JPH10219021A - Uncured synthetic resin foamed particle aggregate, its production, light-weight molding product, its production, light-weight composite material, its production and intermediate for producing the composite material - Google Patents
Uncured synthetic resin foamed particle aggregate, its production, light-weight molding product, its production, light-weight composite material, its production and intermediate for producing the composite materialInfo
- Publication number
- JPH10219021A JPH10219021A JP35235197A JP35235197A JPH10219021A JP H10219021 A JPH10219021 A JP H10219021A JP 35235197 A JP35235197 A JP 35235197A JP 35235197 A JP35235197 A JP 35235197A JP H10219021 A JPH10219021 A JP H10219021A
- Authority
- JP
- Japan
- Prior art keywords
- unsaturated polyester
- synthetic resin
- polyester resin
- aggregate
- uncured
- 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.)
- Pending
Links
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、未硬化状合成樹脂
発泡粒状物集合体及びその製造方法、軽量成形体及びそ
の製造方法並びに軽量成形体に表面材が積層された軽量
複合体及びその製造方法並びに軽量複合体製造のための
中間体に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aggregate of foamed uncured synthetic resin particles, a method for producing the same, a lightweight molded body, a method for producing the same, a lightweight composite in which a surface material is laminated on the lightweight molded body, and a production thereof. The invention relates to a method and to an intermediate for the production of lightweight composites.
【０００２】[0002]
【従来の技術】従来、軽量で強度に優れ、更に耐熱性及
び断熱性にも優れる軽量成形体が開発されてきた。この
軽量成形体には、多数の合成樹脂発泡粒状物（ビーズ）
を不飽和ポリエステル樹脂により加圧接着一体化して得
られる軽量成形体（特開昭５３−７１１７２号公報、特
開昭４８−７２２６８号公報）がある。また構造強度を
高めるために強度が大きい表面材、例えば繊維強化不飽
和ポリエステル樹脂により前記軽量成形体をはさんで積
層した軽量複合体（実公昭６２−２４５２１号公報、特
開昭６３−７１３４４号公報）などがある。これらの軽
量成形体（軽量複合体においては強度の大きい表面材に
はさまれる芯材部分に相当）を製造する方法の最も特徴
的なところは、発泡粒子の接着の役割をはたす液状不飽
和ポリエステル樹脂と発泡粒子との混合物に硬化剤と硬
化促進剤を添加し、型枠に入れた後、必要に応じて加熱
しつつ、プレスする点である。このような従来技術の問
題点として次のことが挙げられる。 （１）硬化剤と硬化促進剤を液状不飽和ポリエステルに
添加することにより、直ちに液状不飽和ポリエステルの
硬化反応が開始されるため、それらの添加後に直ちに発
泡粒子と液状不飽和ポリエステル樹脂混合物をプレス成
形を行なわなければならない。したがって、発泡粒子と
液状不飽ポリエステル樹脂混合物の調製から軽量体又は
複合軽量体の製造までを一貫工程で行う必要があり、作
り置きができず不便である。また、成形操作開始後に何
らかの事情が生じても、成形操作の中断、延期、変更等
が不可能である。また、全ての混合操作を終了し、金型
に投入という段階でその一部がこぼれて不足してしまっ
たような場合には、その混合物全てが無駄になってしま
うということとなる。 （２）軽量成形体を成形する際に、プレス成形工程の、
プレス開始時に、液状不飽和ポリエステル樹脂の一部が
型枠外に流れ出して作業環境を悪化させることがある。
特に、軽量成形体中の発泡粒子の充填率を高めようとす
る場合には、プレス度合を高めることにより、余剰の液
状不飽和ポリエステル樹脂をできる限り型枠から外に排
出させる操作を行なわなければならず（そうしないと発
泡粒子間に不飽和ポリエステル樹脂が均一に回り込まな
い）、その結果、著しく作業環境を悪化させることとな
る。しかも、型枠から流れ出た不飽和ポリエステル樹脂
は既に硬化剤と硬化促進剤が添加されているため、流れ
出たあるいは積極的に排出させた液状不飽和ポリエステ
ル樹脂は他に転用できず廃棄せざるを得ないし、また早
い時期にそれを清掃しないとそこで硬化して取り除くの
が困難になる。2. Description of the Related Art Hitherto, lightweight molded articles which are lightweight, have excellent strength, and have excellent heat resistance and heat insulating properties have been developed. This lightweight molded body contains many synthetic resin foam granules (beads).
Are molded by pressure bonding with an unsaturated polyester resin to obtain a lightweight molded product (JP-A-53-71172, JP-A-48-72268). Further, in order to increase the structural strength, a lightweight composite in which the lightweight molded body is laminated with a surface material having high strength, for example, a fiber-reinforced unsaturated polyester resin (Japanese Utility Model Publication No. 62-24521, Japanese Patent Application Laid-Open No. 63-71344). Gazette). The most characteristic feature of the method for producing these lightweight molded articles (corresponding to the core portion sandwiched between high-strength surface materials in a lightweight composite) is that the liquid unsaturated polyester plays a role of bonding the foamed particles. The point is that a curing agent and a curing accelerator are added to a mixture of the resin and the foamed particles, and the mixture is placed in a mold and then pressed while being heated as necessary. The problems of the conventional technology include the following. (1) Since the curing reaction of the liquid unsaturated polyester is started immediately by adding the curing agent and the curing accelerator to the liquid unsaturated polyester, the mixture of the foamed particles and the liquid unsaturated polyester resin is immediately pressed after the addition. Molding must be performed. Therefore, it is necessary to carry out from the preparation of the mixture of the foamed particles and the liquid unsaturated polyester resin to the production of the light-weight body or the composite light-weight body in an integrated process. Also, even if some circumstances occur after the start of the molding operation, it is impossible to interrupt, postpone, change, etc. the molding operation. If all the mixing operations are completed and part of the mixture is spilled at the stage of being charged into the mold and becomes insufficient, the entire mixture is wasted. (2) When molding a lightweight molded article,
At the start of pressing, a part of the liquid unsaturated polyester resin may flow out of the mold to deteriorate the working environment.
In particular, when trying to increase the filling rate of the expanded particles in the lightweight molded article, by increasing the degree of pressing, an operation of discharging excess liquid unsaturated polyester resin from the mold as much as possible must be performed. Otherwise (unsaturated polyester resin will not uniformly flow between the foamed particles), as a result, the working environment will be significantly deteriorated. In addition, since the unsaturated polyester resin that has flowed out of the mold has a curing agent and a curing accelerator already added, the liquid unsaturated polyester resin that has flowed out or has been actively discharged cannot be diverted to other uses and must be discarded. If it is not obtained, and it is not cleaned early, it hardens there and becomes difficult to remove.
【０００３】[0003]
【発明が解決しようとする課題】本発明の課題は、途中
の段階までで作り置きができ、運搬などの取り扱い性に
優れ、コスト的にも優位性が有り、成形時に環境悪化を
引き起こすことがなく、かつ所定の加熱下にプレス成形
装置によりプレス成形するだけで容易に軽量成形体及び
軽量複合体を製造することができる未硬化状合成樹脂発
泡粒状物集合体及びその製造方法、該集合体より軽量成
形体を製造する方法及びその軽量成形体、並びに該軽量
成形体と表面材とから軽量複合体を製造する方法、その
軽量複合体及びその中間体を提供することである。SUMMARY OF THE INVENTION The object of the present invention is that it can be made up to the middle stage, is excellent in handling such as transportation, has an advantage in cost, and causes environmental deterioration during molding. Uncured synthetic resin foamed granular material aggregate that can easily produce a lightweight molded body and a lightweight composite simply by press molding with a press molding device under predetermined heating, a method for producing the same, and the aggregate It is an object of the present invention to provide a method for producing a lighter-weight molded article, its lightweight molded article, a method for producing a lightweight composite from the lightweight molded article and a surface material, its lightweight composite and its intermediate.
【０００４】[0004]
【課題を解決するための手段】本発明者らは、前記課題
を解決するために鋭意研究を重ねた結果、本発明を完成
するに至った。即ち、本発明によれば、多数の合成樹脂
発泡粒状物を不飽和ポリエステル樹脂を介して一体に結
合させたものであって、該不飽和ポリエステル樹脂は硬
化剤を含有しているが、実質的に未硬化の状態であり、
かつ常温において固体状ないし半固体状を示すことを特
徴とする未硬化状合成樹脂発泡粒状物集合体が提供され
る。本発明によれば、硬化剤と増粘剤とを含有するペー
スト状の不飽和ポリエステル樹脂により表面が覆われた
合成樹脂発泡粒状物の多数個集積体を、前記硬化剤の反
応開始温度より低い温度に保持して前記不飽和ポリエス
テル樹脂と前記増粘剤とを反応させて固体状ないし半固
体状物に形成することを特徴とする前記未硬化状合成樹
脂発泡粒状物集合体を製造する方法が提供される。本発
明によれば、未硬化状合成樹脂発泡粒状物集合体を、硬
化剤の分解温度以上の温度でプレス成形することを特徴
とする軽量成形体の製造方法並びに該軽量成形体が提供
される。本発明によれば、前記軽量成形体と表面材とか
らなる軽量複合体が提供される。本発明によればまた、
前記未硬化状合成樹脂発泡粒状物集合体と表面用素材と
の積層体からなる中間体、並びに該中間体を硬化剤の分
解温度以上の温度でプレス成形することを特徴とする軽
量複合体の製造方法が提供される。Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have completed the present invention. That is, according to the present invention, a large number of synthetic resin foam granules are integrally bonded via an unsaturated polyester resin, and the unsaturated polyester resin contains a curing agent, In an uncured state,
Further, an uncured synthetic resin foamed granular material aggregate which exhibits a solid state or a semi-solid state at ordinary temperature is provided. According to the present invention, a multi-piece aggregate of synthetic resin foam granules whose surface is covered with a paste-like unsaturated polyester resin containing a curing agent and a thickener is lower than the reaction start temperature of the curing agent. A method for producing the uncured synthetic resin expanded granular material aggregate, comprising reacting the unsaturated polyester resin with the thickener while maintaining the temperature to form a solid or semi-solid material. Is provided. ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the lightweight molded object characterized by press-molding the uncured synthetic resin expanded granular material aggregate at the temperature more than the decomposition temperature of a hardening agent, and this lightweight molded object are provided. . According to the present invention, there is provided a lightweight composite comprising the lightweight molded body and a surface material. According to the present invention also
An intermediate comprising a laminate of the uncured synthetic resin expanded granular material aggregate and a surface material, and a lightweight composite, wherein the intermediate is press-molded at a temperature equal to or higher than the decomposition temperature of a curing agent. A manufacturing method is provided.
【０００５】[0005]
【発明の実施の形態】本発明では合成樹脂発泡粒状物
（以下、単に発泡粒状物ともいう）が用いられる。この
発泡粒状物は、表面材なしの軽量成形体を形成するか、
あるいは軽量成形体の少なくとも片面に表面材が一体的
に積層された構造を持つ軽量複合体の軽量成形体部分を
形成するものである。発泡粒状物の多数個を使用し加熱
下でプレス成形して軽量成形体又は軽量複合体を製造す
るに当たっては、事前に、発泡粒状物の多数個を相互に
接着一体化して発泡粒状物の集合体を形成しておく。そ
してその接着一体化は、少なくとも硬化剤と増粘剤を含
有する実質的に未硬化のペースト状の不飽和ポリエステ
ル樹脂を使用して実施される。発泡粒状物を形成する材
料としては、発泡成形可能な従来公知の各種の合成樹脂
が使用可能であるが、この発泡粒状物を接着する役割を
果たす不飽和ポリエステル樹脂との親和性に優れたもの
が望ましい。そのような樹脂としては、具体的には、ポ
リカ−ボネ−ト樹脂、ポリエチレンテレフタレート樹
脂、ポリウレタン樹脂、ポリ塩化ビニル樹脂、アクリル
系樹脂、ナイロン系樹脂などを基材としたものが例示さ
れる。本発明においては、ポリオレフィン系樹脂を好ま
しく用いることができる。この場合のポリオレフィン系
樹脂には、ポリプロピレン、プロピレン−エチレン共重
合体、プロピレン−ブテン−１共重合体、プロピレン−
エチレン−ブテン−１共重合体、分岐低密度ポリエチレ
ン、直鎖状低密度ポリエチレン、高密度ポリエチレン等
のα−オレフィンの単独重合体及び共重合体のほか、従
来公知のそれらの変性体が包含される。また、この場合
の変性体には、ポリオレフィンに変性用のビニルモノマ
ーを含浸させてグラフト共重合させたものや、他のポリ
マーを混合したもの等が包含される。ポリオレフィン系
樹脂を用いるときには、最終的に得られる軽量成形体は
空隙率の少ないものとなり、良好な機械的強度を有する
ものとなる。本発明においては、前記したように発泡粒
状物に不飽和ポリエステル樹脂が付着し、それらの発泡
粒状物相互を結着させることが必要であるが、ポリオレ
フィンの場合、不飽和ポリエステル樹脂に対する付着力
がやや不十分である。したがって、ポリオレフィン系樹
脂を用いる場合には、不飽和ポリエステル樹脂に対する
接着力を高めるように変性した変性ポリオレフィン系樹
脂の使用が有利である。このようなものには、（ｉ）ポ
リオレフィンに、スチレンモノマーや、ビニルトルエン
等のビニル芳香族モノマーを変性用ビニルモノマーとし
て共重合（例えば、グラフト共重合）させたもの、（i
i）ポリオレフィンに対し、その不飽和ポリエステルに
対する接着力を高めるために、不飽和ポリエステルに対
して、ポリオレフィンよりも高い接着力を有する易接着
性重合体を混合したもの等が包含される。このような易
接着性重合体としては、１，２−ポリブタジエン、一般
用ポリスチレン、耐衝撃性ポリスチレン、アクリル系樹
脂、ポリカーボネート、無水マレイン酸グラフト変性ポ
リオレフィン、及びこれら２以上の混合物等が挙げられ
る。本発明で発泡粒状物の原料として用いる合成樹脂
は、前記したように、不飽和ポリエステル樹脂に対する
親和性（接着性）の高いものが好ましいが、余り高すぎ
ると、その不飽和ポリエステル樹脂に溶解するようにな
るので好ましくない。このような場合には、その合成樹
脂を発泡成形するときに、その樹脂に架橋剤（パーオキ
サイド）を配合し、架橋構造を有する発泡粒状物を得る
とともに、この発泡粒状物を原料として用いるのがよ
い。変性用ビニルモノマー又は変性用樹脂の使用量は、
ポリオレフィン１００重量部に対し、１〜２００重量部
が望ましい。発泡粒状物の真密度は、通常０．０２〜
０．３ｇ／ｃｍ3、好ましくは０．０３〜０．２ｇ／ｃ
ｍ3である。発泡粒状物の直径又は最大長さは、通常２
０ｍｍ以下、好ましくは１〜１０ｍｍの範囲にある。発
泡粒状物は発泡体の粉砕品やカットされたものであって
差支えないが、独立気泡率の高い型内成形の可能な発泡
粒子が最も望ましい。BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, synthetic resin foam granules (hereinafter, also simply referred to as foam granules) are used. This foamed granular material forms a lightweight molded body without surface material,
Alternatively, a lightweight molded body portion of a lightweight composite having a structure in which a surface material is integrally laminated on at least one surface of the lightweight molded body is formed. In producing a lightweight molded article or lightweight composite by press-forming under heating using a large number of expanded granules, a large number of expanded granules are bonded and integrated with each other in advance to form a set of expanded granules. Form your body. The bonding and integration are performed using a substantially uncured paste-like unsaturated polyester resin containing at least a curing agent and a thickener. As the material for forming the foamed granules, various known synthetic resins which can be foam-molded can be used, but those having an excellent affinity with the unsaturated polyester resin which plays a role of bonding the foamed granules are used. Is desirable. Specific examples of such a resin include those based on a polycarbonate resin, a polyethylene terephthalate resin, a polyurethane resin, a polyvinyl chloride resin, an acrylic resin, a nylon resin, or the like. In the present invention, a polyolefin resin can be preferably used. Polyolefin resins in this case include polypropylene, propylene-ethylene copolymer, propylene-butene-1 copolymer, propylene-
In addition to α-olefin homopolymers and copolymers such as ethylene-butene-1 copolymer, branched low-density polyethylene, linear low-density polyethylene, and high-density polyethylene, conventionally known modified products thereof are included. You. Further, the modified product in this case includes a product obtained by impregnating a polyolefin with a vinyl monomer for modification and graft-copolymerizing it, or a product obtained by mixing another polymer. When a polyolefin-based resin is used, the finally obtained lightweight molded article has a low porosity and has good mechanical strength. In the present invention, as described above, the unsaturated polyester resin adheres to the foamed granules, and it is necessary to bind the foamed granules to each other. In the case of polyolefin, the adhesion to the unsaturated polyester resin is low. Somewhat insufficient. Therefore, when a polyolefin-based resin is used, it is advantageous to use a modified polyolefin-based resin modified so as to increase the adhesive strength to the unsaturated polyester resin. These include (i) polyolefin copolymerized with a styrene monomer or a vinyl aromatic monomer such as vinyl toluene as a modifying vinyl monomer (for example, graft copolymerization);
i) In order to increase the adhesive strength of the unsaturated polyester with respect to the polyolefin, a mixture of an unsaturated polyester and an easily adhesive polymer having a higher adhesive strength than the polyolefin is included. Examples of such an easily adhesive polymer include 1,2-polybutadiene, general-purpose polystyrene, impact-resistant polystyrene, acrylic resin, polycarbonate, maleic anhydride-grafted polyolefin, and a mixture of two or more of these. As described above, the synthetic resin used as the raw material of the expanded granular material in the present invention preferably has a high affinity (adhesion) to the unsaturated polyester resin, but if it is too high, it will dissolve in the unsaturated polyester resin. Is not preferred. In such a case, when the synthetic resin is foamed, a crosslinking agent (peroxide) is blended with the resin to obtain a foamed granular material having a crosslinked structure, and the foamed granular material is used as a raw material. Is good. The amount of modifying vinyl monomer or modifying resin used is
1 to 200 parts by weight is desirable for 100 parts by weight of the polyolefin. The true density of the expanded granular material is usually 0.02 to
0.3 g / cm 3 , preferably 0.03 to 0.2 g / c
m is 3. The diameter or maximum length of the expanded granules is usually 2
0 mm or less, preferably in the range of 1 to 10 mm. The expanded granular material may be a pulverized product of a foam or a cut product, but an expanded particle having a high closed cell rate and capable of being formed in a mold is most preferable.
【０００６】本発明では、発泡粒状物の多数個からそれ
らの集合体を形成するために、少なくとも硬化剤と増粘
剤が添加された不飽和ポリエステル樹脂混合物（以下、
単に不飽和ポリエステル樹脂混合物ともいう）が用いら
れる。不飽和ポリエステル樹脂としては、不飽和多価カ
ルボン酸と多価アルコ−ルから得られる縮合生成物を、
ビニルモノマ−に溶解させて得られる公知のものが使用
できる。不飽和多価カルボン酸としては、無水マレイン
酸、フマル酸、アジピン酸、無水フタル酸、イソフタル
酸などを例示できる。多価アルコ−ルとしてはエチレン
グリコ−ル、１、３−ブチレングリコ−ル、ジエチレン
グリコ−ル、プロピレングリコ−ルなどを例示できる。
ビニルモノマ−としては、スチレン系モノマーなどを例
示できる。According to the present invention, an unsaturated polyester resin mixture (hereinafter, referred to as a hardening agent and a thickening agent) is added to form an aggregate thereof from a large number of expanded granules.
Simply referred to as an unsaturated polyester resin mixture). As the unsaturated polyester resin, a condensation product obtained from an unsaturated polycarboxylic acid and a polyhydric alcohol,
A known product obtained by dissolving in a vinyl monomer can be used. Examples of the unsaturated polycarboxylic acid include maleic anhydride, fumaric acid, adipic acid, phthalic anhydride, isophthalic acid and the like. Examples of the polyhydric alcohol include ethylene glycol, 1,3-butylene glycol, diethylene glycol, and propylene glycol.
Examples of the vinyl monomer include a styrene monomer.
【０００７】増粘剤は、不飽和ポリエステル樹脂の末端
基のカルボキシル基と反応し、不飽和ポリエステル樹脂
の分子量を増大させ、その結果、不飽和ポリエステル樹
脂を固体状ないし半固体状に形成させるものである。一
般的には、アルカリ土類金属の酸化物や水酸化物を挙げ
ることができる。具体的には、酸化マグネシウムや酸化
カルシウムなどのアルカリ土類金属酸化物や、水酸化マ
グネシウムや水酸化カルシウムなどのアルカリ土類金属
水酸化物を例示することができる。The thickener reacts with the carboxyl group of the terminal group of the unsaturated polyester resin to increase the molecular weight of the unsaturated polyester resin, thereby forming the unsaturated polyester resin in a solid or semi-solid state. It is. Generally, oxides and hydroxides of alkaline earth metals can be mentioned. Specific examples include alkaline earth metal oxides such as magnesium oxide and calcium oxide, and alkaline earth metal hydroxides such as magnesium hydroxide and calcium hydroxide.
【０００８】硬化剤は特定の温度（硬化剤の分解温度）
以上に加熱されると、不飽和ポリエステル樹脂を架橋さ
せるものである。増粘された不飽和ポリエステル樹脂混
合物にて接着一体化された未硬化状合成樹脂発泡粒状物
集合体（以下、単に未硬化集合体ともいう）が硬化剤の
分解温度以上の温度下にプレス成形されたときに、硬化
剤は急激にその作用を開始する。そして、その加熱下で
のプレス状態をしばらく保持すると硬化反応が完結す
る。硬化剤は未硬化集合体の製造時及び保管時に実質的
な分解を起こしてはならないので、具体的には１０時間
半減期を得る温度が４０℃以上のものが望ましい。しか
しながら、この温度が高すぎると、固体状ないし半固体
状に形成された不飽和ポリエステル樹脂混合物の硬化反
応時（プレス成形時）に、発泡粒状物が溶融して気泡構
造が消滅してしまうおそれがあるので、そうならないよ
うに、硬化剤は使用される発泡粒状物の基材樹脂との関
係で選定しなければならない。本発明で好適に使用され
る硬化剤としてはラウロイルパ−オキサイド、ビス（４
−ｔ−ブチルシクロヘキシル）パーオキシジカーボネー
ト、ジメトキシブチルパーオキシジカーボネート、ｔ−
ヘキシルパーオキシ−２−エチルヘキサノエート、ベン
ゾイルパーオキサイド、１，１−ビス（ｔ−ブチルパー
オキシ）−３，３，５−トリメチルシクロヘキサン、ｔ
−ブチルパーオキシベンゾエートなどの有機過酸化物を
例示することができる。The curing agent has a specific temperature (decomposition temperature of the curing agent)
When heated as described above, the unsaturated polyester resin is crosslinked. An uncured synthetic resin expanded granular material aggregate (hereinafter, also simply referred to as an uncured aggregate) bonded and integrated with a thickened unsaturated polyester resin mixture is press-molded at a temperature equal to or higher than the decomposition temperature of a curing agent. When done, the curing agent begins its action rapidly. When the pressed state under the heating is maintained for a while, the curing reaction is completed. Since the curing agent must not substantially decompose during the production and storage of the uncured aggregate, it is desirable that the curing agent has a temperature at which a half-life of 10 hours is obtained at 40 ° C. or higher. However, if the temperature is too high, the foamed granules may melt during the curing reaction (during press molding) of the unsaturated polyester resin mixture formed into a solid or semi-solid state, and the cell structure may disappear. In order to avoid this, the curing agent must be selected in relation to the base resin of the foamed granular material to be used. The curing agents preferably used in the present invention include lauroyl peroxide and bis (4
-T-butylcyclohexyl) peroxydicarbonate, dimethoxybutylperoxydicarbonate, t-
Hexylperoxy-2-ethylhexanoate, benzoyl peroxide, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, t
Organic peroxides such as -butylperoxybenzoate.
【０００９】未硬化集合体を製造するには、まず、液状
の不飽和ポリエステル樹脂に硬化剤と増粘剤を添加混合
し、不飽和ポリエステル樹脂混合物を製造する。硬化剤
の添加割合は、不飽和ポリエステル樹脂１００重量部に
対して、０．１〜１．０重量部、特に０．３〜５．０重
量部が好ましい。増粘剤の添加割合は、不飽和ポリエス
テル樹脂１００重量部に対して、０．２〜１０．０重量
部、特に０．５〜５．０重量部が好ましい。なお、不飽
和ポリエステル混合物には、増粘剤や硬化剤の他に、低
収縮剤、内部離型剤、充填剤、顔料、補強材、難燃剤な
どを必要に応じて添加することができる。特に高強度を
得るためには補強材を添加することが望ましい。補強材
としては、繊維状補強材、粉体状補強材等が挙げられ、
繊維状補強材としては、ガラス繊維、セラミック繊維、
ポリエステル繊維、塩化ビニル・アクリロニトリル共重
合体系繊維、炭素繊維、スチール繊維、アルミニウム繊
維、ホウ素繊維及びこれらの２以上の併用が例示され、
粉体状補強材としては、ガラス粉体と、一般的に無機フ
ィラーと呼ばれるものでシリカ、アルミナ、酸化チタ
ン、酸化鉄、酸化亜鉛、酸化マグネシウム、酸化アンチ
モン、バリウムフェライト、ストロンチウムフェライ
ト、酸化ベリリウム、軽石、タルク、カオリン、マイ
カ、セリサイト、ほう砂、水酸化アルミニウム、水酸化
マグネシウム、炭酸アルミニウム、炭酸カルシウム、硫
酸バリウム、硫酸アンモニウム、亜硫酸カルシウム及び
これらの２以上の併用が例示される。特に、軽量成形体
及び軽量複合体の高強度化のためには、補強材として
は、ガラス繊維、ガラス粉体、無機フィラー及びこれら
の２以上の混合物の群から選択されるものが好ましい。
これらの補強材は、不飽和ポリエステル樹脂１００重量
部に対し、５〜１５０重量部、好ましくは１０〜１００
重量部混合される。これらの補強材は、硬化前の液体状
不飽和ポリエステル樹脂と発泡粒状物に充分に分散混合
していなければならず、分散が不十分な場合には強度の
確保が難しくなる。特に難燃性を得るためには難燃剤を
添加することが望ましい。難燃剤としては、有機系難燃
剤として、テトラブロモビスフェノールＡ、デカブロモ
ジフェニルオキサイド、ヘキサブロモベンゼン、ヘキサ
ブロモシクロドデカン、リン酸アンモニウム、トリクレ
ジルホスフェート、トリエチルフォスフェート、トリス
・β−クロロエチルホスフェート、酸性リン酸エステ
ル、含窒素リン化合物及びこれらの２以上の併用例示さ
れ、また、無機系難燃剤として三酸化アンチモン、四酸
化アンチモン、五酸化アンチモン、アンチモン酸ソー
ダ、酸化錫、燐系化合物（リン酸化合物、ハロゲン含有
リン酸化合物、ポリリン酸化合物、赤リン化合物、赤リ
ン）、水酸化アルミニウム、水酸化マグネシウム、カル
シウムアルミネート水和物、マグネシウムカーボネート
水和物、グアニジン化合物、ジルコニウム化合物、モリ
ブデン化合物、三酸化モリブデン、オクタモリブデン酸
アンチモン、硼酸アンチモン、硼酸マグネシウム、メタ
硼酸亜鉛、メタ硼酸バリウム、硼酸亜鉛、含水硼酸カル
シウム及びこれらの２以上の併用が例示される。これら
の難燃剤は、有機系難燃剤で不飽和ポリエステル樹脂１
００重量部に対し、０．０５〜４０重量部、好ましくは
０．１〜３０重量部混合され、また無機系難燃剤で不飽
和ポリエステル樹脂１００重量部に対し、５〜１５０重
量部、好ましくは１０〜１００重量部混合される。軽量
成形体及び軽量複合体に対して高い難燃効果を発現させ
るためには、前記難燃剤は硬化前の液状不飽和ポリエス
テル樹脂中にできるかぎり均一に分散配合させておく必
要がある。更なる難燃効果の向上のために、発泡粒状物
を構成する樹脂中にも難燃剤を配合しておくこともでき
る。In order to produce an uncured aggregate, first, a curing agent and a thickener are added to and mixed with a liquid unsaturated polyester resin to produce an unsaturated polyester resin mixture. The addition ratio of the curing agent is preferably from 0.1 to 1.0 part by weight, particularly preferably from 0.3 to 5.0 parts by weight, based on 100 parts by weight of the unsaturated polyester resin. The addition ratio of the thickener is preferably 0.2 to 10.0 parts by weight, particularly preferably 0.5 to 5.0 parts by weight, based on 100 parts by weight of the unsaturated polyester resin. In addition to the thickener and the curing agent, a low-shrinkage agent, an internal release agent, a filler, a pigment, a reinforcing material, a flame retardant, and the like can be added to the unsaturated polyester mixture as needed. In particular, it is desirable to add a reinforcing material to obtain high strength. Examples of the reinforcing material include a fibrous reinforcing material, a powdery reinforcing material, and the like.
As the fibrous reinforcing material, glass fiber, ceramic fiber,
Polyester fiber, vinyl chloride-acrylonitrile copolymer fiber, carbon fiber, steel fiber, aluminum fiber, boron fiber and a combination of two or more of these are exemplified.
As the powdery reinforcing material, glass powder and what is generally called an inorganic filler are silica, alumina, titanium oxide, iron oxide, zinc oxide, magnesium oxide, antimony oxide, barium ferrite, strontium ferrite, beryllium oxide, Pumice, talc, kaolin, mica, sericite, borax, aluminum hydroxide, magnesium hydroxide, aluminum carbonate, calcium carbonate, barium sulfate, ammonium sulfate, calcium sulfite and combinations of two or more of these are exemplified. In particular, in order to increase the strength of the lightweight molded article and the lightweight composite, the reinforcing material is preferably selected from the group consisting of glass fiber, glass powder, inorganic filler, and a mixture of two or more thereof.
These reinforcing materials are 5 to 150 parts by weight, preferably 10 to 100 parts by weight, based on 100 parts by weight of the unsaturated polyester resin.
Parts by weight. These reinforcing materials must be sufficiently dispersed and mixed in the liquid unsaturated polyester resin and the foamed granular material before curing, and when the dispersion is insufficient, it is difficult to secure the strength. In particular, in order to obtain flame retardancy, it is desirable to add a flame retardant. As a flame retardant, as an organic flame retardant, tetrabromobisphenol A, decabromodiphenyl oxide, hexabromobenzene, hexabromocyclododecane, ammonium phosphate, tricresyl phosphate, triethyl phosphate, tris-β-chloroethyl phosphate , Acidic phosphate esters, nitrogen-containing phosphorus compounds and combinations of two or more of these. Inorganic flame retardants such as antimony trioxide, antimony tetroxide, antimony pentoxide, sodium antimonate, tin oxide, phosphorus compounds ( Phosphoric acid compound, halogen-containing phosphoric acid compound, polyphosphoric acid compound, red phosphorus compound, red phosphorus), aluminum hydroxide, magnesium hydroxide, calcium aluminate hydrate, magnesium carbonate hydrate, guanidine compound, zirconium compound Molybdenum compounds, molybdenum trioxide, octamolybdate antimony, borate antimony, magnesium borate, metaborate, zinc, barium metaborate, zinc borate, hydrated calcium borate and 2 or in combination of these. These flame retardants are organic flame retardants and unsaturated polyester resins 1
With respect to 100 parts by weight, 0.05 to 40 parts by weight, preferably 0.1 to 30 parts by weight are mixed, and also, with respect to 100 parts by weight of the inorganic polyester resin with the inorganic flame retardant, 5 to 150 parts by weight, preferably 10 to 100 parts by weight are mixed. In order to exhibit a high flame-retardant effect on lightweight molded articles and lightweight composites, it is necessary to disperse and mix the flame retardant as uniformly as possible in the liquid unsaturated polyester resin before curing. In order to further improve the flame retardant effect, a flame retardant may be added to the resin constituting the foamed granular material.
【００１０】次に、不飽和ポリエステル樹脂混合物と、
発泡粒状物とを混合する。この混合は不飽和ポリエステ
ル樹脂がペ−スト状で粘度が低い状態を保持している間
に行う事が重要である。具体的には粘度が１０4ｃｐｓ
以下、好ましくは１０2〜１０3ｃｐｓ（これら粘度は、
いずれも４０℃以下で測定される粘度を意味する）にお
いて行う。不飽和ポリエステル樹脂混合物の粘度が１０
4ｃｐｓを越えると、粘度が高すぎて発泡粒状物表面へ
の薄くかつ均一なコ−ティング（被覆）が困難になった
り、粘着性が低下するので、発泡粒状物同士を接着させ
ることが困難な状態となる。したがって、このような粘
度にならないように、温度の制御に注意を払う必要があ
る。不飽和ポリエステル樹脂混合物の使用量は、発泡粒
状物の表面が全体的に薄く膜状となって付着させること
ができる程度であればよい。不飽和ポリエステル樹脂混
合物は、発泡粒状物１００重量部に対して、２０〜３０
０重量部、好ましくは５０〜１５０重量部である。コ−
テイング操作は、温度を硬化剤が実質的に硬化反応を生
じない温度、通常、４０℃以下以下で行なうべきであ
る。コ−テイング操作は、発泡粒状物と不飽和ポリエス
テル樹脂混合物とを容器内で混合することにより行うこ
とができる。Next, an unsaturated polyester resin mixture,
Mix with foamed granules. It is important to carry out this mixing while the unsaturated polyester resin is kept in a paste-like and low-viscosity state. Specifically, the viscosity is 10 4 cps
Hereinafter, preferably 10 2 to 10 3 cps (these viscosities are
In each case means a viscosity measured at 40 ° C. or lower). The viscosity of the unsaturated polyester resin mixture is 10
When the viscosity exceeds 4 cps, the viscosity is too high, so that thin and uniform coating (coating) on the surface of the expanded granular material becomes difficult, or the adhesiveness is reduced, so that it is difficult to adhere the expanded granular materials to each other. It becomes a state. Therefore, it is necessary to pay attention to the temperature control so as not to have such a viscosity. The amount of the unsaturated polyester resin mixture used may be such that the entire surface of the foamed granular material can be attached as a thin film. The unsaturated polyester resin mixture is 20 to 30 parts by weight based on 100 parts by weight of the expanded granular material.
0 parts by weight, preferably 50 to 150 parts by weight. Co
The tenting operation should be performed at a temperature at which the curing agent does not substantially cause a curing reaction, usually 40 ° C. or less. The coating operation can be performed by mixing the foamed granules and the unsaturated polyester resin mixture in a container.
【００１１】コ−ティング操作が完了後、得られた不飽
和ポリエステル樹脂混合物が表面に付着した発泡粒状物
を、型枠などの中に集積させた状態で収納し、３０〜４
０℃程度の温度雰囲気下で１〜４日放置する。すると増
粘剤の作用により増粘反応が進行し、やがて不飽和ポリ
エステル樹脂混合物の粘度が１０5ｃｐｓ以上に上昇
し、不飽和ポリエステル樹脂が常温において固体状ない
し半固体状を示すようになり、その結果、発泡粒状物未
硬化集合体からなる保形性のある塊状固形物となり、そ
の表面の粘着性が殆どなくなり、取り扱いやすくなる。
この状態では、硬化剤はまだ実質的には分解されていな
い。After completion of the coating operation, the obtained foamed granular material having the unsaturated polyester resin mixture adhered to its surface is stored in a form or the like in a form accumulated in a mold or the like.
It is left for 1 to 4 days in a temperature atmosphere of about 0 ° C. Then, the thickening reaction proceeds by the action of the thickener, and the viscosity of the unsaturated polyester resin mixture eventually increases to 10 5 cps or more, and the unsaturated polyester resin becomes solid or semi-solid at room temperature, As a result, it becomes a shape-retaining lump-shaped solid made of an uncured aggregate of expanded granular material, and its surface has almost no tackiness, which makes it easy to handle.
In this state, the curing agent has not been substantially decomposed yet.
【００１２】なお、前記発泡粒状物集積物を型枠内等に
て放置、増粘させるに当たっては、不飽和ポリエステル
樹脂混合物中のスチレン系モノマーの揮発を防止して行
なう必要がある。具体的には、該集積物の全体をポリエ
チレンシート等の合成樹脂シートで覆っておけば、スチ
レン系モノマーの揮発は防止できる。得られる未硬化集
合体は、発泡粒状物間に空隙を有するものであることが
望ましく、その空隙率の割合が大きいほど、プレス成形
して得られる軽量成形体及び軽量複合体は軽量性に優れ
たものとなる。なお、その空隙率の割合が大きいほど、
不飽和ポリエステル樹脂混合物が薄く均一に発泡粒状物
にコーティングされたことを意味する。また、不飽和ポ
リエステル樹脂混合物により発泡粒状物表面に対して薄
く均一なコーティングをほどこすためには、前記したコ
ーティング時の不飽和ポリエステル樹脂混合物の粘度を
１０4ｃｐｓ以下（好ましくは１０2〜１０3ｃｐｓ）と
し、発泡粒状物を構成する合成樹脂に、不飽和ポリエス
テル樹脂混合物との親和性の高いものを使用する。その
ような発泡粒状物としては、前記した変性ポリオレフィ
ン系樹脂を基材とする発泡粒子が適している。軽量成形
体並びに軽量複合体の軽量化という点においては、未硬
化集合体の空隙率を１０体積％以上にすることが好まし
い。変性ポリオレフィン系樹脂発泡粒子を使用する態様
では、薄く均一にコーティングされる結果、得られる集
合体の空隙率を３０体積％前後まで高めることが可能と
なる。その結果、軽量成形体中の発泡粒状物の割合を８
０〜９９体積％の範囲にまで容易に高めることが可能と
なり、しかも、そのように不飽和ポリエステル樹脂混合
物の使用量が極めて少量であるにもかかわらず、高強度
の軽量成形体を製造することができる。未硬化集合体
は、スチレン系モノマーの蒸発を防止しつつ、硬化剤の
分解温度により低い温度で保管しておけば、所定の期間
加熱プレス成形可能な状態を維持できる。即ち、この状
態で作り置きしたり、又は輸送して軽量成形体を製造す
る場所に運んで、ポリエチレン製シート等の覆いを取り
除けばプレス成形することが可能となる。When the foamed particulate matter aggregate is left in a mold or the like to increase the viscosity, it is necessary to prevent volatilization of the styrene-based monomer in the unsaturated polyester resin mixture. Specifically, volatilization of the styrene monomer can be prevented by covering the whole of the aggregate with a synthetic resin sheet such as a polyethylene sheet. It is desirable that the obtained uncured aggregate has voids between the foamed granules, and as the ratio of the porosity is larger, the lightweight molded article and the lightweight composite obtained by press molding have excellent lightness. It will be. In addition, as the ratio of the porosity is larger,
It means that the unsaturated polyester resin mixture was thinly and uniformly coated on the foamed granules. Further, in order to apply a thin and uniform coating to the foamed granular material surface with the unsaturated polyester resin mixture, the viscosity of the unsaturated polyester resin mixture at the time of the coating is set to 10 4 cps or less (preferably 10 2 to 10 cps). 3 cps), and a synthetic resin having a high affinity with the unsaturated polyester resin mixture is used as the synthetic resin constituting the foamed granular material. As such expanded granules, expanded particles based on the above-mentioned modified polyolefin-based resin are suitable. From the viewpoint of reducing the weight of the lightweight molded article and the lightweight composite, the porosity of the uncured aggregate is preferably set to 10% by volume or more. In the embodiment using the modified polyolefin-based resin foamed particles, as a result of the thin and uniform coating, the porosity of the obtained aggregate can be increased to about 30% by volume. As a result, the ratio of the foamed particulate matter in the lightweight compact was 8
0-99% by volume can be easily increased, and even though the amount of the unsaturated polyester resin mixture used is extremely small, it is possible to produce a high-strength lightweight molded article. Can be. If the uncured aggregate is stored at a temperature lower than the decomposition temperature of the curing agent while preventing evaporation of the styrene-based monomer, a state in which press molding can be performed for a predetermined period can be maintained. That is, press molding can be performed by preparing or storing in this state, or transporting to a place where a lightweight molded body is manufactured, and removing a cover such as a polyethylene sheet.
【００１３】前記プレス成形時の加熱温度は、ポリエス
テル樹脂混合物に含まれる硬化剤の分解温度以上の温度
で行われる。不飽和ポリエステル樹脂混合物は、増粘剤
により増粘されているだけであるので、そのような加熱
下におかれると、初期の段階では熱のために粘度は低下
し、粒状物間の固着力が弱まり、粒状物の移動及び変形
が容易となる。したがって、そのような現象を利用すれ
ば、プレス成形により板状のみならず、浅絞り状にも成
形可能となる。その後、そのような加熱下でプレス状態
を維持しておけば、硬化（架橋）反応の進行と共に粘度
が再び増大し、最終的には完全に硬化する。冷却して型
内から取り出された軽量成形体中に占める発泡粒状物間
の空隙率は、７体積％以下、好ましくは５体積％以下で
ある。未硬化集合体をプレス成形する際のプレスの度合
を高くするほどこの空隙率は小さくでき、この空隙率が
小さいほど高強度の軽量成形体となる。特に、未硬化集
合体とそれから得られる軽量成形体との関係において、
未硬化集合体の見掛けの体積（発泡粒状物間の空隙部を
も含む体積）に対し、軽量成形体の見掛けの体積が２５
〜６０％（見掛けの圧縮率４０〜７５体積％）となるよ
うにプレス成形して得られた軽量成形体は、密度当たり
の曲げ降伏点強度が高まる。なお、さほどの高強度を必
要とせず、透水性や吸音性の機能を利用しようとする場
合には、その空隙率は、高くしてもよい。The heating temperature during the press molding is a temperature higher than the decomposition temperature of the curing agent contained in the polyester resin mixture. Unsaturated polyester resin mixtures are only thickened by thickeners, so when placed under such heating, the viscosity decreases in the early stages due to heat, and the cohesion between the particulates And the movement and deformation of the granular material are facilitated. Therefore, if such a phenomenon is used, not only a plate shape but also a shallow drawing shape can be formed by press molding. Thereafter, if the pressed state is maintained under such heating, the viscosity increases again with the progress of the curing (crosslinking) reaction, and finally the resin is completely cured. The porosity between the foamed particulate matter in the lightweight compact taken out of the mold after cooling is 7% by volume or less, preferably 5% by volume or less. The porosity can be reduced by increasing the degree of pressing at the time of press-forming the uncured aggregate, and the smaller the porosity, the higher the strength of the lightweight molded body. In particular, in the relationship between the uncured aggregate and the lightweight molded body obtained therefrom,
The apparent volume of the uncured aggregate (the volume including voids between the foamed granules) and the apparent volume of the lightweight molded body are 25.
A lightweight molded body obtained by press molding to have a compression yield of 率 60% (apparent compression ratio of 40 to 75% by volume) has an increased bending yield point strength per density. In addition, when not using high strength and trying to use the function of water permeability and sound absorption, the porosity may be increased.
【００１４】次に、本発明の軽量複合体は、軽量成形体
に表面材を積層一体化したものである。この一体化によ
り軽量成形体の強度を著しく高めることが可能となる。
軽量複合体を製造するに当たっては、前記した未硬化集
合体の少なくとも片面（軽量複合体の高強度化のために
は両面が望ましい。）に表面材を積層状態とした中間体
の形態を経由させることが望ましい。このような未硬化
集合体と表面材との積層体からなる中間体（以下、単に
中間体ともいう）を使用すれば、軽量成形体を製造する
要領で、加熱プレス成形することにより容易に軽量複合
体を製造することができる。表面材には、繊維強化熱硬
化性樹脂、繊維強化熱可塑性樹脂、熱硬化性樹脂、熱可
塑性樹脂、金属、木材などの板状体やシート状体が用い
られる。表面材はプレス成形時の温度により化学変化を
受けるものもある。繊維強化樹脂に用いられる強化用繊
維としては、ガラス繊維、炭素繊維、ホウ素繊維、金属
繊維、セラミック繊維、ポリエステル系繊維、塩化ビニ
ル・アクリロニトリル共重合体系繊維、ポリビニルアル
コール系繊維などがある。表面材の厚さは適宜決めるこ
とができるが、一般的には０．１〜５．０ｍｍ、好まし
くは０．３〜２．０ｍｍである。なお、表面材は、中間
体を加熱プレス成形した際に、表面材として軽量成形体
と強固に接着一体化されることが望まれる。なぜなら
ば、その接着強度が高い程、軽量複合体の機械的強度が
高くできるからである。そのような強固な接着性を得よ
うとする観点から、表面材としては、強化用繊維を配し
た未硬化の熱硬化性樹脂からなるものが好ましく、更に
強化用繊維を配した未硬化の不飽和ポリエステル樹脂か
らなるものが望ましく、更には強化用繊維を配した硬化
剤と増粘剤を含有する実質的に未硬化の固体状ないし半
固体状の不飽和ポリエステル樹脂からなるものが最も望
ましい。この場合の強化用繊維を配した硬化剤と増粘剤
を含有する実質的に未硬化の固体状ないし半固体状の不
飽和ポリエステル樹脂からなるものは、未硬化集合体を
構成する不飽和ポリエステル樹脂混合物と極めて近い組
成を有するので、加熱プレス成形時の熱の作用により、
初期の段階で未硬化集合体と表面材をほぼ同時に熱成形
可能な状態とすることができ、その後ほぼ同時に硬化反
応が進行して、ほぼ同時に硬化反応を完了させることが
できる。この組み合わせは、加熱プレス成形効率に優れ
ていると共に、加熱プレス成形前は粘着性が殆んどなく
なっているので取り扱い性にも優れており、更には表面
剤の方も絞り成形が可能となるので、軽量複合体の浅絞
り成形体の製造をも可能にするものである。なお、この
態様において、更に成形効率を高めるためには、未硬化
集合体に使用される硬化剤と表面材に使用される硬化剤
とを同じものとするか、又は違う場合でも分解温度が近
いのものを選択すべきである。Next, the lightweight composite of the present invention is obtained by laminating and integrating a surface material on a lightweight molded article. This integration makes it possible to significantly increase the strength of the lightweight molded body.
In producing the lightweight composite, at least one surface of the uncured aggregate (both surfaces are desirable for increasing the strength of the lightweight composite) is passed through a form of an intermediate in which surface materials are laminated. It is desirable. If an intermediate (hereinafter, also referred to simply as an intermediate) composed of a laminate of such an uncured aggregate and a surface material is used, it can be easily lightweighted by hot press molding in the manner of producing a lightweight molded body. A composite can be produced. As the surface material, a plate or sheet made of fiber-reinforced thermosetting resin, fiber-reinforced thermoplastic resin, thermosetting resin, thermoplastic resin, metal, wood, or the like is used. Some surface materials undergo a chemical change depending on the temperature during press molding. Examples of the reinforcing fibers used in the fiber reinforced resin include glass fibers, carbon fibers, boron fibers, metal fibers, ceramic fibers, polyester fibers, vinyl chloride / acrylonitrile copolymer fibers, and polyvinyl alcohol fibers. Although the thickness of the surface material can be determined as appropriate, it is generally 0.1 to 5.0 mm, preferably 0.3 to 2.0 mm. It is desired that the surface material be firmly bonded and integrated with the lightweight molded body as the surface material when the intermediate is subjected to hot press molding. This is because the higher the adhesive strength, the higher the mechanical strength of the lightweight composite. From the viewpoint of obtaining such strong adhesiveness, the surface material is preferably made of an uncured thermosetting resin provided with reinforcing fibers, and is preferably an uncured non-cured resin provided with reinforcing fibers. Those composed of a saturated polyester resin are desirable, and those composed of a substantially uncured solid or semi-solid unsaturated polyester resin containing a curing agent provided with reinforcing fibers and a thickener are most desirable. In this case, the substantially uncured solid or semi-solid unsaturated polyester resin containing a curing agent having a reinforcing fiber and a thickener is an unsaturated polyester constituting an uncured aggregate. Because it has a composition very close to the resin mixture, the action of heat during hot press molding
At the initial stage, the uncured aggregate and the surface material can be made into a thermoformable state almost simultaneously, and thereafter the curing reaction proceeds almost simultaneously, and the curing reaction can be completed almost simultaneously. This combination is excellent in heat press molding efficiency, and has excellent tackiness because almost no tackiness is formed before hot press molding, and furthermore, the surface agent can be drawn and formed. Therefore, it is also possible to manufacture a shallow drawn compact of a lightweight composite. In this embodiment, in order to further increase the molding efficiency, the curing agent used for the uncured aggregate and the curing agent used for the surface material are the same, or the decomposition temperature is close even if different. You should choose one.
【００１５】強化用繊維を配した硬化剤と増粘剤を含有
する実質的に未硬化の増粘された状態の不飽和ポリエス
テル樹脂からなる表面材は、未硬化集合体を形成するた
めの前記したペースト状の不飽和ポリエステル樹脂混合
物を製造する際に、同時に製造することができる。同一
のペースト状の不飽和ポリエステル樹脂混合物を、一方
でガラス繊維チョップドストランドと混合して表面材を
形成し、他方で発泡粒状物と混合して型枠内等に入れ
て、その集積物を形成すればよい。その際、表面材と集
積物とを重ね合わせた状態でポリエチレン製シート等で
覆って増粘させると、両者（表面材を集積物の上下面に
配した場合には三者）が接着一体化された中間体を得る
ことができる。固体状又は半固体状にまで十分に増粘さ
せた後、プレス成形時にポリエチレン製シートの覆いを
取り除いて一体化された中間体を、軽量成形体を製造す
る場合と同様にして、加熱下でプレス成形すれば容易に
軽量複合体を製造することができる。この態様は、同一
の中間体を連続的に大量に生産する場合や、未硬化集合
体と表面材とを同じ場所で製造する場合に適している。[0015] A surface material comprising a substantially uncured and thickened unsaturated polyester resin containing a curing agent provided with reinforcing fibers and a thickener is used to form an uncured aggregate. When the paste-like unsaturated polyester resin mixture is produced, it can be produced at the same time. The same paste-like unsaturated polyester resin mixture is mixed with glass fiber chopped strands on the one hand to form a surface material, and on the other hand mixed with foamed granules and placed in a mold to form an aggregate do it. At this time, if the surface material and the stack are overlapped and covered with a polyethylene sheet or the like to increase the viscosity, the two (if the surface material is arranged on the upper and lower surfaces of the stack) are bonded and integrated. The obtained intermediate can be obtained. After sufficiently thickening to a solid or semi-solid state, the intermediate body integrated by removing the cover of the polyethylene sheet during press molding, in the same manner as in the case of manufacturing a lightweight molded body, under heating Press molding can easily produce a lightweight composite. This embodiment is suitable when the same intermediate is continuously mass-produced, or when the uncured aggregate and the surface material are manufactured in the same place.
【００１６】また、表面剤と前記集積物とを別々にポリ
エチレン製シート等で覆って増粘させ、固体状ないし半
固体状まで十分に増粘させた後、ポリエチレン製シート
の覆いを取り除いて、未硬化集合体の片面又は両面に表
面剤を重ねあわせた（固着していない）中間体を使用し
ても、軽量成形体を製造する場合と同様にして、加熱下
でプレス成形すれば容易に軽量複合体を製造することが
できる。この態様における表面剤は、同等の組成を持つ
市販の安価なシートモールディングコンパウンド（不飽
和ポリエステル樹脂に硬化剤、増粘剤、充填剤、内部離
型剤、低収縮材、顔料等を混合したペースト状の樹脂混
合物にガラス繊維チョップドストランドを配した後、両
面をフィルムで覆ってシート状とし、これを一定時間お
いて増粘させて、粘着性のない非流動性状態としたも
の）で代用することができるので好ましい。このような
中間体の使用は、少ロット多品種の生産を行なう場合
や、未硬化集合体と表面剤とを別な場所で生産するよう
な場合に有利であると言える。なお、加熱プレス成形時
に必要とされるプレス圧力は、未硬化集合体を構成する
発泡粒状物の基材樹脂の種類や発泡倍率、表面剤の種類
及び有無、更には軽量成形体にどの程度の空隙率をもた
せたいのか等に応じて変化するが、高くともせいぜい３
０ｋｇｆ／ｃｍ2程度である。Further, the surface agent and the above-mentioned aggregate are separately covered with a polyethylene sheet or the like to increase the viscosity, and after sufficiently thickening to a solid or semi-solid state, the covering of the polyethylene sheet is removed. Even if an intermediate in which a surface agent is superimposed (unfixed) on one or both surfaces of the uncured aggregate is used, press molding under heating can be easily performed in the same manner as in the case of manufacturing a lightweight molded body. Lightweight composites can be manufactured. The surface agent in this embodiment is a commercially available inexpensive sheet molding compound having the same composition (a paste obtained by mixing a curing agent, a thickener, a filler, an internal mold release agent, a low shrinkage material, a pigment, etc. with an unsaturated polyester resin). After arranging glass fiber chopped strands in a resin mixture in the form of a sheet, both sides are covered with a film to form a sheet, which is thickened after a certain period of time to make it a non-sticky non-flowable state). It is preferable because it can be used. The use of such an intermediate can be said to be advantageous in the case of producing small lots and many kinds of products, or in the case where the uncured aggregate and the surface agent are produced in different places. The press pressure required at the time of hot press molding is based on the type of the base resin and the expansion ratio of the expanded granular material constituting the uncured aggregate, the type and presence or absence of the surface agent, and how much the light molded body is. Varies depending on whether the porosity is desired, but at most 3
It is about 0 kgf / cm 2 .
【００１７】[0017]
【実施例】以下に本発明の実施例を示す。実施例で得ら
れた軽量成形体及び軽量複合体の効果を確認するため
に、曲げ弾性率、曲げ降伏点強度を、いずれもＪＩＳ
６９１１により測定した。Examples of the present invention will be described below. In order to confirm the effects of the lightweight molded article and the lightweight composite obtained in the examples, the flexural modulus and the flexural yield point strength were both measured according to JIS.
6911.
【００１８】〔未硬化状合成樹脂発泡粒状物集合体及び
軽量成形体の製造例１−１〕エチレン成分量４．０重量
％のプロピレン−エチレンランダム共重合体６０重量
％、耐衝撃性ポリスチレン３０重量％及び１，２−ポリ
ブタジエン１０重量％からなる混合樹脂粒子の架橋化物
（沸騰トルエン中での５時間還流後の不溶分割合が３５
重量％）（変性ポリプロピレン系樹脂粒子）を発泡さ
せ、真密度が０．０９６ｇ／ｃｍ3の発泡粒子を製造し
た。次に、液状不飽和ポリエステル樹脂（日本ユピカ
（株）製の商品名「ユピカ７５０６」）１００重量部と
酸化マグネシウム（増粘剤）１重量部及びラウロイルパ
ーオキサイド（硬化剤）３重量部とを、硬化剤が実質的
に分解する温度未満で予備混合した。続いて、粘着性の
高いペースト状の前記予備混合物１０４重量部と前記発
泡粒子１００重量部とを容器内に入れて、該発泡粒子表
層部の全面が予備混合物で全面被覆されるように混合操
作を行った。次に、内寸法が長さ５００ｍｍ、幅５００
ｍｍ、深さ１００ｍｍの樹脂製型枠を用意し、大判のポ
リエチレン製シートを型枠内壁面に沿わせ、その上か
ら、前記容器内容物の厚みが約６０ｍｍとなるように型
枠内に入れ、更にその上からをポリエチレン製シートで
覆って、３５℃雰囲気下で３日間放置した。型枠から取
り出された未硬化状合成樹脂発泡粒状物集合体は、不飽
和ポリエステル樹脂が常温において固体状ないし半固体
状に増粘された結果、長さ５００ｍｍ、幅５００ｍｍ、
厚み６０ｍｍのサイズ、０．１１ｇ／ｃｍ3の嵩密度、
３１体積％の空隙率を持つもので、保形性に優れ、粘着
性が殆んどない取り扱い易いものであった。次に、この
集合体を長さ４００ｍｍ、幅３００ｍｍ（厚み６０ｍｍ
はそのまま）に切断した。この切断された未硬化集合体
を、長さ４００ｍｍ、幅３００ｍｍ、深さ１００ｍｍの
内寸を有し、かつ内部がポリテトラフルオロエチレン樹
脂で表面処理された１１０℃に加熱されたアルミニウム
製雌金型内に入れ、この雌金型に一致するプレス機構を
有する同材質の１１０℃に加熱された雄金型にてプレス
（プレス圧力は１０ｋｇｆ／ｃｍ2）し、そのままその
温度で４０分間保持した後、６０℃以下に両金型を冷却
し、軽量成形体を取り出し、２３℃、５０％ＲＨの雰囲
気下で４８時間放置した。その軽量成形体は、長さ４０
０ｍｍ、幅３００ｍｍ、厚み４０ｍｍのサイズ、０．１
９ｇ／ｃｍ3の嵩密度、５体積％以下の空隙率を持つも
のであった。また、その軽量成形体は、曲げ弾性率が３
１０ｋｇｆ／ｃｍ2、曲げ降伏点強度が４０ｋｇｆ／ｃ
ｍ2の曲げ物性（いずれもＪＩＳ Ｋ６９１１による測
定）を持つものであった。[Production Example 1-1 of Uncured Synthetic Resin Foamed Granular Material Aggregate and Light-Weight Molded Product 1-1] 60% by weight of a propylene-ethylene random copolymer having an ethylene content of 4.0% by weight, and impact-resistant polystyrene 30 % And 10% by weight of 1,2-polybutadiene in a crosslinked product (the insoluble content after refluxing in boiling toluene for 5 hours is 35%).
(% By weight) (modified polypropylene resin particles) was expanded to produce expanded particles having a true density of 0.096 g / cm 3 . Next, 100 parts by weight of a liquid unsaturated polyester resin (trade name “Yupika 7506” manufactured by Nippon Yupika Co., Ltd.), 1 part by weight of magnesium oxide (thickener) and 3 parts by weight of lauroyl peroxide (curing agent) were added. Premixed below a temperature at which the curing agent substantially decomposes. Subsequently, 104 parts by weight of the paste-like pre-mixture having high tackiness and 100 parts by weight of the foam particles are put into a container, and a mixing operation is performed so that the entire surface of the foam particle surface layer is completely covered with the pre-mixture. Was done. Next, the inner dimensions are 500 mm in length and 500 mm in width.
mm, a resin mold having a depth of 100 mm is prepared, a large-sized polyethylene sheet is placed along the inner wall of the mold, and then placed in the mold so that the thickness of the container contents is about 60 mm. The sheet was further covered with a polyethylene sheet and allowed to stand at 35 ° C. for 3 days. The uncured synthetic resin foam granule aggregate taken out of the mold is a solid or semi-solid thickened unsaturated polyester resin at room temperature, resulting in a length of 500 mm, a width of 500 mm,
60 mm thick, 0.11 g / cm 3 bulk density,
It had a porosity of 31% by volume, was excellent in shape retention, and had little tackiness and was easy to handle. Next, this assembly was 400 mm long and 300 mm wide (60 mm thick).
Was cut as it is). The cut uncured aggregate was heated to 110 ° C. and heated to 110 ° C. having an inner size of 400 mm in length, 300 mm in width, and 100 mm in depth, and the inside of which was surface-treated with polytetrafluoroethylene resin. It was put into a mold, pressed by a male mold of the same material having a press mechanism corresponding to the female mold and heated to 110 ° C. (press pressure: 10 kgf / cm 2 ), and kept at that temperature for 40 minutes. Thereafter, both molds were cooled to 60 ° C. or lower, the lightweight molded body was taken out, and left for 48 hours in an atmosphere of 23 ° C. and 50% RH. The lightweight compact has a length of 40
0 mm, width 300 mm, thickness 40 mm, 0.1
It had a bulk density of 9 g / cm 3 and a porosity of 5% by volume or less. The lightweight molded body has a flexural modulus of 3
10 kgf / cm 2 , bending yield point strength is 40 kgf / c
The material had bending properties of m 2 (measured according to JIS K6911).
【００１９】〔未硬化状合成樹脂発泡粒状物集合体及び
軽量成形体の製造例１−２〕前記製造例１−１と同じ操
作を行って未硬化集合体を製造した。ただし、３５℃雰
囲気下での放置だけを３日から１０日に延長した。この
ものは、ポリエチレン製シートでしっかりと覆って、ス
チレンモノマーの揮発を防止するようにして保存されて
いたので、１０日後であっても、前記製造例１−１と同
じ加熱プレス成形にて製造例１−１と実質的に同一の軽
量成形体を得ることができた。[Production Example 1-2 of Uncured Synthetic Resin Expanded Granular Material Aggregate and Light-Weight Molded Product] An uncured aggregate was produced by performing the same operation as in Production Example 1-1. However, only the standing at 35 ° C. was extended from 3 days to 10 days. This was covered with a polyethylene sheet firmly and stored so as to prevent volatilization of the styrene monomer, so that even after 10 days, it was manufactured by the same hot press molding as in the above-mentioned Production Example 1-1. A substantially same lightweight molded article as in Example 1-1 was obtained.
【００２０】〔未硬化状合成樹脂発泡粒状物集合体及び
軽量成形体の製造例１−３〕加熱プレス時のプレス圧力
を１ｋｇｆ／ｃｍ2に変更して、前記製造例１−１を繰
り返した。得られた軽量成形体は、長さ４００ｍｍ、幅
３００ｍｍ、厚み５０ｍｍのサイズ、０．１６ｇ／ｃｍ
3の嵩密度、１６体積％の空隙率を持つものであった。
また、その軽量成形体は、曲げ弾性率が１２０ｋｇｆ／
ｃｍ2、曲げ降伏点強度が１１ｋｇｆ／ｃｍ2の曲げ物性
（いずれもＪＩＳ Ｋ６９１１による測定）を持つもの
であった。[Production Example 1-3 of Uncured Synthetic Resin Foamed Granular Material Aggregate and Light-Weight Molded Product] The above-mentioned Production Example 1-1 was repeated while changing the pressing pressure at the time of hot pressing to 1 kgf / cm 2 . . The obtained lightweight molded body has a size of 400 mm in length, 300 mm in width and 50 mm in thickness, and 0.16 g / cm.
It had a bulk density of 3 and a porosity of 16% by volume.
The lightweight molded body has a flexural modulus of 120 kgf /
cm 2 and a flexural yield point strength of 11 kgf / cm 2 , all of which had bending properties (measured according to JIS K6911).
【００２１】〔中間体及び軽量複合体の製造例２−１〕
製造例１−１と全く同じ材料の使用及び操作により、発
泡粒子表層部の全体が粘着性の高いペースト状の予備混
合物で被覆されるように容器内で混合操作を行った。そ
の一方で、液状不飽和ポリエステル樹脂１００重量部と
酸化マグネシウム（増粘剤）１重量部及びラウロイルパ
ーオキサイド（硬化剤）３重量部とを、硬化剤が実質的
に分解する温度未満で混合し、これを、４５０ｇ／ｍ2
のチョップドストランドマット上にローラーを用いて浸
透させ、脱泡した厚み１ｍｍの表面剤を２枚用意した。
次に、内寸法が長さ５００ｍｍ、幅５００ｍｍ、深さ１
００ｍｍの樹脂製型枠を用意し、大判のポリエチレン製
シートを型枠内壁面に沿わせ、その上から型枠内に表面
剤を敷き、その上に前記容器内混合物を、その厚みが２
０ｍｍとなるよう型枠内に入れ、その上に表面剤をの
せ、更にその上からポリエチレン製シートで覆って、３
５℃雰囲気下で３日間放置した。なお、ここで使用され
た、表面剤：容器内混合物：表面剤は、２６：４８：２
６の重量比であった。型枠から取り出された中間体（未
硬化状合成樹脂発泡粒状物集合体の上下面に表面剤が接
着されたもの）は、不飽和ポリエステル樹脂が常温にお
いて固体状ないし半固体状に増粘された結果、長さ５０
０ｍｍ、幅５００ｍｍ、厚み２２ｍｍのサイズ、０．２
０ｇ／ｃｍ3の嵩密度、３１体積％の空隙率（表面剤を
取り除いたと仮定した未硬化状合成樹脂発泡粒状物集合
体部分の空隙率）を持つもので、保形性に優れ、粘着性
が殆んどない取り扱い易いものであった。次に、この中
間体を長さ４００ｍｍ、幅３００ｍｍ（厚み２２ｍｍは
そのまま）に切断した。この切断された中間体を、長さ
４００ｍｍ、幅３００ｍｍ、深さ１００ｍｍの内寸を有
し、かつ内部がポリテトラフルオロエチレン樹脂で表面
処理された１１０℃に加熱されたアルミニウム製雌金型
内に入れ、この雌金型に一致するプレス機構を有する同
材質の１１０℃に加熱されている雄金型にてプレス（プ
レス圧力は１０ｋｇｆ／ｃｍ2）し、そのままその温度
で４０分間保持した後、６０℃以下に両金型を冷却し、
軽量複合体を取り出し、２３℃、５０％ＲＨの雰囲気下
で４８時間放置した。その軽量複合体は、長さ４００ｍ
ｍ、幅３００ｍｍ、厚み１０ｍｍのサイズ、０．４９ｇ
／ｃｍ3の嵩密度、５体積％以下の空隙率（表面材を取
り除いたと仮定した軽量成形体部分の空隙率）を持つも
のであった。また、その軽量複合体は、曲げ弾性率が２
１８００ｋｇｆ／ｃｍ2、曲げ降伏点強度が２１０ｋｇ
ｆ／ｃｍ2の曲げ物性（いずれもＪＩＳ Ｋ６９１１に
よる測定）を持つものであった。[Production Example 2-1 of Intermediate and Lightweight Composite]
The mixing operation was performed in a container by using exactly the same material and operation as in Production Example 1-1 such that the entire surface layer of the foamed particles was covered with the paste-like pre-mixture having high adhesiveness. On the other hand, 100 parts by weight of the liquid unsaturated polyester resin, 1 part by weight of magnesium oxide (thickener) and 3 parts by weight of lauroyl peroxide (curing agent) are mixed at a temperature lower than the temperature at which the curing agent is substantially decomposed. , Which is 450 g / m 2
, And two defoamed surface agents having a thickness of 1 mm were prepared by infiltrating into a chopped strand mat using a roller.
Next, the inner dimensions are 500 mm in length, 500 mm in width, and 1 in depth.
A resin mold of 00 mm is prepared, a large-sized polyethylene sheet is placed along the inner wall surface of the mold, a surface agent is laid on the mold from above, and the mixture in the container is placed on the surface of the mold.
0 mm, put a surface agent on top of it, cover it with a polyethylene sheet,
It was left under a 5 ° C. atmosphere for 3 days. The surface agent: mixture in the container: surface agent used here was 26: 48: 2.
The weight ratio was 6. The intermediate (the surface of the uncured synthetic resin foam granule aggregate with surface agents adhered to the upper and lower surfaces of the aggregate of uncured synthetic resin foam) taken out of the mold is increased in viscosity of the unsaturated polyester resin into a solid or semi-solid at room temperature. As a result, length 50
0 mm, width 500 mm, thickness 22 mm, 0.2
It has a bulk density of 0 g / cm 3 and a porosity of 31% by volume (porosity of the uncured synthetic resin foam granule aggregate portion assuming that the surface agent is removed), and has excellent shape retention and adhesiveness. But it was easy to handle. Next, this intermediate product was cut into a length of 400 mm and a width of 300 mm (thickness of 22 mm was maintained). The cut intermediate was placed in an aluminum female mold heated to 110 ° C., having an inner dimension of 400 mm in length, 300 mm in width, and 100 mm in depth, and the inside of which was surface-treated with polytetrafluoroethylene resin. And pressed by a male mold of the same material having a press mechanism corresponding to the female mold and heated to 110 ° C. (press pressure is 10 kgf / cm 2 ), and the temperature is maintained at that temperature for 40 minutes. Cool both molds below 60 ° C,
The lightweight composite was taken out and left under an atmosphere of 23 ° C. and 50% RH for 48 hours. The lightweight composite is 400m long
m, width 300 mm, thickness 10 mm, 0.49 g
/ Cm 3 , having a porosity of 5% by volume or less (porosity of the lightweight molded body portion assuming that the surface material was removed). The lightweight composite has a flexural modulus of 2
1800 kgf / cm 2 , bending yield point strength 210 kg
It had bending physical properties of f / cm 2 (both measured according to JIS K6911).
【００２２】〔中間体及び軽量複合体の製造例２−２〕
前記製造例２−１と同じ操作を行なって中間体を製造し
た。ただし、３５℃雰囲気下での放置を３日から１０日
に延長した。このものは、ポリエチレン製シートでしっ
かりと覆ってスチレンモノマーの揮発を防止するように
して保存されていたので、１０日後であっても、前記製
造例２−１と同じ加熱プレス成形にて製造例２−１と実
質的に同一の軽量複合体を得ることができた。[Production Example 2-2 of Intermediate and Lightweight Composite]
An intermediate was produced in the same manner as in Production Example 2-1. However, the standing at 35 ° C. was extended from 3 days to 10 days. This product was stored in such a manner that it was covered firmly with a polyethylene sheet to prevent volatilization of the styrene monomer, so that even after 10 days, it was manufactured by the same hot press molding as in the above-mentioned Production Example 2-1. A lightweight composite substantially the same as 2-1 was obtained.
【００２３】〔中間体及び軽量複合体製造例２−３〕製
造例１−１を繰り返して、それと同一の未硬化状合成樹
脂発泡粒状物集合体を製造した。次いで、製造開始から
３日後に、同様に、長さ４００ｍｍ、幅３００ｍｍに切
断した。一方、十分に増粘され粘着性が殆んどなくなっ
ている市販のシートモールディングコンパウンド（武田
薬品工業株式会社の商品名「セレクティマットＲ−１０
１」）から、長さ４００ｍｍ、幅３００ｍｍの２枚のシ
ートモールディングコンパウンドを切り出し、それら２
枚のシートモールディングコンパウンドを前記未硬化集
合体の上下面に重ね合わせた状態で、雌金型内に配置
し、製造例２−１と同一条件にて、加熱プレス成形を行
なった。次に、取り出した軽量複合体を２３℃、５０％
ＲＨの雰囲気下で４８時間放置した。得られた軽量複合
体は、長さ４００ｍｍ、幅３００ｍｍ、厚み１１ｍｍの
サイズ、０．５１ｇ／ｃｍ3の嵩密度、５体積％以下の
空隙率（表面材を取り除いたと仮定した軽量成形体部分
の空隙率）を持つものであった。また、その軽量複合体
は、曲げ弾性率が２４５００ｋｇｆ／ｃｍ2、曲げ降伏
点強度が３０１ｋｇｆ／ｃｍ2の曲げ物性（いずれもＪ
ＩＳ Ｋ６９１１による測定）を持つものであった。[Preparation Example 2-3 of Intermediate and Light-Weight Composite] Preparation Example 1-1 was repeated to produce the same uncured synthetic resin foam granule aggregate. Next, three days after the start of production, the pieces were similarly cut into a length of 400 mm and a width of 300 mm. On the other hand, a commercially available sheet molding compound which has been sufficiently thickened and has almost no tackiness (trade name “SELECTIMAT R-10 by Takeda Pharmaceutical Co., Ltd.)
1)), cut out two sheet molding compounds having a length of 400 mm and a width of 300 mm,
Two sheet molding compounds were placed in a female mold in a state of being superposed on the upper and lower surfaces of the uncured aggregate, and hot press molding was performed under the same conditions as in Production Example 2-1. Next, the taken out lightweight composite was heated at 23 ° C. and 50%
It was left under an atmosphere of RH for 48 hours. The obtained lightweight composite has a size of 400 mm in length, 300 mm in width, 11 mm in thickness, a bulk density of 0.51 g / cm 3 , and a porosity of 5% by volume or less (for a lightweight molded body portion assumed to have a surface material removed). (Porosity). The lightweight composite has a flexural modulus of 24,500 kgf / cm 2 and a flexural yield point strength of 301 kgf / cm 2 (both J properties).
IS K6911).
【００２４】〔中間体及び軽量複合体の製造例２−４〕
加熱プレス時のプレス圧力を１ｋｇｆ／ｃｍ2に変更し
て前記製造例２−１を繰り返した。得られた軽量複合体
は、長さ４００ｍｍ、幅３００ｍｍ、厚み１６ｍｍのサ
イズ、０．３２ｇ／ｃｍ3の嵩密度、１６体積％の空隙
率（表面材を取り除いたと仮定した軽量成形体部分の空
隙率）を持つものであった。また、その軽量複合体は、
曲げ弾性率が９６００ｋｇｆ／ｃｍ2、曲げ降伏点強度
が８８ｋｇｆ／ｃｍ2の曲げ物性（いずれもＪＩＳ Ｋ
６９１１による測定）を持つものであった。[Production Example 2-4 of Intermediate and Lightweight Composite]
The above Production Example 2-1 was repeated, except that the press pressure during the heating press was changed to 1 kgf / cm 2 . The obtained lightweight composite had a length of 400 mm, a width of 300 mm, a thickness of 16 mm, a bulk density of 0.32 g / cm 3 , and a porosity of 16% by volume (the voids in the lightweight molded body portion assumed to have the surface material removed). Rate). Also, the lightweight composite,
Flexural properties with a flexural modulus of 9600 kgf / cm 2 and a bending yield point strength of 88 kgf / cm 2 (both JIS K
6911).
【００２５】〔未硬化状合成樹脂発泡粒状物集合体及び
軽量成形体の製造例３−１〕 （ガラス繊維配合による強度向上例）製造例１−１と同
じ素材、及び同じ操作で発泡粒子を製造した。次に液状
不飽和ポリエステル樹脂１００重量部と酸化マグネシウ
ム（増粘剤）１重量部及びラウロイルパーオキサイド
（硬化剤）３重量部、さらに補強材として市販のガラス
繊維（旭ファイバーグラス株式会社の商品名「ＭＦ２０
ＭＨ２−２０」）３０重量部とを、硬化剤が実質的に分
解する温度未満で予備混合した。続いて、粘着性の高い
ペースト状の前記予備混合物１３４重量部と前記発泡粒
子１００重量部とを容器に入れて、該発泡粒子表層部の
全面が予備混合物で全面被覆されるように混合操作を行
った。次に内寸法が長さ５００ｍｍ、幅５００ｍｍ、深
さ１００ｍｍの樹脂製型枠を用意し、大判のポリエチレ
ン製シートを型枠内壁面に沿わせ、その上から、前記容
器内容物の厚みが約６０ｍｍとなるように型枠に入れ、
更にその上から、ポリエチレン製シートで覆って、３５
℃雰囲気下で３日間放置した。型枠から取り出された未
硬化状合成樹脂発泡粒状物集合体は、不飽和ポリエステ
ル樹脂が常温において固体状ないし半固体状に増粘され
た結果、長さ５００ｍｍ、幅５００ｍｍ、厚み６０ｍｍ
のサイズ、０．１６ｇ／ｃｍ3の嵩密度、３１体積％の
空隙間率を持つもので、保形性にすぐれ、粘着性が殆ん
どない取り扱い易いものであった。次に、この未硬化集
合体を長さ３００ｍｍ、幅３００ｍｍ、厚み２６ｍｍに
切断した。この切断された未硬化集合体を長さ３００ｍ
ｍ、幅３００ｍｍ、深さ１３ｍｍの内寸法を有し、かつ
内部がポリテトラフルオロエチレン樹脂で表面処理され
た９０℃に加熱されているアルミニウム製雌金型内に入
れ、この雌金型に一致するプレス機構を有する同材質の
９０℃に加熱された雄金型にてプレス（プレス圧力は１
０ｋｇｆ／ｃｍ2）し、そのままの温度で６０分間保持
した後、軽量成形体を取り出し、２３℃、５０％ＲＨの
雰囲気下で４８時間放置した。その軽量成形体は、長さ
３００ｍｍ、幅３００ｍｍ、厚み１３ｍｍのサイズ、
０．３２ｇ／ｃｍ3の嵩密度、５体積％以下の空隙率を
持つものであった。また、その軽量成形体は、曲げ弾性
率が２９３０ｋｇｆ／ｃｍ2、曲げ降伏点強度が５５．
８ｋｇｆ・ｃｍ2の曲げ物性（いずれもＪＩＳＫ６９１
１による測定）を持つものであった。[Production Example 3-1 of Uncured Synthetic Resin Expanded Granular Material Aggregate and Light-Weight Molded Product] (Example of Strength Improvement by Glass Fiber Blending) Manufactured. Next, 100 parts by weight of liquid unsaturated polyester resin, 1 part by weight of magnesium oxide (thickener), 3 parts by weight of lauroyl peroxide (curing agent), and a commercially available glass fiber as a reinforcing material (trade name of Asahi Fiberglass Co., Ltd.) "MF20
MH2-20 ") and 30 parts by weight were premixed below the temperature at which the curing agent would substantially decompose. Subsequently, 134 parts by weight of the preliminary mixture in the form of a highly sticky paste and 100 parts by weight of the expanded particles are placed in a container, and a mixing operation is performed so that the entire surface of the surface layer of the expanded particles is entirely covered with the preliminary mixture. went. Next, a resin mold having inner dimensions of 500 mm in length, 500 mm in width, and 100 mm in depth was prepared, and a large-sized polyethylene sheet was placed along the inner wall of the mold. Put it in the mold so that it becomes 60 mm,
Then, cover it with a polyethylene sheet and
It was left for 3 days under an atmosphere of ° C. The uncured synthetic resin expanded granular material aggregate taken out from the mold is thickened at 500 mm in length, 500 mm in width and 60 mm in thickness as a result of the unsaturated polyester resin being thickened to a solid or semi-solid state at room temperature.
, A bulk density of 0.16 g / cm 3 , and a void ratio of 31% by volume. It was excellent in shape retention and had little tackiness and was easy to handle. Next, this uncured aggregate was cut into a length of 300 mm, a width of 300 mm, and a thickness of 26 mm. 300 m length of this cut uncured aggregate
m, width 300 mm, depth 13 mm, placed inside an aluminum female mold heated to 90 ° C., surface-treated with polytetrafluoroethylene resin and matched with this female mold Press with a male mold of the same material heated to 90 ° C (press pressure is 1
0 kgf / cm 2 ), and the temperature was maintained at that temperature for 60 minutes. Then, the lightweight molded body was taken out and left under an atmosphere of 23 ° C. and 50% RH for 48 hours. The lightweight molded body is 300 mm long, 300 mm wide, and 13 mm thick.
It had a bulk density of 0.32 g / cm 3 and a porosity of 5% by volume or less. The lightweight molded body had a flexural modulus of 2930 kgf / cm 2 and a flexural yield point strength of 55.5 kgf / cm 2 .
Flexural properties of 8 kgf · cm 2 (both JIS K691
1).
【００２６】〔未硬化状合成樹脂発泡粒状物集合体及び
軽量成形体の製造例３−２〕 （ガラス繊維配合による強度向上例）前記製造例３−１
と同じ発泡粒子を使用し、補強材を不飽和ポリエステル
樹脂１００重量部に対して６０重量部配合した未硬化集
合体を作製した。得られた未硬化集合体は、不飽和ポリ
エステル樹脂が常温において固体状ないし半固体状に増
粘された結果、長さ５００ｍｍ、幅５００ｍｍ、厚み６
０ｍｍのサイズ、０．１７ｇ／ｃｍ3の嵩密度、３１体
積％の空隙率を持つもので、保形性にすぐれ、粘着性が
殆んどない取り扱い易いものであった。次に、前記製造
例３−１と同様の操作で加熱プレス成形を行い、軽量成
形体を得た。その軽量成形体は、長さ３００ｍｍ、幅３
００ｍｍ、厚み１３ｍｍのサイズ、０．３６ｇ／ｃｍ3
の嵩密度、５体積％以下の空隙率を持つものであった。
また、その軽量成形体は、曲げ弾性率が３７００ｋｇｆ
／ｃｍ2、曲げ降伏点強度が５５．９ｋｇｆ／ｃｍ2の曲
げ物性（いずれもＪＩＳ Ｋ６９１１による測定）を持
つものであった。[Production Example 3-2 of Uncured Synthetic Resin Expanded Granular Material Aggregate and Light-Weight Molded Product] (Example of Strength Improvement by Mixing Glass Fiber) Production Example 3-1
Using the same foamed particles as in Example 1, an uncured aggregate was prepared in which the reinforcing material was mixed in an amount of 60 parts by weight with respect to 100 parts by weight of the unsaturated polyester resin. The resulting uncured aggregate had a length of 500 mm, a width of 500 mm, and a thickness of 6 as a result of the unsaturated polyester resin being thickened in a solid or semi-solid state at room temperature.
It had a size of 0 mm, a bulk density of 0.17 g / cm 3 , and a porosity of 31% by volume. It had excellent shape retention and had little tackiness and was easy to handle. Next, hot press molding was performed in the same manner as in Production Example 3-1 to obtain a lightweight molded body. The lightweight molded body is 300mm long and 3mm wide.
00 mm, thickness 13 mm, 0.36 g / cm 3
And had a porosity of 5% by volume or less.
The lightweight molded body has a flexural modulus of 3700 kgf.
/ Cm 2 , and a bending yield point strength of 55.9 kgf / cm 2 , which has bending properties (all measured according to JIS K6911).
【００２７】〔未硬化状合成樹脂発泡状物集合体及び軽
量成形体の製造例３−３〕前記製造例３−１と同じ発泡
粒子を使用し、補強材のみを配合せずに補強材を除いた
未硬化集合体を作製した。得られた未硬化集合体は、不
飽和ポリエステル樹脂が常温において固体状ないし半固
体状に増粘された結果、長さ５００ｍｍ、幅５００ｍ
ｍ、厚み６０ｍｍのサイズ、０．１１ｇ／ｃｍ3の嵩密
度、３１体積％の空隙率を持つもので、保形性にすぐ
れ、粘着性が殆んどない取り扱い易いものであった。次
に、前記製造例３−１と同様の操作で加熱プレス成形を
行い、軽量成形体を得た。その軽量成形体は、長さ３０
０ｍｍ、幅３００ｍｍ、厚み１３ｍｍのサイズ、０．３
１ｇ／ｃｍ3の嵩密度、５体積％以下の空隙率を持つも
のであった。また、その軽量成形体は、曲げ弾性率が１
９７０ｋｇｆ／ｃｍ2、曲げ降伏点強度が４２ｋｇｆ／
ｃｍ2の曲げ物性（いずれもＪＩＳ Ｋ６９１１による
測定）を持つものであった。以上をまとめて示すと表１
のとおりである。[Production Example 3-3 of Uncured Synthetic Resin Foam Aggregate and Light-Weight Molded Product] Using the same foamed particles as in Production Example 3-1 above, a reinforcing material was used without mixing only the reinforcing material. An uncured aggregate was then removed. The resulting uncured aggregate had a length of 500 mm and a width of 500 m as a result of the unsaturated polyester resin being thickened in a solid or semi-solid state at room temperature.
m, having a size of 60 mm in thickness, a bulk density of 0.11 g / cm 3 , and a porosity of 31% by volume, were excellent in shape retention, had little tackiness, and were easy to handle. Next, hot press molding was performed in the same manner as in Production Example 3-1 to obtain a lightweight molded body. The lightweight molded body has a length of 30
0mm, width 300mm, thickness 13mm, 0.3
It had a bulk density of 1 g / cm 3 and a porosity of 5% by volume or less. The lightweight molded body has a flexural modulus of 1
970 kgf / cm 2 , bending yield point strength is 42 kgf / cm 2
The material had a bending physical property of cm 2 (all measured according to JIS K6911). Table 1 summarizes the above.
It is as follows.
【００２８】[0028]
【表１】 [Table 1]
【００２９】〔中間体及び軽量複合体の製造例４−１〕
（難燃剤配合） 製造例１−１と同じ素材、及び同じ操作で発泡粒子を製
造した。次に液状不飽和ポリエステル樹脂１００重量部
と酸化マグネシウム（増粘剤）１重量部及びラウロイル
パーオキサイド（硬化剤）３重量部、さらに補強材とし
て市販のガラス繊維（旭ファイバーグラス株式会社の商
品名「ＭＦ２０ＭＨ２−２０」）３０重量部、及び難燃
剤として水酸化アルミニウム１００重量部とを、硬化剤
が実質的に分解する温度未満で予備混合した。続いて、
粘着性の高いペースト状の前記予備混合物２３４重量部
と前記発泡粒子１００重量部とを容器に入れて、該発泡
粒子表層部の全面が予備混合物で全面被覆されるように
混合操作を行った。次に内寸法が長さ５００ｍｍ、幅５
００ｍｍ、深さ１００ｍｍの樹脂製型枠を用意し、大判
のポリエチレン製シートを型枠内壁面に沿わせ、その上
から、前記容器内容物の厚みが約６０ｍｍとなるように
型枠に入れ、更にその上から、ポリエチレン製シートで
覆って、３５℃雰囲気下で３日間放置した。型枠から取
り出された未硬化状合成樹脂発泡粒状物集合体は、不飽
和ポリエステル樹脂が常温において固体状ないし半固体
状に増粘された結果、長さ５００ｍｍ、幅５００ｍｍ、
厚み６０ｍｍのサイズ、０．２５ｇ／ｃｍ3の嵩密度、
３１体積％の空隙率を持つもので、保形性にすぐれ、粘
着性が殆んどない取り扱い易いものであった。次に、十
分に増粘され粘着性が殆んどなくなっている市販のシー
トモールディングコンパウンド（武田薬品工業株式会社
の商品名「セレクティマットＲ−１０１）から、長さ３
００ｍｍ、幅３００ｍｍのの２枚のシートモールディン
グコンパウンドを切り出し、これを前記未硬化集合体を
長さ３００ｍｍ、幅３００ｍｍ、厚み２８ｍｍに切り出
したものの上下面に重ね合わせた、長さ３００ｍｍ、幅
３００ｍｍ、深さ１５ｍｍの内寸法を有し、かつ内部が
ポリテトラフルオロエチレン樹脂で表面処理された９０
℃に加熱されているアルミニウム製雌金型内に入れ、こ
の雌金型に一致するプレス機構を有する同材質の９０℃
に加熱された雄金型にてプレス（プレス圧力は１０ｋｇ
ｆ／ｃｍ2）し、そのまま温度で６０分間保持した後、
軽量複合体を取り出し、２３℃、５０％ＲＨの雰囲気下
で４８時間放置した。その軽量複合体は、長さ３００ｍ
ｍ、幅３００ｍｍ、厚み１５ｍｍのサイズ、０．６４ｇ
／ｃｍ3の嵩密度、５体積％以下の空隙率を持つもので
あった。燃焼試験（ＪＩＳ Ｄ１２０１による測定）の
結果、自消性であった。[Production Example 4-1 of Intermediate and Lightweight Composite]
(Flame retardant formulation) Expanded particles were produced by the same material and by the same operation as in Production Example 1-1. Next, 100 parts by weight of liquid unsaturated polyester resin, 1 part by weight of magnesium oxide (thickener), 3 parts by weight of lauroyl peroxide (curing agent), and a commercially available glass fiber as a reinforcing material (trade name of Asahi Fiberglass Co., Ltd.) 30 parts by weight of "MF20MH2-20") and 100 parts by weight of aluminum hydroxide as a flame retardant were premixed at a temperature lower than the temperature at which the curing agent substantially decomposes. continue,
234 parts by weight of the paste-like pre-mixture having high adhesiveness and 100 parts by weight of the foam particles were placed in a container, and a mixing operation was performed so that the entire surface of the foam particle surface layer was completely covered with the pre-mixture. Next, the inner dimensions are 500 mm in length and 5 in width
Prepare a resin mold having a thickness of 00 mm and a depth of 100 mm, place a large-sized polyethylene sheet along the inner wall surface of the mold, and put the container into the mold so that the thickness of the container contents is about 60 mm. Furthermore, it was covered with a polyethylene sheet from above and allowed to stand in a 35 ° C. atmosphere for 3 days. The uncured synthetic resin foam granule aggregate taken out of the mold is a solid or semi-solid thickened unsaturated polyester resin at room temperature, resulting in a length of 500 mm, a width of 500 mm,
60 mm thick, 0.25 g / cm 3 bulk density,
It had a porosity of 31% by volume, was excellent in shape retention, had little tackiness, and was easy to handle. Next, a commercially available sheet molding compound (trade name “SELECTIMAT R-101” of Takeda Pharmaceutical Co., Ltd.), which has been sufficiently thickened and has almost no tackiness, has a length of 3 mm.
00 mm, cut out two sheet molding compounds of width 300 mm, and the uncured aggregate was cut out to a length of 300 mm, width of 300 mm, and a thickness of 28 mm, which were superimposed on the upper and lower surfaces, length 300 mm, width 300 mm, 90 having an inner dimension of 15 mm in depth and having the inside surface-treated with polytetrafluoroethylene resin
90 ° C of the same material having a press mechanism corresponding to the female mold placed in an aluminum female mold heated to
Press with a male mold heated to
f / cm 2 ) and hold at that temperature for 60 minutes.
The lightweight composite was taken out and left under an atmosphere of 23 ° C. and 50% RH for 48 hours. The lightweight composite is 300m long
m, size 300mm wide, 15mm thick, 0.64g
/ Cm 3 and a porosity of 5% by volume or less. As a result of a combustion test (measured by JIS D1201), it was self-extinguishing.
【００３０】〔中間体及び軽量複合体の製造例４−２〕
（難燃剤配合） 難燃剤の配合量を不飽和ポリエステル樹脂１００重量部
に対して５０重量部に変更して前記製造例４−１を繰返
して軽量複合体を得た。その軽量複合体は、長さ３００
ｍｍ、幅３００ｍｍ、厚み１５ｍｍのサイズ、０．５８
ｇ／ｃｍ3の嵩密度、５体積％以下の空隙率を持つもの
であった。燃焼試験（ＪＩＳ Ｄ１２０１による測定の
結果、自消性であった。[Production Example 4-2 of Intermediate and Lightweight Composite]
(Blending of Flame Retardant) The amount of the flame retardant was changed to 50 parts by weight with respect to 100 parts by weight of the unsaturated polyester resin, and the above Production Example 4-1 was repeated to obtain a lightweight composite. The lightweight composite has a length of 300
mm, width 300 mm, thickness 15 mm, 0.58
It had a bulk density of g / cm 3 and a porosity of 5% by volume or less. It was self-extinguishing as a result of a combustion test (measurement according to JIS D1201).
【００３１】〔中間体及び軽量複合体の製造例４−３〕
前記製造例４−１の難燃剤のみを配合せず、同じ操作で
軽量複合体を得た。その軽量複合体は、長さ３００ｍ
ｍ、幅３００ｍｍ、厚み１５ｍｍのサイズ、０．５２ｇ
／ｃｍ3の嵩密度、５体積％以下の空隙率を持つもので
あった。燃焼試験（ＪＩＳ Ｄ１２０１による測定）の
結果、遅燃性であった。以上をまとめて示すと表２のと
おりである。[Production Example 4-3 of Intermediate and Lightweight Composite]
A lightweight composite was obtained by the same operation without blending only the flame retardant of Production Example 4-1. The lightweight composite is 300m long
m, size 300mm wide, 15mm thick, 0.52g
/ Cm 3 and a porosity of 5% by volume or less. As a result of a combustion test (measured according to JIS D1201), it was retarded. Table 2 summarizes the above.
【００３２】[0032]
【表２】 [Table 2]
【００３３】[0033]
【発明の効果】本発明の未硬化状合成樹脂発泡体粒状物
集合体は、接着性が殆んどないため取扱い性が良く、保
形性に優れ、作り置きができ、そして加熱下にプレス成
形するだけで容易に軽量成形体及び軽量複合体とするこ
とができるなど顕著な効果を奏するものである。更に、
本発明の軽量成形体及び軽量複合体の製造方法によれ
ば、前記未硬化状合成樹脂発泡体粒状物集合体を出発材
料とすることによって、従来法とは異なり、作り置きし
た途中の段階までのものを用いることができ、運搬など
の取り扱い性に優れ、成形時に環境悪化を引き起こすこ
ともなく、コスト的にも有利に軽量成形体及び軽量複合
体を製造できるものである。また、本発明の、前記未硬
化状合成樹脂発泡体粒状物集合体を用い製造されてなる
軽量成形体及び軽量複合体は、軽量性、断熱性、強度等
において非常に優れるものであり、例えば、建築用部
材、箱材、ビデオやテレビなどの電子機器の載置台、パ
レット床敷材、船舶構造体等の用途に有用である。ま
た、従来の合成木材に置き換えることも可能である。The aggregate of the uncured synthetic resin foam of the present invention has almost no adhesiveness, so that it has good handleability, excellent shape retention, can be prepared, and can be pressed under heating. A remarkable effect is obtained such that a lightweight molded body and a lightweight composite can be easily formed only by molding. Furthermore,
According to the manufacturing method of the lightweight molded article and the lightweight composite of the present invention, by using the uncured synthetic resin foam granular material aggregate as a starting material, unlike the conventional method, up to the stage of the preparatory process It is possible to produce a light-weight molded article and a lightweight composite body with excellent handling properties such as transportation, without causing environmental deterioration at the time of molding, and cost-effectively. Further, the lightweight molded article and the lightweight composite produced by using the uncured synthetic resin foam particulate aggregate of the present invention are extremely excellent in lightness, heat insulation, strength, and the like. It is useful for applications such as building materials, box materials, mounting tables for electronic devices such as videos and televisions, pallet flooring materials, and ship structures. It is also possible to replace it with conventional synthetic wood.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ // Ｂ３２Ｂ 27/36 １０１ Ｂ３２Ｂ 27/36 １０１ (72)発明者 所 寿男 栃木県宇都宮市砥上町282−１ ブランシ ョール砥上103号室──────────────────────────────────────────────────の Continuation of the front page (51) Int.Cl. 6 Identification code FI // B32B 27/36 101 B32B 27/36 101 (72) Inventor Toshio 282-1 Togamicho, Utsunomiya-shi, Tochigi Blanchol Toge 103 Issue room
Claims (26)
エステル樹脂を介して一体に結合させたものであって、
該不飽和ポリエステル樹脂は硬化剤を含有しているが、
実質的に未硬化の状態であり、かつ常温において固体状
ないし半固体状を示すことを特徴とする未硬化状合成樹
脂発泡粒状物集合体。1. A method in which a number of foamed synthetic resin particles are integrally bonded via an unsaturated polyester resin,
Although the unsaturated polyester resin contains a curing agent,
An uncured synthetic resin foamed particulate aggregate which is substantially uncured and exhibits a solid or semi-solid state at ordinary temperature.
かつその空隙率が１０体積％以上である請求項１記載の
未硬化状合成樹脂発泡粒状物集合体。2. A void is present between the synthetic resin foam granules,
The uncured synthetic resin foam particulate aggregate according to claim 1, wherein the porosity is 10% by volume or more.
樹脂を基材樹脂とする請求項１又は２記載の未硬化状合
成樹脂発泡粒状物集合体。3. The uncured synthetic resin foam granule aggregate according to claim 1, wherein the synthetic resin foam granulate comprises a polyolefin resin as a base resin.
の不飽和ポリエステル樹脂により表面が覆われた合成樹
脂発泡粒状物の多数個集積体を前記硬化剤が実質的に反
応を生じない温度に保持して、前記不飽和ポリエステル
樹脂を前記増粘剤と反応させて固体状ないし半固体状物
に形成することを特徴とする請求項１記載の未硬化状合
成樹脂発泡粒状物集合体を製造する方法。4. A multi-piece aggregate of synthetic resin foam granules whose surface is covered with a paste-like unsaturated polyester resin containing a curing agent and a thickener, wherein the curing agent does not substantially react. The uncured synthetic resin expanded granular material aggregate according to claim 1, wherein the unsaturated polyester resin is reacted with the thickener to form a solid or semi-solid material while maintaining the temperature. How to manufacture.
化状合成樹脂発泡粒状物集合体を、該硬化剤の分解点以
上の温度でプレス成形することを特徴とする軽量成形体
の製造方法。5. A lightweight molded article characterized in that the uncured synthetic resin foam particulate aggregate according to any one of claims 1 to 4 is press-molded at a temperature not lower than the decomposition point of the curing agent. Production method.
化状合成樹脂発泡粒状物集合体を、硬化剤の分解点以上
の温度でプレス成形してなる軽量成形体。6. A lightweight molded article obtained by press-molding the uncured synthetic resin foam particulate aggregate according to any one of claims 1 to 4 at a temperature equal to or higher than the decomposition point of a curing agent.
物の割合が８０〜９９体積％である請求項６記載の軽量
成形体。7. The lightweight molded article according to claim 6, wherein the proportion of the synthetic resin foam granules in the lightweight molded article is 80 to 99% by volume.
材とからなる軽量複合体。8. A lightweight composite comprising the lightweight molded article according to claim 6 and a surface material.
めの中間体であって、請求項１乃至３のいずれかに記載
の未硬化状合成樹脂発泡粒状物集合体と表面材との積層
体からなる中間体。9. An intermediate for producing the lightweight composite according to claim 8, wherein the aggregate of the uncured synthetic resin foam granules according to any one of claims 1 to 3 and a surface material. Intermediate consisting of a laminate.
維強化熱可塑性樹脂、熱硬化性樹脂、熱可塑性樹脂、金
属及び木材の中から選択される板状物又はシート状物で
あることを特徴とする請求項９記載の中間体。10. The surface material is a plate or sheet selected from fiber reinforced thermosetting resin, fiber reinforced thermoplastic resin, thermosetting resin, thermoplastic resin, metal and wood. The intermediate according to claim 9, wherein:
はシート状表面材が、硬化剤を含有しているが実質的に
未硬化の状態にある常温において固体状ないし半固体状
の不飽和ポリエステル樹脂を介して一体に結合された繊
維からなる請求項１０記載の中間体。11. A solid or semi-solid unsaturated material at room temperature in which a plate-like or sheet-like surface material made of a fiber-reinforced thermosetting resin contains a curing agent but is in a substantially uncured state. 11. The intermediate according to claim 10, comprising fibers integrally bonded via a polyester resin.
表面剤が接着されている請求項１１記載の中間体。12. The intermediate according to claim 11, wherein the uncured synthetic resin expanded granular material aggregate and the surface agent are adhered.
表面剤が接着することなく重ね合わされている請求項１
１記載の中間体。13. The uncured synthetic resin expanded granular material aggregate and the surface agent are superimposed on each other without bonding.
2. The intermediate according to 1.
中間体を、未硬化の不飽和ポリエステル樹脂中の硬化剤
の分解点以上の温度でプレス成形することを特徴とする
軽量複合体の製造方法。14. A lightweight composite, wherein the intermediate according to claim 9 is press-molded at a temperature not lower than the decomposition point of a curing agent in an uncured unsaturated polyester resin. Production method.
配合してなる請求項１乃至３のいずれかに記載の未硬化
状合成樹脂発泡粒状物集合体。15. The aggregate of foamed uncured synthetic resin particles according to claim 1, wherein a reinforcing material is blended in the unsaturated polyester resin.
配合してなる請求項６又は７記載の軽量成形体。16. The lightweight molded article according to claim 6, wherein a reinforcing material is compounded in the unsaturated polyester resin.
配合してなる請求項８記載の軽量複合体。17. The lightweight composite according to claim 8, wherein a reinforcing material is compounded in the unsaturated polyester resin.
配合してなる請求項９乃至１３のいずれかに記載の中間
体。18. The intermediate according to claim 9, wherein a reinforcing material is compounded in the unsaturated polyester resin.
配合してなる請求項１乃至３、請求項１５のいずれかに
記載の未硬化状合成樹脂発泡粒状物集合体。19. The aggregate of foamed uncured synthetic resin particles according to claim 1, wherein a flame retardant is blended into the unsaturated polyester resin.
配合してなる請求項６乃至７、請求項１６のいずれかに
記載の軽量成形体。20. The lightweight molded article according to claim 6, wherein a flame retardant is blended in the unsaturated polyester resin.
配合してなる請求項８又は１７に記載の軽量複合体。21. The lightweight composite according to claim 8, wherein a flame retardant is blended in the unsaturated polyester resin.
配合してなる請求項９乃至１３、請求項１８のいずれか
に記載の中間体。22. The intermediate according to claim 9, wherein a flame retardant is blended in the unsaturated polyester resin.
機フィラー及びこれらの２以上の混合物の中から選択さ
れる請求項１５に記載の未硬化状合成樹脂発泡粒状物集
合体。23. The uncured synthetic resin foam particulate aggregate according to claim 15, wherein the reinforcing material is selected from glass fiber, glass powder, inorganic filler, and a mixture of two or more thereof.
機フィラー及びこれらの２以上の混合物の中から選択さ
れる請求項１６に記載の軽量成形体。24. The lightweight molded article according to claim 16, wherein the reinforcing material is selected from glass fiber, glass powder, inorganic filler, and a mixture of two or more thereof.
機フィラー及びこれらの２以上の混合物の中から選択さ
れる請求項１７に記載の軽量複合体。25. The lightweight composite according to claim 17, wherein the reinforcement is selected from glass fibers, glass powders, inorganic fillers and mixtures of two or more thereof.
機フィラー及びこれらの２以上の混合物の中から選択さ
れる請求項１８に記載の中間体。26. The intermediate according to claim 18, wherein the reinforcement is selected from glass fibers, glass powders, inorganic fillers and mixtures of two or more thereof.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP35235197A JPH10219021A (en) | 1996-12-05 | 1997-12-05 | Uncured synthetic resin foamed particle aggregate, its production, light-weight molding product, its production, light-weight composite material, its production and intermediate for producing the composite material |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34060796 | 1996-12-05 | ||
| JP8-340607 | 1996-12-05 | ||
| JP35235197A JPH10219021A (en) | 1996-12-05 | 1997-12-05 | Uncured synthetic resin foamed particle aggregate, its production, light-weight molding product, its production, light-weight composite material, its production and intermediate for producing the composite material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH10219021A true JPH10219021A (en) | 1998-08-18 |
Family
ID=26576748
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP35235197A Pending JPH10219021A (en) | 1996-12-05 | 1997-12-05 | Uncured synthetic resin foamed particle aggregate, its production, light-weight molding product, its production, light-weight composite material, its production and intermediate for producing the composite material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH10219021A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001279015A (en) * | 2000-03-31 | 2001-10-10 | Jsp Corp | Method for producing lightweight composite |
| WO2001092387A1 (en) * | 2000-05-30 | 2001-12-06 | Takashi Fujimori | Molded object comprising resin foam and solid particles and process for producing the same |
| JP2003528189A (en) * | 2000-03-17 | 2003-09-24 | ダウ グローバル テクノロジーズ インコーポレーテッド | Method for producing macrocellular acoustic foam |
| JP2012236914A (en) * | 2011-05-12 | 2012-12-06 | Jsp Corp | Composite molding |
| JP2014198381A (en) * | 2013-03-29 | 2014-10-23 | 積水化成品工業株式会社 | Fiber-reinforced composite and method for manufacturing the same |
| EP3170858A4 (en) * | 2014-07-15 | 2017-07-05 | Jsp Corporation | Composite molded article, laminate, and method for producing composite molded article |
-
1997
- 1997-12-05 JP JP35235197A patent/JPH10219021A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003528189A (en) * | 2000-03-17 | 2003-09-24 | ダウ グローバル テクノロジーズ インコーポレーテッド | Method for producing macrocellular acoustic foam |
| JP2001279015A (en) * | 2000-03-31 | 2001-10-10 | Jsp Corp | Method for producing lightweight composite |
| WO2001092387A1 (en) * | 2000-05-30 | 2001-12-06 | Takashi Fujimori | Molded object comprising resin foam and solid particles and process for producing the same |
| JP2012236914A (en) * | 2011-05-12 | 2012-12-06 | Jsp Corp | Composite molding |
| JP2014198381A (en) * | 2013-03-29 | 2014-10-23 | 積水化成品工業株式会社 | Fiber-reinforced composite and method for manufacturing the same |
| EP3170858A4 (en) * | 2014-07-15 | 2017-07-05 | Jsp Corporation | Composite molded article, laminate, and method for producing composite molded article |
| US10369766B2 (en) | 2014-07-15 | 2019-08-06 | Jsp Corporation | Composite molded article, laminate, and method for producing composite molded article |
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