JP2017193467A - Aqueous sizing agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: an aqueous sizing agent that does not require a heat cleaning treatment when using an aqueous sizing agent containing starch, solves decreases in storage stability of a liquid and heat resistance of glass fibers when using a sizing agent containing a silane coupling agent, and can realize stable and excellent weavability and openability; and a glass fiber surface-treated by using the aqueous sizing agent.SOLUTION: Provided is an aqueous sizing agent containing 100 pts.mass of a polyoxyalkylene bisphenol A ether (A), 10-200 pts.mass of a polyalkylene glycol (B), 10-200 pts.mass of a cationic fatty acid amide, and 1-30 pts.mass of a polyoxyalkylene alkyl ester (D), and does not contain starch and a silane coupling agent. Further, provided is the aqueous sizing agent that preferably contains fine particles (E) formed of hydroxyphenyltriazine or polyamide in an amount of 1-50 pts.mass relative to 100 pts.mass of the polyoxyalkylene bisphenol A ether (A).SELECTED DRAWING: None

Description

  The present invention relates to an aqueous sizing agent for imparting bundling and weaving properties to a fiber, a glass fiber surface-treated with the aqueous sizing agent, a glass fiber cloth woven using the glass fiber, a water-spreading treatment, and The present invention relates to a glass fiber cloth subjected to silane coupling treatment, and a prepreg or a composite material using the glass fiber cloth.

  In recent years, with the reduction in weight of electronic devices, there is an increasing demand for thinning glass fiber cloth that is a reinforcing material for printed circuit boards. As an effort to reduce the thickness of glass fiber cloth, we are proceeding with high-density weaving by applying glass fibers with fine counts (single fiber diameter of 5 μm or less). The woven glass fiber cloth is subjected to a fiber-opening process and processed to be thinner than immediately after weaving. By processing the substrate thinner, it is possible to improve the impregnation property of the matrix resin when producing the printed circuit board, and to improve the processing speed of the printed circuit board.

  In order to improve the weaving property, the glass fiber is woven after attaching an aqueous sizing agent containing starch. Glass fiber cloth woven using starch-sized glass fibers is subjected to a heat cleaning process to remove starch in order to prevent adverse effects on mechanical properties, heat resistance, electrical properties, etc. as a substrate material. . Further, the glass fiber cloth is subjected to a surface treatment in order to enhance the adhesiveness of the matrix resin.

  However, in the heat cleaning process, the glass fiber cloth is exposed to a high temperature of 400 ° C. or higher for a long time, so that the glass fiber deteriorates due to heat and the strength thereof decreases. Further, in the surface treatment, the glass fiber cloth is washed by a high-pressure water-washing jet, so that the glass fiber damaged by the heat cleaning process is damaged and fluff is generated. In particular, in a cloth woven with fine count glass fibers and subjected to a heat cleaning process, the influence of these processing steps is large.

  Thus, studies have been made on aqueous sizing agents containing resins that do not require heat cleaning. For example, Patent Document 1 proposes to use an aqueous sizing agent containing an epoxy resin, bisphenol A ether to which ethylene oxide is added, and a silane coupling agent. Patent Document 2 proposes an aqueous sizing agent containing a stearic acid ester of polyethylene glycol.

  However, since the aqueous sizing agent described in Patent Document 1 contains a silane coupling agent, hydrolysis and condensation progress with the passage of time, and the state of the liquid changes. Therefore, the silane monomer couple | bonded with the glass fiber surface reduces, and ensuring of heat resistance becomes difficult for the glass fiber sized with the sizing agent which time passed. Furthermore, since the glass fiber treated with an aqueous sizing agent containing a silane coupling agent is not subjected to heat treatment, unreacted siloxane oligomer remains on the glass fiber surface, and heat resistance is lowered. Further, in the water-based size described in Patent Document 2, since the molecular weight of polyethylene glycol stearate is high, the glass fibers are too focused, making it difficult to open the yarn with the water pressure used in the opening process. Become.

JP 2007-162171 A JP 2000-80570 A

  Therefore, the present invention solves the above-mentioned problems, does not require a heat cleaning process when using an aqueous sizing agent containing starch, and preserves the storage stability of a liquid when using an aqueous sizing agent containing a silane coupling agent. An object of the present invention is to provide a water-based sizing agent that eliminates a decrease in heat resistance and a decrease in heat resistance of glass fibers, and can realize stable and excellent weaving properties and fiber opening properties.

  As a result of intensive studies, the present inventors have found that an aqueous sizing agent in which starch and silane coupling agent are excluded from the sizing agent and a specific amount of a specific component is blended can solve the above problems, and the present invention has been achieved. That is, the gist of the present invention is as follows.

[1] Polyoxyalkylene bisphenol A ether (A) 100 parts by mass, polyalkylene glycol (B) 10-200 parts by mass, cationic fatty acid amide (C) 10-200 parts by mass, polyoxyalkylene alkyl ester ( D) An aqueous sizing agent containing 1 to 30 parts by mass and containing no starch or silane coupling agent.
[2] The aqueous sizing agent according to [1], further comprising 1 to 50 parts by mass of fine particles (E) with respect to 100 parts by mass of the polyoxyalkylene bisphenol A ether (A).
[3] The aqueous sizing agent according to [2], wherein the fine particles (E) are hydroxyphenyltriazine or polyamide.
[4] The aqueous sizing agent according to any one of [1] to [3], wherein the polyoxyalkylene bisphenol A ether (A) has a hydroxyl value of 200 mgKOH / g or less.
[5] A glass fiber that has been surface-treated with the aqueous sizing agent according to any one of [1] to [4].
[6] A glass fiber cloth using the glass fiber according to [5].
[7] The glass fiber cloth according to [6], which has been subjected to water opening treatment and silane coupling treatment.
[8] A prepreg using the glass fiber cloth according to [6] or [7].
[9] A composite material using the glass fiber cloth according to [6] or [7].

  According to the present invention, there is no need for a heat cleaning process when an aqueous sizing agent containing starch is used, and the short pot life when using an aqueous sizing agent containing a silane coupling agent is eliminated, which is stable and excellent. An aqueous sizing agent that achieves weaving and storage stability can be provided. In addition, the glass fiber cloth woven using the glass fiber surface-treated with the aqueous sizing agent of the present invention is excellent in heat resistance and mechanical properties, so that it is used as a reinforcing material for printed circuit boards used in electrical equipment and the like. Can be preferably used.

Hereinafter, the present invention will be described in detail.
The aqueous sizing agent of the present invention contains polyoxyalkylene bisphenol A ether (A), polyalkylene glycol (B), cationic fatty acid amide (C), polyoxyalkylene alkyl ester (D), starch and silane coupling. Contains no agent. The term “not contained” as used herein means that it is not substantially contained, and may be contained in a trace amount as long as the effects of the present invention are not impaired.

  The polyoxyalkylene bisphenol A ether (A) is used for the purpose of covering the surface of the glass fiber, reducing the friction generated during weaving and aging, and suppressing the occurrence of fluff and yarn breakage. Polyoxyalkylene bisphenol A ether is a polyoxyethylene bisphenol A ether because it has high film-forming properties and is highly effective in providing fluff, antistatic properties and lubricity, and is particularly excellent in antistatic properties and suppression of fuzz. It is preferable.

  The polyoxyalkylene bisphenol A ether (A) preferably has a hydroxyl value of 200 mgKOH / g or less. When the hydroxyl value exceeds 200 mgKOH / g, the amount of polyoxyalkylene bisphenol A ether (A) attached to the glass fiber may decrease, and the glass fiber has a high frictional force with each member. Thread breakage may occur. In addition, the spreadability may be lowered.

  Polyalkylene glycol (B) and cationic fatty acid amide (C) are intended to improve the flexibility of glass fibers and to suppress yarn breakage that occurs in the warping process, and polyoxyalkylene bisphenol A ether (A) is glass. Used to adhere more to the fiber surface. Examples of the polyalkylene glycol include polyethylene glycol and polypropylene glycol, and polyethylene glycol is preferable from the viewpoint of antistatic properties. Examples of the cationic fatty acid amide include those composed of polyethyleneamine and a fatty acid. Examples of the polyethyleneamine include diethylenetriamine, triethylenetetramine, and tetraethylenepentamine. Examples include lauric acid, myristic acid, palmitic acid, and stearic acid. By using (B) and (C) in combination, the spreadability is synergistically improved as compared with the case of using (B) alone or the case of using (C) alone.

  The content of the polyalkylene glycol (B) and the cationic fatty acid amide (C) must be 10 to 200 parts by mass with respect to 100 parts by mass of the polyoxyalkylene bisphenol A ether (A). Yes, and preferably 40 to 100 parts by mass. When the contents of (B) and (C) are each less than 10 parts by mass, the glass fiber is reduced in flexibility and weaving property is reduced. In addition, the polyoxyalkylene bisphenol A ether (A) is less likely to be coated on the glass fiber surface, causing fluffing. On the other hand, when the content of (B) and (C) exceeds 200 parts by mass, the charge amount increases and the weaving property of the glass fiber decreases.

  The polyoxyalkylene alkyl ester (D) is used for the purpose of reducing the chargeability of the fiber. Examples of the polyoxyalkylene alkyl ester include polyoxyethylene alkyl ester.

  The content of the polyoxyalkylene alkyl ester (D) is required to be 1 to 30 parts by mass with respect to 100 parts by mass of the polyoxyalkylene bisphenol A ether (A), and 5 to 15 parts by mass. preferable. When the content of (D) is less than 1 part by mass, it becomes difficult to prevent electrification, and the unwinding property of the yarn during weaving is lowered, and the weaving property is lowered. On the other hand, when the content of (D) exceeds 30 parts by mass, the unwinding property from the feeder on the weaving machine is lowered, and the weaving property is lowered.

  The water-based sizing agent of the present invention improves the weaving property and warpability by improving the spreadability, reducing the friction with members that contact the glass fiber by forming minute irregularities on the glass fiber surface. It is preferable to further contain fine particles (E). The fine particles may be either organic or inorganic.

  Examples of organic fine particles include polylactic acid, polyarylate, liquid crystal polymer, polycarbonate, polyphenylene sulfide, polyamide, dimer acid polyamide, polytetrafluoroethylene, polyvinyl chloride, polyester, polyethyleneimine, polyoxymethylene, polyetheretherketone. , Polyurethane, polyvinyl resin, polyolefin resin, polyacrylate, polyurethane acrylate and other fine particles, benzotriazole compounds, benzophenone compounds, triazine compounds, hindered phenol compounds, benzoate compounds and hindered amine compounds And the like. Among these, hydroxyphenyl triazine and polyamide are preferable because of the high effect of improving the spreadability, weaving property, and warping, and polyamide is more preferable because a composite material exhibiting heat resistance can be obtained. The fine particles may be used alone or in combination. The fine particles can be supplied as an aqueous dispersion of organic matter.

  The aqueous dispersion of polyamide includes an anionic type and a cationic type, and the cationic type is preferred. By using a cationic aqueous dispersion, the unwinding property at the time of weaving is increased and the weaving property is easily improved. Moreover, it becomes easy to improve opening property.

  An aqueous dispersion of hydroxyphenyltriazine is available, for example, from BASF as TIVUVIN479-DW. Moreover, as an aqueous dispersion of a cation type polyamide, it can be obtained as M3-C-X20 or M4-C-X025, and as an anionic type aqueous dispersion, it can be obtained as MD-X20 or ME-X25. be able to.

  In addition, as inorganic substances constituting the inorganic fine particles, silicon carbide, aluminum nitride, silica, clay, boron nitride, graphite, metal dichalcogenide, cadmium iodide, silver sulfide, etc., for example, indium, thallium, tin, copper, Examples thereof include a metal inorganic material containing at least one metal selected from the group consisting of zinc, gold, and silver. Especially, since the effect which improves a fiber opening property is high, it is preferable that the inorganic substance which comprises an inorganic fine particle is boron nitride. The fine particles may be used alone or in combination.

  The particle diameter of the fine particles (E) is preferably 0.01 to 1 μm. When the particle diameter of the fine particles (E) is less than 0.01 μm, the glass fiber may have poor sliding properties on the weaving machine and may have poor weaving properties. On the other hand, when the particle diameter of the fine particles (E) exceeds 1 μm, the fine particles do not reach the inside of the glass fiber filament, and the glass fiber may have a reduced openability.

  The content of the fine particles (E) is preferably 1 to 50 parts by mass and more preferably 10 to 30 parts by mass with respect to 100 parts by mass of the polyoxyalkylene bisphenol A ether (A). If the content of the fine particles (E) is less than 1 part by mass, the spreadability may be low. On the other hand, if it exceeds 50 parts by mass, fluff frequently occurs and the weaving property may deteriorate.

  The aqueous sizing agent of the present invention is used by adhering to the surface of fibers such as inorganic fibers, natural fibers, and synthetic fibers. Examples of the inorganic fiber include glass, carbon, graphite, mullite, and aluminum oxide. Examples of natural fibers include cotton, cellulose, natural rubber, flax, hemp, ramie, sisal, and wool. Examples of synthetic fibers include fibers containing thermoplastic resins, such as polyamide, polylactic acid, polyarylate, liquid crystal polymer, polyester, acrylic resin, polycarbonate, polyurethane, polyvinyl resin, and fibers containing polyolefin resin. Can be mentioned.

  The water-based sizing agent of the present invention may further contain a water-soluble resin other than an epoxy resin for the purpose of improving the fiber converging property and suppressing the generation of fluff. Examples of water-soluble resins include acrylic resins, methacrylic resins, polyvinyl alcohol resins, polyvinyl pyrrolidone resins, acryloyl morpholine resins, and the like. The water-soluble resin may be used alone or in combination.

  The aqueous sizing agent of the present invention may further contain a pH adjuster. As the pH adjuster, for example, acetic acid is used.

  The aqueous sizing agent of the present invention may further contain a curing catalyst. Examples of the curing catalyst include tris (dimethylaminomethyl) phenol and trisethylhexylate.

  The aqueous sizing agent of the present invention may further contain an antistatic aid, a thickener, a leveling agent, an antioxidant, a flame retardant, a flame retardant aid, a thermal stabilizer, a fibrous reinforcing material, and a functional filler. . Examples of the functional filler include a heat conductive filler, an electromagnetic wave shielding particle filler, a heat insulating filler, and a high dielectric filler.

  The total concentration of the components in the aqueous sizing agent of the present invention is preferably 2 to 10% by mass. When the total concentration of each component of the aqueous sizing agent is less than 2% by mass, it becomes difficult to uniformly coat the fiber, and the fiber is likely to fluff and the heat resistance and mechanical properties may be lowered. is there. On the other hand, when the total concentration of each component exceeds 10% by mass, the amount of solids attached to the fiber increases, and the weaving property may be deteriorated due to stickiness of the fiber surface and adhesion of excessive fine particles.

  The aqueous sizing agent of the present invention comprises polyoxyalkylene bisphenol A ether (A), polyalkylene glycol (B), cationic fatty acid amide (C), polyoxyalkylene alkyl ester (D), and, if necessary, fine particles (E ) In water. More specifically, (B) may be first mixed with water, (A), (C), (D) may be further added and mixed, or (A), (C), ( D) may be added to and mixed with water containing (B), respectively, or a mixture of (A), (C) and (D) may be added to water containing (B). You may mix. When (E) is included, (B) may be first mixed with water, (A), (C), (D), (E) may be further added and mixed, or (A), (C), (D) and (E) may be added to and mixed with water containing (B), respectively, or (A), (C), (D) and (E) may be mixed. The product may be mixed with the water containing (B).

  For mixing (A) to (D) or (A) to (E), a disper or vibration stirring may be used. Moreover, what is necessary is just to mix the said mixture and an inorganic filler using a stirring blade, a bead mill, a 3 roll mill, and a jet mill, when adding an inorganic filler to the obtained mixture. When using a disper, the rotation speed is preferably 500 to 3000 rpm, when using vibration stirring, the vibration frequency is preferably 30 to 50 Hz, and when using a bead mill, it is preferable to use a chiller. When the number of rotations and the number of vibrations are within the above ranges, and a chiller is used, an aqueous sizing agent can be obtained while suppressing heat generation due to heat of stirring.

  The fiber whose surface is coated with the water-based sizing agent of the present invention is excellent in flexibility, low friction property and low chargeability, and has excellent weaving properties because generation of fluff is suppressed. The aqueous sizing agent of the present invention does not contain starch and a silane coupling agent. Therefore, the heat cleaning process required when using an aqueous sizing agent containing starch is unnecessary, and the occurrence of fluff and yarn breakage can be suppressed. Moreover, the pot life when a silane coupling agent is used can be ignored. The effect obtained by eliminating the need for heat cleaning is particularly remarkable when the number of glass fibers bundled is reduced and the fiber diameter of the glass fibers is reduced as the electronic equipment is reduced in size and thickness. .

  The present invention also relates to a glass fiber whose surface is treated with the aqueous sizing agent of the present invention. From the viewpoint of weaving properties and heat resistance, the amount of the aqueous sizing agent (solid content) attached to the glass fiber is 100 parts by mass in total of the glass fiber and the aqueous sizing agent (solid content) attached to the glass fiber. 0.10 to 0.30 parts by mass, and more preferably 0.15 to 0.25 parts by mass. The glass fiber (glass fiber strand) of this invention is obtained by apply | coating the aqueous sizing agent of this invention to glass fiber by a well-known method (for example, roller sizing method, roller dipping method, spray method).

  Furthermore, this invention relates to the glass fiber cloth using the glass fiber by which the surface was processed with the aqueous sizing agent of this invention. The glass fiber cloth of the present invention can be obtained by weaving glass fibers whose surface is treated with an aqueous sizing agent by a known method (for example, a method using a shuttle loom, an air jet loom, or a lepier loom). Glass fibers for weaving are used, for example, as glass yarn (strands twisted on strands) or roving (strands wound without strands twisted). The glass fiber cloth of the present invention can easily remove the aqueous sizing agent by subjecting it to a water opening treatment. The water opening treatment is usually performed by applying a water pressure of 0.1 to 5.0 MPa. Moreover, the glass fiber cloth subjected to the water opening treatment can be made excellent in heat resistance and mechanical properties by performing a silane coupling treatment.

A composite material can be obtained by impregnating the glass fiber cloth of the present invention with a matrix resin. Examples of the method of impregnating the matrix resin include a method of immersing a glass fiber cloth that has been subjected to a water opening treatment or a silane coupling treatment in a solution of the matrix resin. When the epoxy resin is impregnated as a matrix resin, for example, it is processed into a semi-cured prepreg at 150 to 200 ° C. for 1 to 10 minutes, and 20 to 40 prepregs are laminated, and the pressing pressure is 10 to 40 kg / cm ^2. Heated at 150 to 200 ° C. under vacuum for 1.5 to 2 hours, a cured composite material can be obtained.

  The glass fiber cloth of the present invention is suitably used as a reinforcing material for a glass fiber-resin composite substrate for printed circuit boards. A glass fiber-resin composite substrate using this glass fiber cloth is excellent in heat resistance, and can firmly maintain the interfacial adhesion between the glass fiber and the resin without being affected by soldering heat even in a moisture absorption state.

  The aqueous sizing agent of the present invention does not contain starch and a silane coupling agent unlike conventional aqueous sizing agents. For this reason, by using the water-based sizing agent of the present invention, fluctuations in yarn quality and deterioration of weaving properties when not used for a long time are suppressed. Moreover, the heat cleaning process becomes unnecessary, and the deterioration of the glass fiber that has conventionally occurred in these processes is suppressed. The suppression effect is particularly noticeable when the number of glass fibers bundled is reduced and the fiber diameter of the glass fibers is reduced as the electronic equipment is reduced in size and thickness.

  In view of the above, the glass fiber and glass fiber cloth of the present invention are components of computers such as smartphones, tablets, power devices, personal computers, home game machines; DVD players, DVD recorder components, HDD recorder components, homes. Parts for display power supply units such as TVs, plasma displays, and liquid crystal televisions; parts for mobile phones, various AV equipment, OA equipment, etc .; car stereos, car navigation systems, inverters, lighting, automobile electrical components, automobile engine components, automobiles It can be suitably used for brake members, automobile interior members, aerospace materials, sports applications, outdoor applications, and general industrial materials.

  Examples of the present invention will be specifically described below, but the present invention is not limited to these examples.

A method for measuring and evaluating the characteristics of the aqueous sizing agent, glass fiber, and glass fiber cloth is as follows.
(1) Amount of water-based sizing agent attached to glass fiber The amount of water-based sizing agent attached to glass fiber was measured as follows in accordance with JIS R 3420 as loss on ignition.
The glass fiber to which the aqueous sizing agent was adhered was dried with hot air at 110 ° C. for 1 hour, moisture (water derived from the aqueous sizing agent) was removed from the glass fiber, and the weight W ₁ of the glass fiber after removing the water was measured. Next, the glass fiber is allowed to stand for 30 minutes in an environment at 625 ° C. using an electric furnace, and after further removing the aqueous sizing agent (solid content) from the glass fiber, the aqueous sizing agent (solid content) is removed. The glass fiber weight W ₂ was measured.
The amount of the aqueous sizing agent attached to the glass fiber was calculated from the following equation.
Adhesion amount to glass fiber = ((glass fiber weight W ₁ after moisture removal) − (glass fiber weight W ₂ after water-based sizing agent (solid content) removal)) / (glass fiber weight W ₁ after moisture removal) × 100

(2) Unwinding tension of glass fiber The obtained glass fiber was unwound at a speed of 600 m / min, and the unwinding tension was measured using a tension meter (manufactured by Yokogawa Electronics Corporation).
In the present invention, when the unwinding tension is 3.0 cN or less, it was determined to be acceptable. The unwinding tension is preferably 2.0 cN or less.

(3) Fluff of glass fiber The obtained glass fiber was unwound at a speed of 300 m / min and the number of fluff after passing through the tension bar was measured with a sensor.
In the present invention, when the number of fluffs is 2.5 / 100 m or less, it was determined to be acceptable. The fluff is preferably 1.0 pieces / 100 m or less.

(4) Antistatic property of glass fiber The obtained glass fiber is wound up with a measuring machine, an electrostatic sensor (ZJ-SD100 manufactured by OMRON Corporation) is installed at the lower part of the rotating body which is the winding-up part, and the yarn is arranged. The amount of static electricity generated during the process was measured. The number of windings was 100.
In this invention, when antistatic property was 3.0 kV or less, it was set as the pass. The antistatic property is preferably 1.5 kV or less.

(5) Weaving property of glass fiber The wrapping and flying state of the glass fiber when weaving the glass fiber cloth using an air jet loom manufactured by Tsudakoma Kogyo Co., Ltd. is visually observed, and the weaving time is 1 hour. The number of times weaving was stopped was measured. The weaving of the glass fiber is stopped when the winding failure of the glass fiber around the feed roller occurs, or when the show topic occurs due to unstable feeding.
When it did not stop even once, “◎”, when it stopped once to 4 times, “◯”, when it stopped 5 times or more, “×”.

(6) Opening property of glass fiber cloth The opening property of the glass fiber cloth was evaluated based on the air flow rate of the glass fiber in accordance with JIS R 3420. A fragile permeator manufactured by Toyo Seiki Co., Ltd. was used for measuring the air flow rate.
In the present invention, when the air flow rate is 60 cm ³ / (cm ² · s) or less, it is regarded as acceptable. The air flow rate is preferably 45 cm ³ / (cm ² · s) or less.

(7) Heat resistance of composite material The obtained cured prepreg was given a heat history by wet heat treatment and a solder bath, and the state of the cured prepreg thereafter was evaluated. The wet heat treatment was performed using a pressure cooker under conditions of a water vapor pressure of 1.05 kg / cm ² G, an environmental temperature of 121 ° C., and 12 hours. The heat history by the solder bath was performed by immersing the cured prepreg subjected to the wet heat treatment in water at 20 to 25 ° C. for 15 minutes and then immersing it in a solder bath at 260 ° C. for 25 seconds.
The stuck solder is scraped off from the cured prepreg after being immersed in the solder bath, and the surface of the cured prepreg is observed using a flatbed scanner (manufactured by EPSON). The ratio of the area of (whitening part) was calculated | required. When the ratio of the whitened portion on the surface of the cured prepreg was less than 1%, “◎”, when it was 1% or more but less than 30%, “◯”, when it was 30% or more, “x”, the heat resistance of the composite material was evaluated.

(8) Mechanical properties of composite material The obtained cured composite material was determined for flexural strength and flexural modulus according to the three-point bending test of JIS K 6911. The measurement was performed under the conditions of a measurement speed of 5 mm / min and a fulcrum distance of 16 mm.

(9) Hydroxyl value of polyoxyalkylene bisphenol A ether (A) 10 g of polyoxyalkylene bisphenol A ether (A) was dissolved in 5 mL of a mixed solution of acetic anhydride / pyridine (1/5 by volume), and then 100 ° C. For 1 hour to react acetic anhydride with a hydroxyl group in polyoxyalkylene bisphenol A ether (A). Thereafter, distilled water was further added and stirred at 100 ° C. for 10 minutes to decompose excess acetic anhydride to obtain a sample solution. The sample solution was titrated with a 0.5 mol / L potassium hydroxide aqueous solution to obtain a titer W ₃ (mL). Similarly, titration was also performed when polyoxyalkylene bisphenol A ether was not used (only the above-mentioned mixed solution), and a titer W ₄ (mL) was obtained. The hydroxyl value was calculated from the following formula.
Hydroxyl value (mgKOH / g) = (W ₄ −W ₃ ) × f × 28.05 / 10
(F: Potency of 0.5 mol / L potassium hydroxide aqueous solution)

(10) Average particle diameter of fine particles (E) The average particle diameter was measured using a Microtrac particle size distribution analyzer UPA150 (MODEL No. 9340) manufactured by Nikkiso Co., Ltd.

The material which comprises an aqueous sizing agent is shown below.
(1) Polyoxyalkylene bisphenol A ether (A)
(A1) Polyoxyethylene bisphenol A ether (manufactured by Yoshimura Oil Chemical Co., Ltd., GF690, hydroxyl value 123 mgKOH / g)
(A2) Polyoxyethylene bisphenol A ether (manufactured by Sanyo Chemical Industries, Newpol BPE-60, hydroxyl value 228 mgKOH / g)
(A3) Polyoxypropylene bisphenol A ether (manufactured by Sanyo Chemical Industries, Newpol BP-5P, hydroxyl value 211 mgKOH / g)

(2) Polyalkylene glycol (B)
(B1) Polyethylene glycol (manufactured by Sanyo Chemical Industries, PEG 600)

(3) Cationic fatty acid amide (C)
(C1) Cationic fatty acid amide (manufactured by Yushi Co., Ltd., KSK)

(4) Polyoxyalkylene alkyl ester (D)
(D1) Polyoxyethylene alkyl ester (manufactured by Yushi Kogyo Co., Ltd., Neulan)

(5) Fine particles (E)
(E1) Cationic polyamide aqueous dispersion (manufactured by Unitika, M3-C-X020, solid content concentration 20% by mass, number average particle size 0.083 μm)
(E2) Cationic polyamide aqueous dispersion (manufactured by Unitika, M4-C-X025, solid content concentration 25% by mass, number average particle size 0.043 μm)
(E3) Anionic polyamide aqueous dispersion (manufactured by Unitika Ltd., MD-X020, solid content concentration 22 mass%, number average particle size 0.034 μm)
(E4) Anionic polyamide aqueous dispersion (manufactured by Unitika, ME-X025, solid content concentration: 26% by mass, number average particle diameter: 0.054 μm)
(E5) Hydroxyphenyltriazine aqueous dispersion (manufactured by BASF, TINUVIN 479-DW, solid content concentration 40% by mass, average particle size? Μm)

Examples 1-26, Comparative Examples 1-9
A water-based sizing agent having a concentration of 4 to 8% by mass was prepared by mixing each component of the types and parts by mass shown in Table 1 and water.
The obtained aqueous sizing agent was attached to a glass yarn composed of a plurality of glass fiber filaments (total number of fibers: 40) spun from a nozzle, and the glass fibers were converged into one bundle (strand). The strand was then wound on a cake without twisting. The glass roving unraveled from the obtained cake was wound around a bobbin while twisting (twist number: 0.5Z) to obtain a glass fiber yarn (average fiber diameter: 4.1 μm, count: 1.3 tex). . Thus, a glass fiber for weaving was obtained.
In addition, the adhesion amount of the aqueous sizing agent (solid content) to the glass fiber varies depending on the concentration of the aqueous sizing agent. When the concentration of the aqueous sizing agent is 4 to 8% by mass, the attached amount of the aqueous sizing agent (solid content) is 0 with respect to a total of 100 parts by mass of the glass fiber and the aqueous sizing agent (solid content) attached thereto. .15 to 0.4 parts by mass.
The glass fiber for weaving obtained above was used for both warp and weft to weave with an air jet loom manufactured by Tsuda Koma Kogyo to obtain a glass fiber cloth (roving cloth).
The obtained glass fiber cloth was opened with water, subjected to silane coupling treatment, dried in a drying process at 120 ° C., then immersed in an epoxy resin varnish, taken up from the varnish, and then 150 Heat treatment was carried out at 5 ° C. for 5 minutes and at 170 ° C. for 1.5 to 2 hours to produce a cured prepreg.
In addition, the obtained glass fiber cloth is subjected to fiber opening treatment with water, silane coupling treatment, and drying in a drying process at 120 ° C., then immersed in an epoxy resin varnish and taken up from the varnish. Then, heat treatment was performed at 150 ° C. for 5 minutes, and processed into a semi-cured prepreg. Thirty semi-cured prepregs were stacked and heated at a pressing pressure of 10 to 40 kg / cm ² , a heating temperature of 170 ° C. and a vacuum for 1.5 to 2 hours to prepare a cured composite material.
In the preparation of the cured prepreg and composite material, the opening process with water was performed by applying a water pressure of 0.1 to 5.0 MPa, and the silane coupling process was performed using an aminosilane coupling agent. . Moreover, the varnish which diluted 100 mass parts of epoxy resins of FR-4 composition of NBMA specification with 14 mass parts of methyl ethyl ketone was used as a varnish of an epoxy resin.
Various measurements and evaluations were performed on the obtained sizing agent, glass fiber for weaving, glass fiber cloth, and a cured prepreg and composite material produced from the glass fiber cloth. The results are shown in Table 1.

The glass fibers whose surfaces were treated with the aqueous sizing agents of Examples 1 to 26 were able to be woven stably with the unraveling tension, the amount of fluff generation, and the charge suppressed.
Since the aqueous sizing agent of Example 2 used the aqueous dispersion of polyamide (E1) as the fine particles (E), the weaving property was slightly higher than that of Example 1. Further, the glass fiber cloth obtained therefrom was slightly high in opening property.
In the aqueous sizing agent of Example 3, the content of the polyalkylene glycol (B) was less than the preferred range defined in the present invention, so that the amount of fluff generation was slightly higher compared to Example 2, and the weaving property was It was a little low. In the aqueous sizing agent of Example 4, the content of the polyalkylene glycol (B) was larger than the preferable range defined in the present invention, so that the unraveling tension was slightly higher than in Example 2, and the weaving property was slightly higher. Was low. Further, the glass fiber cloth obtained therefrom had a slightly low opening property.
In the aqueous sizing agent of Example 5, the content of the cationic fatty acid amide (C) was less than the preferred range defined in the present invention, so that the unraveling tension was slightly higher compared to Example 2, and the weaving property It was a little low. In the aqueous sizing agent of Example 6, the content of the cationic fatty acid amide (C) was larger than the preferable range defined in the present invention, so that the charge amount was slightly higher than in Example 2, and the weaving property was increased. It was a little low. Moreover, the openability of the glass fiber cloth obtained therefrom was slightly low.
In the aqueous sizing agent of Example 7, the content of the compound (D) was less than the preferred range specified in the present invention, so that the unraveling tension was slightly higher and the weaving property was slightly lower than in Example 2. It was. In the aqueous sizing agent of Example 8, the content of the compound (D) was larger than the preferred range specified in the present invention, so that the amount of fluff generation was slightly higher and the weaving property was slightly lower than in Example 2. It was.
Since the water-based sizing agents of Examples 9 and 10 used polyoxyalkylene bisphenol A ethers (A2) and (A3) having a hydroxyl value exceeding 200 mgKOH / g, the solubility in water was lowered and the glass fiber coverage was reduced. Declined. Therefore, the amount of fluff generation and the amount of charge was slightly high, and the weaving property was low. Further, the glass fiber cloth obtained therefrom had a slightly low opening property.
In the aqueous sizing agent of Example 11, the content of fine particles (E) was less than the more preferable range defined in the present invention. It was a little low. The aqueous sizing agent of Example 12 had a slightly lower weaving property as compared with Example 2 because the content of fine particles (E) was larger than the more preferable range defined in the present invention.
Since the aqueous sizing agents of Examples 11 and 14 used an anionic polyamide aqueous dispersion as the fine particles (E), they were obtained in comparison with Examples 17 and 20 using a cationic polyamide aqueous dispersion. The glass fiber cloth had a slightly high opening property. Further, since the aqueous sizing agents of Examples 11, 14, 17, and 20 used an aqueous polyamide dispersion, the glass fiber cloth obtained from the aqueous sizing agent was compared with Example 23 using an aqueous hydroxyphenyltriazine dispersion. The spreadability was slightly high.
Similarly, since the aqueous sizing agents of Examples 2 and 13 used an anionic polyamide aqueous dispersion as the fine particles (E), the aqueous sizing agent was compared with Examples 16 and 19 using a cationic polyamide aqueous dispersion. The obtained glass fiber cloth had a slightly high opening property. Moreover, since the aqueous sizing agents of Examples 2, 13, 16, and 19 used polyamide aqueous dispersions, the glass fiber cloths obtained therefrom were compared with Example 22 using hydroxyphenyltriazine aqueous dispersions. The spreadability was slightly high.
Similarly, since the aqueous sizing agents of Examples 12 and 15 used an anionic polyamide aqueous dispersion as the fine particles (E), compared with Examples 18 and 21 using a cationic polyamide aqueous dispersion, The obtained glass fiber cloth had a slightly high opening property. In addition, since the aqueous sizing agents of Examples 12, 15, 18, and 21 used an aqueous polyamide dispersion, the glass fiber cloth obtained therefrom was compared with Example 24 using an aqueous hydroxyphenyltriazine dispersion. The spreadability was slightly high.
Since the aqueous sizing agent of Example 2 used polyalkylene glycol (B) and cationic fatty acid amide (C) in combination, Comparative Example 9 in which (B) was not used and Comparative Example 8 in which (C) was not used In contrast, the spreadability was synergistically improved.
In the aqueous sizing agent of Example 25, since the content of the fine particles (E) was less than the more preferable range defined in the present invention, the openability of the glass fiber cloth obtained therefrom was somewhat in comparison with Example 2. It was low.
The aqueous sizing agent of Example 26 had a slightly lower weaving property as compared with Example 2 because the content of fine particles (E) was larger than the more preferable range defined in the present invention.

In the aqueous sizing agent of Comparative Example 1, the content of polyalkylene glycol (B) was less than the range specified in the present invention, so that the glass fiber was hard, the amount of fluff generation was increased, and the weaving property was low. Therefore, a glass fiber cloth could not be obtained.
In the aqueous sizing agent of Comparative Example 2, the polyalkylene glycol (B) content was larger than the range specified in the present invention, so that the fluff generation amount and the charge amount were high, and the weaving property was low. Moreover, the glass fiber cloth obtained from it had low openability.
In the aqueous sizing agent of Comparative Example 3, since the content of the cationic fatty acid amide (C) was less than the range specified in the present invention, the glass fiber was hard, the amount of fluff generation increased, and the weaving property was low. Therefore, a glass fiber cloth could not be obtained.
In the aqueous sizing agent of Comparative Example 4, the amount of the cationic fatty acid amide (C) was larger than the range specified in the present invention, so that the amount of fluff generation and charge amount was high and the weaving property was low. Moreover, the glass fiber cloth obtained from it had low openability.
In the aqueous sizing agent of Comparative Example 5, since the content of the compound (D) was less than the range specified in the present invention, the unwinding tension and the charge amount were high, and the weaving property was low. Therefore, a glass fiber cloth could not be obtained.
In the aqueous sizing agent of Comparative Example 6, the content of the compound (D) was larger than the range specified in the present invention, so that the unwinding tension was high and the weaving property was low.
Since the aqueous sizing agent of Comparative Example 7 did not contain polyoxyalkylene bisphenol A ether (A), the film-forming property was inferior, the unraveling tension, the fluff generation amount, the charge amount were high, and the weaving property was low. Therefore, a glass fiber cloth could not be obtained.
Since the aqueous sizing agent of Comparative Example 8 did not contain the polyalkylene glycol (B), the film-forming property was inferior, the unraveling tension, the fluff generation amount, the charge amount were high, and the weaving property was low. Therefore, a glass fiber cloth could not be obtained.
Since the aqueous sizing agent of Comparative Example 9 did not contain the cationic fatty acid amide (C), the film-forming property was inferior, the unraveling tension, the fluff generation amount, the charge amount were high, and the weaving property was low. Therefore, a glass fiber cloth could not be obtained.

Claims (9)

  100 parts by weight of polyoxyalkylene bisphenol A ether (A), 10 to 200 parts by weight of polyalkylene glycol (B), 10 to 200 parts by weight of cationic fatty acid amide (C), and polyoxyalkylene alkyl ester (D) 1 An aqueous sizing agent containing ˜30 parts by mass and containing no starch or silane coupling agent.   Furthermore, 1-50 mass parts of microparticles | fine-particles (E) are contained with respect to 100 mass parts of polyoxyalkylene bisphenol A ether (A), The aqueous sizing agent of Claim 1 characterized by the above-mentioned.   The aqueous sizing agent according to claim 2, wherein the fine particles (E) are hydroxyphenyltriazine or polyamide.   The aqueous sizing agent according to any one of claims 1 to 3, wherein the hydroxyl value of the polyoxyalkylene bisphenol A ether (A) is 200 mgKOH / g or less.   A glass fiber that has been surface-treated with the aqueous sizing agent according to claim 1.   A glass fiber cloth using the glass fiber according to claim 5.   The glass fiber cloth according to claim 6, which has been subjected to a water opening treatment and a silane coupling treatment.   A prepreg comprising the glass fiber cloth according to claim 6.   A composite material comprising the glass fiber cloth according to claim 6 or 7.