JPS6044535A - Reinforced thermoplastic resin - Google Patents
Reinforced thermoplastic resinInfo
- Publication number
- JPS6044535A JPS6044535A JP15253683A JP15253683A JPS6044535A JP S6044535 A JPS6044535 A JP S6044535A JP 15253683 A JP15253683 A JP 15253683A JP 15253683 A JP15253683 A JP 15253683A JP S6044535 A JPS6044535 A JP S6044535A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- copolymer
- maleic anhydride
- thermoplastic resin
- glass fibers
- 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
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
この発明はガラス繊維強化熱可塑性樹脂組成物に係わる
ものである。DETAILED DESCRIPTION OF THE INVENTION This invention relates to a glass fiber reinforced thermoplastic resin composition.
ガラス繊維強化熱可塑性樹脂(以下、FRTPという)
は一般に強度、耐熱性、寸法安定性に優れた性能を有し
、各種成形品として広く使用されているが、本発明者等
は更に機械的強度の向上をはかる目的をもって鋭意研究
を重ね、この目的を達成する本発明を完成するに到った
。即ち本発明は無水マレイン酸と不飽和単量体との共重
合体およびシラン系カップリング痢で表面処理したガラ
ス繊維で熱可塑性樹脂を強化してなるガラス繊維強化熱
可・塑性樹脂に存するものでおる。Glass fiber reinforced thermoplastic resin (hereinafter referred to as FRTP)
Generally, it has excellent performance in terms of strength, heat resistance, and dimensional stability, and is widely used in various molded products. The present invention has been completed to achieve the object. That is, the present invention resides in a glass fiber-reinforced thermoplastic resin obtained by reinforcing a thermoplastic resin with glass fibers surface-treated with a copolymer of maleic anhydride and an unsaturated monomer and a silane-based coupling agent. I'll go.
本発明において無水マレイン酸と共重合体を形成する不
飽和単量体としては、スチレン、α−メチルスチレン、
ブタジェン、イソプレン、クロロブレン、2.3−ジク
ロロブタジェン、1.3−uンタジエン、シクロオクタ
ジエン、メチルアクリレート、エチルチクリレート、メ
チルメタクリレート、エチルチクリレート等が挙けられ
、中でも、ブタジェン、スチレンがhtLい。そしてこ
れら尊Iit体は2&!以上併用してもよい。In the present invention, unsaturated monomers that form a copolymer with maleic anhydride include styrene, α-methylstyrene,
Examples include butadiene, isoprene, chlorobrene, 2,3-dichlorobutadiene, 1,3-u-ntadiene, cyclooctadiene, methyl acrylate, ethyl thicrylate, methyl methacrylate, ethyl thicrylate, among others, butadiene and styrene. htL. And these precious Iit bodies are 2&! The above may be used in combination.
本発明における無水マレイン酸共重合体は平均分子量2
000以上であるのが好ましく、無水マレイン酸と不飽
和単量体との割合は特に制限されないが、得られる共重
合体をアルカリ性の水性媒体に可溶にするには無水マレ
イン酸ヲ比較的多目に、例えば60〜75モルチの無水
マレ′イン酸を用いるのがよい。このような割合の共重
合体はアルカリ水溶液に可溶であって、その水溶液に用
いたアルカリ性物質(アルカリ金属。The maleic anhydride copolymer in the present invention has an average molecular weight of 2
The ratio of maleic anhydride to the unsaturated monomer is preferably 000 or more, and the ratio of maleic anhydride to the unsaturated monomer is not particularly limited. For example, 60 to 75 molar maleic anhydride is preferably used. A copolymer having such a proportion is soluble in an alkaline aqueous solution, and the alkaline substance (alkali metal) used in the aqueous solution.
化合物、アンモニア、アミン類)によって塩の形となる
。compounds, ammonia, amines) in the form of salts.
不飽和単量体に対して使用する無水マレイン酸の割合が
小さくなると得られる共重合体の親水度が低下し、この
ようなものに対しては乳化剤を併用し、エマルジョンの
形にしてガラス繊維の表面処理を行なうことができる8
本発明で用いられるシラン系カップリング剤としては、
従来、ガラス繊維の表面処理に用いられたシラン系カッ
プリング剤がいずれも使用できる。具体的にはビニルト
リクロロシラン、ビニル−トリス−β−メトキシエトキ
シシラン、ビニルトリエトキシシラン、γ−アミノプロ
ピルトリエトキシシランカとが挙げられる。そしてこれ
らカップリング剤は1種以上用いることができる。When the ratio of maleic anhydride to the unsaturated monomer is small, the hydrophilicity of the resulting copolymer decreases. 8. The silane coupling agent used in the present invention is as follows:
Any silane coupling agent conventionally used for surface treatment of glass fibers can be used. Specific examples include vinyltrichlorosilane, vinyl-tris-β-methoxyethoxysilane, vinyltriethoxysilane, and γ-aminopropyltriethoxysilanka. One or more types of these coupling agents can be used.
上記無水マレイン酸共重合体とシラン系カップリング剤
との使用割合は広範囲にわたって変え得るが、通常は例
えば前者100重量部に対し、後者0.01〜10重量
部の割合で用いるのがよい。Although the proportions of the maleic anhydride copolymer and the silane coupling agent used can vary over a wide range, it is usually preferable to use, for example, 100 parts by weight of the former and 0.01 to 10 parts by weight of the latter.
無水マレイン酸共重合体とシラン系カップリング剤とは
通常、水性媒体中で混和し、更に必要に応じ、乳化剤又
はその他の助剤例えば増粘剤を加え、これでもってガラ
ス繊維が作られる工程時に、又は作られた後に表面処理
し、これを乾燥すれば、上記共重合体とカップリング剤
からなる被膜がガラス繊維表面に形成される。The maleic anhydride copolymer and the silane coupling agent are usually mixed in an aqueous medium, and if necessary, an emulsifier or other auxiliary agent, such as a thickener, is added, and a glass fiber is produced using this process. When the glass fiber is surface-treated or dried, a coating consisting of the copolymer and the coupling agent is formed on the surface of the glass fiber.
上記表面処理されたガラス繊維によって補強される熱可
塑性樹脂としては従来FRTPに用いられた熱可塑性樹
脂にはいずれも適用でき、具体的にはポリエチレン、ポ
リプロピレンのようなポリオレフィン類、ナイロン、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、ポリカーボネート、アセタール樹脂、ポリフェニレ
ンオキシド、アクリロニトリル−スチレン共重合体など
が挙げられる。As the thermoplastic resin reinforced by the above-mentioned surface-treated glass fibers, any thermoplastic resin conventionally used in FRTP can be applied, and specifically, polyolefins such as polyethylene and polypropylene, nylon, polyethylene terephthalate, Examples include polybutylene terephthalate, polycarbonate, acetal resin, polyphenylene oxide, acrylonitrile-styrene copolymer, and the like.
そしてこれら樹脂は以下の実施例にみられる通シ引張シ
強度、曲げ強度、衝撃強度などの機械的強度に優れた物
性を示し、またナイロン樹脂においては耐水性の向上が
みられるのである。These resins exhibit excellent physical properties such as mechanical strength, such as transverse tensile strength, bending strength, and impact strength, as shown in the following examples, and nylon resins exhibit improved water resistance.
次に本発明の詳細な説明するが、これらは本発明の理解
を助けるための代表的例示に係わるものであり1本″発
明はこれらの例示によって制限されるものでない。Next, the present invention will be described in detail, but these are representative examples to aid understanding of the present invention, and the present invention is not limited to these examples.
実施例 1
無水マレイン酸と下記第1表に示すコモノマーとのほぼ
1対1モル比からなる共重合体をアンモ−ニア性水溶液
(濃& 0.5%)に加えてよく攪拌し、得られた液に
γ−アミノプロピルトリエトキシシランを象加混合し、
処理液を調製する。この場合、上記共重合体(tNjl
形分)2.8重量部に対し、シラン化合物は0.6重量
部の割合で使用する。Example 1 A copolymer consisting of maleic anhydride and a comonomer shown in Table 1 below in a molar ratio of approximately 1:1 was added to an ammoniacal aqueous solution (concentrated & 0.5%) and stirred well to obtain a copolymer. γ-aminopropyltriethoxysilane was added to the solution and mixed,
Prepare the processing solution. In this case, the above copolymer (tNjl
The silane compound is used at a ratio of 0.6 parts by weight to 2.8 parts by weight (form).
上記表面処理液を、溶融紡糸されてフィラメントになっ
てで又(る径13μのガラス繊維に対し、これを回転ド
ラムに巻きとる途中に設けられたアプリケータによって
適用、集束し、しかる後、乾燥して上記共重合体および
カップリング剤からなる組成の被膜で覆われたガラス繊
維束を得た。上記ガラス繊維束を3■の長さに切断し、
ナイロン6、乙に加え、常法に従ってgレット化し、こ
のはレットを射出成形によって成形品とした。このもの
の引張シ強度、曲げ強度、曲げ弾性率、アイゾツト衝撃
強度を下記第1表に示す。第、1表において、SSはス
トランドソリッド、即ちガラス繊維に対し、被覆した固
形分(即ち無水マレイン酸共重合体およびシラン化合物
)(実施例2以下でもSSと略称する。)の重量裂を示
し、またGCはガラスコンテント、即ち強化樹脂中のガ
ラス繊維量を重量%で示すものである。実施例2以下で
も、これをGCと略称する。The above-mentioned surface treatment liquid is applied to glass fibers having a diameter of 13 μm that have been melt-spun into filaments using an applicator installed in the middle of winding them around a rotating drum, and then dried. A glass fiber bundle covered with a coating having a composition consisting of the above copolymer and a coupling agent was obtained.The above glass fiber bundle was cut into a length of 3 cm.
In addition to nylon 6 and Otsu, it was made into a glet according to a conventional method, and this glet was made into a molded product by injection molding. The tensile strength, bending strength, bending modulus and Izot impact strength of this product are shown in Table 1 below. In Table 1, SS indicates the weight difference of the coated solid content (i.e., maleic anhydride copolymer and silane compound) (also abbreviated as SS in Example 2 and below) with respect to the strand solid, i.e., glass fiber. , and GC indicates the glass content, that is, the amount of glass fibers in the reinforced resin in weight percent. This is also abbreviated as GC in Example 2 and below.
実施例 2
この実施例では強化される樹脂としてナイロンを用いる
とき、得られる樹脂成形品の耐水性が著しく向上するこ
とを示す。Example 2 This example shows that when nylon is used as the reinforcing resin, the water resistance of the resulting resin molded product is significantly improved.
無水マレイン酸と共重合するコモノマー、SSおよびG
Cを下記第2表に示すものとし、その他は実施例1にお
けると同様にして表面処理をしたガラス繊維を作υ、こ
れを用いて強化熱可塑性樹脂を製造し、そのものの引張
シ強度を測定した。その結果を下記第2表に示す。Comonomers copolymerized with maleic anhydride, SS and G
C was shown in Table 2 below, and glass fibers were surface-treated in the same manner as in Example 1, and a reinforced thermoplastic resin was manufactured using this, and its tensile strength was measured. did. The results are shown in Table 2 below.
第2表
引張り強度におけるDRYはガラス繊維強化樹脂の成形
品をそのま\測定したものであ、り 、WJliTはそ
の成゛形品t−142℃の熱水中に20時間浸漬”した
後に測定した値である。保持率はW、]l!!T測定値
/ 測定値側定値の値である。なお従来品のガラス繊維
で強化したナイロン6.6における引張シ強度の一例で
はDRY14.4、wgT7.1、保持率49であり、
本発明によるものの耐水性向上は著しいものがある。。DRY in Table 2 tensile strength is measured as is for molded products made of glass fiber reinforced resin, while WJliT is measured after immersing the molded products in hot water at -142°C for 20 hours. The retention rate is the value of W, ]l!!T measured value/measured value side constant value.In addition, an example of the tensile strength of a conventional glass fiber-reinforced nylon 6.6 is DRY14.4. , wgT7.1, retention rate 49,
The water resistance of the product according to the present invention is significantly improved. .
実施例 3
この実施例ではホリブチレンテレフタレートの強化を行
なった。Example 3 In this example, holybutylene terephthalate was reinforced.
無水マレイン酸と共重合するコモノマー、SSおよびG
Cを下記第3表に示すものとし、その他は実施例1にお
けると同様にして赤面処理したガラス繊維を作υ、これ
を用いて強化樹脂を製造した。このものの物性を下記第
3飯に示す。Comonomers copolymerized with maleic anhydride, SS and G
C was shown in Table 3 below, and red-treated glass fibers were produced in the same manner as in Example 1, and a reinforced resin was produced using the glass fibers. The physical properties of this product are shown in Item 3 below.
髪
外お、第3表における実験番号に餅誓等1で用いた共重
合体はマレイン化ポリブタジェンである。In addition, the copolymer used in Experiment No. 1 in Table 3 is maleated polybutadiene.
実施例 4
この実施例ではdセリエチレンテレフタレートの強化を
行った。無水マレイン酸と共重合するコモノマー1.
SSおよびGCを下記餓4表に示すものとし、その他は
実施例1におけると同様にして表m1処理したガラス繊
維を作り、これを用いて強化樹脂を製造した。そのもの
の物性を第4表に示す。Example 4 In this example, d-seriethylene terephthalate was strengthened. Comonomer copolymerized with maleic anhydride 1.
SS and GC were as shown in Table 4 below, and glass fibers treated in Table m1 were prepared in the same manner as in Example 1, and a reinforced resin was manufactured using this. Its physical properties are shown in Table 4.
実施例 5
この実施例ではポリカーボネート(下記表ではPCと略
記する)、ポリオキシメチレン(下記表ではPOMと略
記する)、変性ポリフェニレンオキシド(下記表ではP
POと略記する)、オよびアクリロニトリル−スチレン
共重合体(下記表ではASと略記する〕の強化を行なっ
た。Example 5 This example uses polycarbonate (abbreviated as PC in the table below), polyoxymethylene (abbreviated as POM in the table below), and modified polyphenylene oxide (abbreviated as P in the table below).
(abbreviated as PO), O, and acrylonitrile-styrene copolymer (abbreviated as AS in the table below).
強化される樹脂、無水マレイン酸と共重合するコモノマ
ー、SSおよびGSを下記第5表に示すものとし、その
他は実施例1におけると同様にして表面処御したガラス
繊維を作り、これを用いて強化樹脂1c’M造した。そ
のものの物性を第5表に示す。The resin to be reinforced, the comonomer to be copolymerized with maleic anhydride, SS and GS are as shown in Table 5 below, and a surface-treated glass fiber was prepared in the same manner as in Example 1, and using this. Made of reinforced resin 1c'M. Its physical properties are shown in Table 5.
実施例 に
の実施例ではポリプロピレンの強化を行なった。無水マ
レイン亀と共重合を行なうコモノマーおよびGC″f:
下記第6表に示すものとし、その他は実施例1と同様に
して表面処理したガラス繊維を作夛、これを用いて強化
樹脂を製造した。そのものの物性を下記第6表に示す。In the examples shown in Examples, polypropylene was reinforced. Comonomer and GC″f copolymerized with anhydrous maleic acid:
Glass fibers as shown in Table 6 below were surface-treated in the same manner as in Example 1, and a reinforced resin was produced using the glass fibers. The physical properties of the product are shown in Table 6 below.
第6表Table 6
Claims (1)
ン糸カップリング剤で表面処理したガラス繊維で熱可塑
性樹脂を強化してなるガラス繊維強化熱可塑性樹脂A glass fiber-reinforced thermoplastic resin made by reinforcing a thermoplastic resin with glass fibers surface-treated with a copolymer of maleic anhydride and an unsaturated monomer and a silane thread coupling agent.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP15253683A JPS6044535A (en) | 1983-08-23 | 1983-08-23 | Reinforced thermoplastic resin |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP15253683A JPS6044535A (en) | 1983-08-23 | 1983-08-23 | Reinforced thermoplastic resin |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS6044535A true JPS6044535A (en) | 1985-03-09 |
JPS6137308B2 JPS6137308B2 (en) | 1986-08-22 |
Family
ID=15542584
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP15253683A Granted JPS6044535A (en) | 1983-08-23 | 1983-08-23 | Reinforced thermoplastic resin |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS6044535A (en) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH01278544A (en) * | 1988-04-28 | 1989-11-08 | Tonen Sekiyukagaku Kk | Fiber-reinforced polymer composition |
US7129289B2 (en) | 2001-12-21 | 2006-10-31 | Owens Corning Composites S.P.R.L. | Hydrolization resistant sizing composition |
CN1302031C (en) * | 2005-03-25 | 2007-02-28 | 泰山玻璃纤维股份有限公司 | Use of methacrylic acid tetradecyl ester-maleic anhydride copolymer |
JP2010269995A (en) * | 2009-04-22 | 2010-12-02 | Asahi Kasei Chemicals Corp | Glass fiber sizing agent and glass fiber-reinforced thermoplastic resin composition |
CN113549322A (en) * | 2021-08-02 | 2021-10-26 | 安徽省华晟塑胶股份有限公司 | Lightweight bumper shock absorber spring pad |
CN115926449A (en) * | 2022-12-30 | 2023-04-07 | 青岛海泰科新材料科技有限公司 | High-content glass fiber reinforced nylon 6 composite material and preparation method thereof |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH01207548A (en) * | 1988-02-12 | 1989-08-21 | Fujisash Co | Ventilator for curtain wall |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS4919097A (en) * | 1972-04-14 | 1974-02-20 | ||
JPS52110999A (en) * | 1976-03-12 | 1977-09-17 | Asahi Dow Ltd | Fiber treating composition |
JPS52121059A (en) * | 1976-04-05 | 1977-10-12 | Sumitomo Chem Co Ltd | Improved reinforced polyolefin compositions |
JPS55161836A (en) * | 1979-06-04 | 1980-12-16 | Nippon Steel Chem Co Ltd | Resin composition |
JPS5670055A (en) * | 1979-11-14 | 1981-06-11 | Asahi Chem Ind Co Ltd | Glass-fiber reinforced resin composition |
JPS5986649A (en) * | 1982-11-10 | 1984-05-18 | Daicel Chem Ind Ltd | Glass fiber-reinforced styrene resin composition |
-
1983
- 1983-08-23 JP JP15253683A patent/JPS6044535A/en active Granted
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS4919097A (en) * | 1972-04-14 | 1974-02-20 | ||
JPS52110999A (en) * | 1976-03-12 | 1977-09-17 | Asahi Dow Ltd | Fiber treating composition |
JPS52121059A (en) * | 1976-04-05 | 1977-10-12 | Sumitomo Chem Co Ltd | Improved reinforced polyolefin compositions |
JPS55161836A (en) * | 1979-06-04 | 1980-12-16 | Nippon Steel Chem Co Ltd | Resin composition |
JPS5670055A (en) * | 1979-11-14 | 1981-06-11 | Asahi Chem Ind Co Ltd | Glass-fiber reinforced resin composition |
JPS5986649A (en) * | 1982-11-10 | 1984-05-18 | Daicel Chem Ind Ltd | Glass fiber-reinforced styrene resin composition |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH01278544A (en) * | 1988-04-28 | 1989-11-08 | Tonen Sekiyukagaku Kk | Fiber-reinforced polymer composition |
US7129289B2 (en) | 2001-12-21 | 2006-10-31 | Owens Corning Composites S.P.R.L. | Hydrolization resistant sizing composition |
CN1302031C (en) * | 2005-03-25 | 2007-02-28 | 泰山玻璃纤维股份有限公司 | Use of methacrylic acid tetradecyl ester-maleic anhydride copolymer |
JP2010269995A (en) * | 2009-04-22 | 2010-12-02 | Asahi Kasei Chemicals Corp | Glass fiber sizing agent and glass fiber-reinforced thermoplastic resin composition |
JP2016034897A (en) * | 2009-04-22 | 2016-03-17 | 旭化成ケミカルズ株式会社 | Glass fiber sizing agent and glass fiber-reinforced thermoplastic resin composition |
CN113549322A (en) * | 2021-08-02 | 2021-10-26 | 安徽省华晟塑胶股份有限公司 | Lightweight bumper shock absorber spring pad |
CN113549322B (en) * | 2021-08-02 | 2023-08-15 | 安徽省华晟塑胶股份有限公司 | Light shock absorber spring pad |
CN115926449A (en) * | 2022-12-30 | 2023-04-07 | 青岛海泰科新材料科技有限公司 | High-content glass fiber reinforced nylon 6 composite material and preparation method thereof |
CN115926449B (en) * | 2022-12-30 | 2024-01-19 | 青岛海泰科新材料科技有限公司 | High-content glass fiber reinforced nylon 6 composite material and preparation method thereof |
Also Published As
Publication number | Publication date |
---|---|
JPS6137308B2 (en) | 1986-08-22 |
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