JP4821294B2 - Glass fiber sizing agent - Google Patents

Description

  The present invention relates to a glass fiber sizing agent, a glass fiber bundle that is bundled with the glass fiber sizing agent, and a method for producing a glass fiber fabric using the glass fiber bundle.

  The glass fiber fabric is manufactured by weaving with various weaving machines using a glass fiber bundle formed by bundling glass fiber filaments with a bundling agent as warp and weft. And as a weaving machine for glass fiber fabrics, it is common to use an air jet loom that causes wefts to fly by compressed air.

  In an air jet loom, since a glass fiber bundle flies at a very high speed, fluff is generated in the glass fiber bundle, and a problem that weaving defects and product defects have conventionally occurred. For this reason, the sizing agent used for coating glass fiber bundles requires not only the ability to bundle glass fibers (squeezing property) but also the ability to prevent fuzz (coating property). Various studies have been made on the formulation of (see, for example, Patent Document 1).

  By the way, at the end of the glass fiber fabric woven by the air jet loom, surplus wefts that do not intersect with the warp are protruding, and this is cut with a cutter provided in the air jet loom so that glass of a predetermined width is obtained. A textile fabric is produced. FIG. 1 is a schematic diagram (top view) of an air jet loom. The air jet loom shown in the figure is provided with a nozzle 7 on one side, and the weft 2 is blown by the air jetted intermittently from the nozzle 7 and inserted into the warp 1. When the weft 2 is inserted to a predetermined position, the glass fiber fabric 10 is woven by the heel 3 of the weft 2. Then, the weft 2 a at the end not intersecting with the warp of the glass fiber fabric 10 is separated from the glass fiber fabric 10 by the cutter 5. In order to prevent scattering of the cut weft yarn 2a, the weft yarn 2a is generally entangled with a yarn called a catch cord (hereinafter referred to as "discard yarn") 8. The yarn discarding section 6 composed of the cut weft yarns 2a and the yarn disposal 8 is conveyed through a roll 9 and put into a container for collecting the yarn disposal section 6.

However, even when the weft yarn is entangled with the weft yarn at the end that does not intersect with the warp yarn as described above, the cut weft yarn is scattered if the suppression of the generation of static electricity during weaving is insufficient, There has been a problem of being woven into the glass fiber fabric. In order to solve this problem, there is a technique of adding an antistatic agent to the sizing agent for the purpose of suppressing the generation of static electricity during weaving (see, for example, Patent Document 2).
JP 2003-89554 A Japanese Patent Laid-Open No. 50-20096

  However, the inventions described in Patent Documents 1 and 2 have the following problems. That is, the cationic surfactant-containing glass fiber sizing agent described in Patent Document 1 is effective in suppressing the generation of fuzz, but there is room for improvement in terms of suppressing static electricity during weaving. It was. On the other hand, when the technology described in Patent Document 2 is adopted and a glass fiber bundle is coated using a conventional glass fiber sizing agent to which a general antistatic agent is added, the glass fiber bundle is excessively flexible. There is a problem of becoming. When the glass fiber bundle is excessively flexible, the occurrence of fluff becomes significant when an air jet loom is used to weave the glass fiber fabric.

  Accordingly, an object of the present invention is to provide a glass fiber sizing agent that can effectively prevent the occurrence of fluff in a glass fiber fabric woven by an air jet loom and sufficiently suppress the generation of static electricity during weaving. And Another object of the present invention is to provide a glass fiber bundle that is bundled with such a glass fiber sizing agent, and a method for producing a glass fiber fabric using the glass fiber bundle.

The glass fiber sizing agent of the present invention is a reaction product obtained by reacting a fatty acid with an amine compound represented by the following general formula (1), and a glass fiber sizing agent containing starch, an oil agent, and water, The ratio of the total mass (M _F ) of the fatty acid to the total mass (M _A ) of the amine compound contained in the raw material of the reaction product is M _F / M _A = 2.1 to 2.6.
H ₂ N (R ¹ NH) _n R ¹ NH ₂ (1)
In formula (1), R ¹ represents an alkylene group having 1 to 10 carbon atoms, and n represents an integer of 0 to 10, respectively.

The present inventors have confirmed in previous studies that an aqueous glass fiber sizing agent containing starch as a film-forming agent has an excellent anti-fuzzing performance. The inventors of the present invention have intensively studied whether or not the bundling agent can be imparted with static electricity suppressing performance while maintaining the fluff prevention performance at a high level. As a result, it is obtained by reacting a fatty acid and an amine compound at a reaction ratio in a predetermined range, in particular, a predetermined reaction ratio (M _F / M _A = 2.1 to 2.6) based on the mass of the raw material. It has been found that by adding the reactant to the sizing agent, the sizing agent can be imparted with static electricity suppressing performance.

Further, the sizing agent can be blended with one or more of the above reactants. When two or more of the reactants are blended, the reactants necessarily contain a fatty acid and an amine compound as described above. The ratio of the total mass (M _A ) of the amine compound and the total mass (M _F ) of the fatty acid contained in the raw material for obtaining each reactant is not necessarily required to be reacted at a reaction ratio in the range of Within the range, the inventors found that the static electricity suppressing performance can be obtained in the same manner, and completed the present invention.

  According to the sizing agent for glass fibers of the present invention, it is possible to achieve both high fuzz prevention performance and static electricity suppression performance at a high level. For this reason, it is possible to effectively prevent the occurrence of fluff in the glass fiber fabric even when weaving with an air jet loom where the glass fiber bundle receives a large impact during weaving, and fluff is likely to occur. The generation of static electricity that can be a cause can be sufficiently suppressed.

  Moreover, in the sizing agent for glass fibers of this invention, it is preferable to contain 2-5 mass% of the said reaction materials on the basis of the total mass of the non-volatile component of the said sizing agent for glass fibers. In addition, in this invention, a non-volatile component means the component which does not volatilize, when the sizing agent for glass fibers is apply | coated to a glass fiber filament and it heats to 110 degreeC.

  The glass fiber bundle of the present invention is coated with the glass fiber sizing agent of the present invention.

  Further, the method for producing a glass fiber fabric of the present invention uses the glass fiber bundle of the present invention as a weft, weaves it by flying with compressed air and intersecting with the warp, and the end not intersecting with the warp This is a method of cutting the weft.

  Because glass fiber bundles coated with a glass fiber sizing agent with static electricity control performance are used as wefts, even if the wefts at the ends that do not intersect the warp of the glass fiber fabric are cut during weaving, they will scatter Can be sufficiently prevented. For this reason, it is possible to sufficiently reduce the problem of the cut weft being woven into the glass fiber fabric, that is, the so-called weaving defect.

  According to the present invention, it is possible to provide a glass fiber sizing agent that can effectively prevent the occurrence of fluff in a glass fiber fabric woven by an air jet loom and sufficiently suppress the generation of static electricity during weaving. It becomes. In addition, it is possible to provide a glass fiber bundle that is bundled with the glass fiber sizing agent, and a method for producing a glass fiber fabric using the glass fiber bundle.

The sizing agent for glass fibers of the present invention is a reaction product (hereinafter referred to as “amide reaction product”) obtained by reacting a fatty acid with an amine compound represented by the following general formula (1), starch, oil agent and water. The ratio of the total mass (M _F ) of the fatty acid to the total mass (M _A ) of the amine compound contained in the raw material of the amide reaction product is M _F / M _A = 2.1 It is -2.6.
H ₂ N (R ¹ NH) _n R ¹ NH ₂ (1)
[In Formula (1), R ¹ represents an alkylene group having 1 to 10 carbon atoms, and n represents an integer of 0 to 10, respectively. ]

  Hereinafter, each of the amide reactant, starch, oil and water used for the preparation of the sizing agent for glass fibers of the present invention will be described in detail. First, the amide reactant will be described.

In the amide reaction product of the present invention, the reaction ratio between the fatty acid and the amine compound represented by the general formula (1) is reacted in a predetermined range (M _F / M _A = 2.1 to 2.6). It will be. One or more of these amide reactants can be used as a blending component. By using a sizing agent in which an amide reactant obtained from a raw material within the predetermined range is blended, the generation of static electricity that can cause product defects during weaving can be sufficiently suppressed.

When blending two or more amide reactants, the ratio of the mass of the amine compound and the mass of the fatty acid contained in the raw material for obtaining each amide reactant is not necessarily within the predetermined range, The ratio of the total mass of the fatty acid and the amine compound used in the reaction for obtaining the amide reactant may be within the above range. For this reason, the ratio (M _F / M _A ) of the total mass of the amine compound and the total mass of the fatty acid can be easily adjusted by blending a plurality of amide reactants in which the reaction ratio of the fatty acid and the amine compound is known. it can.

Further, by adjusting the ratio of the total mass of the fatty acid relative to the total weight of the amine compound _(M F _/ M _A) in the above range, the glass fiber bundles and the glass fiber coated with a sizing agent containing the amide reactant The electrostatic potential of the fabric can be controlled. This is because when the amine compound contained in the raw material of the amide reaction product has a relatively large amount of amine compound, the electrostatic potential of the glass fiber bundle and the glass fiber fabric fluctuates to the plus side. This is because it fluctuates to the minus side.

If the ratio of the total mass of fatty acids to the total mass of amine compounds (M _F / M _A ) contained in the raw material of the amide reaction product is less than 2.1, the glass fiber bundle and the glass fiber fabric during weaving are excessively positive. On the other hand, when it exceeds 2.6, it is excessively negatively charged. If the glass fiber bundle and the glass fiber fabric are excessively charged in this manner, static electricity is generated during weaving, the cut wefts are scattered and woven into the glass fiber fabric, or the surrounding dust adheres to the glass fiber fabric. This can cause product defects.

It is ideal to control the electrostatic potential of the glass fiber bundle and the glass fiber fabric in the weaving process to be ± 0 kV. However, these electrostatic potentials are generally on the negative side due to variations in temperature and humidity. Tend to fluctuate greatly. For this reason, it is possible to operate stably if the center value of the electrostatic potential is controlled in advance to be slightly on the plus side. In the sizing agent of the present invention, the ratio of the total mass of the fatty acid to the total mass of the amine compound contained in the raw material of the amide reactant is, as described above, in the range of M _F / M _A = 2.1 to 2.6. There is a need to. By making the ratio within the above range, the electrostatic potential of the glass fiber bundle and the glass fiber fabric during weaving can be controlled in the range of +1.5 to -1.0 kV, and thus the cut weft Can be sufficiently suppressed. The ratio is more preferably in the range of M _F / M _A = 2.2 to 2.5. Thereby, the electrostatic potential of the glass fiber bundle and the glass fiber fabric can be controlled in the range of +1.0 to −0.5 kV, and the scattering of the cut wefts can be further sufficiently suppressed.

  The amine compound and fatty acid for obtaining the amide reaction product will be described.

As the amine compound, a compound represented by the general formula (1) can be used. In the general formula (1), R ¹ is an alkylene group having 1 to 10 carbon atoms, and n is an integer of 0 to 10. Each is shown. Specific examples of the amine compound represented by the general formula (1) include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, and hexaethyleneheptamine. In the present invention, R ¹ is more preferably an alkylene group having 2 to 10 carbon atoms, further preferably an alkylene group having 2 to 6 carbon atoms, and particularly preferably an ethylene group. As for n, 1-8 are more preferable, 1-6 are still more preferable, and 3 is especially preferable. Accordingly, tetraethylenepentamine is preferred as the amine compound.

  On the other hand, examples of the fatty acid to be reacted with the amine compound include saturated or unsaturated fatty acids. In the present invention, it is preferable to use a saturated fatty acid having 6 to 32 carbon atoms. As the fatty acid, a saturated fatty acid having 12 to 30 carbon atoms is more preferable, a saturated fatty acid having 12 to 22 carbon atoms is further preferable, and stearic acid is particularly preferable.

An amide reaction product is obtained by reacting a fatty acid with an amine compound represented by the general formula (1). When the fatty acid is R ¹¹ —COOH (R ¹¹ is a saturated or unsaturated hydrocarbon group), For example, it can be represented by the following general formulas (2) and (3) (wherein R ¹ and n are as defined above).
R ¹¹ —CONH— (R ¹ NH) _n R ¹ NH ₂ (2)
_{^{R 11 -CONH- (R 1 NH)}} n R 1 -NHCO-R 11 ··· (3)

  When two or more kinds of amide reactants are blended, each amide reactant is preferably obtained by a condensation reaction of a fatty acid and an amine compound at the following reaction molar ratio. That is, the reaction molar ratio between the fatty acid and the amine compound is preferably the former / the latter = 1-3, and more preferably 1.3-2. This is because an amide reaction product having a reaction molar ratio of a fatty acid and an amine compound within the above range has a small amount of unreacted fatty acid or amine compound. In particular, the amine compound in which the molar ratio of the reaction between the fatty acid and the amine compound is the former / the latter = 1.3-2 is substantially a mixture represented by the above general formulas (2) and (3). it can.

  When obtaining an amide reaction product from a fatty acid and an amine compound, known reaction conditions and reaction catalysts can be employed, and each of the fatty acid and the amine compound can be used alone or in combination of two or more. In addition, the amide reactant in the present invention may be a product whose pH is adjusted with a weak acid such as acetic acid.

  The content of the amide reactant in the present invention is preferably 2 to 5% by mass, more preferably 2.5 to 4% by mass, based on the total mass of the nonvolatile components of the sizing agent. If the content of the amide reaction product is less than 2% by mass, the static electricity suppression performance by the amide reaction product tends to be insufficient, and if it exceeds 5% by mass, the content of starch in the non-volatile component is relatively Since it decreases, the prevention performance of the fluff of a glass fiber bundle tends to become insufficient.

  Next, the starch used in the present invention will be described. In the present invention, corn starch (corn starch), tapioca starch, wheat starch, sweet potato starch, potato starch, high amylose corn starch, sago starch, rice starch and the like can be used as the starch. Moreover, the amylose extract of a potato starch and the special starch synthesize | combined with the enzyme can also be used. These starches may be subjected to processing such as etherification, esterification, grafting, and crosslinking.

  Examples of the etherified starch include carboxymethyl etherified starch, hydroxyalkyl etherified starch, alkyl etherified starch, benzyl etherified starch, and cationic etherified starch. Examples of the esterified starch include acetate esterified starch, phosphate esterified starch, sulfate esterified starch, nitrate esterified starch, and xanthate esterified starch. In both the etherification and esterification, there is no particular limitation on the degree of starch substitution.

  Grafted starch is a graft polymerized with at least one monomer having an unsaturated double bond such as acrylic acid, acrylic acid ester, methacrylic acid, methacrylic acid ester, acrylamide, styrene, maleic acid, etc. Can be exemplified.

  Examples of the starch further include those obtained by introducing cross-linking to raw starch, and those obtained by introducing cross-linking to the above-mentioned starch that has been etherified, esterified or grafted. In the case of introducing cross-linking, a compound having two or more functional groups reactive with hydroxyl groups in starch or a compound that newly generates a hydroxyl-functional functional group by reaction with hydroxyl groups in starch is used as a crosslinking agent. Used. Examples of such a crosslinking agent include epichlorohydrin, formaldehyde, diepoxide compounds, dialdehyde compounds, and the like.

  The amount of the amylose component and the amount of the amylopectin component in the starch used in the present invention are arbitrary. Regular starch with an amylose component of less than 50% by mass (typically containing about 30% by mass of amylose component and about 70% by mass of amylopectin component), and high amylose type starch (typically containing about 50% by mass of amylose component) In particular, both of about 70% by mass of the amylose component and about 30% by mass of the amylopectin component can be used. It is generally said that the sizing agent containing normal type starch is excellent in adhesiveness, and the starch containing high amylose type starch is excellent in film-forming property. In the present invention, at least a part of the starch used is preferably a high amylose type starch, and more preferably a combination of normal type starch and high amylose type starch. 40-80 mass% is preferable on the basis of the total mass of the non-volatile component of the sizing agent for glass fibers, and the mass of starch is more preferable 45-75 mass%.

  Oils that can be used in the present invention include animal oils such as modified silicone oil and beef tallow oil and hydrogenated products thereof; vegetable oils such as soybean oil, rapeseed oil and palm oil and hydrogenated products thereof; higher saturated fatty acids and higher saturated alcohols Examples of such a condensate (stearate such as lauryl stearate); paraffin wax and the like. The oil agent in the sizing agent for glass fibers has a function of giving a slip to the glass fiber bundle, reducing friction on the machine, and protecting the glass fibers. 5-40 mass% is preferable on the basis of the total mass of the non-volatile component of the sizing agent for glass fibers, and, as for the mass of an oil agent, 10-35 mass% is more preferable.

  The sizing agent for glass fibers of the present invention may contain a surfactant in addition to the amide reactant, starch, and oil agent as a nonvolatile component. Examples of such surfactants include amphoteric surfactants such as carboxybetaine and nonionic surfactants such as polyoxyethylene polyalkyl ether. The content of the surfactant is preferably 0.5 to 5% by mass based on the total weight of the nonvolatile components of the glass fiber sizing agent.

  The sizing agent for glass fibers of the present invention contains water as an essential component. Water may be used as long as it can dissolve or disperse the above-described components. For example, ion-exchanged water or distilled water is preferably used. The mass of water is preferably 80 to 98 mass%, more preferably 90 to 97 mass%, based on the total mass of the sizing agent for glass fibers.

  The sizing agent for glass fibers of the present invention may contain a small amount of preservatives, alcohols such as methanol, ethanol, isopropanol, and other organic solvents in addition to the above essential components.

  The preservative that can be used in the present invention is not particularly limited as long as it can protect components such as starch that are susceptible to decomposition by sputum and bacteria. A suitable preservative is formaldehyde. The mass of the preservative is preferably 0.3 to 2 parts by mass and more preferably 0.3 to 1 part by mass with respect to 100 parts by mass of starch.

  The sizing agent for glass fibers of the present invention can be efficiently produced by a production method as described below. That is, after starch is dispersed in water, it is heated to 90 to 98 ° C. to be gelatinized and cooled to 80 ° C. or lower, and each of the amide reaction product and the aqueous solution (or aqueous dispersion) of the oil agent is used alone. Alternatively, it is added in a mixed state, and further diluted with water as necessary. When adding preservatives or alcohols other than the above essential components, these may be added alone or as an aqueous solution (or aqueous dispersion) to the gelatinized starch solution.

  Next, the glass fiber bundle of the present invention will be described. The glass fiber bundle of the present invention is formed by bundling a plurality of glass fiber filaments with the above-mentioned bundling agent for glass fibers. That is, the glass fiber bundle of the present invention is composed of a plurality of glass fiber filaments and the glass fiber sizing agent of the present invention, and the glass fiber sizing agent is present between the plurality of glass fiber filaments. It functions as an adhesive (binder) for bundling filaments. The sizing agent for glass fibers also has a function of protecting the glass fibers by coating the outer periphery of the glass fiber filaments as a continuous or discontinuous film. In the present invention, the glass fiber sizing agent present in the glass fiber bundle is preferably a non-volatile component of the sizing agent.

  The sizing agent for glass fibers only needs to have a strength sufficient to keep the glass fiber filaments in a bundle shape when the glass fiber bundle is used, and does not need to be uniformly distributed in the glass fiber bundle. That is, from the viewpoint of adhesiveness between glass fiber filaments, the glass fiber sizing agent is preferably distributed at a substantially uniform concentration from the outer edge of the glass fiber bundle toward the center. The glass fiber bundle can be held in the present invention even when the concentration is high and the concentration at the center is low, and this is not a problem in practical use.

  The glass fiber filament used in the glass fiber bundle of the present invention preferably has a filament diameter of 3 to 23 μm, and the glass fiber bundle is preferably formed by bundling 50 to 1200 glass fiber filaments. Examples of the glass composition of the glass fiber filament include E glass, S glass, and C glass. In this invention, it is preferable that the non-volatile component mass of the sizing agent for glass fibers with respect to 100 mass parts of glass fiber filaments is 0.5-1.5 mass parts, and 0.7-1.2 mass parts is more preferable.

  In the glass fiber bundle of the present invention, for example, a glass fiber sizing agent is applied to a glass fiber filament drawn from a platinum nozzle (bushing) using a roller-type applicator, a belt-type applicator, or the like, and the resulting glass fiber bundle is focused by a sizing machine. Thus, the glass fiber filaments can be bundled and then dried at room temperature to 150 ° C. to remove volatile components such as water. In addition, you may give twist suitably.

  Next, the manufacturing method of the glass fiber fabric of this invention is demonstrated. The method for producing a glass fiber fabric of the present invention uses the above-described glass fiber bundle of the present invention as a weft, weaves it by flying with compressed air and intersecting with the warp, and at the end not intersecting with the warp This is a method of cutting a weft.

  In the manufacturing method of the glass fiber fabric of this invention, the glass fiber bundle used as the wound body by winding about 10-200 km around the winding tube (outer diameter: 15-40 cm, length: about 10-60 cm) is used. In view of the production process, it is preferable to unwind the glass fiber bundle from the wound body and use it for weaving.

  In the method for producing a glass fiber fabric of the present invention, a glass fiber bundle of 2 to 200 TEX (preferably 5 to 68 TEX) is used as a warp and a weft, and the weave density is 16 to 64/25 mm in the warp direction. It is preferable to weave so as to be 15-60 pieces / 25 mm in the direction.

  In weaving with an air jet loom, the weft yarn (glass fiber bundle) that is spun by air injection is longer than the width of the glass fiber fabric, so that there exists a weft at the end that does not intersect the warp. Become. A glass fiber fabric having a desired width is produced by cutting the weft yarn at the end with a cutter provided in the air jet loom (see FIG. 1). According to the method for producing a glass fiber fabric of the present invention, since a glass fiber bundle bundled with the glass fiber sizing agent of the present invention is used as the weft, the generation of static electricity during weaving can be sufficiently suppressed, and the cut weft Scattering can be sufficiently prevented. For this reason, the generation | occurrence | production of the weaving fault by which the cut weft is woven in a glass fiber fabric can be reduced efficiently, and the product quality of the obtained glass fiber fabric can also be improved. From the viewpoint of sufficiently suppressing static electricity during weaving, it is preferable to use the glass fiber bundle according to the present invention as a warp. In addition, when using the glass fiber bundle of this invention as a warp, you may apply | coat a secondary sizing agent to a warp prior to weaving.

  From the viewpoint of more reliably preventing the cut wefts from being scattered, it is preferable to cut the yarns in a state in which the wefts at the ends not intersecting with the warp yarns are entangled. Examples of the method of entwining the end portion of the weft and the discarding yarn include a method of plain weaving three or more discarding yarns and the weft yarn at the portion. As discarding yarn, a glass fiber bundle of 2 to 200 TEX (preferably 5 to 68 TEX) can be used. From the viewpoint of more sufficiently suppressing static electricity during weaving, the glass fiber bundle according to the present invention may be used as the yarn.

  Hereinafter, preferred examples of the present invention will be described in more detail, but the present invention is not limited to these examples.

[Manufacture of sizing agent for glass fiber]
Example 1
70 kg of water was added and dispersed in 2.2 kg of etherified high amylose corn starch and 2.2 kg of etherified corn starch. Subsequently, this was heated and heated, gelatinized at 95 ° C. for 30 minutes, and then cooled to 65 ° C. (the obtained liquid was designated as A liquid).

  On the other hand, 1.4 kg of heated beef tallow and 0.5 kg of paraffin wax, 0.1 kg of polyoxyethylene polypropylene ether (HLB16) and 0.1 kg of polyoxyethylene lauryl ether (HLB9) were added with hot water and stirred with a mixer. did. Stirring was continued for 5 minutes and then diluted with hot water to a total mass of 5 kg (the obtained liquid was designated as B liquid).

  Further, 100 g of an amide reaction product (i) obtained by reacting the reaction ratio (molar ratio) of stearic acid and tetraethylenepentamine with the former / the latter = 1.3 and the reaction ratio of the former / the latter = 2. Hot water was added to 100 g of the amide reaction product (ii) obtained by the reaction at 0 to make the total mass 2 kg (the obtained liquid was designated as C liquid). Furthermore, 100 g of formalin solution (formaldehyde 30% by mass aqueous solution) was diluted 10 times with water (the obtained solution is designated as solution D).

Subsequently, after adding all the B liquid, C liquid, and D liquid sequentially to A liquid of 65 degreeC, hot water was added so that the total mass might be set to 100 kg, the glass fiber sizing agent was obtained, and it heat-retained at 60 degreeC. Of the total mass (M _F ) of fatty acid relative to the total mass (M _A ) of the amine compound contained in each raw material of the amide reactants (i) and (ii) used in the preparation of the sizing agent for glass fiber of Example 1 The ratio (M _F / M _A ) was 2.40, and the content of the amide reactant based on the total mass of non-volatile components contained in the sizing agent was 3.0% by mass. In calculating these numerical values, the mass of water generated during the condensation reaction of the amide reactant is ignored, and the same applies to the following examples.

(Example 2)
Glass was obtained in the same manner as in Example 1 except that 100 g of the amide reactant (ii) and 100 g of the amide reactant (iii) were used in place of the amide reactants (i) and (ii). A sizing agent for fibers was obtained. The amide reaction product (iii) was obtained by reacting the reaction ratio (molar ratio) of palmitic acid and tetraethylenepentamine with the former / the latter = 1.3. Of the total mass (M _F ) of the fatty acid relative to the total mass (M _A ) of the amine compound contained in each raw material of the amide reactants (ii) and (iii) used in the preparation of the sizing agent for glass fiber of Example 2 The ratio (M _F / M _A ) was 2.27, and the content of the amide reactant based on the total mass of nonvolatile components contained in the sizing agent was 3.0% by mass.

(Example 3)
Glass was obtained in the same manner as in Example 1 except that 130 g of the amide reactant (iv) and 60 g of the amide reactant (v) were used in place of the amide reactants (i) and (ii). A sizing agent for fibers was obtained. The amide reactant (iv) was obtained by reacting the reaction ratio (molar ratio) of stearic acid and pentaethylenehexamine with the former / the latter = 1.3, and the amide reactant (v) was stearic acid. And the reaction ratio (molar ratio) of diethylenetriamine with the former / the latter = 2.0. Of the total mass (M _F ) of fatty acid with respect to the total mass (M _A ) of the amine compound contained in each raw material of the amide reactants (iv) and (v) used in the preparation of the glass fiber sizing agent of Example 3 The ratio (M _F / M _A ) was 2.20, and the content of the amide reactant based on the total mass of non-volatile components contained in the sizing agent was 2.8% by mass.

(Comparative Example 1)
Instead of using two types of amide reactants (i) and (ii), the same procedure as in Example 1 was performed except that 200 g of one type of amide reactant (i) was used to obtain liquid C. Thus, a sizing agent for glass fiber was obtained. Only the amide reactant (i) was used for the preparation of the glass fiber sizing agent of Comparative Example 1, and the mass of fatty acid relative to the mass of the amine compound (M _A ) contained in the raw material of the amide reactant (i) ( The ratio of M _F ) (M _F / M _A ) was 1.95, and the content of the amide reactant based on the total mass of non-volatile components contained in the sizing agent was 3.0% by mass. .

(Comparative Example 2)
Instead of using two types of amide reactants (i) and (ii), the same procedure as in Example 1 was performed except that 200 g of one type of amide reactant (vi) was used to obtain liquid C. Thus, a sizing agent for glass fiber was obtained. The amide reaction product (vi) was obtained by reacting the reaction ratio (molar ratio) of stearic acid and tetraethylenepentamine with the former / the latter = 1.8. Was used to prepare glass fiber sizing agent of Comparative Example 2, only the amide reactant (vi), amide reactant mass (M _A) to the mass of the fatty acid of the amine compound contained in the raw materials (vi) ratio of _{(M F) (M F /} M a) is 2.70, the content of the amide reaction product relative to the total weight of the nonvolatile components contained in the sizing agent met 3.0 wt% It was.

Table 1 summarizes the amide reactants used for preparing the glass fiber sizing agents of Examples 1 to 3 and Comparative Examples 1 and 2.

[Manufacture of glass fiber bundles]
(Examples 4 to 6 and Comparative Examples 3 and 4)
Using a roll coater, each of the glass fiber sizing agents obtained in Examples 1 to 3 and Comparative Examples 1 and 2 was applied to glass fiber filaments (filament diameter 5 μm), and 200 glass fibers were focused. The glass fiber bundle (variety D450) having a count of 11.2 TEX was obtained by drying for a period of time. In addition, the adhesion amount of the glass fiber sizing agent (nonvolatile component) in the obtained glass fiber bundle was 1.0 part by mass with respect to 100 parts by mass of the glass fiber filament. In addition, what used the sizing agent for glass fibers obtained in Examples 1-3 and Comparative Examples 1 and 2 corresponds to Examples 4 to 6 and Comparative Examples 3 and 4, respectively.

[Manufacture of glass fiber fabrics]
(Examples 7 to 9 and Comparative Examples 5 and 6)
Using the glass fiber bundles obtained in Examples 3 to 6 and Comparative Examples 3 and 4 as warps and wefts, a high-speed air jet loom having the same configuration as the air jet loom shown in FIG. 1 (manufactured by Toyota Industries Corporation, Weaving was performed at JAT) to obtain a glass fiber fabric of IPC specification 1080 type (59 warps / 25 mm, 46 wefts / 25 mm). The wefts at the ends not intersecting with the warp yarns were cut in a state of being entangled with three weft yarns. A glass fiber bundle (variety ECD450-1 / 0) having a count of 11.2 TEX was used as the discarded yarn. The glass fiber sizing agents of Examples 1 to 3 and Comparative Examples 1 and 2 were applied to the warp yarns applied with the glass fiber sizing agents of Examples 1 to 3 and Comparative Examples 1 and 2, respectively. Weft was used. And the thing using the warp and the weft with which the sizing agent for glass fibers of Examples 1-3 and Comparative Examples 1 and 2 was applied corresponds to Examples 7-9 and Comparative Examples 5 and 6, respectively.

(Measurement of electrostatic potential during weaving)
During weaving of Examples 7 to 9 and Comparative Examples 5 and 6, the electrostatic potential of the weft portion at the end not intersecting with the warp was measured by an electrostatic potential meter (trade name: Statilon-M2 manufactured by Sicid Electrostatic Co., Ltd.). ). The measurement location was the weft portion immediately before being cut with a cutter.

[Evaluation of glass fiber fabric]
(Evaluation of fluff)
100 m of glass fiber fabric was prepared by the methods of Examples 7 to 9 and Comparative Examples 5 and 6, and the number of protrusions generated by fluff generated per 50 cm woven length was measured and evaluated according to the criteria shown in Table 2 below.

(Weaving defect evaluation)
Glass fiber fabrics having a weaving length of 2000 m manufactured by the methods of Examples 7 to 9 and Comparative Examples 5 and 6 were visually inspected, and the number of weaving defects generated in the wefts at the cut ends was measured. Evaluation was based on the criteria shown.

The results of electrostatic potential measurement during weaving, evaluation of fluff and evaluation of weaving defects are shown in Table 4 below. The results are shown based on the type of the glass fiber sizing agent applied (described as Examples 1 to 3 and Comparative Examples 1 and 2), the amount and total mass of the non-volatile components, the mass of the amide reactant, and non-volatile The content (mass%) of the amide reactant in the components, the total mass (M _A , M _F ) of each fatty acid and amine compound, and the ratio of the total mass (M _F / M _A ) are also shown.

It is a schematic diagram of an air jet loom.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Warp, 2 ... Weft (glass fiber bundle), 8 ... Discard yarn, 10 ... Glass fiber fabric.

Claims (4)

A reaction product obtained by reacting a fatty acid with an amine compound represented by the following general formula (1), and a sizing agent for glass fiber containing starch, an oil agent and water,
The glass whose ratio of the total mass (M _F ) of the fatty acid to the total mass (M _A ) of the amine compound contained in the raw material of the reactant is M _F / M _A = 2.1 to 2.6 Fiber sizing agent.
H ₂ N (R ¹ NH) _n R ¹ NH ₂ (1)
[In formula (1), ^{R 1} is an alkylene group having 1 to 10 carbon atoms; respectively an integer of n is 0-10. ]   The sizing agent for glass fibers according to claim 1, wherein the reactant is contained in an amount of 2 to 5% by mass based on the total mass of nonvolatile components of the sizing agent for glass fibers.   A glass fiber bundle, which is coated with the glass fiber sizing agent according to claim 1.   A method for producing a glass fiber woven fabric, wherein the glass fiber bundle according to claim 3 is used as a weft, and is weaved by flying with compressed air and intersecting with the warp, and cutting the weft at the end not intersecting with the warp. .

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