JPH07242755A - Glass fiber bundle for reinforcing resin and production of molding material - Google Patents
Glass fiber bundle for reinforcing resin and production of molding materialInfo
- Publication number
- JPH07242755A JPH07242755A JP3103350A JP10335091A JPH07242755A JP H07242755 A JPH07242755 A JP H07242755A JP 3103350 A JP3103350 A JP 3103350A JP 10335091 A JP10335091 A JP 10335091A JP H07242755 A JPH07242755 A JP H07242755A
- Authority
- JP
- Japan
- Prior art keywords
- water
- glass fiber
- resin
- fiber bundle
- forming agent
- 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
Landscapes
- Reinforced Plastic Materials (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、樹脂補強用ガラス繊維
束並びに成形材料の製造法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a glass fiber bundle for resin reinforcement and a molding material.
【０００２】[0002]
【従来の技術】ガラス繊維は、ＦＲＰを製造するための
補強用繊維として広く用いられている。工業用的にはガ
ラス繊維は、プッシングから引出したガラス繊維を多数
集束したガラス繊維束の形態で用いられることが多い
が、その製造工程（採糸工程）、取扱中の毛羽立ち、糸
切れを防止して作業性を向上させ、樹脂との馴染を良好
ならしめるために、シランカップリング剤及び被膜形成
剤を含む集束剤が附与される。このようにして製造され
たガラス繊維束（ストランド）は、乾燥されて樹脂補強
用繊維として用いられる。ストランドの切断物（チョッ
プドストランド、ＣＳと省略）と樹脂を均一に混練し
て、ガラス繊維を樹脂中に分散させたバルグモールディ
ングコンパウンド（ＢＭＣ）はＦＲＰを製造するための
成形材料として使用されている。BACKGROUND OF THE INVENTION Glass fibers are widely used as reinforcing fibers for producing FRP. For industrial use, glass fibers are often used in the form of glass fiber bundles in which a large number of glass fibers pulled out from a pusher are bundled, but the manufacturing process (yarning process), fluffing during handling, and yarn breakage are prevented. A sizing agent containing a silane coupling agent and a film-forming agent is added in order to improve workability and improve compatibility with the resin. The glass fiber bundle (strand) thus produced is dried and used as a resin-reinforcing fiber. A vulg molding compound (BMC), in which a cut product of a strand (chopped strand, abbreviated as CS) and a resin are uniformly kneaded and glass fibers are dispersed in the resin, is used as a molding material for producing FRP. .
【０００３】[0003]
【発明が解決しようとする課題】従来技術は次のような
問題点を有する。前述したように、皮膜形成剤は、スト
ランドの毛羽立、ストランド切断時のモノフィラメント
化等を防止し、作業性を向上させるための必要不可欠な
成分であるが、ストランドを乾燥すると、ストランドを
構成するカラス繊維同志が皮膜形成剤で強く密着する。
このため、ストランド中への樹脂の染み込み（ウエット
アウト）が悪化し、ストランド中に樹脂が均一に含浸し
ない含浸不良が生じ、均質なＦＲＰが得られなくなる。
又、ＢＭＣを製造する際、ＣＳと樹脂を充分混練し、Ｃ
Ｓをバラバラに個々のガラス繊維（モノフィラメント）
に開繊し、樹脂中に均一に分散させる必要があるが、ガ
ラス繊維は皮膜形成剤で強く結合しているため、ＣＳを
開繊するためには、ＣＳと樹脂とを強い撹拌力で長時間
混練する必要がある。このため、混練中にＣＳを構成す
るガラス繊維が寸断され、ＢＭＣを用いて製造したＦＲ
Ｐの強度が低下する。本発明は、前述の従来技術の問題
点を解消し、ウエットアウトが良好なガラス繊維束並び
に強度の大きいＦＲＰが得られるような成形材料の製造
法を提供することを目的としている。The prior art has the following problems. As described above, the film-forming agent is an essential component for improving the workability by preventing strand fluffing, forming a monofilament during strand cutting, etc., but when the strand is dried, it forms the strand. Crow fibers firmly adhere to each other with a film-forming agent.
For this reason, impregnation (wet out) of the resin into the strands deteriorates, impregnation failure occurs in which the resin is not uniformly impregnated into the strands, and uniform FRP cannot be obtained.
Also, when manufacturing BMC, CS and resin are thoroughly kneaded, and C
Separate glass fiber (monofilament)
It is necessary to open the fibers and disperse them evenly in the resin, but since the glass fibers are strongly bound by the film-forming agent, in order to open the CS, the CS and the resin can be stirred with a strong stirring force. Need to knead for hours. For this reason, the glass fibers constituting CS were cut during the kneading, and FR produced using BMC
The strength of P decreases. SUMMARY OF THE INVENTION It is an object of the present invention to solve the above-mentioned problems of the prior art and to provide a method for producing a molding material that can obtain a glass fiber bundle with good wetout and an FRP with high strength.
【０００４】[0004]
【課題を解決するための手段】上記目的を達成するため
に、本発明においては、水に可溶性または水膨潤性の皮
膜形成剤と水に不溶性の皮膜形成剤とを含む集束剤を附
与集束した樹脂補強用ガラス繊維束を樹脂補強用として
使用し、又水に可溶性又は水膨潤性の皮膜形成剤と水に
不溶性の皮膜形成剤とを含む集束剤を附与集束したガラ
ス繊維束を熱硬化性樹脂と混練することにより成形材料
を製造する。To achieve the above object, in the present invention, a sizing agent containing a water-soluble or water-swellable film-forming agent and a water-insoluble film-forming agent is added and focused. The resin-reinforced glass fiber bundle is used as a resin reinforcing material, and a sizing agent containing a water-soluble or water-swellable film-forming agent and a water-insoluble film-forming agent is applied to heat the glass fiber bundle. A molding material is manufactured by kneading with a curable resin.
【０００５】次に、本発明を更に具体的に説明する。本
発明において使用される水に可溶性の皮膜形成剤として
は、ポリエチレンオキサイド、ポリビニールアルコー
ル、ポリビニールピロリドン、メチルセルローズ、可溶
性澱粉等、特にポリエチレンオキサイドを用いるのが適
当である。本発明において使用される水膨潤性の皮膜形
成剤とは、水の作用により膨潤して、結合力が低下する
ような皮膜形成剤を指称し、例えばケン化度の大きいポ
リビニールアルコール、ポリ酢酸ビニール、澱粉等が適
当である。水に可溶性又は水膨潤性の皮膜形成剤はガラ
ス繊維に対する結合力が弱く、水に可溶性又は水膨潤性
の皮膜形成剤のみを用いて集束したガラス繊維束は、湿
潤した状態において指先で軽くつまむと繊維束が潰れ
て、モノフィラメント状になり易い。なお、水に可溶性
の皮膜形成剤と水膨潤性皮膜形成剤を併用することもで
きる。又、水に不溶性の皮膜形成剤としては、ウレタン
樹脂、エポキシ樹脂、フェノール樹脂等、特にウレタン
樹脂を用いるのが適当である。Next, the present invention will be described more specifically. As the water-soluble film-forming agent used in the present invention, polyethylene oxide, polyvinyl alcohol, polyvinylpyrrolidone, methylcellulose, soluble starch and the like, particularly polyethylene oxide, are suitable. The water-swellable film-forming agent used in the present invention refers to a film-forming agent that swells due to the action of water to reduce the binding force. For example, polyvinyl alcohol having a high degree of saponification and polyacetic acid. Vinyl, starch, etc. are suitable. A water-soluble or water-swellable film-forming agent has a weak binding force to glass fibers, and a glass fiber bundle focused only with a water-soluble or water-swellable film forming agent is lightly pinched with a fingertip in a wet state. And the fiber bundle is easily crushed to form a monofilament. A water-soluble film-forming agent and a water-swellable film-forming agent may be used in combination. Further, as the water-insoluble film forming agent, it is suitable to use urethane resin, epoxy resin, phenol resin and the like, especially urethane resin.
【０００６】水に可溶性又は水膨潤の皮膜形成剤の合計
量と水に不溶性の皮膜形成の割合は１：１〜１：１０望
ましくは１：３〜１：７の間とするのが好ましい。この
割合があまり小さすぎると、樹脂の含浸が不充分とな
り、又ガラス繊維束を熱可塑性樹脂と混練する際、ガラ
ス繊維の分散が不充分となる。分散を充分に行わせよう
とすると、混練を強い撹拌力で長時間行う必要が生じ、
このため混練中にガラス繊維が寸断され、成形品の強度
が低下し易く、充分な効果が得られ難い。 又この割合
があまり大きいと、ガラス繊維束に毛羽立ちが生じた
り、ガラス繊維束がモノフィラメント化して団魂状とな
って、得られたＦＲＰの物性が低下し易い。本発明にお
いては、更に、アミノシラン、ビニールシランのような
シランカップリング剤を併用するのが好ましい。The ratio of the total amount of water-soluble or water-swellable film-forming agent to the water-insoluble film-forming agent is preferably 1: 1 to 1:10, and preferably 1: 3 to 1: 7. If this ratio is too small, impregnation of the resin will be insufficient, and when the glass fiber bundle is kneaded with the thermoplastic resin, the dispersion of the glass fibers will be insufficient. In order to sufficiently disperse, it is necessary to carry out kneading with a strong stirring force for a long time,
For this reason, the glass fibers are shredded during the kneading, the strength of the molded product is likely to be lowered, and it is difficult to obtain a sufficient effect. On the other hand, if this ratio is too large, the glass fiber bundle is fluffed, or the glass fiber bundle becomes a monofilament to form a bundle, and the physical properties of the obtained FRP are likely to be deteriorated. In the present invention, it is preferable to further use a silane coupling agent such as aminosilane or vinylsilane.
【０００７】本発明においては、上述した皮膜形成剤と
好ましくはカップリング剤を含む集束剤をガラス繊維に
附与集束してガラス繊維束とする。ガラス繊維束に対す
る皮膜形成剤（合計）及びカップリング剤の附与量は、
夫々、固形分として０．２〜３ｗｔ％，０．００５〜
０．５ｗｔ％望ましくは０．４〜２ｗｔ％，０．０１〜
０．１ｗｔ％とするのが適当である。附与量あまり大き
いと、ウエットアウトが低下し、又ガラス繊維束の開繊
が困難となり、又この量があまり小さいと、採糸等の作
業において毛羽立ちが発生し易い。なお、ガラス繊維の
直径は３〜２０μ、好ましくは５〜１５μ、集束本数は
２０〜１０．０００本、好ましくは４０〜２．０００本
とするのが適当である。なお、集束剤中に更に、ノニオ
ン系、カチオン系のような潤滑剤を含有させることもで
き、本発明の効果を損なうことなく、採糸等の作業性を
向上させることができる。In the present invention, the sizing agent containing the above-mentioned film-forming agent and preferably the coupling agent is added to the glass fiber and bundled to form a glass fiber bundle. The amount of film forming agent (total) and coupling agent added to the glass fiber bundle is
The solid content is 0.2 to 3 wt% and 0.005 respectively.
0.5 wt%, preferably 0.4-2 wt%, 0.01-
It is suitable to set it to 0.1 wt%. If the added amount is too large, the wet-out will be reduced, and it will be difficult to open the glass fiber bundle, and if the added amount is too small, fluffing is likely to occur during operations such as threading. The glass fiber has a diameter of 3 to 20 µ, preferably 5 to 15 µ, and the number of bundles is 20 to 10.000, preferably 40 to 2.000. In addition, the sizing agent may further contain a lubricant such as a nonionic type or a cation type, so that the workability such as the yarn collecting can be improved without impairing the effect of the present invention.
【０００８】上述したガラス繊維束（本ガラス繊維束）
はウエットアウトも良好であり、ＣＳＭ（コンティニュ
アスストランドマット）或は、ＣＭ（チョップマット）
のような形状で用い、ＦＲＰ用の補強繊維として使用す
ることもできるが、本ガラス繊維束は、その切断物を熱
硬化性樹脂と混練し、ＢＭＣを製造するために用いた場
合、特に顕著な効果をうることができる。ＢＭＣを製造
する為に用いる熱硬化性樹脂としては、フェノール樹脂
を用いた場合に特に優れた効果が得られることが判明し
た。フェノール樹脂の縮合に際し、水分が生成し、この
水分が水に可溶性又は水膨潤性の皮膜形成剤と作用し、
皮膜形成剤によるガラス繊維の結合力が低下し、ウエッ
トアウトが向上し開繊が行われ易くなるものと思われ
る。フエノール樹脂としては、レゾール（ベークライト
Ａ）又はレジトール（ベークライトＢ）を用いるのが実
際的であるが、ノボラックに過剰のホルムアルデヒド又
は加熱によりホルムアルデヒドを発生する物質（例えば
ヘキサメチレンジアミン）を加えたものを使用すること
もできる。ＣＳと樹脂の割合は、両者の合計量中に占め
るＣＳの重量割合が５〜６０ｗｔ％望ましくは１０〜５
０ｗｔ％となるように定めるのが適当である。両者の混
合（混練）方法に特に限定はなく、常法を使用できる
が、弱い撹拌力で短時間混合を行った場合でもＣＳ充分
開繊することができ、本発明のＣＳを用いた場合、ガラ
ス繊維の長いＢＭＣを得ることができ、このＢＭＣを用
いて成形したＦＲＰの強度を約２０％乃至それ以上向上
させることができる。なお、ＢＭＣを製造する際、ＣＳ
と樹脂の他に、硬化剤、内部離型剤、炭カル、水マグ、
クレーのような充填材、顔料等の副成分を添加すること
もできる。上述したように、本発明は熱硬化性樹脂とし
てフェノール樹脂を用いた場合に特に著しい効果をうる
ことができる。The above-mentioned glass fiber bundle (this glass fiber bundle)
Has good wet out, CSM (Continuous Strand Mat) or CM (Chop Mat)
Although it can be used as a reinforcing fiber for FRP, the present glass fiber bundle is particularly prominent when the cut product is kneaded with a thermosetting resin to produce BMC. It is possible to obtain various effects. It has been found that a particularly excellent effect can be obtained when a phenol resin is used as the thermosetting resin used for producing BMC. Upon condensation of the phenolic resin, water is generated, and this water acts as a water-soluble or water-swellable film forming agent,
It is considered that the binding force of the glass fiber by the film forming agent is reduced, the wetout is improved, and the fiber opening is facilitated. As the phenol resin, it is practical to use resole (Bakelite A) or resistol (Bakelite B). It can also be used. As for the ratio of CS and resin, the weight ratio of CS in the total amount of both is 5 to 60 wt%, preferably 10 to 5
It is suitable to set it to be 0 wt%. The method for mixing (kneading) both is not particularly limited, and a conventional method can be used, but CS can be sufficiently opened even when mixing is performed for a short time with a weak stirring force, and when the CS of the present invention is used, BMC with long glass fibers can be obtained, and the strength of FRP molded using this BMC can be improved by about 20% or more. When manufacturing BMC, CS
And resin, hardener, internal release agent, calcium carbonate, water mug,
Fillers such as clay and auxiliary components such as pigments can also be added. As described above, the present invention can obtain a particularly remarkable effect when a phenol resin is used as the thermosetting resin.
【０００９】[0009]
【作用】水に可溶性又は水膨潤性の皮膜形成剤と水に不
溶性の皮膜形成剤とを含む集束材を附与収束した樹脂補
強用ガラス繊維束を用いることにより、樹脂中又はＣＳ
に若干含まれる水分、特に樹脂の縮合の際生成する水分
により、ガラス繊維束に樹脂を含浸させる際、或はガラ
ス繊維束と樹脂を混練する際のガラス繊維同志の結合力
を弱め、樹脂の含浸或は樹脂との混合を容易ならしめ
る。By using a glass fiber bundle for resin reinforcement, which is provided with a sizing material containing a water-soluble or water-swellable film-forming agent and a water-insoluble film-forming agent, the glass fiber bundle for resin reinforcement can be used.
The water contained in a little, especially the water generated during the condensation of the resin, weakens the binding force between the glass fibers when impregnating the glass fiber bundle with the resin or when kneading the glass fiber bundle and the resin, Facilitates impregnation or mixing with resin.
【００１０】[0010]
【実施例１】ブッシングから引き出した直径１０μのガ
ラス繊維に、ポリエチレンオキサイド（水に可溶性の皮
膜形成剤）を１ｗｔ％、ウレタンエマルジョン（水に不
溶性の皮膜形成剤）を５ｗｔ％、シランンカップリング
剤を０．２ｗｔ％、ノニオン系潤滑剤を０．５ｗｔ％含
む集束剤を、固形分として１．４ｗｔ％附与し、２，０
００本集束してガラス繊維束となし、乾燥、切断してＣ
Ｓとした。このＣＳ５０重量部とフエノール樹脂（ノボ
ラック型フエノール樹脂）４０重量部、充填材、硬化
剤、内部離型剤の合計量１０重量部とを常法に従って混
練し、ＢＭＣを製造した。このＢＭＣを用いて試験片を
作成し、ＪＩＳＫ６９１１号の試験法に従ってノツチ付
衝撃強度を測定した。強度は８．２Ｋｇｆcm/cm であっ
た。[Example 1] 1 wt% of polyethylene oxide (water-soluble film-forming agent), 5% by weight of urethane emulsion (water-insoluble film-forming agent), and silan coupling to glass fibers having a diameter of 10 µm drawn from a bushing. A sizing agent containing 0.2 wt% of a lubricant and 0.5 wt% of a nonionic lubricant was added as a solid content of 1.4 wt% to obtain 2,0.
00 bundled into a glass fiber bundle, dried and cut into C
S. 50 parts by weight of this CS, 40 parts by weight of a phenol resin (novolak type phenol resin), a total amount of 10 parts by weight of a filler, a curing agent, and an internal release agent were kneaded according to a conventional method to produce BMC. A test piece was prepared using this BMC, and the notched impact strength was measured according to the test method of JIS K6911. The strength was 8.2 Kgfcm / cm 2.
【００１１】[0011]
【実施例２】実施例１のポリエチレンオキサイドに代え
ポリ酢酸ビニール（水膨潤性皮膜形成剤）を用い同様な
実験を行った。強度は８．４Ｋｇｆcm/cm であった。Example 2 A similar experiment was conducted using polyvinyl acetate (water-swellable film forming agent) in place of the polyethylene oxide of Example 1. The strength was 8.4 Kgfcm / cm 2.
【００１２】[0012]
【比較例】実施例１の集束剤に代え、ウレタンエマルジ
ョンを６ｗｔ％、シランカツプリング剤を０．２ｗｔ
％、ノニオン系潤滑剤０．５ｗｔ％を含む集束剤を用
い、実施例と同様な実験を行った。ノッチ付き衝撃強度
は６．０Ｋｇｆcm/cm であった。Comparative Example Instead of the sizing agent of Example 1, 6 wt% urethane emulsion and 0.2 wt% silane coupling agent were used.
%, And a sizing agent containing 0.5 wt% of a nonionic lubricant, an experiment similar to the example was performed. The notched impact strength was 6.0 Kgfcm / cm 2.
【００１３】[0013]
【発明の効果】ガラス繊維束に対する樹脂の含浸性、開
繊性を良好ならしめ、均質な強度の大きいＦＲＰをうる
ことができる。EFFECT OF THE INVENTION By impregnating the resin into the glass fiber bundle and the openability of the glass fiber bundle, it is possible to obtain a uniform and strong FRP.
───────────────────────────────────────────────────── 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 Ｃ０８Ｌ 61:06 ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Internal reference number FI technical display area C08L 61:06
Claims (3)
と水に不溶性の皮膜形成剤とを含む集束剤を附与集束し
た樹脂補強用ガラス繊維束。1. A glass fiber bundle for resin reinforcement, which is bundled with a sizing agent containing a water-soluble or water-swellable film-forming agent and a water-insoluble film-forming agent.
水に不溶性の皮膜形成剤とを含む集束剤を附与集束した
ガラス繊維束を熱硬化性樹脂と混練する成形材料の製造
法。2. A method for producing a molding material, which comprises kneading a glass fiber bundle, which is bundled with a sizing agent containing a water-soluble or water-swellable film-forming agent and a water-insoluble film-forming agent, with a thermosetting resin. .
求項２記載の製造法。3. The method according to claim 2, wherein the thermosetting resin is a phenol resin.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3103350A JPH07242755A (en) | 1990-04-13 | 1991-04-09 | Glass fiber bundle for reinforcing resin and production of molding material |
| JP4091500A JPH0759365B2 (en) | 1991-03-29 | 1992-03-18 | Manufacturing method of resin reinforcement material and manufacturing method of molding material |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9652890 | 1990-04-13 | ||
| JP2-96528 | 1990-04-13 | ||
| JP3103350A JPH07242755A (en) | 1990-04-13 | 1991-04-09 | Glass fiber bundle for reinforcing resin and production of molding material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH07242755A true JPH07242755A (en) | 1995-09-19 |
Family
ID=26437729
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3103350A Pending JPH07242755A (en) | 1990-04-13 | 1991-04-09 | Glass fiber bundle for reinforcing resin and production of molding material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07242755A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006199972A (en) * | 2001-10-23 | 2006-08-03 | Fiber Glass Japan Co Ltd | Chopped strands and molded product of unsaturated polyester resin bmc employing them |
| JP2008520849A (en) * | 2004-11-18 | 2008-06-19 | オウェンス コーニング ファイバーグラス テクノロジー インコーポレイテッド | Nonwoven fabric with improved structure, sound absorption and thermal properties |
| CN115160714A (en) * | 2022-07-21 | 2022-10-11 | 武汉理工大学 | Microwave composite dielectric substrate for high-frequency and high-speed environment and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4877192A (en) * | 1972-01-07 | 1973-10-17 | Johns Manville | |
| JPS5253090A (en) * | 1975-10-24 | 1977-04-28 | Kubota Ltd | Glass fiber used for strengthening cement and like |
| JPS5411331A (en) * | 1977-06-28 | 1979-01-27 | Kubota Ltd | Glass fibers for reinforcing cement |
| JPS5711853A (en) * | 1980-06-04 | 1982-01-21 | Ppg Industries Inc | Water sizing composition,manufacture thereof, glass fiber sized therewith,manufacture thereof and polymer material reinforced with said glass fiber |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006199972A (en) * | 2001-10-23 | 2006-08-03 | Fiber Glass Japan Co Ltd | Chopped strands and molded product of unsaturated polyester resin bmc employing them |
| JP2008520849A (en) * | 2004-11-18 | 2008-06-19 | オウェンス コーニング ファイバーグラス テクノロジー インコーポレイテッド | Nonwoven fabric with improved structure, sound absorption and thermal properties |
| CN115160714A (en) * | 2022-07-21 | 2022-10-11 | 武汉理工大学 | Microwave composite dielectric substrate for high-frequency and high-speed environment and preparation method and application thereof |
| CN115160714B (en) * | 2022-07-21 | 2023-07-14 | 武汉理工大学 | Microwave composite dielectric substrate for high-frequency and high-speed environment and preparation method and application thereof |
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