JP4016082B2 - Modified starch for glass fiber sizing agent, sizing agent, and glass fiber to which it is attached - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a modified starch for a glass fiber sizing agent, which prevents generation of formaldehyde during deoiling and has good yarn properties, a glass fiber sizing agent, and a glass fiber to which this sizing agent is attached.
[0002]
[Prior art]
Bundling agents that act as film forming agents are roughly classified into yarn and roving. As a sizing agent for yarn, starch or a product obtained by chemically modifying starch is used as a main agent. This is because starch has an appropriate film forming force and adhesive force, is easy to fire and deoil, and is relatively inexpensive. In addition to starch, a lubricant, a cationic softening agent, a surfactant, a preservative and the like are added to the sizing agent as an auxiliary 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 the phenomenon of migration in which specific components (generally water-soluble components) migrate to the surface when the applied sizing agent dries the wound yarn package, -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”. Japanese Patent Laid-Open No. 61-270236 states 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 the glass fiber. "Agent" has been proposed.
[0005]
As an improvement in deoiling property, Japanese Patent Application Laid-Open No. 8-104548 discloses “a glass fiber sizing agent containing at least one ammonium sulfate-based compound and glass fiber having 0.001 to 10.00% by weight attached thereto”. Proposed.
[0006]
[Problems to be solved by the invention]
The improvement of the various sizing agents described above is aimed at improving the film properties of the sizing agent coated on the yarn, and the yarn hardness, dust fall, and fluffing of the yarn are evaluated. However, in recent years, formaldehyde gas generated by burning starch and PVA (polyvinyl alcohol) at the time of deoiling (referring to a process for firing a sizing agent coated with yarn) is harmful to the human body from the viewpoint of improving the working environment. It is a problem.
[0007]
An object of the present invention is to provide a modified starch for a glass fiber sizing agent that prevents generation of formaldehyde during deoiling and has good yarn properties, a sizing agent, and a glass fiber to which the sizing agent is attached.
[0008]
[Means for Solving the Problems]
As a result of intensive studies to solve the above-mentioned problems, the inventors have added starch to starch or modified starch for glass fiber sizing agent, characterized in that it contains urea. Or a glass fiber sizing agent characterized by containing a carbamic esterified starch, and the glass fiber to which these sizing agents are attached prevents generation of formalin at the time of deoiling and has good yarn physical properties. It was found that it is effective in solving the problem.
[0009]
DETAILED DESCRIPTION OF THE INVENTION
The modified starch for glass fiber sizing agent of the present invention is characterized in that the starch contains urea or is carbamate-esterified. However, in order to use it as a glass fiber sizing agent, it is approximately 1 at 60 ° C. in a 5% aqueous solution. In order to prepare a viscosity (molecular weight) having a viscosity of ˜50 CPS, hydrolysis treatment or crosslinking treatment must be performed.
As the modified starch for glass fiber sizing agent of the present invention, the starch is added with urea as a powder or an aqueous solution, or the starch and urea are reacted by heating to form a carbamic acid ester. The hydrolysis treatment or cross-linking treatment is an essential treatment, and at least one kind of modification selected from the group of etherification, esterification, and grafting is performed as necessary.
[0010]
The kind of starch used as a raw material is selected from corn starch, tapioca starch, wheat starch, sweet potato starch, potato starch or high amylose corn starch.
[0011]
The modified starch of the present invention is subjected to a low molecular weight treatment as necessary. The low molecular weight treatment is an acid hydrolysis treatment with a mineral acid or organic acid such as sulfuric acid, nitric acid, hydrochloric acid, hydrogen peroxide, hypochlorite. An oxidation treatment with an oxidizing agent such as acid soda. The degree of lowering the molecular weight is indicated by the viscosity resulting from hydrolysis to lower the viscosity (lower molecular weight). A viscosity of about 1 to 50 CPS, preferably 3 to 20 CPS in a 5% aqueous solution at 60 ° C. is preferably used.
[0012]
The modified starch of the present invention may be subjected to one or more kinds of modification selected from the group of etherification, esterification, grafting, and crosslinking treatment as needed in addition to the molecular weight reduction treatment. Etherification includes carboxymethylation, hydroxyalkylation, alkylation, benzylation, cationic etherification and the like. Of these, hydroxyalkylation is particularly effective. Hydroxyalkylation is obtained by reacting starch with 1 · 2-alkylene oxide, ie, ethylene oxide, 1 · 2-propylene oxide, or 1 · 2-butylene oxide. These alkylene oxides are added to corn starch, tapioca starch, wheat starch, sweet potato starch, and potato starch so that the MS value is in the range of 0.03 to 0.26, preferably 0.07 to 0.20. The high amylose corn starch is added so that the MS value is in the range of 0.07 to 0.36, preferably 0.10 to 0.30. Here, the MS value indicating the degree of hydroxyalkylation means the number of moles (Molar Substitution) of hydroxyalkyl groups per anhydroglucose residue of starch.
[0013]
Esterification includes acetate ester, phosphate ester, sulfate ester, nitrate ester, xanthate ester, etc. Among them, acetate ester is effectively used. The degree of esterification is such that the DS value is 0.03 to 0.26, preferably 0.07 to 0.20 for corn starch, tapioca starch, wheat starch, sweet potato starch, and potato starch. It is added to the high amylose corn starch so that the DS value is in the range of 0.07 to 0.36, preferably 0.10 to 0.30. Here, the DS value indicating the degree of esterification refers to the number of substituted ester groups per anhydroglucose residue of starch (Degree of Substitution).
[0014]
Grafting is performed by graft polymerization of one or more radically polymerizable monomers such as vinyl acetate, acrylic acid, acrylic ester, methacrylic acid, methacrylic ester, acrylamide, styrene, maleic acid, and crotonic acid. Obtained. The polymerization is carried out wet or dry using a normal radical polymerization catalyst.
[0015]
The modified starch for a glass fiber sizing agent of the present invention can be adjusted in viscosity by a crosslinking reaction in combination with the above-described low molecular weight treatment, etherification, esterification and grafting. As the crosslinking agent, a reagent having two or more functional groups capable of reacting with a hydroxyl group of starch such as epichlorohydrin, sodium trimetaphosphate, cyanuric chloride, adipic-acetic anhydride, formalin, diepoxide compound, and dialdehyde compound is used. It is done.
[0016]
The modified starch for glass fiber sizing agent of the present invention is characterized in that the starch contains urea or carbamic acid ester, but in addition to using the modified starch containing urea, urea is added when the sizing agent is prepared. By doing so, a urea-containing glass fiber sizing agent can be obtained. The starch carbamic acid ester of the present invention can be obtained by heating urea and starch (at 120 ° C. or higher).
[0018]
The amount of urea to be added to the modified starch for glass fiber sizing agent of the present invention or the amount of urea to be added when carbamate is esterified is 2% to 10%, preferably 3% to 5% with respect to the starch weight.
If the amount of urea added is less than 2%, the generation of formaldehyde cannot be completely eliminated. Moreover, even if the urea addition amount is 10% or more, the effect is not changed and the strength of the starch film is lowered, which is not preferable.
[0019]
The modified starch for glass fiber sizing agent of the present invention is a lubricant usually used for sizing agent for glass fiber (hardened oil hydrogenated to animal and vegetable oil, paraffin wax, condensate of higher saturated fatty acid and higher saturated alcohol, etc.) Cationic softening agents (such as amides or imidazolines obtained by reacting tetraethylenepentamine and stearic acid, reaction products with Poiethyleneimine having about 8 to 18 carbon atoms), surfactants (polyoxyethylene polyalkyl) Ether, polyoxyethylene alkyl ether, etc.) Preservatives and other auxiliaries are added and mixed to form a sizing agent for glass fibers, which is applied to glass filaments.
[0020]
【Example】
Example 1 (Sample preparation)
1000 g of each of corn starch and high amylose corn starch was put into a pressure-resistant blender, and a solution obtained by dissolving 25 g of triethylamine in 100 g of methanol was sprayed with stirring. 120-250 g of 1,2-propylene oxide was added and hydroxypropylated at 50 ° C. for 10 hours. After completion of the reaction, 60% sulfuric acid (20-50 g) diluted with 100 g of methanol was added and hydrolyzed at 45 ° C. for 2-5 hours to lower the viscosity. When it reached a predetermined viscosity, it was neutralized with triethylamine diluted with methanol to stop the hydrolysis reaction, then dried and refined. M. of hydroxypropylation of each starch. S. Values and viscosities at 60 ° C., B-type viscometer, 60 rpm of a 5% aqueous solution are corn starch crosslinked and hydroxypropylated samples S. A cross-linked / hydroxypropylated sample with a value of 0.11, viscosity of 7 CPS and high amylose corn starch. S. The value was 0.16 and the viscosity was 9 CPS. These were prepared by adding 1, 5, 10% of urea to them and mixing them uniformly and by heating them at 130 ° C. for 2 hours to form carbamic esters.
[0021]
Example 2 (Yarn physical property evaluation of sample)
Next, hydrolyzed and hydroxypropylated samples of corn starch and high amylose corn starch obtained in this way, and 1, 5, 10% of urea added to these samples, mixed uniformly, and heated at 130 ° C. for 2 hours 4.0% by weight of each carbamic acid ester, 0.7% by weight of hydrogenated vegetable oil, 0.8% by weight of paraffin wax, 0.25% by weight of acetic acid activated product of a condensate of tetraethylenepentamine and stearic acid %, An emulsifier (polyoxyethylene polypropylene ether) 0.2% by weight and the balance of the present invention consisting of water is used to attach 0.8% to 1.0% by weight of the sizing agent of the present invention. Was woven. Graded according to the level of powder falling in the yarn twisting and warping processes, ranked to 5 ranks based on the number of fluff on the cross surface, and measured values of the arrival timing when weaving the yarn as wefts and wefts The overall number of loom stops caused by the above was judged and the flying performance was graded to 5 ranks. After the cloth was heated and deoiled, the whiteness and coloring degree were comprehensively judged and the deoilability was graded to 5 ranks. Smaller values indicate better results.
[0022]
With respect to the yarn physical properties of the hydrolyzed and hydroxypropylated sample of corn starch, the adhesion rate was 0.89%, dust removal grade 2, fluff grade 2, flying ability grade 1, and oil removal grade 1.
As for the yarn physical properties of corn starch hydrolyzed and hydroxypropylated samples with 1,5, 10% added urea and mixed uniformly, the adhesion rate was 0.91, 0.93, 0.96%, and the powder removal grade was The 2, 2, 1, fluff grades were 2, 2, 2, respectively, the flying grades were 1, 1, 1, respectively, and the deoiling grades were 1, 1, 1, respectively.
The corn starch hydrolyzed and hydroxypropylated samples were added with 1, 5 and 10% urea and mixed uniformly and heated at 130 ° C for 2 hours to form carbamic acid ester. , 0.86, 0.87%, powder fall grades 2, 2, 3, respectively, fluff grades 2, 2, 2, respectively, flightability grades 1, 1, 1, respectively, oil removal grades 1, respectively 1 and 1.
[0023]
The adhesion rate of the hydrolyzed / hydroxypropylated sample of high amylose corn starch was 0.90%, dust removal grade 2, fluff grade 1, flying ability grade 3, and oil removal grade 1.
High amylose corn starch hydrolyzed and hydroxypropylated with 1,5,10% urea and mixed uniformly, the yarn properties were 0.90, 0.93, 0.94%, and powder fall off, respectively. The grades were 2, 1, 1, respectively, the fluff grades were 1, 1, 1, respectively, the flying performance grades were 3, 2, 2, respectively, and the oil removal grades were 1, 1, 1, respectively.
A high amylose corn starch hydrolyzed and hydroxypropylated sample with 1,5, 10% urea added and mixed uniformly and heated at 130 ° C. for 2 hours for carbamic acid ester, the adhesion rate is 0 for each. .87, 0.87, 0.88%, dusting grades are 2, 1, 1, fluff grades are 1, 1, 1, respectively, flying performance grades are 3, 2, 2, respectively, oil removal grades are each 1, 1, 1.
[0024]
Example 3 (formaldehyde quantitative test generated from a sample)
Corn starch, high amylose corn starch hydrolyzed and hydroxypropylated samples examined in Example 2 and 1,5,10% urea added to these samples, and mixed uniformly at 130 ° C. The film of each sample was obtained by pouring 20 ml of 4% paste solution which had been heated for a time and carbamate ester into a 10 cm × 10 cm frame attached to a polyester film and allowed to dry naturally.
[0025]
About 0.8 g of this film is cut into a 1 cm square, placed in a Kjeldahl flask used in the nitrogen determination method, and burned at 450 ° C. for 45 minutes. The gas generated by the combustion was decompressed with an aspirator and blown into 15 ml of ion-exchanged water in the Erlenmeyer flask, and the formaldehyde gas generated by the combustion was dissolved in the ion-exchanged water. Next, 1 ml of the test solution thus obtained and 1 ml of Schiff's solution (a reagent manufactured by Hayashi Junyaku Co., Ltd.) are mixed to develop a red purple color. On the other hand, 37% formaldehyde solution (reagent) is appropriately diluted to prepare 9.25-74.0 ppm (μg / ml) solution, which is used as standard solution, and 1 ml of standard solution and Schiff's solution (reagent manufactured by Hayashi Junyaku Co., Ltd.) 1 ml was mixed to develop reddish purple with different shades. The formaldehyde concentration of the test solution was determined by visual comparison of the red-purple color of the standard solution of known concentration and the red-purple color of the test solution. The amount of formaldehyde generated from the sample (μg / g = ppm) is obtained by multiplying the formaldehyde concentration (μg / ml) of the test solution determined from the standard solution by 15 (ml) and dividing by the weight of the sample (g) formed into a film. The amount of formaldehyde generated per gram of the sample was determined.
[0026]
The amount of generated formaldehyde in the hydrolysis / hydroxypropylated sample of corn starch was 1900 ppm.
In the cornstarch hydrolyzed / hydroxypropylated sample, 1,5,10% urea was added and mixed uniformly, and the amount of generated formaldehyde was 130, 0, 0, respectively.
The corn starch hydrolyzed and hydroxypropylated samples were added with 1, 5 and 10% urea and mixed uniformly and heated at 130 ° C. for 2 hours to form carbamic acid esters. The amount of formaldehyde generated was 140, 10 and 0, respectively. Met.
[0027]
The amount of generated formaldehyde in the hydrolyzed / hydroxypropylated sample of high amylose corn starch was 910 ppm.
The amount of generated formaldehyde was 80, 0, and 0, respectively, when 1,5, 10% of urea was added to the hydrolyzed / hydroxypropylated sample of high amylose corn starch and mixed uniformly.
Hydrolyzed and hydroxypropylated samples of high amylose corn starch were added with 1, 5, 10% urea and mixed uniformly and heated at 130 ° C. for 2 hours to form carbamic acid esters. , 0.
[0028]
【The invention's effect】
The starch of the present invention containing urea or carbamic acid ester is used as a sizing agent for glass fiber sizing agent, or a sizing agent added with urea at the time of sizing agent preparation is used. Glass fiber that does not generate formaldehyde gas during deoiling combustion and has a sizing agent containing urea attached has excellent properties such as excellent deoiling properties, low powdering and fluffing, and good flying properties.

Claims (3)

A modified starch for glass fiber sizing agents, characterized in that the starch contains urea or is carbamate esterified. A glass fiber sizing agent comprising starch containing urea or starch carbamate esterified as a modified starch for glass fiber sizing agent. A glass fiber comprising a sizing agent containing a starch containing urea or a carbamic acid esterified starch as a modified starch for a glass fiber sizing agent .