TWI599687B - Aqueous sizing agent and glass fiber and glass fiber cloth using the same - Google Patents

Description

Aqueous slurry and glass fiber and glass fiber cloth using the same

The present invention relates to an aqueous slurry for imparting bundling property to fibers, a glass fiber surface-treated with the aqueous slurry, and a glass fiber cloth using the glass fiber. (sizing agent: a slurry used to impart rigidity to a fibrous material, referred to herein as a slurry)

Conventionally, as a reinforcing material for a printed circuit board such as an electronic device or an electronic communication device, a glass fiber cloth excellent in properties such as mechanical properties, dimensional stability, heat resistance, and chemical resistance is used.

Further, in order to impart bundling property to the glass fiber, the woven property of the glass fiber is improved, and the productivity of the glass fiber cloth is improved, and the aqueous fiber slurry containing starch is adhered to the glass fiber. Therefore, when the glass fiber cloth is used as a material of a printed circuit board, it is necessary to remove the adhesion to the glass after the glass fiber cloth is manufactured, in order to prevent the starch remaining in the glass fiber from adversely affecting the mechanical properties and electrical properties of the printed circuit board. Fiber starch. Here, in order to remove the starch, the glass fiber cloth is subjected to a heat cleaning treatment.

Further, in order to modify the surface of the glass fiber cloth, a surface treatment (decane coupling treatment) is applied.

However, in the thermal cleaning treatment, the glass fiber cloth is exposed to a high temperature of 400 ° C or higher for a long period of time, so that deterioration of the glass fiber due to heat is caused, and the strength is lowered. Further, since the surface treatment is to wash the glass fiber cloth by a high-pressure water washing jet, the glass fiber which is deteriorated by the heat of the heat cleaning treatment and which has reduced strength is damaged and hairiness is defective. In particular, when a fine count of glass fibers is applied, the influence of such processing steps is greater.

In recent years, with the miniaturization and thinning of electronic devices such as smart phones and tablets, the glass fiber cloth itself of printed circuit board materials has been required to be thinner. In order to make the glass fiber cloth thinner, the fiber diameter of the glass fiber should be made finer and the number of bundles should be reduced. However, if the fiber diameter and the number of the glass fibers are reduced, the defects caused by the above-described thermal cleaning treatment and surface treatment become more remarkable, and in particular, the flexural rigidity of the mechanical properties is remarkably reduced.

Here, water-based slurries which do not require hot cleaning treatment and surface treatment have been discussed. For example, Patent Document 1 proposes the use of an aqueous slurry containing an epoxy resin, a bisphenol A ether to which ethylene oxide is added, and a decane coupling agent.

[prior technical literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2007-162171

However, the epoxy resin as the film forming agent of the aqueous slurry described in Patent Document 1 reacts with the decane coupling agent in a high temperature environment, so the linearity changes, and the glass fiber is fed during the weaving. The roller has a problem of poor attachment.

Further, since the aqueous slurry described in Patent Document 1 contains an epoxy resin, static electricity is likely to be generated, and when the glass fiber is wound up to the feed roller at a high speed, the conveyance becomes unstable and a short weft yarn is produced. Etc. There is a problem that we cannot woven continuously and stably.

Here, the present invention has been made to solve the above problems, and an object of the present invention is to provide a water-based slurry containing starch without using a heat cleaning treatment and a surface treatment, and at the same time suppressing a change in linear quality and an increase in the amount of static electricity generated in a high-temperature environment. A water-based slurry which can achieve stable and excellent woven properties.

The inventors of the present invention have intensively studied to solve the above problems, and as a result, have found that the above object can be attained by using an aqueous slurry containing a decane coupling agent, a film forming agent, an antistatic agent, and a softening agent in a specific ratio, and the present invention has been completed. That is, the gist of the present invention is as follows.

[1] An aqueous slurry containing 100 parts by mass of a decane coupling agent (A), 50 to 700 parts by mass of a film forming agent (B), 10 to 50 parts by mass of an antistatic agent (C), and a softening agent (D) 10 Up to 50 parts by mass, and does not contain starch and epoxy resin.

[2] The aqueous slurry according to [1], wherein the decane coupling agent (A) is N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxy Decane hydrochloride.

[3] The aqueous slurry according to [1] or [2], wherein the film forming agent (B) is a polyoxyalkylene bisphenol A ether.

[4] The aqueous slurry according to [3], wherein the polyoxyalkylene bisphenol A ether is a polyoxyethylene bisphenol A ether.

[5] The aqueous slurry according to [3], wherein the polyoxyalkylene bisphenol A ether has a hydroxyl value of 200 mgKOH/g or less.

[6] A glass fiber treated with the aqueous slurry treating surface according to any one of [1] to [5].

[7] A glass fiber cloth using the glass fiber according to [6].

According to the present invention, it is possible to provide an aqueous slurry containing starch without using a thermal cleaning treatment and a surface treatment, suppressing an increase in the amount of static electricity generated when using an aqueous slurry containing an epoxy resin, and using an epoxy resin in use. The aqueous slurry is a water-based slurry which is stable in a high-temperature environment and which is stable and excellent in texture. Further, the glass fiber cloth using the glass fiber surface-treated with the aqueous slurry of the present invention is excellent in heat resistance and mechanical properties, and thus can be suitably used as a reinforcing material for use as a printed circuit board for an electric machine or the like.

Hereinafter, the present invention will be described in detail.

The present invention relates to an aqueous slurry containing a decane coupling agent (A), a film forming agent (B), an antistatic agent (C), and a softening agent (D). More specifically, the aqueous slurry of the present invention is one in which a decane coupling agent (A), a film forming agent (B), an antistatic agent (C), and a softening agent (D) are dispersed in water. The aqueous slurry of the present invention does not contain starch or epoxy resin. The term "excluding" as used herein means substantially not containing it, and may contain a trace amount as long as it does not impair the effects of the present invention.

The decane coupling agent (A) is used for the purpose of improving the heat resistance of the fiber or fiber/resin composite, and improving the mechanical properties of the fabric or fiber/resin composite using the fiber.

The decane coupling agent (A) is preferably a hydrolyzable decane compound represented by the formula: YR-Si(CH ₃ ) _3-n X _n . The functional group Y may, for example, be a vinyl group, an epoxy group, a methacryl group, an amine group or a fluorenyl group, and among these, a vinyl group, a methacryl group, an amine group or a fluorenyl group is preferable. R may be a linear or branched alkyl group, a phenylene group, a quinone imine group or the like, or may be directly bonded to Y without passing through R. The functional group X may, for example, be an alkoxy group such as a methoxy group or an ethoxy group, a chloro group, an ethyl oxy group, a decyl group, an isopropoxy group or an amine group. N is an integer of 2 or 3. When N is 2 or 3, the plural Xs may be the same or different from each other.

More specifically, such a hydrolyzable decane compound may, for example, be vinyltriethoxydecane, vinyltrimethoxydecane, γ-(methacryloyloxypropyl)trimethoxynonane, β-(3) , 4-epoxycyclohexyl)ethyltrimethoxydecane, γ-glycidoxypropyltrimethoxydecane, γ-glycidoxypropylmethyldiethoxydecane, γ-mercaptopropyl Trimethoxy hydrazine Alkane, γ-aminopropyltriethoxydecane, N-β-(aminoethyl)-γ-aminopropyltrimethoxydecane, N-β-(N-vinylbenzylamino) Ethyl)-γ-aminopropyltrimethoxydecane. Among them, from the viewpoint of heat resistance, the decane coupling agent (A) is preferably N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxydecane.

N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxydecane is excellent in interfacial adhesion between glass fiber and matrix resin, and is excellent in moist heat resistance. A glass fiber suitable for use in materials for printing substrates.

The film forming agent (B) is used for imparting lubricity to the fibers to prevent the fibers from rubbing against the contact equipment, preventing static electricity and suppressing generation of hairiness, and further imparting heat resistance. The film forming agent (B) may, for example, be a polyether polyol or a polyester polyol-like polyol or a derivative thereof. Such poly-poly compounds may, for example, be hexanediol, polyoxypropylene glycol, polyoxypropyl glyceryl ether, polyoxypropyl propyl trimethylolpropane ether, polyoxypropyl sorbitol ether, polyoxyalkylene alkylene The bisphenol A ether preferably does not contain an epoxy group.

Among them, from the viewpoint of suppressing hairiness due to the film and imparting lubricity, the film forming agent (B) is preferably a polyoxyalkylene bisphenol A ether, and more preferably a polyoxyalkylene bisphenol A ether. Or polyoxypropyl bisphenol A ether, in particular, in view of excellent lubricity, a polyoxyethyl bisphenol A ether is further preferred.

The hydroxyl value of the polyoxyalkylene bisphenol A ether is preferably 200 mgKOH/g or less, more preferably 150 mgKOH/g or less. Water dispersibility when the hydroxyl value of polyoxyalkylene bisphenol A ether is 200 mgKOH/g or less It is lifted and can be uniformly covered on the surface of the glass fiber. Further, the change in the linear quality in the high temperature environment and the increase in the amount of static electricity are suppressed. When the hydroxyl value of the polyoxyalkylene bisphenol A ether is more than 200 mgKOH/G, it becomes difficult to disperse in water, and it cannot be made into an aqueous slurry.

The content of the film forming agent (B) must be 50 to 700 parts by mass, preferably 150 to 450 parts by mass, per 100 parts by mass of the decane coupling agent (A). When the content of the film forming agent (B) is less than 50 parts by mass, the generation of hairiness is increased to reduce the weavability. On the other hand, when the content of the film-forming agent (B) exceeds 700 parts by mass, the migration tends to be strong, and it is difficult to obtain a stable thread quality over the entire length, and the weavability is lowered.

The antistatic agent (C) is used for the purpose of reducing the chargeability of the fiber.

The antistatic agent (C) is, for example, an aliphatic polyamine, a polyalkylenealkylalkyl ester, or such a derivative, a quaternary ammonium salt or an inorganic salt, and preferably does not contain an epoxy group. The polyoxyalkylene alkyl ester is exemplified by a polyoxyalkylene ester. The inorganic salt may, for example, be an ammonium salt or a lithium salt. More specifically, the inorganic salt may, for example, be ammonium chloride, ammonium sulfate or lithium chloride.

The content of the antistatic agent (C) must be 10 to 50 parts by mass, preferably 20 to 40 parts by mass, per 100 parts by mass of the decane coupling agent (A). When the content of the antistatic agent (C) is less than 10 parts by mass, it is difficult to prevent charging, so that the unwirdness of the thread at the time of weaving is reduced, and the weavability is lowered. On the other hand, when the content of the antistatic agent (C) exceeds 50 parts by mass, heat resistance and mechanical properties are lowered.

Softener (D) is based on the purpose of enhancing the softness of the fiber And use. The softening agent (D) may, for example, be a fatty acid guanamine, a fatty acid ester, an ethylene glycol or a derivative thereof, and preferably does not contain an epoxy group.

The fatty acid guanamine may, for example, be a polyoxyalkylene fatty acid decylamine such as polyoxyethyl stearyl stearate. Further, the fatty acid guanamine may, for example, be composed of a polyethylamine and a fatty acid. The polyethylamine can be, for example, diethyltriamine, triethylamine or tetraethylamine. The fatty acid may, for example, be lauric acid, myristic acid, palmitic acid or stearic acid.

The fatty acid ester may, for example, be a fatty acid polyoxyalkylene ester of stearic acid polyoxyethylene ester, decyl laurate, isopropyl palmitate, cetyl palmitate or isopropyl stearate. , ethylene glycol adipate, trimethylolpropane trioctylate.

Examples of the ethylene glycols include polyethylene glycol and polypropylene glycol.

The content of the softening agent (D) must be 10 to 50 parts by mass, preferably 20 to 40 parts by mass, per 100 parts by mass of the decane coupling agent (A). When the content of the softening agent (D) is less than 10 parts by mass, flexibility is less likely to occur, and the traveling property is reduced, and the weavability is lowered. On the other hand, when the content of the softening agent (D) exceeds 50 parts by mass, the heat resistance is lowered. Moreover, mechanical properties are also reduced.

The aqueous slurry of the present invention is used by being attached to the surface of fibers such as inorganic fibers, natural fibers, and synthetic fibers. Examples of the inorganic fibers include glass, carbon, graphite, mullite, and alumina. Natural fibers include, for example, cotton, cellulose, natural rubber, linen, hemp, ramie, sisal, and wool. The synthetic fiber may, for example, be a fiber containing a thermoplastic resin. For example, polyamine, polylactic acid, polyaryl lipid, liquid crystal polymer, A fiber of polyester, acrylic resin, polycarbonate, polyurethane, polyvinyl resin, or polyolefin resin.

The fiber coated on the surface of the aqueous slurry of the present invention is excellent in flexibility, low friction, and low chargeability, and suppresses generation of hairiness, so that it has excellent woven properties.

The aqueous slurry of the present invention does not contain an epoxy resin. Therefore, it is possible to suppress the weaving which is stabilized by the change of the linear quality in the high-temperature environment generated when the epoxy resin aqueous slurry is contained. Further, it is possible to suppress an increase in the amount of static electricity generated when an aqueous epoxy resin containing an epoxy resin is used. Here, examples of the epoxy resin include a bisphenol type epoxy resin, an amine type epoxy resin, a novolac type epoxy resin, a cresol type epoxy resin, a resorcinol type epoxy resin, and a phenolphthalein. Alkyl epoxy resin, naphthol aralkyl epoxy resin, dicyclopentadiene epoxy resin, biphenyl skeleton epoxy resin, isocyanate modified epoxy resin, tetraphenylethane epoxy resin, Triphenylmethane type epoxy resin, bismuth type epoxy resin.

The aqueous slurry of the present invention does not contain starch. Therefore, the woven fabric composed of the fiber coated with the aqueous slurry of the present invention can provide excellent heat resistance and mechanical properties without using a hot cleaning treatment and a surface treatment performed when a water-based slurry containing starch is used. The effect that can be obtained by such a process is particularly remarkable when the number of bundled glass fibers is reduced and the fiber diameter of the glass fiber is further reduced as the size and thickness of the electronic device are reduced.

The aqueous slurry of the present invention exhibits low chargeability, and is therefore suitable for use in a polymer film which causes problems when foreign matter is mixed by the generation of static electricity. Rolling, packaging of electronic equipment, painting of automobiles, etc.

The aqueous slurry of the present invention may further contain a water-based resin for the purpose of suppressing the generation of hairiness based on the fiber bundle. Examples of the aqueous resin include a polyvinyl alcohol derivative, a polyvinylpyrrolidone, a styrene-maleic anhydride copolymer, an extended ethyl-maleic anhydride copolymer, a polypropylene decylamine, and a derivative thereof. , polyethylene glycol, styrene-butadiene copolymer, polyvinyl acetate, polyurethane, polyacrylate, vinyl chloride-vinyl acetate copolymer, ethylene vinyl acetate copolymer, ethylene-butyl Alkene-acrylic resin copolymer, polydichloroethylene ethylene, modified polyolefin, dimer acid polyamide, polyester copolymer. The water-based resin may be used singly or in combination.

The aqueous slurry may further contain inorganic particles for the purpose of improving the fiber opening property, the improvement of the woven property, and the improvement of the mechanical properties of the fabric. The material of the inorganic particles is selected from the group consisting of tantalum carbide, aluminum nitride, cerium oxide, clay, boron nitride, graphite, metal dichalcogenide, cadmium iodide, silver sulfide, and the like, and examples thereof include indium, bismuth, and the like. a metal inorganic substance of at least one metal of a group consisting of tin, copper, zinc, gold, and silver. Among them, in view of the effect of improving the high openness, the woven property, and the physical properties of the substrate, the material of the inorganic particles is preferably boron nitride. The inorganic particles may be used singly or in combination.

The aqueous slurry of the present invention may further contain a lubricant or a pH adjuster. As the lubricant, for example, a quaternary ammonium salt of lauryl trimethylammonium chloride, an alkyltrimethylammonium salt or the like can be used. As the pH adjuster, for example, acetic acid can be used.

The aqueous slurry of the present invention may further contain a hardening catalyst. The hardening catalyst can be exemplified by triethyl hexyl (dimethylaminomethyl) phenol. Acid salt. Further, the aqueous slurry of the present invention may further contain a hardener. Examples of the curing agent include aliphatic polyamines, alicyclic polyamines, amine-epoxy addition products, polyamine polyamines, aromatic polyamines, glycidyl ethers, and glycidyl esters.

In the aqueous slurry of the present invention, the total solid concentration of the above (A) to (D) is preferably from 2 to 10% by mass. When the solid content concentration is less than 2% by mass, it is difficult to uniformly coat the fibers, and hairiness is liable to occur, and heat resistance and mechanical properties are reduced. On the other hand, when the solid content concentration is more than 10% by mass, the amount of adhesion of the solid component to the fiber is increased, so that the viscous property on the surface of the fiber and the excessive amount of decane adhere thereto are deteriorated.

The aqueous slurry of the present invention may further contain a tackifier, a leveling agent, an antioxidant, a flame retardant, a flame retardant, a heat stabilizer, a fibrous reinforcing material, and a functional filler. The functional filler may, for example, be a thermally conductive filler, an electromagnetic wave shielding filler, a thermal insulation filler, or a high dielectric filler.

The aqueous slurry of the present invention can be produced by dispersing the above (A) to (D) in water. More specifically, first, the decane coupling agent (A) is mixed in water, and stirred at a temperature of 25 ° C or lower to carry out a hydrolysis reaction. When the hydrolysis reaction proceeds to a certain extent, the film forming agent (B), the antistatic agent (C), and the softening agent (D) are further added and stirred. The above-mentioned (B) to (D) may be separately added to the water containing the above (A) and further mixed, and the mixture of the above (B) to (D) may be added to the water containing the above (A) and mixed.

When a hardener is added to the mixture of the above (A) to (D), a stirring blade, a bead mill, a 3-roll mill, a jet mill, or the like may be used. The mixture of the above (A) to (D) and a hardener are mixed. In the mixture of the above (A) to (D) and the curing agent, when a solid matter such as an inorganic substance is not mixed, it may be mixed by using a disperser or vibration stirring.

When a dispersing machine is used, the number of rotations is preferably from 500 to 3000 rpm. When the vibration is stirred, the number of vibrations is preferably 30 to 50 Hz. When the number of rotations and the number of vibrations are within the above range, it is possible to suppress the heat generated by the heat of the machine and obtain the aqueous slurry. Further, when a bead mill is used to mix the solid matter with the mixture of the above (A) to (D) and the hardener, a cooler can be used in order to suppress heat generation due to stirring heat. By suppressing the heat generation, the reaction promotion of the decane coupling agent can be suppressed, and a stable aqueous slurry can be obtained.

Further, the present invention relates to a glass fiber treated with the above aqueous slurry. From the viewpoint of the woven property and the heat resistance, the amount of the aqueous slurry (solid content) attached to the glass fiber is 100 mass with respect to the total amount of the aqueous slurry (solid content) attached to the glass fiber and the glass fiber. The portion is preferably from 0.15 to 0.3 parts by mass, more preferably from 0.18 to 0.25 parts by mass.

The glass fiber (glass fiber) of the present invention can be obtained, for example, by applying the above-mentioned aqueous slurry to a glass fiber by a known method (for example, a roll anti-seepage method, a roll dipping method, or a spray coating method).

Further, the present invention relates to a glass fiber cloth using glass fibers having a surface treated with the aqueous slurry described above.

The glass fiber cloth of the present invention can be obtained, for example, by woven a glass fiber of a water-based slurry-treated surface by a known method (for example, a method using a shuttle loom, an air jet loom, or a rapier weaving machine). . Glass for weaving The glass fiber can be used, for example, as a Yarn (manufacturer) or a roving (who is not being produced).

The glass fiber cloth of the present invention is suitably used as a reinforcing material for a composite substrate of a glass fiber-resin for a printing substrate. The glass fiber-resin composite substrate using the glass fiber cloth is excellent in heat resistance, and is not affected by solder heat even in a moisture absorbing state, and the interface property between the glass fiber and the resin can be stably maintained.

Since the aqueous slurry of the present invention does not contain an epoxy resin like the conventional aqueous slurry, it is possible to suppress a change in the linear quality and an increase in the amount of static electricity generated in a high-temperature environment. In addition, since the thermal cleaning step and the surface treatment step are not required, deterioration of the glass fibers produced by the steps can be suppressed. Therefore, by using the glass fiber cloth of the present invention, the rigidity of the composite substrate of the glass fiber-resin for the printed substrate can be improved and it is difficult to be broken.

From the above point of view, the glass fiber and the glass fiber cloth of the present invention can be suitably used for components such as smart phones, input panels, power components, personal computers, home game consoles, and the like; DVD players, DVD recorders. Components, components of HDD recorders, components such as home TVs, plasma monitors, LCD TVs, etc.; components of mobile phones, various AV machines, OA machines, etc.; car audio, car navigation systems, inverters, Lighting, automotive electrical components, automotive engine components, automotive brake components, automotive interior components, aerospace materials, sports applications, outdoor applications, general industrial materials.

[Examples]

Hereinafter, embodiments of the present invention will be specifically described, but the present invention It is not limited to the embodiments.

The method for measuring and evaluating the characteristics of the aqueous slurry is as follows.

(1) The amount of water-based slurry applied to the glass fiber

The measurement of the amount of adhesion of the aqueous slurry to the glass fiber was measured in the following manner as a strong heat loss in accordance with JIS R 3420.

The glass fiber to which the aqueous slurry was attached was dried by hot air at 110 ° C to remove moisture (water from the aqueous slurry) from the glass fibers. After measuring the weight W ₁ of the glass fiber after removing the water, the glass fiber was allowed to stand in an electric furnace at 625 ° C for 30 minutes to further remove the aqueous slurry (solid content) from the glass fiber. The weight W ₂ of the glass fiber after removing the aqueous slurry (solid content) was measured.

The amount of the glass-based filler attached to the aqueous slurry can be calculated by the following formula.

Adhesion amount to glass fiber = [(glass fiber weight W ₁ after removal of moisture) - (glass fiber weight W ₂ after removal of aqueous slurry (solid fraction)) / (glass fiber weight W ₁ after removal of moisture) ×100

(2) Unwinding tension of glass fiber

The obtained glass fiber was released at a rate of 600 m/min, and the unwinding tension T1 was measured using a tensiometer (manufactured by Yokogawa Electric Co., Ltd.). Further, the obtained glass fiber was aged at 60 ° C for 24 hours, and the unwinding tension T2 of the glass fiber after the aging treatment was measured. Further, the rate of change in the unwinding tension was determined by the following formula using the unwinding tension T1 of the glass fiber before the aging treatment and the unwinding tension T2 of the glass fiber after the aging treatment.

Rate of change of unwinding tension (%) = (decompression tension T2-decompression tension T1) / (decompression tension T1) × 100

Practically, the rate of change of the unwinding tension is preferably within 20%.

(3) Hairiness of glass fiber

The number of hairiness after the tension bar was released by the obtained glass fiber at a speed of 300 m/min was counted by a detector.

Further, the number of hairiness was counted in the same manner as described above by additionally using glass fibers which were aged at 60 ° C for 24 hours.

(4) Electrostatic properties of glass fiber

The obtained glass fiber was taken up by a ruler, and an electrostatic detector (ZJ-SD100 manufactured by Omron Corporation) was placed in a lower portion of the rotating body of the winding portion, and the amount of static electricity generated by the process of arranging the line was measured. The number of times of taking is set to 100 times.

Further, the amount of static electricity was measured in the same manner as described above by using glass fibers which were aged at 60 ° C for 24 hours.

(5) Weaving of glass fiber

When the glass fiber cloth was woven by an air jet loom manufactured by Tsudakoma Kogyo Co., Ltd., the winding and moving state of the glass fiber to the feed roller were visually observed, and the number of times the weaving was stopped was calculated in one hour of the weaving time. Further, the weaving of the glass fiber is stopped when the glass fiber is poorly attached to the feed roller, or the delivery is unstable, and a short weft yarn is generated.

"◎" when it is not stopped once, "○" when it is stopped once or four times, and "X" when it is stopped five times or more.

In addition, except that the glass fiber which was aged at 60 ° C for 24 hours was used, the glass fiber cloth was woven in the same manner as described above, and the weave of the glass fiber was evaluated. Systematic.

(6) Heat resistance of glass fiber cloth

The obtained glass fiber cloth was impregnated with an epoxy resin to prepare a composite sheet. Then, the composite sheet was subjected to a heat history from the wet heat treatment and the solder bath, and the state of the composite sheet after that was evaluated.

More specifically, the obtained composite sheet was subjected to a wet heat treatment for 6 hours under the conditions of a water vapor pressure of 1.05 kg/cm ² G and an ambient temperature of 121 ° C using a pressure cooker. After the wet heat treatment, the composite sheet was immersed in water at 20 to 25 ° C for 15 minutes. After immersion in water, the composite sheet was pulled up and immersed in a 260 ° C solder bath for 25 seconds. The solder attached to the composite sheet was cut off from the composite sheet immersed in the solder bath. The surface of the composite sheet after the solder was cut off was observed by a lithography machine (manufactured by EPSON Co., Ltd.), and the proportion of the "whitening portion" (the ratio of the area of the whitened portion to the total surface area of the composite sheet) was determined.

When the albino is less than 1%, it is "◎", when it is 1% or more to less than 30%, it is "○", 30% or more is less than 50%, it is "△", and when it is 50% or more, it is "X".

(7) Mechanical properties of glass fiber cloth

The obtained glass fiber cloth was impregnated with an epoxy resin to prepare a composite sheet. A 12-layer laminated composite sheet was pressed by a vacuum press to prepare an FR-4 resin impregnated substrate (a plate of 80 mm × 25 mm). Using this substrate, the flexural strength and the flexural modulus were determined in accordance with the three-point deflection test in accordance with JIS K 6911 under the conditions of a speed of 5 mm/min and a distance between fulcrums of 16 mm.

Further, a glass fiber cloth was produced in the same manner as described below except that the glass fiber was aged at 60 ° C for 24 hours. The glass fiber cloth was also subjected to the same flexural strength and flexural modulus as described above.

(8) The hydroxyl value of the film forming agent

10 g of a film forming agent was dissolved in 5 mL of a mixture of acetic anhydride and pyridine (acetic anhydride/pyridine (volume ratio = 1/5), and then acetic anhydride was reacted with a hydroxyl group in the film forming agent at 100 ° C for 1 hour. Thereafter, distilled water was further added thereto, and the mixture was stirred at 100 ° C for 10 minutes to decompose excess acetic anhydride to obtain a sample liquid. The sample solution was titrated with a 0.5 mol/L potassium hydroxide aqueous solution to determine a titer W ₃ (mL). Similarly, in the case where the film forming agent was not used (only the above-mentioned mixed solution), titration was also performed, and the titer W ₄ (mL) was determined. The hydroxyl value was calculated according to the following formula.

Hydroxyl Price (mgKOH/g) = (W _{4 -} W ₃ ) × f × 28.05/10

(f: titer of 0.5 mol/L potassium hydroxide aqueous solution)

The materials constituting the aqueous slurry are listed below.

(1) decane coupling agent (A)

(A1) a mixed solution of N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxydecane hydrochloride, 90% acetic acid and water (Dongli. Dow Corning Corporation, Z 6032)

(II) Film forming agent (B)

(B1) Polyoxyethyl bisphenol A ether (made by Yoshimura Oil Chemical Co., Ltd., GF690, hydroxyl price 123 mgKOH/g)

(B2) Polyoxyethylene ethyl bisphenol A ether (manufactured by Sanyo Chemical Industries, Inc., NEWPOL BPE-60, hydroxyl value 228 mgKOH/g)

(B3) Polyoxypropyl bisphenol A ether (manufactured by Sanyo Chemical Industries, Inc., NEWPOL BP-5P, hydroxyl value 211 mgKOH/g)

(B4) Bisphenol A type epoxy resin (EPOLIKA, manufactured by SHIKIBO Co., Ltd.)

(B5) Starch (made by Nissho Chemical Co., Ltd., BIOSTARCH)

(III) Antistatic agent (C)

(C1) Polyoxyethylidene Ethyl Ester (NOIRAN, manufactured by Daisei Oil & Fats Industry Co., Ltd.)

(C2) Grade 4 ammonium salt (manufactured by First Industrial Pharmaceutical Co., Ltd., CATIOGEN)

(IV) Softener (D)

(D1) Cationic fatty acid decylamine (KSK, manufactured by Yoshisei Oil & Fats Industry Co., Ltd.)

(D2) cationic polyamidoamine (manufactured by Daiichi Kogyo Co., Ltd., DKS TAFFULON)

(D3) Polyethylene Glycol (Sanyo Chemical Industry Co., Ltd., PEG600)

"Examples 1 to 24 and Comparative Examples 1 to 9"

The above-described decane coupling agent (A), film forming agent (B), antistatic agent (C), and softening agent (D) were mixed with water to prepare an aqueous slurry.

In the preparation of the aqueous slurry, the type of the decane coupling agent (A), the film forming agent (B), the antistatic agent (C), the softening agent (D), and the mixing ratio (parts by mass) of each solid component are used. Change to the one shown in Tables 1 to 3.

The amount of water to be added is adjusted so that the solid content concentration of the aqueous slurry (the concentration of the solid content of the above (A) to (D) is controlled to be in the range of 4 to 8 mass%).

The aqueous slurry obtained above was attached to a plurality of glass fiber filaments, and the glass fibers were bundled into one bundle (strand). Secondly, the strand is taken up without taking the strand and the glass roving is obtained. The strands were unwound from the obtained glass roving, and while being twisted, they were wound around a bobbin to obtain a glass yarn. The glass fiber for weaving is thus obtained. The glass fiber was a glass yarn manufactured by Dynecco Glass Fiber Co., Ltd. (item number: C120O, average fiber diameter: 4.5 μm, total fiber count: 100 pieces, count: 4.2 tex, number of turns = 1.0 Z).

Further, the amount of the aqueous slurry (solid content) of the glass fiber varies depending on the solid content concentration of the aqueous slurry. When the solid content concentration in the aqueous slurry is 4 to 8 mass%, the amount of the aqueous slurry (solid content) is 100 parts by mass based on the total amount of the glass fiber and the aqueous slurry (solid content) attached to the glass fiber. It is 0.15 to 0.4 parts by mass.

The glass fiber for woven fabric obtained above was woven by an air jet loom manufactured by Tsudakoma Kogyo Co., Ltd. to obtain a glass fiber cloth.

The above-described various evaluations were carried out on the aqueous slurry, glass fiber, and glass fiber cloth obtained above. The evaluation results are shown in Tables 1 to 3.

The glass fibers of Examples 1 to 24 suppress the increase in the amount of generation of static electricity, and even when exposed to a high temperature environment, the change in the linear quality is suppressed, and the weaving can be stabilized. Further, the glass fiber cloth thus obtained is excellent in heat resistance and mechanical properties.

Since the glass fiber of Example 6 has a content of the film forming agent smaller than the preferred range of the present invention, the charge amount is slightly higher than that of Example 1, and the woven property is slightly inferior. Further, the glass fiber cloth thus obtained is slightly lower in heat resistance and mechanical properties.

Since the glass fiber of Example 7 has a film forming agent content more than the preferred range of the present invention, the glass fiber cloth thus obtained has a slightly lower mechanical property than that of Example 1.

Since the content of the antistatic agent of the eighth embodiment is less than the preferred range of the present invention, the unwinding tension and the charge amount are slightly higher than those of the first embodiment, and the woven property is slightly inferior. Further, the glass fiber cloth thus obtained has a slightly lower mechanical property.

Since the content of the antistatic agent in the glass fiber of Example 9 was more than the preferred range of the present invention, the unwinding tension was slightly higher than that of Example 1, and the woven property was slightly inferior. Further, the glass fiber cloth thus obtained is slightly lower in heat resistance and mechanical properties.

Since the content of the softening agent in the glass fiber of Example 10 was less than the preferred range of the present invention, the unwinding tension was slightly higher than that of Example 1, and the woven property was slightly inferior. Further, the glass fiber cloth thus obtained has a slightly lower mechanical property.

Since the content of the softening agent in the glass fiber of Example 11 was more than the preferred range of the present invention, the unwinding tension was slightly higher than that of Example 1, and the woven property was slightly inferior. Further, the glass fiber cloth thus obtained is slightly lower in heat resistance and mechanical properties.

Since the glass fibers of Examples 12 and 13 used a film forming agent having a hydroxyl value of more than 200 mgKOH/g, the unwinding tension was too large as compared with Example 1. The weaving property has deteriorated slightly.

In the glass fiber of Comparative Example 1, since an aqueous slurry containing an epoxy resin as a film forming agent was used, deterioration of the wire was changed at the time of high-temperature treatment, and the texture was deteriorated. Further, the glass fiber cloth thus obtained is low in heat resistance.

The glass fiber of Comparative Example 2 is a water-based slurry using a film forming agent made of an epoxy resin, so that the unwinding tension is high, the amount of hairiness is large, and the amount of charge is high, and a film having adhesion (adhesiveness) is formed. The system has deteriorated. Further, the glass fiber cloth thus obtained is low in heat resistance.

In the glass fiber of Comparative Example 3, since the content of the film forming agent was too small, the glass fiber could not be sufficiently formed into a film, and hairiness was generated, and the texture was deteriorated.

In the glass fiber of Comparative Example 4, since the content of the film forming agent was too large, the amount of the aqueous slurry adhering to the surface of the glass fiber was excessive, the glass fiber became sticky, and the texture was deteriorated.

Since the glass fiber of Comparative Example 5 does not contain an antistatic agent, the weaving is unstable due to the influence of static electricity, and the texture is deteriorated.

Since the glass fiber of the comparative example 6 was excessively contained in the content of the antistatic agent, the glass fiber cloth thus obtained was low in heat resistance and mechanical properties.

Since the glass fiber of Comparative Example 7 does not contain a softening agent, the flexibility of the wire is lowered, and the texture is deteriorated.

In the glass fiber of Comparative Example 8, since the content of the softening agent was too large, the heat resistance and mechanical properties of the glass fiber cloth thus obtained were low.

The glass fiber of Comparative Example 9 was used as a film forming agent. The starch is reduced in association with the decane coupling agent, so that the glass fiber cloth thus obtained has low heat resistance.

Claims (6)

An aqueous slurry containing 100 parts by mass of a decane coupling agent (A), 50 to 700 parts by mass of a film forming agent (B), 10 to 50 parts by mass of an antistatic agent (C), and 10 to 50 parts by mass of a softening agent (D) In the case where the starch and the epoxy resin are not contained, the film forming agent (B) is a polyoxyalkylene bisphenol A ether. The aqueous slurry according to claim 1, wherein the decane coupling agent (A) is N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxy. Decane hydrochloride. The aqueous slurry according to claim 1 or 2, wherein the polyoxyalkylene bisphenol A ether is a polyoxyethyl bisphenol A ether. The aqueous slurry according to claim 1 or 2, wherein the polyoxyalkylene bisphenol A ether has a hydroxyl value of 200 mgKOH/g or less. A glass fiber treated with an aqueous slurry treatment surface according to any one of claims 1 to 4. A glass fiber cloth using the glass fiber as described in claim 5 of the patent application.