JPH0880526A - Glass fiber reinforced polyolefin resin composition, manufacture thereof, and molded body formed thereby - Google Patents
Glass fiber reinforced polyolefin resin composition, manufacture thereof, and molded body formed therebyInfo
- Publication number
- JPH0880526A JPH0880526A JP6219223A JP21922394A JPH0880526A JP H0880526 A JPH0880526 A JP H0880526A JP 6219223 A JP6219223 A JP 6219223A JP 21922394 A JP21922394 A JP 21922394A JP H0880526 A JPH0880526 A JP H0880526A
- Authority
- JP
- Japan
- Prior art keywords
- glass fiber
- polyolefin resin
- acid
- modified
- based resin
- 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.)
- Withdrawn
Links
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、優れた表面性状を有す
ると共に、機械的特性、殊に衝撃特性および曲げ強度の
いずれにも優れた成形体を与えるガラス繊維強化ＰＯ系
樹脂組成物およびその製法、並びに該組成物を用いた成
形体に関し、この樹脂組成物は、自動車等の内・外装部
品や家庭電化製品、その他各種の分野に用いられる様々
の成形体の素材として有効に活用することができる。FIELD OF THE INVENTION The present invention relates to a glass fiber reinforced PO resin composition and a glass fiber reinforced PO resin composition having excellent surface properties and giving a molded article excellent in both mechanical properties, particularly impact properties and bending strength. Regarding the production method and a molded article using the composition, the resin composition should be effectively utilized as a raw material for various molded articles used in various fields such as interior / exterior parts of automobiles, home electric appliances, etc. You can
【０００２】[0002]
【従来の技術】ポリエチレンやポリプロピレン等のポリ
オレフィン（以下、ＰＯと略記する）系樹脂は、低比重
で化学的安定性や成形加工性に優れ、しかも非常に安価
であるところから、代表的なプラスチック素材の一つと
して汎用されており、これをガラス繊維と複合した繊維
強化ＰＯ系樹脂も様々の分野で実用化されている。2. Description of the Related Art Polyolefin (hereinafter abbreviated as PO) resins such as polyethylene and polypropylene are typical plastics because they have low specific gravity, excellent chemical stability and moldability, and are extremely inexpensive. It is widely used as one of the materials, and a fiber-reinforced PO-based resin obtained by compounding this with glass fiber has also been put to practical use in various fields.
【０００３】しかしながら、この繊維強化ＰＯ系樹脂に
は耐衝撃性に欠けるという難点が指摘されている。これ
は、ＰＯ系樹脂が無極性であり極性で且つ親水性のガラ
ス繊維等との親和性が悪いためであり、その改善策とし
て、ＰＯ系樹脂に極性基を適当な割合でグラフト又は共
重合させる方法、ポリプロピレンをナイロンでグラフト
変性する方法等が試みられており、これらの中でもマト
リックスを構成するＰＯ系樹脂と酸変性されたＰＯ系樹
脂を併用する方法は、最も簡単で効果的な方法といえる
（たとえば特公昭６１−３７２９９号，特開昭６０−９
０２３９号，同６３−２６４６５１号，同６４−９０２
３８号，特開平１−２４０５４５号等）。However, it has been pointed out that the fiber-reinforced PO resin lacks impact resistance. This is because the PO-based resin is non-polar and has poor affinity with polar and hydrophilic glass fibers and the like, and as a measure for improving it, a polar group is grafted or copolymerized to the PO-based resin at an appropriate ratio. Attempts have been made to modify the polypropylene, graft-modify polypropylene with nylon, and the like. Among these, the method of using the PO-based resin constituting the matrix and the acid-modified PO-based resin together is the simplest and most effective method. It can be said (for example, JP-B-61-37299, JP-A-60-9).
No. 0239, No. 63-264651, No. 64-902
38, JP-A-1-240545).
【０００４】ところが、上記特公昭４５−３６４２１号
以外の従来技術では、ＰＯ系樹脂とガラス繊維との親和
性が改善され、それに伴って引張強度や曲げ強度、曲げ
弾性率は向上するが、反面耐衝撃性は低下するという難
点が生じてくる。即ち、強化用繊維との複合によって耐
衝撃性が高められる理由の一つには、該繊維強化樹脂成
形体が破断するときに該強化繊維がマトリックス樹脂か
ら引き抜けるときのエネルギー吸収によってもたらされ
るという考え方が支配的であり、従って、酸変性ＰＯ系
樹脂の添加等により親和性を高めたＰＯ系樹脂をガラス
繊維と複合した場合、マトリックス樹脂からのガラス繊
維の引き抜けが生じ難くなって耐衝撃性はかえって低下
してくる。However, in the prior arts other than JP-B-45-36421, the affinity between the PO resin and the glass fiber is improved, and the tensile strength, bending strength and bending elastic modulus are improved accordingly, but on the other hand The drawback is that the impact resistance decreases. That is, one of the reasons why the impact resistance is enhanced by the combination with the reinforcing fiber is that the energy absorption when the reinforcing fiber is pulled out from the matrix resin when the fiber-reinforced resin molded product is broken is considered. Therefore, when a PO-based resin whose affinity has been increased by adding an acid-modified PO-based resin or the like is combined with the glass fiber, the glass fiber is less likely to be pulled out from the matrix resin and the impact resistance is improved. On the contrary, it decreases.
【０００５】しかもこの方法では、酸変性ＰＯ系樹脂を
単に強化繊維やＰＯ系樹脂と混合しているだけであるか
ら、酸変性ＰＯ系樹脂が全ての強化繊維表面にむら無く
付着しているとは限らず、多くの酸変性ＰＯ系樹脂はガ
ラス繊維表面に付着しないでＰＯ系マトリックス中に分
散しており、添加量に応じた改質効果が得られないとい
う問題も指摘される。Moreover, in this method, since the acid-modified PO-based resin is simply mixed with the reinforcing fibers and the PO-based resin, it is assumed that the acid-modified PO-based resin is evenly attached to the surface of all the reinforcing fibers. However, it is pointed out that many acid-modified PO-based resins are dispersed in the PO-based matrix without adhering to the surface of the glass fiber, and a modifying effect depending on the added amount cannot be obtained.
【０００６】また、上記の様な耐衝撃性の低下を軽減す
るための手段として、たとえば特公昭６３−３５１７９
号や特公平１−４０８５４号公報等には、合成ゴム等の
如く耐衝撃性に優れた弾性素材を、マトリックスを構成
するＰＯ系樹脂にブレンドすることにより複合材として
の耐衝撃性を高める方法が提案されている。Further, as means for reducing the above-mentioned deterioration of impact resistance, for example, Japanese Patent Publication No. 63-35179.
JP-B-1-40854 and the like disclose a method of enhancing impact resistance as a composite material by blending an elastic material having excellent impact resistance such as synthetic rubber with a PO-based resin forming a matrix. Is proposed.
【０００７】ところが、合成ゴムの様な弾性素材をマト
リックスであるＰＯ系樹脂にブレンドすると、耐衝撃性
自体は改善されるものの、ガラス繊維強化ＰＯ系樹脂に
最も期待される曲げ強度や引張強度が大幅に低下し、本
来の要求特性を満足できなくなるという問題が生じてく
る。However, when an elastic material such as synthetic rubber is blended with a PO-based resin which is a matrix, the impact resistance itself is improved, but the bending strength and tensile strength most expected of the glass fiber reinforced PO-based resin are improved. There is a problem in that the characteristics are significantly reduced and the original required characteristics cannot be satisfied.
【０００８】また上記以外の改善法として、特公昭４５
−３６４２１号公報には、シランカップリング剤とα，
β−エチレン性不飽和カルボン酸またはその酸無水物で
変性された酸変性ＰＯ系樹脂との反応生成物によってガ
ラス繊維を予め被覆しておき、それによりマトリックス
樹脂とガラス繊維との接合一体性を高める方法が開示さ
れている。As an improvement method other than the above, Japanese Patent Publication No.
No. 36421 discloses a silane coupling agent and α,
The glass fiber is pre-coated with a reaction product of an acid-modified PO resin modified with β-ethylenically unsaturated carboxylic acid or an acid anhydride thereof, whereby the bonding integrity between the matrix resin and the glass fiber is improved. A method of enhancing is disclosed.
【０００９】しかしながらこの方法も、基本的にはガラ
ス繊維とマトリックス樹脂との接合力を高めることによ
って物性を高めようとするものであるから、両者の接合
一体性向上によって曲げ強度や引張強度は改善される
が、破断時におけるガラス繊維の引き抜けが起こり難く
なり、耐衝撃性が乏しくなるという点では前記従来技術
と同様の欠点が生じてくる。しかも、ガラス繊維に変性
ＰＯ系樹脂を施す手段として、シランカップリング処理
されたガラス繊維を使用する場合は、加熱溶融された変
性ＰＯ系樹脂にガラス繊維を浸漬してシランと変性ＰＯ
系樹脂を化学反応させる方法、シランカップリングされ
ていないガラス繊維を使用する場合は、シランと変性Ｐ
Ｏ系樹脂を化学反応させた反応生成物をガラス繊維に施
す方法が採用されるが、これらの工程で十分な化学反応
を行なわせるにはかなり長時間を要し、生産性が著しく
損なわれる。However, this method also basically aims to improve the physical properties by increasing the bonding force between the glass fiber and the matrix resin, and therefore the bending strength and the tensile strength are improved by improving the bonding integrity of the two. However, the same drawbacks as those of the above-mentioned prior art arise in that the glass fiber is less likely to be pulled out at the time of breaking and the impact resistance is poor. Moreover, when the silane coupling-treated glass fiber is used as the means for applying the modified PO-based resin to the glass fiber, the glass fiber is immersed in the modified PO-based resin that has been heated and melted, and the silane and the modified PO
The method of chemically reacting the base resin, when using the glass fiber which is not silane coupled, silane and modified P
A method of applying the reaction product obtained by chemically reacting the O-based resin to the glass fiber is adopted, but it takes a considerably long time to perform a sufficient chemical reaction in these steps, and the productivity is remarkably impaired.
【００１０】工業技術の急速な進歩および社会的ニーズ
の複雑化につれて、各種素材に対する要求特性はますま
す厳しくなる傾向があり、ガラス繊維強化ＰＯ系樹脂に
ついても、本来の特性である優れた曲げ強度や引張強度
を悪化させることなく、その耐衝撃強度を高めることが
でき、しかも比較的安価に提供し得る様な技術の確立が
待たれている。Due to the rapid progress of industrial technology and the complication of social needs, the required properties for various materials tend to become more and more severe, and glass fiber reinforced PO-based resins also have excellent bending strength which is the original property. There is a need for establishment of a technique that can increase the impact strength without deteriorating the tensile strength and the tensile strength and can be provided at a relatively low cost.
【００１１】[0011]
【発明が解決しようとする課題】本発明は上記の様な事
情に着目してなされたものであって、その目的は、曲げ
強度や引張強度をあまり低下させることなく耐衝撃強度
を高め、バランスのとれた強度特性を発揮し得る様なガ
ラス繊維強化ＰＯ系樹脂組成物および該樹脂組成物を用
いた高性能の成形体を提供しようとするものである。SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and its purpose is to enhance impact resistance strength and balance without significantly lowering bending strength and tensile strength. The present invention aims to provide a glass fiber reinforced PO resin composition capable of exhibiting excellent strength characteristics and a high-performance molded product using the resin composition.
【００１２】[0012]
【課題を解決するための手段】上記課題を解決すること
のできた本発明に係るガラス繊維強化ＰＯ系樹脂組成物
の製法は、強化用ガラス繊維の集束体のチョップドスト
ランドと酸変性されたＰＯ系樹脂粉末を気流中で混合す
ることにより、強化用ガラス繊維の集束体を開繊すると
共に開繊された強化用ガラス繊維の表面に酸変性された
ＰＯ系樹脂を付着せしめ、該樹脂が表面に付着した強化
用ガラス繊維をＰＯ系樹脂粉末と均一に混合するところ
に要旨が存在する。A method for producing a glass fiber reinforced PO resin composition according to the present invention, which has been able to solve the above-mentioned problems, is a method for producing a chopped strand of a reinforcing glass fiber bundle and an acid-modified PO resin. By mixing the resin powder in an air stream, the bundle of reinforcing glass fibers is opened, and at the same time, the acid-modified PO-based resin is attached to the surface of the opened reinforcing glass fiber. The gist exists in uniformly mixing the adhered glass fiber for strengthening with the PO resin powder.
【００１３】尚、上記本発明を実施するに当たっては、
上記気流中での混合を加熱条件下に行ない、開繊ガラス
繊維表面に酸変性ＰＯ系樹脂を溶融付着させ、あるいは
強化用ガラス繊維の集束体のチョップドストランドと前
記酸変性ＰＯ系樹脂粉末を気流中で混合した後、該混合
物を加熱することにより、開繊ガラス繊維の表面に酸変
性ＰＯ系樹脂を溶融付着させるのが有効である。In carrying out the present invention described above,
Mixing in the above airflow is performed under heating conditions to melt and adhere the acid-modified PO-based resin to the surface of the opened glass fiber, or chopped strands of the reinforcing glass fiber bundle and the acid-modified PO-based resin powder It is effective to melt-adhere the acid-modified PO-based resin to the surface of the opened glass fiber by heating the mixture after mixing in the inside.
【００１４】また、開繊された強化用ガラス繊維の表面
に酸変性ＰＯ系樹脂を付着せしめると共に、あるいは付
着せしめた後に、更に金属および／または金属化合物を
付着せしめ、これをＰＯ系樹脂粉末と均一に混合したも
のは、あるいは表面に酸変性ＰＯ系樹脂が付着したガラ
ス繊維を、金属および／または金属化合物を含むＰＯ系
樹脂粉末と均一に混合したものは、後述する如く、該樹
脂組成物を加熱加圧成形した後の状態でガラス繊維とマ
トリックスを構成するＰＯ系樹脂との界面でトランスク
リスタル構造の晶出物の生成が促進され、性能の一段と
優れた樹脂成形体を与える。Further, the acid-modified PO-based resin is adhered to the surface of the opened reinforcing glass fiber, or after the acid-modified PO-based resin is adhered, a metal and / or a metal compound is further adhered to form a PO-based resin powder. A homogeneous mixture or a homogeneous mixture of glass fibers having an acid-modified PO-based resin adhered to the surface thereof and a PO-based resin powder containing a metal and / or a metal compound is used as described below. After heat-pressing, the formation of crystallized products having a trans-crystal structure is promoted at the interface between the glass fiber and the PO-based resin constituting the matrix, and a resin molded product with further improved performance is provided.
【００１５】従って本発明では、上記方法によって得ら
れる樹脂組成物および該樹脂組成物を成形することによ
って得られる成形体にも特徴を有しており、該成形体の
構成は、表面に酸変性ＰＯ系樹脂または該樹脂と金属お
よび／または金属化合物が付着した強化用ガラス繊維
が、ＰＯ系樹脂マトリックス中に均一に分散され、ある
いは表面に酸変性ＰＯ系樹脂が付着した強化用ガラス繊
維が、金属および／または金属化合物を含むＰＯ系樹脂
マトリックス中に均一に分散され、該強化用ガラス繊維
とＰＯ系樹脂マトリックスとの界面にトランスクリスタ
ル構造の晶出物が存在するところに要旨を有している。Therefore, the present invention is also characterized by the resin composition obtained by the above method and the molded product obtained by molding the resin composition. The structure of the molded product is acid-modified on the surface. The reinforcing glass fiber having the PO resin or the resin and the metal and / or the metal compound attached thereto is uniformly dispersed in the PO resin matrix, or the reinforcing glass fiber having the acid-modified PO resin attached to the surface is It has a gist in that a crystallized product having a trans crystal structure is uniformly dispersed in a PO resin matrix containing a metal and / or a metal compound, and a crystallized product having a trans crystal structure is present at the interface between the reinforcing glass fiber and the PO resin matrix. There is.
【００１６】[0016]
【作用】上記の様に本発明に係るガラス繊維強化ＰＯ系
樹脂組成物の構成は、強化用ガラス繊維の集束体のチョ
ップドストランドと酸変性されたＰＯ系樹脂粉末を気流
中で混合し、強化用ガラス繊維の集束体を開繊すると共
に開繊された強化用ガラス繊維の表面に酸変性されたＰ
Ｏ系樹脂を付着せしめ、該樹脂が表面に付着したガラス
強化用繊維をＰＯ系樹脂粉末と均一に混合するものであ
り、上記気流中での混合を加熱条件下に行ない、開繊ガ
ラス繊維表面に酸変性ＰＯ系樹脂粉末を溶融付着させ、
あるいは強化用ガラス繊維集束体のチョップドストラン
ドと前記酸変性ＰＯ系樹脂粉末を気流中で混合した後、
該混合物を加熱することによって、開繊ガラス繊維の表
面に酸変性ＰＯ系樹脂を万遍なく均一に溶融付着させる
ことにより、開繊ガラス繊維のＰＯ系樹脂に対する親和
性を無駄なく且つ効率よく改善することができる。As described above, the composition of the glass fiber reinforced PO resin composition according to the present invention is reinforced by mixing the chopped strands of the reinforcing glass fiber bundle and the acid-modified PO resin powder in an air stream. The glass fiber bundles for application are opened and acid-modified P is formed on the surface of the opened reinforcing glass fibers.
An O-based resin is adhered, and the glass-reinforcing fiber having the resin adhered to the surface is uniformly mixed with PO-based resin powder, and the mixing in the air stream is performed under heating conditions. Acid-modified PO resin powder is melted and adhered to
Alternatively, after mixing the chopped strands of the reinforcing glass fiber bundle with the acid-modified PO-based resin powder in an air stream,
By heating the mixture, the acid-modified PO-based resin is uniformly melted and adhered to the surface of the open-fiber glass fiber, thereby improving the affinity of the open-fiber glass fiber for the PO-based resin efficiently and efficiently. can do.
【００１７】即ち、上記の方法を採用すれば、ガラス繊
維収束体の開繊と該開繊されたガラス繊維表面への酸変
性ＰＯ系樹脂の付着が同時に効率よく行なわれると共
に、開繊された細いガラス繊維の表面に万遍なく酸変性
ＰＯ系樹脂が付着するので、この様にして処理された表
面処理ガラス繊維をＰＯ系樹脂粉末と混合すると、酸変
性ＰＯ系樹脂の無駄を生じることなく、使用された酸変
性ＰＯ系樹脂は全てがＰＯ系樹脂との親和性向上に有効
に作用することになり、従来法に比べて酸変性ＰＯによ
るガラス繊維の改質処理が著しく簡素化されると共に、
少ない酸変性ＰＯ樹脂の使用量で高い改質効果を得るこ
とができる。That is, when the above-mentioned method is adopted, the opening of the glass fiber bundle and the adhesion of the acid-modified PO-based resin to the surface of the opened glass fiber can be efficiently carried out at the same time, and the fibers are opened. Since the acid-modified PO-based resin is evenly attached to the surface of the thin glass fiber, mixing the surface-treated glass fiber treated in this way with the PO-based resin powder does not waste the acid-modified PO-based resin. All of the acid-modified PO-based resins used are effective in improving the affinity with the PO-based resin, and the glass fiber modification treatment with acid-modified PO is significantly simplified as compared with the conventional method. With
A high modifying effect can be obtained with a small amount of the acid-modified PO resin.
【００１８】上記の様にして得られるガラス繊維強化Ｐ
Ｏ系樹脂組成物が優れた物理的特性を示す理由について
は、現在のところ全てが明らかになっている訳ではない
が、上記の様にガラス繊維の改質が均一且つ万遍なく行
なわれることによって、開繊ガラス繊維とＰＯ系樹脂と
の親和性が適度に高められ、優れた引張強度と曲げ強度
を兼ね備えた複合組成物を与えるものと考えている。殊
に本発明者らが実験により確認したところによると、上
記の様にして得られる表面改質処理された開繊ガラス繊
維とＰＯ系樹脂とを含む組成物を加熱加圧成形して得ら
れる成形体におけるガラス繊維とマトリックスを構成す
るＰＯ系樹脂の界面にはトランスクリスタル構造の晶出
物が生成しており、該トランスクリスタル構造の晶出物
の存在によって上記両物性がよりバランス良く発揮され
ることが確認された。Glass fiber reinforced P obtained as described above
The reasons why the O-based resin composition exhibits excellent physical properties have not been clarified at present, but the above-mentioned modification of the glass fiber is carried out uniformly and uniformly. It is considered that the affinity between the open fiber glass and the PO-based resin is appropriately increased by the above, and a composite composition having excellent tensile strength and bending strength is provided. In particular, the inventors of the present invention have confirmed through experiments that the composition containing the surface-modified open fiber glass and the PO resin obtained as described above can be obtained by heating and pressing. A crystallized product with a trans crystal structure is formed at the interface between the glass fiber and the PO-based resin constituting the matrix in the molded product, and the presence of the crystallized product with the trans crystal structure allows the above physical properties to be exhibited in a better balance. It was confirmed that
【００１９】そして、上記開繊ガラス繊維表面への酸変
性ＰＯ系樹脂の付着に当たり、任意の時期に更に金属お
よび／または金属化合物を付着させておけば、これらに
よって改質処理された開繊ガラス繊維をＰＯ系樹脂粉末
と均一に混合して得られる強化ＰＯ系樹脂組成物を加熱
加圧成形することによって得られる成形体には、該金属
および／または金属化合物の共存によって前述のトラン
スクリスタルの晶出が一層促進される。また同様の趣旨
で、表面に酸変性ＰＯ系樹脂が付着したガラス繊維を、
金属および／または金属化合物を含むＰＯ系樹脂と均一
に混合して得られる強化ＰＯ系樹脂組成物を加熱加圧成
形することによって得られる成形体においても、該金属
および／または金属化合物の共存によって前述のトラン
スクリスタルの晶出が促進される。When the acid-modified PO resin is attached to the surface of the opened glass fibers, if a metal and / or a metal compound is further attached at an arbitrary time, the opened glass modified by the metal and / or metal compound is added. A molded body obtained by heating and pressurizing a reinforced PO resin composition obtained by uniformly mixing fibers with a PO resin powder has a trans-crystal of the above-mentioned transcrystal by coexistence of the metal and / or the metal compound. Crystallization is further promoted. Further, for the same purpose, glass fiber having an acid-modified PO-based resin adhered to its surface is
Also in a molded article obtained by heat-press molding a reinforced PO resin composition obtained by uniformly mixing with a PO resin containing a metal and / or a metal compound, the coexistence of the metal and / or the metal compound Crystallization of the aforementioned trans crystal is promoted.
【００２０】従って本発明では、上記樹脂組成物を加熱
加圧成形することによって得られる成形体にも特徴を有
しており、その構成は、表面に酸変性ＰＯ系樹脂または
該樹脂と金属および／または金属化合物が付着した強化
用ガラス繊維が、ＰＯ系樹脂マトリックス中に均一に分
散され、あるいは表面に酸変性ＰＯ系樹脂が付着した強
化用ガラス繊維が、金属および／または金属化合物を含
むＰＯ系樹脂マトリックス中に均一に分散され、該強化
用ガラス繊維とＰＯ系樹脂マトリックスとの界面にトラ
ンスクリスタル構造の晶出物が存在することによって特
徴付けられる。Therefore, the present invention is also characterized by a molded body obtained by heat-press molding the above resin composition, and the constitution thereof is an acid-modified PO-based resin on the surface or the resin and metal and The reinforcing glass fibers having the metal compound attached thereto are uniformly dispersed in the PO resin matrix, or the glass fibers having the acid-modified PO resin attached to the surface of the reinforcing glass fiber contain metal and / or a metal compound. It is characterized in that it is uniformly dispersed in the system resin matrix, and crystallized substances having a trans crystal structure are present at the interface between the reinforcing glass fiber and the PO system resin matrix.
【００２１】即ちトランスクリスタル構造とは、繊維軸
に対して垂直方向に発達した結晶構造をいい、本発明に
おいては、開繊ガラス繊維の表面において、マトリック
ス樹脂を構成するＰＯ系樹脂の結晶がガラス繊維軸に対
し垂直方向に生成したものであり、それによりガラス繊
維とマトリックス樹脂との一体性が高められ、複合材料
としての曲げ強度や引張強度が著しく高められる。That is, the trans-crystal structure means a crystal structure developed in the direction perpendicular to the fiber axis. In the present invention, the crystal of the PO-based resin constituting the matrix resin is glass on the surface of the opened glass fiber. It is generated in the direction perpendicular to the fiber axis, which enhances the integrity of the glass fiber and the matrix resin, and significantly increases the bending strength and tensile strength of the composite material.
【００２２】ところでトランスクリスタル構造自体は既
に公知であり、例えば、高弾性率の炭素繊維やアラミド
繊維と結晶性ポリマーの界面では、この様なトランスク
リスタル構造の晶出物が生成して繊維と樹脂の一体性が
向上し、界面接着強度その他の機械的特性が高められる
ことが確認されている。By the way, the trans crystal structure itself is already known. For example, at the interface between a high elastic modulus carbon fiber or aramid fiber and a crystalline polymer, a crystallized product of such a trans crystal structure is produced to form fibers and a resin. It has been confirmed that the interlocking property is improved and the interfacial adhesive strength and other mechanical properties are enhanced.
【００２３】従って、ガラス繊維強化ＰＯ系樹脂成形体
においても、この様なトランスクリスタル構造を晶出さ
せることによって物性を改質することが考えられる。と
ころがガラス繊維強化樹脂では、例えばA.Lustiger et.
al;ANTEC'93 p2559-2565, J.Varga, J.Karger-Kocsis;
Composites Science and Technology, Vol.48(1993)p19
1-198等に記載されている様に、ガラス繊維にテンショ
ンを与えたり、或は成形加工時の冷却速度を厳密にコン
トロールする方法などを採用しなければトランスクリス
タル構造の晶出物を生成させることはできないと考えら
れており、操作が煩雑で厳密な管理が必要であるにもか
かわらず、トランスクリスタルが確実に生成するとは限
らず、現にこの様な着想を実用面で有効に活用した例は
存在しない。Therefore, it is conceivable that the glass fiber reinforced PO resin molded article may be modified in its physical properties by crystallizing such a trans crystal structure. However, with glass fiber reinforced resin, for example, A. Lustiger et.
al; ANTEC'93 p2559-2565, J. Varga, J. Karger-Kocsis;
Composites Science and Technology, Vol.48 (1993) p19
As described in 1-198 etc., crystallized substances with a trans crystal structure will be generated unless tension is applied to the glass fiber or a method of strictly controlling the cooling rate during molding is adopted. It is thought that trans-crystals are not always generated reliably, even though the operation is complicated and strict control is required, and an example in which such an idea is effectively utilized practically Does not exist.
【００２４】ところが、前述の如くガラス繊維集束体の
開繊工程で同時に酸変性ＰＯ系樹脂を付着させ、或は更
に金属および／または金属化合物を付着させた表面改質
開繊ガラス繊維を使用し、これをＰＯ系樹脂と均一に混
合した組成物、あるいは開繊工程で酸変性ＰＯ系樹脂を
付着せしめたガラス繊維を金属および／または金属化合
物を含むＰＯ系樹脂と均一に混合した組成物を使用すれ
ば、極一般的な成形加工における冷却条件下でもその界
面にトランスクリスタル構造の晶出物が生成することが
確認された。However, as described above, the surface-modified spread glass fiber to which the acid-modified PO resin is attached at the same time in the opening process of the glass fiber bundle or to which the metal and / or the metal compound is further attached is used. , A composition in which this is uniformly mixed with a PO-based resin, or a composition in which glass fibers to which an acid-modified PO-based resin has been attached in the opening step are uniformly mixed with a PO-based resin containing a metal and / or a metal compound. It was confirmed that, when used, a crystallized product with a trans crystal structure was formed at the interface even under cooling conditions in a very general molding process.
【００２５】ところで、上記の様にトランスクリスタル
晶出物の生成によってガラス繊維とＰＯ系樹脂マトリッ
クスの親和性が高められると、先に述べた様に曲げ強度
等は向上するが、耐衝撃性は低下することが考えられ
る。しかし、トランスクリスタル構造の晶出物が存在す
る本発明の繊維強化ＰＯ系樹脂成形体では、この様な衝
撃強度の低下も見られず、非常にバランスのとれた機械
的特性が得られる。By the way, when the affinity between the glass fiber and the PO-based resin matrix is increased by the formation of the trans crystallized product as described above, the bending strength and the like are improved as described above, but the impact resistance is improved. It is possible that it will decrease. However, in the fiber-reinforced PO-based resin molded product of the present invention in which crystallized substances having a trans-crystal structure are present, such a decrease in impact strength is not observed, and very well-balanced mechanical properties are obtained.
【００２６】この理由は次の様に考えられる。即ち結晶
性ポリマーであるＰＯ系樹脂は、ガラス繊維が存在しな
い部分でも樹脂単独で球晶を形成するので、トランスク
リスタル晶出物と該球晶の部分で新たな界面が形成さ
れ、この部分が衝撃破壊を起こす時の亀裂の進行を分断
する作用を発揮すると共に、この様な系では、マトリッ
クス樹脂中の球晶とトランスクリスタルの間に生じた新
たな界面で、周囲のトランスクリスタル晶出物ごとガラ
ス繊維の引き抜けが起こって衝撃エネルギーを吸収し、
これらが相まって衝撃強度の向上に好結果をもたらして
いるものと考えられる。The reason for this is considered as follows. That is, since the PO-based resin, which is a crystalline polymer, forms spherulites by the resin alone even in the portion where glass fiber does not exist, a new interface is formed between the trans crystallized product and the spherulite, and this portion is In addition to exerting the effect of dividing the progress of cracks when impact fracture occurs, in such a system, a new interface formed between the spherulite and the trans crystal in the matrix resin creates a surrounding trans crystal crystallization product. Every glass fiber pulls out and absorbs impact energy,
It is considered that the combination of these results in favorable improvement in impact strength.
【００２７】ここで使用される酸変性ＰＯ系樹脂とは、
マレイン酸やフマル酸、アクリル酸などのα，β−エチ
レン性不飽和カルボン酸あるいはそれらの酸無水物によ
り酸変性したポリオレフィンであり、好ましい酸変性量
は、酸価で５〜１００ｍｇＫＯＨ／ｇ、より好ましくは
１０〜８０ｍｇＫＯＨ／ｇ、好ましい分子量は、平均分
子量で５，０００〜１００，０００、より好ましくは１
０，０００〜５０，０００の範囲のものである。また、
ガラス繊維集束体を開繊する際に、開繊ガラス繊維表面
に効率良く均一に付着させるため、平均粒子径が８μｍ
程度以下、より好ましくは１〜６μｍの範囲のものを使
用するのが好ましい。The acid-modified PO resin used here is
A polyolefin acid-modified with an α, β-ethylenically unsaturated carboxylic acid such as maleic acid, fumaric acid, or acrylic acid, or an acid anhydride thereof, and a preferable acid modification amount is 5 to 100 mgKOH / g in terms of acid value. The average molecular weight is preferably 5,000 to 100,000, more preferably 1 to 80 mgKOH / g.
It is in the range of 50,000 to 50,000. Also,
When the glass fiber bundle is opened, the average particle diameter is 8 μm so that the glass fiber bundle is efficiently and uniformly attached to the surface.
It is preferable to use a resin having a thickness of not more than about, more preferably 1 to 6 μm.
【００２８】上記酸変性ＰＯ系樹脂あるいはマトリック
スを構成するＰＯ系樹脂におけるポリオレフィンとして
は、ポリエチレン、ポリプロピレンあるいはエチレン−
プロピレン共重合体、更にはそれらのブレンド物やそれ
らに他のポリマーを少量配合したブレンド物等が挙げら
れるが、これらの中でも高結晶性のポリエチレンやポリ
プロピレンは、トランスクリスタル晶出物を最も生成し
易いので好ましい。The polyolefin in the acid-modified PO-based resin or the PO-based resin constituting the matrix is polyethylene, polypropylene or ethylene-
Examples include propylene copolymers, blends thereof, and blends obtained by blending a small amount of other polymers therein. Among them, highly crystalline polyethylene and polypropylene produce the most trans-crystal crystallization. It is preferable because it is easy.
【００２９】また、上記酸変性ＰＯ系樹脂の付着による
トランスクリスタル晶出促進効果を有効に発揮させる意
味から、該酸変性ＰＯ系樹脂の好ましい付着量は、ガラ
ス繊維重量に対する比率で０．０００１〜５０重量％、
より好ましくは０．１〜２０重量％の範囲、ガラス繊維
強化ＰＯ系樹脂組成物中に占める酸変性ＰＯ系樹脂の含
有量で０．００００１〜３０重量％、より好ましくは
０．０３〜８重量％の範囲である。Further, in order to effectively exert the trans-crystal crystallization accelerating effect by the adhesion of the acid-modified PO-based resin, the preferred adhesion amount of the acid-modified PO-based resin is 0.0001 to 0.001 to the glass fiber weight. 50% by weight,
The range is more preferably 0.1 to 20% by weight, the content of the acid-modified PO resin in the glass fiber reinforced PO resin composition is 0.00001 to 30% by weight, and more preferably 0.03 to 8% by weight. % Range.
【００３０】また、金属および／または金属化合物は、
前記酸変性ＰＯ系樹脂との共存によって前述の様なトラ
ンスクリスタルの晶出を一層促進させる効果を有してお
り、それらの具体例としては、カリウム、ナトリウム等
のアルカリ金属、カルシウム、マグネシウム等のアルカ
リ土類金属、アルミニウム等の金属あるいはそれらの金
属の水酸化物、酸化物、炭酸塩、塩化物、硝酸塩、硫酸
塩、カルボン酸塩、フェノラート等が例示されるが、そ
れらの中でも特に好ましいのはカルシウムやアルミニウ
ムなど及びそれらの化合物である。これらの好ましい使
用量は、ガラス繊維強化ＰＯ系樹脂組成物全量中に占め
る比率で０．０００１〜５重量％、より好ましくは０．
００１〜０．１重量％の範囲である。The metal and / or metal compound is
The coexistence with the acid-modified PO-based resin has the effect of further promoting the crystallization of the trans crystal as described above. Specific examples thereof include alkali metals such as potassium and sodium, calcium, magnesium and the like. Alkaline earth metals, metals such as aluminum or hydroxides, oxides, carbonates, chlorides, nitrates, sulfates, carboxylates, phenolates and the like of these metals are exemplified, and among them, particularly preferred Are calcium and aluminum and their compounds. The preferable amount of these used is 0.0001 to 5% by weight, more preferably 0.1% by weight in the total amount of the glass fiber reinforced PO resin composition.
It is in the range of 001 to 0.1% by weight.
【００３１】上記表面改質の対象となる強化用のガラス
繊維集束体は、細いフィラメントが多数集束されたもの
ほど、開繊されてＰＯ系樹脂マトリックス中へ分散され
た状態で均質で優れた強化効果を発揮すると共に、得ら
れる成形体は表面平滑性の高いものが得られるので好ま
しく、最終段階でのマトリックス樹脂中への均一分散性
や成形作業性等を総合的に考慮して最も好ましいのは、
直径が８〜２０μｍ程度のフィラメントを２００〜４０
００本程度、より好ましくは４００〜１２００本程度束
ねたものであり、繊維長さは最終成形品の要求特性によ
っても変わってくるので一律に規定することはできない
が、気流による開繊性や均質混合性等を考慮する１〜５
０ｍｍ程度、より好ましくは５〜２０ｍｍ程度のものを
使用することが望ましい。The glass fiber bundle for strengthening, which is the subject of the above surface modification, is homogeneous and excellent in the state that the finer filaments are bundled, the filaments are opened and dispersed in the PO resin matrix. In addition to exhibiting the effect, the obtained molded article is preferable because it has a high surface smoothness, and is most preferable in consideration of the uniform dispersibility in the matrix resin at the final stage and the molding workability. Is
200 to 40 filaments with a diameter of 8 to 20 μm
About 100 fibers, more preferably about 400 to 1200 fibers, are bundled, and the fiber length varies depending on the required characteristics of the final molded product, so it cannot be specified uniformly, but the openability and homogeneity due to air flow 1-5 considering mixing
It is desirable to use one having a diameter of about 0 mm, more preferably about 5 to 20 mm.
【００３２】尚本発明を実施するに当たっては、上記ガ
ラス繊維以外の強化用繊維として、炭素繊維、金属繊
維、セラミックス繊維、ＳｉＣウイスカー、Ｓ3 Ｎ4 ウ
イスカー等の無機繊維、あるいはポリエステル繊維、ポ
リアミド繊維、アクリル繊維、アラミド繊維等の有機合
成繊維、更には各種の天然繊維などを適量併用すること
も可能であり、また再生資源として回収される古紙の解
砕繊維を適量併用することによって軽量化やコスト低減
等を図ることも可能である。In carrying out the present invention, as reinforcing fibers other than the above-mentioned glass fibers, inorganic fibers such as carbon fibers, metal fibers, ceramic fibers, SiC whiskers, S 3 N 4 whiskers, etc., or polyester fibers, polyamide fibers are used. It is also possible to use an appropriate amount of organic synthetic fibers such as acrylic fiber and aramid fiber, as well as various kinds of natural fibers, and to reduce the weight by using an appropriate amount of crushed fibers of recycled paper recovered as recycled resources. It is also possible to reduce costs.
【００３３】気流中で混合する具体的な方法としては、
例えば図１に示す様な気流混合装置が使用される。即ち
この装置を用いた気流混合に当たっては、横向き円筒状
容器１の上部に設けられた複数のホッパー２ａ，２ｂか
ら、ガラス繊維集束体のチョップドストランドと酸変性
ＰＯ系樹脂粉末、更には必要に応じて金属および／また
は金属化合物を円筒状容器１内へ別々に若しくは同時に
供給し、該容器１の壁面に設けたノズル３から圧縮気体
（空気、あるいは圧縮された窒素ガスや不活性ガス、水
蒸気等）を吹き込んで混合し、チョップドストランドの
開繊と酸変性ＰＯ系樹脂粉末の混合、及び開繊されたガ
ラス繊維表面への該樹脂粉末の付着を並行して行なう。
尚、圧縮気体は図示しないフィルターを通って外部へ放
出される。酸変性ＰＯ系樹脂（更には金属および／また
は金属化合物）の付着された開繊ガラス繊維は、容器１
の適所に設けた排出口からバッチ的に取り出せばよい。
酸変性ＰＯ系樹脂をガラス繊維表面に溶融付着させる場
合は、加熱された圧縮気体を吹き込み、あるいは円筒状
容器１を任意の方法で加熱すればよい。As a concrete method of mixing in an air stream,
For example, an airflow mixing device as shown in FIG. 1 is used. That is, in the air flow mixing using this device, the chopped strands of the glass fiber bundles and the acid-modified PO-based resin powder, and further, if necessary, from the plurality of hoppers 2a and 2b provided in the upper portion of the horizontal cylindrical container 1 are used. Metal and / or metal compound are separately or simultaneously supplied into the cylindrical container 1, and compressed gas (air or compressed nitrogen gas, inert gas, steam, etc.) is supplied from a nozzle 3 provided on the wall surface of the container 1. ) Is blown in and mixed, the chopped strands are opened, the acid-modified PO-based resin powder is mixed, and the resin powder is attached to the opened glass fiber surface in parallel.
The compressed gas is discharged to the outside through a filter (not shown). The opened glass fiber to which the acid-modified PO-based resin (further, metal and / or metal compound) is attached is the container 1
It may be taken out in batches from the discharge port provided at the appropriate place.
When the acid-modified PO-based resin is melted and adhered to the surface of the glass fiber, heated compressed gas may be blown in or the cylindrical container 1 may be heated by an arbitrary method.
【００３４】また、ガラス繊維の長繊維ストランドをロ
ールに通す等によって予備開繊させながら、酸変性ＰＯ
系樹脂粉末や金属および／または金属化合物を散布する
ことによってこれらを予めガラス繊維ストランドに付着
させておき、これをカッターで適当な長さに切断しなが
ら気流混合装置内へ供給して開繊・混合・付着を行なう
ことも可能である。このとき、ガラス繊維表面への酸変
性ＰＯ系樹脂粉末の付着をより効率よく遂行するため、
ガラス繊維や酸変性ＰＯ系樹脂粉末等に電荷を与え、静
電気的に付着させることも有効である。While the long fiber strands of glass fiber are pre-opened by passing them through a roll, etc., acid-modified PO
These are attached to the glass fiber strands in advance by spraying the system resin powder and the metal and / or metal compound, and while cutting this into a suitable length with a cutter, it is fed into the air flow mixing device and opened. It is also possible to mix and attach. At this time, in order to more efficiently adhere the acid-modified PO-based resin powder to the glass fiber surface,
It is also effective to give an electric charge to the glass fiber, the acid-modified PO-based resin powder, or the like to electrostatically adhere them.
【００３５】マトリックス樹脂を構成するＰＯ系樹脂と
強化用ガラス繊維の配合比率も、用途や要求特性によっ
て変わってくるので一律に決めることはできないが、標
準的な比率として挙げるならば、繊維強化樹脂全体中に
占める比率でＰＯ系樹脂が４０〜９０重量％、より好ま
しくは６０〜７０重量％、ガラス繊維が１０〜６０重量
％、より好ましくは３０〜４０重量％の範囲である。The mixing ratio of the PO-based resin constituting the matrix resin and the reinforcing glass fiber cannot be uniformly determined because it varies depending on the application and required characteristics, but if it is mentioned as a standard ratio, the fiber-reinforced resin The PO resin is in the range of 40 to 90% by weight, more preferably 60 to 70% by weight, and the glass fiber is 10 to 60% by weight, more preferably 30 to 40% by weight.
【００３６】本発明における必須の構成成分は上記の通
りであるが、これらに加えて前記本発明の特長を損なわ
ない範囲で他の合成樹脂や無機質フィラー、帯電防止
剤、紫外線吸収剤、可塑剤、着色剤、顔料、染料等を適
量含有させることも勿論可能である。The essential constituents in the present invention are as described above, but in addition to these, other synthetic resins, inorganic fillers, antistatic agents, ultraviolet absorbers, plasticizers are also used within the range not impairing the features of the present invention. Of course, it is also possible to include an appropriate amount of a colorant, a pigment, a dye and the like.
【００３７】また前述の様な構成素材を用いた混練法や
成形法等にも格別の制限はなく、従来のガラス繊維強化
樹脂の製法や成形法に準じて実施すればよい。また本発
明における繊維強化樹脂組成物は、前述の如く表面処理
されたガラス繊維とＰＯ系樹脂等を含むバルキー状の混
合物として提供されるものであるが、該組成物を圧縮し
その表面を加熱して表層部のＰＯ系樹脂を溶融させるこ
とによって皮張りさせた状態の予備成形体、或はこれら
をペレット状や棒状等に加工したもの、あるいは２次成
形加工用として板状等に成形したもの等が包含され、押
出成形、射出成形、射出圧縮成形、圧縮成形等に使用す
ることができる。There is no particular limitation on the kneading method or molding method using the constituent materials as described above, and the method may be carried out in accordance with the conventional glass fiber reinforced resin manufacturing method or molding method. The fiber-reinforced resin composition in the present invention is provided as a bulky mixture containing the glass fiber surface-treated as described above and a PO-based resin. The composition is compressed and the surface is heated. Then, the preform in the state of being covered by melting the PO-based resin in the surface layer is formed, or these are processed into pellets or rods, or formed into a plate or the like for secondary molding. It can be used for extrusion molding, injection molding, injection compression molding, compression molding and the like.
【００３８】[0038]
【実施例】次に本発明の実施例を示すが、本発明はもと
より下記実施例によって制限を受けるものではなく、前
後記の趣旨に適合し得る範囲で適当に変更を加えて実施
することも勿論可能であり、それらはいずれも本発明の
技術的範囲に含まれる。EXAMPLES Next, examples of the present invention will be shown, but the present invention is not limited by the following examples, and may be carried out with appropriate modifications within a range compatible with the gist of the preceding and following description. Of course, it is possible, and all of them are included in the technical scope of the present invention.
【００３９】実施例１ ガラス繊維として、アミノシランコーティング処理され
た直径１３μｍ、長さ１３ｍｍ、１２００フィラメント
が１束からなるチョップドファイバーを使用し、このチ
ョップドファイバーを図１に示した様なエアミキシング
法（混合条件：圧縮空気圧：２ｋｇ／ｃｍ2 ）により開
繊させながら、平均分子量：２０，０００、平均粒径：
３０μｍ、酸価：７０ｍｇＫＯＨ／ｇの酸変性ポリプロ
ピレンを添加して混合し、開繊されたガラス繊維表面に
酸変性ポリプロピレン粉末０．３重量％を付着させた。Example 1 As the glass fiber, a chopped fiber having a diameter of 13 μm, a length of 13 mm, and a bundle of 1200 filaments, which was treated with an aminosilane, was used, and the chopped fiber was mixed by an air mixing method as shown in FIG. Mixing conditions: compressed air pressure: 2 kg / cm 2 ) While opening the fibers, average molecular weight: 20,000, average particle size:
An acid-modified polypropylene of 30 μm and an acid value of 70 mgKOH / g was added and mixed, and 0.3% by weight of the acid-modified polypropylene powder was adhered to the surface of the opened glass fiber.
【００４０】この表面処理された開繊ガラス繊維と、高
結晶性ポリプロピレン粉末（平均粒径：５００μｍ）と
を、重量比率で３０：７０の比率で均一に混合した後、
加熱プレス装置を用いて加熱加圧し、３０ｃｍL ×３０
ｃｍW ×０．４ｃｍT の板状体に成形し、該成形体の
Ｘ，Ｙ軸方向から夫々１０本づつ試験片を切り出し、３
点曲げ試験（ＪＩＳ Ｋ ７０５５）およびノッチ付き
アイゾット衝撃試験（ＪＩＳ Ｋ ７１１０−８４）を
行ない、その物性を調べた。After the surface-treated open glass fiber and the highly crystalline polypropylene powder (average particle size: 500 μm) were uniformly mixed in a weight ratio of 30:70,
Heated and pressurized using a heating press device, 30 cm L x 30
cm W × 0.4 cm T , formed into a plate-like body, and cut out 10 test pieces from each of the X- and Y-axis directions of the formed body, and 3
A point bending test (JIS K 7055) and a notched Izod impact test (JIS K 7110-84) were performed to examine the physical properties thereof.
【００４１】比較例１ ガラス繊維（同前）が全体の３０重量部となる様に、前
述の様な表面処理を行なうことなくそのまま使用し、こ
れを、実施例１で用いたのと同じ酸変性ポリプロピレン
１重量％を予め練り込んだ後に粉砕した高結晶性ポリプ
ロピレン粉末７０重量部とエアミキシング法によって均
一に混練し、以下、上記実施例１と同様にして加熱加圧
成形および強度評価試験を行なった。Comparative Example 1 The glass fiber (same as above) was used as it was without the surface treatment as described above so that the total amount thereof was 30 parts by weight, and the same acid as used in Example 1 was used. 70 parts by weight of highly crystalline polypropylene powder pulverized with 1% by weight of modified polypropylene and then pulverized was uniformly kneaded by an air mixing method, and thereafter, heat and pressure molding and a strength evaluation test were performed in the same manner as in Example 1 above. I did.
【００４２】実施例２ ガラス繊維として、アミノシランコーティング処理され
た直径１３μｍ、長さ１３ｍｍ、１２００フィラメント
が１束からなるチョップドファイバーを使用し、このチ
ョップドファイバーを上記実施例１と同様にして開繊
（但し、混合用の空気として２００℃の熱風を使用し
た）させながら、実施例１で用いたのと同じ酸変性ポリ
プロピレン粉末（平均分子量：２０，０００、平均粒
径：３０μｍ、酸価：７０ｍｇＫＯＨ／ｇ）を添加して
混合し、開繊されたガラス繊維表面に酸変性ポリプロピ
レン粉末０．３重量％を溶融付着させた。この表面処理
された開繊ガラス繊維と高結晶性ポリプロピレン粉末を
実施例１と全く同様の配合比率および方法で均一に混合
した後、同様にして加熱プレス成形、更に物性試験を行
なった。Example 2 As the glass fiber, a chopped fiber having a diameter of 13 μm, a length of 13 mm and a bundle of 1200 filaments, which was treated with an aminosilane, was used. The chopped fiber was opened in the same manner as in Example 1 above. However, the same acid-modified polypropylene powder (average molecular weight: 20,000, average particle size: 30 μm, acid value: 70 mgKOH /) used in Example 1 was used while hot air of 200 ° C. was used as mixing air). g) was added and mixed, and 0.3% by weight of acid-modified polypropylene powder was melted and adhered to the surface of the opened glass fiber. The surface-treated open glass fiber and the highly crystalline polypropylene powder were uniformly mixed in the same mixing ratio and method as in Example 1, followed by hot press molding and further physical property test.
【００４３】実施例３ ガラス繊維として、アミノシランコーティング処理され
た直径１３μｍ、長さ１３ｍｍ、１２００フィラメント
が１束からなるチョップドファイバーを使用し、このチ
ョップドファイバーを上記実施例１と同様にして開繊
（但し、混合用の空気として２００℃の熱風を使用し
た）させながら、実施例１で用いたのと同じ酸変性ポリ
プロピレン粉末（平均分子量：２０，０００、平均粒
径：３０μｍ、酸価：７０ｍｇＫＯＨ／ｇ）を添加して
混合し、開繊されたガラス繊維表面に酸変性ポリプロピ
レン粉末０．３重量％を溶融付着させた。この表面処理
された開繊ガラス繊維と高結晶性ポリプロピレンを重量
比率で５０：５０の比率で均一に混合し、以下実施例１
と全く同様にして加熱プレス成形、更に物性試験を行な
った。Example 3 As the glass fiber, a chopped fiber having a diameter of 13 μm, a length of 13 mm and a bundle of 1200 filaments, which was treated with an aminosilane, was used. However, the same acid-modified polypropylene powder (average molecular weight: 20,000, average particle size: 30 μm, acid value: 70 mgKOH /) used in Example 1 was used while hot air of 200 ° C. was used as mixing air). g) was added and mixed, and 0.3% by weight of acid-modified polypropylene powder was melted and adhered to the surface of the opened glass fiber. The surface-treated open glass fiber and the highly crystalline polypropylene were uniformly mixed at a weight ratio of 50:50, and
The heat press molding and the physical property test were performed in exactly the same manner as in.
【００４４】実施例４ ガラス繊維として、アミノシランコーティング処理され
た直径１３μｍ、長さ１３ｍｍ、１２００フィラメント
が１束からなるチョップドファイバー１００ｇを、実施
例２と同様にしてエアミキシング法により開繊させなが
ら、酸変性ポリプロピレン粉末（同前）を添加して混合
し、開繊されたガラス繊維表面に酸変性ポリプロピレン
粉末０．３重量％を溶融付着させた後、これにカルシウ
ムを０．００５〜０．０１重量％含有する高結晶性ポリ
プロピレン粉末を重量比率で３０：７０の比率で均一に
混合し、以下実施例１と全く同様にして加熱プレス成
形、更に物性試験を行なった。Example 4 As glass fiber, 100 g of chopped fiber having a diameter of 13 μm, a length of 13 mm and a bundle of 1200 filaments, which was treated with aminosilane, was opened by the air mixing method in the same manner as in Example 2, Acid-modified polypropylene powder (same as above) was added and mixed, and 0.3% by weight of acid-modified polypropylene powder was melted and adhered to the surface of the opened glass fiber, and calcium was added thereto in an amount of 0.005-0.01. The highly crystalline polypropylene powder contained in an amount of 30% by weight was uniformly mixed in a weight ratio of 30:70, and hot press molding was performed in the same manner as in Example 1 and a physical property test was performed.
【００４５】物性試験の結果は表１に一括して示す通り
であり、本発明の要件を満足する実施例１〜４と比較例
１を比較すると、曲げ強度および衝撃強度のいずれにお
いても本発明実施例の方が優れており、特に本発明の実
施例３は衝撃強度において非常に優れたものであること
が分かる。尚、図２は、上記実施例３で得た試験片の断
面を顕微鏡によって観察し、マトリックス樹脂とガラス
繊維との界面の状況を観察した結果を示したものであ
り、この写真に見られる様に、界面にはトランスクリス
タル構造の晶出物の生成が認められ、これらが曲げ強度
と衝撃特性に優れた影響を及ぼしていることが分かる。The results of the physical property tests are collectively shown in Table 1. Comparing Examples 1 to 4 satisfying the requirements of the present invention with Comparative Example 1, the present invention is obtained in both bending strength and impact strength. It can be seen that the example is superior, and in particular, the example 3 of the present invention is very excellent in impact strength. Incidentally, FIG. 2 shows the results of observing the cross section of the test piece obtained in Example 3 above with a microscope and observing the condition of the interface between the matrix resin and the glass fiber, as shown in this photograph. In addition, the formation of trans-crystallized crystallized substances was observed at the interface, and it can be seen that these have an excellent effect on the bending strength and impact properties.
【００４６】[0046]
【表１】 [Table 1]
【００４７】[0047]
【発明の効果】本発明は以上の様に構成されており、曲
げ強度や引張強度をあまり低下させることなく耐衝撃強
度を高め、バランスのとれた強度特性を発揮し得る様な
ガラス繊維強化ＰＯ系樹脂成形性を与える組成物および
高性能の成形体を容易且つ比較的安価に提供し得ること
になった。EFFECT OF THE INVENTION The present invention is constituted as described above, and glass fiber reinforced PO capable of exhibiting balanced strength characteristics while enhancing impact strength without significantly lowering bending strength and tensile strength. It has become possible to easily and relatively inexpensively provide a composition giving a resin moldability and a high-performance molded article.
【図１】本発明で採用される気流中での開繊と混合およ
び酸変性ＰＯ系樹脂や核剤の混合付着法を例示する概略
説明図である。FIG. 1 is a schematic explanatory view illustrating a method of opening and mixing in an air stream and a method of mixing and adhering an acid-modified PO-based resin and a nucleating agent, which are adopted in the present invention.
【図２】実施例３で得た本発明成形体におけるトランス
クリスタルの晶出状況を示す図面代用顕微鏡写真であ
る。2 is a drawing-substitute micrograph showing the crystallization state of trans crystals in the molded product of the present invention obtained in Example 3. FIG.
フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 // Ｂ２９Ｋ 23:00 105:08 Ｃ０８Ｌ 23:00 (72)発明者 竹田 隆子 兵庫県神戸市西区高塚台１丁目５番５号 株式会社神戸製鋼所神戸総合技術研究所内 (72)発明者 大塚 剛樹 兵庫県神戸市西区高塚台１丁目５番５号 株式会社神戸製鋼所神戸総合技術研究所内 (72)発明者 安西 美佳 兵庫県神戸市西区高塚台１丁目５番５号 株式会社神戸製鋼所神戸総合技術研究所内Continuation of front page (51) Int.Cl. 6 Identification number Reference number within the agency FI Technical indication location // B29K 23:00 105: 08 C08L 23:00 (72) Inventor Takako Takeda 1 Takatsukadai, Nishi-ku, Kobe-shi, Hyogo 5-5-5 Kobe Steel Co., Ltd., Kobe Research Institute (72) Inventor Takeki Otsuka 1-5-5 Takatsukadai, Nishi-ku, Kobe-shi, Hyogo Kobe Steel Co., Ltd. Kobe Research Laboratory (72) Invention Mika Anzai 1-5-5 Takatsukadai, Nishi-ku, Kobe-shi, Hyogo Prefecture Kobe Steel Works, Ltd. Kobe Research Institute
Claims (9)
ストランドと酸変性されたポリオレフィン系樹脂粉末を
気流中で混合することにより、強化用ガラス繊維の集束
体を開繊すると共に開繊された強化用ガラス繊維の表面
に酸変性されたポリオレフィン系樹脂を付着せしめ、該
樹脂が表面に付着した強化用ガラス繊維をポリオレフィ
ン系樹脂粉末と均一に混合することを特徴とするガラス
繊維強化ポリオレフィン系樹脂組成物の製法。1. A chopped strand of a reinforcing glass fiber bundle and an acid-modified polyolefin-based resin powder are mixed in an air stream to open the reinforcing glass fiber bundle and to open the fiber. Glass fiber reinforced polyolefin resin composition characterized in that an acid-modified polyolefin resin is adhered to the surface of the glass fiber for use and the reinforcing glass fiber having the resin adhered to the surface is uniformly mixed with the polyolefin resin powder. How to make things.
開繊ガラス繊維表面に酸変性されたポリオレフィン系樹
脂を溶融付着させる請求項１に記載のガラス繊維強化ポ
リオレフィン系樹脂組成物の製法。2. Mixing in an air stream under heating conditions,
The method for producing a glass fiber-reinforced polyolefin resin composition according to claim 1, wherein the acid-modified polyolefin resin is melt-adhered to the surface of the opened glass fiber.
ストランドと前記酸変性されたポリオレフィン系樹脂粉
末を気流中で混合した後、該混合物を加熱することによ
り、開繊ガラス繊維の表面に酸変性されたポリオレフィ
ン系樹脂を溶融付着させる請求項１記載のガラス繊維強
化ポリオレフィン系樹脂組成物の製法。3. A chopped strand of a reinforcing glass fiber bundle and the acid-modified polyolefin resin powder are mixed in an air stream, and then the mixture is heated to acid-modified the surface of the opened glass fiber. The method for producing a glass fiber reinforced polyolefin resin composition according to claim 1, wherein the prepared polyolefin resin is melted and adhered.
請求項１〜３のいずれかに記載の方法により酸変性され
たポリオレフィン系樹脂を付着せしめると共に、あるい
は付着せしめた後に、更に金属および／または金属化合
物を付着せしめ、これをポリオレフィン系樹脂粉末と均
一に混合することを特徴とするガラス繊維強化ポリオレ
フィン系樹脂組成物の製法。4. On the surface of the opened reinforcing glass fiber,
A polyolefin-based resin acid-modified by the method according to any one of claims 1 to 3 is adhered, or after being adhered, a metal and / or a metal compound is further adhered, which is uniformly mixed with the polyolefin-based resin powder. A method for producing a glass fiber-reinforced polyolefin-based resin composition, which comprises mixing with
請求項１〜３のいずれかに記載の方法によりポリオレフ
ィン系樹脂を付着させた後、金属および／または金属化
合物を含むポリオレフィン系樹脂粉末と均一に混合する
ことを特徴とするガラス繊維強化ポリオレフィン系樹脂
組成物の製法。5. The surface of the opened reinforcing glass fiber,
A glass fiber reinforced polyolefin resin, characterized in that the polyolefin resin is adhered by the method according to any one of claims 1 to 3 and then uniformly mixed with a polyolefin resin powder containing a metal and / or a metal compound. Method of making the composition.
よって得られる、表面に酸変性されたポリオレフィン系
樹脂が付着したガラス繊維と、ポリオレフィン系樹脂粉
末とが均一に混合されたものであるガラス繊維強化ポリ
オレフィン系樹脂組成物。6. A glass fiber obtained by the method according to any one of claims 1 to 3 in which acid-modified polyolefin resin is adhered to the surface of the glass fiber, and the polyolefin resin powder is uniformly mixed. A certain glass fiber reinforced polyolefin resin composition.
る、表面に酸変性されたポリオレフィン系樹脂と、金属
および／または金属化合物が付着したガラス繊維と、ポ
リオレフィン系樹脂粉末とが均一に混合されたものであ
るガラス繊維強化ポリオレフィン系樹脂組成物。7. A surface-modified polyolefin resin obtained by the method according to claim 4, glass fibers having a metal and / or a metal compound attached thereto, and a polyolefin resin powder are uniformly mixed. A glass fiber reinforced polyolefin-based resin composition which is a product.
る、表面に酸変性されたポリオレフィン系樹脂が付着し
たガラス繊維と、金属および／または金属化合物を含む
ポリオレフィン系樹脂粉末とが均一に混合されたもので
あるガラス繊維強化ポリオレフィン系樹脂組成物。8. The glass fiber obtained by the method according to claim 5 and having an acid-modified polyolefin resin attached to the surface thereof, and a polyolefin resin powder containing a metal and / or a metal compound are uniformly mixed. A glass fiber reinforced polyolefin-based resin composition which is a product.
成物を加熱加圧成形してなり、強化用ガラス繊維とポリ
オレフィン系樹脂マトリックスとの界面にトランスクリ
スタル構造の晶出物が存在することを特徴とするガラス
繊維強化ポリオレフィン系樹脂成形体。9. A resin composition according to any one of claims 6 to 8 is formed by heating under pressure, and a crystallized product having a trans crystal structure is present at the interface between the reinforcing glass fiber and the polyolefin resin matrix. A glass fiber-reinforced polyolefin-based resin molded article characterized by being.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6219223A JPH0880526A (en) | 1994-09-13 | 1994-09-13 | Glass fiber reinforced polyolefin resin composition, manufacture thereof, and molded body formed thereby |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6219223A JPH0880526A (en) | 1994-09-13 | 1994-09-13 | Glass fiber reinforced polyolefin resin composition, manufacture thereof, and molded body formed thereby |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0880526A true JPH0880526A (en) | 1996-03-26 |
Family
ID=16732141
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6219223A Withdrawn JPH0880526A (en) | 1994-09-13 | 1994-09-13 | Glass fiber reinforced polyolefin resin composition, manufacture thereof, and molded body formed thereby |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0880526A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014177026A (en) * | 2013-03-14 | 2014-09-25 | Honda Motor Co Ltd | Joint product of heterogeneous material, and manufacturing method thereof |
| CN106633391A (en) * | 2016-11-29 | 2017-05-10 | 华东理工大学 | Inducing method of transcrystalline structure on polypropylene/glass fiber interface |
-
1994
- 1994-09-13 JP JP6219223A patent/JPH0880526A/en not_active Withdrawn
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014177026A (en) * | 2013-03-14 | 2014-09-25 | Honda Motor Co Ltd | Joint product of heterogeneous material, and manufacturing method thereof |
| US9403344B2 (en) | 2013-03-14 | 2016-08-02 | Honda Motor Co., Ltd. | Bonded body made from different materials and method for producing the same |
| CN106633391A (en) * | 2016-11-29 | 2017-05-10 | 华东理工大学 | Inducing method of transcrystalline structure on polypropylene/glass fiber interface |
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| A300 | Withdrawal of application because of no request for examination |
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