JPH09227174A - Processed starch for glass fiber-seizing agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a processed starch capable of reducing the falling of starch powder and the generation of fuzzes from glass yarns coated with a glass fiber- seizing agent and stabilizing the viscosity of the seizing agent solution. SOLUTION: This processed starch for a glass fiber-seizing agent comprises one or more kinds of starches selected from the group of corn starch, tapioca starch, wheat starch, sweet potato starch and potato starch, subjected to a hydroxyalkylation treatment so as to give a M.S. value of 0.07-0.26 and to a crosslinking treatment so as to give a viscosity of 3-12cps in a 5% aqueous solution at 60 deg.C. The processed starch comprises a high amylose corn starch subjected to a hydroxyalkylation treatment so as to give a M.S. value 0.15-0.36 and to a crosslinking treatment so as to a viscosity of 6-16cps with a B type viscometer at 60rpm in a 5% aqueous solution at 60 deg.C.

Description

Detailed Description of the Invention

[0001]

The present invention relates to a modified starch for a glass fiber sizing agent. Generally, when spinning molten glass from a spinneret in the form of a multifilament, each glass fiber bundles each filament into a bundle of yarn immediately after being spun from the spinneret and applies a sizing agent mainly composed of starch. This is to protect the glass fiber from the effects of bending, abrasion, etc. in the following processes such as unwinding, twisting, knitting, warping, and woven fabric, and to prevent powder dropping, fluffing, and yarn breakage. is there.

[0002]

2. Description of the Related Art As a sizing agent acting as a film-forming agent, starch or a starch obtained by chemically treating and modifying starch is generally used. This is because starch has an appropriate film-forming force and adhesive force, is easy to deoil, and has a relatively low cost. In addition to starch, lubricants and preservatives are added to the sizing agent as auxiliaries. Yarns coated with such a sizing agent show excellent properties and have been used, but various improvements have been proposed.

As an improvement for the applied sizing agent to prevent the phenomenon of migration in which a specific component (generally a water-soluble component) migrates to the surface portion when the wound yarn package is dried. Japanese Patent Publication Sho-53-35
No. 639 discloses that the average particle size after gelatinization is 0.5 to 10
A sizing agent having a micron, a viscosity of 5%, and a crosslinked etherified starch having a viscosity of 30 cps or less at 50 ° C. as a film forming agent ”
Has been proposed.

Further, Japanese Patent Publication No. 4-76338 proposes "a migration-stable vitreous focusing paste composition using an esterified product of starch and octyl succinic anhydride or tetradecyl succinic anhydride".

Further, JP-A-61-270236 discloses "a glass obtained by esterifying a starch or a hydroxyalkylated product with a monovalent lower fatty acid or a monovalent aromatic acid and decomposing the starch molecule with concentrated sulfuric acid. Fiber sizing agents "have been proposed.

[0006]

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention
The sizing agent disclosed in Japanese Patent No. 5639 has an average particle size after gelatinization of 0.
In order to obtain 5 to 10 micron, rice starch which is expensive and has a low production yield must be used, or the degree of crosslinking must be increased to suppress swelling. However, since highly crosslinked starch does not dissolve in water, it is difficult for it to migrate,
Since the film property is poor and the film is not uniform and flexible, the covering of the yarn becomes insufficient, and powder drops and fuzzing increases.

The sizing agent of Japanese Patent Publication No. 4-76338 described above uses a starch having a high emulsifying power having hydrophobicity and hydrophilicity, so that the oil component used together emulsifies with a component of starch which is easily soluble in water. , The starch paste solution and the oil may be integrated so that migration may be difficult. However, originally, the oil component, which is the purpose of adding the oil component, moves to the surface layer of the starch film to improve the slippage of the starch film surface and reduce the frictional resistance, and the oil component of the role of suppressing powder falling and fuzzing is emulsified and Since it is also distributed in the inner layer, the effect of suppressing powder falling and fuzzing becomes poor.

The sizing agent disclosed in JP-A-61-270236 described above is soluble in water because starch is hydroxyalkylated and esterified or esterified and further acid hydrolyzed with concentrated sulfuric acid. Is very high and cross-linked. Therefore, the starch particles are more likely to migrate than those in which the starch particles 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 with time with a shearing force.

[0009]

Means for Solving the Problems As a result of intensive studies made by the present inventors to solve the above-mentioned problems, M. S. Value 0.
Hydroxyalkylated to 07-0.26 and 5%
One or more starches selected from the group consisting of cornstarch, tapioca starch, wheat starch, sweet potato starch, and potato starch, which are cross-linked to have a viscosity of 3 to 12 cps at 60 ° C. in a 60 ° C. B-type viscometer. A modified starch for glass fiber sizing agent. And M.M. S. Value 0.1
Modified starch for glass fiber sizing agent consisting of high amylose cornstarch hydroxyalkylated to 5 to 0.36 and cross-linked so that the viscosity at 60 ° C of a 5% aqueous solution at 60 ° C and 60 rpm is 6 to 16 cps Have been found to be useful in solving the above problems.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The MS value showing the degree of hydroxyalkylation of the present invention means the number of moles of hydroxyalkyl groups per anhydroglucose residue of starch (Molar Sub).
It means a “statement”. The hydroxyalkylation of the present invention is carried out by adding 1,2-alkylene oxide to starch,
That is, ethylene oxide, 1.2-propylene oxide, 1.2-butylene oxide and the like are used. These alkylene oxides have an MS value of 0.07 to 0.26, preferably 0.09 to 0.2, for corn starch, tapioca starch, wheat starch, sweet potato starch, and potato starch.
It is added so as to be in the range of 22, and the high amylose corn starch is added so that the MS value is in the range of 0.15 to 0.36, preferably 0.17 to 0.32.

The modified starch for glass fiber sizing agent of the present invention has a 60 ° C. viscosity of a 5% aqueous solution in combination with the above-mentioned hydroxyalkylation, and corn starch, tapioca starch, wheat starch, sweet potato starch, and potato starch are 3 to 3. 12c
ps preferably 5-10 cps, for high amylose corn starch 6-16 cps preferably 8-14
The viscosity is adjusted by a crosslinking reaction so as to be cps.
As the cross-linking agent, a reagent having two or more functional groups capable of reacting with the hydroxyl group of starch such as epichlorohydrin, sodium trimetaphosphate, cyanuric chloride, adipic-acetic hydride, formalin, diepoxide and dialdehyde is used.

These preferable ranges differ depending on the type of starch used. This is because there is a difference in the starch film properties in the unmodified state, so those with originally good starch film properties have low hydroxyalkylation, and those with originally poor film properties such as high amylose cornstarch have hydroxyalkyl properties. It must be highly advanced. The degree of hydroxyalkylation also depends on the relationship with the degree of crosslinking described below. That is, when the degree of cross-linking is high, the viscosity of the paste solution is less likely to decrease even if the paste solution is subjected to shearing force such as stirring at high temperature for a long time. . When the degree of cross-linking is low, the film property does not deteriorate so much, so it is not necessary to increase hydroxyalkylation so much. In other words, as a result of various examinations by changing and adjusting the type of starch to be used, hydroxyalkylation, and the degree of crosslinking, it was found that the suitable range of hydroxyalkylation is the above range. Therefore, if it deviates from the above-mentioned preferable range, as a result, the state of powder falling off, fluffing, yarn breakage, etc. becomes worse. This seems to be influenced by the degree of flexibility of the film due to hydroxyalkylation.

The modified starch for a glass fiber sizing agent of the present invention is made into a composition for a glass fiber sizing agent by adding and mixing a lubricant, a softening agent, a preservative and other auxiliary agents which are usually used in the paste solution. , Applied to a glass filament and used.

[0014]

【Example】

Example 1 Corn starch, tapioca starch, wheat starch, sweet potato starch,
Potato starch or high amylose cornstarch 1
000g is put into a pressure resistant blender, and methanol 100
g, water 3 g, caustic soda 1 g, triethylamine 20 g
The dissolved solution was sprayed with stirring. 50-200 g of 1,2-propylene oxide or 50-200 g of ethylene oxide, respectively, epichlorohydrin 0.1
˜0.5 g was added, and cross-linked and hydroxyalkylated at 500 ° C. for 10 hours. After the reaction was completed, it was neutralized with sulfuric acid diluted with methanol, dried, and refined. M. of each starch S. Value and 60% of 5% aqueous solution, B type viscometer, 6
The viscosities at 0 rpm are shown in Table 1 for crosslinked and hydroxypropylated samples of corn starch, Table 2 for crosslinked and hydroxypropylated samples of tapioca starch, and Table 3 for crosslinked and hydroxypropylated samples of wheat starch.
Table 4 for crosslinked and hydroxyethylated samples of sweet potato starch, Table 5 for crosslinked and hydroxyethylated samples of potato starch, crosslinked high amylose corn starch
Table 6 shows the hydroxypropylated sample, and Table 7 shows the crosslinked hydroxypropylated sample of high amylose corn starch.

[Table 1]

[Table 2]

[Table 3]

[Table 4]

[Table 5]

[Table 6]

[Table 7]

Example 2 Using each sample obtained in Example 1, a sizing agent composition for a sizing agent shown in Table 8 was prepared, coated on 9 μ408 glass filaments, bundled and wound, and then rewound. Of various characteristics of yarn (fluffing, fluffing) and stability of sizing liquid (70 ℃
The viscosity stability when the stirring blade was stirred at 200 rpm for 1 hour was tested for each starch sample. The results are shown in Table 9,
10, 11, 12, 13, 14, and 15 are shown (in the table, ⊚ indicates a very good state, ∘ indicates a good state, Δ indicates an inferior state, and x indicates an extremely inferior state).

[Table 8]

[Table 9]

[Table 10]

[Table 11]

[Table 12]

[Table 13]

[Table 14]

[Table 15]

Comparative Example 1 1000 g of cornstarch, potato starch or high amylose cornstarch was placed in a pressure resistant blender,
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 while stirring. 50-200 g of 1,2-propylene oxide or 50-200 g of ethylene oxide, respectively,
Hydroxyalkylated at 50 ° C. for 10 hours. After the reaction was completed, 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 the viscosity was reduced, the mixture was neutralized with diluted ammonia water, dried and refined. MS of each starch. Value and 60 of 5% aqueous solution
C., type B viscometer, viscosity at 60 rpm is shown in Table 16 for a hydroxypropylated acid hydrolysis sample of corn starch, in Table 17 for a hydroxyethylated acid hydrolysis sample of potato starch, and in hydroxypropylated acid hydrolysis of high amylose corn starch. Table 18 for degradation samples
It was shown to.

[Table 16]

[Table 17]

[Table 18]

Comparative Example 2 Using each sample obtained in Comparative Example 1, the same test as in Example 2 was conducted. The results are shown in Tables 19, 20, and 21, respectively.

[Table 19]

[Table 20]

[Table 21]

[0018]

The yarn coated with the sizing agent for glass fibers according to the present invention has various properties such as less powder dropping and less fluffing, and also has excellent viscosity stability of the sizing agent sizing liquid.

Claims (2)

[Claims] 1. M. S. Hydroxyalkylated to a value of 0.07 to 0.26, and a 5% aqueous solution has a viscosity of 3 to 60 ° C.
Cornstarch cross-linked to 12 cps,
A modified starch for a glass fiber sizing agent, which comprises at least one starch selected from the group consisting of tapioca starch, wheat starch, sweet potato starch, and potato starch. 2. M. S. Hydroxyalkylated to a value of 0.15 to 0.36 and the viscosity of a 5% aqueous solution at 60 ° C is 6 to
A modified starch for glass fiber sizing agent, which comprises high amylose corn starch cross-linked to 16 cps.