JP5405871B2 - Glass fiber sizing agent and glass fiber bundle - Google Patents
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Description
本発明は、ガラス繊維用集束剤及びガラス繊維束に関するものである。 The present invention relates to a sizing agent for glass fibers and a glass fiber bundle.
従来、ガラス繊維用集束剤としては、例えば、澱粉、環状炭化水素の澱粉エーテルもしくはエステルまたはそれらの置換誘導体、及びワックス及び又は疎水性ゲル−形成物質からなり、破裂していない澱粉粒子を含有することを特徴とするガラス繊維用サイズ（特許文献１）、糊化後の平均粒子径が０．５〜１０ミクロン、粘度が５％、５０℃において８０センチポイズ以下を示す架橋エーテル化デンプンを被膜形成剤とすることを特徴とするガラス繊維用水分散性集束剤（特許文献２）が知られている。 Conventional sizing agents for glass fibers include, for example, starch, starch ethers or esters of cyclic hydrocarbons or substituted derivatives thereof, and wax particles and / or hydrophobic gel-forming substances that contain unruptured starch particles. Glass fiber size (Patent Document 1), average particle diameter after gelatinization of 0.5 to 10 microns, viscosity of 5%, forming a film of crosslinked etherified starch showing 80 centipoise or less at 50 ° C A water-dispersible sizing agent for glass fibers (Patent Document 2) is known, which is characterized by using an agent.
しかしながら、上記特許文献に記載されているような従来のガラス繊維用集束剤は、ガラス繊維（以下「フィラメント」と呼ぶ場合がある）同士の摩擦を抑制する効果が小さく、製織時にガラス繊維の糸切れ、毛羽立ちが起きるという問題があった。例えば、特許文献１には、糊化率が低く粒子が残る澱粉と第２のフィルム形成剤を含むガラス繊維用サイズが開示されているが、フィラメント間の摩擦を抑制する効果が小さかった。また、特許文献２のガラス繊維用水分散性集束剤は、フィルム形成剤として１種の澱粉のみを含有するものであり、フィラメント間の摩擦を抑制する効果を特に高めたものではなかった。 However, the conventional glass fiber sizing agent as described in the above-mentioned patent document has a small effect of suppressing friction between glass fibers (hereinafter sometimes referred to as “filaments”), and the yarn of the glass fiber during weaving. There was a problem of cutting and fluffing. For example, Patent Document 1 discloses a glass fiber size containing starch and a second film-forming agent having a low gelatinization rate and particles remaining, but the effect of suppressing friction between filaments was small. Moreover, the water-dispersible sizing agent for glass fiber of Patent Document 2 contains only one kind of starch as a film forming agent, and has not particularly enhanced the effect of suppressing friction between filaments.
そこで、本発明の目的は、製織時のガラス繊維の糸切れ、毛羽立ちを減少させるガラス繊維用集束剤、及びこのガラス繊維用集束剤を用いたガラス繊維束を提供することにある。 Therefore, an object of the present invention is to provide a glass fiber sizing agent that reduces the breakage and fluffing of glass fibers during weaving, and a glass fiber bundle using the glass fiber sizing agent.
本発明は、フィルム形成剤、潤滑剤及び水を含有するガラス繊維用集束剤であって、フィルム形成剤は、糊化率５〜２５重量％の第１の澱粉、及び糊化率５０〜８０重量％且つアミロペクチンの含有率が７０〜９５重量％の第２の澱粉、を含有する、ガラス繊維用集束剤を提供する。 The present invention is a glass fiber sizing agent containing a film forming agent, a lubricant and water, wherein the film forming agent comprises a first starch having a gelatinization rate of 5 to 25% by weight and a gelatinization rate of 50 to 80. There is provided a glass fiber sizing agent comprising a second starch having a weight percent of amylopectin content of 70 to 95 weight percent.
本発明のガラス繊維用集束剤においては、第１の澱粉の糊化率が所定の低い値に制御されていることから、フィラメント間に澱粉粒子が残りやすくなり、フィラメント同士の摩擦を抑制することができる。また、第２の澱粉の糊化率が所定の高い値に制御されており、アミロペクチンの含有率も高いことから、柔軟な被膜を形成することができる。よって、本発明のガラス繊維用集束剤は、製織時のガラス繊維の糸切れ、毛羽立ちを効果的に減少させることができる。 In the sizing agent for glass fibers of the present invention, since the gelatinization rate of the first starch is controlled to a predetermined low value, starch particles are likely to remain between the filaments and suppress friction between the filaments. Can do. Further, since the gelatinization rate of the second starch is controlled to a predetermined high value and the content of amylopectin is high, a flexible coating can be formed. Therefore, the glass fiber sizing agent of the present invention can effectively reduce yarn breakage and fluffing of the glass fiber during weaving.
ここで、第１の澱粉は架橋米澱粉であることが好ましい。架橋米澱粉は、その架橋構造により加熱時の膨潤と溶解が抑制されるため、フィラメント間に粒子として介在しやすくなり、フィラメント間の摩擦がより防止されやすくなる。 Here, the first starch is preferably cross-linked rice starch. Cross-linked rice starch is less likely to swell and dissolve during heating due to its cross-linked structure, so that it is more likely to intervene as particles between filaments, and friction between filaments is more easily prevented.
第１の澱粉は、糊化後の平均粒径が１〜１２μｍの澱粉であることが好ましい。 The first starch is preferably starch having an average particle size after gelatinization of 1 to 12 μm.
このような糊化後の平均粒径の第１の澱粉を含有するガラス繊維用集束剤は、フィラメント間の間隔をより保ちやすくし、フィラメント間の摩擦をより抑制することができる。 The sizing agent for glass fibers containing the first starch having the average particle diameter after gelatinization can more easily maintain the interval between the filaments and can further suppress the friction between the filaments.
第２の澱粉は、馬鈴薯澱粉又はタピオカ澱粉であることが好ましい。 The second starch is preferably potato starch or tapioca starch.
馬鈴薯澱粉又はタピオカ澱粉は、アミロペクチンの含有率が高く、柔軟性があるため、これらを含むガラス繊維用集束剤で処理したガラス繊維も柔軟性が高くなり、製織時の毛羽立ちを効果的に減少させることができる。 Since potato starch or tapioca starch has a high content of amylopectin and is flexible, glass fibers treated with a glass fiber sizing agent containing these also have high flexibility, effectively reducing fuzz during weaving. be able to.
第１の澱粉の含有量は、第２の澱粉の含有量よりも多いことが好ましい。 The content of the first starch is preferably larger than the content of the second starch.
第１の澱粉の含有量が第２の澱粉の含有量よりも多いことによって、フィラメント間の間隔をより保ちやすくし、フィラメント間の摩擦を抑制する効果がより高まる。 When the content of the first starch is larger than the content of the second starch, it is easier to keep the interval between the filaments, and the effect of suppressing the friction between the filaments is further enhanced.
第１の澱粉及び第２の澱粉の全重量は、ガラス繊維用集束剤の全重量の２．０〜７．０重量％であることが好ましい。 The total weight of the first starch and the second starch is preferably 2.0 to 7.0% by weight of the total weight of the glass fiber sizing agent.
このような組成のガラス繊維集束剤は、製織時の糸切れ、毛羽立ちがより減少できる。 The glass fiber sizing agent having such a composition can further reduce yarn breakage and fluffing during weaving.
また、本発明は、上記ガラス繊維集束剤によりガラス繊維を集束させてなる、ガラス繊維束を提供する。 Moreover, this invention provides the glass fiber bundle formed by bundling glass fiber with the said glass fiber bundling agent.
本発明により、製織時のガラス繊維の糸切れ、毛羽立ちを減少させるガラス繊維用集束剤、及びこのガラス繊維用集束剤を用いたガラス繊維束を提供することができる。 INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a glass fiber sizing agent that reduces glass fiber yarn breakage and fuzz during weaving, and a glass fiber bundle using the glass fiber sizing agent.
以下に、本発明のガラス繊維用集束剤の好適な実施形態について詳細に説明する。 Below, suitable embodiment of the sizing agent for glass fibers of this invention is described in detail.
ガラス繊維用集束剤は、フィルム形成剤として２種類の澱粉を特定比率で含有するが、フィルム形成剤として使用する２種類の澱粉とは、糊化率５〜２５重量％の第１の澱粉と、糊化率５０〜８０重量％且つアミロペクチンの含有率が７０〜９５重量％の第２の澱粉である。 The glass fiber sizing agent contains two types of starch as a film forming agent in a specific ratio, and the two types of starch used as a film forming agent are the first starch having a gelatinization rate of 5 to 25% by weight. The second starch has a gelatinization rate of 50 to 80% by weight and an amylopectin content of 70 to 95% by weight.
澱粉としては、例えば、米澱粉、馬鈴薯澱粉、タピオカ澱粉などの植物由来の澱粉が挙げられる。また、架橋が導入された架橋米澱粉なども使用することができる。 Examples of the starch include plant-derived starches such as rice starch, potato starch and tapioca starch. Cross-linked rice starch introduced with cross-linking can also be used.
「澱粉の糊化」とは、澱粉を水中に懸濁して加熱すると、結晶構造を有する澱粉分子の隙間に水分子が入り込んで、その構造が緩み、澱粉粒が膨張して崩壊し、ゲル状に変化することをいう。例えば、容量１００リットル程度の容器にイオン交換水７０ｋｇを投入し、さらに澱粉３．５ｋｇをイオン交換水中に分散させ、攪拌しながら９４℃まで昇温し、３０分間保温することによって、澱粉を糊化させることができる。その後、７０℃まで冷却することによって、糊化した澱粉を保存することができる。 “Starch gelatinization” means that when starch is suspended in water and heated, water molecules enter the gaps between the starch molecules having a crystalline structure, the structure loosens, the starch granules expand and collapse, and form a gel. It means to change to. For example, 70 kg of ion-exchanged water is put into a container having a capacity of about 100 liters, and further 3.5 kg of starch is dispersed in ion-exchanged water, heated to 94 ° C. with stirring, and kept warm for 30 minutes to paste the starch. It can be made. Then, gelatinized starch can be preserve | saved by cooling to 70 degreeC.
澱粉の糊化率は、例えば、以下の方法で測定することができる。すなわち、上述の方法で糊化した澱粉を試料として１０ｇ程度採取し、その試料の重量を測定する。重量測定後、遠心分離機を用い、４８００ｒｐｍで３０分間遠心分離する。遠心分離後、上澄み液を分離し、その上澄み液中の固形分の重量を測定する。糊化率は以下の式で求めることができる。
糊化率＝（遠心分離後の上澄み液中の固形分の重量）／（遠心分離前の試料の重量）×１００（％）
The gelatinization rate of starch can be measured, for example, by the following method. That is, about 10 g of the starch gelatinized by the above-mentioned method is collected as a sample, and the weight of the sample is measured. After the weight measurement, the sample is centrifuged at 4800 rpm for 30 minutes using a centrifuge. After centrifugation, the supernatant is separated and the weight of the solid content in the supernatant is measured. The gelatinization rate can be obtained by the following formula.
Gelatinization rate = (weight of solid content in supernatant after centrifugation) / (weight of sample before centrifugation) × 100 (%)
第１の澱粉は、糊化率が５〜２５重量％の澱粉であり、糊化後も膨潤した粒子状の澱粉が多く残るため、このような澱粉を含むフィルム形成剤は、フィラメント間の間隔を保つことができ、フィラメント同士の摩擦を抑制する機能を有する。第１の澱粉は、糊化率が１０〜２０重量％の澱粉が好ましく、糊化率が１５〜２０重量％の澱粉がより好ましい。 The first starch is a starch having a gelatinization rate of 5 to 25% by weight, and a large amount of swollen granular starch remains even after gelatinization. Therefore, the film forming agent containing such a starch has a spacing between filaments. And has a function of suppressing friction between filaments. The first starch is preferably starch having a gelatinization rate of 10 to 20% by weight, and more preferably starch having a gelatinization rate of 15 to 20% by weight.
糊化率が５重量％未満の澱粉は、糊化後もほとんど膨潤しないことから、外力が加わった際の形状変化が小さく、フィラメントの束である繊維が硬くなる傾向にある。また、糊化率が２５重量％より高い澱粉は、フィルムを形成しやすいので、フィラメント同士を貼付してしまう割合が高い傾向にあり、貼付されたフィラメント同士が外力により裂けると、フィラメント同士が接触していた部分は保護する層がないので、フィラメントが切れやすくなる傾向にある。 Starch having a gelatinization rate of less than 5% by weight hardly swells even after gelatinization, so that the change in shape when an external force is applied is small, and the fibers that are bundles of filaments tend to be hard. In addition, starch with a gelatinization rate higher than 25% by weight tends to form a film, so the rate of sticking the filaments tends to be high, and if the applied filaments tear due to external force, the filaments contact each other Since there is no protective layer, the filaments tend to break easily.
第１の澱粉は、架橋米澱粉であることも好ましい。米澱粉を架橋した架橋米澱粉は、２ヶ所以上の水酸基間に多官能基を結合させた誘導体であり、その架橋構造により加熱時の膨潤と溶解が抑制されることから、糊化後も粒子の形状が残り、フィラメント間の間隔を保ちやすい。 It is also preferred that the first starch is a crosslinked rice starch. Cross-linked rice starch is a derivative in which polyfunctional groups are bonded between two or more hydroxyl groups, and its cross-linked structure prevents swelling and dissolution during heating. This keeps the shape between the filaments easy to maintain.
また、第１の澱粉は、糊化後の平均粒径が１〜１２μｍである澱粉が好ましい。より好ましくは、糊化後の平均粒径が８〜１２μｍであり、さらに好ましくは、糊化後の平均粒径が９〜１１μｍである。 The first starch is preferably starch having an average particle size of 1 to 12 μm after gelatinization. More preferably, the average particle size after gelatinization is 8 to 12 μm, and more preferably, the average particle size after gelatinization is 9 to 11 μm.
糊化後の平均粒径が１μｍ未満の澱粉では、フィラメント間の間隔が狭くなってしまい、糊化した第２の澱粉がフィラメント間に入り込み、フィラメント同士を貼付してしまうおそれが高くなる傾向にある。また、糊化後の平均粒径が１２μｍより大きい澱粉では、糊化後膨潤した澱粉粒子に外力が加わった際の形状変化が大きくなり、フィラメントを集束させにくくなる傾向にある。 In starch having an average particle size of less than 1 μm after gelatinization, the interval between the filaments is narrowed, and the second starch that has been gelatinized tends to enter between the filaments and stick to the filaments. is there. In addition, starch having an average particle size after gelatinization of more than 12 μm tends to make it difficult to bundle filaments when the external force is applied to starch particles swollen after gelatinization.
第２の澱粉は、上述のとおり、糊化率が５０〜８０重量％であり、且つアミロペクチンの含有率が７０〜９５重量％の澱粉であり、糊化率が５０〜８０重量％と高いため、フィルム形成剤としてフィラメントを被膜する機能に優れ、アミロペクチンの含有率が７０〜９５重量％であるためフィルム形成剤として柔軟性が高くなり、フィラメントが集束したガラス繊維束の柔軟性が高まる。 As described above, the second starch is a starch having a gelatinization rate of 50 to 80% by weight and an amylopectin content of 70 to 95% by weight, and has a high gelatinization rate of 50 to 80% by weight. The film forming agent is excellent in function of coating a filament, and since the amylopectin content is 70 to 95% by weight, the film forming agent is highly flexible, and the flexibility of the glass fiber bundle in which the filaments are gathered is increased.
第２の澱粉は、より好ましくは、糊化率が５０〜７０重量％であり、且つアミロペクチンの含有率が７０〜８０重量％の澱粉である。このような澱粉は、フィラメントを被膜する機能にさらに優れ、フィラメントが集束したガラス繊維束の柔軟性もより高まる。 The second starch is more preferably a starch having a gelatinization rate of 50 to 70% by weight and an amylopectin content of 70 to 80% by weight. Such starch is further excellent in the function of coating the filament, and the flexibility of the glass fiber bundle in which the filaments are gathered is further increased.
第２の澱粉として糊化率が５０重量％未満の澱粉は、皮膜の形成が十分に行わない傾向にあり、また糊化率が８０重量％より高い澱粉は、マイグレーションが発生しやすくなる傾向にある。 As the second starch, starch having a gelatinization rate of less than 50% by weight tends not to form a film sufficiently, and starch having a gelatinization rate higher than 80% by weight tends to cause migration. is there.
第２の澱粉として、アミロペクチンの含有率が７０重量％未満の澱粉は、柔軟性が低く、ガラス繊維ヤーンの柔軟性も低くなるので、エアージェット織機で製織する際に糸切れや毛羽立ちが発生しやすくなる傾向にある。また、アミロペクチンの含有率が９５重量％より高い澱粉は、柔らかくなりすぎ、フィラメントを集束する力が小さくなる傾向にある。 As the second starch, starch having an amylopectin content of less than 70% by weight has low flexibility and low flexibility of the glass fiber yarn. Therefore, when weaving with an air jet loom, thread breakage and fluffing occur. It tends to be easier. Further, starch having an amylopectin content higher than 95% by weight tends to be too soft, and the force for converging filaments tends to be small.
第２の澱粉は、馬鈴薯澱粉又はタピオカ澱粉が好ましい。馬鈴薯澱粉及びタピオカ澱粉はアミロペクチンの含有率が約８０％と高く、柔軟性に優れる。 The second starch is preferably potato starch or tapioca starch. Potato starch and tapioca starch have a high amylopectin content of about 80% and are excellent in flexibility.
ガラス繊維集束剤は、第１の澱粉の含有量が、第２の澱粉の含有量よりも多いことが好ましい。第１の澱粉の含有量が多いことによって、フィルム形成剤としてフィラメント間の間隔を保つ粒子状の澱粉が多くなり、フィラメント間の摩擦をより抑制することができるからである。より好ましくは、第１の澱粉の含有量と、第２の澱粉の含有量の重量比が、５：１〜５：４の範囲にあるガラス繊維集束剤である。 In the glass fiber sizing agent, the content of the first starch is preferably larger than the content of the second starch. This is because when the content of the first starch is large, the amount of particulate starch that keeps the distance between the filaments as a film forming agent increases, and friction between the filaments can be further suppressed. More preferably, the glass fiber sizing agent has a weight ratio of the first starch content to the second starch content in the range of 5: 1 to 5: 4.
第２の澱粉の含有量が第１の澱粉の含有量より多くなると、フィルム形成剤として、フィラメント同士の間隔を保つ粒子状の澱粉が少なくなり、フィラメントの摩擦を抑制する効果が小さくなる傾向にある。 When the content of the second starch is greater than the content of the first starch, the amount of particulate starch that keeps the spacing between the filaments decreases as the film forming agent, and the effect of suppressing the friction of the filaments tends to decrease. is there.
また、ガラス繊維集束剤は、第１の澱粉及び第２の澱粉の全重量が、ガラス繊維用集束剤の全重量の２．０〜７．０重量％であることが好ましい。ガラス繊維集束剤全重量の２．０〜７．０重量％が、第１の澱粉及び第２の澱粉からなるフィルム形成剤であることによって、第１の澱粉がフィラメント間の間隔を保持してフィラメント同士の摩擦を抑制し、第２の澱粉がフィラメント表面に皮膜を形成することで、フィラメント表面の保護と第１の澱粉の粒子をフィラメント表面に固着させるという効果を有する。 In the glass fiber sizing agent, the total weight of the first starch and the second starch is preferably 2.0 to 7.0% by weight of the total weight of the glass fiber sizing agent. Since 2.0 to 7.0% by weight of the total weight of the glass fiber sizing agent is a film forming agent composed of the first starch and the second starch, the first starch maintains the spacing between the filaments. The friction between the filaments is suppressed, and the second starch forms a film on the filament surface, thereby providing an effect of protecting the filament surface and fixing the first starch particles to the filament surface.
第１の澱粉及び第２の澱粉の全重量は、ガラス繊維用集束剤の全重量の２．５〜６．０重量％であることがより好ましく、ガラス繊維用集束剤の全重量の３．０〜５．０重量％であることがさらに好ましい。 The total weight of the first starch and the second starch is more preferably 2.5 to 6.0% by weight of the total weight of the glass fiber sizing agent, and 3% of the total weight of the glass fiber sizing agent. More preferably, it is 0 to 5.0% by weight.
第１の澱粉及び第２の澱粉の全重量が、ガラス繊維集束剤全重量の２．０重量％より小さいと、フィルム形成剤のフィラメントへの付着量が少ないので、フィラメント同士の摩擦の抑制の効果が小さくなる傾向にある。一方、ガラス繊維集束剤全重量の７．０重量％より大きいと、フィルム形成剤のフィラメントへの付着量が多くなりすぎ、フィラメント同士の摩擦の抑制の効果が得られにくくなる傾向にある。 If the total weight of the first starch and the second starch is less than 2.0% by weight of the total weight of the glass fiber sizing agent, the amount of film-forming agent adhering to the filament is small. The effect tends to be small. On the other hand, if it is larger than 7.0% by weight of the total weight of the glass fiber sizing agent, the amount of the film-forming agent attached to the filaments is excessive, and the effect of suppressing friction between the filaments tends to be difficult to obtain.
また、ガラス繊維集束剤に含有される潤滑剤としては、変性シリコーンオイル、牛脂等の動物油及びこの水素添加物、大豆油、ヤシ油、ナタネ油、パーム油等の植物油及びこの水素添加物、高級飽和脂肪酸と高級飽和アルコールの縮合物（ラウリルステアレート等のステアリン酸エステル等）、パラフィンワックス等が挙げられる。この中でも、パーム油及びパラフィンワックスが潤滑剤として好ましい。 The lubricant contained in the glass fiber sizing agent includes animal oils such as modified silicone oil and beef tallow, and hydrogenated products thereof, vegetable oils such as soybean oil, coconut oil, rapeseed oil, and palm oil, and hydrogenated products thereof. Examples include condensates of saturated fatty acids and higher saturated alcohols (stearic acid esters such as lauryl stearate), paraffin wax and the like. Among these, palm oil and paraffin wax are preferable as the lubricant.
潤滑剤の含有率は、ガラス繊維用集束剤の全重量を基準として、０．５〜３．０重量％が好ましい。 The content of the lubricant is preferably 0.5 to 3.0% by weight based on the total weight of the sizing agent for glass fibers.
潤滑剤は、１種を単独で又は２種以上を適宜混合して使用することができる。 One type of lubricant can be used alone, or two or more types can be appropriately mixed and used.
また、ガラス繊維用集束剤に用いられる水は特に限定されるものでなく、上述した成分を溶解又は分散可能であればよく、例えば、イオン交換水、蒸留水が好適に用いられる。水の含有率は、ガラス繊維用集束剤全重量を基準として９０．０〜９７．５重量％であることが好ましい。 Moreover, the water used for the sizing agent for glass fibers is not particularly limited as long as the above-described components can be dissolved or dispersed. For example, ion-exchanged water or distilled water is preferably used. The water content is preferably 90.0 to 97.5% by weight based on the total weight of the glass fiber sizing agent.
ガラス繊維用集束剤は、上記成分の他に、乳化剤、柔軟剤、防腐剤、又はメタノール、エタノール、イソプロパノール等のアルコールやその他有機溶剤を少量含有していてもよい。 In addition to the above components, the glass fiber sizing agent may contain a small amount of emulsifiers, softeners, preservatives, alcohols such as methanol, ethanol, isopropanol, and other organic solvents.
乳化剤としては、例えば、カルボキシベタイン等の両性界面活性剤、ポリオキシエチレンポリアルキルエーテル等のノニオン性界面活性剤等が挙げられ、その含有率は、ガラス繊維用集束剤の全重量を基準として０．０５〜０．３重量％が好ましい。 Examples of the emulsifier include amphoteric surfactants such as carboxybetaine, nonionic surfactants such as polyoxyethylene polyalkyl ether, and the content is 0 based on the total weight of the glass fiber sizing agent. 0.05 to 0.3% by weight is preferable.
柔軟剤としては、例えばテトラエチレンペンタミンとステアリン酸を反応させて得られるアミド又はイミダゾリン等が挙げられる。 Examples of the softener include amide or imidazoline obtained by reacting tetraethylenepentamine and stearic acid.
ガラス繊維用集束剤は、以下に述べるような製造方法により製造することができる。すなわち、澱粉を水に分散させた後、９０〜９８℃に加熱し、一定割合を糊化させて８０℃以下に冷却し、これに、潤滑剤、乳化剤、柔軟剤などの水溶液（又は水分散物）をそれぞれ単独で、もしくは混合した状態で添加し、必要に応じて更に水で希釈する。上記成分以外の防腐剤やアルコール等を添加する場合も、これらを単独又は水溶液（又は水分散物）として、糊化した澱粉溶液に加えればよい。 The sizing agent for glass fibers can be produced by a production method as described below. That is, after starch is dispersed in water, it is heated to 90 to 98 ° C., gelatinized at a certain rate and cooled to 80 ° C. or lower, and then an aqueous solution (or water dispersion) of a lubricant, emulsifier, softener, etc. Are added individually or in a mixed state, and further diluted with water as necessary. When adding preservatives or alcohols other than the above components, these may be added to the gelatinized starch solution alone or as an aqueous solution (or aqueous dispersion).
また、ガラス繊維束は、上述のガラス繊維用集束剤によりフィラメントが複数本集束されてなるものであり、ガラス繊維用集束剤は複数のフィラメント間に存在し、フィラメントを束ねる接着剤（バインダ）として機能している。また、ガラス繊維用集束剤はフィラメントの外周を連続又は不連続膜として被覆し、ガラス繊維束を保護する機能も有している。 The glass fiber bundle is formed by bundling a plurality of filaments with the above-described glass fiber bundling agent, and the glass fiber bundling agent exists between the plurality of filaments and serves as an adhesive (binder) for bundling the filaments. It is functioning. The sizing agent for glass fibers also has a function of protecting the glass fiber bundle by covering the outer periphery of the filament as a continuous or discontinuous film.
ガラス繊維用集束剤は、ガラス繊維束の使用時にガラス繊維（フィラメント）を束状に保っておくだけの強度を有していればよく、ガラス繊維束内に一様に分布している必要はない。すなわち、フィラメント同士の接着性の観点からは、ガラス繊維用集束剤はガラス繊維束の外縁部から中心部へ向けて略均一の濃度で分布していることが好ましいが、例えば、外縁部の濃度が高く中心部の濃度が低い場合であってもフィラメントを保持可能であり実用上問題とならないため、かかる構成のガラス繊維束も本実施形態において採用可能である。 The sizing agent for glass fibers only needs to have a strength sufficient to keep the glass fibers (filaments) in a bundle shape when the glass fiber bundle is used, and it is necessary that the glass fiber bundle is uniformly distributed in the glass fiber bundle. Absent. That is, from the viewpoint of adhesion between filaments, the glass fiber sizing agent is preferably distributed at a substantially uniform concentration from the outer edge portion to the center portion of the glass fiber bundle. Even when the concentration is high and the concentration in the central portion is low, the filament can be held and does not cause a problem in practice. Therefore, a glass fiber bundle having such a configuration can also be employed in this embodiment.
ガラス繊維束に用いられるガラス繊維の直径は、４〜９μｍが好ましく、ガラス繊維束は、かかるガラス繊維（フィラメント）が５０〜４００本集束されてなるものであることが好ましい。フィラメントのガラス組成としては、例えば、Ｅガラス、Ｓガラス、Ｃガラス等が挙げられる。本実施形態において、フィラメントに対するガラス繊維用集束剤の付着率は、フィラメントの全重量に対して、０．５〜２．５重量％であることが好ましく、１．０〜１．５重量％がより好ましい。 The diameter of the glass fiber used for the glass fiber bundle is preferably 4 to 9 μm, and the glass fiber bundle is preferably formed by collecting 50 to 400 glass fibers (filaments). Examples of the glass composition of the filament include E glass, S glass, and C glass. In the present embodiment, the adhesion rate of the glass fiber sizing agent to the filament is preferably 0.5 to 2.5% by weight, and 1.0 to 1.5% by weight based on the total weight of the filament. More preferred.
ガラス繊維束は、例えば、白金ノズル（ブッシング）から引き出されたフィラメントに、ローラー型アプリケーターやベルト型アプリケーター等を用いてガラス繊維用集束剤を塗布し、これを集束機で集束することによってフィラメントを束ね、次いで、これを室温〜１５０℃で乾燥し、水等の揮発成分を除去することにより製造することができる。なお、適宜、加撚を施してもよい。 For example, a glass fiber bundle is obtained by applying a glass fiber sizing agent to a filament drawn from a platinum nozzle (bushing) using a roller type applicator or a belt type applicator. It can be manufactured by bundling and then drying at room temperature to 150 ° C. to remove volatile components such as water. In addition, you may give twist suitably.
ガラス繊維用集束剤は、例えば、毛羽品位によって、その性能を評価することができる。 The performance of the glass fiber sizing agent can be evaluated by, for example, the fluff quality.
［毛羽品位］
毛羽品位とは、ガラス繊維ヤーン１００ｍあたりの毛羽が少ないほど、ガラス繊維ヤーンの品位が良く、ガラス繊維用集束剤の性能が高いことを示し、４つの等級（◎、○、△、×）に分けることができる。ここで、「◎」は最も毛羽の少ない等級であり、順に「○」、「△」と毛羽が多くなり、「×」は最も毛羽が多い等級であることを示す。なお、ガラス繊維ヤーンは、ガラス繊維用集束剤が付着しているガラス繊維を束ねてガラス繊維束にし、撚りをかけることによって得ることができる。
[Fuzzy grade]
The fluff quality indicates that the fewer the fuzz per 100 m of glass fiber yarn, the better the quality of the glass fiber yarn and the higher the performance of the sizing agent for glass fiber. Four grades (◎, ○, △, ×) Can be divided. Here, “◎” is the grade with the least fluff, “◯”, “Δ” and the fluff increase in order, and “x” indicates the grade with the most fluff. The glass fiber yarn can be obtained by bundling glass fibers to which a glass fiber sizing agent is attached to form a glass fiber bundle and twisting the glass fibers.
以下、本発明を実施例により詳述するが、本発明の範囲はこれらの実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example explains in full detail this invention, the scope of the present invention is not limited to these Examples.
（実施例１〜３及び比較例１〜２）
使用する澱粉の組成は、表１のとおりである。
(Examples 1-3 and Comparative Examples 1-2)
Table 1 shows the composition of the starch used.
次に表２の配合組成で、以下の成分を上述のとおり配合させ、ガラス繊維用集束剤を作製した。
フィルム形成剤：架橋米澱粉
馬鈴薯澱粉
タピオカ澱粉
潤滑剤：パーム油
乳化剤Ａ：ポリオキシエチレンラウリルエーテル
乳化剤Ｂ：ポリオキシエチレンポリプロピレンエーテル
柔軟剤：テトラエチレンペンタミンとステアリン酸の縮合物
水
その他：防腐剤
Next, the following components were blended as described above in the blending composition of Table 2 to prepare a glass fiber sizing agent.
Film former: Cross-linked rice starch
Potato starch
Tapioca starch lubricant: Palm oil emulsifier A: Polyoxyethylene lauryl ether emulsifier B: Polyoxyethylene polypropylene ether Softener: Condensation product of tetraethylenepentamine and stearic acid Water: Preservative
上記の各ガラス繊維用集束剤を、上述のようにガラス繊維に用いることによりガラス繊維ヤーンを作製した。その際の、ガラス繊維ヤーンの毛羽品位について、上述の評価方法により、評価を行った。表３に評価結果を示す。 Glass fiber yarns were prepared by using the above glass fiber sizing agents for glass fibers as described above. The fluff quality of the glass fiber yarn at that time was evaluated by the above-described evaluation method. Table 3 shows the evaluation results.
所定の澱粉を２種類使用したガラス繊維集束剤を用いた場合は、実施例１〜３のとおり、ガラス繊維ヤーンの毛羽品位が良好であった。一方、１種類のみの澱粉しか含有しないガラス繊維集束剤を用いた場合は、比較例１及び２のとおり、ガラス繊維ヤーンの毛羽品位が不良であった。 When a glass fiber sizing agent using two types of predetermined starch was used, the fluff quality of the glass fiber yarn was good as in Examples 1 to 3. On the other hand, when a glass fiber sizing agent containing only one type of starch was used, the fluff quality of the glass fiber yarn was poor as in Comparative Examples 1 and 2.
上述のとおり、本発明により、製織時のガラス繊維の糸切れ、毛羽立ちを減少させるガラス繊維用集束剤、及びこのガラス繊維用集束剤を用いたガラス繊維束を提供することができた。 As described above, according to the present invention, it was possible to provide a glass fiber sizing agent that reduces yarn breakage and fluffing during weaving, and a glass fiber bundle using the glass fiber sizing agent.
Claims (6)
前記フィルム形成剤は、
糊化率５〜２５重量％の第１の澱粉、及び
糊化率５０〜８０重量％且つアミロペクチンの含有率が７０〜９５重量％の第２の澱粉、を含有し、
前記第１の澱粉が、架橋米澱粉であり、
前記第１の澱粉の含有量が、前記第２の澱粉の含有量よりも多い、ガラス繊維用集束剤。 A glass fiber sizing agent containing a film forming agent, a lubricant and water,
The film forming agent is
A first starch having a gelatinization rate of 5 to 25% by weight, and a second starch having a gelatinization rate of 50 to 80% by weight and an amylopectin content of 70 to 95% by weight ,
The first starch is a cross-linked rice starch;
A sizing agent for glass fibers , wherein the content of the first starch is greater than the content of the second starch .
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