JP6830613B2 - Fiberglass strands, glass fabrics, and cement products - Google Patents

Description

The present invention relates to glass fiber strands, glass fabrics, and cement products.

Glass fiber strands containing ZrO ₂ and having alkali resistance are widely used as reinforcing materials for GRC (Glassfiber Reinforced Cement), supplement brittleness of cement, and improve tensile strength, bending strength, and impact strength of GRC. Playing a role.

Glass fiber strands are tens to hundreds after applying a glass fiber sizing agent to a glass fiber monofilament obtained by pulling molten glass from a bushing having hundreds to thousands of nozzles using an applicator. After bundling the glass fiber monofilaments, the glass fiber monofilaments are wound into a paper tube to make a cake, and the volatile components of the glass fiber sizing agent are dried to form a film on the surface of the glass fiber monofilaments. Manufactured by.

The glass fiber sizing agent has a function of preventing the surface of the glass fiber monofilament formed in the spinning process from being scratched, a function of preventing fluffing and yarn breakage when the glass fiber monofilament is bundled, and the strength of GRC. It has a function to improve.

In the manufacturing process of GRC, the glass fiber strands come into contact with various members. As a result, fiberglass strands suffer a lot of damage by the time GRC is manufactured. For example, in the FW molding method, which is one of the GRC manufacturing methods, tension is applied to the glass fiber strands in order to accurately wind the glass fiber strands around the mandrel. Specifically, in order to impregnate the cement, the glass fiber strands travel in a cement-filled cement tank and are wound around a mandrel while being tensioned by eyelets. Therefore, glass fiber strands with low tensile strength will be cut when tension is applied by the eyelets.

As described above, if the glass fiber strand is cut during the winding around the mandrel, not only the winding workability around the mandrel is lowered, but also the strength of the GRC is lowered.

On the other hand, cement mortar and concrete used for cement products and outer walls of buildings are prone to cracks due to drying shrinkage, and if such cracks are left for a long period of time, the cracks gradually crack on the surface of the product. It expands from the surface to the back surface, and water invades from one side to cause water leakage, and the strength of the cement product tends to decrease, which is not preferable.

Therefore, it has been attempted to bury a glass woven fabric made of glass fiber strands near the surface of the cement product to prevent the expansion of cracks (glass woven fabric reinforcement).

Usually, this type of glass woven fabric is produced by first driving weft threads composed of a plurality of glass fiber strands between warp threads composed of a plurality of glass fiber strands at regular intervals, and then entwining the warp threads with the weft threads. It is produced by producing a mesh-like raw woven fabric, then applying a resin adhesive such as an emulsion resin or a thermosetting resin dissolved in a solvent to the raw woven fabric, drying and solidifying the raw woven fabric, and sealing the woven fabric. ..

Therefore, the impregnation property of the resin adhesive for sealing into the glass fiber strand is important. Insufficient impregnation of the resin into the glass fiber strands reduces the tensile strength of the glass fabric. When the amount of the sizing agent applied to the glass fiber is reduced in order to improve the impregnation of the resin adhesive, the tensile strength of the glass fiber strand itself decreases, and as a result, fluffing and cutting of the glass fiber strand during the production of the glass fabric are caused. It becomes.

Patent Document 1 describes glass roving for GRC as a sizing agent for glass fibers, which contains 55% by mass or more of an ethylene-vinyl acetate copolymer resin having an ethylene content of 5% by mass or more in the solid content of the sizing agent for glass fibers. It is disclosed.

Japanese Unexamined Patent Publication No. 2003-20151

The glass roving for GRC of Patent Document 1 is harder to cut than the conventional one, but there is room for improvement. Moreover, the impregnation property of the resin adhesive is insufficient.

The present invention has been made in view of the above circumstances, and is composed of glass fiber strands and glass fiber strands having high tensile strength, suppressing fluffing during production of glass woven fabric, and having good impregnation property of a resin adhesive. It is an object of the present invention to provide a glass woven fabric in which a glass fiber strand is sufficiently impregnated with a sealing resin adhesive, and a cement product.

Glass fiber strands of the present invention, the glass fiber monofilaments containing ZrO ₂ or 12 wt%, it is configured to cover the glass fiber monofilaments, (a) a bisphenol A type epoxy resins, and (b) poly It is characterized by having a film layer containing an oxyethylene polyoxypropylene glycol and / or a bisphenol AEO adduct.

Further, in the glass fiber strand of the present invention, it is preferable that the film layer further contains a polyester resin.
The glass fiber strands of the present invention, the (a) bisphenol A type epoxy resins or bisphenol A type epoxy resin and polyester resin, wherein (b) polyoxyethylene polyoxypropylene glycol and / or bisphenol AEO adduct The mass ratio of (a) / (b) = 0.25
It is preferably ~ 3.05.

Further, the glass fiber strand of the present invention preferably has a count of 300 to 4800 tex.

The glass woven fabric of the present invention comprises a plurality of warp threads composed of the glass fiber strands, a plurality of weft threads composed of the glass fiber strands and arranged so as to intersect the warp threads, and at least the above. It is characterized by having a resin adhesive formed at the intersection of the warp and the weft.

In the glass woven fabric of the present invention, the interval between the plurality of warp threads and the interval between the weft threads are 3 to 50 mm, the adhesion rate of the resin adhesive is 5 to 30% by mass, and the basis weight is 60 to 1200 g / m ² . It is preferable to have.

Further, in the glass woven fabric of the present invention, it is preferable that the resin adhesive is at least one resin selected from the group consisting of acrylic resin, styrene-butadiene rubber, polyester resin, and melamine resin.

The cement product of the present invention is characterized by containing the above-mentioned glass woven fabric.

The cement product of the present invention is characterized by containing the above-mentioned glass fiber strands.

According to the present invention, the resin adhesive for sealing is composed of glass fiber strands and glass fiber strands having high tensile strength, suppressing fluffing during production of glass woven fabric, and having good impregnation property of the resin adhesive. Can provide glass woven fabrics and cement products that are fully impregnated with glass fiber strands.

Hereinafter, embodiments for carrying out the present invention will be described, but the present invention is not limited to the following embodiments, and is based on ordinary knowledge of those skilled in the art without departing from the spirit of the present invention. It should be understood that the following embodiments are also modified or improved as appropriate within the scope of the present invention.

The glass fiber strand of the present invention contains a glass fiber monofilament containing 12% by mass or more of ZrO ₂ . Glass fiber monofilaments are obtained by pulling molten glass out of a number of nozzles provided at the bottom of a platinum bushing. The glass fiber monofilament preferably contains ZrO ₂ in an amount of 12 to 20% by mass, more preferably 14 to 18% by mass. Since the glass fiber monofilament containing 12% by mass or more of ZrO ₂ has good alkali resistance, the glass fiber strand or the glass fabric composed of the glass fiber monofilament is less likely to be eroded by the alkali component contained in the cement. Further, when the ZrO _{2 of the} glass fiber monofilament is 20% by mass or less, the glass fiber strand or the glass woven fabric can be manufactured at a relatively low cost.

Examples of the glass fiber monofilament include SiO ₂ 54 to 65% by mass, ZrO ₂ 12 to 20% by mass, Li ₂ O 0 to 5% by mass, Na ₂ O 10 to 17% by mass, and K ₂ O 0.5 to 8 by mass. Glass fiber monofilament containing% by mass, RO (R represents Mg, Ca, Sr, Ba, Zn) 0 to 10% by mass, TiO ₂ 0.5 to 7% by mass, and Al ₂ O _{30 to} 2% by mass. Can be mentioned.

The glass fiber monofilament contains SiO ₂ 57 to 64% by mass, ZrO ₂ 14 to 18% by mass, Li ₂ O 0.5 to 3% by mass, Na ₂ O 11 to 15% by mass, and K ₂ O 1 to 5% by mass. It is preferable to contain RO 0.2 to 8% by mass, TiO ₂ 0.5 to 5% by mass, and Al ₂ O _{30 to 1} % by mass.

The glass fiber strands of the present invention, the glass fiber monofilaments containing ZrO ₂ or 12 wt%, may comprise a glass fiber monofilaments containing ZrO ₂ less than 12 wt%. Examples of the glass fiber monofilament containing less than 12% by mass of ZrO ₂ include glass fiber monofilament made of alkali-resistant glass. For example, SiO ₂ 47 to 58% by mass, Al ₂ O ₃ 3 to 12% by mass, Fe ₂ O _{30 to} 4% by mass, FeO 0 to 4% by mass, MgO 1 to 6% by mass, CaO 12 to 22% by mass. , Na ₂ O 7 to 16% by mass, K ₂ O 0 to 5% by mass, B ₂ O _{30 to} 10% by mass, TiO _{20 to} 4% by mass, MnO 0 to 4% by mass, BaO 0 to 3% by mass. , _P 2 _O 5 0 to 4 _wt%, SO 3 0 to 1 wt%, and a glass fiber monofilaments containing F 0 to 1 wt%.

The glass fiber strand of the present invention can be produced as follows. First, a glass fiber sizing agent is applied to a plurality of glass fiber monofilaments drawn from a nozzle at the bottom of the bushing by an applicator or the like, and these glass fiber monofilaments are bundled into one bundle by a gathering shoe and wound around a collet. Make it a cake. Then, the cake is placed in a dryer, and the solvent (volatile matter) contained in the glass fiber sizing agent is evaporated at 80 to 130 ° C. for about 1 to 30 hours to partially or the entire surface of the glass fiber monofilament. A solid film layer that covers the surface is formed. This gives a glass fiber strand wound around the cake.

The glass fiber sizing agent contains a solvent and the components constituting the film layer shown below. The components constituting the film layer will be described below.

Coating layer comprises (a) a bisphenol A type epoxy resins, and (b) polyoxyethylene polyoxypropylene glycol and / or bisphenol AEO adduct. Further, a polyester resin may be further contained.

The film layer containing (a) bisphenol A type epoxy resin or bisphenol A type epoxy resin and polyester resin , and (b) polyoxyethylene polyoxypropylene glycol and / or bisphenol AEO adduct has a focusing property between glass fiber monofilaments. And protects the surface of the fiberglass monofilament. Therefore, a glass fiber strand having high tensile strength and less fluffing during production of a glass woven fabric can be obtained. Further, the resin adhesive used for sealing the glass fabric sufficiently impregnates the glass fiber strands. Incidentally, (a) a bisphenol A type epoxy resins or, if containing only bisphenol A type epoxy resin and polyester resin or (b) polyoxyethylene polyoxypropylene glycol and / or bisphenol AEO adduct, alone, the resin adhesive Impregnation is low.

Then, (a) a bisphenol A type epoxy resins or the weight ratio of bisphenol A type epoxy resin and polyester resin, and (b) polyoxyethylene polyoxypropylene glycol and / or bisphenol AEO adduct, (a) / ( b) = 0.25 to 3.05 is preferable.
((A) bisphenol A type epoxy resins or bisphenol A type epoxy resin and polyester resin, and (b) the weight ratio of the polyoxyethylene polyoxypropylene glycol and / or bisphenol AEO adduct, (a) / (b ) = 0.25 to 3.05, the focusing property can be further enhanced, the surface can be sufficiently protected, and the impregnation property of the resin adhesive becomes good.

In addition, polyoxyethylene polyoxypropylene glycol is obtained by ring-opening polymerization of ethylene oxide and propylene oxide. Cyclic ethers other than ethylene oxide and propylene oxide may also be polymerized together. The weight average molecular weight of polyoxyethylene polyoxypropylene glycol is preferably 1000 to 2000. Polyoxyethylene When the ethylene oxide of polyoxypropylene glycol is polymerized, the mass ratio of the ethylene oxide monomer is preferably 60 to 90% by mass, preferably 65 to 85% by mass, based on the total amount of the monomers to be polymerized. Is more preferable.

The bisphenol AEO adduct is a compound obtained by adding ethylene oxide to bisphenol A.

The film layer may contain a silane coupling agent. The silane coupling agent has an organic functional group. Examples of the organic functional group include an amino group, an epoxy group, a ureido group, a methacryl group, a vinyl group, a mercapto group, a styryl group and the like. Among these silane coupling agents having an organic functional group, a silane coupling agent having an epoxy group that particularly improves tensile strength is preferable.

In addition, the film layer may contain a lubricant, wax and the like.

The glass fiber strand of the present invention preferably has a count of 300 to 4800 tex. When the count is 300 tex or more, the glass fiber strand has sufficient tensile strength, and fluffing during production of the glass woven fabric and cutting of the glass fiber strand are unlikely to occur. When the count is 4800 tex or less, it is easy to handle the glass fiber strand.

The glass fiber strand of the present invention preferably has a loss on ignition of 0.5 to 1.5% by mass. When the strong heat loss is 0.5% by mass or more, the glass fiber strand has sufficient tensile strength, and fluffing during production of the glass woven fabric and cutting of the glass fiber strand are unlikely to occur. When the loss on ignition is 1.5% by mass or less, the cement is likely to be impregnated into the glass fiber strand in a short time.
The ignition loss is a value obtained by a method according to JIS R3420 (2013).

The glass fiber strand of the present invention can be produced as follows. First, a glass fiber sizing agent is applied to a plurality of glass fiber monofilaments drawn from a nozzle at the bottom of the bushing by an applicator or the like, and these glass fiber monofilaments are bundled into one bundle by a gathering shoe and wound around a collet. Make it a cake. Then, the cake is placed in a dryer, and the solvent (volatile matter) contained in the glass fiber sizing agent is evaporated at 80 to 130 ° C. for about 1 to 30 hours to partially or the entire surface of the glass fiber monofilament. A solid film layer that covers the surface is formed. This gives a glass fiber strand wound around the cake.

The glass fiber sizing agent contains a solvent such as water and an organic solvent, and the components constituting the above-mentioned film. The solvent is preferably pure water, ion-exchanged water, industrial water, distilled water or the like.
Further, the proportion of the components constituting the film contained in the solvent is substantially the same as the proportion of the components constituting the film layer formed after the solvent is evaporated.
The amount of the solvent in the sizing agent for glass fibers is preferably 80 to 99% by mass, and more preferably 85 to 98% by mass.

Next, the glass woven fabric of the present invention will be described. The glass woven fabric of the present invention includes a plurality of warp threads and weft threads composed of the glass fiber strands of the present invention. The plurality of warp threads are aligned in a predetermined direction. Then, the plurality of weft threads are aligned in a direction different from the alignment direction of the warp threads so as to be arranged so as to intersect the plurality of warp threads. For example, the weft threads are aligned in a direction perpendicular to the direction in which the warp threads are aligned.

The spacing between the plurality of warp threads and the spacing between the plurality of weft threads are preferably 3 to 50 mm. If the distance is 3 mm or more, cement can easily enter between the glass fiber strands. If the interval is 50 mm or less, it can be reinforced efficiently. The distance between the plurality of warp threads and the distance between the plurality of weft threads is preferably 5 to 40 mm, more preferably 10 to 35 mm.

A resin adhesive is attached to the intersection of the warp and the weft. As a result, the warp and weft are bonded to form a woven fabric. Acrylic resin, styrene-butadiene rubber, polyester resin, and melamine resin can be used as the resin adhesive, but acrylic resin is particularly preferable because it has excellent alkali resistance and can strengthen the stiffness of the glass woven fabric.

The content of the resin adhesive is preferably 5 to 30% by mass with respect to the total mass of the glass woven fabric. When the content of the resin adhesive is 5% by mass or more, the glass woven fabric is less likely to cause misalignment. Further, when the content of the resin adhesive is 30% by mass or less, the glass woven fabric has sufficient elasticity and is excellent in workability at the time of molding a cement product. The content of the resin adhesive is preferably 7 to 25% by mass, more preferably 10 to 20% by mass, based on the total mass of the glass woven fabric.

The glass woven fabric of the present invention preferably has a basis weight of 60 to 1200 g / m ² . When the basis weight is 60 g / m ² or more, a sufficient reinforcing effect can be obtained. When the basis weight is 1200 g / m ² or less, the impregnation property of cement into the glass woven fabric becomes good.

In addition to the warp and weft, the glass woven fabric of the present invention may have a plurality of third threads that are aligned in a direction different from the warp and weft, such as a triaxial woven fabric. .. In that case, a resin adhesive is attached to the intersection of each thread.
In addition, a plurality of third threads that are aligned in a direction different from the warp and weft threads and a plurality of fourth threads that are aligned in a direction different from the warp threads, weft threads, and the third threads, such as a quadruple woven fabric. May have a thread of. In that case, a resin adhesive is attached to the intersection of each thread.

Next, the cement product of the present invention will be described. The cement products of the present invention include the glass fabrics of the present invention.

The cement product of the present invention contains, for example, cement, sand, aggregate such as kaolin, water, a mortar made of an admixture, and a glass woven fabric.

The cement product of the present invention is preferably produced by the following steps.

The shape of the product is molded in advance with mortar, and the water contained in the mortar is dried. After drying, the glass woven fabric is attached, mortar is supplied to the surface of the glass woven fabric, and the glass woven fabric is embedded. Finally, the moisture in the mortar is dried.

In addition, the cement product of the present invention contains the glass fiber strand of the present invention instead of the glass woven fabric.

The content ratio of the glass fiber strand in the cement product is preferably 10 to 20% by mass. When the content ratio of the glass fiber strand is 10% by mass or more, a sufficient reinforcing effect can be obtained. When the content ratio of the glass fiber strand is 20% by mass or less, the glass fiber strand is not exposed on the surface of the cement product.

The cement product of the present invention is preferably produced by the following steps.

First, the glass fiber strands are impregnated with cement by running the glass fiber strands in a mortar tank in which the mortar is stored (impregnation step). It is preferable to set the traveling speed of the glass fiber strand and the traveling distance of the glass fiber strand in the mortar tank while checking the content of the cement impregnated in the glass fiber strand.

Next, the glass fiber strand impregnated with cement is wound around a mandrel by running in a mortar tank (winding process). The mandrel has a shape corresponding to the shape of the cement product to be manufactured. The mandrel is composed of materials such as metal, ceramic, and plastic. The glass fiber strand may be wound so as to have a single layer with respect to the mandrel, or may be wound so as to have a plurality of layers. It is preferable to wind the glass fiber strands into a plurality of layers because a high-strength cement product can be obtained. Further, it is preferable to wind the glass fiber strand around the mandrel while applying tension to the glass fiber strand by the eyelet because the glass fiber strand can be wound with high accuracy.

The cement and water in the mortar impregnated with the glass fiber strands undergo a hydration reaction over time and solidify. As a result, a strong cement product can be obtained.

Finally, the mandrel is extracted to complete the cement product (extraction process).

The present invention will be described in more detail based on specific examples, but the present invention is not limited to the following examples, and the present invention shall be appropriately modified and carried out without changing the gist thereof. Is possible.

First, the glass composition is SiO ₂ 57.9% by mass, ZrO ₂ 17.2% by mass, Li ₂ O 0.5% by mass, Na ₂ O 14.8% by mass, K ₂ O 1.3% by mass, CaO 0. .9 wt%, weighed so as to TiO 2 _7.4% by mass, various glass raw material obtained by compounding and melt in a glass melting furnace. The molten glass was drawn out from a plurality of nozzles provided in the molded product to obtain a glass fiber monofilament. The diameter of the glass fiber monofilament was about 27 μm. Next, using an applicator, the solid content content ratio was prepared as shown in Tables 1 and 2, and the glass fiber sizing agent dissolved in distilled water was evenly applied to the surface of the glass fiber monofilament. It was applied. Then, 1600 glass fiber monofilaments were bundled by a gathering shoe to form one glass fiber strand, which was further wound around a paper tube to prepare a wound body of the glass fiber strand. Next, the winding body is heated and dried by a dielectric heating device until the sizing agent for glass fibers is solidified and a film layer is formed, and then the paper tube is pulled out from the winding body of the glass fiber strands. After pulling out several layers of glass fiber strands from the innermost layer, the pulled out glass fiber strands were excised. In this way, wound bodies of Examples and Comparative Examples in which 2400 tex glass fiber strands were wound were obtained. The loss on ignition of the glass fiber strands is 0.8% by mass, respectively.

(Tensile strength of glass fiber strand)
The tensile strength of the glass fiber strand was evaluated according to JIS R-3420 (2013) 7.4.3. Specifically, the glass fiber strand is pulled out from the winding body and cut into 350 mm. Set the tension tester with a distance between chucks of 250 mm, and measure the tensile strength of the strands. The tensile strength was converted into N / tex count and compared and evaluated.

(Evaluation of impregnation)
As an evaluation of impregnation property, six glass fiber strands are inserted into a glass tube having a diameter of 6.0 mm, and one end thereof is aligned with the end of the glass tube. The aligned ends were dipped in a colored acrylic emulsion, and 30 minutes later, the height at which the acrylic emulsion was sucked up by a capillary phenomenon was defined as impregnation. The higher the sucked up height, the better the impregnation property of the resin adhesive.

Tables 1 and 2 show the tensile strength and impregnation property of the glass fiber strands in Examples and Comparative Examples.

The samples of Examples 1 to 6 had a high tensile strength of 0.45 N / tex and had a sufficient tensile strength. Further, the permeability was 21 cm or more, and the impregnation property of the resin adhesive into the glass fiber strand was good. On the other hand, Comparative Example 7 which does not contain polyoxyethylene polyoxypropylene glycol and bisphenol AEO adduct, and Comparative Examples 8 to 10 which do not contain bisphenol A type epoxy resin and polyester resin have permeability of 14 to 18 cm and impregnation property. Was low. Further, in Comparative Examples 8 to 10 containing no bisphenol A type epoxy resin and polyester resin, the tensile strength was 0.43 N / tex or less, and the tensile strength was low.

Claims (9)

Glass fiber monofilament containing 12% by mass or more of ZrO ₂ and
It is configured to cover the glass fiber monofilament.
(A) glass fiber strands and having a coating layer comprising a bisphenol A type epoxy resins, and (b) polyoxyethylene polyoxypropylene glycol and / or bisphenol AEO adduct. The glass fiber strand according to claim 1, wherein the film layer further contains a polyester resin. The mass ratios of (a) bisphenol A type epoxy resin or bisphenol A type epoxy resin and polyester resin, and (b) polyoxyethylene polyoxypropylene glycol and / or bisphenol AEO adduct are (a) / (b). The glass fiber strand according to claim 1 or 2 , wherein the value is 0.25 to 3.05. The glass fiber strand according to any one of claims 1 to 3, wherein the count is 300 to 4800 tex. A plurality of warp yarns composed of the glass fiber strand according to any one of claims 1 to 4 and
A plurality of weft threads composed of the glass fiber strand according to any one of claims 1 to 4 and arranged so as to intersect the warp threads.
A glass woven fabric having at least a resin adhesive adhering to the intersections of the warp threads and the weft threads. The spacing between the plurality of warp threads and the spacing between the weft threads is 3 to 50 mm.
The adhesion rate of the resin adhesive is 5 to 30% by mass.
The glass woven fabric according to claim 5 , wherein the basis weight is 60 to 1200 g / m ² . The glass woven fabric according to claim 5 or 6 , wherein the resin adhesive is at least one resin selected from the group consisting of acrylic resin, styrene-butadiene rubber, polyester resin, and melamine resin. A cement product comprising the glass woven fabric according to any one of claims 5 to 7 . A cement product comprising the glass fiber strand according to any one of claims 1 to 4 .