JPH08119682A - Primary sizing agent for glass fiber and glass fiber stuck with the agent - Google Patents
Primary sizing agent for glass fiber and glass fiber stuck with the agentInfo
- Publication number
- JPH08119682A JPH08119682A JP6274265A JP27426594A JPH08119682A JP H08119682 A JPH08119682 A JP H08119682A JP 6274265 A JP6274265 A JP 6274265A JP 27426594 A JP27426594 A JP 27426594A JP H08119682 A JPH08119682 A JP H08119682A
- Authority
- JP
- Japan
- Prior art keywords
- sizing agent
- water
- epoxy resin
- glass fiber
- soluble epoxy
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
- C03C25/10—Coating
- C03C25/24—Coatings containing organic materials
- C03C25/26—Macromolecular compounds or prepolymers
- C03C25/32—Macromolecular compounds or prepolymers obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
- C03C25/36—Epoxy resins
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、ガラスクロスを製織す
る際に必要な一次サイズ剤に関連し、良好な製織性及び
脱油性を持ち、かつマイグレーションを起こしにくいガ
ラス繊維用一次サイズ剤及びそれを付着させたガラス繊
維に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a primary sizing agent required for weaving glass cloth, which has good weavability and deoiling property and is resistant to migration, and a primary sizing agent for glass fiber. And glass fibers having the same attached thereto.
【０００２】[0002]
【従来の技術】通常、ガラスクロスは、澱粉系の集束剤
を施されたガラス繊維を用いて製織される。澱粉系集束
剤を使用したガラスクロスの場合、エポキシ樹脂やポリ
エステル樹脂との親和性をよくする為に加熱による脱油
を行う必要がある。しかしこの加熱脱油はガラス繊維の
性能を低下させる欠点がある。2. Description of the Related Art Generally, glass cloth is woven using glass fibers having a starch-based sizing agent. In the case of a glass cloth using a starch-based sizing agent, it is necessary to remove oil by heating in order to improve the affinity with epoxy resins and polyester resins. However, this heat deoiling has a drawback that the performance of glass fiber is deteriorated.
【０００３】これに対し加熱脱油ではなく水洗により脱
油する方法が開発されている。これは集束剤として水溶
性エポキシ樹脂を使用するものであり、水洗いにより容
易に脱油する事が可能である。しかしこの水溶性エポキ
シ樹脂集束剤はマイグレーションし易いという欠点があ
る。マイグレーションとは、糊付けされチューブ等に巻
き付けられたガラス繊維（以下ケーキと表す）の表層
に、蒸発する水分によって集束剤が集中する現象であ
る。On the other hand, a method of deoiling by washing with water instead of deoiling by heating has been developed. This uses a water-soluble epoxy resin as a sizing agent, and can be easily deoiled by washing with water. However, this water-soluble epoxy resin sizing agent has a drawback that it easily migrates. The migration is a phenomenon in which the sizing agent is concentrated on the surface layer of glass fiber (hereinafter referred to as a cake) which is glued and wound around a tube or the like due to evaporated water.
【０００４】マイグレーションを起こしやすい一次サイ
ズ剤の場合、表層の集束剤付着率は、中央部と比較する
と１０倍以上となる。マイグレーションしたガラス繊維
を用いて製織したクロスはＦＲＰ（繊維補強プラスチッ
ク）とする際、含浸不良等の要因となりＦＲＰの特性は
低下する。In the case of a primary sizing agent which is prone to migration, the sizing agent adhesion rate on the surface layer is 10 times or more as compared with the central portion. When a cloth woven using migrated glass fibers is used as FRP (fiber reinforced plastic), it causes impregnation failure and the like, and the characteristics of FRP deteriorate.
【０００５】[0005]
【発明が解決しようとする課題】解決しようとする課題
は、良好な製織性、及び洗浄性を保ちつつ、マイグレー
ションを起こしにくい一次サイズ剤及びそれを付着させ
たガラス繊維の開発である。The problem to be solved is to develop a primary sizing agent that is resistant to migration while maintaining good weavability and washability, and a glass fiber to which it is attached.
【０００６】[0006]
【課題を解決するための手段】本発明は、一次サイズの
ｐＨを調節し、水溶性エポキシ樹脂の水溶性を変化させ
る事によって前記課題の解決を図ったものである。即
ち、本発明は、少なくとも水溶性エポキシ樹脂を含みか
つｐＨが５．５ー７．５であることを特徴とする一次サ
イズ剤であり、少なくとも水溶性エポキシ樹脂を含みか
つｐＨが５．５ー７．５で、該水溶性エポキシ樹脂が会
合し直径０．５ー５０μｍの粒子を形成している一次サ
イズ剤を付着させたことを特徴とするガラス繊維であ
る。一次サイズ剤のｐＨは５．５ー７．５である必要が
ある。ｐＨが５．５未満であると水溶性エポキシ樹脂が
分子レベルまで溶解し、マイグレーションが大きくな
り、７．５より大きいと溶解性が低下しサイズ調合時、
水溶性エポキシ樹脂が沈殿してしまう。The present invention is intended to solve the above-mentioned problems by adjusting the pH of the primary size and changing the water solubility of the water-soluble epoxy resin. That is, the present invention is a primary sizing agent characterized by containing at least a water-soluble epoxy resin and having a pH of 5.5-7.5, containing at least a water-soluble epoxy resin and having a pH of 5.5-. At 7.5, the glass fiber is characterized in that the water-soluble epoxy resin is associated with a primary sizing agent forming particles having a diameter of 0.5 to 50 μm. The pH of the primary size should be 5.5-7.5. If the pH is less than 5.5, the water-soluble epoxy resin will dissolve to the molecular level and migration will increase, and if it is greater than 7.5, the solubility will decrease and during size preparation,
Water-soluble epoxy resin precipitates.
【０００７】一次サイズ剤のｐＨを５．５ー７．５に調
整する手段としては酢酸、ギ酸等の酸を用いて調整する
方法を用いる。一次サイズの調合時、酸を調合液に投入
する方法と、あらかじめ水溶性エポキシ樹脂に酸を投入
する方法があるが、どちらの方法を用いてもかまわな
い。As a means for adjusting the pH of the primary sizing agent to 5.5-7.5, a method of adjusting with an acid such as acetic acid or formic acid is used. When preparing the primary size, there are a method of adding an acid to the preparation liquid and a method of previously adding an acid to the water-soluble epoxy resin, but either method may be used.
【０００８】水溶性エポキシ樹脂の添加量は一次サイズ
剤に対して１ー２重量％とする事が望ましい。２％より
添加量が多いと一次サイズ剤調合後、放置すると水溶性
エポキシ樹脂が沈殿してしまう場合がある。又、１％よ
り低いと集束力が充分でなくガラス繊維に糊付けした場
合、毛羽が発生しやすい。The amount of the water-soluble epoxy resin added is preferably 1-2% by weight based on the primary sizing agent. If the added amount is more than 2%, the water-soluble epoxy resin may precipitate when left standing after the primary sizing agent is prepared. On the other hand, if it is less than 1%, the bundling force is not sufficient and fluff tends to occur when glued to the glass fiber.
【０００９】エポキシ樹脂を水溶化する手段としてはジ
エタノールアミン等のアミンと反応させてエポキシ樹脂
にアミン付加する方法、エチレングリコール、グリセリ
ン、ポリエチレングリコールと反応させること等を例示
することができる。エポキシ樹脂とジエタノールアミン
とを反応させて水溶化する場合、エポキシ樹脂１モルに
対してジエタノールアミン０．５ー２モルを反応させる
事が望ましい。エポキシ樹脂としては、ビスフェノール
Ａ型、ノボラック型、脂肪族エポキシ樹脂、グリシジル
エステル型、臭素化エポキシ樹脂等を例示する事ができ
るが、いずれのエポキシ樹脂でもかまわない。Examples of means for solubilizing the epoxy resin include a method of reacting with an amine such as diethanolamine to add an amine to the epoxy resin, and a method of reacting with ethylene glycol, glycerin or polyethylene glycol. When the epoxy resin is reacted with diethanolamine to be water-soluble, it is desirable to react 0.5-2 mol of diethanolamine with respect to 1 mol of the epoxy resin. Examples of the epoxy resin include bisphenol A type, novolac type, aliphatic epoxy resin, glycidyl ester type and brominated epoxy resin, but any epoxy resin may be used.
【００１０】本発明の一次サイズ剤には上記必須成分の
他に、表面処理剤、潤滑成分、帯電防止剤等の成分を好
適に添加することができ、本発明の一次サイズ剤の効果
を阻害しなければいかなる他の成分をも添加することが
できる。表面処理剤、潤滑成分、帯電防止剤の場合、水
溶性エポキシ樹脂に対し、０．１ー １重量％程度添加
する事が好ましい。好ましい表面処理剤としてはアミノ
シラン、ジアミノシラン、カチオニックシラン、環状エ
ポキシシラン、グリシドキシシラン、メルカプトシラ
ン、クロロシラン、ウレイドシラン、イミダゾールシラ
ン、ビニルシラン、メタクロリキシシラン等を例示する
ことができるが、複合材料中のマトリクスとの接着性が
良好なものであればいかなるものでも用いる事ができ
る。潤滑成分は、ブチルステアレートが好ましく、帯電
防止剤は、四級アンモニウム塩を用いる事が望ましい。In addition to the above-mentioned essential components, the primary sizing agent of the present invention can be suitably added with components such as a surface treating agent, a lubricating component and an antistatic agent, which hinders the effect of the primary sizing agent of the present invention. If not, any other ingredient can be added. In the case of the surface treatment agent, the lubricant component, and the antistatic agent, it is preferable to add about 0.1 to 1% by weight to the water-soluble epoxy resin. Preferred surface treatment agents include aminosilane, diaminosilane, cationic silane, cyclic epoxysilane, glycidoxysilane, mercaptosilane, chlorosilane, ureidosilane, imidazolesilane, vinylsilane, methacryloxysilane, and the like. Any material having good adhesiveness to the matrix in the material can be used. Butyl stearate is preferably used as the lubricating component, and a quaternary ammonium salt is preferably used as the antistatic agent.
【００１１】本発明の一次サイズ剤は、有効成分１ー３
重量％の範囲で水系の調合液として使用されることが好
ましく、ガラス繊維に対する付着率としては、０．１ー
１重量％が好ましく、特に好ましくは、０．１５ー０．
３０重量％である。The primary sizing agent of the present invention comprises the active ingredient 1-3.
It is preferably used as an aqueous preparation liquid in the range of 0.1 wt%, and the adhesion rate to glass fiber is preferably 0.1-1 wt%, particularly preferably 0.15-0.
It is 30% by weight.
【００１２】[0012]
【作用】本発明のガラス繊維は、製織性に極めて優れ、
水洗処理によりガラス繊維に付着した一次サイズ剤は、
極めて容易に除去できる優れた洗浄性を持ち、なおかつ
マイグレーションが低く抑えられる特徴を持つ。この優
れた性能は、下記の理由によるものと推定している。一
次サイズ剤のｐＨが５．５より低い場合、水溶性エポキ
シ樹脂は、分子レベルまで溶解するが、５．５以上とな
ると水溶性エポキシ樹脂は、分子レベルまで溶解できず
会合し一次サイズ剤は、白濁する。この時水溶性エポキ
シ樹脂は直径０．５ー５０μｍ程度の粒子であることが
好ましく、特に好ましくは１ー５μｍの粒子のコロイド
である。０．５μｍ以下の場合マイグレーションが大き
く、５０μｍ以上の場合サイズ安定性が低下する。The glass fiber of the present invention is extremely excellent in weavability,
The primary sizing agent attached to the glass fiber by the washing treatment is
It has an excellent cleaning property that can be removed extremely easily, and has the feature that migration can be suppressed to a low level. It is estimated that this excellent performance is due to the following reasons. When the pH of the primary sizing agent is lower than 5.5, the water-soluble epoxy resin dissolves to the molecular level, but when the pH is 5.5 or more, the water-soluble epoxy resin cannot dissolve to the molecular level and the primary sizing agent is associated. , Becomes cloudy. At this time, the water-soluble epoxy resin is preferably particles having a diameter of about 0.5 to 50 μm, and particularly preferably a colloid of particles having a diameter of 1 to 5 μm. If it is 0.5 μm or less, migration is large, and if it is 50 μm or more, size stability is reduced.
【００１３】従来品と比較して会合し粒子径の大きい水
溶性エポキシ樹脂を含む本発明の一次サイズ剤は、ガラ
ス繊維に付着させケーキとして巻取った後の乾燥工程
で、水分がケーキ表層に向かって蒸発する流れと共に移
動しにくい。その為、マイグレーションは低く抑えられ
ると考えられる。The primary sizing agent of the present invention containing a water-soluble epoxy resin which is associated with and has a larger particle size than the conventional product has a water content on the surface layer of the cake in a drying step after being attached to glass fiber and wound as a cake. It is difficult to move with the evaporating flow. Therefore, it is considered that migration can be suppressed low.
【００１４】一次サイズ剤中の水溶性エポキシ樹脂の粒
子径は、大きくなるがサイズ剤の収束性、潤滑性は、驚
いたことに若干向上し、製織性に極めて優れている。Although the particle size of the water-soluble epoxy resin in the primary sizing agent increases, the sizing agent's convergence and lubricity are surprisingly slightly improved, and weavability is extremely excellent.
【００１５】ガラス繊維に付着した一次サイズ剤の水洗
処理は、通常、洗浄液に酸を０．１ー１．０重量％添加
した処理液で行われる。会合し粒子径の大きい水溶性エ
ポキシ樹脂は、水に対する溶解性が低下しているが、前
述の酸の添加により会合が解かれて水に対する溶解性が
向上し極めて容易に除去される。The washing treatment of the primary sizing agent adhered to the glass fiber with water is usually carried out with a treatment liquid prepared by adding 0.1 to 1.0% by weight of an acid to the washing liquid. The water-soluble epoxy resin having associated large particle diameter has a low solubility in water, but the addition of the above-mentioned acid breaks the association, improves the solubility in water, and is extremely easily removed.
【００１６】[0016]
【実施例】 次に実施例によって本発明をさらに詳細に
説明する。EXAMPLES Next, the present invention will be described in more detail by way of examples.
【００１７】実施例１ ガラス繊維の紡糸は以下に示すようにして行い、一次サ
イズ剤をガラス繊維に付着させた。即ち電気炉で溶融し
たガラス（Ｅガラス）をプラチナノズルから引き出して
得たガラス繊維にタッチローラー方式により下記に示す
本発明の一次サイズ剤を付着させた。タッチローラー回
転数は、一次サイズ剤の付着率を考慮して設定した。そ
の後、チューブに巻き取ってケーキとし２４時間放置し
風乾した。なおケーキの巻き付け量は３．３ｋｇとし
た。ガラス繊維に対する本発明の一次サイズ剤のケーキ
全体の重量増加より求めた付着率は、０．２０重量％で
あった。 一次サイズ剤 水溶性エポキシ樹脂は、エピコート８２８（成分：ビス
フェノールＡジグリシジルエーテル１００％、油化シェ
ル化学製）１モルに２，２’’−イミノジエタノール
（和光純薬工業製）１モルを４０℃にて付加して合成し
た。この合成品１．０重量％、表面処理剤としてアミノ
プロピルトリエトキシシラン（信越化学製、商品名ＫＢ
Ｅ９０２）０．３重量％、潤滑成分としてブチルステア
レート（松本油脂製、商品名Ｅ−４Ｂ）０．５重量％及
び氷酢酸（純分９９％）０．１重量％添加し、水を加え
て１００重量％とした。Example 1 Spinning of glass fiber was carried out as follows, and a primary sizing agent was attached to the glass fiber. That is, glass (E glass) melted in an electric furnace was drawn out from a platinum nozzle, and the following primary sizing agent of the present invention was attached to the glass fiber obtained by the touch roller method. The rotation number of the touch roller was set in consideration of the adhesion rate of the primary sizing agent. Then, it was wound into a tube to form a cake, which was left for 24 hours and air-dried. The amount of cake wrapped was 3.3 kg. The adhesion rate of the primary sizing agent of the present invention to the glass fiber was 0.20% by weight, which was determined from the increase in the weight of the entire cake. Primary Sizing Agent The water-soluble epoxy resin is 1 mol of Epicoat 828 (component: bisphenol A diglycidyl ether 100%, manufactured by Yuka Shell Chemical Co., Ltd.) and 40 mol of 2,2 ″ -iminodiethanol (manufactured by Wako Pure Chemical Industries). It was added at ℃ and synthesized. 1.0% by weight of this synthetic product, aminopropyltriethoxysilane as a surface treatment agent (manufactured by Shin-Etsu Chemical, trade name KB
E902) 0.3% by weight, butyl stearate (Matsumoto Yushi Co., Ltd., trade name E-4B) 0.5% by weight and glacial acetic acid (pure 99%) 0.1% by weight as lubricating components, and water added To 100% by weight.
【００１８】実施例２ 酢酸添加量を０．０５重量％とした一次サイズ剤を用い
たこと以外は実施例１と同様にしてガラス繊維を製造し
た。ガラス繊維に対する本発明の一次サイズ剤のケーキ
全体の重量増加より求めた付着率は、０．２６重量％で
あった。Example 2 A glass fiber was produced in the same manner as in Example 1 except that a primary sizing agent containing 0.05% by weight of acetic acid was used. The adhesion rate of the primary sizing agent of the present invention to the glass fiber was 0.26% by weight, which was determined from the increase in the weight of the entire cake.
【００１９】実施例３ 実施例１の合成品を２．０重量％とした一次サイズ剤を
用いたこと以外は実施例１と同様にしてガラス繊維を製
造した。ガラス繊維に対する本発明の一次サイズ剤のケ
ーキ全体の重量増加より求めた付着率は、０．３６重量
％であった。Example 3 A glass fiber was produced in the same manner as in Example 1 except that the synthetic product of Example 1 was used in an amount of 2.0% by weight. The adhesion rate of the primary sizing agent of the present invention to the glass fiber was 0.36% by weight, which was determined by increasing the weight of the entire cake.
【００２０】実施例４ 酢酸添加量を０．０５重量％とした一次サイズ剤を用い
たこと以外は実施例３と同様にしてガラス繊維を製造し
た。ガラス繊維に対する本発明の一次サイズ剤のケーキ
全体の重量増加より求めた付着率は、０．３６重量％で
あった。Example 4 A glass fiber was produced in the same manner as in Example 3 except that a primary sizing agent containing 0.05% by weight of acetic acid was used. The adhesion rate of the primary sizing agent of the present invention to the glass fiber was 0.36% by weight, which was determined by increasing the weight of the entire cake.
【００２１】比較例１ 酢酸添加量を０重量％とした一次サイズ剤を用いたこと
以外は実施例３と同様にしてガラス繊維を製造しようと
したが一次サイズ剤に沈殿物が生成したためガラス繊維
の製造を中止した。Comparative Example 1 A glass fiber was tried to be produced in the same manner as in Example 3 except that the primary sizing agent containing 0% by weight of acetic acid was used, but a glass fiber was formed because a precipitate was formed in the primary sizing agent. Was discontinued.
【００２２】比較例２ 実施例１の合成品を３．５重量％とした一次サイズ剤を
用いたこと以外は実施例１と同様にしてガラス繊維を製
造した。ガラス繊維に対する本発明の一次サイズ剤のケ
ーキ全体の重量増加より求めた付着率は、０．４６重量
％であった。一次サイズ剤に若干沈殿が生成したが、攪
拌により再乳化しガラス繊維を製造した。そのため一次
サイズ剤の付着率が高く、製織時、緯糸の飛走性が低下
し、停台が多発した。Comparative Example 2 A glass fiber was produced in the same manner as in Example 1 except that the synthetic product of Example 1 was used in an amount of 3.5% by weight. The adhesion rate of the primary sizing agent of the present invention to the glass fiber determined by increasing the weight of the entire cake was 0.46% by weight. Although some precipitate was formed in the primary sizing agent, it was re-emulsified by stirring to produce glass fiber. Therefore, the adhesion of the primary sizing agent was high, the flying properties of the wefts were reduced during weaving, and many stoppages occurred.
【００２３】比較例３ 実施例１の合成品を０．５重量％とした一次サイズ剤を
用いたこと以外は実施例１と同様にしてガラス繊維を製
造した。ガラス繊維に対する本発明の一次サイズ剤のケ
ーキ全体の重量増加より求めた付着率は、０．２１重量
％であった。Comparative Example 3 A glass fiber was produced in the same manner as in Example 1 except that the synthetic product of Example 1 was used in an amount of 0.5% by weight. The adhesion rate determined by increasing the weight of the primary sizing agent of the present invention as a whole to the glass fiber was 0.21% by weight.
【００２４】上記、実施例及び比較例に用いた一次サイ
ズ剤の組成を表１に示す。Table 1 shows the compositions of the primary sizing agents used in the above Examples and Comparative Examples.
【００２５】ケーキの各部分の付着率測定 紡糸したガラス繊維を２４時間室温で放置した後、ケー
キの各部分から１００ｍずつサンプリングし、その重量
（ａ）を測り、６２５℃雰囲気化で３０分間放置し、ガ
ラス繊維に付着した一次サイズを燃焼させた。燃焼後、
デシケーター中で室温まで冷却し、重量（ｂ）を測定
し、下記の計算式を用いてガラス繊維の各部分の一次サ
イズ付着率を計算した。なお計算式はＪＩＳ Ｒ３４２
０−１９８９に準じた。即ち下記の式により計算した。 付着率（％）＝（ａ−ｂ）／ａ×１００ 付着率測定結果を図１に示す。図１によると本発明の一
次サイズ剤を用いることによりマイグレーションが抑制
されていることが良くわかる。Measurement of the Adhesion Rate of Each Part of the Cake After the spun glass fiber was left at room temperature for 24 hours, 100 m of each part of the cake was sampled, its weight (a) was measured, and it was left in an atmosphere of 625 ° C. for 30 minutes. Then, the primary size attached to the glass fiber was burned. After burning,
After cooling to room temperature in a desiccator, the weight (b) was measured, and the primary size attachment ratio of each part of the glass fiber was calculated using the following formula. The calculation formula is JIS R342.
0-1989. That is, it was calculated by the following formula. Adhesion rate (%) = (ab) / a × 100 The adhesion rate measurement results are shown in FIG. It can be clearly seen from FIG. 1 that migration is suppressed by using the primary sizing agent of the present invention.
【００２６】製織性 １０００ｍ製織して停台回数が１０回未満、及び織物の
毛羽が１平方メートル当たり１０本未満の物を○とす
る。１０００ｍ製織して停台回数が１０回以上２０回未
満、及び織物の毛羽が１平方メートルに２０本以下の物
を△とする。１０００ｍ製織して停台回数２０回以上の
物を×とする。Weaving property: Weaving of 1000 m, the number of stops is less than 10 times, and the number of fluffs of the woven fabric is less than 10 per square meter, which is indicated as ◯. Weaving for 1,000 m, the number of stops is 10 or more and less than 20 and the number of fluffs of the woven fabric is 20 or less per 1 square meter, and is Δ. A piece having a weaving time of 1000 m and a stop count of 20 or more is marked with x.
【００２７】サイズ安定性 一次サイズ調合後、２４時間放置して沈殿物が発生しな
いものを○とする。一次サイズ調合後、２４時間放置す
ると沈殿物が発生するが、攪拌すると再乳化するものを
△とする。一次サイズ調合後、２４時間放置すると沈殿
物が生成し、攪拌しても再乳化しないものを×とする。
上記、実施例及び比較例のガラス繊維の製織性・サイズ
安定性及び製織時の停台回数を表２に示す。Size stability After preparation of the primary size, it is allowed to stand for 24 hours and no precipitate is generated. After preparation for the primary size, a precipitate is generated when left standing for 24 hours, but what is re-emulsified when stirred is indicated as Δ. After preparation of the primary size, a precipitate is formed when left standing for 24 hours and the emulsion is not re-emulsified even with stirring.
Table 2 shows the weavability and size stability of the glass fibers of the above Examples and Comparative Examples, and the number of stops during weaving.
【００２８】[0028]
【発明の効果】以上の様に水溶性エポキシ樹脂を含む一
次サイズ剤のｐＨを５．５ー７．５に調整する事により
製織性及び織物に付着した一次サイズ剤の水洗除去性を
は良好に保ちつつ、しかも水溶性エポキシ樹脂を沈殿し
ないコロイド状の粒子径に調整しているため、本発明の
一次サイズ剤を付着させたガラス繊維のケーキは、乾燥
時のマイグレーションが低く抑えられる。従って、ケー
キの中心から表層にかけて一次サイズ剤が均一に付着し
ているため本発明の一次サイズ剤を付着させたガラス繊
維のケーキを用いた複合材料の機械的性質は優れてい
る。As described above, by adjusting the pH of the primary sizing agent containing the water-soluble epoxy resin to 5.5 to 7.5, the weaving property and the removability of the primary sizing agent adhering to the woven fabric with water can be improved. The glass fiber cake to which the primary sizing agent of the present invention is adhered can be suppressed to have low migration at the time of drying because the colloidal particle size is adjusted so that the water-soluble epoxy resin does not precipitate. Therefore, since the primary sizing agent is uniformly attached from the center of the cake to the surface layer, the mechanical properties of the composite material using the glass fiber cake to which the primary sizing agent of the present invention is attached are excellent.
【表１】 [Table 1]
【表２】 [Table 2]
─────────────────────────────────────────────────────
─────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成７年２月９日[Submission date] February 9, 1995
【手続補正１】[Procedure Amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】図面の簡単な説明[Name of item to be corrected] Brief description of the drawing
【補正方法】追加[Correction method] Added
【補正内容】[Correction content]
【図面の簡単な説明】[Brief description of drawings]
【図１】一次サイズ付着率を示す。FIG. 1 shows the primary size attachment rate.
Claims (4)
つｐＨが５．５ー７．５であることを特徴とするガラス
繊維用一次サイズ剤。1. A primary sizing agent for glass fibers, which comprises at least a water-soluble epoxy resin and has a pH of 5.5 to 7.5.
む請求項１記載のガラス繊維用一次サイズ剤。2. The primary sizing agent for glass fibers according to claim 1, which contains 1-2% by weight of a water-soluble epoxy resin.
ー５０μｍの粒子を形成している請求項１記載のガラス
繊維用一次サイズ剤。3. A water-soluble epoxy resin associates with a diameter of 0.5.
The primary sizing agent for glass fibers according to claim 1, which has a particle size of -50 μm.
つｐＨが５．５ー７．５で、該水溶性エポキシ樹脂が会
合し直径０．５ー５０μｍの粒子を形成している一次サ
イズ剤を付着させたことを特徴とするガラス繊維4. A primary sizing agent containing at least a water-soluble epoxy resin and having a pH of 5.5 to 7.5, which is associated with the water-soluble epoxy resin to form particles having a diameter of 0.5 to 50 μm. Glass fiber characterized by
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6274265A JPH08119682A (en) | 1994-10-14 | 1994-10-14 | Primary sizing agent for glass fiber and glass fiber stuck with the agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6274265A JPH08119682A (en) | 1994-10-14 | 1994-10-14 | Primary sizing agent for glass fiber and glass fiber stuck with the agent |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH08119682A true JPH08119682A (en) | 1996-05-14 |
Family
ID=17539266
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6274265A Pending JPH08119682A (en) | 1994-10-14 | 1994-10-14 | Primary sizing agent for glass fiber and glass fiber stuck with the agent |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH08119682A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003089953A (en) * | 2001-09-14 | 2003-03-28 | Nippon Glass Fiber Kogyo Kk | Heat-resistant glass fiber mat and method of producing the same |
| US6610400B2 (en) | 1999-05-28 | 2003-08-26 | Ppg Industries Ohio, Inc. | Sizing compositions, methods and apparatus for cleaning sized fiber glass strands, yarns and fabrics |
| EP1426348A1 (en) * | 2002-12-05 | 2004-06-09 | Cognis Deutschland GmbH & Co. KG | Use of epoxy resins for coating of glass |
| JP2015028158A (en) * | 2013-07-05 | 2015-02-12 | 三洋化成工業株式会社 | Aqueous epoxy resin composition |
| WO2016103875A1 (en) * | 2014-12-25 | 2016-06-30 | Dic株式会社 | Fiber bundling agent |
-
1994
- 1994-10-14 JP JP6274265A patent/JPH08119682A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6610400B2 (en) | 1999-05-28 | 2003-08-26 | Ppg Industries Ohio, Inc. | Sizing compositions, methods and apparatus for cleaning sized fiber glass strands, yarns and fabrics |
| JP2003089953A (en) * | 2001-09-14 | 2003-03-28 | Nippon Glass Fiber Kogyo Kk | Heat-resistant glass fiber mat and method of producing the same |
| EP1426348A1 (en) * | 2002-12-05 | 2004-06-09 | Cognis Deutschland GmbH & Co. KG | Use of epoxy resins for coating of glass |
| JP2015028158A (en) * | 2013-07-05 | 2015-02-12 | 三洋化成工業株式会社 | Aqueous epoxy resin composition |
| WO2016103875A1 (en) * | 2014-12-25 | 2016-06-30 | Dic株式会社 | Fiber bundling agent |
| JPWO2016103875A1 (en) * | 2014-12-25 | 2017-04-27 | Dic株式会社 | Fiber sizing agent |
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