JP2013213294A - Glass fiber, manufacturing method of glass paper and glass paper - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a glass fiber allowing fiber opening of a glass chopped strand in white water to easily occur, the thickness to be uniform due to no re-aggregation of a glass fiber monofilament without a complex process, and manufacture of glass paper with no re-coagulation remaining on the surface, and to provide a glass paper-manufacturing method using the glass fiber and glass paper containing this glass fiber.SOLUTION: A glass fiber is obtained by treating with a treatment agent containing an amphoteric surfactant comprising an alkyl group having a carbon number of 8 to 22 and a cationic surfactant and is characterized in that when immersed in white water with a viscosity of 5 cP and agitated at 350 rpm, the fiber opening time is 10 to 60 seconds from the start of agitation and the aggregation start time is 10 minutes or more from the start of agitation.

Description

  The present invention relates to a glass fiber used mainly for the production of glass paper, a method for producing a glass paper using the glass fiber, and a glass paper containing the glass fiber.

  Glass fibers are used in various applications from the viewpoints of economy, availability, and excellent reinforcing properties. A collet that rotates after pulling out molten glass made of glass raw material from a platinum spinning device (bushing) installed in a glass fiber manufacturing apparatus and drawing out hundreds to thousands of glass fiber monofilaments. It is made a wound body by winding it with a twill on it. Thereafter, the glass fiber wound around the wound body is used after being processed into various shapes according to the use and purpose. For example, when glass fiber is used as a reinforcing material for glass fiber reinforced resin (FRP, FRTP), the glass fiber drawn from the wound body is cut into a predetermined length by a cutting blade to form a glass chopped strand. When glass fiber is used as a material for automobile ceiling materials, the glass chopped strand is obtained by uniformly dispersing the glass chopped strand and the binder on the net conveyor and fusing the binder by heating. It is used after combining them into a glass mat shape.

  In addition, when glass fiber is used as a building application such as a base fabric for interior building materials or as an electronic material such as a separator of an electric double layer capacitor, a glass chopped strand is made in the same manner as in the manufacture of pulp paper. Used after making glass paper shape. Since glass paper is excellent in strength and dimensional stability, it may be used in various applications in the future.

  Specifically, the glass paper is manufactured by the following steps. First, a treatment agent is attached to a glass fiber monofilament with a diameter of several μm to several tens of μm drawn from the bushing, and the surface thereof is treated. Next, tens to thousands of glass fiber monofilaments subjected to the surface treatment are converged on glass fiber strands using a gathering shoe. Next, a cake is produced by winding the glass fiber strand around a collet. Next, while unwinding the glass fiber strand from the cake, it is cut into a length of, for example, 3 to 50 mm to produce a glass chod strand. Then, the glass chopped strand is put into white water in which water-soluble polymer, surfactant and the like are dissolved, and the glass chopped strand is stirred using a propeller blade or the like, thereby converting the glass chopped strand into a glass fiber monofilament. Glass paper is manufactured by paper-opening the fiberglass monofilament that has been opened and then drying on a mesh conveyor in the same manner as in the case of manufacturing paper from pulp.

  An important point in manufacturing glass paper is that when glass chopped strands are introduced into white water, glass chopped strands consisting of tens to thousands of glass fiber monofilaments are quickly converted into glass fiber monofilaments. It is opened and the opened glass fiber monofilament does not aggregate again in white water. If the glass chopped strand does not rapidly open the glass fiber monofilament, the thickness of the glass paper will not be uniform, and if the glass fiber monofilament aggregates during papermaking, the aggregated glass fiber monofilament will be a lump Thus, it remains on the surface, making it difficult to produce a glass paper with good quality. Examples of an element that affects the opening property of the glass chopped strand and the cohesiveness of the glass fiber monofilament include a treating agent used for the treatment of the glass fiber monofilament. The treatment agent plays a role of converging the glass fiber monofilaments and adjusting the surface state of the glass fiber monofilament, and the bundling property and the surface state change depending on the components contained in the treatment agent. Depending on the surface state, static electricity is generated on the surface of the glass fiber monofilament, and the glass fiber monofilaments tend to aggregate due to electrostatic force or the like.

  For example, Patent Document 1 discloses that even when glass roving is unwound from a wound body at high speed, fluff is not easily generated in the yarn guide, and even if monofilament is quickly opened in white water, and even if the papermaking speed is increased, it is uniform. As a glass roving suitable for the direct cutting method that can produce a glass paper with a sufficient thickness, the amount of fluff generated when a 3500 m dry glass roving is passed in contact with the surfaces of three brass rods. A glass roving having a number average molecular weight of 10,000 to 1,000,000 is disclosed, wherein the glass roving is 100 mg or less and the opening time in white water is 60 seconds or less. And a sizing agent containing a surfactant are applied, and the adhesion amount of the water-soluble polymer is 0.005 to 0.5% by mass.

  Patent Document 2 also provides a glass fiber sheet for an air filter that has good formation, is imparted with a binder, and has good interlayer strength without binder migration when dried in the neutral papermaking method. For the purpose of, using chopped strand glass fiber having an average fiber diameter of 6 to 20 μm and extra fine glass fiber having an average fiber diameter of 0.3 to 4 μm as main raw material components and dispersing using a betaine amphoteric surfactant After adding an anionic surfactant, adding an anionic polyacrylimide-based tackifier to neutral and wet papermaking, the wet paper is coated with a binder containing a water-soluble paper strength agent having a cationic group. A method characterized by applying a liquid and drying is disclosed.

JP 2004-315345 A Japanese Patent Laid-Open No. 04-298208

  The glass roving disclosed in Patent Document 1 is less likely to generate fluff, and since the bundling agent is easily dissolved in white water, it is easy to open the fiber in white water. Whether the monofilament aggregates again is not examined. Therefore, depending on the characteristics of the water-soluble polymer and the surfactant, the glass fiber monofilament may be aggregated again after opening, making it difficult to produce glass paper with good quality.

  The method for producing a glass fiber sheet disclosed in Patent Document 2 is capable of producing a glass fiber sheet for an air filter having a uniform thickness and good interlayer strength. Since the attachment process is complicated, there is a problem in terms of cost.

  The present invention solves the above-mentioned problems, the glass chopped strands are easily opened in white water, and the glass fiber monofilament does not agglomerate again without going through a complicated process. It is possible to provide a glass fiber that is capable of producing a glass paper that is uniform and has no lumps remaining on the surface, a method for producing a glass paper using the glass fiber, and a glass paper containing the glass fiber. Let it be an issue.

  As a result of intensive studies to solve the above-mentioned problems, the present inventor treated glass fibers with a treatment agent containing a predetermined amphoteric surfactant and a cationic surfactant, thereby producing glass chopped strands in white water. It is found that the glass fiber monofilament does not aggregate again after opening, and the contents thereof are presented here.

  That is, the glass fiber of the present invention is treated with an amphoteric surfactant containing an alkyl group having 8 to 22 carbon atoms and a treating agent containing a cationic surfactant, immersed in white water having a viscosity of 5 cP, and 350 rpm When stirring is performed, the opening time is 10 to 60 seconds from the start of stirring, and the aggregation start time is 10 minutes or more from the start of stirring.

  Further, when the glass fiber of the present invention is immersed in white water having a viscosity of 1 cP and stirred at 350 rpm, the fiber opening time is 5 to 30 seconds from the start of stirring, and the aggregation start time is 5 minutes from the start of stirring. The above is preferable.

  Moreover, it is preferable that the glass fiber of this invention contains 5-40 mass parts of cationic surfactant in the said processing agent with respect to 100 mass parts of amphoteric surfactant content.

  Moreover, it is preferable that the glass fiber of this invention is an ignition loss of 0.01-0.3 mass%.

  The method for producing glass paper of the present invention is characterized in that papermaking is performed with white water having a viscosity of 0.1 to 5 cP using the glass fiber described above.

  The glass paper of this invention contains the glass fiber in any one of the said, It is characterized by the above-mentioned.

  According to the present invention, it is possible to provide glass fibers in which glass chopped strands are easily opened in white water, and the glass fiber monofilaments do not aggregate again without going through a complicated process. Moreover, the glass paper manufacturing method using the glass fiber of the present invention makes it possible to manufacture a high-quality glass paper having a uniform thickness and no lumps remaining on the surface.

  DESCRIPTION OF EMBODIMENTS Hereinafter, embodiments for carrying out the present invention will be described. However, the present invention is not limited to the following embodiments, and is based on ordinary knowledge of a person skilled in the art without departing from the gist of the present invention. It should be understood that modifications and improvements as appropriate to the following embodiments also fall within the scope of the present invention.

  The glass fiber of the present invention is treated with an amphoteric surfactant containing an alkyl group having 8 to 22 carbon atoms and a treating agent containing a cationic surfactant, immersed in white water having a viscosity of 5 cP, and stirred at 350 rpm. The opening time is 10 to 60 seconds from the start of stirring, and the aggregation start time is 10 minutes or more from the start of stirring. The details will be described below.

  The glass fiber of the present invention must be treated with a treatment agent containing an amphoteric surfactant containing an alkyl group having 8 to 22 carbon atoms. An amphoteric surfactant is a surfactant that has both anion and cation groups in one molecule. When dissolved in water, the properties of an anionic surfactant are shown in the alkaline region and the cationic interface in the acidic region. Indicates the nature of the active agent. Examples of amphoteric surfactants include imidazoline-type amphoteric surfactants, amidopropyl betaine-type amphoteric surfactants, sulfobetaine-type amphoteric surfactants, amidoamine oxide-type amphoteric surfactants, and carbobetaine-type amphoteric surfactants. . The amphoteric surfactant contains an alkyl group having 8 to 22 carbon atoms. The alkyl group is a hydrophobic group, and the chain length of the alkyl group is one of the factors that determine the hydrophilicity / hydrophobicity of the amphoteric surfactant. In other words, if the carbon chain of the alkyl group is short, the HLB value becomes high (becomes hydrophilic), and the amphoteric surfactant tends to aggregate the opened glass fiber monofilament without remaining on the glass fiber surface. If the carbon chain is long, the HLB value becomes low (becomes hydrophobic), and the openability of the glass chopped strands deteriorates. Therefore, the amphoteric surfactant of the present invention takes into account these balances, The number is 8-22. When the alkyl group has 7 or less carbon atoms, the aggregation resistance is poor, that is, the glass fiber monofilament is aggregated again, which is not preferable. Moreover, when the carbon number of the alkyl group is 23 or more, opening of the glass chopped strand may be delayed, which is not preferable. More preferably, the alkyl group has 10 to 16 carbon atoms. The alkyl group having 8 to 22 carbon atoms may be contained in the amphoteric surfactant, and may be contained in two or more. However, the number of alkyl groups having 8 to 22 carbon atoms is preferably one in the amphoteric surfactant because the dispersibility of the glass fiber monofilament in white water is stable. The alkyl group may be linear or branched. However, it is preferable that the alkyl group having 8 to 22 carbon atoms is linear because the dispersibility of the glass fiber monofilament is improved.

  Examples of the alkyl group having 8 to 22 carbon atoms include linear alkyl groups such as N-octyl group, N-decyl group, N-dodecyl group, N-tetradecyl group, N-hexadecyl group, and tert-octyl. And a branched alkyl group such as a group, a tert-decyl group, an isooctyl group, and an isodecyl group.

  Examples of the amphoteric surfactant containing an alkyl group having 8 to 22 carbon atoms include 2-alkyl-N-carboxymethylimidazolinium betaine, 2-alkyl-N-carboxyethylimidazolinium betaine, and 2-undecyl-N, N. , N- (hydroxyethylcarboxymethyl) -2-imidazoline sodium, 2-cocoyl-2-imidazolinium hydroxide-1-carboxyethyloxy disodium salt, etc., imidazoline-type amphoteric surfactant, amidepropyl laurate Betaine, laurylamidopropyl betaine, stearic acid amidopropyl betaine, oleic acid amidopropyl betaine, palm oil fatty acid amidopropyl betaine, palm oil fatty acid amidopropyl betaine, ricinoleic acid amidopropyl betaine, isostearic acid amide Amidopropyl betaine-type amphoteric surfactants such as propyldimethylaminoacetic acid betaine, myristic acid amidopropyl betaine, lauric acid amidopropyl hydroxysulfobetaine, lauryl hydroxysulfobetaine, coconut oil fatty acid hydroxysulfobetaine, myristic acid amidopropyl hydroxysulfone Betaine, oleamidopropylhydroxysulfobetaine, laurylsulfobetaine, cocosulfobetaine, cocamidopropylhydroxysultain, N-acylamidopropyl-N, N′-dimethyl-N′-β-hydroxypropylammoniosulfobetaine, N , N-dialkyl-N, N-bis (polyoxyethylenesulfuric acid) ammoniobetaine, etc., sulfobetaine-type amphoteric surfactants, lauric acid amidopropyldimethylamino Amidoamine oxide-type amphoteric surfactants such as oxides, carbobetaine-type amphoteric surfactants such as stearyldimethylaminoacetic acid betaine, alkyldimethylaminoacetic acid betaine, fatty acid amidopropyldimethylaminoacetic acid betaine, and alkyldihydroxyethylaminoacetic acid betaine It is done. These amphoteric surfactants may be used alone or in combination of two or more.

  The content of the amphoteric surfactant containing an alkyl group having 8 to 22 carbon atoms is preferably 0.2 to 3.0% by mass with respect to the total amount of the processing agent. When the content of the amphoteric surfactant containing an alkyl group having 8 to 22 carbon atoms is less than 0.2% by mass with respect to the total amount of the treatment agent, the content of the amphoteric surfactant is small, so that the effects of the present invention cannot be exhibited sufficiently. There is a fear. On the other hand, if the content of the amphoteric surfactant containing an alkyl group having 8 to 22 carbon atoms is larger than 3.0% by mass relative to the total amount of the treatment agent, the slipperiness of the glass fiber becomes too strong. This is not preferable because it is difficult to maintain the shape. The more preferable content of the amphoteric surfactant containing an alkyl group having 8 to 22 carbon atoms is 0.5 to 2.5% by mass with respect to the total amount of the treatment agent.

  The glass fiber of the present invention must be treated with a treating agent containing a cationic surfactant. The cationic surfactant refers to a surfactant that is ionized in water (white water) to become an organic cation, and any cationic surfactant can be applied. Examples of cationic surfactants include behenyl trimethyl ammonium chloride, behenyl trimethyl ammonium methosulfate, behentrimonium methosulfate, stearyl trimethyl ammonium chloride, stearyl trimethyl ammonium bromide, cetyl trimethyl ammonium chloride, cetyl trimethyl ammonium bromide, etc. Mono-chain alkyloxyalkyl ammoniums such as chain alkyl ammoniums, stearyloxypropyltrimethylammonium chloride, 3-docosyloxy-2-hydroxypropyltrimethylammonium chloride, docosyloxypropyltrimethylammonium chloride, distearyldimethylammonium chloride, chloride Dicetyldimethylammonium, dicocoyldimethylammonium chloride, etc. Palm oil fatty acid esters such as di-long-chain alkyl ammoniums, alkylamine oxides such as benzalkonium chloride, laurylamine oxide, N-coconut oil fatty acid acyl L-arginine ethyl DL-pyrrolidone carboxylate, cation And fatty acid amides. These cationic surfactants may be used alone or in combination of two or more.

  When the glass fiber of the present invention is immersed in white water having a viscosity of 5 cP and stirred at 350 rpm, the fiber opening time is 10 to 60 seconds from the start of stirring, and the aggregation start time is 10 minutes or more from the start of stirring. is there.

  White water is white water generally used in a papermaking process for making glass fiber, synthetic fiber, and pulp, and has a viscosity of 5 cP. The viscosity of white water can be measured by a known method, and can be measured by a capillary viscometer, a falling ball viscometer, a rotational viscometer or the like described in JIS Z8803 (2011). In the present invention, the viscosity was measured with a B-type rotational viscometer (manufactured by Tokyo Keiki Co., Ltd.). Then, white water having a viscosity of 5 cP is put into a beaker, stirred at 350 rpm, and glass chopped strands are put into the beaker. As an input amount of the glass chopped strand, it is preferable that the glass chopped strand is 2 to 5 g with respect to 500 ml of white water. Moreover, it is preferable that glass chopped strand is 3-50 mm in length. When the length of the glass chopped strand is shorter than 3 mm, it is not preferable because it is difficult to visually check the opening state of the glass chopped strand. Further, if the length of the glass chopped strand is longer than 50 mm, the glass chopped strand is entangled with the stirring rod, and it is not possible to measure the exact opening time. The “x seconds from the start of stirring” refers to the number of seconds from the time when the glass chopped strands are poured into white water and immersed in a beaker that has been previously stirred. In addition, when stirring is started after the glass chopped strand is introduced, the opening time varies depending on the water immersion time before stirring, and it may be difficult to accurately measure the opening time. Judgment whether the glass chopped strand has been opened or not is made visually. Specifically, the object is placed at a position symmetrical to the observer centering on the position of the beaker, and when the glass chopped strand is opened, the white water in the beaker becomes cloudy and the object is visible to the observer. The lost time is defined as the opening time. The agglomeration start time is also visually observed in the same manner as the opening time. Specifically, as described above, when the glass chopped strands are opened, white water becomes cloudy and the object cannot be seen, but the opened glass fiber monofilaments aggregate to increase the transparency of the white water again. Come. The object can be observed again. The time when the object can be observed is defined as the aggregation start time.

  When the fiberglass opening time is less than 10 seconds from the start of stirring, the fiberglass monofilament does not spread throughout the papermaking process because the fiberglass fibers are opened immediately after the introduction of the glass chopped strands. Glass paper cannot be produced, which is not preferable. On the other hand, when the fiber opening time is longer than 60 seconds from the start of stirring, some glass chopped strands remain in an unopened state, and massive glass fibers remain as lumps on the surface of the paper-made glass paper. Therefore, it is not preferable. A more preferable opening time is 10 to 40 seconds from the start of stirring.

  In addition, when the aggregation start time is less than 10 minutes from the start of stirring, the glass fiber monofilaments opened during the paper making process are aggregated again, and remain on the surface of the glass paper during paper making. It is not preferable. A more preferable aggregation start time is 20 minutes or more from the start of stirring.

  Since the glass surface is negatively charged, it is considered that the cationic surfactant is stably adhered to the surface of the glass fiber monofilament treated with the treating agent containing the cationic surfactant due to the positive charge of the cation. However, since the hydrophobic groups are regularly arranged so that the hydrophobic groups are directed outward, the permeability of white water to the glass fiber strand is deteriorated and the opening time is delayed. Therefore, when the amphoteric surfactant is also included in the treatment agent, the negative charge on the glass surface in white water and the cation and anion of the amphoteric surfactant are brought into a dynamic equilibrium state, and the white water permeability is kept good. However, it is considered that aggregation of the glass fiber monofilament can be suppressed.

  Further, when immersed in white water having a viscosity of 1 cP and stirred at 350 rpm, if the opening time is 5 to 30 seconds from the start of stirring and the aggregation start time is 5 minutes or more from the start of stirring, the viscosity is low. Even when white water is used, the glass chopped strands can be opened in an appropriate time, and there is no risk of the glass fiber monofilament agglomerating in a short time, making it possible to handle various types of white water. Further preferred.

  Further, since the viscosity of white water has a proportional correlation with the opening time and the aggregation start time, when the white water is immersed in white water having a viscosity of 5 cP and stirred at 350 rpm, the opening time is 10 to 10 from the start of stirring. 60 seconds, aggregation start time is 10 minutes or more from the start of stirring, and when immersed in white water having a viscosity of 1 cP and stirred at 350 rpm, the opening time is 5 to 30 seconds from the start of stirring. Yes, if the agglomeration start time is 5 minutes or more from the start of stirring, even when glass paper is produced using high-viscosity white water, the fiber opening time is less likely to be excessively long and sufficient for the start of agglomeration. Since time is secured, there is little risk of lumps remaining and non-uniform thickness.

  Moreover, it is preferable that 5-40 mass parts processing agent contains a cationic surfactant with respect to 100 mass parts of amphoteric surfactant content.

  As described above, when the cationic surfactant and the amphoteric surfactant are contained in the treatment agent, both the fiber opening property and the aggregation suppression can be achieved. When the content of the cationic surfactant and the amphoteric surfactant is contained in the treatment agent for 5 to 40 parts by mass of the cationic surfactant with respect to 100 parts by mass of the amphoteric surfactant, the amphoteric surfactant is obtained. It is preferable because deterioration of the opening property of the glass chopped strand due to excess and aggregation of the glass fiber monofilament due to excessive cationic surfactant can be efficiently suppressed. When the amount of the cationic surfactant is less than 5 parts by mass relative to 100 parts by mass of the amphoteric surfactant, the cationic surfactant is less likely to adhere to the glass surface, and the glass surface is negatively charged. The fiber monofilament is liable to aggregate again, which is not preferable. On the other hand, when the cationic surfactant is larger than 40 parts by mass with respect to 100 parts by mass of the amphoteric surfactant, the amount of cationic surfactant that is hardly soluble in white water becomes excessive, so that the glass chopped strand is difficult to open. This is not preferable. The content of the cationic surfactant and the amphoteric surfactant is more preferably 10 to 30 parts by mass of the cationic surfactant with respect to 100 parts by mass of the amphoteric surfactant, and more preferably of the amphoteric surfactant. A cationic surfactant is 15-25 mass parts with respect to 100 mass parts of content.

  In addition to the amphoteric surfactant and the cationic surfactant, the treating agent preferably contains a silane coupling agent for the purpose of protecting the glass fiber surface. As the silane coupling agent, aminosilane, epoxy silane, vinyl silane, acrylic silane, chlorosilane, mercaptosilane, and ureidosilane can be used. Among these, γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β-, which has improved boiling characteristics and is less colored even when added, is added. (Aminoethyl) -N′-β- (aminoethyl) -γ-aminopropyltriethoxysilane, γ-anilinopropyltrimethoxysilane, and 3-glycidoxypropyltrimethoxysilane are preferable. These silane coupling agents may be used alone or in combination of two or more.

  Besides, urethane resin, bisphenol A novolak type epoxy resin, bisphenol F novolak type epoxy resin, biphenyl type bifunctional epoxy resin, biphenyl modified novolak type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, naphthol -Cresol co-condensed novolak epoxy resin, naphthol-Phenol co-condensed novolac epoxy resin, dicyclopentadiene-phenol addition reaction epoxy resin, triphenylmethane epoxy resin, phenol novolac epoxy resin Cresol novolac epoxy resin, tetraphenyl Epoxy resins such as ethane type epoxy resin and naphthol novolac type epoxy resin, acrylic ester polymer, acrylic ester-vinyl acetate Other binders such as polymers, acrylic resins such as acrylate-styrene copolymers, fatty acid amides, and quaternary ammonium salts, synthetic alcohols, natural alcohols, fatty acid esters Nonionic surfactants, neutralizing agents such as ammonia and sodium hydroxide, and antistatic agents can be included in appropriate amounts, and the mixing ratio of each component can be determined as necessary. That's fine.

  Also, amphoteric surfactants and cationic surfactants are preferable because they can be easily applied to glass fibers by dissolving them in a solvent. Examples of the solvent include water, toluene, xylene, methyl ethyl ketone, phenyl ether derivatives, tetrahydrofuran (THF), and the like, and water that is difficult to volatilize and difficult to ignite is preferable.

  The glass fiber of the present invention is produced by the following production method. First, the molten glass is drawn out from a bushing having several hundred to several thousand heat-resistant nozzles, and then cooled to obtain a glass fiber monofilament. Next, a processing agent is applied to the glass fiber monofilament with an applicator or other application device, and several hundred to several thousand glass fiber monofilaments are drawn to form a glass fiber strand, and then the glass fiber strand is turned into a collet that rotates. A winding body is obtained by winding while twilling.

  And after setting it as a wound body, it is set as the glass chopped strand which pulled out the glass fiber strand from the wound body and cut | disconnected to predetermined length. In addition, you may have the drying process which dries the water | moisture content adhering to glass fiber, and also winds up the glass fiber strand composite body which combined several glass fiber strands, produces roving, and from roving A glass chopped strand obtained by cutting the drawn glass fiber strand composite may be used. Various drying means may be used as the drying step, and a plurality of drying means may be used in combination as necessary. Examples of such drying means include dielectric heating, hot air heating, and radiant heating.

  The properties of the glass fiber are also determined by the glass composition. As the glass composition of the glass fiber of the present invention, E glass (alkali content 2.0% or less), A glass (alkali-containing glass) AR glass (alkali-resistant glass composition) , C glass (acid-resistant alkali lime-containing glass composition), D glass (composition realizing low dielectric constant), S glass (composition realizing high strength and high elastic modulus), T glass (high strength, high elastic modulus) NE glass (a composition that realizes a low dielectric constant and a low dielectric loss tangent), and H glass (a composition that realizes a high dielectric constant) can be applied.

  The glass fiber of the present invention may have various cross-sectional shapes such as a circle, an ellipse, a rectangle, a mayu shape, a polygonal shape, a circle shape, and a star shape, as the yarn cross-sectional shape orthogonal to the longitudinal direction. In order to obtain such a modified cross-sectional shape, it is only necessary to cool the glass fiber in which the shape of the heat-resistant nozzle during spinning is appropriately deformed.

  The glass fiber of the present invention preferably has a loss on ignition of 0.01 to 0.3% by mass.

  The ignition loss can be measured according to JIS R 3420 (2006). When the loss on ignition is less than 0.01% by mass, it is difficult to bundle the glass fiber monofilaments into one glass fiber strand, and the handling property of the glass fibers may be deteriorated. On the other hand, when the ignition loss is larger than 0.3% by mass, the convergence is good, but the slipperiness of the glass fiber becomes too strong, so that it is difficult to maintain the shape of the wound body, which is not preferable in handling. More preferable ignition loss is 0.04 to 0.25% by mass, and more preferably 0.06 to 0.1% by mass.

  The method for producing glass paper of the present invention is characterized in that papermaking is performed with white water having a viscosity of 1 to 10 cP using the glass fiber.

  Specifically, it is produced by dispersing glass chopped strands obtained by cutting the glass fibers into 3 to 50 mm in white water, then making paper with a paper machine, and drying the paper. By using white water having a viscosity of 1 to 10 cP for papermaking, the opening time of the glass chopped strand is in an appropriate range, and the aggregation start time of the glass fiber monofilament is sufficiently long. As a result, it is possible to produce a glass paper having a uniform thickness and less occurrence of lumps.

  The drying and curing step is usually performed at 100 to 250 ° C., more preferably at 150 to 200 ° C. for several seconds to several minutes with a hot air dryer or drum dryer, but by infrared, far infrared, or high frequency heating. Or a combination thereof.

  The glass paper of this invention contains the said glass fiber, It is characterized by the above-mentioned.

  By containing the glass fiber, a glass paper having a uniform thickness and less generation of lumps can be obtained.

  Moreover, the glass paper of this invention may contain glass fiber other than this invention, a synthetic fiber, carbon fiber, a pulp, etc. in a suitable quantity, as long as the performance of this invention is not impaired.

  Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited thereto.

[Production of treatment agent]
Example 1
The treatment agent of Example 1 is 0.24% by mass of a cationic fatty acid amide (tetraethylenepentamine stearate condensate Sofnon HG-180 (manufactured by Toho Chemical Industry Co., Ltd.)), which is a cationic surfactant, and an amphoteric surfactant. 0.83% by mass of laurylamidopropylbetaine (Marpovister LAP (manufactured by Matsumoto Yushi Seiyaku Co., Ltd.)) as the agent, 3-glycidoxypropyltrimethoxysilane (SH6040 (Toray Dow Corning Co., Ltd.) as the silane coupling agent Manufactured)) is prepared by mixing homogeneously with ion-exchanged water so that the content is 0.23% by mass. The ratio of cationic surfactant / amphoteric surfactant × 100 is 28.9%.

(Example 2)
The treating agent of Example 2 was the same as that of Example 1 except that stearyldimethylaminoacetic acid betaine (Marpovister MS (manufactured by Matsumoto Yushi Seiyaku Co., Ltd.)) was used instead of laurylamidopropylbetaine.

(Example 3)
The treating agent of Example 3 is the same as that of Example 3 except that the cationic fatty acid amide is 0.48% by mass, laurylamidopropylbetaine is 1.66% by mass, and 3-glycidoxypropyltrimethoxysilane is 0% by mass. Same as 1.

Example 4
The treating agent of Example 4 was the same as that of Example 3 except that stearyldimethylaminoacetic acid betaine was used in place of laurylamidopropylbetaine.

(Example 5)
The treating agent of Example 5 is the same treating agent as that of Example 2.

(Example 6)
The treatment agent of Example 6 is 0.12% by mass of a cationic fatty acid amide, a polyethylene glycol type nonionic surfactant (polyoxyethylene lauryl ether score roll 100 (manufactured by Kao Corporation)) which is a nonionic surfactant. It was prepared by intimately mixing in ion-exchanged water so that 0.12% by mass, laurylamidopropylbetaine was 0.83% by mass, and 3-glycidoxypropyltrimethoxysilane was 0.23% by mass. . The ratio of cationic surfactant / amphoteric surfactant × 100 is 14.5%.

(Example 7)
The treating agent of Example 7 was the same as that of Example 6 except that stearyldimethylaminoacetic acid betaine was used in place of laurylamidopropylbetaine.

(Example 8)
The treating agent of Example 8 is 0.24% by mass of cationic fatty acid amide, 0.4% by mass of laurylamidopropylbetaine, and 0% by mass of 3-glycidoxypropyltrimethoxysilane, and is a cationic surfactant. / Same as Example 6 except that the amphoteric surfactant × 100 is 60%.

Example 9
The treating agent of Example 9 is the same treating agent as Example 6.

(Example 10)
The treating agent of Example 10 is the same treating agent as Example 8.

(Comparative Example 1)
The treatment agent of Comparative Example 1 was 0.61% by mass of cationic fatty acid amide, 0.46% by mass of polyethylene glycol type nonionic surfactant, and 0.23% by mass of 3-glycidoxypropyltrimethoxysilane. Thus, it is prepared by mixing homogeneously with ion-exchanged water.

(Comparative Example 2)
The treating agent of Comparative Example 2 is the same as Comparative Example 1 except that the cationic fatty acid amide is 0.2% by mass and the polyethylene glycol type nonionic surfactant is 0.87% by mass.

(Comparative Example 3)
The treating agent of Comparative Example 3 is the same as Comparative Example 1 except that the cationic fatty acid amide is 0.92% by mass and the polyethylene glycol type nonionic surfactant is 0.15% by mass.

(Comparative Example 4)
The treating agent of Comparative Example 4 was 0.05% by mass of a cationic fatty acid amide, 0.04% by mass of a polyethylene glycol type nonionic surfactant, and 0.02% by mass of 3-glycidoxypropyltrimethoxysilane. Thus, it is prepared by mixing homogeneously with ion-exchanged water.

(Comparative Example 5)
The treating agent of Comparative Example 5 was prepared by intimately mixing in ion-exchanged water so that laurylamidopropylbetaine was 0.1% by mass and 3-glycidoxypropyltrimethoxysilane was 0.02% by mass. It is. In addition, cationic surfactant / amphoteric surfactant × 100 is 0%.

[Production of glass chopped strands]
A molten glass having an E glass composition homogeneously melted in a glass melting furnace is continuously drawn out from a heat-resistant bushing having tens to thousands of nozzles, and is obtained on the surface of the obtained glass fiber monofilament having an average diameter of 10 μm. The above-mentioned treatment agent was applied while changing the rotation speed of the applicator roller so that the ignition loss described in Tables 1 and 2 described later was obtained. Thereafter, 5000 glass fiber monofilaments coated with the treatment agent were gathered by a gathering shoe to form glass fiber strands, which were wound on a paper tube to form a wound body. Next, a glass fiber strand was drawn from the wound body, and was cut using a cutting device so as to have a length of 13 mm by a glass fiber cutting device, thereby obtaining a glass chopped strand.

[Measurement of opening time and aggregation start time]
500 g of white water was put into a beaker, white water was stirred at 350 rpm using a propeller type blade having a blade diameter of 70 mm, and 3 g of glass chopped strand was put therein. As described above, the time from the time of flooding was defined as the opening time. In addition to the dispersant, in Examples 1 to 4, 6 to 8 and Comparative Examples 1 to 5, the viscosity of white water was adjusted to 5 cP by adding a thickener. Using this white water, the opening time and aggregation start time were measured. In Examples 5, 9, and 10, the opening time and aggregation start time were measured using white water having a viscosity of about 1 cP.

[Thickness uniformity of glass paper]
A glass chopped strand was made to produce a 30 mm × 30 mm glass paper, and the thickness of the glass paper after the production was visually confirmed. By visual observation, when the difference between the thickest part and the thinnest part was 1 mm or more, it was evaluated as x, and when the difference between the thickest part and the thinnest part was 1 mm or less, it was evaluated as ◯. The white water viscosity conditions used for papermaking were the same as those used for the measurement of the opening time and the aggregation start time described above.

[Presence or absence of glass paper waste]
The surface of the previously described 30 mm × 30 mm glass paper was visually confirmed. If the glass fiber monofilament aggregates and there is a part that appears whiter than the periphery, and the diameter of the part is 3 mm or more, it is evaluated as x, and the glass fiber monofilament aggregates and there is a part that appears whiter than the periphery When it was not, or even if it existed, it was evaluated as ◯ when the diameter of the part was less than 3 mm.

  Tables 1 and 2 show the treatment agent composition, white water viscosity, loss on ignition, opening time, aggregation start time, glass paper thickness uniformity, and glass paper dullness in each example and comparative example. The presence or absence is described.

  As is clear from Tables 1 and 2, in Examples 1 to 10, glass paper having a uniform thickness and no lumps was obtained. On the other hand, in Comparative Examples 1 and 2, agglomeration occurred easily and a lot of lumps occurred. In Comparative Example 3, since the glass fiber was not opened, the thickness was not uniform, and many holes were observed in the glass paper. Moreover, the glass fiber which is not opened existed as a waste. In Comparative Examples 4 and 5, since the fiber opening was too early, the glass fiber did not spread as a whole, and aggregation occurred easily, resulting in many lumps.

Claims (6)

  Opening time when treated with an amphoteric surfactant containing an alkyl group having 8 to 22 carbon atoms and a treating agent containing a cationic surfactant, soaked in white water with a viscosity of 5 cP, and stirred at 350 rpm However, it is 10 to 60 seconds from the start of stirring, and the aggregation start time is 10 minutes or more from the start of stirring.   When immersed in white water having a viscosity of 1 cP and stirred at 350 rpm, the opening time is 5 to 30 seconds from the start of stirring, and the aggregation start time is 5 minutes or more from the start of stirring. Item 2. The glass fiber according to Item 1.   The glass fiber according to claim 1 or 2, wherein the cationic surfactant is contained in the treatment agent in an amount of 5 to 40 parts by mass with respect to 100 parts by mass of the amphoteric surfactant.   The glass fiber according to any one of claims 1 to 3, wherein the loss on ignition is 0.01 to 0.3% by mass. It is a manufacturing method of the glass paper using the glass fiber as described in any one of Claim 1 to 4, Comprising:
A method for producing glass paper, which comprises making paper with white water having a viscosity of 1 to 10 cP.   A glass paper comprising the glass fiber according to any one of claims 1 to 4.