JPS62295940A - Polypropylene molding material - Google Patents
Polypropylene molding materialInfo
- Publication number
- JPS62295940A JPS62295940A JP14735087A JP14735087A JPS62295940A JP S62295940 A JPS62295940 A JP S62295940A JP 14735087 A JP14735087 A JP 14735087A JP 14735087 A JP14735087 A JP 14735087A JP S62295940 A JPS62295940 A JP S62295940A
- Authority
- JP
- Japan
- Prior art keywords
- glass fiber
- component
- polypropylene
- mixture
- molding material
- 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.)
- Granted
Links
- 239000012778 molding material Substances 0.000 title claims abstract description 10
- -1 Polypropylene Polymers 0.000 title claims description 34
- 239000004743 Polypropylene Substances 0.000 title claims description 34
- 229920001155 polypropylene Polymers 0.000 title claims description 34
- 239000003365 glass fiber Substances 0.000 claims abstract description 25
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 12
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000007822 coupling agent Substances 0.000 claims abstract description 9
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003822 epoxy resin Substances 0.000 claims abstract description 5
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 5
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000003795 chemical substances by application Substances 0.000 abstract description 10
- 230000000704 physical effect Effects 0.000 abstract description 9
- 150000002978 peroxides Chemical class 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 4
- 230000003014 reinforcing effect Effects 0.000 description 4
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000004513 sizing Methods 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- MASNVFNHVJIXLL-UHFFFAOYSA-N ethenyl(ethoxy)silicon Chemical compound CCO[Si]C=C MASNVFNHVJIXLL-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 229920001384 propylene homopolymer Polymers 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
３、発明の詳細な説明
本発明は優れた物性を有するガラス繊維強化ポリプロピ
レン成形材料に関する。Detailed Description of the Invention 3. Detailed Description of the Invention The present invention relates to a glass fiber reinforced polypropylene molding material having excellent physical properties.
一般にポリプロピレンは優れた物理的、化学的特性を有
し、汎用の成形材料として広く用いられている。しかし
ながらその耐熱性、剛性の改良を主目的としてガラス繊
維などの補強材で強化する場合、他の熱可塑性樹脂１例
えばナイロン、ポリカーボネート、スチレン系樹脂等に
比較して補強効果が小さく単純に混合するだけでは実用
上満足すべき複合材料は得られない。Generally, polypropylene has excellent physical and chemical properties and is widely used as a general-purpose molding material. However, when reinforcing it with a reinforcing material such as glass fiber with the main purpose of improving its heat resistance and rigidity, it has a small reinforcing effect compared to other thermoplastic resins such as nylon, polycarbonate, and styrene resins, so it is difficult to mix easily. A practically satisfactory composite material cannot be obtained by using only this method.
これは基本的にはポリプロピレンが反応性の官能基を有
しておらずガラス繊維との接着性が悪いことに基因して
いるが、この欠点を補うためシラン系のカップリング剤
などを用いてガラス繊維の表面処理をおこなうことは通
常なされており、ある程度の効果は得られているが、満
足すべき結果は得られていない。This is basically due to the fact that polypropylene does not have reactive functional groups and has poor adhesion to glass fibers, but to compensate for this drawback, silane-based coupling agents are used. Surface treatment of glass fibers is commonly performed, and although some effects have been obtained, satisfactory results have not been obtained.
また、シラン系カップリング剤でガラス繊維の表面処理
を行いそのカップリング剤と反応性の官能基を有し、か
つポリプロピレンとの相溶性に優れた適当な化合物を第
三成分として添加する方法もあり、実際におこなわれて
いる例もあるか、この場合も又充分満足すべき結果は得
られていない。Another method is to surface-treat the glass fiber with a silane coupling agent and add a suitable compound as a third component that has a functional group reactive with the coupling agent and is highly compatible with polypropylene. There are some examples where this has actually been done, but in this case too, fully satisfactory results have not been obtained.
又、別な方法としてアクリル酸、無水マレイン酸に代表
される不飽和カルボン酸をポリプロピレンと共重合させ
たり、あるいはグラフト重合させた変性ポリプロピレン
を用いろこトモ報告されており、かなりの効果をあげて
はいるが。In addition, it has been reported that another method is to copolymerize unsaturated carboxylic acids such as acrylic acid and maleic anhydride with polypropylene, or to use modified polypropylene obtained by graft polymerization. Although it is.
いまだ充分とはいいがたい。しかしながら、この方法に
よればカルボキシル基とガラス繊維の処理剤であるシラ
ン系カップリング剤との間に強固な化学結合が形成され
２ これによりポリプロピレンとガラス繊維の間番こ優
れた接着性があられれ、変性ポリプロピレンを使用した
系では。It's hard to say that it's still sufficient. However, according to this method, a strong chemical bond is formed between the carboxyl group and the silane coupling agent used as a treatment agent for glass fiber.2 This results in excellent adhesion between the polypropylene and the glass fiber. However, in systems using modified polypropylene.
シラン系カップリング剤のみ使用した系とか。A system that uses only a silane coupling agent.
第三成分を添加した系よりは、はるカリこ耐熱性。Much more heat resistant than systems with a third component added.
機械的強度の向上がみられるが、その効果とともに変性
ポリプロピレンの使用は種々の問題を発生させた。特に
変性ポリプロピレンはベース甜脂であるポリプロピレン
に比較して、はるかに吸湿性であるため、押出加工時に
発泡等の問題を発生させて、操業の安定性を悪くシ、又
物性面においても発泡にともない気泡を含むことからガ
ラス繊維とマｌ−’Ｊフックス脂の界面にボイドを発生
させること゛にもなり、変性ポリプロピレンを用いて接
着性を向上させた効果も結果的には充分にあられれない
という場合が多かった。Although the mechanical strength has been improved, along with this effect, the use of modified polypropylene has also caused various problems. In particular, modified polypropylene is much more hygroscopic than polypropylene, which is the base sugar, so it can cause problems such as foaming during extrusion processing, worsening operational stability, and also has poor foaming properties. The inclusion of air bubbles also creates voids at the interface between the glass fiber and the Maru-'J Fuchs resin, and the effect of improving adhesion using modified polypropylene may not be fully realized as a result. In many cases, there was no.
本発明はポリプロピレンをガラス繊維にて補強する場合
に変性ポリプロピレンを用い、かつ前述した如き問題も
解消し、従来のものに比較して物性面で飛躍的に向上し
たガラス繊維強化ポリプロピレン成形材料に関する。The present invention relates to a glass fiber-reinforced polypropylene molding material that uses modified polypropylene when reinforcing polypropylene with glass fibers, solves the above-mentioned problems, and has dramatically improved physical properties compared to conventional molding materials.
本発明はポリプロピレン（９）８９〜５７ ｗｔ％およ
ＣＦｊｆラス繊維に対して０．０２〜０．２ ＰＨＲの
アミノシラン系カップリング剤および０．２〜１．２
ＰＨＲのエポキシ樹脂で処理したガラス繊維ＩＢ）１１
〜４３ｗｔ％からなる混合物（Ａ十Ｂ）に対して。The present invention uses an aminosilane coupling agent of 0.02-0.2 PHR and 0.2-1.2 PHR for polypropylene (9) 89-57 wt% and CFJF lath fiber.
Glass fiber treated with PHR epoxy resin IB) 11
For a mixture (A+B) consisting of ~43 wt%.
ガラス繊維■に対してのアクリル酸又は無水マレイン酸
の比率が０．０１〜０．０６の範囲になるようにアクリ
ル酸又は無水マレイン酸を含む変性ポリプロピレン０を
添加した混合物（Ａ＋Ｂ＋Ｃ）をベント型押出機で減圧
度５００ｗＨｇ以上の減圧状態で押出加工して得られる
強じんなガラス繊維強化ポリプロピレン成形材料に関す
るものであり、具体的な検討結果については実施例に示
す。A mixture (A+B+C) in which modified polypropylene containing acrylic acid or maleic anhydride (0) was added so that the ratio of acrylic acid or maleic anhydride to glass fiber (2) was in the range of 0.01 to 0.06 was made into a vent type. The present invention relates to a strong glass fiber-reinforced polypropylene molding material obtained by extrusion processing using an extruder under reduced pressure of 500 wHg or more, and specific study results are shown in Examples.
本発明に用いられるポリプロピレンは一般的にポリプロ
ピレンの名称でいわれる結晶性ポリプロピレンのことで
あり、プロピレンの単独重合体およびプロピレンの共重
合体中の含有率が１５ｗｔ％以下の他のα−オレフィン
、例工ばエチレンとの本質的に結晶性である共重合体を
意味するものである。又、ガラス繊維の処理剤としては
カップリング剤としてアミノシランを０．０２〜０．２
ＰＨＲ，集束剤として０．２〜１．２ ＰＨＲのエポ
キシ樹脂を添加したものがよく、カップリング剤として
は他にビニルンラン、アクリル７ラン、エポキシシラン
等又、集束剤としては酸ビ等を二ついて検討をおこなっ
たが、上述した処理剤を用いる場合に並びうるような結
果は得られなかった。又、添加量についてはカップリン
グ剤の場合はガラス繊維に対して０．０２ ＰＨＲ以上
、好ましくは０．０４ ＰＨＲ以上がよく、上限は０、
２ ＰＨＲまでが実用的であり、それ以上添加しても機
械的物性、耐熱性等の物性面で向上はみられない。又、
集束剤の場合は０．２ ＰＨＲ以上。The polypropylene used in the present invention is a crystalline polypropylene generally referred to as polypropylene, and other α-olefins with a content of 15 wt% or less in propylene homopolymers and propylene copolymers, For example, an essentially crystalline copolymer with ethylene is meant. In addition, as a treatment agent for glass fibers, aminosilane is used as a coupling agent at 0.02 to 0.2
It is best to add an epoxy resin with a PHR of 0.2 to 1.2 PHR as a sizing agent, and as a coupling agent, vinyl run, acrylic 7 run, epoxy silane, etc., and as a sizing agent, vinyl oxide, etc. However, no results were obtained that would be comparable to those obtained when using the above-mentioned processing agent. In addition, in the case of a coupling agent, the amount to be added is preferably 0.02 PHR or more, preferably 0.04 PHR or more, and the upper limit is 0.
Up to 2 PHR is practical, and adding more than that will not improve physical properties such as mechanical properties and heat resistance. or,
0.2 PHR or higher for sizing agents.
好ましくは０．３ ＰＨＲ以上がよく上限は１．２ Ｐ
ＨＲまでが実用的であり、それ以上添加しても物性面で
の向上はあまりみられず、逆に熱安定性の点で着色等の
問題が発生してくる。又、混合物中のガラス繊維濃度は
ガラス繊維の補強効果が顕著になる１１ｗｔ％以上４３
ｗｔ％までが実際的であり、それ以上になると物性面で
のバランスが悪くなり、製造面でも難しくなる。Preferably 0.3 PHR or more, and the upper limit is 1.2 PHR
Up to HR is practical, and adding more than that will not improve much in terms of physical properties, and on the contrary, problems such as coloring will occur in terms of thermal stability. In addition, the glass fiber concentration in the mixture is 11 wt% or more, at which the reinforcing effect of glass fiber becomes noticeable43.
Up to wt% is practical, and if it exceeds that, the balance in terms of physical properties will be poor and manufacturing will also become difficult.
又２本発明に用いられる変性ポリプロピレンは所定量の
ポリプロピレンに無水マレイン酸又はアクリル酸を有機
過酸化物ととも番こ添加し。The modified polypropylene used in the present invention is prepared by adding maleic anhydride or acrylic acid to a predetermined amount of polypropylene along with an organic peroxide.
一般に用いられる押出機中で溶融混練し、製造される。It is produced by melt-kneading in a commonly used extruder.
変性ポリプロピレン中の無水マレイン酸又はアクリル酸
の濃度は任意でよいが変性ボリプロピレンの熱安定性、
グラフト率等から２，０〜６．０ｗｔ％ぐらいが適当で
あり、又混合物中（７） 無水−ｖレイン酸又はアクリ
ル酸の濃度は混合物中のガラス繊維濃度（処理剤の量）
により決定され、ガラス繊維に対して前述した処理剤濃
度であればガラス繊維とアクリル酸又は無水マレイン酸
の比率が０．０１〜０．０６が適当であり。The concentration of maleic anhydride or acrylic acid in the modified polypropylene may be arbitrary, but the thermal stability of the modified polypropylene
Approximately 2.0 to 6.0 wt% is appropriate based on the graft ratio, etc., and the concentration of (7) anhydrous leic acid or acrylic acid in the mixture is determined by the glass fiber concentration (amount of treatment agent) in the mixture.
If the above-mentioned concentration of the treatment agent is determined for the glass fiber, the ratio of glass fiber to acrylic acid or maleic anhydride is suitably 0.01 to 0.06.
０、Ｏ１以下では変性効果が不充分であり、 ０．０６
以上であれば特に熱安定性の点で実用上問題が発生する
。If it is less than 0, O1, the denaturing effect is insufficient, and 0.06
If it is more than that, a practical problem will occur especially in terms of thermal stability.
又１本発明では前述したポリプロピレン、ガラス繊維、
変性ポリプロピレンを混合する場合にベント型押出機を
用いてベント部分より真空ポンプ等の設備にて減圧状態
で押出加工し、製品のＶＭ（揮発分）を０．１ｗｔ％以
下にすることを特徴としている。変性ポリプロピレンは
吸湿性であるため減圧ではない一般の条件（大気解放下
）で押出加工をおこなうと成形品が発泡し。In addition, in the present invention, the above-mentioned polypropylene, glass fiber,
When mixing modified polypropylene, a vented extruder is used to extrude from the vent part under reduced pressure with equipment such as a vacuum pump, and the VM (volatile content) of the product is reduced to 0.1 wt% or less. There is. Modified polypropylene is hygroscopic, so if it is extruded under normal conditions (open to the atmosphere) without reduced pressure, the molded product will foam.
操業の安定性を悪くシ、物性面でもマトリックスポリマ
ーとガラス繊維の接着状態を不良にするため１期πした
程の効果力そ得られない。そのため従来までは変性ポリ
プロピレンの予備乾燥等がおこなわれてきたが、予備乾
燥では表面付着水分を若干取り除くという程度の効果し
かなく、はなはだ不充分である。The stability of operation is poor, and in terms of physical properties, the adhesion between the matrix polymer and the glass fibers is poor, so it is not as effective as the first stage. For this reason, the modified polypropylene has heretofore been subjected to pre-drying, but pre-drying only has the effect of slightly removing moisture adhering to the surface and is extremely insufficient.
又、ＶＭ（揮発分）については実施例にも示すが、０．
１ｗｔ％以下にすることが必要であり、減圧状態で加工
すればある程度の物性を有するものは得られるが、０．
１ｗｔ％以上のＶＭ（揮発分）を含んでおれば満足すべ
き物性のものは得られない。Further, as for VM (volatile content), as shown in the examples, 0.
It is necessary to reduce the amount to 1 wt% or less, and if processed under reduced pressure, products with certain physical properties can be obtained, but 0.
If it contains 1 wt% or more of VM (volatile matter), satisfactory physical properties cannot be obtained.
なお、ＶＭ（揮発分）は試料的１０ｇｒを１０５℃恒温
乾燥器内で５時間加熱乾燥した後の揮発分を重量％であ
られしたものを意味する。In addition, VM (volatile content) means the volatile content obtained by heating and drying a sample of 10 gr in a constant temperature dryer at 105° C. for 5 hours, expressed as weight percent.
又１本発明の成形材料に一般的な各種の酸化防止剤、紫
外線吸収剤等の安定剤および一般的な顔料、無機充填剤
等の添加は任意になし得る。Further, various antioxidants, stabilizers such as ultraviolet absorbers, general pigments, inorganic fillers, etc. which are commonly used in the molding material of the present invention may be optionally added.
ｌ）−！ａ束剤
ａ：エポキシ樹脂
ｂ：酢酸ビニル樹脂
２）カップリング剤
Ｃ：ｒ−アミノブロピルトリメトキンンランｄ；ビニル
エトキシシラン
ｅ ： ｒ−メタアクリロキシプロピルトリメトキシシ
ラン３）配合処方
（Ａ）ベースポリプロピレン（住友ノープレン０Ｗ ５
０１ 、 ＭＩ＝８ ） ５０ｗｔ％、所定の処理をお
こなった０ガラス繊維３０ｗｔ％（混合物（Ａ＋Ｂ）に
おいてＡは６２．５ｗｔ％、Ｂは３７．５ｗｔ％に相当
する）、アクリル酸変性ポリプロピレン（アクリル酸含
量４．０ｗｔ％） ２０ｗｔ％をリボンプレンダーを使
用して混合。l)-! a Bundling agent a: Epoxy resin b: Vinyl acetate resin 2) Coupling agent C: r-aminopropyltrimethoxylene d; Vinylethoxysilane e: r-methacryloxypropyltrimethoxysilane 3) Combination formulation (A) Base polypropylene (Sumitomo Noprene 0W 5
01, MI=8) 50 wt%, 30 wt% of predetermined treated 0 glass fiber (corresponding to 62.5 wt% of A and 37.5 wt% of B in the mixture (A+B)), acrylic acid-modified polypropylene (acrylic Acid content: 4.0 wt%) 20 wt% was mixed using a ribbon blender.
４）テストピース
上記混合物をベント型押出機（Ｌ／Ｄ＝２５゜Ｃ−Ｒ，
＝３．３．６５ｔＭＡφ）にて減圧度６８０ｍＨｇの条
件で押出造粒しく樹脂温度２３０℃）、射出成形機にて
所定のテストピースを作成（樹脂温度２５０℃）。4) Test piece The above mixture was passed through a vented extruder (L/D=25°C-R,
= 3.3.65 tMAφ) at a reduced pressure of 680 mHg (resin temperature: 230°C), and a predetermined test piece was prepared using an injection molding machine (resin temperature: 250°C).
Claims (1)
維に対して０．０２〜０．２ＰＨＲのアミノシラン系カ
ップリング剤および０．２〜１．２ＰＨＲのエポキシ樹
脂で処理したガラス繊維（Ｂ）１１〜４３ｗｔ％からな
る混合物（Ａ＋Ｂ）に対して、ガラス繊維（Ｂ）に対し
てのアクリル酸又は無水マレイン酸の重量比率が０．０
１〜０．０６の範囲になるようにアクリル酸又は無水マ
レイン酸を含む変性ポリプロピレン（Ｃ）を添加した混
合物（Ａ＋Ｂ＋Ｃ）をベント型押出機で減圧状態で押出
加工して得られるＶＭ（揮発分）０．１ｗｔ％以下の強
じんなポリプロピレン成形材料。Polypropylene (A) 89-57 wt% and glass fiber (B) 11-43 wt% treated with 0.02-0.2 PHR aminosilane coupling agent and 0.2-1.2 PHR epoxy resin The weight ratio of acrylic acid or maleic anhydride to glass fiber (B) is 0.0 for the mixture (A+B) consisting of
The VM (volatile content ) Tough polypropylene molding material of 0.1 wt% or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14735087A JPS62295940A (en) | 1987-06-12 | 1987-06-12 | Polypropylene molding material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14735087A JPS62295940A (en) | 1987-06-12 | 1987-06-12 | Polypropylene molding material |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1845277A Division JPS53102948A (en) | 1977-02-21 | 1977-02-21 | Polypropylene molding material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62295940A true JPS62295940A (en) | 1987-12-23 |
| JPS6352051B2 JPS6352051B2 (en) | 1988-10-17 |
Family
ID=15428197
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14735087A Granted JPS62295940A (en) | 1987-06-12 | 1987-06-12 | Polypropylene molding material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62295940A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5376701A (en) * | 1990-01-15 | 1994-12-27 | Exxon Chemical Patents Inc. | Thermoplastic polymer fibre composition |
| WO2005001276A1 (en) * | 2003-06-30 | 2005-01-06 | Toyo Roki Seizo Kabushiki Kaisha | Fiber-reinforced resin composition for parts of air intake system of internal combustion engine |
| CN102516642A (en) * | 2011-11-23 | 2012-06-27 | 安徽宜万丰电器有限公司 | Automobile support and manufacturing method thereof |
| CN103342858A (en) * | 2013-06-29 | 2013-10-09 | 金发科技股份有限公司 | Chopped glass fiber reinforced polypropylene composite material and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS497335A (en) * | 1972-05-11 | 1974-01-23 | ||
| JPS502167A (en) * | 1973-05-16 | 1975-01-10 | ||
| JPS525391A (en) * | 1975-06-24 | 1977-01-17 | Central Glass Co Ltd | Sizing component of glass fibre |
| JPS528054A (en) * | 1975-07-10 | 1977-01-21 | Mitsui Petrochem Ind Ltd | Glass-fiber reinforced polyolefin composition |
-
1987
- 1987-06-12 JP JP14735087A patent/JPS62295940A/en active Granted
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS497335A (en) * | 1972-05-11 | 1974-01-23 | ||
| JPS502167A (en) * | 1973-05-16 | 1975-01-10 | ||
| JPS525391A (en) * | 1975-06-24 | 1977-01-17 | Central Glass Co Ltd | Sizing component of glass fibre |
| JPS528054A (en) * | 1975-07-10 | 1977-01-21 | Mitsui Petrochem Ind Ltd | Glass-fiber reinforced polyolefin composition |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5376701A (en) * | 1990-01-15 | 1994-12-27 | Exxon Chemical Patents Inc. | Thermoplastic polymer fibre composition |
| WO2005001276A1 (en) * | 2003-06-30 | 2005-01-06 | Toyo Roki Seizo Kabushiki Kaisha | Fiber-reinforced resin composition for parts of air intake system of internal combustion engine |
| US7834078B2 (en) | 2003-06-30 | 2010-11-16 | Toyo Roki Seizo Kabushiki Kaisha | Fiber-reinforced resin composition for parts of air intake system of internal combustion engine |
| CN102516642A (en) * | 2011-11-23 | 2012-06-27 | 安徽宜万丰电器有限公司 | Automobile support and manufacturing method thereof |
| CN103342858A (en) * | 2013-06-29 | 2013-10-09 | 金发科技股份有限公司 | Chopped glass fiber reinforced polypropylene composite material and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6352051B2 (en) | 1988-10-17 |
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