51-67625 discloses that inorganic foam particles and foam particles filled in gaps are bonded to each other. A synthetic resin foam mixed with a foam-expandable inorganic powder, wherein the amount of the inorganic powder mixed with the synthetic resin foam is such that when foamed, the volume of the foam becomes larger than the gap between the foam particles. It is described that this foam is a heat insulating material, and that a foamed molded article composed of an inorganic foam, an inorganic powder, and a resin foam can be obtained by foaming.
【0005】しかしながら、これらはいずれも、本来の
発泡成形ボードからすると、断熱性などの特性を低下し
成形体としても制約が多いのみか、必ずしも所期の耐熱
性・難燃性が得られていない。[0005] However, in the case of these foamed boards, the properties such as heat insulating properties are reduced and the molded articles are limited in many cases, or the desired heat resistance and flame retardancy are not necessarily obtained. Absent.
【0006】[0006]
【発明が解決しようとする課題】本発明は、これらの事
情に鑑み、従来の樹脂発泡成形ボードの断熱性や軽量
さ、或いは取り扱いが容易でかつ低コスト等の特性を損
なうことなく、火災などの加熱に対して優れた、耐熱性
を発揮して火災の際に溶融収縮することなく、また燃焼
せずかつ火災が犠牲者を伴う大きな要因となっている黒
煙や有毒なガスの発生を抑制することのできる成形体の
提供を課題とする。SUMMARY OF THE INVENTION In view of these circumstances, the present invention provides a conventional resin foam molded board which can be used for a fire or the like without impairing the heat insulating property and light weight, or the properties such as easy handling and low cost. It excels in heating, exhibits heat resistance, does not melt and shrink in the event of a fire, does not burn, and generates black smoke and toxic gas, which is a major factor that causes casualties in fires. An object is to provide a compact that can be suppressed.
【0007】[0007]
【課題を解決するための手段】本発明は、多孔性発泡樹
脂粒子外周をホウ素系無機化合物及び熱硬化性樹脂から
なる混合物層で被覆した多孔性発泡樹脂からなる成形体
であり、その多孔性発泡樹脂粒子がポリスチレン樹脂か
らなり、ホウ素系無機化合物がホウ酸であり、熱硬化性
樹脂がフェノール樹脂とすることで従来の発泡ポリスチ
レンと同様の製法により容易にかつ安価に得ることがで
きる。また、上記熱硬化性樹脂に、ホウ素系無機化合物
の外、ガラス繊維、炭素繊維などの繊維強化材及び、又
はシリカ、シラス、タルクなどの無機粉粒体を添加する
ことにより、耐熱性・難燃性を更に向上させ或いこれに
加えて強度、剛性等の他の特性を向上する。SUMMARY OF THE INVENTION The present invention relates to a molded article made of a porous foamed resin in which the outer periphery of a porous foamed resin particle is coated with a mixture layer composed of a boron-based inorganic compound and a thermosetting resin. When the foamed resin particles are made of a polystyrene resin, the boron-based inorganic compound is boric acid, and the thermosetting resin is a phenol resin, it can be easily and inexpensively obtained by the same production method as the conventional foamed polystyrene. Further, by adding a fiber-reinforced material such as glass fiber and carbon fiber and / or an inorganic powder such as silica, shirasu, and talc to the thermosetting resin, in addition to the boron-based inorganic compound, heat resistance and difficulty are improved. It further improves the flammability or, in addition, other properties such as strength, rigidity.
【0008】また、上記成形体の製造方法として、発泡
剤を含有する樹脂粒子をホウ素系無機化合物を添加した
熱硬化性樹脂により被覆し、発泡成形処理を行うことに
より所定の形状の成形体とするものであり、また、上記
被覆工程に先立って、樹脂粒子を所定の比率で予備発泡
させることにより、ホウ素系無機化合物を含有する樹脂
被覆層の厚さを調整し、本発泡成形工程を円滑に行うこ
とができる。[0008] Further, as a method for producing the molded article, a resin article containing a foaming agent is coated with a thermosetting resin to which a boron-based inorganic compound is added, and a foamed molding treatment is performed to obtain a molded article having a predetermined shape. In addition, prior to the coating step, the resin particles are pre-foamed at a predetermined ratio to adjust the thickness of the resin coating layer containing the boron-based inorganic compound, thereby facilitating the main foam molding step. Can be done.
【0009】多孔性発泡樹脂粒子外周をホウ素系無機化
合物及び熱硬化性樹脂からなる混合物層で被覆した多孔
性発泡樹脂からなる成形体は、いわゆるポリスチレン発
泡成形体等と同様に気泡状の構造によって効果的に断熱
性を発揮することができる。この構造が火災などの加熱
に対して混合層が効果的に耐熱性・難燃性を発揮するメ
カニズムに寄与しているものと考えられる。ホウ素系無
機化合物と熱硬化性樹脂との混合物からなる被覆層が、
この様な加熱に際してどのような反応を生じるのか厳密
な反応メカニズムなどは明かではないが、熱硬化性樹脂
は加熱に伴って硬化してその気泡状の構造を保つと考え
られ、そして、さらに高温度になってホウ素系無機化合
物のガラス化が進行すると、これらの硬化して気泡状の
形状を保つ熱硬化性樹脂を溶融したガラスが覆って外気
から遮断することにより、その焼失を防止するものと考
えられる。ホウ素化合物のガラス化する反応は広く知ら
れており、例えばホウ酸は、メタホウ酸(HBO2)を
経由してピロホウ酸(H2B4O7)に変化してガラス状
となり、さらに高温で無水ホウ酸(B2O3)に変化する
が、ナトリウム塩などの存在でガラス状化が容易に進行
する。したがって、火災などの加熱により硬化して気泡
状の構造を保つ熱硬化性樹脂とこの熱硬化性樹脂の硬化
する過程で溶融して硬化した樹脂を被覆して外気から遮
断し、更に高温度での反応を防止するものであれば、熱
硬化性樹脂とそれに混合すべき無機化合物の組合せは上
記の例に限らない。A molded article made of a porous foamed resin in which the outer periphery of the porous foamed resin particles is coated with a mixture layer of a boron-based inorganic compound and a thermosetting resin has a cellular structure like a so-called polystyrene foam molded article. Effective heat insulation can be exhibited. It is considered that this structure contributes to a mechanism in which the mixed layer effectively exhibits heat resistance and flame retardance against heating such as fire. A coating layer composed of a mixture of a boron-based inorganic compound and a thermosetting resin,
The exact mechanism of the reaction that occurs during such heating is not clear, but it is believed that the thermosetting resin cures with heating and retains its cellular structure. When the temperature rises and the vitrification of the boron-based inorganic compound proceeds, these are cured and the thermosetting resin that keeps the bubble-like shape is covered with the melted glass and shielded from the outside air to prevent its burning. it is conceivable that. The reaction of vitrifying a boron compound is widely known. For example, boric acid is converted into pyroboric acid (H 2 B 4 O 7 ) via metaboric acid (HBO 2 ) to become glassy, and further at a high temperature. It changes to boric anhydride (B 2 O 3 ), but vitrification proceeds easily in the presence of a sodium salt or the like. Therefore, it is covered with a thermosetting resin that is cured by heating such as a fire to maintain a cellular structure and a resin that has been melted and cured in the process of curing the thermosetting resin, and is shielded from the outside air. The combination of the thermosetting resin and the inorganic compound to be mixed therewith is not limited to the above example as long as the reaction is prevented.
【0010】加熱が進行するとこれらの反応領域もそれ
に伴ってある程度進行するが、上記の多孔性発泡樹脂構
造が維持されることから加熱の及ぶ範囲も限定され、一
定以上に進行することはない。したがって、当初多孔性
発泡樹脂の形状を支持した樹脂はその加熱過程で多孔性
発泡樹脂外周を被覆する熱硬化性樹脂層に融合して一体
となり、次いでホウ素系無機化合物のガラス層に取り込
まれて一体となると考えられるが、これらの多孔性発泡
樹脂の形状が維持されることにより成形体内部への熱伝
達が遮断されてそれ以上の進行は阻止されるから、例
え、加熱に伴ってこれらの樹脂が燃焼しても、その範囲
はこれらの表面領域に限られたものとなるから、黒煙や
有毒なガスの発生も防止することができる。As the heating progresses, these reaction regions also progress to some extent. However, since the above-mentioned porous foamed resin structure is maintained, the range of the heating is also limited, and the progress does not proceed beyond a certain level. Therefore, the resin that initially supported the shape of the porous foamed resin was fused and integrated with the thermosetting resin layer covering the outer periphery of the porous foamed resin in the heating process, and then incorporated into the glass layer of the boron-based inorganic compound. Although it is considered that they are integrated, heat transfer to the inside of the molded article is blocked by maintaining the shape of these porous foamed resins and further progress is prevented. Even if the resin is burned, the range is limited to these surface areas, so that generation of black smoke and toxic gas can be prevented.
【0011】これらの成形体の軽量性、強度、耐水性や
素材としての安定性等の特性も、多孔性発泡樹脂粒子外
周を覆うホウ素系無機化合物及び熱硬化性樹脂からなる
混合物層自体が比較的軽量で薄いこと、化学的に安定で
あること及び一定の強度を有するものであり、さらにこ
れらの成形体において求められる強度は比較的均一な面
荷重に対するものであることから本来の多孔性発泡樹脂
粒子による成形体の強度などの特性が良く保たれる。The properties of these molded articles, such as light weight, strength, water resistance and stability as a material, are also comparable to those of the mixture layer itself composed of a boron-based inorganic compound and a thermosetting resin covering the outer periphery of the porous foamed resin particles. It is thin and light, chemically stable, and has a certain strength. Further, the strength required for these molded articles is for a relatively uniform surface load. The properties such as the strength of the molded body due to the resin particles are well maintained.
【0012】このような成形体を製造する方法として、
従来の発泡ポリスチレン等の発泡成形工程を利用するこ
とにより効率的かつ効果的に製造することができるので
あって、多孔性発泡樹脂粒子を形成するためには発泡剤
を含有或いは発泡ガスを含浸させて発泡前処理を行った
ポリスチレンビーズなどの粒子状の樹脂を、ホウ素系無
機化合物を混合した熱硬化性樹脂で被覆し、これを加熱
により発泡成形処理して成形体とすることにより、成形
体を構成する多孔性発泡樹脂は、本来の気泡状構造を形
成する樹脂層に対してホウ素系無機化合物を混合した熱
硬化性樹脂層を重ねた複数の層からなるものとすること
ができる。As a method for producing such a molded article,
It can be efficiently and effectively manufactured by utilizing a conventional foam molding process such as expanded polystyrene.In order to form porous foamed resin particles, a foaming agent is contained or a foaming gas is impregnated. A resin in the form of particles, such as polystyrene beads, which has been subjected to a pre-foaming treatment, is coated with a thermosetting resin in which a boron-based inorganic compound is mixed, and this is subjected to a foam molding treatment by heating to form a molded body. May be composed of a plurality of layers in which a thermosetting resin layer obtained by mixing a boron-based inorganic compound with a resin layer forming an original cellular structure is laminated.
【0013】この構造によって、本来の気泡状構造を構
成する樹脂のみでは達成することができなかった耐熱性
や難燃性などの性質を成形体に付与することができる。
ホウ素系無機化合物を混合した熱硬化性樹脂を気泡状構
造を形成する樹脂に被覆するには、液状の熱硬化性樹脂
前駆体又は未硬化の熱硬化性樹脂を種々の周知・慣用の
方法で塗布しても良く、また溶剤に溶解して塗布後溶剤
を蒸散させてもよい。これらの方法は、熱硬化性樹脂の
種類や性質に応じて適宜の方法で良いのであって、上記
の発泡工程の加熱などの条件下で適度の粘性、流動性を
有していて発泡によって形成される気泡状構造の粒子の
表面に均一な被膜を生成することができれば良い。この
発泡成形の工程を利用することにより、格別の工程を要
することなく上記した所定の複数の層構造を有する多孔
性発泡樹脂からなる成形体を製造することができる。According to this structure, properties such as heat resistance and flame retardancy, which cannot be achieved only by the resin constituting the original cellular structure, can be imparted to the molded article.
In order to coat a thermosetting resin mixed with a boron-based inorganic compound on a resin forming a cellular structure, a liquid thermosetting resin precursor or an uncured thermosetting resin can be coated by various well-known and commonly used methods. It may be applied, or may be dissolved in a solvent to evaporate the solvent after application. These methods may be any appropriate method depending on the type and properties of the thermosetting resin, and have appropriate viscosity and fluidity under conditions such as heating in the above foaming step and are formed by foaming. It is sufficient that a uniform coating can be formed on the surface of the particles having a cellular structure. By utilizing this foam molding step, a molded article made of the porous foamed resin having the above-described predetermined plural layer structure can be manufactured without requiring any special step.
【0014】[0014]
【実施例】以下、具体的な実施例により説明する。図1
は、本発明のホウ素系無機化合物を含有する樹脂によっ
て被覆した多孔性発泡樹脂粒子からなる成形体で、従来
の発泡ポリスチレンと同様に気泡状の樹脂2同士が密着
して一体に成形された構造からなる。The present invention will be described below with reference to specific examples. FIG.
Is a molded article made of porous foamed resin particles coated with a resin containing the boron-based inorganic compound of the present invention, and has a structure in which cellular resins 2 are closely adhered to each other and integrally molded in the same manner as conventional foamed polystyrene. Consists of
【0015】図2は、図1の成形体の拡大図で、多孔性
発泡樹脂粒子2の外周面にホウ素系無機化合物を含有す
る熱硬化性樹脂の被覆層3が形成されており、この被覆
層を介して多孔性発泡樹脂が密着して一体化されてい
る。この気泡状構造を構成する樹脂は、発泡などの手法
により微小な中空体を形成できるものであれば格別の制
限は無く、たとえばポリスチレン、ポリエチレン、ポリ
プロピレン、ポリ塩化ビニル等の汎用プラスチック及び
ポリアミド,ポリカーボネート、変性ポリフェニレンエ
ーテル、ポリエーテルスルフォン、ポリエステル、ABS
などのエンジニアリングプラスチックなどが適用でき
る。なお、ポリスチレンを多孔性発泡樹脂に用いる場
合、ポリスチレンは、軟化点が80〜100℃と低く、
長期連続使用温度は50℃とされているところからこの
様な温度以上の環境で使用される場合には軟化点が高
く、強度の高いポリカーボネート樹脂、ポリアミド樹脂
などのエンジニアリングプラスチックを用いる必要があ
る。FIG. 2 is an enlarged view of the molded article of FIG. 1, in which a coating layer 3 of a thermosetting resin containing a boron-based inorganic compound is formed on the outer peripheral surface of the porous foamed resin particles 2. The porous foamed resin is tightly integrated via the layer. The resin constituting the cellular structure is not particularly limited as long as it can form a minute hollow body by a method such as foaming. For example, general-purpose plastics such as polystyrene, polyethylene, polypropylene, and polyvinyl chloride, and polyamides and polycarbonates , Modified polyphenylene ether, polyether sulfone, polyester, ABS
Such as engineering plastics can be applied. When using polystyrene for the porous foamed resin, the polystyrene has a low softening point of 80 to 100 ° C.,
Since the long-term continuous use temperature is set to 50 ° C., when used in an environment at such a temperature or higher, it is necessary to use engineering plastics such as polycarbonate resins and polyamide resins having a high softening point and high strength.
【0016】また、ホウ素系無機化合物を含有する熱硬
化性樹脂として、フェノール樹脂のほか、尿素樹脂、メ
ラミン樹脂、グアナミン樹脂、シリコーン樹脂、ポリイ
ミド或いはポリアミドイミド樹脂のような耐熱性樹脂な
どが使用可能である。As the thermosetting resin containing a boron-based inorganic compound, a phenol resin, a heat-resistant resin such as a urea resin, a melamine resin, a guanamine resin, a silicone resin, a polyimide or a polyamide-imide resin can be used. It is.
【0017】ホウ素系無機化合物として、ホウ酸(H3
BO3)の外、ホウ砂(Na2B4O7・10H2O)等が
適する。As the boron-based inorganic compound, boric acid (H 3
In addition to BO 3 ), borax (Na 2 B 4 O 7 .10H 2 O) or the like is suitable.
【0018】また、これらの樹脂の組合せは、多孔性発
泡樹脂が密着して一体化した成形体とするために、気泡
状構造を形成する樹脂とホウ素系無機化合物を含有する
樹脂との間で一定の密着性が必要であるが、相互に密着
性が充分でなくともこれら双方の樹脂に対して密着性の
ある樹脂を中間層として両者の密着性を改善することも
可能である。In order to form a molded article in which a porous foamed resin is adhered and integrated, a combination of these resins is used between a resin forming a cellular structure and a resin containing a boron-based inorganic compound. Although a certain degree of adhesion is required, it is also possible to improve the adhesion between the two resins by using a resin having adhesion to both resins as an intermediate layer even if the adhesion between the two is not sufficient.
【0019】更に、上記の熱硬化性樹脂のほか、これに
他の熱硬化性樹脂や熱可塑性樹脂を加えてブレンドする
ことにより、適宜の硬度、柔軟性、靭性や強度などを付
与することができ、例えば、ポリアミド樹脂、ポリビニ
ルフォルマール樹脂、ポリエーテルスルフォン樹脂、末
端基がカルボン酸のアクリルニトリルポリブタジェン共
重合体などを用いることができる。Further, in addition to the above thermosetting resin, another thermosetting resin or a thermoplastic resin is added thereto and blended to provide appropriate hardness, flexibility, toughness, strength and the like. For example, a polyamide resin, a polyvinyl formal resin, a polyether sulfone resin, an acrylonitrile polybutadiene copolymer having a carboxylic acid terminal group, or the like can be used.
【0020】また、ホウ素系無機化合物を含有する熱硬
化性樹脂層は、気泡状構造の外層を構成し耐熱性・難燃
性を付与するが、通常発泡工程を経て気泡状の構造を形
成するためにその温度での固化若しくは半硬化した状態
にある。この樹脂層に対して、ガラス短繊維や炭素短繊
維、或いは合成樹脂繊維や天然繊維等を添加して強度、
耐熱性などの特性を向上することができる。The thermosetting resin layer containing a boron-based inorganic compound constitutes an outer layer having a cellular structure and imparts heat resistance and flame retardancy, but usually forms a cellular structure through a foaming step. Therefore, it is in a solidified or semi-cured state at that temperature. To this resin layer, by adding short glass fiber or short carbon fiber, or synthetic resin fiber or natural fiber, the strength,
Properties such as heat resistance can be improved.
【0021】さらに、これらのホウ素系無機化合物に加
えて、各種の無機化合物を添加して種々の特性を付与す
ることができる。このような材料として、アルミナや珪
酸アルミニウム(Al2SiO5)、水酸化アルミニウム
(Al(OH)3)、水酸化マグネシウム(Mg(O
H)2)、シリカやシラスバルーン等の微粒子、粉体を
加えて耐熱性、難燃性等の特性を改善することができ
る。その他、Alなどの金属粉末、生石灰、二価アルカ
リ等の無機化合物の粉末も用途に応じて用いることがで
きる。Further, in addition to these boron-based inorganic compounds, various inorganic compounds can be added to impart various properties. Such materials include alumina, aluminum silicate (Al 2 SiO 5 ), aluminum hydroxide (Al (OH) 3 ), magnesium hydroxide (Mg (O
H) 2 ), fine particles such as silica and shirasu balloon, and powder can be added to improve properties such as heat resistance and flame retardancy. In addition, a powder of a metal such as Al, or a powder of an inorganic compound such as quicklime or divalent alkali can be used according to the intended use.
【0022】更に、これらの成形体は、そのままの場合
これらの素材の色合いに応じてほぼ白色を呈するが、こ
れにチタン白や各種の色を呈する顔料や染料を添加する
ことにより任意の色、色調とする事ができる。これらの
成形体は、通常壁材などの間に介挿して断熱性のある建
材などとして用いられる事が多いため一般に外観に関心
を持たれることは少ないが、表面層となるホウ素系無機
化合物を含有する熱硬化性樹脂層の厚さや添加する材料
の種類によって直接壁材などの表面を表した部位に使用
することができる。これらの用途に適した色調、性状の
外観とすることにより、これらの着色若しくは表面仕上
げのされた成形体として外観の優れた特性を発揮するこ
とができる。Furthermore, these molded articles, if they are as they are, exhibit almost white color according to the color of these materials. However, by adding titanium white or pigments or dyes exhibiting various colors, any desired color can be obtained. Can be a color tone. Since these molded articles are usually used as a heat-insulating building material by being interposed between wall materials and the like, they are generally less interested in appearance, but a boron-based inorganic compound serving as a surface layer is not used. Depending on the thickness of the thermosetting resin layer to be contained and the type of material to be added, it can be used directly on the surface of a wall material or the like where the surface is represented. By providing a color tone and properties suitable for these uses, it is possible to exhibit excellent appearance characteristics as a colored or surface-finished molded article.
【0023】次に本発明の成形体の製造方法を、その工
程に沿って説明する。ここでは、従来から広く用いられ
ている発泡剤を含有したポリスチレンビーズを用いた例
によって具体的に説明する。基本的な工程はビーズ法ポ
リスチレンフォームの製法と同様である。 (1)原料の調整 原料には既に発泡剤含浸等による前処理を行ない発泡剤
を含有するポリスチレンビーズを用いる。ビーズの直径
は、成形体の用途などによって異なるが、大略直径1.
0〜0.2mm程度の市販のポリスチレンビーズ原粒で
よい。 (2)予備発泡工程 原料ビーズを目的の製品により、10〜80倍程度に予備発
泡を行う。この処理によりビーズ表面積を適度に増大さ
せて後工程の熱硬化性樹脂の被覆厚さを調節することが
できる。従って、形成すべき熱硬化性樹脂被覆の厚さや
原料ビーズの粒度などにより、この工程は必ずしも必要
ではない。 (3)被覆工程 予備発泡ビーズ、熱硬化性樹脂及びホウ素系無機化合物
を攪拌混合し、所定の厚さの被覆層を形成する。熱硬化
性樹脂としてフェノール樹脂(レゾール)、ホウ素系無
機化合物としてホウ酸(H3BO3)をそれぞれ原料ビー
ズ100部(重量)に対して30〜100部(PHR)
及び30〜100部(PHR)を添加する。熱硬化性樹
脂には、フェノールスルホン酸、トルエンスルフォン酸
等の硬化促進剤を所要量加える。レゾールは、液状でホ
ウ酸を添加しても容易に混合され、予備発泡ビーズ表面
を均一に被覆すると共にビーズ同士が相互に付着しない
など取り扱いが容易である。 (4)本発泡工程(成形工程) 被覆工程後の予備発泡済みビーズを金型に収容し、加熱
して発泡成形する。板厚などによって条件が異なるが、
125℃前後、1乃至3分間程度加熱することにより、予備
発泡ビーズを本発泡させて金型内で成形する。Next, the method for producing a molded article of the present invention will be described along its steps. Here, a specific description will be given using an example using polystyrene beads containing a foaming agent which has been widely used in the past. The basic steps are the same as the method for producing a polystyrene foam by the bead method. (1) Preparation of Raw Materials As the raw materials, polystyrene beads containing a foaming agent that has already been subjected to a pretreatment such as impregnation with a foaming agent are used. The diameter of the beads varies depending on the use of the molded article and the like.
Commercially available polystyrene beads of about 0 to 0.2 mm may be used. (2) Pre-foaming step The raw beads are pre-foamed to about 10 to 80 times depending on the target product. By this treatment, the surface area of the beads can be appropriately increased, and the coating thickness of the thermosetting resin in the subsequent step can be adjusted. Therefore, this step is not always necessary depending on the thickness of the thermosetting resin coating to be formed, the particle size of the raw material beads, and the like. (3) Coating Step The pre-expanded beads, the thermosetting resin, and the boron-based inorganic compound are stirred and mixed to form a coating layer having a predetermined thickness. A phenol resin (resole) as a thermosetting resin, and boric acid (H 3 BO 3 ) as a boron-based inorganic compound are each 30 to 100 parts (PHR) based on 100 parts (weight) of raw material beads.
And 30 to 100 parts (PHR). A required amount of a curing accelerator such as phenolsulfonic acid and toluenesulfonic acid is added to the thermosetting resin. The resol is in a liquid state and is easily mixed even when boric acid is added, and is easy to handle such that the surface of the pre-expanded beads is uniformly coated and the beads do not adhere to each other. (4) Main Foaming Step (Molding Step) The pre-foamed beads after the covering step are housed in a mold and heated to foam and mold. Conditions vary depending on plate thickness, etc.
By heating at about 125 ° C. for about 1 to 3 minutes, the pre-expanded beads are fully expanded and molded in a mold.
【0024】本発泡によりビーズは、その外表面のホウ
素系無機化合物含有熱硬化性樹脂被覆層と共に膨張して
互いに接し、加熱によってこれらの内外層の樹脂層が融
着すると共に、隣接するビーズの外表面の熱硬化性樹脂
層とも融着して多孔性発泡樹脂同士が細胞状に相互に結
合して一体となり、金型に沿った一定の形状の成形体と
なる。Due to the main foaming, the beads expand together with the boron-containing inorganic compound-containing thermosetting resin coating layer on the outer surface thereof and come into contact with each other. The porous foamed resin is fused together with the thermosetting resin layer on the outer surface to be combined with each other in a cell-like manner to form a single-piece molded body along the mold.
【0025】加熱手段として、オートクレーブにて順次
バッチ作業で加熱処理する外、金型に金属製以外のもの
が使用できる場合は、高周波加熱によっても良い。ある
いは、ボードなどの板状材の場合には熱板プレスによる
多段式スチームプレス法も適する。また、スチームなど
の加熱手段を備えたいわゆる自動成形機等も好適に使用
できる。発泡工程の加熱温度は、熱硬化性樹脂や添加す
るホウ素系無機化合物の種類などによって異なるが、そ
の加熱によって熱硬化性樹脂がある程度硬化反応を生
じ、またホウ酸などのホウ素系無機化合物の分解が進行
して多孔性発泡樹脂同士を結合する樹脂混合層が形成さ
れる。As a heating means, in addition to heat treatment by batch operation in an autoclave sequentially, when a mold other than metal can be used, high-frequency heating may be used. Alternatively, in the case of a plate-like material such as a board, a multistage steam press method using a hot plate press is also suitable. Also, a so-called automatic molding machine having a heating means such as steam can be suitably used. The heating temperature in the foaming step varies depending on the type of the thermosetting resin and the boron-based inorganic compound to be added, but the heating causes the thermosetting resin to undergo a certain degree of curing reaction, and the decomposition of the boron-based inorganic compound such as boric acid. Progresses to form a resin mixed layer that bonds the porous foamed resins together.
【0026】耐熱性及び他の特性試験の結果 上記の製造方法によって形成した耐熱・難燃性ボードに
ついて各種の特性試験を行った結果を示す。Results of heat resistance and other property tests The results of various property tests performed on the heat-resistant and flame-retardant board formed by the above-described manufacturing method are shown.
【0027】 区 分 摘要 熱伝導率 発泡体の熱伝導率 0.04w/m・k (京都電子工業製熱伝導率計TC31を用いた熱線法による。) 燃焼試験 酸素指数:38.7 JIS K7201 A1号 長さ50mm以上燃焼時間 防炎性能試験 残炎時間:0秒 残時間 :0秒 炭化面積:0cm2 発炎・くすぶり:なし 日本防炎協会「防炎製品の性能試験基準」ローパーティション部門 45゜ メッケルバーナー法による50mm×200mm×25mmの試験片を0.2mm厚のアルミ 箔で被覆した供試体使用 その他の物性 密度 0.76g/m3 圧縮強さ 42N/cm2 吸水量 0.31g/100cm2 JIS A 9511の4.6、4.9及び4.11による。 本発明の成形体の用途は、従来のポリスチレンやポリウ
レタンなどの発泡成形体の用途においてその耐熱性・難
燃性の特性を発揮できる外、その特性により従来適用で
きなかった用途にも安全に用いることができる。また、
熱硬化性樹脂層に添加した繊維強化材や粉粒状の無機材
料或いはブレンドした樹脂の組み合わせにより新たな特
性を付与され、今後各種の用途に向けて適用されること
が期待できる。例えば、次のような用途が挙げられる。 建材:屋根、壁、天井、床などの断熱材、各種用途向け
軽量難燃性ボード:パネル、建具、パーティションな
ど、各種用途向け断熱構造材:冷暖房用ダクト、保冷。
保温設備の断熱材、各種成形品:マネキンなど。Classification Summary Thermal conductivity Thermal conductivity of foam 0.04 w / m · k (by the hot wire method using thermal conductivity meter TC31 manufactured by Kyoto Denshi Kogyo) Combustion test Oxygen index: 38.7 JIS K7201 No. A1 Length 50mm or more Burning time Flameproofing performance test Afterflame time: 0 seconds Residual time: 0 seconds Carbonized area: 0 cm 2 Flames / smoldering: None Japanese fire protection association "Performance test standards for flameproofing products" Low partition section 45 ゜ Using a specimen in which a 50 mm × 200 mm × 25 mm test piece by the Meckel burner method is coated with 0.2 mm thick aluminum foil. Other physical properties Density 0.76 g / m 3 Compressive strength 42 N / cm 2 Water absorption 0.31 g / 100 cm 2 According to JIS A 9511 4.6, 4.9 and 4.11. The use of the molded article of the present invention is not only capable of exhibiting its heat resistance and flame retardant properties in the use of conventional foamed molded articles such as polystyrene and polyurethane, but also used safely in applications which could not be conventionally applied due to its properties. be able to. Also,
New characteristics are provided by a combination of a fiber reinforced material, a powdery inorganic material, or a blended resin added to the thermosetting resin layer, and it can be expected to be applied to various uses in the future. For example, the following uses are possible. Construction materials: Insulation materials for roofs, walls, ceilings, floors, etc., lightweight flame-retardant boards for various applications: Panels, fittings, partitions, etc. Insulation structure materials for various applications: Cooling / heating ducts, cooling.
Insulation material for thermal insulation equipment, various molded products: mannequins, etc.
【0028】このように、本発明の耐熱、難燃性成形体
は、これらの各種の用途向け発泡成形体として、従来の
発泡ポリスチレンやポリウレタンフォームなどの成形体
と同様の軽量、断熱性を有していて同様に用いることが
できると共に、耐熱性・難燃性に優れていて火災などの
災害対策に安全面で寄与することができる。さらに、多
孔性発泡樹脂の外周面を被覆する熱硬化性樹脂層はその
樹脂の種類を適当に選ぶ外、これに他の種類の樹脂や無
機・有機物質を加えてブレンドすることによりより好適
な性質、たとえば柔軟性、強度、硬度などを付与するこ
とができる。As described above, the heat-resistant and flame-retardant molded article of the present invention has the same lightweight and heat-insulating properties as conventional molded articles such as expanded polystyrene and polyurethane foam as foam molded articles for these various uses. In addition to being able to be used similarly, it is excellent in heat resistance and flame retardancy, and can contribute to safety measures for disasters such as fires. Further, the thermosetting resin layer covering the outer peripheral surface of the porous foamed resin is not only appropriately selected for the type of the resin, but also more suitable by adding another type of resin or an inorganic or organic substance and blending it. Properties such as flexibility, strength, hardness and the like can be imparted.
【図1】本発明のホウ素系化合物を含有する樹脂によっ
て被覆した多孔性発泡樹脂からなる成形体。FIG. 1 shows a molded article made of a porous foamed resin coated with a resin containing the boron compound of the present invention.
【図2】多孔性発泡樹脂の断面構造。FIG. 2 is a cross-sectional structure of a porous foamed resin.
1 成形体 2 多孔性発泡樹脂粒子 3 ホウ素系無機化合物含有熱硬化性樹脂 DESCRIPTION OF SYMBOLS 1 Molded object 2 Porous expanded resin particle 3 Thermosetting resin containing boron-based inorganic compound
フロントページの続き Fターム(参考) 4F074 AA32 AC34 AC36 AE04 AG01 CA38 CA46 CA49 CC04Y CE57 CE73 CE88 DA07 DA18 DA32 DA37 4F212 AA13 AA36 AA37 AB02 AB05 AB16 AB25 AC01 AD04 AD16 AE10 AG03 AG20 AH47 UA02 UB01 UF01 UF06 UG07 UN13Continued on front page F-term (reference) 4F074 AA32 AC34 AC36 AE04 AG01 CA38 CA46 CA49 CC04Y CE57 CE73 CE88 DA07 DA18 DA32 DA37 4F212 AA13 AA36 AA37 AB02 AB05 AB16 AB25 AC01 AD04 AD16 AE10 AG03 AG20 AH47 UA02 UB01 UF01 UF01UF
Claims (5)
樹脂からなる混合物層で被覆した多孔性発泡樹脂からな
る成形体。1. A molded article composed of a porous foamed resin whose outer periphery is covered with a mixture layer composed of a boron-based inorganic compound and a thermosetting resin.
からなり、ホウ素系無機化合物がホウ酸であり、熱硬化
性樹脂がフェノール樹脂であることを特徴とする請求項
1記載の成形体。2. The molded article according to claim 1, wherein the porous foamed resin is a polystyrene resin, the boron-based inorganic compound is boric acid, and the thermosetting resin is a phenol resin.
物の外、ガラス繊維、炭素繊維などの繊維強化材及び、
又はシリカ、シラス、タルクなどの無機粉粒体が添加さ
れていることを特徴とする請求項1又は2記載の成形
体。3. The thermosetting resin further includes a fiber-reinforced material such as glass fiber and carbon fiber, in addition to the boron-based inorganic compound,
The molded product according to claim 1, wherein an inorganic powder such as silica, shirasu, and talc is added.
機化合物を添加した熱硬化性樹脂により被覆し、発泡成
形処理を行って所定の形状の成形体とするホウ素系無機
化合物を含有する樹脂被覆多孔性発泡樹脂からなる成形
体の製造方法。4. A resin containing a boron-based inorganic compound, which is obtained by coating resin particles containing a foaming agent with a thermosetting resin to which a boron-based inorganic compound has been added, and subjecting the resin to foam molding to form a molded article having a predetermined shape. A method for producing a molded article comprising a coated porous foamed resin.
した樹脂粒子を所定の比率で予備発泡させることを特徴
とする請求項4記載のホウ素系無機化合物を含有する樹
脂被覆多孔性発泡樹脂からなる成形体の製造方法。5. The resin-coated porous foamed resin containing a boron-based inorganic compound according to claim 4, wherein the resin particles containing a foaming agent are prefoamed at a predetermined ratio prior to the coating step. A method for producing a molded article comprising:
Priority Applications (1)
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JP35261899A JP2001164031A (en) | 1999-12-13 | 1999-12-13 | Moldings comprising porous foam resin having heat- resistant and flame-retardant resin mixture layer and molding production thereof |
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Application Number | Priority Date | Filing Date | Title |
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JP35261899A JP2001164031A (en) | 1999-12-13 | 1999-12-13 | Moldings comprising porous foam resin having heat- resistant and flame-retardant resin mixture layer and molding production thereof |
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ID=18425284
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