JPH10166434A - Composite blow molded product and molding method - Google Patents
Composite blow molded product and molding methodInfo
- Publication number
- JPH10166434A JPH10166434A JP33690696A JP33690696A JPH10166434A JP H10166434 A JPH10166434 A JP H10166434A JP 33690696 A JP33690696 A JP 33690696A JP 33690696 A JP33690696 A JP 33690696A JP H10166434 A JPH10166434 A JP H10166434A
- Authority
- JP
- Japan
- Prior art keywords
- mold
- resin
- thermosetting resin
- thermoplastic resin
- temperature
- 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
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- Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、熱硬化性樹脂と熱
可塑性樹脂との複合成形法に関する。更に詳しくは、熱
可塑性樹脂の表面に、金型賦型面を正確に転写した熱硬
化性樹脂が強固に密着した外観良好な複合中空成形品と
該中空品を得るための複合ブロー成形法に関するもので
ある。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composite molding method of a thermosetting resin and a thermoplastic resin. More specifically, the present invention relates to a composite hollow molded product having a good appearance in which a thermosetting resin having a mold-molded surface accurately transferred to a surface of a thermoplastic resin is firmly adhered to the surface and a composite blow molding method for obtaining the hollow product. Things.
【０００２】[0002]
【従来の技術】従来、熱可塑性樹脂は、その成形性の良
さから各分野で広く利用されているが、その表面硬度、
耐熱性、耐化学薬品性、耐炎性、耐摩耗性等が不足して
いるために、利用拡大上の障害になっていた。一方、熱
硬化性樹脂は、上記諸性質は熱可塑性樹脂に勝るが成形
性、賦形性に乏しい。そこでこれらの樹脂を一体化する
事によって、互いの長所を生かした成形品を得る事が望
まれている。そこで熱可塑性樹脂のブロー成形による天
板などは表面の硬度、耐薬品性等を付与するためにブロ
ー成形品を作成した後に接着剤等を用いてオモテ面にす
でに硬化したメラミン樹脂板等を張っている。2. Description of the Related Art Conventionally, thermoplastic resins have been widely used in various fields because of their good moldability.
Insufficient heat resistance, chemical resistance, flame resistance, abrasion resistance, etc. hindered the expansion of use. On the other hand, a thermosetting resin has the above-mentioned properties better than a thermoplastic resin, but is poor in moldability and shapeability. Therefore, it is desired to obtain a molded product that takes advantage of each other by integrating these resins. Therefore, a top plate made of blow-molded thermoplastic resin is made of blow-molded product in order to impart surface hardness, chemical resistance, etc., and then a hardened melamine resin plate or the like is attached to the front surface using an adhesive or the like. ing.
【０００３】また、木材製の化粧板を作成するには、一
般に該板の上に未硬化の熱硬化性樹脂を塗布した後に加
熱や紫外線により硬化させたり、未硬化の熱硬化性樹脂
を含む含浸紙を上面においた後に加熱プレスして複合化
する方法などがある。In order to prepare a decorative board made of wood, generally, an uncured thermosetting resin is applied on the board and then cured by heating or ultraviolet rays, or contains an uncured thermosetting resin. There is a method in which impregnated paper is placed on the upper surface and then heated and pressed to form a composite.
【０００４】また、射出成形においては、特公平７−５
５５１３公報において射出成形金型内にて未硬化の熱硬
化性樹脂と熱硬化性樹脂の複合成形法が記載されてい
る。In injection molding, Japanese Patent Publication No. 7-5
No. 5513 describes a composite molding method of an uncured thermosetting resin and a thermosetting resin in an injection mold.
【０００５】[0005]
【発明が解決しようとする課題】数種の熱可塑性樹脂材
料を積層する多層ブロー成形は、それぞれの材料の特性
を生かした方法として広く利用されているが、熱可塑性
樹脂の特性には限界があり、更に高度な耐薬品性、表面
硬度、耐熱性を有する熱硬化性樹脂との複合化が望まれ
ている。しかしながら、熱可塑性樹脂と熱硬化性樹脂
は、一般には相溶性がなく単に熱融着させるだけでは充
分な密着強度を得ることは困難である。また複数の熱可
塑性樹脂は、異なるシリンダーにて可塑化し、パリソン
と呼ばれる管状の樹脂体を形成時に多層化出来るが、熱
硬化性樹脂は加熱により、硬化するため所望の最終形状
に賦形した後に加熱硬化する必要がある。Multilayer blow molding, in which several kinds of thermoplastic resin materials are laminated, is widely used as a method utilizing the characteristics of each material, but the characteristics of thermoplastic resins are limited. There is a demand for a composite with a thermosetting resin having higher chemical resistance, surface hardness and heat resistance. However, thermoplastic resins and thermosetting resins are generally incompatible and it is difficult to obtain sufficient adhesion strength by simply heat-sealing. In addition, a plurality of thermoplastic resins can be plasticized in different cylinders and can be multilayered at the time of forming a tubular resin body called a parison, but the thermosetting resin is cured by heating, after shaping into a desired final shape, Heat curing is required.
【０００６】また、熱可塑性樹脂をブロー成形した後に
硬化した熱硬化性樹脂板等を接着剤等を介して張り合わ
せる方法は、製造工数が増え手間がかかるといった問題
や、ほぼ平面形状の部分しか複合化できないといった制
限がある。A method of bonding a thermosetting resin plate or the like cured after blow molding a thermoplastic resin via an adhesive or the like involves a problem that the number of manufacturing steps is increased and labor is required, and that only a substantially planar portion is used. There is a limitation that it cannot be combined.
【０００７】一方、木材と熱硬化性樹脂の紫外線を用い
る複合化法は、紫外線硬化の設備が高価であったり、手
間がかかるといった問題ある。また加熱プレスによる複
合法では、一般に軟化温度の低い熱可塑性樹脂との複合
法には利用困難である。[0007] On the other hand, the compounding method using ultraviolet light of wood and a thermosetting resin has a problem that the equipment for curing ultraviolet light is expensive and time-consuming. Further, it is generally difficult to use a composite method by a heat press in a composite method with a thermoplastic resin having a low softening temperature.
【０００８】更に射出成形による金型内での複合化で
は、溶融樹脂を、成形品の大きさに比べて小さなゲート
と呼ばれる部分から金型内に射出充填する。この時、特
にゲート付近では、溶融樹脂は高速で金型内に挿入され
る。このため金型内に予め塗布しておいた未硬化の熱硬
化性樹脂が流れ出したり、未硬化の熱硬化性樹脂を含浸
しておいた基材にしわがよるといった問題が生じてい
た。また射出成形で作成困難な中空成形品や、大型天板
形状では、当然のことながら本発明で作成される成形品
を得ることは出来ない。[0008] Further, in compounding in a mold by injection molding, a molten resin is injected and filled into a mold from a portion called a gate which is smaller than the size of a molded product. At this time, especially near the gate, the molten resin is inserted into the mold at a high speed. For this reason, there has been a problem that the uncured thermosetting resin previously applied into the mold flows out or the base material impregnated with the uncured thermosetting resin becomes wrinkled. In addition, it is naturally impossible to obtain a molded product produced by the present invention with a hollow molded product difficult to produce by injection molding or a large top plate shape.
【０００９】更に通常のブロー成形では射出成形のよう
にあまり金型を高温に温度調節しないため、単に射出成
形で用いた方法（特公平７−５５５１３）をブロー成形
に適用しただけでは、加熱時間が非常に長くかかったり
して、成形サイクルが伸び、実施困難と考えられてい
た。Further, in ordinary blow molding, since the temperature of the mold is not so much adjusted to a high temperature as in injection molding, if the method used in injection molding (Japanese Patent Publication No. 7-55513) is simply applied to blow molding, the heating time will be reduced. It took a very long time, and the molding cycle was extended, and it was considered difficult to carry out.
【００１０】[0010]
【課題を解決するための手段】即ち、本発明は、熱可塑
性樹脂の表面に、金型賦型面を正確に転写したほぼ均一
肉厚の熱硬化性樹脂が強固に密着した複合中空成形品と
該成形品を得るためのブロー成形法を提供することにあ
る。これによって、熱可塑性樹脂と熱硬化性樹脂のそれ
ぞれの特長を生かした複合成形品を簡便に作成できる。That is, the present invention provides a composite hollow molded article in which a thermosetting resin having a substantially uniform thickness, on which a mold-molding surface is accurately transferred, is firmly adhered to the surface of a thermoplastic resin. And a blow molding method for obtaining the molded article. This makes it possible to easily produce a composite molded product utilizing the characteristics of the thermoplastic resin and the thermosetting resin.
【００１１】以下に本発明を具体的に説明する。Hereinafter, the present invention will be described specifically.
【００１２】本発明の複合成形品の製造に際して、まず
未硬化の熱硬化性樹脂或いはその混合物を、金型内の所
望の位置に存在せしめる。In the production of the composite molded article of the present invention, an uncured thermosetting resin or a mixture thereof is first placed in a desired position in a mold.
【００１３】未硬化の熱硬化性樹脂の存在形態として
は、該熱硬化性樹脂或いは混合物をフイルム、布、延伸
性のある材料等の基材に塗布したり含浸したものを、金
型内に挿入する。基材は、熱可塑性樹脂と熱硬化性樹脂
とを複合化した後、取り去っても良いし、複合化後その
まま使用しても良い。基材としては特に制限はないが、
三次元形状の複合成形品を得るためには、延伸性を有す
るものが好ましく、更に好ましくは軟化した熱可塑性樹
脂と接触する時に破壊せず、かつゴム状弾性を有するも
のが望ましい。The uncured thermosetting resin is present in a mold in which the thermosetting resin or the mixture is applied or impregnated to a base material such as a film, a cloth, or an extensible material. insert. The substrate may be removed after the thermoplastic resin and the thermosetting resin are combined, or may be used as it is after the combination. The substrate is not particularly limited,
In order to obtain a three-dimensional composite molded article, one having stretchability is preferred, and more preferably one which does not break when contacting with a softened thermoplastic resin and has rubber-like elasticity.
【００１４】また、別の未硬化の熱硬化性樹脂の存在形
態としては、未硬化の熱硬化性樹脂或いはその混合物を
直接金型賦形面に塗布しておいても良い。塗布法として
は、はけ塗りでもスプレーガンによる塗布でも構わな
い。直接金型賦形面に塗布した場合、基材を用いる方法
に比べ、より複雑な形状の成形品作成が可能となる。ま
た塗布する場合は、塗布時から熱可塑性樹脂と複合化す
る間に、重力によって移動しないような粘度に調整する
ことが望ましい。更に好ましくは、塗布後に固形物とし
て金型に付着するもの、例えば熱硬化性樹脂のプレポリ
マー等を溶剤に溶かし塗布後に溶剤を揮発させることが
望ましい。As another form of the uncured thermosetting resin, the uncured thermosetting resin or a mixture thereof may be directly applied to the mold imprinting surface. As a coating method, brushing or coating with a spray gun may be used. When directly applied to the mold imprinting surface, it is possible to create a molded article having a more complicated shape than the method using a substrate. In the case of application, it is desirable to adjust the viscosity so as not to move by gravity during the compounding with the thermoplastic resin from the time of application. More preferably, it is desirable to dissolve a substance that adheres to the mold as a solid after application, such as a prepolymer of a thermosetting resin, in a solvent and volatilize the solvent after application.
【００１５】更に、密着性の悪い熱可塑性樹脂と熱硬化
性樹脂を複合化する場合には、未硬化の熱硬化性樹脂に
反応性モノマーを添加したり、未硬化の熱硬化性樹脂を
金型に塗布した上に接着剤や熱硬化型接着剤を更に塗布
してもよいし、同様に未硬化の熱硬化性樹脂を基材に塗
布した場合も更に接着剤又は熱硬化型接着剤を塗布して
もよいし、未硬化の熱硬化性樹脂を含浸した基材に接着
剤や熱硬化型接着剤を塗布してもよい。Further, when a thermoplastic resin and a thermosetting resin having poor adhesion are compounded, a reactive monomer is added to the uncured thermosetting resin, or the uncured thermosetting resin is mixed with gold. An adhesive or a thermosetting adhesive may be further applied on the mold, or an uncured thermosetting resin may be applied to the substrate in the same manner. An adhesive or a thermosetting adhesive may be applied to a substrate impregnated with an uncured thermosetting resin.
【００１６】次に、ブロー成形機によりパリソンと呼ば
れる軟化した管状の熱可塑性樹脂体を解放した金型の間
に押し出しそれを挟み込むように金型を閉じ、圧縮空気
を送り込んでパリソンを金型に押しつける。それと同時
に熱可塑性樹脂と熱硬化性樹脂とを一体、複合化する。
この時、軟化した熱可塑性樹脂は、ほぼ均一に膨らみ金
型に接触するため、金型に塗布されていた未硬化の熱硬
化性樹脂に対して射出成形法で大きく影響するようなせ
ん断力が発生しない。すなわち、射出成形で問題となる
複合時における未硬化の熱硬化性樹脂の流れが起きにく
い。また未硬化の熱硬化性樹脂を基材に含浸或いは塗布
して挿入しておいた場合も、平面形状で有れば、しわの
発生、流れの問題も起きない。更に三次元形状を有する
複合成形品の作成においても基材に延伸性、更に好まし
くはゴム弾性を有するものを用いれば容易に良品が複合
できる。Next, a blow-molding machine extrudes a softened tubular thermoplastic resin body called a parison into a released mold, closes the mold so as to sandwich it, and sends compressed air to the parison into the mold. Press on. At the same time, the thermoplastic resin and the thermosetting resin are integrated and combined.
At this time, the softened thermoplastic resin swells almost uniformly and comes into contact with the mold, so that a shear force that greatly affects the uncured thermosetting resin applied to the mold by the injection molding method is used. Does not occur. That is, the flow of the uncured thermosetting resin during compounding, which is a problem in injection molding, hardly occurs. Also, when the base material is impregnated or coated with an uncured thermosetting resin and inserted, as long as the base material has a planar shape, wrinkles and flow problems do not occur. Furthermore, in the production of a composite molded article having a three-dimensional shape, a non-defective article can be easily composited by using a substrate having stretchability, more preferably rubber elasticity.
【００１７】熱硬化性樹脂を硬化させるには、硬化温度
以上に金型温度を設定する必要がある。該熱硬化性樹脂
は熱可塑性樹脂との複合化の前に硬化させても良いが、
満足できる密着強度を得る為、更に三次元形状を有する
複合成形品を得るためには、熱可塑性樹脂と複合化し、
金型に圧縮空気によって賦型しながら、熱硬化性樹脂を
硬化させることが望ましい。In order to cure a thermosetting resin, it is necessary to set a mold temperature higher than a curing temperature. Although the thermosetting resin may be cured before compounding with the thermoplastic resin,
In order to obtain a satisfactory molded product having a three-dimensional shape, in order to obtain a satisfactory adhesion strength, it is compounded with a thermoplastic resin.
It is desirable to cure the thermosetting resin while shaping the mold with compressed air.
【００１８】ここで昇温前の金型温度は、昇温が容易で
かつ熱可塑性樹脂が固化できる温度に、温調水等を冷媒
を用いた温調機で制御しておくことが、本発明を達成
し、実用的なものにするのには好ましい。具体的には、
金型を急加熱する前の金型温度を摂氏表示（℃）で熱硬
化性樹脂を硬化させる時の金型温度の３分の１以上に温
度制御しておくことが望ましい。Here, it is important that the temperature of the mold before temperature rise is controlled to a temperature at which the temperature can be easily raised and the thermoplastic resin can be solidified by a temperature controller using a coolant such as temperature-regulated water. It is preferred to achieve the invention and make it practical. In particular,
It is desirable to control the temperature of the mold before rapidly heating the mold to one third or more of the mold temperature when the thermosetting resin is cured in degrees Celsius (° C.).
【００１９】熱硬化性樹脂を硬化させる金型温度制御の
一つの方法としては、金型表面温度を該熱硬化性樹脂の
硬化温度以上でかつ成形する熱可塑性樹脂の固化温度以
下に設定しても良い。しかしながら一般に熱可塑性樹脂
の固化温度の多くは熱硬化性樹脂が速やかに架橋・硬化
する温度よりも低いために極めて限られた組み合わせの
材料しかこの方法では複合化出来ない。As one method of controlling the temperature of the mold for curing the thermosetting resin, the surface temperature of the mold is set to be equal to or higher than the curing temperature of the thermosetting resin and equal to or lower than the solidification temperature of the thermoplastic resin to be molded. Is also good. However, since most of the solidification temperatures of thermoplastic resins are generally lower than the temperature at which the thermosetting resin rapidly crosslinks and cures, only a very limited number of combinations of materials can be combined by this method.
【００２０】そこで熱硬化性樹脂を硬化させる金型温度
制御の好ましい方法として、熱硬化性樹脂の硬化時に
は、熱可塑性樹脂を金型に賦型しながら、金型表面温度
を熱硬化性樹脂の硬化温度以上に加熱し、熱硬化性樹脂
の硬化後に熱可塑性樹脂を冷却固化するように金型温度
を下げる方法が考えられる。このように金型温度を成形
品を作成する１サイクル中に昇温、冷却するには、金型
内に導入する加熱媒体によるもの、電熱によるもの、赤
外線加熱によるものレーザー光によるもの等があるが、
特に金型を急加熱、急冷却する効果的な方法として高周
波誘導による金型加熱があげられる。Therefore, as a preferable method of controlling the temperature of the mold for curing the thermosetting resin, at the time of curing the thermosetting resin, the surface temperature of the mold is controlled while shaping the thermoplastic resin into the mold. A method in which the temperature of the mold is lowered so that the thermoplastic resin is cooled and solidified after the thermosetting resin is cured by heating to a curing temperature or higher is considered. As described above, in order to raise and cool the mold temperature during one cycle of forming a molded article, there are a method using a heating medium introduced into the mold, a method using electric heating, a method using infrared heating, a method using laser light, and the like. But,
In particular, as an effective method for rapidly heating and rapidly cooling a mold, there is a mold heating by high frequency induction.
【００２１】金型の加熱は、金型全体を加熱しても良い
が、熱効率の点から熱硬化性樹脂が接触する金型キャビ
ティ面を選択的に加熱しても良い。また、熱硬化性樹脂
を成形品の特定部分に複合化する場合は、該部分のみを
選択的に加熱しても良い。更に高周波誘導加熱等によっ
て金型を昇温する時には、通常の金型温調による金型冷
却を停止させることが急速な金型加熱にはより効果的で
ある。高周波誘導加熱によるブロー成形金型加熱法の詳
細な説明については、特開昭５７−３６６１０公報に開
示されている。For heating the mold, the entire mold may be heated, or the mold cavity surface with which the thermosetting resin contacts may be selectively heated from the viewpoint of thermal efficiency. When the thermosetting resin is combined with a specific portion of the molded article, only that portion may be selectively heated. Further, when the temperature of the mold is raised by high-frequency induction heating or the like, it is more effective to stop the mold cooling by ordinary mold temperature control for rapid mold heating. A detailed description of the blow molding die heating method using high-frequency induction heating is disclosed in Japanese Patent Application Laid-Open No. 57-36610.
【００２２】熱可塑性樹脂は、該材料の軟化温度或いは
融点以下に設定させた金型によって、冷却固化され、賦
形される。金型の冷却は、通常の温調水を用いて金型を
冷却しても良いし、特に冷却効率の良いチラー水や、特
殊な冷却媒体を用いても良い。The thermoplastic resin is cooled and solidified by a mold set below the softening temperature or melting point of the material, and is shaped. For cooling the mold, the mold may be cooled using normal temperature-regulated water, or chiller water having particularly high cooling efficiency or a special cooling medium may be used.
【００２３】更に、温調水は、金型冷却時と金型急加熱
前の温度設定のためには、異なる温度の冷却媒体を切り
替えて用いても良い。具体的な一例を示せば、まず金型
温度を、温水を用いて７０℃に設定しておき、熱硬化性
樹脂を金型表面に塗布、熱可塑性樹脂のパリソンを開放
した金型間に下げ、型締め後、圧縮空気を注入し、熱可
塑性樹脂を金型内面に押しつけると同時に、熱硬化性樹
脂と一体化、温調水を止め、直ちに高周波誘導加熱にて
金型温度を１４０℃まで急加熱、３分間１４０±５℃に
保持し、０℃のチラー水にて金型温度を５０℃まで急冷
却、型開きと同時にチラー水を止め別系統の温調機から
９０℃の温調水を循環させ、型開き、製品取り出し中に
型温を７０℃に設定する。以後、上記操作を繰り返す。Further, the temperature control water may be switched between different cooling media for setting the temperature at the time of cooling the mold and before the rapid heating of the mold. As a specific example, first, the mold temperature is set to 70 ° C. using hot water, a thermosetting resin is applied to the mold surface, and the thermoplastic resin parison is lowered between the opened molds. After the mold is closed, pressurized air is injected and the thermoplastic resin is pressed against the inner surface of the mold. At the same time, the thermosetting resin is integrated, the temperature control water is stopped, and the mold temperature is immediately raised to 140 ° C by high frequency induction heating. Rapid heating, hold at 140 ± 5 ° C for 3 minutes, rapidly cool the mold temperature to 50 ° C with 0 ° C chiller water, stop the chiller water at the same time as opening the mold, and adjust the temperature to 90 ° C from another system temperature controller The water is circulated, the mold is opened, and the mold temperature is set at 70 ° C. during product removal. Thereafter, the above operation is repeated.
【００２４】また、本発明の複合中空成形品は、熱硬化
性樹脂と熱可塑性樹脂が強固に複合したものを提供する
ことにもある。ここで強固に密着とは、表面に被覆した
熱硬化性樹脂層に幅１ｍｍ間隔で縦、横１１本づつの切
り込みを入れ、セロテープで表面層を剥がすクロスカッ
ト・剥離テストにおいて、表面の熱硬化性樹脂層の剥離
が無いことである。更に本発明の成形品は、複合部分が
複雑な三次元形状であっても、表面に熱硬化性樹脂層が
ほぼ均一に複合化したものも提供できる。ここで言うほ
ぼ均一との好ましい状態は、熱可塑性樹脂の表面に被覆
している熱硬化性樹脂層の９０％以上の領域において、
熱硬化性樹脂層の肉厚変動が、平均肉厚の±５０％以内
であることである。The composite hollow molded article of the present invention also provides a composite in which a thermosetting resin and a thermoplastic resin are firmly composited. Here, the term "strong adhesion" means that a thermosetting resin layer coated on the surface is cut 11 times in length and width at intervals of 1 mm and the surface layer is peeled off with a cellophane tape. That is, there is no peeling of the conductive resin layer. Further, the molded article of the present invention can provide a molded article in which a thermosetting resin layer is almost uniformly composited on the surface even if the composite portion has a complicated three-dimensional shape. The preferred state of substantially uniform here is that in a region of 90% or more of the thermosetting resin layer covering the surface of the thermoplastic resin,
The variation in the thickness of the thermosetting resin layer is within ± 50% of the average thickness.
【００２５】本発明で言う熱硬化性樹脂とは、充分に高
い温度まで加熱した時、架橋・硬化する樹脂を総称する
物である。架橋は、自然に行われるもの、架橋のために
硬化剤又は触媒を含むものを含み、通常熱可塑性樹脂と
言われる樹脂であっても、過酸化物等の触媒により架橋
するものであっても、本発明に含まれる。本発明に好適
な熱硬化性樹脂の例を挙げれば、フェノール樹脂（Ｐ
Ｆ）、アミノ樹脂（例えば、ユリア樹脂（ＵＦ）、メラ
ミン樹脂（ＭＦ）、ベンゾグアミン樹脂）等のホルムア
ルデヒド系樹脂。また、ジアリルフタレート（アリル樹
脂）（ＤＡＰ）、不飽和ポリエステル樹脂（ＵＰ）、エ
ポキシ樹脂（ＥＰ）、熱硬化性ポリウレタン（ＰＵ
Ｒ）、シリコーン（ＳＩ）等であり、常温で固体状のプ
レポリマーが存在するものが、特に望ましい。これらの
樹脂は、必要であれば、触媒や増量剤、ガラス繊維、マ
イカ、炭酸カルシュウム等の補強剤を含んでも良い。The term "thermosetting resin" as used in the present invention is a generic term for resins which crosslink and cure when heated to a sufficiently high temperature. Crosslinking is carried out naturally, including those containing a curing agent or a catalyst for crosslinking, even if the resin is usually called a thermoplastic resin, or even if it is crosslinked with a catalyst such as a peroxide. , Included in the present invention. As an example of a thermosetting resin suitable for the present invention, a phenol resin (P
F) and formaldehyde resins such as amino resins (eg, urea resin (UF), melamine resin (MF), benzogamine resin). Also, diallyl phthalate (allyl resin) (DAP), unsaturated polyester resin (UP), epoxy resin (EP), thermosetting polyurethane (PU
R), silicone (SI) and the like, in which a solid prepolymer is present at room temperature, are particularly desirable. These resins may contain a reinforcing agent such as a catalyst, a bulking agent, glass fiber, mica, and calcium carbonate, if necessary.
【００２６】又、冷却・固化後の金型面からの離型を容
易にするために外部離型剤を用いてもよいが、生産性の
点等から、熱硬化性樹脂混合物に内部離型剤を加えた方
が望ましい。An external release agent may be used to facilitate release from the mold surface after cooling and solidification. However, from the viewpoint of productivity, etc., an internal release agent is added to the thermosetting resin mixture. It is desirable to add an agent.
【００２７】本発明の熱硬化性樹脂と複合する熱可塑性
樹脂とは、ポリエチレン、ポリプロピレン等のオレフィ
ン系樹脂、ポリスチレン、スチレン−アクリロニトリル
共重合体、ＡＢＳ樹脂、スチレン−無水マレン酸共重合
体等のスチレン系樹脂、ポリ塩化ビニル、塩化ビニル−
酢酸ビニル共重合体（ＥＶＡ）等の塩化ビニル系樹脂、
ポリエチレンテレフタレート、ポリブチレンテレフタレ
ート等のポリエステル系樹脂、ポリカーボネート系樹
脂、ポリアミド系樹脂、ポリフェニレンエーテル系樹
脂、ポリオキシメチレン系樹脂、ポリメチルメタクリレ
ート系樹脂ポリエーテルイミド樹脂、ポリフェニレンサ
ルファイド樹脂等のいわいるスーパーエンジニアリング
樹脂、セルロースアセテート等の繊維素誘導体樹脂及び
これらのブレンド物等が挙げられ、これらはガラス繊維
や鉄粉、タルク、炭酸カルシウム等の充填剤、可塑剤等
の通常の樹脂添加剤を含んでも良い。また、上記樹脂の
ポリマーブレンドやポリマーアロイも本発明の熱可塑性
樹脂として使用できる。The thermoplastic resin composited with the thermosetting resin of the present invention includes olefin resins such as polyethylene and polypropylene, polystyrene, styrene-acrylonitrile copolymer, ABS resin, styrene-maleic anhydride copolymer and the like. Styrene resin, polyvinyl chloride, vinyl chloride
Vinyl chloride resins such as vinyl acetate copolymer (EVA),
Super engineering such as polyester resin such as polyethylene terephthalate and polybutylene terephthalate, polycarbonate resin, polyamide resin, polyphenylene ether resin, polyoxymethylene resin, polymethyl methacrylate resin polyetherimide resin, polyphenylene sulfide resin, etc. Resins, cellulose derivative resins such as cellulose acetate and blends thereof, and the like.These may include ordinary resin additives such as glass fibers, iron powder, talc, fillers such as calcium carbonate, and plasticizers. . Further, polymer blends and polymer alloys of the above resins can also be used as the thermoplastic resin of the present invention.
【００２８】[0028]
【発明の実施の形態】本発明の熱硬化性樹脂を金型内に
て硬化させるブロー成型用金型の一例を図１に示す。DESCRIPTION OF THE PREFERRED EMBODIMENTS FIG. 1 shows an example of a blow molding die for curing the thermosetting resin of the present invention in the die.
【００２９】[0029]
【００３０】[0030]
【実施例１】底面が直径９ｃｍの円形で、高さ２１ｃｍ
である円筒型ボトル形状成形品をブロー成形した。Embodiment 1 A bottom surface is a circle having a diameter of 9 cm and a height of 21 cm.
Was blow-molded.
【００３１】金型の主要構成部は、図１の通りである。
熱硬化性樹脂としては、ＤＡＰ樹脂を利用した。使用し
たＤＡＰ樹脂混合物の組成としては、ＤＡＰのプレポリ
マー（２〜２０量体）９２部、ＤＡＰモノマー６部、過
酸化べンゾイル２部、フロロカーボン化合物と合成有機
酸エステル誘導体を主成分とする内部離型剤０．３部を
アセトン１００部に溶解した。The main components of the mold are as shown in FIG.
DAP resin was used as the thermosetting resin. The composition of the DAP resin mixture used was as follows: 92 parts of a prepolymer (2 to 20 mer) of DAP, 6 parts of DAP monomer, 2 parts of benzoyl peroxide, an inner part mainly composed of a fluorocarbon compound and a synthetic organic acid ester derivative. 0.3 parts of the release agent was dissolved in 100 parts of acetone.
【００３２】これを更に３倍にアセトンで希釈したもの
をスプレーガンで直接金型面に５０μｍの厚みで塗布し
た。この際金型温度は６０℃に予め温調しておき溶剤で
あるアセトンの揮発を促した。金型表面に塗布され、固
着した粉体状のプレポリマー混合物は、固形分が８２．
６％であった。また、金型表面に塗布された粉体状のプ
レポリマーの混合物の密度ρｒと硬化物の密度ρｓとの
比（ρｒ／ρｓ）は、０．９５であった。This was further diluted with acetone three times and applied directly to the mold surface with a spray gun to a thickness of 50 μm. At this time, the mold temperature was previously adjusted to 60 ° C. to promote the evaporation of acetone as a solvent. The powdery prepolymer mixture applied to and fixed to the mold surface has a solid content of 82.
6%. The ratio (ρr / ρs) between the density ρr of the mixture of the powdery prepolymer applied to the mold surface and the density ρs of the cured product was 0.95.
【００３３】次いで熱可塑性樹脂としてＡＢＳ樹脂を用
い、樹脂温度２３０℃で可塑化し、パリソンを開放した
金型間にぶらさげ、それを挟み込むように金型を閉じ、
圧縮空気を送り込んで金型に熱可塑性樹脂を押しつける
と同時にあらかじめ塗布しておいた熱硬化性樹脂と一体
化した。更に、両樹脂が一体化すると同時に金型内面を
高周波誘導加熱にて急速に昇温し、熱可塑性樹脂表面に
複合化された熱硬化性樹脂を硬化させた。金型温度は１
４０±５℃で２分間加熱し、加熱後直ちに温調水にて金
型を６０℃に冷却し、２０秒間該温度で保持した。金型
加熱、冷却の間、６ｋｇ／ｃｍ2の圧縮空気で熱可塑性
樹脂は、金型内面に押し圧しつづけ、冷却後、圧縮空気
を抜き、型を開いて成形品を取り出した。Next, ABS resin was used as a thermoplastic resin, plasticized at a resin temperature of 230 ° C., the parison was hung between open molds, and the mold was closed so as to sandwich it.
Compressed air was sent to press the thermoplastic resin into the mold, and at the same time integrated with the thermosetting resin that had been applied in advance. Further, at the same time when the two resins were integrated, the inner surface of the mold was rapidly heated by high-frequency induction heating to cure the thermosetting resin composited on the thermoplastic resin surface. Mold temperature is 1
The mold was heated at 40 ± 5 ° C. for 2 minutes, immediately after heating, the mold was cooled to 60 ° C. with temperature-regulated water, and kept at the temperature for 20 seconds. During heating and cooling of the mold, the thermoplastic resin was continuously pressed against the inner surface of the mold with 6 kg / cm 2 of compressed air. After cooling, the compressed air was released, the mold was opened, and the molded product was taken out.
【００３４】この複合成形品の外観は、良好であり、通
常に成形したＡＢＳ樹脂の外観と同等或いはそれ以上に
金型賦形面を正確に転写している。また熱硬化性樹脂層
の９６％の肉厚が、平均肉厚４５μｍの±１０％以内の
肉厚であった。The appearance of the composite molded article is good, and the imprinted surface of the mold is accurately transferred to the same level as or better than the appearance of the normally molded ABS resin. The thickness of 96% of the thermosetting resin layer was within ± 10% of the average thickness of 45 μm.
【００３５】又、ＤＡＰ樹脂の密着性をクロスカット・
セロテープ剥離テストした結果も１００／１００で全く
剥がれず、充分な密着性を得た。又，ＤＡＰ樹脂層の表
面硬度は、鉛筆硬度で２Ｈあり、ＡＢＳ樹脂の表面硬さ
ＨＢに比較して格段に向上している。Further, the adhesion of the DAP resin is determined by cross-cutting.
As a result of the cellophane tape peeling test, no peeling was found at 100/100, and sufficient adhesion was obtained. The surface hardness of the DAP resin layer is 2H in pencil hardness, which is much higher than the surface hardness HB of the ABS resin.
【００３６】[0036]
【実施例２】縦３０ｃｍ、横５０ｃｍ、厚さ５ｃｍの事
務機器用天板形状成形品をブロー成形した。EXAMPLE 2 A top plate for office equipment having a length of 30 cm, a width of 50 cm and a thickness of 5 cm was blow-molded.
【００３７】熱硬化性樹脂としては、ＤＡＰ樹脂を利用
した。使用したＤＡＰ樹脂混合物の組成としては、ＤＡ
Ｐのプレポリマー（２〜２０量体）９２部、ＤＡＰモノ
マー６部、過酸化べンゾイル２部、フロロカーボン化合
物と合成有機酸エステル誘導体を主成分とする内部離型
剤０．３部をアセトン１００部に溶解したものを、スプ
レーガンにてポリエステルフィルムに塗布し、乾燥し
て、溶媒のアセトンを揮発させたものを、金型内の天板
オモテ面が形成される側にフィルム送り装置にて挿入し
た。該フィルムは、ＤＡＰ樹脂が熱可塑性樹脂と直接一
体化されるように、ＤＡＰ塗布面を金型の中央部、即ち
パリソン側に向けて挿入した。As the thermosetting resin, a DAP resin was used. The composition of the DAP resin mixture used was DA
92 parts of a prepolymer (2 to 20 mer) of P, 6 parts of DAP monomer, 2 parts of benzoyl peroxide, 0.3 part of an internal mold release agent containing a fluorocarbon compound and a synthetic organic acid ester derivative as main components, and acetone 100 parts The solution dissolved in the part was applied to a polyester film with a spray gun, dried and the solvent acetone was volatilized, and a film feeder was used on the side where the top plate front surface in the mold was formed. Inserted. The film was inserted with the DAP application surface facing the center of the mold, ie, the parison side, so that the DAP resin was directly integrated with the thermoplastic resin.
【００３８】次いで熱可塑性樹脂としてＡＢＳ樹脂を樹
脂温度２３０℃で可塑化し、パリソンを開放した金型間
にぶらさげ、それを挟み込むように金型を閉じ、圧縮空
気を送り込んで金型に熱可塑性樹脂を押しつけると同時
にあらかじめ挿入しておいた熱硬化性樹脂と一体化し
た。更に、両樹脂が一体化すると同時に金型温度を高周
波誘導加熱にて急速に加熱し、熱可塑性樹脂表面に複合
化された熱硬化性樹脂を硬化させた。金型温度が１４０
±５℃で２分間保たれる様に加熱し、加熱後直ちに温調
水にて金型を６０℃に冷却、１分間該温度で保持した。
金型加熱、冷却の間、６ｋｇ／ｃｍ2の圧縮空気で熱可
塑性樹脂は、金型に押し圧しつづけ、冷却後、圧縮空気
を抜き、型を開いて成形品を取り出した。成形品取り出
し後、バリを除去すると同時に、ポリエステルフィルム
を剥がした。Next, an ABS resin as a thermoplastic resin is plasticized at a resin temperature of 230 ° C., the parison is hung between open molds, the mold is closed so as to sandwich the parison, and compressed air is fed to the thermoplastic resin to form the thermoplastic resin. At the same time as pressing, and integrated with the thermosetting resin previously inserted. Further, at the same time when the two resins were integrated, the mold temperature was rapidly heated by high-frequency induction heating to cure the thermosetting resin composited on the thermoplastic resin surface. Mold temperature is 140
The mold was heated so as to be kept at ± 5 ° C. for 2 minutes, and immediately after the heating, the mold was cooled to 60 ° C. with temperature-regulated water, and kept at the temperature for 1 minute.
During heating and cooling of the mold, the thermoplastic resin was continuously pressed against the mold with 6 kg / cm 2 of compressed air. After cooling, the compressed air was released, the mold was opened, and the molded product was taken out. After removing the molded product, the burr was removed and the polyester film was peeled off.
【００３９】[0039]
【実施例３】縦３０ｃｍ、横５０ｃｍ、厚さ５ｃｍの事
務機器用天板形状成形品をブロー成形した。Example 3 A top plate for office equipment having a length of 30 cm, a width of 50 cm and a thickness of 5 cm was blow-molded.
【００４０】化粧板作成用に市販されている未硬化のメ
ラミン系熱硬化性樹脂を含む含浸紙を金型内の天板オモ
テ面が形成される側にフィルム送り装置にて挿入した。A commercially available impregnated paper containing an uncured melamine-based thermosetting resin for making a decorative board was inserted into the mold on the side of the mold where the front surface of the top plate was formed by a film feeder.
【００４１】次いで熱可塑性樹脂としてＡＢＳ樹脂を用
い、樹脂温度２３０℃で可塑化し、パリソンを開放した
金型間にぶらさげ、それを挟み込むように金型を閉じ、
圧縮空気を送り込んで金型に熱可塑性樹脂を押しつける
と同時にあらかじめ挿入しておいた熱硬化性樹脂と一体
化した。更に、両樹脂が一体化すると同時に金型内面を
高周波誘導加熱にて急速に昇温し、熱可塑性樹脂表面に
複合化された熱硬化性樹脂を硬化させた。金型温度は１
３０±５℃で３分間加熱し、加熱後直ちに温調水にて金
型を６０℃に冷却し、１分間該温度で保持した。金型加
熱、冷却の間、６ｋｇ／ｃｍ2の圧縮空気で熱可塑性樹
脂は、金型に押し圧しつづけ、冷却後、圧縮空気を抜
き、型を開いて成形品を取り出した。成形品取り出し
後、バリを除去した。Next, an ABS resin was used as a thermoplastic resin, plasticized at a resin temperature of 230 ° C., the parison was hung between open molds, and the mold was closed so as to sandwich it.
Compressed air was fed to press the thermoplastic resin into the mold, and at the same time integrated with the thermosetting resin previously inserted. Further, at the same time when the two resins were integrated, the inner surface of the mold was rapidly heated by high-frequency induction heating to cure the thermosetting resin composited on the thermoplastic resin surface. Mold temperature is 1
The mold was heated at 30 ± 5 ° C. for 3 minutes, immediately after heating, the mold was cooled to 60 ° C. with temperature-controlled water, and kept at the temperature for 1 minute. During heating and cooling of the mold, the thermoplastic resin was continuously pressed against the mold with 6 kg / cm 2 of compressed air. After cooling, the compressed air was released, the mold was opened, and the molded product was taken out. After removing the molded product, burrs were removed.
【００４２】この複合成形品の外観は、良好であった。
又、ＤＡＰ樹脂の密着性をクロスカット・セロテープ剥
離テストした結果も１００／１００で全く剥がれず、充
分な密着性を得た。又，ＤＡＰ樹脂層の表面硬度は、鉛
筆硬度で２Ｈあり、ＡＢＳ樹脂の表面硬さＨＢに比較し
て格段に向上している。更に熱硬化性樹脂を複合化した
天板表面にクロロホルムを滴下して硬化テストを行った
所、表面にしみ、樹脂の溶融等は認められなかった。更
に表面に一体化した含浸紙にしわ、破れ等はなく極めて
外観は良好であった。The appearance of the composite molded article was good.
In addition, the cross-cut / cellotape peel test of the adhesion of the DAP resin was 100/100. The surface hardness of the DAP resin layer is 2H in pencil hardness, which is much higher than the surface hardness HB of the ABS resin. Furthermore, when a curing test was performed by dropping chloroform onto the surface of the top plate in which the thermosetting resin was composited, no smearing of the resin was observed on the surface. Furthermore, the impregnated paper integrated on the surface did not have wrinkles or tears, and the appearance was extremely good.
【００４３】以上のことより、これまでに得ることの出
来なかった表面特性を有するブロー成形製天板を生産性
良く作成出来た。As described above, a blow-molded top plate having surface characteristics that could not be obtained until now can be produced with high productivity.
【００４４】[0044]
【発明の効果】本発明の複合ブロー成形方法を用いれ
ば、均一な肉厚の熱硬化性樹脂が熱可塑性樹脂の表面に
被覆した、表面硬度、耐薬品性等の優れた複合中空成形
品、すなわち熱硬化性樹脂の高度な物性、化学特性と熱
可塑性樹脂の良成形性を生かした複合中空成形品を容易
に得ることが出来る。According to the composite blow molding method of the present invention, a composite hollow molded product having a uniform thickness of a thermosetting resin coated on the surface of a thermoplastic resin and having excellent surface hardness, chemical resistance and the like can be obtained. That is, it is possible to easily obtain a composite hollow molded article utilizing the advanced physical properties and chemical properties of the thermosetting resin and the good moldability of the thermoplastic resin.
【図１】本発明に用いられる複合射出成形用金型の断面
図の概略概念図の一例である。 １：ブロー成形用金型 ２：インダクターコイル ３：温調用冷却水管FIG. 1 is an example of a schematic conceptual diagram of a cross-sectional view of a composite injection molding die used in the present invention. 1: Mold for blow molding 2: Inductor coil 3: Cooling water pipe for temperature control
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｂ２９Ｌ 9:00 22:00 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 6 Identification code FI B29L 9:00 22:00
Claims (10)
確に転写したほぼ均一肉厚の熱硬化性樹脂が強固に密着
した複合中空成形品。1. A composite hollow molded article in which a thermosetting resin having a substantially uniform thickness on which a mold-molding surface has been accurately transferred is firmly adhered to the surface of a thermoplastic resin.
分の形状が三次元形状であることを特徴とする請求項１
に記載の中空成形品。2. The shape of a composite portion of a thermoplastic resin and a thermosetting resin is a three-dimensional shape.
The hollow molded article according to 1.
接着剤を用いてまたは接着剤を用いないで強固に密着し
ていることを特徴とする請求項１又は２に記載の中空成
形品。3. The hollow molding according to claim 1, wherein the thermosetting resin and the thermoplastic resin are firmly adhered to each other with or without a thermosetting adhesive. Goods.
状態の熱硬化性樹脂を存在せしめた状態で、該金型内に
熱可塑性樹脂をブロー成形し、熱可塑性樹脂と熱硬化性
樹脂とを一体化させる過程で又は一体化させた後に、熱
硬化性樹脂を硬化させながら又は硬化後に熱可塑性樹脂
部分を賦型、冷却固化して複合成形品を得ることを特徴
とする複合ブロー成形法。4. In a state where an uncured thermosetting resin is present at a desired position in a blow molding mold, a thermoplastic resin is blow-molded in the mold, and the thermoplastic resin and the thermosetting resin are mixed. A composite blow, wherein the thermoplastic resin portion is molded and cooled and solidified while curing or after curing the thermosetting resin in the process of or after the resin is integrated, thereby obtaining a composite molded product. Molding method.
態で行い、熱可塑性樹脂の固化を金型を冷却した状態で
行うことを特徴とする請求項４に記載の成形法。5. The molding method according to claim 4, wherein the curing of the thermosetting resin is performed in a state where the temperature of the mold is raised, and the solidification of the thermoplastic resin is performed in a state where the mold is cooled.
利用することを特徴とする請求項４又は５に記載の成形
法。6. The molding method according to claim 4, wherein the method of raising the temperature of the mold uses high-frequency induction heating.
（℃）表示で熱硬化性樹脂を硬化させる温度の３分の１
以上に温調しておくことを特徴とする請求項４〜６のい
ずれかに記載の成形法。7. The mold temperature before heating the mold is one third of the temperature at which the thermosetting resin is cured in degrees Celsius (° C.).
The molding method according to any one of claims 4 to 6, wherein the temperature is adjusted as described above.
せしめることを特徴とする請求項４〜７のいずれかに記
載の成形法。8. The molding method according to claim 4, wherein a thermosetting resin is applied to an inner surface of the mold to be present.
金型内に存在せしめることを特徴とする請求項４〜８の
いずれかに記載の成形法。9. The molding method according to claim 4, wherein a base material coated or impregnated with a thermosetting resin is present in a mold.
脂のプレポリマー、または、プレポリマーとモノマーと
の混合物であることを特徴とする請求項４〜９のいずれ
かに記載の成形法。10. The molding according to claim 4, wherein the uncured thermosetting resin is a thermosetting resin prepolymer or a mixture of a prepolymer and a monomer. Law.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33690696A JPH10166434A (en) | 1996-12-17 | 1996-12-17 | Composite blow molded product and molding method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33690696A JPH10166434A (en) | 1996-12-17 | 1996-12-17 | Composite blow molded product and molding method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH10166434A true JPH10166434A (en) | 1998-06-23 |
Family
ID=18303738
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP33690696A Pending JPH10166434A (en) | 1996-12-17 | 1996-12-17 | Composite blow molded product and molding method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH10166434A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015183164A (en) * | 2014-03-26 | 2015-10-22 | 東レ株式会社 | Prepreg and method of manufacturing the same, and carbon fiber reinforced composite material |
| JP2021008124A (en) * | 2019-03-20 | 2021-01-28 | 日精エー・エス・ビー機械株式会社 | Method for manufacturing resin container and blow molding device |
-
1996
- 1996-12-17 JP JP33690696A patent/JPH10166434A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015183164A (en) * | 2014-03-26 | 2015-10-22 | 東レ株式会社 | Prepreg and method of manufacturing the same, and carbon fiber reinforced composite material |
| JP2021008124A (en) * | 2019-03-20 | 2021-01-28 | 日精エー・エス・ビー機械株式会社 | Method for manufacturing resin container and blow molding device |
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