JP3949746B2 - Chemical starch for glass fiber sizing agent - Google Patents

Description

【００１５】
実施例２
実施例１で得た各試料を用いて表２に示す集束剤用糊剤組成物を調製し、９μ４０８本の硝子フィラメントに塗布し、集束、巻き取り後、巻き返して得たヤーンの諸特性（粉落ち、毛羽立ち）試験及び糊液の安定性（７０℃で攪拌翼を２００ｒｐｍで１時間攪拌したときの粘度安定性）試験を各澱粉試料について行った。結果を表３に示す（表中◎は非常によい状態、○はよい状態、△は劣る状態、×は非常に劣る状態をそれぞれ表す）。
【表２】

【表３】

【００１６】
比較例１
ハイアミロースコーンスターチ１０００ｇを耐圧ブレンダーに投入し、メタノール１００ｇに水３ｇ、苛性ソーダ１ｇ、トリエチルアミン２０ｇを溶解した溶液を攪拌しながら噴霧した。１,２−プロピレンオキシドを５０〜２００ｇまたはエチレンオキシドを５０〜２００ｇそれぞれ添加し、５０℃で１０時間ヒドロキシアルキル化した。反応終了後、濃硫酸５ｇをメタノール７０ｇで希釈し、４０℃で２〜５時間攪拌し酸加水分解による低粘度化を行った。低粘度化終了後希アンモニア水で中和し、乾燥し、精粉した。それぞれの澱粉のＭ．Ｓ．値と５％水溶液の６０℃、Ｂ型粘度計、６０ｒｐｍにおける粘度を、表４に示した。
【表４】

【００１７】
比較例２
比較例１で得た各試料を用いて、実施例２と同様の試験を行った。結果を表５に示す。
【表５】

【００１８】
【発明の効果】
本発明の硝子繊維用集束剤を塗布したヤーンは、粉落ちや毛羽立ちが少ないという優れた諸特性を有し、集束剤糊液の粘度安定性にも優れている。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a modified starch for a glass fiber sizing agent. In general, when glass fibers are spun from a spinneret in the form of multifilaments, glass fibers are bundled into a bundle of yarns immediately after being spun from the spinneret and a sizing agent mainly composed of starch is applied. This is to protect the glass fiber from the effects of bending, abrasion, etc. that are received in the next process such as rewinding, twisting, winding, warping, woven fabric, etc., and preventing powder falling, fluffing, yarn breakage, etc. is there.
[0002]
[Prior art]
As a sizing agent that acts as a film forming agent, starch or a product obtained by chemically modifying starch is usually used. This is because starch has an appropriate film forming force and adhesive force, is easy to deoil, and is relatively inexpensive. In addition to starch, lubricants and preservatives are added as auxiliaries to the sizing agent.
Yarns coated with such a sizing agent exhibit excellent properties and have been used so far, but various improvements have been proposed.
[0003]
As an improvement to prevent a phenomenon in which a specific component (generally a component that is easily soluble in water) migrates to the surface portion when the applied sizing agent dries the wound yarn package, it is improved. No. -35639 proposes “a sizing agent using a cross-linked etherified starch having a mean particle diameter after gelatinization of 0.5 to 10 microns, a viscosity of 5% and a viscosity of 30 cps or less at 50 ° C. as a film forming agent”. Has been.
[0004]
Japanese Patent Publication No. 4-76338 proposes a “moving-stable glass bundling paste composition using an esterified product of starch and octyl succinic anhydride or tetradecyl succinic anhydride”.
[0005]
JP-A-61-270236 discloses that “starch or hydroxyalkylated product is esterified with a monovalent lower fatty acid or monovalent aromatic acid and the starch molecules are decomposed with concentrated sulfuric acid to concentrate glass fibers. "Agent" has been proposed.
[0006]
[Problems to be solved by the invention]
The above-mentioned sizing agent disclosed in JP-B-53-35639 uses rice starch that is expensive and has a low production yield in order to reduce the average particle size after gelatinization to 0.5 to 10 microns, or suppress swelling. The degree of crosslinking must be increased. However, since the highly crosslinked starch is not soluble in water, it is difficult to migrate. However, the film property is poor and the film does not become a uniform and flexible film, so that the coating of the yarn becomes insufficient, resulting in powder falling and fluffing.
[0007]
Since the sizing agent of the above Japanese Patent Publication No. 4-76338 uses starch having hydrophobicity and hydrophilicity and high emulsifying power, the oil component used in combination is emulsified with a component that is easily soluble in water of starch. Migration may be difficult because the liquid and oil are integrated. However, the oil component that originally has the purpose of adding the oil component is shifted to the surface layer of the starch film to improve the slipping of the starch film surface to reduce the frictional resistance, and the oil component that plays a role in suppressing powder falling and fluffing is emulsified. Since it is also distributed in the inner layer, the effect of suppressing powder falling and fluffing becomes poor.
[0008]
The sizing agent described in JP-A-61-270236 has a very high solubility in water because the starch is hydroxyalkylated and esterified or esterified and further subjected to acid hydrolysis with concentrated sulfuric acid. Higher and cross-linked. Therefore, migration is easier than starch particles that are less likely to swell. In addition, the hydrolyzed product has a problem that the stability of the paste solution as a sizing agent generally tends to decrease in viscosity over time when subjected to a shearing force.
[0009]
[Means for Solving the Problems]
As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that M.M. S. Glass fiber sizing agent comprising high amylose corn starch hydroxypropylated to a value of 0.15 to 0.21 and crosslinked to give a 5% aqueous solution at 60 ° C., a B-type viscometer, and a viscosity at 60 rpm of 6 to 10 cps It was found that the modified starch is useful for solving the above problems.
[0010]
DETAILED DESCRIPTION OF THE INVENTION
M. indicating the degree of hydroxyalkylation of the present invention. S. The value refers to the number of moles of hydroxyalkyl groups per anhydroglucose residue of starch (Molar Substitution). In the hydroxypropylation of the present invention, 1,2-propylene oxide is used for starch. Hydroxypropylation is described in M.M. S. It is added so that the value is in the range of 0.15 to 0.21.
[0011]
The modified starch for a glass fiber sizing agent of the present invention is adjusted by a crosslinking reaction so that the 60 ° C. viscosity of a 5% aqueous solution becomes 6 to 10 cps in combination with the hydroxypropylation described above. As the cross-linking agent, a reagent having two or more functional groups capable of reacting with starch hydroxyl groups such as epichlorohydrin, sodium trimetaphosphate, cyanuric chloride, adipic-acetic anhydride, formalin, diepoxide, and dialdehyde is used.
[0012]
As a result of various investigations by changing, adjusting and varying the degree of hydroxypropylation and crosslinking, it was found that the preferred range of hydroxypropylation is the above range. Therefore, if the above preferred range is not satisfied, the result of powder falling, fluffing, yarn breakage, etc. will be deteriorated. This seems to be influenced by the degree of flexibility of the film due to hydroxypropylation.
[0013]
The modified starch for glass fiber sizing agent of the present invention becomes a composition for glass fiber sizing agent by adding and mixing lubricants, softeners, preservatives, and other auxiliaries that are usually used in the paste solution. Used by applying to.
[0014]
【Example】
Example 1
1000 g of high amylose corn starch was put into a pressure-resistant blender, and a solution prepared by dissolving 3 g of water, 1 g of caustic soda and 20 g of triethylamine in 100 g of methanol was sprayed with stirring. 1,2-Propylene oxide (50-200 g) was added together with epichlorohydrin (0.1-0.5 g), and crosslinked and hydroxypropylated at 50 ° C. for 10 hours. After the reaction, the mixture was neutralized with sulfuric acid diluted with methanol, dried and refined. M. of each starch. S. Table 1 shows the values and the viscosity of a 5% aqueous solution at 60 ° C., a B-type viscometer, and 60 rpm.
[Table 1]

[0015]
Example 2
Using each sample obtained in Example 1, the sizing agent composition for sizing agent shown in Table 2 was prepared, applied to 9 μ408 glass filaments, and after focusing, winding, and various properties of the yarn obtained by rewinding ( Each starch sample was subjected to a powder fall off and fluffing test and a stability of the paste liquid (viscosity stability when the stirring blade was stirred at 200 rpm for 1 hour at 70 ° C.). The results are shown in Table 3 (in the table, ◎ represents a very good state, ○ represents a good state, Δ represents an inferior state, and x represents a very inferior state).
[Table 2]

[Table 3]

[0016]
Comparative Example 1
1000 g of high amylose corn starch was put into a pressure-resistant blender, and a solution prepared by dissolving 3 g of water, 1 g of caustic soda and 20 g of triethylamine in 100 g of methanol was sprayed with stirring. 50-200 g of 1,2-propylene oxide or 50-200 g of ethylene oxide was added, respectively, and hydroxyalkylated at 50 ° C. for 10 hours. After completion of the reaction, 5 g of concentrated sulfuric acid was diluted with 70 g of methanol and stirred at 40 ° C. for 2 to 5 hours to reduce the viscosity by acid hydrolysis. After completion of the viscosity reduction, the mixture was neutralized with dilute aqueous ammonia, dried and refined. M. of each starch. S. Table 4 shows the values and the viscosity of a 5% aqueous solution at 60 ° C., a B-type viscometer, and 60 rpm.
[Table 4]

[0017]
Comparative Example 2
The same test as in Example 2 was performed using each sample obtained in Comparative Example 1. The results are shown in Table 5.
[Table 5]

[0018]
【The invention's effect】
The yarn coated with the glass fiber sizing agent of the present invention has excellent properties such as less powdering and fluffing and is excellent in viscosity stability of the sizing agent paste.

Claims (1)

M.M. S. A modified starch for a glass fiber sizing agent comprising high amylose corn starch which has been hydroxypropylated to a value of 0.15 to 0.21 and has been crosslinked to give a 5% aqueous solution having a 60 ° C. viscosity of 6 to 10 cps.