JP2003221784A - Film-forming agent, warp sizing agent for glass fiber woven fabric and warp for glass fiber woven fabric attaching the same sizing agent - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a sizing agent having excellent dividing property after sizing, reduced in damage of a film by friction and capable of providing a warp having slight fluff and a glass fiber yarn for warp to which the sizing agent is attached in order to prepare a glass fiber woven fabric having slight fluff. <P>SOLUTION: The film-forming agent and the warp sizing agent for glass fiber woven fabrics are each obtained by formulating a polyvinyl alcohol with a hydroxyalkylated starch and/or an acetylated starch and the decomposed product of a cationized starch or the decomposed product of a cationized hydroxyalkylated starch or by formulating the polyvinyl alcohol with the decomposed product of the cationized starch and/or the decomposed product of the cationized hydroxyalkylated starch. The warp for glass fiber woven fabrics is obtained by attaching the sizing agent to the glass fiber yarn warp. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a film forming agent, a sizing agent used for warps for glass fiber fabrics, and a warp for glass fiber fabrics to which the sizing agent is attached.

[0002]

2. Description of the Related Art Glass fibers for textiles are wound into a cake by attaching a primary sizing agent containing starch and a nonionic lubricant and a cationic lubricant as main components by a roller applicator when the glass fibers are spun. , Twist it and wind it up on a bobbin as a glass fiber yarn. Next, in general, the step of preparing warp yarns for glass fiber cloth is performed by using the glass fiber yarn wound on a bobbin to determine the number of warp yarns, the length,
Wind the warp beam with equal tension according to the density and width. This glass fiber is drawn on a sizing machine with a constant tension and passed through a sizing agent. As a result, the sizing agent is sufficiently impregnated, and then the excess sizing agent is squeezed out by the sizing roll and the squeezing roll.
Thousands of sheet-shaped glass fiber warps with sizing agent are dried, and adjacent yarns are glued by passing them separately above and below a long round bar that is perpendicular to the sheet advancing direction called a dividing rod. The individual yarns are separated into individual yarns and wound into a weaving beam. Since the adjacent yarns partially adhere to each other during drying because they are glued in a sheet shape, when peeled off with a dividing rod, the fibers of the strongly adhered part are broken and cause fluff.

This sizing agent is used in the process of weaving glass cloth for the purpose of protecting the glass fiber yarn warp from bending and friction. The components of the sizing agent are usually used in combination with polyvinyl alcohol, starch, lubricant, plasticizer, preservative and the like. Polyvinyl alcohol and starch are used for adhesion and film formation to protect the glass fiber of the yarn from any bending and rubbing on the loom. For example, polyvinyl alcohol has a partial saponification degree of 88 ± 2 moles, a viscosity of 5.0 ± 1.0 mPa · s (4%, 20 ° C.), and starch is a common starch such as corn starch or a chemically modified product such as hydroxylalkylated. The etherified starch, the acetylated esterified starch, and the crosslinked starch reacted with a crosslinking agent such as epichlorohydrin are used. Lubricants are used to lubricate the yarn, reduce friction on the loom, and protect the glass fibers. Types of lubricants include hydrogenated hardened oils of animal and vegetable oils, paraffin wax, esters of higher saturated fatty acids and higher saturated alcohols, and the like. As the plasticizer, a compound having a hydroxyl group, an amino acid or an amide group, such as glycerin, ethylene glycol or urea is used.

[0004]

Although such a sizing agent is still used, the glass fiber yarn is easily fluffed due to the speeding up of the sizing machine and the loom, and the glass fabric is impregnated with an epoxy resin or the like. Since the electric circuit printed on the copper-clad laminate has become highly accurate, defects due to the fluff of the glass fabric are likely to occur, and the glass fiber fabric is required to be further improved in quality. Thousands of glass fiber yarns are drawn out from the warping beam and glued with a sizing agent to form a sheet, and adjacent yarns are partially bonded during drying. After drying, the fibers are separated one by one with a dividing rod, but if the adhesion between the yarns is strong, they are forcibly divided, and there is the problem that the glass fibers are partially cut and fluff occurs. Further, there is a problem that due to the high speed of the loom, the warp yarns are severely rubbed on the loom due to "sacks" or the like, and the partially cut portions are further damaged, resulting in severe fluffing. The present invention solves the above-mentioned problems, has excellent splittability after sizing, and reduces damage to the film due to friction, and a sizing agent and a sizing agent that can obtain warps with less fluff. It is intended to make a glass fiber fabric with less fluff by providing a glass fiber yarn for warp attached.

[0005]

In order to achieve the above object, the present inventors have developed polyvinyl alcohol, hydroxyalkylated starch and / or acetylated starch into a cationized starch decomposition product and / or cationized hydroxyalkylated starch. A sizing agent containing starch degradation products or polyvinyl alcohol with cationizing starch degradation products and / or cationizing hydroxyalkylated starch degradation products is applied to the warp beam wound glass fiber warp. When a sheet-shaped product is dried and wound on a weaving beam, it is separated into individual glass fiber yarns, but it is easy to use a dividing rod without partial cutting of the glass fiber that causes fluff. I found that I can divide.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The film forming agent of the present invention comprises polyvinyl alcohol, hydroxyalkylated starch and / or
Alternatively, acetylated starch is blended with a cationized starch degradation product and / or cationized hydroxyalkylated starch degradation product, or polyvinyl alcohol is blended with a cationized starch degradation product and / or a cationized hydroxyalkylated starch degradation product. Obtained. With respect to the respective compounding amounts, 20 to 80 parts by mass of the hydroxyalkylated starch and / or acetylated starch cationized starch decomposition product, cationized starch decomposition product and / or cationized hydroxyalkyl are added to 100 parts by mass of polyvinyl alcohol. It is preferable to blend 2 to 80 parts by mass of the hydrolyzed starch decomposition product. When the hydroxyalkylated starch or acetylated starch cationized starch decomposition product is not mixed,
It is preferable to mix 2 to 150 parts by mass of the cationized starch decomposition product and / or the cationized hydroxyalkylated starch decomposition product with respect to 100 parts by mass of polyvinyl alcohol.

The polyvinyl alcohol used in the present invention has a saponification degree of 88 ± 2 mol and a viscosity of 5.0 ± 1.0.
Partially saponified polyvinyl alcohol of mPa · s (4%, 20 ° C.) is preferably used. However, since the cationized starch hydrolyzate and the cationized hydroxyalkylated starch hydrolyzate of the present invention have extremely low viscosities, the polyvinyl alcohol used when a large amount of them is mixed has a saponification degree of 8 or less.
8 ± 2 mol of partially saponified polyvinyl alcohol, viscosity exceeds 6.0 mPa · s (4%, 20 ° C), about 30 mP
Those up to a · s (4%, 20 ° C.) are also preferably used.

The hydroxyalkylated starch is a raw material starch selected from corn starch, tapioca starch, wheat starch, sweet potato starch, potato starch or high amylose corn starch, which is 1,2-alkylene oxide, that is, ethylene oxide, 1,2-propylene oxide, 1 , 2-butylene oxide. These alkylene oxides are corn starch, tapioca starch, wheat starch,
MS value of 0.0 for sweet potato starch and potato starch
3 to 0.26, preferably 0.07 to 0.20, so that the high amylose corn starch has an MS value of 0.07 to 0.36, preferably 0.10.
It is added so as to be in the range of 0.30. Here, the MS value indicating the degree of hydroxyalkylation means the number of moles of hydroxyalkyl groups per anhydrous glucose residue of starch (Mo
lar Substitution).

The acetylated starch is obtained by acting acetic anhydride or vinyl acetate on a raw material starch selected from corn starch, tapioca starch, wheat starch, sweet potato starch, potato starch or high amylose corn starch. These acetylating agents are added to cornstarch, tapioca starch, wheat starch, sweet potato starch, and potato starch so that the DS value is in the range of 0.03 to 0.25, preferably 0.05 to 0.15. However, for high amylose corn starch, the DS value is 0.07 to 0.36, preferably 0.
It is added so as to be in the range of 10 to 0.30. Here, the DS value indicating the degree of esterification means the number of substituted acetyl groups per starch anhydrous glucose residue (Degree of Substitu
tion). For example, a DS value of 0.01 means that one hydroxyl group is substituted with an acetyl group for 100 glucose units.

These hydroxyalkylated starch or acetylated starch are approximately 5 to 70 m in 5% aqueous solution at 60 ° C.
Those having a viscosity of Pa · s are preferably used. Therefore, when the viscosity after etherification and acetylation is higher than this viscosity range, modification such as molecular weight reduction treatment or crosslinking treatment is performed as necessary to reduce the viscosity.

The hydroxyalkylated starch or acetylated starch of the present invention is subjected to a low molecular weight treatment or a crosslinking treatment to reduce the viscosity, if necessary. The molecular weight reduction treatment is sulfuric acid,
Acid hydrolysis treatment with mineral acids such as nitric acid and hydrochloric acid and organic acids, and oxidation treatment with oxidizing agents such as hydrogen peroxide and sodium hypochlorite. The viscosity of the hydroxyalkylated starch or acetylated starch of the present invention can be adjusted by a crosslinking reaction. As the cross-linking agent, a reagent having two or more functional groups capable of reacting with the hydroxyl groups of starch such as epichlorohydrin, sodium trimetaphosphate, cyanuric chloride, adipic-acetic hydride, formalin, diepoxide compound, and dialdehyde compound is used. To be The degree of the lowering of the viscosity is shown by the result of hydrolysis to lower the viscosity (lowering the molecular weight) and the result of suppressing the swelling of starch by the crosslinking treatment. A viscosity of 5% aqueous solution at 60 ° C. of about 5 to 70 mPa · s, preferably 1 to 50 mPa · s is preferably used.

The cationized starch decomposition product of the present invention has a viscosity of about 1 to 2000 mPa · s at 50 ° C. in an aqueous solution at 60 ° C., and is a polyvinyl alcohol, hydroxyalkylated starch or acetylated starch cationized starch decomposition product or cation. By blending the hydrolyzed hydroxyalkylated starch decomposition product, the viscosity after blending can be adjusted to a low viscosity.

In the present invention, the cationized starch decomposition product refers to a cationized starch decomposition product. The starch degradation product refers to dextrin, oligosaccharide, maltose, glucose, etc. obtained by hydrolyzing starch with an acid or an enzyme, and in the present invention, reduction obtained by reducing the reducing sugar contained in these starch degradation products by hydrogenation or the like. Also includes starch syrup, maltitol, and sorbitol. Further, not only those obtained by cationizing these starch decomposition products but also those obtained by cationizing hydroxyalkylated hydroxyalkylated starch decomposition products are preferably used.

The hydroxyalkylated starch decomposition product is obtained by adding 1,2-alkylene oxide or 1 to the above starch decomposition product.
-It is obtained by reacting a halogeno-2-hydroxyalkane. As the 1,2-alkylene oxide, ethylene oxide, 1,2-propylene oxide,
It is preferable to use 1,2-butylene oxide or the like.
As the 1-halogeno-2-hydroxyalkane, it is preferable to use ethylene chlorohydrin, 1-halogeno-2-hydroxypropane, 1-halogeno-2-hydroxybutane and the like. The MS value of the hydroxyalkylated starch hydrolyzate is preferably 0.05 to 1.8, and more preferably 0.2 to 1.0.

A cationizing agent is reacted with the starch decomposition product or the hydroxyalkylated starch decomposition product prepared as described above. The cationizing agent used is 2,3-
Epoxypropyltrialkylammonium salt (glycidyltrialkylammonium salt) or 3-halogeno-2-hydroxytrialkylammonium salt is used alone or as a mixture. Further, the anion of the ammonium salt may be inorganic or organic as long as it can be an anion, and generally it is preferably a halogen ion and a chlorine ion. Is most preferred.

Of the 2,3-epoxypropyltrialkylammonium salts (glycidyltrialkylammonium salts), those which can be preferably used in the present invention are exemplified by 2,3-epoxypropyltrimethylammonium chloride and 2,3. -Epoxypropyltriethylammonium chloride, 2,3-epoxypropyltripropylammonium chloride, 2,3-epoxypropyldimethyloctylammonium chloride,
2,3-epoxypropyl dimethyldecyl ammonium chloride, 2,3-epoxypropyl dimethyllauryl ammonium chloride, 2,3-epoxypropyl dimethyl myristyl ammonium chloride, 2,3-
Examples thereof include epoxypropyl dimethyl palmityl ammonium chloride, 2,3-epoxy propyl dimethyl dodecyl ammonium chloride, and 2,3-epoxy propyl dimethyl octadecyl ammonium chloride.

Of the 3-halogeno-2-hydroxytrialkylammonium salts, those which can be preferably used in the present invention are exemplified by 3-halogeno-2-hydroxytrimethylammonium chloride and 3-halogeno-2.
-Hydroxytriethylammonium chloride, 3-
Halogeno-2-hydroxytripropylammonium chloride, 3-halogeno-2-hydroxydimethyloctylammonium chloride, 3-halogeno-2-hydroxydimethyllaurylammonium chloride, 3-
Halogeno-2-hydroxydimethylmyristylammonium chloride, 3-halogeno-2-hydroxydimethylpalmitylammonium chloride, 3-halogeno-
2-Hydroxydimethyl dodecyl ammonium chloride, 3-halogeno-2-hydroxydimethyl octadecyl ammonium chloride, etc. can be mentioned.

The reaction between the starch decomposition product or the hydroxyalkylated starch decomposition product and the above cationizing agent is carried out in the presence of water and an alkaline substance. That is, a starch decomposition product or a hydroxyalkylated starch decomposition product, a cationizing agent,
The reaction is allowed to proceed by adding water and an alkaline substance. The order of adding the cationizing agent, water and the alkaline substance is arbitrary. The reaction temperature is preferably about 40 to 80 ° C.
The reaction between the decomposed product of starch or the decomposed product of hydroxyalkylated starch and the cationizing agent is performed by converting the hydrogen atom from the hydroxyl group mainly bonded to carbon at 6-position, 2-position or 3-position of the decomposed product of starch or decomposed product of hydroxyalkylated starch. It is considered that the carbon atom at the 3-position of the cationizing agent is bonded by an ether bond. In addition, starch hydrolysis, cationization,
In the description so far, the hydroxyalkylation reaction has been described as an example in which hydrolysis is performed first, but any order may be performed first. For example, hydroxyalkylation may be performed first, followed by cationization, and finally acid or enzymatic hydrolysis. The degree of cationization is represented by the nitrogen content of a cationized starch decomposition product or a hydroxyalkylated starch decomposition product. The nitrogen content of the cationized starch decomposition product or cationized hydroxyalkylated starch decomposition product of the present invention is preferably 0.2 to 3.5% by mass. When the nitrogen content is less than 0.2% by mass, the degree of cationization is low and the effect of the present invention may not be expected. Further, even if the nitrogen content exceeds 3.5% by mass, further improvement of the effect of the present invention cannot be expected, and the performance is saturated.

The decomposed product of starch or the decomposed product of hydroxyalkylated starch is soluble in cold water, and the reaction product is obtained as an aqueous solution. This aqueous solution is obtained as a mixture containing unreacted starch decomposition product or hydroxyalkylated starch decomposition product in addition to the cationized product. 20-80 parts by mass of hydroxyalkylated starch and / or acetylated starch cationized starch decomposition product, and 2 parts of cationized starch decomposition product and / or cationized hydroxyalkylated starch decomposition product per 100 parts by mass of polyvinyl alcohol. When 80 parts by mass is blended and no hydroxyalkylated starch or acetylated starch cationized starch decomposition product is blended, polyvinyl alcohol 10
The cationized starch decomposition product and / or the cationized hydroxyalkylated starch decomposition product is added in an amount of 2 to 1 with respect to 0 part by mass.
By blending 50 parts by mass, the effect of having excellent splittability after sizing according to the present invention, reducing damage to the film due to friction, and obtaining a warp with less fluff can be obtained. 2 to 1 of this cationized starch decomposition product or cationized hydroxyalkylated starch decomposition product
50 parts by mass means that the aqueous solution obtained at various concentrations has a pure content (solid content) of 10 to 150 parts by mass.

The hydroxyalkylated starch or acetylated starch of the present invention has the effect of lowering the tear strength of the film when blended with polyvinyl alcohol, and therefore can exhibit excellent splittability after gluing. However, if the amount of addition is large, the flexibility of the film is lowered and the film is easily damaged when an external force is applied. 20 to 80 parts by mass is blended with 100 parts by mass of polyvinyl alcohol. When the blending amount is less than 20 parts by mass, the dividability is insufficient, and when it is more than 80 parts by mass, the film is damaged by friction. Not reduced enough. When the cationized starch decomposition product and / or the cationized hydroxyalkylated starch decomposition product is blended with polyvinyl alcohol, hydroxyalkylated starch or acetylated starch,
The elongation of the film is increased, the flexibility is improved, and the film is less likely to be damaged even when an external force is applied. The amount of the cationized starch decomposition product and / or the cationized hydroxyalkylated starch decomposition product when the hydroxyalkylated starch or acetylated starch cationized starch decomposition product is mixed with polyvinyl alcohol is 2 to 80 parts by mass. When the hydroxyalkylated starch or acetylated starch cationized starch decomposition product is not blended, 2 to 150 parts by mass are blended. When the amount is less than 2 parts by mass, the damage of the film due to friction is not sufficiently reduced.
When the amount is more than 150 parts by mass or 150 parts by mass, the flexibility is increased but the film strength is lowered, which is not preferable.

The warp sizing agent for glass fiber woven fabric of the present invention is attached to glass yarn warped by a sizing machine, dried and wound into a weaving beam. The glass composition, glass fiber diameter, cross-sectional shape and strand of the yarn It is applicable to any warped yarn without being limited to the number of filaments and the number of twists constituting the. The amount of solid content of the sizing agent containing the warp sizing agent for glass fiber fabric of the present invention, which is attached to the yarn, is 0.001 to 15.0% by mass, preferably 0.1 to 5.0% by mass.
It is 5.0% by mass, more preferably 0.5 to 2.0% by mass. If the adhered amount of the sizing agent is 0.001% by mass or less, the effect as a sizing agent does not appear, and if it is 15% by mass or more, the adhesive strength becomes too strong and the dividability deteriorates.

[0022]

In the glass fiber for warp used in the present invention, the primary sizing agent is already attached when the molten glass is drawn out from the platinum nozzle, spun and wound up. The sizing agent of the present invention is attached on the glass fiber sizing agent. A sizing agent containing a warp sizing agent for glass fiber fabric has little tackiness when wet. Therefore, it is easy to control the amount of adhesion by the mangle, and it is easy to separate from the adjacent glass fiber yarn due to vibration during drying, etc. Even if it is adhered, the adhesive agent existing between them is low in adhesiveness It is considered that the yarn is easy to move and the amount of the sizing agent between the adjacent yarns is small, which results in a good splittability that cannot be obtained by the conventional sizing agent.

[0023]

The present invention will be described in more detail with reference to the following examples. <Example 1> 1000 g of high amylose cornstarch
Was charged into a pressure blender, and a solution of 25 g of triethylamine dissolved in 100 g of methanol was sprayed while stirring. 1,2-Propylene oxide (150 g) and epichlorohydrin (0.2 g) were added, and the mixture was crosslinked and hydroxypropylated at 50 ° C. for 12 hours. After completion of the reaction, it was neutralized with sulfuric acid, dried and refined. The crosslinked hydroxypropylated high amylose corn starch (Sample 1) was hydroxypropylated M. S. The value is 0.13,
The viscosity of a 5% aqueous solution at 60 ° C., type B viscometer, 60 rpm was 22 mPa · s.

Example 2 1000 g of acid-treated corn starch whose viscosity has been lowered by acid treatment with sulfuric acid is added to 150 parts of water.
Put in a beaker containing 0g, then vinyl acetate 12
0 g was added, and 3% caustic soda was added dropwise to maintain the pH at 8 and acetylated at 40 ° C. for 4 hours with stirring. After completion of the reaction, it was neutralized with sulfuric acid, dried and refined. D. of acetylation of the resulting acetylated corn starch (Sample 2). S.
The value was 0.08, and the viscosity of a 5% aqueous solution at 60 ° C., type B viscometer, at 60 rpm was 15 mPa · s.

Example 3 1000 g of oxidized tapioca starch whose viscosity has been reduced by oxidation treatment with hydrogen peroxide, 300 g of sodium sulfate, and 15 g of caustic soda are placed in a pressure resistant reaction vessel containing 1500 g of water, and then 1,2-propylene. 150 g of oxide was added and hydroxypropylated at 45 ° C. for 20 hours. After completion of the reaction, it was neutralized with sulfuric acid, dried and refined. The hydroxypropylated tapioca starch (Sample 3) obtained was hydroxypropylated M. S. The value is 0.12, 5% aqueous solution at 60 ° C., B-type viscometer, 6
The viscosity at 0 rpm was 20 mPa · s.

<Example 4> As the reduced starch syrup, "DIATOL" manufactured by Sanei Saccharification Co., Ltd. was prepared. This "Diatol" is a monosaccharide alcohol (sorbitol) 10
Weight% or less, disaccharide alcohol 50 to 56% by weight, trisaccharide alcohol 15 to 25% by weight, tetrasaccharide or higher sugar alcohol 2
It has a sugar alcohol composition of 0 to 25% by mass,
It is in the form of an aqueous solution having a concentration of 70% by mass. To 200 g of this reduced starch syrup aqueous solution, 20 g of a sodium hydroxide aqueous solution having a concentration of 15% by mass (0.09 mol per 1 mol of anhydrous glucose unit of reduced starch syrup) was added, and then as a cationizing agent having a concentration of 80% by mass. Add 80 g of glycidyl trimethyl ammonium chloride aqueous solution (0.5 mol to 1 mol of anhydrous glucose unit of reduced starch syrup) and warm to 5
The reaction was carried out at 0 ° C for 7 hours. After the completion of the reaction, the reaction solution was neutralized with concentrated nitric acid, and then electrodialysis was performed to remove uncationized and ring-opened cationizing agents that did not react with reducing starch syrup. Electrodialysis is carried out using a Micro Acilyzer G3 manufactured by Asahi Kasei Co., Ltd. and a cartridge A having a molecular weight cutoff of 300.
C-220-40 was used. The concentration of the obtained cationized reduced starch syrup (Sample 4) in the form of an aqueous solution was 55.0% by mass, the nitrogen content was 3.0% by mass, and the 50% aqueous solution was 60 ° C.
The viscosity was 50 mPa · s.

<Example 5> In Example 3, when the hydroxypropylation was completed, it was not neutralized, and subsequently, 380 g of an aqueous glycidyltrimethylammonium chloride solution having a concentration of 80% by mass was added as a cationizing agent and heated to 5
The reaction was carried out at 0 ° C for 7 hours. After completion of the reaction, the reaction solution was neutralized with concentrated nitric acid and washed with water to prepare a hydroxypropylated M. S. The value was 0.12 and the nitrogen content was 2.7% by mass. This was not dried but redispersed in water and subjected to an enzyme denaturation treatment according to a conventional method. The enzymatically modified cationized hydroxypropylated tapioca starch degradation product (Sample 5) was adjusted to an aqueous solution having a concentration of 60% by mass. 50% aqueous solution 60 ° C
The viscosity was 360 mPa · s.

Example 6 To 200 g of sorbitol (in the form of an aqueous solution having a concentration of 70% by mass), 20 g of an aqueous sodium hydroxide solution having a concentration of 15% by mass was added, and then as a cationizing agent, glycidyl trimethyl having a concentration of 80% by mass was added. Add 80 g of ammonium chloride aqueous solution and heat to 50 ° C.
And reacted for 7 hours. After the reaction was completed, the reaction solution was neutralized with concentrated nitric acid, and then the cationized sorbitol formed (Sample 6)
Was adjusted to a concentration of 60% by mass. The nitrogen content was 3.0 mass%, and the viscosity was 18 mPa · s at 60 ° C. in a 50% aqueous solution.

Example 7 Partially Saponified Polyvinyl Alcohol (Nippon Gosei Co., Ltd., Part No. GL-5) 3.5k
g, 1.5 kg of cross-linked hydroxypropylated high amylose corn starch (Sample 1) and 1.0 kg of cationized sorbitol (Sample 6) were dispersed in 70 kg of water, heated to 90 ° C., stirred and held for 10 minutes, and then 65 ℃
To liquid (liquid A). In a separate container, 500 g of paraffin emulsion (solid content 30% by mass) (solution B) and 100 g of formalin (solution C) are prepared. Solution A to solution B,
After adding the liquid C in order, water is added to adjust the total mass to 100 kg and the temperature is kept at 60 ° C. This glue is warped with G75
Using a sizing machine (manufactured by Tsuda Koma Kogyo Co., Ltd.), 1.16% by mass of solid content was attached to 0.7Z yarn (400 filaments, twist number 0.7 times / 25 mm),
After drying, it is divided and wound up on a weaving beam, and the weaving density is 44 warps / 2 by a high-speed air jet loom (made by Tsuda Koma Kogyo)
It was woven into a glass fabric of 5 mm and 32 wefts / 25 mm.
When the evaluation results described below were carried out <Evaluation of dividing property>
Was 1 and <fluff evaluation> was 1. <Evaluation of splittability> The splittability is evaluated by gluing the warp yarns and drying them, then dividing the adjacent yarns up and down with a splitting rod, and measuring the length from the splitting rod to the place where the warp yarns are actually split. It was measured and classified into 7 ranks. 1 indicates the longest, and 7 indicates the shortest, and the longer the length is, the easier it is to divide. If 3-4 or less, it is sufficiently durable for normal use. <Evaluation of fluff> The fluff is evaluated by counting the number of fluffs on the surface of the woven fabric after weaving with a loom and classifying into 7 ranks. 1 is the smallest and 7 is the largest. If there is enough, it can withstand normal use.

Example 8 Polyvinyl alcohol (Product No. GL-5) 3.5% by mass Acetylated corn starch (Sample 2) 1.5% by mass Cationized reducing starch syrup (Sample 4) 1.0% by mass Hydrogenated cottonseed oil 1 0.0 mass% polyoxyethylene ether 0.1 mass% formalin 0.1 mass% water 92.8 mass% A paste having the above composition was prepared in the same manner as in Example 7, and manufactured to warp E255 1.0Z ( 200 filaments,
A sizing machine (made by Tsudakoma Kogyo Co., Ltd.) was used to adhere 1.20% by mass to a yarn having a twist number of 1.0 times / 25 mm, and a high-speed air jet loom (made by Tsudakoma Kogyo Co., Ltd.) was used. The woven fabric has a weaving density of 60 warps / 25 mm and wefts 58/25 mm. Evaluation results <
Dividability evaluation> was 1 and <fluff evaluation> was 2.

<Example 9> Polyvinyl alcohol (product number GL-5) 2.0% by mass Polyvinyl alcohol (Kuraray Co., Ltd. product number 217) 1.5% by mass Cationized sorbitol (sample 6) 2.5% by mass Paraffin Emulsion (solid content 30% by mass) 0.7% by mass Formalin 0.1% by mass Water 93.2% by mass E255 1.0Z (warped) prepared by preparing a sizing agent having the above composition in the same manner as in Example 7. 200 filaments,
A sizing machine (manufactured by Tsuda Koma Kogyo Co., Ltd.) was used to adhere 1.25% by mass to a yarn of 1 twist / 25 mm), and a high-speed air jet loom (manufactured by Tsudakoma Kogyo Co., Ltd.) was used.
The weaving density is 60 warps / 25mm, wefts 58/2
It was a glass fabric of 5 mm. Evaluation results <
Dividability evaluation> was 2, and <fluff evaluation> was 1.

<Example 10> Polyvinyl alcohol (product number GL-5) 1.4% by mass Polyvinyl alcohol (Kuraray Co., Ltd. product number 217) 1.6% by mass Cationized reducing starch syrup (sample 4) 3.0% by mass Paraffin emulsion (solid content 45% by mass) 0.4% by mass Formalin 0.1% by mass Water 93.5% by mass A sizing agent having the above composition was prepared in the same manner as in Example 7, and warped G75 0.7Z. Using a sizing machine (manufactured by Tsudakoma Kogyo Co., Ltd.), 1.17 mass% of the filaments was applied to a yarn (400 filaments, twisted number of 0.7 times / 25 mm), and a high-speed air jet loom (Tsukoma Kogyo ( Co., Ltd.)
And weaving density is 44 warps / 25 mm, 32 wefts / 2
It was a glass fabric of 5 mm. Evaluation results <
Dividability evaluation> was 1 and <fluff evaluation> was 2.

<Comparative Example 1> 1.5 kg of cross-linked hydroxypropylated high amylose corn starch (sample 1) and 1.0 kg of cationized sorbitol (sample 6) were added, but partially saponified polyvinyl alcohol (Nippon Gosei Co., Ltd.) was used. A glass woven fabric was produced in the same manner as in Example 7 except that 6.0 kg of product No. GL-5) was added. The adhered solid content was 1.16% by mass. As a result of evaluation, <dividing property evaluation> was 6 and <fluff evaluation> was 5.

<Comparative Example 2> 3.5 kg of partially saponified polyvinyl alcohol (Nippon Gosei, product number GL-5) and cross-linked hydroxypropylated high amylose corn starch without adding 1.0 kg of cationized sorbitol (Sample 6). (Sample 1) Example 7 except that 2.0 kg was added
A glass fabric was prepared in the same manner as in. The adhered solid content is 1.2
It was 1% by mass. When the evaluation results were performed, the <dividing property evaluation> was 5, and the <fluff evaluation> was 4.

Comparative Example 3 4.0% by mass of polyvinyl alcohol (product number GL-5) and polyvinyl alcohol (Kuraray Co., Ltd. product number 217) were added without adding 3.0% by mass of cationized reduced starch syrup (sample 4). ) A glass fabric was prepared in the same manner as in Example 10 except that 2.0 mass was added.
The adhered solid content is 1.23% by mass. As a result of evaluation, <dividing property evaluation> was 7 and <fluff evaluation> was 6.

Comparative Example 4 3.0% by mass of cationized reduction starch syrup (Sample 4) was added to 0.1% by mass, 1.5% by mass of polyvinyl alcohol (product number GL-5) was added to 5.0% by mass,
And polyvinyl alcohol (Kuraray Co., Ltd. product number 21)
7) A glass woven fabric was produced in the same manner as in Example 10 except that 1.3% by mass was added to 0.5% by mass and the addition amount was changed. The adhered solid content was 1.21% by mass.
When the evaluation results were performed, the <dividing property evaluation> was 5, and the <fluff evaluation> was 4.

[0037]

As described above, since the glass fiber warp glued with the sizing agent according to the present invention can be easily divided after drying, the occurrence of fluff of the warp is small. Further, since it has excellent abrasion resistance, the glass fabric using this warp has an extremely small amount of fluff as compared with the conventional product.

Claims (6)

[Claims] 1. A film forming agent comprising polyvinyl alcohol, hydroxyalkylated starch and / or acetylated starch, and a cationized starch decomposition product and / or a cationized hydroxyalkylated starch decomposition product blended therein. 2. A film forming agent comprising a polyvinyl alcohol mixed with a cationized starch decomposition product and / or a cationized hydroxyalkylated starch decomposition product. 3. A warp for a glass fiber woven fabric, comprising polyvinyl alcohol, hydroxyalkylated starch and / or acetylated starch mixed with a cationized starch decomposition product and / or a cationized hydroxyalkylated starch decomposition product. Paste. 4. A warp sizing agent for glass fiber woven fabric, characterized in that polyvinyl alcohol is blended with a cationized starch decomposition product and / or a cationized hydroxyalkylated starch decomposition product. 5. A sizing agent comprising polyvinyl alcohol, a hydroxyalkylated starch and / or an acetylated starch, and a cationized starch decomposition product and / or a cationized hydroxyalkylated starch decomposition product mixed therein is attached. Warp for glass fiber fabric. 6. A warp yarn for glass fiber woven fabric, comprising a sizing agent prepared by blending a cationized starch decomposition product and / or a cationized hydroxyalkylated starch decomposition product to polyvinyl alcohol.